WO2023184786A1 - 一种模板剂及其制备方法和应用 - Google Patents

一种模板剂及其制备方法和应用 Download PDF

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WO2023184786A1
WO2023184786A1 PCT/CN2022/105557 CN2022105557W WO2023184786A1 WO 2023184786 A1 WO2023184786 A1 WO 2023184786A1 CN 2022105557 W CN2022105557 W CN 2022105557W WO 2023184786 A1 WO2023184786 A1 WO 2023184786A1
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template agent
diene
vinyl
intermediate product
cysteamine
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PCT/CN2022/105557
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English (en)
French (fr)
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何新耀
李玉博
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佳化化学科技发展（上海）有限公司
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Publication of WO2023184786A1 publication Critical patent/WO2023184786A1/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
    • C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
    • C08G83/002—Dendritic macromolecules
    • C08G83/003—Dendrimers
    • C08G83/004—After treatment of dendrimers
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C04B24/24—Macromolecular compounds
    • C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B24/2605—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing polyether side chains
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
    • C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
    • 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
    • C08G65/2603—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
    • C08G65/2696—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 process or apparatus used
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
    • C04B2103/30—Water reducers, plasticisers, air-entrainers, flow improvers
    • C04B2103/302—Water reducers

Definitions

  • This application belongs to the technical field of polymer material preparation, and specifically relates to a template agent and its preparation method and application.
  • Polycarboxylate water-reducing admixture is the latest generation of concrete admixtures and is called the third generation of high-performance water-reducing admixtures. Compared with the previous generation of naphthalene-based water-reducing agents, polycarboxylate water-reducing agents have the characteristics of higher water-reducing rate and better adaptability to cement. At the same time, there is no process wastewater in the production process of polycarboxylate water-reducing agents. and waste, it is a green and environmentally friendly material.
  • Polyether macromonomer is the most important raw material in the synthesis of water-reducing agents, accounting for 90% of the ingredients in the water-reducing agent. Its performance directly determines the performance of the polycarboxylate water-reducing agent.
  • the most important indicators in the water-reducing agent polyether macromonomer are the double bond retention rate, molecular weight distribution, and particle size. At present, most polyether manufacturers can make the double bond retention rate of polyether macromonomers greater than 90% by controlling the process and catalysts. However, there is no good method to control the monomer retention rate in the process of preparing polyether macromonomers. Particle size and particle size distribution. How to control the particle size and molecular weight distribution of polyether macromonomers to improve the performance of polycarboxylate superplasticizer products has become one of the key areas of concern in the admixture industry.
  • the technical problem to be solved by this application is to overcome the defects in the prior art that the particle size and distribution of the polycarboxylate water-reducing agent are difficult to control, thereby providing a template agent and its preparation method and application.
  • This application provides a template agent whose raw materials include polyamine, diene and hydrogen halide;
  • the diene is a symmetrical monomer.
  • the template agent has the following structural formula:
  • the terminal group of the diene is a double bond
  • the terminal group of the polyamine is an amino group; further, the two terminal groups of the polyamine are amino groups;
  • the molar amount of the diene is at least 60 times the molar amount of the polyamine.
  • the template agent also satisfies at least one of (1)-(3),
  • the diene is at least one of 1,3-butadiene, epoxy acrylate and 1,3-divinylcyclobutane;
  • the polyamine is at least one of triethylenetetramine, ethylenediamine and 1,4-butanediamine;
  • the template agent also satisfies at least one of (1)-(2),
  • the raw materials of the template agent also include hydroxyl-containing compounds
  • the hydroxyl-containing compound is sodium hydroxide and/or potassium hydroxide
  • the hydrogen halide is at least one of hydrogen bromide, hydrogen chloride and hydrogen iodide.
  • the raw materials of the template agent also include cysteamine and/or organic solvents
  • the molar ratio of the cysteamine to the polyamine is 1: (25-37).
  • the organic solvent may be, but is not limited to, at least one of dimethyl sulfoxide, acetone, tetrahydrofuran, and N,N-dimethylformamide.
  • the raw materials of the template include triethylenetetramine, 1,3-butadiene and cysteamine, wherein the molar ratio of cysteamine and triethylenetetramine is 1: (34-36), triethylenetetramine The molar ratio to 1,3-butadiene is 1: (74-76).
  • This application also provides a method for preparing a template agent, which includes the following steps:
  • step (3) after adding hydrogen halide to complete the addition reaction, a step of adding a hydroxyl-containing compound to perform a substitution reaction is also included.
  • adding the diene also includes the step of adding cysteamine
  • step (2) include adding diene and cysteamine alternately to the first intermediate product at least twice, and obtaining the second intermediate product after double bond addition and amino addition. ;
  • the molar amount of diene added for the first time in step (2) is 1.9-2.1 times that of diene in step (1); the molar amount of diene added for the second time in step (2) is 1.9-2.1 times that of diene added in step (2). 1.9-2.1 times the amount of diene added for the first time.
  • the preparation method of the template agent provided in this application specifically includes the following steps:
  • the specific steps of alternately adding diene and cysteamine to the first intermediate product are: add diene to the first intermediate product at room temperature, stir for 8-12h, and then place it at 60-80°C for reaction for 15 -30h, carry out double bond addition reaction, then add cysteamine, stir for 20-60min, carry out amino addition reaction, then add diene and cysteamine in sequence and repeat the above steps to obtain the second intermediate product.
  • the amount of diene added in step (3) is (1.9-2.1) times the amount of diene added last time in step (2).
  • this application provides a vinyl-terminated polyoxypropylene polyoxyethylene ether macromonomer, the raw materials include the above template agent or the template agent prepared by the above method;
  • the vinyl-terminated polyoxypropylene polyoxyethylene ether macromonomer has the following structural formula:
  • R 1 is hydrogen or methyl
  • R 2 is C1-C4 alkylene
  • R 3 is hydrogen, methyl or ethyl
  • m is any number between 0-6, n is any number between 10-150 number.
  • this application also provides a method for preparing vinyl-terminated polyoxypropylene polyoxyethylene ether macromonomer, including the following steps:
  • Terminal vinyl ether, template agent and catalyst are mixed, and after initiation, propylene oxide and ethylene oxide are added in sequence, and the vinyl-terminated polyoxypropylene polyoxyethylene ether macromonomer is obtained after polymerization reaction.
  • the mass ratio of the terminal vinyl ether and template agent is 1: (0.001-0.02);
  • the terminal vinyl ether is at least one of 4-hydroxybutyl vinyl ether, diethylene glycol monovinyl ether and 2-hydroxyethyl vinyl ether;
  • the temperature of the polymerization reaction is 90-120°C;
  • the amount of catalyst used is 0.1-0.3% of the total mass of raw materials.
  • the total mass of raw materials refers to the total mass of terminal vinyl ether, template agent, propylene oxide and ethylene oxide.
  • the preparation method of the above-mentioned vinyl-terminated polyoxypropylene polyoxyethylene ether macromonomer specifically includes the following steps:
  • the molar ratio of terminal vinyl ether and propylene oxide added in step (1) is 1:(0-6).
  • the mass ratio of propylene oxide and ethylene oxide is (0-336): (440-6600).
  • the catalyst is a Lewis acid catalyst, such as boron trifluoride ether, aluminum trichloride, ferric chloride, and boron trifluoride ether is preferred.
  • the amount of catalyst used is 0.1-0.3% of the total mass of raw materials, and the raw materials include terminal vinyl ether, template agent, propylene oxide and ethylene oxide.
  • the pH adjuster is an acid solution, and the acid solution is at least one of phosphoric acid, acetic acid, benzoic acid and citric acid.
  • this application provides a water-reducing agent whose raw materials include the above-mentioned vinyl-terminated polyoxypropylene polyoxyethylene ether macromonomer or the vinyl-terminated polyoxypropylene polyoxyethylene ether macromonomer prepared by the above-mentioned preparation method. body.
  • the template agent provided by this application.
  • the raw materials of the template agent include polyamines, dienes and hydrogen halides.
  • the dienes are symmetrical monomers.
  • the template agent is a nano-narrow band dendritic macromolecule template agent with high specific surface area and molecular weight distribution. Narrow, the raw materials of this template include dienes, and dienes are symmetrical monomers that can react directly with polyamines. Adding dienes with a symmetrical structure can make the addition reaction product unique, and the entire reaction has fewer by-products. Improving the yield of the template agent is helpful to obtain a template agent with a dendritic macromolecular structure.
  • the template agent provided in this application has a unique high surface area effect.
  • the particle size of the vinyl-terminated polyoxypropylene polyoxyethylene ether macromonomer is 15-30nm, the dispersion index is 1.003-1.01, and the particle size and distribution Controllable, overcoming the problem of uncontrollable size and distribution of large monomers used to prepare water-reducing agents in the prior art.
  • the vinyl-terminated polyoxypropylene polyoxyethylene ether macromonomer can be used as a water-reducing agent in concrete. Used, water-reducing agents have high water-reducing effect and low production costs.
  • This application provides a template agent, which uses symmetrical dienes, polyamines, cysteamine, hydrogen halide and hydroxyl-containing compounds as raw materials.
  • the diene has a symmetrical structure and can fully react with the polyamines to form the core of the macromolecule of the template agent.
  • a dendritic macromolecular structure is formed.
  • a three-dimensional dendritic macromolecular structure similar to a spherical structure is formed.
  • the template obtained is a nanoscale material, and High specific surface area.
  • the template agent has a three-dimensional spherical structure, and the end group is a functional hydroxyl group, which has an excellent hydrophilic effect.
  • the spherical structure is relatively unique; and because the surface of the template agent has multi-functional functional groups, plus a highly branched The molecular structure can make the template agent have excellent comprehensive properties.
  • the preparation method of the template agent provided in this application uses symmetrical dienes and polyamines as raw materials, first obtains the core of the template agent through an addition reaction, and then alternately adds dienes and cysteamine to perform double bond addition. Reaction and amino addition reaction, symmetrical dienes can fully react with polyamines, and dendrimers can be formed by alternately adding dienes and cysteamine, and then adding hydrogen halide and hydroxyl-containing compounds for addition and substitution reactions to obtain
  • the terminal group is a hydroxyl group and has a three-dimensional space similar to the spherical structure of the dendritic macromolecule template agent.
  • the template agent has a high specific surface area and overcomes the particle size and size of the large monomers used to prepare water reducing agents in the prior art. The problem of uncontrollable distribution; at the same time, repeated addition of dienes can make the template agent have a high surface area effect.
  • the vinyl-terminated polyoxypropylene polyoxyethylene ether macromonomer provided by this application is used as a raw material using the template agent provided by this application.
  • the particle size and size of the vinyl-terminated polyoxypropylene polyoxyethylene ether macromonomer obtained are: The distribution is controllable, the particle size is 15-30nm, the dispersion index is 1.003-1.01, and the weight average molecular weight is 400-6000.
  • the water-reducing agent produced by this monomer has good water-reducing effect, high early strength of concrete, and the water-reducing agent is When applied, the amount of addition is small and the production cost is low.
  • the water-reducing agent provided by this application and the vinyl-terminated polyoxypropylene polyoxyethylene ether macromonomer provided by this application are used as raw materials.
  • the particle size of the water-reducing agent is 92-120nm.
  • the water-reducing rate is related to the early stage of concrete. The strength has been significantly improved.
  • This embodiment provides a template agent and a preparation method thereof.
  • the preparation method of the template agent includes the following steps:
  • This embodiment provides a vinyl-terminated polyoxypropylene polyoxyethylene ether macromonomer and a preparation method thereof, wherein the designed molecular weight of the monomer is 3000, and the preparation method includes the following steps:
  • This embodiment provides a vinyl-terminated polyoxypropylene polyoxyethylene ether macromonomer and a preparation method thereof.
  • the designed molecular weight of the monomer is 2000.
  • the preparation method includes the following steps:
  • template agent prepared in Example 1 Add 88g of 2-hydroxyethyl vinyl ether, 3.8g of boron trifluoride ether and 0.8g of template agent (template agent prepared in Example 1) into a 2L high-pressure reaction kettle, seal it, start stirring, and raise the temperature to 110°C Then start to introduce 380g of propylene oxide gas to initiate the polymerization reaction. When the pressure in the reactor does not change, control the temperature in the reactor to 110°C, and then introduce 1400g of ethylene oxide within 5 hours. After the addition is completed, it is matured at a constant temperature. React for 1 hour. When the pressure of the reaction kettle no longer drops, start cooling the reaction kettle.
  • This embodiment provides a vinyl-terminated polyoxypropylene polyoxyethylene ether macromonomer and a preparation method thereof.
  • the designed molecular weight of the monomer is 3000.
  • the preparation method includes the following steps:
  • This comparative example provides a vinyl-terminated polyoxypropylene polyoxyethylene ether macromonomer and a preparation method thereof.
  • the preparation method includes the following steps:
  • This comparative example provides a template agent and a preparation method thereof.
  • the preparation method of the template agent includes the following steps:
  • This comparative example also provides a vinyl-terminated polyoxypropylene polyoxyethylene ether macromonomer and a preparation method thereof.
  • the preparation method includes the following steps:
  • This comparative example provides a template agent and a preparation method thereof.
  • the preparation method of the template agent includes the following steps:
  • This comparative example provides a vinyl-terminated polyoxypropylene polyoxyethylene ether macromonomer and a preparation method thereof.
  • the preparation method includes the following steps:
  • This test example provides the physical and chemical indicators of the vinyl-terminated polyoxypropylene polyoxyethylene ether macromonomer prepared in Examples 2-4 and Comparative Examples 1-3.
  • the test method for polyethylene glycol residual content is: headspace gas chromatography; wherein, chromatographic column: HP-1 30m ⁇ 0.32mm ⁇ 5.0um; column temperature: 60°C (Hold 7min), heating rate 40 °C/min; end temperature 250°C (Hold 8min); injector: 200°C; detector (FID): 250°C; column flow: 1.0ml/min; split ratio: 5:1.
  • test method for residual dioxane is: determination of free dioxane by headspace gas chromatography; chromatographic column: HP-1 30m ⁇ 0.32mm ⁇ 5.0um; column temperature: 60°C (Hold 7min), heating rate 40°C/ min; end temperature 250°C (Hold 8min); injector: 200°C; detector (FID): 250°C; column flow: 1.0ml/min; split ratio: 5:1.
  • the test method of molecular weight distribution index is: measured by gel chromatography; the test instrument is Shimadzu DGU-20A gel permeation chromatography; the detector is RID-20A differential refractive index detector; the chromatographic column is 2 water phase Columns Shedox SB-803 and SB-802.5 are connected in series, the column temperature is 40°C; detection conditions: mobile phase 0.1mol/l NaNO3 aqueous solution, flow rate is 0.8ml/min; sample concentration is 5-10mg/mL.
  • Particle size analysis is conducted in accordance with the standard GB/T 29022-2012, using dynamic light scattering (DLS) testing.
  • DLS dynamic light scattering
  • the vinyl-terminated polyoxypropylene polyoxyethylene ether monomer prepared by using the template agent of the present application contains less impurities such as polyethylene glycol and dioxane; and the vinyl-terminated polyoxypropylene polyoxyethylene
  • the particle size of the oxyethylene ether monomer is 15-30nm, and the molecular weight distribution is narrow, that is, the dispersion index is controllable and small.
  • This test example provides the performance test of the water-reducing agent prepared in Examples 2-4 and Comparative Examples 1-3 as raw materials (monomer A) respectively.
  • the preparation method of water reducing agent includes the following steps:
  • the slurry test refers to the standard GB/T 8077-2000 "Test Methods for Homogeneity of Concrete Admixtures", and the concrete test refers to GB/T 50080-2002 "Standards for Test Methods for Performance of Ordinary Concrete Mixtures”.
  • the commercially available water-reducing agents are the water-reducing and collapse-preserving polycarboxylate water-reducing agent PC-1 (brand name: BASF RHEOPLUS 410) with a solid content of 40% and the water-reducing and collapse-preserving polycarboxylic acid water-reducing agent PC- 2 (the brand name is SILKROAD SRE110).
  • the cement used is conch cement P.O 42.5 grade.
  • the amount of water-reducing agent added to the cement slurry is shown in Table 1, and the water-cement ratio is 0.29.
  • the amount of water reducing agent added to concrete is 0.40% relative to the weight of cement.
  • the water reduction rate, slump and slump time loss of each water reducing agent are shown in Table 2.

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  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
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Abstract

本申请属于高分子材料制备技术领域，具体涉及一种模板剂及其制备方法和应用。该模板剂的原料包括多元胺、二烯烃和卤化氢，二烯烃为对称单体，该模板剂为纳米窄带树状大分子模板剂，比表面积高，分子量分布窄，该模板剂的原料包括二烯烃，且二烯烃为对称单体，可以与多元胺直接进行反应，加入对称结构的二烯烃可以使得加成反应的产物唯一，且整个反应副产物较少，提高模板剂的收率，有助于得到具有树枝大分子结构的模板剂。

Description

一种模板剂及其制备方法和应用
交叉引用
本申请要求在2022年3月30日提交中国国家知识产权局、申请号为202210330583.9、发明名称为“一种模板剂及其制备方法和应用”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。
技术领域
本申请属于高分子材料制备技术领域，具体涉及一种模板剂及其制备方法和应用。
背景技术
聚羧酸减水剂是最新一代的混凝土外加剂，被称为第三代高性能减水剂。与上一代的萘系减水剂相比，聚羧酸减水剂具有更高的减水率、更好的水泥适应性等特点，同时聚羧酸减水剂的生产过程中无工艺性废水和废弃产生，属于绿色环保型材料。
聚醚大单体是减水剂合成中最重要的原料，占减水剂中90％的成分，它的性能直接决定了聚羧酸减水剂的性能。减水剂聚醚大单体中最重要的指标是双键保留率和分子量分布、粒径尺寸。目前大多数的聚醚厂家通过控制工艺过程和催化剂均可以使聚醚大单体的双键保留率大于90％，但是在制备聚醚大单体过程中还没有很好的方法控制单体的粒径尺寸以及粒径的分布。如何控制聚醚大单体的粒径大小、分子量分布，从而改善聚羧酸减水剂产品的性能已经成为外加剂行业重点关注的领域之一。
发明内容
因此，本申请要解决的技术问题在于克服现有技术中聚羧酸减水剂的粒径 尺寸及其分布较难控制等缺陷，从而提供了一种模板剂及其制备方法和应用。
为此，本申请提供了以下技术方案。
本申请提供了一种模板剂，其原料包括多元胺、二烯烃和卤化氢；
所述二烯烃为对称单体。
所述模板剂具有如下结构式：
Figure PCTCN2022105557-appb-000001
所述二烯烃的端基基团为双键；
所述多元胺的端基基团为氨基；进一步地，多元胺的两个端基基团为氨基；
所述二烯烃的摩尔量至少是多元胺的摩尔量的60倍。
所述模板剂还满足(1)-(3)中的至少一项，
(1)所述二烯烃为1,3-丁二烯、环氧丙烯酸酯和1,3-二乙烯基环丁烷中的至少一种；
(2)所述多元胺为三乙烯四胺、乙二胺和1,4-丁二胺中的至少一种；
(3)所述多元胺与所述二烯烃的摩尔比为1：(60-80)。
所述模板剂还满足(1)-(2)中的至少一项，
(1)所述模板剂的原料还包括含羟基化合物；
可选地，所述含羟基化合物为氢氧化钠和/或氢氧化钾；
(2)所述卤化氢为溴化氢、氯化氢和碘化氢中的至少一种。
所述模板剂的原料还包括半胱胺和/或有机溶剂；
可选地，所述半胱胺与所述多元胺的摩尔比为1：(25-37)。
所述有机溶剂可以是但不限于二甲基亚砜、丙酮、四氢呋喃、N,N-二甲基甲酰胺中的至少一种。
所述模板剂的原料包括三乙烯四胺，1,3-丁二烯和半胱胺，其中，半胱胺和三乙烯四胺的摩尔比为1：(34-36)，三乙烯四胺和1,3-丁二烯的摩尔比为1：(74-76)。本申请还提供了一种模板剂的制备方法，包括以下步骤，
(1)多元胺与部分二烯烃反应，得到第一中间产物；
(2)在第一中间产物中至少加入两次二烯烃，经双键加成后得到第二中间产物；
(3)在第二中间产物中加入二烯烃进行双键加成反应，双键加成反应完成后加入卤化氢进行加成反应，得到模板剂。
所述步骤(3)中，加入卤化氢完成加成反应之后还包括加入含羟基化合物进行取代反应的步骤。
所述步骤(2)中，在加入所述二烯烃的同时还包括加入半胱胺的步骤；
可选地，所述步骤(2)的具体步骤包括，在所述第一中间产物中至少两次交替加入二烯烃和半胱胺，经双键加成和氨基加成后得到第二中间产物；
可选地，在所述第一中间产物中交替加入二烯烃和半胱胺，交替次数两次，经双键加成和氨基加成后得到第二中间产物；
可选地，步骤(2)中第一次加入二烯烃的摩尔量是步骤(1)二烯烃的1.9-2.1倍；步骤(2)中第二次加入二烯烃的摩尔量是步骤(2)中第一次加入二烯烃的1.9-2.1倍。
本申请提供的模板剂的制备方法，具体包括以下步骤：
(1)多元胺与部分二烯烃混合，在室温下搅拌8-12h，然后置于60-80℃下反应15-30h，然后依次加入半胱胺和有机溶剂，搅拌20-60min后，用冰水洗涤，得到白色固体，即第一中间产物。
(2)在第一中间产物中交替加入二烯烃和半胱胺，交替次数为2次，加入二烯烃进行双键加成反应，加入半胱胺进行氨基加成反应，经两次双键加成反应和氨基加成反应后得到第二中间产物；其中，第二次二烯烃的用量是第一次二烯烃用量的(1.9-2.1)倍，第二次半胱胺的用量为第一次半胱胺用量的(1.9-2.1)倍，反应温度均为60-80℃。
其中，在第一中间产物中交替加入二烯烃和半胱胺的具体步骤为：在室温条件下在第一中间产物中加入二烯烃，搅拌8-12h，然后置于60-80℃下反应15-30h，进行双键加成反应，再加入半胱胺，搅拌20-60min，进行氨基加成反应，再依次加入二烯烃和半胱胺重复上述步骤，即得第二中间产物。
(3)在第二中间产物中加入二烯烃，在60-80℃下加成反应15-30h，然后通入卤化氢，并在过氧化苯甲酰的作用下，在80-120℃进行加成反应，反应时间为12-24h，加成反应结束后加入含羟基化合物，在60-100℃下进行取代反应， 反应时间为12-24h，然后得到模板剂。
其中，卤化氢和含羟基化合物的用量均为过量。
步骤(3)中加入的二烯烃的用量为步骤(2)中最后一次加入二烯烃用量的(1.9-2.1)倍。
此外，本申请提供了一种端乙烯基聚氧丙烯聚氧乙烯醚大单体，原料包括上述模板剂或上述方法制得的模板剂；
所述端乙烯基聚氧丙烯聚氧乙烯醚大单体具有如下结构式：
Figure PCTCN2022105557-appb-000002
其中，R 1为氢或甲基；R 2为C1-C4的亚烷基；R 3为氢、甲基或乙基；m为0-6间的任意数，n为10-150间的任意数。
进一步地，本申请还提供了一种端乙烯基聚氧丙烯聚氧乙烯醚大单体的制备方法，包括以下步骤，
端乙烯基醚、模板剂和催化剂混合，经引发后依次加入氧化丙烯和氧化乙烯，经聚合反应后得到所述端乙烯基聚氧丙烯聚氧乙烯醚大单体。
所述端乙烯基醚和模板剂的质量比为1：(0.001-0.02)；
可选地，所述端乙烯基醚为4-羟丁基乙烯基醚、二乙二醇单乙烯基醚和2-羟乙基乙烯基醚中的至少一种；
可选地，所述聚合反应的温度为90-120℃；
可选地，所述催化剂的用量为原料总质量的0.1-0.3％。原料总质量是指端乙烯基醚、模板剂、氧化丙烯和氧化乙烯的总质量。
上述端乙烯基聚氧丙烯聚氧乙烯醚大单体的制备方法具体包括以下步骤：
(1)端乙烯基醚、模板剂和催化剂混合，用氮气置换后，搅拌，升温至100-120℃，开始通入氧化丙烯，引发聚合反应；
(2)然后连续性通入氧化乙烯，在5h内将氧化乙烯加完，这期间控制温度为90-110℃，加料完毕后恒温熟化0.8-1.5h，待压力不再下降时，降温至60-90℃，加pH调节剂调pH至6-7，脱气后用吸附剂精制过滤得到端乙烯基聚氧丙烯聚氧乙烯醚大单体；
其中，步骤(1)中加入的端乙烯基醚与氧化丙烯的摩尔比为1:(0-6)。氧化丙烯和氧化乙烯的质量比为(0-336)：(440-6600)。
所述催化剂为路易斯酸催化剂，如三氟化硼乙醚，三氯化铝、三氯化铁，优先选择三氟化硼乙醚。其中，催化剂的用量为原料总质量的0.1-0.3％，原料包括端乙烯基醚、模板剂、氧化丙烯和氧化乙烯。
所述pH调节剂为酸溶液，酸溶液为磷酸、醋酸、苯甲酸和柠檬酸中的至少一种。
更进一步地，本申请提供了一种减水剂，其原料包括上述端乙烯基聚氧丙烯聚氧乙烯醚大单体或上述制备方法制得的端乙烯基聚氧丙烯聚氧乙烯醚大单体。
本申请技术方案，具有如下优点：
1.本申请提供的模板剂，该模板剂的原料包括多元胺、二烯烃和卤化氢，二烯烃为对称单体，该模板剂为纳米窄带树状大分子模板剂，比表面积高，分子量分布窄，该模板剂的原料包括二烯烃，且二烯烃为对称单体，可以与多元胺直接进行反应，加入对称结构的二烯烃可以使得加成反应的产物唯一，且整个反应副产物较少，提高模板剂的收率，有助于得到具有树枝大分子结构的模 板剂。本申请提供的模板剂具有独特的高表面积效应，制得的端乙烯基聚氧丙烯聚氧乙烯醚大单体的粒径为15-30nm，分散指数为1.003-1.01，粒径尺寸及其分布可控，克服了现有技术中用于制备减水剂的大单体尺寸和分布不可控的问题，同时该端乙烯基聚氧丙烯聚氧乙烯醚大单体在混凝土中可以作为减水剂使用，减水剂的减水效果高且生产成本低。
2.本申请提供模板剂，以对称的二烯烃、多元胺、半胱胺、卤化氢和含羟基化合物作为原料，二烯烃具有对称结构可以与多元胺充分反应，形成模板剂大分子的核，经与二烯烃和半胱胺交替加成后形成树枝大分子结构，加入卤化氢和含羟基化合物后，形成三维空间立体类似球状结构的树枝大分子结构，得到的模板剂为纳米级材料，且比表面积高。
该模板剂具有三维空间立体类球状结构，端基为功能性的羟基基团，亲水效果极佳，该球状结构较为独特；又由于该模板剂表面具有多功能性官能团，加上高度分支的分子结构，可以使模板剂具有优异的综合性能。
3.本申请提供的模板剂的制备方法，该方法通过以对称的二烯烃和多元胺为原料，先加成反应得到模板剂的核，再交替加入二烯烃和半胱胺进行双键加成反应和氨基加成反应，对称的二烯烃可以与多元胺进行充分反应，经交替加入二烯烃和半胱胺可以形成树枝大分子，然后加入卤化氢和含羟基化合物进行加成和取代反应后得到端基为羟基基团且具有三维空间立体类似球状结构的树枝大分子模板剂，该模板剂的比表面积高，克服了现有技术中用于制备减水剂的大单体的粒径尺寸及分布不可控的问题；同时二烯烃进行重复加成，可以使模板剂具有高表面积效应。
4.本申请提供的端乙烯基聚氧丙烯聚氧乙烯醚大单体，以本申请提供的模板剂作为原料，得到的端乙烯基聚氧丙烯聚氧乙烯醚大单体的粒径尺寸及分布可控，粒径为15-30nm，分散指数为1.003-1.01，重均分子量为400-6000，该单 体制得的减水剂的减水效果好，混凝土早期强度高，且减水剂在应用时，添加量少，生产成本低。
在制备端乙烯基聚氧丙烯聚氧乙烯醚大单体的过程中不会产生二噁烷等副产品，副产物少，不腐蚀不锈钢反应釜，有效解决了酸性催化剂在工业化生产中不可避免的实际应用难题。
5.本申请提供的减水剂，本申请提供的端乙烯基聚氧丙烯聚氧乙烯醚大单体作为原料制得的减水剂的粒径为92-120nm，减水率和混凝土的早期强度均得到显著提升。
具体实施方式
提供下述实施例是为了更好地进一步理解本申请，并不局限于所述最佳实施方式，不对本申请的内容和保护范围构成限制，任何人在本申请的启示下或是将本申请与其他现有技术的特征进行组合而得出的任何与本申请相同或相近似的产品，均落在本申请的保护范围之内。
实施例中未注明具体实验步骤或条件者，按照本领域内的文献所描述的常规实验步骤的操作或条件即可进行。所用试剂或仪器未注明生产厂商者，均为可以通过市购获得的常规试剂产品。
实施例1
本实施例提供了一种模板剂及其制备方法，该模板剂的制备方法包括以下步骤，
(1)将0.01mol三乙烯四胺和0.05mol 1,3-丁二烯混合，在室温下搅拌10h，然后升温至70℃后反应24h，依次加入0.05mol半胱胺和5ml二甲基亚砜，室温下搅拌30min后用冰水洗涤，得到白色固体，即第一中间产物。
(2)室温条件下先在第一中间产物中加入0.1mol 1,3-丁二烯，搅拌10h， 然后置于70℃下反应24h，进行双键加成反应，再加入0.1mol半胱胺，搅拌30min进行氨基加成反应，再降温至室温，然后加入0.2mol 1,3-丁二烯，搅拌10h，然后置于70℃下反应24h，进行双键加成反应，再加入0.2mol半胱胺，搅拌30min进行氨基加成反应后得到第二中间产物。
(3)在第二中间产物中加入0.4mol 1,3-丁二烯，在70℃下反应24h，然后通入过量HBr气体，在0.2mol过氧化苯甲酰的作用下，在90℃下进行加成反应，时间为18h，反应结束后加入过量的NaOH固体，在80℃下进行取代反应，18h后，得到模板剂。
实施例2
本实施例提供了一种端乙烯基聚氧丙烯聚氧乙烯醚大单体及其制备方法，其中，该单体的设计分子量为3000，制备方法包括以下步骤，
将50g 2-羟乙基乙烯基醚(分子量为88.11)、1.85g三氟化硼乙醚和0.5g模板剂(实施例1制得的模板剂)加入到2L高压反应釜中，密闭，开启搅拌，升温至110℃后开始通入95g环氧丙烷，引发聚合反应，控制反应釜温度不高于100±5℃，然后在5h内通入1600g环氧乙烷，加料完毕后恒温熟化反应1h，待反应釜压力不再下降时，开始给反应釜降温，待反应釜温度降至70±5℃后，加入磷酸，调pH至6-7后，脱气后趁热通过硅藻土和硅酸镁铝吸附剂过滤，得到端乙烯基聚氧丙烯聚氧乙烯醚大单体。
实施例3
本实施例提供了一种端乙烯基聚氧丙烯聚氧乙烯醚大单体及其制备方法，该单体的设计分子量为2000，制备方法包括以下步骤，
将88g 2-羟乙基乙烯基醚、3.8g三氟化硼乙醚和0.8g模板剂(实施例1制得的模板剂)加入到2L高压反应釜中，密闭，开启搅拌，升温至110℃后开始通入380g环氧丙烷气体，引发聚合反应，待反应釜内压力不载变化时，控制反 应釜内温度为110℃，然后在5h内通入1400g环氧乙烷，加料完毕后恒温熟化反应1h，待反应釜压力不再下降时，开始给反应釜降温，待反应釜温度降至80±5℃后，加入醋酸，调pH至6-7后，脱气后趁热通过硅藻土和硅酸镁铝吸附剂过滤，得到端乙烯基聚氧丙烯聚氧乙烯醚大单体。
实施例4
本实施例提供了一种端乙烯基聚氧丙烯聚氧乙烯醚大单体及其制备方法，该单体的设计分子量为3000，制备方法包括以下步骤，
将120g 4-羟基丁基乙烯基醚(分子量为116.16)、3.5g三氟化硼乙醚和0.5g模板剂(实施例1制得的模板剂)加入到2L高压反应釜中，密闭，开启搅拌，升温至115℃后开始通入150g环氧丙烷，引发聚合反应，待反应釜内压力不再变化时，控制反应釜内温度为110℃，然后在5h内通入2800g环氧乙烷，加料完毕后恒温熟化反应1h，待反应釜压力不再下降时，开始给反应釜降温，待反应釜温度降至80±5℃后，加入磷酸，调pH至6-7后，趁热通过硅藻土和硅酸镁铝吸附剂过滤，得到端乙烯基聚氧丙烯聚氧乙烯醚大单体。
对比例1
本对比例提供了一种端乙烯基聚氧丙烯聚氧乙烯醚大单体及其制备方法，制备方法包括以下步骤，
将50g 2-羟乙基乙烯基醚和1.85g三氟化硼乙醚加入到2L高压反应釜中，密闭，开启搅拌，升温至110℃后开始通入95g环氧丙烷，引发聚合反应，控制反应釜温度为105℃，然后在5h内通入1600g环氧乙烷，加料完毕后恒温熟化反应1h，待反应釜压力不再下降时，开始给反应釜降温，待反应釜温度降至70±5℃后，加入磷酸，调pH至6-7后，脱气后趁热通过硅藻土和硅酸镁铝吸附剂过滤，得到端乙烯基聚氧丙烯聚氧乙烯醚大单体。
对比例2
本对比例提供了一种模板剂及其制备方法，该模板剂的制备方法包括以下步骤，
(1)将0.01mol三乙烯四胺和0.05mol甲基丙烯酰氧基丙烯酸丙酯混合，在室温下搅拌10h，然后升温至70℃后反应24h，依次加入0.05mol半胱胺和5ml二甲基亚砜，室温下搅拌30min后用冰水洗涤，得到白色固体，即第一中间产物。
(2)室温条件下先在第一中间产物中加入0.1mol甲基丙烯酰氧基丙烯酸丙酯，搅拌10h，然后置于80℃下反应20h，进行双键加成反应，再加入0.1mol半胱胺，搅拌30min进行氨基加成反应，再降温至室温，然后加入0.2mol甲基丙烯酰氧基丙烯酸丙酯，搅拌10h，然后置于80℃下反应20h，进行双键加成反应，再加入0.2mol半胱胺，搅拌30min进行氨基加成反应后得到第二中间产物，反应温度为80℃，时间为20h。
(3)在第二中间产物中加入0.4mol甲基丙烯酰氧基丙烯酸丙酯，反应温度为80℃，时间为20h，然后通入过量HBr气体，在0.2mol过氧化苯甲酰的作用下，在90℃下进行加成反应，反应18h，反应结束后加入过量的NaOH固体，在80℃下进行取代反应，反应18h后，得到模板剂。
本对比例还提供了一种端乙烯基聚氧丙烯聚氧乙烯醚大单体及其制备方法，制备方法包括以下步骤，
将50g 2-羟乙基乙烯基醚、1.85g三氟化硼乙醚和0.5g模板剂(由本例制得的模板剂)加入到2L高压反应釜中，密闭，开启搅拌，升温至110℃后开始通入95g环氧丙烷，引发聚合反应，控制反应釜温度为100±5℃，然后在5h内通入1600g环氧乙烷，加料完毕后恒温熟化反应1h，待反应釜压力不再下降时，开始给反应釜降温，待反应釜温度降至80±5℃后，加入磷酸调pH至6-7后，脱气后趁热通过硅藻土和硅酸镁铝吸附剂过滤，得到端乙烯基聚氧丙烯聚 氧乙烯醚大单体。
对比例3
本对比例提供了一种模板剂及其制备方法，该模板剂的制备方法包括以下步骤，
(1)将0.01mol三乙烯四胺和0.05mol1,3-丁二烯混合，在室温下搅拌10h，然后升温至70℃后反应24h，依次加入0.05mol半胱胺和5ml二甲基亚砜，室温下搅拌30min后用冰水洗涤，得到白色固体，即第一中间产物。
(2)室温条件下先在第一中间产物中加入0.1mol 1,3-丁二烯，搅拌10h，然后置于70℃下反应24h，进行双键加成反应，再加入0.1mol半胱胺，搅拌30min进行氨基加成反应，再降温至室温，然后加入0.2mol 1,3-丁二烯，搅拌10h，然后置于70℃下反应24h，进行双键加成反应，再加入0.2mol半胱胺，搅拌30min进行氨基加成反应后得到第二中间产物。
(3)在第二中间产物中加入0.4mol 1,3-丁二烯，在70℃下反应24h后得到模板剂。
本对比例提供了一种端乙烯基聚氧丙烯聚氧乙烯醚大单体及其制备方法，制备方法包括以下步骤，
将50g 2-羟乙基乙烯基醚、1.85g三氟化硼乙醚和0.5g模板剂(由本例制得的模板剂)加入到2L高压反应釜中，密闭，开启搅拌，升温至110℃后开始通入95g环氧丙烷，引发聚合反应，控制反应釜温度在110±5℃，然后在5h内通入1600g环氧乙烷，加料完毕后恒温熟化反应1h，待反应釜压力不再下降时，开始给反应釜降温，待反应釜温度降至80±5℃后，加入磷酸调pH至6-7，后，趁热通过硅藻土和硅酸镁铝吸附剂过滤，得到端乙烯基聚氧丙烯聚氧乙烯醚大单体。
试验例1
本试验例提供了实施例2-4和对比例1-3制得的端乙烯基聚氧丙烯聚氧乙烯醚大单体的理化指标。
聚乙二醇残余量(PEG％)的测试方法为：顶空气相色谱法；其中，色谱柱：HP-1 30m×0.32mm×5.0um；柱温：60℃(Hold 7min)，升温速率40℃/min；终止温度250℃(Hold 8min)；进样器：200℃；检测器(FID)：250℃；柱流量：1.0ml/min；分流比：5:1。
二噁烷残余量的测试方法为：顶空气相色谱法测定游离二噁烷；色谱柱：HP-1 30m×0.32mm×5.0um；柱温：60℃(Hold 7min)，升温速率40℃/min；终止温度250℃(Hold 8min)；进样器：200℃；检测器(FID)：250℃；柱流量：1.0ml/min；分流比：5:1。
分子量分布指数的测试方法为：采用凝胶色谱法测得；测试仪器为岛津DGU-20A型凝胶渗透色谱；检测器为RID-20A型示差折光率检测器；色谱柱为2根水相柱Shedox SB-803和SB-802.5串联，柱温是40℃；检测条件：流动相0.1mol/l NaNO3水溶液，流速是0.8ml/min；配样浓度为5-10mg/mL。
粒径分析按照标准GB/T 29022-2012，采用动态光散射法(DLS)测试。
表1 实施例2-4和对比例1-3单体的理化指标
Figure PCTCN2022105557-appb-000003
Figure PCTCN2022105557-appb-000004
通过上述实验结果可以知道的是，采用本申请模板剂制备的端乙烯基聚氧丙烯聚氧乙烯醚单体中聚乙二醇和二噁烷等杂质含量少；以及该端乙烯基聚氧丙烯聚氧乙烯醚单体的粒径在15-30nm，分子量分布窄，即分散指数可控，较小。
试验例2
本试验例提供了实施例2-4和对比例1-3分别作为原料(单体A)制得的减水剂的性能测试。
减水剂的制备方法包括以下步骤：
(1)取30g单体A和44.5g水置于带有温度计和搅拌器的四口圆底烧瓶中，搅拌均匀，得到混合溶液A；
(2)取2g丙烯酸、0.05g维生素C和15g水混合均匀，得混合水溶液B，备用；
取0.08g巯基丙酸(链转移剂)和10.5g水混合均匀，得混合溶液C；
(3)控制混合溶液A温度为30℃，加入0.1g双氧水，然后同时滴加混合溶液B和混合溶液C，混合溶液B的滴加时间为1.5h，混合溶液C的滴加时间为2h，待全部滴加结束后，在30℃、常压下熟化1.5h，补水稀释，得到固含量为30％的聚羧酸减水剂。
净浆试验参照GB/T 8077-2000《混凝土外加剂匀质性试验方法》标准，混凝土试验参照GB/T50080-2002《普通混凝土拌合物性能试验方法标准》。
作为对比的市售减水剂为40％固含量的减水保塌型聚羧酸减水剂PC-1(牌号为：BASF RHEOPLUS 410)和减水保塌型聚羧酸减水剂PC-2(牌号为SILKROAD SRE110)。水泥使用海螺水泥P.O 42.5级。在水泥净浆中减水剂的添加量见表1，水灰比为0.29。在混凝土中减水剂的添加量相对于水泥重量的0.40％。各减水剂的减水率、塌落度和塌落经时损失，检测结果如表2所示。
表2 各减水剂的性能测试结果
Figure PCTCN2022105557-appb-000005
根据表2的实验结果可以看出，本申请制得的减水剂具有高保塌效果，保塌效果优异。
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。而由此所引申出的显而易见的变化或变动仍处于本申请创造的保护范围之中。

Claims (13)

  1. 一种模板剂，其特征在于，其原料包括多元胺、二烯烃和卤化氢；
    所述二烯烃为对称单体。
  2. 根据权利要求1所述的模板剂，其特征在于，所述二烯烃的端基基团为双键；
    所述多元胺的端基基团为氨基；
    所述二烯烃的摩尔量至少是多元胺的摩尔量的60倍。
  3. 根据权利要求2所述的模板剂，其特征在于，还满足(1)-(3)中的至少一项，
    (1)所述二烯烃为1,3-丁二烯、环氧丙烯酸酯和1,3-二乙烯基环丁烷中的至少一种；
    (2)所述多元胺为三乙烯四胺、乙二胺和1,4-丁二胺中的至少一种；
    (3)所述多元胺与所述二烯烃的摩尔比为1：(60-80)。
  4. 根据权利要求1-3任一项所述的模板剂，其特征在于，还满足(1)-(2)中的至少一项，
    (1)所述模板剂的原料还包括含羟基化合物；
    可选地，所述含羟基化合物为氢氧化钠和/或氢氧化钾；
    (2)所述卤化氢为溴化氢、氯化氢和碘化氢中的至少一种。
  5. 根据权利要求1-4任一项所述的模板剂，其特征在于，所述模板剂的原 料还包括半胱胺和/或有机溶剂；
    可选地，所述半胱胺与所述多元胺的摩尔比为1：(25-37)。
  6. 根据权利要求1-5任一项所述的模板剂，其特征在于，所述模板剂的原料包括三乙烯四胺，1,3-丁二烯和半胱胺；
    可选地，三乙烯四胺，1,3-丁二烯的摩尔比为1：(74-76)；
    半胱胺和三乙烯四胺的摩尔比为1：(34-36)。
  7. 一种模板剂的制备方法，其特征在于，包括以下步骤，
    (1)多元胺与部分二烯烃反应，得到第一中间产物；
    (2)在第一中间产物中至少加入两次二烯烃，经双键加成后得到第二中间产物；
    (3)在第二中间产物中加入二烯烃进行双键加成反应，双键加成反应完成后加入卤化氢进行加成反应，得到模板剂。
  8. 根据权利要求7所述的制备方法，其特征在于，所述步骤(3)中，加入卤化氢完成加成反应之后还包括加入含羟基化合物进行取代反应的步骤。
  9. 根据权利要求7或8所述的制备方法，其特征在于，所述步骤(2)中，在加入所述二烯烃的同时还包括加入半胱胺的步骤；
    可选地，所述步骤(2)的具体步骤包括，在所述第一中间产物中至少两次交替加入二烯烃和半胱胺，经双键加成和氨基加成后得到第二中间产物；
    可选地，在所述第一中间产物中交替加入二烯烃和半胱胺，交替次数两次，经双键加成和氨基加成后得到第二中间产物；
    可选地，步骤(2)中第一次加入二烯烃的摩尔量是步骤(1)二烯烃的1.9-2.1倍；步骤(2)中第二次加入二烯烃的摩尔量是步骤(2)中第一次加入二烯烃的1.9-2.1倍。
  10. 一种端乙烯基聚氧丙烯聚氧乙烯醚大单体，其特征在于，原料包括权利要求1-6任一项所述的模板剂或权利要求7-9任一项所述方法制得的模板剂；
    所述端乙烯基聚氧丙烯聚氧乙烯醚单体具有如下结构式：
    Figure PCTCN2022105557-appb-100001
    其中，R 1为氢或甲基；R 2为C1-C4的亚烷基；R 3为氢、甲基或乙基；m为0-6间的任意数，n为10-150间的任意数。
  11. 一种权利要求10所述的端乙烯基聚氧丙烯聚氧乙烯醚大单体的制备方法，其特征在于，包括以下步骤，
    端乙烯基醚、模板剂和催化剂混合，经引发后依次加入氧化丙烯和氧化乙烯，经聚合反应后得到所述端乙烯基聚氧丙烯聚氧乙烯醚大单体。
  12. 根据权利要求11所述的制备方法，其特征在于，所述端乙烯基醚和模板剂的质量比为1：(0.001-0.02)；
    可选地，所述端乙烯基醚为4-羟丁基乙烯基醚、二乙二醇单乙烯基醚和2-羟乙基乙烯基醚中的至少一种；
    可选地，所述聚合反应的温度为90-120℃；
    可选地，所述催化剂的用量为原料总质量的0.1-0.3％。
  13. 一种减水剂，其特征在于，其原料包括权利要求10所述的端乙烯基聚 氧丙烯聚氧乙烯醚大单体或权利要求11-12任一项所述制备方法制得的端乙烯基聚氧丙烯聚氧乙烯醚大单体。
PCT/CN2022/105557 2022-03-30 2022-07-13 一种模板剂及其制备方法和应用 WO2023184786A1 (zh)

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