CN118146748A - Starch-based particle board adhesive with high water resistance and quick solidification and preparation method thereof - Google Patents
Starch-based particle board adhesive with high water resistance and quick solidification and preparation method thereof Download PDFInfo
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- CN118146748A CN118146748A CN202410311268.0A CN202410311268A CN118146748A CN 118146748 A CN118146748 A CN 118146748A CN 202410311268 A CN202410311268 A CN 202410311268A CN 118146748 A CN118146748 A CN 118146748A
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- 230000001070 adhesive effect Effects 0.000 title claims abstract description 171
- 239000000853 adhesive Substances 0.000 title claims abstract description 170
- 229920002472 Starch Polymers 0.000 title claims abstract description 136
- 235000019698 starch Nutrition 0.000 title claims abstract description 134
- 239000008107 starch Substances 0.000 title claims abstract description 134
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 81
- 239000002245 particle Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 238000007711 solidification Methods 0.000 title description 15
- 230000008023 solidification Effects 0.000 title description 15
- 239000000178 monomer Substances 0.000 claims abstract description 111
- 238000004132 cross linking Methods 0.000 claims abstract description 63
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 57
- 239000003999 initiator Substances 0.000 claims abstract description 41
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 27
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 20
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 14
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 12
- 239000000839 emulsion Substances 0.000 claims description 32
- 238000006243 chemical reaction Methods 0.000 claims description 23
- 239000011093 chipboard Substances 0.000 claims description 12
- 238000006116 polymerization reaction Methods 0.000 claims description 12
- 238000010559 graft polymerization reaction Methods 0.000 claims description 11
- 235000013336 milk Nutrition 0.000 claims description 11
- 239000008267 milk Substances 0.000 claims description 11
- 210000004080 milk Anatomy 0.000 claims description 11
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 9
- 239000002023 wood Substances 0.000 claims description 9
- XMPZTFVPEKAKFH-UHFFFAOYSA-P ceric ammonium nitrate Chemical group [NH4+].[NH4+].[Ce+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O XMPZTFVPEKAKFH-UHFFFAOYSA-P 0.000 claims description 8
- 230000001105 regulatory effect Effects 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 7
- OMNKZBIFPJNNIO-UHFFFAOYSA-N n-(2-methyl-4-oxopentan-2-yl)prop-2-enamide Chemical compound CC(=O)CC(C)(C)NC(=O)C=C OMNKZBIFPJNNIO-UHFFFAOYSA-N 0.000 claims description 7
- 229920002261 Corn starch Polymers 0.000 claims description 5
- 239000008120 corn starch Substances 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical group [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 4
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 claims description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 240000003183 Manihot esculenta Species 0.000 claims description 2
- 235000016735 Manihot esculenta subsp esculenta Nutrition 0.000 claims description 2
- 240000004922 Vigna radiata Species 0.000 claims description 2
- 235000010721 Vigna radiata var radiata Nutrition 0.000 claims description 2
- 235000011469 Vigna radiata var sublobata Nutrition 0.000 claims description 2
- 239000012295 chemical reaction liquid Substances 0.000 claims description 2
- 239000011094 fiberboard Substances 0.000 claims description 2
- 239000011120 plywood Substances 0.000 claims description 2
- 229920001592 potato starch Polymers 0.000 claims description 2
- 229940100486 rice starch Drugs 0.000 claims description 2
- 229940100445 wheat starch Drugs 0.000 claims description 2
- 238000005903 acid hydrolysis reaction Methods 0.000 claims 1
- 238000010521 absorption reaction Methods 0.000 abstract description 15
- 239000000243 solution Substances 0.000 description 37
- 230000000694 effects Effects 0.000 description 34
- 238000007731 hot pressing Methods 0.000 description 21
- 239000000047 product Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 7
- 238000012986 modification Methods 0.000 description 6
- 230000004048 modification Effects 0.000 description 6
- 238000003756 stirring Methods 0.000 description 5
- 238000009826 distribution Methods 0.000 description 4
- 239000003292 glue Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 229920000881 Modified starch Polymers 0.000 description 3
- 239000004368 Modified starch Substances 0.000 description 3
- 235000019426 modified starch Nutrition 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000010979 pH adjustment Methods 0.000 description 2
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- 230000008569 process Effects 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
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- IVJISJACKSSFGE-UHFFFAOYSA-N formaldehyde;1,3,5-triazine-2,4,6-triamine Chemical compound O=C.NC1=NC(N)=NC(N)=N1 IVJISJACKSSFGE-UHFFFAOYSA-N 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
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- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 239000000463 material Substances 0.000 description 1
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- 231100000252 nontoxic Toxicity 0.000 description 1
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- 231100000956 nontoxicity Toxicity 0.000 description 1
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- 238000007254 oxidation reaction Methods 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- ODGAOXROABLFNM-UHFFFAOYSA-N polynoxylin Chemical compound O=C.NC(N)=O ODGAOXROABLFNM-UHFFFAOYSA-N 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
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- 230000009257 reactivity Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
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- 238000010008 shearing Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
Landscapes
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention discloses a high-water-resistance quick-curing starch-based adhesive for a particle board and a preparation method thereof, and belongs to the technical field of adhesive preparation. The starch-based adhesive for the particle board comprises a component A and a component B; the component A comprises the following components in parts by mass: 140-160 parts of starch, 200-300 parts of water, 20-25 parts of concentrated hydrochloric acid, 12-18 parts of dilute nitric acid, 25-40 parts of sodium hydroxide solution, 4-8 parts of an initiator, 12-20 parts of a hydrophobic monomer, 25-32 parts of a crosslinking monomer and 3-7 parts of an emulsifier; the component B comprises the following components in parts by mass: 12-15 parts of post-crosslinking agent. The starch-based shaving board adhesive effectively solves the problems of insufficient water resistance and long curing time of the starch adhesive in the prior art, and can improve the water resistance and the water absorption thickness expansion rate of the prepared shaving board to reach 5 percent on the premise of keeping a higher curing speed.
Description
Technical Field
The invention relates to a starch-based chipboard adhesive with high water resistance and quick curing and a preparation method thereof, belonging to the technical field of adhesive preparation.
Background
In recent years, with the rapid development of economy, the domestic wood consumption speed is remarkably improved, and the demand of wood resources is continuously increased. The artificial board is used as a product for efficiently utilizing wood and improving the utilization rate of wood resources, and the demand of the artificial board is also increasing. However, with the expansion of the adhesive industry, the problems of the currently used wood adhesives are also increasingly prominent.
Most artificial board products in the market use traditional adhesives, mainly 'trialdehyde' resin glue, including phenolic glue, urea-formaldehyde glue and melamine formaldehyde glue. The adhesives have low cost and relatively superior performance, but the problems of environmental pollution and health hazard are serious, formaldehyde release problems exist in the production process and the final product, and the adhesives pose a threat to the environment and public health. Therefore, there is an urgent need to develop an environmentally friendly, high performance and nontoxic wood adhesive.
The starch is used as a natural degradable and environment-friendly regenerated material, and is widely applied in the processing industry due to the characteristics of wide sources, low cost, no toxicity and the like. Compared with common adhesives in the market, the starch-based adhesive not only can reduce the cost, but also can reduce the influence on the environment.
The wood-based panel in the market at present is mostly produced by adopting a hot-pressing technology, wherein the shaving board is a typical representative, and the hot-pressing process time is shorter, so that the adhesive is required to have higher curing activity, be rapidly cured at the hot-pressing temperature, and have lower viscosity and good water resistance. However, conventional starch-based adhesives suffer from high viscosity, lack of thermosetting properties and poor water resistance, which point to the necessity of developing advanced adhesive formulations in this field.
Aiming at the requirement of the particle board on the performance of the adhesive, a starch-based adhesive with high curing speed is developed in the patent CN 114591707A, and the curing efficiency is greatly improved, but the main effect of a single monomer is to provide the effect of crosslinking modification, the monomer is hydrophilic colloid, the water resistance of the adhesive is not greatly improved by grafting the monomer onto starch, and the single crosslinking modification cannot meet the scene with higher requirement on water resistance in outdoor use and the like. Therefore, it is necessary to further improve the water resistance of the adhesive so as to meet the requirement of more application scenes of the starch-based adhesive.
Disclosure of Invention
Technical problem
The modified starch-based adhesive has limited single monomer modification effect when being applied to preparing the shaving board, the monomer is hydrophilic, the hydrophobicity of the adhesive cannot be improved after grafting, and the water resistance of the shaving board is required to be further improved, so that the water resistance of the shaving board is insufficient, and the preparation requirement of the modern shaving board is difficult to meet.
Technical proposal
In order to solve the problems, the invention provides a starch-based chipboard adhesive with high water resistance and quick curing and a preparation method thereof; according to the method, a hydrophobic monomer and a crosslinking monomer are grafted to starch through a graft copolymerization reaction, the crosslinking monomer is grafted to the starch, crosslinking sites are provided, so that the adhesive has curing performance, and the crosslinking monomer with high crosslinking reaction activity is selected, so that the curing speed of the adhesive can be effectively improved, and the adhesive has rapid curing performance; the hydrophobic monomer is grafted to the starch, so that the initial water resistance of the grafted modified starch-based adhesive can be improved; in addition, the hydrophobic monomer is also provided with a crosslinking group which can participate in the crosslinking reaction, so that the synergistic effect of composite crosslinking can be generated, and the curing effect of the adhesive is further improved. Meanwhile, the grafted molecular chains formed by the hydrophobic monomer on the starch molecule have different properties from those generated by the crosslinking monomer, the two molecular chains repel each other, so that crosslinking sites on the respective molecular chains are exposed, the crosslinking reaction of the post-crosslinking agent and the adhesive is greatly promoted, the mechanical strength and the water resistance of the adhesive are improved, and compared with the CN 114591707A, the adhesive has more perfect water resistance through the grafting modification of the double monomers, and the water resistance of the prepared shaving board is further improved; in addition, in order to improve the grafting effect of the monomer on the starch and the distribution uniformity of the crosslinking monomer, aiming at the technical characteristics of grafting modification by using double monomers, the process is optimized, two monomers are firstly mixed, and as one of the two monomers is a water-soluble monomer and the other is a hydrophobic monomer which are mutually insoluble, an emulsifying agent is added into the system, then an emulsion is formed through ultrasonic treatment, and then a small amount of initiator is added into the monomer emulsion, and the monomers are prepolymerized at a lower temperature to generate a monomer oligomer with lower polymerization degree, thereby being beneficial to forming a grafted molecular chain with higher molecular weight on the starch in the grafting copolymerization reaction with the starch, improving the performance of the adhesive, ensuring that the distribution of the grafted molecular chain is more uniform, ensuring that the distribution of reaction sites of the crosslinking reaction is more uniform and improving the crosslinking effect; the obtained adhesive is added with a post-crosslinking agent before use and uniformly mixed to be dissolved, and can be rapidly crosslinked with the grafted modified starch adhesive during hot pressing to form a three-dimensional network structure, so that the water resistance of the adhesive is further improved; in addition, the crosslinking agent with high reactivity is selected, so that the crosslinking reaction is easier to carry out, and the curing speed is improved.
The invention provides a starch-based shaving board adhesive which is quickly cured at a medium-low temperature, wherein the starch-based shaving board adhesive comprises a component A and a component B; the component A comprises the following components in parts by mass: 140-160 parts of starch, 200-300 parts of water, 20-25 parts of concentrated hydrochloric acid, 12-18 parts of dilute nitric acid, 25-40 parts of sodium hydroxide solution, 4-8 parts of an initiator, 12-20 parts of a hydrophobic monomer, 25-32 parts of a crosslinking monomer and 3-7 parts of an emulsifier; the component B comprises the following components in parts by mass: 12-15 parts of post-crosslinking agent.
In one embodiment, the starch comprises any one or a combination of several of corn starch, waxy corn starch, tapioca starch, wheat starch, potato starch, rice starch, mung bean starch.
In one embodiment, the concentrated hydrochloric acid is 12 to 15mol/L concentrated hydrochloric acid.
In one embodiment, the sodium hydroxide solution is a sodium hydroxide solution having a concentration of 10 to 15 mol/L.
In one embodiment, the dilute nitric acid is a nitric acid solution of 0.5 to 1 mol/L.
In one embodiment, the initiator is ceric ammonium nitrate.
In one embodiment, the emulsifier is cetyltrimethylammonium bromide.
In one embodiment, the hydrophobic monomer is one or a mixture of two of glycidyl methacrylate and methyl methacrylate.
In one embodiment, the crosslinking monomer is one or a mixture of diacetone acrylamide and methacrylic acid.
In one embodiment of the present invention, the post-crosslinking agent is one or a mixture of ethylenediamine and glutaraldehyde.
Preferably, the component A comprises, by mass, 150 parts of corn starch, 220 parts of water, 21.5 parts of a 12mol/L concentrated hydrochloric acid solution, 36 parts of a 10mol/L sodium hydroxide solution, 15 parts of a 0.5mol/L dilute nitric acid solution, 6.5 parts of ceric ammonium acid, 5 parts of cetyl trimethyl ammonium bromide, 15 parts of glycidyl methacrylate and 27 parts of diacetone acrylamide.
Preferably, the component B comprises 13.5 parts by weight of ethylenediamine.
The second object of the invention is to provide a preparation method of the starch-based shaving board adhesive, which comprises the following steps:
(1) Starch and water are prepared into starch milk with the mass ratio of 30-50% based on the dry basis of the starch, the starch milk is stirred uniformly, the temperature is raised to 50-60 ℃, and 4-8 mol/L hydrochloric acid is added for acidolysis; adding sodium hydroxide solution after acidolysis, adjusting the pH to 3-5, and then gelatinizing to obtain gelatinized starch emulsion;
(2) Adding a crosslinking monomer into water to prepare a crosslinking monomer solution, and then adding a hydrophobic monomer and an emulsifier into the crosslinking monomer solution to form a monomer emulsion;
(3) Adding an initiator into dilute nitric acid to prepare an initiator solution, adding 10-20% of the total volume of the initiator solution into the monomer emulsion, uniformly mixing and carrying out prepolymerization to obtain a prepolymerized monomer emulsion;
(4) Regulating the temperature of the gelatinized starch emulsion solution obtained in the step (1) to 50-70 ℃, then, regulating the total volume of the initiator solution to 50-80%, and then, adding a sodium hydroxide solution to regulate the pH value to 3-5 to obtain a reaction solution I;
(5) Dropwise adding the pre-polymerized monomer emulsion obtained in the step (3) into the reaction liquid I obtained in the step (4) for graft polymerization, adding the rest initiator solution after the dropwise adding is completed, then adding sodium hydroxide solution, adjusting the pH to 3-5, and preserving the heat for 30-45 min to obtain a starch-based emulsion modified by graft polymerization;
(6) Heating the starch-based emulsion modified by graft polymerization in the step (5) to 75-85 ℃, and preserving heat for 90-120 min again to obtain a polymerization modified adhesive;
(7) And (3) cooling the polymerization modified adhesive obtained in the step (6) to 30-50 ℃, and regulating the pH of the adhesive to 5-7 to obtain the starch-based adhesive for the particle board.
In one embodiment, the acidolysis in step (1) is carried out for a time period of 2 to 4 hours.
In one embodiment, the gelatinization in step (1) is carried out at a temperature of 60 to 90℃for a period of 30 to 60 minutes.
In one embodiment, the temperature of the prepolymerization in step (3) is 40 to 50℃and the time is 10 to 20 minutes.
In one embodiment, the dripping time of the pre-polymerized monomer emulsion in the step (5) is controlled to be 90-120 min.
The third object of the invention is the use of a starch-based chipboard adhesive as described above for the thermocompression bonding of chipboards, plywood, fiberboard, wood blocks.
In one embodiment, the starch-based particle board adhesive is added with a post-crosslinking agent and stirred and mixed uniformly before thermocompression bonding.
In one embodiment, the thermocompression bonding temperature is 120 to 150 ℃ and the pressure is 6 to 10MPa.
The invention controls the five key variables of initiator addition, monomer proportion, reaction time and crosslinking pH, and uses a novel preparation process of the grafting modified adhesive, so that the prepared adhesive has certain water resistance on the premise of meeting the low viscosity requirement, and after the crosslinking agent is added, the adhesive is hot pressed to prepare the shaving board, the adhesive can be quickly solidified, the water resistance can be further improved, the effect of high water resistance is finally achieved, and the performance of the shaving board is improved.
The invention performs accurate control aiming at the following key points:
① Initiator addition amount
The addition amount of the initiator is not less than 12% of the total amount of the monomers: too low an addition amount of initiator will result in a reduced grafting effect of the hydrophobic monomer and the crosslinking monomer on the starch, and a reduced curing speed; too high an initiator addition will result in a reduced graft chain length, reduced cross-linking strength, and increased oxidation of starch, reduced molecular weight of starch, and reduced particle board strength; in addition, the addition of dilute nitric acid to the initiator solution increases the initiation effect, and the grafting effect of the addition of the initiator in portions increases.
② Grafting monomer addition
The addition of the grafting monomers (hydrophobic monomer and crosslinking monomer) should not be less than 22% of the starch used: the small addition amount of the grafting monomer can lead to the reduction of the storage stability and the bonding strength of the starch adhesive, and the reduction of hydrophobic groups and crosslinking groups grafted on the starch can lead to the reduction of the mechanical strength and the water resistance; too high an addition amount of the grafting monomer has little effect on improving the mechanical property and the water resistance of the adhesive.
③ Monomer ratio
The proportion of the hydrophobic monomer is 25% -40% of the total monomer addition: the addition of the hydrophobic monomer is small, so that the water resistance of the starch adhesive is insufficient, the addition of the hydrophobic monomer is too high, the amount of crosslinking monomers grafted to the starch is small, the number of crosslinkable groups is insufficient, the crosslinking effect is poor, and finally, the water resistance and the curing performance of the adhesive are reduced.
④ Reaction time
The total time of the grafting reaction (step (5) and step (6) above) must not be less than 3.5 hours: too short or too long a reaction time affects the grafting effect of the monomer on the starch, resulting in a decrease in the adhesive strength and a deterioration in the water resistance of the adhesive.
⑤ Cross-linking pH
The pH in the system at the time of curing crosslinking (step (7) above) is not lower than 5.5: too low pH during crosslinking can lead to reduced crosslinking activity of the adhesive, poor curing effect and failure to achieve the effect of rapid curing.
Advantageous effects
(1) The invention destroys the crystal structure of the starch by gelatinizing the starch, so that monomer molecules can better enter between starch molecules, more monomers react with the starch, and the reaction efficiency and grafting effect are improved. The chain length of a grafted molecular chain is increased, the polymerization degree is increased, the distribution uniformity of crosslinking monomers is improved, and the activity and the crosslinking strength of subsequent crosslinking reactions are improved by carrying out prepolymerization treatment on the grafting monomers; the grafting efficiency of the monomer is improved by a method of adding an initiator in batches; after the post-crosslinking agent is added, the cross-linking reaction can be carried out by hot pressing, a three-dimensional reticular structure is formed, and stronger water resistance and bonding strength are ensured;
(2) According to the invention, the hydrophobic monomer and the crosslinking monomer are combined and grafted on the starch, so that the adhesive has certain water resistance; on the other hand, the grafting crosslinking monomer has the characteristic of high crosslinking reaction activity, and endows the adhesive with rapid curing performance, so that the adhesive strength and water resistance of the adhesive can be improved; the crosslinking groups on the hydrophobic monomer can also participate in crosslinking reaction, and the two grafting monomers can generate synergistic effect of composite crosslinking so as to ensure that the prepared adhesive has high water resistance; and the grafted molecular chains formed by the two monomers on the starch have different properties and repel each other, so that the exposure of crosslinking sites is promoted, and the effect of crosslinking reaction is improved. The grafting monomer used in the invention is matched with the post-crosslinking agent, so that the problems of easy solidification in the reaction process of the starch adhesive and slower solidification speed in use are solved, the solidification speed of the adhesive is improved, the solidification speed is reduced to be within 90 seconds, and the production efficiency of the shaving board is improved;
(3) The particle board prepared by the starch adhesive has various performances meeting the performance requirements of the P2 type shaving board in GB/T4897-2015, can be soaked in water at 20 ℃ for 2 hours without damage, has a water absorption thickness expansion rate of 5%, has high water resistance, and further improves the application of the starch-based adhesive.
Detailed Description
The invention will be further described in connection with the following embodiments, it being understood that these examples are for illustrative purposes only and are not intended to limit the scope of the invention.
Determination of adhesive cure time:
Adding 30g of adhesive and 2.5g of post-crosslinking agent into a beaker respectively, fully mixing, transferring 2.0g of the mixture into a test tube, inserting a stirring rod into the test tube, putting into a beaker filled with boiling water, starting timing, and solidifying the sample under stirring; when the stirring rod cannot stir, stopping timing, and taking the measured time as the curing time, performing three parallel experiments on each sample, and taking an average value.
Example 1
A starch-based shaving board adhesive with high water resistance and quick solidification, which comprises the following formula:
The preparation method of the starch-based shaving board adhesive comprises the following steps:
(1) Preparing starch and water into starch milk with the starch mass fraction of 50%, uniformly stirring and mixing, and heating to 60 ℃;
(2) Preparing 18ml of 12mol/L concentrated hydrochloric acid into 6.5mol/L dilute hydrochloric acid solution, adding the 6.5mol/L dilute hydrochloric acid solution into the starch milk obtained in the step (1) for acidolysis for 2 hours, then adding 10mol/L sodium hydroxide solution, adjusting the pH to 4, and maintaining at 80 ℃ for 30 minutes for gelatinization;
(3) 27g of a crosslinking monomer (diacetone acrylamide) is added into 60ml of water, 15g of a hydrophobic monomer (glycidyl methacrylate) and 5g of an emulsifier (cetyl trimethyl ammonium bromide) are added into the crosslinking monomer aqueous solution after dissolution, and ultrasonic treatment is carried out to obtain a monomer emulsion;
(4) Adding 6.5g of initiator (ceric ammonium nitrate) into 15ml of dilute nitric acid to prepare an initiator solution, adding 2.5ml of the initiator solution into the monomer emulsion obtained in the step (3), heating to 45 ℃, prepolymerizing for 15min, and then cooling the system to normal temperature;
(5) Cooling the gelatinized starch milk obtained in the step (2) to 60 ℃, adding 10ml of the initiator solution prepared in the step (4), and then adding sodium hydroxide solution to adjust the pH to 4;
(6) Dripping the monomer emulsion obtained in the step (4) after the pre-polymerization treatment into the starch emulsion obtained in the step (5) after the pH adjustment at a constant speed for graft polymerization, wherein the dripping time is controlled to be 100min, and the reaction temperature is kept to be 60 ℃; after the dripping is finished, adding the rest initiator solution, then adding sodium hydroxide solution to adjust the pH to 4, and preserving the heat for 30min; obtaining starch-based emulsion modified by graft polymerization;
(7) Heating the reaction kettle to 82.5 ℃, and preserving heat for 90min again to obtain a graft polymerization modified adhesive;
(8) Cooling the polymerization modified adhesive obtained in the step (7) to 45 ℃, and adjusting the pH of the adhesive to 6 to obtain a starch-based adhesive;
(9) Before the preparation of the shaving board, 13.5g of post-crosslinking agent (ethylenediamine) is added into the adhesive prepared in the step (8), and the mixture is stirred and mixed uniformly, and then the shaving board is subjected to hot pressing.
The adhesive product obtained by the embodiment is milky white in appearance, low in viscosity and strong in fluidity, and meets the requirements of a shaving board. The curing time of the adhesive is measured, and the result shows that the curing time of the adhesive for the starch-based shaving board is 103s; and hot-pressing for 5min at 135 ℃ and 10MPa, wherein the water absorption thickness expansion rate of the obtained shaving board is 4%, and the requirements of the national standard P2 type shaving board are met.
Example 2
A starch-based shaving board adhesive with high water resistance and quick solidification, which comprises the following formula:
The preparation of the starch-based particle board adhesive was carried out with reference to example 1, only with reduced initiator usage in step (4), and other operations and parameters unchanged.
The adhesive product obtained by the embodiment is milky white in appearance, low in viscosity and strong in fluidity, and meets the requirements of a shaving board. The curing time of the adhesive is measured, and the result shows that the curing time of the adhesive for the starch-based shaving board is 226s; and hot-pressing for 5min at 135 ℃ and 10MPa, wherein the water absorption thickness expansion rate of the obtained shaving board is 19%, and the requirements of the national standard P2 type shaving board are not met.
The influence of the addition amount of the initiator on the viscosity of the adhesive is proved by the examples 1 and 2, and the result shows that the use amount of the initiator is too small, the initiation effect is poor, the grafting effect is poor, the curing performance of the adhesive is influenced, and finally the strength and the water resistance of the particle board are influenced.
Example 3
A starch-based shaving board adhesive with high water resistance and quick solidification, which comprises the following formula:
The preparation method of the starch-based particle board adhesive is carried out according to the example 1, wherein the initiator type is replaced only in the step (4), and other operations and parameters are unchanged.
The influence of the initiator type on the curing time of the adhesive is proved by the examples 1 and 3, and the results show that the monomer and starch grafting effect is good at the reaction temperature of 60 ℃ by using the ceric ammonium nitrate initiator, the prepared adhesive has good curing performance and can meet the requirement of fast curing of the chipboard adhesive, and the starch adhesive prepared by using ammonium persulfate to initiate monomer grafting has poor grafting effect, so that the adhesive has poor curing performance, longer curing time at the hot pressing temperature of 135 ℃, low curing efficiency and poor water resistance, and can not meet the requirement of the chipboard adhesive.
Example 4
A starch-based shaving board adhesive with high water resistance and quick solidification, which comprises the following formula:
The preparation of the starch-based particle board adhesive was carried out with reference to example 1, and the amounts of crosslinking monomer (diacetone acrylamide) and hydrophobic monomer (glycidyl methacrylate) were adjusted to 18g and 10g only in step (3), with other operations and parameters unchanged.
The adhesive product obtained by the embodiment is milky white in appearance, low in viscosity and strong in fluidity, and meets the requirements of a shaving board. The curing time of the adhesive is measured, and the result shows that the curing time of the adhesive for the starch-based shaving board is 278s; and hot-pressing for 5min at 135 ℃ and 10MPa, wherein the water absorption thickness expansion rate of the obtained shaving board is 27%, and the requirements of the national standard P2 type shaving board are not met.
The effect of the addition amount of the grafting monomer on the curing performance of the adhesive is proved by examples 1 and 4, and the data show that the addition amount of the monomer is too small, the grafting amount of the monomer on starch is small, the water-resistant groups and the crosslinkable groups on the starch adhesive are too small, the water resistance and the curing performance of the adhesive are affected, and finally the strength and the water resistance of the shaving board are reduced.
Example 5
A starch-based shaving board adhesive with high water resistance and quick solidification, which comprises the following formula:
The preparation method of the starch-based particle board adhesive is carried out according to the example 1, and only the amounts of the crosslinking monomer (diacetone acrylamide) and the hydrophobic monomer (glycidyl methacrylate) in the step (3) are adjusted to 17g and 25g, and other operations and parameters are unchanged.
The adhesive product obtained by the embodiment is milky white in appearance, low in viscosity and strong in fluidity, and meets the requirements of a shaving board. The curing time of the adhesive is measured, and the result shows that the curing time of the adhesive for the starch-based shaving board is 198s; and hot-pressing for 5min at 135 ℃ and 10MPa, wherein the water absorption thickness expansion rate of the obtained shaving board is 18%, and the requirements of the national standard P2 type shaving board are not met.
The effect of the monomer ratio on the adhesive properties is demonstrated by examples 1, 5, the above results show that: when the proportion of the hydrophobic monomer is increased, the proportion of the crosslinking monomer is reduced, the curing performance of the adhesive is reduced, and the curing speed and the water resistance of the adhesive are reduced.
Example 6
A starch-based shaving board adhesive with high water resistance and quick solidification, which comprises the following formula:
The preparation method of the starch-based shaving board adhesive is carried out according to the example 1, wherein only the cross-linking monomer in the step (3) is replaced by methacrylic acid, the hydrophobic monomer is replaced by methyl methacrylate, and other operations and parameters are unchanged.
The adhesive product obtained by the embodiment is milky white in appearance, low in viscosity and strong in fluidity, and meets the requirements of a shaving board. The curing time of the adhesive is measured, and the result shows that the curing time of the adhesive for the starch-based shaving board is 153s; and hot-pressing for 5min at 135 ℃ and 10MPa, wherein the water absorption thickness expansion rate of the obtained shaving board is 12%, and the requirements of the national standard P2 type shaving board are not met.
The effect of the grafting monomer on the curing time of the adhesive is demonstrated by examples 1, 6. The adhesive prepared by using the crosslinking monomer diacetone acrylamide and the hydrophobic monomer glycidyl methacrylate and ethylenediamine at the hot-pressing temperature of 135 ℃ has shorter curing time, can meet the requirement of quick curing of the chipboard adhesive, and the adhesive prepared by using the crosslinking monomer methacrylic acid and the hydrophobic monomer methyl methacrylate and ethylenediamine has longer curing time at the hot-pressing temperature of 135 ℃ and has low curing efficiency and poor water resistance, and can not meet the requirement of the chipboard adhesive.
Example 7
A starch-based shaving board adhesive with high water resistance and quick solidification, which comprises the following formula:
the preparation method of the starch-based shaving board adhesive is carried out according to the example 1, only ethylenediamine in the step (9) is replaced by glutaraldehyde, and other operations and parameters are unchanged.
The adhesive product obtained by the embodiment is milky white in appearance, low in viscosity and strong in fluidity, and meets the requirements of a shaving board. The curing time of the adhesive is measured, and the result shows that the curing time of the adhesive for the starch-based shaving board is 214s; and hot-pressing for 5min at 135 ℃ and 10MPa, wherein the water absorption thickness expansion rate of the obtained shaving board is 24%, and the requirements of the national standard P2 type shaving board are not met.
The effect of the postcrosslinker on the curing time of the adhesive is demonstrated by examples 1, 7, the results indicated above being that: the ethylene diamine which is a post-crosslinking agent is added to rapidly solidify at 135 ℃, and glutaraldehyde which is other post-crosslinking agents is added to reduce the solidifying performance of the adhesive, the solidifying speed is reduced, the water resistance is reduced, and the performance of the adhesive is affected.
Example 8
A starch-based shaving board adhesive with high water resistance and quick solidification, which comprises the following formula:
the preparation method of the starch-based shaving board adhesive is carried out according to the embodiment 1, and only the dripping time and the heat preservation time in the step (6) are adjusted, specifically:
(6) Dripping the monomer emulsion obtained in the step (4) after the pre-polymerization treatment into the starch emulsion obtained in the step (5) after the pH adjustment at a constant speed for graft polymerization, wherein the dripping time is controlled to be 60min, and the reaction temperature is kept to be 60 ℃; after the dripping is finished, adding the rest initiator solution, then adding sodium hydroxide solution to adjust the pH to 4, and preserving the heat for 18min; to obtain the starch-based emulsion modified by graft polymerization.
The adhesive product obtained by the embodiment is milky white in appearance, low in viscosity and strong in fluidity, and meets the requirements of a shaving board. The curing time of the adhesive is measured, and the result shows that the curing time of the adhesive for the starch-based shaving board is 260s; and hot-pressing for 5min at 135 ℃ and 10MPa, wherein the water absorption thickness expansion rate of the obtained shaving board is 21%, and the requirements of the national standard P2 type shaving board are not met.
The effect of reaction time on the curing time of the adhesive is demonstrated by examples 1, 8; the above results indicate that reducing the polymerization time of monomer grafting results in a decrease in the grafting ratio of the monomer to starch, thereby affecting the curing speed of the adhesive and the effect of crosslinking, resulting in a longer curing time and a decrease in water resistance.
Example 9
A starch-based shaving board adhesive with high water resistance and quick solidification, which comprises the following formula:
the preparation method of the starch-based shaving board adhesive is carried out according to the embodiment 1, and only the pH value of the adhesive in the step (8) is adjusted, specifically:
(8) And (3) cooling the polymerization modified adhesive obtained in the step (7) to 45 ℃, and adjusting the pH of the adhesive to 4 to obtain the starch-based adhesive.
The adhesive product obtained by the embodiment is milky white in appearance, low in viscosity and strong in fluidity, and meets the requirements of a shaving board. The curing time of the adhesive is measured, and the result shows that the curing time of the adhesive for the starch-based shaving board is 168s; and hot-pressing for 5min at 135 ℃ and 10MPa, wherein the water absorption thickness expansion rate of the obtained shaving board is 16%, and the requirements of the national standard P2 type shaving board are not met.
The effect of crosslinking pH on the curing time of the adhesive is demonstrated by examples 1, 9. The above results show that, under the condition of ph=6, the ethylenediamine added as the post-crosslinking agent can be rapidly cured at a lower temperature, while the ethylenediamine added as the post-crosslinking agent under the condition of ph=4 has a slower curing speed, and the water resistance after curing is poor, so that the performance of the adhesive is affected.
Comparative example 1
The preparation of the starch adhesive is carried out with reference to example 1 in patent CN 114591707A.
Formula (mass/g):
The preparation method of the starch-based shaving board adhesive comprises the following steps:
(1) Starch and water are prepared into starch milk with the concentration of 45% based on the mass ratio of starch dry basis, and the starch milk is uniformly stirred and heated to 60 ℃;
(2) Diluting 18g of 12mol/L concentrated hydrochloric acid solution to 1mol/L, adding the diluted solution into starch milk for acidolysis for 2.5 hours, and then adding 10mol/L sodium hydroxide solution to adjust the pH to 4; regulating the temperature of the starch milk after acidolysis to 80 ℃, and after pregelatinization for 40min, keeping the reaction temperature unchanged at 80 ℃;
(3) 4g of initiator is dissolved in 5g of dilute nitric acid to prepare an initiator solution, 1.96g of emulsifier is dissolved in 24.8g of water to prepare a 5% emulsifier solution, 15g of crosslinking monomer is fully added into the emulsifier, and pre-emulsification is carried out through a high-speed shearing machine to prepare pre-emulsion.
(4) And (3) adding all the initiator solution prepared in the step (3) into the starch emulsion pre-gelatinized in the step (2), simultaneously dripping the pre-emulsion into the reaction system pre-gelatinized in the step (2) at a constant speed within 90min, adding 4g of initiator solution prepared by dissolving 5g of initiator in dilute nitric acid again after dripping is completed, and carrying out heat preservation reaction for 90min.
(5) And (3) cooling the emulsion subjected to crosslinking modification in the step (4) to 50 ℃, and regulating the pH to 6 to obtain the starch adhesive.
(6) When in use, the obtained starch adhesive and the binary cross-linking agent are mixed in advance uniformly and then the hot pressing of the shaving board is carried out.
The adhesive product obtained in the comparative example 1 is milky white in appearance, low in viscosity and high in fluidity, and meets the requirements of shaving boards. The measurement of the adhesive curing time shows that the adhesive curing time of the starch-based shaving board is 60s.
The flakeboard obtained in the comparative example 1 has a water absorption thickness expansion rate of 10% and does not meet the requirements of national standard P2 type flakeboards under the conditions of 135 ℃ and 10MPa for 5 min.
And hot-pressing for 5min at 170 ℃ and 11MPa, wherein the water absorption thickness expansion rate of the shaving board obtained in the comparative example 1 is 6%, and the requirements of the national standard P2 type shaving board are met.
It was demonstrated by example 1 and comparative example 1 that the addition of hydrophobic monomers to starch-based particle board adhesives further improved the water resistance of the adhesives and reduced the hot press temperature for particle board preparation. Under the hot pressing condition provided by patent CN 114591707A, the expansion rate of the water absorption thickness of the shaving board prepared in comparative example 1 is 6%, and the expansion rate of the water absorption thickness of the shaving board prepared in example 1 is lower; under the hot pressing condition of the invention, the expansion rate of the water absorption thickness of the shaving board prepared in the comparative example 1 is increased to 10%, and the water resistance is seriously reduced.
The above examples are not intended to limit the scope of the invention nor the order of execution of the steps described. The present invention is obviously modified by a person skilled in the art in combination with the prior common general knowledge, and falls within the scope of protection defined by the claims of the present invention.
Claims (10)
1. The starch-based chipboard adhesive is characterized by comprising a component A and a component B; the component A comprises the following components in parts by mass: 140-160 parts of starch, 200-300 parts of water, 20-25 parts of concentrated hydrochloric acid, 12-18 parts of dilute nitric acid, 25-40 parts of sodium hydroxide solution, 4-8 parts of an initiator, 12-20 parts of a hydrophobic monomer, 25-32 parts of a crosslinking monomer and 3-7 parts of an emulsifier; the component B comprises the following components in parts by mass: 12-15 parts of post-crosslinking agent.
2. The starch-based particle board adhesive of claim 1, wherein the starch comprises any one or a combination of several of corn starch, waxy corn starch, tapioca starch, wheat starch, potato starch, rice starch, mung bean starch.
3. The starch-based chipboard adhesive of claim 1, wherein the concentrated hydrochloric acid is 12-15 mol/L of concentrated hydrochloric acid; the sodium hydroxide solution is 10-15 mol/L sodium hydroxide solution; the dilute nitric acid is nitric acid solution with the concentration of 0.5-1 mol/L.
4. The starch-based particle board adhesive of claim 1, wherein the initiator is ceric ammonium nitrate; the emulsifier is cetyl trimethyl ammonium bromide.
5. The starch-based particle board adhesive of claim 1, wherein the hydrophobic monomer is one or a mixture of two of glycidyl methacrylate and methyl methacrylate; the crosslinking monomer is one or a mixture of diacetone acrylamide and methacrylic acid; the post-crosslinking agent is one or a mixture of two of ethylenediamine and glutaraldehyde.
6. A starch-based adhesive for particle boards according to any one of claims 1 to 7, characterized in that the preparation method comprises the steps of:
(1) Starch and water are prepared into starch milk with the mass ratio of 30-50% based on the dry basis of the starch, the starch milk is stirred uniformly, the temperature is raised to 50-60 ℃, and 4-8 mol/L hydrochloric acid is added for acidolysis; adding sodium hydroxide solution after acidolysis, adjusting the pH to 3-5, and then gelatinizing to obtain gelatinized starch emulsion;
(2) Adding a crosslinking monomer into water to prepare a crosslinking monomer solution, and then adding a hydrophobic monomer and an emulsifier into the crosslinking monomer solution to form a monomer emulsion;
(3) Adding an initiator into dilute nitric acid to prepare an initiator solution, adding 10-20% of the total volume of the initiator solution into the monomer emulsion, uniformly mixing and carrying out prepolymerization to obtain a prepolymerized monomer emulsion;
(4) Regulating the temperature of the gelatinized starch emulsion solution obtained in the step (1) to 50-70 ℃, then, regulating the total volume of the initiator solution to 50-80%, and then, adding a sodium hydroxide solution to regulate the pH value to 3-5 to obtain a reaction solution I;
(5) Dropwise adding the pre-polymerized monomer emulsion obtained in the step (3) into the reaction liquid I obtained in the step (4) for graft polymerization, adding the rest initiator solution after the dropwise adding is completed, then adding sodium hydroxide solution, adjusting the pH to 3-5, and preserving the heat for 30-45 min to obtain a starch-based emulsion modified by graft polymerization;
(6) Heating the starch-based emulsion modified by graft polymerization in the step (5) to 75-85 ℃, and preserving heat for 90-120 min again to obtain a polymerization modified adhesive;
(7) And (3) cooling the polymerization modified adhesive obtained in the step (6) to 30-50 ℃, and regulating the pH of the adhesive to 5-7 to obtain the starch-based adhesive for the particle board.
7. The starch-based particle board adhesive of claim 6, wherein the acid hydrolysis time of step (1) is 2-4 hours; the gelatinization temperature in the step (1) is 60-90 ℃ and the time is 30-60 min.
8. The starch-based particle board adhesive of claim 6, wherein the temperature of the pre-polymerization in step (3) is 40-50 ℃ for 10-20 min; the dripping time of the pre-polymerized monomer emulsion in the step (5) is controlled to be 90-120 min.
9. Use of a starch-based chipboard adhesive according to any one of claims 1 to 8 in the thermocompression bonding of chipboards, plywood, fiberboard, wood blocks.
10. The use according to claim 9, wherein the starch-based particle board adhesive is mixed with the post-crosslinking agent before thermocompression bonding; the temperature of the hot-press bonding is 120-150 ℃ and the pressure is 6-10 MPa.
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| CN202410311268.0A CN118146748A (en) | 2024-03-19 | 2024-03-19 | Starch-based particle board adhesive with high water resistance and quick solidification and preparation method thereof |
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| CN202410311268.0A CN118146748A (en) | 2024-03-19 | 2024-03-19 | Starch-based particle board adhesive with high water resistance and quick solidification and preparation method thereof |
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