CN117586144A - Preparation method and application of nucleating agent for recycling PET (polyethylene terephthalate) - Google Patents
Preparation method and application of nucleating agent for recycling PET (polyethylene terephthalate) Download PDFInfo
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- CN117586144A CN117586144A CN202311728405.2A CN202311728405A CN117586144A CN 117586144 A CN117586144 A CN 117586144A CN 202311728405 A CN202311728405 A CN 202311728405A CN 117586144 A CN117586144 A CN 117586144A
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- 239000002667 nucleating agent Substances 0.000 title claims abstract description 38
- 238000004064 recycling Methods 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 229920000139 polyethylene terephthalate Polymers 0.000 title description 56
- 239000005020 polyethylene terephthalate Substances 0.000 title description 56
- -1 polyethylene terephthalate Polymers 0.000 title description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 claims abstract description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 18
- ALYNCZNDIQEVRV-UHFFFAOYSA-N 4-aminobenzoic acid Chemical compound NC1=CC=C(C(O)=O)C=C1 ALYNCZNDIQEVRV-UHFFFAOYSA-N 0.000 claims description 15
- 239000012153 distilled water Substances 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 238000002425 crystallisation Methods 0.000 abstract description 18
- 230000008025 crystallization Effects 0.000 abstract description 18
- 238000000034 method Methods 0.000 abstract description 18
- 239000002994 raw material Substances 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 3
- 238000012986 modification Methods 0.000 abstract description 2
- 230000004048 modification Effects 0.000 abstract description 2
- HVBSAKJJOYLTQU-UHFFFAOYSA-N 4-aminobenzenesulfonic acid Chemical compound NC1=CC=C(S(O)(=O)=O)C=C1 HVBSAKJJOYLTQU-UHFFFAOYSA-N 0.000 abstract 2
- 229950000244 sulfanilic acid Drugs 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 17
- 238000002156 mixing Methods 0.000 description 17
- 230000000694 effects Effects 0.000 description 10
- 238000001746 injection moulding Methods 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 235000013361 beverage Nutrition 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 238000005452 bending Methods 0.000 description 6
- 238000011084 recovery Methods 0.000 description 5
- 239000013078 crystal Substances 0.000 description 4
- 238000010899 nucleation Methods 0.000 description 4
- 230000006911 nucleation Effects 0.000 description 4
- 238000012545 processing Methods 0.000 description 3
- 239000012752 auxiliary agent Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- FMZUHGYZWYNSOA-VVBFYGJXSA-N (1r)-1-[(4r,4ar,8as)-2,6-diphenyl-4,4a,8,8a-tetrahydro-[1,3]dioxino[5,4-d][1,3]dioxin-4-yl]ethane-1,2-diol Chemical compound C([C@@H]1OC(O[C@@H]([C@@H]1O1)[C@H](O)CO)C=2C=CC=CC=2)OC1C1=CC=CC=C1 FMZUHGYZWYNSOA-VVBFYGJXSA-N 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229940087101 dibenzylidene sorbitol Drugs 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 230000003631 expected effect Effects 0.000 description 1
- XMHIUKTWLZUKEX-UHFFFAOYSA-N hexacosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCC(O)=O XMHIUKTWLZUKEX-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C233/00—Carboxylic acid amides
- C07C233/64—Carboxylic acid amides having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings
- C07C233/81—Carboxylic acid amides having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by carboxyl groups
-
- 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
- C08K5/16—Nitrogen-containing compounds
- C08K5/20—Carboxylic acid amides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/24—Crystallisation aids
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
Abstract
The invention discloses a preparation method and application of a nucleating agent for recycled PET, and relates to the technical field of recycled PET modification. The nucleating agent for the recovered PET is synthesized by taking sulfanilic acid, terephthaloyl chloride and sodium hydroxide as raw materials through chemical reaction, so that the problems of low crystallization temperature and poor rigidity of the recovered PET are solved, and the industrial development process of recycling the recovered PET is promoted.
Description
Technical Field
The invention relates to a preparation method and application of a nucleating agent for recycling PET, and belongs to the technical field of high polymer materials.
Background
Polyethylene terephthalate (PET) is an engineering plastic with excellent performance, and is widely applied to the aspects of food, beverage packaging and the like. However, the continuous accumulation of the content of a large amount of PET which is extremely difficult to be degraded by air or microorganisms in the natural environment causes serious harm to the production and life of human beings. Therefore, how to realize the effective utilization of PET and reduce or even stop the harm caused by the PET is a problem to be solved in the field of PET recovery.
At present, the utilization mode of recovering PET at home and abroad mainly adopts mechanical recovery with simple method and low cost. However, since the recovered PET molecular chain contains an ester bond, a trace amount of moisture can break the molecular chain at a high temperature during the secondary processing of mechanical recovery, so that the crystallization temperature is reduced, the rigidity is reduced, and the requirement of a high-performance product is difficult to meet. Therefore, the PET material needs to be modified in the secondary processing process so as to achieve the purpose of improving the crystallization temperature and obtaining the recovered PET material with higher rigidity.
The Chinese patent with publication number of CN 114292285A synthesizes a novel auxiliary agent for improving the mechanical property of the recovered PET through dibenzylidene sorbitol and montan ceric acid, the method fully considers the compatibility of the auxiliary agent and even the influence of a crystal structure on the toughness of the recovered PET, but sorbitol nucleating agent cannot exert the function of controlling the spatial arrangement of the main chain plane of the recovered PET molecule to the maximum extent, and has no definite data for improving the rigidity of the recovered PET.
Disclosure of Invention
The invention provides a preparation method and application of a nucleating agent for recycling PET, which have stable molecular structure and can provide heterogeneous nucleation sites for recycling PET. The microstructure of the PET crystal material can provide an attached crystal surface for the recovered PET, so that the spatial arrangement of the main chain plane of the recovered PET molecule is controlled, the crystallization temperature and the bending strength of the recovered PET are greatly improved, and the problems in the prior art are effectively solved.
The invention provides a nucleating agent for recycling PET, which is characterized by comprising the following characteristics:
the preparation method of the nucleating agent for recycling PET is characterized by comprising the following steps of:
13.71. 13.71 g para-aminobenzoic acid was dissolved in 200 mL acetone and stirred at 25℃for 30 min at 800 rpm using an electric stirrer; subsequently 7.58, mL terephthaloyl chloride was added and the reaction was stirred at 800 rpm using an electric stirrer at 25 ℃ for 12 h; after the reaction was completed, the obtained solid was washed with 500 mL acetone and 1000 mL distilled water, respectively. Subsequently, 200. 200 mL acetone and 3.2. 3.2 g sodium hydroxide were added, the reaction was stirred at 25℃with an electric stirrer at 800 rpm for 8 h, the resulting solid was washed with distilled water to neutrality, and dried at 80℃to constant weight to obtain the nucleating agent for recycled PET.
The preparation method of the nucleating agent for recycling PET has the advantages that various reaction conditions and parameters are optimal conditions through experimental verification.
The invention also provides application of the nucleating agent for recycling PET, which is characterized in that the use amount of the nucleating agent is 0.1-1% of the mass of the recycled PET.
Preferably, the nucleating agent is used in an amount of 0.5%.
The addition amount of the nucleating agent synthesized by the method must be proper, the addition amount is too small to reach the expected effect, and the excessive addition amount can cause the agglomeration of the nucleating agent to influence the action effect. The addition amount is a better condition verified by the test.
Compared with the prior art, the invention has the following technical effects.
The nucleating agent for recycling PET has a long strip-shaped microscopic morphology, can induce the recycling PET to be attached to crystallize, promotes the conversion of a molecular structure from a cis-amorphous state to a trans-crystalline state by controlling the spatial arrangement of the main chain plane of the recycling PET molecule, obviously shortens the crystallization induction period, and promotes the rearrangement of a molecular chain, thereby promoting the crystallization of the recycling PET and improving the crystallization temperature of the recycling PET.
The nucleating agent for recycling PET has a special molecular structure, can be used as a heterogeneous nucleating agent to refine and recycle PET spherulites on one hand, promote ordered arrangement of crystals, improve the proportion of rigid parts, and can chemically react with the tail end of a molecular chain of recycling PET on the other hand, so that the molecular structure of part of recycling PET is changed, the proportion of rigid chain segments is improved, and further the bending strength of the nucleating agent is improved.
The nucleating agent for recycling PET has a stable chemical structure, and can ensure the normal performance of the nucleating agent in the whole processing process.
Detailed description of the preferred embodiments
In order to make the technical problems, technical solutions and advantageous effects to be solved by the present invention more apparent, the present invention will be further described in detail with reference to the following examples, and it should be understood that the specific examples described herein are only for explaining the present invention and are not intended to limit the present invention. The raw materials, reagents and equipment used in the invention are conventional and commercially available in the technical field.
Example 1
13.71. 13.71 g para-aminobenzoic acid (CAS: 150-13-0) was dissolved in 200 mL acetone and stirred at 25℃for 30 min at 800 rpm using an electric stirrer; subsequently 7.58. 7.58 mL terephthaloyl chloride (CAS: 100-20-9) was added and the reaction was stirred at 800 rpm using an electric stirrer at 25℃for 12 h; after the reaction was completed, the obtained solid was washed with 500 mL acetone and 1000 mL distilled water, respectively. Subsequently, 200. 200 mL acetone and 3.2. 3.2 g sodium hydroxide (CAS: 1310-73-2) were added, the reaction was stirred at 25℃with an electric stirrer at 800 rpm for 8 h, the resulting solid was washed with distilled water to neutrality, and dried at 80℃to constant weight to obtain the nucleating agent for recycled PET.
And (3) conventionally mixing the recovered PET (beverage bottle recovered material) and the nucleating agent in a high-speed mixer according to the mass ratio of 100:0.5 (the mixing rotating speed is 3000 rpm, the mixing time is 5 min), extruding in a conventional double-screw extruder, granulating, and performing injection molding on an injection molding machine to obtain a test sample. The flexural strength was measured according to the method specified in GB/T22906.6-2008, the crystallization temperature was measured according to the method specified in GB/T19466.3-2004, and the specific data are shown in Table 1.
Example 2
This example is substantially the same as example 1, except that the nucleating agent synthesized in example 1 was used to prepare samples with recycled PET (beverage bottle recovery) at a mass ratio of 100:0.1, and the test data are shown in Table 1.
Example 3
This example is substantially the same as example 1, except that the nucleating agent synthesized in example 1 was used to prepare samples at a mass ratio of 100:1 with recycled PET (beverage bottle recovery), and the test data are shown in Table 1.
Comparative example 1
And extruding and granulating the pure recovered PET (beverage bottle recovered material) in a conventional double-screw extruder, and performing injection molding on an injection molding machine to obtain a test sample. The flexural strength was measured according to the method specified in GB/T22906.6-2008, the crystallization temperature was measured according to the method specified in GB/T19466.3-2004, and the specific data are shown in Table 1.
Comparative example 2
The preparation method comprises the steps of conventionally mixing the recovered PET (beverage bottle recovered material) and the para-aminobenzoic acid in a high-speed mixer according to a mass ratio of 100:0.5 (mixing rotating speed of 3000 rpm, mixing time of 5 min), extruding in a conventional double-screw extruder, granulating, and molding on an injection molding machine to obtain a test sample. The flexural strength was measured according to the method specified in GB/T22906.6-2008, the crystallization temperature was measured according to the method specified in GB/T19466.3-2004, and the specific data are shown in Table 1.
Comparative example 3
The preparation method comprises the steps of conventionally mixing the recycled PET (beverage bottle recycled material) and terephthaloyl chloride in a high-speed mixer according to a mass ratio of 100:0.5 (mixing rotation speed of 3000 rpm, mixing time of 5 min), extruding in a conventional double-screw extruder, granulating, and performing injection molding on an injection molding machine to obtain a test sample. The flexural strength was measured according to the method specified in GB/T22906.6-2008, the crystallization temperature was measured according to the method specified in GB/T19466.3-2004, and the specific data are shown in Table 1.
Comparative example 4
And (3) conventionally mixing the recovered PET (beverage bottle recovered material) and sodium hydroxide in a high-speed mixer according to a mass ratio of 100:0.5 (mixing rotating speed of 3000 rpm, mixing time of 5 min), extruding in a conventional double-screw extruder, granulating, and performing injection molding on an injection molding machine to obtain a test sample. The flexural strength was measured according to the method specified in GB/T22906.6-2008, the crystallization temperature was measured according to the method specified in GB/T19466.3-2004, and the specific data are shown in Table 1.
Comparative example 5
After 13.71 and g of para-aminobenzoic acid, 7.58 and mL of terephthaloyl chloride and 3.2 and g of sodium hydroxide are simply mixed in a high-speed mixer (mixing speed: 3000 rpm, mixing time: 5 min), and after the mixture and recovered PET (beverage bottle recovered material) are conventionally mixed in the high-speed mixer according to a mass ratio of 0.5:100 (mixing speed: 3000 rpm, mixing time: 5 min), the mixture is extruded in a conventional twin-screw extruder, granulated and injection molded on an injection molding machine to obtain a test sample. The flexural strength was measured according to the method specified in GB/T22906.6-2008, the crystallization temperature was measured according to the method specified in GB/T19466.3-2004, and the specific data are shown in Table 1.
Table 1 test results for each of examples and comparative examples
| Flexural Strength (MPa) | Crystallization temperature (. Degree. C.) | |
| Example 1 | 89.9 | 213.4 |
| Example 2 | 85.6 | 208.9 |
| Example 3 | 86.5 | 210.3 |
| Comparative example 1 | 60.8 | 186.1 |
| Comparative example 2 | 66.9 | 192.2 |
| Comparative example 3 | 61.2 | 186.9 |
| Comparative example 4 | 62.8 | 188.1 |
| Comparative example 5 | 68.7 | 195.8 |
From the experimental results in Table 1, it is understood that the bending strength and crystallization temperature of the nucleating agent for recycled PET prepared in examples 1-3 by adding the present invention are relatively high. Example 1, wherein the addition amount was 0.5%, was most preferable. Compared with the pure recovered PET in comparative example 1, the nucleating agent synthesized by the invention has the effect of obviously improving the bending strength and crystallization temperature of the recovered PET. In addition, too much or too little of the nucleating agent may decrease the bending strength and crystallization temperature of the recycled PET.
The nucleating agent for recycled PET prepared by the invention is synthesized by chemical reaction so that all chain segments can act simultaneously, while comparative examples 2-7 are only single raw materials or simple mixing of the raw materials, and do not perform complete chemical reaction, thus the effects can not be fully exerted. Among them, the para-aminobenzoic acid added in comparative example 2 can exert a certain heterogeneous nucleation effect, improving the bending strength and crystallization temperature of the recycled PET, but has limited effect. The terephthaloyl chloride added in comparative example 3 had little lifting effect. The sodium hydroxide added in comparative example 4 is strongly basic and only plays a weak heterogeneous nucleation role. Meanwhile, the comparative example 5 added with the para-aminobenzoic acid, the terephthaloyl chloride and the sodium hydroxide has the best effect, but does not undergo chemical reaction, does not form a unique chemical structure, and can only play a certain heterogeneous nucleation role. Thus, the improvement effect is significantly different from that of example 1.
The foregoing description of the preferred embodiment of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, and alternatives falling within the spirit and principles of the invention.
Claims (5)
1. The nucleating agent for recycling PET is characterized by comprising the following molecular structure:
2. the nucleating agent for recycling PET according to claim 1, which is prepared as follows:
13.71. 13.71 g para-aminobenzoic acid was dissolved in 200 mL acetone and stirred at 25℃for 30 min at 800 rpm using an electric stirrer; subsequently 7.58, mL terephthaloyl chloride was added and the reaction was stirred at 800 rpm using an electric stirrer at 25 ℃ for 12 h; after the reaction was completed, the obtained solid was washed with 500 mL acetone and 1000 mL distilled water, respectively. Subsequently, 200. 200 mL acetone and 3.2. 3.2 g sodium hydroxide were added, the reaction was stirred at 25℃with an electric stirrer at 800 rpm for 8 h, the resulting solid was washed with distilled water to neutrality, and dried at 80℃to constant weight to obtain the nucleating agent for recycled PET.
3. Use of a nucleating agent for recycled PET according to claim 1 or 2 in recycled PET.
4. Use of a nucleating agent for recycled PET according to claim 3, in recycled PET, characterized in that: the usage amount of the nucleating agent for recycling PET is 0.1% -1% of the mass of the recycling PET.
5. Use of a nucleating agent for recycled PET according to claim 3, in recycled PET, characterized in that: the consumption of the nucleating agent for recycling PET is 0.5% of the mass of the recycling PET.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311728405.2A CN117586144A (en) | 2023-12-15 | 2023-12-15 | Preparation method and application of nucleating agent for recycling PET (polyethylene terephthalate) |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311728405.2A CN117586144A (en) | 2023-12-15 | 2023-12-15 | Preparation method and application of nucleating agent for recycling PET (polyethylene terephthalate) |
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| Publication Number | Publication Date |
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| CN117586144A true CN117586144A (en) | 2024-02-23 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN202311728405.2A Pending CN117586144A (en) | 2023-12-15 | 2023-12-15 | Preparation method and application of nucleating agent for recycling PET (polyethylene terephthalate) |
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| CN (1) | CN117586144A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117603103A (en) * | 2023-12-15 | 2024-02-27 | 太原科技大学 | Synthesis method of PET flame retardant/nucleation auxiliary agent and application of PET flame retardant/nucleation auxiliary agent in PET recovery |
| CN117603103B (en) * | 2023-12-15 | 2024-06-28 | 太原科技大学 | Synthesis method of PET flame retardant/nucleation auxiliary agent and application of PET flame retardant/nucleation auxiliary agent in PET recovery |
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2023
- 2023-12-15 CN CN202311728405.2A patent/CN117586144A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117603103A (en) * | 2023-12-15 | 2024-02-27 | 太原科技大学 | Synthesis method of PET flame retardant/nucleation auxiliary agent and application of PET flame retardant/nucleation auxiliary agent in PET recovery |
| CN117603103B (en) * | 2023-12-15 | 2024-06-28 | 太原科技大学 | Synthesis method of PET flame retardant/nucleation auxiliary agent and application of PET flame retardant/nucleation auxiliary agent in PET recovery |
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