CN115073281B - Preparation method of woody oil-based unsaturated diacid, application of woody oil-based unsaturated diacid in preparation of polyamide and prepared polyamide - Google Patents
Preparation method of woody oil-based unsaturated diacid, application of woody oil-based unsaturated diacid in preparation of polyamide and prepared polyamide Download PDFInfo
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- 239000004952 Polyamide Substances 0.000 title claims abstract description 78
- 229920002647 polyamide Polymers 0.000 title claims abstract description 78
- 238000002360 preparation method Methods 0.000 title claims abstract description 39
- 238000000034 method Methods 0.000 claims abstract description 27
- 239000003921 oil Substances 0.000 claims description 125
- 239000000178 monomer Substances 0.000 claims description 63
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 51
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 42
- 239000003760 tallow Substances 0.000 claims description 42
- 238000005406 washing Methods 0.000 claims description 27
- 238000001035 drying Methods 0.000 claims description 26
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 20
- 239000000194 fatty acid Substances 0.000 claims description 20
- 229930195729 fatty acid Natural products 0.000 claims description 20
- 150000004665 fatty acids Chemical class 0.000 claims description 19
- 238000000746 purification Methods 0.000 claims description 17
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 16
- 238000000967 suction filtration Methods 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 15
- 239000011261 inert gas Substances 0.000 claims description 13
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 12
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 12
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 12
- FCDPQMAOJARMTG-UHFFFAOYSA-M benzylidene-[1,3-bis(2,4,6-trimethylphenyl)imidazolidin-2-ylidene]-dichlororuthenium;tricyclohexylphosphanium Chemical compound C1CCCCC1[PH+](C1CCCCC1)C1CCCCC1.CC1=CC(C)=CC(C)=C1N(CCN1C=2C(=CC(C)=CC=2C)C)C1=[Ru](Cl)(Cl)=CC1=CC=CC=C1 FCDPQMAOJARMTG-UHFFFAOYSA-M 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 6
- AYEKOFBPNLCAJY-UHFFFAOYSA-O thiamine pyrophosphate Chemical compound CC1=C(CCOP(O)(=O)OP(O)(O)=O)SC=[N+]1CC1=CN=C(C)N=C1N AYEKOFBPNLCAJY-UHFFFAOYSA-O 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 3
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- 239000011259 mixed solution Substances 0.000 claims 2
- 239000002994 raw material Substances 0.000 abstract description 22
- 238000006243 chemical reaction Methods 0.000 abstract description 16
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- 230000006386 memory function Effects 0.000 abstract description 9
- 239000002028 Biomass Substances 0.000 abstract description 7
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 6
- 150000001336 alkenes Chemical class 0.000 abstract description 5
- 238000000354 decomposition reaction Methods 0.000 abstract description 5
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 5
- 230000007062 hydrolysis Effects 0.000 abstract description 4
- 230000002194 synthesizing effect Effects 0.000 abstract description 3
- 239000008204 material by function Substances 0.000 abstract description 2
- 235000019198 oils Nutrition 0.000 description 119
- 229920000263 Rubber seed oil Polymers 0.000 description 33
- 229920006021 bio-based polyamide Polymers 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 13
- 150000004985 diamines Chemical class 0.000 description 12
- 239000003054 catalyst Substances 0.000 description 11
- 235000015112 vegetable and seed oil Nutrition 0.000 description 10
- 238000005481 NMR spectroscopy Methods 0.000 description 9
- 229920000642 polymer Polymers 0.000 description 7
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- 238000002329 infrared spectrum Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 235000019484 Rapeseed oil Nutrition 0.000 description 4
- 238000005865 alkene metathesis reaction Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000013067 intermediate product Substances 0.000 description 4
- 230000005311 nuclear magnetism Effects 0.000 description 4
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 3
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 3
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 3
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 3
- 239000005642 Oleic acid Substances 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- -1 fatty acid esters Chemical class 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 2
- SBLKVIQSIHEQOF-UPHRSURJSA-N Octadec-9-ene-1,18-dioic-acid Chemical compound OC(=O)CCCCCCC\C=C/CCCCCCCC(O)=O SBLKVIQSIHEQOF-UPHRSURJSA-N 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000004359 castor oil Substances 0.000 description 2
- 235000019438 castor oil Nutrition 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000000113 differential scanning calorimetry Methods 0.000 description 2
- 235000019197 fats Nutrition 0.000 description 2
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- 239000010773 plant oil Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
- 239000004416 thermosoftening plastic Substances 0.000 description 2
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 description 2
- SBLKVIQSIHEQOF-OWOJBTEDSA-N (e)-octadec-9-enedioic acid Chemical compound OC(=O)CCCCCCC\C=C\CCCCCCCC(O)=O SBLKVIQSIHEQOF-OWOJBTEDSA-N 0.000 description 1
- BTXXTMOWISPQSJ-UHFFFAOYSA-N 4,4,4-trifluorobutan-2-one Chemical compound CC(=O)CC(F)(F)F BTXXTMOWISPQSJ-UHFFFAOYSA-N 0.000 description 1
- BQACOLQNOUYJCE-FYZZASKESA-N Abietic acid Natural products CC(C)C1=CC2=CC[C@]3(C)[C@](C)(CCC[C@@]3(C)C(=O)O)[C@H]2CC1 BQACOLQNOUYJCE-FYZZASKESA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- 241000219226 Acer truncatum Species 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 241000208688 Eucommia Species 0.000 description 1
- 241001299699 Idesia Species 0.000 description 1
- OYHQOLUKZRVURQ-HZJYTTRNSA-N Linoleic acid Chemical compound CCCCC\C=C/C\C=C/CCCCCCCC(O)=O OYHQOLUKZRVURQ-HZJYTTRNSA-N 0.000 description 1
- 235000006484 Paeonia officinalis Nutrition 0.000 description 1
- 244000170916 Paeonia officinalis Species 0.000 description 1
- 240000003152 Rhus chinensis Species 0.000 description 1
- 235000014220 Rhus chinensis Nutrition 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 235000019498 Walnut oil Nutrition 0.000 description 1
- 244000248162 Xanthoceras sorbifolium Species 0.000 description 1
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001408 amides Chemical group 0.000 description 1
- 229920001222 biopolymer Polymers 0.000 description 1
- 239000010495 camellia oil Substances 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 235000001122 chang geng bian tao Nutrition 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000005686 cross metathesis reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 239000012761 high-performance material Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 235000020778 linoleic acid Nutrition 0.000 description 1
- OYHQOLUKZRVURQ-IXWMQOLASA-N linoleic acid Natural products CCCCC\C=C/C\C=C\CCCCCCCC(O)=O OYHQOLUKZRVURQ-IXWMQOLASA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000004006 olive oil Substances 0.000 description 1
- 235000008390 olive oil Nutrition 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- 239000002383 tung oil Substances 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 239000008170 walnut oil Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/09—Preparation of carboxylic acids or their salts, halides or anhydrides from carboxylic acid esters or lactones
-
- 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
- C08G69/34—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids using polymerised unsaturated fatty acids
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Polyamides (AREA)
Abstract
The invention relates to the technical field of bio-based functional materials, in particular to a preparation method of woody oil-based unsaturated diacid, application of the woody oil-based unsaturated diacid in preparation of polyamide and the prepared polyamide. The method takes woody grease as a raw material, and obtains woody oil-based unsaturated diacid through hydrolysis and olefin double decomposition, so as to realize the chemical conversion of the woody grease and fully utilize the biomass resource of woody oil crops; the woody oil-based unsaturated diacid is used for synthesizing polyamide, the mechanical and thermal properties of the polyamide can be effectively improved, the polyamide has excellent mechanical properties and shape memory function, the breaking strength is 18.9-34.1MPa, the breaking elongation is 138.2-216.4%, the Young modulus is 114.4-240.4MPa, and the toughness is 28.9-37.7MJ/m 3 。
Description
Technical Field
The invention relates to the technical field of bio-based functional materials, in particular to a preparation method of woody oil-based unsaturated diacid, application of the woody oil-based unsaturated diacid in preparation of polyamide and the prepared polyamide.
Background
Polyamide commonly known as nylon refers to a high molecular polymer with a large number of amide functional groups (-NH-CO-) repeating units in the main chain. In the polymers, amide bonds can form hydrogen bonds among molecular chains of the polymers, so that the polymers have excellent performance, and the polymers are widely applied to various fields of aerospace, electronics, automobiles, clothing, transportation and the like. At present, AABB type polyamide is mainly obtained by polycondensation reaction of dibasic acid and diamine.
With the development of society, the increasing decrease of fossil resources and the increasing increase of environmental problems, the preparation of polyamides using biomass resources has become a hot spot for research in various countries of the world today. At present, the main biomass raw materials for preparing polyamide comprise polysaccharide, cellulose, terpenes, abietic acid, vegetable oil and the like. In 2010, the global capacity of these bio-based monomers reached 4 ten thousand tons/year. While bio-based polyamides are a popular product (about 5% of the current biopolymer market), their use in high performance materials is becoming increasingly important due to their excellent properties. Thus, the development of environmentally friendly biobased polyamide materials to gradually or even completely replace the same petroleum-based polyamides would be a necessary trend. Among them, vegetable oils are an object of attention of many researchers.
The current research on vegetable oil-based polyamides mainly involves castor oil, rapeseed oil, etc. Arkema company produced PA11 using castor oil as a main raw material. Mathias et al (Linear unsaturated polyamides: nylon 6u18 and 18 u18.Macromolecular Chemistry and Physics,2004,205,2438-2442.) synthesized unsaturated biobased PA6U18 and PA18U18 from biobased octadec-9-enedioic acid prepared from oleic acid as a starting material with hexamethylenediamine and octadecadienediamine, respectively. Fradet et al (Unsaturated polyamides from bio-based Z-octadec-9-enedioic acid. Macromolecular Chemistry and Physics,2008,209,64-74.) synthesized a series of unsaturated biobased polyamides containing double bond structures from biobased Z-octadeca-9-enedioic acid prepared from oleic acid and rapeseed oil, respectively, with aliphatic, alicyclic, and semiaromatic diamines. Verous et al (Polymer acids-based thermoplastic bio-polyamides: reaction kinetics, properties and structures. Polymer,2010,51 (25), 5895-5902.) synthesized thermoplastic biobased polyamides of different chain lengths from biobased Dimer acid monomers prepared from natural vegetable oleic acid and linoleic acid with ethylenediamine, hexamethylenediamine, and octylenediamine, respectively, and had low crystallinity and good fluidity, and were widely used in the fields of inks, varnishes, and heat seal coatings. Aman Ullah et al (Synthesis and Characterization of Unsaturated Biobased Polyamides from Plant oil. ACS Sustainable chem. Eng.2020,8, 8049-8058.) synthesized two biobased polyamides with tensile strength of 0.5-18MPa and strain of 8% -139% using dimethyl 9-octadecenodiate and para-xylylenediamine or diethylenetriamine as raw materials.
China is a large country for producing woody oil crops, and the woody oil crops have the advantages of rich yield, repeated adoption, no land competition with grains and the like. However, the sources of the reported bio-based monomer raw materials are limited, and particularly, the research on preparing the bio-based polyamide by the woody grease is very little, and how to realize the chemical conversion of the woody grease so as to fully utilize the biomass resource of the woody oil crops becomes a current difficult problem; and the polyamide synthesized by the existing bio-based monomer raw material has the problem of insufficient mechanical and thermal properties.
Disclosure of Invention
The invention provides a preparation method of woody oil-based unsaturated diacid, which aims to solve the technical problem of how to realize chemical conversion of woody grease so as to fully utilize biomass resources of woody oil crops.
A method for preparing woody oil-based unsaturated diacid comprises taking woody oil as raw material, hydrolyzing, and subjecting to olefin metathesis to obtain woody oil-based unsaturated diacid; the woody oil comprises any one of tea oil, walnut oil, peony oil, rubber seed oil, chinese tallow kernel oil, acer truncatum seed oil, idesia polycarpa seed oil, amygdalus pedunculata oil, eucommia seed oil, samara oil seed oil, guangdong Pi wood oil, shiny-leaved yellowhorn oil, tung oil, olive oil and Rhus chinensis oil.
The beneficial effects are that: the method takes woody grease as a raw material, and obtains woody oil-based unsaturated diacid through hydrolysis and olefin double decomposition, so as to realize the chemical conversion of the woody grease and fully utilize the biomass resource of woody oil crops; and the woody oil-based unsaturated diacid is used for synthesizing the polyamide, so that the mechanical and thermal properties of the polyamide can be effectively improved.
Preferably, the method for preparing the woody oil-based unsaturated diacid comprises the following steps:
taking 100 parts of woody grease and 0.1-1 part of catalyst according to parts by weight, and reacting for 24-48 hours at 40-50 ℃ under the protection of inert gas; then adding 500-1000 parts of organic reagent for purification and washing, carrying out suction filtration and drying to obtain the woody oil-based unsaturated diacid monomer.
The beneficial effects are that: when the woody oil-based unsaturated diacid is prepared, the woody oil-based unsaturated diacid monomer is prepared only by hydrolyzing woody oil and performing olefin double decomposition reaction and then purifying and washing by using an organic reagent, and the woody oil-based unsaturated diacid monomer has the advantages of simple method and convenient operation and is beneficial to pushing the utilization of woody oil crops.
Preferably, the catalyst is a second generation Grubbs catalyst.
Preferably, the organic reagent is ethyl acetate, and ethyl acetate is used for washing 2-3 times to remove unreacted raw materials and generated impurities.
The beneficial effects are that: the reaction product is directly mixed with ethyl acetate for purification and washing, and compared with the traditional method adopting silica gel column purification or mixed liquid washing of n-hexane and ethyl acetate, the method has the advantages of simpler operation and higher purification efficiency.
Preferably, the woody oil-based unsaturated diacid monomer has the structure:
the invention provides an application of a preparation method of woody oil-based unsaturated diacid in preparing polyamide, and aims to solve the technical problem of how to overcome the defect of insufficient mechanical and thermal properties of polyamide synthesized from bio-based monomer raw materials.
Preferably, the application of the preparation method of woody oil-based unsaturated diacid in preparing polyamide comprises the following steps:
(1) Taking 100 parts of woody grease and 0.1-1 part of catalyst according to parts by weight, and reacting for 24-48 hours at 40-50 ℃ under the protection of inert gas; then adding 500-1000 parts of organic reagent for purification and washing, carrying out suction filtration and drying to obtain the woody oil-based unsaturated diacid monomer;
(2) Mixing 100 parts of woody oil-based unsaturated diacid monomer, 100 parts of diamine monomer, 100-400 parts of cosolvent, 600-1300 parts of catalyst and 300-800 parts of solvent under the protection of inert gas;
(3) Placing the mixed system in an oil bath pan and continuously stirring, heating to 70-90 ℃ and keeping for 0.5-1.5h; then gradually heating the temperature to 150-170 ℃ and keeping the temperature for 2-6h;
(4) Cooling to room temperature, adding a precipitator for precipitation, washing, purifying, and then carrying out suction filtration and drying to obtain the woody oil-based unsaturated polyamide.
The beneficial effects are that: the woody oil-based unsaturated diacid monomer is prepared from woody oil and fat serving as raw materials, then is mixed with diamine monomer under the auxiliary conditions of cosolvent, catalyst, solvent and the like, is heated and stirred for reaction under the protection of inert gas, and is subjected to precipitation, washing, purification, suction filtration and drying to obtain the woody oil-based unsaturated polyamide; in the process of preparing the polyamide, the woody oil-based unsaturated polyamide with excellent mechanical property and shape memory function is obtained by regulating and controlling the reaction conditions of the woody oil-based unsaturated diacid monomer and the diamine monomer.
The mechanical properties of the polyamide are as follows: the breaking strength is 16-45Mpa, the breaking elongation is 20-300%, the Young modulus is 100-300MPa, and the toughness is 3-40MJ/m 3 The method comprises the steps of carrying out a first treatment on the surface of the The polyamide film with fixed shape is heated and folded into any shape, cooled to room temperature and fixed into the shape, and after re-heating, the polyamide film can be quickly restored to the original fixed shape without applying any external force, and has excellent shape memory function.
Preferably, the diamine monomer in the step (2) is 1, 6-hexamethylenediamine; the cosolvent is lithium chloride; the catalyst is one or two compositions of pyridine and TPP; the solvent is NMP (N-methylpyrrolidone).
Preferably, the precipitating agent in the step (4) is methanol, and the washing agent is V Methanol ：V Deionized water =1:1, the drying conditions are 65-75 ℃ vacuum oven drying for 45-50h.
In a third aspect, the present invention provides a woody oil-based unsaturated polyamide obtained by applying the preparation method in the preparation of polyamide, wherein the woody oil-based unsaturated polyamide has the following structural formula:
wherein m=100-500.
The invention has the advantages that:
1. the method takes woody grease as a raw material, and obtains woody oil-based unsaturated diacid through hydrolysis and olefin double decomposition, so as to realize the chemical conversion of the woody grease and fully utilize the biomass resource of woody oil crops; and the woody oil-based unsaturated diacid is used for synthesizing the polyamide, so that the mechanical and thermal properties of the polyamide can be effectively improved.
2. When the woody oil-based unsaturated diacid is prepared, the woody oil-based unsaturated diacid monomer is prepared only by carrying out hydrolysis and olefin double decomposition reaction on woody oil and then purifying and washing by using an organic reagent, and the method has the advantages of simplicity and convenience in operation and is beneficial to pushing the utilization of woody oil crops.
3. The woody oil-based unsaturated diacid monomer is prepared from woody oil and fat serving as raw materials, then is mixed with diamine monomer under the auxiliary conditions of cosolvent, catalyst, solvent and the like, is heated and stirred for reaction under the protection of inert gas, and is subjected to precipitation, washing, purification, suction filtration and drying to obtain the woody oil-based unsaturated polyamide; in the process of preparing the polyamide, the woody oil-based unsaturated polyamide with excellent mechanical property and shape memory function is obtained by regulating and controlling the reaction conditions of the woody oil-based unsaturated diacid monomer and the diamine monomer.
4. The mechanical properties of the polyamide are as follows: the breaking strength is 18.9-34.1MPa, the breaking elongation is 138.2-216.4%, the Young modulus is 114.4-240.4MPa, and the toughness is 28.9-37.7MJ/m 3 The method comprises the steps of carrying out a first treatment on the surface of the The polyamide film with fixed shape is heated and folded into any shape, cooled to room temperature and fixed into the shape, and after re-heating, the polyamide film can be quickly restored to the original fixed shape without applying any external force, and has excellent shape memory function.
Drawings
FIG. 1 shows the nuclear magnetism of the raw materials, intermediate products and target products of the preparation process in example 1 of the present application 1 H NMR chart;
FIG. 2 is a graph of the differential scanning calorimeter results of examples 1 and 2 of the present application;
FIG. 3 is a schematic diagram of the preparation route of the rubber seed oil-based unsaturated diacid in example 1 of the present application;
FIG. 4 shows the nuclear magnetism of the raw materials, intermediate products and target products of the preparation process in example 2 of the present application 1 H NMR chart;
FIG. 5 is an infrared spectrum analysis chart of example 5 and example 6 of the present application;
FIG. 6 is a graph showing the results of stress-strain testing performed on a biobased polyamide sample in example 9 of the present application;
FIG. 7 is a graph showing the shape change and recovery of the bio-based polyamide sample in example 10 of the present application.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions in the embodiments of the present invention will be clearly and completely described in the following in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The embodiment discloses a preparation method of woody oil-based unsaturated diacid, which comprises the following steps:
preparation of rubber seed oil-based unsaturated diacid monomer: taking 100 parts by weight of rubber seed oil fatty acid and 0.6 part by weight of second generation Grubbs catalyst, and reacting for 24 hours at 45 ℃ under the protection of nitrogen; then 700 parts of ethyl acetate is added for purification and washing for 3-6 times, and the rubber seed oil-based unsaturated diacid monomer is obtained after suction filtration and drying.
Performing nuclear magnetic resonance analysis on the raw materials, the intermediate products and the target products in the preparation process of the embodiment to obtain a nuclear magnetic resonance hydrogen spectrogram 1 H NMR is shown in FIG. 1. As can be seen from FIG. 1, the position of about 5.25ppm of the peak on the tertiary carbon in the middle of the three ester bonds of the rubber seed oil triglyceride completely disappeared in the nuclear magnetic resonance chart of the rubber seed oil precursor, indicating that the hydrolysis reaction of the rubber seed oil has completely occurred to give the rubber seed oil fatty acid. The 2.80ppm position in the rubber seed oil fatty acid completely disappears in the nuclear magnetism of the rubber seed oil diacid monomer, which indicates that the rubber seed oil fatty acid completely undergoes olefin metathesis reaction to obtain the rubber seed oil-based diacid monomer, and the monomer is the rubber seed oil-based E-octadeca-9-enediacid.
In addition, the rubber seed oil-based unsaturated diacid monomer prepared in this example was analyzed by differential scanning calorimetry, and the differential scanning calorimeter results are shown in fig. 2. The rubber seed oil-based unsaturated diacid monomer has an obvious melting point at 99 ℃, and the purified rubber seed oil-based E-octadeca-9-enediacid monomer is proved to be of a trans structure, so that the successful preparation of the rubber seed oil-based E-octadeca-9-enediacid monomer is further proved.
According to the analysis, the specific reaction process for preparing the rubber seed oil-based unsaturated diacid is shown in fig. 3, rubber seed oil (such as a compound of formula I) is hydrolyzed to obtain rubber seed oil fatty acid (such as a compound of formula II-1, II-2 and II-3), and the rubber seed oil fatty acid is subjected to olefin metathesis reaction to obtain a rubber seed oil-based E-octadeca-9-enediacid monomer (such as a compound of formula III).
Example 2
The embodiment discloses a preparation method of woody oil-based unsaturated diacid, which comprises the following steps:
preparation of Chinese tallow kernel oil-based unsaturated diacid monomer: taking 100 parts by weight of Chinese tallow kernel oil fatty acid and 0.5 part by weight of second generation Grubbs catalyst, and reacting for 24 hours at 45 ℃ under the protection of nitrogen; then adding 800 parts of ethyl acetate for purification and washing for 3-6 times, and carrying out suction filtration and drying to obtain the Chinese tallow kernel oil-based unsaturated diacid monomer.
Performing nuclear magnetic resonance analysis on the raw materials, intermediate products and target products in the preparation process to obtain a nuclear magnetic resonance hydrogen spectrogram 1 H NMR is shown in FIG. 4. From fig. 4, it can be seen that the position of about 5.25ppm of the peak on the tertiary carbon in the middle of three ester bonds of the Chinese tallow kernel oil triglyceride completely disappears in the nuclear magnetic pattern of the Chinese tallow kernel oil fatty acid, which indicates that the Chinese tallow kernel oil has completely undergone hydrolysis reaction to obtain the Chinese tallow kernel oil fatty acid. The position of 2.80ppm in the Chinese tallow kernel oil fatty acid completely disappears in the nuclear magnetism of the Chinese tallow kernel oil diacid monomer, which indicates that the Chinese tallow kernel oil fatty acid has completely undergone olefin metathesis reaction to obtain the Chinese tallow kernel oil diacid monomer, and the monomer is Chinese tallow kernel oil-based E-octadeca-9-enediacid.
In addition, the Chinese tallow kernel oil-based unsaturated diacid monomer prepared in the embodiment is analyzed by using a differential scanning calorimetry method, and the differential scanning calorimetric result is shown in figure 2. The method can be used for proving that the purified Chinese tallow kernel oil-based E-octadeca-9-enediacid monomer has a trans-structure when the Chinese tallow kernel oil-based unsaturated diacid monomer has an obvious melting point at 99 ℃, and further proving that the Chinese tallow kernel oil-based E-octadeca-9-enediacid monomer is successfully prepared.
Example 3
The embodiment discloses a preparation method of woody oil-based unsaturated diacid, which comprises the following steps:
taking 100 parts by weight of Chinese tallow kernel oil fatty acid and 0.1 part by weight of second generation Grubbs catalyst, and reacting for 48 hours at 50 ℃ under the protection of nitrogen; then adding 500 parts of ethyl acetate for purification and washing for 3-6 times, and carrying out suction filtration and drying to obtain the woody oil-based unsaturated diacid monomer.
Example 4
The embodiment discloses a preparation method of woody oil-based unsaturated diacid, which comprises the following steps:
taking 100 parts by weight of Chinese tallow kernel oil fatty acid and 1 part by weight of a second generation Grubbs catalyst, and reacting for 24 hours at 40 ℃ under the protection of nitrogen; then 1000 parts of ethyl acetate is added for purification and washing for 3-6 times, and the woody oil-based unsaturated diacid monomer is obtained after suction filtration and drying.
Comparative example 1
The embodiment discloses a preparation method of woody oil-based unsaturated diacid, which comprises the following steps:
taking 100 parts by weight of Chinese tallow kernel oil fatty acid and 0.01 part by weight of second generation Grubbs catalyst, and reacting for 48 hours at 45 ℃ under the protection of nitrogen; then adding 200 parts of ethyl acetate for purification and washing for 3-6 times, and carrying out suction filtration and drying to obtain the woody oil-based unsaturated diacid monomer.
The conversion and yield of the woody oil-based unsaturated diacid prepared in examples 1-4, comparative example 1 were measured, and the comparative results of the respective preparation schemes are shown in Table 1.
TABLE 1 comparison of preparation schemes of woody oil-based unsaturated diacids
As can be seen from Table 1, the preparation of the woody vegetable oil to the unsaturated diacid requires a proper catalyst amount, because the woody vegetable oil contains more unsaturated fatty acid and has more double bonds, if the catalyst amount is smaller, the synthesis of the unsaturated diacid is unfavorable, the conversion rate and the yield are lower, and the conversion rate and the yield of the woody vegetable oil to the unsaturated diacid can be greatly improved by increasing the catalyst amount.
Example 5
The embodiment discloses an application of a preparation method of woody oil-based unsaturated diacid in preparing polyamide, which comprises the following steps:
(1) Taking 100 parts by weight of rubber seed oil fatty acid and 0.6 part by weight of second generation Grubbs catalyst, and reacting for 24 hours at 45 ℃ under the protection of nitrogen; then 700 parts of ethyl acetate is added for purification and washing for 3-6 times, and the rubber seed oil-based unsaturated diacid monomer is obtained after suction filtration and drying.
(2) 100 parts of rubber seed oil-based unsaturated diacid monomer, 100 parts of 1, 6-hexamethylenediamine, 300 parts of lithium chloride, 600 parts of pyridine and 200 parts of TPP are added to 400 parts of NMP (N-methylpyrrolidone) and mixed under the protection of inert gas.
(3) Placing the mixed system in an oil bath pan and continuously stirring, heating to 80 ℃ and keeping for 1h; the temperature was then gradually increased to 160℃and maintained for 6h.
(4) After cooling to room temperature, methanol was added to precipitate, followed by a mixture of methanol and pure water (V Methanol ：V Deionized water =1:1), washing, purifying, suction filtering, drying in a vacuum oven at 70 ℃ for 48 hours, and drying to obtain the rubber seed oil-based unsaturated polyamide.
The raw materials and the target product in the preparation process of the embodiment are subjected to infrared spectrum analysis, and the obtained infrared spectrum is shown in fig. 5. As can be seen from the figure, 1696cm of the rubber seed oil-based unsaturated diacid monomer -1 The stretching vibration peak of the carboxylic acid carbonyl at the position completely disappears and is converted into 1632cm of polyamide -1 An amide carbonyl stretching vibration peak at the position; at the same time, 1534cm of the unsaturated polyamide can be seen in the infrared -1 N-H bending vibration peak at 1218cm -1 C-N stretching vibration peak at 3307cm -1 These demonstrate successful preparation of the rubber seed oil based unsaturated polyamide at the N-H stretching vibration peaks. And the rubber seed oil-based unsaturated polyamide has the following structural formula:
where m=100-500.
Example 6
The embodiment discloses an application of a preparation method of woody oil-based unsaturated diacid in preparing polyamide, which comprises the following steps:
(1) Taking 100 parts by weight of Chinese tallow kernel oil fatty acid and 0.5 part by weight of second generation Grubbs catalyst, and reacting for 24 hours at 45 ℃ under the protection of nitrogen; then adding 800 parts of ethyl acetate for purification and washing for 3-6 times, and carrying out suction filtration and drying to obtain the Chinese tallow kernel oil-based unsaturated diacid monomer.
(2) 100 parts of Chinese tallow kernel oil-based unsaturated diacid monomer, 100 parts of 1, 6-hexamethylenediamine, 300 parts of lithium chloride, 600 parts of pyridine and 200 parts of TPP are added into 400 parts of NMP (N-methylpyrrolidone) and mixed under the protection of inert gas.
(3) Placing the mixed system in an oil bath pan and continuously stirring, heating to 80 ℃ and keeping for 1h; the temperature was then gradually increased to 160℃and maintained for 6h.
(4) After cooling to room temperature, methanol was added to precipitate, followed by a mixture of methanol and pure water (V Methanol ：V Deionized water =1:1), washing, purifying, suction filtering, drying in a vacuum oven at 70 ℃ for 48 hours, and drying to obtain the Chinese tallow kernel oil-based unsaturated polyamide.
The raw materials and the target product in the preparation process of the embodiment are subjected to infrared spectrum analysis, and the obtained infrared spectrum is shown in fig. 5. From the figure, 1696cm of the Chinese tallow kernel oil-based unsaturated diacid monomer can be seen -1 The stretching vibration peak of the carboxylic acid carbonyl at the position completely disappears and is converted into 1632cm of polyamide -1 An amide carbonyl stretching vibration peak at the position; at the same time, 1534cm of the unsaturated polyamide can be seen in the infrared -1 N-H bending vibration peak at 1218cm -1 C-N stretching vibration peak at 3307cm -1 These can demonstrate successful preparation of the Chinese tallow kernel based unsaturated polyamide at the N-H stretching vibration peak. And the structural formula of the Chinese tallow kernel oil-based unsaturated polyamide is as follows:
where m=100-500.
Example 7
The embodiment discloses an application of a preparation method of woody oil-based unsaturated diacid in preparing polyamide, which comprises the following steps:
(1) Taking 100 parts by weight of Chinese tallow kernel oil fatty acid and 0.5 part by weight of second generation Grubbs catalyst, and reacting for 24 hours at 45 ℃ under the protection of nitrogen; then adding 800 parts of ethyl acetate for purification and washing for 3-6 times, and carrying out suction filtration and drying to obtain the Chinese tallow kernel oil-based unsaturated diacid monomer.
(2) 100 parts of Chinese tallow kernel oil-based unsaturated diacid monomer, 100 parts of 1, 6-hexamethylenediamine, 100 parts of lithium chloride, 500 parts of pyridine and 100 parts of TPP are added into 300 parts of NMP (N-methylpyrrolidone) and mixed under the protection of inert gas.
(3) Placing the mixed system in an oil bath pan and continuously stirring, heating to 70 ℃ and keeping for 1.5h; the temperature was then gradually increased to 150℃and maintained for 4h.
(4) After cooling to room temperature, methanol was added to precipitate, followed by a mixture of methanol and pure water (V Methanol ：V Deionized water =1:1), washing, purifying, suction filtering, drying in a vacuum oven at 65 ℃ for 50 hours, and drying to obtain the Chinese tallow kernel oil-based unsaturated polyamide.
Example 8
The embodiment discloses an application of a preparation method of woody oil-based unsaturated diacid in preparing polyamide, which comprises the following steps:
(1) Taking 100 parts by weight of Chinese tallow kernel oil fatty acid and 0.5 part by weight of second generation Grubbs catalyst, and reacting for 24 hours at 45 ℃ under the protection of nitrogen; then adding 800 parts of ethyl acetate for purification and washing for 3-6 times, and carrying out suction filtration and drying to obtain the Chinese tallow kernel oil-based unsaturated diacid monomer.
(2) 100 parts of Chinese tallow kernel oil-based unsaturated diacid monomer, 100 parts of 1, 6-hexamethylenediamine, 400 parts of lithium chloride, 700 parts of pyridine and 600 parts of TPP are added into 800 parts of NMP (N-methylpyrrolidone) and mixed under the protection of inert gas.
(3) Placing the mixed system in an oil bath pan and continuously stirring, heating to 90 ℃ and keeping for 0.5h; the temperature was then gradually increased to 170℃and maintained for 2h.
(4) After cooling to room temperature, methanol was added to precipitate, followed by a mixture of methanol and pure water (V Methanol ：V Deionized water =1:1), washing, purifying, suction filtering, drying in a vacuum oven at 75 ℃ for 45 hours, and drying to obtain the Chinese tallow kernel oil-based unsaturated polyamide.
Comparative example 2
This comparative example provides a process for preparing a rubber seed oil-based unsaturated polyamide by the melt process comprising the steps of: the rubber seed oil-based unsaturated diacid monomer prepared in the example 1 and diamine react in an inert gas atmosphere according to a molar ratio of 1:1, a gradual heating method is adopted to reach 220 ℃, the temperature is kept for 3-6 hours, the cooling is carried out to room temperature, and the rubber seed oil-based unsaturated polyamide can be obtained after fishing out.
Comparative example 3
The comparative example provides a method for preparing Chinese tallow kernel oil-based unsaturated polyamide by a melting method, which comprises the following steps: the Chinese tallow kernel oil-based unsaturated diacid monomer prepared in the example 2 and diamine are reacted in an inert gas atmosphere according to the mol ratio of 1:1, the temperature is gradually raised to 220 ℃, the temperature is kept for 3 to 6 hours, the temperature is cooled to the room temperature, and the Chinese tallow kernel oil-based unsaturated polyamide can be obtained after fishing out.
Example 9
The biobased polyamide obtained in examples 5 to 8 and comparative examples 2 to 3 was heated at 220℃for 20 minutes while pressurizing for 20 minutes to melt-tablet the same into a film, and then a film sample was cut into dumbbell-shaped bars and the bars were stretched at a speed of 10mm/min, whereby mechanical properties were tested.
Stress-strain tests were performed on the biobased polyamide samples of examples 5-8, comparative examples 2-3, and the stress-strain curves are shown in FIG. 6. As can be seen from the figure, the woody oil-based polyamide prepared by the method has better mechanical properties than the polyamide obtained by directly adopting a melt polymerization method.
The biobased polyamide samples of examples 5-8, comparative examples 2-3 were subjected to the tensile strength, elongation at break, toughness, and Young's modulus test, and the test results are shown in Table 2.
TABLE 2 mechanical test results
| Sample of | Draw god strength (Mpa) | Elongation at break (%) | Toughness (MJ/m) 3 ) |
| Example 5 | 19.3 | 216.4 | 32.8 |
| Example 6 | 34.1 | 144.2 | 37.7 |
| Example 7 | 18.9 | 190.1 | 28.9 |
| Example 8 | 24.3 | 138.2 | 30.9 |
| Comparative example 2 | 18.5 | 33.4 | 5.6 |
| Comparative example 3 | 18.8 | 25.3 | 3.9 |
As can be seen from table 2, the woody oil-based polyamide prepared in the examples of the present application has excellent mechanical properties, which are significantly superior to those of the unsaturated polyamide prepared by the melt process. In addition, according to reference (Synthesis and Characterization of Unsaturated Biobased Polyamides from Plant oil. Acs sustaiable chem. Eng.2020,8, 8049-8058.) it uses unsaturated rapeseed oil fatty acid esters as raw materials, and under microwave radiation, cross-metathesis reaction occurs to produce E-octadeca-9-ene diester; then polymerizing E-octadeca-9-ene diester, p-dimethyl diamine and diethylenetriamine under the traditional heating condition to obtain two bio-based polyamides, wherein the pulling strength of the two bio-based polyamides is 18.45+/-1.23 MPa and 1.85+/-0.15 MPa respectively; the elongation at break is 22.11+ -1.57%, 71.69 + -3.91%, respectively. Therefore, the mechanical properties of the woody oil-based polyamide prepared by the method are obviously superior to those of the polyamide prepared by taking rapeseed oil as a raw material in the prior art.
Example 10
The biobased polyamide obtained in example 5 and comparative example 2 was heated at 220℃for 20 minutes while pressurizing for 20 minutes, melt-pressed into square film-like test pieces, and subjected to shape memory function test, shape change state and recovery process as shown in FIG. 7.
First, the sample of example 5 was heated to 150 ℃ and cooled to room temperature to obtain a permanent shape (see fig. 7 a); then heating the sample to 120 ℃, folding the sample into a windmill shape, and cooling the sample to room temperature to fix the sample into the windmill shape (shown in fig. 7 b); the windmill-shaped sample was then reheated to 120 ℃ and returned to a square sample within 40 seconds without any external force (as shown in fig. 7 c-f), indicating that the bio-based polyamide prepared in this application has excellent shape memory function.
The use principle and the advantages are that: the method comprises the steps of preparing woody oil-based unsaturated diacid monomer by taking woody oil as a raw material, mixing the woody oil-based unsaturated diacid monomer with diamine monomer under the auxiliary conditions of cosolvent, catalyst, solvent and the like, heating and stirring under the protection of inert gas for reaction, and then precipitating, washing, purifying and drying to obtain woody oil-based unsaturated polyamide; in the process of preparing the polyamide, the woody oil-based unsaturated polyamide with excellent mechanical property and shape memory function is obtained by regulating and controlling the reaction conditions of the woody oil-based unsaturated diacid monomer and the diamine monomer.
The mechanical properties of the polyamide are as follows: the breaking strength is 18.9-34.1MPa, the breaking elongation is 138.2-216.4%, the Young modulus is 114.4-240.4MPa, and the toughness is 28.9-37.7MJ/m 3 The method comprises the steps of carrying out a first treatment on the surface of the The polyamide film with fixed shape is heated and folded into any shape, cooled to room temperature and fixed into the shape, and after re-heating, the polyamide film can be quickly restored to the original fixed shape without applying any external force, and has excellent shape memory function.
The above embodiments are only for illustrating the technical solution of the present invention, and are not limiting; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit and scope of the technical solutions of the embodiments of the present invention.
Claims (1)
1. Use of a woody oil-based unsaturated diacid in the preparation of a polyamide characterized in that: the method comprises the following steps:
(1) Taking 100 parts by weight of Chinese tallow kernel oil fatty acid and 0.5 part by weight of second generation Grubbs catalyst, and reacting for 24 hours at 45 ℃ under the protection of nitrogen; then adding 800 parts of ethyl acetate for purification and washing for 3-6 times, and carrying out suction filtration and drying to obtain the Chinese tallow kernel oil-based unsaturated diacid monomer;
(2) Adding 100 parts of Chinese tallow kernel oil-based unsaturated diacid monomer, 100 parts of 1, 6-hexamethylenediamine, 300 parts of lithium chloride, 600 parts of pyridine and 200 parts of TPP into 400 parts of NMP (N-methylpyrrolidone) and mixing under the protection of inert gas;
(3) Placing the mixed system in an oil bath pan and continuously stirring, heating to 80 ℃ and keeping for 1h; then gradually heating the temperature to 160 ℃ and keeping for 6 hours;
(4) Cooling to room temperature, precipitating with methanol, washing with mixed solution of methanol and pure water, and purifying, wherein the mixed solution is V Methanol ：V Deionized water And (2) carrying out suction filtration, and drying in a vacuum oven at 70 ℃ for 48 hours to obtain the Chinese tallow kernel oil-based unsaturated polyamide.
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