CA1091383A

CA1091383A - Epoxy-functional polysiloxane polymers

Info

Publication number: CA1091383A
Application number: CA249,381A
Authority: CA
Inventors: Eugene R. Martin
Original assignee: Wacker Chemical Corp
Current assignee: Wacker Chemical Corp
Priority date: 1975-04-07
Filing date: 1976-04-01
Publication date: 1980-12-09
Also published as: JPS5853655B2; FR2307005A1; DE2615077A1; AT354732B; AU499062B2; JPS51121099A; IT1058081B; AU1179876A; GB1518591A; NL7603534A; ATA247576A; FR2307005B1; BE840471A

Abstract

ABSTRACT OF THE DISCLOSURE

Novel branched chain epoxy-functional polysiloxane polymers are prepared by reacting a trialkoxy-containing epoxy-functional organo-silicon compound with a cyclic organosiloxane selected from the group consisting of organocyclotrisiloxanes and organocyclotetrasiloxanes in the presence of a catalytic amount of a lithium compound selected from the group consisting of lithium alkyls, lithium aryls, lithium hydrides, lithium hydroxide and lithium alkoxides. The reaction may be carried out in water and, in one specific reaction, the trialkoxy is reacted with water in the presence of the catalyst at an elevated temperature prior to the addition of the cylic organosiloxane. The catalyst may be basic catalysts other than lithium catalysts. These epoxy-functional poly-siloxane polymers may be used as reactive intermediates for preparing copolymers, as sizing agents, and as protective coatings.

Description

1091;~3 .
The present invention relates to epoxy-functional organopoly-siloxanes and more particularly to epoxy-functional organopolysiloxanes which are obtained from the reaction of organopolysiloxanes and epoxy containing silicon compounds in the presence of a base catalyst.
Heretofore, epoxy containing organosilicon compounds have been prepared by reacting an organopolysiloxane with a dialkali metal salt and thereafter reacting the resultant product with an epihalohydrin.
(See United States Patent No. 2,997,458 to Lewis.) Also, United States Patent No. 3,660,434 to Patterson discloses reacting aminosilanes with silanols having terminal double bonds and thereafter reacting the resul-tant product with epoxide compounds. Organosilicon epoxides are also disclosed in United States Patent No. 3,455,877 to Plueddemann in which these organosilicon epoxides are prepared by reacting organosilicon com-pounds containing a C=C group with peracids or by reacting an unsaturated organic compound containing at least one epoxy group with a silicon com-- pound containing at least one SiH group in the presence of a platinum compound.
- The above-described processes for preparing epoxy containing organosilicon compounds have several disadvantages. For example, if a ' 20 monoepoxy-funct:ional dimethylpolysiloxane composition is desired, the above-described processes require a siloxane having one amino-functional group or one SiH group, or a siloxane which contains one C=C group.
Althoygh it is known that the aforementioned organo-functional can be prepared by equilibration, condensation, or cohydrolysis, each process leads to a random distribution of the functional groups. Thus, some of the molecules contain more than one organo-functional group, others contain one, and still others contain no functional groups. Therefore, conversion of the organo-functional group to an epoxide results in the same random distribution.
It is an object of one aspect of this invention to provide a new class of epoxy-functional polysiloxane polymers.
An object of another aspect of this invention is to provide a 109i383 process for preparing a broad spectrum of epoxy-functional polysiloxanes.
An object of a further aspect of this invention is to provide a process for preparing epoxy-functional polysiloxanes without first having . to prepare aminosilanes, vinyl containing siloxanes or SiH containing siloxanes.
An object of a still further aspect of this invention is to pro-` vide a process for preparing epoxy-functional polysiloxanes substantially ~ free of condensation by-products.
An object of a still further aspect of this invention is to pro-vide a process for preparing epoxy-functional polysiloxanes substantially free from SiH unsaturated impurities.
An object of a still further aspect of this invention is to pro-vide a process for preparing epoxy-functional siloxanes which are substan-tially free from equilibration which leads to a random distribution of the epoxy functionality.
In accordance with an aspect of this invention, organosilicon compounds containing an epoxy or substituted epoxy-functional group are re-acted with an organopolysiloxane in the presence of a base catalyst and an aprotic solvent, if desired.
Thus, by one broad aspect of thls invention, a process is pro-vided for preparing branched chain epoxy-functional polysiloxane polymers which comprises reacting an organosilicon compound of the formula ~ -ASi(OR)3 wherein A is a radical containing at least one epoxy group and R is a mono-` valent hydrocarbon radical having from 1 to 18 carbon atoms with a cyclic organosiloxane selected from the group consisting of organocyclotrisiloxanes and organocyclotetrasiloxanes in the presence of a catalytic amount of ; lithium compound selected from the group consisting of lithium alkyls, lithium aryls, lithium hydrides, lithium hydroxide and lithium alkoxides.

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:, ' , It was discovered that the molecular weight of the polymers was a function of the alkoxy to cyclotrisiloxane molar ratio. Furthermore, it is believed that the lighium catalyst first reacts with the cyclo-.

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~10913~33 trisiloxane to form a linear siloxane terminated with a lithium cation which then condenses with the epoxy-functional silane to form an epoxy-functional alkoxy endblocked siloxane and the lithium alkoxide. The lithium alkoxide further reacts with more of the cyclotrisiloxane to form more lithium endblocked siloxane which then condenses with the epoxy-func-tional alkoxy silane or epoxy-functional alkoxy endblocked siloxane. This series of reactions is repeated until all the cyclotrisiloxane has been consumed. Since lighium compounds are the catalysts employed, little, if any, equilibration occurs, see e.g., United States Patent No. 3,483,270 to Bostick. Since equilibration does not occur, the epoxy-functional alkoxy endblocked siloxane or epoxy-functional alkoxysilane are not lithium ter-minated which would lead to a random distribution of functionality in the siloxane. Thus, employing the process of an aspect of this invention, a broad spectrum of new compositions can be prepared including monoepoxy-func-tional siloxanes in which no equilibration occurs.
Furthermore, a substantially pure epoxy-functional polysiloxy polymer of another aspect of this invention is obtained which is substan-tially free of SiH groups, unsaturated organic groups and condensation by-products by the process of the first aspect of this invention described above.
By preferred variants of the invention, the lithium catalyst compound may be a lithium alkyl; or a lithium aryl; or a lithium alkoxide;
or a lithium hydride; or a lithium hydroxide.
By another variant, the silane may be gamma-glycidoxypropyltri-methoxysilane.
- In another variant, the organosilicon compound is a silane of the formula _ 3 _ ' ~ - 1091383 - ~ O ~ Z

( R )4-e-b where R is selected from the group consisting of hydrogen anù monovale~t ': - 3 ~

109i3~

hydrocarbon radicals having from 1 to 18 carbon atoms, R~ is a monovalent hydrocarbon radical having from 1 to 18 carbon atoms, R" is selected from the group consisting of divalent hydrocarbon radicals having from 2 to 18 carbon atoms and the corresponding divalent hgdrocarbon radicals containing C-O-C linkages, X is selected from the class consisting of hydrogen and a monovalent hydrocarbon radical containing a single carbon atom or a group of carbon atoms interconnected by single or multiple bonds which may contain groups selected from the group consisting of hydrogen, alkyl, hydroxyl, slkoxyj amino and cyclic hydrocarbons, Z is selected from the group consis-ting of OR, R and OSiR3', and R and R' are the same as above, b is a numberof from 1 to 3 and e is a number of from 0 to 2.
In still another variant the cyclic organopolysiloxane has the formula ~ R
~ sio J

., Z
wherein R is selected from the group consisting of monovalent hydrocarbon radicals having from 1 to 18 carbon atoms and z is 3 or 4.

By one specific variant, the cyclic organosiloxane is hexa-methylcyclotrisiloxane.
By another specific variant, the organocyclopolysiloxane is 1,2,3-trimethyl-1,2,3-triphenylcyclotrisiloxane.
In another variant, the reaction is conducted in the presence of an aprotic solvent.
By a variation thereof, the solvent is present in an amount of from 0.5 to 80 percent by weight based on the weight of the composition.
By yet another variation, the aprotic solvent may be tetra hy-droturaD or ethylene glycol dimetùyl ether.

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1091;~

.; Examples of suitable organosilicon compounds which may be em-ployed in the process of aspects of this invention are epoxy-functional silanes of the formula ~ O ~ Z
f ~ ~ le or epoxy-functional siloxanes of the formula [ ~ R R 3 2 ~

: wherein the R(s), which may be the same or different, represent hydrogen ; or monovalent hydrocarbon radicals having from 1 to 18 carbon atoms, R' is a monovalent hydrocarbon radical having from l to 18 carbon atoms, R" is a divalent hydrocarbon radical, e.g. an alkylene radical, an arylene 20 radical or alkenylene radical having from 2 to 18 carbon atoms, or an oxyalkylene radical containing C - O - C linkages, R"' ~s a radical selected from the group consisting of Ro 5 and R3Sio 5~ x represents hy-. drogen or a monovalent radical consisting of a single carbon atom or car-bon atoms interconnected by a single or multiple bond which contains additional groups, e.g. hydrogen, alkyl, alkoxy, amino, cyclic hydrocarbon groups or combinations thereof, Z is a group selected from the class con-sisting of OR, R or OSiR'3, R and R' are the same :

. . .

1~J9~.383 as above, a is a number of from 1 to 20,000, b is a number of from 1 to 3, c is a number of from 0 to 3 and e is a number of from 0 to 2 when c is equal to 0, then at least one Z must be OR.
Among the hydrocarbon radicals represented by R and R' are alkyl radicals having from 1 to 18 carbon atoms, e.g., methyl, ethyl, propyl, butyl, octyl, dodecyl, octadecyl and the like; cycloalkyl radicals, e.g., cyclopentyl, cyclohexyl, cycloheptyl and the like; mononuclear and binu-clear aryl radicals, e.g., phenyl, naphthyl and the like; aralkyl radicals;
e.g,, benzyl, phenylethyl, phenylpropyl, phenylbutyl and the like; alkaryl -- 10 radicals, e.g., tolyl, xylyl, ethylphenyl and thelike; R" is an alkylene radical such as, for example, ethylene, propylene, butylene, pentamethylene, hexamethylene, octamethylene, dodecylmethylene, hexadecylmethylene and octadecylmethylene; arylene radicals such as, for example, phenylene, bi-phenylene and the corresponding alkylene and arylene radicals containing - an oxygen atom. Other radicals represented by R" are vinylene, propenylene, butenylene and the like.
In the epoxy-functional organosilicon compounds represented aobve, X may also have one or more oxirane oxygen atoms attached to vicinal carbon atoms. When the R(s) are taken together with the vicinal carbon atoms, they can represent a cyclic group such as, for example, a cyclohex-ane ring or a cyclopentane ring, substituted or unsubstituted with other groups, e.g., alkyl,aryl substituents and the like. Thus, the epoxy-, containing organosilicon compounds may be selected from the class consist-ing of monoepoxides and polyepoxides, particularly monoepoxides, diepoxides and triepoxides or mixtures thereof.
Examples of suitable organosilicon compounds are silanes . .

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i09~.383 ` or siloxanes such as, for example, gamma-glycidoxypropyltriethoxysilane,4,5-epoxypentyltriethoxysilane, gamma-glycidoxypropyltripropoxysilane, gamma-glycidoxybutyltriethoxysilane, gamma-glycidoxypropyltributoxysilane, gamma-glycidoxypropyltrimethoxysilane, gamma-glycidoxyhexyltriethoxysilane, gamma-glycidoxyoctyltriethoxysilane, gamma-glycidoxyhexyltributoxysilane, glycidoxy-o,p-phenyltriethoxysilane, 5,6-epoxyhexyltrimethoxysilane, 5,6-epoxyhexyltributoxysilane, 7,8-epoxyoctyltrimethoxysilane, 7,8-epoxyoctyl-tripropoxysilane, 9,10-epoxydecyltrimethoxysilane, 9,10-epoxydecyltri-propoxysilane, beta-3,4-)epoxycyclohexyl)ethyltrimethoxysilane, beta-3,4-(epoxycyclohexyl)propyltributoxysilane, 1,3-bis-(3-glycidoxypropyl) tetra-methoxydisiloxane, and the partial hydrolysis products thereof.
; The epoxy-functional organosilicon compounds are mixed with cyclic organopolysiloxanes, and thereafter reacted in the presence of a base catalyst and an aprotic solvent. The resulting epoxy or substituted epoxy-functional polysiloxane polymers may have a ratio of epoxy to siloxane units (R'2SiO) of from 1 to 20,000 to 20,000 to 3 The epoxy containing silanes employed in this reaction may be prepared in accordance with the process described in U.S. Patent 3,057,901 to Plueddemann. For example, epoxy containing silicon compounds may be prepared by the addition of an allylglycidoxy propyl ether or butadiene monoepoxide to a compound containing SiH groups in the presence of a plati-num catalyst at temperatures below 100C.
Another process f~r preparing these epoxy containing silicon compounds is to oxidize an unsaturated hydrocarbon substituent on a silicon with peracetic acid.

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Epoxy containing organosilicon compounds have been pre-pared in accordance with the process disclosed in ~.S. Patent No. 2,997,458 to D.W. Lewis, in which one mole of an organo-siloxane is reacted with from one to two moles of a dialkali metal salt of a compound having at least two phenolic groups at a temperature of from 175 to 200C. and thereafter the re-action product is reacted with at least two moles of an epihalo-hydrin at a temperature of from 70 C to 140 C.
Any of the above epoxy containing organosilicon compounds can be employed in preparing the epoxy-functional polysiloxane polymers of this invention. Thus, epoxy-silanes such as, for example, gammaglycidoxypropyltrimethoxysilane, 4,5-epoxypentyl-: triethoxysilane and silanes or siloxanes can be reacted with :- cyclic organopolysiloxanes to form the epoxy-functional poly-. siloxane polymers of this invention.
The eyclic siloxanes employed in the preparation of the . polymers of aspects of this invention may be represented by the formula R ' `' LSiO~
R' z ' ~
wherein z is 3 or 4. These organopolysiloxanes can be hexamethyl-,~:

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1~J91383 cyclotrisiloxane, hexaphenylcyclotrisiloxane, 1,2,3-trimethyl-1,2,3-tri-phenylcyclotrisiloxane, 1,2,3-trimethyl-1,2,3-trivinylcyclotrisiloxane.
It is preferred that an organocyclotrisiloxane be employed instead of the organocyclotetrasiloxanes because the rate of polymerization of the cyclo-tetrasiloxane is considerably slower than that of the organocyclotrisilox-ane and reactions substantially free from equilibration are obtained.
Examples of suitable compounds are lithium alkoxides such as, for example, lithium methoxide, lithium butoxidep lithium alkyls, e.g.
ethyl lithium, isopropyl lithium, n-butyl lithium, vinyl lithium and the like; lithium aryls such as, for example, phenyl lithium and the like;
lithium hydride, lithium aluminum hydride, lithium silanoate and lithium hydroxide.
The amount of catalyst is not critical; however, it is preferred that from 0.0001 mole percent to 1.0 mole percent of catalyst be employed to effect the reaction and that the mole ratio of catalyst to alkoxy groups ` present in the epoxy-functional silane or siloxanes does not exceed 1 to 12. However, it is recognized that greater amounts may be used, but it is the intent of this invention to provide a catalyst system which does not react with the reactive epoxy group.
Generally, it is desirable to remove or destroy the catalysts after the reactlon because their presence will adversely affect the pro-- perties of the resulting polymer. The base catalyst, for example, may be removed by washing with water. Also, the base catalysts may be destroyed by neutralizing them with acid reagents, i.e., they may be neutralized by ` the addition of an acid. More specifically, the lithium type catalysts may be effectively neutra-.~

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. .
lized by the addition of an organic acid such as acetic acid.
In general, the reaction of the cyclic siloxanes with the epoxy-functional silane or siloxane can be carried out at temperatures ranging from 25~C, up to 150~C. or higher for times varying from a few minutes to several hours. Although it is not essential, it is preferred that the - reaction be conducted in the presence of an inert atmosphere.
The reaction may be conducted in the absence or presence of a silvent. It is preferred that an aprotic solvent which is capable of cooFdinating with the cation be employed. The term "aprotic solvent" is intended to mean any organic solvent that is free of active protons which will interfere with the growing anionic polymerization centers. These may include solvents such as, for example, various tertiary amines such as, for example, triethylamine, tributylamine, pyridine and the like. Other suitable solvents are dimethyl sulfoxide, dioxane, alkyl ethers; glycols ;~ such as, for example, diethylene glycol diethylether, diethylene glycol dimethyl ether, diethoxyethane, tetrahydrofuran and mixtures of solvents having different boiling points permits the process of aspects of this in-vention to be practiced at variable temperatures. However, it is pre-ferred that certain special dipolar aprotic solvents having electron do-! 20 nating centers be employed. These solvents are chosen such that their '' electron-donating centers are capable of forming coordination complexes with the cation, thereby coordinating with the cation and thus enhancing its : reactivity by virtue of such coordination.
Certain other hydrocarbon solvents which do not coordinate with the cation can be employed with the aprotic solvents described above to provide more intimate contact between the reactants.

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~V9~383 Examples of suitable solvents are aliphatic hydrocarbons such as hexane, heptane, octane and aromatic hydrocarbons such as benzene, toluene, xylene and the like. It is preferred in the practice of aspects of this invention that from 0.05 to 10 percent of the aprotic solvent having Lewis base characteristics be employed.
The epoxy-functional siloxane polymers of aspects of this inven-tion may be used as intermediates in the preparation of copolymers contain-ing organopolysiloxane segments which may be used in the formation of various coating compositions. In addition, these epoxy-functional siloxane polymers may be used as sizing agents and as protective coatings for paper and fabrics.
Various embodiments of this invention are illustrated in the fol-lowing examples in which all parts are by weight unless otherwise specified.

:
A reaction vessel containing 222 parts of hexamethylcyclotrisilox-ane, 200 parts of benzene and 22 parts of diethylene glycol dimethyl ether is heated to 60C. after which time 23.6 parts of gamma-glycidoxypropyl-trimethoxysilane and 2 parts of n-butyllithium are added. The reaction mixture is heated to reflux temperature and maintained at this temperature for 2.5 hour. The catalyst is neutralized by the addition of 2 parts of acetic acid and the reaction product filtered. The solvent is removed at 130C. at 2 mm Hg over a period of 4 hours. A clear fluid product is recovered. Nuclear magnetic resonance analysis of the product shows the following groups to be present in the indicated mole ratio:

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Groups Actual Theoretical O
~ \
C 2 2 3 6 0.32 0.33 CH30- 1.0 1.0 (CH3)2SiO 10.4 10.0 The resulting product has a viscosity of approximately 45 cs. at 25C.

In a comparison example, the procedure of Example 1 is repeated except that gamm-glycidoxypropyltrimethoxysilane is omitted. The sesult-ing product is a fluid having a viscosity of 2200 cs. at 25~C. This ex-ample demonstrates that the molecular weight of the epoxy-functional silox-ane is a function of the gamma-glycidoxypropyltrimethoxysilane.

Example 1 is repeated except that 111 parts of octamethylcyclo-' tetrasiloxane (D4) are substituted for the hexamethylcyclotrisiloxane (D3) and the reaction mixture is refluxed for 8.5 hours. Analysis of the re-sulting product shows that 11 percent of the D4 polymerized. This example demonstrates that the cyclotrisiloxanes are more suitable for preparing epoxy-functional sllox es using a lithiut catalyst.

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The procedure of Example 1 is repeated except that 1~3.2 parts of hexamethylcyclotrisiloxane, 13.3 parts of ethylene glycol dimethyl ether, 119.9 parts of benzene, 24.3 parts of gamma-clycidoxypropyltri-methoxysilane~ and 0.064 part of n-butyl lithium are employed. A fluid having a viscosity of 23 cs. at 25C, is obtained.
EX~MPLE S
To a reactor containing 24 parts of gamma-glycidoxypropyltri-methoxysilane, 0.3 part of lithium hydroxide and 248 parts of methanol are -` 10 added 1.35 parts of distilled water over a period of 30 minutes. The con-tents of the reactor are heated to reflux temperature and refluxed for 3 hours. The volatiles are removed at a temperature of 125C. (3mm Hg) over a period of four hours. A sample of the resulting reaction product is - analyzed by N.M.R.

` . Groups Mol e Rati o CH30- 1.5 O~ -CH2CHCH20C3H6si- 1.0 155.4 parts of hexamethylcyclotrisiloxane, 30.0 parts of tetra-hydrofuran, and 120 parts of benzene are added to`the reactor containing the above reaction product. The reactants are heated to reflux tempera-; ture and maintained at this temperature for 2.5 hours. 0.12 part of gla-cial acetic acid is then added and the volatiles removed under vacuum (2 mm Hg) for 4 hours at 100C. The product has a viscosity of 125 cs. at 25C. Analysis by N.M.R. shows the following groups to be present.

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Groups Mole Ratio CH30- 1.5 (CH3)2sjo 21.0 o CH2-CHCH20C3H6Si- 1.0 ~, .

EX~MPLE 6 Polyepoxy-functional dimethylpolysiloxanes containing trialkyl-siloxy units are prepared in accordance with the procedure described in Example 5 except that 54 parts of water are mixed with 298 parts of methanol and added to a reactor containing 0.6 part of lithium hydroxide, 208 parts of trimethylmethoxysilane and 472.6 parts of gamma-glycidoxypropyltrime-thoxysilane.
About 1221 parts of hexamethylcyclotrisiloxane, 1020 parts of benzene and 200 parts of tetrahydrofuran are added to the above product and reacted in accordance with the procedure described in Example 5.

Nuclear Magnetic Resonance analysis shows the following groups to be pre-sent.

G roup s Mo l e Ra t i o CH3S1~ 52.5 CH30- 1 . 0 O
,, . CH2CHCH20C3H6Si- - 1.0 ', ~
. ..

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10~383 -~` SUPPLEMENTARY DISCLOSURE
The Principal Disclosure provided a process for preparing epoxy-functional polysiloxane polymers by reacting na epoxy-functional organosilicon compound with a cyclic organosiloxane in the presence of a lithium compound. As described in the Principal Disclosure, this was an improvement on prior art procedures. One such procedure for preparing epoxy-substituted siloxanes was described in United States Patent No.

3,761,444 to Mendicino, in which lower molecular weight expoy-substituted siloxanes were equilibrated with other siloxanes in the presence of water, a silanol and a basic equilibration catalyst to form siloxane copolymers containing the substituents of both the epoxy siloxane and the other siloxanes.
The procedures described above and in the Principal Disclosure for preparing epoxy-containing organosilicon compounds had several disad-vantages. For example, if a monoepoxy-functional dimethylpolysiloxane composition were desired, the above-described procedures required a ; siloxane having a single amino-functional group or one SiH group, or a siloxane which contained C=C group. Although it is known that the afore-mentioned organofunctional siloxanes could be prepared by equilibration, condensation, or cohydrolysis, each process leads to a random distribu-, tion of the functional groups. Thus, some of the molecules contained ¦ more than one organofunctional group, others contained one, and still i others contained no functional groups. Therefore, conversion of the organofunctional group to an epoxide results in the same random distribu-tion.
- Accordingly, the present Supplementary Disclosure provides still further improvements in the process and compositions provided by the Principal Disclosure.
Accordingly~ by a broad aspect of the invention now pro-vided by the present Supplementary Disclosure, :,' E
.
,. .
, ., , , -. - ..
. , - ~ , . . ~ . . ` . ., ~ , 10~13~3 . . a composition is provided comprising epoxy-functional polysiloxane polymers of the general formula A ~ (OSi)a OR J

'? in which A is a radical containing at least one epoxy group, R is a .. . . ... . . . . . . . . . ..
monovalent hydrocarbon radical having from 1 to 18 carbon atoms, and a is a number of from 1 to 20,000.
By a variant thereof, A is a radical of the formula ; I .
C ~ \ C L R
L R R J b ; in which R is selected from the class consisting of hydrogen and R and when the R'(s) are taken together with the vicinal carbon atoms, may ~, represent substituted and unsubstituted cyclic hydrocarbons, Rll i5 selected from the class consisting of a divalent hydrocarbon radical, a trivalent hydrocarbon radical, a tetravalent hydrocarbon radical, an oxyalkylene radical and oxyarylene radical having C-0-C linkages, X is .
;: selected from the class consisting of hydrogen and a monovalent hydro-carbon radical consisting of a single carbon atom or a group of carbon atoms interconnected by a single or multiple bond which contains addi- I.
tional groups selected from the class consisting of hydrogen, alkyl, ~. hydroxyl, alkoxy and cyclic hydrocarbons, and b is a number of from 1 to 3.
;: By a variation thereof, R is a methyl radical.
- By another variation, the epoxy-functional polysiloxane has the : formula . . .
. . . .

,;

..... . .

,. : .
., / \ ~ (CH3)2 CH2 2oc3H6 si t (OSi)lo OCH3~

By a further variation, the epoxy-functional polysiloxane has the formula Gi2C~2Si - ~ (OSi)lo OC33 ]

By yet another variation, the epoxy-functional polysiloxane has ~ the formula - ~H2 \ n CH

CH
O r (CH3)2 CH2 ~cH-c~2-o-cH2-cH-cH2-oc3H6si L ( Si)lo OCH

.
By a further variation, R' represents an alkyl radical.

By another variation, X is hydrogen and the R'(s) together with the vicinal carbon atoms form a cyclic hydrocarbon.
By yet another variation, R" is an alkylene radical.
By another variation, R" is an oxyalkylene radical having C-O-C
linkages.
By still another aspect, the composition comprises expoxy-func-tional polysiloxane polymers of the formula '' : .

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.. . . -'. '. '. .' ' ' ~ ~ . .- :. :

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lO9i383 , , ~ (CH3)2 ; A - Si t (osi) OR~
.~ 3 `
where A is a radical containing at least one epoxy group, R is a monovalent hydrocarbon radical having from 1 to 18 carbon atoms and a is a number of from 1 to 20,000.
. As described above, these epoxy-functional polysiloxane polymers are preferably prepared by reacting organosilicon compounds containing an epoxy-functional group with cyclic organopolysiloxanes in the presence of a basic catalyst and an aprotic solvent, if desired.
Examples of suitable organosilicon compounds which may be reacted with the cyclic organopolysiloxanes are epoxy-functional silanes of the formula Ze (A)d Si(OR)4_e_d or epoxy-functional siloxanes having the formula : 20 ~ [(A)d - SiO4 d ¦ R' .` in which A is a radical which contains at least one epoxy group and may be represented by the general formula . ~ /0 ; ~x c f; R
:- R" R"
. g .
. :

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10~138~

in which R is a monovalent hydrocarbon radical having from 1 to 18 carbon atoms, Rl is a radical selected from the class consisting of R"Oo 5 and R3SiOo 5 in which R" is hydrogen or R and when the R"(s) are hydrocarbon - radicals, they can be taken together with the vicinal carbon atoms, to represent a cyclic group, e.g. a cyclohexane ring or cylopentane ring which may be unsubstituted or substituted with aIkyl or aryl substituents, R"' may represent a divalent, trivalent-tetravalent radical, e.g. an alkylene r~
cal, an arylene radical having up to 18 carbon atoms or an oxyalkylene, or oxyarylene radical containing C-O-C linkages, X represents hydrogen or a monovalent radical consisting of a single carbon atom or a group of carbon atoms interconnected by a single or multiple bond which contains additional groups, e.g. hydrogen, alkyl, hydroxyl, alkoxy and cyclic hydrocarbons, Z
is a group selected fr~m the class consisting of OR". R or OSiRj where R
and R" are the same as above, a is a nu~ber of from 1 to 20,000, c is a number of from 0 to 3, d is a number of from 1 to 3, e is a number of from O to 2 and when c is equal to 0, then at least one Z must be OR" and g is a nu~ber of from 1 to 3.
; Among the hydrccarbon radicals represented by R are alkyl radicals having from 1 to 18 carbon atoms, e.g., methyl, ethyl, propyl, butyl, octyl, ; 20 dodecyl, octadecyl and the Iike; cycloaLkyl radicals, e.g., cyclopentyl, cyclohexyl, cycloheptyl and the like; mononuclear and binuclear aryl radi-cals, e.g., phenyl, naphthyl and the like; aralkyl radicals, e.g., benzyl, phenylethyl, p~enylpropyl, phenylbutyl and the like; alkaryl radicals, e.g., tolyl, xylyo, ethylphenyl and the like. Radicals represented by R" are alkylene radicals e.g. ethylene, propylene, butylene, pentamethylene, - hexamethylene, octamethylene, dodecylmethylene, hexadecylmethylene and octadecylmethylene; arylene radicals e.g. phenylene, biphenylene and the ; corresponding alkylene and arylene radicals containing an oxygen atom.
Other radicals represented by R" are vinylene, propenylene, butenylene an_ the like.

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.
-10913~3 The epoxy~functional organosilicon compounds represented above may contain monoepoxides and polyepoxides, particularly monoepoxides, diepoxides and triepoxides.
As taught in the Principal Disclosure, examples of suitable organosilicon ccmpounds are silanes or siloxanes e.g. gamma-glycidoxypropyl-triethoxysilane, 4,5-epoxypentyltriethoxysilane, gamma-glycidoxypropyltri-propoxysilane, gamma-glycidoxybutyltriethoxysilane, g~l~l~-glycidoxypropyl-tributoxysilane, gamma-glycidoxypropyltrimethoxysilane, gamma-glycidoxy-he~yltriethoxysilane, gamma-glycidoxyoctyltriethoxysilane, gamma-glycidoxy-hexyltributoxysilane,glycidoxy-o,-phenyltriethoxysilane, 5,6-epoxyhexyl-trimethoxysilane, 5,6-epoxyhexyltributoxysilane, 7,8-epoxyoctyltrimethoxy-silane, 7,8-ep~xyoctyltripropoxysilane, 9,10-epoxydecyltrImethoxysilane, 9,10-epoxydecyltripropoxysilane, beta-3,4-(epoxycyclohexyl-ethyltrimethoxy-silane, beta-3,4-(epoxycyclohe~yl)propyltributoxysilane, 1,3-bis-(3-gly-cidoxypropyl) tetramethoxydisiloxane, and partial hydrolysis products ` thereof.
Other epoxy-functional silanes or siloxanes which ~ay be employed according to the present Supplementary Disclosure are those having the formwla 0~7~

~ -CH2(-CH2)X-Si(OcH3)3~ and ' .

~'. ~ , . ' .
0~ 1 ' .
L CH2 -CH-(cH2-o)x-cH2-~ 2cH-cH2-oc3H6 ( 3 3 p . . .
: E - 5D 20 _ ~091383 where a is the same as the above and x is a number of fram 0 to 20.
The cyclic siloxanes employed in the preparation of the polymers of aspects of this invention as no~ provided by this Supplementary Disclo-sure may be represented by the formula R
I -sio-- R _ z wherein R is the same as akove and z is 3 to 6.
Examples of suitable catalysts for use in the process according to an aspect of the invention now provided by t~e present Supplementary Disclosure are aLkali metal alkoxides e.g. lithium methoxiae, potassiuf~
methoxide, sodium methoxide, and lithium butoxide; alkali met~l alkyls, e.g.
ethyl lithium, ethyl potassium, ethyl sodium, isopropyl lithium, n-butyl lithium, vinyl lithium and the li~e; a alkali aryls, e.g. phenyl lithium, phenyl sodium and the like; alkali metal hydrides, e.g. sodium, potassium and lithium hydride; aLkali metal silanoates, e.g. sodium, potassium and lithium silanoates, and hydroxides, e.g. sodium, potassium lithium and tetramethyl ammonium hydroxides.
Various embodiments of this invention as naw provided by this Supplementary Disclosure are illustrated in.the following examples in which .:. .
- all parts by are ~y weight unless otherwlse specified.
In Example 1 of the Principal Disclosure, it was determined that the resulting product has a viscosity of approximately 45 cs. at 25C and can be represented by the following structural fornwla . . .
? 0 ~ ~ (CH3)2 . CH2-CHCH2 oC3H6Si - L (Si)lO OCH3~ 3 E . -SD2l-.. . . .
.. . ~ . . .
. . . ~
~ . ... ~ , , Exa~ple 7 A reaction vessel containing 222 parts of oct~methylcyclotetra-siloxane, 23.6 parts of gamma-glycidoxypropyltrImethoxysilane and 0.2 part of potassium hydroxide are heated to 145C and m~intained at this tempera-ture for 2.5 hours. The catalyst is neutralized by the a~;tion of 0.2 part of acetic acid and the reaction product filtered. me volatiles are removed at 130C at 2 mm Hg over a period of 4 hours. A clear liquid pr~-duct is recovered. Nuclear magnetic resonance analysis of the product shows the following groups to be present in the indicated mol ratio:

Groups Actual Theoretical / \ ' ' l CH2CH ~H20C3H6Si_ 0.33 0.33 . CH30- 1.0 1.0 ~ -(CH3)2Sjo 10.2 10.0 The resulting product has a viscosity of approximately 55 cs. at J~. 25C and can be represented by the follow mg structural formula 2~
., .

o - 1~~ C H 3 ) 2 CH2-CHCH2 oC3H6si -- L (OSi )10 - CH3~ 3 , .

109i38~
Example 8 The procedure of Ex~mple 7 is repeated except that 24.7 parts of a silane of the forn~la \~
~ -CH2-CH2 5j(.0CH3)3 is substituted for the ga~ma-glycido~ypropyltrimethoxysilane.
.. Analysis shows that the resultant product has the following forn~la . 10 ~ ~ (CH3)2 ~ CH2CH2si l ~ )10 3 J

.
Example 9 The procedure of Example 7.is repeated except th~t 37.6 parts ' of a silane of the formula , '. CH2-I~o .

. CH
. . CH

`, ' /\ 1 ' -CH2-CH-CH20-CH2 CH~CH2 C3H6 Si(CH3)3 is substituted for the gamm2-glycidoxypropyltrImethoxysilane.

E` - SD 23 -.'' ' ' l~9i38;~

: Analysis indicated that the re~ultant product ha~ the following formNla - CH

H 2 C- C H - CH 2 - O - C H 2 - C H - C H 2 C 3H 6 5 ~ [ ( O S i ) 1 o OC H 3]
: 3 , .

. .
. .
., .~
.`:

,.' ~

. .

, ."

Claims

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

1. A process for preparing epoxy-functional polymers which comprises reacting an organosilicon compound of the formula ASi(OR)3 wherein A is a radical containing at least one epoxy group and R is a monovalent hydrocarbon radical having from 1 to 18 carbon atoms with a cyclic organosiloxane selected from the group con-sisting of organocyclotrisiloxanes and organocyclotetrasiloxanes in the presence of a catalytic amount of a lithium compound sel-ected from the group consisting of lithium alkyls, lithium aryls, lithium hydrides, lithium hydroxide and lithium alkoxides.

2. The process of claim 1 wherein the lithium compound is a lithium alkyl.

3. The process of claim 1 wherein the lithium compound is a lithium aryl.

4. The process of claim 1 wherein the lithium compound is a lithium alkoxide.

5. The process of claim 1 wherein the lithium compound is lithium hydride.

6. The process of claim 1 wherein the lithium compound is lithium hydroxide.

7. The process of claim 6 wherein said silane is gamma-glycidoxypropyltrimethoxysilane.

8. The process of claim 1 wherein said cyclic organopolysiloxane has the formula wherein R' is selected from the group consisting of monovalent hydro-carbon radicals having from 1 to 18 carbon atoms and z is 3 or 4.

9. The process of claim 8 wherein the cyclic organosiloxane is hexamethylcyclotrisiloxane.

10. The process of claim 8 wherein the organocyclopolysiloxane is 1,2,3-trimethyl-1,2,3-triphenylcyclotrisiloxane.

11. The process of claim 1 wherein the reaction is conducted in the presence of an aprotic solvent.

12. The process of claim 11 wherein the solvent is present in an amount of from 0.5 to 80 percent by weight based on the weight of the composition.

13. The process of claim 11 wherein the aprotic solvent is ethyl-ene glycol dimethyl ether.

CLAIMS SUPPORTED BY THE SUPPLEMENTARY DISCLOSURE

14. A composition comprising epoxy-functional polysiloxane polymers of the formula in which A is a radical containing at least one epoxy group, R is a monovalent hydrocarbon radical having from 1 to 18 carbon atms, and a is a number of from 1 to 20,000.

15. The composition of claim 14 wherein A is a radical of the formula in which R' is selected from the class consisting of hydrogen and R, and wherein the R'(s) are taken together with the vicinal carbon atoms, may represent substituted and unsubstituted cyclic hydrocarbons, R" is selected from the class consisting of a divalent hydrocarbon radical, a trivalent hydrocarbon radical, a tetravalent hydrocarbon radical, an oxyalkylene radical and oxyarylene radical having C-O-C linkages, X is selected from the class consisting of a single carbon atom or a group of carbon atoms interconnected by a single or multiple bond which contains additional groups selected from the class consisting of hydrogen, alkyl; hydroxyl, alkoxy and cyclic hydrocarbons, and b is a num-ber of from 1 to 3.

16. The composition of claim 14 wherein R is a methyl radical.

17. The composition of claim 14 wherein the epoxy-functional polysiloxane has the formula

18. The composition of claim 14 wherein the epoxy-functional polysiloxane has the formula

19. The composition of claim 14 wherein the epoxy-functional polysiloxane has the formula

20. The composition of claim 15 wherein R' represents an alkyl radical

21. The composition of claim 15 wherein X is hydrogen and the R'(s) together with the vicinal carbon atoms form a cyclic hydrocarbon.

22. The composition of claim 15 wherein R" is an alkylen radical.

23. The composition of claim 15 wherein R" is an oxyalkylene radical having C-O-C linkages.

24. A composition comprising epoxy-functional polysiloxane polymers of the formula where A is a radical containing at least one epoxy group, R
is a monovalent hydrocarbon radical having from 1 to 18 carbon atoms and a is a number from 1 to 20,000.