CN109536126A - A kind of resistance to boiling water vegetable protein base based Wood Adhesives and its preparation method and application - Google Patents
A kind of resistance to boiling water vegetable protein base based Wood Adhesives and its preparation method and application Download PDFInfo
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 114
- 239000000853 adhesive Substances 0.000 title claims abstract description 96
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 96
- 239000002023 wood Substances 0.000 title claims abstract description 66
- 108010082495 Dietary Plant Proteins Proteins 0.000 title claims abstract description 60
- 238000009835 boiling Methods 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000004814 polyurethane Substances 0.000 claims abstract description 32
- 229920002635 polyurethane Polymers 0.000 claims abstract description 32
- 239000003822 epoxy resin Substances 0.000 claims abstract description 26
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 26
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 21
- 235000012054 meals Nutrition 0.000 claims description 33
- 239000000843 powder Substances 0.000 claims description 12
- 239000002612 dispersion medium Substances 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 238000004132 cross linking Methods 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 6
- 150000003077 polyols Chemical class 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 239000004970 Chain extender Substances 0.000 claims description 4
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical group C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 4
- 238000000265 homogenisation Methods 0.000 claims description 3
- 229920005862 polyol Polymers 0.000 claims description 3
- 241000208140 Acer Species 0.000 claims description 2
- 235000017060 Arachis glabrata Nutrition 0.000 claims description 2
- 244000105624 Arachis hypogaea Species 0.000 claims description 2
- 235000010777 Arachis hypogaea Nutrition 0.000 claims description 2
- 235000018262 Arachis monticola Nutrition 0.000 claims description 2
- 240000001548 Camellia japonica Species 0.000 claims description 2
- 244000025254 Cannabis sativa Species 0.000 claims description 2
- 235000012766 Cannabis sativa ssp. sativa var. sativa Nutrition 0.000 claims description 2
- 235000012765 Cannabis sativa ssp. sativa var. spontanea Nutrition 0.000 claims description 2
- 235000019779 Rapeseed Meal Nutrition 0.000 claims description 2
- 235000004443 Ricinus communis Nutrition 0.000 claims description 2
- 240000008042 Zea mays Species 0.000 claims description 2
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 claims description 2
- 235000002017 Zea mays subsp mays Nutrition 0.000 claims description 2
- 230000009471 action Effects 0.000 claims description 2
- 235000009120 camo Nutrition 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 claims description 2
- 235000005607 chanvre indien Nutrition 0.000 claims description 2
- 235000018597 common camellia Nutrition 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 235000005822 corn Nutrition 0.000 claims description 2
- 235000012343 cottonseed oil Nutrition 0.000 claims description 2
- 239000011487 hemp Substances 0.000 claims description 2
- 239000012948 isocyanate Substances 0.000 claims description 2
- 150000002513 isocyanates Chemical class 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- 239000002609 medium Substances 0.000 claims description 2
- 230000003472 neutralizing effect Effects 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 235000020232 peanut Nutrition 0.000 claims description 2
- 238000012545 processing Methods 0.000 claims description 2
- 239000004456 rapeseed meal Substances 0.000 claims description 2
- 235000020238 sunflower seed Nutrition 0.000 claims description 2
- 238000010792 warming Methods 0.000 claims description 2
- 235000013339 cereals Nutrition 0.000 claims 1
- 235000013312 flour Nutrition 0.000 claims 1
- 239000007787 solid Substances 0.000 abstract description 4
- 230000009257 reactivity Effects 0.000 abstract description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 12
- 239000011120 plywood Substances 0.000 description 12
- 238000000034 method Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 6
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 4
- 238000007731 hot pressing Methods 0.000 description 4
- 108090000623 proteins and genes Proteins 0.000 description 4
- 102000004169 proteins and genes Human genes 0.000 description 4
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 239000003292 glue Substances 0.000 description 3
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- 239000000126 substance Substances 0.000 description 3
- 235000013311 vegetables Nutrition 0.000 description 3
- 230000032683 aging Effects 0.000 description 2
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 2
- -1 polytetramethylene Polymers 0.000 description 2
- 230000036316 preload Effects 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 241000219000 Populus Species 0.000 description 1
- 108010073771 Soybean Proteins Proteins 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
- GZCGUPFRVQAUEE-SLPGGIOYSA-N aldehydo-D-glucose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O GZCGUPFRVQAUEE-SLPGGIOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000009775 high-speed stirring Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 229940001941 soy protein Drugs 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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- 231100000331 toxic Toxicity 0.000 description 1
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Classifications
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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
- C09J189/00—Adhesives based on proteins; Adhesives based on 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
- C09J11/08—Macromolecular additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
本发明涉及一种耐沸水植物蛋白基木材胶黏剂及其制备方法和应用。所述植物蛋白基木材胶黏剂含有水性聚氨酯粘合剂、水性环氧树脂交联剂；其中，所述水性聚氨酯粘合剂和水性环氧树脂交联剂质量之和占耐沸水植物蛋白基木材胶黏剂总质量的5‑15％；优选7‑11％；进一步优选10‑11％。本发明所述植物蛋白基木材胶黏剂具有固含量高，制备工艺简单、反应活性强，胶接强度高等优点，解决了普通植物蛋白基胶黏剂耐水性差，尤其是耐沸水性差的问题，能够满足户外人造板用胶黏剂的耐水强度要求。The invention relates to a boiling water-resistant vegetable protein-based wood adhesive and a preparation method and application thereof. The vegetable protein-based wood adhesive contains a water-based polyurethane adhesive and a water-based epoxy resin cross-linking agent; wherein, the sum of the mass of the water-based polyurethane adhesive and the water-based epoxy resin cross-linking agent accounts for the boiling water-resistant vegetable protein-based adhesive. 5-15% of the total mass of the wood adhesive; preferably 7-11%; more preferably 10-11%. The vegetable protein-based wood adhesive of the invention has the advantages of high solid content, simple preparation process, strong reactivity and high bonding strength, and solves the problem of poor water resistance, especially poor boiling water resistance, of common vegetable protein-based adhesives. It can meet the water resistance strength requirements of adhesives for outdoor wood-based panels.
Description
技术领域technical field
本发明涉及一种胶黏剂，特别涉及一种人造板用耐沸水植物蛋白基木材胶黏剂及其制备方法和应用。The invention relates to an adhesive, in particular to a boiling water-resistant vegetable protein-based wood adhesive for wood-based panels and a preparation method and application thereof.
背景技术Background technique
我国是世界人造板生产和消费大国，人造板总产量、胶合板产量、家具产量、木质地板产量连续多年位居世界第一位。人造板行业的持续快速发展，不断增加木材工业胶黏剂的需求。my country is the world's largest producer and consumer of wood-based panels. The total output of wood-based panels, plywood production, furniture production, and wooden floor production ranks first in the world for many years. The sustained and rapid development of the wood-based panel industry has continuously increased the demand for adhesives in the wood industry.
目前，三醛类胶黏剂(脲醛树脂、酚醛树脂和三聚氰胺树脂)用量仍在木材胶黏剂用量中占主导地位，而其在生产及使用过程中释放的有毒有害物质以及化石资源的本质不断敦促人们对于环保型胶黏剂的开发。利用大宗农产品等可再生资源生产环保型的绿色化工产品为环保木材胶黏剂的开发带来了新的机遇。At present, the amount of trialdehyde adhesives (urea-formaldehyde resin, phenolic resin and melamine resin) is still dominant in the amount of wood adhesives, while the toxic and harmful substances released during production and use and the nature of fossil resources continue to Urge people to develop environmentally friendly adhesives. The use of renewable resources such as bulk agricultural products to produce environmentally friendly green chemical products has brought new opportunities for the development of environmentally friendly wood adhesives.
现有植物蛋白基胶黏剂普遍存在粘度大、固化速度慢、固体含量低、成本较高、耐水性差、施工困难等问题，尤其是耐沸水性差问题突出，阻碍了植物蛋白基胶黏剂进一步开发与推广应用。Existing vegetable protein-based adhesives generally have problems such as high viscosity, slow curing speed, low solid content, high cost, poor water resistance, and difficult construction, especially the problem of poor boiling water resistance, which hinders the further development of vegetable protein-based adhesives. Develop and promote applications.
发明内容SUMMARY OF THE INVENTION
为解决上述技术问题，本发明提供一种人造板用耐沸水植物蛋白基木材胶黏剂。本发明引入水性聚氨酯粘合剂、水性环氧树脂交联剂，于蛋白基质间构建复合交联体系，能够在大大提高固化产物交联密度和耐水性能的同时，显著提高蛋白胶黏剂的固体含量。实验结果表明，改性胶黏剂制备的胶合板胶合强度完全能够满足国标中II类胶合板要求。In order to solve the above technical problems, the present invention provides a boiling water-resistant vegetable protein-based wood adhesive for wood-based panels. The invention introduces water-based polyurethane adhesive and water-based epoxy resin cross-linking agent to build a composite cross-linking system between protein substrates, which can greatly improve the cross-linking density and water resistance of the cured product, and at the same time significantly improve the solid content of the protein adhesive. content. The experimental results show that the bonding strength of the plywood prepared by the modified adhesive can fully meet the requirements of class II plywood in the national standard.
本发明的技术方案如下。The technical solution of the present invention is as follows.
一种耐沸水植物蛋白基木材胶黏剂，含有水性聚氨酯粘合剂、水性环氧树脂交联剂；A boiling water-resistant vegetable protein-based wood adhesive, comprising a water-based polyurethane adhesive and a water-based epoxy resin cross-linking agent;
其中，所述水性聚氨酯粘合剂和水性环氧树脂交联剂质量之和占耐沸水植物蛋白基木材胶黏剂总质量的5-15％；优选7-11％；进一步优选10-11％。Wherein, the sum of the mass of the water-based polyurethane adhesive and the water-based epoxy resin cross-linking agent accounts for 5-15% of the total mass of the boiling water-resistant vegetable protein-based wood adhesive; preferably 7-11%; more preferably 10-11% .
所述水性聚氨酯粘合剂与水性环氧树脂交联剂的质量比为：(1-25)：(1-20)；优选(2-20)：(2-15)；进一步优选(3-4)：(1-2)：或优选(2-3)：1。The mass ratio of the water-based polyurethane adhesive to the water-based epoxy resin crosslinking agent is: (1-25): (1-20); preferably (2-20): (2-15); more preferably (3- 4): (1-2): or preferably (2-3): 1.
其中，所述水性聚氨酯粘合剂可选自市售的本领域技术人员所掌握的常规水性聚氨酯粘合剂，在本发明中优选采用如下方法自制。Wherein, the water-based polyurethane adhesive can be selected from commercially available conventional water-based polyurethane adhesives mastered by those skilled in the art, and in the present invention, the following method is preferably used for self-preparation.
所述水性聚氨酯粘合剂的自制方法如下：The self-made method of described water-based polyurethane adhesive is as follows:
(1)在氮气保护、催化剂作用下，异氰酸酯与多元醇于70-80℃反应2-3小时；(1) Under nitrogen protection and catalyst action, isocyanate and polyol react at 70-80°C for 2-3 hours;
(2)升温至80-90℃，加入含有亲水基团扩链剂，继续反应1-1.5小时；(2) warming up to 80-90°C, adding a chain extender containing a hydrophilic group, and continuing to react for 1-1.5 hours;
(3)降温至70℃，加入多元醇扩链剂，继续反应5-6小时；(3) cooling to 70°C, adding polyol chain extender, and continuing to react for 5-6 hours;
(4)常温下，加入中和剂反应0.5-1小时，高速搅拌乳化后，出料，制得水性聚氨酯粘合剂；(4) at normal temperature, add neutralizing agent to react for 0.5-1 hour, after high-speed stirring and emulsification, discharge material to obtain water-based polyurethane adhesive;
其中，所述多元醇选自聚四亚甲基乙二醇醚(PTMG)、MDI或HDI、1,4丁二醇等。Wherein, the polyol is selected from polytetramethylene glycol ether (PTMG), MDI or HDI, 1,4 butanediol and the like.
其中，所述水性环氧树脂交联剂选自缩水甘油醚、PAE(聚酰胺环氧氯丙烷树脂)等。Wherein, the water-based epoxy resin crosslinking agent is selected from glycidyl ether, PAE (polyamide epichlorohydrin resin) and the like.
作为本发明优选实施方式之一，所述耐沸水植物蛋白基木材胶黏剂，包括如下重量份的组分：植物蛋白粕(粉)20-40份、水性聚氨酯粘合剂1-25份、水性环氧树脂交联剂1-20份，分散介质60-80份。As one of the preferred embodiments of the present invention, the boiling water-resistant vegetable protein-based wood adhesive includes the following components by weight: 20-40 parts of vegetable protein meal (powder), 1-25 parts of water-based polyurethane adhesive, 1-20 parts of water-based epoxy resin cross-linking agent, 60-80 parts of dispersion medium.
优选地，所述耐沸水植物蛋白基木材胶黏剂，包括如下重量份的组分：植物蛋白粕(粉)25-35份、水性聚氨酯粘合剂2-20份、水性环氧树脂交联剂2-15份、分散介质65-75份。Preferably, the boiling water-resistant vegetable protein-based wood adhesive comprises the following components by weight: 25-35 parts of vegetable protein meal (powder), 2-20 parts of water-based polyurethane adhesive, water-based epoxy resin cross-linking 2-15 parts of agent, 65-75 parts of dispersion medium.
进一步优选，所述耐沸水植物蛋白基木材胶黏剂，包括如下重量份的组分：植物蛋白粕(粉)25-35份、水性聚氨酯粘合剂6-8份、水性环氧树脂交联剂2-4份、分散介质65-75份。Further preferably, the boiling water-resistant vegetable protein-based wood adhesive includes the following components by weight: 25-35 parts of vegetable protein meal (powder), 6-8 parts of water-based polyurethane adhesive, water-based epoxy resin cross-linking 2-4 parts of agent, 65-75 parts of dispersion medium.
更进一步优选，所述耐沸水植物蛋白基木材胶黏剂，包括如下重量份的组分：植物蛋白粕(粉)32-35份、水性聚氨酯粘合剂6-8份、水性环氧树脂交联剂2-4份、分散介质65-70份。More preferably, the boiling water-resistant vegetable protein-based wood adhesive includes the following components in parts by weight: 32-35 parts of vegetable protein meal (powder), 6-8 parts of water-based polyurethane adhesive, and water-based epoxy resin adhesive. 2-4 parts of joint agent, 65-70 parts of dispersion medium.
其中，所述植物蛋白粕(粉)选自葵花籽粕粉、麻枫树粕粉、花生粕粉、油茶子粕、蓖麻粕、棉籽粕粉、菜子粕、玉米胚芽粕、酒精糟中的一种或几种。Wherein, the vegetable protein meal (powder) is selected from sunflower seed meal, hemp maple meal, peanut meal, camellia seed meal, castor meal, cottonseed meal, rapeseed meal, corn germ meal, and distillers grains. one or more.
其中，所述分散介质为软化水。Wherein, the dispersion medium is demineralized water.
本发明还提供上述耐沸水植物蛋白基木材胶黏剂的制备方法，包括：The present invention also provides the preparation method of the above-mentioned boiling water-resistant vegetable protein-based wood adhesive, comprising:
S1、将植物蛋白粕(粉)加入分散介质中，搅拌均匀；S1. Add vegetable protein meal (powder) into the dispersing medium and stir evenly;
S2、按比例加入水性聚氨酯粘合剂，搅拌均匀；S2. Add water-based polyurethane adhesive in proportion and stir evenly;
S3、按配比加入水性环氧树脂交联剂，均质处理，得到耐沸水植物蛋白基木材胶黏剂。S3, adding a water-based epoxy resin cross-linking agent according to the proportion, and homogenizing treatment to obtain a boiling water-resistant vegetable protein-based wood adhesive.
上述S3中，均质处理的压力为20-40MPa。In the above S3, the pressure of the homogenization treatment is 20-40MPa.
本发明还提供上述耐沸水植物蛋白基木材胶黏剂在木材加工中的应用；优选所述木材为人造板。The present invention also provides the application of the above-mentioned boiling water-resistant vegetable protein-based wood adhesive in wood processing; preferably, the wood is an artificial board.
本发明还提供一种木材加工品，含有上述耐沸水植物蛋白基木材胶黏剂。The present invention also provides a wood processed product, which contains the above-mentioned boiling water-resistant vegetable protein-based wood adhesive.
本发明所述技术方案取得的有益效果如下：The beneficial effects obtained by the technical solution of the present invention are as follows:
本发明利用水性聚氨酯粘合剂具有反应活性高、结构可调节及强度性能优异的优点，使其与水性环氧树脂交联剂复配，并于蛋白基质间构建致密的分子交联网络，从而大大提高固化产物交联密度和耐水性能，同时还显著提高植物蛋白基胶黏剂的固体含量。实验结果表明，采用本发明所述的胶黏剂制备的胶合板的胶合强度完全能够满足国标中II类胶合板要求。The invention utilizes the advantages of high reactivity, adjustable structure and excellent strength properties of the water-based polyurethane adhesive, so that it can be compounded with the water-based epoxy resin cross-linking agent, and a dense molecular cross-linked network is constructed between the protein substrates, thereby It greatly improves the crosslinking density and water resistance of the cured product, and also significantly increases the solid content of the vegetable protein-based adhesive. The experimental results show that the bonding strength of the plywood prepared by using the adhesive of the present invention can fully meet the requirements of class II plywood in the national standard.
本发明方法工艺简单，操作方便，具有制造成本低、可再生，环保无污染等优点，可减少在生产、制备及应用过程中产生的危害。The method of the invention has the advantages of simple process, convenient operation, low manufacturing cost, reproducibility, environmental protection and no pollution, etc., and can reduce the harm in the process of production, preparation and application.
具体实施方式Detailed ways
以下实施例用于说明本发明，但不用来限制本发明的范围。在不背离本发明精神和实质的情况下，对本发明方法、步骤或条件所作的修改或替换，均属于本发明的范围。The following examples are intended to illustrate the present invention, but not to limit the scope of the present invention. Modifications or substitutions made to the methods, steps or conditions of the present invention without departing from the spirit and essence of the present invention all belong to the scope of the present invention.
若为特别指明，实施例中所用的技术手段为本领域技术人员所熟知的常规手段。If specified, the technical means used in the examples are conventional means well known to those skilled in the art.
本发明中涉及到的百分号“％”，若未特别说明，食指质量百分比；但溶液的百分比，除另有规定外，是指溶液100ml中含有溶质若干克；液体之间的百分比，是指20℃时容量的比例。The percentage sign "%" involved in the present invention, unless otherwise specified, refers to the mass percentage; but the percentage of the solution, unless otherwise specified, means that 100ml of the solution contains several grams of solute; the percentage between the liquids is Refers to the ratio of capacity at 20°C.
下述实施例中，所述水性聚氨酯粘合剂由聚四亚甲基乙二醇醚(PTMG)、MDI或HDI、1,4丁二醇等原料采用上述方法自制。In the following examples, the water-based polyurethane adhesive is made from raw materials such as polytetramethylene glycol ether (PTMG), MDI or HDI, 1,4 butanediol and the like by the above method.
实施例1耐沸水植物蛋白基木材胶黏剂的制备Example 1 Preparation of Boiling Water Resistant Vegetable Protein-Based Wood Adhesive
一种人造板用耐沸水植物蛋白基木材胶黏剂，配方：软化水65Kg、植物蛋白粕35Kg、水性聚氨酯粘合剂8Kg、水性环氧树脂交联剂(缩水甘油醚)4Kg。A boiling water-resistant vegetable protein-based wood adhesive for wood-based panels, the formula is as follows: 65Kg of softened water, 35Kg of vegetable protein meal, 8Kg of water-based polyurethane adhesive, and 4Kg of water-based epoxy resin cross-linking agent (glycidyl ether).
上述耐沸水植物蛋白基木材胶黏剂的制备方法，包括以下步骤：The preparation method of the above-mentioned boiling water-resistant vegetable protein-based wood adhesive, comprises the following steps:
S1在配有搅拌器的反应釜中，按配比加入软化水、植物蛋白粕搅拌均匀；S1 In the reactor equipped with agitator, add demineralized water and vegetable protein meal according to the proportion and stir evenly;
S2按配比加入水性聚氨酯粘合剂并搅拌均匀；S2 is added with water-based polyurethane adhesive according to the proportion and stirred evenly;
S3按配比加入水性环氧树脂交联剂(缩水甘油醚)并进行均质机处理，均质处理的压力为25MPa。S3 is added with a water-based epoxy resin cross-linking agent (glycidyl ether) according to the proportion and processed by a homogenizer, and the pressure of the homogenization treatment is 25MPa.
以相同的工艺制备三批平行样品，所得到的胶黏剂的性能质量指标见表1。Three batches of parallel samples were prepared in the same process, and the performance and quality indicators of the obtained adhesives are shown in Table 1.
实施例2耐沸水植物蛋白基木材胶黏剂的制备Example 2 Preparation of Boiling Water Resistant Vegetable Protein-Based Wood Adhesive
一种人造板用耐沸水植物蛋白基木材胶黏剂，配方：软化水70Kg、植物蛋白粕30Kg、水性聚氨酯粘合剂7Kg、水性环氧树脂交联剂(PAE)3Kg。A boiling water-resistant vegetable protein-based wood adhesive for wood-based panels, the formula is as follows: 70Kg of softened water, 30Kg of vegetable protein meal, 7Kg of water-based polyurethane adhesive, and 3Kg of water-based epoxy resin cross-linking agent (PAE).
制备方法与实施例1相同。The preparation method is the same as that of Example 1.
以相同的方法制备三批平行样品，制得到的胶黏剂的性能质量指标见表1。Three batches of parallel samples were prepared in the same way, and the performance and quality indexes of the obtained adhesives are shown in Table 1.
实施例3耐沸水植物蛋白基木材胶黏剂的制备Example 3 Preparation of Boiling Water Resistant Vegetable Protein-Based Wood Adhesive
一种人造板用耐沸水植物蛋白基木材胶黏剂，配方：软化水75Kg、植物蛋白粕25Kg、水性聚氨酯粘合剂6Kg、水性环氧树脂交联剂(PAE)2Kg。A boiling water-resistant vegetable protein-based wood adhesive for wood-based panels, the formula is as follows: 75Kg of softened water, 25Kg of vegetable protein meal, 6Kg of water-based polyurethane adhesive, and 2Kg of water-based epoxy resin cross-linking agent (PAE).
制备方法与实施例1相同。The preparation method is the same as that of Example 1.
以相同的方法制备三批平行样品，制得到的胶黏剂的性能质量指标见表1。Three batches of parallel samples were prepared in the same way, and the performance and quality indexes of the obtained adhesives are shown in Table 1.
表1豆蛋白胶黏剂的性能指标Table 1 Performance index of soy protein adhesive
对照例1Comparative Example 1
一种人造板用耐沸水植物蛋白基木材胶黏剂，配方：软化水75Kg、植物蛋白粕25Kg。A boiling water-resistant vegetable protein-based wood adhesive for wood-based panels, the formula is: softened water 75Kg, vegetable protein meal 25Kg.
制备方法与实施例1相同。The preparation method is the same as that of Example 1.
对照例2Comparative Example 2
一种人造板用耐沸水植物蛋白基木材胶黏剂，配方：软化水75Kg、植物蛋白粕25Kg、水性聚氨酯粘合剂(同实施例1)6Kg。A boiling water-resistant vegetable protein-based wood adhesive for wood-based panels, the formula is: 75Kg of softened water, 25Kg of vegetable protein meal, and 6Kg of water-based polyurethane adhesive (same as Example 1).
制备方法与实施例1相同。The preparation method is the same as that of Example 1.
对照例3Comparative Example 3
一种人造板用耐沸水蛋白基胶黏剂，包括以下成分：软化水75Kg、植物蛋白粕25Kg、交联剂(同实施例1)2Kg。A boiling water-resistant protein-based adhesive for wood-based panels, comprising the following components: 75Kg of softened water, 25Kg of vegetable protein meal, and 2Kg of cross-linking agent (same as in Example 1).
制备方法与实施例1相同。The preparation method is the same as that of Example 1.
试验例Test example
分别采用本发明实施例1-3和对照例1-3的产品制造三层450×450mm胶合板。Three layers of 450×450 mm plywood were produced by using the products of Examples 1-3 and Comparative Examples 1-3 of the present invention, respectively.
杨木单板：含水率干燥到6-14％；厚1.6mm；Poplar veneer: dry to 6-14% moisture content; thickness 1.6mm;
单板胶黏剂采用本发明实施例1-3的产品和对照例1-3的产品。The veneer adhesive used the products of Examples 1-3 of the present invention and the products of Comparative Examples 1-3.
按以下正常工艺制备胶合板：Prepare plywood as follows:
施胶：芯板双面施胶，涂胶量为300-360g/m2。Sizing: The core board is double-sided, and the amount of glue is 300-360g/m2.
陈化方式及时间：闭合陈化，10-30分钟。Ageing method and time: closed ageing, 10-30 minutes.
预压压力及时间：预压30分钟，压力0.8MPa。Preload pressure and time: preload for 30 minutes, pressure 0.8MPa.
热压压力：1.2MPa，热压温度为120℃，热压时间为70s/mm。Hot pressing pressure: 1.2MPa, hot pressing temperature is 120℃, hot pressing time is 70s/mm.
按GB/T17657-1999《人造板及饰面人造板理化性能实验方法》检测方法对生产的胶合板产品进行性能检测，检测结果见表2。According to GB/T17657-1999 "Experimental method for physical and chemical properties of wood-based panels and veneer wood-based panels", the performance of the plywood products produced is tested, and the test results are shown in Table 2.
表2胶接胶合板的甲醛释放量与胶合强度Table 2 Formaldehyde emission and bonding strength of glued plywood
实验结果表明，经热压处理后，本发明所得胶黏剂制造的胶合板的甲醛释放量都很低(为木材本体甲醛释放)，胶合板的耐沸水胶合强度均达到国标中II类胶合板标准(杨木≥0.70MPa)。The experimental results show that, after the hot-pressing treatment, the formaldehyde emission of the plywood made by the adhesive of the present invention is very low (for the formaldehyde emission of the wood body), and the boiling water-resistant gluing strength of the plywood all reaches the standard of Class II plywood in the national standard (Yang et al. wood ≥ 0.70MPa).
虽然，上文中已经用一般性说明及具体实施方案对本发明作了详尽的描述，但在本发明基础上，可以对之作一些修改或改进，这对本领域技术人员而言是显而易见的。因此，在不偏离本发明精神的基础上所做的这些修改或改进，均属于本发明要求保护的范围。Although the present invention has been described in detail above with general description and specific embodiments, it is obvious to those skilled in the art that some modifications or improvements can be made on the basis of the present invention. Therefore, these modifications or improvements made without departing from the spirit of the present invention fall within the scope of the claimed protection of the present invention.
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| CN110819276A (en) * | 2019-11-25 | 2020-02-21 | 浙江升华云峰新材股份有限公司 | High-strength low-formaldehyde glue and preparation method thereof |
| CN111171277A (en) * | 2020-01-20 | 2020-05-19 | 北京林业大学 | Polyurethane elastic cross-linking agent and high-strength vegetable protein adhesive and its application |
| CN115477921A (en) * | 2022-09-27 | 2022-12-16 | 南京林业大学 | A vegetable meal-based adhesive |
| CN115851223A (en) * | 2022-11-22 | 2023-03-28 | 中国林业科学研究院木材工业研究所 | Chemical activated lignin modified vegetable protein adhesive and preparation method thereof |
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| JP2017056715A (en) * | 2015-09-18 | 2017-03-23 | 王子ホールディングス株式会社 | Laminate |
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| CN104927757A (en) * | 2015-07-02 | 2015-09-23 | 青岛农业大学 | Preparation method of environment-friendly biomass adhesive |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110819276A (en) * | 2019-11-25 | 2020-02-21 | 浙江升华云峰新材股份有限公司 | High-strength low-formaldehyde glue and preparation method thereof |
| CN110819276B (en) * | 2019-11-25 | 2021-10-01 | 浙江升华云峰新材股份有限公司 | High-strength low-formaldehyde glue and preparation method thereof |
| CN111171277A (en) * | 2020-01-20 | 2020-05-19 | 北京林业大学 | Polyurethane elastic cross-linking agent and high-strength vegetable protein adhesive and its application |
| CN111171277B (en) * | 2020-01-20 | 2024-04-19 | 北京林业大学 | Polyurethane elastic crosslinking agent, high-strength and high-toughness vegetable protein adhesive and application |
| CN115477921A (en) * | 2022-09-27 | 2022-12-16 | 南京林业大学 | A vegetable meal-based adhesive |
| CN115477921B (en) * | 2022-09-27 | 2024-03-19 | 南京林业大学 | A kind of plant meal-based adhesive |
| CN115851223A (en) * | 2022-11-22 | 2023-03-28 | 中国林业科学研究院木材工业研究所 | Chemical activated lignin modified vegetable protein adhesive and preparation method thereof |
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