CN103289068B - The preparation method of glycerin modification unsaturated polyester resin - Google Patents
The preparation method of glycerin modification unsaturated polyester resin Download PDFInfo
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- CN103289068B CN103289068B CN201310190280.2A CN201310190280A CN103289068B CN 103289068 B CN103289068 B CN 103289068B CN 201310190280 A CN201310190280 A CN 201310190280A CN 103289068 B CN103289068 B CN 103289068B
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- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 title claims abstract description 78
- 235000011187 glycerol Nutrition 0.000 title claims abstract description 39
- 229920006337 unsaturated polyester resin Polymers 0.000 title claims abstract description 33
- 230000004048 modification Effects 0.000 title claims abstract description 25
- 238000012986 modification Methods 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 33
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- 238000004132 cross linking Methods 0.000 claims abstract description 5
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 68
- 239000002253 acid Substances 0.000 claims description 38
- 238000009413 insulation Methods 0.000 claims description 29
- 238000010792 warming Methods 0.000 claims description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- 239000000463 material Substances 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 15
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 14
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 12
- 239000003112 inhibitor Substances 0.000 claims description 12
- 230000003647 oxidation Effects 0.000 claims description 12
- 238000007254 oxidation reaction Methods 0.000 claims description 12
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 239000002994 raw material Substances 0.000 claims description 9
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 8
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 8
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 8
- 229960000583 acetic acid Drugs 0.000 claims description 7
- 239000012362 glacial acetic acid Substances 0.000 claims description 7
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 claims description 6
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 6
- 150000001991 dicarboxylic acids Chemical class 0.000 claims description 6
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 6
- JFCQEDHGNNZCLN-UHFFFAOYSA-N glutaric acid Chemical compound OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 claims description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 6
- 239000000178 monomer Substances 0.000 claims description 6
- 150000007518 monoprotic acids Chemical class 0.000 claims description 6
- 229920006395 saturated elastomer Polymers 0.000 claims description 6
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 claims description 6
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 claims description 5
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 5
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 claims description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 4
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 4
- NPAIMXWXWPJRES-UHFFFAOYSA-N butyltin(3+) Chemical compound CCCC[Sn+3] NPAIMXWXWPJRES-UHFFFAOYSA-N 0.000 claims description 4
- 239000001530 fumaric acid Substances 0.000 claims description 4
- 229940051250 hexylene glycol Drugs 0.000 claims description 4
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 4
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 4
- 239000011976 maleic acid Substances 0.000 claims description 4
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims description 3
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 claims description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 3
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 claims description 3
- XZKRXPZXQLARHH-UHFFFAOYSA-N buta-1,3-dienylbenzene Chemical compound C=CC=CC1=CC=CC=C1 XZKRXPZXQLARHH-UHFFFAOYSA-N 0.000 claims description 3
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 3
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 claims description 3
- 235000019253 formic acid Nutrition 0.000 claims description 3
- NWVVVBRKAWDGAB-UHFFFAOYSA-N hydroquinone methyl ether Natural products COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 claims description 3
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 3
- 235000019260 propionic acid Nutrition 0.000 claims description 3
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 3
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 3
- XRCRJFOGPCJKPF-UHFFFAOYSA-N 2-butylbenzene-1,4-diol Chemical compound CCCCC1=CC(O)=CC=C1O XRCRJFOGPCJKPF-UHFFFAOYSA-N 0.000 claims description 2
- 229930185605 Bisphenol Natural products 0.000 claims description 2
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 2
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 2
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 238000000034 method Methods 0.000 abstract description 5
- 230000035484 reaction time Effects 0.000 abstract description 5
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 238000003860 storage Methods 0.000 abstract description 3
- 239000002699 waste material Substances 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 229920005989 resin Polymers 0.000 description 8
- 239000011347 resin Substances 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 5
- -1 titanate ester Chemical class 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 3
- 229920006305 unsaturated polyester Polymers 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 2
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000002928 artificial marble Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 description 1
- 239000001639 calcium acetate Substances 0.000 description 1
- 235000011092 calcium acetate Nutrition 0.000 description 1
- 229960005147 calcium acetate Drugs 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- JEHCHYAKAXDFKV-UHFFFAOYSA-J lead tetraacetate Chemical compound CC(=O)O[Pb](OC(C)=O)(OC(C)=O)OC(C)=O JEHCHYAKAXDFKV-UHFFFAOYSA-J 0.000 description 1
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 description 1
- 229940071125 manganese acetate Drugs 0.000 description 1
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical group [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- ANOBYBYXJXCGBS-UHFFFAOYSA-L stannous fluoride Chemical compound F[Sn]F ANOBYBYXJXCGBS-UHFFFAOYSA-L 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
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- Macromonomer-Based Addition Polymer (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The present invention relates to a kind of preparation method of unsaturated polyester resin, particularly relate to a kind of preparation method of glycerin modification unsaturated polyester resin.The present invention includes polycondensation and crosslinking reaction, in polycondensation, add organic tin catalyzer.The present invention adopts organic tin catalyzer to shorten the reaction times, adds storage cycle.This invention synthesis technique is simple, and with short production cycle, excellent product performance, environmental protection produces without " three wastes ".
Description
Technical field
The present invention relates to a kind of preparation method of unsaturated polyester resin, particularly relate to a kind of preparation method of glycerin modification unsaturated polyester resin.
Background technology
Unsaturated polyester resin is generated through polycondensation by unsaturated dibasic acid, monounsaturated dicarboxylic acid, dibasic alcohol, owing to containing unsaturated double-bond in molecular resin chain, therefore can with double bond containing monomer, as the reaction such as vinylbenzene, vinyl toluene generates 3-D solid structure, form insoluble not molten thermosetting resin.But unsaturated polyester generally also exists poor toughness, the slightly shortcoming such as not high.And flexible unsaturated polyester resin is a special kinds in unsaturated polyester resin, can in self-vulcanizing, after solidification, snappiness is good, is widely used in the techniques such as the wood-imitated products such as furniture, floor and artificial marble.
In conventional synthesis technique, use a large amount of polyvalent alcohols can cause the problems such as wayward, the later stage easy gel of reaction.Glycerine is modal one in polyvalent alcohol, and market value is also lower, the dibasic alcohol that the glycerine fictitious hosts utilizing price more cheap is higher, can the overall production cost reducing unsaturated polyester resin, can ensure again the better quality of unsaturated polyester simultaneously.But the waste material produced in the production process of glycerin modification unsaturated polyester resin and waste water have certain pollution to environment, and the production cycle is also long.
Summary of the invention
The object of this invention is to provide a kind of preparation method of glycerin modification unsaturated polyester resin, this method reduce production cost, shorten the production cycle, environmentally safe.
The preparation method of glycerin modification unsaturated polyester resin of the present invention, comprises polycondensation and crosslinking reaction, adds organic tin catalyzer in polycondensation.
Raw materials by weight portion is counted:
Described organic tin catalyzer is the one in dibutyl tin, stannous octoate or Mono-n-butyltin.
Described saturated monoprotic acid is one or both in phenylformic acid, Glacial acetic acid, formic acid or propionic acid.
Described monounsaturated dicarboxylic acid is one or more in Tetra hydro Phthalic anhydride, m-phthalic acid, succinic acid, pentanedioic acid or hexanodioic acid.
Described unsaturated dibasic acid is the one in maleic acid, MALEIC ANHYDRIDE or FUMARIC ACID TECH GRADE.
Described dibasic alcohol is one or both in ethylene glycol, propylene glycol, butyleneglycol, glycol ether, dipropylene glycol, neopentyl glycol or hexylene glycol.
Described oxidation inhibitor is ditertbutylparacresol, methylene radical bis-phenol, antioxidant 1010, one or both in irgasfos 168.
Described stopper is one or both in Resorcinol, methyl hydroquinone, p-ten.-butylcatechol, Tert. Butyl Hydroquinone or para benzoquinone.
Described crosslinkable monomers is the one in vinylbenzene, Vinylstyrene, chloro-styrene, methyl methacrylate, butyl acrylate or Phthalic acid, diallyl ester.
The preparation method of glycerin modification unsaturated polyester resin of the present invention, its concrete steps are as follows:
(1) polycondensation: under high pure nitrogen protection, glycerine, dibasic alcohol, monounsaturated dicarboxylic acid, saturated monoprotic acid, oxidation inhibitor and organic tin catalyzer are dropped in the reactor with thermometer, agitator, condenser, stir, be warming up to material water outlet, at 160-180 DEG C of insulation 0.5-1.5 hour; After insulation terminates, be warming up to 200-210 DEG C until acid number drops to below 20mgKOH/g, be then cooled to 155-165 DEG C and drop into unsaturated dibasic acid, be warming up to material water outlet, at 160-180 DEG C of insulation 0.5-1.5 hour; After insulation terminates, be warming up to 200-210 DEG C until acid number drops to below 58mgKOH/g, under vacuum tightness-0.07--0.098MPa, polycondensation is to acid number lower than 40mgKOH/g, is cooled to 180 DEG C and adds stopper;
(2) crosslinking reaction: be cooled to 120-130 DEG C and add crosslinkable monomers, namely obtains product glycerin modification unsaturated polyester resin after stirring.
The present invention's glycerine carrys out modified unsaturated polyester resin, substantially increases the snappiness of resin, meanwhile, adds saturated monoprotic acid and comes to carry out polycondensation with glycerine, prevent from occurring gel in reaction process, and increase the shelf-time of resin in the present invention.
The conventional catalyst adopted during unsaturated polyester resin synthesis is titanate ester catalyzer and acetate catalyst, wherein titanate ester catalyzer is metatitanic acid four methyl esters, tetrabutyl titanate or titanium isopropylate, and acetate type catalyzer is manganese acetate, zinc acetate, Cobaltous diacetate, calcium acetate, Lithium Acetate or plumbic acetate.Compared with conventional catalyst, high, the easy completion of cure of unsaturated polyester reactive behavior of the catalyst preparing that the present invention adopts, cost is low, resin cured matter good toughness, heat release slowly, Heat stability is good, overcome titanium compound resins act when being subject to the weather such as ambient conditions such as summer high temperature simultaneously and go out storage cycle and to shorten phenomenon.
The resin reaction time of employing conventional catalyst and organic tin catalyzer and other performance comparison are as following table:
Beneficial effect of the present invention is as follows:
Compared with prior art, the present invention adopts organic tin catalyzer to shorten the reaction times, adds storage cycle.This invention synthesis technique is simple, and with short production cycle, excellent product performance, environmental protection produces without " three wastes ".
Embodiment
Below in conjunction with embodiment, the present invention is described further.
Comparative example 1
Composition of raw materials is as follows:
(1) glycerine 12 parts, (2) ethylene glycol 16 parts, (3) propylene glycol 9 parts, (4) 8 parts, phenylformic acid, (5) m-phthalic acid 15 parts, 0.006 part, (6) oxidation inhibitor, (7) tetrabutyl titanate 0.0078 part, (8) maleic acid 15 parts, (9) Resorcinol 0.0096 part, (10) vinylbenzene 40 parts;
Under high pure nitrogen protection, by above-mentioned formula, (1) ~ (7) are dropped in the reactor with thermometer, agitator, condenser, stir.Be rapidly heated to material water outlet, 160 DEG C of insulations 0.5 hour.Insulation terminates rear slow intensification, is warming up to 200 DEG C of polycondensations until acid number drops to below 20mgKOH/g.Then be cooled to 155 DEG C of inputs (8), rapid temperature increases, to material water outlet, is incubated 0.5 hour at 160 DEG C.Insulation terminates rear slow intensification, be warming up to 200 DEG C of polycondensations until acid number drops to below 58mgKOH/g, under vacuum tightness-0.07MPa polycondensation to acid number lower than 40mgKOH/g, be cooled to 180 DEG C to add (9), be cooled to 120 DEG C to add (10), after stirring, namely obtain product glycerin modification unsaturated polyester resin.
Embodiment 1
Composition of raw materials is as follows:
(1) glycerine 12 parts, (2) ethylene glycol 16 parts, (3) propylene glycol 9 parts, (4) 8 parts, phenylformic acid, (5) m-phthalic acid 15 parts, 0.006 part, (6) oxidation inhibitor, (7) dibutyl tin 0.0078 part, (8) maleic acid 15 parts, (9) Resorcinol 0.0096 part, (10) vinylbenzene 40 parts;
Under high pure nitrogen protection, by above-mentioned formula, (1) ~ (7) are dropped in the reactor with thermometer, agitator, condenser, stir.Be rapidly heated to material water outlet, 160 DEG C of insulations 0.5 hour.Insulation terminates rear slow intensification, is warming up to 200 DEG C of polycondensations until acid number drops to below 20mgKOH/g.Then be cooled to 155 DEG C of inputs (8), rapid temperature increases, to material water outlet, is incubated 0.5 hour at 160 DEG C.Insulation terminates rear slow intensification, be warming up to 200 DEG C of polycondensations until acid number drops to below 58mgKOH/g, under vacuum tightness-0.07MPa polycondensation to acid number lower than 40mgKOH/g, be cooled to 180 DEG C to add (9), be cooled to 120 DEG C to add (10), after stirring, namely obtain product glycerin modification unsaturated polyester resin.
Embodiment 2
Composition of raw materials is as follows:
(1) glycerine 8 parts, (2) glycol ether 14 parts, (3) neopentyl glycol 10 parts, (4) 16 parts, Glacial acetic acid, (5) Tetra hydro Phthalic anhydride 14 parts, (6) oxidation inhibitor 0.025 part of (7) stannous octoate 0.0225 part, (8) MALEIC ANHYDRIDE 25 parts, (9) Resorcinol 0.0125 part, (10) methyl methacrylate 37 parts;
Under high pure nitrogen protection, by above-mentioned formula, (1) ~ (7) are dropped in the reactor with thermometer, agitator, condenser, stir.Be rapidly heated to material water outlet, 170 DEG C of insulations 1 hour.Insulation terminates rear slow intensification, is warming up to 210 DEG C of polycondensations until acid number drops to below 20mgKOH/g.Then be cooled to 165 DEG C of inputs (8), rapid temperature increases, to material water outlet, is incubated 1 hour at 170 DEG C.Insulation terminates rear slow intensification, be warming up to 210 DEG C of polycondensations until acid number drops to below 58mgKOH/g, under vacuum tightness-0.08MPa polycondensation to acid number lower than 40mgKOH/g, be cooled to 180 DEG C to add (9), be cooled to 130 DEG C to add (10), after stirring, namely obtain product glycerin modification unsaturated polyester resin.
Embodiment 3
Composition of raw materials is as follows:
(1) glycerine 14 parts, (2) glycol ether 14 parts, (3) 6 parts, phenylformic acid, (4) 13 parts, Glacial acetic acid, (5) succinic acid 9 parts, 0.03 part, (6) oxidation inhibitor, (7) dibutyl tin 0.00825 part, (8) FUMARIC ACID TECH GRADE 30 parts, (9) methyl hydroquinone 0.0125 part, (10) Vinylstyrene 39 parts;
Under high pure nitrogen protection, by above-mentioned formula, (1) ~ (7) are dropped in the reactor with thermometer, agitator, condenser, stir.Be rapidly heated to material water outlet, 180 DEG C of insulations 1.5 hours.Insulation terminates rear slow intensification, is warming up to 210 DEG C of polycondensations until acid number drops to below 20mgKOH/g.Then be cooled to 165 DEG C of inputs (8), rapid temperature increases, to material water outlet, is incubated 1.5 hours at 180 DEG C.Insulation terminates rear slow intensification, be warming up to 210 DEG C of polycondensations until acid number drops to below 58mgKOH/g, under vacuum tightness-0.098MPa polycondensation to acid number lower than 40mgKOH/g, be cooled to 180 DEG C to add (9), be cooled to 130 DEG C to add (10), after stirring, namely obtain product glycerin modification unsaturated polyester resin.
Embodiment 4
Composition of raw materials is as follows:
(1) glycerine 13 parts, (2) dipropylene glycol 8 parts, (3) hexylene glycol 21 parts, 10 parts, (4) Glacial acetic acid, (5) propionic acid 5 parts, (6) pentanedioic acid 12 parts, 0.0135 part, (7) oxidation inhibitor, (8) Mono-n-butyltin 0.0125 part, (9) MALEIC ANHYDRIDE 18 parts, (10) p-ten.-butylcatechol 0.00925 part, (11) butyl acrylate 13 parts, (12) vinylbenzene 26 parts;
Under high pure nitrogen protection, by above-mentioned formula, (1) ~ (8) are dropped in the reactor with thermometer, agitator, condenser, stir.Be rapidly heated to material water outlet, 160 DEG C of insulations 1.5 hours.Insulation terminates rear slow intensification, is warming up to 210 DEG C of polycondensations until acid number drops to below 20mgKOH/g.Then be cooled to 165 DEG C of inputs (9), rapid temperature increases, to material water outlet, is incubated 1.5 hours at 180 DEG C.Insulation terminates rear slow intensification, be warming up to 200 DEG C of polycondensations until acid number drops to below 58mgKOH/g, under vacuum tightness-0.07MPa polycondensation to acid number lower than 40mgKOH/g, be cooled to 180 DEG C to add (10), be cooled to 120 DEG C to add (11), (12) namely obtain product glycerin modification unsaturated polyester resin after stirring.
Embodiment 5
Composition of raw materials is as follows:
(1) glycerine 9 parts, (2) glycol ether 14 parts, (3) butyleneglycol 5 parts, 10 parts, (4) Glacial acetic acid, (5) 2 parts, formic acid, (6) hexanodioic acid 20 parts, 0.0135 part, (7) oxidation inhibitor, (8) dibutyl tin 0.0225 part, (9) FUMARIC ACID TECH GRADE 23 parts, (10) para benzoquinone 0.0101 part, (11) chloro-styrene 6 parts, (12) vinylbenzene 19 parts;
Under high pure nitrogen protection, by above-mentioned formula, (1) ~ (8) are dropped in the reactor with thermometer, agitator, condenser, stir.Be rapidly heated to material water outlet, 170 DEG C of insulations 0.5 hour.Insulation terminates rear slow intensification, is warming up to 210 DEG C of polycondensations until acid number drops to below 20mgKOH/g.Then be cooled to 165 DEG C of inputs (9), rapid temperature increases, to material water outlet, is incubated 1 hour at 180 DEG C.Insulation terminates rear slow intensification, be warming up to 200 DEG C of polycondensations until acid number drops to below 58mgKOH/g, under vacuum tightness-0.08MPa polycondensation to acid number lower than 40mgKOH/g, be cooled to 180 DEG C to add (10), be cooled to 130 DEG C to add (11), (12) namely obtain product glycerin modification unsaturated polyester resin after stirring.
Embodiment 6
Composition of raw materials is as follows:
(1) glycerine 13 parts, (2) ethylene glycol 8 parts, (3) hexylene glycol 21 parts, 3 parts, (4) Glacial acetic acid, (5) 16 parts, phenylformic acid, (6) Tetra hydro Phthalic anhydride 10 parts, 0.0097 part, (7) oxidation inhibitor, (8) Mono-n-butyltin 0.0316 part, (9) MALEIC ANHYDRIDE 20 parts, (10) Resorcinol 0.02 part, (11) Phthalic acid, diallyl ester 14 parts, (12) vinylbenzene 15 parts;
Under high pure nitrogen protection, by above-mentioned formula, (1) ~ (8) are dropped in the reactor with thermometer, agitator, condenser, stir.Be rapidly heated to material water outlet, 180 DEG C of insulations 1 hour.Insulation terminates rear slow intensification, is warming up to 210 DEG C of polycondensations until acid number drops to below 20mgKOH/g.Then be cooled to 165 DEG C of inputs (9), rapid temperature increases, to material water outlet, is incubated 1 hour at 180 DEG C.Insulation terminates rear slow intensification, be warming up to 200 DEG C of polycondensations until acid number drops to below 58mgKOH/g, under vacuum tightness-0.098MPa polycondensation to acid number lower than 40mgKOH/g, be cooled to 180 DEG C to add (10), be cooled to 120 DEG C to add (11), (12) namely obtain product glycerin modification unsaturated polyester resin after stirring.
The reaction times of comparative example 1 and enforcement profit 1 and other performance comparison are as following table:
| Project | Comparative example 1 | Embodiment 1 |
| Reaction times (the first step)/h | 15 | 9 |
| Acid number/mgKOH/g | 33 | 20 |
| Gelation time/min | 28 | 10 |
| Steady state/h | 21 | 53 |
Above in each embodiment the technical indicator of gained resin as following table:
Claims (8)
1. a preparation method for glycerin modification unsaturated polyester resin, comprises polycondensation and crosslinking reaction, it is characterized in that adding organic tin catalyzer in polycondensation;
Raw materials by weight portion used is counted:
Glycerine 5-15 parts
8-20 parts, saturated monoprotic acid
Monounsaturated dicarboxylic acid 5-15 parts
Unsaturated dibasic acid 15-30 parts
Dibasic alcohol 10-30 parts
0.005-0.03 part, oxidation inhibitor
Organic tin catalyzer 0.005-0.05 part
Stopper 0.005-0.02 part
Crosslinkable monomers 25-40 parts;
Described preparation method's concrete steps are as follows:
(1) polycondensation: under high pure nitrogen protection, glycerine, dibasic alcohol, monounsaturated dicarboxylic acid, saturated monoprotic acid, oxidation inhibitor and organic tin catalyzer are dropped in the reactor with thermometer, agitator, condenser, stir, be warming up to material water outlet, at 160-180 DEG C of insulation 0.5-1.5 hour; After insulation terminates, be warming up to 200-210 DEG C until acid number drops to 20 below mgKOH/g, be then cooled to 155-165 DEG C and drop into unsaturated dibasic acid, be warming up to material water outlet, at 160-180 DEG C of insulation 0.5-1.5 hour; After insulation terminates, be warming up to 200-210 DEG C until acid number drops to 58 below mgKOH/g, under vacuum tightness-0.07--0.098MPa, polycondensation is to acid number lower than 40 mgKOH/g, is cooled to 180 DEG C and adds stopper;
(2) crosslinking reaction: be cooled to 120-130 DEG C and add crosslinkable monomers, namely obtains product glycerin modification unsaturated polyester resin after stirring.
2. the preparation method of glycerin modification unsaturated polyester resin according to claim 1, is characterized in that described organic tin catalyzer is the one in dibutyl tin, stannous octoate or Mono-n-butyltin.
3. the preparation method of glycerin modification unsaturated polyester resin according to claim 1, is characterized in that described saturated monoprotic acid is one or both in phenylformic acid, Glacial acetic acid, formic acid or propionic acid.
4. the preparation method of glycerin modification unsaturated polyester resin according to claim 1, is characterized in that described monounsaturated dicarboxylic acid is one or more in Tetra hydro Phthalic anhydride, m-phthalic acid, succinic acid, pentanedioic acid or hexanodioic acid.
5. the preparation method of glycerin modification unsaturated polyester resin according to claim 1, is characterized in that described unsaturated dibasic acid is the one in maleic acid, MALEIC ANHYDRIDE or FUMARIC ACID TECH GRADE.
6. the preparation method of glycerin modification unsaturated polyester resin according to claim 1, is characterized in that described dibasic alcohol is one or both in ethylene glycol, propylene glycol, butyleneglycol, glycol ether, dipropylene glycol, neopentyl glycol or hexylene glycol; Described oxidation inhibitor is ditertbutylparacresol, methylene radical bis-phenol, antioxidant 1010, one or both in irgasfos 168.
7. the preparation method of glycerin modification unsaturated polyester resin according to claim 1, is characterized in that described stopper is one or both in Resorcinol, methyl hydroquinone, p-ten.-butylcatechol, Tert. Butyl Hydroquinone or para benzoquinone.
8. the preparation method of glycerin modification unsaturated polyester resin according to claim 1, is characterized in that described crosslinkable monomers is the one in vinylbenzene, Vinylstyrene, chloro-styrene, methyl methacrylate, butyl acrylate or Phthalic acid, diallyl ester.
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| CN103755938A (en) * | 2014-01-06 | 2014-04-30 | 南通天和树脂有限公司 | High-ductility unsaturated polyester resin under low-temperature environment |
| CN103951793A (en) * | 2014-04-15 | 2014-07-30 | 吴桥昊通树脂有限公司 | Method for producing unsaturated polyester resin by using glycerinum |
| CN106832141A (en) * | 2017-02-24 | 2017-06-13 | 江苏赛鑫树脂有限公司 | A kind of glycerin modification unsaturated polyester resin and preparation method thereof |
| CN109206561A (en) * | 2018-09-11 | 2019-01-15 | 惠州市固德尔合成材料有限公司 | A method of unsaturated polyester resin is prepared with glycerol |
| CN110092874A (en) * | 2019-04-23 | 2019-08-06 | 广西华砻树脂有限公司 | A kind of glycerin modification unsaturated polyester resin and preparation method thereof for daylighting tile |
| CN110172294A (en) * | 2019-05-28 | 2019-08-27 | 广西华砻树脂有限公司 | A kind of unsaturated polyester resin for coating and preparation method thereof |
| CN114456688A (en) * | 2022-01-26 | 2022-05-10 | 大一(云浮)新材料科技有限公司 | General PE paint for bottom surface and preparation method and construction method thereof |
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| CN1325914A (en) * | 2000-05-29 | 2001-12-12 | 桂林市万和有限责任公司 | Air-dried unsaturated polyester resin for putty |
| CN102219882A (en) * | 2011-05-04 | 2011-10-19 | 肇庆福田化学工业有限公司 | Method for synthesizing unsaturated polyester resin by utilizing glycerol |
| CN102558453A (en) * | 2011-11-15 | 2012-07-11 | 湖州红剑聚合物有限公司 | Mono-acid blocked unsaturated polyester resin and preparation method for same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1325914A (en) * | 2000-05-29 | 2001-12-12 | 桂林市万和有限责任公司 | Air-dried unsaturated polyester resin for putty |
| CN102219882A (en) * | 2011-05-04 | 2011-10-19 | 肇庆福田化学工业有限公司 | Method for synthesizing unsaturated polyester resin by utilizing glycerol |
| CN102558453A (en) * | 2011-11-15 | 2012-07-11 | 湖州红剑聚合物有限公司 | Mono-acid blocked unsaturated polyester resin and preparation method for same |
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