CN100494232C - Method for synthesizing phenylethene /acrylonitrile/ N-phenyl maleimide terpolymer by one-step method - Google Patents
Method for synthesizing phenylethene /acrylonitrile/ N-phenyl maleimide terpolymer by one-step method Download PDFInfo
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- CN100494232C CN100494232C CNB2007100690416A CN200710069041A CN100494232C CN 100494232 C CN100494232 C CN 100494232C CN B2007100690416 A CNB2007100690416 A CN B2007100690416A CN 200710069041 A CN200710069041 A CN 200710069041A CN 100494232 C CN100494232 C CN 100494232C
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- mercaptan
- dodecyl
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- ester
- dodecyl mercaptan
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- HIDBROSJWZYGSZ-UHFFFAOYSA-N 1-phenylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC=C1 HIDBROSJWZYGSZ-UHFFFAOYSA-N 0.000 title claims abstract description 30
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 238000000034 method Methods 0.000 title claims abstract description 18
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 229920001897 terpolymer Polymers 0.000 title claims description 7
- 230000002194 synthesizing effect Effects 0.000 title claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 238000001035 drying Methods 0.000 claims abstract description 16
- 239000003999 initiator Substances 0.000 claims abstract description 9
- 238000001816 cooling Methods 0.000 claims abstract 2
- 239000012986 chain transfer agent Substances 0.000 claims description 18
- 238000009835 boiling Methods 0.000 claims description 15
- -1 acetic acid n-dodecyl mercaptan ester Chemical class 0.000 claims description 10
- 239000002994 raw material Substances 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 8
- 239000000375 suspending agent Substances 0.000 claims description 8
- 229940094933 n-dodecane Drugs 0.000 claims description 7
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical group C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 6
- WQAQPCDUOCURKW-UHFFFAOYSA-N butanethiol Chemical compound CCCCS WQAQPCDUOCURKW-UHFFFAOYSA-N 0.000 claims description 6
- 239000001506 calcium phosphate Substances 0.000 claims description 6
- 229910000389 calcium phosphate Inorganic materials 0.000 claims description 6
- 235000011010 calcium phosphates Nutrition 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 claims description 6
- 239000004159 Potassium persulphate Substances 0.000 claims description 5
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 5
- 235000019394 potassium persulphate Nutrition 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 4
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 claims description 4
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 claims description 4
- 229920001451 polypropylene glycol Polymers 0.000 claims description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 4
- VVWRJUBEIPHGQF-UHFFFAOYSA-N propan-2-yl n-propan-2-yloxycarbonyliminocarbamate Chemical compound CC(C)OC(=O)N=NC(=O)OC(C)C VVWRJUBEIPHGQF-UHFFFAOYSA-N 0.000 claims description 4
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 4
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 claims description 4
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 3
- 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 3
- 239000004160 Ammonium persulphate Substances 0.000 claims description 3
- 108010010803 Gelatin Proteins 0.000 claims description 3
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims description 3
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 3
- 235000019395 ammonium persulphate Nutrition 0.000 claims description 3
- YQHLDYVWEZKEOX-UHFFFAOYSA-N cumene hydroperoxide Chemical compound OOC(C)(C)C1=CC=CC=C1 YQHLDYVWEZKEOX-UHFFFAOYSA-N 0.000 claims description 3
- 239000008273 gelatin Substances 0.000 claims description 3
- 229920000159 gelatin Polymers 0.000 claims description 3
- 235000019322 gelatine Nutrition 0.000 claims description 3
- 235000011852 gelatine desserts Nutrition 0.000 claims description 3
- 239000001095 magnesium carbonate Substances 0.000 claims description 3
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 3
- 229960001708 magnesium carbonate Drugs 0.000 claims description 3
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 3
- 235000014380 magnesium carbonate Nutrition 0.000 claims description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 3
- 229920000609 methyl cellulose Polymers 0.000 claims description 3
- 239000001923 methylcellulose Substances 0.000 claims description 3
- KZCOBXFFBQJQHH-UHFFFAOYSA-N octane-1-thiol Chemical compound CCCCCCCCS KZCOBXFFBQJQHH-UHFFFAOYSA-N 0.000 claims description 3
- 229920000620 organic polymer Polymers 0.000 claims description 3
- WMXCDAVJEZZYLT-UHFFFAOYSA-N tert-butylthiol Chemical compound CC(C)(C)S WMXCDAVJEZZYLT-UHFFFAOYSA-N 0.000 claims description 3
- YAJYJWXEWKRTPO-UHFFFAOYSA-N 2,3,3,4,4,5-hexamethylhexane-2-thiol Chemical compound CC(C)C(C)(C)C(C)(C)C(C)(C)S YAJYJWXEWKRTPO-UHFFFAOYSA-N 0.000 claims description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- HIZCIEIDIFGZSS-UHFFFAOYSA-N carbonotrithioic acid Chemical compound SC(S)=S HIZCIEIDIFGZSS-UHFFFAOYSA-N 0.000 claims description 2
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 2
- 235000012204 lemonade/lime carbonate Nutrition 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 150000002978 peroxides Chemical class 0.000 claims description 2
- 125000005634 peroxydicarbonate group Chemical group 0.000 claims description 2
- KRIOVPPHQSLHCZ-UHFFFAOYSA-N phenyl propionaldehyde Natural products CCC(=O)C1=CC=CC=C1 KRIOVPPHQSLHCZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000001384 succinic acid Substances 0.000 claims description 2
- 229920001577 copolymer Polymers 0.000 abstract description 6
- 239000003607 modifier Substances 0.000 abstract description 4
- 229920000642 polymer Polymers 0.000 abstract description 4
- 238000001914 filtration Methods 0.000 abstract description 3
- 239000002861 polymer material Substances 0.000 abstract description 3
- 238000002360 preparation method Methods 0.000 abstract description 3
- 238000010557 suspension polymerization reaction Methods 0.000 abstract description 3
- 239000003795 chemical substances by application Substances 0.000 abstract description 2
- 238000010438 heat treatment Methods 0.000 abstract description 2
- 229920000891 common polymer Polymers 0.000 abstract 1
- 239000000047 product Substances 0.000 description 22
- 238000010792 warming Methods 0.000 description 13
- 238000003756 stirring Methods 0.000 description 12
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 6
- 239000000178 monomer Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 150000003949 imides Chemical class 0.000 description 2
- 230000010534 mechanism of action Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- 239000004141 Sodium laurylsulphate Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The present invention discloses preparation process of N-phenyl maleimide copolymer. N-phenyl maleimide, styrene, acrylonitrile, chain transferring agent, and initiator are mixed, added into water, and reacted at 20-120 deg.c and 0.05-0.3 MPa for 0.5-10 hr; and through maintaining the pressure unchanged after finishing reaction, heating to boil, cooling, filtering and drying, product is obtained. The present invention synthesizes the copolymer through a suspension polymerization process and simple post treatment, and the produced copolymer has excellent heat resisting performance, and may be applied as heat resisting polymer and heat resisting modifier for PVC and other common polymer material.
Description
Technical field
The present invention relates to a kind of preparation method of multipolymer, especially relate to the method for synthesizing styrene/vinyl cyanide/N-phenylmaleimide terpolymer.
Background technology
The thermotolerance of macromolecular material is an importance of its performance, and the acid imide polymkeric substance is subjected to common concern with its superior resistance toheat.N-phenylmaleimide conduct a member wherein is a kind of novel stable on heating monomer of developing in recent years of resin that improves.Styrene/acrylonitrile/N-phenylmaleimide terpolymer (St/AN/N-PMI) is owing to introduced N-phenylmaleimide (N-PMI), and imide ring-type structure increases in the molecular chain, and the resistance toheat of polymkeric substance significantly improves.As the heat-proof modifier of commodity polymer materials such as thermally stable polymer and PVC, the St/AN/N-PMI multipolymer has wide application prospect.
At present synthetic St/AN/N-PMI multipolymer mainly adopts the mode of letex polymerization, as people such as Yang Liting (" synthetic resins and plastics " 2000 in article " N-phenylmaleimide/styrene/acrylonitrile emulsion copolymers and PVC blend ", 17 (3): be that emulsifying agent, Potassium Persulphate are initiator with the sodium lauryl sulphate 36), the emulsion copolymers that has synthesized St/AN/N-PMI, and with the PVC blend.But letex polymerization aftertreatment difficulty, and the products obtained therefrom particle diameter is small easily forms dust etc. and causes loss and pollute, and can not directly apply to industrial production, must form copolymer pellet by granulation and just can use.
In addition, after Chinese invention patent 95190019.6 discloses the multipolymer of maleimide and aromatic vinyl monomer,, form the method for graft copolymer again with the vinyl cyanide monomer polymerization.But this method needs just can obtain desired product through two steps, and technology is comparatively complicated.
Summary of the invention
The invention provides the method for a kind of employing suspension polymerization, single stage method synthesizing styrene/vinyl cyanide/N-phenylmaleimide terpolymer (St/AN/N-PMI).
The method of a kind of single stage method synthesizing styrene/vinyl cyanide/N-phenylmaleimide terpolymer, mixing raw material, chain-transfer agent, suspension agent and initiator are added in the entry, at 20～120 ℃, pressure 0.05～0.3MPa, reacted 0.5～10 hour, after reaction was finished, the constant boiling that is warmed up to that keep-ups pressure was cooled off, filtration, drying obtain finished product again; Described mixing raw material is N-phenylmaleimide, vinylbenzene and vinyl cyanide, and its mass percent consists of: N-phenylmaleimide 15～55%; Vinylbenzene 25～50%; Vinyl cyanide 16～50%.
The quality of described water is N-phenylmaleimide, vinylbenzene and three kinds of raw materials quality summations of vinyl cyanide 0.1～10 times.
In every 100g mixing raw material, the chain-transfer agent consumption is that 0.01～10g, suspension agent consumption are that 0.1～15g, initiator amount are 0.01～15g, and described mixing raw material is N-phenylmaleimide, vinylbenzene and vinyl cyanide.
Described chain-transfer agent is C
1～C
12Monohydroxy-alcohol, C
1～C
12At least a in mercaptan or the thiol derivative.
C
1～C
12Monohydroxy-alcohol, C
1～C
12Mercaptan is as: Virahol, n-butyl mercaptan, tert-butyl mercaptan, octyl mercaptan, positive Dodecyl Mercaptan, tert-dodecyl mercaptan or mercaptoethanol etc.
The derivative of mercaptan is as acetic acid n-dodecyl mercaptan ester, Succinic Acid list-n-dodecyl mercaptan ester, oxalic acid two-n-dodecyl mercaptan ester, phenylformic acid n-dodecyl mercaptan ester, list-dodecyl sodium sulfate, three-n-dodecane sulfenyl methane, trithiocarbonic acid two-dodecyl ester, 1-n-dodecane sulfenyl ethapon or beta-phenyl-β-n-dodecane sulfenyl ethyl phenyl ketone.
Described suspension agent is at least a in water soluble organic polymer thing or the water-fast inorganic powder.The mechanism of action of polymer suspension agent mainly is to be adsorbed on the drop surface, forms layer protecting film, plays a part protective colloid.Surface (or interface) tension force is reduced, help drop and disperse.The mechanism of action of inorganic powder is that fine powder is adsorbed on the drop surface, plays a part mechanical isolation.
The water soluble organic polymer thing is as salt, methylcellulose gum or the gelatin etc. of the salt of polyvinyl alcohol, the salt of POLYPROPYLENE GLYCOL, polymethyl acrylic acid.Water-fast inorganic powder is as magnesiumcarbonate, lime carbonate, calcium phosphate or talcum powder etc.
Described initiator comprises general known organo-peroxide, inorganic peroxide or azo-compound.As: dibenzoyl peroxide, peroxy dicarbonates, isopropyl benzene hydroperoxide, dicumyl peroxide, Potassium Persulphate, ammonium persulphate, Diisopropyl azodicarboxylate or 2,2'-Azobis(2,4-dimethylvaleronitrile) etc.
The present invention uses the mode of suspension polymerization to synthesize the multipolymer of St/AN/N-PMI, can directly obtain granular product, and aftertreatment is simple, after reaction finishes, only need be warming up to the boiling slaking, more after filtration, drying, get final product final product.Adopt " one kettle way " to obtain product, further simplified technology., described multipolymer has good resistance toheat, can be used as the heat-proof modifier of commodity polymer materials such as thermally stable polymer and PVC.
Embodiment
Embodiment 1
357gN-PMI, 180gSt, 163gAN and 5ml chain-transfer agent Virahol are mixed in the adding 2000mL water, add the 10g polyvinyl alcohol again, stir 20～30min, add the 1g Potassium Persulphate then, in about 70 ℃, react 5h.Reaction is warming up to the boiling slaking after finishing, and refilters the product that drying obtains white granular.
Embodiment 2
280gN-PMI, 250gSt, 170gAN and 5ml chain-transfer agent Virahol are mixed in the adding 1000mL water, add the 10g sodium polymethacrylate again, stir 20～30min, add the 1g isopropyl benzene hydroperoxide then, in about 85 ℃, react 2h.Reaction is warming up to the boiling slaking after finishing, and refilters the product that drying obtains white granular.
Embodiment 3
238gN-PMI, 350gSt, 112gAN and 5ml chain-transfer agent DDM dodecyl mercaptan are mixed in the adding 2000mL water, add the 15g polyvinyl alcohol again, stir 20～30min, add the 1g dibenzoyl peroxide then, in about 60 ℃, react 7h.Reaction is warming up to the boiling slaking after finishing, and refilters the product that drying obtains white granular.
Embodiment 4
175gN-PMI, 300gSt, 225gAN and 15ml chain-transfer agent acetic acid n-dodecyl mercaptan ester are mixed in the adding 5000mL water, add the 25g POLYPROPYLENE GLYCOL again, stir 20～30min, add the 2g dibenzoyl peroxide then, under pressurized conditions, in about 40 ℃, react 6h.Reaction is warming up to the boiling slaking after finishing, and refilters the product that drying obtains white granular.
Embodiment 5
126gN-PMI, 224gSt, 350gAN and 10ml chain-transfer agent mercaptoethanol are mixed in the adding 1000mL water, add 20g calcium phosphate again, stir 20～30min, add the 1.5g Diisopropyl azodicarboxylate then, in about 90 ℃, react 5h.Reaction is warming up to the boiling slaking after finishing, and refilters the product that drying obtains white granular.
Embodiment 6
152gN-PMI, 300gSt, 248gAN and 15ml chain-transfer agent tert-butyl mercaptan are mixed in the adding 3000mL water, add 15g calcium phosphate again, stir 20～30min, add the 2g ammonium persulphate then, in about 80 ℃, react 3h.Reaction is warming up to the boiling slaking after finishing, and refilters the product that drying obtains white granular.
Embodiment 7
120gN-PMI, 300gSt, 280gAN and 10ml chain-transfer agent n-butyl mercaptan are mixed in the adding 1500mL water, add the 20g methylcellulose gum again, stir 20～30min, add the 0.5g Diisopropyl azodicarboxylate then, in about 80 ℃, react 3h.Reaction is warming up to the boiling slaking after finishing, and refilters the product that drying obtains white granular.
Embodiment 8
200gN-PMI, 200gSt, 300gAN and 5ml chain-transfer agent octyl mercaptan are mixed in the adding 2000mL water, add the 10g gelatin again, stir 20～30min, add the 1g Potassium Persulphate then, in about 50 ℃, react 7h.Reaction is warming up to the boiling slaking after finishing, and refilters the product that drying obtains white granular.
Embodiment 9
200gN-PMI, 350gSt, 150gAN and 5ml chain-transfer agent mercaptoethanol are mixed in the adding 2400mL water, add 20g magnesiumcarbonate again, stir 20～30min, add the 2.5g 2,2'-Azobis(2,4-dimethylvaleronitrile) then, in about 60 ℃, react 7h.Reaction is warming up to the boiling slaking after finishing, and refilters the product that drying obtains white granular.
Embodiment 10
150gN-PMI, 350gSt, 250gAN and 5ml chain-transfer agent three-n-dodecane sulfenyl methane blended are added in the 3500mL water, add 10g calcium phosphate again, stir 20～30min, add the 1g dibenzoyl peroxide then, under pressurized conditions, in about 45 ℃, react 3h.Reaction is warming up to the boiling slaking after finishing, and refilters the product that drying obtains white granular.
Embodiment 11
180gN-PMI, 350gSt, 120gAN and 5ml chain-transfer agent list-dodecyl sodium sulfate is mixed in the adding 1000mL water, add the 10g POLYPROPYLENE GLYCOL again, stir 20～30min, add the 1g dicumyl peroxide then, in about 80 ℃, react 3h.Reaction is warming up to the boiling slaking after finishing, and refilters the product that drying obtains white granular.
Embodiment 12
228gN-PMI, 360gSt, 112gAN and 20ml chain-transfer agent DDM dodecyl mercaptan are mixed in the adding 3500mL water, add 20g calcium phosphate again, stir 20～30min, add the 1g dibenzoyl peroxide then, in about 70 ℃, react 5h.Reaction is warming up to the boiling slaking after finishing, and refilters the product that drying obtains white granular.
Performance test
The St/AN/N-PMI multipolymer of embodiment 1,2,3,4,5 preparations is carried out performance test, and every index and result are as shown in table 1.
Each trade mark product index of table 1
| Embodiment | 1 | 2 | 3 | 4 | 5 |
| The trade mark | HRR-51 | HRR-40 | HRR-34 | HRR-25 | HRR-18 |
| The N-PMI massfraction | 51％ | 40％ | 34％ | 25％ | 18％ |
| Second-order transition temperature/℃ | 192.5～201.6 | 163.3～167.3 | 146.2～150.7 | 140.3～145.5 | 131.7～134.8 |
| GPC/10 4 | 50.4～60.7 | 39.6～45.3 | 30.5～34.7 | 20.3～25.8 | 15.6～20.1 |
| Vicat softening point/℃ | 202.3～205.2 | 166.8～170.5 | 150.1～156.8 | 124.2～135.5 | 117.2～123.2 |
| Melt index/g/10min | 0.9～2.0 | 1.1～2.9 | 1.3～3.0 | 2.1～4.3 | 8.3～12.5 |
By data in the table 1 as can be seen, the character of its resistance toheats of embodiment such as the second-order transition temperature of multipolymer, Vicat softening point all raises with the increase of multipolymer N-PMI content, the resistance toheat that is multipolymer improves along with the increase of its N-PMI content, can select the multipolymer of different N-PMI content as heat-proof modifier according to different resin modified demands.
Also St/AN/N-PMI multipolymer (HRR-34) product of embodiment 3 is added in the ABS resin in addition, measured every index of ABS resin after the modification, its result is as shown in table 2.
Table 2 is the every index of ABS resin after the modification of HRR-34 product
Annotate: in the table 1
#, 2
#Be respectively the index of HRR-34 product interpolation 40%, 50% in the ABS resin,
3
#For not adding the ABS resin of heat-resistant agent.
By data in the table 2 as can be seen, the interpolation of HRR-34 product all has some improvement to ABS resin resistance toheat and mechanical property etc.
Claims (5)
1, the method of a kind of single stage method synthesizing styrene/vinyl cyanide/N-phenylmaleimide terpolymer, it is characterized in that: with mixing raw material, chain-transfer agent, suspension agent and initiator add in the entry, the quality of described water is 0.1～10 times of mixing raw material quality, in every 100g mixing raw material, the chain-transfer agent consumption is 0.01～10g, the suspension agent consumption is 0.1～15g, initiator amount is 0.01～15g, at 20～120 ℃, pressure 0.05～0.3MPa, reacted 0.5～10 hour, after reaction is finished, the constant boiling that is warmed up to, cooling again keep-up pressure, filter, drying obtains finished product; Described mixing raw material is N-phenylmaleimide, vinylbenzene and vinyl cyanide, and its mass percent consists of: N-phenylmaleimide 15～55%; Vinylbenzene 25～50%; Vinyl cyanide 16～50%;
Described chain-transfer agent is C
1～C
12Monohydroxy-alcohol, C
1～C
12At least a in mercaptan, acetic acid n-dodecyl mercaptan ester, Succinic Acid list-n-dodecyl mercaptan ester, oxalic acid two-n-dodecyl mercaptan ester, phenylformic acid n-dodecyl mercaptan ester, list-dodecyl sodium sulfate, three-n-dodecane sulfenyl methane, trithiocarbonic acid two-dodecyl ester, 1-n-dodecane sulfenyl ethapon or beta-phenyl-β-n-dodecane sulfenyl ethyl phenyl ketone;
Described suspension agent is at least a in water soluble organic polymer thing or the water-fast inorganic powder.
2, method according to claim 1 is characterized in that: described C
1～C
12Monohydroxy-alcohol, C
1～C
12Mercaptan is Virahol, n-butyl mercaptan, tert-butyl mercaptan, octyl mercaptan, positive Dodecyl Mercaptan, tert-dodecyl mercaptan or mercaptoethanol.
3, method according to claim 1 is characterized in that: described suspension agent is at least a in salt, methylcellulose gum, gelatin, magnesiumcarbonate, lime carbonate, calcium phosphate or the talcum powder of salt, polymethyl acrylic acid of salt, the POLYPROPYLENE GLYCOL of polyvinyl alcohol.
4, method according to claim 1 is characterized in that: described initiator is organo-peroxide, inorganic peroxide or azo-compound.
5, method according to claim 4 is characterized in that: described initiator is dibenzoyl peroxide, peroxy dicarbonates, isopropyl benzene hydroperoxide, dicumyl peroxide, Potassium Persulphate, ammonium persulphate, Diisopropyl azodicarboxylate or 2,2'-Azobis(2,4-dimethylvaleronitrile).
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| CN101538347B (en) * | 2009-02-06 | 2013-11-13 | 上海华谊（集团）公司 | Maleimide copolymer and synthetic method thereof |
| CN101824115B (en) * | 2009-03-03 | 2011-12-07 | 复旦大学 | One-step method for synthesizing styrene/ N-benzyl maleimide/ maleic anhydride terpolymer |
| CN101914178B (en) * | 2010-07-30 | 2012-05-16 | 宁波镇洋化工发展有限公司 | Preparation method of dutrex-unsaturated nitrile-cyclenes heat-resistant copolymer |
| CN102786622B (en) * | 2012-08-02 | 2014-06-18 | 田岳南 | Processing modifying agent applied to polyvinyl chloride pipe materials and pipe fittings |
| CN103059221A (en) * | 2013-01-22 | 2013-04-24 | 上海华谊（集团）公司 | Method for preparing high-performance maleimide copolymer by using suspension method |
| US10435495B2 (en) * | 2014-06-27 | 2019-10-08 | Lotte Advanced Materials Co., Ltd. | Copolymers and thermoplastic resin composition comprising the same |
| WO2022097962A1 (en) * | 2020-11-05 | 2022-05-12 | 주식회사 엘지화학 | Method for preparing polymer |
| CN117106131B (en) * | 2023-08-28 | 2024-04-12 | 恒光新材料(江苏)股份有限公司 | Explosion polymerization method for preventing N-phenylmaleimide copolymerization system |
| CN117264105A (en) * | 2023-09-25 | 2023-12-22 | 安徽恒光聚氨酯材料有限公司 | Production process and production system of N-phenylmaleimide polymer |
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