Water-soluble polymer thickening agent and preparation method thereof

Abstract

The water-soluble polymer thickening agent is obtained by neutralizing functional modified polyether and glacial acetic acid, and the functional modified polyether is prepared from the following raw materials: mixed long-chain alkyl glycidyl ether and common polyether in a molar ratio of 1: (1.1-1.2); the addition amount of the aluminum isopropoxide is 0.03-0.05% of the sum of the mass of the mixed long-chain alkyl glycidyl ether and the mass of the common polyether. The invention also provides a preparation method of the water-soluble polymer thickening agent. The preparation method comprises the following steps: (1) preparing mixed long-carbon-chain alkyl glycidyl ether; (2) preparing common polyether; (3) preparing functional modified polyether; and (4) preparing the water-soluble polymer thickening agent. The invention aims to prepare a thickening agent which is relatively strong in bond energy and stable in chemical performance, so that the thickening agent can stably play a role at a relatively high temperature and in a relatively harsh pH environment, and is slightly influenced by pH and temperature.

Description

Technical Field

[0001] The invention relates to the technical field of thickeners, and in particular to a water-soluble polymer thickener and a preparation method thereof. Background Art

[0002] Since the 1970s, various functional polymer materials have been developed and applied in succession to meet market demand. Traditional general-purpose polyethers are not resistant to acid, alkali and high temperature due to the presence of active hydroxyl groups at the end of the molecular chain, and are prone to produce more foam when used as surfactants. In addition, when ordinary polyethers containing alkenyl groups react with other active groups, the presence of hydroxyl groups will affect the reaction of alkenyl groups, ultimately resulting in decreased product purity and the addition of complex by-products. As a result, countries around the world have increased their research and development efforts on functional polyethers, and have successively developed a number of functional polyethers, and some varieties have entered the stage of industrial production. These functional polyethers are widely used in chemical, civil, electronic, textile, printing and dyeing and other industries.

[0003] Among various functional polyethers, dialkyl-terminated E0 and P0 copolyethers are new varieties with more development prospects. Alkyl-terminated polyethers refer to polyethers in which the hydrogen on the terminal hydroxyl group of the polyether is replaced by an alkyl group. The special structure of alkyl-terminated polyethers gives it special physical and chemical properties, which determines its application value in many fields. Linear alkyl glycidyl ether-terminated modified polyethers are a type of water-soluble polymer thickeners. At a small addition amount, the viscosity of the aqueous solution can be greatly increased, and it has the advantages of acid and alkali resistance and shear resistance.

[0004] At present, alkyl glycidyl ether generally adopts fatty alcohol and epichlorohydrin as raw materials, first obtains the intermediate of chlorohydrin ether structure by ring-opening addition, and then removes hydrogen chloride ring closure to obtain product under the action of alkaline solution. However, in the current report on alkyl glycidyl ether, the alkyl part is mostly a single fatty chain, and the report on the synthesis of mixed long-chain alkyl glycidyl ether is less, and the synthesis method generally requires the combined use of multiple catalysts, and the method is relatively complicated and difficult to industrialization. Application number is that a kind of synthetic method of C12-14 mixed alkyl glycidyl ether is announced in the patent of 200810230035.9, which uses C12-14 alcohol as raw material, reacts with epichlorohydrin under the catalysis of Lewis acid catalyst, and then adds another kind of Lewis acid catalyst to make the reaction further proceed. In this method, multiple catalysts are combined, and the method is relatively complicated and difficult to industrial production. Based on this, the present invention proposes a water-soluble polymer thickener and its preparation method. Summary of the invention

[0005] The purpose of the present invention is to provide a water-soluble polymer thickener and a preparation method thereof. The prepared thickener has strong bond energy and stable chemical properties, so that it can stably function under higher temperatures and harsher pH environments and is less affected by pH and temperature.

[0006] In a first aspect, the present invention provides a water-soluble polymer thickener obtained by neutralizing a functional modified polyether with glacial acetic acid, wherein the molecular structure of the functional modified polyether is shown in Structural Formula 1: Structural formula 1.

[0007] Furthermore, the functional modified polyether preparation raw material includes a mixed long-chain alkyl glycidyl ether and a common polyether in a molar ratio of 1:1.1-1.2; and also includes 0.03-0.05% of aluminum isopropoxide added in an amount equal to the sum of the mass of the mixed long-chain alkyl glycidyl ether and the common polyether.

[0008] Furthermore, the raw materials for preparing the mixed long-chain alkyl glycidyl ether include C 12-14 alcohol, epichlorohydrin, a phase transfer catalyst and an aqueous sodium hydroxide solution, wherein C 12-14 The molar ratio of alcohol to epichlorohydrin is 1:1.1-1.5; the amount of phase transfer catalyst added is 12-14 0.3-0.7% of alcohol mass; C 12-14 The molar ratio of alcohol to sodium hydroxide aqueous solution is 1:1-1.5.

[0009] Furthermore, the phase transfer catalyst is tetrabutylammonium bromide.

[0010] Furthermore, the mass concentration of the sodium hydroxide aqueous solution is 14-16%.

[0011] Furthermore, the raw materials for preparing the common polyether include propylene alcohol, ethylene oxide and propylene oxide in a weight ratio of (250-280): (210-230): (56-60), and sodium hydroxide in an amount of 0.08% by weight of the total weight of propylene alcohol, propylene oxide and ethylene oxide.

[0012] In a second aspect, the present invention provides a method for preparing a water-soluble polymer thickener, the steps comprising: Preparation of mixed long carbon chain alkyl glycidyl ethers: C 12-14 Alcohol, epichlorohydrin and a phase transfer catalyst are mixed to undergo a ring-opening addition reaction to obtain an intermediate product; epichlorohydrin is added dropwise, and the reaction temperature is controlled at 55-60°C; The ring-opening reaction equation is as follows:

[0013] After the epichlorohydrin is added dropwise, the mixture is kept warm and aged for 2-4 hours; the intermediate product is mixed with a sodium hydroxide aqueous solution for a ring-closing reaction to obtain a mixed long-chain alkyl glycidyl ether; the reaction temperature is controlled at 55-60° C.; after the sodium hydroxide aqueous solution is added dropwise, the mixture is kept warm and aged for 2-4 hours; The closed-loop reaction equation is as follows:

[0014] (2) Preparation of ordinary polyether: Propylene alcohol is mixed with ethylene oxide and propylene oxide, and ordinary polyether is obtained under the catalysis of sodium hydroxide; after the propylene oxide is added dropwise, the mixture is kept warm and aged for 2-3 hours, and the reaction temperature is controlled at 110-120°C; (3) Preparation of functional modified polyether: The prepared mixed long-chain alkyl glycidyl ether is mixed with common polyether and aluminum isopropoxide to react to obtain functional modified polyether; the reaction time is controlled within 1-2 h, and the reaction temperature is controlled within 80-120°C; The reaction equation for preparing functional modified polyether is as follows:

[0015] (4) Preparation of a water-soluble polymer thickener: The obtained functionally modified polyether is added to glacial acetic acid for neutralization to obtain a water-soluble polymer thickener.

[0016] Furthermore, in the step (1), the epichlorohydrin is added dropwise for a time period of 1-4 h; the sodium hydroxide aqueous solution is added dropwise for a time period of 3-4 h.

[0017] Furthermore, in the step (2), propylene oxide and ethylene oxide are added dropwise; ethylene oxide is added dropwise directly without degassing, and the addition time is controlled within 1-4 h.

[0018] Furthermore, the molar ratio of the glacial acetic acid to the sodium hydroxide is 1-1.5:1.

[0019] The beneficial effects of the present invention are: The present invention provides a method for preparing a water-soluble polymer thickener, wherein a single phase transfer catalyst and a solvent-free method are used to synthesize C 12-14 The alkyl glycidyl ether end-capped modified polyether introduces hydrophobic groups into the polyether. The hydrophobic interaction between the hydrophobic groups can form hydrophobic micro-regions, thereby increasing the hydrodynamic volume of the polymer and making the polymer have a greater thickening ability (higher viscosity). The present invention uses a single phase transfer catalyst and a solvent-free method to synthesize C 12-14Alkyl glycidyl ether has high product yield and simple operation. The synthesized thickener has stable thickening effect and is little affected by pH and temperature. It can work synergistically with polyether-modified polysiloxane to ensure that the product can perform stably in various extreme application systems.

[0020] The present invention adopts a single phase transfer catalyst and synthesizes C12-14 alkyl glycidyl ether by a solvent-free method. The polyether modified by end-capping of long-chain alkyl glycidyl ether is a kind of water-soluble polymer thickener, which can greatly improve the viscosity of the aqueous solution at a relatively small addition amount, and has the advantages of small viscosity-temperature change, anti-shear and the like. The synthesized thickener has only bonds such as COC, CC and CH in its molecular structure, and its bonding electron cloud mass is very large, so the bond energy is relatively strong and the chemical properties are stable, so that it can stably play a role under higher temperature and harsher pH environment, and is little affected by pH and temperature. DETAILED DESCRIPTION

[0021] The technical solution of the present invention is described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention. Example

[0022] This embodiment provides a water-soluble polymer thickener. The preparation method of the water-soluble polymer thickener (taking the preparation of 1 kg of product as an example) includes the following steps: 1. Preparation of mixed long carbon chain alkyl glycidyl ethers: 315 g C 12-14 alcohol, 98 g of epichlorohydrin and 1.575 g of tetrabutylammonium bromide as a phase transfer catalyst were mixed for ring-opening addition reaction to obtain an intermediate product; epichlorohydrin was added dropwise, the addition time was controlled at 3 h, and the reaction temperature was controlled at 57 °C; after the epichlorohydrin was added dropwise, the mixture was kept warm for 3 h; The ring-opening reaction equation is as follows:

[0023] In a further embodiment, C 12-14 The molar ratio of alcohol to epichlorohydrin is 1:1.1-1.5; the amount of phase transfer catalyst added is 12-14 0.3-0.7% of alcohol mass; 414 g of the intermediate product and 300 g of a sodium hydroxide aqueous solution with a mass concentration of 15% were mixed for a closed-ring reaction to obtain a mixed long-chain alkyl glycidyl ether; the sodium hydroxide aqueous solution was added dropwise, the addition time was controlled at 3.5 h, and the reaction temperature was controlled at 57°C; after the sodium hydroxide aqueous solution was added dropwise, the mixture was kept warm and aged for 3 h; The closed-loop reaction equation is as follows:

[0024] In a further embodiment, C 12-14 The molar ratio of alcohol to sodium hydroxide aqueous solution is 1:1-1.5; the mass concentration of sodium hydroxide aqueous solution is 14-16%.

[0025] 2. Preparation of ordinary polyether: 265 g of propylene alcohol, 222 g of ethylene oxide and 58 g of propylene oxide were mixed, and ordinary polyether was prepared under the catalysis of 0.436 g of sodium hydroxide; propylene oxide and ethylene oxide were added by dropwise addition, and after the addition of propylene oxide was completed, the mixture was kept warm and aged for 2.5 hours, and ethylene oxide was directly added dropwise without degassing, and the addition time was controlled at 3 hours, and the reaction temperature was controlled at 115°C; The added amount of sodium hydroxide is 0.08% of the total mass of propylene alcohol, propylene oxide and ethylene oxide.

[0026] 3. Preparation of functional modified polyether: 455 g of the obtained mixed long-chain alkyl glycidyl ether was mixed with 545 g of common polyether and 0.3 g of aluminum isopropoxide to react to obtain functional modified polyether; the reaction time was controlled at 1.5 h and the reaction temperature was controlled at 100°C; The reaction equation for preparing functional modified polyether is as follows:

[0027] In a further embodiment, the molar ratio of the mixed long-chain alkyl glycidyl ether to the common polyether is 1:1.1-1.2; the amount of aluminum isopropoxide added is 0.03-0.05% of the sum of the mass of the mixed long-chain alkyl glycidyl ether and the common polyether; 4. Preparation of water-soluble polymer thickener: The obtained functionally modified polyether was neutralized by adding 0.5 g of glacial acetic acid to obtain a water-soluble polymer thickener.

[0028] In a further embodiment, the molar ratio of glacial acetic acid to sodium hydroxide is 1-1.5:1.

[0029] Performance testing method: At room temperature (25°C) and 170s -1Under the continuous shearing condition, the apparent viscosity of the solution with thickener added is measured over time. The effect of shearing time on the solution with thickener added is shown in the following table: Table 1

[0030] Through high temperature and high pressure rheometer experiments, at 25℃, 170s -1 Under the following conditions, the viscosity can reach 60-80mPa·s, at 90℃, 170 s -1 Under the conditions, the viscosity can reach 40 - 66mPa·s, at 120℃, 170 s -1 Under certain conditions, the viscosity can reach 30 - 44mPa·s.

[0031] Finally, it should be noted that the above embodiments are only used to illustrate the present invention and are not intended to limit the technical solutions described in the present invention. Those skilled in the art should understand that the present invention can still be modified or replaced by equivalents. All technical solutions and improvements that do not depart from the spirit and scope of the present invention should be included in the scope of the claims of the present invention.

Claims

1. A water-soluble polymer thickener, characterized in that: It is obtained by neutralizing a functional modified polyether with glacial acetic acid, wherein the molecular structure of the functional modified polyether is shown in Structural Formula 1: Structural formula 1.

2. A water-soluble polymer thickener according to claim 1, characterized in that: The functional modified polyether preparation raw materials include mixed long-chain alkyl glycidyl ether and common polyether in a molar ratio of 1:1.1-1.2; and also include 0.03-0.05% of aluminum isopropoxide added in an amount equal to the sum of the mass of the mixed long-chain alkyl glycidyl ether and the common polyether.

3. A water-soluble polymer thickener according to claim 2, characterized in that: The raw materials for preparing the mixed long-chain alkyl glycidyl ether include C 12-14 alcohol, epichlorohydrin, a phase transfer catalyst and an aqueous sodium hydroxide solution, wherein C 12-14 The molar ratio of alcohol to epichlorohydrin is 1:1.1-1.5; the amount of phase transfer catalyst added is 12-14 0.3-0.7% of alcohol mass; C 12-14 The molar ratio of alcohol to sodium hydroxide aqueous solution is 1:1-1.

5.

4. A water-soluble polymer thickener according to claim 3, characterized in that: The phase transfer catalyst is tetrabutylammonium bromide.

5. A water-soluble polymer thickener according to claim 3, characterized in that: The mass concentration of the sodium hydroxide aqueous solution is 14-16%.

6. A water-soluble polymer thickener according to claim 2, characterized in that: The raw materials for preparing the common polyether include propylene alcohol, ethylene oxide and propylene oxide in a weight ratio of (250-280): (210-230): (56-60), and sodium hydroxide in a weight percentage of 0.08% of the total weight of propylene alcohol, propylene oxide and ethylene oxide.

7. The method for preparing a water-soluble polymer thickener according to any one of claims 1 to 6, characterized in that the steps include: (1) Preparation of mixed long carbon chain alkyl glycidyl ethers: C 12-14 Alcohol, epichlorohydrin and a phase transfer catalyst are mixed for a ring-opening addition reaction to obtain an intermediate product; epichlorohydrin is added dropwise, and the reaction temperature is controlled at 55-60°C; after the epichlorohydrin is added dropwise, the mixture is kept warm for 2-4 hours; the intermediate product is mixed with a sodium hydroxide aqueous solution for a ring-closing reaction to obtain a mixed long-chain alkyl glycidyl ether; the reaction temperature is controlled at 55-60°C; after the sodium hydroxide aqueous solution is added dropwise, the mixture is kept warm for 2-4 hours; (2) Preparation of ordinary polyether: Propylene alcohol is mixed with ethylene oxide and propylene oxide, and ordinary polyether is obtained under the catalysis of sodium hydroxide; after the propylene oxide is added dropwise, the mixture is kept warm and aged for 2-3 hours, and the reaction temperature is controlled at 110-120°C; (3) Preparation of functional modified polyether: The prepared mixed long-chain alkyl glycidyl ether is mixed with common polyether and aluminum isopropoxide to react to obtain functional modified polyether; the reaction time is controlled within 1-2 h, and the reaction temperature is controlled within 80-120°C; (4) Preparation of a water-soluble polymer thickener: The obtained functionally modified polyether is added to glacial acetic acid for neutralization to obtain a water-soluble polymer thickener.

8. The method for preparing a water-soluble polymer thickener according to claim 7, characterized in that: In the step (1), the epichlorohydrin is added dropwise for 1-4 h; the sodium hydroxide aqueous solution is added dropwise for 3-4 h.

9. The method for preparing a water-soluble polymer thickener according to claim 7, characterized in that: In the step (2), propylene oxide and ethylene oxide are added dropwise; ethylene oxide is added dropwise directly without degassing, and the addition time is controlled within 1-4 h.

10. The method for preparing a water-soluble polymer thickener according to claim 7, characterized in that: The molar ratio of the glacial acetic acid to the sodium hydroxide is 1-1.5:1.

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