CN108504034A - 新型hmf低聚物 - Google Patents
新型hmf低聚物 Download PDFInfo
- Publication number
- CN108504034A CN108504034A CN201810162862.2A CN201810162862A CN108504034A CN 108504034 A CN108504034 A CN 108504034A CN 201810162862 A CN201810162862 A CN 201810162862A CN 108504034 A CN108504034 A CN 108504034A
- Authority
- CN
- China
- Prior art keywords
- hmf
- carbon
- unit
- linked
- oligomers
- 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
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 44
- 229920005989 resin Polymers 0.000 claims abstract description 32
- 239000011347 resin Substances 0.000 claims abstract description 32
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 31
- 150000001721 carbon Chemical group 0.000 claims abstract description 9
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims abstract description 8
- 239000002131 composite material Substances 0.000 claims abstract description 6
- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 claims description 141
- 239000000178 monomer Substances 0.000 claims description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 10
- 150000001720 carbohydrates Chemical class 0.000 claims description 7
- 239000002028 Biomass Substances 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical group C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 5
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 claims description 5
- 150000002373 hemiacetals Chemical class 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- 229920002678 cellulose Polymers 0.000 claims description 4
- 239000001913 cellulose Substances 0.000 claims description 4
- 150000002402 hexoses Chemical class 0.000 claims description 4
- RJGBSYZFOCAGQY-UHFFFAOYSA-N hydroxymethylfurfural Natural products COC1=CC=C(C=O)O1 RJGBSYZFOCAGQY-UHFFFAOYSA-N 0.000 claims description 4
- 239000007900 aqueous suspension Substances 0.000 claims description 3
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 claims 1
- 238000002360 preparation method Methods 0.000 abstract description 14
- 239000002023 wood Substances 0.000 abstract description 10
- 239000003795 chemical substances by application Substances 0.000 abstract description 8
- 229920003180 amino resin Polymers 0.000 abstract description 6
- 150000002989 phenols Chemical class 0.000 abstract description 4
- CETXOEGRUBXUAL-UHFFFAOYSA-N 3-(hydroxymethyl)furan-2-carbaldehyde Chemical class OCC=1C=COC=1C=O CETXOEGRUBXUAL-UHFFFAOYSA-N 0.000 abstract 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 abstract 1
- 150000002240 furans Chemical class 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 14
- 150000001728 carbonyl compounds Chemical class 0.000 description 7
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 6
- 150000001299 aldehydes Chemical class 0.000 description 6
- 239000004202 carbamide Substances 0.000 description 6
- 235000014633 carbohydrates Nutrition 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 150000001241 acetals Chemical class 0.000 description 5
- 238000010485 C−C bond formation reaction Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229930091371 Fructose Natural products 0.000 description 3
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 description 3
- 239000005715 Fructose Substances 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- UDHXJZHVNHGCEC-UHFFFAOYSA-N Chlorophacinone Chemical compound C1=CC(Cl)=CC=C1C(C=1C=CC=CC=1)C(=O)C1C(=O)C2=CC=CC=C2C1=O UDHXJZHVNHGCEC-UHFFFAOYSA-N 0.000 description 2
- 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 2
- -1 HMF modified urea-formaldehyde Chemical class 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 125000003172 aldehyde group Chemical group 0.000 description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 238000006471 dimerization reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000008103 glucose Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000004312 hexamethylene tetramine Substances 0.000 description 2
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- 238000010335 hydrothermal treatment Methods 0.000 description 2
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 230000020477 pH reduction Effects 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 description 1
- 239000004831 Hot glue Substances 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- 229920002522 Wood fibre Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000012271 agricultural production Methods 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011093 chipboard Substances 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- 239000011094 fiberboard Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 231100000206 health hazard Toxicity 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 239000002699 waste material Substances 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
- C08G2/00—Addition polymers of aldehydes or cyclic oligomers thereof or of ketones; Addition copolymers thereof with less than 50 molar percent of other substances
- C08G2/10—Polymerisation of cyclic oligomers of formaldehyde
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27N—MANUFACTURE BY DRY PROCESSES OF ARTICLES, WITH OR WITHOUT ORGANIC BINDING AGENTS, MADE FROM PARTICLES OR FIBRES CONSISTING OF WOOD OR OTHER LIGNOCELLULOSIC OR LIKE ORGANIC MATERIAL
- B27N3/00—Manufacture of substantially flat articles, e.g. boards, from particles or fibres
- B27N3/002—Manufacture of substantially flat articles, e.g. boards, from particles or fibres characterised by the type of binder
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
- C08L61/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08L61/22—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds
- C08L61/24—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds with urea or thiourea
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27N—MANUFACTURE BY DRY PROCESSES OF ARTICLES, WITH OR WITHOUT ORGANIC BINDING AGENTS, MADE FROM PARTICLES OR FIBRES CONSISTING OF WOOD OR OTHER LIGNOCELLULOSIC OR LIKE ORGANIC MATERIAL
- B27N3/00—Manufacture of substantially flat articles, e.g. boards, from particles or fibres
- B27N3/02—Manufacture of substantially flat articles, e.g. boards, from particles or fibres from particles
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/40—Radicals substituted by oxygen atoms
- C07D307/42—Singly bound oxygen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/40—Radicals substituted by oxygen atoms
- C07D307/46—Doubly bound oxygen atoms, or two oxygen atoms singly bound to the same carbon atom
- C07D307/48—Furfural
- C07D307/50—Preparation from natural products
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D407/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00
- C07D407/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00 containing two hetero rings
- C07D407/06—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00 containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
-
- 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
- C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
- C08G12/04—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds
- C08G12/10—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds with acyclic compounds having the moiety X=C(—N<)2 in which X is O, S or —N
- C08G12/12—Ureas; Thioureas
-
- 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
- C08G16/00—Condensation polymers of aldehydes or ketones with monomers not provided for in the groups C08G4/00 - C08G14/00
- C08G16/02—Condensation polymers of aldehydes or ketones with monomers not provided for in the groups C08G4/00 - C08G14/00 of aldehydes
- C08G16/025—Condensation polymers of aldehydes or ketones with monomers not provided for in the groups C08G4/00 - C08G14/00 of aldehydes with heterocyclic organic compounds
- C08G16/0256—Condensation polymers of aldehydes or ketones with monomers not provided for in the groups C08G4/00 - C08G14/00 of aldehydes with heterocyclic organic compounds containing oxygen in the ring
- C08G16/0262—Furfuryl alcohol
-
- 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
- C08G6/00—Condensation polymers of aldehydes or ketones only
-
- 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
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
- C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
- C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
- C08G61/125—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one oxygen atom in the ring
-
- 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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
- C08G65/36—Furfuryl alcohol
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L97/00—Compositions of lignin-containing materials
- C08L97/02—Lignocellulosic material, e.g. wood, straw or bagasse
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J161/00—Adhesives based on condensation polymers of aldehydes or ketones; Adhesives based on derivatives of such polymers
- C09J161/02—Condensation polymers of aldehydes or ketones only
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B21/00—Layered products comprising a layer of wood, e.g. wood board, veneer, wood particle board
- B32B21/04—Layered products comprising a layer of wood, e.g. wood board, veneer, wood particle board comprising wood as the main or only constituent of a layer, which is next to another layer of the same or of a different material
-
- 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
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/34—Monomer units or repeat units incorporating structural elements in the main chain incorporating partially-aromatic structural elements in the main chain
- C08G2261/344—Monomer units or repeat units incorporating structural elements in the main chain incorporating partially-aromatic structural elements in the main chain containing heteroatoms
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Forests & Forestry (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Phenolic Resins Or Amino Resins (AREA)
- Dry Formation Of Fiberboard And The Like (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Furan Compounds (AREA)
- Chemical And Physical Treatments For Wood And The Like (AREA)
Abstract
本发明涉及一种新型碳连接的5‑羟甲基糠醛(HMF)低聚物，其至少包含一种第一HMF单元和一种第二HMF单元，并且其特征在于，第一HMF单元和第二HMF单元通过碳‑碳键连接，涉及第一HMF单元的呋喃环的位置3或4处的芳香键合碳原子。本发明还涉及该新型HMF低聚物在基于酚类化合物和/或氨基塑料成型剂制备可热固化树脂中以及在制备木材复合材料产品中作为反应性羰基化合物的用途。
Description
本发明涉及新型HMF低聚物及其制备方法。本发明特别地涉及新型碳连接的HMF低聚物。这些低聚物在基于酚类化合物和/或氨基塑料成型剂制备可热固化树脂中以及在制备木材复合材料中可以用作反应性羰基化合物。
5-羟甲基糠醛(HMF)
是一种重要的平台化学物质，并且作为众多合成的起始化合物具有显著的意义。此外，已知，在基于酚类化合物和/或氨基塑料成型剂制备可热固化树脂中，反应性羰基化合物例如甲醛(其对健康有害)可至少部分地被HMF代替。在行业杂志European Journal ofWood Products中，描述了HMF改性脲-甲醛树脂，为了制备它，最高达约30wt％的甲醛被纯化的结晶HMF替代(N.Esmaeili et al.,DOI 10.1007/s0017-016-1072-8)。
HMF溶液中的线性和支化低聚物的出现是已知的(例如，DE 10 2014 112 240A1)。在其它实施例中，在水热条件下在由碳水化合物和含碳水化合物的生物质制造HMF期间形成HMF低聚物，并且可通过NMR、IR和质谱法检测。此外，可以通过HPLC分析追踪它们的形成。
来自HMF的已知的低聚化合物是获得自单独的HMF单体或单独单体的醛和/或羟基与由HMF单体组成的HMF低聚物的连接。HMF单体最终代表形成的HMF低聚物的单元。HMF低聚物是线性或更多或更少高度支化的，并且具有醚、半缩醛和/或缩醛键。在酸性条件下以及在碱性条件下均可形成HMF低聚物。
线性HMF低聚物通常包括包含以下各项的结构元件：通过醚键连接的类型的单元，
和/或通过形成半缩醛连接的类型单元
此外，支化HMF低聚物可以含有具有连接以形成缩醛的类型单元的结构元件
在这些连接中，曲线表示所示结构元件是HMF低聚物的一部分。HMF低聚物通常具有所示类型的多个相同或不同的结构元件。末端HMF单元通过醛或羟甲基基团结合。
发明人已发现，除了带有醚，半缩醛和/或缩醛键的HMF低聚物之外，碳连接的HMF低聚物(其中单元通过碳-碳键连接)在酸性条件和碱性条件两者下形成。作为实例，这些键可以在亲电攻击第一HMF单体的醛基或第二HMF单体的呋喃环的3或4位中的碳原子上HMF低聚物的HMF单元或HMF低聚物的HMF单元期间形成。
因此，本发明的主题是新型碳连接的HMF低聚物，其包括至少一个第一HMF单元和(至少)一个第二HMF单元，并且其特征在于，第一HMF单元和第二HMF单元通过碳-碳键连接，该碳-碳键连接涉及(包含，条件是，with involvement of)第一HMF单元的呋喃环的位置3或4处的芳香键合碳原子。
与HMF单体相比，来自至少两个链接的HMF单元/单体的化合物在本发明的含义内被指定为"HMF低聚物"。在上下文中，HMF低聚物和HMF聚合物之间的过渡是连续的。在本发明的含义内，"HMF低聚物"被理解为具有最高达3000g/mol的摩尔质量的化合物。
在本发明的含义内，HMF低聚物被指定为"碳连接的HMF低聚物"，条件是至少两个HMF单元通过碳-碳键连接，该碳-碳键连接涉及两个HMF单元中的一个的呋喃环的位置3或4处的芳香键合碳原子。
根据本发明的有利配置，第一单元的芳香族键合碳原子与第二HMF单元的醛碳原子相连。
所提出的用于形成碳-碳键的机理是，碳-碳键形成涉及在酸中和在碱中芳香键合的碳原子和醛碳原子，如在图1和2中给出。由此，可以清楚的是，除了别的事实之外，与仅通过HMF的醛和/羟基形成键的HMF低聚物相比，具有通过碳-碳键连接的HMF低聚物同时也具有更多的游离的官能醛基和/或羟基。这解释了基于额外的碳-碳键的较高交联程度也是有利的，由此在HMF低聚物中可获得较高密度的游离醛基和羟基。
根据本发明的另一有利的配置，碳连接HMF低聚物具有2至20HMF单元，优选2至10个HMF单元，特别优选2至4个HMF单元。具有2至10个单元的HMF低聚物在温和条件下(这意味着室温和常压)容易溶于水。
根据本发明的另一有利配置，除了涉及芳香键合的碳的连接的第一和第二HMF单元，碳连接的HMF低聚物包含至少一个另外的单元，其以醚半缩醛或缩醛键的形式连接到HMF单元。
本发明的另一个主题是制备碳连接的HMF低聚物的方法，其中该方法包括在水热条件下处理含纤维素的生物质的水性悬浮液和/或至少一种己糖的水性碳水化合物溶液和/或一种水性5-羟甲基糠醛溶液。
在用于制备5-HMF(单体)的水热条件下，处理碳水化合物或由碳水化合物衍生的化合物的生物质(例如基于植物的原料)是已知的，并且其提供了将起始材料暴露于含水介质中的压力和高温。发明人已经发现，在处理含纤维素的生物质的含水悬浮液和/或至少一种己糖的水性碳水化合物溶液和/或一种水性5-羟甲基糠醛溶液(在水热条件下)的过程中形成碳连接的HMF低聚物。
由于其低成本因素，含纤维素的生物质(其经常作为农业生产的废物来积累)是特别优选的。优选的己糖是果糖或葡萄糖，特别地，它们可以是果糖或果糖和葡萄糖的混合物。
优选的水热条件是饱和蒸汽压力和150℃至250℃的温度。这具有以下优点：根据起始原料，在数分钟至数小时内完成HMF低聚物的形成。
本发明的另一个主题是制备碳连接的HMF低聚物的方法，其中该方法包括将HMF单体和/或HMF低聚物的更高或更低纯的溶液暴露于导致HMF低聚物的形成的条件。优选地，HMF溶液暴露的条件包括溶液的碱化或酸化和/或加热。
发明人已发现，例如通过用水由结晶HMF制备的水性HMF溶液老化，形成HMF低聚物。在这个方面，可以使用本领域技术人员熟悉的分析手段，如HPLC和NMR光谱法来确定HMF低聚物的量和分子量。
在温和条件下(即，常压和室温)形成HMF低聚物可以持续数小时，数天或数周。可通过酸化，碱化，和加热来加速老化过程。
优选地，进行制造过程直到达到碳连接的HMF低聚物的所需量，或反应停止。
在这个方面，本领域技术人员应当清楚的是通过水热处理制备碳连接的HMF低聚物可与通过老化制备碳连接HMF低聚物结合。因此，例如，然后可以在常压下老化由水热处理获得的水溶液。
优选地，至少一种碳连接的HMF在制备结束时存在于水溶液中。
进一步优选的是影响碳连接的HMF低聚物或碳连接的HMF低聚物的含量、尺寸和/或浓度。特别优选地，通过在至少一种过滤装置上对含有碳连接的HMF低聚物的溶液进行过滤来影响碳连接的HMF低聚物或碳连接的HMF低聚物的含量。例如，在DE 10 2014 112 240A1中描述了在水热碳化之后处理(通过过滤)HMF水溶液。
碳连接的HMF低聚物非常适合作为可热固化树脂中的组分，其优选通过酚类化合物和/或氨基塑料成型剂与反应性羰基化合物特别是醛的缩聚而获得。具有氨基塑料成型剂脲、三聚氰胺和双氰胺的氨基树脂、酚醛树脂或氨基苯酚树脂可以作为实施例来提及。通过随后固化树脂来得到热固性塑料材料。
碳连接的HMF低聚物具有非常(高)的反应性并且具有额外的交联能力。它们在可热固化树脂中作为反应性羰基化合物是非常有效的。所获得的树脂通过特别好的加工性能，例如非常高的反应性来区分。使用碳连接的HMF低聚物来制备可热固化的树脂的主要优点是反应性羰基化合物如甲醛(其对健康有危害)可以完全省去。
通过缩聚制备可热固化树脂是以本身已知的方式进行的。合适的溶剂以及合适的反应条件如反应温度和pH原则上是本领域技术人员已知。优选地，在含水溶剂中进行反应。
碳连接的HMF低聚物可用于与其他反应性羰基化合物的混合物中。优选地，将至少一种HMF低聚物用于与至少一种HMF单体的混合物中和/或与含有醚，半缩醛和/或缩醛键的至少一种其他HMF低聚物的混合物中。甚至少量的碳连接HMF低聚物足以制备具有非常(高)的反应性的羰基化合物。
碳连接的HMF低聚物特别适合由含木质纤维素的材料，例如刨花、木纤维或木屑制备复合材料。根据本技术领域中公知的方法制备木材复合材料。木材复合材料可以如下获得：通过使含木质纤维素的材料与含有碳连接的HMF低聚物的可热固化树脂接触，然后固化树脂(其与交联相关)。优选通过压制提供有含木质纤维素的材料的树脂来进行固化。
以下实施例仅仅用作对本发明的解释说明，并不旨在以任何方式限制本发明。
实施例1:
实施例1显示了含有结构元件的碳连接的HMF低聚物的一部分，结构元件包括碳-碳键，该碳-碳键涉及第一HMF单元的呋喃环的芳香键碳原子和第二HMF单元的醛基碳原子。
为了清楚起见，如曲线所示，示出了碳连接HMF低聚物的一部分。实施例1中未示出的末端HMF单元优选通过醛或羟甲基基团结合。
实施例2:
刨花板面板的制造
a)制备含有HMF低聚物的HMF溶液：
通过在45℃和30毫巴(mbar)下在旋转蒸发器中减少体积，同时浓缩和老化结晶HMF的16％水溶液，直至相对于溶液，HMF的浓度为50wt％。
b)脲-HMF树脂的制备和性能比较：
制备脲与HMF的摩尔比不同的两种树脂。第一树脂(以下表示为UH(1:0.5))以脲与HMF的比例为1:0.5进行制备。第二树脂(以下表示为UH(1:0.25))以脲与HMF的比例为1:0.25进行制备。树脂的固体含量为约58％。对于这两种树脂，使用400ml的来自a)的50％的HMF溶液。对于这两种树脂，首先脲在pH 2下与HMF反应2.5小时，温度为90℃，然后在20℃的温度下反应数小时。在该过程中，观察到树脂粘度的变化。
表1:作为时间函数的粘度增加
树脂UH(1:0.5)(粘度为1275mPa.s)和树脂UH(1:0.25)(粘度为65mPa.s)用于后续压制刨花。将树脂分别与刨花和六亚甲基四胺混合，然后在220℃下压制以生产尺寸为250mm×250mm×16mm的面板。相对于木材的量，干木材的负载量为10wt％树脂固体。为了测试各种压制时间和各种固化剂的量的影响，使用不同时间和不同量的六亚甲基四胺产生多个面板。使用两种树脂UH(1:0.5)和UH(1:0.25)的刨花板面板所获得的值列于表2中。
为了比较，通过在45℃的较低温度下使树脂UH(1:0.5)的组分反应来制备第三树脂(UH45(1:0.5))。树脂UH45(1:0.5)还用于将刨花压制成尺寸为250mm×250mm×16mm的刨花板，这些刨花板面板所获得的值也在表2中给出。
用树脂生产的面板的比较表明，原则上，在较长的压制时间下获得了较好的内部粘合强度值。
使用脲与HMF的摩尔比为1:0.5，面板3和4获得较高值52N/mm2和55N/mm2。这些值可归因于7.5分钟的压制时间与用于制备树脂的高温90℃相关联。
面板1和2以及5和6示出了在制备树脂期间的温度的影响。
即使使用较少量的HMF生产的面板在延长了压制时间时也产生了令人满意的结果，如面板7至10所示。
关于固化剂，发现不同量的固化剂是稍微明显至不明显，条件是使用一定比例的HMF制成面板，如面板3至6所示。通过固化剂的量明显地更强烈地影响面板7和10(使用较低比例的HMF)。这些值表明，作为使用的HMF低聚物的阳性性质的结果，可大幅降低固化剂的需要量，可得到具有相同或相当的内部粘结强度的产品。
根据NF EN 319(AFNOR 1993)的内部粘合强度(IB)：
通过下式表示以[N/mm2]计的内部粘合强度
其中Fmax是断裂时的力，a是面板的宽度，以及b是面板的长度
对于具有在13mm至20mm范围内的厚度的刨花板和纤维板面板，NF EN 319(AFNOR1993)规定了≤0.35N/mm2的内部粘合强度。
通过切割出在c)下生产的面板，获得用于对内部粘合强度进行研究的面板。它们的尺寸为50mm×50mm。在切割之前，面板在干燥器中在20℃和65％的相对湿度下稳定。
通过热熔粘合剂将面板紧固到背衬上。根据NF EN 319(AFNOR 1993)，垂直于面板的平面，机械地进行内部粘合强度的测定。
表2：刨花板的生产参数和刨花板的性能
从权利要求和附图中可以推断出进一步的优点和有利的配置，
其中，
图1示出了基于两个HMF分子的二聚在酸性条件下碳-碳键形成的建议机理，以及
图2示出了基于两个HMF分子的二聚在碱性条件下碳-碳键形成的建议机理。
无论是单独地以及彼此的任何组合中，本发明的所有特征对于本发明都是重要的。
Claims (8)
1.新型碳连接的HMF低聚物，包含至少一种第一HMF单元和一种第二HMF单元，其特征在于，第一HMF单元和第二HMF单元通过碳-碳键连接，所述碳-碳键涉及所述第一HMF单元的呋喃环的位置3或4处的芳香键合的碳原子。
2.根据权利要求1所述的HMF低聚物，其特征在于，所述第一HMF单元的芳香键合的碳原子与所述第二HMF单元的醛碳原子相连。
3.根据权利要求1或权利要求2所述的HMF低聚物，其特征在于，所述碳连接的HMF低聚物具有2至20个HMF单元，优选2至10个HMF单元，特别优选2至4个HMF单元。
4.根据前述权利要求中一项所述的HMF低聚物，其特征在于，除了涉及芳香键合的碳的连接的所述第一HMF单元和所述第二HMF单元外，所述碳连接的HMF低聚物含有至少一种另外的单元，所述至少一种另外的单元通过形成醚、半缩醛或缩醛键连接到HMF单元。
5.用于制造HMF低聚物的方法，其中所述方法包括在水热条件下处理含纤维素的生物质的水性悬浮液和/或至少一种己糖的水性碳水化合物溶液和/或一种水性5-羟甲基糠醛溶液。
6.用于制造HMF低聚物的方法，其中所述方法包括在正常压力下将HMF单体和/或HMF低聚物的更高或更低纯的溶液暴露于导致HMF低聚物形成的条件。
7.根据权利要求1至4中一项所述的HMF低聚物用于制造可热固化树脂的用途。
8.根据权利要求1至4中一项所述的HMF低聚物用于由含木质纤维素的材料制造复合材料的用途。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP17158249.7A EP3366712A1 (de) | 2017-02-27 | 2017-02-27 | Neue hmf-oligomere |
| EP17158249.7 | 2017-02-27 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108504034A true CN108504034A (zh) | 2018-09-07 |
Family
ID=58347050
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810162862.2A Pending CN108504034A (zh) | 2017-02-27 | 2018-02-27 | 新型hmf低聚物 |
Country Status (10)
| Country | Link |
|---|---|
| US (1) | US10703849B2 (zh) |
| EP (1) | EP3366712A1 (zh) |
| JP (1) | JP2018140984A (zh) |
| CN (1) | CN108504034A (zh) |
| AU (1) | AU2018201399A1 (zh) |
| BR (1) | BR102018003729A2 (zh) |
| CA (1) | CA2996552A1 (zh) |
| MX (1) | MX2018002375A (zh) |
| PH (1) | PH12018000060A1 (zh) |
| RU (1) | RU2018106887A (zh) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP4255946A1 (en) | 2021-05-26 | 2023-10-11 | Lignum Technologies AG | Modified aminoplastic adhesive resin, procedure of its preparation and composite materials prepared using this modified aminoplastic adhesive resin |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102702144A (zh) * | 2012-06-15 | 2012-10-03 | 复旦大学 | 一种生物质纤维素制备呋喃类及糠醛类化合物的方法 |
| CN105773763A (zh) * | 2016-03-15 | 2016-07-20 | 东北林业大学 | 耐湿热低成本绝缘酚醛树脂层压板的制备方法 |
| US20160355631A1 (en) * | 2014-02-20 | 2016-12-08 | The University Of Western Ontario | Formaldehyde-free phenolic resins, downstream products, their synthesis and use |
Family Cites Families (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2776948A (en) * | 1953-08-03 | 1957-01-08 | Dendrol Inc | Synthetic resins derived from hydroxymethylfurfural and phenols |
| US2937158A (en) | 1956-06-28 | 1960-05-17 | Francis H Snyder And Associate | Process for forming resins from phenols and hydropyrolysis products of lignocellulose |
| US4048126A (en) | 1976-07-22 | 1977-09-13 | Cpc International Inc. | Process for producing carbohydrate-phenol condensation resins |
| US4524164A (en) * | 1983-12-02 | 1985-06-18 | Chemical Process Corporation | Thermosetting adhesive resins |
| US4692478A (en) | 1986-03-14 | 1987-09-08 | Chemical Process Corporation | Process for preparation of resin and resin obtained |
| US20080207795A1 (en) | 2007-01-19 | 2008-08-28 | Henry Colleen M | Binder Formulations Utilizing Furanic Components |
| US9162998B2 (en) | 2011-12-13 | 2015-10-20 | Basf Se | Preparation of 5-hydroxymethylfurfural (HMF) from saccharide solutions in the presence of a solvent having a boiling point greater than 60° C. and less than 200° C. (at standard pressure, called low boiler for short) |
| US9156802B2 (en) | 2011-12-13 | 2015-10-13 | Basf Se | Separating off 5-hydroxymethylfurfural (HMF) from reaction solutions by steam distillation |
| IN2014DN07205A (zh) | 2012-03-23 | 2015-04-24 | Kao Corp | |
| EP2813494A1 (de) | 2013-06-12 | 2014-12-17 | Basf Se | Verfahren zur Herstellung von 5-Hydroxymethylfurfural (HMF) |
| NO2681399T3 (zh) | 2014-08-26 | 2018-04-07 | ||
| US9725552B2 (en) | 2014-10-14 | 2017-08-08 | Industrial Technology Research Institute | HMF-based phenol formaldehyde resin |
| FR3049612A1 (fr) | 2016-04-01 | 2017-10-06 | Michelin & Cie | Composition adhesive aqueuse comportant une resine thermodurcissable |
-
2017
- 2017-02-27 EP EP17158249.7A patent/EP3366712A1/de not_active Withdrawn
-
2018
- 2018-02-26 BR BR102018003729-3A patent/BR102018003729A2/pt not_active Application Discontinuation
- 2018-02-26 PH PH12018000060A patent/PH12018000060A1/en unknown
- 2018-02-26 RU RU2018106887A patent/RU2018106887A/ru not_active Application Discontinuation
- 2018-02-26 MX MX2018002375A patent/MX2018002375A/es unknown
- 2018-02-26 CA CA2996552A patent/CA2996552A1/en not_active Abandoned
- 2018-02-26 US US15/904,814 patent/US10703849B2/en not_active Expired - Fee Related
- 2018-02-27 AU AU2018201399A patent/AU2018201399A1/en not_active Abandoned
- 2018-02-27 CN CN201810162862.2A patent/CN108504034A/zh active Pending
- 2018-02-27 JP JP2018033321A patent/JP2018140984A/ja active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102702144A (zh) * | 2012-06-15 | 2012-10-03 | 复旦大学 | 一种生物质纤维素制备呋喃类及糠醛类化合物的方法 |
| US20160355631A1 (en) * | 2014-02-20 | 2016-12-08 | The University Of Western Ontario | Formaldehyde-free phenolic resins, downstream products, their synthesis and use |
| CN105773763A (zh) * | 2016-03-15 | 2016-07-20 | 东北林业大学 | 耐湿热低成本绝缘酚醛树脂层压板的制备方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| CA2996552A1 (en) | 2018-08-27 |
| PH12018000060A1 (en) | 2019-04-29 |
| MX2018002375A (es) | 2018-11-09 |
| US10703849B2 (en) | 2020-07-07 |
| BR102018003729A2 (pt) | 2018-11-06 |
| RU2018106887A (ru) | 2019-08-26 |
| EP3366712A1 (de) | 2018-08-29 |
| JP2018140984A (ja) | 2018-09-13 |
| AU2018201399A1 (en) | 2018-09-13 |
| US20180244823A1 (en) | 2018-08-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108501164B (zh) | 用于制造木质复合材料的方法以及通过该方法可获得的木质复合材料 | |
| KR102100602B1 (ko) | 탄수화물계 결합제 시스템 및 이의 제조 방법 | |
| JP2014525488A5 (zh) | ||
| US10781280B2 (en) | Method for producing thermosetting phenolic resins and phenolic resins obtainable by the method | |
| EP2222907B1 (en) | Resin for producing an inorganic fiber material | |
| KR101922644B1 (ko) | 바인더 조성물, 물품 및 물품 제조방법 | |
| US20180244825A1 (en) | Process for the manufacture of thermally curable resins as well as resins obtainable by the process | |
| EP3887474B1 (en) | Process for preparing a solution of lignin in an aqueous medium | |
| RU2753759C2 (ru) | Связующее вещество для дерева, не содержащее формальдегид | |
| CN108504034A (zh) | 新型hmf低聚物 | |
| Dunky | Natural Crosslinkers for Naturally‐Based Adhesives | |
| US11667792B2 (en) | Process for preparing a solution of lignin in an aqueous medium | |
| SU1118655A1 (ru) | Композици дл изготовлени древесноволокнистых плит сухим способом | |
| STUECKER et al. | Organosolv Lignin in Phenol-Formaldehyde Resins-Effect of Molecular Weight and Lignin Methylolation | |
| JP2022133876A5 (zh) | ||
| SI8712426A8 (sl) | Postopek za pripravo sečninsko-cimetaldehidnih smol |
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 | ||
| REG | Reference to a national code |
Ref country code: HK Ref legal event code: DE Ref document number: 1260361 Country of ref document: HK |
|
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20180907 |
|
| WD01 | Invention patent application deemed withdrawn after publication |