Note: Descriptions are shown in the official language in which they were submitted.
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WO 96J38~01 PCT/US96107042
ALKYL-TIN PVC STABILIZERS WITH ADDED AROMATIC ETHER
ALCOHOL TO PRFVE~IT PRECIPITATION
The present invention relates to liquid
stabilizer systems for vinyl halide resin
compositions, and to resinous compositions of such
products. More particularly, it relates to liquid
stabilizer systems including a tin-organo sulfur
compound and an additive therefor.
It is well known that vinyl halide resins
undergo undesirable changes when they are exposed to
heat or to light, and that these changes lead to
discoloration and to deterioration of the mechanical
properties of compositions containing such resins.
Since elevated temperatures are required for the
5 processing and/or formulation of compositions
containing these resins, and since the resins are
exposed to heat, to light, or both, when they are
subsequently used, it is necessary to incorporate in
the vinyl halide compositions stabilizers that will
inhibit or prevent discoloration, or loss of physical
integrity, when they are exposed to such conditions.
Organo tin compounds that contain sulfur
have long been recognized as highly effective heat
stabilizers for vinyl halide resin compositions.
Examples include organo tin ethanol mercaptides such
as those disclosed in U.S. Patent No. 4,059,562;
organotin aliphatic mercaptides as disclosed in U_S.
Patent No. 2,726,227; dialkyltin sulfides as disclosed
in U.S. Patent No. 2,746,946; monoalkyltin sulfides as
disclosed in U.S. Patent No. 3,021,302; reaction
products of organotin trihalides with sodium
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1 alkylmercaptide and sodium sulfide, as disclosed in
U.S. Patent No. 3,442,852; and monomeric tetra- ,
functional organo tin mono- or di-alkyl di- or tri-
(alkyl thioglycolate) or (mercapto alkyl carboxylate)
compounds such as disclosed in U.S. Patent No.
5,032,634.
A thorough historical review of organotin
and organotin-sulfur compounds in stabilizing
polyvinyl chloride compositions appears in the
~~plastics Additives and Modifiers Handbook" (J.
Edenbaum, Van Nostrand Reinhold, 1992, at pp. 309-326,
Chapter 19: Dworkin, "Polyvinyl chloride processing
stabilizers: tin and its derivatives".
Combinations of alkyl tin sulfides and alkyl
mercaptides are useful liquid stabilizers for vinyl
halide resins, but have long been known to exhibit a
tendency to form precipitates on formation, or on
standing. The precipitates generally have a higher
tin content than the liquid product, but are
considerably less effective as stabilizers. Thus, the
formation of the precipitates represents an
undesirable economic loss, in the stabilization
efficiency which is lost, in the cost of the product
which is lost to the precipitate, as well as in the
input of material and energy necessary to attempt to
redissolve or otherwise handle the precipitates.
In particular, as pointed out in U.S. Patent
No. 4,059,562, organotin ethanol mercaptides are
subject to cloudiness and decomposition in storage.
According to that patent, avoiding the cloudiness and
decomposition requires formulating the mercaptides
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-3
~- with 10 to 400 of a liquid alcohol component that
comprises a glycol and an alkyl acid phosphate.
There thus remains a need to formulate
liquid stabilizers for vinyl halide compositions,
which do not exhibit a tendency to form precipitates
and yet which otherwise can be formulated effectively
into vinyl halide resin compositions.
The present invention is directed to a
homogeneous liquid stabilizer composition for
polyvinyl halide) compositions which exhibits a
reduced tendency to form precipitate on standing,
comprising
(a) an aromatic ether alcohol of formula (1)
Ar-O- (CHzCH(X)O)nH (1)
wherein Ar is aryl containing 6 to 10 carbon atoms;
X independently in each occurrence is -H or
- CH 3 ; and
n is 1 to 5; and
(b) an alkyl phenol of formula (2)
A,, - C, H,~ ~, OH ( 2 )
wherein k is 1 or 2 and A is straight or branched
alkyl containing 1 to 12 carbon atoms provided that
the total number of carbon atoms in said 1 or 2 alkyl
groups A is 6 to 24; and
(c) an admixture of alkyl tin compounds
including one or more butyltin alkyl mercaptides
' corresponding to formula (3)
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-4
(R1) Sri (-SRz) 4_a
one or more butyltin hydroxyethyl
mercaptides corresponding to formula (4)
,
(R' ) aSri (-SCHZCHiOH) 4_a (4 )
and one or more compounds selected from the group
consisting of dibutyl tin sulfides corresponding to
formula (5a) and monobutyl tin sulfides corresponding
to formula (5b)
(R') ~SnS (5a) (R'Sn)~S3 (5b)
-5 wherein R' is a butyl group; a is 1 to 2; and R
independently at each occurrence is straight or
branched alkyl or alkenyl having 8 to 16 carbon atoms.
The foregoing composition can optionally be
admixed with one or more methyltin compounds selected
from the group consisting of methyltin mercaptides
corresponding to formula (3) wherein R' is methyl,
methyltin hydroxyethyl mercaptides corresponding to
formula (4) wherein R' is methyl, dimethyl tin
sulfides corresponding to formula (5a) wherein R1 is
methyl, and monomethyl tin sulfides corresponding to
formula (5b) wherein R' is methyl. When any such
methyltin compound is present, the total amount of all
such methyltin compounds present, as a ratio (on an
equivalents basis) to the total amount of all
compounds present corresponding to formulas (3), (4),
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~- (5a) and (5b) wherein R1 is butyl, is up to 1:1 ,
generally 1:99 to 1:1.
The components (a), (b) and (c) are present
in such amounts relative to each other that the
composition containing components (a), (b), and (c) is
a homogeneous liquid which does not exhibit the
formation of haze or precipitates on formation and is
stable against formation of precipitates on standing,
even prolonged standing.
The present invention is also directed to
vinyl halide resin compositions containing such a
stabilizer composition in an amount thereof effective
to impart to the vinyl halide resin increased
stability against heat-mediated degradation of the
Z-5 polymer composition.
Further, the present invention is directed
to a method of providing stability against precipitate
formation of a liquid stabilizer composition which
comprises one or more compounds of the foregoing group
(c), comprising admixing into said composition one or
more compounds of the foregoing formula (1) and one or
more compounds of the foregoing formula (2) in amounts
thereof effective to provide stability against
precipitate formation of said admixture.
The present invention surprisingly affords
numerous advantages, heretofore unavailable, to
stabilizer compositions containing one or more
compounds of formula (3). Preferably, the stabilizer
compositions of the present invention comprise an
admixture of at least one compound represented by
formula (3), at least one compound represented by
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formula (4), and at least one compound represented by
formula (5a) or by formula (5b).
Referring again to formula (3), the radical
R'= is an alkyl group, or an alkenyl group containing
up to 3 carbon-carbon double bonds, and overall'
contains 8 to 16 carbon atoms. R' can be straight-
chained or branched, and is preferably straight. The
preferred embodiments of R' are alkyl containing 10 to
14 carbon atoms, and most preferably Rz is an alkyl
group which contains 12 carbon atoms, i.e. lauryl.
The radical R1 in each of formulas (3), (4),
(5a) and (5b) denotes a butyl radical containing 4
carbon atoms, i.e. n-butyl, isobutyl, sec-butyl or
tent-butyl. Preferred embodiments of the present
invention include those wherein R1 is n-butyl and
those wherein compounds of the formulas (3), (4), (5a)
and/or (5b) in which R1 is methyl are present together
with compounds of any of said formulas wherein R1 is
n-butyl.
Again referring to formula (3) there are 2
or 3 groups of the formula Rz-S-, and 1 or 2 groups of
the formula R1, provided that the total number of both
of said groups present is 4.
In the composition and method of the present
invention, there are present hydroxyethyl mercaptides
corresponding to formula (4) and sulfides
corresponding to formulas (5a) and/or (5b), in which
R~ and a are as defined above.
It has now been discovered that liquid
stabilizer compositions containing one or more
alkylmercaptide compounds of formula (3), one or more
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l hydroxyethyl mercaptide compounds of formula (4), and
one or more sulfides of either or both of formulas
.
(5a) and (5b), are surprisingly and effectively
rendered resistant to formation of precipitate by the
presence of effective amounts of one or more compounds
of each of formulas (1) and (2) as described herein.
In the compounds of the formula (1)
1~
Ar-O- (CHzCH(X)O)nH (1)
the group Ar can be a monocyclic or bicyclic aryl
group containing 6 to 10 carbon atoms. Preferably, Ar
is phenyl. This compound of formula (1) contains 1 to
repeating alkoxy units. As can be seen, each
occurrence of the substituent X can be hydrogen or
methyl, although it is preferred that each occurrence
of the substituent X in a given compound is the sane.
The compound of the formula (1) should be water-
insoluble, by which is meant that it exhibits a
solubility of less than 3 grams per 100 milliliters of
water.
Compounds of formula (1) can be synthesized
in a straightforward manner by reaction of the
corresponding aryloxy precursor, e.g. phenol, and
alkylene oxide such as ethylene oxide or propylene
oxide whereby the aryl group is attached to one end
thereof. Compounds of formula (1) which exhibit
satisfactory performance in the compositions of the
present invention are also commercially available.
For instance, ethylene glycol phenyl ether (having the
' formula C,;HSOC~HaOH) and propylene glycol phenyl ether
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-8-
(also termed 1-phenoxy-2-propanol, having the formula
C,,H,,OC,H,,OFi) are commercially available as,
respectively, "*Dowanol EPh" and "*Dowanol PPh" from Dow
Chemical Company.
S Compounds of formula (2), known as
alkylphenols, are generally commercially available and
can readily be synthesized by straightforward
synthetic techniques. There can be one or two alkyl
substituents A in formula (2), and when two such
substituents are present they cart be the same or
different. Each substituent A is straight or branched
alkyl containing 1 to 12 carbon atoms, provided that
the total number of carbon atoms in the one or two A
groups present is 6 to 24. Each A contains preferably
6 to 12 carbon atoms. The alkyl substituents A and
the -OH group can be ortho,.rneta or para to each
other. Examples of suitable compounds of formula (2)
include hexylplienol , heptylphenol , sec-octylphenol ,
tert-octylphenol, diisopropylphenol, nonylphenol,
dinonylphenol, and didodecylphenol.
Satisfactory ratios of the amounts of
aromatic ether alcohol(s) of formula (1) and the alkyl
phenols) of formula (2) to each other and to the one
or more compounds of formulas (3), (4), (5a) and (5b)
present in the composition, can be ascertained for any
particular formulations being employed, for instance
by formulating a given composition and assessing its
tendency to form precipitate upon formulation and upon
standing for a given length of time at a specified
temperature.
*trade-mark
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The relative amounts of the compounds of
formula (3) , of formula (4) , and of formulas (5a)
and/or (5b) present in the composition are
conveniently expressed as equivalents. The ratio in
equivalents of the amount of all alkyl mercaptide of
formula (3) present, to the amount of all hydroxyethyl
mercaptide of formula (4) present, is preferably 60:40
to 80:20. The ratio in equivalents of the amount of
all mercaptide together, of formulas (3) and (4),
present to the amount present of sulfide of formulas
(5a) and (5b), is preferably 55:45 to 75:25. It
should be understood that the number of equivalents
present of a given compound is proportional to the
number of moles thereof present, through the equation
5 (no. of equivalents) - (no. of moles) x (valence).
For the compounds referred to in the foregoing ratios
and precursors thereof, the amounts thereof and the
number of equivalents thereof are related as follows:
No. of equivalents
Compound per one mole
Alkyl mercaptan (R1SH)
2-Mercaptoethanol (HOCH.,CHzSH) 1
Sodium sulfide (NaZS) 2
Dialkyltin dialkyl mercaptide 2
(formula (3), a=2)
Monoalkyltin trialkyl mercaptide 3
(formula (3), a=1)
Dialkyltin bis(hydroxyethyl mercaptide) 2
(formula (4) , a=2)
Monalkyltin tris(hydroxyethyl mercaptide) 3
(formula (4) , a=1)
Dialkyltin sulfide 2
(formula (5a) )
Monoalkyltin ~mlfide
(formula (5b) )
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The ratio of the amount of the one or more
compounds of formula (1) present in the composition of
the present invention to the total amount of all
compounds of formulas (3) , (4) , (5a) and (5b) is ,
preferably 3 to 7 wt. a.
The ratio of the amount of the one or more
compounds of formula (2) present in the composition of
the present invention to the total amount of all
compounds of formulas (3) , (4) , (5a) and (5b) is
preferably 4 to 10 wt. o.
Without intending to be bound by any
particular explanation of the operation of the
invention, the invention has been observed to exhibit
behavior consistent with the proposition that since
the aromatic ether alcohol is essentially water
insoluble, this insolubility assists in retaining the
tin compounds of formula (3) and sulfides thereof in
the stabilizer product. This behavior retains the
full stabilization capability of the tin compounds and
simultaneously avoids contamination of waste water
streams generated during the synthesis of the
compounds. In addition, the aromatic ether alcohol
appears to contribute uniformity to the organic phase
that is formed, while solubilizing the various species
of the stabilizer composition to form a homogeneous
liquid product. The aromatic ether alcohol also
reduces the water content in the organic phase, thus
effectively reducing the time and the severity of the
conditions (e. g. temperature) necessary to dry (e. g.
remove water from) the product.
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In the present invention, and particularly
in those embodiments comprising tin compounds
substituted with both methyl and butyl groups, it has
also been determined that the stability against
precipitate formation is further enhanced if the
liquid composition also contains an effective amount
of a mercaptoalkyl ester of one or more linear fatty
acids containing 16 to 20 carbon atoms and 0-3 carbon-
carbon double bonds. The mercaptoalkyl substituent
can be straight or branched and can contain 1 to 4
carbon atoms; the preferred mercaptoalkyl substituent
is 2-mercaptoethyl. Contemplated for purposes of this
invention are mixtures of such esters, including
especially mixtures of a given ester (e.g. the 2
mercaptoethyl esters) of a mixture of fatty acids
conforming to the foregoing definition. One preferred
embodiment of this aspect of the invention is "2-
mercapto tallate", that is, the 2-mercaptoethyl esters
of tall oil fatty acids. Tall oil fatty acids are a
recognized commercial product comprising a mixture of
saturated and unsaturated fatty acids, predominately
C,~-C,~, in length. Typical tall oil fatty acids include
mixtures comprising generally about 0.1 wt.o palmitic
acid, 0.3 wt.a palmitoleic acid, 2.1 wt.o stearic
acid, 48.5 wt.o oleic acid, 43.1 wt.o linoleic acid
(various isomers), 3.5 wt.o pinolenic acid, and 1.1
wt.o eicosenoic acid, it being recognized that each of
the values are expressed as ~ 100.
Typically, the mercaptoalkyl fatty acid
ester component is about 3 wt.% to about 10 wt.o of
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Z- the liquid stabilizer composition, and more preferably
about 5 wt.o to about 7 wt.% thereof.
Compounds of formulas (3), (4), (5a) and
(5b) and admixtures thereof can be prepared in
straightforward manner by reacting precursors as
described herein. The precursors are readily
available commercially and can themselves be
synthesized readily.
In general, compounds of formula (3) and (4)
can be prepared by reacting monoalkyl tin trihalide,
dialkyl tin dihalide, or a mixture thereof (wherein
the halide i.s prefer-abl.y chloride) , with one or more
alkyl mercaptans of the formula R2SH, with 2-
mercaptoethanol or (preferably) with both of one or
more of said alkyl mercaptans and 2-mercaptoethanol,
wherein Rz is as defined herein. The reaction is
preferably carried out in an aqueous alkaline solution
containing, for example, ammonium hydroxide, potassium
hydroxide or sodium hydroxide. The product is
recovered as a hydrophobic liquid phase separating
from the aqueous phase, for instance in a separatory
funnel, followed by stripping and filtering undesired
side products.
Similarly, compositions including sulfides
of one or more compounds of formulas (5a) and/or (5b),
including monoalkyl tin sulfides, dialkyl tin
sulfides, or both, can be made by carrying out the
aforementioned reaction in aqueous alkaline solution
and then adding a solution of a sulfide such as sodium
sulfide in water, thereby to convert remaining
trihalides and/or dihalides to sulfide. The desired
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1 product is recovered as a hydrophobic liquid phase
separating from an aqueous brine phase in a decanting
vessel such as a separatory funnel, and stripping and
filtering undesirable side products.
The compound or compounds of formulas (1)
and (2) present according to the present invention are
preferably added to the reaction mixture during the
aforementioned series of synthesis steps, although it
is preferred to add the ether of formula (1) prior to
addition of the sulfide reagent and to add the
alkylphenol after addition of the sulfide reagent.
Addition of the compounds of formulas (1) and (2) can
also be effected following recovery of the composition
as separated from the aqueous phase, but this is less
Z-5 preferred as the tin-based stabilizer would still be
vulnerable to precipiate formation during the period
before the aromatic ether and the alkyl. phenol are
added.
It will of course be recognized that the
reagents described herein should be added in the
appropriate amounts effective to form, following their
reaction, compositions which exhibit the desired
conformity to the empirical formulas, and which
exhibit the ranges of amounts and ratios, described
herein. Identification of those amounts of reagents
is a straightforward matter for those familiar with
this field of technology.
Synthesis of the liquid stabilizer
composition in accordance with the present invention
exhibits rapid phase separation, thereby facilitating
synthesis and minimizing the need to remove entrained
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water. Thus, the organic phase formed in the
synthesis generally contains surprisingly reduced
amounts of water on the order of 1 to 100, and often 1
to 50.
The liquid stabilizer compositions of the
present invention are preferably used to advantage in
combination with vinyl halide resins, preferably
polyvinyl cloride resins. The term "polyvinyl
chloride" as used herein is inclusive of any polymer
formed at least in part of the recurring group (-CHC1-
CX,-)~, and having a chlorine content in excess of 400.
In this formula, each of the X groups can be either
hydrogen or chlorine, and p is the number of units in
each polymer chain. In polyvinyl chloride
homopolymers, each of the X groups is hydrogen. Thus,
the terms "PVC" and "polyvinyl chloride" include not
only polyvinyl chloride homopolymers but also after-
chlorinated polyvinyl chlorides, as well as copolymers
of vinyl chloride in a major proportion with other
copolymerizable monomers in moderate proportion such
as copolymers of vinyl chloride and vinyl acetate,
copolymers of vinyl chloride with malefic or fumaric
acids or esters, and copolymers of vinyl chloride with
styrene. The stabilizer compositions are effective
also with mixtures of polyvinyl chloride in major
proportion with a minor proportion of other synthetic
resins such as chlorinated polyethylene or copolymers
of acrylonitrile, butylene and styrene.
Stabilizer compositions of the present
invention can be used with plasticized polyvinyl
chloride resin compositions of conventional
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-15
1 formulation. Conventional plasticizers well known to
those skilled in the art can be employed such as, for
example, dioctyl phthalate, octyl diphenylphospate,
and epoxidized soybean oil. Particularly useful
plasticizers are the epoxidized esters having from 20
to 150 carbon atoms.
The stabilizer compositions of the present
invention are used in small but effective amounts to
impart heat stability, that is, enhanced resistance to
heat-mediated deterioration of the PVC or other
polyvinyl chloride resin. That is, "heat-mediated
deterioration" includes deterioration which is due to
exposure to excessive heat, as well as deterioration
which is initiated or accelerated by exposure to heat.
Effective heat stability is afforded generally by
adding about 0.5 to about 5 phr (parts by weight per
hundred parts by weight of resin) of the stabilizer
composition. Preferred amounts of the stabilizer are
generally in the range of about 1 to 4 phr. The
liquid stabilizer can be compounded into the resin
formulation in accordance with conventional
compounding techniques abundantly familiar to one of
ordinary skill in this art.
The stabilized polyvinyl chloride resin
composition comprising these components can also
contain conventional additional additives such as
antioxidants, lubricity agents, flame retardants,
fillers., pigments, and the like, in relative amounts
effective to fulfill the desired functions of each
such ingredient. These ingredients can be added, if
desired, prior to, during, or subsequent to the step
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Z. in which the heat stabilizer composition of the
present invention is compounded into the polyvinyl
chloride composition.
The homogeneous liquid stabilizer
compositions prepared in accordance with the teachings
of the present invention have been found to exhibit
little or no precipitation upon standing at ambient
temperature for a year or longer.
In addition, polyvinyl chloride formulations
prepared with the liquid stabilizer compositions of
the present invention have been found to exhibit not
only notable heat stability, but also superior
whiteness, color ho7.d, and long-term dynamic
stability.
The invention will be described further in
the following examples, which are intended for
illustration and should not be deemed limiting of the
scope of the present invention.
25
35
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a- EXAMPLE 1
Into a 2-liter beaker were charged 385.0 g
of an aqueous solution of monobutyl tin trichloride,
the solution containing 19.6 wt.o Cl (2.127 moles Cl),
and 100.0 g of water. Then, 201.5 g of 97 wt.o lauryl
mercaptan (0.9678 mole active) and 32.5 g (0.4148
mole) of 2-mercapto ethanol were added to the beaker
at 60-65°C. followed by 276.5 grams of a 20 wt.o
sodium hydroxide solution (1.3825 moles NaOH). This
mixture was agitated for 30 minutes, following which
18.0 grams of "Dowanol PPh" propylene glycol phenyl
ether was added, followed by a solution of 48.4 grams
( 0 . 3722 mole) of NazS ( 60 0 ) in 200 grams of water .
The final aliquot was added carefully to a final pH of
7Ø Then 24.0 grams of nonyl phenol was added, and
the mixture was agitated for about 1 hour at 60-65°C.
The mixture was transferred to a separatory funnel and
allowed to settle for 1-2 hours. The liquid
stabilizer formed as a liquid product above the
aqueous phase in the separatory funnel. It was
recovered from the funnel and was found to weigh 438.4
grams. This product was transferred to a 3-neck flask
and stripped (of water) at 20 mm pressure and 105°C.
The weight of the product remaining after the
stripping step was 403.0 grams. This corresponds to a
moisture content of 8.9o in the product prior to
stripping. The stripped product was filtered through
a celluosic filter medium and the final product
weighed 379.0 grams.
3~ The tin and sulfur contents of. this product,
based on the reactants, were 20.20 tin, ll.Oo
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mercaptan sulfur, and 2.9% sulfide sulfur (i.e. on an
equivalents basis, a ratio of SH:S of about (1.90:1).
10
20
30
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1- EXAMPLE 2
The procedure employed in Example 1 was
carried out with 237.5 grams of a mixture of
monobutyltin trichloride and dibutyl tin dichloride
comprising 31.75 wt.o Cl(2.127 moles C1) and 200.0
grams of water, followed by 201.5 grams of lauryl
mercaptan (97o active), 32.5 grams of 2-mercapto
ethanol, 276.5 grams of sodium hydroxide (200
solution), 18.0 grams of propylene glycol phenyl
ether, a solution of 48.4 grams of Na2S in 200.0 grams
of water, and then 24.0 grams of nonyl phenol.
The weight of the recovered organic product,
which was in the upper layer, was 455.4 grams; the
weight following the stripping of water was 438.2
~-5 grams. This corresponded to a moisture content of
3.8o in the product before stripping. The final
product obtained after filtration weighed 420.0 grams.
The tin and sulfur contents of this product,
based on the amounts of the reactants, were 21.50 tin,
10.3a mercaptan sulfur, and 2.7o sulfide sulfur (i.e.
on an equivalents basis, a ratio of SH:S of about
1.9:1).
30
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Z- EXAMPLE 3
The procedure employed in Example 1 was
carried out with 118.7 grams of a mixture of monobutyl
tin trichloride and dibutyl tin dichloride comprising
31.75 wt.o C1 (1.0635 moles C1), 91.7 grams of a
mixture of a 75:25 (weight) mixture of monomethyl tin
trichloride: dimethyl tin dichloride comprising 41.1
wt.o Cl (1.0635 moles C1) and 200.0 grams of water,
followed by 201.5 grams of lauryl mercaptan (970),
32.5 grams of 2-mercapto ethanol, 276.5 grams of a 20
wt.o sodium hydroxide solution, 18.0 grams of
propylene glycol phenyl ether, then a solution of 48.4
grams of Na,S in 200 grams of water, followed by 24.0
grams of nonyl phenol and 25.0 of 2-mercaptoethyl
1-5 tallate (9.2 wt%-SH) .
The weight of the recovered organic product,
which was in the upper layer, was 449.5 grams; the
weight following the stripping of water was 429.0
grams. This corresponded to a moisture content of 4.8
wt_a in the product before stripping. The final
product obtained after filtration weighed 411.0 grams,
The tin and sulfur contents of this product
based on the amounts of the reactants, were 21.5 0
tin, 10.90 mercaptan sulfur, and 2.7o sulfide sulfur
(i.e. on an equivalents basis, a ratio of SH:S of
about 2:1).
By comparison, omission of the nonylphenol
and phenoxypropanol additives from the foregoing
preparative procedures results in products that are
immediately seen to be unsatisfactory because of_ the
formation of haze, or appreciable formation of solids, '
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1 or both (representing increased amounts of product
values removed upon subsequent filtration and thereby
lost).
10
20
30
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EXAMPLES 4-5
PVC formulations containing various
stabilizers weue made in accordance with the following
compositions, and were tested for color stability in a
"dynamic Brabender" procedure wherein the PVC
formulation was heated in a continuous mixer and
torque rheometer and periodically sampled to monitor
color changes and melt viscosity.
Siding Formulation
PVC homopolymer ( "*Oxy 225", Oxy 100.0 (all in
par is
Chemical Corp.) by wt.)
Acrylic copolymer processing aids
("K-125", Rohm & ~laas) 2.0
("K-175", Rohm & Haas) 1.0
Acrylic polymer
blend,
impact modifier 7.0
("KM-323B", Rohm & Haas)
Calcium stearate 1.0 '
Paraffin wax (m.p. approx. 165F) 1.0
Titanium dioxide . 10.0
Stabilizer 1.0
Clear PVC Formulation
PVC homopolymer ("Oxy 225", Oxy Chemical Corp.)
100.0
Diisooctyl phthalate
5.0
Acrylic copolymer processing aid
( "K-120N" , 8011111 ~& Haas )
1.5
Oxidized polyethylene ("AC 629A", Allied-Signal)
0.2
Stabilizer
1.5
Samples of the sic?ing and clear formulations
containing, in turn, each of the stabilizers described
*trade-mark
CA 02221558 1997-11-19
R'O 96/38501 PCT/US96/07042
-23
1 in Examples 1, 2 and 3 were found to be equivalent or
superior to formulations containing different
stabilizers (not containing the aryl ether alcohols)
in whiteness, color hold and long-term dynamic
stability. Thus, it can be seen that the compositions
of the present invention are effective stabilizers in
addition to their virtues in exhibiting a reduced
tendency to form precipitate on standing.
15
25
35
