CN114774055A - Adhesive for plywood without formaldehyde, preparation method of adhesive, plywood and preparation method of plywood - Google Patents
Adhesive for plywood without formaldehyde, preparation method of adhesive, plywood and preparation method of plywood Download PDFInfo
- Publication number
- CN114774055A CN114774055A CN202210461137.1A CN202210461137A CN114774055A CN 114774055 A CN114774055 A CN 114774055A CN 202210461137 A CN202210461137 A CN 202210461137A CN 114774055 A CN114774055 A CN 114774055A
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- Prior art keywords
- cellulose ether
- adhesive
- parts
- plywood
- mass
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- 230000001070 adhesive effect Effects 0.000 title claims abstract description 82
- 239000000853 adhesive Substances 0.000 title claims abstract description 81
- 239000011120 plywood Substances 0.000 title claims abstract description 68
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 title description 2
- 229920003086 cellulose ether Polymers 0.000 claims abstract description 31
- 235000013312 flour Nutrition 0.000 claims abstract description 25
- 239000007864 aqueous solution Substances 0.000 claims abstract description 18
- 239000000945 filler Substances 0.000 claims abstract description 14
- 238000004513 sizing Methods 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 85
- 238000007731 hot pressing Methods 0.000 claims description 45
- 239000012948 isocyanate Substances 0.000 claims description 35
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 28
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 28
- 239000003292 glue Substances 0.000 claims description 25
- 150000002513 isocyanates Chemical class 0.000 claims description 25
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 24
- 238000003825 pressing Methods 0.000 claims description 24
- -1 dihydroxypropyl Chemical group 0.000 claims description 22
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 claims description 21
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 claims description 21
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 claims description 21
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 229920013821 hydroxy alkyl cellulose Polymers 0.000 claims description 19
- 239000005056 polyisocyanate Substances 0.000 claims description 15
- 229920001228 polyisocyanate Polymers 0.000 claims description 15
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 13
- 239000000243 solution Substances 0.000 claims description 13
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 11
- 239000002023 wood Substances 0.000 claims description 11
- 244000166124 Eucalyptus globulus Species 0.000 claims description 9
- 239000000835 fiber Substances 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 7
- GRVDJDISBSALJP-UHFFFAOYSA-N methyloxidanyl Chemical group [O]C GRVDJDISBSALJP-UHFFFAOYSA-N 0.000 claims description 5
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 5
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 4
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 claims description 4
- 238000006136 alcoholysis reaction Methods 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 4
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 4
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 4
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 4
- 239000001863 hydroxypropyl cellulose Substances 0.000 claims description 4
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 claims description 4
- 238000006116 polymerization reaction Methods 0.000 claims description 4
- 229920006389 polyphenyl polymer Polymers 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- 241000219000 Populus Species 0.000 claims description 3
- 239000005995 Aluminium silicate Substances 0.000 claims description 2
- 235000018185 Betula X alpestris Nutrition 0.000 claims description 2
- 235000018212 Betula X uliginosa Nutrition 0.000 claims description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical group COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 2
- 229920000896 Ethulose Polymers 0.000 claims description 2
- 239000001859 Ethyl hydroxyethyl cellulose Substances 0.000 claims description 2
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 claims description 2
- 239000004354 Hydroxyethyl cellulose Substances 0.000 claims description 2
- 229920001479 Hydroxyethyl methyl cellulose Polymers 0.000 claims description 2
- 235000008331 Pinus X rigitaeda Nutrition 0.000 claims description 2
- 241000018646 Pinus brutia Species 0.000 claims description 2
- 235000011613 Pinus brutia Nutrition 0.000 claims description 2
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- 235000012211 aluminium silicate Nutrition 0.000 claims description 2
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 2
- 235000019326 ethyl hydroxyethyl cellulose Nutrition 0.000 claims description 2
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 claims description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000010445 mica Substances 0.000 claims description 2
- 229910052618 mica group Inorganic materials 0.000 claims description 2
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000000454 talc Substances 0.000 claims 1
- 229910052623 talc Inorganic materials 0.000 claims 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 abstract description 39
- 238000007761 roller coating Methods 0.000 abstract description 9
- 239000010410 layer Substances 0.000 description 14
- 229920000538 Poly[(phenyl isocyanate)-co-formaldehyde] Polymers 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 8
- 238000010998 test method Methods 0.000 description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 125000003636 chemical group Chemical group 0.000 description 5
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 4
- 229920002545 silicone oil Polymers 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 230000032683 aging Effects 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 229920002678 cellulose Polymers 0.000 description 3
- 239000001913 cellulose Substances 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical group CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
- 229920001400 block copolymer Polymers 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 125000005113 hydroxyalkoxy group Chemical group 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 239000008107 starch Substances 0.000 description 2
- 235000019698 starch Nutrition 0.000 description 2
- 239000002562 thickening agent Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 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 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 238000009700 powder processing Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000001119 stannous chloride Substances 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- RCIVOBGSMSSVTR-UHFFFAOYSA-L stannous sulfate Chemical compound [SnH2+2].[O-]S([O-])(=O)=O RCIVOBGSMSSVTR-UHFFFAOYSA-L 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 229910000375 tin(II) sulfate Inorganic materials 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27D—WORKING VENEER OR PLYWOOD
- B27D1/00—Joining wood veneer with any material; Forming articles thereby; Preparatory processing of surfaces to be joined, e.g. scoring
- B27D1/04—Joining wood veneer with any material; Forming articles thereby; Preparatory processing of surfaces to be joined, e.g. scoring to produce plywood or articles made therefrom; Plywood sheets
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27D—WORKING VENEER OR PLYWOOD
- B27D1/00—Joining wood veneer with any material; Forming articles thereby; Preparatory processing of surfaces to be joined, e.g. scoring
- B27D1/04—Joining wood veneer with any material; Forming articles thereby; Preparatory processing of surfaces to be joined, e.g. scoring to produce plywood or articles made therefrom; Plywood sheets
- B27D1/08—Manufacture of shaped articles; Presses specially designed therefor
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B21/00—Layered products comprising a layer of wood, e.g. wood board, veneer, wood particle board
- B32B21/04—Layered products comprising a layer of wood, e.g. wood board, veneer, wood particle board comprising wood as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B21/042—Layered products comprising a layer of wood, e.g. wood board, veneer, wood particle board comprising wood as the main or only constituent of a layer, which is next to another layer of the same or of a different material of wood
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B21/00—Layered products comprising a layer of wood, e.g. wood board, veneer, wood particle board
- B32B21/14—Layered products comprising a layer of wood, e.g. wood board, veneer, wood particle board comprising wood board or veneer
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/06—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the heating method
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
- B32B37/1284—Application of adhesive
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
Landscapes
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- Forests & Forestry (AREA)
- Physics & Mathematics (AREA)
- Fluid Mechanics (AREA)
- Inorganic Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention discloses an adhesive for a formaldehyde-free plywood and a preparation method thereof, and a plywood and a preparation method thereof. The adhesive is prepared from the following raw materials in parts by weight: 160 parts of modified cellulose ether aqueous solution, 20-60 parts of flour and 5-60 parts of filler. The plywood without formaldehyde addition with excellent performance can be prepared by adopting a roller coating mode for sizing.
Description
Technical Field
The invention relates to the field of formaldehyde-free adhesive systems, in particular to a formaldehyde-free adhesive for plywood and a preparation method thereof, and plywood and a preparation method thereof.
Background
The plywood is an important component of the artificial board industry, and the yield of the Chinese plywood accounts for more than 50 percent of the yield of all artificial boards. The prior adhesive for producing the domestic plywood mainly comprises a urea-formaldehyde resin adhesive (containing modification) and a phenolic resin adhesive. The most outstanding problem of the formaldehyde adhesive is that the adhesive contains free formaldehyde, and the prepared plywood can release formaldehyde which is extremely harmful to human bodies in the using process. With the economic development and social progress, the environmental protection and health awareness of people is remarkably improved, and the concern on the formaldehyde release problem in the artificial board is close.
The adhesive for the plywood without formaldehyde is needed.
Patent CN110872481A discloses an adhesive for aldehyde-free plywood and a preparation method thereof, wherein the adhesive comprises polyvinyl alcohol, a thickener, a defoaming agent, phosphoric acid, copper salt, flour, deionized water and polyfunctional isocyanate, and because the polyvinyl alcohol and the isocyanate can react to generate carbamate, in order to ensure sufficient operation time, the patent inhibits the reaction activity by adding phosphoric acid and reduces the viscosity increase rate of the system, however, because the phosphoric acid is introduced, the adhesive is acidic, the aging of the adhesive layer and wood can be accelerated, and the durability of the obtained board can be reduced.
Patent CN113831892A discloses an adhesive for aldehyde-free plywood, a preparation method thereof and plywood containing the adhesive, wherein the adhesive comprises monocarboxyl modified silicone oil modified polyvinyl alcohol, polyisocyanate, filler and a thickening agent, the molecular chain regularity and the number of polar hydroxyl groups of the polyvinyl alcohol are reduced through the monocarboxyl modified silicone oil modified polyvinyl alcohol, and the incompatibility and steric hindrance effect of monocarboxyl silicone oil chain segments and the polyisocyanate reduce the reactivity of the modified polyvinyl alcohol and the polyisocyanate, thereby prolonging the service life of the adhesive. However, in the process of modifying polyvinyl alcohol by monocarboxyl modified silicone oil, stannous chloride or stannous sulfate is required to be added as a catalyst, which can cause trace heavy metals in the adhesive and the final plate.
Disclosure of Invention
The invention aims to provide a formaldehyde-free adhesive for plywood and a preparation method thereof, and plywood prepared by using the adhesive and a preparation method of the plywood. The adhesive system has stable viscosity and long working life, and can be used for preparing the formaldehyde-free plywood with higher strength.
In order to realize the purpose of the invention, the invention adopts the following technical scheme:
the adhesive for the formaldehyde-free plywood comprises the following raw materials in parts by weight: 160 parts of modified cellulose ether aqueous solution, 20-60 parts of flour and 5-60 parts of filler.
The modified cellulose ether is a multifunctional isocyanate modified hydroxyalkyl cellulose ether including, but not limited to, one or more of hydroxyethyl cellulose ether, hydroxypropyl cellulose ether, preferably hydroxypropyl cellulose ether.
Further, the hydroxyalkyl cellulose ether comprises one or more of dihydroxypropyl cellulose ether, ethyl hydroxyethyl cellulose ether, methyl hydroxyethyl cellulose ether, hydroxypropyl methyl cellulose ether, hydroxyethyl carboxymethyl cellulose ether, hydroxypropyl carboxymethyl cellulose ether, preferably hydroxypropyl methyl cellulose ether (HPMC).
The aqueous modified cellulose ether solution comprises: 0.5-6 parts by mass of hydroxyalkyl cellulose ether, 0-10 parts by mass of polyvinyl alcohol, 20-55 parts by mass of polyfunctional isocyanate and 100 parts by mass of water.
In some preferred embodiments of the present invention, the polyvinyl alcohol is added in an amount other than 0.
In the invention, the polymerization degree of the polyvinyl alcohol is 1600-2600, and the alcoholysis degree (mole fraction) is 86.0-90.0%. Polyvinyl alcohol is a polymer with a large number of strong hydrophilic hydroxyl groups, and strong hydrogen bonds exist between intermolecular and intramolecular hydroxyl groups, so that the dissolution of the polyvinyl alcohol to water is obviously hindered. The residual acetate groups of partially alcoholized polyvinyl alcohol are inherently hydrophobic, but can weaken hydrogen bonds between adjacent molecules and within molecules, so the presence of a suitable amount of residual acetate groups can improve the water solubility of the polyvinyl alcohol. The dense hydroxyl groups in the molecular chain of the polyvinyl alcohol can react with isocyanate groups to generate carbamate.
In the present invention, the polyfunctional isocyanate is preferably selected from one or more of aromatic polyisocyanates (including araliphatic polyisocyanates), aliphatic polyisocyanates (including alicyclic polyisocyanates); preferably an aromatic polyisocyanate; more preferably one or more of toluene diisocyanate, diphenylmethane diisocyanate and polymethylene polyphenyl polyisocyanates (also known as polymeric MDI or PMDI).
Polymethylene polyphenyl polyisocyanates have an average molecular weight of 320-420, an average functionality of 2.5-3.0 and a viscosity of about 150-250cP at 25 ℃. Cellulose ether is a generic name of a series of cellulose derivatives generated by the reaction of alkali cellulose and an etherifying agent under certain conditions, and is a product of cellulose macromolecules with hydroxyl groups partially or completely substituted by ether groups. Hydroxyalkyl cellulose ether refers to cellulose ether with hydroxyalkyl as the substituent, which is more soluble in water. The structural unit simultaneously has hydroxyalkoxyl, methoxyl and unreacted hydroxyl groups, and the hydroxyalkoxyl is an active group and can react with isocyanate groups; the group is a hydrophilic group, and the branched chain is longer, thereby playing a certain plasticizing role in the chain. Methoxy is a hydrophobic group, and the structure is relatively short. In the invention, the hydroxypropyl methyl cellulose ether contains 4-12% of hydroxypropyl (mass fraction) and 23-32% of methoxyl (mass fraction).
The polyvinyl alcohol and hydroxyalkyl cellulose ether contain abundant hydroxyl groups, and can react with-NCO in polyfunctional isocyanate to form a polyvinyl alcohol-isocyanate-hydroxyalkyl cellulose ether block copolymer.
In the present invention, the preparation method of the modified cellulose ether comprises the following steps:
(1) completely dissolving 0.5-6 parts by mass of hydroxyalkyl cellulose ether and 0-10 parts by mass of polyvinyl alcohol in 100 parts by mass of water;
(2) adding 20-55 parts by mass of polyfunctional isocyanate, mixing and reacting to obtain the polyfunctional isocyanate modified hydroxyalkyl cellulose ether.
In the preparation method of the modified cellulose ether, the reaction time of the step (2) can be 3-10min, and the reaction can be carried out at room temperature.
Preferably, the viscosity of the hydroxyalkyl cellulose ether at 20 ℃ is 300-6000cp, preferably 400-5000cp and more preferably 4000-5000 cp.
The flour is an active filler containing protein and starch components, can prevent resin from excessively permeating into wood, and can also prevent the phenomenon of glue shortage caused by short aging time, high resin fluidity and extrusion of glue solution during pressurization. Meanwhile, starch in the flour can absorb moisture, certain moisture can be kept in the glue layer after glue is coated, the fluidity of the glue is increased, the surface of the wood is wetted, and a small amount of glue is infiltrated into the wood, so that the glue is firmer.
The filler can improve the solid content of the adhesive, improve the fluidity of the adhesive and the like. The filler in the invention is one or a combination of more of calcium carbonate, barium sulfate, montmorillonite, kaolin, mica powder, talcum powder and wood powder.
The invention also provides a preparation method of the adhesive for the formaldehyde-free plywood, which comprises the step of uniformly mixing 125-160 parts by weight of modified cellulose ether aqueous solution, 20-60 parts by weight of flour and 5-60 parts by weight of filler by stirring.
The invention also provides a plywood which comprises the adhesive.
The invention also provides a preparation method of the formaldehyde-free plywood, which comprises the following steps:
(1) applying the adhesive of the invention on the surface of the veneer;
(2) carrying out veneer assembly on the glued veneers according to the odd layer principle and the mutually vertical fiber directions of the adjacent veneers, and prepressing after the closed-end display of the plate blank;
(3) and carrying out hot pressing on the obtained plate blank to obtain the plywood.
The veneer material includes, but is not limited to, poplar, eucalyptus, pine, birch and the like, the water content is 7-40 wt%, and the single-side glue application amount is 150-250g/m2(ii) a Assembling within 1h after sizing; pre-pressing within 3 hours after the glue is applied and the assembly is carried out, wherein the pre-pressing pressure is 0.7-1.0MPa, and the pre-pressing time is 0.5-6 hours; the hot pressing temperature is 110-160 ℃, the hot pressing pressure is 0.1-1.0MPa, and the hot pressing factor is 0.5-4 min/mm.
As understood by those skilled in the art, in step (3), hot pressing is performed in a hot press: the plate blank is heated and pressurized, mass transfer and heat transfer are carried out in the plate blank through water vapor convection, and the adhesive is solidified and forms strong bonding.
The invention has the following advantages and positive effects:
(1) the adhesive for preparing the formaldehyde-free plywood provided by the invention is low in cost, moderate in viscosity and fluidity, and particularly suitable for a roller coating gluing process, and the prepared board is high in strength and equivalent in formaldehyde release amount to raw wood.
(2) The invention uses the high reaction activity of isocyanate to realize the copolymerization reaction of polyvinyl alcohol, isocyanate and hydroxyalkyl cellulose ether at room temperature by modifying the hydroxyalkyl cellulose ether with polyfunctional isocyanate, the method is simple and easy to implement, the product has good initial viscosity and moderate chemical reaction activity, and is particularly suitable for being used as an adhesive for plywood. The pH value of the adhesive system provided by the invention is close to 7, and the adhesive system has no obvious acidity or alkalinity, can not cause the aging of the adhesive and wood, and has the durability of boards; meanwhile, the adhesive system provided by the invention does not contain heavy metals, and is more environment-friendly and safer.
(3) According to the invention, the polyfunctional isocyanate and the hydroxyalkyl cellulose ether are reacted to obtain the high molecular weight block copolymer, and the high molecular weight can enable an adhesive system to have better initial viscosity. Meanwhile, as most or all of the isocyanate takes part in the chemical reaction, the content of the isocyanate group with high reaction activity remained in the system is obviously reduced, and then the isocyanate group is mixed with the flour and the filler, so that the prepared glue solution has better chemical stability, the technical indexes such as the viscosity, the fluidity, the wettability and the like of the system are more stable, the longer operation time can be given, and the method is more suitable for the actual production process. In the prior art, all components of the adhesive are directly mixed to prepare a glue solution for use, and due to the existence of the filler, the collision probability of isocyanate and molecules of active hydrogen-containing compounds such as polyvinyl alcohol, hydroxyalkyl cellulose ether and the like is reduced, the chemical reaction rate is reduced, the viscosity of a system is continuously increased, the fluidity and the wettability are continuously reduced, the process index is continuously changed, and the industrial production is not facilitated.
The specific implementation mode is as follows:
embodiments of the present invention are further illustrated by the following examples, but the present invention is not limited to the examples listed, and is intended to include any other known variations within the scope of the invention as claimed.
Polymethylene polyphenyl Polyisocyanate (PMDI): a functionality of about 2.7, a viscosity of 180-250cP at 25 deg.C, an NCO content of 30.5-32%, Vanhua Chemicals group Ltd;
toluene Diisocyanate (TDI): 67 + -2% of 2, 4-body content, 33 + -2% of 4, 4-body content, 6-8% of freezing point, 3cP of viscosity at 25 deg.C, Wanhua chemical group, Inc.;
hydroxypropyl methylcellulose ether 9071, 11% hydroxypropyl content (mass fraction), 28.5% methoxy content (mass fraction), 2% aqueous solution viscosity 5000cp at 20 ℃, wawa chemical group ltd;
hydroxypropyl methylcellulose ether 9070, hydroxypropyl content (mass fraction) 5%, methoxyl content (mass fraction) 26.5%, 2% aqueous solution viscosity 400cp at 20 deg.C, Vanhua chemical group GmbH;
hydroxypropyl methylcellulose ether 9075, hydroxypropyl content (mass fraction) 11%, methoxyl content (mass fraction) 29.6%, 2% aqueous solution viscosity of 20000cp at 20 deg.C, Vanhua chemical group GmbH;
1788 polyvinyl alcohol, 1600-inch of polymerization degree, 1850 alcoholysis degree (mole fraction) of 86.0-90.0%, Anhui Wei group, Limited liability company;
2488, the degree of polymerization 2300-2600%, the degree of alcoholysis (mole fraction) of 86.0-90.0%, Anhui Wei group, Limited liability company;
flour, commercially available edible flour;
calcium carbonate, 800 mesh, Lingshou county poplar mineral powder processing plant;
wood flour, 400 mesh, Wanhua chemical group, Inc.;
the eucalyptus veneer has the water content of 15 percent and the thickness of 1.7 mm.
Example 1
Preparation of aqueous modified cellulose ether solution:
(1) 0.5kg of hydroxypropyl methylcellulose ether 9071 and 4kg of polyvinyl alcohol 2488 are completely dissolved in 100kg of water;
(2) adding 55kg of polyfunctional isocyanate PMDI, mixing and reacting for 3min to obtain the polyfunctional isocyanate modified hydroxypropyl methyl cellulose ether.
Preparing an adhesive for plywood:
159.5kg of modified cellulose ether aqueous solution, 60kg of flour and 40kg of calcium carbonate are stirred and evenly mixed to obtain the adhesive for formaldehyde-free plywood.
Preparing the formaldehyde-free plywood:
(a) glue is applied to the eucalyptus veneer in a roller coating mode, and the glue application amount is 160g/m2；
(b) Assembling immediately after sizing; assembling the veneers into a veneer assembly according to the odd layer principle and the mutually vertical fiber directions of the adjacent veneers, wherein the number of the plate blank layers is 9;
(c) pre-pressing within 30min after assembly, wherein the pre-pressing pressure is 0.7MPa, and the pre-pressing time is 0.5 h;
(d) and (3) feeding the pre-pressed plate blank into a hot press, wherein the hot pressing temperature is 120 ℃, the hot pressing pressure high pressure section is 0.8MPa, the hot pressing pressure low pressure section is 0.3MPa, the hot pressing time is 9min, and the hot pressing time ratio of the hot pressing pressure high pressure section to the low pressure section is 3:2, so as to obtain the formaldehyde-free additional plywood.
And (3) testing the I-type bonding strength and formaldehyde release amount by a dryer method of the obtained plate according to a GBT 17657-2013 artificial plate and a veneer artificial plate physical and chemical property test method. The results are shown in Table 1.
The length of the pot life of the system can be compared more accurately by testing the viscosity increase condition of the system. The specific method comprises the following steps: after the adhesive is prepared, the viscosity of the system is monitored for 2 hours at 25 ℃ by using a viscometer, and the result is shown in table 1.
Example 2
Preparation of aqueous modified cellulose ether solution:
(1) 0.75kg of hydroxypropyl methylcellulose ether 9071 was completely dissolved in 100kg of water together with 4kg of polyvinyl alcohol 2488;
(2) adding 43kg of polyfunctional isocyanate PMDI, mixing and reacting for 4min to obtain the polyfunctional isocyanate modified hydroxypropyl methyl cellulose ether.
Preparing an adhesive for plywood:
147.75kg of the obtained modified cellulose ether aqueous solution, 35kg of flour and 35kg of calcium carbonate are stirred and uniformly mixed to obtain the adhesive for the formaldehyde-free plywood.
Preparing the formaldehyde-free plywood:
(a) glue is applied to the eucalyptus veneer in a roller coating mode, and the glue application amount is 200g/m2；
(b) After sizing, standing for 10min and then assembling; assembling the veneers into a veneer assembly according to the odd layer principle and the mutually vertical fiber directions of the adjacent veneers, wherein the number of the plate blank layers is 9;
(c) pre-pressing within 2 hours after assembly, wherein the pre-pressing pressure is 1.0MPa, and the pre-pressing time is 6 hours;
(d) and (3) conveying the pre-pressed plate blank into a hot press, wherein the hot pressing temperature is 140 ℃, the hot pressing pressure high-pressure section is 0.8MPa, the hot pressing pressure low-pressure section is 0.1MPa, the hot pressing time is 23min, and the hot pressing time ratio of the hot pressing pressure high-pressure section to the low-pressure section is 3:2, so that the formaldehyde-free added plywood is obtained.
The plate property test method is the same as that of example 1. The results are shown in Table 1. The viscosity build of the adhesive system is shown in table 2.
Example 3
Preparation of aqueous modified cellulose ether solution:
(1) 4kg of hydroxypropyl methylcellulose ether 9070 and 2kg of polyvinyl alcohol 2488 were completely dissolved in 100kg of water;
(2) adding 25kg of polyfunctional isocyanate PMDI, mixing and reacting for 10min to obtain the polyfunctional isocyanate modified hydroxypropyl methyl cellulose ether.
Preparing an adhesive for a plywood:
and (3) stirring 131kg of the obtained modified cellulose ether aqueous solution, 20kg of flour and 60kg of wood flour until the modified cellulose ether aqueous solution, the flour and the wood flour are uniformly mixed to obtain the formaldehyde-free adhesive for the plywood.
Preparing the formaldehyde-free plywood:
(a) glue is applied to the eucalyptus veneer in a roller coating mode, and the glue application amount is 250g/m2；
(b) After sizing, placing for 1h and then assembling; carrying out veneer assembly on veneers according to the odd layer principle and the mutually vertical fiber directions of the adjacent veneers, wherein the number of the plate blank layers is 9;
(c) pre-pressing within 1h after assembly, wherein the pre-pressing pressure is 1.0MPa, and the pre-pressing time is 4 h;
(d) and (3) feeding the pre-pressed plate blank into a hot press, wherein the hot pressing temperature is 160 ℃, the hot pressing pressure high pressure section is 0.8MPa, the hot pressing pressure low pressure section is 0.1MPa, the hot pressing time is 60min, and the hot pressing time ratio of the hot pressing pressure high pressure section to the low pressure section is 3:2, so as to obtain the formaldehyde-free plywood.
The plate property test method was the same as in example 1. The results are shown in Table 1. The viscosity increase of the adhesive system is shown in table 2.
Example 4
Preparation of aqueous modified cellulose ether solution:
(1) 6kg of hydroxypropyl methylcellulose ether 9070 were completely dissolved in 100kg of water;
(2) adding 32kg of polyfunctional isocyanate PMDI, mixing and reacting for 6min to obtain the polyfunctional isocyanate modified hydroxypropyl methyl cellulose ether.
Preparing an adhesive for a plywood:
and (3) stirring 138kg of the obtained modified cellulose ether aqueous solution, 40kg of flour and 35kg of calcium carbonate until the modified cellulose ether aqueous solution, the flour and the calcium carbonate are uniformly mixed to obtain the formaldehyde-free adhesive for the plywood.
Preparing a formaldehyde-free plywood:
(a) glue is applied to the eucalyptus veneer in a roller coating mode, and the glue application amount is 200g/m2；
(b) After sizing, placing for 0.5h and then assembling; carrying out veneer assembly on veneers according to the odd layer principle and the mutually vertical fiber directions of the adjacent veneers, wherein the number of the plate blank layers is 9;
(c) pre-pressing within 1h after assembly, wherein the pre-pressing pressure is 1.0MPa, and the pre-pressing time is 1 h;
(d) and (3) feeding the pre-pressed plate blank into a hot press, wherein the hot pressing temperature is 130 ℃, the hot pressing pressure high pressure section is 0.8MPa, the hot pressing pressure low pressure section is 0.1MPa, the hot pressing time is 45min, and the hot pressing time ratio of the hot pressing pressure high pressure section to the low pressure section is 3:2, so as to obtain the formaldehyde-free additional plywood.
The plate property test method was the same as in example 1. The results are shown in Table 1. The viscosity increase of the adhesive system is shown in table 2.
Example 5
Preparation of aqueous modified cellulose ether solution:
(1) completely dissolving 3kg of hydroxypropyl methylcellulose ether 9070 and 10kg of polyvinyl alcohol 1788 in 100 parts of water;
(2) adding 28kg of polyfunctional isocyanate PMDI and 2kg of TDI, mixing and reacting for 10min to obtain the polyfunctional isocyanate copolymerization modified hydroxypropyl methyl cellulose ether.
Preparing an adhesive for plywood:
and (3) stirring 141kg of the obtained modified cellulose ether aqueous solution, 30kg of flour and 18kg of calcium carbonate until the modified cellulose ether aqueous solution, the flour and the calcium carbonate are uniformly mixed to obtain the formaldehyde-free adhesive for the plywood.
Preparing the formaldehyde-free plywood:
(a) glue is applied to the eucalyptus veneer in a roller coating mode, and the glue application amount is 200g/m2；
(b) Placing the mixture after sizing and immediately assembling; carrying out veneer assembly on veneers according to the odd layer principle and the mutually vertical fiber directions of the adjacent veneers, wherein the number of the plate blank layers is 9;
(c) pre-pressing within 3 hours after assembly, wherein the pre-pressing pressure is 1.0MPa, and the pre-pressing time is 4 hours;
(d) and (3) feeding the pre-pressed plate blank into a hot press, wherein the hot pressing temperature is 150 ℃, the hot pressing pressure high pressure section is 1MPa, the hot pressing pressure low pressure section is 0.1MPa, the hot pressing time is 30min, and the hot pressing time ratio of the hot pressing pressure high pressure section to the low pressure section is 3:2, so as to obtain the formaldehyde-free plywood.
The plate property test method is the same as that of example 1. The results are shown in Table 1. The viscosity increase of the adhesive system is shown in table 2.
Example 6
Preparation of aqueous modified cellulose ether solution:
(1) 1.5kg of hydroxypropyl methylcellulose ether 9071 was completely dissolved in 100kg of water;
(2) adding 45kg of polyfunctional isocyanate PMDI, mixing and reacting for 3min to obtain the polyfunctional isocyanate modified hydroxypropyl methyl cellulose ether.
Preparing an adhesive for a plywood:
146.5kg of modified cellulose ether aqueous solution, 60kg of flour and 40kg of calcium carbonate are stirred and uniformly mixed to obtain the adhesive for the formaldehyde-free plywood.
Preparing a formaldehyde-free plywood:
(a) glue is applied to the eucalyptus veneer in a roller coating mode, and the glue application amount is 180g/m2；
(b) Assembling immediately after sizing; carrying out veneer assembly on veneers according to the odd layer principle and the mutually vertical fiber directions of the adjacent veneers, wherein the number of the plate blank layers is 9;
(c) pre-pressing within 30min after assembly, wherein the pre-pressing pressure is 0.7MPa, and the pre-pressing time is 0.5 h;
(d) and (3) feeding the pre-pressed plate blank into a hot press, wherein the hot pressing temperature is 120 ℃, the hot pressing pressure high-pressure section is 0.8MPa, the hot pressing pressure low-pressure section is 0.3MPa, the hot pressing time is 9min, and the hot pressing time ratio of the hot pressing pressure high-pressure section to the low-pressure section is 3:2, so as to obtain the formaldehyde-free added plywood.
The plate properties were measured in the same manner as in example 1, and the results are shown in Table 1. The viscosity growth of the adhesive system is shown in table 1.
Comparative example 1
0.5kg of hydroxypropyl methyl cellulose ether 9071, 4kg of polyvinyl alcohol 2488, 100kg of water, 55kg of polyfunctional isocyanate PMDI, 60kg of flour and 40kg of calcium carbonate are stirred for 3min to uniformly mix the materials, and the formaldehyde-free adhesive for adding the plywood is obtained.
The preparation process of the plywood without formaldehyde addition is the same as that of the example 1.
The plate property test method is the same as that of example 1. The results are shown in Table 1.
Comparative example 2
1.5kg of hydroxypropyl methyl cellulose ether 9071, 100kg of water, 55kg of polyfunctional isocyanate PMDI, 60kg of flour and 40kg of calcium carbonate are stirred for 3min to uniformly mix the materials, and the formaldehyde-free adhesive for the plywood is obtained.
The preparation process of the plywood without formaldehyde addition is the same as that of the example 1.
The plate property test method is the same as that of example 1. The results are shown in Table 1.
Comparative example 3
The hydroxypropyl methylcellulose ether 9071 in example 1 was replaced with 9075, and the types and amounts of the remaining materials were the same as in example 1.
The plywood without formaldehyde is prepared by the same process as that of example 1.
The plate property test method was the same as in example 1. The results are shown in Table 1.
Comparative example 4
The veneer used was subjected to a dryer formaldehyde emission test in the same manner as in example 1. The results are shown in Table 1.
Table 1 plywood performance test results
The performance test results of the plates of examples 1-6 and comparative examples 1-3 show that the adhesive prepared by directly mixing the multifunctional isocyanate modified hydroxypropyl methyl cellulose ether and the filler has better adhesive property and higher plate bonding strength than the adhesive prepared by directly mixing various materials; the formaldehyde emission test results of examples 1-6 and comparative example 4 show that the formaldehyde emission of the plywood obtained by the adhesive system provided by the invention is equivalent to that of a raw material veneer, and the plywood really belongs to formaldehyde-free added plywood.
The viscosity tracking results of the adhesives in the examples 1-6 and the comparative examples 1-2 show that the viscosity change of the adhesive system provided by the invention is smaller and more stable in 2h, the working life is longer, the adhesive system is more suitable for a roller coating sizing process, and the actual production requirements can be met. The adhesive systems of comparative examples 1 and 2 showed a faster viscosity increase and a shorter pot life. In the comparative example 3, hydroxypropyl methyl cellulose ether with a more obvious tackifying effect is used, a glue solution system has obvious thixotropy, the components are not uniformly mixed, the viscosity difference of adhesives at different sampling parts is large, and the actual use requirements cannot be met.
The results of the above examples and comparative examples are combined, and it is shown that the working life of the adhesive system can be prolonged by modifying the copolymerization of the polyfunctional isocyanate and the hydroxypropyl methyl cellulose ether and adding the filler, and the sheet material performance is more excellent.
It should be noted that the above-mentioned embodiments illustrate only preferred embodiments of the present invention, and are not intended to limit the scope of the present invention, and although the present invention has been described in detail with reference to preferred embodiments, it will be understood by those skilled in the art that various changes and modifications can be made to the technical solution of the present invention or equivalents thereof without departing from the scope of the present invention as defined in the claims.
Claims (10)
1. The adhesive for the formaldehyde-free plywood is characterized by comprising the following raw materials in parts by weight: 160 parts of modified cellulose ether aqueous solution, 20-60 parts of flour and 5-60 parts of filler.
2. The adhesive of claim 1 wherein the modified cellulose ether is a multifunctional isocyanate modified hydroxyalkyl cellulose ether comprising one or more of hydroxyethyl cellulose ether, hydroxypropyl cellulose ether, preferably hydroxypropyl cellulose ether;
preferably, the hydroxyalkyl cellulose ether comprises one or more of dihydroxypropyl cellulose ether, ethyl hydroxyethyl cellulose ether, methyl hydroxyethyl cellulose ether, hydroxypropyl methyl cellulose ether, hydroxyethyl carboxymethyl cellulose ether, hydroxypropyl carboxymethyl cellulose ether, preferably hydroxypropyl methyl cellulose ether.
3. The adhesive of claim 2 wherein the aqueous modified cellulose ether solution comprises: 0.5-6 parts by mass of hydroxyalkyl cellulose ether, 0-10 parts by mass of polyvinyl alcohol, 20-55 parts by mass of polyfunctional isocyanate and 100 parts by mass of water.
4. The adhesive as claimed in claim 2 or 3, wherein the degree of polymerization of the polyvinyl alcohol is 1600-2600, and the degree of alcoholysis is 86.0-90.0%;
preferably, the multifunctional isocyanate is selected from one or more of aromatic polyisocyanate and aliphatic polyisocyanate; preferably an aromatic polyisocyanate; more preferably one or more of toluene diisocyanate, diphenylmethane diisocyanate and polymethylene polyphenyl polyisocyanate;
preferably, the hydroxypropyl methyl cellulose ether contains 4-12% of hydroxypropyl by mass and 23-32% of methoxyl by mass;
preferably, the viscosity of the 2 wt% aqueous solution of the hydroxyalkyl cellulose ether at 20 ℃ is 300-6000cp, preferably 400-5000cp, and more preferably 4000-5000 cp.
5. The adhesive according to any one of claims 1 to 4, wherein the preparation method of the modified cellulose ether comprises the following steps:
(1) completely dissolving 0.5-6 parts by mass of hydroxyalkyl cellulose ether and 0-10 parts by mass of polyvinyl alcohol in 100 parts by mass of water;
(2) adding 20-55 parts by mass of polyfunctional isocyanate, mixing and reacting to obtain the polyfunctional isocyanate modified hydroxyalkyl cellulose ether.
6. The adhesive of claim 5, wherein the reaction time of step (2) is 3-10 min.
7. The adhesive according to any one of claims 1 to 6, wherein the filler is one or more of calcium carbonate, barium sulfate, montmorillonite, kaolin, mica powder, talc and wood powder.
8. The method for preparing the adhesive according to any one of claims 1 to 7, wherein 125-160 parts by weight of the modified cellulose ether aqueous solution, 20-60 parts by weight of flour and 5-60 parts by weight of filler are stirred until being uniformly mixed, so as to obtain the formaldehyde-free adhesive for plywood.
9. Plywood characterized in that it comprises the adhesive according to any one of claims 1 to 7 or prepared by the preparation method according to claim 8.
10. A method for preparing a plywood, comprising the following steps:
(1) applying the adhesive according to any one of claims 1 to 7 or the adhesive prepared by the preparation method according to claim 8 on the surface of a veneer;
(2) the glued veneers are assembled into a veneer blank according to the odd layer principle and the fiber directions of the adjacent veneers are mutually vertical, and the prepressing is carried out after the closed opening of the veneer blank is laid;
(3) carrying out hot pressing on the obtained plate blank to obtain the plywood;
preferably, the veneer material includes, but is not limited to, poplar, eucalyptus, pine, birch, etc., the water content is 7 wt% -40 wt%,
preferably, the single-side sizing amount is 150-250g/m2；
Preferably, assembly is carried out within 1h after sizing; pre-pressing within 3 hours after the glue is applied and the assembly is carried out, wherein the pre-pressing pressure is 0.7-1.0MPa, and the pre-pressing time is 0.5-6 hours;
preferably, the hot-pressing temperature is 110-160 ℃, the hot-pressing pressure is 0.1-1.0MPa, and the hot-pressing factor is 0.5-4 min/mm.
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| CN115537168A (en) * | 2022-10-17 | 2022-12-30 | 金陵科技学院 | Preparation method of water-resistant bi-component natural biomass cellulose-based polyurethane building sealant and product thereof |
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