CN114008168A - 制备粘合树脂的方法 - Google Patents
制备粘合树脂的方法 Download PDFInfo
- Publication number
- CN114008168A CN114008168A CN202080043811.3A CN202080043811A CN114008168A CN 114008168 A CN114008168 A CN 114008168A CN 202080043811 A CN202080043811 A CN 202080043811A CN 114008168 A CN114008168 A CN 114008168A
- Authority
- CN
- China
- Prior art keywords
- ether
- diglycidyl
- diglycidyl ether
- triglycidyl
- polyglycidyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
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Classifications
-
- 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
- C09J171/00—Adhesives based on polyethers obtained by reactions forming an ether link in the main chain; Adhesives based on derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/62—Alcohols or phenols
- C08G59/621—Phenols
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- 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
- B27N1/00—Pretreatment of moulding material
- B27N1/003—Pretreatment of moulding material for reducing formaldehyde gas emission
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- 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
- B27N1/00—Pretreatment of moulding material
- B27N1/02—Mixing the material with binding agent
- B27N1/0209—Methods, e.g. characterised by the composition of the agent
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- 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
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B19/00—Layered products comprising a layer of natural mineral fibres or particles, e.g. asbestos, mica
- B32B19/06—Layered products comprising a layer of natural mineral fibres or particles, e.g. asbestos, mica next to a fibrous or filamentary layer
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
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Abstract
本发明涉及制备粘合树脂的方法,将固体形式或在水中的分散体形式的木质素与交联剂和任选的一种或多种添加剂混合,然后添加碱性溶液。粘合树脂可用于例如以下的制造中:层合物、矿棉绝缘物和木制品,比如胶合板、定向刨花板(OSB)、层压单板木材(LVL)、中密度纤维板(MDF)、高密度纤维板(HDF)、镶木地板、曲面胶合板、贴面刨花板、贴面MDF或刨花板、层合物或矿棉绝缘物。
Description
技术领域
本发明涉及制备粘合树脂的方法,其中木质素以固体形式或在水中的分散体形式提供并且将木质素与以下的一种或多种物质和任选的一种或多种添加剂混合,然后添加碱性溶液,所述一种或多种物质为:甘油二缩水甘油醚、二甘油聚缩水甘油醚、聚甘油聚缩水甘油醚、甘油三缩水甘油醚、山梨糖醇聚缩水甘油醚、烷氧基化甘油聚缩水甘油醚、三羟甲基丙烷三缩水甘油醚、三羟甲基丙烷二缩水甘油醚、聚氧亚丙基二醇二缩水甘油醚、聚氧亚丙基二醇三缩水甘油醚、环己烷二甲醇的二缩水甘油醚、间苯二酚二缩水甘油醚、异山梨醇二缩水甘油醚、季戊四醇四缩水甘油醚、乙二醇二缩水甘油醚、具有2-9个乙二醇单元的聚乙二醇二缩水甘油醚、具有1-5个丙二醇单元的丙二醇二缩水甘油醚、六氢邻苯二甲酸二缩水甘油酯和/或具有3-6个碳原子的线性碳链的末端二醇的二缩水甘油醚,或选自以下的交联剂:碳水化合物的二缩水甘油醚、三缩水甘油醚或聚缩水甘油醚,碳水化合物的二缩水甘油酯、三缩水甘油酯或聚缩水甘油酯,水杨酸、香草酸或4-羟基苯甲酸的二缩水甘油醚或二缩水甘油酯,环氧化或缩水甘油基取代的植物基酚类化合物(比如单宁(tannin)、腰果酚、腰果间二酚(cardol)、漆树酸)或环氧化植物基油(比如菜籽油、亚麻籽油、大豆油),三(4-羟基苯基)甲烷三缩水甘油醚,N,N-双(2,3-环氧丙基)苯胺,对-(2,3-环氧丙氧基-N,N-双(2,3-环氧丙基)苯胺,双羟甲基呋喃二的缩水甘油醚,和具有选自以下的官能团的交联剂:二缩水甘油酰胺、三缩水甘油酰胺、聚缩水甘油酰胺、二缩水甘油酯、三缩水甘油酯、聚缩水甘油酯、二缩水甘油基叠氮化物、三缩水甘油基叠氮化物、聚缩水甘油基叠氮化物、二缩水甘油基甲基丙烯酸酯、三缩水甘油基甲基丙烯酸酯和聚缩水甘油基甲基丙烯酸酯。粘合树脂可用于例如制造层合物、矿棉绝缘物和木制品,比如胶合板、定向刨花板(OSB)、层压单板木材(LVL)、中密度纤维板(MDF)、高密度纤维板(HDF)、镶木地板、曲面(curved,弯曲)胶合板、贴面刨花板、贴面MDF、层合物或矿棉绝缘物。粘合树脂还可用于例如复合材料、模塑配混物、铸造应用以及纸、木材或金属基材的涂料(层)。
背景技术
木质素,一种芳香族聚合物,是例如木材中的主要成分,是地球上仅次于纤维素的最丰富的碳源。近年来,随着从制浆过程中以高纯度、固体和颗粒化的形式提取木质素的技术的发展和商业化,它作为目前源自石化行业的主要芳香族化学前体的可能的可再生替代品引起了人们的极大关注。
木质素是一种多环芳烃网络,在酚-甲醛胶粘剂生产期间作为苯酚的合适替代品已被广泛研究。这些在层合物和结构木制品(比如胶合板、定向刨花板和纤维板)的制造期间使用。在合成这样的胶粘剂期间,可部分地被木质素替换的酚与甲醛在碱性或酸性催化剂的存在下反应以形成高度交联的芳族树脂,称作酚醛清漆(novolacs)(在使用酸性催化剂时)或甲阶酚醛树脂(resoles,热固性酚醛树脂)(在使用碱性催化剂时)。目前,仅有限量的酚可被木质素替换,原因是木质素反应性较低。
在制备包含木质素的树脂时的一个问题是甲醛的使用,当在含甲醛的树脂中使用木质素时,比如木质素-酚-甲醛树脂。基于甲醛的树脂释放甲醛,这是有毒的挥发性有机化合物。涉及降低或消除甲醛释放的现有的和提出的立法已经引起用于木材胶粘剂应用的不含甲醛的树脂的开发。
Jingxian Li R等(Green Chemistry,2018,20,1459-1466)描述了包含甘油二缩水甘油醚和木质素的树脂的制备,其中木质素以固体形式提供。文章中描述的技术的一个问题是长压制时间和高压制温度。3片层胶合板样品在150℃的温度下压制15分钟以完全地使树脂固化。
Engelmann G和Ganster J(Holzforschung,2014,68,435-446)描述了具有低分子量硫酸盐木质素和连苯三酚的生物基环氧树脂的制备,其中木质素组分由来自硫酸盐木质素的丙酮萃取组成。
发明内容
已经令人惊奇地发现如果将木质素分散在合适的交联剂(比如缩水甘油醚)中,交联反应可被碱性溶液催化。这导致快速固化的具有优异反应性、粘合强度和耐水性的树脂。
当分散在缩水甘油醚中的木质素与水和碱混合时,木质素变得溶解在碱性溶液中。此外,木质素结构中的酚羟基脱质子并且自由地与缩水甘油醚的环氧基反应。这催化了反应并且改进了粘合剂的反应性和性能。因此,可容易地制备粘合树脂,其中可避免使用甲醛。在制造例如层合物、矿棉绝缘物和木制品,比如胶合板、定向刨花板(OSB)、层压单板木材(LVL)、中密度纤维板(MDF)、镶木地板、曲面胶合板、贴面刨花板、贴面MDF或刨花板(particle boards,碎料板)、层合物或矿棉绝缘物时,根据本发明的粘合树脂显著地使反应加速并且因此降低了压制时间并且能够使用较低的压制温度用于固化粘合树脂。粘合树脂还可用于例如复合材料、模塑配混物、铸造应用以及纸、木材或金属基材的涂料(层)。
本发明因此涉及制备粘合树脂的方法,其中将固体形式或在水中的分散体形式的木质素与以下的一种或多种物质混合,然后添加碱性溶液,所述一种或多种物质为:甘油二缩水甘油醚、二甘油聚缩水甘油醚、聚甘油聚缩水甘油醚、甘油三缩水甘油醚、山梨糖醇聚缩水甘油醚、烷氧基化甘油聚缩水甘油醚、三羟甲基丙烷三缩水甘油醚、三羟甲基丙烷二缩水甘油醚、聚氧亚丙基二醇二缩水甘油醚、聚氧亚丙基二醇三缩水甘油醚、环己烷二甲醇的二缩水甘油醚、间苯二酚二缩水甘油醚、异山梨醇二缩水甘油醚、季戊四醇四缩水甘油醚、乙二醇二缩水甘油醚、具有2-9个乙二醇单元的聚乙二醇二缩水甘油醚、具有1-5个丙二醇单元的丙二醇二缩水甘油醚、六氢邻苯二甲酸二缩水甘油酯和/或具有3-6个碳原子的线性碳链的末端二醇的二缩水甘油醚,选自以下的交联剂:碳水化合物的二缩水甘油醚、三缩水甘油醚或聚缩水甘油醚,碳水化合物的二缩水甘油酯、三缩水甘油酯或聚缩水甘油酯,水杨酸、香草酸或4-羟基苯甲酸的二缩水甘油醚或二缩水甘油酯,环氧化或缩水甘油基取代的植物基酚类化合物(比如单宁、腰果酚、腰果间二酚、漆树酸)或环氧化植物基油(比如菜籽油、亚麻籽油、大豆油),三(4-羟基苯基)甲烷三缩水甘油醚,N,N-双(2,3-环氧丙基)苯胺,对-(2,3-环氧丙氧基-N,N-双(2,3-环氧丙基)苯胺,双羟甲基呋喃的二缩水甘油醚,和具有选自以下的官能团的交联剂:二缩水甘油酰胺、三缩水甘油酰胺、聚缩水甘油酰胺、二缩水甘油酯、三缩水甘油酯、聚缩水甘油酯、二缩水甘油基叠氮化物、三缩水甘油基叠氮化物、聚缩水甘油基叠氮化物、二缩水甘油基甲基丙烯酸酯、三缩水甘油基甲基丙烯酸酯和聚缩水甘油基甲基丙烯酸酯。
本发明的一个方面是制备粘合树脂的方法,其中将固体形式的木质素与一种或多种交联剂和/或一种或多种缩水甘油醚混合,然后添加碱性溶液,其中交联剂的环氧指数高于4eq/kg。环氧指数可根据ISO 3001测定。优选地,交联剂的环氧指数高于5eq/kg。交联剂为脂族缩水甘油醚,或优选地为芳族缩水甘油醚。优选地,交联剂是脂族的。
缩水甘油醚可以是多官能环氧化物并且根据本发明的方法可使用比如单官能、双官能、三官能和/或四官能的环氧化物的混合物。
本发明因此涉及能够使用上述方法获得的粘合树脂并且涉及粘合树脂在在层合物、矿棉绝缘物和木制品,比如胶合板、定向刨花板(OSB)、层压单板木材(LVL)、中密度纤维板(MDF)和刨花板中的用途。根据本发明的粘合树脂还可用在涂料(层)中或用于涂料(层),比如施加在金属表面或木材或其他基材上的涂料(层)。本发明还涉及使用粘合树脂制造的这样的层合物、矿棉绝缘物和木制品,比如胶合板、定向刨花板(OSB)、层压单板木材(LVL)、中密度纤维板(MDF)、高密度纤维板(HDF)、镶木地板、曲面胶合板、贴面刨花板、贴面MDF、层合物或矿棉绝缘物。根据本发明的粘合树脂还可用于复合材料、模塑配混物、铸造应用以及纸、木材或金属基材的涂料(涂层)的制造中。
具体实施方式
在整个本发明说明书中,表述“木质素”意在包括任何种类的木质素,例如源自硬木、软木或环状(annula)植物的木质素。木质素优选是在例如硫酸盐工艺中产生的碱性木质素。优选地,在根据本发明的方法中使用之前,木质素已经被纯化或分离。在根据本发明的方法中使用之前,可将木质素从黑液分离并且任选地将木质素进一步纯化。纯化典型地使得木质素的纯度为至少90%,优选至少95%。因此,根据本发明的方法使用的木质素优选含有小于10%、优选小于5%杂质。可随后通过使用WO2006031175中公开的方法将木质素从黑液分离。可随后通过使用称作LignoBoost工艺的方法将木质素从黑液分离。
木质的粒径优选使得颗粒的50重量%的粒径大于100微米。优选地,颗粒的至少20重量%的粒径大于300微米。优选地,颗粒的至少80重量%的粒径小于1000微米。优选地,颗粒的水分含量小于40重量%。
根据本发明使用的以下物质用作交联剂:甘油二缩水甘油醚、二甘油聚缩水甘油醚、聚甘油聚缩水甘油醚、甘油三缩水甘油醚、山梨糖醇聚缩水甘油醚、烷氧基化甘油聚缩水甘油醚、三羟甲基丙烷三缩水甘油醚、三羟甲基丙烷二缩水甘油醚、聚氧亚丙基二醇二缩水甘油醚、聚氧亚丙基二醇三缩水甘油醚、环己烷二甲醇的二缩水甘油醚、间苯二酚二缩水甘油醚、异山梨醇二缩水甘油醚、季戊四醇四缩水甘油醚、乙二醇二缩水甘油醚、具有2-9个乙二醇单元的聚乙二醇二缩水甘油醚(优选2-5个乙二醇单元,比如2-3或4-5个亚乙基单元)、具有1-3个丙二醇单元或4-5个丙二醇单元的丙二醇二缩水甘油醚、六氢邻苯二甲酸二缩水甘油酯和/或具有3-6个碳原子的线性碳链的末端二醇的二缩水甘油醚。可使用具有较多官能环氧基的缩水甘油醚,比如甘油二缩水甘油醚、甘油三缩水甘油醚和山梨糖醇聚缩水甘油醚。可使用具有二至九个(比如2至4或2至6)亚烷基二醇基团的其他缩水甘油醚,比如二乙二醇二缩水甘油醚、三乙二醇二缩水甘油醚、二丙二醇二缩水甘油醚和三亚丙基二缩水甘油醚。随着两个缩水甘油醚基之间的链长度变长,树脂变得更有柔性,这可负面影响其性能。在固化期间,其产生胶粘剂。根据本发明,还可使用选自以下的交联剂:碳水化合物的二缩水甘油醚、三缩水甘油醚或聚缩水甘油醚,碳水化合物的二缩水甘油酯、三缩水甘油酯或聚缩水甘油酯,水杨酸、香草酸、或4-羟基苯甲酸的二缩水甘油醚或二缩水甘油酯,环氧化或缩水甘油基取代的植物基酚类化合物(比如单宁、腰果酚、腰果间二酚、漆树酸)或环氧化植物基油(比如菜籽油、亚麻籽油、大豆油),三(4-羟基苯基)甲烷三缩水甘油醚,N,N-双(2,3-环氧丙基)苯胺,对-(2,3-环氧丙氧基-N,N-双(2,3-环氧丙基)苯胺,双羟甲基呋喃的二缩水甘油醚,和具有选自以下的官能团的交联剂:二缩水甘油酰胺、三缩水甘油酰胺、聚缩水甘油酰胺、二缩水甘油酯、三缩水甘油酯、聚缩水甘油酯、二缩水甘油基叠氮化物、三缩水甘油基叠氮化物、聚缩水甘油基叠氮化物、二缩水甘油基甲基丙烯酸酯、三缩水甘油基甲基丙烯酸酯和聚缩水甘油基甲基丙烯酸酯。在固化期间,其产生胶粘剂。典型地,根据本发明的粘合树脂为并且施加至例如贴面的表面,比如在胶合板的制造中。当在加热下将贴面压制在一起时,粘合树脂中发生交联,产生胶粘剂。
碱性溶液的pH优选在10至14的范围内。合适的碱的实例包括氢氧化钠、氢氧化钾、氨或其他有机碱,及其混合物。在一个实施方式中,碱性溶液中的碱的量优选为溶液的0.1重量%至15重量%,比如溶液的0.1重量%至10重量%。在一个实施方式中,碱性溶液是水性的。碱性溶液可包含添加剂,比如比如脲、单宁、溶剂、表面活性剂、分散试剂和填料。
木质素(干重量)和以下物质的总量之间的重量比优选在1:10至10:1的范围内:甘油二缩水甘油醚、二甘油聚缩水甘油醚、聚甘油聚缩水甘油醚、甘油三缩水甘油醚、山梨糖醇聚缩水甘油醚、烷氧基化甘油聚缩水甘油醚、三羟甲基丙烷三缩水甘油醚、三羟甲基丙烷二缩水甘油醚、聚氧亚丙基二醇二缩水甘油醚、聚氧亚丙基二醇三缩水甘油醚、环己烷二甲醇的二缩水甘油醚、间苯二酚二缩水甘油醚、异山梨醇二缩水甘油醚、季戊四醇四缩水甘油醚、乙二醇二缩水甘油醚、具有2-9个乙二醇单元的聚乙二醇二缩水甘油醚、具有1-5个丙二醇单元的丙二醇二缩水甘油醚、六氢邻苯二甲酸二缩水甘油酯和/或具有3-6个碳的线性碳链的末端二醇的二缩水甘油醚,或选自以下的交联剂:碳水化合物的二缩水甘油醚、三缩水甘油醚或聚缩水甘油醚、碳水化合物的二缩水甘油酯、三缩水甘油酯或聚缩水甘油酯、水杨酸、香草酸或4-羟基苯甲酸的二缩水甘油醚或二缩水甘油酯、环氧化或缩水甘油基取代的植物基酚类化合物(比如单宁、腰果酚、腰果间二酚、漆树酸)或环氧化植物基油(比如菜籽油、亚麻籽油、大豆油)、三(4-羟基苯基)甲烷三缩水甘油醚、N,N-双(2,3-环氧丙基)苯胺、对-(2,3-环氧丙氧基-N,N-双(2,3-环氧丙基)苯胺、双羟甲基呋喃的二缩水甘油醚,和具有选自以下的官能团的交联剂:二缩水甘油酰胺、三缩水甘油酰胺、聚缩水甘油酰胺、二缩水甘油酯、三缩水甘油酯、聚缩水甘油酯、二缩水甘油基叠氮化物、三缩水甘油基叠氮化物、多缩水甘油基叠氮化物、二缩水甘油基甲基丙烯酸酯、三缩水甘油基甲基丙烯酸酯和聚缩水甘油基甲基丙烯酸酯。粘合树脂中木质素的量优选为5重量%至50重量%,其以木质素的干重量和粘合树脂的总重量计算。
粘合树脂还可包含添加剂,比如脲、单宁、溶剂和填料。
粘合树脂中脲的量可为0-40%,优选5-20%,其以脲的干重量和粘合树脂的总重量计算。
还可向粘合树脂添加填料和/或硬化剂。这样的填料和/或硬化剂的实例包括石灰石、纤维素、碳酸钠和淀粉。
木质素与缩水甘油醚的反应性可通过将木质素改性而提高,所述改性为通过以下方式改性:乙醛酸化(glyoxylation,乙醛化)、醚化、酯化或提高木质素羟基含量或羧基含量或胺含量或巯基含量的任何其他方法。
可在根据本发明的粘合树脂中使用的其他溶剂为甘油、乙二醇、聚乙二醇、丙二醇、聚丙二醇、山梨糖醇和/或任何具有3-6个碳原子的线性碳链的末端二醇。
固体形式或在水中的分散体形式的木质素优选在室温下与缩水甘油醚混合,比如在15℃至30℃的温度下。混合优选进行约5分钟至2小时。优选地,在混合期间监控混合物的粘度,以连续方式监控或通过采取样品并且测定其粘度的方式监控。在添加碱性溶液之后,混合优选进行至少1分钟,比如1分钟至约2小时。优选地,在碱性溶液之后在混合期间也监控混合物的粘度,以连续方式监控或通过采取样品并且测定其粘度的方式监控。混合还可通过在木质素颗粒上提供缩水甘油醚而进行,比如通过将缩水甘油醚喷洒到木质素颗粒上,任选地然后进行干燥。
实施例
通过将40g的木质素分散到60g的聚甘油聚缩水甘油醚和30g的甘油中而制备第一组分。通过混合17.4g的50%氢氧化钠溶液和49.8g的水而制备第二组分。使用顶部搅拌器在室温下将两个组分混合并且搅拌20分钟。
使用Automated Bonding Evaluation System(ABES)拉伸测试机在搭接(lap-joint)测试中对粘合剂进行测试。
出于此目的,使用切成105x20 mm料块(pieces)的厚度为0.6mm的相对薄的榉木贴面。将树脂施加至两个料块的一个端部的一侧上5mmx 20mm的区域。将一系列试样的涂覆树脂的重叠端部在热压机中以5kg/m2的压力压制在一起,在150℃的压制温度下使用90秒的压制时间。
在评估之前,在室温下将所有样品浸没在水中24小时。条件化和未条件化的5个测试试样的平均数据示于表1中。
表1:使用ABES的剪切强度
实施例2:
通过将40g的木质素分散到60g的聚乙二醇二缩水甘油醚中而制备第一组分。通过混合22.6g的50%氢氧化钠溶液和80g的水而制备第二组分。使用顶部搅拌器在室温下将第一和第二组分混合并且搅拌20分钟。
使用Automated Bonding Evaluation System(ABES)拉伸测试机在搭接测试中对粘合剂进行测试。
出于此目的,使用切成105x20 mm料块的厚度为0.6mm的相对薄的榉木贴面。将树脂施加至两个料块的一个端部的一侧上5mm x 20mm的区域。将一系列试样的涂覆树脂的重叠端部在热压机中以5kg/m2的压力压制在一起,在150℃的压制温度下使用90秒的压制时间。
在评估之前,在室温下将所有样品浸没在水中24小时。条件化和未条件化的5个测试试样的平均数据示于表2中。
表2:使用ABES的剪切强度
鉴于以上对本发明的详细描述,其他修改和变化对于本领域技术人员将变得显而易见。然而,显然,在不脱离本发明的精神和范围的情况下,可以实现这样的其他修改和变化。
Claims (13)
1.制备粘合树脂的方法,其中将固体形式或在水中的分散体形式的木质素与以下的一种或多种物质和任选的一种或多种添加剂混合,然后添加碱性溶液,所述一种或多种物质为:甘油二缩水甘油醚、二甘油聚缩水甘油醚、聚甘油聚缩水甘油醚、甘油三缩水甘油醚、山梨糖醇聚缩水甘油醚、烷氧基化甘油聚缩水甘油醚、三羟甲基丙烷三缩水甘油醚、三羟甲基丙烷二缩水甘油醚、聚氧亚丙基二醇二缩水甘油醚、聚氧亚丙基二醇三缩水甘油醚、环己烷二甲醇的二缩水甘油醚、间苯二酚二缩水甘油醚、异山梨醇二缩水甘油醚、季戊四醇四缩水甘油醚、乙二醇二缩水甘油醚、具有2-9个乙二醇单元的聚乙二醇二缩水甘油醚、具有1-5个丙二醇单元的丙二醇二缩水甘油醚、六氢邻苯二甲酸二缩水甘油酯和/或具有3-6个碳原子的线性碳链的末端二醇的二缩水甘油醚,或选自以下的交联剂:碳水化合物的二缩水甘油醚、三缩水甘油醚或聚缩水甘油醚、碳水化合物的二缩水甘油酯、三缩水甘油酯或聚缩水甘油酯,水杨酸、香草酸或4-羟基苯甲酸的二缩水甘油醚或二缩水甘油酯,环氧化或缩水甘油基取代的植物基酚类化合物(比如单宁、腰果酚、腰果间二酚、漆树酸)或环氧化植物基油(比如菜籽油、亚麻籽油、大豆油),三(4-羟基苯基)甲烷三缩水甘油醚,N,N-双(2,3-环氧丙基)苯胺,对-(2,3-环氧丙氧基-N,N-双(2,3-环氧丙基)苯胺,双羟甲基呋喃的二缩水甘油醚,和具有选自以下的官能团的交联剂:二缩水甘油酰胺、三缩水甘油酰胺、聚缩水甘油酰胺、二缩水甘油酯、三缩水甘油酯、聚缩水甘油酯、二缩水甘油基叠氮化物、三缩水甘油基叠氮化物、聚缩水甘油基叠氮化物、二缩水甘油基甲基丙烯酸酯、三缩水甘油基甲基丙烯酸酯和聚缩水甘油基甲基丙烯酸酯。
2.根据权利要求1所述的方法,其中将固体形式的木质素与以下的一种或多种物质和任选的一种或多种添加剂混合,然后添加碱性溶液,所述一种或多种物质为:甘油二缩水甘油醚、二甘油聚缩水甘油醚、聚甘油聚缩水甘油醚、甘油三缩水甘油醚、山梨糖醇聚缩水甘油醚、烷氧基化甘油聚缩水甘油醚、三羟甲基丙烷三缩水甘油醚、三羟甲基丙烷二缩水甘油醚、聚氧亚丙基二醇二缩水甘油醚、聚氧亚丙基二醇三缩水甘油醚、环己烷二甲醇的二缩水甘油醚、间苯二酚二缩水甘油醚、异山梨醇二缩水甘油醚、季戊四醇四缩水甘油醚、乙二醇二缩水甘油醚、具有2-9个乙二醇单元的聚乙二醇二缩水甘油醚、具有1-5个丙二醇单元的丙二醇二缩水甘油醚、六氢邻苯二甲酸二缩水甘油酯和/或具有3-6个碳原子的线性碳链的末端二醇的二缩水甘油醚。
3.根据权利要求1或2所述的方法,其中所述醚为聚甘油聚缩水甘油醚。
4.根据权利要求1-3中任一项所述的方法,其中一种添加剂为溶剂。
5.根据权利要求1-4中任一项所述的方法,其中基于干木质素计算的木质素和甘油二缩水甘油醚和/或乙二醇二缩水甘油醚的总量之间的重量比为1:10至10:1。
6.根据权利要求1-5中任一项所述的方法,其中一种添加剂是脲、单宁、表面活性剂、分散试剂、填料和/或溶剂。
7.根据权利要求6所述的方法,其中溶剂为甘油、乙二醇、聚乙二醇、丙二醇、聚丙二醇、山梨糖醇和/或任何具有3-6个碳原子的线性碳链的末端二醇。
8.根据权利要求1-7中任一项所述的方法,其中木质素通过以下方式改性:乙醛酸化、醚化、酯化或提高木质素羟基含量或羧基含量或胺含量或巯基含量的任何其他方法。
9.制备粘合树脂的方法,其中将固体形式的木质素与一种或多种交联剂和/或一种或多种缩水甘油醚混合,然后添加碱性溶液,其中交联剂的环氧指数高于4eq/kg。
10.能够通过权利要求1-9中任一项的方法获得的粘合树脂。
11.根据权利要求10的粘合树脂在制造层合物、矿棉绝缘物、木制品比如胶合板、定向刨花板(OSB)、层压单板木材(LVL)、中密度纤维板(MDF)、高密度纤维板(HDF)、镶木地板、曲面胶合板、贴面刨花板、贴面MDF、层合物或矿棉绝缘物中的用途。
12.根据权利要求10的粘合树脂的用途,其中在以下的制备中将粘合树脂提供至表面:层合物、矿棉绝缘物、木制品比如胶合板、定向刨花板(OSB)、层压单板木材(LVL)、中密度纤维板(MDF)、高密度纤维板(HDF)、镶木地板、曲面胶合板、贴面刨花板、贴面MDF或刨花板、层合物或矿棉绝缘物,并且其中当表面暴露于压力和加热时,发生形成胶粘剂的粘合树脂的固化。
13.根据权利要求12所述使用粘合树脂制造的层合物、矿棉绝缘物、木制品比如胶合板、定向刨花板(OSB)、层压单板木材(LVL)、中密度纤维板(MDF)、高密度纤维板(HDF)、镶木地板、曲面胶合板、贴面刨花板、贴面MDF或刨花板、层合物或矿棉绝缘物。
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EP3818126A4 (en) * | 2018-07-02 | 2022-03-23 | Stora Enso Oyj | METHOD FOR PREPARING A BONDING RESIN |
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JP2011116930A (ja) * | 2009-10-27 | 2011-06-16 | Panasonic Electric Works Co Ltd | 植物由来接着剤と植物由来組成物および木質複合材料 |
US20150344737A1 (en) * | 2012-12-18 | 2015-12-03 | Akzo Nobel Coatings International B.V. | Lignin Based Coating Compositions |
CN107532060A (zh) * | 2015-04-15 | 2018-01-02 | Fp创新研究中心 | 作为木材粘合剂中的成分的高残留含量(hrc)硫酸盐/碱木质素 |
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MXPA06012174A (es) * | 2004-04-20 | 2007-04-19 | Oregon State | Adhesivos lignocelulosicos libres de formaldehido y materiales mixtos hechos a partir de los adhesivos. |
SE0402201D0 (sv) | 2004-09-14 | 2004-09-14 | Stfi Packforsk Ab | Method for separating lignin from black liquor |
US8377853B2 (en) * | 2006-04-20 | 2013-02-19 | M-I L.L.C. | Aqueous gels for well bore strengthening |
DE102010008393A1 (de) * | 2010-02-10 | 2011-10-06 | Technische Universität Dresden | Substrat zur Bodenverbesserung mit Wasser speichernder Eigenschaft, Verfahren zur Herstellung und dessen Verwendung |
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US20150329753A1 (en) * | 2014-05-16 | 2015-11-19 | Board Of Trustees Of The Leland Stanford Junior University | Biobased lignin adhesives for plywood applications and manufacturing of improved wood-based products |
CN108192547B (zh) * | 2017-12-29 | 2020-09-18 | 武汉市科达云石护理材料有限公司 | 高填充高韧性环氧石材胶粘剂及其制备方法 |
SE544555C2 (en) * | 2018-07-02 | 2022-07-12 | Stora Enso Oyj | An epoxy bonding resin obtainable from black liquor lignin |
EP3818126A4 (en) * | 2018-07-02 | 2022-03-23 | Stora Enso Oyj | METHOD FOR PREPARING A BONDING RESIN |
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Patent Citations (4)
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US20040089418A1 (en) * | 2002-05-13 | 2004-05-13 | State Board Of Higher Education On Behalf Of Oregon State University | Formaldehyde-free lignocellulosic adhesives and composites made from the adhesives |
JP2011116930A (ja) * | 2009-10-27 | 2011-06-16 | Panasonic Electric Works Co Ltd | 植物由来接着剤と植物由来組成物および木質複合材料 |
US20150344737A1 (en) * | 2012-12-18 | 2015-12-03 | Akzo Nobel Coatings International B.V. | Lignin Based Coating Compositions |
CN107532060A (zh) * | 2015-04-15 | 2018-01-02 | Fp创新研究中心 | 作为木材粘合剂中的成分的高残留含量(hrc)硫酸盐/碱木质素 |
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BR112021025809A2 (pt) | 2022-02-08 |
SE1950773A1 (en) | 2020-12-25 |
JP2022539516A (ja) | 2022-09-12 |
US20220243105A1 (en) | 2022-08-04 |
CA3141289A1 (en) | 2020-12-30 |
EP3986973A4 (en) | 2023-05-03 |
SE543597C2 (en) | 2021-04-13 |
WO2020261087A1 (en) | 2020-12-30 |
EP3986973A1 (en) | 2022-04-27 |
AU2020307468A1 (en) | 2021-12-16 |
KR20220025743A (ko) | 2022-03-03 |
CL2021003339A1 (es) | 2022-08-26 |
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