CN112480327A - Method for preparing unsaturated polyester resin by using waste PET (polyethylene terephthalate) product - Google Patents
Method for preparing unsaturated polyester resin by using waste PET (polyethylene terephthalate) product Download PDFInfo
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- CN112480327A CN112480327A CN202011302889.0A CN202011302889A CN112480327A CN 112480327 A CN112480327 A CN 112480327A CN 202011302889 A CN202011302889 A CN 202011302889A CN 112480327 A CN112480327 A CN 112480327A
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- 229920000139 polyethylene terephthalate Polymers 0.000 title claims abstract description 82
- 229920006337 unsaturated polyester resin Polymers 0.000 title claims abstract description 52
- 238000000034 method Methods 0.000 title claims abstract description 14
- 239000002699 waste material Substances 0.000 title claims abstract description 11
- 239000005020 polyethylene terephthalate Substances 0.000 title abstract description 71
- -1 polyethylene terephthalate Polymers 0.000 title abstract description 4
- 239000003085 diluting agent Substances 0.000 claims abstract description 15
- 239000000178 monomer Substances 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims abstract description 10
- 238000002360 preparation method Methods 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 7
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims abstract description 6
- 125000004386 diacrylate group Chemical group 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims description 45
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 38
- 239000000047 product Substances 0.000 claims description 30
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 24
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 24
- 239000002253 acid Substances 0.000 claims description 18
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 15
- 238000001816 cooling Methods 0.000 claims description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 239000007857 degradation product Substances 0.000 claims description 12
- 238000004821 distillation Methods 0.000 claims description 12
- 239000003112 inhibitor Substances 0.000 claims description 10
- 238000006116 polymerization reaction Methods 0.000 claims description 10
- XESZUVZBAMCAEJ-UHFFFAOYSA-N 4-tert-butylcatechol Chemical compound CC(C)(C)C1=CC=C(O)C(O)=C1 XESZUVZBAMCAEJ-UHFFFAOYSA-N 0.000 claims description 8
- 239000005711 Benzoic acid Substances 0.000 claims description 8
- 235000010233 benzoic acid Nutrition 0.000 claims description 8
- 229940120693 copper naphthenate Drugs 0.000 claims description 8
- SEVNKWFHTNVOLD-UHFFFAOYSA-L copper;3-(4-ethylcyclohexyl)propanoate;3-(3-ethylcyclopentyl)propanoate Chemical compound [Cu+2].CCC1CCC(CCC([O-])=O)C1.CCC1CCC(CCC([O-])=O)CC1 SEVNKWFHTNVOLD-UHFFFAOYSA-L 0.000 claims description 8
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 8
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 239000004246 zinc acetate Substances 0.000 claims description 6
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 5
- KUDUQBURMYMBIJ-UHFFFAOYSA-N 2-prop-2-enoyloxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC(=O)C=C KUDUQBURMYMBIJ-UHFFFAOYSA-N 0.000 claims description 4
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 claims description 4
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- XOJWAAUYNWGQAU-UHFFFAOYSA-N 4-(2-methylprop-2-enoyloxy)butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCCOC(=O)C(C)=C XOJWAAUYNWGQAU-UHFFFAOYSA-N 0.000 claims description 3
- SAPGBCWOQLHKKZ-UHFFFAOYSA-N 6-(2-methylprop-2-enoyloxy)hexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCCCCOC(=O)C(C)=C SAPGBCWOQLHKKZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000012752 auxiliary agent Substances 0.000 claims description 3
- AOJOEFVRHOZDFN-UHFFFAOYSA-N benzyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC1=CC=CC=C1 AOJOEFVRHOZDFN-UHFFFAOYSA-N 0.000 claims description 3
- ZDQNWDNMNKSMHI-UHFFFAOYSA-N 1-[2-(2-prop-2-enoyloxypropoxy)propoxy]propan-2-yl prop-2-enoate Chemical compound C=CC(=O)OC(C)COC(C)COCC(C)OC(=O)C=C ZDQNWDNMNKSMHI-UHFFFAOYSA-N 0.000 claims description 2
- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical compound CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-UHFFFAOYSA-N 0.000 claims description 2
- NQSLZEHVGKWKAY-UHFFFAOYSA-N 6-methylheptyl 2-methylprop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C(C)=C NQSLZEHVGKWKAY-UHFFFAOYSA-N 0.000 claims description 2
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 claims description 2
- YCCCTDWBNCWPAX-UHFFFAOYSA-N OC(=O)C=C.OC(=O)C=C.OC(=O)C1=CC=CC=C1C(O)=O Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C1=CC=CC=C1C(O)=O YCCCTDWBNCWPAX-UHFFFAOYSA-N 0.000 claims description 2
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 claims description 2
- FSDNTQSJGHSJBG-UHFFFAOYSA-N piperidine-4-carbonitrile Chemical compound N#CC1CCNCC1 FSDNTQSJGHSJBG-UHFFFAOYSA-N 0.000 claims description 2
- FBCQUCJYYPMKRO-UHFFFAOYSA-N prop-2-enyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC=C FBCQUCJYYPMKRO-UHFFFAOYSA-N 0.000 claims description 2
- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 0.000 claims description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 abstract description 12
- 239000002994 raw material Substances 0.000 abstract description 10
- 238000004064 recycling Methods 0.000 abstract description 5
- 230000036541 health Effects 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 4
- 238000011161 development Methods 0.000 abstract description 3
- 238000003912 environmental pollution Methods 0.000 abstract description 3
- 230000035622 drinking Effects 0.000 description 4
- 239000008213 purified water Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 231100000357 carcinogen Toxicity 0.000 description 2
- 239000003183 carcinogenic agent Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 235000014171 carbonated beverage Nutrition 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 239000011152 fibreglass Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 235000015203 fruit juice Nutrition 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000009512 pharmaceutical packaging Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005464 sample preparation method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 235000013616 tea Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/01—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to unsaturated polyesters
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
The invention discloses a method for preparing unsaturated polyester resin by using waste PET (polyethylene terephthalate) products. The preparation raw materials comprise: 70-80 parts of recovered PET unsaturated polyester resin intermediate and 20-30 parts of active diluent, and the process comprises the following steps: and mixing the recovered PET unsaturated polyester resin intermediate with an active diluent, and stirring for 1 hour at the temperature of 70-85 ℃ to obtain the product. The invention has the advantages that: according to the invention, the unsaturated polyester resin is prepared by recycling PET products, and the mixture of diacrylate monomers and methacrylate monomers is used as the reactive diluent, so that the problems of environmental pollution and health caused by the traditional method of using styrene as the reactive diluent are solved; the unsaturated polyester resin prepared by using the recycled PET as the raw material meets the requirements of green recycling and sustainable development, and the prepared product has better comprehensive performance.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a method for preparing unsaturated polyester resin by using waste PET (polyethylene terephthalate) products.
Background
PET is widely used not only for packaging carbonated beverages, drinking water, fruit juice, tea beverages, and the like, but also in a variety of fields such as food, chemical industry, pharmaceutical packaging, and the like, and more than 50 million tons of PET are used for manufacturing PET bottles every year. If the PET product is not recycled, white contamination can occur in the environment. The unsaturated polyester resin has good physical properties, corrosion resistance, glossiness and fullness, is simple and convenient to process and low in cost, and can be widely applied to industries such as glass fiber reinforced plastic composite materials, gel coat resins, artware and the like as a raw material. Therefore, the recycled waste PET products are degraded into unsaturated polyester resin, so that the problem of environmental pollution can be solved, the recycled PET products can be used as a new raw material resource, and the strategic requirements of green recycling and sustainable development of high polymer materials are met.
At present, the degradation of waste PET products into unsaturated polyester resin in the industry has the following problems: firstly, the unsaturated polyester resin produced by taking recycled PET bottle flakes as raw materials usually takes styrene with strong volatility as an active diluent, the styrene is harmful to human health, the list of carcinogens published by International cancer research institution of world health organization in 2017, 10 and 27 days is preliminarily prepared for reference, and the styrene is in the list of 2B carcinogens. Secondly, the volatility of the unsaturated polyester resin product is also one of the important parameters of the performance of the unsaturated polyester resin product, organic solvents are inevitably contained in the resin, and the organic components can be volatilized due to the excessively high volatility. Finally, if the unsaturated polyester resin product produced by taking the recycled PET bottle flakes as the raw material has a highly crosslinked rigid benzene ring structure after curing, the problems of low toughness, high brittleness, high shrinkage and the like of the cured product are easily caused, so that the impact strength, the tensile strength and the bending strength of the material are not high, and the application of the material in production practice is greatly limited.
Disclosure of Invention
In order to reduce the pollution of PET wastes, the invention recycles the PET wastes to prepare unsaturated polyester resin, does not add styrene as an active diluent, simultaneously solves the volatility problem of the unsaturated polyester resin, and has the advantages of excellent comprehensive performance of the prepared product, high impact strength, tensile strength and bending strength and simple process.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for preparing unsaturated polyester resin by using waste PET products comprises the following raw materials by weight: 70-80 parts of recovered PET unsaturated polyester resin intermediate and 20-30 parts of active diluent, and the process comprises the following steps: and mixing the recovered PET unsaturated polyester resin intermediate with an active diluent, and stirring for 1 hour at the temperature of 70-85 ℃ to obtain the product.
Further, the recycled PET unsaturated polyester resin intermediate comprises the following raw material components (by weight): 160-180 parts of recycled PET bottle flakes, 90-110 parts of diethylene glycol, 5-8 parts of glycerol, 60-80 parts of maleic anhydride, 11-15 parts of benzoic acid and a proper amount of auxiliaries. The auxiliary agent comprises: 0.0005 to 0.0006 part of zinc acetate catalyst, 0.00004 to 0.00005 part of copper naphthenate accelerator, 0.0002 to 0.0003 part of hydroquinone polymerization inhibitor and 0.00004 to 0.00005 part of p-tert-butylcatechol polymerization inhibitor.
The preparation process of the recovered PET type unsaturated polyester resin intermediate comprises the following steps:
(1) mixing the recovered PET bottle flakes, diethylene glycol, glycerol and a catalyst, introducing nitrogen into a reaction system, heating to 218-220 ℃ under a continuous stirring state, controlling the temperature of a distillation head to be less than or equal to 105 ℃, and keeping the temperature until the acid value of the system is reduced to 5 +/-2 mgKOH/g, so as to obtain a clear and transparent recovered PET degradation product;
(2) cooling the obtained recycled PET degradation product to be below 145 ℃, sequentially adding maleic anhydride, benzoic acid and polymerization inhibitor hydroquinone into a reaction system, continuously heating to 180-190 ℃, keeping the temperature for 45 minutes, controlling the temperature of a distillation head to be less than or equal to 105 ℃, continuously heating to 210-215 ℃, and keeping the temperature for 2 hours until the acid value of the product is reduced to 29-33 mgKOH/g;
(3) vacuumizing and decompressing to react until the acid value of the reaction system is reduced to 11-17 mgKOH/g, which is the reaction end point. And cooling the reaction materials to 70-85 ℃, adding a polymerization inhibitor hydroquinone, an accelerator copper naphthenate and a polymerization inhibitor p-tert-butyl catechol into the reaction system, and stirring and mixing for 1 hour. And continuously cooling to room temperature, and crushing the product to obtain the recovered PET type unsaturated polyester resin intermediate.
Further, the reactive diluent is a mixture of diacrylate monomers and methacrylate monomers; wherein the diacrylate monomers include: one or more of 1, 6-hexanediol dimethacrylate, 1, 6-hexanediol diacrylate, 1, 4-butanediol dimethacrylate, ethylene glycol dimethacrylate, tripropylene glycol diacrylate, dipropylene glycol diacrylate, ethylene glycol diacrylate and phthalic acid diacrylate; the methacrylate monomers include: one or more of methyl methacrylate, allyl methacrylate, butyl methacrylate, t-butyl methacrylate, isobutyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate and isooctyl methacrylate.
By adopting the technical scheme, compared with the prior art, the invention has the following technical effects:
according to the invention, the unsaturated polyester resin is prepared by recycling PET products, and the mixture of diacrylate monomers and methacrylate monomers is used as the reactive diluent, so that the problems of environmental pollution and health caused by the traditional method of using styrene as the reactive diluent are solved; the unsaturated polyester resin prepared by using the recycled PET as the raw material meets the requirements of green recycling and sustainable development, and the prepared product has better comprehensive performance.
Detailed description of the invention
In order to make the purpose, technical solution and positive effect of the embodiments of the present invention more clear, the technical solution in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are a part of the embodiments of the present invention, but not all of the embodiments.
In the following examples, the raw materials and reagents used were all industrial products; the reactions mentioned below can be carried out in reaction apparatuses customary in the art, generally in reaction vessels; the reactions mentioned below were carried out under an inert atmosphere, which is a conventional inert atmosphere, which is a nitrogen atmosphere in the examples described below.
Example 1
1. Preparation of recycled PET bottle flakes:
the bottle bodies of the Wahaha drinking purified water (500ml bottles) sold by Hangzhou Wahaha group Limited in the market are collected, the labels of the bottle bodies are removed, and the bottle bodies are cut, cleaned and dried to obtain the recovered PET bottle flakes.
2. Preparation of recovered PET type unsaturated polyester resin intermediate
(1) 171.25kg of recovered PET bottle chips, 101.00kg of diethylene glycol, 6kg of glycerol and 0.56g of zinc acetate are mixed, nitrogen is introduced into a reaction system, the temperature is raised to 218 ℃ under the condition of continuous stirring, the temperature of a distillation head is controlled to be less than or equal to 105 ℃, and the temperature is maintained until the acid value of the system is reduced to 5 +/-2 mgKOH/g, so that clear and transparent recovered PET degradation products are obtained.
(2) And cooling the obtained recovered PET degradation product to below 145 ℃, sequentially adding 70kg of maleic anhydride, 13.5kg of benzoic acid and 0.12g of hydroquinone (1) into the reaction system, continuously heating to 190 ℃, keeping the temperature for 45 minutes, controlling the temperature of a distillation head to be less than or equal to 105 ℃, continuously heating to 210 ℃, and keeping the temperature for 2 hours until the acid value of the product is reduced to 29-33 mgKOH/g.
(3) Vacuumizing and decompressing to react until the acid value of the reaction system is reduced to 11-17 mgKOH/g, which is the reaction end point. When the reaction mass was cooled to 70 ℃, 0.15g of hydroquinone (2), 0.046g of copper naphthenate and 0.041g of p-tert-butylcatechol were added to the reaction system, and stirred and mixed for 1 hour. And continuously cooling to room temperature, and crushing the product to obtain the recovered PET type unsaturated polyester resin intermediate.
3. Preparation of unsaturated polyester resins
26kg of 1, 4-butanediol dimethacrylate and 66kg of methyl methacrylate are sequentially added into a reaction system, the temperature of the system is kept at 70 ℃, and the mixture is stirred and mixed for 1 hour, so that the recycled PET type styrene-free unsaturated polyester resin can be obtained.
Example 2
1. Preparing recycled PET bottle flakes:
the bottle bodies of the Wahaha drinking purified water (500ml bottles) sold by Hangzhou Wahaha group Limited in the market are collected, the labels of the bottle bodies are removed, and the bottle bodies are cut, cleaned and dried to obtain the recovered PET bottle flakes.
2. Preparation of recovered PET type unsaturated polyester resin intermediate
(1) 160kg of recycled PET bottle chips, 90kg of diethylene glycol, 5kg of glycerol and 0.5g of zinc acetate are mixed, nitrogen is introduced into a reaction system, the temperature is raised to 219 ℃ under the condition of continuous stirring, the temperature of a distillation head is controlled to be less than or equal to 105 ℃, and the temperature is maintained until the acid value of the system is reduced to 5 +/-2 mgKOH/g, so that clear and transparent recycled PET degradation products are obtained.
(2) And cooling the obtained recovered PET degradation product to below 145 ℃, sequentially adding 60kg of maleic anhydride, 11kg of benzoic acid and 0.05g of hydroquinone (1) into the reaction system, continuously heating to 180 ℃, keeping the temperature for 45 minutes, controlling the temperature of a distillation head to be less than or equal to 105 ℃, continuously heating to 212 ℃, keeping the temperature for 2 hours, and reducing the acid value of the product to 29-33 mgKOH/g.
(3) Vacuumizing and decompressing to react until the acid value of the reaction system is reduced to 11-17 mgKOH/g, which is the reaction end point. When the reaction mass was cooled to 75 ℃, 0.15g of hydroquinone (2), 0.05g of copper naphthenate and 0.04g of p-tert-butylcatechol were added to the reaction system, and stirred and mixed for 1 hour. And continuously cooling to room temperature, and crushing the product to obtain the recovered PET type unsaturated polyester resin intermediate.
3. Unsaturated polyester resin
24.00kg of 1, 6-hexanediol dimethacrylate and 62.00kg of methyl methacrylate are sequentially added into a reaction system, the temperature of the system is kept at 85 ℃, and the mixture is stirred and mixed for 1 hour, so that the recycled PET type styrene-free unsaturated polyester resin can be obtained.
Example 3
1. Preparing recycled PET bottle flakes:
the bottle bodies of the Wahaha drinking purified water (500ml bottles) sold by Hangzhou Wahaha group Limited in the market are collected, the labels of the bottle bodies are removed, and the bottle bodies are cut, cleaned and dried to obtain the recovered PET bottle flakes.
2. Preparation of recovered PET type unsaturated polyester resin intermediate
(1) 165kg of recycled PET bottle chips, 105.00kg of diethylene glycol, 7kg of glycerol and 0.6g of zinc acetate are mixed, nitrogen is introduced into a reaction system, the temperature is raised to 220 ℃ under the condition of continuous stirring, the temperature of a distillation head is controlled to be less than or equal to 105 ℃, and the temperature is maintained until the acid value of the system is reduced to 5 +/-2 mgKOH/g, so that clear and transparent recycled PET degradation products are obtained.
(2) And cooling the obtained recovered PET degradation product to below 145 ℃, sequentially adding 80kg of maleic anhydride, 13.5kg of benzoic acid and 0.05g of hydroquinone (1) into the reaction system, continuously heating to 185 ℃, keeping the temperature for 45 minutes, controlling the temperature of a distillation head to be less than or equal to 105 ℃, continuously heating to 213 ℃, and keeping the temperature for 2 hours until the acid value of the product is reduced to 29-33 mgKOH/g.
(3) Vacuumizing and decompressing to react until the acid value of the reaction system is reduced to 11-17 mgKOH/g, which is the reaction end point. When the reaction mass was cooled to 80 ℃, 0.23g of hydroquinone (2), 0.04g of copper naphthenate and 0.045g of p-tert-butylcatechol were put into the reaction system, and stirred and mixed for 1 hour. And continuously cooling to room temperature, and crushing the product to obtain the recovered PET type unsaturated polyester resin intermediate.
3. Unsaturated polyester resin
26.00kg of ethylene glycol dimethacrylate and 66.00kg of methyl methacrylate are sequentially added into a reaction system, the temperature of the system is kept at 75 ℃, and the mixture is stirred and mixed for 1 hour, so that the recycled PET type styrene-free unsaturated polyester resin can be obtained.
Example 4
1. Preparing recycled PET bottle flakes:
the bottle bodies of the Wahaha drinking purified water (500ml bottles) sold by Hangzhou Wahaha group Limited in the market are collected, the labels of the bottle bodies are removed, and the bottle bodies are cut, cleaned and dried to obtain the recovered PET bottle flakes.
2. Preparation of recovered PET type unsaturated polyester resin intermediate
(1) Mixing 180kg of recycled PET bottle chips, 110kg of diethylene glycol, 8kg of glycerol and 0.6g of zinc acetate, introducing nitrogen into a reaction system, heating to 218 ℃ under the condition of continuous stirring, controlling the temperature of a distillation head to be less than or equal to 105 ℃, and preserving heat until the acid value of the system is reduced to 5 +/-2 mgKOH/g, thereby obtaining a clear and transparent recycled PET degradation product.
(2) And cooling the obtained recovered PET degradation product to below 145 ℃, sequentially adding 70kg of maleic anhydride, 15kg of benzoic acid and 0.14g of hydroquinone (1) into the reaction system, continuously heating to 190 ℃, keeping the temperature for 45 minutes, controlling the temperature of a distillation head to be less than or equal to 105 ℃, continuously heating to 215 ℃, keeping the temperature for 2 hours, and reducing the acid value of the product to 29-33 mgKOH/g.
(3) Vacuumizing and decompressing to react until the acid value of the reaction system is reduced to 11-17 mgKOH/g, which is the reaction end point. When the reaction mass was cooled to 85 ℃, 0.16g of hydroquinone (2), 0.045g of copper naphthenate and 0.05g of p-tert-butylcatechol were put into the reaction system, and stirred and mixed for 1 hour. And continuously cooling to room temperature, and crushing the product to obtain the recovered PET type unsaturated polyester resin intermediate.
3. Unsaturated polyester resin
26.00kg of ethylene glycol dimethacrylate and 66.00kg of benzyl methacrylate are sequentially added into a reaction system, the temperature of the system is kept at 80 ℃, and the mixture is stirred and mixed for 1 hour, so that the recycled PET type styrene-free unsaturated polyester resin can be obtained.
Effect example 1
The recycled PET type styrene-free unsaturated polyester resins obtained in examples 1 to 4 of the present invention were subjected to physical property tests, and the specific test results are shown in the following tables.
Effect example 2
2% of initiator methyl ethyl ketone peroxide is added into the recycled PET type styrene-free unsaturated polyester resin prepared in the embodiments 1-4 of the invention and is uniformly mixed, the mixture is placed in an oven at 85 ℃ for 2 hours, the sample preparation method of a casting body is carried out according to GB/T8237, and the specific test results are shown in the following table.
As can be seen from the above table, the recycled PET type styrene-free unsaturated polyester resins of examples 1 to 4 have excellent overall mechanical properties after curing. Meanwhile, the reactive diluent selected by the invention has the characteristics of low odor, high boiling point and high flash point, so the recycled PET type styrene-free unsaturated polyester resin prepared by the embodiments 1 to 4 of the invention has the characteristic of low VOC emission.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are only exemplary embodiments of the present invention, and are not intended to limit the present invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (2)
1. A method for preparing unsaturated polyester resin by using waste PET products is characterized in that a recovered PET unsaturated polyester resin intermediate is mixed with a reactive diluent, and the mixture is stirred for 1 hour at the temperature of 70-85 ℃ to obtain a product, wherein the recovered PET unsaturated polyester resin intermediate accounts for 70-80 parts by weight, and the reactive diluent accounts for 20-30 parts by weight; the method is characterized in that the recovered PET unsaturated polyester resin intermediate is prepared from the following components (by weight): 160-180 parts of recovered PET bottle flakes, 90-110 parts of diethylene glycol, 5-8 parts of glycerol, 60-80 parts of maleic anhydride, 11-15 parts of benzoic acid and a proper amount of auxiliary agent; the auxiliary agent comprises: 0.0005 to 0.0006 part of zinc acetate catalyst, 0.00004 to 0.00005 part of copper naphthenate accelerator, 0.0002 to 0.0003 part of hydroquinone serving as a polymerization inhibitor, and 0.00004 to 0.00005 part of p-tert-butylcatechol serving as a polymerization inhibitor; the preparation process of the recovered PET type unsaturated polyester resin intermediate comprises the following steps:
(1) mixing the recovered PET bottle flakes, diethylene glycol, glycerol and a catalyst, introducing nitrogen into a reaction system, heating to 218-220 ℃ under a continuous stirring state, controlling the temperature of a distillation head to be less than or equal to 105 ℃, and keeping the temperature until the acid value of the system is reduced to 5 +/-2 mgKOH/g, so as to obtain a clear and transparent recovered PET degradation product;
(2) cooling the obtained recycled PET degradation product to be below 145 ℃, sequentially adding maleic anhydride, benzoic acid and polymerization inhibitor hydroquinone into a reaction system, continuously heating to 180-190 ℃, keeping the temperature for 45 minutes, controlling the temperature of a distillation head to be less than or equal to 105 ℃, continuously heating to 210-215 ℃, and keeping the temperature for 2 hours until the acid value of the product is reduced to 29-33 mgKOH/g;
(3) vacuumizing and decompressing for reaction, taking the reaction end point when the acid value of a reaction system is reduced to 11-17 mgKOH/g, cooling the reaction materials to 70-85 ℃, adding a polymerization inhibitor hydroquinone, an accelerant copper naphthenate and a polymerization inhibitor p-tert-butyl catechol into the reaction system, stirring and mixing for 1 hour, continuously cooling to room temperature, and crushing the product to obtain the recovered PET type unsaturated polyester resin intermediate.
2. The method for preparing unsaturated polyester resin using waste PET articles as claimed in claim 1, wherein the reactive diluent is a mixture of diacrylate monomer and methacrylate monomer; wherein the diacrylate monomers include: one or more of 1, 6-hexanediol dimethacrylate, 1, 6-hexanediol diacrylate, 1, 4-butanediol dimethacrylate, ethylene glycol dimethacrylate, tripropylene glycol diacrylate, dipropylene glycol diacrylate, ethylene glycol diacrylate and phthalic acid diacrylate; the methacrylate monomers include: one or more of methyl methacrylate, allyl methacrylate, butyl methacrylate, t-butyl methacrylate, isobutyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate and isooctyl methacrylate.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102225986A (en) * | 2011-04-21 | 2011-10-26 | 苏州巨峰电气绝缘系统股份有限公司 | Environmentally-friendly type solvent-free impregnating resin and preparation method thereof |
| CN103819620A (en) * | 2013-12-11 | 2014-05-28 | 浙江天和树脂有限公司 | PET recovery type unsaturated polyester mold pressing well lid resin, and preparation method and application thereof |
| CN105367769A (en) * | 2015-12-17 | 2016-03-02 | 肇庆福田化学工业有限公司 | Method for synthesizing unsaturated polyester resin by utilizing PET |
| CN105980466A (en) * | 2014-02-11 | 2016-09-28 | 阿克苏诺贝尔化学品国际有限公司 | Process for curing (meth)acrylate-containing UP or VE resin |
| CN107955113A (en) * | 2017-11-29 | 2018-04-24 | 华南理工大学 | A kind of flexible unsaturated polyester resin of no styrene and preparation method thereof |
| CN109734890A (en) * | 2018-11-29 | 2019-05-10 | 常州华科聚合物股份有限公司 | A kind of preparation method of no styrene unsaturated-resin |
-
2020
- 2020-11-19 CN CN202011302889.0A patent/CN112480327A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102225986A (en) * | 2011-04-21 | 2011-10-26 | 苏州巨峰电气绝缘系统股份有限公司 | Environmentally-friendly type solvent-free impregnating resin and preparation method thereof |
| CN103819620A (en) * | 2013-12-11 | 2014-05-28 | 浙江天和树脂有限公司 | PET recovery type unsaturated polyester mold pressing well lid resin, and preparation method and application thereof |
| CN105980466A (en) * | 2014-02-11 | 2016-09-28 | 阿克苏诺贝尔化学品国际有限公司 | Process for curing (meth)acrylate-containing UP or VE resin |
| CN105367769A (en) * | 2015-12-17 | 2016-03-02 | 肇庆福田化学工业有限公司 | Method for synthesizing unsaturated polyester resin by utilizing PET |
| CN107955113A (en) * | 2017-11-29 | 2018-04-24 | 华南理工大学 | A kind of flexible unsaturated polyester resin of no styrene and preparation method thereof |
| CN109734890A (en) * | 2018-11-29 | 2019-05-10 | 常州华科聚合物股份有限公司 | A kind of preparation method of no styrene unsaturated-resin |
Non-Patent Citations (1)
| Title |
|---|
| 翁祖祺等: "《中国玻璃钢工业大全》", 29 February 1992, 国防工业出版社 * |
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