CN105924560A - Salt-fog-resistant vinylidene chloride copolymer latex - Google Patents
Salt-fog-resistant vinylidene chloride copolymer latex Download PDFInfo
- Publication number
- CN105924560A CN105924560A CN201610405582.0A CN201610405582A CN105924560A CN 105924560 A CN105924560 A CN 105924560A CN 201610405582 A CN201610405582 A CN 201610405582A CN 105924560 A CN105924560 A CN 105924560A
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- Prior art keywords
- monomer
- agent
- reactor
- vinylidene chloride
- copolymer latex
- Prior art date
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- 239000004816 latex Substances 0.000 title claims abstract description 47
- 229920000126 latex Polymers 0.000 title claims abstract description 47
- 229920001577 copolymer Polymers 0.000 title claims abstract description 38
- 239000000178 monomer Substances 0.000 claims abstract description 51
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 25
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 150000003839 salts Chemical class 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims description 26
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 claims description 25
- 238000003756 stirring Methods 0.000 claims description 23
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- -1 acrylic ester Chemical class 0.000 claims description 13
- 239000008367 deionised water Substances 0.000 claims description 13
- 229910021641 deionized water Inorganic materials 0.000 claims description 13
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- 239000007789 gas Substances 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 238000007599 discharging Methods 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- 239000003002 pH adjusting agent Substances 0.000 claims description 8
- 238000010792 warming Methods 0.000 claims description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 7
- CCJAYIGMMRQRAO-UHFFFAOYSA-N 2-[4-[(2-hydroxyphenyl)methylideneamino]butyliminomethyl]phenol Chemical compound OC1=CC=CC=C1C=NCCCCN=CC1=CC=CC=C1O CCJAYIGMMRQRAO-UHFFFAOYSA-N 0.000 claims description 7
- 239000000839 emulsion Substances 0.000 claims description 7
- 239000003999 initiator Substances 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 5
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 4
- 239000012875 nonionic emulsifier Substances 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- 230000000977 initiatory effect Effects 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 2
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims description 2
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- 150000001336 alkenes Chemical class 0.000 claims description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M methacrylate group Chemical group C(C(=C)C)(=O)[O-] CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 2
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims 1
- DUIOKRXOKLLURE-UHFFFAOYSA-N 2-octylphenol Chemical group CCCCCCCCC1=CC=CC=C1O DUIOKRXOKLLURE-UHFFFAOYSA-N 0.000 claims 1
- 229940051841 polyoxyethylene ether Drugs 0.000 claims 1
- 229920000056 polyoxyethylene ether Polymers 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 7
- 239000000853 adhesive Substances 0.000 abstract description 3
- 230000001070 adhesive effect Effects 0.000 abstract description 3
- 239000002245 particle Substances 0.000 abstract description 2
- 238000003860 storage Methods 0.000 abstract description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 12
- 235000019394 potassium persulphate Nutrition 0.000 description 12
- 238000000576 coating method Methods 0.000 description 11
- 239000011248 coating agent Substances 0.000 description 10
- 238000007334 copolymerization reaction Methods 0.000 description 7
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 6
- 238000006073 displacement reaction Methods 0.000 description 6
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 6
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 5
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 4
- 230000004888 barrier function Effects 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000010408 film Substances 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 239000005033 polyvinylidene chloride Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- 229920002126 Acrylic acid copolymer Polymers 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 210000000481 breast Anatomy 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 229920006026 co-polymeric resin Polymers 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 238000007033 dehydrochlorination reaction Methods 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229920001038 ethylene copolymer Polymers 0.000 description 1
- 239000007888 film coating Substances 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000005755 formation reaction Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- OVHHHVAVHBHXAK-UHFFFAOYSA-N n,n-diethylprop-2-enamide Chemical compound CCN(CC)C(=O)C=C OVHHHVAVHBHXAK-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 239000006072 paste Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- JHJUUEHSAZXEEO-UHFFFAOYSA-M sodium;4-dodecylbenzenesulfonate Chemical compound [Na+].CCCCCCCCCCCCC1=CC=C(S([O-])(=O)=O)C=C1 JHJUUEHSAZXEEO-UHFFFAOYSA-M 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
Classifications
-
- 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
- C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
- C08F214/02—Monomers containing chlorine
- C08F214/04—Monomers containing two carbon atoms
- C08F214/08—Vinylidene chloride
-
- 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
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/26—Emulsion polymerisation with the aid of emulsifying agents anionic
-
- 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
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/30—Emulsion polymerisation with the aid of emulsifying agents non-ionic
-
- 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
- C08F2/00—Processes of polymerisation
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
-
- 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
- C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
- C09D127/02—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
- C09D127/04—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C09D127/08—Homopolymers or copolymers of vinylidene chloride
-
- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Polymerisation Methods In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses salt-fog-resistant vinylidene chloride copolymer latex. Factors with influence on polymerization reaction such as a polymerization monomer formula, an emulsifier formula, polymerization reaction temperature and time and a feeding manner are optimized to optimize a polymerization method. The prepared vinylidene chloride copolymer latex has high storage stability, uniform particle size distribution and strong adhesive force, and a product coated with the vinylidene chloride copolymer latex has high water resistance and salt fog resistance.
Description
Technical field
The present invention relates to a kind of metachloroethylene copolymer latex, particularly relate to a kind of salt fog resistance vinylidene chloride,
The copolymer emulsion of vinyl chloride, acrylate and acrylamide.
Background technology
DOW chemical company of the U.S. in 1932 has started the research of vinylidene chloride polymerization, but vinylidene chloride homopolymer
Softening temperature is sufficiently close to decomposition temperature, and is crystalline polymer.Equal in order to improve vinylidene chloride
The softening temperature of polymers and degree of crystallinity, obtain being total to of classes such as vinyl-chloride-containing, acrylate, acrylonitrile in succession
Aggressiveness.In the fifties in last century, inclined chlorine copolymer resins and latex all have their application report, glue at that time
Newborn is mainly used for dip-coating paper and makees coating.
At present, vinylidene chloride copolymer latex coating has good wearability, moisture resistance, oil resistant, resistance to because of it
The excellent properties such as chemical drugs etch, barrier and anti-flammability, are widely used in packaging for foodstuff, automobile
The fields such as industry, the fire-retardant processing of fiber and concrete curing.But it is domestic to aqueous metachloroethylene copolymer glue
The research of breast is less, and the product of actual application has not been entered into market, mainly due to the emulsion-stabilizing after polymerization
Property bad, long-term place after the easiest breakdown of emulsion of emulsion, coalescence, the adhesive force of film, salt spray resistance reach not simultaneously
Index request to coating.
US3351991A discloses a kind of barrier based on metachloroethylene copolymer/heat sealability coating, the most partially
Vinyl chloride copolymer is formed by vinylidene chloride, acrylonitrile, methyl methacrylate and unsaturated fatty acid copolymerization.
This coating is used for crystalline polypropylene film coating, to improve the heat sealability of goods, moisture-proof and barrier.
US3736303A discloses a kind of latex based on metachloroethylene copolymer, this metachloroethylene copolymer by
The vinylidene chloride of 70-95%, the vinyl unsaturated sulfonic acid of 0.1-3.0%, the vinyl unsaturated carboxylic acid of 0-5%
Other unsaturated vinyl monomer copolymerization with 2-29.9% form.This latex paint is for painting polyethylene or poly-
Ethylene base material, modified by chemical copolymerization, to improve the adhesion under high humidity environment.
EP0261337A2 discloses a kind of terpolymer latex, this copolymer by 80-87.5% vinylidene chloride,
The methyl methacrylate of 7-14.5% and the acrylic acid copolymer of 4.5-6.5% form.This latex paint is used for being coated with
Polypropylene fibre, to improve barrier and the thermostability of goods.
CN101033276A discloses a kind of auto-deposition based on vinylidene chloride-acrylate copolymer latex and is coated with
Material and each method processed.With vinylidene chloride and acrylate as monomer, synthesize vinylidene chloride-acrylate copolymer
Latex, adds dispersible pigment color paste, hydrogen peroxide, iron powder, Fluohydric acid. and deionized water and is configured to autodeposition coatings,
Alternative electrophoretic paint, for the application of metal base, is also applied for body of a motor car, vehicle frame and smallclothes metal device
The application of part.
CN103059192A discloses a kind of polyvinylidene chloride copolymer latex for inner, external wall coating and system thereof
Method and application, this PVDC copolymer latex is by the mixing containing a certain amount of vinylidene chloride, vinyl chloride and acrylate
Monomer, auxiliary agent, initiator, emulsifying agent containing dodecylbenzene sodium sulfonate and OP-10 or OP-4 are through being once polymerized
Method prepares.This PVDC latex makes stable system, can place 24 months not breakdown of emulsion, nothings at 30 DEG C under RH70%
Precipitation, do not destroyed by calcium ions and magnesium ions during use, with its prepare inner, external wall coating have environmental protection, waterproof,
The features such as protection against the tide, anti-flammability.
Above patent has been directed to comonomer and has carried out modified polyvinilidene vinyl chloride, but latex still suffers from dehydrochlorination
Reaction, easily variable color, colour stability is bad, the easy variable color of thin film after coating, foaming, it is impossible to time long
Between keep clear, colorless state, prior art does not has can solve this problem well.
Summary of the invention
Not enough for prior art, the present invention provides a kind of with vinylidene chloride as main monomer, vinyl chloride, propylene
Acid esters and acrylamide monomer carry out the metachloroethylene copolymer latex of the salt fog resistance of modification by copolymerization.
To achieve the above object of the invention, the present invention can use any one technical scheme following:
One aspect of the present invention provide a kind of salt fog resistance metachloroethylene copolymer latex, described copolymer emulsion by
The raw material of following parts by weight is made by emulsion polymerization: mix monomer 100 parts, emulsifying agent 0.5-5 part, draw
Send out agent 0.05-0.5 part, pH adjusting agent 0.05-2 part, chain-transferring agent 0.05-0.2 part and deionized water 50-400
Part；
Described mix monomer consists of the following components in percentage by weight: vinylidene chloride 50-90%, vinyl chloride
5-30%, acrylic ester monomer 1-20% and acrylamide monomers 1-5%；
Described emulsifying agent is amphoteric emulsifier and/or nonionic emulsifier；
Described initiator is azo compound or persulfate；
Described pH adjusting agent is hydrophosphate or bicarbonate；
Described chain-transferring agent is aliphatic mercaptan；
The metachloroethylene copolymer latex of described salt fog resistance prepares as follows:
(1) in reactor, add deionized water and emulsifying agent, start stirring, use high pure nitrogen replacement
In system, residual air is less than 30ppm to oxygen content in still；
(2) add in still stir under Vinyl Chloride Monomer, part initiator and pH adjusting agent, room temperature pre-dispersed
20-30min；
(3) reactor is warming up to 40-80 DEG C, improves reactor speed of agitator, adds vinylidene chloride monomer and third
Olefin(e) acid esters monomer and residue initiator, keep reactor reaction pressure set polymerization pressure ±
0.01MPa；
(4) then drip acrylamide monomers, control reaction temperature 40-80 DEG C；
(5) when polymerization pressure declines 0.1-0.3MPa, add chain-transferring agent, stop stirring, reduce
Reaction temperature, residual gas in releasing reactor, discharging obtains metachloroethylene copolymer latex；
Described raw material is made up of the component of following weight portion: mix monomer 100 parts, emulsifying agent 1-3 part, initiation
Agent 0.1-0.3 part, pH adjusting agent 0.5-1 part, chain-transferring agent 0.08-0.15 part and deionized water 80-200 part；
Described acrylic ester monomer is selected from methacrylate, acrylic acid methyl ester., ethyl acrylate, propylene
Acid N-butyl and acrylic acid-2-ethyl caproite in one or more；
Described acrylic amide is selected from 2-acrylamide, 2-Methacrylamide, N hydroxymethyl acrylamide,
One or more in N, N-diethyl-2-acrylamide；
Described amphoteric emulsifier is selected from alkyl phenol polyethenoxy ether sodium sulfate salt；Nonionic emulsifier is selected from octyl group
Phenol polyethenoxy ether or NPE.
The present invention is by aggregation Monomer Formations, emulsifiers formula, polymeric reaction temperature and time, charging
Modes etc. affect the factor of polyreaction, optimize polymerization, are obtained by the preparation method of the present invention
Metachloroethylene copolymer latex due to polymerization in introduce vinyl chloride, unsaturated fatty acid and acrylamide monomer,
Make whole molecular structure can strengthen the flexibility of molecule segment, the property that resin is excellent can be given,
It is widely used in the fields such as packaging, automobile, food service industry, there is preferable market prospect.With prior art phase
Ratio, the method have the advantages that
1, copolymerization is carried out by vinylidene chloride, vinyl chloride, unsaturated fatty acid and four kinds of monomers of acrylamide,
Optimize the chain structure of main chain, improve the stability of latex, resistance to water and salt fog resistance；
2, by adjusting, improving emulsifier and coupling, improve the storage stability of latex, particle diameter is equal
Even, adhesion is strong；
3, by optimizing processing step, introduce different monomers at different polymerization stages, the most effectively control poly-
Close reaction rate, the composition of copolymer and the molecular weight of copolymer, form the inclined chloroethene that composition is relatively uniform
Alkene copolymer latex.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is further described, but does not limit the invention to this
A little detailed description of the invention.One skilled in the art would recognize that and present invention encompasses Claims scope
Interior potentially included all alternatives, improvement project and equivalents.
Embodiment 1
500g deionized water and emulsifying agent (10g OPEO is added in 2L reactor
(X-100)), starting stirring, in using high pure nitrogen displacement system, residual air is less than to oxygen content in still
30ppm；In still, add 90g Vinyl Chloride Monomer, 0.2g potassium peroxydisulfate and 3g sodium bicarbonate, stir under room temperature
Pre-dispersed 25min；Reactor is warming up to 60 DEG C, improves reactor speed of agitator, adds 347g vinylidene chloride list
Body and 50g acrylic acid-2-ethyl caproite base monomer and 0.8g potassium peroxydisulfate, keep reactor reaction pressure setting
Polymerization pressure ± 0.01MPa；Then dropping N hydroxymethyl acrylamide monomer 10g, controls reaction temperature
60℃；When polymerization pressure declines 0.2MPa, add n-dodecyl mercaptan 1g, stop stirring, fall
Low reaction temperatures, residual gas in releasing reactor, discharging obtains metachloroethylene copolymer latex.It is prepared into
The performance parameter of the vinylidene chloride copolymer latex arrived is as shown in table 1.
Embodiment 2
500g deionized water and (10g OPEO (X-100)) is added in 2L reactor,
Starting stirring, in using high pure nitrogen displacement system, residual air is less than 30ppm to oxygen content in still；In still
Add and stir pre-dispersed 25min under 90g Vinyl Chloride Monomer, 0.2g potassium peroxydisulfate and 3g sodium bicarbonate, room temperature；Instead
Answer still to be warming up to 60 DEG C, improve reactor speed of agitator, add 325g vinylidene chloride monomer and 76g acrylic acid-2-
Ethyl hexyl ester based monomer and 0.8g potassium peroxydisulfate, keep reactor reaction pressure setting polymerization pressure
±0.01MPa；Then dropping N hydroxymethyl acrylamide monomer 10g, controls reaction temperature 60 DEG C；When polymerization is anti-
When answering pressure to decline 0.2MPa, add n-dodecyl mercaptan 1g, stop stirring, reduce reaction temperature, release
Putting residual gas in reactor, discharging obtains metachloroethylene copolymer latex.The vinylidene chloride prepared is altogether
The performance parameter of agglomerating latex is as shown in table 1.
Embodiment 3
500g deionized water and emulsifying agent (10g OPEO is added in 2L reactor
(X-100)), starting stirring, in using high pure nitrogen displacement system, residual air is low to oxygen content in still
In 30ppm；90g Vinyl Chloride Monomer, 0.1g potassium peroxydisulfate and 3g sodium bicarbonate, room temperature is added in still
The lower pre-dispersed 25min of stirring；Reactor is warming up to 60 DEG C, improves reactor speed of agitator, adds 334g
Vinylidene chloride monomer and 50g acrylic acid-2-ethyl caproite base monomer and 0.9g potassium peroxydisulfate, keep reactor
Reaction pressure set polymerization pressure ± 0.01MPa；Then dropping N hydroxymethyl acrylamide monomer
24g, controls reaction temperature 60 DEG C；When polymerization pressure declines 0.2MPa, add dodecyl
Mercaptan 1g, stops stirring, reduces reaction temperature, and residual gas in releasing reactor, discharging obtains inclined chloroethene
Alkene copolymer latex.The performance parameter of the vinylidene chloride copolymer latex prepared is as shown in table 1.
Embodiment 4
500g deionized water and compound emulsifying agent ((5g OPEO is added in 2L reactor
(X-100) and 5g alkyl phenol polyethenoxy ether sodium sulfate salt (VA-50)), start stirring, use High Purity Nitrogen
In gas displacement system, residual air is less than 30ppm to oxygen content in still；In still add 90g Vinyl Chloride Monomer,
Pre-dispersed 25min is stirred under 0.2g potassium peroxydisulfate and 3g sodium bicarbonate, room temperature；Reactor is warming up to 60 DEG C, carries
High reactor speed of agitator, add 347g vinylidene chloride monomer and 50g acrylic acid-2-ethyl caproite base monomer and
0.8g potassium peroxydisulfate, keep reactor reaction pressure set polymerization pressure ± 0.01MPa；Then drip
Add N hydroxymethyl acrylamide monomer 10g, control reaction temperature 60 DEG C；When polymerization pressure declines 0.2MPa
Time, add n-dodecyl mercaptan 1g, stop stirring, reduce residue gas in reaction temperature, releasing reactor
Body, discharging obtains metachloroethylene copolymer latex.The performance parameter of the vinylidene chloride copolymer latex prepared
As shown in table 1.
Comparative example 1
500g deionized water and emulsifying agent (10g OPEO is added in 2L reactor
(X-100)), starting stirring, in using high pure nitrogen displacement system, residual air is low to oxygen content in still
In 30ppm；90g Vinyl Chloride Monomer, 0.1g potassium peroxydisulfate and 3g sodium bicarbonate, room temperature is added in still
The lower pre-dispersed 25min of stirring；Reactor is warming up to 60 DEG C, improves reactor speed of agitator, adds 360g
Vinylidene chloride monomer and 50g acrylic acid-2-ethyl caproite base monomer and 0.9g potassium peroxydisulfate, keep reactor
Reaction pressure set polymerization pressure ± 0.01MPa, control reaction temperature 60 DEG C；Work as polyreaction
When pressure declines 0.2MPa, add n-dodecyl mercaptan 1g, stop stirring, reduce reaction temperature, release
Putting residual gas in reactor, discharging obtains metachloroethylene copolymer latex.The vinylidene chloride prepared is altogether
The performance parameter of agglomerating latex is as shown in table 1.
Comparative example 2
500g deionized water and emulsifying agent (10g OPEO is added in 2L reactor
(X-100)), starting stirring, in using high pure nitrogen displacement system, residual air is low to oxygen content in still
In 30ppm；90g Vinyl Chloride Monomer, 0.1g potassium peroxydisulfate and 3g sodium bicarbonate, room temperature is added in still
The lower pre-dispersed 25min of stirring；Reactor is warming up to 60 DEG C, improves reactor speed of agitator, adds 385g
Vinylidene chloride monomer and 0.9g potassium peroxydisulfate, keep reactor reaction pressure setting polymerization pressure
±0.01MPa；Then dropping N hydroxymethyl acrylamide monomer 24g, controls reaction temperature 60 DEG C；When poly-
When closing reaction pressure decline 0.2MPa, add n-dodecyl mercaptan 1g, stop stirring, reduce and react temperature
Degree, residual gas in releasing reactor, discharging obtains metachloroethylene copolymer latex.The inclined chlorine prepared
The performance parameter of ethylene copolymer latex is as shown in table 1.
Table 1: embodiment 1-4 and the physical index contrast comparing vinylidene chloride latex prepared by 1-2
Knowable to table 1 data, the present invention introduces unsaturated fatty acid and acrylamide two on main polymer chain
Kind of monomer carries out copolymerization, and have employed emulsifiers formula and the polymerization technique of optimization, have adjusted the chain group of main chain
Become and structure, improve surface tension and the viscosity of latex, improve the stability of latex.
Embodiment 5
The latex spreader that embodiment 1-4 and comparative example 1-2 prepare is coated uniformly on through degreasing and rust removal
On iron plate, coating thickness is emulsion thick about 120 μm, and film forming after 60 DEG C of baking and curing 30min, according to state
Family's its hardness of standard test (GB/T 6739-1996), adhesive force (GB/T 1720-1979), resistance to water
And salt fog resistance (GB/T 1771-91) (GB1733-93).
Table 2: vinylidene chloride latex coating performance prepared by embodiment 1-5 compares
Knowable to table 2 data, the present invention introduces unsaturated fatty acid and acrylamide two on main polymer chain
Kind of monomer carries out copolymerization, and have employed emulsifiers formula and the polymerization technique of optimization, and the latex prepared has
Standby excellent film performance, improves resistance to water and salt fog resistance.
Claims (1)
1. the metachloroethylene copolymer latex of a salt fog resistance, it is characterised in that: described copolymer emulsion by with
The raw material of lower parts by weight is made by emulsion polymerization: mix monomer 100 parts, emulsifying agent 0.5-5 part, initiation
Agent 0.05-0.5 part, pH adjusting agent 0.05-2 part, chain-transferring agent 0.05-0.2 part and deionized water 50-400 part；
Described mix monomer consists of the following components in percentage by weight: vinylidene chloride 50-90%, vinyl chloride
5-30%, acrylic ester monomer 1-20% and acrylamide monomers 1-5%；
Described emulsifying agent is amphoteric emulsifier and/or nonionic emulsifier；
Described initiator is azo compound or persulfate；
Described pH adjusting agent is hydrophosphate or bicarbonate；
Described chain-transferring agent is aliphatic mercaptan；
The metachloroethylene copolymer latex of described salt fog resistance prepares as follows:
(1) in reactor, add deionized water and emulsifying agent, start stirring, use high pure nitrogen replacement
In system, residual air is less than 30ppm to oxygen content in still；
(2) add in still stir under Vinyl Chloride Monomer, part initiator and pH adjusting agent, room temperature pre-dispersed
20-30min；
(3) reactor is warming up to 40-80 DEG C, improves reactor speed of agitator, adds vinylidene chloride monomer and third
Olefin(e) acid esters monomer and residue initiator, keep reactor reaction pressure set polymerization pressure ±
0.01MPa；
(4) then drip acrylamide monomers, control reaction temperature 40-80 DEG C；
(5) when polymerization pressure declines 0.1-0.3MPa, add chain-transferring agent, stop stirring, reduce
Reaction temperature, residual gas in releasing reactor, discharging obtains metachloroethylene copolymer latex；
Described raw material is made up of the component of following weight portion: mix monomer 100 parts, emulsifying agent 1-3 part, initiation
Agent 0.1-0.3 part, pH adjusting agent 0.5-1 part, chain-transferring agent 0.08-0.15 part and deionized water 80-200 part；
Described acrylic ester monomer is selected from methacrylate, acrylic acid methyl ester., ethyl acrylate, acrylic acid
One or more in N-butyl and acrylic acid-2-ethyl caproite；
Described acrylic amide is selected from 2-acrylamide, 2-Methacrylamide, N hydroxymethyl acrylamide, N, N-
One or more in diethyl-2-acrylamide；
Described amphoteric emulsifier is selected from alkyl phenol polyethenoxy ether sodium sulfate salt；Nonionic emulsifier is selected from octyl phenol
Polyoxyethylene ether or NPE.
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| CN105062164B (en) * | 2015-08-20 | 2016-12-21 | 广州市金万正印刷材料有限公司 | A kind of aqueous wear-resistant coating, aqueous wear-resistant thin film and its preparation method and application |
| CN108884352B (en) * | 2016-03-18 | 2021-03-09 | 索尔维公司 | Water-based anticorrosion coating composition |
| CN109438608B (en) * | 2018-11-07 | 2021-07-13 | 长春工业大学 | Preparation method of vinylidene chloride copolymer aqueous emulsion for degradable tableware |
| CN111518235A (en) * | 2020-06-29 | 2020-08-11 | 天津城建大学 | Water-based vinylidene chloride copolymer resin and preparation method thereof |
| CN112625164B (en) * | 2020-12-18 | 2022-09-06 | 杭州电化新材料有限公司 | Functional group monomer modified water-based epichlorohydrin emulsion and preparation method thereof |
| CN112552445B (en) * | 2020-12-18 | 2022-09-06 | 杭州电化新材料有限公司 | Reactive emulsifier modified chlorinated polyether emulsion and preparation method thereof |
| CN113502077A (en) * | 2021-07-01 | 2021-10-15 | 广东连邦新材料股份有限公司 | Preparation method of graphene high-performance fireproof coating |
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| CN104403042A (en) | 2015-03-11 |
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| CN105859944B (en) | 2018-01-19 |
| CN105924560B (en) | 2017-12-19 |
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