CN105924560B - A kind of metachloroethylene copolymer latex of salt fog resistance - Google Patents
A kind of metachloroethylene copolymer latex of salt fog resistance Download PDFInfo
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- CN105924560B CN105924560B CN201610405582.0A CN201610405582A CN105924560B CN 105924560 B CN105924560 B CN 105924560B CN 201610405582 A CN201610405582 A CN 201610405582A CN 105924560 B CN105924560 B CN 105924560B
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- 239000004816 latex Substances 0.000 title claims abstract description 46
- 229920000126 latex Polymers 0.000 title claims abstract description 46
- 229920001577 copolymer Polymers 0.000 title claims abstract description 39
- 150000003839 salts Chemical class 0.000 title claims abstract description 14
- 239000000178 monomer Substances 0.000 claims abstract description 46
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 24
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 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 23
- 238000003756 stirring Methods 0.000 claims description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims description 15
- -1 azo compound Chemical class 0.000 claims description 15
- 239000002253 acid Substances 0.000 claims description 13
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- 239000003999 initiator Substances 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 238000007599 discharging Methods 0.000 claims description 8
- 238000006073 displacement reaction Methods 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- 238000010792 warming Methods 0.000 claims description 8
- 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
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 239000003002 pH adjusting agent Substances 0.000 claims description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 239000000839 emulsion Substances 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 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
- 150000001336 alkenes Chemical class 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- DUIOKRXOKLLURE-UHFFFAOYSA-N 2-octylphenol Chemical group CCCCCCCCC1=CC=CC=C1O DUIOKRXOKLLURE-UHFFFAOYSA-N 0.000 claims description 2
- 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
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 2
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 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
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 claims 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
- 150000002148 esters Chemical class 0.000 claims 1
- 229940074391 gallic acid Drugs 0.000 claims 1
- 235000004515 gallic acid Nutrition 0.000 claims 1
- 229940051841 polyoxyethylene ether Drugs 0.000 claims 1
- 229920000056 polyoxyethylene ether Polymers 0.000 claims 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims 1
- 239000002245 particle Substances 0.000 abstract description 2
- 238000003860 storage Methods 0.000 abstract description 2
- 238000000576 coating method Methods 0.000 description 12
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical class [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
- 239000011248 coating agent Substances 0.000 description 10
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 6
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 6
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- 229910052708 sodium Inorganic materials 0.000 description 6
- 239000003643 water by type Substances 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 5
- 238000007334 copolymerization reaction Methods 0.000 description 5
- 238000006722 reduction reaction Methods 0.000 description 5
- 150000001408 amides Chemical class 0.000 description 4
- 230000004888 barrier function Effects 0.000 description 4
- 238000000034 method Methods 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
- 239000003973 paint Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000005033 polyvinylidene chloride Substances 0.000 description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-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
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 238000010422 painting Methods 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000000126 substance Substances 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
- LGXVIGDEPROXKC-UHFFFAOYSA-N 1,1-dichloroethene Chemical class ClC(Cl)=C LGXVIGDEPROXKC-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
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-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
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000002585 base Substances 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
- 230000008859 change Effects 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 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
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000003292 glue Substances 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
- 239000000463 material Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 229920001897 terpolymer Polymers 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 a kind of metachloroethylene copolymer latex of salt fog resistance.The present invention influences the factor of polymerisation by optimizing polymerized monomer formula, emulsifiers formula, polymeric reaction temperature and time, feed way etc., optimizes polymerization.The metachloroethylene copolymer latex being prepared by the present invention possesses excellent storage stability, and particle diameter distribution is uniform, and adhesion is strong, and its product being coated with possesses excellent water resistance and salt fog resistance.
Description
Technical field
The present invention relates to a kind of metachloroethylene copolymer latex, more particularly to a kind of vinylidene chloride of salt fog resistance, chloroethene
The copolymer emulsion of alkene, acrylate and acrylamide.
Background technology
DOW chemical companies of the U.S. in 1932 have started the research of vinylidene chloride polymerization, but vinylidene chloride homopolymer softening temperature
Degree is sufficiently close to decomposition temperature, and is crystalline polymer.In order to improve the softening temperature of vinylidene chloride homopolymer and
Crystallinity, a kind of EVA such as vinyl-chloride-containing, acrylate, acrylonitrile is obtained in succession.In the fifties in last century, inclined chlorine copolymerization
Resin and latex all have their application report, and latex was mainly used for dip-coating paper and makees coating at that time.
At present, vinylidene chloride copolymer latex coating is because it has good wearability, moisture resistance, oil resistant, chemical-resistant resistance
The excellent properties such as etch, barrier and anti-flammability, it is widely used in packaging for foodstuff, the fire-retardant processing of auto industry, fiber
And the field such as concrete curing.But the domestic research to water-based metachloroethylene copolymer latex is less, and the product of practical application is also
Market is not entered into, bad mainly due to the stability of emulsion after polymerization, emulsion is easily demulsified, coalesced very much after long-term placement, simultaneously
Adhesive force, the salt spray resistance of film do not reach the index request of coating.
US3351991A discloses a kind of barrier based on metachloroethylene copolymer/heat sealability coating, wherein inclined chloroethene
Alkene copolymer is formed by the copolymerization of vinylidene chloride, acrylonitrile, methyl methacrylate and unrighted acid.The coating is used to crystallize
Polypropylene screen coating, to improve the heat sealability of product, moisture-proof and barrier.
US3736303A discloses a kind of latex based on metachloroethylene copolymer, and the metachloroethylene copolymer is by 70-
95% vinylidene chloride, 0.1-3.0% vinyl unsaturated sulfonic acid, 0-5% vinyl unsaturated carboxylic acid and 2-29.9%
Other unsaturated vinyl monomers copolymerization form.The latex paint is used for painting polyethylene or polyethylene base material, passes through chemistry
Modification by copolymerization, to improve the adhesion under high humidity environment.
EP0261337A2 discloses a kind of terpolymer latex, and the copolymer is by 80-87.5% vinylidene chlorides, 7-
14.5% methyl methacrylate and 4.5-6.5% acrylic acid copolymer form.It is fine that the latex paint is used for painting polypropylene
Dimension, to improve the barrier of product and heat resistance.
CN101033276A discloses a kind of autodeposition coatings and system based on vinylidene chloride-acrylate copolymer latex
Each method.Using vinylidene chloride and acrylate as monomer, vinylidene chloride-acrylate copolymer latex is synthesized, adds pigment
Mill base, hydrogen peroxide, iron powder, hydrofluoric acid and deionized water are configured to autodeposition coatings, alternative electrophoretic paint, for metal base
Application, it is also applied for the application of body of a motor car, vehicle frame and smallclothes metal device.
CN103059192A discloses a kind of polyvinylidene chloride copolymer latex for inner, external wall coating and its preparation method and should
With, the PVDC copolymer latexes by the mix monomer containing a certain amount of vinylidene chloride, vinyl chloride and acrylate, auxiliary agent, initiator,
Emulsifying agent containing neopelex and OP-10 or OP-4 is made through a polymerization.The PVDC latex makes stable system,
Can place and not be demulsified within 24 months, without precipitation at 30 DEG C, under RH70%, not destroyed by calcium ions and magnesium ions during use, with its it is obtained in,
Exterior coating has the characteristics that environmental protection, waterproof, 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 change colour, colour stability is bad, and the film after coating easily changes colour, bubbled, it is impossible to clear, colorless state is kept for a long time,
Prior art is no can to solve this problem well.
The content of the invention
In view of the shortcomings of the prior art, the present invention provides one kind using vinylidene chloride as main monomer, vinyl chloride, acrylate and third
Acrylamide monomer carries 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 following technical scheme：
One aspect of the present invention provides a kind of metachloroethylene copolymer latex of salt fog resistance, and the copolymer emulsion is by following
The raw material of parts by weight is made up of emulsion polymerization：100 parts of mix monomer, emulsifying agent 0.5-5 parts, initiator 0.05-0.5 parts,
PH adjusting agent 0.05-2 parts, chain-transferring agent 0.05-0.2 parts and deionized water 50-400 parts；
The 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%；
The emulsifying agent is amphoteric emulsifier and/or nonionic emulsifier；
The initiator is azo compound or persulfate；
The pH adjusting agent is hydrophosphate or bicarbonate；
The chain-transferring agent is aliphatic mercaptan；
The metachloroethylene copolymer latex of the salt fog resistance is made as follows：
(1) deionized water and emulsifying agent are added in reactor, starts stirring, using being remained in high pure nitrogen displacement system
Oxygen content is less than 30ppm in air to kettle；
(2) VCM, part initiator and pH adjusting agent are added in kettle, stirs pre-dispersed 20- at room temperature
30min；
(3) reactor is warming up to 40-80 DEG C, improves reactor speed of agitator, adds vinylidene chloride monomer and acrylate
Class monomer and remaining initiator, reactor reaction pressure is kept in ± the 0.01MPa of setting polymerization pressure；
(4) acrylamide monomers, 40-80 DEG C of controlling reaction temperature is then added dropwise；
(5) when polymerization pressure declines 0.1-0.3MPa, chain-transferring agent is added, stops stirring, reduces reaction temperature,
Residual gas in releasing reactor, discharging obtain metachloroethylene copolymer latex；
The raw material is made up of the component of following parts by weight：100 parts of mix monomer, emulsifying agent 1-3 parts, initiator 0.1-
0.3 part, pH adjusting agent 0.5-1 parts, chain-transferring agent 0.08-0.15 parts and deionized water 80-200 parts；
The acrylic ester monomer is selected from methacrylate, methyl acrylate, ethyl acrylate, n-butyl acrylate
With it is more than one or both of acrylic acid-2-ethyl caproite；
The acrylic amide is selected from 2- acrylamides, 2- Methacrylamides, N hydroxymethyl acrylamide, N, N- diethyls
It is more than one or both of base -2- acrylamides；
The amphoteric emulsifier is selected from alkyl phenol polyethenoxy ether sodium sulfate salt；Nonionic emulsifier is selected from octyl phenol polyoxy
Vinethene or NPE.
The present invention is by optimizing the shadows such as polymerized monomer formula, emulsifiers formula, polymeric reaction temperature and time, feed way
The factor of polymerisation is rung, optimizes polymerization, the metachloroethylene copolymer latex obtained by the preparation method of the present invention
Due to introducing vinyl chloride, unrighted acid and acrylamide monomer in polymerization so that can strengthen in whole molecular structure point
It the flexibility of subchain section, can assign resin excellent property, be widely used in the fields such as packaging, automobile, food service industry, have
There are preferable market prospects.Compared with prior art, the invention has the advantages that：
1st, it is copolymerized by four kinds of vinylidene chloride, vinyl chloride, unrighted acid and acrylamide monomers, optimizes master
The chain structure of chain, improve the stability, water resistance and salt fog resistance of latex；
2nd, by adjusting, improving emulsifier and matching, the storage stability of latex, uniform particle sizes, adhesion are improved
Power is strong；
3rd, by optimize technique step, different monomers is introduced in different polymerization stages, are advantageous to effectively control polymerisation
The molecular weight of speed, the composition of copolymer and copolymer, formed and form relatively uniform metachloroethylene copolymer latex.
Embodiment
The present invention is further described with reference to specific embodiment, but does not limit the invention to these tools
Body embodiment.One skilled in the art would recognize that present invention encompasses may include in Claims scope
All alternatives, improvement project and equivalents.
Embodiment 1
500g deionized waters and emulsifying agent (10g OPEOs (X-100)) are added in 2L reactors, is started
Stirring, is less than 30ppm using oxygen content in residual air to kettle in high pure nitrogen displacement system；90g vinyl chloride is added in kettle
Monomer, 0.2g potassium peroxydisulfates and 3g sodium acid carbonates, stir pre-dispersed 25min at room temperature；Reactor is warming up to 60 DEG C, improves reaction
Kettle speed of agitator, 347g vinylidene chloride monomers and 50g acrylic acid-2-ethyl caproite base monomers and 0.8g potassium peroxydisulfates are added, protected
Hold ± 0.01MPa of the reactor reaction pressure in setting polymerization pressure；N hydroxymethyl acrylamide monomer is then added dropwise
10g, 60 DEG C of controlling reaction temperature；When polymerization pressure declines 0.2MPa, n-dodecyl mercaptan 1g is added, stops stirring
Mix, reduction reaction temperature, residual gas in releasing reactor, discharging obtains metachloroethylene copolymer latex.What is be prepared is inclined
The performance parameter of chloroethylene copolymer latex is as shown in table 1.
Embodiment 2
500g deionized waters and (10g OPEOs (X-100)) are added in 2L reactors, starts stirring,
30ppm is less than using oxygen content in residual air to kettle in high pure nitrogen displacement system；Added in kettle 90g VCMs,
0.2g potassium peroxydisulfates and 3g sodium acid carbonates, stir pre-dispersed 25min at room temperature；Reactor is warming up to 60 DEG C, improves reactor and stirs
Mix rotating speed, 325g vinylidene chloride monomers and 76g acrylic acid-2-ethyl caproite base monomers and 0.8g potassium peroxydisulfates are added, keep anti-
Kettle reaction pressure is answered in ± the 0.01MPa of setting polymerization pressure；N hydroxymethyl acrylamide monomer 10g, control is then added dropwise
60 DEG C of reaction temperature processed；When polymerization pressure declines 0.2MPa, n-dodecyl mercaptan 1g is added, stops stirring, is reduced
Reaction temperature, residual gas in releasing reactor, discharging obtain metachloroethylene copolymer latex.The vinylidene chloride being prepared is total to
The performance parameter of agglomerating latex is as shown in table 1.
Embodiment 3
500g deionized waters and emulsifying agent (10g OPEOs (X-100)) are added in 2L reactors, is started
Stirring, is less than 30ppm using oxygen content in residual air to kettle in high pure nitrogen displacement system；90g vinyl chloride is added in kettle
Monomer, 0.1g potassium peroxydisulfates and 3g sodium acid carbonates, stir pre-dispersed 25min at room temperature；Reactor is warming up to 60 DEG C, improves reaction
Kettle speed of agitator, 334g vinylidene chloride monomers and 50g acrylic acid-2-ethyl caproite base monomers and 0.9g potassium peroxydisulfates are added, protected
Hold ± 0.01MPa of the reactor reaction pressure in setting polymerization pressure；N hydroxymethyl acrylamide monomer is then added dropwise
24g, 60 DEG C of controlling reaction temperature；When polymerization pressure declines 0.2MPa, n-dodecyl mercaptan 1g is added, stops stirring
Mix, reduction reaction temperature, residual gas in releasing reactor, discharging obtains metachloroethylene copolymer latex.What is be prepared is inclined
The performance parameter of chloroethylene copolymer latex is as shown in table 1.
Embodiment 4
Added in 2L reactors 500g deionized waters and compound emulsifying agent ((5g OPEOs (X-100) and
5g alkyl phenol polyethenoxy ether sodium sulfates salt (VA-50)), stirring is started, using residual air in high pure nitrogen displacement system extremely
Oxygen content is less than 30ppm in kettle；90g VCMs, 0.2g potassium peroxydisulfates and 3g sodium acid carbonates are added in kettle, is stirred at room temperature
Mix pre-dispersed 25min；Reactor is warming up to 60 DEG C, improves reactor speed of agitator, adds 347g vinylidene chloride monomers and 50g third
Olefin(e) acid -2- ethyl hexyls ester based monomer and 0.8g potassium peroxydisulfates, keep reactor reaction pressure setting polymerization pressure ±
0.01MPa；N hydroxymethyl acrylamide monomer 10g, 60 DEG C of controlling reaction temperature is then added dropwise；When polymerization pressure declines
During 0.2MPa, n-dodecyl mercaptan 1g is added, stopping is stirred, reduction reaction temperature, residual gas in releasing reactor, discharging
Obtain metachloroethylene copolymer latex.The performance parameter for the vinylidene chloride copolymer latex being prepared is as shown in table 1.
Comparative example 1
500g deionized waters and emulsifying agent (10g OPEOs (X-100)) are added in 2L reactors, is started
Stirring, is less than 30ppm using oxygen content in residual air to kettle in high pure nitrogen displacement system；90g vinyl chloride is added in kettle
Monomer, 0.1g potassium peroxydisulfates and 3g sodium acid carbonates, stir pre-dispersed 25min at room temperature；Reactor is warming up to 60 DEG C, improves reaction
Kettle speed of agitator, 360g vinylidene chloride monomers and 50g acrylic acid-2-ethyl caproite base monomers and 0.9g potassium peroxydisulfates are added, protected
Hold ± 0.01MPa of the reactor reaction pressure in setting polymerization pressure, 60 DEG C of controlling reaction temperature；Work as polymerization pressure
When declining 0.2MPa, n-dodecyl mercaptan 1g is added, stopping is stirred, reduction reaction temperature, residual gas in releasing reactor,
Discharging obtains metachloroethylene copolymer latex.The performance parameter for the vinylidene chloride copolymer latex being prepared is as shown in table 1.
Comparative example 2
500g deionized waters and emulsifying agent (10g OPEOs (X-100)) are added in 2L reactors, is started
Stirring, is less than 30ppm using oxygen content in residual air to kettle in high pure nitrogen displacement system；90g vinyl chloride is added in kettle
Monomer, 0.1g potassium peroxydisulfates and 3g sodium acid carbonates, stir pre-dispersed 25min at room temperature；Reactor is warming up to 60 DEG C, improves reaction
Kettle speed of agitator, 385g vinylidene chloride monomers and 0.9g potassium peroxydisulfates are added, keep reactor reaction pressure anti-in setting polymerization
Answer ± the 0.01MPa of pressure；N hydroxymethyl acrylamide monomer 24g, 60 DEG C of controlling reaction temperature is then added dropwise；Work as polymerisation
When pressure declines 0.2MPa, n-dodecyl mercaptan 1g is added, stopping is stirred, reduction reaction temperature, remaining in releasing reactor
Gas, discharging obtain metachloroethylene copolymer latex.The performance parameter for the vinylidene chloride copolymer latex the being prepared such as institute of table 1
Show.
Table 1：Embodiment 1-4 and the physical index contrast for comparing vinylidene chloride latex prepared by 1-2
It was found from the data of table 1, the present invention introduces two kinds of monomers of unrighted acid and acrylamide on main polymer chain
It is copolymerized, and employs the emulsifiers formula and polymerization technique of optimization, is have adjusted the chain the Nomenclature Composition and Structure of Complexes of main chain, improve glue
The surface tension and viscosity of breast, improve the stability of latex.
Embodiment 5
Latex made from embodiment 1-4 and comparative example 1-2 is coated uniformly on spreader to the iron plate by degreasing and rust removal
On, thickness is coated as 120 μm or so thick emulsions, film forming after 60 DEG C of baking and curing 30min, its hardness is determined according to national standard
(GB/T 6739-1996), adhesive force (GB/T 1720-1979), water resistance (GB1733-93) and salt fog resistance (GB/T
1771-91)。
Table 2：Vinylidene chloride latex coating performance prepared by embodiment 1-5 compares
It was found from the data of table 2, the present invention introduces two kinds of monomers of unrighted acid and acrylamide on main polymer chain
It is copolymerized, and employs the emulsifiers formula and polymerization technique of optimization, the latex being prepared possesses excellent film performance,
Improve water resistance and salt fog resistance.
Claims (1)
- A kind of 1. metachloroethylene copolymer latex of salt fog resistance, it is characterised in that：The copolymer emulsion is by following parts by weight Several raw materials are made up of emulsion polymerization：100 parts of mix monomer, emulsifying agent 1-3 parts, initiator 0.1-0.3 parts, pH adjusting agent 0.5-1 parts, chain-transferring agent 0.08-0.15 parts and deionized water 80-200 parts；The mix monomer consists of the following components in percentage by weight：Vinylidene chloride 50-90%, vinyl chloride 5-30%, propylene Esters of gallic acid monomer 1-20% and acrylamide monomers 1-5%；The emulsifying agent is amphoteric emulsifier and/or nonionic emulsifier；The initiator is azo compound or persulfate；The pH adjusting agent is hydrophosphate or bicarbonate；The chain-transferring agent is aliphatic mercaptan；The metachloroethylene copolymer latex of the salt fog resistance is made as follows：(1) deionized water and emulsifying agent are added in reactor, stirring is started, using residual air in high pure nitrogen displacement system Oxygen content is less than 30ppm in kettle；(2) VCM, part initiator and pH adjusting agent are added in kettle, stirs pre-dispersed 20-30min at room temperature；(3) reactor is warming up to 40-80 DEG C, improves reactor speed of agitator, adds vinylidene chloride monomer and esters of acrylic acid list Body and remaining initiator, reactor reaction pressure is kept in ± the 0.01MPa of setting polymerization pressure；(4) acrylamide monomers, 40-80 DEG C of controlling reaction temperature is then added dropwise；(5) when polymerization pressure declines 0.1-0.3MPa, chain-transferring agent is added, stops stirring, reduce reaction temperature, release Residual gas in reactor, discharging obtain metachloroethylene copolymer latex；The acrylic ester monomer is selected from methacrylate, methyl acrylate, ethyl acrylate, n-butyl acrylate and third It is more than one or both of olefin(e) acid -2- ethylhexyls；The acrylic amide be selected from 2- acrylamides, 2- Methacrylamides, N hydroxymethyl acrylamide, N, N- diethyl- It is more than one or both of 2- acrylamides；The 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 |
| BR112018068257B1 (en) * | 2016-03-18 | 2022-08-09 | Solvay Sa | AQUEOUS COATING COMPOSITION AND ITS MANUFACTURING METHOD |
| CN107011476B (en) * | 2017-05-25 | 2019-05-07 | 蔡辉 | A kind of wood moulding PVC resin specially and its preparation method and application |
| 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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| CN105859944B (en) | 2018-01-19 |
| CN105924560A (en) | 2016-09-07 |
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