WO2005070635A1

WO2005070635A1 - The water-proof composite sheet

Info

Publication number: WO2005070635A1
Application number: PCT/CN2005/000016
Authority: WO
Inventors: Tianrui Ren
Original assignee: Institute Of Process Engineering, Chinese Academy Of Sciences
Priority date: 2004-01-15
Filing date: 2005-01-05
Publication date: 2005-08-04
Also published as: CN100368167C; CN1640640A

Abstract

The present invention relates to a water-proof composite sheet. The sheet is produced by blending 20-70wt% vegetable fiber, 10-60wt% pulverized coal ash and 5-40wt% binder and subsequent molding the resultant blend, where said vegetable fiber includes fiber powder produced from stalks of crops or the like, said pulverized coal ash includes coal powder with a combustion loss of less than 10 % in a variety of industries, and said binder is a mixture comprising maleic anhydride, fhthalic anhydride, polyhidric alcohol, styrene or homologues thereof, and also comprises melamine, acrylic acid or rosin and dicyclopentadiene. The water-proof composite sheet of the present invention also comprises 10-40wt% new or old plastic. Said water-proof composite sheet exhibits high strength, good water proofness and reduced pollution of the environment due to fact that most of materials employed are wastes from industry and agriculture. Said water-proof composite sheet can be widely used in the sheet-manufacturing industry, furniture-manufacturing industry and the industry of material for decoration and architecture, and also used for producing material for automotive interior decoration.

Description

一种复合防水板材及其制备方法和用途技术领域 Composite waterproof sheet, preparation method and application thereof

本发明涉及一种复合防水板材及其制备方法和用途。背景技术 The invention relates to a composite waterproof sheet and a preparation method and application thereof. Background technique

家具制造业与建筑装潢业需要大量地消耗木材，造成了世界森林的急剧下降与土地荒漠化，于是世界各国出台各种政策，限制森林的砍伐，使得建材业原料紧张。另一方面，粉煤灰与秸秆是当今工业与农业生产中的两大废弃物。据统计，全世界粉煤灰与秸秆的排放量分别约为 1.6 亿吨 / 年和 29亿吨 /年，而在中国其为 1.1亿吨 /年和 6亿吨 /年。另夕卜，随着塑料消费需求的增加，废旧塑料的总量也在不断扩大，美国年生产废旧塑料超过 1600万吨，中国年生产废旧塑料超过 1400万吨。这三种废弃物对人类的生态环境造成了巨大的压力，因而将粉煤灰、秸秆以及废旧塑料的再利用成为全球性的研究热点，尤其是人们希望通过各种技术，将这些废弃物作为木材的替代品用于建材业。 The furniture manufacturing and construction and decoration industries need to consume a large amount of wood, which has caused a sharp decline in the world ’s forests and land desertification. Therefore, various countries around the world have introduced various policies to limit the deforestation of forests and make raw materials in the building materials industry tight. On the other hand, fly ash and straw are two major wastes in today's industrial and agricultural production. According to statistics, the emissions of fly ash and straw worldwide are about 160 million tons / year and 2.9 billion tons / year respectively, while in China they are 110 million tons / year and 600 million tons / year. In addition, with the increase in consumer demand for plastics, the total amount of waste plastics is also expanding. The annual production of waste plastics in the United States exceeds 16 million tons, and the annual production of waste plastics in China exceeds 14 million tons. These three kinds of waste have caused tremendous pressure on the human ecological environment, so the reuse of fly ash, straw and waste plastic has become a global research hotspot, especially people hope to use these wastes as Wood substitutes are used in the building materials industry.

已经有许多专利报道，利用桔秆来制备人造板材。在 US 6103377和 "CN 96108108 中公开了釆用提纯后的植物纤维也就是纸纤维制备高密度板材的技术；在 US 5656129和 CN 01100009中公开了采用提纯的小麦秸秆与木质纤维制备低密度、中密度和高密度板材专利。但是这些技术制得的板材强度低，不防水防火，并且在生产过程中易造成环境污染。在 CN 95117473 中公开了用甲醛、尿素、三聚氰氨和氨水调治的胶与秸秆直接压制板材，这类方法生产的板材，虽然强度比较好，但是容易产生对人体有毒的甲醛气体，而且防水性也比较差。 Numerous patents have reported the use of orange stalks to make artificial boards. US 6103377 and "CN 96108108 disclose the technology of preparing high-density boards using purified plant fibers, that is, paper fibers; US 5656129 and CN 01100009 disclose the use of purified wheat straw and wood fibers to prepare low-density, medium- Density and high-density board patents. However, boards made by these technologies have low strength, are not waterproof and fireproof, and are easy to cause environmental pollution during production. CN 95117473 discloses the use of formaldehyde, urea, melamine, and ammonia to treat Glue and straw directly press the plate. Although the plate produced by this method has good strength, it is easy to produce formaldehyde gas that is toxic to humans and has poor water resistance.

由于粉煤灰具有机械强度高和重量轻的特点，在 GB 1468165和 CN 91102499中公开了将其直接压縮制备天花板材；在 CN 99211198中公开了制备防火板材的技术。发明内容 Due to the characteristics of high mechanical strength and light weight, fly ash is disclosed in GB 1468165 and CN 91102499 for directly compressing and preparing ceiling materials; and CN 99211198 is disclosed in the technology of preparing fire-proof boards. Summary of the invention

本发明的目的在于克服已有技术制得的板材强度低，不防水防火，在生产过程中易造成环境污染的缺陷，从而提供一种高强度、防水、不易造成环境污染的复合防水板材。本发明的目的是通过如下的技术方案实现的： The purpose of the present invention is to overcome the defects that the sheet made by the prior art has low strength, is not waterproof and fireproof, and is easy to cause environmental pollution during the production process, so as to provide a composite waterproof sheet with high strength, water resistance, and less likely to cause environmental pollution. The object of the present invention is achieved by the following technical solutions:

本发明提供一种复合防水板材，由如下组份通过共混模压聚合制成：植物纤维 20〜70重量份； The present invention provides a composite waterproof sheet made of the following components through blend molding polymerization: 20 to 70 parts by weight of vegetable fiber;

粉煤灰 10〜60重量份； 10 ~ 60 parts by weight of fly ash;

粘合剂 5〜40重量份； 5 ~ 40 parts by weight of adhesive;

所述的植物纤维包括农作物的秸秆、各种树木的枝衩为原料制成的纤维粉末，以及木材加工所生成的木屑；所述的农作物包括小麦、水稻、玉米、棉花、甘蔗； ' The plant fibers include straws of agricultural crops, fiber powder made from branches of various trees as raw materials, and wood chips generated from wood processing; the crops include wheat, rice, corn, cotton, and sugar cane;

所述的粉煤灰包括了火力发电厂、炼钢厂、化工厂和其它行业的烧失量低于 10%的燃煤粉体； . The fly ash includes coal-fired powder with a loss on ignition of thermal power plants, steel plants, chemical plants and other industries of less than 10%;.

所述的粘合剂为由顺丁烯二酸酐、邻苯二甲酸酐、多元醇、苯乙烯或其同系物按重量份 10: 15： 10： 30的比例制得的混合物； The adhesive is a mixture prepared from maleic anhydride, phthalic anhydride, polyhydric alcohol, styrene, or a homologue thereof in a proportion of 10: 15: 10: 30 by weight;

所述的粘合剂还包括三聚氰胺、丙烯酸、或松香和双环戊二烯。本发明提供的复合防水板材，其原料组份还包括：塑料 10〜40重量份；所述的塑料选自聚乙烯（PE)、聚氯乙烯（PVC)、聚苯乙烯 (PS)、乙烯一醋酸乙烯共聚物 (EVA)、聚胺酯 (PU)、聚丙烯 (PP)、聚碳酸酯 (PC)、邻苯二甲酸乙二醇酯（PET)、 ABS树脂、 SBS树脂中的一种或几种的混合物，可以是新塑料，也可以是废旧塑料，即上所述各种回收的热塑性塑料的粉体以任意比例的共混粉体。 The adhesive also includes melamine, acrylic, or rosin and dicyclopentadiene. The composite waterproof sheet provided by the present invention further comprises: 10 to 40 parts by weight of plastic; the plastic is selected from polyethylene (PE), polyvinyl chloride (PVC), polystyrene (PS), and ethylene-1 One or more of vinyl acetate copolymer (EVA), polyurethane (PU), polypropylene (PP), polycarbonate (PC), polyethylene phthalate (PET), ABS resin, SBS resin The mixture may be a new plastic or a waste plastic, that is, a blend of powders of the various recycled thermoplastics described above in any proportion.

本发明提供一种上述复合防水板材的制备方法，包括如下步骤： The invention provides a method for preparing the composite waterproof sheet, which includes the following steps:

1 ) 将植物纤维干燥后，粉碎至长度低于 50毫米； 1) After drying the plant fibers, crush them to a length of less than 50 mm;

2) 在室温下，先将 5〜40重量份的粘合剂与粘合剂重量 2%的过氧化引发剂混合均匀后，再与 20〜70重量份步骤 1 ) 的经粉碎的植物纤维混合，制成预模压料； 2) At room temperature, first mix 5 ~ 40 parts by weight of the binder with 2% by weight of the peroxidation initiator, and then mix with 20 ~ 70 parts by weight of the crushed plant fiber in step 1). , Made into pre-molded material;

3 ) 将 10〜60重量份的粉煤灰倒入步骤 2) 的预模压料中，混合均匀制成模压料； 3) Pour 10 ~ 60 parts by weight of fly ash into the pre-molding material of step 2), mix it uniformly to make a molding material;

4) 将步骤 3 ) 制得的模压料填在模压机的模腔中，于 5Mpa条件下 110°C加热 10分钟，在维持此压力下冷却到 80°C，停止加压；冷却至 50 °C以下，打开模腔，得到复合防水板材，修边备用； 4) Fill the molding material obtained in step 3) in the cavity of the molding machine, and heat it at 110 ° C for 10 minutes under the condition of 5Mpa. Cool it to 80 ° C while maintaining this pressure, and stop pressing; cool to 50 ° Below C, open the mold cavity to obtain a composite waterproof sheet and trim it for future use;

所述的植物纤维包括农作物的秸秆、各种树木的枝杈为原料制成的纤维粉末，以及木材加工所生成的木屑；所述的农作物包括小麦、水稻、玉米、棉花、甘蔗；所述的粉煤灰包括了火力发电厂、炼钢厂、化工厂和其它行业的烧失量低于 10%的燃煤粉体； The plant fibers include straws of crops, fiber powder made from branches of various trees as raw materials, and wood chips generated from wood processing; the crops include wheat, rice, corn, cotton, and sugar cane; The fly ash includes coal-fired powders with a loss on ignition of less than 10% in thermal power plants, steel plants, chemical plants and other industries;

所述的粘合剂还包括三聚氰胺、丙烯酸、或松香和双环戊二烯。 The adhesive also includes melamine, acrylic, or rosin and dicyclopentadiene.

所述步骤 1 ) 的植物纤维长度优选 5〜20毫米。 The length of the plant fiber in step 1) is preferably 5-20 mm.

所述的过氧化引发剂为过氧化氢、过氧化苯甲酰胺或过硫酸胺。 The peroxidation initiator is hydrogen peroxide, benzamide peroxide or amine persulfate.

本发明提供的复合防水板材的制备方法，还包括在步骤 3 ) 中加入 10〜40重量份的塑料。 The method for preparing a composite waterproof sheet provided by the present invention further comprises adding 10 to 40 parts by weight of plastic in step 3).

所述的塑料选自聚乙烯（PE)、聚氯乙烯（PVC)、聚苯乙烯 (PS)、乙烯一醋酸乙烯共聚物 (EVA：)、聚胺酯 (PU)、聚丙烯 (PP：)、聚碳酸酯 (PC)、邻苯二甲酸乙二醇酯（PET)、 ABS树脂、 SBS树脂中的一种或几种的混合物，可以是新塑料，也可以是废旧塑料。 The plastic is selected from polyethylene (PE), polyvinyl chloride (PVC), polystyrene (PS), ethylene-vinyl acetate copolymer (EVA :), polyurethane (PU), polypropylene (PP :), polymer One or more of carbonate (PC), polyethylene phthalate (PET), ABS resin, and SBS resin may be a new plastic or a waste plastic.

本发明利用植物纤维、粉煤灰或 /和塑料，采用材料接枝技术与半互穿聚合物网络 (Semi- IPN, Semi-interpenetrating polymer network,) ¾ 制备的高强度防水复合板材具有优越的防水、耐腐蚀、抗冲击性、隔音与防虫等效果，材料完全不含有甲醛，是一种新型的环保材料。可用于制备各种家具、室内外装修与建筑材料中。 The high-strength waterproof composite board prepared by using plant fiber, fly ash or / and plastic, using a material grafting technology and a semi-interpenetrating polymer network (Semi-IPN, Semi-interpenetrating polymer network,) has superior waterproof performance. , Corrosion resistance, impact resistance, sound insulation and insect resistance, the material does not contain formaldehyde at all, is a new type of environmentally friendly materials. It can be used in the preparation of various furniture, interior and exterior decoration and building materials.

本发明提供的复合防水板材及其制备方法的优益之处在于： The advantages of the composite waterproof sheet provided by the present invention and its preparation method are:

1、复合防水板材主要原料之一的秸秆，其表面存在大量的羟基，可与粘合剂形成酉旨键和大量的氢键，在板材中的作用是增加人造板材的韧性，减少人造板材的单位重量，提高人造板材的抗弯曲性能； 1. Straw, one of the main raw materials of composite waterproof sheet, has a large number of hydroxyl groups on the surface, which can form bond bonds and a large number of hydrogen bonds with the adhesive. Its role in the sheet is to increase the toughness of the artificial sheet and reduce the Unit weight, improve the bending resistance of artificial board;

2、复合防水板材主要原料之一的粉煤灰，是一类多羟基的无机矿物质，不仅重量轻，而且可以提高人造板材的抗冲击性能； 2. Fly ash, which is one of the main raw materials of composite waterproof sheet, is a kind of polyhydroxy inorganic mineral, which is not only light in weight, but also can improve the impact resistance of artificial sheet;

3、复合防水板材主要原料之一的的粘合剂，主要组分为丁二烯酸酐、苯酐、多元醇和苯乙烯，具有少量的自由羧基，在制备复合板材的过程中与秸秆表面的基以及粉煤灰表面的羟基发生酯化，形成了体形结构，提高了板材的防水性和强度；当粘合剂中加入三聚氰胺时，可以生成星状的聚酰胺，与粘合剂中的聚酯和聚苯乙烯形成了互穿高聚物网络结构（IPN) 的粘合剂，对于防水与防腐性能均有极大的提高；当加入松香和双环戊二烯时，可以提高粘合剂的流动性与应用的表面光洁度； 3. The adhesive of one of the main raw materials of composite waterproof sheet, the main components are butadiene anhydride, phthalic anhydride, polyol and styrene, with a small number of free carboxyl groups. The hydroxyl groups on the surface of the fly ash are esterified to form a body structure, which improves the waterproofness and strength of the board. When melamine is added to the adhesive, a star-shaped polyamide can be formed. Polystyrene forms an interpenetrating polymer network structure (IPN) adhesive, which greatly improves waterproof and anticorrosive properties; when rosin and dicyclopentadiene are added, the fluidity of the adhesive can be improved And applied surface finish;

4、复合防水板材主要原料之一的塑料，加入复合板材中可以减低粘合剂的用量，同时提高了复合板材的可加工性与可饰性； 4. Plastic, one of the main raw materials of composite waterproof sheet, can be added to the composite sheet to reduce viscosity. The amount of the mixture improves the processability and decorability of the composite board;

5、本发明采用的原材料大部分是工农业的废弃产品，所以不但原料资源丰富，而且价格低廉；同时为桔秆、粉煤灰和废旧塑料的再利用提供了巨大的市场，降低了对环境造成的污染； 5. Most of the raw materials used in the present invention are waste products of industry and agriculture, so not only the raw material resources are rich, but the price is low; at the same time, it provides a huge market for the reuse of orange straw, fly ash and waste plastics, and reduces the environmental impact. The pollution caused;

6、本发明的全部生产流程不产生任何的废水和废气，环保卫生。具体实施方式 6. The whole production process of the present invention does not generate any waste water and waste gas, and is environmentally friendly and sanitary. detailed description

本发明使用的秸秆是直接从农田收割来的农作物的茎部，晾干到自由水分含量^;于 15%，用秸秆粉碎机粉碎到长度低于 50毫米，最好是 5〜 20毫米， $1」备成秸杆粉末，备用。其中不同秸秆的化学成分列于表 1，在本发明中最常使用的是小麦秸秆和水稻秸秆。 The straw used in the present invention is the stem of a crop harvested directly from the farmland and dried to a free moisture content of ^; at 15%, pulverized with a straw pulverizer to a length of less than 50 mm, preferably 5 to 20 mm, $ 1 Prepare straw powder for future use. The chemical composition of different straws is listed in Table 1. The most commonly used in the present invention are wheat straw and rice straw.

表 1、秸秆的主要组成 Table 1.The main composition of straw

名称粗蛋白粗纤维灰分钙磷无氮浸出物稻草 4.8 35.1 17.0 0.21 0.08 35 Name Crude protein Crude fiber Ash Calcium Phosphorus Nitrogen-free extract Straw 4.8 35.1 17.0 0.21 0.08 35

小麦秸 3.2 43.6 7.2 0.16 0.08 38.6 大麦秸 3.6 41.6 6.9 0.35 0.10 39.5 玉米秸 5.7 34.3 6.9 0.6 0.1 51.3 蚕豆秸 8.4 41.5 8.4 - - 34.0 燕麦秸 3.8 49.0 7.6 0.27 0.1 40.1 Wheat straw 3.2 43.6 7.2 0.16 0.08 38.6 Barley straw 3.6 41.6 6.9 0.35 0.10 39.5 Corn straw 5.7 34.3 6.9 0.6 0.1 51.3 Broad bean straw 8.4 41.5 8.4--34.0 Oat straw 3.8 49.0 7.6 0.27 0.1 40.1

本发明使用的粉煤灰要求烧失量低于 10%，否则其中未燃尽的炭粒含量高，造成吸水性大，强度低，易风化，不利于复合板材的性能。该粉煤灰的化学组成如表 2所示。 The fly ash used in the present invention requires a loss on ignition of less than 10%, otherwise the content of unburned carbon particles therein is high, resulting in large water absorption, low strength, easy weathering, and detriment to the performance of the composite sheet. The chemical composition of the fly ash is shown in Table 2.

表 2粉煤灰的化学组成（％)

实施例 1、讳 ij备复合防水板材 I Table 2 Chemical composition of fly ash (%)

Example 1. Preparation of composite waterproof sheet I

在室温下，先将粘合剂——顺丁烯二酸酐（工业级）、邻苯二甲酸酐 At room temperature, first the adhesives-maleic anhydride (industrial grade), phthalic anhydride

(工业级）、丙二醇（工业级）、苯乙烯（工业级）质量比是 10: 15： 10： 30的混合物 100g, 与 2g过氧化氢混合均匀后，再与 100g长度为 5〜20 毫米的小麦稻秆混合，制成预模压料；将 100g的电厂粉煤灰（300 目）倒入此预模压料中，混合均匀制成模压料。 (Industrial grade), propylene glycol (industrial grade), styrene (industrial grade) with a mass ratio of 10: 15: 10: 30, 100g, mixed with 2g of hydrogen peroxide, and then with 100g of 5 to 20 mm in length Wheat and straw are mixed to make a pre-molded material; 100 g of power plant fly ash (300 mesh) Pour into this pre-molding material, mix it evenly to make a molding material.

为了利于脱模，在模具中刷少量机油，取 130g模压料填入模腔，用手按平即可，盖上模具上模板压实。将平板硫化压机上下加热板加热到 110°C，使已装料模具在硫化压机上升压到 5MPa，保压、保温 10分钟后，停止加热；在保压的状态下冷却到 80°C。停止加压。将模板冷却至 50 以下，开模取出样品，得到复合防水板材 I，修边备用。在以后的试验中，该板材样品将被加工为小条，一块样品加工 4-6个小条以进行力学性能的按下述方法对复合防水板材 I进行测试，该板材的密度为 l .lg/cm³，吸水率为 1.1 % ,冲击强度为 4096.01 (KJ/m²),静弯曲强度为 20.822Mpa，防虫实验的 AG小于 G1的 0.1%。 In order to facilitate demolding, brush a small amount of oil in the mold, fill 130g of molding material into the mold cavity, press it by hand, and cover it with the mold on the mold to compact. The upper and lower heating plates of the plate vulcanizing press are heated to 110 ° C, so that the charged mold is increased to 5 MPa on the vulcanizing press, and the heating is stopped after 10 minutes of holding and holding; cool to 80 ° under the pressure holding state C. Stop pressurizing. The template is cooled to below 50, and the sample is opened to obtain a composite waterproof sheet I, which is trimmed for later use. In subsequent tests, the sheet sample will be processed into small strips, and one sample is processed into 4-6 strips for mechanical properties. The composite waterproof sheet I is tested according to the following method, and the density of the sheet is l.lg. / cm ³ , the water absorption is 1.1%, the impact strength is 4096.01 (KJ / m ² ), the static bending strength is 20.822Mpa, and the AG of the insect control experiment is less than 0.1% of G1.

测试实验一、对板材的密度、吸水率的测定方法 Test experiment I. Method for measuring the density and water absorption of the board

用云石机、木锯、钢锯等切割工具切割出用于测量的试件，其尺寸为：宽度 b=15 ± 0.1mm,长度 L=23 ±0.5mm，厚度 δ = (5—25 )mm±0.1mm。测量精度为 0.1mm。通过游标卡尺测量，达到该精度后，选取感量为 O.Olg 的天平称重，记录每个试样的质量 G1 (精确到 0.01g)。 Use a cutting tool such as a marble machine, a wood saw, or a hacksaw to cut the test piece for measurement. The dimensions are: width b = 15 ± 0.1mm, length L = 23 ± 0.5mm, and thickness δ = (5-25) mm ± 0.1mm. The measurement accuracy is 0.1mm. Measure with a vernier caliper. After reaching the accuracy, select a balance with a sensitivity of O. Olg and weigh it. Record the mass G1 of each sample (accurate to 0.01g).

取容器装满蒸馏水，并使容器内的水温保持在 20±5°C。将质量为 G1 的试件浸入容器内的蒸馏水中，在 20±5°C的水温下保持 24h。取出试件，用纱布或者吸水纸吸干试件表面水分，立刻称重0。精度为 0.01g。 Fill the container with distilled water and keep the water temperature in the container at 20 ± 5 ° C. The test piece of mass G1 was immersed in distilled water in the container and kept at a water temperature of 20 ± 5 ° C for 24 hours. Remove the test piece, blot the surface of the test piece with gauze or absorbent paper, and immediately weigh 0. The accuracy is 0.01g.

按照下列公式计算每个试件的密度和 24h吸水率 W ( % ), 精确到 0.1 Calculate the density and water absorption W (%) of each test piece according to the following formula, accurate to 0.1

%。 %.

密度 =质量 Gl I (长度 Lx宽度 bx厚度 δ ) Density = Mass Gl I (length Lx width bx thickness δ)

吸水率 W= (G-Gl ) /Gl Water absorption W = (G-Gl) / Gl

G—浸水后试件的重量， g G—weight of test piece after immersion in water, g

Gl—浸水前试件的重量, g。 Gl—weight of test piece before immersion in water, g.

测试实验二、试样的冲击测试 Test experiment two, impact test of the sample

用云石机、木锯、钢锯等切割出用于材料的冲击韧性、静曲强度的试件尺寸为：宽度 b=15 ±0.1mm，长度 L二 120±0.5mm，厚度 δ二（5—25) mm±0.1mm。通过游标卡尺测量，准确记录每个样条的长度、宽度、厚度精确到（0.001mm)。 Use a marble stone machine, wood saw, hacksaw, etc. to cut the test pieces for impact toughness and static bending strength of the material. The dimensions are: width b = 15 ± 0.1mm, length L = 120 ± 0.5mm, thickness δ = 2 (5 —25) mm ± 0.1mm. With vernier caliper measurement, accurately record the length, width, and thickness of each spline to (0.001mm).

釆取常规的简支梁方式在冲击机上测定冲击功（冲击吸收能）。试验时将摆锤挂在机架的扬臂上，摆锤杆的中心线与通过摆锤杆中心的铅垂线成为 α的扬角，此时摆键具有一定位能。然后让摆锤自由下落，位能转变为动能打在试样上。试样断裂成两半后，摆锤的剩余能量使摆锤上升到一定高度， β角为升角。女 Π果，以 w表示摆锤的重量， 1表示摆锤摆杆长度。记录冲击测试机上的冲击功（冲击吸收能）数据。 The conventional simple supported beam method was used to measure the impact energy (impact absorption energy) on the impact machine. Hang the pendulum on the lifting arm of the rack during the test, the center line of the pendulum rod and the plumb line passing through the center of the pendulum rod Become a lift angle of α, at this time the pendulum key has a positioning energy. Then let the pendulum fall freely, the potential energy is transformed into kinetic energy and hit the sample. After the sample breaks into two halves, the residual energy of the pendulum causes the pendulum to rise to a certain height, and the angle β is the rising angle. For female fruit, w is the weight of the pendulum, and 1 is the length of the pendulum. Record the impact energy (impact absorption energy) data on the impact tester.

冲击强度=冲击功 /试样的横截面积 Impact strength = impact energy / cross-sectional area of the specimen

其中，横截面积=试样宽度 L X试样厚度 S Where cross-sectional area = sample width L X sample thickness S

测试实验三、试样的弯曲性能测试 Test experiment three, bending performance test of the sample

用云石机、木锯、锯等切割出用于材料的冲击韧性、静曲强度的试件尺寸为：宽度 b=15 ± 0.1mm，长度 L= 120±0.5mm，厚度 δ = (5—25) mm±0.1mm。通过游标卡尺测量，准确记录每个样条的长度、宽度、厚度精确到（0.001mm)。 The size of the test piece used for impact toughness and static bending strength of the material is cut with a marble machine, wood saw, saw, etc .: width b = 15 ± 0.1mm, length L = 120 ± 0.5mm, thickness δ = (5— 25) mm ± 0.1mm. With vernier caliper measurement, accurately record the length, width and thickness of each spline to (0.001mm).

使用万能材料测试仪 (INSTRON-1121 )对试样的弯曲性能进行测试。测试条件是，温度 23°C，在 5mm/min下弯曲。按下式计算弯曲强度： β二 3PL/2bd² A universal material tester (INSTRON-1121) was used to test the bending properties of the specimens. The test conditions were a temperature of 23 ° C and a bend at 5mm / min. Calculate the bending strength according to the following formula: β 二 3PL / 2bd ²

式中 P为破坏载荷， L为样条跨距， b为样条宽度， d为样条厚度。样条在载荷的作用下的形变称为挠度，样条随着载荷的增加，其挠度也增加，计算弯曲模量 E=L³m/4bd³,m为载荷—挠度曲线上直线的斜率。直接由万能材料测试仪（INSTRON-1121 ) 所附带软件计算得出。 Where P is the failure load, L is the spline span, b is the spline width, and d is the spline thickness. The deformation of a spline under load is called deflection. As the load increases, the deflection of the spline also increases. Calculate the bending modulus E = L ³ m / 4bd ³ , where m is the slope of the straight line on the load-deflection curve. Calculated directly by the software attached to the universal material tester (INSTRON-1121).

测试实验四、防虫实验 Test Experiment IV. Pest Control Experiment

取用云石机、木锯、钢锯等切割工具切割出用于材料的密度、吸水率测量的试件尺寸为：宽度 b=15 ±0.1mm，长度 L=23 ±0.5mm，厚度 δ = (5— 25 ) mm±0.1mm。测量精度为 0.1mm。通过游标卡尺测量，达到该精度后，选取感量为 O.Olg的天平称重，记录每个试样的质量 G1 (精确到 0.01g)。 Take the cutting tools such as marble machine, wood saw, hacksaw, etc. to cut the test pieces for measuring the density and water absorption of the material. The dimensions are: width b = 15 ± 0.1mm, length L = 23 ± 0.5mm, thickness δ = (5—25) mm ± 0.1mm. The measurement accuracy is 0.1mm. Measure with a vernier caliper. After reaching this accuracy, select a balance with a sensitivity value of 0.01 kg and record the mass G1 (accurate to 0.01g) of each sample.

取三块该样品放入带通风装置的玻璃器皿，放入 100-120只白蚁。观察三日后试样的外观是否被白蚁啃食。称量试样记录试样的质量 G2，计算其差值 AG。 Take three pieces of this sample and place them in a glassware with ventilation, and put in 100-120 termites. Observe whether the appearance of the sample after three days was eaten by termites. Weigh the sample, record the mass G2 of the sample, and calculate the difference AG.

实施例 2、制备复合防水板材 II Example 2. Preparation of composite waterproof sheet II

在室温下，先将粘合剂——顺丁烯二酸酐（工业级）、邻苯二甲酸酐 (工业级）、丙二醇（工业级）、苯乙烯（工业级）质量比是 10: 15： 10： 30的混合物 100g，与 2g过氧化苯甲酰胺混合均匀后，再与 100g长度为 5〜20毫米的小麦秸秆、毘合，制成预模压料；将 100g聚氯乙烯（PVC) 细粉（北京有机化工二厂，建材 5型）和 100g的电厂粉煤灰（300目）混合均匀后倒入此预模压料中，混合均勾制成模压料。 At room temperature, the mass ratio of the adhesive—maleic anhydride (industrial grade), phthalic anhydride (industrial grade), propylene glycol (industrial grade), and styrene (industrial grade) is 10: 15: 10: 30 mixture of 100g, mixed with 2g of benzamide peroxide, and then mixed with 100g of wheat straw with a length of 5 to 20 mm to make a pre-molded material; 100g of polyvinyl chloride (PVC) Fine powder (Beijing Organic Chemical Plant No.2, Building Material Type 5) and 100g of power plant fly ash (300 mesh) are mixed uniformly and poured into this pre-molded material, and the mixture is hooked into a molded material.

为了利于脱模，在模具中刷少量机油，取 140g模压料填入模腔，用手按平即可，盖上模具上模板压实。将平板硫化压机上下加热板加热到 110°C，使已装料模具在硫化压机上升压到 5MPa，保压、保温 10分钟后，停止加热；在保压的状态下冷却到 80° ( 。停止加压。将模板冷却至 50°C 以下，开模取出样品，得到复合防水板材 II，修边备用。 In order to facilitate demolding, brush a small amount of oil in the mold, fill 140g of molding material into the mold cavity, press it flat with your hands, and cover the mold on the mold to compact. Heat the upper and lower heating plates of the plate vulcanizing press to 110 ° C, make the charged mold pressurize to 5MPa on the vulcanizing press, and stop heating after holding and holding for 10 minutes. (. Stop pressing. Cool the template to below 50 ° C, open the mold and take out the sample to obtain a composite waterproof sheet II, which is trimmed for later use.

按实施例 1中的方法对复合防水板材 II进行测试，该板材的密度为 Ug/cm3、吸水率为 1.0%，冲击强度为 4501.03 (KJ/m²), 静弯曲强度为 35.853MPa, 防虫实验的 AG小于 G1的 0.1%。 The composite waterproof sheet II was tested according to the method in Example 1. The density of the sheet was Ug / cm3, the water absorption was 1.0%, the impact strength was 4501.03 (KJ / m ² ), and the static bending strength was 35.853MPa. The AG is less than 0.1% of G1.

实施例 3〜29、制备复合防水板材 ΙΠ〜ΧΧΙΧ Examples 3 to 29. Preparation of composite waterproof sheet ΙΠ ~ ΧΧΙΧ

按实施例 1、 2 的方法制备复合防水板材 ΠΙ〜ΧΧΙΧ，并按实施例 1 的方法对其进行测试，列于表 3、表 4。 The composite waterproof sheet II ~ XIXIX was prepared according to the methods of Examples 1 and 2, and tested according to the method of Example 1, which are listed in Tables 3 and 4.

表 3、复合防水板材的组成 Table 3.Composition of composite waterproof sheet

*为方便起见，下表中将顺丁烯二酸酐 (Α)、邻苯二甲酸酐 (Β：)、丙二醇 (C：)、苯乙烯 (D)、三聚気胺 (E)、丙烯酸 (F)、松香 (G)、双环戊二烯 (H)依次用 A、 B、 C、 D、 E、 F、 G表示 * For convenience, maleic anhydride (A), phthalic anhydride (B :), propylene glycol (C :), styrene (D), melamine (E), acrylic acid ( F), rosin (G), and dicyclopentadiene (H) are represented by A, B, C, D, E, F, and G in that order.

实植物纤维及 Plant fiber and

粉煤灰及其塑料及其粘合剂及其施苴 z、 Fly ash and its plastic and its binder and its application

所占重量份所占重量份所占重量份例所占重量份 Percent by weight Percent by weight Percent by weight Example Percent by weight

火力发 A:B:C:D= 水稻聚乙烯 Firepower A: B: C: D = Rice Polyethylene

3 20 电厂的 25 40 10:15:10:30 5 秸秆 (PE) 3 20 25 25 10 10: 15: 10: 30 in power plant 5 Straw (PE)

粉煤灰 (wt%) Fly ash (wt%)

火力发 A:B:C:D= 水稻聚乙烯 Firepower A: B: C: D = Rice Polyethylene

4 20 电厂的 15 40 10:15:10:30 25 秸秆 (PE) 4 20 of the power plant 15 40 10: 15: 10: 30 25 Straw (PE)

粉煤灰 (Wt% ) Fly Ash (Wt%)

火力发 A:B:C:D= 水稻聚乙烯 Firepower A: B: C: D = Rice Polyethylene

5 20 电厂的 20 20 10:15:10:30 40 秸秆 (PE) 5 20 Power plant 20 20 10: 15: 10: 30 40 Straw (PE)

粉煤灰 (wt%) Fly ash (wt%)

火力发 A:B:C:D二水稻聚乙烯 Firepower A: B: C: D Two Rice Polyethylene

6 40 电厂的 20 20 10:15:10:30 20 秸秆 (PE) 6 40 Power plant 20 20 10: 15: 10: 30 20 Straw (PE)

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910000/S00ZN3/X3d SC90.0/S00Z ΛΧ 910000 / S00ZN3 / X3d SC90.0 / S00Z Λχ

910000/S00ZN3/X3d SC90.0/S00Z OAV XVIII 1.42 0.10 2789.58 67.46 0.02910000 / S00ZN3 / X3d SC90.0 / S00Z OAV XVIII 1.42 0.10 2789.58 67.46 0.02

XIX 1.10 0.10 2689.64 68.97 0.00XIX 1.10 0.10 2689.64 68.97 0.00

XX 1.00 0.80 2578.98 56.36 0.02XX 1.00 0.80 2578.98 56.36 0.02

XXI 0.90 0.20 2178.69 59.54 0.01XXI 0.90 0.20 2178.69 59.54 0.01

XXII 1.10 1.00 3258.95 46.24 0.04XXII 1.10 1.00 3258.95 46.24 0.04

XXIII 1.20 2.00 3145.39 56.58 0.00XXIII 1.20 2.00 3145.39 56.58 0.00

XXIV 1.26 3.00 2987.27 49.78 0.02XXIV 1.26 3.00 2987.27 49.78 0.02

XXV 0.90 1.00 2568.84 46.36 0.06XXV 0.90 1.00 2568.84 46.36 0.06

XXVI 1.10 0.60 2596.35 38.57 0.04XXVI 1.10 0.60 2596.35 38.57 0.04

XXVII 1.15 0.50 2498.35 56.69 0.00XXVII 1.15 0.50 2498.35 56.69 0.00

XXVIII 1.20 0.10 3002.00 55.14 0.00XXVIII 1.20 0.10 3002.00 55.14 0.00

XXIX 1.20 0.10 3988.25 75.67 0.00 根据表 4中的测试的数据可以看出，本发明提供的复合防水板材的防水性能明显高于现有的板材。它的最高吸水率远低于其它板材 8%的吸水率。就其力学性能而言，它的静弯曲强度也远高于其它板材 16MPa的数值；同时，它具有较高的抗冲击性能，几乎达到相同质量的工程塑料的抗冲击性能。本发明提供的复合防水板材具有优良的防虫性能，白蚁无法啃食该材料。在生产本品的过程中完全不产生污水和废气，是一种纯绿色产品，完全不含甲醛，并且在生产的过程中能消耗大量工业废品粉煤灰、农田废弃物秸秆以及各种废旧塑料。 XXIX 1.20 0.10 3988.25 75.67 0.00 According to the test data in Table 4, it can be seen that the waterproof performance of the composite waterproof sheet provided by the present invention is significantly higher than the existing sheet. Its maximum water absorption is much lower than the 8% water absorption of other panels. In terms of its mechanical properties, its static bending strength is also much higher than the value of 16MPa for other plates; at the same time, it has high impact resistance and almost reaches the impact resistance of engineering plastics of the same quality. The composite waterproof sheet provided by the present invention has excellent insect-proof performance, and termites cannot eat the material. In the process of producing this product, no sewage and exhaust gas are generated at all. It is a pure green product, completely free of formaldehyde, and can consume a large amount of industrial waste fly ash, farm waste straw and various waste plastics .

本发明提供的复合防水板材具有防水、防潮、结实、好用的特点，利于加工，可以用于制造柜子、桌子、掎子、地板、门窗、打轻质龙骨、隔断、制作包装箱、家装仿木材料等用途。 The composite waterproof board provided by the invention has the characteristics of waterproof, moisture-proof, strong and easy to use, and is convenient for processing. It can be used for manufacturing cabinets, tables, ladles, floors, doors and windows, light-weight keels, partitions, making packing boxes, home improvement imitations. Wood materials and other uses.

使用本专利生产的 0.5 X 0.5米 ²的板材为原料，用木工锯子、钢锯、云石机等木工工具进行切割加工，制成各种形状的板材，然后使用刨子、角磨机等工具刨平表面，再用木螺丝、粘胶等制作成为桌子、台面、门板以及以上所述的各种建筑材料。板材的外表面可以刮腻子、打磨、喷刷各种油漆、可以粘贴各种表面。或者定做相应的模具，直接压制成为所需要的形状的产品，例如成型整体门、窗、地板等。材料的外表面的装饰过程既可以在成品完成后再贴面，也可以在压制前铺垫上外表面材料直接成型。 Use the 0.5 X 0.5 m ² sheet produced by this patent as the raw material, use woodworking saws, hacksaws, marble machines and other woodworking tools to cut and process into various shapes of plates, and then use planers, angle grinders and other tools to plan The flat surface is made of wood screws, glue, etc. to form a table, a countertop, a door panel and various construction materials described above. The outer surface of the board can be putty, sanded, sprayed with various paints, and can be pasted on various surfaces. Or customize the corresponding mold, and directly press it into the product with the required shape, such as forming a whole door, window, floor, etc. The decoration process of the outer surface of the material can either be veneered after the finished product is completed, or the outer surface material can be directly formed before the pressing.

Claims

权利要求 Rights request

1、一种复合防水板材，由如下组份通过共混模压聚合制成： 1. A composite waterproof sheet made of the following components through blending and compression polymerization:

植物纤维 20〜70重量份； 20 ~ 70 parts by weight of vegetable fiber;

粉煤灰 10〜60重量份； 10 ~ 60 parts by weight of fly ash;

粘合剂 5〜40重量份； 5 ~ 40 parts by weight of adhesive;

所述的植物纤维包括农作物的秸秆、各种树木的枝杈为原料制成的纤维粉末，以及木材加工所生成的木屑； The plant fiber includes stalks of crops, fiber powder made from branches of various trees as raw materials, and wood chips generated from wood processing;

所述的粉煤灰包括了火力发电厂、炼钢厂、化工厂和其它行业的烧失量低于 10%的燃煤粉体； The fly ash includes coal-fired powder with a loss on ignition of less than 10% in thermal power plants, steel plants, chemical plants and other industries;

所述的粘合剂为由顺丁烯二酸酐、邻苯二甲酸酐、多元醇、苯乙烯或其同系物按重量份 10:15:10:30的比例制得的混合物。 The adhesive is a mixture prepared from maleic anhydride, phthalic anhydride, polyhydric alcohol, styrene, or a homologue thereof in a ratio of 10: 15: 10: 30 by weight.

2、如权利要求 1所述的复合防水板材，其特征在于，所述的粘合剂还包括三聚氰胺、丙烯酸、或松香和双环戊二烯。 2. The composite waterproof sheet according to claim 1, wherein the adhesive further comprises melamine, acrylic, or rosin and dicyclopentadiene.

3、如权利要求 1所述的复合防水板材，其特征在于，其组份还包括: 塑料 10〜40重量份。 3. The composite waterproof sheet according to claim 1, further comprising: 10 to 40 parts by weight of plastic.

4、如权利要求 3所述的复合防水板材，其特征在于，所述的塑料选自聚乙烯、聚氯乙烯、聚苯乙烯、乙烯一醋酸乙烯共聚物、聚胺酯、聚丙烯、聚碳酸酯、邻苯二甲酸乙二醇酯、 ABS树脂、 SBS树脂中的一种或几种的混合物。 4. The composite waterproof sheet according to claim 3, wherein the plastic is selected from the group consisting of polyethylene, polyvinyl chloride, polystyrene, ethylene-vinyl acetate copolymer, polyurethane, polypropylene, polycarbonate, A mixture of one or more of ethylene phthalate, ABS resin, and SBS resin.

5、一种权利要求 1所述的复合防水板材的制备方法，包括如下步骤: 5. A method for preparing a composite waterproof sheet according to claim 1, comprising the following steps:

所述的植物纤维包括农作物的秸秆、各种树木的枝杈为原料制成的纤维粉末，以及木材加工所生成的木屑； The plant fiber includes fiber made from straw of crops and branches of various trees as raw materials. Powder, and sawdust from wood processing;

6、如权利要求 5所述的复合防水板材的制」备方法，其特征在于，所述的粘合剂还包括三聚氰胺、丙烯酸、或松香禾 Π双环戊二烯。 6. The method for preparing a composite waterproof sheet according to claim 5, wherein the adhesive further comprises melamine, acrylic acid, or rosin and dicyclopentadiene.

7、如权利要求 5 所述的复合防水板材的 §1」备方法，其特征在于，所述步骤 1 ) 的植物纤维长度为 5〜20毫米。 7. The method of §1 "of the composite waterproof sheet according to claim 5, wherein the length of the plant fiber in said step 1) is 5-20 mm.

8、如权利要求 5 所述的复合防水板材的 §!J备方法，其特征在于，所述步骤 2) 的过氧化引发剂为过氧化氢、过氧化苯甲酰胺或过硫酸胺。 8. The method for preparing a composite waterproof sheet according to claim 5, wherein the peroxidation initiator in step 2) is hydrogen peroxide, benzamide peroxide, or amine persulfate.

9、如权利要求 5所述的复合防水板材的^ J备方法，其特征在于，所述的复合防水板材的制备方法，还包括在步骤 3 ) 中加入 10〜40重量份的塑料。 9. The method for preparing a composite waterproof sheet according to claim 5, wherein the method for preparing the composite waterproof sheet further comprises adding 10 to 40 parts by weight of plastic in step 3).

10、如权利要求 9所述的复合防水板材的备方法，其特征在于，所述的塑料选自聚乙烯、聚氯乙烯、聚苯乙烯、乙烯一醋酸乙烯共聚物、聚胺酯、聚丙烯、聚碳酸酯、邻苯二甲酸乙二醇酉旨、 ABS树脂、 SBS树脂中的一种或几种的混合物。 10. The method for preparing a composite waterproof sheet according to claim 9, wherein the plastic is selected from the group consisting of polyethylene, polyvinyl chloride, polystyrene, ethylene-vinyl acetate copolymer, polyurethane, polypropylene, and poly A mixture of one or more of carbonate, ethylene phthalate, ABS resin, and SBS resin.

11、一种权利要求 1所述的复合防水板材在各种家具、办公设备、汽车内饰、室内外装修与建筑材料中的非承重墙体、吊顶、地板及不拆卸模板材料中的用途。 11. The use of the composite waterproof sheet according to claim 1 in non-load-bearing walls, suspended ceilings, floors and non-removable formwork materials in various furniture, office equipment, automotive interiors, interior and exterior decoration and building materials.