CN105924559A - Preparation Method of shock-resistant vinyl chloride copolymer resin - Google Patents
Preparation Method of shock-resistant vinyl chloride copolymer resin Download PDFInfo
- Publication number
- CN105924559A CN105924559A CN201610412730.1A CN201610412730A CN105924559A CN 105924559 A CN105924559 A CN 105924559A CN 201610412730 A CN201610412730 A CN 201610412730A CN 105924559 A CN105924559 A CN 105924559A
- Authority
- CN
- China
- Prior art keywords
- vinyl chloride
- monomer
- copolymer resin
- reaction temperature
- chloride 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.)
- Granted
Links
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 229920006026 co-polymeric resin Polymers 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 230000035939 shock Effects 0.000 title abstract description 11
- 239000000178 monomer Substances 0.000 claims abstract description 62
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 21
- 239000002270 dispersing agent Substances 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims description 46
- 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
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 24
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 16
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 14
- -1 azo compound Chemical class 0.000 claims description 13
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 238000007599 discharging Methods 0.000 claims description 12
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 claims description 12
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 claims description 12
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical group OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 claims description 11
- 229910052756 noble gas Inorganic materials 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 239000003999 initiator Substances 0.000 claims description 9
- 238000006136 alcoholysis reaction Methods 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 239000003002 pH adjusting agent Substances 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 239000000725 suspension Substances 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 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
- 229920002678 cellulose Polymers 0.000 claims description 2
- 239000001913 cellulose Substances 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
- 239000002994 raw material Substances 0.000 claims description 2
- 238000010792 warming Methods 0.000 claims description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims 1
- 238000010276 construction Methods 0.000 abstract description 33
- 238000012545 processing Methods 0.000 abstract description 6
- 230000004888 barrier function Effects 0.000 abstract description 2
- 235000013305 food Nutrition 0.000 abstract description 2
- 230000000379 polymerizing effect Effects 0.000 abstract 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 30
- 229920005989 resin Polymers 0.000 description 27
- 239000011347 resin Substances 0.000 description 27
- 229920000642 polymer Polymers 0.000 description 21
- 239000002245 particle Substances 0.000 description 20
- 238000004458 analytical method Methods 0.000 description 16
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 15
- 229920001577 copolymer Polymers 0.000 description 11
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 8
- 229910000831 Steel Inorganic materials 0.000 description 8
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 8
- 238000002347 injection Methods 0.000 description 8
- 239000007924 injection Substances 0.000 description 8
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 8
- 229910052753 mercury Inorganic materials 0.000 description 8
- 230000005311 nuclear magnetism Effects 0.000 description 8
- 239000010959 steel Substances 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 4
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 4
- 235000017557 sodium bicarbonate Nutrition 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 229920000915 polyvinyl chloride Polymers 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000005755 formation reaction Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- LGXVIGDEPROXKC-UHFFFAOYSA-N 1,1-dichloroethene Chemical compound ClC(Cl)=C LGXVIGDEPROXKC-UHFFFAOYSA-N 0.000 description 1
- WYGWHHGCAGTUCH-UHFFFAOYSA-N 2-[(2-cyano-4-methylpentan-2-yl)diazenyl]-2,4-dimethylpentanenitrile Chemical compound CC(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)C WYGWHHGCAGTUCH-UHFFFAOYSA-N 0.000 description 1
- IGDCJKDZZUALAO-UHFFFAOYSA-N 2-prop-2-enoxypropane-1,3-diol Chemical compound OCC(CO)OCC=C IGDCJKDZZUALAO-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- 239000004970 Chain extender Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 101100115801 Streptomyces mobaraensis daip gene Proteins 0.000 description 1
- 208000004761 Supernumerary Tooth Diseases 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 238000005937 allylation reaction Methods 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- ZPOLOEWJWXZUSP-AATRIKPKSA-N bis(prop-2-enyl) (e)-but-2-enedioate Chemical compound C=CCOC(=O)\C=C\C(=O)OCC=C ZPOLOEWJWXZUSP-AATRIKPKSA-N 0.000 description 1
- ZPOLOEWJWXZUSP-WAYWQWQTSA-N bis(prop-2-enyl) (z)-but-2-enedioate Chemical compound C=CCOC(=O)\C=C/C(=O)OCC=C ZPOLOEWJWXZUSP-WAYWQWQTSA-N 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 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
- 238000004806 packaging method and process Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer 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
- C08F214/06—Vinyl 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
- C08F2/20—Aqueous medium with the aid of macromolecular dispersing agents
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polymerisation Methods In General (AREA)
- Graft Or Block Polymers (AREA)
Abstract
The invention discloses a preparation method of shock-resistant vinyl chloride copolymer resin. The polymerizing method is optimized by optimizing polymerization factors, such as a monomer formula, a dispersant formula, polymerization temperature and time, and a feeding pattern. The products prepared by vinyl chloride copolymer resin have the advantages of excellent processability, barrier property, flame retardance, and shock resistance, are widely applied to fields of construction, package, automobiles, food processing and the like, and has great market prospect.
Description
The present invention is application number: 2014108369832, the applying date: 2014-12-29, denomination of invention:
The divisional application of the vinyl chloride copolymer resin planting resistance to impact and preparation method thereof.
Technical field
The present invention relates to a kind of vinyl chloride copolymer resin and preparation method thereof, particularly relate to a kind of resistance to impact
The copolymer resin of vinyl chloride, vinylidene chloride, acrylate and maleic anhydride and preparation method thereof.
Background technology
Though polrvinyl chloride prepared at laboratory the most as far back as 1835, but because of poor heat stability, processing should
With never breaking through.Arrived eighties of last century end of the twenties, occur in that of both break through: one is plasticising,
Goodrich companies in 1933 have delivered the patent adding plasticizer；Another is copolymerization, and PVC is served structure
Improve, be conducive to processing.The chloroethylene copolymer species produced in the world at present not less than dozens, kind board
Number more.Poor due to the processing type of polrvinyl chloride, impact strength, dissolubility etc., can not meet some special
Different purposes, the therefore new polrvinyl chloride kind of development.
VDC-VC copolymer resins from 1936 come out since, U.S. DOW, Japan Wu Yu, the Northeast electrification,
Company's competitively Development and Production such as East Asia synthesis go out VDC-VC suspension copolymer resin.Domestic open from the eighties in 20th century
Begin to study synthesis technique and the performance of VDC-VC copolymer resins, have accumulated certain theoretical basis and technology.Work
Use free radical to suspend in industry and emulsion is polymerized VDC-VC polymer processed, mainly with VDC as main monomer, by
React to monomer chain tra nsfer etc. in existing, cause the formation of unstable structure in polymer chain, the heat of polymer
Less stable, affects processing characteristics.
US4983311A describes a kind of vinyl chloride copolymer, hydroxyl and two groups of carboxylic acid group by all mixing
Liquid polymerization is simultaneously introduced in polymer adhesive.In being preferable to carry out one, vinyl chloride, glycerol monoallyl
Ether, acetone, benzoyl peroxide first phthalein are added by fed-batch mode, and maleic acid, vinylidene chloride and methanol are logical
Cross quantitative feeding mode to add.But owing to employing multi-solvents, the dependence to solvent causes environmental problem
And add the cost of production.
US5912082A disclose a kind of to vinyl chloride or vinyl chloride and other mixture of vinyl monomer with contain
Carboxylic monomer is polymerized, thus the method obtaining vinyl chloride copolymer.Hydroxyl monomer is by dihydroxy
Base or polyhydroxy-alcohol part allylation obtain.This copolymer is prepared by suspension polymerization, hydroxyl
There is the character substantially changing polymer, plasticizer absorption rate substantially increases and drying time significantly reduces.
It addition, hydroxyl becomes the reflecting point of post-polymerization due to its polarity and activity.But owing to carboxylic monomer enters
Having arrived polrvinyl chloride main chain, resin heat stability in the course of processing is inadequate, easily decomposes and makes goods variable color.
CN101386661A discloses the preparation method of a kind of polychloroethylene with high polymerization degree, vinyl chloride main monomer with
Diallyl fumarate, DAIP and/or diallyl maleate comonomer use and suspend
Copolymerization process obtains high polymerization degree vinyl chloride copolymer resin, employs the compound system of chain extender/chain-transferring agent
Shorten the response time, solve polymeric reaction temperature difficulty control problem, and improve the processability of goods,
Improve its mechanical property.But the method is faced with the difficult separation and recycling of monomer and resin, and cost produces
Higher.
CN103265658A discloses the synthetic method of a kind of heat resistant type chloroethylene copolymer resin, uses emulsion to gather
Conjunction method is by Vinyl Chloride Monomer and second comonomer or second comonomer and Third monomer, poly-under anaerobic airtight condition
Closing reaction, polymerization temperature is 45-65 DEG C, when reaction temperature reaches set temperature value, starts to add initiator
And, prepare copolymer emulsion, this LS is dried and i.e. prepares polyvinyl chloride copolymer.But the method is adopted
The resin prepared with emulsion polymerization way is difficult to obtain controlled grain diameter and porosity, and molecular weight
Distribution width.
Summary of the invention
Not enough for prior art, the present invention provides a kind of with vinyl chloride as main monomer, vinylidene chloride, propylene
Acid esters and maleic anhydride monomer carry out resistance to impact vinyl chloride copolymer resin and the preparation thereof of modification by copolymerization
Method.
To achieve the above object of the invention, the present invention provides the preparation of a kind of resistance to impact vinyl chloride copolymer resin
Method, described copolymer resin is made up by suspension polymerisation of the raw material of following parts by weight: mix monomer 100
Part, dispersant 0.1-1 part, initiator 0.05-0.3 part, pH adjusting agent 0.1-2 part, chain-transferring agent 0.05-0.2
Part and deionized water 100-300 part；
Described mix monomer consists of the following components in percentage by weight: vinyl chloride 60-90%, vinylidene chloride
5-30%, acrylate 1-10% and maleic anhydride (MA) 1-5%；
Described dispersant is hydroxypropyl methyl cellulose and/or polyvinyl alcohol (PVA)；
Described initiator is azo compound or persulfate；
Described pH adjusting agent is hydrophosphate or bicarbonate；
Described chain-transferring agent is aliphatic mercaptan；
Described preparation method comprises the steps:
(1) under the protection of noble gas, Vinyl Chloride Monomer, dispersant, part initiator, pH are adjusted
Joint agent and deionized water join reactor, pre-dispersed 20-30min under room temperature；
(2) heat up and control at reaction temperature 30-70 DEG C react 15-45min, then add vinylidene chloride and
Crylic acid ester mixture monomer；
(3) after completing monomer interpolation, add residue initiator, control to react at reaction temperature 30-70 DEG C
15-30min；
(4) reactor temperature is warming up to 40-80 DEG C, drips maleic anhydride monomer；
(5) when polymerization pressure declines 0.1-0.3MPa, add chain-transferring agent, stop stirring, reduce
Reaction temperature, residual gas in releasing reactor, discharging；
(6) discharging is through filtering, washing and dried, obtains vinyl chloride copolymer resin；
Described dispersant consists of the following components in percentage by weight: polyvinyl alcohol (PVA) 20-80% and hydroxypropyl
Ylmethyl cellulose 20-80%；
The alcoholysis degree of described polyvinyl alcohol (PVA) is 69-89mol%, the hydroxyl of described hydroxypropyl methyl cellulose
Propyl group content is 4-12mol%.
The present invention is by aggregation Monomer Formations, dispersant formulation, 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
Vinyl chloride copolymer resin product, has relatively high resin particle diameter, owing to introducing vinylidene chloride, no in polymerization
Satisfied fatty acid and maleic anhydride so that the flexibility of molecule segment in whole molecular structure, can be strengthened,
The property that resin is excellent can be given, as reduce resin melt temperature, improve resin heat stability,
Strengthen the impact resistance of goods, be widely used in the fields such as building, packaging, automobile, food service industry, have relatively
Good market prospect.Compared with prior art, the method have the advantages that
1, by introducing vinylidene chloride, unsaturated fatty acid and maleic anhydride on polrvinyl chloride main chain,
Optimizing the chain structure of main chain, the intensity of vinyl chloride copolymer resin particle is higher, the most broken, uses the longevity
Life is long, and its fabricated product has excellent impact resistance, the transparency, barrier and anti-flammability；
2, by adjusting, improving dispersant dosage and coupling, bulky grain and little granule, holding can be eliminated
Particle diameter compares concentration, and grain form is regular, fine and close, has relatively low porosity and relatively high apparent density, particle diameter
Resin ratio between 0.2-0.25mm is more than 85%, and apparent density is at 0.55-0.75g/ml.
3, introduce different monomers at different polymerization stages, be conducive to effectively controlling polymerization rate, copolymer
Composition and the molecular weight of copolymer, form the relatively uniform vinyl chloride copolymer of composition；
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
Under the protection of noble gas, in 10L rustless steel autoclave add 6L high purity deionized water,
2688g Vinyl Chloride Monomer, 18g sodium peroxydisulfate, 28g sodium bicarbonate and 185g hydroxypropyl methyl cellulose (hydroxyl
Propyl group content is 6.3mol%), it is stirred at room temperature pre-dispersed 25min, heats up and control reaction temperature 55 DEG C
Lower reaction 30min, then adds 148g vinylidene chloride monomer and 93g n-butyl acrylate monomer, completes list
After body adds, then add 2g sodium peroxydisulfate and control to react at reaction temperature 55 DEG C 20min, then dripping 60g
Maleic anhydride monomer, heats up and controls reaction temperature 60 DEG C, when polymerization pressure declines 0.2MPa
Time, add 18g n-dodecyl mercaptan and stop stirring, reducing residue in reaction temperature, releasing reactor
Gas, discharging and through filter, washing and dried, obtain 2535g vinyl chloride copolymer resin.Through unit
Element analysis, nuclear-magnetism, infrared analysis confirm vinyl chloride construction unit shared mole hundred in vinyl chloride copolymer resin
Dividing content is 89.2%；Molar content shared by vinylidene chloride construction unit is 5.2%；N-butyl acrylate
Molar content shared by construction unit is 3.4%；Molar content shared by maleic anhydride construction unit
It is 2.2%.
Polymer data: resin particle diameter 213 μm that Coulter particle size analyzer measures；AutoPore-IV
The resin apparent density that-9510 mercury injection apparatuses measure is 0.68g/cm3, porosity is 55%, is specifically shown in Table 1.
Mechanical properties of polymer: hot strength (GB/T1040-2006) is 67.3MPa, shock strength (GB/T
1843-1996) it is 28.3KJ/m2, specifically it is shown in Table 1.
Embodiment 2
Under the protection of noble gas, in 10L rustless steel autoclave add 6L high purity deionized water,
2412g Vinyl Chloride Monomer, 16g sodium peroxydisulfate, 28g sodium bicarbonate and 185g hydroxypropyl methyl cellulose (hydroxyl
Propyl group content is 6.3mol%), it is stirred at room temperature pre-dispersed 25min, heats up and control reaction temperature 55 DEG C
Lower reaction 30min, then adds 296g vinylidene chloride monomer and 242g n-butyl acrylate monomer, completes list
After body adds, then add 4g sodium peroxydisulfate and control to react at reaction temperature 55 DEG C 20min, then dripping 60g
Maleic anhydride monomer, heats up and controls reaction temperature 60 DEG C, when polymerization pressure declines 0.2MPa
Time, add 18g n-dodecyl mercaptan and stop stirring, reducing residue in reaction temperature, releasing reactor
Gas, discharging and through filter, washing and dried, obtain 2619g vinyl chloride copolymer resin.Through unit
Element analysis, nuclear-magnetism, infrared analysis confirm vinyl chloride construction unit shared mole hundred in vinyl chloride copolymer resin
Dividing content is 78.4%；Molar content shared by vinylidene chloride construction unit is 10.5%；N-butyl acrylate
Molar content shared by construction unit is 9.0%；Molar content shared by maleic anhydride construction unit
It is 2.1%.
Polymer data: resin particle diameter 223 μm that Coulter particle size analyzer measures；AutoPore-IV
The resin apparent density that-9510 mercury injection apparatuses measure is 0.62g/cm3, porosity is 49%, is specifically shown in Table 1.
Mechanical properties of polymer: hot strength (GB/T1040-2006) is 65.3MPa, shock strength (GB/T
1843-1996) it is 31.4KJ/m2, specifically it is shown in Table 1.
Embodiment 3
Under the protection of noble gas, in 10L rustless steel autoclave add 6L high purity deionized water,
2088g Vinyl Chloride Monomer, 14g sodium peroxydisulfate, 28g sodium bicarbonate and 185g hydroxypropyl methyl cellulose (hydroxyl
Propyl group content is 6.3mol%), it is stirred at room temperature pre-dispersed 25min, heats up and control reaction temperature 55 DEG C
Lower reaction 30min, then adds 603g vinylidene chloride monomer and 153g n-butyl acrylate monomer, completes list
After body adds, then add 6g sodium peroxydisulfate and control to react at reaction temperature 55 DEG C 20min, then dripping 146g
Maleic anhydride monomer, heats up and controls reaction temperature 60 DEG C, when polymerization pressure declines 0.2MPa
Time, add 18g n-dodecyl mercaptan and stop stirring, reducing residue in reaction temperature, releasing reactor
Gas, discharging and through filter, washing and dried, obtain 2608g vinyl chloride copolymer resin.Through unit
Element analysis, nuclear-magnetism, infrared analysis confirm vinyl chloride construction unit shared mole hundred in vinyl chloride copolymer resin
Dividing content is 68.8%；Molar content shared by vinylidene chloride construction unit is 20.4%；N-butyl acrylate
Molar content shared by construction unit is 5.5%；Molar content shared by maleic anhydride construction unit
It is 5.3%, is specifically shown in Table 1.
Polymer data: resin particle diameter 234 μm that Coulter particle size analyzer measures；AutoPore-IV
The resin apparent density that-9510 mercury injection apparatuses measure is 0.58g/cm3, porosity is 45%, is specifically shown in Table 1.
Mechanical properties of polymer: hot strength (GB/T1040-2006) is 59.7MPa, shock strength (GB/T
1843-1996) it is 34.8KJ/m2, specifically it is shown in Table 1.
Embodiment 4
Under the protection of noble gas, in 10L rustless steel autoclave add 6L high purity deionized water,
1804g Vinyl Chloride Monomer, 12g sodium peroxydisulfate, 28g sodium bicarbonate and 185g hydroxypropyl methyl cellulose (hydroxyl
Propyl group content is 6.3mol%), it is stirred at room temperature pre-dispersed 25min, heats up and control reaction temperature 55 DEG C
Lower reaction 30min, then adds 743g vinylidene chloride monomer and 303g n-butyl acrylate monomer, completes list
After body adds, then add 8g sodium peroxydisulfate and control to react at reaction temperature 55 DEG C 20min, then dripping 152g
Maleic anhydride monomer, heats up and controls reaction temperature 60 DEG C, when polymerization pressure declines 0.2MPa
Time, add 18g n-dodecyl mercaptan and stop stirring, reducing residue in reaction temperature, releasing reactor
Gas, discharging and through filter, washing and dried, obtain 2643g vinyl chloride copolymer resin.Through unit
Element analysis, nuclear-magnetism, infrared analysis confirm vinyl chloride construction unit shared mole hundred in vinyl chloride copolymer resin
Dividing content is 58.0%；Molar content shared by vinylidene chloride construction unit is 25.6%；N-butyl acrylate
Molar content shared by construction unit is 10.9%；Molar content shared by maleic anhydride construction unit
It is 5.5%.
Polymer data: resin particle diameter 252 μm that Coulter particle size analyzer measures；AutoPore-IV
The resin apparent density that-9510 mercury injection apparatuses measure is 0.56g/cm3, porosity is 42%, is specifically shown in Table 1.
Mechanical properties of polymer: hot strength (GB/T1040-2006) is 58.7MPa, shock strength (GB/T
1843-1996) it is 35.2KJ/m2, specifically it is shown in Table 1.
Embodiment 5
Under the protection of noble gas, in 10L rustless steel autoclave add 6L high purity deionized water,
2408g Vinyl Chloride Monomer, 12g sodium peroxydisulfate, 28g sodium bicarbonate, 125g hydroxypropyl methyl cellulose (hydroxyl
Propyl group content is 6.3mol%) and 60g polyvinyl alcohol (alcoholysis degree is 65%), it is stirred at room temperature pre-dispersed
25min, heats up and controls to react at reaction temperature 55 DEG C 30min, then adding 296g vinylidene chloride monomer
With 242g n-butyl acrylate monomer, after completing monomer interpolation, then add 4g sodium peroxydisulfate and control reaction
React 20min, then dropping 60g maleic anhydride monomer at temperature 55 DEG C, heat up and control reaction temperature
Spend 60 DEG C, when polymerization pressure declines 0.2MPa, add 18g n-dodecyl mercaptan and stop stirring,
Reduce reaction temperature, residual gas in releasing reactor, discharging and through filter, washing and dried,
To 2635g vinyl chloride copolymer resin.Vinyl chloride copolymer is confirmed through elementary analysis, nuclear-magnetism, infrared analysis
In resin, molar content shared by vinyl chloride construction unit is 77.9%；Shared mole of vinylidene chloride construction unit
Percentage composition is 11.0%；Molar content shared by n-butyl acrylate construction unit is 8.9%；Maleic
Molar content shared by dicarboxylic anhydride construction unit is 2.2%.
Polymer data: resin particle diameter 219 μm that Coulter particle size analyzer measures；AutoPore-IV
The resin apparent density that-9510 mercury injection apparatuses measure is 0.65g/cm3, porosity is 47%, is specifically shown in Table 1.
Mechanical properties of polymer: hot strength (GB/T1040-2006) is 66.1MPa, shock strength (GB/T
1843-1996) it is 32.4KJ/m2, specifically it is shown in Table 1.
Embodiment 6
Under the protection of noble gas, in 10L rustless steel autoclave add 6L high purity deionized water,
2415g Vinyl Chloride Monomer, 12g sodium peroxydisulfate, 28g sodium bicarbonate, 95g hydroxypropyl methyl cellulose (hydroxyl
Propyl group content is 6.3mol%) and 90g polyvinyl alcohol (alcoholysis degree is 65%), it is stirred at room temperature pre-dispersed
25min, heats up and controls to react at reaction temperature 55 DEG C 30min, then adding 296g vinylidene chloride monomer
With 242g n-butyl acrylate monomer, after completing monomer interpolation, then add 4g sodium peroxydisulfate and control reaction
React 20min, then dropping 60g maleic anhydride monomer at temperature 55 DEG C, heat up and control reaction temperature
Spend 60 DEG C, when polymerization pressure declines 0.2MPa, add 18g n-dodecyl mercaptan and stop stirring,
Reduce reaction temperature, residual gas in releasing reactor, discharging and through filter, washing and dried,
To 2642g vinyl chloride copolymer resin.Vinyl chloride copolymer is confirmed through elementary analysis, nuclear-magnetism, infrared analysis
In resin, molar content shared by vinyl chloride construction unit is 78.0%；Shared mole of vinylidene chloride construction unit
Percentage composition is 10.8%；Molar content shared by n-butyl acrylate construction unit is 9.0%；Maleic
Molar content shared by dicarboxylic anhydride construction unit is 2.2%.
Polymer data: resin particle diameter 216 μm that Coulter particle size analyzer measures；AutoPore-IV
The resin apparent density that-9510 mercury injection apparatuses measure is 0.73g/cm3, porosity is 44%, is specifically shown in Table 1.
Mechanical properties of polymer: hot strength (GB/T1040-2006) is 66.8MPa, shock strength (GB/T
1843-1996) it is 34.5KJ/m2, specifically it is shown in Table 1.
Embodiment 7
Under the protection of noble gas, in 10L rustless steel autoclave add 6L high purity deionized water,
2407g Vinyl Chloride Monomer, 12g sodium peroxydisulfate, 28g sodium bicarbonate, 60g hydroxypropyl methyl cellulose (hydroxyl
Propyl group content is 6.3mol%) and 125g polyvinyl alcohol (alcoholysis degree is 65%), it is stirred at room temperature pre-point
Dissipate 25min, heat up and control to react at reaction temperature 55 DEG C 30min, then adding 296g vinylidene chloride list
Body and 242g n-butyl acrylate monomer, after completing monomer interpolation, then add 4g sodium peroxydisulfate and control anti-
Answer reaction 20min at temperature 55 DEG C, then dropping 60g maleic anhydride monomer, heat up and control reaction
Temperature 60 C, when polymerization pressure declines 0.2MPa, adds 18g n-dodecyl mercaptan and stops stirring
Mix, reduce reaction temperature, residual gas in releasing reactor, discharging and through filter, washing and dried,
Obtain 2624g vinyl chloride copolymer resin.Chloroethylene copolymer is confirmed through elementary analysis, nuclear-magnetism, infrared analysis
In resin, molar content shared by vinyl chloride construction unit is 77.8%；Rub shared by vinylidene chloride construction unit
Your percentage composition is 11.0%；Molar content shared by n-butyl acrylate construction unit is 9.1%；Along fourth
Molar content shared by enedioic acid acid anhydride construction unit is 2.1%.
Polymer data: resin particle diameter 217 μm that Coulter particle size analyzer measures；AutoPore-IV
The resin apparent density that-9510 mercury injection apparatuses measure is 0.68g/cm3, porosity is 46%, is specifically shown in Table 1.
Mechanical properties of polymer: hot strength (GB/T1040-2006) is 65.9MPa, shock strength (GB/T
1843-1996) it is 31.0KJ/m2, specifically it is shown in Table 1.
Embodiment 8
Under the protection of noble gas, in 10L rustless steel autoclave add 6L high purity deionized water,
2395g Vinyl Chloride Monomer, 12g sodium peroxydisulfate, 28g 2,2'-Azobis(2,4-dimethylvaleronitrile), 60g hydroxypropyl methyl cellulose
(hydroxypropyl content is 6.3mol%) and 125g polyvinyl alcohol (alcoholysis degree is 65%), be stirred at room temperature
Pre-dispersed 25min, heats up and controls to react at reaction temperature 55 DEG C 30min, then adding the inclined chloroethene of 296g
Alkene monomer and 241g acrylic acid-2-ethyl caproite monomer, after completing monomer interpolation, then it is different to add 4g azo two
Heptonitrile also controls to react at reaction temperature 55 DEG C 20min, then dropping 60g maleic anhydride monomer, rises
Temperature also controls reaction temperature 60 DEG C, when polymerization pressure declines 0.2MPa, adds 18g dodecyl
Mercaptan also stops stirring, reduces reaction temperature, residual gas in releasing reactor, discharging through filtering, washing
Wash and dried, obtain 2648g vinyl chloride copolymer resin.Through elementary analysis, nuclear-magnetism, infrared analysis
Confirm that in vinyl chloride copolymer resin, molar content shared by vinyl chloride construction unit is 78.1%；Vinylidene chloride
Molar content shared by construction unit is 10.9%；Molar content shared by n-butyl acrylate construction unit
It is 9.0%；Molar content shared by maleic anhydride construction unit is 2.0%.
Polymer data: resin particle diameter 235 μm that Coulter particle size analyzer measures；AutoPore-IV
The resin apparent density that-9510 mercury injection apparatuses measure is 0.75g/cm3, porosity is 42%, is specifically shown in Table 1.
Mechanical properties of polymer: hot strength (GB/T1040-2006) is 63.2MPa, shock strength (GB/T
1843-1996) it is 38.7KJ/m2, specifically it is shown in Table 1.
Table 1: vinyl chloride copolymer resin Performance comparision prepared by embodiment 1-8
Knowable to table 1 data, the present invention is by introducing vinylidene chloride, unsaturated lipid on polrvinyl chloride main chain
Fat acid and maleic anhydride, and adjust whole, improve dispersant dosage and vinyl chloride that coupling prepares altogether
Copolymer resin, grain form is regular, fine and close, has relatively low porosity and relatively high apparent density, and it processes system
Product possess excellent tensile property and erosion-resisting characteristics.
Claims (1)
1. the preparation method of the vinyl chloride copolymer resin of a resistance to impact, it is characterised in that
Described copolymer resin is made up by suspension polymerisation of the raw material of following parts by weight: mix monomer 100 parts,
Dispersant 0.1-1 part, initiator 0.05-0.3 part, pH adjusting agent 0.1-2 part, chain-transferring agent 0.05-0.2 part
With deionized water 100-300 part；
Described mix monomer consists of the following components in percentage by weight: vinyl chloride 60-90%, vinylidene chloride
5-30%, acrylate 1-10% and maleic anhydride (MA) 1-5%；
Described dispersant is hydroxypropyl methyl cellulose and/or polyvinyl alcohol (PVA)；
Described initiator is azo compound or persulfate；
Described pH adjusting agent is hydrophosphate or bicarbonate；
Described chain-transferring agent is aliphatic mercaptan；
Described method comprises the steps:
(1) under the protection of noble gas, by Vinyl Chloride Monomer, dispersant, part initiator, pH regulator
Agent and deionized water join reactor, pre-dispersed 20-30min under room temperature；
(2) heat up and control to react at reaction temperature 30-70 DEG C 15-45min, then adding vinylidene chloride and third
Olefin(e) acid ester mix monomer；
(3) after completing monomer interpolation, add residue initiator, control to react at reaction temperature 30-70 DEG C
15-30min；
(4) reactor temperature is warming up to 40-80 DEG C, drips maleic anhydride monomer；
(5) when polymerization pressure declines 0.1-0.3MPa, add chain-transferring agent, stop stirring, reduce
Reaction temperature, residual gas in releasing reactor, discharging；
(6) discharging is through filtering, washing and dried, obtains vinyl chloride copolymer resin；
Described dispersant consists of the following components in percentage by weight: polyvinyl alcohol (PVA) 20-80% and hydroxypropyl
Ylmethyl cellulose 20-80%；
The alcoholysis degree of described polyvinyl alcohol (PVA) is 69-89mol%, the hydroxyl of described hydroxypropyl methyl cellulose
Propyl group content is 4-12mol%.
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| CN201610412730.1A CN105924559B (en) | 2014-12-29 | 2014-12-29 | A kind of preparation method of the vinyl chloride copolymer resin of impact resistance |
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| CN201610412730.1A CN105924559B (en) | 2014-12-29 | 2014-12-29 | A kind of preparation method of the vinyl chloride copolymer resin of impact resistance |
| CN201410836983.2A CN104448092B (en) | 2014-12-29 | 2014-12-29 | Preparation method of impact-resistant chloroethylene copolymer resin |
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| CN201410836983.2A Expired - Fee Related CN104448092B (en) | 2014-12-29 | 2014-12-29 | Preparation method of impact-resistant chloroethylene copolymer resin |
| CN201610412735.4A Expired - Fee Related CN106008780B (en) | 2014-12-29 | 2014-12-29 | A kind of preparation method of the vinyl chloride copolymer resin of impact resistance |
| CN201610414680.0A Active CN105968246B (en) | 2014-12-29 | 2014-12-29 | A kind of preparation method of the vinyl chloride copolymer resin of impact resistance |
| CN201610412284.4A Expired - Fee Related CN105859943B (en) | 2014-12-29 | 2014-12-29 | A kind of preparation method of the vinyl chloride copolymer resin of impact resistance |
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| CN201610414680.0A Active CN105968246B (en) | 2014-12-29 | 2014-12-29 | A kind of preparation method of the vinyl chloride copolymer resin of impact resistance |
| CN201610412284.4A Expired - Fee Related CN105859943B (en) | 2014-12-29 | 2014-12-29 | A kind of preparation method of the vinyl chloride copolymer resin of impact resistance |
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| CN108084318A (en) * | 2017-12-28 | 2018-05-29 | 宁波俐辰新能源有限公司 | A kind of nuisanceless flame-resistant high-temperature-resistant polyvinyl chloride and its manufacturing method |
| KR102251268B1 (en) * | 2018-04-30 | 2021-05-12 | 주식회사 엘지화학 | Vinyl chloride polymer and preparation method thereof |
| CN109369839B (en) * | 2018-09-21 | 2020-12-29 | 无锡洪汇新材料科技股份有限公司 | Self-crosslinking vinyl chloride copolymer emulsion and preparation method thereof |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6295306A (en) * | 1985-10-22 | 1987-05-01 | Toagosei Chem Ind Co Ltd | Production of vinylidene chloride copolymer |
| JPH0493301A (en) * | 1990-08-10 | 1992-03-26 | Kuraray Co Ltd | Dispersing agent and dispersion stabilizer for suspension polymerization of vinyl monomer |
| JPH05179167A (en) * | 1991-12-27 | 1993-07-20 | Mitsubishi Heavy Ind Ltd | Conductive coating material for preventing adhesion of marine organism |
| US20030162927A1 (en) * | 2002-02-26 | 2003-08-28 | Shin-Etsu Chemical Co., Ltd. | Method of producing a vinyl chloride-based polymer |
| CN101314627A (en) * | 2008-06-04 | 2008-12-03 | 中国农业大学 | Film-forming agent for seed clothing sheet and preparation method thereof |
| CN101367898A (en) * | 2008-08-27 | 2009-02-18 | 浙江巨化股份有限公司电化厂 | PVDC copolymerization emulsion, preparation and uses thereof |
| CN102459372A (en) * | 2009-05-15 | 2012-05-16 | 阿肯马法国公司 | Method for preparing a suspension of pvc grafted onto an elastomer |
| CN102850867A (en) * | 2012-09-04 | 2013-01-02 | 海南必凯水性涂料有限公司 | Heat-seal polyvinylidene chloride emulsion used for coating, and preparation method thereof |
| CN103059192A (en) * | 2012-12-26 | 2013-04-24 | 海南必凯水性涂料有限公司 | Polyvinyl dichloride (PVDC) latex used for interior and exterior wall coating materials and preparation method thereof and application thereof |
| CN103193918A (en) * | 2013-05-06 | 2013-07-10 | 南通瑞普埃尔生物工程有限公司 | Vinyl chloride-vinylidene chloride (VDC)/acrylic acid (AA)/methyl methacrylate (MMA)/acrylonitrile (AN) copolymerized polyvinyl dichloride (PVDC) emulsion and preparation method thereof |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1064848A (en) * | 1962-11-17 | 1967-04-12 | Kureha Chemical Ind Co Ltd | Method for the production of vinyl resins |
| GB1385326A (en) * | 1971-09-20 | 1975-02-26 | Bp Chem Int Ltd | Co-polymerisation process |
| JPS5358592A (en) * | 1976-11-09 | 1978-05-26 | Kureha Chem Ind Co Ltd | Preparation of vinylidene chloride-vinyl chloride copolymer |
| US5294684A (en) * | 1990-05-22 | 1994-03-15 | Shin-Etsu Chemical Co., Ltd. | Process for producing vinyl chloride resin |
| EP0633273A1 (en) * | 1993-07-05 | 1995-01-11 | Shin-Etsu Chemical Co., Ltd. | Process for producing vinyl chloride polymers |
| EP2057201B1 (en) * | 2006-08-25 | 2009-12-23 | Clariant Finance (BVI) Limited | Oil-, water- and soil-repellent perfluoroalkylethyl methacrylate copolymers |
| CN103467664B (en) * | 2013-09-13 | 2015-09-30 | 四川凯本新材料科技有限公司 | A kind of preparation method of fire-retardant, anti-impact, high workability chlorovinyl Special Resin |
-
2014
- 2014-12-29 CN CN201610412730.1A patent/CN105924559B/en not_active Expired - Fee Related
- 2014-12-29 CN CN201410836983.2A patent/CN104448092B/en not_active Expired - Fee Related
- 2014-12-29 CN CN201610412735.4A patent/CN106008780B/en not_active Expired - Fee Related
- 2014-12-29 CN CN201610414680.0A patent/CN105968246B/en active Active
- 2014-12-29 CN CN201610412284.4A patent/CN105859943B/en not_active Expired - Fee Related
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6295306A (en) * | 1985-10-22 | 1987-05-01 | Toagosei Chem Ind Co Ltd | Production of vinylidene chloride copolymer |
| JPH0493301A (en) * | 1990-08-10 | 1992-03-26 | Kuraray Co Ltd | Dispersing agent and dispersion stabilizer for suspension polymerization of vinyl monomer |
| JPH05179167A (en) * | 1991-12-27 | 1993-07-20 | Mitsubishi Heavy Ind Ltd | Conductive coating material for preventing adhesion of marine organism |
| US20030162927A1 (en) * | 2002-02-26 | 2003-08-28 | Shin-Etsu Chemical Co., Ltd. | Method of producing a vinyl chloride-based polymer |
| CN101314627A (en) * | 2008-06-04 | 2008-12-03 | 中国农业大学 | Film-forming agent for seed clothing sheet and preparation method thereof |
| CN101367898A (en) * | 2008-08-27 | 2009-02-18 | 浙江巨化股份有限公司电化厂 | PVDC copolymerization emulsion, preparation and uses thereof |
| CN102459372A (en) * | 2009-05-15 | 2012-05-16 | 阿肯马法国公司 | Method for preparing a suspension of pvc grafted onto an elastomer |
| CN102850867A (en) * | 2012-09-04 | 2013-01-02 | 海南必凯水性涂料有限公司 | Heat-seal polyvinylidene chloride emulsion used for coating, and preparation method thereof |
| CN103059192A (en) * | 2012-12-26 | 2013-04-24 | 海南必凯水性涂料有限公司 | Polyvinyl dichloride (PVDC) latex used for interior and exterior wall coating materials and preparation method thereof and application thereof |
| CN103193918A (en) * | 2013-05-06 | 2013-07-10 | 南通瑞普埃尔生物工程有限公司 | Vinyl chloride-vinylidene chloride (VDC)/acrylic acid (AA)/methyl methacrylate (MMA)/acrylonitrile (AN) copolymerized polyvinyl dichloride (PVDC) emulsion and preparation method thereof |
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| Publication number | Publication date |
|---|---|
| CN105859943B (en) | 2017-12-19 |
| CN105968246B (en) | 2018-03-20 |
| CN104448092B (en) | 2017-02-22 |
| CN105859943A (en) | 2016-08-17 |
| CN105968246A (en) | 2016-09-28 |
| CN106008780A (en) | 2016-10-12 |
| CN104448092A (en) | 2015-03-25 |
| CN106008780B (en) | 2017-11-17 |
| CN105924559B (en) | 2017-12-08 |
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