CN116970117A - Preparation method and application of high-light-transmittance low-haze transparent copolymer material - Google Patents
Preparation method and application of high-light-transmittance low-haze transparent copolymer material Download PDFInfo
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- CN116970117A CN116970117A CN202310692317.5A CN202310692317A CN116970117A CN 116970117 A CN116970117 A CN 116970117A CN 202310692317 A CN202310692317 A CN 202310692317A CN 116970117 A CN116970117 A CN 116970117A
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- 229920001577 copolymer Polymers 0.000 title claims abstract description 43
- 239000000463 material Substances 0.000 title claims abstract description 42
- 238000002834 transmittance Methods 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- 238000010526 radical polymerization reaction Methods 0.000 claims abstract description 8
- 239000012780 transparent material Substances 0.000 claims abstract description 4
- 239000000178 monomer Substances 0.000 claims description 42
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 29
- 238000000034 method Methods 0.000 claims description 24
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 claims description 16
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- -1 acrylic ester Chemical class 0.000 claims description 10
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 6
- 239000012752 auxiliary agent Substances 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 239000007809 chemical reaction catalyst Substances 0.000 claims description 4
- 238000010924 continuous production Methods 0.000 claims description 4
- 238000009826 distribution Methods 0.000 claims description 4
- 239000003999 initiator Substances 0.000 claims description 4
- 230000009477 glass transition Effects 0.000 claims description 3
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 claims description 2
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 claims description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 claims description 2
- MPMBRWOOISTHJV-UHFFFAOYSA-N but-1-enylbenzene Chemical compound CCC=CC1=CC=CC=C1 MPMBRWOOISTHJV-UHFFFAOYSA-N 0.000 claims description 2
- 125000002924 primary amino group Chemical class [H]N([H])* 0.000 claims 1
- 239000002861 polymer material Substances 0.000 abstract description 11
- 239000000243 solution Substances 0.000 description 14
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 12
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 11
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 10
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- 239000000047 product Substances 0.000 description 8
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical group COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 7
- 238000001125 extrusion Methods 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 7
- 150000003141 primary amines Chemical class 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 239000011259 mixed solution Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- HIDBROSJWZYGSZ-UHFFFAOYSA-N 1-phenylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC=C1 HIDBROSJWZYGSZ-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 229920001897 terpolymer Polymers 0.000 description 4
- 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 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 239000012467 final product Substances 0.000 description 3
- WYKYCHHWIJXDAO-UHFFFAOYSA-N tert-butyl 2-ethylhexaneperoxoate Chemical group CCCCC(CC)C(=O)OOC(C)(C)C WYKYCHHWIJXDAO-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 2
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- RZXMPPFPUUCRFN-UHFFFAOYSA-N p-toluidine Chemical compound CC1=CC=C(N)C=C1 RZXMPPFPUUCRFN-UHFFFAOYSA-N 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 2
- 238000010557 suspension polymerization reaction Methods 0.000 description 2
- FVQMJJQUGGVLEP-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOOC(C)(C)C FVQMJJQUGGVLEP-UHFFFAOYSA-N 0.000 description 1
- BQTPKSBXMONSJI-UHFFFAOYSA-N 1-cyclohexylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1CCCCC1 BQTPKSBXMONSJI-UHFFFAOYSA-N 0.000 description 1
- DMWVYCCGCQPJEA-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane Chemical compound CC(C)(C)OOC(C)(C)CCC(C)(C)OOC(C)(C)C DMWVYCCGCQPJEA-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- AFBPFSWMIHJQDM-UHFFFAOYSA-N N-methyl-N-phenylamine Natural products CNC1=CC=CC=C1 AFBPFSWMIHJQDM-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- CHIHQLCVLOXUJW-UHFFFAOYSA-N benzoic anhydride Chemical compound C=1C=CC=CC=1C(=O)OC(=O)C1=CC=CC=C1 CHIHQLCVLOXUJW-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000003311 flocculating effect Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229940094933 n-dodecane Drugs 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- SWAXTRYEYUTSAP-UHFFFAOYSA-N tert-butyl ethaneperoxoate Chemical compound CC(=O)OOC(C)(C)C SWAXTRYEYUTSAP-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- GSECCTDWEGTEBD-UHFFFAOYSA-N tert-butylperoxycyclohexane Chemical compound CC(C)(C)OOC1CCCCC1 GSECCTDWEGTEBD-UHFFFAOYSA-N 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 238000004383 yellowing Methods 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
-
- 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
- C08F8/00—Chemical modification by after-treatment
- C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
- C08F8/32—Introducing nitrogen atoms or nitrogen-containing groups by reaction with amines
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The application relates to the field of transparent materials, in particular to a preparation method and application of a high-light-transmittance low-haze transparent copolymer material. The preparation method of the copolymer material comprises the following steps: (1) preparing a reaction material; (2) free radical polymerization; (3) imidization reaction. The preparation method of the transparent copolymer material with high light transmittance and low haze provided by the application adopts the imidization reaction of the continuous reaction, can effectively improve the transparency of the finally obtained product, and reduces the haze, so that the transparent copolymer material can be well applied to high transparent polymer materials, and the influence on the transparency and the haze of the polymer materials is avoided.
Description
Technical Field
The application relates to the field of transparent materials, in particular to a preparation method and application of a high-light-transmittance low-haze transparent copolymer material.
Background
As the application of polymer materials in the production and living of people is more and more widespread, the performance requirements for the polymer materials are gradually improved. The high-transparency polymer materials such as ABS and PMMA are widely used, and the use of heat-resistant agents is gradually increased along with the increase of the high-temperature application environments of the high-transparency polymer materials such as ABS and PMMA, and strict requirements on the heat-resistant agents in the high-transparency polymer materials on not affecting the transparency, haze, stability and good self-compatibility of the materials are met.
The existing heat-resistant agent of the high-transparency polymer is also usually made of transparent copolymer materials, and the preparation method of the copolymer materials is usually made of suspension polymerization, emulsion polymerization, solution polymerization and other methods, so that the process is not environment-friendly, meanwhile, the obtained product has more residues, the purity of the product is not high, excessive maleimide monomers are left, the product has high yellowness and high haze, and the use of the final product is greatly influenced. Chinese patent CN201810825402.3 provides a preparation method of a terpolymer heat-resistant agent, and the conventional preparation method is adopted, so that the properties of transparency, haze and the like of the finally obtained heat-resistant agent still have room for improvement.
Accordingly, in order to solve the above problems, the present application provides a method for preparing a transparent copolymer material having high light transmittance and low haze.
Disclosure of Invention
In order to solve the above problems, the first aspect of the present application provides a method for preparing a transparent copolymer material with high light transmittance and low haze, comprising the steps of: (1) preparing a reaction material; (2) free radical polymerization; (3) imidization reaction.
As a preferred embodiment, the reactor for radical polymerization is a full-mixing reactor or a tubular reactor.
As a preferred embodiment, the free radical polymerization and imidization steps are continuous process production processes.
As a preferred embodiment, the reaction mass comprises: styrene monomer, acrylic ester monomer, maleimide monomer, unsaturated carboxylic anhydride monomer, initiator, reaction catalyst, primary amine, auxiliary agent and solvent.
As a preferable scheme, the mass ratio of the styrene monomer, the acrylic ester monomer, the maleimide monomer and the unsaturated carboxylic anhydride monomer is 1-20: 10 to 70:0 to 50:1 to 10.
As a preferable scheme, the mass ratio of the styrene monomer, the acrylic ester monomer, the maleimide monomer and the unsaturated carboxylic anhydride monomer is 2-8: 15-25: 0 to 20:4 to 5.
As a preferable scheme, the mass ratio of the styrene monomer, the acrylic ester monomer, the maleimide monomer and the unsaturated carboxylic anhydride monomer is 2-5: 18 to 22:0 to 10:4 to 4.5.
As a preferable scheme, the mass ratio of the styrene monomer, the acrylic ester monomer, the maleimide monomer and the unsaturated carboxylic anhydride monomer is 3:19.5:0:4.2.
as a preferable embodiment, the styrene monomer is at least one of styrene, α -methylstyrene, p-methylstyrene, and ethylstyrene.
As a preferable embodiment, the styrene monomer is styrene.
As a preferred embodiment, the unsaturated carboxylic anhydride monomer is at least one of maleic anhydride and itaconic anhydride.
As a preferred embodiment, the unsaturated carboxylic anhydride monomer is maleic anhydride.
As a preferred embodiment, the acrylic monomer is methyl methacrylate.
As a preferable scheme, the maleimide monomer is at least one of N-phenylmaleimide and N-cyclohexylmaleimide.
As a preferred embodiment, the primary amine is at least one of aniline, cyclohexylamine, and p-toluidine.
As a preferred embodiment, the primary amine is aniline.
As a preferred embodiment, the initiator is at least one of benzoyl oxide, azobisisobutyronitrile, t-butyl peroxy-2-ethylhexanoate, 2, 5-dimethyl-2, 5-bis (t-butylperoxy) hexane, 1' -bis (t-butylperoxy) -3, 5-trimethylcyclohexane, di-t-butyl peroxide, t-butyl peroxy-2-ethylcarbonate, t-butyl peroxy acetate, 1-bis (t-butylperoxy) cyclohexane.
As a preferred embodiment, the initiator is tert-butyl peroxy-2-ethylhexanoate
As a preferable scheme, the reaction catalyst is at least one of triethylamine, tripropylamine and p-toluenesulfonic acid.
As a preferred embodiment, the reaction catalyst is triethylamine or p-toluenesulfonic acid.
As a preferred embodiment, the auxiliary agent is a molecular weight regulator.
As a preferable scheme, the solvent is at least one of ethylbenzene, toluene, butanone, methyl isobutyl ketone, cyclohexanone and propylene glycol methyl ether acetate.
As a preferred embodiment, when a fully hybrid reactor is used, the specific operation of step (2) is: adding a monomer solution obtained by mixing a styrene monomer, an acrylic ester monomer, a maleimide monomer, an unsaturated carboxylic anhydride monomer and a solvent into a fully-mixed reactor according to the addition speed of 8-10 parts/h and 1-1.2 parts/h, and continuously conveying the obtained polymerization solution into a double-screw extrusion devolatilizer at the speed of 9-11 parts/h after reacting for 2-10 hours at the temperature of 80-160 ℃ and keeping the same feeding speed in the process; the specific operation of the step (3) is as follows: and (3) feeding the mixed solution of primary amine, catalyst and auxiliary agent into a second section of cylinder of a double-screw extrusion devolatilizer at the speed of 0.5-1 part/h, wherein the extrusion temperature of the devolatilization extruder is 200-250 ℃, and the residence time is 8-12 min, and performing devolatilization and reaction to obtain the polymer which is the required copolymer.
As a preferred embodiment, when a tubular reactor is used, the specific operation of step (2) is: adding a monomer solution obtained by mixing a styrene monomer, an acrylic ester monomer, a maleimide monomer, an unsaturated carboxylic anhydride monomer and a solvent into a tubular reactor 1 according to the addition speed of 8-10 parts/h and 1-1.2 parts/h respectively, reacting for 2-10 hours at the temperature of 80-160 ℃, and continuously conveying the obtained polymerization solution into the tubular reactor 2 at the speed of 9-11 parts/h; the specific operation of the step (3) is as follows: and (2) feeding the mixed solution of primary amine, catalyst and auxiliary agent into a tubular reactor 2 at a speed of 0.8-1 part/h, wherein the reaction temperature in the tubular reactor 2 is 120-180 ℃ and the reaction time is 4-8 hours, and then conveying the polymerization solution into a double-screw extrusion devolatilizer for devolatilization, thus obtaining the polymer which is the required copolymer.
As a preferred embodiment, the transparent copolymer prepared has a glass transition temperature of 140 to 200 ℃.
As a preferred embodiment, the transparent copolymer prepared has a glass transition temperature of 160 to 190 ℃.
As a preferable embodiment, the molecular weight of the transparent copolymer obtained by the preparation is 50000-150000 and the molecular weight distribution is 1.5-2.5.
As a preferable embodiment, the molecular weight of the transparent copolymer obtained by the preparation is 80000-120000, and the molecular weight distribution is 2-2.5.
In the application, the imidization reaction of the continuous reaction can effectively improve the transparency of the final product and reduce the haze, so that the product can be well applied to high-transparency polymer materials, and the transparency and the color of the polymer materials are prevented from being influenced. The inventors consider that: the method for directly adding primary amine into the prepolymer system can directly promote the primary amine and unsaturated anhydride to directly generate imidization reaction in the main monomer prepolymer, and avoids the phenomenon that a great amount of maleimide monomer remains in the existing suspension polymerization, emulsion polymerization, solution polymerization and other methods through the continuous production process, thereby further avoiding the negative influence of the residual maleimide monomer on transparency, haze and color and avoiding yellowing of products.
The second aspect of the application provides an application of the preparation method of the high-light-transmittance low-haze transparent copolymer material, comprising an application of the preparation method in preparation of a ternary or multi-component copolymer transparent material.
The beneficial effects are that:
1. the preparation method of the transparent copolymer material with high light transmittance and low haze provided by the application can effectively obtain the ternary transparent polymer with low molecular weight distribution coefficient, is suitable for being used as a compatilizer of materials such as plastic alloy and the like, and can not influence the viscosity and other properties of the plastic alloy as much as possible.
2. The preparation method of the transparent copolymer material with high light transmittance and low haze solves the problem that the appearance of the corresponding terpolymer product produced by the prior art is too yellow and the appearance of the final product is influenced.
3. The preparation method of the transparent copolymer material with high light transmittance and low haze provided by the application adopts the imidization reaction of the continuous reaction, can effectively improve the transparency of the finally obtained product, and reduces the haze, so that the transparent copolymer material can be well applied to high transparent polymer materials, and the influence on the transparency and the haze of the polymer materials is avoided.
4. The preparation method of the transparent copolymer material with high light transmittance and low haze provided by the application has strong continuity, can discard the use of finished maleimide monomers and reduce the use amount of maleic anhydride, has fewer chemical reagent residues, and greatly reduces the production cost of the product.
5. The preparation method of the transparent copolymer material with high light transmittance and low haze provided by the application is environment-friendly, has low waste yield, does not influence the quality of reaction equipment due to the problems of monomer residue and the like, and prolongs the service life of the equipment.
Drawings
FIG. 1 is an infrared test spectrum of a styrene-methyl methacrylate-maleimide copolymer obtained in example 1 of the present application.
Detailed Description
Example 1
Example 1 provides a method for preparing a transparent copolymer material with high light transmittance and low haze, which comprises the following steps in parts by mass: (1) 4.2 parts of maleic anhydride, 3.0 parts of styrene, 19.5 parts of methyl methacrylate and 15 parts of butanone are added into a dissolution tank 1 and stirred until insoluble substances are absent; adding 0.03 part of tert-butyl peroxy-2-ethylhexanoate and 5 parts of butanone into a material mixing tank 2, and uniformly stirring; adding 4.0 parts of aniline and 0.15 part of p-toluenesulfonic acid into a material mixing tank 3, and uniformly mixing; (2) Continuously adding the materials in the dissolving tank 1 and the material preparing tank 2 into a full-mixing reactor at the speed of 8.93 parts per hour and 1.07 parts per hour respectively, wherein the temperature is 105 ℃, after the reaction time is 3 hours, continuously conveying the polymerization solution into a double-screw extrusion devolatilizer at the speed of 10 parts per hour, and keeping the same feeding speed in the process; (3) And (3) injecting the pre-mixed aniline and p-toluenesulfonic acid solution into a second barrel of a devolatilization extruder according to 0.85 part/h, wherein the extrusion temperature of the devolatilization extruder is 240 ℃, and the residence time is 8min, and performing devolatilization and reaction to obtain the polymer which is the required copolymer.
In this example, the free radical polymerization and imidization reaction steps are continuous process production processes
Example 2
Example 2 provides a method for preparing a transparent copolymer material with high light transmittance and low haze, which comprises the following steps in parts by mass: (1) 4.2 parts of maleic anhydride, 3.0 parts of styrene, 19.5 parts of methyl methacrylate and 15 parts of butanone are added into a dissolution tank 1 and stirred until the azophenylmaleimide is dissolved; adding 0.03 part of tert-butyl peroxy-2-ethylhexanoate and 5 parts of butanone into a material mixing tank 2, and uniformly stirring; 4.0 parts of aniline and 0.15 part of p-toluenesulfonic acid are added into a material mixing tank 3; (2) Mixing uniformly, then continuously adding the materials in the dissolution tank 1 and the dosing tank 2 into the tubular reactor 1 at the speed of 8.93 parts/h and 1.07 parts/h respectively, wherein the temperature is 105 ℃, the reaction time is 3h, and then conveying the polymerization solution into the tubular reactor 2 at the speed of 10 parts/h; (3) Meanwhile, injecting mixed solution of aniline and triethylamine at the inlet of a tubular reactor 2 at the speed of 0.85 part/h, wherein the reaction temperature of the tubular reactor 2 is 150 ℃ and the reaction time is 5h, and then conveying the polymerization solution into a double-screw extrusion devolatilizer for devolatilization, so as to obtain the polymer which is the required copolymer.
Comparative example 1
The weight portions are as follows: 200 parts of deionized water is injected into a reaction vessel, 2 parts of sodium dodecyl benzene sulfonate is added, then the reaction vessel is put into a constant-temperature water bath to be constant temperature to 30 ℃, and simultaneously nitrogen is introduced into a reaction light and stirred for 10 minutes until the sodium dodecyl benzene sulfonate is completely dissolved; weighing 72 parts of methyl methacrylate, 11 parts of styrene and 17 parts of N-phenylmaleimide to prepare a mixed solution; adding the prepared mixed solution into a reaction container, stirring quickly, then adding a potassium persulfate solution (comprising 0.25 part of potassium persulfate and 50 parts of water), heating to 75 ℃, reacting for 4 hours, cooling after the reaction is finished, adding 5 parts of antioxidant, continuing stirring for 20 minutes, discharging, flocculating, cooling, filtering, and drying to obtain the methyl methacrylate/styrene/N-phenyl maleimide terpolymer. (suspension method)
Comparative example 2
The weight portions are as follows: methyl methacrylate/styrene/N-phenylmaleimide terpolymer, the preparation raw materials comprise: 21.6 parts of methyl methacrylate, 3.3 parts of styrene, 0.004 part of azodiisobutyronitrile, 30 parts of butanone and 5.1 parts of maleimide (recrystallized twice from an aqueous ethanol solution (ethanol-water volume ratio 1:1)).
Mixing the preparation raw materials, stirring until all solids are completely dissolved, continuously adding the solution into a polymerization kettle for 5 hours at the reaction temperature of 60 ℃, continuously reacting for 2 hours after the addition is completed, taking out the reaction liquid, freezing the reaction liquid by liquid nitrogen, precipitating by methanol, and drying in vacuum until the weight is constant. (solution method)
Evaluation of Performance
Monomer residue test: test conditions: gas chromatography: shimadzu GC-2014; injection port temperature: 280 ℃ chromatographic column: micropolarity chromatographic column HP-5 temperature conditions: after 5 minutes at 80 ℃, the temperature was raised to 280 ℃ at 20 ℃/min and maintained at 280 ℃ for 10 minutes. A detector: FID, temperature 280 ℃.
The steps are as follows: 0.5g of the sample was dissolved in 5ml of a tetrahydrofuran solution containing 1% n-dodecane as an internal standard, then 5ml of n-hexane was added and shaken to precipitate out, the supernatant was taken and injected into GC, and the content of maleimide monomer was obtained by the coefficient of peak area with the internal standard, and the results are shown in Table 1.
Transparency and haze test: test methods referring to GB/T2410, 10 samples were tested for each comparative example, and the average of the measured values is reported in Table 1.
TABLE 1
Claims (10)
1. A preparation method of a transparent copolymer material with high light transmittance and low haze is characterized by comprising the following steps: the method comprises the following steps: (1) preparing a reaction material; (2) free radical polymerization; (3) imidization reaction.
2. The method for preparing a high light transmittance low haze transparent copolymer material according to claim 1, wherein: the reactor for free radical polymerization is a full-mixing reactor or a tubular reactor.
3. The method for preparing a high light transmittance low haze transparent copolymer material according to claim 2, wherein: the free radical polymerization and imidization reaction steps are continuous production processes.
4. The method for preparing a high light transmittance low haze transparent copolymer material according to claim 3, wherein: the reaction mass comprises: styrene monomer, acrylic ester monomer, maleimide monomer, unsaturated carboxylic anhydride monomer, initiator, reaction catalyst, primary amine, auxiliary agent and solvent.
5. The method for preparing a high light transmittance low haze transparent copolymer material according to claim 4, wherein: the mass ratio of the styrene monomer to the acrylic ester monomer to the maleimide monomer to the unsaturated carboxylic anhydride monomer is 1-20: 10 to 70:0 to 50:1 to 10.
6. The method for preparing a high light transmittance low haze transparent copolymer material according to claim 5, wherein: the styrene monomer is at least one of styrene, alpha-methyl styrene, p-methyl styrene and ethyl styrene.
7. The method for preparing a high light transmittance low haze transparent copolymer material according to claim 6, wherein: the unsaturated carboxylic anhydride monomer is at least one of maleic anhydride and itaconic anhydride.
8. The method for preparing a high light transmittance low haze transparent copolymer material according to claim 7, wherein: the glass transition temperature of the prepared transparent copolymer is 140-200 ℃.
9. The method for preparing a high light transmittance low haze transparent copolymer material according to claim 8, wherein: the molecular weight of the prepared transparent copolymer is 50000-150000, and the molecular weight distribution is 1.5-2.5.
10. Use of the method for preparing a high light transmittance low haze transparent copolymer material according to any one of claims 1 to 9, characterized in that: the preparation method is applied to the preparation of the ternary or multi-component copolymer transparent material.
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