CN116462600B - Multifunctional aliphatic long-chain diester, preparation method, application and prepared functional polyamide thereof - Google Patents
Multifunctional aliphatic long-chain diester, preparation method, application and prepared functional polyamide thereof Download PDFInfo
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- 150000005690 diesters Chemical class 0.000 title claims abstract description 60
- 239000004952 Polyamide Substances 0.000 title claims abstract description 59
- 229920002647 polyamide Polymers 0.000 title claims abstract description 59
- 125000001931 aliphatic group Chemical group 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- ANLABNUUYWRCRP-UHFFFAOYSA-N 1-(4-nitrophenyl)cyclopentane-1-carbonitrile Chemical compound C1=CC([N+](=O)[O-])=CC=C1C1(C#N)CCCC1 ANLABNUUYWRCRP-UHFFFAOYSA-N 0.000 claims abstract description 56
- XPQPWPZFBULGKT-UHFFFAOYSA-N undecanoic acid methyl ester Natural products CCCCCCCCCCC(=O)OC XPQPWPZFBULGKT-UHFFFAOYSA-N 0.000 claims abstract description 56
- 239000000178 monomer Substances 0.000 claims abstract description 50
- 239000004593 Epoxy Substances 0.000 claims abstract description 27
- NHQDETIJWKXCTC-UHFFFAOYSA-N 3-chloroperbenzoic acid Chemical compound OOC(=O)C1=CC=CC(Cl)=C1 NHQDETIJWKXCTC-UHFFFAOYSA-N 0.000 claims abstract description 26
- -1 amine compounds Chemical class 0.000 claims abstract description 23
- 238000007142 ring opening reaction Methods 0.000 claims abstract description 6
- 238000006735 epoxidation reaction Methods 0.000 claims abstract description 4
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 46
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical group ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 20
- 239000002904 solvent Substances 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 11
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 10
- 239000003960 organic solvent Substances 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 6
- 239000005457 ice water Substances 0.000 claims description 6
- 239000012298 atmosphere Substances 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 125000003158 alcohol group Chemical group 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000006068 polycondensation reaction Methods 0.000 abstract description 13
- 230000015572 biosynthetic process Effects 0.000 abstract description 6
- 229920000642 polymer Polymers 0.000 abstract description 5
- 238000003786 synthesis reaction Methods 0.000 abstract description 5
- 238000011084 recovery Methods 0.000 abstract description 4
- 230000002194 synthesizing effect Effects 0.000 abstract description 3
- 239000004359 castor oil Substances 0.000 abstract description 2
- 235000019438 castor oil Nutrition 0.000 abstract description 2
- 125000000524 functional group Chemical group 0.000 abstract 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 abstract description 2
- 238000001308 synthesis method Methods 0.000 abstract description 2
- 230000001105 regulatory effect Effects 0.000 abstract 1
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 229940057499 anhydrous zinc acetate Drugs 0.000 description 10
- 239000003921 oil Substances 0.000 description 10
- 235000019198 oils Nutrition 0.000 description 10
- DJWUNCQRNNEAKC-UHFFFAOYSA-L zinc acetate Chemical group [Zn+2].CC([O-])=O.CC([O-])=O DJWUNCQRNNEAKC-UHFFFAOYSA-L 0.000 description 10
- 238000001035 drying Methods 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 239000012299 nitrogen atmosphere Substances 0.000 description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 238000005481 NMR spectroscopy Methods 0.000 description 5
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 238000002390 rotary evaporation Methods 0.000 description 5
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical class [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 125000004185 ester group Chemical group 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 238000001953 recrystallisation Methods 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 235000015112 vegetable and seed oil Nutrition 0.000 description 4
- 239000008158 vegetable oil Substances 0.000 description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 3
- 239000002861 polymer material Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- RRAFCDWBNXTKKO-UHFFFAOYSA-N eugenol Chemical compound COC1=CC(CC=C)=CC=C1O RRAFCDWBNXTKKO-UHFFFAOYSA-N 0.000 description 2
- 229920001002 functional polymer Polymers 0.000 description 2
- 150000003335 secondary amines Chemical group 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- NPBVQXIMTZKSBA-UHFFFAOYSA-N Chavibetol Natural products COC1=CC=C(CC=C)C=C1O NPBVQXIMTZKSBA-UHFFFAOYSA-N 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 239000005770 Eugenol Substances 0.000 description 1
- UVMRYBDEERADNV-UHFFFAOYSA-N Pseudoeugenol Natural products COC1=CC(C(C)=C)=CC=C1O UVMRYBDEERADNV-UHFFFAOYSA-N 0.000 description 1
- 238000005865 alkene metathesis reaction Methods 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000005102 attenuated total reflection Methods 0.000 description 1
- 229920013724 bio-based polymer Polymers 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005686 cross metathesis reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 229960002217 eugenol Drugs 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 125000003142 tertiary amide group Chemical group 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C229/00—Compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C229/02—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton
- C07C229/04—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated
- C07C229/22—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated the carbon skeleton being further substituted by oxygen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C227/04—Formation of amino groups in compounds containing carboxyl groups
- C07C227/06—Formation of amino groups in compounds containing carboxyl groups by addition or substitution reactions, without increasing the number of carbon atoms in the carbon skeleton of the acid
- C07C227/08—Formation of amino groups in compounds containing carboxyl groups by addition or substitution reactions, without increasing the number of carbon atoms in the carbon skeleton of the acid by reaction of ammonia or amines with acids containing functional groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/14—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with organic peracids, or salts, anhydrides or esters thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/38—Compounds containing oxirane rings with hydrocarbon radicals, substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D303/40—Compounds containing oxirane rings with hydrocarbon radicals, substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals by ester radicals
- C07D303/42—Acyclic compounds having a chain of seven or more carbon atoms, e.g. epoxidised fats
-
- 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
- C08G69/44—Polyester-amides
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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)
- Polyamides (AREA)
Abstract
The invention discloses a multi-functionality fat long-chain diester, a preparation method, application and prepared functional polyamide. The multi-functional aliphatic long chain diester is obtained by taking castor oil derivative methyl undecylenate containing terminal double bonds as a raw material, adopting m-CPBA to carry out double bond epoxidation, synthesizing an epoxy monomer, and carrying out epoxy ring opening reaction by using amine compounds, wherein the structural formula is as followsThe diester monomer can be used in the synthesis of bio-based functional polyamides by self-polycondensation or copolycondensation. The performance of the multifunctional aliphatic long-chain diester monomer applied to the polymer can be effectively regulated and controlled through the functional groups, the synthesis method is simple and efficient, a new thought is provided for synthesizing the functional polyamide, the functional polyamide prepared by self-polycondensation has good elastic recovery, and the functional polyamide prepared by copolycondensation has excellent mechanical properties.
Description
Technical Field
The invention relates to the technical field of vegetable oil functional polymer materials, in particular to a multifunctional aliphatic long-chain diester, a preparation method, application and prepared functional polyamide.
Background
In recent years, due to the increasingly growing environmental problems and the continuous exhaustion of fossil fuels, bio-based polymer materials are increasingly applied due to the characteristics of wide sources of raw materials, easiness in structural modification and the like, and particularly, the vegetable oil has the advantages of world-wide availability, biodegradability, reproducibility, sustainability and low toxicity compared with petroleum resources, so that the vegetable oil functional polymer materials are well developed.
Vegetable oils can participate in a wide variety of modifications and reactions to produce a variety of different monomers and polymer precursors, particularly long chain alpha, omega-difunctional compounds in which the long methylene sequence renders the molecular chain softer and can impart useful properties such as hydrophobicity or crystallinity, and are of great importance in the synthesis of long chain aliphatic polymers. The main methods for synthesizing the alpha, omega-difunctional compounds at present are olefin metathesis (Le,Samart et al.Efficient Conversion of Renewable Unsaturated Fatty Acid Methyl Esters by Cross-Metathesis with Eugenol.ACS Omega 3,11041-11049(2018))、 isomerization-hydroxycarbonylation (Goldbach,Falivene et al.Single-Step Access to Long-Chainα,ω-Dicarboxylic Acids by Isomerizing Hydroxycarbonylation of Unsaturated Fatty Acids.ACS Catalysis 6,8229-8238(2016))、 biotechnological enzyme catalysis method (Lu,Ness et al.Biosynthesis of monomers for plastics from renewable oils.J Am Chem Soc 132,15451-15455(2010)) and the like, but most of the methods have the problems of expensive catalysts, harsh reaction conditions, difficult product separation and the like, so that a feasible approach is still lacking in how to simply and efficiently synthesize the aliphatic long-chain alpha, omega-difunctional compounds.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a fatty long-chain alpha, omega-difunctional monomer containing functional groups such as secondary amine and hydroxyl, a preparation method thereof and a functional polyamide prepared by the same, wherein the preparation method is simple and efficient, the condition is mild, and the synthesized functional polyamide has excellent mechanical properties.
The invention solves the technical problems by the following technical means:
a multi-functionality aliphatic long chain diester having the structural formula:
the invention also provides a preparation method of the multi-functionality fatty long-chain diester, which takes methyl undecylenate as a raw material, epoxidizes terminal double bonds to obtain methyl undecylenate epoxy monomers, and then uses amine compounds to perform epoxy ring-opening reaction to obtain the multi-functionality fatty long-chain diester.
Preferably, the preparation method of the multi-functionality fat long-chain diester comprises the following steps:
s1, uniformly mixing methyl undecylenate and an organic solvent to obtain a methyl undecylenate solution; uniformly mixing 3-chloroperoxybenzoic acid with an organic solvent to obtain a 3-chloroperoxybenzoic acid solution;
S2, under the ice water bath condition, mixing a 3-chloroperoxybenzoic acid solution with a methyl undecylenate solution, then carrying out a reaction, adding anhydrous sodium carbonate, continuing the reaction to obtain a reaction solution, and carrying out post-treatment to obtain a methyl undecylenate epoxy monomer;
S3, dissolving the methyl undecylenate epoxy monomer in a solvent, adding an amine compound, and then reacting to obtain the multi-functionality aliphatic long-chain diester.
Preferably, in S2, the mass ratio of 3-chloroperoxybenzoic acid in the 3-chloroperoxybenzoic acid solution to methyl undecylenate and anhydrous sodium carbonate in the methyl undecylenate solution is 11-66:10-60:5-30 parts; in S3, the mass ratio of the amine compound to the methyl undecylenate epoxy monomer is 6-66:10-22.
Preferably, in S1, the organic solvent is dichloromethane; in S3, the solvent is an alcohol solvent, and the amine compound is ammonia water.
Preferably, the alcohol solvent is absolute ethanol.
Preferably, in S2, the 3-chloroperoxybenzoic acid solution and the methyl undecylenate solution are mixed and then reacted for 0.5 to 1 hour; adding anhydrous sodium carbonate to continue the reaction for 16 hours to obtain a reaction solution; in S3, the temperature of the reaction is room temperature and the time is 12-36h.
Preferably, in S1, the mass-volume ratio of the methyl undecylenate to the organic solvent is 10-60g:40-240mL; the mass volume ratio of the 3-chloroperoxybenzoic acid to the organic solvent is 11-66g:66-396mL.
Preferably, in S2, the post-treatment includes washing the reaction solution with water, a saturated sodium thiosulfate solution, a saturated sodium bicarbonate solution, a saturated saline solution, and an overbased alumina column to remove acid, drying over anhydrous sodium sulfate, and rotary evaporation treatment.
Preferably, in S3, the reaction further comprises recrystallizing the product after completion of the reaction.
Preferably, in S3, the mass volume ratio of the methyl undecylenate epoxy monomer to the solvent is 10-22g:10-45ml.
The invention also provides application of the multi-functionality fatty long-chain diester in preparation of polyamide.
The invention also provides a functional polyamide which is prepared by adopting the polyfunctional aliphatic long-chain diester as a monomer to perform self-polycondensation or copolycondensation with a diamine compound.
The invention also provides a preparation method of the functional polyamide, which comprises the following steps: 2-8 parts by weight of polyfunctional aliphatic long-chain diester and 4X 10 -3-1.6×10-2 parts by weight of catalyst are heated to 88-90 ℃ to melt under the inert gas atmosphere, and then reacted for 3 hours; heating the reaction solution to 98-100 ℃ for reaction for 3 hours; then heating to 140-200 ℃ to react into solid state, and obtaining the functional polyamide.
The invention also provides a preparation method of the functional polyamide, which comprises the following steps: heating 4-8 parts by weight of polyfunctional aliphatic long-chain diester, 0.8-2.5 parts by weight of diamine compound and 8×10 -3-1.6×10-2 parts by weight of catalyst to 88-90 ℃ under inert gas atmosphere to melt, and then reacting for 3 hours; heating the reaction solution to 98-100 ℃ for reaction for 3 hours; then heating to 135-145 ℃ to react into solid state, thus obtaining the functional polyamide.
Preferably, in the preparation method of the functional polyamide, the catalyst is anhydrous zinc acetate; the diamine compound is 1, 6-hexamethylenediamine.
The invention has the advantages that:
(1) According to the invention, epoxy ring opening is carried out by using amine compounds after double bond epoxidation to prepare the multi-functionality aliphatic long-chain diester, wherein the existence of functional group secondary amine and hydroxyl can effectively regulate and control the performance of polyamide in the process of being applied to polyamide synthesis.
(2) The multi-functionality fatty long-chain diester is obtained by epoxidation of castor oil derivative methyl undecylenate and ring-opening synthesis of amine compounds, the synthesis method is simple, the reaction is carried out at room temperature and normal pressure, no extra expensive catalyst is needed, and the product is purified by simple recrystallization, so that the method is simple and efficient.
(3) The functional polyamide synthesized by self-polycondensation of the polyfunctional aliphatic long-chain diester monomer has good rebound resilience, and the elastic recovery rate can reach 97.6% at most after cyclic stretching for 5 times.
(4) The functional polyamide synthesized by copolycondensation of the polyfunctional aliphatic long-chain diester monomer has good mechanical properties, and specific mechanical property parameters are as follows: the breaking strength of the functional polyamide is 4-43MPa, and the breaking elongation is 170-265%.
Drawings
FIG. 1 is a nuclear magnetic resonance spectrum of methyl undecylenate, methyl undecylenate epoxy monomer and polyfunctional aliphatic long chain diester of example 1 of the present invention;
FIG. 2 is an infrared spectrum of methyl undecylenate, methyl undecylenate epoxy monomer and polyfunctional aliphatic long chain diester of example 1 of the present invention;
FIG. 3 is a nuclear magnetic resonance spectrum of the polyfunctional aliphatic long-chain diester prepared in examples 2 to 4 of the present invention;
FIG. 4 is an infrared spectrum of the multifunctional aliphatic long-chain Diester (DHMUA) of example 1 and the self-polycondensation functional polyamide prepared in example 5 of the present invention;
FIG. 5 is a cyclic tensile stress-strain curve of the self-polycondensing functional polyamide prepared in examples 5-8 according to the invention;
FIG. 6 is an infrared spectrum of the multifunctional aliphatic long-chain Diester (DHMUA) of example 1 and the copolycondensation functional polyamide prepared in example 9 of the present invention;
FIG. 7 is a uniaxial tensile stress-strain curve of copolycondensation functional polyamides prepared in examples 9-13 according to the present invention.
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.
The test materials, reagents and the like used in the examples described below are commercially available unless otherwise specified.
Those of skill in the art, without any particular mention of the techniques or conditions, may follow the techniques or conditions described in the literature in this field or follow the product specifications.
Example 1
A method for preparing a multi-functionality fat long chain diester, comprising the following steps: 60g of methyl undecylenate was dissolved in 240mL of methylene chloride to obtain a methyl undecylenate solution, and 66g of 3-chloroperoxybenzoic acid was dissolved in 396mL of methylene chloride to obtain a 3-chloroperoxybenzoic acid solution. Under the ice water bath condition, uniformly mixing the methyl undecylenate solution and the 3-chloroperoxybenzoic acid solution, adding 30g of anhydrous sodium carbonate for continuous reaction for 16h after reacting for 1h, respectively washing the obtained product by liquid separation of water, saturated sodium thiosulfate solution, saturated sodium bicarbonate solution and saturated saline solution until the solution is clear and transparent, removing acid by an over-alkaline alumina column, drying by anhydrous sodium sulfate, and removing the solvent by rotary evaporation to obtain the methyl undecylenate epoxy monomer. Dissolving 22g of methyl undecylenate epoxy monomer by using 45mL of absolute ethyl alcohol, adding 66g of ammonia water (mass fraction is 25-28%) into the solution, reacting for 12 hours at room temperature, and recrystallizing the obtained product by using methanol to obtain white powdery solid, wherein the white powdery solid is polyfunctional aliphatic long-chain diester; the specific reaction formula is as follows:
As can be seen by comparing the nuclear magnetic resonance hydrogen spectra of methyl undecylenate and methyl undecylenate epoxy monomers in FIG. 1, the characteristic absorption peaks at k, j at 4.91-4.99ppm and 5.79ppm in FIG. 1 completely disappeared, and the characteristic absorption peaks at k ', j' at 2.43ppm,2.71ppm and 2.87ppm appear, indicating that methyl undecylenate has been completely converted to methyl undecylenate epoxy monomer. The occurrence of the characteristic peaks of k "at 2.44-2.52ppm and 2.67-2.73ppm after ring opening demonstrates successful preparation of the multi-functionality long-chain aliphatic diester monomer, MU in fig. 2 represents methyl undecylenate, EMU represents methyl undecylenate epoxy monomer, DHMUA represents multi-functionality long-chain aliphatic diester, and the variation of the characteristic peaks of carbon-carbon double bonds, epoxy groups, secondary amines and hydroxyl groups in the figure also demonstrates successful preparation of the multi-functionality long-chain aliphatic diester monomer.
Example 2
A method for preparing a multi-functionality fat long chain diester, comprising the following steps: 40g of methyl undecylenate was dissolved in 160mL of methylene chloride to obtain a methyl undecylenate solution, and 44g of 3-chloroperoxybenzoic acid was dissolved in 264mL of methylene chloride to obtain a 3-chloroperoxybenzoic acid solution. Under the ice water bath condition, uniformly mixing the methyl undecylenate solution and the 3-chloroperoxybenzoic acid solution, adding 21.30g of anhydrous sodium carbonate for continuous reaction for 16h after reacting for 1h, respectively washing the obtained product by separating water, saturated sodium thiosulfate solution, saturated sodium bicarbonate solution and saturated saline solution until the solution is clear and transparent, removing acid from the over-alkaline alumina column, drying the over-alkaline alumina column, and removing the solvent by rotary evaporation to obtain the methyl undecylenate epoxy monomer. 22g of methyl undecylenate epoxy monomer is dissolved by using 23mL of absolute ethyl alcohol, 33g of ammonia water (mass fraction is 25-28%) is added into the solution to react for 36 hours at room temperature, methanol recrystallization is carried out, and white powder solid is obtained after drying, namely the polyfunctional aliphatic long-chain diester. As shown in FIG. 3, the nuclear magnetic resonance hydrogen spectrum of the multi-functional aliphatic long-chain diester monomer prepared in this example shows high purity.
Example 3
A method for preparing a multi-functionality fat long chain diester, comprising the following steps: 20g of methyl undecylenate was dissolved in 80mL of methylene chloride to obtain a methyl undecylenate solution, and 22g of 3-chloroperoxybenzoic acid was dissolved in 132mL of methylene chloride to obtain a 3-chloroperoxybenzoic acid solution. Under the ice water bath condition, uniformly mixing the methyl undecylenate solution and the 3-chloroperoxybenzoic acid solution, adding 10g of anhydrous sodium carbonate for continuous reaction for 16h after reacting for 0.5h, respectively washing the obtained product by separating water, saturated sodium thiosulfate solution, saturated sodium bicarbonate solution and saturated saline solution until the solution is clear and transparent, removing acid from the over-alkaline alumina column, drying the over-alkaline alumina column, and removing the solvent by rotary evaporation to obtain the methyl undecylenate epoxy monomer. 14.5g of methyl undecylenate epoxy monomer is dissolved by using 15mL of absolute ethyl alcohol, 13.6g of ammonia water (mass fraction is 25-28%) is added into the solution to react for 24 hours at room temperature, methanol recrystallization is carried out, and white powder solid is obtained after drying, namely the polyfunctional aliphatic long-chain diester. As shown in FIG. 3, the nuclear magnetic resonance hydrogen spectrum of the multi-functional aliphatic long-chain diester monomer prepared in this example shows high purity.
Example 4
A method for preparing a multi-functionality fat long chain diester, comprising the following steps: 10g of methyl undecylenate was dissolved in 40mL of methylene chloride to obtain a methyl undecylenate solution, and 11g of 3-chloroperoxybenzoic acid was dissolved in 66mL of methylene chloride to obtain a 3-chloroperoxybenzoic acid solution. Under the ice water bath condition, uniformly mixing the methyl undecylenate solution and the 3-chloroperoxybenzoic acid solution, adding 5g of anhydrous sodium carbonate for continuous reaction for 16h after reacting for 1h, respectively washing the obtained product by liquid separation of water, saturated sodium thiosulfate solution, saturated sodium bicarbonate solution and saturated saline solution until the solution is clear and transparent, removing acid by an over-alkaline alumina column, drying by anhydrous sodium sulfate, and removing the solvent by rotary evaporation to obtain the methyl undecylenate epoxy monomer. 10g of methyl undecylenate epoxy monomer is dissolved by using 10mL of absolute ethyl alcohol, 6g of ammonia water (mass fraction is 25-28%) is added into the solution to react for 36h at room temperature, methanol recrystallization is carried out, and white powder solid is obtained after drying, namely the polyfunctional aliphatic long-chain diester. As shown in FIG. 3, the nuclear magnetic resonance hydrogen spectrum of the multi-functional aliphatic long-chain diester monomer prepared in this example shows high purity.
Example 5
A preparation method of self-polycondensation functional polyamide comprises the following steps: 8.00g of the polyfunctional aliphatic long-chain diester monomer of example 1 and 16mg of anhydrous zinc acetate were added to a reaction vessel, the mixture was melted in an oil bath at 90℃under a nitrogen atmosphere and reacted for 3 hours, then the temperature was raised to 100℃and reacted for 3 hours, and then the temperature was raised to 180℃and reacted for 2.5 hours, and the product was taken out to obtain the self-polycondensation functional polyamide.
As shown in FIG. 4, after the polyfunctional aliphatic long-chain diester monomer of the present invention is reacted according to example 5, the peak of the ester group at 1742cm -1 is obviously weakened, the peak of the ester group carbonyl group newly generated after the reaction is shifted to 1735cm -1, and the occurrence of the peak of the tertiary amide group carbonyl group at 1613cm -1 newly generated represents a successful reaction, namely, the polyfunctional aliphatic long-chain diester monomer is successfully self-polycondensed to synthesize the functional polyamide.
Example 6
A preparation method of self-polycondensation functional polyamide comprises the following steps: 4.00g of the polyfunctional aliphatic long-chain diester monomer of example 1 and 8mg of anhydrous zinc acetate were added to a reaction vessel, the mixture was melted in an oil bath at 89℃under a nitrogen atmosphere and reacted for 3 hours, then the temperature was raised to 99℃and reacted for 3 hours, and then the temperature was raised to 160℃and reacted for 3 hours to obtain the self-polycondensation functional polyamide.
Example 7
A preparation method of self-polycondensation functional polyamide comprises the following steps: 2.00g of the polyfunctional aliphatic long-chain diester monomer of example 1 and 4mg of anhydrous zinc acetate were added to a reaction vessel, the mixture was melted in an oil bath at 88℃under a nitrogen atmosphere and reacted for 3 hours, then the temperature was raised to 98℃and reacted for 3 hours, and then the temperature was raised to 140℃and reacted for 3 hours, and the product was taken out to obtain the self-polycondensation functional polyamide.
Example 8
A preparation method of self-polycondensation functional polyamide comprises the following steps: 4.00g of the polyfunctional aliphatic long-chain diester monomer of example 1 and 8mg of anhydrous zinc acetate were added to a reaction vessel, the mixture was melted in an oil bath at 90℃under a nitrogen atmosphere and reacted for 3 hours, then the temperature was raised to 100℃and reacted for 3 hours, and then the temperature was raised to 200℃and reacted for 2 hours, and the product was taken out to obtain the self-polycondensation functional polyamide.
The cyclic tensile stress-strain diagram shown in fig. 5 shows that the self-polycondensing functional polyamides described in examples 5-8 have a high elastic recovery.
Example 9
A preparation method of copolycondensation functional polyamide comprises the following steps: 8.00g of the polyfunctional aliphatic long-chain diester monomer in example 1, 2.50g of 1, 6-hexamethylenediamine and 16mg of anhydrous zinc acetate were charged into a reaction vessel, the mixture was melted in an oil bath at 88℃under a nitrogen atmosphere and reacted for 3 hours, then the temperature was raised to 98℃and reacted for 3 hours, then the temperature was raised to 140℃and reacted for 1.5 hours, and the product was taken out to obtain the copolycondensation functional polyamide.
As shown in FIG. 6, after the multi-functional long-chain aliphatic diester monomer is reacted according to the embodiment 9, the peak of the ester group is obviously weakened, the peak of the carbonyl group of the ester group after the reaction is deviated, the appearance of the characteristic peak of the newly generated amide group, which represents the successful reaction, namely the successful copolycondensation of the multi-functional long-chain aliphatic diester monomer and the 1, 6-hexamethylenediamine, is shown in the reaction process.
Example 10
A preparation method of copolycondensation functional polyamide comprises the following steps: 4.00g of the polyfunctional aliphatic long-chain diester monomer of example 1, 1.045g of 1, 6-hexamethylenediamine and 8mg of anhydrous zinc acetate were charged into a reaction vessel, the mixture was melted in an oil bath at 88℃under a nitrogen atmosphere and reacted for 3 hours, then the temperature was raised to 99℃and reacted for 3 hours, then the temperature was raised to 140℃and reacted for 2 hours, and the product was taken out to obtain the copolycondensation functional polyamide.
Example 11
A preparation method of copolycondensation functional polyamide comprises the following steps: 6.00g of the polyfunctional aliphatic long-chain diester monomer of example 1, 1.254g of 1, 6-hexamethylenediamine and 12mg of anhydrous zinc acetate were charged into a reaction vessel, the mixture was melted in an oil bath at 89℃under a nitrogen atmosphere and reacted for 3 hours, then the temperature was raised to 100℃and reacted for 3 hours, then the temperature was raised to 135℃and reacted for 2 hours, and the product was taken out to obtain the copolycondensation functional polyamide.
Example 12
A preparation method of copolycondensation functional polyamide comprises the following steps: 8.00g of the polyfunctional aliphatic long-chain diester monomer of example 1, 1.254g of 1, 6-hexamethylenediamine and 16mg of anhydrous zinc acetate were charged into a reaction vessel, the mixture was melted in an oil bath at 90℃under a nitrogen atmosphere and reacted for 3 hours, then the temperature was raised to 100℃and reacted for 3 hours, then the temperature was raised to 140℃and reacted for 2.5 hours, and the product was taken out to obtain the copolycondensation functional polyamide.
Example 13
A preparation method of copolycondensation functional polyamide comprises the following steps: 7.656g of the polyfunctional aliphatic long-chain diester monomer in example 1, 0.8g of 1, 6-hexamethylenediamine and 15mg of anhydrous zinc acetate were added into a reaction vessel, the mixture was melted in an oil bath at 90 ℃ under nitrogen atmosphere and then reacted for 3 hours, then the temperature was raised to 100 ℃ and reacted for 3 hours, then the temperature was raised to 145 ℃ and reacted for 2.5 hours, and the product was taken out to obtain the copolycondensation functional polyamide.
The stress-strain diagram shown in fig. 7 shows that the copolycondensation functional polyamides described in examples 9-13 have good mechanical properties.
Table 1 shows the performance statistics of the self-polycondensing functional polyamides prepared in examples 5-8 according to the invention; table 2 shows the performance statistics of copolycondensation functional polyamides prepared in examples 9-13 of the present invention;
TABLE 1
TABLE 2
The performance statistics shown in Table 1 show the specific elastic recovery of the self-polycondensing functional polyamides described in examples 5-8; the performance data statistics shown in Table 2 show the specific stress and strain values for copolycondensation functional polyamides described in examples 9-13; from tables 1 and 2, it is apparent that such a polyfunctional aliphatic long-chain Diester (DHMUA) can be used in polyamide synthesis to prepare functional polyamides having various properties.
The specific performance test method in the application is as follows:
fourier transform infrared spectroscopy (FTIR)
And (3) placing a sample to be tested in a vacuum drying oven for drying treatment, using a Fourier infrared spectrometer (Bruker Tensor 27) tester, adopting a KBr tabletting method for a solid sample, adopting ATR (attenuated total reflection) for a liquid and polymer sample (polymer is hot pressed into uniform slices), and measuring the wave number to be 4000-500cm -1.
Nuclear magnetic resonance spectrum analysis (1 H-NMR)
5-10Mg of the sample was dissolved in 0.5mL of deuterated chloroform and measured by AGILENT DD2 Hz nuclear magnetic resonance spectroscopy.
Analysis of mechanical Properties
The mechanical properties of the sample bars are tested according to GB/T1040.3-2006, the stretching rate is 20mm/min, and the stress strain stretching test is carried out under the room temperature condition. Repeatedly measuring each sample by uniaxial stretching for 3 times, and calculating an average value; cycle stretching was performed 5 times at 10%, 20%, 30%, 40%, 50% step increase of the initial gauge (example 8 cycle stretching 3 times to 30% of the initial gauge due to weaker performance).
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 (10)
1. A multi-functionality aliphatic long chain diester characterized by: the structural formula is as follows:
2. A process for the preparation of the multifunctional aliphatic long-chain diester of claim 1, wherein: methyl undecylenate is used as a raw material, terminal double bonds are subjected to epoxidation to obtain methyl undecylenate epoxy monomers, and then amine compounds are used for epoxy ring-opening reaction to obtain the multi-functionality aliphatic long-chain diester.
3. The method for producing a multi-functional aliphatic long-chain diester according to claim 2, wherein: the method comprises the following steps:
s1, uniformly mixing methyl undecylenate and an organic solvent to obtain a methyl undecylenate solution; uniformly mixing 3-chloroperoxybenzoic acid with an organic solvent to obtain a 3-chloroperoxybenzoic acid solution;
S2, under the ice water bath condition, mixing a 3-chloroperoxybenzoic acid solution with a methyl undecylenate solution, then carrying out a reaction, adding anhydrous sodium carbonate, continuing the reaction to obtain a reaction solution, and carrying out post-treatment to obtain a methyl undecylenate epoxy monomer;
S3, dissolving the methyl undecylenate epoxy monomer in a solvent, adding an amine compound, and then reacting to obtain the multi-functionality aliphatic long-chain diester.
4. A process for the preparation of a multi-functional aliphatic long chain diester according to claim 3, wherein: in S2, the mass ratio of the 3-chloroperoxybenzoic acid in the 3-chloroperoxybenzoic acid solution to the methyl undecylenate in the methyl undecylenate solution to the anhydrous sodium carbonate is 11-66:10-60:5-30 parts; in S3, the mass ratio of the amine compound to the methyl undecylenate epoxy monomer is 6-66:10-22.
5. A process for the preparation of a multi-functional aliphatic long chain diester according to claim 3, wherein: in S1, the organic solvent is dichloromethane; in S3, the solvent is an alcohol solvent, and the amine compound is ammonia water.
6. A process for the preparation of a multi-functional aliphatic long chain diester according to claim 3, wherein: in S2, mixing 3-chloroperoxybenzoic acid solution and methyl undecylenate solution, and then reacting for 0.5-1h; adding anhydrous sodium carbonate to continue the reaction for 16 hours to obtain a reaction solution; in S3, the temperature of the reaction is room temperature and the time is 12-36h.
7. Use of the multi-functional aliphatic long-chain diester according to claim 1 for the preparation of polyamides.
8. A functional polyamide comprising the polyfunctional aliphatic long-chain diester according to claim 1 as a monomer, which is self-polycondensed or copolypolycondensed with a diamine compound.
9. A process for the preparation of a functional polyamide as claimed in claim 8, comprising the steps of: 2-8 parts by weight of polyfunctional aliphatic long-chain diester and 4X 10 -3-1.6×10-2 parts by weight of catalyst are heated to 88-90 ℃ to melt under the inert gas atmosphere, and then reacted for 3 hours; heating the reaction solution to 98-100 ℃ for reaction for 3 hours; then heating to 140-200 ℃ to react into solid state, and obtaining the functional polyamide.
10. A process for the preparation of a functional polyamide as claimed in claim 8, comprising the steps of: heating 4-8 parts by weight of polyfunctional aliphatic long-chain diester, 0.8-2.5 parts by weight of diamine compound and 8×10 -3-1.6×10-2 parts by weight of catalyst to 88-90 ℃ under inert gas atmosphere to melt, and then reacting for 3 hours; heating the reaction solution to 98-100 ℃ for reaction for 3 hours; then heating to 135-145 ℃ to react into solid state, thus obtaining the functional polyamide.
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| US8841470B1 (en) * | 2010-08-26 | 2014-09-23 | The United States Of America, As Represented By The Secretary Of Agriculture | Process for preparation of nitrogen-containing vegetable oil-based lubricant additive |
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| US8841470B1 (en) * | 2010-08-26 | 2014-09-23 | The United States Of America, As Represented By The Secretary Of Agriculture | Process for preparation of nitrogen-containing vegetable oil-based lubricant additive |
| CN112707834A (en) * | 2019-10-24 | 2021-04-27 | 中国石油化工股份有限公司 | Ester compound and preparation method and application thereof |
| CN113024804A (en) * | 2021-04-25 | 2021-06-25 | 安徽农业大学 | Application of polyesteramide as reusable hot melt adhesive |
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