CN114349957A - Preparation method of weather-aging-resistant polyamide resin - Google Patents
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Abstract
The invention relates to a preparation method of weather-proof polyamide resin, which comprises the following steps: mixing an end-capping reagent with a molar ratio of 0.99-1.01 with an aromatic compound containing a binary active group and water, mixing the end-capping reagent with a molar ratio of 0.99-1.01 with an organosilicon containing a binary active group and water, mixing 1, 6-hexanediamine, 1, 6-adipic acid and water with a molar ratio of 0.99-1.01, and uniformly mixing the obtained solution to obtain a mixed polyamide salt D solution; and heating the polyamide salt D solution to obtain a polyamide melt E, and carrying out underwater granulation and drying on the polyamide melt E by using a granulator to obtain the weather-aging-resistant polyamide resin. The weather-resistant polyamide resin can be used as an engineering plastic material to prepare products with requirements on initial physical and mechanical properties, weather resistance and yellowness, and is applied to the fields of automobiles, electronic appliances and the like.
Description
Technical Field
The invention relates to preparation of polyamide resin, in particular to preparation of weather-aging-resistant polyamide resin.
Background
The polyamide is mainly resin which contains repeated amide groups (-NHCO-) on the molecular main chain and is obtained by ring-opening polymerization of diamine and diacid or lactam. As the variety with the largest output, the largest variety and the widest application in engineering plastics, the polyamide has good comprehensive properties including mechanical property, heat resistance, abrasion resistance, chemical resistance and self-lubrication, has low friction coefficient, certain flame retardance and easy processing, is suitable for being filled with glass fiber and other fillers for reinforcing and modifying, improves the performance and expands the application range.
Polyamide 66 is one of the main varieties of polyamide materials, has high melting point, high strength, good wear resistance and good comprehensive properties, but is easy to generate oxidation reaction under high-temperature conditions, has strong water absorption and poor weather resistance, and gradually turns yellow and ages in the using process to finally cause the reduction of mechanical strength. In order to improve the weather resistance of the polyamide 66, relevant auxiliaries can be added during the previous polymerization or during the subsequent processing to improve the performance. The subsequent processing mode is a method which is commonly adopted at present due to low requirements on process equipment, but also brings other problems, such as hidden dangers of uneven dispersion of the auxiliary agent, easy precipitation, easy decomposition of the low molecular weight auxiliary agent and the like, and meanwhile, the subsequent processing addition increases a process flow compared with the early polymerization process addition, so that the phase change improves the cost in all aspects; the early-stage polymerization modification method has high requirements on modification aids and equipment, and the weather-resistant effect after modification is difficult to accurately control, so that the modification method is difficult to popularize and use in the actual production process.
Disclosure of Invention
The technical problem is as follows: the invention aims to disclose a preparation method of a weather-aging-resistant polyamide resin, which overcomes the defects in the prior art. The weather-resistant polyamide resin can be used as an engineering plastic material to prepare products with requirements on initial physical and mechanical properties, weather resistance and yellowness, and is applied to the fields of automobiles, electronic appliances and the like.
The technical scheme is as follows: the preparation method of the weather-aging-resistant polyamide resin comprises the following preparation steps:
step a: mixing an end-capping reagent with the molar ratio of 0.99-1.01 with an aromatic compound containing a binary active group and water, and reacting at 60-65 ℃ for 30-60 minutes to obtain an A salt solution with the mass concentration of 5-15%;
step b: mixing an end capping agent with the molar ratio of 0.99-1.01 with organic silicon containing a binary active group and water, and reacting at 60-65 ℃ for 30-60 minutes to obtain a B salt solution with the mass concentration of 5-15%;
step c: mixing 1, 6-hexamethylene diamine, 1, 6-adipic acid and water in a molar ratio of 0.99-1.01, and reacting at 60-65 ℃ for 30-60 minutes to obtain a C salt solution with a mass concentration of 40-60%;
step d: uniformly mixing the salt solution A, the salt solution B and the salt solution C according to the solute molar ratio of 0.01-5: 5000-50000 to obtain a mixed polyamide salt solution D;
step e: heating the polyamide salt D solution to 150-160 ℃ under the protection of nitrogen with the pressure of 0.2-0.28 MPa, and reacting for 30-70 minutes;
step f: gradually raising the temperature to 200-230 ℃, slowly raising the system pressure to 1.7-1.95 MPa along with the temperature rise, maintaining the pressure of 1.7-1.95 MPa, continuously reacting for 50-75 minutes, and controlling the heat transfer power of the system during the period, and raising the temperature to 265-275 ℃ at a constant speed;
step g: maintaining the temperature of the system at 265-275 ℃, reducing the pressure of the system to-0.05-0 MPa, and reducing the pressure for 50-80 minutes to obtain a polyamide melt E, and carrying out underwater pelletizing and drying on the polyamide melt E by using a pelletizer to obtain the weather-aging-resistant polyamide resin.
The preparation step e is carried out in the presence of a catalyst, which is a phosphorus-based polymerization catalyst, added in an amount of 150 to 300ppm by weight.
The end-capping reagent contains a compound represented by the following formula (I) and/or (II):
wherein the content of the first and second substances,
r1 is a carboxylic acid group or a hydrazide group, and R2 is a carboxylic acid group or an amino group.
The aromatic compound containing the binary active group is one or more of aromatic dibasic acid and aromatic diamine.
The aromatic dibasic acid is selected from one or more of phthalic acid, benzene diacetic acid and isomers thereof.
The aromatic diamine is selected from one or more of phenylenediamine, xylylenediamine and isomers thereof.
The aromatic dibasic acid is one or more than one of terephthalic acid and terephthalic diacetic acid;
preferably, the aromatic diamine is one or more of p-phenylenediamine and p-xylylenediamine;
when R1 is a hydrazide group and/or R2 is an amino group, the aromatic compound containing the binary active group is aromatic dibasic acid;
when R1 is carboxylic acid group and/or R2 is carboxylic acid group, the aromatic compound containing binary active group is aromatic diamine.
The organosilicon containing binary active groups contains compounds shown in the following formula (III):
wherein the content of the first and second substances,
r3 is a carboxylic acid group or an amino group;
r3 is carboxy when R1 is a hydrazide group and/or R2 is an amino group;
r3 is amino when R1 is a carboxylic acid group and/or R2 is a carboxylic acid group.
Has the advantages that: the weather-aging-resistant polyamide resin obtained by the method has low initial yellowness index and strong light and heat resistance, and effectively slows down the reduction of the physical and mechanical properties of the product when used at high temperature for a long time. In addition, the chroma retention degree is good, the extraction resistance of the product is excellent, and the risk that the antioxidant migrates and precipitates along with the change of time and environment does not exist. The applicant unexpectedly finds that the effective photothermal resistant component of the product can be effectively combined with the polyamide molecular chain segment, the physical and mechanical properties and the chromaticity retention rate of the product are very excellent, and the service performance is difficult to deteriorate under a long-term high-temperature environment.
The weather-resistant polyamide resin can be used as an engineering plastic material to prepare products with requirements on initial physical and mechanical properties, weather resistance and yellowness, and is applied to the fields of automobiles, electronic appliances and the like; the product can be further subjected to solid-phase tackifying to prepare a high-viscosity product, and the yellowness and chroma of the product cannot be obviously increased due to the solid-phase tackifying.
Detailed Description
The preparation of the polyamide according to the invention is described in detail below with reference to the examples. The examples are given to facilitate a better understanding of the invention by a person skilled in the art and are not intended to limit the invention in any way.
The raw materials related to the examples are all commercial products and can be obtained in the market;
as an example, the phosphorus-based polymerization catalyst is sodium hypophosphite;
the invention relates to the following raw materials:
| R1 | R2 | R3 | |
| end-capping reagent I-1 | Carboxyl group | / | / |
| End-capping reagent I-2 | Hydrazide group | / | / |
| End capping agent II-1 | / | Carboxyl group | / |
| End capping agent II-2 | / | Amino group | / |
| Organosilicon III-1 containing binary active groups | / | / | Amino group |
| Organosilicon III-2 containing binary active groups | / | / | Carboxyl group |
Aromatic diamine 1: a mixture of p-phenylenediamine and p-phenylenediamine,
aromatic diamine 2: a reaction product of p-xylylenediamine,
aromatic dibasic acid 1: the amount of terephthalic acid is such that,
aromatic dibasic acid 2: p-phenylenediacetic acid.
Example 1
Step a: mixing a blocking agent I-1 and a blocking agent II-1 with aromatic diamine 1 and water in a molar ratio of 1.00, wherein the molar ratio of the blocking agent I-1 to the blocking agent II-1 is 1:1, reacting at 60 ℃ for 40 minutes to obtain a salt solution A with the mass concentration of 10%;
step b: mixing a blocking agent I-1 and a blocking agent II-1 with a molar ratio of 1.00, organosilicon III-1 containing binary active groups and water, wherein the molar ratio of the blocking agent I-1 to the blocking agent II-1 is 1:1, reacting at 60 ℃ for 40 minutes to obtain a B salt solution with the mass concentration of 10%;
step c: mixing 1, 6-hexanediamine with the molar ratio of 1.00, 1, 6-adipic acid and water, and reacting for 60 minutes at 60 ℃ to obtain a C salt solution with the mass concentration of 50%;
step d: uniformly mixing the solution of the salt A, the solution of the salt B and the solution of the salt C according to the solute molar ratio of 5:5:5000 to obtain a mixed polyamide salt solution D;
step e: heating the mixed polyamide salt D solution to 150 ℃ under the protection of nitrogen with the pressure of 0.2MPa, wherein the reaction time is 70 minutes, and 300ppm of sodium phosphite is added in the process;
step f: gradually raising the temperature to 200 ℃, slowly raising the system pressure to 1.7MPa along with the temperature rise, maintaining the pressure of 1.7MPa, and continuously reacting for 75 minutes, wherein the heat transfer power of the system is controlled during the period, and the temperature is raised to 270 ℃ at a constant speed;
step g: maintaining the temperature of the system at 270 ℃, reducing the pressure of the system to 0MPa, and reducing the pressure for 60 minutes to obtain a polyamide melt E, and carrying out underwater pelletizing and drying on the polyamide melt E by using a pelletizer to obtain the weather-resistant polyamide resin.
Example 2
Step a: mixing a blocking agent I-2 and a blocking agent II-2 with an aromatic dibasic acid 1 and water in a molar ratio of 1.00, wherein the molar ratio of the blocking agent I-2 to the blocking agent II-2 is 3: 2, reacting at 65 ℃ for 30 minutes to obtain a salt solution A with the mass concentration of 5%;
step b: mixing a blocking agent I-2 and a blocking agent II-2 with organosilicon III-2 containing binary active groups and water in a molar ratio of 1.00, wherein the molar ratio of the blocking agent I-2 to the blocking agent II-2 is 3: 2, reacting at 65 ℃ for 30 minutes to obtain a B salt solution with the mass concentration of 5%;
step c: mixing 1, 6-hexanediamine with the molar ratio of 1.00, 1, 6-adipic acid and water, and reacting for 60 minutes at 65 ℃ to obtain a C salt solution with the mass concentration of 40%;
step d: uniformly mixing the solution of the salt A, the solution of the salt B and the solution of the salt C according to the solute molar ratio of 0.1:5:10000 to obtain a mixed polyamide salt solution D;
step e: heating the mixed polyamide salt D solution to 160 ℃ under the protection of nitrogen with the pressure of 0.25MPa, wherein the reaction time is 60 minutes, and 300ppm of sodium phosphite is added in the process;
step f: gradually raising the temperature to 230 ℃, slowly raising the system pressure to 1.95MPa along with the temperature rise, maintaining the pressure of 1.95MPa, and continuously reacting for 50 minutes, wherein during the reaction, the heat transfer power of the system is controlled, and the temperature is raised to 275 ℃ at a constant speed;
step g: and maintaining the temperature of the system at 275 ℃, reducing the pressure of the system to 0MPa, and reducing the pressure for 50 minutes to obtain a polyamide melt E, and carrying out underwater granulation and drying on the polyamide melt E by using a granulator to obtain the weather-resistant polyamide resin.
Example 3
Step a: mixing a blocking agent I-2 with a molar ratio of 1.00, an aromatic dibasic acid 2 and water, and reacting at 60 ℃ for 60 minutes to obtain a salt solution A with a mass concentration of 15%;
step b: mixing a blocking agent I-2 with a molar ratio of 1.00, organosilicon III-2 containing a binary active group and water, and reacting at 60 ℃ for 60 minutes to obtain a B salt solution with a mass concentration of 15%;
step c: mixing 1, 6-hexanediamine with the molar ratio of 1.00, 1, 6-adipic acid and water, and reacting for 30 minutes at 65 ℃ to obtain a C salt solution with the mass concentration of 60%;
step d: uniformly mixing the solution of the salt A, the solution of the salt B and the solution of the salt C according to the solute molar ratio of 1:0.01:45000 to obtain a mixed polyamide salt solution D;
step e: heating the mixed polyamide salt D solution to 160 ℃ under the protection of nitrogen with the pressure of 0.28MPa, wherein the reaction time is 30 minutes, and 150ppm of sodium phosphite is added in the process;
step f: gradually raising the temperature to 200 ℃, slowly raising the system pressure to 1.7MPa along with the temperature rise, maintaining the pressure of 1.7MPa, and continuously reacting for 60 minutes, wherein the heat transfer power of the system is controlled during the period, and the temperature is raised to 265 ℃ at a constant speed;
step g: maintaining the temperature of the system at 265 ℃, reducing the pressure of the system to-0.05 MPa, and reducing the pressure for 80 minutes to obtain a polyamide melt E, and carrying out underwater pelletizing and drying on the polyamide melt E by a pelletizer to obtain the weather-resistant polyamide resin.
Example 4
Step a: mixing a blocking agent I-1 and a blocking agent II-1 with aromatic diamine 2 and water in a molar ratio of 1.00, wherein the molar ratio of the blocking agent I-1 to the blocking agent II-1 is 3: 7, reacting at 60 ℃ for 40 minutes to obtain a salt solution A with the mass concentration of 10%;
step b: mixing a blocking agent I-1 and a blocking agent II-1 with a molar ratio of 1.00, organosilicon III-1 containing binary active groups and water, wherein the molar ratio of the blocking agent I-1 to the blocking agent II-1 is 1:1, reacting at 60 ℃ for 40 minutes to obtain a B salt solution with the mass concentration of 10%;
step c: mixing 1, 6-hexanediamine with the molar ratio of 1.00, 1, 6-adipic acid and water, and reacting for 60 minutes at 60 ℃ to obtain a C salt solution with the mass concentration of 50%;
step d: uniformly mixing the salt solutions A, B and C according to the solute molar ratio of 1:1:25000 to obtain a mixed polyamide salt solution D;
step e: heating the mixed polyamide salt D solution to 150 ℃ under the protection of nitrogen with the pressure of 0.2MPa, wherein the reaction time is 70 minutes, and 300ppm of sodium phosphite is added in the process;
step f: gradually raising the temperature to 200 ℃, slowly raising the system pressure to 1.7MPa along with the temperature rise, maintaining the pressure of 1.7MPa, and continuously reacting for 75 minutes, wherein the heat transfer power of the system is controlled during the period, and the temperature is raised to 270 ℃ at a constant speed;
step g: maintaining the temperature of the system at 270 ℃, reducing the pressure of the system to 0MPa, and reducing the pressure for 60 minutes to obtain a polyamide melt E, and carrying out underwater pelletizing and drying on the polyamide melt E by using a pelletizer to obtain the weather-resistant polyamide resin.
Comparative example 1
Step a: mixing 1, 6-hexanediamine with the molar ratio of 1.00, 1, 6-adipic acid and water, and reacting for 30 minutes at 65 ℃ to obtain a C salt solution with the mass concentration of 60%;
step b: adding a blocking agent I-2, an aromatic dibasic acid 2 and a binary active group organosilicon III-2 into a C salt solution at the same time, and uniformly mixing the blocking agent I-2, the aromatic dibasic acid 2, the binary active group organosilicon III-2 and the C salt solution according to a solute molar ratio of 1:1:0.01:45000 to obtain a mixed polyamide salt D solution;
step c: gradually raising the temperature to 200 ℃, slowly raising the system pressure to 1.7MPa along with the temperature rise, maintaining the pressure of 1.7MPa, and continuously reacting for 60 minutes, wherein the heat transfer power of the system is controlled during the period, and the temperature is raised to 265 ℃ at a constant speed;
step d: maintaining the temperature of the system at 265 ℃, reducing the pressure of the system to-0.05 MPa, and reducing the pressure for 80 minutes to obtain a polyamide melt E, and carrying out underwater pelletizing and drying on the polyamide melt E by a pelletizer to obtain the polyamide resin.
Comparative example 2
Step a: mixing 1, 6-hexanediamine with the molar ratio of 1.00, 1, 6-adipic acid and water, and reacting for 60 minutes at 60 ℃ to obtain a C salt solution with the mass concentration of 50%;
step b: heating the mixed polyesteramide D solution to 150 ℃ under the protection of nitrogen with the pressure of 0.2MPa, wherein the reaction time is 70 minutes, 300ppm of sodium phosphite is added in the process, and 700ppm of antioxidant 1098 is added;
step c: gradually raising the temperature to 200 ℃, slowly raising the system pressure to 1.7MPa along with the temperature rise, maintaining the pressure of 1.7MPa, and continuously reacting for 75 minutes, wherein the heat transfer power of the system is controlled during the period, and the temperature is raised to 270 ℃ at a constant speed;
step d: maintaining the temperature of the system at 270 ℃, reducing the pressure of the system to 0MPa, and reducing the pressure for 60 minutes to obtain a polyamide melt E, and carrying out underwater pelletizing and drying on the polyamide melt E by using a pelletizer to obtain the polyamide resin.
Comparative example 3
Step a: mixing a blocking agent I-1 and a blocking agent II-1 with aromatic diamine 1 and water in a molar ratio of 1.00, wherein the molar ratio of the blocking agent I-1 to the blocking agent II-1 is 1:1, reacting at 60 ℃ for 40 minutes to obtain a salt solution A with the mass concentration of 10%;
step b: mixing 1, 6-hexanediamine with the molar ratio of 1.00, 1, 6-adipic acid and water, and reacting for 60 minutes at 60 ℃ to obtain a C salt solution with the mass concentration of 50%;
step c: uniformly mixing the salt solutions A and C according to the solute molar ratio of 5:5000 to obtain a mixed polyamide salt solution D;
step d: heating the mixed polyamide salt D solution to 150 ℃ under the protection of nitrogen with the pressure of 0.2MPa, wherein the reaction time is 70 minutes, and 300ppm of sodium phosphite is added in the process;
step e: gradually raising the temperature to 200 ℃, slowly raising the system pressure to 1.7MPa along with the temperature rise, maintaining the pressure of 1.7MPa, and continuously reacting for 75 minutes, wherein the heat transfer power of the system is controlled during the period, and the temperature is raised to 270 ℃ at a constant speed;
step f: maintaining the temperature of the system at 270 ℃, reducing the pressure of the system to 0MPa, and reducing the pressure for 60 minutes to obtain a polyamide melt E, and carrying out underwater pelletizing and drying on the polyamide melt E by using a pelletizer to obtain the polyamide resin.
The polyamide resins of the foregoing examples 1 to 4, comparative examples 1 to 3 were subjected to sample preparation and tested for properties according to the following criteria:
the present invention is provided as an exemplary embodiment of the present invention, but the present invention is merely an example and is not to be construed as limiting. Modifications of the present invention that are obvious to those skilled in the art are also intended to be included within the scope of the appended claims.
Claims (10)
1. A method for preparing a weather-resistant polyamide resin, characterized in that the method comprises the following preparation steps:
step a: mixing an end-capping reagent with the molar ratio of 0.99-1.01 with an aromatic compound containing a binary active group and water, and reacting at 60-65 ℃ for 30-60 minutes to obtain an A salt solution with the mass concentration of 5-15%;
step b: mixing an end capping agent with the molar ratio of 0.99-1.01 with organic silicon containing a binary active group and water, and reacting at 60-65 ℃ for 30-60 minutes to obtain a B salt solution with the mass concentration of 5-15%;
step c: mixing 1, 6-hexamethylene diamine, 1, 6-adipic acid and water in a molar ratio of 0.99-1.01, and reacting at 60-65 ℃ for 30-60 minutes to obtain a C salt solution with a mass concentration of 40-60%;
step d: uniformly mixing the salt solution A, the salt solution B and the salt solution C according to the solute molar ratio of 0.01-5: 5000-50000 to obtain a mixed polyamide salt solution D;
step e: heating the polyamide salt D solution to 150-160 ℃ under the protection of nitrogen with the pressure of 0.2-0.28 MPa, and reacting for 30-70 minutes;
step f: gradually raising the temperature to 200-230 ℃, slowly raising the system pressure to 1.7-1.95 MPa along with the temperature rise, maintaining the pressure of 1.7-1.95 MPa, continuously reacting for 50-75 minutes, and controlling the heat transfer power of the system during the period, and raising the temperature to 265-275 ℃ at a constant speed;
step g: maintaining the temperature of the system at 265-275 ℃, reducing the pressure of the system to-0.05-0 MPa, and reducing the pressure for 50-80 minutes to obtain a polyamide melt E, and carrying out underwater pelletizing and drying on the polyamide melt E by using a pelletizer to obtain the weather-aging-resistant polyamide resin.
2. The process for preparing a weather-resistant polyamide resin as claimed in claim 1, wherein the preparation step e is carried out in the presence of a catalyst which is a phosphorus-based polymerization catalyst and is added in an amount of 150 to 300ppm by weight.
3. The process for producing a weather-resistant polyamide resin as claimed in claim 1, wherein the end-capping agent contains a compound represented by the following formula (I) and/or (II):
wherein the content of the first and second substances,
r1 is a carboxylic acid group or a hydrazide group, and R2 is a carboxylic acid group or an amino group.
4. The method of claim 1, wherein the aromatic compound containing a divalent active group is one or more of an aromatic dibasic acid and an aromatic diamine.
5. The method of claim 4, wherein the aromatic dibasic acid is selected from the group consisting of phthalic acid, phenylenediacetic acid and isomers thereof.
6. The method of claim 4, wherein the aromatic diamine is selected from the group consisting of phenylenediamine, xylylenediamine, and isomers thereof.
7. The method for preparing weather-resistant polyamide resin as claimed in claim 5, wherein the aromatic dibasic acid is preferably one or more of terephthalic acid and terephthalic diacetic acid;
8. the method of claim 5, wherein the aromatic diamine is one or more of p-phenylenediamine and p-xylylenediamine;
9. the method of claim 3, wherein when R1 is a hydrazide group and/or R2 is an amino group, the aromatic compound containing a divalent reactive group is an aromatic dibasic acid;
when R1 is carboxylic acid group and/or R2 is carboxylic acid group, the aromatic compound containing binary active group is aromatic diamine.
10. The method of claim 1, wherein the organosilicon containing divalent reactive groups comprises a compound of the following formula (III):
wherein the content of the first and second substances,
r3 is a carboxylic acid group or an amino group;
r3 is carboxy when R1 is a hydrazide group and/or R2 is an amino group;
r3 is amino when R1 is a carboxylic acid group and/or R2 is a carboxylic acid group.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10330477A (en) * | 1997-05-27 | 1998-12-15 | Ems Inventa Ag | Production of weather-resistant polyamide, weather-resistant polyamide and its use |
| CN103204989A (en) * | 2013-04-15 | 2013-07-17 | 福建景丰科技有限公司 | Method for preparing nylon 6 for fibers from hindered amine prepolymerization unit |
| CN104136541A (en) * | 2012-02-29 | 2014-11-05 | 东丽株式会社 | Polyamide resin composition with excellent color tone |
| CN107216848A (en) * | 2017-07-11 | 2017-09-29 | 南通协鑫热熔胶有限公司 | A kind of PUR of flexible polyamide containing organosilicon and preparation method thereof |
| CN109749080A (en) * | 2018-12-26 | 2019-05-14 | 浙江新和成特种材料有限公司 | Semi-aromatic polyamide resin and preparation method thereof |
-
2020
- 2020-10-13 CN CN202011087980.5A patent/CN114349957B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10330477A (en) * | 1997-05-27 | 1998-12-15 | Ems Inventa Ag | Production of weather-resistant polyamide, weather-resistant polyamide and its use |
| CN104136541A (en) * | 2012-02-29 | 2014-11-05 | 东丽株式会社 | Polyamide resin composition with excellent color tone |
| CN103204989A (en) * | 2013-04-15 | 2013-07-17 | 福建景丰科技有限公司 | Method for preparing nylon 6 for fibers from hindered amine prepolymerization unit |
| CN107216848A (en) * | 2017-07-11 | 2017-09-29 | 南通协鑫热熔胶有限公司 | A kind of PUR of flexible polyamide containing organosilicon and preparation method thereof |
| CN109749080A (en) * | 2018-12-26 | 2019-05-14 | 浙江新和成特种材料有限公司 | Semi-aromatic polyamide resin and preparation method thereof |
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