CA1303279C - Composition based on an aqueous dispersion of an addition polymer - Google Patents
Composition based on an aqueous dispersion of an addition polymerInfo
- Publication number
- CA1303279C CA1303279C CA000517764A CA517764A CA1303279C CA 1303279 C CA1303279 C CA 1303279C CA 000517764 A CA000517764 A CA 000517764A CA 517764 A CA517764 A CA 517764A CA 1303279 C CA1303279 C CA 1303279C
- Authority
- CA
- Canada
- Prior art keywords
- epoxysilane
- alkyl
- polymer
- addition polymer
- alkoxy
- 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.)
- Expired - Lifetime
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D125/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Coating compositions based on derivatives of such polymers
- C09D125/02—Homopolymers or copolymers of hydrocarbons
- C09D125/04—Homopolymers or copolymers of styrene
- C09D125/08—Copolymers of styrene
- C09D125/14—Copolymers of styrene with unsaturated esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/42—Introducing metal atoms or metal-containing groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/541—Silicon-containing compounds containing oxygen
- C08K5/5435—Silicon-containing compounds containing oxygen containing oxygen in a ring
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J125/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Adhesives based on derivatives of such polymers
- C09J125/02—Homopolymers or copolymers of hydrocarbons
- C09J125/04—Homopolymers or copolymers of styrene
- C09J125/08—Copolymers of styrene
- C09J125/14—Copolymers of styrene with unsaturated esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
- C08L2666/28—Non-macromolecular organic substances
Abstract
The invention relates to a composition based on an aqueous dispersion of an addition polymer of one or more olefinically unsa-turated monomers, emulsion stabilizers and/or emulsifiers and a sili-con compound The addition polymer comprises monomer units containing acid groups and the silicon compound used is an epoxysilane with the for-mula
Description
3L3~
The invention relates to a composition ~ased on an aqueous dispersion of an addition polymer of one or more olefini-cally unsaturated monomers, an emulsion stabilizer and/or emulsifier and a silicon compound. Optionally the composition may yet contain other usual additives.
In the Netherlands patent 173974 adhesives are described consisting of polymeric binding agents, fillers and water, in which the polymeric binding agents comprise certain alkoxysilane compounds. These silicon compounds are added during the polymeri-zation and are incorporated in the polymer molecule. The silicon compounds hydrolize to form hydroxyl groups. The wet tensile strength of these adhesives is insufficient.
The object of the invention is to pro~ide a composition based on an aqueous dispersion of an addition polymer of one or more olefinically unsaturated monomers, an emulsion stabilizer and/or emulsifiers and a silicon compound which adheres well to mineral and organic substrates, particularly also under wet conditions .
According to one aspect of the present invention there is provided adhesive composition based on a compositioned based on an aqueous dispersion of a styrene-acrylate polymer and a silicon compound, said polymer comprising between 4% by weight an 8% by weight monomer units containing acid groups, and con-taining no monomer units with nitrogen groups which are reactable with epoxy groups, and said silicon compound being an epoxysilane having the formula:
~L3t~
- la - 22772-1077 R-O-R1-Si~ R3 \ R4 wherein in said formula:
R is epoxy alkyl ~C1~Cg), R1 is alkyl (C1-C~), ox phenyl, ;~ is alkoxy (C1-C4~, alk~l (C1-C4) or phenyl, R3 and R4 are alkoxy (C1-C4) or OH wherein the epoxysilane is added at a pH between 1.5 and 8.
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. ...
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The invention relates to a composition ~ased on an aqueous dispersion of an addition polymer of one or more olefini-cally unsaturated monomers, an emulsion stabilizer and/or emulsifier and a silicon compound. Optionally the composition may yet contain other usual additives.
In the Netherlands patent 173974 adhesives are described consisting of polymeric binding agents, fillers and water, in which the polymeric binding agents comprise certain alkoxysilane compounds. These silicon compounds are added during the polymeri-zation and are incorporated in the polymer molecule. The silicon compounds hydrolize to form hydroxyl groups. The wet tensile strength of these adhesives is insufficient.
The object of the invention is to pro~ide a composition based on an aqueous dispersion of an addition polymer of one or more olefinically unsaturated monomers, an emulsion stabilizer and/or emulsifiers and a silicon compound which adheres well to mineral and organic substrates, particularly also under wet conditions .
According to one aspect of the present invention there is provided adhesive composition based on a compositioned based on an aqueous dispersion of a styrene-acrylate polymer and a silicon compound, said polymer comprising between 4% by weight an 8% by weight monomer units containing acid groups, and con-taining no monomer units with nitrogen groups which are reactable with epoxy groups, and said silicon compound being an epoxysilane having the formula:
~L3t~
- la - 22772-1077 R-O-R1-Si~ R3 \ R4 wherein in said formula:
R is epoxy alkyl ~C1~Cg), R1 is alkyl (C1-C~), ox phenyl, ;~ is alkoxy (C1-C4~, alk~l (C1-C4) or phenyl, R3 and R4 are alkoxy (C1-C4) or OH wherein the epoxysilane is added at a pH between 1.5 and 8.
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. ...
.. .
~3~3~t~
According to a preferred embodiment of the invention, 0~1-5 %twt), preferably about 0.3-1.5 X(wt), epoxysilane is used, based on the addition polymer.
According to a further preferred embodiment of the invention, S the epoxysilane is added at a pH between 1.5 and 8, more specifically at a pH between 4 and 6.
Examples of suitable epoxysilane are particularly:
gLycidoxyalkyl trialkoxysilanes, glycidoxyphenyl trialkoxysilanes, glycidoxyalkyl dialkoxyalkylsilanes, glycidoxyphenyl dialkoxyalkylsilanes, glyc;doxyalkyl dialakoxyphenylsilanes, glyc;doxyphenyl dialkoxyphenylsilanes, and glycidoxyphenyl dialkoxyalkylsilanes and mixtures hereof~
According to a preferred embodiment of the invention, the epoxys;lane used ;s an epoxysilane with thel formula R-0-R1-Si ~ R3 where R = epoxyalkyl ~C1-C4), R1 _ alkyl ~C1-C4), R2, R3 and R4 = alkoxy ~C1~C4) According to a further preferred embodiment of the invention, 3-glycidoxyprapyltrimethoxysilane is used as epoxysilane.
; In US-A-4,032,487 and US-A-4,077,932 compositions are described consisting of acryLate dispersions based on ni~rogen con-taining monomers and epoxysilanes.
In the composition according to the invention, however, an entirely different addition polymer is used because the polymer contains no amino monomer. In additionr the epoxys`;lane according to the invention is added at a pH between 1.5 and 8 and at a temperature between 20~C
and 30~C. The present invention therefore relates to a simpler and cheaper compos;tion~
~?3~
- 3 _ 22772-1077 Aqueous dispersionsof addition polymers can be prepared via processes as described in the Netherlands patents 160278 and 161769.
The monomers used in the addition polymers according to the invention consist wholly or largely of monomers which do not contain any reactive groups other than the e~hylenic:unsatu-ration. Examples of these are the alkylacrylates, alkylmeth-acrylates, dialkylmaleates, dialkylfumarates, vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl pivalate, vinyl-2-ethylhexoate, vinyl stearate, vinyl laurate and/or vinyl versatate, vinyl ethers, vinyl chloride, alkenes such as ethylene, propylene or isobutene, butadiene, styrene, vinyltoluene, alphamethylstyrene or acrylonitrile. Mixtures of these monomers are also used. In many cases also monomers are used, in relatively small amounts, e.g. between 0.1 and 10%(wt), which, in addition to the ethylenic unsaturation, also contain other reactive groups such as carboxyl groups, sulphonic acid groups, phosphate groups, amide groups, hydroxyl groups, alkoxy-methyl amide groups or epoxy groups. Examples of such monomers are acrylic aci.d, methacrylic acid, fumaric acid, maleic acid, crotonic acid, itaconic acid, hydroxyethylacrylate, hydroxyethyl-methacrylate, hydroxypropylmethacrylate, ethylene~lycolmonoallyl-ether, N-methylolacrylamide, N-methylolmethacrylamide, n-butoxy-methylacrylamide, acrylamidopropanesulphonic acid, n-butoxy-methylmethacrylamide, glycidylacrylate, glycidylmethacrylate, allylglycidylether and vinylsulphonic acid.
~3~3Z~
- 3a - 22772-1077 In amounts up to 10 %(wt) at most, alkenically poly-unsaturated monomers, such as triallylcyanurate, divinylmaleate, divinyladipate, vinylcrotonate and ethyleneglycoldiacrylate ester, can be used.
According to a preferred embodiment of the invention, styreneacrylate copolymer is applied as addition polymer comprising monomer units containing acid groups.
According to the invention the addition polymer con-tains between 4 ~(wt) and 8 %(wt) monomer units containing acid groups, relative to the addition polymer. Preferably acrylic acid and/or methacrylic acid and/or itaco-~3~3~
nic acid are used as monomer un;ts conta;ning acid groups.
The acid used may also be phosphoric acid esters of hydroxyethyl-~meth)-acrylate.
The addit10n polymer may be in the form of a dispersion powder or in the form of an aqueous dispersion.
As catalys~ systems for the polymerization of the olefini-cally unsaturated monomers initiators can be used which dissolve either in the aqueous phase or in the monomer or in both. Examples of ~ suitable types of compounds are persulphates, hydrogen peroxides, ; 10 organic peroxides, such as hydroperoxides and azo compounds, whetheror not in comb;nation w;th reductants. Depending on the nature of the monomers and on the desired properties of the polymer and on the desired size of the polymer particles, various kinds of emulsifiers can be used e;ther separately or in combination. ~enerally both 1~ anionic and non-ionic emulsifiers can be used. Optionally, protective coiloids can also be used. In many cases a mixture of an anionic and a non-ionic emulsifier is the most sat;sfactory. A few examples of su;table classes o~f compounds are alkylbenzenesulphonates and alkyl ~C10-C1g) sulphates, mono/dialkylphosphates, ~C10-C1g) fatty acid salts, polyglycolethers of ~Cg-C1g) alcohols or alkylphenols and block copoLymers of ethylene oxide and propylene ox;de~
The amount o~ emuls;f;er or comb;nation of emulsif;ers used depends on the type of monomer and on the type of emulsifier. Generally an amount between 0.1 and 10 %(wt) is used, based on the total amount of solid, and more specifically an amount between 0.5 and 5 %~wt).
The polymerization can be effected by first producing a pre-emuls;on of the monomers and a part of the total amount of water and emuls;f;ers and subsequently starting the polymerization with the aid of a catalyst whereas the metering time of the pre-emulsion and the catalyst is between 2 and 5 hours. On the other hand it is possible to first polymerize part of the monomers in emulsion and to add more monomers stepwise, separately or mixed. In addition, it is possible to first polymerize a monomer or a combination of monomers of a certain type and to subsequently add other monomers or combinations of mono-mers, so that polymer particles w;th a laminated structure are formed.
~3~
- 5 - 22772~1077 The concentration of acid groups can be different for each layer for instance with a high concentration of acid groups on the outside of the particle and a low concentration in the centre of the particle. The amount of acid required may then be less than 2.0 ~(wt), for example between 0.5 and 1.0 ~(wt), based on the total polymer. ~ survey of various possible polymerization methods is to be found in the Netherlands patent application 7309796 published January 6, 1974. The reaction temperature during the polymerization may be between -15C and 100C, preferably between 20C and 90C. If the polymerization is car-ried out below 0C, an antifreeze like ethyleneglycol must be added~
During the polymerization other compounds may also be present, for instance chain length regulators, such as mercaptans, and buffers, such as sodium bicarbonate. In addition, substances like plasticizers, crosslinking agents, flow-promoting agents, thickeners, colourants or pigments, etc. may be present during the polymerization or be added after the polymerization~
The pH of the dispersion can be adjusted with ammonia, amines or lye.
It is also possible to react part of the acid groups after the polymeriza-tion with calcium ions or zinc ions, such as calcium acetate or zinc ammonium acetate, in such a manner that at least 2 ~(wt), preferahly 4 %(wt), of acid groups remains, relative to the additlon polymer.
.
.~
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- 5a - 22772-1077 The epoxysilane is preferably added after the polymerization of the addition polymer. The epoxysilane may, however, also be added during the polymerization. In addition, a combination of polymerizable vinylsilane and epoxysilane may be usedt in which case the vinylsilane is added during the polymerization and the epoxysilane after the polymerization.
The composition according to the invention is used, for instance, as raw material for the adhesive industry, for coatings such as synthetic plastering materials, coating agents for the building industry, paints, etc.
The invention is further elucidated by means of the following examples without, however, being restricted thereto.
Example I
, A mixture consisting of an aqueous pre-emulsion of the mono-mers styrene, butylacrylate and acrylic acid (weight ratio 45/50/S) is polymerized at 80 ~C with 2.5 %twt) of an anionic emulsifier (nonyl-phenyl 10 ethylene oxide sulphate), based on the monomers. Themetering time of the pre-emuls;on is 3 hours. As catalyst 0,5 % by weight of ammoniumpersulfate is used.
After 2 hours' after-react;on at 85~C, the dispersion formed is cooled to 25 DC and subsequently 1.25 % of 3-glyc;doxypropyltrimethoxysilane trelative to the addition polymer) is added. The pH, between 2,0 and 3,0, ;s brought to 5~0 using ammonia~ The dry substance content of the d;spersion is S0 %~ The minimum film-forming temperature tMFT) is 16DC
tmeasured according to DIN 537~7).
Example II
_, _ The process of example I is repeated with the difference that 0~75 %~wt) instead of 1.25 %twt) of 3-glycidoxypropyltrimethoxysilane is added~
Example III
, . ~ _ The process o~ example I is repeated w;th the difference that 2 %twt) ;nstead of 1.25 %twt) of 3-glycidoxypropyltrimethoxysilane is added.
Comparative example 1 . _ The process of example I is repeated with the difference that 1 c25 %twt) of an incorporated vinyltrist2-methoxyethoxys;lane) is pre-; 25 sent instead of 3-glycidoxypropyltr;methoxysilane~
Example IV
The process of example I is repeated with the difference that the styrenetbutylacrylate/acrylic acid weight ratio is 48/47/5.
; The amount of 3-glycidoxypropyltrimethoxysilane is 1.2S %, based on the addition polymer. The MFT ;s 23 ~C.
~3~3Z~
Example V
The process of example I is repeated with ~he difference that 8 X~wt) acrylic acid is used instead of 5 X(wt) acrylic acid.
~n~ o:. ~
The process of example I is repeated, but now with addition of methyltrimethoxysilane (1 n25 %twt), based on the monomer) instead of 3-glycidoxypropyltrimethoxysil3ne.
Example VI
The dispersion subsequently serve as the base for tile adhe-sives w;th the following compositions:Dispersions according to example I up to and ;nclud;ng V and 1 wp to and in-cluding 2 115 parts by weight Water 175 parts by weight 15 Methylhydroxyl cellulose th;ckener, Tylose MH 6000XP 3.7 parts by weight ex. Kalle Chemie Ant;foam, Hercules~1512 M, ex Hercules 1.0 parts by weight Fung;cide, Formalin 2.7 parts by we;gh~
ZO 8utylglycolacetate f;lm former, ex UCC 5.8 parts by we;ght Quartz powder, Snowwh;t ~ LZM, MOSA 676 parts by weight Maastr;cht Tltanium wh;te, Kornos~A, ex Kronos 14 parts by weight Titan GmbH
Z5 Th;s compos;t;on ;s mixed for ten minutes, upon which 8 parts by weight of 2~am;no 2methylpropanol 95 % tex Angus GmbH) and water are~
added in a weight ratio of 1 : 1.
Of these tile adhesives the tensile strength is determined with the a;d of ceramic t;les~ S x 5 cm, glued to concrete tiles (DIN
18156). Tile adhesives of a good dispersion may be required to have a wet tens;le strength of at least 0.50 Nimm2.
~ad!e-~nar~
~13~3~
Result:
Tensile strength dry wet in N/mm2 in N/mm2 I 2 . 32 0 . 80 II 1.76 0.58 III 2.20 0.83 1.98 0.41 IV 2 . 79 1 . 44 10 V 2.59 0~59 2 1.57 detached , ... _ _ _ These examples show that the tens;le strength requirement is complied with excellently by the addition, to the add;t;on polymer according to the invent;on, of an epoxys;lane accord;ng to the invent;on~
' '
According to a further preferred embodiment of the invention, S the epoxysilane is added at a pH between 1.5 and 8, more specifically at a pH between 4 and 6.
Examples of suitable epoxysilane are particularly:
gLycidoxyalkyl trialkoxysilanes, glycidoxyphenyl trialkoxysilanes, glycidoxyalkyl dialkoxyalkylsilanes, glycidoxyphenyl dialkoxyalkylsilanes, glyc;doxyalkyl dialakoxyphenylsilanes, glyc;doxyphenyl dialkoxyphenylsilanes, and glycidoxyphenyl dialkoxyalkylsilanes and mixtures hereof~
According to a preferred embodiment of the invention, the epoxys;lane used ;s an epoxysilane with thel formula R-0-R1-Si ~ R3 where R = epoxyalkyl ~C1-C4), R1 _ alkyl ~C1-C4), R2, R3 and R4 = alkoxy ~C1~C4) According to a further preferred embodiment of the invention, 3-glycidoxyprapyltrimethoxysilane is used as epoxysilane.
; In US-A-4,032,487 and US-A-4,077,932 compositions are described consisting of acryLate dispersions based on ni~rogen con-taining monomers and epoxysilanes.
In the composition according to the invention, however, an entirely different addition polymer is used because the polymer contains no amino monomer. In additionr the epoxys`;lane according to the invention is added at a pH between 1.5 and 8 and at a temperature between 20~C
and 30~C. The present invention therefore relates to a simpler and cheaper compos;tion~
~?3~
- 3 _ 22772-1077 Aqueous dispersionsof addition polymers can be prepared via processes as described in the Netherlands patents 160278 and 161769.
The monomers used in the addition polymers according to the invention consist wholly or largely of monomers which do not contain any reactive groups other than the e~hylenic:unsatu-ration. Examples of these are the alkylacrylates, alkylmeth-acrylates, dialkylmaleates, dialkylfumarates, vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl pivalate, vinyl-2-ethylhexoate, vinyl stearate, vinyl laurate and/or vinyl versatate, vinyl ethers, vinyl chloride, alkenes such as ethylene, propylene or isobutene, butadiene, styrene, vinyltoluene, alphamethylstyrene or acrylonitrile. Mixtures of these monomers are also used. In many cases also monomers are used, in relatively small amounts, e.g. between 0.1 and 10%(wt), which, in addition to the ethylenic unsaturation, also contain other reactive groups such as carboxyl groups, sulphonic acid groups, phosphate groups, amide groups, hydroxyl groups, alkoxy-methyl amide groups or epoxy groups. Examples of such monomers are acrylic aci.d, methacrylic acid, fumaric acid, maleic acid, crotonic acid, itaconic acid, hydroxyethylacrylate, hydroxyethyl-methacrylate, hydroxypropylmethacrylate, ethylene~lycolmonoallyl-ether, N-methylolacrylamide, N-methylolmethacrylamide, n-butoxy-methylacrylamide, acrylamidopropanesulphonic acid, n-butoxy-methylmethacrylamide, glycidylacrylate, glycidylmethacrylate, allylglycidylether and vinylsulphonic acid.
~3~3Z~
- 3a - 22772-1077 In amounts up to 10 %(wt) at most, alkenically poly-unsaturated monomers, such as triallylcyanurate, divinylmaleate, divinyladipate, vinylcrotonate and ethyleneglycoldiacrylate ester, can be used.
According to a preferred embodiment of the invention, styreneacrylate copolymer is applied as addition polymer comprising monomer units containing acid groups.
According to the invention the addition polymer con-tains between 4 ~(wt) and 8 %(wt) monomer units containing acid groups, relative to the addition polymer. Preferably acrylic acid and/or methacrylic acid and/or itaco-~3~3~
nic acid are used as monomer un;ts conta;ning acid groups.
The acid used may also be phosphoric acid esters of hydroxyethyl-~meth)-acrylate.
The addit10n polymer may be in the form of a dispersion powder or in the form of an aqueous dispersion.
As catalys~ systems for the polymerization of the olefini-cally unsaturated monomers initiators can be used which dissolve either in the aqueous phase or in the monomer or in both. Examples of ~ suitable types of compounds are persulphates, hydrogen peroxides, ; 10 organic peroxides, such as hydroperoxides and azo compounds, whetheror not in comb;nation w;th reductants. Depending on the nature of the monomers and on the desired properties of the polymer and on the desired size of the polymer particles, various kinds of emulsifiers can be used e;ther separately or in combination. ~enerally both 1~ anionic and non-ionic emulsifiers can be used. Optionally, protective coiloids can also be used. In many cases a mixture of an anionic and a non-ionic emulsifier is the most sat;sfactory. A few examples of su;table classes o~f compounds are alkylbenzenesulphonates and alkyl ~C10-C1g) sulphates, mono/dialkylphosphates, ~C10-C1g) fatty acid salts, polyglycolethers of ~Cg-C1g) alcohols or alkylphenols and block copoLymers of ethylene oxide and propylene ox;de~
The amount o~ emuls;f;er or comb;nation of emulsif;ers used depends on the type of monomer and on the type of emulsifier. Generally an amount between 0.1 and 10 %(wt) is used, based on the total amount of solid, and more specifically an amount between 0.5 and 5 %~wt).
The polymerization can be effected by first producing a pre-emuls;on of the monomers and a part of the total amount of water and emuls;f;ers and subsequently starting the polymerization with the aid of a catalyst whereas the metering time of the pre-emulsion and the catalyst is between 2 and 5 hours. On the other hand it is possible to first polymerize part of the monomers in emulsion and to add more monomers stepwise, separately or mixed. In addition, it is possible to first polymerize a monomer or a combination of monomers of a certain type and to subsequently add other monomers or combinations of mono-mers, so that polymer particles w;th a laminated structure are formed.
~3~
- 5 - 22772~1077 The concentration of acid groups can be different for each layer for instance with a high concentration of acid groups on the outside of the particle and a low concentration in the centre of the particle. The amount of acid required may then be less than 2.0 ~(wt), for example between 0.5 and 1.0 ~(wt), based on the total polymer. ~ survey of various possible polymerization methods is to be found in the Netherlands patent application 7309796 published January 6, 1974. The reaction temperature during the polymerization may be between -15C and 100C, preferably between 20C and 90C. If the polymerization is car-ried out below 0C, an antifreeze like ethyleneglycol must be added~
During the polymerization other compounds may also be present, for instance chain length regulators, such as mercaptans, and buffers, such as sodium bicarbonate. In addition, substances like plasticizers, crosslinking agents, flow-promoting agents, thickeners, colourants or pigments, etc. may be present during the polymerization or be added after the polymerization~
The pH of the dispersion can be adjusted with ammonia, amines or lye.
It is also possible to react part of the acid groups after the polymeriza-tion with calcium ions or zinc ions, such as calcium acetate or zinc ammonium acetate, in such a manner that at least 2 ~(wt), preferahly 4 %(wt), of acid groups remains, relative to the additlon polymer.
.
.~
~3~3Z7~
- 5a - 22772-1077 The epoxysilane is preferably added after the polymerization of the addition polymer. The epoxysilane may, however, also be added during the polymerization. In addition, a combination of polymerizable vinylsilane and epoxysilane may be usedt in which case the vinylsilane is added during the polymerization and the epoxysilane after the polymerization.
The composition according to the invention is used, for instance, as raw material for the adhesive industry, for coatings such as synthetic plastering materials, coating agents for the building industry, paints, etc.
The invention is further elucidated by means of the following examples without, however, being restricted thereto.
Example I
, A mixture consisting of an aqueous pre-emulsion of the mono-mers styrene, butylacrylate and acrylic acid (weight ratio 45/50/S) is polymerized at 80 ~C with 2.5 %twt) of an anionic emulsifier (nonyl-phenyl 10 ethylene oxide sulphate), based on the monomers. Themetering time of the pre-emuls;on is 3 hours. As catalyst 0,5 % by weight of ammoniumpersulfate is used.
After 2 hours' after-react;on at 85~C, the dispersion formed is cooled to 25 DC and subsequently 1.25 % of 3-glyc;doxypropyltrimethoxysilane trelative to the addition polymer) is added. The pH, between 2,0 and 3,0, ;s brought to 5~0 using ammonia~ The dry substance content of the d;spersion is S0 %~ The minimum film-forming temperature tMFT) is 16DC
tmeasured according to DIN 537~7).
Example II
_, _ The process of example I is repeated with the difference that 0~75 %~wt) instead of 1.25 %twt) of 3-glycidoxypropyltrimethoxysilane is added~
Example III
, . ~ _ The process o~ example I is repeated w;th the difference that 2 %twt) ;nstead of 1.25 %twt) of 3-glycidoxypropyltrimethoxysilane is added.
Comparative example 1 . _ The process of example I is repeated with the difference that 1 c25 %twt) of an incorporated vinyltrist2-methoxyethoxys;lane) is pre-; 25 sent instead of 3-glycidoxypropyltr;methoxysilane~
Example IV
The process of example I is repeated with the difference that the styrenetbutylacrylate/acrylic acid weight ratio is 48/47/5.
; The amount of 3-glycidoxypropyltrimethoxysilane is 1.2S %, based on the addition polymer. The MFT ;s 23 ~C.
~3~3Z~
Example V
The process of example I is repeated with ~he difference that 8 X~wt) acrylic acid is used instead of 5 X(wt) acrylic acid.
~n~ o:. ~
The process of example I is repeated, but now with addition of methyltrimethoxysilane (1 n25 %twt), based on the monomer) instead of 3-glycidoxypropyltrimethoxysil3ne.
Example VI
The dispersion subsequently serve as the base for tile adhe-sives w;th the following compositions:Dispersions according to example I up to and ;nclud;ng V and 1 wp to and in-cluding 2 115 parts by weight Water 175 parts by weight 15 Methylhydroxyl cellulose th;ckener, Tylose MH 6000XP 3.7 parts by weight ex. Kalle Chemie Ant;foam, Hercules~1512 M, ex Hercules 1.0 parts by weight Fung;cide, Formalin 2.7 parts by we;gh~
ZO 8utylglycolacetate f;lm former, ex UCC 5.8 parts by we;ght Quartz powder, Snowwh;t ~ LZM, MOSA 676 parts by weight Maastr;cht Tltanium wh;te, Kornos~A, ex Kronos 14 parts by weight Titan GmbH
Z5 Th;s compos;t;on ;s mixed for ten minutes, upon which 8 parts by weight of 2~am;no 2methylpropanol 95 % tex Angus GmbH) and water are~
added in a weight ratio of 1 : 1.
Of these tile adhesives the tensile strength is determined with the a;d of ceramic t;les~ S x 5 cm, glued to concrete tiles (DIN
18156). Tile adhesives of a good dispersion may be required to have a wet tens;le strength of at least 0.50 Nimm2.
~ad!e-~nar~
~13~3~
Result:
Tensile strength dry wet in N/mm2 in N/mm2 I 2 . 32 0 . 80 II 1.76 0.58 III 2.20 0.83 1.98 0.41 IV 2 . 79 1 . 44 10 V 2.59 0~59 2 1.57 detached , ... _ _ _ These examples show that the tens;le strength requirement is complied with excellently by the addition, to the add;t;on polymer according to the invent;on, of an epoxys;lane accord;ng to the invent;on~
' '
Claims (5)
1. Adhesive composition based on an aqueous dispersion of a styrene-acrylate polymer and a silicon compound, said polymer comprising between 4% by weight an 8% by weight monomer units containing acid groups, and containing no monomer units with nitrogen groups which are reachable with epoxy groups, and said silicon compound being an epoxysilane having the formula:
wherein in said formula:
R is epoxy alkyl (C1-C4), R1 is alkyl (C1-C4), or phenyl, R2 is alkoxy (C1-C4), alkyl (C1-C4) or phenyl, R3 and R4 are alkoxy (C1-C4) or OH wherein the epoxysilane is added at a pH between 1.5 and 8.
wherein in said formula:
R is epoxy alkyl (C1-C4), R1 is alkyl (C1-C4), or phenyl, R2 is alkoxy (C1-C4), alkyl (C1-C4) or phenyl, R3 and R4 are alkoxy (C1-C4) or OH wherein the epoxysilane is added at a pH between 1.5 and 8.
2. A composition according to claim 1, wherein the amount of epoxysilane, relative to the addition polymer, is 0.1 to 5%(wt.).
3. A composition according to claim 1, wherein the epoxysilane has the formula where R is epoxyalkyl (C1-C4), R1 is alkyl (C1-C4), R2, R3 and R4 are each independently alkoxy (C1-C4).
4. A composition according to claim 3, wherein the epoxy-silane is 3-glycidoxypropyltrimethoxysilane.
5. A moulded product comprising an adhesive composition according to any one of claims 1 to 4.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| NL8502463 | 1985-09-10 | ||
| NL8502463A NL8502463A (en) | 1985-09-10 | 1985-09-10 | COMPOSITION BASED ON A WATERY DISPERSION OF AN ADDITION POLYMER. |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1303279C true CA1303279C (en) | 1992-06-09 |
Family
ID=19846524
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000517764A Expired - Lifetime CA1303279C (en) | 1985-09-10 | 1986-09-09 | Composition based on an aqueous dispersion of an addition polymer |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US5100955A (en) |
| EP (1) | EP0214696B1 (en) |
| AT (1) | ATE53398T1 (en) |
| CA (1) | CA1303279C (en) |
| DE (1) | DE3671756D1 (en) |
| ES (1) | ES2001297A6 (en) |
| NL (1) | NL8502463A (en) |
| PT (1) | PT83351B (en) |
Families Citing this family (36)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB8710912D0 (en) * | 1987-05-08 | 1987-06-10 | Unilever Plc | Emulsion copolymerisation |
| GB8829147D0 (en) * | 1988-12-14 | 1989-01-25 | Unilever Plc | Emulsion polymers |
| DE3911945A1 (en) * | 1989-04-12 | 1990-10-25 | Basf Ag | AQUEOUS RESIN DISPERSION |
| DE3918704A1 (en) * | 1989-06-08 | 1990-12-13 | Huels Chemische Werke Ag | METHOD FOR THE PRODUCTION OF WAESSEN, SILICONE-MODIFIED PLASTIC DISPERSIONS AND THEIR USE |
| GB2251246A (en) * | 1990-12-05 | 1992-07-01 | Brickmatch Ltd | A composition suitable for application to stonework or brickwork |
| FR2684107B1 (en) * | 1991-11-27 | 1995-06-23 | Rhone Poulenc Chimie | AQUEOUS DISPERSIONS OF STYRENE-ACRYLATE CARBOXYL POLYMERS AND THEIR USES AS BINDERS IN ADHESIVE AND COATING COMPOSITIONS. |
| DE4329089A1 (en) * | 1993-08-30 | 1995-03-02 | Huels Chemische Werke Ag | Process for the preparation of aqueous silanol group-modified plastic dispersions |
| DE69420378T2 (en) * | 1993-12-23 | 1999-12-30 | Nitto Denko Corp | Process for the preparation of an aqueous dispersion of an acrylic polymer, acrylic polymer thus prepared, and pressure sensitive adhesive containing this polymer |
| US5852095A (en) * | 1994-04-20 | 1998-12-22 | Asahi Kasei Kogyo Kabushiki Kaisha | Aqueous, silicone-modified acrylate polymer emulsion |
| US5977210A (en) * | 1995-01-30 | 1999-11-02 | Xerox Corporation | Modified emulsion aggregation processes |
| US5698628A (en) * | 1995-02-27 | 1997-12-16 | Kanegafuchi Kagaku Kogyo Kabushiki Kaisha | Resin composition suitable as water-based paint and process for forming coating films having excellent stain resistance |
| US6127462A (en) * | 1995-04-12 | 2000-10-03 | Osi Specialities, Inc. | Compositions of epoxysilane and reactive polymer with cure catalyst and methods of preparation |
| US6369139B1 (en) | 1995-04-12 | 2002-04-09 | Crompton Corporation | Compositions of epoxysilane emulsion additives in waterbased reactive polymer dispersions and methods of preparation |
| US6627682B1 (en) | 1995-04-12 | 2003-09-30 | Crompton Corporation | Epoxy compositions |
| US5686523A (en) * | 1995-05-26 | 1997-11-11 | Osi Specialties, Inc. | Aqueous curable silane/polymer compositions |
| US5827922A (en) * | 1995-05-26 | 1998-10-27 | Osi Specialties, Inc. | Aqueous silylated polymer curable compositions with tin catalysts |
| US6069200A (en) * | 1995-05-26 | 2000-05-30 | Ck Witco Corporation | Aqueous silylated polymer curable compositions |
| AU708172B2 (en) * | 1996-02-26 | 1999-07-29 | Rohm And Haas Company | Dual-cure latex compositions |
| US5998549A (en) * | 1996-05-31 | 1999-12-07 | 3M Innovative Properties Company | Durable, low surface energy compounds and articles, apparatuses, and methods for using the same |
| ES2244976T3 (en) * | 1996-10-02 | 2005-12-16 | General Electric Company | COMPOSITIONS OF ADDITIVES OF AN EPOXISILAN EMULSION IN DISPERSIONS OF WATER-BASED REACTIVE POLYMERS, AND PROCEDURES FOR THEIR PREPARATION. |
| DE19704553A1 (en) * | 1997-02-06 | 1998-08-13 | Wacker Chemie Gmbh | Joint sealants with improved resilience |
| ES2270490T3 (en) * | 1997-12-15 | 2007-04-01 | General Electric Company | LATEX SEALANTS CONTAINING EPOXISILANS. |
| GB0009017D0 (en) * | 2000-04-12 | 2000-05-31 | Evode Ltd | Water-resistant adhesive |
| EP1288269A1 (en) * | 2001-08-28 | 2003-03-05 | Sicpa Holding S.A. | Water-based screen printing ink |
| DE10154030A1 (en) * | 2001-11-02 | 2003-05-22 | Basf Coatings Ag | Effect generator, aqueous coating material, process for its preparation and its use |
| AU2003236347A1 (en) | 2002-04-08 | 2003-10-20 | Kaneka Corporation | Organic polymers having at the ends epoxy- and/or oxetanyl-containing silicon groups and process for production thereof |
| DE102005051588A1 (en) | 2005-10-27 | 2007-05-03 | Wacker Polymer Systems Gmbh & Co. Kg | Silane-modified dispersion powder |
| US7807739B2 (en) | 2006-02-14 | 2010-10-05 | Rohm And Haas Company | Aqueous emulsion polymer |
| CA2734137C (en) * | 2010-03-05 | 2015-08-11 | Basf Se | Styrene-butadiene-based binders and methods of preparing and using same |
| WO2012013663A2 (en) | 2010-07-28 | 2012-02-02 | Basf Se | Use of perlite based effect pigments for finishes with antique, or patina appearance |
| US9309351B2 (en) | 2010-12-16 | 2016-04-12 | Basf Se | Styrene-acrylic-based binders and methods of preparing and using same |
| EP2599844A1 (en) | 2011-12-02 | 2013-06-05 | PPG Industries Ohio Inc. | Coating composition for a food or beverage can |
| TWI521032B (en) * | 2012-06-28 | 2016-02-11 | 羅門哈斯公司 | Wet glue |
| CN104342073A (en) * | 2014-10-31 | 2015-02-11 | 中科院广州化学有限公司 | Organic silicon modified phenyl emulsion pressure-sensitive adhesive with high release force and low residue as well as preparation method thereof and application |
| CN105801739B (en) * | 2016-04-11 | 2018-09-14 | 华南理工大学 | A kind of styrene-acrylic emulsion and the high PVC interiro wall latex paint of resistance to scrub prepared therefrom |
| EP3981842A1 (en) * | 2020-10-09 | 2022-04-13 | Hilti Aktiengesellschaft | Fire-protection coating composition and use thereof |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3816235A (en) * | 1972-08-18 | 1974-06-11 | Owens Corning Fiberglass Corp | Glass fiber size composition |
| US4077932A (en) * | 1974-03-21 | 1978-03-07 | Borden, Inc. | Acrylate adhesive aqueous dispersions |
| NL161769C (en) * | 1975-09-25 | 1980-03-17 | Synres Internationaal Nv | PROCESS FOR PREPARING STABLE AQUEOUS EMULSIONS OF ADDITION POLYMERS AND COPOLYMERS. |
| NL160278C (en) * | 1975-09-25 | 1979-10-15 | Synres Internationaal Nv | PROCEDURE FOR PREPARING Aqueous EMULSIONS OF ADDITIONAL POLYMERS. |
| US4291095A (en) * | 1977-08-03 | 1981-09-22 | Owens-Corning Fiberglass Corporation | Coating composition for glass fibers |
| US4594379A (en) * | 1980-05-29 | 1986-06-10 | Nippon Sheet Glass Co., Ltd. | Non-fogging coating composition and a shaped article coated therewith |
| FR2483448B1 (en) * | 1980-05-29 | 1985-12-20 | Nippon Sheet Glass Co Ltd | ANTI-FOG COATING COMPOSITION, SHAPED ARTICLE COATED WITH SUCH COMPOSITION AND PROCESS FOR PREPARING THE SAME |
| US4439494A (en) * | 1982-03-01 | 1984-03-27 | General Electric Company | Silyl-polyacrylates for polycarbonate substrates |
| JPS58152074A (en) * | 1982-03-05 | 1983-09-09 | Mitsui Toatsu Chem Inc | Adhesive composition for ceramic tile |
| JPS6018554A (en) * | 1983-07-11 | 1985-01-30 | Nippon Seika Kk | Coating composition |
-
1985
- 1985-09-10 NL NL8502463A patent/NL8502463A/en not_active Application Discontinuation
-
1986
- 1986-09-08 AT AT86201532T patent/ATE53398T1/en active
- 1986-09-08 EP EP86201532A patent/EP0214696B1/en not_active Expired - Lifetime
- 1986-09-08 DE DE8686201532T patent/DE3671756D1/en not_active Expired - Lifetime
- 1986-09-09 ES ES8601716A patent/ES2001297A6/en not_active Expired
- 1986-09-09 CA CA000517764A patent/CA1303279C/en not_active Expired - Lifetime
- 1986-09-10 PT PT83351A patent/PT83351B/en not_active IP Right Cessation
-
1991
- 1991-02-15 US US07/656,034 patent/US5100955A/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| ATE53398T1 (en) | 1990-06-15 |
| US5100955A (en) | 1992-03-31 |
| DE3671756D1 (en) | 1990-07-12 |
| PT83351B (en) | 1989-01-17 |
| NL8502463A (en) | 1987-04-01 |
| ES2001297A6 (en) | 1988-05-01 |
| EP0214696B1 (en) | 1990-06-06 |
| PT83351A (en) | 1986-10-01 |
| EP0214696A1 (en) | 1987-03-18 |
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