CN113174042A - Preparation method and product of self-repairable self-flame-retardant polyamide material based on disulfide bonds - Google Patents
Preparation method and product of self-repairable self-flame-retardant polyamide material based on disulfide bonds Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 41
- 239000004952 Polyamide Substances 0.000 title claims abstract description 39
- 229920002647 polyamide Polymers 0.000 title claims abstract description 39
- 239000003063 flame retardant Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 150000004985 diamines Chemical class 0.000 claims abstract description 17
- 239000011261 inert gas Substances 0.000 claims abstract description 6
- 239000002253 acid Substances 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 30
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 claims description 25
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 7
- 229910052710 silicon Inorganic materials 0.000 claims description 7
- 239000010703 silicon Substances 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 6
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 6
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 6
- 239000000178 monomer Substances 0.000 claims description 6
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 claims description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 4
- VHRGRCVQAFMJIZ-UHFFFAOYSA-N cadaverine Chemical group NCCCCCN VHRGRCVQAFMJIZ-UHFFFAOYSA-N 0.000 claims description 4
- YYSCJLLOWOUSHH-UHFFFAOYSA-N 4,4'-disulfanyldibutanoic acid Chemical compound OC(=O)CCCSSCCCC(O)=O YYSCJLLOWOUSHH-UHFFFAOYSA-N 0.000 claims description 3
- 239000001361 adipic acid Substances 0.000 claims description 3
- 235000011037 adipic acid Nutrition 0.000 claims description 3
- 238000007599 discharging Methods 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 239000001569 carbon dioxide Substances 0.000 claims description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 2
- YMHQVDAATAEZLO-UHFFFAOYSA-N cyclohexane-1,1-diamine Chemical compound NC1(N)CCCCC1 YMHQVDAATAEZLO-UHFFFAOYSA-N 0.000 claims description 2
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical compound [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- GUUVPOWQJOLRAS-UHFFFAOYSA-N Diphenyl disulfide Chemical compound C=1C=CC=CC=1SSC1=CC=CC=C1 GUUVPOWQJOLRAS-UHFFFAOYSA-N 0.000 claims 2
- XBNOMKROXZGMFW-UHFFFAOYSA-N 3-[(3-hydroxyphenyl)disulfanyl]phenol Chemical compound OC1=CC=CC(SSC=2C=C(O)C=CC=2)=C1 XBNOMKROXZGMFW-UHFFFAOYSA-N 0.000 claims 1
- WXAIEIRYBSKHDP-UHFFFAOYSA-N 4-phenyl-n-(4-phenylphenyl)-n-[4-[4-(4-phenyl-n-(4-phenylphenyl)anilino)phenyl]phenyl]aniline Chemical group C1=CC=CC=C1C1=CC=C(N(C=2C=CC(=CC=2)C=2C=CC=CC=2)C=2C=CC(=CC=2)C=2C=CC(=CC=2)N(C=2C=CC(=CC=2)C=2C=CC=CC=2)C=2C=CC(=CC=2)C=2C=CC=CC=2)C=C1 WXAIEIRYBSKHDP-UHFFFAOYSA-N 0.000 claims 1
- JMLPVHXESHXUSV-UHFFFAOYSA-N dodecane-1,1-diamine Chemical compound CCCCCCCCCCCC(N)N JMLPVHXESHXUSV-UHFFFAOYSA-N 0.000 claims 1
- XGSHEASGZHYHBU-UHFFFAOYSA-N tetradecane-1,1-diamine Chemical compound CCCCCCCCCCCCCC(N)N XGSHEASGZHYHBU-UHFFFAOYSA-N 0.000 claims 1
- 150000003568 thioethers Chemical class 0.000 claims 1
- FRXCPDXZCDMUGX-UHFFFAOYSA-N tridecane-1,1-diamine Chemical compound CCCCCCCCCCCCC(N)N FRXCPDXZCDMUGX-UHFFFAOYSA-N 0.000 claims 1
- UHUUYVZLXJHWDV-UHFFFAOYSA-N trimethyl(methylsilyloxy)silane Chemical compound C[SiH2]O[Si](C)(C)C UHUUYVZLXJHWDV-UHFFFAOYSA-N 0.000 claims 1
- XJIAZXYLMDIWLU-UHFFFAOYSA-N undecane-1,1-diamine Chemical compound CCCCCCCCCCC(N)N XJIAZXYLMDIWLU-UHFFFAOYSA-N 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 9
- 238000012360 testing method Methods 0.000 abstract description 7
- 230000035484 reaction time Effects 0.000 abstract description 5
- HQQHEPWTAFWIRC-UHFFFAOYSA-N N[SiH](N)O[SiH](N)N Chemical compound N[SiH](N)O[SiH](N)N HQQHEPWTAFWIRC-UHFFFAOYSA-N 0.000 abstract 1
- 239000006227 byproduct Substances 0.000 abstract 1
- WHALSQRTWNBBCV-UHFFFAOYSA-N s-aminosulfanylthiohydroxylamine Chemical compound NSSN WHALSQRTWNBBCV-UHFFFAOYSA-N 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 10
- 238000006116 polymerization reaction Methods 0.000 description 10
- 238000010521 absorption reaction Methods 0.000 description 7
- -1 furan methylamine diester Chemical class 0.000 description 6
- 238000007872 degassing Methods 0.000 description 4
- HQHCYKULIHKCEB-UHFFFAOYSA-N tetradecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCCC(O)=O HQHCYKULIHKCEB-UHFFFAOYSA-N 0.000 description 4
- LWBHHRRTOZQPDM-UHFFFAOYSA-N undecanedioic acid Chemical compound OC(=O)CCCCCCCCCC(O)=O LWBHHRRTOZQPDM-UHFFFAOYSA-N 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 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 description 2
- MERLDGDYUMSLAY-UHFFFAOYSA-N 4-[(4-aminophenyl)disulfanyl]aniline Chemical compound C1=CC(N)=CC=C1SSC1=CC=C(N)C=C1 MERLDGDYUMSLAY-UHFFFAOYSA-N 0.000 description 2
- OWJKJLOCIDNNGJ-UHFFFAOYSA-N 4-[[4-hydroxybutyl(dimethyl)silyl]oxy-dimethylsilyl]butan-1-ol Chemical compound OCCCC[Si](C)(C)O[Si](C)(C)CCCCO OWJKJLOCIDNNGJ-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- YQLZOAVZWJBZSY-UHFFFAOYSA-N decane-1,10-diamine Chemical compound NCCCCCCCCCCN YQLZOAVZWJBZSY-UHFFFAOYSA-N 0.000 description 2
- SZVDGKFPAMSDKN-UHFFFAOYSA-N furan;methanamine Chemical compound NC.C=1C=COC=1 SZVDGKFPAMSDKN-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- DXNCZXXFRKPEPY-UHFFFAOYSA-N tridecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCC(O)=O DXNCZXXFRKPEPY-UHFFFAOYSA-N 0.000 description 2
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- 239000004953 Aliphatic polyamide Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 238000005698 Diels-Alder reaction Methods 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 238000012695 Interfacial polymerization Methods 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 229910002808 Si–O–Si Inorganic materials 0.000 description 1
- 150000001263 acyl chlorides Chemical class 0.000 description 1
- 229920003231 aliphatic polyamide Polymers 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000007112 amidation reaction Methods 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000006184 cosolvent Substances 0.000 description 1
- QYQADNCHXSEGJT-UHFFFAOYSA-N cyclohexane-1,1-dicarboxylate;hydron Chemical compound OC(=O)C1(C(O)=O)CCCCC1 QYQADNCHXSEGJT-UHFFFAOYSA-N 0.000 description 1
- VKIRRGRTJUUZHS-UHFFFAOYSA-N cyclohexane-1,4-diamine Chemical compound NC1CCC(N)CC1 VKIRRGRTJUUZHS-UHFFFAOYSA-N 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 150000002019 disulfides Chemical class 0.000 description 1
- QFTYSVGGYOXFRQ-UHFFFAOYSA-N dodecane-1,12-diamine Chemical compound NCCCCCCCCCCCCN QFTYSVGGYOXFRQ-UHFFFAOYSA-N 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 235000001968 nicotinic acid Nutrition 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- KLNPWTHGTVSSEU-UHFFFAOYSA-N undecane-1,11-diamine Chemical compound NCCCCCCCCCCCN KLNPWTHGTVSSEU-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- 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
- C08G69/42—Polyamides containing atoms other than carbon, hydrogen, oxygen, and nitrogen
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyamides (AREA)
Abstract
本发明公开了一种基于二硫键的可自修复自阻燃聚酰胺材料的制备方法，包括如下步骤：1）将二元胺、二元酸、二氨基硅醚和二氨基二硫醚单体混合；2）在惰性气体氛围下，体系于190‑280℃、1.0‑2.0MPa保持0.5‑3h，之后在0.5‑3h内将体系压力降至常压，然后抽真空0.5‑5h，出料即得。和现有技术相比，本发明反应过程中没有副产物产生，且大大缩短反应时间、提高反应效率。测试结果表明，本发明所制备的可自修复的自阻燃聚酰胺材料具有优异的机械性能，自修复效率（120℃）可达98%，自阻燃等级可达V‑0级别，能够很好地解决使用过程中的裂纹问题和聚酰胺易燃问题。The invention discloses a preparation method of a self-repairable and self-flame-retardant polyamide material based on disulfide bonds, comprising the following steps: 1) monobasic diamine, dibasic acid, diaminosilyl ether and diaminodisulfide 2) In an inert gas atmosphere, the system is kept at 190-280°C and 1.0-2.0MPa for 0.5-3h, then the system pressure is reduced to normal pressure within 0.5-3h, and then vacuumed for 0.5-5h, and the material is discharged That's it. Compared with the prior art, no by-products are produced in the reaction process of the present invention, the reaction time is greatly shortened, and the reaction efficiency is improved. The test results show that the self-healable self-flame-retardant polyamide material prepared by the present invention has excellent mechanical properties, the self-healing efficiency (120° C.) can reach 98%, and the self-flame retardant grade can reach V-0 level, which can be very good. It is a good solution to the problem of cracks and flammability of polyamide during use.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a preparation method and a product of a self-repairable self-flame-retardant polyamide material based on disulfide bonds.
Background
Polyamides refer to a class of polymers that contain amide groups in the main chain. The intermolecular hydrogen bonding has excellent properties such as high strength, high toughness, high impact strength, excellent wear resistance, excellent alkali resistance and the like. Polyamide is one of five engineering plastics, and the application field of the polyamide is very wide. However, the occurrence of microcracks during use has a great limit to the service life and mechanical strength of the material. The artificial self-repairing polyamide (SHPA) can recover mechanical properties and original functions when being injured, and has important significance for prolonging service life, improving durability, reducing maintenance cost and the like. With the development of bionics and material science, various well-designed SHPAs have emerged over the past decades. Due to its wide range of potential applications, it has attracted the attention of various subject researchers, from traditional protective products to the latest fashion consumer electronics.
Patent CN 111732727A discloses a preparation method of a self-repairable polyamide material based on Diels-Alder. The method is a three-step method. Firstly, obtaining furan methylamine diester through acrylic ester and furan methylamine, and then carrying out polycondensation with polyether diamine to obtain a prepolymer. Piperazine reacts with butenedioic acid diester and then reacts with furan methylamine to generate star-shaped tetra-amide. The self-repairing polyamide material obtained by the method has high mechanical strength and certain self-repairing efficiency. However, the reaction steps are complicated and require a long time period.
Patent CN 111690132 a discloses a preparation method of a self-repairable polyamide material based on disulfide bonds. Because the diamine with disulfide has lower reactivity, the method prepares the diamine with disulfide into acyl chloride in the presence of cosolvent, and then carries out interfacial polymerization on the prepared diacyl chloride and the diamine, thereby obtaining the polyamide material based on disulfide bond and capable of self-repairing. The polyamide film material capable of self-repairing prepared by the method has excellent mechanical properties, and has certain room temperature self-repairing performance on microcracks in the using process. However, the method is a two-step operation, the reaction period is long, the yield is not high, the solvent used in the reaction process has certain toxicity, the operation requirement is high, and the method is not beneficial to mass production.
Patent CN 110317740a discloses a method for preparing self-repairable conductive polyamide by using two-dimensional materials such as carbon nanotubes. The polyamide matrix in the method is prepared from dimer fatty acid and diethylenetriamine. However, the reflux time is 30 hours, and the cost is high.
In addition, fire safety is an important property of the material in use. The polyamide material, in particular the aliphatic polyamide material belongs to the combustible material, and harmful gas escapes during combustion. The fire-proof and flame-retardant property has very important significance for polyamide materials. Therefore, the polyamide material which is fast and efficient, can self-repair and is self-flame retardant and the preparation method thereof are developed, and the polyamide material has very high application value.
Disclosure of Invention
The invention aims to provide a preparation method of a novel self-repairing self-flame-retardant polyamide material based on disulfide bonds, and the invention also aims to provide a product prepared by the method. By introducing dynamic disulfide bonds in the polymerization process, the self-healing self-flame-retardant polyamide material with a homogeneous system is synthesized by a random copolymerization method. The method greatly shortens the reaction time, improves the reaction efficiency, and can quickly and efficiently obtain the polyamide material with higher molecular weight.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a disulfide bond-based self-repairing self-flame-retardant polyamide material comprises the following steps:
1) mixing diamine, diacid, disulfide and silicon ether;
2) keeping the system at the temperature of 190-280 ℃ and the pressure of 1.0-2.0MPa for 0.5-3h under the inert gas atmosphere, then reducing the system pressure to the normal pressure within 0.5-3h, vacuumizing to the negative pressure, keeping the pressure for 0.5-5h, and discharging to obtain the catalyst.
Preferably, in the step 1), the molar ratio of the diamine, the dibasic acid, the silicon ether and the disulfide is (0.75-1.5): (4.55-4.95): (3.25-3.5): (0.25-1.0).
Preferably, in the step 1), the diamine is one or more of pentamethylene diamine, hexamethylene diamine, decamethylene diamine, undecamethylene diamine, dodecamethylene diamine, tridecylene diamine, tetradecylene diamine and cyclohexane diamine.
Further preferably, the dibasic acid is one or more of adipic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, cyclohexanedicarboxylic acid and terephthalic acid.
Further preferably, the disulfide is one or more of 4,4 '-diaminodiphenyl disulfide, 3' -diaminodiphenyl disulfide, dithiodiethylamine, 3 '-dithiodipropylamine, 3' -dihydroxydiphenyl disulfide, 4 '-dicarboxydiphenyl disulfide and 4,4' -dithiodibutanoic acid.
More preferably, the silicon ether is one or more of bisaminopropyltetramethylsiloxane, 1, 3-bis (4-hydroxybutyl) tetramethyldisiloxane and dipentapropyltetramethylsiloxane.
Preferably, in step 1), the inert gas is one or two of nitrogen, argon and carbon dioxide.
Preferably, in the step 2), vacuumizing is performed again until the negative pressure is maintained for 0.5-5 h.
Meanwhile, the invention also provides the self-repairing self-flame-retardant polyamide material based on the disulfide bond prepared by the method.
Compared with the prior art, the melt polymerization method adopted by the invention has the advantages that only water is generated in the reaction process, the side reaction is less, no solvent is needed, the reaction time is greatly shortened, the reaction efficiency is improved, the self-repairing self-flame-retardant elastomer material with stable quality can be quickly and efficiently obtained, and the melt polymerization method has the following remarkable advantages:
(1) the polymerization is carried out through amidation reaction among monomers, so that the yield is high, the operation is simple, a catalyst is not needed, the reaction time is short, the efficiency is high, the cost is low, and the batch production is facilitated;
(2) the self-repairing self-flame-retardant polyamide is prepared by melt polymerization, and the molecular weight of the product can be controlled by controlling the reaction time, the vacuumizing time and the acid-amine charge ratio. The method can rapidly prepare products with higher molecular weight and large melt viscosity;
(3) the reaction of the invention does not need organic solvent and does not discharge micromolecular organic matters, thus being green and environment-friendly.
Drawings
FIG. 1 is an infrared characteristic spectrum of a self-repairable self-flame-retardant polysilicamide material obtained in example 1 of the invention;
FIG. 2 shows the self-repairable self-flame-retardant polysilicamide material obtained in example 1 of the invention1H nuclear magnetic characteristic spectrum.
Detailed Description
The present invention will be further described with reference to the following examples, but the present invention is not limited thereto.
Example 1:
the self-repairable self-flame-retardant polyamide material based on the disulfide bond and the preparation method thereof comprise the following steps:
1) 1093g (4.75mol) of dodecanedioic acid, 264g (1.5mol) of decamethylenediamine, 900g (3.5mol) of bisaminopropyltetramethylsiloxane, 62g (0.25mol) of 4,4' -diaminodiphenyl disulfide were charged in a 5L autoclave;
2) replacing the gas with inert gas nitrogen for 5 times, then pressurizing to 0.3MPa, starting heating and stirring to 190 ℃, wherein the pressure is 1.7MPa, maintaining the pressure for 3 hours, then deflating, deflating for 3 hours, vacuumizing for 5 hours, then inflating to normal pressure, and then discharging.
Example 2:
the procedure of example 2 was as in example 1 except that the polymerization temperature, the degassing time and the evacuation time were varied, wherein the polymerization temperature was 280 ℃, the degassing time was 0.5h and the evacuation time was 0.5h, and the specific ratios are shown in Table 1.
Example 3:
the procedure of example 3 was as in example 1 except that the polymerization temperature, the degassing time and the evacuation time were varied, wherein the polymerization temperature was 240 ℃, the degassing time was 1.5h and the evacuation time was 2.5h, and the specific ratios are shown in Table 1.
Example 4:
the procedure of example 4 was as in example 3, except that the kind of diamine and disulfide was changed, wherein the diamine was hexamethylenediamine and the disulfide was 3, 3' -diaminodiphenyldisulfide. The specific ratio is shown in table 1.
Example 5:
the procedure of example 5 was as in example 3, except that the kind of diamine and disulfide was changed, wherein the diamine was 1, 4 cyclohexanediamine and the disulfide was dithiodiethylamine. The specific ratio is shown in table 1.
Example 6:
the procedure of example 6 was as in example 3 except that the type of diacid and disulfide was varied, wherein the diacid was terephthalic acid and the disulfide was dithiodiethylamine. The specific ratio is shown in table 1.
Example 7:
the procedure of example 7 is as in example 3, except that the type of diacid and disulfide is varied, wherein the diacid is 1, 4 cyclohexanedicarboxylic acid and the disulfide is 3, 3' -diaminodiphenyl disulfide. The specific ratio is shown in table 1.
Example 8:
the procedure of example 8 is as in example 3, except that the type of diacid and disulfide is varied, the diacid being adipic acid and the disulfide being 4,4' -dicarboxydiphenyl disulfide. The specific ratio is shown in table 1.
Comparative example 1
The synthesis of this comparative example differs from that of example 1 only in that the monomers synthesized are diamines, diacids and diaminosiloxanes without disulfides.
Comparative example 2
The synthesis of the polyamide of this comparative example differs from that of example 1 only in that the monomers synthesized are diamines, diacids and no silicon and disulfide.
The specific components and proportions of the examples and comparative examples are shown in Table 1
TABLE 1 Components and proportions of examples 1-8 and comparative examples 1-2
In other embodiments, the dibasic acid may also be selected from one of sebacic acid, undecanedioic acid, tridecanedioic acid, tetradecanedioic acid. The disulfide may be selected from one of 3, 3 '-dithiodipropylamine and 4,4' -dithiodibutanoic acid. The silicon ether can be selected from one of 1, 3-bis (4-hydroxybutyl) tetramethyldisiloxane and dipentylpretaethyltetramethylsiloxane, and details in the examples are not repeated.
Testing of the product Structure of the invention
The product prepared by the method is subjected to structure determination by adopting infrared spectroscopy (FT-IR) and nuclear magnetic resonance hydrogen spectrum (F)1H-NMR) test results confirmed that the product obtained in the present invention is a polysilicamide. The following description will be made by taking example 1 as an example. FIG. 1 and FIG. 2 show the IR (FT-IR) and NMR spectra of the polysilicamide obtained in example 11H-NMR) test results.
In the IR spectrum of FIG. 1, Si-CH is simultaneously present3The stretching vibration absorption peak of the middle C-H bond (795cm-1) Stretching vibration absorption peak of Si-O-Si bond (1041cm-1)，Si-CH3Middle C-H bending deformation absorption peak (1252cm-1) Absorption peaks of C-N stretching vibration and C ═ O in-plane bending vibration in amide bond (1537cm-1) C ═ O bond stretching vibration absorption peak (1637cm-1) The stretching vibration absorption peak of C-H bond in methylene (2928cm-1) Expansion and contraction vibration absorption peak of N-H bond (3305cm-1) Thus, the successful synthesis of PA1212/Si12 series copolymer was confirmed.
FIG. 2 is a schematic diagram of the utilization of1H-NMR measured chemical shifts of hydrogen atoms in the product of example 1 and calibrated.
From the results of fig. 1 and 2, the product obtained in example 1 was polysilamide.
Testing of the physical Properties of the products of the invention
In the examples of the present invention, the physical properties of the obtained polysilicamide were characterized, and the measurement instruments and the measurement standards used for the characterization are shown below.
TABLE 2 test items, instruments and standards
Examples 1-8 reflect the results of testing a variety of samples of polysilicamide prepared by the melt polymerization process, as shown in table 3.
TABLE 3 Properties of Polysilamides obtained in examples 1 to 8 and comparative examples 1 to 2
Mechanical properties were characterized and the material and repair effects were calculated by tensile testing for examples 1-8 and comparative examples 1-2.
As can be seen from Table 3, in examples 1 to 8, the self-repairable self-flame-retardant polyamide material obtained by using different monomers and ratios has excellent mechanical properties, self-repair efficiency and self-flame-retardant performance.
In comparative example 1, since no disulfide bond-carrying monomer was introduced, no self-repairing effect was obtained. And the introduction of disulfide is equivalent to or more excellent in mechanical strength and self-flame retardant effect.
In comparative example 2, since no silyl ether and no disulfide bond were introduced, the self-repairing and self-flame-retardant properties were not exhibited.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (9)
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Citations (3)
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| WO2014029966A1 (en) * | 2012-08-24 | 2014-02-27 | Croda International Plc | Polyimide composition |
| CN109293916A (en) * | 2018-09-30 | 2019-02-01 | 郑州大学 | Polyamide/siloxane copolymer and preparation method thereof |
| CN111690132A (en) * | 2020-06-01 | 2020-09-22 | 电子科技大学 | Preparation method of self-repairing polyamide packaging material for lithium battery soft package |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2014029966A1 (en) * | 2012-08-24 | 2014-02-27 | Croda International Plc | Polyimide composition |
| CN109293916A (en) * | 2018-09-30 | 2019-02-01 | 郑州大学 | Polyamide/siloxane copolymer and preparation method thereof |
| CN111690132A (en) * | 2020-06-01 | 2020-09-22 | 电子科技大学 | Preparation method of self-repairing polyamide packaging material for lithium battery soft package |
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