CA1239721A - Polysiloxanes and the use thereof in the production of silane modified alkylene-alkyl acrylate copolymers - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE
Polysiloxanes prepared by reacting a diester and a monomeric silane and the use of the polysiloxanes to produce silane modified, water-curable copolymers by reacting the polysiloxanes with alkylene-alkyl acrylate copolymers in the presence of an organo titanate catalyst. The copolymers so produced can be extruded about electrical conductors and water-cured providing insulation or jacketing thereon.

Description

fly :

POLYSILOXAN~S AND TOE US TOUGH
IN THE PRODUCTION OF SOLON MODIFIED ALXYL~E-ALKYD ACRYLATE COPOLYMERS

SUMMARY OF THE INVENTION

This invention relates to polysiloxanes and the use thereof in the production of Solon modified alkylene-alkyl acrylate copolymers. The Solon modified alky~ene-alkyl acrylate copolymers can be extruded about electrical conduct ions and water cured to cross lined products, providing insulation or jacketing thereon which is free of undesirable odors and desirable interval voids. Being free of undesir-able internal voids, the insulation or jacketing is character-iced my improved physical and electrical properties such a tensile strength, elongation, insulation resistance and ho like. Also, the p~lysilo~anes this invention are characterized by improved thermal stability and as a result, the inane modified copol~mers produced therefrom are cozily of being subjected to longer prove sing cycles at elevated temperatures without undergoing undesirable thermal degrade-Sheehan I

~2~7~1 D-13532 I

BACKGROUND OF REINVENTION

Water curable, Solon modifies copolymers of alkaline-alkyd acrylates and a process for the preparation thereof by reacting a mixture containing a monomeric Solon and an alkaline Lyle acrylate copolymer are described in detail in US Patent 4,291,136 to Michael J. Coffey, granted September 22, 1981. The Solon modified copolymers can be extruded about electrical conductors, such as wire and cable, and water cured to cross linked products to provide coatings thereon ox excellent quality.
It is customary, prior to extruding Solon modified alXylene alkyd acrylate copolymers about wires and cables, to insure removal therefrom of undesirable volatile.
the presence of undesirable volatilize could lead to the formation of voids in the extruded product, marring its appearance, regrading its physical and electrical properties and, in some instances, shortening its working life In addition, the presence of undesirable volatile causes odor problems at the extrude and in the coated wire or cable.
Obviously, removal of such volatile from the Solon modified copolymers, by a subsequent de~o~atilization step after preparation of toe copolymer~, increases the time and cost required to produce a coated product.

D-13532- Eel I

DESCRIPTION OF TO}: INVENTION

The present invention provides for polysiloxanes and the use thereof in the production of Solon modified copolymers of alkylene-alkyl acrylates which are free of desirable low boiling volatile and consequently need not be subjected to a subsec~uen'c devolati~ation step. The Solon modified keep-mews, prepared in accordance with the present invention, can be directly extruded about wires and cables and water-cured to cross linked products to provide insulation or jacketing thereon, free of undesirable voids and odors. Furthermore, the polyp selections of this invention are characterized by improved ~ermal stability and the Solon modified, water-curable alkylene-alkyl acrylate copolymers produced therefrom are capable of being subjected to longer processing cycles in the production of extruded products without undergoing undesirable thermal degradation.

The polysiloxanes of this invention fall within the scope of idealized Formula I bullock:

FORUM I:

_ _ O _ _ - Syria n - O Creole C - - O (R) n six _ V V y D~13532-C-1 wherein each R and Al, which can be toe same or different, are hydrocarbon radicals; each V, which can be the same or different it hydrogen, a hydrocarbon radical or a hydrolyzable group; each I, which can be the same or different is a hydrolyzable group; x and y are integers each having a value of at least 1, generally AL TV 20 inclusive, preferably 5 to in inclusive and each n, which can be the same or different is an integer having valve of at least one, generally one to 10~0 inclusive, preferably 2 to 25 inclusive.

Illustrative of suitable diva lent hydrocarbon radicals for R are alkaline radicals having one to 18 carbon atoms inclusive, preferably one to 6 kern atoms inclusive such as ethylene, ethylene, propylene, battalion, hexylene and the like: aureole and cycloaliphatic radicals having 5 to 18 carbon atoms inclusive, preferably 6 to 8 carbon atoms inclusive such as cyclohexylene, phenylene and the like.

Illustrative of suitable hydrocarbon radicals for I are cycloaliphatic and aureole radicals as defined for R.

As stated, each V can be hydrogen, a hydrocarbon radical or a hydrolyzable group. Illustrative of such hydrocarbon radicals or hydrolyzable groups are alXyl radicals having one to 18 rarb~n a inclusive, preferably one to 6 carbon D-13532~
I

atoms inclusive such as methyl, ethyl n-propyl, isopropyl, n-butyl, n-hexyl and the like; alkoxy radicals having one to 18 carbon atoms inclusive, preferably one to 6 carbon atoms inclusive Suckle as methoxy, ethics propoxy, hexoxy, dodecyloxy, methoxyethoxy and the like; aureole radicals having 6 to 8 carbon atoms inclusive such as phenol, methyl phenol, ethyl phenol, ox phenol and the like; cycloali-phatic radical having 5 to 8 carbon atoms inclusive such as cyclopentyl, cyclohexyl, oxycyclohexyl and the like.

2, as previously stated, is a hydrolyzable group among which can be noted alkoxy radicals as previous-lye described for Vet ox aureole radicals such as ox phenol and the like; oxyaliphatic radicals such as owe Huxley and the like; halogens such as chlorine and the like and other hydrolyzable grouts as further described in US.
Patent 3,458,420 to John B. Wiggly, patented October 29 1968~

Polysiloxanes can be prepared by reacting a dip ester having the formula:

FORMULA I I .

O O
R;~_o_~_Rl_c owe wherein each R2, which can be the same or different, are hydrocarbon radicals as defined or V and Al is as previous-lye defined with a monomeric Solon falling within the scope of Formula III.

FORMULA III
_ O V

3 if l R courtesies no wherein R3 it a hydrocarbon radical, a for example, an alkyd .
radical having one to 18 carbon atoms inclusive, preferably one to four carbon atoms inclusive such a methyl, eel n-propyl, i60propyl, n-butyl and the like: alkaline radical having two to 18 carbon atom inclusive, preferably two to 4 carbon atom inclusive such a ethylene, propylene and the like; aureole radical having I to ten carbon atop inelu~ive such a phenol, bouncily and eke like. Other variable are a previously defined.
Exemplary ox suitable illness falling within the scope of Formula If are the following:

C~3 OH ~C-C-O(CH2)35i(0CH2~H3)3 ~-methacryloxypropyltriethoxy Solon o OH
Al 1 3 SHEA C O(CH2~2l 3 acetooxyethylme~hyldimethoxy Solon OUCH
SHEA
SHEA C-~-o(c~2)35i(oc~3)3 ~-methacryloxypropyl~ri~ethoxy Milan o SHEA C-0(~2)~5~CH3)3 acetooxypropyltrimethoxy Solon $~3~2~ D-135~2-C-I

CH3-C~o(cH2~3si~9cH2~H3~ aceeooxypropyltriethoxy inane SHEA
CH2=~~c~O(cHz)3si~c2Hgoc~3~3 ~-methacryloxypropyl-~ri~-V (2-methoxyethoxy~ Solon CH3-C-o-cH2c~25l(ocH3~3 acetooxye~hyl~rimethoxy inane CH3-c-o-cH2cHzsi(ocH2~H333 acetooxyethyltriethoxy inane O
CH3-C-o-cH2cH~si(oc2H4oc~3~3 acetooxyethyl-t~is-(2-methoxy-ethics) inane SHEA
SCHICK C SHEA 3)3 B-methacryloxye~hyltrimethoxy inane Toe polysiloxane6 generally have a vacua of about 100 centistoke~ to about 1000 centi~toke~ preferably about 150 centi6toke~ to about 250 centi~toke~, a determined using a Gardner viscosity tube at a temperature wherein R3 it a ~yd~9ca~bon radical, a cry ~xa~pl~, an alkyd radical havinq~ee to lug carbon atop inclusive parboil on to four Cobb aye inc~u6iv~ 6UC~ et~ylO ethyl Nepal i~opropylO -burl and two lit; annul radical having two to 18 carbon atop incl~t~lvo, parboil rho to Corey atom inclu6iv~ suck a Tulane, replan and thy like: aureole radical having six to ten capon Tao clove such a Honeywell bouncily an the like. ought varlable0 art a eve dined.
Exemplary ox 6u~tabl~ 8ilane~ Allen within thy kiwi ox Formula It art eye following:

CHZ~c-c-o(c~2)3s~(oc8zc83)3 ~-methacryloYy~ropyl~rie~hoYy Lyon ~æ~7Z~ D-l3~32-c-l I Cal If 3 CH3-C-o~cH2~25i-o~3 acetooxyethyamethyld;methoxy Solon I
OH
SCHICK C-(CH2335~5~3]3 ~-methacryloxypropyltrime~hoxy Milan Sol CH3~C~(CH~)35i(CH3~3 a~etooxyp~Qpyl~rimethoxy Milan .
Chihuahuas) ace~ooxypropyltr~ethoxy Solon I
Ho -O(c~2)35i(0c~H~ocH3)3 ~-me~hac~ylo%ypropyl-tri~-O (2-~et~oxyethoxy) inane o CH3-C-o-cH2c~si(oc~3~3 acetooxyethylt~imethoxy Sloan 3 C-o-cH2cH2si(oc~2c~3g3 acetooxyethyltr~Pthoxy Milan CH3-C-o-cHzcH;~si(OC2H40CE~3)3 acetooxyethyl-tris-(Z-methoxy-epoxy Milan SHEA
CH22c-c-o~2~2~i~oc~333 ~-methac~yloxyethyltrimethoxy aye O

Toe ~olys~loxane~ generally ha a ~i~co~ity of about 100 scientists Jo abut 1000 ~enti~okes ~re~erablr about 150 centistoke~ to about 250 ce~ti6toke~ detrain using a adder viscosity tube at Tartar of 25C.
The reaction between a divester of Formula II and a moo-metric Sweeney of Formula and mixtures whereof is conveniently catalyzed by the use of an organ metallic catalyst such all a metal carboxy1ate or an organ titan ate. Among suitable metal ~23~72~ D-l3532-c-l carboxylates can be noted-dibutyltin dilaurate, stuns acetate, stunk ooze, lead naphthenate~ zinc octet, iron 2-ethyl hexoate and the like. Conditions employed for the production of polysiloxanes; reaction temperatures, amity of materials and the like, using metal carboxylates as catalysts ore the same as subsequently described with respect to the use of organ titanates.
For purposes of the present invention, organ titanates are preferrer. Organ titan ate catalysts combine with the polysiloxanes to produce organ titan ate modlfi~d polysiloxanes.~ These polysiloxanes can be used as such, without the use of additional organ ~itanate catalyst, to react with alkylene-alkyl acrylate copo.lymers~ as will be explained.
Suitable organ titanates fall within the scope of Formula IV.

FORMULA IV:

Tory wherein each R4, which can be the same or different, is hydrogen or a hydrocarbon radical having one to 18 carbon atoms inkwell-size, preferably one to 14 carbon atoms inclusive, with at least one R4 being a hydrocarbon radical.
Exemplary of suitable hydrocarbon radicals are alkyd radicals such as methyl, ethyl, n-propyl, isopropyl, bottle, octal, laurel myristyl, stroll and the like; cycloaliphatic radicals such as cyclopentyl, suckle and the like; aureole I D-13532~C-I

radicals such as phenol, methylphenyl, chlorophenyl and the like; alkaryl radicals such as bouncily and thy like.
Particularly desirable titanates falling within the scope of Formula IV are those wherein each R4 is alXyl having one to 18 carbon atoms inclusive, preferably one to 14 carbon atoms inclusive, exemplified by tetrabutyl titan ate, twitter-isopropyl ~itanate and the like.
Organ tints falling with the scope of Formula IVY
are known compounds and can be conveniently prepared as described in So Patent 2,984,641 to Leon E. Wolinski, patented May 16~ 1961.
. Other suitable organ titanates are the organ titanium chelates such as tetraoctylene glycol titanium, triethanol amine titan ate, titanium acutely acetonate, titanium lactate and the like.
The catalyst, preferably an organ titan ate, is used in an amount sufficient to catalyze the reaction between the divester and monomeric Solon.

As a rule, the amount of catalyst used is on the order of about 0.001 to about 25 percent by weight, preferably about 0.5 to about S percent by weight, based on the weight Solon.
The temperature at which the reaction is conducted can be varies over a wide range, for example, from about70C to about 200C. A temperature in the range ox about 100C to about 150C is preferred.

D-13532~C-l I

The reaction between the divester and the monomeric Solon can ye conducted under atmospheric, sub atmospheric or super atmospheric pressure. It is preferred to conduct the later stages of the reaction under sub atmospheric pressure to allow for more facile removal of volatile byproducts Completion of the reaction is evidenced by cessation of the evolution of volatile and the weight volume of volatile collected as compared to the theoretical weight/v~lume~ Alternatively, the reaction can be run to a desired viscosity level and the reactants cooled to stop the reaction.
The repeating units of the polysiloxane, as shown in Formula I, can ye varied by varying the mole ratio of the monomeric Solon and divester reactants. For purposes of stoichiometric calculations, 2 molecules of a monomeric Solon are deemed to react with one molecule of the divester, with x and y, in such case, each being onelvarying the mole ratio, results in varying the number of repeating unit.
For example, as it seen from Example it the mole ratio of monomeric Solon to divester is 10 to 1. In that case, x and y, in the formula of the polysiloxane, ideally would be equal to 5. In carrying out the reaction, at least about a stoichiometric amount of reactants is used.
The alkylene-alkyl acrylate copolymers with which the polysiloxanes are reacted to form the Solon modified copolymers are known copolymers produced by reacting an alkene with an allele acrylate~

Suitable alikeness are ethylene, propylene, buttonhole, isobutylene, pentene-l, 2-methylbutene-1, 3-methylbutene-1 Helene, heptene-l, octene-l and the live.
The alkaline moiety of the alkylene-alkyl acrylate copolymer generally contains from 2 to 18 carbon atoms in-elusive, preferably 2 o 3 carbon atoms inclusive.

Suitable alkyd acrylate monomers which are cop~lymeriz-Ed with the alkenes,fall within the scope of the following formula:

FORMULA V:
. _ SHUCKS

OURS

wherein R4 is hydrogen or methyl and R5 is alkyd having one to 8 carbon atoms inclusive. Illustrative compounds encompassed by this formula are: methyl acrylate, ethyl acrylate, t-bottle acrylate, methyl methacrylate, n-butyl acrylate, n-butyl-methacrylate, 2-ethylhexyl acrylate and the like.
Alkylene-alkyl cruelty polymers generally huge a density ~ASTM D-150S with conditioning as in ASTM D 147-7~) of about O.g2 to about 0.94 and a melt index tASTM-1238 at 44 psi tested pressure) of about 0.5 to about 500 decigrams per minute.

For purposes of the present invention, the preferred copolymex is a copolymer of alkylene-alkyl acrylate, generally having about one to about 50 percent by weight Coronado alkyd acrylate, preferably having about 2 to about 20 percent by weight combined alkyd acrylateO
The production of a Solon modified copol~mer of an al~ylene-alkyl acrylate is carried out by reacting a polyp selection, as described, with a copolymer of an alkaline-alkyd a~rylate in the presence of an organ titanatP catalyst.

In owe infitance6 wherein the poly~iloxane contain combined organ titan ate, additional organ titan ate catalyst may not be necessary. e6pe~ially when at least 0.5 percent by weight organ titan ate, bayed on the weight of the inane was used in the preparation of the poly6iloxane.
he amount of organ titan ate catalyst added to the reaction mixture it a catalytic amount, sufficient Jo catalyze the reaction between the p~ly~iloxane and the copolymer.
A preferred amount is from about 0.001 to about 50 percent by weigh, most preferably about 0.1 to about 25 percent by weight based on the weight of the poly6iloxane.
The amount of poly~iloxane used can vary from about 0.05 to about 10 and preferably about 0.3 Jo about 5 percent by weight based on the weight of the copolymer.
The temperature at which this reaction is tarried out it not critical and can vary conveniently, from about ~0C to about 250~C and preferably from about 150~C

to about kiwi The reaction can be carried out at atmospheric, tub-atmospheric or super atmospheric pressure, although atmospheric pressure it preferred.
Completion of the reaction is evidellced by measurement of no further viscosity change.
Recovery of the inane modified copolymel it effected by allowing the contents of the reaction flask to cool and discharging the product into a suitable receiver for storage preferably under an inert gas blanket.
The reaction can be carried out in any suitable apparatus, preferably an apparatus in which the copolymer it subjected to mechanical working such as a Bra bender mixer, a Danbury mixer or an extrude. The poly~iloxane can ye added to the fluxed copslymer and the organ titan ate, if needed then added. Alternatively, the organ titan ate, if needed, can ye added to the copolymer prior to the addition of the polysiloxane. Also organ titan ate and polysi~oxane can be premixed and added to the fluxed cop~lymer.
The reaction between the polysiloxane and the alkaline-alkyd acrylate copolymer can be depicted as shown below:

--Iris + zfs~tR~¦ L'--Rl--C~--~R~ so aU~lene-aIkyl acrylate cDpolymer Dwight trademark ~3~7 D-13532-C-l ._ I o V
I
~C~C- O'ER- Six V x wherein the variables are as previously defined.
The curing or cross linking of the Solon modified alkyd lene-alkyl acrylate copolymer is effected by exposing the co-polymer to moisture. The moisture present in the atmosphere is usually sufficient to permit curing to occur over a period of 48 hours.
The rate of curing, in a matter of 30 minutes, can be accelerated by exposure to an artificially humidified atoms-phone or immersion in water and heaving to elevated tempera-lures or by exposure to steam.
Generally, curing is effected at temperatures on the or-don of about 23C to about 100C, preferably about 70C to about 100C.
Additionally, the cross linking may be carried out in the presence of a sullenly condensation catalyst. A unique feature of this invention is that the rros51inking reaction can be car fled out at significant rates in the absence of added sullenly condensation catalyst. The organ titan ate catalysts or gala-lust residues present in the production of the Solon modified copolymers also catalyze the cross lining reaction.

Alternatively a wide vouch of Muriel which lung-Shea a 6ilanol condell~ation cataly6tl; and which are known in thy art can be employed in the ranking prows. Such ~2397~1 D-135~2-C-I

materials include metal carboxylates previously described;
organic base such us ethyl amine, hexylamine, dibu~ylamine, pardon and the like and Audi such as mineral acid and fatty acids and the like To the Solon modified copolymers of this invention can be added various additives in amounts well known id the art, such as filler among which can be mentioned carbon black, clay, talc (magnesium silicate, calcium carbonate, silica, aluminum hydroxide and the like, antioxidant, lubricant and the like.
The Solon modified copolymers can be rendered flame retardant by the addition thereto of halogen containing flame retardants such as ethylene-bis(tetrabromophthalimide), decay bromodiphenyl oxide, chlorinated polyethylene, polyvinyl color-ire and ~alogenated paraffin waxes alone, or in admixture with organic or inorganic antimony compounds such as antimony oxide and/or alkaline earth metal oxide, carbonates, hydroxides and .
sulfates. among such alkaline earth metal compound can be noted calcium oxide, calcium carbonate, calcium hydroxide, eel-alum sulfate, magnesium oxide, magnesium carbonate, magnesium hydroxide and magnesium sulfate.
Mixtures of reactants, catalyst and additives can be used, if Jo Doria.
The following examples further illustrate toe present invention and are no intended to limit the scope whereof.

D-13532 C-l Preparation of a poly~i1Oxane based on acetooxyethyl~ri-methoxy Solon and di~ethyltereph~halate.
Into a dry one liver, 3-necked flask, equipped with a mechanical stirrer, thermometer nitrogen gas inlet tube and take-off condenser, there was charged 356.7 grams (1.71~ moles of acetooxyethyltrimethoxy Sloan, The acetooxyethyltrimethoxy Solon was heated to a temperature of 80C and at this point, 3.33 cc (3~2 grams) of twitter-isopropyl titan ate were added to the flask by means of a syringe. Heating was continued and when the contents of the flask reached a temperature of 107C, methyl acetate began to distill. After 102.6 grams of methyl acetate were collected, 33.0 grams (0.17 motel of dim ethyl-terephthalate were added to the contents of the flask.
The contents of the flask were then brought to a tempera-lure of 140C and maintained at this temperature, while under a vacuum of 10 inches until cessation of volatile.
Total amount of distillate recovered: 122.6 grams Theoretical amount of distillate: 125.8 grams The polysiloxane recovered in an amount of 270.3 grams, ha the following idealized formula:

~23~
_ OH 3 9 t 5C--CH2--CH2~ I I lQc~2 C~2 - S it ooze 3 and was a highly rescues material.

Preparation of a polysiloxane based on acetooxyethyl-trimethoxy Solon and dimethyliso~hthalate.
Into a dried, one liter, 3-necked flask, equipped with a mechanical stirrer, thermometer, nitrogen gas inlet tube and take-off condenser, there was charged 356.7 grams (1.71 moles) of acetooxyethyltrimethoxy Solon. The I, acetooxyethyltrimethoxy Solon was heated to a temperature of 80~C and at this point, 3.33 cc (3.2 grams) of twitter-isopropyl titan ate were added to the flask by means of a syringe Heating was continued and when the contents of the flask reached a temperature of 107C, methyl acetate began to distill. Afterl117.6 grams of methyl acetate were collected, 33.0 grams (0.17 mole ox dim ethyl-is~phthalate were added to the contents of the flask.
The contents of the flask were then brought to a temperature of 140C and maintained at this temperature, while under a vacuum of lo inches, until cessation of volatilize, I

D-13532-C-~

Total amount of distillate recovered: 123.7 grams Theoretical amount of distillate: 12508 grams The polysiloxane recovered, in an amount of 269~2 grams had the following idealized formula:

OH 0 I Chihuahuas i C ox it 5 Viscosity ox the poly6iloxane - Z50 centi~tokes -determined at a temperature of 25C using a Gardner vacuity tube.

Preparation of a poly6iloxane based on acetooxyethyl-trimet~oxy inane and dimethylisophthala~e.
Into a tried, one fleer, 3-necked flask, equipped wit h a mechanical swearer thermometer, nitrogen isle tube and take-off condenser, there was charged 356.7 gram (1.71 mole of acetooxyethyltrimethoxy inane and 33.0 gram of dim ethyl-i~ophthalate. The convents of the flask were heated Jo a temperature of 80C and at this point 3.33 I I grams) of ~23~72~ D-13532-C-I

tetraisopropyl Tut wile added to the flask by means of a syringe. The Canaanite of the flask were then brought Jo a temperature of lode and maintained at this temperature, while under a vacuum of lo ionic, until cessation of Yola~iles.

The total amount of distillate recovered: 123.6 grams Theoretical amount of distillate: 125.8 gram The polysiloxa~e recovered, in an amount of 269.3 grams, had the following idealized formula-_ l OUCH 8 11 ITCH
SHEA SHEA SHEA- - C C - oCH2CH2-Si - -OUCH

Viscosity of the polysiloxane - 340 centistokes -determined at a temperature of 25C using a Gardner viscosity tube.

.

Preparation of a polysiloxane based on acetooxyethyl-trimethoxy solely and dimethylisophthalate.
Into a dried, one Lowry nicked flask, equipped with a mechanical stirrer, thermometer nitrogen gas inlet tube and takeoff condenser, there was charged 2140 grams (10.3 moles) of acetooxyethyltrimethoxy Solon. The acetooxyethyltri-methoxy six aye was heated to a temperature of 30C and at this punt cc (19 grams) of tetraisopropyl titan at were added to the flask by means ox a syringe. Heating was continued and when the contents of the flask reached a temperature of 107C3 methyl acetate began to distill.
After 366~5 grams of methyl acetate were collected, 198 grams (1.02 moles) of dimethylisoph~halate were added to the flask. The contexts ox the flask were then brought to a temperature of 140C and maintained at this temperature, while under a vacuum of 10 inches, until cessation of vote it lies .

Total amount of distillate recovered: 728.4 grams Theoretical amount of distillate: 760.2 grams The polysiloxane recovered, in an amount of 1628.6 grams had the following idealized formula:

I Ho r ITCH 1 SHEA ~si~CH~CH~ C _ oCH2CH~-Si - - SHEA

OOZE ¦ 3 .

I D-13532-C-l -Preparation of a water cured, Solon modified alkaline alkali acrylate copolymer by reacting a mixture containing the polysiloxane of Example 4 and a cvpolymer of ethylene-ethyl act late.
To Composition A, the formulation of which is noted below, there was added:

Percent by Weight Based On Weight of composition_ Polysiloxane of Example 4 1.42 Tetraisopropyl ~itanate ` 0.24 Dibutyltin Dilaurate 0.06 Composition A
Ethylene-ethyl acrylate copolymer Melt Index 1.3 Percent by weight combined Ethyl acrylate - 15 56.1 Talc coated with one percent Zinc Stewart 21.7 Ethylene bis(tetrabromophthalimide3 16.3 Calcium carbonate coated with Calcium Stewart 2.6 Antimony trioxides containing 3 percent by weight white mineral oil I
2,2-dihydro-2~3~4-te~ramethylquinoline 0.6 (antioxidant) Vinyl tris-(2-methoxyethoxy) Solon 0.2 (lubricant) I

.

D-13532~
I

All ingredient, with he exception of the or~ano into the poly6iloxane of Example 4 and the dibutyl-yin dilaurate were mixed Jo homogeneity in a Bra bender*
mixer which had bee preheated to a temperature of 160C.
After ~omogeniety way attained, the organ titan ate, the dibutyltin dilaurate and the polysiloxane were introduced into the Bra bender mixer. The mixture was reacted for 20 minutes at a temperature of 175C and the resultant composition containing the water curable, inane modified alkylene-alkyl acrylate copolymer way discharged hot into a polyethylene bag and kept under a blanket of argon.
Sample of the composition were used to prepare test plague, having dimension of 3 inches by B inches by Owls inch in a press, under the following conditions:

Pressure 5000 pi Temperature 130~C
Time Cycle 5 minute eye plaques were cured by being immersed fox 16 house water bat, icky was at a empress of 70~C and the eye for degree of Corey awoke g to toe Mennonite Remoter ten, describe on detail US 4.01~,95Z~ granter April 19. 1977.

trademark I

.~. .

23~

Munson Remoter test - 59 ;noh/lb~.
The result of the Monsanto Remoter text indicated high level ox cur, The ~ompo~ion of Example 5 way; extruded onto a wire by eke following procedure:
An initial feed, Formulaeiun A of Example 5, was fed into a 2 1/2, 20 to 1 (length Jo dimmer) Rowley ~xtrud2r wherein the inlay feed weft combined with a second feed, also described in Example I of polysiloxane, tetraisopropyl eighteen and dibutyltin dilaurate. The amount of second Peed was 1.8S percent by weight of the first feed. The weight ratio of polysiloxane to tetraisopropyl titan ate to d;butyltin dilaurat~ way about 24 to 4 to I The resultant, Wright composition was extruded onto a ~14 AWN solid copper wiry under the following conditions:

Cycle 1-2 minutes Compound temperature SEIKO

The coaxed wire was fed through a water Tao, which way at ambient temperatures, with the result that toe composition ox ye wise cured Jo a croszlink~d product having a thickness of about 30 my triadic 123~7;2:~ D-13532 c- t The polysiloxane of Example 2 and a polysiloxane t produced according to Example 3 of So Patent 4,328,323, were tested for thermal stability according to the Therm Gravimetric Analysis test described in detail in Section 9 of Ho I. Dupont deNemo~rs Manual entitled instruction Manual 990 Thermal Analyzer and Melissa Time for each sample to lose ten percent of its weight at the temperature indicated 'is tabulated below:

Polysiloxane of Example 2 25 minutes 7 minutes Polysiloxane of Example 3 of US. 4,328,~3 10 minutes 4 minute

Claims (9)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A process of preparing a water curable, silane modified alkylene-alkyl acrylate copolymer which comprises reacting a mixture containing an alkylene-alkyl acrylate copolymer, an organo titanate catalyst and a polysiloxane having the formula:

wherein each R is a hydrocarbon radical, R1 is a hydrocarbon radical, each V is hydrogen, a hydrocarbon radical or a hydrolyzable group, Z is hydrolyzable group, each n is an integer having a value of at least one, and x and y are integers each having a value of at least 1.

2. A process as defined in claim 1 wherein the alkylene-alkyl acrylate copolymer is ethylene-ethyl acrylate copolymer.

3. A process as defined in claim 1 wherein in the formula of the polysiloxane: each R is alkylene, R1 is arylene or a cycloaliphatic radical, V is hydrogen, a hydrocarbon radical or a hydrolyzable group, Z is a hydrolyzable group, each n is an integer having a value of one to 1000 inclusive and x and y are integers each having a value of 1 to 20 inclusive.

4. A process as defined in claim 1 wherein in the formula of the polysiloxane, each Z is methoxy, each V is methoxy, each R is -CH2CH2-, R1 is phenylene and x and y each have a value of 5.

5. A process as defined in claim 1 wherein the organo titanate is present in an amount of about 0.1 to about 25 percent by weight based on the weight of the polysiloxane.

6. A process as defined in claim 1 conducted at a tempera-ture of about 80°C to about 250°C.

7. A process a defined in claim 1 conducted at a tempera-ture of about 150°C to about 200°C.

8. A process as defined in claim 1 wherein the organo titanate has the formula:
Ti(OH4)4 wherein each R4 is hydrogen or a hydrocarbon radical, with one of said R4 being a hydrocarbon radical.

9. A process as defined in claim 8 wherein the organo titanate is tetraisopropyl titanate.