CN116178979A - Anti-cracking low-formaldehyde multi-layer board and preparation method thereof - Google Patents
Anti-cracking low-formaldehyde multi-layer board and preparation method thereof Download PDFInfo
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- CN116178979A CN116178979A CN202310196089.2A CN202310196089A CN116178979A CN 116178979 A CN116178979 A CN 116178979A CN 202310196089 A CN202310196089 A CN 202310196089A CN 116178979 A CN116178979 A CN 116178979A
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- lignin
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- WSFSSNUMVMOOMR-UHFFFAOYSA-N formaldehyde Substances O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 title claims abstract description 84
- 238000005336 cracking Methods 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 229920005610 lignin Polymers 0.000 claims abstract description 73
- 229920005992 thermoplastic resin Polymers 0.000 claims abstract description 55
- 239000002699 waste material Substances 0.000 claims abstract description 51
- 239000000835 fiber Substances 0.000 claims abstract description 27
- 239000012948 isocyanate Substances 0.000 claims abstract description 26
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 26
- 239000004744 fabric Substances 0.000 claims abstract description 22
- 239000003607 modifier Substances 0.000 claims abstract description 19
- 239000002994 raw material Substances 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims description 25
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 239000000203 mixture Substances 0.000 claims description 16
- 239000002023 wood Substances 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 241000872931 Myoporum sandwicense Species 0.000 claims description 13
- 239000003795 chemical substances by application Substances 0.000 claims description 11
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 11
- 239000003755 preservative agent Substances 0.000 claims description 11
- 230000002335 preservative effect Effects 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 238000007731 hot pressing Methods 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 229920005989 resin Polymers 0.000 claims description 7
- 239000011347 resin Substances 0.000 claims description 7
- 239000000243 solution Substances 0.000 claims description 7
- RTTZISZSHSCFRH-UHFFFAOYSA-N 1,3-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC(CN=C=O)=C1 RTTZISZSHSCFRH-UHFFFAOYSA-N 0.000 claims description 6
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 6
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical group C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- HZWXJJCSDBQVLF-UHFFFAOYSA-N acetoxysulfonic acid Chemical compound CC(=O)OS(O)(=O)=O HZWXJJCSDBQVLF-UHFFFAOYSA-N 0.000 claims description 6
- 239000000428 dust Substances 0.000 claims description 6
- 238000002791 soaking Methods 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 5
- 230000001105 regulatory effect Effects 0.000 claims description 5
- 238000005507 spraying Methods 0.000 claims description 5
- 238000003892 spreading Methods 0.000 claims description 5
- 230000007480 spreading Effects 0.000 claims description 5
- 238000004078 waterproofing Methods 0.000 claims description 5
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 4
- 239000004800 polyvinyl chloride Substances 0.000 claims description 4
- 244000166124 Eucalyptus globulus Species 0.000 claims description 3
- 239000004743 Polypropylene Substances 0.000 claims description 3
- 241000219000 Populus Species 0.000 claims description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 3
- -1 polypropylene Polymers 0.000 claims description 3
- 229920001155 polypropylene Polymers 0.000 claims description 3
- 239000012286 potassium permanganate Substances 0.000 claims description 3
- 229920013716 polyethylene resin Polymers 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 10
- 230000008569 process Effects 0.000 abstract description 8
- 230000007797 corrosion Effects 0.000 abstract description 4
- 238000005260 corrosion Methods 0.000 abstract description 4
- 230000006835 compression Effects 0.000 abstract description 3
- 238000007906 compression Methods 0.000 abstract description 3
- 239000011230 binding agent Substances 0.000 abstract description 2
- 239000011734 sodium Substances 0.000 description 12
- 230000001070 adhesive effect Effects 0.000 description 11
- 239000000853 adhesive Substances 0.000 description 10
- 125000003118 aryl group Chemical group 0.000 description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 150000001299 aldehydes Chemical class 0.000 description 4
- 230000017858 demethylation Effects 0.000 description 4
- 238000010520 demethylation reaction Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 4
- 230000009257 reactivity Effects 0.000 description 4
- JQWHASGSAFIOCM-UHFFFAOYSA-M sodium periodate Chemical compound [Na+].[O-]I(=O)(=O)=O JQWHASGSAFIOCM-UHFFFAOYSA-M 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 241000282414 Homo sapiens Species 0.000 description 3
- 230000001965 increasing effect Effects 0.000 description 3
- 241001391944 Commicarpus scandens Species 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 229920001807 Urea-formaldehyde Polymers 0.000 description 2
- 238000010521 absorption reaction 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
- 238000005452 bending Methods 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 231100000956 nontoxicity Toxicity 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- ZNZYKNKBJPZETN-WELNAUFTSA-N Dialdehyde 11678 Chemical compound N1C2=CC=CC=C2C2=C1[C@H](C[C@H](/C(=C/O)C(=O)OC)[C@@H](C=C)C=O)NCC2 ZNZYKNKBJPZETN-WELNAUFTSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 239000004826 Synthetic adhesive Substances 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 239000012434 nucleophilic reagent Substances 0.000 description 1
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 230000001568 sexual effect Effects 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27N—MANUFACTURE BY DRY PROCESSES OF ARTICLES, WITH OR WITHOUT ORGANIC BINDING AGENTS, MADE FROM PARTICLES OR FIBRES CONSISTING OF WOOD OR OTHER LIGNOCELLULOSIC OR LIKE ORGANIC MATERIAL
- B27N3/00—Manufacture of substantially flat articles, e.g. boards, from particles or fibres
- B27N3/007—Manufacture of substantially flat articles, e.g. boards, from particles or fibres and at least partly composed of recycled material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
- B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
- B27K3/02—Processes; Apparatus
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
- B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
- B27K3/52—Impregnating agents containing mixtures of inorganic and organic compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27N—MANUFACTURE BY DRY PROCESSES OF ARTICLES, WITH OR WITHOUT ORGANIC BINDING AGENTS, MADE FROM PARTICLES OR FIBRES CONSISTING OF WOOD OR OTHER LIGNOCELLULOSIC OR LIKE ORGANIC MATERIAL
- B27N3/00—Manufacture of substantially flat articles, e.g. boards, from particles or fibres
- B27N3/08—Moulding or pressing
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
- C08H6/00—Macromolecular compounds derived from lignin, e.g. tannins, humic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L97/00—Compositions of lignin-containing materials
- C08L97/02—Lignocellulosic material, e.g. wood, straw or bagasse
-
- C—CHEMISTRY; METALLURGY
- 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
- C08K3/02—Elements
- C08K3/08—Metals
- C08K2003/0806—Silver
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Forests & Forestry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Biochemistry (AREA)
- Dry Formation Of Fiberboard And The Like (AREA)
Abstract
The invention relates to the technical field of multi-layer boards, in particular to an anti-cracking low-formaldehyde multi-layer board and a preparation method thereof; comprises the raw materials of 200 to 300 parts of forestry waste, 40 to 60 parts of fiber cloth, 20 to 40 parts of modified lignin, 5 to 8 parts of isocyanate, 10 to 30 parts of thermoplastic resin and 3 to 10 parts of modifier; the invention takes forestry waste and fiber cloth as main raw materials, takes modified lignin and isocyanate as binders, adds thermoplastic resin to assist in bonding, and adds corrosion resistance and waterproof performance to the modifier to prepare a multilayer board; the prepared multilayer board has the advantages of less formaldehyde release, higher strength, strong compression resistance and crack resistance, difficult cracking in the processing and using processes, stable structure, capability of being used in application places with higher strength requirements and expanded application range of the multilayer board.
Description
Technical Field
The invention relates to the technical field of multi-layer boards, in particular to an anti-cracking low-formaldehyde multi-layer board and a preparation method thereof.
Background
The artificial board occupies an important position in modern furniture and decoration industries, a series of formaldehyde emission limits are set for guaranteeing the requirements of human beings on living environment, the standards of GB/T39598-2021 artificial board indoor bearing limit guideline based on limiting formaldehyde release amount and GB/T39600-2021 artificial board and product formaldehyde release amount grading are set for gradually enhancing the 'health and environment protection' concepts of consumers, and the requirements of people on living environment are higher and higher.
The adhesive can be used in a large amount in the production process of the artificial board, raw materials of the traditional adhesive (also called petroleum-based adhesive) can pollute the production process, the prepared product can generate toxic and harmful gas to influence the environment and human health, and in the synthetic adhesive for the artificial board, the application is more widely used as the traditional aldehyde adhesive, and potential formaldehyde release and hazard exist in the production and use processes of the adhesive. Therefore, the artificial board adhesive is developed towards the directions of no toxicity, no harm and better cementing performance, and therefore, the multilayer board is developed to have low formaldehyde release or no formaldehyde release, and simultaneously has higher strength and better cracking resistance, and has positive significance for the practical application requirements of the multilayer board.
Disclosure of Invention
The invention aims to provide an anti-cracking low-formaldehyde multi-layer board and a preparation method thereof, and the prepared multi-layer board has the advantages of less formaldehyde release amount, higher strength, strong compression resistance and cracking resistance, difficulty in cracking in the processing and using processes, stable structure, capability of being used in application places with higher strength requirements and wide application range of the multi-layer board.
In order to achieve the above purpose, the present invention provides the following technical solutions:
an anti-cracking low-formaldehyde multi-layer board comprises the following raw materials in parts by weight: 200-300 parts of forestry waste, 40-60 parts of fiber cloth, 20-40 parts of modified lignin, 5-8 parts of isocyanate, 10-30 parts of thermoplastic resin and 3-10 parts of modifier;
the preparation method of the anti-cracking low-aldehyde multilayer board comprises the following steps:
step one: mixing the modified lignin with isocyanate in parts by weight, and stirring and mixing for 5-15 min at the speed of 80-120 r/min to obtain a mixture;
step two: taking thermoplastic resin in parts by weight, adding 0.5-1 times of absolute ethyl alcohol by mass of the thermoplastic resin, transferring the thermoplastic resin into a reaction kettle, adding 0.01-0.02 times of maleic anhydride by mass of the thermoplastic resin and 0.1-0.2 times of dicumyl peroxide by mass of the maleic anhydride, and reacting for 30-90 min at 200-400 ℃ in a nitrogen atmosphere to obtain molten thermoplastic resin;
step three: taking forestry waste in parts by mass, adding 5% concentrated sulfuric acid-acetic anhydride solution with the mass of 2-3 times that of the forestry waste, and soaking for 8-12 hours to obtain modified forestry waste;
step four: uniformly mixing the molten thermoplastic resin obtained in the second step and the modified forestry waste obtained in the third step, transferring the mixture into a die for multiple times, spreading a layer of fiber cloth with the thickness of 3-8 layers in each die, uniformly spraying the mixture obtained in the first step on each layer of fiber cloth, uniformly adding a modifier, and hot-pressing at 190-240 ℃ for 3-5 min to obtain the anti-cracking low-formaldehyde multi-layer board.
Further preferably, the forestry waste is branch waste of eucalyptus and poplar, the forestry waste is washed to remove dust, then dried, crushed and sieved by a 20-mesh sieve to obtain the wood chip-shaped forestry waste.
Further preferably, the modified lignin is prepared by taking a certain massAdding lignin, deionized water, stirring, adding NaOH aqueous solution of 0.1mol/L, regulating pH to 8-9, and adding Na of a certain mass 2 SO 3 Heating to 90 ℃ in water bath, and carrying out reflux reaction for 2-3 h to obtain demethylated lignin; adding NaIO with a certain mass into the demethylated lignin 4 And rapidly stirring at a speed of 100-150 r/min for 3-5 min to obtain the modified lignin.
Further preferably, the modified lignin comprises the following raw materials in percentage by mass: deionized water: na (Na) 2 SO 3 ：NaIO 4 ＝10：15～25：1：1～4。
Under the condition of NaOH aqueous solution, hydroxymethyl and Na in lignin molecules 2 SO 3 Nucleophilic substitution reaction of ions, conversion of lignin into sulfite pulp, further oxidation with sodium periodate, exposing O - Can further react with lignin to reduce the methoxy content of the modified lignin and improve the reactivity; in addition, the beta-O-4 bond in lignin molecules is easily oxidized and cracked by sodium periodate, so that aldehyde is generated, and dialdehydes are also possibly generated. In addition, the reactivity of the aromatic ring is increased as the demethylation produces a greater proportion of aromatic hydroxyl groups.
The equations involved in modifying lignin are:
Na 2 SO 3 +2H 2 O→SO 3 2- +2H + +2OH - +2Na + ；
further preferably, the isocyanate is diphenylmethane diisocyanate and m-xylylene isocyanate, and the mass ratio is 2:2 to 3.
Further preferably, the thermoplastic resin is one or more of polypropylene resin, polyvinyl chloride resin and polyethylene resin.
Further preferably, the modifier is preservative and waterproofing agent, and the mass ratio is 2: 1-3, wherein the preservative is one of potassium permanganate, nano silver and hydrogen peroxide, and the waterproof agent is wood wax oil.
The invention has the beneficial effects that:
1. according to the invention, forestry waste and fiber cloth are used as main raw materials, modified lignin and isocyanate adhesive are used as binders, thermoplastic resin is added to assist in bonding, the modifier increases corrosion resistance and waterproof performance, and the low-formaldehyde multi-layer board is manufactured, wherein the fiber cloth is mixed in the multi-layer board to enhance the cracking resistance of the board, the thermoplastic resin not only has a bonding effect, but also wraps and firmly bonds fine forestry waste in the multi-layer board with the assistance of the thermoplastic resin, so that the multi-layer board is not easy to crack in the processing and using processes, and the finally manufactured multi-layer board has the characteristics of cracking resistance and low formaldehyde.
2. The method comprises the steps of processing and using eucalyptus and poplar branch forestry waste, washing to remove dust, airing, crushing and sieving to form wood dust with similar particle size, and processing a subsequent multilayer board, so that the forestry waste can be recycled, and further economic value is generated; the forestry waste wood chips with similar particle sizes are easy to form a uniform and stable structure in the subsequent multilayer board processing process, and after being mixed with the mixture of the modified lignin and isocyanate for hot pressing, the forestry waste wood chips are stable in structure and not easy to break or crack due to internal stress. And 5% concentrated sulfuric acid-acetic anhydride solution is used for soaking forestry waste, the acid anhydride and hydroxyl groups on the surface of the forestry waste undergo esterification reaction, polar groups on the surface of the forestry waste are reduced, amorphous substances on the surface of the forestry waste are removed, the polarity of the surface of the forestry waste is reduced, the free energy of the surface is increased, and the polarity of the forestry waste is similar to that of thermoplastic resin, so that the compatibility between the forestry waste and the thermoplastic resin is improved, and the aim of improving the physical and mechanical properties of the multilayer board is fulfilled.
3. The invention is woven by adopting the fiber cloth as the carbon fiber, the weaving is precise, the strength is high, the fiber cloth is embedded in the multi-layer board, and the modified lignin, the isocyanate and the thermoplastic resin are hot pressed with forestry waste to form a stable whole, so that the manufactured multi-layer board has higher strength, is not easy to break and crack, enhances the strength of the wood multi-layer board, reduces the production cost of the fiber cloth mixed board, enables the wood multi-layer board to be used in application places with higher strength requirements, and expands the application range of the multi-layer board.
4. The invention adopts modified lignin, takes lignin as raw material, lignin as a natural polymer compound, has abundant sources, is the second most renewable resource next to cellulose in nature, however, methoxy on lignin aromatic ring leads lignin steric hindrance to become larger so as to influence the reaction activity, the demethylation modification can improve the phenolic hydroxyl content so as to improve the lignin reaction activity, and the lignin is prepared by using nucleophilic reagent Na under the condition of NaOH aqueous solution 2 SO 3 Reacts with lignin to remove methoxy on lignin aromatic ring, and then passes through NaIO 4 Oxidation to expose O - Can further react with lignin, and the demethylation generates a larger proportion of aromatic hydroxyl groups, thereby increasing the reactivity of aromatic rings; in addition, lignin molecules contain aliphatic hydroxyl, phenolic hydroxyl, methoxy and other functional groups, which influence the reactivity and chemical properties of lignin, and particularly hydroxyl and aromatic structures are the most critical functional groups for determining the properties of polymers. The structures of lignin have a hydroxyl group near the beta-O-4 bond and another lignin in the aliphatic moiety; the ether linkage of the beta-O-4 bond is easily replaced by NaIO 4 Cleavage to form an aldehyde or dialdehyde, the aldehyde can react with the hydroxyl-activated active phenolic sites to form a stronger hardened network. Through Na 2 SO 3 Demethylation and NaIO 4 The oxidized lignin has good viscosity, can be used in the processing of multi-layer board materials, plays a role of a tackifier, and unlike the traditional urea-formaldehyde resin adhesive, does not release a large amount of formaldehyde, is a substance with low formaldehyde content or no formaldehyde release, meets the requirement of increasingly-enhanced environment-friendly market, and can be distributed around fibers and among fine fibers in the fibers to form a strong skeleton structure with cellulose and semi-fibers.
5. To improve the adhesive properties of simple lignin adhesives, isocyanates are usedCompounding sexual lignin, wherein isocyanate is diphenylmethane diisocyanate and m-xylylene isocyanate according to the mass ratio of 2: 2-3, wherein the isocyanate-NCO in the isocyanate can generate a crosslinking reaction, the-NCO can react with the-OH on the surface of the fiber to form a chemical bond, the excellent bonding effect can be achieved with a small amount of the isocyanate, the isocyanate and the modified lignin are compounded, the bonding capability of the lignin can be enhanced, and meanwhile, the CO generated in the hot pressing process due to the large amount of the isocyanate can be avoided 2 Avoiding CO 2 And the phenomena of hollowness and the like caused by the multilayer board are bad.
6. The thermoplastic resin is a high molecular polymer, is in a viscous state at high temperature, has certain viscosity, is solidified to form a solid at low temperature, is changed into a viscous state in the hot pressing process of the wood multi-layer board, can wrap forestry waste wood dust, forms an integral body by coexistence of the thermoplastic resin and the wood dust after solidification, can replace the traditional urea formaldehyde resin adhesive for processing the multi-layer board, has no formaldehyde release, can avoid harm of formaldehyde to the environment and human, and has low price, no toxicity and no harm, high strength and capability of enhancing the fracture resistance of the multi-layer board; the thermoplastic resin is grafted and modified, maleic anhydride is grafted on the thermoplastic resin under the action of the initiator dicumyl peroxide in a molten state, so that the surface polarity of the thermoplastic resin is enhanced, the interface compatibility of the thermoplastic resin and forestry waste wood chips is improved, the thermoplastic resin can obtain a good interface compatibility effect in the processing process of the multilayer board, and the structural stability of the manufactured multilayer board is facilitated.
7. The use of the modifier can improve the corrosion resistance and the water resistance of the multilayer board by adding the preservative and the waterproof agent into the multilayer board, so that the prepared multilayer board not only has better strength, less formaldehyde release and better cracking resistance, but also has certain water resistance and corrosion resistance.
Detailed Description
The following description of the present invention will be made clearly and fully, and it is apparent that the embodiments described are only some, but not all, of the embodiments of the present invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
An anti-cracking low-formaldehyde multi-layer board comprises the following raw materials in parts by weight: 200 parts of forestry waste, 40 parts of fiber cloth, 20 parts of modified lignin, 5 parts of isocyanate, 10 parts of thermoplastic resin and 3 parts of modifier;
the modified lignin is prepared by taking lignin of a certain mass, adding deionized water of a certain mass, stirring and mixing uniformly, adding 0.1mol/L NaOH aqueous solution, regulating pH to 8, and then adding Na of a certain mass 2 SO 3 Heating to 90 ℃ in water bath, and carrying out reflux reaction for 2 hours to obtain demethylated lignin; adding NaIO with a certain mass into the demethylated lignin 4 Rapidly stirring at a speed of 100r/min for 3min to obtain modified lignin; wherein the mass ratio of the raw materials in the modified lignin is lignin: deionized water: na (Na) 2 SO 3 ：NaIO 4 ＝10：15：1：1；
The isocyanate is diphenylmethane diisocyanate and m-xylylene isocyanate, and the mass ratio is 2:2, mixing; the thermoplastic resin is polypropylene resin; the modifier is preservative and waterproofing agent according to the mass ratio of 2:1, mixing, wherein the preservative is potassium permanganate, and the waterproof agent is wood wax oil;
the preparation method of the anti-cracking low-aldehyde multilayer board comprises the following steps:
step one: mixing the modified lignin with isocyanate in parts by weight, and stirring and mixing for 5min at the speed of 80r/min to obtain a mixture;
step two: taking thermoplastic resin in parts by weight, adding absolute ethyl alcohol with the mass of 0.5 time of the thermoplastic resin, transferring the thermoplastic resin into a reaction kettle, adding maleic anhydride with the mass of 0.01 time of the thermoplastic resin and dicumyl peroxide with the mass of 0.1 time of the maleic anhydride, and reacting for 30min at 200 ℃ in a nitrogen atmosphere to obtain molten thermoplastic resin;
step three: taking forestry waste in parts by mass, adding 5% concentrated sulfuric acid-acetic anhydride solution with the mass of 2 times that of the forestry waste, and soaking for 8 hours to obtain modified forestry waste;
step four: and (3) uniformly mixing the molten thermoplastic resin obtained in the second step with the modified forestry waste obtained in the third step, transferring the mixture into a die for multiple times, spreading a layer of fiber cloth every 2mm thick in the die, uniformly spraying the mixture obtained in the first step on each layer of fiber cloth, uniformly adding a modifier, and hot-pressing at 190 ℃ for 3min to obtain the anti-cracking low-formaldehyde multi-layer board.
Example 2
An anti-cracking low-formaldehyde multi-layer board comprises the following raw materials in parts by weight: 300 parts of forestry waste, 60 parts of fiber cloth, 40 parts of modified lignin, 8 parts of isocyanate, 30 parts of thermoplastic resin and 10 parts of modifier;
the modified lignin is prepared by taking lignin of a certain mass, adding deionized water of a certain mass, stirring and mixing uniformly, adding 0.1mol/L NaOH aqueous solution, regulating pH to 9, and then adding Na of a certain mass 2 SO 3 Heating to 90 ℃ in water bath, and carrying out reflux reaction for 3 hours to obtain demethylated lignin; adding NaIO with a certain mass into the demethylated lignin 4 Rapidly stirring at 150r/min for 5min to obtain modified lignin; wherein the mass ratio of the raw materials in the modified lignin is lignin: deionized water: na (Na) 2 SO 3 ：NaIO 4 ＝10：25：1：4；
The isocyanate is diphenylmethane diisocyanate and m-xylylene isocyanate, and the mass ratio is 2:3, mixing; the thermoplastic resin is polyvinyl chloride resin; the modifier is preservative and waterproofing agent according to the mass ratio of 2:3, mixing, wherein the preservative is nano silver, and the waterproof agent is wood wax oil;
the preparation method of the anti-cracking low-aldehyde multilayer board comprises the following steps:
step one: mixing the modified lignin with isocyanate in parts by weight, and stirring and mixing for 15min at the speed of 120r/min to obtain a mixture;
step two: taking thermoplastic resin in parts by weight, adding absolute ethyl alcohol with the mass of 1 time of the thermoplastic resin, transferring the thermoplastic resin into a reaction kettle, adding maleic anhydride with the mass of 0.02 time of the thermoplastic resin and dicumyl peroxide with the mass of 0.2 time of the maleic anhydride, and reacting at 400 ℃ for 90min in a nitrogen atmosphere to obtain molten thermoplastic resin;
step three: taking forestry waste in parts by mass, adding 5% concentrated sulfuric acid-acetic anhydride solution with the mass of 3 times that of the forestry waste, and soaking for 12 hours to obtain modified forestry waste;
step four: and (3) uniformly mixing the molten thermoplastic resin obtained in the second step with the modified forestry waste obtained in the third step, transferring the mixture into a die for multiple times, spreading a layer of fiber cloth in the die every 4mm thick, uniformly spraying the mixture obtained in the first step on each layer of fiber cloth, uniformly adding a modifier, and hot-pressing at 240 ℃ for 5min to obtain the anti-cracking low-formaldehyde multi-layer board.
Example 3
An anti-cracking low-formaldehyde multi-layer board comprises the following raw materials in parts by weight: 250 parts of forestry waste, 50 parts of fiber cloth, 30 parts of modified lignin, 7 parts of isocyanate, 20 parts of thermoplastic resin and 6 parts of modifier;
the modified lignin is prepared by taking lignin of a certain mass, adding deionized water of a certain mass, stirring and mixing uniformly, adding 0.1mol/L NaOH aqueous solution, regulating pH to 9, and then adding Na of a certain mass 2 SO 3 Heating to 90 ℃ in water bath, and carrying out reflux reaction for 3 hours to obtain demethylated lignin; adding NaIO with a certain mass into the demethylated lignin 4 Rapidly stirring at 120r/min for 4min to obtain modified lignin; wherein the mass ratio of the raw materials in the modified lignin is lignin: deionized water: na (Na) 2 SO 3 ：NaIO 4 ＝10：20：1：3；
The isocyanate is diphenylmethane diisocyanate and m-xylylene isocyanate, and the mass ratio is 2:3, mixing; the thermoplastic resin is polyvinyl chloride resin; the modifier is preservative and waterproofing agent according to the mass ratio of 2:2, mixing, wherein the preservative is hydrogen peroxide, and the waterproof agent is wood wax oil;
the preparation method of the anti-cracking low-aldehyde multilayer board comprises the following steps:
step one: mixing the modified lignin with isocyanate in parts by weight, and stirring and mixing for 10min at a speed of 100r/min to obtain a mixture;
step two: taking thermoplastic resin in parts by weight, adding absolute ethyl alcohol with the mass of 0.7 times of the thermoplastic resin, transferring the thermoplastic resin into a reaction kettle, adding maleic anhydride with the mass of 0.01 times of the thermoplastic resin and dicumyl peroxide with the mass of 0.2 times of the maleic anhydride, and reacting at 300 ℃ for 60min in a nitrogen atmosphere to obtain molten thermoplastic resin;
step three: taking forestry waste in parts by mass, adding 5% concentrated sulfuric acid-acetic anhydride solution with the mass of 3 times that of the forestry waste, and soaking for 10 hours to obtain modified forestry waste;
step four: and (3) uniformly mixing the molten thermoplastic resin obtained in the second step with the modified forestry waste obtained in the third step, transferring the mixture into a die for multiple times, spreading a layer of fiber cloth in each layer of the die until the thickness reaches 3mm, uniformly spraying the mixture obtained in the first step on each layer of fiber cloth, uniformly adding a modifier, and hot-pressing at 220 ℃ for 4min to obtain the anti-cracking low-formaldehyde multi-layer board.
And (3) testing:
the physical properties of the anti-cracking low-formaldehyde multi-layer plates prepared in examples 1 to 3 are detected according to the standard GB/T17657-2013 artificial board and decorative artificial board physicochemical property test method, and formaldehyde release amount is tested by referring to the standard GB18580-2017 artificial board for interior decoration materials and formaldehyde release limit in products thereof, wherein the standard requirement formaldehyde release amount is lower than 0.124mg/m 3 The limit is identified as E1 and the results obtained are shown in the table:
| example 1 | Example 2 | Example 3 | |
| Surface bonding Strength (MPa) | 1.58 | 1.89 | 1.76 |
| Static bending strength (MPa) | 25.49 | 32.14 | 28.65 |
| 24h Water absorption thickness expansion Rate (%) | 6.3 | 5.1 | 5.7 |
| Formaldehyde emission (mg/m) 3 ) | 0.001 | 0.001 | 0.001 |
As shown in the table, the anti-cracking low-formaldehyde multi-layer board prepared by the method has better surface bonding strength and static bending strength, lower 24-hour water absorption thickness expansion rate, lower formaldehyde release amount, strong compression and crack resistance and less formaldehyde release amount.
The foregoing is merely illustrative of the present invention, and the present invention is not limited thereto, and any person skilled in the art will readily recognize that variations or substitutions are within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (7)
1. An anti-cracking low-formaldehyde multi-layer board is characterized by comprising the following raw materials in parts by weight: 200-300 parts of forestry waste, 40-60 parts of fiber cloth, 20-40 parts of modified lignin, 5-8 parts of isocyanate, 10-30 parts of thermoplastic resin and 3-10 parts of modifier;
the preparation method of the anti-cracking low-aldehyde multilayer board comprises the following steps:
step one: mixing the modified lignin with isocyanate in parts by weight, and stirring and mixing for 5-15 min at the speed of 80-120 r/min to obtain a mixture;
step two: taking thermoplastic resin in parts by weight, adding 0.5-1 times of absolute ethyl alcohol by mass of the thermoplastic resin, transferring the thermoplastic resin into a reaction kettle, adding 0.01-0.02 times of maleic anhydride by mass of the thermoplastic resin and 0.1-0.2 times of dicumyl peroxide by mass of the maleic anhydride, and reacting for 30-90 min at 200-400 ℃ in a nitrogen atmosphere to obtain molten thermoplastic resin;
step three: taking forestry waste in parts by mass, adding 5% concentrated sulfuric acid-acetic anhydride solution with the mass of 2-3 times that of the forestry waste, and soaking for 8-12 hours to obtain modified forestry waste;
step four: uniformly mixing the molten thermoplastic resin obtained in the second step and the modified forestry waste obtained in the third step, transferring the mixture into a die for multiple times, spreading a layer of fiber cloth with the thickness of 3-8 layers in each die, uniformly spraying the mixture obtained in the first step on each layer of fiber cloth, uniformly adding a modifier, and hot-pressing at 190-240 ℃ for 3-5 min to obtain the anti-cracking low-formaldehyde multi-layer board.
2. The anti-cracking low-formaldehyde multi-layer board according to claim 1, wherein the forestry waste is branch waste of eucalyptus and poplar, the forestry waste is washed to remove dust, then dried, crushed and sieved by a 20-mesh sieve to obtain the wood chip-shaped forestry waste.
3. The anti-cracking low-formaldehyde multiwall sheet of claim 1, wherein: the modified lignin is prepared by taking lignin with a certain mass, adding deionized water with a certain mass, stirring and mixing uniformly, adding 0.1mol/L NaOH aqueous solution, regulating pH to 8-9, and then adding Na with a certain mass 2 SO 3 Heating to 90 ℃ in water bath, and carrying out reflux reaction for 2-3 h to obtain demethylated lignin; adding NaIO with a certain mass into the demethylated lignin 4 And rapidly stirring at a speed of 100-150 r/min for 3-5 min to obtain the modified lignin.
4. A crack-resistant low-formaldehyde multiwall sheet as claimed in claim 3, wherein: the modified lignin comprises the following raw materials in percentage by mass: deionized water: na (Na) 2 SO 3 ：NaIO 4 ＝10：15～25：1：1～4。
5. The anti-cracking low-formaldehyde multiwall sheet of claim 1, wherein: the isocyanate is diphenylmethane diisocyanate and m-xylylene isocyanate, and the mass ratio is 2:2 to 3.
6. The anti-cracking low-formaldehyde multiwall sheet of claim 1, wherein: the thermoplastic resin is one or more of polypropylene resin, polyvinyl chloride resin and polyethylene resin.
7. The anti-cracking low-formaldehyde multiwall sheet of claim 1, wherein: the modifier is preservative and waterproofing agent according to the mass ratio of 2: 1-3, wherein the preservative is one of potassium permanganate, nano silver and hydrogen peroxide, and the waterproof agent is wood wax oil.
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