阅读说明：本技术 一种含缩醛键的多丙烯酸酯及其制备方法和应用 (Polyacrylate containing acetal bond and preparation method and application thereof ) 是由 李智慧 李大爱 赵琳 李钟玉 于 2021-09-03 设计创作，主要内容包括：本发明公开了一种含缩醛键的多丙烯酸酯的制备方法及其在交联剂中的应用,其制备方法是：将多元醇和无水四氢呋喃混合,对甲苯磺酸作催化剂,将2-(乙烯氧基)乙基丙烯酸酯在室温条件下,缓慢加入到上述体系中,采用磁力搅拌,得到含缩醛键的多丙烯酸酯,该产物结构中有缩醛键,具有酸降解功能；同时结构中有多个丙烯酸酯键,可以和巯基发生典型的巯基-烯迈克加成反应。因此,合成的含缩醛键的多丙烯酸酯是一种重要的具有酸降解功能的交联剂。本发明的优点是,所用到的试剂及原料常见易得,反应速率快,反应条件温和,操作方法简单,在高分子领域内具有广泛的应用前景。(The invention discloses a preparation method of polyacrylate containing acetal bond and application thereof in a cross-linking agent, wherein the preparation method comprises the following steps: mixing polyhydric alcohol and anhydrous tetrahydrofuran, taking p-toluenesulfonic acid as a catalyst, slowly adding 2- (vinyloxy) ethyl acrylate into the system at room temperature, and stirring by magnetic force to obtain polyacrylate containing acetal bonds, wherein the product has the acetal bonds and has an acid degradation function; meanwhile, a plurality of acrylate bonds are arranged in the structure, and typical mercapto-alkene Michael addition reaction can be carried out on the acrylate bonds and mercapto. Therefore, the synthesized polyacrylate containing acetal bond is an important crosslinking agent with acid degradation function. The method has the advantages of common and easily obtained reagents and raw materials, high reaction rate, mild reaction conditions, simple operation method and wide application prospect in the polymer field.)

1. A polyacrylate containing an acetal linkage, characterized in that:

the molecular structural formula is as follows:

2. the polyacrylate having an acetal linkage according to claim 1, wherein:

the R group is:

3. the process for producing an acetal bond-containing polyacrylate according to claim 1 or 2, characterized in that: the method comprises the following steps:

the method comprises the following steps: adding polyol and an acid catalyst into a reaction vessel filled with a first solvent, and stirring and mixing to form a first mixture;

step two: slowly adding 2- (ethyleneoxy) ethyl acrylate dropwise to the first mixture;

step three: after the dropwise addition is finished, reacting for 3-5h, after the reaction is finished, adding organic base into the system, adjusting the pH value of the problem to 7-8, concentrating, adding dichloromethane, extracting once by using dichloromethane, drying, and concentrating again to obtain a product;

the structural formula of the 2- (ethyleneoxy) ethyl acrylate is as follows:

the structural formula of the polyol is as follows:

4. the method for producing an acetal bond-containing polyacrylate according to claim 3, characterized in that:

the first solvent is anhydrous tetrahydrofuran.

5. The method for producing an acetal bond-containing polyacrylate according to claim 3, characterized in that:

the acid catalyst is p-toluenesulfonic acid.

6. The method for producing an acetal bond-containing polyacrylate according to claim 3, characterized in that:

the organic base is triethylamine.

7. The method for producing an acetal bond-containing polyacrylate according to claim 3, characterized in that:

the molar ratio of the functional groups of the polyol to the 2- (ethyleneoxy) ethyl acrylate fed in the first mixture is: 1: 1.1-1.3.

8. The method for producing an acetal bond-containing polyacrylate according to claim 3, characterized in that:

the mass fraction of the sum of the mass of the polyhydric alcohol and the mass of the 2- (ethyleneoxy) ethyl acrylate in the reaction system is 30-50%.

9. The method for producing an acetal bond-containing polyacrylate according to claim 3, characterized in that:

the mass fraction of the acid catalyst is 0.04-0.08% of the mass of the anhydrous tetrahydrofuran.

10. Use of the acetal bond-containing polyacrylate according to claim 1, wherein:

the cross-linking agent is applied to degradable membrane materials.

Technical Field

The invention belongs to the field of organic synthesis, and particularly relates to a preparation method and application of polyacrylate containing acetal bonds.

Background

Crosslinking is the process of linking linear or branched macromolecules between chains by covalent bonding through a crosslinking agent to form macromolecules with a net or body structure. The cross-linking agent is also called as a curing agent, plays a role in bridging and connecting in the cross-linking process, and can enable a plurality of linear or branched molecules to be mutually bonded together to form a polymer with a larger molecular weight and a reticular structure so as to enhance the mechanical property and stability of the material. In the aqueous coating industry, the use of crosslinking agents is often used to improve the application properties of the coating film, such as the water resistance, solvent resistance, and hardness of the film. Therefore, in the field of polymers, crosslinking agents are widely used.

In general, for the internal crosslinking agent, vinyl monomers such as acrylic acid, methacrylic acid, hydroxyethyl acrylate, etc. need to undergo a crosslinking reaction under heating or radiation conditions when used; external cross-linking agents, such as polyisocyanates, polyols, etc., are generally added prior to use and then cross-linked at room temperature, heat or radiation. The cross-linking agent can be used for connecting polymer main chains and can be used as a cross-linking agent with multiple reaction sites, and can also be used as a cross-linking monomer to prepare a cross-linking material with better performance. For example, trimethylolpropane triacrylate containing multiple reactive sites, acrylate monomers containing 3 double bonds in the molecular structure can be used not only for crosslinking polymers, but also as crosslinking monomers.

The document "improving the mechanical property of the aqueous fluorine-containing acrylic resin by crosslinking modification" ([ J ].2020, 33 (02): 1-5) discloses that trimethylolpropane triacrylate (TMPTA) is used as a crosslinking agent, and the tensile strength, hardness and thermal stability of an emulsion film can be effectively improved by adding the TMPTA.

The influence of a TMPTA crosslinking system on the performance of a cationic acrylate leather finishing agent is disclosed in the document (J. Chinese leather, 2008 (11): 13-16.) trimethylolpropane triacrylate (TMPTA) is used as a crosslinking monomer and reacts with an acrylate monomer to synthesize an acrylic resin emulsion, so that the dry-wet rubbing resistance and the solvent resistance of finished leather are improved.

Although the conventional crosslinking agents have certain advantages in enhancing the performance of the material, the conventional crosslinking agents have problems in the subsequent use process, such as: the problems of environmental unfriendliness, difficult degradation, high cost, low crosslinking degree and the like are solved, and the novel degradable crosslinking agent capable of improving the crosslinking degree is required to be developed to meet the requirements of production and life. Based on the idea, when the cross-linking agent is designed, some groups which are relatively easy to degrade can be introduced, so that the subsequent degradation of the material is realized; in addition, some reactive sites are introduced into the cross-linking agent to improve the cross-linking degree.

Disclosure of Invention

In view of the disadvantages of the prior art, the present invention aims to provide a polyacrylate containing acetal bond, which has acid-sensitive property; in addition, the acrylic ester modified polyurethane contains a plurality of active sites of acrylic ester, and can effectively improve the crosslinking degree.

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

a polyacrylate having an acetal linkage, which comprises a polyacrylate having an acetal linkage,

the molecular structural formula is as follows:

as a further improvement of the present invention,

the R group is:

as another object of the present invention, there is provided a process for producing an acetal bond-containing polyacrylate,

the method comprises the following steps:

the method comprises the following steps: adding polyol and an acid catalyst into a reaction vessel filled with a first solvent, and stirring and mixing to form a first mixture;

step two: slowly adding 2- (ethyleneoxy) ethyl acrylate dropwise to the first mixture;

step three: after the dropwise addition is finished, reacting for 3-5h, after the reaction is finished, adding organic base into the system, adjusting the pH value of the problem to 7-8, concentrating, adding dichloromethane, extracting once by using dichloromethane, drying, concentrating again, passing the obtained crude product through a column by using a column chromatography method, selecting ethyl acetate and petroleum ether with a certain volume ratio as a developing agent, concentrating the collected product, placing the concentrated product in a vacuum drying oven, and maintaining the pressure for 24h to obtain a product;

the structural formula of the 2- (ethyleneoxy) ethyl acrylate is as follows:

the structural formula of the polyol is as follows:

as a further improvement of the present invention,

the first solvent is anhydrous tetrahydrofuran.

As a further improvement of the present invention,

the acid catalyst is p-toluenesulfonic acid.

As a further improvement of the present invention,

the organic base is triethylamine.

As a further improvement of the present invention,

the molar ratio of the functional groups of the polyol to the 2- (ethyleneoxy) ethyl acrylate fed in the first mixture is: 1: 1.1-1.3;

as a further improvement of the invention, the mass ratio of the polyol to the 2- (ethyleneoxy) ethylacrylate and in the system is 30% to 50%.

As a further improvement of the present invention,

the mass fraction of the acid catalyst is 0.04-0.08% of the mass of the anhydrous tetrahydrofuran.

The invention also provides application of the polyacrylate containing acetal bonds as a cross-linking agent in degradable membrane materials.

The principle of the invention is as follows: the polyol is reacted with 2- (ethyleneoxy) ethyl acrylate, the reaction scheme is as follows:

the invention has the beneficial effects that: 1. the method has the advantages of cheap and easily-obtained raw materials, high reaction rate, mild reaction conditions and simple and easy operation;

2. the polyacrylate containing acetal bond obtained by the invention can be degraded into corresponding alcohol and acetaldehyde under acidic condition, and the degradation route is as follows:

3. the polyacrylate containing acetal bond obtained by the invention can provide a plurality of reactive sites, can generate crosslinking reaction with multi-sulfydryl, multi-amino and the like, and can be prepared into corresponding degradable materials, thus being relatively environment-friendly.

Drawings

FIG. 1 is a nuclear magnetic hydrogen spectrum of a product obtained in example 1 of the present invention;

FIG. 2 is a reaction scheme provided in example 2 of the present invention;

FIG. 3 is a film provided in example 2 of the present invention;

FIG. 4 is a film contact angle provided in example 2 of the present invention;

FIG. 5 is a surface topography before acid degradation as provided in example 2 of the present invention;

FIG. 6 is a surface topography after acid degradation as provided in example 2 of the present invention;

Detailed Description

The invention will be further described in detail with reference to the following examples, which are given in the accompanying drawings.

Example 1:

the method comprises the following steps: 0.84g of pentaerythritol and 5.2mg of p-toluenesulfonic acid catalyst are stirred in 6.5g of anhydrous tetrahydrofuran for about 5 min;

step two: 3.68g of 2-mono (ethyleneoxy) ethyl acrylate was slowly added to the above system.

Step three: after reacting for 5h, dropwise adding 2 drops of triethylamine into the system, then concentrating the system, extracting the obtained crude product for 2 times by using dichloromethane, drying, concentrating, purifying the obtained mixed solution by adopting a column chromatography method, and passing the mixed solution through a column by using ethyl acetate and petroleum ether with the volume ratio of 1: 2.5 to obtain the product.

And concentrating the collected target substance, and maintaining the pressure in a vacuum drying oven for 24h for later use. And then performing nuclear magnetic hydrogen spectrum characterization on the obtained nuclear magnetic hydrogen spectrum, wherein the nuclear magnetic information shown in figure 1 is as follows:

¹H NMR(400MHz，CDCl₃)δ6.34(dd，J＝17.3，1.1Hz，4H)，6.07(dd，J＝17.3，10.4Hz，4H)，5.76(d，J＝10.5Hz，4H)，4.62(dd，J＝5.0，1.4Hz，4H)，4.21(dd，J＝11.2，6.7Hz，8H)，3.70(dd，J＝7.3，4.8Hz，4H)，3.62-3.49(m，8H)，3.27(d，J＝9.0Hz，4H)，1.18(t，J＝6.9Hz，12H)。

example 2:

0.70g of the product obtained in example 1, 0.53g of trimethylolpropane tris (3-mercaptopropionic acid) ester, was taken in 1.2g of anhydrous tetrahydrofuran, and after completely dissolving, it was transferred to a petri dish, and placed in a closed vessel containing an atmosphere of triethylamine, and by a fumigation method, a film was obtained, the reaction route of which is shown in FIG. 2, and the film is shown in FIG. 3. A few films were taken and the contact angle of the surface was measured to be 68.80 deg., as shown in FIG. 4, indicating that the surface was somewhat hydrophilic. Cutting off two small membranes with the same size, and soaking one membrane in pure methanol; soaking the other part of the film in 1mol/L hydrochloric acid methanol solution for 50h respectively, airing, and observing the change of the surface appearance of the film through an electron microscope, wherein the appearance of the film which is not soaked in acid is not obviously changed and only slightly swells, as shown in figure 5; the surface of the acid-soaked film was uneven due to partial degradation of the polymer, as shown in FIG. 6.

The principle of the invention is as follows: the polyol is reacted with 2- (ethyleneoxy) ethyl acrylate, the reaction scheme is as follows:

the invention has the beneficial effects that: 1. the method has the advantages of cheap and easily-obtained raw materials, high reaction rate, mild reaction conditions and simple and easy operation;

2. the polyacrylate containing acetal bond obtained by the invention can be degraded into corresponding alcohol and acetaldehyde under acidic condition, and the degradation route is as follows:

3. the polyacrylate containing acetal bond obtained by the invention can provide a plurality of reactive sites, can generate crosslinking reaction with multi-sulfydryl, multi-amino and the like, and can be prepared into corresponding degradable materials, thus being relatively environment-friendly.

The above description is only a preferred embodiment of the present invention, and the protection scope of the present invention is not limited to the above embodiments, and all technical solutions belonging to the idea of the present invention belong to the protection scope of the present invention. It should be noted that modifications and embellishments within the scope of the invention may occur to those skilled in the art without departing from the principle of the invention, and are considered to be within the scope of the invention.