Note: Descriptions are shown in the official language in which they were submitted.
Back,~lounc! of th~ Invention
_
Inorganic materlals have lon(~ been used as
fillers, pigments, rein~orcenents and chemic:al reactants
in polymers. In general, these inorganic materials are
hydrophilic, that is, easily wetted b~y water or able to
absorb water, but their co~patibility with organic polymers
is limited. Because of this limited compatibility, the
full potential of color, reinforcement, or chemical
reactivity of the inorganic materials is not realized.
To overcome these difficulties, wettirlg agents
have been used to minirnize interfacial tension: but
wetting agents, too, have serious deficiencies. In
particular, relatively large proportions are necessary
to produce adequate wetting of the finely divided in-
organics. When used in large proportions, the wetting
agents marked,y detract from the properties of the
finished coTnposite. Coupling agents have been developed
to overco~e this difficulty. These fall into two main
classes. The first, the more widely ùsed, are trialkoxy
organo tunctional silanes. Their actiYity is based upon
chemical interaction between the alkoxy portion of the
silane and filler and the chemical reaction of the
organo functlonal por~ion with the poly~er matrix. This
provides a direct chemical link betweeD the polymer and
filler. But silanes have drawbacks. ~hey are typically
highly fla~Tnable, di~ricult -to handle, and not easily
worked into many polyrner systems. Where the polymers do
not contain functional groups or where the filler does
not contain acidic protons, the silanes are often
-- 1 --
lnefrectlve because o~ theil inabLlity to intelact.
For example~ silanes are ineffect:lve in therrnoplastic
hydrocarbons and flllers~ suctl ns carbon black, and -to
a large degree~ calcium carbonate and sulfur
The second group oi coupling agents includes
the organo-titanates which may be prepared by reacting
tetraalkyl titanates with aliphatic or aromatic carboxylic
acids. Of par-ticular interest are the di- or trialkoxy
acyl titanates or certain al~oxy triacyl titanates.
These titanates, however, have serious drawbacks: e.g.
they tend to decompose at tenperatures frequently used
in preparing many polymers; they tend to discolor certain
inorganic materials used with polymer systems; and they
are not compatible with many polymer systems.
~etails_o~ the Invention
The sub~ject invention relates to three novel
alkoxy titanium salts and their uses. The first class
may be represented by the following for~ula:
(I) (RO)zTi(A)x(B)y
wherein R is a rnonovalent alkyl, alkeny~, alkynyl or aralkyl
group having from l to about 30 carbon ~toms or a sub-
stituted derivative thereof. The R gr~up may be
saturated or unsaturated, linear or bra~ched, and may
have from l to 6 substitutions includin~ halogen, amino,
epoxy, cyano, ether, thioether, carbony~, aromatic nitro,
or acetal. In a particular molccule~ a'll of the R
~I'OUpS may be the same or different, so long as they fall
within the above class. lt is preferre~ that the R
-- 2
group be alkyl having 1 -to 6 carbon atoms and be all
the same.
The monovalent group (A) may be thioaryloxy,
sulfonic, sul~inic~ diester py~rophosphate and diester
phosphate. The thioaryloxy group may be a substituted
or unsubstituted thiophenoxy or thionaphthyloxy group
containing up to about 60 carbon atoms. It may be
substituted by alkyl~ alkenyl, aryl, aralkyl, alkaryl,
halo, amino, epoxy~ ether, thioethera ester, cyano,
carbonyl, or aromatic nitro groups. Preferably no more
than three substituents per aromatic ring are present.
The thioaryloxy groups whereir. the aryl is phenyl or
naphthyl are pre~erred.
The sul~onic, sulfinic, diester pyrophosphate
; 15 and diester phosphate ligand, respectivelyg are repre-
sented by the following formulas:
-OS02R", -OSOR", (R"0)2P(O)OP(OH)(O)- and (R"0)2P(O)O-
wherein R" may be the same as R' as defined below.
Where A is a sulfinic group, it is preferred that R"
- 20 be phenyl, a substituted phenyl or an alkaryl group
having ~rom 5 to 24 carbon atoms in the alkyl chain.
Where ~ is a sulfonic group, x in ~ormula I must be 3
or R" must be an amino-substituted or an alkyl-substituted
phenyl or naphthyl group, said alkyl group having from
5 to 24 carbon atoms. Where A is a phosphate group, it
is pre~erred that the R" group have from 6 to 24 carbon
atoms, and where A is a pyrophosphate group, it is
pre~erred that the R" group be alkyl having up to 12
carbon atoms
~,
., .
The monovalen-t group (B) may be acyloxy (OCOR') or
aryloxy (OAr), R' may be hydrogen or a monovalent organic
group having from 1 -to about 100 carbon atoms; particularly,
an alkyl, alkenyl, aryl, aralkyl or alkaryl group. The
aryl groups may be substituted or unsubstituted phenyl
or naphthyl groups, preferably containing up to 60
carbon atoms. Additionally~ the R' group may be
substituted with halo, amino, epoxy~ ether~ thioether3
ester3 cyano, carboxyl and/or aromatlc nitro substituents~
Generally up to about six substituents may occur per
R' group. The R' group may contain intermediate hetero
atoms such as sulfur or nitrogen in the main or pendant
substituents R' is preferably a long chain group
having 18 carbon atoms. Most desirably, all R's are
the same. In formula (I), the sum of x, y and 2 must
be 4; x and z may be 1~ 2 or 3; and y may be 0, 1 or 2.
Preferred are those compounds where z = 1.
The second class of compounds falling within
the scope of the present invention may be represented
by the following formula:
(II) (RO)Ti(OCOR')p(OAr)q
In the aforesaid formula, R and R' are as defined abovej
p+q must be 3; p may be 0~ 1 or 2; and q may be 1, 2 or 3.
OAr is as defined above. These organo-titanate compounds
having one or more of these long carbon chains are
particularly effective for coupling agents used in
connection with low density polyethylene. They increase
the modulus o~ the products as well as their density.
- 4 -
The third class ~f c~mpounds may be represented
as follo~s:
(III) (R~)Ti(0C~Rb)3
~gain, ~ is defined as above~ The Rb of the (OCO~b)
group ~ay be -the same as R' as previously deflned, except
that the total number of carbol~ atoms in the three Rb
groups is not more than 14. It is preferred that all
groups be vinyl, methylviny:L or aminomethyl
A wide variety of ligands, subject to the limita-
1~ tions heretofore expressed, may be used in the practice
of this invention. The most suitable depends upon the ~:
filler-polymer system and to a lesser degree upon the
curative and/or extender systems employed
Examples of specific R ligands are: methyl,
propyl, cyclopropyl, cyclohexyl, tetraethyloctadecyl,
2,4-dichlorobenzyl, 1,-(3-bromo-4-nitro-7-acetylnaphthyl)-
ethyl, 2-cyano-~uryl, 3-thiomethyl-2-ethoxy~l-propyl and
methallyl
Examples o~ A ligands useful in the practice of
this invention include 11-thiopropyl-12-phenyloctadecyl-
sul~onic, 2-nitrophenylsulfinic, di-2-omega-chlorooctyl)-
phenyl phosphato, diisonicotinyl pyrophosphato, 2-nitro-
3-iodo-4-fluorothiophenoxy, phenylsulfinic, 4-amino-2-bromo-7-
:~ naphthylsulfonic, diphenyl pyrophosphato, die-thylhexyl
pyrophosphato, di-sec-hexylphenyl phosphato, dilauryl
phosphato, methylsulfonic, laurylsulfonic and 3-methoxy-
naphthalene sulfinic Examples of B ligands are 2-meth-
allylphenoxy, 3-cyano-4-methoxy-6-benzoylphenoxy and 2,4-
dinitro-6-octyl-7-(2-bromo-3-ethoxyphenyl)-1-naphthyloxy.
!,
._,','
~xa~ples o~ the ~' groups are numerous These
include straight chain~ brnnched chain and cyclic alkyl
groups such as hexyl, heptyl, octyl, decyl, dodecyl,
tetradecyl, pentadecyl, hexadec~/l, octadecyl, nonadecyl,
eicosyl, docosyl, tetracosyl, cyclohexyl, cycloheptyl,
and cyclooctyl. Alkenyl groups include hexenyl~ octenyl
and dodecenyl.
Halo-substituted groups include bromohexyl,
chlorooctadecyl, iodotetradecyl and chlorooctadecenyl.
One or more halogen atoms may be present, as ~or example
in difluorohexyl or tetrabromooctyl. Ester-substituted
aryl and alkyl groups include ~-carboxyethylcapryl and
3-carboxymethyltoluyl. Amino-~ubstituted groups include
aminocaproyl, aminostearyl~ aminohexyl, aminolauryl and
diaminooctyl.
In addition to the foregoing aliphatic groups,
groups containing hetero-atoms, such as oxygen, sulfur
or nitrogen, in the chain may also be used. Examples
of these radicals are ethers of the alkoxyalkyl type,
including methoxyhexyl and ethoxydecyl. Alkylthioalkyl
groups include methylthiododecyl groups. Primary, secondary
and tertiary amines may also serve as the terminal portion
of the hydrophobic group. These include diisopropylamino,
methylaminohexyl, and aminodecyl
The aryl groups include the phenyl and naphthyl
groups and substituted derivatives. Substituted alkyl
derivatives include toluyl, xylyl, pseudocumyl, mesityl,
isodurenyl, durenyl, pentamethylphenyl, ethylphenyl, n-
propylphenyl, cumyl, 1,3,5-triethylphenyl, styryl, allyl-
phenyl, diphenylmethyl, triphenylmethyl, tetraphenylmethyl,
' ~
.
1~3~5-triphenylphenyl Nitro- and halo-substituted
ma~ be e~emplified by chloronitropheny:L, chlorodinitro-
phenyl~ dinitrotoluol, and trinitroxylyl.
Amine-subs-tituted components incl~de methylamino-
toluyl, tri~ethylaminophenyl, diethylaminophenyl, amino-
methylphenyl, diaminophenyl, et;hoxyaminophenyl, chloro-
aminophenyl, bromoaminophenyl and phenylaminophenyl.
r~alo-substituted aryl groups include fluoro-, chloro-,
bromo-, iodophenyl, chlorotoluyl, bromotoluyl3 methoxy-
bromophenyl, dimethylaminobromophenyl, trichlorophenyl,
bromochlorophenyl, and bromoiodophenyl.
Groups derived from aromatic carboxylic acids are
also useful. These include methylcarboxylphenyl, di-
methylaminocarboxyltoluyl, laurylcarboxyltoluyl, nitro-
carboxyltoluyl, and aminocarboxylphenyl. Groups derived
from substituted alkyl esters and amides of benzoic acid
may also be used. These include aminocarboxylphenyl and
methoxycarboxyphenyl.
Titanates wherein R' is an epoxy group include
tall oil epoxides (a mixture of 6 to 22 carbon alkyl
groups) containing an average of one epoxy group per
molecule and glycidol ethers of lauryl or stearyl alcohol.
Substituted naphthyl groups include nitronaphthyl,
chloronaphthyl, aminonaphthyl and carboxynaphthyl groups.
.~
.~ .
P~ in the third class of compounds has a
total of up to 14 carbon atoms. For example, each Rb
may be isopropenyl, vinyl, 2-a.minoethyl~ l-aminopropyl,
hydro.Yymethyl~ 2~2-clichloroethyl~ trimethoxymethyl,
cyanomethyl and acetylmethyl.
Illustrative o~ the compounds o:~ the instant
invention are: (i-C3H70)Ti(0sOc6Hl~NH2)3; (1~C3H7)Ti(
C6H4C12H25)2(S2C6H4NH2); (i-C3H7)Ti[p(o)(ocsHl7)2]3;
( 3 7 )Ti(oc6H4c(cH3)2c6Hs)3; (i-c3H7o)Ti[op(o)(oc H )] ;
(C6Hll)Ti(C6H4NH2)3; (nG4.H9)2Ti[Po(oc6Hl~c8Hl7)2]2;
~c6H5o(cH2)3o]Ti[oco(cH2)6s(o)(ocH3)2]3;
[cH3o(cH2)2o]2Ti(ococ6H4cl)[op(o)(oH)op(o)(ocH3)2];
(cH3o)Ti(2-scloH7)3 and (i-C3H70)(ncl2H25o)Ti(o3o2c6H5)2-
- 8 -
D
Examples OI' the thlrcl class of the organo-
titanates OI7 the in~ention are~ C3H70)Ti[OCOC(C~3)=C ~ )3;
) (OCOCH2~c)3; (C6~ 0)Ti(OcOcH~OcH3)2(0cocHclc~3);
(CH30)Ti(OCOCC13)3; (c2Hso)Ti(ococ~Brcl~cl)(ococ6~l~)(oco-
CH3 ~ ); and (i-C3H70)Ti(OCOC2H5)(0COC~ CN)~OCOCE~N(CH3)2].
Another composition of matter of the invention
comprises the reaction products of the aforesaid classes
of alkoxy titani~m salts with inorganic materials,
especially when x in the above formula is 3. The amount
of the titanate reacted is at least 0.01 part, preferably
from 0.1 to 5 parts, and most preferably between 0.2 and 2
parts, per 100 parts of inorganic solid. The optimum
proportions required are a function of the inorganic solid
and the alkoxy titani~m s~lt selected, and the degree of
the co~inution, i.e., the effective surface area, of
the inorganic solid. The reaction of the titanate takes
place on the surface c~ the inorganic ~iller. The RO
group splits off and an organic hydrophobic surface layer
is formed on the inorganic solid~ The unmodified inorganic
solid is dif1icult to disperse in an organic medium
because of its hydrophilic surface. The organo-titanium
compound may be incorporated into an organic medium (low
molecular weight liquids or higher molecular weight polymeric
solids) with the inorganic solid. Alt~rnatively, the
organo-titanate may be first reacted with the inorganic
solld in the absence of an organic medium and thereafter
admixed with the latter.
~ Y-~3
By means o~ the present invention, the dispersion
of inorganic materials in organic polymer media is
improved and achieves (1) improved rheology or higher
loading o~ the dispersate in the organic medi~; (2)
higher degrees o~ reinforcement by the use of ~illers,
thereby resulting in improved physical proper-ties in the
~illed polymer; (3) more complete utilization o~ chemical
reactivity, thereby reducing the quantity of inorganic
reactive solids required; (4) more e~icient use o~
pigments and opaci~iers; (5) higher inorganic-t~-organic
ratios in a dispersion; and (6) shorter mixing times to
achieve dispersion.
Also, according to the invention herein, the
reaction with the R0 groups may be carried out neat
or in an organic medium -to ~or~ a liquid, solid, or paste-
like solid dispers on which can be used in the compounding
of the final polymeric system. Such dispersions are very
stable~ i.e., having little tendency to settle~ separate,
or harden on storage to a non-dispersible state.
Moreover, the invention simpli~ies the making o~
inorganic dispersions in organic media by providing a
means to eliminate the solvent, to reduce the cost o~
processing equipment, and to reduce the time and energy
required to disperse an inorganic solid material in a
liquid or polymeric organic solid
The present invention results in the formation
ol a reinforced polymer which has a lower melt viscosity,
improved physical properties, and better pigmenting
characteristics than the prior art materials.
-- 10 --
LD' .
The practice o~ the present inYsntion achieves
a product comprisinS natural or synthetic polymers
whlch contain particulate or fibrous inorganic ~aterials
which reinforce, pigment or che~ically react with the
5 poly~er to produce a product havin~ superior physlcal
properties, better processing characteristics, and more
efficient utilization of pigments.
Amongst the advantages gained by the practice
of this embodiment of the present invention is the option
of dispensing with the use o~ volatile and flammable
solvents and the attendant need to dry the filler or to
recover solvents. Furthermore, multi-molecular layer
formation is minimized. Also3 the dispersions of the
present invention are non-oxidi~ing~
The inorganic materials may be particulate or
fibrous and o~ varied shape or size, so lon~ as the surfaces
are reactive with the hydrolyzable group of the organo-
titanium compound. Examples of inorganic reinforcing
materials include metals 3 clay, carbon ~lack, calciurn
carbonate, barium sulfate, silica, mica, glass and asbestos.
Reactive inorganic materials include the metal oxides of
zinc, ma~nesium, lead, and calcium and aluminum~ iron
filings and turnings, and sulfur Exam les of inorganic
- pigments include titanium dioxide, iron oxides, zinc
chromate~ u:Ltramarine blue. As a practical matter, the
particle size of the inor~anlc materials should not be
greater than 1 mrn, prererably from 0 1 micron to 500 micron.
It is lmperative that the alkox~ ti-tanium salt be
properly a~nixed with the lnor~anic ma-terial to permit
the surface of the latter to react sufficiently The
3~
optimum amount o~ the alkoxy titani~ salt to be used is
dependent on the e~fect to be achieved, the available
surface area of and the bonded water in the inorganic
material.
Reaction is ~acilitated by admixing under the
proper conditions. Optim~n results depend on the properties
of the alko~y titani~m salt~ namely, whether it is a
liquid or solid, and its decomposition and flash points.
The particle size, the geometry of the particles, the
speci~ic gravity, the chemical composition, among other
things, must be considered. Additionally, the treated
inorganic material must be thoroughly admixed with the
polymeric medium. The appropriate mixing conditions depend
on the type of polymer~ whether it is thermoplastic or
thermosetting, its chemlcal s-tructure~ etc.~ as will be
readily understood by those skilled in the art.
Where the inorganic material is pretreated with
the organic titanate~ it may be admixed in any convenient
type of intensive mixer, such as a Henschel or Hobart
mixer or a Waring blender. Even hand mixing may be employed.
The optimum time and temperature are determined to obtain
substantlal reaction between the inorganic material and
the organic titanate. Mixing is performed under conditions
at which the organic titanate is in the liquid phase, at
temperatures below the decompositi~n temperature. While
it is desirable that the bulk of the hydrolyzable groups
be reacted in this step, this is not essential where the
materials are later admixed with a polymer, since the
substantial completion of the reactinn may take place in
this latter miYing step.
3~
Polymer processing, e.~, ligh shear mixing,
is generally performed at a -tem~erature well above the
second order t;ransition temperature of t;he polymer,
Aesirably at a temperature ~here the polymer will have a
low melt viscosity. F'or exam]?le3 low density polyethylene
is best processed at a temperature range oE 170 to 230 C.;
high density polyethylene from 200 to 245 C.; polystyrene
from 230 to 260 C.; and polypropylene from 230 to 290 C.
Temperatures for mixing other polymers are known to those
skilled in the art and may be determined by reference to
existing literature. A variety of mixing equipment may
be used, e g., two-roll mills, Banbury mixers, double
concentric screws, counter or co-rotating twin screws and
ZSK type of lrlerner and Pfaulder and Busse mixers.
When the organic titanate and the inorganic
materials are dry-blended, thorough mixing and/or reaction
is not readily achieved and the reaction !nay be substantially
completed when the treated filler is admixed with the
polymer. In this latter step, the organic titanate may
also react with the polymeric material if one or more of
the R' groups is reactive with the polymer.
The treated filler may be incorporated in any of
the conventional polymeric materials, whether thermoplastic
or thermosetting, whether rubber or plastic. The amount
of filler depends on the particular polymeric material,
the filler and the property requirements of the finished
product. Broadly, from 10 to 500 parts ot filler may be
used per 100 parts of polymer, preferably from 20 to 250
parts. The optimum amount may be readily determined by one
skilled in the art.
To illustrate further the invention, attention is
directed to the following examples. In certain of these
, - ' ' ~'
examples, the n~mber of ligands per molecule ls expressed
~or a mixed n-~mber. In such cases, it should be unders-tood
~hat the structural formula represen-ts a blend of compounds
and the m~xed number is the average number of such ligands
in the blend.
Examples ~ to C describe the preparatiorl of compounds
within the scope of formulas (I) and (II) above
Example A: Preparation o~ Isooctyloxy Tri(cum~l ~henoxy~ Titanium
To a pyrex-lined metal vessel~ equipped with an
agitator, internal heating and cooling means, a vapor
condenser and a distillate -trap, is added 1 mole of
isooctanol, 3 moles of mixed isomer cumyl phenol and
2 liters of mixed isomer xylene. The reactor is stirred,
flushed with nitrogen and 4.~ moles of sodamide are added
at a controlled rate and with cooling to maintain the ~-
reaction mass at a temperature not over about 100~ C.
By-product ammonia is vented. The sodamide treatment
forms a heavy slurry which is refluxed for about 10
minutes to remove dissolved ammonia. The reactor contents
are then cooled to about 90 C. and maintained at this
temperature while 1 mole of TiC14 is added over a period
of three hours. After the TiC14 addition~ the resulting
mixture is refluxed for 2 hours~ cooled to about loOD C.
and filtered. The filter cake is washed with about 500 cc
of xylene and discharged. The washings are combined with
mother liquor and charged to a still. Volatiles are
removed to g-Lve a bottoms having a boiling point at 10 mm
Hg of over 1';0 C. weighing about 800 g. (This is over
95~ of` theor~.) Elemental analysis of bottoms product,
a heavy dark red paste or glossy solid, is consistent
~ith the formula (i-C8H170)Ti~OC6H4C(CH3)2C6H5]3.
_ lL~ _
,. 1~
Example B: Preparation of
(CH30)o 6Ti[OP(O)(O~)OP(O)(OC~H17)2]3 1~
A reactor such as that described in Example A
is charged with 1 mole of tetramethyl titanate. There-
after~ with stirring, 3.4 moles of dioctyl pyrophosphoricacid is added over about a one hour period. F~ternal
cooling is maintained during the additlon to maintain a
reaction mass temperature in the 20 to 55 C. range.
The reaction mixture formed is distilled to bottoms
temperature of 150 C. to reJnove substantially all by-
product methanol. Elemental analysis of the residual
pale yellow heavy oil is consistent with the for~ula
(CH30)o ~Ti~op(o)(oH)op(o)(oc8Hl7)2]3-4- ~he yield is
over 95~ of theory.
~xample C: Preparation of
(o-ClC6H4CH20)l.2Ti(Os02c6H4N~I2)2.8
In a reactor such as that described in Example A,
a solution o~ 1 mole of tetraisopropyl titanate in 2 liters
of 2,6-dimethylnaphthalene is heated at 200 C. While
maintaining this te~nperature for a period of 2.5 hours,
1.25 moles of ortho-chlorobenzyl alcohol and 2.8 moles of
mixed isomers of aminobenzene sulfonic acid are added
sequentially. By-product volat~les (mainly methanol) are
continuously removed by distillation. After cooling, the
resulting grey solid is filtered, washed with cyclohexane
and vacuum overl dried to give about 565 g (82~ yield) of
~rey solid procluct. Salcl product is found to have an
- 15 -
3.~$ ~
elemental analysis and OH number consistent with the
above ~ormula.
- 16 -
........ . . .. . .
~. :
r~
To illustrate further the invention7 the following
example sho-~s the preparatLon of a compound within the
scope of lormula (III) above:
~Yample D: Preparation of (i-C~H70)0.7Ti(OCOC(C~I3)=C~I2)3.3
One mole of tetraisopropyl titanate is added to
a vessel sucn as described in E~ample A, and stirring
commenced. Liquid methacrylic acid is added at a
controlled rate so that the eYothermic reaction is main-
tained belo~ about 180- C. until 3.50 moles of the acid
are added. Iso~ropanol is removed from the reaction
product by distillation at 150~ C. at 50 mm Hg to remove
volatiles.
The organic titanate thus produced has an average
of 3.3 moles of methacrylate per molecule. The product
structure is determined by ascertaining the isopropanol
liberated from the reaction and the residual methacrylic
acid. From 3.1 to 3.3 moles of isopropanol are recovered.
About 0.2 mole methacrylic acid plus isopropyl methacrylate
are detected. The physical properties of the product are:
Specific Gravity at 24 C. 0.92
Flash Point (COC), C. 120
Pour Point, C. About 130
Decomposition Point, ~C. Above 200
Appearance Tan Solid
- 17 -
Th~ follow~ e~am~ st,rate the use o~
the nlko~y -titanium snlts o~` the instant invention as
couplin~ aC~ents in inorganic-filled polymer systeos
All par-ts are by weight unless other~ise indicated.
Example 1
A master formulation w~s prepared containing
100 parts of chlorosulfonated chlorinated polyethylene
(Hypalon 40~ a trade~ark of E. I. duPont deNemours & Co.,
Inc.), 4 parts of ~inely divided magne~ium oxide~ 2 parts
of low molecular weight polyethylene, ~1~ parts of calcium
carbonate, 30 parts of a highly arom2t~c oil (Kenplast RD,
a trademark of Kenrich Petroche~icals~ Inc~), 3 parts
of pentaerythritol 200, a~d 2 parts of an accelerator
(Tetrone A, a trademark of E. I. duPon~ deNemours & Co.~
Inc,), Four formulations were tested. The first consisted
of the foregoing formulation without more, and served as
a control. To Formulations A~ B and C, respectively,
1~, based on the filler, of the followi~g compounds of
the invention were added:
(i-C3H70)o gTi(S2CoH4C12H2~)3.1;
(i~C3H70)o 6Ti[PO(iC8H17 )2~3.4
(i-C H70)1 1T~(oso2c6H4cl2H25)l.7(oso2c6H4N 2)1.2
All of the formulations were cured at 152 C. for
30 minutes. Table A shows the properties of the four
compounds as originally tested and after oven aging for
seven days at 121 C.
- 18 -
~3.~`$
T~BLE ~
Formulat:ion l~o.
Ori~inal
Properties at 24 C. Con-trol ~ B C
20G~ Modullls~ psi 5~0 460 L~70 1~60
300~ ~Sodulus, psi 670 540 560 540
Tensile Strength,
psi 2170 2170 1840 1940
Ultimate Rlongation,
percent 540 550 530 530
Shore A Hardness 65 63 65 65
Crescent Tear
Resistance, ~/In.
(AS~S D624 ~ Die C) 196 175 188 273
Rheometer at 171 C
3 Arc, 20~ Motor,
100 Scale
ML-lb.-in. 14~5 15~25 13 12~5
~F-lb.-in 49 55 ~ 5 53 50
Ts-2~ min 3~0 2~67 2~76 3~09
Tc-90, min. 14~2516~73 18rl7 18~23
Oven Aged 7 Days
at 121 c~ ~
200% Modulus, psi 95O 800 970 865
300% Modulus~ psi 1150 990 1270 1135
Tensile Strength,
psi 1770 1700 2000 1850
Ultimate Rlongation,
percent 420 435 410 425
Shore A Hardness 73 73 72 73
Hot Tear Rec;istance
at 121 C ~ ~ ~t/In.
(AS~S D624 - Di~ C) 1~3 153 186 233
Percent Ch~nge on ~ging
Tensile -19.5 -22 +9 ~5
Elongation -22 -21 -23 -20
Tear Resistance ~7 -13 -1 -15
- 19 --
r~
The abo~e datn cl~arly show, ,Imon~ other things,
that the formulations of` t~le :Lnventlon have a lower
modulus than t~e controi. Additionally, in the case of`
For~ulation C~ there is a marlsed im~r~vement in tear
resistance.
Exa~Dle 2
_
This example shows the utility of (i~C3H70)o gTi~
(OS02C6H5C12E125)3 1 for implo~ring the properties of polyvinyl
chloride plastisols. One hundred parts o~ a PVC resin
(Geon 121, a trademark of B. F. Goodrich Chemical Co.),
100 parts of dioctylphthalate, 3 parts of a b~ri~m-cadmium
stabilizer and 10 parts of calcium car~onate were prepared~
to form a control. A second formulation was prepared,
except that 10 parts of the calcium carbonate containing
1~ (based on calcium carbonate) of the aforementioned
organo-titanate compound are added in place of the u~modified
calcium carbonate. Table B shows the viscosity at the
time period indicated at 24 C. and the original properties
of molded samples obtained after the two weeks o~ plastisol
aging at 24 C. The molding was perfor~ed at 171 C.
T~BLE B
Formulation ~o. _
ControlD
LTV Brookfield Viscosit~
at 21 C., #2 Spindle at 12 R~
Initial 1250 830
1 l~eek 1637 1650
2 Weeks 1650 1815
Original Pro ~
100~ Modulus, psi 520 440
Tensile Strength, psi 1890 1610
Ultlmate Elongation, ,~440 440
Shore A Elardness 67 64
- 20 -
3~
In the case of ~'ormulation D, it will be noted
that there is a lower initial viscosity. This is an
advantage f~r polyvinyl chlori~e plastisols, since low
viscosity reduces the energy requirements f`or mixing.
The reduced modulus and hardness of the produ(t of
Formulation D is o~ importance, since in the prior art
it was necessary to use substantial amounts of plasticizer
to achieve such properties. Furthermore, with plasticizer
alone, it is not possib~le to reduce hardness and modulus,
while holding the elongation constant.
Example 3
This example shows the utility of the compounds
of the invention in modifying the properties of a calcium
carbonate-filled flexible polyvinyl chloride formulation.
A control containing 100 parts of a PVC resin having a
mediurnmDlecular weight, 1 part o~ a stabilizer (DS 207,
a trademark of NL Industries), 67 parts of dioctyl
phthalate, and 50 parts of finely divided calcium carbonate,
was prepared. In addition, five other formulations were
prepared having the same composition as the control, except
that each was modified by hot blending at about 88~ C. for
3 minutes in a blender with 0.5~ by weight, based on the
calcium carbonate, of the ~ollowing compounds, respectively:
Formulation No. Organotitanate Compound
E (i-c3H7o)Ti(oso2c6H4cl2H25)3
- 21 -
,
- .
~ ?~
H ( i - C 3H70) 1 3T i ( OC oC6H4N~I2) 2.7
J (i-C3H70)o 5Ti[OP(O)(OC~EI17)~3 5
The following table shows the proper-ties of the
control and the ~ormulations embodying the teachings of
the inven-cion:
TABLE C
Fo~mulation No.
Original Properties Control E H J
Hardness, Shore A 80 78 80 79
~lodulus, 100~, psi 912 733 892 856
Tensile, psi 1790 1693 1791 1750
Ultimate Elon~ation,
percent 300 310 320 340
The above data clearly show the advantages of the
formulations of the invention. Formulations E and J show
a reduced modulus and increased elongation without
impairment of tensile strength. Formulation H shows
increased elongation without loss o~ modulus or hardness.
Example 4
To show the utility of the invention for modifying
the properties of carbon black-~illed styrene-butadiene
copolymer rubber, ~our formula-tions were prepared. Two
served as the control. The first, Control 1, contained
100 parts of styrene-butadiene polymer, 50 parts of HAF-type
25 carbon black~ 4 parts zinc oxide, 2 parts sulfur, 1 part
: - 2~ -
L~' .
-
of an accelerator (Santocurc NS, a trademark of MonsantoCo.), 1 part o~ s-tearic acidg 10 parts of an aromatic
extender oil and 2 parts o~ an antioxidant (Neozone ~,
a trademark o~ E. I D duPont deNemours ~ Co., Inc.). The
second control was the same as the first, except that
tne carbon black was pretreated with l$ of Ca~OCl)2 at
38 C, for one minute to improve receptivity of the carbon
black to titanate coupling~
Formulations L and 2;1 were identical to Control 2,
except that they also con-tained, respectively, 2 parts of
(i C3H70)o 8Ti(oso2c6H4 ~ )3 2 and (i-c3~l7o)l oTi(C6~
H4C(CH3)2coH5)3.
Table D below shows the physical properties o~
the four formulations after being cured at 166 C. for
3 minutes.
TABL~ D
Formulation No.
Original Pro~erties Control 1 Control 2 L M
300~ Modulus, psi1050 740 ~50 1660
400$ Modulus, psi11~50 1260 1420 2540
Tensile, psi 2500 2290 2920 2680
Ultimate Elongation3
percent 550 560 620 420
~ Set at Break 18 .12 12 3
The advantages of the invention are shown by
the above data. Note that Formulation L shows increases
ln both the elongation and the tensile strength, while
Formulation M shows increased modulus and substantially
reduced permanent set at break~ This retention of
- 23 ~
dimensional s~ability at brlak is ~ parti~ularly useful
propeIty for such applications as shock absorbers.
Exa~ple 5
This e~Yample shows the compounds of this invention
ln protecting mineral-filled polyethylene from attack by
aqueous acid.
~o 1" x 3" x 1/8" test specimens of 50 weight
percent magnesium silicate-~illed high density polyethylene
are injection molded in identical fashion~ except that
the magnesium silicate used in one is pretreated at about
38 C. with 1 wt. ~ of (CH30)1 2Ti(S2C6~I4C12H25)~ 8
for 1.5 minutes in an intensive mixer. The resulting
specimens are then evaluated for acid etch resistance by
placing a drop of 85~ aqueous hydrochloric acid on each,
covering with a petri dish and oven aging at 38~ C. for
24 hours. Visual inspection of the aged test specimens
shows that the untreated specimen has substantially more
surface discoloration than has the trèated one. Similar
observations are made when the magnesium silicate is
replaced by a like proportion anhydrous calcium sulfate.
Example 6
This example shows a comparison of property
modifieation using compounds of the instant invention and
commercially available trialkoxy vinyl silane coupling
agent CH2=CH Si(OCH2CH20CH3)3 in cla~-filled peroxide-cured
- ethylene-propylene-diene terpolymer (EP~I). The compound
of the invention used was the formula (i-C3H70)o 7Ti[OCOC-
~ 24 -
3~
~C~3)=CH2] ~ Four for~nulatlons were prepared. Each
co~ltained 100 parts by ~ei~ht of EP~;I (Vistnlon 2504, a
tradenark of E,~,~on Corporation), 1.5 p~rts of an anti-
oxiùant (~gerite Resin D, a trade!llark of R. T. Vanderbilt
Co., Inc.), 5 parts of zinc oxide~ 20 parts of` an aliphatic
extender oil (S~mpar 2280, a trade~nark of Sun Oil Company),
5 parts of a 5:1 by weight paste of red lead in a viscous
oil,, and 6 parts of dicwnyl peroxide. In addition to
the above, Composition 1 contained 90 parts of a hard
clay pretreated with 1~ of the aforementioned silane
plus 2 parts per weight of the silane; Composition 2
contained 90 parts by weigh-t of a silane-pretreated
commercially available hard clay and 2 parts by weight
of the compound of the invention; and Composition 3
contained hard clay pretreated with 1~ by weight of the
aforementioned titanate plus 2 parts by weight OI the
titanate. Composition 4 was identical to Composition 3,
except that only 10 parts of the aliphatic extender oil -
were employed.
The aforesaid compositions were cured for 20
minutes at 171 C. The following Table shows the results
obtained.
TABLE E
Co~nposition No.
Original Properties 1 2 3 4
.. ... , . _ _ . . . .
?00~ Modulus, psi 4~5 377 Ll38 684
300~; Modulus, psi 803 576 605 862
Tensile, psi 9401000 1009 1048
Elongation at Break, ~6 381 740 750 527
Shore A Hardness 6062 63 67
-- 25 -
3 ~
The aforesaid Table clearly shows the advantages
of the invention as compared to the use of silane
coupling agents. Compositions Nos. 2~ 3 ancl 4 showed
increased elongation at the break and Compositions 2
and 3 lncreased hardness. ~lso, Composition 1~ showecl
increased modulus and tensile strength as compared to
the silane composition. It is particularly noteworthy
that Composition 4 shows 38$ greater elongation at the
break, despite the elimination of 50~ of the aliphatic
extender oil plasticizer.
- 26 -
3,. ~ 9~
EYample 7
j This example teaches the use of compounds of
this invention, viz.~ (R) (CH30)Ti(OCOCH=CH2)3~ (S)
(i-C3H70)Ti[0C0C(CH3)=CH2]3, (T) (i-C~70)2Ti(0S02CH2CH2CoCH=cH2)2
and (U) (BrcH~cH2o)TiL(op(o)(ocH2cH=cH2)2]3 as flex property
modifiers for polyester resin.
Formulations were prepared containing 100 parts of
a cobalt activated polyester resin (GR 643~ R trademark of
W R. Grace Co.), 1 part of met~yl ethyl ketone peroxide,
60 parts of high surface area calcium carbonate, and 0.3
part of alkoxy titanium salt, as indicated in the Table
below.
Samples measuring 1/2" x 5" x 1/8" thick were
cast and cured at ambient temperature for 30 minutes.
The castings were testeA and the results shown in Table F
below:
TABLE F
Alkoxy Flex Flexural
Titanium Salt Modulus psiStrength psi
None 1.5 x 106 4 x 103
R 3.5 x 106 7 x 103
S 4.0 x 106 10 x 103
T 2.0 x 106 6 x 103
U 1.0 x 106 8 x 103
:
The above data establish clearly the improved
flexurQl properties obtained by the use of the organo-
titanates of the invention.
. ~ .
. ~ . ,
- - . - . :
In selec-ting the particular organo-titan~te
co~pound, the :iater content o~ the inorganic ~iller
~ust be considered. I~ free or loosely bound water is
present (e.g., water-washed clays, hydrated silica,
alumina gel, magnesium silicate, talc, fiberglass, and
alu~inu~ silica-te), the pyrophosphate coupling agents
are particularly pre~erred. This is shown in the
~ollowing examples
Exa~ple 8
A blend o~ 30 parts ~y ~eight of kaolin, non-
calcined water-washed clay, and 70 parts of mineral oil
was prepared. To portions of such blends were added o.6
parts by Neight of three of the organo-titanate compounds
of the instant invention. Brookfield viscosities of the
four dispersions are compared in Table G below.
Table G
Brookfield Viscosity
Alkoxy Titanium Saltcps at 25u C.
None 19~000
Isopropyl triisostearoyl titanate 8,200
Isopropyl tri(diisooctylphos-
phato)titanate 5,200
Isopropyl tri(dioctylpyrophos-
phato)titanate 700
The above table clearly shows that each of the
compounds of the instant invention reduces the viscosity
of the clay-mineral oil dispersion. However, it will be
noted that the isopropyl tri(dioctylpyrophosphato)titanate
æives unexpec:tedly superior viscosity reduction, This
markedly lowers energy require~ents for mixing.
- 28 -
D
3 3,~
Example 9
The viscosi~y reduction o~ isopropyl tri(di-
octylpyrophosphate)titanate is also effective with
kaolin (non-calcined water-washed soft clay) dispersed
in a chlorinated paraf~in. To demonstrate this, a
mixture containing 30 parts by weight of kaolin and
70 parts by weight of a chlorinated paraffin having a
molecular weight of about 580 was prepared. The
Brookfield viscosity was deter~ined in the absence of
the organo-titanate and with the addition of 0.3 part
by weight. The test results showed the Brookfield
viscosity, cps at 25 C., was reduced ~rom 903000 to
18,000 by the titanate addition.
Example 10
This example shows the viscosity reduction of
isopropyl tri(dioctylpyrophosphate)titanate on a
dispersion of talc in a heavy mineral oil. The control -
contained 60~ by weight of talc and 40~ by weight of a
heavy mineral oil (flash point ca. 105 C ). In the
titanate-treated formulation, 1.8 parts o~ the aforesaid
compound was dry-blended at 85' C in a Waring blender
with the talc (3~ by weight based on talc) The control
had a Brook~ield viscosity at 25D C. of 26,500 In -~
contrast, the formulation of the invention had a
viscosity of only 11,000. Talc is another example of
a filler having a high water content.
- 29 _
:
.~
': . ~ ` `' `: ~
F~YaTnp le 11
The ef~ect of the organo-titanates of the -lnstant
invention on the impact strength of polyvinyl chloride
(PVC) is shown in this example. The relative Gardner
i~pact strength of a composition containing 100~ rigid
PVC ~,~as compared -to a filled composition containing 40~
of a fine grind calcium carbomlte (particle size of 1 to
2 microns). Samples of the filled compositions were also
admixed ~7ith varying amounts of the alkoxy titanate salts
of the invention as specifically shown in Table H below.
All of the tests in the table below show the filled
composition ~ith the exception of the first run, which
is 100~ rigid PVC~
Table H
Pts. by Wt,/ Relative
Alkoxy Titanate_Salt 100 Pts. of Filler Gardner Impact
.. ... . _
None (100~ PVC) 100
None (Filled PVC) 12
Isopropyl tri(dioctyl- 0.4 51
20phosphato) titanate 1,2 79
Isopropyl tri(dioctyl- 0.4 108
pyrophosphato)titanate 1.2 113
The above table clearly shows that the impact
strength of the filled PVC is improved in each and every
case by the addition of the titanates. Most striking
is the improvement resulting from the addition o~ the
pyrophosphate compound, Here the Gardner impact strength
exceeds that of the 100~ PVC composition.
- 30 -
