CN113667087A - Hydroxyl-terminated polyisoprene polyurethane synthesized by biological method and preparation method and application thereof - Google Patents
Hydroxyl-terminated polyisoprene polyurethane synthesized by biological method and preparation method and application thereof Download PDFInfo
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- terminated polyisoprene
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- 229920001195 polyisoprene Polymers 0.000 title claims abstract description 65
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 43
- 239000004814 polyurethane Substances 0.000 title claims abstract description 43
- 238000010170 biological method Methods 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title abstract description 13
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims abstract description 68
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000000178 monomer Substances 0.000 claims abstract description 15
- 239000004970 Chain extender Substances 0.000 claims abstract description 14
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 39
- 238000006243 chemical reaction Methods 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 23
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 16
- 239000012044 organic layer Substances 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 239000012043 crude product Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- 230000001376 precipitating effect Effects 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- 239000012153 distilled water Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 230000002194 synthesizing effect Effects 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- VFDYEMVVNIPATA-UHFFFAOYSA-N 2-ethyl-2-(hydroxymethyl)propane-1,3-diol;propane-1,2,3-triol Chemical compound OCC(O)CO.CCC(CO)(CO)CO VFDYEMVVNIPATA-UHFFFAOYSA-N 0.000 claims description 2
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims description 2
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 claims description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 2
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 2
- 230000000379 polymerizing effect Effects 0.000 claims description 2
- 238000003825 pressing Methods 0.000 claims description 2
- 239000000600 sorbitol Substances 0.000 claims description 2
- 238000010025 steaming Methods 0.000 claims description 2
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims description 2
- 229920003225 polyurethane elastomer Polymers 0.000 abstract description 11
- 238000003786 synthesis reaction Methods 0.000 abstract description 5
- 238000004260 weight control Methods 0.000 abstract description 2
- 239000000853 adhesive Substances 0.000 abstract 1
- 230000001070 adhesive effect Effects 0.000 abstract 1
- 239000002994 raw material Substances 0.000 description 13
- 238000012360 testing method Methods 0.000 description 10
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000000855 fermentation Methods 0.000 description 5
- 230000004151 fermentation Effects 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical group C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 3
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 239000008103 glucose Substances 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000012258 culturing Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000001963 growth medium Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000011218 seed culture Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- YHQXBTXEYZIYOV-UHFFFAOYSA-N 3-methylbut-1-ene Chemical compound CC(C)C=C YHQXBTXEYZIYOV-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- UUIRDIWGVMSEBE-UHFFFAOYSA-N acetylene propan-2-one Chemical compound C#C.CC(C)=O UUIRDIWGVMSEBE-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 229960000723 ampicillin Drugs 0.000 description 1
- AVKUERGKIZMTKX-NJBDSQKTSA-N ampicillin Chemical compound C1([C@@H](N)C(=O)N[C@H]2[C@H]3SC([C@@H](N3C2=O)C(O)=O)(C)C)=CC=CC=C1 AVKUERGKIZMTKX-NJBDSQKTSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 241000101345 bacterium G_02 Species 0.000 description 1
- 239000011942 biocatalyst Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 229960005091 chloramphenicol Drugs 0.000 description 1
- WIIZWVCIJKGZOK-RKDXNWHRSA-N chloramphenicol Chemical compound ClC(Cl)C(=O)N[C@H](CO)[C@H](O)C1=CC=C([N+]([O-])=O)C=C1 WIIZWVCIJKGZOK-RKDXNWHRSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000006471 dimerization reaction Methods 0.000 description 1
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000000895 extractive distillation Methods 0.000 description 1
- XPVUBPISXXCAGT-UHFFFAOYSA-N formaldehyde 2-methylprop-1-ene Chemical compound O=C.CC(C)=C XPVUBPISXXCAGT-UHFFFAOYSA-N 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 229920006247 high-performance elastomer Polymers 0.000 description 1
- 239000000411 inducer Substances 0.000 description 1
- BPHPUYQFMNQIOC-NXRLNHOXSA-N isopropyl beta-D-thiogalactopyranoside Chemical compound CC(C)S[C@@H]1O[C@H](CO)[C@H](O)[C@H](O)[C@H]1O BPHPUYQFMNQIOC-NXRLNHOXSA-N 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000013520 petroleum-based product Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/69—Polymers of conjugated dienes
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/6576—Compounds of group C08G18/69
- C08G18/6582—Compounds of group C08G18/69 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6588—Compounds of group C08G18/69 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
Abstract
The invention discloses hydroxyl-terminated polyisoprene polyurethane synthesized by a biological method, a preparation method and application thereof, belonging to the technical field of chemical synthesis. To provide a polyurethane having a high tensile strength, a high heat resistance and a high stability. The invention synthesizes hydroxyl-terminated polyisoprene by using an isoprene monomer synthesized by a biological method, and then carries out polymerization reaction with toluene diisocyanate to obtain hydroxyl-terminated polyisoprene polyurethane, wherein the polymerization reaction is carried out according to the following molar ratio: toluene diisocyanate in a molar ratio of 1:1.05 to 1:1.7, toluene diisocyanate: and the molar ratio of the chain extender is 2: 1-4: 1. The hydroxyl-terminated polyisoprene prepared by using the biological isoprene has the advantages of narrow molecular weight distribution, easy molecular weight control and the like; the polyurethane elastomer prepared from the biological isoprene has the advantages of excellent heat resistance, low modulus, high elongation and excellent adhesive force.
Description
Technical Field
The invention belongs to the technical field of chemical synthesis, and particularly relates to hydroxyl-terminated polyisoprene polyurethane synthesized by a biological method, and a preparation method and application thereof.
Background
The polyurethane elastomer is a high-performance elastomer, also called polyurethane rubber, and is an elastic polymer material containing more urethane groups in molecular chains. Because the polyurethane elastomer has a large number of polar groups, hydrogen bonds can be formed in molecules and among molecules, and the soft segment and the hard segment can form a micro-phase region and generate micro-phase separation. The polyurethane elastomer has excellent wear resistance and toughness due to the structural characteristics, is called wear-resistant rubber, can adjust the variety and the proportion of raw materials due to various polyurethane raw materials, and is suitable for various fields.
Although polyurethane elastomers have excellent mechanical properties and abrasion resistance, there are some problems. Taking polyurethane tires as an example, the heat resistance of the polyurethane tire is not high, and under high-frequency dynamic load, the temperature of the rubber tire can reach 120 ℃ in high-speed running, and the general service temperature of the polyurethane material cannot be higher than 80 ℃. During the driving and braking process, the temperature of the tire rises sharply and exceeds the melting point or the softening temperature of the polyurethane material, so that the use of the polyurethane tire is restricted. There is a need for polyurethanes with high tensile strength, high heat resistance and high stability.
Researchers have found that the main factor contributing to poor heat resistance of polyurethane elastomers is the ether bond in their molecular chains. When the temperature is raised to above 60 ℃, the hydrogen bonding effect mainly based on ether bonds disappears, so that the mechanical properties of the polyurethane elastomer such as tear strength, tear strength and the like are greatly reduced. Therefore, the content of ether bonds in the molecular chain of the polyurethane is improved, and the heat resistance of the polyurethane can be improved. The hydroxyl-terminated polyisoprene does not contain ether bond in molecular structure, replaces polyether type oligomer as an elastomer prepared by the raw material of polyurethane, is expected to reduce sensitivity and improve the thermal stability of the product.
At present, a bottleneck exists in the preparation of isoprene which is a main raw material of hydroxyl-terminated polyisoprene. The conventional isoprene is mainly prepared by a petroleum-based raw material isopentane, an isopentene dehydrogenation method, a chemical synthesis method (including an isobutene-formaldehyde method, an acetylene-acetone method and a propylene dimerization method) and a cracked C5 fraction extractive distillation method. However, the raw materials for producing isoprene by a chemical method mainly come from petroleum-based products, are non-renewable and have great pollution to the environment. With the increasing exhaustion of fossil resources, the source of raw materials has become a bottleneck problem restricting the preparation of isoprene.
In recent years, a new route for preparing isoprene by using renewable resources such as glucose and the like as raw materials and using a biocatalyst has been proposed, has the advantages of green and safe properties, sustainable raw materials, high product quality and the like, and has become a new direction for isoprene synthesis. However, due to the difference of synthetic raw materials and synthetic routes, the components of the biological isoprene product are different from those of the chemical isoprene product. For example, the main impurities in chemically processed isoprene include cyclopentadiene, piperylene, etc.; the biological isoprene does not contain cyclopentadiene, piperylene and the like, but contains some impurities such as oxygen-containing compounds and the like. Whether the biological isoprene can be used for preparing hydroxyl-terminated polyisoprene or not is not reported, and further polyurethane synthesis is not yet reported.
Disclosure of Invention
The invention aims to provide a polyurethane which is prepared by taking biological isoprene as a raw material and has high tensile strength, heat resistance and stability.
The invention provides hydroxyl-terminated polyisoprene polyurethane synthesized by a biological method, which comprises the following components: hydroxyl-terminated polyisoprene, toluene diisocyanate and a chain extender.
Further defined, the mole ratio of the hydroxyl-terminated polyisoprene, the toluene diisocyanate and the chain extender is as follows:
hydroxyl-terminated polyisoprene: toluene diisocyanate-1: 1.05 to 1:1.7, toluene diisocyanate: the chain extender is 2: 1-4: 1.
The invention also provides a method for preparing the hydroxyl-terminated polyisoprene polyurethane, which is to synthesize the hydroxyl-terminated polyisoprene polyurethane by using an isoprene monomer synthesized by a biological method.
Further limited, the method is to synthesize hydroxyl-terminated polyisoprene by using an isoprene monomer synthesized by a biological method, and then carry out polymerization reaction with toluene diisocyanate to obtain hydroxyl-terminated polyisoprene polyurethane.
Further defined, the method includes the steps of:
(1) adding hydroxyl-terminated polyisoprene into a three-port reactor, adjusting the temperature of an oil bath to 120 ℃, dehydrating for 2h under the condition of vacuum degree of-0.0095 MPa, and cooling to 90 ℃;
(2) adding a catalyst, stirring and mixing fully and uniformly;
(3) adding toluene diisocyanate, stirring uniformly, introducing nitrogen, reacting for 2-10 h until the system is fully mixed, and pre-polymerizing;
(4) adding a chain extender, continuing to react for 2-6 hours, carrying out the whole reaction process under the protection of nitrogen and under the heating condition of 60-90 ℃, precipitating and washing the mixed solution obtained by the reaction through methanol, and carrying out vacuum drying for 24 hours at 40 ℃ to obtain the hydroxyl-terminated polyisoprene polyurethane.
Further defined, the catalyst of step (3) is dibutyltin dilaurate.
Further defined, the chain extender in the step (4) is 1, 4-butanediol, 1, 6-hexanediol, glycerol trimethylolpropane, triethylene glycol, neopentyl glycol, sorbitol or diethanolamine.
Further defined, the method of synthesizing hydroxyl-terminated polyisoprene:
1) synthesizing 100g of isoprene monomer, 100g of methanol and 50% of H2O 230 g by a biological method, and uniformly mixing; controlling the temperature to keep the reaction system at the temperature of 108 ℃ and 122 ℃, and stopping the reaction after the reaction time is 5-7 h;
2) when the temperature in the kettle is reduced to 50 ℃, pressing the mixture out of the kettle to obtain a crude product;
3) and (3) placing the crude product in a three-neck flask, steaming to remove residual monomers and methanol/ethanol, then transferring an organic layer into a separating funnel, washing with distilled water at 100 ℃ for three times, standing for layering, taking the organic layer, and distilling under reduced pressure at 80 ℃ and 100.6kPa for 2 hours to obtain the transparent hydroxyl-terminated liquid polyisoprene.
Further defined, the hydroxyl-terminated polyisoprene has a molecular weight of 4000-.
The invention also provides application of the hydroxyl-terminated polyisoprene polyurethane in the fields of military affairs, anti-counterfeiting, encryption, clothing and medicine.
Has the advantages that: the hydroxyl-terminated polyisoprene prepared by using the biological isoprene has the advantages of narrow molecular weight distribution, easy molecular weight control and the like; the polyurethane elastomer prepared from the biological isoprene has the advantages of excellent heat resistance, low modulus and high elongation, and the preparation of the polyurethane elastomer from the biological isoprene can solve the bottleneck problem of raw materials and has the advantages of raw material sustainability and the like.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
The construction method of the engineering bacterium G02 is disclosed in the patent grant publication No. CN 106350476B.
Example 1 preparation of Bio-isoprene
And respectively inoculating the monoclonals of the engineering strain G02 to 5ml of seed culture medium, and culturing at 37 ℃ and 220rpm for 12-18 h to obtain a first-stage seed solution. Transferring 1ml of the first-level seeds to 100ml of a seed culture medium, and culturing at 37 ℃ and 220rpm for 12-18 h to obtain a second-level seed solution. Inoculating the secondary seeds into a 5L small fermentation tank filled with 2L fermentation medium according to the proportion of 1:100, adding ampicillin with the final concentration of 100 mug/mL, chloramphenicol with the final concentration of 34 mug/mL and glucose with the base sugar of 20-30 g/L. By adding ammonia water, the pH is kept at 7.0, the initial rotating speed is 400rpm, and the dissolved oxygen is controlled at 5-10%. The culture temperature is 37 ℃, when the culture is carried out until OD600 is within the range of 15-20, inducers IPTG and VB12 are added until the final concentrations are 0.5mM and 5 mu M respectively, the fermentation is carried out for 48-60 h at 30 ℃, the concentration of residual glucose is always maintained within the range of 0.1-0.5 g/L in the culture process, and the residual quantity of glycerol is below 1 g/L. And the fermentation tail gas enters a separation device after being subjected to water removal and carbon dioxide removal. Adopts high-strength activated carbon fiber (the specific surface area is 1200 m)2/kg) adsorbing low-concentration isoprene fermentation tail gas, desorbing the saturated adsorbed activated carbon fiber by using steam, and freezing and collecting isoprene by using a condenser.
The biological isoprene is analyzed by HPLC, and the result shows that the biological isoprene does not contain impurities such as cyclopentadiene, piperylene and the like, unlike the chemical isoprene. And the component analysis of the bio-based isoprene product obtained by separation proves that the purity of the product reaches 99.65 percent.
Example 2 preparation of Bioterminal hydroxypolyisoprene
100g of the biogenetic isoprene monomer prepared in example 1, 100g of methanol, and H were charged into a 0.5L autoclave2O2(50%) 30g, mixing well; controlling the temperature to keep the reaction system at (110 +/-2) DEG C, and stopping the reaction after the reaction time is 7 h; when the temperature in the kettle is reduced to 50 ℃, the mixture is pressed out of the kettle. And (3) placing the crude product in a 500mL three-neck flask, evaporating residual monomers and methanol/ethanol by using a rotary evaporator, then transferring an organic layer into a separating funnel, washing the organic layer with distilled water at 100 ℃ for three times, standing the organic layer for layering, taking the organic layer, and carrying out reduced pressure distillation for 2 hours at 80 ℃ and 100.6kPa to obtain the transparent hydroxyl-terminated liquid polyisoprene.
The relative molecular weight test adopts a 150C type GPC gel permeation chromatograph, tetrahydrofuran is used as a mobile phase, and a polystyrene standard molecular weight sample is used as a standard sample. By testing, initiator H2O2The content of the isoprene in the monomer biological method is 30%, the reaction temperature is controlled to be (110 +/-2) DEG C, the reaction time is 7 hours, the number average molecular weight of the prepared hydroxyl-terminated polyisoprene can be controlled to be 4000-5000, and the molecular weight distribution is 1.2.
Example 3 preparation of Bioterminal hydroxypolyisoprene
100g of the biogenetic isoprene monomer prepared in example 1, 100g of methanol, and H were charged into a 0.5L autoclave2O2(50%) 20g, mixing well; controlling the temperature to keep the reaction system at (120 +/-2) DEG C, and stopping the reaction after 5h of reaction time; when the temperature in the kettle is reduced to 50 ℃, the mixture is pressed out of the kettle. And (3) placing the crude product in a 500mL three-neck flask, evaporating residual monomers and methanol/ethanol by using a rotary evaporator, then transferring an organic layer into a separating funnel, washing the organic layer with distilled water at 100 ℃ for three times, standing the organic layer for layering, taking the organic layer, and carrying out reduced pressure distillation for 2 hours at 80 ℃ and 100.6kPa to obtain the transparent hydroxyl-terminated liquid polyisoprene.
By testing, initiator H2O2The method comprises the steps of accounting for 20% of isoprene content in a monomer biological method, controlling the reaction temperature to be (120 +/-2) DEG C, controlling the reaction time to be 5h, controlling the number average molecular weight of the prepared hydroxyl-terminated polyisoprene to be 4300-5200, and controlling the molecular weight distribution to be 1.25.
Example 4 preparation of polyurethane Using biobased hydroxyl terminated Polyisoprene
Taking a certain amount of hydroxyl-terminated liquid polyisoprene obtained in example 2, placing the hydroxyl-terminated liquid polyisoprene in a three-port reaction vessel, adjusting the temperature of an oil bath to 120 ℃, dehydrating for 2 hours under the condition of vacuum degree of minus 0.0095MPa, and cooling to 90 ℃; adding catalyst dibutyltin dilaurate (the total formula mass is 0.5%), stirring and fully mixing uniformly; adding a small excess of Toluene Diisocyanate (TDI), uniformly stirring, introducing nitrogen, reacting for 2-10 h until the system is fully mixed and prepolymerized; adding a metered chain extender 1, 4-butanediol, continuing to react for 2-6 h, carrying out the whole addition and chain extension reaction process under the protection of nitrogen and the heating condition of 60-90 ℃, precipitating and washing the mixed solution obtained by the reaction by using methanol, and carrying out vacuum drying for 24h at 40 ℃ to obtain the hydroxyl-terminated polyisoprene type polyurethane. Wherein the hydroxyl-terminated polyisoprene: toluene diisocyanate molar ratio is 1: 1.5; toluene diisocyanate: the molar ratio of 1, 4-butanediol was 3: 1. .
And (3) testing mechanical properties: on the prepared polyurethane elastomer film, 5 dumbbell-shaped samples with uniform thickness and no air bubbles are respectively cut by a cutter, the thickness and the width are respectively measured at the two ends and the middle part of the sample, the average value of the thickness and the width is calculated, then a stretching experiment is carried out on a stretching machine, the average tensile strength and the elongation at break of the 5 samples are taken as the tensile strength and the elongation at break of the sample, a WSM type universal electronic stretching experiment machine is used for measuring the tensile strength and the elongation at break of the PUE, a 500N sensor is adopted during the test, the tensile rate is 100mm/min, and the specification of the sample is 20mm multiplied by 4mm multiplied by 2 mm. Tests show that the prepared hydroxyl-terminated polyisoprene polyurethane has the tensile strength of 13.12MPa and the elongation at break of 332 percent.
And (3) testing thermal stability: using a thermogravimetric analyzer, the initial temperature is room temperature, the final temperature is 600 ℃, and the heating rate is 10 ℃/min. The initial decomposition temperature of the prepared hydroxyl-terminated polyisoprene polyurethane reaches 315 ℃ through testing. Exhibits excellent thermal stability.
Example 5 preparation of polyurethane Using biobased hydroxyl-terminated Polyisoprene
Taking a certain amount of hydroxyl-terminated liquid polyisoprene obtained in example 3, placing the hydroxyl-terminated liquid polyisoprene in a three-port reaction vessel, adjusting the temperature of an oil bath to 120 ℃, dehydrating for 2 hours under the condition of vacuum degree of minus 0.0095MPa, and cooling to 90 ℃; adding catalyst dibutyltin dilaurate (the total formula mass is 0.5%), stirring and fully mixing uniformly; adding a small excess of Toluene Diisocyanate (TDI), uniformly stirring, introducing nitrogen, reacting for 2-10 h until the system is fully mixed and prepolymerized; adding a metered chain extender 1, 4-butanediol, continuing to react for 2-6 h, carrying out the whole addition and chain extension reaction process under the protection of nitrogen and the heating condition of 60-90 ℃, precipitating and washing the mixed solution obtained by the reaction by using methanol, and carrying out vacuum drying for 24h at 40 ℃ to obtain the hydroxyl-terminated polyisoprene type polyurethane. Wherein the hydroxyl-terminated polyisoprene: toluene diisocyanate molar ratio is 1: 1.06; toluene diisocyanate: the molar ratio of 1, 4-butanediol was 2: 1.
Tests show that the prepared hydroxyl-terminated polyisoprene polyurethane has the tensile strength of 12.11MPa and the elongation at break of 310 percent. The prepared hydroxyl-terminated polyisoprene polyurethane has the initial decomposition temperature of 290 ℃ and shows excellent thermal stability.
Example 6 preparation of polyurethane Using biobased hydroxyl-terminated Polyisoprene
Taking a certain amount of hydroxyl-terminated liquid polyisoprene obtained in example 3, placing the hydroxyl-terminated liquid polyisoprene in a three-port reaction vessel, adjusting the temperature of an oil bath to 120 ℃, dehydrating for 2 hours under the condition of vacuum degree of minus 0.0095MPa, and cooling to 90 ℃; adding catalyst dibutyltin dilaurate (the total formula mass is 0.5%), stirring and fully mixing uniformly; adding a small excess of Toluene Diisocyanate (TDI), uniformly stirring, introducing nitrogen, reacting for 2-10 h until the system is fully mixed and prepolymerized; adding a metered chain extender 1, 4-butanediol, continuously reacting for 6 hours, carrying out the whole addition and chain extension reaction process under the protection of nitrogen and the heating condition of 80 ℃, precipitating and washing the mixed solution obtained by the reaction by using methanol, and carrying out vacuum drying for 24 hours at 40 ℃ to obtain the hydroxyl-terminated polyisoprene type polyurethane. Wherein the hydroxyl-terminated polyisoprene: toluene diisocyanate molar ratio is 1: 1.7; toluene diisocyanate: the molar ratio of 1, 4-butanediol was 4: 1.
Tests show that the prepared hydroxyl-terminated polyisoprene polyurethane has the tensile strength of 14.11MPa and the elongation at break of 280 percent. The initial decomposition temperature of the prepared hydroxyl-terminated polyisoprene polyurethane reaches 298 ℃. Exhibits excellent thermal stability.
Claims (10)
1. The hydroxyl-terminated polyisoprene polyurethane synthesized by a biological method is characterized by comprising the following components: hydroxyl-terminated polyisoprene, toluene diisocyanate and a chain extender.
2. The hydroxyl-terminated polyisoprene polyurethane as claimed in claim 1, wherein the molar ratio of the hydroxyl-terminated polyisoprene, toluene diisocyanate and chain extender is as follows:
hydroxyl-terminated polyisoprene: toluene diisocyanate-1: 1.05 to 1:1.7, toluene diisocyanate: the chain extender is 2: 1-4: 1.
3. A method of preparing the hydroxyl terminated polyisoprene polyurethane of claim 1, wherein the hydroxyl terminated polyisoprene polyurethane is synthesized from a biologically synthesized isoprene monomer.
4. The method as claimed in claim 3, wherein the hydroxyl-terminated polyisoprene polyurethane is obtained by synthesizing hydroxyl-terminated polyisoprene from isoprene monomer synthesized by biological method and then carrying out polymerization reaction with toluene diisocyanate.
5. A method according to claim 3, characterized in that the method comprises the steps of:
(1) adding hydroxyl-terminated polyisoprene into a three-port reactor, adjusting the temperature of an oil bath to 120 ℃, dehydrating for 2h under the condition of vacuum degree of-0.0095 MPa, and cooling to 90 ℃;
(2) adding a catalyst, stirring and mixing fully and uniformly;
(3) adding toluene diisocyanate, stirring uniformly, introducing nitrogen, reacting for 2-10 h until the system is fully mixed, and pre-polymerizing;
(4) adding a chain extender, continuing to react for 2-6 hours, carrying out the whole reaction process under the protection of nitrogen and under the heating condition of 60-90 ℃, precipitating and washing the mixed solution obtained by the reaction through methanol, and carrying out vacuum drying for 24 hours at 40 ℃ to obtain the hydroxyl-terminated polyisoprene polyurethane.
6. The method of claim 5, wherein the catalyst of step (3) is dibutyltin dilaurate.
7. The method of claim 5, wherein the chain extender of step (4) is 1, 4-butanediol, 1, 6-hexanediol, glycerol trimethylolpropane, triethylene glycol, neopentyl glycol, sorbitol or diethanolamine.
8. The method of claim 3, wherein the method for synthesizing hydroxyl-terminated polyisoprene comprises:
1) 100g of isoprene monomer, 100g of methanol and 50 percent of H by mass are synthesized by a biological method2O230g, and uniformly mixing; controlling the temperature to keep the reaction system at the temperature of 108 ℃ and 122 ℃, and stopping the reaction after the reaction time is 5-7 h;
2) when the temperature in the kettle is reduced to 50 ℃, pressing the mixture out of the kettle to obtain a crude product;
3) and (3) placing the crude product in a three-neck flask, steaming to remove residual monomers and methanol/ethanol, then transferring an organic layer into a separating funnel, washing with distilled water at 100 ℃ for three times, standing for layering, taking the organic layer, and distilling under reduced pressure at 80 ℃ and 100.6kPa for 2 hours to obtain the transparent hydroxyl-terminated liquid polyisoprene.
9. The method as claimed in claim 3, wherein the hydroxyl-terminated polyisoprene has a molecular weight of 4000-.
10. Use of the hydroxyl-terminated polyisoprene polyurethane according to claim 1 or 2 in military, security, encryption, apparel and medical applications.
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