CN104356272B - The micro-suspension polymerization of styrene-N-phenylmaleimide-acrylonitrile - Google Patents
The micro-suspension polymerization of styrene-N-phenylmaleimide-acrylonitrile Download PDFInfo
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- CN104356272B CN104356272B CN201410584385.0A CN201410584385A CN104356272B CN 104356272 B CN104356272 B CN 104356272B CN 201410584385 A CN201410584385 A CN 201410584385A CN 104356272 B CN104356272 B CN 104356272B
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- phenylmaleimide
- polymerization
- styrene
- acrylonitrile
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- LVUDMQWOFGGAFN-UHFFFAOYSA-N 1-phenylpyrrole-2,5-dione;prop-2-enenitrile;styrene Chemical compound C=CC#N.C=CC1=CC=CC=C1.O=C1C=CC(=O)N1C1=CC=CC=C1 LVUDMQWOFGGAFN-UHFFFAOYSA-N 0.000 title claims description 22
- 238000010557 suspension polymerization reaction Methods 0.000 title claims description 8
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 69
- PPBRXRYQALVLMV-UHFFFAOYSA-N styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 50
- 229920001897 terpolymer Polymers 0.000 claims abstract description 43
- HIDBROSJWZYGSZ-UHFFFAOYSA-N 1-phenylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC=C1 HIDBROSJWZYGSZ-UHFFFAOYSA-N 0.000 claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- NLHHRLWOUZZQLW-UHFFFAOYSA-N acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000008346 aqueous phase Substances 0.000 claims abstract description 24
- 239000000178 monomer Substances 0.000 claims abstract description 22
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 18
- 230000035484 reaction time Effects 0.000 claims abstract description 18
- 239000003999 initiator Substances 0.000 claims abstract description 15
- 238000003756 stirring Methods 0.000 claims abstract description 15
- 238000010792 warming Methods 0.000 claims abstract description 10
- 239000002519 antifouling agent Substances 0.000 claims abstract description 8
- 150000001875 compounds Chemical class 0.000 claims abstract description 7
- 239000003002 pH adjusting agent Substances 0.000 claims abstract description 7
- 239000008367 deionised water Substances 0.000 claims abstract description 4
- 235000012970 cakes Nutrition 0.000 claims abstract description 3
- 238000001914 filtration Methods 0.000 claims abstract description 3
- IISBACLAFKSPIT-UHFFFAOYSA-N Bisphenol A Chemical group C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 15
- LQZZUXJYWNFBMV-UHFFFAOYSA-N Dodecanol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 claims description 15
- 229940106691 bisphenol A Drugs 0.000 claims description 15
- HFQQZARZPUDIFP-UHFFFAOYSA-M sodium;2-dodecylbenzenesulfonate Chemical compound [Na+].CCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O HFQQZARZPUDIFP-UHFFFAOYSA-M 0.000 claims description 15
- PJKVFARRVXDXAD-UHFFFAOYSA-N 2-naphthaldehyde Chemical compound C1=CC=CC2=CC(C=O)=CC=C21 PJKVFARRVXDXAD-UHFFFAOYSA-N 0.000 claims description 14
- UIIMBOGNXHQVGW-UHFFFAOYSA-M NaHCO3 Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 14
- WJBBNWUFOLRXAL-UHFFFAOYSA-N (4-propan-2-ylphenyl) 2,2,5,5-tetramethylhexaneperoxoate Chemical compound CC(C)C1=CC=C(OOC(=O)C(C)(C)CCC(C)(C)C)C=C1 WJBBNWUFOLRXAL-UHFFFAOYSA-N 0.000 claims description 13
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 239000000725 suspension Substances 0.000 claims description 10
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 7
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 7
- BVKZGUZCCUSVTD-UHFFFAOYSA-N Carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 6
- -1 peroxy dicarbonate- 2-Octyl Nitrite Chemical compound 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 5
- OMPJBNCRMGITSC-UHFFFAOYSA-N Incidol Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Natural products OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 239000001099 ammonium carbonate Substances 0.000 claims description 4
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 4
- UFWIBTONFRDIAS-UHFFFAOYSA-N naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 4
- 150000002989 phenols Chemical class 0.000 claims description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 150000004782 1-naphthols Chemical class 0.000 claims description 2
- 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 claims description 2
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 2
- PRKQVKDSMLBJBJ-UHFFFAOYSA-N Ammonium carbonate Chemical compound N.N.OC(O)=O PRKQVKDSMLBJBJ-UHFFFAOYSA-N 0.000 claims description 2
- 210000000481 Breast Anatomy 0.000 claims description 2
- 229940031574 HYDROXYMETHYL CELLULOSE Drugs 0.000 claims description 2
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 claims description 2
- RCEAADKTGXTDOA-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCCCCCC[Na] Chemical compound OS(O)(=O)=O.CCCCCCCCCCCC[Na] RCEAADKTGXTDOA-UHFFFAOYSA-N 0.000 claims description 2
- XAPRFLSJBSXESP-UHFFFAOYSA-N Oxycinchophen Chemical compound N=1C2=CC=CC=C2C(C(=O)O)=C(O)C=1C1=CC=CC=C1 XAPRFLSJBSXESP-UHFFFAOYSA-N 0.000 claims description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M Potassium bicarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 2
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 2
- 239000004141 Sodium laurylsulphate Substances 0.000 claims description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N Stearyl alcohol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 2
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 2
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N azanium;hydron;carbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 2
- FYLJKQFMQFOLSZ-UHFFFAOYSA-N cyclohexylperoxycyclohexane Chemical group C1CCCCC1OOC1CCCCC1 FYLJKQFMQFOLSZ-UHFFFAOYSA-N 0.000 claims description 2
- 229920003063 hydroxymethyl cellulose Polymers 0.000 claims description 2
- 239000001863 hydroxypropyl cellulose Substances 0.000 claims description 2
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 claims description 2
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- NCIAGQNZQHYKGR-UHFFFAOYSA-N naphthalene-1,2,3-triol Chemical class C1=CC=C2C(O)=C(O)C(O)=CC2=C1 NCIAGQNZQHYKGR-UHFFFAOYSA-N 0.000 claims description 2
- 239000011736 potassium bicarbonate Substances 0.000 claims description 2
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 2
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 2
- 229940094025 potassium bicarbonate Drugs 0.000 claims description 2
- 239000001184 potassium carbonate Substances 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 239000001187 sodium carbonate Substances 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 235000019333 sodium laurylsulphate Nutrition 0.000 claims description 2
- 229940068984 Polyvinyl Alcohol Drugs 0.000 claims 1
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 claims 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims 1
- 239000011575 calcium Substances 0.000 claims 1
- 229910052791 calcium Inorganic materials 0.000 claims 1
- 235000001465 calcium Nutrition 0.000 claims 1
- 229940071676 hydroxypropylcellulose Drugs 0.000 claims 1
- 150000002500 ions Chemical class 0.000 claims 1
- 235000015320 potassium carbonate Nutrition 0.000 claims 1
- 235000017550 sodium carbonate Nutrition 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 32
- 239000004793 Polystyrene Substances 0.000 abstract 2
- 229920002223 polystyrene Polymers 0.000 abstract 2
- 239000002245 particle Substances 0.000 description 23
- 238000004017 vitrification Methods 0.000 description 21
- 239000007787 solid Substances 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 17
- 239000012065 filter cake Substances 0.000 description 13
- 229920001577 copolymer Polymers 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- 125000004435 hydrogen atoms Chemical class [H]* 0.000 description 7
- KEAYESYHFKHZAL-UHFFFAOYSA-N sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 7
- 239000011734 sodium Substances 0.000 description 7
- 229910052708 sodium Inorganic materials 0.000 description 7
- 206010013786 Dry skin Diseases 0.000 description 5
- 230000001804 emulsifying Effects 0.000 description 5
- 239000000839 emulsion Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 230000005070 ripening Effects 0.000 description 5
- 238000002156 mixing Methods 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 230000000630 rising Effects 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N iso-propanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- OTEKOJQFKOIXMU-UHFFFAOYSA-N 1,4-bis(trichloromethyl)benzene Chemical compound ClC(Cl)(Cl)C1=CC=C(C(Cl)(Cl)Cl)C=C1 OTEKOJQFKOIXMU-UHFFFAOYSA-N 0.000 description 1
- DGVVWUTYPXICAM-UHFFFAOYSA-N 2-mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 1
- 229960003563 Calcium Carbonate Drugs 0.000 description 1
- 229920001451 Polypropylene glycol Polymers 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H Tricalcium phosphate Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 229940059913 ammonium carbonate Drugs 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 235000010216 calcium carbonate Nutrition 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- XYXGFHALMTXBQX-UHFFFAOYSA-L carboxylatooxy carbonate Chemical compound [O-]C(=O)OOC([O-])=O XYXGFHALMTXBQX-UHFFFAOYSA-L 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 230000000977 initiatory Effects 0.000 description 1
- 239000004530 micro-emulsion Substances 0.000 description 1
- 239000004531 microgranule Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N oxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- JHLVQVPUILZTNX-UHFFFAOYSA-N prop-2-enenitrile;pyrrole-2,5-dione Chemical compound C=CC#N.O=C1NC(=O)C=C1 JHLVQVPUILZTNX-UHFFFAOYSA-N 0.000 description 1
- 230000001681 protective Effects 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- SONHXMAHPHADTF-UHFFFAOYSA-M sodium;2-methylprop-2-enoate Chemical compound [Na+].CC(=C)C([O-])=O SONHXMAHPHADTF-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229920000638 styrene acrylonitrile Polymers 0.000 description 1
- 239000000375 suspending agent Substances 0.000 description 1
- 230000002194 synthesizing Effects 0.000 description 1
Abstract
The invention discloses a kind of aqueous phase microsuspension polymerization method of polystyrene N phenyl maleimide acrylonitrile terpolymer, comprise the following steps: 1) polymerization: in polymeric kettle, put into the monomer being made up of styrene, acrylonitrile and N phenyl maleimide, and put into deionized water, compound emulsifying agent, initiator, anti-fouling agent and pH adjusting agent, stirring, is warming up to 40～85 DEG C and is polymerized；Polymerization reaction time is 2～7 hours；2) centrifugal, be dried: after polymerization reaction time arrives, add account for the 0.1 of total weight of monomer～the terminator of 1 ‰ thus terminate polyreaction, filter, after gained filtration cakes torrefaction polystyrene N phenyl maleimide acrylonitrile terpolymer.The method of the present invention has the advantage that monomer conversion is high.
Description
Technical field
The present invention relates to a kind of polymerization of styrene-N-phenylmaleimide-acrylonitrile terpolymer, i.e. benzene
The aqueous phase microsuspension polymerization method of ethylene-N-phenylmaleimide-acrylonitrile terpolymer.
Background technology
N-phenylmaleimide (be called for short PMI) is a kind of rigid heat resistant monomer, its copolymer be widely used in ABS,
The resins such as PVC, SAN, PMMA heat resistance modified, wherein styrene-N-phenylmaleimide-acrylonitrile terpolymer is one
Plant excellent ABS heat-proof modifier.Existing preparation method is specific as follows:
1), patent CN200710069041.6 reports one-step method suspension polymerisation and generates styrene-N-benzyl maleimide
Amine-acrylonitrile terpolymer.Once put into suspending agent, chain-transferring agent, styrene, acrylonitrile, N-phenylmaleimide, draw
Sending out agent, heat up polymerization, and recurring obtains terpolymer, and technical process is simple, it is easy to industrialization, white granular solids
(particle mean size 150～500 μm), causes certain difficulty to application processing, the vitrification point of copolymer and Vicat softening point
It need to improve.
2), document " N-phenylmaleimide/styrene/acrylonitrile emulsion copolymers is blended with PVC " proposes emulsion
The method of copolymerization, need to be through the techniques such as emulsifying, polymerization, breakdown of emulsion, complex technical process, it is difficult to realize industrialization:
Suspending drops is carried out radical polymerization under dispersant, mechanical agitation in water by the monomer dissolved with initiator
Method be suspension polymerisation, product has dispersant residual, thus affects the performance of its polymer；With water as solvent, at breast
Under the effect of agent and by means of mechanical agitation, make monomer be dispersed into emulsion in water, initiator cause and carry out poly-
It is collectively referred to as emulsion to be polymerized, but this complex process, it is difficult to industrialization；Microsuspension polymerization uses special composite emulsifying system to need emulsifying
Agent-indissoluble auxiliary agent microemulsion, this composite emulsifying system is strong to polymer monomer microgranule protective capability, with oil-soluble initiator initiation
Polymerization, the granularity a kind of polymerization methods between emulsion polymerization and suspension polymerisation, the work of the existing suspension polymerisation of microsuspension polymerization
Skill process is simple, be prone to industrialized advantage, the fine size of emulsion polymerization that simultaneously possesses again, the polymerized segment advantage such as uniformly,
The performance of polymer can be significantly improved, be to improve performance of copolymer in recent years and one of main polymerisation means of rising.
Summary of the invention
The technical problem to be solved is to provide the polystyrene-N-phenyl maleoyl that a kind of monomer conversion is high
The aqueous phase microsuspension polymerization method of imines-acrylonitrile terpolymer.
In order to solve above-mentioned technical problem, the present invention provides a kind of polystyrene-N-phenylmaleimide-acrylonitrile three
The aqueous phase microsuspension polymerization method of membered copolymer；Comprise the following steps:
1) polymerization:
In polymeric kettle, put into the monomer being made up of styrene, acrylonitrile and N-phenylmaleimide, and put into nothing
Ionized water (deionized water), compound emulsifying agent, initiator, anti-fouling agent and pH adjusting agent, stirring, it is warming up to 40～85 DEG C (relatively
Good is 60～65 DEG C) it is polymerized；Polymerization reaction time is 2～7 hours (preferably 6～7 hours)；
In monomer, styrene, acrylonitrile, N-phenylmaleimide weight content be respectively 24～57%, 23～25%,
18～51%；
Compound emulsifying agent is 1～12% (preferably 2.5～3%, more preferably 2.75%) of total monomer weight, and initiator is
The 0.6 of total monomer weight～2.4 ‰ (preferably 1.2～1.3 ‰, more preferably 1.25 ‰), anti-fouling agent is total monomer weight
0.1～1 ‰, pH adjusting agent is 0.1～10 ‰ (preferably 2～3 ‰, more preferably 2.5 ‰) of total monomer weight；
2) centrifugal, dry:
After polymerization reaction time arrives, add account for total weight of monomer 0.1～1 ‰ (preferably 0.12～0.13 ‰, be more preferably
0.125 ‰) terminator thus terminate polyreaction, filter, after gained filtration cakes torrefaction (forced air drying) polystyrene-N-benzene
Base maleimide-acrylonitrile terpolymer.
Aqueous phase microsuspension polymerization as the styrene-N-phenylmaleimide-acrylonitrile terpolymer of the present invention
The improvement of method: deionized water is 1～5 times (preferably 1.5～2 times) of total monomer weight.
Aqueous phase microsuspension polymerization as the styrene-N-phenylmaleimide-acrylonitrile terpolymer of the present invention
Further improvements in methods: described compound emulsifying agent is made up of emulsifying agent A and emulsifying agent B；Described emulsifying agent A's and emulsifying agent B
Weight ratio is: 10:1～1:1；
Emulsifying agent A is at least one in sodium lauryl sulphate, dodecylbenzene sodium sulfonate, dodecyl sodium sulfate；
Emulsifying agent B be OPEO, lauryl alcohol, tetradecyl alchohol, octadecanol, polyvinyl alcohol, hydroxymethyl cellulose,
At least one in hydroxypropyl cellulose.
Aqueous phase microsuspension polymerization as the styrene-N-phenylmaleimide-acrylonitrile terpolymer of the present invention
Further improvements in methods: described initiator is oil-soluble initiator；
Described oil-soluble initiator is azodiisobutyronitrile, 2,2'-Azobis(2,4-dimethylvaleronitrile), dibenzoyl peroxide, peroxidating two carbon
Acid-2-Octyl Nitrite, di-cyclohexylperoxy di-carbonate, peroxy dicarbonate hexichol oxygen ethyl ester, peroxidating double (3,5,5-tri-
Methyl vinyl), at least one in cumyl peroxyneodecanoate.
Aqueous phase microsuspension polymerization as the styrene-N-phenylmaleimide-acrylonitrile terpolymer of the present invention
Further improvements in methods: described anti-fouling agent is polyhydric phenols；
Described polyhydric phenols be 1-naphthols, beta naphthal, 1,3-dihydroxy naphthlene, Isosorbide-5-Nitrae-dihydroxy naphthlene, 1,2,3-trihydroxynaphthalenes, 1,
At least one in 4,5,8-tetrahydroxy naphthalene, Neville acid.
Aqueous phase microsuspension polymerization as the styrene-N-phenylmaleimide-acrylonitrile terpolymer of the present invention
Further improvements in methods: described terminator is bisphenol-A and/or acetone semicarbazone thiourea.
Aqueous phase microsuspension polymerization as the styrene-N-phenylmaleimide-acrylonitrile terpolymer of the present invention
Further improvements in methods: described pH adjusting agent be sodium hydroxide, potassium hydroxide, ammonia, sodium carbonate, sodium bicarbonate, potassium carbonate,
At least one in potassium bicarbonate, calcium carbonate, ammonium carbonate, ammonium hydrogen carbonate.
Aqueous phase microsuspension polymerization as the styrene-N-phenylmaleimide-acrylonitrile terpolymer of the present invention
Further improvements in methods: step 1) stirring be 25～35 DEG C stir 20～40 minutes.
The aqueous phase microsuspension polymerization side of the polystyrene-N-phenylmaleimide-acrylonitrile terpolymer of the present invention
Method, use composite emulsifying system, oil-soluble initiator cause polymerization, reaction terminates, add terminator, more by centrifugation, air blast do
Dry obtain styrene-N-phenylmaleimide-acrylonitrile terpolymer.
The present invention with micro suspension aqueous polymerization process synthesizing styrene-N-phenylmaleimide-acrylonitrile terpolymer,
In the present invention, anti-fouling agent can play antiseized still and can regulate again the effect of polymerization.
The method using the present invention prepares styrene-N-phenylmaleimide-acrylonitrile terpolymer, has as follows
Technical advantage:
1, yield is high, can reach 99.5%；
2, gained copolymer pellet is thinner, in powder, particle mean size up to 100 μm below, it is easy to later stage application processing；
3, on the premise of the N-phenylmaleimide containing equal proportion, the polymerization of the present invention is used to make copolymer have
There are higher vitrification point and Vicat softening point, so that polymer has more preferable application performance.
Detailed description of the invention
Embodiment 1, a kind of aqueous phase microsuspension polymerization method containing 18%PMI terpolymer, follow the steps below successively:
1) polymerization
Be sequentially added in 2000ml there-necked flask styrene 228g, acrylonitrile 100g, N-phenylmaleimide 72g,
Water 800g, dodecylbenzene sodium sulfonate 10g, lauryl alcohol 1g, cumyl peroxyneodecanoate 0.5g, beta naphthal 0.4g, carbonic acid
Hydrogen sodium 1g, 30 DEG C are stirred 30 minutes, and heat up 60～65 DEG C of reaction 6h；
2) centrifugal, dry
After polymerization reaction time arrives, add 0.05g bisphenol-A thus terminate polyreaction, filter, 100 DEG C of drums of gained filter cake
Air-dry dry 1 hour, obtain white powdery solids (polystyrene-N-phenylmaleimide-acrylonitrile terpolymer) 390g,
Yield 97.5%.
3) test result
Vitrification point: 135.7～138.7 DEG C；Vicat softening point: 120.3～124.2 DEG C；Particle mean size: 75 μm.
Embodiment 2, a kind of aqueous phase microsuspension polymerization method containing 25%PMI terpolymer, follow the steps below successively:
1) polymerization
Be sequentially added in 2000ml there-necked flask styrene 208g, acrylonitrile 92g, N-phenylmaleimide 100g,
Water 800g, dodecylbenzene sodium sulfonate 10g, lauryl alcohol 1g, cumyl peroxyneodecanoate 0.5g, beta naphthal 0.4g, carbonic acid
Hydrogen sodium 1g, 30 DEG C are stirred 30 minutes, and heat up 60～65 DEG C of reaction 6h；
2) centrifugal, dry
After polymerization reaction time arrives, add 0.05g bisphenol-A thus terminate polyreaction, filter, 100 DEG C of drums of gained filter cake
Air-dry dry 1 hour, obtain white powdery solids (polystyrene-N-phenylmaleimide-acrylonitrile terpolymer) 394g,
Yield 98.5%.
3) test result
Vitrification point: 145.3～150.4 DEG C；Vicat softening point: 130.3～138.0 DEG C；Particle mean size: 81 μm.
Embodiment 3, a kind of aqueous phase microsuspension polymerization method containing 34%PMI terpolymer, follow the steps below successively:
1) polymerization:
Be sequentially added in 2000ml there-necked flask styrene 168g, acrylonitrile 96g, N-phenylmaleimide 136g,
Water 800g, dodecylbenzene sodium sulfonate 10g, lauryl alcohol 1g, cumyl peroxyneodecanoate 0.5g, beta naphthal 0.4g, carbonic acid
Hydrogen sodium 1g, 30 DEG C are stirred 30 minutes, and heat up 60～65 DEG C of reaction 6h；
2) centrifugal, dry:
After polymerization reaction time arrives, add 0.05g bisphenol-A thus terminate polyreaction, filter, 100 DEG C of drums of gained filter cake
Air-dry dry 1 hour, obtain white powdery solids (polystyrene-N-phenylmaleimide-acrylonitrile terpolymer) 396g,
Yield 99%.
3) test result
Vitrification point: 150.2～154.7 DEG C；Vicat softening point: 155.1～160.8 DEG C；Particle mean size: 85 μm.
Embodiment 4, a kind of aqueous phase microsuspension polymerization method containing 40%PMI terpolymer, follow the steps below successively:
1) polymerization
Be sequentially added in 2000ml there-necked flask styrene 150g, acrylonitrile 90g, N-phenylmaleimide 160g,
Water 800g, dodecylbenzene sodium sulfonate 10g, lauryl alcohol 1g, cumyl peroxyneodecanoate 0.5g, beta naphthal 0.4g, carbonic acid
Hydrogen sodium 1g, 30 DEG C are stirred 30 minutes, and heat up 60～65 DEG C of reaction 6h；
2) centrifugal, dry
After polymerization reaction time arrives, add 0.05g bisphenol-A thus terminate polyreaction, filter, 100 DEG C of drums of gained filter cake
Air-dry dry 1 hour, obtain white powdery solids (polystyrene-N-phenylmaleimide-acrylonitrile terpolymer) 398g,
Yield 99.5%.
3) test result
Vitrification point: 168.2～172.2 DEG C；Vicat softening point: 171.5～176.4 DEG C；Particle mean size: 88 μm.
Embodiment 5, a kind of aqueous phase microsuspension polymerization method containing 51%PMI terpolymer, follow the steps below successively:
1) polymerization
Be sequentially added in 2000ml there-necked flask styrene 96g, acrylonitrile 100g, N-phenylmaleimide 204g,
Water 800g, dodecylbenzene sodium sulfonate 10g, lauryl alcohol 1g, cumyl peroxyneodecanoate 0.5g, beta naphthal 0.4g, carbonic acid
Hydrogen sodium 1g, 30 DEG C are stirred 30 minutes, and heat up 60～65 DEG C of reaction 6h；
2) centrifugal, dry
After polymerization reaction time arrives, add 0.05g bisphenol-A thus terminate polyreaction, filter, 100 DEG C of drums of gained filter cake
Air-dry dry 1 hour, obtain white powdery solids (polystyrene-N-phenylmaleimide-acrylonitrile terpolymer) 395g,
Yield 98.75%.
3) test result
Vitrification point: 197.6～205.7 DEG C；Vicat softening point: 205.8～208.9 DEG C；Particle mean size: 92 μm.
Comparative example 1, suspension polymerization containing 18%PMI terpolymer, follow the steps below successively:
1) reaction
Styrene 228g, acrylonitrile 100g, the mixing of N-phenylmaleimide 72g, 6ml chain-transferring agent mercaptoethanol are added
Enter in 800g water, add 20g calcium phosphate, stir 30 minutes, be subsequently adding 0.8g azodiisobutyronitrile, be warming up to 90 DEG C instead
5h, reaction is answered to terminate, temperature rising reflux ripening 2 hours, filter, 100 DEG C of forced air dryings 1 hour, obtain white granular solid 320g,
Yield 80%.
2) test result
Vitrification point 131.5～134.6 DEG C；Vicat softening point: 117.2～123.2 DEG C；Particle mean size: 230 μm.
Comparative example 2, suspension polymerization containing 25%PMI terpolymer, follow the steps below successively:
1) reaction
By styrene 208g, acrylonitrile 92g, N-phenylmaleimide 100g, 9ml chain-transferring agent n-dodecyl mercaptan
Ester is mixed to join in 800g water, adds 25g POLYPROPYLENE GLYCOL, stirs 30 minutes, adds 1.2g dibenzoyl peroxide, rises
Temperature is to 40 DEG C of reaction 6h, and reaction terminates, temperature rising reflux ripening 2 hours, filters, and 100 DEG C of forced air dryings 1 hour obtain white particle
Shape solid 325g, yield 81.25%.
2) test result
Vitrification point 140.2～145.3 DEG C；Vicat softening point: 124.3～135.6 DEG C；Particle mean size: 250 μm.
Comparative example 3, suspension polymerization containing 34%PMI terpolymer, follow the steps below successively:
1) reaction
By styrene 168g, acrylonitrile 96g, the mixing of N-phenylmaleimide 136g, 3ml chain-transferring agent DDM dodecyl mercaptan
Join in 800g water, add 9g polyvinyl alcohol, stir 30 minutes, be subsequently adding 0.7g dibenzoyl peroxide, be warming up to
60 DEG C of reaction 7h, reaction terminates, and is warming up to the ripening 2h that seethes with excitement, and filters, and 100 DEG C of forced air dryings 1 hour obtain white granular solid
330g, yield 82.5%.
2) test result
Vitrification point 146.2～150.6 DEG C；Vicat softening point: 150.0～156.5 DEG C；Particle mean size: 245 μm.
Comparative example 4, suspension polymerization containing 40%PMI terpolymer, follow the steps below successively:
1) reaction
Styrene 150g, acrylonitrile 90g, the mixing of N-phenylmaleimide 160g, 3ml chain-transferring agent isopropanol are added
In 800g water, add 8g sodium polymethacrylate, stir 30 minutes, be subsequently adding 0.7g peroxy dicarbonate hexichol oxygen second
Base ester, is warming up to 85 DEG C of reaction 2h, and reaction terminates, and is warming up to the ripening 2h that seethes with excitement, and filters, and 100 DEG C of forced air dryings 1 hour obtain white
Coloured particles shape solid 334g, yield 83.5%.
2) test result
Vitrification point 163.1～167.2 DEG C；Vicat softening point: 168.5～170.3 DEG C；Particle mean size: 238 μm.
Comparative example 5, suspension polymerization containing 51%PMI terpolymer, follow the steps below successively:
1) reaction
Styrene 96g, acrylonitrile 100g, the mixing of N-phenylmaleimide 204g, 3ml chain-transferring agent isopropanol are added
In 800g water, add 8g polyvinyl alcohol, stir 30 minutes, be subsequently adding 0.8g azodiisobutyronitrile, be warming up to 70 DEG C instead
Answer 6h, reaction to terminate, be warming up to the ripening 2h that seethes with excitement, filter, 100 DEG C of forced air dryings 1 hour, obtain white granular solid 352g,
Yield 88%.
2) test result
Vitrification point 192.2～201.8 DEG C；Vicat softening point: 201.9～206.1 DEG C；Particle mean size: 220 μm.
The concrete reaction condition of above-mentioned each case, result are summarized in table 1
Table 1 each case reaction condition, result collect
Embodiment 4 carries out each formula adjustment, and the contrast of gained case is as follows:
Comparative example 6-1
1) polymerization
Be sequentially added in 2000ml there-necked flask styrene 150g, acrylonitrile 90g, N-phenylmaleimide 160g,
Water 800g, dodecylbenzene sodium sulfonate 11g, cumyl peroxyneodecanoate 0.5g, beta naphthal 0.4g, sodium bicarbonate 1g, 30
DEG C stirring 30 minutes, heats up 60～65 DEG C react 6h；
2) centrifugal, dry
After polymerization reaction time arrives, add 0.05g bisphenol-A thus terminate polyreaction, filter, 100 DEG C of drums of gained filter cake
Air-dry dry 1 hour, obtain white granular solid 390g, yield 97.5%.
3) test result
Vitrification point: 163.2～166.3 DEG C；Vicat softening point: 166.4～169.4 DEG C；Particle mean size: 200 μm.
Comparative example 6-2
1) polymerization
Be sequentially added in 2000ml there-necked flask styrene 150g, acrylonitrile 90g, N-phenylmaleimide 160g,
Water 800g, lauryl alcohol 11g, cumyl peroxyneodecanoate 0.5g, beta naphthal 0.4g, sodium bicarbonate 1g, 30 DEG C are stirred 30 points
Clock, heat up 60～65 DEG C of reaction 6h, implode, this failure of an experiment.
Comparative example 6-3
1) polymerization
Be sequentially added in 2000ml there-necked flask styrene 150g, acrylonitrile 90g, N-phenylmaleimide 160g,
Water 800g, dodecylbenzene sodium sulfonate 5.5g, lauryl alcohol 5.5g, cumyl peroxyneodecanoate 0.5g, beta naphthal 0.4g, carbon
Acid hydrogen sodium 1g, 30 DEG C are stirred 30 minutes, and heat up 60～65 DEG C of reaction 6h；
2) centrifugal, dry
After polymerization reaction time arrives, add 0.05g bisphenol-A thus terminate polyreaction, filter, 100 DEG C of drums of gained filter cake
Air-dry dry 1 hour, obtain white powdery solids 392g, yield 98%.
3) test result
Vitrification point: 164.5～168.7 DEG C；Vicat softening point: 169.0～172.3 DEG C；Particle mean size: 77 μm.
Comparative example 6-4
1) polymerization
Be sequentially added in 2000ml there-necked flask styrene 150g, acrylonitrile 90g, N-phenylmaleimide 160g,
Water 800g, dodecylbenzene sodium sulfonate 10g, lauryl alcohol 1g, cumyl peroxyneodecanoate 0.5g, sodium bicarbonate 1g, 30 DEG C
Stirring 30 minutes, heat up 60～65 DEG C of reaction 6h；
2) centrifugal, dry
After polymerization reaction time arrives, add 0.05g bisphenol-A thus terminate polyreaction, filter, 100 DEG C of drums of gained filter cake
Air-dry dry 1 hour, obtain white granular solid 396g, yield 99%.
3) test result
Vitrification point: 167.2～171.7 DEG C；Vicat softening point: 170.3～175.4 DEG C；Particle mean size: 178 μm.
Comparative example 6-5
1) polymerization
Be sequentially added in 2000ml there-necked flask styrene 150g, acrylonitrile 90g, N-phenylmaleimide 160g,
Water 800g, dodecylbenzene sodium sulfonate 10g, lauryl alcohol 1g, cumyl peroxyneodecanoate 0.5g, beta naphthal 0.4g, 30 DEG C
Stirring 30 minutes, heat up 60～65 DEG C of reaction 6h；
2) centrifugal, dry
After polymerization reaction time arrives, add 0.05g bisphenol-A thus terminate polyreaction, filter, 100 DEG C of drums of gained filter cake
Air-dry dry 1 hour, obtain white granular solid 380g, yield 95%.
3) test result
Vitrification point: 167.3～171.9 DEG C；Vicat softening point: 171.3～176.4 DEG C；Particle mean size: 124 μm.
Comparative example 6-6
1) polymerization
Be sequentially added in 2000ml there-necked flask styrene 150g, acrylonitrile 90g, N-phenylmaleimide 160g,
Water 800g, dodecylbenzene sodium sulfonate 10g, lauryl alcohol 1g, cumyl peroxyneodecanoate 0.5g, 30 DEG C are stirred 30 minutes,
Heat up 60～65 DEG C of reaction 6h；
2) centrifugal, dry
After polymerization reaction time arrives, add 0.05g bisphenol-A thus terminate polyreaction, filter, 100 DEG C of drums of gained filter cake
Air-dry dry 1 hour, obtain white granular solid 382g, yield 95.5%.
3) test result
Vitrification point: 166.9～171.9 DEG C；Vicat softening point: 171.5～175.7 DEG C；Particle mean size: 184 μm.
Comparative example 6-7
1) polymerization
Be sequentially added in 2000ml there-necked flask styrene 150g, acrylonitrile 90g, N-phenylmaleimide 160g,
Water 800g, dodecylbenzene sodium sulfonate 10g, lauryl alcohol 1g, azodiisobutyronitrile 0.5g, beta naphthal 0.4g, sodium bicarbonate 1g, 30
DEG C stirring 30 minutes, heats up 60～65 DEG C react 6h；
2) centrifugal, dry
After polymerization reaction time arrives, add 0.05g bisphenol-A thus terminate polyreaction, filter, 100 DEG C of drums of gained filter cake
Air-dry dry 1 hour, obtain white powdery solids 396g, yield 99%.
3) test result
Vitrification point: 164.3～168.2 DEG C；Vicat softening point: 167.5～170.2 DEG C；Particle mean size: 85 μm.
Comparative example 6-8
1) polymerization
Be sequentially added in 2000ml there-necked flask styrene 150g, acrylonitrile 90g, N-phenylmaleimide 160g,
Water 800g, dodecylbenzene sodium sulfonate 10g, lauryl alcohol 1g, double (3,5, the 5-pivaloyl) 0.5g of peroxidating, beta naphthal
0.4g, sodium bicarbonate 1g, 30 DEG C are stirred 30 minutes, and heat up 60～65 DEG C of reaction 6h；
2) centrifugal, dry
After polymerization reaction time arrives, add 0.05g bisphenol-A thus terminate polyreaction, filter, 100 DEG C of drums of gained filter cake
Air-dry dry 1 hour, obtain white powdery solids 375g, yield 93.75%.
3) test result
Vitrification point: 165.4～170.0 DEG C；Vicat softening point: 170.3～175.1 DEG C；Particle mean size: 95 μm.
Comparative example 6-9
1) polymerization
Be sequentially added in 2000ml there-necked flask styrene 150g, acrylonitrile 90g, N-phenylmaleimide 160g,
Water 800g, dodecylbenzene sodium sulfonate 10g, lauryl alcohol 1g, peroxy dicarbonate-2-Octyl Nitrite 0.5g, beta naphthal 0.4g, carbon
Acid hydrogen sodium 1g, 30 DEG C are stirred 30 minutes, and heat up 60～65 DEG C of reaction 6h；
2) centrifugal, dry
After polymerization reaction time arrives, add 0.05g bisphenol-A thus terminate polyreaction, filter, 100 DEG C of drums of gained filter cake
Air-dry dry 1 hour, obtain white granular solid 380g, yield 95%.
3) test result
Vitrification point: 164.9～170.1 DEG C；Vicat softening point: 170.5～174.9 DEG C；Particle mean size: 90 μm.
Embodiment 4, comparative example 6-1～comparative example 6-9 contrast reaction condition summary sheet 2, result summary sheet 3.
Table 2 reaction condition summary sheet
Table 3 comparing result summary sheet
| Comparative example | Yield/% | Particle mean size/μm | Vitrification point/DEG C | Vicat softening point/DEG C |
| Embodiment 4 | 99.5 | 88 | 168.2～172.2 | 171.5～176.4 |
| 6-1 | 97.5 | 200 | 163.2～166.3 | 166.4～169.4 |
| 6-2 | --- | --- | --- | --- |
| 6-3 | 98 | 77 | 164.5～168.7 | 169.0～172.3 |
| 6-4 | 99 | 178 | 167.2～171.7 | 170.3～175.4 |
| 6-5 | 95 | 124 | 167.3～171.9 | 171.3～176.4 |
| 6-6 | 95.5 | 184 | 166.9～171.9 | 171.5～175.7 |
| 6-7 | 99 | 85 | 164.3～168.2 | 167.5～170.2 |
| 6-8 | 93.75 | 95 | 165.4～170.0 | 170.3～175.1 |
| 6-9 | 95 | 90 | 164.9～170.1 | 170.5～174.9 |
Finally, it should also be noted that exemplified as above is only some specific embodiments of the present invention.Obviously, the present invention is not
It is limited to above example, also has the most many deformation.Those of ordinary skill in the art directly can lead from present disclosure
The all deformation gone out or associate, are all considered as protection scope of the present invention.
Claims (7)
1. the aqueous phase microsuspension polymerization method of styrene-N-phenylmaleimide-acrylonitrile terpolymer, is characterized in that bag
Include following steps:
1) polymerization:
In polymeric kettle, put into the monomer being made up of styrene, acrylonitrile and N-phenylmaleimide, and put into without ion
Water, compound emulsifying agent, initiator, anti-fouling agent and pH adjusting agent, stirring, it is warming up to 40～85 DEG C and is polymerized；Polyreaction
Time is 2～7 hours；
In monomer, styrene, acrylonitrile, N-phenylmaleimide weight content be respectively 24～57%, 23～25%, 18～
51%；
Compound emulsifying agent is the 1～12% of total monomer weight, and initiator is the 0.6～2.4 ‰ of total monomer weight, and anti-fouling agent is
The 0.1～1 ‰ of total monomer weight, pH adjusting agent is the 0.1～10 ‰ of total monomer weight；
Described compound emulsifying agent is made up of emulsifying agent A and emulsifying agent B, and the weight ratio of described emulsifying agent A and emulsifying agent B is: 10:1
～1:1, emulsifying agent A are at least one in sodium lauryl sulphate, dodecylbenzene sodium sulfonate, dodecyl sodium sulfate, breast
Agent B is OPEO, lauryl alcohol, tetradecyl alchohol, octadecanol, polyvinyl alcohol, hydroxymethyl cellulose, hydroxy propyl cellulose
At least one in element；
Described initiator is oil-soluble initiator；
Described anti-fouling agent is polyhydric phenols；
2) centrifugal, dry:
After polymerization reaction time arrives, add account for the 0.1 of total weight of monomer～the terminator of 1 ‰ thus terminate polyreaction, filter, institute
Styrene-N-phenylmaleimide-acrylonitrile terpolymer is obtained after obtaining filtration cakes torrefaction.
The aqueous phase micro suspension of styrene-N-phenylmaleimide-acrylonitrile terpolymer the most according to claim 1
Polymerization, is characterized in that:
Described deionized water is 1～5 times of total monomer weight.
The aqueous phase of styrene-N-phenylmaleimide-acrylonitrile terpolymer the most according to claim 1 and 2 is micro-
Suspension polymerization, is characterized in that:
Described oil-soluble initiator be azodiisobutyronitrile, 2,2'-Azobis(2,4-dimethylvaleronitrile), dibenzoyl peroxide, peroxy dicarbonate-
2-Octyl Nitrite, di-cyclohexylperoxy di-carbonate, peroxy dicarbonate hexichol oxygen ethyl ester, double (3,5, the 5-front threes of peroxidating
Base acetyl), at least one in cumyl peroxyneodecanoate.
The aqueous phase micro suspension of styrene-N-phenylmaleimide-acrylonitrile terpolymer the most according to claim 3
Polymerization, is characterized in that:
Described polyhydric phenols be 1-naphthols, beta naphthal, 1,3-dihydroxy naphthlene, Isosorbide-5-Nitrae-dihydroxy naphthlene, 1,2,3-trihydroxynaphthalenes, Isosorbide-5-Nitrae, 5,
At least one in 8-tetrahydroxy naphthalene, Neville acid.
The aqueous phase micro suspension of styrene-N-phenylmaleimide-acrylonitrile terpolymer the most according to claim 4
Polymerization, is characterized in that:
Described terminator is bisphenol-A and/or acetone semicarbazone thiourea.
The aqueous phase micro suspension of styrene-N-phenylmaleimide-acrylonitrile terpolymer the most according to claim 5
Polymerization, is characterized in that:
Described pH adjusting agent is sodium hydroxide, potassium hydroxide, ammonia, sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, carbonic acid
At least one in calcium, ammonium carbonate, ammonium hydrogen carbonate.
The aqueous phase micro suspension of styrene-N-phenylmaleimide-acrylonitrile terpolymer the most according to claim 1
Polymerization, is characterized in that: step 1) stirring be 25～35 DEG C stir 20～40 minutes.
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