CN104725260A - Method for degrading PET and synthesizing unsaturated polyester resin - Google Patents
Method for degrading PET and synthesizing unsaturated polyester resin Download PDFInfo
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- CN104725260A CN104725260A CN201510031907.9A CN201510031907A CN104725260A CN 104725260 A CN104725260 A CN 104725260A CN 201510031907 A CN201510031907 A CN 201510031907A CN 104725260 A CN104725260 A CN 104725260A
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Abstract
The invention discloses a method for degrading PET and preparing an unsaturated polyester resin. The method for degrading PET comprises the following steps: simultaneously adding ethanol amine and dihydric alcohol into PET, wherein the mol ratio of the ethanol amine to dihydric alcohol is 1:10-2:5, heating at the temperature of 160-210 DEG C in the presence of an organic metal catalyst and keeping the temperature for 1-4h. The PET can be degraded in a short reaction time at a low reaction temperature so that the production efficiency is greatly increased.
Description
Technical field
The present invention relates to the degradation method of a kind of PET,
Background technology
China has become the maximum production and consumption country of PET and UPR (unsaturated polyester resin), a large amount of PET urgently recycles, and PET (polyethylene terephthalate) has pyrolysis, biological degradation, chemical degradation (hydrolysis, aminolysis, alcoholysis) etc. to reclaim approach.Pyrolysis recovery value is low, and biological degradation efficiency is low, difficult industrialization, in chemical degradation, alcoholysis recovery value is high, had many enterprises to drop in industrial production at present, but shortcoming also clearly at thermoplastic polyester and unsaturated polyester resin industry, speed of reaction is low, and requirement condition is more.
Recycle the PET of tens0000 tons every year in unsaturated polyester resin industry, synthesis terephthalic unsaturated polyester resin, has the lower thermal expansivity of neighbour benzene-type resins for universal use, better corrosion-resistant, physicals and sufficient raw cheap.But too time consumption and energy consumption in alcoholysis reaction process, have impact on production efficiency, meanwhile, temperature of reaction is high, long reaction time, and the color of resin of synthesis is dark, and even permeability is bad, constrains the recycling of PET in unsaturated polyester industry to a certain extent.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of unsaturated polyester resin, to solve the above-mentioned problems in the prior art.
Technical scheme provided by the invention is as follows:
A degradation method of PET, comprises the steps: in PET, adds thanomin and dibasic alcohol simultaneously, and thanomin and dibasic alcohol mol ratio are 1:10-2:5, heat under organo-metallic catalyst existent condition, and Heating temperature is 160-210 DEG C, insulation 1-4h.
In a preferred embodiment of the present invention, thanomin and dibasic alcohol mol ratio are 1:5, heat under organo-metallic catalyst existent condition, at 160 DEG C of insulation 1h, and 190 DEG C of insulation 1h.
In another preferred embodiment of the present invention, thanomin and dibasic alcohol mol ratio are 1:10, heat under organo-metallic catalyst existent condition, at 160 DEG C of insulation 1h, and 210 DEG C of insulation 2h.
In still another preferred embodiment of the present invention, thanomin and dibasic alcohol mol ratio are 1:5, heat under organo-metallic catalyst existent condition, at 160 DEG C of insulation 1h, and 190 DEG C of insulation 1h.
Wherein, dibasic alcohol of the present invention comprises ethylene glycol, propylene glycol, glycol ether, dipropylene glycol methyl propanediol, at least one in neopentyl glycol, dihydroxyphenyl propane.
In the present invention, the amount of PET can be 1-2 times of total amount of liquid, is preferably 1.3 times.
Another technical scheme of the present invention is:
A preparation method for unsaturated polyester resin, comprises the steps:
1) in PET, add thanomin and dibasic alcohol, thanomin and dibasic alcohol mol ratio are 1:10-2:5, heat under organo-metallic catalyst existent condition simultaneously, and Heating temperature is 160-210 DEG C, insulation 1-4h.
2) become solution shape after PET degraded, adding unsaturated dibasic acid and monounsaturated dicarboxylic acid esterification, fully after reaction, cooling, adds linking agent and other auxiliary agent.
Wherein, step 1) dibasic alcohol comprises ethylene glycol, propylene glycol, glycol ether, dipropylene glycol methyl propanediol, at least one in neopentyl glycol, dihydroxyphenyl propane.
Wherein, step 1) amount of PET be the 1-2 of total amount of liquid doubly.
Reaction formula of the present invention is as follows:
The present invention introduces monoethanolamine and dibasic alcohol and organo-metallic catalyst and jointly degrades, it is low that PET separates temperature in monoethanolamine amine, just can aminolysis at 100 DEG C, the more important thing is that thanomin makes PET start aminolysis at lesser temps, PET particle is attenuated, and surface-area sharply increases, thus dibasic alcohol and PET speed of reaction are increased, according to technical scheme of the present invention, finally make PET can degrade under shorter reaction times and lower temperature of reaction, greatly enhance productivity.
Embodiment
Raw material sources: PET is recycled PET
Embodiment 1
Thanomin: dibasic alcohol (ethylene glycol) mol ratio is 0:10, catalyzer is Mono-n-butyltin, and consumption is 0.1% of PET weight,
PET consumption is 1.3 times (weight ratios) of total amount of liquid (thanomin+ethylene glycol), is warming up to 190 DEG C of degraded 1h, then is warming up to 210 degree of degraded 1h.
Embodiment 2
Thanomin: dibasic alcohol (ethylene glycol) mol ratio is 0:10, catalyzer is Mono-n-butyltin, and consumption is 0.1% of PET weight,
PET consumption is 1.3 times (weight ratios) of total amount of liquid, is warming up to 160 DEG C of degraded 1h, then is warming up to 190 degree of degraded 1h.
Embodiment 3
Thanomin: dibasic alcohol (propylene glycol) mol ratio is 0:10, catalyzer is Mono-n-butyltin, and consumption is 0.1% of PET weight,
PET consumption is 1.3 times (weight ratios) of total amount of liquid, is warming up to 210 DEG C of degraded 4h.
Embodiment 4
Thanomin: dibasic alcohol (propylene glycol) mol ratio is 1:10, catalyzer is Mono-n-butyltin, and consumption is 0.1% of PET weight,
PET consumption is 1.3 times (weight ratios) of total amount of liquid, is warming up to 160 DEG C of degraded 1h, then is warming up to 190 degree of degraded 1h.
Embodiment 5
Thanomin: dibasic alcohol (dihydroxyphenyl propane) mol ratio is 1:10, catalyzer is Mono-n-butyltin, and consumption is 0.1% of PET weight,
PET consumption is 1.3 times (weight ratios) of total amount of liquid, is warming up to 160 DEG C of degraded 2h, then is warming up to 190 degree of degraded 1h.
Embodiment 6
Thanomin: dibasic alcohol (dihydroxyphenyl propane) mol ratio is 1:10, catalyzer is Mono-n-butyltin, and consumption is 0.1% of PET weight,
PET consumption is 1.3 times (weight ratios) of total amount of liquid, is warming up to 160 DEG C of degraded 1h, then is warming up to 210 degree of degraded 2h.
Embodiment 7
Thanomin: dibasic alcohol (ethylene glycol) mol ratio is 1:5, catalyzer is Mono-n-butyltin, and consumption is 0.1% of PET weight,
PET consumption is 1.3 times (weight ratios) of total amount of liquid, is warming up to 160 DEG C of degraded 2h, then is warming up to 190 degree of degraded 2h.
Embodiment 8
Thanomin: dibasic alcohol (ethylene glycol) mol ratio is 1:5, catalyzer is Mono-n-butyltin, and consumption is 0.1% of PET weight,
PET consumption is 1.3 times (weight ratios) of total amount of liquid, is warming up to 160 DEG C of degraded 1h, then is warming up to 190 degree of degraded 2h.
Embodiment 9
Thanomin: dibasic alcohol (glycol ether) mol ratio is 2:5, catalyzer is Mono-n-butyltin, and consumption is 0.1% of PET weight,
PET consumption is 1.3 times (weight ratios) of total amount of liquid, is warming up to 160 DEG C of degraded 2h.
Each embodiment experimental result is as follows:
Embodiment 10
In the PET solution that embodiment 6 is obtained, add unsaturated dibasic acid (MALEIC ANHYDRIDE) and monounsaturated dicarboxylic acid (Tetra hydro Phthalic anhydride) esterification, the weight ratio between PET solution, unsaturated dibasic acid, monounsaturated dicarboxylic acid three is 6:3:1.After abundant reaction, cooling, adds linking agent and other auxiliary agent.Obtained product effect is yellow transparent thick liquid.
Embodiment 11
In the PET solution that embodiment 7 is obtained, add unsaturated dibasic acid (MALEIC ANHYDRIDE) and monounsaturated dicarboxylic acid (Tetra hydro Phthalic anhydride) esterification, the weight ratio between PET solution, unsaturated dibasic acid, monounsaturated dicarboxylic acid three is 6:3:1.After abundant reaction, cooling, adds linking agent and other auxiliary agent.Obtained product effect is pale yellow transparent thick liquid.
Claims (9)
1. a degradation method of PET, comprises the steps: in PET, adds thanomin and dibasic alcohol simultaneously, and thanomin and dibasic alcohol mol ratio are 1:10-2:5, heat under organo-metallic catalyst existent condition, and Heating temperature is 160-210 DEG C, insulation 1-4h.
2. the degradation method of a kind of PET as claimed in claim 1, is characterized in that, comprises the steps: in PET, add thanomin and dibasic alcohol, thanomin and dibasic alcohol mol ratio are 1:5, heat under organo-metallic catalyst existent condition simultaneously, at 160 DEG C of insulation 1h, 190 DEG C of insulation 1h.
3. the degradation method of a kind of PET as claimed in claim 1, is characterized in that: in PET, adds thanomin and dibasic alcohol simultaneously, thanomin and dibasic alcohol mol ratio are 1:10, heat under organo-metallic catalyst existent condition, at 160 DEG C of insulation 1h, 210 DEG C of insulation 2h.
4. the degradation method of a kind of PET as claimed in claim 1, is characterized in that: in PET, adds thanomin and dibasic alcohol simultaneously, thanomin and dibasic alcohol mol ratio are 1:5, heat under organo-metallic catalyst existent condition, at 160 DEG C of insulation 1h, 190 DEG C of insulation 1h.
5. the degradation method of a kind of PET as described in any one of Claims 1-4, is characterized in that: dibasic alcohol comprises ethylene glycol, propylene glycol, glycol ether, dipropylene glycol methyl propanediol, at least one in neopentyl glycol, dihydroxyphenyl propane.
6. the degradation method of a kind of PET as claimed in claim 1, is characterized in that: the amount of PET is 1-2 times of total amount of liquid.
7. a preparation method for unsaturated polyester resin, comprises the steps:
1) in PET, add thanomin and dibasic alcohol, thanomin and dibasic alcohol mol ratio are 1:10-2:5, heat under organo-metallic catalyst existent condition simultaneously, and Heating temperature is 160-210 DEG C, insulation 1-4h;
2) become solution shape after PET degraded, then add unsaturated dibasic acid and monounsaturated dicarboxylic acid esterification, fully after reaction, cooling, adds linking agent and other auxiliary agent.
8. the preparation method of a kind of unsaturated polyester resin as claimed in claim 7, it is characterized in that: step 1) dibasic alcohol comprises ethylene glycol, propylene glycol, glycol ether, dipropylene glycol methyl propanediol, at least one in neopentyl glycol, dihydroxyphenyl propane.
9. the preparation method of a kind of unsaturated polyester resin as claimed in claim 7, is characterized in that: step 1) amount of PET be the 1-2 of total amount of liquid doubly.
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| CN201510031907.9A CN104725260B (en) | 2015-01-22 | 2015-01-22 | The degraded of PET a kind of and the method for synthesizing unsaturated polyester resin |
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| CN201510031907.9A CN104725260B (en) | 2015-01-22 | 2015-01-22 | The degraded of PET a kind of and the method for synthesizing unsaturated polyester resin |
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| CN104725260B CN104725260B (en) | 2017-08-29 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109942431A (en) * | 2019-04-02 | 2019-06-28 | 苏州湘园新材料股份有限公司 | A kind of aromatic diol class compound and preparation method thereof |
| CN110180597A (en) * | 2019-05-22 | 2019-08-30 | 漳州亚邦化学有限公司 | A kind of composite catalyst and PET biodegrading process for PET degradation |
Citations (4)
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|---|---|---|---|---|
| US5380793A (en) * | 1993-07-13 | 1995-01-10 | Ashland Oil, Inc. | Styrene soluble unsatured polyester resin from polyethylene terephthalate |
| CN101137694A (en) * | 2005-01-18 | 2008-03-05 | 亚什兰许可和知识产权有限公司 | Low viscosity unsaturated polyester resin with reduced voc emission levels |
| CN101948670A (en) * | 2010-10-15 | 2011-01-19 | 济南大学 | Preparation method and application of water-based polymer adhesive |
| CN102120721A (en) * | 2011-01-12 | 2011-07-13 | 江南大学 | Method for preparing epoxy resin curing agent by degrading polyethylene terephthalate with glycerine |
-
2015
- 2015-01-22 CN CN201510031907.9A patent/CN104725260B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5380793A (en) * | 1993-07-13 | 1995-01-10 | Ashland Oil, Inc. | Styrene soluble unsatured polyester resin from polyethylene terephthalate |
| CN101137694A (en) * | 2005-01-18 | 2008-03-05 | 亚什兰许可和知识产权有限公司 | Low viscosity unsaturated polyester resin with reduced voc emission levels |
| CN101948670A (en) * | 2010-10-15 | 2011-01-19 | 济南大学 | Preparation method and application of water-based polymer adhesive |
| CN102120721A (en) * | 2011-01-12 | 2011-07-13 | 江南大学 | Method for preparing epoxy resin curing agent by degrading polyethylene terephthalate with glycerine |
Non-Patent Citations (3)
| Title |
|---|
| VIJAYKUMAR SINHA ET AL.: "Pet Waste Management by Chemical Recycling: A Review", 《J POLYM ENVIRON》 * |
| 杨俊辉: "废弃PET的化学降解与回收研究", 《包装工程》 * |
| 王晓春 等: "PET降解研究", 《合成纤维》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109942431A (en) * | 2019-04-02 | 2019-06-28 | 苏州湘园新材料股份有限公司 | A kind of aromatic diol class compound and preparation method thereof |
| CN110180597A (en) * | 2019-05-22 | 2019-08-30 | 漳州亚邦化学有限公司 | A kind of composite catalyst and PET biodegrading process for PET degradation |
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| CN104725260B (en) | 2017-08-29 |
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