CN114349957B - Preparation method of weather-resistant polyamide resin - Google Patents
Preparation method of weather-resistant polyamide resin Download PDFInfo
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- CN114349957B CN114349957B CN202011087980.5A CN202011087980A CN114349957B CN 114349957 B CN114349957 B CN 114349957B CN 202011087980 A CN202011087980 A CN 202011087980A CN 114349957 B CN114349957 B CN 114349957B
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- 229920006122 polyamide resin Polymers 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000004952 Polyamide Substances 0.000 claims abstract description 43
- 229920002647 polyamide Polymers 0.000 claims abstract description 43
- 238000002156 mixing Methods 0.000 claims abstract description 32
- 150000003839 salts Chemical class 0.000 claims abstract description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000001361 adipic acid Substances 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 10
- 150000001491 aromatic compounds Chemical class 0.000 claims abstract description 9
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- 239000012266 salt solution Substances 0.000 claims description 30
- 238000006243 chemical reaction Methods 0.000 claims description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 16
- 239000000243 solution Substances 0.000 claims description 16
- 239000002253 acid Substances 0.000 claims description 14
- 125000003118 aryl group Chemical group 0.000 claims description 14
- 125000002843 carboxylic acid group Chemical group 0.000 claims description 14
- 150000004984 aromatic diamines Chemical class 0.000 claims description 13
- 125000003277 amino group Chemical group 0.000 claims description 12
- 230000008569 process Effects 0.000 claims description 12
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 10
- 238000012546 transfer Methods 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- FGUUSXIOTUKUDN-IBGZPJMESA-N C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 Chemical compound C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 FGUUSXIOTUKUDN-IBGZPJMESA-N 0.000 claims description 7
- GNFTZDOKVXKIBK-UHFFFAOYSA-N 3-(2-methoxyethoxy)benzohydrazide Chemical compound COCCOC1=CC=CC(C(=O)NN)=C1 GNFTZDOKVXKIBK-UHFFFAOYSA-N 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 5
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 3
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 239000011574 phosphorus Substances 0.000 claims description 3
- 239000002685 polymerization catalyst Substances 0.000 claims description 3
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 claims description 2
- MMEDJBFVJUFIDD-UHFFFAOYSA-N 2-[2-(carboxymethyl)phenyl]acetic acid Chemical compound OC(=O)CC1=CC=CC=C1CC(O)=O MMEDJBFVJUFIDD-UHFFFAOYSA-N 0.000 claims description 2
- GKXVJHDEWHKBFH-UHFFFAOYSA-N [2-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC=C1CN GKXVJHDEWHKBFH-UHFFFAOYSA-N 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims 3
- 239000002981 blocking agent Substances 0.000 abstract description 38
- 229920006351 engineering plastic Polymers 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 4
- 239000000047 product Substances 0.000 description 9
- 230000035484 reaction time Effects 0.000 description 6
- NCPXQVVMIXIKTN-UHFFFAOYSA-N trisodium;phosphite Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])[O-] NCPXQVVMIXIKTN-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 4
- 239000012752 auxiliary agent Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 229920002302 Nylon 6,6 Polymers 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000002715 modification method Methods 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical group FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 1
- OKOBUGCCXMIKDM-UHFFFAOYSA-N Irganox 1098 Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)NCCCCCCNC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 OKOBUGCCXMIKDM-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 150000003951 lactams Chemical class 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
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- Polyamides (AREA)
Abstract
The invention relates to a preparation method of weather-resistant polyamide resin, which comprises the following steps: mixing a blocking agent with a molar ratio of 0.99-1.01 with an aromatic compound containing a binary active group and water, mixing a blocking agent with a molar ratio of 0.99-1.01 with organosilicon containing a binary active group and water, mixing 1, 6-hexamethylenediamine, 1, 6-adipic acid and water with a molar ratio of 0.99-1.01, uniformly mixing the obtained solution, and obtaining a mixed polyamide salt D solution; and heating the polyamide salt D solution to obtain a polyamide melt E, and carrying out underwater pelleting and drying on the polyamide melt E by a pelleting machine to obtain the weather-resistant polyamide resin. The weather-proof polyamide resin can be used as engineering plastic material to prepare products with requirements on initial physical and mechanical properties, weather resistance and yellowness, and can be 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-resistant polyamide resin.
Background
The polyamide is mainly resin with repeated amide groups (-NHCO-) on the main chain of the molecule obtained by ring-opening polymerization of diamine and diacid or lactam. As the variety with the largest yield, the largest variety and the largest application in engineering plastics, the polyamide has good comprehensive properties including mechanical property, heat resistance, abrasion resistance, chemical resistance and self-lubricating property, has low friction coefficient, has certain flame retardance, is easy to process, is suitable for filling and reinforcing modification by glass fiber and other fillers, improves the performance and expands the application range.
As one of the main varieties of polyamide materials, the polyamide 66 has higher melting point, higher 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, gradually turns yellow and ages in the use process, and finally leads to the reduction of mechanical strength. To improve the weatherability of polyamide 66, relevant auxiliaries may be added during the preliminary polymerization or during subsequent processing to improve its properties. The subsequent processing mode is a method which is generally adopted at present due to low requirements on process equipment, but other problems such as uneven dispersion of the auxiliary agent, easy precipitation, easy decomposition of the low molecular weight auxiliary agent and the like are brought along, and meanwhile, compared with the prior polymerization process, the subsequent processing addition adds a process flow, so that the phase change increases the cost in all aspects; the modification method of the early polymerization has higher requirements on modification auxiliary agents and equipment, and the weather-proof 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
Technical problems: the invention aims to disclose a preparation method of weather-resistant polyamide resin, which overcomes the defects in the prior art. The weather-proof polyamide resin can be used as engineering plastic material to prepare products with requirements on initial physical and mechanical properties, weather resistance and yellowness, and can be applied to the fields of automobiles, electronic appliances and the like.
The technical scheme is as follows: the preparation method of the weather-resistant polyamide resin comprises the following preparation steps:
step a: mixing a blocking agent with the molar ratio of 0.99-1.01, an aromatic compound containing a binary active group and water, and reacting for 30-60 minutes at 60-65 ℃ to obtain an A salt solution with the mass concentration of 5-15%;
step b: mixing a blocking agent with the molar ratio of 0.99-1.01 with organosilicon containing binary active groups and water, and reacting for 30-60 minutes at 60-65 ℃ to obtain a B salt solution with the mass concentration of 5-15%;
step c: mixing 1, 6-hexamethylenediamine, 1, 6-adipic acid and water with the molar ratio of 0.99-1.01, and reacting for 30-60 minutes at the temperature of 60-65 ℃ to obtain a salt solution with the 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 0.01-5:0.01-5:5000-50000 to obtain a mixed polyamide salt D solution;
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 increasing the temperature to 200-230 ℃, slowly increasing the system pressure to 1.7-1.95 MPa along with the temperature increase, maintaining the pressure of 1.7-1.95 MPa, and continuing the reaction for 50-75 minutes, wherein during the reaction, the heat transfer power of the system is controlled, and the temperature is increased 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 minus 0.05-0 MPa, reducing the pressure for 50-80 minutes to obtain a polyamide melt E, and carrying out underwater pelleting and drying on the polyamide melt E by a pelleting machine to obtain the weather-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 agent comprises a compound shown as the following formula (I) and/or (II):
wherein,,
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, benzenediacetic 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 of terephthalic acid and terephthalic 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 an aromatic binary acid;
when R1 is a carboxylic acid group and/or R2 is a carboxylic acid group, the aromatic compound containing the binary active group is an aromatic diamine.
The organosilicon containing the binary active group contains a compound shown in the following formula (III):
wherein,,
r3 is a carboxylic acid group or an amino group;
r3 is carboxyl when R1 is a hydrazide group and/or R2 is an amino group;
when R1 is a carboxylic acid group and/or R2 is a carboxylic acid group, R3 is an amino group.
The beneficial effects are that: the weather-resistant polyamide resin obtained by the method has low initial yellowness index and strong light and heat resistance, and can effectively slow down the physical and mechanical property reduction of the product after long-term use at high temperature. In addition, the chromaticity retention is good, the extraction resistance of the product is excellent, and the risk of migration and precipitation of the antioxidant along with the change of time and environment does not exist. The applicant has found that the effective light and heat 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 are excellent, and the service performance is difficult to deteriorate in a long-term high-heat environment.
The weather-resistant polyamide resin can be used as engineering plastic materials to prepare products with requirements on initial physical and mechanical properties, weather resistance and yellowness, and can be applied to the fields of automobiles, electronic appliances and the like; the product of the invention can be further subjected to solid-phase tackifying to prepare a high-viscosity product, and the yellowness and chromaticity of the product of the invention can not 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 presented to facilitate a better understanding of the invention and are not intended to limit the invention in any way.
The raw materials involved in the examples are all commercial products and are commercially available;
as an example, the phosphorus-based polymerization catalyst is sodium hypophosphite;
the raw materials related to the invention are as follows:
| R1 | R2 | R3 | |
| blocking agent I-1 | Carboxyl group | / | / |
| Blocking agent I-2 | Hydrazide groups | / | / |
| Blocking agent II-1 | / | Carboxyl group | / |
| Blocking agent II-2 | / | Amino group | / |
| Organic containing binary active groupsSilicon III-1 | / | / | Amino group |
| Organosilicon III-2 containing binary active groups | / | / | Carboxyl group |
Aromatic diamine 1: p-phenylenediamine is used to produce a mixture of p-phenylenediamine,
aromatic diamine 2: the reaction product of p-xylylenediamine,
aromatic dibasic acid 1: terephthalic acid is used as a catalyst in the production of terephthalic acid,
aromatic dibasic acid 2: terephthaloyl acid.
Example 1
Step a: mixing a blocking agent I-1, a blocking agent II-1 and aromatic diamine 1 in a molar ratio of 1.00 and water, wherein the molar ratio of the blocking agent I-1 to the blocking agent II-1 is 1:1, reacting for 40 minutes at 60 ℃ to obtain an A salt solution with the mass concentration of 10%;
step b: mixing a blocking agent I-1, a blocking agent II-1 and organosilicon III-1 containing binary active groups in a molar ratio of 1.00 with water, wherein the molar ratio of the blocking agent I-1 to the blocking agent II-1 is 1:1, reacting for 40 minutes at 60 ℃ to obtain a salt solution B with the mass concentration of 10%;
step c: mixing 1, 6-hexamethylenediamine, 1, 6-adipic acid and water in a molar ratio of 1.00, and reacting at 60 ℃ for 60 minutes to obtain a salt solution with a mass concentration of 50%;
step d: uniformly mixing the salt A, the salt B and the salt C according to a solute molar ratio of 5:5:5000 to obtain a mixed polyamide salt D solution;
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 increasing the temperature to 200 ℃, slowly increasing the system pressure to 1.7MPa along with the temperature increase, maintaining the pressure of 1.7MPa, and continuing the reaction for 75 minutes, wherein during the reaction, the heat transfer power of the system is controlled, and the temperature is increased to 270 ℃ at a constant speed;
step g: maintaining the temperature of the system at 270 ℃, reducing the pressure of the system to 0MPa, reducing the pressure for 60 minutes to obtain a polyamide melt E, and carrying out underwater pelleting and drying on the polyamide melt E by a pelleting machine to obtain the weather-resistant polyamide resin.
Example 2
Step a: mixing a blocking agent I-2 and a blocking agent II-2 in a molar ratio of 1.00 with an aromatic dibasic acid 1 and water, wherein the molar ratio of the blocking agent I-2 to the blocking agent II-2 is 3:2, reacting for 30 minutes at 65 ℃ to obtain an A salt solution with the mass concentration of 5%;
step b: mixing a blocking agent I-2 and a blocking agent II-2 with a molar ratio of 1.00, organosilicon III-2 containing binary active groups and water, wherein the molar ratio of the blocking agent I-2 to the blocking agent II-2 is 3:2, reacting for 30 minutes at 65 ℃ to obtain a salt solution B with the mass concentration of 5%;
step c: mixing 1, 6-hexamethylenediamine, 1, 6-adipic acid and water in a molar ratio of 1.00, and reacting at 65 ℃ for 60 minutes to obtain a salt solution with a mass concentration of 40%;
step d: uniformly mixing the salt A, the salt B and the salt C according to a solute molar ratio of 0.1:5:10000 to obtain a mixed polyamide salt D solution;
step e: heating the mixed polyamide salt D solution to 160 ℃ under the protection of nitrogen with the pressure of 0.25MPa, and adding 300ppm of sodium phosphite in the process, wherein the reaction time is 60 minutes;
step f: gradually increasing the temperature to 230 ℃, slowly increasing the system pressure to 1.95MPa along with the temperature increase, maintaining the pressure of 1.95MPa, and continuing the reaction for 50 minutes, wherein the heat transfer power of the system is controlled during the reaction, and the temperature is increased to 275 ℃ at a uniform speed;
step g: maintaining the temperature of the system at 275 ℃, reducing the pressure of the system to 0MPa, reducing the pressure for 50 minutes to obtain a polyamide melt E, and performing underwater pelleting and drying on the polyamide melt E by a pelleting machine to obtain the weather-resistant polyamide resin.
Example 3
Step a: mixing a blocking agent I-2 with a molar ratio of 1.00, aromatic dibasic acid 2 and water, and reacting at 60 ℃ for 60 minutes to obtain an A salt solution 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 salt solution B with a mass concentration of 15%;
step c: mixing 1, 6-hexamethylenediamine, 1, 6-adipic acid and water in a molar ratio of 1.00, and reacting at 65 ℃ for 30 minutes to obtain a salt solution with a mass concentration of 60%;
step d: uniformly mixing the salt A, the salt B and the salt C according to the solute molar ratio of 1:0.01:45000 to obtain a mixed polyamide salt D solution;
step e: heating the mixed polyamide salt D solution to 160 ℃ under the protection of nitrogen with the pressure of 0.28MPa, and adding 150ppm sodium phosphite in the process, wherein the reaction time is 30 minutes;
step f: gradually increasing the temperature to 200 ℃, slowly increasing the system pressure to 1.7MPa along with the temperature increase, maintaining the pressure of 1.7MPa, and continuing the reaction for 60 minutes, wherein during the reaction, the heat transfer power of the system is controlled, and the temperature is increased to 265 ℃ at a uniform speed;
step g: maintaining the temperature of the system at 265 ℃, reducing the pressure of the system to minus 0.05MPa for 80 minutes to obtain a polyamide melt E, and carrying out underwater pelleting and drying on the polyamide melt E by a pelleting machine to obtain the weather-resistant polyamide resin.
Example 4
Step a: mixing a blocking agent I-1, a blocking agent II-1, an 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 an A salt solution with the mass concentration of 10%;
step b: mixing a blocking agent I-1, a blocking agent II-1 and organosilicon III-1 containing binary active groups in a molar ratio of 1.00 with water, wherein the molar ratio of the blocking agent I-1 to the blocking agent II-1 is 1:1, reacting for 40 minutes at 60 ℃ to obtain a salt solution B with the mass concentration of 10%;
step c: mixing 1, 6-hexamethylenediamine, 1, 6-adipic acid and water in a molar ratio of 1.00, and reacting at 60 ℃ for 60 minutes to obtain a salt solution with a mass concentration of 50%;
step d: uniformly mixing the salt A, the salt B and the salt C according to the solute molar ratio of 1:1:25000 to obtain a mixed polyamide salt D solution;
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 increasing the temperature to 200 ℃, slowly increasing the system pressure to 1.7MPa along with the temperature increase, maintaining the pressure of 1.7MPa, and continuing the reaction for 75 minutes, wherein during the reaction, the heat transfer power of the system is controlled, and the temperature is increased to 270 ℃ at a constant speed;
step g: maintaining the temperature of the system at 270 ℃, reducing the pressure of the system to 0MPa, reducing the pressure for 60 minutes to obtain a polyamide melt E, and performing underwater pelleting and drying on the polyamide melt E by a pelleting machine to obtain the weather-resistant polyamide resin.
Comparative example 1
Step a: mixing 1, 6-hexamethylenediamine, 1, 6-adipic acid and water in a molar ratio of 1.00, and reacting at 65 ℃ for 30 minutes to obtain a salt solution with a mass concentration of 60%;
step b: the preparation method comprises the steps of simultaneously adding an end capping agent I-2, an aromatic dibasic acid 2 and organosilicon III-2 with a binary active group into a salt solution C, and uniformly mixing the end capping agent I-2, the aromatic dibasic acid 2 and the organosilicon III-2 with the binary active group with the salt solution C according to a solute molar ratio of 1:1:0.01:45000 to obtain a mixed polyamide salt D solution;
step c: gradually increasing the temperature to 200 ℃, slowly increasing the system pressure to 1.7MPa along with the temperature increase, maintaining the pressure of 1.7MPa, and continuing the reaction for 60 minutes, wherein during the reaction, the heat transfer power of the system is controlled, and the temperature is increased to 265 ℃ at a uniform speed;
step d: maintaining the temperature of the system at 265 ℃, reducing the pressure of the system to minus 0.05MPa for 80 minutes to obtain a polyamide melt E, and carrying out underwater pelleting and drying on the polyamide melt E by a pelleting machine to obtain the polyamide resin.
Comparative example 2
Step a: mixing 1, 6-hexamethylenediamine, 1, 6-adipic acid and water in a molar ratio of 1.00, and reacting at 60 ℃ for 60 minutes to obtain a salt solution with a mass concentration of 50%;
step b: 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, 300ppm of sodium phosphite is added in the process, and 700ppm of antioxidant 1098 is added in the process;
step c: gradually increasing the temperature to 200 ℃, slowly increasing the system pressure to 1.7MPa along with the temperature increase, maintaining the pressure of 1.7MPa, and continuing the reaction for 75 minutes, wherein during the reaction, the heat transfer power of the system is controlled, and the temperature is increased to 270 ℃ at a constant speed;
step d: maintaining the temperature of the system at 270 ℃, reducing the pressure of the system to 0MPa, reducing the pressure for 60 minutes to obtain a polyamide melt E, and carrying out underwater pelleting and drying on the polyamide melt E by a pelleting machine to obtain the polyamide resin.
Comparative example 3
Step a: mixing a blocking agent I-1, a blocking agent II-1 and aromatic diamine 1 in a molar ratio of 1.00 and water, wherein the molar ratio of the blocking agent I-1 to the blocking agent II-1 is 1:1, reacting for 40 minutes at 60 ℃ to obtain an A salt solution with the mass concentration of 10%;
step b: mixing 1, 6-hexamethylenediamine, 1, 6-adipic acid and water in a molar ratio of 1.00, and reacting at 60 ℃ for 60 minutes to obtain a salt solution with a mass concentration of 50%;
step c: uniformly mixing the salt A and the salt C according to a solute molar ratio of 5:5000 to obtain a mixed polyamide salt D solution;
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 increasing the temperature to 200 ℃, slowly increasing the system pressure to 1.7MPa along with the temperature increase, maintaining the pressure of 1.7MPa, and continuing the reaction for 75 minutes, wherein during the reaction, the heat transfer power of the system is controlled, and the temperature is increased to 270 ℃ at a constant speed;
step f: maintaining the temperature of the system at 270 ℃, reducing the pressure of the system to 0MPa, reducing the pressure for 60 minutes to obtain a polyamide melt E, and carrying out underwater pelleting and drying on the polyamide melt E by a pelleting machine 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 testing for properties according to the following criteria:
the invention described above is provided as an example embodiment of the invention, but it is merely an example and is not to be construed as limiting. Variations of the present invention that are apparent to those skilled in the art are also included within the scope of the appended claims.
Claims (7)
1. A method for preparing weather-resistant polyamide resin, which is characterized by comprising the following preparation steps:
step a: the molar ratio is 0.99 to 1.01:1, an end capping agent is mixed with an aromatic compound containing binary active groups and water, and reacts for 30 to 60 minutes at the temperature of 60 to 65 ℃ to obtain an A salt solution with the mass concentration of 5 to 15 percent;
step b: the molar ratio is 0.99 to 1.01:1, mixing the end-capping agent with organosilicon containing binary active groups and water, and reacting for 30-60 minutes at 60-65 ℃ to obtain a B salt solution with the mass concentration of 5-15%;
step c: the molar ratio is 0.99 to 1.01:1, 6-hexamethylenediamine, 1, 6-adipic acid and water are mixed and reacted for 30 to 60 minutes at the temperature of between 60 and 65 ℃ to obtain a salt solution with the mass concentration of 40 to 60 percent;
step d: uniformly mixing the salt solution A, the salt solution B and the salt solution C according to the solute molar ratio of 0.01-5:0.01-5:5000-50000 to obtain a mixed polyamide salt D solution;
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 increasing the temperature to 200-230 ℃, slowly increasing the system pressure to 1.7-1.95 MPa along with the temperature increase, maintaining the pressure of 1.7-1.95 MPa, and continuing the reaction for 50-75 minutes, wherein during the reaction, the heat transfer power of the system is controlled, and the temperature is increased 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 minus 0.05-0 MPa for 50-80 minutes to obtain a polyamide melt E, and carrying out underwater pelleting and drying on the polyamide melt E by a pelletizer to obtain weather-resistant polyamide resin;
the end-capping agent comprises a compound shown as the following formula (I) and/or (II):
wherein,,
r1 is a carboxylic acid group or a hydrazide group, and R2 is a carboxylic acid group or an amino group;
when R1 is a hydrazide group and/or R2 is an amino group, the aromatic compound containing the binary active group is an aromatic binary acid;
when R1 is a carboxylic acid group and/or R2 is a carboxylic acid group, the aromatic compound containing the binary active group is aromatic diamine;
the organosilicon containing the binary active group contains a compound shown in the following formula (III):
wherein,,
r3 is a carboxylic acid group or an amino group;
r3 is carboxyl when R1 is a hydrazide group and/or R2 is an amino group;
when R1 is a carboxylic acid group and/or R2 is a carboxylic acid group, R3 is an amino group.
2. The process for the preparation of a polyamide resin resistant to weathering according to claim 1, characterized in that 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.
3. The method for preparing weather-resistant polyamide resin as claimed in claim 1, wherein the aromatic compound containing the binary active group is one of an aromatic diacid and an aromatic diamine.
4. The method for producing a weather-resistant polyamide resin as claimed in claim 3, wherein the aromatic dibasic acid is one or more selected from the group consisting of phthalic acid, benzenediacetic acid and isomers thereof.
5. The method for producing a weather-resistant polyamide resin as claimed in claim 3, wherein the aromatic diamine is one or more selected from the group consisting of phenylenediamine, xylylenediamine and isomers thereof.
6. The method for producing a weather-resistant polyamide resin as claimed in claim 4, wherein the aromatic dibasic acid is one or more of terephthalic acid and terephthaloyl acetic acid.
7. The method for producing a weather-resistant polyamide resin as claimed in claim 5, wherein the aromatic diamine is one or more of p-phenylenediamine and p-xylylenediamine.
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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 |
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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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