CN114085517A - 一种木质素改性的水性聚氨酯薄膜及其制备方法 - Google Patents
一种木质素改性的水性聚氨酯薄膜及其制备方法 Download PDFInfo
- Publication number
- CN114085517A CN114085517A CN202111492704.1A CN202111492704A CN114085517A CN 114085517 A CN114085517 A CN 114085517A CN 202111492704 A CN202111492704 A CN 202111492704A CN 114085517 A CN114085517 A CN 114085517A
- Authority
- CN
- China
- Prior art keywords
- lignin
- polyurethane film
- waterborne polyurethane
- acid
- parts
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920006264 polyurethane film Polymers 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 229920005610 lignin Polymers 0.000 claims abstract description 35
- 239000004814 polyurethane Substances 0.000 claims abstract description 33
- 229920002635 polyurethane Polymers 0.000 claims abstract description 33
- 239000000839 emulsion Substances 0.000 claims abstract description 24
- 229920005862 polyol Polymers 0.000 claims abstract description 14
- 239000003960 organic solvent Substances 0.000 claims abstract description 13
- 150000001875 compounds Chemical class 0.000 claims abstract description 12
- 150000003077 polyols Chemical class 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000006185 dispersion Substances 0.000 claims abstract description 9
- -1 oxime compound Chemical class 0.000 claims abstract description 9
- 229920000768 polyamine Polymers 0.000 claims abstract description 9
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 9
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 9
- 238000010438 heat treatment Methods 0.000 claims abstract description 8
- 239000004970 Chain extender Substances 0.000 claims abstract description 7
- 239000002253 acid Substances 0.000 claims abstract description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical group CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 20
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 150000002009 diols Chemical class 0.000 claims description 9
- 238000000576 coating method Methods 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- LPMBTLLQQJBUOO-KTKRTIGZSA-N (z)-n,n-bis(2-hydroxyethyl)octadec-9-enamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)N(CCO)CCO LPMBTLLQQJBUOO-KTKRTIGZSA-N 0.000 claims description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 6
- 239000011248 coating agent Substances 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 239000011521 glass Substances 0.000 claims description 6
- DZCCLNYLUGNUKQ-UHFFFAOYSA-N n-(4-nitrosophenyl)hydroxylamine Chemical compound ONC1=CC=C(N=O)C=C1 DZCCLNYLUGNUKQ-UHFFFAOYSA-N 0.000 claims description 6
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 5
- 238000004821 distillation Methods 0.000 claims description 5
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 5
- 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 5
- 229940008841 1,6-hexamethylene diisocyanate Drugs 0.000 claims description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 4
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 4
- VEZUQRBDRNJBJY-UHFFFAOYSA-N cyclohexanone oxime Chemical compound ON=C1CCCCC1 VEZUQRBDRNJBJY-UHFFFAOYSA-N 0.000 claims description 4
- 230000001804 emulsifying effect Effects 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
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 4
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 claims description 4
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 claims description 4
- 229920001610 polycaprolactone Polymers 0.000 claims description 3
- 239000004632 polycaprolactone Substances 0.000 claims description 3
- 229920000515 polycarbonate Polymers 0.000 claims description 3
- 239000004417 polycarbonate Substances 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 claims description 2
- JVYDLYGCSIHCMR-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)butanoic acid Chemical compound CCC(CO)(CO)C(O)=O JVYDLYGCSIHCMR-UHFFFAOYSA-N 0.000 claims description 2
- DMJZWFZICOEEAJ-UHFFFAOYSA-N 2-(4-bromothiophen-3-yl)sulfanylpropanoic acid Chemical compound OC(=O)C(C)SC1=CSC=C1Br DMJZWFZICOEEAJ-UHFFFAOYSA-N 0.000 claims description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- 239000005711 Benzoic acid Substances 0.000 claims description 2
- AKNUHUCEWALCOI-UHFFFAOYSA-N N-ethyldiethanolamine Chemical compound OCCN(CC)CCO AKNUHUCEWALCOI-UHFFFAOYSA-N 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 2
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 claims description 2
- 235000011054 acetic acid Nutrition 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 235000010233 benzoic acid Nutrition 0.000 claims description 2
- 229920005551 calcium lignosulfonate Polymers 0.000 claims description 2
- RYAGRZNBULDMBW-UHFFFAOYSA-L calcium;3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy-4-(3-sulfonatopropyl)phenoxy]propane-1-sulfonate Chemical compound [Ca+2].COC1=CC=CC(CC(CS([O-])(=O)=O)OC=2C(=CC(CCCS([O-])(=O)=O)=CC=2)OC)=C1O RYAGRZNBULDMBW-UHFFFAOYSA-L 0.000 claims description 2
- JGUQDUKBUKFFRO-CIIODKQPSA-N dimethylglyoxime Chemical compound O/N=C(/C)\C(\C)=N\O JGUQDUKBUKFFRO-CIIODKQPSA-N 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 2
- XJRAOMZCVTUHFI-UHFFFAOYSA-N isocyanic acid;methane Chemical compound C.N=C=O.N=C=O XJRAOMZCVTUHFI-UHFFFAOYSA-N 0.000 claims description 2
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 229920000728 polyester Polymers 0.000 claims description 2
- 229920000570 polyether Polymers 0.000 claims description 2
- 229920000921 polyethylene adipate Polymers 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- 229920005552 sodium lignosulfonate Polymers 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- GXAWBMKGEAFJFM-UHFFFAOYSA-N azanium;3-hydroxy-2-(hydroxymethyl)-2-methylpropanoate Chemical compound [NH4+].OCC(C)(CO)C([O-])=O GXAWBMKGEAFJFM-UHFFFAOYSA-N 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 15
- 230000000694 effects Effects 0.000 abstract description 6
- 238000011065 in-situ storage Methods 0.000 abstract description 5
- 238000004064 recycling Methods 0.000 abstract description 5
- 230000007062 hydrolysis Effects 0.000 description 6
- 238000006460 hydrolysis reaction Methods 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000010907 mechanical stirring Methods 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000008439 repair process Effects 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 229920001730 Moisture cure polyurethane Polymers 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Chemical group 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- AGBQKNBQESQNJD-UHFFFAOYSA-M lipoate Chemical group [O-]C(=O)CCCCC1CCSS1 AGBQKNBQESQNJD-UHFFFAOYSA-M 0.000 description 1
- 235000019136 lipoic acid Nutrition 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 238000002464 physical blending Methods 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000007634 remodeling Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 229960002663 thioctic acid Drugs 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- 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
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3819—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen
-
- 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
-
- 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
- C08G18/44—Polycarbonates
-
- 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
- C08G18/48—Polyethers
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
-
- 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
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6633—Compounds of group C08G18/42
-
- 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
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
-
- 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
- C08G18/675—Low-molecular-weight compounds
- C08G18/677—Low-molecular-weight compounds containing heteroatoms other than oxygen and the nitrogen of primary or secondary amino groups
- C08G18/678—Low-molecular-weight compounds containing heteroatoms other than oxygen and the nitrogen of primary or secondary amino groups containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
- C08J2375/14—Polyurethanes having carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2497/00—Characterised by the use of lignin-containing materials
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
本发明涉及一种木质素改性的水性聚氨酯薄膜及其制备方法,属于水性聚氨酯材料的制备技术领域。所述水性聚氨酯薄膜包括低聚物多元醇、多元异氰酸酯、亲水性扩链剂、肟基化合物、多元胺化合物、酸类化合物、有机溶剂和木质素。本发明将木质素以水相原位填加的方式引入到合成的聚氨酯乳液中,实现了木质素在水性聚氨酯体系中的原位纳米分散效果,加热固化得到水性聚氨酯薄膜,极大地提高了力学性能,并有效保留了自修复功能,提高了材料的循环使用性能。
Description
技术领域
本发明涉及一种木质素改性的水性聚氨酯薄膜及其制备方法,属于水性聚氨酯材料的制备技术领域。
背景技术
近年来,随着人们环保意识的提高,材料的安全问题越来越受到人们的广泛关注。水性聚氨酯材料是以水作为分散介质,具有环保、安全可靠,易储存等优点目前广泛应用于涂料、胶粘剂、织物涂层与整理剂、皮革涂饰剂、纸张和纤维表面处理剂等领域。普通的水性聚氨酯材料在使用的过程中,其表面和内部会不可避免地出现损伤,导致材料的性能变差,使用寿命减少,而且强度不是很高,耐水解性能也较差。现在大多数具有自修复功能的水性聚氨酯多采用石油化工产品为原料,价格昂贵且不可再生。因此,寻找合适的方法实现水性聚氨酯自修复和提高耐水解性及力学性能是现实而重要的问题。
国内外研究人员主要通过在聚氨酯中接枝硅、环氧树脂、聚丙烯酸树脂、有机氟等方法来提高其性能。CN102093530A通过引入有机硅来改性水性聚氨酯,采用物理共混的方法,提高耐水解性,耐高温性,但是有机硅和聚氨酯链段的相容性不好,常规分散效果不好,需要大量的有机溶剂,而且,这些改性实验材料大多来自石油化工资源,价格昂贵且不可再生。CN109337043A公开了一种无溶剂性自修复水性聚氨酯的制备方法,通过硫辛酸和碳碳双键封端制备聚氨酯预聚体,该方法虽然无溶剂,绿色环保,但是也同样存在原价贵且强度低的特点。
与石化资源相比,生物质资源丰富,具有无毒、可再生、价格低廉、生物相容性好等优点。利用天然可再生生物质对高分子材料进行改性已成为研究热点,木质素作为一种来源于植物的天然高分子聚合物,从植物中提取,来源广泛,价格便宜。目前献有对于水性聚氨酯/木质素复合材料的研究报道,Yuanbin Lai等人报道了一种木质素基水性聚氨酯乳液的制备方法(Industrial Crops&Products,2021,170,113739),然而上述制备方法虽然应用了生物基材料木质素,但是其并没有自修复功能,并且力学强度也没有有效地提高。
发明内容
本发明针对上述问题,提供了一种木质素改性的水性聚氨酯乳液及其制备方法,本发明将木质素以水相原位填加的方式引入到本发明所合成的聚氨酯乳液中,实现了木质素在水性聚氨酯体系中的原位纳米分散效果,加热固化得到水性聚氨酯薄膜,极大地提高了力学性能,并有效保留了自修复功能,提高了材料的循环使用性能。本发明的技术方案如下:
一种木质素改性的水性聚氨酯薄膜,包括以下质量份的原料:
低聚物多元醇100份;
多元异氰酸酯50-100份;
亲水性扩链剂5-15份;
肟基化合物20-30份;
多元胺化合物5-15份;
酸类化合物5-15份;
有机溶剂30-100份;
木质素10-20份。
优选的,所述低聚物多元醇包括但不限于聚醚二元醇、聚酯二元醇、聚己内脂二元醇、聚碳酸酯二元醇、聚己二酸乙二醇或聚四氢呋喃醚中的至少一种;优选的,所述低聚物多元醇的羟值为40-80mgKOH/g,更优选羟值范围为50-60mgKOH/g。
优选的,本发明中所述的多元异氰酸酯可广泛取自市面上各种可以满足水性聚氨酯生产的多异氰酸酯产品;所述多异氰酸酯包括但不限于甲苯二异氰酸酯、异佛尔酮二异氰酸酯、甲烷二异氰酸酯、1,6-六亚甲基二异氰酸酯或二环己基甲烷二异氰酸酯中的至少一种。
优选的,所述亲水性扩链剂选自2,2-二羟甲基丁酸、2,2-二羟甲基丙酸,2,2-二羟甲基丙酸铵,N甲基二乙醇胺,N乙基二乙醇胺,油酸二乙醇酰胺中的至少一种。
优选的,所述肟基化合物选自丁二酮肟、丁醛肟或环己酮肟、对苯醌二肟中的至少一种。
优选的,所述多元胺选自三乙胺、乙二胺、1,4-丁二胺、1,6-己二胺或1,3-丙二胺中的至少一种;更优选的,所述多元胺为三乙胺或乙二胺。
优选的,所述酸类化合物选自硫酸、盐酸、磷酸、硝酸、甲酸、乙酸、乙二酸、苯甲酸中的至少一种。
优选的,所述有机溶剂为丙酮或丁酮。
优选的,所述木质素选自碱木质素、脱碱木质素、木质素磺酸钠或木质素磺酸钙中的至少一种。
进一步的,上述木质素改性的水性聚氨酯薄膜的制备方法,步骤如下:
将多元异氰酸酯和低聚物多元醇加入到反应容器中进行搅拌,并逐渐升温到80-90℃,反应1-3小时后加入亲水性扩链剂,1-2小时后加入肟基化合物,反应一个小时后每隔半小时加入10-15份有机溶剂,保持反应温度在80-90℃,反应3-5小时后降温至50-60℃,加入多元胺或酸类化合物,反应0.5-1小时,倒出前加入丙酮降低粘度,后将反应物从反应容器中倒出,加入去离子水在高速分散机下进行乳化,减压蒸馏除去丙酮,最后加入木质素再进行高速机械混合,即得到稳定的高强度自修复特性的改性水性聚氨酯乳液;在玻璃板上涂抹自修复水性聚氨酯乳液并固化,得到自修复水性聚氨酯薄膜。本发明与现有技术相比具有以下优点:
实现了所合成的水性聚氨酯与木质素的原位纳米复合,整个过程不需外加高污染有机溶剂,不需高能耗剪切混合设备,即可以实现极佳的水相纳米分散,绿色环保;本发明所制备的木质素/水性聚氨酯体系,即可实质性提高水性聚氨酯薄膜的机械强度和耐水解性能,又同时有效保留了水性聚氨酯薄膜的自修复效果,提高了循环利用能力;此外,木质素的引入显著提升了材料抗紫外线吸收能力,延长了使用稳定性。
附图说明
图1为未加木质素的水性聚氨酯薄膜与添加质量分数3%木质素的水性聚氨酯薄膜强度对比。添加木质素后可有效提高薄膜的最高强度;
图2为未加木质素的水性聚氨酯薄膜与添加质量分数3%木质素的聚氨酯薄膜在65℃下浸泡20小时后的强度对比,结果表明,添加木质素后强度几乎不变,说明可有效提高其耐水解性;
图3为完全切断的聚氨酯薄膜在140℃下修复1小时后与完好的聚氨酯薄膜强度对比,其强度达到初始样品的80%以上,说明其具有良好的修复能力;
图4为聚氨酯薄膜被切成毫米尺寸碎片,在145℃下使用10MPa的压力加热10min实现材料重塑后的相片,证明材料具有良好的循环使用特性。
具体实施方式
下面结合具体实施例来进一步描述本发明,本发明的优点和特点将会随着描述而更为清楚。但实施例仅是范例性的,并不对本发明的范围构成任何限制。本领域技术人员应该理解的是,在不偏离本发明的精神和范围下可以对本发明技术方案的细节和形式进行修改或替换,但这些修改和替换均落入本发明的保护范围内。
实施例1:一种木质素改性的水性聚氨酯薄膜及其制备方法
将19.78g1,6-六亚甲基二异氰酸酯,2.62g异佛尔酮二异氰酸酯和30g分子量为2000的聚己内酯多元醇加入到三口瓶中,开动机械搅拌,并逐渐升温到85℃,反应1小时后加入2.15g油酸二乙醇酰胺,1小时后加入7.67g对苯醌二肟,一小时后每隔半小时加入5mL丙酮,保持反应温度在85℃,反应3小时后降温至60℃,待温度降至60℃加入1.75g盐酸,反应0.5小时后,倒出加入150mL去离子水在高速分散机下进行乳化,减压蒸馏除去有机溶剂,最后保留一半未改性乳液,一半乳液加入0.88g碱木质素再进行高速机械混合,即得到稳定的高强度自修复特性的改性水性聚氨酯乳液。在玻璃板上涂抹自修复水性聚氨酯乳液并在烘箱中105℃固化2小时,得到自修复水性聚氨酯薄膜。
实施例2:一种木质素改性的水性聚氨酯薄膜及其制备方法
将15.32g 1,6-六亚甲基二异氰酸酯和3.75g甲苯二异氰酸酯,24g分子量为2000的聚四氢呋喃醚多元醇加入到三口瓶中,开动机械搅拌,并逐渐升温到85℃,反应1小时后加入2.65g油酸二乙醇酰胺,1小时后加入7.67g对苯醌二肟,一小时后每隔半小时加入5mL丙酮,保持反应温度在85℃,反应3小时后降温至60℃,待温度降至60℃加入1.50g盐酸,反应0.5小时后,倒出加入150mL去离子水在高速分散机下进行乳化,减压蒸馏除去有机溶剂,最后保留一半未改性乳液,一半乳液加入0.88g碱木质素再进行高速机械混合,即得到稳定的高强度自修复特性的改性水性聚氨酯乳液。在玻璃板上涂抹自修复水性聚氨酯乳液并在烘箱中105℃固化2小时,得到自修复水性聚氨酯薄膜。
实施例3:一种木质素改性的水性聚氨酯薄膜及其制备方法
将19.78g异佛尔酮二异氰酸酯,3.21g甲苯二异氰酸酯和26g分子量为2000的聚碳酸酯多元醇加入到三口瓶中,开动机械搅拌,并逐渐升温到85℃,反应1小时后加入2.20g油酸二乙醇酰胺,1小时后加入5.77g对苯醌二肟,一小时后每隔半小时加入5mL丙酮,保持反应温度在85℃,反应3小时后降温至60℃,待温度降至60℃加入1.85g盐酸,反应0.5小时后,倒出加入150mL去离子水在高速分散机下进行乳化,减压蒸馏除去有机溶剂,最后保留一半未改性乳液,一半乳液加入0.88g碱木质素再进行高速机械混合,即得到稳定的高强度自修复特性的改性水性聚氨酯乳液。在玻璃板上涂抹自修复水性聚氨酯乳液并在烘箱中105℃固化2小时,得到自修复水性聚氨酯薄膜。
实施例4:一种木质素改性的水性聚氨酯薄膜及其制备方法
将14.78g异佛尔酮二异氰酸酯和4.34g甲苯二异氰酸酯和26g分子量为2000的聚四氢呋喃醚多元醇加入到三口瓶中,开动机械搅拌,并逐渐升温到85℃,反应1小时后加入2.8g油酸二乙醇酰胺,1小时后加入6.67g对苯醌二肟,一小时后每隔半小时加入5mL丙酮,保持反应温度在85℃,反应3小时后降温至60℃,待温度降至60℃加入3.55g盐酸,反应0.5小时后,倒出加入150mL去离子水在高速分散机下进行乳化,减压蒸馏除去有机溶剂,最后保留一半未改性乳液,一半乳液加入0.88g碱木质素再进行高速机械混合,即得到稳定的高强度自修复特性的改性水性聚氨酯乳液。在玻璃板上涂抹自修复水性聚氨酯乳液并在烘箱中105℃固化2小时,得到自修复水性聚氨酯薄膜。
试验例:对实施例1中所制备的自修复水性聚氨酯薄膜进行了强度性能测试,用裁刀将薄膜裁成哑铃型,在质构仪上进行拉伸测试,测试结果如图1所示。对实施例2中所制备的自修复水性聚氨酯薄膜进行了耐水解性能测试,未加木质素的水性聚氨酯薄膜与添加质量分数3%木质素的聚氨酯薄膜在65℃下浸泡20小时后,在质构仪上进行强度测试,测试结果如图2所示。对实施例3所制备的自修复水性聚氨酯薄膜进行了自修复实验,实验步骤为:用干净刀片用刀片将未改性水性聚氨酯薄膜切断,将被切断的水性聚氨酯薄膜切口对齐,放入150℃烘箱中,于20min后取出。质构仪测修复前后强度,结果如图3所示。对实施例4所制备的自修复水性聚氨酯薄膜进行了再循环性能测试,实验步骤为:将未改性薄膜剪成碎片,在10MPa,145℃下10分钟后查看重塑效果,结果如图4所示。
Claims (10)
1.一种木质素改性的水性聚氨酯薄膜,其特征在于,所述水性聚氨酯薄膜包括以下质量份的原料:
低聚物多元醇100份;
多元异氰酸酯50-100份;
亲水性扩链剂5-15份;
肟基化合物20-30份;
多元胺化合物5-15份;
酸类化合物5-15份;
有机溶剂30-100份;
木质素10-20份。
2.根据权利要求1所述的水性聚氨酯薄膜,其特征在于,所述低聚物多元醇包括但不限于聚醚二元醇、聚酯二元醇、聚己内脂二元醇、聚碳酸酯二元醇、聚己二酸乙二醇或聚四氢呋喃醚中的至少一种。
3.根据权利要求1所述的水性聚氨酯薄膜,其特征在于,所述低聚物多元醇的羟值为40-80mgKOH/g;优选的,所述低聚物多元醇的羟值为50-60mgKOH/g。
4.根据权利要求1所述的水性聚氨酯薄膜,其特征在于,所述多异氰酸酯包括但不限于甲苯二异氰酸酯、异佛尔酮二异氰酸酯、甲烷二异氰酸酯、1,6-六亚甲基二异氰酸酯或二环己基甲烷二异氰酸酯中的至少一种。
5.根据权利要求1所述的水性聚氨酯薄膜,其特征在于,所述亲水性扩链剂选自2,2-二羟甲基丁酸、2,2-二羟甲基丙酸,2,2-二羟甲基丙酸铵,N甲基二乙醇胺,N乙基二乙醇胺,油酸二乙醇酰胺中的至少一种。
6.根据权利要求1所述的水性聚氨酯薄膜,其特征在于,所述肟基化合物选自丁二酮肟、丁醛肟或环己酮肟、对苯醌二肟中的至少一种。
7.根据权利要求1所述的水性聚氨酯薄膜,其特征在于,所述多元胺选自三乙胺、乙二胺、1,4-丁二胺、1,6-己二胺或1,3-丙二胺中的至少一种;更优选的,所述多元胺为三乙胺或乙二胺。
8.根据权利要求1所述的水性聚氨酯薄膜,其特征在于,所述酸类化合物选自硫酸、盐酸、磷酸、硝酸、甲酸、乙酸、乙二酸、苯甲酸中的至少一种;所述有机溶剂为丙酮或丁酮。
9.根据权利要求1所述的水性聚氨酯薄膜,其特征在于,所述木质素选自碱木质素、脱碱木质素、木质素磺酸钠或木质素磺酸钙中的至少一种。
10.如上述1-9任一项所述木质素改性的水性聚氨酯薄膜的制备方法,步骤如下:
将多元异氰酸酯和低聚物多元醇加入到反应容器中进行搅拌,并逐渐升温到80-90℃,反应1-3小时后加入亲水性扩链剂,1-2小时后加入肟基化合物,反应一个小时后每隔半小时加入10-15份有机溶剂,保持反应温度在80-90℃,反应3-5小时后降温至50-60℃,加入多元胺或酸类化合物,反应0.5-1小时,倒出前加入丙酮降低粘度,后将反应物从反应容器中倒出,加入去离子水在高速分散机下进行乳化,减压蒸馏除去丙酮,最后加入木质素再进行高速机械混合,即得到稳定的高强度自修复特性的改性水性聚氨酯乳液;在玻璃板上涂抹自修复水性聚氨酯乳液并固化,得到自修复水性聚氨酯薄膜。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202111492704.1A CN114085517A (zh) | 2021-12-08 | 2021-12-08 | 一种木质素改性的水性聚氨酯薄膜及其制备方法 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202111492704.1A CN114085517A (zh) | 2021-12-08 | 2021-12-08 | 一种木质素改性的水性聚氨酯薄膜及其制备方法 |
Publications (1)
Publication Number | Publication Date |
---|---|
CN114085517A true CN114085517A (zh) | 2022-02-25 |
Family
ID=80306896
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202111492704.1A Pending CN114085517A (zh) | 2021-12-08 | 2021-12-08 | 一种木质素改性的水性聚氨酯薄膜及其制备方法 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN114085517A (zh) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN115304735A (zh) * | 2022-09-19 | 2022-11-08 | 广东睿鹏材料科学有限公司 | 一种纳米几丁质基聚氨酯及其制备方法 |
CN115386063A (zh) * | 2022-09-19 | 2022-11-25 | 广东拓普合成科技股份有限公司 | 一种木质素基水性聚氨酯及其制备方法 |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1939950A (zh) * | 2006-10-13 | 2007-04-04 | 武汉理工大学 | 一种木质素改性水性聚氨酯的制备方法 |
CN103613733A (zh) * | 2013-12-05 | 2014-03-05 | 天津工业大学 | 一种制备木质素型水性聚氨酯复合材料的新方法 |
CN104628982A (zh) * | 2015-02-13 | 2015-05-20 | 陕西科技大学 | 一种碱木质素基水性聚氨酯的制备方法 |
CN107805308A (zh) * | 2016-09-09 | 2018-03-16 | 翁秋梅 | 一种具有杂化交联网络的动态聚合物及其应用 |
-
2021
- 2021-12-08 CN CN202111492704.1A patent/CN114085517A/zh active Pending
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1939950A (zh) * | 2006-10-13 | 2007-04-04 | 武汉理工大学 | 一种木质素改性水性聚氨酯的制备方法 |
CN103613733A (zh) * | 2013-12-05 | 2014-03-05 | 天津工业大学 | 一种制备木质素型水性聚氨酯复合材料的新方法 |
CN104628982A (zh) * | 2015-02-13 | 2015-05-20 | 陕西科技大学 | 一种碱木质素基水性聚氨酯的制备方法 |
CN107805308A (zh) * | 2016-09-09 | 2018-03-16 | 翁秋梅 | 一种具有杂化交联网络的动态聚合物及其应用 |
Non-Patent Citations (1)
Title |
---|
刘欢欢: "木质素/聚氨酯胶粘剂的绿色制备及其综合性能分析", 《中国优秀硕士学位论文全文数据库(电子期刊),工程科技Ⅰ辑》 * |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN115304735A (zh) * | 2022-09-19 | 2022-11-08 | 广东睿鹏材料科学有限公司 | 一种纳米几丁质基聚氨酯及其制备方法 |
CN115386063A (zh) * | 2022-09-19 | 2022-11-25 | 广东拓普合成科技股份有限公司 | 一种木质素基水性聚氨酯及其制备方法 |
CN115386063B (zh) * | 2022-09-19 | 2024-02-27 | 广东拓普合成科技股份有限公司 | 一种木质素基水性聚氨酯及其制备方法 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN114085517A (zh) | 一种木质素改性的水性聚氨酯薄膜及其制备方法 | |
NAYAK | Natural oil-based polymers: opportunities and challenges | |
Malik et al. | Mechanical and thermal properties of castor oil–based polyurethane adhesive: effect of TiO2 filler | |
Han et al. | Hyperbranched polymer assisted curing and repairing of an epoxy coating | |
Zhang et al. | Castor-oil-based UV-curable hybrid coatings with self-healing, recyclability, removability, and hydrophobicity | |
CN109456459B (zh) | 一种提高水性聚氨酯耐水或耐溶剂性的方法 | |
CN115181232B (zh) | 一种聚氨酯材料及其制备方法和应用 | |
CN111019076A (zh) | 快速uv固化的超支化聚氨酯丙烯酸酯及其制备方法 | |
CN113583617B (zh) | 一种自修复反应型聚氨酯热熔胶及其制备方法 | |
CN113444221A (zh) | 一种环氧树脂改性水性聚氨酯的制备方法 | |
CN115232465A (zh) | 一种可在海水中实现自修复的强韧自修复材料的制备方法 | |
Liu et al. | Synthesis and characterization of interpenetrating polymer networks (IPNs) based on UV curable resin and blocked isocyanate/polyols | |
Zhang et al. | New kinds of lignin/non-isocyanate polyurethane hybrid polymers: Facile synthesis, smart properties and adhesive applications | |
CN112980376A (zh) | 一种水性聚氨酯胶粘剂及其制备方法 | |
Sangaletti et al. | Biobased boronic ester vitrimer resin from epoxidized linseed oil for recyclable carbon fiber composites | |
CN115558074B (zh) | 聚氨酯弹性体及其制备方法 | |
CN115785782A (zh) | 耐风沙磨损的水性聚氨酯涂料及其制备与应用方法 | |
Xu et al. | Fully biomass-derived polyurethane based on dynamic imine with self-healing, rapid degradability, and editable shape memory capabilities | |
CN114409921B (zh) | 一种改性木质素多元醇及其聚氨酯热熔胶的制备方法 | |
CN111518257B (zh) | 一种水性聚氨酯鞋胶及其制备方法 | |
CN114736646A (zh) | 一种纳米甲壳质增强水性聚氨酯胶粘剂的制备方法 | |
CN111234337B (zh) | 一种具有自修复功能的环氧化天然橡胶复合材料及其制备方法 | |
CN114213618A (zh) | 一种端羟基液体聚丁二烯橡胶改性水性聚氨酯树脂及其制备方法 | |
CN114276514B (zh) | 一种聚氨酯-丙烯酸杂化树脂和应用 | |
CN113736050A (zh) | 一种自修复、可回收的植物油基聚氨酯材料及其制备方法与应用 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
RJ01 | Rejection of invention patent application after publication | ||
RJ01 | Rejection of invention patent application after publication |
Application publication date: 20220225 |