CN117624230A - Preparation method and application of recycled polypropylene double-effect auxiliary agent - Google Patents
Preparation method and application of recycled polypropylene double-effect auxiliary agent Download PDFInfo
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- CN117624230A CN117624230A CN202311728503.6A CN202311728503A CN117624230A CN 117624230 A CN117624230 A CN 117624230A CN 202311728503 A CN202311728503 A CN 202311728503A CN 117624230 A CN117624230 A CN 117624230A
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- recycled polypropylene
- auxiliary agent
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- polypropylene
- effect
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- -1 polypropylene Polymers 0.000 title claims abstract description 86
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 78
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 78
- 239000012752 auxiliary agent Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title abstract description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 238000004064 recycling Methods 0.000 claims abstract description 5
- 239000000654 additive Substances 0.000 claims abstract description 4
- 230000000996 additive effect Effects 0.000 claims abstract description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 26
- 239000012153 distilled water Substances 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 229960004050 aminobenzoic acid Drugs 0.000 claims description 4
- 230000009977 dual effect Effects 0.000 claims description 4
- 238000005303 weighing Methods 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 238000002425 crystallisation Methods 0.000 abstract description 27
- 230000008025 crystallization Effects 0.000 abstract description 27
- ALYNCZNDIQEVRV-UHFFFAOYSA-N 4-aminobenzoic acid Chemical compound NC1=CC=C(C(O)=O)C=C1 ALYNCZNDIQEVRV-UHFFFAOYSA-N 0.000 abstract description 15
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 abstract description 12
- 239000003063 flame retardant Substances 0.000 abstract description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 10
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 6
- 239000011574 phosphorus Substances 0.000 abstract description 6
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 5
- 238000010899 nucleation Methods 0.000 abstract description 4
- 230000006911 nucleation Effects 0.000 abstract description 4
- 230000000052 comparative effect Effects 0.000 description 27
- 238000002156 mixing Methods 0.000 description 26
- 230000000694 effects Effects 0.000 description 16
- 238000001746 injection moulding Methods 0.000 description 15
- 238000012360 testing method Methods 0.000 description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 11
- 229910052760 oxygen Inorganic materials 0.000 description 11
- 239000001301 oxygen Substances 0.000 description 11
- 239000000543 intermediate Substances 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 230000002195 synergetic effect Effects 0.000 description 7
- 239000002699 waste material Substances 0.000 description 5
- 239000002667 nucleating agent Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 230000002411 adverse Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- 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
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a preparation method and application of a recycled polypropylene double-effect auxiliary agent, wherein bis (dimethylamino) phosphorus chlorate, para aminobenzoic acid and potassium hydroxide are used for reaction to obtain the recycled polypropylene double-effect auxiliary agent, an aromatic amide salt segment in the auxiliary agent can play an excellent heterogeneous nucleation role in recycled polypropylene, the crystallization performance of the recycled polypropylene is improved, and the recycled polypropylene double-effect auxiliary agent contains rich nitrogen and phosphorus elements and can bring good flame retardant performance to the recycled polypropylene. The recycled polypropylene added with the double-effect additive prepared by the method has excellent flame retardance and crystallization performance and has important significance for recycling the recycled polypropylene.
Description
Technical Field
The invention relates to a preparation method and application of a recycled polypropylene double-effect auxiliary agent, and belongs to the technical field of high polymer materials.
Background
Polypropylene is widely used in various industries due to its excellent properties, and with the rapid development of various industries, waste polypropylene has become a waste polymer material with a high yield in recent years. In the recycling process, the waste polypropylene is influenced by factors such as light, heat, external force and the like, so that the crystallization performance of the waste polypropylene is poor, and the application of the waste polypropylene to high-performance products is influenced. With the rapid development of society, security issues become increasingly important. In addition, in the application fields of buildings, electronic and electrical equipment and the like, strict regulation requirements are provided for the flame retardant property of the material. Therefore, the recycled polypropylene is endowed with flame retardant property, the crystallization property is improved, the safety is greatly improved, the application range is enlarged, and the resource consumption is reduced, so that the environment-friendly and sustainable concept is met.
At present, the research on double-effect auxiliary agents which enable the recycled polypropylene to have flame retardance and improve crystallization performance is less. Therefore, in order to widen the application range, development of a double-effect auxiliary agent aiming at improving the crystallization performance of the recycled polypropylene and endowing flame retardant performance is needed, so that the practical problem of the recycled polypropylene is solved.
Disclosure of Invention
In order to solve the technical problems in the prior art, the invention provides a preparation method and application of a recycled polypropylene double-effect auxiliary agent, which have stable molecular structure, can improve the crystallization performance of recycled polypropylene, have nitrogen-phosphorus synergistic flame retardant effect, and can widen the high-valued application range of the recycled polypropylene.
The invention provides a recycled polypropylene double-effect auxiliary agent which is characterized in that the molecular structure is shown as the following formula:
the preparation method of the recycled polypropylene double-effect auxiliary agent is characterized by comprising the following steps of:
dissolving 13.71-g-aminobenzoic acid in 100 mL acetone at 25 ℃, adding 7.1-mL-bis (dimethylamino) phosphorus chlorate into a system, heating the system to 50 ℃, stirring for reaction for 24-h, washing the obtained solid with acetone, distilled water at 80 ℃ and distilled water at 25 ℃ in sequence after the reaction is finished, and drying at 80 ℃ to constant weight to obtain an intermediate A; and then weighing 13.56 g intermediate A and 100 mL acetone, placing into a flask, adding 2.8 g potassium hydroxide into the system, heating the system to 50 ℃ and stirring for reaction for 6 h, washing the obtained solid with acetone, distilled water at 80 ℃ and distilled water at 25 ℃ in sequence to neutrality after the reaction is finished, and drying at 80 ℃ to constant weight to obtain the recycled polypropylene double-effect auxiliary agent.
The invention uses acetone, distilled water at 80 ℃ and distilled water at 25 ℃ to wash in turn, which can fully remove unreacted impurities. In addition, the drying temperature of the product is too high or too low to ensure the drying effect. The impurity removal and drying conditions are the preferable conditions verified by the test.
The various reaction conditions and parameters in the preparation method of the recycled polypropylene double-effect auxiliary agent are all superior conditions verified by tests.
In addition, the application of the recycled polypropylene double-effect auxiliary agent provided by the invention has the advantage that the addition amount of the special auxiliary agent is 0.5% -2%.
Preferably, the addition amount of the double-effect auxiliary agent is 1% of the recycled polypropylene.
The addition amount of the double-effect auxiliary agent for the recycled polypropylene synthesized by the invention needs to be proper, so that the double-effect can be exerted, and the recycled polypropylene can obtain better flame retardant property and crystallization property.
Compared with the prior art, the invention has the following technical effects.
1. The recycled polypropylene double-effect auxiliary agent contains rich nitrogen and phosphorus elements, and can exert nitrogen and phosphorus synergistic flame retardance, so that the recycled polypropylene has better flame retardance.
2. The aromatic amide salt chain segment of the recycled polypropylene double-effect auxiliary agent can play an excellent heterogeneous nucleation role in the recycled polypropylene matrix, and plays a role in improving crystallization temperature.
3. The recycled polypropylene double-effect auxiliary agent is prepared by chemical combination of reactants, can achieve flame retardance, nucleation effect and stable molecular structure, and has the advantages of no decomposition, small addition amount and obvious effect in the hot processing process of recycled polypropylene. The effect is better than that of a compound auxiliary agent which is physically compounded by a single nucleating agent and a flame retardant.
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 limited thereto. All the raw materials in the examples are conventional raw materials and commercially available products without special description. The effect of the present invention on the flame retardant properties and crystallization properties of recycled polypropylene is further illustrated by comparing specific examples of the present invention with comparative examples.
Example 1
Dissolving 13.71. 13.71 g para aminobenzoic acid (CAS: 150-13-0) in 100 mL acetone at 25 ℃, adding 7.1 mL bis (dimethylamino) phosphorus chlorate (CAS: 1605-65-8) into the system, heating the system to 50 ℃, stirring to react for 24 h, washing the obtained solid with acetone, distilled water at 80 ℃ and distilled water at 25 ℃ in sequence after the reaction is finished, and drying at 80 ℃ until the weight is constant to obtain an intermediate A; then 13.56 g intermediate A and 100 mL acetone are weighed and put into a flask, 2.8 g potassium hydroxide (CAS: 1310-58-3) is added into the system, the temperature of the system is raised to 50 ℃ and stirred for reaction of 6 h, after the reaction is finished, the obtained solid is washed to be neutral by acetone, distilled water at 80 ℃ and distilled water at 25 ℃ in sequence, and the obtained solid is dried to constant weight at 80 ℃ to obtain the recycled polypropylene double-effect auxiliary agent.
And (3) conventionally mixing the recycled polypropylene (the recycled material of the electrical appliance shell) and the recycled polypropylene double-effect auxiliary agent in a high-speed mixer according to a mass ratio of 100:1 (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 limiting oxygen index of the samples was determined according to the method described in GB/T2406.2-2009 standard, the crystallization temperature of the samples was determined according to the method described in GB/T19466.3-2004 standard, and the specific data are shown in Table 1.
Example 2
This example is substantially the same as example 1 except that the mass ratio of recycled polypropylene (electrical appliance housing regrind) to recycled polypropylene dual-purpose auxiliary is 100:0.5, and the test data are shown in Table 1.
Example 3
This example is essentially the same as example 1 except that the mass ratio of recycled polypropylene (electrical appliance housing regrind) to recycled polypropylene dual effect additive is 100:2, and the test data are shown in table 1.
Comparative example 1
And extruding and granulating the pure recycled polypropylene (recycled material of the electrical appliance shell) in a conventional double-screw extruder, and performing injection molding on an injection molding machine to obtain a test sample. The limiting oxygen index of the samples was determined according to the method described in GB/T2406.2-2009 standard, the crystallization temperature of the samples was determined according to the method described in GB/T19466.3-2004 standard, and the specific data are shown in Table 1.
Comparative example 2
And (3) conventionally mixing the recycled polypropylene (the recycled material of the electrical appliance shell) and the para-aminobenzoic acid in a high-speed mixer according to a mass ratio of 100:1 (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 limiting oxygen index of the samples was determined according to the method described in GB/T2406.2-2009 standard, the crystallization temperature of the samples was determined according to the method described in GB/T19466.3-2004 standard, and the specific data are shown in Table 1.
Comparative example 3
And (3) conventionally mixing the recycled polypropylene (electrical equipment shell recycled material) and the bis (dimethylamino) phosphorus chlorate in a high-speed mixer according to a mass ratio of 100:1 (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 limiting oxygen index of the samples was determined according to the method described in GB/T2406.2-2009 standard, the crystallization temperature of the samples was determined according to the method described in GB/T19466.3-2004 standard, and the specific data are shown in Table 1.
Comparative example 4
And (3) conventionally mixing the recycled polypropylene (the electrical equipment shell recycled material) and potassium hydroxide in a high-speed mixer according to a mass ratio of 100:1 (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 limiting oxygen index of the samples was determined according to the method described in GB/T2406.2-2009 standard, the crystallization temperature of the samples was determined according to the method described in GB/T19466.3-2004 standard, and the specific data are shown in Table 1.
Comparative example 5
And (3) conventionally mixing the recycled polypropylene (the recycled material of the electrical appliance shell) and the intermediate A in a high-speed mixer according to a mass ratio of 100:1 (the mixing rotating speed is 3000 rpm, the mixing time is 5 min), extruding and granulating in a conventional double-screw extruder, and performing injection molding on an injection molding machine to obtain a test sample. The limiting oxygen index of the samples was determined according to the method described in GB/T2406.2-2009 standard, the crystallization temperature of the samples was determined according to the method described in GB/T19466.3-2004 standard, and the specific data are shown in Table 1.
Comparative example 6
The 13.56 g intermediate A and 2.8 g potassium hydroxide are physically mixed in a high-speed mixer (mixing rotation speed of 3000 rpm, mixing time of 5 min), and are subjected to conventional mixing with recycled polypropylene (electrical appliance shell reclaimed material) in the high-speed mixer according to a mass ratio of 1:100 (mixing rotation speed of 3000 rpm, mixing time of 5 min), extruded in a conventional twin-screw extruder, granulated and injection molded on an injection molding machine to obtain a test sample. The limiting oxygen index of the samples was determined according to the method described in GB/T2406.2-2009 standard, the crystallization temperature of the samples was determined according to the method described in GB/T19466.3-2004 standard, and the specific data are shown in Table 1.
Comparative example 7
The preparation method comprises the steps of physically mixing 13.71, g p-aminobenzoic acid, 7.1, mL bis (dimethylamino) phosphorus chlorate and 2.8, g potassium hydroxide in a container (mixing speed of 3000 rpm, mixing time of 5 min), carrying out conventional mixing with recycled polypropylene (electrical appliance shell reclaimed material) in a high-speed mixer according to a mass ratio of 1:100 (mixing speed of 3000 rpm, mixing time of 5 min), extruding in a conventional twin-screw extruder, granulating, and carrying out injection molding on an injection molding machine to obtain a test sample. The limiting oxygen index of the samples was determined according to the method described in GB/T2406.2-2009 standard, the crystallization temperature of the samples was determined according to the method described in GB/T19466.3-2004 standard, and the specific data are shown in Table 1.
Table 1 test results for each of examples and comparative examples
| Limiting oxygen index (%) | Crystallization temperature (. Degree. C.) | |
| Example 1 | 30.6 | 130.5 |
| Example 2 | 28.4 | 127.1 |
| Example 3 | 28.7 | 127.3 |
| Comparative example 1 | 17 | 116.1 |
| Comparative example 2 | 18.4 | 118.6 |
| Comparative example 3 | 20.7 | 116.9 |
| Comparative example 4 | 17.2 | 116.3 |
| Comparative example 5 | 25.5 | 120.2 |
| Comparative example 6 | 25.8 | 120.7 |
| Comparative example 7 | 24.2 | 115.9 |
As can be seen from the experimental results in Table 1, the limiting oxygen index and crystallization temperature of the recycled polypropylene double-effect auxiliary agent prepared in examples 1-3 are higher than those of the comparative examples. Example 1, in which the addition amount was 1%, was optimal. Compared with the pure recovered polypropylene of the comparative example 1, the recovered polypropylene double-effect auxiliary agent synthesized by the invention has the effect of obviously improving the flame retardant property and crystallization temperature of the recovered polypropylene. However, too much or too little of the double-effect auxiliary agent for the recycled polypropylene can have adverse effects on the limiting oxygen index and crystallization temperature of the recycled polypropylene.
The recycled polypropylene double-effect auxiliary agent prepared by the invention is synthesized by chemical reaction, and can play a role in improving the flame retardant property and crystallization temperature of the recycled polypropylene. Comparative examples 2 to 7 were, however, only simple mixtures of the individual raw materials, intermediates or raw materials, and did not achieve complete chemical reactions, and therefore the above-mentioned synergistic effects could not be fully exerted. Among them, the para-aminobenzoic acid added in comparative example 2 can be used as heterogeneous nucleating agent to raise the crystallization temperature of recycled polypropylene, but the nitrogen-phosphorus-free synergistic system of para-aminobenzoic acid has little effect on the improvement of flame retardant property. The bis (dimethylamino) chlorate added in the comparative example 3 is liquid, has little effect on the improvement of crystallization temperature, but contains rich nitrogen and phosphorus elements, and can play a role in nitrogen and phosphorus synergistic flame retardance on the recycled polypropylene. The potassium hydroxide added in comparative example 4 as a heterogeneous nucleating agent had only a weak effect on increasing the crystallization temperature of the recovered polypropylene. Meanwhile, in the comparative example 7 in which p-aminobenzoic acid, phosphorus bis (dimethyl) chlorate and potassium hydroxide are added, the complete chemical reaction is not performed, and only certain heterogeneous nucleation and nitrogen-phosphorus synergistic flame retardance effects are achieved, so that the improvement effect is only better than that of the comparative examples 2, 3 and 4 in which single components are added. And the comparative example 5 only added with the intermediate A can be used as a heterogeneous nucleating agent and has a nitrogen-phosphorus synergistic system to obviously improve the crystallization and flame retardant properties of the recycled polypropylene, but has limited lifting effect because the recycled polypropylene is not subjected to complete chemical reaction. Comparative example 6, in which intermediate A and potassium hydroxide were added, was the best solution in comparative example, but was still quite different from example 1 because it did not undergo complete chemical reaction.
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 utility model provides a recovered polypropylene double-effect auxiliary agent which is characterized in that the molecular structure is shown in the following figure:
2. the recycled polypropylene double-effect auxiliary agent according to claim 1, which is prepared by the following method:
dissolving 13.71-g-aminobenzoic acid in 100 mL acetone at 25 ℃, adding 7.1-mL-bis (dimethylamino) phosphorus chlorate into a system, heating the system to 50 ℃, stirring for reaction for 24-h, washing the obtained solid with acetone, distilled water at 80 ℃ and distilled water at 25 ℃ in sequence after the reaction is finished, and drying at 80 ℃ to constant weight to obtain an intermediate A; and then weighing 13.56 g intermediate A and 100 mL acetone, placing into a flask, adding 2.8 g potassium hydroxide into the system, heating the system to 50 ℃ and stirring for reaction for 6 h, washing the obtained solid with acetone, distilled water at 80 ℃ and distilled water at 25 ℃ in sequence to neutrality after the reaction is finished, and drying at 80 ℃ to constant weight to obtain the recycled polypropylene double-effect auxiliary agent.
3. Use of a recycled polypropylene dual effect co-agent according to claim 1 or 2 in recycling polypropylene.
4. The use of a recycled polypropylene dual effect additive in recycled polypropylene as claimed in claim 3, wherein: the dosage of the double-effect auxiliary agent for recycling polypropylene is 0.5% -2% of the mass of the recycled polypropylene.
5. The use of a recycled polypropylene dual effect additive in recycled polypropylene as claimed in claim 3, wherein: the dosage of the double-effect auxiliary agent for recycling polypropylene is 1% of the mass of the recycled polypropylene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311728503.6A CN117624230A (en) | 2023-12-15 | 2023-12-15 | Preparation method and application of recycled polypropylene double-effect auxiliary agent |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202311728503.6A CN117624230A (en) | 2023-12-15 | 2023-12-15 | Preparation method and application of recycled polypropylene double-effect auxiliary agent |
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| CN202311728503.6A Pending CN117624230A (en) | 2023-12-15 | 2023-12-15 | Preparation method and application of recycled polypropylene double-effect auxiliary agent |
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| Country | Link |
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