CN114163632A - Anti-yellowing copolyamide and preparation method thereof - Google Patents
Anti-yellowing copolyamide and preparation method thereof Download PDFInfo
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- CN114163632A CN114163632A CN202210004884.2A CN202210004884A CN114163632A CN 114163632 A CN114163632 A CN 114163632A CN 202210004884 A CN202210004884 A CN 202210004884A CN 114163632 A CN114163632 A CN 114163632A
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- acid
- yellowing
- dibasic acid
- aliphatic
- lactam
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- 238000004383 yellowing Methods 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 52
- 239000002253 acid Substances 0.000 claims abstract description 47
- -1 aliphatic diamine Chemical class 0.000 claims abstract description 41
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 40
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 21
- 125000003118 aryl group Chemical group 0.000 claims abstract description 21
- 150000003951 lactams Chemical class 0.000 claims abstract description 21
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 21
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 20
- 238000010438 heat treatment Methods 0.000 claims abstract description 19
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 13
- 239000000203 mixture Substances 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000007599 discharging Methods 0.000 claims abstract description 10
- 238000011049 filling Methods 0.000 claims abstract description 10
- 239000003381 stabilizer Substances 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims abstract description 9
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 5
- 238000004321 preservation Methods 0.000 claims abstract description 3
- PVNIIMVLHYAWGP-UHFFFAOYSA-N Niacin Chemical compound OC(=O)C1=CC=CN=C1 PVNIIMVLHYAWGP-UHFFFAOYSA-N 0.000 claims description 26
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 15
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 claims description 14
- 229960003512 nicotinic acid Drugs 0.000 claims description 13
- 235000001968 nicotinic acid Nutrition 0.000 claims description 13
- 239000011664 nicotinic acid Substances 0.000 claims description 13
- 239000003795 chemical substances by application Substances 0.000 claims description 11
- 239000004014 plasticizer Substances 0.000 claims description 11
- 239000002667 nucleating agent Substances 0.000 claims description 10
- QFGCFKJIPBRJGM-UHFFFAOYSA-N 12-[(2-methylpropan-2-yl)oxy]-12-oxododecanoic acid Chemical compound CC(C)(C)OC(=O)CCCCCCCCCCC(O)=O QFGCFKJIPBRJGM-UHFFFAOYSA-N 0.000 claims description 8
- 239000001361 adipic acid Substances 0.000 claims description 8
- 235000011037 adipic acid Nutrition 0.000 claims description 8
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 8
- 229910052708 sodium Inorganic materials 0.000 claims description 8
- 239000011734 sodium Substances 0.000 claims description 8
- VHRGRCVQAFMJIZ-UHFFFAOYSA-N cadaverine Chemical compound NCCCCCN VHRGRCVQAFMJIZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000003963 antioxidant agent Substances 0.000 claims description 5
- 230000003078 antioxidant effect Effects 0.000 claims description 5
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 4
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 4
- 239000012760 heat stabilizer Substances 0.000 claims description 4
- 239000004611 light stabiliser Substances 0.000 claims description 4
- 239000000314 lubricant Substances 0.000 claims description 4
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 claims description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 4
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 claims description 4
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 claims description 4
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 claims description 4
- HQHCYKULIHKCEB-UHFFFAOYSA-N tetradecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCCC(O)=O HQHCYKULIHKCEB-UHFFFAOYSA-N 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 claims description 2
- JZUHIOJYCPIVLQ-UHFFFAOYSA-N 2-methylpentane-1,5-diamine Chemical compound NCC(C)CCCN JZUHIOJYCPIVLQ-UHFFFAOYSA-N 0.000 claims description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 2
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 claims description 2
- 239000002216 antistatic agent Substances 0.000 claims description 2
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 2
- 150000004985 diamines Chemical class 0.000 claims description 2
- JMLPVHXESHXUSV-UHFFFAOYSA-N dodecane-1,1-diamine Chemical compound CCCCCCCCCCCC(N)N JMLPVHXESHXUSV-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
- 239000012744 reinforcing agent Substances 0.000 claims description 2
- 239000006224 matting agent Substances 0.000 claims 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 abstract description 14
- 230000000694 effects Effects 0.000 abstract description 9
- 150000001875 compounds Chemical class 0.000 abstract description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 14
- 150000001412 amines Chemical class 0.000 description 10
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- 239000004952 Polyamide Substances 0.000 description 9
- 229920002647 polyamide Polymers 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 230000018044 dehydration Effects 0.000 description 8
- 238000006297 dehydration reaction Methods 0.000 description 8
- 229920006122 polyamide resin Polymers 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- 239000004698 Polyethylene Substances 0.000 description 7
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 7
- 239000000155 melt Substances 0.000 description 7
- 229920000573 polyethylene Polymers 0.000 description 7
- FXDGCBFGSXNGQD-FAESFXMKSA-L disodium;(1s,2s,3r,4r)-bicyclo[2.2.1]heptane-2,3-dicarboxylate Chemical compound [Na+].[Na+].C1C[C@H]2[C@@H](C([O-])=O)[C@@H](C(=O)[O-])[C@@H]1C2 FXDGCBFGSXNGQD-FAESFXMKSA-L 0.000 description 6
- 230000001737 promoting effect Effects 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- 125000003277 amino group Chemical group 0.000 description 5
- 239000004831 Hot glue Substances 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 229920006141 Polyamide 5X Polymers 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- TVIDDXQYHWJXFK-UHFFFAOYSA-N dodecanedioic acid Chemical compound OC(=O)CCCCCCCCCCC(O)=O TVIDDXQYHWJXFK-UHFFFAOYSA-N 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 125000000542 sulfonic acid group Chemical group 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 230000005923 long-lasting effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 150000003053 piperidines Chemical class 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000009958 sewing Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004753 textile 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
- C08G69/36—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino acids, 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
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/04—Preparatory processes
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Proteomics, Peptides & Aminoacids (AREA)
- Polyamides (AREA)
Abstract
The invention relates to a yellowing-resistant copolyamide and a preparation method thereof, which comprises the following steps: (1) putting aliphatic dibasic acid and/or aromatic dibasic acid, aliphatic diamine, lactam, water, a stabilizer and other auxiliaries into a polymerization reaction kettle according to a formula ratio, heating to 80-150 ℃, and reacting at constant temperature for 0.5-1 h; (2) filling nitrogen into the reaction kettle to replace air, and continuously heating to 220-240 ℃ for heat preservation reaction for 2-3 h; (3) after the reaction index reaches the qualified range, adding an end-capping reagent, stirring for 0.5-1 h, fully dissolving and uniformly mixing, and finally vacuumizing until the index is qualified; (4) and introducing nitrogen to remove vacuum, and discharging while the mixture is hot to obtain the yellowing-resistant copolyamide. The preparation process is simple, and the sulfonic compound is added in the polymerization stage, so that the amino content is reduced to achieve the effect of resisting phenol yellowing, and the durability and uniformity of the phenol yellowing resistance can be better improved.
Description
Technical Field
The invention belongs to the technical field of polyamide bonding materials, and particularly relates to anti-yellowing copolyamide and a preparation method thereof, which can be used in the fields of adhesives, textile fibers, fabric linings and the like.
Background
The copolyamide hot melt adhesive becomes a very important hot melt adhesive material in the market by virtue of excellent comprehensive properties such as adhesive strength, heat resistance, solvent resistance and the like. At present, the copolyamide bonding material on the market is not limited to a single form of hot melt adhesive, develops into forms of net films, strips, fibers and the like gradually, and has very wide application prospect.
However, the copolyamide molecular chain is easy to generate chain segment fracture under the condition of long-time illumination, so that the molecules are degraded, and the performances such as thermal stability, light stability, weather resistance and the like are relatively poor; the terminal amino group and the terminal nitrogen-containing structure of the copolyamide molecular chain are also oxidized by oxygen or the like to form a chromophore containing a carbon-nitrogen double bond, resulting in yellowing. In addition, some of the attachments of the copolyamide during use are bonded to terminal groups such as amino groups contained therein by catalysis of an external nitrogen oxide or the like to form colored substances, thereby causing yellowing.
At present, for the improvement of the yellowing and poor stability of copolyamide, patent CN111269413A mainly includes adding an anti-yellowing agent, a stabilizer, etc. to modify it by a melt blending method; the antioxidant is copper salt of organic acid and inorganic copper salt; the anti-yellowing agent is phosphate, phosphite or hypophosphite. Patent CN103184607A discloses an anti-yellowing polyamide fiber sewing thread, which is obtained by continuously adding carboxylic acid of C2-C20 into polyamide polymer in a screw extruder, and performing processes such as melt mixing, etc., wherein the terminal of polyamide molecular chain of fiber-forming polymer is formed by chemical reaction between carboxylic acid of C2-C20 and terminal amino group of polyamide polymer molecular chain. Patent CN111269414A discloses a yellowing-resistant polyamide resin and a preparation method thereof, wherein dibasic acid amine salt prepared by deoxygenated water is adopted, and by using anaerobic operation treatment, the generation of byproducts is effectively inhibited, so that the yellowing resistance of a polyamide material under the conditions of high temperature and illumination is improved; patent CN105802208A discloses a yellowing resistant polyamide composition obtained by melt blending process with polyamide component using anti-aging agent including heat stabilizer, light stabilizer and amino functional group end capping agent (polycarboxylic acid, preferably citric acid). Patent CN112759760A discloses a high and low temperature aging resistant toughened polyamide 5X resin, and a preparation method and an application thereof, wherein the polyamide 5X resin is terminated with a fatty diacid containing a flexible chain (a fatty diacid with a carbon atom number greater than that of the diacid) during polymerization, so that the content of terminal amino groups in the polyamide resin can be reduced, and the yellowing resistance of the obtained polyamide resin at high temperature and in subsequent processing and injection molding processes is obviously improved, and the aging resistance is good. Patent CN105037713A introduces piperidine compounds with steric hindrance effect and light/heat stabilization effect as light/heat stabilizers during the reaction process.
However, the above prior art has the following disadvantages: when the polyamide resin is modified by adopting a stabilizer and the like, the problem of uneven dispersion of the additive often occurs, so that the polyamide resin product has a phenomenon of partial yellowing in the use process; moreover, the post-modification process of melt blending is adopted, so that the process is complicated, and the cost is increased.
In addition, patent CN109705342A discloses a yellowing-resistant polyamide resin, and a raw material and a production method thereof, wherein monofunctional isocyanate enters polyamide resin particles along with an organic solvent to perform a blocking reaction on the terminal of a polyamide molecular chain, so as to convert a terminal amino group and a terminal carboxyl group into an m-phenyl group, and the obtained polyamide resin has good yellowing resistance. However, the technique adopts an organic solvent and a single raw material to carry out end capping reaction, and has certain influence on the mechanical property, the bonding strength, the stability and the like of the copolyamide material.
Therefore, the development of homogeneous and long-lasting yellowing resistant copolyamides remains an important issue today.
Disclosure of Invention
The invention starts from a copolyamide monomer, captures free amine, amino at the tail end of a molecular chain and a nitrogen-containing structure, reacts and terminates the free amine and the amino and the nitrogen-containing structure by adding a sulfonic group in a polymerization stage, and adjusts the addition amount of the sulfonic group to control the content of the amino, so that the yellowing-resistant copolyamide with excellent, durable and uniform yellowing resistance and the preparation method thereof are provided, and the defects that the yellowing-resistant copolyamide prepared by adopting an additive stabilizer through post-modification processes such as screw extrusion and the like in the prior art is relatively poor in uniformity and durability, complicated in preparation process and the like are overcome.
The purpose of the invention is realized by the following technical scheme:
the preparation method of the yellowing-resistant copolyamide is characterized by comprising the following steps:
(1) putting aliphatic dibasic acid and/or aromatic dibasic acid, aliphatic diamine, lactam, water, a stabilizer and other auxiliaries into a polymerization reaction kettle according to a formula ratio, heating to 80-150 ℃, and reacting at constant temperature for 0.5-1 h;
(2) filling nitrogen into the reaction kettle to replace air, and continuously heating to 220-240 ℃ for heat preservation reaction for 2-3 h;
(3) after the reaction index reaches the qualified range, adding an end-capping reagent, stirring for 0.5-1 h, fully dissolving and uniformly mixing to enable the mixture to react with the amino end groups and the free amine, and finally vacuumizing until the index is qualified;
(4) introducing nitrogen to remove vacuum, and discharging while the mixture is hot to obtain the yellowing-resistant copolyamide;
the molar ratio of the aliphatic dibasic acid to the aromatic dibasic acid to the aliphatic diamine is (0.97-1.02): 1; the total amount of the three components accounts for 50 to 60 percent of the total mass of the aliphatic dibasic acid, the aromatic dibasic acid, the aliphatic diamine and the lactam;
the dosage of the lactam accounts for 40 to 50 percent of the total mass of the aliphatic dibasic acid, the aromatic dibasic acid, the aliphatic diamine and the lactam;
the amount of the water accounts for 5-10% of the total mass of the aliphatic dibasic acid, the aromatic dibasic acid, the aliphatic diamine and the lactam;
the end-capping reagent is 5-sulfonic acid group nicotinic acid and/or 5-sulfonic acid group isophthalic acid; the use amount of the end capping agent is that the molar ratio of total carboxylic acid to diamine in the added system is (1.03-1.1): 1.
the aliphatic dibasic acid is one or more of succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid and tetradecanedioic acid; the aromatic dibasic acid is one or more of terephthalic acid, isophthalic acid and phthalic acid; the aliphatic diamine is one or more of 1, 4-butanediamine, 1, 5-pentanediamine, 2-methylpentanediamine, hexanediamine, decanediamine and dodecanediamine; the lactam is one or more of cyclic lactams with 6-12 carbon atoms; the stabilizer is one or more of a heat stabilizer, a light stabilizer, a hindered phenol antioxidant and a pentaerythritol ester antioxidant; the dosage of the stabilizer accounts for 0.05-1% of the total mass of the aliphatic dibasic acid, the aromatic dibasic acid, the aliphatic diamine and the lactam;
the other auxiliary agents comprise one or more of reinforcing agent, lubricant, plasticizer, nucleating agent, antistatic agent and delustering agent; the nucleating agent is one of sodium carboxylate, and the dosage of the nucleating agent accounts for 0.1-1% of the total mass of the aliphatic dibasic acid, the aromatic dibasic acid, the aliphatic diamine and the lactam; the dosage of the plasticizer accounts for 0.5 to 1 percent of the total mass of the aliphatic dibasic acid, the aromatic dibasic acid, the aliphatic diamine and the lactam; the dosage of the lubricant accounts for 0.5 to 1.5 percent of the total mass of the aliphatic dibasic acid, the aromatic dibasic acid, the aliphatic diamine and the lactam.
Compared with the prior art, the invention has the following advantages:
the preparation process is simple, and free amine and terminal amino are captured, reacted and blocked by adding the sulfonic compound in the polymerization stage, so that the amino content is reduced to achieve the effect of resisting phenol yellowing; in addition, compared with the existing method of adding a modifier into a screw extruder, the method for carrying out end capping and phenol yellow resistance in the polymerization stage can better improve the durability and uniformity of phenol yellow resistance; the main chain of the sulfonic end-capping agent contains polar groups, and the compatibility with a copolyamide matrix is good, so that the phenolic yellowing resistant effect can be better exerted.
Detailed Description
The invention is further illustrated by the following specific examples, which are intended to be illustrative only and not limiting.
Comparative example 1
Weighing 285.6g of caprolactam, 36.9g of adipic acid, 102.1g of sebacic acid, 58.1g of dodecanedioic acid, 117.3g of hexamethylenediamine, 30g of water, 0.6g of antioxidant 1010, 1.8g of plasticizer, 1.5g of nucleating agent and 3g of polyethylene wax in a reaction kettle provided with a stirrer, an air inlet, a condenser pipe and a temperature and pressure testing device, putting the materials into a polymerization reaction kettle, heating to 80-150 ℃, and reacting at constant temperature for 0.5 h;
continuing heating to 240 ℃ and 220 ℃, filling nitrogen into the reaction kettle after the reaction dehydration is basically finished, replacing the air in the reaction kettle, reacting for 2-3h until the reaction dehydration is finished and vacuumizing is carried out to reach the preset molecular weight; introducing nitrogen to relieve vacuum, and discharging while hot. The sample was labeled as control.
Example 1
The preparation method of the yellowing-resistant copolyamide is characterized by comprising the following steps:
(1) in a reaction kettle provided with a stirrer, an air inlet, a condenser pipe and a temperature and pressure testing device, weighing 36.9g of adipic acid, 102.1g of sebacic acid, 58.1g of dodecanedioic acid, 117.3g of hexamethylenediamine, 285.6g of caprolactam, 30g of water, 0.6g of antioxidant 1010, 1.8g of plasticizer, 1.5g of sodium carboxylate (Milliken HPN-68L) as a nucleating agent and 3g of polyethylene wax, putting the weighed materials into the polymerization reaction kettle, heating to 150 ℃, and carrying out constant-temperature reaction for 0.5 h;
(2) filling nitrogen into the reaction kettle to replace air in the reaction kettle, continuously heating to 230 ℃, preserving heat and reacting for 3 hours, and promoting the raw materials in the reaction kettle to carry out reactions such as molten salt, dehydration, polymerization and the like;
(3) after the melt index reaches 25-30 g/10min, adding 6g of 5-sulfonic nicotinic acid, stirring for 30min, fully dissolving and uniformly mixing to enable the mixture to react with terminal amino and free amine, and finally vacuumizing until the index is qualified;
(4) introducing nitrogen to remove vacuum, and discharging while the mixture is hot to obtain the yellowing-resistant copolyamide; the sample was labeled sample 1.
Example 2
The preparation method of the yellowing-resistant copolyamide is characterized by comprising the following steps:
(1) in a reaction kettle provided with a stirrer, an air inlet, a condenser pipe and a temperature and pressure testing device, weighing 36.9g of adipic acid, 102.1g of sebacic acid, 58.1g of dodecanedioic acid, 117.3g of hexamethylenediamine, 285.6g of caprolactam, 30g of water, 0.6g of antioxidant 1010, 1.8g of plasticizer, 1.5g of sodium carboxylate (Milliken HPN-68L) as a nucleating agent and 3g of polyethylene wax, putting the weighed materials into the polymerization reaction kettle, heating to 150 ℃, and carrying out constant-temperature reaction for 0.5 h;
(2) filling nitrogen into the reaction kettle to replace air in the reaction kettle, continuously heating to 230 ℃, preserving heat and reacting for 3 hours, and promoting the raw materials in the reaction kettle to carry out reactions such as molten salt, dehydration, polymerization and the like;
(3) after the melt index reaches 25-30 g/10min, adding 10g of 5-sulfonic nicotinic acid, stirring for 30min, fully dissolving and uniformly mixing to enable the 5-sulfonic nicotinic acid to react with terminal amino and free amine, and finally vacuumizing until the index is qualified;
(4) introducing nitrogen to remove vacuum, and discharging while the mixture is hot to obtain the yellowing-resistant copolyamide; the sample was labeled sample 2.
Example 3
The preparation method of the yellowing-resistant copolyamide is characterized by comprising the following steps:
(1) in a reaction kettle provided with a stirrer, an air inlet, a condenser pipe and a temperature and pressure testing device, weighing 36.9g of adipic acid, 102.1g of sebacic acid, 58.1g of dodecanedioic acid, 117.3g of hexamethylenediamine, 285.6g of caprolactam, 30g of water, 0.6g of antioxidant 1010, 1.8g of plasticizer, 1.5g of sodium carboxylate (Milliken HPN-68L) as a nucleating agent and 3g of polyethylene wax, putting the weighed materials into the polymerization reaction kettle, heating to 150 ℃, and carrying out constant-temperature reaction for 0.5 h;
(2) filling nitrogen into the reaction kettle to replace air in the reaction kettle, continuously heating to 230 ℃, preserving heat and reacting for 3 hours, and promoting the raw materials in the reaction kettle to carry out reactions such as molten salt, dehydration, polymerization and the like;
(3) after the melt index reaches 25-30 g/10min, adding 16g of 5-sulfonic nicotinic acid, stirring for 30min, fully dissolving and uniformly mixing to enable the 5-sulfonic nicotinic acid to react with terminal amino and free amine, and finally vacuumizing until the index is qualified;
(4) introducing nitrogen to remove vacuum, and discharging while the mixture is hot to obtain the yellowing-resistant copolyamide; the sample was labeled sample 3.
Example 4
The preparation method of the yellowing-resistant copolyamide is characterized by comprising the following steps:
(1) in a reaction kettle provided with a stirrer, an air inlet, a condenser pipe and a temperature and pressure testing device, 73.6g of adipic acid, 121.7g of dodecanedioic acid, 119.9g of hexamethylenediamine, 284.8g of caprolactam, 30g of water, 0.6g of antioxidant 1010, 1.8g of plasticizer, 1.5g of sodium carboxylate (Milliken HPN-68L) and 3g of polyethylene wax are weighed and put into the polymerization reaction kettle, the temperature is raised to 150 ℃, and the constant temperature reaction is carried out for 0.5 h;
(2) filling nitrogen into the reaction kettle to replace air in the reaction kettle, continuously heating to 230 ℃, preserving heat and reacting for 3 hours, and promoting the raw materials in the reaction kettle to carry out reactions such as molten salt, dehydration, polymerization and the like;
(3) after the melt index reaches the range of 5-10 g/10min, adding 10g of 5-sulfonic acid nicotinic acid, stirring for 30min, fully dissolving and uniformly mixing to enable the 5-sulfonic acid nicotinic acid to react with terminal amino and free amine, and finally vacuumizing until the index is qualified;
(4) introducing nitrogen to remove vacuum, and discharging while the mixture is hot to obtain the yellowing-resistant copolyamide; the sample was labeled sample 4.
Example 5
The preparation method of the yellowing-resistant copolyamide is characterized by comprising the following steps:
(1) in a reaction kettle provided with a stirrer, an air inlet, a condenser pipe and a temperature and pressure testing device, weighing 90.4g of sebacic acid, 102.9g of dodecanedioic acid, 153.9g of decanediamine, 252.8g of caprolactam, 30g of water, 0.6g of antioxidant 1010, 1.8g of plasticizer, 1.5g of sodium carboxylate (Milliken HPN-68L) and 3g of polyethylene wax, putting the mixture into the polymerization reaction kettle, heating to 150 ℃, and reacting at constant temperature for 0.5 h;
(2) filling nitrogen into the reaction kettle to replace air in the reaction kettle, continuously heating to 230 ℃, preserving heat and reacting for 3 hours, and promoting the raw materials in the reaction kettle to carry out reactions such as molten salt, dehydration, polymerization and the like;
(3) after the melt index reaches the range of 25-30 g/10min, adding 10g of 5-sulfonic nicotinic acid, stirring for 30min, fully dissolving and uniformly mixing to enable the 5-sulfonic nicotinic acid to react with terminal amino and free amine, and finally vacuumizing until the index is qualified;
(4) introducing nitrogen to remove vacuum, and discharging while the mixture is hot to obtain the yellowing-resistant copolyamide; the sample was labeled sample 5.
Example 6
The preparation method of the yellowing-resistant copolyamide is characterized by comprising the following steps:
(1) weighing 92.6g of adipic acid, 126g of dodecanedioic acid, 120.6g of 1, 5-pentanediamine, 260.7g of caprolactam, 30g of water, 0.6g of antioxidant 1010, 1.8g of plasticizer, 1.5g of sodium carboxylate (Milliken HPN-68L) and 3g of polyethylene wax in a reaction kettle provided with a stirrer, an air inlet, a condenser pipe and a temperature and pressure testing device, putting the weighed materials into the polymerization reaction kettle, heating to 150 ℃, and reacting at constant temperature for 0.5 h;
(2) filling nitrogen into the reaction kettle to replace air in the reaction kettle, continuously heating to 230 ℃, preserving heat and reacting for 3 hours, and promoting the raw materials in the reaction kettle to carry out reactions such as molten salt, dehydration, polymerization and the like;
(3) after the melt index reaches the range of 5-10 g/10min, adding 10g of 5-sulfonic acid nicotinic acid, stirring for 30min, fully dissolving and uniformly mixing to enable the 5-sulfonic acid nicotinic acid to react with terminal amino and free amine, and finally vacuumizing until the index is qualified;
(4) introducing nitrogen to remove vacuum, and discharging while the mixture is hot to obtain the yellowing-resistant copolyamide; the sample was labeled sample 6.
The samples were tested for phenol yellowing rating according to the method of SN/T2468-2010 and the acid value of the product was determined according to the GB/T2895-2008 standard, the results of which are shown in the following table:
TABLE 1 phenol yellowing rating and acid number
From the test results of the samples 1-3 and the comparative sample in the table 1, it can be obtained that the phenolic yellowing resistance grade of the final product is gradually increased by adding different amounts of the sulfonic end capping agent in the formula of the copolyamide, namely the phenolic yellowing resistance effect is gradually obvious; in addition, the phenol yellow resistant effect is obvious along with the increase of the addition amount of the sulfonic acid group end capping agent through the increase of the corresponding acid value along with the increase of the addition amount, namely the system is gradually acidic;
from the test results of the comparative sample and samples 4-6 in table 1, it can be seen that the sulfonic acid group capping agent in the same proportion has a certain phenol yellow resistance effect in different copolyamide systems, wherein the phenol yellow resistance effect is relatively more pronounced in systems with a slightly higher melt index than in systems with a slightly lower melt index due to the difference in viscosity of the systems.
Claims (7)
1. The preparation method of the yellowing-resistant copolyamide is characterized by comprising the following steps:
(1) putting aliphatic dibasic acid and/or aromatic dibasic acid, aliphatic diamine, lactam, water, a stabilizer and other auxiliaries into a polymerization reaction kettle according to a formula ratio, heating to 80-150 ℃, and reacting at constant temperature for 0.5-1 h;
(2) filling nitrogen into the reaction kettle to replace air, and continuously heating to 220-240 ℃ for heat preservation reaction for 2-3 h;
(3) after the reaction index reaches the qualified range, adding an end-capping reagent, stirring for 0.5-1 h, fully dissolving and uniformly mixing, and finally vacuumizing until the index is qualified;
(4) and introducing nitrogen to remove vacuum, and discharging while the mixture is hot to obtain the yellowing-resistant copolyamide.
2. The method for preparing yellowing-resistant copolyamide according to claim 1, wherein the molar ratio of the aliphatic dibasic acid to the aromatic dibasic acid to the aliphatic diamine is (0.97-1.02): 1; the total amount of the three components accounts for 50 to 60 percent of the total mass of the aliphatic dibasic acid, the aromatic dibasic acid, the aliphatic diamine and the lactam;
the dosage of the lactam accounts for 40 to 50 percent of the total mass of the aliphatic dibasic acid, the aromatic dibasic acid, the aliphatic diamine and the lactam;
the amount of the water accounts for 5-10% of the total mass of the aliphatic dibasic acid, the aromatic dibasic acid, the aliphatic diamine and the lactam;
the end-capping reagent is 5-sulfonic acid group nicotinic acid and/or 5-sulfonic acid group isophthalic acid; the use amount of the end capping agent is that the molar ratio of total carboxylic acid to diamine in the added system is (1.03-1.1): 1.
3. the method for preparing yellowing-resistant copolyamide according to claim 1, wherein the aliphatic dibasic acid is one or more of succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, and tetradecanedioic acid; the aromatic dibasic acid is one or more of terephthalic acid, isophthalic acid and phthalic acid; the aliphatic diamine is one or more of 1, 4-butanediamine, 1, 5-pentanediamine, 2-methylpentanediamine, hexanediamine, decanediamine and dodecanediamine; the lactam is one or more of cyclic lactams with 6-12 carbon atoms.
4. The method for preparing yellowing-resistant copolyamide according to claim 1, wherein the stabilizer is one or more of a heat stabilizer, a light stabilizer, a hindered phenol antioxidant and a pentaerythritol ester antioxidant; the dosage of the stabilizer accounts for 0.05-1% of the total mass of the aliphatic dibasic acid, the aromatic dibasic acid, the aliphatic diamine and the lactam.
5. The method for preparing yellowing-resistant copolyamide according to claim 1, wherein the other auxiliaries comprise one or more of reinforcing agents, lubricants, plasticizers, nucleating agents, antistatic agents and matting agents.
6. The preparation method of the yellowing-resistant copolyamide according to claim 1, wherein the nucleating agent is one of sodium carboxylate salts, and the amount of the nucleating agent is 0.1-1% of the total mass of the aliphatic dibasic acid, the aromatic dibasic acid, the aliphatic diamine and the lactam; the dosage of the plasticizer accounts for 0.5 to 1 percent of the total mass of the aliphatic dibasic acid, the aromatic dibasic acid, the aliphatic diamine and the lactam; the dosage of the lubricant accounts for 0.5 to 1.5 percent of the total mass of the aliphatic dibasic acid, the aromatic dibasic acid, the aliphatic diamine and the lactam.
7. A yellowing-resistant copolyamide produced according to the preparation method of the yellowing-resistant copolyamide according to any one of claims 1-6.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116042169A (en) * | 2022-12-27 | 2023-05-02 | 南通天洋新材料有限公司 | Preparation method of phenol yellowing-resistant copolyamide hot melt adhesive |
| CN118440659A (en) * | 2024-05-17 | 2024-08-06 | 上海东睿新材料股份有限公司 | Copolyamide hot melt adhesive and preparation method thereof |
Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009079886A1 (en) * | 2007-12-14 | 2009-07-02 | Kingfa Science & Technology Co., Ltd. | A semiaromatic polyamide and the preparation method thereof |
| JP2012136796A (en) * | 2010-12-27 | 2012-07-19 | Toyobo Co Ltd | Interpolyamide fiber |
| CN102918083A (en) * | 2010-05-28 | 2013-02-06 | 罗地亚经营管理公司 | Sulfonate-modified polyamide having improved barrier properties |
| CN103122492A (en) * | 2011-11-18 | 2013-05-29 | 东丽纤维研究所（中国）有限公司 | Anti-yellowing polyamide fiber and method for manufacturing same |
| CN103254425A (en) * | 2012-02-17 | 2013-08-21 | 上海东睿化学有限公司 | Blocked copolyamide hot melt adhesive and preparation method thereof |
| CN107868455A (en) * | 2016-09-28 | 2018-04-03 | 河南智联寰宇知识产权运营有限公司 | High temperature resistant nylon graphene composite functional material and preparation method thereof |
| CN109536119A (en) * | 2018-12-03 | 2019-03-29 | 上海天洋热熔粘接材料股份有限公司 | A kind of copolyamide hot melt adhesive and preparation method thereof |
| CN109705338A (en) * | 2018-11-26 | 2019-05-03 | 东华大学 | A kind of low melting-point PA6 elastomer and preparation method thereof |
| CN109705342A (en) * | 2019-01-11 | 2019-05-03 | 中仑塑业（福建）有限公司 | A kind of color inhibition polyamide and its raw materials for production and production method |
| CN111040721A (en) * | 2019-12-02 | 2020-04-21 | 上海天洋热熔粘接材料股份有限公司 | Low-VOC copolyamide hot melt adhesive and preparation method thereof |
| CN111138852A (en) * | 2019-12-26 | 2020-05-12 | 上海金发科技发展有限公司 | Polyamide compound for improving laser weldability |
| WO2021065205A1 (en) * | 2019-09-30 | 2021-04-08 | 東洋紡株式会社 | Inorganic reinforced semi-aromatic polyamide resin composition |
| CN113185688A (en) * | 2021-03-31 | 2021-07-30 | 上海庚彩新材料科技有限公司 | Copolyamide and preparation method thereof |
| CN113845657A (en) * | 2021-10-27 | 2021-12-28 | 中仑塑业（福建）有限公司 | Semi-aromatic polyamide resin and preparation method thereof |
-
2022
- 2022-01-04 CN CN202210004884.2A patent/CN114163632A/en active Pending
Patent Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009079886A1 (en) * | 2007-12-14 | 2009-07-02 | Kingfa Science & Technology Co., Ltd. | A semiaromatic polyamide and the preparation method thereof |
| CN102918083A (en) * | 2010-05-28 | 2013-02-06 | 罗地亚经营管理公司 | Sulfonate-modified polyamide having improved barrier properties |
| JP2012136796A (en) * | 2010-12-27 | 2012-07-19 | Toyobo Co Ltd | Interpolyamide fiber |
| CN103122492A (en) * | 2011-11-18 | 2013-05-29 | 东丽纤维研究所（中国）有限公司 | Anti-yellowing polyamide fiber and method for manufacturing same |
| CN103254425A (en) * | 2012-02-17 | 2013-08-21 | 上海东睿化学有限公司 | Blocked copolyamide hot melt adhesive and preparation method thereof |
| CN107868455A (en) * | 2016-09-28 | 2018-04-03 | 河南智联寰宇知识产权运营有限公司 | High temperature resistant nylon graphene composite functional material and preparation method thereof |
| CN109705338A (en) * | 2018-11-26 | 2019-05-03 | 东华大学 | A kind of low melting-point PA6 elastomer and preparation method thereof |
| CN109536119A (en) * | 2018-12-03 | 2019-03-29 | 上海天洋热熔粘接材料股份有限公司 | A kind of copolyamide hot melt adhesive and preparation method thereof |
| CN109705342A (en) * | 2019-01-11 | 2019-05-03 | 中仑塑业（福建）有限公司 | A kind of color inhibition polyamide and its raw materials for production and production method |
| WO2021065205A1 (en) * | 2019-09-30 | 2021-04-08 | 東洋紡株式会社 | Inorganic reinforced semi-aromatic polyamide resin composition |
| CN111040721A (en) * | 2019-12-02 | 2020-04-21 | 上海天洋热熔粘接材料股份有限公司 | Low-VOC copolyamide hot melt adhesive and preparation method thereof |
| CN111138852A (en) * | 2019-12-26 | 2020-05-12 | 上海金发科技发展有限公司 | Polyamide compound for improving laser weldability |
| CN113185688A (en) * | 2021-03-31 | 2021-07-30 | 上海庚彩新材料科技有限公司 | Copolyamide and preparation method thereof |
| CN113845657A (en) * | 2021-10-27 | 2021-12-28 | 中仑塑业（福建）有限公司 | Semi-aromatic polyamide resin and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 周光勇;张晓春;刘金华;: "DM系列抗黄变剂在锦纶织物上的应用", 印染, no. 14, pages 41 - 43 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116042169A (en) * | 2022-12-27 | 2023-05-02 | 南通天洋新材料有限公司 | Preparation method of phenol yellowing-resistant copolyamide hot melt adhesive |
| CN118440659A (en) * | 2024-05-17 | 2024-08-06 | 上海东睿新材料股份有限公司 | Copolyamide hot melt adhesive and preparation method thereof |
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