CN117887358A - Modified bio-based wood adhesive and preparation method and application thereof - Google Patents
Modified bio-based wood adhesive and preparation method and application thereof Download PDFInfo
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- CN117887358A CN117887358A CN202410123853.8A CN202410123853A CN117887358A CN 117887358 A CN117887358 A CN 117887358A CN 202410123853 A CN202410123853 A CN 202410123853A CN 117887358 A CN117887358 A CN 117887358A
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- 230000001070 adhesive effect Effects 0.000 title claims abstract description 86
- 239000000853 adhesive Substances 0.000 title claims abstract description 85
- 238000002360 preparation method Methods 0.000 title claims abstract description 43
- 239000002023 wood Substances 0.000 title claims abstract description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 54
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 38
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000002028 Biomass Substances 0.000 claims abstract description 15
- 235000000346 sugar Nutrition 0.000 claims abstract description 15
- 238000004519 manufacturing process Methods 0.000 claims abstract description 13
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- 238000000034 method Methods 0.000 claims abstract description 12
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- 239000002994 raw material Substances 0.000 claims abstract description 10
- 238000003763 carbonization Methods 0.000 claims abstract description 8
- 239000011120 plywood Substances 0.000 claims description 53
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- SYEWHONLFGZGLK-UHFFFAOYSA-N 2-[1,3-bis(oxiran-2-ylmethoxy)propan-2-yloxymethyl]oxirane Chemical compound C1OC1COCC(OCC1OC1)COCC1CO1 SYEWHONLFGZGLK-UHFFFAOYSA-N 0.000 claims description 8
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- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 7
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- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
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- 239000011259 mixed solution Substances 0.000 claims description 4
- CBOLARLSGQXRBB-UHFFFAOYSA-N 1-(oxiran-2-yl)-n,n-bis(oxiran-2-ylmethyl)methanamine Chemical compound C1OC1CN(CC1OC1)CC1CO1 CBOLARLSGQXRBB-UHFFFAOYSA-N 0.000 claims description 3
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 3
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- 244000215068 Acacia senegal Species 0.000 claims description 2
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- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 2
- 229920002907 Guar gum Polymers 0.000 claims description 2
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- IMQLKJBTEOYOSI-GPIVLXJGSA-N Inositol-hexakisphosphate Chemical compound OP(O)(=O)O[C@H]1[C@H](OP(O)(O)=O)[C@@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@@H]1OP(O)(O)=O IMQLKJBTEOYOSI-GPIVLXJGSA-N 0.000 claims description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 2
- GUBGYTABKSRVRQ-PICCSMPSSA-N Maltose Natural products O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@@H]1O[C@@H]1[C@@H](CO)OC(O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-PICCSMPSSA-N 0.000 claims description 2
- IMQLKJBTEOYOSI-UHFFFAOYSA-N Phytic acid Natural products OP(O)(=O)OC1C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C1OP(O)(O)=O IMQLKJBTEOYOSI-UHFFFAOYSA-N 0.000 claims description 2
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- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
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- 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
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- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 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
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- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 abstract description 4
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Abstract
The invention provides a modified bio-based adhesive, a preparation method and application thereof, belonging to the technical field of adhesive preparation; according to the invention, biomass sugar is used as a raw material, and the modified biobased hydrothermal carbon is obtained by reacting with a modifier under the hydrothermal carbonization condition, so that the active reaction sites of the hydrothermal carbon are increased; the modified biobased hydrothermal carbon has high reactivity, is convenient for being fully crosslinked with isocyanate, glycidyl ether, hydroxymethyl and polyurethane crosslinking agents and reacts with adhesive substrates to generate enough bonding force; the modified bio-based adhesive does not release formaldehyde completely in the use process, has high interfacial reaction activity with wood, and has good cementing property and water resistance; the modified bio-based adhesive is simple in preparation method and excellent in performance, and can be suitable for production of artificial boards.
Description
Technical Field
The invention belongs to the technical field of adhesive preparation, and particularly relates to a modified bio-based adhesive, and a preparation method and application thereof.
Background
At present, formaldehyde-based adhesives are mainly used in the wood industry, wherein urea-formaldehyde resins, phenolic resins and melamine-formaldehyde resins are most popular, and the formaldehyde-based adhesives have excellent adhesive property and water resistance. However, the three adhesives have non-negligible disadvantages, on one hand, the raw materials for producing the adhesives need to be obtained from petrochemical products, and nonrenewable fossil resources need to be consumed in the production process; on the other hand, formaldehyde can be released in the production and use processes of the adhesive, and the adhesive can cause great harm to the environment and human bodies. Therefore, the wood adhesive industry needs to develop a renewable, non-toxic and harmless environment-friendly adhesive.
Biomass sugars are widely found in nature and can be used to prepare wood adhesives, but sugars are rich in hydroxyl groups, resulting in poor water resistance. Therefore, it is required to chemically modify biomass sugars, and to improve the water resistance of bio-based wood adhesives by chemical modification, thereby increasing the added value thereof.
Content
Aiming at some defects existing in the prior art, the invention provides a modified bio-based adhesive, and a preparation method and application thereof; according to the invention, biomass sugar is used as a raw material, and the modified biobased hydrothermal carbon is obtained by reacting with a modifier under the hydrothermal carbonization condition, so that the active reaction sites of the hydrothermal carbon are increased; the modified biobased hydrothermal carbon has high reactivity, is convenient for being fully crosslinked with isocyanate, glycidyl ether, hydroxymethyl and polyurethane crosslinking agents and reacts with adhesive substrates to generate enough bonding force; the modified bio-based adhesive does not release formaldehyde completely in the use process, has high interfacial reaction activity with wood, and has good cementing property and water resistance; the modified bio-based adhesive is simple in preparation method and excellent in performance, and can be suitable for production of artificial boards.
The present invention achieves the above technical object by the following means.
The invention firstly provides a modified bio-based adhesive, which is prepared based on modified bio-based hydrothermal carbon; the modified biobased hydrothermal carbon is grafted with active functional group-NH on the surface of the biobased hydrothermal carbon 2 and-COOH;
the modified bio-based adhesive comprises the following raw materials in parts by weight: 8-10 parts of modified biobased hydrothermal carbon, 24-30 parts of dispersing agent, 2-3 parts of cross-linking agent and 2-3 parts of additive.
The invention also provides a preparation method of the modified bio-based adhesive, which comprises the following steps:
(1) Preparation of modified biobased hydrothermal carbon:
dispersing biomass sugar and a modifier in water, stirring and mixing uniformly to obtain a mixed solution, carrying out hydrothermal carbonization reaction on the mixed solution, and cooling, separating, drying, grinding and sieving after the reaction is finished to obtain modified biobased hydrothermal carbon;
(2) Preparation of modified biobased adhesive:
and (3) placing the modified biobased hydrothermal carbon in a mortar, adding a dispersing agent, a cross-linking agent and an additive into the mortar, and grinding until the mixture is uniformly mixed to obtain the modified biobased adhesive.
Preferably, in the step (1), the reaction raw materials in the preparation process of the modified bio-based hydrothermal carbon are 28-32 parts of biomass sugar, 8-12 parts of modifier and 128-132 parts of water in parts by weight.
Preferably, in the step (1), the biomass sugar comprises one or more of glucose, fructose, starch, maltose, cellulose, hemicellulose and chitosan.
Preferably, in the step (1), the modifier comprises one or more of acrylamide, acrylic acid, diethylenetriamine, urea and citric acid.
Preferably, in the step (1), the conditions of the hydrothermal carbonization reaction are: reacting for 2-8 h at 180-210 ℃.
Preferably, in the step (1), the sieving is performed by a 300-100 mesh sieve, and the pore diameter is 0.054-0.15mm.
Preferably, in the step (2), 8-10 parts of modified biobased hydrothermal carbon, 24-30 parts of dispersing agent, 2-3 parts of cross-linking agent and 2-3 parts of additive are calculated in parts by weight.
Preferably, in the step (2), the dispersing agent comprises one or more of a polyvinyl alcohol solution, a gelatin solution, a guar gum solution and a gum arabic solution with 5-10% wt.
Preferably, in the step (2), the cross-linking agent comprises one or more of glycerol triglycidyl ether, triglycidyl amine, epoxidized soybean oil, ammonium polyphosphate, isophorone diisocyanate, a silane coupling agent and borax.
Preferably, in the step (2), the additive comprises one or more of aldehyde cellulose, tannin, zinc chloride, montmorillonite, kaolin, phytic acid and nano wood fiber.
The invention also provides application of the modified bio-based adhesive in manufacturing artificial boards.
Preferably, the artificial board comprises plywood, chipboard or medium density fiberboard.
Preferably, the preparation steps of the artificial board include:
(1) Coating the modified bio-based adhesive on two sides of a middle veneer, assembling blanks of the middle veneer and the veneers of the upper and lower contact surfaces in a mode that the fiber directions of the veneers are mutually perpendicular, and applying load cold pressing above the plywood at room temperature after assembling the blanks to obtain the plywood;
(2) And carrying out hot pressing treatment on the plywood subjected to cold pressing to obtain the artificial board.
Preferably, in the step (1), the sizing amount of the modified bio-based adhesive is 180-210 g/m 2 ；
The cold pressing condition is that the load of 0.5-0.8 Mpa is used for 30-60 min.
Preferably, in the step (2), the hot pressing condition is that the hot pressing is performed for 800-1000 seconds under the conditions of 120-160 ℃ and 1.0-1.4 MPa.
Compared with the prior art, the invention has the beneficial effects that:
(1) The raw material of the modified bio-based adhesive is biomass sugar, the biomass sugar widely exists in the natural world, and compared with fossil resources, the bio-based sugar is renewable, wide in source and low in price. In addition, the renewable biological matrix material is used as the main raw material, thereby conforming to sustainable development, no formaldehyde is released in the preparation and use processes, being green and environment-friendly and conforming to ecological civilization construction requirements and green development concepts.
(2) The invention hydrolyzes and repolymerizes biomass sugar through the hydrothermal carbonization of modifier and biomass sugarActive functional groups (-NH) are grafted on the surface of the hydrothermal carbon in the process of forming coke 2 I—cooh), increases the active reactive sites of the biobased hydrothermal carbon. The modified biobased hydrothermal carbon has high reactivity, is convenient for fully crosslinking with isocyanate, epoxy, hydroxymethyl and polyurethane crosslinking agents and generating enough bonding force with adhesive substrates, successfully prepares the biobased formaldehyde-free adhesive, and can be applied to the production of plywood, shaving board, fiber board and the like in artificial boards.
(3) The modified bio-based adhesive has good adhesive strength and water resistance, and the performance index meets the requirements (more than or equal to 0.7 MPa) of class II plywood specified in the national standard GB/T9846-2015. The modified bio-based adhesive prepared by the invention has low cost and simple preparation method, and is beneficial to industrial production. The method can reduce the dependence of the wood industry on the synthetic resin based on petrochemical resources, has good application prospect in the field of artificial board adhesives, and has important significance for the development of the wood industry and the coping with petrochemical crisis problems.
Drawings
FIG. 1 is a biobased hydrothermal charcoal X-ray photoelectron spectroscopy.
Fig. 2 is a schematic view of plywood assembly and dimensions.
Fig. 3 is a schematic diagram of a tensile test.
FIG. 4 is a graph of wet bond strength for a bio-based adhesive.
Detailed Description
The following detailed description of the invention is provided in further detail, but the scope of the invention is not limited thereto, but any modifications or substitutions within the basic spirit of the present embodiment are still within the scope of the present invention as claimed. In the present invention, the materials and equipment used are commercially available products unless otherwise specified, and in the following examples, the conventional methods in the art are used unless otherwise specified. Any combination of the embodiments or technical features described below may be used to form new embodiments.
Example 1:
(1) Preparation of modified biobased hydrothermal carbon:
30 parts by weight of anhydrous glucose, 130 parts by weight of water and 10 parts by weight of acrylamide are added into a beaker, uniformly mixed at normal temperature, and poured into a high-pressure reaction kettle to react for 2.5 hours at 180 ℃. And after the reaction is finished, solid and liquid of the product are separated, the solid product is dried and ground, and the solid product is filtered by a 200-mesh screen to obtain the modified bio-based hydrothermal carbon powder.
(2) Preparation of modified biobased adhesive:
10 parts by weight of hydrothermal carbon powder is placed in a mortar, 30 parts by weight of 10% wt polyvinyl alcohol solution is added, 3 parts by weight of glycerol triglycidyl ether and 3 parts by weight of tannin are added, and the mixture is ground for 10 minutes and uniformly mixed to obtain the modified bio-based adhesive.
The prepared modified bio-based adhesive is used for manufacturing a plywood, and the preparation steps of the plywood are as follows:
(1) Making a three-layer plywood by using a poplar veneer with the thickness of 1.5mm, wherein the moisture content of the poplar veneer is controlled to be 5-8%;
according to 210g/m 2 Uniformly coating modified bio-based adhesive on two sides of the middle layer poplar veneer, forming blanks with the upper and lower layers of poplar veneer in a mode that the two layers of poplar veneer are mutually perpendicular to the fiber direction of the wood board, and applying 0.5Mpa load above the plywood for cold pressing for 60 minutes at room temperature after forming the blanks;
(2) The cold-pressed plywood was hot-pressed at 150℃and 1.0MPa for 900 seconds. The three-layer plywood after the hot pressing is processed into the plywood shown in figure 2 according to the national standard GB/T17657-2013.
The wet bond strength of the plywood was tested as indicated by the tensile force in fig. 3, and the test results are shown in fig. 4. As can be seen from FIG. 4, the wet bonding strength of the modified bio-based adhesive in the embodiment is 1.52MPa, and the performance index meets the requirements (more than or equal to 0.7 MPa) of class II plywood specified in the national standard GB/T9846-2015.
Example 2:
(1) Preparation of modified biobased hydrothermal carbon:
30 parts by weight of anhydrous glucose, 130 parts by weight of water and 10 parts by weight of acrylic acid were added to a beaker, stirred sufficiently at normal temperature for 10 minutes, and poured into a high-pressure reaction kettle to react at 180 ℃ for 2.5 hours. And after the reaction is finished, solid and liquid of the product are separated, the solid product is dried and ground, and the solid product is filtered by a 200-mesh screen to obtain the modified bio-based hydrothermal carbon powder.
(2) Preparation of modified biobased adhesive:
10 parts by weight of hydrothermal carbon powder is placed in a mortar, 30 parts by weight of 10% wt polyvinyl alcohol solution is added, 3 parts by weight of glycerol triglycidyl ether and 3 parts by weight of tannin are added, and the mixture is ground for 10 minutes and uniformly mixed to obtain the modified bio-based adhesive.
The prepared modified bio-based adhesive is used for manufacturing a plywood, and the preparation steps of the plywood are as follows:
(1) Making a three-layer plywood by using a poplar veneer with the thickness of 1.5mm, wherein the moisture content of the poplar veneer is controlled to be 5-8%;
according to 210g/m 2 Uniformly coating modified bio-based adhesive on two sides of the middle layer poplar veneer, forming blanks with the upper and lower layers of poplar veneer in a mode that the two layers of poplar veneer are mutually perpendicular to the fiber direction of the wood board, and applying 0.5Mpa load above the plywood for cold pressing for 60 minutes at room temperature after forming the blanks;
(2) The cold-pressed plywood was hot-pressed at 150℃and 1.0MPa for 900 seconds. The three-layer plywood after the hot pressing is processed into the plywood shown in figure 2 according to the national standard GB/T17657-2013.
The wet bond strength of the plywood was tested as indicated by the tensile force in fig. 3, and the test results are shown in fig. 4. As can be seen from fig. 4, the wet bonding strength of the bio-based adhesive in the embodiment is 1.37MPa, and the performance index meets the requirements (more than or equal to 0.7 MPa) of class ii plywood specified in the national standard GB/T9846-2015.
Example 3:
(1) Preparation of modified biobased hydrothermal carbon:
30 parts by weight of fructose, 130 parts by weight of water and 10 parts by weight of acrylamide were added to a beaker, stirred well at normal temperature for 10 minutes, and poured into a high-pressure reaction kettle to react at 180 ℃ for 2.5 hours. And after the reaction is finished, solid and liquid of the product are separated, the solid product is dried and ground, and the solid product is filtered by a 200-mesh screen to obtain the modified bio-based hydrothermal carbon powder.
(2) Preparation of modified biobased adhesive:
10 parts by weight of hydrothermal carbon powder is placed in a mortar, 30 parts by weight of 10% wt polyvinyl alcohol solution is added, 3 parts by weight of glycerol triglycidyl ether and 3 parts by weight of tannin are added, and the mixture is ground for 10 minutes and uniformly mixed to obtain the modified bio-based adhesive.
The prepared modified bio-based adhesive is used for manufacturing a plywood, and the preparation steps of the plywood are as follows:
(1) Making a three-layer plywood by using a poplar veneer with the thickness of 1.5mm, wherein the moisture content of the poplar veneer is controlled to be 5-8%;
according to 210g/m 2 Uniformly coating modified bio-based adhesive on two sides of the middle layer poplar veneer, forming blanks with the upper and lower layers of poplar veneer in a mode that the two layers of poplar veneer are mutually perpendicular to the fiber direction of the wood board, and applying 0.5Mpa load above the plywood for cold pressing for 60 minutes at room temperature after forming the blanks;
(2) The cold-pressed plywood was hot-pressed at 150℃and 1.0MPa for 900 seconds. The three-layer plywood after the hot pressing is processed into the plywood shown in figure 2 according to the national standard GB/T17657-2013.
The wet bond strength of the plywood was tested as indicated by the tensile force in fig. 3, and the test results are shown in fig. 4. As can be seen from fig. 4, the wet bonding strength of the bio-based adhesive in the embodiment is 1.24MPa, and the performance index meets the requirements (more than or equal to 0.7 MPa) of class ii plywood specified in the national standard GB/T9846-2015.
Example 4:
(1) Preparation of modified biobased hydrothermal carbon:
30 parts by weight of fructose, 130 parts by weight of water and 10 parts by weight of acrylic acid were added to a beaker, stirred sufficiently at normal temperature for 10 minutes, and poured into a high-pressure reaction kettle to react at 180 ℃ for 2.5 hours. And after the reaction is finished, solid and liquid of the product are separated, the solid product is dried and ground, and the solid product is filtered by a 200-mesh screen to obtain the modified bio-based hydrothermal carbon powder.
(2) Preparation of modified biobased adhesive:
10 parts by weight of hydrothermal carbon powder is placed in a mortar, 30 parts by weight of 10% wt polyvinyl alcohol solution is added, 3 parts by weight of glycerol triglycidyl ether and 3 parts by weight of tannin are added, and the mixture is ground for 10 minutes and uniformly mixed to obtain the modified bio-based adhesive.
The prepared modified bio-based adhesive is used for manufacturing a plywood, and the preparation steps of the plywood are as follows:
(1) Making a three-layer plywood by using a poplar veneer with the thickness of 1.5mm, wherein the moisture content of the poplar veneer is controlled to be 5-8%;
according to 210g/m 2 Uniformly coating modified bio-based adhesive on two sides of the middle layer poplar veneer, forming blanks with the upper and lower layers of poplar veneer in a mode that the two layers of poplar veneer are mutually perpendicular to the fiber direction of the wood board, and applying 0.5Mpa load above the plywood for cold pressing for 60 minutes at room temperature after forming the blanks;
(2) The cold-pressed plywood was hot-pressed at 150℃and 1.0MPa for 900 seconds. The three-layer plywood after the hot pressing is processed into the plywood shown in figure 2 according to the national standard GB/T17657-2013.
The wet bond strength of the plywood was tested as indicated by the tensile force in fig. 3, and the test results are shown in fig. 4. As can be seen from fig. 4, the wet bonding strength of the bio-based adhesive in the embodiment is 1.44MPa, and the performance index meets the requirements (more than or equal to 0.7 MPa) of class ii plywood specified in the national standard GB/T9846-2015.
Example 5:
(1) Preparation of modified biobased hydrothermal carbon:
28 parts by weight of anhydrous glucose, 128 parts by weight of water, 4 parts by weight of acrylic acid and 4 parts by weight of diethylenetriamine are added into a beaker, then stirred sufficiently for 10 minutes at normal temperature, poured into a high-pressure reaction kettle and reacted for 2 hours at 210 ℃. And after the reaction is finished, solid and liquid of the product are separated, the solid product is dried and ground, and the solid product is filtered by a 200-mesh screen to obtain the modified bio-based hydrothermal carbon powder.
(2) Preparation of modified biobased adhesive:
10 parts by weight of hydrothermal carbon powder is placed in a mortar, 30 parts by weight of gelatin solution with the weight of 10 percent is added, 3 parts by weight of glycerol triglycidyl ether and 3 parts by weight of tannin are added, and the mixture is ground for 10 minutes and uniformly mixed, so that the modified bio-based adhesive is obtained.
Example 6:
(1) Preparation of modified biobased hydrothermal carbon:
32 parts by weight of fructose, 132 parts by weight of water, 6 parts by weight of acrylic acid and 6 parts by weight of acrylamide are added into a beaker, stirred sufficiently at normal temperature for 10 minutes, and poured into a high-pressure reaction kettle to react for 8 hours at 180 ℃. And after the reaction is finished, solid and liquid of the product are separated, the solid product is dried and ground, and the solid product is filtered by a 200-mesh screen to obtain the modified bio-based hydrothermal carbon powder.
(2) Preparation of modified biobased adhesive:
8 parts by weight of hydrothermal carbon powder is taken and placed in a mortar, 28 parts by weight of 10% wt polyvinyl alcohol solution is added, 2 parts by weight of triglycidyl amine and 3 parts by weight of aldehyde cellulose are added, and the mixture is ground for 10 minutes and uniformly mixed, so that the modified bio-based adhesive is obtained.
Example 7:
(1) Preparation of modified biobased hydrothermal carbon:
30 parts by weight of fructose, 130 parts by weight of water and 10 parts by weight of acrylic acid are added into a beaker, stirred sufficiently at normal temperature for 10 minutes, and poured into a high-pressure reaction kettle to react for 2.5 hours at 180 ℃. And after the reaction is finished, solid and liquid of the product are separated, the solid product is dried and ground, and the solid product is filtered by a 200-mesh screen to obtain the modified bio-based hydrothermal carbon powder.
(2) Preparation of modified biobased adhesive:
8 parts by weight of hydrothermal carbon powder is taken and placed in a mortar, 24 parts by weight of 5% wt polyvinyl alcohol solution is added, 2 parts by weight of epoxidized soybean oil and 3 parts by weight of zinc chloride are added, and the mixture is ground for 10 minutes and uniformly mixed, so that the modified bio-based adhesive is obtained.
Comparative example 1:
(1) Preparation of biobased hydrothermal carbon:
30 parts by weight of anhydrous glucose and 130 parts by weight of water are added into a beaker, stirred fully for 10 minutes at normal temperature, and poured into a high-pressure reaction kettle to react for 2.5 hours at 180 ℃. And after the reaction is finished, solid-liquid separation is carried out on the product, the solid product is dried, ground and filtered through a 200-mesh screen, and the bio-based hydrothermal carbon powder is obtained.
(2) Preparation of the bio-based adhesive:
10 parts by weight of the bio-based hydrothermal carbon powder is placed in a mortar, 30 parts by weight of 10% wt polyvinyl alcohol solution is added, 3 parts by weight of glycerol triglycidyl ether and 3 parts by weight of tannin are added, grinding is carried out for 10 minutes, and the bio-based adhesive is obtained.
The prepared bio-based adhesive is used for manufacturing a plywood, and the preparation steps of the plywood are as follows:
(1) Making a three-layer plywood by using a poplar veneer with the thickness of 1.5mm, wherein the moisture content of the poplar veneer is controlled to be 5-8%;
according to 210g/m 2 Uniformly coating a biological base adhesive on two sides of the middle layer poplar veneer, forming blanks with the upper and lower layers of poplar veneers in a mode that the two layers of poplar veneers are mutually perpendicular to the fiber direction of the wood board, and applying 0.5Mpa load above the plywood for cold pressing for 60 minutes at room temperature after forming the blanks;
(2) The cold-pressed plywood was hot-pressed at 150℃and 1.0MPa for 900 seconds. The three-layer plywood after the hot pressing is processed into the plywood shown in figure 2 according to the national standard GB/T17657-2013.
The wet bond strength of the plywood was tested as indicated by the tensile force in fig. 3, and the test results are shown in fig. 4. As can be seen from fig. 4, the wet bonding strength of the bio-based adhesive in the embodiment is 1.13MPa, and the performance index meets the requirements (more than or equal to 0.7 MPa) of class ii plywood specified in the national standard GB/T9846-2015.
In summary, biomass sugar is used as a raw material, and the modified biobased hydrothermal carbon is obtained through the reaction of the modifier under the hydrothermal carbonization condition, so that the active reaction sites of the modified biobased hydrothermal carbon are increased; the modified biobased hydrothermal carbon has high reactivity, is convenient for being fully crosslinked with isocyanate, epoxy, hydroxymethyl and polyurethane crosslinking agents and generating enough bonding force with adhesive substrates; the modified bio-based adhesive does not release formaldehyde completely in the use process, has high interfacial reaction activity with wood, and has good cementing property and water resistance; the modified bio-based adhesive is simple in preparation method and excellent in performance, and can be suitable for production of artificial boards.
The examples are preferred embodiments of the present invention, but the present invention is not limited to the above-described embodiments, and any obvious modifications, substitutions or variations that can be made by one skilled in the art without departing from the spirit of the present invention are within the scope of the present invention.
Claims (9)
1. The preparation method of the modified bio-based wood adhesive is characterized by comprising the following steps of:
(1) Preparation of modified biobased hydrothermal carbon:
dispersing biomass sugar and a modifier in water, uniformly mixing to obtain a mixed solution, carrying out hydrothermal carbonization reaction on the mixed solution, and cooling, separating, drying, grinding and sieving after the reaction is finished to obtain modified biobased hydrothermal carbon;
(2) Preparation of modified biobased adhesive:
and (3) placing the modified biobased hydrothermal carbon in a mortar, adding a dispersing agent, a cross-linking agent and an additive into the mortar, and grinding until the mixture is uniformly mixed to obtain the modified biobased adhesive.
2. The preparation method of the modified bio-based adhesive according to claim 1, wherein in the step (1), the reaction raw materials in the preparation process of the modified bio-based hydrothermal carbon are 28-32 parts by weight of biomass sugar, 8-12 parts by weight of modifier and 128-132 parts by weight of water.
3. The method for preparing a modified biobased adhesive according to claim 1, wherein in the step (1), the biomass saccharide is one or more of glucose, fructose, starch, maltose, cellulose, hemicellulose and chitosan;
the modifier is one or more of acrylamide, acrylic acid, diethylenetriamine, urea and citric acid.
4. The method for preparing a modified biobased adhesive according to claim 1, wherein in the step (1), the hydrothermal carbonization reaction time is 1 to 10 hours, and the reaction temperature is 160 to 240 ℃.
5. The method for preparing a modified biobased adhesive according to claim 1, wherein in the step (2), 8-10 parts by weight of modified biobased hydrothermal carbon, 24-30 parts by weight of dispersing agent, 2-3 parts by weight of crosslinking agent and 2-3 parts by weight of additive are calculated.
6. The method for preparing a modified biobased adhesive according to claim 1, wherein in the step (2), the dispersing agent comprises one or more of a polyvinyl alcohol solution, a gelatin solution, a guar gum solution and a gum arabic solution in an amount of 5-10% by weight;
the cross-linking agent comprises one or more of glycerol triglycidyl ether, triglycidyl amine, epoxidized soybean oil, ammonium polyphosphate, isophorone diisocyanate, a silane coupling agent and borax;
the additive comprises one or more of aldehyde cellulose, tannin, zinc chloride, montmorillonite, kaolin, phytic acid and nano wood fiber.
7. The modified biobased adhesive prepared by the method of any one of claims 1 to 6, wherein the modified biobased adhesive is prepared based on modified biobased hydrothermal carbon; the modified biobased hydrothermal carbon is grafted with active functional group-NH on the surface of the biobased hydrothermal carbon 2 and-COOH;
the modified bio-based adhesive comprises the following raw materials in parts by weight: 8-10 parts of modified biobased hydrothermal carbon, 24-30 parts of dispersing agent, 2-3 parts of cross-linking agent and 2-3 parts of additive.
8. The use of the modified biobased adhesive of claim 7 in the manufacture of artificial boards.
9. The use according to claim 8, wherein the artificial board comprises plywood, chipboard or medium density fiberboard.
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