CA1073323A - Compositions containing thiofunctional polysiloxanes - Google Patents
Compositions containing thiofunctional polysiloxanesInfo
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- CA1073323A CA1073323A CA268,219A CA268219A CA1073323A CA 1073323 A CA1073323 A CA 1073323A CA 268219 A CA268219 A CA 268219A CA 1073323 A CA1073323 A CA 1073323A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
- C08L83/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C33/00—Moulds or cores; Details thereof or accessories therefor
- B29C33/56—Coatings, e.g. enameled or galvanised; Releasing, lubricating or separating agents
- B29C33/60—Releasing, lubricating or separating agents
- B29C33/62—Releasing, lubricating or separating agents based on polymers or oligomers
- B29C33/64—Silicone
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
- C08G77/24—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen halogen-containing groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
- C08G77/28—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen sulfur-containing groups
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Paints Or Removers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Silicon Polymers (AREA)
- Moulds For Moulding Plastics Or The Like (AREA)
- Lubricants (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
Compositions containing particularly recited proportions of certain specifically recited branched or linear organopolysiloxanes and certain specifically recited thiofunctional polysiloxanes having at least one mercaptan group are provided herein. These compositions are effective as corrosion inhibitors, as release agents for metal substrates and as multiple release agents in preparing molded articles. These compositions avoid the disadvantages of the formation of a residue on the metal surface, especially when heated to elevated temperatures.
Compositions containing particularly recited proportions of certain specifically recited branched or linear organopolysiloxanes and certain specifically recited thiofunctional polysiloxanes having at least one mercaptan group are provided herein. These compositions are effective as corrosion inhibitors, as release agents for metal substrates and as multiple release agents in preparing molded articles. These compositions avoid the disadvantages of the formation of a residue on the metal surface, especially when heated to elevated temperatures.
Description
:
iL~73323 having the general formula RfSiO4 f wherein R is selected from the group consisting of a monovalent hydro-carbon radical and a halogenated monovalent hydrocarbon radical each having from 1 to 18 carbon atoms, M is selected from the class consisting of Rl(SR"')y, and R"
SH
~ R", R~ is selected from the group consisting of a substituted and unsub-stituted divalent, trivalent and tetravalent hydrocarbon radical, a hydrocarbon ether, a hydrocarbon thioether, a hydrocarbon ester and a hydrocarbon thioester in which R' is attached to a silicon atom via a silicon-carbon bond, R" is selected from the group consisting of hydrogen and a monovalent hydrocarbon radical, R"' is selected from the group consisting of R" and a radical represented by the formula R""X, wherein X is a radical selected from the group consisting of O O
HC-, OCR, OH and a cyanoalkyl radical, R"" isla divalent hydrocarbon radical free of aliphatic unsaturation having from 1 to 18 carbon atoms, and when M is Rl(SRl'l)y, at least one R"' is hydrogen, f is 0, 1 or 2, g i.s 0, 1 or 2, h is 1, 2 or 3 and y is a number of from 1 to 3.
By another variant of this aspect, the composition contains (1) an organopolysiloxane which is free of aliphatic unsaturation and has from 1.75 to 2.25 organic radicals per silicon atom and (2) a th;o-functional polysiloxane fluid having at least one mercaptan group per molecule, the organopolysiloxane (1) being present in an amount of from 10 to 99.9 percent by weigh~ and the thiofunctional polysiloxane fluid
iL~73323 having the general formula RfSiO4 f wherein R is selected from the group consisting of a monovalent hydro-carbon radical and a halogenated monovalent hydrocarbon radical each having from 1 to 18 carbon atoms, M is selected from the class consisting of Rl(SR"')y, and R"
SH
~ R", R~ is selected from the group consisting of a substituted and unsub-stituted divalent, trivalent and tetravalent hydrocarbon radical, a hydrocarbon ether, a hydrocarbon thioether, a hydrocarbon ester and a hydrocarbon thioester in which R' is attached to a silicon atom via a silicon-carbon bond, R" is selected from the group consisting of hydrogen and a monovalent hydrocarbon radical, R"' is selected from the group consisting of R" and a radical represented by the formula R""X, wherein X is a radical selected from the group consisting of O O
HC-, OCR, OH and a cyanoalkyl radical, R"" isla divalent hydrocarbon radical free of aliphatic unsaturation having from 1 to 18 carbon atoms, and when M is Rl(SRl'l)y, at least one R"' is hydrogen, f is 0, 1 or 2, g i.s 0, 1 or 2, h is 1, 2 or 3 and y is a number of from 1 to 3.
By another variant of this aspect, the composition contains (1) an organopolysiloxane which is free of aliphatic unsaturation and has from 1.75 to 2.25 organic radicals per silicon atom and (2) a th;o-functional polysiloxane fluid having at least one mercaptan group per molecule, the organopolysiloxane (1) being present in an amount of from 10 to 99.9 percent by weigh~ and the thiofunctional polysiloxane fluid
(2) being present in an amount of from 90 to 0.1 percent by weight based on the weight of the organopolysiloxane (1~ and the thiofunctional ~ - 3 -: , r polysiloxane fluid (2), the thiofunctional polysiloxane fluid (2) con-tains siloxane copolymers having from 0.1 to 99~9 mol percent of units of ~he formula Rg Mh~i4_(h+g) and from 99.9 to 0.1 mol percent of at least one other siloxane unit having the general formula RfSiO4 f wherein R is selected from the group consisting of a monovalent hydro-carbon radical and a halogenated monovalent hydrocarbon radicalS each having from 1 to 18 carbon atoms, M is a mercaptan containing radical of the formula R'(SR"') , R' is selected from the group consisting of a substituted and unsubstituted divalent, trivalent and tetravalent hydro-carbon radical, a hydrocarbon ether, a hydrocarbon thioether, a hydro-carbon ester and a hydrocarbon thioester in which R' is attached to a silicon atom via a silicon-carbo~ bond, R"' is selected from the group consisting of hydrogen, a monovalent hydrocarbon radical and a radical represented by the formula R""X, wherein X is a radical selected from the group consisting of ~ O
H -, O R, OH and a cyanoalkyl radical, R"" is a divalent hydrocarbon radical free of aliphatic unsaturation having from 1 to 18 carbon atoms, and at least one R"' is hydrogen, f is 0, 1 or 2 9 g is 0, 1 or 2, h is 1, 2 or 3, and y is a number of from 1 to 3.
By a further variant of this aspect, the composition contains (1) an organopolysiloxane which is free of aliphatic unsaturation and has from 1.75 to 2.25 organic radicals per silicon atom and (2) a thio-functional polysiloxane fluid having at least one mercaptan group per molecule, the organopo~ysiloxane tl.) being present in an amount of from 10 to 99.9 percent by weight and the thiofunctional polysiloxane fluid - 3a-. : : ::,.: ~ :
:~73323 (2) being present in an amount of from 90 to 0.1 percent by weight based on ~he weight of the organopolysiloxane (1) and the thiofunctional polysiloxane fluid (2), the thiofunctional polysiloxane fluid (2) con-tains siloxane copolymers having from 0.1 to 99.9 mol percent of units of the formula Rg MhSi4-(h~g+l) and from 99.9 to 0~1 mol percent of at least one other siloxane unit having the general formula RfSiO4 f wherein R is selected from the group consisting of a monovalent hydro-carbon radical and a halogenated monovalent hydrocarbon radical each having from 1 to 18 carbon atoms, M i9 a mercaptan containing radical of the formula R"
SH
R"
R" is selected from the group consisting of hydrogen and a monovalent hydrocarbon radical, f is 0, 1 or 2, ~ is 0 or 1, h is 1 and the sum of g ~ h is 1 or 2.
By still another variant of this aspect, the composition con-tains (1) an organopolysiloxane which is free of aliphatic unsaturation and has from 1.75 to 2.25 organic radicals per silicon atom and (2) a thiofunctional polysiloxane fluid having at least one mercaptan group per molecule, the organopclysiloxane (1) being present in an amount of from 10 to 99.9 percent by weight and the thiofunctional polysiloxane fluid (2) being present in an amount of from 90 to 0.1 percent by weight based on the weight of the organopolysiloxane (1) and the thiofunctional polysiloxane fluid (2), the thiofunctional polysiloxane :Eluid (2~ is 7 3b -, . ~. , ,'. '' ~ :
.. , .. ~
: ; , ', '' ' ' :
1~733Z3 obtained f~om the reaction of a cyclic trisiloxane of. the formula Ma R~6_a) Si3 3 with a silicon compound in the presence of an acid catalyst having a pKa value below 1, the silicon compound is selected from the class consis-ting of silanes of the formula Rc (M)b~i(OR )3-(b~c) and siloxanes of the formula lo Y ~ sio t -f Sl~-- S~ ~
wherein R i5 selected from the group consisting of a monovalent hydro-carbon radical and a halogenated monovalent hydrocarbon radical, each having from 1 to 18 carbon atoms, M is selected from the class consisting of R'(SR"') , and SH
~. R"
in which R' is selected from the group consisting of a subs-tituted and unsubstituted divalent, trivalent and tetravalent hydrocarbon radical having from 1 to 18 carbon atoms, a hydrocarbon ether, a hydrocarbon thioether, a hydrocarbon ester and a hydrocarbon thioester, in which R' is attached to a silicon atom via a silicon-carbon bond, R" is selected from the group consisting of hydrogen and a monovalent hydrocarbon radical having from 1 to 18 carbon atoms, R"' is selected from the group consist~ng of R" and a radical represented by the formula R""X, wherein X is a radical selected from the group consisting of O O
HC-, O R, and OH and a cyanoalkyl radical, in which R"" is a divalent hydrocarbon " radical free of aliphatic unsaturation having from 1 to 18 carbon atoms, - 3c -. ;
: ` ` .................... . .
: ~ .:, : ':' - :
Y is a radical selected from the class consisting of R3SiOl/2~ and 13-e (R"O) SiOl/2 wherein R and R" are the same as above, and when M is R~(SRI'7)y, at least on R"' is hydrogen, a is a number of from 0 to 6, b is a number of from 0 to 3, c is a number of from O to 2 and the sum of b+c is from 1 to 2, d is a number of from 0 to 2 and when d is 1 or 2 the sum of _+b+m is at least 1 and when d is 1 to 3, m and n are each equal to a number of from 0 to 20,000 and the sum of m~n is at least :L and ~ is a number of from 1 to 3.
By one variation thereof, the thionfunctional polysiloxane is obtained from the reaction of a cyclic trisiloxane of the formula MaR(6-a) S~3O3 with a silicon compound in the presence of an acid catalyst having a pK ~alue below 1, the silicon compound is selected from the class con-sisting of silanes of the formula ~Rc (M)bSi(OR )3-(b~c) and siloxanes of the formula ~ R2 3 ~: R R3 e m wherein R is selected from the group consisting of a monovalent hydro-carbon radical and a halogenated monovalent hydrocarbon radical each having from 1 to 18 carbon atoms, M is selected from the class consisting of R'(SR"') , and R"
~ SH
~ R'l ~ - 3d -'' ' .
: ' , '. ' .. ' -: ' : - ;
733'~3 in which R' is selected from the group consisting of a substituted and unsubstituted divalent, trivalent and tetravalent hydrocarbon radical having from 1 to 18 carbon atoms, a hydrocarbon ether, a hydrocarbon thioether, a hydrocarbon es~er and a hydrocarbon thioester in which R' is attached to a silicon atom via a silicon--carbon bond, R" is selected from the group consisting of hydrogen and a monovalent hydrocarbon radical having from 1 to 18 carbon atoms, R"~ is selected from the group consisting of R" and a radical represented by the formula R"'7X, wherein X is a radical selected ~rom the group consisting of O 0 HC-, OCR, OH and a cyanoalkyl radical, in which R"" is a divalent hydrocarbon radical free of aliphatic unsaturation having from 1 to 18 carbon atoms, Y is a radical selected from the class consisting of R3Si01/2, and l3-e (R")eSil/2 where R and R" are th~ same as above, and when M is R'(SR"')y, at least one R"' is hydrogen, a is a number of from 0 to 6, b is a number of from 0 to 3, c is a number of from 0 to 2 and the sum of b~c is from 1 to 2, d is a number of from 0 to 2 and the sum of a-~b+d is at least 1, e is a number of from 1 to 3, m and n are each equal to a number of from 0 to 999 and the sum of m+n is at least 1 and y is a number of from 1 to 3.
By another variation thereof, the cyclic trisiloxane is represented by the formula M R Si O
a 6-a 3 3 wherein R is selected from the group consisting of a monovalent hydro-carbon radical and a halogenated monovalent hydrocarbon radical each having from 1 to 18 carbon atoms, a is a number of from 0 to 6, M is selected from the class consisting of R'(SR"') , in which at least one R"' is hydrogen, and ~ - 3e -, ,,, "' ', ~: ~;' : :
R"
SH
R~
wherein R~ is selected from the group consisting of substituted and unsubstituted divalent, trivalent and tetravalent hydrocarbon radicals free of aliphatic unsaturation having from 1 to 18 carbon atoms, hydro-carbon ether, hydrocarbon thioether, hydrocarbon ester and hydrocarbon thioester radicals, in which R' is attached to a silicon atom via a silicon-carbon bond, R" is selected from the group consisting of hydrogen and a monovalent hydrocarbon radical having from 1 to 18 carbon atoms, R"' is selected from the group consisting of R" and a radical represented by the formula R""X,wherein X is a radical selected from the group consisting of O O
HC-, OIR, OH and a cyanoalkyl radical, in which R"" is a divalent hydrocarbon radical free of aliphatic unsaturation having from 1 to 18 carbon atoms and y is a number of from 1 to 3.
By a further variation, an organodisiloxane is included in the preparation of the thiofunctional polysiloxane fluid, the organodi-siloxane having the formula 2~ MaR(6-a) si2 wherein R is a monovalent hydrocarbon radical having from 1 to 18 carbon atoms, M i8 selected from the class consisting of R'~SR"') , and R"
SH
\ I R"
whereinR' is selected from the group consisting of a substituted and unsubstituted divalent, trivalent and tetravalent hydrocarbon radical having from 1 to 18 carbon atoms, a hydrocarbon ether, a hydrocarbon thioether, a hydrocarbon ester, and a hydrocarbon thioester, in which R' is attached to a silicon atom via a silicon-carbon bond, R" is selected ~ - 3f -,' ~
;. , ~L~733Z3 from the group consisting of hydrogen and a monovalent hydrocarbon radi-cal having from 1 to 18 carbon atoms, R"' is selected from the group consisting of R" and a radical represented by the formula R""X, wherein X is a radical selected from the group consisting of O O
HC-, O~R, OH and a cyanoalkyl radical, R"" is a divalent hydrocarbon radical free of aliphatic unsaturation having from 1 to 18 carbon atoms9 and when M is R~(SR"~) , at least one R"~ is hydrogen, a is a number of from 0 to 6 and y is a number of from 1 to 3.
By yet another variant, an organodisiloxane is included in the reaction, the organodisiloxane having the formula Ma (6-a) 2 wherein R is selected from the group consisting of a monovalent hydro-carbon radical and a halogenated monovalent hydrocarbon radical each having from 1 to 18 carbon atoms, M is selected from the class consisting of R'(SR"'~ , and R"
/ ~ SH
\ I R"
~O wherein R~ is selected from the group consisting of a substituted and unsubstituted divalent, trivalent and tetravalent.hydrocarbon radical having from 1 to 18 carbon atoms, a hydrocarbon ether, a hydrocarbon thioether, a hydrocarbon ester, and a hydrocarbon thioester in which R' is attached to a silicon atom via a silicon-carbon bond, R" is selected from the group consisting of hy.drogen and a monovalent hydrocar.bon radical having from 1 to 18 carbon atoms, R"l is selected from the group consisting of R" and a radical represented by the formula R""X, wherein X is a radical selected from the group consisting of O O
H -, O R, OH and a cyanoalkyl radical, R"" is a divalent hydrocarbon radical free of - 3g _ :
aliphatic unsaturation having from 1 to 1~ carbon atoms~ and ~hen M is R~(SR"') , at least one R"' is hydrogen, a is a number of from 0 to 6 and y is a number of from 1 to 3.
By another variation, the thiofunctional fluid is prepared in the presence of a hydrocarbon solvent, e.g. heptane.
By another variation, the thiofunctional polysiloxane fluid is prepared at a temperature up to 200C.
By still another variation, the thiofunctional polysiloxane fluid is prepared in the presence of a prot:Lc compound.
By yet another variation, the compositions contain an organic solvent.
By specific variants, the organodisiloxane is hexamethyldi-siloxane; or the disiloxane is di(3-mercaptopropyl)tetramethyldisiloxane;
or the cyclic trisiloxane is hexamethylcyclotrisiloxane; or the silicon compound is a mercaptoalkylhydrocarbonoxysilane; or the silicon com-pound is mercaptopropyltrimethoxysilane; or the organopolysiloxane is a polydimethylsiloxane fluid.
By another aspect of this invention, a method is provided for rendering a metal corrosion resistant which comprises: applying a com-position containing a thiofunctional polysiloxane having at least onemercaptan group per molecule in an amount of from 0.1 to 90 percent by weight and from 99.9 to 10 percent by weight of an organopolysiloxane based on the weight of the thiofunctional polysiloxane and the organo-polysiloxane to a metal surface and thereafter heating the coated sur-face to an elevated temperature.
By specific variants thereof, the composition is one of those described hereabove.
By another aspect, a method is provided for imparting release properties to a metal surface which comprises applying a composition containing a thiofunctional polysiloxane having at least one mercaptan ~ - 3h -.. ~ , " .. ,, 1 , ~ ;' ,' ' ' , ' '' ";
:~733~:3 group per molecule in an amount of from 0.1 to 90 percent by weight and from 99.9 to 10 percent by weight of an organopolysiloxane based on the weight of the thiofunctional polysiloxane and the organopolysiloxane.
By specific variants thereof, the composition is one of those described hereabove.
By another aspect of this invention, an improved method is pFo-vided for obtaining multiple release in preparation of molded articles by applying a moldable material to a mold surface and allowing the resultant material to solidify, the improvement which comprises: apply-ing a release composition to the mold surface, the release composition containing (1) from 10 to 99.9 percent by weight of an organopolysiloxane and (Z) from 90 to 0.1 percent by weight of a thiofunctional polysiloxane having at least one mercaptan group per molecule based on the weight of the organopolysiloxane tl) and the thiofunctional polysiloxane fluid (2).
By specific variants thereof, the composition is one of those described hereabove.
By a variant thereof, the moldable material is the reaction product of an organic polyisocyanate and an organic compound having at least two groups bearing Zerewitinoff active hydrogen atoms.
Organopolysiloxanes employed in the compositions of various aspects of this invention may be represented by the general formula I R
.. -sio-L I x wherein the R(s~, which may be-the same or different, represent mono-valent hydrocarbon radicals or halogenated monovalent hydrocarbon radi-cals having from 1 to 18 carbon atoms and x is a number greater than 8.
Radicals represented by R above are alkyl radicals, e.g.
methyl, ethyl, propyl, butyl, octyl, dodecyl and octadecyl; aryl radicals, e.g., phenyl, diphenyl and naphthyl radicals; cycloalkyl . ~
i ~ - 3i -'' ' ' ,: ::
::
:, ,,, ~L~73323 radicals, e.g., cyclobutyl, cyclopentyl and cyclohexyl; alkaryl radi-cals, e.g., tolyl, xylyl, ethylphenyl; aralkyl radicals, e.g., ben~yl, ~<-phenylethyl, ~-phenylethyl and o<-phenylbutyl; and the halo sub-stituted radicals enumerated above.
The organopolysiloxanes may be any linear or branched chained compound, preferably a fluid, having an average of from 1.75 to 2.25 organic radicals per silicon atom. Generally, it is preferred that the organopolysiloxane be free of terminal-hydroxyl groups; however, a small number of terminal-hydroxyl groups will not materially affect the release properties of the composition. The organopolysiloxane may have a minor amount of molecules having only one hydroxyl group or there may be a small number of molecules carrying an excess of two hydroxyl groups;
however, as mentioned
H -, O R, OH and a cyanoalkyl radical, R"" is a divalent hydrocarbon radical free of aliphatic unsaturation having from 1 to 18 carbon atoms, and at least one R"' is hydrogen, f is 0, 1 or 2 9 g is 0, 1 or 2, h is 1, 2 or 3, and y is a number of from 1 to 3.
By a further variant of this aspect, the composition contains (1) an organopolysiloxane which is free of aliphatic unsaturation and has from 1.75 to 2.25 organic radicals per silicon atom and (2) a thio-functional polysiloxane fluid having at least one mercaptan group per molecule, the organopo~ysiloxane tl.) being present in an amount of from 10 to 99.9 percent by weight and the thiofunctional polysiloxane fluid - 3a-. : : ::,.: ~ :
:~73323 (2) being present in an amount of from 90 to 0.1 percent by weight based on ~he weight of the organopolysiloxane (1) and the thiofunctional polysiloxane fluid (2), the thiofunctional polysiloxane fluid (2) con-tains siloxane copolymers having from 0.1 to 99.9 mol percent of units of the formula Rg MhSi4-(h~g+l) and from 99.9 to 0~1 mol percent of at least one other siloxane unit having the general formula RfSiO4 f wherein R is selected from the group consisting of a monovalent hydro-carbon radical and a halogenated monovalent hydrocarbon radical each having from 1 to 18 carbon atoms, M i9 a mercaptan containing radical of the formula R"
SH
R"
R" is selected from the group consisting of hydrogen and a monovalent hydrocarbon radical, f is 0, 1 or 2, ~ is 0 or 1, h is 1 and the sum of g ~ h is 1 or 2.
By still another variant of this aspect, the composition con-tains (1) an organopolysiloxane which is free of aliphatic unsaturation and has from 1.75 to 2.25 organic radicals per silicon atom and (2) a thiofunctional polysiloxane fluid having at least one mercaptan group per molecule, the organopclysiloxane (1) being present in an amount of from 10 to 99.9 percent by weight and the thiofunctional polysiloxane fluid (2) being present in an amount of from 90 to 0.1 percent by weight based on the weight of the organopolysiloxane (1) and the thiofunctional polysiloxane fluid (2), the thiofunctional polysiloxane :Eluid (2~ is 7 3b -, . ~. , ,'. '' ~ :
.. , .. ~
: ; , ', '' ' ' :
1~733Z3 obtained f~om the reaction of a cyclic trisiloxane of. the formula Ma R~6_a) Si3 3 with a silicon compound in the presence of an acid catalyst having a pKa value below 1, the silicon compound is selected from the class consis-ting of silanes of the formula Rc (M)b~i(OR )3-(b~c) and siloxanes of the formula lo Y ~ sio t -f Sl~-- S~ ~
wherein R i5 selected from the group consisting of a monovalent hydro-carbon radical and a halogenated monovalent hydrocarbon radical, each having from 1 to 18 carbon atoms, M is selected from the class consisting of R'(SR"') , and SH
~. R"
in which R' is selected from the group consisting of a subs-tituted and unsubstituted divalent, trivalent and tetravalent hydrocarbon radical having from 1 to 18 carbon atoms, a hydrocarbon ether, a hydrocarbon thioether, a hydrocarbon ester and a hydrocarbon thioester, in which R' is attached to a silicon atom via a silicon-carbon bond, R" is selected from the group consisting of hydrogen and a monovalent hydrocarbon radical having from 1 to 18 carbon atoms, R"' is selected from the group consist~ng of R" and a radical represented by the formula R""X, wherein X is a radical selected from the group consisting of O O
HC-, O R, and OH and a cyanoalkyl radical, in which R"" is a divalent hydrocarbon " radical free of aliphatic unsaturation having from 1 to 18 carbon atoms, - 3c -. ;
: ` ` .................... . .
: ~ .:, : ':' - :
Y is a radical selected from the class consisting of R3SiOl/2~ and 13-e (R"O) SiOl/2 wherein R and R" are the same as above, and when M is R~(SRI'7)y, at least on R"' is hydrogen, a is a number of from 0 to 6, b is a number of from 0 to 3, c is a number of from O to 2 and the sum of b+c is from 1 to 2, d is a number of from 0 to 2 and when d is 1 or 2 the sum of _+b+m is at least 1 and when d is 1 to 3, m and n are each equal to a number of from 0 to 20,000 and the sum of m~n is at least :L and ~ is a number of from 1 to 3.
By one variation thereof, the thionfunctional polysiloxane is obtained from the reaction of a cyclic trisiloxane of the formula MaR(6-a) S~3O3 with a silicon compound in the presence of an acid catalyst having a pK ~alue below 1, the silicon compound is selected from the class con-sisting of silanes of the formula ~Rc (M)bSi(OR )3-(b~c) and siloxanes of the formula ~ R2 3 ~: R R3 e m wherein R is selected from the group consisting of a monovalent hydro-carbon radical and a halogenated monovalent hydrocarbon radical each having from 1 to 18 carbon atoms, M is selected from the class consisting of R'(SR"') , and R"
~ SH
~ R'l ~ - 3d -'' ' .
: ' , '. ' .. ' -: ' : - ;
733'~3 in which R' is selected from the group consisting of a substituted and unsubstituted divalent, trivalent and tetravalent hydrocarbon radical having from 1 to 18 carbon atoms, a hydrocarbon ether, a hydrocarbon thioether, a hydrocarbon es~er and a hydrocarbon thioester in which R' is attached to a silicon atom via a silicon--carbon bond, R" is selected from the group consisting of hydrogen and a monovalent hydrocarbon radical having from 1 to 18 carbon atoms, R"~ is selected from the group consisting of R" and a radical represented by the formula R"'7X, wherein X is a radical selected ~rom the group consisting of O 0 HC-, OCR, OH and a cyanoalkyl radical, in which R"" is a divalent hydrocarbon radical free of aliphatic unsaturation having from 1 to 18 carbon atoms, Y is a radical selected from the class consisting of R3Si01/2, and l3-e (R")eSil/2 where R and R" are th~ same as above, and when M is R'(SR"')y, at least one R"' is hydrogen, a is a number of from 0 to 6, b is a number of from 0 to 3, c is a number of from 0 to 2 and the sum of b~c is from 1 to 2, d is a number of from 0 to 2 and the sum of a-~b+d is at least 1, e is a number of from 1 to 3, m and n are each equal to a number of from 0 to 999 and the sum of m+n is at least 1 and y is a number of from 1 to 3.
By another variation thereof, the cyclic trisiloxane is represented by the formula M R Si O
a 6-a 3 3 wherein R is selected from the group consisting of a monovalent hydro-carbon radical and a halogenated monovalent hydrocarbon radical each having from 1 to 18 carbon atoms, a is a number of from 0 to 6, M is selected from the class consisting of R'(SR"') , in which at least one R"' is hydrogen, and ~ - 3e -, ,,, "' ', ~: ~;' : :
R"
SH
R~
wherein R~ is selected from the group consisting of substituted and unsubstituted divalent, trivalent and tetravalent hydrocarbon radicals free of aliphatic unsaturation having from 1 to 18 carbon atoms, hydro-carbon ether, hydrocarbon thioether, hydrocarbon ester and hydrocarbon thioester radicals, in which R' is attached to a silicon atom via a silicon-carbon bond, R" is selected from the group consisting of hydrogen and a monovalent hydrocarbon radical having from 1 to 18 carbon atoms, R"' is selected from the group consisting of R" and a radical represented by the formula R""X,wherein X is a radical selected from the group consisting of O O
HC-, OIR, OH and a cyanoalkyl radical, in which R"" is a divalent hydrocarbon radical free of aliphatic unsaturation having from 1 to 18 carbon atoms and y is a number of from 1 to 3.
By a further variation, an organodisiloxane is included in the preparation of the thiofunctional polysiloxane fluid, the organodi-siloxane having the formula 2~ MaR(6-a) si2 wherein R is a monovalent hydrocarbon radical having from 1 to 18 carbon atoms, M i8 selected from the class consisting of R'~SR"') , and R"
SH
\ I R"
whereinR' is selected from the group consisting of a substituted and unsubstituted divalent, trivalent and tetravalent hydrocarbon radical having from 1 to 18 carbon atoms, a hydrocarbon ether, a hydrocarbon thioether, a hydrocarbon ester, and a hydrocarbon thioester, in which R' is attached to a silicon atom via a silicon-carbon bond, R" is selected ~ - 3f -,' ~
;. , ~L~733Z3 from the group consisting of hydrogen and a monovalent hydrocarbon radi-cal having from 1 to 18 carbon atoms, R"' is selected from the group consisting of R" and a radical represented by the formula R""X, wherein X is a radical selected from the group consisting of O O
HC-, O~R, OH and a cyanoalkyl radical, R"" is a divalent hydrocarbon radical free of aliphatic unsaturation having from 1 to 18 carbon atoms9 and when M is R~(SR"~) , at least one R"~ is hydrogen, a is a number of from 0 to 6 and y is a number of from 1 to 3.
By yet another variant, an organodisiloxane is included in the reaction, the organodisiloxane having the formula Ma (6-a) 2 wherein R is selected from the group consisting of a monovalent hydro-carbon radical and a halogenated monovalent hydrocarbon radical each having from 1 to 18 carbon atoms, M is selected from the class consisting of R'(SR"'~ , and R"
/ ~ SH
\ I R"
~O wherein R~ is selected from the group consisting of a substituted and unsubstituted divalent, trivalent and tetravalent.hydrocarbon radical having from 1 to 18 carbon atoms, a hydrocarbon ether, a hydrocarbon thioether, a hydrocarbon ester, and a hydrocarbon thioester in which R' is attached to a silicon atom via a silicon-carbon bond, R" is selected from the group consisting of hy.drogen and a monovalent hydrocar.bon radical having from 1 to 18 carbon atoms, R"l is selected from the group consisting of R" and a radical represented by the formula R""X, wherein X is a radical selected from the group consisting of O O
H -, O R, OH and a cyanoalkyl radical, R"" is a divalent hydrocarbon radical free of - 3g _ :
aliphatic unsaturation having from 1 to 1~ carbon atoms~ and ~hen M is R~(SR"') , at least one R"' is hydrogen, a is a number of from 0 to 6 and y is a number of from 1 to 3.
By another variation, the thiofunctional fluid is prepared in the presence of a hydrocarbon solvent, e.g. heptane.
By another variation, the thiofunctional polysiloxane fluid is prepared at a temperature up to 200C.
By still another variation, the thiofunctional polysiloxane fluid is prepared in the presence of a prot:Lc compound.
By yet another variation, the compositions contain an organic solvent.
By specific variants, the organodisiloxane is hexamethyldi-siloxane; or the disiloxane is di(3-mercaptopropyl)tetramethyldisiloxane;
or the cyclic trisiloxane is hexamethylcyclotrisiloxane; or the silicon compound is a mercaptoalkylhydrocarbonoxysilane; or the silicon com-pound is mercaptopropyltrimethoxysilane; or the organopolysiloxane is a polydimethylsiloxane fluid.
By another aspect of this invention, a method is provided for rendering a metal corrosion resistant which comprises: applying a com-position containing a thiofunctional polysiloxane having at least onemercaptan group per molecule in an amount of from 0.1 to 90 percent by weight and from 99.9 to 10 percent by weight of an organopolysiloxane based on the weight of the thiofunctional polysiloxane and the organo-polysiloxane to a metal surface and thereafter heating the coated sur-face to an elevated temperature.
By specific variants thereof, the composition is one of those described hereabove.
By another aspect, a method is provided for imparting release properties to a metal surface which comprises applying a composition containing a thiofunctional polysiloxane having at least one mercaptan ~ - 3h -.. ~ , " .. ,, 1 , ~ ;' ,' ' ' , ' '' ";
:~733~:3 group per molecule in an amount of from 0.1 to 90 percent by weight and from 99.9 to 10 percent by weight of an organopolysiloxane based on the weight of the thiofunctional polysiloxane and the organopolysiloxane.
By specific variants thereof, the composition is one of those described hereabove.
By another aspect of this invention, an improved method is pFo-vided for obtaining multiple release in preparation of molded articles by applying a moldable material to a mold surface and allowing the resultant material to solidify, the improvement which comprises: apply-ing a release composition to the mold surface, the release composition containing (1) from 10 to 99.9 percent by weight of an organopolysiloxane and (Z) from 90 to 0.1 percent by weight of a thiofunctional polysiloxane having at least one mercaptan group per molecule based on the weight of the organopolysiloxane tl) and the thiofunctional polysiloxane fluid (2).
By specific variants thereof, the composition is one of those described hereabove.
By a variant thereof, the moldable material is the reaction product of an organic polyisocyanate and an organic compound having at least two groups bearing Zerewitinoff active hydrogen atoms.
Organopolysiloxanes employed in the compositions of various aspects of this invention may be represented by the general formula I R
.. -sio-L I x wherein the R(s~, which may be-the same or different, represent mono-valent hydrocarbon radicals or halogenated monovalent hydrocarbon radi-cals having from 1 to 18 carbon atoms and x is a number greater than 8.
Radicals represented by R above are alkyl radicals, e.g.
methyl, ethyl, propyl, butyl, octyl, dodecyl and octadecyl; aryl radicals, e.g., phenyl, diphenyl and naphthyl radicals; cycloalkyl . ~
i ~ - 3i -'' ' ' ,: ::
::
:, ,,, ~L~73323 radicals, e.g., cyclobutyl, cyclopentyl and cyclohexyl; alkaryl radi-cals, e.g., tolyl, xylyl, ethylphenyl; aralkyl radicals, e.g., ben~yl, ~<-phenylethyl, ~-phenylethyl and o<-phenylbutyl; and the halo sub-stituted radicals enumerated above.
The organopolysiloxanes may be any linear or branched chained compound, preferably a fluid, having an average of from 1.75 to 2.25 organic radicals per silicon atom. Generally, it is preferred that the organopolysiloxane be free of terminal-hydroxyl groups; however, a small number of terminal-hydroxyl groups will not materially affect the release properties of the composition. The organopolysiloxane may have a minor amount of molecules having only one hydroxyl group or there may be a small number of molecules carrying an excess of two hydroxyl groups;
however, as mentioned
- 3~ -, il l ~(~733Z3 :
previously, it is preferred that the organopolysiloxane be substan-tially free of hydroxyl groups. It is preferred that the poly-¦siloxanes have a viscosity of between 5 a~d 1,000,000 cs., ¦and more preferably between 50 cs. and 300,000 cs. at 25C.
iAlso, it is possible to combine high and low viscosity fluids to ¦
. form a fluid having the desired viscosity. High molecular ~Yeight gums.may also be employed; however,.it is preferred that these gums !:
. be dissolved in ~n organic solYent before they are combined with : . the thiofunctional polysiloxanes.
1~ The thiofunctional polysiloxanes employed in the composi-tion of aspects of this invention may be prepared by reacting a disiloxane : and/or a hydroxy or hydrocarbonoxy containing silane or siloxane with a cyclic trisiloxane in the presence of an acid catalyst in which at least one of the above organosilicon compounds contain a mercaptan group. ii l Disiloxanes which may be used in the compositions of aspects .
I ¦ of this invention may be represented by th~ for~lla .
(~)6-a I (M)aSi20 llwhlle the cyclic siloxanes are represented by the formula il (R~6-a.
(M)asi3o3 herein R, which may be the sa~e or different, represents a mono- ¦
valent hydrocarbon radical or a halogenated monovalent hydrocarbon radical having up to 18 carbon atoms, M is a group represented by ¦Ithe for ulae R'(SR"')y,in which at least one R"' is hydrogen, and SH
_4_ ,,. ' , ~, l l0733za la is a number of from 0 to 6 and y is a number of from 1 to 3.
¦ Suitable examples of organosilicon compounds which may be i . . Ireacted with the disiloxanes and/or cyclic trisiloxanes are silanes 1f the general formula .
I Ic .
I . ~M~bSi- (OR")3_ (b~c) -.' ' I . '.
or siloxanes o~ the general formula . - .;.
¦ . R2-d R R3-e l Y ~ Md ~ SiO ~ Si(0 ")e ¦~n which R is a.monovalent hydrocarbon radical or a halogenated ¦hydrocarbon radical having from 1 to 18 carbon atoms, M is a group represented by the formula R'(SR"')y,wherein at least one R"' is . !!hydrogen,and - - .
~15 . R~ . .
:~ ~ SH .
. , .
R' is substituted or unsubstituted divalent, trivalent or tetra-. Ivalent hydrocarbon radicals free of aliphatic unsat~rat;on ha~ing ¦~rom 1 to 18 carbon atoms, hydrocarbon ether9 hydrocarbon thioether, hydrocarbon ester and hydrocarbon thioester radicals in which R' is ~attached to the silicon atom via a silicon carbon bond, R" is hydrogen or a monovalent hydrocarbon radical having ~rom 1 to 18 ¦ carbon atoms, R"' may be the same as R" or a radical represented by llthe for ula R""X, wherein X is Il HC-, ¦! 5_ .
1~ .
~733Z3 . -OOCR, OH or a cyanoalky1 radical, wherein R"" is a divalent hydro-jl carbon radical free of aliphatic unsaturation having from 1 to lE
carbon atoms, Y is a radical of the formula R3SiOl/2, and .
~ . I3-e . . :
(R~)esiol/2 Iwhere R and R" are the sa~e as above, b is a number of from O to 3, . Ic is.a number of from O to 2 and the sum of b~c is from.l to 2, d 1.
. is a number of from O to 2, e is a number of from 1 to 3? m and n !ar~ each equal to a number of from O to 999 and the sum of m~n is ¦ i.
at least 1. . .
. Examples of suitable monovalent hydrocarbon radicals represented by R ~re alkyl radicals, e. -g., . methyl, ethyl, propyl, I
; ¦Ibutyl, pentyl, hexyl, octyl, decyl, octadecyl; aryl radicals, e. g., I
¦I phenyl, diphenyl and naphthyl; alkaryl radicals, e.. g., tolyl, .15 lIxylyl and ethylphenyl; aralkyl radicals, -e~ g., benzyl, c~-phenyl- I
!ethyl,.~-phenylethyl, ~ -phenylbutyl and cycloalkyl radicals, e. g., i I~ cyclobutyl, cyclopentyl and cyclohexyl radicals; halogenated ¦hydrocarbon radicals, e. g.,. chloromethyl, bro~oethyl, fluoroethyl,.
¦tetrafluoroethyl., trifluorotolyl, hexafluoroxylyl and the like. ¦
~ Examples of suitable divalent hydrocarbon radicals r~pre-sented.by R' and R"" are ethylene, trimethylene, tetra~ethylene, ¦Ihexamethylene, octamethylene and the like. Suitable examples o~
trivalent and tetravalent hydrocarbon radicals are represer,ted by ¦the for~ulae =CHCH2-, =CHCH2CH2-~ =C~tCH2)3-, =CH~CH2)4-, ~=CH(CH2)-17~ =CCH2-~ =C(cH2)2-~ -CCH~-, --C(CH2)2- 9 -C~CH2~3-C~3 C2H5 j -C(CH2)17-, --C~HCH2-, -C~H(CH2)2-CH3 C2Hs .¦
jand the like. .
-6~
0 ~ ;3 Z ~
Suitable examples of monovalent hydrocarbon radicals ¦ represented by R" are alkyl radicals, e. g., methyl, ethyl, propyl, ! butyl, pentylj hexyl, octyl, decyl, octadecyl; aryl radicals, e- 8-, ¦ phenyl, diphenyl and naphthyl; alkaryl radicals, e. g., tolyl, ~ .. -1 xylyl and ethylphenyl; ara~kyl radicals, e. g., benzyl,c~ -phenyl-; . ¦ethyl, ~g-phenylethyl, ~ -phenylbutyl and cycloalkyl radicals, e. gO~
¦ cyclobutyl, cyclopentyl and cyc10hexyl radicals. . :
¦ Suitable examples of R'(SR"')y groups include -CH2SH, ¦-C2H4SH C3H6SH (HSCH2)2CHCH2CH2- (HSCH2C~2)(HSCH2)CH(CH2)4-(HSCH2CH2)3CCH2CH2- ~ (HSC1~2CH2) (HscH2)cHcH(cH2sH)c~l2cH2cH2-, ,I l~s(cH2)5cH(cH2cH2sH)cH2cH2cH(cH2cH3)-, (HSCH2CH2)2CHCH2CH2-, .
~ (Hsc~l2)2c~scH2cH~cH2-, ,(HSCH2)2(C2~15)CCH2SCH2CH2CH3-~
¦ (Hsc~l2)3ccH2scH2cH2cH2-~ (HscH2)(tisc~i2cl~2cH2cH2)~s~2 ~ 2 . ¦ (HSC~2CH2)2CHCH2SCH2CH2CH2-, (HSCH2)2(C2H5)CCH2S~H2CH2S(CH2)3- ' 15~HSCH2)3CCH2S(CH2)3s(cH2)3-~ . . .
, S ' .' '. .
(~ISCH2 ) 3CHCH3CH2CSCH2CH2CH2 , .
S . ' ' . ~:, (HSCH2)3~C~12Csc~l2cH2cH2- ' ~0 ' . S . .
. ~HscH2)2(c~H5)cc~2sccH2cl~2cH2-~ .; . .
, I , ' ,, .
¦(Hs&H2)2(c2H5)ccH2scH2cH(cH3)cocH2cH2cH2-, .
I O .
25 ¦(HSCH2)3CCH2SCH2CH(CH3)COCH2CH2CH2- and the like. ¦
Hydroxy and hydrocarbonoxy containing silane; which may be en)ployed are silanes, e. g., 3-mercaptopropyltrimethoxysilane, 2-mercaptoethyltriethoxysilane, w-mercaptodecyltriethoxy-ilane, 2-_7 ., I ~ ' , .' l ~733Z3 mercaptohexyltripropoxysilane, w-mercaptoamyltriethoxysilane, 2-¦(triethoxysilyl)ethyl butyl thioether, 3-(triethoxysilyl)propyl ¦ butyl thioether, 4-~triethoxysilyl)butyl methyl thioether, 2-(methyldiethoxysilyl)ethyl methyl thioether, 2-(methyldiethoxy-silyl)ethyl phenyl thioether, 2-(methyldiethoxysilyl)ethyl dodecyl thioether, 6-(trimethoxysilyl)hexyl ethyl thioether, methyltri- ;
ethoxysilane~. dimethyldiethoxysilane, trimethylethoxysilane, imethylsllane diol, diphenylsilane diol and the like.
The corresponding siloxanes or copolymers thereof which contain at least one or more alkoxy or hydroxy groups may also be employed. Sui.table.examples o~ these polysiloxanes are monoethoxy endblocked beta-mercaptoethyl propylpolysiloxane or methyldiethoxy silyl endbloc~ed beta-mercaptobutyl methylpolysiloxane, monohydroxy endblocked beta-mercaptoethyl ~ethylpolysil`oxane, dihydroxy end-,15 blocked dimethylpolysiloxane,diethoxy endblocked dimethylpoly- ¦
siloxane and the like.
. Other hydroxy and/or hydroca.rbonoxy si~icon.compounds which may be. employed as one of the initial reactants ~ith theI ~;
disiloxane and/or cyclic trisiloxane are the silacyclopentane thiol ~:
jlcompounds disclosed in U.S. Patent 3,655,713 to Le Grow.
¦ Examples of suitable disiloxanes are hexamethyldisiloxane, ¦ hexaethyldisiloxane, hexapropyldisiloxane, hexaoctyldisiloxane, di- .
~3-mercaptopropyl)tetramethyldisiloxane and the li~e. EY~amples of l~suitable cyclic silox~anes are hexamethylcyclotrisiloxa,.e, hexa~ hyl-lltrisiloxane, hexaphenyltrisiloxane, hexabutyltrisiloxane, hexaoctyl-~trisilox2ne, 1,2,3-trim2thyl 1,2,3-triphenylcyclotrisiloxane and tnP-like. ' .
j Catalysts ~Ihich may be employed in eEfecting the reartion -8- :
I
I ~ . . ..
1(~73323 between a disiloxane and/or a hydroxy and/or hydrocarbonoxy containing silane or siloxane and a cyclic trisiloxane in which at least one of the reactants contains a mercaptan group are acid clays and organic and inorganic acids having a pK value less than 1.0 and more preferably below 0.7 in aqueous solutions. Suitable acid catalyst which may be employed are benzosulfonic acid, para-toluene-sulfonic acid, sulfuric acid, sul-furous acid, nitric acid, perchloric acid, hydrochloric acid and acid clays~ e.g. those known by the Trade Marks of Filtrol No. 13 and No. 24 (available from Filtrol Corporation).
Although the amount of catalyst is not critical, it is pre-ferred that from 0.003 percent up to 10 percent by weight of catalyst based on the total weight of the reactants, i.e., the silicon containing compounds used in the preparation of thè thionfunctional polysiloxanes be employed. Greater amounts of catalyst may be used; however, it is the intent of aspects of this invention to provide a catalyst system which does not alter the functionality of the resultant composition.
Generally, it is desirable to remove or destroy the catalysts after the reaction is complete because their presence will adversely affect the properties of the resulting composition. The catalysts may be removed, for example, by washing with water or they ma~ be destroyed by neutralizing with basic reagents. In addition, certain catalyst, e.g., acid clays, may be removed by filtering the reaction mixture.
The reactions may be conducted at any temperature ranging from 25C. up to 200C. over a period of time ranging from 0.5 hour up to several days and, if desired, in the presence of a hydrocarbon solven~.
Under certain condltions, for example, when an anhydrous catalyst is employed, a catalytic amount of a ~_ 9 _ .:
. ! , .' . .
protic compound is required to effect the reaction. The term protic compound refers to compounds having a reacti~e hydrogen 9 e. g., ¦¦alcohols, e.g., methanol, ethanol, propanol, butanol and water. The ¦lamount of protic compound is not cri~ical ancl may range ~I from O.OOOl to 1O percent based on the total weight of the silicon containing reactants.
- The reaction may be conducted at atmospheric, subatmos-pheric or superatmospheric pressure in the absence of a solvent;
IhoweYer, ~hen a solvent is employed~ it may be employed in an amount- ~;
¦of from '.1 to 50 percent by weight based on tne sllicon con-¦taining reactants. Examples of suitable hydrocarbon solvents are ¦
~heptane, benzene, toluene, xylene and the like. It is, however, pre~erred that the reaction be conducted in an inert atmosphere.
I Other thiofunctional polysiloxanes which may be employed I ;
¦in the release composition of aspects of this invention are siloxane copolymers :, :
Icontaining from O.l to 99.9 mole percent o~ units of the formula I , . , MhSiO~ .
and from 99.9 to O.l mole percen~ o~ at least one oth2r siloxan~
unit having the general formula : j RfSiO4_~
¦¦in which R and M are the same as above, ~ is O, l or 2, 9 is ~ ¦
¦¦1 or 2 and h is 1 to 2. These copolymers may also contain R"O and ¦¦R3SjO units in which R and R" are the same as above.
These thiofunctional polysiloxanes can be prepared by ¦reacting hydroxyl containing polysiloxanes with silanes containing 11 ~ ~
! -lo- -..... ~ ... . ... .
mercaptan groups or by the cohydrolysis of chloroalkylchlorosilanes, dialkyldichlorosilanes and trimethylchlorosilanes and thereafter reacting r the chloroalkyl groups with sulfur containing compounds to form poly-siloxanes having mercaptan functionality. Thiofunctional polysiloxanes, e.g., those described in United States Patent No. 3,346,~05 oo Viventi in which 4 -chloroalkyl containing polyciloxanes are reacted with sodium sulfohydride in the presence of dimethylformamide may be employed in the compositions of other aspects of this invention. Other thiofunctional polysiloxanes which may be employed in the compositions of aspec~s of this invention are those prepared in accordance with United States Patent No. 2,960,492 to Morton and No. 3,388,144 to Musolf et al.
The compositions of aspects of this invention can contain from 0.1 percent to 90 percent by weight of thiofunctional polysiloxanes and from 10 percent to 99.9 percent by weight of the organopolysiloxanes.
It is preferred that the composition contain from 1.0 to 30 percent by weight of the thiofunctional polysiloxanes and from 70 percent to 99 per-cent by weight of the organopolysiloxanes based on the weight of the thiofunctional polysiloxanes and the organopolysiloxanes. ~;
Although it is not essential, the composition of aspects of this invention may be diluted with organic solvents to form a solution contain-ing from 0.1 percent to 99 percent and more preferably from 1.0 to 20 percent by weight based on the weight of the composition, i.e., solvent and the siloxanes. Suitable examples of organic solvents are aliphatic hydrocarbons~ e.g., hexane, heptane, octane; aromatic hydrocarbons, e.g., benzene, toluene, xylene, ethylbenzene, naphtha; halogenated hydrocarbons, e.g., methylene chloride, perchloroethylene, trichloroethylene~ carbon tetrachloride, ethers and ~3323 polyethers, e.g. diethyl ether3 dimethyl ether, dibutyl ether, diethylene glycol dimethyl ether', diethylene glycol diethyl ether and the like.
Preferably the'solvent employed in the compositions of aspects of this invention is methylene chloride or perchloroethylene.
Metals and alloys which may be treated with the composition of aspects of this invention are those below and including magnesium in the electromotive series. The metals and alloys include aluminum~ brass, bronze, copper, chromium, iron, magnesium, nickel, lead, silver, silver-plate, sterling silver', tin, beryllium, bronze and zinc.
1~ Any method kno~n in the art may be employed to apply the com-positions of aspects of this invention to a metal surface as long as it results in the deposition of a continuous film. The composition may be applied to the metal surface by dipping, spraying, wiping or brushing.
The coated surface may be used immediately or may be heated to an elevated temperature such as, for example, from 100 to 300C. The heating step accelerates the rate of reaction of the release coating with the metal surface, thereby improving the passivating effect of the coating in certain applications.
The thickness of the coating applied to the metal surface is not critical and may vary from a very thin film to a relatively heavy coat such as those in excess of Ool inch. A coating thickness ranging from 0.01 to Q.10 inch is preferred, although from an economic point of view, a thin film having a thicknesæ of only a few Angstrom units can be employed. Generally, the thickness of the coating can be regulated by the mode of application.
The compositions of aspects of this invention may be applied to metal substrates which are used for molding thermal plastic and thermo-se-tting materials, e.g., polyurethanes, polyethylene, epoxy resins and the like.
Polyurethanes which are well known in the art are prepared by reacting an organic compound having at least two active hydrogen atoms as determined by the Zerewitinoff method with a polyisocya-nate. Other reactants, e.g, chain extending agents and gas-generating materials may also be employed, depending on -the parti-cular polyurethane article desired. For example, in the formation of a cellar material, a gas-generating material, e.g., water, is generally incorporated in the composition.
Suitable examples of polyisocyanates are diisocyanates, e.g., alkylene diisocyanates, e.g, hexamethylene diisocyanate and decamethylenediisocyana-te, and arylene diisocyanates, e.g., phenyl-ene diisocyanates, toluene diisocyanates and mixtures thereo~.
Compounds having two or more active hydrogen atoms as determined by the Zerewitinoff method are polyalkylene polyols, e.g., polyesters, polyethers, alkylene glycols, polymercaptans, polyamines and the like.
The composition of aspects of this invention may be used as a release agent for molding epoxy resins. ~`hese compounds have an oxirane epoxy equivalency greater than one, that is, compounds having an average of more than one oxirane epoxy group, e.g., --C -- C--O
per molecule. The epoxy containing compounds in which the oxygen of -the epoxy group is attached to vicinal carbon atoms, can be saturated or unsaturated, aliphatic, cycloalipha-tic, or hetero-cyclic, and can be substituted with substituents, e.g,, halogen atoms, alkyl groups, ether groups and the ]ike.
Examples of suitable polyepoxides are the polyglycidyl ethers of polyhydric phenols, polyglycidyl ethers of the bis-(hydroxyphenyl)alkanes, polyglycidyl ethers of` polyhydric alcohols, `
polyglycidyl esters of polycarboxylic acids, polyglycidyl deriva-' tives of aromatic amines and aminophenols.
These polyepoxides are reacted with curing agents to form ;
hard insoluble infusible products. The curing agents for the products include ma-terials which are preferably acidic or basic, e.g., poly basic acids and their anhydrides, acids which contain sulfur, nitrogen, phosphrous or halogens and bases, e.g., amine-con-taining compounds.
0-ther curing agents which may be used in curing -the epoxy ~`
resins are boron trifluoride and complexes of boron trifluoride with amines, ethers, phenols and the like, ~riedel-Crafts metal salts, e.g., aluminum chloride, zinc chloride, and o-ther salts, e.g., zinc fluoborate, magnesium perchlorate and zinc fluosilicate;
inorganic acids and partial esters, e.g., phosphoric acid and partial esters thereof including n-butyl orthothiophosphate, diethyl orthophosphate and hexaethyltetraphosphate and polyamides containing active and/or carboxyl groups.
The thermosetting or thermal plastic materials are applied to a mold whose surface has been coated with the release composition af aspects of this invention and the plastic materials are cured at temperatures ranging from room temperature up to 250C.
In certain applications, e.g., in the molding of poly-urethane parts, the thiofunctional polysiloxane compositions, when used as -the sole release agent impart satisfactory release --lar--.,.., ".~ ., 3~733Z3 properties. However, these composition have the disadvantage of forming a residue on the mold surface which either has to be removed or the mold has to be discarded. Thus, a considerable economic advantage is obtained by employing the compositions of aspects of this invention. Furthermore, when the conven-tional thiofunctional polysiloxane compositions are used as the sole release agent at temperatures of from 150 C to 200 C on metal substra-tes the rate of forma-tion of the release properties or deforms the surface of the released part. However, when the compositions of aspects of this invention are employed, the formation of residue is not apparent and subsequent release proper-ties are not subs-tantially impaired.
Embodiments of -this invention are further illustrated by the following examples in which all parts are by weight unless otherwise specified.
A thiofunctional polysiloxane is prepared by adding 28.2 parts of 3-mercaptopropyltrimethoxysilane, 0.5 part of water, an~
25.5 parts of Filtrol No. 13 acid clay (available from Filtrol Corporation) to a reaction vessel containing 1276 parts of hexa-methylcyclotrisiloxane heated to 70C. The vessel is heated to100C. and maintained at this temperature for three hours. The contents of the vessel are then cooled to 60C. and filtered. The ~CI 73323 vola-tiles are stripped off for 8 hours a-t 200C. a-t less than 1 torr. A clear, transparen-t liquid is obtained having a viscosity of 100 cs. at 25C. Nuclear Magnetic Resonance (NMR) analysis shows that the product has a mole ratio of CH30:HSC3H6:Si(CH3)2 of 3:1:100. The SH content of the product is about 0.43 percent.
The resultan-t composi-tion is applied as a thick film to the metal panels and a layer of Epoxical Urethane No. 1850 Foam "B"
Pak, (the Trade Mark of a product available from U.S. Gypsum) is then applied to the coated panels. The panels are -then heated in a forced air oven at 100 C. for two minutes, then removed from the oven and cooled. Adhesion of the urethane to the coa-ted panels is -then de-termined. The resul-ts are illus-tra-ted in Table I. After repeated applica-tions, a build up of residue is observed on -the mold surface.
_ MPLE 2 A mercaptofunc-tional fluid is prepared by adding 39.2 parts of 3-mercaptopropyltrimethoxysilane to a reaction vessel con-taining 592 parts of a hydroxyl terminated dimethylpolysiloxane having a viscosity of 350 cs. at 25C. and containing 2.43 percent by weigh-t of hydroxyl groups. The reactants are heated to 200 C.
for one hour and then vacuum stripped for two hours at 200C. at less than 1 torr. A clear product having a viscosity of 72.1 cs. at 25 C. is obtained which by Nuclear Magnetic Resonance has a ratio of CH30:HSC3H6:Si(CH3) of 1.58:1.0:32.4. The percent of SH is 0.79 percent.
The resultant composition is applied as a thick film to metal panels and a layer of Epoxical Urethane No. 1850 Foam "B" Pak (available from U.S. Gypsum) is then applied to the coa-ted panels.
~7;~3Z3 The panels are then placed in a forced air oven a-t 100C. for two minutes, then removed from the oven and cooled. Adhesion of the urethane to the coated panels is determined. The results are shown in Table I. After repeated application, a build up of residue on the coated panels is observed.
100 parts of the mercaptofunctional fluid prepared in accordance with Example 1 are mixed with 900 parts of a trimethylsilyl-endblocked dimethylpolysiloxane having a viscosity of 10 350 cs. at 25C. ~
The resultant composition is applied as a thick film to ~ .
metal panels and a layer of Epoxical Urethane No. 1850 Foam "B" Pak (available from U.S. Gypsum) is then applied -to the coated panels.
The panels are -then placed in a forced air oven at 100 C. for two minutes, then removed from the oven and cooled. Adhesion of the urethane to the coated panels is de-termined. The results are shown in Table I. After repeated applications no residue build up is observed on the surface.
lO0 parts of the mercap-tofunctional fluid prepared in accordance with Example 2 are mixed with 900 parts of a tri-methylsilyl-endblocked dimethylpolysiloxane having a viscosity of 350 cs. at 25C.
The resultant composition is applied as a thick film to metal panels and a layer of Epoxical Urethane No. 1850 Foam "B" Pak (available from U.S. Gypsum) is then applied to the coated panels.
; ~
~733~3 The panels are then placed in a forced air oven at 100 C. for two minutes, then removed from the oven and cooled. Adhesion of the urethane to the coa-ted panels is determined. The results are shown in Table 1.
EXAMPLE S
(a) In a comparison example, a trimetylsilyl-endblocked dimethylpolysiloxane (350 cs. at 25 C.) is applied to metal panels.
A layer of Epoxical Urethane No. 1850 Foam "B" Pak (available from U.S. Gypsum) is applied to the coated panels and placed in a forced air oven at 100C. for two minutes, then removed and cooled.
Adhesion of` the urethane to the coated metal panels is determined, The results are shown in Table 1.
(b) In a comparison example, a layer of Epoxical Urethane No. 1850 Foam "B" Palc (available from U.S. Gypsum) is applied to uncoated metal panels and placed in a forced air oven at 100C.
for two minutes, then removed and cooled. Adhesion of the urethane to metal panels is determined. The results are shown in Table 1.
'~.
The procedure of Example 1 is repea-ted except that a film of the thiofunctional fluid prepared in accordance with Example 1 is applied to the panels and the coated panels are then hea-ted to 200C for 2 hours and cooled to room temperature prior to the application of -the urethane layer. Although the urethane is readily removed from the metal panels, a build up of residue on the panels is observed.
~lo 733~:3 The procedure of Example 2 is repeated except tha-t a ~ilm of the thiofunctional fluid prepared in accordance with Example 2 is applied to the panels and the coated panels ar,e then heated to 200C. for 2 hours and cooled -to room temperature prior to -the application of the urethane layer. Al-though the urethane is readily removed from the metal panels, a build up of residue is observed on the panels.
10 The procedure o~ Example 3 is repeated except that the panels are coated with a film of the blend of Example 3 and heated to 200 C. for 2 hours and then cooled prior to the application of the urethane layer. Excellent release properties are observed withou-t any trace of residue build up on -the panels.
The procedure of Example ~ is repeated except tha-t the panels are coated wi-th a film of the blend of Example ~ and heated to 200 C. for 2 hours and then cooled prior to -the application of the urethane layer. Excellent release proper-ties are observed wi-thout any trace of residue build up on the panels.
___ The prooedure of Example 3 is repeated except that 90 parts of the thiofunctional fluid is mixed with 10 parts of a tri-me-thylsilyl-endblocked dimethylpolysiloxane fluid (100 cs. at 25 C) and applied to a metal substrate. Again excellen-t release proper-1~733Z3 ; -ties are observed between a urethane layer applied -thereto and the coated metal substrate. No residue build up is observed on the metal substrate a~ter repeated applications.
_ The composition prepared in accordance with Example 3 is applied to the surface of a metal mold. An epoxy resin containing the following ingredients is poured into the coated mold and heated to 100C. for 2 hours and then increased -to 160 C. for 6 hours. The epoxy resin is easily released from the mold.
~redients Parts Diglycidylether of 2,2-bis(p-hyAroxyphenyl)pentane having an epoxy equivalency of 181 100.0 Piperidine 2.0 Methyl-endomethylene tetra- ~;
hydrophthalic anhydride 85.0 Good release properties are observed even after making several castings of the epoxy resin in the same mold without the application of addi-tional release agent. Again, residue build up is not observed on the mold surface.
AMPLE 12_ The procedure of Example 11 is repeated except that the composition prepared in accordance with Example 4 is applied to -the surface of a metal mold. A composition containing the following ingredients is applied to the coated mold and heated to a tempera-~73323 ture of 150C. for 2 hours.
Ingredients 'Parts Liquid epoxy resin ~available from Union Carbide Corporation and identified'by the Trade Mark "ERL-2774i') 100.O
Tetrapropenyl succinic anhydride ~prepared'by heating together' equimolar proportions of maleic . anhydride and the tetramer of propylene) 150.0 Dimethylbenzylamine 1.5 The solid resin casting thus formed is easily removed from the mold.
The above process is repeated several times and each time the solid casting is easily removed from the mold without a trace of residue build up on the mold surface.
The liquid epoxy resin i6 a polyglycidyl ether oE a polyhydric phenol prepared from epichlorohydrin and bisphenol and has a Durrans melting point of 10C., an epoxy value of 0.52 epoxide equivalent per 100 grams and a hydroxyl value of 0.08 hydroxyl equivalent per 100 gramsO
.
The process of Example 1 is repeated except that 31 parts of 2-mercaptoethyltriethoxysilane is substituted for 3-mercaptopropyltri-methoxysilane. The resultant product has a viscosity of 95 cs. at 25C.
Nuclear Magnetic Resonance (NMR) analysis of the product shows that the ratio of C2H50:HSC2H5:Si(CH3)2 is 3:1:96. The percent of SH in the pro-duct is 0.41 percent.
\
.11 1:
~733~3 :
.' . .
¦ The product exhibits excellent release properties when ¦applied to a copper substrate prior to the application of a poly-¦urethane layer. After repeated applications of the polyurethane ¦layer a residue is observed on the copper substrate.
l . .
Two copper panels are thoroughly cleaned with a commercial I ;
polishing compound. To one panel is applied the composition gT
xample 3 and the exccss is removed. In this manner, the rlon-Itreated panel serves as a control. Both panels are placed in a ¦humid H2S chamber which consists of an aqueous solution of sodium ¦sul~ide to which dilute formic acid is periodically added. Within ¦20 minutes, the untreated panel is badly discolored. The treated ¦panel shows no evidence of discoloration.
I
~
previously, it is preferred that the organopolysiloxane be substan-tially free of hydroxyl groups. It is preferred that the poly-¦siloxanes have a viscosity of between 5 a~d 1,000,000 cs., ¦and more preferably between 50 cs. and 300,000 cs. at 25C.
iAlso, it is possible to combine high and low viscosity fluids to ¦
. form a fluid having the desired viscosity. High molecular ~Yeight gums.may also be employed; however,.it is preferred that these gums !:
. be dissolved in ~n organic solYent before they are combined with : . the thiofunctional polysiloxanes.
1~ The thiofunctional polysiloxanes employed in the composi-tion of aspects of this invention may be prepared by reacting a disiloxane : and/or a hydroxy or hydrocarbonoxy containing silane or siloxane with a cyclic trisiloxane in the presence of an acid catalyst in which at least one of the above organosilicon compounds contain a mercaptan group. ii l Disiloxanes which may be used in the compositions of aspects .
I ¦ of this invention may be represented by th~ for~lla .
(~)6-a I (M)aSi20 llwhlle the cyclic siloxanes are represented by the formula il (R~6-a.
(M)asi3o3 herein R, which may be the sa~e or different, represents a mono- ¦
valent hydrocarbon radical or a halogenated monovalent hydrocarbon radical having up to 18 carbon atoms, M is a group represented by ¦Ithe for ulae R'(SR"')y,in which at least one R"' is hydrogen, and SH
_4_ ,,. ' , ~, l l0733za la is a number of from 0 to 6 and y is a number of from 1 to 3.
¦ Suitable examples of organosilicon compounds which may be i . . Ireacted with the disiloxanes and/or cyclic trisiloxanes are silanes 1f the general formula .
I Ic .
I . ~M~bSi- (OR")3_ (b~c) -.' ' I . '.
or siloxanes o~ the general formula . - .;.
¦ . R2-d R R3-e l Y ~ Md ~ SiO ~ Si(0 ")e ¦~n which R is a.monovalent hydrocarbon radical or a halogenated ¦hydrocarbon radical having from 1 to 18 carbon atoms, M is a group represented by the formula R'(SR"')y,wherein at least one R"' is . !!hydrogen,and - - .
~15 . R~ . .
:~ ~ SH .
. , .
R' is substituted or unsubstituted divalent, trivalent or tetra-. Ivalent hydrocarbon radicals free of aliphatic unsat~rat;on ha~ing ¦~rom 1 to 18 carbon atoms, hydrocarbon ether9 hydrocarbon thioether, hydrocarbon ester and hydrocarbon thioester radicals in which R' is ~attached to the silicon atom via a silicon carbon bond, R" is hydrogen or a monovalent hydrocarbon radical having ~rom 1 to 18 ¦ carbon atoms, R"' may be the same as R" or a radical represented by llthe for ula R""X, wherein X is Il HC-, ¦! 5_ .
1~ .
~733Z3 . -OOCR, OH or a cyanoalky1 radical, wherein R"" is a divalent hydro-jl carbon radical free of aliphatic unsaturation having from 1 to lE
carbon atoms, Y is a radical of the formula R3SiOl/2, and .
~ . I3-e . . :
(R~)esiol/2 Iwhere R and R" are the sa~e as above, b is a number of from O to 3, . Ic is.a number of from O to 2 and the sum of b~c is from.l to 2, d 1.
. is a number of from O to 2, e is a number of from 1 to 3? m and n !ar~ each equal to a number of from O to 999 and the sum of m~n is ¦ i.
at least 1. . .
. Examples of suitable monovalent hydrocarbon radicals represented by R ~re alkyl radicals, e. -g., . methyl, ethyl, propyl, I
; ¦Ibutyl, pentyl, hexyl, octyl, decyl, octadecyl; aryl radicals, e. g., I
¦I phenyl, diphenyl and naphthyl; alkaryl radicals, e.. g., tolyl, .15 lIxylyl and ethylphenyl; aralkyl radicals, -e~ g., benzyl, c~-phenyl- I
!ethyl,.~-phenylethyl, ~ -phenylbutyl and cycloalkyl radicals, e. g., i I~ cyclobutyl, cyclopentyl and cyclohexyl radicals; halogenated ¦hydrocarbon radicals, e. g.,. chloromethyl, bro~oethyl, fluoroethyl,.
¦tetrafluoroethyl., trifluorotolyl, hexafluoroxylyl and the like. ¦
~ Examples of suitable divalent hydrocarbon radicals r~pre-sented.by R' and R"" are ethylene, trimethylene, tetra~ethylene, ¦Ihexamethylene, octamethylene and the like. Suitable examples o~
trivalent and tetravalent hydrocarbon radicals are represer,ted by ¦the for~ulae =CHCH2-, =CHCH2CH2-~ =C~tCH2)3-, =CH~CH2)4-, ~=CH(CH2)-17~ =CCH2-~ =C(cH2)2-~ -CCH~-, --C(CH2)2- 9 -C~CH2~3-C~3 C2H5 j -C(CH2)17-, --C~HCH2-, -C~H(CH2)2-CH3 C2Hs .¦
jand the like. .
-6~
0 ~ ;3 Z ~
Suitable examples of monovalent hydrocarbon radicals ¦ represented by R" are alkyl radicals, e. g., methyl, ethyl, propyl, ! butyl, pentylj hexyl, octyl, decyl, octadecyl; aryl radicals, e- 8-, ¦ phenyl, diphenyl and naphthyl; alkaryl radicals, e. g., tolyl, ~ .. -1 xylyl and ethylphenyl; ara~kyl radicals, e. g., benzyl,c~ -phenyl-; . ¦ethyl, ~g-phenylethyl, ~ -phenylbutyl and cycloalkyl radicals, e. gO~
¦ cyclobutyl, cyclopentyl and cyc10hexyl radicals. . :
¦ Suitable examples of R'(SR"')y groups include -CH2SH, ¦-C2H4SH C3H6SH (HSCH2)2CHCH2CH2- (HSCH2C~2)(HSCH2)CH(CH2)4-(HSCH2CH2)3CCH2CH2- ~ (HSC1~2CH2) (HscH2)cHcH(cH2sH)c~l2cH2cH2-, ,I l~s(cH2)5cH(cH2cH2sH)cH2cH2cH(cH2cH3)-, (HSCH2CH2)2CHCH2CH2-, .
~ (Hsc~l2)2c~scH2cH~cH2-, ,(HSCH2)2(C2~15)CCH2SCH2CH2CH3-~
¦ (Hsc~l2)3ccH2scH2cH2cH2-~ (HscH2)(tisc~i2cl~2cH2cH2)~s~2 ~ 2 . ¦ (HSC~2CH2)2CHCH2SCH2CH2CH2-, (HSCH2)2(C2H5)CCH2S~H2CH2S(CH2)3- ' 15~HSCH2)3CCH2S(CH2)3s(cH2)3-~ . . .
, S ' .' '. .
(~ISCH2 ) 3CHCH3CH2CSCH2CH2CH2 , .
S . ' ' . ~:, (HSCH2)3~C~12Csc~l2cH2cH2- ' ~0 ' . S . .
. ~HscH2)2(c~H5)cc~2sccH2cl~2cH2-~ .; . .
, I , ' ,, .
¦(Hs&H2)2(c2H5)ccH2scH2cH(cH3)cocH2cH2cH2-, .
I O .
25 ¦(HSCH2)3CCH2SCH2CH(CH3)COCH2CH2CH2- and the like. ¦
Hydroxy and hydrocarbonoxy containing silane; which may be en)ployed are silanes, e. g., 3-mercaptopropyltrimethoxysilane, 2-mercaptoethyltriethoxysilane, w-mercaptodecyltriethoxy-ilane, 2-_7 ., I ~ ' , .' l ~733Z3 mercaptohexyltripropoxysilane, w-mercaptoamyltriethoxysilane, 2-¦(triethoxysilyl)ethyl butyl thioether, 3-(triethoxysilyl)propyl ¦ butyl thioether, 4-~triethoxysilyl)butyl methyl thioether, 2-(methyldiethoxysilyl)ethyl methyl thioether, 2-(methyldiethoxy-silyl)ethyl phenyl thioether, 2-(methyldiethoxysilyl)ethyl dodecyl thioether, 6-(trimethoxysilyl)hexyl ethyl thioether, methyltri- ;
ethoxysilane~. dimethyldiethoxysilane, trimethylethoxysilane, imethylsllane diol, diphenylsilane diol and the like.
The corresponding siloxanes or copolymers thereof which contain at least one or more alkoxy or hydroxy groups may also be employed. Sui.table.examples o~ these polysiloxanes are monoethoxy endblocked beta-mercaptoethyl propylpolysiloxane or methyldiethoxy silyl endbloc~ed beta-mercaptobutyl methylpolysiloxane, monohydroxy endblocked beta-mercaptoethyl ~ethylpolysil`oxane, dihydroxy end-,15 blocked dimethylpolysiloxane,diethoxy endblocked dimethylpoly- ¦
siloxane and the like.
. Other hydroxy and/or hydroca.rbonoxy si~icon.compounds which may be. employed as one of the initial reactants ~ith theI ~;
disiloxane and/or cyclic trisiloxane are the silacyclopentane thiol ~:
jlcompounds disclosed in U.S. Patent 3,655,713 to Le Grow.
¦ Examples of suitable disiloxanes are hexamethyldisiloxane, ¦ hexaethyldisiloxane, hexapropyldisiloxane, hexaoctyldisiloxane, di- .
~3-mercaptopropyl)tetramethyldisiloxane and the li~e. EY~amples of l~suitable cyclic silox~anes are hexamethylcyclotrisiloxa,.e, hexa~ hyl-lltrisiloxane, hexaphenyltrisiloxane, hexabutyltrisiloxane, hexaoctyl-~trisilox2ne, 1,2,3-trim2thyl 1,2,3-triphenylcyclotrisiloxane and tnP-like. ' .
j Catalysts ~Ihich may be employed in eEfecting the reartion -8- :
I
I ~ . . ..
1(~73323 between a disiloxane and/or a hydroxy and/or hydrocarbonoxy containing silane or siloxane and a cyclic trisiloxane in which at least one of the reactants contains a mercaptan group are acid clays and organic and inorganic acids having a pK value less than 1.0 and more preferably below 0.7 in aqueous solutions. Suitable acid catalyst which may be employed are benzosulfonic acid, para-toluene-sulfonic acid, sulfuric acid, sul-furous acid, nitric acid, perchloric acid, hydrochloric acid and acid clays~ e.g. those known by the Trade Marks of Filtrol No. 13 and No. 24 (available from Filtrol Corporation).
Although the amount of catalyst is not critical, it is pre-ferred that from 0.003 percent up to 10 percent by weight of catalyst based on the total weight of the reactants, i.e., the silicon containing compounds used in the preparation of thè thionfunctional polysiloxanes be employed. Greater amounts of catalyst may be used; however, it is the intent of aspects of this invention to provide a catalyst system which does not alter the functionality of the resultant composition.
Generally, it is desirable to remove or destroy the catalysts after the reaction is complete because their presence will adversely affect the properties of the resulting composition. The catalysts may be removed, for example, by washing with water or they ma~ be destroyed by neutralizing with basic reagents. In addition, certain catalyst, e.g., acid clays, may be removed by filtering the reaction mixture.
The reactions may be conducted at any temperature ranging from 25C. up to 200C. over a period of time ranging from 0.5 hour up to several days and, if desired, in the presence of a hydrocarbon solven~.
Under certain condltions, for example, when an anhydrous catalyst is employed, a catalytic amount of a ~_ 9 _ .:
. ! , .' . .
protic compound is required to effect the reaction. The term protic compound refers to compounds having a reacti~e hydrogen 9 e. g., ¦¦alcohols, e.g., methanol, ethanol, propanol, butanol and water. The ¦lamount of protic compound is not cri~ical ancl may range ~I from O.OOOl to 1O percent based on the total weight of the silicon containing reactants.
- The reaction may be conducted at atmospheric, subatmos-pheric or superatmospheric pressure in the absence of a solvent;
IhoweYer, ~hen a solvent is employed~ it may be employed in an amount- ~;
¦of from '.1 to 50 percent by weight based on tne sllicon con-¦taining reactants. Examples of suitable hydrocarbon solvents are ¦
~heptane, benzene, toluene, xylene and the like. It is, however, pre~erred that the reaction be conducted in an inert atmosphere.
I Other thiofunctional polysiloxanes which may be employed I ;
¦in the release composition of aspects of this invention are siloxane copolymers :, :
Icontaining from O.l to 99.9 mole percent o~ units of the formula I , . , MhSiO~ .
and from 99.9 to O.l mole percen~ o~ at least one oth2r siloxan~
unit having the general formula : j RfSiO4_~
¦¦in which R and M are the same as above, ~ is O, l or 2, 9 is ~ ¦
¦¦1 or 2 and h is 1 to 2. These copolymers may also contain R"O and ¦¦R3SjO units in which R and R" are the same as above.
These thiofunctional polysiloxanes can be prepared by ¦reacting hydroxyl containing polysiloxanes with silanes containing 11 ~ ~
! -lo- -..... ~ ... . ... .
mercaptan groups or by the cohydrolysis of chloroalkylchlorosilanes, dialkyldichlorosilanes and trimethylchlorosilanes and thereafter reacting r the chloroalkyl groups with sulfur containing compounds to form poly-siloxanes having mercaptan functionality. Thiofunctional polysiloxanes, e.g., those described in United States Patent No. 3,346,~05 oo Viventi in which 4 -chloroalkyl containing polyciloxanes are reacted with sodium sulfohydride in the presence of dimethylformamide may be employed in the compositions of other aspects of this invention. Other thiofunctional polysiloxanes which may be employed in the compositions of aspec~s of this invention are those prepared in accordance with United States Patent No. 2,960,492 to Morton and No. 3,388,144 to Musolf et al.
The compositions of aspects of this invention can contain from 0.1 percent to 90 percent by weight of thiofunctional polysiloxanes and from 10 percent to 99.9 percent by weight of the organopolysiloxanes.
It is preferred that the composition contain from 1.0 to 30 percent by weight of the thiofunctional polysiloxanes and from 70 percent to 99 per-cent by weight of the organopolysiloxanes based on the weight of the thiofunctional polysiloxanes and the organopolysiloxanes. ~;
Although it is not essential, the composition of aspects of this invention may be diluted with organic solvents to form a solution contain-ing from 0.1 percent to 99 percent and more preferably from 1.0 to 20 percent by weight based on the weight of the composition, i.e., solvent and the siloxanes. Suitable examples of organic solvents are aliphatic hydrocarbons~ e.g., hexane, heptane, octane; aromatic hydrocarbons, e.g., benzene, toluene, xylene, ethylbenzene, naphtha; halogenated hydrocarbons, e.g., methylene chloride, perchloroethylene, trichloroethylene~ carbon tetrachloride, ethers and ~3323 polyethers, e.g. diethyl ether3 dimethyl ether, dibutyl ether, diethylene glycol dimethyl ether', diethylene glycol diethyl ether and the like.
Preferably the'solvent employed in the compositions of aspects of this invention is methylene chloride or perchloroethylene.
Metals and alloys which may be treated with the composition of aspects of this invention are those below and including magnesium in the electromotive series. The metals and alloys include aluminum~ brass, bronze, copper, chromium, iron, magnesium, nickel, lead, silver, silver-plate, sterling silver', tin, beryllium, bronze and zinc.
1~ Any method kno~n in the art may be employed to apply the com-positions of aspects of this invention to a metal surface as long as it results in the deposition of a continuous film. The composition may be applied to the metal surface by dipping, spraying, wiping or brushing.
The coated surface may be used immediately or may be heated to an elevated temperature such as, for example, from 100 to 300C. The heating step accelerates the rate of reaction of the release coating with the metal surface, thereby improving the passivating effect of the coating in certain applications.
The thickness of the coating applied to the metal surface is not critical and may vary from a very thin film to a relatively heavy coat such as those in excess of Ool inch. A coating thickness ranging from 0.01 to Q.10 inch is preferred, although from an economic point of view, a thin film having a thicknesæ of only a few Angstrom units can be employed. Generally, the thickness of the coating can be regulated by the mode of application.
The compositions of aspects of this invention may be applied to metal substrates which are used for molding thermal plastic and thermo-se-tting materials, e.g., polyurethanes, polyethylene, epoxy resins and the like.
Polyurethanes which are well known in the art are prepared by reacting an organic compound having at least two active hydrogen atoms as determined by the Zerewitinoff method with a polyisocya-nate. Other reactants, e.g, chain extending agents and gas-generating materials may also be employed, depending on -the parti-cular polyurethane article desired. For example, in the formation of a cellar material, a gas-generating material, e.g., water, is generally incorporated in the composition.
Suitable examples of polyisocyanates are diisocyanates, e.g., alkylene diisocyanates, e.g, hexamethylene diisocyanate and decamethylenediisocyana-te, and arylene diisocyanates, e.g., phenyl-ene diisocyanates, toluene diisocyanates and mixtures thereo~.
Compounds having two or more active hydrogen atoms as determined by the Zerewitinoff method are polyalkylene polyols, e.g., polyesters, polyethers, alkylene glycols, polymercaptans, polyamines and the like.
The composition of aspects of this invention may be used as a release agent for molding epoxy resins. ~`hese compounds have an oxirane epoxy equivalency greater than one, that is, compounds having an average of more than one oxirane epoxy group, e.g., --C -- C--O
per molecule. The epoxy containing compounds in which the oxygen of -the epoxy group is attached to vicinal carbon atoms, can be saturated or unsaturated, aliphatic, cycloalipha-tic, or hetero-cyclic, and can be substituted with substituents, e.g,, halogen atoms, alkyl groups, ether groups and the ]ike.
Examples of suitable polyepoxides are the polyglycidyl ethers of polyhydric phenols, polyglycidyl ethers of the bis-(hydroxyphenyl)alkanes, polyglycidyl ethers of` polyhydric alcohols, `
polyglycidyl esters of polycarboxylic acids, polyglycidyl deriva-' tives of aromatic amines and aminophenols.
These polyepoxides are reacted with curing agents to form ;
hard insoluble infusible products. The curing agents for the products include ma-terials which are preferably acidic or basic, e.g., poly basic acids and their anhydrides, acids which contain sulfur, nitrogen, phosphrous or halogens and bases, e.g., amine-con-taining compounds.
0-ther curing agents which may be used in curing -the epoxy ~`
resins are boron trifluoride and complexes of boron trifluoride with amines, ethers, phenols and the like, ~riedel-Crafts metal salts, e.g., aluminum chloride, zinc chloride, and o-ther salts, e.g., zinc fluoborate, magnesium perchlorate and zinc fluosilicate;
inorganic acids and partial esters, e.g., phosphoric acid and partial esters thereof including n-butyl orthothiophosphate, diethyl orthophosphate and hexaethyltetraphosphate and polyamides containing active and/or carboxyl groups.
The thermosetting or thermal plastic materials are applied to a mold whose surface has been coated with the release composition af aspects of this invention and the plastic materials are cured at temperatures ranging from room temperature up to 250C.
In certain applications, e.g., in the molding of poly-urethane parts, the thiofunctional polysiloxane compositions, when used as -the sole release agent impart satisfactory release --lar--.,.., ".~ ., 3~733Z3 properties. However, these composition have the disadvantage of forming a residue on the mold surface which either has to be removed or the mold has to be discarded. Thus, a considerable economic advantage is obtained by employing the compositions of aspects of this invention. Furthermore, when the conven-tional thiofunctional polysiloxane compositions are used as the sole release agent at temperatures of from 150 C to 200 C on metal substra-tes the rate of forma-tion of the release properties or deforms the surface of the released part. However, when the compositions of aspects of this invention are employed, the formation of residue is not apparent and subsequent release proper-ties are not subs-tantially impaired.
Embodiments of -this invention are further illustrated by the following examples in which all parts are by weight unless otherwise specified.
A thiofunctional polysiloxane is prepared by adding 28.2 parts of 3-mercaptopropyltrimethoxysilane, 0.5 part of water, an~
25.5 parts of Filtrol No. 13 acid clay (available from Filtrol Corporation) to a reaction vessel containing 1276 parts of hexa-methylcyclotrisiloxane heated to 70C. The vessel is heated to100C. and maintained at this temperature for three hours. The contents of the vessel are then cooled to 60C. and filtered. The ~CI 73323 vola-tiles are stripped off for 8 hours a-t 200C. a-t less than 1 torr. A clear, transparen-t liquid is obtained having a viscosity of 100 cs. at 25C. Nuclear Magnetic Resonance (NMR) analysis shows that the product has a mole ratio of CH30:HSC3H6:Si(CH3)2 of 3:1:100. The SH content of the product is about 0.43 percent.
The resultan-t composi-tion is applied as a thick film to the metal panels and a layer of Epoxical Urethane No. 1850 Foam "B"
Pak, (the Trade Mark of a product available from U.S. Gypsum) is then applied to the coated panels. The panels are -then heated in a forced air oven at 100 C. for two minutes, then removed from the oven and cooled. Adhesion of the urethane to the coa-ted panels is -then de-termined. The resul-ts are illus-tra-ted in Table I. After repeated applica-tions, a build up of residue is observed on -the mold surface.
_ MPLE 2 A mercaptofunc-tional fluid is prepared by adding 39.2 parts of 3-mercaptopropyltrimethoxysilane to a reaction vessel con-taining 592 parts of a hydroxyl terminated dimethylpolysiloxane having a viscosity of 350 cs. at 25C. and containing 2.43 percent by weigh-t of hydroxyl groups. The reactants are heated to 200 C.
for one hour and then vacuum stripped for two hours at 200C. at less than 1 torr. A clear product having a viscosity of 72.1 cs. at 25 C. is obtained which by Nuclear Magnetic Resonance has a ratio of CH30:HSC3H6:Si(CH3) of 1.58:1.0:32.4. The percent of SH is 0.79 percent.
The resultant composition is applied as a thick film to metal panels and a layer of Epoxical Urethane No. 1850 Foam "B" Pak (available from U.S. Gypsum) is then applied to the coa-ted panels.
~7;~3Z3 The panels are then placed in a forced air oven a-t 100C. for two minutes, then removed from the oven and cooled. Adhesion of the urethane to the coated panels is determined. The results are shown in Table I. After repeated application, a build up of residue on the coated panels is observed.
100 parts of the mercaptofunctional fluid prepared in accordance with Example 1 are mixed with 900 parts of a trimethylsilyl-endblocked dimethylpolysiloxane having a viscosity of 10 350 cs. at 25C. ~
The resultant composition is applied as a thick film to ~ .
metal panels and a layer of Epoxical Urethane No. 1850 Foam "B" Pak (available from U.S. Gypsum) is then applied -to the coated panels.
The panels are -then placed in a forced air oven at 100 C. for two minutes, then removed from the oven and cooled. Adhesion of the urethane to the coated panels is de-termined. The results are shown in Table I. After repeated applications no residue build up is observed on the surface.
lO0 parts of the mercap-tofunctional fluid prepared in accordance with Example 2 are mixed with 900 parts of a tri-methylsilyl-endblocked dimethylpolysiloxane having a viscosity of 350 cs. at 25C.
The resultant composition is applied as a thick film to metal panels and a layer of Epoxical Urethane No. 1850 Foam "B" Pak (available from U.S. Gypsum) is then applied to the coated panels.
; ~
~733~3 The panels are then placed in a forced air oven at 100 C. for two minutes, then removed from the oven and cooled. Adhesion of the urethane to the coa-ted panels is determined. The results are shown in Table 1.
EXAMPLE S
(a) In a comparison example, a trimetylsilyl-endblocked dimethylpolysiloxane (350 cs. at 25 C.) is applied to metal panels.
A layer of Epoxical Urethane No. 1850 Foam "B" Pak (available from U.S. Gypsum) is applied to the coated panels and placed in a forced air oven at 100C. for two minutes, then removed and cooled.
Adhesion of` the urethane to the coated metal panels is determined, The results are shown in Table 1.
(b) In a comparison example, a layer of Epoxical Urethane No. 1850 Foam "B" Palc (available from U.S. Gypsum) is applied to uncoated metal panels and placed in a forced air oven at 100C.
for two minutes, then removed and cooled. Adhesion of the urethane to metal panels is determined. The results are shown in Table 1.
'~.
The procedure of Example 1 is repea-ted except that a film of the thiofunctional fluid prepared in accordance with Example 1 is applied to the panels and the coated panels are then hea-ted to 200C for 2 hours and cooled to room temperature prior to the application of -the urethane layer. Although the urethane is readily removed from the metal panels, a build up of residue on the panels is observed.
~lo 733~:3 The procedure of Example 2 is repeated except tha-t a ~ilm of the thiofunctional fluid prepared in accordance with Example 2 is applied to the panels and the coated panels ar,e then heated to 200C. for 2 hours and cooled -to room temperature prior to -the application of the urethane layer. Al-though the urethane is readily removed from the metal panels, a build up of residue is observed on the panels.
10 The procedure o~ Example 3 is repeated except that the panels are coated with a film of the blend of Example 3 and heated to 200 C. for 2 hours and then cooled prior to the application of the urethane layer. Excellent release properties are observed withou-t any trace of residue build up on -the panels.
The procedure of Example ~ is repeated except tha-t the panels are coated wi-th a film of the blend of Example ~ and heated to 200 C. for 2 hours and then cooled prior to -the application of the urethane layer. Excellent release proper-ties are observed wi-thout any trace of residue build up on the panels.
___ The prooedure of Example 3 is repeated except that 90 parts of the thiofunctional fluid is mixed with 10 parts of a tri-me-thylsilyl-endblocked dimethylpolysiloxane fluid (100 cs. at 25 C) and applied to a metal substrate. Again excellen-t release proper-1~733Z3 ; -ties are observed between a urethane layer applied -thereto and the coated metal substrate. No residue build up is observed on the metal substrate a~ter repeated applications.
_ The composition prepared in accordance with Example 3 is applied to the surface of a metal mold. An epoxy resin containing the following ingredients is poured into the coated mold and heated to 100C. for 2 hours and then increased -to 160 C. for 6 hours. The epoxy resin is easily released from the mold.
~redients Parts Diglycidylether of 2,2-bis(p-hyAroxyphenyl)pentane having an epoxy equivalency of 181 100.0 Piperidine 2.0 Methyl-endomethylene tetra- ~;
hydrophthalic anhydride 85.0 Good release properties are observed even after making several castings of the epoxy resin in the same mold without the application of addi-tional release agent. Again, residue build up is not observed on the mold surface.
AMPLE 12_ The procedure of Example 11 is repeated except that the composition prepared in accordance with Example 4 is applied to -the surface of a metal mold. A composition containing the following ingredients is applied to the coated mold and heated to a tempera-~73323 ture of 150C. for 2 hours.
Ingredients 'Parts Liquid epoxy resin ~available from Union Carbide Corporation and identified'by the Trade Mark "ERL-2774i') 100.O
Tetrapropenyl succinic anhydride ~prepared'by heating together' equimolar proportions of maleic . anhydride and the tetramer of propylene) 150.0 Dimethylbenzylamine 1.5 The solid resin casting thus formed is easily removed from the mold.
The above process is repeated several times and each time the solid casting is easily removed from the mold without a trace of residue build up on the mold surface.
The liquid epoxy resin i6 a polyglycidyl ether oE a polyhydric phenol prepared from epichlorohydrin and bisphenol and has a Durrans melting point of 10C., an epoxy value of 0.52 epoxide equivalent per 100 grams and a hydroxyl value of 0.08 hydroxyl equivalent per 100 gramsO
.
The process of Example 1 is repeated except that 31 parts of 2-mercaptoethyltriethoxysilane is substituted for 3-mercaptopropyltri-methoxysilane. The resultant product has a viscosity of 95 cs. at 25C.
Nuclear Magnetic Resonance (NMR) analysis of the product shows that the ratio of C2H50:HSC2H5:Si(CH3)2 is 3:1:96. The percent of SH in the pro-duct is 0.41 percent.
\
.11 1:
~733~3 :
.' . .
¦ The product exhibits excellent release properties when ¦applied to a copper substrate prior to the application of a poly-¦urethane layer. After repeated applications of the polyurethane ¦layer a residue is observed on the copper substrate.
l . .
Two copper panels are thoroughly cleaned with a commercial I ;
polishing compound. To one panel is applied the composition gT
xample 3 and the exccss is removed. In this manner, the rlon-Itreated panel serves as a control. Both panels are placed in a ¦humid H2S chamber which consists of an aqueous solution of sodium ¦sul~ide to which dilute formic acid is periodically added. Within ¦20 minutes, the untreated panel is badly discolored. The treated ¦panel shows no evidence of discoloration.
I
~
Claims (27)
1. A composition comprising a branched or linear organopoly-siloxane which is substantially free of aliphatic unsaturation and hydroxyl groups and has from 1.75 to 2.25 organic radicals per silicon atom and a thiofunctional polysiloxane fluid having at least one mercap-tan group per molecule, said organopolysiloxane being present in an amount of from 10 to 99.9 percent by weight and said thiofunctional polysiloxane fluid being present in an amount of from 90 to 0.1 percent by weight based on the weight of the organopolysiloxane and the thio-functional polysiloxane fluid, said thiofunctional polysiloxane fluid contains siloxane copolymers having from 0.1 to 99.9 mole percent of units of the formula and from 99.9 to 0.1 mole percent of at least one other siloxane unit having the general formula wherein R is selected from the group consisting of a monovalent hydro-carbon radical and a halogenated monovalent hydrocarbon radical each having from 1 to 18 carbon atoms, M is selected from the class consisting of R'(SR"')y, and , R' is selected from the group consisting of a substituted and unsub-stituted divalent, trivalent and tetravalent hydrocarbon radical, a hydrocarbon ether, a hydrocarbon thioether, a hydrocarbon ester and a hydrocarbon thioester in which R' is attached to a silicon atom via a silicon-carbon bond, R" is selected from the group consisting of hydrogen and a monovalent hydrocarbon radical, R"' is selected from the group consisting of R" and a radical represented by the formula R""X, wherein X is a radical selected from the group consisting of , , OH and a cyanoalkyl radical, R"" is a divalent hydrocarbon radical free of aliphatic unsaturation having from 1 to 18 carbon atoms, and when M is R'(SR"')y, at least one R"' is hydrogen, f is 0, 1 or 2, g is 0, 1 or 2, h is 1, 2 or 3 and y is a number of from 1 to 3.
2. A composition containing (1) an organopolysiloxane which is free of aliphatic unsaturation and has from 1.75 to 2.25 organic radicals per silicon atom and (2) a thiofunctional polysiloxane fluid having at least one mercaptan group per molecule, said organopolysiloxane (1) being present in an amount of from 10 to 99.9 percent by weight and said thio-functional polysiloxane fluid (2) being present in an amount of from 90 to 0.1 percent by weight based on the weight of the organopolysiloxane (1) and the thiofunctional polysiloxane fluid (2), said thiofunctional polysiloxane fluid (2) contains siloxane copolymers having from 0.1 to 99.9 mol percent of units of the formula and from 99.9 to 0.1 mol percent of at least one other siloxane unit having the general formula wherein R is selected from the group consisting of a monovalent hydro-carbon radical and a halogenated monovalent hydrocarbon radical, each having from 1 to 18 carbon atoms, M is a mercaptan containing radical of the formula R'(SR"')y, R' is selected from the group consisting of a substituted and unsubstituted divalent, trivalent and tetravalent hydro-carbon radical, a hydrocarbon ether, a hydrocarbon thioether, a hydro-carbon ester and a hydrocarbon thioester in which R' is attached to a silicon atom via a silicon-carbon bond, R"' is selected from the group consisting of hydrogen, a monovalent hydrocarbon radical and a radical represented by the formula R""X, wherein X is a radical selected from the group consisting of , , OH and a cyanoalkyl radical, R"" is a divalent hydrocarbon radical free of aliphatic unsaturation having from 1 to 18 carbon atoms, and at least one R"' is hydrogen, f is 0, 1 or 2, g is 0, 1 or 2, h is 1, 2 or 3, and y is a number of from 1 to 3.
3. A composition containing (1) an organopolysiloxane which is free of aliphatic unsaturation and has from 1.75 to 2.25 organic radicals per silicon atom and (2) a thiofunctional polysiloxane fluid having at least one mercaptan group per molecule, said organopolysiloxane (1) being present in an amount of from 10 to 99.9 percent by weight and said thiofunctional polysiloxane fluid (2) being present in an amount of from 90 to 0.1 percent by weight based on the weight of the organo-polysiloxane (1) and the thiofunctional polysiloxane fluid (2), said thiofunctional polysiloxane fluid (2) contains siloxane copolymers having from 0.1 to 99.9 mol percent of units of the formula and from 99.9 to 0.1 mol percent of at least one other siloxane unit having the general formula wherein R is selected from the group consisting of a monovalent hydro-carbon radical and a halogenated monovalent hydrocarbon radical each having from 1 to 18 carbon atoms, M is a mercaptan containing radical of the formula , R" is selected from the group consisting of hydrogen and a monovalent hydrocarbon radical, f is 0, 1 or 2, g is 0 or 1, h is 1 and the sum of g + h is 1 or 2.
4. A composition containing (1) an organopolysiloxane which is free of aliphatic unsaturation and has from 1.75 to 2.25 organic radicals per silicon atom and (2) a thiofunctional polysiloxane fluid having at least one mercaptan group per molecule, said organopolysiloxane (1) being present in an amount of from 10 to 99.9 percent by weight and said thiofunctional polysiloxane fluid (2) being present in an amount of from 90 to 0.1 percent by weight based on the weight of the organopolysiloxane (1) and the thiofunctional polysiloxane fluid (2), said thiofunctional polysiloxane fluid (2) is obtained from the reaction of a cyclic tri-siloxane of the formula Ma R(6-a) Si303 with a silicon compound in the presence of an acid catalyst having a pKa value below 1, said silicon compound is selected from the class consis-ting of silanes of the formula and siloxanes of the formula wherein R is selected from the group consisting of a monovalent hydro-carbon radical and a halogenated monovalent hydrocarbon radical, each having from 1 to 18 carbon atoms, M is selected from the class consisting of R'(SR"')y, and in which R' is selected from the group consisting of a substituted and unsubstituted divalent, trivalent and tetravalent hydrocarbon radical having from 1 to 18 carbon atoms, a hydrocarbon ether, a hydrocarbon thioether, a hydrocarbon ester and a hydrocarbon thioester, in which R' is attached to a silicon atom via a silicon-carbon bond, R" is selected from the group consisting of hydrogen and a monovalent hydrocarbon radical having from 1 to 18 carbon atoms, R"' is selected from the group consisting of R" and a radical represented by the formula R""X, wherein X is a radical selected from the group consisting of , , and OH and a cyanoalkyl radical, in which R"" is a divalent hydrocarbon radical free of aliphatic unsaturation having from 1 to 18 carbon atoms, Y is a radical selected from the class consisting of R3SiO1/2, and wherein R and R" are the same as above, and when M is R'(SR"')y, at least one R"' is hydrogen, a is a number of from 0 to 6, b is a number of from 0 to 3, c is a number of from 0 to 2 and the sum of b+c is from 1 to 2, d is a number of from 0 to 2 and when d is 1 or 2 the sum of a+b+m is at least 1 and when d is 1 to 3, m and n are each equal to a number of from 0 to 20,000 and the sum of m+n is at least 1 and y is a number of from 1 to 3.
5. The composition of claim 1 wherein the thiofunctional polysiloxane is obtained from the reaction of a cyclic trisiloxane of the formula MaR(6-a) Si3O3 with a silicon compound in the presence of an acid catalyst having a pK value below 1, said silicon compound is selected from the class con-sisting of silanes of the formula and siloxanes of the formula wherein R is selected from the group consisting of a monovalent hydro-carbon radical and a halogenated monovalent hydrocarbon radical each having from 1 to 18 carbon atoms, M is selected from the class consisting of R'(SR"')y, and in which R' is selected from the group consisting of a substituted and unsubstituted divalent, trivalent and tetravalent hydrocarbon radical having from 1 to 18 carbon atoms, a hydrocarbon ether, a hydrocarbon thioether, a hydrocarbon ester and a hydrocarbon thioester in which R' is attached to a silicon atom via a silicon-carbon bond, R" is selected from the group consisting of hydrogen and a monovalent hydrocarbon radical having from 1 to 18 carbon atoms, R"' is selected from the group consisting of R" and a radical represented by the formula R""X, wherein X is a radical selected from the group consisting of , , OH and a cyanoalkyl radical, in which R"" is a divalent hydrocarbon radical free of aliphatic unsaturation having from 1 to 18 carbon atoms, Y is a radical selected from the class consisting of R3SiO1/2, and where R and R" are the same as above, and when M is R'(SR"')y, at least one R"' is hydrogen, a is a number of from 0 to 6 9 b is a number of from 0 to 3, c is a number of from 0 to 2 and the sum of b+c is from 1 to 2, d is a number of from 0 to 2 and the sum of a+b+d is at least 1, e is a number of from 1 to 3, m and n are each equal to a number of from 0 to 999 and the sum of m+n is at least 1 and y is a number of from 1 to 3.
6. The composition of claim 5 wherein the cyclic trisiloxane is represented by the formula MaR6-aSi3O3 wherein R is selected from the group consisting of a monovalent hydro-carbon radical and a halogenated monovalent hydrocarbon radical each having from 1 to 18 carbon atoms, a is a number of from 0 to 6, M is selected from the class consisting of R'(SR"')y, in which at least one R"' is hydrogen, and wherein R' is selected from the group consisting of substituted and unsubstituted divalent, trivalent and tetravalent hydrocarbon radicals free of aliphatic unsaturation having from 1 to 18 carbon atoms, hydro-carbon ether, hydrocarbon thioether, hydrocarbon ester and hydrocarbon thioester radicals, in which R' is attached to a silicon atom via a silicon-carbon bond, R" is selected from the group consisting of hydrogen and a monovalent hydrocarbon radical having from 1 to 18 carbon atoms, R"' is selected from the group consisting of R" and a radical represented by the formula R""X, wherein X is a radical selected from the group consisting of , , OH and a cyanoalkyl radical, in which R"" is a divalent hydrocarbon radical free of aliphatic unsaturation having from 1 to 18 carbon atoms and y is a number of from 1 to 3.
7. The composition of claim 4 wherein an organodisiloxane is included in the preparation of the thiofunctional polysiloxane fluid, said organodisiloxane having the formula MaR(6-a) Si2O
wherein R is a monovalent hydrocarbon radical having from 1 to 18 carbon atoms, M is selected from the class consisting of R'(SR"')y, and wherein R' is selected from the group consisting of a substituted and unsubstituted divalent, trivalent and tetravalent hydrocarbon radical having from 1 to 18 carbon atoms, a hydrocarbon ether, a hydrocarbon thioether, a hydrocarbon ester, and a hydrocarbon thioester, in which R' is attached to a silicon atom via a silcon-carbon bond, R" is selected from the group consisting of hydrogen and a monovalent hydrocarbon radi-cal having from 1 to 18 carbon atoms, R"' is selected from the group consisting of R" and a radical represented by the formula R""X, wherein X is a radical selected from the group consisting of , , OH and a cyanoalkyl radical, R"" is a divalent hydrocarbon radical free of aliphatic unsaturation having from 1 to 18 carbon atoms, and when M is R'(SR"')y, at least one R"' is hydrogen, a is a number of from 0 to 6 and y is a number of from 1 to 3.
wherein R is a monovalent hydrocarbon radical having from 1 to 18 carbon atoms, M is selected from the class consisting of R'(SR"')y, and wherein R' is selected from the group consisting of a substituted and unsubstituted divalent, trivalent and tetravalent hydrocarbon radical having from 1 to 18 carbon atoms, a hydrocarbon ether, a hydrocarbon thioether, a hydrocarbon ester, and a hydrocarbon thioester, in which R' is attached to a silicon atom via a silcon-carbon bond, R" is selected from the group consisting of hydrogen and a monovalent hydrocarbon radi-cal having from 1 to 18 carbon atoms, R"' is selected from the group consisting of R" and a radical represented by the formula R""X, wherein X is a radical selected from the group consisting of , , OH and a cyanoalkyl radical, R"" is a divalent hydrocarbon radical free of aliphatic unsaturation having from 1 to 18 carbon atoms, and when M is R'(SR"')y, at least one R"' is hydrogen, a is a number of from 0 to 6 and y is a number of from 1 to 3.
8. The composition of claim 1 wherein an organodisiloxane is included in the reaction, said organodisiloxane having the formula MaR(6-a) Si2O
wherein R is selected from the group consisting of a monovalent hydro-carbon radical and a halogenated monovalent hydrocarbon radical each having from 1 to 18 carbon atoms, M is selected from the class consisting of R'(SR"')y, and wherein R' is selected from the group consisting of a substituted and unsubstituted divalent, trivalent and tetravalent hydrocarbon radical having from 1 to 18 carbon atoms, a hydrocarbon ether, a hydrocarbon thioether, a hydrocarbon ester, and a hydrocarbon thioester in which R' is attached to a silicon atom via a silicon-carbon bond, R" is selected from the group consisting of hydrogen and a monovalent hydrocarbon radical having from 1 to 18 carbon atoms, R"' is selected from the group consisting of R" and a radical represented by the formula R""X, wherein X is a radical selected from the group consisting of , , OH and a cyanoalkyl radical, R"" is a divalent hydrocarbon radical free of aliphatic unsaturation having from 1 to 18 carbon atoms, and when M is R'(SR"')y, at least one R"' is hydrogen, a is a number of from 0 to 6 and y is a number of from 1 to 3.
wherein R is selected from the group consisting of a monovalent hydro-carbon radical and a halogenated monovalent hydrocarbon radical each having from 1 to 18 carbon atoms, M is selected from the class consisting of R'(SR"')y, and wherein R' is selected from the group consisting of a substituted and unsubstituted divalent, trivalent and tetravalent hydrocarbon radical having from 1 to 18 carbon atoms, a hydrocarbon ether, a hydrocarbon thioether, a hydrocarbon ester, and a hydrocarbon thioester in which R' is attached to a silicon atom via a silicon-carbon bond, R" is selected from the group consisting of hydrogen and a monovalent hydrocarbon radical having from 1 to 18 carbon atoms, R"' is selected from the group consisting of R" and a radical represented by the formula R""X, wherein X is a radical selected from the group consisting of , , OH and a cyanoalkyl radical, R"" is a divalent hydrocarbon radical free of aliphatic unsaturation having from 1 to 18 carbon atoms, and when M is R'(SR"')y, at least one R"' is hydrogen, a is a number of from 0 to 6 and y is a number of from 1 to 3.
9. The composition of claims 2, 3 or 4 wherein the thio-functional polysiloxane fluid is prepared in the presence of a hydro-carbon solvent.
10. The composition of claims 2, 3 or 4 wherein the thio-functional polysiloxane fluid is prepared in the presence of a hydro-carbon solvent, said solvent being heptane.
11. The composition of claims 2, 3 or 4 wherein the thio-functional polysiloxane fluid is prepared at a temperature up to 200°C.
12. The composition of claims 2, 3 or 4 wherein the thio-functional polysiloxane fluid is prepared in the presence of a protic compound.
13. The composition of claims 2, 3 or 4 wherein the organodi-siloxane is hexamethyldisiloxane.
14. The composition of claims 2, 3 or 4 wherein the disiloxane is di(3-mercaptopropyl)tetramethyldisiloxane.
15. The composition of claims 2, 3 or 4 wherein the cyclic trisiloxane is hexamethylcyclotrisiloxane.
16. The composition of claims 2, 3 or 4 wherein the silicon compound is a mercaptoalkylhydrocarbonoxysilane.
17. The composition of claims 2, 3 or 4 wherein the silicon compound is mercaptopropyltrimethoxysilane.
18. The composition of claims 2, 3 or 4 which contains an inert organic solvent.
19. The composition of claims 2, 3 or 4 wherein the organo-polysiloxane is a polydimethylsiloxane fluid.
20. A method for rendering a metal corrosion resistant which comprises: applying a composition containing (1) from 10 to 99.9 per-cent by weight of an organopolysiloxane and (2) from 90 to 0.1 percent by weight of a thiofunctional polysiloxane having at least one mercaptan group per molecule in an amount based on the weight of the organopoly-siloxane (1) and thiofunctional polysiloxane (2) to a metal surface and thereafter heating the coated surface to an elevated temperature.
21. The method of claim 16 which comprises applying a composi-tion as claimed in claims 2, 3 or 4.
22. A method for imparting release properties to a metal sur-face which comprises: applying a composition containing (1) from 10 to 99.9 percent by weight of an organopolysiloxane and (2) from 90 to 0.1 percent by weight of a thiofunctional polysiloxane having at least one mercaptan group per molecule based on the weight of the organopolysilox-ane (1) and thiofunctional polysiloxane (2) to the metal surface.
23. The method of claim 22 which comprises applying a composi-tion as claimed in claims 2, 3 or 4.
24. The method of claim 23 wherein the coated metal surface is heated to an elevated temperature.
25. An improved method for obtaining multiple release in preparation of molded articles by applying a moldable material to a mold surface and allowing the resultant material to solidify, the improvement which comprises: applying a release composition to said mold surface, said release composition containing (1) from 10 to 99.9 percent by weight of an organopolysiloxane and (2) from 90 to 0.1 percent by weight of a thiofunctional polysiloxane having at least one mercaptan group per molecule based on the weight of the organopolysiloxane (1) and the thio-functional polysiloxane fluid (2).
26. The method of claim 25 which comprises applying a composi-tion as claimed in claims 2, 3 or 4.
27. The improved process of claim 26 wherein the moldable material is the reaction product of an organic polysisocyanate and an organic compound having at least two groups bearing Zerewitinoff active hydrogen atoms.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US64440475A | 1975-12-29 | 1975-12-29 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1073323A true CA1073323A (en) | 1980-03-11 |
Family
ID=24584777
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA268,219A Expired CA1073323A (en) | 1975-12-29 | 1976-12-20 | Compositions containing thiofunctional polysiloxanes |
Country Status (10)
| Country | Link |
|---|---|
| JP (3) | JPS6045222B2 (en) |
| AT (1) | AT358279B (en) |
| AU (1) | AU506914B2 (en) |
| BE (1) | BE849895A (en) |
| CA (1) | CA1073323A (en) |
| DE (1) | DE2656828C2 (en) |
| FR (1) | FR2337180A1 (en) |
| GB (1) | GB1570780A (en) |
| IT (1) | IT1066797B (en) |
| NL (1) | NL184011C (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5695614A (en) * | 1979-12-28 | 1981-08-03 | Kitsudo:Kk | Manufacture of plastic mold for self separating type plastic molding |
| JPS5827809B2 (en) * | 1980-01-29 | 1983-06-11 | エス ダブリユ エス シリコンス コ−ポレ−シヨン | Thiofunctional polysiloxane polymer and method for producing the same |
| JPS5959759A (en) * | 1982-09-30 | 1984-04-05 | Pentel Kk | Solid painting material |
| JPS62109895A (en) * | 1985-11-06 | 1987-05-21 | Toray Silicone Co Ltd | Surface treating agent composition for rubber |
| GB9619139D0 (en) | 1996-09-13 | 1996-10-23 | Unilever Plc | Process for stamping detergent bars |
| WO2007053051A1 (en) * | 2005-11-03 | 2007-05-10 | Oleg Leonidovich Kulikov | Method of processing of a thermoplastic polymeric material, material by using a coated die |
| JP6034170B2 (en) * | 2012-12-07 | 2016-11-30 | 東芝電子管デバイス株式会社 | X-ray tube device and method for manufacturing the same |
| CN112831274B (en) * | 2021-02-24 | 2022-01-28 | 烟台大学 | Hydrosulphonyl-terminated polysiloxane water-based release agent |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1102251A (en) * | 1964-02-04 | 1968-02-07 | Union Carbide Corp | Treatment of metal surfaces |
| US4029827A (en) * | 1974-07-24 | 1977-06-14 | Xerox Corporation | Mercapto functional polyorganosiloxane release agents for fusers in electrostatic copiers |
| GB2139392B (en) * | 1983-05-05 | 1986-10-22 | Standard Telephones Cables Ltd | Display device |
-
1976
- 1976-12-08 NL NLAANVRAGE7613658,A patent/NL184011C/en not_active IP Right Cessation
- 1976-12-15 DE DE2656828A patent/DE2656828C2/en not_active Expired
- 1976-12-20 CA CA268,219A patent/CA1073323A/en not_active Expired
- 1976-12-21 IT IT52712/76A patent/IT1066797B/en active
- 1976-12-23 AU AU20851/76A patent/AU506914B2/en not_active Expired
- 1976-12-23 GB GB53945/76A patent/GB1570780A/en not_active Expired
- 1976-12-28 JP JP51160966A patent/JPS6045222B2/en not_active Expired
- 1976-12-28 BE BE173667A patent/BE849895A/en not_active IP Right Cessation
- 1976-12-28 AT AT971976A patent/AT358279B/en not_active IP Right Cessation
- 1976-12-28 FR FR7639237A patent/FR2337180A1/en active Granted
-
1977
- 1977-03-28 JP JP3344477A patent/JPS53102364A/en active Pending
- 1977-03-28 JP JP3344377A patent/JPS5394518A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| DE2656828C2 (en) | 1982-05-06 |
| NL7613658A (en) | 1977-07-01 |
| NL184011B (en) | 1988-10-17 |
| IT1066797B (en) | 1985-03-12 |
| AT358279B (en) | 1980-08-25 |
| AU2085176A (en) | 1978-06-29 |
| JPS5282956A (en) | 1977-07-11 |
| JPS5394518A (en) | 1978-08-18 |
| AU506914B2 (en) | 1980-01-31 |
| JPS6045222B2 (en) | 1985-10-08 |
| FR2337180B1 (en) | 1981-06-19 |
| FR2337180A1 (en) | 1977-07-29 |
| ATA971976A (en) | 1980-01-15 |
| DE2656828A1 (en) | 1977-07-07 |
| GB1570780A (en) | 1980-07-09 |
| NL184011C (en) | 1989-03-16 |
| JPS53102364A (en) | 1978-09-06 |
| BE849895A (en) | 1977-06-28 |
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| Date | Code | Title | Description |
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| MKEX | Expiry |