阅读说明：本技术 一种高分子乳化剂、及其制备方法、及其应用 (High-molecular emulsifier, and preparation method and application thereof ) 是由 陆小辉 闫辉 管莹 唐友江 于 2021-09-01 设计创作，主要内容包括：本发明涉及高分子合成技术领域,公开了一种高分子乳化剂、及其制备方法、及其应用,包括如下步骤：S1油脂脂肪酸、植物油酸和多元醇共混,经酯化脱水得到第一中间体；S2向第一中间体中加入三苯乙烯基苯酚聚氧乙烯-聚氧丙烯嵌段聚醚共混,再经磷酸化处理,得到第二中间体；S3第二中间体经胺中和,得到高分子乳化剂。本申请得到的高分子乳化剂,乳化性能优良,在少量助溶剂下,即可得到低粘度水性醇酸树脂、涂料,有利于降低涂料的VOCs。(The invention relates to the technical field of polymer synthesis, and discloses a polymer emulsifier, a preparation method and application thereof, wherein the preparation method comprises the following steps: s1, blending the fatty acid of the grease, the vegetable oleic acid and the polyalcohol, and obtaining a first intermediate through esterification and dehydration; s2 adding tristyrylphenol polyoxyethylene-polyoxypropylene block polyether into the first intermediate, blending, and carrying out phosphorylation treatment to obtain a second intermediate; and neutralizing the S3 second intermediate by amine to obtain the macromolecular emulsifier. The high-molecular emulsifier obtained by the method has excellent emulsifying property, can obtain low-viscosity water-based alkyd resin and paint under the condition of a small amount of cosolvent, and is favorable for reducing VOCs of the paint.)

1. The preparation method of the polymer emulsifier is characterized by comprising the following steps:

s1, blending the fatty acid of the grease, the vegetable oleic acid and the polyalcohol, and obtaining a first intermediate through esterification and dehydration;

s2 adding tristyrylphenol polyoxyethylene-polyoxypropylene block polyether into the first intermediate, blending, and carrying out phosphorylation treatment to obtain a second intermediate;

and neutralizing the S3 second intermediate by amine to obtain the macromolecular emulsifier.

2. The method for preparing a polymeric emulsifier according to claim 1, wherein the molar mass ratio of the fatty acid oil, the vegetable oleic acid, the polyhydric alcohol, and the tristyrylphenol polyoxyethylene-polyoxypropylene block polyether is 0.5-1.5: 1: 0.5-1.

3. The method for preparing a polymeric emulsifier according to claim 1 or 2, wherein the oil raw material in the oil fatty acid comprises at least one of catalpol oil, safflower oil, sunflower seed oil, cottonseed oil, grapeseed oil, dehydrated castor oil, grain oil, peanut oil, or evening primrose oil.

4. The method for producing a polymeric emulsifier according to claim 1 or 2, wherein the vegetable oleic acid comprises at least one of eleostearic acid, linoleic acid, linolenic acid, eleostearic acid, or dehydrated castor oil.

5. A method for preparing a polymeric emulsifier according to claim 1 or 2, wherein the polyol comprises at least one of trimethylolpropane, pentaerythritol, or neopentyl glycol.

6. The method for producing a polymeric emulsifier according to claim 1 or 2, wherein the reagent used for the phosphorylation is P₂O₅And at least one of phosphoric acid and polyphosphoric acid, wherein the molar mass ratio of the reagent to the polyhydric alcohol is 0.75-1: 1.

7. The method for preparing the polymeric emulsifier according to claim 1, wherein the amine comprises dimethylethanolamine and/or triethanolamine, and the amine is neutralized to have a pH value of 7 to 8.

8. The method for producing a polymeric emulsifier according to claim 1, wherein the reaction is stopped when the acid value is less than 1mgKOH/g in the esterification dehydration step.

9. A polymeric emulsifier obtained by the production method according to any one of claims 1 to 8.

10. Use of a polymeric emulsifier prepared according to any one of claims 1 to 8 in a waterborne alkyd resin.

Technical Field

The invention relates to the technical field of polymer synthesis, in particular to a polymer emulsifier, a preparation method and application thereof.

Background

With the increasing awareness of the environment protection of people and the stricter environmental regulations of various countries, the reduction of the content of VOC in the coating is a current research hotspot.

The VOCs of the traditional oil industrial coating is generally more than 300g/L, while the VOCs of the water industrial coating can be less than 60g/L and even zero, which puts requirements on lower VOCs for the main film forming material-resin of the water industrial coating. In the process of solving the problem of water-based resin and reducing VOCs (volatile organic compounds) of resin, the traditional resin mostly adopts a mode of directly introducing hydrophilic groups into high molecular resin to achieve the aim. However, this method has several problems as follows: (1) although the water dilutability of the resin can be realized, the obtained resin is usually high in viscosity, and a large amount of organic cosolvent is required to be added in the later-stage paint preparation, so that the indexes of VOCs are indirectly sacrificed; (2) because a large number of hydrophilic groups are introduced into molecules, the hydrophilic groups are usually positioned in a polyester molecular chain segment and are irregularly distributed, when a solvent system is changed or the environmental temperature is changed, macromolecules are wound and curled, the hydrophilic groups are isolated, and the hydrophilicity is changed, so that the storage stability of the resin or the coating is influenced; (3) the hydrophilicity of the resin can not be flexibly adjusted along with the application scene, and the later paint preparation application is restricted.

Disclosure of Invention

< problems to be solved by the present invention >

The current waterborne alkyd resin has the problems of high VOCs index, poor stability and strong application limitation.

< technical solution adopted in the present invention >

In view of the above technical problems, the present invention aims to provide a polymeric emulsifier, a preparation method thereof, and applications thereof.

The specific contents are as follows:

the invention provides a preparation method of a high-molecular emulsifier, which comprises the following steps:

s1, blending the fatty acid of the grease, the vegetable oleic acid and the polyalcohol, and obtaining a first intermediate through esterification and dehydration;

s2 adding tristyrylphenol polyoxyethylene-polyoxypropylene block polyether into the first intermediate, blending, and carrying out phosphorylation treatment to obtain a second intermediate;

and neutralizing the S3 second intermediate by amine to obtain the macromolecular emulsifier.

Secondly, the invention provides a high molecular emulsifier obtained by the preparation method.

Thirdly, the invention provides the application of the high molecular emulsifier in the waterborne alkyd resin.

< technical mechanism adopted in the present invention >

(1) Unsaturated double bonds contained in the molecules of the high molecular emulsifier can be oxidized and co-crosslinked with alkyd resin to form a film, so that the high molecular emulsifier cannot migrate to the surface of the coating, and the water resistance of the coating is not influenced;

(2) triphenylethylene phenol polyoxyethylene-polyoxypropylene block polyether is used as an emulsifier, when a nonionic hydrophilic chain segment is introduced, due to the strong lipophilicity of a triphenylethylene phenol group, two ends of the nonionic hydrophilic chain segment are both in an oil phase, the drying process of a paint film can be further reduced, and the migration process of the emulsifier to the surface of the paint film is reduced when the paint film is soaked in water, so that the water resistance of the paint film is improved;

(3) the hydroxyl-containing polyester is subjected to phosphorylation treatment to obtain polyester phosphate, and then amine neutralization is carried out to obtain a protonated phosphate hydrophilic group. The phosphate ester has good affinity to metal base materials, so that the coating is endowed with good adhesion to metal finally, and the corrosion resistance (salt spray resistance) of the coating is improved.

< advantageous effects achieved by the present invention >

(1) The prepared high molecular emulsifier has good compatibility with the traditional long-oil alkyd resin, strong affinity to the long-oil alkyd resin and excellent emulsifying capacity, can obtain low-viscosity water-based alkyd resin and paint under the condition of a small amount of cosolvent, and is beneficial to reducing VOCs of the paint;

(2) the polymer emulsifier has good emulsifying capacity on the long-oil alkyd resin, and can form a stable nonionic and anionic hydrophilic layer on the surface layer of long-oil alkyd resin colloidal particles, and the resin exists in the form of colloidal particles, so that intermolecular winding can be greatly reduced, and the whole resin dispersion system can have lower viscosity in the presence of a small amount of cosolvent, thereby achieving the purpose of low VOCs.

(3) The proportion of the high-molecular emulsifier and the resin to be emulsified is high in adjustability, so that water-dispersible alkyd resins with different degrees of hydrophilicity can be obtained to meet different application scenes.

Detailed Description

In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.

The invention provides a preparation method of a high-molecular emulsifier, which comprises the following steps:

s1, blending the fatty acid of the grease, the vegetable oleic acid and the polyalcohol, and obtaining a first intermediate through esterification and dehydration;

s2 adding tristyrylphenol polyoxyethylene-polyoxypropylene block polyether into the first intermediate, blending, and carrying out phosphorylation treatment to obtain a second intermediate;

and neutralizing the S3 second intermediate by amine to obtain the macromolecular emulsifier.

In particular, the amount of the solvent to be used,

s1 blending the fatty acid of the grease, the vegetable oleic acid and the polyhydric alcohol, introducing nitrogen, heating to 180-220 ℃, carrying out heat preservation treatment, carrying out esterification dehydration to obtain a first intermediate, and cooling to 50-75 ℃.

S2 adding tristyrylphenol polyoxyethylene-polyoxypropylene block polyether into the first intermediate, blending for 15-45 min, carrying out phosphorylation treatment, adding reagents used for phosphorylation treatment in batches, carrying out heat preservation for 1.5-4 h at 60-100 ℃, adding deionized water, and carrying out heat preservation for 1h to obtain a second intermediate;

and (3) cooling the second intermediate of S3 to 30-50 ℃, and neutralizing with amine to obtain the polymer emulsifier.

In the invention, the molar mass ratio of the fatty acid, the vegetable oleic acid, the polyalcohol and the tristyrylphenol polyoxyethylene-polyoxypropylene block polyether is 0.5-1.5: 1: 0.5-1.

In the invention, the oil raw material in the oil fatty acid comprises at least one of catalpol oil, safflower oil, sunflower seed oil, cottonseed oil, grape seed oil, dehydrated castor oil, grain oil, peanut oil or evening primrose oil.

In the present invention, the vegetable oil acid includes at least one of eleostearic acid, linoleic acid, linolenic acid, eleostearic acid, or dehydrated castor oil.

In the present invention, the polyol includes at least one of trimethylolpropane, pentaerythritol, or neopentyl glycol.

In the present invention, the reagent used for the phosphorylation is P₂O₅And at least one of phosphoric acid and polyphosphoric acid, wherein the molar mass ratio of the reagent to the polyhydric alcohol is 0.75-1: 1.

In the invention, the molar mass ratio of the deionized water to the polyhydric alcohol is 0.75-1: 1.

In the invention, the amine comprises dimethylethanolamine and/or triethanolamine, and the amine is neutralized until the pH value is 7-8.

In the present invention, the reaction is stopped when the acid value is less than 1mgKOH/g in the esterification dehydration step.

In the present invention, the triphenylvinylphenol polyoxyethylene-polyoxypropylene block polyether has EO and PO of (10-20) and (2-8).

Secondly, the invention provides a high molecular emulsifier which is obtained by the preparation method.

Thirdly, the invention provides the application of the high molecular emulsifier in the waterborne alkyd resin.

< example >

Example 1

Adding 0.5mol of catalpol oil fatty acid, 1.5mol of eleostearic acid and 1mol of trimethylolpropane into a reactor, introducing nitrogen for protection, heating to 200 ℃, performing dehydration esterification reaction until the acid value is less than 1mgKOH/g, and cooling to 60 ℃; adding 1mol of tristyrylphenol polyoxyethylene-polyoxyethylene propylene block polyether (EO: PO 16:2), and stirring for 30 min; adding 1mol of phosphorus pentoxide into 3 batches, and reacting for 2 hours at the temperature of 60 ℃; adding 1mol of deionized water, and keeping the temperature for 1 hour. And cooling to 40 ℃, adding 1mol of dimethylethanolamine for neutralization to enable the pH value to be 7-8, and obtaining a polymer emulsifier sample 1.

Example 2

Adding 1.5mol of catalpol oil fatty acid, 0.5mol of eleostearic acid and 1mol of trimethylolpropane into a reactor, heating to 200 ℃, introducing nitrogen for protection, performing dehydration esterification until the acid value is less than 1mgKOH/g, and cooling to 60 ℃; adding 1mol of tristyrylphenol polyoxyethylene-polyoxypropylene block polyether (EO: PO 16:2), and stirring for 30 min; adding 1mol of phosphorus pentoxide into 3 batches, and reacting for 2 hours at the temperature of 60 ℃; adding 1mol of deionized water, and keeping the temperature for 1 hour. And cooling to 40 ℃, adding 1mol of dimethylethanolamine for neutralization to enable the pH value to be 7-8, and obtaining a polymer emulsifier sample 2.

Example 3

Adding 1mol of catalpol oil fatty acid, 1mol of eleostearic acid and 1mol of trimethylolpropane into a reactor, introducing nitrogen for protection, heating to 200 ℃, performing dehydration esterification reaction until the acid value is less than 1mgKOH/g, and cooling to 60 ℃; adding 0.5mol of tristyrylphenol polyoxyethylene-polyoxypropylene block polyether (EO: PO 16:2), and stirring for 30 min; adding 0.75mol of phosphorus pentoxide into 3 batches, and reacting for 2 hours at the temperature of 60 ℃; adding 0.75mol of deionized water, and keeping the temperature for 1 hour. And cooling to 40 ℃, adding 0.75mol of dimethylethanolamine for neutralization to enable the pH value to be 7-8, and obtaining a polymer emulsifier sample 3.

Example 4

Adding 1mol of catalpol oil fatty acid, 1mol of eleostearic acid and 1mol of trimethylolpropane into a reactor, introducing nitrogen for protection, heating to 200 ℃, performing dehydration esterification reaction until the acid value is less than 1mgKOH/g, and cooling to 60 ℃; adding 0.5mol of tristyrylphenol polyoxyethylene-polyoxypropylene block polyether (EO: PO 16:2), and stirring for 30 min; adding polyphosphoric acid (1 mol for converting into phosphorus pentoxide) in 3 batches, and reacting for 2 hours at 60 ℃. And cooling to 40 ℃, adding 1mol of dimethylethanolamine for neutralization to enable the pH value to be 7-8, and obtaining a polymer emulsifier sample 4.

Example 5

Adding 1mol of catalpol oil fatty acid, 1mol of eleostearic acid and 1mol of trimethylolpropane into a reactor, introducing nitrogen for protection, heating to 200 ℃, performing dehydration esterification reaction until the acid value is less than 1mgKOH/g, and cooling to 60 ℃; adding 1mol of tristyrylphenol polyoxyethylene-polyoxypropylene block polyether (EO: PO 16:2), and stirring for 30 min; adding polyphosphoric acid (1 mol for converting into phosphorus pentoxide) in 3 batches, and reacting for 2 hours at 60 ℃. And cooling to 40 ℃, adding 1mol of dimethylethanolamine for neutralization to enable the pH value to be 7-8, and obtaining a polymer emulsifier sample 5.

Example 6

Adding 1mol of catalpol oil fatty acid, 1mol of eleostearic acid and 1mol of trimethylolpropane into a reactor, introducing nitrogen for protection, heating to 200 ℃, performing dehydration esterification reaction until the acid value is less than 1mgKOH/g, and cooling to 60 ℃; adding 0.5mol of tristyrylphenol polyoxyethylene-polyoxypropylene block polyether (EO: PO 16:2), and stirring for 30 min; adding polyphosphoric acid (0.75 mol for converting into phosphorus pentoxide) in 3 batches, and reacting for 2 hours at 60 ℃. And cooling to 40 ℃, adding 1mol of dimethylethanolamine for neutralization to enable the pH value to be 7-8, and obtaining a polymer emulsifier sample 6.

Example 7

Adding 1mol of catalpol oil fatty acid, 1mol of eleostearic acid and 1mol of trimethylolpropane into a reactor, introducing nitrogen for protection, heating to 200 ℃, performing dehydration esterification reaction until the acid value is less than 1mgKOH/g, and cooling to 60 ℃; adding 0.5mol of tristyrylphenol polyoxyethylene-polyoxypropylene block polyether (EO: PO 16:2), and stirring for 30 min; adding polyphosphoric acid (0.75 mol for converting into phosphorus pentoxide) in 3 batches, and reacting for 2 hours at 60 ℃. And cooling to 40 ℃, adding 1mol of triethanolamine for neutralization to enable the pH value to be 7-8, and obtaining a polymer emulsifier sample 7.

Example 8

Adding 0.5mol of catalpol oil fatty acid, 1.5mol of eleostearic acid and 1mol of trimethylolpropane into a reactor, introducing nitrogen for protection, heating to 200 ℃, performing dehydration esterification reaction until the acid value is less than 1mgKOH/g, and cooling to 60 ℃; adding 1mol of tristyrylphenol polyoxyethylene-polyoxypropylene block polyether (EO: PO ═ 20:8), and stirring for 30 min; adding 1mol of phosphorus pentoxide into 3 batches, and reacting for 2 hours at the temperature of 60 ℃; adding 1mol of deionized water, and keeping the temperature for 1 hour. And cooling to 40 ℃, adding 1mol of dimethylethanolamine for neutralization to enable the pH value to be 7-8, and obtaining a polymer emulsifier sample 8.

Example 9

Adding 0.5mol of cottonseed oil fatty acid, 1.5mol of linoleic acid and 1mol of pentaerythritol into a reactor, introducing nitrogen for protection, heating to 190 ℃, performing dehydration esterification reaction until the acid value is less than 1mgKOH/g, and cooling to 70 ℃; adding 1mol of tristyrylphenol polyoxyethylene-polyoxyethylene propylene block polyether (EO: PO ═ 12:8), and stirring for 35 min; adding 1mol of phosphorus pentoxide into 3 batches, and reacting for 4 hours at the temperature of 75 ℃; adding 1mol of deionized water, and keeping the temperature for 1 hour. And cooling to 35 ℃, adding 1mol of dimethylethanolamine for neutralization to enable the pH value to be 7-8, and obtaining a polymer emulsifier sample 9.

Example 10

Adding 1mol of evening primrose oil fatty acid, 1mol of dehydrated castor oil and 1mol of trimethylolpropane into a reactor, introducing nitrogen for protection, heating to 220 ℃, performing dehydration esterification reaction until the acid value is less than 1mgKOH/g, and cooling to 50 ℃; adding 0.75mol of tristyrylphenol polyoxyethylene-polyoxyethylene propylene block polyether (EO: PO ═ 14:6), and stirring for 30 min; adding 1mol of phosphorus pentoxide into 3 batches, and reacting for 3 hours at the temperature of 75 ℃; adding 1mol of deionized water, and keeping the temperature for 1 hour. And cooling to 30 ℃, adding 1mol of dimethylethanolamine for neutralization to enable the pH value to be 7-8, and obtaining a polymer emulsifier sample 10.

< test example >

Experimental group

The polymer emulsifier samples 1 to 8 prepared in the examples were used as samples. Neutralizing a long-oil alkyd resin liquid with oil content of 50-60% by using organic amine, adjusting the pH value to 7-8, adding a polymer emulsifier sample with 5% of the mass of the resin, stirring for 30min at room temperature, adding a proper amount of water, stirring at a low speed for dispersion, and diluting the solid content of the resin to 40% to obtain semi-transparent water-dispersible alkyd resin 1-8, which is represented by E1-E8.

Control group

Blank group: neutralizing the long-oil alkyd resin liquid with the oil content of 50-60% by using organic amine, adjusting the pH value to 7-8, adding a proper amount of water, stirring at a low speed for dispersion, and diluting the solid content of the resin to 40%. Blank set is denoted C1.

Comparison group: adding 1mol of soybean oil fatty acid, 1mol of trimethylolpropane and 0.75mol of phthalic anhydride into a reactor, introducing nitrogen for protection, gradually heating to 200 ℃, performing dehydration esterification reaction until the acid value is less than 10mgKOH/g, and cooling to 150 ℃; adding 0.45mol of trimellitic anhydride, gradually heating to 175 ℃, reacting until the acid value is 50mgKOH/g, cooling to 100 ℃ to obtain an intermediate, adding ethylene glycol monobutyl ether to dilute the intermediate to 75% (mass fraction), cooling to 60 ℃, adding 0.9mol of triethylamine to neutralize, adjusting the pH value to 7-8, and adding water to dilute to obtain the traditional waterborne alkyd resin. The control group is denoted by C2.

The samples E1-E8 and C1-C2 were used for the performance test of the water-dispersed resin and paint, and the test results are shown in Table 1.

TABLE 1 measurement results of Properties of Water-dispersible alkyd resins and paints

The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.