CN114133508A - High-performance lignin-based polyurethane and preparation method thereof - Google Patents
High-performance lignin-based polyurethane and preparation method thereof Download PDFInfo
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- CN114133508A CN114133508A CN202210040925.3A CN202210040925A CN114133508A CN 114133508 A CN114133508 A CN 114133508A CN 202210040925 A CN202210040925 A CN 202210040925A CN 114133508 A CN114133508 A CN 114133508A
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- lignin
- based polyurethane
- polyurethane
- diisocyanate
- catalyst
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- 229920005610 lignin Polymers 0.000 title claims abstract description 146
- 239000004814 polyurethane Substances 0.000 title claims abstract description 75
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 74
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 229920005862 polyol Polymers 0.000 claims abstract description 22
- 150000003077 polyols Chemical class 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 13
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 60
- 239000003054 catalyst Substances 0.000 claims description 28
- -1 cyclic ester Chemical class 0.000 claims description 25
- 239000003513 alkali Substances 0.000 claims description 15
- 229920005906 polyester polyol Polymers 0.000 claims description 14
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 claims description 14
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 13
- 239000003960 organic solvent Substances 0.000 claims description 11
- 125000005442 diisocyanate group Chemical group 0.000 claims description 9
- OZJPLYNZGCXSJM-UHFFFAOYSA-N 5-valerolactone Chemical compound O=C1CCCCO1 OZJPLYNZGCXSJM-UHFFFAOYSA-N 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 238000006116 polymerization reaction Methods 0.000 claims description 7
- 150000001412 amines Chemical class 0.000 claims description 6
- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical compound CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 5
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 4
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 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 description 4
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 claims description 4
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 4
- YFHICDDUDORKJB-UHFFFAOYSA-N trimethylene carbonate Chemical compound O=C1OCCCO1 YFHICDDUDORKJB-UHFFFAOYSA-N 0.000 claims description 4
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 claims description 4
- 239000002655 kraft paper Substances 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- SBJCUZQNHOLYMD-UHFFFAOYSA-N 1,5-Naphthalene diisocyanate Chemical compound C1=CC=C2C(N=C=O)=CC=CC2=C1N=C=O SBJCUZQNHOLYMD-UHFFFAOYSA-N 0.000 claims description 2
- SVYKKECYCPFKGB-UHFFFAOYSA-N N,N-dimethylcyclohexylamine Chemical compound CN(C)C1CCCCC1 SVYKKECYCPFKGB-UHFFFAOYSA-N 0.000 claims description 2
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 claims description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- 238000000465 moulding Methods 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 57
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 15
- 239000002253 acid Substances 0.000 abstract description 13
- 239000000463 material Substances 0.000 abstract description 10
- 239000012948 isocyanate Substances 0.000 abstract description 3
- 150000002513 isocyanates Chemical class 0.000 abstract description 3
- 230000009257 reactivity Effects 0.000 abstract description 3
- 238000004132 cross linking Methods 0.000 abstract description 2
- 229920000728 polyester Polymers 0.000 abstract description 2
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 abstract 1
- 230000002708 enhancing effect Effects 0.000 abstract 1
- 238000005580 one pot reaction Methods 0.000 abstract 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical group ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 90
- 239000000047 product Substances 0.000 description 54
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 52
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 44
- 238000001035 drying Methods 0.000 description 34
- 239000006228 supernatant Substances 0.000 description 34
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 33
- 229910052757 nitrogen Inorganic materials 0.000 description 22
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 14
- 239000004810 polytetrafluoroethylene Substances 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 238000010791 quenching Methods 0.000 description 12
- 230000000171 quenching effect Effects 0.000 description 12
- 238000001291 vacuum drying Methods 0.000 description 11
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid group Chemical group C(C1=CC=CC=C1)(=O)O WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 10
- 229920001610 polycaprolactone Polymers 0.000 description 10
- 239000004632 polycaprolactone Substances 0.000 description 10
- 239000002244 precipitate Substances 0.000 description 10
- 238000005406 washing Methods 0.000 description 10
- 230000001376 precipitating effect Effects 0.000 description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 8
- 238000001816 cooling Methods 0.000 description 8
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 6
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 6
- 239000005711 Benzoic acid Substances 0.000 description 5
- 235000010233 benzoic acid Nutrition 0.000 description 5
- 238000004090 dissolution Methods 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical compound C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 description 4
- AKEUNCKRJATALU-UHFFFAOYSA-N 2,6-dihydroxybenzoic acid Chemical group OC(=O)C1=C(O)C=CC=C1O AKEUNCKRJATALU-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 150000007524 organic acids Chemical group 0.000 description 4
- 150000007530 organic bases Chemical class 0.000 description 4
- 239000003377 acid catalyst Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- ASMQGLCHMVWBQR-UHFFFAOYSA-M diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(=O)([O-])OC1=CC=CC=C1 ASMQGLCHMVWBQR-UHFFFAOYSA-M 0.000 description 3
- 229940098779 methanesulfonic acid Drugs 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 229940068886 polyethylene glycol 300 Drugs 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 230000004580 weight loss Effects 0.000 description 3
- ZXHZWRZAWJVPIC-UHFFFAOYSA-N 1,2-diisocyanatonaphthalene Chemical compound C1=CC=CC2=C(N=C=O)C(N=C=O)=CC=C21 ZXHZWRZAWJVPIC-UHFFFAOYSA-N 0.000 description 2
- FVKFHMNJTHKMRX-UHFFFAOYSA-N 3,4,6,7,8,9-hexahydro-2H-pyrimido[1,2-a]pyrimidine Chemical compound C1CCN2CCCNC2=N1 FVKFHMNJTHKMRX-UHFFFAOYSA-N 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000012975 dibutyltin dilaurate Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 229920000747 poly(lactic acid) Polymers 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 2
- YOIAWAIKYVEKMF-UHFFFAOYSA-N trifluoromethanesulfonic acid Chemical compound OS(=O)(=O)C(F)(F)F.OS(=O)(=O)C(F)(F)F YOIAWAIKYVEKMF-UHFFFAOYSA-N 0.000 description 2
- ODIGIKRIUKFKHP-UHFFFAOYSA-N (n-propan-2-yloxycarbonylanilino) acetate Chemical compound CC(C)OC(=O)N(OC(C)=O)C1=CC=CC=C1 ODIGIKRIUKFKHP-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- VVEMXQMSJUUTFO-UHFFFAOYSA-N 2,6-dihydroxybenzoic acid Chemical compound OC(=O)C1=C(O)C=CC=C1O.OC(=O)C1=C(O)C=CC=C1O VVEMXQMSJUUTFO-UHFFFAOYSA-N 0.000 description 1
- CSDQQAQKBAQLLE-UHFFFAOYSA-N 4-(4-chlorophenyl)-4,5,6,7-tetrahydrothieno[3,2-c]pyridine Chemical compound C1=CC(Cl)=CC=C1C1C(C=CS2)=C2CCN1 CSDQQAQKBAQLLE-UHFFFAOYSA-N 0.000 description 1
- PXRKCOCTEMYUEG-UHFFFAOYSA-N 5-aminoisoindole-1,3-dione Chemical compound NC1=CC=C2C(=O)NC(=O)C2=C1 PXRKCOCTEMYUEG-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004433 Thermoplastic polyurethane Substances 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229920000704 biodegradable plastic Polymers 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229920005611 kraft lignin Polymers 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000002464 physical blending Methods 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 239000012974 tin catalyst Substances 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
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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
- C08G18/40—High-molecular-weight compounds
- C08G18/64—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63
- C08G18/6492—Lignin containing materials; Wood resins; Wood tars; Derivatives thereof
-
- 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
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
- C08G18/4269—Lactones
- C08G18/4277—Caprolactone and/or substituted caprolactone
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses high-performance lignin-based polyurethane and a preparation method thereof. The invention adopts a one-pot method to prepare the product, simplifies the reaction and saves the operation time. The invention synthesizes a new lignin grafted product with a star-shaped structure, the hydroxyl value and reactivity of lignin are increased by grafting polyester, the hydroxyl value of the obtained grafted product is 33-57 mg KOH/g, and the lowest acid value is 0.9mg KOH/g. The modified lignin is easier to react with isocyanate to generate carbamate and improve the crosslinking density, thereby enhancing the mechanical property of polyurethane. The lignin polyurethane polyol obtained by the invention has a novel structure, and can completely replace the traditional petrochemical polyol to be applied to the preparation of polyurethane materials.
Description
Technical Field
The invention belongs to the field of polymer material compounding and application thereof, and particularly relates to high-performance lignin polyurethane and a preparation method thereof.
Background
Polyurethane (PU) is a polymer having repeating structural units of urethane segments obtained by reacting a di-or poly-organic isocyanate with a polyol compound (polyether polyol or polyester polyol). However, as the world's economic development has become more and more important as the petroleum resources have been exhausted, various high-molecular monomers derived from petroleum have been seriously troubled, thereby limiting the sources of raw materials for the polyurethane industry. In order to develop green energy and low-carbon economy, the preparation of environment-friendly materials by using wood biological raw materials becomes a research hotspot.
As a natural biological polymer with the reserve second to cellulose, the lignin is low in price and rich in reserve, and has the advantages of high thermal stability, good biodegradability, strong oxidation resistance and the like. At present, less than 2 percent of lignin produced industrially is reasonably utilized. The reasons for the limited use of lignin today are mainly the complex and varied structure, high polydispersity, brittle material and immiscibility with other polymer matrices.
Polycaprolactone is a popular bioplastic and is widely used in polyurethane synthesis. The thermoplastic polyurethane synthesized by taking polycaprolactone as the soft segment not only has excellent water resistance similar to polyether polyurethane, but also has excellent degradability. The polycaprolactone chain segment is introduced on the lignin skeleton through graft modification, so that the miscibility of the polycaprolactone chain segment with a polymer matrix can be improved. The obtained graft product can replace the traditional polyester polyol to be introduced into a polyurethane material, thereby not only solving the problems of petroleum resource shortage and environmental pollution, but also improving the mechanical property of the polyurethane material.
CN109337345A proposes a preparation method of lignin polyurethane composite material: uniformly mixing the components of polyurethane, lignin, a flame retardant, an antioxidant, an ultraviolet absorbent and the like, adding the mixture into an extruder, and carrying out melting, extrusion and granulation to obtain the lignin polyurethane composite material. However, the invention only achieves the purpose of adding lignin into the material through physical blending, so that the performance strength of the obtained product is low.
Disclosure of Invention
The purpose of the invention is as follows: the invention aims to solve the technical problem of the prior art and provides high-performance lignin-based polyurethane and a preparation method thereof, and the preparation method can reduce the production cost of the polyurethane and solve the defect of poor mechanical property of the polyurethane.
The invention idea is as follows: grafting a lactone monomer onto a lignin skeleton in a graft from mode, and then reacting with isocyanate and lignin to obtain polyurethane; the lignin-based polyester polyol with a new star structure is obtained after grafting modification, so that the reactivity of the lignin-based polyester polyol is enhanced; in addition, the addition of lignin can increase the mechanical property of polyurethane and reduce the production cost of the polyurethane, so as to solve the problems of high price and poor mechanical property of the polyurethane.
The technical scheme is as follows: a process for preparing high-performance lignin-base polyurethane includes polymerizing the lignin-contained polyester polyol with diisocyanate, lignin and organic amine catalyst in solvent, solidifying and shaping. Taking MDI, lignin and polycaprolactone polyol containing lignin as an example, the reaction path (polyurethane synthesis process) is shown as follows.
The preparation method of the lignin-containing polyester polyol comprises the step of reacting cyclic ester, lignin and a catalyst under the protection of inert gas, wherein epsilon-caprolactone is taken as an example, and the reaction path is shown as follows.
Wherein, the cyclic ester, the lignin and the organic catalyst are moisture-free substances obtained after drying; preferably, the cyclic ester is treated with calcium hydride overnight to remove water and purified by distillation under reduced pressure; the lignin needs to be placed in a vacuum drying box for water removal overnight before reaction.
Wherein the cyclic ester is any one or combination of more of epsilon-caprolactone, delta-valerolactone, lactide and trimethylene carbonate, and epsilon-caprolactone is preferred.
The lignin comprises any one or combination of alkali lignin, organic solvent lignin and kraft paper lignin, and preferably alkali lignin.
Wherein, the catalyst is any one or combination of several of organic catalyst and metal catalyst; preferably, the catalyst is an organic catalyst.
Wherein the organic catalyst is organic acid or organic base catalyst, and the metal catalyst is tin catalyst (such as stannous octoate).
Wherein the organic acid catalyst is any one or a combination of more of Citric Acid (CA), diphenyl phosphate (DPP), methanesulfonic acid (MSA), trifluoromethanesulfonic acid (Triflate) and 2, 6-dihydroxybenzoic acid (2, 6-dihydroxybenzoic acid); the organic base catalyst is any one or a combination of more of 1,5, 7-triazabicyclo [4.4.0] dec-5-ene (TBD), 1, 8-diazabicyclo [5.4.0] undec-7-ene (DBU) and 4-Dimethylaminopyridine (DMAP), and the structural formula of the organic base catalyst is shown as a formula I;
preferably, the organic catalyst is an organic acid catalyst to facilitate the dissolution of lignin; further preferably, the organic catalyst is 2, 6-dihydroxybenzoic acid.
Wherein the mass part ratio of the cyclic ester, the lignin and the organic catalyst is 60-98 parts: 2-40 parts (preferably 2-10 parts): 1-3 parts; preferably, the ratio of the three is 90 parts: 10 parts of: and 2 parts.
Wherein, organic solvent can be added in the preparation process of the lignin-containing polyol, and the polymerization is carried out in the solution, so that the materials are mixed more uniformly, and the molecular weight distribution of the product is lower; if the organic solvent is not added, the polymerization is carried out in bulk, which is more beneficial to the generation of grafting, and the molecular weight of the product is higher; wherein, the dosage of the solvent is not specifically required, so that the monomer concentration is 0.8-1.4 mol/L.
Wherein the reaction is carried out at 25-150 ℃ for 1-24 h.
After the reaction is finished, adding a solution containing a quenching agent for quenching and dissolving a product after the reaction liquid is cooled, separating, purifying and concentrating the obtained mixture, adding an organic solvent into the concentrated solution for precipitation, and drying in vacuum to obtain the product.
Wherein the quenching agent is benzoic acid or triethylamine; wherein the organic acid catalyst is quenched by triethylamine, and the organic base catalyst is quenched by benzoic acid; the solvent in the solution containing the quencher is Dichloromethane (DCM); wherein the dosage of the quenching agent is 1-5 times of the molar weight of the catalyst; the amount of DCM is not specifically required and the product is dissolved.
Wherein, the separation and purification comprises dissolving the mixture in an organic solvent, centrifuging and collecting the supernatant; washing the precipitate with organic solvent for three times, centrifuging, and collecting supernatant; mixing the obtained supernatants, and concentrating under reduced pressure; wherein the organic solvent is dichloromethane; wherein the centrifugation is carried out at 3000rpm for 3-5 min.
Wherein the organic solvent used for precipitation is selected from one or two of methanol and n-hexane, and the dosage of the organic solvent is 20-100 times of the volume of the collected concentrated solution; preferably, the concentrate is precipitated by addition to cold methanol at-20 ℃.
Preferably, after 6 hours of precipitation, it is centrifuged again and the purified solid product is dried overnight under vacuum.
Wherein the hydroxyl value of the obtained lignin-based polyester polyol is 33-57 mg KOH/g, and the lowest acid value is 0.9mg KOH/g.
Wherein, the diisocyanate is any one or combination of a plurality of 2, 4-toluene diisocyanate (2,4-TDI), 2, 6-toluene diisocyanate (2,6-TDI), 1, 5-Naphthalene Diisocyanate (NDI), Hexamethylene Diisocyanate (HDI) and diphenylmethane diisocyanate (MDI).
The lignin comprises any one or combination of alkali lignin, organic solvent lignin and kraft paper lignin, and preferably alkali lignin.
Wherein the organic amine catalyst is any one or a combination of N, N-dimethylcyclohexylamine, trimethylene diamine, triethylene diamine, triethylamine, triethanolamine and N, N-dimethylethanolamine.
Wherein the mass part ratio of the lignin-containing polyester polyol to the diisocyanate to the lignin is 5-50 parts: 50 parts of: 5-45 parts of a solvent; the mass portion ratio of the organic amine catalyst to the total mass portion of the polyester polyol containing lignin to the diisocyanate and the lignin is 0.1-0.3: 1 part; preferably 0.2 part: 1 part.
Wherein the solvent is N, N-dimethylformamide, and the dosage of the solvent has no specific requirement.
Wherein the temperature of the polymerization reaction is 80-90 ℃, and the time of the polymerization reaction is 60-80 min.
Wherein the curing temperature is 60-100 ℃, and the curing time is 12-24 h.
In the above process, the reaction is carried out under the protection of inert gas, specifically, the reaction container is vacuumized first, and then inert gas is charged; the inert gas is nitrogen.
The lignin-based polyurethane prepared by the method is within the protection scope of the invention.
Compared with the prior art, the invention has the following advantages:
1. the invention provides a preparation method of high-performance lignin polyurethane, which does not need to activate or acylate lignin, simplifies the reaction and saves the operation time; the preparation method is environment-friendly and low in cost, and the device used in the reaction process is simple in structure and convenient to operate.
2. The invention modifies lignin by ring-opening polymerization of cyclic ester to prepare lignin-based polyol, thereby improving hydroxyl value and reactivity of lignin. The lignin-based polyol, the lignin and the diisocyanate are blended in different proportions, and the structure of the synthesized novel polyurethane is adjusted, so that petrochemical products are avoided, and the resource consumption is reduced.
3. The ternary lignin-based polyurethane prepared by the invention has a novel structure, the modified lignin improves the crosslinking density, the material uniformity is better, the rigidity of the unmodified lignin is stronger, the tensile strength of the material reaches 62.4MPa, the elongation at break reaches 707%, the right-angle tearing strength reaches 49.94KN/m, and the mechanical property of the polyurethane prepared by only using the lignin or lignin polyol is better than that of the polyurethane prepared by only using the lignin or lignin polyol.
4. The invention partially or completely replaces aliphatic polyol with lignin-containing polyester polyol, adds lignin in the material, expands the application of the lignin, and has good guidance and application values in high-strength bio-based polyurethane and industrial application of the lignin.
Drawings
FIG. 1 is a graph of the thermal weight loss (TG) of the lignin polyurethane of example 1.
FIG. 2 is a graph of the thermal weight loss (TG) of the lignin polyurethane of example 6.
Detailed Description
The invention will be better understood from the following examples. However, it is easily understood by those skilled in the art that the contents described in the embodiments are only for illustrating the present invention and should not be limited to the invention described in detail in the claims.
In the following examples:
the monomer conversion rate calculation method comprises the following steps: the reaction mixture is subjected to nuclear magnetic resonance hydrogen spectrometry, wherein the integral of the polyester is divided by the sum of the integral of the polymer and the integral of the monomer.
The hydroxyl value detection method comprises the following steps: measuring the hydroxyl value according to GB/T12008.3-2009;
the detection method of the acid value comprises the following steps: acid number was determined according to HG/T2708-;
the detection method of the performance of the polyurethane comprises the following steps: the tensile strength and elongation at break of the polyurethane were determined using a CMT 2206(SANS) tensile tester according to GB/T6344-. The right angle tear strength was measured in a CMT 2206(SANS) tensile tester according to QB/T1130 standard.
The thermal weight loss detection method comprises the following steps: determined according to Discovery TGA 550 thermogravimetric analyzer.
In the comparative example, the polyethylene glycol 300 means that the molecular weight of polyethylene glycol is 300.
Example 1
The first step is as follows: weighing caprolactone (1.80g), alkali lignin (0.20g) and 2, 6-dihydroxy benzoic acid (0.04g), adding into a reaction tube together with a magnetic stirrer under the protection of nitrogen, reacting at 130 deg.C and 500rpm for 60min, cooling to room temperature, quenching with triethylamine (0.1g) in dichloromethane (5mL), dissolving completely, and collecting small part1HNMR analysis (CDCl)3As a deuterated reagent). Adding 15mL of dichloromethane into the rest part for dissolving and centrifuging, and collecting supernatant; washing the precipitate with dichloromethane solution for three times, centrifuging, and collecting supernatant; and combining the obtained supernatants, concentrating under reduced pressure to 5-10 mL, precipitating the product by using excessive (about 50mL) cold methanol, and drying in vacuum to constant weight to obtain the lignin-containing polycaprolactone polyol. The conversion of caprolactone is 98.5%, the hydroxyl value is 57mg KOH-g, acid value 0.9mg KOH/g.
The second step is that: placing the grafted product and lignin in a vacuum drying oven for overnight drying, and redistilling DMF to remove water; the grafted product (5.0g), alkali lignin (5.0g), MDI (10.0g), triethylamine (0.04g) and DMF (25mL) were taken and added into a reaction flask under the protection of nitrogen and reacted for 60min under an oil bath at the temperature of 90 ℃. And after the reaction is finished, pouring the product into a polytetrafluoroethylene mold, and drying in an oven at 60 ℃ for 24 hours to obtain a lignin-based polyurethane sample. The tensile strength of the obtained polyurethane is 53.6MPa, the elongation at break is 586%, and the right-angle tear strength is 32.61 kN/m.
Example 2
The first step is as follows: caprolactone (1.90g), alkali lignin (0.10g) and trifluoromethanesulfonic acid (0.04g) were weighed into a reaction tube under a nitrogen atmosphere with a magnetic stirrer. Reacting at 130 deg.C and 400rpm for 60min, cooling to room temperature, quenching with dichloromethane solution (5mL) of triethylamine (0.1g), adding 15mL dichloromethane for dissolving, centrifuging, and collecting supernatant; washing the precipitate with dichloromethane solution for three times, centrifuging, and collecting supernatant; and combining the obtained supernatants, concentrating under reduced pressure to 5-10 mL, precipitating the product by using excessive (about 50mL) cold methanol, and drying in vacuum to constant weight to obtain the lignin-containing polycaprolactone polyol. The conversion of caprolactone was 97.7%, the hydroxyl value was 50mg KOH/g, and the acid value was 1.1mg KOH/g.
The second step is that: placing the grafted product and lignin in a vacuum drying oven for overnight drying, and redistilling DMF to remove water; the grafted product (5.0g), lignin (4.0g), 2,4-TDI (8.0g), triethylamine (0.02g) and DMF (25mL) were added to a reaction flask under nitrogen protection and reacted for 60min in an oil bath at 90 ℃. And after the reaction is finished, pouring the product into a polytetrafluoroethylene mold, and drying for 21 hours in an oven at 70 ℃ to obtain a lignin-based polyurethane sample. The tensile strength of the polyurethane obtained was 39.3MPa, the elongation at break was 451%, and the right-angle tear strength was 23.67 kN/m.
Example 3
The first step is as follows: caprolactone (1.70g), alkali lignin (0.30g) and diphenyl phosphate (0.02g) were weighed into a reaction tube under a nitrogen atmosphere with a magnetic stirrer. Reacting at 110 ℃ and 500rpm for 360min, cooling to room temperature, quenching with a dichloromethane solution (5mL) of triethylamine (0.1g), adding 15mL of dichloromethane for dissolving, centrifuging, and collecting a supernatant; washing the precipitate with dichloromethane solution for three times, centrifuging, and collecting supernatant; and combining the obtained supernatants, concentrating under reduced pressure to 5-10 mL, precipitating the product by using excessive (about 50mL) cold methanol, and drying in vacuum to constant weight to obtain the lignin-containing polycaprolactone polyol. The conversion of caprolactone was 98.2%, the hydroxyl value was 53mg KOH/g, and the acid value was 1.0mg KOH/g.
The second step is that: placing the grafted product and lignin in a vacuum drying oven for overnight drying, and redistilling DMF to remove water; the grafted product (10.0g), lignin (5.0g), 2,6-TDI (10.0g), triethylamine (0.06g) and DMF (25mL) were added to a reaction flask under nitrogen protection and reacted for 60min in an oil bath at 90 ℃. And after the reaction is finished, pouring the product into a polytetrafluoroethylene mold, and drying in an oven at 80 ℃ for 18h to obtain a lignin-based polyurethane sample. The tensile strength of the obtained polyurethane is 62.4MPa, the elongation at break is 707 percent, and the right-angle tear strength is 28.01 kN/m.
Example 4
The first step is as follows: caprolactone (1.84g), alkali lignin (0.16g) and citric acid (0.04g) were weighed into a reaction tube under a nitrogen blanket with a magnetic stirrer. Reacting at 150 deg.C and 500rpm for 120min, cooling to room temperature, quenching with dichloromethane solution (5mL) of triethylamine (0.1g), adding 15mL dichloromethane for dissolving, centrifuging, and collecting supernatant; washing the precipitate with dichloromethane solution for three times, centrifuging, and collecting supernatant; and combining the obtained supernatants, concentrating under reduced pressure to 5-10 mL, precipitating the product by using excessive (about 50mL) cold methanol, and drying in vacuum to constant weight to obtain the lignin-containing polycaprolactone polyol. The caprolactone conversion was 94.6%, the hydroxyl value was 47mg KOH/g, and the acid value was 3.2mg KOH/g.
The second step is that: placing the grafted product and lignin in a vacuum drying oven for overnight drying, and redistilling DMF to remove water; the grafted product (5.0g), lignin (5.0g), NDI (10.0g), triethylamine (0.04g) and DMF (25mL) were taken and added to a reaction flask under nitrogen protection and reacted for 60min under an oil bath at 90 ℃. And after the reaction is finished, pouring the product into a polytetrafluoroethylene mold, and drying in an oven at 90 ℃ for 15h to obtain a lignin-based polyurethane sample. The tensile strength of the polyurethane obtained is 55.9MPa, the elongation at break is 521%, and the right-angle tear strength is 29.44 kN/m.
Example 5
The first step is as follows: valerolactone (1.6g), alkali lignin (0.4g) and 1,5, 7-triazabicyclo [4.4.0] dec-5-ene (0.04g) were weighed out and added to a reaction tube together with a magnetic stirrer under nitrogen protection. Reacting at 130 deg.C and 500rpm for 240min, cooling to room temperature, quenching with benzoic acid (0.1g) in dichloromethane (5mL), adding 15mL dichloromethane for dissolution, and collecting supernatant; washing the precipitate with dichloromethane solution for three times, centrifuging, and collecting supernatant; and combining the obtained supernatants, concentrating the combined supernatants to 5-10 mL under reduced pressure, precipitating the product by using excessive (about 50mL) cold methanol, and drying the product in vacuum to constant weight to obtain the lignin-containing polypentanolide polyol. The valerolactone conversion was 97.4%, the hydroxyl value was 42mg KOH/g, and the acid value was 2.6mg KOH/g.
The second step is that: placing the grafted product and lignin in a vacuum drying oven for overnight drying, and redistilling DMF to remove water; the graft product (1.0g), lignin (9.0g), HDI (10.0g), triethylamine (0.04g) and DMF (25mL) were taken, added to a reaction flask under nitrogen protection, and reacted for 60min under an oil bath at 90 ℃. And after the reaction is finished, pouring the product into a polytetrafluoroethylene mold, and drying in an oven at 100 ℃ for 12h to obtain a lignin-based polyurethane sample. The tensile strength of the obtained polyurethane is 16.6MPa, the elongation at break is 91 percent, and the right-angle tear strength is 49.94 kN/m.
Example 6
The first step is as follows: lactide (1.96g), alkali lignin (0.04g) and methanesulfonic acid (0.06g) were weighed into a reaction tube under a nitrogen blanket with a magnetic stirrer. Reacting at 55 ℃ and 400rpm for 16h, cooling to room temperature, quenching with a dichloromethane solution (5mL) of triethylamine (0.1g), adding 15mL of dichloromethane for dissolution, and collecting a supernatant; washing the precipitate with dichloromethane solution for three times, centrifuging, and collecting supernatant; and combining the obtained supernatants, concentrating the combined supernatants to 5-10 mL under reduced pressure, precipitating the product by using excessive (about 50mL) cold methanol, and drying the product in vacuum to constant weight to obtain the lignin-containing polylactide polyol. The conversion of lactide was 91.2%, the hydroxyl value was 48mg KOH/g, and the acid value was 1.7mg KOH/g.
The second step is that: placing the grafted product and lignin in a vacuum drying oven for overnight drying, and redistilling DMF to remove water; the grafted product (2.0g), lignin (8.0g), MDI (10.0g), triethylamine (0.04g) and DMF (25mL) were taken and added to a reaction flask under nitrogen protection and reacted for 70min under an oil bath at 85 ℃. And after the reaction is finished, pouring the product into a polytetrafluoroethylene mold, and drying in an oven at 60 ℃ for 24 hours to obtain a lignin-based polyurethane sample. The tensile strength of the obtained polyurethane is 23.3MPa, the elongation at break is 137 percent, and the right-angle tear strength is 40.09 kN/m.
Example 7
The first step is as follows: trimethylene carbonate (1.40g), organosolv lignin (0.60g), 1, 8-diazabicyclo [5.4.0] undec-7-ene (0.04g), and N, N-dimethylformamide (10mL) were weighed into a reaction flask under nitrogen with a magnetic stirrer. Reacting at 80 ℃ and 500rpm for 12h, cooling to room temperature, quenching with a dichloromethane solution (5mL) of benzoic acid (0.1g), adding 15mL of dichloromethane for dissolution, centrifuging, and collecting the supernatant; washing the precipitate with dichloromethane solution for three times, centrifuging, and collecting supernatant; and combining the obtained supernatants, concentrating the combined supernatants to 5-10 mL under reduced pressure, precipitating the product by using excessive (about 50mL) cold methanol, and drying the product in vacuum to constant weight to obtain the lignin-containing polycarbonate polyol. The conversion of trimethylene carbonate was 84.6%, the hydroxyl value was 33mg KOH/g, and the acid value was 1.5mg KOH/g.
The second step is that: placing the grafted product and lignin in a vacuum drying oven for overnight drying, and redistilling DMF to remove water; the grafted product (3.0g), lignin (7.0g), MDI (10.0g), triethylamine (0.04g) and DMF (25mL) were taken and added to a reaction flask under nitrogen protection and reacted for 80min under an oil bath at 80 ℃. And after the reaction is finished, pouring the product into a polytetrafluoroethylene mold, and drying in an oven at 60 ℃ for 24 hours to obtain a lignin-based polyurethane sample. The tensile strength of the polyurethane obtained was 32.3MPa, the elongation at break was 267% and the right angle tear strength was 36.91 kN/m.
Example 8
The first step is as follows: lactide (1.20g), kraft lignin (0.8g), 4-dimethylaminopyridine (0.04g) and tetrahydrofuran (10mL) were weighed into a reaction flask under a nitrogen blanket with a magnetic stirrer. Reacting at 25 deg.C and 500rpm for 24h, cooling to room temperature, quenching with benzoic acid (0.1g) in dichloromethane (5mL), adding 15mL dichloromethane for dissolution, centrifuging, and collecting supernatant; washing the precipitate with dichloromethane solution for three times, centrifuging, and collecting supernatant; and combining the obtained supernatants, concentrating the combined supernatants to 5-10 mL under reduced pressure, precipitating the product by using excessive (about 50mL) cold methanol, and drying the product in vacuum to constant weight to obtain the lignin-containing polylactide polyol. The conversion of lactide was 72.5%, the hydroxyl value was 34mg KOH/g, and the acid value was 1.9mg KOH/g.
The second step is that: placing the grafted product and lignin in a vacuum drying oven for overnight drying, and redistilling DMF to remove water; the grafted product (4.0g), lignin (6.0g), MDI (10.0g), triethylamine (0.04g) and DMF (25mL) were taken and added to a reaction flask under nitrogen protection and reacted for 80min under an oil bath at 85 ℃. And after the reaction is finished, pouring the product into a polytetrafluoroethylene mold, and drying in an oven at 60 ℃ for 24 hours to obtain a lignin-based polyurethane sample. The tensile strength of the obtained polyurethane is 43.6MPa, the elongation at break is 433 percent, and the right-angle tear strength is 37.99 kN/m.
Example 9
The first step is as follows: caprolactone (1.60g), alkali lignin (0.40g) and stannous octoate (0.04g) were weighed into a reaction tube under nitrogen with a magnetic stirrer. The reaction was carried out at 130 ℃ and 400rpm for 240min, after which the reaction was quenched with liquid nitrogen. Adding 15mL of dichloromethane for dissolving and centrifuging, and collecting supernatant; washing the precipitate with dichloromethane solution for three times, centrifuging, and collecting supernatant; and combining the obtained supernatants, concentrating under reduced pressure to 5-10 mL, precipitating the product by using excessive (about 50mL) cold methanol, and drying in vacuum to constant weight to obtain the lignin-containing polycaprolactone polyol. The caprolactone conversion was 97.2%, the hydroxyl value was 33mg KOH/g, and the acid value was 1.1mg KOH/g.
The second step is that: placing the grafted product and lignin in a vacuum drying oven for overnight drying, and redistilling DMF to remove water; the grafted product (6.0g), lignin (4.0g), MDI (10.0g), triethylamine (0.04g) and DMF (25mL) were taken and added to a reaction flask under nitrogen protection and reacted for 70min under an oil bath at 90 ℃. And after the reaction is finished, pouring the product into a polytetrafluoroethylene mold, and drying in an oven at 60 ℃ for 24 hours to obtain the lignin-based polyurethane sample. The tensile strength of the polyurethane obtained was 43.1MPa, the elongation at break was 650%, and the right-angle tear strength was 31.17 kN/m.
Example 10
The first step is the same as example 1.
The second step is that: placing the grafted product and lignin in a vacuum drying oven for overnight drying, and redistilling DMF to remove water; the grafted product (9.0g), lignin (1.0g), MDI (10.0g), triethylamine (0.04g) and DMF (25mL) were taken and added to a reaction flask under nitrogen protection and reacted for 60min under an oil bath at 90 ℃. And after the reaction is finished, pouring the product into a polytetrafluoroethylene mold, and drying in an oven at 60 ℃ for 24 hours to obtain a lignin-based polyurethane sample. The tensile strength of the obtained polyurethane is 30.7MPa, the elongation at break is 414 percent, and the right-angle tear strength is 20.11 kN/m.
Comparative example 1
Polyethylene glycol 300(10.0g), MDI (10.0g), triethylamine (0.04g) and DMF (25mL) were added to the reaction flask under nitrogen protection and reacted for 60min in an oil bath at 80 ℃. And after the reaction is finished, pouring the product into a polytetrafluoroethylene mold, and putting the polytetrafluoroethylene mold into a 60-DEG C oven for drying for 24h to obtain a polyurethane sample. The tensile strength of the obtained polyurethane is 11.6MPa, the elongation at break is 231%, and the right-angle tear strength is 8.01 kN/m.
Comparative example 2
Alkali lignin (5.0g), polyethylene glycol 300(5.0g), MDI (10g), dibutyltin dilaurate (0.04g) and DMF (25mL) were added into a reaction flask under the protection of nitrogen, and reacted for 60min under an oil bath at 80 ℃. And after the reaction is finished, pouring the product into a polytetrafluoroethylene mold, and drying in an oven at 60 ℃ for 24 hours to obtain the lignin-based polyurethane sample. The tensile strength of the obtained polyurethane is 19.5MPa, the elongation at break is 153%, and the right-angle tear strength is 30.39 kN/m.
Comparative example 3
Alkali lignin (5.0g), MDI (10g), dibutyltin dilaurate (0.04g) and DMF (25mL) were taken, added into a reaction flask under the protection of nitrogen, and reacted for 60min under an oil bath at the temperature of 80 ℃. And after the reaction is finished, pouring the product into a polytetrafluoroethylene mold, and drying in an oven at 60 ℃ for 24 hours to obtain the lignin-based polyurethane sample. The resulting polyurethane was highly brittle and could not be tested for mechanical properties.
TABLE 1 Performance index of Lignin-based polyurethane polyols
TABLE 2 characterization of Properties of Lignin-based polyurethanes
The present invention provides a high performance lignin-based polyurethane and a method for preparing the same, and a plurality of methods and ways for implementing the technical scheme, and the above description is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, a plurality of improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be regarded as the protection scope of the present invention. All the components not specified in the present embodiment can be realized by the prior art.
Claims (10)
1. A preparation method of lignin-based polyurethane is characterized by comprising the steps of carrying out polymerization reaction on lignin-containing polyester polyol, diisocyanate, lignin and an organic amine catalyst in a solvent, and carrying out curing molding to obtain the lignin-based polyurethane.
2. The method for preparing lignin-based polyurethane according to claim 1, wherein the lignin-containing polyester polyol is prepared by reacting cyclic ester, lignin and a catalyst under the protection of inert gas.
3. The method for preparing the lignin-based polyurethane according to claim 2, wherein the cyclic ester is any one or a combination of epsilon-caprolactone, delta-valerolactone, lactide and trimethylene carbonate.
4. The method for preparing the lignin-based polyurethane according to claim 2, wherein the catalyst is any one or a combination of organic catalyst and metal catalyst.
5. The method for preparing the lignin-containing polyol according to claim 2, wherein the mass part ratio of the cyclic ester, the lignin and the catalyst is 60-98 parts: 2-40 parts of: 1-3 parts.
6. The method for preparing lignin-based polyurethane according to claim 1, wherein the diisocyanate is any one or a combination of 2, 4-toluene diisocyanate, 2, 6-toluene diisocyanate, hexamethylene diisocyanate, 1, 5-naphthalene diisocyanate and diphenylmethane diisocyanate; the lignin comprises any one or a combination of more of alkali lignin, organic solvent lignin and kraft paper lignin; the organic amine catalyst is any one or a combination of N, N-dimethylcyclohexylamine, trimethylene diamine, triethylene diamine, triethylamine, triethanolamine and N, N-dimethylethanolamine.
7. The preparation method of the lignin-based polyurethane according to claim 1, wherein the mass ratio of the lignin-containing polyester polyol, the diisocyanate and the lignin is 5-50 parts: 50 parts of: 5-45 parts of a solvent; the mass portion ratio of the organic amine catalyst to the total mass portion ratio of the lignin-containing polyester polyol, the diisocyanate and the lignin is 0.1-0.3: 1 part.
8. The method for preparing the lignin-based polyurethane according to claim 1, wherein the polymerization temperature is 80 to 90 ℃ and the polymerization time is 60 to 80 min.
9. The method for preparing the lignin-based polyurethane according to claim 1, wherein the curing temperature is 60-100 ℃ and the curing time is 12-24 hours.
10. A lignin-based polyurethane produced by the production method according to any one of claims 1 to 9.
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Citations (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102718962A (en) * | 2012-06-27 | 2012-10-10 | 淄博德信联邦化学工业有限公司 | Segmented polyether compound modified lignin and preparation method thereof |
| CN105637036A (en) * | 2013-08-13 | 2016-06-01 | 能源实验室2000有限公司 | Process for the preparation of lignin based polyurethane products |
| CN108117650A (en) * | 2016-11-29 | 2018-06-05 | 中国石油化工股份有限公司 | A kind of biological plastics film of polycaprolactone grafting lignin and preparation method thereof |
| CN108559046A (en) * | 2018-01-09 | 2018-09-21 | 长春工业大学 | A kind of ozonisation modified lignin resin polyurethane and preparation method thereof |
| CN109485824A (en) * | 2018-10-12 | 2019-03-19 | 华南理工大学 | A kind of thermosetting property lignin-base polyurethane elastomer of recyclable processing and preparation method thereof |
| CN109504052A (en) * | 2018-12-13 | 2019-03-22 | 湖南绿燊环保科技有限公司 | Biomass toughener for polydactyl acid and preparation method thereof, polydactyl acid and preparation method thereof |
| CN110790889A (en) * | 2019-11-20 | 2020-02-14 | 苏州市雄林新材料科技有限公司 | Polarity-controllable TPU film and preparation method thereof |
| CN111187428A (en) * | 2020-02-19 | 2020-05-22 | 华南农业大学 | Lignin-based polyol, modified lignin-based polyurethane material, modified lignin-based polyurethane film, and preparation method and application thereof |
| CN112057672A (en) * | 2020-07-14 | 2020-12-11 | 广东工业大学 | PCL-lignin nanofiber scaffold material and preparation method thereof |
| CN112280263A (en) * | 2020-10-26 | 2021-01-29 | 怀化学院 | Lignin-based biodegradable polymer composite film and preparation method thereof |
| CN112390998A (en) * | 2020-11-16 | 2021-02-23 | 深圳市正旺环保新材料有限公司 | Environment-friendly plastic bag and preparation method thereof |
| CN112724361A (en) * | 2020-12-10 | 2021-04-30 | 桐乡市昇威电子商务服务有限公司 | Nitrogen-phosphorus-containing lignin-based intumescent flame retardant modified polyurethane elastomer and preparation method thereof |
| CN113004557A (en) * | 2021-02-26 | 2021-06-22 | 江南大学 | Intrinsic ultraviolet shielding polyurethane lignin composite film and preparation method thereof |
| CN113817130A (en) * | 2021-09-26 | 2021-12-21 | 华南理工大学 | Solvent-free lignin-based polyurethane elastomer capable of being repeatedly processed and preparation method thereof |
| CN113861363A (en) * | 2021-08-12 | 2021-12-31 | 江南大学 | Preparation method of anti-ultraviolet transparent lignin-based polyurethane elastomer |
-
2022
- 2022-01-14 CN CN202210040925.3A patent/CN114133508B/en active Active
Patent Citations (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102718962A (en) * | 2012-06-27 | 2012-10-10 | 淄博德信联邦化学工业有限公司 | Segmented polyether compound modified lignin and preparation method thereof |
| CN105637036A (en) * | 2013-08-13 | 2016-06-01 | 能源实验室2000有限公司 | Process for the preparation of lignin based polyurethane products |
| CN108117650A (en) * | 2016-11-29 | 2018-06-05 | 中国石油化工股份有限公司 | A kind of biological plastics film of polycaprolactone grafting lignin and preparation method thereof |
| CN108559046A (en) * | 2018-01-09 | 2018-09-21 | 长春工业大学 | A kind of ozonisation modified lignin resin polyurethane and preparation method thereof |
| CN109485824A (en) * | 2018-10-12 | 2019-03-19 | 华南理工大学 | A kind of thermosetting property lignin-base polyurethane elastomer of recyclable processing and preparation method thereof |
| CN109504052A (en) * | 2018-12-13 | 2019-03-22 | 湖南绿燊环保科技有限公司 | Biomass toughener for polydactyl acid and preparation method thereof, polydactyl acid and preparation method thereof |
| CN110790889A (en) * | 2019-11-20 | 2020-02-14 | 苏州市雄林新材料科技有限公司 | Polarity-controllable TPU film and preparation method thereof |
| CN111187428A (en) * | 2020-02-19 | 2020-05-22 | 华南农业大学 | Lignin-based polyol, modified lignin-based polyurethane material, modified lignin-based polyurethane film, and preparation method and application thereof |
| CN112057672A (en) * | 2020-07-14 | 2020-12-11 | 广东工业大学 | PCL-lignin nanofiber scaffold material and preparation method thereof |
| CN112280263A (en) * | 2020-10-26 | 2021-01-29 | 怀化学院 | Lignin-based biodegradable polymer composite film and preparation method thereof |
| CN112390998A (en) * | 2020-11-16 | 2021-02-23 | 深圳市正旺环保新材料有限公司 | Environment-friendly plastic bag and preparation method thereof |
| CN112724361A (en) * | 2020-12-10 | 2021-04-30 | 桐乡市昇威电子商务服务有限公司 | Nitrogen-phosphorus-containing lignin-based intumescent flame retardant modified polyurethane elastomer and preparation method thereof |
| CN113004557A (en) * | 2021-02-26 | 2021-06-22 | 江南大学 | Intrinsic ultraviolet shielding polyurethane lignin composite film and preparation method thereof |
| CN113861363A (en) * | 2021-08-12 | 2021-12-31 | 江南大学 | Preparation method of anti-ultraviolet transparent lignin-based polyurethane elastomer |
| CN113817130A (en) * | 2021-09-26 | 2021-12-21 | 华南理工大学 | Solvent-free lignin-based polyurethane elastomer capable of being repeatedly processed and preparation method thereof |
Non-Patent Citations (11)
| Title |
|---|
| JANG, SU-HEE .ETAL: "Construction of sustainable polyurethane-based gel-coats containing poly(ε-caprolactone)-grafted lignin and their coating performance", 《PROGRESS IN ORGANIC COATINGS》 * |
| JANG, SU-HEE .ETAL: "Construction of sustainable polyurethane-based gel-coats containing poly(ε-caprolactone)-grafted lignin and their coating performance", 《PROGRESS IN ORGANIC COATINGS》, vol. 120, 31 July 2018 (2018-07-31), pages 234 - 239, XP093021987, DOI: 10.1016/j.porgcoat.2018.04.008 * |
| KÜHNEL, ISABELL ; SAAKE, BODO ; LEHNEN, RALPH: "Comparison of different cyclic organic carbonates in the oxyalkylation of various types of lignin", REACTIVE & FUNCTIONAL POLYMERS, vol. 120, pages 83 - 91, XP085226872, DOI: 10.1016/j.reactfunctpolym.2017.09.011 * |
| LANG, JASON M. ; SHRESTHA, UMESH M. ; DADMUN, MARK: "The Effect of Plant Source on the Properties of Lignin-Based Polyurethanes", FRONTIERS IN ENERGY RESEARCH, vol. 6, pages 1 - 12 * |
| T. HATAKEYAMA;Y. IZUTA;S. HIROSE: "Phase transitions of lignin-based polycaprolactones and their polyurethane derivatives", 《POLYMER》 * |
| T. HATAKEYAMA;Y. IZUTA;S. HIROSE: "Phase transitions of lignin-based polycaprolactones and their polyurethane derivatives", 《POLYMER》, vol. 43, 28 February 2002 (2002-02-28), pages 1177 - 1182, XP004312436, DOI: 10.1016/S0032-3861(01)00714-5 * |
| 王治民;杨晓慧;周永红;: "木质素基聚氨酯薄膜的研究进展", 化工新型材料, no. 07, pages 13 - 15 * |
| 王治民等: "木质素基聚氨酯薄膜的研究进展", 《化工新型材料》 * |
| 王治民等: "木质素基聚氨酯薄膜的研究进展", 《化工新型材料》, no. 07, 15 July 2013 (2013-07-15), pages 13 - 15 * |
| 田静,杨益琴,宋君龙: "木质素的化学改性及其在高分子材料中的应用", 《纤维素科学与技术》 * |
| 田静,杨益琴,宋君龙: "木质素的化学改性及其在高分子材料中的应用", 《纤维素科学与技术》, vol. 26, no. 04, 31 December 2018 (2018-12-31), pages 76 - 85 * |
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