WO2018095356A1 - 一种氟钛杂化阻燃剂及其制备方法与应用 - Google Patents

一种氟钛杂化阻燃剂及其制备方法与应用 Download PDF

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WO2018095356A1
WO2018095356A1 PCT/CN2017/112576 CN2017112576W WO2018095356A1 WO 2018095356 A1 WO2018095356 A1 WO 2018095356A1 CN 2017112576 W CN2017112576 W CN 2017112576W WO 2018095356 A1 WO2018095356 A1 WO 2018095356A1
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flame retardant
epoxy resin
fluorine
curing agent
titanium
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戴李宗
吴海洋
袁丛辉
刘诚
李云同
吴俣哲
罗伟昂
陈国荣
何凯斌
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Xiamen University
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/13—Phenols; Phenolates
    • C08K5/136—Phenols containing halogens
    • 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
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/28—Titanium compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/10—Transparent films; Clear coatings; Transparent materials

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  • the invention belongs to the technical field of organic flame retardant, and particularly relates to a fluorine titanium hybrid flame retardant and a preparation method and application thereof.
  • Epoxy resins include both epoxy-based oligomers and epoxy-containing low molecular compounds.
  • the epoxy resin has good mechanical properties, strong adhesion, small cure shrinkage, excellent electrical insulation performance, good processability, stability and chemical resistance.
  • Epoxy resin is widely used in the fields of water conservancy, transportation, machinery, electronics, home appliances, automobiles and aerospace as a resin matrix for adhesives, coatings and composite materials. With the increasing requirements for the reliability and safety of epoxy resins in these fields, heat resistance and flame retardancy have become more and more important.
  • a widely used method for improving the flame retardancy of epoxy resins is to add a flame retardant.
  • Fluoropolymer which has many excellent properties such as heat resistance, corrosion resistance, hydrophobic oil, electrical insulation, low friction coefficient, low toxicity, non-combustibility, etc.
  • heat resistance of the modified epoxy resin is improved, on the other hand, in the high temperature environment, the intermolecular rearrangement can be increased, and a highly stable carbon layer is deposited on the surface to protect the internal polymer crosslinked network. effect.
  • the large volume of trifluoromethyl (CF 3 ) introduced in the epoxy resin can further hinder the movement of the molecular segment of the polymer, while the CF 3 group can be enriched on the surface of the epoxy resin, making the ring of high surface energy Oxygen resin has excellent water and oil resistance.
  • CF 3 trifluoromethyl
  • Titanium is an effective flame retardant element, which can effectively reduce the flame propagation rate.
  • the flame retardant of titanium flame retardant on wool fiber was studied.
  • Dai Lizong et al. (a silicon-phosphorus titanium three-element synergistic flame-retardant epoxy resin and its preparation method, 201610200021.7) using phosphorus-containing organotitanium hybrid silsesquioxane modified epoxy resin to introduce titanium metal into silicon phosphorus
  • the flame retardant effect is improved.
  • the existing technical solutions for the flame retardant modification of epoxy resin by using fluorine element combined with titanium element have the defects of complex formula and harsh reaction conditions.
  • the present invention is directed to such a deficiency, and adopts two resource-rich, inexpensive and readily available raw materials for mild organic synthesis of the reaction conditions, and the epoxy resin is modified, and the addition of a small amount not only maintains the transparency and mechanical properties of the resin, but also Greatly improved its heat resistance and flame retardancy.
  • Another object of the present invention is to provide a process for producing the above fluorine-titanium hybrid flame retardant.
  • a fluorine-titanium hybrid flame retardant whose molecular structural formula is:
  • R is CH 3 CH 2 CH 2 CH 2 - or
  • hexafluorobisphenol A in an organic solvent, dissolve and stir at 20 to 50 ° C, then add butyl titanate dropwise, and react at room temperature for 8 to 24 hours after the completion of the addition. Finally, the solvent is removed and purified to obtain a fluorotitanium hybridization resistance.
  • the fuel agent the molar ratio of the above hexafluorobisphenol A to butyl titanate is 1:4.0 to 5.0, and the volume ratio of hexafluorobisphenol A to the organic solvent is 1 g:30 to 50.
  • the above fluorine-titanium hybrid flame retardant is used in the preparation of a flame-retardant epoxy resin.
  • a certain amount of epoxy resin in a reaction vessel raise the temperature to 60-110 ° C, and then add the fluorine-titanium hybrid flame retardant according to a ratio of 0.1-50 wt%.
  • the agent is stirred until it is in a uniform transparent state, and then the curing agent is added to the stoichiometric ratio until completely dissolved and uniformly mixed, and then poured into a mold, and a temperature-increasing program is set for curing to obtain the flame-retardant epoxy resin.
  • the epoxy resin is a bisphenol A type epoxy resin, a bisphenol F type epoxy resin or a novolac type epoxy resin.
  • the curing agent is an amine curing agent, an acid anhydride curing agent, a boron amine complex or an amine group-containing boric acid ester curing agent.
  • the heating program is: 120 ° C for 5 h, then at 140 ° C for 2 h, and finally at 180 ° C for 2 h.
  • the flame retardant epoxy resin prepared by using the fluorine-titanium hybrid flame retardant of the invention has simple and mild reaction conditions and high yield; the product purification operation is simple and easy to industrialize; the prepared epoxy resin has high transparency and ensures excellent resistance. Under the premise of thermal and mechanical properties, the flame retardant effect is good, the scope of application is wide, and it meets environmental protection requirements.
  • Example 1 is a synthetic route diagram of a fluorine-titanium hybrid flame retardant synthesized in Example 1.
  • Example 2 is an infrared spectrum of a fluorine-titanium hybrid flame retardant synthesized in Example 1.
  • Example 3 is a nuclear magnetic resonance spectrum of a fluorine-titanium hybrid flame retardant synthesized in Example 1.
  • 0.336 g (0.001 mol) of hexafluorobisphenol A and 20 mL of ethanol were added to a 50 mL three-neck round bottom flask, and 0.17 g (0.0005 mol) of butyl titanate was dissolved in 6 mL of ethanol, and dissolved uniformly.
  • the mixed liquid was dropped into the above three-necked flask, and the reaction was stirred at room temperature for 24 hours. After completion of the reaction, the solvent was removed by rotary evaporation to obtain a crude product, which was repeatedly washed three times with ethanol and lyophilized to obtain a fluorotitanium hybrid flame retardant in a yield of about 96%.
  • the synthetic route diagram of the fluorine-titanium hybrid flame retardant is shown in FIG.
  • the infrared spectrum of the fluorine-titanium hybrid flame retardant is shown in Fig. 2.
  • the 994 cm -1 peak is a characteristic absorption peak of the -Ti-OC 6 H 4 - group.
  • the nuclear magnetic resonance spectrum of the fluorotitanium hybrid flame retardant is shown in Fig.
  • Pure epoxy resin is the control group, weigh 20g epoxy resin E-51, raise the temperature of 90 ° C, add 5g curing agent 4,4 '-diaminodiphenylmethane, stir evenly, pour into the mold, keep at 120 ° C 5h, then incubated at 140 ° C for 2 h, and finally at 180 ° C for 2 h.
  • the prepared flame retardant epoxy resin was tested to have an oxygen index of 25.4% according to the method of GB/T 2406.2-2009.
  • the prepared flame retardant epoxy resin was tested to have an oxygen index of 28.9% according to the method of GB/T 2406.2-2009.
  • the prepared flame retardant epoxy resin was tested to have an oxygen index of 27.8% according to the method of GB/T 2406.2-2009.
  • the prepared flame retardant epoxy resin was tested to have an oxygen index of 27.8% according to the method of GB/T 2406.2-2009.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
  • Epoxy Resins (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)

Abstract

涉及一种氟钛杂化阻燃剂及其制备方法与应用，其特征在于：其分子结构式为：式（I）其中R为CH 3CH 2CH 2CH 2 - 或式（II）所述的氟钛杂化阻燃剂制备阻燃性环氧树脂反应条件简单温和、产率高；产物提纯操作简单，易于工业化；所制备的环氧树脂透明度高，且在保证了优良耐热性和力学性能的前提下，阻燃效果好、适用范围广、符合环保要求。

Description

一种氟钛杂化阻燃剂及其制备方法与应用 技术领域
本发明属于有机阻燃技术领域，具体涉及一种氟钛杂化阻燃剂及其制备方法与应用。
背景技术
环氧树脂既包括环氧基的低聚物，也包括含环氧基的低分子化合物。环氧树脂力学性能好、附着力强、固化收缩率小、电绝缘性能优良、工艺性好、稳定性以及抗化学药品性优良。环氧树脂作为胶粘剂、涂料和复合材料等的树脂基体，广泛应用于水利、交通、机械、电子、家电、汽车及航空航天等领域。随着这些领域对环氧树脂可靠性与安全性的要求日益增高，尤其是耐热性、阻燃性越来越引起重视。目前广泛采用的提高环氧树脂阻燃性的方法是添加阻燃剂。
含氟聚合物，具有耐热、耐腐蚀、憎水憎油、电绝缘、低摩擦系数及低毒、不燃性等多种优异性能，用有机氟改性环氧树脂一方面由于C-F键能很大，使得改性环氧树脂的耐热性能得到提高，另一方面在高温环境下能增加分子间重排，在表面沉积出现高稳定性的碳层，起到保护内部聚合物交联网络的作用。环氧树脂中引入的大体积的三氟甲基(CF3)可进一步阻碍了聚合物分子链段的运动，同时CF3基团能富集在环氧树脂的表面，使高表面能的环氧树脂具有优异的防水、防油性能。戴李宗等(一种含氟自润滑型织物涂层材料及其制备方法，公开号CN103410003A)将含氟单体与环氧氯丙烷合成了含氟环氧树脂涂料，用酸酐型固化剂固化并添加活性稀释剂，得到了绿色环保环氧固化体系。
钛是一种有效的阻燃元素，可有效降低火焰传播速率，20世纪70年代已有钛阻燃剂对羊毛纤维的阻燃研究。戴李宗等(一种硅磷钛三元素协同阻燃环氧树脂及其制备方法，201610200021.7)采用含磷有机钛杂化倍半硅氧烷改性环氧树脂，将金属钛引入到硅磷协同体系中，提高了阻燃效果。
现有利用氟元素与钛元素结合对环氧树脂进行阻燃改性的技术方案存在配方复杂，反应条件苛刻等缺陷。本发明针对这种不足，采用两种资源丰富，廉价易得的原料进行反应条件温和的有机杂化合成，对环氧树脂进行改性，少量添加不仅可以保持树脂的透明度和力学性能，更极大提高了其耐热阻燃性。
发明内容
本发明的目的在于提供一种氟钛杂化阻燃剂。
本发明的另一目的在于提供上述氟钛杂化阻燃剂的制备方法。
本发明的再一目的在于提供上述氟钛杂化阻燃剂的应用。
本发明的技术方案如下：
一种氟钛杂化阻燃剂，其分子结构式为：
Figure PCTCN2017112576-appb-000001
其中R为CH3CH2CH2CH2-或
Figure PCTCN2017112576-appb-000002
上述氟钛杂化阻燃剂的制备方法，其合成反应式如下：
Figure PCTCN2017112576-appb-000003
具体如下：
称取六氟双酚A于有机溶剂中，20～50℃下溶解搅拌，接着滴加钛酸丁酯，滴加完毕后室温反应8～24h，最后除去溶剂并提纯后得到氟钛杂化阻燃剂；上述六氟双酚A与钛酸丁酯的摩尔比为1∶4.0～5.0，六氟双酚A与有机溶剂的体积比为1g∶30～50。
上述氟钛杂化阻燃剂在制备阻燃性环氧树脂中的应用。
在本发明的一个优选实施方案中，具体为：称取一定量的环氧树脂于反应容器内，升温到60～110℃，再按照0.1～50wt％的比例加入所述氟钛杂化阻燃 剂，搅拌至呈均一透明状态，接着按照化学计量比加入固化剂至完全溶解且混合均匀，再倒入模具中，设定升温程序进行固化，得到所述阻燃性环氧树脂。
进一步优选的，所述环氧树脂为双酚A型环氧树脂、双酚F型环氧树脂或线性酚醛型环氧树脂。
进一步优选的，所述固化剂为胺类固化剂、酸酐类固化剂、硼胺配合物或带胺基的硼酸酯类固化剂。
进一步优选的，所述升温程序为：120℃保持5h，然后在140℃保温2h，最后在180℃保温2h。
本发明的有益效果是：
用本发明的氟钛杂化阻燃剂制备阻燃性环氧树脂反应条件简单温和、产率高；产物提纯操作简单，易于工业化；所制备的环氧树脂透明度高，且在保证了优良耐热性和力学性能的前提下，阻燃效果好、适用范围广、符合环保要求。
附图说明
图1为实施例1中所合成的氟钛杂化阻燃剂的合成路线图。
图2为实施例1中所合成的氟钛杂化阻燃剂的红外谱图。
图3为实施例1中所合成的氟钛杂化阻燃剂的核磁共振氢谱图。
具体实施方式
以下通过具体实施方式结合附图，对本发明的技术方案进行进一步的说明和描述。
实施例1
将0.336g(0.001mol)的六氟双酚A和20mL乙醇加入到50mL的三口圆底烧瓶中，再将0.17g(0.0005mol)的钛酸丁酯溶于6mL的乙醇中，溶解均匀后，将该混合液滴加到上述三口烧瓶中，室温下搅拌反应24h。反应结束后旋转蒸发除去溶剂得到粗产物，反复用乙醇洗涤三次并冻干后得到氟钛杂化阻燃剂，产率约为96％。
所述氟钛杂化阻燃剂的合成路线图见图1所示。所述氟钛杂化阻燃剂红外谱图见图2所示。994cm-1谱峰为-Ti-O-C6H4-基团的特征吸收峰。所述氟钛杂化阻燃剂核磁共振氢谱图见图3，1H NMR(CDCl3，500MHz)δ(ppm)：9.84(1H，ph-OH)，7.89(1H，C-CH-CH)，7.49(1H，CH-CH-C)，7.36(1H，C-CH-CH)，6.74(1H，CH-CH-C)，3.48(2H，O-CH2-CH2)，1.46(4H，CH2-CH2-CH2)，0.92(3H，CH2-CH3)。
实施例2
纯环氧树脂的制备
纯环氧树脂为对照组，称取20g环氧树脂E-51，升高温度90℃，加入5g固化剂4，4’-二氨基二苯甲烷，搅拌均匀后倒入模具，在120℃保持5h，然后在140℃保温2h，最后在180℃保温2h。
将所制备的阻燃性环氧树脂按照GB/T 2406.2-2009方法测试其氧指数为25.4％。
将所制备的阻燃性环氧树脂按照GB/T 2408-2008方法测试其垂直燃烧等级结果如表1所示。
实施例3
称取20g环氧树脂E-51，升温到100℃，加入0.25g实施例1制备的氟钛杂化阻燃剂，阻燃剂的添加质量按照质量百分比计算，氟钛杂化阻燃剂为环氧树脂的1％，边搅拌边采用抽真空除去小分子物质，完全溶解后加入5g的4，4’-二氨基二苯甲烷，搅拌均匀后倒入模具，在120℃保持5h，然后在140℃保温2h，最后在180℃保温2h，阻燃性环氧树脂。
将所制备的阻燃性环氧树脂按照GB/T 2406.2-2009方法测试其氧指数为28.9％。
将所制备的阻燃性环氧树脂按照GB/T 2408-2008方法测试其垂直燃烧等级结果如表1所示。
实施例4
称取20g环氧树脂E-51，升温到100℃，加入0.77g氟钛杂化阻燃剂，阻燃剂的添加质量按照质量百分比计算，氟钛杂化阻燃剂为环氧树脂的3％，边搅拌边采用抽真空除去小分子物质，完全溶解后加入5g的4，4’-二氨基二苯甲烷，搅拌均匀后倒入模具，在120℃保持5h，然后在140℃保温2h，最后在180℃保温2h，阻燃性环氧树脂。
将所制备的阻燃性环氧树脂按照GB/T 2406.2-2009方法测试其氧指数为27.8％。
将所制备的阻燃性环氧树脂按照GB/T 2408-2008方法测试其垂直燃烧等级结果如表1所示。
实施例5
称取20g环氧树脂E-51，升温到100℃，加入1.316g氟钛杂化阻燃剂，阻燃剂的添加质量按照质量百分比计算，氟钛杂化阻燃剂为环氧树脂的5％，边搅拌边采用抽真空除去小分子物质，完全溶解后加入5g的4，4’-二氨基二苯甲烷，搅拌均匀后倒入模具，在120℃保持5h，然后在140℃保温2h，最后在180℃保温2h，阻燃性环氧树脂。
将所制备的阻燃性环氧树脂按照GB/T 2406.2-2009方法测试其氧指数为27.8％。
将所制备的阻燃性环氧树脂按照GB/T 2408-2008方法测试其垂直燃烧等级结果如表1所示。
表1
Burning Grade t1(s) t2(s) Dripping
对照组 NR ＞30s / Yes
实施例2 V-1 12 2 NO
实施例3 V-1 11 21 NO
实施例4 V-1 22 12 NO
以上所述，仅为本发明的较佳实施例而已，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 (7)

  1. 一种氟钛杂化阻燃剂，其特征在于：其分子结构式为：
    Figure PCTCN2017112576-appb-100001
    其中R为CH3CH2CH2CH2-或
    Figure PCTCN2017112576-appb-100002
  2. 如权利要求1所述的一种氟钛杂化阻燃剂的制备方法，其特征在于：其合成反应式如下：
    Figure PCTCN2017112576-appb-100003
    具体如下：
    称取六氟双酚A于有机溶剂中，20～50℃下溶解搅拌，接着滴加钛酸丁酯，滴加完毕后室温反应8～24h，最后除去溶剂并提纯后得到氟钛杂化阻燃剂；上述六氟双酚A与钛酸丁酯的摩尔比为1∶4.0～5.0，六氟双酚A与有机溶剂的体积比为1g∶30～50。
  3. 权利要求1所述的氟钛杂化阻燃剂在制备阻燃性环氧树脂中的应用。
  4. 如权利要求3所述的应用，其特征在于：具体为：称取一定量的环氧树脂于反应容器内，升温到60～110℃，再按照0.1～50wt％的比例加入所述氟钛杂化阻燃剂，搅拌至呈均一透明状态，接着按照化学计量比加入固化剂至完全溶解且混合均匀，再倒入模具中，设定升温程序进行固化，得到所述阻燃性环氧树脂。
  5. 如权利要求4所述的应用，其特征在于：所述环氧树脂为双酚A型环氧树脂、双酚F型环氧树脂或线性酚醛型环氧树脂。
  6. 如权利要求4所述的应用，其特征在于：所述固化剂为胺类固化剂、酸酐类固化剂、硼胺配合物或带胺基的硼酸酯类固化剂。
  7. 如权利要求4所述的应用，其特征在于：所述升温程序为：120℃保持5h，然后在140℃保温2h，最后在180℃保温2h。
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