CN108676153B - Method for preparing unsaturated polyester resin by degrading PET bottle flakes - Google Patents
Method for preparing unsaturated polyester resin by degrading PET bottle flakes Download PDFInfo
- Publication number
- CN108676153B CN108676153B CN201810902778.XA CN201810902778A CN108676153B CN 108676153 B CN108676153 B CN 108676153B CN 201810902778 A CN201810902778 A CN 201810902778A CN 108676153 B CN108676153 B CN 108676153B
- Authority
- CN
- China
- Prior art keywords
- polyester resin
- unsaturated polyester
- pet bottle
- temperature
- degrading
- 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
Images
Classifications
-
- 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
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/52—Polycarboxylic acids or polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/50—Phosphorus bound to carbon only
Abstract
The invention discloses a method for preparing unsaturated polyester resin by degrading PET bottle flakes, which comprises the steps of adding PET bottle flakes, deionized water, organic unsaturated dibasic acid and micromolecular diol into a microwave high-pressure reactor, dissolving the organic unsaturated dibasic acid in the deionized water under stirring, adding an antioxidant, and reacting under certain pressure, temperature and microwave frequency; removing 90% of water in a system from the PET hydrolysate by a reduced pressure distillation method at a certain temperature, adding small molecular diol, refluxing the water on a synthesis device of unsaturated polyester resin, measuring the acid value, vacuumizing, and measuring the acid value again; and (3) after the temperature is reduced, adding a polymerization inhibitor and styrene, uniformly stirring, discharging and storing, and measuring the viscosity and the solidification time of the mixture. The method has the advantages of simple and convenient process, cheap raw materials and mild reaction conditions, and is suitable for wide popularization and application.
Description
Technical Field
The invention relates to the field of PET bottle flake degradation, in particular to a method for preparing unsaturated polyester resin by degrading PET bottle flakes.
Background
China has become the largest country for producing and consuming PET and unsaturated polyester resin, the usage amount of domestic PET bottles is rapidly increased, more and more waste PET is discharged into the nature, and a large amount of PET needs to be recycled. Currently, PET has recovery ways such as pyrolysis, biodegradation, chemical degradation (hydrolysis, aminolysis and alcoholysis) and the like. The pyrolysis recycling value is low, the biodegradation efficiency is low, the industrialization is difficult to realize, and the chemical degradation is an important way for degrading the PET at present.
In the unsaturated polyester resin industry, tens of thousands tons of PET are recycled to synthesize the p-benzene unsaturated polyester resin every year, and the p-benzene unsaturated polyester resin has lower thermal expansion coefficient and better corrosion resistance than the o-benzene general resin. However, degradation of PET by chemical means is often directed to the chemical activity present in the ester groups of PET. In order to realize the chemical reaction of PET molecules, a catalyst is often required to be added, the commonly used hydrolysis catalyst is strong acid and strong base, and the alcoholysis reaction is often carried out by adding metal salts (0.5-1.5% of the mass of PET) such as zinc acetate and the like. This part of the catalyst is difficult to separate and purify from the product after the alcoholysis process, and similar strong acid and alkali substances can cause damage to equipment.
If PET hydrolyzates or alcoholyzes to produce unsaturated polyester resins, the residual catalyst will have an effect on the properties of the unsaturated resins.
Accordingly, those skilled in the art have been devoted to developing a method for preparing unsaturated polyester resin by degradation of PET bottle flakes without using a catalyst.
Disclosure of Invention
The prior art mainly realizes the degradation recovery of PET through aminolysis, alcoholysis or hydrolysis of ester bonds in the PET, and thus additional catalyst is required. These catalysts typically include strong acids, strong bases, and alkali metal acetates or other organometallic catalysts. The residues of the catalyst can bring influence on the next application of PET degradation products such as hydrolysate, alcoholysis products and the like, such as influencing the reaction activity of the PET degradation products in the polycondensation reaction and the like. In view of the defects in the prior art, the technical problem to be solved by the invention is that no catalyst is used in the PET degradation process, and the application of PET degradation products in unsaturated polyester resin is prevented from being influenced by catalyst residues.
In order to achieve the above object, the present invention provides a method for preparing unsaturated polyester resin by degrading PET bottle flakes, comprising the following steps:
step 1, hydrolysis of PET: adding PET bottle flakes, deionized water, organic unsaturated dibasic acid and micromolecular diol into a microwave high-pressure reactor, dissolving the organic unsaturated dibasic acid in the deionized water under stirring, adding an antioxidant, and reacting under certain pressure, temperature and microwave frequency.
Step 2, preparation of unsaturated polyester resin: removing 90% of water in the PET hydrolysate at a certain temperature by a reduced pressure distillation method, adding small molecular diol, refluxing the water on a synthesis device of unsaturated polyester resin, measuring the acid value, vacuumizing, and measuring the acid value again.
And 3, stirring and storing: after the temperature is reduced, adding a polymerization inhibitor and monomer styrene, stirring uniformly, discharging and storing, and measuring the viscosity and the solidification time of the mixture.
Further, the mass ratio of the PET bottle flakes to the deionized water to the organic unsaturated dibasic acid to the micromolecular diol is 100: 1000-2000: 100-500: 100-200.
Further, the organic unsaturated dibasic acid comprises maleic acid, itaconic acid and fumaric acid.
Further, the small molecule diol comprises ethylene glycol, monoethylene glycol, 1, 4-butanediol, 1, 2-propanediol and 1, 3-propanediol.
Further, the antioxidant is triphenylphosphine.
Further, the antioxidant triphenylphosphine is 1-3 parts.
Further, the pressure of the step 1 is controlled to be 0.2-0.5 MPa.
Further, the temperature of the step 1 is controlled to be 90-150 ℃.
Further, the microwave frequency of the step 1 is controlled at 300-500W.
Further, the temperature of the step 2 is 80-100 ℃.
Further, the pressure of the step 2 is 100-500 Pa.
Further, the small molecule alcohol in the step 2 is 100-800 parts.
Further, the reaction conditions of refluxing the water on the unsaturated polyester resin synthesizer in the step 2 are 1-2 hours at 150 ℃, 1-2 hours at 170 ℃, 1-2 hours at 180 ℃, 1-2 hours at 200 ℃ and 1-2 hours at 220 ℃.
Further, the acid value of the step 2 is measured to be 25 to 30mgKOH/g, and the acid value is measured to be 15 to 20mgKOH/g again.
Further, the temperature of the step 3 is reduced to 150 ℃.
Further, the polymerization inhibitor in the step 3 is hydroquinone.
Further, 1-3 parts of polymerization inhibitor hydroquinone in the step 3.
Further, the styrene in the step 3 is 300 parts.
Further, the step 3 measures the viscosity to be 2000-5000mPa.s (25 ℃), and the setting time to be 10-20min (25 ℃).
The invention has the following beneficial effects:
1. a catalyst is not used in the PET degradation process, so that the influence of catalyst residues on the application of PET degradation products in unsaturated polyester resin is avoided;
2. the triphenyl phosphine is used as an activator of organic unsaturated dibasic acid to accelerate the degradation of PET on one hand, and is used as an antioxidant in the synthetic process of unsaturated polyester resin on the other hand to ensure the oxidative degradation of the unsaturated polyester resin in the synthetic process;
3. the micromolecular diol is added in the hydrolysis process, so that the PET is dissolved in the micromolecular diol in the hydrolysis process, and the hydrolysis reaction is more favorably carried out.
The preparation method of the unsaturated polyester resin has the advantages of simple and convenient process, easy operation, cheap raw materials, mild reaction conditions, safety and environmental protection, and is beneficial to realizing industrialized expansion application.
The conception, the specific structure and the technical effects of the present invention will be further described with reference to the accompanying drawings to fully understand the objects, the features and the effects of the present invention.
Drawings
FIG. 1 is a flow chart of the degradation of PET bottle flakes to produce unsaturated polyester resin according to a preferred embodiment of the present invention;
Detailed Description
The technical contents of the preferred embodiments of the present invention will be more clearly and easily understood by referring to the drawings attached to the specification. The present invention may be embodied in many different forms of embodiments and the scope of the invention is not limited to the embodiments set forth herein.
If there is an experimental method not specified specific conditions, it is usually carried out according to conventional conditions, such as the relevant instructions or manuals.
Example 1:
hydrolysis of PET
PET bottle chips, deionized water, maleic acid and propylene glycol according to a mass ratio of 100: 1100: 200: 150, adding the mixture into a microwave high-pressure reactor, dissolving maleic acid into deionized water under stirring, adding 1.5 parts of triphenyl phosphine, controlling the pressure at 0.3Mpa, the temperature at 120 ℃, the microwave frequency at 400W, and reacting for 50 minutes to obtain the PET hydrolysate.
2. Preparation of unsaturated polyester resins
After microwave reaction, PET hydrolysate is removed from the system by a reduced pressure distillation method at 95 ℃ and 105Pa, then 100 parts of propylene glycol is added, water is refluxed on a synthesizer of unsaturated polyester resin, the mixture is discharged at 150 ℃ for 1.5 hours, at 170 ℃ for 1.5 hours, at 180 ℃ for 1.5 hours, at 200 ℃ for 1.5 hours and at 220 ℃ for 1.5 hours, the acid value is measured to be 28.6mgKOH/g, and the mixture is vacuumized until the acid value is 16 mgKOH/g.
3. Stirring and storing
Reducing the temperature to 150 ℃, adding 2 parts of polymerization inhibitor hydroquinone, adding 160 parts of styrene, stirring uniformly, discharging and storing. The viscosity was determined to be 2500 mPas (25 ℃ C.) and the setting time 16min (25 ℃ C.).
Example 2:
hydrolysis of PET
PET bottle chips, deionized water, maleic acid and propylene glycol according to a mass ratio of 100: 1100: 200: 150, adding the mixture into a microwave high-pressure reactor, dissolving maleic acid into deionized water under stirring, adding 1.5 parts of triphenyl phosphine, controlling the pressure at 0.35Mpa, the temperature at 120 ℃, the microwave frequency at 4500W, and reacting for 50 minutes to obtain the PET hydrolysate.
2. Preparation of unsaturated polyester resins
After microwave reaction, PET hydrolysate is removed from the system by a reduced pressure distillation method at 95 ℃ and 105Pa, then 70 parts of ethylene glycol is added, water is refluxed on a synthesis device of unsaturated polyester resin, the mixture is discharged at 150 ℃ for 1.5 hours, at 170 ℃ for 1.5 hours, at 180 ℃ for 1.5 hours, at 200 ℃ for 1.5 hours and at 220 ℃ for 1.5 hours, the acid value is measured to be 25.3mgKOH/g, and the mixture is vacuumized until the acid value is 15.2 mgKOH/g.
3. Stirring storage
Reducing the temperature to 150 ℃, adding 2 parts of polymerization inhibitor hydroquinone, adding 150 parts of styrene, stirring uniformly, discharging and storing. The viscosity was measured to be 4000 mPas (25 ℃ C.) and the setting time was 12min (25 ℃ C.).
The foregoing detailed description of the preferred embodiments of the invention has been presented. It should be understood that numerous modifications and variations could be devised by those skilled in the art in light of the present teachings without departing from the inventive concepts. Therefore, the technical solutions available to those skilled in the art through logic analysis, reasoning and limited experiments based on the prior art according to the concept of the present invention should be within the scope of protection defined by the claims.
Claims (9)
1. A method for preparing unsaturated polyester resin by degrading PET bottle chips is characterized by comprising the following steps:
step 1, hydrolysis of PET: and (2) mixing the following components in percentage by mass as 100: 1000-2000: 100-500: adding 100-200 PET bottle chips, deionized water, organic unsaturated dibasic acid and micromolecular diol into a microwave high-pressure reactor, dissolving the organic unsaturated dibasic acid in the deionized water under stirring, adding an antioxidant, and reacting under certain pressure, temperature and microwave frequency;
step 2, preparation of unsaturated polyester resin: removing 90% of water in a system from the PET hydrolysate by a reduced pressure distillation method at a certain temperature, adding small molecular diol, refluxing the water on a synthesis device of unsaturated polyester resin, measuring the acid value, vacuumizing, and measuring the acid value again;
and 3, stirring and storing: and (3) after the temperature is reduced, adding a polymerization inhibitor and styrene, uniformly stirring, discharging and storing, and measuring the viscosity and the solidification time of the mixture.
2. The method for preparing unsaturated polyester resin by degrading PET bottle flakes according to claim 1, wherein the organic unsaturated dibasic acid comprises maleic acid, itaconic acid and fumaric acid.
3. The method for preparing unsaturated polyester resin by degrading PET bottle flakes according to claim 1, wherein the antioxidant is triphenyl phosphine.
4. The method for preparing unsaturated polyester resin by degrading PET bottle flakes according to claim 1, wherein the polymerization inhibitor is hydroquinone.
5. The method for preparing unsaturated polyester resin by degrading PET bottle chips as claimed in claim 1, wherein the pressure of step 1 is controlled to be 0.2-0.5MPa, the temperature is controlled to be 90-150 ℃, and the wave frequency is controlled to be 300-500W.
6. The method for preparing unsaturated polyester resin by degrading PET bottle chips as claimed in claim 1, wherein the temperature of step 2 is 80-100 ℃, and the pressure is 100-500 Pa.
7. The method for preparing unsaturated polyester resin by degrading PET bottle chips as claimed in claim 1, wherein the reaction conditions of refluxing water on the unsaturated polyester resin synthesizer in the step 2 are 150 ℃ for 1-2 hours, 170 ℃ for 1-2 hours, 180 ℃ for 1-2 hours, 200 ℃ for 1-2 hours, and 220 ℃ for 1-2 hours.
8. The method for preparing unsaturated polyester resin by degradation of PET bottle chips according to claim 1, wherein the acid value measured in step 2 is 25 to 30mgKOH/g, and the acid value measured again is 15 to 20 mgKOH/g.
9. The method for preparing unsaturated polyester resin by degrading PET bottle chips as claimed in claim 1, wherein the viscosity of step 3 is 2000-5000m Pa.s and the solidification time is 10-20min when measured at 25 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810902778.XA CN108676153B (en) | 2018-08-09 | 2018-08-09 | Method for preparing unsaturated polyester resin by degrading PET bottle flakes |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810902778.XA CN108676153B (en) | 2018-08-09 | 2018-08-09 | Method for preparing unsaturated polyester resin by degrading PET bottle flakes |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108676153A CN108676153A (en) | 2018-10-19 |
| CN108676153B true CN108676153B (en) | 2020-09-04 |
Family
ID=63816221
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810902778.XA Expired - Fee Related CN108676153B (en) | 2018-08-09 | 2018-08-09 | Method for preparing unsaturated polyester resin by degrading PET bottle flakes |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108676153B (en) |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4166896A (en) * | 1976-02-23 | 1979-09-04 | Owens-Corning Fiberglas Corporation | Polyester production |
| CN1617904A (en) * | 2002-02-01 | 2005-05-18 | 株式会社久保田 | Method of depolymerizing polyethylene terephthalate and process for producing polyester resin |
| CN101066904A (en) * | 2007-06-06 | 2007-11-07 | 温州大学 | Catalytic depolymerization process of poly-glycol telephthalate unde microwave irradiation |
| 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 |
| CN103951817A (en) * | 2014-04-15 | 2014-07-30 | 吴桥昊通树脂有限公司 | Synthetic method of unsaturated polyester resin for producing agglomerated stones |
| CN104311749A (en) * | 2014-10-29 | 2015-01-28 | 福建永悦科技有限公司 | Unsaturated polyester resin for polyester concrete and preparation method of unsaturated polyester resin |
| CN104892852A (en) * | 2015-04-16 | 2015-09-09 | 黄亨利 | Formula and production process of PET |
-
2018
- 2018-08-09 CN CN201810902778.XA patent/CN108676153B/en not_active Expired - Fee Related
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4166896A (en) * | 1976-02-23 | 1979-09-04 | Owens-Corning Fiberglas Corporation | Polyester production |
| CN1617904A (en) * | 2002-02-01 | 2005-05-18 | 株式会社久保田 | Method of depolymerizing polyethylene terephthalate and process for producing polyester resin |
| CN101066904A (en) * | 2007-06-06 | 2007-11-07 | 温州大学 | Catalytic depolymerization process of poly-glycol telephthalate unde microwave irradiation |
| 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 |
| CN103951817A (en) * | 2014-04-15 | 2014-07-30 | 吴桥昊通树脂有限公司 | Synthetic method of unsaturated polyester resin for producing agglomerated stones |
| CN104311749A (en) * | 2014-10-29 | 2015-01-28 | 福建永悦科技有限公司 | Unsaturated polyester resin for polyester concrete and preparation method of unsaturated polyester resin |
| CN104892852A (en) * | 2015-04-16 | 2015-09-09 | 黄亨利 | Formula and production process of PET |
Non-Patent Citations (3)
| Title |
|---|
| Chemical Recycling of Poly(ethylene terephthalate);George P. Karayannidis，等;《Macromolecular Materials and Engineering》;20071231;第128-146页 * |
| PET废弃物水解及醇解化学回收技术研究;邓玉明，等;《塑料制造》;20110731;第49-53页 * |
| 废弃PET 的醇解及其不饱和聚酯树脂的制备与表征;刘华夏，等;《材料研究与应用》;20150930;第9卷(第3期);第166-171页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108676153A (en) | 2018-10-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US3911048A (en) | Process for the continuous preparation of unsaturated polyesters | |
| CZ299908B6 (en) | Method of waste polyethyleneterephthalate chemical depolymerization | |
| US20050096482A1 (en) | Method of depolymerizing polyethylene terephthalate and process for producing polyester resin | |
| CN101531773A (en) | Method for recovering waste polyethylene glycol terephthalate | |
| US20170306086A1 (en) | Process for Manufacturing Medium and High Molecular Weight Polyesters | |
| JP2008527160A (en) | Low viscosity unsaturated polyester resin with reduced VOC release | |
| JP2009532515A (en) | Method for directly producing polyester articles for packaging and articles obtained therefrom | |
| JPH09221565A (en) | Method for recycling waste cured unsaturated polyester resin | |
| WO2019174656A1 (en) | Method of obtaining terephthalic acid from waste polyethylene terephthalate | |
| JP2003292594A (en) | Method for producing polyester resin | |
| CN108676153B (en) | Method for preparing unsaturated polyester resin by degrading PET bottle flakes | |
| CN108623796B (en) | Method for producing p-benzene unsaturated polyester resin by using waste terephthalic acid | |
| CN107857896A (en) | A kind of ester composition from PTA substandard goods and preparation method thereof | |
| CN1304924A (en) | Process for depolymerizing waste glycol tere-phthalate | |
| JP2004250561A (en) | Method for producing polyester resin | |
| JP3444870B2 (en) | Depolymerization method of polyethylene terephthalate | |
| US9487622B2 (en) | Process for the preparation of modified poly(alkylene terephthalate) employing an in-situ titanium-containing catalyst | |
| JP2008001847A (en) | Method for producing aliphatic polyester | |
| JP3035273B2 (en) | Method and apparatus for synthesizing unsaturated polyester resin | |
| CN111471166A (en) | Method for improving polyester polycondensation reaction rate | |
| JP2005097521A (en) | Method for depolymerizing polyester | |
| KR102648713B1 (en) | Methods for plastic depolymerization | |
| CN105712833B (en) | A kind of method that paraxylene is prepared by waste PET hydrogenation degraded | |
| EP2242787A2 (en) | Process for manufacturing medium and high molecular weight polyesters | |
| CN116970130A (en) | Environment-friendly unsaturated polyester resin and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for 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: 20200904 Termination date: 20210809 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |