CN114507344A - Alcoholysis-resistant polyamide resin and preparation method and application thereof - Google Patents
Alcoholysis-resistant polyamide resin and preparation method and application thereof Download PDFInfo
- Publication number
- CN114507344A CN114507344A CN202011279967.XA CN202011279967A CN114507344A CN 114507344 A CN114507344 A CN 114507344A CN 202011279967 A CN202011279967 A CN 202011279967A CN 114507344 A CN114507344 A CN 114507344A
- Authority
- CN
- China
- Prior art keywords
- pressure
- polyamide resin
- alcoholysis
- nylon
- salt
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920006122 polyamide resin Polymers 0.000 title claims abstract description 125
- 238000006136 alcoholysis reaction Methods 0.000 title claims abstract description 102
- 238000002360 preparation method Methods 0.000 title abstract description 17
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 53
- 150000003839 salts Chemical class 0.000 claims abstract description 47
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 35
- 239000004952 Polyamide Substances 0.000 claims abstract description 29
- 229920002647 polyamide Polymers 0.000 claims abstract description 29
- 229920000642 polymer Polymers 0.000 claims abstract description 29
- 229920002302 Nylon 6,6 Polymers 0.000 claims abstract description 24
- 125000003277 amino group Chemical group 0.000 claims abstract description 24
- 239000002994 raw material Substances 0.000 claims abstract description 24
- 239000000178 monomer Substances 0.000 claims abstract description 19
- 238000002156 mixing Methods 0.000 claims abstract description 17
- 150000008431 aliphatic amides Chemical class 0.000 claims abstract description 11
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 9
- 239000000463 material Substances 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims description 40
- 239000004677 Nylon Substances 0.000 claims description 29
- 229920001778 nylon Polymers 0.000 claims description 29
- 238000006460 hydrolysis reaction Methods 0.000 claims description 25
- 230000007062 hydrolysis Effects 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 16
- 238000005086 pumping Methods 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 125000004432 carbon atom Chemical group C* 0.000 claims description 11
- 239000002981 blocking agent Substances 0.000 claims description 10
- 150000008430 aromatic amides Chemical class 0.000 claims description 9
- 230000003068 static effect Effects 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 229920000572 Nylon 6/12 Chemical class 0.000 claims description 7
- 150000004985 diamines Chemical class 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- 239000003054 catalyst Substances 0.000 claims description 6
- 150000003951 lactams Chemical class 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- 239000004593 Epoxy Substances 0.000 claims description 5
- 150000001412 amines Chemical class 0.000 claims description 5
- YWJUZWOHLHBWQY-UHFFFAOYSA-N decanedioic acid;hexane-1,6-diamine Chemical class NCCCCCCN.OC(=O)CCCCCCCCC(O)=O YWJUZWOHLHBWQY-UHFFFAOYSA-N 0.000 claims description 5
- XLDBGFGREOMWSL-UHFFFAOYSA-N n,n'-bis[2,6-di(propan-2-yl)phenyl]methanediimine Chemical compound CC(C)C1=CC=CC(C(C)C)=C1N=C=NC1=C(C(C)C)C=CC=C1C(C)C XLDBGFGREOMWSL-UHFFFAOYSA-N 0.000 claims description 5
- 229920006111 poly(hexamethylene terephthalamide) Chemical class 0.000 claims description 5
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 claims description 4
- 229920000007 Nylon MXD6 Chemical class 0.000 claims description 4
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 claims description 4
- DPBLXKKOBLCELK-UHFFFAOYSA-N pentan-1-amine Chemical compound CCCCCN DPBLXKKOBLCELK-UHFFFAOYSA-N 0.000 claims description 4
- -1 phosphate compound Chemical class 0.000 claims description 4
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical compound CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 claims description 3
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 claims description 3
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- JMLPVHXESHXUSV-UHFFFAOYSA-N dodecane-1,1-diamine Chemical compound CCCCCCCCCCCC(N)N JMLPVHXESHXUSV-UHFFFAOYSA-N 0.000 claims description 3
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 3
- KJOMYNHMBRNCNY-UHFFFAOYSA-N pentane-1,1-diamine Chemical compound CCCCC(N)N KJOMYNHMBRNCNY-UHFFFAOYSA-N 0.000 claims description 3
- 239000010452 phosphate Substances 0.000 claims description 3
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 claims description 2
- QVYARBLCAHCSFJ-UHFFFAOYSA-N butane-1,1-diamine Chemical compound CCCC(N)N QVYARBLCAHCSFJ-UHFFFAOYSA-N 0.000 claims description 2
- SYECJBOWSGTPLU-UHFFFAOYSA-N hexane-1,1-diamine Chemical compound CCCCCC(N)N SYECJBOWSGTPLU-UHFFFAOYSA-N 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims 1
- 239000012141 concentrate Substances 0.000 claims 1
- 239000000243 solution Substances 0.000 description 29
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 13
- 239000003365 glass fiber Substances 0.000 description 12
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 12
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 9
- 230000014759 maintenance of location Effects 0.000 description 9
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 9
- 230000032683 aging Effects 0.000 description 8
- 239000002131 composite material Substances 0.000 description 8
- 229920005989 resin Polymers 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 239000012752 auxiliary agent Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 239000002667 nucleating agent Substances 0.000 description 3
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- VHRGRCVQAFMJIZ-UHFFFAOYSA-N cadaverine Chemical compound NCCCCCN VHRGRCVQAFMJIZ-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- TVIDDXQYHWJXFK-UHFFFAOYSA-N dodecanedioic acid Chemical compound OC(=O)CCCCCCCCCCC(O)=O TVIDDXQYHWJXFK-UHFFFAOYSA-N 0.000 description 2
- 229920006351 engineering plastic Polymers 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000012760 heat stabilizer Substances 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 229920001912 maleic anhydride grafted polyethylene Polymers 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229920005992 thermoplastic resin Polymers 0.000 description 2
- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- DDLUSQPEQUJVOY-UHFFFAOYSA-N nonane-1,1-diamine Chemical compound CCCCCCCCC(N)N DDLUSQPEQUJVOY-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000000080 wetting agent Substances 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
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
- C08G69/28—Preparatory processes
-
- 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
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Polyamides (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides alcoholysis-resistant polyamide resin and a preparation method and application thereof. The polyamide resin comprises the following raw material components in percentage by mass: 97.8 to 99.98 percent of comonomer and 0.0043 to 0.011 percent of end capping agent; the comonomer comprises the following components in percentage by mass: 80-92% of nylon 66 salt and 5-15% of aliphatic amide monomer; the molar concentration of the terminal carboxyl in the polyamide resin is 10-25 mmol/kg; the molar ratio of the terminal amino groups to the terminal carboxyl groups in the polyamide resin is more than or equal to 4: 1. The alcoholysis-resistant polyamide resin is prepared by reacting a comonomer with an end-capping reagent to obtain a polyamide polymer, mixing the polyamide polymer with an optional alcoholysis-resistant reagent, and slicing and granulating. The alcoholysis-resistant polyamide resin provided by the invention has good alcoholysis resistance and good mechanical properties, and is suitable for being used as a vehicle material.
Description
Technical Field
The invention belongs to the field of polyamide resin, and particularly relates to alcoholysis-resistant polyamide resin and a preparation method and application thereof.
Background
The polyamide is a general name of thermoplastic resin containing repeated amide groups on a molecular main chain, the name of the thermoplastic resin is determined by the specific carbon atom number of a synthetic monomer, and the polyamide is the most important engineering plastic, has better mechanical property, heat resistance, abrasion resistance, chemical resistance and self-lubricating property, has lower friction coefficient, certain flame retardance and easy processing, so that the product is widely applied, almost covers each field and is the most widely applied variety of five engineering plastics. However, due to the existence of amide groups, in an environment with high temperature and high humidity, polyamide is easy to undergo hydrolysis reaction, once the hydrolysis reaction occurs, the polyamide product is rapidly degraded, so that the product performance is greatly reduced, the service life is shortened, and the application value is lost, so that how to prepare the hydrolysis and alcoholysis resistant polyamide resin is very important.
CN102516761A discloses a hydrolysis and alcoholysis resistant nylon 66 composite material and a preparation method thereof. The hydrolysis and alcoholysis resistant nylon 66 composite material prepared by the technology comprises, by weight, 51.8-84.5 parts of nylon resin, 15-40 parts of chopped glass fiber, 0.1-0.6 part of nucleating agent, 0.1-0.6 part of heat stabilizer, 0.1-1.0 part of alcoholysis resistant auxiliary agent, 0.1-5 parts of blocking agent and 0.1-1.0 part of lubricant, and the preparation method comprises the following steps: uniformly mixing the nylon 66 resin, the antioxidant, the hydrolysis resistance agent, the blocking agent, the nucleating agent and the lubricant which are dried in advance at a high speed, feeding the mixture and the glass fiber into a double-screw extruder, and extruding and granulating. Although the nylon 66 composite material prepared by the technical scheme has good high-temperature thermal oxidation aging resistance and corrosion resistance of ethylene glycol and water solution thereof, the property of nylon resin is modified.
CN101613527A discloses an alcoholysis-resistant nylon composite material and a preparation method thereof, wherein the nylon composite material prepared by the technology contains nylon, short glass fibers, a glass fiber exposure prevention adjusting auxiliary agent, a nucleating agent, a coloring agent, a heat stabilizer and an alcoholysis-resistant auxiliary agent, and has excellent physical and chemical properties. The short glass fiber adopted in the technical scheme is treated by the silane coupling agent, and the silane wetting agent is coated on the surface of the short glass fiber, so that the alcoholysis resistance of the nylon composite material is improved, but the alcoholysis resistance of the alcoholysis resistance nylon composite material is mainly provided by the short glass fiber treated by the silane coupling agent, and the property of the nylon resin is not improved.
CN106987122A discloses hydrolysis-resistant short glass fiber reinforced nylon 66 and a preparation method thereof. The hydrolysis-resistant short glass fiber reinforced nylon 66 prepared by the technology comprises the following raw material components in parts by weight: 35-50 parts of nylon 66, 50-60 parts of glass fiber, 0.5-1.0 part of antioxidant, 1.0 part of black master batch, 0.1-0.5 part of calcium stearate and 0.1-0.5 part of maleic anhydride grafted polyethylene wax; the preparation method comprises the steps of weighing, mixing, stirring, melt extrusion, cooling, drying and the like. According to the technical scheme, the maleic anhydride grafted polyethylene wax with high molecular weight is added, so that the overall polarity of the material is reduced, and the water absorption capacity of the material is reduced, so that the hydrolysis resistance of the chopped glass fiber reinforced nylon 66 is improved, but the property of the nylon 66 resin is not improved.
Therefore, in the prior art, the method for improving alcoholysis resistance of the nylon composite material generally comprises the steps of adding an alcoholysis resistance auxiliary agent or filler, such as glass fiber, to the nylon material; the introduction of the alcoholysis resistance auxiliary agent or the filler can not only influence the microcosmic continuity of the nylon material to cause the change of mechanical properties, but also increase the processing difficulty of the polymer and improve the preparation cost. Therefore, how to make the polyamide resin have better alcoholysis resistance and excellent mechanical properties by modifying the polyamide resin without adding other alcoholysis resistance aids is a problem to be solved at present.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide an alcoholysis-resistant polyamide resin and a preparation method and application thereof. According to the invention, the occurrence of hydrolysis/alcoholysis reaction is reduced by limiting the molar concentration of the terminal carboxyl groups and the molar ratio of the terminal amino groups to the terminal carboxyl groups in the polyamide resin, and the prepared polyamide resin has excellent alcoholysis resistance and better mechanical property, and simultaneously reduces the influence of secondary melting on the performance of polyamide products.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides an alcoholysis-resistant polyamide resin, which comprises the following raw material components in percentage by mass: 97.8 to 99.98 percent of comonomer and 0.0043 to 0.011 percent of end capping agent;
the copolymerization unit comprises the following components in percentage by mass: 80-92% of nylon 66 salt and 5-15% of aliphatic amide monomer;
the molar concentration of the terminal carboxyl in the polyamide resin is 10-25 mmol/kg;
the molar ratio of the terminal amino group to the terminal carboxyl group in the polyamide resin is not less than 4:1, for example, 4.2:1, 4.5:1, 4.8:1, 5:1, 5.2:1, 5.5:1, 5.8:1, 6:1, 6.2:1, 6.5:1, 6.8:1, 7:1, 7.2:1, 7.5:1, 7.8:1, 8:1, 8.2:1, 8.5:1, or 8.7: 1.
In the present invention, a polyamide resin is prepared from specific raw material components and proportions, and the molar concentration of the terminal carboxyl groups and the molar ratio of the terminal amino groups to the terminal carboxyl groups of the polyamide resin are further defined by controlling the content of the end-capping agent. When the molar concentration of the terminal carboxyl groups in the polyamide resin is 10-25mmol/kg and the molar ratio of the terminal amino groups to the terminal carboxyl groups is more than or equal to 4:1, the polyamide resin has excellent hydrolysis resistance. When the molar concentration of the terminal carboxyl groups in the polyamide resin is small or large or the molar ratio of the terminal amino groups to the terminal carboxyl groups is less than 4:1, the hydrolysis resistance of the polyamide resin is poor.
In the present invention, the comonomer may be 97.8%, 98.2%, 98.5%, 98.8%, 99%, 99.3%, 99.5%, 99.98%, or the like in mass%.
The mass percentage of the capping agent may be 0.0043%, 0.005%, 0.0055%, 0.006%, 0.0065%, 0.007%, 0.0075%, 0.008%, 0.0085%, 0.009%, 0.0095%, 0.01%, or 0.011%, etc.
The mass percentage of the nylon 66 salt may be 80%, 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, 90%, 91%, 92%, or the like.
The aliphatic amide monomer may be 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15% or the like in mass%.
The molar concentration of the terminal carboxyl groups in the polyamide resin may be 10mmol/kg, 12mmol/kg, 15mmol/kg, 18mmol/kg, 20mmol/kg, 23mmol/kg, 25mmol/kg or the like.
It should be noted that, since the reaction of acid and amine to form polymer polyamide is reversible reaction, the reaction degree cannot reach 100%, so the molar concentration of terminal carboxyl group in polyamide resin is hardly lower than 10 mmol/kg; when the molar concentration of the terminal carboxyl groups is larger, the hydrolysis of the polyamide is accelerated by the catalytic action of the acid, so that the hydrolysis (alcoholysis) resistance of the prepared polyamide resin is reduced.
The following is a preferred technical solution of the present invention, but not a limitation to the technical solution provided by the present invention, and the object and advantageous effects of the present invention can be better achieved and achieved by the following preferred technical solution.
In a preferred embodiment of the present invention, the aliphatic amide monomer is a nylon salt and/or a lactam.
Preferably, at least one of the diamine and the diacid used for preparing the nylon salt has 7 to 15 carbon atoms (for example, 7, 8, 9, 10, 11, 12, 13, 14 or 15 carbon atoms), and more preferably 8 to 12 carbon atoms.
Illustratively, the diamine from which the nylon salt is made is selected from the group consisting of nonanediamine, decanediamine, dodecanediamine; the diacid is selected from azelaic acid, sebacic acid and dodecanedioic acid.
Preferably, the nylon salt is selected from any one of nylon 610 salt, nylon 612 salt and nylon 1212 salt or the combination of at least two of the nylon 610 salt, the nylon 612 salt and the nylon 1212 salt.
Preferably, the lactam has a number of carbon atoms of from 7 to 15 (which may be, for example, 7, 8, 9, 10, 11, 12, 13, 14 or 15), more preferably from 8 to 12.
Preferably, the lactam is decanolactam and/or dodecanolactam.
In the invention, the alcoholysis resistance of the polyamide resin can be improved by copolymerization of the aliphatic amide monomer with a specific number of carbon atoms and the nylon 66 salt, and if the number of carbon atoms in the aliphatic amide monomer is less, the alcoholysis resistance of the prepared polyamide resin is poorer; if the number of carbon atoms in the aliphatic amide monomer is large, the mechanical property of the prepared polyamide resin is poor.
As a preferred technical scheme of the invention, the end-capping reagent is monoamine and/or diamine.
Preferably, the monoamine is selected from any one of ammonia monohydrate, ethylamine, n-propylamine, n-butylamine, n-pentylamine, n-hexylamine, or benzylamine, or a combination of at least two thereof.
Preferably, the diamine is selected from any one of pentanediamine, hexanediamine, butanediamine, decanediamine or dodecanediamine or a combination of at least two thereof.
Preferably, the molar concentration of the terminal amino groups in the polyamide resin is 64 to 140mmol/kg, and may be, for example, 64mmol/kg, 70mmol/kg, 75mmol/kg, 80mmol/kg, 85mmol/kg, 90mmol/kg, 95mmol/kg, 100mmol/kg, 105mmol/kg, 110mmol/kg, 115mmol/kg, 120mmol/kg, 125mmol/kg, 130mmol/kg, 135mmol/kg or 140 mmol/kg.
Preferably, the molar ratio of the terminal amino groups to the terminal carboxyl groups in the polyamide resin is 4:1 to 10:1, and may be, for example, 4:1, 4.5:1, 5:1, 5.5:1, 6:1, 6.5:1, 7:1, 7.5:1, 8:1, 8.5:1, 9:1, 9.5:1, or 10: 1.
In a preferred embodiment of the present invention, the comonomer further comprises an aromatic amide monomer.
Preferably, the aromatic amide monomer is selected from any one of or a combination of at least two of nylon 6I salt, nylon 6T salt or nylon MXD6 salt.
Preferably, the mass percentage of the aromatic amide monomer to the comonomer is 3 to 5%, and may be, for example, 3%, 3.2%, 3.4%, 3.6%, 3.8%, 4%, 4.2%, 4.4%, 4.6%, 4.8%, or 5%.
In the invention, the aromatic amide monomer is used, so that the hydrolysis condition of the polyamide resin can be destroyed, and the mechanical property of the polyamide resin can be enhanced, therefore, the polyamide resin formed by copolymerizing the aromatic amide monomer, the nylon 66 salt and the aliphatic amide monomer has lower water absorption, better hydrolysis resistance and better mechanical property.
Preferably, the raw material components of the polyamide resin further comprise an alcoholysis resistance agent.
Preferably, the alcoholysis resistance agent is selected from any one or a combination of at least two of bis (2, 6-diisopropylphenyl) carbodiimide, macromolecular hindered amine and phosphate compounds, epoxy polymer hydrolysis resistance agent and polycarbodiimide.
Preferably, the alcoholysis resistance agent is 0.1 to 2% by mass of the raw polyamide resin component, and may be, for example, 0.1%, 0.3%, 0.5%, 0.7%, 1%, 1.2%, 1.4%, 1.6%, 1.8%, 2%, or the like.
In the present invention, the raw material composition of the polyamide resin further includes a catalyst for accelerating the reaction rate of the raw material of the polyamide resin, the catalyst used in the present invention is a catalyst known in the art, and may be, for example, sodium hypophosphite, and the content of the catalyst is 0.01 to 0.2% by mass, and may be, for example, 0.01%, 0.02%, 0.04%, 0.06%, 0.08%, 0.1%, 0.12%, 0.14%, 0.16%, 0.18%, or 0.2% by mass, based on the raw material composition of the polyamide resin.
In a preferred embodiment of the present invention, the relative viscosity of the polyamide resin is 2.4 to 3.1, and may be, for example, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3, or 3.1.
Preferably, the polyamide resin has a relative viscosity of 2.55 to 2.6, which may be, for example, 2.55, 2.56, 2.57, 2.58, 2.6, etc.
In a second aspect, the present invention provides a method for preparing the alcoholysis resistance polyamide resin, comprising the following steps:
(1) carrying out a reaction on a comonomer and a terminating agent to obtain a polyamide polymer;
(2) and (2) mixing the polyamide polymer obtained in the step (1) with an optional alcoholysis-resistant agent, and then slicing and granulating to obtain the alcoholysis-resistant polyamide resin.
In addition, since the molar concentration of the terminal carboxyl groups and the molar concentration of the terminal amino groups of the polyamide resin obtained by mixing the polyamide polymer and the optional alcoholysis resistance agent and pelletizing the mixture cannot be tested, the molar concentration of the terminal carboxyl groups and the molar concentration of the terminal amino groups of the polyamide resin according to the present invention refer to the molar concentration of the terminal carboxyl groups and the molar concentration of the terminal amino groups of the polyamide polymer obtained in step (1).
In a preferred embodiment of the present invention, the comonomer is a concentrated comonomer solution.
Preferably, the solvent of the comonomer solution is desalted water.
Preferably, the concentration is carried out in a concentration tank.
Preferably, the pressure in the concentration tank is 0.2 to 0.3MPa, and may be, for example, 0.2MPa, 0.22MPa, 0.24MPa, 0.26MPa, 0.28MPa or 0.3 MPa.
Preferably, the concentrated comonomer solution has a mass concentration of 75-85%, for example 75%, 76%, 77%, 78%, 79%, 80%, 81%, 82%, 83%, 84%, or 85%, etc.
Preferably, the blocking agent is a blocking agent solution.
Preferably, the solvent of the capping agent solution is desalted water.
Preferably, the concentration of the blocking agent solution is 45 to 55% by mass, and may be, for example, 45%, 46%, 47%, 48%, 49%, 50%, 51%, 52%, 53%, 54%, 55%, or the like.
As a preferred embodiment of the present invention, the temperature of the reaction in the step (1) is 250 to 270 ℃, and may be, for example, 250 ℃, 252 ℃, 255 ℃, 258 ℃, 260 ℃, 263 ℃, 265 ℃, 267 ℃ or 270 ℃.
Preferably, the reaction in step (1) comprises stages of temperature rise and pressure rise, pressure maintaining and temperature rise, pressure relief and vacuum pumping.
Preferably, in the temperature and pressure raising, the rate of temperature raising is 1.5-2 ℃/min, and may be, for example, 1.5 ℃/min, 1.6 ℃/min, 1.7 ℃/min, 1.8 ℃/min, 1.9 ℃/min, 2 ℃/min or the like.
Preferably, the time for raising the temperature and the pressure is 15-25min, for example, 15min, 16min, 17min, 18min, 19min, 20min, 21min, 22min, 23min, 24min or 25 min.
The pressure for raising the temperature and pressure is preferably 1.6 to 1.85MPa, and may be, for example, 1.6MPa, 1.68MPa, 1.72MPa, 1.75MPa, 1.77MPa, 1.8MPa, 1.82MPa or 1.85 MPa.
Preferably, the pressure of the holding pressure is 1.6 to 1.85MPa, and may be, for example, 1.6MPa, 1.67MPa, 1.71MPa, 1.74MPa, 1.77MPa, 1.8MPa, 1.82MPa, 1.85MPa, or the like.
Preferably, the pressure holding time is 60-75min, such as 60min, 62min, 65min, 67min, 70min, 72min or 75 min.
Preferably, the temperature for pressure and temperature increase is 250-270 ℃, for example, 250 ℃, 252 ℃, 255 ℃, 258 ℃, 260 ℃, 263 ℃, 265 ℃, 267 ℃ or 270 ℃ and the like.
Preferably, the pressure relief comprises a first pressure relief phase, a second pressure relief phase and a third pressure relief phase.
Preferably, the pressure of the reaction after the first pressure relief stage is 0.4 to 0.5MPa (for example, 0.4MPa, 0.42MPa, 0.44MPa, 0.46MPa, 0.48MPa, or 0.5MPa, etc.), the pressure of the reaction after the second pressure relief stage is 0.15 to 0.25MPa (for example, 0.15MPa, 0.17MPa, 0.19MPa, 0.21MPa, 0.23MPa, or 0.25MPa, etc.), and the pressure of the reaction after the third pressure relief stage is 0.095 to 0.15MPa (for example, 0.095MPa, 0.097MPa, 0.099MPa, 0.11MPa, 0.13MPa, or 0.15MPa, etc.).
Preferably, the pressure relief rate is 0.01-0.05MPa/min, and may be, for example, 0.01MPa/min, 0.015MPa/min, 0.02MPa/min, 0.025MPa/min, 0.03MPa/min, 0.035MPa/min, 0.04MPa/min, 0.045MPa/min, 0.01MPa/min, or the like.
Preferably, after the vacuum-pumping stage, the degree of vacuum of the reaction is-0.035 to-0.025 MPa, and may be, for example, -0.035MPa, -0.033MPa, -0.03MPa, -0.027MPa or-0.025 MPa.
Preferably, the time for maintaining the vacuum degree is 7-12min, for example, 7min, 8min, 9min, 10min, 11min or 12min, etc.
Preferably, the reaction is carried out in the presence of nitrogen.
Preferably, in the step (2), the mixing method is mixing by a mixer.
Preferably, the mixers are feed mixers and static mixers.
As a preferred technical scheme of the invention, the preparation method comprises the following steps:
(1) adding the comonomer solution into a concentration tank with the pressure of 0.2-0.3MPa for concentration, reacting the concentrated comonomer solution with the mass concentration of 75-85%, the capping reagent solution with the mass concentration of 45-55% and a catalyst in a nitrogen atmosphere, and performing temperature rise and pressure rise, pressure maintaining and temperature rise, pressure relief and vacuum pumping to obtain a polyamide polymer; wherein, when the temperature and the pressure are increased, the rate of temperature increase is 1.5-2 ℃/min, the time is 15-25min, the pressure of temperature increase and pressure increase is 1.6-1.85MPa, the pressure is 1.6-1.85MPa when the pressure and the temperature are maintained, the time is 60-75min, the temperature of pressure maintaining and temperature increase is 250-;
(2) and (2) mixing the polyamide polymer obtained in the step (1) and an optional alcoholysis-resistant agent through a feed mixer and a static mixer, and then slicing and granulating to obtain the alcoholysis-resistant polyamide resin.
In a third aspect, the invention provides a use of the alcoholysis resistant polyamide resin as described above as a material for vehicles.
Compared with the prior art, the invention has at least the following beneficial effects:
the alcoholysis-resistant polyamide resin is prepared by specific raw material components and proportions, the molar concentration of terminal carboxyl groups of the polyamide resin and the molar ratio of terminal amino groups to terminal carboxyl groups are particularly limited, and the probability of occurrence of hydrolysis/alcoholysis reaction of the polyamide resin is reduced, so that the prepared alcoholysis-resistant polyamide resin has good hydrolysis resistance and good mechanical properties, the tensile strength of the alcoholysis-resistant polyamide resin is 93-112 MPa, the alcoholysis aging-resistant tensile strength of the alcoholysis-resistant polyamide resin is 51-73 MPa, the tensile strength retention rate is not lower than 52%, the surface performance of the alcoholysis-resistant polyamide resin is good, and the alcoholysis-resistant polyamide resin is suitable for use.
Detailed Description
The technical solution of the present invention is further illustrated by the following specific examples. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Some of the raw material sources in the examples and comparative examples are as follows:
polycarbodiimide: shanghai Yuen chemical Co., Ltd., UN-03;
macromolecular hindered amine and phosphate ester compounds: hiplacamide AO-200, Shanghai Raji industries, Ltd;
epoxy polymer hydrolysis resistance agent: sandwell AH81, Sandwell, Inc. of Dongguan.
Example 1
The embodiment provides an alcoholysis-resistant polyamide resin (relative viscosity of 2.40) which comprises the following raw material components in percentage by mass:
wherein the comonomer comprises the following components in percentage by mass: 92% of nylon 66 salt, 5% of nylon 612 salt and 3% of nylon MXD6 salt, wherein the alcoholysis resistance agent consists of bis (2, 6-diisopropylphenyl) carbodiimide and polycarbodiimide (UN-03) according to the mass ratio of 1: 2.
The preparation method of the alcoholysis-resistant polyamide resin comprises the following steps:
(1) adding a comonomer solution with the mass concentration of 57% into a concentration tank with the pressure of 0.25MPa for concentration, reacting the concentrated comonomer solution with the mass concentration of 80%, a hexamethylenediamine solution with the mass concentration of 50% and sodium hypophosphite in a nitrogen atmosphere, and performing heating and pressurizing, pressure maintaining and heating, pressure relief and vacuum pumping to obtain a polyamide polymer; wherein, when the temperature and the pressure are raised, the rate of the temperature rise is 1.8 ℃/min, the time is 20min, the pressure of the temperature and the pressure rise is 1.7MPa, the pressure is 1.85MPa, the time is 65min, the temperature of the pressure maintaining and the temperature is 260 ℃, the pressure relief comprises a first pressure relief stage, a second pressure relief stage and a third pressure relief stage, the pressure of the reaction is 0.45MPa after the first pressure relief stage, the pressure relief rate is 0.045MPa/min, the pressure of the reaction is 0.2MPa after the second pressure relief stage, the pressure relief rate is 0.03MPa/min, the pressure of the reaction is 0.1MPa after the third pressure relief stage, the pressure relief rate is 0.0102MPa/min, the vacuum degree of the reaction is-0.025 MPa after the vacuum pumping, and the time for maintaining the vacuum degree is 10 min;
(2) mixing the polyamide polymer obtained in the step (1) and an alcoholysis-resistant agent through a feed mixer and a static mixer, and then slicing and granulating to obtain an alcoholysis-resistant polyamide resin;
wherein the polyamide resin has a carboxyl end group concentration of 14mmol/kg, an amino end group concentration of 140mmol/kg, and a molar ratio of the amino end group to the carboxyl end group of 10: 1.
Example 2
This example provides an alcoholysis-resistant polyamide resin (relative viscosity of 2.60) comprising the following raw material components in percentage by mass:
wherein the comonomer comprises the following components in percentage by mass: 80% of nylon 66 salt, 15% of nylon 610 salt and 5% of nylon 6T salt, wherein the alcoholysis resistance agent consists of high-efficiency macromolecular hindered amine and phosphate ester compound (Hiparamide A0-200) and epoxy polymer hydrolysis resistance agent (Sanwell AH81) according to the mass ratio of 1:1.
The preparation method of the alcoholysis-resistant polyamide resin comprises the following steps:
(1) adding a nylon salt solution with the mass concentration of 56.75% and a laurolactam solution with the mass concentration of 50% into a concentration tank with the pressure of 0.25MPa for concentration, reacting a comonomer solution with the mass concentration of 80%, a capping reagent solution with the mass concentration of 50% and sodium hypophosphite after concentration under the protection of nitrogen, and obtaining a polyamide polymer after temperature and pressure rise, pressure maintaining and rise, pressure relief and vacuum pumping; wherein, when the temperature and the pressure are raised, the rate of temperature rise is 1.8 ℃/min, the time is 20min, the pressure of temperature rise and pressure rise is 1.7MPa, the pressure is 1.8MPa, the time is 60min, the temperature of pressure maintaining and temperature rise is 260 ℃, the pressure relief comprises a first pressure relief stage, a second pressure relief stage and a third pressure relief stage, the pressure of the reaction is 0.45MPa after the first pressure relief stage, the pressure relief rate is 0.05MPa/min, the pressure of the reaction is 0.2MPa after the second pressure relief stage, the pressure relief rate is 0.03MPa/min, the pressure of the reaction is 0.1MPa after the third pressure relief stage, the pressure relief rate is 0.01MPa/min, the vacuum degree of the reaction is-0.035 MPa after the vacuum pumping, and the time for maintaining the vacuum degree is 10 min;
(2) mixing the polyamide polymer obtained in the step (1) and an alcoholysis-resistant agent through a feed mixer and a static mixer, and then slicing and granulating to obtain an alcoholysis-resistant polyamide resin;
wherein the polyamide resin has a carboxyl end group concentration of 25mmol/kg, an amino end group concentration of 100mmol/kg, and a molar ratio of the amino end group to the carboxyl end group of 4: 1.
Example 3
The embodiment provides an alcoholysis-resistant polyamide resin (with a relative viscosity of 3.10) which comprises the following raw material components in percentage by mass:
wherein the comonomer comprises the following components in percentage by mass: 86% of nylon 66 salt, 10% of nylon 612 salt and 4% of nylon 6I salt.
The preparation method of the alcoholysis-resistant polyamide resin comprises the following steps:
(1) adding a comonomer solution with the mass concentration of 57% into a concentration tank with the pressure of 0.2MPa for concentration, reacting the concentrated comonomer solution with the mass concentration of 75%, an ammonia monohydrate solution with the mass concentration of 45% and sodium hypophosphite under the protection of nitrogen, and obtaining a polyamide polymer after heating up and boosting, pressure maintaining and heating up, pressure relief and vacuum pumping; wherein, when the temperature and the pressure are raised, the rate of temperature rise is 1.7 ℃/min, the time is 25min, the pressure of temperature and pressure rise is 1.85MPa, the pressure is 1.85MPa, the time is 75min, the temperature of pressure maintaining and temperature rise is 250 ℃, the pressure relief comprises a first pressure relief stage, a second pressure relief stage and a third pressure relief stage, the pressure of the reaction is 0.4MPa after the first pressure relief stage, the pressure relief rate is 0.045MPa/min, the pressure of the reaction is 0.15MPa after the second pressure relief stage, the pressure relief rate is 0.03MPa/min, the pressure of the reaction is 0.095MPa after the third pressure relief stage, the pressure relief rate is 0.0102MPa/min, the vacuum degree of the reaction is-0.03 MPa after the vacuum pumping, and the time for maintaining the vacuum degree is 12 min;
(2) mixing the polyamide polymer obtained in the step (1) and polycarbodiimide (UN-03) through a feeding mixer and a static mixer, and then slicing and granulating to obtain alcoholysis-resistant polyamide resin;
wherein the polyamide resin has a carboxyl end group concentration of 10mmol/kg, an amino end group concentration of 80mmol/kg, and a molar ratio of the amino end group to the carboxyl end group of 8: 1.
Example 4
This example provides an alcoholysis-resistant polyamide resin (relative viscosity of 2.60) comprising the following raw material components in percentage by mass:
wherein the comonomer comprises the following components in percentage by mass: 90% of nylon 66 salt and 10% of nylon 612 salt.
The preparation method of the alcoholysis-resistant polyamide resin comprises the following steps:
(1) adding a nylon salt solution with the mass concentration of 56.75% and a decanolactam solution with the mass concentration of 50% into a concentration tank with the pressure of 0.3MPa for concentration, reacting a comonomer solution with the mass concentration of 85%, a pentamethylene diamine solution with the mass concentration of 55% and sodium hypophosphite after concentration under the protection of nitrogen, and obtaining a polyamide polymer after temperature and pressure rise, pressure maintaining and rise, pressure relief and vacuum pumping; wherein, when the temperature and the pressure are raised, the rate of temperature rise is 2 ℃/min, the time is 15min, the pressure of temperature rise and pressure rise is 1.6MPa, the pressure is 1.6MPa, the time is 72min, the temperature of pressure maintaining and temperature rise is 270 ℃, the pressure relief comprises a first pressure relief stage, a second pressure relief stage and a third pressure relief stage, after the first pressure relief stage, the pressure of reaction is 0.5MPa, the pressure relief rate is 0.045MPa/min, after the second pressure relief stage, the pressure of reaction is 0.25MPa, the pressure relief rate is 0.03MPa/min, after the third pressure relief stage, the pressure of reaction is 0.15MPa, the pressure relief rate is 0.0102MPa/min, after the vacuum pumping, the vacuum degree of reaction is-0.025 MPa, and the time for maintaining the vacuum degree is 10 min;
(2) mixing the polyamide polymer obtained in the step (1) and an epoxy polymer hydrolysis resistant agent (Sanwell AH81) through a feeding mixer and a static mixer, and then slicing and granulating to obtain alcoholysis-resistant polyamide resin;
wherein the concentration of the terminal carboxyl groups of the polyamide resin is 18mmol/kg, the concentration of the terminal amino groups is 108mmol/kg, and the molar ratio of the terminal amino groups to the terminal carboxyl groups is 6: 1.
Example 5
This example provides an alcoholysis-resistant polyamide resin (relative viscosity of 2.60) comprising the following raw material components in percentage by mass:
wherein the comonomer comprises the following components in percentage by mass: 90% of nylon 66 salt, 5% of decanolactam, 5% of nylon MXD6 salt and a capping agent, wherein the capping agent consists of ammonia monohydrate and hexamethylene diamine in a mass ratio of 1: 1.7.
The preparation method of the alcoholysis-resistant polyamide resin comprises the following steps:
(1) adding a comonomer solution with the mass concentration of 57.3% into a concentration tank with the pressure of 0.23MPa for concentration, reacting the concentrated comonomer solution with the mass concentration of 82%, a hexamethylenediamine solution with the mass concentration of 48% and sodium hypophosphite under the protection of nitrogen, and obtaining a polyamide polymer after heating up and boosting, pressure maintaining and heating up, pressure relief and vacuum pumping; wherein, when the temperature and the pressure are raised, the rate of the temperature rise is 1.9 ℃/min, the time is 22min, the pressure of the temperature and the pressure rise is 1.82MPa, the pressure is 1.82MPa, the time is 68min, the temperature of the pressure maintaining and the temperature is 265 ℃, the pressure relief comprises a first pressure relief stage, a second pressure relief stage and a third pressure relief stage, the pressure of the reaction is 0.48MPa after the first pressure relief stage, the pressure relief rate is 0.045MPa/min, the pressure of the reaction is 0.21MPa after the second pressure relief stage, the pressure relief rate is 0.03MPa/min, the pressure of the reaction is 0.1MPa after the third pressure relief stage, the pressure relief rate is 0.0102MPa/min, the vacuum degree of the reaction is-0.025 MPa after the vacuum pumping, and the time for maintaining the vacuum degree is 10 min;
(2) mixing the polyamide polymer obtained in the step (1) and bis (2, 6-diisopropylphenyl) carbodiimide through a feed mixer and a static mixer, and then slicing and granulating to obtain alcoholysis-resistant polyamide resin;
wherein the polyamide resin has a carboxyl end group concentration of 16mmol/kg, an amino end group concentration of 64mmol/kg, and a molar ratio of amino end groups to carboxyl end groups of 4: 1.
Example 6
This example provides an alcoholysis-resistant polyamide resin (relative viscosity of 2.60) comprising the following raw material components in percentage by mass:
wherein the comonomer comprises the following components in percentage by mass: 82% of nylon 66 salt, 15% of nylon 1212 salt and 3% of nylon 6T salt; the blocking agent consists of n-hexylamine and hexamethylene diamine in a mass ratio of 1: 0.85.
The alcoholysis resistant polyamide resin was prepared in the same manner as in example 1.
Wherein the concentration of the terminal carboxyl groups of the polyamide resin is 12mmol/kg, the concentration of the terminal amino groups is 72mmol/kg, and the molar ratio of the terminal amino groups to the terminal carboxyl groups is 6: 1.
Example 7
This example provides an alcoholysis-resistant polyamide resin (relative viscosity of 2.60) which differs from example 2 only in that the starting components contained 2.0% by mass of alcoholysis-resistant agent, 97.8% by mass of comonomer, 0.193% by mass of sodium hypophosphite, and the other conditions being the same as in example 2, and the polyamide resin was prepared with a concentration of terminal carboxyl groups of 25mmol/kg, a concentration of terminal amino groups of 100mmol/kg, and a molar ratio of terminal amino groups to terminal carboxyl groups of 4: 1.
Example 8
This example provides an alcoholysis resistant polyamide resin (relative viscosity of 2.60) differing from example 5 only in that the starting components contained no bis (2, 6-diisopropylphenyl) carbodiimide and the comonomer content was 99.98% by mass, and the polyamide resin prepared under the same conditions as in example 5 had a carboxyl end group concentration of 16mmol/kg, an amino end group concentration of 64mmol/kg and a molar ratio of amino end groups to carboxyl end groups of 4: 1.
Comparative example 1
This comparative example provides an alcoholysis resistant polyamide resin (relative viscosity 2.60) which differs from example 6 only in that the comonomer does not contain nylon 1212 salt and nylon 6T salt, the mass percent of nylon 66 salt is 100%, and the other conditions are the same as in example 6, and the polyamide resin prepared has a carboxyl end group concentration of 12mmol/kg, an amino end group concentration of 72mmol/kg, and a molar ratio of amino end groups to carboxyl end groups of 6: 1.
Comparative example 2
This comparative example provides an alcoholysis-resistant polyamide resin (relative viscosity of 2.60) which differs from example 4 only in that pentanediamine is not added to the starting components and the mass percent of nylon 66 salt is 90.5%, but otherwise the conditions are the same as in example 4, and the polyamide resin obtained has a carboxyl end group concentration of 84mmol/kg, an amino end group concentration of 42mmol/kg and a molar ratio of amino end groups to carboxyl end groups of 1: 2.
Comparative example 3
This comparative example provides an alcoholysis-resistant polyamide resin (relative viscosity 2.60) which differs from example 2 in that the amount of hexamethylenediamine added is 0.0035% and the mass percent of sodium hypophosphite is 0.1035%, and the polyamide resin prepared under otherwise the same conditions as in example 2 has a carboxyl end group concentration of 42mmol/kg, an amino end group concentration of 84mmol/kg, and a molar ratio of amino end groups to carboxyl end groups of 2: 1.
Comparative example 4
This comparative example provides an alcoholysis-resistant polyamide resin (relative viscosity of 2.60) which differs from example 5 only in that the mass percent of the blocking agent is 0.0037% and the mass percent of the sodium hypophosphite is 0.0163%, wherein the blocking agent consists of ammonia monohydrate and hexamethylenediamine in a mass ratio of 1.52:1, and otherwise the conditions are the same as those in example 5, and the polyamide resin prepared has a carboxyl end group concentration of 22mmol/kg, an amino end group concentration of 66mmol/kg, and a molar ratio of amino end groups to carboxyl end groups of 3: 1.
The properties of the polyamide resins provided in the above examples were tested according to the following test criteria:
and (3) testing tensile strength: according to the national standard GB/T1040.1-2018, the sample size is 150 multiplied by 10 multiplied by 4mm, and the stretching speed is 5 mm/min;
and (3) alcoholysis resistance test: placing the sample in a mixed solution of ethylene glycol and water with a volume ratio of 1:1, soaking for 48 hours at 135 ℃, and evaluating alcoholysis resistance by using a tensile strength retention rate;
surface properties: observing the change of the appearance of the sample after the alcoholysis resistance test, wherein if the sample has no obvious deformation, the surface is good if the sample has no damage; if the sample has no obvious deformation, the surface is slightly damaged, namely, the sample is slightly poor.
Tensile strength retention ratio: tensile strength retention ═ alcoholysis aging resistant tensile strength/tensile strength × 100%.
The test results of the above properties are shown in the following table 1:
TABLE 1
As can be seen from the results in Table 1, the polyamide resin prepared by the method of the invention has the specific raw material components and proportions, the molar concentration of the terminal carboxyl groups and the molar ratio of the terminal amino groups to the terminal carboxyl groups of the polyamide resin are particularly limited, and the probability of hydrolysis/alcoholysis reaction of the polyamide resin is reduced, so that the polyamide resin has better hydrolysis resistance and better mechanical properties. The polyamide resin prepared by the invention has the tensile strength of 93-112 MPa, the alcoholysis aging resistant tensile strength of 51-73 MPa, the tensile strength retention rate of not less than 52 percent and good surface performance, and is suitable for use.
Compared with example 6, if only nylon 66 salt is contained in the comonomer of the polyamide resin, and the polyamide resin does not contain aliphatic amide resin and aromatic amide resin (comparative example 1), the prepared polyamide resin has poor mechanical properties, the tensile strength is 90MPa, the alcoholysis aging resistant tensile strength is 46MPa, the tensile strength retention rate is 51 percent, and the surface property is poor.
Compared with example 4, if the raw material components of the polyamide resin do not contain the end-capping agent (comparative example 2), the prepared polyamide resin has poor alcoholysis resistance, alcoholysis aging resistance tensile strength of 37MPa and tensile strength retention rate of 40 percent.
Compared with example 2, if the content of the end-capping reagent in the raw material components of the polyamide resin is less (comparative example 3), the concentration of the terminal carboxyl groups in the prepared polyamide resin is higher, and the mol ratio of the terminal amino groups to the terminal carboxyl groups is smaller, so that the alcoholysis resistance of the polyamide resin is poor, the alcoholysis aging resistance tensile strength is 39MPa, and the tensile strength retention rate is lower than 42%.
Compared with example 5, if the content of the end-capping reagent in the raw material components of the polyamide resin is less, and the mol ratio of the terminal amino group to the terminal carboxyl group of the prepared alcoholysis-resistant polyamide resin is smaller (comparative example 4), the mechanical properties are poor, the tensile strength is 89MPa, the alcoholysis aging-resistant tensile strength is 41MPa, and the tensile strength retention rate is 46%.
The applicant states that the present invention is illustrated by the above examples to show the detailed process equipment and process flow of the present invention, but the present invention is not limited to the above detailed process equipment and process flow, i.e. it does not mean that the present invention must rely on the above detailed process equipment and process flow to be implemented. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (10)
1. The alcoholysis-resistant polyamide resin is characterized by comprising the following raw material components in percentage by mass: 97.8 to 99.98 percent of comonomer and 0.0043 to 0.011 percent of end capping agent;
the comonomer comprises the following components in percentage by mass: 80-92% of nylon 66 salt and 5-15% of aliphatic amide monomer;
the molar concentration of the terminal carboxyl in the polyamide resin is 10-25 mmol/kg;
the molar ratio of the terminal amino groups to the terminal carboxyl groups in the polyamide resin is more than or equal to 4: 1.
2. Alcoholysis resistant polyamide resin according to claim 1, characterized in that the aliphatic amide monomer is a nylon salt and/or a lactam;
preferably, at least one of the diamines or diacids used to prepare the nylon salt has 7 to 15 carbon atoms, more preferably 8 to 12 carbon atoms;
preferably, the nylon salt is selected from any one of nylon 610 salt, nylon 612 salt and nylon 1212 salt or the combination of at least two of the nylon 610 salt, the nylon 612 salt and the nylon 1212 salt;
preferably, the number of carbon atoms of the lactam is from 7 to 15, more preferably from 8 to 12;
preferably, the lactam is decanolactam and/or dodecanolactam.
3. Alcoholysis resistant polyamide resin according to claim 1 or 2, characterized in that the end-capping agent is a monoamine and/or a diamine;
preferably, the monoamine is selected from any one or a combination of at least two of ammonia monohydrate, ethylamine, n-propylamine, n-butylamine, n-pentylamine, n-hexylamine or benzylamine;
preferably, the diamine is selected from any one or a combination of at least two of pentanediamine, hexanediamine, butanediamine, decanediamine or dodecanediamine;
preferably, the molar concentration of the terminal amino groups in the polyamide resin is 64-140 mmol/kg;
preferably, the molar ratio of the terminal amino groups to the terminal carboxyl groups in the polyamide resin is from 4:1 to 10: 1.
4. Alcoholysis resistant polyamide resin according to any of claims 1-3, characterized in that the comonomer further comprises aromatic amide monomers;
preferably, the aromatic amide monomer is selected from any one of or a combination of at least two of nylon 6I salt, nylon 6T salt or nylon MXD6 salt;
preferably, the aromatic amide monomer accounts for 3-5% of the mass of the comonomer;
preferably, the raw material components of the polyamide resin further comprise an alcoholysis resistance agent;
preferably, the alcoholysis resistance agent is selected from any one or a combination of at least two of bis (2, 6-diisopropylphenyl) carbodiimide, macromolecular hindered amine and phosphate compound, epoxy polymer hydrolysis resistance agent or polycarbodiimide;
preferably, the alcoholysis resistance agent accounts for 0.1-2% of the raw material components of the polyamide resin by mass.
5. Alcoholysis resistant polyamide resin according to any of claims 1 to 4, characterized in that the polyamide resin has a relative viscosity of 2.4 to 3.1;
preferably, the polyamide resin has a relative viscosity of 2.55 to 2.65.
6. An alcoholysis resistant polyamide resin according to any one of claims 1 to 5 prepared by a process comprising the steps of:
(1) carrying out a reaction on a comonomer and a terminating agent to obtain a polyamide polymer;
(2) and (2) mixing the polyamide polymer obtained in the step (1) with an optional alcoholysis-resistant agent, and then slicing and granulating to obtain the alcoholysis-resistant polyamide resin.
7. The method of claim 6, wherein the comonomer is a concentrated comonomer solution;
preferably, the solvent of the comonomer solution is desalted water;
preferably, the concentration method is to concentrate in a concentration tank;
preferably, the pressure of the concentration tank is 0.2-0.3 MPa;
preferably, the mass concentration of the concentrated comonomer solution is 75-85%;
preferably, the blocking agent is a blocking agent solution;
preferably, the solvent of the capping agent solution is desalted water;
preferably, the mass concentration of the end-capping reagent solution is 45-55%.
8. The method for preparing the compound of claim 6 or 7, wherein the temperature of the reaction in the step (1) is 250 to 270 ℃;
preferably, the reaction in the step (1) comprises the stages of temperature rise and pressure rise, pressure maintaining and temperature rise, pressure relief and vacuum pumping;
preferably, in the temperature and pressure raising, the temperature raising rate is 1.5-2 ℃/min;
preferably, the time for raising the temperature and the pressure is 15-25 min;
preferably, the pressure for raising the temperature and the pressure is 1.6-1.85 MPa;
preferably, the pressure of the pressure maintaining is 1.6-1.85 MPa;
preferably, the pressure maintaining time is 60-75 min;
preferably, the temperature for maintaining pressure and raising temperature is 250-270 ℃;
preferably, the pressure relief comprises a first pressure relief phase, a second pressure relief phase and a third pressure relief phase;
preferably, after the first pressure relief stage, the pressure of the reaction is 0.4-0.5MPa, after the second pressure relief stage, the pressure of the reaction is 0.15-0.25MPa, and after the third pressure relief stage, the pressure of the reaction is 0.095-0.15 MPa;
preferably, the pressure relief rate is 0.01-0.05 MPa/min;
preferably, after the vacuumizing stage, the vacuum degree of the reaction is-0.035 to-0.025 MPa;
preferably, the time for maintaining the vacuum degree is 7-12 min;
preferably, the reaction is carried out in the presence of nitrogen;
preferably, in step (2), the mixing method is mixing by a mixer;
preferably, the mixers are feed mixers and static mixers.
9. The method according to any one of claims 6 to 8, characterized by comprising the steps of:
(1) adding the comonomer solution into a concentration tank with the pressure of 0.2-0.3MPa for concentration, reacting the concentrated comonomer solution with the mass concentration of 75-85%, the capping reagent solution with the mass concentration of 45-55% and a catalyst in a nitrogen atmosphere, and performing temperature rise and pressure rise, pressure maintaining and temperature rise, pressure relief and vacuum pumping to obtain a polyamide polymer; wherein, when the temperature and the pressure are increased, the rate of temperature increase is 1.5-2 ℃/min, the time is 15-25min, the pressure of temperature increase and pressure increase is 1.6-1.85MPa, the pressure is 1.6-1.85MPa when the pressure and the temperature are maintained, the time is 60-75min, the temperature of pressure maintaining and temperature increase is 250-;
(2) and (2) mixing the polyamide polymer obtained in the step (1) and an optional alcoholysis resistance agent through a feed mixer and a static mixer, and then slicing and granulating to obtain the alcoholysis resistance polyamide resin.
10. Use of an alcoholysis resistant polyamide resin according to any of claims 1 to 5 as a material for vehicles.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011279967.XA CN114507344B (en) | 2020-11-16 | 2020-11-16 | Alcoholysis-resistant polyamide resin and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011279967.XA CN114507344B (en) | 2020-11-16 | 2020-11-16 | Alcoholysis-resistant polyamide resin and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114507344A true CN114507344A (en) | 2022-05-17 |
| CN114507344B CN114507344B (en) | 2024-01-23 |
Family
ID=81546360
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011279967.XA Active CN114507344B (en) | 2020-11-16 | 2020-11-16 | Alcoholysis-resistant polyamide resin and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114507344B (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101200542A (en) * | 2006-12-15 | 2008-06-18 | 上海杰事杰新材料股份有限公司 | Method for preparing high temperature nylon |
| JP2009298854A (en) * | 2008-06-10 | 2009-12-24 | Ube Ind Ltd | Composite material containing polyamide resin and layered silicate |
| JP2011105822A (en) * | 2009-11-16 | 2011-06-02 | Mitsubishi Gas Chemical Co Inc | Thermoplastic resin composition excellent in hydrolysis resistance |
| CN102516761A (en) * | 2011-12-04 | 2012-06-27 | 上海金发科技发展有限公司 | Hydrolysis-resistant alcoholysis-resistant nylon 66 composite material and preparation method thereof |
| CN111892743A (en) * | 2020-06-30 | 2020-11-06 | 金发科技股份有限公司 | Polyamide recovery process and polyamide obtained by recovery process |
-
2020
- 2020-11-16 CN CN202011279967.XA patent/CN114507344B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101200542A (en) * | 2006-12-15 | 2008-06-18 | 上海杰事杰新材料股份有限公司 | Method for preparing high temperature nylon |
| JP2009298854A (en) * | 2008-06-10 | 2009-12-24 | Ube Ind Ltd | Composite material containing polyamide resin and layered silicate |
| JP2011105822A (en) * | 2009-11-16 | 2011-06-02 | Mitsubishi Gas Chemical Co Inc | Thermoplastic resin composition excellent in hydrolysis resistance |
| CN102516761A (en) * | 2011-12-04 | 2012-06-27 | 上海金发科技发展有限公司 | Hydrolysis-resistant alcoholysis-resistant nylon 66 composite material and preparation method thereof |
| CN111892743A (en) * | 2020-06-30 | 2020-11-06 | 金发科技股份有限公司 | Polyamide recovery process and polyamide obtained by recovery process |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114507344B (en) | 2024-01-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR100951519B1 (en) | Polymer mixture of aliphatic polyamides and partially aromatic polyamides, moulded articles thereof and use thereof | |
| EP2861660B1 (en) | Thermoplastic melt-mixed composition with amino acid heat stabilizer | |
| CN104231262A (en) | Preparation method for organic phosphorus copolymerized antiflaming polyamide material | |
| CN110982063A (en) | Semi-aromatic polyamide resin and preparation method thereof | |
| CN111073275A (en) | Bio-based nylon composite material and preparation method and application thereof | |
| CN105153690A (en) | Chloride salt stress corrosion cracking resistant polyamide composition and preparation method therefor and application thereof | |
| CZ20012273A3 (en) | Process for preparing branched polyamides and use thereof | |
| CN114507344B (en) | Alcoholysis-resistant polyamide resin and preparation method and application thereof | |
| CN111217996B (en) | 4-arm star-shaped nylon and preparation method thereof | |
| CN102532545B (en) | Long-carbon-chain semi-aromatic polyamide imide and synthetic method thereof | |
| CN111073278A (en) | Polyamide composite material and preparation method thereof | |
| CN115572387A (en) | Preparation method of low-melting-point copolymerized flame-retardant polyamide | |
| CN113429782B (en) | Transparent polyamide resin and preparation method thereof | |
| CN115093700A (en) | Nylon elastomer material and preparation method thereof | |
| CN114426665B (en) | Antioxidant polyamide material and preparation method thereof | |
| CN114933701A (en) | Preparation method of low-temperature toughened MC nylon 6 composite material | |
| CN110964197B (en) | Preparation method and application of rapid prototyping polyamide | |
| CN111040439B (en) | Polyamide material with excellent wear resistance, and preparation method and application thereof | |
| CN115725070A (en) | High-temperature-resistant semi-aromatic polyamide, preparation method thereof, composition and molded product | |
| CN113461934A (en) | High-melting-point transparent nylon material and preparation method thereof | |
| CN112048085A (en) | Preparation process of biodegradable resin-based composite material | |
| CN112126165A (en) | Polypropylene composite material with self-repairing performance after high-temperature aging and preparation method thereof | |
| CN115975181B (en) | Ternary polymerization transparent nylon and preparation method thereof | |
| CN113956470B (en) | High-toughness transparent resin and preparation method thereof | |
| CN111100451A (en) | Modified liquid crystal polyester resin composite material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |