WO2021114619A1 - 一种炔二醇嵌段聚醚及其合成方法 - Google Patents

一种炔二醇嵌段聚醚及其合成方法 Download PDF

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WO2021114619A1
WO2021114619A1 PCT/CN2020/099059 CN2020099059W WO2021114619A1 WO 2021114619 A1 WO2021114619 A1 WO 2021114619A1 CN 2020099059 W CN2020099059 W CN 2020099059W WO 2021114619 A1 WO2021114619 A1 WO 2021114619A1
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acetylene glycol
synthesizing
catalyst
glycol block
block copolymer
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French (fr)
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殷其文
郏超伟
糜泽峰
高洪军
裘碧菡
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浙江皇马新材料科技有限公司
浙江皇马科技股份有限公司
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Priority to KR1020227023420A priority Critical patent/KR20220114004A/ko
Publication of WO2021114619A1 publication Critical patent/WO2021114619A1/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
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/002—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds
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    • 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
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
    • C08G65/2606—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups
    • C08G65/2609—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups containing aliphatic hydroxyl groups
    • 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
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • C08G65/2642—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds characterised by the catalyst used
    • C08G65/269—Mixed catalyst systems, i.e. containing more than one reactive component or catalysts formed in-situ
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    • 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
    • C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G2650/22—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the initiator used in polymerisation
    • C08G2650/24—Polymeric initiators
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G2650/28—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type
    • C08G2650/58—Ethylene oxide or propylene oxide copolymers, e.g. pluronics
    • 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
    • C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G2650/28—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type
    • C08G2650/60—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type containing acetylenic group
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G2650/62—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the nature of monomer used
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids

Definitions

  • the present invention relates to a block polyether and its synthesis method. More specifically, it relates to a kind of acetylene glycol as an initiator and ethylene oxide and/or propylene oxide to react and synthesize under the action of a composite catalyst. Block polyether method.
  • the acetylene glycol gemini surfactant has two hydrophilic groups, the triple bond is located in the center of the hydrocarbon chain, and the ethoxy and hydroxyl groups are symmetrically distributed on both sides of the triple bond.
  • This special molecular structure makes it have Good ability to reduce surface tension, defoaming and anti-foaming capabilities, etc., are widely used in water-based coatings, printing inks, adhesives, building materials and other fields.
  • Patent CN102304029A discloses an ethoxylated 2,4,7,9-tetramethyl-tetramethyl group by reacting with a base such as sodium hydroxide, trimethylamine or triethylamine as a catalyst in a solvent such as ether, benzene or toluene. 5-decyne-4,7-diol method. In this method, the reaction is carried out in a solvent, which is easy to volatilize or easy to produce pollution, the process is complicated, and the cost is relatively high.
  • Patent CN108517031A discloses the use of 2,4,7,9-tetramethyl-5-decyne-4,7-diol as the initiator and the acidic ionic liquid 1-butyl-3-methylimidazole dihydrogen phosphate Salt, 1-butyl-3-methylimidazole hydrogensulfate or 1-butyl-3-methylimidazole trifluoromethanesulfonate as solvent and acid catalyst, and organic bases such as trimethylamine, triethylamine, etc.
  • the basic catalyst is used for polymerization reaction. After the reaction, anhydrous ether, tetrahydrofuran, methyl ethyl ether, etc. are used as the extractant to separate the ethoxylated 2,4,7,9-tetramethyl-5-decyne-4 ,7-diol.
  • the method has complicated process and high cost, and it is difficult to realize industrialized production.
  • acetylene glycol multifunctional surfactants synthesized in the prior art are based on triethylamine as a catalyst.
  • the synthesized product has high color, and requires post-treatment, or needs to be reacted and extracted in a solvent. The process is complicated and the cost is relatively high. High, easy to cause pollution; and most of them are polymerized with ethylene oxide, the penetration performance and defoaming performance of the product are still lagging behind that of silicone or fluorine surfactants; both color and performance problems are limited
  • the present invention provides an acetylene glycol block polyether.
  • the specific scheme is as follows:
  • the molecular formula of the acetylene glycol block polyether is:
  • R 1 and R 4 are independently selected from C 3 to C 10 alkyl groups
  • R 2 and R 3 are methyl or ethyl
  • m ranges from 0 to 6
  • n ranges from 3 to 15.
  • a method for synthesizing acetylene glycol block polyether including the following steps:
  • the temperature is controlled and degassed, and the temperature is lowered to neutralize (the acid selected for neutralization is at least one of phosphoric acid, hydrochloric acid, citric acid and acetic acid, preferably acetic acid) to obtain the product.
  • the acid selected for neutralization is at least one of phosphoric acid, hydrochloric acid, citric acid and acetic acid, preferably acetic acid
  • the composite catalyst is a mixture of a metal alkyl catalyst and an organic base catalyst.
  • the acetylene glycol initiator in the step (1) is selected from 4,7-dimethyl-5-decyne-4,7-diol, 2,4,7,9-tetramethyl-5- Decyne, 2,5,8,11-tetramethyl-6-dodecyne-5,8-diol, 2,3,5,8,10,11-hexamethyl-6-dodecyne- One or more of 5,8diol or 7,10-diol.
  • the alkyl metal catalyst is a mixture of one or more of nBuLi, CaEt 2 , AlEt 3 and ZnEt 3
  • the organic base catalyst is one of dimethylamine, trimethylamine, triethylamine and N-toluidine One or more mixtures.
  • the composite catalyst is a mixture of AlEt 3 and triethylamine in a weight ratio of 1:1 to 8; the dosage of the composite catalyst is 0.01% to 2% of the amount of the acetylene glycol initiator substance,
  • the composite catalyst is a mixture of AlEt 3 and triethylamine in a weight ratio of 1:1 to 6; the amount of the composite catalyst is 0.05% to 1% of the amount of the acetylene glycol initiator substance.
  • the reaction temperature in the step (a) is 60-150°C, preferably the reaction temperature is 60-130°C.
  • the reaction temperature in the step (b) is 50-120°C, preferably 55-110°C.
  • the degassing temperature in the step (c) is 60-120°C, preferably 100°C-110°C, and the degassing time is 1 hour.
  • the idea of the synthesis method of the acetylene glycol block polyether of the present invention is: under the action of a composite catalyst, the reaction temperature and pressure are controlled, and the acetylene glycol is successively polymerized with propylene oxide and ethylene oxide to obtain the acetylene glycol block. Segment polyether.
  • the composite catalyst includes a mixture selected from alkyl metal catalysts and organic base catalysts.
  • acetylene glycol surfactant mainly uses its properties of low foam, foam suppression and high surface activity.
  • the gap between the system foam liquid membrane is increased, the discharge rate is accelerated, and the foaming property is reduced.
  • the branched PO chain enhances its permeability and makes its application performance more excellent; the acetylenic glycol surfactant has a deep color
  • Most of the problems are caused by the triethylamine catalyst.
  • the metal alkyl catalyst itself has very low activity, but it can form a stable when mixed with the organic base catalyst.
  • the complex compound, the catalytic activity is improved, and the amount of the catalyst is reduced, so that the synthesized acetylene glycol surfactant has a lighter color, which solves the problem of the darker color in the traditional synthesis process of the acetylene glycol surfactant and the need for post-treatment.
  • the pressure in the present invention all refer to gauge pressure; the usage ratio in the present invention all refer to the molar ratio; the measurement method of chromaticity in the specific implementation of the present invention adopts GB/T605-2006; the test method of the hydroxyl value of the product in the specific implementation of the invention adopts GB/T7383-2007 (Determination of Hydroxyl Value of Nonionic Surfactant); The surface tension and dynamic surface tension of the product in the specific implementation of the present invention adopt the bubble pressure method.
  • the acetylene glycol block polyether designed and synthesized by the present invention has a low color base and no need for post-treatment, so the production process is simple and the production cost is low; secondly, the defoaming performance and static and dynamic surface tension of the product More prominent, wider application performance.
  • Example 1 The other settings are the same as those of Example 1.
  • the difference lies in the type of catalyst, the ratio and the amount of addition, the ratio of PO/EO, the sequence of reactions, and the reaction temperature in the corresponding period.
  • the specific relevant parameters are shown in Table 1.
  • Table 1 Process parameter setting table of Examples 1-10
  • Table 2 Index test table of Examples 1-10
  • Comparative Examples 1 to 5 have the same settings as Example 1, except that the types of catalysts are different.
  • the specific test indicators are shown in Table 3.

Abstract

本发明涉及一种炔二醇嵌段聚醚及其合成方法，本发明在复合催化剂的作用下，控制反应温度和压力，炔二醇依次与环氧丙烷，环氧乙烷进行聚合反应，得到炔二醇嵌段聚醚。所述的复合催化剂包括选自烷基金属催化剂和有机碱催化剂所组成的混合物。本发明设计合成的炔二醇嵌段聚醚色泽底，且无需后处理，所以生产工艺简单，生产成本低；其次，产品的消泡性能和静态、动态表面张力更突出，应用性能更广。

Description

一种炔二醇嵌段聚醚及其合成方法 技术领域
本发明涉及一种嵌段聚醚及其的合成方法，更具体的讲，是涉及一种炔二醇为起始剂与环氧乙烷和/或环氧丙烷在复合催化剂的作用下反应合成嵌段聚醚的方法。
背景技术
炔二醇双子表面活性剂因其具有两个亲水基团，三键位于碳氢链的中央，在三键的两侧对称的分布乙氧基和羟基，这种特殊的分子结构使其具有良好的降低表面张力的能力、消泡和抑泡的能力等，广泛应用于水性涂料、印刷油墨、粘合剂、建筑材料等领域。
专利CN102304029A公开了一种以氢氧化钠、三甲胺或三乙胺等碱为催化剂，在乙醚、苯或甲苯等溶剂中进行反应合成乙氧基化2,4,7,9-四甲基-5-癸炔-4,7-二醇的方法。本方法在溶剂进行反应，溶剂易挥发或易产生污染，工艺繁琐，成本较高。
专利CN108517031A公开了以2,4,7,9-四甲基-5-癸炔-4,7-二醇为起始剂，以酸性离子液体1-丁基-3-甲基咪唑磷酸二氢盐、1-丁基-3-甲基咪唑硫酸氢盐或1-丁基-3-甲基咪唑三氟甲烷磺酸盐为溶剂和酸性催化剂，并以有机碱三甲胺、三乙胺等为碱性催化剂进行聚合反应，反应后以醚无水乙醚、四氢呋喃、甲基乙基醚等为萃取剂分离得到乙氧基化2,4,7,9-四甲基-5-癸炔-4,7-二醇。该方法工艺繁琐，成本较高，难以实现工业化生产。
现有技术合成的炔二醇类多功能表面活性剂多是以三乙胺为催化剂，合成的产品色度较高，需后处理，或需在溶剂中进行反应、萃取，工艺繁琐，成本较高，易产生污染；且多是用环氧乙烷进行聚合，产品的渗透性能以及 消泡性能与硅酮类或氟类表面活性剂相比还有差距；无论是色泽问题还是性能问题都限制了炔二醇类多功能表面活性剂的应用范围，尤其是在一些要求较高的领域。
发明内容：
为克服现有技术的不足，本发明提供了一种炔二醇嵌段聚醚，具体方案如下：
所述的炔二醇嵌段聚醚分子式为：
Figure PCTCN2020099059-appb-000001
其中，R 1、R 4独自选自C 3～C 10的烷基，R 2和R 3为甲基或乙基，m取值范围为0～6，n的取值范围为3～15。
一种炔二醇嵌段聚醚的合成方法，包括如下步骤：
a)向反应釜中依次加入复合催化剂和预热好的炔二醇起始剂，排氮3～4次，110℃脱水1小时；控制反应温度，缓慢滴加环氧丙烷进行聚醚反应，熟化后，调节温度进行脱气，除掉未反应的环氧丙烷；
b)控制反应温度，滴加环氧乙烷，进行聚醚反应，并熟化；
c)反应结束后控温脱气，降温中和(中和选用的酸为磷酸、盐酸、柠檬酸和醋酸中的至少一种，优选醋酸)得到产品。
所述的复合催化剂为烷基金属催化剂和有机碱催化剂的混合物。
所述步骤(1)中的炔二醇起始剂选自4,7-二甲基-5-癸炔-4,7-二醇、2,4,7,9-四甲基-5-癸炔、2,5,8,11-四甲基-6-十二炔-5,8-二醇、2,3,5,8,10,11-六甲基-6-十二炔-5,8二醇或7,10-二醇中一种或多种。
所述炔二醇起始剂:PO:EO＝1:0～8:1～20。
所述炔二醇起始剂:PO:EO＝1:0～6:3～15.
所述烷基金属催化剂为nBuLi、CaEt 2、AlEt 3和ZnEt 3中的一种或多种的混合物，所述有机碱催化剂为二甲胺、三甲胺、三乙胺和N-甲苯胺中的一种或多种的混合物。
所述复合催化剂为AlEt 3和三乙胺按重量比1:1～8的混合物；复合催化剂用量为炔二醇起始剂物质的量的0.01％～2％，
所述复合催化剂为AlEt 3和三乙胺按重量比1:1～6的混合物；复合催化剂用量为炔二醇起始剂物质的量的0.05％～1％。
所述步骤(a)的反应温度为60～150℃，优选反应温度为60～130℃。
所述步骤(b)的反应温度为50～120℃，优选55～110℃。
所述步骤(c)的脱气温度为60～120℃，优选100℃～110℃，脱气时间为1小时。
本发明炔二醇嵌段聚醚的合成方法思路为：在复合催化剂的作用下，控制反应温度和压力，炔二醇依次与环氧丙烷，环氧乙烷进行聚合反应，得到炔二醇嵌段聚醚。所述的复合催化剂包括选自烷基金属催化剂和有机碱催化剂所组成的混合物。
炔二醇表面活性剂的应用主要运用了其低泡、抑泡和高表面活性的性质，我们根据表面活性剂性质与结构的关系，设计了一种嵌段共聚物，PO嵌段的引入，使体系泡沫液膜间的空隙增大，排液速率加快，起泡性降低，同时带 支链的PO链增强了其渗透性，使其应用性能更加优异；炔二醇表面活性剂色泽深的问题多是因为三乙胺催化剂引起的，我们将适量的烷基金属催化剂与有机碱催化剂进行复配作为复合催化剂，烷基金属催化剂本身活性很低，但与有机碱催化剂混合后可形成稳定的络合物，催化活性提高，催化剂的用量减少，从而合成的炔二醇表面活性剂颜色较浅，解决了炔二醇表面活性剂传统合成工艺中颜色较深需要后处理的问题。
本发明中的压力均指表压；本发明中使用量比例均指摩尔比；本发明具体实施中色度的测量方法采用GB/T605-2006；本发明具体实施中产品的羟值测试方法采用GB/T7383-2007(非离子表面活性剂羟值的测定)；本发明具体实施中产品的表面张力和动态表面张力采用泡压法。
与现有的技术相比，本发明设计合成的炔二醇嵌段聚醚色泽底，且无需后处理，所以生产工艺简单，生产成本低；其次，产品的消泡性能和静态、动态表面张力更突出，应用性能更广。
具体实施方式
实施例1
在2.5L压力反应釜中加入1mol(226g)2,4,7,9-四甲基-5-癸炔-4,7-二醇和0.113g的AlEt 3与二甲胺(1:3)组成的复合催化剂；开启搅拌，用氮气置换釜内气体3次，升温至110℃左右，真空脱水1小时；将温度控制在100℃～105℃之间，缓缓滴加9mol环氧乙烷，将压力控制在0.35Mpa以下，熟化0.5小时左右，直至反应压力基本不变；然后将反应温度控制在65℃～70℃之间，缓慢滴加1mol环氧丙烷，将压力控制在0.35Mpa以下，并熟化3小时左右，直至反应压力基本不变；反应结束后，将温度控制在100℃左右， 真空脱气1小时，除去未反应的环氧乙烷和环氧丙烷或部分催化剂；将温度降到65℃，用醋酸中和，冷却得到炔二醇嵌段聚醚产品，取样进行性能测试。
实施例2～10
其它与实施例1的设置相同，区别在于催化剂的种类、配比和添加量，PO/EO的配比、反应的先后顺序以及相应时段的反应温度，具体相关参数如表1所示。
表1：实施例1～10的工艺参数设置表
Figure PCTCN2020099059-appb-000002
为了进一步说明效果，对实施例1～10的静态表面张力、动态表面张力、色泽和羟值进行检测，为便于比较，将其列于表2。
表2：实施例1～10的指标测试表
Figure PCTCN2020099059-appb-000003
Figure PCTCN2020099059-appb-000004
对比例1～5
对比例1～5与实施例1设置相同，只是催化剂的种类不同，具体测试指标如表3所示。
表3：对比例1～5的指标测试表
Figure PCTCN2020099059-appb-000005
本说明书中公开的所有特征，或公开的所有方法或过程中的步骤，除了互相排斥的特征和/或步骤以外，均可以以任何方式组合。

Claims (10)

  1. 一种炔二醇嵌段聚醚，其特征在于，所述的炔二醇嵌段聚醚分子式为：
    Figure PCTCN2020099059-appb-100001
    其中，R 1、R 4独自选自C 3～C 10的烷基，R 2和R 3为甲基或乙基，m取值范围为0～6，n的取值范围为3～15。
  2. 一种如权利要求所述的炔二醇嵌段聚醚的合成方法，其特征在于，包括如下步骤：
    a)向反应釜中依次加入复合催化剂和预热好的炔二醇起始剂，排氮，脱水；控制反应温度，缓慢滴加环氧丙烷进行聚醚反应，熟化后，调节温度进行脱气，除掉未反应的环氧丙烷；
    b)控制反应温度，滴加环氧乙烷，进行聚醚反应，并熟化；
    c)反应结束后升温脱气，降温中和得到产品；
    所述的复合催化剂为烷基金属催化剂和有机碱催化剂的混合物。
  3. 如权利要求2所述的一种炔二醇嵌段共聚物的合成方法，其特征在于：所述步骤(1)中的炔二醇起始剂选自4,7-二甲基-5-癸炔-4,7-二醇、2,4,7,9-四甲基-5-癸炔、2,5,8,11-四甲基-6-十二炔-5,8-二醇、2,3,5,8,10,11-六甲基-6-十二炔-5,8二醇或7,10-二醇中一种或多种。
  4. 如权利要求2所述的一种炔二醇嵌段共聚物的合成方法，其特征在于：所述炔二醇起始剂:PO:EO＝1:0～8:1～20。
  5. 如权利要求2所述的一种炔二醇嵌段共聚物的合成方法，其特征在于：所述炔二醇起始剂:PO:EO＝1:0～6:3～15.
  6. 如权利要求2所述的一种炔二醇嵌段共聚物的合成方法，其特征在于：所述烷基金属催化剂为nBuLi、CaEt 2、AlEt 3和ZnEt 3中的一种或多种的混合物，所述有机碱催化剂为二甲胺、三甲胺、三乙胺和N-甲苯胺中的一种或多种的混合物。
  7. 如权利要求2所述的一种炔二醇嵌段共聚物的合成方法，其特征在于：所述复合催化剂为AlEt 3和三乙胺按重量比1:1～8的混合物；复合催化剂用量为炔二醇起始剂物质的量的0.01％～2％。
  8. 如权利要求2所述的一种炔二醇嵌段共聚物的合成方法，其特征在于：所述复合催化剂为AlEt 3和三乙胺按重量比1:1～6的混合物；所述复合催化剂用量为炔二醇起始剂物质的量的0.05％～1％。
  9. 如权利要求2所述的一种炔二醇嵌段共聚物的合成方法，其特征在于：所述步骤(a)的反应温度为60～150℃，所述步骤(b)的反应温度为50～120℃。
  10. 如权利要求2所述的一种炔二醇嵌段共聚物的合成方法，其特征在于：所述步骤(a)的反应温度为60～130℃，所述步骤(b)的反应温度为55～110℃。
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