CA1339227C - Graft polymers made from (meth)acrylic acid derivatives and silicone resins - Google Patents
Graft polymers made from (meth)acrylic acid derivatives and silicone resinsInfo
- Publication number
- CA1339227C CA1339227C CA000557417A CA557417A CA1339227C CA 1339227 C CA1339227 C CA 1339227C CA 000557417 A CA000557417 A CA 000557417A CA 557417 A CA557417 A CA 557417A CA 1339227 C CA1339227 C CA 1339227C
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- weight
- allyl
- acrylic acid
- graft
- polymerization
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- 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
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/12—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes
- C08F283/122—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes on to saturated polysiloxanes containing hydrolysable groups, e.g. alkoxy-, thio-, hydroxy-
Abstract
A graft polymer produced by free-radical polymerization of (a) 10 to 90% by weight, preferably 30-65% by weight, of an oligomeric alkoxy-functional silicone resin, and (b) 90 to 10% by weight, preferably 35-70% by weight, of a mixture of (meth)acrylic acid derivatives and optionally vinyl compounds, wherein the sum of components (a) and (b) is always 100% by weight. The graft polymer so produced is useful as an impregnation agent, in particular, for building protection.
Description
Graft polymers made from (meLh)acrylic acid derivatives and silicone resins BACKGROUND OF THE INVENTION
FIELD OF THE INVENTION
The invention relates to graft polymers made from (meth)acrylic acid derivatives and alkoxy-functional silicone resins, a process for their preparation, and their use as impregnating agents, in particular, in building protection.
The use of silicone resins of various composition as impregnating agents, waterproofing~agents and buil-ding-protection agents has long been known. Alkoxy-functional, oligomeric siloxanes which crosslink under the action of moisture, if appropriate in the presence of a catalyst, have proven particularly advantageous for ~hese uses.
Furthermore, the use of mixtures comprising co-polymers of methyl methacrylate and siloxane resins for pigmented paints or impregnating agents has been dis-closed by DE-OS (German Published Application) 2,150,736, DE-OS (German Published Application) 2,352,242 and DE-AS (German Published Specification) 1,671,280. The advantage of such mix~ures is the simple preparation, but the disadvantage is serious and com-prises a tightly limited compatibility between siloxaneresin and polymethyl methacrylate, Le A 24 997 - 1 -This incompatibili~y of the polymers necessarily leads to separation of ~he mix~ure componen~s during film forma~ion and on pene~ra~ion in~o ~he building material.In order ~o limi~ ~he incompatibili~y and ~en-dency ~owards separa~ion of ~he componen~s, firs~lyhigh-aroma~ic solven~s and secondly applica~ion from grea~ly dilu~ed solution are necessary.
Combina~ions of siloxane resins and acrylate resins are very desirable. After all, besides wa~er repulsion, silicone resins also have excellent water vapor perme-ability, whereas acrylate resins offer be~er pigment binding capacity and better protection agains~, for example, calcification. On the oLher hand, the wa~er vapor permeability of acryla~e and methacryla~e co-polymer films is low.
Pain~s and impregna~ing agents which combine the advan~ages of bo~h sys~ems and comprise compa~ible, non-separa~ing, highly hydrolysis-resistant combinations are therefore very advan~ageous and desirable.
SUMMARY OF THE INVENTION
The invention has ~he objec~ of providing compat-ible silicone/acryla~e resin combina~ions for impreg-nating agen~s and ex~erior wall paints which crosslinkby means of a~mospheric mois~ure.
It was possible ~o achieve the objec~ by providing alkoxysilicone resinl(meLh)acryla~e graf~ polymers which are linked in a hydrolysis-stable manner.
The invention ~herefore rela~es ~o alkoxysilicone resin/(meth)acrylate graft polymers, a process for their preparation, and ~heir use as pain~s and impregnating agen~s.
The inven~ion rela~es ~o graf~ polymers which are characterized in ~hat free radical polymerization is carried ou~ in ~he presence of Le A 24 997 - 2 -1. 10 - 90% by weight, preferably 30 - 65% by weight, of an oligomeric, alkoxy-functional silicone resin, and 2. 90 - 10% by weight, preferably 35 - 70% by weight, of a mixture of components consisting essentially of (i) (meth)_ acrylic acids selected from the group consisting of acrylic acid and methacrylic acid, (ii) alkyl ester derivatives of said acrylic acid or said methacrylic acid,(iii) OH functional derivatives of said acrylic acid or methacrylic acid, where the sum of the components is always 100% by weight, and the alkoxy-functional silicone resin corresponds to the general formula RXsi(oR )y~4~x~y and x has a value of 0.75 to 1.7, and y has a value of 0.2 to 2, and where R denotes a linear or branched alkyl radical having 1-20 C atoms, an alkylaryl radical and/or an optionally substituted aryl radical, R' denotes a linear or branched alkyl radical having 1 to 18 C atoms.
Preferably component2. above is composed of:
a) 0.2 - 99.8% by weight, preferably 15 - 95% by weight, of methacrylates, b) 99.8 - 0.2% by weight, preferably 95 - 15% by weight, of acrylates, and c) 0 - 80% by weight, preferably 0 - 20% by weight, of (meth)acrylic acid (meth)acrylamide, (meth)acrylonitrile, vinyl aromatics, ~-olefins, vinyl esters, allyl compounds, iso-~, - 3 -propenyl compounds, or polyfunctional derivatives thereof, or mixtures thereof, - 3a -133922~
and furthermore to a process for the preparation thereof by free-radical graft polymerization in solution or in the solid phase, and to the use as impregnating agents or paints, in particular in building protection, of the graft polymers thus obtained.
DETAILED DESCRIPTION OF THE INVENTION
The silicone resins used according to the invention as the graft base are known products whose preparation is described in W. Noll, Chemie und Technologie der Silicone ~Chemistry and technology of the silicones], 2nd edition, Verlag Chemie, Weinheim, 1968, pp. 551 ff.
~5 The alkoxy groups present can optionally be methoxy, ethoxy, isopropoxy or butoxy groups. For economic rea-sons and due to its high reactivity, the methoxy group is particularly preferred here. Similarly, the silicone resins contain, besides methyl and phenyl, alkyl substi-tuents having linear or branched chains of the general formula CnH2n+1 where n = 2-20 on silicon. Particularly preferred silicone resins are those which have branched alkyl substituents on the Si atom. Furthermore, the si-licone resins can contain tri- or tetrafunctional bran-ching points. The viscosities of solutions of these re-sins in alcohols or hydrocarbons are low in order toensure good penetration, for example, in building ma-terials. In a solid after hydrolysis of the alkoxy groups of 60 - 65% by weight, the viscosity of the so-lutions used is preferably below 2000 mPa.s, and more preferably below 200 mPa.s.
Suitable solvents are preferably aromatic hydro-carbons; aliphatic hydrocarbons; alcohols; such as ethanol or isopropanol; esters, such as butyl acetate;
or mixtures thereof.
Le A 24 997 - 4 -' 1339227 Acrylic acid , methacrvlic acid and their deriva-tives, preferably their alkyl esters, are monomers that can be employed according to the invention for the graft reaction. The methyl, ethyl, isopropyl, propyl, n-butyl, isobutyl and higher alkyl esters having up to 25 C atoms in the alkyl component are examples of alkyl esters for use in the present invention. OH functional ester deri-vatives of acrylic and methacrylic acid can likewise beemployed. Particular effects can be achieved by copoly-meriza~ion of, if appropriate, mixtures of vinyl aroma-tics, such as styrene or ~-methylstyrene, (meth~acrylo-nitrile, (meth)acrylic acid or vinyl acetate, ~-olefins, allyl and isopropanyl compounds, or the polyfunctional derivatives thereof with alkyl (meth)acrylates.
The polymerization can be initiated by known free-radical ;nitiators based on azo compounds or peroxide compounds, such as, for example, dibenzoyl peroxide, 4,4'-dichlorobenzoyl peroxide, di-tert.-butyl peroxide, dicumyl peroxide, tert.-butyl pivalate, tert.-butyl peroctoate and cyclohexyl percarbonate, or redox systems comprising peroxide or hydroperoxide components on the one hand and reducing agents on the other hand, at temperatures between -80~C and +250~C, preferred poly-merization temperatures being l50~C to l180~C. The poly-merization can furthermore be initiated photochemically or by radiation activation. The polymerization is carried out in solution or without addition of solvent.
Suitable solvents are the abovementioned aliphatic or aromatic hydrocarbons, Le A 24 997 - 5 -alcohols, ketones or esters. Preferred solvents or sol-vent mixtures are those ~hose flashpoint according to DIN ;s above 21~C.
The molecular ~eight of the graft polymer com-ponent is controlled by the reaction temperature, solvent, type and amount of initiator, and, if appropriate, by molecular-~eight regulators. The graft reaction itself and the graft yield can be controlled by graft activators.
Suitable graft activators are graft- and transfer-active monomers. Graft activators ~hich can be employed are allyl compounds; such as allyl alcohol, allyl acetate and other allyl esters of aliphatic or aromatic carboxylic acids; allyl carbonate derivatives, diallyl and polyallyl compounds, such as diallyl phthalate, triallyl cyanurate, triallyl citrate, allyl ethers and diallyl ethers. Impor-tant graft activators are furthermore vinyl acetate, acry-lonitrile, vinyl chloride, ethylene, propene, isobutylene or 1-butene and diisobutylene as examples from the series comprising active ~-olefins. The graft reaction accord-ing to the invention is preferably carried out using 0.01to 20X by weight of graft activators, relative to the total sum of the reaction components employed, and the products thus obtained.
By means of the graft reaction, it is possible to combine acrylate and alkoxysiloxane resin components which are incompatible per se to a clear film-compatible coat-ing resin.
The mixtures described above of specific silicone resins (DE-OS (German Published Specification) 2,352,242) and methyl polymethacrylate (DE-AS (German Published Specification) 1,671,280) can be employed as exterior pro-tecting paints only from specific solvent combinations having a lo~ solids content or only in certain combina-tions. Physically, they are mixtures of incompatible poly-mers. A drastic improvement in compatibility of the Le A 24 997 - 6 -silicone resin and acrylate resin component can be achie-ved through the graft reaction. Furthermore, separation of the silicone and the acrylate resin component is avoi-ded through the binding of the graft resin component to the silicone resin via a hydrolysis-stable Si-C bond, so that the building material is also adequately protected in the entire penetration region. furthermore, it is pos-sible to obtain a pigmented paint having high color sta-bility and gloss retention by adding to the graft poly-mer solution inorganic or organic colored pigments ~hichoccurs under the conditions ~hich are conventional in industry.
The impregnating agents and paints according to the invention can be crosslinked by atmospheric moisture.
Catalysts can be employed to accelerate the crosslinking reaction. These catalysts are kno~n and described, for example, in W. Noll, Chemie und Technologie der Silicone ~Chemistry and technology of the silicones], 2nd edition, 1968, pp. 181 ff. In general, the crosslinking catalysts used are soluble organometallic compounds, such as Sn, Mn or Fe derivatives. The amount of catalyst, relative to the solids, depends on various factors, such as substitu-ents, film hardness desired and hardening time, and is usually 0.01-5% by weight, preferably 0.5-2% by ~eight.
The graft polymers according to the invention are used as impregnating agents for building materials and concrete, furthermore as exterior ~all paints.
The subject-matter of the present invention will be illustrated in greater detail with reference to the follo~ing examples.
For the experiments described below, the silicone resins corresponding to the follo~ing formulae are used:
Silicone resin A: (Me)o.7(i-Bu)o~3si(o)1~os(oMe)o 9 Me = methyl radical i-8u = isobutyl radical Silicone resin B: MeSi(0)1 1(0Me)o 8 Le A 24 997 _ 7 _ Silicone resin C: (Me)1.0R0.2R 0.1Si(o)1.o(oMe)o-7 R = C12-alkyl radical R' = C14-alkyl radical The solids specified in the examples Yere deter-mined after cleaving off the alkoxy groups, by hydrolysisof the alkoxy groups, by hydrolysis using alcoholic hydro-chloric acid, evaporating off the acid and the volatile components in a drying cabinet at 105~C for 3 hours.
Unless other~ise stated, the viscosities of the graft polymer solutions Yere determined using a Haake Vis-kotester at 23~C.
Example 1:
11 kg of silicone resin A (100% strength) and 2.5 kg of test benzine (benzine fraction having the boiling point range 155~C-185~C) are heated to 100~C under a stream of nitrogen.
2 solutions are then pumped in simultaneously and uniformly Yithin 2 hours:
Solution 1: 5.1 kg of isobutyl methacrylate 1.0 kg of n-butyl acrylate and 1.0 kg of hydroxypropyl methacrylate Solution 2: 4.4 kg of test benzine (benzine fraction 155~C-185~C) 0.2 kg of tert.-butyl peroctoate and 0.25 kg of ditert.-butyl peroxide The reaction is then carried out to completion for 1 hour at 120~C
and 2 hours at 130~C.
After cool;ng, catalysis is effected Yith 150 9 of dibutyltin dilaurate. The product then has a viscosity of 172 mPa.s and a solids content of 60.5%. A film pro-duced using this solution is highly transparent, has im-peccable Yater- and C02-repellent properties and has high Yater vapor permeability.
Le A 24 997 - 8 -Example 2:
In a 5 liter. reactor, 1.6 kg of silicone resin A and 0.4 kg of test benzine (benzine fraction 155 -S 185~C) are heated to 112~C under nitrogen.
Solution 1 and 2 are pumped in within 2 hours:
Solution 1: 800 9 of isobutyl methacrylate 200 9 of methyl methacrylate 175 9 od n-butyl acrylate and 150 9 of 3-hydroxyethyl methacrylate Solution 2: 1 kg of test benzine and 35 9 of tert.-butyl peroctoate.
~hen the addition is complete, the mixture is stirred for 2 hours at 112~C and 1 hour at 120~C.
After cooling, the product has a solids content of 61.0X by weight and a viscosity of 1700 mPa.s. After addition of 0.5% by weight of dibutyltin dilaurate, rela-tive to the solids content, the film has completely har-dened and is highly transparent after 24 hours.
Example 3:
Test as a water-repellent impregnating agent for mineral building materials A graft polymer prepared in accordance with the process described above and having the composition shown in Example 1 is diluted to about 9% by weight with test benzine. Test samples of various building materials are prepared by dipping once into the impregnating solution.
The immersion time is 30 seconds. The samples thus pre-pared are stored for 6 days at 23~C and a relative humidity of about 50% and subsequently dried at 50~C for 24 hours.
The capillary absorption of water at an immer-sion depth of 3 mm is then determined.
Compared to untreated test samples (values in brac-kets), the following results are obtained.
Le A 24 997 _ 9 _ ~ater absorption in Z by weight 2 hours 6 hours 24 hours Lime-cement plaster 0.6 (11.4) 0.7 (11.6) 1.0 (11.6) Cement mortar 0.3 ( 6.1) 0.5 ( 6.4) 0.8 ( 6.4) Lime sand brick 0.3 (11.9) O.S (12.0) 0.9 (12.2) From the values, it can be seen that the untrea-ted building materials are saturated with ~ater after only 2 hours, whereas the test samples treated ~ith the graft polymer according to the invention exhibited only a slight increase in weight even after storing for 24 hours in ~ater.
Example 3a Comparison experiment The experiment from Example 3 is repeated using a 9% strength solution of a resin prepared by polymeriza-tion of isobutyl methacrylate.
~ater absorption in % by ~eight 2 hours 6 hours 24 hours Lime-cement plaster 0.8 (11.4) 1.5 (11.6) 2.9 (11.6) Cement mortar 0.4 ( 6.1) 1.0 ( 6.4) 2.4 ( 6.4) Lime sand brick 0.4 (11.9) 0.8 (12.0) 1.8 (12.2) From the values, it can be seen that the good waterproofing sho~n in Example 3 is not achieved.
Example 4:
Test for water vapor and carbon dioxide perme-a~ y The diffusion resistance figures ~ are tested in accordance with DIN 53 122 giving the follo~ing values ~hen the solution of the graft polymer from Example 3 is used H20 2,460 ~2 2,350,000 Example 4a Comparison experiment The test in Example 4 are repeated using a commer-cially available impregnating agent based on polysiloxane Le A 24 997 (A) and the isobutyl methacrylate polymer (a) used in Example 3a.
H20 (A) 0 (~) 26,500 ~ C~2 (A) 0 (P) 2,000,000 The values found show that the graft polymer according to the invention puts up a high resistance against penetration of carbon dioxide into the building material, while the water vapor permeability is scarcely affected. This property profile is desired (prevention of carbonation damage).
The comparison experiments show that commercially available impregnating agents based on polysiloxane have no carbonation protection, whereas pure polyacrylate res-ins, while exhibiting adequate carbonation protection, do not exhibit the high water vapor permeability required for building protection.
Literature: R. Engelfried, Defazet issue 9 - 1977 pages 353-359.
Example 5~
Preparation of a pigmented building protection paint The good physical properties regarding building shown in Examples 3 and 4 permit the preparation of a pigmented exterior wall coating, which is prepared, for example, according to the following recipe:
Graft polymer 60% strength solution in test benzine 300.00 parts by weight Titanium dioxide rutile type75.59 parts by weight Iron oxide pigment (yellow)5.94 parts by weight 30 Iron oxide pigment (black5.94 parts by weight Chromium oxide green1.84 parts by weight Talcum 56.69 parts by weight Solvent for correcting the viscosity40 to 100.00 parts by weight Application takes place by brushing. 2 coats are applied 24 hours apart. The dry film thickness is Le A 24 997 133922~
80 to 120 ~m. The test in an accelerated weathering apparatus according to DIN 53 2~1 produces no visible changes after a test time of 2000 hours.
It will be appreciated that the instant specifica-tion and claims are set forth by way of illustration and not limitation, and that various modifications and changes may be made without departing from the spirit and scope of the present invention.
Le A 24 997 - 12 -
FIELD OF THE INVENTION
The invention relates to graft polymers made from (meth)acrylic acid derivatives and alkoxy-functional silicone resins, a process for their preparation, and their use as impregnating agents, in particular, in building protection.
The use of silicone resins of various composition as impregnating agents, waterproofing~agents and buil-ding-protection agents has long been known. Alkoxy-functional, oligomeric siloxanes which crosslink under the action of moisture, if appropriate in the presence of a catalyst, have proven particularly advantageous for ~hese uses.
Furthermore, the use of mixtures comprising co-polymers of methyl methacrylate and siloxane resins for pigmented paints or impregnating agents has been dis-closed by DE-OS (German Published Application) 2,150,736, DE-OS (German Published Application) 2,352,242 and DE-AS (German Published Specification) 1,671,280. The advantage of such mix~ures is the simple preparation, but the disadvantage is serious and com-prises a tightly limited compatibility between siloxaneresin and polymethyl methacrylate, Le A 24 997 - 1 -This incompatibili~y of the polymers necessarily leads to separation of ~he mix~ure componen~s during film forma~ion and on pene~ra~ion in~o ~he building material.In order ~o limi~ ~he incompatibili~y and ~en-dency ~owards separa~ion of ~he componen~s, firs~lyhigh-aroma~ic solven~s and secondly applica~ion from grea~ly dilu~ed solution are necessary.
Combina~ions of siloxane resins and acrylate resins are very desirable. After all, besides wa~er repulsion, silicone resins also have excellent water vapor perme-ability, whereas acrylate resins offer be~er pigment binding capacity and better protection agains~, for example, calcification. On the oLher hand, the wa~er vapor permeability of acryla~e and methacryla~e co-polymer films is low.
Pain~s and impregna~ing agents which combine the advan~ages of bo~h sys~ems and comprise compa~ible, non-separa~ing, highly hydrolysis-resistant combinations are therefore very advan~ageous and desirable.
SUMMARY OF THE INVENTION
The invention has ~he objec~ of providing compat-ible silicone/acryla~e resin combina~ions for impreg-nating agen~s and ex~erior wall paints which crosslinkby means of a~mospheric mois~ure.
It was possible ~o achieve the objec~ by providing alkoxysilicone resinl(meLh)acryla~e graf~ polymers which are linked in a hydrolysis-stable manner.
The invention ~herefore rela~es ~o alkoxysilicone resin/(meth)acrylate graft polymers, a process for their preparation, and ~heir use as pain~s and impregnating agen~s.
The inven~ion rela~es ~o graf~ polymers which are characterized in ~hat free radical polymerization is carried ou~ in ~he presence of Le A 24 997 - 2 -1. 10 - 90% by weight, preferably 30 - 65% by weight, of an oligomeric, alkoxy-functional silicone resin, and 2. 90 - 10% by weight, preferably 35 - 70% by weight, of a mixture of components consisting essentially of (i) (meth)_ acrylic acids selected from the group consisting of acrylic acid and methacrylic acid, (ii) alkyl ester derivatives of said acrylic acid or said methacrylic acid,(iii) OH functional derivatives of said acrylic acid or methacrylic acid, where the sum of the components is always 100% by weight, and the alkoxy-functional silicone resin corresponds to the general formula RXsi(oR )y~4~x~y and x has a value of 0.75 to 1.7, and y has a value of 0.2 to 2, and where R denotes a linear or branched alkyl radical having 1-20 C atoms, an alkylaryl radical and/or an optionally substituted aryl radical, R' denotes a linear or branched alkyl radical having 1 to 18 C atoms.
Preferably component2. above is composed of:
a) 0.2 - 99.8% by weight, preferably 15 - 95% by weight, of methacrylates, b) 99.8 - 0.2% by weight, preferably 95 - 15% by weight, of acrylates, and c) 0 - 80% by weight, preferably 0 - 20% by weight, of (meth)acrylic acid (meth)acrylamide, (meth)acrylonitrile, vinyl aromatics, ~-olefins, vinyl esters, allyl compounds, iso-~, - 3 -propenyl compounds, or polyfunctional derivatives thereof, or mixtures thereof, - 3a -133922~
and furthermore to a process for the preparation thereof by free-radical graft polymerization in solution or in the solid phase, and to the use as impregnating agents or paints, in particular in building protection, of the graft polymers thus obtained.
DETAILED DESCRIPTION OF THE INVENTION
The silicone resins used according to the invention as the graft base are known products whose preparation is described in W. Noll, Chemie und Technologie der Silicone ~Chemistry and technology of the silicones], 2nd edition, Verlag Chemie, Weinheim, 1968, pp. 551 ff.
~5 The alkoxy groups present can optionally be methoxy, ethoxy, isopropoxy or butoxy groups. For economic rea-sons and due to its high reactivity, the methoxy group is particularly preferred here. Similarly, the silicone resins contain, besides methyl and phenyl, alkyl substi-tuents having linear or branched chains of the general formula CnH2n+1 where n = 2-20 on silicon. Particularly preferred silicone resins are those which have branched alkyl substituents on the Si atom. Furthermore, the si-licone resins can contain tri- or tetrafunctional bran-ching points. The viscosities of solutions of these re-sins in alcohols or hydrocarbons are low in order toensure good penetration, for example, in building ma-terials. In a solid after hydrolysis of the alkoxy groups of 60 - 65% by weight, the viscosity of the so-lutions used is preferably below 2000 mPa.s, and more preferably below 200 mPa.s.
Suitable solvents are preferably aromatic hydro-carbons; aliphatic hydrocarbons; alcohols; such as ethanol or isopropanol; esters, such as butyl acetate;
or mixtures thereof.
Le A 24 997 - 4 -' 1339227 Acrylic acid , methacrvlic acid and their deriva-tives, preferably their alkyl esters, are monomers that can be employed according to the invention for the graft reaction. The methyl, ethyl, isopropyl, propyl, n-butyl, isobutyl and higher alkyl esters having up to 25 C atoms in the alkyl component are examples of alkyl esters for use in the present invention. OH functional ester deri-vatives of acrylic and methacrylic acid can likewise beemployed. Particular effects can be achieved by copoly-meriza~ion of, if appropriate, mixtures of vinyl aroma-tics, such as styrene or ~-methylstyrene, (meth~acrylo-nitrile, (meth)acrylic acid or vinyl acetate, ~-olefins, allyl and isopropanyl compounds, or the polyfunctional derivatives thereof with alkyl (meth)acrylates.
The polymerization can be initiated by known free-radical ;nitiators based on azo compounds or peroxide compounds, such as, for example, dibenzoyl peroxide, 4,4'-dichlorobenzoyl peroxide, di-tert.-butyl peroxide, dicumyl peroxide, tert.-butyl pivalate, tert.-butyl peroctoate and cyclohexyl percarbonate, or redox systems comprising peroxide or hydroperoxide components on the one hand and reducing agents on the other hand, at temperatures between -80~C and +250~C, preferred poly-merization temperatures being l50~C to l180~C. The poly-merization can furthermore be initiated photochemically or by radiation activation. The polymerization is carried out in solution or without addition of solvent.
Suitable solvents are the abovementioned aliphatic or aromatic hydrocarbons, Le A 24 997 - 5 -alcohols, ketones or esters. Preferred solvents or sol-vent mixtures are those ~hose flashpoint according to DIN ;s above 21~C.
The molecular ~eight of the graft polymer com-ponent is controlled by the reaction temperature, solvent, type and amount of initiator, and, if appropriate, by molecular-~eight regulators. The graft reaction itself and the graft yield can be controlled by graft activators.
Suitable graft activators are graft- and transfer-active monomers. Graft activators ~hich can be employed are allyl compounds; such as allyl alcohol, allyl acetate and other allyl esters of aliphatic or aromatic carboxylic acids; allyl carbonate derivatives, diallyl and polyallyl compounds, such as diallyl phthalate, triallyl cyanurate, triallyl citrate, allyl ethers and diallyl ethers. Impor-tant graft activators are furthermore vinyl acetate, acry-lonitrile, vinyl chloride, ethylene, propene, isobutylene or 1-butene and diisobutylene as examples from the series comprising active ~-olefins. The graft reaction accord-ing to the invention is preferably carried out using 0.01to 20X by weight of graft activators, relative to the total sum of the reaction components employed, and the products thus obtained.
By means of the graft reaction, it is possible to combine acrylate and alkoxysiloxane resin components which are incompatible per se to a clear film-compatible coat-ing resin.
The mixtures described above of specific silicone resins (DE-OS (German Published Specification) 2,352,242) and methyl polymethacrylate (DE-AS (German Published Specification) 1,671,280) can be employed as exterior pro-tecting paints only from specific solvent combinations having a lo~ solids content or only in certain combina-tions. Physically, they are mixtures of incompatible poly-mers. A drastic improvement in compatibility of the Le A 24 997 - 6 -silicone resin and acrylate resin component can be achie-ved through the graft reaction. Furthermore, separation of the silicone and the acrylate resin component is avoi-ded through the binding of the graft resin component to the silicone resin via a hydrolysis-stable Si-C bond, so that the building material is also adequately protected in the entire penetration region. furthermore, it is pos-sible to obtain a pigmented paint having high color sta-bility and gloss retention by adding to the graft poly-mer solution inorganic or organic colored pigments ~hichoccurs under the conditions ~hich are conventional in industry.
The impregnating agents and paints according to the invention can be crosslinked by atmospheric moisture.
Catalysts can be employed to accelerate the crosslinking reaction. These catalysts are kno~n and described, for example, in W. Noll, Chemie und Technologie der Silicone ~Chemistry and technology of the silicones], 2nd edition, 1968, pp. 181 ff. In general, the crosslinking catalysts used are soluble organometallic compounds, such as Sn, Mn or Fe derivatives. The amount of catalyst, relative to the solids, depends on various factors, such as substitu-ents, film hardness desired and hardening time, and is usually 0.01-5% by weight, preferably 0.5-2% by ~eight.
The graft polymers according to the invention are used as impregnating agents for building materials and concrete, furthermore as exterior ~all paints.
The subject-matter of the present invention will be illustrated in greater detail with reference to the follo~ing examples.
For the experiments described below, the silicone resins corresponding to the follo~ing formulae are used:
Silicone resin A: (Me)o.7(i-Bu)o~3si(o)1~os(oMe)o 9 Me = methyl radical i-8u = isobutyl radical Silicone resin B: MeSi(0)1 1(0Me)o 8 Le A 24 997 _ 7 _ Silicone resin C: (Me)1.0R0.2R 0.1Si(o)1.o(oMe)o-7 R = C12-alkyl radical R' = C14-alkyl radical The solids specified in the examples Yere deter-mined after cleaving off the alkoxy groups, by hydrolysisof the alkoxy groups, by hydrolysis using alcoholic hydro-chloric acid, evaporating off the acid and the volatile components in a drying cabinet at 105~C for 3 hours.
Unless other~ise stated, the viscosities of the graft polymer solutions Yere determined using a Haake Vis-kotester at 23~C.
Example 1:
11 kg of silicone resin A (100% strength) and 2.5 kg of test benzine (benzine fraction having the boiling point range 155~C-185~C) are heated to 100~C under a stream of nitrogen.
2 solutions are then pumped in simultaneously and uniformly Yithin 2 hours:
Solution 1: 5.1 kg of isobutyl methacrylate 1.0 kg of n-butyl acrylate and 1.0 kg of hydroxypropyl methacrylate Solution 2: 4.4 kg of test benzine (benzine fraction 155~C-185~C) 0.2 kg of tert.-butyl peroctoate and 0.25 kg of ditert.-butyl peroxide The reaction is then carried out to completion for 1 hour at 120~C
and 2 hours at 130~C.
After cool;ng, catalysis is effected Yith 150 9 of dibutyltin dilaurate. The product then has a viscosity of 172 mPa.s and a solids content of 60.5%. A film pro-duced using this solution is highly transparent, has im-peccable Yater- and C02-repellent properties and has high Yater vapor permeability.
Le A 24 997 - 8 -Example 2:
In a 5 liter. reactor, 1.6 kg of silicone resin A and 0.4 kg of test benzine (benzine fraction 155 -S 185~C) are heated to 112~C under nitrogen.
Solution 1 and 2 are pumped in within 2 hours:
Solution 1: 800 9 of isobutyl methacrylate 200 9 of methyl methacrylate 175 9 od n-butyl acrylate and 150 9 of 3-hydroxyethyl methacrylate Solution 2: 1 kg of test benzine and 35 9 of tert.-butyl peroctoate.
~hen the addition is complete, the mixture is stirred for 2 hours at 112~C and 1 hour at 120~C.
After cooling, the product has a solids content of 61.0X by weight and a viscosity of 1700 mPa.s. After addition of 0.5% by weight of dibutyltin dilaurate, rela-tive to the solids content, the film has completely har-dened and is highly transparent after 24 hours.
Example 3:
Test as a water-repellent impregnating agent for mineral building materials A graft polymer prepared in accordance with the process described above and having the composition shown in Example 1 is diluted to about 9% by weight with test benzine. Test samples of various building materials are prepared by dipping once into the impregnating solution.
The immersion time is 30 seconds. The samples thus pre-pared are stored for 6 days at 23~C and a relative humidity of about 50% and subsequently dried at 50~C for 24 hours.
The capillary absorption of water at an immer-sion depth of 3 mm is then determined.
Compared to untreated test samples (values in brac-kets), the following results are obtained.
Le A 24 997 _ 9 _ ~ater absorption in Z by weight 2 hours 6 hours 24 hours Lime-cement plaster 0.6 (11.4) 0.7 (11.6) 1.0 (11.6) Cement mortar 0.3 ( 6.1) 0.5 ( 6.4) 0.8 ( 6.4) Lime sand brick 0.3 (11.9) O.S (12.0) 0.9 (12.2) From the values, it can be seen that the untrea-ted building materials are saturated with ~ater after only 2 hours, whereas the test samples treated ~ith the graft polymer according to the invention exhibited only a slight increase in weight even after storing for 24 hours in ~ater.
Example 3a Comparison experiment The experiment from Example 3 is repeated using a 9% strength solution of a resin prepared by polymeriza-tion of isobutyl methacrylate.
~ater absorption in % by ~eight 2 hours 6 hours 24 hours Lime-cement plaster 0.8 (11.4) 1.5 (11.6) 2.9 (11.6) Cement mortar 0.4 ( 6.1) 1.0 ( 6.4) 2.4 ( 6.4) Lime sand brick 0.4 (11.9) 0.8 (12.0) 1.8 (12.2) From the values, it can be seen that the good waterproofing sho~n in Example 3 is not achieved.
Example 4:
Test for water vapor and carbon dioxide perme-a~ y The diffusion resistance figures ~ are tested in accordance with DIN 53 122 giving the follo~ing values ~hen the solution of the graft polymer from Example 3 is used H20 2,460 ~2 2,350,000 Example 4a Comparison experiment The test in Example 4 are repeated using a commer-cially available impregnating agent based on polysiloxane Le A 24 997 (A) and the isobutyl methacrylate polymer (a) used in Example 3a.
H20 (A) 0 (~) 26,500 ~ C~2 (A) 0 (P) 2,000,000 The values found show that the graft polymer according to the invention puts up a high resistance against penetration of carbon dioxide into the building material, while the water vapor permeability is scarcely affected. This property profile is desired (prevention of carbonation damage).
The comparison experiments show that commercially available impregnating agents based on polysiloxane have no carbonation protection, whereas pure polyacrylate res-ins, while exhibiting adequate carbonation protection, do not exhibit the high water vapor permeability required for building protection.
Literature: R. Engelfried, Defazet issue 9 - 1977 pages 353-359.
Example 5~
Preparation of a pigmented building protection paint The good physical properties regarding building shown in Examples 3 and 4 permit the preparation of a pigmented exterior wall coating, which is prepared, for example, according to the following recipe:
Graft polymer 60% strength solution in test benzine 300.00 parts by weight Titanium dioxide rutile type75.59 parts by weight Iron oxide pigment (yellow)5.94 parts by weight 30 Iron oxide pigment (black5.94 parts by weight Chromium oxide green1.84 parts by weight Talcum 56.69 parts by weight Solvent for correcting the viscosity40 to 100.00 parts by weight Application takes place by brushing. 2 coats are applied 24 hours apart. The dry film thickness is Le A 24 997 133922~
80 to 120 ~m. The test in an accelerated weathering apparatus according to DIN 53 2~1 produces no visible changes after a test time of 2000 hours.
It will be appreciated that the instant specifica-tion and claims are set forth by way of illustration and not limitation, and that various modifications and changes may be made without departing from the spirit and scope of the present invention.
Le A 24 997 - 12 -
Claims (8)
1. A method of protecting a building constructed of mineral building materials comprising applying to said building a solution in organic solvents of a graft polymer, curing the presence of humidity in order to impregnate said material wherein said graft polymer has been obtained by free radical polymerization of a) 10 to 90% by weight of an alkoxy-functional silicone resin corresponding to the formula where x = 0.75 - 1.7;
y = 0.2 - 2;
R denotes a linear or branched alkyl radical having 1 to 20 C atoms, an alkaryl radical or an unsubstituted or substituted aryl radical having up to 20 C atoms, and R' represents a linear or branched alkyl radical having 1 to 18 C atoms, and b) 90 to 10% by weight of a mixture of components consisting essentially of (i) (meth)acrylic acids selected from the group consisting of acrylic acid and methacrylic acid, (ii) alkyl ester derivatives of said acrylic acid or said methacrylic acid, (iii) OH functional derivatives of said acrylic acid or methacrylic acid, wherein the sum of (a) and (b) is always 100% by weight.
y = 0.2 - 2;
R denotes a linear or branched alkyl radical having 1 to 20 C atoms, an alkaryl radical or an unsubstituted or substituted aryl radical having up to 20 C atoms, and R' represents a linear or branched alkyl radical having 1 to 18 C atoms, and b) 90 to 10% by weight of a mixture of components consisting essentially of (i) (meth)acrylic acids selected from the group consisting of acrylic acid and methacrylic acid, (ii) alkyl ester derivatives of said acrylic acid or said methacrylic acid, (iii) OH functional derivatives of said acrylic acid or methacrylic acid, wherein the sum of (a) and (b) is always 100% by weight.
2. A method according to claim 1, wherein the polymerization is initiated by a free radical initiator.
3. A method according to claim 1, wherein the polymerization is conducted in the presence of a solvent.
4. A method according to claim 1, wherein the polymerization is conducted in the presence of a graft activator selected from the group consisting of allyl compounds, vinyl acetate, acrylonitrile, vinyl chloride, ethylene, propene, isobutylene, N-butene and diisobutylene.
5. A method according to claim 4, wherein the amount of activator is 0.01 to 20% by weight relative to the total sum of (a) and (b).
6. A method according to claim 1, wherein the alkyl ester has up to 25 C atoms in the alkyl part.
7. A method according to claim 2, wherein the free radical initiator is selected from the group consisting of dibenzoyl peroxide, 4,4'-dichlorobenzoyl peroxide, di-tert.-butyl peroxide, dicumyl peroxide, tert.-butyl pivalate, tert.-butyl peroctoate and cyclohexyl percarbonate.
8. A method according to claim 4, wherein the allyl compound is selected from the group consisting of allyl alcohol, allyl acetate, allyl carbonate derivative, diallyl phthalate, triallyl cyanurate, triallyl citate, allyl ether and diallyl ether.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19873702542 DE3702542A1 (en) | 1987-01-29 | 1987-01-29 | GRAFT POLYMERISATE MADE OF (METH) ACRYLIC ACID DERIVATIVES AND SILICONE RESINS |
| DEP3702542.2 | 1987-01-29 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1339227C true CA1339227C (en) | 1997-08-05 |
Family
ID=6319732
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000557417A Expired - Fee Related CA1339227C (en) | 1987-01-29 | 1988-01-27 | Graft polymers made from (meth)acrylic acid derivatives and silicone resins |
Country Status (8)
| Country | Link |
|---|---|
| EP (1) | EP0278259B1 (en) |
| JP (1) | JPS6420212A (en) |
| BR (1) | BR8800348A (en) |
| CA (1) | CA1339227C (en) |
| DE (2) | DE3702542A1 (en) |
| ES (1) | ES2035112T3 (en) |
| NO (1) | NO170026B (en) |
| ZA (1) | ZA88580B (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NZ222904A (en) * | 1987-01-15 | 1989-09-27 | Glidden Co | Acrylic modified silicone resins |
| DE68922526T2 (en) * | 1988-06-15 | 1995-09-21 | Kansai Paint Co Ltd | Water-dispersible resin composition, water-dispersible paint and method of painting with this composition. |
| DE4124167A1 (en) * | 1991-07-20 | 1993-01-21 | Synthopol Chemie Dr Koch | COPOLYMERIZATION SOLUTIONS BASED ON ADDITIONAL PRODUCTS (ALPHA), (BETA) -IN-ACID CARBOXYLIC ACID WITH GLYCIDYL REPELLERS, AND THEREOF MIXED POLYMERIZABLE (ALPHA), (BETA) -UNITENATE-SUBSTITUTED MONOMERERS |
| DE4240108A1 (en) * | 1992-11-28 | 1994-06-01 | Herberts Gmbh | Polysiloxane-containing binders, their preparation, coating compositions containing them and their use |
| DE4310005C2 (en) * | 1993-03-27 | 1996-09-05 | Degussa | Process for impregnating building materials and impregnated building material |
| DE19535824A1 (en) * | 1995-09-26 | 1997-03-27 | Wacker Chemie Gmbh | Pre-crosslinked silicone elastomer particles with an organopolymer shell as a formulation component in powder coatings |
| DE102010039168A1 (en) | 2010-08-10 | 2012-02-16 | Schwering & Hasse Elektrodraht Gmbh | Electro-insulating varnishes of modified polymers and electrical conductors made therefrom with improved lubricity |
| DE102010039169A1 (en) * | 2010-08-10 | 2012-02-16 | Universität Paderborn | Self-structuring surfaces through PDMS phase separations in hard polymer coatings |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2072178A5 (en) * | 1969-12-24 | 1971-09-24 | Ford France | Siloxane-modified acrylic lacquer coatings - prodn |
| FR2387254A2 (en) * | 1977-04-13 | 1978-11-10 | Sws Silicones Corp | Oil-resistant modified polyorganosiloxanes - for materials contacting hydraulic liqs., lubricants etc. |
| US4528301A (en) * | 1983-06-23 | 1985-07-09 | Gbf, Inc. | Oxygen permeable, styrene based, contact lens material |
-
1987
- 1987-01-29 DE DE19873702542 patent/DE3702542A1/en not_active Withdrawn
-
1988
- 1988-01-14 NO NO880146A patent/NO170026B/en unknown
- 1988-01-19 ES ES198888100650T patent/ES2035112T3/en not_active Expired - Lifetime
- 1988-01-19 EP EP88100650A patent/EP0278259B1/en not_active Expired - Lifetime
- 1988-01-19 DE DE8888100650T patent/DE3875353D1/en not_active Expired - Lifetime
- 1988-01-22 JP JP63010995A patent/JPS6420212A/en active Pending
- 1988-01-27 CA CA000557417A patent/CA1339227C/en not_active Expired - Fee Related
- 1988-01-28 ZA ZA880580A patent/ZA88580B/en unknown
- 1988-01-28 BR BR8800348A patent/BR8800348A/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| ZA88580B (en) | 1988-07-28 |
| NO170026B (en) | 1992-05-25 |
| JPS6420212A (en) | 1989-01-24 |
| EP0278259B1 (en) | 1992-10-21 |
| NO880146L (en) | 1988-08-01 |
| BR8800348A (en) | 1988-09-20 |
| NO880146D0 (en) | 1988-01-14 |
| EP0278259A2 (en) | 1988-08-17 |
| DE3875353D1 (en) | 1992-11-26 |
| ES2035112T3 (en) | 1993-04-16 |
| EP0278259A3 (en) | 1990-08-01 |
| DE3702542A1 (en) | 1988-08-11 |
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