GB2075995A - Modified Acrylate Polymers and Surface Coverings Comprising Them - Google Patents
Modified Acrylate Polymers and Surface Coverings Comprising Them Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
- C07D295/16—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms
- C07D295/18—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms by radicals derived from carboxylic acids, or sulfur or nitrogen analogues thereof
- C07D295/182—Radicals derived from carboxylic acids
- C07D295/185—Radicals derived from carboxylic acids from aliphatic carboxylic acids
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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
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
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Abstract
Cross-linked acrylate- acetoacetamide polymers, prepared by the reaction of at least one polyfunctional acrylate with at least one diacetoacetamide in the presence of a catalyst capable of promoting the reaction. The polymers have utility in wear layer composition for surface coverings.
Description
SPECIFICATION
Modified Acrylate Polymers and Surface Coverings Comprising Them
This invention relates to polymers more especially to modified acrylate polymers and to coatings or films produced from these polymers.
The resilient flooring industry is continually searching for new abrasion-resistant polymeric compositions which will serve as wear layers for decorative surface coverings, especially thermoplastic floor coverings.
Such compositions must have good film-forming properties and must yield layers with good abrasion-resistant properties.
According to this invention, there is provided a crosslinked acrylate-acetoacetamide polymer obtainable by, and advantageously produced by, the reaction of at least one polyfunctional acrylate with at least one diacetoacetamide in the presence of a catalyst capable of promoting the reaction between the polyfunctional acrylate and the diacetoacetamide.
Also, according to this invention, there is provided a thermoplastic surface, especially a floor, covering coated with a wear layer composition comprising a crosslinked acrylate-acetoacetamide polymer obtainable by, and advantageously produced by, the reaction of at least one polyfunctional acrylate with at least one diacetoacetamide in the presence of a catalyst capable of promoting the reaction between the polyfunctional acrylate and the diacetoacetamide.
As the polyfunctional acrylate, there is advantageously used at least one compound of the formula R-(O-C(O)-CH=CH2)4, R1-(O-C(O)-CH=CH2)3, or R2-(O-C(O)-CH=CH2)2 wherein R represents
R1 represents
wherein R3 represents hydrogen or (C, to C3) alkyl;R2 represents: a (C1 to C,O) alkylene group, a (Ca to
C4) alkyl substituted (C, to C,O) alkylene group, (C2H4O)a(C2H4),
(CH2CH2CH2CH2O)cCH2CH2CH2CH2, where a is an integer from 1 to 20; b is an integer from 1 to 10; and c is an integer from 1 to 5, a cycloalkylene group, a cycloalkane bearing two (C, to C3) alkylene groups,
Examples of suitable polyfunctional acrylates are trimethylol propane triacrylate, pentaerythritol tetraacrylate, hexane dioi diacrylate, polyethylene glycol (200) diacrylate, ethylene glycol diacrylate, tripropylene glycol diacrylate, trimethyl hexane diol diacrylate, 1 4-cyclohexane dimethanol diacrylate, dibutylene glycol diacrylate, 1,4-cyclohexane diacrylate, dipropylene glycol di-2-acrylyl-ethyl ether, methylehebis(4-cyclohexane-2-acrylyl-ethyl urethane) 2,2,4-trimethylhexanebis(2-acrylyl-ethyl urethane), and isophorone di(2-acrylyl-ethyl urethane).
In Examples VII to IX there are described methods for the preparation of each of the urethanecontaining diacrylates, and the invention also provides these compounds.
As the diacetoacetamide, there is preferably used one or more compounds having the formula R4-(NH-C(0)-CH2-C(O)-CH3)2 wherein R4 represents: a (C, to C,O) alkylene group, a (C, to C4) alkyl substituted (C, to C,O) alkylene group, (C2H4O)dC2H4, -(CH2CH0)6-(CH2CH)-, a cycloalkylene group, a cycloalkane bearing two (C, to C3) alkylene groups, H6C3O(C2H4O)f(C2H4)OC3H6-, wherein d is an integer from 1 to 6; e is an integer from 1 to 6; and f is an integer from 1 to 4.
Representative examples of the above diacetoacetamides are isophorone diacetoacetamide, diethylene glycol di-3-acetoacetamide propyl ether, N,N'-bis(propyl-3-acetaoacetamide)-piperazine, 1 ,4-cyclohexanebis(methylacetoacetamide), 1 ,3-cyclohexanebis(methylacetoacetamide), 2,2,4- trimethylhexamethylenediacetoacetamide, 1 ,3-propanediacetoaceta mide, diethyleneglycol-di-2acetoacetamide-ethyl ether, dipropyleneglycol diacetoacetamide propyl ether, 1,4cyclohexanebis(acetoacetamide), and trimethylhexamethylene diacetoacetamide.
Methods for preparing diacetoacetamides suitable for use in this invention are described in
Examples I to VI below, and the invention also provides these compounds.
The amounts of polyfunctional acrylate and diacetoacetamide can be varied within relatively wide ranges. Preferably, about 1 to about 2 moles of polyfunctional acrylate are employed for every mole of diacetoacetamide. Best results are usually obtained when the polyfunctional acrylate is reacted with the diacetoacetamide in a mole ratio of from about 1.2 to about 1.4 moles of polyfunctional acrylate to about 1 mole of diacetoacetamide.
As the catalyst to promote the reaction,a Michael reaction, use can be made of any Michael reaction-type catalyst, many of which are w'ell known, and commonly employed to promote condensation. Particularly suitable are strong basic catalysts, such, for example, as sodium methoxide, sodium metal, sodium ethylate, and benzyltrimethylammonium methoxide. Catalytic amounts of materials may be selected in accordance with well known principles in the polymer art, the amount being one sufficient to promote the polycondensation reaction. For further information relating to the
Michael reaction mechanism, see 'The Michael Reaction" by E. D. Bergmann et al., Organic Reactions.
.Vol. 10, chapter 3, pages 179-555, and Modern Synthetic Reactions, H. O. House, 2nd Ed. (1972), pages 595-623, both herein incorporated by reference.
The polymerization reaction can be carried out using the reactants as the only reaction medium since both the polyfunctional acrylates and the diacetoacetamides are normally in the liquid state and/or they can be uniformly blended together.
Especially if the acrylate-acetoacetamide polymer is to be employed to produce a wear layer composition, polymerization may be carried out in the presence of optional ingredients, especially those typically employed in wear layer compositions, e.g., in the proportions normally used therein, for example, surfactants, and heat and light stabilizers.
The following examples illustrate the invention:
Example 1
This example demonstrates a method for the preparation of isophorone diacetoacetamide.
About 85 grams (0.5 mole) of isophorone diamine (3-aminomethyl 3,5,5trimethylcyclohexylamine) and about 325 milliliters of methylene chloride were added to a reaction vessel with stirring.
The contents of the reaction vessel were cooled to and maintained at a temperature of about 1 50C and about 80 grams (0.95 mole) of diketene were added to the contents of the reaction vessel over a period of about 1 hour.
The temperature of the contents of the reaction vessel was held at about 1 50C for about 1 3/4 hours and the resulting reaction product was transferred to a separating funnel and acidified with dilute hydrochloric acid.
The reaction product was washed twice, once with about 250 milliliters of water and about 50 milliliters of saturated sodium chloride solution and a second time with about 250 milliliters of water, about 50 milliliters of saturated sodium bicarbonate solution and a sufficient amount (about 5 ml) of saturated NaHCO3 solution to neutralize the separating funnel contents to a pH of about 6.
After the second washing, the methylene chloride layer containing the reaction product was dried with anhydrous magnesium sulfate. The magnesium sulfate was filtered off; the methylene chloride was removed by vacuum distillation and the resulting product, isophorone diacetoacetamide, was recovered in a yield of about 132 grams. It was a viscous light yellow liquid.
Example II
This example demonstrates a method for the preparation of diethyleneglycol diacetoacetamide propyl ether.
About 66 grams (0.3 mole) of diethyleneglycol diaminopropyl ether (commercially available from
Union Carbide Corporation, designated "Polyglycoldiamine H-221") and about 230 milliliters of
methylene chloride were added to a reaction vessel with stirring.
The contents of the reaction vessel were cooled to and maintained at a temperature of about
1 50C, and about 50.4 grams (0.6 mole) of diketene were added to the contents of the reaction vessel over a period of about 1 hour.
The temperature of the contents of the reaction vessel was held at about 1 00C for a period of about 4 hours and the methylene chloride was removed by vacuum distillation.
The resulting reaction product was dissolved in isopropyl alcohol and recrystallized from the alcohol. The resulting product, diethyleneglycol diacetoacetamide propyl ether, was recovered as a white solid, with a melting point range of about 620 to 63 OC.
Example Ill
This example demonstrates a method for the preparation of N,N'-bis(propyl-3-acetoacetamide)piperazine.
The procedure of Example I was followed, with the exception that the contents of the reaction vessel were held at 100 to 1 50C for a period of about 4 hours instead of the 1 3/4 hours in Example I.
Ingredients Amount
diketene 50.4 grams (0.6 mole)
N,N'-bis(aminopropyl)piperazine 60 grams (0.3 mole)
methylene chloride 250 milliliters
The resulting product, N,N'-bis(propyl-3-acetaoacetam ide)-piperazine, was recovered in a yield of about 92 grams as a viscous light yellow liquid.
Example IV
This example demonstrates a method for the preparation of 1,4cyclohexanebis(methylacetoacetamide).
The procedure of Example II was followed, with the exception that the contents of the reaction vessel were held at about 1 50C for about 2 hours.
Ingredients Amount
diketene 33.6 grams (0.4 mole)
1,4 cyclohexanebis (methylamine) 28.4 grams (0.2 mole)
methylene chloride 100 milliliters
The resulting crude product, 1 ,4-cyclohexanebis(methylacetoacetamide), was recovered and recrystallized from isopropyl alcohol. As recrystallized, the product was white with a melting point range of about 1400 to 1 43 OC.
Example V
This example demonstrates a method for the preparation of 1,3cyclohexanebis(methylacetoacetamide).
The procedure of Example II was followed, with the exceptions that chloroform was substituted for the methylene chloride and, rather than recrystallizing from isopropyl alcohol, the reaction product was washed in benzene.
Ingredients Amount
diketene 84 grams (1 mole)
1,3-cyclohexanebis (methylamine) 71 grams (0.5 mole)
chloroform 250 milliliters
The benzene insoluble fraction of the reaction product, 1,3- cyclohexanebis(methylacetoacetamide) was recovered; it was a light yellow solid, melting point range about 1050 toll 50C.
Example VI
This example demonstrates a method for the preparation of 2,2,4trimethylhexamethylenediacetoacetamide.
The procedure of Example I was followed with the exception that the contents of the reaction vessel were held at 100 to 1 5 OC for a period of about 2 hours instead of the 1 3/4 hours in Example I.
Ingredients Amount
diketene 49.2 grams (0.59 mole)
trimethylhexanediamine 45.3 grams (0.31 mole)
methylene chloride 1 50 milliliters
The resulting product 2,2,4-trimethylhexamethylenediacetoacetamide, was recovered as a light yellow viscous liquid in a yield of about 89 grams.
Example VII
This example demonstrates the preparation of a urethane containing diacrylate.
About 1 mole of methylenebis-4-cyclohexane isocyanate (designated "Hylene W", commercially available from E. I. du Pont de Nemours and Co.) and about 2 moles of hydroxyethylacrylate and about 0.05 grams of dibutyltin dilaurate catalyst were added to a reaction vessel at room temperature, with stirring. The temperature of the reaction vessel was increased to about 600C. After about 3 hours, the resulting reaction product, methylenebis(4-cyclohexane-2-acrylethylurethane) having the formula
was recovered.
Example VIII
This example demonstrates the preparation of a urethane-containing diacrylate.
About 1 mole of 2,2,4-trimethylhexane diisocyanate (designated "TMDI", commercially available from Thorson Chemical Co.) and about 2 moles of hydroxyethylacrylate and about 0.05 gram of dibutyitin dilaurate catalyst were added to a reaction vessel at room temperature, with stirring. The temperature of the reaction vessel was increased to about 600C. After about 3 hours, the resulting reaction product, 2,2,4-trimethylhexane-bis(2-acrylyl-ethyl urethane), having the formula
was recovered.
Example IX
This example demonstrates the preparation of a urethane containing diacrylate.
About 1 mole of 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (designated "IPDI" isophorone diisocyanate, commercially available from Thorson Chemical Co.) and about 2 moles of hydroxyethyl acrylate and about 0.05 gram of dibutyltin diiaurate catalyst were added to a reaction vessel at room temperature, with stirring. The temperature of the reaction vessel was increased to about 600C. After about 3 hours, the resulting reaction product, isophorone di(2-acrylyl-ethyl urethane), having the formula
was recovered.
Example X
This example demonstrates the preparation of a polymer film of this invention.
About 3.8 grams of hexanediol diacrylate, about 4.6 grams of the 2,2,4trimethylhexamethylenediacetoacetamide of Example IV, about .01 gram of a 30% by weight polyethyleneoxide siloxane surfactant (Dow Corning DC-193) in methanol solution and about 0.03 gram of a 40% by weight benzyltrimethyl ammonium methoxide in methanol catalyst solution were added to a reaction vessel at room temperature with stirring.
The resulting reaction mixture was coated on a glass surface using a Bird applicator to a coating thickness of about 0.003 inch (about 0.08 mm).
The coating was non-tacky after about 1 hour and was allowed to cure overnight at a temperature of about 600C.
The resulting cured polymer film was removed from the glass surface and observed to be clear and colorless. The film was tested by differential scanning calorimetery (using a Du Pont 900 Thermal
Analyzer) and found to have a Tg range of about 180 to about 300C with a Tg midpoint of about 240C.
The cured polymer film was also subjected to a steel wool scratch test and observed to exhibit good scratch resistance.
Example Xl The following ingredients were reacted using substantially the procedure of Example X.
Ingredients Amount hexanediol diacrylate 3.5 grams N,N'-bis(propyl-3-acetoacetamide)-piperazine of Example lil 4.8 grams 3% by weight "DC-193" in methanol solution 0.01 grams 40% by weight benzyltrimethyl ammonium methoxide in methanol
catalyst solution 0.03 grams
The resulting mixture was coated on a glass surface and cured at about 1 60C for about 16 hours.
The resulting cured polymer film was removed from the glass surface and observed to be clear and colorless. The film was tested and found to have a T, range of about 170 to 31 OC with a Tg midpoint of about 240C. The polymer film was found to exhibit good scratch resistance.
Example XII
The following ingredients were reacted using substantially the procedure of Example X.
Ingredients Amount hexanediol diacrylate 6.6 grams 1,3-cyclohexanebis (methylacetaoacetamide) of Example V 4.6 grams diethyleneglycol diacetoacetamide propyl ether of Example Il 2.4 grams 30% by weight "DC-193" in methanol solution 0.05 grams 40% by weight benzyltrimethyl ammonium methoxide in methanol
catalyst solution 0.01 grams
The resulting mixture was coated on a glass surface and cured at about 1 60C for about 1 6 hours.
The resulting cured polymer film was removed from the glass surface and observed to be clear and colorless. The film was tested and found to have a Tg range of about 170 to 35 OC with a Tg midpoint of about 260C. The polymer film was found to exhibit good scratch resistance.
Example XIII
The following ingredients were reacted using substantially the procedure of Example X.
Ingredients Amount hexanediol diacrylate 7.0 grams 2,2,4-trimethylhexamethylenediacetoacetamide of Example VI 4.8 grams 1 ,3 cyclohexanebis(methylacetoacetamide) of Example V 2.0 grams 30% by weight "DC-193" in methanol solution 0.05 grams 40% by weight benzyltrimethyl ammonium methoxide in methanol
catalyst solution 0.10 grams
The resulting mixture was coated on a glass surface and cured at about 1 60C for about 16 hours.
The resulting cured polymer film was removed from the glass surface and observed to be clear and colorless. The film was tested and found to have a Tg range of about 170 to 350C with a Tg midpoint of about 280C. The polymer film was found to exhibit good scratch resistance.
Example XIV
The following ingredients were reacted using substantially the procedure of Example X.
Ingredients Amount polyethylene glycol 200 diacrylate 3.1 grams isophorone diacetoacetamide of Example I 1.1 grams 1,4-cyclohexanebis(methylacetoacetamide) of Example IV 1.0 grams 40% by weight benzyltrimethyl ammonium methoxide in methanol
catalyst solution 0.05 grams
The resulting mixture was transferred to an aluminum dish and was tack-free after curing for 20 minutes at 600C. The polymer composition was allowed to cure at 600C for about 16 hours.
The cured polymer was observed to be clear and light yellow in color and found to have a T, range of about 11 to 270C and a Tg midpointof 190C.
The following Table I contains Examples XV through XXVII. All polymer compositions were prepared using substantially the procedure of Example XIV but were catalyzed using 0.05 gram of a 10% by weight sodium ethylate in ethanol solution per every 5 grams of the total amount of polyfunctional acrylate and diacetoacetamide.
Table I
Tg of Cured Acrylate-lsophorone Diacetoacetamide
Polymer Compositions
Ingredients andAmount Tg
Example No. (Moles) Range Midpoint
XV 1.0 EGDA' 1.0 IPDAA 45--61 530
XVI 1.2 EGDA' 1.0 IPDAA 4157 490
XVII 1.4 EGDA' 1.0 IPDAA 28--50 370
XVIII 1.OHDDA3 1.0 IPDAA 17--46 320
XIX 1.2 HDDA3 1.0 IPDAA 27--49 380
XX 1.4 HDDA3 1.0 IPDAA 24---51 380
XXI 1.6 HDDA3 1.0 IPDAA 11.370 240
XXII 1.0 TPGDA4 1.0 IPDAA 11-36 240
XXIII 1.2 TPGDA4 1.0 IPDAA 14.380 260
XXIV 1.6TPGDA4 1.OlPDAA 1638 270
XXV 1.0PEG200DA5 1.OlPDAA 15--40 280
XXVI 1.2 PEG200DA5 1.0 IPDAA 16--39 290
XXVII 1.6 PEG200DA5 1.0 IPDAA 226 140 EGDA--ethylene glycol diacrylate 2IPDAA--isophorone diacetoacetamide HDDA-hexanedioldiacrylate 4TPGDA-tripropylene glycol diacrylate 5PEG200DA-polyethylene glycol 200 diacrylate
The following Table II contains Examples XXVIII through XXXII. All polymer films were prepared using substantially the procedure of Example X and were catalyzed using 0.4 grams of a 15% by weight sodium methylate in methanol solution per every 8 grams of the total amount of polyfunctional acrylate and diacetoacetamide.
Table II
Tg of Cured Acrylate-Acetoacetamide Polymer Films
Tg
Example No. Ingredients and Amount (Moles) Range Midpoint
XXVIII 1.40 HDDA 1.0TMHMDAA 2537 310
XXIX 1.33 HDDA1 .05TMPTA3 1.0TMHMDAA2 27--40 330
XXX 1.25 HDDA' .10TMPTA3 1.0TMHMDAA2 30--45 380
XXXI 1.18HDDA' .15TMPTA3 1.0TMHMDAA2 3246 390
XXXII 1.10HDDA' .20TMPTA3 1.0TMHMDAA2 30--47 390 HDDA--hexanedioldiacrylate 2TMHMDAA-trimethylhexamethylenediacetoacetamide 3TMPTA-trimethylolpropane triacrylate
Example XXXIII
This example demonstrates the preparation of a polymer film of this invention using the urethanecontaining diacrylate of Example VIII.
About 3.6 grams of the urethane-containing diacrylate of Example VEIL, about 1.4 grams of polyethylene glycol 200 diacrylate, about 3.2 grams of trimethylhexamethylenediacetoacetamide, 0.03 gram of a 30% by weight "DC-1 93" in methanol solution, and about 0.07 gram of a 40% by weight benzyltrimethyl ammonium methoxide in methanol catalyst solution were added to a reaction vessel at room temperature, with stirring.
The resulting mixture was coated on a glass surface using a Bird applicator to a coating or film thickness of 0.003 inch (0.08 mm).
The polymer coating was allowed to cure for about 1 6 hours at a temperature of about 700 C.
The resulting cured polymer film was removed from the glass surface and observed to be clear, colorless, and flexible.
Example XXXIV
This example demonstrates the preparation of a polymer film of this invention using the urethanecontaining diacrylate of Example IX.
About 3.0 grams of the urethane-containing diacrylate of Example IX, about 2.2 grams of polyethylene glycol 200 diacrylate, about 3.2 grams of trimethylhexamethylenediacetoacetamide, 0.03 gram of a 30% by weight "DC-193" in methanol solution, and about 0.07 gram of a 40% by weight benzyltrimethyl ammonium methoxide in methanol catalyst solution were added to a reaction vessel at room temperature, with stirring.
The resulting mixture was coated on a glass surface using a Bird applicator to a coating or film thickness of 0.003 inch (0.08 mm).
The polymer coating was allowed to cure for about 1 6 hours at a temperature of about 7O0C.
The resulting cured polymer film was removed from the glass surface and observed to be clear, colorless, and flexible.
Example XXXV
This example demonstrates the preparation of a polymer film of this invention using the urethanecontaining diacrylate of Example VII.
About 3.7 grams of the urethane-containing diacrylate of Example VII, about 1.4 grams of polyethylene glycol 200 diacrylate, about 3.2 grams of trimethylhexamethylenediacetoacetamide, 0.03 gram of a 30% by weight "DC-193" in methanol solution, and about 0.07 gram of a 40% by weight benzyltrimethyl ammonium methoxide in methanol catalyst solution were added to a reaction vessel at room temperature, with stirring.
The resulting mixture was coated on a glass surface using a Bird applicator to a coating or film thickness of 0.003 inch.
The polymer coating was allowed to cure for about 1 6 hours at a temperature of about 700C.
The resulting cured polymer film was removed from the glass surface and observed to be clear, colorless, and flexible.
Example XXXVI
This example demonstrates the preparation of a thermoplastic floor covering coated with a wear layer composition comprising a cross-linked acrylate-acetoacetamide polymer of this invention.
About 7.5 grams of hexanediol diacrylate, about 4.0 grams of tripropylene glycol diacrylate, about 8.6 grams of trimethylhexamethylene diacetoacetamide, 2.1 grams of 1,3cyclohexanebis(methylacetoacetamide) and 0.15 grams of a 40% by weight benzyltrimethyl ammonium methoxide in methanol catalyst solution were added to a mixing vessel with stirring at room temperature.
The resulting wear layer composition was applied using a conventional applicator, a Bird applicator, to a 1 2"x 12" (30 cmx30 cm) white vinyl tile and cured at 60 C for about 16 hours.
The resulting cured acrylate-acetoacetamide polymer wear layer on the tile was observed to be clear and colorless.
The wear layer coated tile was tested for gloss retention using an art recognized traffic wheel test. The initial gloss value, before testing, was 86. After 30 minutes of testing, the gloss value was 77.
After 60 minutes of testing, the gloss value was 69. And after 90 minutes of testing, the gloss value was 69. The wear layer was also subjected to an art recognized steel wool scratch test and found to exhibit good scratch resistance.
Claims (14)
1. A crosslinked acrylate-acetoacetamide polymer produced by the reaction of at least one polyfunctional acrylate with at least one diacetoacetamide in the presence of a catalyst capable of promoting the reaction between the polyfunctional acrylate and the diacetoacetamide.
2. A polymer as claimed in claim 1 in which the acrylate has the formula R-(0-C(0)-CH=CH2)4 wherein R represents
3. A polymer as claimed in claim 1 in which the acrylate has the formula R1-(0-C(O)-CH=CH2)3 wherein R1 represents
and R3 represents hydrogen or (C, to C3) alkyl.
4. A polymer as claimed in claim 1 in which the acrylate has the formula R2-(0-C(O)-CH=CH2)2 wherein R2 represents: a (C1 to C,O) alkylene group, a (C, to C4) alkyl substituted (C, to C10) alkylene group, (C2H4O)a,-(C2H4)--,--(CH2CHO)b(CH2CH),(CH2CH2CH2CH2O)CH2CH2CH2CH2 wherein a is an integer from 1 to 20, b is an integer from 1 to 1 0 and c is an integer from 1 to 5, a cycloalkylene group, a cycloalkane bearing two (C, to C3) alkylene groups,
5. A polymer as claimed in claim 2, having units derived from two or more acrylates as specified in any one or more of claims 2 to 4.
6. A polymer as claimed in any one of claims 1 to 5, in which the diacetoacetamide is a compound of the formula R4-(NH-C(O)-CH2C(0)-CH3)2 wherein R4 represents: a (C, to C,O) alkylene group, a (C, to C4) alkyl substituted (C, to C,O) alkylene group,(C2H4O)d--C2H4--,
a cycloalkylene group, a cycloalkane bearing two (C, to C3) alkylene groups, H6C3O(C2H4O)f--(C2H4)--OC3H6,
in which d is an integer from 1 to 6; e is an integer from 1 to 6; and f is an integer from 1 to 4, or a mixture of two or more such compounds.
7. A polymer as claimed in any one of claims 1 to 6, wherein the polyfunctional acrylate and the diacetoacetamide are reacted in a mole ratio of from 1 to 2 moles of polyfunctional acrylate to 1 mole of diacetoacetamide.
8. A crosslinked polymer as claimed in claim 7 wherein the polyfunctional acrylate and the diacetoacetamide are reacted in a mole ratio of from 1.2 to 1.4 moles of polyfunctional acrylate to 1 mole of diacetoacetamide.
9. A crosslinked polymer as claimed in any one of claims 1 to 8, wherein the catalyst is a strong base.
1 0. A crosslinked polymer as claimed in claim 1, substantially as described in any one of
Examples X to XXXVI.
11. A thermoplastic floor covering coated with a wear layer composition comprising a crosslinked polymer as claimed in any one of claims 1 to 10.
12. A thermoplastic floor covering as claimed in claim 1, substantially as described in Example
XXXVI.
13. A surface covering having a wear layer comprising a crosslinked polymer as claimed in any one of claims 1 to 10.
14. Any new and novel composition of matter, article or process described herein.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB8015886A GB2075995B (en) | 1980-05-13 | 1980-05-13 | Modified acrylate polymers and surface coverings comprising them |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB8015886A GB2075995B (en) | 1980-05-13 | 1980-05-13 | Modified acrylate polymers and surface coverings comprising them |
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| Publication Number | Publication Date |
|---|---|
| GB2075995A true GB2075995A (en) | 1981-11-25 |
| GB2075995B GB2075995B (en) | 1984-07-04 |
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| Application Number | Title | Priority Date | Filing Date |
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| GB8015886A Expired GB2075995B (en) | 1980-05-13 | 1980-05-13 | Modified acrylate polymers and surface coverings comprising them |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1995017568A1 (en) * | 1993-12-22 | 1995-06-29 | The Amtico Company Limited | Floor coverings |
| WO1996037563A1 (en) * | 1995-05-26 | 1996-11-28 | Ad Aerospace Finishes V.O.F. | Coating composition having improved adhesion to substrate |
-
1980
- 1980-05-13 GB GB8015886A patent/GB2075995B/en not_active Expired
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1995017568A1 (en) * | 1993-12-22 | 1995-06-29 | The Amtico Company Limited | Floor coverings |
| WO1996037563A1 (en) * | 1995-05-26 | 1996-11-28 | Ad Aerospace Finishes V.O.F. | Coating composition having improved adhesion to substrate |
| US6057001A (en) * | 1995-05-26 | 2000-05-02 | Ad Aerospace Finishes V.O.F. | Coating composition having improved adhesion to substrate |
| US6689423B1 (en) | 1995-05-26 | 2004-02-10 | Akzo Aerospace Finishes V.O.F. | Coating composition having improved adhesion to substrate |
Also Published As
| Publication number | Publication date |
|---|---|
| GB2075995B (en) | 1984-07-04 |
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| Date | Code | Title | Description |
|---|---|---|---|
| PCNP | Patent ceased through non-payment of renewal fee |