WO2019034149A1 - 一种制备丙二醇苯醚的催化剂及丙二醇苯醚的合成方法 - Google Patents

一种制备丙二醇苯醚的催化剂及丙二醇苯醚的合成方法 Download PDF

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WO2019034149A1
WO2019034149A1 PCT/CN2018/101121 CN2018101121W WO2019034149A1 WO 2019034149 A1 WO2019034149 A1 WO 2019034149A1 CN 2018101121 W CN2018101121 W CN 2018101121W WO 2019034149 A1 WO2019034149 A1 WO 2019034149A1
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phenyl ether
propylene glycol
glycol phenyl
catalyst
propylene oxide
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PCT/CN2018/101121
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English (en)
French (fr)
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梁国强
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佳化化学（茂名）有限公司
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Priority to PL18846367.3T priority Critical patent/PL3626340T3/pl
Priority to EP18846367.3A priority patent/EP3626340B1/en
Priority to US16/627,938 priority patent/US11091416B2/en
Publication of WO2019034149A1 publication Critical patent/WO2019034149A1/zh

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
    • B01J31/0255—Phosphorus containing compounds
    • B01J31/0267—Phosphines or phosphonium compounds, i.e. phosphorus bonded to at least one carbon atom, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, the other atoms bonded to phosphorus being either carbon or hydrogen
    • B01J31/0268—Phosphonium compounds, i.e. phosphine with an additional hydrogen or carbon atom bonded to phosphorous so as to result in a formal positive charge on phosphorous
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/02—Preparation of ethers from oxiranes
    • C07C41/03—Preparation of ethers from oxiranes by reaction of oxirane rings with hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/02—Ethers
    • C07C43/20—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring
    • C07C43/23—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring containing hydroxy or O-metal groups
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
    • B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
    • B01J2231/4277—C-X Cross-coupling, e.g. nucleophilic aromatic amination, alkoxylation or analogues
    • B01J2231/4288—C-X Cross-coupling, e.g. nucleophilic aromatic amination, alkoxylation or analogues using O nucleophiles, e.g. alcohols, carboxylates, esters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
    • B01J2231/48—Ring-opening reactions
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • C07C2527/14—Phosphorus; Compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • C07C2531/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • C07C2531/24—Phosphines

Definitions

  • the invention belongs to the technical field of chemical industry, and particularly relates to a catalyst for preparing propylene glycol phenyl ether and a method for synthesizing propylene glycol phenyl ether.
  • Propylene glycol phenyl ether is a colorless transparent liquid with mild odor and non-toxic and environmentally friendly properties. Propylene glycol phenyl ether is a typical high-efficiency film-forming auxiliary. After adding the latex system, it can be redistributed in the aqueous phase and the polymerization phase. Its partition coefficient in the two phases is extremely small, thus ensuring excellent film forming performance and good performance. The plasticizing effect and the appropriate evaporation rate balance. Propylene glycol phenyl ether has a strong solubility for most latexes, and its water-soluble properties ensure that it is completely absorbed by the latex particles, giving the latex paint the best color uniformity and coalescence. Excellent storage stability.
  • Propylene glycol phenyl ether can also be used as an excellent high-boiling organic solvent and modifier to replace the solvent of isophorone, cyclohexanone, benzyl alcohol or ethylene glycol phenyl ether. Due to its non-toxicity, good miscibility, moderate volatilization rate, excellent coalescence and coupling ability, low surface tension, it is widely used in automotive and automotive refinish coatings, electrophoretic coatings, industrial baking varnishes and ships, containers, wood coatings, etc. field.
  • propylene glycol phenyl ether generally adopts two synthetic processes, one is to produce propylene glycol phenyl ether by using chloropropanol and phenol as a reaction substrate, but chloropropanol is used as a substrate, and a large amount of waste is easily generated.
  • the second method for synthesizing propylene glycol phenyl ether is to carry out ring-opening polymerization of phenol and propylene oxide (PO) to form propylene glycol phenyl ether under the catalysis of a basic catalyst such as sodium hydroxide or potassium hydroxide.
  • the method is an industrial production method mainly used at present, but the catalyst is used to catalyze the synthesis of the product.
  • propylene glycol phenyl ether also contains metal ions such as potassium metal and sodium ions, and cannot be directly applied to industrial fields where metal ions are strictly restricted. Subsequent processing of the product is required to remove metal ions, complicating the operation of the entire process and increasing the production cost of propylene glycol phenyl ether.
  • the technical problem to be solved by the invention is to overcome the metal ion contained in the propylene glycol phenyl ether catalyzed by the catalyst in the prior art, and can not be directly applied to the industrial field where the metal ion is strictly restricted, and the subsequent metal ion removal operation leads to the whole process.
  • the operation process is complicated and the production cost is increased.
  • a catalyst capable of producing propylene glycol phenyl ether which is free of metal ions and which does not require subsequent metal ion removal operations.
  • the first aspect of the invention provides the use of a quaternary phosphonium salt compound as a catalyst for the preparation of propylene glycol phenyl ether.
  • the above quaternary phosphonium salt compound is used as a catalyst for preparing propylene glycol phenyl ether.
  • the quaternary phosphonium salt compound is selected from the group consisting of methyl triphenylphosphonium bromide, ethyl triphenylphosphonium bromide, and propyl three. Any one or a combination of phenylphosphonium bromide or butyltriphenylphosphonium bromide.
  • the above quaternary phosphonium salt compound is preferably used as a catalyst for preparing propylene glycol phenyl ether, and the molar fraction of any one of the components is from 1 to 99 parts.
  • a second aspect of the present invention provides a method for synthesizing propylene glycol phenyl ether, comprising the steps of: mixing phenol with the above quaternary phosphonium salt compound, and then adding propylene oxide under anaerobic conditions, the phenol and the ring The oxypropane is polymerized to form the propylene glycol phenyl ether.
  • the molar ratio of the phenol to the propylene oxide is 1: (1-1.15).
  • the quaternary phosphonium salt compound is added in an amount of from 0.05% to 0.3% by mass of the phenol to the propylene oxide.
  • the polymerization reaction is carried out under the conditions of a temperature of 100 to 160 ° C and a pressure of ⁇ 1.0 MPa.
  • the method for synthesizing the above propylene glycol phenyl ether preferably further comprises: adding the temperature to 80 ° C before the step of adding the propylene oxide, then controlling the temperature to 80 to 160 ° C, the pressure ⁇ 1.0 MPa, adding the The step of propylene oxide.
  • the method for synthesizing the above propylene glycol phenyl ether preferably further comprises: after adding propylene oxide, controlling the temperature at 100 to 160 ° C, and aging for 2 to 10 hours to obtain the propylene glycol phenyl ether; and then controlling the temperature at 100 to 130 ° C, And the step of vacuuming at 100 to 130 °C.
  • the quaternary phosphonium salt compound provided by the invention as a catalyst for preparing propylene glycol phenyl ether
  • the quaternary phosphonium salt compound as a catalyst has high catalytic efficiency, and the catalytically synthesized propylene glycol phenyl ether does not contain metal ions such as potassium and sodium. Improve the quality and environmental friendliness of synthetic products. After the synthesis of propylene glycol phenyl ether by using the quaternary phosphonium salt catalyst, the subsequent operation of removing metal ions is not required, which simplifies the production process and reduces the production cost.
  • the quaternary phosphonium salt compound has high relative stability as a catalyst, and the quality of the catalytically synthesized propylene glycol phenyl ether is stable, the repeatability between batches is good, and the requirements for the reaction conditions and the strength of the equipment are lowered.
  • the quaternary phosphonium salt compound provided by the present invention as a catalyst for preparing propylene glycol phenyl ether is methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, propyltriphenylphosphonium bromide or butyltriphenylbenzene. Any one or a combination of the above-mentioned compounds as a catalyst for preparing propylene glycol phenyl ether, which has the characteristics of high thermal stability, easy availability, no pollution, and no need to separate from the product. It is an economical and environmentally friendly catalyst that can reduce the synthesis cost of propylene glycol phenyl ether and promote the environmental impact of the synthesis process.
  • the method for synthesizing propylene glycol phenyl ether provided by the present invention by using the above quaternary phosphonium salt compound as a reaction catalyst, the synthesized propylene glycol phenyl ether does not contain metal ions, and does not require subsequent metal ion removal operation, thereby improving product quality. It simplifies the operation process of the entire synthesis process and reduces the production cost of propylene glycol phenyl ether.
  • the method for synthesizing propylene glycol phenyl ether provided by the invention reduces the addition of the catalyst under the premise of ensuring the catalytic activity and product quality of the catalyst by controlling the reaction temperature, pressure, time, and the ratio of addition of phenol and propylene oxide.
  • the amount of propylene glycol phenyl ether produced by the above method is small, and does not require a subsequent rectification purification step, and can be directly applied to industrial production and application.
  • the method for synthesizing propylene glycol phenyl ether provided by the present invention ensures high catalytic activity of the catalyst by controlling the temperature and pressure of the reaction, and the vacuuming step after the end of the reaction effectively removes the substrate which is not completely reacted.
  • the present embodiment provides a method for synthesizing propylene glycol phenyl ether, which specifically comprises the following steps:
  • the propylene oxide feed valve is closed, and the temperature is maintained at 100 to 110 ° C for 8 hours. After the completion of the reaction, the temperature was controlled to 100 to 110 ° C, and evacuation was carried out for 1 hour. The temperature is lowered to below 80 ° C to obtain a propylene glycol phenyl ether product.
  • the present embodiment provides a method for synthesizing propylene glycol phenyl ether, which specifically comprises the following steps:
  • the propylene oxide feed valve is closed, and the temperature is maintained at 130 to 140 ° C for 4 hours. After the end of the reaction, the temperature was controlled to 110 to 120 ° C, and evacuation was carried out for 2.5 hours. The temperature is lowered to 80 ° C to obtain a propylene glycol phenyl ether product.
  • the present embodiment provides a method for synthesizing propylene glycol phenyl ether, which specifically comprises the following steps:
  • the propylene oxide feed valve is closed, and the temperature is maintained at 150 to 160 ° C for 4 hours. After the end of the reaction, the temperature was controlled to 120 to 130 ° C, and evacuation was carried out for 2 hours. The temperature is lowered to below 80 ° C to obtain a propylene glycol phenyl ether product.
  • the present embodiment provides a method for synthesizing propylene glycol phenyl ether, which specifically comprises the following steps:
  • the propylene oxide feed valve is closed, and the temperature is maintained at 130 to 140 ° C for 2 hours. After the end of the reaction, the temperature was controlled to 110 to 120 ° C, and evacuation was carried out for 3 hours. The temperature is lowered to below 40 ° C to obtain a propylene glycol phenyl ether product.
  • the present embodiment provides a method for synthesizing propylene glycol phenyl ether, which specifically comprises the following steps:
  • a catalyst a combination of methyltriphenylphosphonium bromide and ethyltriphenylphosphonium bromide, the catalyst is added in an amount of 0.15% of the sum of the masses of phenol and propylene oxide, wherein The molar fraction of methyltriphenylphosphonium bromide was 1 part, and the molar fraction of ethyltriphenylphosphonium bromide was 99 parts.
  • the mixture was purged with nitrogen, and then the temperature was raised to 80 ° C.
  • the propylene oxide in the metering tank was started to be added to the reaction vessel to continue the temperature rise, and the reaction temperature was controlled at 100 to 110 ° C, and the reaction pressure was ⁇ 1.0 MPa.
  • the propylene oxide feed valve is closed, and the temperature is maintained at 120 to 130 ° C for 4 hours. After the completion of the reaction, the temperature was controlled to 100 to 110 ° C, and evacuation was carried out for 3 hours. The temperature is lowered to below 80 ° C to obtain a propylene glycol phenyl ether product.
  • the present embodiment provides a method for synthesizing propylene glycol phenyl ether, which specifically comprises the following steps:
  • a catalyst a composition of ethyltriphenylphosphonium bromide and propyltriphenylphosphonium bromide, the catalyst is added in an amount of 0.1% of the sum of the masses of phenol and propylene oxide, wherein The molar fraction of ethyltriphenylphosphonium bromide was 30, and the molar fraction of propyltriphenylphosphonium bromide was 70.
  • the temperature was raised to 80 ° C, and propylene oxide in the metering tank was started to be added to the reaction vessel to continue the temperature rise, and the reaction temperature was controlled at 150 to 160 ° C, and the reaction pressure was ⁇ 1.0 MPa.
  • the propylene oxide feed valve is closed, and the temperature is maintained at 100 to 120 ° C for 6 hours. After the end of the reaction, the temperature was controlled at 105 to 115 ° C, and evacuation was carried out for 3 hours. The temperature is lowered to below 80 ° C to obtain a propylene glycol phenyl ether product.
  • the present embodiment provides a method for synthesizing propylene glycol phenyl ether, which specifically comprises the following steps:
  • a catalyst a combination of methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, propyltriphenylphosphonium bromide, and butyltriphenylphosphonium bromide,
  • the amount of the catalyst added is 0.3% of the sum of the masses of phenol and propylene oxide, wherein the molar fraction of methyltriphenylphosphonium bromide is 1, and the molar fraction of ethyltriphenylphosphonium bromide is 25, propyl.
  • the molar fraction of triphenylphosphonium bromide was 25, and the molar fraction of butyltriphenylphosphonium bromide was 49.
  • the temperature was raised to 80 ° C, and propylene oxide in the metering tank was started to be added to the reaction vessel to continue the temperature rise, and the reaction temperature was controlled at 150 to 160 ° C, and the reaction pressure was ⁇ 1.0 MPa.
  • the propylene oxide feed valve is closed, and the temperature is maintained at 150 to 160 ° C for 4 hours. After the end of the reaction, the temperature was controlled to 120 to 130 ° C, and evacuation was carried out for 2 hours. The temperature is lowered to below 80 ° C to obtain a propylene glycol phenyl ether product.
  • Example 1 The content of metal ions in the propylene glycol phenyl ether prepared in Example 1 - Example 7 was determined by flame photometer analysis, and the results were examined using an AquaTint automatic colorimeter (purchased from Roewe, Germany) in Example 1 - Example 7. The color of the prepared product, the results are shown in Table 1:
  • the propylene glycol phenyl ether is catalyzed by a quaternary phosphonium salt catalyst, and the potassium and sodium ions in the product are all 0, no need to remove potassium, sodium or rectification, and propylene glycol phenyl ether can be directly applied to the concentration of metal ions. Strictly restricted industrial areas.
  • the synthesis method of the propylene glycol phenyl ether provided above simplifies the operation process of the whole synthesis process, reduces the synthesis cost of the propylene glycol phenyl ether, and the industrial application range of the synthesized propylene glycol phenyl ether is wide.

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Abstract

一种季膦盐类化合物作为催化剂制备丙二醇苯醚的催化剂的应用。还提供了一种丙二醇苯醚的合成方法，将苯酚和季膦盐类化合物混合，然后在无氧条件下加入环氧丙烷，所述苯酚与所述环氧丙烷发生聚合反应，生成所述丙二醇苯醚。制备的丙二醇苯醚杂质少且不含钾、钠等金属离子，不需要进行后续去除金属离子的操作和精馏分离，降低了成本，能够直接应用于高标准的工业化生产。

Description

一种制备丙二醇苯醚的催化剂及丙二醇苯醚的合成方法 技术领域
本发明属于化工技术领域，具体涉及一种制备丙二醇苯醚的催化剂及丙二醇苯醚的合成方法。
背景技术
丙二醇苯醚为无色透明液体，气味温和，具有无毒环保的特性。丙二醇苯醚是典型的高效成膜助剂，加入乳胶体系之后，能够在水相和聚合相中进行重新分配，它在两相中的分配系数极小，从而保证了优异的成膜效能、良好的增塑效应以及适宜的挥发速率平衡性。丙二醇苯醚对绝大多数乳胶均具有极强的溶解能力，水溶性小的特性，确保了它被乳胶微粒完全吸收，从而赋予了乳胶漆最好的展色均一性和聚结性能，同时具备优良的贮存稳定性。丙二醇苯醚还可以作为优良的高沸点有机溶剂和改性助剂，代替毒性或气味较大的异佛乐酮、环己酮、苯甲醇或乙二醇苯醚系列溶剂。因其无毒性、混溶性好、挥发速率适中，优异的聚结及偶合能力，较低的表面张力，而广泛用于汽车及汽车修补涂料，电泳涂料，工业烤漆和船舶，集装箱，木器涂料等领域。
目前丙二醇苯醚的生产一般采用两种合成工艺，一种是以氯丙醇与苯酚作为反应底物生产丙二醇苯醚，但以氯丙醇作为底物，易产生大量废物。丙二醇苯醚合成的第二种方法是用氢氧化钠、氢氧化钾等碱性催化剂的催化作用下，苯酚与环氧丙烷(PO)发生开环聚合反应生成丙二醇苯醚。该法是目前主要应用的一种工业生产方法，但采用上述催化剂催化合成产品， 产物丙二醇苯醚中还含有金属钾、钠离子等金属离子，无法直接应用于对金属离子严格限制的工业领域，后续需要对产物进行进一步的处理以去除金属离子，使得整个工艺的操作过程复杂、丙二醇苯醚的生产成本增加。
发明内容
本发明要解决的技术问题在于克服现有技术中的催化剂所催化合成的丙二醇苯醚中含有金属离子，不能直接应用于对金属离子严格限制的工业领域，后续的金属离子去除操作导致整个工艺的操作过程复杂、生产成本增加的问题。从而提供一种能够制备不含金属离子，不需要后续金属离子去除操作的制备丙二醇苯醚的催化剂。
为此，本发明第一方面提供了季膦盐类化合物作为制备丙二醇苯醚的催化剂的应用。
上述的季膦盐类化合物作为制备丙二醇苯醚的催化剂的应用，优选地，所述季膦盐类化合物选自甲基三苯基溴化膦、乙基三苯基溴化膦、丙基三苯基溴化膦或丁基三苯基溴化膦中的任一种化合物或几种的组合物。
上述的季膦盐类化合物作为制备丙二醇苯醚的催化剂的应用，优选地，所述组合物中任一组分的摩尔份数为1-99份。
本发明第二方面提供了一种丙二醇苯醚的合成方法，包括以下步骤：将苯酚和上述的季膦盐类化合物混合，然后在无氧条件下加入环氧丙烷，所述苯酚与所述环氧丙烷发生聚合反应，生成所述丙二醇苯醚。
上述的丙二醇苯醚的合成方法，优选地，所述苯酚与所述环氧丙烷的摩尔比为1:(1-1.15)。
上述的丙二醇苯醚的合成方法，优选地，所述季膦盐类化合物的加入量为所述苯酚与所述环氧丙烷质量和的0.05％-0.3％。
上述的丙二醇苯醚的合成方法，优选地，所述聚合反应的条件为：温度100～160℃，压力≤1.0MPa。
上述的丙二醇苯醚的合成方法，优选地，还包括：在所述加入环氧丙烷的步骤前，将温度升高至80℃，然后控制温度80～160℃，压力≤1.0MPa，加入所述环氧丙烷的步骤。
上述的丙二醇苯醚的合成方法，优选地，还包括：加入环氧丙烷后，控制温度100～160℃，熟化2～10小时，制得所述丙二醇苯醚；然后控制温度100～130℃，并在100～130℃下抽真空的步骤。
本发明相对现有技术具有如下优点：
1.本发明提供的季膦盐类化合物作为制备丙二醇苯醚的催化剂的应用，季膦盐类化合物作为催化剂具有高的催化效率，而且催化合成的丙二醇苯醚中不含有钾、钠等金属离子，提高了合成产品的质量与环境友好性。在应用季膦盐催化剂合成丙二醇苯醚后，不需要后续去除金属离子的操作，简化了生产工艺，降低了生产成本。季膦盐类化合物作为催化剂相对稳定性高，使催化合成的丙二醇苯醚的质量稳定，批次之间的重复性好，降低了对反应条件的要求和对设备强度的要求。
2.本发明提供的作为制备丙二醇苯醚催化剂的季膦盐类化合物为甲基三苯基溴化膦、乙基三苯基溴化膦、丙基三苯基溴化膦或丁基三苯基溴化膦中的任一种化合物或几种的组合物，上述的化合物作为制备丙二醇苯醚 的催化剂，同时具有热稳定性高、容易获得、无污染和不需要与产品进行分离等特点，能够降低丙二醇苯醚的合成成本以及催过合成过程对环境的影响，是一种经济、环境友好型催化剂。
3.本发明提供的丙二醇苯醚的合成方法，通过应用上述的季膦盐类化合物作为反应催化剂，合成的丙二醇苯醚中不含金属离子，不需要后续的金属离子去除操作，提高了产品质量，简化了整个合成工艺的操作流程，降低了丙二醇苯醚的生产成本。
4.本发明提供的丙二醇苯醚的合成方法，通过控制反应温度、压力、时间，以及苯酚和环氧丙烷的添加比例，在保证催化剂的催化活性和产品质量的前提下，降低了催化剂的添加量，利用上述方法生成的丙二醇苯醚中杂质少，不需要后续的精馏纯化步骤，能够直接适用于工业生产和应用。
5.本发明提供的丙二醇苯醚的合成方法，通过控制反应的温度和压力，保证催化剂的高的催化活性，反应结束后的抽真空步骤有效去除未完全反应的底物。
具体实施方式
以下通过具体实施例来说明本发明的实施方式，除非另外说明，本发明中所公开的实验方法均采用本技术领域常规技术，实施例中所用到的试剂和原料均可由市场购得。
实施例1
本实施例提供一种丙二醇苯醚的合成方法，具体包括以下步骤：
(1)在2升的高压反应釜中，加入苯酚10摩尔；向计量罐中加入环氧丙烷10摩尔。
(2)继续向反应釜中加入催化剂：甲基三苯基溴化膦，催化剂的加量为苯酚与环氧丙烷质量之和的0.05％。封釜后进行氮气置换，然后升温到80℃，开始将计量罐中的环氧丙烷加入反应釜中，继续升温，控制反应温度100～110℃，反应压力≤1.0MPa。
(3)加完环氧丙烷后，关闭环氧丙烷进料阀，在100～110℃下继续维持恒温8小时。反应结束后控制温度为100～110℃，抽真空1小时。降温到80℃以下，即得丙二醇苯醚产品。
实施例2
本实施例提供一种丙二醇苯醚的合成方法，具体包括以下步骤：
(1)在2升的高压反应釜中，加入苯酚10摩尔；向计量罐中加入环氧丙烷10.3摩尔。
(2)继续向反应釜中加入催化剂：乙基三苯基溴化膦，催化剂的加量为苯酚与环氧丙烷质量之和的0.2％。封釜后进行氮气置换，然后升温到80℃，开始将计量罐中的环氧丙烷加入反应釜中，继续升温，控制反应温度100～110℃，反应压力≤1.0MPa。
(3)加完环氧丙烷后，关闭环氧丙烷进料阀，在130～140℃下继续维持恒温4小时。反应结束后控制温度为110～120℃，抽真空2.5小时。降温到80℃，即得丙二醇苯醚产品。
实施例3
本实施例提供一种丙二醇苯醚的合成方法，具体包括以下步骤：
(1)在2升的高压反应釜中，加入苯酚10摩尔；向计量罐中加入环氧丙烷10.5摩尔。
(2)继续向反应釜中加入催化剂：丙基三苯基溴化膦，催化剂的加量为苯酚与环氧丙烷质量之和的0.3％。封釜后进行氮气置换，然后升温到80℃，开始将计量罐中的环氧丙烷加入反应釜中，继续升温，控制反应温度150～160℃，反应压力≤1.0MPa。
(3)加完环氧丙烷后，关闭环氧丙烷进料阀，在150～160℃下继续维持恒温4小时。反应结束后控制温度为120～130℃，抽真空2小时。降温到80℃以下，即得丙二醇苯醚产品。
实施例4
本实施例提供一种丙二醇苯醚的合成方法，具体包括以下步骤：
(1)在2升的高压反应釜中，加入苯酚10摩尔；向计量罐中加入环氧丙烷11摩尔。
(2)继续向反应釜中加入催化剂：丁基三苯基溴化膦，催化剂的加量为苯酚与环氧丙烷质量之和的0.3％。封釜后进行氮气置换，然后升温到80℃，开始将计量罐中的环氧丙烷加入反应釜中，继续升温，控制反应温度120～130℃，反应压力≤1.0MPa。
(3)加完环氧丙烷后，关闭环氧丙烷进料阀，在130～140℃下继续维持恒温2小时。反应结束后控制温度为110～120℃，抽真空3小时。降温到40℃以下，即得丙二醇苯醚产品。
实施例5
本实施例提供一种丙二醇苯醚的合成方法，具体包括以下步骤：
(1)在2升的高压反应釜中，加入苯酚10摩尔；向计量罐中加入环氧丙烷11.5摩尔。
(2)继续向反应釜中加入催化剂：甲基三苯基溴化膦和乙基三苯基溴化膦的组合物，催化剂的加量为苯酚与环氧丙烷质量之和的0.15％，其中甲基三苯基溴化膦的摩尔份数为1份，乙基三苯基溴化膦的摩尔份数为99份。封釜后进行氮气置换，然后升温到80℃，开始将计量罐中的环氧丙烷加入反应釜中，继续升温，控制反应温度100～110℃，反应压力≤1.0MPa。
(3)加完环氧丙烷后，关闭环氧丙烷进料阀，在120～130℃下继续维持恒温4小时。反应结束后控制温度为100～110℃，抽真空3小时。降温到80℃以下，即得丙二醇苯醚产品。
实施例6
本实施例提供一种丙二醇苯醚的合成方法，具体包括以下步骤：
(1)在2升的高压反应釜中，加入苯酚10摩尔；向计量罐中加入环氧丙烷11.3摩尔。
(2)继续向反应釜中加入催化剂：乙基三苯基溴化膦和丙基三苯基溴化膦的组合物，催化剂的加量为苯酚与环氧丙烷质量之和的0.1％，其中乙基三苯基溴化膦的摩尔份数为30，丙基三苯基溴化膦的摩尔份数为70。封釜后进行氮气置换，然后升温到80℃，开始将计量罐中的环氧丙烷加入反应釜中，继续升温，控制反应温度150～160℃，反应压力≤1.0MPa。
(3)加完环氧丙烷后，关闭环氧丙烷进料阀，在100～120℃下继续维持恒温6小时。反应结束后控制温度为105～115℃，抽真空3小时。降温到80℃以下，即得丙二醇苯醚产品。
实施例7
本实施例提供一种丙二醇苯醚的合成方法，具体包括以下步骤：
(1)在2升的高压反应釜中，加入苯酚10摩尔；向计量罐中加入环氧丙烷10.1摩尔。
(2)继续向反应釜中加入催化剂：甲基三苯基溴化膦、乙基三苯基溴化膦、丙基三苯基溴化膦和丁基三苯基溴化膦的组合物，催化剂的加量为苯酚与环氧丙烷质量之和的0.3％，其中甲基三苯基溴化膦的摩尔份数为1，乙基三苯基溴化膦的摩尔份数为25，丙基三苯基溴化膦的摩尔份数为25，丁基三苯基溴化膦的摩尔份数为49。封釜后进行氮气置换，然后升温到80℃，开始将计量罐中的环氧丙烷加入反应釜中，继续升温，控制反应温度150～160℃，反应压力≤1.0MPa。
(3)加完环氧丙烷后，关闭环氧丙烷进料阀，在150～160℃下继续维持恒温4小时。反应结束后控制温度为120～130℃，抽真空2小时。降温到80℃以下，即得丙二醇苯醚产品。
检测例1
利用火焰光度计分析测定实施例1-实施例7中所制备的丙二醇苯醚中金属离子的含量，利用AquaTint全自动色度仪(购于德国罗威邦)检测实施例1-实施例7中所制备产物的色度，结果如表1所示：
表1 实施例1-实施例7所述的合成方法制备的丙二醇苯醚检测结果
Figure PCTCN2018101121-appb-000001
Figure PCTCN2018101121-appb-000002
由表1可知，利用季膦盐催化剂催化合成丙二醇苯醚，产品中钾、钠离子均为0，不需进行去除钾、钠处理或精馏分离，丙二醇苯醚能够直接应用于对金属离子浓度严格限制的工业领域。同时上述提供的丙二醇苯醚的合成方法简化了整个合成工艺的操作过程，降低了丙二醇苯醚的合成成本，合成的丙二醇苯醚的工业适用范围广。
显然，上述实施例仅仅是为清楚地说明所作的举例，而并非对实施方式的限定。对于所属领域的普通技术人员来说，在上述说明的基础上还可以做出其它不同形式的变化或变动。这里无需也无法对所有的实施方式予以穷举。而由此所引伸出的显而易见的变化或变动仍处于本发明创造的保护范围之中。

Claims (9)

  1. 季膦盐类化合物作为制备丙二醇苯醚的催化剂的应用。
  2. 根据权利要求1所述的季膦盐类化合物作为制备丙二醇苯醚的催化剂的应用，其特征在于，所述季膦盐类化合物选自甲基三苯基溴化膦、乙基三苯基溴化膦、丙基三苯基溴化膦或丁基三苯基溴化膦中的任一种化合物或几种的组合物。
  3. 根据权利要求2所述的季膦盐类化合物作为制备丙二醇苯醚的催化剂的应用，其特征在于，所述组合物中任一组分的摩尔份数为1-99份。
  4. 一种丙二醇苯醚的合成方法，其特征在于，包括以下步骤：将苯酚和权利要求1-3任一项所述的季膦盐类化合物混合，然后在无氧条件下加入环氧丙烷，所述苯酚与所述环氧丙烷发生聚合反应，生成所述丙二醇苯醚。
  5. 根据权利要求4所述的丙二醇苯醚的合成方法，其特征在于，所述苯酚与所述环氧丙烷的摩尔比为1:(1-1.15)。
  6. 根据权利要求4或5所述的丙二醇苯醚的合成方法，其特征在于，所述季膦盐类化合物的加入量为所述苯酚与所述环氧丙烷质量和的0.05％-0.3％。
  7. 根据权利要求4-6任一项所述的丙二醇苯醚的合成方法，其特征在于，所述聚合反应的条件为：温度100～160℃，压力≤1.0MPa。
  8. 根据权利要求7所述的丙二醇苯醚的合成方法，其特征在于，还包括：在所述加入环氧丙烷的步骤前，将温度升高至80℃，然后控制温度80～160℃，压力≤1.0MPa，加入所述环氧丙烷的步骤。
  9. 根据权利要求8所述的丙二醇苯醚的合成方法，其特征在于，还包括：加入环氧丙烷后，控制温度100～160℃，熟化2～10小时，制得所述丙二醇苯醚；然后控制温度100～130℃，并在100～130℃下抽真空的步骤。
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