CN113512399B - A kind of activated lignin modified aldehyde-free soybean meal-based adhesive and preparation method and application - Google Patents
A kind of activated lignin modified aldehyde-free soybean meal-based adhesive and preparation method and application Download PDFInfo
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- 229920005610 lignin Polymers 0.000 title claims abstract description 66
- 239000000853 adhesive Substances 0.000 title claims abstract description 58
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 58
- 235000019764 Soybean Meal Nutrition 0.000 title claims abstract description 56
- 239000004455 soybean meal Substances 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims description 14
- 239000000843 powder Substances 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000002612 dispersion medium Substances 0.000 claims abstract description 18
- 239000003054 catalyst Substances 0.000 claims abstract description 17
- 239000002994 raw material Substances 0.000 claims abstract description 11
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 9
- 239000012744 reinforcing agent Substances 0.000 claims abstract description 8
- 239000002245 particle Substances 0.000 claims abstract description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 45
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 16
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 12
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical group Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 12
- 239000000725 suspension Substances 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 239000002023 wood Substances 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 239000003039 volatile agent Substances 0.000 claims description 3
- 239000003292 glue Substances 0.000 claims description 2
- 238000012545 processing Methods 0.000 claims description 2
- 238000012986 modification Methods 0.000 abstract description 5
- 230000004048 modification Effects 0.000 abstract description 5
- 239000002861 polymer material Substances 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 239000011159 matrix material Substances 0.000 abstract description 2
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- 230000002708 enhancing effect Effects 0.000 abstract 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 10
- 108010073771 Soybean Proteins Proteins 0.000 description 7
- 239000011120 plywood Substances 0.000 description 7
- 235000019710 soybean protein Nutrition 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- 238000004026 adhesive bonding Methods 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 238000011161 development Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 241000219000 Populus Species 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical group OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000002440 industrial waste Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000002154 agricultural waste Substances 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000000852 hydrogen donor Substances 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 235000018102 proteins Nutrition 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 238000011160 research Methods 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
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
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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
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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
- 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
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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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- Chemical & Material Sciences (AREA)
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- Inorganic Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
本发明属于高分子材料技术领域，提供了一种活化木质素改性无醛豆粕基胶黏剂，由以下重量份计的原料组成：豆粕粉末30份，交联剂1份，改性增强剂3‑5份，催化剂0.1份，分散介质水70份，其中，豆粕粉末中蛋白含量为53％，粒径为250目，所述改性增强剂为活化木质素。本发明选用豆粕粉末为基质，活化木质素为改性增强剂，原料易得，所制备的无醛豆粕基胶黏剂，胶黏剂预压性和胶接性能高，降低了胶黏剂热压温度和时间，胶黏效率高、无有害物质释放物、工艺性好、成本低，可工业化应用。
The invention belongs to the technical field of polymer materials, and provides an activated lignin-modified aldehyde-free soybean meal-based adhesive, which is composed of the following raw materials in parts by weight: 30 parts of soybean meal powder, 1 part of a crosslinking agent, and a modified reinforcing agent. 3-5 parts, 0.1 part of catalyst, and 70 parts of dispersion medium water, wherein the protein content in the soybean meal powder is 53%, the particle size is 250 meshes, and the modification enhancing agent is activated lignin. In the present invention, soybean meal powder is selected as the matrix, activated lignin is used as the modified reinforcing agent, the raw materials are easy to obtain, and the prepared aldehyde-free soybean meal-based adhesive has high precompression and bonding performance of the adhesive, and reduces the heat of the adhesive. Pressure temperature and time, high adhesive efficiency, no release of harmful substances, good manufacturability, low cost, and can be industrially applied.
Description
技术领域technical field
本发明属于高分子材料技术领域，具体涉及一种活化木质素改性无醛豆粕基胶黏剂及制备方法及应用。The invention belongs to the technical field of polymer materials, and in particular relates to an activated lignin modified aldehyde-free soybean meal-based adhesive and a preparation method and application thereof.
背景技术Background technique
随着经济的发展的与进步，人们对于环保意识也越来越强，传统胶黏剂的环保的问题越来越被诟病，首先就是甲醛含量的释放，大大影响着传统醛类胶黏剂的环保性能。其次是对于化石资源的依赖。为了减少污染和较少胶黏剂生产对于化石资源的依赖，近年来对于新型环保类胶黏剂的研究更加重视，其中大豆蛋白胶黏剂被广发研究，由于大豆蛋白来源广泛，环保而且胶接性能优良，被认为有巨大的应用前景。With the development and progress of the economy, people's awareness of environmental protection has become stronger and stronger, and the environmental protection of traditional adhesives has been criticized more and more. The first is the release of formaldehyde content, which greatly affects the performance of traditional aldehyde adhesives. Environmental performance. The second is the dependence on fossil resources. In order to reduce pollution and reduce the dependence of adhesive production on fossil resources, more attention has been paid to the research of new environmentally friendly adhesives in recent years. Among them, soybean protein adhesives have been widely studied. Due to the wide range of soybean protein sources, environmental protection and adhesive bonding It has excellent performance and is considered to have huge application prospects.
但是大豆蛋白胶黏剂在实际应用中还是有许多问题。大豆蛋白的耐水性差、湿剪切强度低，使其广泛利用产生了巨大阻碍。However, there are still many problems in the practical application of soybean protein adhesives. The poor water resistance and low wet shear strength of soy protein hinder its widespread use.
木质素在自然界中的含量相当高，是仅次于纤维素的第二大自然高分子材料，也是除石油资源外唯一可以提供芳香基化合物的能源材料。木质素的高效开发利用对节约化石资源和保护环境都有着相当重要的意义。The content of lignin in nature is quite high, it is the second natural polymer material after cellulose, and it is also the only energy material that can provide aromatic compounds other than petroleum resources. The efficient development and utilization of lignin is of great significance for saving fossil resources and protecting the environment.
发明内容SUMMARY OF THE INVENTION
本发明克服了现有技术中传统醛类胶黏剂释放甲醛的问题，提供一种活化木质素改性无醛豆粕基胶黏剂及制备方法及应用。该胶黏剂交联密度高、耐水胶接性能好、稳定性高、干强度好；能够满足胶黏剂的耐水和工艺要求，胶黏剂成本低，保证了生物质胶黏剂的实用性能。The invention overcomes the problem of releasing formaldehyde from traditional aldehyde-based adhesives in the prior art, and provides an activated lignin-modified aldehyde-free soybean meal-based adhesive and a preparation method and application thereof. The adhesive has high cross-linking density, good water-resistant bonding performance, high stability and good dry strength; it can meet the water resistance and process requirements of the adhesive, and the cost of the adhesive is low, ensuring the practical performance of the biomass adhesive. .
本发明提供一种活化木质素改性无醛豆粕基胶黏剂，由以下重量份计的原料组成：豆粕粉末30份，交联剂1份，改性增强剂3-5份，催化剂0.1份，分散介质水70份，其中，豆粕粉末中蛋白含量为53％，粒径为250目；The invention provides an activated lignin-modified aldehyde-free soybean meal-based adhesive, which is composed of the following raw materials in parts by weight: 30 parts of soybean meal powder, 1 part of a crosslinking agent, 3-5 parts of a modified reinforcing agent, and 0.1 part of a catalyst , 70 parts of dispersion medium water, wherein the protein content in the soybean meal powder is 53%, and the particle size is 250 meshes;
所述改性增强剂为活化木质素。The modified reinforcing agent is activated lignin.
作为优选，所述交联剂为氯化铁。Preferably, the crosslinking agent is ferric chloride.
作为优选，所述催化剂为重量分数50％的氢氧化钠溶液。Preferably, the catalyst is a sodium hydroxide solution with a weight fraction of 50%.
作为优选，所述活化木质素的制备方法，包括以下步骤：Preferably, the preparation method of the activated lignin comprises the following steps:
称取木质素、Ru/Fe3O4/Mo催化剂和甲醇分别依次加入到高压反应器中，用氮气保护，室温下加压至3Mpa，加温至200℃，磁力搅拌均匀，反应4h，反应结束后，高压反应器自然冷却和减压，过滤去除不溶性组分，在真空条件下去除所有挥发物，得到活化木质素油状产物。The lignin, Ru/Fe 3 O 4 /Mo catalyst and methanol were weighed and added to the high-pressure reactor in sequence, protected with nitrogen, pressurized to 3Mpa at room temperature, heated to 200°C, magnetically stirred, and reacted for 4h. After the end, the high-pressure reactor is naturally cooled and depressurized, insoluble components are removed by filtration, and all volatiles are removed under vacuum conditions to obtain an activated lignin oily product.
作为优选，所述木质素、Ru/Fe3O4/Mo催化剂和甲醇的质量比为10:3:50。Preferably, the mass ratio of the lignin, Ru/Fe 3 O 4 /Mo catalyst and methanol is 10:3:50.
本发明还提供一种活化木质素改性无醛豆粕基胶黏剂的制备方法，包括以下步骤：The present invention also provides a preparation method of activated lignin modified aldehyde-free soybean meal-based adhesive, comprising the following steps:
1)按照前述所述的一种活化木质素改性无醛豆粕基胶黏剂中的质量配比，称量各组分原料；1) according to the mass ratio in the aforementioned activated lignin modified aldehyde-free soybean meal-based adhesive, weigh each component raw material;
2)将活化木质素油状产物加入分散介质水中，并搅拌24h获得均匀活化木质素悬浮液；2) adding the activated lignin oily product into the dispersion medium water, and stirring for 24h to obtain a uniform activated lignin suspension;
3)将豆粕粉末、交联剂和催化剂分别依次加入步骤2)中制得的活化木质素悬浮液中，室温下搅拌均匀0.5h，出料，制得活化木质素改性无醛豆粕基胶黏剂。3) Add soybean meal powder, cross-linking agent and catalyst to the activated lignin suspension prepared in step 2) in sequence, stir evenly for 0.5 h at room temperature, and discharge to obtain activated lignin modified aldehyde-free soybean meal base glue adhesive.
本发明还提供一种如前述所述的活化木质素改性无醛豆粕基胶黏剂在木材加工和人造板材中的应用。The present invention also provides the application of the activated lignin-modified aldehyde-free soybean meal-based adhesive in wood processing and artificial boards.
与现有技术相比，本发明的有益效果是：Compared with the prior art, the beneficial effects of the present invention are:
1、本发明选用豆粕粉末，工业废弃物木质素为基质，原料易得，所制备的活化木质素改性无醛豆粕基胶黏剂，胶黏剂预压性和胶接性能高，胶黏效率高、无有害物质释放物、工艺性好、成本低，可工业化应用。1. The present invention selects soybean meal powder, industrial waste lignin as a matrix, and raw materials are easy to obtain, and the prepared activated lignin modified aldehyde-free soybean meal-based adhesive has high precompression and bonding performance of the adhesive, and the adhesive High efficiency, no harmful substance release, good manufacturability, low cost, and can be industrially applied.
2、本发明胶黏剂易形成交联结构，交联密度大，反应温度低，制备胶黏剂性能稳定、弱界面层明显下降，成本降低，干/湿强度好，产品质量稳定提高。2. The adhesive of the present invention is easy to form a cross-linked structure, has high cross-linking density, low reaction temperature, stable performance of the prepared adhesive, significantly reduced weak interface layer, reduced cost, good dry/wet strength, and stable improvement of product quality.
3、本发明使用的原材料具有生物相容性好、生物可降解、可再生性强、原料来源广、价格低廉等特点，可以很好地缓解石油资源紧缺以及合成材料对生物体和环境造成的负面影响等问题。3. The raw materials used in the present invention have the characteristics of good biocompatibility, biodegradability, strong renewability, wide source of raw materials, low price, etc., which can well alleviate the shortage of petroleum resources and the effects of synthetic materials on organisms and the environment. negative effects, etc.
4、本发明使用的原材料为农业废弃物豆粕和工业废弃物木质素，它们的高效开发利用对节约化石资源和保护环境都有着相当重要的意义。4. The raw materials used in the present invention are agricultural waste soybean meal and industrial waste lignin, and their efficient development and utilization are of great significance for saving fossil resources and protecting the environment.
附图说明Description of drawings
图1为本发明中采用实施例和对照例所得的胶黏剂制作的胶合板的胶合强度柱形图。FIG. 1 is a bar graph of the bonding strength of the plywood made of the adhesives obtained in the examples and the comparative examples in the present invention.
具体实施方式Detailed ways
为了理解本发明，下面结合具体实施例对本发明作进一步说明。应当理解。此处所描述的具体实施例仅仅用以理解本发明，并不用于限定本发明。本领域的技术人员在不背离本发明的宗旨和精神的情况下，可以对本发明进行各种修改和替换，均属于本发明的范围。In order to understand the present invention, the present invention will be further described below with reference to specific embodiments. should be understood. The specific embodiments described herein are only used to understand the present invention, and are not intended to limit the present invention. Those skilled in the art can make various modifications and substitutions to the present invention without departing from the spirit and spirit of the present invention, which all belong to the scope of the present invention.
下述实施例中所使用的实验方法如无特殊说明，均为常规操作方法。The experimental methods used in the following examples are all conventional operation methods unless otherwise specified.
总方案：Overall plan:
一种活化木质素改性无醛豆粕基胶黏剂，由以下重量份计的原料组成：豆粕粉末30份，交联剂1份，改性增强剂3-5份，催化剂0.1份，分散介质水70份，其中，豆粕粉末中蛋白含量为53％，粒径为250目；An activated lignin-modified aldehyde-free soybean meal-based adhesive is composed of the following raw materials in parts by weight: 30 parts of soybean meal powder, 1 part of a crosslinking agent, 3-5 parts of a modified reinforcing agent, 0.1 part of a catalyst, and a dispersion medium 70 parts of water, wherein the protein content in the soybean meal powder is 53%, and the particle size is 250 mesh;
所述改性增强剂为活化木质素。The modified reinforcing agent is activated lignin.
所述交联剂为氯化铁。The crosslinking agent is ferric chloride.
所述催化剂为重量分数50％的氢氧化钠溶液。The catalyst is a sodium hydroxide solution with a weight fraction of 50%.
所述活化木质素的制备方法，包括以下步骤：The preparation method of the activated lignin comprises the following steps:
称取木质素、Ru/Fe3O4/Mo催化剂和甲醇分别依次加入到高压反应器中，用氮气保护，室温下加压至3Mpa，加温至200℃，磁力搅拌均匀，反应4h，反应结束后，高压反应器自然冷却和减压，过滤去除不溶性组分，在真空条件下去除所有挥发物，得到活化木质素油状产物。The lignin, Ru/Fe 3 O 4 /Mo catalyst and methanol were weighed and added to the high-pressure reactor in sequence, protected with nitrogen, pressurized to 3Mpa at room temperature, heated to 200°C, magnetically stirred, and reacted for 4h. After the end, the high-pressure reactor is naturally cooled and depressurized, insoluble components are removed by filtration, and all volatiles are removed under vacuum conditions to obtain an activated lignin oily product.
所述木质素、Ru/Fe3O4/Mo催化剂和甲醇的质量比为10:3:50。The mass ratio of the lignin, Ru/Fe 3 O 4 /Mo catalyst and methanol is 10:3:50.
实施例1Example 1
一种活化木质素改性无醛豆粕基胶黏剂的制备方法，包括以下步骤：A preparation method of activated lignin-modified aldehyde-free soybean meal-based adhesive, comprising the following steps:
1)称取豆粕粉末30kg，氯化铁1kg，活化木质素油状产物3kg，50％的氢氧化钠溶液0.1kg，分散介质水70kg；1) take by weighing soybean meal powder 30kg, ferric chloride 1kg, activated lignin oily product 3kg, 50% sodium hydroxide solution 0.1kg, dispersion medium water 70kg;
2)将活化木质素油状产物加入分散介质水中，并搅拌24h获得均匀活化木质素悬浮液；2) adding the activated lignin oily product into the dispersion medium water, and stirring for 24h to obtain a uniform activated lignin suspension;
3)将豆粕粉末、氯化铁和氢氧化钠溶液分别依次加入步骤2)中制得的活化木质素悬浮液中，室温下搅拌均匀0.5h，出料，制得活化木质素改性无醛豆粕基胶黏剂。3) Add soybean meal powder, ferric chloride and sodium hydroxide solution to the activated lignin suspension prepared in step 2) in sequence, stir evenly for 0.5 h at room temperature, and discharge to obtain activated lignin modified aldehyde-free Soybean meal based adhesive.
实施例2Example 2
一种活化木质素改性无醛豆粕基胶黏剂的制备方法，包括以下步骤：A preparation method of activated lignin-modified aldehyde-free soybean meal-based adhesive, comprising the following steps:
1)称取豆粕粉末30kg，氯化铁1kg，活化木质素油状产物4kg，50％的氢氧化钠溶液0.1kg，分散介质水70kg；1) take by weighing soybean meal powder 30kg, ferric chloride 1kg, activated lignin oily product 4kg, 50% sodium hydroxide solution 0.1kg, dispersion medium water 70kg;
2)将活化木质素油状产物加入分散介质水中，并搅拌24h获得均匀活化木质素悬浮液；2) adding the activated lignin oily product into the dispersion medium water, and stirring for 24h to obtain a uniform activated lignin suspension;
3)将豆粕粉末、氯化铁和氢氧化钠溶液分别依次加入步骤2)中制得的活化木质素悬浮液中，室温下搅拌均匀0.5h，出料，制得活化木质素改性无醛豆粕基胶黏剂。3) Add soybean meal powder, ferric chloride and sodium hydroxide solution to the activated lignin suspension prepared in step 2) in sequence, stir evenly for 0.5 h at room temperature, and discharge to obtain activated lignin modified aldehyde-free Soybean meal based adhesive.
实施例3Example 3
一种活化木质素改性无醛豆粕基胶黏剂的制备方法，包括以下步骤：A preparation method of activated lignin-modified aldehyde-free soybean meal-based adhesive, comprising the following steps:
1)称取豆粕粉末30kg，氯化铁1kg，活化木质素油状产物5kg，50％的氢氧化钠溶液0.1kg，分散介质水70kg；1) take by weighing soybean meal powder 30kg, ferric chloride 1kg, activated lignin oily product 5kg, 50% sodium hydroxide solution 0.1kg, dispersion medium water 70kg;
2)将活化木质素油状产物加入分散介质水中，并搅拌24h获得均匀活化木质素悬浮液；2) adding the activated lignin oily product into the dispersion medium water, and stirring for 24h to obtain a uniform activated lignin suspension;
3)将豆粕粉末、氯化铁和氢氧化钠溶液分别依次加入步骤2)中制得的活化木质素悬浮液中，室温下搅拌均匀0.5h，出料，制得活化木质素改性无醛豆粕基胶黏剂。3) Add soybean meal powder, ferric chloride and sodium hydroxide solution to the activated lignin suspension prepared in step 2) in sequence, stir evenly for 0.5 h at room temperature, and discharge to obtain activated lignin modified aldehyde-free Soybean meal based adhesive.
为检测本发明所制备的活化木质素改性无醛豆粕基胶黏剂的性能，本发明还设置了对比例。In order to test the performance of the activated lignin modified aldehyde-free soybean meal-based adhesive prepared by the present invention, a comparative example is also set in the present invention.
对照例1Comparative Example 1
一种胶黏剂的制备方法，包括以下步骤：A preparation method of an adhesive, comprising the following steps:
1)称取豆粕粉末30kg，质量百分比为50％的氢氧化钠溶液0.1kg，分散介质水70kg；1) take by weighing 30kg of soybean meal powder, the mass percent is 0.1kg of 50% sodium hydroxide solution, and 70kg of dispersion medium water;
2)将豆粕粉末加入分散介质水中，并搅拌均匀；2) Add the soybean meal powder to the dispersion medium water, and stir evenly;
3)将氢氧化钠溶液加入步骤2)中所得溶液中，室温下搅拌均匀0.5h，出料，制得胶黏剂。3) Add sodium hydroxide solution to the solution obtained in step 2), stir evenly for 0.5 h at room temperature, and discharge to obtain an adhesive.
对照例2Comparative Example 2
一种胶黏剂的制备方法，包括以下步骤：A preparation method of an adhesive, comprising the following steps:
1)称取豆粕粉末30kg，活化木质素油状产物5kg，质量百分比为50％的氢氧化钠溶液0.1kg，分散介质水70kg；1) take by weighing soybean meal powder 30kg, activated lignin oily product 5kg, mass percent is 50% sodium hydroxide solution 0.1kg, dispersion medium water 70kg;
2)将活化木质素油状产物加入分散介质水中，并搅拌24h获得均匀活化木质素悬浮液；2) adding the activated lignin oily product into the dispersion medium water, and stirring for 24h to obtain a uniform activated lignin suspension;
3)将豆粕粉末、氯化铁和氢氧化钠溶液分别依次加入步骤2)中制得的活化木质素悬浮液中，室温下搅拌均匀0.5h，出料，制得活化木质素改性无醛豆粕基胶黏剂。3) Add soybean meal powder, ferric chloride and sodium hydroxide solution to the activated lignin suspension prepared in step 2) in sequence, stir evenly for 0.5 h at room temperature, and discharge to obtain activated lignin modified aldehyde-free Soybean meal based adhesive.
对照例3Comparative Example 3
一种胶黏剂的制备方法，包括以下步骤：A preparation method of an adhesive, comprising the following steps:
1)称取豆粕粉末30kg，氯化铁1kg，质量百分比为50％的氢氧化钠溶液0.1kg，分散介质水70kg；1) take by weighing 30kg of soybean meal powder, 1kg of ferric chloride, 0.1kg of 50% sodium hydroxide solution by mass percentage, 70kg of dispersion medium water;
2)将豆粕粉末加入分散介质水中，并搅拌均匀；2) Add the soybean meal powder to the dispersion medium water, and stir evenly;
3)将氯化铁和氢氧化钠溶液分别依次加入步骤2)中制得的分散液中，室温下搅拌均匀0.5h，出料，制得活化木质素改性无醛豆粕基胶黏剂。3) Add ferric chloride and sodium hydroxide solution to the dispersion obtained in step 2) in sequence, stir evenly for 0.5 h at room temperature, and discharge to obtain activated lignin modified aldehyde-free soybean meal-based adhesive.
选用实施例1至实施例3所制得的活化木质素改性无醛豆粕基胶黏剂和对照例1至对照例3所制得的胶黏剂，制备三层胶合板，选用杨木单板，其含水率低于10％，尺寸为40cm*40cm*0.15cm，按照以下工艺制备：The activated lignin-modified aldehyde-free soybean meal-based adhesive prepared in Examples 1 to 3 and the adhesive prepared in Comparative Example 1 to Comparative Example 3 were selected to prepare three-layer plywood, and poplar veneer was selected. , its moisture content is less than 10%, the size is 40cm*40cm*0.15cm, and it is prepared according to the following process:
施胶：芯板双面施胶，涂胶量为350-400g/m2；Sizing: double-sided gluing on the core board, the gluing amount is 350-400g/m 2 ;
压合：压力1MPa、温度120℃、时间为6分钟。Lamination: pressure 1MPa, temperature 120°C, time 6 minutes.
按GB/T17657-1999《人造板及饰面人造板理化性能实验方法》检测方检测方法对生产的胶合板产品进行性能检测，检测其甲醛释放量和胶合强度，检测结果如表1所示。According to GB/T17657-1999 "Experimental Methods for Physical and Chemical Properties of Wood-based Panels and Finished Wood-based Panels", the performance of the produced plywood products was tested, and the formaldehyde emission and bonding strength were tested. The test results are shown in Table 1.
其中，N表示未添加Among them, N means not added
表1Table 1
由表1可知，活化木质素添加越多，活化木质素改性无醛豆粕基胶黏剂的胶合强度越大。It can be seen from Table 1 that the more activated lignin is added, the greater the bonding strength of the activated lignin-modified aldehyde-free soybean meal-based adhesive.
采用实施例1、实施例2和实施例3所制备的活化木质素改性无醛豆粕基胶黏剂制造的胶合板，与对比例1至对比例3所制得的胶黏剂制造的胶合板相比，甲醛释放量更低，胶合强度更高。本发明所制作的胶合板的胶合强度按国标II胶合板检测最高可达1.87MPa(杨木≥0.7MPa)，由对比例制得的胶黏剂比对照组显著提高。The plywood produced by using the activated lignin-modified aldehyde-free soybean meal-based adhesive prepared in Example 1, Example 2 and Example 3 is similar to the plywood produced by the adhesive prepared in Comparative Example 1 to Comparative Example 3. The formaldehyde emission is lower and the bonding strength is higher. The gluing strength of the plywood produced by the invention can be up to 1.87MPa (poplar ≥ 0.7MPa) according to the national standard II plywood test, and the adhesive prepared by the comparative example is significantly higher than that of the control group.
木质素通过Ru/Fe3O4/Mo催化剂改性可以生成木质素基儿茶酚结构，并且相较于超声处理的木质素活化效果更好，所以我们利用Ru/Fe3O4/Mo催化剂对木质素进行催化降解处理，并将木质素基儿茶酚结构引入大豆蛋白胶黏剂中使其与大豆蛋白形成复合交联网络。并且木质素本身同样富含大量的酚羟基作为供氢体，可与羧基、羟基、氨基等蛋白质官能团形成共价键和氢键。从而大大提高了大豆蛋白的耐水交接性能，不管是干剪切强度还是湿剪切强度都有不同程度的增加。Lignin can be modified by Ru/Fe 3 O 4 /Mo catalyst to generate lignin-based catechol structure, and the activation effect of lignin is better than that of ultrasonic treatment, so we use Ru/Fe 3 O 4 /Mo catalyst The lignin was catalytically degraded, and the lignin-based catechol structure was introduced into the soybean protein adhesive to form a complex cross-linked network with soybean protein. And lignin itself is also rich in a large number of phenolic hydroxyl groups as hydrogen donors, which can form covalent bonds and hydrogen bonds with protein functional groups such as carboxyl, hydroxyl, and amino groups. Thereby, the water-resistance handover performance of soybean protein is greatly improved, and both dry shear strength and wet shear strength have different degrees of increase.
以上所述，仅是本发明的较佳实施例而已，并非对本发明作任何形式上的限制，虽然本发明已以较佳实施例揭露如上，然而并非用以限定本发明，任何熟悉本专业的技术人员，在不脱离本发明技术方案范围内，当可利用上述揭示的技术内容做出些许更动或修饰为等同变化的等效实施例，但凡是未脱离本发明技术方案的内容，依据本发明的技术实质对以上实施例所作的任何的简单修改、等同变化与修饰，均仍属于本发明技术方案的范围内。The above descriptions are only preferred embodiments of the present invention, and are not intended to limit the present invention in any form. Although the present invention has been disclosed above with preferred embodiments, it is not intended to limit the present invention. The technical personnel, within the scope of the technical solution of the present invention, can make some changes or modifications to equivalent examples of equivalent changes by using the technical content disclosed above, but any content that does not depart from the technical solution of the present invention, according to the present invention. Any simple modifications, equivalent changes and modifications made to the above embodiments by the technical essence of the invention still fall within the scope of the technical solutions of the present invention.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013112445A1 (en) * | 2012-01-23 | 2013-08-01 | Hercules Incorporated | Method for the preparation of wood composite from soy flour |
| JP2017132852A (en) * | 2016-01-26 | 2017-08-03 | 日本化薬株式会社 | Modified lignin, epoxy resin, and method for producing the same |
| WO2019120956A1 (en) * | 2017-12-22 | 2019-06-27 | Universidad De Valladolid | Ultra-fast lignin depolymerization process |
| CN110272716A (en) * | 2019-07-23 | 2019-09-24 | 北京林业大学 | A kind of toughness is without aldehyde dregs of beans base based Wood Adhesives and preparation method thereof |
| CN112175558A (en) * | 2020-10-22 | 2021-01-05 | 彭娜 | Modified lignin weather-resistant adhesive and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016141126A1 (en) * | 2015-03-04 | 2016-09-09 | Solenis Technologies, L.P. | Method of making lignocellulosic composites |
-
2021
- 2021-04-29 CN CN202110475388.0A patent/CN113512399B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013112445A1 (en) * | 2012-01-23 | 2013-08-01 | Hercules Incorporated | Method for the preparation of wood composite from soy flour |
| JP2017132852A (en) * | 2016-01-26 | 2017-08-03 | 日本化薬株式会社 | Modified lignin, epoxy resin, and method for producing the same |
| WO2019120956A1 (en) * | 2017-12-22 | 2019-06-27 | Universidad De Valladolid | Ultra-fast lignin depolymerization process |
| CN110272716A (en) * | 2019-07-23 | 2019-09-24 | 北京林业大学 | A kind of toughness is without aldehyde dregs of beans base based Wood Adhesives and preparation method thereof |
| CN112175558A (en) * | 2020-10-22 | 2021-01-05 | 彭娜 | Modified lignin weather-resistant adhesive and preparation method thereof |
Non-Patent Citations (4)
| Title |
|---|
| Jing Luo等."An eco-friendly wood adhesive from soy protein and lignin: performance properties".《The Royal Society of Chemistry》.2015,第5卷第100849-100855页. * |
| Jiongjiong Li等."Facile design of tough, strong, and UV-shielding soy protein-based composite films".《Industrial Crops&Products》.2021,第166卷第113474页. * |
| Sarocha Pradyawong等."Adhesion properties of soy protein adhesives enhanced by biomass lignin".《International Journal of Adhesion and Adhesives》.2017,第75卷第66-73页. * |
| 李宁等."不同木质素磺酸钠对豆粕胶黏剂性能的影响".《精细化工》.2021,第38卷(第1期),第206-211页. * |
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