WO2020087550A1 - 一种纤维素/三聚氰胺甲醛复合树脂及其制备方法 - Google Patents

一种纤维素/三聚氰胺甲醛复合树脂及其制备方法 Download PDF

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WO2020087550A1
WO2020087550A1 PCT/CN2018/113930 CN2018113930W WO2020087550A1 WO 2020087550 A1 WO2020087550 A1 WO 2020087550A1 CN 2018113930 W CN2018113930 W CN 2018113930W WO 2020087550 A1 WO2020087550 A1 WO 2020087550A1
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Prior art keywords
cellulose
melamine formaldehyde
composite resin
powder
formaldehyde composite
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PCT/CN2018/113930
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English (en)
French (fr)
Inventor
刘海林
刘和文
潘杨笠
岳夕阳
王赞
刘青萌
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安徽绿之态新材料有限公司
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Priority to US16/307,149 priority Critical patent/US11053383B1/en
Publication of WO2020087550A1 publication Critical patent/WO2020087550A1/zh

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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L61/00Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
    • C08L61/20Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
    • C08L61/26Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds
    • C08L61/28Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds with melamine
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00Compositions of cellulose, modified cellulose or cellulose derivatives
    • C08L1/02Cellulose; Modified cellulose
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/06Polymer mixtures characterised by other features having improved processability or containing aids for moulding methods
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/14Polymer mixtures characterised by other features containing polymeric additives characterised by shape
    • C08L2205/16Fibres; Fibrils

Definitions

  • the present application relates to the technical field of polymer materials, in particular to a cellulose / melamine formaldehyde composite resin and a preparation method thereof.
  • Melamine formaldehyde resin also known as melamine resin
  • melamine resin is obtained by polycondensation of melamine and formaldehyde in a suitable medium.
  • the resin is widely used in daily necessities such as porcelain tableware and electrical appliances.
  • melamine formaldehyde resin has the disadvantages of high brittleness, poor toughness, and easy to crack under stress.
  • Cellulose biomass powders such as plant stalks, crop straw powders, cereal husk powders, and cereal flours, are widely used in melamine formaldehyde resins.
  • This melamine formaldehyde resin / cellulose powder composite material is manufactured by high-temperature molding.
  • This melamine formaldehyde resin / cellulose powder molded product has poor strength and is more likely to fall apart than melamine resin. In order to increase strength, products are often made thick and heavy.
  • Toughening modifiers are generally added during synthesis from the preparation of melamine resins.
  • Chinese Patent No. 25, 2009 Publication No .: CN101585953A discloses a method for preparing melamine formaldehyde molding compound. Melamine and modifier are added to the kettle for reaction to obtain melamine formaldehyde molding compound.
  • the modifier is polyvinyl alcohol, polyethylene glycol, p-toluene sulfonamide, dicyandiamide, and benzomelamine, any one or more of which can be mixed in any ratio. After modification, the strength and toughness of the molding compound are improved.
  • Cipheral Patent November 16, 2016 discloses an amino molding compound powder used for processing melamine tableware and its preparation method. It consists of melamine resin molding compound, wood fiber, and sodium citrate , Titanium dioxide and zinc stearate.
  • the melamine formaldehyde resin produced in the prior art still has various problems such as high brittleness, easy to drop, and the addition of biomass cellulose powder with poor composite strength and complex composition, the strength of the resulting melamine formaldehyde resin / cellulose powder molded product It can break easily when it is poor, stressed or dropped.
  • this application proposes a cellulose / melamine formaldehyde composite resin and its preparation method, which has a good toughening effect, effectively improves the shortcomings of poor strength, easy to break when stressed or dropped, and the process is simple ,low cost.
  • a cellulose / melamine formaldehyde composite resin proposed in this application its raw materials include, by weight percentage: melamine formaldehyde resin 30-90%, cellulose powder 5-60%, curing agent 0.01-0.1%, inorganic filler 0-20% , Surface modifier 1-5%, dimer acid 1-20%.
  • the surface modifier is at least one of zinc stearate, calcium stearate, and silicon-anhui coupling agent.
  • the cellulose powder is at least one of plant stalk powder, cereal powder, and cereal husk powder.
  • This application uses plant stem powder, grain flour, grain hull powder, which is a natural renewable plant fiber, as a raw material for production. It is purely natural, non-polluting, and non-toxic. Plant stem powder, grain flour, and grain hull powder are discarded. In the past, the treatment of the crops was a problem. The long-term stacking caused the surrounding environment to be dirty and messy. The incineration process will bring serious air pollution, generate a large amount of carbon dioxide and sulfur dioxide, and will also bury the hidden danger of fire and even destroy the soil structure.
  • Plant stalk powder, grain flour, and grain hull powder are renewable biopolymer materials with huge output on the earth.
  • crop waste resources in addition to being safe and environmentally friendly, it is harmless to the human body and can replace traditional materials.
  • plastic, melamine, etc. this natural renewable plant fiber is used as a raw material for production.
  • This pays more attention to health and environmental protection concepts. It has no potential impact and harm on human bodies. This is an environmentally friendly high
  • the efficient production method not only realizes the farmers' income generation again, brings objective and practical benefits to the farmers, but also protects the atmosphere and soil environment. More importantly, it avoids the problems of felling trees and chemical pollution in the production of traditional materials. After being discarded, it can be degraded in the natural environment, which reduces the environmental pollution in the process of agricultural waste disposal, and its degradability further eliminates white pollution.
  • the inorganic filler is at least one of alumina, calcium carbonate, silica, and montmorillonite.
  • the alumina, calcium carbonate, silica, and montmorillonite added in this application as inorganic fillers can weaken the strength of the product caused by the addition of a large amount of cellulose powder, and can increase the strength of the product.
  • the preparation method of the cellulose / melamine formaldehyde composite resin proposed in this application is obtained by stirring the raw materials, sieving, and molding.
  • the above raw materials are solid powders.
  • the stirring time is 10-30 min, and the temperature during stirring is 40-60 ° C.
  • the screen used for sieving is 80 mesh.
  • the molding temperature is 140-180 ° C.
  • the molding pressure is 500-2000 kN
  • the molding time is 2-10 min.
  • Dimer acid can react with melamine formaldehyde resin to introduce a flexible chain structure.
  • the toughening effect is obvious, which can significantly improve the brittleness of melamine formaldehyde resin products.
  • Dimer acid is used as a traditional chemical product at a price Low; Compared with the melamine formaldehyde resin in the prior art, the present application adds a toughening agent during the stirring process, and the process is simple.
  • a cellulose / melamine formaldehyde composite resin its raw materials include: melamine formaldehyde resin 88.9kg, cellulose powder 5kg, curing agent 0.1kg, surface modifier 5kg, dimer acid 1kg.
  • a cellulose / melamine formaldehyde composite resin its raw materials include: melamine formaldehyde resin 30.99kg, cellulose powder 8kg, curing agent 0.01kg, inorganic filler 10kg, surface modifier 1kg, dimer acid 10kg.
  • a cellulose / melamine formaldehyde composite resin the raw materials of which include: melamine formaldehyde resin 30kg, plant stem 28.98kg, curing agent 0.02kg, montmorillonite 20kg, zinc stearate 1kg, dimer acid 20kg.
  • a cellulose / melamine formaldehyde composite resin its raw materials include: melamine formaldehyde resin 45kg, cellulose powder 32.94kg, curing agent 0.06kg, inorganic filler 12kg, surface modifier 5kg, dimer acid 5kg.
  • the cellulose powder is cereal powder and cereal skin powder.
  • the inorganic filler is alumina and montmorillonite.
  • the surface modifier is zinc stearate and silicon-anhui coupling agent.
  • the preparation method of the above cellulose / melamine formaldehyde composite resin includes the following steps: the above raw materials are stirred for 10 minutes, the temperature during the stirring is 60 ° C., passed through an 80 mesh sieve, and molded at 140 ° C. for 10 minutes, and the molding pressure is 500-kN. .
  • a cellulose / melamine formaldehyde composite resin its raw materials include: melamine formaldehyde resin 35.97kg, cellulose powder 60kg, curing agent 0.03kg, inorganic filler 1kg, surface modifier 1kg, dimer acid 2kg.
  • Cellulose powder includes plant stalk powder, grain powder, and grain hull powder.
  • Inorganic fillers include alumina, calcium carbonate, silica, and montmorillonite.
  • Surface modifiers include zinc stearate, calcium stearate, and silicon-anhui coupling agent.
  • the preparation method of the above cellulose / melamine formaldehyde composite resin includes the following steps: the above raw materials are stirred for 30 minutes, the temperature during the stirring is 40 ° C., passed through an 80-mesh sieve, and molded at 180 ° C. for 2 minutes, and the molding pressure is 1980 kN.
  • a cellulose / melamine formaldehyde composite resin the raw materials of which include: melamine formaldehyde resin 40kg, rice husk powder 50kg, curing agent 0.1kg, alumina 5kg, zinc stearate 2kg, dimer acid 3kg.
  • the preparation method of the above cellulose / melamine formaldehyde composite resin includes the following steps: the above raw materials are stirred for 10 minutes, the temperature during the stirring is 60 ° C, passed through an 80-mesh sieve, and molded at 150 ° C for 5 minutes, and the molding pressure is 2000 kN.
  • a cellulose / melamine formaldehyde composite resin its raw materials include: melamine formaldehyde resin 40kg, rice husk powder 50kg, curing agent 0.1kg, alumina 5kg, zinc stearate 2kg.
  • the preparation method of the above cellulose / melamine formaldehyde composite resin includes the following steps: stirring the above raw materials for 10 minutes, the temperature during the stirring is 60 ° C., passing through an 80-mesh sieve, molding at 150 ° C. for 5 min, and molding pressure at 2000 kN.
  • a cellulose / melamine formaldehyde composite resin its raw materials include: melamine formaldehyde resin 40kg, bamboo fiber powder 40kg, curing agent 0.1kg, calcium stearate 5kg, dimer acid 15kg.
  • the preparation method of the above cellulose / melamine formaldehyde composite resin includes the following steps: the above raw materials are stirred for 20 minutes, the temperature during the stirring is 50 ° C., passed through an 80-mesh sieve, molded at 150 ° C. for 5 minutes, and the molded pressure is 2000 kN.
  • a cellulose / melamine formaldehyde composite resin its raw materials include: melamine formaldehyde resin 40kg, bamboo fiber powder 40kg, curing agent 0.1kg, calcium stearate 5kg.
  • the preparation method of the above cellulose / melamine formaldehyde composite resin includes the following steps: the above raw materials are stirred for 20 minutes, the temperature during the stirring is 50 ° C., passed through an 80-mesh sieve, and molded at 150 ° C. for 5 minutes, and the molding pressure is 2000 kN.
  • a cellulose / melamine formaldehyde composite resin its raw materials include: melamine formaldehyde resin 30kg, rice straw powder 50kg, curing agent 0.1kg, 300 mesh silica powder 10kg, silane coupling agent KH-550 2kg, calcium stearate 3kg, 5kg dimer acid.
  • the preparation method of the above cellulose / melamine formaldehyde composite resin includes the following steps: the above raw materials are stirred for 20 minutes, the temperature during the stirring is 50 ° C., passed through an 80-mesh sieve, and molded at 160 ° C. for 2 minutes, and the molding pressure is 2000 kN.
  • a cellulose / melamine formaldehyde composite resin its raw materials include: melamine formaldehyde resin 30kg, rice straw powder 50kg, curing agent 0.1kg, 300 mesh silica powder 10kg, silane coupling agent KH-550 2kg, calcium stearate 3kg.
  • the preparation method of the above cellulose / melamine formaldehyde composite resin includes the following steps: the above raw materials are stirred for 20 minutes, the temperature during the stirring is 50 ° C., passed through an 80-mesh sieve, and molded at 160 ° C. for 2 minutes, and the molding pressure is 2000 kN.
  • a cellulose / melamine formaldehyde composite resin its raw materials include: melamine formaldehyde resin 40kg, corn starch 50kg, curing agent 0.1kg, calcium stearate 5kg, dimer acid 5kg.
  • the preparation method of the above cellulose / melamine formaldehyde composite resin includes the following steps: the above raw materials are stirred for 20 minutes, the temperature during the stirring is 50 ° C., passed through an 80-mesh sieve, and molded at 160 ° C. for 2 min.
  • the molding pressure is 2000 kN.
  • a cellulose / melamine formaldehyde composite resin its raw materials include: melamine formaldehyde resin 40kg, corn starch 40kg, curing agent 0.1kg, calcium stearate 5kg.
  • the preparation method of the above cellulose / melamine formaldehyde composite resin includes the following steps: the above raw materials are stirred for 20 minutes, the temperature during the stirring is 50 ° C, passed through an 80-mesh sieve, and molded at 160 ° C for 2 minutes, and the molding pressure is 2000 kN.
  • the cellulose / melamine formaldehyde composite resin obtained in Example 6-9 and the cellulose / melamine formaldehyde composite resin obtained in Comparative Example were respectively made into samples with a size of 5 cm ⁇ 20 cm ⁇ 0.5 cm, and the samples were subjected to a drop test as follows : Place the sample parallel to the ground at a height of 2m, and then let it fall freely. Test 50 times in parallel for each group of samples. Count the damage (cracks or breaks) after the drop. The results are as follows:
  • this application introduces a flexible chain structure through the reaction of dimer acid and melamine formaldehyde resin, which has obvious toughening effect and can significantly improve the brittleness of melamine formaldehyde resin products.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

一种纤维素/三聚氰胺甲醛复合树脂,其原料按重量百分比包括:三聚氰胺甲醛树脂30-90%,纤维素粉5-60%,固化剂0.01-0.1%,无机填料0-20%,表面改性剂1-5%,二聚酸1-20%。该树脂制备方法包括如下步骤:将原料进行搅拌,过筛,模压成型即得。制备的纤维素/三聚氰胺甲醛复合树脂强度增加,经2米高自由跌落测试,碎裂率显著降低。由此,现有技术中纤维素/三聚氰胺甲醛树脂模压制品存在的脆性大,强度差,容易因跌落而脆裂、破碎的问题得以解决。该复合树脂具有广泛的应用前景。

Description

一种纤维素/三聚氰胺甲醛复合树脂及其制备方法
本申请要求于2018年10月31日提交中国专利局、申请号为201811285171.8、申请名称为一种纤维素/三聚氰胺甲醛复合树脂及其制备方法的中国专利申请的优先权,其全部内容通过引用结合在本申请中。
技术领域
本申请涉及高分子材料技术领域,尤其涉及一种纤维素/三聚氰胺甲醛复合树脂及其制备方法。
背景技术
三聚氰胺甲醛树脂又称密胺树脂是由三聚氰胺和甲醛在合适介质中通过缩聚反应得到。该树脂广泛用于制造仿瓷餐具、电器等日用品。但是,三聚氰胺甲醛树脂具有脆性大、韧性差、受应力容易碎裂等缺点。纤维素类生物质粉料,如植物茎秆、作物秸秆粉、谷类皮壳粉、谷粉广泛应用于三聚氰胺甲醛树脂中,这种三聚氰胺甲醛树脂/纤维素粉复合材料通过高温模压制成产品。这种三聚氰胺甲醛树脂/纤维素粉模压制品的强度差,比密胺树脂更容易跌碎。为了增加强度,制品往往要做的很厚、笨重。
一般从密胺树脂的制备合成时加入增韧改性剂。中国专利2009年11月25日(公开号:CN101585953A)公开了一种三聚氰胺甲醛模塑料的制备方法,三聚氰胺和改性剂同时加入釜中反应得到三聚氰胺甲醛模塑料。其中改性剂为聚乙烯醇、聚乙二醇、对甲苯磺酰胺、双氰胺和苯代三聚氰胺 中的一种或几种的任意比混合物,改性后提高了模塑料的强度和韧性。
中国专利2016年11月16日(公开号:CN106117968A)公开了一种用于加工密胺餐具的氨基模塑料料粉及其制备方法,它是由密胺树脂模塑料、木质纤维、柠檬酸钠、钛白粉以及硬脂酸锌组成。
由于现有技术生产的三聚氰胺甲醛树脂仍然不同程度地存在脆性大、易掉块等问题,加上复合强度较差、成分复杂的生物质纤维素粉,所得三聚氰胺甲醛树脂/纤维素粉模压制品强度差、受力或跌落时易破碎。
发明内容
基于背景技术存在的技术问题,本申请提出了一种纤维素/三聚氰胺甲醛复合树脂及其制备方法,增韧效果好,有效改善了强度差、受力或跌落时易破碎等缺点,而且工艺简单,成本低。
本申请提出的一种纤维素/三聚氰胺甲醛复合树脂,其原料按重量百分比包括:三聚氰胺甲醛树脂30-90%,纤维素粉5-60%,固化剂0.01-0.1%,无机填料0-20%,表面改性剂1-5%,二聚酸1-20%。
优选地,表面改性剂为硬脂酸锌、硬脂酸钙、硅皖偶联剂中至少一种。
本申请通过加入表面改性剂,尤其是硬脂酸锌、硬脂酸钙、硅皖偶联剂,一方面可提高粒子的相容性,另一方面可避免不同粒子之间由于表面电荷不同产生的聚集现象。
优选地,纤维素粉为植物茎秆粉、谷粉、谷类皮壳粉中至少一种。
本申请以植物茎秆粉、谷粉、谷类皮壳粉这种天然可再生植物纤维为生产原料,纯天然、无污染、无任何毒害,植物茎秆粉、谷粉、谷类皮壳 粉是废弃的农作物,以往的处理很是问题,长时间堆放导致周围环境又脏又乱,焚烧处理又会带来严重污染空气,产生大量二氧化碳、二氧化硫,还会埋下火灾的隐患,甚至破坏土壤结构。
植物茎秆粉、谷粉、谷类皮壳粉为地球上产量巨大的可再生性生物高分子材料,利用这些农作物废料资源,除具有安全环保外,更是对人体无害,可以取替传统材质如塑料、密胺等,以这种天然可再生植物纤维为生产原料,与传统材料相比较,更注重健康和环保理念,对人的身体无任何潜在影响和危害,这是一种环保的高效益生产方式,不仅实现农民的再次创收,为农民带来了客观的实际利益,还保护了大气、土壤的环境,更重要的,它避免了传统材料生产中产生的砍伐树木、化工污染等问题,丢弃后可自然环境下降解,减低了农业废料处理过程中对环境的污染,其可降解性还进一步消除了白色污染。
优选地,无机填料为氧化铝、碳酸钙、二氧化硅、蒙脱土中至少一种。
本申请加入的氧化铝、碳酸钙、二氧化硅、蒙脱土作为无机填料,可减弱大量添加纤维素粉造成的产品强度的消弱,可提高产品的强度。
本申请提出的上述纤维素/三聚氰胺甲醛复合树脂制备方法,将原料进行搅拌,过筛,模压成型即得。
上述原料均为固体粉末。
优选地,搅拌时间为10-30min,搅拌过程中温度为40-60℃。
优选地,过筛所用筛网为80目。
优选地,模压成型温度为140-180℃,模压成型压力为500-2000kN,模压成型时间为2-10min。
本申请以二聚酸为增韧剂,二聚酸可以与三聚氰胺甲醛树脂反应引入柔性链结构,增韧效果明显,可以显著改善三聚氰胺甲醛树脂制品的脆性,其中二聚酸作为传统化工产品,价格低;本申请与现有技术的三聚氰胺甲醛树脂相比,增韧剂在搅拌过程中添加,工艺简单。
具体实施方式
下面,通过具体实施例对本申请的技术方案进行详细说明。
实施例1
一种纤维素/三聚氰胺甲醛复合树脂,其原料包括:三聚氰胺甲醛树脂88.9kg,纤维素粉5kg,固化剂0.1kg,表面改性剂5kg,二聚酸1kg。
实施例2
一种纤维素/三聚氰胺甲醛复合树脂,其原料包括:三聚氰胺甲醛树脂30.99kg,纤维素粉8kg,固化剂0.01kg,无机填料10kg,表面改性剂1kg,二聚酸10kg。
实施例3
一种纤维素/三聚氰胺甲醛复合树脂,其原料包括:三聚氰胺甲醛树脂30kg,植物茎秆28.98kg,固化剂0.02kg,蒙脱土20kg,硬脂酸锌1kg,二聚酸20kg。
实施例4
一种纤维素/三聚氰胺甲醛复合树脂,其原料包括:三聚氰胺甲醛树脂45kg,纤维素粉32.94kg,固化剂0.06kg,无机填料12kg,表面改性剂5kg,二聚酸5kg。
纤维素粉为谷粉、谷类皮壳粉。
无机填料为氧化铝、蒙脱土。
表面改性剂为硬脂酸锌、硅皖偶联剂。
上述纤维素/三聚氰胺甲醛复合树脂制备方法,包括如下步骤:将上述原料进行搅拌10min,搅拌过程中温度为60℃,过80目筛,140℃模压成型10min,模压成型压力为500-kN即得。
实施例5
一种纤维素/三聚氰胺甲醛复合树脂,其原料包括:三聚氰胺甲醛树脂35.97kg,纤维素粉60kg,固化剂0.03kg,无机填料1kg,表面改性剂1kg,二聚酸2kg。
纤维素粉包括植物茎秆粉、谷粉、谷类皮壳粉。
无机填料包括氧化铝、碳酸钙、二氧化硅、蒙脱土中。
表面改性剂包括硬脂酸锌、硬脂酸钙、硅皖偶联剂。
上述纤维素/三聚氰胺甲醛复合树脂制备方法,包括如下步骤:将上述原料进行搅拌30min,搅拌过程中温度为40℃,过80目筛,180℃模压成型2min,模压成型压力为1980kN即得。
实施例6
一种纤维素/三聚氰胺甲醛复合树脂,其原料包括:三聚氰胺甲醛树脂40kg,稻壳粉50kg,固化剂0.1kg,氧化铝5kg,硬脂酸锌2kg,二聚酸3kg。
上述纤维素/三聚氰胺甲醛复合树脂制备方法,包括如下步骤:将上述原料进行搅拌10min,搅拌过程中温度为60℃,过80目筛,150℃模压成 型5min,模压成型压力为2000kN即得。
对比例1
一种纤维素/三聚氰胺甲醛复合树脂,其原料包括:三聚氰胺甲醛树脂40kg,稻壳粉50kg,固化剂0.1kg,氧化铝5kg,硬脂酸锌2kg。
上述纤维素/三聚氰胺甲醛复合树脂制备方法,包括如下步骤:将上述原料进行搅拌10min,搅拌过程中温度为60℃,过80目筛,150℃模压成型5min,模压成型压力为2000kN即得。
实施例7
一种纤维素/三聚氰胺甲醛复合树脂,其原料包括:三聚氰胺甲醛树脂40kg,竹纤维粉40kg,固化剂0.1kg,硬脂酸钙5kg,二聚酸15kg。
上述纤维素/三聚氰胺甲醛复合树脂制备方法,包括如下步骤:将上述原料进行搅拌20min,搅拌过程中温度为50℃,过80目筛,150℃模压成型5min,模压成型压力为2000kN即得。
对比例2
一种纤维素/三聚氰胺甲醛复合树脂,其原料包括:三聚氰胺甲醛树脂40kg,竹纤维粉40kg,固化剂0.1kg,硬脂酸钙5kg。
上述纤维素/三聚氰胺甲醛复合树脂制备方法,包括如下步骤:将上述原料进行搅拌20min,搅拌过程中温度为50℃,过80目筛,150℃模压成型5min,模压成型压力为2000kN即得。
实施例8
一种纤维素/三聚氰胺甲醛复合树脂,其原料包括:三聚氰胺甲醛树脂30kg,稻秸秆粉50kg,固化剂0.1kg,300目二氧化硅粉10kg,硅烷偶联 剂KH-550 2kg,硬脂酸钙3kg,二聚酸5kg。
上述纤维素/三聚氰胺甲醛复合树脂制备方法,包括如下步骤:将上述原料进行搅拌20min,搅拌过程中温度为50℃,过80目筛,160℃模压成型2min,模压成型压力为2000kN即得。
对比例3
一种纤维素/三聚氰胺甲醛复合树脂,其原料包括:三聚氰胺甲醛树脂30kg,稻秸秆粉50kg,固化剂0.1kg,300目二氧化硅粉10kg,硅烷偶联剂KH-550 2kg,硬脂酸钙3kg。
上述纤维素/三聚氰胺甲醛复合树脂制备方法,包括如下步骤:将上述原料进行搅拌20min,搅拌过程中温度为50℃,过80目筛,160℃模压成型2min,模压成型压力为2000kN即得。
实施例9
一种纤维素/三聚氰胺甲醛复合树脂,其原料包括:三聚氰胺甲醛树脂40kg,玉米淀粉50kg,固化剂0.1kg,硬脂酸钙5kg,二聚酸5kg。
上述纤维素/三聚氰胺甲醛复合树脂制备方法,包括如下步骤:将上述原料进行搅拌20min,搅拌过程中温度为50℃,过80目筛,160℃模压成型2min,模压成型压力为2000kN即得。
对比例4
一种纤维素/三聚氰胺甲醛复合树脂,其原料包括:三聚氰胺甲醛树脂40kg,玉米淀粉40kg,固化剂0.1kg,硬脂酸钙5kg。
上述纤维素/三聚氰胺甲醛复合树脂制备方法,包括如下步骤:将上述原料进行搅拌20min,搅拌过程中温度为50℃,过80目筛,160℃模压成 型2min,模压成型压力为2000kN即得。
将实施例6-9所得纤维素/三聚氰胺甲醛复合树脂和对比例所得纤维素/三聚氰胺甲醛复合树脂分别制成尺寸为5cm×20cm×0.5cm的试样,将该试样进行跌落测试,具体如下:将试样与地面平行放置,高度为2m,然后让其自由坠落,每组试样平行测试50次,统计跌落后出现损坏(裂纹或折断)的情况,其结果如下所示:
测试项目 测试结果
实施例6 1%
对比例1 35%
实施例7 2%
对比例2 38%
实施例8 4%
对比例3 46%
实施例9 1%
对比例4 32%
由上表可知:本申请通过采用二聚酸与三聚氰胺甲醛树脂反应引入柔性链结构,增韧效果明显,可以显著改善三聚氰胺甲醛树脂制品的脆性。
以上所述,仅为本申请较佳的具体实施方式,但本申请的保护范围并不局限于此,任何熟悉本技术领域的技术人员在本申请揭露的技术范围内,根据本申请的技术方案及其申请构思加以等同替换或改变,都应涵盖在本申请的保护范围之内。

Claims (8)

  1. 一种纤维素/三聚氰胺甲醛复合树脂,其特征在于,其原料按重量百分比包括:三聚氰胺甲醛树脂30-90%,纤维素粉5-60%,固化剂0.01-0.1%,无机填料0-20%,表面改性剂1-5%,二聚酸1-20%。
  2. 根据权利要求1所述纤维素/三聚氰胺甲醛复合树脂,其特征在于,纤维素粉为植物茎秆粉、谷粉、谷类皮壳粉中至少一种。
  3. 根据权利要求1-2任一项所述纤维素/三聚氰胺甲醛复合树脂,其特征在于,无机填料为氧化铝、碳酸钙、二氧化硅、蒙脱土中至少一种。
  4. 根据权利要求1-3任一项所述纤维素/三聚氰胺甲醛复合树脂,其特征在于,表面改性剂为硬脂酸锌、硬脂酸钙、硅皖偶联剂中至少一种。
  5. 一种如权利要求1-4任一项所述纤维素/三聚氰胺甲醛复合树脂制备方法,其特征在于,包括如下步骤:将原料进行搅拌,过筛,模压成型即得。
  6. 根据权利要求5所述纤维素/三聚氰胺甲醛复合树脂制备方法,其特征在于,搅拌时间为10-30min,搅拌过程中温度为40-60℃。
  7. 根据权利要求5或6所述纤维素/三聚氰胺甲醛复合树脂制备方法,其特征在于,过筛所用筛网为80目。
  8. 根据权利要求5-7任一项所述纤维素/三聚氰胺甲醛复合树脂制备方法,其特征在于,模压成型温度为140-180℃,模压成型压力为500-2000kN,模压成型时间为2-10min。
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113004653A (zh) * 2021-04-25 2021-06-22 晋江市旭佰日用品有限责任公司 一种环保无毒密胺树脂餐具及其制备方法

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111592734B (zh) * 2020-05-07 2023-02-17 安徽绿之态秸秆制品有限公司 一种增强增韧的植物纤维-密胺树脂复合材料及其制备方法
CN111647172B (zh) * 2020-05-07 2022-03-08 安徽绿之态秸秆制品有限公司 一种稻壳粉的改性方法、改性稻壳粉和复合材料
CN112280110A (zh) * 2020-10-14 2021-01-29 安徽昌悌进出口贸易有限公司 一种家具用材料
CN112175241A (zh) * 2020-10-14 2021-01-05 安徽昌悌进出口贸易有限公司 一种儿童餐具及其制备方法
CN112143045B (zh) * 2020-10-14 2022-05-27 安徽昌悌进出口贸易有限公司 一种仿瓷瓶及其制备方法
CN114231047B (zh) * 2021-12-29 2023-04-11 厦门糠宝瑞新材料科技有限公司 一种可降解材料及其制备方法和应用
CN115466484A (zh) * 2022-03-16 2022-12-13 深圳市德艺科技实业有限公司 一种含天然纤维的密胺树脂制品及其制备方法

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101585953A (zh) * 2009-06-23 2009-11-25 中国林业科学研究院林产化学工业研究所 三聚氰胺甲醛模塑料的制备方法
CN102875755A (zh) * 2012-09-20 2013-01-16 中国石油化工股份有限公司 一种三聚氰胺甲醛树脂的增韧改性方法
CN105038120A (zh) * 2015-07-30 2015-11-11 德清县联诚氨基塑料制品有限公司 一种密胺树脂
CN108084649A (zh) * 2017-12-29 2018-05-29 溧阳市乔森塑料有限公司 改性三聚氰胺甲醛模塑料及其制备方法和应用
CN108084646A (zh) * 2017-12-20 2018-05-29 贺州宝兴新材料有限公司 一种密胺树脂
CN108178899A (zh) * 2017-12-29 2018-06-19 溧阳市乔森塑料有限公司 改性三聚氰胺甲醛模塑料及其制备方法

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2310004A (en) * 1935-09-28 1943-02-02 Ciba Products Corp Triazine-aldehyde condensation product
US2582303A (en) * 1947-10-16 1952-01-15 American Cyanamid Co Hot-moldable compositions comprising melamine-formaldehyde resin and acrylonitrile copolymer
US2841571A (en) * 1954-11-02 1958-07-01 American Cyanamid Co Resinous composition
US20070299218A1 (en) * 2006-06-22 2007-12-27 Syh-Tau Yeh Solder-resistant flexible thermosetting epoxy resin system
CN102321339B (zh) * 2011-08-02 2013-01-16 广东榕泰实业股份有限公司 一种可注射成型的氨基树脂组合物及其制备方法
CN102924867A (zh) * 2012-11-01 2013-02-13 开化瑞达塑胶科技有限公司 一种化妆品瓶盖用材料及其生产工艺
CN103113716B (zh) * 2013-01-28 2015-06-24 北京化工大学常州先进材料研究院 一种二聚酸改性环氧树脂增韧碳纤维预浸料的制备方法
WO2015196134A1 (en) * 2014-06-20 2015-12-23 Solazyme, Inc. Wood composites
CN106117968A (zh) 2016-06-26 2016-11-16 襄汾县瑞德合成材料有限公司 一种用于加工密胺餐具的氨基模塑料料粉及其制备方法
CN106243753A (zh) * 2016-07-29 2016-12-21 安徽科邦树脂科技有限公司 一种核桃壳植物纤维合成树脂及其制备工艺
CN107286574A (zh) * 2017-06-27 2017-10-24 浙江联诚氨基材料有限公司 一种微波炉加热用密胺模塑料及制备方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101585953A (zh) * 2009-06-23 2009-11-25 中国林业科学研究院林产化学工业研究所 三聚氰胺甲醛模塑料的制备方法
CN102875755A (zh) * 2012-09-20 2013-01-16 中国石油化工股份有限公司 一种三聚氰胺甲醛树脂的增韧改性方法
CN105038120A (zh) * 2015-07-30 2015-11-11 德清县联诚氨基塑料制品有限公司 一种密胺树脂
CN108084646A (zh) * 2017-12-20 2018-05-29 贺州宝兴新材料有限公司 一种密胺树脂
CN108084649A (zh) * 2017-12-29 2018-05-29 溧阳市乔森塑料有限公司 改性三聚氰胺甲醛模塑料及其制备方法和应用
CN108178899A (zh) * 2017-12-29 2018-06-19 溧阳市乔森塑料有限公司 改性三聚氰胺甲醛模塑料及其制备方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
WANG, DUOREN: "7 Dimer Acid", SYNTHETIC RESIN AND ENGINEERING PLASTIC PRODUCTION TECHNOLOGY, 31 August 2001 (2001-08-31), CHINA , pages 20 - 21, XP009520639, ISBN: 7-5019-3312-X *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113004653A (zh) * 2021-04-25 2021-06-22 晋江市旭佰日用品有限责任公司 一种环保无毒密胺树脂餐具及其制备方法

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