CN104327216B - Terpolymer used for hard polyvinyl chloride and preparation method thereof - Google Patents
Terpolymer used for hard polyvinyl chloride and preparation method thereof Download PDFInfo
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- 229920001897 terpolymer Polymers 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 229920000915 polyvinyl chloride Polymers 0.000 title abstract description 19
- 239000004800 polyvinyl chloride Substances 0.000 title abstract description 19
- 239000000839 emulsion Substances 0.000 claims abstract description 23
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical group CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims abstract description 16
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims abstract description 15
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000003999 initiator Substances 0.000 claims abstract description 13
- 229920001577 copolymer Polymers 0.000 claims abstract description 10
- 239000002270 dispersing agent Substances 0.000 claims abstract description 7
- 239000012792 core layer Substances 0.000 claims abstract 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 26
- 238000006243 chemical reaction Methods 0.000 claims description 26
- 238000002156 mixing Methods 0.000 claims description 22
- 238000010792 warming Methods 0.000 claims description 16
- 238000006392 deoxygenation reaction Methods 0.000 claims description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 13
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 10
- 235000019394 potassium persulphate Nutrition 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 8
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 8
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 8
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 7
- 239000004141 Sodium laurylsulphate Substances 0.000 claims description 7
- 235000019333 sodium laurylsulphate Nutrition 0.000 claims description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 230000000379 polymerizing effect Effects 0.000 claims description 6
- 230000005070 ripening Effects 0.000 claims description 6
- 229920002689 polyvinyl acetate Polymers 0.000 claims description 5
- 239000011118 polyvinyl acetate Substances 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 4
- 239000001488 sodium phosphate Substances 0.000 claims description 4
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 4
- JHJUUEHSAZXEEO-UHFFFAOYSA-M sodium;4-dodecylbenzenesulfonate Chemical compound [Na+].CCCCCCCCCCCCC1=CC=C(S([O-])(=O)=O)C=C1 JHJUUEHSAZXEEO-UHFFFAOYSA-M 0.000 claims description 4
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims description 4
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- IVKNZCBNXPYYKL-UHFFFAOYSA-N 2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[4-(2,4,4-trimethylpentan-2-yl)phenoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethanol Chemical compound CC(C)(C)CC(C)(C)C1=CC=C(OCCOCCOCCOCCOCCOCCOCCOCCOCCOCCO)C=C1 IVKNZCBNXPYYKL-UHFFFAOYSA-N 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 claims description 2
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 claims description 2
- 229920000053 polysorbate 80 Polymers 0.000 claims description 2
- 229910000160 potassium phosphate Inorganic materials 0.000 claims description 2
- 235000011009 potassium phosphates Nutrition 0.000 claims description 2
- 239000011258 core-shell material Substances 0.000 claims 1
- 239000000178 monomer Substances 0.000 abstract description 10
- 238000012545 processing Methods 0.000 abstract description 6
- 239000008367 deionised water Substances 0.000 abstract description 5
- 229910021641 deionized water Inorganic materials 0.000 abstract description 5
- 238000005516 engineering process Methods 0.000 abstract description 4
- 239000003513 alkali Substances 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000010410 layer Substances 0.000 abstract 2
- 239000012752 auxiliary agent Substances 0.000 abstract 1
- 239000011347 resin Substances 0.000 description 14
- 229920005989 resin Polymers 0.000 description 14
- 239000003607 modifier Substances 0.000 description 10
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Substances [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 5
- -1 methacrylic acid alkane Chemical class 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- OBDRUIIBHOMNPP-UHFFFAOYSA-N butyl prop-2-enoate;ethenyl acetate;methyl 2-methylprop-2-enoate Chemical compound CC(=O)OC=C.COC(=O)C(C)=C.CCCCOC(=O)C=C OBDRUIIBHOMNPP-UHFFFAOYSA-N 0.000 description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 235000021355 Stearic acid Nutrition 0.000 description 3
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 3
- 235000013539 calcium stearate Nutrition 0.000 description 3
- 239000008116 calcium stearate Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- UQLDLKMNUJERMK-UHFFFAOYSA-L di(octadecanoyloxy)lead Chemical compound [Pb+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O UQLDLKMNUJERMK-UHFFFAOYSA-L 0.000 description 3
- 230000000977 initiatory effect Effects 0.000 description 3
- 239000011256 inorganic filler Substances 0.000 description 3
- 229910003475 inorganic filler Inorganic materials 0.000 description 3
- OCWMFVJKFWXKNZ-UHFFFAOYSA-L lead(2+);oxygen(2-);sulfate Chemical compound [O-2].[O-2].[O-2].[Pb+2].[Pb+2].[Pb+2].[Pb+2].[O-]S([O-])(=O)=O OCWMFVJKFWXKNZ-UHFFFAOYSA-L 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 3
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 3
- 229920005604 random copolymer Polymers 0.000 description 3
- 239000008117 stearic acid Substances 0.000 description 3
- 239000004408 titanium dioxide Substances 0.000 description 3
- 239000006057 Non-nutritive feed additive Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- 230000004927 fusion Effects 0.000 description 2
- UMKARVFXJJITLN-UHFFFAOYSA-N lead;phosphorous acid Chemical compound [Pb].OP(O)O UMKARVFXJJITLN-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000010008 shearing Methods 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 125000005250 alkyl acrylate group Chemical group 0.000 description 1
- SYWDWCWQXBUCOP-UHFFFAOYSA-N benzene;ethene Chemical group C=C.C1=CC=CC=C1 SYWDWCWQXBUCOP-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- HUTDDBSSHVOYJR-UHFFFAOYSA-H bis[(2-oxo-1,3,2$l^{5},4$l^{2}-dioxaphosphaplumbetan-2-yl)oxy]lead Chemical compound [Pb+2].[Pb+2].[Pb+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O HUTDDBSSHVOYJR-UHFFFAOYSA-H 0.000 description 1
- 239000004035 construction material Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- XPNLOZNCOBKRNJ-UHFFFAOYSA-N ethyl prop-2-enoate;methyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C=C.COC(=O)C(C)=C XPNLOZNCOBKRNJ-UHFFFAOYSA-N 0.000 description 1
- 238000010559 graft polymerization reaction Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000007943 implant Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- SCUZVMOVTVSBLE-UHFFFAOYSA-N prop-2-enenitrile;styrene Chemical compound C=CC#N.C=CC1=CC=CC=C1 SCUZVMOVTVSBLE-UHFFFAOYSA-N 0.000 description 1
- HXHCOXPZCUFAJI-UHFFFAOYSA-N prop-2-enoic acid;styrene Chemical group OC(=O)C=C.C=CC1=CC=CC=C1 HXHCOXPZCUFAJI-UHFFFAOYSA-N 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- MZSDGDXXBZSFTG-UHFFFAOYSA-M sodium;benzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=CC=C1 MZSDGDXXBZSFTG-UHFFFAOYSA-M 0.000 description 1
- 229920000638 styrene acrylonitrile Polymers 0.000 description 1
Abstract
The invention belongs to the processing auxiliary agent field used for hard polyvinyl chloride, and concretely relates to a terpolymer used for hard polyvinyl chloride and a preparation method thereof. The terpolymer is characterized in that a core layer and a shell layer with mass ratio of 3: 1-4: 1 are prepared by employing a grafting emulsion polymerisation technology, wherein the core layer is prepared by a vinyl acetate monomer, deionized water, a dispersant, an emulsifier, an alkalescence medium and an initiator; and the shell layer is prepared by methyl methacrylate, butyl acrylate monomer, the emulsifier and the initiator. According to the invention, yield is high as more than 98%, the emulsion stability is good, melt-strength and balance torque are greatly increased, water resistance, alkali resistance and heat resistance of the copolymer are increased, production cost is greatly reduced, and cost performance can be increased. The invention also provides a preparation method which has the advantages of simple process and simple operation.
Description
Technical field
The invention belongs to RPVC with processing aid field and in particular to a kind of RPVC ternary altogether
Polymers and preparation method thereof.
Background technology
China is that world RPVC PVC produces and consumption big country, related PVC product have wide market ring
Border, existing dynamics has range again.Swift and violent based on urban and rural buildings engineering, traffic engineering, environmental project, the energy and hydraulic engineering etc.
Development, PVC construction material, the market demand of engineering material increasingly improve, and are currently one of maximum plastics variety of China's yield.
Hard PVC does not contain softening agent, therefore, easy-formation, less brittle, nontoxic pollution-free, the holding time is long, is widely used in section bar, abnormal shape
The industries such as material, sheet material, tubing, foamed board, building template, wood moulding, have very big development and application values.
PVC work in-process needs to be separated into uniform molten state ability molding by heating and shearing, but polyvinyl chloride resin itself
Transmission to heat and shearing force is not strong, and fusion time is longer, and the melt of formation is uneven, affects products appearance and mechanicalness
Can, after adding modifier, fluidity of molten, deformability and the product surface gloss of polyvinyl chloride resin can be obviously improved
Etc. characteristic.Aggregated reaction and be obtained modifier substantially can be subdivided into following five big class：Methyl methacrylate-propylene
Acid butyl ester random copolymer, methyl methacrylate-ethyl acrylate random copolymer, styrene-acrylonitrile random copolymer,
Esters of acrylic acid-phenylethylene blending resin and the inorganic filler blending resin being mixed with nano modification.Methyl methacrylate-
Its advantage of butyl acrylate (or ethyl acrylate) copolymer is to have excellent processing characteristics, heat resistance, can give system
The wider processing temperature scope of product, higher melt strength, good surface smoothness and dimensional stability；Styrene-
Vinyl cyanide modifier compares for esters of acrylic acid modifier, has obvious cost advantage, but because of benzene
Ethylene contains unsaturated double-bond, and uvioresistant and ageing resistace are general, and styrene is poor with the PVC compatibility simultaneously, processing
Scope is narrower, and melt plasticizing is slow, and product surface fineness is bad；The inorganic filler blending resin being mixed with nano modification is by above-mentioned
Based on two big class modifiers, then it is equipped with the implants such as nano-calcium carbonate, silicon dioxide, mica powder, thus reducing product
Price.Addition is bigger, and the mechanical properties decrease of hard PVC product is more obvious, and such as product fragility increases, melt in the course of processing
Plasticizing is slow, and surface smoothness declines, dimensional stability is unable to reach expectation index etc..
The present inventor finds in research PVC modifier technology path and market application process, methacrylic acid alkane
Base ester, alkyl-acrylates resin and acrylonitrile, styrene resin are improving processing aid and the PVC compatibility and plasticizing
Aspect has certain advantage, but is as the petrochemical industry prices of raw materials and goes up and force PVC modifier to produce, apply factory
Family has to, by adding substantial amounts of inorganic filler, carry out reduces cost to seek enterprise development with this.Ultimately form vicious cycle,
Seriously hinder hard PVC product industry integral level, deviate national " to mould Dai Gang, to mould Dai Mu " overall planning.
Content of the invention
It is an object of the invention to provide a kind of RPVC terpolymer, good emulsion stability, greatly improve
Melt strength and counter balance torque, improve resistance to water, alkali resistance and the heat resistance of copolymer, and the present invention also provides its preparation side
Method, reduces production cost, improves yield, and preparation process is simple, easy and simple to handle.
RPVC terpolymer of the present invention, is 3 by mass ratio:1-4:1 stratum nucleare and shell are adopted
Made with graft emulsion polymerization technique,
Wherein：Stratum nucleare is made up of the raw material of following mass fraction：100 parts of vinyl acetate monomer, water 250-300 part, point
Powder 0.01-0.1 part, emulsifying agent 0.05-2.0 part, alkaline medium 0.5-2.0 part and initiator 0.01-0.05 part；
Shell is made up of the raw material of following mass fraction：Methyl methacrylate 80-95 part, butyl acrylate 5-20 part,
Emulsifying agent 0.5-3.0 part and initiator 0.01-0.05 part.
Dispersant is for one of polyvinyl alcohol 1788 or polyvinyl alcohol 1799 or two kinds with arbitrary proportion mixing.
Emulsifying agent is one or more of sodium lauryl sulphate, dodecylbenzene sodium sulfonate, OP-10 or tween 80
With arbitrary proportion mixing.
Initiator be one or more of potassium peroxydisulfate, Ammonium persulfate., sodium sulfite or sodium bicarbonate with arbitrarily than
Example mixing.
Alkaline medium is one of potassium hydroxide, sodium hydroxide, sodium carbonate, potassium phosphate or sodium phosphate or two kinds with any
Ratio mixes.
Stratum nucleare is polyvinyl acetate, and shell is poly- (butyl acrylate-methyl ester) copolymer.
The present invention also provides the preparation method of RPVC terpolymer, comprises the following steps：
(1) by vinyl acetate monomer, water, dispersant, emulsifying agent and alkaline medium addition reaction unit, nitrogen deoxygenation,
Stir under the mixing speed of 50-300r/min, be warming up to 45 DEG C -55 DEG C, add initiator, controlling reaction temperature is in 55-60
DEG C reaction, obtain stratum nucleare emulsion；
(2) emulsifying agent, methyl methacrylate and butyl acrylate are added sequentially to the stratum nucleare emulsion that step (1) obtains
In, nitrogen deoxygenation, stirs under the mixing speed of 50-300r/min, is warming up to 40 DEG C -50 DEG C, add initiator, control reaction
Temperature, at 50-55 DEG C, reacts 2-3h；
(3) intensification ripening, cooling discharge, it is spray-dried, obtain product.
Step (1) prepares stratum nucleare, and stratum nucleare is polyvinyl acetate；Step (2) is graft shell layer outer in stratum nucleare, shell
For poly- (butyl acrylate-methyl ester) copolymer.
Step (1) is preferably：First, by part vinyl acetate monomer, water, dispersant, alkaline medium and part emulsifying
Agent adds reaction unit, nitrogen deoxygenation, stirs 30min, be warming up to 45 DEG C -55 DEG C under the mixing speed of 50-300r/min, control
Reaction temperature processed is 55-60 DEG C, using semi-continuous emulsion polymerizing method by remaining vinyl acetate monomer, emulsifying agent and initiator
Divide 3-5 time and cause polymerization, obtain stratum nucleare emulsion.
The quality that in step (1), vinyl acetate monomer adds first is the 15-25% of its gross mass, and emulsifying agent adds first
The quality entering is the 15-25% of its gross mass.
In step (3), slaking reaction temperature is 80 DEG C, and drop temperature is 40 DEG C.
The present invention utilizes methyl methacrylate under alkaline medium by semi-continuous emulsion polymerizing method, graft polymerization process
Ester, butyl acrylate are grafted to polyvinyl acetate surface, form copolymer emulsion, finally spray-dried prepare polyvinyl acetate
Ester/methyl methacrylate/butyl acrylate copolymer.This copolymer can be widely applied to the processing life of rigid PVC products
Produce, the such as industry such as section bar, profile shapes, sheet material, tubing, foamed board, building template, wood moulding, successfully substitute tradition and property at present
The single modifier of energy.
Compared with prior art, the present invention has advantages below：
(1) high income, reaches more than 98%, good emulsion stability；
(2) on the premise of ensureing degree of plasticification, greatly improve melt strength and counter balance torque, be suitable for the difference range of work；
(3) resistance to water, alkali resistance and the heat resistance of copolymer are improved；
(4) present invention also provides its preparation method, rational technology, and step is simple.
Specific embodiment
With reference to embodiment, the present invention will be further described.
Embodiment 1
(1) by 225kg vinyl acetate monomer, 3750kg deionized water, 0.15kg polyvinyl alcohol 1788,0.11kg 12
Alkyl sodium sulfate, 7.5kg sodium carbonate medium add reaction unit, logical nitrogen deoxygenation, stir under the mixing speed of 50r/min
30min, is warming up to 45 DEG C, adds potassium peroxydisulfate 0.03kg, controls temperature to be 55 DEG C of reaction 1h, using semi-continuous emulsion polymerizing side
Remaining 1225kg vinyl acetate monomer, 0.64kg sodium lauryl sulphate, 0.12kg potassium peroxydisulfate are divided equally 3 initiations and are gathered by method
Close, 55 DEG C of reaction 2h prepare stratum nucleare emulsion；
(2) 7.5kg sodium lauryl sulphate, 1200kg methyl methacrylate, 75kg butyl acrylate are sequentially added
In the stratum nucleare emulsion obtaining to step (1), nitrogen deoxygenation, stir 30min under the mixing speed of 50r/min, be warming up to 40 DEG C,
Add potassium peroxydisulfate 0.15kg, controlling reaction temperature reacts 2h at 50 DEG C；
(3) it is warming up to 78 DEG C of ripenings, is cooled to 38 DEG C of dischargings, be spray-dried, obtain product, yield is 99.3%.
Poly- (vinyl acetate-acrylic butyl ester-methyl methacrylate) terpolymer nucleocapsid ratio of this technique synthesis
For 4:1st, shell methyl methacrylate/butyl acrylate is than for 16:1, solid content=monomer/(monomer+water)=42.2%.
Embodiment 2
(1) by 300kg vinyl acetate monomer, 4125kg deionized water, 0.75kg polyvinyl alcohol 1799,3kg dodecane
Base benzene sulfonic acid sodium salt, 18kg potassium hydroxide medium add reaction unit, logical nitrogen deoxygenation, stir under the mixing speed of 150r/min
30min, is warming up to 50 DEG C, adds Ammonium persulfate. 0.09kg, 58 DEG C of reaction 1h, using semi-continuous emulsion polymerizing method by residue
1200kg vinyl acetate monomer, 12kg dodecylbenzene sodium sulfonate, 0.36kg Ammonium persulfate. are divided equally 3 initiations and are polymerized, 58 DEG C
Reaction 2h prepares stratum nucleare emulsion；
(2) 30kg dodecylbenzene sodium sulfonate, 1350kg methyl methacrylate, 150kg butyl acrylate are added successively
Enter in the stratum nucleare emulsion obtaining to step (1), nitrogen deoxygenation, stirs 30min under the mixing speed of 150r/min, is warming up to 50
DEG C, add potassium peroxydisulfate 0.45kg, controlling reaction temperature reacts 3h at 55 DEG C；
(3) it is warming up to 80 DEG C of ripenings, is cooled to 40 DEG C of dischargings, be spray-dried, obtain product, yield is 99.1%.
Poly- (vinyl acetate-acrylic butyl ester-methyl methacrylate) terpolymer nucleocapsid ratio of this technique synthesis
For 3.7:1st, shell methyl methacrylate/butyl acrylate is than for 9:1, solid content=monomer/(monomer+water)=42.3%.
Embodiment 3
(1) by 375kg vinyl acetate monomer, 4500kg deionized water, 1.5kg polyvinyl alcohol 1788,7.5kg OP-
10th, 30kg sodium phosphate medium adds reaction unit, logical nitrogen deoxygenation, stirs 30min under the mixing speed of 300r/min, heats up
To 55 DEG C, add potassium peroxydisulfate 0.19kg, 60 DEG C of reaction 1h, using semi-continuous emulsion polymerizing method by remaining 1125kg acetic acid second
Allyl ester monomer, 22.5kg sodium lauryl sulphate, 0.56kg sodium bicarbonate divide equally 3 initiation polymerizations, and 60 DEG C of reaction 2h prepare
Stratum nucleare emulsion；
(2) 45kg sodium lauryl sulphate, 1425kg methyl methacrylate, 300kg butyl acrylate are sequentially added
In the stratum nucleare emulsion obtaining to step (1), nitrogen deoxygenation, stirs 30min under the mixing speed of 300r/min, is warming up to 45
DEG C, add potassium peroxydisulfate 0.75kg, controlling reaction temperature reacts 2.5h at 52 DEG C；
(3) it is warming up to 81 DEG C of ripenings, is cooled to 42 DEG C of dischargings, be spray-dried, obtain product, yield is 98.9%.
Poly- (vinyl acetate-acrylic butyl ester-methyl methacrylate) terpolymer nucleocapsid ratio of this technique synthesis
For 3.4:1st, shell methyl methacrylate/butyl acrylate is than for 4.75:1, solid content=monomer/(monomer+water)=
42.1%.
Embodiment 4
(1) by 1500kg vinyl acetate monomer, 4500kg deionized water, 1.5kg polyvinyl alcohol 1788,30kgOP-10,
30kg sodium phosphate medium adds reaction unit, logical nitrogen deoxygenation, stirs 30min, be warming up under the mixing speed of 300r/min
50 DEG C, add potassium peroxydisulfate 0.75kg, 55 DEG C of reaction 1h；
(2) 45kg sodium lauryl sulphate, 1425kg methyl methacrylate, 300kg butyl acrylate are sequentially added
In the stratum nucleare emulsion obtaining to step (1), nitrogen deoxygenation, stirs 30min under the mixing speed of 300r/min, is warming up to 45
DEG C, add potassium peroxydisulfate 0.75kg, controlling reaction temperature reacts 2.5h at 55 DEG C；
(3) it is warming up to 80 DEG C of ripenings, is cooled to 40 DEG C of dischargings, be spray-dried, obtain product, yield is 98.0%.
Poly- (vinyl acetate-acrylic butyl ester-methyl methacrylate) terpolymer nucleocapsid ratio of this technique synthesis
For 3.4:1st, shell methyl methacrylate/butyl acrylate is than for 4.75:1, solid content=monomer/(monomer+water)=
42.1%..
Contrast test：
Sub- by 1.5 parts of the mass fraction product that Example 1-4 prepares respectively, 100 parts of PVC (SG-6), dibasic
2.5 parts of lead phosphate, 2.5 parts of tribasic lead sulfate, 0.5 part of calcium stearate, 0.15 part of stearic acid, 0.35 part of OPE,
10 parts of titanium dioxide, 20 parts of Calcium Carbonate and 2.6 parts of lead stearate, are mixed to get resin, and Tables 1 and 2 is shown in properties test.
Comparative example 1
(Shandong Shituo High Molecular Weight Material Co., Ltd. produces to take pure acrylic acid esters modifier by mass fraction
PA-20) 1.5 parts, 100 parts of PVC (SG-6), 2.5 parts of dibasic lead phosphite, 2.5 parts of tribasic lead sulfate, calcium stearate
0.5 part, 0.15 part of stearic acid, 0.35 part of OPE, 10 parts of titanium dioxide, 20 parts of Calcium Carbonate and 2.6 parts of lead stearate, mix
Conjunction obtains resin, and Tables 1 and 2 is shown in properties test.
Comparative example 2
(Shandong Shituo High Molecular Weight Material Co., Ltd. produces to take phenylethylene modifier by mass fraction
YM-02) 1.5 parts, 100 parts of PVC (SG-6), 2.5 parts of dibasic lead phosphite, 2.5 parts of tribasic lead sulfate, calcium stearate 0.5
Part, 0.15 part of stearic acid, 0.35 part of OPE, 10 parts of titanium dioxide, 20 parts of Calcium Carbonate and 2.6 parts of lead stearate, mixing
Obtain resin, Tables 1 and 2 is shown in properties test.
Table 1 is that the rheological property to resin is compared.
The rheological property of table 1 resin
| Numbering | Fusion time (S) | Counter balance torque (Nm) | Highest moment of torsion (Nm) | Degree of plasticification |
| Embodiment 1 | 65 | 24 | 29 | Excellent |
| Embodiment 2 | 60 | 24 | 29 | Excellent |
| Embodiment 3 | 63 | 24 | 28 | Excellent |
| Embodiment 4 | 60 | 23 | 28 | Excellent |
| Comparative example 1 | 145 | 22 | 28 | Well |
| Comparative example 2 | 150 | 20 | 27 | Poor |
Table 2 is that the metal-stripping performance to resin is compared.Test condition is mill formula double roller Plasticator, front roller temperature
Spend for 185 DEG C, rear roll temperature is 180 DEG C.
The metal-stripping performance of table 2 resin
| 0min | 5min | 10min | 15min | 20min | 30min | |
| Embodiment 1 | ☆ | ☆ | ☆☆ | |||
| Embodiment 2 | ☆☆ | ☆☆☆ | ||||
| Embodiment 3 | ☆ | ☆ | ☆☆ | |||
| Embodiment 4 | ☆ | ☆☆ | ||||
| Comparative example 1 | ☆ | ☆☆ | ☆☆☆ | |||
| Comparative example 2 | ☆ | ☆☆ | ☆☆☆ |
Wherein, the metal-strippings that represent better more, and ☆, and to represent metal-stripping poorer.
Claims (8)
1. a kind of preparation method of RPVC terpolymer it is characterised in that：It is 3 by mass ratio:1-4:1 core
Layer and shell are made using graft emulsion polymerization technique,
Wherein：Stratum nucleare is made up of the raw material of following mass fraction：100 parts of vinyl acetate monomer, water 250-300 part, dispersant
0.01-0.1 part, emulsifying agent 0.05-2.0 part, alkaline medium 0.5-2.0 part and initiator 0.01-0.05 part；
Shell is made up of the raw material of following mass fraction：Methyl methacrylate 80-95 part, butyl acrylate 5-20 part, emulsifying
Agent 0.5-3.0 part and initiator 0.01-0.05 part；
Comprise the following steps：
（1）First, part vinyl acetate monomer, water, dispersant, alkaline medium and partial emulsifier are added reaction unit,
Nitrogen deoxygenation, stirs 30min under the mixing speed of 50-300r/min, is warming up to 45 DEG C -55 DEG C, and controlling reaction temperature is 55-
60 DEG C, using semi-continuous emulsion polymerizing method, remaining vinyl acetate monomer, emulsifying agent and initiator are divided 3-5 time to cause and gather
Close, obtain stratum nucleare emulsion；
（2）Emulsifying agent, methyl methacrylate and butyl acrylate are added sequentially to step（1）In the stratum nucleare emulsion obtaining,
Nitrogen deoxygenation, stirs under the mixing speed of 50-300r/min, is warming up to 40 DEG C -50 DEG C, adds initiator, controls reaction temperature
Degree, at 50-55 DEG C, reacts 2-3h；
（3）Intensification ripening, cooling discharge, it is spray-dried, obtain product.
2. RPVC terpolymer according to claim 1 preparation method it is characterised in that：Dispersant
For one of polyvinyl alcohol 1788 or polyvinyl alcohol 1799 or two kinds with arbitrary proportion mixing.
3. RPVC terpolymer according to claim 1 preparation method it is characterised in that：Emulsifying agent
Mixed with arbitrary proportion for one or more of sodium lauryl sulphate, dodecylbenzene sodium sulfonate, OP-10 or tween 80.
4. RPVC terpolymer according to claim 1 preparation method it is characterised in that：Initiator
Mixed with arbitrary proportion for one or more of potassium peroxydisulfate or Ammonium persulfate..
5. RPVC terpolymer according to claim 1 preparation method it is characterised in that：Alkalescence is situated between
Matter is one of potassium hydroxide, sodium hydroxide, sodium carbonate, potassium phosphate or sodium phosphate or two kinds with arbitrary proportion mixing.
6. RPVC terpolymer according to claim 1 preparation method it is characterised in that：Stratum nucleare is
Polyvinyl acetate, shell is poly-（Butyl acrylate-methyl ester）Copolymer.
7. RPVC terpolymer according to claim 1 preparation method it is characterised in that：Step
（1）The quality that middle vinyl acetate monomer adds first is the 15-25% of its gross mass, and the quality that emulsifying agent adds first is it
The 15-25% of gross mass.
8. RPVC terpolymer according to claim 1 preparation method it is characterised in that：Step
（3）Middle slaking reaction temperature is 78-81 DEG C, and drop temperature is 38-42 DEG C.
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