CN114656626A - Reworkable thermosetting resin based on polyethylene terephthalate and preparation method thereof - Google Patents
Reworkable thermosetting resin based on polyethylene terephthalate and preparation method thereof Download PDFInfo
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- CN114656626A CN114656626A CN202011534499.6A CN202011534499A CN114656626A CN 114656626 A CN114656626 A CN 114656626A CN 202011534499 A CN202011534499 A CN 202011534499A CN 114656626 A CN114656626 A CN 114656626A
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- polyethylene terephthalate
- thermosetting resin
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- 229920000139 polyethylene terephthalate Polymers 0.000 title claims abstract description 132
- 239000005020 polyethylene terephthalate Substances 0.000 title claims abstract description 132
- -1 polyethylene terephthalate Polymers 0.000 title claims abstract description 104
- 229920005989 resin Polymers 0.000 title claims abstract description 94
- 239000011347 resin Substances 0.000 title claims abstract description 94
- 229920001187 thermosetting polymer Polymers 0.000 title claims abstract description 92
- 238000002360 preparation method Methods 0.000 title abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 64
- 239000000178 monomer Substances 0.000 claims abstract description 38
- 239000004593 Epoxy Substances 0.000 claims abstract description 37
- 239000013067 intermediate product Substances 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 20
- 239000000203 mixture Substances 0.000 claims abstract description 20
- 229920005862 polyol Polymers 0.000 claims abstract description 19
- 150000003077 polyols Chemical class 0.000 claims abstract description 19
- 238000001035 drying Methods 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 14
- 239000000654 additive Substances 0.000 claims description 11
- 230000000996 additive effect Effects 0.000 claims description 11
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 10
- 150000003512 tertiary amines Chemical class 0.000 claims description 10
- 239000003963 antioxidant agent Substances 0.000 claims description 8
- 230000003078 antioxidant effect Effects 0.000 claims description 8
- 239000003381 stabilizer Substances 0.000 claims description 6
- 125000003700 epoxy group Chemical group 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 4
- 125000001931 aliphatic group Chemical group 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical compound NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 claims description 3
- 239000000344 soap Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 2
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 11
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- 238000005520 cutting process Methods 0.000 description 10
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- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 238000006136 alcoholysis reaction Methods 0.000 description 5
- 238000004064 recycling Methods 0.000 description 5
- 239000004634 thermosetting polymer Substances 0.000 description 5
- BYEAHWXPCBROCE-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropan-2-ol Chemical group FC(F)(F)C(O)C(F)(F)F BYEAHWXPCBROCE-UHFFFAOYSA-N 0.000 description 4
- KUBDPQJOLOUJRM-UHFFFAOYSA-N 2-(chloromethyl)oxirane;4-[2-(4-hydroxyphenyl)propan-2-yl]phenol Chemical compound ClCC1CO1.C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 KUBDPQJOLOUJRM-UHFFFAOYSA-N 0.000 description 4
- LLLVZDVNHNWSDS-UHFFFAOYSA-N 4-methylidene-3,5-dioxabicyclo[5.2.2]undeca-1(9),7,10-triene-2,6-dione Chemical compound C1(C2=CC=C(C(=O)OC(=C)O1)C=C2)=O LLLVZDVNHNWSDS-UHFFFAOYSA-N 0.000 description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
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- 229910021645 metal ion Inorganic materials 0.000 description 4
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- 150000003384 small molecules Chemical class 0.000 description 4
- IRAGEBXSFXWYNX-UHFFFAOYSA-N 2-(1,3,5-triazinan-1-yl)ethanol Chemical compound OCCN1CNCNC1 IRAGEBXSFXWYNX-UHFFFAOYSA-N 0.000 description 3
- GQBHYWDCHSZDQU-UHFFFAOYSA-N 4-(2,4,4-trimethylpentan-2-yl)-n-[4-(2,4,4-trimethylpentan-2-yl)phenyl]aniline Chemical compound C1=CC(C(C)(C)CC(C)(C)C)=CC=C1NC1=CC=C(C(C)(C)CC(C)(C)C)C=C1 GQBHYWDCHSZDQU-UHFFFAOYSA-N 0.000 description 3
- 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 description 3
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- VTFXHGBOGGGYDO-UHFFFAOYSA-N 2,4-bis(dodecylsulfanylmethyl)-6-methylphenol Chemical compound CCCCCCCCCCCCSCC1=CC(C)=C(O)C(CSCCCCCCCCCCCC)=C1 VTFXHGBOGGGYDO-UHFFFAOYSA-N 0.000 description 2
- WPMYUUITDBHVQZ-UHFFFAOYSA-N 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoic acid Chemical compound CC(C)(C)C1=CC(CCC(O)=O)=CC(C(C)(C)C)=C1O WPMYUUITDBHVQZ-UHFFFAOYSA-N 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- OWMVSZAMULFTJU-UHFFFAOYSA-N bis-tris Chemical compound OCCN(CCO)C(CO)(CO)CO OWMVSZAMULFTJU-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 150000002148 esters Chemical group 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
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- 239000007924 injection Substances 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
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- 150000002989 phenols Chemical class 0.000 description 2
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- 229960004063 propylene glycol Drugs 0.000 description 2
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- 231100000331 toxic Toxicity 0.000 description 2
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- JWCYRADIWYQGTO-UHFFFAOYSA-N 1,1-bis(2,4-ditert-butylphenyl)-2,2-bis(hydroxymethyl)propane-1,3-diol phosphorous acid Chemical compound P(O)(O)O.C(C)(C)(C)C1=C(C=CC(=C1)C(C)(C)C)C(O)(C(CO)(CO)CO)C1=C(C=C(C=C1)C(C)(C)C)C(C)(C)C JWCYRADIWYQGTO-UHFFFAOYSA-N 0.000 description 1
- VNQNXQYZMPJLQX-UHFFFAOYSA-N 1,3,5-tris[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]-1,3,5-triazinane-2,4,6-trione Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CN2C(N(CC=3C=C(C(O)=C(C=3)C(C)(C)C)C(C)(C)C)C(=O)N(CC=3C=C(C(O)=C(C=3)C(C)(C)C)C(C)(C)C)C2=O)=O)=C1 VNQNXQYZMPJLQX-UHFFFAOYSA-N 0.000 description 1
- DWKJNNWQZHJJSH-UHFFFAOYSA-N 2-amino-2-(2-hydroxyethyl)butane-1,1,1,4-tetrol Chemical compound OCCC(C(O)(O)O)(N)CCO DWKJNNWQZHJJSH-UHFFFAOYSA-N 0.000 description 1
- AIBRSVLEQRWAEG-UHFFFAOYSA-N 3,9-bis(2,4-ditert-butylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP1OCC2(COP(OC=3C(=CC(=CC=3)C(C)(C)C)C(C)(C)C)OC2)CO1 AIBRSVLEQRWAEG-UHFFFAOYSA-N 0.000 description 1
- QRLSTWVLSWCGBT-UHFFFAOYSA-N 4-((4,6-bis(octylthio)-1,3,5-triazin-2-yl)amino)-2,6-di-tert-butylphenol Chemical compound CCCCCCCCSC1=NC(SCCCCCCCC)=NC(NC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=N1 QRLSTWVLSWCGBT-UHFFFAOYSA-N 0.000 description 1
- ZVVFVKJZNVSANF-UHFFFAOYSA-N 6-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]hexyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCCCCCCOC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 ZVVFVKJZNVSANF-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- FSVCELGFZIQNCK-UHFFFAOYSA-N N,N-bis(2-hydroxyethyl)glycine Chemical compound OCCN(CCO)CC(O)=O FSVCELGFZIQNCK-UHFFFAOYSA-N 0.000 description 1
- DBYHNAIXTVQWTK-UHFFFAOYSA-N P(O)(O)O.P(O)(O)O.C(C)(C)(C)C1=C(C=CC(=C1)C(C)(C)C)C1=CC=C(C=C1)C1=CC=CC=C1.C(C)(C)(C)C1=C(C=CC(=C1)C(C)(C)C)C1=CC=C(C=C1)C1=CC=CC=C1.C(C)(C)(C)C1=C(C=CC(=C1)C(C)(C)C)C1=CC=C(C=C1)C1=CC=CC=C1.C(C)(C)(C)C1=C(C=CC(=C1)C(C)(C)C)C1=CC=C(C=C1)C1=CC=CC=C1 Chemical compound P(O)(O)O.P(O)(O)O.C(C)(C)(C)C1=C(C=CC(=C1)C(C)(C)C)C1=CC=C(C=C1)C1=CC=CC=C1.C(C)(C)(C)C1=C(C=CC(=C1)C(C)(C)C)C1=CC=C(C=C1)C1=CC=CC=C1.C(C)(C)(C)C1=C(C=CC(=C1)C(C)(C)C)C1=CC=C(C=C1)C1=CC=CC=C1.C(C)(C)(C)C1=C(C=CC(=C1)C(C)(C)C)C1=CC=C(C=C1)C1=CC=CC=C1 DBYHNAIXTVQWTK-UHFFFAOYSA-N 0.000 description 1
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 1
- 238000000944 Soxhlet extraction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- JRPRCOLKIYRSNH-UHFFFAOYSA-N bis(oxiran-2-ylmethyl) benzene-1,2-dicarboxylate Chemical compound C=1C=CC=C(C(=O)OCC2OC2)C=1C(=O)OCC1CO1 JRPRCOLKIYRSNH-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
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- 238000010586 diagram Methods 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
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- 125000004185 ester group Chemical group 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- SIGPWCVHTYIKME-UHFFFAOYSA-N hexamethanol Chemical compound OC.OC.OC.OC.OC.OC SIGPWCVHTYIKME-UHFFFAOYSA-N 0.000 description 1
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- GGUBFICZYGKNTD-UHFFFAOYSA-N triethyl phosphonoacetate Chemical compound CCOC(=O)CP(=O)(OCC)OCC GGUBFICZYGKNTD-UHFFFAOYSA-N 0.000 description 1
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
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-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/91—Polymers modified by chemical after-treatment
- C08G63/914—Polymers modified by chemical after-treatment derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/916—Dicarboxylic acids and dihydroxy compounds
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- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention relates to a reworkable thermosetting resin based on polyethylene terephthalate and a preparation method thereof, wherein the preparation method comprises the following steps: mixing polyethylene terephthalate, polyol and epoxy monomer to obtain a mixture; carrying out a first reaction on the mixture at a first temperature to obtain an intermediate product; and drying the intermediate product and then carrying out a second reaction to obtain the reworkable thermosetting resin based on the polyethylene terephthalate. The preparation method disclosed by the invention is simple in synthesis process, short in path, high in efficiency and suitable for industrial production, and the obtained reworkable thermosetting resin based on the polyethylene terephthalate contains hydroxy ester, can be recycled and reprocessed by using traditional processing modes such as extrusion molding, compression molding and injection molding, and is strong in universality.
Description
Technical Field
The invention relates to the technical field of macromolecules, in particular to a reworkable thermosetting resin based on polyethylene terephthalate and a preparation method thereof.
Background
Thermosetting resins play an important role in the contemporary human society because of their advantages of good mechanical properties, heat resistance, chemical resistance, etc. However, the thermosetting resin cannot be dissolved or melted after curing, and thus cannot be recycled and reprocessed.
The reprocessable thermosetting resin not only has the advantages of good mechanical property, heat resistance, chemical corrosion resistance and the like of the thermosetting resin, but also can realize reprocessing and recycling under certain conditions, and has better application prospect. However, conventional reworkable thermoset resins are generally synthesized from small molecule monomers and must incorporate Zn in the crosslinked network2+The plasma metal ions can promote the network topology transformation, thereby realizing macroscopic reprocessing and recycling. The reworkable thermosetting resin with metal ions has a long synthetic path, is easy to pollute the environment in the recovery process, and generally cannot be reworked by traditional modes such as extrusion molding, injection molding and the like, so that the scale application of the resin is greatly limited.
Disclosure of Invention
In view of the above, there is a need to provide a reworkable thermosetting resin based on polyethylene terephthalate, which has a simple synthesis process, an environmentally friendly recycling process, and is suitable for various reworking methods, and a method for preparing the same.
A method of preparing a reworkable thermosetting resin based on polyethylene terephthalate comprising:
mixing polyethylene terephthalate, polyol and epoxy monomer to obtain a mixture;
carrying out a first reaction on the mixture at a first temperature to obtain an intermediate product; and
and drying the intermediate product and then carrying out a second reaction to obtain the reworkable thermosetting resin based on the polyethylene terephthalate.
In one embodiment, the polyol comprises at least one of glycerol, pentaerythritol, tertiary amine-containing polyols.
In one embodiment, the epoxy monomer contains more than two epoxy groups. The epoxy monomer comprises at least one of glycidyl ether epoxy monomer, glycidyl ester epoxy monomer, glycidyl amine epoxy monomer, linear aliphatic epoxy monomer and phenolic epoxy monomer.
In one embodiment, the first temperature is 240 ℃ to 290 ℃;
in one embodiment, the reaction temperature of the second reaction is 120-210 ℃, and the reaction time is 4-16 h.
In one embodiment, the first reaction is carried out in a twin screw extruder.
In one embodiment, the mixture further includes an additive, the additive includes at least one of an antioxidant and a stabilizer, wherein the antioxidant includes at least one of an aromatic amine compound and a hindered phenol compound, and the stabilizer includes at least one of a basic lead salt compound, a metal soap compound and a phosphite compound.
The mass ratio of the polyethylene terephthalate, the additive, the polyol and the epoxy monomer is 100:0.1-2:0.2-15: 0.5-10.
In the preparation method of the reworkable thermosetting resin based on the polyethylene terephthalate, the polyol can catalyze the alcoholization reaction and can also carry out the crosslinking reaction with the polyethylene terephthalate (PET), and the method has no influence on the environment, and the epoxy monomer can not react with the polyol and the PET. The preparation method does not need to add extra catalyst. Therefore, the preparation method of the reworkable thermosetting resin based on the polyethylene terephthalate has the advantages of simple synthesis process, short path and high efficiency, and is suitable for industrial production.
A reworkable thermosetting resin based on polyethylene terephthalate, which is obtained by the above-described preparation method, the reworkable thermosetting resin based on polyethylene terephthalate including a hydroxyl ester in a molecular chain thereof.
The reworkable thermosetting resin based on polyethylene terephthalate of the present invention contains hydroxyl ester, and under proper reaction conditions, the hydroxyl ester can generate ester exchange reaction, so as to promote the change of the micro topological structure of the cross-linked network of the reworkable thermosetting resin based on polyethylene terephthalate, and the great change of the micro topological structure can change the macro topography of the reworkable thermosetting resin based on polyethylene terephthalate, thereby realizing the recovery and reprocessing of the reworkable thermosetting resin. Therefore, the reworkable thermosetting resin based on the polyethylene terephthalate can be loosened without adding a catalyst such as metal ions, can be molded by traditional processing methods such as extrusion molding, compression molding and injection molding, and has strong universality.
In addition, the raw materials of the reworkable thermosetting resin based on polyethylene terephthalate of the present invention are low toxic or non-toxic, so that the reworkable thermosetting resin based on polyethylene terephthalate is green and environmentally friendly.
Drawings
FIG. 1 is a diagram of a product of a reworkable thermosetting resin based on polyethylene terephthalate obtained in example 1 of the present invention;
FIG. 2 is a graph of the gel content of the reworkable thermosetting resin based on polyethylene terephthalate obtained in example 1, example 2 and example 4 of the present invention;
FIG. 3 is a TGA curve of PET and a reworkable thermoset resin based on polyethylene terephthalate obtained in example 1, example 2, example 4 of the present invention;
FIG. 4 is a DSC curve of PET and a reworkable thermoset resin based on polyethylene terephthalate obtained in example 1, example 2, example 4, example 5 of the present invention;
FIG. 5 is a graph of the tensile strength of PET and a polyethylene terephthalate-based reworkable thermoset obtained from example 1, example 2, example 4, example 5 of the present invention;
FIG. 6 is a graph of creep resistance of PET and a reworkable thermoset resin based on polyethylene terephthalate obtained in example 2 of the present invention;
FIG. 7 is an external view of a product obtained by reworking the polyethylene terephthalate-based reworkable thermosetting resin obtained in example 1 of the present invention;
FIG. 8 is a graph of the melt index of a reworkable thermosetting resin based on polyethylene terephthalate obtained in example 1, example 2, example 4 and example 10 of the present invention.
Detailed Description
The reworkable thermosetting resin based on polyethylene terephthalate and the preparation method thereof provided by the present invention will be further described below.
The invention provides a preparation method of reworkable thermosetting resin based on polyethylene terephthalate, which comprises the following steps:
s1, mixing polyethylene terephthalate, polyol and epoxy monomer to obtain a mixture;
s2, carrying out a first reaction on the mixture at a first temperature to obtain an intermediate product;
and S3, drying the intermediate product and then carrying out a second reaction to obtain the reworkable thermosetting resin based on the polyethylene terephthalate.
In step S1, the PET may be dried in a vacuum environment to remove moisture before use, so as to avoid hydrolysis of PET during processing and influence reaction and product quality.
The polyol in step S1 includes at least one of glycerin, pentaerythritol, and a tertiary amine-containing polyol, preferably a tertiary amine-containing polyol, and more preferably BIS (2-hydroxyethyl) amino (trimethylol) methane (BIS-TRIS). The polyhydric alcohol is selected because phenyl groups are generally not present around the hydroxyl groups, so that the steric hindrance of the hydroxyl groups is small and the reactivity is high. The polyol has the following functions: a first reaction with PET and as a catalyst, catalyzing the first and second reactions.
In step S1, the structural formula of the epoxy monomer contains two or more epoxy groups, the epoxy monomer includes one of a glycidyl ether epoxy monomer, a glycidyl ester epoxy monomer, a glycidyl amine epoxy monomer, a linear aliphatic epoxy monomer, an alicyclic epoxy monomer, and a novolac epoxy monomer, preferably a glycidyl ether epoxy monomer, and more preferably 2, 2-bis (4-glycidoxyphenyl) propane (DER 332).
In step S1, the raw material of the method for preparing a reworkable thermosetting resin based on ethylene terephthalate further includes an additive including at least one of an antioxidant and a stabilizer.
Wherein the antioxidant comprises at least one of aromatic amine compounds and hindered phenol compounds, specifically, the hindered phenol compounds comprise tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid]Pentaerythritol ester (antioxidant 1010), (3- (1, 1-dimethylethyl) -beta- [3- (1, 1-dimethylethyl) -4-hydroxyphenyl]-1, 2-ethylene 4-hydroxy-beta-methylbenzoate) (antioxidant 0)3) Beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid octadecanoic carbonate (antioxidant 1076), hexanediol bis [3, 5-di-tert-butyl-4-hydroxyphenyl ]]Acrylate (antioxidant 259), (1,3,5 tris (3, 5-di-tert-butyl-4-hydroxybenzyl) -1,3, 5-triazine-2, 4,6(1H,3H,5H) -trione) (antioxidant 3114).
The stabilizer comprises at least one of basic lead salt compounds, metal soap compounds and phosphite ester compounds, wherein the phosphite ester compounds comprise triphenyl phosphate, triethyl phosphonoacetate, (bis (2, 4-di-tert-butylphenyl) pentaerythritol phosphite), tetrakis (2, 4-di-tert-butylphenyl-4, 4' biphenyl) bisphosphite and tris (2, 4-di-tert-butylphenyl) phosphite.
In one or more embodiments, the additive is preferably an antioxidant 1010. The function of the additive is to greatly weaken adverse factors such as degradation, oxidation and the like in the first reaction process and reduce side reactions as much as possible so as to ensure that the final product is consistent with the expected product as much as possible.
In step S1, the mass ratio of the PET, the additive, the polyol, and the epoxy monomer is 100:0.1-2:0.2-15:0.5-10, which can be specifically adjusted according to the specific selection of the polyol, the epoxy monomer, and the additive, so as to obtain the reworkable thermosetting resin based on ethylene terephthalate with good properties such as crosslinking degree, mechanical strength, and thermal stability.
In step S2, the first reaction is an alcoholysis reaction, wherein the alcoholysis reaction is substantially a transesterification reaction represented by the following formula (1),
r, R therein1、R2The hydroxyl groups are different or the same substituent groups, and the ester groups are derived from the polyhydric alcohol and the PET.
As can be seen from formula (1), the intermediate product obtained in the first reaction contains, in addition to the alcoholyzed PET segment, small molecules containing hydroxyl groups.
In one or more embodiments, the first reaction is preferably carried out in a twin screw extruder. The set temperature of the double-screw extruder is 240-290 ℃; the set temperature is divided into three stages of rising, leveling and falling. In one or more embodiments, the set temperature is divided into 11 consecutive intervals, wherein the temperature steps of the first 3-4 consecutive intervals are increased or consistent, the temperature steps of the middle 4-5 consecutive intervals are consistent, and the temperature steps of the last 3-4 consecutive intervals are decreased or consistent.
In addition, the ratio of the feeding rate of the double-screw extruder to the host speed of the double-screw extruder is 1: 5-20; the feeding speed of the double-screw extruder is 1rpm-10rpm, and the main machine speed of the double-screw extruder is 50rpm-120 rpm. The ratio of the feed rate to the main machine rate of the twin-screw extruder has a large influence on the reaction process. When the ratio of the feeding speed to the host machine speed is too low, the filling degree of materials between the screws is very low, and adverse phenomena such as machine surge and the like can be caused; the low filling degree also causes weak shearing action of the screw on the materials, so that the raw materials cannot be fully contacted and reacted; at the same time, too low a filling degree can lead to a large amount of air in the raw material melt, and easily lead to the oxidation of the raw material and the product. When the ratio of the feeding speed to the host machine speed is too high, the filling degree of materials among the screws is too high, the shearing work borne by the materials is large, and excessive heat is easily generated, so that the raw materials and products are pyrolyzed. Therefore, the ratio of the feeding speed to the main machine speed is kept in a proper range, so that the dispersion of the filler is facilitated, the raw materials and the products can be prevented from being oxidized or pyrolyzed, and the normal operation of the machine and the normal operation of the reaction are ensured.
In step S3, before the second reaction, the intermediate product needs to be dried to avoid hydrolysis of the intermediate product. In one or more embodiments, the drying process is: and (3) placing the intermediate product in a forced air oven at 80-120 ℃ to remove surface water stains, and then transferring the intermediate product into a vacuum oven at 120-150 ℃ to continue drying for 10-16 h to obtain a dried intermediate product.
And after the drying is finished, carrying out a second reaction on the dried intermediate product, wherein in the second reaction, the reaction temperature is 120-210 ℃, and the reaction time is 4-16 h. In one or more embodiments, the second reaction is performed in a vacuum oven.
The substance of the second reaction is a reaction of an epoxy group and a hydroxyl group represented by the following formula (2) or (3),
wherein R is3、R4、R5Are the same or different substituents.
Specifically, the second reaction comprises: the epoxy monomer and the alcoholysis PET chain segment are crosslinked to obtain the reworkable thermosetting resin based on the ethylene terephthalate, and the epoxy monomer and the small molecule with hydroxyl generated after alcoholysis react. Wherein, the product obtained by the reaction of the epoxy monomer and the hydroxyl-containing micromolecule generated after alcoholysis can be crosslinked with the network structure of the reworkable thermosetting resin based on the ethylene terephthalate to form a part of the network structure, thereby eliminating the adverse effect of the hydroxyl-containing micromolecule and improving the atom utilization rate.
Because of the moderate reactivity of the epoxy monomers used in the present invention, they do not react directly with the polyol in the first reaction, nor react poorly in the second reaction. The crosslinking reaction of the epoxy monomer with the PET segment and the reaction of the alcoholysis-generated small molecule with hydroxyl are substantially the reaction of the epoxy group and the hydroxyl as shown in the formula (2) or the formula (3).
In one or more embodiments, the tertiary amine is contained in the system, and the catalytic action of the tertiary amine is strong, so that the reaction rate of the second reaction is high, the temperature of the second reaction can be set to be 120-180 ℃, and the reaction time can be set to be 2-6 h, so that the energy is saved and the production efficiency is improved on the premise of ensuring that the reaction is fully carried out.
In one or more embodiments, if the tertiary amine is contained in the system but the catalytic effect of the tertiary amine is weak or the tertiary amine is not contained in the system, the reaction rate of the second reaction is slow, and the temperature of the second reaction can be set to be 180-210 ℃ and the reaction time can be set to be 6-16 h to ensure that the reaction is fully performed.
The preparation method of the reworkable thermosetting resin based on the polyethylene terephthalate provided by the invention does not use resin micromolecules as raw materials, but directly starts from PET, and has short preparation route. Therefore, the preparation method of the reworkable thermosetting resin based on the polyethylene terephthalate has simple synthesis process and short path, and is suitable for industrial production.
A reworkable thermosetting resin based on polyethylene terephthalate, which is obtained by the above preparation method, and which includes a hydroxyl ester in a molecular chain.
The reworkable thermosetting resin based on polyethylene terephthalate of the present invention contains hydroxyl ester, and under proper reaction conditions, the hydroxyl ester can generate ester exchange reaction, so as to promote the change of the micro topological structure of the cross-linked network of the reworkable thermosetting resin based on polyethylene terephthalate, and the great change of the micro topological structure can change the macro topography of the reworkable thermosetting resin based on polyethylene terephthalate, thereby realizing the recovery and reprocessing of the reworkable thermosetting resin. Therefore, the reworkable thermosetting resin based on the polyethylene terephthalate can be loosened without adding a catalyst such as metal ions, can be molded by traditional processing methods such as extrusion molding, compression molding and injection molding, and has strong universality.
In one or more embodiments, the hydroxyl and/or tertiary amine contained in the polyethylene terephthalate-based reworkable thermosetting resin each catalyzes a transesterification reaction to promote a change in the micro-topology of the crosslinked network of the polyethylene terephthalate-based reworkable thermosetting resin, further facilitating its recovery and rework.
In addition, the raw materials of the reworkable thermosetting resin based on polyethylene terephthalate of the present invention are low toxic or non-toxic, so that the reworkable thermosetting resin based on polyethylene terephthalate is environmentally friendly.
Hereinafter, the reworkable thermosetting resin based on polyethylene terephthalate and the preparation method thereof according to the present invention will be further described by the following specific examples.
Example 1
2kg of PET pellets were poured into an enamel pan and spread to a thickness of about 20mm, and dried at 150 ℃ for 12 hours in a vacuum atmosphere to remove moisture therefrom. After the PET particles are cooled to room temperature along with the oven, the PET particles are fully and uniformly mixed with 5g of Irgafos 126, 5g of Irganox 1010, 10g of pentaerythritol, 10g of ethylene glycol, 25g of CYD-128E and 25g of DER 354 to prepare raw materials for later use. Starting an oil pump of the double-screw extruder, setting parameters of the double-screw extruder, setting a feeding speed of 4rpm, a main machine speed of 80rpm, setting 11 heating intervals to be 250 ℃, 260 ℃, 270 ℃, 260 ℃ and 250 ℃ respectively, setting a tractor speed to be a proper value to continuously cut granules, slowly pouring a prepared raw material mixture into a feed inlet of the double-screw extruder, ensuring that all materials enter a screw, carrying out a first reaction, extruding and cutting granules.
Pouring the intermediate product, namely the plastic particles after being extruded and cut into granules, into an enamel tray to be spread, moving the enamel tray into a blowing oven at 90 ℃ to remove surface water stains, and then transferring the enamel tray into a vacuum oven at 110 ℃ to continue drying for 12 hours to obtain dry solid mixture particles. The solid mixture particles fully dried were transferred to a vacuum oven at 180 ℃ for a second reaction for 10 hours, followed by natural cooling to room temperature to obtain a reworkable thermosetting resin based on polyethylene terephthalate as shown in fig. 1.
Example 2
2kg of PET pellets were poured into an enamel pan and spread to a thickness of about 20mm, and dried at 150 ℃ for 12 hours in a vacuum atmosphere to remove moisture therefrom. After the PET particles are cooled to room temperature along with the oven, the PET particles are fully and uniformly mixed with 5g of Irganox 565, 5g of Irganox 1726, 10g of 1, 2-propylene glycol, 10g of ethylene glycol, 40g of YDF-162 and 60g of DER332 to prepare raw materials for later use. Starting a double-screw extruder oil pump, setting parameters of the double-screw extruder, setting the feeding speed to be 4rpm, the speed of a main machine to be 80rpm, setting the temperatures to be 250 ℃, 260 ℃, 270 ℃, 260 ℃ and 250 ℃ in 11 heating intervals respectively, setting the speed of a tractor to be a proper value to continuously cut granules, slowly pouring a prepared raw material mixture into a feed inlet of the double-screw extruder, ensuring that all materials enter a screw, carrying out a first reaction, and extruding and cutting granules.
Pouring the intermediate product, namely the plastic particles after being extruded and cut into granules, into an enamel tray to be spread, moving the enamel tray into a blowing oven at 90 ℃ to remove surface water stains, and then transferring the enamel tray into a vacuum oven at 110 ℃ to continue drying for 12 hours to obtain dry solid mixture particles. And (3) transferring the fully dried solid mixture particles into a vacuum oven at 180 ℃ for secondary reaction for 10 hours, and then naturally cooling to room temperature to obtain the reworkable thermosetting resin based on the polyethylene terephthalate.
Example 3
2kg of PET pellets were poured into an enamel pan and spread to a thickness of about 20mm, and dried at 150 ℃ for 12 hours in a vacuum atmosphere to remove moisture therefrom. After the PET particles are cooled to room temperature along with the oven, the PET particles are fully and uniformly mixed with 5g of Irganox 5057, 5g of Irganox 1726, 30g of 1, 2-propylene glycol, 10g of pentaerythritol, 10g of GEPN-638 and 10g of DER 331 to prepare a raw material for later use. Starting an oil pump of the double-screw extruder, setting parameters of the double-screw extruder, setting the feeding speed to be 4rpm, the speed of a main machine to be 80rpm, setting the temperatures of 250 ℃, 260 ℃, 270 ℃, 260 ℃ and 250 ℃ in 11 heating intervals respectively, setting the speed of a tractor to be a proper value to continuously cut granules, slowly pouring a prepared raw material mixture into a feed inlet of the double-screw extruder, ensuring that all materials enter a screw, carrying out a first reaction, extruding and cutting granules.
Pouring the intermediate product, namely the plastic particles after being extruded and cut into granules, into an enamel tray to be spread, moving the enamel tray into a blowing oven at the temperature of 90 ℃ to remove surface water stains, and then transferring the enamel tray into a vacuum oven at the temperature of 110 ℃ to be continuously dried for 12 hours to obtain dry solid mixture particles. And (3) transferring the fully dried solid mixture particles into a vacuum oven at 180 ℃ for secondary reaction for 10 hours, and then naturally cooling to room temperature to obtain the reworkable thermosetting resin based on the polyethylene terephthalate.
Example 4
2kg of PET pellets were poured into an enamel pan and spread to a thickness of about 20mm, and dried at 150 ℃ for 12 hours in a vacuum atmosphere to remove moisture therefrom. After the PET particles are cooled to room temperature along with an oven, the PET particles are fully and uniformly mixed with 5g of Irganox 5057, 3g of Tinuvin XT 55, 1g of triethanolamine, 1g of pentaerythritol, 20g of DER 354 and 20g of DER 331 to prepare a raw material for later use. Starting an oil pump of the double-screw extruder, setting parameters of the double-screw extruder, setting the feeding speed of 4rpm, the speed of a main machine of 80rpm, setting the temperatures of 250 ℃, 260 ℃, 270 ℃, 260 ℃ and 250 ℃ in 11 heating intervals respectively, setting the speed of a traction machine to be a proper value to continuously cut granules, slowly pouring a prepared raw material mixture into a feed port of the double-screw extruder, ensuring that all materials enter the screw, carrying out a first reaction, and extruding and cutting granules.
Pouring the intermediate product, namely the plastic particles after being extruded and cut into granules, into an enamel tray to be spread, moving the enamel tray into a blowing oven at the temperature of 90 ℃ to remove surface water stains, and then transferring the enamel tray into a vacuum oven at the temperature of 110 ℃ to be continuously dried for 12 hours to obtain dry solid mixture particles. And (3) transferring the fully dried solid mixture particles into a vacuum oven at 180 ℃ for secondary reaction for 10 hours, and then naturally cooling to room temperature to obtain the reworkable thermosetting resin based on the polyethylene terephthalate.
Example 5
2kg of PET pellets were poured into an enamel pan and spread to a thickness of about 20mm, and dried at 150 ℃ for 12 hours in a vacuum atmosphere to remove moisture therefrom. After the PET particles are cooled to room temperature along with an oven, the PET particles are fully and uniformly mixed with 2g of Irganox 5057, 5g of Tinuvin XT 55, 1g of triethanolamine, 1g of pentaerythritol, 20g of DER 354 and 20g of DER 331 to prepare raw materials for later use. Starting an oil pump of the double-screw extruder, setting parameters of the double-screw extruder, setting the feeding speed of 4rpm, the speed of a main machine of 80rpm, setting the temperatures of 250 ℃, 260 ℃, 270 ℃, 260 ℃ and 250 ℃ in 11 heating intervals respectively, setting the speed of a traction machine to be a proper value to continuously cut granules, slowly pouring a prepared raw material mixture into a feed port of the double-screw extruder, ensuring that all materials enter the screw, carrying out a first reaction to obtain an intermediate product, and extruding and cutting the granules.
Pouring the intermediate product, namely the plastic particles after being extruded and cut into granules, into an enamel tray to be paved, moving the enamel tray into a blowing oven at 90 ℃ to remove surface water stains, and then transferring the enamel tray into a vacuum oven at 110 ℃ to continue drying for 12 hours to obtain dry solid mixture particles. And (3) transferring the fully dried solid mixture particles into a vacuum oven at 180 ℃ for secondary reaction for 10 hours, and then naturally cooling to room temperature to obtain the reworkable thermosetting resin based on the polyethylene terephthalate.
Example 6
2kg of PET pellets were poured into an enamel pan and spread to a thickness of about 20mm, and dried at 150 ℃ for 12 hours in a vacuum atmosphere to remove moisture therefrom. After the PET particles are cooled to room temperature along with an oven, the PET particles are fully and uniformly mixed with 5g of Tinuvin XT 55, 20g of 1,3, 5-triazine-2, 4, 6-triene tertiary nitrogen-based hexamethanol, 30g of pentaerythritol, 5g of DER 750 and 5g of EPICLON-738 to prepare raw materials for later use. Starting an oil pump of the double-screw extruder, setting parameters of the double-screw extruder, setting the feeding speed to be 4rpm, the speed of a main machine to be 80rpm, setting the temperatures to be 250 ℃, 260 ℃, 270 ℃, 260 ℃ and 250 ℃ in 11 heating intervals respectively, setting the speed of a tractor to be a proper value to continuously cut granules, slowly pouring a prepared raw material mixture into a feeding port of the double-screw extruder, ensuring that all materials enter a screw, carrying out a first reaction to obtain an intermediate product, and extruding and cutting the granules.
Pouring the intermediate product, namely the plastic particles after being extruded and cut into granules, into an enamel tray to be paved, moving the enamel tray into a blowing oven at 90 ℃ to remove surface water stains, and then transferring the enamel tray into a vacuum oven at 110 ℃ to continue drying for 12 hours to obtain dry solid mixture particles. And (3) transferring the fully dried solid mixture particles into a vacuum oven at 180 ℃ for secondary reaction for 10 hours, and then naturally cooling to room temperature to obtain the reworkable thermosetting resin based on the polyethylene terephthalate.
Example 7
2kg of PET particles were poured into an enamel pan to be spread out to a thickness of about 10mm, and dried at 120 ℃ for 16 hours in a vacuum atmosphere to remove water therefrom. After the PET particles are cooled to room temperature along with an oven, the PET particles are fully and uniformly mixed with 2g of Tinuvin XT 55, 2g of 1,3, 5-triazine-2, 4, 6-triene trinitrogen-hexamethanol, 1g of hydroxyethyl hexahydro-s-triazine, 2g of pentaerythritol and 10g of EPICLON-738 to prepare a raw material for later use. Starting an oil pump of the double-screw extruder, setting parameters of the double-screw extruder, setting the feeding speed to be 5rpm, the speed of a main machine to be 60rpm, setting the temperatures to be 260 ℃, 270 ℃, 260 ℃ and 250 ℃ in 11 heating intervals respectively, setting the speed of a tractor to be a proper value to continuously cut granules, slowly pouring a prepared raw material mixture into a feed inlet of the double-screw extruder, ensuring that all materials enter a screw, carrying out a first reaction to obtain an intermediate product, and extruding and cutting the granules.
Pouring the intermediate product, namely the plastic particles after being extruded and cut into granules, into an enamel tray for paving, transferring into a blast oven at 85 ℃ for removing surface water stains, and then transferring into a vacuum oven at 130 ℃ for continuously drying for 10 hours to obtain dried solid mixture particles. And (3) transferring the fully dried solid mixture particles into a vacuum oven at 170 ℃ for a second reaction for 11h, and naturally cooling to room temperature to obtain the reworkable thermosetting resin based on the polyethylene terephthalate.
Example 8
2kg of PET pellets were poured into an enamel pan and spread to a thickness of about 12mm, and dried at 100 ℃ for 16 hours in a vacuum atmosphere to remove water therefrom. After the PET particles were cooled to room temperature in the oven, they were thoroughly and uniformly mixed with 5g of Tinuvin XT 55, 5g of Irgastab PUR 70, 20g of bis (2-hydroxyethyl) amino (trihydroxymethyl) methane, 10g of hydroxyethylhexahydro-s-triazine, 10g of glycerol, 10g of diglycidyl phthalate and 10g of DER 331 to prepare a starting material for use. Starting a double-screw extruder oil pump, setting parameters of the double-screw extruder, setting the feeding speed to be 3rpm, the speed of a main machine to be 50rpm, setting the heating time of 11 heating areas to be 250 ℃, 270 ℃, 280 ℃, 270 ℃ and 260 ℃ respectively, setting the speed of a tractor to be a proper value to continuously granulate, slowly pouring a prepared raw material mixture into a feed inlet of the double-screw extruder, ensuring that all materials enter a screw, carrying out a first reaction to obtain an intermediate product, and extruding and granulating the intermediate product.
Pouring the intermediate product, namely the plastic particles after being extruded and cut into granules, into an enamel tray to be spread flat, moving the enamel tray into a blast oven at 100 ℃ to remove surface water stains, and then transferring the enamel tray into a vacuum oven at 130 ℃ to be continuously dried for 10 hours to obtain dry solid mixture particles. And (3) transferring the fully dried solid mixture particles into a vacuum oven at 170 ℃ for secondary reaction for 13h, and naturally cooling to room temperature to obtain the reworkable thermosetting resin based on the polyethylene terephthalate.
Example 9
2kg of PET particles were poured into an enamel pan and spread to a thickness of about 10mm, and dried at 120 ℃ for 16 hours in a vacuum atmosphere to remove moisture therefrom. After the PET particles are cooled to room temperature along with an oven, the PET particles are fully and uniformly mixed with 10g of Irgastab PUR 70, 20g of N, N-dihydroxyethylglycine, 30g of hydroxyethyl hexahydro-s-triazine, 50g of glycerol, 50g of tetraglycidol diaminodiphenylmethane and 50g of CYD-128E to prepare a raw material for later use. Starting an oil pump of the double-screw extruder, setting parameters of the double-screw extruder, setting a feeding speed to be 4rpm, a main machine speed to be 50rpm, setting 11 heating intervals to be 240 ℃, 250 ℃, 260 ℃, 270 ℃, 260 ℃, 250 ℃ and 250 ℃ respectively, setting a tractor speed to be a proper value to continuously cut granules, slowly pouring a prepared raw material mixture into a feed port of the double-screw extruder, ensuring that all materials enter a screw, carrying out a first reaction, obtaining an intermediate product, and extruding and cutting granules.
Pouring the intermediate product, namely the plastic particles after being extruded and cut into granules, into an enamel tray to be paved, moving the enamel tray into a blast oven at 80 ℃ to remove surface water stains, and then transferring the enamel tray into a vacuum oven at 120 ℃ to continue drying for 10 hours to obtain dry solid mixture particles. And (3) transferring the fully dried solid mixture particles into a vacuum oven at 160 ℃ for a second reaction for 12 hours, and naturally cooling to room temperature to obtain the reworkable thermosetting resin based on the polyethylene terephthalate.
Example 10
2kg of PET particles were poured into an enamel pan to be spread out to a thickness of about 20mm, and dried at 150 ℃ for 12 hours in a vacuum environment to remove moisture therefrom. After the PET particles are cooled to room temperature along with an oven, the PET particles are fully and uniformly mixed with 10g of Irgastab PUR 70, 4g of pentaerythritol, 5g of CYD-128E and 5g of DER 354 to prepare a raw material for later use. Starting an oil pump of the double-screw extruder, setting parameters of the double-screw extruder, setting a feeding speed to be 4rpm, a main machine speed to be 80rpm, setting 11 heating intervals to be 250 ℃, 260 ℃, 270 ℃, 260 ℃ and 250 ℃ respectively, setting a tractor speed to be a proper value to continuously cut granules, slowly pouring a prepared raw material mixture into a feed port of the double-screw extruder, ensuring that all materials enter a screw, carrying out a first reaction, obtaining an intermediate product, and extruding and cutting granules.
Pouring the intermediate product, namely the plastic particles after being extruded and cut into granules, into an enamel tray to be paved, moving the enamel tray into a blowing oven at 90 ℃ to remove surface water stains, and then transferring the enamel tray into a vacuum oven at 110 ℃ to continue drying for 12 hours to obtain dry solid mixture particles. And (3) transferring the fully dried solid mixture particles into a vacuum oven at 180 ℃ for secondary reaction for 10 hours, and then naturally cooling to room temperature to obtain the reworkable thermosetting resin based on the polyethylene terephthalate.
The reworkable thermosetting resins based on polyethylene terephthalate obtained in the above examples were subjected to the following characteristics:
the results of the gel content test are shown in fig. 2, in which the column 201, column 202, and column 203 are graphs of the gel content of the reworkable thermosetting resin obtained in example 1, example 2, and example 4 after treatment for 24 hours by soxhlet extraction (the extractant is hexafluoroisopropanol), and the column 204, column 205, and column 206 are graphs of the gel content of the reworkable thermosetting resin obtained in example 1, example 2, and example 4 after treatment for 48 hours by solvent immersion (the solvent is hexafluoroisopropanol). As can be seen from FIG. 2, the polyethylene terephthalate-based resin obtained according to the present invention is insoluble in hexafluoroisopropanol, while PET is soluble in hexafluoroisopropanol, indicating that the resulting product is a reworkable thermosetting resin of a crosslinked structure, in accordance with expectations;
thermogravimetric (TGA) characterization and results are shown in fig. 3, wherein curve 301 is the TGA curve of PET, and curves 302, 303 and 304 are the TGA curves of the reprocessable thermosetting resins obtained in example 1,2 and 4, respectively. As can be seen from fig. 3, the obtained reworkable thermosetting resin based on polyethylene terephthalate has good thermal stability, similar to PET.
Differential Scanning Calorimetry (DSC) characterization was performed, and the results are shown in fig. 4, where curve 401 is a DSC curve of PET, and curves 402, 403, 404, and 405 are DSC curves of the reworkable thermosetting resins obtained in example 1, example 2, example 4, and example 5, respectively. As can be seen from FIG. 4, the products obtained in examples 1 and 2 have a cold crystallization peak, which indicates that the molecular chain movement is difficult, and are reprocessable thermosetting resins having a crosslinked structure.
The results of the tensile test are shown in fig. 5, in which a column 501 is the tensile strength of PET, and columns 502, 503, 504, and 505 are the tensile strengths of the reworkable thermosetting resin based on polyethylene terephthalate obtained in examples 1,2, 4, and 5, respectively. As can be seen from fig. 5, the resulting reworkable thermosetting resin based on polyethylene terephthalate has a higher breaking strength than PET.
The creep resistance test results are shown in FIG. 6, where curve 601 is the creep resistance curve for the reworkable thermoset resin based on polyethylene terephthalate obtained in example 2 and curve 602 is the creep resistance curve for PET. As can be seen from fig. 6, the reworkable thermosetting resin based on polyethylene terephthalate provided by the present invention has better creep resistance than PET.
The results of the melt index test are shown in fig. 8, in which the column 801, the column 802, the column 803, and the column 804 are the melt indices of the reworkable thermosetting resin based on polyethylene terephthalate obtained in example 10, example 1, example 2, and example 4, respectively. The reworkable thermosetting resin based on polyethylene terephthalate obtained in the above 3 examples can be subjected to injection molding reworking.
Application example 1
The reworkable thermosetting resin based on the polyethylene terephthalate obtained in the embodiment 1 of the invention is hot-pressed and molded in a flat vulcanizing press to obtain a uniform and transparent reworkable thermosetting resin film; the film is cut into fragments with different sizes and then is subjected to hot press molding by a flat vulcanizing machine, and a uniform and transparent reworkable thermosetting resin film shown as 701 in fig. 7 can be obtained, and the reworkable thermosetting resin film can still be obtained after the recycling for at least 4 times.
Application example 2
The reworkable thermosetting resin based on polyethylene terephthalate obtained in example 1 of the present invention was injection molded. Turning on a starting power supply of the injection molding machine and releasing an emergency stop button, setting and confirming various molding parameters (such as temperature, pressure, injection speed and the like) on an operation panel, and preheating and heating a charging barrel and the like; after the temperature reaches the preset temperature, cleaning the charging barrel; and then starting a motor of the machine, checking each molding parameter again and ensuring that the machine can work normally, closing the safety door and starting injection molding, thus obtaining a reworkable thermosetting resin injection molding sample, and obtaining a product as shown by 702 in figure 7.
Application example 3
The reworkable thermosetting resin based on polyethylene terephthalate obtained in example 1 of the present invention was subjected to extrusion molding. Starting the oil pump of the double-screw extruder, setting the parameters of the double-screw extruder, the feeding rate and the host speed, adjusting the heating temperature of each heating interval, setting the speed of the tractor to a proper value to continuously cut into granules, slowly pouring the reprocessed thermosetting resin granules which are dried in advance into the feed inlet of the double-screw extruder, and extruding and cutting into granules. The obtained granules are cooled and then subjected to the extrusion molding process, and after at least 3 times of recycling, reworkable thermosetting resin granules with good morphology and good performance, such as 703 shown in fig. 7, can still be obtained.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent should be subject to the appended claims.
Claims (10)
1. A method for preparing a reworkable thermosetting resin based on polyethylene terephthalate, comprising:
mixing polyethylene terephthalate, polyol and epoxy monomer to obtain a mixture;
carrying out a first reaction on the mixture at a first temperature to obtain an intermediate product; and
and drying the intermediate product and then carrying out a second reaction to obtain the reworkable thermosetting resin based on the polyethylene terephthalate.
2. The method of preparing a reworkable thermosetting resin based on polyethylene terephthalate of claim 1, wherein the polyol comprises at least one of glycerol, pentaerythritol, tertiary amine containing polyols.
3. The method of claim 1, wherein the epoxy monomer comprises two or more epoxy groups.
4. The method of preparing a reworkable thermosetting resin according to claim 1, wherein the epoxy monomer comprises at least one of glycidyl ether type epoxy monomer, glycidyl ester type epoxy monomer, glycidyl amine type epoxy monomer, linear aliphatic type epoxy monomer, and novolac type epoxy monomer.
5. The method of preparing a reworkable thermosetting resin based on polyethylene terephthalate according to claim 1, wherein the first temperature is from 240 ℃ to 290 ℃.
6. The method of preparing a reworkable thermosetting resin based on polyethylene terephthalate according to claim 1, wherein the second reaction has a reaction temperature of 120 ℃ to 210 ℃ and a reaction time of 4h to 16 h.
7. The method of preparing a reworkable thermosetting resin based on polyethylene terephthalate according to claim 1, wherein the first reaction is carried out in a twin screw extruder.
8. The method for preparing the reworkable thermosetting resin based on polyethylene terephthalate according to any one of claims 1 to 7, wherein the mixture further comprises an additive, wherein the additive comprises at least one of an antioxidant and a stabilizer, wherein the antioxidant comprises at least one of an aromatic amine compound and a hindered phenol compound, and the stabilizer comprises at least one of a basic lead salt compound, a metal soap compound and a phosphite compound.
9. The method of claim 8, wherein the mass ratio of the polyethylene terephthalate, the additive, the polyol, and the epoxy monomer is 100:0.1-2:0.2-15: 0.5-10.
10. A reworkable thermosetting resin based on polyethylene terephthalate, characterized in that it is obtained by the production method according to any one of claims 1 to 9, and a hydroxyl ester is included in a molecular chain of the reworkable thermosetting resin based on polyethylene terephthalate.
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