CN104725260B - The degraded of PET a kind of and the method for synthesizing unsaturated polyester resin - Google Patents
The degraded of PET a kind of and the method for synthesizing unsaturated polyester resin Download PDFInfo
- Publication number
- CN104725260B CN104725260B CN201510031907.9A CN201510031907A CN104725260B CN 104725260 B CN104725260 B CN 104725260B CN 201510031907 A CN201510031907 A CN 201510031907A CN 104725260 B CN104725260 B CN 104725260B
- Authority
- CN
- China
- Prior art keywords
- pet
- dihydric alcohol
- monoethanolamine
- organo
- mol ratio
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Macromonomer-Based Addition Polymer (AREA)
- Polyesters Or Polycarbonates (AREA)
- Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
Abstract
The invention discloses the degraded of PET a kind of and the preparation method of unsaturated polyester resin, PET biodegrading process comprises the following steps：In PET, while adding monoethanolamine and dihydric alcohol, monoethanolamine and dihydric alcohol mol ratio are 1:10‑2:5, heated under conditions of organo-metallic catalyst presence, heating-up temperature is 160 210 DEG C, is incubated 1 4h.PET of the present invention can degrade under shorter reaction time and relatively low reaction temperature, greatly improve production efficiency.
Description
Technical field
The present invention relates to a kind of PET biodegrading process,
Background technology
China has become the maximum production and consumption countries of PET and UPR (unsaturated polyester resin), and substantial amounts of PET is urgently
Processing to be recycled, PET (PET) has pyrolysis, biodegradation, chemical degradation (hydrolysis, aminolysis, alcoholysis) etc.
Recovery approach.Pyrolysis recovery value is low, and biodegradable efficiency is low, hardly possible industrialization, and alcoholysis recovery value is high in chemical degradation, at present
In thermoplastic polyester and unsaturated polyester resin industry have had many enterprise's input industrial productions, but shortcoming is also very bright
Aobvious, reaction rate is low, it is desirable to which condition is more.
In the PET of unsaturated polyester resin industry ten tens of thousands of tons of recycling every year, terephthalic unsaturated polyester tree is synthesized
Fat, with the lower thermal coefficient of expansion of neighbour benzene-type resins for universal use, more preferable corrosion-resistant, physical property and sufficient raw
It is cheap.But during alcoholysis reaction too time consumption and energy consumption, have impact on production efficiency, meanwhile, reaction temperature is high, during reaction
Between it is long, the color of resin of synthesis is deep, or even permeability is bad, and PET returning in unsaturated polyester (UP) industry is constrained to a certain extent
Receive and utilize.
The content of the invention
It is an object of the invention to provide a kind of preparation method of unsaturated polyester resin, to solve to exist in the prior art
Above mentioned problem.
The technical scheme that the present invention is provided is as follows：
A kind of PET biodegrading process, comprises the following steps：In PET, while adding monoethanolamine and dihydric alcohol, monoethanolamine
It is 1 with dihydric alcohol mol ratio:10-2:5, heated under conditions of organo-metallic catalyst presence, heating-up temperature is 160-210
DEG C, it is incubated 1-4h.
In the preferred embodiment of the present invention, monoethanolamine and dihydric alcohol mol ratio are 1:5, deposited in organo-metallic catalyst
Heat under the conditions, 1h, 190 DEG C of insulation 1h are incubated at 160 DEG C.
In another preferred embodiment of the present invention, monoethanolamine and dihydric alcohol mol ratio are 1:10, in metal organic catalysis
Agent is heated under conditions of existing, and 1h, 210 DEG C of insulation 2h are incubated at 160 DEG C.
In still another preferred embodiment of the present invention, monoethanolamine and dihydric alcohol mol ratio are 1:5, in organo-metallic catalyst
Heated in the presence of under conditions of, 1h, 190 DEG C of insulation 1h are incubated at 160 DEG C.
Wherein, dihydric alcohol of the present invention includes ethylene glycol, propane diols, diglycol, dipropylene glycol first
At least one of base propane diols, neopentyl glycol, bisphenol-A.
In the present invention, PET amount can be 1-2 times, preferably 1.3 times of total amount of liquid.
The present invention another technical scheme be：
A kind of preparation method of unsaturated polyester resin, comprises the following steps：
1) in PET, while adding monoethanolamine and dihydric alcohol, monoethanolamine and dihydric alcohol mol ratio are 1:10-2:5, having
Organic metal catalyst is heated under conditions of existing, and heating-up temperature is 160-210 DEG C, is incubated 1-4h.
2) unsaturated dibasic acid and monounsaturated dicarboxylic acid esterification are being added into solution shape after PET degradeds, it is cold fully after reaction
But, crosslinking agent and other auxiliary agents are added.
Wherein, step 1) dihydric alcohol include ethylene glycol, propane diols, diglycol, dipropylene glycol methyl-prop two
At least one of alcohol, neopentyl glycol, bisphenol-A.
Wherein, step 1) PET amount is 1-2 times of total amount of liquid.
The reaction equation of the present invention is as follows：
Degraded jointly present invention introduces MEA and dihydric alcohol and organo-metallic catalyst, PET is in MEA amine
Solve temperature low, can aminolysis at 100 DEG C, it is often more important that monoethanolamine makes PET start aminolysis in lower temperature, become PET particles
Carefully, surface area is sharply increased, so that dihydric alcohol and the increase of PET reaction rates, according to technical scheme, finally make
PET can degrade under shorter reaction time and relatively low reaction temperature, greatly improve production efficiency.
Embodiment
Raw material sources：PET is recycled PET
Embodiment 1
Monoethanolamine：Dihydric alcohol (ethylene glycol) mol ratio is 0:10, catalyst is Mono-n-butyltin, and consumption is PET weight
0.1%,
Amount of PET is 1.3 times (weight ratios) of total amount of liquid (monoethanolamine+ethylene glycol), is warming up to 190 DEG C of degraded 1h, then
It is warming up to 210 degree of degraded 1h.
Embodiment 2
Monoethanolamine：Dihydric alcohol (ethylene glycol) mol ratio is 0:10, catalyst is Mono-n-butyltin, and consumption is PET weight
0.1%,
Amount of PET is 1.3 times (weight ratios) of total amount of liquid, is warming up to 160 DEG C of degraded 1h, then be warming up to 190 degree of degradeds
1h。
Embodiment 3
Monoethanolamine：Dihydric alcohol (propane diols) mol ratio is 0:10, catalyst is Mono-n-butyltin, and consumption is PET weight
0.1%,
Amount of PET is 1.3 times (weight ratios) of total amount of liquid, is warming up to 210 DEG C of degraded 4h.
Embodiment 4
Monoethanolamine：Dihydric alcohol (propane diols) mol ratio is 1:10, catalyst is Mono-n-butyltin, and consumption is PET weight
0.1%,
Amount of PET is 1.3 times (weight ratios) of total amount of liquid, is warming up to 160 DEG C of degraded 1h, then be warming up to 190 degree of degradeds
1h。
Embodiment 5
Monoethanolamine：Dihydric alcohol (bisphenol-A) mol ratio is 1:10, catalyst is Mono-n-butyltin, and consumption is PET weight
0.1%,
Amount of PET is 1.3 times (weight ratios) of total amount of liquid, is warming up to 160 DEG C of degraded 2h, then be warming up to 190 degree of degradeds
1h。
Embodiment 6
Monoethanolamine：Dihydric alcohol (bisphenol-A) mol ratio is 1:10, catalyst is Mono-n-butyltin, and consumption is PET weight
0.1%,
Amount of PET is 1.3 times (weight ratios) of total amount of liquid, is warming up to 160 DEG C of degraded 1h, then be warming up to 210 degree of degradeds
2h。
Embodiment 7
Monoethanolamine：Dihydric alcohol (ethylene glycol) mol ratio is 1:5, catalyst is Mono-n-butyltin, and consumption is PET weight
0.1%,
Amount of PET is 1.3 times (weight ratios) of total amount of liquid, is warming up to 160 DEG C of degraded 2h, then be warming up to 190 degree of degradeds
2h。
Embodiment 8
Monoethanolamine：Dihydric alcohol (ethylene glycol) mol ratio is 1:5, catalyst is Mono-n-butyltin, and consumption is PET weight
0.1%,
Amount of PET is 1.3 times (weight ratios) of total amount of liquid, is warming up to 160 DEG C of degraded 1h, then be warming up to 190 degree of degradeds
2h。
Embodiment 9
Monoethanolamine：Dihydric alcohol (diglycol) mol ratio is 2:5, catalyst is Mono-n-butyltin, and consumption is PET
The 0.1% of weight,
Amount of PET 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 PET solution made from embodiment 6, unsaturated dibasic acid (maleic anhydride) and monounsaturated dicarboxylic acid are added
(phthalic anhydride) is esterified, and the weight ratio between PET solution, unsaturated dibasic acid, monounsaturated dicarboxylic acid three is 6:3:1.Fill
Divide after reaction, cooling adds crosslinking agent and other auxiliary agents.Obtained product effect is yellow transparent thick liquid.
Embodiment 11
In PET solution made from embodiment 7, unsaturated dibasic acid (maleic anhydride) and monounsaturated dicarboxylic acid are added
(phthalic anhydride) is esterified, and the weight ratio between PET solution, unsaturated dibasic acid, monounsaturated dicarboxylic acid three is 6:3:1.Fill
Divide after reaction, cooling adds crosslinking agent and other auxiliary agents.Obtained product effect is pale yellow transparent thick liquid.
Claims (4)
1. a kind of PET biodegrading process, comprises the following steps：In PET, while add monoethanolamine and dihydric alcohol, monoethanolamine and
Dihydric alcohol mol ratio is 1:10-2:5, heated under conditions of organo-metallic catalyst presence, heating-up temperature is 160-210 DEG C,
1-4h is incubated, the organo-metallic catalyst is Mono-n-butyltin；
Wherein, the dihydric alcohol is at least one of ethylene glycol, propane diols, diglycol, neopentyl glycol；
PET amount is 1-2 times of total amount of liquid.
2. a kind of PET biodegrading process as claimed in claim 1, it is characterised in that comprise the following steps：In PET, simultaneously
Monoethanolamine and dihydric alcohol are added, monoethanolamine and dihydric alcohol mol ratio are 1:5, add under conditions of organo-metallic catalyst presence
Heat, 1h, 190 DEG C of insulation 1h are incubated at 160 DEG C.
3. a kind of PET biodegrading process as claimed in claim 1, it is characterised in that：In PET, at the same add monoethanolamine and
Dihydric alcohol, monoethanolamine and dihydric alcohol mol ratio are 1:10, heated under conditions of organo-metallic catalyst presence, in 160 DEG C of guarantors
Warm 1h, 210 DEG C of insulation 2h.
4. a kind of preparation method of unsaturated polyester resin, comprises the following steps：
1) in PET, while adding monoethanolamine and dihydric alcohol, monoethanolamine and dihydric alcohol mol ratio are 1:10-2:5, in organic gold
Metal catalyst is heated under conditions of existing, and heating-up temperature is 160-210 DEG C, is incubated 1-4h；The organo-metallic catalyst is single
Butyl tin oxide；Wherein, dihydric alcohol is at least one of ethylene glycol, propane diols, diglycol, neopentyl glycol；PET's
Measure as 1-2 times of total amount of liquid；
2) into solution shape after PET degradeds, unsaturated dibasic acid and monounsaturated dicarboxylic acid esterification are added, fully after reaction, cooling, plus
Enter crosslinking agent and other auxiliary agents.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| 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 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| 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 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104725260A CN104725260A (en) | 2015-06-24 |
| CN104725260B true CN104725260B (en) | 2017-08-29 |
Family
ID=53449742
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510031907.9A Expired - Fee Related CN104725260B (en) | 2015-01-22 | 2015-01-22 | The degraded of PET a kind of and the method for synthesizing unsaturated polyester resin |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104725260B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US12037452B2 (en) | 2021-03-25 | 2024-07-16 | Far Eastern New Century Corporation | Amide group-containing polyether-ester material and preparation method thereof, molded article and forming method thereof |
Families Citing this family (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 |
| CN110180597B (en) * | 2019-05-22 | 2022-04-12 | 漳州亚邦化学有限公司 | Composite catalyst for PET degradation and PET degradation method |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Family Cites Families (2)
| 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 |
| CN102120721B (en) * | 2011-01-12 | 2013-08-07 | 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 (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Non-Patent Citations (1)
| Title |
|---|
| 废弃PET的化学降解与回收研究;杨俊辉;《包装工程》;20080430;第29卷(第4期);第27-30页 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US12037452B2 (en) | 2021-03-25 | 2024-07-16 | Far Eastern New Century Corporation | Amide group-containing polyether-ester material and preparation method thereof, molded article and forming method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104725260A (en) | 2015-06-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP3212703B1 (en) | Polymeric plasticizer compositions | |
| CN103265668B (en) | The preparation method of terephthalic unsaturated polyester resin | |
| CN104059214B (en) | Preparation method of high-hardness thermoplastic polyurethane elastomer | |
| CN104725260B (en) | The degraded of PET a kind of and the method for synthesizing unsaturated polyester resin | |
| CN105585704A (en) | Bio-polyether ester elastomer and preparation method therefor | |
| CN106854277A (en) | A kind of super quick-drying alkide resin and preparation method thereof | |
| CN103951817A (en) | Synthetic method of unsaturated polyester resin for producing agglomerated stones | |
| CN102206311A (en) | Saturated polyester for sheet moulding compound or bulk molding compound (SMC/BMC) low-shrinking agent and preparation method thereof | |
| CN101775125A (en) | Non-aromatic nucleus structure poly-hexahydrobenzene phthalic anhydride dihydric alcohol ester plasticizer and preparation method thereof | |
| CN110643023B (en) | Method for preparing unsaturated polyester resin from waste PETG | |
| CN106349502B (en) | Mixed type polyacid ester plasticizer and preparation method thereof | |
| CN102336042A (en) | Polyester composite film and its preparation method | |
| CN107459636B (en) | Polyester heat shrinkable film with low initial shrinkage temperature and preparation method thereof | |
| CN106432704A (en) | Unsaturated polyester resin and preparation method thereof | |
| CN102964576A (en) | Modified polyester and preparation method thereof | |
| CN103102647B (en) | Preparation method of polyester film with high heat shrinkage | |
| CN102838737A (en) | Aluminum polyester resin and preparation method and application thereof | |
| EP3995482B1 (en) | Diester-based material production unit and diester-based material production system including the same | |
| CN103483569A (en) | High-flexible polyester heat shrinkage film and preparation method thereof | |
| CN110180597A (en) | A kind of composite catalyst and PET biodegrading process for PET degradation | |
| KR102489173B1 (en) | System for Heat Exchange and System for Manufacturing Di-ester based Composition Comprising the Same | |
| CN102964575A (en) | Modified polyester and preparation method thereof | |
| EP2749584B1 (en) | Process for Manufacturing Polyethylene Terephthalate | |
| CN102153736A (en) | High hydroxyl polyester resin for polyurethane elastic solidifying agent and preparation method thereof | |
| JP2019131636A (en) | polyester |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20170829 Termination date: 20180122 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |