WO2015014093A1 - 基于木素胶的制备无甲醛人造板的方法 - Google Patents

基于木素胶的制备无甲醛人造板的方法 Download PDF

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WO2015014093A1
WO2015014093A1 PCT/CN2014/000356 CN2014000356W WO2015014093A1 WO 2015014093 A1 WO2015014093 A1 WO 2015014093A1 CN 2014000356 W CN2014000356 W CN 2014000356W WO 2015014093 A1 WO2015014093 A1 WO 2015014093A1
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lignin
formaldehyde
wood
preparing
straw
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PCT/CN2014/000356
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English (en)
French (fr)
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朱松柏
谢星鹏
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有机木材集团有限公司
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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
    • C08L97/00—Compositions of lignin-containing materials
    • C08L97/02—Lignocellulosic material, e.g. wood, straw or bagasse
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
    • C08H6/00—Macromolecular compounds derived from lignin, e.g. tannins, humic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L97/00—Compositions of lignin-containing materials
    • C08L97/005—Lignin
    • 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
    • C09J197/00—Adhesives based on lignin-containing materials
    • C09J197/005—Lignin

Definitions

  • the invention belongs to the technical field of artificial board production, and particularly relates to an adhesive and a molding method of the artificial board.
  • the adhesive for wood-based panels accounts for 70% of the total amount of adhesives in the world, and the three major rubbers (urea resin (UF), phenolic resin (PF), melamine-formaldehyde resin (MF)) are easy to use.
  • urea resin UF
  • PF phenolic resin
  • MF melamine-formaldehyde resin
  • the advantage of low price has always been the long-term dependence of producers.
  • formaldehyde released during the production and use process has caused harm to the human body, the sales of its products are receiving more and more among the consumers. resistance.
  • more than 1 million tons of formaldehyde is used in fiberboard every year in China, causing serious environmental pollution, including pollution in the production process and indoor air pollution caused by use. Therefore, domestic and foreign scholars have been working on low formaldehyde and formaldehyde-free plates, but there is no major breakthrough in terms of basic theory or process technology.
  • Paper waste lignin is a by-product of the paper industry, with an annual output of more than 10 million tons.
  • China's application of lignin is still very small, and paper waste lignin has not been well utilized.
  • Most of the high-concentration black liquor is burned for the recovery of alkali, and only the combustion is released. The heat is not of high value.
  • a considerable amount of lignin in low concentrations is emitted into the water body, causing serious water pollution. Therefore, it is necessary to develop and utilize the waste wood lignin resources to increase the recycling value.
  • lignin like an adhesive, is distributed around cellulose and hemicellulose, mainly distributed in the S2 layer (the largest total amount) and the composite intercellular layer (the highest concentration) of the fiber cells. It has a strong adhesion to cellulose fibers, making it a strong skeleton structure. According to this characteristic and principle of lignin, people have been working on the development of lignin-based adhesives for many years.
  • As an adhesive there are two ways to apply lignin in industry. One is directly used as an adhesive, and the other is blended with other adhesives such as phenolic and urea-formaldehyde.
  • lignin When lignin itself is used as an adhesive, it requires a certain acidity, and the hot pressing temperature is high, which requires a longer hot pressing time than other glues. At the same time, the lignin compression will make the product appear black, increase the post-processing procedure of the production, and the physical properties and water resistance of the product have major defects; in view of the above deficiencies, people try to adopt the modified method to change the lignin performance.
  • Common modification methods include methylolation, phenolation, oxidation, and the like.
  • lignin-phenolic aldehyde (LPF) glue lignin-urea aldehyde (LUF) glue
  • LMF lignin-melamine
  • LPU lignin- Polyurethane rubber
  • these lignin adhesives contain a large amount of formaldehyde, which limits the use of fiberboard, and also produces more formaldehyde-containing waste gas during the production process and use.
  • LPF lignin-phenolic aldehyde
  • LMF lignin-urea aldehyde
  • LMF lignin-melamine
  • LPU lignin- Polyurethane
  • the present invention proposes a method for preparing a formaldehyde-free wood-based panel from lignin, and the wood-based panel produced by the method is environmentally friendly and formaldehyde-free.
  • a method for preparing a formaldehyde-free artificial board based on lignin glue according to the present invention is a lignin adhesive formed by acetylation of paper waste lignin and a granule formed by pulverizing straw by air pulverization technology.
  • a method of mixing and hot pressing a formed panel is a lignin adhesive formed by acetylation of paper waste lignin and a granule formed by pulverizing straw by air pulverization technology.
  • Paper waste lignin contains a large amount of phenolic hydroxyl groups, alcoholic hydroxyl groups and carboxyl groups, and has a high polarity, resulting in a high softening point and difficulty in plasticizing.
  • One of the technical points of the present invention is that the lignin of papermaking waste is acetylated by acetic anhydride, so that the modified lignin has good thermoplasticity and hot meltability.
  • the papermaking waste lignin modification method is: using a mixture of 4-dimethylaminopyridine and pyridine (1:1-3, V:V) as a catalyst, the amount is 3-5%, at 30 -50 ⁇ acetylation of lignin with a mixture of acetic anhydride/acetic acid (1: 1, V: V) (solid-liquid ratio 1:1-2), reaction time 3-5h, degree of acetylation of lignin When it reaches 1.1/C9 or above, the glass point transfer temperature (Tg) of lignin is reduced to below 170 °C, thereby forming lignin rubber.
  • Tg glass point transfer temperature
  • the straw is pulverized to a straw particle size of 50-80 microns using an air pulverization technique.
  • a method for preparing a formaldehyde-free artificial board by using lignin gum and straw granules is to prepare a formaldehyde-free artificial board by a secondary hot pressing method, specifically:
  • the first hot pressing Mixing the lignin gum with the straw granules at a medium and low temperature of 140-160 ° C, paving in the mold, the amount of lignin is 10%-30% of the total raw material, and then hot pressing , hot pressing pressure is 3-7Mpa, holding pressure for 3-10 minutes, pressure relief; at this temperature, the hemicellulose in the straw fiber is deacetylated to produce acetic acid, and acetic acid partially dissolves the lignin to disperse the lignin to the straw Forming a particle-lignin gum complex between the particles;
  • Second hot pressing increase the hot pressing temperature to 170-200 ° C, increase the pressure to 8-12 MPa, hold pressure for 8-15 minutes, moisture content Maintain 3 to 5%, then relieve pressure and cool; acetylated lignin melts at 170 C, enters the straw cell wall, and interpenetrates and plasticizes between lignin and cellulose and hemicellulose components.
  • High-strength Interpenetrating Polymer (INP) structure increase the hot pressing temperature to 170-200 ° C, increase the pressure to 8-12 MPa, hold pressure for 8-15 minutes, moisture content Maintain 3 to 5%, then relieve pressure and cool; acetylated lignin melts at 170 C, enters the straw cell wall, and interpenetrates and plasticizes between lignin and cellulose and hemicellulose components.
  • High-strength Interpenetrating Polymer (INP) structure increase the hot pressing temperature to 170-200 ° C, increase the pressure to 8-12 MPa, hold pressure for 8-15
  • the advantages of the present invention are as follows: (1)
  • the acetylated lignin adhesive is an environmentally friendly formaldehyde-free fiberboard binder, and the industrial lignin from the paper mill is subjected to acetylation to reduce the Tg to below 170 ,.
  • the acetylated lignin is melted under the condition of 170 ⁇ in the high-temperature molding process of the subsequent fiberboard, and enters the straw cell wall, and interpenetration and plasticization occur between the lignin and the cellulose and hemicellulose components.
  • the production process and products developed by the invention have no formaldehyde pollution problem, and the problem of formaldehyde pollution caused by ordinary fiberboard is solved from the source.
  • Straw fiberboard is more traditional
  • Formaldehyde-containing fiberboards have higher physical strength, water resistance and durability.
  • the modulus of elasticity is above 4,000 MPa, which is comparable to high-grade wood.
  • the specific implementation process for preparing formaldehyde-free artificial board by using the technical scheme of the present invention is divided into three steps: preparation of lignin gum, preparation of straw granules, preparation of formaldehyde-free artificial board by using lignin glue and straw granules, as follows
  • the preparation process is specifically exemplified as follows:
  • the straw was pulverized to a straw particle size of 70 ⁇ m by air pulverization technique.
  • the raw materials were prepared according to the thickness of the sheet of 5 mm, the density of 0.7 g/cm3, and the lignin content of 30%, wherein the size of the corn stover powder was 70 um.
  • Fibreboard hot pressing process The hot pressing is carried out in two stages.
  • the specific hot pressing process parameters are: first stage hot pressing temperature 140 ⁇ , boosting to 5 MPa, holding pressure about 5 min, pressure relief; second stage temperature rising to 190 °C, the pressure is increased to 10Mpa, the pressure is kept for 10 minutes, the pressure is relieved, and the cooling is formed.
  • the straw was pulverized to a straw particle size of 80 ⁇ m by air pulverization technique.
  • the raw materials were prepared according to the thickness of the sheet of 5 mm, the density of 0.7 g/cm3, and the lignin content of 30%, wherein the size of the corn stover powder was 80 um.
  • Fibreboard hot pressing process The hot pressing is carried out in two stages.
  • the specific hot pressing process parameters are: first stage hot pressing temperature 160 ° C, boosting to 4 Mpa, holding pressure about 5 min, pressure relief; second stage temperature rise At 190 °C, the pressure is increased to l lMpa, the pressure is maintained for 9 minutes, the pressure is relieved, and the molding is cooled.
  • the straw granules formed by the air pulverization technique in the actual application process should have a particle size of 50-80 micrometers.
  • the technical objects described in the present invention can be achieved by using various technical parameters in the technical solutions described in the present invention.

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  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
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  • Forests & Forestry (AREA)
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Abstract

一种基于木素胶的制备无甲醛人造板的方法，是利用造纸废木素乙酰化后形成的木素胶胶黏剂与采用空气粉碎技术粉碎秸秆形成的颗粒经混合并热压而形成的人造板的方法。特别的，木素乙酰化是采用4-二甲氨基吡啶和吡啶混合物（1:1-3，V:V）为催化剂在常温下进行的。乙酰化木素胶黏剂不含有甲醛，且乙酰化能在常温下快速反应；生产的人造板具有更高的物理强度、耐水性和耐久性。

Description

说 明 书 基于木素胶的制备无甲醛人造板的方法 技术领域
[0001] 本发明属于人造板生产的技术领域， 具体涉及到人造板的胶黏剂和成型方法。
： 景拔术： V：：：：：：：：： ^
[0002] 人造板用胶粘剂占世界胶粘剂总量的 70%之多， 而其中的三大胶 （脲醛树脂 (UF)、 酚醛树脂 (PF)、 三聚氰胺一甲醛树脂 (MF) ) 以其使用方便、 价格低廉的优势一直以来受到生 产者的长期依赖， 但是， 自其被证实在生产和使用过程中释放的甲醛会对人体造成伤害以 来， 其产品的销售在广大消费者中正接受越来越大的阻力。 据统计， 我国每年有 100万吨以 上的甲醛用于纤维板， 引起严重的环境污染， 包括生产过程的污染和使用中引起的室内空气 污染。 因此， 国内外学者一直致力于低甲醛和无甲醛板的研究， 但目前无论在基础理论方面 还是工艺技术方面尚没有重大突破。
[0003] 造纸废木素是造纸工业的副产物， 我国每年产量约有 1000 多万吨。 但时至今日， 我 国对木素的应用仍然很少， 造纸废木素还没有得到很好的高值化利用， 大多数高浓黑液是为 了回收碱而燃烧掉， 只利用了燃烧所放出的热量，其利用价值不高。 相当多的低浓度中的木 素被排放至水体， 造成严重的水污染。 因此如何开发利用造纸废木素资源以提高其回收利用 价值就显得非常必要。
[0004] 天然植物中,木素就象胶黏剂一样， 分布在纤维素和半纤维素的周围， 主要分布在纤 维细胞的 S2层 （总量最大） 和复合胞间层 （浓度最高）， 对纤维素纤维具有很强的粘合作 用， 使之成为强有力的骨架结构。 根据木素的这一特性和原理， 多年来， 人们纷纷致力于基 于木素的胶黏剂开发工作。 作为胶粘剂， 目前木素在工业上的应用有两种途径， 一是直接作 为胶粘剂， 二是与酚醛、 脲醛等其它胶粘剂共混改性后使用。 木素本身作为胶黏剂使用时， 要求有一定的酸度， 而且热压温度偏高， 与其它胶相比需要更长的热压时间。 同时木素压缩 后会使产品呈现黑色， 增加了生产的后加工程序， 而且产品的物理性能、 耐水性都存在较大 缺陷； 针对以上不足， 人们尝试采用改性的方法以改变木质素性能， 常见的改性方法包括羟 甲基化、 酚化、 氧化法等。 而利用木素对酚醛、 脲醛改性方面， 国内外主要集中在木素-酚 醛 （LPF ) 胶， 木素 -脲醛 （LUF ) 胶， 木素-三聚氰氨 （LMF ) 胶， 木素-聚氨酯 （LPU) 胶 等品种， 已取得多项突破， 但是这些木素胶粘剂含有大量的甲醛， 限制了纤维板的使用范 围， 其生产过程和使用过程中也产生较多含甲醛废气。 而木素直接作为胶粘剂使用时存在玻 璃点转移温度高、 成型时不易融熔化与分散。 说 明 书
发明内容
[0005Γ针对现有技术存在的问题， 本发明提出了一种 ¾于木素 的制备无甲醛人造板的方 法， 利用该方法生产的人造板环保无甲醛。
[0006] 本发明所述的一种基于木素胶的制备无甲醛人造板的方法是利用造纸废木素乙酰化 后形成的木素胶胶黏剂与采用空气粉碎技术粉碎秸秆形成的颗粒经混合并热压而形成的人造 板的方法。
[0007] 造纸废木素含有大量的酚羟基、 醇羟基和羧基， 极性大， 致使其软化点高， 难以塑 化。 本发明的一个技术点就是通过乙酸酐对造纸废弃的木素进行乙酰化， 使改性后的木素具 有良好的热塑性和热熔融性。
[0008] 所述造纸废弃的木素改性的方法为： 采用 4-二甲氨基吡啶和吡啶混合物 （1 :1-3， V:V) 为催化剂,用量为 3-5%，， 在 30-50Ό下利用乙酸酐 /乙酸混合液 （1 : 1， V： V ) 对木素 进行乙酰化 （固液比为 1 :1-2)， 反应时间为 3-5h， 木素的乙酰化度达到 1.1/C9以上， 使得木 素的玻璃点转移温度 （Tg) 降到 170°C以下， 由此形成木素胶， 具体化学反应过程如下：
Figure imgf000003_0001
利用空气粉碎技术将秸秆粉碎到至 50-80微米尺寸的秸秆颗粒。
[0009] 利用木素胶和秸秆颗粒制备无甲醛人造板的方法是采用二次热压法制备无甲醛人造 板， 具体为：
第一次热压： 在中低温 140-160°C条件下， 将木素胶与秸秆颗粒混合均匀， 在模具中铺装， 木素用量为总原料的 10%-30%， 然后进行热压， 热压压力为 3-7Mpa， 保压 3-10分钟， 卸 压； 在此温度下秸秆纤维中的半纤维素脱乙酰基， 产生乙酸， 乙酸对木素进行部分溶解使木 素分散至秸秆颗粒之间形成颗粒-木素胶复合体；
第二次热压： 将热压温度升至 170-200°C， 压力提高至 8-12Mpa， 保压 8-15分钟， 含水率为 保持为 3— 5%， 然后泄压， 冷却； 乙酰化木素在 170 C条件下发生熔融， 进入秸秆细胞壁， 木素与纤维素、 半纤维素组分之间发生互穿和塑化， 产生高强度的互穿网络聚合物 (Interpenetrating Polymer, 简称 INP) 结构。
[0010] 本发明的优点在于： （1 ) 乙酰化木素胶黏剂是环境友好的不含甲醛的纤维板粘合 剂， 来自造纸厂的工业木素经过乙酰化处理后 Tg下降到 170Ό以下， 使得后续纤维板的高 温成型过程中乙酰化木素在 170Ό条件下发生熔融， 进入秸秆细胞壁， 木素与纤维素、 半纤 维素组分之间发生互穿和塑化。 （2) 本发明开发的生产工艺过程和产品均无甲醛污染问题， 从源头上解决了采用普通纤维板引起室内装修的甲醛污染问题。 （3 ) 秸秆纤维板较传统的
说
含甲醛纤维板具有更高的物理强度、 耐水性和耐久性。 尤其是弹性模量达到 4000MPa 以 上， 可以与高档次木材相媲美。
书
具体实施:方式:：： ..
[0011] 利用本发明所述的技术方案制备无甲醛人造板的具体实施过程分为木素胶的制备、 秸 秆颗粒的制备、 利用木素胶和秸秆颗粒制备无甲醛人造板三个步骤， 如下具体举例其制备过 程， 具体如下：
实施例一
( 1 )木素胶的制备
称取 30g干燥后的造纸废木素， 加入 30g乙酸酐和 30g醋酸， 然后加入 3%的催化剂， 在 30 °C反应 5h， 然后减压蒸发、 干燥， 粉碎， 得到纳米级乙酰化木素胶。
[0012] (2) 秸秆颗粒
利用空气粉碎技术将秸秆粉碎到至 70微米尺寸的秸秆颗粒。
[0013] (3 ) 无甲醛人造板的制备
按照板材厚度 5mm， 密度 0.7g/cm3、 木素用量 30%的要求准备原料， 其中玉米秸秆粉末的 尺寸为 70um。
[0014] 纤维板热压工艺： 热压分两段进行， 具体热压工艺参数为： 第一段热压温度 140Ό , 升压至 5Mpa， 保压 5min左右， 卸压； 第二段温度升至 190°C， 压力提高至 10Mpa， 保压 lOmin, 卸压， 冷却成型。
[0015] 利用本发明所述技术方案制备的无甲醛人造板材的物理性能指标： 静曲强度： 21.4MPa、 弹性模量 3768.2MPa、 24h吸水厚度膨胀率： 8.4%， 内结合强度： 1.6MPa; 游离 甲醛： 未检出。
[0016] 实施例二 说 明 书
( 1 )木素胶的制备
称取 100g干燥后的造纸废木素， 加入 100g乙酸酐和 100g醋酸， 然后加入 5%的催化剂， 在 45Ό反应 4h， 然后减压蒸发、 干燥， 粉碎， 得到纳米级乙酰化木素胶。
[0017] (2)秸秆颗粒
利用空气粉碎技术将秸秆粉碎到至 80微米尺寸的秸秆颗粒。
[0018] (3 )无甲醛人造板的制备
按照板材厚度 5mm， 密度 0.7g/cm3、 木素用量 30%的要求准备原料， 其中玉米秸秆粉末的 尺寸为 80um。
[0019] 纤维板热压工艺： 热压分两段进行， 具体热压工艺参数为： 第一段热压温度 160°C， 升压至 4Mpa， 保压 5min左右， 卸压； 第二段温度升至 190 °C， 压力提高至 l lMpa, 保压 9min, 卸压， 冷却成型。
[0020] 需要特别说明的是， 在实际应用过程中秸秆利用空气粉碎技术粉碎形成的秸秆颗粒 的粒度尺寸应在 50-80微米之间。 利用本发明所述的技术方案中的各项技术参数均能实现本 发明所述的技术目的。

Claims

权 利 要 求 书
1. —种基亍木素胶的制备无甲醛人造板的方法是利用造紙废木素乙酰 后形成的木素胶胶 黏剂与釆用空气粉碎 tt术粉碎稻秆形成的颗粒经混合并热压面形成的人造板的方法 β
2. 翻权利要求 1所述的一种基于木素跤的制备无甲醛人造板諭方法， 其特征在于： 厨逮木 素乙酰化的方法为：
釆用体 ft比为 1:1-3的 4-二甲氩基吡 1«和吡啶混合物为催化剂， 用量为 3-5%, 在 30-50 C下 利用体积比为 1 : 1的乙酸酐或乙酸混合液对木素进行乙酜化, 反应时间为 3-5h, 木素 «乙» 化度达到 1.1/C9以上， 使得木 ^的玻璃点转移温度降到 17CTC以下， 由此形成木素胶。
3. 如权利要求 1所述酌一种基于木素腔的制备无甲醛人造极 W方法， 其特征在于： 所述采 用空气粉碎技术粉碎穆秆形成的颗粒尺寸的大小为 50-80微米。
4. 如权利要求 1所述 tt—种基于木索胶的劇备无屮酸人造板的方法， 其特征在于: 利用木 素胶和秸秆颗粒制备无甲醛人造板的方法是采用二次热压法制备无甲醒人造板， 具体为： 第一次热 Jfc 在中低温 14<H6(TC条件下， 将木素胶与 ft秆颗粒《合均匀， 在模具中铺装， 木素用量为总癒料的 10%-30%, 然后 «行热 ， 热压 15力为 5Mpa， 保压 3-10分钟》 卸 压； 在此温度下桔秆奸维中翁半纤维素脱乙睡基， 产生乙酸， 乙酸对术素进行部分渗解使木 素分散至秸 ff颗粒之闻形成颗粒-木素胶复合体；
第二次热压： 梅热£温度升至 170-20<rC， £Ε力提髙至 lOMpa, 保 ^ 15分钟， 含水率为保 持为 3— 5%, 然后泄压， 冷却; 乙酰化木素在 170*0条件下发生熔融, 进入秸秆细胞壁. 木 素与好维素、 半纤维素组分之间发生 :穿和塑化， 产生高强度的互穿网络聚合物结构。
5. 如权利要求 2所述 »—种基于木素胶的制备无甲薩人造板 方法， 其特征在子； 所述木 素乙酰化过程中 Θ液体积比为 1 : 1-2。
PCT/CN2014/000356 2013-07-30 2014-04-01 基于木素胶的制备无甲醛人造板的方法 WO2015014093A1 (zh)

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