阅读说明：本技术 一种基于天然油脂的水性扩链剂制备方法 (Preparation method of water-based chain extender based on natural oil ) 是由 关仲翔 关汉杰 姚文佩 于 2020-07-27 设计创作，主要内容包括：本发明提供了一种基于天然油脂的水性扩链剂制备方法,包括以下步骤：S1.将含有不饱和键的天然油脂与质子酸发生加成反应,使天然油脂的不饱和键充分饱和,得加成油脂；S2.将加成油脂与碱溶液发生羟基取代反应和皂化反应,得到含羟基和金属离子的化合物；S3.加入饱和盐水,析出,提纯得到金属基二醇类的水性扩链剂。该水性扩链剂制备方法采用了天然油脂与含氢化合物的加成反应,然后与碱溶液的羟基取代反应和皂化反应,最后析出提纯获得产品,整个制备工序简单可靠,容易操作；其制备得到的水性扩链剂可直接应用于水性树脂生产,避免羧酸盐法需要加胺类成盐剂产生的臭味。(The invention provides a preparation method of a water-based chain extender based on natural oil, which comprises the following steps: s1, carrying out addition reaction on natural oil containing unsaturated bonds and protonic acid to fully saturate the unsaturated bonds of the natural oil to obtain addition oil; s2, carrying out hydroxyl substitution reaction and saponification reaction on the addition grease and an alkali solution to obtain a compound containing hydroxyl and metal ions; and S3, adding saturated saline water, precipitating, and purifying to obtain the metal-based glycol aqueous chain extender. The preparation method of the water-based chain extender adopts the addition reaction of natural oil and a hydrogen-containing compound, then the addition reaction and the saponification reaction of the natural oil and an alkaline solution, and finally the product is obtained by precipitation and purification, and the whole preparation process is simple and reliable and is easy to operate; the prepared water-based chain extender can be directly applied to the production of water-based resin, and the odor generated by adding amine salt forming agents into a carboxylate method is avoided.)

1. A preparation method of a water-based chain extender based on natural oil is characterized by comprising the following steps:

s1, carrying out addition reaction on natural oil containing unsaturated bonds and protonic acid to fully saturate the unsaturated bonds of the natural oil to obtain addition oil;

s2, carrying out hydroxyl substitution reaction and saponification reaction on the addition grease and an alkali solution to obtain a compound containing hydroxyl and metal ions;

and S3, adding saturated saline water, precipitating, and purifying to obtain the metal-based glycol aqueous chain extender.

2. The preparation method of the aqueous chain extender, according to the claim 1, is characterized in that the aqueous chain extender comprises the following components by weight: 30-130 parts of natural oil, 1-20 parts of protonic acid, 50-120 parts of ethanol, 30-100 parts of alkali solution and 300 parts of saturated saline.

3. The method for preparing an aqueous chain extender according to claim 1, wherein in S2, after obtaining the compound containing hydroxyl groups and metal ions, the acidification is continued to obtain a compound containing hydroxyl groups and carboxyl groups; then adding saturated brine for precipitation, and purifying to obtain the carboxyl diol aqueous chain extender.

4. The method for preparing an aqueous chain extender according to any one of claims 1 to 3, wherein the natural oil or fat comprises at least two of linoleic acid, ricinoleic acid, soybean oil or safflower oil.

5. The preparation method of the aqueous chain extender according to claim 4, wherein the natural oil is linoleic acid and ricinoleic acid according to the weight ratio of 10: 90 of fatty acids mixed together.

6. Process for the preparation of an aqueous chain extender according to any one of claims 1 to 3The method is characterized in that the protonic acid comprises HCl and H₂S、H₂SO₄Or one of HAC.

7. The method for preparing an aqueous chain extender according to any one of claims 1 to 3, wherein the alkali solution is one of KOH, NaOH or ammonia water to prepare an aqueous solution with a concentration of 8 to 30%.

8. The method of preparing an aqueous chain extender of any of claims 1 to 3 wherein the saturated brine is KCl or NaCl saturated solution.

9. An aqueous chain extender, characterized in that it is prepared by the method for preparing an aqueous chain extender according to any one of claims 1 to 3.

Technical Field

The invention relates to the technical field of organic polymer synthesis, in particular to a preparation method of a water-based chain extender based on natural oil.

Background

At present, the most critical material for producing the waterborne polyurethane is a functional chain extender, and a more commonly used chain extender is diol with carboxyl, such as dimethylolpropionic acid DMPA or dimethylolbutyric acid DMBA. The chain extender brings carboxyl into a main chain through chain extension, and then a salt forming agent (such as triethylamine TEA) is added to enable a polymer to generate water solubility, so that water-based resins such as water-based emulsion or water-based dispersion are obtained. Due to the addition of amine salt formers, the product tends to have amine odor, while amine nitrogen is a fertilizer, making aqueous products prone to spoilage.

In recent years, the manufacturing industry of waterborne polyurethane also develops a chain extender without adding a salt forming agent, such as diaminosulfonate, the chain extender carries soluble metal ions, and the salt forming agent is not required to be added, so that the smell of waterborne products is reduced. However, the chain extender has extremely high unit price and complex and fussy production process.

The fatty acid chain of natural oils and fats does not contain a hydroxyl group, and further does not contain a carboxyl group and a metal ion, and ricinoleic acid alone has a hydroxyl group, and in general, it cannot be a chain extender of dihydroxy.

Patent application with publication number CN107556452A discloses a castor oil based hydrophilic chain extender and a preparation method thereof. The application starts from castor oil, hydroxyl is introduced by utilizing sulfydryl-alkene light click reaction to obtain an intermediate, then carboxyl is generated by ester group hydrolysis reaction (or ricinoleic acid is generated by ester group hydrolysis reaction of castor oil, and then hydroxyl is introduced by utilizing sulfydryl-alkene light click reaction), a hydrophilic chain extender containing at least two hydroxyl groups and one carboxyl group is prepared, and the hydrophilic chain extender is applied to the preparation of anionic waterborne polyurethane emulsion. The preparation method of the patent application is carried out under the illumination condition by adding the photoinitiator, and in the subsequent treatment process, the unreacted photoinitiator, namely the byproduct, still needs to be treated, so that the problem of complicated working procedures still exists.

Therefore, how to synthesize an aqueous chain extender from natural oil and fat which are renewable resources, replace an organic solvent with aqueous, and improve the sustainable utilization of raw materials and the degradability of products is a technical problem to be solved by those skilled in the art.

Disclosure of Invention

In order to solve the problems in the prior art, the invention provides a preparation method of a natural oil-based aqueous chain extender, which comprises the steps of carrying out addition reaction on natural oil containing unsaturated bonds and a hydrogen-containing compound, fully saturating the unsaturated bonds, then carrying out reaction on the saturated unsaturated bonds and an alkaline solution, substituting halogen or other functional groups with hydroxyl groups and simultaneously carrying out saponification reaction, and then carrying out precipitation and purification to obtain the metal-based diol or carboxyl diol aqueous chain extender. The aqueous chain extender can be directly applied to the production of aqueous resin, and avoids the odor generated by adding amine salt forming agent in the carboxylate method.

In order to achieve the purpose, the invention provides the following technical scheme:

a preparation method of a water-based chain extender based on natural oil comprises the following steps:

s1, carrying out addition reaction on natural oil containing unsaturated bonds and protonic acid to fully saturate the unsaturated bonds of the natural oil to obtain addition oil;

s2, carrying out hydroxyl substitution reaction and saponification reaction on the addition grease and an alkali solution to obtain a compound containing hydroxyl and metal ions;

and S3, adding saturated saline water, precipitating, and purifying to obtain the metal-based glycol aqueous chain extender.

As further description of the technical scheme of the invention, the aqueous chain extender comprises the following components in parts by weight: 30-130 parts of natural oil, 1-20 parts of protonic acid, 50-120 parts of ethanol, 30-100 parts of alkali solution and 300 parts of saturated saline.

As a further description of the technical scheme of the invention, in S2, after obtaining a compound containing hydroxyl and metal ions, continuing acidification to obtain a compound containing hydroxyl and carboxyl; then adding saturated brine for precipitation, and purifying to obtain the carboxyl diol aqueous chain extender.

By further acidifying the product, another important aqueous chain extender is formed: a carboxyl group-containing dihydroxy chain extender. The product containing metal ions can be directly applied to the production of aqueous resin, and the odor generated by adding amine salt forming agents in the carboxylate method is avoided.

As a further description of the technical solution of the present invention, the natural oil includes at least two of linoleic acid, ricinoleic acid, soybean oil, or safflower oil.

Linoleic acid contains two olefinic bonds, ricinoleic acid contains one olefinic bond and one hydroxyl, wherein the olefinic bond is added by a hydrogen-containing compound such as hydrogen halide, then the olefinic bond reacts with an alkali solution to replace halogen by the hydroxyl, water-soluble ions can be introduced while saponification reaction is carried out, and finally the hydroxyl is introduced into the olefinic bond, so that the product is accurately introduced into the two hydroxyl and water-soluble ions, and the dihydric alcohol with metal ions is obtained; if acidification is carried out, the product is a diol with carboxyl groups.

As further description of the technical scheme of the invention, the natural oil is linoleic acid and ricinoleic acid, and the weight ratio of the natural oil to the linoleic acid is 10: 90 of fatty acids mixed together.

Linoleic acid and ricinoleic acid are common fatty acid feedstocks that can be utilized, and products containing other fatty acids require purification. The natural oil and fat containing other fatty acids may be soybean oil (linoleic acid 60%, oleic acid 35%), safflower oil (70% linoleic acid), etc.

As a further description of the technical solution of the present invention, the protonic acid comprises one of HCl, H2S, H2SO4 or HAC. The protonic acid mentioned above is a compound that can donate a proton.

As further description of the technical scheme of the invention, the alkali solution is one of KOH, NaOH or ammonia water which is prepared into an aqueous solution with the concentration of 8-30%.

As a further description of the technical scheme of the invention, the saturated saline is KCl or NaCl saturated solution.

In the above-mentioned raw materials and solvent, the oil and fat are dissolved in ethanol to be used as a reaction medium, so that the addition reaction proceeds rapidly.

Wherein, the structural formula of the natural oil is as follows:

(1) linoleic acid:

(2) ricinoleic acid:

the olefinic bond in the above-mentioned linoleic acid and ricinoleic acid is added with hydrogen halide and then reacted with alkali solution, the halogen element is substituted by hydroxyl group, and at the same time, saponification reaction is made to produce metal soap. The product is dihydroxy substance with metal ions, and can be used for synthesizing chain extender of water-based resin. The structural formula of the product related to the chain extender is as follows:

(1) dihydroxy sodium linoleate

(2) Dihydroxy sodium ricinoleate

(3) Dihydroxyricinoleic acid/dihydroxylinoleic acid (re-acidified product):

the invention also provides a water-based chain extender, which is prepared by adopting the preparation method of the water-based chain extender.

The product has double hydroxyl groups, can be used as a raw material for synthesizing resins such as polyurethane, polyester and the like, and can also be used as a chain extender.

Based on the technical scheme, the invention has the following technical effects:

(1) according to the preparation method of the natural oil-based water-based chain extender, the raw materials are natural and renewable, and the prepared product has water-soluble metal ions or carboxyl and can be used for producing water-based resin; in addition, the product is prepared from natural raw materials, can be naturally degraded, reduces the pollution to the environment, and meets the requirements of environmental protection and sustainable production.

(2) According to the preparation method of the natural oil based water-based chain extender, the product is a product with water-soluble metal ions, can be directly applied to the production of water-based resin, does not need to add an amine salt forming agent additionally, and avoids the odor generated by adding the amine salt forming agent in a carboxylate method.

(3) The preparation method of the water-based chain extender adopts the addition reaction of the natural oil and the hydrogen-containing compound, then the hydroxyl substitution reaction and the saponification reaction of the natural oil and the hydrogen-containing compound, and finally the product is obtained by precipitation and purification.

Detailed Description

In order that the invention may be more fully understood, reference will now be made to the specific embodiments illustrated. The invention provides a preferred embodiment. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.

Carrying out the step

A preparation method of a water-based chain extender based on natural oil comprises the following steps:

s1, carrying out addition reaction on natural oil containing unsaturated bonds and protonic acid to fully saturate the unsaturated bonds of the natural oil to obtain addition oil;

s2, carrying out hydroxyl substitution reaction and saponification reaction on the addition grease and an alkali solution to obtain a compound containing hydroxyl and metal ions;

and S3, adding saturated saline water, precipitating, and purifying to obtain the metal-based glycol aqueous chain extender.

The aqueous chain extender comprises the following components in parts by weight: 30-130g of natural oil, 1-20g of protonic acid, 50-120g of ethanol, 30-100g of alkali solution and 300g of saturated saline.

The natural oil consists of linoleic acid and ricinoleic acid, and the mixing ratio of the linoleic acid to the ricinoleic acid is 10: 90.

the protonic acid is halide, and the alkali solution is KOH, NaOH or ammonia water to prepare 8-30% concentration water solution.