WO2023185048A1 - 一种高温快速固化的淀粉基刨花板胶黏剂及其制备方法 - Google Patents

一种高温快速固化的淀粉基刨花板胶黏剂及其制备方法 Download PDF

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WO2023185048A1
WO2023185048A1 PCT/CN2022/135350 CN2022135350W WO2023185048A1 WO 2023185048 A1 WO2023185048 A1 WO 2023185048A1 CN 2022135350 W CN2022135350 W CN 2022135350W WO 2023185048 A1 WO2023185048 A1 WO 2023185048A1
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starch
adhesive
add
initiator
cross
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French (fr)
Inventor
金俊男
吴栋栋
张蒙威
尹健
程力
顾正彪
洪雁
李兆丰
李才明
班宵逢
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Jiangnan University
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Jiangnan University
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J103/00—Adhesives based on starch, amylose or amylopectin or on their derivatives or degradation products
    • C09J103/02—Starch; Degradation products thereof, e.g. dextrin
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • C09J151/02—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to polysaccharides
    • 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
    • B27N3/002—Manufacture of substantially flat articles, e.g. boards, from particles or fibres characterised by the type of binder
    • 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
    • B27N3/04—Manufacture of substantially flat articles, e.g. boards, from particles or fibres from fibres
    • 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
    • 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
    • B27N3/20—Moulding or pressing characterised by using platen-presses
    • B27N3/203—Moulding or pressing characterised by using platen-presses with heating or cooling means
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F251/00—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/08—Macromolecular additives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
    • C09J5/06—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers involving heating of the applied adhesive
    • 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

Definitions

  • the invention relates to a high-temperature rapid curing starch-based particle board adhesive and a preparation method thereof, and belongs to the technical field of adhesive preparation.
  • Starch is a naturally degradable, environmentally friendly and renewable substance with the characteristics of wide sources, low price, non-toxic and pollution-free. Compared with common adhesives on the market, using starch to replace petroleum-based monomers is environmentally friendly and can significantly reduce costs. Therefore, starch-based wood adhesives have great potential for development in the future.
  • common artificial boards on the market are made by hot pressing, and particleboard is an indispensable type of artificial boards.
  • the hot pressing process of particle board takes a short time and the temperature is high.
  • the adhesive needs to be able to withstand high temperatures and be able to solidify quickly at high temperatures. At the same time, the adhesive needs to have a low viscosity and a certain degree of water resistance.
  • traditional starch adhesives have high viscosity and are not durable.
  • thermosetting low-viscosity starch-based adhesive which has greatly improved its water resistance and dry strength.
  • it has long curing time and low curing efficiency. Low-level problems still make it difficult to promote wider application of starch-based adhesives.
  • the starch adhesive prepared in the past has long curing time and poor curing efficiency during the hot pressing process, resulting in long hot pressing time and low production efficiency for particleboards, which cannot meet the needs of modern particleboard preparation.
  • the present invention provides a starch-based particleboard adhesive that can be quickly cured at high temperatures and a preparation method thereof.
  • the present invention selects a cross-linking monomer that does not self-crosslink during the reaction process to ensure that The low viscosity of starch adhesive, and the binary cross-linking agent matched with the cross-linking monomer is added before use, which can quickly cross-link with the cross-linking monomer at high temperature to ensure better thermosetting and water resistance. It ensures the faster curing speed of starch adhesive and meets the needs of particle board adhesive.
  • the present invention conducts extensive research on the control of three key steps: acidolysis time, initiator addition amount, cross-linking monomer addition amount, and reaction temperature, so that the prepared adhesive can maintain low viscosity while adding binary cross-linking monomers.
  • the combined agent can be quickly solidified during hot pressing, greatly shortening the hot pressing time, and improving the production efficiency of particleboards while ensuring water resistance and thermosetting properties. All properties of the particleboard pressed with the adhesive prepared by the present invention can meet the performance requirements of the P2 type particleboard in the national standard GB/T 4897-2015 particleboard. Compared with previous research, the curing time of the starch adhesive reduced to less than 70 seconds.
  • control points In terms of key control points, the present invention performs precise control on the following control points:
  • acidolysis time should not be less than 2h. If the acidolysis time is too short, the acidolysis effect is poor, resulting in high viscosity of the starch adhesive, which is not suitable for particleboard; if the acidolysis time is too long, the starch will be excessively disintegrated, resulting in low monomer grafting efficiency, which directly affects the water resistance and thermosetting properties.
  • the amount of initiator added should not be less than 5% of the starch dosage. Dissolving in dilute nitric acid can improve the initiating efficiency. Adding too little initiator will lead to poor grafting effect and prolong the heat setting time. At the same time, add the initiator in batches. Better results.
  • cross-linking monomer should not be less than 10% of the starch dosage. Adding too little cross-linking monomer directly leads to a reduction in the bonding strength and water resistance of the starch adhesive.
  • reaction temperature shall not be lower than 75°C. If the reaction temperature is too high or too low, it will affect the reaction efficiency of the cross-linking monomer and result in insufficient water resistance and thermosetting properties of the adhesive.
  • the added amount of binary cross-linking agent should not be less than 10% of the starch dosage. Adding too little binary cross-linking agent will prolong the curing time of the adhesive.
  • the first object of the present invention is to provide a high-temperature and rapid-curing starch-based particleboard adhesive.
  • the formula of the starch-based particleboard adhesive includes: (in parts by mass)
  • the second object of the present invention provides a method for preparing a high-temperature rapid-curing starch-based particleboard adhesive.
  • the preparation method is as follows:
  • Starch milk made of starch is used as the main raw material. After acidolysis, the pH is adjusted and pre-gelatinized; the emulsifier solution and part of the initiator solution are prepared separately; the emulsifier solution and cross-linking monomer are pre-emulsified. form a pre-emulsion; add part of the configured initiator solution to the above-mentioned pre-gelatinized starch emulsion. After the grafting reaction occurs, add the remaining initiator to keep warm. After the reaction is completed, the temperature is lowered to adjust the pH to prepare a starch adhesive. ; When using starch adhesive, mix it evenly with the binary cross-linking agent before use.
  • the preparation method is as follows:
  • step (2) Warm the starch milk in step (1) to 60°C, add hydrochloric acid diluted to 0.8 ⁇ 1.2mol/L for acidolysis, and then add sodium hydroxide solution to adjust the pH to 3 ⁇ 5; adjust the starch milk after acidolysis temperature to 70 ⁇ 90°C, pre-gelatinized to produce pre-gelatinized starch milk;
  • step (3) Add all the initiator solution in step (3) to the pregelatinized starch milk in step (2), and at the same time, add the pregelatinized starch milk in step (3) dropwise at a constant speed to the pregelatinized starch in step (2).
  • the reconfigured initiator solution is: add dilute nitric acid to the remaining initiator accounting for 40% to 70% of the total mass of the initiator to form an initiator. agent solution, and insulate it again to obtain a cross-linked modified mixed emulsion system;
  • step (4) Cool the mixed emulsion system that has been cross-linked and modified in step (4) to 30 to 50°C, and adjust the pH of the emulsion to 6 to 8 to obtain a starch adhesive.
  • the preparation method is as follows:
  • step (2) Warm the starch milk in step (1) to 60°C, add hydrochloric acid diluted to 0.8 to 1.2 mol/L for acidolysis for 2 to 4 hours, and then add sodium hydroxide solution to adjust the pH to 3 to 5; after acidolysis Adjust the temperature of the starch milk to 70-90°C and pre-gelatinize it for 30-60 minutes to make pre-gelatinized starch milk;
  • step (3) Add all the initiator solution in step (3) to the pregelatinized starch milk in step (2), and at the same time, add the pregelatinized starch milk in step (3) dropwise at a constant speed to the pregelatinized starch in step (2).
  • the dripping time is controlled at 90 to 120 minutes.
  • the reconfigured initiator solution is: the remainder accounts for 40% to 70% of the total mass of the initiator. Add dilute nitric acid to the initiator to form an initiator solution, and keep it warm for 90 to 120 minutes again to obtain a cross-linked modified mixed emulsion system;
  • step (4) Cool the mixed emulsion system that has been cross-linked and modified in step (4) to 30 to 50°C, and adjust the pH of the emulsion to 6 to 8 to obtain a starch adhesive.
  • the starch is any one or a combination of corn starch, waxy corn starch, tapioca starch, wheat starch, and potato starch.
  • the acidolysis time of step (2) is 2 to 4 hours.
  • the concentration of hydrochloric acid diluted in step (2) is 1 mol/L.
  • the reaction temperature in step (2) is 80°C.
  • the pregelatinization time of step (2) is 30 to 60 minutes.
  • the dropping time of step (4) is controlled between 90 and 120 minutes.
  • the holding time of step (4) is 90 to 120 minutes.
  • the concentrated hydrochloric acid is 12 mol/L concentrated hydrochloric acid.
  • the sodium hydroxide solution is a sodium hydroxide solution with a concentration of 10 mol/L.
  • the dilute nitric acid is a 0.5 mol/L nitric acid solution.
  • the initiator is cerium nitrate salt.
  • the emulsifier is disodium decyl polyoxyethylene (6) ether sulfosuccinate.
  • the cross-linking monomer is one or a mixture of two types of diacetone acrylamide and hydroxybutyl methacrylate.
  • the binary cross-linking agent is one or a mixture of adipic acid dihydrazide and succinic acid dihydrazide.
  • the third object of the present invention is to provide the high-temperature and rapid-curing starch-based particleboard adhesive prepared above for use in the hot-pressure bonding of particleboards, plywood, fiberboards, and wood blocks.
  • a starch adhesive and a binary cross-linking agent are used in combination when applying a high-temperature rapid-curing starch-based particleboard adhesive.
  • the hot-pressing bonding method of the particleboard is to mix the adhesive and the shavings evenly and then lay them under a hot-pressing pressure of 3-11MPa and a hot-pressing temperature of 130°C-180°C. Pressed and formed at high temperature.
  • the present invention reduces the viscosity of the starch adhesive through acidolysis to ensure lower viscosity during application.
  • the reaction efficiency is improved by dropping cross-linking monomers.
  • the selected cross-linking monomers will not cross-link at room temperature and reaction temperature, and can react with the binary cross-linking agent during hot pressing after adding the binary cross-linking agent. Rapid cross-linking occurs to form a macromolecular network structure, which reduces the curing time of the adhesive while ensuring strong water resistance and bonding strength.
  • cross-linking monomer combined with the binary cross-linking agent used in the present invention solves the problem of long curing time of starch adhesive at high temperature in the past, and further reduces the curing time of starch adhesive to less than 70 seconds. , improving the production efficiency of particleboard.
  • step (2) Warm the starch milk in step (1) to 60°C, dilute 18g of 12mol/L concentrated hydrochloric acid solution to 1mol/L, add it to the starch milk for acidolysis, acidolyze for 2.5h, and then add 10mol/L hydrogen Adjust the pH of the sodium oxide solution to 4; adjust the temperature of the acidolyzed starch milk to 80°C. After pre-gelatinization for 40 minutes, the reaction temperature remains unchanged at 80°C;
  • step (3) Add all the initiator solution configured in step (3) to the pregelatinized starch emulsion in step (2), and at the same time, add the pre-emulsion dropwise into the pregelatinized starch milk in step (2) within 90 minutes.
  • an initiator solution prepared by dissolving 4g of initiator in 5g of dilute nitric acid add an initiator solution prepared by dissolving 4g of initiator in 5g of dilute nitric acid, and keep the reaction for 90 minutes to obtain a cross-linked modified mixed emulsion system.
  • step (4) Cool the cross-linked modified mixed emulsion system in step (4) to 50°C and adjust the pH to 6 to obtain a starch adhesive.
  • the appearance of the product obtained in this example is milky white, shiny, and has a low initial viscosity, which meets the requirements for particleboard use. Refer to the method of "Measurement of adhesive curing time" above to measure the curing time.
  • the obtained adhesive curing time is 60s.
  • the water absorption thickness expansion rate of the obtained particleboard was 6%, which meets the requirements of the national standard P2 type particleboard.
  • step (2) Warm the starch milk in step (1) to 60°C, dilute 18g of 12mol/L concentrated hydrochloric acid solution to 1mol/L, add it to the starch milk for acidolysis, acidolyze for 1 hour, and then add 10mol/L hydrogen oxide Adjust the pH of the sodium solution to 4; adjust the temperature of the acidolyzed starch milk to 80°C. After pre-gelatinization for 40 minutes, the reaction temperature remains unchanged at 80°C;
  • step (3) Add all the initiator solution configured in step (3) to the pregelatinized starch emulsion in step (2), and at the same time, add the pre-emulsion dropwise into the pregelatinized starch milk in step (2) within 90 minutes.
  • an initiator solution prepared by dissolving 4g of initiator in 5g of dilute nitric acid add an initiator solution prepared by dissolving 4g of initiator in 5g of dilute nitric acid, and keep the reaction for 90 minutes to obtain a cross-linked modified mixed emulsion system.
  • step (4) Cool the cross-linked modified mixed emulsion system in step (4) to 50°C and adjust the pH to 6 to obtain a starch adhesive.
  • the product obtained in this embodiment has a milky white appearance, poor fluidity, and high viscosity, which cannot meet the use requirements of particleboard and has no application value.
  • step (2) Warm the starch milk in step (1) to 60°C, dilute 18g of 12mol/L concentrated hydrochloric acid solution to 1mol/L, add it to the starch milk for acidolysis, acidolyze for 4 hours, and then add 10mol/L hydrogen oxide Adjust the pH of the sodium solution to 4; adjust the temperature of the acidolyzed starch milk to 80°C. After pre-gelatinization for 40 minutes, the reaction temperature remains unchanged at 80°C;
  • step (3) Add all the initiator solution configured in step (3) to the pregelatinized starch emulsion in step (2), and at the same time, add the pre-emulsion dropwise into the pregelatinized starch milk in step (2) within 90 minutes.
  • an initiator solution prepared by dissolving 4g of initiator in 5g of dilute nitric acid add an initiator solution prepared by dissolving 4g of initiator in 5g of dilute nitric acid, and keep the reaction for 90 minutes to obtain a cross-linked modified mixed emulsion system.
  • step (4) Cool the cross-linked modified mixed emulsion system in step (4) to 50°C and adjust the pH to 6 to obtain a starch adhesive.
  • the appearance of the product obtained in this example is milky white, shiny, and the initial viscosity is very low.
  • the curing time of the obtained adhesive is 140s. Leave it for a period of time. There will be delamination in the future and it will have no application value.
  • Examples 1, 2, and 3 are used to prove the effect of acidolysis time on the viscosity of the adhesive. From the above data, it can be seen that if the acidolysis time is too short, the acidolysis effect is poor, resulting in the adhesive having too high viscosity and poor fluidity, which cannot meet the requirements. Particleboard needs to be used, but if the acid hydrolysis time is too long, the starch will be excessively disintegrated, the reaction effect will be poor, the curing time will become longer, and the rapid curing effect cannot be achieved.
  • step (2) Warm the starch milk in step (1) to 60°C, dilute 18g of 12mol/L concentrated hydrochloric acid solution to 1mol/L, add it to the starch milk for acidolysis, acidolyze for 2.5h, and then add 10mol/L hydrogen Adjust the pH of the sodium oxide solution to 4; adjust the temperature of the acidolyzed starch milk to 80°C. After pre-gelatinization for 40 minutes, the reaction temperature remains unchanged at 80°C;
  • step (3) Add all the initiator solution configured in step (3) to the pregelatinized starch emulsion in step (2), and at the same time, add the pre-emulsion dropwise into the pregelatinized starch milk in step (2) within 90 minutes.
  • an initiator solution prepared by dissolving 4g of initiator in 5g of dilute nitric acid add an initiator solution prepared by dissolving 4g of initiator in 5g of dilute nitric acid, and keep the reaction for 90 minutes to obtain a cross-linked modified mixed emulsion system.
  • step (4) Cool the cross-linked modified mixed emulsion system in step (4) to 50°C and adjust the pH to 6 to obtain a starch adhesive.
  • the appearance of the product obtained in this example is milky white, shiny, and has a low initial viscosity, which meets the requirements for particleboard use. Refer to the method of "Measurement of adhesive curing time" above to measure the curing time.
  • the obtained adhesive curing time is 150s.
  • Examples 1 and 4 are used to prove the impact of cross-linking monomers on the curing time of adhesives. From the significance analysis of the above data, it can be seen that the adhesive prepared using diacetone acrylamide and adipic acid dihydrazide are used together. The curing time is short and can meet the requirements for rapid curing of particleboard adhesives. However, the adhesive prepared using N-hydroxyethylacrylamide and adipic acid dihydrazide have a long curing time and low curing efficiency. Meet the needs of particleboard adhesives.
  • step (2) Warm the starch milk in step (1) to 60°C, dilute 18g of 12mol/L concentrated hydrochloric acid solution to 1mol/L, add it to the starch milk for acidolysis, acidolyze for 2.5h, and then add 10mol/L hydrogen Adjust the pH of the sodium oxide solution to 4; adjust the temperature of the acidolyzed starch milk to 80°C. After pre-gelatinization for 40 minutes, the reaction temperature remains unchanged at 80°C;
  • step (3) Add all the initiator solution configured in step (3) to the pregelatinized starch emulsion in step (2), and at the same time, add the pre-emulsion dropwise into the pregelatinized starch milk in step (2) within 90 minutes.
  • an initiator solution prepared by dissolving 4g of initiator in 5g of dilute nitric acid add an initiator solution prepared by dissolving 4g of initiator in 5g of dilute nitric acid, and keep the reaction for 90 minutes to obtain a cross-linked modified mixed emulsion system.
  • step (4) Cool the cross-linked modified mixed emulsion system in step (4) to 50°C and adjust the pH to 6 to obtain a starch adhesive.
  • the appearance of the product obtained in this example is milky white, shiny, and has a low initial viscosity, which meets the requirements for particleboard use.
  • step (2) Warm the starch milk in step (1) to 60°C, dilute 18g of 12mol/L concentrated hydrochloric acid solution to 1mol/L, add it to the starch milk for acidolysis, acidolyze for 2.5h, and then add 10mol/L hydrogen Adjust the pH of the sodium oxide solution to 4; adjust the temperature of the acidolyzed starch milk to 80°C. After pre-gelatinization for 40 minutes, the reaction temperature remains unchanged at 80°C;
  • step (3) Add all the initiator solution configured in step (3) to the pregelatinized starch emulsion in step (2), and at the same time, add the pre-emulsion dropwise into the pregelatinized starch milk in step (2) within 90 minutes.
  • an initiator solution prepared by dissolving 4g of initiator in 5g of dilute nitric acid add an initiator solution prepared by dissolving 4g of initiator in 5g of dilute nitric acid, and keep the reaction for 90 minutes to obtain a cross-linked modified mixed emulsion system.
  • step (4) Cool the cross-linked modified mixed emulsion system in step (4) to 50°C and adjust the pH to 6 to obtain a starch adhesive.
  • the appearance of the product obtained in this example is milky white, shiny, and has a low initial viscosity, which meets the requirements for particleboard use.
  • Measurement of Adhesive Curing Time method to measure the curing time. The resulting adhesive cannot be cured.
  • step (2) Warm the starch milk in step (1) to 60°C, dilute 18g of 12mol/L concentrated hydrochloric acid solution to 1mol/L, add it to the starch milk for acidolysis, acidolyze for 2.5h, and then add 10mol/L hydrogen Adjust the pH of the sodium oxide solution to 4; adjust the temperature of the acidolyzed starch milk to 80°C. After pre-gelatinization for 40 minutes, lower the temperature to 70°C for reaction;
  • step (3) Add all the initiator solution configured in step (3) to the pregelatinized starch emulsion in step (2), and at the same time, add the pre-emulsion dropwise into the pregelatinized starch milk in step (2) within 90 minutes.
  • an initiator solution prepared by dissolving 4g of initiator in 5g of dilute nitric acid add an initiator solution prepared by dissolving 4g of initiator in 5g of dilute nitric acid, and keep the reaction for 90 minutes to obtain a cross-linked modified mixed emulsion system.
  • step (4) Cool the cross-linked modified mixed emulsion system in step (4) to 50°C and adjust the pH to 6 to obtain a starch adhesive.
  • the appearance of the product obtained in this example is milky white, shiny, and has a low initial viscosity, which meets the requirements for particleboard use. Refer to the method of "Measurement of adhesive curing time" above to measure the curing time. The obtained adhesive curing time is 90s.
  • the water absorption thickness expansion rate of the obtained particleboard was 10%, which exceeded 8% and did not meet the requirements of the national standard P2 type particleboard.
  • step (2) Warm the starch milk in step (1) to 60°C, dilute 24g of 12mol/L concentrated hydrochloric acid solution to 1.5mol/L, add it to the starch milk for acidolysis, acidolyze for 2.5h, and then add 10mol/L Adjust the pH of the sodium hydroxide solution to 4; adjust the temperature of the acidolyzed starch milk to 80°C. After pre-gelatinization for 40 minutes, the reaction temperature remains unchanged at 80°C;
  • step (3) Add all the initiator solution configured in step (3) to the pregelatinized starch emulsion in step (2), and at the same time, add the pre-emulsion dropwise into the pregelatinized starch milk in step (2) within 90 minutes.
  • an initiator solution prepared by dissolving 4g of initiator in 5g of dilute nitric acid add an initiator solution prepared by dissolving 4g of initiator in 5g of dilute nitric acid, and keep the reaction for 90 minutes to obtain a cross-linked modified mixed emulsion system.
  • step (4) Cool the cross-linked modified mixed emulsion system in step (4) to 50°C and adjust the pH to 6 to obtain a starch adhesive.
  • the appearance of the product obtained in this example is milky white, shiny, and has a low initial viscosity, which meets the requirements for particleboard use.
  • the curing time of the obtained adhesive is 100s, and delamination occurs after being left for a period of time, which has no application value.
  • Examples 1, 7, and 8 are used to prove the impact of reaction conditions on the curing time of the adhesive. From the significance analysis of the above data, it can be seen that too low a reaction temperature will affect the grafting efficiency of the monomer, resulting in a prolongation of the curing time. Too high an acid hydrolysis concentration will cause excessive disintegration and reduce reaction efficiency, and stratification will also occur. Therefore, the optimal reaction conditions are that the concentration of hydrochloric acid is 1 mol/L and the reaction temperature is 80°C.
  • step (2) Warm the starch milk in step (1) to 60°C, dilute 18g of 12mol/L concentrated hydrochloric acid solution to 1mol/L, add it to the starch milk for acidolysis, acidolyze for 2.5h, and then add 10mol/L hydrogen Adjust the pH of the sodium oxide solution to 4; adjust the temperature of the acidolyzed starch milk to 80°C. After pre-gelatinization for 40 minutes, the reaction temperature remains unchanged at 80°C;
  • step (3) Add all the initiator solution configured in step (3) to the pregelatinized starch emulsion in step (2), and at the same time, add the pre-emulsion dropwise into the pregelatinized starch milk in step (2) within 90 minutes.
  • an initiator solution prepared by dissolving 4g of initiator in 5g of dilute nitric acid add an initiator solution prepared by dissolving 4g of initiator in 5g of dilute nitric acid, and keep the reaction for 90 minutes to obtain a cross-linked modified mixed emulsion system.
  • step (4) Cool the cross-linked modified mixed emulsion system in step (4) to 50°C and adjust the pH to 6 to obtain a starch adhesive.
  • the appearance of the product obtained in this example is milky white, shiny, and has a low initial viscosity, which meets the requirements for particleboard use. Refer to the method of "Measurement of adhesive curing time" above to measure the curing time.
  • the obtained adhesive curing time is 65s.
  • the water absorption thickness expansion rate of the obtained particleboard was 7%, which meets the requirements of the national standard P2 type particleboard.
  • step (2) Warm the starch milk in step (1) to 60°C, dilute 18g of 12mol/L concentrated hydrochloric acid solution to 1mol/L, add it to the starch milk for acidolysis, acidolyze for 2 hours, and then add 10mol/L hydrogen oxide Adjust the pH of the sodium solution to 4; adjust the temperature of the acidolyzed starch milk to 80°C. After pre-gelatinization for 30 minutes, the reaction temperature remains unchanged at 80°C;
  • step (3) Add all the solution prepared in step (3) to the pregelatinized starch milk in step (2), and at the same time, add the cross-linking monomer dropwise into the pregelatinized starch milk in step (2) within 105 minutes.
  • step (3) add 10g of an initiator solution with a mass concentration of 3%, and keep the reaction for 105 minutes to obtain a cross-linked modified mixed emulsion system.
  • step (4) Cool the cross-linked modified mixed emulsion system in step (4) to 50°C and adjust the pH to 5 to obtain a starch adhesive.
  • the appearance of the product obtained in this example is milky white, shiny, and has a low initial viscosity, which meets the requirements for particleboard use. Refer to the method of "Measurement of adhesive curing time" above to measure the curing time.
  • the obtained adhesive curing time is 120s.
  • step (2) Warm the starch milk in step (1) to 60°C, dilute 18g of 12mol/L concentrated hydrochloric acid solution to 1mol/L, add it to the starch milk for acidolysis, acidolyze for 2 hours, and then add 10mol/L hydrogen oxide Adjust the pH of the sodium solution to 4; adjust the temperature of the acidolyzed starch milk to 80°C. After pre-gelatinization for 30 minutes, the reaction temperature remains unchanged at 80°C;
  • step (3) Add all the solution prepared in step (3) to the pregelatinized starch milk in step (2), and at the same time, add the cross-linking monomer dropwise into the pregelatinized starch milk in step (2) within 105 minutes.
  • step (3) add 10g of an initiator solution with a mass concentration of 3%, and keep the reaction for 105 minutes to obtain a cross-linked modified mixed emulsion system.
  • step (4) Cool the cross-linked modified mixed emulsion system in step (4) to 50°C and adjust the pH to 5 to obtain a starch adhesive.
  • the appearance of the product obtained in this example is milky white, shiny, and has a low initial viscosity, which meets the requirements for particleboard use. Refer to the method of "Measurement of Adhesive Curing Time" above to measure the curing time.
  • the obtained adhesive curing time is 130s.
  • step (2) Warm the starch milk in step (1) to 60°C, dilute 18g of 12mol/L concentrated hydrochloric acid solution to 1mol/L, add it to the starch milk for acidolysis, acidolyze for 2.5h, and then add 10mol/L hydrogen Adjust the pH of the sodium oxide solution to 4; adjust the temperature of the acidolyzed starch milk to 80°C. After pre-gelatinization for 40 minutes, the reaction temperature remains unchanged at 80°C;
  • step (3) Add all the initiator solution configured in step (3) to the pregelatinized starch emulsion in step (2), and at the same time, add the pre-emulsion dropwise into the pregelatinized starch milk in step (2) within 90 minutes.
  • an initiator solution prepared by dissolving 4g of initiator in 5g of dilute nitric acid add an initiator solution prepared by dissolving 4g of initiator in 5g of dilute nitric acid, and keep the reaction for 90 minutes to obtain a cross-linked modified mixed emulsion system.
  • step (4) Cool the cross-linked modified mixed emulsion system in step (4) to 50°C and adjust the pH to 6 to obtain a starch adhesive.
  • the appearance of the product obtained in this example is milky white, shiny, and has a low initial viscosity, which meets the requirements for particleboard use. Refer to the method of "Measurement of Adhesive Curing Time" above to measure the curing time.
  • the obtained adhesive curing time is 110s.

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Abstract

本发明公开了一种高温快速固化的淀粉基刨花板胶黏剂及其制备方法，属于胶粘剂制备技术领域。本发明选用了一种在反应过程不会发生自交联的交联单体来保证淀粉胶黏剂的低粘度，而在使用前加入与交联单体配套的二元交联剂，与交联单体在高温下发生快速交联来保证较好的热固性以及耐水性，同时保证了淀粉胶黏剂较快的固化速度，满足刨花板胶黏剂的需求，解决了以往淀粉胶黏剂高温下固化时间长的问题，进一步降低了淀粉胶黏剂的固化时间，降低至60s左右，提高了刨花板的生产效率。制备的刨花板各项性能均符合GB/T 4897-2015刨花板的性能要求，可在20℃水中浸泡2h不崩解，且吸水厚度膨胀率在7％，耐水性较好，能广泛应用于刨花板、胶合板、纤维板、木块的热压粘接。

Description

一种高温快速固化的淀粉基刨花板胶黏剂及其制备方法 技术领域
本发明涉及一种高温快速固化的淀粉基刨花板胶黏剂及其制备方法，属于胶黏剂制备技术领域。
背景技术
近年来，随着中国经济的快速发展，城镇建筑和室内外装饰装修行业发展迅速，推动了我国人造板行业的快速增长和扩张，2018年我国人造板的产量已超过世界上其他国家人造板产量总和，随之而来的则是胶黏剂行业的迅猛发展。市面上绝大多数人造板使用的传统胶黏剂主要是酚醛胶、脲醛胶和三聚氰胺甲醛胶，价格便宜，但污染和健康安全隐患较为严重，制备过程和所制得的人造板都存在游离甲醛释放，导致环境污染并危害公众健康。因此，有必要开发一种环境友好、耐水性能好、粘接性能好的天然资源胶粘剂。
淀粉是一种天然可降解、环保可再生的物质，具有来源广泛、价格低廉、无毒无污染等特点。相较于市面上常见的胶黏剂而言，使用淀粉取代石油基单体，对环境友好的同时也能够大幅降低成本。因此，淀粉基木材胶黏剂在未来具有很大发展潜力。目前，市面上常见的人造板都是通过热压而成，而刨花板是人造板中不可或缺的一类。刨花板热压过程时间短、温度高，需要胶黏剂能耐高温同时能在高温下快速固化，同时需要胶黏剂粘度较低且具有一定的耐水性，而传统的淀粉胶黏剂粘度高、不耐高温、缺少热固性且耐水性差。针对上述刨花板胶黏剂的要求，本研究团队之前制备了具有热固性的低黏度淀粉基胶黏剂，且在耐水性、干强度等方面做到了较大的提升，但存在固化时间长，固化效率低等问题，还难以推动淀粉基胶黏剂的更广泛的应用。
发明内容
[技术问题]
以往制备的淀粉胶黏剂在热压过程中由于固化时间长，固化效率差等问题导致刨花板的热压时间长，生产效率低，不能满足现代刨花板制备需求。
[技术方案]
为解决上述问题，本发明提供了一种在高温能快速固化的淀粉基刨花板胶黏剂及其制备方法，本发明选用了一种在反应过程不会发生自交联的交联单体来保证淀粉胶黏剂的低粘度，而在使用前加入与交联单体配套的二元交联剂，与交联单体在高温下能发生快速交联来保证较好的热固性以及耐水性，同时保证了淀粉胶黏剂较快的固化速度，满足刨花板胶黏剂的需 求。本发明对酸解时间、引发剂添加量、交联单体添加量、反应温度三个关键步骤的控制进行了大量的研究，使得制备的胶黏剂在保持低黏度的同时，加入二元交联剂后在热压时能快速固化，大大缩短了热压时间，在保证了耐水性以及热固性的前提下，提高了刨花板的生产效率。用本发明制备的胶黏剂压制的刨花板的各项性能均能达到国标GB/T 4897-2015刨花板中的P2型刨花板的性能要求，与之前的研究相比，将淀粉胶黏剂的固化时间降低至70s以内。
本发明在关键控制点方面，针对如下控制点进行精准控制：
①酸解时间，酸解时间不低于2h。酸解时间过短，酸解效果较差导致淀粉胶黏剂粘度过高，不适用于刨花板；酸解时间过长，淀粉过度崩解导致单体接枝效率低，直接影响耐水性以及热固性。
②引发剂添加量不得低于淀粉用量的5％，溶于稀硝酸能提高引发效率，引发剂的添加量过少会导致接枝效果变差，延长热固时间，同时分批添加引发剂的效果更佳。
③交联单体添加量不低于淀粉用量的10％。交联单体的添加量过少直接导致淀粉胶黏剂粘结强度以及耐水性的降低。
④反应温度不得低于75℃。反应温度过高过低均会影响交联单体的反应效率，会使胶黏剂的耐水性以及热固性不足。
⑤二元交联剂添加量不少于淀粉用量的10％。二元交联剂添加量过少会导致胶黏剂固化时间的延长。
本发明第一个目的提供了一种高温快速固化的淀粉基刨花板胶黏剂，所述的淀粉基刨花板胶黏剂的配方包括：(以质量份数计)
Figure PCTCN2022135350-appb-000001
本发明第二个目的提供了一种高温快速固化的淀粉基刨花板胶黏剂的制备方法，所述制备方法如下：
以淀粉制成的淀粉乳为主要原料，对其进行酸解处理后，调节pH并进行预糊化；分别 配置乳化剂溶液和部分引发剂溶液；将乳化剂溶液和交联单体预乳化制成预乳液；将配置好的部分引发剂溶液加到上述预糊化后的淀粉乳中，待发生接枝反应后，加入剩余引发剂保温，反应完毕后降温调节pH，制得淀粉胶黏剂；淀粉胶黏剂使用时，与二元交联剂混合均匀后使用。
在本发明的一种实施方式中，所述制备方法具体如下：
(1)将淀粉与水配成以淀粉干基计质量比为30％～50％的浓度的淀粉乳，搅拌均匀，备用；
(2)将步骤(1)中的淀粉乳升温至60℃，加入稀释为0.8～1.2mol/L的盐酸酸解，然后加入氢氧化钠溶液调节pH至3～5；酸解后调节淀粉乳的温度至70～90℃，预糊化制成预糊化淀粉乳；
(3)取占引发剂总质量30％～60％的引发剂加稀硝酸配置成引发剂溶液，取一定质量的乳化剂加水，配置成质量浓度为2％～6％的乳化剂溶液，将配置的乳化剂溶液与10～20g交联单体混合后用高速剪切机进行预乳化制成预乳液；
(4)将步骤(3)中的引发剂溶液全部加入到步骤(2)中的预糊化淀粉乳中，同时将步骤(3)中的预乳液匀速滴加入步骤(2)中预糊化淀粉乳中，滴加完成后加入再次加入重新配置的引发剂溶液；所述重新配置的引发剂溶液为：将剩余的占引发剂总质量40％～70％的引发剂加稀硝酸配置成引发剂溶液，再次保温，得到交联改性后的混合乳液体系；
(5)将步骤(4)中交联改性后的混合乳液体系降温至30～50℃，调节乳液pH至6～8，即可得到淀粉胶黏剂。
在本发明的一种实施方式中，所述制备方法具体如下：
(1)将淀粉与水配成以淀粉干基计质量比为30％～50％的浓度的淀粉乳，搅拌均匀，备用；
(2)将步骤(1)中的淀粉乳升温至60℃，加入稀释为0.8～1.2mol/L的盐酸酸解2～4h，然后加入氢氧化钠溶液调节pH至3～5；酸解后调节淀粉乳的温度至70～90℃，预糊化30～60min，制成预糊化淀粉乳；
(3)取占引发剂总质量30％～60％的引发剂加稀硝酸配置成引发剂溶液，取一定质量的乳化剂加水，配置成质量浓度为2％～6％的乳化剂溶液，将配置的乳化剂与10～20g交联单体混合后用高速剪切机进行预乳化制成预乳液；
(4)将步骤(3)中的引发剂溶液全部加入到步骤(2)中的预糊化淀粉乳中，同时将步骤(3)中的预乳液匀速滴加入步骤(2)中预糊化淀粉乳中，滴加时间控制在90～120min，滴加完成后加入再次加入重新配置的引发剂溶液，所述重新配置的引发剂溶液为：将剩余的 占引发剂总质量40％～70％的引发剂加稀硝酸配置成引发剂溶液，再次保温90～120min，得到交联改性后的混合乳液体系；
(5)将步骤(4)中交联改性后的混合乳液体系降温至30～50℃，调节乳液pH至6～8，即可得到淀粉胶黏剂。
在本发明的一种实施方式中，所述淀粉为玉米淀粉、蜡质玉米淀粉、木薯淀粉、小麦淀粉、马铃薯淀粉中的任意一种或多种的组合。
在本发明的一种实施方式中，步骤(2)酸解时间为2～4h。
在本发明的一种实施方式中，步骤(2)稀释的盐酸浓度为1mol/L。
在本发明的一种实施方式中，步骤(2)反应温度为80℃。
在本发明的一种实施方式中，步骤(2)预糊化时间30～60min。
在本发明的一种实施方式中，步骤(4)滴加时间控制在90～120min。
在本发明的一种实施方式中，步骤(4)保温时间90～120min。
在本发明的一种实施方式，所述浓盐酸为12mol/L的浓盐酸。
在本发明的一种实施方式中，所述氢氧化钠溶液为浓度为10mol/L的氢氧化钠溶液。
在本发明的一种实施方式中，所述稀硝酸为0.5mol/L的硝酸溶液。
在本发明的一种实施方式中，所述引发剂为硝酸铈盐。
在本发明的一种实施方式中，所述乳化剂为磺基琥珀酸癸基聚氧乙烯(6)醚酯二钠。
在本发明的一种实施方式中，所述交联单体为双丙酮丙烯酰胺、甲基丙烯酸羟丁酯一种或两种的混合。
在本发明的一种实施方式中，所述二元交联剂为己二酸二酰肼、丁二酸二酰肼中的一种或两种混合。
本发明的第三个目的提供上述制得的高温快速固化的淀粉基刨花板胶黏剂应用于刨花板、胶合板、纤维板、木块的热压粘接。
在本发明的一种实施方式中，高温快速固化的淀粉基刨花板胶黏剂应用时将淀粉胶黏剂和二元交联剂复合使用
在本发明的一种实施方式中，所述刨花板的热压粘接的方法是将胶黏剂与刨花均匀混合铺装后，在3-11MPa的热压压力，130℃-180℃的热压温度下压制成形。
[有益效果]：
(1)本发明通过酸解降低淀粉胶黏剂的粘度，保证应用时具有较低的粘度。通过滴加交联单体的方式提高反应效率，选取的交联单体在常温及反应温度下不会发生交联，而在加入二元交联剂后热压时能与二元交联剂发生快速交联，形成大分子网络结构，降低胶黏剂固化 时间的同时保证了较强的耐水性以及胶合强度。
(2)本发明采用的交联单体配合二元交联剂的形式解决了以往淀粉胶黏剂在高温下固化时间长的问题，进一步降低了淀粉胶黏剂的固化时间，降低至70s以内，提高了刨花板的生产效率。
(3)本发明中淀粉胶黏剂制备的刨花板各项性能均符合GB/T 4897-2015中P2型刨花板的性能要求，可在20℃水中浸泡2h不崩解，且吸水厚度膨胀率在7％，耐水性较好，进一步完善了淀粉基胶黏剂的应用。
具体实施方式
下面结合实施方式对本发明进一步说明，应理解的是，这些实施例仅用于例证的目的，并不限制本发明的保护范围。
胶黏剂固化时间的测定：
取30g胶黏剂和0.5g二元交联剂分别添加到烧杯中并充分混合。将烧杯中2.0g的混合物转移到试管中。将搅拌棒插入试管中。将试管和搅拌棒放入装有沸水的烧杯中，立即启动秒表，样品在搅拌下固化。当搅拌棒无法抬起时，秒表立即停止，测得的时间即代表其固化时间，每个样品做三次平行实验，取其平均值。
实施例1
配方(质量/g)：
Figure PCTCN2022135350-appb-000002
工艺流程：
(1)将淀粉与水配成以淀粉干基计质量比为45％的浓度的淀粉乳，搅拌均匀，备用；
(2)将步骤(1)中的淀粉乳升温至60℃，将18g 12mol/L浓盐酸溶液稀释为1mol/L，加入淀粉乳中进行酸解，酸解2.5h，然后加入10mol/L氢氧化钠溶液调节pH至4；调节酸 解后的淀粉乳的温度至80℃，预糊化40min后，反应温度保持80℃不变；
(3)取4g引发剂溶于5g稀硝酸中配成引发剂溶液，取1.96g乳化剂溶于24.8g水配成5％的乳化剂溶液，将15g交联单体全部加入到乳化剂中，并通过高速剪切机进行预乳化制成预乳液。
(4)将步骤(3)中配置的引发剂溶液全部加入步骤(2)中预糊化后的淀粉乳中，同时将预乳液在90min内匀速滴加入步骤(2)中预糊化后的反应体系中，在滴加完成后再次加入4g引发剂溶于5g稀硝酸中配成的引发剂溶液，保温反应90min，得到交联改性后的混合乳液体系。
(5)将步骤(4)中交联改性后的混合乳液体系降温至50℃，调节pH至6，即可得到淀粉胶黏剂。
(6)在使用时将得到的淀粉胶黏剂与二元交联剂预先混合均匀再进行刨花板热压。
本实施例所得到的产品外观是乳白色，有光泽，初粘度较低，符合刨花板使用需求。参考上文“胶黏剂固化时间的测定”的方法测定固化时间，得到的胶黏剂固化时间为60s。
在170℃，11MPa的条件下热压5min，得到的刨花板吸水厚度膨胀率为6％，符合国标P2型刨花板的要求。
实施例2
配方(质量/g)：
Figure PCTCN2022135350-appb-000003
工艺流程：
(1)将淀粉与水配成以淀粉干基计质量比为45％的浓度的淀粉乳，搅拌均匀，备用；
(2)将步骤(1)中的淀粉乳升温至60℃，将18g 12mol/L浓盐酸溶液稀释为1mol/L，加入淀粉乳中进行酸解，酸解1h，然后加入10mol/L氢氧化钠溶液调节pH至4；调节酸解 后的淀粉乳的温度至80℃，预糊化40min后，反应温度保持80℃不变；
(3)取4g引发剂溶于5g稀硝酸中配成引发剂溶液，取1.96g乳化剂溶于24.8g水配成5％的乳化剂溶液将15g交联单体全部加入到乳化剂中，并通过高速剪切机进行预乳化制成预乳液。
(4)将步骤(3)中配置的引发剂溶液全部加入步骤(2)中预糊化后的淀粉乳中，同时将预乳液在90min内匀速滴加入步骤(2)中预糊化后的反应体系中，在滴加完成后再次加入4g引发剂溶于5g稀硝酸中配成的引发剂溶液，保温反应90min，得到交联改性后的混合乳液体系。
(5)将步骤(4)中交联改性后的混合乳液体系降温至50℃，调节pH至6，即可得到淀粉胶黏剂。
(6)在使用时将得到的淀粉胶黏剂与二元交联剂预先混合均匀再进行刨花板热压。
本实施例所得到的产品外观是乳白色，流动性差，粘度较高，不能满足刨花板使用需求，没有应用价值。
实施例3
配方(质量/g)：
Figure PCTCN2022135350-appb-000004
工艺流程：
(1)将淀粉与水配成以淀粉干基计质量比为45％的浓度的淀粉乳，搅拌均匀，备用；
(2)将步骤(1)中的淀粉乳升温至60℃，将18g 12mol/L浓盐酸溶液稀释为1mol/L，加入淀粉乳中进行酸解，酸解4h，然后加入10mol/L氢氧化钠溶液调节pH至4；调节酸解后的淀粉乳的温度至80℃，预糊化40min后，反应温度保持80℃不变；
(3)取4g引发剂溶于5g稀硝酸中配成引发剂溶液，取1.96g乳化剂溶于24.8g水配成 5％的乳化剂溶液，将15g交联单体全部加入到乳化剂中，并通过高速剪切机进行预乳化制成预乳液。
(4)将步骤(3)中配置的引发剂溶液全部加入步骤(2)中预糊化后的淀粉乳中，同时将预乳液在90min内匀速滴加入步骤(2)中预糊化后的反应体系中，在滴加完成后加入4g引发剂溶于5g稀硝酸中配成的引发剂溶液，保温反应90min，得到交联改性后的混合乳液体系。
(5)将步骤(4)中交联改性后的混合乳液体系降温至50℃，调节pH至6，即可得到淀粉胶黏剂。
(6)在使用时将得到的淀粉胶黏剂与二元交联剂预先混合均匀再进行刨花板热压。
本实施例所得到的产品外观是乳白色，有光泽，初粘度很低，参考上文“胶黏剂固化时间的测定”的方法测定固化时间，得到的胶黏剂固化时间为140s，放置一段时间以后出现分层现象，无应用价值。
通过实施例1、2、3来证明酸解时间对胶黏剂粘度的影响，由以上数据可知，酸解时间过短，酸解效果差，导致胶黏剂粘度过高，流动性差，不能满足刨花板使用需求，而酸解时间过长，淀粉过度崩解，反应效果差，固化时间变长，无法达到快速固化的效果。
实施例4
配方(质量/g)：
Figure PCTCN2022135350-appb-000005
工艺流程：
(1)将淀粉与水配成以淀粉干基计质量比为45％的浓度的淀粉乳，搅拌均匀，备用；
(2)将步骤(1)中的淀粉乳升温至60℃，将18g 12mol/L浓盐酸溶液稀释为1mol/L，加入淀粉乳中进行酸解，酸解2.5h，然后加入10mol/L氢氧化钠溶液调节pH至4；调节酸 解后的淀粉乳的温度至80℃，预糊化40min后，反应温度保持80℃不变；
(3)取4g引发剂溶于5g稀硝酸中配成引发剂溶液，取1.96g乳化剂溶于24.8g水配成5％的乳化剂溶液，将15g交联单体全部加入到乳化剂中，并通过高速剪切机进行预乳化制成预乳液。
(4)将步骤(3)中配置的引发剂溶液全部加入步骤(2)中预糊化后的淀粉乳中，同时将预乳液在90min内匀速滴加入步骤(2)中预糊化后的反应体系中，在滴加完成后再次加入4g引发剂溶于5g稀硝酸中配成的引发剂溶液，保温反应90min，得到交联改性后的混合乳液体系。
(5)将步骤(4)中交联改性后的混合乳液体系降温至50℃，调节pH至6，即可得到淀粉胶黏剂。
(6)在使用时将得到的淀粉胶黏剂与二元交联剂预先混合均匀再进行刨花板热压。
本实施例所得到的产品外观是乳白色，有光泽，初粘度较低，符合刨花板使用需求。参考上文“胶黏剂固化时间的测定”的方法测定固化时间，得到的胶黏剂固化时间为150s。
在170℃，11MPa的条件下进行热压5min，，得到的刨花板吸水厚度膨胀率为15％，不符合国标P2型刨花板的要求。
通过实施例1、4来证明交联单体对胶黏剂固化时间的影响，由以上数据经过显著性分析可知，使用双丙酮丙烯酰胺制备的胶黏剂与己二酸二酰肼配合使用的固化时间较短，能满足刨花板胶黏剂快速固化的要求，而使用N-羟乙基丙烯酰胺制备的胶黏剂与己二酸二酰肼配合使用的固化时间较长，固化效率低，无法满足刨花板胶黏剂的需求。
实施例5
配方(质量/g)：
Figure PCTCN2022135350-appb-000006
工艺流程：
(1)将淀粉与水配成以淀粉干基计质量比为45％的浓度的淀粉乳，搅拌均匀，备用；
(2)将步骤(1)中的淀粉乳升温至60℃，将18g 12mol/L浓盐酸溶液稀释为1mol/L，加入淀粉乳中进行酸解，酸解2.5h，然后加入10mol/L氢氧化钠溶液调节pH至4；调节酸解后的淀粉乳的温度至80℃，预糊化40min后，反应温度保持80℃不变；
(3)取4g引发剂溶于5g稀硝酸配成引发剂溶液，取1.96g乳化剂溶于24.8g水配成5％的乳化剂溶液，将15g交联单体全部加入到乳化剂中，并通过高速剪切机进行预乳化制成预乳液。
(4)将步骤(3)中配置的引发剂溶液全部加入步骤(2)中预糊化后的淀粉乳中，同时将预乳液在90min内匀速滴加入步骤(2)中预糊化后的反应体系中，在滴加完成后再次加入4g引发剂溶于5g稀硝酸中配成的引发剂溶液，保温反应90min，得到交联改性后的混合乳液体系。
(5)将步骤(4)中交联改性后的混合乳液体系降温至50℃，调节pH至6，即可得到淀粉胶黏剂。
本实施例所得到的产品外观是乳白色，有光泽，初粘度较低，符合刨花板使用需求。参考上文“胶黏剂固化时间的测定”的方法不添加二元交联剂测定固化时间，得到的胶黏剂无法固化，无法使用。
实施例6
配方(质量/g)：
Figure PCTCN2022135350-appb-000007
工艺流程：
(1)将淀粉与水配成以淀粉干基计质量比为45％的浓度的淀粉乳，搅拌均匀，备用；
(2)将步骤(1)中的淀粉乳升温至60℃，将18g 12mol/L浓盐酸溶液稀释为1mol/L， 加入淀粉乳中进行酸解，酸解2.5h，然后加入10mol/L氢氧化钠溶液调节pH至4；调节酸解后的淀粉乳的温度至80℃，预糊化40min后，反应温度保持80℃不变；
(3)取4g引发剂溶于5g稀硝酸配成引发剂溶液，取1.96g乳化剂溶于24.8g水配成5％的乳化剂溶液，将15g交联单体全部加入到乳化剂中，并通过高速剪切机进行预乳化制成预乳液。
(4)将步骤(3)中配置的引发剂溶液全部加入步骤(2)中预糊化后的淀粉乳中，同时将预乳液在90min内匀速滴加入步骤(2)中预糊化后的反应体系中，在滴加完成后再次加入4g引发剂溶于5g稀硝酸中配成的引发剂溶液，保温反应90min，得到交联改性后的混合乳液体系。
(5)将步骤(4)中交联改性后的混合乳液体系降温至50℃，调节pH至6，即可得到淀粉胶黏剂。
(6)在使用时将得到的淀粉胶黏剂与二元交联剂预先混合均匀再进行刨花板热压。
本实施例所得到的产品外观是乳白色，有光泽，初粘度较低，符合刨花板使用需求。参考上文“胶黏剂固化时间的测定”的方法测定固化时间，得到的胶黏剂无法固化。
通过实施例1、5、6来证明二元交联剂对胶黏剂固化时间的影响，由以上数据经过显著性分析可知，在添加了二元交联剂以后胶黏剂能快速固化，而不添加二元交联剂或添加其他的二元交联剂的胶黏剂完全无法固化，无法在刨花板中应用。
实施例7
配213方(质量/g)：
Figure PCTCN2022135350-appb-000008
工艺流程：
(1)将淀粉与水配成以淀粉干基计质量比为45％的浓度的淀粉乳，搅拌均匀，备用；
(2)将步骤(1)中的淀粉乳升温至60℃，将18g 12mol/L浓盐酸溶液稀释为1mol/L，加入淀粉乳中进行酸解，酸解2.5h，然后加入10mol/L氢氧化钠溶液调节pH至4；调节酸解后的淀粉乳的温度至80℃，预糊化40min后，降温至70℃进行反应；
(3)取4g引发剂溶于5g稀硝酸配成引发剂溶液，取1.96g乳化剂溶于24.8g水配成5％的乳化剂溶液，将15g交联单体全部加入到乳化剂中，并通过高速剪切机进行预乳化制成预乳液。
(4)将步骤(3)中配置的引发剂溶液全部加入步骤(2)中预糊化后的淀粉乳中，同时将预乳液在90min内匀速滴加入步骤(2)中预糊化后的反应体系中，在滴加完成后再次加入4g引发剂溶于5g稀硝酸中配成的引发剂溶液，保温反应90min，得到交联改性后的混合乳液体系。
(5)将步骤(4)中交联改性后的混合乳液体系降温至50℃，调节pH至6，即可得到淀粉胶黏剂。
(6)在使用时将得到的淀粉胶黏剂与二元交联剂预先混合均匀再进行刨花板热压。
本实施例所得到的产品外观是乳白色，有光泽，初粘度较低，符合刨花板使用需求。参考上文“胶黏剂固化时间的测定”的方法测定固化时间，得到的胶黏剂固化时间为90s。
在170℃，11MPa的条件下进行热压5min，得到的刨花板吸水厚度膨胀率为10％，超过了8％，不符合国标P2型刨花板的要求。
实施例8
配方(质量/g)：
Figure PCTCN2022135350-appb-000009
工艺流程：
(1)将淀粉与水配成以淀粉干基计质量比为45％的浓度的淀粉乳，搅拌均匀，备用；
(2)将步骤(1)中的淀粉乳升温至60℃，将24g 12mol/L浓盐酸溶液稀释为1.5mol/L，加入淀粉乳中进行酸解，酸解2.5h，然后加入10mol/L氢氧化钠溶液调节pH至4；调节酸解后的淀粉乳的温度至80℃，预糊化40min后，反应温度保持80℃不变；
(3)取4g引发剂溶于5g稀硝酸配成引发剂溶液，取1.96g乳化剂溶于24.8g水配成5％的乳化剂溶液，将15g交联单体全部加入到乳化剂中，并通过高速剪切机进行预乳化制成预乳液。
(4)将步骤(3)中配置的引发剂溶液全部加入步骤(2)中预糊化后的淀粉乳中，同时将预乳液在90min内匀速滴加入步骤(2)中预糊化后的反应体系中，在滴加完成后再次加入4g引发剂溶于5g稀硝酸中配成的引发剂溶液，保温反应90min，得到交联改性后的混合乳液体系。
(5)将步骤(4)中交联改性后的混合乳液体系降温至50℃，调节pH至6，即可得到淀粉胶黏剂。
(6)在使用时将得到的淀粉胶黏剂与二元交联剂预先混合均匀再进行刨花板热压。
本实施例所得到的产品外观是乳白色，有光泽，初粘度较低，符合刨花板使用需求。参考上文“胶黏剂固化时间的测定”的方法测定固化时间，得到的胶黏剂固化时间为100s，且放置一段时间后出现分层现象，无应用价值。
通过实施例1、7、8来证明反应条件对胶黏剂固化时间的影响，由以上数据经过显著性分析可知，反应温度过低会影响单体的接枝效率，导致固化时间的延长，而酸解浓度过高会导致过度崩解降低反应效率，同时还会出现分层的现象。因此最优的反应条件是盐酸浓度为1mol/L，反应温度为80℃。
实施例9
配方(质量/g)：
Figure PCTCN2022135350-appb-000010
Figure PCTCN2022135350-appb-000011
工艺流程：
(1)将淀粉与水配成以淀粉干基计质量比为45％的浓度的淀粉乳，搅拌均匀，备用；
(2)将步骤(1)中的淀粉乳升温至60℃，将18g 12mol/L浓盐酸溶液稀释为1mol/L，加入淀粉乳中进行酸解，酸解2.5h，然后加入10mol/L氢氧化钠溶液调节pH至4；调节酸解后的淀粉乳的温度至80℃，预糊化40min后，反应温度保持80℃不变；
(3)取4g引发剂溶于5g稀硝酸配成引发剂溶液，取1.96g乳化剂溶于24.8g水配成5％的乳化剂溶液，将15g交联单体全部加入到乳化剂中，并通过高速剪切机进行预乳化制成预乳液。
(4)将步骤(3)中配置的引发剂溶液全部加入步骤(2)中预糊化后的淀粉乳中，同时将预乳液在90min内匀速滴加入步骤(2)中预糊化后的反应体系中，在滴加完成后再次加入4g引发剂溶于5g稀硝酸中配成的引发剂溶液，保温反应90min，得到交联改性后的混合乳液体系。
(5)将步骤(4)中交联改性后的混合乳液体系降温至50℃，调节pH至6，即可得到淀粉胶黏剂。
(6)在使用时将得到的淀粉胶黏剂与二元交联剂预先混合均匀再进行刨花板热压。
本实施例所得到的产品外观是乳白色，有光泽，初粘度较低，符合刨花板使用需求。参考上文“胶黏剂固化时间的测定”的方法测定固化时间，得到的胶黏剂固化时间为65s。
在170℃，11MPa的条件下热压5min，得到的刨花板吸水厚度膨胀率为7％，符合国标P2型刨花板的要求。
实施例10
配方(质量/g)：
Figure PCTCN2022135350-appb-000012
工艺流程：
(1)将淀粉与水配成以淀粉干基计质量比为45％的浓度的淀粉乳，搅拌均匀，备用；
(2)将步骤(1)中的淀粉乳升温至60℃，将18g 12mol/L浓盐酸溶液稀释为1mol/L，加入淀粉乳中进行酸解，酸解2h，然后加入10mol/L氢氧化钠溶液调节pH至4；调节酸解后的淀粉乳的温度至80℃，预糊化30min后，反应温度保持80℃不变；
(3)取0.91g引发剂溶于35g水配成引发剂溶液，取1.96g乳化剂溶于24.8g水配成5％的乳化剂溶液。
(4)将步骤(3)中配置的溶液全部加入步骤(2)中预糊化后的淀粉乳中，同时将交联单体在105min内匀速滴加入步骤(2)中预糊化后的反应体系中，在滴加完成后加入10g质量浓度为3％的引发剂溶液，保温反应105min，得到交联改性后的混合乳液体系。
(5)将步骤(4)中交联改性后的混合乳液体系降温至50℃，调节pH至5，即可得到淀粉胶黏剂。
(6)在使用时将得到的淀粉胶黏剂与二元交联剂预先混合均匀再进行刨花板热压。
本实施例所得到的产品外观是乳白色，有光泽，初粘度较低，符合刨花板使用需求。参考上文“胶黏剂固化时间的测定”的方法测定固化时间，得到的胶黏剂固化时间为120s。
在170℃，11MPa的条件下热压5min，得到的刨花板吸水厚度膨胀率为10％，不符合国标P2型刨花板的要求。
实施例11
配方(质量/g)：
Figure PCTCN2022135350-appb-000013
工艺流程：
(1)将淀粉与水配成以淀粉干基计质量比为45％的浓度的淀粉乳，搅拌均匀，备用；
(2)将步骤(1)中的淀粉乳升温至60℃，将18g 12mol/L浓盐酸溶液稀释为1mol/L，加入淀粉乳中进行酸解，酸解2h，然后加入10mol/L氢氧化钠溶液调节pH至4；调节酸解 后的淀粉乳的温度至80℃，预糊化30min后，反应温度保持80℃不变；
(3)取0.91g引发剂溶于35g水配成引发剂溶液，取1.96g乳化剂溶于24.8g水配成5％的乳化剂溶液。
(4)将步骤(3)中配置的溶液全部加入步骤(2)中预糊化后的淀粉乳中，同时将交联单体在105min内匀速滴加入步骤(2)中预糊化后的反应体系中，在滴加完成后加入10g质量浓度为3％的引发剂溶液，保温反应105min，得到交联改性后的混合乳液体系。
(5)将步骤(4)中交联改性后的混合乳液体系降温至50℃，调节pH至5，即可得到淀粉胶黏剂。
(6)在使用时将得到的淀粉胶黏剂与二元交联剂预先混合均匀再进行刨花板热压。
本实施例所得到的产品外观是乳白色，有光泽，初粘度较低，符合刨花板使用需求。参考上文“胶黏剂固化时间的测定”的方法测定固化时间，得到的胶黏剂固化时间为130s。
在170℃，11MPa的条件下热压5min，得到的刨花板吸水厚度膨胀率为12％，不符合国标P2型刨花板的要求。
实施例12
配方(质量/g)：
Figure PCTCN2022135350-appb-000014
工艺流程：
(1)将淀粉与水配成以淀粉干基计质量比为45％的浓度的淀粉乳，搅拌均匀，备用；
(2)将步骤(1)中的淀粉乳升温至60℃，将18g 12mol/L浓盐酸溶液稀释为1mol/L，加入淀粉乳中进行酸解，酸解2.5h，然后加入10mol/L氢氧化钠溶液调节pH至4；调节酸解后的淀粉乳的温度至80℃，预糊化40min后，反应温度保持80℃不变；
(3)取4g引发剂溶于5g稀硝酸中配成引发剂溶液，取1.96g乳化剂溶于24.8g水配成5％的乳化剂溶液，将15g交联单体全部加入到乳化剂中，并通过高速剪切机进行预乳化制成 预乳液。
(4)将步骤(3)中配置的引发剂溶液全部加入步骤(2)中预糊化后的淀粉乳中，同时将预乳液在90min内匀速滴加入步骤(2)中预糊化后的反应体系中，在滴加完成后再次加入4g引发剂溶于5g稀硝酸中配成的引发剂溶液，保温反应90min，得到交联改性后的混合乳液体系。
(5)将步骤(4)中交联改性后的混合乳液体系降温至50℃，调节pH至6，即可得到淀粉胶黏剂。
(6)在使用时将得到的淀粉胶黏剂与二元交联剂预先混合均匀再进行刨花板热压。
本实施例所得到的产品外观是乳白色，有光泽，初粘度较低，符合刨花板使用需求。参考上文“胶黏剂固化时间的测定”的方法测定固化时间，得到的胶黏剂固化时间为110s。
在170℃，11MPa的条件下热压5min，得到的刨花板吸水厚度膨胀率为9％，不符合国标P2型刨花板的要求。
虽然本发明已以较佳实施例公开如上，但其并非用以限定本发明，任何熟悉此技术的人，在不脱离本发明的精神和范围内，都可做各种的改动与修饰，因此本发明的保护范围应该以权利要求书所界定的为准。

Claims (10)

  1. 一种高温快速固化的淀粉基刨花板胶黏剂，所述的淀粉基刨花板胶黏剂的配方，以质量份数计包括：
    Figure PCTCN2022135350-appb-100001
    所述配方中引发剂为硝酸铈盐。
  2. 根据权利要求1所述淀粉基刨花板胶黏剂，其特征在于，所述配方中淀粉为玉米淀粉、蜡质玉米淀粉、木薯淀粉、小麦淀粉、马铃薯淀粉中的任意一种或多种的组合。
  3. 根据权利要求1所述淀粉基刨花板胶黏剂，其特征在于，所述配方中乳化剂为磺基琥珀酸癸基聚氧乙烯(6)醚酯二钠。
  4. 根据权利要求1所述淀粉基刨花板胶黏剂，其特征在于，所述配方中交联单体为双丙酮丙烯酰胺、甲基丙烯酸羟丁酯一种或两种的混合。
  5. 根据权利要求1所述淀粉基刨花板胶黏剂，其特征在于，所述配方中二元交联剂为己二酸二酰肼、丁二酸二酰肼中的一种或两种混合。
  6. 根据权利要求1-5所述淀粉基刨花板胶黏剂，其特征在于，具体制备方法如下：
    (1)将淀粉与水配成以淀粉干基计质量比为30％～50％的浓度的淀粉乳，搅拌均匀，备用；
    (2)将步骤(1)中的淀粉乳升温至60℃，加入稀释为0.8～1.2mol/L的盐酸酸解，然后加入氢氧化钠溶液调节pH至3～5；酸解后调节淀粉乳的温度至70～90℃，预糊化制成预糊化淀粉乳；
    (3)取占引发剂总质量30％～60％的引发剂加稀硝酸配置成引发剂溶液，取一定质量的乳化剂加水，配置成质量浓度为2％～6％的乳化剂溶液，将配置的乳化剂溶液与10～20g交联单体混合后用高速剪切机进行预乳化制成预乳液；
    (4)将步骤(3)中的引发剂溶液全部加入到步骤(2)中的预糊化淀粉乳中，同时将步骤(3)中的预乳液匀速滴加入步骤(2)中预糊化淀粉乳中，滴加完成后加入再次加入重新 配置的引发剂溶液；所述重新配置的引发剂溶液为：将剩余的占引发剂总质量40％～70％的引发剂加稀硝酸配置成引发剂溶液，再次保温，得到交联改性后的混合乳液体系；
    (5)将步骤(4)中交联改性后的混合乳液体系降温至30～50℃，调节乳液pH至6～8，与二元交联剂混合均匀即可得到淀粉胶黏剂。
  7. 根据权利要求6所述淀粉基刨花板胶黏剂，其特征在于，步骤(2)酸解时间为2～4h。
  8. 根据权利要求6所述淀粉基刨花板胶黏剂，其特征在于，步骤(2)预糊化时间30～60min。
  9. 根据权利要求6所述淀粉基刨花板胶黏剂，其特征在于，步骤(4)滴加时间控制在90～120min。
  10. 权利要求1-9任一所述的高温快速固化的淀粉基刨花板胶黏剂在刨花板、胶合板、纤维板、木块的热压粘接中的应用。
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