Note: Descriptions are shown in the official language in which they were submitted.
2 ~ 2 2 ~
SPE CIFICAT ION ~ ;
Polyvinyl chloride resins, properly formulated, can
be processed by standard plastics processing techniques
(including calendering, extrusion, injection and compression
molding, blow molding, rotational molding, slush and dip ~ -
molding, solution casting, electrostatic spray and fluidized bed ~` `
coating), to form awide variety of end products, including
plastic sheeting, furniture for both indoor and outdoor use,
house sidings and other building components, and motor
vehicle components, such as dashboards, seat coverings, floor
mats, door panels, arm and head rests, body side moldings,
window trim moldings, seat corners and head liners, door
and window knobs, and crash dashboards.
Compounding components such as plasticizers,
~5 stabilizers, lubricants, impact modifiers, processing aids,
fillers, colorants, antistatic agents, tackifiers, flame
~, ~
retardants, fungicides, antiblocking agents, etcO make the
processing into these various end use components feasible -~
without noticeable deterioration of the polymer. In the absence ;
20 o such components, the resin would degrade during heat
processing, liberating hydrogen chloride, discolor and become
brittle, and stick to the equipment. `~
This success in stabilizing the polymer during heat
. .. .
processing has only been achieved after many years of
25 development of the heat stabilizing systems that are now
~ ',. '
2~22~3~
widely accepted as conventional. However, as Norman L
Perry, Chapter 17, Encyclopedia of PVC, Volume 2,
(Marcel Dekker, Inc. New York and Basel, 1977) has noted
at page 873, satisfactoryprotection against discoloration
5 under processing temperature conditions does not necessarily
ensure protection against discoloration thereafter when exposed ~ ~;
to moderately hot temperatures over a long period~
In fact, protection against discoloration at moderate
temperatures over long periods is a particular problem with
motor vehicle components. Depending upon their location ~ ~
in the vehicle, they may be exposed to varying amounts of ~ `
light, and also different rather high (above atmospheric)
temperatures in use, and these differences can degrade motor `
vehicle components at differing rates. While normally it can
15 be expected that the heat stabilizer systems capable of
protecting the resin against degradation and discoloration
during heat processing will not be completely consumed
during such processing, and can be expected to contribute to
stabilization following the processing, in fact the available
20 heat stabilizers normally used are not sufficiently effective to
prevent discoloration of motor vehicle components arising from
exposure to moderate temperatures in use. It is a problem
that,failing a solution, the automobile industry has had to live
with
~ ~2 ~
Struber Theory and Practice of Vinyl Compounding
(a publication OI Argus Chemical Corporation, 1968)
recommends specific heat stabilizer systems for use in
automotive upholstery and flooring compounds, to provide
5 moderate temperature aging stability in use. The organotin
compounds, both mercaptides and maleate types, are effective,
but relatively expensive, and also usually impart an objectionable
odor that precludes their use~ Some barium/cadmium fatty `
acid salt stabilizers with high cadmium content are also
10 effective. Struber notes that generally those compounds
which tend to discolor most rapidly under moderate
temperature conditions have received the greatest exposure to
high temperature processing, making it quite clear that reliance ~
is being placed on the residual amounts of heat stabilizers that `
are present in the composition after heat processing. The ~ ; ;
. ... .
higher temperature heat processing conditions evidently have
consumed a larger proportion of such stabilizers,accounting ~ -
for their lesser stability and shorter life in useO However,~ -
simply increasing the amounts of heat stabilizers employed, ~;
20 even of the recommended types, has not been successful in
resolving the moderate temperature ageing stability problem,
particularly in motor vehicle components, and it is apparent ~
that something more is needed~ ~-
In accordance with the present invention, this something ;
25 more is provided in the form of a ~ rdiketone. The invention
. .- .
, . ~ . ~ ,.
3 ~ `
"','',
~:'..'.'...'.'.'
~ ~.;..
2~22~3~ -
employs a conventional heat stabilizer system, particularly ~ `
and preferably one of the barium/cadmium organic acid salt ~ ;
types, in a sufficient amount to provide heat stability during
heat processing, with the B-diketone serving the function of
5 providing resistance to discoloration at moderate temperatures
after the composition has been put in the form of the motor
vehicle component, by any appropriate forming or shaping ~ ~
procedure. Thus, the B-diketone is not serving the function ~-
of a heat processing stabilizer, in the composition of the
present invention, and indeed it has been demonstrated that
even in the absence of the B-diketone, the compositions are
stable under conventional heat processing conditions. The
B-diketone provides only the desired moderate temperature
stability thereafter, and this whether or not residues of the ;
heat stabilizers remain in the shaped product.
Ebel, Burger and Herrle, German patent No. 1, 073, 201,
UO S~ patent NoO 3, 001, 970, disclose that polyvinyl chloride ;
or polyvinylidene chloride when combined with up to about
10% of a dibenzoylmethane of the formula~
R
o/CO\ ~ CO~
in which R is hydrogen or a hydroxyl residue, display an
improved resistance to deterioration when exposed to light.
25 Additional substituents can be present on one or both benzene
;'.'~'.;''''.'
`''" ',','.'
4 ~ -
-'''.~'''
2 ~
,`.
rings that do not impart water solubility. Dibenzoylmethane,
-oxydibenzoylmethane, 2-oxy- 5-ch lorodibenzoylmethane,
and 2-oxy-5-methyldibenzoylmethane, are mentioned as
examples~ In Example 1, it is furthler demonstrated that the
5 dibenzoylmethane also improves resistance to deterioration
at temperatures as high as 160C. These results are obtained ~ ;
with polyvinyl chloride, polyvinylidene chloride, and copolymers
of vinylidene chloride and vinyl chloride with other copolymerizable
monom ers.
Crochemore and Gay, U.S. patent No. 4, 102, 839, `
seemingly unaware of the contribution of the Ebel et al patent,
propose compositions for stabilizing vinyl chloride polymers
against thermodegradation composed of a divalent metal salt ;
of an organic carboxylic àcid, in combination with a ~-diketone
15 or a B ketoaldehyde. The latter has the formula:
R l-CO--CHRz--CO-R 3 ' , ::
in which each of Rl and R3, which may be the same or different,
represent a linear or branched alkyl or alkenyl radical having
from 1 to 36 carbon atoms, an aralkyl radical having from
20 7 to 36 carbon a.toms or an aryl or cycloaliphatic radical having
less than 14 carbon atoms, said cycloaliphatic radical optionally
containing one or more carbon-carbon double bonds, the aliphatic ; `
chains oE said radicals optionally containing one ~
O . .~
25 ~, --C~} radical; one of Rl or R3 can represent a hydrogen `~
' '. '.~ `.''.
2~2~
atom; R2 represents a hydrogen atom~ a radical of the formula
~RI, or -CO~R4, wherein R4 represents an aLkyl radical
having from 1 to 36 carbon atoms or cm aryl radical if Rl and R3
are not aromatic, or a radical of the :Eormula~
/ C~R
--CHR4--CH
C~R3
wherein Rl~ R3 and Rg are as defined above;
or R1 and R2 together represent a divalent radical as
an aLkylene radical having from 1 to 12 carbon atoms or a
cyclo aLkylene radical having less than 14 carbon atoms, these `:
radicals can be substituted by an aliphatic radical having from
1 to 18 carbon atoms;
in R" R2 and R3 the carbon atoms adjacent the indicated
carbonyl groups are not doubly bonded to carbon atom and no :
more than one of said carbon atom is contained in an aromatic
ring.
The R, ~nd R3 substituents may be substituted with a
member selected from the group consisting of halo, aryl or
cycloaliphatic groups having less than 14 carbon atoms, which . ..
~ . .
aliphatic moieties may include ~, -COO- or -C~ linkages
within their chains. ~ `.
These stabilizer combinations are used to impart
resistance to the high temperatures of 180 to 200C undergone
by the polymer during the manufacture of various shaped articles ~ -
. ~, .... ...
6 -
...................................................................... ..... -. - . -
~:".'' '`'''.
2 ~
by molding, extrusion and plastic processes. These processes - -
require high temperatures in order to bring the polymer to a
sufficiently soft state, and the degradation in question occurs
at these processing temperatures. Accordingly, the working
5 Examples test the effectiveness of the stabilizer combinations
, -.
by the usual oven heat test as 10 x 20 mm test samples cut
from sheets prepared by calendering at 180C. The results
show that in the absence of the B-diketone the compositions
have very poor heat stability under the test conditions.
Gay U.S. patent NoO 4, 123, 399 discloses similar ` ;
stabilizer compositions containing a pair of organic acid salts ;
of calcium and zinc, a polyol, and a ~-diketone of like formula
to No. 4,102, 839, ~he working Examples~of the Gay patent `~
also demonstrate the important contribution of the ~-diketone ; `;
to heat stability during high temperature processing of the ~ ~
polymer chloride resin composition. ~;
- ~ ~
Minagawa, Sekiguchi and Nakazawa U.S. patent
NoO 4, 221, 687 provides anti-yellowing additives for
environmentally acceptable stabilized vinyl chloride polymer ~;
20 compositions from which arsenic, cadmium, lead, mercury and
~ ,
thallium are substantially excluded, comprising at least one
basic inorganic compound of lithium, sodium, potassium, - -
magnesium, calcium, strontium, barium, zinc, titanium,
aluminum, zirconium or tin, and a 1, 3-diketone compound `;- -;
25 represented by the formula~
": '
'~22~
".,.~ ~ .
M(R-C--CR'-C-R")n ~: ~
O O ~
in which R is a hydrocarbon group having 1 to 18 carbon atoms,
R' is a hydrogen atom, an acyl group R"'~, or a hydrocarbon
O
group having 1 to 18 carbon atoms, R' is a hydrogen atom or
a hydrocarbon group having 1 to 18 carbon atoms, M is a
hydrogen or one of the metals lithium, sodium, potassium,~ ~ -
magnesium, calcium, strontium, barium, zinc, aluminum :
10 and antimony9 and n is the valence of the metal from 1 to 3
Minagawa, Sekiguchi and Nakazawa U.S. patent
NoO 4, 244, 848 provide environmentally acceptable stabilizer
compositions for enhancing the resistance to deterioration ~: . .. `
upon heating at 175C of a vinyl chloride polymer *om which ~.`
lead, cadmium, mercury, thallium and arsenic are
substantially excluded, comprising at least one zinc, alkali ~ ;
. . .. . .;
metal or alkaline earth metal organic phosphate ester salt .
and at least one ~-diketone compound having from 5 to about
30 carbon atoms, which is a cyclic or open chain ~-dikelone, : ~-
or a æinc, alkali metal or alkaline earth metal salt thereofO . ~
Ito, Murnajiri, Kimura and Sekiguchi U.S~ patent ` -.
No. 4, 252, 698 provide anti-yellowing additives for
environmentally acceptable stabilized vinyl chloride polymer
compositions from which arsenic, beryllium, cadmium, lead,
mercury, and thallium are substantially excluded, comprising
~ .~ .....
:`',~'~.,."''".
., .... ~
:'- .", .,
at least one overbased sulfonate or phenolate compound of ~.
lithium, sodium, potassium, magnesium, calcium, strontium,
barium, zinc, titanium, aluminum, zirconium, or tin, and a ~ .
1, 3-diketone compound having 5 to 30 carbon atoms, which is ;:
a cyclic or open-chain 1, 3-diketone or a lithium, sodium, ; ~
potassium, magnesium, calcium, strontium, barium, zinc, -~ ~;
aluminum, tin or zirconium salt thereof. ; ~ ~
Minagawa, Nakahara and Kitsukawa U. S. patent - ~:
NOn 4, 282,141 provide additive compositions for improving ` :
the color stability of vinyl chloride polymers stabilized with ~ .
environmentally acceptable stabilizers comprising a 1, 3- ~`
diketone or a sodium, potassium, lithium, magnesium, barium,
calcium, tin or strontium salt thereof and an organic phosphite ` ;
having the formula ;~
R 1 ~ .
OR6 ;
Ra~ ORs
wherein R1 is a phenyl, cycloalkyl, t-butyl, or t-amyl group, .- --
R2 and R3 are each a hydrogen atom or phenyl, cycloalkyl, or
an alkyl group having one to five carbon atoms, R4 is a hydrogen . -: i
atom or a methyl group, and each of R5 and R6 independently is
a hydrogen atom, an aLkyl group having 1 to 18 carbon atoms, - i
a cycloalkyl group having 5 to 20 carbon atoms, an aryl group `~ :
having 6 to 12 carbon atoms, or an ether-substituted group
having 3 to 80 carbon atoms and 1 to about 4Q ether oxygen atomsO
. . .
9 .......
~2~J~
J. Darby U. S0 patent No. 2, 669, 548 of ;
February 16, 1954 discloses halogen-containing resin
compositions having improved stability containing a mixture
of a zinc salt and a calcium chelate derivative of a 1, 3
5 dicarbonylic compound capable of keto-enol tautomerism~
Zinc salts can be zinc salts of organic acids and zinc salts
of weak inorganic acids, for example zinc acetate, zinc
propionate, zinc octanoate, zinc ricinoleate stearate, and ~ ~
zinc salts ~f carbonic, silicic, and boric acids. Calcium " ~;
chelates can be derivatives of B-diketones, ~-ketoacids, ~ ~
and the esters of B-ketoacids, for example the calcium ~ ;
chelates of ethyl acetoacetate, phenyl acetoacetate,
acetoacetic acid, acetylacetone, benzoylacetone, and
diac etylac etone.
LoL~ Wood UOS. patent No. 3,492, 267 of January 27, 1970
discloses zinc complexes of B-dicarbonyl compounds used as -- `
stabilizing additives for chlorine-containing polymers in
general, and polyvinyl chloride in particular. The zinc
complexes possess the general formula: ~ -
/CH
R--C Cl--R '
O O ~ ' .` .
Zn/
2 5R~ C--R ' -
CH /
- . ,. ' .'
... .......
~', '
:-: ...
~ ~ ~ 2 ~ '3 ~
wherein R and R' are the same or dli~erent and are each
hydrogen or an alkyl, alkoxy, phenyl or phenoxy group.
Preferably when R represents an alkyl or alkoxy group, it
contains 1 to 20 carbon atoms.
L. Weisfeld U. SO patent No. 3, 493, 536 of February 3, 1970
: .
discloses that diaroylmethane compounds of the general formula
~ : .
C6H5CO CHP~-COC6H5 wherein R is hydrogen or a monovalent
hydrocarbon radical provide stabilizing action against the " ~-
,. ~
sensitizing effect of bismuth or antimony compounds on chlorine~
contalning materials. -~
U. S. patent No. 3, 346, 536 of Octol~er 10, 1967 discloses
a stabiliæer combination of a ketoacetic acid compound, which `
can be an ester or an acid anhydride dimer thereof, with a
. :~, . .;
metal salt of an organic acicl~ The ketoacetic acid esters - ~
. -.. - . ~
15 have the formula:
(R--CI--CH2--CI{))~R ' .' . '. - . '.'`''`
O ~ ,, ,. ~ ~,,
~ ,
wherein R is an inert organic group having from one to `
about thirty carbon atoms, R' is an inert organic radical
. ~. .
20 having from one to about thirty carbon atoms, and x is ; ~ `;
a number from one to ten. The ester molecule has a total - -
of at least eight carbon atoms. - -
The ketoacetic acid anhydride dimers have the
formula: ;
-. .'~'
2 ~ 3
~a) l l H (b) ll R
~CI-R or f ~ R
RJ~OJ~o R ~;
R II
5R lOOC~
R O~J=O
R s again as above and Rl is hydrogen or R'.
It i9 further disclosed that this stabilizer combination
can be used with additional heat stabilizers, among which ~ ~ `
phenols and organic triphosphites and acid phosphites are ;~
preferred.
In all of these patents, the compositions are described ` `
as heat stabilizing compositions, capable of improving the
resistance of the polymer to deterioration when exposed to ` `
elevated temperatures during heat processing. ~ ``
In accordance with the present invention, improved ` -
resistance to deterioration of motor vehicle components made ` `
of polyvinyl chloride resin compositions is obtained b~
combining with the polyvinyl chloride resin, at least one heat
20 stabilizer other than a B-diketone or metal salt
thereof in a sufficient amount to provide resistance to deterioration
during heat processing, and a B-diketone in a sufficient amount
to provide, after formation into a motor vehicle component,
resistance to deterioration at moderate temperatures. ~ ~ ~
.- ,.,-,.-
12
~,,
2 ~
The B-diketones in accordance with the invention ~;
have the formula:
M(R ll_CR '_CI_R ")t~ ~
O O .`:'.,''.,'
When in this formula M is a hydrogen atom, the ~ -
formula becomes
H(R--C--CR'--C--R")
O O ~. ~, :,'
which is a way to indicate by a single expression that the ~ ";`
., ~, .. . . .
hydrogen atom can be linked in more than one way, as ~ `
in the tautomeric formulas I to III (i. e. formulas of compounds
in readily movable equilibrium with one another) j ; `
R~ CHR'--Cl--R" ~R-C_CR'-C-R" =R-C-CR'=f`-R"
(I) (II) (m) ;`"~
the latter two of which are identical when R and R" are the
same and non-identical when R and R" are different. The ~ `-
relative proportions of tautomers I, II, and III in the B-diketone
compounds is a function of the identity of R and R"; for
example the enol content (i. e. combined; content of the C=C ~ ~ ;
containing tautomers II and III) has been reported as 76. 4% or ~`
diacetylmethane (R_R"=methyl) and 89. 2% for acetylbenzoylmethane
(P~=methyl, P~'=phenyl) (see A. Gero. J. Organic ChemO 1954,
vol. 19, p. 1960- 1970).
When M is a metal, the formula:
IVM(R{~ CR'-~CI-R")n n=the valence of the metal M `~
O O ~,
13
2~22~3~ :ï
indicates that, while numerous structural formulas canbe
written differing in the location of various linkages (as ~:
illustrated for zinc acetylbenzoylmethane by formulas V to . . ;
~TIII bel~w),all are equivalent representations of a single ~ `
:. ~
compound which is better representecl as a "hybrid" of all .
formulas than by any single one. In formulas IV to VII, Ph .
represents phenyl and Me represents methyl.
Ph Ph
C=O O~C '
10 V CH Zn CH
f_o o=f ~ `
Me . Me :.
Ph Ph
C--O . O--C .
15 VI CH Zn . CH ;; - ~
/~ ~ / ` "'.''".'''','~''''''`'
c o o f ~ ! .. : ~ ` `
Me Me
fh Ph
C=O;, . O=C
VII CH Zn CH ~ ~
C--0 0--C , . ...... : ~ :
Me M~ ~ .
. . . ~ .`;,.. .:
14
:
2 ~
~' ':'." ~`,'
Ph
C~ C .,,~
D \ ~
VIIICH Zn CH
Cl--O . --I
. ..
In the formula of ~-diketone metal compounds, n is ;
the valence of the metal and the number of ~-diketone groups
per metal atom, as shown: ` " `
M Ll Na K Mg Ca Sr Ba Zn Al Sb
n 1 1 1 2 2 2 2 2 3 3 . .~
Hydrocarbon groups R, R', R" and R"' can be open ~ ~ .
chain or cyclic and include such aliphatic, cycloaliphatic and .
aromatic hydrocarbon groups as alkyl and alkenyl groups ~
having from 11 to 18 carbon atoms; aL~yl cycloaLkyl, alkyl cycloaLkenyl .: :
15 and aLkyl cycloaL~ylaLkylene having from 11 to 18 carbon atoms,
and alkylcycloalkyl groups having from 11 to 18 carbon atoms, and ~ :
non-condensed aryl groups (including araL~cyl, cycloalkylaryl, and
alkyaryl) having 6 to 18 carbon atoms, for example undecyl, - ::
dodecyl, tridecyl, pentadecyl, heptadec-3-en- 1-yl, n-octadecyl,
20 ricinoleyl, linoleyl, linolenyl, decyl cyclohexyl, hexyl
cyclohexyl, cyclododecyl, phenyl, m-tolyl, p-ethylphenyl,
t-butylphenyl, benzyl, cyclohexylphenyl, phenylpropyl and
nonylbenzyL The aryl groups may contain one or two halogen ring
substituents, such as fluorine, chlorine or bromine.
.:
2 ~ 2 2 g ~ ~
. ~. .
` ~ ' ' '
ALkoxyhydrocarbon R, R', R" and R"' groups -
include n-decoxymethyl, 2-dodecoxyethyl, 2-methoxyphenyl, i
and 4-n-octoxyphenylbenzyl. R, R', R" and R"' alkylene-
. ~ . ~..
dioxyhydrocarbon groups include 3(ethylenedioxydodecyl) ~ - -
5 and 3, 4-methylenedioxyphenyL R ' can be hydrogen, but
not R and R", and only one of R and R" can be aliphatic or
cycloaliphatic.
;:: . ~.: i
Illustrative ~-diketone compounds that can be used
include the B-diketones listed below and the aluminum,
antimony, barium, calcium, lithium, magnesium, potassium, ` i
sodium, strontium, and zinc derivatives thereof. `
: ~' ,.'
'~' `'`~';;~
' ~'' '
~ -
.'. '''~' ~''.
'','
':.
16
2 ~ 2 2 ~
.'- .- ` ` `.
. ...~ ~.....
.., ~ .. ... ..
No. 1
)odecanoyl-benzoyl~
CllH~3--C--CH---C~) methane .
O o
No.2 `~ ``
~ Tride anoyl-benzoyl-
C~,H"5--C--CH~--C~ me~hane - .
o o : :~
No. 3
. O~:lu~ al~oyl-b~ oyl~m~hulle `
Cl7H3s--I_CH~
O ., O .::
Nv. 4 .
lru~ ul~oyl b~ oyl~nl~lh~
.CI3H~7--ll--CH3 ~
'`' ~.''`.:
''~ . ,'`;~
17 ~: ` ;:~
2~22~3~ ;
. No. 5
/~ Pen~adecanoyl~benzoyl~
Cl,~3l --C--CH2--C~) methane
No. S
Dibellzoylme~llune . `:
~C--CH~--C~
No. 7 Phenylacetyl benzoyl-methane
(~C--CH2--C--CH ~)
~0. 8
~ c9Hls Benzoyl-nonylbenzoyl-methane
~ ICl--~H~--ICl ~
'~
;'~
.
18
2a22,J~}s :~
``:
No. 9
~ ~ Octylhexa hydrobenzoyl
C8H,7 ~C--CH2--ICl~c8Hl7 octylbenzoyl methane
No. 10
1l ~ Benzoyl-p methoxyben70yl-methane
~C--CH2--C~OCH3 -
No. 11
O O A Di(p methoxybenzoyl)methane
CH30~C--CH2--C~OCH3
No. i2
A 1l 1l ~ Di(p-chlorobenzoyl)methune
Cl ~--C~CH2--C~CI
No. 13 -
~0 0~ Di(3,4-methylenedioxybenzoyl)methane : `
CH2 ~ O O /--~ CH2 ' ': ~-
O~)C--CH2--C~O . ,~
No. 14
O O
/--\ " 1,1-Dodecanoyl- 1-benzoylnonane
~C--I H--C--C
C8HI7
f`
;:
- 2 ~ ~ 2 ~
~
,:,.`
No. 15 O O
` "~
Alpha-dodecanoyl-alpha-
~C--Cf.~ C--CllH23 benzoyl-toluene
., ~ .
5 No. 16 ~ Di(p-t-butylbenzoyl)methane
t-C4Hg--~0~--C--CH2--C~t~C4H9
~ O O -
No. I7 j ; .
Il Il ~ Benzoyl-nonade~anoyl
10~C--CH~--C--Cl8H37 methane
, . . ' ' ' ., ! ' . ' . . ,
_ . . " ' ' ' .
The polyvinyl chloride resin compositions in accordance
with the invention containing a B-diketone and at least one heat
stabilizer are stable without the ~-diketone under the normal
heat processing conditions, as determined by the usual heat
stability tests The B-diketone does not apparently contribute :.
to stability under the normal heat processing conditions, since
the polyvinyl chloride resin compositions are sufficiently stable
without it, but .it does impart stability under moderate temperatures
after shaping in the form of the motor vehicle componeslt, ~ ~:
demonstrating that it does survive the previous heat processing,
~'.
f
t ~
'; '~`~'
.! -
;: ~
While any known heat stabilizer for polyvinyl chloride
~, resins can be used, the preferred heat stabilizers are alkali metal and
polyvalent metal salts of organic nonnitrogenous monocarboxylic
acids, having from six to twenty Eour carbon atoms. The
~' 5 polyvalent metal is preferably a bivalent nontransition metal,
includingbarium, calcium, cadmium, magnesium, strontium,
stannous tin and zincO
i3 The aliphatic, aromatic, alicyclic and oxygen-
'! containing heterocyclic organic acids are operable as a class~ ;
By the term "aliphatic acid" is meant any open chain carboxylic
acid, substituted, if desired, with nonreactive groups, such as
halogen, sulfur and hydroxyl. By the term "alicyclic" it will be
understood that there is intended any cyclic acid in which the
ring is nonaromatic and composed solely of carbon atoms, and
such acids may if desired have inert, nonreactive substituents
such as halogen, hydroxyl, alkyl radicals, alkenyl radicals and
other carbocyclic ring structures condensed therewith. The
oxygen-containing heterocyclic compounds can be aromatic or ~
non-aromatic and can include oxygen and carbon in the ring ~ -
structure, such as aLkyl-substituted furoic acid~ The aromatic
acids likewise can have nonreactive ring substituents such as
halogen, aLt{yl and aLkenyl groups, and other saturated or
aromatic rings condensed therewith.
As exemplary of the acids which can be used in the form
of their metal salts there can be mentioned the following: -
21
:
2 ~ 2 2 ~
-.,
hexoic acid, 2-ethylhexoic acid, n-octoic acid, isooctoic acid,
3, 5, 5-trimethyl hexoic acid, capric acid, undecyclic acid,
lauric acid, myristic acid, palmitic acid, margaric acid,
stearic acid, oleic acid, ricinoleic acid, behenic acid,
5 chlorocaproic acid, hydroxy-capric acid, ethyl acetoacetic
acid, benzoic acid, phenyl-acetic acid, butylbenzoic acid,
ethylbenzoic acid, propylbenzoic acid, hexylbenzoic acid,
salicylic acid, naphthoi~ acid, 1-naphthal~ne acetic acid,
orthobenzoyl benzoic acid, naphthenic acids derived from~ ~;
10 petroleum, abietic acid, dihydroabietic acid, hexahydrobenzoic
acid, and methyl furoic acid, as well as partially esterified ~ `
dibasic acids such as monobutyl phthalate, isooctyl maleate,
ethylene glycol maleate, and 2-ethoxy ethylmaleate.
In combination with the above metal salts of organic
15 acids, or in lieu thereof, a metal salt of a hydrocarbon-
substituted phenol can be used. The hydrocarbon substituents
contain from four to twenty-four carbon atoms each. The
metal can be an aL~ali metal or alkaline earth metal such as
sodium, potassiumO lithium, calcium, strontium, magnesium
~o and barium. Among such polyvalent metal phenolates there
canbe mentioned the magnesium, barium, calcium, strontium,
tin and zinc salts of n-butyl phenol, t-nonyl phenol, n-decyl ~
phenol, t-dodecyl phenol, t-octyl phenol, isohexyl phenol,~ ~ -
octadecyl phenol, diisobutyl phenol, methyl propyl phenol,
25 diamyl phenol, methyl isohexyl phenol, methyl t-octyl phenol,
22
.:
''"''~
2 ~
di-t-nonyl phenol, ortho or para phenyl phenol. The modified
metal phenolates disclosed by M~ Pollock in U.SO patent
No. 3, 630,979 of December 28, 1971 and by M Minagawa in
U. S. patent No. 3, 733, 288 of May :15, 1973 are also suitableO ;
Mixtures of salts of various metals can be used, such
as mixed zinc and tin salts with the aLkaline earth metal salts,
e.gO, barium and zinc stearates, as in U.S. patent No. 2,446,976.
In lieu of but preferably in addition to the polyvalent
metal salt, organic phosphites can be used.
The organic phosphite can be any organic phosphite
having one or more organic radicals attached to phosphorus
through oxygen. These radicals can be monovalent radicals
in the case of the triphosphites, diphosphites and monophospbites,
which can be defined by the formula:
R l~P~R 3
R2 '-`
in which Rl, R2 and R3 are selected from the group consisting
of hydrogen, alkyl, alkenyl, aryl, aLkaryl, araLkyl, and
cycloalkyl groups having from one to about thirty carbon atoms
Also included are the organic phosphites having a
bivalent organic radical forming a heterocyclic ring with the
phosphorus of the type:
/ O\ '~ :~
2 5 R~ P--~R
O .,
in which Rq is a bivalent organic radical selected from the ~
~ ~ ~ s~
group consisting of alkylene, arylene, ara~ylene,
aLkarylene and cycloaLkylene radicals having from two to
about thirty carbon atoms, and R5 is a monovalent organic
radical as defined above in the case of R1, R2 and R3. `~ Also useful in the compositions of the invention are
mixed heterocyclic-open chain phosphites of the type: . O\ /0
~ 0/ 0/
10 More complex phosphites are formed from trivalent
organic radicals, of the type:
/O\ / O\ /O\ /OH
R~O--/ HO-R~ / ~R~ / \ OH
in which R~ is a trivalent organic radical of any of the types
of Rl to R5, inclusive, as defined above,
A particularly useful class of complex phosphite are
the tetraoxadiphosphaspiro undecanes of the formula :
~OCH8~ ~ CH20 \
Ri~P / C\ P--~R2
OCH2 CH2O/
where Rl and P~2 are selected from the group consisting of
aryl, aLkyl, aryloxyethyl, alkyloxyethyl, aryloxyethoxyethyl,
aLkyloxyethoxyethyl and aLkyloxypolyethoxyethylO
An especially preferred class of organic phosphites -
have a bicyclic aromatic group attached to phosphorus through
oxygen, with no or one or more pnenolic hydroxyl groups on
24
2~22~
either or both of the aromatic rings" These phosphites ~ ~;
are characterized by the formula: :
7 0~ / 7 : ~ `
0/ \0 ' ~
/ --r ~ ~ :
(HO)r"--A~p
O
in which Ar is a mono or bicyclic aromatic nucleus and m
is an integer of from 0 to about 5. Z is one or a plurality of : .
organic radicals as defined above for Rl to R6, taken singly ~ ~ .
or together in sufficient number to satisfy the valences of the ~;
two phosphite oxygen atoms. Z can also be hydrogen, and
can include additional bicyclic aromatic groups of the type
~HO)~"-Ar,
The term "organic phosphite" as used herein is
inclusive of the above-described mono-, di- and triphosphites. ~i`
Usually, the phosphite will not have more than about sixty
carbon atomsO
Exemplary are monophenyl di-2-ethylhexyl phosphite,
diphenyl mono-2-ethylhexyl phosphite, di-isooctyl monotolyl
phosphite, tri-2-ethylhexyl phosphite, phenyl dicyclohexyl
phosphite, phenyl diethyl phosphite, triphenyl phosphite, ~ -
tricresyl phosphite, tri(dimethylphenyl) phosphite,
trioctadecyl phosphite, triisooctyl phosphite, tridodecyl
phosphite, isooctyl diphenyl phosphite, diisooctyl phenyl
~ ;:
~ ,''.
` :
phosphite, tri(t-octylphenyl) phosphite, tri(t-nonylphenyl)
phosphite, benzyl methyl isopropy:L phosphite, butyl dicresyl
phosphite, isooctyl di(octylphenyl) phosphite, di(2-ethylhexyl)
(isooctylphenyl) phosphite, tri(2-c~yclohexylphenyl) phosphite,
tri-a-naphthyl phosphite, tri(phenylphenyl) phosphite, tri(2-
phenyl ethyl) phosphite, monododecyl phosphite, di(p-tert-
butyl phenyl) phosphite, decyl phenyl phosphite, tert-butyl~
phenyl 2-ethylhexyl phosphite, ethylene phenyl phosphite,
ethylene t-butyl phosphite, ethylene isohexyl phosphite,
ethylene isooctyl phosphite, ethylene cyclohexyl phosphite,
2-phenoxy- 1, 3, 2-dioxaphosphorinane, 2-butoxy- 1, 3, 2-dioxaphos-
phorinane, 2-octoxy-5, 5-dimethyl~dioxaphosphorinane,
2-cyclohexyloxy-5, 5-diethyl dioxaphosphorinane, monophenyl
phosphite, 2-ethylhexyl phosphite, isooctyl phosphite, cresyl
phosphite, t-octylphenyl phosphite, t-butyl phosphite, diphenyl
phosphite, diisooctyl phosphite, dicresyl phosphite, dioctylphenyl `:
phosphite, didodecyl phosphite, di-a-naphthyl phosphite, ethylene
phosphite, butyl cresyl phosphite, phenyl-mono-2-ethylhexyl ~;
phosphite, isooctyl monotolyl phosphite and phenyl cyclohexyl
phosphite~
Exemplary pentaerythrityl phosphites are 3, 9-diphenoxy-
2, 4, 8, 10-tetraoxa-3, 9-diphosphaspiro-(5, 5)-undecane (diphenyl- ~:
pentaerythritol-diphosphite), 3, 9 di(decyloxy)-2, 4, 8, 10-
tetraoxa-3, 9-diphosphaspiro-(5, 5)-undecane, 3, 9-di(isodecyloxy)-
2, 4, 8, 10-tetraoxa-3, 9-diphosphaspiro-(5, 5) -undecane, 3, 9- -: .
26 :
~ ~ x ~
di(octadecyloxy)-2, 4, 8, 10-tetraoxa-3, 9-diphosphaspiro-(5, 5)-
undecane, 3-phenoxy-9-isodecyloxy-2, 4, 8, 10-tetraoxa-3, 9-
diphosphaspiro-(5, 5)-undecane, 3, 9-di(methoxy)-2, 4, 8, 10-
tetraoxa-3, 9-diphosphaspiro-(5, 5)-undecane, 3, 9-di(lauryloxy)-
2, 4, 8, 10-tetraoxa-3, 9-diphosphaspiro-(5, 5)-undecane,
3, 9-di-p-tolyoxy-2, 4, 8, 10-tetraoxa-3, 9-diphosphaspiro-(5, 5)-
undecane; 3, 9-di(methoxyethoxy)-2, 4, 8, 10-tetraoxa-3, 9-
diphosphaspiro-(5, 5)-undecane; 3-methoxyethyloxy-9- ~:~
isodecyloxy-2, 4, 8, 10-tetraoxa-3, 9-diphosphaspiro-(5, 5)-
undecane; 3, 9-di(ethoxyethoxy)-2, 4, 8, 10-tetraoxa-3, 9-
diphosphaspiro-(5, 5)-undecane; 3, 9-di(butoxyethoxy)-2, 4, 8, 10
tetraoxa-3, 9-diphosphaspiro-(5, 5)-undecane; 3-methoxyethoxy- .
9-butoxyethoxy-2, 4, 8, 10-tetraoxa-3, 9-diphosphaspiro-(5, 5)-
undecane; 3, 9-di(methoxyethoxyethoxy)-2, 4, 8, 10-tetraoxa-3, 9-
diphosphaspiro-(5, 5)-undecane; 3, 9-di(butoxyethoxyethoxy-
2, 4, 8, 10-tetraoxa-3, 9-diphosphaspiro-(5, 5)-undecane; 3, 9
di(methoxyethoxyethoxyethoxy)-2, 4, 8, 10-tetraoxa-3, 9-
diphosphaspiro-(5, 5)-undecane; 3, 9-di(methoxy(polyethoxy)
ethyloxy)-2, 4, 8, 10-tetraoxa-3, 9-diphosphaspiro-(5, 5)-undecane :
(where the (polyethoxy)ethoxy group has an average molecular
weight of 350), 3, 9-di(methoxy(polyethoxy)ethoxy)-2, 4, 8, 10- .
tetraoxa-3, 9-cliphosphaspiro-(5, 5)-undecane (where the
(polyethoxy)-ethoxy group has an average molecular weight of
550).
27
~. - -.,
~2~
Exemplary of the bis aryl phosphites are: bis(4, 4'- :
thio-bis(2-tertiary-butyl- 5-methyl-phenol)) isooctyl phosphite,
mono(4, 4'-thio-bis(2-tertiary-butyl-5-methyl-phenol)) di-
phenyl phosphite, tri-(4, 4'-n-butlidene-bis(2-tertiary-butyl- :; ;
5 5-methyl-phenol)) phosphite, (4, 4'-benzylidene-bis(2-
tertiary-butyl-5-methyl-phenol)) diphenyl phosphite, isooctyl
2,2'-bis(parahydroxyphenyl) propane phosphite, tridecyl 4,4'-
n-butylidene-bis(2-tertiary-butyl-5-methyl-phenol) phosphite, ` .
4, 4'-thiobis(2-tertiary-butyl-5-methylphenol) phosphite, 2- ~:
ethylhexyl-2, 2'-methylene-bis(4-methyl-6-1'-methylcyclohexyl) ~
phenol phosphite, tri(2, 2 ' -bis- (para-hydroxyphenyl) propane) ::
phosphite, tri(4, 4'-thio-bis(2-tertiary-butyl-5-methyl-phenol) ;~
phosphite, isooctyl-(2, 6-bis(2'-hydroxy-3, 5-dinonylbenzyl)-4- : ;
nonyl phenyl)) phosphite, tetratridecyl 4, 4'-n-butylidene- -~
15 bis(2-tertiary-butyl-5-methyl phenyl) diphosphite, tetra-isooctyl
4, 4'-thiobis(2-tertiary-butyl-5-methyl phenyl) diphosphite, 2, 2'~
methylene-bis(4-methyl-6-1'-methyl cyclohexyl phenyl) ~-
polyphosphite, isooctyl-4, 4'-isopropylidene-bis-phenyl- - .
polyphosphite, 2-ethylhexyl-2, 2'-methylene-bis(4-methyl-6, 1'- :
20 methyl-cyclohexyl) phenyl triphosphite, tetratridecyl-4,4'-
oxydiphenyl diphosphite, tetra-n-dodecyl-4, 4'-n-butylidenebis -
(2-tertiary-butyl-5-methylphenyl) diphosphite, tetra-tridecyl-
4, 4'-iso-propylidene bisphenyl diphosphite, hexatridecyl butane- .
1, 1, 3-tris(2'-rnethyl-5'-tertiary-butylphenyl-4') triphosphite. ~ ~
'':.
28
~.
::;`
2 ~
Preferred classes of additional stabilizers that can
be used include the phenols, aliphatic polyhydroxy compounds;
esters, amides, and hydrazides of thioalkylenedicarboxylic
acids and nitrilotrialkylenetricarboxylic acids; ketoacetic
acid compounds; and organic nitrogen compounds such as the
esters of betaaminocrotonic acid, diphenylthiourea, and
2-phenylindole. Phenol stabilizers can be included in amounts
corresponding to 0. 01 to about 0. 2 parts per 100 parts of
polymer being stabilized~ Typical phenol stabilizers are
butylated hydroxy-toluene (BHT), 4, 4'-isopropylidenebisphenol, -~
and 1, 1, 3 -tris(2 ' -methyl-4 ' -hydroxy- 5' -t-butylphenyl) butaneO
The phenol stabilizers contain one or more phenolic
hydro~yl groups, and one or more phenolic nuclei and can
contain from about eight to about three hundred carbon atoms
In addition, the phenolic nucleus can contain any oxy or thio
ether group.
The a~cyl-substituted phenols and polynuclear phenols, ~ "
because of their molecular weight, have a higher boiling point,
and therefore are preferred because of their lower volatility.
There can be one or a plurality of alkyl groups of one or more
carbon atoms. The alkyl group or groups including any alkylene
groups between phenol nuclei preferably aggregate at least
four carbon atomsO The longer the alkyl or aLkylene chain,
the better the compatibility with polypropylene, inasmuch as
the phenolic compound then acquires more of an aliphatic ~ ~
-,'' . ''
29 ~
'`'~
hydrocarbon character, and therefore there is no upper limit
on the number of aLkyl carbon atoms. Usually, from the
standpoint of availability, the compound will not have more
than about eighteen carbon atoms in an alkyl, alicyclidene ;
and alkylene group, and a total of not over about fifty carbon
atoms. The compounds may have from one to four alkyl
radicals per phenol nucleus
The phenol contains at least one and preferably at least
two phenolic hydroxyls, the two or more hydroxyls being
in the same ring, if there is only one. In the case of bicyclic
phenols, the rings can be linked by thio or oxyether groups, ~
or by alkylene, alicyclidene or arylidene groups. -
The monocyclic phenols which can be employed have
the structure: ;
(R),~l~(O~)x2 ;
::
R is selected from the group consisting of hydrogen;
halogen; and organic radicals containing from one to about ;~
thirty carbon atoms, such as alkyl, aryl, alkenyl, a~aryl,
araLkyl, cycloalkenyl, cycloalkyl, aLkoxy, and acyl ~
R'IC-- ~ -
O :'. .
where R' is aryl, alkyl or cycloa~yl. ~ -
, .~. . .
x, and x2 are integers from one to four, and the sum of ~
xl and x2 does not exceed six. -
,' ~''.',
: :-'',
The polycyclic phenol employed in the stabilizer
combination is one having at least two aromatic nuclei linked ~ -
by a polyvalent linking radical, as clefined by the formula:
( I r)~ Y-( I r)~l2
(OH)"~l (H)n~a
wherein Y is a polyvalent linking group selected from the
group consisting of oxygen; carbonyl; sulfur; sulfinyl;
aromatic, aliphatic and cycloaliphatic hydrocarbon groups;
and oxyhydrocarbon, thiohydrocarbon and heterocyclic groups.
The linking group can have from one up to twenty carbon atoms
Ar is a phenolic nucleus which can be a phenyl or a
polycar~oxylic group having condensed or separate phenyl
rings: each Ar group contains at least one free phenolic
hydroxyl group up to a total of fiveO The Ar rings can also
include additional rings connected by additional linking nuclei
of the type Y, for example, Ar-Y--A~Y-Ar.
ml and m2 are numbers from one to five, and n1 and -
n2 are numbers of one or greater, and preferably from one
,.-....
to four.
The aromatic nucleus Ar can, in addition to phenolic
hydroxyl groups, include one or more inert substituents. -
Examples of such inert substituents include hydrogen,
halogen atoms~ e. g. chlorine, bromine and fluorine; organic
radicals containing from one to about thirty carbon atoms,~ `
25 such as alkyl, aryl, alkaryl, aralkyl, cycloalkenyl, cycloalkyl,
alkoxy, aryloxy and acyloxy
" ~
31 ~
~ ~ 2 r t c~ ~3 ~
R ' C-O ~ ~
O . ~
where R' is aryl, alkyl or cycloalkyl, or thiohydrocarbon ~;
groups having from one to about thirty carbon atoms, and ~ .
5 carboxyl
-C~ :''
O ;~
groups. Usually, however, each aromatic nucleus will not
have more than about eighteen carbon atoms in any
hydrocarbon substituent groupO The Ar group can have from -:
one to four substituent groups per nucleus.
Typical aromatic nuclei include phenyl, naphthyl,
phenanthryl, triphenylenyl, anthracenyl, pyrenyl, chrysenyl, ~
and fluorenyl groupsO ~ -;
When Ar is a benzene nuc leus, the polyhydric .
polycyclic phenol has the structure: -
;~. ~ . : .. .~ .
~~ OH~ ~0~ :' ~ '``''
E~ YT~
~ y~ R~
wherein Rl, R2 and R3 are inert substituent groups as . ~
de~cribed in the previous paragraph, ml and m3 are integers~- .
from one to a maximum of five, m2 is an integer from one . -
to a maximum of four, xl and X3 are integers from zero to ~ -
four, and x2 is an integer from zero to three; Yl is an integer - .
from zero to about six and Y2 is an integer from one to five, ~:
preferably one or two
32
2 ?~ 2 2 ~
Preferably, the hydroxyl groups are located ortho and/
or para to Y.
Exemplary Y groups are alkylene, alkylidene, and
alkenylene arylene, aLkyl arylene, arylalkylene, cycloalkylene,
5 cycloalkylidene, and oxa- and thia-substituted such groups;
carbonyl groups, tetrahydrofuranes, esters and triazino groups~
The Y groups are usually bi, tri, or tetravalent, connecting two, .:
three or four Ar groupsO However, higher valence Y groups, ``
connecting more than four Ar groups, can also be used. ` `
10 According to their constitution, the Y groups can be assigned
to subgenera as follows~
. ~:
(1) Y groups where at least one carbon in a chain or
cyclic arrangement connect the aromatic groups, such as
--CEt~CE3r-;--(CHI~;~CH~;
~ ~ ,
15 -O~OEr,
~O;-C~
~ J ~
X ' .',~'
CH, C~
CH_;_C~ b~ C~_; ....
7 b~, C2~ C~3
cHr b--C~ CH~}C~
33 `~
,
1 . ' ' ' ' ' '" ' ' ' ; ~ '
~22~5 `
,,``.
-C~C}; o_; ~ C.
o~,)~: {~C~<~
~, o~c~l :`.````.'`'`
--CH~--~ J--C}~
Y ' ,- .,
10--CH~ ~ H~ I2C~ /CEI~,
--~r,c C~3-- - .
' H b c~
15-EC/I~ C~; b~
CE~ ~OH;
H3~\l/C~ /~H-- ~Ht
(2) Y groups where only atoms other than carbon link . ~
the aromatic rings, such as ~ .
-O~ ~, --S- and-(S)x--
O O
where x is a number from one to ten;
(3) Y groups made up of more than a single atom :
including both carbon and other atoms linking the aromatic
nuclei, such as
34
2 ~
--C ~3:~0--i~ C H--C ~I~ O--C ~I~C
H~
~0~ ~ '.. -':` '.'
--O--CH~C~I~O--;--C~Irt 8 tC}~
--C~.~ S~C~;--S--CH~ S--;--C ~ CH~
--C~C~ ~--CH~;--c--o--~c~ o--c--;
10C1--C~I~OOCC}~iC~
O O
c~ cH~a O c~c~o a C~I2C~
15N~ \N ;--C~S--; ~;
~o N
20--CH~S--CH~; a~d ¦ S ~
Although the relation of effectiveness of chemical structure `
is insufficiently understood, any of the most effective phenols
have Y groups of subgenus (1), and accordingly this is
preferredO Some of these phenois can be prepared by the
25 aLkylation of phenols or alkyl phenols with polyunsaturated
hydrocarbons such as dicyclopentadiene or butadiene,
~.~
-` 2 ~ 2 2 ~
:: ,.. ..
. -. :`,
Representative phenols include guaiacol, resorcinol ``.
monoacetate, vanillin, butyl salicylate, 2, 6-ditert-butyl-4- ` ` `
methyl phenol, 2-tert-butyl-4-methoxy phenol, 2, 4-dinonyl
phenol, 2, 3, 4, 5-tetradecyl phenol, tetrahydro~ naphthol, ~ ~ ;
o-, m- and p-cresol, o-, m- and p-phenylphenol, o-, m-
and p-xylenols, the carvenols, symmetrical xylenol, thymol,
o-, m- and p-nonylphenol, o-, m- and p-dodecylphenol,
and o-, m- and p-octyl-phenol, o- and m-tertbutyl-p-hydroxy- ~ ~ `
anisole, p-n-decyloxy-phenol, p-n-decyloxy-cresol, nonyl-n- `. .
decyloxy-cresol, eugenol, isoeugenol, glyceryl monosalicylate,
methyl-p-hydroxy-cinnamate, 4-benzyloxy-phenol, p-acetyl-
am inophenol, p-stearyl-am inophenol methyl-p-hydroxybenzoate,
p-di-chlorobenzoyl-aminophenol and p-hydroxysalicyl anilideO .
E~emplary polyhydric phenols are orcinol, propyl gallate, ` ~
cetechol, resorcinol, 4-octyl-resorcinol, 4-dodecyl-resorcinol, .
4-octadecyl-catechol, 4-isooctyl-phloroglucinol, pyrogallol, :
hexahydroxybenzene, 4-isohexylcatechol, 2, 6-ditertiary-butyl- ~ -
resorcinol, 2, 6-diisopropyl-phloro~lucinol.
Exemplary polyhydric polycyclic phenols methylene-
bis-(2, 6-ditertiarybutyl-phenol), 2, 2-bis-(4-hydroxyphenyl)-
propane, methylene-bis(p-cresol), 4, 4'-benzylidenebis-(2-
tertiary butyl-5-methylphenol), 4, 4'-cyclohexylidenebis-(2-tertiary
butylphenol), 2, 2'-methylene-bis(4-methyl-6-(1'-methyl-
cyclohexyl)-phenol), 2, 6-bis(2'-hydroxy-3'-tertiary-butyl-5'-
methylbenzyl)-4-methylphenol, (2-tertiary-butyl-5-methyl-
36 :
: .
~22~3~
phenol)! 2, 2'-bis(4-hydroxy-phenyl) butane, ethylenebis- i
(p-cresol), 4, 4'-oxobis-phenol, 4, 4'-oxobis(3-methyl-5-
isopropyl-phenol), 4, 4'-oxobis-(3-methyl-phenol), 2, 2'-oxobis-
(4-dodecyl-phenol), 2, 2'-oxobis-(4-methyl-5-tertiary-butyl-
phenol), 4, 4'-thio-bis-phenol; 4, 41-thio-bis-(3-methyl-6- ; ~`.tertiary-butyl-phenol), 2, 2'-thio-bis-(4-methyl-6-tertiary- ~:
butyl-phenol), 4, 4' -n-butylidene- (2- t-butyl- 5-methyl-phenol),
2, 2'-methylene-bis-(4-methyl-6-(1'-methyl-cyclohexyl)-
phenol), 4, 4'-cyclohexylenebis-(2-tertiary-butyl-phenol),
2, 6-bis-(2'-hydroxy-3'-t'-butyl-5'-methyl-benzyl)-4-methyl-
phenol, 4, 4'-oxobis(naphthalene-1, 5-diol), 1, 3'-bis(naphthalene-
2, 5-diol)propane, and 2, 2'-butylenebis-(naphthalene-2,7-diol),
(3-rnethyl- 5-tert-butyl-4-hydroxyphenyl)-4'-hydroxyphenyl) ;
propane, 2, 2'-methylenebis-(4-methyl-5-isopropylphenol),
2, 2'-methyl~nebis-(5-tert-butyl-4-chlorophenol), (3, 5-di-tert- -:
butyl-4-hydroxyphenyl)-(4'-hydroxyphenyl) ethane, (2-hydroxy~
phenyl)-(3', 5'-di-tert-butyl-4', 4-hydroxyphenyl)ethane, 2, 2'-
methylenebis-(4-octylphenol), 4, 4'-propylenebis-(2-tert-
butyl-phenol), 2, 2'-isobutylenebis-(4-nonylphenol), 2, 4-bis-
(4-hydroxy-3-t-butylphenoxy)-6-(n-octylthio)-1, 3, 5-triazine,
2, 4, 6-tris(4-hydroxy-3-t-butylphenoxy)-1, 3, 5-triazine, 2, 2'-
bis-(3-t-butyl-4-hydroxyphenyl) thiazolo-(5,4-d) thiazole,
2, 2'-bis(3-methyl-5-t-butyl-4-hydroxyphenyl) thiazolo-(5, 4-d)-
thiazole, 4, 4'-bis(4-hydroxy-phenyl) pentanoic acid octadecyl
ester, cyclopentylene-4, 4'-bisphenol, 2-ethylbutylene-4, 4'- ~ -~
'; ~ ''
37 ~
, ~,
2~.2~
bisphenol, 4, 4'-cyclooctylenebis(2-cyclohexylphenol), B, .B-
thiodiethanol-bis(3 -tert-butyl-4 -hydroxyphenoxy ac etate), 1, 4-
butane-diobis(3-tert-butyl-4-hydroxyphenoxy acetate), .
pentaerythritoltetra(4-hydroxyphenol propionate), 2, 4, 4'-tri- :~
hydroxy benzophenone, bis(2-tert-butyl-3-hydroxy-5- ~ ~.
methylphenyl sulfide, bis(2-tert-butyl-4-hydroxy-5-methyl-
phenyl) sulfide, bis(2-tert-butyl-4-hydroxy-5-methyl-
phenyl sulfoxide), bis-(3-ethyl-5-tert-butyl-4-hydroxy
benzyl) sulfide, bis(2-hydroxy-4-methyl-6-tert-butyl-
phenyl) sulfide, 4, 4'-bis(4-hydroxyphenyl) pentanoic acid
octadecyl thiopropionate ester, 1,1, 3-tris(2'-methyl-4'-
hydroxy-5'-tert-butylphenyl) butane, 1, 1, 3-tris-(1-methyl-3-
hydroxy-4-tert-butylphenyl) butane, 1, 8-bis(2-hydroxy-5- ` ~ ~:
methylbenzoyl-n-octane, 2, 2'-ethylene-bis-[4'-(3-tert-butyl-
4-hydroxyphenyl)-thiazole], 1-methyl-3-(3-methyl-5-tert-
butyl-4-hydroxybenzyl)-naphthalene, 2, 2'-(2-butene) `~
bis-(4-methoxy-6-tert-butyl phenol) and pentaerythritol -
hydroxyphenyl propionate~
A particularly desirable class of polyhydric polycyclic
phenols are the dicyclopentadiene polyphenols, which are of
the type:
R~
Rl . n .
38
~ ~ ~ ,7 ~
in which Rl and R2 are lower a~{yl, and can be the same or
different, and n is the number of the groups enclosed by the
brackets, and is usually from 1 to about 5, These are
described in U. S, patent NoO 3, 567, 683, dated March 2, 1971
5 to Spacht. A commercially available member of this class is
Wingstay L, exemplified by the dicyclopentadiene
tri(2-tert-butyl-4-methyl-phenol) of the formula:
0~: ,0~ " 0~';~ :
c(}~
H~ Er~ ~r~ ;
The polyhydric polycyclic phenols used in the invention
can also be condensation products of phenol or a~yl-phenols
with hydrocarbons having a bicyclic ring structure and a double
bond or two or more double bonds, such as cY-pinene, B-pinene,
15 dipentene, limonene, vinylcyclohexene, dicyclopentadiene,
allo-ocimene, isopreneandbutadiene. Thesecondensatlon ~ d
products are usually obtained under acidic conditions in the ~ --
form of more or less complex mixtures of monomeric and
polymeric compounds. However, it is usually not necessary ~ -
20 to isolate the individual constituentsO The entire reaction
product merely freed from the acidic condensation catalyst and
unchanged starting material, can be used with excellent resultsO
While the exact structure of these phenolic condensation products
39
is uncertain, the Y groups linking the phenolic nuclei all fall
into the preferred subgenus 1. For method of preparation,
see, e.g., U S. patent No. 3, 124, 555, U,S. patent No.
3, 242,135, British patent No~ 961, 5040
Aliphatic polyhydroxy compounds can be included
in amounts corresponding to 0.1 to about 1 part per 100
parts of polymer being stabilized. Typical aliphatic
polyhydroxy compounds are glycerol, polyglycerol,
monodi-, and tri-pentaerythritol, mannitol, sorbitol, and
partial esters of these with saturated and unsaturated fatty
acids having 6 to 22 carbon atoms.
The esters, amides, and hydrazides of thiodialkylene
dicarboxylic acids and nitrilotri-aL"ylenetricarboxylic acids
can be included in amounts corresponding to 0.1 to about 1
part per 100 parts of polymerO Typical of these are
dimethyl thiodipropionate, dilauryl and distearyl thiodipropionates, -~
2, 2 '-thiobis(acetyl ethanolamine), 3, 3 '-thiobis(propionyl-
diisopropanolamine, nitrilotriacetic acid (NTA) propylene
glycol ester, NIA tris(ethylamide), NTA bis (hydroxyethyl)
N-butylamide, 3, 3~-thiodipropionyldihydrazide and 6, ~
thiodihexanoyldihydrazide. ~ ;
The thiodipropionic acid ester has the following
formula:
Ft lOOCCH2CH2--~CH2CH2COOY
-,'''.'
in which Rl is an organic radical selected from the group ~;
consisting of hydrocarbon radicals such as aLkyl, alkenyl,
aryl, cycloalkyl, mixed a~yl aryl, and mixed alkyl cycloalkyl ~`
radicals; and esters thereof with aliphatic carboxylic acids;
5 and Y is selected from the group consisting of (a) hydrogen,
(b) a second R radical R2, which can be the same or different
from the R, radical, (c) a polymeric chain of n thiodipropionic ~;
acid ester units:
R 1O[OCCH2CH2SCH2CH2COOXO]nOCCH2CH2-~CH2CH2COOZ ~ :
10 wherein Z is hydrogen, R2 or M; n is the number of
thiodipropionic acid ester units in the chain; and X is a
bivalent hydrocarbon group of the type of Rl; the value of n
can range upwards from 1, but there is no upper limit on n
.
except as is governed by the ratio of carbon atoms to sulfur :: .
. . .
atoms as stated below; and (d) a polyvalent metal M of .
. . .
Group II of the Periodic Table such as zinc, calcium, cadmium,
barium, magnesium and strontium. ~
The molecular weights of the R and Y radicals are taken - .
such that with the remainder of the molecule, the thiodipropionic : `
20 ester has a total of from about ten to about sixty carbon atoms
per sulfur atom. . `
Accordingl~, the various thiodipropionic ac id ester .: ~
species coming within the above-mentioned categories within ;.
the general formula can be defined as follows: ~
~.,
41 ~`
2 ~
(a) R lOOCCH2CH2SCH2CH2COOH
(b) RlOOCCH2CH2SCH2CH2COOR2
(c) R~O[()CCH2CH2SCHzCH2COOX-O]nOCCH2CH2SCH2CH2COOZ ~ ~;
(d) [RlOOCCH2~H2ScH2cH2c0o]2M
5 In the above formulae, Rl and R2, M, X and Z are the same
as before. In the polymer (c), as in the other forms of
thiodipropionic acid esters, the total number of carbon atoms
per sulfur atom is within the range from about ten to about
sixty.
The R radical of these esters is important in furnishing
compatibility with the polypropylene. The Y radical is ;
desirably a different radical, R2 or M or a polymer, where `
R is rather low in molecular weight, so as to compensate for
this in obtaining the optimum compatibility and nonvolatilityO
Where Y is a metal, the thiodipropionic acid ester furnishes `
the beneficial properties of the polyvalent metal salt which is ;
described belowO
The aryl, alkyl, aL'senyl and cycloalkyl groups may, if -
desired, contain inert~ nonreactive substituents such as
2û halogen and other carbocyclic and heterocyclic ring structures
condensed therewithO ~-
Typical R radicals are, for example, methyl, ethyl,
propyl, isopropyl, butyl, isobutyl, t-butyl, amyl, isoamyl, -~
n-octyl, isooctyl, 2-ethyl hexyl, t-octyl, decyl, dodecyl,
25 octadecyl, allyl, hexenyl, linoleyl, ricinoleyl, oleyl, phenyl,
'-''''.'
' .
42
'.
2 ~ 2 2 ~
xylyl, tolyl, ethylphenyl, naphthyl, cyclohexyl, benzyl,
cyclopentyl, methylcyclohexyl, ethylcyclohexyl, and ;
naphthenyl, hydroxyethyl, hydroxypropyl, glyceryl, sorbityl,
pentaerythrityl, and polyoxyalkylene radicals such as those
5 derived from diethylene glycol, triethylene glycol,
polyoxypropylene glycol, polyoxyethylene glycol, and .
polyoxypropyleneoxyethylene glycol, and esters thereof with
any of the organic acids named below in the discussion of the ~.
polyvalent metal salts, including in addition those organic acids ` `
having from two to five carbon atoms, such as acetic, propionic, . `
butyric and valeric acids~ `
Typical X radicals are alkylene radicals such as
ethylene, tetramethylene, he~amethylene, decamethylene, ~ ~.
alkyl- and aryl-substituted a~cylene radicals such as 1, 2- ~: .
15 propylene,
CH~ ICHI CH~ snd
--C:~CE--,_CH~C--CH~,~ nd--CH--;
1H1 b~
arytene radicals such as phenyIene
{}' ' .`'
20 methylenephe~ylene
-C~
dimethyIene phellylene,
_CH~CH~
43
2 ~ ~ 2 ~
and alieyclene radicals such as cyclohe~ylc~e
<3~
a~d cyclopentylene -
~ .. ~, .
1-~ r ~
\/ .. .;
As exemplary of the thiodipropionic acid esters ~: `
which can be used, there can be mentioned the following:
monolauryl thiodipropionic acid, dilauryl thiodipropionate, ~ .
butyl stearyl thiodipropionate, di(2- ethylhexyl)- thiodipropionate,
diisodecylthiodipropionate, isodecyl phenyl thiodipropionate,
.: :.,:
benzyl lauryl thiodipropionate, benzyl phenyl thiodipropionate, ; :~
the diester of mixed coconut fatty alcohols and thiodipropionic . `
acid, the diester of mixed tallow fatty alcohols and
thiodipropionic acid, the acid ester of mixed cottonseed oil .
fatty alcohols and thiodipropionic acid, the acid ester of mixed ~ ~`
soybean oil fatty alcohols and thiodipropionic acid, cyclohexyl ;
. .
nonyl thiodipropionate, monooleyl thiodipropionic acid,
hydroxyethyl lauryl thiodipropionate, monoglyceryl thiodipropionic ~ ~`
acid, glyceryl monostearate monothiodipropionate, sorbityl
isodecyl thiodipropionate, the polyester of diethylene glycol ~ ~.
and thiodipropionic acid, the polyester of triethylene glycol - ~ .
and thiodipropionic acid, the polyester of hexamethylene glycol :~
and thiodipropionic acid, the polyester of pentaerythritol and
thiodipropionic acid, the polyester of octamethylene glycol and -
",~
44
2 ~ 3 ~
~'``''~
thiodipropionic acid, the polyester of p-clibenzyl alcohol and ; -
thiodipropionic acid, ethylbenzyl lauryl thiodipropionate, ~ -
strontium stearyl thiodipropionate, magnesium oleyl thiodipropionate,
calcium dodecylbenzyl thiodipropionate, and mono(dodecylbenzyl)
5 thiodipropionic acid.
These esters are for the most part known compounds, ~`
but where they are not available, they are readily prepared by
esterification of thiodipropionic acid and the corresponding "
alcohol,
Ketoacetic acid compounds that can be used with the
stabilizer compositions of this invention in amounts of about
0O 05 to about 0~ 5 parts per 100 parts of polymer being
stabilized include 2-ethylhexyl acetoacetate, glyceryl
tris(acetoacetate) and dehydroacetic acid.
The keto acetic acid compound should be nonvolatile
and stable at processing temperatures. It should also be
nitrogen-free. In general, compounds having at least eight
carbon atoms in the molecule fulfill these requirements. The
free keto acetic acids, for some reason that is unknown, do
20 not possess the stabilizing effectiveness of the esters or of
the anhydride dimers. However, metal salts of these keto
acids can be used as the metal salt component of the stabilizer
combination oE the invention, and in combination with the ester
and/or anhydride dimer have excellent stabilizing effectiveness.
:~
~2~
The keto acetic acid esters of this invention have the
following general formula:
(R-CI--CH2--Cl--O),~R ' .`.. .,
o O '~
5 wherein R is an inert organic group having from one to about
thirty carbon atoms, R' is an inert organic radical having
from one to about thirty carbon atoms, and x is a number
from on0 to ten. The ester molecule has a total of at least
eight carbon atoms
R and R' can be hydrocarbon groups, and can b~ allcyl,
allcenyl, aryl, aLkylaryl, aryl allcyl, cycloallcyl, cycloallcenyl,
and heterocyclicO The open chain groups can be straight or
branched, and the cyclic and alicyclic groups can be saturated
or unsaturated. The R and R' groups can also be substituted by -~
15 inert groups such as halogen (fluorine, chlorine, bromine and
iodine) alkoxy or epoxy -C--C'- hydroxy OH and ether
O ' `
- C~C- groups. There will not usually be more than ten of
such substituents, depending of course upon the number of
20 available substituent positions in the R and R' groups.
Thus, the R' radical for example can include free
hydroxyl OH groups, up to a practical maximum of ten, but
generally not more than one hydroxyl group per carbon atom,
and the R' raclical can carry a plurality of R-CI-CH2-C~
- -
46 ~-
~2~
::`..;
ester groups, up to a total of about ten, the value of x. It will `
be understood that where R' has more than one OH group, the
value of x represents only an average value of the number of i;
possible ester species that may exist, dependent on the total number
5 of H groups on R'. For instance, in the case of a di-ester
(x=~), where R' has three free OH groups, there can also be ~.;
pentaester, tetraester, triester and monoester species presentO .
Indeed, in such cases, x can be a decimal number, for instance,
2, 5, indicating the presence of a mixture of monoester, diester, .
triester and higher ester species in proportions to give this
average value for xO Those skilled in the art will perceive the
increased possibilities as x increases to ten or more.
Exemplary R and R' hydrocarbon groups are methyl,
ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl,
tert-butyl, n-amyl, iso-amyl, tert-amyl, hexyl, heptyl, tert-
octyl, 20ethyl hexyl, isononyl, decyl, undecyl, dodecyl, ~ ~:
palmityl, stearyl, oleyl, ricinoleyl,linoleyl, linolenyl, behenyl,
tridecyl, phenyl, xylyl, tolyl, naphthyl, cyclohexyl, methyl-
cyclohexyl, cyclopentyl, tetrahydrofurfuryl, cycloheptyl,
isononylphenyl, iEuryl, and pyranylO :
Exemplary hydroxy-substituted R' groups include . :~
hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 1-hydroxyamyl,
2-hydroxyamyl, 2, 2-dimethylol propyl, 2, 2-dihydroxyamyl,
1,1-methylol hydroxybutyl, 2-(di-hydroxyethyl)-butyl, ;
47
~ ~ 2 ~
1-(dihydroxy ethyl) propyl, 3-4 dihydroxyheptyl, 4-5 dihydroxyoctyl, `
7, 8-dihydroxyhepta-decyl, 6, 7-dihydroxytetradecyl, 1, 2, 3- ;
trimethylol octadecyl, 1, 2, 3, 4, 5, 6-hexahydroxy heptyl,
10-hydroxyeicosyl, 2, 3-dihydroxypropyl, 4-hydroxybutyl, 3, 4-
dihydroxybutyl, 2, 3, 4-trihydroxybutyl, 1, 3, 4-trihydroxybutylO ~ .:
These esters are readily prepared according to known ~ ~ `
procedures by transesterification of a simple ester of the
corresponding keto acetic acid, such as ethyl acetoacetate, :
with the corresponding alcohol. If the corresponding keto
acetic acid is stable, direct esterification is possible If a ~ -
polyhydric alcohol is used, mixed esters of the acid and : `.
alcohol are obtained, according to the molar proportions of :
each, and mixtures of the various possible esters will also be .:
present in most case. .:~
Typical esters are:
(2)Is~C,E[~ C E[2~ 5
.(3~~8
c~ o
~P~ r~
2 5 a~"GE~ p~ ;
48
2~2~
' ::
Q ; ;`:
5~ QE~9O~ "O'~
. O `:`
,a~--~a~ ,C~I,aO~
O ~`~`.'~'`.
~)lCH~ sC~H~ . ; ;
(~0)C~8Ht7C CE?C--O--C3H7-iso :-
O ~ ~ " ~ ~ r~
. , o 11
., ~. ., ,;, . 1 ~. , : ' ,
~13) a~ r~ -, ~E~-~B~a~E
(14) ~ O~t~
CEt--I a~ o--CH, ~--QH~OE
Q3~
~i~t` [ClI~--OE~--O--GHs--37
tl6) ;- OHsll-a~ O~
pHt.--Q--CH~--O--,~ H~
tl~t ~o3~H~ ~?~
. - :
49 .::
(18) [a~7~5~ H~ 0~ ]?G~[O~
. ~ g.a~ .Q..~H,~
. ~20) [t~rt-O~H9--C--C~It~--Q 4.H~ Q~
'21`
. ~ll~a~ o~ 3-~ ~HaO~
0 (~ IQ~a~C.. eE~ a~ (CHa~H)~
s~ ~ ~ 7 : ~
.' . . O~[r~C~ Q~ -Q-~;
(2~ QH~--~Cl~ ¢.--.Q}~C--Q ¢aH~
(25) C~Ha~H--~ O~ ¢--O:EIi~--O ~35~III lso
(2û) OH~C)H?--O~CHrCH~ O~C--O--OH~O:~aOE~
(~ ¢~
~a~ O~--pH~--O--OHI¢H~Q--C,HaCH~Q~
~28) OH~O:EI~[O OHa--OH~I?--0--~3HaC--OlI~11 OOH~
(2,~ [Ç~ --Q--JQ:~p~I~[QQH~q~ a ~ -
~ G H O
` ~ ''
~ -\
- 2~22~
The keto acid anhydride dimers have the ormula: ~
S ~ r
II. R
R~OO0~ :
~ Lo "",
O ',` ` "
R is again as above and Rl is hydrogen or R'. ~;
Exemplary are dehydroacetic acid, isodehydroacetic
acid, dehydropropionyl acetic acid, dehydrobenzoyl acetic
acid, isodehydro-3,4-dichlorobenzoylacetic acid, and esters
of isodehydroacetic acid such as the methyl, ethyl, n-butyl ;~:
2~ethyl hexyl and glyceryl esters.
Organic nitrogen compounds that can be used with
the stabilizer compositions of this invention in amounts of
about 0, 05 to about 0. 5 parts per 100 parts of polymer being l`
stabilized include 2-ethylhexyl 3-aminocrotonate, 1,4-butanediol
bis(3-aminocrotonate) and 2, 2'-thiodiethyl 3-aminocrotonate;
thiocarbanilide and 2-phenylindole, 1, 3-dibutylthiourea, :
phenylurea, and p-ethoxyphenylureaO ~.
The stabilizer compositions of this invention are
effective with any vinyl chloride polymer. The term "vinyl -.
chloride polymer" as used herein is inclusive of any polymer ~-
formed at least in part of the recurring group,
51
2~22~
` ,
X .
-CH C-
~1 X '","'
and having a chlorine content in excess of 4û% In this
group, the X groups can each be either hydrogen or chlorineO ;~
In polyvinyl chloride homopolymers, each of the ~ groups is ~ ~
hydrogen. Thus, the term includes not only polyvinyl chloride ~;
homopolymers but also after chlorinated polyvinyl chlorides as ~-
a class, for example, those disclosed in British patent
No. 893, 288 and also copolymers of vinyl chloride in a major
proportion and other copolymerizable monomers in a minor
proportion, such as copolymers of vinyl chloride and vinyl `;
acetate, copolymers of vinyl chloridewith maleic or fumaric
acids or esters, and copolymers of vinyl chloride with styrene,
~5 propylene, ethylene, 1-hexene, or vinyl n-dodecyl ether. The
invention also is applicable to mixtures of polyvinyl chloride in ;
a major proportion with a minor proportion of other synthetic `
resins such as chlorinated polyethylene or copolymers of
acrylonitrile with butadiene and styrene.
The invention is of application to the stabilization of
rigid polyvinyl chloride resin compositions, that is, resin
compositions which are formulated to withstand high processing
temperatures, of the order of 190C and higher, and of
plasticized polyvinyl chloride resin compositions of conventional
formulation where resistance to heat distortion is not a requisiteO
The respective definitions of rigid and plasticized resins are as
follows. The rigid resins are those resins to which plastici~ers
~ ~ ~ 2 ~
are not added, and which are generally worked at about 190C.
The ASTM definition (1961 D-883, Part 9, page 804) is as
follows: :
"a plastic which has a stiffness or apparent modulus
5 of elasticity greater than 7000 grams per square centimeter
(100, 000 psi) at 23Co "
The plasticized resin would therefore have a modulus
of elasticity of less than 7000 grams per square centimeter, `~
and would have added to it the plasticizer compound, i'
Conventional plasticizers well known to those skilled in the
art can be employed such as, for example, dioctyl phthalate,
octyl diph0nyl phosphate and epoxidized soybean oil.
The preparation of the stabilized polymer composition
is easily accomplished by conventional procedures. The
selected stabilizer combination along with such compounding
ingredients as plasticizers, colors, lubricants, antistatic
agents etc. as may be needed, is blended with the polymer
being stabilized, using, for instance, plastic mixing rollers,
at a temperature at which the mix is fluid and thorough blending
facilitated, typically at from 120 to 180C for a time sufficient
to form a homogeneous sheet, five minutes, usually~ After the ~:
mass is formed, it is sheeted off in the usual way, :~
. ~ ,...-.,
53 :.~
~'2~3~ :
A sufficient amount of the heat stabilizer or combination
is used to improve the resistance of the synthetic polymer to
deterioration in physical properties during heat processing,
including, for example, discoloration, reduction in melt
viscosity and embrittlementO Very small amounts are usually ~ ~
adequate, Amounts within the range from about 0O 001 to about ~`;
5% total heat stabilizers by weight of the polymer are
satisfactory. Preferably, from 0.01 to 3% is employed, for
optimum stabilization~
The ~-diketone is used in an amount to impart resistance to ~; -
deterioration when exposed to moderate temperatures within the
range from about 150 to about 215F after heat processing,
including, for example, discoloration and embrittlement.
Very small amounts are usually adequate. Amounts within the ~;
range from about 0. 001 to about 5% B-diketone by weight of the
polymer are satisfactoryO Preferably, from 0. 01 to 3% is ~ ~
employed, for optimum effect~ -
When all components are solid$, the stabilizer
systems of the invention are readily rendered in solid particulate
form, comprising a blend of: `
(a) B-diketone in an amount of from about 10 to about ;~
35 parts by weight; `
(b) heat stabilizer in an amount of from about 10 to about
35 parts by weight, including, for example,
(1) a polyvalent met al organic acid salt in an amount
of from about 10 to about 35 parts by weight; ; -`
~`
54 ~
''`'
~2~3~
(2) a phenolic antioxidant in an amount from about
~ ... ..
lû to about 35 parts by weight;
(3) other heat or light stabilizers.
When the stabilizer is a liquid, the B-diketone can be
dissolved therein, with gentle warming and agitation if
necessary. Particularly preferred ~-diketones found soluble
in liquid stabilizers include dibenzoylmethane and stearoylbenzoylmethaneO
The stabilizer compositions OI the invention can
include any conventional polyvinyl chloride resin additives,
including in addition lubricants such as stearic acid, paraffin
wax, polyethylene wax, stearamide, petrolatum, and natural
waxes, as well as emulsifiers, antistatic agents, flame- `
proofing agents, pigments and fillers.
The stabilizer compositions of the invention can be
compounded with polyvinyl chloride resins, properly formulated,
and shaped by standard plastics processing techniques
(including calendering, extrusion, injection and compression ~` ;;
molding, blow molding, rotational molding, slush and dip
molding, solution casting, electrostatic spray and fluidized bed
coating), to form a wide variety of motor vehicle components
for both interior and exterior use, such as dashboards, seat
coverings, floor mats, door panels~ arm and head rests,
receptacles, compartments, body side moldings, window trim ~ -
moldings, seat corners and head liners, door and window knobs, `
and crash dashboards~ j
. .,-~,.
,- ' ~''
, . ..
~
~22~3~
Compounding components such as plasticizers, : -
stabilizers, lubricants, impact modifiers, processing aids, ~: `
fillers, colorants, antistatic agent's, tackifiers, flame
retardants, fungicides, antiblocking agents, etc. can be ~ `~
5 incorporated to facilitate processing of such motor vehicle
components
The following Examples in the opinion of the inventors
represent preferred embodiments of their invention.
56
2 ~ 3 ~3
Examples 1 to 5
Polyvinyl chloride resin compositions were made up
having the following formulation:
Ingredient Parts by Weight ~:
:
Polyvinyl chloride homopolymer 100 ;
(Diamond 450)
Dioctyl phthalate 50 : ~
Drapex 6. 8 (epoxidized soybean oil) 8 ~:
Calcium carbonate (Atomite) 20 ~.
Stearic acid 0.3 . :;~
~
Stabilizer 2. 5 ~ `
Composed of ~
~arlum non~l phenate (120 5% Ba, 21,2
approx, 5UU/o solution) .:
Zinc 2-ethyl hexoate (8. 5% Zn, 21. 2 .
50% solution) -. `
,-, ., ~:
Phenyl diisodecyl phosphite 42.6
Stearoyl benzoyl methane 0 to 5 as noted
in Table I
Mineral spirits 10 to 15 to make ~:
up difference in ~::
w~ight of stearoyl .
benzoyl methane
. ~ -. .
The stabilizer system, dioctyl phthalate, epoxidized .
. ~
soybean oil, calcium carbonate and stearic acid were blended ~ ~:
with the polyvinyl chloride resin on a two-roll mill, and then `
sheeted offO To determine heat processing stability, samples ..
25 were cut off from the sheets and heated in a Geer oven at 350F
and at 375F, for up to two hours. Samples were withdrawn at
'
:,,.
57 .~
~ ~ ~ 2 c~ ~ ~3
fifteen minute intervals to follow the progress of any .
deterioration, as evidenced by discoloration and/or embrittlementO
Deterioration was rated according to the following scale~
Ratin~ Color
0 Unchanged ~ ;~
First perceptible
discoloration ~yellow or buff) :
2 Very pale discoloration
(yellow or buff)
3 Pale yellow or buff .
4 Light yellow or buff
Yellow ~ ~
6 Deep yellow ."`
7 Yellow with black edges . ;. `.
8 Dark yellow brown : -
g Dark brown
Black
The results are shown in Tables I and II:
58
~ ~ 2 s~
Table I
Color Rating at 350C
Control Examplés - -
2 3 4 5 ..
Amount of B-diketone none ~ ~ ~ ~Y ~7c
Time (minutes)
O O O O O O O .,.'.
0 0 0 0 0 0 `-
0 0 0 0 0 o
0 0 0 0 0 0 ``.:
0 0 0 0 0 0 ~ `
1 1 1 1 1 1 .~
105 2 2 2 2 2 2 `
120 3 3 3 3 3 3
... .
:
59 ~:
r
Table II " ~
-
Color Rating at 375F ` ~
ControlExamples ; ~ .;
2 3 4 -5
5Amount of ~-diketone none1~ ~ ~ ~FYo 5~0
Time (minutes) `.
O O O O O O O '`" '
0 0 0 0 0 0 ``~.
0 0 0 0 0 0 ~``
3 3 3 3 3 3 ~:
7 7 7 7 7 7 ``` `:
8 8 8 8 8 8 ``
9 9 9 9 9 9 :
105 10 10 10 10 10 10 `:
The results in Tables I and II show that the ~-diketone,
stearoyl benzoyl methane, has no noticeable effect on heat `
stability at 350 and 375F, since the Control is equivalent to
any of Examples 1 to 5.
Samples also were placed in a Geer oven and held at
20 215F for up to seven days to simulate the moderate
temperatures experienced by a motor vehicle component in a -
motor vehicle, such as automobile, with the following results: `~
Table III .
Color Rating at 215F ; . .
Control Examples _ _
2 3 4 5 :
Amount of B-diketone none ~ ~Y. ~ ~o 5
Tirne (days)
O O O O O O O ',',
o O O O O O -."`,"
2 0 0 0 0 0 0 .`.
: - .
3
4 1 0 0 0 0 0 `
1 0 0 0 0 0 `.
6 2 0 0 0 0 0 .-
7 2 0 0 0 0 0 :.
The ~-diketone, stearoyl benzoyl methane, clearly :
overcomes the instability evidenced by the Control, even in an
amount as low as 1%,
~;
2 ,~
. ,~
Examples 6 to 9
Polyvirlyl chloride resin compositions were made up . .~.
having the following formulation: - :
Ingredient Parts by Wei~ht .. -
.~ ,
Polyvinyl chloride 100 :
homopolymer ~
Dioctyl phthalate 50
Drapex 6. 8 5 ~
(epoxidized soybean oil) ~.
Calcium carbonate 20 `;
(Atom ite) ` ~
Stearic ac id 0. 3 `~:
Stabilizer 3. 0 . ` .
Controls Exam~les
Composed of: 1 2 _ 7 8 9
Barium nonyl phenate 21. 2 21.2 21.221.2 21. 2 210 2
solution 120 5% Ba
Zinc 2-ethyl hexoate 21,2 - 21.221.2 21.2 - ~ .
(8D 5% Zn) (50% solution)
Phenyl diisodecyl 42. 6 42. 6 42. 642. 6 42. 6 42. 6 ;
phosphite
ZnCl2 ~ phenyl diisodecyl - 15 - _ _ 15 :
phosphite (PDDP) ~:
Stearoyl benzoyl - - 1. 00. 25 0. 5 lo O
m ethane
Mineral spirits 15.0 1500 14. 0 14. 75 14. 5 15. 0 ~
:~:
62
,/ .
~ ~ 7J ~ i ~
The stabilizer system and other ingredients (dioctyl
phthalate, epoxidized soybean oil, calcium carbonate and
stearic acid) were blended with the ~olyvinyl chloride resin -` `
on a two-roll mill, and then sheeted off. Samples were cut . ~
off from the sheet and heated in a Geer oven at 350F and . .
375F for up to two hours~ Samples were withdrawn at fifteen ;;.
minute intervals to follow the progress of any deterioration as
evidenced by discoloration and/or embrittlement. Deterioration
was rated according to the scale of Examples 1 to 5. The .
results are shown in Tables IV to VI: `
Table IV
Color Rating at 350F
Controls Examples
Time (minutes) 1 2 6 7 8
. ~ .
o o o 0 o o 0
0 o 0 0 o 0
0 1 0 0 0 1 `~
0 2 0 0 0 2
3 3
1 4 1 1 1 4
105 7 5 7 7 7 5
120 7 5
`',
~'~
'~ ': ' ~
63 ~ .
: ~ "
Table V
Color Rating at 375F ~":
Controls Exar~ple~
Time (minutes) 1 2 6 7 8 9 - `
0 0 0 0 0 0 0 .
~ 0 0 0 `-`
0 0 0 0 0 0 ~ -
7 5 7 7 7 5 :
9 7 9 9 9 7
10 10 10 10 .
The results in Tables IV and V show that the B-diketone,
stearoyl benzoyl methane, contributes no noticeable improvement ~ .:
to heat stability at 350 and 375F.
Samples also were placed in a Geer oven and held at
15 215F for up to seven days to simulate the moderate temperatures
experienced by a motor vehicle component in a motor vehicle
such as an automobile, with the following results:
~ .
64
J' ~
Table VI ~. .
Color Rating at 215F
Control~Exam~les
Time (d_ys) 1 2 6 7 8 9
O O OOOOO -`':'.'.
1 0 0 0 0 0 0
2 1 1 0 0 0 0 ~-
3 1 1 0 0 0 0 ~ -
4 2 2 0 0 0 0 ~;"`
2 2 0
6 3 3 0
7 3 3 0 1 1 1 ~`
The ~-diketone, stearoyl benzoyl methane, clearly
improves stability at 215F after heat processing, as ` ~:
evidenced by comparison of Controls 1 and 2 with Examples 6 to 9.
'',`''
~ ~ 2 r~
Example 10
Polyvinyl chloride resin compositions wsre made up `
~ .~
having the following formulation: ~ .
Ingredient Parts by Weight ` .
5Polyvinyl chloride
homopolymer 100 :
Dioctyl phthalate 50 - ::
Drapex 6, 8 .
(epoxidized soybean oil) 5
Calcium carbonate 20 `
Stearic ac id 0, 3
Stabilizer 3,`0
Stabilizer composed of: ControlExample 10
Diphenyl isodecyl phosphite 40 40 . ~ ~:
Isooctyl thioglycolate trithio-10 10 :
phosphite
Diphenyl phosphite 4 4
Antioxidant 4 4
Barium nonyl phenate-barium 28 28 -~:
carbonate
Zinc chloride phenyl diisodecyl 18 18 :~:
phosphite
Stearoyl benzoyl methane - 1. 0 -~
66
:
2~22~-.g'3 ~;
',.,'..~,
The stabilizer system and other ingredients (dioctyl~ ~;
phthalate, epoxidized soybean oil, calcium carbonate and - ~;
stearic acid) were blended with the polyvinyl chloride resin -~
on a two-roll mill, and then sheeted off. Samples were cut` ~:
off from the sheet and heated in a Geer oven at 350F and
375F for up to two hours. Samples were withdrawn at fifteen.:
minute intervals to follow the progress of any deterioration as ` ~
evidenced by discoloration and/or embrittlement. Deterioration :~ `
was rated accordin~ to the scale of Examples 1 to 5. The
results are shown in Tables VII to IX.
Table VII ~ :
;.
Color Rating at 350F
Time (minutes) C~ntrol Example 10 `
O O O ~:
0 0 `
0 o ~
0 0 ~;
2 2 ` ~;
3 3
105 4 4 --:
120 5 5
~;-
67 :~
~ ?.~ r3`-~ ~.'.. ''.
Table VIII
:. :
Color Rating at 375F ::
Time (minutes) Control Example 10
O O o , `.:
0 o ;~
1 1
2 2
2 2 .`
3 3 :.
10 90 4 4 `~ `
105 5 5
120 7 7 :
The results in Tables VII and VIII show that the B- ~
diketone, stearoyl benzoyl methane, contributes no noticeable : :-
improvement to heat stability at 350 and 375F.
Samples also were placed in a Geer oven and held at ~ -
215F for up to seven days to simulate the moderate temperatures
experienced by a motor vehicle component in a motor vehicle` ~.
such as an automobile, with the following results~
'''~'
68
2 ~ 2 ~
Table ~
, ......
Color Rating at 215F
Time (days) Example 10 Control ~
O O O ' .'
0 o
2 0
3 0
4 0 2 `-
o 3 ~:
6 1 4 `
7 2 4
The ~-diketone, stearoyl benzoyl methane, clearly
improves stability at 215F after heat processing, as
evidenced by comparison of the Control with Example lOo ~ `
69 `~
~22~
Examples 11 to 14 .. ~
:
Polyvinyl chloride resin compositions were made up ~
ha~ing the following formulation: :
Ingredient Parts by Weight
.
Polyvinyl chloride homopolymer
(Oxy 9400) 100
Santicizer 711 (mixed C7-C11
alk~l phthalate) 30
Drapex 6. 8 (epoxidized soybean oil) 5O 0 .::
Omyalite 90T (calcium carbonate) 15 ;~
Loxol GT-71 (fatty ester lubricant) 0~25 .~.
Mic rocheck l lD ~fungic ide) 3 . 0 ; .~ .
TiO2 (R101) 0.25
Dibenzoyl methane 0. 3 ; .
Stabilizer 2, 5
Examples _
1_ 12 13 14
Stabilizer composed of: ;
Barium nonyl phenate
solution 50% (12. 5% Ba) 14.7 17. 6 ~ _
Ba nonyl phenate-Ba 2-
ethyl hexoate (12% Ba) 14.7 17. 6 - -
Ba nonyl phenate-BaCO3
(27% Ba) - - 24, 9 28 ~:
Zinc 2-ethyl he~oate (22% Zn) 1.3 1.6 207
Cd benzoate tallate solution
(14% Cd) 33, 3 20,0
Cd 2 ethyl he~oate benzoate
tallate solutio.n (14% Cd) 14. 7 17. 6
~2,~3~
. ';:':
Examples . .~ .
li 12 13 14 ~ -
.: ;,
Cd 2-ethyl hexoate
(10% Cd) in PDDP - - 41. 2
Diphenyl isodecyl phosphite 140 5 17.4 - 40 ~. .;
Phenyl diisodecyl phosphite
(PDDP) 21. 2
Triphenyl phosphite 3O 2 3, 8
Diphenyl phosphite 0. 31 1. 6 3 4 ~ .
ZnCl2~ phenyl diisodecyl : :
phosphite - - - 18
Isooctyl thioglycolate
trithiophosphite - - - 10
Oleic acid - 0. 8 0. 6 -
Mineral spirits 1. 4 0, 85 5
Cinnamic acid - 0, 75 0, 35
Antioxidant 1. 0 0. 4 1 4
Dibenzoyl methane 1200 12,0 1200 12. 5
In addition, four Controls were made up exactly like
Examples 11, 12, 13 and 14, but without the dibenzoyl methaneO ~ ::
The stabilizer system and other ingredients were -
blended with the polyvinyl chloride resin on a two-roll mill
and then sheeted off. Samples were cut off from the sheets
and heated in a Geer oven at 350F and 375F for up to two
hours. Samples were withdrawn at fifteen minute intervals ~;
and their appearance observed according to the color rating ~;
chart of Examples 1 to 5O The results are shown in Tables ~ . ;
X and XIo
71
~ 2 ~
Table X ~;
Color Rating at 350F
Controls Examples
Time (minutes) 1 2 3 411l ~2 13 114
0 0 0 0 0 0 0 0 0 `-
0 0 0 0 0 0 0
0 0 0 0 0 0 0 0
0 0 0 0 0 0 0 0
0 0 1 1 0 0 0 0 ;
0 0 1 1 0 0 0 0
1 1 2 2 1 1 1 1
105 1 1 2 2
120 1 1 2 2 1 1 1 2 ;~
Table :XI
Color P~ating at 375F
Controls Examl~les
Time ~minutes) 1 2 3 411 12` 13 14 :
o O O O O O O O O '~
0 0 0 0 0 0 0 0
0 0 0 1 0
0 0 0 1 0 0 :
1 1 1 2 1 1 0 1 :;~
3 3 3 3 2 2 1 2 ;~
5 5 5 4 3 3 3
105 7 7 7 5 5 5 5 5 :~
120 8 8 8 7 7 7 7 7 :
,':~
72 .
The dibenzoyl methane clearly contributes no noticeable
effect on heat stabilitsT at 350 and 375F.
Samples also were placed in a Geer oven and
held at 215F for up to seven days to simulate the moderate .:
temperatures experienced by a motor vehicle component in ~ .
a motor vehicle, such as an automobile, with the following results:
Table. XII
Color Rating at 215F
C trols Examples
Time (days) 1 2 3 4 fl
0 0 0 0 0 0 0 0 0 `';`~`~
0 0 0 0 ~;
2 1 1 2 2 0 0 0 0
3 2 2 3 3 0 0 0 0
4 3 3 4 4 0 0 0 0 ;
4 4 5 5 0 0 1 1 `~
6 5 5 6 5 1 1 2 2
q 6 6 7 6 2 2 3 3 ~:~
The ~-diketone, dibenzoyl methane, markedly improves
stability at moderate temperatures after heat processing.
On the other hand, the B-diketone has no noticeable effect :
on stability at low temperatures of the order of 120F (50C)o ` -
This is shown by exposure to fluorescent light in a QUV
fluorescent bulb weathering device, operating at 120F (50C)
in a 4 hour cycle, with the lights on 4 hours and then off 4 hours, ~
for up to 16 days. The samples so exposed gave the following ~ ~;
results~
73 ~
2~22~
Table XlII
QUV Exposure at 120~F ` ~.
Controls Examples
Time ~hours) 1 2 3 4 11 12 13- 14 :
_
o 0 0 0 0 0 0 0 0 ~`
118 1 1 1 1 1 1 1 1 ~`
283 2 2 2 2 2 2 2 2 :
379 2 2 2 2 2 2 2 2
. ..
74
2 ~ ~.' 2 h ~3 5
Examples 15 to 17 : -.
Polyvinyl chloride resin compositions were made up
having the following formulation: ~ ~
Ingredient Parts by Weight ~ .
Polyvinyl chloride homopolymer . .
(Tenneco 22 5) 100
Santiciz~r 711 (mixed C7-C11
alkyl phthalate plasticizer) 30
Drapex 6. 8 epoxldized soybean oil 4. 5 : .
2-hydroxy-4-n-octoxy benzophenone 1. 0 ~: .
Stearic acid 0,25 " -
Stabilizer 3. ;
Examples ~::
Control 15 16 17
Stabilizer composed of:
Barium nonyl phenate BaCO3
(27% Ba) 3, 92 16 16 16 ~
Barium nonyl phenate ~ .
(12. 5% Ba) 24.81 - - - ; -
Cd 2-ethyl-hexoate (20% Cd) 3, 92 - - ~
Cd benzoate-2-ethyl hexoate
tallate (14% Cd) 43,1 50 50 50
Zn~2-ethyl hexoate 1. 3 1. 5 1. 5 lo 5
Diphenyl phosphite 4 4 4 4 -~
Diphenyl isodecyl phosphite 17 17 17 17 ~`;
Oleic acid 0. 67 - - .
Cinnamic acid 0.4 0. 5 0. 5 oO 5
Antioxidant 1.0
Dibenzoyl methane - 2. 5 5.0 7. 5 ~ .
Hydrocarbon diluent - 8. 5 600 3O 5
''.''''''
'
f)-
The stabilizer system and other ingredients were blended
with the polyvinyl chloride resin on a two-roll mill, and
then sheeted off. Samples were cut off from the sheets and
heated in a Geer oven at 350F and 375F for up to two .5:
hours. Samples were withdrawn at fifteen minute intervals,
and the discoloration rated according to the scale in
Examples 1 to 5~ The results are shown in Tables XIV and XV
Table XIV
Color Rating at 350F
Examples ~.
Time ~minutes)Control 1516 1~
.
O O O O O
0 0 0 0
0 0 0 0
0 0 0
1 1 1 1
105 1 1 1 1
120 2 2 2 2
- ~:
76 ~:
2~
Table XV ~
, .
Color Rating~ at 375~F
Examples
Time (minutes)Control 15 16 17
0 0 0 0 0
0 0 0 0 ~
0 0 0 0 --
1 1 1 1 -
2 2 2 2
3 3 3 4
105 5 5 5 6
120 7 7 7 8 ~;
The ~-diketone, dibenzoyl methane, clearly does not
contribute to heat stability at 350 or 375F.
A plate-out test was run on all four resin compositions.
Red pigment was added to the composition and the mix milled `~
on the two-roll mill for five minutes at 325F, and sheeted off
The clean-up sheet run thereafter was exactly the same in all -
four cases, showing the ~-diketone had no effect. ~ -
Thick press-polished panels were prepared from each
composition, and were indistinguishable, one from the other,
again showing the B-diketone had no effect.
Samples also were placed in a Geer oven and held at
25 215F for up to fourteen days, to simulate the moderate
77 --
temperatures experienced by motor vehicle components in a
motor vehicle such as an automobile, with the following results:
Table XVI
Color Rating at 215F ~ ~
Examples _ ~ .
~) Control 15 16 17 . .
O O O O O
0 0
2 0 0 0 ~
1~ 3 1 0 0 0 ;
4 1 0 0
1 0 0 0
6 2 0 0 0 ~ .
7 2
8 3 1 1 1 ~:
9 3 1 1 1 ..
3 1 1 1 `` .
11 4
12 4 2 2 2 :
13 5 2 2 2 .
14 5 2 2 2 -
The B-diketone clearly improves resistance to
discoloration at 215F after heat-processing.
.. ..
.
78 -
~ ~ ~ 2 ~
Example 18
Polyvinyl chloride resin connpositions were made up . ~ `
having the following formulation~
Ingredient Parts by Weight ~ -
P olyvinyl chloride homopolym er ~ .
(Tenneco 225) 100
Santicizer 711 (mixed C7-C11 :.
a~yl phthalate plasticizer) 30 -
Drapex 6. 8 epoxidized soybean oil 4
Blue dye 0.01 "~``
Stearic acid 0.25
Stabilizer 3. 0 ~ .
Control Exam~le 18 `~
Stabilizer composed of~
Barium nonyl phenate BaCO3 ;
(27~o Ba) 32.5 16 ~ ~ :
Cd 2-ethyl-hexoate (20% Cd) - 50
Cd benzoate-2-ethyl hexoate
tallate (14% Cd) 27.4 -. . ~ -
Zn~ 2-ethyl hexoate (22% Zn) 3~1 1. 5
~ .` `.~ ~
Diphenyl phosphite 1. 6 4
Diphenyl isodecyl phosphite - 1~
Diphenyl 2-ethyl hexyl - `.
phosphite 35.
Cinnam ic acid - . 5
Mineral Spirits - 8. 5 ~ ,
Dibenzoyl methane 2, 5
79
2 ~J ~ .3 ~
The stabilizer system and other ingredients were ~ .
blended with the polyvinyl chloride resin on a two-roll mill, -
and then sheeted offO
Blue-tinted convertible rear window press-polished
panels were prepared from each composition, and clippings ~`
taken from each were placed in a Geer oven and held at 215F
for up to fourteen days, to simulate the moderate temperatures
experienced by such rear windows when installed in an :;
automobile, with the following results: -:
: :.
`';
', ',..'
~
2 ~ 2 2 ~
`..',;;
Table XVII
Color at 215F
Time (days) Control Example 18 ` :~
0 Blue Blue ::
1 Unchanged Unchanged `
2 . Faded Blue Unchanged `
Barely Perceptible Unchanged
3 Blue Tint " ~` `
4 Light Gray Unchanged .`~
Gray Tan Faded Blue ;.
6 Light Tan Faded Blue
7 Light Tan Faded Blue : `
8 Light Tan Faded Blue : ~
9 Light Tan Barely Perceptible : ~`
Blue Tint
Medium Tan Barely Perceptible
Blue Tint .::
11 Medium Tan Light Gray ` .~`
12 Dark Tan Light Gray
13 Dark Tan Gray Tan
14 Dark Tan Gray Tan
The ~ diketone clearly improves resistance to
discoloration at 215F after heat-processing. ~
81 ., ~ '':
2 ~ 2 ,~
Example 19
Polyvinyl chloride resin compositions were made up
having the following formulation~
Ingredient Parts by Weight
Polyvinyl chloride homopolymer ~ -
(Tenneco 225) 100
Santicizer 711 (mixed C7-C11
aL~yl phthalate plasticizer) 35
Drapex 6. 8 epoxidized soybean oil 5 `
Atomite (CaCO3) 20
Stearic acid 0. 25 .
Stabilizer 2. 5
Control E:xample 19
.:
...: .
Stabilizer composed of ~
Barium nonyl phenate BaCO3 ~::
(27~o Ba) 32. 5 16
Cd 2-ethyl-hexoate (20% Cd) 27.4 50 ~
Cd benzoate-2-ethyl hexoate ~ `. .`
Tallate (14% C'd)
Zn. 2-ethyl hexoate 3.1 lo 5 `
Diphenyl phosphite 1.6 4 -
Diphenyl isodecyl phosphite - 17
Diphenyl 2-ethyl hexyl
phosphite 3 5
Cinnamic acid - 0. 5 ~-
Mineral Spirits - 8. 5
Dibenzoyl methane - 2. 5
' ' ''
82 ~
The stabilizer system and other ingredients were
blended with the polyvinyl chloride resin on a two-roll mill,
and then sheeted off~ Samples were cut off from the sheets -~:
and heated in a Geer oven at 350F and 375F for up to two
hours, Samples were withdrawn at fifteen minute intervals, :~
and the discoloration rated according to the scale in ;;
Examples 1 ,to 5. The results are shown in Tables XVIII and XIXo ~ ~'
Table XVIII
Color Rating at 350~F
.:
10~Time (minutes) Control Example 19 ,
O '`.'.'
.~.'
0 0 ~-:
0 0 ',~:
0 0 '`~
105 1 1 - :''`''-
120 2 2
~.~..' ;.
83 `:
~ ~ 2 ~ ~3 c3 l3 :
Table X~
Color Rating at 3753F
Time (minutes) ~~ohtrolExample 19
O `'`;
~.
0 0 -:
1 1 . :. .
1 1 :`
2 2 .
3 3 . ~ i
105 5 5 ` ````
120 7 7 ::
The ~-diketone, dibenzoyl methane, clearly does not
contribute to heat stability at 350 or 375F.
Glove compartment boxes were prepared from each ..
composition, The boxes were placed in a Geer oven and
held at 215F for up to fourteen days, to simulate the moderate -;
temperatures experienced by such components in an . .~`
automobile, with the following results:
~ J~ f~ 3
Table XX _ ~:
Color at 215 F
~) Control : Example 19 ;~
0 White White ~.
1 Unchanged Unchanged
2 Unchanged Unchanged
3 Dirty White Unchanged
4 Dirty White Unchanged :
Light Tan Unchanged ~-
6 Light Tan Unchanged
7 Light Tan Dirty White
8 Medium Tan Dirty White
9 Medium Tan Dirty White :;
Medium Tan Dirty White
11 Dark Tan Dirty White ; :
12 Dark Tan Dirty White
13 Dark Tan Light Tan :
14 Dark Tan Light Tan
The ~-diketone clearly improves resistance to
20 discoloration at 215F after heat-processing.
8 5
?~
Examples 20 to 24 `
- , .
Polyvinyl chloride resin compositions were made up
having the following formulation: ~
Ingredient Parts by Weight -
Polyvinyl chloride homopolymer
(Oxy 9400) 100
~antici~r 711 (mixed C7-C11 -` `
allcyl phthalate) 30
Drapex 6.8 (epoxidized soybean oil) 5.0
Omyalite 90T (CaC03) 15 -:
L~xiol GT-71 (fat~y ester lubricant~ O. 25
Microcheck 1 lD (fungic ide) 3.0 ` `
T iO2 (R 101) ' 0.25 `
Heat ~tabilizer 2. 5
~ ':
Controls Examples
2 20 21 22 23 24 `
Heat stabilizer composed of: -
. . .
Ba nonyl phenate-
BaCO3 (27% Ba) 2409 24.~ 24.9 24.9 24,9 24.9 24,9
Zinc 2-ethyl hexoate `
(22% Zn) 2.7 2.7 2.7 2.7 2.7 2.7 207
Cd 2-ethyl hexoate ~-
(10% Cd) 41.2 41.2 41.2 41.2 41.2 41.2 41.2
Phenyl diisodecyl
pho~phite 21.2 21.2 21.2 21.2 2102 21.2 2102
Diphenyl phosphite 3 3 3 3 3 3 3
Oleic acid 006 0.6 0.6 006 0,6 006 006
Mineral spirits 5 5 5 5 5 5 5
Cinnamic acid 0.35 0.35 0.35 0.35 0.35 0.35 0O35
30 Antioxidant
86 -~
2 ~ 3 : ~
Parts by Weight per 100 Parts of Polymer
Other Stabilizers Controls Examples
added sepa ately 1 _2 _ 21 22 23 24
2-Hydroxy-4-octyl~
oxybenzophenone 0~ 5 2, 5 0. 5 0O 5 1.0 0O 5 0~ 5 -"
Stearoyl benzoyl :
methane - 0, 2 0. 5 - - 0. 5 0O 5
Dibenzoyl methane - - - 0.2 0, 5
The stabilizer system and other ingredients were . ~"
blended with the polyvinyl chloride resin on a two-roll mill
and then sheeted off~ Samples were cut off from the sheets
and heated in a Geer oven at 350F and 375F for up to two : .
hours~ Samples were withdrawn at fifteen minute intervals ~
and their appearance observed according to the color rating ` .
chart of Examples 1 to 5~ The results are shown in Tables
X~ and XX,
87 :
2 ~ 2 2 ~ 3 r3
~'-,','''~
.",,
Table X~ : .
Color Rating at 350F . :
Controls Examples
Time (minutes) 1 2 ~) 21 22 23 24 : :
0 0 0 0 0 0 0 0 ..
0 0 0 0 0 0 0
0 0 0 0 0 0 0
4 5 0 0 0 0 0 0 0 `
0 0 0 0 `
0 0 o 0 0 0 0 -:.
105 1 ~ 1 1 1 1 1 `
120
Table ~II
t5 Color Rating at 375F
Controls E:xamples ` ~ `
Time (minutes) 1 Z ~ Z ~ 24
O O O O O O O O ''~'
0 0 0 0 0 0 0 ~
~0 30 0 0 0 0 0 0 0 ` .
0 0 0 0 0 o 0
0 0 0 0 0 0
0 0 0 0 o 0 0 ``~
1 1 1 1 1 1 1
105 1 1 1 1 1 1 1 .
120
~'''.'
88 ~ ~
2 2 ~
. ................................................................... ~ -, . .
:``'
The dibenzoyl methane clearly contributes no noticeable `- `
effect on heat stability at 350 and 375F. . .
Samples also were placed in a Geer oven and
held at 250F for up to seven days to simulate the moderate
temperatures experienced by a motor vehicle component in -- ~
a motor vehicle, such as an automobile, with the following `
results: ;
.,
Table XXIII
Color at 250F ::
Controls Examples
Time (days) 1 2 20 21 22 23 24
0 White Wllite White White White Wllite White
Pink Off White White White White White
White
2 Tan Tan Pink Off Off Off Off
White White White White
3 Tan Tan Pink Off Off Off Pink :`.
White White White .
4 Tan Tan Pink Pink Pink Off Pink
White
Dark Tan Pink Pink Pink Pink Pink
Tan
6 Dark Tan Pink Pink Pink Pink Pink ~:~
Tan
7 Dark Tan Tan ~'ink Pink Pink Pink
Tan
The B-diketones dibenzoyl methane and stearoyl dibenzoyl
methane markedly improve stability at moderate temperatures
after heat processing.
~ .
89
-~` 2~22~.5 ~ ~
,.,, :.'.:.'...
xample 25
. .
Polyvinyl chloride resin compositions were made up; `;
having the following formulation: "
In~redient Parts by Wei~
Polyvinyl chloride homop~lymer
(Oxy 9400) 100
Santici~er 711 (mixed C7-C11 ~`
alkyl phthalate) 30
Drapex 6. 8 (epoxidize,d soybean oil) 5. 0
Omyalite 90T (CaCO3) 15
Lorol GT-71 (fatty ester lubricant) 0, 25
.
TiO2 (R101) 0.25
Stabilizer 2, 5
Control Example 25
Stabilizer composed of:
, :
Ba nonyl phenate-BaCO3
(27% Ba) 21 21
Zinc 2-ethyl hexoate
(22% Zn) 4.6 4.6
Cd 2-ethyl hexoate
benzoate tallate solution
(14% Cd) 17 17 ~;
Dlphenyl isodecyl
phosphite 3 5 3 5
Diphenyl phosphite 1, 5 1. 5
Aromatic hydrocarbon -
diluent 15.9 10. 9
Tall oil fatty acid 3 3
Antioxidant 2 2 ~
Dibenzoyl rnethane - 5 ~ -
-, .."~
`~ 202~5 :: ~
The stabilizer systern and other ingredients were :
blended with the polyvinyl chloride resin on a two-roll mill `-
and then sheeted off. Samples were cut off from the sheets
and heated in a Geer oven at 350F and 375F for up to two
hours. Samples were withdrawn at fifteen minute intervals
and their appearance observed according to the color rating
chart of Examples 1 to 5. The results are shown in Tables `
~IV anc~
Table XXIV
Color Rating at 350F
.~
Time (minutes) Control Example 25
O O
0 0
0 0 :~
0 ~`
0 0
0 0
105 1 1 :~
120 1 1
91
~ ` 2 ~ 2 2 g ~
`: `
Table X~
Color Rating at 375F ` -~
Time (minutes) Control Example 25 ~ -.
O O O ~, .
0 0
` ~` ~`.`
0
0 `:
.
10 90
105 2 2 .
120 3
The dibenzoyl methane clearly contributes no noticeable .
effect on heat stability at 350 and 375F,
Samples also were placed in a Geer oven and held
at 250F for up to eight days to simulate the moderate
temperatures experienced by a motor vehicle component in
a motor vehicle, such as an automobile, with the following
results:
92 ~ ;:
2~22~5 ~ ~:
Table X~
Color at 2 50 F
Time (days) Control Example 25
0 White White `
1 Off White White
2 Light Tan Off White
3 Light Tan Off White
4 Light Tan Off White
Tan Light Tan ~: `
6 Dark Tan Dark Tan -:
7 Dark Tan Dark Tan .
8 Dark Tan Dark Tan
The ~-diketone, dibenzoyl methane, markedly improves ~:
stability at moderate temperatures after heat processing.
,~" ~.
93
2~228~
Example 26 -
Polyvinyl chloride resin compositions were made up
having the following formulation~
Ingredlent Parts by Weight
5 Polyvinyl chloride homopolymer
(Oxy9400) 100
Santl~izer 711 (mixed C7-C11
ah'cyl phthalate) 30
Drapex 6. 8 (epoxidized soybean oil) 5J O
Omyalite 90T (CaCO3) 15
LorolGT-71 (fatty ester lubricant) 0. 25 `;
T iO2 (R 101) 0. 2 5 -
Stabilizer 2. 5
Control Example 26
15 Stabilizer composed of:
Barium nonyl phenate solvent `
(50%) (12. 5% Ba) 14.7 - ;
Ba nonyl phenate-Ba 2-ethyl
hexoate (12. 5% Ba) 14. 7 14. 66 `-
Ba nonyl phenate-BaCO3 `-
(27% Ba) 6.79
Zinc 2-ethyl hexoate - ~
(22% Zn) 1.3 1.33 ~ `
Cd benzoate tallate solvent
(14% Cd) 33. 3 33.3
Cd 2-ethyl hexoate benzoate ~
tallate (14% Cd) 14. 7 14. 67 ~`
Diphenyl isodecyl phosphite 14. 5 14. 53 ~ -
Triphenyl phosphite 3. 2 3. 3 ~;
Diphenyl phosphite 0. 31 1. 33
Mineral spirits 1. 4 4~ 8 ;
Antioxidant 1. 0 0. 33
Dibenzoyl methane - 5. 0 ~ ;~
~ 4
2022~S
The stabilizer system and other ingredients were
blended with the polyvinyl chloride resin on a two-roll mill
and then sheeted off. Samples were cut off from the sheets
and heated in a Geer oven at 350F and 375F for up to two .
hours. Samples were withdrawn at fifteen minute intervals
and their appearance observed according to the color rating :
chart of Examples 1 to 5. The results are shown in Tables
XXVII and xx~TmO
Table ~VII :"
Color Rating at 350F
Time (minutes) Control Example 26
.
O O O ~ ~
0 0 ;
0 0 .
0 0 :
0
0 o `,
105 1 1 -
120
~:
`` 2 0 2 2 8 ~
Table X~III
-, ~
Color Rating at 375F : .
Time (minutes) ControlExample 26 ~ :
O O ' ;~`
0
0
~5 0 0
0 `
9Q 1 1 .-`~
105
120
The dibenzoyl methane clearly contributes no noticeable ~ ~:
effect on heat stability at 350 and 375F. `
Samples also were placed in a Geer oven and held
at 250F for up to eight days to simulate the moderate
temperatures experienced by a motor vehicle component in -
a motor vehicle, such as an automobile, with the following
results~
96
2~228~
Table X~
Colorat250F :
_ . ,
Time (days) Control Example 26
0 White White
. .
1 White White
2 White White - ~
3 Off White Off White ~ ::
4 Light Tan Off White
Light Tan Off White ;;
6 Tan Light Tan
7 Tan Light Tan
8 Tan Light Tan
The B-diketone, dibenzoyl methane, markedly improves
stability at moderate temperatures after heat processing. :~
. ~. . .
97 .
.:
2~228~S
Examples 27 and 28
Polyvinyl chloride resin compositions were made up
having the following formulation:
gredient Parts by Weight
Polyvinyl chloride homopolymer ~ -
(Tenneco 225) 100
Santicizer 711 (mixed C7-Cll
aLkyl phthalate plasticizer) 35
Drapex 6. 8 epoxidized soybean oil 5
Atomite (CaCO3) 20 ~;
Stearic acid 0~,25
Stabilizer 29 5
Control Example 27 Example 28
Stabilizer connposed of ~
,
13arium nonyl phenate B aC03
(27% Ba) 3. 92 16 16
.... ~
Barium nonyl phenate -~
( 12. 5% Ba) 24, 81 - -
Cd 2-ethyl-hexoate (20% Cd) 3O 92 - -
Cd benzoate-2-ethyl hexoate
tallate (14% Cd) 43.1 50 50
Zn~ 2-ethyl hexoate (22 Yo Zn) 1. 3 1. 5 1. 5
Diphenyl phosphite 4 4 4
Diphenyl isodecyl phosphite 17 17 17
Oleic acid 0O 67
Cinnamic acid 0.4 0. 5 0O 5
Antioxidant 1, 0 - -
Dibenzoyl methane - 59 0 5O 0 ~ - -
Hydrocarbon diluent - 6. 0 6. 0
Zinc chelate of dibenzoyl
methane - - 60 5
98
~ ',.`'
2~22~
The zinc 2-ethyl hexoate and dibenzoyl methane formed
the zinc chelate of dibenzoyl methane in situ. ~ `;
The stabilizer system and other ingredients were blended
with the polyvinyl chloride resin on a two-roll mill, and
then sheeted off. Samples were cut off from the sheets and ;.
heated in a Geer oven at 350F and 375F for up to two
hoursO Samples were withdrawn at fifteen minute intervals,
and the discoloration rated according to the scale in
Examples 1 to 5. The results are shown in Tables X~ and
XX~Io
Table XXX
Color Rating at 350F
Time (minutes) ControlExample~27 Example 28
O O O o :
15 15 0 `
0 o 0
0
o o o .
0
20 90
105
120 2 2 2 ~-
'~
, ~
.
~`` 2022~
Table XXXI ~ `:
Color Rating at 375F ~:
; - .
Time (minutes) Control Example 27 Example 28
O '` '~
O O ` ;: `
0 0 ` `
O o O
1 1 1 .
2 2 2 ``
105 2 2 2
120 3 3
The ~inc chelate of the ~-diketone, dibenzoyl methane, : ;~
clearly does not contribute to heat stability at 350 or 375F~
A plate-out test was run on all four resin compositions . ;;;
Red pigment was added to the composition and the mix milled ;
on the two-roll mill for five minutes at 325F, and sheeted off, ;
The clean-up sheet run thereafter was exactly the same in all
four cases, showing the zinc chelate of the B-diketone had no
20 effect.
Thick press-polished panels were prepared from each `
composition, and were indistinguishable, one from the other,
again showing the zinc chelate of the B-diketone had no effect. :
Samples also were placed in a Geer oven and held at
25 215F for up to sixteen days, to simulate the moderate
temperatures experienced by motor vehicle components in a -
motor vehicle such as an automobile, with the following results; ~
100 .....
,.~ .
.'-.'
: ` 2i~2~5
Table XXXII ; ~:
Color Rating at 215F
Time (days)Control Example 27 Example 28
O O O O
1 0 0 0 `~`
2 0 0 0
3 0 0 0
4 1 0 ~ ~ `
O
6 2 0 0
7 2 1 ~ `
8 3
9 3
11 4
12 4 2 2
13 5 2 2
14 5 2 2 ~ ~
2 2 ~ .
16 5 2 2 :-
The zinc chelate of dibenzoyl methane clearly improves
resistancè to discoloration at 215F after heat-processing.
~... ~,.
,.'-",''',''''
101
.. - .
''~",,'
2~2~5 ~ :
A blue dye was then added with the stabilizer system --
and other ingredients of the polyvi.nyl chloride resin composition -~
described above, and blended with the polyvinyl chloride resin
on a two-roll mill, and then sheeted off.
Blue-tinted press-polished convertible rear window ~ ~
panels were prepared from each composition, and clippings ;; .
taken from each were placed in a Geer oven and heated at 215F
for up to sixteen days, to simulate the moderate temperatures :.
experienced by such rear windows when installed in an .~;~
automobileO The results were the same as in Table XX~IL ~`
The Zn chelate of dibenzoyl methane clearly improved
.
resistance to discoloration at 215F after heat-processing. ~ "
", -
',`,"..-'~.
102
- 2~2~
Exam~les 29 to 32
Polyvinyl chloride resin compositions were made up
having the following formulation:
Ingredient Parts by Weight ~ ;~
Polyvinyl chloride homopolymer ~ :
(~eon llOX 450) 100
D~octyl phthalate 40 :
Drapex 6, 8 epoxidized soybean oil 5 ;`
Atomite (CaC09) 20
Stearic acid 0.2
Stabilizer 2, 5
Examples
Control 29 30 31 32
Stabilizer composed of: ~.
Barium nonyl phenate Ba.CO3 ~ .
(27~o Ba) 3. 92 3. 92 ~6 16 16 ;
Barium nonyl phenate
(12. 5% Ba) 24. 81 24. 81
Cd 2-ethyl-hexoate (20% Cd) 3, 92 3. 92
~ -.;
Cd benzoate-2-ethyl hexoate
tallate (14% Cd) 43.1 43.1 50 50 50 .
Zn~ 2-ethyl hexoate (22% Zn) 1. 3 1. 3 1. 5 1. 5 lo 5 `~
Diphenyl phosphite 4 4 4 4 4
Diphenyl isodecyl phosphite 17 17 17 17 17 . .
2 5 Oleic acid 0. 67 0.67 _ .
. . .
Cinnamic acid 0.. 4 0.4 0. 5 0~ 5 0. 5
.. . ...
Antioxidant 1. 0 1. 0 - - -
Dibenzoyl methane - - 2. 5
Hydrocarbon diluent - - 2. 5 8. 5 80 5
Cadmium chelate of ~ .
dibenzoyl methane - 0.1 - 20 5 40 0 ~
'''",'
103 ~;.
2~228~
The cadmium 2-ethyl hexoate and dibenzoyl methane formed ~ ~ ~
the cadmium chelate of di~enzoyl methane in SitU in Example 290 ~ .
The stabilizer system and other ingredients were blended ;
with the polyvinyl chloride resin on a two-roll mill, and
then sheeted off. Samples were cut off from the sheets and
heated in a Gëer oven at 350F and 375F.for up to two ~:
hours. Samples were withdrawn at fifteen minute intervals,
and the discoloration rated accorcling to the scale in -
Examples 1 to 5O The results are shown in Tables ~XIII and XXXIV
Table ~xm
Color Rating at 350F
Examples ; `
Time (minutes) Control 2~ 32
O O ~O O O O ;`
0 0 0 0 0
~;
; ~`
0 ; ~ "
~` ~
1 1 1 1 1 ~`:
105 1 1 1 1 1 -
120 2 2 2 2 2
' ` .
,,
~,~
. ~',.'
104
Table ~XIV
~. ~
Color Rating at 375F ~ ~
: .
Examples -
Time (minutes)Control 29 30 31 32
-
0 0 o
0 o 0 - :~
0 o 0
1 1 1 1 1 .
1 1 1 1 1 .---i
2 ~ 2 2 2
3 3 3 3 3 -
105 5 5 5 5 5
120 10 10 10 10 10 ~;
The cadmium chelate of dibenzoyl me~hane clearly does not
contribute to heat stability at 350 or 375F, ;~`
A plate-out test was run on all four resin compositions. . .
Red pigment was added to the composition and the mix milled
- :........
on the two-roll mill for five minutes at 325F, and sheeted offO `
The clean-up sheet run thereafter was exactly the same in all .
Iour cases, showing the cadmium chelate of the B-diketone had no effect~
Thick press-polished panels were prepared from each
composition, and were indistinguishable, one from the other, : ` .
again showing the cadmium chelate of the B-diketone had no effect. --
Samples also were placed in a Geer oven and held at
215F for up to fourteen days, to simulate the moderate -
' ~"','
: .
105 ~ ~
2~2285~
temperatures experienced by motor vehicle components in a
motor vehicle such as an automobile, with the following results:
Table XXXV ;
Color Rating at 215F
Examples ~ `.
Time (days) Control 29 30 31 32
O O O
, 0 0 O
2 0 0
3 ```
4 1 o o 0 1 :
1 0 0 0 1 ;
6 2 0 0 0 1 :~
7 2 1 1 1 1 `
8 3 2 1 1 ~ `.
9 4
3 1 1 1 `
11 6 4 1 1 1 :-
12 6 4 1 1 1 :-
13 7 4
14 7 5 1 1 1 -
The cadmium chelate of dibenzoyl methane clearly improves -
resistance to discoloration at 215F after heat-processing. Example - .:
29 sh~ws that even Oo l chelate is helpful, but Examples 30 and 31 ~ `
25 show that 2. 5 and 4 of chelate are better.
106 ` .
2~22~S
A blue dye was then added with the stabilizer system
and other ingredients of the polyvinyl chloride resin composition
described above, and blended with the polyvinyl chloride resin
on a two-roll mill, and then sheeted off, ~:
Blue-tinted press `polished convertible rear window
panels were prepared from each composition, and clippings ~`
taken from each were placed in a Geer oven and heated at 215F ~
for up to sixteen days, to simulate the moderate temperatures `- `
experienced by such rear windows when installed in an ~ ~`
automobile. The results were the same as in Table XX~
The cadmium chelate of dibenzoyl methane clearly :
.,.~-. .
improved re~istance to discoloration at 215F after heat-processingO
;
:
~,
.
'''`'''''~
;~
107 `
