CN101720341A - 复合木板 - Google Patents
复合木板 Download PDFInfo
- Publication number
- CN101720341A CN101720341A CN200780050375A CN200780050375A CN101720341A CN 101720341 A CN101720341 A CN 101720341A CN 200780050375 A CN200780050375 A CN 200780050375A CN 200780050375 A CN200780050375 A CN 200780050375A CN 101720341 A CN101720341 A CN 101720341A
- Authority
- CN
- China
- Prior art keywords
- binding agent
- wood board
- acid
- composite wood
- plate
- 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.)
- Granted
Links
- 239000002023 wood Substances 0.000 title claims abstract description 68
- 239000002131 composite material Substances 0.000 title claims abstract description 34
- 239000011230 binding agent Substances 0.000 claims abstract description 163
- 239000002245 particle Substances 0.000 claims abstract description 5
- 229920005989 resin Polymers 0.000 claims description 60
- 239000011347 resin Substances 0.000 claims description 60
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 33
- 235000000346 sugar Nutrition 0.000 claims description 33
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 239000011093 chipboard Substances 0.000 claims description 14
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 12
- 238000010521 absorption reaction Methods 0.000 claims description 11
- 239000007864 aqueous solution Substances 0.000 claims description 11
- 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 claims description 9
- 239000008103 glucose Substances 0.000 claims description 8
- 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 claims description 7
- 239000007795 chemical reaction product Substances 0.000 claims description 7
- 229910021529 ammonia Inorganic materials 0.000 claims description 6
- 239000011094 fiberboard Substances 0.000 claims description 6
- 239000000376 reactant Substances 0.000 description 113
- 239000002253 acid Substances 0.000 description 105
- 239000000463 material Substances 0.000 description 66
- 235000014633 carbohydrates Nutrition 0.000 description 65
- 238000006243 chemical reaction Methods 0.000 description 60
- 150000001720 carbohydrates Chemical class 0.000 description 57
- 239000000203 mixture Substances 0.000 description 54
- -1 carboxylic acid ammonium salt Chemical class 0.000 description 47
- 239000000126 substance Substances 0.000 description 43
- 229920002451 polyvinyl alcohol Polymers 0.000 description 32
- 230000007062 hydrolysis Effects 0.000 description 29
- 238000006460 hydrolysis reaction Methods 0.000 description 29
- 238000000034 method Methods 0.000 description 23
- 239000000853 adhesive Substances 0.000 description 22
- 230000001070 adhesive effect Effects 0.000 description 22
- 150000001412 amines Chemical class 0.000 description 22
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 21
- 238000002360 preparation method Methods 0.000 description 21
- 239000000835 fiber Substances 0.000 description 20
- 150000001875 compounds Chemical class 0.000 description 19
- 229920000642 polymer Polymers 0.000 description 19
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 18
- 150000003839 salts Chemical class 0.000 description 18
- 238000012360 testing method Methods 0.000 description 18
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 17
- 238000004519 manufacturing process Methods 0.000 description 17
- 239000000047 product Substances 0.000 description 17
- 239000007787 solid Substances 0.000 description 15
- 239000000243 solution Substances 0.000 description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 14
- 229920002689 polyvinyl acetate Polymers 0.000 description 14
- 239000011118 polyvinyl acetate Substances 0.000 description 14
- 150000003863 ammonium salts Chemical class 0.000 description 13
- 150000004676 glycans Chemical class 0.000 description 13
- 229920001282 polysaccharide Polymers 0.000 description 13
- 239000005017 polysaccharide Substances 0.000 description 13
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 12
- AIJULSRZWUXGPQ-UHFFFAOYSA-N Methylglyoxal Chemical compound CC(=O)C=O AIJULSRZWUXGPQ-UHFFFAOYSA-N 0.000 description 12
- 239000003513 alkali Substances 0.000 description 12
- 125000000217 alkyl group Chemical group 0.000 description 12
- 239000003365 glass fiber Substances 0.000 description 12
- 239000000178 monomer Substances 0.000 description 12
- 239000004135 Bone phosphate Substances 0.000 description 11
- PEDCQBHIVMGVHV-UHFFFAOYSA-N glycerol group Chemical group OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 11
- 229960001031 glucose Drugs 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 9
- 150000008065 acid anhydrides Chemical class 0.000 description 9
- 239000000654 additive Substances 0.000 description 9
- 229910052799 carbon Inorganic materials 0.000 description 9
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 9
- 229910052698 phosphorus Inorganic materials 0.000 description 9
- 239000011574 phosphorus Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 8
- 229920002522 Wood fibre Polymers 0.000 description 8
- LPQOADBMXVRBNX-UHFFFAOYSA-N ac1ldcw0 Chemical compound Cl.C1CN(C)CCN1C1=C(F)C=C2C(=O)C(C(O)=O)=CN3CCSC1=C32 LPQOADBMXVRBNX-UHFFFAOYSA-N 0.000 description 8
- 238000009998 heat setting Methods 0.000 description 8
- 229920001296 polysiloxane Polymers 0.000 description 8
- 229910000077 silane Inorganic materials 0.000 description 8
- 229920001187 thermosetting polymer Polymers 0.000 description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 7
- 150000001323 aldoses Chemical class 0.000 description 7
- 150000001721 carbon Chemical group 0.000 description 7
- 229920002678 cellulose Polymers 0.000 description 7
- 239000001913 cellulose Substances 0.000 description 7
- 150000002148 esters Chemical class 0.000 description 7
- 150000002584 ketoses Chemical group 0.000 description 7
- 238000011068 loading method Methods 0.000 description 7
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 239000002025 wood fiber Substances 0.000 description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 6
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- JFCQEDHGNNZCLN-UHFFFAOYSA-N glutaric acid Chemical compound OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 6
- LVHBHZANLOWSRM-UHFFFAOYSA-N itaconic acid Chemical compound OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 6
- 235000018102 proteins Nutrition 0.000 description 6
- 108090000623 proteins and genes Proteins 0.000 description 6
- 102000004169 proteins and genes Human genes 0.000 description 6
- XISYMCYXGZPFRD-OVNWPFPBSA-N triazanium;2-hydroxypropane-1,2,3-tricarboxylate;(2r,3s,4r,5r)-2,3,4,5,6-pentahydroxyhexanal Chemical compound [NH4+].[NH4+].[NH4+].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O XISYMCYXGZPFRD-OVNWPFPBSA-N 0.000 description 6
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 5
- 229920002125 Sokalan® Polymers 0.000 description 5
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 5
- 230000002378 acidificating effect Effects 0.000 description 5
- 230000000996 additive effect Effects 0.000 description 5
- 230000004523 agglutinating effect Effects 0.000 description 5
- 125000001931 aliphatic group Chemical group 0.000 description 5
- 125000003545 alkoxy group Chemical group 0.000 description 5
- 150000001413 amino acids Chemical class 0.000 description 5
- 238000005452 bending Methods 0.000 description 5
- 238000007334 copolymerization reaction Methods 0.000 description 5
- 239000011162 core material Substances 0.000 description 5
- MLUCVPSAIODCQM-NSCUHMNNSA-N crotonaldehyde Chemical compound C\C=C\C=O MLUCVPSAIODCQM-NSCUHMNNSA-N 0.000 description 5
- MLUCVPSAIODCQM-UHFFFAOYSA-N crotonaldehyde Natural products CC=CC=O MLUCVPSAIODCQM-UHFFFAOYSA-N 0.000 description 5
- 125000000392 cycloalkenyl group Chemical group 0.000 description 5
- 125000000753 cycloalkyl group Chemical group 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 125000001072 heteroaryl group Chemical group 0.000 description 5
- 230000036961 partial effect Effects 0.000 description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 5
- 239000000088 plastic resin Substances 0.000 description 5
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 239000002210 silicon-based material Substances 0.000 description 5
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 5
- 125000002769 thiazolinyl group Chemical group 0.000 description 5
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 230000033228 biological regulation Effects 0.000 description 4
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 125000004122 cyclic group Chemical group 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 235000011187 glycerol Nutrition 0.000 description 4
- 229910052736 halogen Inorganic materials 0.000 description 4
- 150000002367 halogens Chemical class 0.000 description 4
- 229920001519 homopolymer Polymers 0.000 description 4
- 150000001261 hydroxy acids Chemical group 0.000 description 4
- 238000006386 neutralization reaction Methods 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 235000019198 oils Nutrition 0.000 description 4
- 238000005457 optimization Methods 0.000 description 4
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 4
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 4
- 238000005507 spraying Methods 0.000 description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- GVNWZKBFMFUVNX-UHFFFAOYSA-N Adipamide Chemical class NC(=O)CCCCC(N)=O GVNWZKBFMFUVNX-UHFFFAOYSA-N 0.000 description 3
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 3
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 3
- 229930182474 N-glycoside Natural products 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 description 3
- 229930006000 Sucrose Natural products 0.000 description 3
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 3
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 3
- 150000001299 aldehydes Chemical class 0.000 description 3
- 229910052728 basic metal Inorganic materials 0.000 description 3
- 239000004202 carbamide Substances 0.000 description 3
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- 239000012986 chain transfer agent Substances 0.000 description 3
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical compound [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 3
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- 150000002341 glycosylamines Chemical class 0.000 description 3
- 150000002402 hexoses Chemical class 0.000 description 3
- 238000012423 maintenance Methods 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- HNEGQIOMVPPMNR-UHFFFAOYSA-N methylfumaric acid Natural products OC(=O)C(C)=CC(O)=O HNEGQIOMVPPMNR-UHFFFAOYSA-N 0.000 description 3
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 description 3
- 229940059574 pentaerithrityl Drugs 0.000 description 3
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 3
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- MEIRRNXMZYDVDW-MQQKCMAXSA-N (2E,4E)-2,4-hexadien-1-ol Chemical compound C\C=C\C=C\CO MEIRRNXMZYDVDW-MQQKCMAXSA-N 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 2
- NGCDGPPKVSZGRR-UHFFFAOYSA-J 1,4,6,9-tetraoxa-5-stannaspiro[4.4]nonane-2,3,7,8-tetrone Chemical compound [Sn+4].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O NGCDGPPKVSZGRR-UHFFFAOYSA-J 0.000 description 2
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 2
- IZFHMLDRUVYBGK-UHFFFAOYSA-N 2-methylene-3-methylsuccinic acid Chemical compound OC(=O)C(C)C(=C)C(O)=O IZFHMLDRUVYBGK-UHFFFAOYSA-N 0.000 description 2
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 description 2
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- 125000003368 amide group Chemical group 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 150000008064 anhydrides Chemical group 0.000 description 2
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- 230000027455 binding Effects 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
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- 239000011248 coating agent Substances 0.000 description 2
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- 238000010586 diagram Methods 0.000 description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 2
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Images
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- 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
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- 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
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- C—CHEMISTRY; METALLURGY
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L5/00—Compositions of polysaccharides or of their derivatives not provided for in groups C08L1/00 or C08L3/00
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
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Abstract
在复合木板的堆叠体中,该木板包含木材颗粒和有机粘结剂。
Description
技术领域
本发明涉及复合木板,例如碎料板(particle board),定向刨花板(orientated strand board)和木纤维板(wood fibre board),且特别涉及包含生物树脂(bioresin)和/或具有低甲醛或无甲醛粘结剂的复合木板。
背景技术
生物树脂是创造用于描述衍生自生物来源的树脂或树脂配制剂的术语。因此,许多传统的树脂例如基于蛋白质的大豆、胶原或酪蛋白,或者来自纤维素或淀粉的碳水化合物衍生物,基于天然橡胶的粘合剂和天然酚类粘合剂如单宁或木质素可以全部归类为生物树脂。它们是可再生的聚合物且具有低的环境影响力,代表着对于现有的石油驱动体系的替代品。
对生物树脂体系的兴趣主要来自对无污染环境越来越多的规定和公众关注,以及对基于有限的石油化工来源的产品的可持续替代品的需求。商业热固性树脂的制备和使用面临着主要归因于形成配制剂基础的单体组分这样的规定。势不可挡地,这些树脂基于蜜胺,苯酚,脲,甲醛,苯乙烯或异氰酸酯起始材料。
对于在碎料板(PB)、定向刨花板(OSB)、中等密度纤维板(MDF)和木纤维板的制造中涉及的安装,甲醛、苯酚和异氰酸酯的排放通常受到管制,在England和Wales它们处于Pollution Prevention and Control Regulations(2000),SI19的管理下。向空气中的排放限制在5mg/m3。特别地,手册记录操作员应当使用尽可能最少排放甲醛的树脂。所用树脂的选择应当连续地评估以保证最少排放的发生。问题可能存在关注于工作场所中的高甲醛水平和从板材产品本身中缓慢释放的甲醛,特别是在产品使用期限的开始时。
生物树脂产品可以提供热固性树脂的可替代的、可再生来源,它们将开始解决有限资源的耗尽问题并且具有更好的排放分布(profile),特别是当无甲醛地配制时。虽然无甲醛的材料,例如siisocyanate和单宁树脂已变得可获得,目前制备的MDF中的大约85%都使用了甲醛树脂,对应于欧洲市场为大约2百万吨/年。在这些树脂中,尽管最近几年已实现甲醛含量的减少,但付出的代价是较长的加工时间,由它们制备的板材产品的内部粘接和弯曲强度的降低以及溶胀和水分吸收的增加。因此,在市场中现在存在明确的对于新型环境更友好的树脂的需求,所述树脂在价格、性能和能够适应现有复合材料制造工艺方面有竞争性。
发明内容
根据一个方面,本发明提供一种如权利要求1中限定的复合木板。其它方面限定在其它独立权利要求中。在从属权利要求中限定了优选的和/或可选择的特征。
与实验室试验制造的木板不同,该复合木板优选为工业制造的复合木板。这种复合木板可以具有至少30cm×30cm的尺寸,它可以具有至少50cm×80cm的尺寸,有可能是至少1m×2m。
该复合木板可以具有被修整和/或切割和/或机械加工的边缘。
该复合木板可以作为包括多个排列和/或粘结在一起的木板的包装提供,例如为了有助于运输;它还可以包括包封薄膜,例如塑料材料。该包装可以包括托盘,它可以通过经由机械上升设备和/或叉车式卡车处理而适应。
该复合板材可以具有至少11mm、至少12mm或至少15mm的标称厚度。
该复合木板的固化时间优选为少于25分钟。
粘结剂可以:
·基于还原糖;和/或
·基于reductosis;和/或
·基于含醛的糖;和/或
·包括碳水化合物反应物和胺反应物的至少一种反应产物;和/或
·包括还原糖和胺反应物的至少一种反应产物;和/或
·包括碳水化合物反应物和多元羧酸铵盐反应物的至少一种反应产物;和/或
·包括由梅拉德反应(Maillard reaction)得到的至少一种反应产物。
附图简述
涉及本发明的实验室规模试验的非限制性实施例参考以下附图进行描述:
图1显示实施例2中板材的切割方式
图2显示压制时间对于实施例2中具有BS1树脂的碎料板的IB的影响
图3显示压制时间对于实施例2中具有BS1-SOK树脂的碎料板的IB的影响
图4显示与实施例2有关的在20℃下24小时后的厚度溶胀
图5显示与实施例2有关的在20℃下24小时后的水分吸收
图6显示压制时间对于与实施例2有关的具有BS1树脂的定向刨花板的IB的影响
图7显示用于制备蛋白黑素的许多举例说明性反应物
图8说明了当使还原糖与氨基化合物反应时梅拉德反应的示意图
具体实施方式
实施例1a:
用于构造木纤维板组合物的多元羧酸铵-糖粘结剂的制备
含水柠檬酸三铵-葡萄糖(1∶6)粘结剂通过以下一般性的程序制备:在1加仑的反应容器中混合粉末状的葡萄糖一水合物(915g)和粉末状的无水柠檬酸(152.5g),向其中加入880g的蒸馏水。在搅拌下向该混合物中加入265g的19%的氨水,搅拌连续几分钟以实现固体的完全溶解。向得到的溶液中加入3.3g的SILQUEST A-1101硅烷以制备pH值-8-9的溶液(使用pH试纸),其中该溶液包含大约50%溶解的葡萄糖一水合物和溶解的柠檬酸铵固体(作为溶液总重量的百分比);2g这种溶液的样品在400°F下热固化30分钟,它会产生30%的固体(重量损失归因于热固性粘结剂形成期间的脱水)。其中硅烷而不是SILQUEST A-1101包括在柠檬酸三铵-葡萄糖(1∶6)粘结剂中,用SILQUEST A-187硅烷、HYDROSIL 2627硅烷或Z-6020硅烷进行替换。当将添加剂包括在柠檬酸三铵-葡萄糖(1∶6)粘结剂中以制备粘结剂变体时,将该标准溶液分配在300g等分试样的瓶中,然后向其中供应各种添加剂。
图1所示为干燥的(未固化的)柠檬酸三铵-葡萄糖(1∶6)粘结剂的FT-IR光谱,其中该光谱作为来自10g在真空中干燥的30%(溶解的粘结剂固体)的粘结剂样品的显微薄膜(microscopic film)而获得。图2所示为固化的柠檬酸三铵-葡萄糖(1∶6)梅拉德粘结剂的FT-IR光谱,其中该光谱作为来自10g固化后的30%(溶解的粘结剂固体)的粘结剂样品的显微薄膜而获得。当将除柠檬酸之外的多元羧酸、除葡萄糖之外的糖、和/或添加剂用于制备含水的多元羧酸铵-糖粘结剂变体时,使用如以上描述的用于制备含水柠檬酸三铵-葡萄糖(1∶6)粘结剂相同的一般性程序。对于多元羧酸铵-糖粘结剂变体,有必要进行调节以便适应包含的例如代替柠檬酸的二元羧酸或聚合物多元羧酸,或者适应包含的例如代替葡萄糖的丙糖,或者适应包含的例如一种或多种添加剂。这种调节包括,例如,调节必需用于生成铵盐的氨水的体积,调节必需用于获得期望的多元羧酸铵与糖的摩尔比的反应物的克数,和/或包括处于期望的重量百分比的添加剂。
几种方法用于制备用这种柠檬酸三铵-葡萄糖(1∶6)粘结剂粘接的木纤维板/片材。一种典型的方法如下,该方法制备了结实的、均匀的样品:将处于各种各样的松木刨花和锯屑形式的木材由当地农场供应商店购买。用如收到时状态的木材以及分隔成刨花和锯屑组分的材料制备木纤维板样品,首先在烘箱中在大约200°F下干燥木材过夜,对于木材刨花这种干燥导致除去14-15%的水分,且对于锯屑除去大约11%的水分。之后,将干燥的木材放置在8英寸高×12英寸宽×10.5英寸深的塑料容器(大概尺寸)中。按照上述方法制备柠檬酸三铵-葡萄糖(1∶6)粘结剂(36%的粘结剂固体),并且之后当将容器从垂直方向倾斜30-40度且缓慢旋转(大约5-15rpm)时将160g粘结剂通过液压喷嘴喷涂在塑料容器中的400g木材样品上。在这一处理期间,将木材温和地翻滚,同时它变得均匀涂布。
将树脂处理(resinated)的木材样品放置在可折叠框架中并在以下条件下在加热的压板之间压缩:树脂处理的木材刨花,300psi;树脂处理的锯屑,600psi。对于每一种树脂处理的样品,固化条件为350°F下25-30分钟。所得到的样品板为大约10英寸长×10英寸宽,且在修整之前为大约0.4英寸厚,内部粘接良好,表面光滑且当在带锯上修整时进行净切割(clean cut)。制备的每种修整样品板的修整样品密度和尺寸如下:来自木材刨花的样品板,密度~54pcf,尺寸~8.3英寸长×9英寸宽×0.36英寸厚;来自锯屑的样品板,密度~44pcf,尺寸~8.7英寸长×8.8英寸宽×0.41英寸厚。每种样品板的估计的粘结剂含量为~12.6%。
实施例1b:
试验以下样品以便对比标准碎料板和定向刨花板和使用新型试验粘结剂制备的相似产品的挠曲强度和拉伸强度:
·由Builders Lumber购买的商购获得的1/2英寸碎料板
·由Builders Lumber购买的商购获得的1/2英寸定向刨花板(OSB)
·按照上述制备的试验木材碎料板
8.75×8.87×0.414371.9gm.44.1lbs3 12.6%粘结剂
·按照上述制备的试验木材刨花板(shavings board)
8.37×9×0.336361.2gm.54.4lbs3 12.6%粘结剂
试验的板材各自为大约83/4平方英寸。当购买时来自builders的板材为大约2ft×4ft。将这些板材切割为大约83/4平方英寸,以致从各种产品一致地收集样品。
试验结果列于表1-5中:
表1概述的结果
表2详细数据-标准碎料板(商店购买)
表3详细数据-试验的碎料板
表4详细数据-标准定向刨花板(商店购买)
表5详细数据-试验的定向刨花板
实施例2
使用两种实验树脂,BS1和BS1-SOK(50%的固体含量)。用这两种树脂体系制造碎料板(PB)、定向刨花板(OSB)和中等密度纤维板(MDF)。
试验碎料板的制造
制造单层碎料板。用于制造碎料板的木屑为用于商业碎料板制造的木屑,这些木屑由木材类物质的混合物组成并且认为其主要由再生木材组成。使用木屑之前将其过筛以除去过大的材料和碎片。树脂处理前,干燥木屑至恒定的水分含量(MC)。在下文中,水分含量将表达为包含在木材中的水分的重量在烘箱干燥的木材重量中的百分比。
将12%或14%的树脂加入到木屑中(树脂固体的重量相对干燥木材的重量)。在Kenwood或Drum共混器中将树脂和木屑共混在一起。测量干燥木屑的水分含量和经喷涂木屑的水分含量;表6中总结了这些信息。为了获得650kg/m3的目标密度,根据水分含量调整每块板材的木屑质量。
将树脂、添加剂和木屑共混后,将所得到的“配料”转移到成形室中并且在用于最后凝固和树脂固化的热压之前轻轻地压缩。
使用220℃的目标压板温度和5-12分钟的总压制时间压制板材。板材为500mm×500mm或300mm×300mm平方且为12mm厚。从热压中移去之后,给板材贴上标签并且冷却后修整边缘。
试验的定向刨花板的制造
筛选薄片并且分离为核心和表面薄片。大尺寸的薄片用于表面层,小尺寸的用于核心层。
在两个共混器中将表面材料与14%的BS1树脂(用于木材的树脂,基于干重)和水共混。将树脂与水通过静态混合器混合。添加水以便降低树脂的粘度并且将薄片的MC增加到12%。
在单个共混器中将核心材料与12%的BS1树脂和水共混。目标核心薄片的MC为10-12%。
将共混的材料传送到三个成形位置,表面、核心和表面。表面成形器平行于机器方向排列薄片,而核心成形器垂直于机器方向排列薄片。薄片的排列通过成形位置中一系列叶片或辊实现。
表7中显示了板材的信息。PB-1到PB-11用BS1树脂制备,PB12到PB14用BS1-SOK树脂制备。
表6碎料板信息
表7定向刨花板信息
试验中等密度纤维板的制造:
使用标准原材料:由Kronospan获得的碎片状软木(主要是云杉)。
将12%的BS1树脂加入MDF(树脂固体的重量相对干燥纤维的重量)中。共混前和共混后MC分别为8.26%和16.23%。
使用220℃的目标压板温度和10分钟的总压制时间压制板材。
用于试验的样品的制备
冷却后将每种板材切割成规定的图案,细节参见图1。
样品尺寸(位置1-12)为50mm×50mm平方,位置13和14的样品宽度为50mm。
对于每种板材根据EN319试验六个样品(位置1、3、5、8、10和12)的内部粘接强度,根据EN317试验六个(位置2、4、6、7、9和11)的厚度溶胀和水分吸收。根据EN310试验来自位置13和14的两个的弯曲弹性模量和弯曲强度。
试验
内部粘接强度
·横向内部粘接强度。(对于PB为EN 319且对于OSB为EN 300)。
水分吸收&厚度溶胀
·在水中在20℃下24小时后的厚度溶胀(EN 317)
·在水中在20℃下24小时后的水分吸收
弯曲弹性模量和弯曲强度
·弹性模量(MOE),(EN 310)
·弯曲强度(MOR)
碎料板的试验结果
表8总结了碎料板内部粘接强度(IB)的结果。
图2和3显示了压制时间对IB的影响。可以注意到PB-3到PB-9分享了相同的加工(温度和时间)且IB在误差范围内变化,因此图2中包括了具有STD0.03的0.43N/mm2的平均值。图2和3还表明来自标准物的对于IB的通常要求为0.4N/mm2。
很明显,PB-1和PB-12中压制了5分钟的树脂由于并不充分的压制时间而没有产生出显著的粘接强度,当将压制时间增加到9分钟(PB-2和PB-13)时粘接强度得以改进,对于具有BS1树脂的PB(PB-3到PB-9),当进一步将压制时间增加到10分钟时获得了高于标准值的粘接强度。但是具有BS1-SOK树脂体系的样品,IB(PB14)低于标准要求。
对于其中添加了蜡的PB-10,看上去其对于IB没有显著的影响。
对于具有14%的树脂装载量(比其它板材高2%)的PB-11,它的IB为0.5N/mm2。这表明树脂装载量的增加将会提高粘接强度。
表8板材的内部粘接强度
图4和5总结了厚度溶胀和水分吸收的试验结果。
PB-8、9和10在相同的温度和时间下加工,PB-8、9和10之间的不同之处仅在于在PB-10中添加了蜡,0.8%的蜡。
PB-8和PB-9之间在厚度溶胀和水分吸收方面没有显著的差别,厚度溶胀和水分吸收均比标准要求的高很多,如图6中实线所示。添加了蜡明显具有显著的差别,样品具有最低的厚度溶胀和水分吸收,其还低于标准的要求。这表明使用蜡有助于改进厚度溶胀和水分吸收。
弯曲弹性模量和弯曲强度
仅对在220℃下压制10分钟制备的板材(PB-8和PB-9)试验了弹性模量和弯曲强度。对于MOE的平均值为2314N/mm2,其具有257.68的STD,这比标准要求的1800N/mm2高很多。这意味着板材要硬地多。对于MOR的平均值为10.4N/mm2,这比要求的14N/mm2低。为了改进MOR以适应要求,正确的方法可以是增加树脂的装载量。
定向刨花板(OSB)的结果
图6总结了定向刨花板的内部粘接结果,实线表明对于OSB标准(EN 300)要求其为0.28N/mm2。
IB总是低于要求值,为了改进具有BS1树脂的OSB板材的粘接强度,应当考虑加工参数和/或树脂装载量。
弯曲弹性模量和弯曲强度
试验板材OSB-2和OSB-3的MOR和MOE,结果总结于表9中。标准要求它们为18N/mm2和2500N/mm2。虽然IB较低,但是OSB-2和OSB-3都具有比用于普通目的板材所要求的更高的MOR和MOE。不仅纤维和树脂之间的粘接强度而且纤维尺寸和取向都有利于MOR和MOE。
当前值也高于对于用于干燥和潮湿条件下的20N/mm2和3500N/mm2的承重板的要求,但是,低于对于重型承重板的28N/mm2和4800N/mm2的要求。
表9OSB的MOR和MOE结果
MOR,N/mm2 | STD | MOE,N/mm2 | STD | |
OSB-2 | 26.47 | 4.11 | 4158.0 | 564.58 |
OSB-3 | 24.89 | 2.42 | 3861.9 | 428.73 |
中等密度板的结果
内部粘接强度
仅仅显示中等密度板的一个实验。压制温度为220℃且压制时间为10分钟。IB的平均值为0.43N/mm2,其具有0.03的STD,这高于标准要求的0.4N/mm2。
弯曲弹性模量和弯曲强度
对于MOR的平均值为22.26N/mm2,其具有1.31的STD,这比标准要求的14N/mm2高了60%。对于MOE的平均值为2771.62N/mm2,其具有204.17的STD,这比要求的1800N/mm2高了50%以上。
注意到的是14N/mm2和1800N/mm2是对于在干燥条件下使用的普通目的板材的要求。对于在干燥或潮湿条件下使用的承重板,该要求为18N/mm2和2500N/mm2,以及0.45N/mm2的IB。虽然IB略低,但是当前的MOR和MOE值比这一要求更高。但是,采用加工的最优化,MDF必须达到所有对于承重板或者甚至是对于重型承重板的要求。
来自实施例2的结果的讨论:
压制时间和树脂装载量在用BS1树脂制备的碎料板的IB中起到了重要的作用,IB随着压制时间和树脂装载量的增加而增加。但是,对于用BS1-SOK树脂制备的碎料板,IB随着压制时间的增加而变化,并且其还总是低于标准的要求。期望加工参数的优化以带来改进。
通过在碎料板中添加蜡改进了厚度溶胀和水分吸收,所述值低于标准的要求。优化会带来改进。
用BS1树脂制备的定向刨花板具有比标准要求更低的IB,但是具有比标准要求更高的MOR和MOE。IB强烈地取决于纤维和基质之间的粘接强度,但是,MOR和MOE将受益于纤维尺寸和取向。
通过使用BS1树脂,中等密度纤维板显示了比普通目的板材的要求更高的机械性质,有可能通过优化加工而达到用于承重板的要求。
具有BS1树脂的定向刨花板的问题在于较低的IB,为了改进这一性能,正确的前进方向可以是增加树脂的装载量。
具有BS1树脂的中等密度板材表现出优良的性能,加工的优化可以满足承重板或者甚至重型承重板的要求。
尽管将特定的粘结剂用于实施例中,其它粘结剂特别是以下讨论的粘结剂可以用于本发明的上下文中。
粘结剂的讨论:
与本发明有关的可使用的固化的或未固化的粘结剂可以包含以下特征中的一种或多种或它们的组合。此外,根据本发明的材料可以包含以下特征中的一种或多种或它们的组合。
首先应当理解的是该粘结剂可以用于多种制造应用以产生或促进非集合或松散集合的物质集合体中的内聚力。集合体包括两种或更多种组分。粘结剂在集合体的至少两种组分中产生或促进了内聚力。例如,主题粘结剂能够使物质的集合体保持在一起,使得物质以抵抗分离的方式粘合。这里描述的粘结剂可以用于任何材料的制造。
本发明粘结剂的一种潜在的特征在于它们不含甲醛。因此,粘结剂配置于其上的材料也可以是不含甲醛的。此外,本发明的粘结剂与其它已知的粘结剂相比可以具有降低的三甲基胺含量。关于本发明粘结剂的化学构成,它们可以包括酯和/或聚酯化合物。该粘结剂可以包括酯和/或聚酯化合物连同植物油例如大豆油。此外,该粘结剂可以包括酯和/或聚酯化合物连同有机酸的钠盐。该粘结剂可以包括无机酸的钠盐。该粘结剂还可以包括有机酸的钾盐。而且,该粘结剂可以包括无机酸的钾盐。描述的粘结剂可以包括酯和/或聚酯化合物连同粘土添加剂例如蒙脱土。
此外,本发明的粘结剂可以包括梅拉德反应的产物。例如,参见图8。如图8中所示,梅拉德反应产生了蛋白黑素,即高分子量、呋喃环且含氮的聚合物,它取决于反应物和它们的制备条件而有不同的结构。蛋白黑素表现出随着加热的温度和时间增加的C∶N比,不饱和度以及化学芳香性。(参见Ames,J.M.TheMaillard Browning Reaction-更新版,Chemistry and Industry(GreatBritain),1988,7,558-561,其中公开的内容通过引用并入本发明)。因此,主题粘结剂可以通过梅拉德反应制造并且因此含有蛋白黑素。应当理解的是主题粘结剂可以包含蛋白黑素,或者其它梅拉德反应产物,所述产物通过单独的方法产生并且然后简单地添加到构成粘结剂的组合物中。粘结剂中的蛋白黑素可以是水不溶性的。此外,该粘结剂可以是热固性粘结剂。
制备蛋白黑素的梅拉德反应物可以包括与还原糖碳水化合物反应物反应的胺反应物。例如,单体的多元羧酸的铵盐可以与(i)醛糖或酮糖形式的单糖或(ii)多糖或(iii)它们的组合反应。在另一种变形中,聚合物多元羧酸的铵盐可以与(i)醛糖或酮糖形式的单糖或(ii)多糖,或(iii)它们的组合接触。在另一个变形中,氨基酸可以与(i)醛糖或酮糖形式的单糖或(ii)多糖,或(iii)它们的组合接触。此外,肽可以与(i)醛糖或酮糖形式的单糖或(ii)多糖,或(iii)它们的组合接触。而且,蛋白质可以与(i)醛糖或酮糖形式的单糖或(ii)多糖,或(iii)它们的组合接触。
还应当理解的是粘结剂可以包括在梅拉德反应的非糖变体中制备的蛋白黑素。在这些反应中,胺反应物与非碳水化合物羰基反应物接触。在一个说明性的变体中,单体的多元羧酸的铵盐与非碳水化合物羰基反应物接触,例如丙酮醛,乙醛,巴豆醛,2-糠醛,醌,抗坏血酸或类似物,或者是它们的组合。在另一个变形中,聚合物多元羧酸的铵盐可以与非碳水化合物羰基反应物接触,例如丙酮醛,乙醛,巴豆醛,2-糠醛,醌,抗坏血酸或类似物,或者是它们的组合。还在另一个说明性的变体中,氨基酸可以与非碳水化合物羰基反应物接触,例如丙酮醛,乙醛,巴豆醛,2-糠醛,醌,抗坏血酸或类似物,或者是它们的组合。在另一个说明性的变体中,肽可以与非碳水化合物羰基反应物接触,例如丙酮醛,乙醛,巴豆醛,2-糠醛,醌,抗坏血酸或类似物,或者是它们的组合。仍然在另一个说明性的变体中,蛋白质可以与非碳水化合物羰基反应物接触,例如丙酮醛,乙醛,巴豆醛,2-糠醛,醌,抗坏血酸或类似物,或者是它们的组合。
这里讨论的蛋白黑素可以由蛋白黑素反应物化合物生成。这些反应物化合物在碱性pH值下配置在水溶液中并且因此并不是腐蚀性的。即,碱性溶液阻止或抑制了由例如酸带来的化学分解导致的物质(例如金属)的腐蚀或磨损。反应物化合物可以包括还原糖碳水化合物反应物和胺反应物。此外,反应物化合物可以包括非碳水化合物羰基反应物和胺反应物。
还应当理解的是这里描述的粘结剂可以由蛋白黑素反应物化合物本身制备。即,一旦混合了梅拉德反应物,这种混合物可以起到本发明粘结剂的作用。这些粘结剂可以用于制造未固化的无甲醛的物质,例如纤维性材料。
在选择性的方案中,由梅拉德反应的反应物制造的粘结剂可以固化。这些粘结剂可以用于制造固化的无甲醛的物质,例如,纤维性组合物。这些组合物是耐水的,正如上面指出的,包括水不溶性蛋白黑素。
应当理解的是这里描述的粘结剂可以用于从非集合或松散集合的物质的集合体制造产品。例如,这些粘结剂可以用于制造纤维产品。在一个说明性的实施方案中,粘结剂可以用于制备纤维素组合物。关于纤维素组合物,粘结剂可以用于粘接纤维素物质以制造例如具有期望物理性质(例如机械强度)的木纤维板。
本发明的一个实施方案涉及一种由非集合或松散集合的物质的集合体制造产品的方法。这种方法可以包括使纤维与可热固化的含水粘结剂接触。这种粘结剂可以包括(i)多元羧酸铵盐反应物和(ii)还原糖碳水化合物反应物。这两种反应物为蛋白黑素反应物(即,当在引发梅拉德反应的条件下反应时这些反应物产生蛋白黑素)。这种方法可以进一步包括从与纤维接触的粘结剂中除去水分(即,粘结剂是脱水的)。这种方法还可以包括使与纤维接触的粘结剂固化(例如,使粘结剂热固化)。
使用这种方法的实施例为制造纤维素材料。这种方法可以包括使纤维素材料(例如,纤维素纤维)与可热固化的、含水粘结剂接触。该粘结剂可以包括(i)多元羧酸铵盐反应物和(ii)还原糖碳水化合物反应物。正如以上所指出的,这两种反应物是蛋白黑素反应物化合物。这种方法还可以包括从与纤维素材料接触的粘结剂中除去水分。正如前述,这种方法还可以包括使粘结剂固化(例如,热固化)。
描述了纤维性产品,其包括与纤维素纤维接触的粘结剂,例如在木材刨花或锯屑的毡中的那些物质。所述毡可以加工以形成一种类型或多种类型的木纤维板产品。在一个变体中,粘结剂是未固化的。在这种变体中,未固化的粘结剂可以用于将纤维素纤维保持在一起。在选择性的方案中,固化的粘结剂可以用于将纤维素纤维保持在一起。
正如这里使用的,“无甲醛”这一短语表示作为干燥和/或固化的结果,粘结剂或结合了粘结剂的材料释放出小于大约1ppm的甲醛。该1ppm基于用于测量甲醛释放的样品的重量。
固化说明粘结剂已经被暴露在以至于引发化学变化的条件下。这些化学变化的实例包括但不限于(i)共价键接,(ii)粘结剂组分的氢键结合,以及在粘结剂中的聚合物和/或低聚物的化学交联。与未固化的粘结剂相比,这些变化可以增加粘结剂的耐久性和耐溶剂性。固化粘结剂会导致形成热固性材料。此外,固化可以包括蛋白黑素的生成。这些蛋白黑素可以由梅拉德反应从蛋白黑素反应无化合物生成。此外,与未固化的粘结剂相比,固化的粘结剂可以导致集合体中物质之间粘合的增加。固化可以通过例如热,电磁辐射或电子束引发。
在粘结剂中的化学变化导致水释放的情况中,例如聚合和交联,固化可以通过高于仅由干燥产生的释放的水量进行测定。用于测量干燥期间释放的水量和相比于当固化粘结剂时释放的水量的技术是现有技术中公知的。
根据以上段落,未固化的粘结剂是没有被固化的粘结剂。
正如这里使用的,术语“碱性”表示具有大于或等于大约7的pH值的溶液。例如,溶液的pH值可以小于或等于大约10。此外,溶液可以具有大约7到大约10的pH值,或者是大约8到大约10,或者是大约9到大约10。
正如这里使用的,术语“铵”包括但不限于+NH4,+NH3R1和+NH2R1R2,其中R1和R2各自独立的选自+NH2R1R2,且其中R1和R2选自烷基,环烷基,烯基,环烯基,杂环基,芳基和杂芳基。
术语“烷基”指的是碳原子的饱和单价链,其可以任选地是支化的;术语“环烷基”指的是碳原子的单价链,其中的一部分形成环;术语“烯基”指的是包括至少一个双键的碳原子不饱和单价链,其可以任选地是支化的;术语“环烯基”指的是碳原子的不饱和单价链,其中的一部分形成环;术语“杂环基”指的是碳原子和杂原子的单价链,其中杂原子选自氮、氧和硫,其中包括至少一个杂原子的一部分形成环;术语“芳基”指的是碳原子的芳族单环或多核环,例如苯基,萘基以及类似基团;以及术语“杂芳基”指的是碳原子和至少一个选自氮、氧和硫的杂原子的芳族单环或多核环,例如吡啶基,嘧啶基,吲哚基,苯并噁唑基以及类似基团。可以理解的是烷基、环烷基、烯基、环烯基和杂环基中的每一种可以任选地被独立选择的基团(例如烷基、卤代烷基,羟烷基,氨基烷基,羧酸和其衍生物,包括酯、酰胺和腈,羟基,烷氧基,酰氧基,氨基,烷基和二烷基氨基,酰氨基,硫代和类似基团,以及它们的组合)所取代。可以进一步理解的是芳基和杂芳基中的每一种可以任选地被一种或多种独立选择的取代基所取代,例如卤素,羟基,氨基,烷基或二烷基氮基,烷氧基,烷基磺酰基,氰基,硝基和类似的基团。
正如这里所使用的,术语“多元羧酸”表示二元羧酸、三元羧酸、四元羧酸、五元羧酸和类似的单体的多元羧酸,以及酸酐和它们的组合,还有聚合物多元羧酸,酸酐,共聚物和它们的组合。一方面,多元羧酸铵盐反应物是足够的非挥发性的以便将其保持可获得用于与梅拉德反应(以下讨论)的碳水化合物反应物反应的能力最大化。另一方面,多元羧酸铵盐反应物可以被其它化学官能团取代。说明性地,单体的多元羧酸可以是二元羧酸,包括但不限于不饱和脂族二元羧酸,饱和脂族二元羧酸,芳族二元羧酸,不饱和环状二元羧酸,饱和环状二元羧酸,它们的羟基取代的衍生物以及类似物。或者,说明性地,多元羧酸(一种或多种)本身可以是三元羧酸,包括但不限于不饱和脂族三元羧酸,饱和脂族三元羧酸,芳族三元羧酸,不饱和环状三元羧酸,饱和环状三元羧酸,它们的羟基取代的衍生物以及类似物。应当理解是任何这种多元羧酸可以是任选地取代的,例如用羟基,卤素,烷基,烷氧基以及类似基团取代。在一个变体中,多元羧酸是饱和脂族三元羧酸,柠檬酸。其它合适的多元羧酸预期包括但不限于乌头酸,己二酸,壬二酸,丁烷四羧酸二氢化物,丁烷三羧酸,氯菌酸,柠康酸,二环戊二烯-马来酸加合物,二亚乙基三胺五乙酸,二戊烯和马来酸的加合物,乙二胺四乙酸(EDTA),完全马来酸化的松香,马来酸化的妥尔油脂肪酸,富马酸,戊二酸,间苯二甲酸,衣康酸,用过氧化钾氧化为醇、然后羧酸的马来酸化的松香,马来酸,苹果酸,中康酸,通过KOLBE-Schmidt反应与二氧化碳反应以引入3-4个羧基的双酚A或双酚F,草酸,邻苯二甲酸,癸二酸,琥珀酸,酒石酸,对苯二甲酸,四溴邻苯二甲酸,四氯邻苯二甲酸,四氢化邻苯二甲酸,偏苯三酸,苯均三酸和类似物,以及酸酐和它们的组合。
说明性地,聚合物多元羧酸可以是酸,例如聚丙烯酸,聚甲基丙烯酸,聚马来酸和类似的聚合物多元羧酸,它们的共聚物,它们的酸酐和它们的混合物。商购获得的聚丙烯酸的实例包括AQUASET-529(Rohm & Haas,Philadelphia,PA,USA),CRITERION 2000(Kemira,Helsinki,Finland,Europe),NF1(H.B.Fuler,St.Paul,MN,USA)和SOKALAN(BASF,Ludwigshafen,Germany,Europe)。关于SOKALAN,它是一种丙烯酸和马来酸的水溶性聚丙烯酸类共聚物,具有大约4000的分子量。AQUASET-529是一种包含用丙三醇交联的聚丙烯酸的组合物,其还包含次磷酸钠作为催化剂。CRITERION 2000是一种聚丙烯酸部分成盐的酸性溶液,具有大约2000的分子量。关于NF1,这是一种包含羧酸官能度和羟基官能度以及不具有官能度的单元的共聚物,NF1还包含链转移剂,例如次磷酸钠或有机磷酸盐催化剂。
此外,包括聚合物多元羧酸的组合物还预期可用于制备这里描述的粘结剂,例如U.S.专利Nos.5,318,990,5,661,213,6,136,916和6,331,350中描述的那些组合物,其中公开的内容通过引用并入本发明。特别地,在U.S.专利Nos.5,318,990和6,331,350中,描述了一种聚合物多元羧酸、多元醇和催化剂的水溶液。
正如U.S.专利Nos.5,318,990和6,331,350中所描述的,聚合物多元羧酸包括包含多于一个侧挂羧基的有机聚合物或低聚物。该聚合物多元羧酸可以是由不饱和羧酸制备的均聚物或共聚物,包括但并不必要限于丙烯酸,甲基丙烯酸,巴豆酸,异巴豆酸,马来酸,肉桂酸,2-甲基马来酸,衣康酸,2-甲基衣康酸,α,β-亚甲基戊二酸以及类似物。选择性地,聚合物多元羧酸可以由不饱和酸酐制备,包括但并不必要限于马来酸酐,衣康酸酐,丙烯酸酐,甲基丙烯酸酐以及类似物,还有它们的混合物。这些酸和酸酐的聚合方法是化学领域中公知的。该聚合物多元羧酸可以额外地包括一种或多种前述不饱和羧酸或酸酐和一种或多种乙烯基化合物的共聚物,包括但并不必要限于苯乙烯,α-甲基苯乙烯,丙烯腈,甲基丙烯腈,丙烯酸甲酯,丙烯酸乙酯,丙烯酸正丁酯,丙烯酸异丁酯,甲基丙烯酸甲酯,甲基丙烯酸正丁酯,甲基丙烯酸异丁酯,甲基丙烯酸缩水甘油酯,乙烯基甲基醚,乙酸乙烯酯以及类似物。制备这些共聚物的方法是现有技术中公知的。该聚合物多元羧酸可以包括聚丙烯酸的均聚物和共聚物。该聚合物多元羧酸,特别是聚丙烯酸聚合物的分子量可以小于10000,小于5000,或者大约为3000或更小。例如,其分子量可以是2000。
正如U.S.专利Nos.5,318,990和6,331,350中所描述的,多元醇(在包括聚合物多元羧酸的组合物中)包含至少两个羟基。该多元醇应该是足够的非挥发性的,使得它将基本上保持可获得用于在加热和固化操作期间与组合物中的聚合物多元羧酸反应。该多元醇可以是带有至少两个羟基的分子量小于大约1000的化合物,例如乙二醇,丙三醇,季戊四醇,三羟甲基丙烷,山梨醇,蔗糖,葡萄糖,间苯二酚,儿茶酚,焦棓酚,乙醇酸脲,1,4-环己烷二醇,二乙醇胺,三乙醇胺和某些反应性多元醇,例如,β-羟烷基酰胺,例如举例来说有双[N,N-二(β-羟乙基)]己二酰胺,或者它可以是含有至少两个羟基的加成聚合物,例如聚乙烯醇,部分水解的聚乙酸乙烯酯和羟乙基(甲基)丙烯酸酯、羟丙基(甲基)丙烯酸酯的均聚物或共聚物以及类似的物质。
正如U.S.专利Nos.5,318,990和6,331,350中所描述的,催化剂(在包括聚合物多元羧酸的组合物中)为可以是分子量小于大约1000的化合物的含磷促进剂,例如,碱金属多磷酸盐,碱金属二氢磷酸盐,多磷酸和烷基次磷酸,或者它可以是带有含磷基团的低聚物或聚合物,例如丙烯酸和/或马来酸在次磷酸钠的存在下形成的加成聚合物,由烯属不饱和单体在磷盐链转移剂或终止剂的存在下制备的加成聚合物,以及含有酸官能化单体残基的加成聚合物,例如,共聚的phosphoethyl甲基丙烯酸酯,以及类似的膦酸酯,共聚的乙烯基磺酸单体和它们的盐。基于聚合物多元羧酸和多元醇的总重量,含磷促进剂可以在大约1%到大约40%重量的水平下使用。基于聚合物多元羧酸和多元醇的总重量,可以使用大约2.5%到大约10%重量水平的含磷促进剂。这种催化剂的实例包括但不限于次磷酸钠,亚磷酸钠,亚磷酸钾,焦磷酸二钠,焦磷酸四钠,三聚磷酸钠,六偏磷酸钠,磷酸钾,聚偏磷酸钾,多磷酸钾,三聚磷酸钾,三偏磷酸钠和四偏磷酸钠以及它们的混合物。U.S.专利Nos.5,661,213和6,136,916中描述的预期用于制备这里描述的粘结剂的包括聚合物多元羧酸的组合物包括聚合物多元羧酸、包含至少两个羟基的多元醇和含磷促进剂的水溶液,其中羧酸基团的当量数与羟基的当量数之比为大约1∶0.01到大约1∶3。
正如U.S.专利Nos.5,661,213和6,136,916中公开的,聚合物多元羧酸可以是含有至少两个羧酸基团的聚酯或含有至少两种共聚的羧酸官能化单体的加成聚合物或低聚物。聚合物多元羧酸优选为由至少一种烯属不饱和单体形成的加成聚合物。加成聚合物可以是加成聚合物在含水介质中的溶液形式,例如溶解于碱性介质的碱溶性树脂;含水分散体的形式,例如,乳液聚合的分散体;或者是含水悬浮体的形式。加成聚合物必须含有至少两个羧酸基团,酸酐基团或它们的盐。烯属不饱和羧酸,例如甲基丙烯酸,丙烯酸,巴豆酸,富马酸,马来酸,2-甲基马来酸,衣康酸,2-甲基衣康酸,α,β-亚甲基戊二酸,单烷基马来酸酯和富马酸单烷基酯;烯属不饱和酸酐,例如,马来酸酐,衣康酸酐,丙烯酸酐和甲基丙烯酸酐,以及它们的盐,基于加成聚合物的重量,可以使用的水平为大约1%到100%。另外的烯属不饱和单体可以包括丙烯酸酯单体,包括丙烯酸甲酯,丙烯酸乙酯,丙烯酸丁酯,丙烯酸2-乙基己酯,丙烯酸癸酯,甲基丙烯酸甲酯,甲基丙烯酸丁酯,甲基丙烯酸异癸酯,丙烯酸羟乙基酯,甲基丙烯酸羟乙基酯和甲基丙烯酸羟丙基酯;丙烯酰胺或取代的丙烯酰胺;苯乙烯或取代的苯乙烯;丁二烯;乙酸乙烯酯或其它乙烯基酯;丙烯腈或甲基丙烯腈以及类似物。包含至少两个羧酸基团、酸酐基团或它们的盐的加成聚合物可以具有大约300到大约10,000,000的分子量。也可以使用大约1000到大约250,000的分子量。当加成聚合物是具有羧酸、酸酐或它们的盐的碱溶性树脂时,基于加成聚合物的总重量,可以使用大约5%到大约30%的含量,以及大约10,000到大约100,000的分子量。制备这些加成聚合物的方法是现有技术中公知的。
正如U.S.专利Nos.5,661,213和6,136,916中描述的,多元醇(在包括聚合物多元羧酸的组合物中)包含至少两个羟基并且应该是足够的非挥发性的,使得它基本上保持可获得用于在加热和固化操作期间与组合物中的聚合物多元羧酸反应。该多元醇可以是带有至少两个羟基的分子量小于大约1000的化合物,例如乙二醇,丙三醇,季戊四醇,三羟甲基丙烷,山梨醇,蔗糖,葡萄糖,间苯二酚,儿茶酚,焦棓酚,乙醇酸脲,1,4-环己烷二醇,二乙醇胺,三乙醇胺和某些反应性多元醇,例如,β-羟烷基酰胺,例如,双[N,N-二(β-羟乙基)]己二酰胺,双[N,N-二(β-羟丙基)]壬二酰胺,双[N,N-二(β-羟丙基)]己二酰胺,双[N,N-二(β-羟丙基)]戊二酰胺,双[N,N-二(β-羟丙基)]琥珀酰胺,和双[N-甲基-N-(β-羟乙基)]草酰胺,或者它可以是含有至少两个羟基的加成聚合物,例如聚乙烯醇,部分水解的聚乙酸乙烯酯和羟乙基(甲基)丙烯酸酯、羟丙基(甲基)丙烯酸酯的均聚物或共聚物以及类似的物质。
正如U.S.专利Nos.5,661,213和6,136,916中描述的,含磷促进剂(在包括聚合物多元羧酸的组合物中)可以是分子量小于大约1000的化合物,例如碱金属次磷酸盐,碱金属亚磷酸盐,碱金属多磷酸盐,碱金属二氢磷酸盐,多磷酸和烷基次磷酸,或者它可以是带有含磷基团的低聚物或聚合物,例如丙烯酸和/或马来酸在次磷酸钠的存在下形成的加成聚合物,由烯属不饱和单体在磷盐链转移剂或终止剂的存在下制备的加成聚合物,以及含有酸官能化单体残基的加成聚合物,例如,共聚的phosphoethyl甲基丙烯酸酯,以及类似的膦酸酯,共聚的乙烯基磺酸单体和它们的盐。基于多元酸和多元醇的总重量,含磷促进剂可以在大约1%到大约40%重量的水平下使用。基于多元酸和多元醇的总重量,可以使用大约2.5%到大约10%重量水平的含磷促进剂。
正如这里使用的,术语“胺碱”包括但不限于氨,伯胺,即NH2R1,和仲胺,即NHR1R2,其中R1和R2各自独立的在NHR1R2中选择,且其中R1和R2选自烷基,环烷基,烯基,环烯基,杂环基,芳基和杂芳基,正如这里所定义的。说明性地,胺碱在足以促进热固化粘结剂在热固化期间形成的条件下基本上是挥发性的或者基本上是非挥发性的。说明性地,胺碱可以基本上是挥发性碱,例如,氨,乙胺,二乙胺,二甲胺和乙基丙基胺。选择性的,胺碱可以基本上是非挥发性碱,例如苯胺,1-萘胺,2-萘胺、和对氨基苯酚。
正如这里使用的,还原糖表示一种或多种含有醛基的糖,或者可以是异构化的,即互变异构的,以便包含醛基,所述基团在梅拉德反应条件下与氨基反应,并且所述基团可以用例如Cu+2氧化以提供羧酸。还应当理解的是任何这种碳水化合物反应物可以任选地是取代的,例如用羟基、卤素、烷基、烷氧基和类似的基团取代。进一步还应理解的是在任何这种碳水化合物反应物中,存在一个或多个手性中心,并且预期在每个手性中心处的两种可能的光学异构体包括在这里所述的本发明中。此外,还应当理解的是不同的混合物,包括外消旋混合物,或任何这种碳水化合物反应物的不同光学异构体的其它非对应异构体混合物,以及它们的不同几何异构体都可以用于这里描述的一个或几个实施方案中。
图7表示用于梅拉德反应的反应物的实例。胺反应物的实例包括蛋白质,肽,氨基酸,聚合物多元羧酸的铵盐和单体的多元羧酸的铵盐。如图所示,铵可以是[+NH4]x,[+NH3R1]x和[+NH2R1R2]x,其中x为至少大约1。对于+NH2R1R2,R1和R2各自独立地选择。此外,R1和R2选自烷基,环烷基,烯基,环烯基,杂环基,芳基和杂芳基,正如以上所述。图1也举例说明了用于制备蛋白黑素的还原糖反应物的实例,包括醛糖或酮糖形式的单糖,多糖或它们的组合。说明性地用于制备蛋白黑素的非碳水化合物羰基反应物也如图1中所示,并且包括不同的醛,例如丙酮醛和糠醛,以及例如抗坏血酸和醌的化合物。
图8显示了梅拉德反应的示意图,其在蛋白黑素的制备中达到顶点。在它的初始阶段中,梅拉德反应涉及碳水化合物反应物,例如,还原糖(注意碳水化合物反应物可以来自能够在梅拉德反应条件下产生还原糖的物质)。该反应还包括缩合碳水化合物反应物(例如还原糖)和胺反应物,即具有氨基的化合物。换句话说,碳水化合物反应物和胺反应物是用于梅拉德反应的蛋白黑素反应物。这两种成分的缩合产生了N-取代的葡基胺。为了更详细的描述梅拉德反应,参见Hodge,J.E.Chemistry of Browning Reactions in Model Systems J.Agric.Food Chem.1953,1,928-943,其中公开的内容通过引用并入本发明。在梅拉德反应中具有游离氨基的化合物可以以氨基酸的形式存在。游离氨基还可以来自蛋白质,其中游离的氨基可以例如赖氨酸残基的α-氨基和/或末端氨基酸的ε-氨基的形式获得。
这里描述的进行梅拉德反应的另一方面在于,最初,正如以上所述,梅拉德反应物水溶液(其也为粘结剂)具有碱性pH值。但是,一旦将该溶液配置在非集合或松散集合的物质的集合体上,并且引发固化,该pH值就下降(即,粘结剂变成酸性的)。应当理解的是当制造材料时,与粘结剂固化后(即,当粘结剂是酸性时)相比,在固化前(即,当粘结剂溶液是碱性时)粘结剂和在制造中使用的机械组件之间接触的量更大。碱性组合物比酸性组合物的腐蚀性小。因此,制造过程的腐蚀性降低。
应当理解的是通过使用这里描述的梅拉德反应物水溶液,用于制造玻璃纤维的机械并不暴露在酸性溶液中,因为正如以上所述,梅拉德反应物溶液的pH值是碱性的。此外,在制造期间,仅仅在将粘结剂施加于纤维之后的时间内产生酸性条件。一旦将粘结剂施加于纤维,与将粘结剂施加于纤维之前的时间相比,粘结剂和结合了粘结剂的材料相对较少地与机械组件接触。因此,制造玻璃纤维(以及其它材料的制造)的腐蚀性降低。
不受理论束缚,梅拉德反应的多元羧酸铵盐和还原糖反应物的共价反应(该反应如本文所述基本上在热固化过程中发生以产生不同结构的棕色含氮聚合物和共聚物的蛋白黑素)被认为包括氨与还原糖碳水化合物反应物的醛结构部分的初始梅拉德反应以提供N-取代的葡基胺,如图8所示。氨如此消耗(其中氨和还原糖碳水化合物反应物结合物起潜在酸催化剂的作用)将预期导致pH值降低,该降低认为促进了多元羧酸的酯化过程和/或脱水以提供其相应的酸酐衍生物。在pH值<7时,N-取代的葡基胺的Amadori重排产物,即1-氨基-1-脱氧-2-酮糖将预期主要经历1,2-烯醇化,作为蛋白黑素产生的前奏,当例如,涉及戊糖时形成糠醛,或当例如,涉及己糖时形成羟甲基糠醛。与蛋白黑素的产生并行地、同时地或顺序地,可以发生涉及蛋白黑素、多元羧酸和/或其相应的酸酐衍生物、和残余碳水化合物的酯化过程,该过程引起广泛的交联。伴随糖脱水反应,于是产生可以经历聚合的共轭双键,产生由聚酯加合物组成的耐水热固性粘结剂,该聚酯加合物通过碳-碳单键的网络互连。与上述反应一致,在本文描述的固化粘结剂的FT-IR谱图中的1734cm-1附近发生强吸收,该吸收在预计为酯羰基C-O振动的1750-1730cm-1的范围之内。
以下论述涉及(i)碳水化合物和胺反应物的实例,它们可以用于梅拉德反应和(ii)如何将这些反应物结合。首先,应当理解,将充当梅拉德反应中的反应物的任何碳水化合物和/或具有伯或仲氨基的化合物可以用于本发明的粘结剂。此类化合物可以由本领域普通技术人员采用在此公开的准则确定和使用。
至于示例性的反应物,还应理解的是,使用多元羧酸的铵盐作为胺反应物是梅拉德反应中的有效反应物。多元羧酸的铵盐可以通过用胺碱中和酸基产生,从而产生多元羧酸铵盐基团。完全的中和(即,基于当量计算的大约100%)可以排除在粘结剂形成之前任何将多元羧酸(一种或多种)中的酸基滴定或部分中和的需要。然而,可以预期的是,低于完全中和不会抑制粘结剂的形成。应指出,将多元羧酸(一种或多种)的酸基中和可以在多元羧酸(一种或多种)与碳水化合物(一种或多种)混合之前或之后进行。
至于碳水化合物反应物,它可以包括含有一种或多种还原糖的一种或多种反应物。在一个方面中,任何碳水化合物反应物应该是足够非挥发性的以使其保持可获得用于与多元羧酸铵盐反应物进行反应的能力最大化。该碳水化合物反应物可以是呈其醛糖或酮糖形式的单糖,包括丙糖、丁糖、戊糖、己糖或庚糖;或多糖;或它们的结合物。碳水化合物反应物可以是还原糖,或能够在热固化条件下就地产生一种或多种还原糖的反应物。例如,当丙糖充当碳水化合物反应物时,或与其它还原糖和/或多糖结合使用时,可以使用丙醛糖或丙酮糖,例如分别为甘油醛和二羟基丙酮。当丁糖充当碳水化合物反应物时,或与其它还原糖和/或多糖结合使用时,可以使用丁醛糖,例如赤藓糖和苏糖;和丁酮糖,如赤藓酮糖。当戊糖充当碳水化合物反应物时,或与其它还原糖和/或多糖结合使用时,可以使用戊醛糖,如核糖、阿拉伯糖、木糖和来苏糖;和戊酮糖,如核酮糖、阿拉伯酮糖、木酮糖和lyxulose。当己糖充当碳水化合物反应物时,或与其它还原糖和/或多糖结合使用时,可以使用己醛糖,如葡萄糖(即,右旋糖)、甘露糖、半乳糖、阿洛糖、阿卓糖、塔罗糖、古洛糖和艾杜糖;和己酮糖,如果糖、阿洛酮糖、山梨糖和塔格糖。当庚糖充当碳水化合物反应物时,或与其它还原糖和/或多糖结合使用时,可以使用庚酮糖如景天庚酮糖。此类碳水化合物反应物的尚且未知天然存在的其它立体异构体也认为可用于制备在此描述的粘结剂组合物。当多糖充当碳水化合物时,或与单糖结合使用时,可以使用蔗糖、乳糖、麦芽糖、淀粉和纤维素。
另外,梅拉德反应中的碳水化合物反应物可以与非碳水化合物多羟基反应物结合使用。可以与所述碳水化合物反应物结合使用的非碳水化合物多羟基反应物的实例包括但不限于,三羟甲基丙烷、甘油、季戊四醇、聚乙烯醇、部分水解的聚乙酸乙烯酯、完全水解的聚乙酸乙烯酯和它们的混合物。在一个方面中,该非碳水化合物多羟基反应物是足够非挥发性的以使其保留可获得用于与单体或聚合物多元羧酸反应物进行反应的能力最大化。应领会,非碳水化合物多羟基反应物的疏水性可以是确定如在此所述制备的粘结剂的物理性能的一个因素。
当部分水解的聚乙酸乙烯酯充当非碳水化合物多羟基反应物时,可以使用可商购的化合物如87-89%水解的聚乙酸乙烯酯,如DuPont ELVANOL 51-05。DuPont ELVANOL 51-05具有大约22,000-26,000Da的分子量和大约5.0-6.0厘泊的粘度。认为可用于制备在此描述的粘结剂组合物的其它部分水解的聚乙酸乙烯酯包括但不限于,分子量和粘度与ELVANOL 51-05不同的87-89%水解的聚乙酸乙烯酯,如DuPont ELVANOL 51-04、ELVANOL 51-08、ELVANOL 50-14、ELVANOL 52-22、ELVANOL 50-26、ELVANOL 50-42;和分子量、粘度和/或水解度与ELVANOL 51-05不同的部分水解的聚乙酸乙烯酯,例如DuPont ELVANOL51-03(86-89%水解)、ELVANOL 70-14(95.0-97.0%水解)、ELVANOL70-27(95.5-96.5%水解)、ELVANOL 60-30(90-93%水解)。认为可用于制备在此描述的粘结剂组合物的其它部分水解的聚乙酸乙烯酯包括但不限于,Clariant MOWIOL 15-79、MOWIOL 3-83、MOWIOL 4-88、MOWIOL 5-88、MOWIOL 8-88、MOWIOL 18-88、MOWIOL 23-88、MOWIOL 26-88、MOWIOL 40-88、MOWIOL 47-88和MOWIOL 30-92,以及Celanese CELVOL 203、CELVOL 205、CELVOL 502、CELVOL504、CELVOL 513、CELVOL 523、CELVOL 523TV、CELVOL 530、CELVOL 540、CELVOL540TV、CELVOL 418、CELVOL 425和CELVOL 443。还认为有用的是可以从其它商业供应商获得的类似的或相似的部分水解聚乙酸乙烯酯。
当完全水解的聚乙酸乙烯酯充当非碳水化合物多羟基反应物时,可以使用分子量为大约27,000Da的Clariant MOWIOL 4-98。认为有用的其它完全水解的聚乙酸乙烯酯包括但不限于,DuPont ELVANOL 70-03(98.0-98.8%水解)、ELVANOL 70-04(98.0-98.8%水解)、ELVANOL 70-06(98.5-99.2%水解)、ELVANOL90-50(99.0-99.8%水解)、ELVANOL 70-20(98.5-99.2%水解)、ELVANOL70-30(98.5-99.2%水解)、ELVANOL 71-30(99.0-99.8%水解)、ELVANOL70-62(98.4-99.8%水解)、ELVANOL 70-63(98.5-99.2%水解)、ELVANOL70-75(98.5-99.2%水解)、Clariant MOWIOL 3-98、MOWIOL 6-98、MOWIOL 10-98、MOWIOL 20-98、MOWIOL 56-98、MOWIOL 28-99和Celanese CELVOL 103、CELVOL107、CELVOL 305、CELVOL 310、CELVOL 325、CELVOL 325LA和CELVOL 350,以及得自其它商业供应商的类似的或相似的完全水解聚乙酸乙烯酯。
上述梅拉德反应物可以结合来制备包括碳水化合物反应物和胺反应物的含水组合物。这些含水粘结剂代表未固化粘结剂的实例。如下所论述,这些含水组合物可以用作本发明的粘结剂。这些粘结剂是无甲醛、可固化、碱性、含水粘结剂组合物。另外,如上所指出,梅拉德反应物的碳水化合物反应物可以与非碳水化合物多羟基反应物结合使用。因此,提及碳水化合物反应物的任何时候,应当理解它可以与非碳水化合物多羟基反应物结合使用。
在一个示例性的实施方案中,梅拉德反应物的水溶液可以包括(i)一种或多种多元羧酸的铵盐反应物和(ii)含有还原糖的一种或多种碳水化合物反应物。在让它与待粘结材料接触之前,这一溶液的pH值可以大于或等于大约7。此外,这一溶液可以具有小于或等于大约10的pH值。多元羧酸反应物(一种或多种)的摩尔数与碳水化合物反应物(一种或多种)的摩尔数的比例可以为大约1∶4-大约1∶15。在一个实例中,粘结剂组合物中的多元羧酸反应物(一种或多种)的摩尔数与碳水化合物反应物(一种或多种)的摩尔数的比例为大约1∶5。在另一个实例中,多元羧酸反应物(一种或多种)的摩尔数与碳水化合物反应物(一种或多种)的摩尔数的比例为大约1∶6。在又一个实例中,多元羧酸反应物(一种或多种)的摩尔数与碳水化合物反应物(一种或多种)的摩尔数的比例为大约1∶7。
如上所述,含水粘结剂组合物包括(i)一种或多种多元羧酸的铵盐反应物和(ii)含有还原糖的一种或多种碳水化合化反应物。应理解的是,当单体或聚合物多元羧酸的铵盐用作胺反应物时,铵离子的摩尔当量可以等于或可以不等于多元羧酸上存在的酸式盐基团(acid salt group)的摩尔当量。在一个示例性的实例中,当三元羧酸用作多元羧酸反应物时,铵盐可以是一取代(monobasic)、二取代(dibasic)或三取代(tribasic)的。因此,铵离子的摩尔当量可以按小于或大致等于多元羧酸中存在的酸式盐基团的摩尔当量的量存在。因此,当多元羧酸反应物是二元羧酸时,该盐可以是一取代或二取代的。此外,铵离子的摩尔当量可以按小于或大致等于聚合物多元羧酸中存在的酸式盐基团的摩尔当量的量存在,等等。当使用二元羧酸的一取代盐时,或当使用三元羧酸的二取代盐时,或当铵离子的摩尔当量按小于聚合物多元羧酸中存在的酸式盐基团的摩尔当量的量存在时,粘结剂组合物的pH值可以要求调节到达到碱性。
所述未固化、无甲醛、可热固化、碱性、含水粘结剂组合物可以用来制造许多不同的材料。具体来说,通过将这些粘结剂置于与待粘结的物质接触,可以使用所述粘结剂在非集合或松散集合的物质中产生或促进内聚力。许多熟知的技术可以用来将该含水粘结剂置于与待粘结的材料接触。例如,可以经由辊涂装置将该含水粘结剂喷涂(例如在粘结玻璃纤维过程中)或施加。可以在玻璃纤维绝缘产品的制备过程中将这些含水粘结剂施加到玻璃纤维的毡上(例如,喷涂到该毡上)。一旦让该含水粘结剂与玻璃纤维接触,来自该玻璃纤维的残余热(应指出,该玻璃纤维由熔融玻璃制成并且因此包含残余热)和穿过该纤维毡的空气流将使水从粘结剂中蒸发(即,除去)。将水除去使粘结剂的剩余组分作为粘性或半粘性高固体液体的涂层保留在纤维上。这一粘性或半粘性高固体液体的涂层起粘结剂作用。此时,该纤维毡还没有被固化。换言之,该未固化的粘结剂用来粘结该毡中的玻璃纤维。
另外,应当理解,可以将上面描述的含水粘结剂固化。例如,任何上面描述的含水粘结剂可以配置(例如,喷涂)在待粘结的材料上,然后加热。例如,在制备玻璃纤维绝缘产品的情况下,在已经将含水粘结剂施加到纤维毡上之后,将该粘结剂涂覆的纤维毡转移至固化炉中。在该固化炉中,将该毡加热(例如,大约300°F-大约600°F)并且固化该粘结剂。该固化的粘结剂是将该毡的玻璃纤维粘接在一起的无甲醛、耐水性热固化粘结剂。应指出,可以顺序地、同时地或并行地进行干燥和热固化。
至于制造水不溶性粘结剂,当固化时,应理解的是,多元羧酸反应物(一种或多种)上存在的酸式盐基团的摩尔当量数与碳水化合物反应物(一种或多种)上存在的羟基的摩尔当量数的比例可以为大约0.04∶1-大约0.15∶1。在固化后,这些配制剂产生耐水性热固性粘结剂。在一个变体中,碳水化合物反应物(一种或多种)上存在的羟基的摩尔当量数为多元羧酸反应物(一种或多种)上存在的酸式盐基团的摩尔当量数的大约二十五倍。在另一个变体中,碳水化合物反应物(一种或多种)上存在的羟基的摩尔当量数为多元羧酸反应物(一种或多种)上存在的酸式盐基团的摩尔当量数的大约十倍。在又一个变体中,碳水化合物反应物(一种或多种)上存在的羟基的摩尔当量数为多元羧酸反应物(一种或多种)上存在的酸式盐基团的摩尔当量数的大约六倍。
在本发明的其它实施方案中,已经固化的粘结剂可以配置在待粘结的材料上。如上所指出,大多数固化的粘结剂通常将包含水不溶性蛋白黑素。因此,这些粘结剂还将是耐水的热固性粘结剂。
如下所论述,可以将各种添加剂引入粘结剂组合物中。这些添加剂为本发明粘结剂赋予附加的合乎需要的特性。例如,粘结剂可以包括含硅偶联剂。许多含硅偶联剂可从Dow-Corning Corporation,Petrarch Systems商购,和通过General Electric Company商购。示例性地,含硅偶联剂包括化合物例如甲硅烷基醚(silyl ether)和烷基甲硅烷基醚(alkylsilyl ether),它们中的每一种可以是任选地取代的,例如被卤素、烷氧基、氨基等取代。在一个变体中,该含硅化合物是氨基-取代的硅烷,例如γ-氨丙基三乙氧基硅烷(GeneralElectric Silicones,SILQUEST A-1101;Wilton,CT;USA)。在另一个变体中,含硅化合物是氨基-取代的硅烷,例如,氨乙基氨丙基三甲氧基硅烷(Dow Z-6020;Dow Chemical,Midland,MI;USA)。在另一个变体中,含硅化合物是γ-缩水甘油氧基丙基三甲氧基硅烷(General Electric Silicones,SILQUEST A-187)。在又一个变体中,含硅化合物是正丙基胺硅烷(Creanova(从前是HulsAmerica)HYDROSIL 2627;Creanova;Somerset,NJ.;U.S.A.)。
基于溶解的粘结剂固体,所述含硅偶联剂通常按大约0.1wt%-大约1wt%存在于该粘结剂中(即,基于添加到水溶液中的固体的重量,大约0.1%-大约1%)。在一个应用中,可以将这些含硅化合物中的一种或多种添加到含水未固化的粘结剂中。然后将该粘结剂施加到待粘结的材料上。之后,如果需要的话,可以将粘结剂固化。这些含硅氧烷的化合物提高了该粘结剂粘附于在其上配置该粘结剂的物质(例如玻璃纤维)的能力。例如,提高该粘结剂粘附于该物质的能力改进了其在非集合或松散集合的物质(一种或多种)中产生或促进内聚力的能力。
包括含硅氧烷偶联剂的粘结剂可以如下制备:将一种或多种多元羧酸反应物的大约10-大约50wt%的水溶液(已经用胺碱中和或就地中和)与含有还原糖的一种或多种碳水化合物反应物的大约10-50wt%的水溶液、和有效量含硅偶联剂混合。在一个变体中,一种或多种多元羧酸反应物和一种或多种碳水化合物反应物(后者含有还原糖)可以作为固体结合,与水混合,然后用含水胺碱(以中和一种或多种多元羧酸反应物)和含硅偶联剂处理该混合物以产生各多元羧酸反应物和各碳水化合物反应物的10-50wt%的水溶液。
在另一个示例性的实施方案中,本发明的粘结剂可以包括一种或多种缓蚀剂。这些缓蚀剂阻止或抑制了由化学分解所引起的物质如金属的腐蚀或磨损,该化学分解由酸造成。当缓蚀剂包括在本发明的粘结剂中时,与其中不存在缓蚀剂的粘结剂的腐蚀性相比,降低了该粘结剂的腐蚀性。在一个实施方案中,这些缓蚀剂可以用来降低本文描述的含玻璃纤维的组合物的腐蚀性。示例性地,缓蚀剂包括以下物质中的一种或多种:除尘油,或磷酸一铵、偏硅酸钠五水合物、蜜胺、草酸锡(II)和/或甲基含氢硅氧烷流体乳液(methylhydrogen siliconefluid emulsion)。当包括在本发明粘结剂中时,基于溶解的粘结剂固体,缓蚀剂通常按大约0.5wt%-大约2wt%存在于该粘结剂中。
通过遵循所公开的准则,本领域普通技术人员将能改变含水粘结剂的反应物的浓度以制备各种各样的粘结剂组合物。具体来说,含水粘结剂组合物可以经配制具有碱性pH值。例如,pH值为大于或等于大约7至小于或等于大约10。可以被操控的粘结剂反应物的实例包括(i)多元羧酸反应物(一种或多种),(ii)胺碱,(iii)碳水化合物反应物(一种或多种),(iv)含硅偶联剂和(V)缓蚀剂化合物。让本发明的含水粘结剂(例如未固化的粘结剂)的pH值在碱性范围内抑制了与该粘结剂接触的材料,例如制造方法中使用的机器(例如,在制造玻璃纤维中)的腐蚀。应指出,当将酸性粘结剂的腐蚀性与本发明的粘结剂相比时,情况尤其如此。因此,机械设备的“使用期限”增加,同时这些机器的维护成本减小。另外,标准设备可以与本发明的粘结剂一起使用,而不是必须使用将与酸性粘结剂接触的较耐腐蚀性的机器组件,例如不锈钢组件。因此,本文公开的粘结剂降低了所粘结材料的制造成本。
Claims (20)
1.一种包含木材颗粒和有机粘结剂的复合木板。
2.根据权利要求1的复合木板,其中该粘结剂基本上无甲醛,优选无甲醛。
3.根据前述任一项权利要求的复合木板,其中该板具有至少1800N/mm2的弹性模量(MOE)。
4.根据前述任一项权利要求的复合木板,其中该板具有至少2500N/mm2的弹性模量(ME)。
5.根据前述任一项权利要求的复合木板,其中该板具有至少14N/mm2的弯曲强度(MOR)。
6.根据前述任一项权利要求的复合木板,其中该板具有至少18N/mm2的弯曲强度(MOR)。
7.根据前述任一项权利要求的复合木板,其中该板具有至少0.028N/mm2的内部粘接强度(IB)。
8.根据前述任一项权利要求的复合木板,其中该板具有至少0.4N/mm2的内部粘接强度(IB)。
9.根据前述任一项权利要求的复合木板,其中该板具有在20℃下在水中24小时后小于或等于12%的厚度溶胀,优选小于或等于10%。
10.根据前述任一项权利要求的复合木板,其中该板具有在20℃下在水中24小时后小于或等于40%的水分吸收,优选小于或等于30%。
11.根据前述任一项权利要求的复合木板,其中该板是木材碎料板。
12.根据前述任一项权利要求的复合木板,其中该板是定向刨花板。
13.根据前述任一项权利要求的复合木板,其中该板是纤维板,优选为中等密度纤维板。
14.根据前述任一项权利要求的复合木板,其中该板具有在8-18%重量范围内的树脂含量(干燥树脂重量相对干燥木材颗粒重量),优选为10-16%重量,更优选为12-14%重量。
15.根据前述任一项权利要求的复合木板,其中该板具有基于还原糖的粘结剂。
16.根据前述任一项权利要求的复合木板,其中该板具有包含至少一种梅拉德反应产物的粘结剂。
17.根据前述任一项权利要求的复合木板,其中该板具有粘结剂,该粘结剂基于通过固化包含柠檬酸、氨和葡萄糖的水溶液获得的反应产物。
18.根据前述任一项权利要求的复合木板,其中该板包含蜡。
19.根据权利要求18的复合木板,其中该板包含在0.1-2%重量范围内的蜡,优选为0.5-1%重量。
20.根据前述任一项权利要求的复合木板,其中该粘结剂是生物树脂。
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PCT/EP2007/050746 WO2008089847A1 (en) | 2007-01-25 | 2007-01-25 | Composite wood board |
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2007
- 2007-01-25 US US12/524,522 patent/US8501838B2/en active Active
- 2007-01-25 BR BRPI0721232-1A patent/BRPI0721232B1/pt active IP Right Grant
- 2007-01-25 EP EP07704140A patent/EP2108026A1/en not_active Withdrawn
- 2007-01-25 WO PCT/EP2007/050746 patent/WO2008089847A1/en active Application Filing
- 2007-01-25 CN CN2007800503757A patent/CN101720341B/zh active Active
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2013
- 2013-06-12 US US13/915,968 patent/US8901208B2/en active Active
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- 2014-12-01 US US14/556,409 patent/US20150152266A1/en not_active Abandoned
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- 2015-06-09 US US14/734,765 patent/US9447281B2/en active Active
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- 2018-05-21 US US15/985,055 patent/US20180265706A1/en not_active Abandoned
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- 2019-02-28 US US16/288,345 patent/US20190194463A1/en not_active Abandoned
- 2019-07-18 US US16/515,490 patent/US11453780B2/en active Active
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2022
- 2022-08-22 US US17/893,056 patent/US20220396700A1/en not_active Abandoned
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- 2023-01-31 US US18/103,763 patent/US20230193037A1/en not_active Abandoned
- 2023-05-16 US US18/197,865 patent/US20230303845A1/en not_active Abandoned
- 2023-08-21 US US18/236,030 patent/US20230392016A1/en not_active Abandoned
- 2023-10-30 US US18/497,909 patent/US20240059897A1/en not_active Abandoned
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2024
- 2024-01-09 US US18/408,521 patent/US20240141172A1/en not_active Abandoned
- 2024-05-24 US US18/673,381 patent/US20240309211A1/en active Pending
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Also Published As
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EP2108026A1 (en) | 2009-10-14 |
US20230303845A1 (en) | 2023-09-28 |
US8501838B2 (en) | 2013-08-06 |
US11453780B2 (en) | 2022-09-27 |
US20240059897A1 (en) | 2024-02-22 |
US20150267055A1 (en) | 2015-09-24 |
US20170349751A1 (en) | 2017-12-07 |
US20230193037A1 (en) | 2023-06-22 |
US20160355681A1 (en) | 2016-12-08 |
US20190338129A1 (en) | 2019-11-07 |
CN101720341B (zh) | 2013-06-12 |
BRPI0721232A2 (pt) | 2013-01-01 |
BRPI0721232B1 (pt) | 2023-01-24 |
US20240141172A1 (en) | 2024-05-02 |
US8901208B2 (en) | 2014-12-02 |
US20230392016A1 (en) | 2023-12-07 |
US20220396700A1 (en) | 2022-12-15 |
US20240309211A1 (en) | 2024-09-19 |
US20140116291A1 (en) | 2014-05-01 |
US20150152266A1 (en) | 2015-06-04 |
US20190194463A1 (en) | 2019-06-27 |
WO2008089847A1 (en) | 2008-07-31 |
US20100087571A1 (en) | 2010-04-08 |
US9447281B2 (en) | 2016-09-20 |
US10000639B2 (en) | 2018-06-19 |
US20180265706A1 (en) | 2018-09-20 |
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