CN114395131A - Preparation of low-density high-molecular-weight degradable bio-based polyamide elastomer material - Google Patents
Preparation of low-density high-molecular-weight degradable bio-based polyamide elastomer material Download PDFInfo
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- CN114395131A CN114395131A CN202210118243.XA CN202210118243A CN114395131A CN 114395131 A CN114395131 A CN 114395131A CN 202210118243 A CN202210118243 A CN 202210118243A CN 114395131 A CN114395131 A CN 114395131A
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- 229920001971 elastomer Polymers 0.000 title claims abstract description 57
- 239000000806 elastomer Substances 0.000 title claims abstract description 57
- 239000000463 material Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 229920006021 bio-based polyamide Polymers 0.000 title claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 57
- 239000004952 Polyamide Substances 0.000 claims abstract description 47
- 229920002647 polyamide Polymers 0.000 claims abstract description 47
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 14
- 150000004985 diamines Chemical class 0.000 claims abstract description 13
- 238000005886 esterification reaction Methods 0.000 claims abstract description 11
- 239000000178 monomer Substances 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 6
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 4
- 239000002253 acid Substances 0.000 claims abstract description 3
- 150000003839 salts Chemical class 0.000 claims abstract description 3
- 238000005809 transesterification reaction Methods 0.000 claims abstract description 3
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 15
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 10
- 229920000728 polyester Polymers 0.000 claims description 10
- 229920000570 polyether Polymers 0.000 claims description 10
- 238000007599 discharging Methods 0.000 claims description 7
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 150000003863 ammonium salts Chemical class 0.000 claims description 5
- 229920000642 polymer Polymers 0.000 claims description 5
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- 239000001307 helium Substances 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- 238000009833 condensation Methods 0.000 claims description 2
- 230000005494 condensation Effects 0.000 claims description 2
- 238000005520 cutting process Methods 0.000 claims description 2
- YQLZOAVZWJBZSY-UHFFFAOYSA-N decane-1,10-diamine Chemical compound NCCCCCCCCCCN YQLZOAVZWJBZSY-UHFFFAOYSA-N 0.000 claims description 2
- 150000002009 diols Chemical class 0.000 claims description 2
- QFTYSVGGYOXFRQ-UHFFFAOYSA-N dodecane-1,12-diamine Chemical compound NCCCCCCCCCCCCN QFTYSVGGYOXFRQ-UHFFFAOYSA-N 0.000 claims description 2
- 230000032050 esterification Effects 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 238000012544 monitoring process Methods 0.000 claims description 2
- 238000010992 reflux Methods 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims 3
- 150000002148 esters Chemical group 0.000 claims 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052799 carbon Inorganic materials 0.000 abstract description 2
- 238000011161 development Methods 0.000 abstract description 2
- 238000006386 neutralization reaction Methods 0.000 abstract description 2
- 238000012545 processing Methods 0.000 abstract description 2
- 125000004185 ester group Chemical group 0.000 description 3
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000013001 point bending Methods 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 239000004632 polycaprolactone Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/40—Polyamides containing oxygen in the form of ether groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/48—Polymers modified by chemical after-treatment
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2230/00—Compositions for preparing biodegradable polymers
Abstract
The invention discloses a preparation method of a low-density high-molecular-weight degradable bio-based polyamide elastomer material, belonging to the technical field of bio-based material processing, wherein a one-step continuous polymerization reaction process is adopted, and the one-step continuous synthesis reaction is divided into five reaction stages; the first stage is the salt forming reaction of dibasic acid and diamine monomer; the second stage is the prepolymerization of polyamide; the third stage is the polymerization of the polyamide elastomer; the fourth stage is esterification reaction of polyamide elastomer; the fifth stage is the transesterification of the esterified polyamide elastomer. The polyamide elastomer material has the advantages that the problems that the polyamide elastomer material cannot be naturally degraded, the molecular weight is low, and the mechanical property is poor are solved, the polyamide elastomer material is lighter and high in elasticity, the Shore hardness is adjustable, the polyamide elastomer material belongs to a bio-based material, and the development concept of carbon neutralization is met.
Description
Technical Field
The invention belongs to the technical field of processing of bio-based materials, and particularly relates to a preparation method of a low-density high-molecular-weight degradable bio-based polyamide elastomer material.
Background
The polyamide elastomer is a block copolymer containing an aliphatic polyvinyl soft segment and a polyamide hard segment in a molecular main chain. The polyamide elastomer materials on the market today are not naturally degradable, have low molecular weight and poor mechanical properties. Seriously affecting its application.
Disclosure of Invention
The invention aims to solve the existing problems and provides a preparation method of a low-density high-molecular-weight degradable bio-based polyamide elastomer material.
The invention is realized by the following technical scheme:
the preparation method of the low-density high-molecular-weight degradable bio-based polyamide elastomer material is characterized in that a one-step continuous polymerization reaction process is adopted, and the one-step continuous synthesis reaction is divided into five reaction stages;
the first stage is the salt forming reaction of the monomer of the dibasic acid and the diamine:
accurately weighing bio-based azelaic acid and hexamethylene diamine (or decamethylene diamine or dodecamethylene diamine) in equal molar ratio, adding deionized water in equal mass into a polymerization reaction kettle according to the mass sum of the azelaic acid and the corresponding diamine, starting stirring at a speed of 200-250 r/min, setting the reaction temperature at 50-80 ℃ and reacting for 1-2 h to complete the preparation reaction of ammonium salt;
the second stage is a prepolymerization of the polyamide:
continuously heating the prepared ammonium salt to 90-130 ℃ for reaction for 1-2 h, keeping the pressure in the reaction kettle at 0.1-0.4 MPa, stirring at the speed of 150-200 r/min, continuously discharging water vapor generated in the reaction kettle in the reaction process, monitoring the quality of the discharged water vapor in real time through a condensation reflux device, stopping discharging the water vapor until the quality of the discharged water vapor is 60-90% of the quality of the initially added deionized water, and finishing the prepolymerization reaction;
the third stage is the polymerization of the polyamide elastomer:
after the polyamide prepolymerization reaction is finished, immediately adding amine-terminated polyether and dicarboxylic acid through a constant-pressure feeding tank on a reaction kettle, under the protection of inert gas helium, continuously increasing the reaction temperature to 180-220 ℃, maintaining the reaction pressure in the reaction kettle to be 0.5-2.5 MPa, stirring at a speed of 100-150 r/min, slowly reducing the pressure in the reaction kettle to be normal pressure after reacting for 1-3 h, simultaneously increasing the temperature to 230-260 ℃, and then continuously reacting for 1-2 h to obtain a polyamide elastomer polymer;
the fourth stage is the esterification of the polyamide elastomer:
after the polymerization reaction of the polyamide elastomer is finished, immediately adding dihydric alcohol into a polyamide elastomer polymer through a constant-pressure feeding tank, simultaneously adjusting the reaction temperature to 220-250 ℃, controlling the pressure in a reaction kettle to be 0.01-0.2 MPa, and stirring at a speed of 100-150 r/min, so as to start esterification reaction, and finishing the esterification reaction when no condensate is discharged, thereby obtaining a polyamide elastomer esterified substance;
the fifth stage is the transesterification of the esterified polyamide elastomer:
immediately adding a polyester component and a catalyst into the polyamide elastomer esterified substance through a constant-pressure feeding tank after the esterification reaction of the polyamide elastomer is finished, raising the temperature to 250-280 ℃, vacuumizing to 500-800 Pa, adjusting the stirring speed to 50-100 r/min, carrying out the ester exchange reaction for 1-4 h under the condition, and discharging, cutting and drying after the ester exchange reaction is finished to obtain the degradable bio-based polyamide elastomer copolymer.
Further, based on the total mass of the azelaic acid, the diamine and the amine-terminated polyether, the amount of the amine-terminated polyether is 10 wt% -60 wt%, and the amount of the azelaic acid and the diamine monomer is 90 wt% -40 wt%.
Further, the dicarboxylic acid is equimolar to the polyetheramine and is used in an amount of the mass of the polyetheramine/the relative molecular weight of the dicarboxylic acid.
Further, the number average molecular weight of the polyamide elastomer prepolymer is 1000-5000; the molar ratio of the polyamide elastomer prepolymer to the diol is 1:2.1 to 1: 2.2.
Further, the amount of the polyester component is 1 to 60 wt%, preferably 10 to 50 wt%, based on the total mass of the azelaic acid and diamine monomers.
Further, the amount of the polyester component is 10 wt% to 50 wt% based on the total mass of the azelaic acid and diamine monomers.
Further, the catalyst is used in an amount of 0.1 to 2 wt% based on the total amount of the polyester component.
Further, the catalyst is used in an amount of 0.5 to 1 wt% based on the total amount of the polyester component.
Compared with the prior art, the invention has the following advantages:
the polyamide elastomer material has the advantages that the problems that the polyamide elastomer material cannot be naturally degraded, the molecular weight is low, and the mechanical property is poor are solved, the polyamide elastomer material is lighter and high in elasticity, the Shore hardness is adjustable, the polyamide elastomer material belongs to a bio-based material, and the development concept of carbon neutralization is met.
Detailed Description
For further explanation of the present invention, reference will now be made to the following specific examples.
The preparation method of the low-density high-molecular-weight degradable bio-based polyamide elastomer material is characterized in that a one-step continuous polymerization reaction process is adopted, and the one-step continuous synthesis reaction is divided into five reaction stages;
the first stage reaction: adding 940g of azelaic acid, 860g of decanediamine and 1800g of deionized water into a 10L polymerization kettle, starting stirring at a speed of 250r/min, setting the reaction temperature at 70 ℃, and reacting for 1h to obtain ammonium sebacoyldecamethylenediamine, thereby completing the preparation reaction of ammonium salt;
in the second stage of reaction, the temperature of the reaction system is continuously increased to 110 ℃, meanwhile, the pressure in the reaction kettle is kept at 0.2MPa, the stirring speed is 200r/min, and the water vapor generated in the reaction kettle is continuously discharged in the reaction process until the mass of the discharged water vapor is 80% of the mass of the initially added deionized water, and the exhaust is stopped to obtain polyamide 69(PA69) prepolymer;
and (3) a third-stage reaction: immediately adding 1200g of amine-terminated polyether with molecular weight of 2000 and 122g of sebacic acid into a constant-pressure feeding tank, continuously heating to 210 ℃ under the protection of helium, maintaining the pressure at 1.6MPa, continuously stirring at a rotating speed of 150r/min for reaction for 2 hours, slowly reducing the pressure in the reaction kettle to normal pressure, simultaneously heating to 250 ℃, and continuously reacting for 1 hour to obtain a polyamide 69 elastomer polymer;
and a fourth stage reaction: adding 1200g of butanediol into a polymerization kettle, simultaneously heating to 230 ℃, adjusting the pressure in the reaction kettle to be 0.1MPa, and stirring at a speed of 100r/min to perform esterification reaction until no condensate is discharged, and completing the esterification reaction to obtain an esterified polyamide 69 elastomer;
and a fifth stage reaction: immediately adding 700g of polycaprolactone and 4g of tetraalkoxy metal compound into a polymerization reaction kettle, simultaneously heating to 260 ℃, vacuumizing to 500Pa, stirring at the speed of 50-100 r/min, continuously carrying out ester exchange reaction for 3h, then finishing the reaction, discharging, cooling, granulating, and drying to obtain the finished product of the degradable polyamide elastomer copolymer.
The prepared degradable polyamide elastomer copolymer finished product is subjected to performance test, and specific test data are shown in the following table 1.
TABLE 1
| Physical Properties | 1 | 2 | 3 | 4 | 5 |
| Number average molecular weight | 46000 | 52000 | 48000 | 54000 | 56000 |
| Elongation at Break (%) | >900 | >900 | >950 | >950 | >950 |
| Tensile Strength (MPa) | 62 | 58 | 63 | 66 | 69 |
| Notched impact Strength (KJ/m)2) | NB | NB | NB | NB | NB |
| Melting Point (. degree.C.) | 191.4 | 197.3 | 196.1 | 201.2 | 202.6 |
| Shore hardness (D) | 35 | 43 | 46 | 42 | 39 |
| Density (g-cm-3) | 1.05 | 1.04 | 1.03 | 1.02 | 1.01 |
| Whether or not the three-point bending process is broken | Whether or not | Whether or not | Whether or not | Whether or not | Whether or not |
| Biodegradation Rate (%) | 95 | 88 | 92 | 87 | 82 |
As can be seen from table 1 above, the bio-based polyamide elastomer material prepared by the method of the present application is naturally degradable, has high molecular weight and excellent mechanical properties, and has the advantages of lighter weight, high elasticity and adjustable shore hardness.
Claims (8)
1. The preparation method of the low-density high-molecular-weight degradable bio-based polyamide elastomer material is characterized in that a one-step continuous polymerization reaction process is adopted, and the one-step continuous synthesis reaction is divided into five reaction stages;
the first stage is the salt forming reaction of the monomer of the dibasic acid and the diamine:
accurately weighing bio-based azelaic acid and hexamethylene diamine (or decamethylene diamine or dodecamethylene diamine) in equal molar ratio, adding deionized water in equal mass into a polymerization reaction kettle according to the mass sum of the azelaic acid and the corresponding diamine, starting stirring at a speed of 200-250 r/min, setting the reaction temperature at 50-80 ℃ and reacting for 1-2 h to complete the preparation reaction of ammonium salt;
the second stage is a prepolymerization of the polyamide:
continuously heating the prepared ammonium salt to 90-130 ℃ for reaction for 1-2 h, keeping the pressure in the reaction kettle at 0.1-0.4 MPa, stirring at the speed of 150-200 r/min, continuously discharging water vapor generated in the reaction kettle in the reaction process, monitoring the quality of the discharged water vapor in real time through a condensation reflux device, stopping discharging the water vapor until the quality of the discharged water vapor is 60-90% of the quality of the initially added deionized water, and finishing the prepolymerization reaction;
the third stage is the polymerization of the polyamide elastomer:
after the polyamide prepolymerization reaction is finished, immediately adding amine-terminated polyether and dicarboxylic acid through a constant-pressure feeding tank on a reaction kettle, under the protection of inert gas helium, continuously increasing the reaction temperature to 180-220 ℃, maintaining the reaction pressure in the reaction kettle to be 0.5-2.5 MPa, stirring at a speed of 100-150 r/min, slowly reducing the pressure in the reaction kettle to be normal pressure after reacting for 1-3 h, simultaneously increasing the temperature to 230-260 ℃, and then continuously reacting for 1-2 h to obtain a polyamide elastomer polymer;
the fourth stage is the esterification of the polyamide elastomer:
after the polymerization reaction of the polyamide elastomer is finished, immediately adding dihydric alcohol into a polyamide elastomer polymer through a constant-pressure feeding tank, simultaneously adjusting the reaction temperature to 220-250 ℃, controlling the pressure in a reaction kettle to be 0.01-0.2 MPa, and stirring at a speed of 100-150 r/min, so as to start esterification reaction, and finishing the esterification reaction when no condensate is discharged, thereby obtaining a polyamide elastomer esterified substance;
the fifth stage is the transesterification of the esterified polyamide elastomer:
immediately adding a polyester component and a catalyst into the polyamide elastomer esterified substance through a constant-pressure feeding tank after the esterification reaction of the polyamide elastomer is finished, raising the temperature to 250-280 ℃, vacuumizing to 500-800 Pa, adjusting the stirring speed to 50-100 r/min, carrying out the ester exchange reaction for 1-4 h under the condition, and discharging, cutting and drying after the ester exchange reaction is finished to obtain the degradable bio-based polyamide elastomer copolymer.
2. The preparation method of the low-density high-molecular-weight degradable biological polyamide elastomer material as claimed in claim 1, wherein the amount of the amine-terminated polyether is 10-60 wt% and the amount of the azelaic acid and diamine monomer is 90-40 wt% based on the total mass of the azelaic acid, diamine and amine-terminated polyether.
3. The preparation method of the low-density high-molecular-weight degradable bio-based polyamide elastomer material of claim 1, wherein the dicarboxylic acid is used in an equimolar ratio of the dicarboxylic acid to the polyether amine, and the molar ratio is the mass of the polyether amine/the relative molecular weight of the polyether amine.
4. The preparation method of the low-density high-molecular-weight degradable bio-based polyamide elastomer material as claimed in claim 1, wherein the number average molecular weight of the polyamide elastomer prepolymer is 1000-5000; the molar ratio of the polyamide elastomer prepolymer to the diol is 1:2.1 to 1: 2.2.
5. Preparation of a low density high molecular weight degradable bio-based polyamide elastomer material according to claim 1, characterized in that the polyester component is used in an amount of 1 to 60 wt%, preferably 10 to 50 wt%, based on the total mass of azelaic acid and diamine monomers.
6. The preparation of a low-density high-molecular-weight degradable bio-based polyamide elastomer material as claimed in claim 1, wherein the polyester component is used in an amount of 10 wt% to 50 wt% based on the total mass of the azelaic acid and diamine monomers.
7. The preparation method of the low-density high-molecular-weight degradable bio-based polyamide elastomer material of claim 1, wherein the catalyst is used in an amount of 0.1-2 wt% based on the total amount of the polyester component.
8. The preparation method of the low-density high-molecular-weight degradable bio-based polyamide elastomer material of claim 1, wherein the catalyst is used in an amount of 0.5-1 wt% based on the total amount of the polyester component.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4331786A (en) * | 1979-10-02 | 1982-05-25 | Ato Chimie | Moldable and/or extrudable polyether-ester-amide block copolymers |
| CN110003464A (en) * | 2019-03-18 | 2019-07-12 | 军事科学院系统工程研究院军需工程技术研究所 | A kind of polyamide elastomer and preparation method thereof |
| CN110016134A (en) * | 2019-03-18 | 2019-07-16 | 军事科学院系统工程研究院军需工程技术研究所 | A kind of lasting uvioresistant poly amide elastomer and preparation method thereof |
| CN111019122A (en) * | 2019-12-24 | 2020-04-17 | 浙江新和成特种材料有限公司 | Semi-aromatic polyamide thermoplastic elastomer and continuous production method thereof |
| CN111349232A (en) * | 2020-04-22 | 2020-06-30 | 建湖县兴隆尼龙有限公司 | Nylon elastomer material and preparation method thereof |
| CN113307968A (en) * | 2021-07-01 | 2021-08-27 | 郑州大学 | Polyamide elastomer with shape memory and preparation method thereof |
-
2022
- 2022-02-08 CN CN202210118243.XA patent/CN114395131A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4331786A (en) * | 1979-10-02 | 1982-05-25 | Ato Chimie | Moldable and/or extrudable polyether-ester-amide block copolymers |
| CN110003464A (en) * | 2019-03-18 | 2019-07-12 | 军事科学院系统工程研究院军需工程技术研究所 | A kind of polyamide elastomer and preparation method thereof |
| CN110016134A (en) * | 2019-03-18 | 2019-07-16 | 军事科学院系统工程研究院军需工程技术研究所 | A kind of lasting uvioresistant poly amide elastomer and preparation method thereof |
| CN111019122A (en) * | 2019-12-24 | 2020-04-17 | 浙江新和成特种材料有限公司 | Semi-aromatic polyamide thermoplastic elastomer and continuous production method thereof |
| CN111349232A (en) * | 2020-04-22 | 2020-06-30 | 建湖县兴隆尼龙有限公司 | Nylon elastomer material and preparation method thereof |
| CN113307968A (en) * | 2021-07-01 | 2021-08-27 | 郑州大学 | Polyamide elastomer with shape memory and preparation method thereof |
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