WO2018095362A1 - 一种磷杂菲结构反应型阻燃剂及其应用 - Google Patents

一种磷杂菲结构反应型阻燃剂及其应用 Download PDF

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WO2018095362A1
WO2018095362A1 PCT/CN2017/112584 CN2017112584W WO2018095362A1 WO 2018095362 A1 WO2018095362 A1 WO 2018095362A1 CN 2017112584 W CN2017112584 W CN 2017112584W WO 2018095362 A1 WO2018095362 A1 WO 2018095362A1
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flame retardant
preparing
reactive flame
epoxy resin
phosphaphenanthrene
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PCT/CN2017/112584
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戴李宗
柳超
陈国荣
黄佳美
许一婷
曾碧榕
罗伟昂
袁丛辉
何凯斌
刘新瑜
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厦门大学
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
    • C07F9/6581—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and nitrogen atoms with or without oxygen or sulfur atoms, as ring hetero atoms
    • C07F9/6584—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and nitrogen atoms with or without oxygen or sulfur atoms, as ring hetero atoms having one phosphorus atom as ring hetero atom
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/50—Amines
    • C08G59/5033—Amines aromatic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/62—Alcohols or phenols
    • C08G59/621—Phenols
    • C08G59/623—Aminophenols

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  • the invention relates to a flame retardant, in particular to a phosphorus phenanthrene structure reactive flame retardant and application thereof.
  • epoxy resin Since the invention of epoxy resin by both Castan and Greenlee in 1936, epoxy resin has been used in transportation, infrastructure construction, ship and marine, aerospace and electrical engineering for almost all aspects of social life due to its good physical and chemical properties. Has a wide range of applications. Despite this, due to the flammability of general-purpose epoxy resins, they are not suitable for use in many fields. With the development of the epoxy resin industry in the direction of refinement, the development of new and efficient flame retardants to improve the flame retardant ability of epoxy resin has become a research hotspot.
  • epoxy resin flame retardants are various in variety and classification methods are also different. According to the elemental content of the flame retardant, it can be classified into a phosphorus-based, nitrogen-based, silicon-based, fluorine-based flame retardant or a synergistic flame retardant containing two or more elements. According to whether the flame retardant has a functional group capable of reacting with the epoxy resin, it can be further classified into an additive type and a reactive type flame retardant.
  • the reactive flame retardant has a long-lasting flame retardant effect, does not migrate in the epoxy resin, and can maintain or improve its mechanical properties while improving the flame retardancy of the epoxy resin.
  • Gao et al. (Gao LP, Wang DY, Wang YZ, et al. Polymer Degradation and Stability, 2008, 93(7): 1308-1315.) synthesized a single-reactive functional group of phosphorus-containing monomer DODPP, and then different proportions The DODPP reacts with DGEBA to obtain different phosphorus content epoxy resins. When the phosphorus addition amount is 2.5%, the obtained cured product can be tested to a V-0 level by UL-94, and the LOI value is 30.2%. The heat release test resulted in a decrease in the values of HRR, PHRR, and Av-HRR.
  • Murias (Murias P, Maciejewski H, Galina H. European Polymer Journal, 2012, 48(4): 769-773.) synthesized two kinds of siloxanes having an amino group or an epoxy group, respectively, and Ethyltetramine is a curing agent and co-cured with a low molecular weight epoxy (E6) to obtain an epoxy cured product.
  • E6 low molecular weight epoxy
  • the invention relates to a phosphorus phenanthrene structure reactive flame retardant and application thereof.
  • the phenanthroline structure reactive flame retardant comprises tetramethylol phosphine sulfate (THPS), aniline, glacial acetic acid, p-hydroxybenzaldehyde (4-HBA) and 9,10-dihydro-9-oxa-10 - a phosphorus phenanthrene-10-oxide (DOPO) reaction.
  • THPS tetramethylol phosphine sulfate
  • aniline aniline
  • glacial acetic acid glacial acetic acid
  • 4-HBA p-hydroxybenzaldehyde
  • DOPO 9,10-dihydro-9-oxa-10 - a phosphorus phenanthrene-10-oxide
  • the catalyst p-toluenesulfonic acid is used in an amount of from 1% to 10% by mass of the substance I;
  • the solvent is toluene; the reaction temperature is from 100 ° C to 180 ° C; and the reaction time is from 8 to 20 h.
  • the molar ratio of DOPO, 4-HBA and substance I in step (2) can be 4:3:1-6:5:1, and the amount of catalyst p-toluenesulfonic acid is 2%-8 of the mass fraction of substance I. %.
  • the reaction temperature is from 120 ° C to 160 ° C, and the reaction time is from 10 to 16 hours.
  • the flame retardant contains three hydroxyl groups in the molecular structure, which can react with the epoxy group and participate in the curing of the epoxy resin. Compared with the common reactive flame retardant, its functionality is higher, and the modified epoxy resin is more firmly bonded to the matrix.
  • the flame retardant has a plurality of benzene rings and a fused ring structure in the molecular structure, and the phosphorus, carbon and nitrogen atoms form a six-membered heterocyclic ring, and therefore, it has higher thermal stability and hydrolysis resistance.
  • the relative molecular mass of the flame retardant is 1321, which is better than that of the small molecule flame retardant in the epoxy resin without migration.
  • Example 1 is a nuclear magnetic resonance spectrum of the flame retardant of Example 1.
  • Example 2 is a nuclear magnetic phosphorus spectrum of the flame retardant of Example 1.
  • the preparation steps and flame retardant test steps of the pure epoxy resin and the flame retardant modified epoxy resin are as follows.
  • the reaction type flame retardant-modified epoxy resin was obtained by keeping it for 2 hours. In this way, 6.39 g, 10.66 g of the flame retardant (corresponding to a phosphorus content of 3%, 5%, respectively) was added to 20 g of epoxy resin to prepare a modified epoxy resin.

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  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Fireproofing Substances (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Epoxy Resins (AREA)

Abstract

本发明公开了一种磷杂菲结构反应型阻燃剂及其应用，其制备方法是将9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物(DOPO)、对羟基苯甲醛(4—HBA)和5—氨基甲基—1,3—二苯基—1,3,5—二氮磷杂环在一定条件下反应可得到一种含多羟基、多苯环刚性结构的反应型阻燃剂。与普通阻燃剂相比，其具有多官能度、分子结构稳定、耐水解性好、在环氧树脂中不易发生迁移的特点，同时，能显著提高环氧树脂阻燃性能。

Description

一种磷杂菲结构反应型阻燃剂及其应用 技术领域
本发明涉及一种阻燃剂，尤其是一种磷杂菲结构反应型阻燃剂及其应用。
背景技术
自1936年卡斯坦与格林利同时发明环氧树脂以来，环氧树脂因其具有良好的物理、化学性能而在交通运输、基础设施建设、船舶和海洋、宇航以及电气工程等几乎社会生活的方方面面有着广泛的应用。尽管如此，由于通用型环氧树脂易燃的特点，其在很多领域均不能满足使用要求。而随着环氧树脂行业朝着精细化的方向发展，开发新型高效的阻燃剂以提高环氧树脂的阻燃能力已成为研究热点。
目前，环氧树脂阻燃剂种类多样，分类方法也有所不同。根据阻燃剂所含的元素分，可分为磷系、氮系、硅系、氟系阻燃剂或者含有两种或以上元素的协同阻燃剂。根据阻燃剂有无能与环氧树脂反应的官能团又可分为添加型和反应型阻燃剂。反应型阻燃剂具有阻燃效果持久、不会在环氧树脂中发生迁移，且在提高环氧树脂阻燃能力同时也可保持或提高其机械性能等特点。
Gao等(Gao LP，Wang DY，Wang YZ，et al.Polymer Degradation and Stability，2008，93(7):1308-1315.)合成了一种单反应官能团的含磷单体DODPP，然后将不同比例的DODPP与DGEBA反应，得到不同含磷量的环氧树脂。当磷添加量达2.5％时，得到的固化物经过UL-94测试可达V-0级，LOI值30.2％。热释放测试得到HRR，PHRR，Av-HRR的值均会减小。Murias(Murias P，Maciejewski H，Galina H.European Polymer Journal，2012，48(4):769-773.)等合成了两种端基分别带有氨基或环氧基的硅氧烷，并以三亚乙基四胺为固化剂，与低分子量的环氧(E6)共固化得到环氧固化物，当硅氧烷的加入量增大时，得到的环氧固化物的LOI值也从21.9％提高到23.9％，且冲击强度会有明显提高。
发明内容
本发明涉及一种磷杂菲结构反应型阻燃剂及其应用。
所述磷杂菲结构反应型阻燃剂由四羟甲基硫酸膦(THPS)、苯胺、冰醋酸、对羟基苯甲醛(4—HBA)及9，10-二氢-9-氧杂-10-磷杂菲-10-氧化物(DOPO)反应所得。
所述磷杂菲结构反应型阻燃剂结构式如下：
Figure PCTCN2017112584-appb-000001
所述磷杂菲结构反应型阻燃剂合成路线如下：
Figure PCTCN2017112584-appb-000002
所述的磷杂菲结构反应型阻燃剂合成步骤如下：
(1)5—氨基甲基—1,3—二苯基—1,3,5—二氮磷杂环(以下称为物质Ⅰ)的合成方法参照Frank A Drake Jr G L.The Journal of Organic Chemistry,1972,37(17):2752-2755；
(2)在三口瓶中加入DOPO、4-HBA和物质Ⅰ，再加入催化量的对甲苯磺酸，通氮气保护，升温并磁力搅拌，反应一定时间；
(3)反应完成后用以硅胶为固定相的柱色谱进行分离。
其中，所述物质Ⅰ、4-羟基苯甲醛、DOPO的摩尔比为1：2-6：3-7；
所述催化剂对甲苯磺酸用量为物质Ⅰ质量分数的1％-10％；
所述溶剂采用甲苯；反应温度为100℃-180℃；反应时间为8-20h。
所述多官能度反应型阻燃剂的制备方法特征在于包括以下步骤：
1、步骤(2)中DOPO、4-HBA和物质Ⅰ三者的摩尔比可为4：3：1—6：5：1，催化剂对甲苯磺酸用量为物质Ⅰ质量分数的2％—8％。反应温度为120℃—160℃，反应时间为10—16h。
2、步骤(3)中柱色谱进行分离时展开剂为乙酸乙酯：石油醚＝4:1(体积比)，每100mL展开剂中加入5mL冰醋酸。
本发明所述的阻燃剂具有如下优点：
(1)该阻燃剂分子结构中含有三个羟基，可与环氧基反应，参与环氧树脂固化。与普通反应型阻燃剂相比，其官能度更高，改性环氧树脂后与基体结合更牢固。
(2)该阻燃剂分子结构中有多个苯环及稠环结构，且磷、碳、氮原子形成了一个六元杂环，因此，其具有更高的热稳定性和耐水解性。
(3)该阻燃剂相对分子质量为1321，相比小分子阻燃剂，其能更好的存在于环氧树脂中而不发生迁移。
附图说明
图1为实施例1阻燃剂核磁氢谱谱图。
图2为实施例1阻燃剂核磁磷谱谱图。
具体实施方式
下面通过实施例对本发明做进一步说明。
实施例1
在三口瓶中分别加入2.16g(0.01mol)、0.732g(0.006mol)、0.722g(0.002mol)的DOPO、4-HBA和物质Ⅰ，再加入0.0864g(相对物质Ⅰ的质量分数为4％)的对甲苯磺酸，通氮气保护，升温到130℃，磁力搅拌反应12h。反应完成后以硅胶为固定相，乙酸乙酯：石油醚＝4:1为展开剂，每100mL展开剂中加入5mL冰醋酸，柱色谱进行分离得到产物。
核磁谱图见图1和图2。
实施例2
在三口瓶中分别加入2.592g(0.012mol)、0.732g(0.006mol)、0.722g(0.002mol)的DOPO、4-HBA和物质Ⅰ，再加入0.0864g(相对物质Ⅰ的质量分数为4％)的对甲苯磺酸，通氮气保护，升温到130℃，磁力搅拌反应16h。
反应完成后以硅胶为固定相，乙酸乙酯：石油醚＝4:1为展开剂，每100mL展开剂中加入5mL冰醋酸，柱色谱进行分离得到产物。
实施例3
在三口瓶中分别加入2.592g(0.012mol)、0.976g(0.008mol)、0.722g(0.002mol) 的DOPO、4-HBA和物质Ⅰ，再加入0.0864g(相对物质Ⅰ的质量分数为4％)的对甲苯磺酸，通氮气保护，升温到130℃，磁力搅拌反应16h。反应完成后以硅胶为固定相，乙酸乙酯：石油醚＝4:1为展开剂，每100mL展开剂中加入5mL冰醋酸，柱色谱进行分离得到产物。
实施例4
在三口瓶中分别加入2.592g(0.012mol)、0.732g(0.006mol)、0.722g(0.002mol)的DOPO、4-HBA和物质Ⅰ，再加入0.0864g(相对物质Ⅰ的质量分数为4％)的对甲苯磺酸，通氮气保护，升温到130℃，磁力搅拌反应12h。反应完成后以硅胶为固定相，乙酸乙酯：石油醚＝4:1为展开剂，每100mL展开剂中加入5mL冰醋酸，柱色谱进行分离得到产物。
纯环氧树脂及该阻燃剂改性的环氧树脂制备及阻燃测试步骤如下。
(1)纯环氧树脂的制备
称取20g环氧树脂E-51，升温到100℃，加入4g固化剂4,4’-二氨基二苯甲烷，搅拌均匀后倒入模具，在120℃保温4小时，然后在140℃保温2小时，最后在160℃保温2小时。
(2)反应型阻燃剂改性的环氧树脂的制备
称取20g环氧树脂E-51，升温到100℃，加入2.13g该阻燃剂(所含磷元素的质量为环氧树脂质量的1％，以下阻燃剂添加量均以磷元素质量计)，搅拌溶解后在真空下抽除小分子物质，加入4g固化剂4,4’-二氨基二苯甲烷，搅拌均匀后倒入模具，在120℃保温4小时，然后在140℃保温2小时，最后在160℃
保温2小时，即得该反应型阻燃剂改性的环氧树脂。按此方法，分别添加6.39g、10.66g该阻燃剂(对应磷元素含量分别为3％、5％)到20g环氧树脂中制成改性环氧树脂。
(3)将所得样品按照GB/T 2406.2-2009方法测试其氧指数。
测试结果见表1
表1 不同磷含量改性环氧树脂极限氧指数测试结果
Figure PCTCN2017112584-appb-000003
以上所述，仅为本发明较佳实施例而已，故不能依此限定本发明实施的范围，即依本发明专利范围及说明书内容所作的等效变化与修饰，皆应仍属本发明涵盖的范围内。

Claims (10)

  1. 一种磷杂菲结构反应型阻燃剂，其特征在于分子结构如下：
    Figure PCTCN2017112584-appb-100001
  2. 如权利要求1所述一种磷杂菲结构反应型阻燃剂的合成路线如下：
    Figure PCTCN2017112584-appb-100002
  3. 如权利要求1所述一种磷杂菲结构反应型阻燃剂的制备方法，包括以下步骤：
    在氮气保护下，向容器中依次加入反应物5—氨基甲基—1,3—二苯基—1,3,5—二氮磷杂环、4-羟基苯甲醛、DOPO和溶剂，再加入对甲苯磺酸作为催化剂，升温反应一段时间，得到淡黄色溶液，浓缩，除去溶剂，将所得物质通过柱色谱进行分离即得一种磷杂菲结构反应型阻燃剂；其中，
    所述的5—氨基甲基—1,3—二苯基—1,3,5—二氮磷杂环、4-羟基苯甲醛、DOPO的摩尔比为1：2-6：3-7；
    所述催化剂对甲苯磺酸用量为5—氨基甲基—1,3—二苯基—1,3,5—二氮磷杂环质量分数的1％-10％；
    所述溶剂采用甲苯；反应温度为100℃-180℃；反应时间为8-20h。
  4. 如权利要求3所述一种磷杂菲结构反应型阻燃剂的制备方法，其特征在于所述的5—氨基甲基—1,3—二苯基—1,3,5—二氮磷杂环、4-羟基苯甲醛、DOPO的摩尔比为1：3-5：4-6。
  5. 如权利要求3所述一种磷杂菲结构反应型阻燃剂的制备方法，其特征在于所述催化剂对甲苯磺酸用量为5—氨基甲基—1,3—二苯基—1,3,5—二氮磷杂 环质量分数的2％—8％。
  6. 如权利要求3所述一种磷杂菲结构反应型阻燃剂的制备方法，其特征在于所述溶剂采用甲苯；反应温度为120℃—160℃；反应时间为10—16h。
  7. 如权利要求3所述一种磷杂菲结构反应型阻燃剂的制备方法，其特征在于所述柱色谱以300-400目硅胶为固定相，乙酸乙酯：石油醚体积比＝4:1为流动相，每100mL展开剂中加入5mL冰醋酸。
  8. 如权利要求1所述一种磷杂菲结构反应型阻燃剂在制备阻燃高分子材料中的应用。
  9. 一种阻燃高分子材料的制备方法，包括如下步骤：称取环氧树脂预聚体升温至一定温度，搅拌，加入一定质量分数的权利要求1所述的磷杂菲结构反应型阻燃剂，搅拌至混合物呈均一透明的状态，按化学计量比加入固化剂直至完全溶解，倒入铝制模具中，设置升温程序进行固化得到阻燃环氧树脂。
  10. 如权利要求9所述一种阻燃高分子材料的制备方法，其特征在于在称取环氧树脂预聚体升温至85～100℃，搅拌时间为20～40min；加入磷杂菲结构反应型阻燃剂质量分数为1～30％，继续搅拌时间为40～80min；程序升温过程为在120～130℃固化4h，继续在130～150℃保温2h，最后在150～170℃保温2h。
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