CA2036816A1 - Emulsion polymerisation - Google Patents
Emulsion polymerisationInfo
- Publication number
- CA2036816A1 CA2036816A1 CA002036816A CA2036816A CA2036816A1 CA 2036816 A1 CA2036816 A1 CA 2036816A1 CA 002036816 A CA002036816 A CA 002036816A CA 2036816 A CA2036816 A CA 2036816A CA 2036816 A1 CA2036816 A1 CA 2036816A1
- Authority
- CA
- Canada
- Prior art keywords
- emulsion
- vinyl
- weight
- alkanoate
- copolymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- 239000000839 emulsion Substances 0.000 title claims abstract description 47
- 229920001577 copolymer Polymers 0.000 claims abstract description 20
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 16
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 12
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical compound [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 claims abstract description 12
- 125000005250 alkyl acrylate group Chemical group 0.000 claims abstract description 8
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 7
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 6
- 239000008199 coating composition Substances 0.000 claims abstract 3
- 239000000178 monomer Substances 0.000 claims description 19
- 239000007787 solid Substances 0.000 claims description 10
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 9
- 239000005977 Ethylene Substances 0.000 claims description 9
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical group CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 8
- 229920001567 vinyl ester resin Polymers 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- YCUBDDIKWLELPD-UHFFFAOYSA-N ethenyl 2,2-dimethylpropanoate Chemical compound CC(C)(C)C(=O)OC=C YCUBDDIKWLELPD-UHFFFAOYSA-N 0.000 claims description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 2
- 239000000203 mixture Substances 0.000 abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 16
- 230000035699 permeability Effects 0.000 abstract description 2
- 239000011258 core-shell material Substances 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 16
- 239000012071 phase Substances 0.000 description 12
- 238000000576 coating method Methods 0.000 description 10
- 239000000126 substance Substances 0.000 description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 238000007792 addition Methods 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000000049 pigment Substances 0.000 description 4
- -1 propylene butylene Chemical group 0.000 description 4
- 229910000077 silane Inorganic materials 0.000 description 4
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- ZMRUPTIKESYGQW-UHFFFAOYSA-N propranolol hydrochloride Chemical compound [H+].[Cl-].C1=CC=C2C(OCC(O)CNC(C)C)=CC=CC2=C1 ZMRUPTIKESYGQW-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- 102100035115 Testin Human genes 0.000 description 2
- 101710070533 Testin Proteins 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 229920006254 polymer film Polymers 0.000 description 2
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 description 2
- 239000004296 sodium metabisulphite Substances 0.000 description 2
- 235000010262 sodium metabisulphite Nutrition 0.000 description 2
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 2
- 235000019830 sodium polyphosphate Nutrition 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 2
- 239000002562 thickening agent Substances 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- DAFHKNAQFPVRKR-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylpropanoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)C DAFHKNAQFPVRKR-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- OAOABCKPVCUNKO-UHFFFAOYSA-N 8-methyl Nonanoic acid Chemical compound CC(C)CCCCCCC(O)=O OAOABCKPVCUNKO-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- XUKUURHRXDUEBC-KAYWLYCHSA-N Atorvastatin Chemical compound C=1C=CC=CC=1C1=C(C=2C=CC(F)=CC=2)N(CC[C@@H](O)C[C@@H](O)CC(O)=O)C(C(C)C)=C1C(=O)NC1=CC=CC=C1 XUKUURHRXDUEBC-KAYWLYCHSA-N 0.000 description 1
- FERIUCNNQQJTOY-UHFFFAOYSA-M Butyrate Chemical compound CCCC([O-])=O FERIUCNNQQJTOY-UHFFFAOYSA-M 0.000 description 1
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Natural products CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 1
- RUPBZQFQVRMKDG-UHFFFAOYSA-M Didecyldimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCC[N+](C)(C)CCCCCCCCCC RUPBZQFQVRMKDG-UHFFFAOYSA-M 0.000 description 1
- 229920000896 Ethulose Polymers 0.000 description 1
- 239000001859 Ethyl hydroxyethyl cellulose Substances 0.000 description 1
- 240000002989 Euphorbia neriifolia Species 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 241001315609 Pittosporum crassifolium Species 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- NOZAQBYNLKNDRT-UHFFFAOYSA-N [diacetyloxy(ethenyl)silyl] acetate Chemical compound CC(=O)O[Si](OC(C)=O)(OC(C)=O)C=C NOZAQBYNLKNDRT-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 238000005904 alkaline hydrolysis reaction Methods 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 239000003139 biocide Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011449 brick Substances 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920003086 cellulose ether Polymers 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013530 defoamer Substances 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- GFJVXXWOPWLRNU-UHFFFAOYSA-N ethenyl formate Chemical compound C=COC=O GFJVXXWOPWLRNU-UHFFFAOYSA-N 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- WOXXJEVNDJOOLV-UHFFFAOYSA-N ethenyl-tris(2-methoxyethoxy)silane Chemical compound COCCO[Si](OCCOC)(OCCOC)C=C WOXXJEVNDJOOLV-UHFFFAOYSA-N 0.000 description 1
- 235000019326 ethyl hydroxyethyl cellulose Nutrition 0.000 description 1
- QJQZEJFUIOWFMS-UHFFFAOYSA-N formaldehyde;sulfanediol Chemical compound O=C.OSO QJQZEJFUIOWFMS-UHFFFAOYSA-N 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- LNMQRPPRQDGUDR-UHFFFAOYSA-N hexyl prop-2-enoate Chemical compound CCCCCCOC(=O)C=C LNMQRPPRQDGUDR-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- KQNPFQTWMSNSAP-UHFFFAOYSA-N isobutyric acid Chemical compound CC(C)C(O)=O KQNPFQTWMSNSAP-UHFFFAOYSA-N 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- ZBJVLWIYKOAYQH-UHFFFAOYSA-N naphthalen-2-yl 2-hydroxybenzoate Chemical compound OC1=CC=CC=C1C(=O)OC1=CC=C(C=CC=C2)C2=C1 ZBJVLWIYKOAYQH-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229940065472 octyl acrylate Drugs 0.000 description 1
- ANISOHQJBAQUQP-UHFFFAOYSA-N octyl prop-2-enoate Chemical compound CCCCCCCCOC(=O)C=C ANISOHQJBAQUQP-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 description 1
- 235000019982 sodium hexametaphosphate Nutrition 0.000 description 1
- LGORLCOUTMVEAC-UHFFFAOYSA-M sodium;2-nonylphenolate Chemical compound [Na+].CCCCCCCCCC1=CC=CC=C1[O-] LGORLCOUTMVEAC-UHFFFAOYSA-M 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000002076 thermal analysis method Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
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
- C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
- C09D151/003—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
-
- 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
- C08F263/00—Macromolecular compounds obtained by polymerising monomers on to polymers of esters of unsaturated alcohols with saturated acids as defined in group C08F18/00
- C08F263/02—Macromolecular compounds obtained by polymerising monomers on to polymers of esters of unsaturated alcohols with saturated acids as defined in group C08F18/00 on to polymers of vinyl esters with monocarboxylic acids
Abstract
Abstract Emulsion copolymers having a core-shell structure with alkyl alkanoate, alkylene, alkyl acrylate and vinyl silane in the core and vinyl alkanoate in the shell are usable in pigmented surface coating compositions. These compositions have desired water permeability tensile strength and elongation properties at low temperatures.
The compositions provide bridging for cracks present or developing in the surface.
The compositions provide bridging for cracks present or developing in the surface.
Description
- ~3~81~
E~JLSION POLYMERISATION
Field of the Invention This invention relates to copolymer emulsions suitable for use as thick flexible coatings for concrete, brick, bitumen felt and other surfaces. They are usable on vertical, hoFizontal and sloping surfaces.
Backqround to the_invention:
The use of flexible coatings to protect surfaces from damage whether by physical or chemical means is well known. Such surface coatings will be expected to provide a decorative appearance when used internally or externally.
The invention provides copolymer emulsions suitable for incorporation in surface coatings. These coatings are ' 203~g~
E~JLSION POLYMERISATION
Field of the Invention This invention relates to copolymer emulsions suitable for use as thick flexible coatings for concrete, brick, bitumen felt and other surfaces. They are usable on vertical, hoFizontal and sloping surfaces.
Backqround to the_invention:
The use of flexible coatings to protect surfaces from damage whether by physical or chemical means is well known. Such surface coatings will be expected to provide a decorative appearance when used internally or externally.
The invention provides copolymer emulsions suitable for incorporation in surface coatings. These coatings are ' 203~g~
sufficiently flexible to provide bridging across any cracks that may develop in the substrate due to movement and the products of the invention are effective even at relatively low temperatures. ~hey possess the necessary combination of water retention and permeability properties.
General description of the invention The invention provides a copolymer emulsion comprising a core/shell structure in which the core comprises by weight:
i) from about 10% to about 60% of vinyl C1 to C4 alkanoate, ii) from about 10% to about 30% of C2 to C4 alkylene, iii) from about 1% to about 10% of alkyl (C2 to C12 acrylate iv) from about 10% to about 40% of vinyl esters having the general formula R1R2R3CCOOCHCH2 wherein Rl R2 and R3 are each alkyl groups having at least one carbon atom and Rl + R2 + R3 have from 6 to 9 carbon atoms (vinyl versatates)~
v) from about 0.1% to about 5% by weight of a vinyl silane and vi) the shell, which comprises from about 5% to about 40% by weight of the total copolymer solids, comprises vinyl C1 to C4 alkanoate at a level of at least 80%.
The copolymer will have a Tg in the range about 0C to about -30C, preferably ~5C to -20C. The Tg is obtained within a suitable range by selection of the monomers and their content. Tg of a copolymer may be calculated from the monomer values or measured using Dynamic Mechanical Thermal Analysis (D~TA).
~: ::
2~3~81~
- ~ - R3068 The solids contents of the emulsions will usually be in the ranye 35~ to 70% by weight, preferably 45% to 60%
to provide cost effective provision of the film forming solidsO
The weight mean particle size of the emulsion particles will usually be in the range 0.5 to 3.0 microns as measured by using a Joyce Loebl disc centrifuge.
Although vinyl acetate is the preferred vinyl alkanoate monomer because of its availability, cost and known reactivity, other vinyl esters within the class defined are usa~le, in particular vinyl formate, propionate, butyrate and isobutyrate. The vinyl alkanoate monomer will be present at a level of about 10%
to ensure the copolymer has the desired properties and amounts above about 60~ are unlikely to be cost effective, preferably a level above about 40% will be used.
The preferred alkylene is ethylene but other ethylenic hydrocarbons, for example propylene butylene and isobutene are usable. Preferably tha level is above about 15%.
The alkyl acrylate monomers are present to provide physical softening of the copolymers and are preferably present at a level above about 3~ and below about 8%.
The chain length of the alkyl group is preferably in the range 4 to 10. A preferred alkyl acrylate is 2-ethyl hexyl acry~ate but butyl acrylate, hexyl acrylate and octyl acrylate are also satisfactory.
The vinyl esters of versatic acids are obtained from Shell Chemicals of Chester England under the Trade Mark ~, .
, ' :' .
~3~
- 4 - ~30~8 "Veova". The pre~erred levels of vinyl versatates are from about 15% and to about 30% of the m~nomer composition. The presence of these monomers psrmits balancing of the polymer Tg and improves alkaline hydrolysis resistance.
The vinyl silane is preferably present at a level of up to about 2% for cost effectiveness. The vinyl silanes have the general formula CH2=CH-Si(oX)3 wherein X
represents separately hydrogen, acyl, an unsubstituted alkyl radical or an alkoxy substituted alkyl radical with, at most, two of the X radicals being hydrogen.
Examples of these silanes are vinyl triethoxy silane, vinyl trimethoxy silane, vinyl-tris (beta-methoxy ethoxy)~
silane and vinyl triacetoxy silane.
The presence of the alkyl acrylate and vinyl silane components togPther provide the desired balance between tensile strength and elonga~ion, particularly at low temperatures.
Functional monomexs may be included in the shell, for example monomers capable of hardening the total emulsion such as vinyl pivalate and dimethly maleate. These hardening monomer~ may be present at a level of 0 to 20~ by weight of the shell, with the desired characteri tics being obtained at a cost/effective level usually in the range 5% to I0~. Hardening monomers may also be included in the core to provide the desired product features. Preferably the al~ylene content of the shell is kept a~ low as possible.
Methods for preparing the copolymer emulsions of the invention are well characterised in the literature.
Polymer Synthesis (vols I and III) by Sandler & Karo (Academic Press 1974) and Preparative Methods of Polymer ~, . :.:
. :. , ::
~ ,.
~ ~ 3 ~
Chemistry (2nd Ed) by Sorenson and Campbell (Interscience 1968) provide preparative information. Methoden der Organischen Chemie (Houben-Wey~ Band XIV published by George Thieme Verlag Stuttgart (1961j also provides preparative descriptions.
The copolymer emulsions of the invention are usable in paints intended for surface coatings; these compositions will usually comprise (by weight):
i) 3~ to 35% dry weight copolymer solids, ii) 5% to 35% aqueous phase including water present in emulsion, iii) 5% to 55% filler, and iv) 5~ to 30% pigment Pigmented compositions of use as roof treating compositions usually comprise (by weight of solids)~
Thickener eg cellulose ether 1.5 to 3.5%
Dispersant eg sodium polyphosphate 0.75 to 2.0%
Preservative 0.05 to 0.2%
De~oamer 0.1 to 0.3%
Pigment 5 to 30%
Filler 5 to 55%
Coalescing solvent eg alcohol ester 1 to 3%
Emulsion copolymer dry solids 3 to 35%
Water, including emulsion aqueous base remainder The fillers will include quartz powder, kaolin, silica and milled minerals; the pigments include titanium dioxide, zinc oxide and xinc sulphide.
The coatings formed by these compositions have water uptake level which allows response to changing weather 2~3681~
conditions. A water uptake which is too high can lead to disintegration as the coating becomes spongy. At the other extremP a highly water resistant coating will not allow moisture between it and the substrate to escape with consequent damage from moisture retention or freezing.
These coatings will be applied by conventional means, for example, by spray, bush or roller. They are usable in protection or repair situations.
Test methods:
The following procedures were used to test emulsions prepared according to the invention.
i~ Tensile strength/elongation: An emulsion sample ~,entrifuged to remove air was drawn down to a 0.63 mm film on a ptfe coated glass plate and dried for 7 days at 21C and 65% relative humidity. For room temperature testing 1 cm by 5 cm test samples were prepared and mounted on a cardboard mount. The mounted specimen was clamped hetween a pair of jaws spaced 3 cm apart of an Instron apparatus and the jaws separated at 50 cm/min. Wet tests were performed on specimen dried films immersed in water at 21C for 24 hours before mounting.
Tests were performed over a range of temperatures by using an Instron en~ironment cabinet.
ii) The tensile strength/elongation tests on pigmented products were performed using procedure (i) but with a wet drawn down film o~ 0.25 mm thickness.
i ~3~6 iii) Water uptake: Dried (5 cm x 5 cm) films of the emulsion or pi~mented product were prepared as in methods (i) or ~ii) and immersed in water at 21C.
Water uptake was determined by weighing after 1 day and 7 days.
When reporting the elongation results the use of a +
sign indicates the sample did not break at the maximum extension available with the machine at the test conditions.
Specific description of the invention Copolymer emulsions were prepared to illustrate the invention.
% wt.
Vinyl Acetate ) 39.00 VeoVa 9 * ) monomer 25.00 2-Ethylhexyl Acrylate ) phase 1 5.00 Silane A172 ** ) 1.00 Vinyl Acetate (monomer phase 2) 10.00 , Ethylene 20.00 Stabilisin~ System Natrosol 2S0 LR *** 1.00 Perlankrol FN 65 **** 3.08 Initi.ator System Sodium persulphate 0.45 Formaldehyde sulphoxylate (Formosul)0.28 .. . .
. ~ . .
: : :, , ' ~..
~3~
- ~ - R3068 Finishing o~f stage t-butyl hydroperoxide 0.30 Sodium metabisulphite 0~20 T~ (C) -8.0 * a vinyl ester of versatic acid in which R1+R2+R3 is 7.
** vinyl-tris (beta-methoxyethoxy) silane obtainable from Union Carbide of USA.
*** hydroxy e$hyl cellulose obtainable from Hercules Chemicals Ltd of London England.
**** sodium nonyl phenol 20E0 sulphate obtainable from Lankro Chemicals of Manchester England.
The Natrosol 250 LR (54 gm.) and the 65% aqueous solution of Perlankrol FN65 (166~2 gm.) w re dissolved in deionised water (3700 gm) at 50C. The solution was then cooled to 30C and the pH adjusted with formic acid. The ferric chloride and 3.5% of the Formosul (O.5 gm.~ was added and the water phase immediately loaded to a stirred 10 litre reactor.
The reactor (at 30C), was purged twice with nitrogen to 7 Bar (guage) and then once with ethylene to 7 Bar (guage). 25% of monomer phase 1 (945 gm.) and 70%
of the ethylene (756 gm.) were then added and the internal temperature stabilised at 30C.
The continuous additions of the remainder of monomer phase 1 and the initiators (24.3 gm. of sodium persulphate and 14.6 gm. of Formosul each in 625 gm. of deionised water) was then commenced. The initiators were added over seven hours with the first quarter hour and last half hour at double rate, and the monomer over five houxs. The internal temperature was allowed to rise to ., . :
.
:: : ,' ' .~ ~
203681~
55C over the first 30 minutes of additions and was then maintained at 54-56C until the end of the continuous additions. At 55C the reactor pressure was increased and maintained at 65 Bar (guage~ until the remainder of the ethylene had been added (approximately two hours).
When monomer phase 1 addition was complete, monomer phase 2 (540 gm.) was added over one hour. When all additions were added the reaction mass was cooled to 50C and the finishing off stage (16.2 gm of t-butyl hydroperoxide and 10.8 gm. of sodium metabisulphite each in 150 gm. of deionised water) was added to the reactor in separate streams over thirty minutes whilst cooling the emulsion to 30C. The emulsion was then discharged to a degassing tank. the solidc content was 50% and weight means particle size 1.5 micron.
The tensile strength and elongation of this emulsion were measured and the results given in Table I.
Table I
Temperature(C) Tensile Strength (Kg/cm2) Elongation(%) Dry Wet Dry Wet 21 6.1 1.8 2150 1465 0 35.8 NM 339 NM
37.3 NM 339 NM
-10 37.5 NM 254 NM
M - Not measured as wet properties cannot be measured below 0C.
., ` , ~' ' ~3~8~
~xample 2 ~comparison) Copol~mer emulsions A, B and C were prepared using the procedure of Example 1. They were subjected to the tensile strength and elongation tests described previously at a number of temperatures (room temperature 2~C).
The compositions of A, B and C were (by weight):
A B* C
Yinyl acetate ) 3534.5 40 Veova 9 ~ Phase 25 25 25 2 ethyl hexyl acrylate) 1 5 5 None Silane A172 ) none0.5 None Vinyl acetate (Phase 2) 10 10 10 Ethylene 25 25 25 Tg (C) -10 -10 -6.5 * B was a composition according to the invention having solids content of 50~ and weight mean particle size of 0.74 micron.
The change in Tg for composition C is not unexpected because the composition has been balanced for comparison purposes. The properties of these emulsions are given in Tables II and III. The benefit obtained by including the vinyl silane in emulsion B is clearly seen and comparison of B and C shows the benefit of including the vinyl silane and alkyl acrylate together.
~, :
. 2~368-l ~
Table II
Room Temperature Testing Tensil~ Strength (Kg/cm~) Dry Wet A B C A B C
1.8 3.4 2.1 0.7 1.5 1.1 The three emulsions were satisfactory on elongation to the limits of the test machine.
Table III
Low Temperature Testin~
Temperature Tensile strength Elongation (%) ~Kg/cm ) A B C A B C
0C 18.923.238.1 350 350 350 -5C 36.338.237.6 350 350 275 -10C 41.043.038.2 266 275 258 -15C 40.742.540.5 175 225 158 These lower temperature results show the benefits obtained by incorporating vinyl silane and alkyl acrylate together.
, ::
2~3fi8~ 6 Example 3 ~comparison) Copolymer emulsions D and E were prepared using the procedure of Example 1 with the excaption that all the athylene charge was introduced initially. The compositions of D and E were (by weight):
D E*
Vinyl acetate ) 49 39 Veova 9 ) Phase 25 25 2 ethyl hexyl acrylate) 1 5 5 Silane A172 Vinyl a~etate (Phase 2) none 10 Ethylene 20 20 Tg (C) -7.5 -8.0 The properties o~ these emulsions are given in Tables IV & V.
* E was a composition according to the invention having a solids content of 50% and a weight mean particle size of 2.5 micron.
Table IV
Room Temperature Testing Tensile strength (Kg/cm ) Elongation %
Dry Wet Dry Wet D E D E D E D E
10.1 7.9 5.4 ~.7 1000 10331375 1733 ~, :
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The presence of the shell formed by the phase 2 vinyl acetate is seen to improve the wet characteristics of the emulsion.
Table V
Low Temperat~ure~ Testin~
Temperature Tensile strength Elongation %
kg/cm2 Example D E D E
0C 32.5 43. ~ 350+ 350+
32.6 43.4 350+ 350 -10 32.1 43.1 300 275 -15 34.2 46.0 275 170 The presence of the shell is seen to give considerable improvement to the tensile strength at these lower temperatures while the elongation, although reduced, is still at a satisfactory level.
Example 4 (comparison) The effect of vinyl silane at a level of 1% was investigated by comparing composition E from Example 3 with a composition F containing no vinyl silane and with 40% vinyl acetate in the core. The ethylene charge was introduced initially but otherwise the pxocedure of Example 1 was followed. Composition E had a Tg of -8. ooc and composition F a Tg of -7.0C.
The properties of these emulsions are given in Tables VI
and VII
.
~ , , ' ' ' .
2~36~
Table VI
Room Temperature Testing Tensile strength (Kg/~m2) Elongation %
Dry Wet Dry Wet F E F E F E F E
2.1 7.9 1.0 8.7 2166+ 1033 2166+ 1733 Table VII
Low Temperature Testing Temperature Tensile strength Elongation %
kg/cm2 Example F E F E
0C 28.7 43.8 350~ 350+
-5 34.4 43.4 350+ 350 -10 33.5 43.1 283 275 :~--15 34.7 46.0 241 170 Thus the presence of the vinyl silane has a clear effect on the tensile strength while retaining effective elongation properties.
Example 5 Compounds containing pigments and intended for roof treatment were prepared using a standard test commercial formulation and emulsions of the invention. The test roofing compound had the composition in parts by weight:
,: ~ ~. . . . .
. . , . . ;; . . . ~ . :
- 2~8~ `
~ 15 - R3068 Materials Parts by Weiqht i) Bermocoll E3209 (5% soln) 56 ii) Calgon S (5% soln) 25 iii) Acticide MPM
iv) Hercules 1512 M 2 v~ Tioxide RCR 2 176 vi) Queensfil 25 124 vii) Texanol 20 Water 48 Emulsion 548 i) Thickener. Ethyl hydroxyethyl cellulose.
Obtainable from Berol Kemi (UK) Ltd., Watford, England.
ii) Dispersant. Sodium polyphosphate. Obtainable from Albright and Wilson, Phosphate Group, Trinity St., Oldbury, Warley, England.
iii) Mercurial biocide. Obtainable from Thor Chemicals UK Ltd., Cheadle Hulme, England.
iv) Defoamer. Obtainable from Hercules Chemicals Ltd., London, England.
v) Titanium dioxide. Obtainable from Tioxide UK Ltd., Billingham, England.
vi) Extender. Obtainable from ECC International Ltd., St. Austell, England.
vii) Coalescing agent. Obtainable from Eastman Chemicals International A.G., Hemel Hempstead, England.
20~68~
The emulsions of the invention, ie Example I and compositions B and E, were formulated into the above roofing compound together with composition F as comparison. The tensile strength and elongation were measure~ and are given in Table VIII.
Table VIII
Emulsion E ~ B Ex I
Tensile strength (Kg/cm ) 21C dry 1008 3.0 NM 14.6 21C wet 5O7 1.6 NN 6.3 0C 58.0 28.3 NM 53.6 -5C 92.0 72.9 32.5 92.6 -10C 114.0 110.0 63.6 110.0 -15C 11800 110.0 40.1 113.6 Elongation (%) 21C dry 1500 2166 NM 1350 21C wet 1116 1733 NM 833 0C 350+ 350+ NM 350+
-5C 350 350+ 350 343 -1~C 207 293 241 250 water uptake (%) NM 47 28 25 Comparison of E and F demonstrates the application properties of the emulsions reflect the test results of the emulsions.
The water uptake of the polymer films and films of the pigmented roofing compounds were measured for the four emulsions quoted above; the results are given in Table IX.
', ' ' ~ , ':
'-Table IX
Water uptake (~?
Polymer film Pigmented film Example I 25 10 Composition B 28 11 Composition E 30 11 Composition F 47 17 These results demonstrate the reduction in water sensitiv.ity obtained when using the copolymer emulsions of the invention.
,. : , , , , ~ : , , , .:
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General description of the invention The invention provides a copolymer emulsion comprising a core/shell structure in which the core comprises by weight:
i) from about 10% to about 60% of vinyl C1 to C4 alkanoate, ii) from about 10% to about 30% of C2 to C4 alkylene, iii) from about 1% to about 10% of alkyl (C2 to C12 acrylate iv) from about 10% to about 40% of vinyl esters having the general formula R1R2R3CCOOCHCH2 wherein Rl R2 and R3 are each alkyl groups having at least one carbon atom and Rl + R2 + R3 have from 6 to 9 carbon atoms (vinyl versatates)~
v) from about 0.1% to about 5% by weight of a vinyl silane and vi) the shell, which comprises from about 5% to about 40% by weight of the total copolymer solids, comprises vinyl C1 to C4 alkanoate at a level of at least 80%.
The copolymer will have a Tg in the range about 0C to about -30C, preferably ~5C to -20C. The Tg is obtained within a suitable range by selection of the monomers and their content. Tg of a copolymer may be calculated from the monomer values or measured using Dynamic Mechanical Thermal Analysis (D~TA).
~: ::
2~3~81~
- ~ - R3068 The solids contents of the emulsions will usually be in the ranye 35~ to 70% by weight, preferably 45% to 60%
to provide cost effective provision of the film forming solidsO
The weight mean particle size of the emulsion particles will usually be in the range 0.5 to 3.0 microns as measured by using a Joyce Loebl disc centrifuge.
Although vinyl acetate is the preferred vinyl alkanoate monomer because of its availability, cost and known reactivity, other vinyl esters within the class defined are usa~le, in particular vinyl formate, propionate, butyrate and isobutyrate. The vinyl alkanoate monomer will be present at a level of about 10%
to ensure the copolymer has the desired properties and amounts above about 60~ are unlikely to be cost effective, preferably a level above about 40% will be used.
The preferred alkylene is ethylene but other ethylenic hydrocarbons, for example propylene butylene and isobutene are usable. Preferably tha level is above about 15%.
The alkyl acrylate monomers are present to provide physical softening of the copolymers and are preferably present at a level above about 3~ and below about 8%.
The chain length of the alkyl group is preferably in the range 4 to 10. A preferred alkyl acrylate is 2-ethyl hexyl acry~ate but butyl acrylate, hexyl acrylate and octyl acrylate are also satisfactory.
The vinyl esters of versatic acids are obtained from Shell Chemicals of Chester England under the Trade Mark ~, .
, ' :' .
~3~
- 4 - ~30~8 "Veova". The pre~erred levels of vinyl versatates are from about 15% and to about 30% of the m~nomer composition. The presence of these monomers psrmits balancing of the polymer Tg and improves alkaline hydrolysis resistance.
The vinyl silane is preferably present at a level of up to about 2% for cost effectiveness. The vinyl silanes have the general formula CH2=CH-Si(oX)3 wherein X
represents separately hydrogen, acyl, an unsubstituted alkyl radical or an alkoxy substituted alkyl radical with, at most, two of the X radicals being hydrogen.
Examples of these silanes are vinyl triethoxy silane, vinyl trimethoxy silane, vinyl-tris (beta-methoxy ethoxy)~
silane and vinyl triacetoxy silane.
The presence of the alkyl acrylate and vinyl silane components togPther provide the desired balance between tensile strength and elonga~ion, particularly at low temperatures.
Functional monomexs may be included in the shell, for example monomers capable of hardening the total emulsion such as vinyl pivalate and dimethly maleate. These hardening monomer~ may be present at a level of 0 to 20~ by weight of the shell, with the desired characteri tics being obtained at a cost/effective level usually in the range 5% to I0~. Hardening monomers may also be included in the core to provide the desired product features. Preferably the al~ylene content of the shell is kept a~ low as possible.
Methods for preparing the copolymer emulsions of the invention are well characterised in the literature.
Polymer Synthesis (vols I and III) by Sandler & Karo (Academic Press 1974) and Preparative Methods of Polymer ~, . :.:
. :. , ::
~ ,.
~ ~ 3 ~
Chemistry (2nd Ed) by Sorenson and Campbell (Interscience 1968) provide preparative information. Methoden der Organischen Chemie (Houben-Wey~ Band XIV published by George Thieme Verlag Stuttgart (1961j also provides preparative descriptions.
The copolymer emulsions of the invention are usable in paints intended for surface coatings; these compositions will usually comprise (by weight):
i) 3~ to 35% dry weight copolymer solids, ii) 5% to 35% aqueous phase including water present in emulsion, iii) 5% to 55% filler, and iv) 5~ to 30% pigment Pigmented compositions of use as roof treating compositions usually comprise (by weight of solids)~
Thickener eg cellulose ether 1.5 to 3.5%
Dispersant eg sodium polyphosphate 0.75 to 2.0%
Preservative 0.05 to 0.2%
De~oamer 0.1 to 0.3%
Pigment 5 to 30%
Filler 5 to 55%
Coalescing solvent eg alcohol ester 1 to 3%
Emulsion copolymer dry solids 3 to 35%
Water, including emulsion aqueous base remainder The fillers will include quartz powder, kaolin, silica and milled minerals; the pigments include titanium dioxide, zinc oxide and xinc sulphide.
The coatings formed by these compositions have water uptake level which allows response to changing weather 2~3681~
conditions. A water uptake which is too high can lead to disintegration as the coating becomes spongy. At the other extremP a highly water resistant coating will not allow moisture between it and the substrate to escape with consequent damage from moisture retention or freezing.
These coatings will be applied by conventional means, for example, by spray, bush or roller. They are usable in protection or repair situations.
Test methods:
The following procedures were used to test emulsions prepared according to the invention.
i~ Tensile strength/elongation: An emulsion sample ~,entrifuged to remove air was drawn down to a 0.63 mm film on a ptfe coated glass plate and dried for 7 days at 21C and 65% relative humidity. For room temperature testing 1 cm by 5 cm test samples were prepared and mounted on a cardboard mount. The mounted specimen was clamped hetween a pair of jaws spaced 3 cm apart of an Instron apparatus and the jaws separated at 50 cm/min. Wet tests were performed on specimen dried films immersed in water at 21C for 24 hours before mounting.
Tests were performed over a range of temperatures by using an Instron en~ironment cabinet.
ii) The tensile strength/elongation tests on pigmented products were performed using procedure (i) but with a wet drawn down film o~ 0.25 mm thickness.
i ~3~6 iii) Water uptake: Dried (5 cm x 5 cm) films of the emulsion or pi~mented product were prepared as in methods (i) or ~ii) and immersed in water at 21C.
Water uptake was determined by weighing after 1 day and 7 days.
When reporting the elongation results the use of a +
sign indicates the sample did not break at the maximum extension available with the machine at the test conditions.
Specific description of the invention Copolymer emulsions were prepared to illustrate the invention.
% wt.
Vinyl Acetate ) 39.00 VeoVa 9 * ) monomer 25.00 2-Ethylhexyl Acrylate ) phase 1 5.00 Silane A172 ** ) 1.00 Vinyl Acetate (monomer phase 2) 10.00 , Ethylene 20.00 Stabilisin~ System Natrosol 2S0 LR *** 1.00 Perlankrol FN 65 **** 3.08 Initi.ator System Sodium persulphate 0.45 Formaldehyde sulphoxylate (Formosul)0.28 .. . .
. ~ . .
: : :, , ' ~..
~3~
- ~ - R3068 Finishing o~f stage t-butyl hydroperoxide 0.30 Sodium metabisulphite 0~20 T~ (C) -8.0 * a vinyl ester of versatic acid in which R1+R2+R3 is 7.
** vinyl-tris (beta-methoxyethoxy) silane obtainable from Union Carbide of USA.
*** hydroxy e$hyl cellulose obtainable from Hercules Chemicals Ltd of London England.
**** sodium nonyl phenol 20E0 sulphate obtainable from Lankro Chemicals of Manchester England.
The Natrosol 250 LR (54 gm.) and the 65% aqueous solution of Perlankrol FN65 (166~2 gm.) w re dissolved in deionised water (3700 gm) at 50C. The solution was then cooled to 30C and the pH adjusted with formic acid. The ferric chloride and 3.5% of the Formosul (O.5 gm.~ was added and the water phase immediately loaded to a stirred 10 litre reactor.
The reactor (at 30C), was purged twice with nitrogen to 7 Bar (guage) and then once with ethylene to 7 Bar (guage). 25% of monomer phase 1 (945 gm.) and 70%
of the ethylene (756 gm.) were then added and the internal temperature stabilised at 30C.
The continuous additions of the remainder of monomer phase 1 and the initiators (24.3 gm. of sodium persulphate and 14.6 gm. of Formosul each in 625 gm. of deionised water) was then commenced. The initiators were added over seven hours with the first quarter hour and last half hour at double rate, and the monomer over five houxs. The internal temperature was allowed to rise to ., . :
.
:: : ,' ' .~ ~
203681~
55C over the first 30 minutes of additions and was then maintained at 54-56C until the end of the continuous additions. At 55C the reactor pressure was increased and maintained at 65 Bar (guage~ until the remainder of the ethylene had been added (approximately two hours).
When monomer phase 1 addition was complete, monomer phase 2 (540 gm.) was added over one hour. When all additions were added the reaction mass was cooled to 50C and the finishing off stage (16.2 gm of t-butyl hydroperoxide and 10.8 gm. of sodium metabisulphite each in 150 gm. of deionised water) was added to the reactor in separate streams over thirty minutes whilst cooling the emulsion to 30C. The emulsion was then discharged to a degassing tank. the solidc content was 50% and weight means particle size 1.5 micron.
The tensile strength and elongation of this emulsion were measured and the results given in Table I.
Table I
Temperature(C) Tensile Strength (Kg/cm2) Elongation(%) Dry Wet Dry Wet 21 6.1 1.8 2150 1465 0 35.8 NM 339 NM
37.3 NM 339 NM
-10 37.5 NM 254 NM
M - Not measured as wet properties cannot be measured below 0C.
., ` , ~' ' ~3~8~
~xample 2 ~comparison) Copol~mer emulsions A, B and C were prepared using the procedure of Example 1. They were subjected to the tensile strength and elongation tests described previously at a number of temperatures (room temperature 2~C).
The compositions of A, B and C were (by weight):
A B* C
Yinyl acetate ) 3534.5 40 Veova 9 ~ Phase 25 25 25 2 ethyl hexyl acrylate) 1 5 5 None Silane A172 ) none0.5 None Vinyl acetate (Phase 2) 10 10 10 Ethylene 25 25 25 Tg (C) -10 -10 -6.5 * B was a composition according to the invention having solids content of 50~ and weight mean particle size of 0.74 micron.
The change in Tg for composition C is not unexpected because the composition has been balanced for comparison purposes. The properties of these emulsions are given in Tables II and III. The benefit obtained by including the vinyl silane in emulsion B is clearly seen and comparison of B and C shows the benefit of including the vinyl silane and alkyl acrylate together.
~, :
. 2~368-l ~
Table II
Room Temperature Testing Tensil~ Strength (Kg/cm~) Dry Wet A B C A B C
1.8 3.4 2.1 0.7 1.5 1.1 The three emulsions were satisfactory on elongation to the limits of the test machine.
Table III
Low Temperature Testin~
Temperature Tensile strength Elongation (%) ~Kg/cm ) A B C A B C
0C 18.923.238.1 350 350 350 -5C 36.338.237.6 350 350 275 -10C 41.043.038.2 266 275 258 -15C 40.742.540.5 175 225 158 These lower temperature results show the benefits obtained by incorporating vinyl silane and alkyl acrylate together.
, ::
2~3fi8~ 6 Example 3 ~comparison) Copolymer emulsions D and E were prepared using the procedure of Example 1 with the excaption that all the athylene charge was introduced initially. The compositions of D and E were (by weight):
D E*
Vinyl acetate ) 49 39 Veova 9 ) Phase 25 25 2 ethyl hexyl acrylate) 1 5 5 Silane A172 Vinyl a~etate (Phase 2) none 10 Ethylene 20 20 Tg (C) -7.5 -8.0 The properties o~ these emulsions are given in Tables IV & V.
* E was a composition according to the invention having a solids content of 50% and a weight mean particle size of 2.5 micron.
Table IV
Room Temperature Testing Tensile strength (Kg/cm ) Elongation %
Dry Wet Dry Wet D E D E D E D E
10.1 7.9 5.4 ~.7 1000 10331375 1733 ~, :
,, : .
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.
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The presence of the shell formed by the phase 2 vinyl acetate is seen to improve the wet characteristics of the emulsion.
Table V
Low Temperat~ure~ Testin~
Temperature Tensile strength Elongation %
kg/cm2 Example D E D E
0C 32.5 43. ~ 350+ 350+
32.6 43.4 350+ 350 -10 32.1 43.1 300 275 -15 34.2 46.0 275 170 The presence of the shell is seen to give considerable improvement to the tensile strength at these lower temperatures while the elongation, although reduced, is still at a satisfactory level.
Example 4 (comparison) The effect of vinyl silane at a level of 1% was investigated by comparing composition E from Example 3 with a composition F containing no vinyl silane and with 40% vinyl acetate in the core. The ethylene charge was introduced initially but otherwise the pxocedure of Example 1 was followed. Composition E had a Tg of -8. ooc and composition F a Tg of -7.0C.
The properties of these emulsions are given in Tables VI
and VII
.
~ , , ' ' ' .
2~36~
Table VI
Room Temperature Testing Tensile strength (Kg/~m2) Elongation %
Dry Wet Dry Wet F E F E F E F E
2.1 7.9 1.0 8.7 2166+ 1033 2166+ 1733 Table VII
Low Temperature Testing Temperature Tensile strength Elongation %
kg/cm2 Example F E F E
0C 28.7 43.8 350~ 350+
-5 34.4 43.4 350+ 350 -10 33.5 43.1 283 275 :~--15 34.7 46.0 241 170 Thus the presence of the vinyl silane has a clear effect on the tensile strength while retaining effective elongation properties.
Example 5 Compounds containing pigments and intended for roof treatment were prepared using a standard test commercial formulation and emulsions of the invention. The test roofing compound had the composition in parts by weight:
,: ~ ~. . . . .
. . , . . ;; . . . ~ . :
- 2~8~ `
~ 15 - R3068 Materials Parts by Weiqht i) Bermocoll E3209 (5% soln) 56 ii) Calgon S (5% soln) 25 iii) Acticide MPM
iv) Hercules 1512 M 2 v~ Tioxide RCR 2 176 vi) Queensfil 25 124 vii) Texanol 20 Water 48 Emulsion 548 i) Thickener. Ethyl hydroxyethyl cellulose.
Obtainable from Berol Kemi (UK) Ltd., Watford, England.
ii) Dispersant. Sodium polyphosphate. Obtainable from Albright and Wilson, Phosphate Group, Trinity St., Oldbury, Warley, England.
iii) Mercurial biocide. Obtainable from Thor Chemicals UK Ltd., Cheadle Hulme, England.
iv) Defoamer. Obtainable from Hercules Chemicals Ltd., London, England.
v) Titanium dioxide. Obtainable from Tioxide UK Ltd., Billingham, England.
vi) Extender. Obtainable from ECC International Ltd., St. Austell, England.
vii) Coalescing agent. Obtainable from Eastman Chemicals International A.G., Hemel Hempstead, England.
20~68~
The emulsions of the invention, ie Example I and compositions B and E, were formulated into the above roofing compound together with composition F as comparison. The tensile strength and elongation were measure~ and are given in Table VIII.
Table VIII
Emulsion E ~ B Ex I
Tensile strength (Kg/cm ) 21C dry 1008 3.0 NM 14.6 21C wet 5O7 1.6 NN 6.3 0C 58.0 28.3 NM 53.6 -5C 92.0 72.9 32.5 92.6 -10C 114.0 110.0 63.6 110.0 -15C 11800 110.0 40.1 113.6 Elongation (%) 21C dry 1500 2166 NM 1350 21C wet 1116 1733 NM 833 0C 350+ 350+ NM 350+
-5C 350 350+ 350 343 -1~C 207 293 241 250 water uptake (%) NM 47 28 25 Comparison of E and F demonstrates the application properties of the emulsions reflect the test results of the emulsions.
The water uptake of the polymer films and films of the pigmented roofing compounds were measured for the four emulsions quoted above; the results are given in Table IX.
', ' ' ~ , ':
'-Table IX
Water uptake (~?
Polymer film Pigmented film Example I 25 10 Composition B 28 11 Composition E 30 11 Composition F 47 17 These results demonstrate the reduction in water sensitiv.ity obtained when using the copolymer emulsions of the invention.
,. : , , , , ~ : , , , .:
- ~
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Claims (12)
1. A copolymer emulsion, having a Tg in the range from about 0°C to about -30°C, comprising a core/shell structure in which the core comprises by weight:
i) from about 10% to about 60% of vinyl C1 to C4 alkanoate, ii) from about 10% to about 30% of C2 to C4 alkylene, iii) from about 1% to about 10% of alkyl (C2 to C12) acrylate, iv) from about 10% to about 40% of vinyl esters having the general formula R1R2R3CCOOCHCH2 wherein R1 R2 and R3 are each alkyl groups having at least one carbon atom and R1 + R2 + R3 have from 6 to 9 carbon-atoms, v) from about 0.1% to about 5% by weight of a vinyl silane and vi) the shell, which comprises from about 5% to about 40% by weight of the total copolymer solids, comprises vinyl C1 to C4 alkanoate at a level of at least 80%.
i) from about 10% to about 60% of vinyl C1 to C4 alkanoate, ii) from about 10% to about 30% of C2 to C4 alkylene, iii) from about 1% to about 10% of alkyl (C2 to C12) acrylate, iv) from about 10% to about 40% of vinyl esters having the general formula R1R2R3CCOOCHCH2 wherein R1 R2 and R3 are each alkyl groups having at least one carbon atom and R1 + R2 + R3 have from 6 to 9 carbon-atoms, v) from about 0.1% to about 5% by weight of a vinyl silane and vi) the shell, which comprises from about 5% to about 40% by weight of the total copolymer solids, comprises vinyl C1 to C4 alkanoate at a level of at least 80%.
2. An emulsion as claimed in claim 1 wherein the vinyl alkanoate is present in the range above about 40%.
3. An emulsion as claimed in claim 1 or 2 wherein the alkylene monomer is present at a level above about 15%.
4. An emulsion as claimed in any preceding claim wherein the alkyl acrylate is present in the range from about 3% to about 8%.
5. An emulsion as claimed in any preceding claim wherein the chain length of the alkyl group in the alkyl acrylate is from 4 to 10.
6. An emulsion as claimed in any preceding claim wherein the vinyl alkanoate is vinyl acetate.
7. An emulsion as claimed in any preceding claim wherein the alkylene monomer is ethylene.
8. An emulsion as claimed in any preceding claim wherein the solids content is in the range 35% to 70% by weight.
9. An emulsion as claimed in any preceding claim wherein the shell contains form 0% to 20%by weight of hardening monomer selected from vinyl pivalate and dimethl maleate.
10. The use of the copolymer emulsion as defined in any preceding claim in pigmented surface coating compositions.
11. Pigmented surface coating compositions containing an effective amount, preferably from about 3% to about 35%
solids, of an emulsion claimed in any of claims 1 to 9.
solids, of an emulsion claimed in any of claims 1 to 9.
12. A copolymer emulision as claimed in claim 1 and substantially as described herein.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP90301973 | 1990-02-23 | ||
EP90301973.5 | 1990-02-23 |
Publications (1)
Publication Number | Publication Date |
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CA2036816A1 true CA2036816A1 (en) | 1991-08-24 |
Family
ID=8205305
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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CA002036816A Abandoned CA2036816A1 (en) | 1990-02-23 | 1991-02-21 | Emulsion polymerisation |
Country Status (6)
Country | Link |
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US (1) | US5073578A (en) |
EP (1) | EP0444827B1 (en) |
AT (1) | ATE127133T1 (en) |
AU (1) | AU7126191A (en) |
CA (1) | CA2036816A1 (en) |
DE (1) | DE69112453T2 (en) |
Families Citing this family (31)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE4306831A1 (en) * | 1993-03-04 | 1994-09-08 | Wacker Chemie Gmbh | Core-shell copolymer dispersions whose shell contains hydrolyzable, organosilicon comonomers |
EP0614919A1 (en) * | 1993-03-12 | 1994-09-14 | Shell Internationale Researchmaatschappij B.V. | A latex composition containing polymer particles having core/shell structure |
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US4569964A (en) * | 1983-10-27 | 1986-02-11 | The Dow Chemical Company | Heat/light stable interpenetrating polymer network latexes |
US4616057A (en) * | 1985-07-10 | 1986-10-07 | Sun Chemical Corporation | Polymer emulsion containing an interpenetrating polymer network |
AU596439B2 (en) * | 1986-08-20 | 1990-05-03 | Glidden Company, The | Emulsion polymers containing acrylonitrile or vinylidene chloride |
DE3763666D1 (en) * | 1986-11-14 | 1990-08-16 | Johannes Loebbert | DEVICE FOR HYGIENIC WASTE RECORDING IN HOSPITALS, LABORATORIES AND SIMILAR INSTITUTES. |
DE3731760A1 (en) * | 1987-09-22 | 1989-03-30 | Texaco Ag | WAESSED PLASTIC DISPERSION |
US4942086A (en) * | 1988-09-09 | 1990-07-17 | National Starch And Chemical Investment Holding Corporation | Two-stage heat resistant binders for nonwovens |
US4975320A (en) * | 1989-02-01 | 1990-12-04 | Air Products And Chemicals, Inc. | Nonwoven products bonded with binder emulsions of copolymers of vinyl acetate/ethylene/incompatible comonomer/latent crosslinking comonomer |
-
1991
- 1991-02-21 AT AT91301413T patent/ATE127133T1/en not_active IP Right Cessation
- 1991-02-21 EP EP91301413A patent/EP0444827B1/en not_active Expired - Lifetime
- 1991-02-21 CA CA002036816A patent/CA2036816A1/en not_active Abandoned
- 1991-02-21 US US07/658,922 patent/US5073578A/en not_active Expired - Lifetime
- 1991-02-21 AU AU71261/91A patent/AU7126191A/en not_active Abandoned
- 1991-02-21 DE DE69112453T patent/DE69112453T2/en not_active Expired - Fee Related
Also Published As
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DE69112453D1 (en) | 1995-10-05 |
EP0444827A1 (en) | 1991-09-04 |
DE69112453T2 (en) | 1996-02-29 |
AU7126191A (en) | 1991-08-29 |
ATE127133T1 (en) | 1995-09-15 |
EP0444827B1 (en) | 1995-08-30 |
US5073578A (en) | 1991-12-17 |
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EEER | Examination request | ||
FZDE | Discontinued |