CA2018002A1 - Curable silicone caulk compositions - Google Patents
Curable silicone caulk compositionsInfo
- Publication number
- CA2018002A1 CA2018002A1 CA002018002A CA2018002A CA2018002A1 CA 2018002 A1 CA2018002 A1 CA 2018002A1 CA 002018002 A CA002018002 A CA 002018002A CA 2018002 A CA2018002 A CA 2018002A CA 2018002 A1 CA2018002 A1 CA 2018002A1
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- CA
- Canada
- Prior art keywords
- parts
- curable silicone
- silanol
- radicals
- linker
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
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Abstract
CURABLE SILICONE CAULK COMPOSITIONS
Abstract of the Disclosure Curable silicone caulk compositions are provided using a nonionically stabilized silanol-terminated polydi-organosiloxane, water, a silane cross-linker, a tin condensa-tion catalyst, and calcium carbonate.
Abstract of the Disclosure Curable silicone caulk compositions are provided using a nonionically stabilized silanol-terminated polydi-organosiloxane, water, a silane cross-linker, a tin condensa-tion catalyst, and calcium carbonate.
Description
2~8~2 RD-ig 814 K C _ ~ QS T T~ 5 R~-e~.c~_t ~Rel~_~ ReQlica~i~n This applica~ion is a continuation in part of copending ap~lication Serial No. 200,482, filed May 3, 1988.
Bac~ou~1 of the ~vent~o~
Prior to the present invention, curable silicone emulsions providing a~ elastomer upon water removal were shown by J.F. Hyde et al., U.S. Patent 2,891,920. It was found that the compositions of Hyde e~ al. required either a strong acid or a strong base to achieve stability of the emulsion. As a result, Hyde et al.'s silicone emulsions were limited in use due to their adverse effects on various sub-strates. Improved results are shown by D.E. Findlay et al., U.S. Patent 3,294,725, employing a surface acti~e sulfonic acid catalyst to achieve a stable emulsion and allow for the copolymerization of organosiloxanes and silacarbanes. An additional procedure for making silicon rubber latexes is shown by J. Cekada, vr., U.S. Patent 3,355,406, utllizing silsesquioxanes to reinforce the polymer.
The present invention is based on the discovery that stable aqueous curable silicone latex compositicns can be made by initially emulsifying silanol-terminated poly-diorganosiloxane in the presence of a nonionic surfactant, such as an alkylaryloxypoly(ethyleneoxy)ethanol followed by a pH adjus~ment up to 5 with a carboxylic acid, such as suc-cinic acid. Also used in the emulsion are alkyltrialkoxysi-2S lane, for example methyltrimethoxysilane and a tin catalyst,such as a stannoxane, hydroxystannoxane, or a monomethoxy tin compound. Among the preferred tin compounds are stannoxanes of the formula, ~ 8~ 19,814 (R)2SnX-O-Sn(Rl)2OH , (l) where R and R1 are selected from the same or differen~ C(l-a) alkyl radicals, and p-eferably butyl, and X is a halocen rad-ical, or an acyloxy radical, and is preferably chloro.
S In aàdition, calcium carbona~e is utilized in the resulting curable silicone composltion. The resulting sili-cone caulk has been found to have superior shelf life, such as six months or more, and elastomers resulting from the removal of water from such caulking compounds have been found to have excellent physical properties.
S~ ~n~ ^ f t~ ~ e ~ r - ^ n There is p-o~ided by the presen~ invention, a sili-cone caulking composit`on comprising by weight, (A) lO0 parts of a base formulation consisting essentially of an aqueous emulsion having 40 to 60% by weight solids and a pH in the range of about 4 to 6, of a silanol-terminate~ poly-diorganosiloxane having a molecular weight of about sx103 to about 15x103, and an effective amount of a nonionic surfàctant, (B) O.l to 5 parts and preferably 0.5 to l.S part of a silane cross-linker, (C) 25 to 70 parts of calcium carbonate, and (~) 0.3 to 2 parts and preferably 0.4 to l.5 part of a stannoxane catalyst.
The aoueous emulsion of the silanol-terminated polydiorganosiloxane are preferably made by agitating a lin-ear silanol-terminated polydiorganosiloxane in an aqueous RD-1~,814 ;2r)18~)0~
medla ln the presence of 1~ to 5~ by weight of total e~ulsion of a nonionic surfactant. The pH or the emulsion can be adjusted to 4 to 6 by add ng a sarboxylic acid such as s~c-cinic acid.
The silanol-terminated polydiorganosiloxanes wnich can be used in the practice of the present invention have organo radicals attached to silicon which are selected f~om C~ 3), monovalent hydrocarbon radicals, and C~l_l3) monova-lent hydrocarbon radicals substi~uted with radicals inert during equilibration. Some of the organo radicals a_e, or example, C(l-8) alkyl radicals such as methyl, ethyl, ?ro?yl, butyl, pentyl, hexyl; haloalkyl radicals such as ~- 'uoro-propyl; and cyanoal~yl radicals such as cyanoethyi and cyano-propyl. In addition, the organo radicals attached to silicon can be selected f-o~ alkenyl radicals such as vinyl -adicals;
allyl radicals; alkylaryl radicals such as ethyl, phenyl; ar.d - arylalkyl radicals such as tolyl, xylyl, etc. The monovalent organo radicals also can be aryl radicals such as phenyl, halophenyl such as chlorophenyl, bromophenyl, naphthyl -adi-2C cals, anthryl radicals, etc.
Silanol-~e-minated polydiorganosiloxanes useful in the practice of the invention are shown by W. Noll, "Che~is-try and Technology of Sillcones", Academic P_ess, ~ew York (1968) p. 2~0. They can be prepared by the polymerization of 2~ cyclic siloxanes, such as octamethyltetracyclosiloxanes, using acidic or basic catalysts. These silanolorganosilox-anes can be e~ulsified in water with nonionic emulsifying agents, such as alkylaryloxypoly(etheneoxy)ethanol. Useful nonionic emulsifying agents are the nonionic surfactant which can be used in the practice of the invention are, 'or exam-ple, saponins, condensation products of fatty acids with ethyleneoxide such as dodecylether of tetraethyleneoxide, anà
Z n ~ 2 ~3-13,814 condensation products of e~hyleneoxlde with sorbitan t-i-oleate.
Acldic colloidal silica also can be used in the practice of the invention in the silicone caulking comDosi-tion which can be present at from 1 to 10 percent based ontotal weigAt of comoosition.
There is also u~ilized in the caulking composition of the present invention, a trialkoxyorganosilane cross-linker, such as methyltrimethoxysilane, to erfect a satisfac-tory cure in the resulting elastomer. Additional tr~alkoxy-organosiloxanes are, for example, methyltrie~hoxysilane, e~hyltriethoxysilane, and methyltr propoxysllane.
The caulk composltions of the present inven~ion have been found to have optimum shelf s~ability when there s employed from about 0.3% to 0.6% by weight of stannoxane o.
formula (1). Stannoxanes of formula (1) and method fo- mak-ing are shown by U.S. Patent 3,664,997. Preferably, he stannoxanes of formula (1) include compounds such as (C4H7)2SnCl-O-(C4H7)2SnOH, and Q
(C4H7)2Sn(OCCH3)-O(C4H7)2SnOH .
Other tin compounds which can be used are, ~or example, o (C4H7)25n(O~CH3)(OCH3).
In order that those skilled in the art will be be~-ter able ~o practice the present nven~on, the following example is given by way of illustration and not by way of limitation. ~ll par~s are by weight.
2~8~ RD-19,814 Example A base emulsion is prepared by passing through a Gaulin homogenizer a mixture of a~out S000 grams of a silanol-terminated polydimethylsilxoane, about S000 grams of water and about 200 grams of polyethylene glycol ether. Thè
p~ of the resulting mlxture is adjusted by adding up to 200 grams of succinic acid. There is obtained a base formulation having about 60~ solids and a pH of 4-5 of a silanol-termi-nated polydimethylsiloxane having an MW of about 10,000.
A mixture of lS00 g of the above base formulation is blended with 900 grams of ground calcium carbonate in a Ross double planetary mixer for 30-60 m nutes, degassed, passed through a high shear Semco mixer for 15 minutes, and dispensed in~o anaerobic cartridges.
lS The above cartridges containing the base mixture are then catalyzed by injecting them with methyltzimethoxysi-lane, and in certain cases, acidic colloidal silica, along with toluene, and a tin curing catalyst. The following cur-able mixtures are prepared, which are shown in grams based on 100 parts of the base mixture, where "MTMS" is methyltrimeth-oxysilane, "bu" is butyl, and "Laur" is CH3(CH2)10C- :
2~ 3C3~
~ 3 ~I 5 MTMS 0.5 0.5 0.5 0.5 0.5 0.5 toluene _ _ _ _ 1.0 1.0 colloidal silica _ 3.0 _ _ 3.0 5 bu2Sn~O~aur)2 0.33 _ _ _ _ bu2Sn(OMe))Laur) _ 0.5 0.5 _ _ [bu2Sn(OLaur)2O _ _ _ 0.5 _ bu2SnCl-O-Snbu7O~ _ _ _ _ _ 0.5 0.5 The materials are thoroughly mixed using a Semkit mixer. the materials are then cured for one week prior to tensile property measurement. Tensile properties are meas-ured according to ASTM Standard D412 and the following results are obtained, where Shore A is hardness, and TS is tensile strength:
15 _ 1 _ 2 3 4 5 6 5~o~e A 19 (251~ 2s(28)~ 17 (12~ -22 ~2~ '14 ~15) 15~12)~
TS (p~i) 93(76)178(166)130(108)148(118)162(181)159(187) Strain (~) 398(219) 551t527) 638(625)513(501)595 (6B21 6s6t694) * Numbers in parentheses refer to pro~erties obtained from materials aged in the tube for two weeks and a one week cure period.
** Numbers in parentheses refer to properties obtained from materials aged in the tube for one month and one week cure period.
5 **~ Numbers in parentheses refer to pro?erties obtained from materials aged in the tube for two months and one week cure period.
RD-i9 814 8~)0;2 The above results show t:hat the stannoxanes are valuable condensation catalysts and materials formulated with these catalysts maintain their elonga~lon upon aging.
Although the above resu:Lts are directed to only a few of the very many variables which can be used in the prac-tice of the present invention, it should be understood that the present invention is directed to a much broader variety of caulk compositions utilizing stannoxanes, sllanol-termi-nated polydiorganosiloxanes, cross-linking silanes, as shown in the description preceding these examples.
Bac~ou~1 of the ~vent~o~
Prior to the present invention, curable silicone emulsions providing a~ elastomer upon water removal were shown by J.F. Hyde et al., U.S. Patent 2,891,920. It was found that the compositions of Hyde e~ al. required either a strong acid or a strong base to achieve stability of the emulsion. As a result, Hyde et al.'s silicone emulsions were limited in use due to their adverse effects on various sub-strates. Improved results are shown by D.E. Findlay et al., U.S. Patent 3,294,725, employing a surface acti~e sulfonic acid catalyst to achieve a stable emulsion and allow for the copolymerization of organosiloxanes and silacarbanes. An additional procedure for making silicon rubber latexes is shown by J. Cekada, vr., U.S. Patent 3,355,406, utllizing silsesquioxanes to reinforce the polymer.
The present invention is based on the discovery that stable aqueous curable silicone latex compositicns can be made by initially emulsifying silanol-terminated poly-diorganosiloxane in the presence of a nonionic surfactant, such as an alkylaryloxypoly(ethyleneoxy)ethanol followed by a pH adjus~ment up to 5 with a carboxylic acid, such as suc-cinic acid. Also used in the emulsion are alkyltrialkoxysi-2S lane, for example methyltrimethoxysilane and a tin catalyst,such as a stannoxane, hydroxystannoxane, or a monomethoxy tin compound. Among the preferred tin compounds are stannoxanes of the formula, ~ 8~ 19,814 (R)2SnX-O-Sn(Rl)2OH , (l) where R and R1 are selected from the same or differen~ C(l-a) alkyl radicals, and p-eferably butyl, and X is a halocen rad-ical, or an acyloxy radical, and is preferably chloro.
S In aàdition, calcium carbona~e is utilized in the resulting curable silicone composltion. The resulting sili-cone caulk has been found to have superior shelf life, such as six months or more, and elastomers resulting from the removal of water from such caulking compounds have been found to have excellent physical properties.
S~ ~n~ ^ f t~ ~ e ~ r - ^ n There is p-o~ided by the presen~ invention, a sili-cone caulking composit`on comprising by weight, (A) lO0 parts of a base formulation consisting essentially of an aqueous emulsion having 40 to 60% by weight solids and a pH in the range of about 4 to 6, of a silanol-terminate~ poly-diorganosiloxane having a molecular weight of about sx103 to about 15x103, and an effective amount of a nonionic surfàctant, (B) O.l to 5 parts and preferably 0.5 to l.S part of a silane cross-linker, (C) 25 to 70 parts of calcium carbonate, and (~) 0.3 to 2 parts and preferably 0.4 to l.5 part of a stannoxane catalyst.
The aoueous emulsion of the silanol-terminated polydiorganosiloxane are preferably made by agitating a lin-ear silanol-terminated polydiorganosiloxane in an aqueous RD-1~,814 ;2r)18~)0~
medla ln the presence of 1~ to 5~ by weight of total e~ulsion of a nonionic surfactant. The pH or the emulsion can be adjusted to 4 to 6 by add ng a sarboxylic acid such as s~c-cinic acid.
The silanol-terminated polydiorganosiloxanes wnich can be used in the practice of the present invention have organo radicals attached to silicon which are selected f~om C~ 3), monovalent hydrocarbon radicals, and C~l_l3) monova-lent hydrocarbon radicals substi~uted with radicals inert during equilibration. Some of the organo radicals a_e, or example, C(l-8) alkyl radicals such as methyl, ethyl, ?ro?yl, butyl, pentyl, hexyl; haloalkyl radicals such as ~- 'uoro-propyl; and cyanoal~yl radicals such as cyanoethyi and cyano-propyl. In addition, the organo radicals attached to silicon can be selected f-o~ alkenyl radicals such as vinyl -adicals;
allyl radicals; alkylaryl radicals such as ethyl, phenyl; ar.d - arylalkyl radicals such as tolyl, xylyl, etc. The monovalent organo radicals also can be aryl radicals such as phenyl, halophenyl such as chlorophenyl, bromophenyl, naphthyl -adi-2C cals, anthryl radicals, etc.
Silanol-~e-minated polydiorganosiloxanes useful in the practice of the invention are shown by W. Noll, "Che~is-try and Technology of Sillcones", Academic P_ess, ~ew York (1968) p. 2~0. They can be prepared by the polymerization of 2~ cyclic siloxanes, such as octamethyltetracyclosiloxanes, using acidic or basic catalysts. These silanolorganosilox-anes can be e~ulsified in water with nonionic emulsifying agents, such as alkylaryloxypoly(etheneoxy)ethanol. Useful nonionic emulsifying agents are the nonionic surfactant which can be used in the practice of the invention are, 'or exam-ple, saponins, condensation products of fatty acids with ethyleneoxide such as dodecylether of tetraethyleneoxide, anà
Z n ~ 2 ~3-13,814 condensation products of e~hyleneoxlde with sorbitan t-i-oleate.
Acldic colloidal silica also can be used in the practice of the invention in the silicone caulking comDosi-tion which can be present at from 1 to 10 percent based ontotal weigAt of comoosition.
There is also u~ilized in the caulking composition of the present invention, a trialkoxyorganosilane cross-linker, such as methyltrimethoxysilane, to erfect a satisfac-tory cure in the resulting elastomer. Additional tr~alkoxy-organosiloxanes are, for example, methyltrie~hoxysilane, e~hyltriethoxysilane, and methyltr propoxysllane.
The caulk composltions of the present inven~ion have been found to have optimum shelf s~ability when there s employed from about 0.3% to 0.6% by weight of stannoxane o.
formula (1). Stannoxanes of formula (1) and method fo- mak-ing are shown by U.S. Patent 3,664,997. Preferably, he stannoxanes of formula (1) include compounds such as (C4H7)2SnCl-O-(C4H7)2SnOH, and Q
(C4H7)2Sn(OCCH3)-O(C4H7)2SnOH .
Other tin compounds which can be used are, ~or example, o (C4H7)25n(O~CH3)(OCH3).
In order that those skilled in the art will be be~-ter able ~o practice the present nven~on, the following example is given by way of illustration and not by way of limitation. ~ll par~s are by weight.
2~8~ RD-19,814 Example A base emulsion is prepared by passing through a Gaulin homogenizer a mixture of a~out S000 grams of a silanol-terminated polydimethylsilxoane, about S000 grams of water and about 200 grams of polyethylene glycol ether. Thè
p~ of the resulting mlxture is adjusted by adding up to 200 grams of succinic acid. There is obtained a base formulation having about 60~ solids and a pH of 4-5 of a silanol-termi-nated polydimethylsiloxane having an MW of about 10,000.
A mixture of lS00 g of the above base formulation is blended with 900 grams of ground calcium carbonate in a Ross double planetary mixer for 30-60 m nutes, degassed, passed through a high shear Semco mixer for 15 minutes, and dispensed in~o anaerobic cartridges.
lS The above cartridges containing the base mixture are then catalyzed by injecting them with methyltzimethoxysi-lane, and in certain cases, acidic colloidal silica, along with toluene, and a tin curing catalyst. The following cur-able mixtures are prepared, which are shown in grams based on 100 parts of the base mixture, where "MTMS" is methyltrimeth-oxysilane, "bu" is butyl, and "Laur" is CH3(CH2)10C- :
2~ 3C3~
~ 3 ~I 5 MTMS 0.5 0.5 0.5 0.5 0.5 0.5 toluene _ _ _ _ 1.0 1.0 colloidal silica _ 3.0 _ _ 3.0 5 bu2Sn~O~aur)2 0.33 _ _ _ _ bu2Sn(OMe))Laur) _ 0.5 0.5 _ _ [bu2Sn(OLaur)2O _ _ _ 0.5 _ bu2SnCl-O-Snbu7O~ _ _ _ _ _ 0.5 0.5 The materials are thoroughly mixed using a Semkit mixer. the materials are then cured for one week prior to tensile property measurement. Tensile properties are meas-ured according to ASTM Standard D412 and the following results are obtained, where Shore A is hardness, and TS is tensile strength:
15 _ 1 _ 2 3 4 5 6 5~o~e A 19 (251~ 2s(28)~ 17 (12~ -22 ~2~ '14 ~15) 15~12)~
TS (p~i) 93(76)178(166)130(108)148(118)162(181)159(187) Strain (~) 398(219) 551t527) 638(625)513(501)595 (6B21 6s6t694) * Numbers in parentheses refer to pro~erties obtained from materials aged in the tube for two weeks and a one week cure period.
** Numbers in parentheses refer to properties obtained from materials aged in the tube for one month and one week cure period.
5 **~ Numbers in parentheses refer to pro?erties obtained from materials aged in the tube for two months and one week cure period.
RD-i9 814 8~)0;2 The above results show t:hat the stannoxanes are valuable condensation catalysts and materials formulated with these catalysts maintain their elonga~lon upon aging.
Although the above resu:Lts are directed to only a few of the very many variables which can be used in the prac-tice of the present invention, it should be understood that the present invention is directed to a much broader variety of caulk compositions utilizing stannoxanes, sllanol-termi-nated polydiorganosiloxanes, cross-linking silanes, as shown in the description preceding these examples.
Claims (5)
1. A silicone latex composition comprising by weight, (A) 100 parts of a base formulation consisting essentially of an aqueous emulsion having 40 to 60% by weight solids and a pH in the range of about 4 to 6, of a silanol-terminated poly-diorganosiloxane and an effective amount of a nonionic surfactant, (B) 0.1 to 5 parts a of a silane cross-linker, (C) 25 to 70 parts of calcium carbonate, and (D) 0.3 to 2 parts of a stannoxane catalyst.
2. A caulk composition in accordance with claim 1, where the polydiorganosiloxane is a silanol-terminated polydimethylsiloxane.
3. A caulk composition in accordance with claim 1, where the stannoxane is .
4. A caulk composition in accordance with claim 1, where the silane cross-linker is methyltrimethoxysilane.
5. The invention as defined in any of the preceding claims including any further features of novelty disclosed.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US07/416,340 US5034455A (en) | 1988-05-31 | 1989-10-03 | Curable silicone caulk compositions |
| US416,340 | 1989-10-06 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2018002A1 true CA2018002A1 (en) | 1991-12-08 |
Family
ID=23649558
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002018002A Abandoned CA2018002A1 (en) | 1989-10-03 | 1990-05-31 | Curable silicone caulk compositions |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA2018002A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10513609B2 (en) | 2013-06-25 | 2019-12-24 | Dow Global Technologies Llc | Polyolefin elastomer and polysiloxane blends |
-
1990
- 1990-05-31 CA CA002018002A patent/CA2018002A1/en not_active Abandoned
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10513609B2 (en) | 2013-06-25 | 2019-12-24 | Dow Global Technologies Llc | Polyolefin elastomer and polysiloxane blends |
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