阅读说明：本技术 一种超高固含的羟基丙烯酸聚合物及其制备方法、应用 (Ultrahigh-solid-content hydroxyl acrylic polymer and preparation method and application thereof ) 是由 刘明星 孙学武 周静静 于 2020-12-28 设计创作，主要内容包括：本发明属于高分子材料制备技术领域,特别涉及一种超高固含的羟基丙烯酸聚合物及其制备方法、应用,所述的方法包括：(1)将聚乙二醇、甲基丙烯酸缩水甘油酯加入到四口烧瓶中,通氮气保护,搅拌并升温至溶剂回流,滴加混合单体D1与引发剂,然后在120℃保温反应1h；(2)继续滴加混合单体D2和引发剂,控制在2h滴完,然后在120℃保温反应1h；(3)升温至140℃,继续滴加混合单体D3和引发剂,控制在2h滴完,然后在140℃保温反应1h；(4)降温至50℃,用旋转真空蒸发器脱除少量溶剂和未完全反应的单体,滴加适量中和剂中和pH值至7.5-8.5,出料,即得羟基丙烯酸聚合物；本发明所制备的羟基丙烯酸聚合物的固含量高达98％。(The invention belongs to the technical field of high molecular material preparation, and particularly relates to a hydroxyl acrylic polymer with ultrahigh solid content, a preparation method and application thereof, wherein the method comprises the following steps: (1) adding polyethylene glycol and glycidyl methacrylate into a four-neck flask, introducing nitrogen for protection, stirring, heating until a solvent flows back, dropwise adding a mixed monomer D1 and an initiator, and then carrying out heat preservation reaction for 1h at 120 ℃; (2) continuously dropwise adding the mixed monomer D2 and the initiator, controlling the dropwise adding to be finished within 2h, and then carrying out heat preservation reaction at 120 ℃ for 1 h; (3) heating to 140 ℃, continuously dropwise adding the mixed monomer D3 and the initiator, controlling the dropwise adding to be finished within 2 hours, and then carrying out heat preservation reaction for 1 hour at 140 ℃; (4) cooling to 50 ℃, removing a small amount of solvent and incompletely reacted monomers by using a rotary vacuum evaporator, dropwise adding a proper amount of neutralizing agent to neutralize the pH value to 7.5-8.5, and discharging to obtain a hydroxyl acrylic polymer; the solid content of the hydroxyl acrylic polymer prepared by the invention is up to 98 percent.)

1. A preparation method of a hydroxyl acrylic polymer with ultrahigh solid content is characterized by comprising the following steps:

(1) adding polyethylene glycol and glycidyl methacrylate into a four-neck flask provided with a thermometer, a stirrer, a condensation reflux device and a constant pressure funnel, introducing nitrogen for protection, stirring, heating until a solvent is refluxed, dropwise adding a mixed solution of a mixed monomer D1 and an initiator, controlling the dropwise adding to be finished within 2 hours, and then carrying out heat preservation reaction for 1 hour at 120 ℃;

(2) continuously dropwise adding a mixed solution of a mixed monomer D2 and an initiator, controlling the dropwise adding to be finished within 2h, and then carrying out heat preservation reaction for 1h at 120 ℃;

(3) heating to 140 ℃, continuously dropwise adding a mixed solution of the mixed monomer D3 and the initiator, controlling the dropwise adding to be finished within 2 hours, and then carrying out heat preservation reaction for 1 hour at 140 ℃;

(4) cooling to 50 ℃, removing a small amount of solvent and incompletely reacted monomers by using a rotary vacuum evaporator, dropwise adding a proper amount of neutralizing agent to neutralize the pH value to 7.5-8.5, and discharging to obtain the hydroxyl acrylic polymer.

2. The method according to claim 1, wherein the mixed monomer D1, the mixed monomer D2 and the mixed monomer D3 are each a mixture of a hydrophilic acrylic monomer and a hydrophobic acrylic monomer;

and, wherein: in the mixed monomer D1, the hydrophilic acrylic monomer accounts for 60 wt% or more; in the mixed monomer D2, the hydrophobic acrylic acid monomer accounts for 60 wt% or more; in the mixed monomer D3, the hydrophilic acrylic monomer accounts for 70 wt% or more.

3. The method of claim 2, wherein the hydrophilic acrylic monomer is selected from one or more of acrylic acid, methyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, and acrylamide.

4. The method of claim 2, wherein the hydrophobic acrylic monomer is selected from one or more of methyl methacrylate, ethyl acrylate, butyl acrylate, cyclohexyl, acrylonitrile, and styrene.

5. The method of claim 1, wherein the polyethylene glycol is selected from the group consisting of polyethylene glycol 200 and polyethylene glycol 400.

6. The method of claim 1, wherein the initiator is di-tert-butyl peroxide (DTBP) or di-tert-amyl peroxide (DTAP).

7. The method of claim 1, wherein the neutralizing agent is at least one selected from the group consisting of triethylamine, triethanolamine, and dimethylethanolamine.

8. A hydroxyacrylic polymer prepared according to the process of any one of claims 1 to 7.

9. The use of the hydroxyacrylic acid polymer as claimed in claim 8, characterized in that the hydroxyacrylic acid polymer is dispersed in water, and then mixed with the curing agent according to the molar ratio NCO/OH 1.2-1.5 and stirred uniformly to obtain the coating.

Technical Field

The invention belongs to the technical field of preparation of high polymer materials, and particularly relates to a hydroxyl acrylic polymer with ultrahigh solid content, and a preparation method and application thereof.

Background

The hydroxyl acrylic acid aqueous dispersion is generally low in molecular weight and narrow in molecular weight distribution, and the weight average molecular weight Mw is 2000-10000. The synthesis process comprises the steps of uniformly mixing acrylate soft and hard monomers, functional monomers and non-functional monomers, adding an initiator to carry out free radical solution polymerization to generate a hydroxyl acrylic polymer, then neutralizing with amine, adding water to carry out high-speed shearing dispersion, and finally removing all or part of organic solvents to obtain the product. The aqueous dispersion with higher hydroxyl value can be prepared by the method, and the aqueous dispersion has good emulsification effect on a polyisocyanate curing agent, is beneficial to the compatibility of a hydroxyl component and an isocyanate component, so that the appearance of a coating film is good, and the crosslinking density of the coating film is improved to have excellent coating film performance.

The traditional solvent type acrylic resin is competitive with environment-friendly varieties such as water-based, high-solid, powder and photocuring, and the market share is gradually reduced. High-solid acrylic resins developed on the basis of conventional solvent-type resins have been rapidly developed. Compared with the traditional solvent-based paint, the high-solid acrylic resin greatly reduces the content of organic volatile matters in a paint system, saves curing energy consumption, has the characteristics of light color, light retention, color retention and weather resistance, convenient construction and the like, and becomes an important variety of high-grade paint resin. The traditional acrylic resin is a linear polymer obtained by free radical polymerization of ethylene monomers, has serious intermolecular entanglement at higher concentration, has higher movement resistance and shows higher flow viscosity, thereby bringing difficulty to the direct application of the acrylic resin. In addition, some active functional groups in the molecular structure are coated by long chains, so that the reaction activity is reduced due to steric hindrance. The solid content of the high-solid hydroxyl acrylic resin popularized in the market at present is generally 60-70%, and a mercaptan chain transfer agent is widely used in the synthesis process to reduce the molecular weight of the resin, so that the mercaptan odor in the product is difficult to remove.

It is known that graft polymers are one of the important means for realizing the functionalization of high molecular materials. The graft structure polymer has a small hydrodynamic volume and a low solution viscosity. Therefore, the preparation of the hydroxyl acrylic resin with the graft structure can obviously improve the solid content and reduce the use amount of the organic solvent. The preparation method mainly comprises three methods, namely a macromonomer method, a coupling method and an active center method, and in recent years, a novel method for synthesizing a comb-shaped polymer by using the macromonomer attracts attention. The macromonomer is a linear polymer having a polymerizable group at the terminal, and a graft copolymer having a uniform branched molecular weight can be obtained very conveniently by copolymerization of the macromonomer. The macromonomer is a polymer and has a polymerizable function, and generally speaking, it is a prepolymer having a polymerizable functional group such as a double bond (or a hydroxyl group or a carboxyl group) at the end of the main chain and having a molecular weight of several thousands to several tens of thousands. The synthesis of the macromer generally comprises: preparation of prepolymer and introduction of terminal functional groups. The prepolymer can be prepared by radical chain transfer polymerization and living polymerization, such as Atom Transfer Radical Polymerization (ATRP), Group Transfer Polymerization (GTP), etc. And the Catalytic Chain Transfer Polymerization (CCTP) adopts a high-efficiency Chain transfer catalyst (II-valent or III-valent cobalt complex) to prepare the methacrylate macromonomer with double bonds at the tail end in one step under mild reaction conditions. Therefore, it has been receiving attention in recent years. In addition, the Sanmu group of Jiangsu, China, filed for an invention patent named "improved hydroxy acrylic resin" on 19.6.2003, patent No. 03131971.8, published as 28.1.2004, and publication No. CN 1470539A. The invention provides a hydroxyl acrylic resin with excellent solvent resistance and oil resistance, which comprises a methacrylic monomer, an acrylic monomer, styrene, an initiator and a solvent copolymerization reaction, wherein at least one of the comonomers is a hydroxyl-containing monomer, and the hydroxyl-containing acrylic resin is characterized in that 3-10 wt% of acrylonitrile/or 5-12 wt% of methyl acrylate, 3-10 wt% of isobutyl methacrylate and/or 1.5-5 wt% of cyclohexyl methacrylate functional monomers are added in the copolymerization reaction. The copolymerized hydroxy acrylic resin has strong oil resistance (such as 0# diesel oil, 90# gasoline and the like) and solvent resistance (such as butanol, butyl ester and the like), and special requirements on oil resistance and solvent resistance are met. The invention has the characteristics of oil resistance, solvent resistance, simple process and low production cost.

Disclosure of Invention

Aiming at the defects in the prior art, one of the purposes of the invention is to provide a preparation method of a hydroxy acrylic polymer with ultrahigh solid content, and the solid content of the hydroxy acrylic polymer prepared by the method can reach more than 98%.

It is a second object of the present invention to provide an ultra-high solid content hydroxyacrylic acid polymer.

The third purpose of the invention is to provide the application of the hydroxyl acrylic polymer with ultrahigh solid content.

In order to achieve the above object, the present invention provides a method for preparing an ultra-high solid content hydroxyacrylic acid polymer, comprising the steps of:

(1) adding polyethylene glycol and glycidyl methacrylate into a four-neck flask provided with a thermometer, a stirrer, a condensation reflux device and a constant pressure funnel, introducing nitrogen for protection, stirring, heating until a solvent is refluxed, dropwise adding a mixed solution of a mixed monomer D1 and an initiator, controlling the dropwise adding to be finished within 2 hours, and then carrying out heat preservation reaction for 1 hour at 120 ℃;

(2) continuously dropwise adding a mixed solution of a mixed monomer D2 and an initiator, controlling the dropwise adding to be finished within 2h, and then carrying out heat preservation reaction for 1h at 120 ℃;

(3) heating to 140 ℃, continuously dropwise adding a mixed solution of the mixed monomer D3 and the initiator, controlling the dropwise adding to be finished within 2 hours, and then carrying out heat preservation reaction for 1 hour at 140 ℃;

(4) cooling to 50 ℃, removing a small amount of solvent and incompletely reacted monomers by using a rotary vacuum evaporator, dropwise adding a proper amount of neutralizing agent to neutralize the pH value to 7.5-8.5, and discharging to obtain the hydroxyl acrylic polymer.

In a further technical scheme, the mixed monomer D1, the mixed monomer D2 and the mixed monomer D3 are all a mixture of hydrophilic acrylic monomers and hydrophobic acrylic monomers;

and, wherein: in the mixed monomer D1, the hydrophilic acrylic monomer accounts for 60 wt% or more; in the mixed monomer D2, the hydrophobic acrylic acid monomer accounts for 60 wt% or more; in the mixed monomer D3, the hydrophilic acrylic monomer accounts for 70 wt% or more.

In a further technical scheme, the hydrophilic acrylic monomer is selected from more than one of acrylic acid, methyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate and acrylamide.

In a further technical scheme, the hydrophobic acrylic monomer is selected from more than one of methyl methacrylate, ethyl acrylate, butyl acrylate, cyclohexyl, acrylonitrile and styrene.

In a further embodiment, the polyethylene glycol is selected from polyethylene glycol 200 or polyethylene glycol 400.

In a further technical scheme, the initiator is di-tert-butyl peroxide (DTBP) or di-tert-amyl peroxide (DTAP).

In a further technical scheme, the neutralizing agent is selected from at least one of triethylamine, triethanolamine and dimethylethanolamine.

The hydroxyl acrylic polymer with ultrahigh solid content is prepared according to the preparation method.

The application of the hydroxyl acrylic polymer with ultrahigh solid content is characterized in that the hydroxyl acrylic polymer is dispersed by adding water, and then is mixed with a curing agent according to the molar ratio of NCO/OH (1.2-1.5) and stirred uniformly to obtain the coating. The curing agent is selected from one of Bayer 2547 and Bayer 2655.

According to the technical scheme, polyethylene glycol and glycidyl methacrylate are used as a priming solvent, so that the priming solvent not only plays a role of a solvent, but also can participate in a polymerization reaction, and the solid content of the hydroxyl acrylic polymer prepared by the invention is up to 98%; furthermore, the acrylic monomers selected in the invention are monomers containing hydroxyl/carboxyl, are easy to disperse when used, are matched with a water-based curing agent for use, have excellent film forming effect, and are particularly high in fullness, the glossiness can reach 60 degrees and above, and the hardness can reach 2H.

Additional features and advantages of the invention will be set forth in the detailed description which follows.

Detailed Description

The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.

The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.

The invention provides a preparation method of a hydroxyl acrylic polymer with ultrahigh solid content, which comprises the following steps:

(1) adding polyethylene glycol and glycidyl methacrylate into a four-neck flask provided with a thermometer, a stirrer, a condensation reflux device and a constant pressure funnel, introducing nitrogen for protection, stirring, heating until a solvent is refluxed, dropwise adding a mixed solution of a mixed monomer D1 and an initiator, controlling the dropwise adding to be finished within 2 hours, and then carrying out heat preservation reaction for 1 hour at 120 ℃;

(2) continuously dropwise adding a mixed solution of a mixed monomer D2 and an initiator, controlling the dropwise adding to be finished within 2h, and then carrying out heat preservation reaction for 1h at 120 ℃;

(3) heating to 140 ℃, continuously dropwise adding a mixed solution of the mixed monomer D3 and the initiator, controlling the dropwise adding to be finished within 2 hours, and then carrying out heat preservation reaction for 1 hour at 140 ℃;

(4) cooling to 50 ℃, removing a small amount of solvent and incompletely reacted monomers by using a rotary vacuum evaporator, dropwise adding a proper amount of neutralizing agent to neutralize the pH value to 7.5-8.5, and discharging to obtain the hydroxyl acrylic polymer.

The mixed monomer D1, the mixed monomer D2 and the mixed monomer D3 are all mixtures of hydrophilic acrylic monomers and hydrophobic acrylic monomers; and, wherein: in the mixed monomer D1, the hydrophilic acrylic monomer accounts for 60 wt% or more; in the mixed monomer D2, the hydrophobic acrylic acid monomer accounts for 60 wt% or more; in the mixed monomer D3, the hydrophilic acrylic monomer accounts for 70 wt% or more.

Further, according to the method provided by the present invention, the kind of the hydrophilic acrylic monomer is not particularly limited, and may be specifically selected from at least one of acrylic acid, methyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate and acrylamide.

According to the method provided by the invention, the type of the hydrophobic acrylic monomer is not particularly limited, and the hydrophobic acrylic monomer can be selected from more than one of methyl methacrylate, ethyl acrylate, butyl acrylate, cyclohexyl, acrylonitrile and styrene.

In the invention, the polyethylene glycol is selected from polyethylene glycol 200 or polyethylene glycol 400.

The initiator is di-tert-butyl peroxide (DTBP) or di-tert-amyl peroxide (DTAP).

The neutralizing agent is at least one of triethylamine, triethanolamine and dimethylethanolamine.

The preparation method of the ultra-high solid content hydroxyacrylic acid polymer provided by the present invention is further illustrated by the following specific examples.

Example 1

A method for preparing a hydroxyacrylic acid polymer, comprising the steps of:

(1) adding 12 parts of polyethylene glycol 200 and 20 parts of glycidyl methacrylate into a four-neck flask provided with a thermometer, a stirrer, a condensation reflux device and a constant pressure funnel, introducing nitrogen for protection, stirring and heating until a solvent is refluxed, dropwise adding a mixed solution of a mixed monomer D1 and 0.2 part of initiator di-tert-butyl peroxide, controlling the dropping within 2 hours, and then carrying out heat preservation reaction at 120 ℃ for 1 hour;

(2) continuously dropwise adding a mixed solution of a mixed monomer D2 and 0.4 part of initiator di-tert-butyl peroxide, controlling the dropwise addition within 2 hours, and then carrying out heat preservation reaction at 120 ℃ for 1 hour;

(3) heating to 140 ℃, continuously dropwise adding a mixed solution of a mixed monomer D3 and 0.6 part of initiator di-tert-butyl peroxide, controlling the dropwise addition within 2 hours, and then carrying out heat preservation reaction at 140 ℃ for 1 hour;

(4) cooling to 50 ℃, removing a small amount of solvent and incompletely reacted monomers by using a rotary vacuum evaporator, dropwise adding a proper amount of 2 parts of neutralizing agent triethylamine to neutralize the pH value to 8.0, and discharging to obtain the hydroxyl acrylic polymer.

Wherein the mixed monomer D1 comprises 2 parts of acrylic acid, 3 parts of methyl acrylate, 7 parts of hydroxyethyl methacrylate and 3 parts of methyl methacrylate; the mixed monomer D2 comprises 11 parts of methyl methacrylate, 6 parts of ethyl acrylate, 3 parts of acrylonitrile and 5 parts of methyl acrylate; the mixed monomer D3 contains 9 parts of hydroxyethyl methacrylate, 5 parts of acrylamide and 4 parts of butyl acrylate.

Example 2

This example is essentially the same as the preparation of the hydroxyacrylic acid polymer in example 1, except that, among the starting materials used in the preparation:

2008 parts of polyethylene glycol;

26 parts of glycidyl methacrylate;

the mixed monomer D1 comprises 6 parts of acrylic acid, 12 parts of hydroxypropyl methacrylate and 3 parts of butyl acrylate, and 0.2 part of di-tert-butyl peroxide corresponding to the mixed monomer D1;

the mixed monomer D2 contains 12 parts of methyl methacrylate, 7 parts of acrylonitrile and 6 parts of methyl acrylate; 0.5 part of di-tert-butyl peroxide corresponding to the mixed monomer D2;

the mixed monomer D3 contains 5 parts of methyl acrylate, 6 parts of hydroxypropyl methacrylate, 3 parts of acrylamide and 6 parts of acrylonitrile; 0.8 part of di-tert-butyl peroxide corresponding to the mixed monomer D3;

3 parts of neutralizing agent triethylamine;

the rest is unchanged, and the hydroxyl acrylic polymer is prepared.

Example 3

This example is essentially the same as the preparation of the hydroxyacrylic acid polymer in example 1, except that, among the starting materials used in the preparation:

20014 parts of polyethylene glycol;

16 parts of glycidyl methacrylate;

the mixed monomer D1 comprises 7 parts of methyl acrylate, 9 parts of hydroxypropyl methacrylate, 2 parts of acrylamide and 5 parts of styrene, and the initiator corresponding to the mixed monomer D1 is di-tert-amyl peroxide and is used in an amount of 0.5 part;

the mixed monomer D2 comprises 10 parts of butyl acrylate, 3 parts of acrylonitrile, 6 parts of styrene and 8 parts of acrylic acid; and the initiator corresponding to the mixed monomer D2 is di-tert-amyl peroxide, and the using amount is 0.7 part;

the mixed monomer D3 comprises 3 parts of acrylic acid, 5 parts of hydroxyethyl methacrylate, 2 parts of acrylamide and 4 parts of styrene; and the initiator corresponding to the mixed monomer D3 is di-tert-amyl peroxide, and the using amount is 0.8 part;

the neutralizer is triethanolamine, and the dosage is 2 parts;

the rest is unchanged, and the hydroxyl acrylic polymer is prepared.

Example 4

This example is essentially the same as the preparation of the hydroxyacrylic acid polymer in example 1, except that, among the starting materials used in the preparation:

20010 parts of polyethylene glycol;

22 parts of glycidyl methacrylate;

the mixed monomer D1 comprises 2 parts of acrylic acid, 1 part of methyl acrylate, 9 parts of hydroxyethyl methacrylate and 5 parts of cyclohexyl, and the initiator corresponding to the mixed monomer D1 is di-tert-amyl peroxide, and the using amount is 0.2 part;

the mixed monomer D2 contains 3 parts of methyl methacrylate, 9 parts of ethyl acrylate, 2 parts of styrene and 3 parts of methyl acrylate; and the initiator corresponding to the mixed monomer D2 is di-tert-amyl peroxide, and the using amount is 0.3 part;

the mixed monomer D3 comprises 4 parts of acrylic acid, 10 parts of hydroxyethyl methacrylate, 7 parts of acrylamide and 8 parts of ethyl acrylate; the initiator corresponding to the mixed monomer D3 is di-tert-amyl peroxide, and the using amount is 1 part;

the neutralizer is dimethylethanolamine, and the using amount is 3 parts;

the rest is unchanged, and the hydroxyl acrylic polymer is prepared.

In the invention, the neutralizer Triethylamine (TEA) is chemically pure and is purchased from chemical reagents of national drug group, Inc.;

the monomers are all industrial products, and are produced in the Beijing Oriental chemical industry;

polyethylene glycol, industrial products, Jiangsu Haian petrochemical plants;

initiator, analytically pure, cheng rui chemical limited, denna.

And (3) performance testing:

1. the solid contents of the hydroxyacrylic polymers prepared in examples 1 to 4 were measured according to the regulations of GB/T2793-.

2. Application example: the hydroxy acrylic polymer prepared in the above examples 1 to 4 was dispersed in water, and then mixed with a curing agent at a molar ratio NCO/OH of 1.5 and stirred uniformly to obtain a coating; the curing agent is selected from Bayer 2547.

Specifically, 110 parts by weight of a hydroxyacrylic acid polymer, 12 parts by weight of water and 25477 parts by weight of a curing agent were used to prepare a varnish, the varnish was coated on a clean glass plate, the thickness of the coating film was 20 μm, the varnish was dried at room temperature for 7 days, and the performance was tested and the test results were summarized in table 1.

Table 1:

	example 1	Example 2	Example 3	Example 4
					Solid content	98％	98％	98％	99％
Gloss/60 °	94	95	93	95
					Hardness of	2H	2H	2H	2H

The test data show that the solid content of the hydroxyl acrylic polymer provided by the invention is up to 98% or more, and the glossiness can reach 60 degrees or more and the hardness can reach 2H after the hydroxyl acrylic polymer is matched with a water-based curing agent for use.

The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.

It should be noted that the various features described in the above embodiments may be combined in any suitable manner without departing from the scope of the invention. The invention is not described in detail in order to avoid unnecessary repetition.

In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.