CN109096430A - A kind of novel reactive quadripolymer and preparation method thereof - Google Patents
A kind of novel reactive quadripolymer and preparation method thereof Download PDFInfo
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- CN109096430A CN109096430A CN201810826665.6A CN201810826665A CN109096430A CN 109096430 A CN109096430 A CN 109096430A CN 201810826665 A CN201810826665 A CN 201810826665A CN 109096430 A CN109096430 A CN 109096430A
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- 238000002360 preparation method Methods 0.000 title abstract description 12
- 239000000178 monomer Substances 0.000 claims abstract description 57
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 14
- -1 acrylic ester Chemical class 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000004519 manufacturing process Methods 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims description 31
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 23
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 21
- 239000002904 solvent Substances 0.000 claims description 9
- 229920006397 acrylic thermoplastic Polymers 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 239000003999 initiator Substances 0.000 claims description 7
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 7
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 claims description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 claims description 5
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 5
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 150000001336 alkenes Chemical class 0.000 claims description 4
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical group CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 claims description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 3
- 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 2
- 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 2
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical group CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 150000002632 lipids Chemical class 0.000 claims 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims 1
- 235000019400 benzoyl peroxide Nutrition 0.000 claims 1
- 150000004702 methyl esters Chemical class 0.000 claims 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims 1
- 229920000728 polyester Polymers 0.000 abstract description 13
- 229910045601 alloy Inorganic materials 0.000 abstract description 10
- 239000000956 alloy Substances 0.000 abstract description 10
- 229920003023 plastic Polymers 0.000 abstract description 8
- 239000004033 plastic Substances 0.000 abstract description 8
- 238000000034 method Methods 0.000 abstract description 7
- 230000007613 environmental effect Effects 0.000 abstract description 5
- 150000002148 esters Chemical group 0.000 abstract description 5
- 238000012662 bulk polymerization Methods 0.000 abstract description 3
- 238000005809 transesterification reaction Methods 0.000 abstract description 3
- 238000012805 post-processing Methods 0.000 abstract description 2
- 239000002351 wastewater Substances 0.000 abstract description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical group CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 8
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical group COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 8
- 229920001577 copolymer Polymers 0.000 description 8
- 239000004970 Chain extender Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- FFODZTFGFDDGQQ-UHFFFAOYSA-N 2-methylprop-2-enoic acid;5-phenylpenta-2,4-dienenitrile Chemical compound CC(=C)C(O)=O.N#CC=CC=CC1=CC=CC=C1 FFODZTFGFDDGQQ-UHFFFAOYSA-N 0.000 description 1
- 229910000967 As alloy Inorganic materials 0.000 description 1
- WXQDFOGZIYLEGP-UHFFFAOYSA-N C(C(C)C)#N.C(C(C)C)#N.[N] Chemical compound C(C(C)C)#N.C(C(C)C)#N.[N] WXQDFOGZIYLEGP-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- WURBFLDFSFBTLW-UHFFFAOYSA-N benzil Chemical group C=1C=CC=CC=1C(=O)C(=O)C1=CC=CC=C1 WURBFLDFSFBTLW-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- KVNRLNFWIYMESJ-UHFFFAOYSA-N butyronitrile Chemical compound CCCC#N KVNRLNFWIYMESJ-UHFFFAOYSA-N 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 125000003438 dodecyl group Chemical group [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])* 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 1
- 125000005456 glyceride group Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/08—Styrene
- C08F212/10—Styrene with nitriles
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/12—Monomers containing a branched unsaturated aliphatic radical or a ring substituted by an alkyl radical
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses a kind of novel chemically-reactive quadripolymers, the quadripolymer is made of following composition: aromatic vinyl monomer, acrylic monomer, acrylic ester monomer, glycidyl methacrylate, and the weight average molecular weight of quadripolymer is 80000-200000.Also disclose the production method of the novel chemically-reactive quadripolymer.The preparation method of quadripolymer of the present invention is bulk polymerization, and process flow is simple, preparation process environmental protection, no waste water, and post-processing is simple；Product degree of purity prepared by the present invention is high, meets the low smell of auto plastics, low-residual, the low environmental requirement distributed；Product prepared by the present invention contains esters structure, micro transesterification can occur with polyester plastics, be conducive to the compatibility for improving quadripolymer and polyester.Meanwhile the structure defers to the principle of similar compatibility, the compatilizer being more suitable as polyester and ABS alloy greatlys improve the mechanical property of alloy.
Description
Technical field
The present invention relates to high molecular material auxiliary agent synthesis technical fields, and in particular to a kind of novel reactivity is quarternary copolymerized
Object and preparation method thereof.
Background technique
Glycidyl methacrylate (GMA) has very high since its molecular structure contains double bond and epoxy group
Activity, so the copolymer containing glycidyl methacrylate be commonly used for alloy compatilizer or engineering resin it is special
It is the chain extender of condensation resin, one for becoming developing material field containing glycidyl methacrylate polymer at present grinds
Study carefully hot spot.If the ADR series of BASF is the copolymer of styrene and glycidyl methacrylate, be commonly used for PC,
The chain extender of the plastics such as PET, PBT, PA increases the viscosity and molecular weight of plastics, improves the mechanical property of plastics.Patent
CN201110372158 provides the preparation method of glycidyl methacrylate graft ABS a kind of, and the patent is using melting
The mode of grafting prepares glycidyl methacrylate graft ABS, can be used as the compatilizer of ABS class alloy, but its methyl-prop
The actual content of olefin(e) acid ethylene oxidic ester is only 0.1-3wt%, and reaction efficiency is not high, and preparation process smell is larger, remains not
Reaction monomers are more.Patent CN200910048853 provides a kind of styrene, acrylonitrile, glycidyl methacrylate three
The preparation method of membered copolymer, the patent use suspension polymerization, and it is sweet that products obtained therefrom contains higher Glycidyl methacrylate
Glyceride content is suitable as compatilizer, dumb light agent and the polyester chain extender of ABS class alloy, but the mode of its suspension polymerisation can be residual
Dispersing agent, initiator etc. are stayed, product degree of purity is inadequate.Meanwhile relying solely on the reactivity of glycidyl methacrylate
The compatilizer of ABS and polyester can not be improved well, and mechanical property improves limited.S.L.Sun etc. [S.L.Sun.Polymer,
2005,46,7632-7643] ABS-co-GMA is synthesized by way of emulsion polymerization, the preparation method process is complicated, and product is pure
Cleanliness is low, and products obtained therefrom is easy to appear defect in use process.
Summary of the invention
In order to solve the above technical problems, the technical solution adopted by the present invention is that: a kind of novel chemically-reactive quadripolymer, institute
It states quadripolymer to be made of following composition: 45-85 parts of aromatic vinyl monomer, 10-30 parts of acrylic monomer, 1-
The weight average molecular weight of 10 parts of acrylic ester monomer, 0.5-20 parts of glycidyl methacrylate, quadripolymer is
80000-200000。
The aromatic vinyl monomer includes styrene monomer or α-methylstyrene as a preferred embodiment of the above solution,
Monomer.
The acrylic monomer is acrylonitrile as a preferred embodiment of the above solution,.
The acrylics monomer is methyl acrylate, methyl methacrylate, propylene as a preferred embodiment of the above solution,
One of acetoacetic ester, butyl acrylate, hydroxy-ethyl acrylate, hydroxypropyl acrylate are a variety of.
A kind of production method of novel chemically-reactive quadripolymer, it is described to include the following steps:
Step 1: 45 parts -85 parts of aromatic vinyl monomer, 10 parts -30 parts of acrylonitrile monemer, 1 part -10 parts are weighed
Acrylics monomer, 0-30 parts of solvent, 0-0.5 parts of oil-soluble initiator and 0.1 part -1 part of molecular weight regulator,
By partially aromatic vinyl monomer, part propylene nitrile monomer, part acrylic acid lipid monomer, whole solvents, whole oil
It is reacted after mixing evenly in soluble initiator and whole molecular weight regulators investment reaction kettle, reaction temperature 60-140
DEG C, reacting kettle inner pressure 0.1-1.2MPa；
Step 2: weighing 0.5-20 parts of glycidyl methacrylate, by whole methyl propenoic acid glycidyls
Remaining aromatic vinyl monomer, remaining acrylonitrile monemer, remaining acrylics list in ester monomer and step 1
Body, which is added dropwise in reaction kettle, to react, and when conversion ratio reaches 40%-70%, reaction solution is injected vacuum volatilization device, is then existed
150-250 DEG C, remove unreacted monomer under the vacuum condition of pressure 4-100KPa, obtain aromatic vinyl monomer, acrylonitrile
Monomer, acrylics monomer and glycidyl methacrylate quadripolymer.
The unreacted monomer is recycled by condenser and is used as a preferred embodiment of the above solution,.
The oil-soluble initiator is azodiisobutyronitrile, cumyl peroxide and mistake as a preferred embodiment of the above solution,
Any one in dibenzoyl is aoxidized, the molecular weight regulator is lauryl mercaptan, and the solvent is ethylbenzene.
The working principle of the invention is: a kind of novel reactive quadripolymer is synthesized by way of bulk polymerization,
The copolymer includes aromatic vinyl monomer, acrylonitrile monemer, acrylics monomer and glycidyl methacrylate
Monomer.Caused first by heat or a small amount of initiator causes a large amount of macromolecular radical of generation, is i.e. chain causes, and then presses
Free radical polymerization is carried out according to the mode of the kineticses such as chain growth, chain termination, obtains quadripolymer.When system heat of reaction
It is not high, it is not necessary that solvent is added.When reaction heat is higher, needs to be added the solvent of 10-30% in system, be conducive to radiate.It should
Quadripolymer can be reacted due to containing glycidyl methacrylate with the terminal hydroxy group of polyester, when GMA content is higher
When, it can be crosslinked with polyester, so the chain extender of polyester and alloy compatilizer, delustering agent.Simultaneously as the quadripolymer
Containing esters structure, transesterification can occur with polyester plastics, and defer to the principle of similar compatibility, so the quadripolymer is special
It is suitable as the compatilizer and chain extender of polyester alloy.
The beneficial effects of the present invention are:
1, preparation method of the invention is bulk polymerization, and process flow is simple, preparation process environmental protection, no waste water, post-processing
Simply.
2, the product degree of purity prepared by the present invention is high, meets the low smell of auto plastics, low-residual, the low environmental protection distributed are wanted
It asks.
3, quadripolymer of the invention can occur micro transesterification with polyester plastics, be conducive to mention containing esters structure
The compatibility of high quadripolymer and polyester.Meanwhile the structure defers to the principle of similar compatibility, be more suitable as polyester with
The compatilizer of ABS alloy greatlys improve the mechanical property of alloy.
Detailed description of the invention
Fig. 1 is copolymer D molecular weight GPC test result figure.
Specific embodiment
The present invention is described in detail combined with specific embodiments below.Following embodiment will be helpful to the technology of this field
Personnel further understand the present invention, but the invention is not limited in any way.It should be pointed out that the ordinary skill of this field
For personnel, without departing from the inventive concept of the premise, various modifications and improvements can be made.These belong to the present invention
Protection scope.
Embodiment 1
By 37.5 parts of styrene monomers, 12.5 parts of acrylonitrile monemers, 1 part of methyl methacrylate and 0.1 part of dodecyl
It is stirred evenly in mercaptan investment reaction kettle, temperature of reaction kettle is 130 DEG C, pressure 0.6MPa.By remaining 36 parts of styrene lists
Body, 12 parts of acrylonitrile monemers, 1 part of glycidyl methacrylate monomer dropping to reaction kettle, when conversion ratio reaches 70%,
Solution is injected into vacuum volatilization device, after remove unreacted monomer under 220 DEG C, the vacuum condition of pressure 10KPa, obtain benzene second
Alkene, acrylonitrile, methyl methacrylate and glycidyl methacrylate quadripolymer A, composition and performance are shown in Table 1.
Unreacted monomer is recycled by condenser and is used.
Embodiment 2
By 30 parts of ethylbenzene, 20 parts of α-methylstyrenemonomers, 4 parts of acrylonitrile monemers, 5 parts of butyl acrylates, 0.01 part of idol
It is stirred evenly in nitrogen bis-isobutyronitrile and 1 part of lauryl mercaptan investment reaction kettle, temperature of reaction kettle is 80 DEG C, and pressure is
0.1MPa.By remaining 44 parts of α-methylstyrenemonomers, 12 parts of acrylonitrile, 5 parts of butyl acrylates, 10 parts of methacrylic acid contractings
Water glyceride monomers are added dropwise to reaction kettle, when conversion ratio reaches 40%, by solution inject vacuum volatilization device, after 150 DEG C, pressure
Unreacted monomer is removed under the vacuum condition of power 4KPa, obtains styrene, acrylonitrile, butyl acrylate and Glycidyl methacrylate
Glyceride quadripolymer B, composition and performance are shown in Table 1.Unreacted monomer is recycled by condenser and is used.
Embodiment 3
30 parts of ethylbenzene, 29 parts of styrene monomers, 10 parts of acrylonitrile monemers, 1 part of methyl acrylate, 0.5 part of azo two is different
It is stirred evenly in butyronitrile and 0.5 part of lauryl mercaptan investment reaction kettle, temperature of reaction kettle is 60 DEG C, pressure 0.2MPa.It will
Remaining 44.5 parts of styrene monomers, 12 parts of acrylonitrile monemers, 0.5 part of glycidyl methacrylate monomer dropping to reaction
Solution is injected vacuum volatilization device when conversion ratio reaches 45% by kettle, after taken off under 250 DEG C, the vacuum condition of pressure 100KPa
Except unreacted monomer, styrene, acrylonitrile, methyl acrylate and glycidyl methacrylate quadripolymer C are obtained,
Composition and performance see table 1.Unreacted monomer is recycled by condenser and is used.
Embodiment 4
By 20 parts of ethylbenzene, 39 parts of styrene monomers, 13 parts of acrylonitrile monemers, 2 parts of hydroxypropyl acrylates and 0.3 part of dodecane
It is stirred evenly in base mercaptan investment reaction kettle, temperature of reaction kettle is 120 DEG C, pressure 1.2MPa.By remaining 30 parts of styrene
Monomer, 10 parts of acrylonitrile monemers, 2 parts of hydroxypropyl acrylates are added dropwise to reaction kettle, and when conversion ratio reaches 50%, solution is injected
Vacuum volatilization device, after remove unreacted monomer under 200 DEG C, the vacuum condition of pressure 4KPa, obtain styrene, acrylonitrile, first
Base methyl acrylate and hydroxypropyl acrylate quadripolymer D, composition and performance are shown in Table 1 and molecular weight test the result is shown in Figure 1.
Unreacted monomer is recycled by condenser and is used.
1 quadripolymer of table composition and performance
Comparative example 1
ABS-g-GMA polymer E is prepared according to the method that CN201110372158 is provided, performance table is shown in Table 1.
Comparative example 2
Styrene-acrylonitrile methacrylic acid is prepared according to the method that the patent of Patent No. CN200910048853 provides
Glycidyl ester copolymer F, performance are shown in Table 1.
Wherein, weight average molecular weight and its distribution are tested by gel permeation chrommatograph (GPC), and solvent is tetrahydrofuran；
Melt index testing standard is ASTM D1238；Copolymer test condition is 200 DEG C of * 5kg, unit g/10min；
Volatile organic substance content (TVOC) testing standard is VDA277, unit ppm；
By the above test result it is found that quadripolymer molecular weight prepared by the present invention and initiation and content, molecular weight tune
Section agent content, reaction temperature are inversely proportional, and melt index is positively correlated with molecular weight substantially.Preparation method product residue list of the invention
Body is few, product degree of purity is high, particularly suitable as low compatilizer, chain extender or the delustering agent for distributing low smell alloy.
Compared with old technology, copolymer residual monomer prepared by the present invention is lower, product degree of purity is high, reactivity
Height is suitable as alloy compatilizer, dumb light agent etc., meets environmental protection, low-residual etc. and requires.
Specific embodiments of the present invention are described above.It is to be appreciated that the invention is not limited to above-mentioned
Particular implementation, those skilled in the art can make various deformations or amendments within the scope of the claims, this not shadow
Ring substantive content of the invention.
Claims (9)
1. a kind of novel chemically-reactive quadripolymer, which is characterized in that the quadripolymer is made of following composition: 45-85
Part aromatic vinyl monomer, 10-30 parts of acrylic monomer, 1-10 parts of acrylic ester monomer, 0.5-20 parts
Glycidyl methacrylate, the weight average molecular weight of quadripolymer are 80000-200000.
2. novel chemically-reactive quadripolymer as described in claim 1, which is characterized in that the aromatic vinyl monomer packet
Include styrene monomer or α-methylstyrenemonomer.
3. novel chemically-reactive quadripolymer as described in claim 1, which is characterized in that the acrylic monomer is propylene
Nitrile.
4. novel chemically-reactive quadripolymer as described in claim 1, which is characterized in that the acrylics monomer is third
E pioic acid methyl ester, methyl methacrylate, ethyl acrylate, butyl acrylate, hydroxy-ethyl acrylate, one in hydroxypropyl acrylate
Kind is a variety of.
5. a kind of production method of novel chemically-reactive quadripolymer as described in claim 1, which is characterized in that described to include
Following steps:
Step 1: 45 parts -85 parts of aromatic vinyl monomer, 10 parts -30 parts of acrylonitrile monemer, the third of 1 part -10 parts are weighed
Olefin(e) acid lipid monomer, 0-30 parts of solvent, 0-0.5 parts of oil-soluble initiator and 0.1 part -1 part of molecular weight regulator, by portion
Divide aromatic vinyl monomer, part propylene nitrile monomer, part acrylic acid lipid monomer, whole solvents, whole oil-solubles
It is reacted after mixing evenly in initiator and whole molecular weight regulators investment reaction kettle, reaction temperature is 60-140 DEG C,
Reacting kettle inner pressure is 0.1-1.2MPa；
Step 2: weighing 0.5-20 parts of glycidyl methacrylate, by whole glycidyl methacrylate lists
Remaining aromatic vinyl monomer, remaining acrylonitrile monemer, remaining acrylics monomer drop in body and step 1
It adds in reaction kettle and reacts, when conversion ratio reaches 40%-70%, reaction solution is injected into vacuum volatilization device, then in 150-250
DEG C, remove unreacted monomer under the vacuum condition of pressure 4-100KPa, obtain aromatic vinyl monomer, acrylonitrile monemer, third
Olefin(e) acid lipid monomer and glycidyl methacrylate quadripolymer.
6. the production method of novel chemically-reactive quadripolymer as claimed in claim 5, which is characterized in that the unreacted list
Body is recycled by condenser and is used.
7. the production method of novel chemically-reactive quadripolymer as claimed in claim 5, which is characterized in that the oil-soluble draws
Hair agent is any one in azodiisobutyronitrile, cumyl peroxide and dibenzoyl peroxide.
8. the production method of novel chemically-reactive quadripolymer as claimed in claim 5, which is characterized in that the molecular weight tune
Section agent is lauryl mercaptan.
9. the production method of novel chemically-reactive quadripolymer as claimed in claim 5, which is characterized in that the solvent is second
Benzene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810826665.6A CN109096430A (en) | 2018-07-25 | 2018-07-25 | A kind of novel reactive quadripolymer and preparation method thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109988263A (en) * | 2019-04-02 | 2019-07-09 | 嘉兴华雯化工有限公司 | A kind of anhydride macromolecule chain extender and preparation method thereof |
| CN114806098A (en) * | 2021-01-22 | 2022-07-29 | 武汉顺威赛特工程塑料有限公司 | A kind of low warpage reinforced PBT material and preparation method thereof |
| CN115466350A (en) * | 2021-11-29 | 2022-12-13 | 上海涵点科技有限公司 | Reactive chain extender with high-activity groups and application thereof |
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| JPH0665321A (en) * | 1992-08-19 | 1994-03-08 | Kanegafuchi Chem Ind Co Ltd | Heat stabilizer and thermoplastic resin composition |
| CN1909977A (en) * | 2004-01-16 | 2007-02-07 | 布鲁尔科技公司 | Spin-on protective coatings for wet-etch processing of microelectronic substrates |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0665321A (en) * | 1992-08-19 | 1994-03-08 | Kanegafuchi Chem Ind Co Ltd | Heat stabilizer and thermoplastic resin composition |
| CN1909977A (en) * | 2004-01-16 | 2007-02-07 | 布鲁尔科技公司 | Spin-on protective coatings for wet-etch processing of microelectronic substrates |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109988263A (en) * | 2019-04-02 | 2019-07-09 | 嘉兴华雯化工有限公司 | A kind of anhydride macromolecule chain extender and preparation method thereof |
| CN114806098A (en) * | 2021-01-22 | 2022-07-29 | 武汉顺威赛特工程塑料有限公司 | A kind of low warpage reinforced PBT material and preparation method thereof |
| CN115466350A (en) * | 2021-11-29 | 2022-12-13 | 上海涵点科技有限公司 | Reactive chain extender with high-activity groups and application thereof |
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Address after: No. 448, outer ring road, Jiaxing Port District, Jiaxing, Zhejiang Applicant after: Jiaxing Huawen Chemical Co., Ltd Address before: No. 448, outer ring road, Jiaxing Port District, Jiaxing, Zhejiang Applicant before: JIAXING HUAWEN CHEMICAL Co.,Ltd. |
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Application publication date: 20181228 |