WO2024032065A1 - 一种黄豆苷原生物基酚醛树脂及其制备方法和应用 - Google Patents

一种黄豆苷原生物基酚醛树脂及其制备方法和应用 Download PDF

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WO2024032065A1
WO2024032065A1 PCT/CN2023/094113 CN2023094113W WO2024032065A1 WO 2024032065 A1 WO2024032065 A1 WO 2024032065A1 CN 2023094113 W CN2023094113 W CN 2023094113W WO 2024032065 A1 WO2024032065 A1 WO 2024032065A1
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daidzein
phenolic resin
preparation
bio
parts
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PCT/CN2023/094113
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English (en)
French (fr)
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袁新华
覃远
孟付良
周大鹏
吴忆彤
孟献丰
张侃
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江苏大学
杭摩新材料集团股份有限公司
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Priority claimed from CN202210960941.4A external-priority patent/CN115073684B/zh
Application filed by 江苏大学, 杭摩新材料集团股份有限公司 filed Critical 江苏大学
Priority to GBGB2404566.8A priority Critical patent/GB202404566D0/en
Publication of WO2024032065A1 publication Critical patent/WO2024032065A1/zh

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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
    • C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
    • C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
    • C08G8/08—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ
    • C08G8/24—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ with mixtures of two or more phenols which are not covered by only one of the groups C08G8/10 - C08G8/20

Definitions

  • the invention belongs to the field of bio-based polymer materials, and specifically relates to a daidzein bio-based phenolic resin and its preparation method and application.
  • Biomass modification is a hot topic in current research, and it is undoubtedly a wise choice in the context of environmental pollution and the increasing shortage of fossil resources. Biomass has large resource reserves in nature, is particularly diverse, and comes from a wide range of sources. It has great development prospects as a renewable energy source. Introducing biomass into phenolic resin can not only improve performance, but also reduce costs and produce higher economic benefits. Therefore, the development of modified phenolic resin with better performance, low price, and environmental protection has huge potential in practical applications.
  • biomass-modified phenolic resins mainly include biomass-modified phenolic resins such as lignin, tung oil, linseed oil, starch, rosin, bio-oil, cardanol, etc. These modified resins have different properties and each has its own advantages and disadvantages. , also began to be applied. However, current bio-based phenolic resins also have some shortcomings. Compared with petroleum compounds, biomass has relatively low activity and higher reaction conditions. The introduction of biomass results in uneven product quality and other defects.
  • the present invention provides a daidzein bio-based phenolic resin and its preparation method and application.
  • This method uses the natural compound daidzein, which is a flavonoid phenol source, to replace part of the phenol. Under the action of a certain proportion of catalyst, it reacts with formaldehyde to obtain daidzein biobase.
  • Phenolic Resin The natural compound daidzein is a renewable resource with abundant sources, low price and reduced cost.
  • the preparation method provided by the invention is simple to operate.
  • the prepared daidzein bio-based phenolic resin is a green phenolic resin with excellent performance.
  • a preparation method of pro-didzein bio-based phenolic resin including the following steps:
  • step (1) Gradually heat the reaction mixture in step (1) to a certain temperature, and stir the reaction at this temperature for a period of time;
  • step (3) Cool the reaction mixture in step (2) to room temperature, wash it several times in an ultrasonic cleaner with absolute ethanol and deionized water, and place the product in a vacuum oven to dry and dehydrate at a certain temperature to obtain daidzein.
  • Original bio-based phenolic resin product
  • step (1) in terms of parts by mass, the phenol is 10 parts, the daidzein is 0.5-2 parts, the formaldehyde solution is 13-19 parts, and the sodium hydroxide is 0.2-0.8 parts, wherein the formaldehyde solution is The mass percentage concentration is 37%.
  • the reaction temperature is 95-105°C, and the reaction time is 1-1.5 h.
  • the reaction temperature is 115-125°C, and the reaction time is 1.5-3h.
  • the drying and dehydration temperature is 50-70°C and the time is 24 hours.
  • the ultrasonic cleaning involves washing several times with absolute ethanol and deionized water in an ultrasonic cleaning machine.
  • the present invention also provides the application of the daidzein bio-based phenolic resin prepared by the preparation method described in the previous scheme for preparing friction and friction materials, ablation-resistant materials or damping materials.
  • the daidzein biobased phenolic resin prepared by the present invention has good acid resistance, mechanical properties, and heat resistance, and can be widely used in industries such as anti-corrosion engineering, adhesives, flame retardant materials, and grinding wheel manufacturing;
  • the method of the present invention uses the natural compound daidzein, a flavonoid phenol source, to partially replace phenol to prepare phenolic resin, which can greatly reduce the residual phenol content of the phenolic resin.
  • the present invention introduces the highly rigid structural unit of daidzein, which greatly improves the strength of the phenolic resin. Expand the application fields of phenolic resin.
  • Figure 1 shows the infrared spectra of ordinary phenolic resin a and daidzein biobased phenolic resin b;
  • Figure 2 shows the curing temperature DSC curves of ordinary phenolic resin a and daidzein bio-based phenolic resin b;
  • Figure 3 is the thermogravimetric TG diagram of ordinary phenolic resin
  • Figure 4 is the thermogravimetric TG diagram of pro-didzein bio-based phenolic resin
  • Figure 5 is a cross-sectional SEM scan of ordinary phenolic resin
  • Figure 6 is a cross-sectional SEM scan of daidzein bio-based phenolic resin.
  • reaction mixture was cooled to room temperature, washed three times with absolute ethanol and deionized water in an ultrasonic cleaner, and the product was dried and dehydrated in a vacuum oven at 50-70°C for 24 hours to obtain proto-didzein bio-based phenolic resin.
  • step (3) Cool the stirred reaction mixture obtained in step (2) to room temperature, wash it three times with absolute ethanol and deionized water in an ultrasonic cleaner, and place the product in a vacuum oven to dry and dehydrate at 60°C. After 24 hours, daidzein biobased phenolic resin was obtained.
  • the tensile strength of the daidzein biobased phenolic resin prepared in Example 1 is 19MPa, the elongation rate is 2.41%, the hardness is 121.74HRR, the curing peak temperature is 169.2°C, and the residual rate at 800 degrees is 61.76%.
  • step (3) Cool the stirred reaction mixture obtained in step (2) to room temperature, wash it three times with absolute ethanol and deionized water in an ultrasonic cleaner, and place the product in a vacuum oven to dry and dehydrate at 60°C. After 24 hours, daidzein biobased phenolic resin was obtained.
  • the tensile strength of the daidzein biobased phenolic resin prepared in Example 2 is 20 MPa, the elongation rate is 2.45%, the hardness is 119HRR, the curing peak temperature is 160.2°C, and the residual rate at 800 degrees is 62.15%.
  • step (3) Cool the stirred reaction mixture obtained in step (2) to room temperature, wash it three times with absolute ethanol and deionized water in an ultrasonic cleaner, and place the product in a vacuum oven to dry and dehydrate at 60°C. After 24 hours, daidzein biobased phenolic resin was obtained.
  • the tensile strength of the daidzein biobased phenolic resin prepared in Example 3 is 39MPa, the elongation rate is 2.705%, the hardness is 119.78HRR, the curing peak temperature is 162.4°C, and the residual rate at 800 degrees is 57.75%.
  • step (3) Cool the stirred reaction mixture obtained in step (2) to room temperature, wash it three times with absolute ethanol and deionized water in an ultrasonic cleaner, and place the product in a vacuum oven to dry and dehydrate at 60°C. After 24 hours, daidzein biobased phenolic resin was obtained.
  • the tensile strength of the daidzein biobased phenolic resin prepared in Example 4 is 32MPa, the elongation rate is 3.31%, the hardness is 120.38HRR, the curing peak temperature is 158.7°C, and the residual rate at 800 degrees is 61.93%.
  • step (3) Cool the stirred reaction mixture obtained in step (2) to room temperature, wash it three times with absolute ethanol and deionized water in an ultrasonic cleaner, and place the product in a vacuum oven to dry at 70°C. After dehydration for 24 hours, daidzein biobased phenolic resin was obtained.
  • the tensile strength of the daidzein biobased phenolic resin prepared in Example 5 is 36MPa, the elongation rate is 2.51%, the hardness is 119.88HRR, the curing peak temperature is 162.2°C, and the residual rate at 800 degrees is 62.96%.
  • step (3) Cool the stirred reaction mixture obtained in step (2) to room temperature, wash it three times with absolute ethanol and deionized water in an ultrasonic cleaner, and place the product in a vacuum oven to dry and dehydrate at 70°C. After 24 hours, daidzein biobased phenolic resin was obtained.
  • the tensile strength of the daidzein biobased phenolic resin prepared in Example 6 is 23MPa, the elongation rate is 2.05%, the hardness is 119.34HRR, the curing peak temperature is 156.5°C, and the residual rate at 800 degrees is 61.25%.
  • step (3) Cool the stirred reaction mixture obtained in step (2) to room temperature, wash it three times with absolute ethanol and deionized water in an ultrasonic cleaner, and place the product in a vacuum oven to dry and dehydrate at 60°C. After 24 hours, daidzein biobased phenolic resin was obtained.
  • the tensile strength of the daidzein biobased phenolic resin prepared in Example 7 is 21 MPa, the elongation rate is 2.01%, the hardness is 118.98HRR, the curing peak temperature is 155.3°C, and the residual rate at 800 degrees is 59.94%.
  • the tensile strength of the ordinary phenolic resin prepared in Comparative Example 1 is 26MPa, the elongation rate is 2.13%, the hardness is 122.78HRR, the curing peak temperature is 139.5°C, and the residual rate at 800 degrees is 58.14%.
  • the preparation method of daidzein bio-based phenolic resin utilizes the resource-rich and low-price daidzein and adopts a simple synthetic modification method.
  • the prepared daidzein bio-based phenolic resin is: It is a green phenolic resin with excellent performance. The thermal stability and heat resistance of the product have been greatly improved. According to Figures 1-6 and Table 1, it can be seen that the pro-didzein bio-based phenolic resins prepared by different synthesis processes have differences in tensile strength, elongation rate, curing temperature, and residual rate at 800 degrees Celsius, but there is basically no difference in hardness.
  • Example 3 In terms of tensile strength alone, Example 3 has the best strength, reaching 39MPa, while pure phenolic resin is only 26MPa; Example 4 has the highest tensile rate, reaching 3.31%, which is higher than the tensile strength of pure phenolic resin with the same curing process. The rate should be high. Comparing the thermal properties, it was found that the thermal stability and heat resistance of daidzein bio-based phenolic resin were greatly improved.
  • the prodaidzein bio-based phenolic resin prepared by the invention has excellent mechanical properties and heat resistance, and can be widely used in friction materials, flame retardant materials, grinding wheel manufacturing and other industries.

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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)
  • Phenolic Resins Or Amino Resins (AREA)

Abstract

本发明属于生物基聚合物材料领域，公开了一种黄豆苷原生物基酚醛树脂及其制备方法和应用。本发明利用来源丰富，价格低廉的天然化合物黄豆苷，减少成本，同时本发明提供的制备方法操作简单，并且本发明制备的黄豆苷原生物基酚醛树脂具有优异的力学性能、耐热性能，可广泛应用于胶粘剂、阻燃材料、砂轮片制造等行业。

Description

一种黄豆苷原生物基酚醛树脂及其制备方法和应用
本申请要求于2022年08月11日提交中国专利局、申请号为CN202210960941.4、发明名称为“一种黄豆苷原生物基酚醛树脂的制备方法”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
本发明属于生物基聚合物材料领域，具体涉及一种黄豆苷原生物基酚醛树脂及其制备方法和应用。
背景技术
自从1905年，美国科学家巴克兰对酚醛树脂进行系统而广泛的研究，酚醛树脂的商业应用得到尝试，并且在长达一百年的发展历程中，由于酚醛树脂优异的性能，使其得到了诸多应用。传统且重要的组成成分是苯酚和甲醛，其合成的酚醛树脂性能优异，但同样存在致命的缺陷，资源短缺，高毒性及致癌，高交联度造成的脆性断裂直接制约其发展应用。因此，如何改性酚醛树脂，绿色环保，拓展产品品种及应用领域具有广阔的研究前景。
生物质改性是当下研究的热点，对于环境污染和化石资源日益短缺的背景下，无疑是明智的选择。生物质在自然界资源储量大，种类尤为繁多，来源广泛，作为可再生能源极具发展前景。在酚醛树脂中引用生物质不仅可以提高性能，还能够降低成本，产生较高的经济效益，因此开发出性能更优异，且价格低廉、环保的改性酚醛树脂，在实际应用中存在巨大潜力。
目前常用的生物质改性酚醛树脂主要有诸如木质素、桐油、亚麻油、淀粉、松香、生物油、腰果酚等生物质改性酚醛树脂，这些改性树脂的性能各异，各有优缺点，也开始得到应用。但目前生物基酚醛树脂也存在一些缺点，生物质与石油化合物相比活性相对低，反应条件更高，引入生物质造成产物质量不均匀等缺陷。
发明内容
针对目前酚醛树脂生产存在的问题，本发明提供了一种黄豆苷原生物基酚醛树脂及其制备方法和应用。本方法采用黄酮类酚源天然化合物黄豆苷原替代部分苯酚，在一定比例催化剂作用下，与甲醛反应得到黄豆苷原生物基 酚醛树脂。天然化合物黄豆苷原为可再生资源，来源丰富，价格低廉，减少成本，同时本发明提供的制备方法操作简单，制备的黄豆苷原生物基酚醛树脂为绿色化酚醛树脂，且性能优异。
本发明的技术方案是：
一种黄豆苷原生物基酚醛树脂的制备方法，包括如下步骤：
(1)在搅拌条件下，按比例将黄豆苷原、苯酚和甲醛溶液，混合均匀，再加入氢氧化钠，将反应混合物逐渐加热至一定温度，回流反应一段时间；
(2)将步骤(1)的反应混合物逐渐升温至一定温度，并在该温度下搅拌反应一段时间；
(3)将步骤(2)的反应混合物冷却至室温，用无水乙醇、去离子水分别在超声清洗机中洗涤数遍，将产物置于真空烘箱中于一定温度下干燥脱水，得到黄豆苷原生物基酚醛树脂产物。
优选的，步骤(1)中，按质量份，所述苯酚为10份，黄豆苷原为0.5～2份，甲醛溶液为13～19份，氢氧化钠为0.2～0.8份，其中，甲醛溶液的质量百分浓度为37％。
优选的，步骤(1)中，所述反应温度为95～105℃，反应时间为1～1.5h。
优选的，步骤(2)中，所述反应温度为115～125℃，反应时间为1.5～3h。
优选的，步骤(3)中，所述的干燥脱水温度为50～70℃，时间为24h。
优选的，步骤(3)中，所述超声清洗是用无水乙醇、去离子水分别在超声清洗机中洗涤数遍。
本发明还提供了前述方案所述的制备方法制备得到的黄豆苷原生物基酚醛树脂用于制备摩擦磨阻材料、耐烧蚀材料或阻尼材料的应用。
本发明的有益效果为：
(1)本发明制备的黄豆苷原生物基酚醛树脂具有良好的耐酸性能、力学性能、耐热性能，可广泛应用于防腐蚀工程、胶粘剂、阻燃材料和砂轮片制造等行业；
(2)本发明方法采用黄酮类酚源天然化合物黄豆苷原部分替代苯酚制备酚醛树脂，可大大降低酚醛树脂残酚含量。
(3)本发明引入黄豆苷原的高刚性结构单元，大大改善酚醛树脂的强度， 拓宽酚醛树脂应用领域。
附图说明
图1为普通酚醛树脂a和黄豆苷原生物基酚醛树脂b的红外谱图；
图2为普通酚醛树脂a和黄豆苷原生物基酚醛树脂b的固化温度DSC曲线；
图3为普通酚醛树脂的热重TG图；
图4为黄豆苷原生物基酚醛树脂的热重TG图；
图5为普通酚醛树脂的断面SEM扫描图；
图6为黄豆苷原生物基酚醛树脂的断面SEM扫描图。
具体实施方式
在配备有机械搅拌器，回流冷凝器的250mL三口烧瓶中，加入苯酚10份，黄豆苷原0.5～2份，甲醛溶液13～19份，其中，甲醛溶液的质量百分浓度为37％，混合均匀，再加入0.2～0.8份氢氧化钠，将反应混合物逐渐加热至95～105℃，反应1～1.5h。然后将反应混合物逐渐升温至115～125℃，反应时间为1.5～3h。最后将反应混合物冷却至室温，用无水乙醇、去离子水分别在超声清洗机中洗涤三遍，将产物置于真空烘箱中于50～70℃下干燥脱水24h，得到黄豆苷原生物基酚醛树脂。
为使本发明的上述目的、特征和优点能够更加明显易懂，下面结合具体实施例进一步说明本发明的技术方案。但是本发明不限于所列出的实施例，还应包括在本发明所要求的权利范围内其他任何公知的改变。
实施例1
(1)在配备有机械搅拌器，回流冷凝器的250mL三口烧瓶中，加入苯酚10份，黄豆苷原0.5份，甲醛溶液13份，混合均匀，再加入0.2份氢氧化钠，将反应混合物逐渐加热至105℃，回流反应1h；
(2)将所述步骤(1)得到的回流反应混合物逐渐升温至115℃，搅拌反应1.5h；
(3)将所述步骤(2)得到的搅拌反应混合物冷却至室温，用无水乙醇、去离子水分别在超声清洗机中洗涤三遍，将产物置于真空烘箱中于60℃下干燥脱水24h，得到黄豆苷原生物基酚醛树脂。
实施例1制备的黄豆苷原生物基酚醛树脂拉伸强度为19MPa，拉伸率为2.41％，硬度为121.74HRR，固化峰温度为169.2℃，800度残余率为61.76％。
实施例2
(1)在配备有机械搅拌器，回流冷凝器的250mL三口烧瓶中，加入苯酚10份，黄豆苷原1份，甲醛溶液13份，混合均匀，再加入0.4份氢氧化钠，将反应混合物逐渐加热至95℃，回流反应1h；
(2)将所述步骤(1)得到的回流反应混合物逐渐升温至115℃，搅拌反应1.5h；
(3)将所述步骤(2)得到的搅拌反应混合物冷却至室温，用无水乙醇、去离子水分别在超声清洗机中洗涤三遍，将产物置于真空烘箱中于60℃下干燥脱水24h，得到黄豆苷原生物基酚醛树脂。
实施例2制备的黄豆苷原生物基酚醛树脂拉伸强度为20MPa，拉伸率为2.45％，硬度为119HRR，固化峰温度为160.2℃，800度残余率为62.15％。
实施例3
(1)在配备有机械搅拌器，回流冷凝器的250mL三口烧瓶中，加入苯酚10份，黄豆苷原1.5份，甲醛溶液15份，混合均匀，再加入0.6份氢氧化钠，将反应混合物逐渐加热至105℃，回流反应1h；
(2)将所述步骤(1)得到的回流反应混合物逐渐升温至115℃，搅拌反应2h；
(3)将所述步骤(2)得到的搅拌反应混合物冷却至室温，用无水乙醇、去离子水分别在超声清洗机中洗涤三遍，将产物置于真空烘箱中于60℃下干燥脱水24h，得到黄豆苷原生物基酚醛树脂。
实施例3制备的黄豆苷原生物基酚醛树脂拉伸强度为39MPa，拉伸率为2.705％，硬度为119.78HRR，固化峰温度为162.4℃，800度残余率为57.75％。
实施例4
(1)在配备有机械搅拌器，回流冷凝器的250mL三口烧瓶中，加入苯酚10份，黄豆苷原1.5份，甲醛溶液17份，混合均匀，再加入0.6份氢氧化钠，将反应混合物逐渐加热至105℃，回流反应1h；
(2)将所述步骤(1)得到的回流反应混合物逐渐升温至120℃，搅拌反应2h；
(3)将所述步骤(2)得到的搅拌反应混合物冷却至室温，用无水乙醇、去离子水分别在超声清洗机中洗涤三遍，将产物置于真空烘箱中于60℃下干燥脱水24h，得到黄豆苷原生物基酚醛树脂。
实施例4制备的黄豆苷原生物基酚醛树脂拉伸强度为32MPa，拉伸率为3.31％，硬度为120.38HRR，固化峰温度为158.7℃，800度残余率为61.93％。
实施例5
(1)在配备有机械搅拌器，回流冷凝器的250mL三口烧瓶中，加入苯酚10份，黄豆苷原1.5份，甲醛溶液17份，混合均匀，再加入0.8份氢氧化钠，将反应混合物逐渐加热至95℃，回流反应1.5h；
(2)将所述步骤(1)的得到的回流反应混合物逐渐升温至125℃，搅拌反应2.5h；
(3)将所述步骤(2)的得到的搅拌反应混合物冷却至室温，用无水乙醇、去离子水分别在超声清洗机中洗涤三遍，将产物置于真空烘箱中于70℃下干燥脱水24h，得到黄豆苷原生物基酚醛树脂。
实施例5制备的黄豆苷原生物基酚醛树脂拉伸强度为36MPa，拉伸率为2.51％，硬度为119.88HRR，固化峰温度为162.2℃，800度残余率为62.96％。
实施例6
(1)在配备有机械搅拌器，回流冷凝器的250mL三口烧瓶中，加入苯酚10份，黄豆苷原1.5份，甲醛溶液19份，混合均匀，再加入0.6份氢氧化钠，将反应混合物逐渐加热至95℃，回流反应1.5h；
(2)将所述步骤(1)得到的回流反应混合物逐渐升温至125℃，搅拌反应2.5h；
(3)将所述步骤(2)得到的搅拌反应混合物冷却至室温，用无水乙醇、去离子水分别在超声清洗机中洗涤三遍，将产物置于真空烘箱中于70℃下干燥脱水24h，得到黄豆苷原生物基酚醛树脂。
实施例6制备的黄豆苷原生物基酚醛树脂拉伸强度为23MPa，拉伸率为2.05％，硬度为119.34HRR，固化峰温度为156.5℃，800度残余率为61.25％。
实施例7
(1)在配备有机械搅拌器，回流冷凝器的250mL三口烧瓶中，加入苯酚10份，黄豆苷原2份，甲醛溶液19份，混合均匀，再加入0.6份氢氧化钠，将反应混合物逐渐加热至105℃，回流反应1.5h；
(2)将所述步骤(1)得到的回流反应混合物逐渐升温至125℃，搅拌反应3h；
(3)将所述步骤(2)得到的搅拌反应混合物冷却至室温，用无水乙醇、去离子水分别在超声清洗机中洗涤三遍，将产物置于真空烘箱中于60℃下干燥脱水24h，得到黄豆苷原生物基酚醛树脂。
实施例7制备的黄豆苷原生物基酚醛树脂拉伸强度为21MPa，拉伸率为2.01％，硬度为118.98HRR，固化峰温度为155.3℃，800度残余率为59.94％。
对比例1
在配备有机械搅拌器，回流冷凝器的250mL三口烧瓶中，加入苯酚10份，甲醛溶液17份，混合均匀，再加入0.6份氢氧化钠，将反应混合物逐渐加热至60℃，反应0.5h。然后将得到的反应混合物逐渐升温至90℃，反应时间为4h。最后将得到反应混合物冷却至室温，用无水乙醇、去离子水分别在超声清洗机中洗涤三遍，将产物置于真空烘箱中于60℃下干燥脱水24h，得到普通酚醛树脂。
对比例1制备的普通酚醛树脂拉伸强度为26MPa，拉伸率为2.13％，硬度为122.78HRR，固化峰温度为139.5℃，800度残余率为58.14％
将本发明实施例1-7制备的黄豆苷原生物基酚醛树脂性能和对比例1制备的普通酚醛树脂进行对比，结果如图1-6和表1所示
表1

综上所述，本发明提供的黄豆苷原生物基酚醛树脂的制备方法，利用资源丰富、价格低廉的黄豆苷原，采用操作简单的合成改性方法，制备的黄豆苷原生物基酚醛树脂为绿色化酚醛树脂，且性能优异，产品热稳定性、耐热性能都有较大的提高。根据图1-6及表1可知，不同合成工艺制备得到的黄豆苷原生物基酚醛树脂在拉伸强度和拉伸率、固化温度以及800摄氏度残余率上有差别，而硬度基本没有差别。单独以拉伸强度来看，实施例3的强度最好，达到39MPa，而纯酚醛树脂仅仅26MPa；实施例4的拉伸率最高，达到3.31％，比相同固化工艺的纯酚醛树脂的拉伸率要高。对比热性能发现，黄豆苷原生物基酚醛树脂热稳定性、耐热性能均有较大提高。本发明制备的黄豆苷原生物基酚醛树脂具有优异的力学性能、耐热性能，可广泛应用于摩擦材料、阻燃材料、砂轮片制造等行业。
以上所述仅是本发明的优选实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也应视为本发明的保护范围。

Claims (11)

  1. 一种黄豆苷原生物基酚醛树脂的制备方法，其特征在于，包括如下步骤：
    (1)在搅拌条件下，按比例将黄豆苷原、苯酚和甲醛溶液，混合均匀，再加入氢氧化钠，将反应混合物逐渐加热至一定温度，回流反应一段时间；
    (2)将所述步骤(1)得到的回流反应混合物逐渐升温至一定温度，并在该温度下搅拌反应一段时间；
    (3)将所述步骤(2)得到的搅拌反应混合物冷却至室温，超声清洗，将产物置于真空烘箱中于一定温度下干燥脱水，得到黄豆苷原生物基酚醛树脂。
  2. 根据权利要求1所述的制备方法，其特征在于，步骤(1)中，按质量份，所述苯酚为10份，黄豆苷原为0.5～2份，甲醛溶液为13～19份，氢氧化钠为0.2～0.8份，其中，甲醛溶液的质量百分浓度为37％。
  3. 根据权利要求1所述的制备方法，其特征在于，步骤(1)中，所述回流反应的温度为95～105℃，反应时间为1～1.5h。
  4. 根据权利要求1所述的制备方法，其特征在于，步骤(2)中，所述搅拌反应的温度为115～125℃，反应时间为1.5～3h。
  5. 根据权利要求1所述的制备方法，其特征在于，步骤(3)中，所述干燥脱水的温度为50～70℃，时间为24h。
  6. 根据权利要求1所述的制备方法，其特征在于，步骤(3)中，所述超声清洗是用无水乙醇、去离子水分别在超声清洗机中洗涤数遍。
  7. 根据权利要求6所述的制备方法，其特征在于，所述洗涤的次数为三次。
  8. 权利要求1～7任一项所述制备方法制备的黄豆苷原生物基酚醛树脂。
  9. 根据权利要求8所述的黄豆苷原生物基酚醛树脂，其特征在于，拉伸强度大于19MPa，拉伸率大于2.01％，洛氏硬度大于118.98HRR，固化峰温度大于155.3℃，800度残余率大于57.75％。
  10. 根据权利要求9所述的黄豆苷原生物基酚醛树脂，其特征在于，拉伸强度为19～39MPa，拉伸率为2.01～3.31％，洛氏硬度为118.98～121.74HRR，固化峰温度为155.3～169.2℃，800度残余率大于57.75～62.96％。
  11. 将权利要求1～7任一项所述制备方法制备的黄豆苷原生物基酚醛树 脂或权利要求8～10任一项所述黄豆苷原生物基酚醛树脂用于制备摩擦磨阻材料、耐烧蚀材料或阻尼材料的用途。
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