阅读说明：本技术 一种水溶性复合树脂液制作方法 (Preparation method of water-soluble composite resin liquid ) 是由 唐志龙 周诗彪 唐文龙 邱丽萍 郭娓 肖安国 申有名 于 2019-11-24 设计创作，主要内容包括：本发明公开了一种水溶性复合树脂液制作方法,包括如下步骤：S1、预先制备阳离子型水性聚氨酯；在装有搅拌器、回流器、冷凝器的反应釜中,按3：1的摩尔比加入甲苯二异氰酸酯和经真空干燥脱水处理的聚乙二醇,逐步生温到60℃,保温反应3小时制得初聚体。降温至40℃以下,向上述初聚体内滴加一定量的亲水扩链剂N-甲基二乙醇胺-丙酮溶液,滴完后升温至60℃,保温反应1小时;本发明选用软硬不同、分子量不同、极性较大的水溶性树脂进行复合；由于树脂分子软硬互补、互容增塑,加之分子间的极性氢键的作用,使得该复合树脂涂层材料有较高的机械强度、较高的韧性和适宜的弹性,从而保证了防水膜层的力学强度以及其耐冷热循环不破裂。(The invention discloses a preparation method of water-soluble composite resin liquid, which comprises the following steps: s1, preparing cationic waterborne polyurethane in advance; in a reaction kettle provided with a stirrer, a reflux device and a condenser, the reaction is carried out according to the proportion of 3: adding toluene diisocyanate and polyethylene glycol subjected to vacuum drying and dehydration treatment according to the molar ratio of 1, gradually heating to 60 ℃, and carrying out heat preservation reaction for 3 hours to obtain a protomer. Cooling to below 40 ℃, dropwise adding a certain amount of hydrophilic chain extender N-methyldiethanolamine-acetone solution into the primary polymer, heating to 60 ℃ after dropwise adding, and carrying out heat preservation reaction for 1 hour; the resin molecules complement each other in hardness and are mutually compatible and plasticized, and the polar hydrogen bonds among the molecules act, so that the composite resin coating material has high mechanical strength, high toughness and proper elasticity, and the mechanical strength of the waterproof film layer and the cold and hot cycle resistance of the waterproof film layer are ensured without cracking.)

1. A method for preparing water-soluble composite resin liquid is characterized in that: the method comprises the following steps:

s1, preparing a polyvinyl alcohol solution;

adding 800Kg of deionized water into a reaction kettle, heating to 80 ℃, adding 300Kg of 1788 type polyvinyl alcohol while stirring, heating to above 95 ℃ after the polyvinyl alcohol is basically dissolved, and continuously keeping the temperature and stirring until the polyvinyl alcohol is completely dissolved to obtain a polyvinyl alcohol solution for later use;

s2, preparing a pre-polymerization mixed solution by using a polyvinyl alcohol solution;

respectively adding 80-120 parts of lignocellulose aqueous solution with the weight concentration of 20%, 300 parts of polyamide resin aqueous solution with the weight concentration of 50% and 250 parts of polyvinyl alcohol aqueous solution with the weight concentration of 30% into a reaction kettle, heating to 60-70 ℃ while stirring, preserving heat and stirring for 1-2 hours, sampling and analyzing, and obtaining prepolymer mixed solution for later use after no suspended matter and no precipitate are generated;

s3, preparing cationic waterborne polyurethane; in a reaction kettle provided with a stirrer, a reflux device and a condenser, the reaction is carried out according to the proportion of 3: 1, adding toluene diisocyanate and polyethylene glycol subjected to vacuum drying dehydration treatment, gradually heating to 60 ℃, and carrying out heat preservation reaction for 3 hours to obtain a protomer; cooling to below 40 ℃, dropwise adding a certain amount of hydrophilic chain extender N-methyldiethanolamine-acetone solution into the primary polymer, heating to 60 ℃ after dropwise adding, and carrying out heat preservation reaction for 1 hour to obtain a polyurethane prepolymer containing tertiary amine with a certain molecular weight; cooling the prepolymer to below 40 ℃, adding a certain amount of glacial acetic acid into the system for neutralization, adding a certain amount of acetone for dilution, and quickly stirring and mixing to obtain an intermediate; slowly adding a certain amount of deionized water into the intermediate body, stirring at a high speed for 3 hours, dropwise adding dilute hydrochloric acid to adjust the pH value of the system to 5-7, and removing acetone in vacuum to obtain a cationic waterborne polyurethane solution;

s4, compounding water-soluble resin, namely adding 150 parts of polyethylene oxide aqueous solution with the weight concentration of 50%, 150 parts of water-soluble epoxy resin aqueous solution with the weight concentration of 50% and 300 parts of cationic aqueous polyurethane solution with the solid content of 50% into the prepolymerization mixed solution, heating to 85-90 ℃, and then stirring for 2-3 hours under heat preservation;

s5, sampling and analyzing the compound;

and S6, cooling to room temperature after the detection is qualified, filtering, metering and packaging.

2. The method for producing a water-soluble composite resin liquid according to claim 1, wherein: and (3) after the polyvinyl alcohol in the S1 is completely dissolved, adding 200Kg of deionized water into the reaction kettle, cooling to room temperature while stirring, and filtering to obtain a polyvinyl alcohol solution for later use.

3. The method for producing a water-soluble composite resin liquid according to claim 2, wherein: 100-150 parts of 30 wt% aqueous sodium polyacrylate solution was further added to the S2.

4. The method for producing a water-soluble composite resin liquid according to claim 3, wherein: the dosage of the hydrophilic chain extender N-methyldiethanolamine-acetone solution in the S3 is 5-6% of the mass of the protomer.

5. The method for producing a water-soluble composite resin liquid according to claim 4, wherein: the neutralization degree of glacial acetic acid in the S3 is 80-100%.

6. The method for producing a water-soluble composite resin liquid according to claims 1 to 5, wherein: the complex detection requires: no suspended matter, no precipitate and no unpleasant organic solvent smell; the PH value is 5-7, the solid content of the composite resin liquid is 35-40 percent; the specific gravity is 1.20-1.25 Kg/L; the acid value is less than 5 mgKOH/g; the viscosity was measured by a smear-4 viscometer at 90-100 sec/25 ℃.

7. The method for producing a water-soluble composite resin liquid according to claim 6, wherein: the sampling analysis of the compound in the S5 also comprises a compound coating film test, wherein the surface drying of the coating film is less than 5 minutes/25 ℃, and the actual drying is less than 12 hours/25 ℃; the coating hardness reaches HB pencil hardness; flexibility 1 mm.

8. The method for producing a water-soluble composite resin liquid according to claim 7, wherein: the compound film coating test also comprises a circling method for testing the adhesive force, and the adhesive force of the circling method reaches level 1; the tensile strength of the coating film is 15-17 MPa; the elongation at break of the coating is 80-100%.

Technical Field

The invention belongs to the technical field of production of composite resin liquid, and particularly relates to a preparation method of water-soluble composite resin liquid.

Background

The resin generally refers to an organic polymer which has a softening or melting range after being heated, tends to flow by an external force when softened, and is solid, semi-solid, or liquid at room temperature. Broadly defined, any high molecular compound that can be used as a raw material for processing plastic products is called a resin; organic substances which have an indefinite but usually high relative molecular weight and which are solid, medium solid, pseudo solid or sometimes liquid at ordinary temperatures. Has a softening or melting temperature range, tends to flow under an external force, and often breaks into a shell-like shape. Broadly refers to polymers or prepolymers used as plastic substrates. Generally insoluble in water and soluble in organic solvents. The thermoplastic resin and the thermosetting resin are classified according to the characteristics of different processing behaviors;

at present, the water-soluble composite resin is more and more widely applied, but the preparation process of the water-soluble composite resin is complicated at present, the mechanical strength of a finished product is low, and the toughness and elasticity are not ideal, so that the inventor provides a preparation method of the water-soluble composite resin liquid by integrating various factors.

Disclosure of Invention

The invention aims to: in order to solve the technical problems related to the background technology, a preparation method of a water-soluble composite resin liquid is provided.

The technical scheme adopted by the invention is as follows:

a preparation method of water-soluble composite resin liquid comprises the following steps:

s1, preparing cationic waterborne polyurethane in advance;

in a reaction kettle provided with a stirrer, a reflux device and a condenser, the reaction is carried out according to the proportion of 3: adding toluene diisocyanate and polyethylene glycol subjected to vacuum drying and dehydration treatment according to the molar ratio of 1, gradually heating to 60 ℃, and carrying out heat preservation reaction for 3 hours to obtain a protomer. And (3) cooling to below 40 ℃, dropwise adding a certain amount (5-6% of the mass of the prepolymer) of a hydrophilic chain extender N-methyldiethanolamine-acetone solution into the prepolymer, heating to 60 ℃ after dropwise adding, and carrying out heat preservation reaction for 1 hour to obtain the tertiary amine-containing polyurethane prepolymer with a certain molecular weight. And (3) cooling the prepolymer to below 40 ℃, adding a certain amount of glacial acetic acid into the system for neutralization (the neutralization degree is 80-100%), adding a certain amount of acetone for dilution, and quickly stirring and mixing to obtain an intermediate. Slowly adding a certain amount of deionized water into the intermediate body, stirring at a high speed for 3 hours, dropwise adding dilute hydrochloric acid to adjust the pH value of the system to 5-7, and removing acetone in vacuum to obtain a cationic waterborne polyurethane solution;

s202, preparing a polyvinyl alcohol solution;

adding 800Kg of deionized water into a reaction kettle, heating to 80 ℃, adding 300Kg of 1788 type polyvinyl alcohol while stirring, heating to above 95 ℃ after the polyvinyl alcohol is basically dissolved, continuing to keep the temperature and stir until the polyvinyl alcohol is completely dissolved, adding 200Kg of deionized water into the reaction kettle, cooling to room temperature while stirring, filtering, and packaging for later use.

S203, compounding of the composite resin liquid:

adding 80-120 parts of 20% by weight lignocellulose aqueous solution, 300 parts of 50% by weight polyamide resin aqueous solution, 250 parts of 30% by weight polyvinyl alcohol aqueous solution and 150 parts of 30% by weight sodium polyacrylate aqueous solution into a reaction kettle respectively, heating to 60-70 ℃ while stirring, keeping the temperature and stirring for 1-2 hours, sampling and analyzing, after no suspended matter and no precipitate, respectively adding 150 parts of polyethylene oxide aqueous solution with the weight concentration of 50%, 150 parts of water-soluble epoxy resin aqueous solution with the weight concentration of 50% and 300 parts of cationic aqueous polyurethane solution with the solid content of 50%, heating to 85-90 ℃, then preserving heat and stirring for 2-3 hours, sampling and analyzing: no suspended matter, no precipitate and no unpleasant organic solvent smell; the PH value is 5-7, the solid content of the composite resin liquid is 35-40 percent; the specific gravity is 1.20-1.25 Kg/L; the acid value is less than 5 mgKOH/g; viscosity of 90-100 seconds/25 ℃ measured by a smear-4 viscometer; the surface drying of the coating is less than 5 minutes/25 ℃, and the actual drying is less than 12 hours/25 ℃; the coating hardness reaches HB pencil hardness; the flexibility is 1 mm; the adhesive force of the circling method reaches 1 level; the tensile strength of the coating film is 15-17 MPa; the elongation at break of the coating is 80-100%.

And (4) cooling to room temperature after the conventional indexes are detected to be qualified, filtering, metering and packaging.

In summary, due to the adoption of the technical scheme, the invention has the beneficial effects that:

1. the invention selects water-soluble resins with different hardness, different molecular weights and larger polarity for compounding; obtaining water-soluble composite resin liquid; the resin molecules complement each other in hardness and are mutually compatible and plasticized, and the polar hydrogen bonds among the molecules act, so that the composite resin coating material has high mechanical strength, high toughness and proper elasticity, and the mechanical strength of the waterproof film layer and the cold and hot cycle resistance of the waterproof film layer are ensured without cracking.

2. The aqueous composite resin liquid is yellowish, transparent and odorless, and can be used for preparing colorless and waterproof and anti-seepage coatings with various colors according to different application aspects and application requirements.

3. The aqueous composite resin liquid can be selected from low molecular weight resin molecules which can permeate into base materials such as cement, wood and the like, so that the adhesive force of a waterproof coating material is improved, the waterproof leakage performance of the base material is improved while the waterproof leakage of the coating is formed, namely the double waterproof leakage effect of the coating and the base material is formed, and the waterproof leakage effect is improved.

Drawings

FIG. 1 is a schematic diagram of the structure of the present invention.

Detailed Description

In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.

A preparation method of water-soluble composite resin liquid comprises the following steps:

s1, preparing a polyvinyl alcohol solution;

adding 800Kg of deionized water into a reaction kettle, heating to 80 ℃, adding 300Kg of 1788 type polyvinyl alcohol while stirring, heating to above 95 ℃ after the polyvinyl alcohol is basically dissolved, and continuously keeping the temperature and stirring until the polyvinyl alcohol is completely dissolved to obtain a polyvinyl alcohol solution for later use;

s2, preparing a pre-polymerization mixed solution by using a polyvinyl alcohol solution;

respectively adding 100 parts of lignocellulose aqueous solution with the weight concentration of 20%, 250 parts of polyamide resin aqueous solution with the weight concentration of 50% and 180 parts of polyvinyl alcohol aqueous solution with the weight concentration of 30% into a reaction kettle, heating to 65 ℃ while stirring, preserving heat and stirring for 2 hours, sampling and analyzing, and obtaining pre-polymerization mixed solution for later use after no suspended matter and no precipitate exist;

s3, preparing cationic waterborne polyurethane; in a reaction kettle provided with a stirrer, a reflux device and a condenser, the reaction is carried out according to the proportion of 3: adding toluene diisocyanate and polyethylene glycol subjected to vacuum drying and dehydration treatment according to the molar ratio of 1, gradually heating to 60 ℃, and carrying out heat preservation reaction for 3 hours to obtain a protomer. Cooling to below 40 ℃, dropwise adding a certain amount of hydrophilic chain extender N-methyldiethanolamine-acetone solution into the primary polymer, heating to 60 ℃ after dropwise adding, and carrying out heat preservation reaction for 1 hour to obtain a polyurethane prepolymer containing tertiary amine with a certain molecular weight; cooling the prepolymer to below 40 ℃, adding a certain amount of glacial acetic acid into the system for neutralization, adding a certain amount of acetone for dilution, and quickly stirring and mixing to obtain an intermediate; slowly adding a certain amount of deionized water into the intermediate body, stirring at a high speed for 3 hours, dropwise adding dilute hydrochloric acid to adjust the pH value of the system to 6, and removing acetone in vacuum to obtain a cationic waterborne polyurethane solution;

s4, compounding water-soluble resin, namely adding 150 parts of polyethylene oxide aqueous solution with the weight concentration of 50%, 200 parts of water-soluble epoxy resin aqueous solution with the weight concentration of 50% and 250 parts of cationic aqueous polyurethane solution with the solid content of 50% into the prepolymerization mixed solution, heating to 85 ℃, and then keeping the temperature and stirring for 3 hours;

s5, sampling and analyzing the compound;

and S6, cooling to room temperature after the detection is qualified, filtering, metering and packaging.

And (3) after the polyvinyl alcohol in the S1 is completely dissolved, adding 200Kg of deionized water into the reaction kettle, cooling to room temperature while stirring, and filtering to obtain a polyvinyl alcohol solution for later use.

100 parts of 30% by weight aqueous sodium polyacrylate solution was also added to the S2.

The dosage of the hydrophilic chain extender N-methyldiethanolamine-acetone solution in the S3 is 6% of the mass of the prepolymer; the neutralization degree of glacial acetic acid in the S3 is 80%.

The resulting water-soluble resin was tested: no suspended matter, no precipitate and no unpleasant organic solvent smell; the PH value is 6, the solid content of the composite resin liquid is 35 percent; the specific gravity is 1.20 Kg/L; the acid value is less than 5 mgKOH/g; viscosity 90 seconds/25 ℃ measured with a smear-4 viscometer; coating film surface drying at 4 min/25 deg.c and solid drying at 10 hr/25 deg.c; the coating hardness reaches HB pencil hardness; the flexibility is 1 mm; testing the adhesive force by a circling method, wherein the adhesive force of the circling method reaches 1 grade; the tensile strength of a coating film is 16 MPa; the elongation at break of the coating film was 85%.

The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.