CN116375361A - Active group-rich water-soluble resin film forming agent for glass fibers and preparation method thereof - Google Patents
Active group-rich water-soluble resin film forming agent for glass fibers and preparation method thereof Download PDFInfo
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- CN116375361A CN116375361A CN202310251279.XA CN202310251279A CN116375361A CN 116375361 A CN116375361 A CN 116375361A CN 202310251279 A CN202310251279 A CN 202310251279A CN 116375361 A CN116375361 A CN 116375361A
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- Prior art keywords
- forming agent
- water
- film forming
- monomer
- soluble resin
- Prior art date
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- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 155
- 239000003365 glass fiber Substances 0.000 title claims abstract description 113
- 239000011347 resin Substances 0.000 title claims abstract description 94
- 229920005989 resin Polymers 0.000 title claims abstract description 94
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000000178 monomer Substances 0.000 claims abstract description 109
- 238000006243 chemical reaction Methods 0.000 claims abstract description 72
- 239000002904 solvent Substances 0.000 claims abstract description 26
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 23
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 23
- 150000008064 anhydrides Chemical class 0.000 claims abstract description 18
- 230000004224 protection Effects 0.000 claims abstract description 11
- 239000000853 adhesive Substances 0.000 claims abstract description 7
- 230000001070 adhesive effect Effects 0.000 claims abstract description 7
- 239000003999 initiator Substances 0.000 claims description 77
- 238000000034 method Methods 0.000 claims description 60
- 230000008569 process Effects 0.000 claims description 53
- 238000006386 neutralization reaction Methods 0.000 claims description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 33
- 238000006116 polymerization reaction Methods 0.000 claims description 28
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 27
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 26
- 238000002156 mixing Methods 0.000 claims description 25
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 24
- 239000007864 aqueous solution Substances 0.000 claims description 23
- 239000011259 mixed solution Substances 0.000 claims description 23
- 239000003513 alkali Substances 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 21
- 239000007800 oxidant agent Substances 0.000 claims description 19
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 238000004513 sizing Methods 0.000 claims description 18
- 239000003638 chemical reducing agent Substances 0.000 claims description 17
- -1 amine compounds Chemical class 0.000 claims description 16
- 230000001590 oxidative effect Effects 0.000 claims description 15
- 238000004321 preservation Methods 0.000 claims description 15
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 14
- KDSNLYIMUZNERS-UHFFFAOYSA-N 2-methylpropanamine Chemical compound CC(C)CN KDSNLYIMUZNERS-UHFFFAOYSA-N 0.000 claims description 14
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 14
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 14
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 claims description 14
- 239000002994 raw material Substances 0.000 claims description 14
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 13
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 13
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 13
- 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 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 12
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 12
- 238000010528 free radical solution polymerization reaction Methods 0.000 claims description 12
- 230000000977 initiatory effect Effects 0.000 claims description 12
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 12
- 230000003472 neutralizing effect Effects 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 12
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 12
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims description 12
- 230000009471 action Effects 0.000 claims description 10
- 239000007789 gas Substances 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 230000001681 protective effect Effects 0.000 claims description 10
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 9
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 9
- 239000007822 coupling agent Substances 0.000 claims description 9
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 8
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 8
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 8
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 8
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 claims description 8
- 229940001584 sodium metabisulfite Drugs 0.000 claims description 8
- 235000010262 sodium metabisulphite Nutrition 0.000 claims description 8
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims description 7
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 7
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 claims description 7
- 239000003431 cross linking reagent Substances 0.000 claims description 7
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 7
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 7
- 239000000314 lubricant Substances 0.000 claims description 7
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 7
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 7
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 claims description 7
- BHRZNVHARXXAHW-UHFFFAOYSA-N sec-butylamine Chemical compound CCC(C)N BHRZNVHARXXAHW-UHFFFAOYSA-N 0.000 claims description 7
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 6
- 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 6
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 claims description 6
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-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 6
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 6
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 6
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 6
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 6
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 claims description 6
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 6
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 6
- 239000002585 base Substances 0.000 claims description 6
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 6
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 6
- 239000011976 maleic acid Substances 0.000 claims description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 6
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 claims description 6
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 6
- 235000010265 sodium sulphite Nutrition 0.000 claims description 6
- MNCGMVDMOKPCSQ-UHFFFAOYSA-M sodium;2-phenylethenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C=CC1=CC=CC=C1 MNCGMVDMOKPCSQ-UHFFFAOYSA-M 0.000 claims description 6
- BWYYYTVSBPRQCN-UHFFFAOYSA-M sodium;ethenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C=C BWYYYTVSBPRQCN-UHFFFAOYSA-M 0.000 claims description 6
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- 150000008065 acid anhydrides Chemical class 0.000 claims description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 5
- 239000004677 Nylon Substances 0.000 abstract description 17
- 229920001778 nylon Polymers 0.000 abstract description 17
- 150000001875 compounds Chemical class 0.000 abstract description 11
- 239000011159 matrix material Substances 0.000 abstract description 8
- 230000003014 reinforcing effect Effects 0.000 abstract description 6
- 150000001735 carboxylic acids Chemical class 0.000 abstract 1
- 239000002131 composite material Substances 0.000 description 21
- 238000005303 weighing Methods 0.000 description 17
- 238000012360 testing method Methods 0.000 description 9
- 206010020112 Hirsutism Diseases 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 8
- 230000006641 stabilisation Effects 0.000 description 8
- 238000011105 stabilization Methods 0.000 description 8
- 238000001816 cooling Methods 0.000 description 7
- 238000012545 processing Methods 0.000 description 7
- 230000032683 aging Effects 0.000 description 6
- 150000001412 amines Chemical class 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000007599 discharging Methods 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 238000005491 wire drawing Methods 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 230000001276 controlling effect Effects 0.000 description 4
- 238000007380 fibre production Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229920006254 polymer film Polymers 0.000 description 4
- 238000009835 boiling Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 230000006750 UV protection Effects 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000011152 fibreglass Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000011534 incubation Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920006264 polyurethane film Polymers 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 229940079827 sodium hydrogen sulfite Drugs 0.000 description 2
- 229940001482 sodium sulfite Drugs 0.000 description 2
- 239000000057 synthetic resin Substances 0.000 description 2
- 229920003002 synthetic resin Polymers 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 239000000805 composite resin Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000012681 fiber drawing Methods 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229940100528 polyoxyl 8 stearate Drugs 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000011208 reinforced composite material Substances 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
- C03C25/10—Coating
- C03C25/24—Coatings containing organic materials
- C03C25/26—Macromolecular compounds or prepolymers
- C03C25/28—Macromolecular compounds or prepolymers obtained by reactions involving only carbon-to-carbon unsaturated bonds
-
- 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
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Reinforced Plastic Materials (AREA)
- Surface Treatment Of Glass Fibres Or Filaments (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention provides a water-soluble resin film forming agent for glass fibers, which comprises, by mass, 15-55 parts of acrylic acid, 1-20 parts of unsaturated carboxylic acid containing double bonds and/or unsaturated anhydride containing double bonds, 1-10 parts of cohesive monomer, 1-10 parts of adhesive monomer, 1-10 parts of functional monomer and 40-80 parts of solvent. The film forming agent is applied as a film forming agent in a glass fiber impregnating compound, is particularly suitable for reinforcing the glass fiber film forming agent for nylon resin, provides good protection for glass fibers in a glass fiber preparation process, and can be combined with related active groups in the impregnating compound and matrix resin in a reaction way.
Description
Technical Field
The invention belongs to the technical field of film forming agents for glass fibers, relates to a water-soluble resin film forming agent for glass fibers, a preparation method and application thereof, and a sizing agent for glass fibers, and particularly relates to a water-soluble resin film forming agent rich in active groups for glass fibers, a preparation method and application thereof, and a sizing agent for glass fibers.
Background
In the technical field of glass fiber manufacturing, the sizing agent is extremely important for the production and application of glass fibers. Firstly, in the glass fiber drawing process, the sizing agent plays a role in lubrication, adhesion and protection, so that the phenomenon that the drawing operation cannot be performed due to broken filaments and flying filaments caused by serious abrasion of glass fibers is avoided; second, the sizing imparts the technical properties necessary for various processing techniques of the fiberglass product and the fiberglass reinforcement, such as mechanical properties, penetration, saturation, stiffness, cutting, dispersion, antistatic properties, banding, flowability, and the like. Therefore, the technical level of the sizing agent is one of the preconditions for the development of the glass fiber industry and the glass fiber reinforced composite material industry, and the maximum use amount of the film forming agent in the sizing agent formula often plays a decisive role in the performance of the sizing agent and is the most critical component in the sizing agent.
Nylon is commonly called polyamide, PA for short, is a resin material general term for repeated amide groups, and comprises aliphatic, aliphatic-aromatic and aromatic polyamides, and is mainly prepared by polycondensation of dibasic acid and diamine or amino acid. The nylon resin has higher tensile strength and good impact toughness, and has wider temperature application range. Glass fiber reinforced PA composite materials are commonly used in industry, and have the characteristics of lower density, low price and recycling, and meanwhile, the modified composite materials have the advantages of higher mechanical property, hardness, load deformation temperature, better dimensional stability and the like. The glass fiber reinforced nylon resin used is generally of two types, namely long glass fiber reinforced and chopped glass fiber reinforced.
However, the hydrolysis resistance, ageing resistance and thermo-oxidative resistance of the glass fiber reinforced PA composite material need to be further improved, and the service life of the composite material is relatively short. The glass fiber reinforced PA composite material is also limited to be applied to working conditions such as high temperature, high humidity, sun, rain, etc., such as automobile parts, radiator tanks, engine hoods, air inlet pipes, high-speed rail clips, insulating gauge blocks, etc.
Therefore, taking the technical problems of glass fiber processability and PA composite material performance enhancement as a starting point, how to develop a special film forming agent for the glass fiber impregnating compound for reinforcing PA, solves the problems of the prior glass fiber reinforced PA composite material, and further improves the performance and service life of the composite material, thereby widening the application depth and width of the glass fiber reinforced PA composite material, having great significance and being one of the problems of a plurality of first-line researchers in the industry.
Disclosure of Invention
In view of the above, the technical problem to be solved by the invention is to provide a water-soluble resin film-forming agent for glass fibers, a preparation method and application thereof, a sizing agent for glass fibers, and particularly a water-soluble resin film-forming agent rich in active groups for glass fibers. The water-soluble resin film forming agent provided by the invention can provide the required bundling property of glass fibers, low hairiness and other processing performances, and on the other hand, endows the glass fibers with good compatibility with nylon resin.
The invention provides a water-soluble resin film forming agent for glass fibers, which comprises the following raw materials in parts by mass:
and (3) an alkaline neutralizer.
Preferably, the double bond-containing unsaturated carboxylic acid comprises one or more of methacrylic acid, itaconic acid and maleic acid;
the unsaturated acid anhydride containing double bonds comprises maleic anhydride;
the cohesive monomer comprises one or more of vinyl acetate, methyl acrylate and methyl methacrylate;
the viscous monomer comprises one or more of butyl acrylate, 2-ethylhexyl acrylate and isooctyl acrylate;
the weight average molecular weight of the water-soluble resin film forming agent is 1000-200000.
Preferably, the functional monomer comprises one or more of hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, glycidyl acrylate, glycidyl methacrylate, N-methylolacrylamide, sodium vinylsulfonate and sodium styrenesulfonate;
the alkaline neutralizer comprises one or more of sodium hydroxide, ammonia water and organic amine compounds;
the organic amine compound comprises one or more of diethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, sec-butylamine, ethanolamine, diethanolamine and triethanolamine;
The dosage of the alkaline neutralizer is controlled to be 2 to 7.5 of the pH value of the system.
Preferably, the solvent comprises one or more of water, methanol, ethanol, propanol, isopropanol, butanol and isobutanol;
the water-soluble resin film forming agent is a water-soluble resin film forming agent rich in active groups;
the raw materials also comprise an initiator;
the water-soluble resin film forming agent is prepared from raw materials through a solution polymerization process under the conditions of nitrogen protection, heating and stirring;
the solution polymerization process includes a pre-polymerization base neutralization process or a post-polymerization base neutralization process.
The invention provides a preparation method of the water-soluble resin film forming agent for glass fiber, which is characterized by comprising a pre-polymerization alkali neutralization process or a post-polymerization alkali neutralization process;
the pre-polymerization alkali neutralization process comprises the following steps:
1) Mixing acrylic acid, unsaturated carboxylic acid containing double bonds and/or unsaturated anhydride containing double bonds, cohesive monomer, viscous monomer and functional monomer, and then adding an alkaline neutralizer for mixing and dissolving to obtain a mixed solution;
2) Under the action of protective gas, adding an initiator aqueous solution and a mixed solution into a solvent for reaction at a reaction temperature, and then carrying out heat preservation reaction to obtain a water-soluble resin film forming agent;
The post-polymerization alkali neutralization process comprises the following steps:
(1) Mixing acrylic acid, unsaturated carboxylic acid containing double bonds and/or unsaturated anhydride containing double bonds, cohesive monomer, viscous monomer and functional monomer to obtain a mixed solution;
(2) Under the action of protective gas, adding an initiator aqueous solution and a mixed solution into a solvent at a reaction temperature, reacting, and then carrying out heat preservation reaction to obtain an intermediate system;
(3) And adding an alkaline neutralizer into the intermediate system obtained in the step to neutralize, thereby obtaining the water-soluble resin film forming agent.
Preferably, the specific mode of adding the alkaline neutralizing agent in the step 1) and the step (3) is selected from the group consisting of slowly adding the alkaline neutralizing agent and stirring while adding until the alkaline neutralizing agent and the alkaline neutralizing agent are completely mutually dissolved;
the temperature of the miscibility in the step 1) is less than or equal to 40 ℃;
in the initiator aqueous solution, the mass ratio of water to the initiator is (10-100): 1, a step of;
the mode of adding the initiator aqueous solution and the mixed solution into the solvent comprises dropwise adding;
the dripping time is 1-6 hours.
Preferably, the reaction temperature is 65-95 ℃;
the temperature of the heat preservation reaction is 85-95 ℃;
the time of the heat preservation reaction is 0.5-2 hours;
the temperature of the intermediate system is less than or equal to 60 ℃;
The pH value of the neutralization is controlled to be 2-7.5.
Preferably, the initiator comprises a thermal initiation system initiator or a redox system initiator;
the thermal initiation system initiator accounts for 0.05-5% of the mass of the monomer;
the thermal initiation system initiator comprises one or more of ammonium persulfate, potassium persulfate, sodium persulfate, benzoyl peroxide, dicumyl peroxide, azobisisobutyronitrile and azobisisoheptonitrile;
the redox system initiator accounts for 0.05-5% of the mass of the monomer;
the redox system initiator includes an oxidizing agent and a reducing agent;
the molar ratio of the oxidant to the reducing agent is 1: (0.5-1);
the oxidant comprises one or more of ammonium persulfate, potassium persulfate, sodium persulfate, hydrogen peroxide and tert-butyl hydroperoxide;
the reducing agent comprises one or more of sodium sulfite, sodium bisulfite, sodium metabisulfite and sodium formaldehyde sulfoxylate;
the monomers include acrylic acid, double bond-containing unsaturated carboxylic acid and/or double bond-containing unsaturated anhydride, cohesive monomer, adhesive monomer and functional monomer.
The invention provides the application of the water-soluble resin film forming agent in glass fiber treatment, wherein the water-soluble resin film forming agent is prepared by any one of the technical schemes or the preparation method is used for preparing the water-soluble resin film forming agent in glass fiber treatment.
The invention also provides a sizing agent for glass fibers, which comprises a film forming agent, a coupling agent, a second film forming agent, a crosslinking agent and a lubricant;
the film forming agent comprises the water-soluble resin film forming agent according to any one of the technical schemes or the water-soluble resin film forming agent prepared by the preparation method according to any one of the technical schemes.
The invention provides a water-soluble resin film forming agent for glass fibers, which comprises, by mass, 15-55 parts of acrylic acid, 1-20 parts of unsaturated carboxylic acid containing double bonds and/or unsaturated anhydride containing double bonds, 1-10 parts of cohesive monomer, 1-10 parts of adhesive monomer, 1-10 parts of functional monomer and 40-80 parts of solvent. Compared with the prior art, the film forming agent is prepared by taking the carboxylic acid monomer containing unsaturated double bonds as a main monomer through a solution polymerization process. On one hand, the high molecular polymer is uniform in film formation after drying and water loss, and the processing performance requirement of glass fiber on the film forming agent can be fully met after the molecular weight is controlled and the modified monomer is added for copolymerization through the synthesis process; on the other hand, the unsaturated double bond carboxylic acid monomer can provide a large number of active groups with strong polarity and reactivity for the film forming agent, which is favorable for providing bridging of reaction for the coupling agent and the film forming agent, thereby greatly improving the performance of the composite material; on the other hand, a certain hydrophilic functional group is endowed to the polymer film forming agent, and an ionic hydrophilic structure can be formed in water after the polymer film forming agent reacts with an alkaline neutralizer, so that the film forming agent is endowed with good water solubility, and the film forming agent is uniformly coated on the surface of the glass fiber and is environment-friendly.
The water-soluble resin film forming agent with rich active groups for glass fibers can provide the required bundling property, low hairiness and other processing performances for the glass fibers, and on the other hand, the glass fibers and nylon resin are endowed with good compatibility. The invention is especially suitable for reinforcing glass fiber main (or auxiliary) film forming agent for nylon resin, can be used as a special impregnating agent for coating glass fiber to improve the surface property of glass fiber when being compounded with other components in the impregnating agent, is especially suitable for reinforcing glass fiber film forming agent for nylon resin, provides good protection for glass fiber in glass fiber preparation process, and can react and combine rich active groups with relevant active groups in the impregnating agent and matrix resin, and the prepared glass fiber has good interface strength with various matrix resins, and has good mechanical property, water resistance, ultraviolet aging resistance and thermal oxidation resistance.
Experimental results show that the active group-rich water-soluble resin film forming agent provided by the invention is used together with other impregnating agent components such as a coupling agent, a second film forming agent, a crosslinking agent, a lubricant and the like, so that the glass fiber-rich water-soluble resin film forming agent has the advantages of stable wire drawing operation, good glass fiber coating effect, smooth glass fiber production, good chopping property, fluidity, small hairiness and the like in the glass fiber manufacturing process. And the prepared glass fiber has good compatibility and interface strength with composite matrix resin, and the prepared composite material has excellent mechanical properties, and the spline tensile strength, the bending strength and the impact strength are obviously improved compared with the conventional impregnating compound formula, so that the water boiling resistance, the ultraviolet resistance test and the thermal oxidation resistance are improved.
Detailed Description
For a further understanding of the present invention, preferred embodiments of the invention are described below in conjunction with the examples, but it should be understood that these descriptions are merely intended to illustrate further features and advantages of the invention and are not limiting of the invention claims.
All the raw materials of the present invention are not particularly limited in their sources, and may be purchased on the market or prepared according to conventional methods well known to those skilled in the art.
All raw materials of the invention are not particularly limited in purity, and the invention preferably adopts analytical purity or purity requirements conventional in the field of glass fiber film forming agent preparation.
All raw materials of the invention, the brands and abbreviations of which belong to the conventional brands and abbreviations in the field of the related application are clear and definite, and the person skilled in the art can purchase from the market or prepare by the conventional method according to the brands, abbreviations and the corresponding application.
The invention provides a water-soluble resin film forming agent for glass fibers, which comprises the following raw materials in parts by mass:
and (3) an alkaline neutralizer.
In the present invention, the acrylic acid is added in an amount of 15 to 55 parts by weight, preferably 20 to 50 parts by weight, more preferably 25 to 45 parts by weight, still more preferably 30 to 40 parts by weight.
In the present invention, the double bond-containing unsaturated carboxylic acid and/or double bond-containing unsaturated acid anhydride is added in an amount of 1 to 20 parts by weight, may be 5 to 16 parts by weight, and is preferably 9 to 12 parts by weight.
In the present invention, the cohesive monomer may be added in an amount of 1 to 10 parts by weight, may be 3 to 8 parts by weight, and preferably 5 to 6 parts by weight.
In the present invention, the adhesive monomer is added in an amount of 1 to 10 parts by weight, may be 3 to 8 parts by weight, and is preferably 5 to 6 parts by weight.
In the present invention, the functional monomer is added in an amount of 1 to 10 parts by weight, preferably 3 to 8 parts by weight, more preferably 5 to 6 parts by weight.
In the present invention, the solvent may be added in an amount of 40 to 80 parts by weight, preferably 45 to 75 parts by weight, more preferably 50 to 70 parts by weight, and still more preferably 55 to 65 parts by weight.
In the present invention, the double bond-containing unsaturated carboxylic acid preferably includes one or more of methacrylic acid, itaconic acid, and maleic acid, more preferably methacrylic acid, itaconic acid, or maleic acid.
In the present invention, the double bond-containing unsaturated acid anhydride preferably includes maleic anhydride.
In the present invention, the cohesive monomer preferably includes one or more of vinyl acetate, methyl acrylate and methyl methacrylate, more preferably vinyl acetate, methyl acrylate or methyl methacrylate.
In the present invention, the adhesive monomer preferably includes one or more of butyl acrylate, 2-ethylhexyl acrylate and isooctyl acrylate, more preferably butyl acrylate, 2-ethylhexyl acrylate or isooctyl acrylate.
In the present invention, the weight average molecular weight of the water-soluble resin film-forming agent is preferably 1000 to 200000, more preferably 5000 to 160000, and still more preferably 9000 to 120000.
In the present invention, the functional monomer preferably includes one or more of hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, glycidyl acrylate, glycidyl methacrylate, N-methylolacrylamide, sodium vinylsulfonate, and sodium styrene sulfonate, more preferably hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, glycidyl acrylate, glycidyl methacrylate, N-methylolacrylamide, sodium vinylsulfonate, or sodium styrene sulfonate.
In the present invention, the alkaline neutralizing agent preferably includes one or more of sodium hydroxide, ammonia and an organic amine compound, more preferably sodium hydroxide, ammonia or an organic amine compound.
In the present invention, the organic amine compound preferably includes a fatty amine compound and/or an alcohol amine compound, more preferably a fatty amine compound or an alcohol amine compound. The organic amine compound preferably comprises one or more of diethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, sec-butylamine, ethanolamine, diethanolamine and triethanolamine, more preferably diethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, sec-butylamine, ethanolamine, diethanolamine or triethanolamine. In particular, the fatty amine compound preferably includes one or more of diethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine and sec-butylamine. The alcohol amine compound preferably comprises one or more of ethanolamine, diethanolamine and triethanolamine
In the present invention, the amount of the alkaline neutralizing agent is preferably 2 to 7.5, more preferably 3 to 6.5, and still more preferably 3.5 to 5.5, as the pH of the control system.
In the present invention, the solvent preferably includes one or more of water, methanol, ethanol, propanol, isopropanol, butanol and isobutanol, more preferably water, methanol, ethanol, propanol, isopropanol, butanol or isobutanol.
In the present invention, the water-soluble resin film-forming agent is preferably a water-soluble resin film-forming agent rich in active groups.
In the present invention, the raw materials further preferably include an initiator.
In the invention, the water-soluble resin film forming agent is preferably prepared from raw materials through a solution polymerization process under the conditions of nitrogen protection, heating and stirring.
In the present invention, the solution polymerization process preferably includes a pre-polymerization base neutralization process or a post-polymerization base neutralization process.
The invention provides a preparation method of the water-soluble resin film forming agent for glass fiber, which is characterized by comprising a pre-polymerization alkali neutralization process or a post-polymerization alkali neutralization process;
the pre-polymerization alkali neutralization process comprises the following steps:
1) Mixing acrylic acid, unsaturated carboxylic acid containing double bonds and/or unsaturated anhydride containing double bonds, cohesive monomer, viscous monomer and functional monomer, and then adding an alkaline neutralizer for mixing and dissolving to obtain a mixed solution;
2) Under the action of protective gas, adding an initiator aqueous solution and a mixed solution into a solvent for reaction at a reaction temperature, and then carrying out heat preservation reaction to obtain a water-soluble resin film forming agent;
the post-polymerization alkali neutralization process comprises the following steps:
(1) Mixing acrylic acid, unsaturated carboxylic acid containing double bonds and/or unsaturated anhydride containing double bonds, cohesive monomer, viscous monomer and functional monomer to obtain a mixed solution;
(2) Under the action of protective gas, adding an initiator aqueous solution and a mixed solution into a solvent at a reaction temperature, reacting, and then carrying out heat preservation reaction to obtain an intermediate system;
(3) And adding an alkaline neutralizer into the intermediate system obtained in the step to neutralize, thereby obtaining the water-soluble resin film forming agent.
In the present invention, the pre-polymerization alkali neutralization process comprises the steps of:
1) Mixing acrylic acid, unsaturated carboxylic acid containing double bonds and/or unsaturated anhydride containing double bonds, cohesive monomer, viscous monomer and functional monomer, and then adding an alkaline neutralizer for mixing and dissolving to obtain a mixed solution;
2) Under the action of protective gas, adding the initiator aqueous solution and the mixed solution into a solvent for reaction at the reaction temperature, and then carrying out heat preservation reaction to obtain the water-soluble resin film forming agent.
The invention firstly mixes acrylic acid, unsaturated carboxylic acid containing double bonds and/or unsaturated anhydride containing double bonds, cohesive monomer, viscous monomer and functional monomer, and then adds alkaline neutralizer for mixing and dissolving to obtain mixed solution.
In the present invention, the specific mode of adding the alkaline neutralizing agent in the step 1) and the step (3) is preferably selected from the group consisting of slowly adding the alkaline neutralizing agent while stirring until the alkaline neutralizing agent is completely dissolved in each other.
In the present invention, the temperature of the miscibility in the step 1) is preferably 40 ℃ or lower, more preferably 35 ℃ or lower, and still more preferably 30 ℃ or lower.
In the present invention, the above-mentioned pre-polymerization alkali neutralization process, although it is a pre-polymerization alkali neutralization process, is characterized in that the pH value of the product after the completion of the reaction is controlled.
Under the action of protective gas, the initiator aqueous solution and the mixed solution are added into a solvent for reaction at the reaction temperature, and the water-soluble resin film forming agent is obtained after the heat preservation reaction.
In the invention, in the aqueous initiator solution, the mass ratio of water to the initiator is preferably (10 to 100): 1, more preferably (30 to 80): 1, more preferably (50 to 60): 1.
in the present invention, the means for adding the aqueous initiator solution and the mixed solution to the solvent preferably includes dropping.
In the present invention, the time for the dropping is preferably 1 to 6 hours, more preferably 2 to 5 hours, and still more preferably 3 to 4 hours.
In the present invention, the reaction temperature is preferably 65 to 95 ℃, more preferably 70 to 90 ℃, and still more preferably 75 to 85 ℃.
In the present invention, the temperature of the incubation reaction is preferably 85 to 95 ℃, more preferably 87 to 93 ℃, and still more preferably 89 to 91 ℃.
In the present invention, the time for the incubation reaction is preferably 0.5 to 2 hours, more preferably 0.8 to 1.7 hours, and still more preferably 1.1 to 1.4 hours.
In the present invention, the post-polymerization alkali neutralization process comprises the steps of:
(1) Mixing acrylic acid, unsaturated carboxylic acid containing double bonds and/or unsaturated anhydride containing double bonds, cohesive monomer, viscous monomer and functional monomer to obtain a mixed solution;
(2) Under the action of protective gas, adding an initiator aqueous solution and a mixed solution into a solvent at a reaction temperature, reacting, and then carrying out heat preservation reaction to obtain an intermediate system;
(3) And adding an alkaline neutralizer into the intermediate system obtained in the step to neutralize, thereby obtaining the water-soluble resin film forming agent.
The invention firstly mixes acrylic acid, unsaturated carboxylic acid containing double bonds and/or unsaturated anhydride containing double bonds, cohesive monomer, viscous monomer and functional monomer to obtain mixed solution.
Under the action of protective gas, the initiator aqueous solution and the mixed solution are added into a solvent at the reaction temperature to react, and then the intermediate system is obtained after the heat preservation reaction.
In the present invention, the temperature of the intermediate system is preferably 60 ℃ or lower, more preferably 55 ℃ or lower, and still more preferably 50 ℃ or lower.
In the present invention, the pH of the neutralization is preferably controlled to 2 to 7.5, more preferably 3 to 6.5, and still more preferably 4 to 5.5.
In the present invention, the initiator preferably includes a thermal initiation system initiator or a redox system initiator.
In the present invention, the thermal initiation system initiator preferably accounts for 0.05 to 5% of the mass of the monomer, more preferably 0.5 to 4%, still more preferably 1 to 3%, still more preferably 1.5 to 2%.
In the present invention, the thermal initiator preferably includes one or more of ammonium persulfate, potassium persulfate, sodium persulfate, benzoyl peroxide, dicumyl peroxide, azobisisobutyronitrile and azobisisoheptonitrile, more preferably ammonium persulfate, potassium persulfate, sodium persulfate, benzoyl peroxide, dicumyl peroxide, azobisisobutyronitrile or azobisisoheptonitrile.
In the present invention, the redox system initiator preferably accounts for 0.05 to 5% of the mass of the monomer, more preferably 0.5 to 4%, still more preferably 1 to 3%, still more preferably 1.5 to 2%.
In the present invention, the redox system initiator preferably includes an oxidizing agent and a reducing agent.
In the present invention, the molar ratio of the oxidizing agent to the reducing agent is preferably 1: (0.5 to 1), more preferably 1: (0.6 to 0.9), more preferably 1: (0.7-0.8).
In the present invention, the oxidizing agent preferably includes one or more of ammonium persulfate, potassium persulfate, sodium persulfate, hydrogen peroxide, and t-butyl hydroperoxide, more preferably ammonium persulfate, potassium persulfate, sodium persulfate, hydrogen peroxide, or t-butyl hydroperoxide.
In the present invention, the reducing agent preferably includes one or more of sodium sulfite, sodium hydrogen sulfite, sodium metabisulfite and sodium formaldehyde sulfoxylate, more preferably sodium sulfite, sodium hydrogen sulfite, sodium metabisulfite or sodium formaldehyde sulfoxylate.
In the present invention, the monomer preferably includes acrylic acid, double bond-containing unsaturated carboxylic acid and/or double bond-containing unsaturated acid anhydride, cohesive monomer, adhesive monomer, and functional monomer.
And finally, adding an alkaline neutralizer into the intermediate system obtained in the step to neutralize to obtain the water-soluble resin film forming agent.
The invention provides the application of the water-soluble resin film forming agent in glass fiber treatment, wherein the water-soluble resin film forming agent is prepared by any one of the technical schemes or the preparation method is used for preparing the water-soluble resin film forming agent in glass fiber treatment.
In the present invention, the glass fiber treatment preferably includes a treatment for improving the surface properties of the glass fiber.
In the present invention, the application preferably includes an application in the preparation process of a glass fiber reinforced PA (nylon) composite material.
The invention provides a sizing agent for glass fibers, which comprises a film forming agent, a coupling agent, a second film forming agent, a crosslinking agent and a lubricant;
the film forming agent comprises the water-soluble resin film forming agent according to any one of the technical schemes or the water-soluble resin film forming agent prepared by the preparation method according to any one of the technical schemes.
The invention is a complete and refined integral technical scheme, better ensures the components and performance of the film forming agent, further improves the compatibility of glass fiber and nylon resin in the glass fiber composite material and the mechanical property of the composite material performance, and the water-soluble resin film forming agent rich in active groups for the glass fiber and the preparation method thereof specifically comprise the following steps:
The preparation method of the active group-rich water-soluble resin film forming agent for glass fibers comprises the following steps:
the comonomer is prepared by a solution polymerization process under the conditions of initiator, nitrogen protection, heating and stirring, and the mass ratio of raw materials of the synthetic resin formula is as follows:
component A: acrylic acid 15% -55%;
component B: 1-20% of unsaturated carboxylic acid (anhydride) containing double bonds, including one or more of methacrylic acid, itaconic acid, maleic anhydride and maleic acid.
Component C: 1-10% of cohesive monomer, which comprises one or more of vinyl acetate, methyl acrylate and methyl methacrylate.
Component D: 1-10% of viscous monomer, which comprises one or more of butyl acrylate, 2-ethylhexyl acrylate and isooctyl acrylate.
Component E: 0.1 to 6 percent of functional monomer, and one or more of hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, glycidyl acrylate, glycidyl methacrylate, N-methylolacrylamide, sodium vinylsulfonate and sodium styrenesulfonate.
Component F: the dosage of the alkaline neutralizer is controlled to be pH 2-7.5 of the system, and the alkaline neutralizer comprises one or more of sodium hydroxide, ammonia water and organic amine.
Component G: 40% -80% of solvent, including one or more of water, methanol, ethanol, propanol, isopropanol, butanol and isobutanol.
Specifically, the solution polymerization process may be selected in one of two ways:
(1) Pre-polymerization alkali neutralization process
S1, respectively weighing monomers according to a proportion, mixing and mutually dissolving, weighing an alkaline neutralizer according to a proportion, slowly adding the alkaline neutralizer into the mixed monomers, stirring the alkaline neutralizer while adding the alkaline neutralizer until the alkaline neutralizer is completely mutually dissolved, and controlling the temperature of a system to be lower than 40 ℃ in the process of mixing and dissolving;
s2, preparing an initiator into an initiator aqueous solution according to a proportion, wherein the mass ratio of water to the initiator is 10:1-100:1;
s3, adding a proportioning solvent into a reaction kettle according to the proportion, introducing nitrogen, stirring and heating to the reaction temperature, dropwise adding the mixed monomer prepared in the step S1 and an initiator for reaction, wherein the dropwise adding time is 1-6 hours, the reaction temperature is 65-95 ℃, the temperature is kept for reaction for 0.5-2 hours after the dropwise adding is finished, and the product is obtained through cooling, discharging and filtering.
(2) Post-polymerization alkali neutralization process
S1, weighing monomers according to a proportion, and mixing and mutually dissolving;
s2, preparing an initiator into an initiator aqueous solution according to a proportion, wherein the mass ratio of water to the initiator is 10:1-100:1;
s3, adding a proportioning solvent into a reaction kettle according to the proportion, introducing nitrogen, stirring and heating to the reaction temperature, dropwise adding the mixed monomer prepared in the step S1 and an initiator for reaction, wherein the dropwise adding time is 1-6 hours, the reaction temperature is 65-95 ℃, and after dropwise adding, the temperature is 85-95, the reaction is kept for 0.5-2 hours, and the temperature is reduced to below 60 ℃;
S4: and (3) weighing the alkaline neutralizer according to the weight, slowly adding the alkaline neutralizer into a reaction kettle for neutralization, stirring the alkaline neutralizer while adding the alkaline neutralizer until the alkaline neutralizer is completely dissolved with each other, cooling, discharging and filtering to obtain a product.
Specifically, the initiator is selected according to two initiation modes:
(1) The thermal initiation system is adopted, and the initiator accounts for 0.05-5% of the mass ratio of the monomer and comprises one or more of ammonium persulfate, potassium persulfate, sodium persulfate, benzoyl peroxide, dicumyl peroxide, azobisisobutyronitrile and azobisisoheptonitrile.
(2) Or a redox system can be adopted, and the initiator is used by combining more than one oxidant and more than one reducing agent, wherein the oxidant accounts for 0.05-5% of the mass of the monomer, and the mol ratio of the oxidant to the reducing agent is 1:1-1:0.5. The oxidant comprises one or more of ammonium persulfate, potassium persulfate, sodium persulfate, hydrogen peroxide and tert-butyl hydroperoxide; the reducing agent comprises one or more of sodium sulfite, sodium bisulfite, sodium metabisulfite and sodium formaldehyde sulfoxylate (sodium metabisulfite). The oxidant and the reducing agent are separately configured and separately added dropwise.
Specifically, the organic amine in the alkaline neutralizer is as follows: wherein the fatty amine comprises diethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, sec-butylamine and the like, and the alcohol amine comprises one or more of ethanolamine, diethanolamine, triethanolamine and the like.
Specifically, the weight average molecular weight of the water-soluble resin is 1000-200000.
Further:
the comonomer is prepared by a solution polymerization process under the conditions of initiator, nitrogen protection, heating and stirring, and the synthesis preparation method can adopt a pre-polymerization alkali neutralization process or a post-polymerization alkali neutralization process, and is concretely as follows:
(1) Pre-polymerization alkali neutralization process
S1, respectively weighing monomers according to a proportion, mixing and mutually dissolving, weighing an alkaline neutralizer according to a proportion, slowly adding the alkaline neutralizer into the mixed monomers, stirring the alkaline neutralizer while adding the alkaline neutralizer until the alkaline neutralizer is completely mutually dissolved, and controlling the temperature of a system to be lower than 40 ℃ in the process of mixing and dissolving;
s2, preparing an initiator into an initiator aqueous solution according to a proportion, wherein the mass ratio of water to the initiator is 10:1-100:1;
s3, adding a proportioning solvent into a reaction kettle according to the proportion, introducing nitrogen, stirring and heating to the reaction temperature, dropwise adding the mixed monomer prepared in the step S1 and an initiator for reaction, wherein the dropwise adding time is 1-6 hours, the reaction temperature is 65-95 ℃, the temperature is kept for reaction for 0.5-2 hours after the dropwise adding is finished, and the product is obtained through cooling, discharging and filtering.
(2) Post-polymerization alkali neutralization process
S1, weighing monomers according to a proportion, and mixing and mutually dissolving;
s2, preparing an initiator into an initiator aqueous solution according to a proportion, wherein the mass ratio of water to the initiator is 10:1-100:1;
S3, adding a proportioning solvent into a reaction kettle according to the proportion, introducing nitrogen, stirring and heating to the reaction temperature, dropwise adding the mixed monomer prepared in the step S1 and an initiator for reaction, wherein the dropwise adding time is 1-6 hours, the reaction temperature is 65-95 ℃, and after dropwise adding, the temperature is 85-95, the reaction is kept for 0.5-2 hours, and the temperature is reduced to below 60 ℃;
s4: and (3) weighing the alkaline neutralizer according to the weight, slowly adding the alkaline neutralizer into a reaction kettle for neutralization, stirring the alkaline neutralizer while adding the alkaline neutralizer until the alkaline neutralizer is completely dissolved with each other, cooling, discharging and filtering to obtain a product.
In the synthesis process, the raw materials of the synthetic resin formula are as follows in mass ratio:
component A: acrylic acid 15-55%. The acrylic acid is used as a main monomer of the invention, can provide excellent synthesis stability, meets the design performance requirement of the film forming agent, and has low relative cost.
Component B: 1-20% of unsaturated carboxylic acid (anhydride) containing double bonds, including one or more of methacrylic acid, itaconic acid, maleic anhydride and maleic acid. By introducing different unsaturated carboxylic acid (anhydride) monomers containing double bonds, the carboxylic acid density in the molecular structure of the polymer can be adjusted in a wider range, and meanwhile, the molecular weight, film forming performance and glass fiber performance of the high polymer are provided with larger optimization adjusting space, so that the application range of the series film forming agent is widened.
Component C: 1-10% of cohesive monomer, which comprises one or more of vinyl acetate, methyl acrylate and methyl methacrylate. The introduction of the monomer can adjust the film-forming mechanical property of the polymer in a certain range, and endow the glass fiber with necessary processing property.
Component D: 1-10% of viscous monomer, which comprises one or more of butyl acrylate, 2-ethylhexyl acrylate and isooctyl acrylate. The monomer is introduced, so that the bundling performance of the film forming agent on glass fibers can be improved, the hardness of the film forming agent and glass fiber yarns can be regulated, and the chopping performance can be improved.
Component E: 0.1 to 6 percent of functional monomer, and one or more of hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, glycidyl acrylate, glycidyl methacrylate, N-methylolacrylamide, sodium vinylsulfonate and sodium styrenesulfonate. The introduction of the functional monomer can endow the film forming agent with more crosslinking property, improve the specific mechanical properties of the film forming agent and glass fiber yarns, and simultaneously, part of the functional monomer can further regulate the water-soluble property of the high molecular polymer.
Component F: the dosage of the alkaline neutralizer is controlled to be 2 to 7.5 of the PH value of the system, and the alkaline neutralizer comprises one or more of sodium hydroxide, ammonia water and organic amine. The organic amines in the alkaline neutralizer are: wherein the fatty amine comprises diethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, sec-butylamine and the like, and the alcohol amine comprises one or more of ethanolamine, diethanolamine, triethanolamine and the like.
Component G: and the solvent is 40-80 percent and comprises one or more of deionized water, methanol, ethanol, propanol, isopropanol, butanol and isobutanol.
The water-soluble resin prepared by the process and the formula has the synthetic molecular weight controlled between 1000 and 200000. Too low a molecular weight, poor film forming properties; the molecular weight is too high, the water solubility of the resin is poor, the viscosity of the aqueous solution is too high or the agglomeration gel is easy to occur in the synthesis process.
In the solution polymerization process, the initiator can be selected from one of the following two initiation modes:
(1) Adopts a thermal initiation system: the initiator accounts for 0.05 to 5 percent of the mass of the monomer and comprises one or more of ammonium persulfate, potassium persulfate, sodium persulfate, benzoyl peroxide, dicumyl peroxide, azobisisobutyronitrile and azobisisoheptonitrile.
(2) Redox systems may also be employed: the initiator is used by combining more than one oxidant and more than one reducing agent, wherein the oxidant accounts for 0.05-5% of the mass of the monomer, and the mol ratio of the oxidant to the reducing agent is 1:1-1:0.5. The oxidant comprises one or more of ammonium persulfate, potassium persulfate, sodium persulfate, hydrogen peroxide and tert-butyl hydroperoxide; the reducing agent comprises one or more of sodium sulfite, sodium bisulfite, sodium metabisulfite and sodium formaldehyde sulfoxylate (sodium metabisulfite). The oxidant and the reducing agent are separately configured and separately added dropwise.
The invention provides the active group-rich water-soluble resin film forming agent for the glass fiber, and the preparation method and the application thereof, and the impregnating compound for the glass fiber. The invention takes carboxylic acid monomer containing unsaturated double bond as main monomer, and prepares the film forming agent through solution polymerization technology. On one hand, the high molecular polymer is uniform in film formation after drying and water loss, and the processing performance requirement of glass fiber on the film forming agent can be fully met after the molecular weight is controlled and the modified monomer is added for copolymerization through the synthesis process; on the other hand, the unsaturated double bond carboxylic acid monomer can provide a large number of active groups with strong polarity and reactivity for the film forming agent, which is favorable for providing bridging of reaction for the coupling agent and the film forming agent, thereby greatly improving the performance of the composite material; on the other hand, a certain hydrophilic functional group is endowed to the polymer film forming agent, and an ionic hydrophilic structure can be formed in water after the polymer film forming agent reacts with an alkaline neutralizer, so that the film forming agent is endowed with good water solubility, and the film forming agent is uniformly coated on the surface of the glass fiber and is environment-friendly.
The water-soluble resin film forming agent with rich active groups for glass fibers can provide the required bundling property, low hairiness and other processing performances for the glass fibers, and on the other hand, the glass fibers and nylon resin are endowed with good compatibility. The invention is especially suitable for reinforcing glass fiber main (or auxiliary) film forming agent for nylon resin, can be used as a special impregnating agent for coating glass fiber to improve the surface property of glass fiber when being compounded with other components in the impregnating agent, is especially suitable for reinforcing glass fiber film forming agent for nylon resin, provides good protection for glass fiber in glass fiber preparation process, and can react and combine rich active groups with relevant active groups in the impregnating agent and matrix resin, and the prepared glass fiber has good interface strength with various matrix resins, and has good mechanical property, water resistance, ultraviolet aging resistance and thermal oxidation resistance.
Experimental results show that the active group-rich water-soluble resin film forming agent provided by the invention is used together with other impregnating agent components such as a coupling agent, a second film forming agent, a crosslinking agent, a lubricant and the like, so that the glass fiber-rich water-soluble resin film forming agent has the advantages of stable wire drawing operation, good glass fiber coating effect, smooth glass fiber production, good chopping property, fluidity, small hairiness and the like in the glass fiber manufacturing process. And the prepared glass fiber has good compatibility and interface strength with composite matrix resin, and the prepared composite material has excellent mechanical properties, and the spline tensile strength, the bending strength and the impact strength are obviously improved compared with the conventional impregnating compound formula, so that the water boiling resistance, the ultraviolet resistance test and the thermal oxidation resistance are improved.
For further explanation of the present invention, the following describes a water-soluble resin film forming agent for glass fiber, its preparation method, application, and a sizing agent for glass fiber in detail with reference to examples, but it should be understood that these examples are implemented on the premise of the technical solution of the present invention, and detailed embodiments and specific operation procedures are given only for further explanation of the features and advantages of the present invention, and not for limitation of the claims of the present invention, and the scope of protection of the present invention is not limited to the examples described below.
Example 1
Step 1: respectively weighing 200g of acrylic acid, 100g of methacrylic acid, 15g of methyl acrylate, 20g of butyl acrylate and 10g of glycidyl acrylate, mixing and dissolving, weighing 45g of 25% ammonia water of an alkaline neutralizer according to a proportion, slowly adding the mixture into a mixed monomer, stirring the mixture while adding until the mixture is completely dissolved, and controlling the temperature of a system to be lower than 40 ℃ in the process of mixing and dissolving;
step 2: weighing 7g of initiator ammonium persulfate dissolved in water to prepare 100g of initiator aqueous solution;
step 3: 510g of deionized water is added into a reaction kettle, nitrogen is introduced, the temperature is raised to the reaction temperature of 80 ℃ by stirring, the mixed monomer prepared in the step 1 and the initiator solution in the step 2 are dripped for 2 hours, the reaction temperature of 80+/-2 ℃, the temperature is kept for 1 hour after dripping, the reaction is carried out at 90+/-2 ℃, the temperature is reduced, the material is discharged and filtered, and the solid content is 36.3%.
Example 2
Step 1: respectively weighing 240g of acrylic acid, 60g of methacrylic acid, 40g of itaconic acid, 30g of vinyl acetate, 20g of butyl acrylate and 10g of hydroxyethyl acrylate, mixing and dissolving, weighing 50g of alkaline neutralizer isopropylamine according to a proportion, slowly adding into a mixed monomer, stirring while adding until the mixture is completely dissolved, and controlling the temperature of a system to be lower than 40 ℃ in the process of mixing and dissolving;
Step 2: weighing 10g of t-butyl hydroperoxide as an initiator, dissolving 10g of t-butyl hydroperoxide in water to prepare 100g of oxidation initiator aqueous solution, and weighing 7.5g of white suspending block in water to prepare 100g of reduction initiator aqueous solution;
step 3: 350g of deionized water is added into a reaction kettle, nitrogen is introduced, the temperature is raised to 75 ℃, the mixed monomer prepared in the step 1 and the initiator solution in the step 2 are dropwise added for reaction, the dropwise adding time is 3 hours, the reaction temperature is 75+/-2 ℃, the temperature is kept at 90+/-2 ℃ after the dropwise adding is finished for reaction for 1 hour, the product is obtained through cooling, discharging and filtering, and the solid content is 46.5%.
Example 3
Step 1, respectively weighing 170g of acrylic acid, 30g of methacrylic acid, 20g of vinyl acetate, 20g of butyl acrylate, 10g of glycidyl methacrylate and 5g of hydroxyethyl acrylate, mixing and dissolving to form a mixed monomer;
step 2, weighing 12.5g of initiator sodium persulfate dissolved in water to prepare 100g of initiator aqueous solution;
adding 400g of deionized water, 200g of isopropanol and 20g of maleic anhydride into a reaction kettle, introducing nitrogen, stirring and heating to 85 ℃ (maleic anhydride is dissolved in the process), then dropwise adding the mixed monomer prepared in the step 1 and the initiator solution in the step 2 for reaction for 4 hours, wherein the reaction temperature is 85+/-2 ℃, and after dropwise adding, keeping the temperature for reaction for 1 hour at 90+/-2 ℃;
Step 4: slowly dropwise adding diethylamine to adjust the pH of the system to 3-4 under the stirring state of cooling to below 60 ℃ after heat preservation, cooling, discharging and filtering to obtain the product, wherein the solid content of the resin is 35.5%.
The glass fiber rich active group water-soluble resin film forming agent 6.0%, polyurethane film forming agent 6.0%, coupling agent 0.95% (gamma-aminopropyl triethoxysilane), lubricant 0.05% (polyethylene glycol 400 monostearate), cross-linking agent 1%, deionized water 86.0% prepared according to the invention are prepared into the impregnating compound according to the general method of industry.
Meanwhile, the comparative example is that the film forming agent only uses 12 percent of polyurethane film forming agent to prepare the impregnating compound, and other impregnating compound components are the same.
The 4 groups of impregnating compounds are applied to the production of glass fibers, the corresponding glass fibers are dried and chopped to prepare chopped strand products, and meanwhile, the wire drawing process, hairiness, fluidity and chopped performance in the glass fiber production process are evaluated. And then carrying out melt blending and granulation on the corresponding chopped glass fiber product and nylon resin by a double-screw extrusion process to prepare glass fiber reinforced nylon resin granules, preparing a composite material test spline by an injection molding process, and carrying out comprehensive evaluation on composite material performance by adopting the following evaluation method:
(1) Tensile strength and modulus were measured using ISO527 test standard;
(2) Flexural strength and modulus were measured using ISO178 test standard;
(3) Impact strength was measured using the ISO179Charpy test standard;
(4) Boiling conditions: in water: the ratio of glycol is 1:1, and the retention rate of the tensile strength of the sample bar is tested after the sample bar is boiled for 48 hours at the temperature of 120 ℃;
(5) Ultraviolet light aging conditions: testing the retention rate of the tensile strength of the sample bar after the light wavelength is 50nm and the temperature is 50 ℃ and irradiation is carried out for 480 hours;
(6) Thermal oxidative aging test conditions: the retention of tensile strength of the bars was tested after aging for 480 hours at 150 ℃.
Referring to table 1, table 1 shows the comparative test results of the production process for preparing glass fiber reinforced nylon resin according to the examples and comparative examples provided by the present invention.
TABLE 1
| Film forming agent | Impregnating compound | Wire drawing operation | Oiling rate m/min | Hairiness g/coil | Chopping property | Fluidity of the product |
| Example 1 | Stabilization | Stabilization | 20 | 0.08 | Good quality | Good quality |
| Example 2 | Stabilization | Stabilization | 20 | 0.09 | Good quality | Good quality |
| Example 3 | Stabilization | Stabilization | 20 | 0.08 | Good quality | Good quality |
| Comparative example | Stabilization | Stabilization | 20 | 0.13 | Good quality | Good quality |
Referring to table 2, table 2 shows the comparative performance test results of glass fiber reinforced nylon resin composite materials prepared in examples and comparative examples provided by the present invention.
TABLE 2
From the results, the active group-rich water-soluble resin film forming agent for glass fibers can be used with other sizing agent components such as a coupling agent, a second film forming agent, a crosslinking agent, a lubricant and the like to prepare sizing agents with good compounding performance. The film forming agent has the advantages of stable wiredrawing operation, good glass fiber coating effect, smooth glass fiber production, good chopping property, fluidity, small hairiness and the like in use. And the prepared glass fiber and composite matrix resin have good compatibility, interface strength and mechanical property.
The present invention has been described in detail with respect to a reactive group-rich water-soluble resin film forming agent for glass fibers, a method of preparing the same, applications thereof, a sizing agent for glass fibers, and specific examples of which are provided herein to illustrate the principles and embodiments of the invention and to assist in understanding the methods of the invention and its core ideas, including the best mode, and to also enable any person skilled in the art to practice the invention, including making and using any devices or systems, and performing any incorporated methods. It should be noted that it will be apparent to those skilled in the art that various modifications and adaptations of the invention can be made without departing from the principles of the invention and these modifications and adaptations are intended to be within the scope of the invention as defined in the following claims. The scope of the patent protection is defined by the claims and may include other embodiments that occur to those skilled in the art. Such other embodiments are intended to be within the scope of the claims if they have structural elements that do not differ from the literal language of the claims, or if they include equivalent structural elements with insubstantial differences from the literal language of the claims.
Claims (10)
1. The water-soluble resin film forming agent for the glass fiber is characterized by comprising the following raw materials in parts by mass:
15-55 parts by weight of acrylic acid;
1-20 parts by weight of unsaturated carboxylic acid containing double bonds and/or unsaturated anhydride containing double bonds;
1-10 parts by weight of cohesive monomer;
1-10 parts by weight of a viscous monomer;
1-10 parts by weight of functional monomer;
40-80 parts by weight of a solvent;
and (3) an alkaline neutralizer.
2. The water-soluble resin film-forming agent according to claim 1, wherein the double bond-containing unsaturated carboxylic acid comprises one or more of methacrylic acid, itaconic acid, and maleic acid;
the unsaturated acid anhydride containing double bonds comprises maleic anhydride;
the cohesive monomer comprises one or more of vinyl acetate, methyl acrylate and methyl methacrylate;
the viscous monomer comprises one or more of butyl acrylate, 2-ethylhexyl acrylate and isooctyl acrylate;
the weight average molecular weight of the water-soluble resin film forming agent is 1000-200000.
3. The water-soluble resin film-forming agent according to claim 1, wherein the functional monomer comprises one or more of hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, glycidyl acrylate, glycidyl methacrylate, N-methylolacrylamide, sodium vinylsulfonate, and sodium styrenesulfonate;
The alkaline neutralizer comprises one or more of sodium hydroxide, ammonia water and organic amine compounds;
the organic amine compound comprises one or more of diethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, sec-butylamine, ethanolamine, diethanolamine and triethanolamine;
the dosage of the alkaline neutralizer is controlled to be 2 to 7.5 of the pH value of the system.
4. The water-soluble resin film-forming agent of claim 1, wherein the solvent comprises one or more of water, methanol, ethanol, propanol, isopropanol, butanol, and isobutanol;
the water-soluble resin film forming agent is a water-soluble resin film forming agent rich in active groups;
the raw materials also comprise an initiator;
the water-soluble resin film forming agent is prepared from raw materials through a solution polymerization process under the conditions of nitrogen protection, heating and stirring;
the solution polymerization process includes a pre-polymerization base neutralization process or a post-polymerization base neutralization process.
5. A method for producing the water-soluble resin film-forming agent for glass fibers according to any one of claims 1 to 4, wherein the production method comprises a pre-polymerization alkali neutralization process or a post-polymerization alkali neutralization process;
The pre-polymerization alkali neutralization process comprises the following steps:
1) Mixing acrylic acid, unsaturated carboxylic acid containing double bonds and/or unsaturated anhydride containing double bonds, cohesive monomer, viscous monomer and functional monomer, and then adding an alkaline neutralizer for mixing and dissolving to obtain a mixed solution;
2) Under the action of protective gas, adding an initiator aqueous solution and a mixed solution into a solvent for reaction at a reaction temperature, and then carrying out heat preservation reaction to obtain a water-soluble resin film forming agent;
the post-polymerization alkali neutralization process comprises the following steps:
(1) Mixing acrylic acid, unsaturated carboxylic acid containing double bonds and/or unsaturated anhydride containing double bonds, cohesive monomer, viscous monomer and functional monomer to obtain a mixed solution;
(2) Under the action of protective gas, adding an initiator aqueous solution and a mixed solution into a solvent at a reaction temperature, reacting, and then carrying out heat preservation reaction to obtain an intermediate system;
(3) And adding an alkaline neutralizer into the intermediate system obtained in the step to neutralize, thereby obtaining the water-soluble resin film forming agent.
6. The preparation method according to claim 5, wherein the specific mode of adding the alkaline neutralizing agent in the step 1) and the step (3) is selected from the group consisting of slowly adding the alkaline neutralizing agent while stirring until the alkaline neutralizing agent is completely dissolved;
The temperature of the miscibility in the step 1) is less than or equal to 40 ℃;
in the initiator aqueous solution, the mass ratio of water to the initiator is (10-100): 1, a step of;
the mode of adding the initiator aqueous solution and the mixed solution into the solvent comprises dropwise adding;
the dripping time is 1-6 hours.
7. The method according to claim 5, wherein the reaction temperature is 65 to 95 ℃;
the temperature of the heat preservation reaction is 85-95 ℃;
the time of the heat preservation reaction is 0.5-2 hours;
the temperature of the intermediate system is less than or equal to 60 ℃;
the pH value of the neutralization is controlled to be 2-7.5.
8. The method of claim 5, wherein the initiator comprises a thermal initiation system initiator or a redox system initiator;
the thermal initiation system initiator accounts for 0.05-5% of the mass of the monomer;
the thermal initiation system initiator comprises one or more of ammonium persulfate, potassium persulfate, sodium persulfate, benzoyl peroxide, dicumyl peroxide, azobisisobutyronitrile and azobisisoheptonitrile;
the redox system initiator accounts for 0.05-5% of the mass of the monomer;
the redox system initiator includes an oxidizing agent and a reducing agent;
The molar ratio of the oxidant to the reducing agent is 1: (0.5-1);
the oxidant comprises one or more of ammonium persulfate, potassium persulfate, sodium persulfate, hydrogen peroxide and tert-butyl hydroperoxide;
the reducing agent comprises one or more of sodium sulfite, sodium bisulfite, sodium metabisulfite and sodium formaldehyde sulfoxylate;
the monomers include acrylic acid, double bond-containing unsaturated carboxylic acid and/or double bond-containing unsaturated anhydride, cohesive monomer, adhesive monomer and functional monomer.
9. Use of the water-soluble resin film-forming agent according to any one of claims 1 to 4 or the water-soluble resin film-forming agent prepared by the preparation method according to any one of claims 5 to 8 in glass fiber treatment.
10. A sizing agent for glass fibers, characterized in that the sizing agent comprises a film forming agent, a coupling agent, a second film forming agent, a crosslinking agent and a lubricant;
the film forming agent comprises the water-soluble resin film forming agent according to any one of claims 1 to 4 or the water-soluble resin film forming agent prepared by the preparation method according to any one of claims 5 to 8.
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