CA1225767A - Organosiloxane-oxyalkylene copolymers - Google Patents
Organosiloxane-oxyalkylene copolymersInfo
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- CA1225767A CA1225767A CA000454428A CA454428A CA1225767A CA 1225767 A CA1225767 A CA 1225767A CA 000454428 A CA000454428 A CA 000454428A CA 454428 A CA454428 A CA 454428A CA 1225767 A CA1225767 A CA 1225767A
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- organosiloxane
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- 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
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
- C08G77/46—Block-or graft-polymers containing polysiloxane sequences containing polyether sequences
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Organic Chemistry (AREA)
- Silicon Polymers (AREA)
- Paints Or Removers (AREA)
Abstract
Abstract of the Disclosure ORGANOSILOXANE-OXYALKYLENE COPOLYMERS
Organosiloxane-oxyalkylene copolymers in which at least one silicon atom of an organosiloxane unit has attached thereto a group -X(OR)nO?iR'(OR")2-a in which X is a divalent hydrocarbon group, R is an alkylene group, n is an integer of at least 2, Z is an organic substi-tuent containing an epoxy group, R' is lower alkyl, vinyl or phenyl, R" is alkyl or alkoxyalkyl and a is 0 or 1, at least 40 percent of the total substituents in the copolymer being methyl.
The copolymers are film forming and may be applied to contlnuous or porous substrates from aqueous or non-aqueous solutions.
Organosiloxane-oxyalkylene copolymers in which at least one silicon atom of an organosiloxane unit has attached thereto a group -X(OR)nO?iR'(OR")2-a in which X is a divalent hydrocarbon group, R is an alkylene group, n is an integer of at least 2, Z is an organic substi-tuent containing an epoxy group, R' is lower alkyl, vinyl or phenyl, R" is alkyl or alkoxyalkyl and a is 0 or 1, at least 40 percent of the total substituents in the copolymer being methyl.
The copolymers are film forming and may be applied to contlnuous or porous substrates from aqueous or non-aqueous solutions.
Description
~57~7 ORGANOSILOXANE-OXYALKYLENE COPOLYMERS
This invention relates to copolymers comprising organosiloxane units and oxyalkylene units, and also re-lates to a process ~or preparing such copolymers.
Copolymers comprising siloxane units and oxyalkylene units are now well known and have been commercially employed in applications such as surfactants for polyure-thane foams and as textile fibre lubricants. In U.K.
Patent 1 29C 687 there are disclosed siloxane-polyoxyalk-ylene block copolymers in which there are present methoxy groups attached to silicon atoms. It is stated in the said patent that a preferred application of the block co-polymers is in the treatment of hydrophobic fibres to improve their soil resistance. European Patent Applica-tion 32 310 also discloses copolymers containing siloxane units, oxyalkylene units and silicon-bonded hydrolysable groups, and the use of such cGpolymers for treating textiles. In the above described prior art copolymers the methoxy groups or hydrolysable groups are attached to a silicon atom in the siloxane chain either directly or by way of an aliphatic hydrocarbon linkage.
According to the present invention there are pro-vided organosiloxane-oxyalkylene copolymers wherein at least one silicon atom of an organosiloxane unit has attached thereto a group represented by the general
This invention relates to copolymers comprising organosiloxane units and oxyalkylene units, and also re-lates to a process ~or preparing such copolymers.
Copolymers comprising siloxane units and oxyalkylene units are now well known and have been commercially employed in applications such as surfactants for polyure-thane foams and as textile fibre lubricants. In U.K.
Patent 1 29C 687 there are disclosed siloxane-polyoxyalk-ylene block copolymers in which there are present methoxy groups attached to silicon atoms. It is stated in the said patent that a preferred application of the block co-polymers is in the treatment of hydrophobic fibres to improve their soil resistance. European Patent Applica-tion 32 310 also discloses copolymers containing siloxane units, oxyalkylene units and silicon-bonded hydrolysable groups, and the use of such cGpolymers for treating textiles. In the above described prior art copolymers the methoxy groups or hydrolysable groups are attached to a silicon atom in the siloxane chain either directly or by way of an aliphatic hydrocarbon linkage.
According to the present invention there are pro-vided organosiloxane-oxyalkylene copolymers wherein at least one silicon atom of an organosiloxane unit has attached thereto a group represented by the general
2~ formula z -X(OR)nOsiR a(OR )2-a wherein X represents a divalent hydrocarbon group having from 2 to 8 carbon atoms, R represents an alkylene group having from 2 to 4 carbon atoms, n is an integer of at least 2, Z represents an organic group composed of 7~7 carbon, hydrogen and oxygen and having therein at least one epoxy group, R' represents a lower alkyl, vinyl or phenyl group, R" represents an alkyl or an alkoxyalkyl group having less than 7 carbon atoms and a has a value of 0 or 1, the remaining silicon-bonded substituents in the organosiloxane units being selecte~ from hydrogen atoms, monovalent hydrocarbon groups and groups represen-ted by the general formula -X(OR)nOG
wherein X and R are as hereinabove defined and G repres-ents a hydrogen atom, a monovalent hydrocarbon group having from 1 to 10 carbon atoms or an acyl group having from 2 to 6 carbon atoms, at least 40 percent of the total substituents bonded to siloxane silicon atoms in the copolymer being methyl.
In the general formula above ~(OR)n~ represents an oxyalkylene block having at least 2, preferabl~ from 2 to 50 oxyalkylene units OR. The oxyalkylene units are pref-erably oxyethylene or oxypropylene or combinations of the two, for example -(OC2H4)6(OC3H6)6-. The group X which links the oxyalkylene block to the siloxane silicon atom may have from 2 to 8 carbons, but, in view of the more ready availability of the polyoxyalkylene precursor, is preferably the propylene group -(CH2)3.
The substituent Z is an epoxidised monovalent organic group composed of carbon, hydrogen and oxygen.
o Examples of such groups include the group -CH2CH
and those represented by the general formula / O\
wherein Q represents a divalent hydrocarbon group e.g.
ethylene, butylene, phenylene, cyclohexylene and ~2 -CH2C~ ~ or an ether oxygen-containing group such as -CH2C~12OCH2CH2 and -CH2C~2OC~(CH3)CH2-. Pr~ferably Z
,,~ O~
represents the group -(CH2)3OCH2CH - CH2.
S As the R" groups there may be present any alkyl or alkoxyalkyl group havlng less than 7 carbon atoms e.g.
methyl, ethyl, propyl, methoxyethyl and ethoxyethyl, the preferred copolymers being those wherein R" represents methyl, ethyl or methoxyethyl. The R' groups, when pre-sent, may be Cl 4 alkyl, vinyl or phenyl.
At least one of the above oxyalkylene containing groups should be present in the copolymer. The number present in any particular case will depend upon such factors as the size of the copolymer molecule desired and the balance sought between the properties bestowed by the siloxane and oxyalkylene portions. The remaining substi-tuents on the siloxane silicon atoms may be selected from hydrogen atoms, monovalent hydrocarbon groups e.g. ethyl, propyl, 2,4,4-trimethylpentyl, vinyl, allyl and phenyl and silicon-free oxyalkylene groups of the formula -X(OR)nOG, wherein G is for example ethyl, butyl or acetyl; with the proviso that at least 40 percent of the total siloxane silicon-bonded substituents are methyl groups. The preferred copolymers of this invention are those wherein the oxyalkylene groups (OR)n are oxyethyl-ene and comprise at least 35% of the total weight of the copolymer.
The copolymers of this invention may take any of the molecular configurations available to such copolymers provided such configuration is consistent with the pres-ence of terminal silyl groups on the oxyalkylene-contain-ing group or groups. For example, they may be of the ABA
configuration wherein A represents the _ 5 _ ~2 ~ 57 6'~
-X(~R)nosiR a(OR )2-a group and B represents a linear sîloxane portion e.g.
-(M2SiO)b wherein each M individually represents an organic substi~uent such as -CH3 and b is an. integer of at least 2. Alternatively the copolymer may be of the so-called "rake" configuration wherein the oxyalkylene-containing groups are pendant from a siloxane chain as in M IM M M
MSiO--- - SiO- _ -SiO- - SiM
M M A M
Y z in which y is zero or an integer and z is an integer.
According to yet another configuration the oxyalkylene-containing (A) groups may be present both in the pendantpositions and attached to the terminal silicon atoms of the siloxane chain. It will thus be apparent that in addition to the siloxane units having oxyalkylene groups attached thereto the copolymers of this invention may also comprise monofunctional M3SiO~ units, difunctional M2SiO and trifunctional MSiO3/2 units. If desired, small proportions of tetrafunctional SiO2 units may also be present.
The copolymers of this invention can be obtained by reacting together (A) an organosiloxane-oxyalkylet~e copolymer wherein at least one silicon atom of an organo-siloxane unit has attached thereto a group of the general formula -X(OR)nOH
the remaining silicon-bonded substituents in the organo-siloxane units being selected from hydrogen atoms, mono-valent hydrocarbon groups and groups represented by the general formula -X(OR)nOG, at least ~0 percent of the - 6 ~22~i7Ej7 total substituents bonded to siloxane silicon atoms in the copolymer being methyl groups, and (B) an organo-silane ZSiR'a(OR )3-a wherein X, R, ~, R', R" and a are as hereinbefore defined and G represents a monovalent hydrocarbon group having from 1 to 10 carbon atoms or an acyl g:roup having from 2 to 6 carbon atoms.
Organosiloxane-oxyalkylene copolymers (A) employed in the said preparative process are a known class of materials. Such copolymers and methods for their prepa~
ration are described in, for example, British Patents ~02 467 and 1 ll~3 206, The silanes (B) are also known substances and have been disclosed in, for example, British Patent 83~ 326.
Some reaction between (A) and (B) to form the organosiloxane-oxyalkylene copolymers of this invention is believed to occur at normal ambient temperatures. It is preferred, however, to expedite the reaction by the use of higher temperatures, for example, from about 60C
to 180C. If desired the reaction may be carried forward in the presence of a transesterification catalyst, for example zinc tetrafluoroborate, an organic tin compound e.g. stannous octoate or a titanium compound e.g. tetra-2S butyl titanate. Where subsequent reaction of thecopolymer via the epoxy groups is envisaged the preferred catalysts are those which also function to open the epoxy ring e.g. zinc tetrafluoroborate.
The relative molar proportions of the reactants employed may be varied to achieve substantially complete reaction of the available COH groups, or to induce only partial reaction whereby the resulting copolymer product contains both silylated and non-silylated oxyalkylene groups.
~ ~257~7 The molecular weight of the copolymers of this invention may vary widely and the copolymers may range from mobile liquids to gummy or waxy solids. When a sufficient proportion of oxyethylene units is present the copolymers are water-soluble. The copolymers may there-fore be formed into curable films on continuous, porous or fibrous substrates from aqueous or non aqueous solutions. Curing of the copolymers into films will take place in the absence of a curing catalyst. It is, how-ever, generally preferred to accelerate the cure by theaddition of a siloxane condensation catalyst. A wide variety of such catalysts are known and include, for example acids, bases and metal organic compounds such as the ~etal carboxylates e.g. dibutyltin dilaurate, stannous octoate and zinc octoate and titanium alkoxides and chelates. Certain substances e.g. zinc tetrafluoro-borate and stannous octoate can function both as a trans-esterification catalyst during the preparation of the siloxane-oxyalkylene copolymer and subsequently as a curing catalyst therefor.
It is also preferred to effect drying and curing of the films at elevated temperatures. The actual temp-erature employed will depend to some extent on the nature and heat resistance of the substrate, temperatures in the range from about 80C to about 180C being generally appropriate.
If desired the copolymers of the invention may be mixed with fillers, pigments and other additives to produce compositions curable to rubbery solids having paintable surfaces.
The following examples in which Me represents methyl illustrate the invention.
- 8 - ~2 ~ 7 Example 1 To a 20 litre split-necked flask equipped with a stirrer, condenser and thermometer was charged 12,500g of a siloxane-oxyalkylene copolymer of average composition E (CH2C~2)12(cH2)3siMe2Oo 5¦ 2 (SiMe2O)14. The flask was heated to 9QC and a 40~-by weight aqueous solution (26ml) of zinc tetrafluoroborate added and dissolved with stirring. This was follow~d by the addition over 2 minutes of the silane.
/\
(MeO)3Si(CH2)3OCH2CH - CH2 (2458.7g), the reaction mixture then being maintained at 90C for a further 2 hours. On cooling there was obtained 14,870g (99.5%) of a clear, amber, water-soluble liquid.
When an aqueous solution (15% by weight) of the liquid was coated Oll to aluminium and dried at 150C for
wherein X and R are as hereinabove defined and G repres-ents a hydrogen atom, a monovalent hydrocarbon group having from 1 to 10 carbon atoms or an acyl group having from 2 to 6 carbon atoms, at least 40 percent of the total substituents bonded to siloxane silicon atoms in the copolymer being methyl.
In the general formula above ~(OR)n~ represents an oxyalkylene block having at least 2, preferabl~ from 2 to 50 oxyalkylene units OR. The oxyalkylene units are pref-erably oxyethylene or oxypropylene or combinations of the two, for example -(OC2H4)6(OC3H6)6-. The group X which links the oxyalkylene block to the siloxane silicon atom may have from 2 to 8 carbons, but, in view of the more ready availability of the polyoxyalkylene precursor, is preferably the propylene group -(CH2)3.
The substituent Z is an epoxidised monovalent organic group composed of carbon, hydrogen and oxygen.
o Examples of such groups include the group -CH2CH
and those represented by the general formula / O\
wherein Q represents a divalent hydrocarbon group e.g.
ethylene, butylene, phenylene, cyclohexylene and ~2 -CH2C~ ~ or an ether oxygen-containing group such as -CH2C~12OCH2CH2 and -CH2C~2OC~(CH3)CH2-. Pr~ferably Z
,,~ O~
represents the group -(CH2)3OCH2CH - CH2.
S As the R" groups there may be present any alkyl or alkoxyalkyl group havlng less than 7 carbon atoms e.g.
methyl, ethyl, propyl, methoxyethyl and ethoxyethyl, the preferred copolymers being those wherein R" represents methyl, ethyl or methoxyethyl. The R' groups, when pre-sent, may be Cl 4 alkyl, vinyl or phenyl.
At least one of the above oxyalkylene containing groups should be present in the copolymer. The number present in any particular case will depend upon such factors as the size of the copolymer molecule desired and the balance sought between the properties bestowed by the siloxane and oxyalkylene portions. The remaining substi-tuents on the siloxane silicon atoms may be selected from hydrogen atoms, monovalent hydrocarbon groups e.g. ethyl, propyl, 2,4,4-trimethylpentyl, vinyl, allyl and phenyl and silicon-free oxyalkylene groups of the formula -X(OR)nOG, wherein G is for example ethyl, butyl or acetyl; with the proviso that at least 40 percent of the total siloxane silicon-bonded substituents are methyl groups. The preferred copolymers of this invention are those wherein the oxyalkylene groups (OR)n are oxyethyl-ene and comprise at least 35% of the total weight of the copolymer.
The copolymers of this invention may take any of the molecular configurations available to such copolymers provided such configuration is consistent with the pres-ence of terminal silyl groups on the oxyalkylene-contain-ing group or groups. For example, they may be of the ABA
configuration wherein A represents the _ 5 _ ~2 ~ 57 6'~
-X(~R)nosiR a(OR )2-a group and B represents a linear sîloxane portion e.g.
-(M2SiO)b wherein each M individually represents an organic substi~uent such as -CH3 and b is an. integer of at least 2. Alternatively the copolymer may be of the so-called "rake" configuration wherein the oxyalkylene-containing groups are pendant from a siloxane chain as in M IM M M
MSiO--- - SiO- _ -SiO- - SiM
M M A M
Y z in which y is zero or an integer and z is an integer.
According to yet another configuration the oxyalkylene-containing (A) groups may be present both in the pendantpositions and attached to the terminal silicon atoms of the siloxane chain. It will thus be apparent that in addition to the siloxane units having oxyalkylene groups attached thereto the copolymers of this invention may also comprise monofunctional M3SiO~ units, difunctional M2SiO and trifunctional MSiO3/2 units. If desired, small proportions of tetrafunctional SiO2 units may also be present.
The copolymers of this invention can be obtained by reacting together (A) an organosiloxane-oxyalkylet~e copolymer wherein at least one silicon atom of an organo-siloxane unit has attached thereto a group of the general formula -X(OR)nOH
the remaining silicon-bonded substituents in the organo-siloxane units being selected from hydrogen atoms, mono-valent hydrocarbon groups and groups represented by the general formula -X(OR)nOG, at least ~0 percent of the - 6 ~22~i7Ej7 total substituents bonded to siloxane silicon atoms in the copolymer being methyl groups, and (B) an organo-silane ZSiR'a(OR )3-a wherein X, R, ~, R', R" and a are as hereinbefore defined and G represents a monovalent hydrocarbon group having from 1 to 10 carbon atoms or an acyl g:roup having from 2 to 6 carbon atoms.
Organosiloxane-oxyalkylene copolymers (A) employed in the said preparative process are a known class of materials. Such copolymers and methods for their prepa~
ration are described in, for example, British Patents ~02 467 and 1 ll~3 206, The silanes (B) are also known substances and have been disclosed in, for example, British Patent 83~ 326.
Some reaction between (A) and (B) to form the organosiloxane-oxyalkylene copolymers of this invention is believed to occur at normal ambient temperatures. It is preferred, however, to expedite the reaction by the use of higher temperatures, for example, from about 60C
to 180C. If desired the reaction may be carried forward in the presence of a transesterification catalyst, for example zinc tetrafluoroborate, an organic tin compound e.g. stannous octoate or a titanium compound e.g. tetra-2S butyl titanate. Where subsequent reaction of thecopolymer via the epoxy groups is envisaged the preferred catalysts are those which also function to open the epoxy ring e.g. zinc tetrafluoroborate.
The relative molar proportions of the reactants employed may be varied to achieve substantially complete reaction of the available COH groups, or to induce only partial reaction whereby the resulting copolymer product contains both silylated and non-silylated oxyalkylene groups.
~ ~257~7 The molecular weight of the copolymers of this invention may vary widely and the copolymers may range from mobile liquids to gummy or waxy solids. When a sufficient proportion of oxyethylene units is present the copolymers are water-soluble. The copolymers may there-fore be formed into curable films on continuous, porous or fibrous substrates from aqueous or non aqueous solutions. Curing of the copolymers into films will take place in the absence of a curing catalyst. It is, how-ever, generally preferred to accelerate the cure by theaddition of a siloxane condensation catalyst. A wide variety of such catalysts are known and include, for example acids, bases and metal organic compounds such as the ~etal carboxylates e.g. dibutyltin dilaurate, stannous octoate and zinc octoate and titanium alkoxides and chelates. Certain substances e.g. zinc tetrafluoro-borate and stannous octoate can function both as a trans-esterification catalyst during the preparation of the siloxane-oxyalkylene copolymer and subsequently as a curing catalyst therefor.
It is also preferred to effect drying and curing of the films at elevated temperatures. The actual temp-erature employed will depend to some extent on the nature and heat resistance of the substrate, temperatures in the range from about 80C to about 180C being generally appropriate.
If desired the copolymers of the invention may be mixed with fillers, pigments and other additives to produce compositions curable to rubbery solids having paintable surfaces.
The following examples in which Me represents methyl illustrate the invention.
- 8 - ~2 ~ 7 Example 1 To a 20 litre split-necked flask equipped with a stirrer, condenser and thermometer was charged 12,500g of a siloxane-oxyalkylene copolymer of average composition E (CH2C~2)12(cH2)3siMe2Oo 5¦ 2 (SiMe2O)14. The flask was heated to 9QC and a 40~-by weight aqueous solution (26ml) of zinc tetrafluoroborate added and dissolved with stirring. This was follow~d by the addition over 2 minutes of the silane.
/\
(MeO)3Si(CH2)3OCH2CH - CH2 (2458.7g), the reaction mixture then being maintained at 90C for a further 2 hours. On cooling there was obtained 14,870g (99.5%) of a clear, amber, water-soluble liquid.
When an aqueous solution (15% by weight) of the liquid was coated Oll to aluminium and dried at 150C for
3 minutes a cro~slinked, water-insoluble, hydrophilic film was obtained.
Example 2 192G of the siloxane-oxyalkylene copolymer employed in Example 1 and lgm of concentrated hydrochloric acid were heated with stirring to 90C. 37.8G of the silane / O\
(MeO)3SiCH2CH2CH2oCH2CH C~l2 were added and the mixture maintained at 90C for 2 hours. On cooling there was obtained 223g (97%) of a clear, amber, water-soluble liquid. When an aqueous sol-ution (15% by weight) of the liquid was coated onto alum-inium and dried for 3 minutes at 150C a crosslinked 25 water insoluble film was obtained.
Example 3 Employing the procedure of Example 1 a siloxane-oxyalkylene copolymer (240g) of average composition ~5~6~7 g Me3Si(OSiMe2)9tOSiMe)30SiMe3 (CH2)3(OcH2cH2)l2 and the silane /o\
(MeO)3Si(CH2)3OCH2CH - CH2 ~70.8g) were reacted at 90 - 100C in the presence of a 40% by weight aqueous solution (3ml) of zinc tetrafluoroborate.
The reaction product (304g) was a clear, amber-coloured liquid which formed clear aqueous solutions. On drying these solutions (10% by weight) at 150C for 3 minutes clear crosslinked hydrophilic films were obtained.
Example 4 150.9G of a siloxane-oxyalkylene copolymer having the average composition EO(CH2CH20)7 s(C~12)3siMe20.~ 2 ( 2 l~.5 was heated to 80C with stirring. A 40% by weight aqueous solution (2ml) of Zn(BF4)2 was then added, ~ollowed by 117 . 2g of the silane /\
(MeO)3Si(CH2)30CH2-CH-CH2 The mixture was maintained at 80C for 2 hours and then allowed to cool. A slightly ha~y water-soluble liquid was obtained. When a 10% by weigh~ aqueous solution of this liquid was dried at 150C a crosslinked, water-insoluble film resulted.
Example 2 192G of the siloxane-oxyalkylene copolymer employed in Example 1 and lgm of concentrated hydrochloric acid were heated with stirring to 90C. 37.8G of the silane / O\
(MeO)3SiCH2CH2CH2oCH2CH C~l2 were added and the mixture maintained at 90C for 2 hours. On cooling there was obtained 223g (97%) of a clear, amber, water-soluble liquid. When an aqueous sol-ution (15% by weight) of the liquid was coated onto alum-inium and dried for 3 minutes at 150C a crosslinked 25 water insoluble film was obtained.
Example 3 Employing the procedure of Example 1 a siloxane-oxyalkylene copolymer (240g) of average composition ~5~6~7 g Me3Si(OSiMe2)9tOSiMe)30SiMe3 (CH2)3(OcH2cH2)l2 and the silane /o\
(MeO)3Si(CH2)3OCH2CH - CH2 ~70.8g) were reacted at 90 - 100C in the presence of a 40% by weight aqueous solution (3ml) of zinc tetrafluoroborate.
The reaction product (304g) was a clear, amber-coloured liquid which formed clear aqueous solutions. On drying these solutions (10% by weight) at 150C for 3 minutes clear crosslinked hydrophilic films were obtained.
Example 4 150.9G of a siloxane-oxyalkylene copolymer having the average composition EO(CH2CH20)7 s(C~12)3siMe20.~ 2 ( 2 l~.5 was heated to 80C with stirring. A 40% by weight aqueous solution (2ml) of Zn(BF4)2 was then added, ~ollowed by 117 . 2g of the silane /\
(MeO)3Si(CH2)30CH2-CH-CH2 The mixture was maintained at 80C for 2 hours and then allowed to cool. A slightly ha~y water-soluble liquid was obtained. When a 10% by weigh~ aqueous solution of this liquid was dried at 150C a crosslinked, water-insoluble film resulted.
Claims (6)
1. An organosiloxane-oxyalkylene copolymer wherein at least one silicon atom of an organosiloxane unit has attached there-to a group represented by the general formula -X(OR0nO?iR'a(OR'')2-a wherein X represents a divalent hydrocarbon group having from 2 to 8 carbon atoms, R represents an alkylene group having from 2 to 4 carbon atoms, n is an integer of at least 2, Z
represents an organic group composed of carbon, hydrogen and oxygen and having therein at least one epoxy group, R' repre-sents a lower alkyl, vinyl or phenyl group, R" represents an alkyl or an alkoxyalkyl group having less than 7 carbon atoms and a has a value of 0 or 1, the remaining silicon- bonded substituents in the organosiloxane units being selected from hydrogen atoms, monovalent hydrocarbon groups and groups rep-resented by the general formula -X(OR)nOG
wherein X and R are as hereinabove defined and G represents a hydrogen atom, a monovalent hydrocarbon group having from 1 to 10 carbon atoms or an acyl group having from 2 to 6 carbon atoms, at least 40 percent of the total substituents bonded to siloxane silicon atoms in the copolymer being methyl groups.
represents an organic group composed of carbon, hydrogen and oxygen and having therein at least one epoxy group, R' repre-sents a lower alkyl, vinyl or phenyl group, R" represents an alkyl or an alkoxyalkyl group having less than 7 carbon atoms and a has a value of 0 or 1, the remaining silicon- bonded substituents in the organosiloxane units being selected from hydrogen atoms, monovalent hydrocarbon groups and groups rep-resented by the general formula -X(OR)nOG
wherein X and R are as hereinabove defined and G represents a hydrogen atom, a monovalent hydrocarbon group having from 1 to 10 carbon atoms or an acyl group having from 2 to 6 carbon atoms, at least 40 percent of the total substituents bonded to siloxane silicon atoms in the copolymer being methyl groups.
2. An organosiloxane-oxyalkylene copolymer as claimed in Claim 1 wherein the OR units are selected from oxyethylene units, oxypropylene units and mixtures of such units.
3. An organosiloxane-oxyalkylene copolymer as claimed in Claim 1 wherein R" represents a group selected from methyl, ethyl and methoxyethyl groups.
4. A process for the preparation of an organosiloxane-oxyalkylene copolymer as defined in Claim 1 which comprises reacting together (A) an organosiloxane-oxyalkylene copolymer wherein at least one silicon atom of an organosiloxane unit has attached thereto a group represented by the general formula -X(OR)nOH
the remaining silicon-bonded substituents in the organosi-loxane units being selected from hydrogen atoms, monovalent hydrocarbon groups and groups represented by the general formula -X(OR)nOG
at least 40 percent of the total substituents bonded to siloxane silicon atoms in the copolymer being methyl groups, and (B) an organosilane ZSiR'a(OR'')3-a wherein X, R, Z, R', R'' and a are as defined in Claim 1 and G
represents a monovalent hydrocarbon group having from 1 to 10 carbon atoms or an acyl group having from 2 to 6 carbon atoms.
the remaining silicon-bonded substituents in the organosi-loxane units being selected from hydrogen atoms, monovalent hydrocarbon groups and groups represented by the general formula -X(OR)nOG
at least 40 percent of the total substituents bonded to siloxane silicon atoms in the copolymer being methyl groups, and (B) an organosilane ZSiR'a(OR'')3-a wherein X, R, Z, R', R'' and a are as defined in Claim 1 and G
represents a monovalent hydrocarbon group having from 1 to 10 carbon atoms or an acyl group having from 2 to 6 carbon atoms.
5. A process as claimed in Claim 4 wherein the reaction is carried out in the presence of a transesterification catalyst.
6. A process for coating a substrate which comprises apply-ing thereto an organosiloxane-oxyalkylene copolymer as defined in Claim 1 and thereafter curing the applied copolymer.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB838314125A GB8314125D0 (en) | 1983-05-21 | 1983-05-21 | Polysiloxane-polyoxyalkylene copolymers |
| GB8314125 | 1983-05-21 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1225767A true CA1225767A (en) | 1987-08-18 |
Family
ID=10543156
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000454428A Expired CA1225767A (en) | 1983-05-21 | 1984-05-16 | Organosiloxane-oxyalkylene copolymers |
Country Status (8)
| Country | Link |
|---|---|
| JP (1) | JPS59221334A (en) |
| CA (1) | CA1225767A (en) |
| CH (1) | CH670183GA3 (en) |
| DE (1) | DE3418880A1 (en) |
| FR (1) | FR2546171B1 (en) |
| GB (1) | GB8314125D0 (en) |
| IT (1) | IT1214461B (en) |
| NL (1) | NL8401526A (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02114636U (en) * | 1989-02-27 | 1990-09-13 | ||
| DE4208447C1 (en) * | 1992-03-17 | 1993-06-03 | Th. Goldschmidt Ag, 4300 Essen, De | Silicone(s) with silicon-carbon linked residues contg. basic N and alkoxy gps. - by reacting silicone(s) contg. hydroxy-alkyl gps. with amino:alkyl-alkoxy-silane(s) in presence of non-equilibrating acid catalyst |
| DE4219070A1 (en) * | 1992-06-11 | 1993-12-16 | Goldschmidt Ag Th | Process for the preparation of polyether siloxanes |
| EP2352779B1 (en) * | 2008-12-05 | 2017-10-18 | Evonik Degussa GmbH | Polyethersiloxanes carrying alkoxysilyl groups and method for the production thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4184004A (en) * | 1978-04-21 | 1980-01-15 | Union Carbide Corporation | Treatment of textile fabrics with epoxy-polyoxyalkylene modified organosilicones |
-
1983
- 1983-05-21 GB GB838314125A patent/GB8314125D0/en active Pending
-
1984
- 1984-05-11 NL NL8401526A patent/NL8401526A/en not_active Application Discontinuation
- 1984-05-15 CH CH239284A patent/CH670183GA3/de unknown
- 1984-05-16 CA CA000454428A patent/CA1225767A/en not_active Expired
- 1984-05-17 IT IT8420961A patent/IT1214461B/en active
- 1984-05-18 FR FR8407736A patent/FR2546171B1/en not_active Expired
- 1984-05-21 JP JP59100730A patent/JPS59221334A/en active Granted
- 1984-05-21 DE DE19843418880 patent/DE3418880A1/en not_active Withdrawn
Also Published As
| Publication number | Publication date |
|---|---|
| GB8314125D0 (en) | 1983-06-29 |
| IT1214461B (en) | 1990-01-18 |
| FR2546171A1 (en) | 1984-11-23 |
| DE3418880A1 (en) | 1984-11-22 |
| CH670183GA3 (en) | 1989-05-31 |
| JPS6323212B2 (en) | 1988-05-16 |
| NL8401526A (en) | 1984-12-17 |
| FR2546171B1 (en) | 1987-07-10 |
| JPS59221334A (en) | 1984-12-12 |
| IT8420961A0 (en) | 1984-05-17 |
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