CN110003398B - Polyvinyl alcohol modified waterborne polyurethane-acrylate emulsion - Google Patents
Polyvinyl alcohol modified waterborne polyurethane-acrylate emulsion Download PDFInfo
- Publication number
- CN110003398B CN110003398B CN201910350349.0A CN201910350349A CN110003398B CN 110003398 B CN110003398 B CN 110003398B CN 201910350349 A CN201910350349 A CN 201910350349A CN 110003398 B CN110003398 B CN 110003398B
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- CN
- China
- Prior art keywords
- polyvinyl alcohol
- parts
- polyurethane
- acrylate emulsion
- acrylic monomer
- 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.)
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- 239000004372 Polyvinyl alcohol Substances 0.000 title claims abstract description 63
- 229920002451 polyvinyl alcohol Polymers 0.000 title claims abstract description 63
- 239000000839 emulsion Substances 0.000 title claims abstract description 23
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000000178 monomer Substances 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000002360 preparation method Methods 0.000 claims abstract description 16
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 14
- 239000008367 deionised water Substances 0.000 claims abstract description 13
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 13
- 239000003999 initiator Substances 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 12
- 229920005862 polyol Polymers 0.000 claims abstract description 11
- 150000003077 polyols Chemical class 0.000 claims abstract description 11
- 150000002433 hydrophilic molecules Chemical class 0.000 claims abstract description 8
- 239000003054 catalyst Substances 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims description 30
- 238000010438 heat treatment Methods 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 17
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims description 16
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 15
- 238000001816 cooling Methods 0.000 claims description 12
- 230000018044 dehydration Effects 0.000 claims description 12
- 238000006297 dehydration reaction Methods 0.000 claims description 12
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical group N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 11
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 11
- 229920000570 polyether Polymers 0.000 claims description 11
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 9
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 9
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical group COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 8
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 8
- JVYDLYGCSIHCMR-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)butanoic acid Chemical compound CCC(CO)(CO)C(O)=O JVYDLYGCSIHCMR-UHFFFAOYSA-N 0.000 claims description 7
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 7
- 238000004321 preservation Methods 0.000 claims description 7
- 239000000243 solution Substances 0.000 claims description 7
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 6
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 6
- 229910052797 bismuth Inorganic materials 0.000 claims description 6
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 6
- 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 6
- 238000002156 mixing Methods 0.000 claims description 6
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 6
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 claims description 5
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 5
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 5
- 230000003472 neutralizing effect Effects 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 229920005906 polyester polyol Polymers 0.000 claims description 4
- ASUUYDBHVNPPRZ-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)octanoic acid Chemical compound CCCCCCC(CO)(CO)C(O)=O ASUUYDBHVNPPRZ-UHFFFAOYSA-N 0.000 claims description 2
- UHAMPPWFPNXLIU-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)pentanoic acid Chemical compound CCCC(CO)(CO)C(O)=O UHAMPPWFPNXLIU-UHFFFAOYSA-N 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 2
- 238000006136 alcoholysis reaction Methods 0.000 claims description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 claims description 2
- YBRBMKDOPFTVDT-UHFFFAOYSA-N tert-butylamine Chemical compound CC(C)(C)N YBRBMKDOPFTVDT-UHFFFAOYSA-N 0.000 claims description 2
- 229920002554 vinyl polymer Polymers 0.000 claims 4
- 230000001070 adhesive effect Effects 0.000 abstract description 26
- 239000000853 adhesive Substances 0.000 abstract description 23
- 229920002635 polyurethane Polymers 0.000 abstract description 9
- 239000004814 polyurethane Substances 0.000 abstract description 9
- 239000002023 wood Substances 0.000 abstract description 9
- 238000000576 coating method Methods 0.000 abstract description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 abstract description 4
- 229920000642 polymer Polymers 0.000 abstract description 3
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 7
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 150000002009 diols Chemical class 0.000 description 7
- 229920000728 polyester Polymers 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- 229920000178 Acrylic resin Polymers 0.000 description 4
- 239000004925 Acrylic resin Substances 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 239000004615 ingredient Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 3
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 229920001568 phenolic resin Polymers 0.000 description 3
- 229920001807 Urea-formaldehyde Polymers 0.000 description 2
- 238000004026 adhesive bonding Methods 0.000 description 2
- GZCGUPFRVQAUEE-SLPGGIOYSA-N aldehydo-D-glucose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O GZCGUPFRVQAUEE-SLPGGIOYSA-N 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000005038 ethylene vinyl acetate Substances 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- -1 waterproof coatings Substances 0.000 description 2
- JZLWSRCQCPAUDP-UHFFFAOYSA-N 1,3,5-triazine-2,4,6-triamine;urea Chemical compound NC(N)=O.NC1=NC(N)=NC(N)=N1 JZLWSRCQCPAUDP-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 239000004826 Synthetic adhesive Substances 0.000 description 1
- 229920006223 adhesive resin Polymers 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- KVBYPTUGEKVEIJ-UHFFFAOYSA-N benzene-1,3-diol;formaldehyde Chemical compound O=C.OC1=CC=CC(O)=C1 KVBYPTUGEKVEIJ-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 239000012943 hotmelt Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 239000011120 plywood Substances 0.000 description 1
- 229920000909 polytetrahydrofuran Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/006—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
-
- 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
- C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
- C08G18/348—Hydroxycarboxylic acids
-
- 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
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
-
- 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
-
- 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
- C08G18/4804—Two or more polyethers of different physical or chemical nature
- C08G18/4812—Mixtures of polyetherdiols with polyetherpolyols having at least three hydroxy groups
-
- 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
- C08G18/4825—Polyethers containing two hydroxy groups
-
- 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
- C08G18/4829—Polyethers containing at least three hydroxy groups
-
- 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
- C08G18/40—High-molecular-weight compounds
- C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
- C08G18/6212—Polymers of alkenylalcohols; Acetals thereof; Oxyalkylation products thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—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
- C08G18/6625—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/34
-
- 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
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- 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
- C08G18/6692—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/34
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- 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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
-
- 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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
- C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention discloses a polyvinyl alcohol modified waterborne polyurethane-acrylate emulsion, which relates to the technical field of adhesive product preparation and is prepared from the following raw materials in parts by weight: 20-50 parts of diisocyanate, 100-400 parts of macromolecular polyol, 2-9 parts of micromolecular hydrophilic compound, 1-5 parts of catalyst, 500 parts of acrylic monomer, 1-5 parts of oil-soluble initiator, 60-200 parts of polyvinyl alcohol, 100-400 parts of deionized water and 1-3 parts of neutralizer; the highly crosslinked macromolecular polymer obtained by the invention has the advantages of polyurethane, acrylate and polyvinyl alcohol, has excellent adhesive property, water resistance and mechanical property, is environment-friendly and safe, has low cost, and can be applied to the fields of wood adhesives, coatings and the like.
Description
The technical field is as follows:
the invention relates to the technical field of adhesive product preparation, and particularly relates to a polyvinyl alcohol modified waterborne polyurethane-acrylate emulsion.
Background art:
the adhesives used in wood processing in China mainly belong to two fields of artificial board manufacturing and wooden product production, and urea-formaldehyde resin (UF) adhesive, phenol-formaldehyde resin (PF) adhesive and melamine-formaldehyde resin adhesive are three major synthetic adhesives most applied to artificial board industry. Distinguishing according to different purposes, namely phenolic resin adhesive and isocyanate resin adhesive for manufacturing the waterproof structure type artificial board; manufacturing a melamine-urea co-condensation resin adhesive for the moisture-proof and water-resistant artificial boards; the cross-linked wood is manufactured by using an aqueous polymer-isocyanate adhesive or a resorcinol formaldehyde resin adhesive; polyvinyl acetate emulsion glue (white latex), ethylene-vinyl acetate copolymer resin (EVA) hot melt glue, etc. are widely used in furniture manufacture. The formaldehyde-free aqueous polymer material adhesive is gradually and widely applied to the field of wood adhesives, such as polyurethane resin, acrylic resin and other environment-friendly adhesives.
The waterborne polyurethane takes water as a dispersion medium, does not contain or contain a small amount of organic solvent, and is widely applied to various industries due to the advantages of meeting the environmental protection requirement, high strength and the like. The acrylic resin is a high polymer material formed by copolymerizing acrylic monomers and is mainly applied to the fields of textiles, waterproof coatings, wood adhesives and the like. Polyvinyl alcohol has low price, good strength, good degradation performance and gas barrier performance, and is widely used in the fields of adhesives, coatings and the like. Meanwhile, the polyvinyl alcohol is easy to dissolve in water, contains a large amount of hydroxyl, can be subjected to grafting reaction with isocyanate groups in polyurethane, and then is subjected to copolymerization reaction with acrylic monomers, so that the polyvinyl alcohol modified waterborne polyurethane-acrylate emulsion can be obtained. Integrates the advantages of polyurethane, acrylate and polyvinyl alcohol, has the characteristics of excellent performance, good environmental protection performance, low cost and the like, and can be applied to the fields of adhesives, coatings and the like.
The invention content is as follows:
the invention aims to solve the technical problem of providing a polyvinyl alcohol modified waterborne polyurethane-acrylate emulsion, wherein the polyvinyl alcohol and acrylic resin modified waterborne polyurethane are introduced, so that the prepared polyvinyl alcohol modified waterborne polyurethane-acrylate emulsion has the advantages of polyurethane, acrylate and polyvinyl alcohol, has excellent adhesive property, water resistance and mechanical property, is environment-friendly and safe, has low cost, and can be applied to the fields of wood adhesives, coatings and the like.
The technical problem to be solved by the invention is realized by adopting the following technical scheme:
a polyvinyl alcohol modified waterborne polyurethane-acrylate emulsion is prepared from the following raw materials in parts by weight:
20-50 parts of diisocyanate, 100-400 parts of macromolecular polyol, 2-9 parts of micromolecular hydrophilic compound, 1-5 parts of catalyst, 500 parts of acrylic monomer, 1-5 parts of oil-soluble initiator, 60-200 parts of polyvinyl alcohol, 100-400 parts of deionized water and 1-3 parts of neutralizer.
The diisocyanate is selected from one or two of 4,4 '-diphenylmethane diisocyanate MDI-100, 2, 4-diphenylmethane diisocyanate, mixture MDI-50 of 4,4' -diphenylmethane diisocyanate and isophorone diisocyanate.
The macromolecular polyol is the mixture of polyether polyol and polyester polyol, and is selected from one or two of polyether polyol and polyester polyol with the functionality of 2-4 and the number average molecular weight of 1000-5000.
The small molecular hydrophilic compound is selected from one or more of dimethylolpropionic acid, dimethylolbutyric acid, dimethylolpentanoic acid and dimethyloloctanoic acid.
The catalyst is selected from one of dibutyltin dilaurate and organic bismuth.
The acrylic monomer is selected from methyl methacrylate, methacrylic acid, ethyl acrylate, butyl acrylate and acrylonitrile.
The oil-soluble initiator is azobisisobutyronitrile.
The alcoholysis degree of the polyvinyl alcohol is more than 80%, the polymerization degree is 500-3000, and the mass fraction of the polyvinyl alcohol aqueous solution is 10-30%.
The neutralizing agent is selected from one of triethylamine, tert-butylamine, triethanolamine and diethanolamine.
The preparation method of the polyvinyl alcohol modified waterborne polyurethane-acrylate emulsion comprises the following steps:
(1) preparing a polyurethane prepolymer:
adding macromolecular polyol and micromolecular hydrophilic compounds into a four-neck flask, uniformly stirring, heating to 90-100 ℃, performing vacuum dehydration, cooling to 60 ℃ after dehydration, adding diisocyanate, dropwise adding a catalyst, heating to 75 ℃, and performing heat preservation reaction;
(2) preparation of acrylic monomer mixture:
mixing acrylic monomer and oil-soluble initiator, and stirring uniformly;
(3) preparation of aqueous polyvinyl alcohol solution:
adding polyvinyl alcohol into deionized water, heating to 80-90 ℃, and stirring until the polyvinyl alcohol is completely dissolved;
(4) preparing polyvinyl alcohol modified waterborne polyurethane-acrylate emulsion:
adding the prepared acrylic monomer mixture into the polyurethane prepolymer, stirring uniformly, then adding a polyvinyl alcohol aqueous solution, quickly stirring to uniformly disperse the prepolymer, adding a neutralizing agent, heating to 70 ℃, keeping the temperature not more than 80 ℃, cooling to 40-50 ℃ after the reaction is finished, and curing.
The invention has the beneficial effects that:
(1) the invention introduces polyvinyl alcohol and acrylic resin modified waterborne polyurethane, the polyvinyl alcohol contains more hydroxyl groups, the polyvinyl alcohol is grafted with isocyanate groups in the polyurethane prepolymer, after the polyurethane prepolymer is dispersed, an acrylic monomer and hydroxyl-terminated polyurethane-polyvinyl alcohol macromolecules are copolymerized under the action of a temperature rise and an initiator to obtain a highly crosslinked macromolecular polymer, and the highly crosslinked macromolecular polymer has the advantages of polyurethane, acrylate and polyvinyl alcohol, has excellent adhesive property, water resistance and mechanical property, is environment-friendly, safe and low in cost, and can be applied to the fields of wood adhesives, coatings and the like.
(2) The micromolecule hydrophilic compound contains hydroxyl and carboxyl in the structure, the hydroxyl and isocyanate group react, the carboxyl endows the prepared polyurethane prepolymer with hydrophilicity, the polyurethane prepolymer has a self-emulsifying function, an additional emulsifier is not needed, deionized water is added for dispersing, emulsifying and neutralizing to form salt, and the stability of the system is improved.
The specific implementation mode is as follows:
in order to make the technical means, the creation characteristics, the achievement purposes and the effects of the invention easy to understand, the invention is further described with the specific embodiments.
Example 1
The ingredient table is as follows:
(1) preparing a polyurethane prepolymer:
adding polytetrahydrofuran triol 3000, polyether diol 2000 and dimethylolpropionic acid into a four-mouth flask, uniformly stirring, heating to 100 ℃, performing vacuum dehydration for 1h, cooling to 60 ℃ after dehydration, adding diisocyanate MDI, dropwise adding dibutyltin dilaurate, heating to 75 ℃, and performing heat preservation reaction for 3 h;
(2) preparation of acrylic monomer mixture:
mixing methyl methacrylate, ethyl acrylate, acrylonitrile and an oil-soluble initiator AIBN, and uniformly stirring;
(3) preparation of aqueous polyvinyl alcohol solution:
adding polyvinyl alcohol into deionized water, heating to 85 ℃, and stirring until the polyvinyl alcohol is completely dissolved;
(4) preparing polyvinyl alcohol modified waterborne polyurethane-acrylate emulsion:
adding the prepared acrylic monomer mixture into the polyurethane prepolymer, stirring uniformly, then adding a polyvinyl alcohol aqueous solution, quickly stirring to uniformly disperse the prepolymer, adding triethylamine, heating to 70 ℃, keeping the temperature for reaction for 2 hours, controlling the temperature not to exceed 80 ℃, cooling to 50 ℃ after the reaction is finished, and curing for 1 hour.
Example 2
The ingredient table is as follows:
| raw materials | Dosage of | Raw materials | Dosage of | Raw materials | Dosage of |
| Polyester diol 4000 | 100g | Methacrylic acid methyl ester | 120g | Polyvinyl alcohol | 150g |
| Polyether triol 3000 | 120g | Acrylic acid ethyl ester | 90g | Deionized water | 310g |
| Diisocyanate MDI | 38g | Acrylic acid butyl ester | 60g | Triethylamine | 3g |
| Dimethylolpropionic acid | 4g | Acrylonitrile | 15g | ||
| Dibutyl tin dilaurate | 2g | AIBN | 3g |
(1) Preparing a polyurethane prepolymer:
adding polyester diol 4000, polyether triol 3000 and dimethylolpropionic acid into a four-neck flask, uniformly stirring, heating to 100 ℃, performing vacuum dehydration for 1h, cooling to 60 ℃ after dehydration, adding diisocyanate MDI, dropwise adding dibutyltin dilaurate, heating to 75 ℃, and performing heat preservation reaction for 3 h;
(2) preparation of acrylic monomer mixture:
mixing methyl methacrylate, ethyl acrylate, butyl acrylate, acrylonitrile and an oil-soluble initiator AIBN, and uniformly stirring;
(3) preparation of aqueous polyvinyl alcohol solution:
adding polyvinyl alcohol into deionized water, heating to 85 ℃, and stirring until the polyvinyl alcohol is completely dissolved;
(4) preparing polyvinyl alcohol modified waterborne polyurethane-acrylate emulsion:
adding the prepared acrylic monomer mixture into the polyurethane prepolymer, stirring uniformly, then adding a polyvinyl alcohol aqueous solution, quickly stirring to uniformly disperse the prepolymer, adding triethylamine, heating to 70 ℃, keeping the temperature for reaction for 2 hours, controlling the temperature not to exceed 80 ℃, cooling to 50 ℃ after the reaction is finished, and curing for 1 hour.
Example 3
The ingredient table is as follows:
| raw materials | Dosage of | Raw materials | Dosage of | Raw materials | Dosage of |
| Polyester diol 2000 | 120g | Methacrylic acid methyl ester | 90g | Polyvinyl alcohol | 170g |
| Polyether triol 5000 | 90g | Acrylic acid ethyl ester | 100g | Deionized water | 350g |
| Diisocyanate IPDI | 41g | Acrylic acid butyl ester | 150g | Triethanolamine | 4g |
| Dimethylolbutanoic acid | 5g | Acrylonitrile | 16g | ||
| Organic bismuth | 3g | AIBN | 3g |
(1) Preparing a polyurethane prepolymer:
adding polyester diol 2000, polyether triol 5000 and dimethylolbutyric acid into a four-neck flask, uniformly stirring, heating to 100 ℃, performing vacuum dehydration for 1h, cooling to 60 ℃ after dehydration, adding diisocyanate IPDI, dropwise adding organic bismuth, heating to 75 ℃, and performing heat preservation reaction for 3 h;
(2) preparation of acrylic monomer mixture:
mixing methyl methacrylate, ethyl acrylate, butyl acrylate, acrylonitrile and an oil-soluble initiator AIBN, and uniformly stirring;
(3) preparation of aqueous polyvinyl alcohol solution:
adding polyvinyl alcohol into deionized water, heating to 85 ℃, and stirring until the polyvinyl alcohol is completely dissolved;
(4) preparing polyvinyl alcohol modified waterborne polyurethane-acrylate emulsion:
adding the prepared acrylic monomer mixture into the polyurethane prepolymer, stirring uniformly, then adding a polyvinyl alcohol aqueous solution, quickly stirring to uniformly disperse the prepolymer, adding triethanolamine, heating to 70 ℃, keeping the temperature for reaction for 2 hours, controlling the temperature not to exceed 80 ℃, cooling to 50 ℃ after the reaction is finished, and curing for 1 hour.
Example 4
The ingredient table is as follows:
| raw materials | Dosage of | Raw materials | Dosage of | Raw materials | Dosage of |
| Polyester triol 5000 | 150g | Methacrylic acid methyl ester | 60g | Polyvinyl alcohol | 150g |
| Polyether diol 1000 | 100g | Acrylic acid ethyl ester | 900g | Deionized water | 320g |
| Diisocyanate IPDI | 48g | Acrylic acid butyl ester | 160g | Triethanolamine | 4.5g |
| Dimethylolbutanoic acid | 6g | Acrylonitrile | 15g | ||
| Organic bismuth | 4g | AIBN | 3g |
(1) Preparing a polyurethane prepolymer:
adding polyester triol 5000, polyether diol 1000 and dimethylolbutyric acid into a four-neck flask, uniformly stirring, heating to 100 ℃, performing vacuum dehydration for 1h, cooling to 60 ℃ after dehydration, adding diisocyanate IPDI, dropwise adding organic bismuth, heating to 75 ℃, and performing heat preservation reaction for 3 h;
(2) preparation of acrylic monomer mixture:
mixing methyl methacrylate, ethyl acrylate, butyl acrylate, acrylonitrile and an oil-soluble initiator AIBN, and uniformly stirring;
(3) preparation of aqueous polyvinyl alcohol solution:
adding polyvinyl alcohol into deionized water, heating to 85 ℃, and stirring until the polyvinyl alcohol is completely dissolved;
(4) preparing polyvinyl alcohol modified waterborne polyurethane-acrylate emulsion:
adding the prepared acrylic monomer mixture into the polyurethane prepolymer, stirring uniformly, then adding a polyvinyl alcohol aqueous solution, quickly stirring to uniformly disperse the prepolymer, adding triethanolamine, heating to 70 ℃, keeping the temperature for reaction for 2 hours, controlling the temperature not to exceed 80 ℃, cooling to 50 ℃ after the reaction is finished, and curing for 1 hour.
Comparative example 1
The same procedure as in example 4 was repeated except that comparative example 1 in which the acrylic monomer mixture was not added was used as a control.
Comparative example 2
The same procedure as in example 4 was repeated except that comparative example 2, in which the aqueous polyvinyl alcohol solution was not added, was used.
Comparative example 3
The same procedure was repeated except that comparative example 3 in which no dimethylolbutyric acid was added was used as a control in example 4.
The emulsions obtained in examples 1 to 4 and comparative examples 1 to 3 were used as wood adhesives, plywood test pieces were prepared in accordance with the national standard GB/T17657-2013, and the bonding strengths were measured, the results of which are shown in Table 1.
Adhesive bonding Properties of the adhesives prepared in Table 1
As can be seen from Table 1, in example 4, the addition of the small-molecule hydrophilic compound and the modification of the polyurethane by the acrylic monomer and the polyvinyl alcohol can achieve the technical effect of significantly improving the gluing performance of the prepared emulsion as the wood adhesive.
The foregoing shows and describes the general principles and broad features of the present invention and advantages thereof. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (5)
1. A polyvinyl alcohol modified waterborne polyurethane-acrylate emulsion is characterized in that: the feed is prepared from the following raw materials in parts by weight:
41-50 parts of diisocyanate, 100 parts of macromolecular polyol, 2-5 parts of micromolecular hydrophilic compound, 1-5 parts of catalyst, 500 parts of acrylic monomer, 1-5 parts of oil-soluble initiator, 60-200 parts of polyvinyl alcohol, 100 parts of deionized water and 400 parts of neutralizer;
the preparation method comprises the following steps:
(1) preparing a polyurethane prepolymer:
adding macromolecular polyol and micromolecular hydrophilic compounds into a four-neck flask, uniformly stirring, heating to 90-100 ℃, performing vacuum dehydration, cooling to 60 ℃ after dehydration, adding diisocyanate, dropwise adding a catalyst, heating to 75 ℃, and performing heat preservation reaction;
(2) preparation of acrylic monomer mixture:
mixing acrylic monomer and oil-soluble initiator, and stirring uniformly;
(3) preparation of aqueous polyvinyl alcohol solution:
adding polyvinyl alcohol into deionized water, heating to 80-90 ℃, and stirring until the polyvinyl alcohol is completely dissolved;
(4) preparing polyvinyl alcohol modified waterborne polyurethane-acrylate emulsion:
adding the prepared acrylic monomer mixture into a polyurethane prepolymer, uniformly stirring, then adding a polyvinyl alcohol aqueous solution, rapidly stirring to uniformly disperse the prepolymer, adding a neutralizing agent, heating to 70 ℃, carrying out heat preservation reaction, controlling the temperature not to exceed 80 ℃, cooling to 40-50 ℃ after the reaction is finished, and curing;
the diisocyanate is selected from one or two of 4,4 '-diphenylmethane diisocyanate MDI-100, 2, 4-diphenylmethane diisocyanate, mixture MDI-50 of 4,4' -diphenylmethane diisocyanate and isophorone diisocyanate;
the macromolecular polyol is a mixture of polyether polyol and polyester polyol, and is selected from one or two of polyether polyol and polyester polyol with the functionality of 2-3 and the number average molecular weight of 2000-5000;
the small molecular hydrophilic compound is selected from one or more of dimethylolpropionic acid, dimethylolbutyric acid, dimethylolpentanoic acid and dimethyloloctanoic acid;
the acrylic monomer is selected from methyl methacrylate, methacrylic acid, ethyl acrylate, butyl acrylate and acrylonitrile.
2. The polyvinyl alcohol-modified aqueous polyurethane-acrylate emulsion according to claim 1, characterized in that: the catalyst is selected from one of dibutyltin dilaurate and organic bismuth.
3. The polyvinyl alcohol-modified aqueous polyurethane-acrylate emulsion according to claim 1, characterized in that: the oil-soluble initiator is azobisisobutyronitrile.
4. The polyvinyl alcohol-modified aqueous polyurethane-acrylate emulsion according to claim 1, characterized in that: the alcoholysis degree of the polyvinyl alcohol is more than 80%, the polymerization degree is 500-3000, and the mass fraction of the polyvinyl alcohol aqueous solution is 10-30%.
5. The polyvinyl alcohol-modified aqueous polyurethane-acrylate emulsion according to claim 1, characterized in that: the neutralizing agent is selected from one of triethylamine, tert-butylamine, triethanolamine and diethanolamine.
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| CN114395103B (en) * | 2021-09-30 | 2024-05-03 | 明新梅诺卡(江苏)新材料有限公司 | Aqueous polyurethane impregnating resin for microfiber synthetic leather and preparation method thereof |
| CN114836150A (en) * | 2022-06-06 | 2022-08-02 | 太尔化工（南京）有限公司 | Environment-friendly adhesive and preparation method thereof |
| CN115197434A (en) * | 2022-07-14 | 2022-10-18 | 江西辙炜新材料科技有限公司 | Paper product moisturizing emulsion, and preparation method and application thereof |
| CN116063895B (en) * | 2022-12-23 | 2024-11-26 | 中华制漆(新丰）有限公司 | Water-resistant wood paint and preparation method thereof |
| CN117698177B (en) * | 2023-11-21 | 2024-07-05 | 江苏华信高新材料有限公司 | Preparation method of circulating PETG mirror substrate |
| CN118126658A (en) * | 2024-02-20 | 2024-06-04 | 石嘴山市润邦工贸有限公司 | Composite adhesive for preparing industrial briquette and preparation method thereof |
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