WO2022147942A1 - 含活性环氧基团的二烷基次膦酸酯化物及其制备和应用 - Google Patents

含活性环氧基团的二烷基次膦酸酯化物及其制备和应用 Download PDF

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WO2022147942A1
WO2022147942A1 PCT/CN2021/094488 CN2021094488W WO2022147942A1 WO 2022147942 A1 WO2022147942 A1 WO 2022147942A1 CN 2021094488 W CN2021094488 W CN 2021094488W WO 2022147942 A1 WO2022147942 A1 WO 2022147942A1
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epoxy group
active epoxy
flame retardant
dialkyl
preparation
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PCT/CN2021/094488
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French (fr)
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李金忠
陈章明
雷华
杨建伟
王家凯
曹俊华
王海峰
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江苏利思德新材料有限公司
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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
    • C07F9/655—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having oxygen atoms, with or without sulfur, selenium, or tellurium atoms, as the only ring hetero atoms
    • C07F9/65502—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having oxygen atoms, with or without sulfur, selenium, or tellurium atoms, as the only ring hetero atoms the oxygen atom being part of a three-membered ring
    • C07F9/65505—Phosphonic acids containing oxirane groups; esters thereof
    • 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
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
    • C08K5/5313—Phosphinic compounds, e.g. R2=P(:O)OR'
    • 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

Definitions

  • the invention relates to the field of dialkyl phosphinates, in particular to a dialkyl phosphinate containing active epoxy groups and its preparation and application.
  • Organophosphates are the main varieties of organophosphorus, which are mainly obtained by reacting phosphoric acid, phosphorous acid, methylphosphonic acid, etc. with alcohols. Common organic phosphates include triethyl phosphate, trimethyl phosphite, dimethyl methyl phosphonate, diethyl ethyl phosphonate and the like.
  • hypophosphorous acid and its derivatives have been widely used because of their good flame retardant properties.
  • the metal salts of hypophosphorous acid and its derivatives (such as the patented technology of CN1660857A, CN106967116A, etc.) are widely used, and these metal salt compounds are usually added in the form of fillers because they have no reactivity.
  • the reactive flame retardant can react with the matrix polymer, and the flame retardant structure enters the polymer molecular chain, which has a higher flame retardant efficiency and can greatly reduce the flame retardant efficiency. dosage of the agent.
  • salt compounds are usually solid powders, which are not suitable for some application systems that require transparency. Therefore, it is necessary to develop reactive and liquid flame retardants.
  • the dialkyl phosphinic acid group has better flame retardant properties, and the epoxy group has the reactivity to continue the ring-opening reaction.
  • the combination of the two can exert two characteristics of flame retardant properties and epoxy activity.
  • compounds are usually liquids at room temperature. Therefore, it is both reactive and liquid, and has a flame retardant function.
  • the present invention provides a dialkylphosphinate ester compound containing an active epoxy group, which is flame retardant compared to the metal salts of hypophosphorous acid and its derivatives. It contains reactive active epoxy groups, has high flame retardant efficiency, and is liquid and can meet the advantages of transparent applications; and the molecule contains two P-C bonds at the same time, which is not a chemical under the key monitoring of the OPCW. It is convenient for production and promotion.
  • a dialkyl phosphinate compound containing an active epoxy group the structure is shown in any of the following formulas (I) and (II):
  • R 1 and R 2 are independently selected from C 1 -C 24 alkyl (including alkane groups, etc.), cycloalkyl, aryl or alkenyl, and R 3 is independently selected A straight-chain or branched alkylene group from C 1 -C 10 , or an arylene group, an alkylarylene group or an arylalkylene group of C 6 -C 10 , m is an integer from 1 to 3, and n is 1 -3 integer.
  • R 1 and R 2 respectively include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, phenyl, alkenyl and the like.
  • R 3 includes but is not limited to: methylene, ethylene, phenylene and the like.
  • the present invention provides a novel organic phosphoric acid ester compound that has not been reported in the literature.
  • it has two core characteristic structures, that is, a dialkyl hypophosphorous acid structure and an epoxy structure.
  • the dialkyl hypophosphorous acid structure has good flame retardancy, while the epoxy structure is reactive and can undergo ring-opening reactions with various organic groups to form alcohols or esters, or as a monomer of epoxy resins for Preparation of epoxy resin polymers.
  • the structural compound is usually liquid, and it does not affect the transparency of the material when applied to the polymer.
  • dialkyl phosphinate ester containing active epoxy group has the following structure ( III) shows:
  • the active epoxy group-containing dialkyl phosphinate has the following structure (VII ) as shown:
  • the present invention also provides the preparation method of the dialkyl phosphinic acid ester compound containing active epoxy groups, which comprises: using the dialkyl phosphinic acid metal salt and the halogenated epoxy compound as raw materials, and reacting to obtain the dialkyl phosphinic acid ester compound. the dialkyl phosphinate containing reactive epoxy groups;
  • the reaction process is as follows:
  • M is a metal element, selected from one or more of sodium, potassium, calcium, magnesium, aluminum, zinc, barium, X is selected from one or more of fluorine, chlorine, bromine, iodine, and k is The number of valence states of the metal element M.
  • the dialkyl phosphinic acid metal salt participates in the reaction in a solid form
  • the halogenated epoxy compound is a liquid
  • the reaction is a liquid-solid reaction.
  • the above reaction process can be carried out under the action of a catalyst, and the catalyst is preferably a phase transfer catalyst, including cationic polyalkyl quaternary ammonium salt compounds, cationic halogenated polyalkyl quaternary ammonium salt compounds, anionic alkyl sulfate compounds, and alkyl quaternary ammonium salt compounds.
  • a phase transfer catalyst including cationic polyalkyl quaternary ammonium salt compounds, cationic halogenated polyalkyl quaternary ammonium salt compounds, anionic alkyl sulfate compounds, and alkyl quaternary ammonium salt compounds.
  • Preferred catalysts include: polyalkylammonium chlorides, polyalkylammonium bromides, alkyl sulfates, alkylsulfonates, alkylbenzenesulfonates, fatty alcohol polyoxyethylene ethers, alkylphenol polyoxyethylenes Ether, alkyl phosphate, polyethylene glycol, polyol, etc.
  • the reaction can be carried out without adding a catalyst for a long time, or one or more of the catalysts can be added to accelerate the reaction.
  • the temperature of the reaction is 40-200° C.
  • the pressure is 0-5 MPa
  • the time is 0.1-20 hours.
  • a high-purity epoxy group-containing dialkyl phosphinate compound can be obtained through post-processing techniques such as filtration and distillation.
  • the synthesis process can be carried out batchwise or continuously.
  • a series of reaction devices such as pipeline reactors, can be used to carry out the reaction.
  • the present invention also provides the application of the dialkyl phosphinate containing active epoxy groups in preparation or as a flame retardant.
  • phosphate ester flame retardants such as phosphate ester flame retardants, triethyl phosphate (TEP), tributyl phosphate (TBP), trioctyl phosphate, triphenyl phosphate Esters (TPP), Tris (xylylene) Phosphate (TXP), Tris (2-chloroisopropyl) Phosphate (TCPP), Tris (2-chloroethyl) Phosphate (TCEP), 3-Tris (Di) Chloropropyl) Phosphate (TDCPP); Dimethyl Methyl Phosphonate (DMMP); Diethyl Ethyl Phosphonate (DEEP), etc.
  • TEP triethyl phosphate
  • TBP triethyl phosphate
  • TBP tributyl phosphate
  • trioctyl phosphate triphenyl phosphate Esters
  • TPP Tris (xylylene) Phosphate
  • Nitrogen-containing flame retardants such as ammonium polyphosphate, melamine cyanurate, Melamine polyphosphate, piperazine, piperazine phosphate, piperazine pyrophosphate, etc.
  • Alkyl hypophosphites such as aluminum diethylphosphinate, aluminum ethylbutylphosphinate, aluminum dibutylphosphinate
  • Inorganic flame retardants such as aluminum hydroxide, zinc oxide, tin oxide, etc., according to different epoxy application systems, choose different flame retardant dosages.
  • the amount of the flame retardant is between 1-35wt%.
  • the amount of flame retardant is between 1-25 wt%.
  • the present invention also provides the application of the active epoxy group-containing dialkyl phosphinate in the preparation of flame retardant materials
  • the flame retardant materials include epoxy materials, polyesters, polyurethane materials, flame retardant materials At least one of carbon fiber materials, flame-retardant glass fiber materials, and alcohol compounds.
  • the epoxy material can use the dialkyl phosphinate of the present invention as a reactive flame retardant to participate in the synthesis of epoxy resin.
  • C 1 -C 24 and the like all refer to the number of carbon atoms contained in the group.
  • alkyl is a group formed by the loss of any hydrogen atom on the molecule of an alkane compound.
  • the alkane compounds include straight-chain alkanes, branched-chain alkanes, and the like.
  • Aryl is the same.
  • alkylene is a group formed by losing any two hydrogen atoms on the molecule of an alkane compound.
  • the alkane compounds include straight chain alkanes and branched chain alkanes. The same is true for "arylene”.
  • the main advantages of the present invention include:
  • the flame retardant molecule contains dialkyl phosphinic acid and active epoxy group, Two characteristic structures.
  • the dialkyl phosphinate of the present invention contains an unopened active epoxy group, which can be added to the epoxy resin system, and at the same time participates in the reaction and is combined with the epoxy compound, and has reactivity.
  • the molecular structure can be The reaction enters the polymer molecular chain, which greatly reduces the amount of flame retardant.
  • the dialkyl phosphinate of the present invention can be used to prepare a flame retardant epoxy material, and the flame retardant can be used alone or mixed with other flame retardants.
  • the epoxy material containing the flame retardant has good flame retardant properties.
  • the dialkyl phosphinate compound of the present invention is usually liquid and does not affect the transparency of the base material.
  • the dialkyl phosphinate compound of the present invention can also prepare phosphorus-containing alcohol and ester compounds with flame retardant function.
  • Fig. 1 is the schematic diagram of the nuclear magnetic resonance phosphorus spectrum of the product obtained in Example 1 of the present invention.
  • Fig. 2 is the schematic diagram of the hydrogen nuclear magnetic resonance spectrum of the product obtained in Example 1 of the present invention.
  • Fig. 3 is the nuclear magnetic resonance phosphorus spectrum schematic diagram of the raw material sodium diethyl hypophosphite used in the embodiment of the present invention 1;
  • Fig. 4 is the hydrogen nuclear magnetic resonance spectrum schematic diagram of the raw material sodium diethyl hypophosphite used in the embodiment of the present invention 1;
  • Fig. 5 is the hydrogen nuclear magnetic resonance spectrum schematic diagram of the raw material epichlorohydrin used in the embodiment of the present invention 1;
  • the raw materials are purchased through commercial channels.
  • NMR Nuclear Magnetic Resonance
  • the molecular structures of the prepared compounds can be determined by 31 P NMR and 1 H NMR.
  • the calculation method of the yield is: (weight of product/theoretical weight of product) ⁇ 100%.
  • the peaks between the offsets 3.7-4.3 represent the new structure (PO-CH 2 ), and the offsets are between 0.9-1.8
  • the peaks in between represent the hydrogens of the two ethyl groups attached to the phosphorus atom, and the peaks between the offsets 2.4-2.9 represent the epoxy group structure. It is shown that the obtained compound is an epoxy group-containing dialkyl phosphinate represented by formula (III), and the object of the present invention is achieved.
  • the compound of formula (III) prepared in Example 1 and the epoxy resin curing agent DDS are mixed uniformly in a certain proportion, a small amount of sampling is performed to test the DSC curve, and the reaction of the compound of formula (III) and DDS is judged according to the exothermic peak in the DSC curve.
  • the DSC curve obtained from the test is shown in Figure 6.
  • the DSC curve of DDS alone shows that because DDS is a solid, there is a melting point peak at 179.3°C, which is an endothermic process; while the compound of structure (III) (glycidyl diethylphosphinate) has a melting point peak at 218.3°C.
  • the exothermic peak indicates that the compound of structure (III) itself undergoes a ring-opening reaction and emits heat; while there are two exothermic peaks on the DSC curve of the compound of structure (III) and DDS mixture, namely 210.0 °C and 264.1 °C.
  • the peaks are obviously different from the exothermic peaks of the individual compounds of structure (III): one is that the exothermic peaks advance from 218 °C to 210 °C; The self-ring-opening exotherm is 0.04623 mW/mg, while the exotherm of structure (III) compound and DDS mixture is 0.2142 mW/mg, which is significantly larger than that of structure (III) compound alone.
  • the dialkyl phosphinate prepared in Example 1 of the present invention is added to the epoxy resin, and its specific operation process is as follows:
  • Example 2 Identical to Example 2, except that the system does not add the glycidyl diethyl hypophosphite obtained in Example 1, the specific formula composition is shown in Table 1, and the oxygen index results are shown in Table 2.
  • Example 2 The same as Example 2, except that the flame retardant in Example 2 is replaced by aluminum diethylphosphinate, the specific formula composition is shown in Table 1, and the oxygen index results are shown in Table 2.
  • the limiting oxygen index of the epoxy resin is greatly improved.
  • Oxygen resin content 10% increased from 18 to 33, while relative to the conventional additive type aluminum dialkyl phosphinate (non-reactive, powder) flame retardant, in the case of the same addition, the oxygen index is only from From 18 to 27, the flame retardant performance is not as good as that of epoxy group-containing dialkyl phosphinates, showing that epoxy group-containing dialkyl phosphinates have higher resistance than hypophosphite flame retardants. combustion performance.

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Abstract

一种含活性环氧基团的二烷基次膦酸酯化物及其制备和作为阻燃剂、制备阻燃材料中的应用。结构如下式(I)、(II)任一所示。式(I)、(II)中，R 1、R 2分别独立选自C 1-C 24的烷基、环烷基、芳基或烯基，R 3独立地选自C 1-C 10的直链或支链亚烷基，或者C 6-C 10的亚芳基、烷基亚芳基或芳基亚烷基，m为1-3的整数，n为1-3的整数。制备方法：以二烷基次膦酸金属盐和卤代环氧化合物为原料反应得到。优点在于：同时具有二烷基次膦酸和环氧活性基团两种结构；活性环氧基团，可制备醇、酯和环氧树脂；可以用作阻燃剂，单独使用或者与其它阻燃剂混合后使用。

Description

含活性环氧基团的二烷基次膦酸酯化物及其制备和应用 技术领域
本发明涉及二烷基次膦酸酯化物领域，具体涉及一种含活性环氧基团的二烷基次膦酸酯化物及其制备和应用。
背景技术
有机磷酸酯是有机磷系的主要品种，其主要由磷酸、亚磷酸、甲基膦酸等与醇反应得到有机磷酸酯类。常见的有机磷酸酯有磷酸三乙酯、亚磷酸三甲酯、甲基膦酸二甲酯、乙基膦酸二乙酯等。
次磷酸的有机磷酸酯报道较少，二烷基次膦酸的酯报道更少，而含有环氧基团的二烷基次膦酸酯未见报道。而次磷酸及其衍生物由于具有较好的阻燃性能，已广泛应用。但较多的是次磷酸及其衍生物的金属盐(如公开号为CN1660857A、CN106967116A的专利技术等)应用较多，而这些金属盐类化合物由于没有反应活性，通常是以填充物的形式加入的到聚合物基体中，添加量较大，而反应性阻燃剂由于与基体聚合物可发生反应，阻燃结构进入聚合物分子链上，具有更高的阻燃效率，可大幅降低阻燃剂的用量。另外，盐类化合物通常是固体粉末，对于一些要求透明的应用体系则不能适用。因此，开发具有反应活性，又是液体的阻燃剂是很有必要的。
二烷基次膦酸基团具有较佳的阻燃特性，环氧基团具有继续开环反应的反应活性，二者结合可以发挥出阻燃特性和环氧活性的两种特点，同时这类化合物与金属盐不同，常温通常是液体。因此满足既有反应活性，又是液体，并有阻燃功能。
发明内容
针对上述技术问题以及本领域存在的不足之处，本发明提供了一种含活性环氧基团的二烷基次膦酸酯化物，相较于次磷酸及其衍生物的金属盐类阻燃剂，含有可反应性活性环氧基团，阻燃效率高，且为液体可满足透 明应用等优点；且分子中同时含有两个P-C键，不属于国际禁化武组织重点监控的化学品，生产及推广使用方便。
一种含活性环氧基团的二烷基次膦酸酯化物，结构如下式(I)、(II)任一所示：
Figure PCTCN2021094488-appb-000001
式(I)、(II)中，R 1、R 2分别独立选自C 1-C 24的烷基(包括链烷基等)、环烷基、芳基或烯基，R 3独立地选自C 1-C 10的直链或支链亚烷基，或者C 6-C 10的亚芳基、烷基亚芳基或芳基亚烷基，m为1-3的整数，n为1-3的整数。
R 1、R 2分别包括但不限定于：甲基、乙基、正丙基、异丙基、正丁基、仲丁基、异丁基、叔丁基、苯基、烯基等。
R 3包括但不限定于：亚甲基、亚乙基、亚苯基等。
本发明提供了一种未见文献报道的新型有机磷酸酯化合物，在其结构式中，具有两个核心特征结构，即，二烷基次磷酸结构和环氧结构。二烷基次磷酸结构具有很好的阻燃性，而环氧结构具有反应活性，可以与多种有机基团发生开环反应，形成醇或酯，或者作为环氧树脂的单体，用于制备环氧树脂聚合物。同时该结构化合物通常是液体，应用于聚合物中不影响材料的透明性。
当R 1，R 2均为乙基、R 3为亚甲基，m＝1和n＝1时，所述的含活性环氧基团的二烷基次膦酸酯化物，结构如下式(III)所示：
Figure PCTCN2021094488-appb-000002
当R 1为乙基，R 2为丁基、R 3为亚甲基，m＝1和n＝1时，所述的含活性环氧基团的二烷基次膦酸酯化物，结构如下式(IV)所示：
Figure PCTCN2021094488-appb-000003
当R 1为甲基，R 2为乙基、R 3为亚甲基，m＝1和n＝1时，所述的含活性环氧基团的二烷基次膦酸酯化物，结构如下式(V)所示：
Figure PCTCN2021094488-appb-000004
当R 1为乙基，R 2为苯基、R 3为亚甲基，m＝1和n＝1时，所述的含活性环氧基团的二烷基次膦酸酯化物，结构如下式(VI)所示：
Figure PCTCN2021094488-appb-000005
当R 1，R 2均为乙基、R 3为亚乙基，m＝1和n＝1时所述的含活性环氧基团的二烷基次膦酸酯化物，结构如下式(VII)所示：
Figure PCTCN2021094488-appb-000006
本发明还提供了所述的含活性环氧基团的二烷基次膦酸酯化物的制备方法，包括：以二烷基次膦酸金属盐和卤代环氧化合物为原料，反应得到所述含活性环氧基团的二烷基次膦酸酯化物；
反应过程如下：
Figure PCTCN2021094488-appb-000007
其中，M为金属元素，选自钠、钾、钙、镁、铝、锌、钡中的一种或多种，X选自氟、氯、溴、碘中的一种或多种，k为金属元素M的价态数。
上述反应过程中，二烷基次膦酸金属盐以固体形式参与反应，卤代环氧化合物为液体，反应是液-固反应。
上述反应过程可在催化剂作用下进行，所述的催化剂优选为相转移催化剂，包括阳离子多烷基季铵盐化合物，阳离子卤代多烷基季铵盐化合物，阴离子烷基硫酸盐化合物，烷基苯磺酸盐，非离子表面活性剂，季膦盐等。优选的催化剂包括：多烷基氯化铵、多烷基溴化铵、烷基硫酸盐、烷基磺酸盐、烷基苯磺酸盐、脂肪醇聚氧乙烯醚、烷基酚聚氧乙烯醚、烷基磷酸酯，聚乙二醇，聚多元醇等。上述反应过程可以选择不加入催化剂长时间反应，或加入所述催化剂中的一种或多种，从而加速反应。
作为优选，所述反应的温度为40-200℃，压力为0-5MPa，时间为0.1-20 小时。
反应完成后，可通过过滤、蒸馏等后处理工艺，可以得到高纯度的含环氧基团的二烷基次膦酸酯化合物。
该合成工艺可以为间歇式或连续式进行。连续式工艺中可采用一系列的反应装置，如管道式反应器进行反应。
本发明还提供了所述的含活性环氧基团的二烷基次膦酸酯化物在制备或作为阻燃剂中的应用。
本领域技术人员可以根据实际需要，将本发明的二烷基次膦酸酯化物作为阻燃剂单独使用或者与其它阻燃剂混合后使用。此处所述的其它阻燃剂包括(1)磷酸酯阻燃剂，如磷酸酯阻燃剂，磷酸三乙酯(TEP)，磷酸三丁酯(TBP)，磷酸三辛酯，磷酸三苯酯(TPP)，磷酸三(二甲苯)酯(TXP)，三(2-氯异丙基)磷酸酯(TCPP)、三(2-氯乙基)磷酸酯(TCEP)、3-三(二氯丙基)磷酸酯(TDCPP)；甲基膦酸二甲酯(DMMP)；乙基膦酸二乙酯(DEEP)等(2)含氮阻燃剂，如聚磷酸铵，氰尿酸三聚氰胺，聚磷酸三聚氰胺，哌嗪，磷酸哌嗪，焦磷酸哌嗪等(3)烷基次磷酸盐，如二乙基次膦酸铝，乙基丁基次膦酸铝，二丁基次膦酸铝等；(4)无机阻燃剂，如氢氧化铝，氧化锌，氧化锡等，根据不同的环氧应用体系，选择不同的阻燃剂用量。通常情况下，该阻燃剂用量在1-35wt％之间。可选地，阻燃剂用量在1-25wt％之间。
本发明还提供了所述的含活性环氧基团的二烷基次膦酸酯化物在制备阻燃材料中的应用，所述阻燃材料包括环氧材料、聚酯、聚氨酯材料、阻燃碳纤维材料、阻燃玻璃纤维材料、醇类化合物中的至少一种。
所述环氧材料可采用本发明的二烷基次膦酸酯作为反应型阻燃剂，参与环氧树脂的合成。
本发明中，C 1-C 24等均指基团中所包含的碳原子数。
本发明中，“烷基”是由烷烃化合物分子上失去任意一个氢原子所形成的基团。所述烷烃化合物包括直链烷烃、支链烷烃等。“芳基”同理。
本发明中，“亚烷基”是由烷烃化合物分子上失去任意二个氢原子所形成的基团。所述烷烃化合物包括直链烷烃、支链烷烃。“亚芳基”同理。
本发明与现有技术相比，主要优点包括：
1、提供了具有式(I)、(II)的含活性环氧基团的二烷基次膦酸酯化 物，该阻燃剂分子中含二烷基次膦酸和活性环氧基团，两种特征结构。
2、本发明的二烷基次膦酸酯，含有未开环的活性环氧基团，可以添加入环氧树脂体系，同时参与反应结合于环氧化合物中，具有反应活性，该分子结构可以反应进入聚合物分子链中，大幅降低阻燃剂用量。
3、利用本发明的二烷基次膦酸酯可以用来制备阻燃环氧材料，该阻燃剂单独使用或者与其它阻燃剂混合后使用。含有该阻燃剂的环氧材料具有良好的阻燃性能。
4、本发明的二烷基次膦酸酯化合物通常是液体，不影响基体材料的透明性。
5、本发明的二烷基次膦酸酯化合物还可以制备具有阻燃功能的含磷的醇和酯类化合物。
附图说明
图1为本发明实施例1所得产物的核磁共振磷谱示意图；
图2为本发明实施例1所得产物的核磁共振氢谱示意图；
图3为本发明实施例1所用原料二乙基次磷酸钠的核磁共振磷谱示意图；
图4为本发明实施例1所用原料二乙基次磷酸钠的核磁共振氢谱示意图；
图5为本发明实施例1所用原料环氧氯丙烷的核磁共振氢谱示意图；
图6为实施例2中式(III)化合物与环氧树脂固化剂DDS混合物的DSC曲线。
具体实施方式
下面结合附图及具体实施例，进一步阐述本发明。应理解，这些实施例仅用于说明本发明而不用于限制本发明的范围。下列实施例中未注明具体条件的操作方法，通常按照常规条件，或按照制造厂商所建议的条件。
如无特别说明，原料均通过商业途径购买。
核磁共振(NMR)测试：所用型号为AVANCE DMX 400MHz，瑞士Bruker公司；测试方法为：
1H NMR，以CDCl 3为溶剂，四甲基硅烷内标；
31P NMR，以氘代氯仿为溶剂，85％磷酸外标，扫描次数为64次；
通过 31P NMR和 1H NMR可以确定所制备化合物的分子结构。
以下实施例中，产率的计算方法为：(产物重量/产物理论重量)×100％。
实施例1 具有式(III)中的结构的化合物制备
Figure PCTCN2021094488-appb-000008
向装有搅拌器、温度计的压力釜中加入288g(2mol)二乙基次膦酸酸钠，6.0g催化剂多烷基溴化铵，600g环氧氯丙烷，开启搅拌，通入氮气置换三次，升温至110-120℃，保温搅拌10小时后开启真空，脱去未反应完的环氧氯丙烷。产物经过滤，蒸馏提纯，得到液体成品338g，转化率95％。
通过对所得到产物进行NMR-P谱和NMR-H谱进行表征，结果如附图1(磷谱核磁)和附图2(氢谱核磁)所示。通过与图3(二乙基次磷酸钠磷谱核磁)对比可以知道，在图1中，偏移量60-65ppm间的峰代表了二乙基次磷酸结构，新合成的化合物中含有二乙基次磷酸结构，但与二乙基次磷酸钠的略有偏移。通过对比图2和图4、图5的氢谱核磁，可以发现在图2中，偏移量3.7-4.3之间的峰代表了新结构(P-O-CH 2)，偏移量0.9-1.8之间的峰代表了与磷原子相连接的两个乙基的氢，偏移量2.4-2.9之间的峰代表了环氧基团结构。显示了所得到的化合物为式(III)所示的含环氧基团的二烷基次膦酸酯，实现了本发明的目标。
含环氧活性基团的二烷基次膦酸酯的应用
实施例2 制备阻燃环氧材料
1)式(III)化合物与DDS的反应
将实施例1制备的式(III)化合物与环氧树脂固化剂DDS按一定比例混合均匀，少量取样测试DSC曲线，根据DSC曲线中的放热峰来判断 式(III)化合物与DDS的反应。测试得到的DSC曲线如图6所示。
从结果看，单独DDS的DSC曲线显示，DDS由于是固体，在179.3℃有一个熔点峰，为吸热过程；而结构(III)化合物(二乙基次膦酸缩水甘油酯)在218.3℃的放热峰，说明了结构(III)化合物自身发生了开环反应，放出热量；而结构(III)化合物和DDS混合物的DSC曲线上，存在两个放热峰，即210.0℃和264.1℃放热峰，相比单独的结构(III)化合物的放热峰，明显不同：一是放热峰提前，从218℃前移到210℃；二是放热量明显不同，单独的结构(III)化合物的自开环放热量为0.04623mW/mg，而结构(III)化合物和DDS混合物的放热量为0.2142mW/mg，放热量明显比单独的结构(III)化合物大。这些结果说明了结构(III)化合物与DDS发生了反应，显示其反应活性。
2)阻燃环氧材料的制备
将本发明实施例1制备的二烷基次膦酸酯，加入环氧树脂中，其具体操作过程为：
固化剂DDS和丁酮在杯子中溶解，加入到环氧树脂E-44中，加入实施例1获得的二乙基次磷酸缩水甘油酯，搅拌分散1分钟，倒入四氟模具中，真空40℃1h脱出丁酮，升温至120℃1h，120℃1h，180℃1h，降温、放出真空制得2mm厚的样板。具体配方见表1中。
对比例1
与实施例2相同，除了体系不添加实施例1制得的二乙基次磷酸缩水甘油酯，具体配方组成见表1，氧指数结果见表2.
对比例2
与实施例2相同，除了把实施例2中的阻燃剂替换为二乙基次膦酸铝外，具体配方组成见表1，氧指数结果见表2。
表1 环氧样板制备配方
原料名称 实施例2 对比例1 对比例2
环氧树脂(g) 50 50 50
实施例1二烷基次膦酸酯(g) 5 0 0
二乙基次膦酸铝(g) 0 0 5
固化剂DDS(g) 15 15 15
丁酮(g) 45 45 45
按表1配方准备各原料并制板，将制得的板切割成120×10×2mm的样条，每五根一组，测试氧指数对照，氧指数是材料阻燃性能的一种表征方法，氧指数越大，表示材料的阻燃性能越好。结果见表2。
表2 极限氧指数测试结果
测试项 实施例2 对比例1 对比例2
氧指数(LOI) 33 18 27
通过应用结果看，加入本发明的含环氧基团的二烷基次膦酸酯，相比于不加阻燃剂，环氧树脂的极限氧指数大幅提升，在体系中加入5g(占环氧树脂含量10％)从18提高到33，而相对于常规的添加型的二烷基次膦酸铝(无反应活性，粉末)阻燃剂，在加入量相同的情况下，氧指数只是从18提高到27，阻燃性能不如含环氧基团的二烷基次膦酸酯，显示了含环氧基团的二烷基次膦酸酯比次磷酸盐阻燃剂具有更高的阻燃性能。
此外应理解，在阅读了本发明的上述描述内容之后，本领域技术人员可以对本发明作各种改动或修改，这些等价形式同样落于本申请所附权利要求书所限定的范围。

Claims (10)

  1. 一种含活性环氧基团的二烷基次膦酸酯化物，其特征在于，结构如下式(I)、(II)任一所示：
    Figure PCTCN2021094488-appb-100001
    式(I)、(II)中，R 1、R 2分别独立选自C 1-C 24的烷基、环烷基、芳基或烯基，R 3独立地选自C 1-C 10的直链或支链亚烷基，或者C 6-C 10的亚芳基、烷基亚芳基或芳基亚烷基，m为1-3的整数，n为1-3的整数。
  2. 根据权利要求1所述的含活性环氧基团的二烷基次膦酸酯化物，其特征在于，结构如下式(III)所示：
    Figure PCTCN2021094488-appb-100002
  3. 根据权利要求1所述的含活性环氧基团的二烷基次膦酸酯化物，其特征在于，结构如下式(IV)所示：
    Figure PCTCN2021094488-appb-100003
  4. 根据权利要求1所述的含活性环氧基团的二烷基次膦酸酯化物，其特征在于，结构如下式(V)所示：
    Figure PCTCN2021094488-appb-100004
  5. 根据权利要求1所述的含活性环氧基团的二烷基次膦酸酯化物，其特征在于，结构如下式(VI)所示：
    Figure PCTCN2021094488-appb-100005
  6. 根据权利要求1所述的含活性环氧基团的二烷基次膦酸酯化物，其特征在于，结构如下式(VII)所示：
    Figure PCTCN2021094488-appb-100006
  7. 根据权利要求1～6任一权利要求所述的含活性环氧基团的二烷基次膦酸酯化物的制备方法，其特征在于，包括：以二烷基次膦酸金属盐和卤代环氧化合物为原料，反应得到所述含活性环氧基团的二烷基次膦酸酯化物；
    反应过程如下：
    Figure PCTCN2021094488-appb-100007
    其中，M为金属元素，选自钠、钾、钙、镁、铝、锌、钡中的一种或多种，X选自氟、氯、溴、碘中的一种或多种，k为金属元素M的价态数。
  8. 根据权利要求7所述的制备方法，其特征在于，所述反应的温度为40-200℃，压力为0-5MPa，时间为0.1-20小时。
  9. 根据权利要求1～6任一权利要求所述的含活性环氧基团的二烷基次膦酸酯化物在制备或作为阻燃剂中的应用。
  10. 根据权利要求1～6任一权利要求所述的含活性环氧基团的二烷基次膦酸酯化物在制备阻燃材料中的应用，其特征在于，所述阻燃材料包括环氧材料、聚酯、聚氨酯材料、阻燃碳纤维材料、阻燃玻璃纤维材料、醇类化合物中的至少一种。
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