阅读说明：本技术 一种羟基丙烯酸树脂的连续生产方法 (Continuous production method of hydroxyl acrylic resin ) 是由 李小龙 娄智兴 葛源 王威 芦潇 肖淑焕 焦玉坤 刘太恩 于 2020-12-29 设计创作，主要内容包括：本发明涉及一种羟基丙烯酸树脂的连续生产方法。本发明的连续生产方法采用羟基丙烯酸树脂的连续生产装置,在不增加原料成本的基础上,实现羟基丙烯酸树脂连续生产,并稳定获得高品质的羟基丙烯酸树脂产品,提高了生产效率以及生产过程的安全性。(The invention relates to a continuous production method of hydroxyl acrylic resin. The continuous production method of the invention adopts the continuous production device of the hydroxyl acrylic resin, realizes the continuous production of the hydroxyl acrylic resin on the basis of not increasing the cost of raw materials, stably obtains high-quality hydroxyl acrylic resin products, and improves the production efficiency and the safety of the production process.)

1. A continuous production method of hydroxyl acrylic resin is characterized in that the continuous production method is carried out in a continuous production device which comprises a material mixing system (1), a material conveying system (2), a polymerization reaction unit (3), a receiving unit (4) and a heat exchange system,

wherein the outlet of the mixing system (1) is connected with the inlet of the material conveying system (2), the outlet of the material conveying system (2) is connected with the inlet of the polymerization reaction unit (3), the outlet of the polymerization reaction unit (3) is connected with the inlet of the receiving unit (4),

the heat exchange system comprises a reaction temperature control system (5) and a material heat exchange system, the material heat exchange system comprises a first material heat exchange system (6-1) and a second material heat exchange system (6-2), and the solid content of the hydroxyl acrylic resin is 50-90%.

2. The continuous production method according to claim 1, wherein the mixing system (1) comprises at least a first mixer (1-1), a second mixer (1-2) and optionally a third mixer (1-3), the first mixer (1-1), the second mixer (1-2) and the third mixer (1-3) being used to mix a first mixed solution, a second mixed solution and a third mixed solution, respectively, wherein the first mixed solution comprises a part or all of the monomers, the second mixed solution comprises a part or all of the initiators, and the third mixed solution comprises one or more of the monomers, the solvent and the initiator.

3. The continuous production process according to claim 1 or 2, wherein the polymerization reaction unit (3) is a continuous channel reactor in any combination of a microchannel reactor and a tubular reactor.

4. The continuous production method according to claim 2, wherein the first material heat exchange system (6-1) is used for primary cooling of the hydroxyl acrylic resin and preheating of the first mixed solution, and the second material heat exchange system (6-2) is used for secondary cooling of the hydroxyl acrylic resin and preheating of the second mixed solution; the temperature of the hydroxyl acrylic resin is reduced to 70-100 ℃ through the first stage, the first mixed solution is preheated to 110-200 ℃, the temperature of the hydroxyl acrylic resin is reduced to 55-75 ℃ through the second stage, and the second mixed solution is preheated to 70-100 ℃.

5. The continuous production method according to claim 1, wherein an outlet of the mixing system (1) is connected with an inlet of the material conveying system (2), an outlet of the material conveying system (2) is connected with an inlet of mixed liquor of the material heat exchange system, an outlet of the mixed liquor of the material heat exchange system is connected with an inlet of the polymerization reaction unit (3), an outlet of the polymerization reaction unit (3) is connected with a resin inlet of the material heat exchange system, and a resin outlet of the material heat exchange system is connected with an inlet of the receiving unit (4).

6. The continuous production method according to claim 1 or 2, characterized in that the mixing system (1) comprises at least a first mixer (1-1), a second mixer (1-2) and optionally a third mixer (1-3), the continuous production method comprising the steps of:

step 1: respectively feeding a monomer to be mixed, a solvent and an initiator into a first mixer (1-1), a second mixer (1-2) and an optional third mixer (1-3) for premixing to obtain a first mixed solution, a second mixed solution and an optional third mixed solution; the first mixed solution comprises a part or all of monomers, the second mixed solution comprises a part or all of initiators, and the third mixed solution comprises one or more of monomers, solvents and initiators;

step 2: continuously conveying the first mixed solution and the second mixed solution to the material heat exchange system through the material conveying system (2), preheating the first mixed solution and the second mixed solution in the material heat exchange system, then feeding the first mixed solution and the second mixed solution into the polymerization reaction unit (3), continuously conveying an optional third mixed solution to the polymerization reaction unit (3) through the material conveying system (2), and reacting the first mixed solution, the second mixed solution and the optional third mixed solution at the temperature of 160-230 ℃ and the pressure of 1-5 MPa for a total residence time of 1-20 min to obtain a hydroxyl acrylic resin;

and step 3: and hydroxyl acrylic resin flowing out of the polymerization reaction unit (3) enters the material heat exchange system to be cooled and then enters the receiving unit (4).

7. The continuous production method according to claim 6, wherein the first mixed liquid and the second mixed liquid are continuously conveyed to a first material heat exchange system (6-1) and a second material heat exchange system (6-2) respectively through the material conveying system (2), and enter the polymerization reaction unit (3) after the first material heat exchange system (6-1) and the second material heat exchange system (6-2) are preheated respectively;

the temperature of the hydroxyl acrylic resin is reduced to 70-100 ℃ through the first stage of the material heat exchange system, and the temperature of the hydroxyl acrylic resin is reduced to 55-75 ℃ through the second stage of the material heat exchange system; the first mixed liquid is preheated to 110-200 ℃ through the material heat exchange system, and the second mixed liquid is preheated to 70-100 ℃ through the material heat exchange system.

8. The continuous production method according to claim 2, wherein the monomers include a hydroxyl monomer, a carboxyl monomer, a hard monomer and a soft monomer,

the hydroxyl monomer is one or more of hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate and hydroxybutyl acrylate,

the carboxyl monomer is at least one of acrylic acid and methacrylic acid,

the hard monomer is one or more of styrene, methyl acrylate, methyl methacrylate, ethyl methacrylate and isobornyl acrylate,

the soft monomer is one or more of ethyl acrylate, isooctyl methacrylate, butyl acrylate, butyl methacrylate and lauryl acrylate,

the mass of the hydroxyl monomer accounts for 12-40% of the total mass of the monomers, the mass of the carboxyl monomer accounts for 0.1-3.8% of the total mass of the monomers, and the mass of the hard monomer and the mass of the soft monomer both account for 20-60% of the total mass of the monomers.

9. The continuous production method according to claim 2, wherein the mass ratio of the monomer, the solvent and the initiator is 45 to 89:10 to 50:1 to 5.

10. The continuous production method according to claim 2, wherein the solvent is one or more of propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol butyl ether, propylene glycol methyl ether acetate, ethylene glycol ethyl ether acetate, toluene, xylene, mineral spirits No. 100, butyl acetate, isobutyl acetate, n-butanol, and isobutanol;

the initiator is at least one of di-tert-butyl peroxide, di-tert-amyl peroxide, diisopropyl peroxide, tert-butyl peroxyacetate, tert-butyl cumyl peroxide and di-tert-butyl diisopropylperoxide.

Technical Field

The invention relates to a production method of hydroxyl acrylic resin, in particular to a continuous production method of hydroxyl acrylic resin.

Background

After the hydroxyl acrylic resin and the isocyanate curing agent act, the coating has the properties of high hardness, high gloss, high fullness, excellent adhesion, leveling property, toughness, weather resistance, corrosion resistance, quick drying and the like, can be used for preparing PU (polyurethane) two-component paint, automobile refinishing paint, wood furniture polyester paint, mechanical finish, high-gloss finish, finishing paint, varnish, colored paint and the like, and is widely applied to the fields of automobiles, machinery, furniture and the like.

Many studies on the synthesis of the hydroxy acrylic resin are limited to a mode of slowly dropwise reacting at a lower reaction temperature and then keeping the temperature for a longer time, and the quality of the hydroxy acrylic resin directly obtained by the mode is often poor, and filtration treatment is needed before packaging. The preparation method of the hydroxy acrylic resin disclosed in CN104231148A comprises the following steps: adding a part of solvent into a reaction kettle in advance, heating to a reflux temperature, dropwise adding a mixture of a first part of monomer, a chain transfer agent and an initiator at a temperature of not higher than 130 ℃ for 2-5 h, then preserving heat for 1-2 h, dropwise adding the rest of initiator and solvent for 0.5-1 h, continuing to react for 2-4 h, finally cooling to below 70 ℃, and filtering to obtain the hydroxyl acrylic resin. The preparation method of the hydroxy acrylic resin disclosed in CN102766263B comprises the following steps: the method comprises the steps of adding a mixture with a solvent as a main component into a reaction kettle in advance, controlling the reaction temperature to be 105-115 ℃, dropwise adding a monomer and a catalyst for 3-4 hours, then preserving heat for 0.5-2 hours at 100-120 ℃, heating to 115-125 ℃, dropwise adding the catalyst, then preserving heat for 4.5-6.5 hours, dropwise adding a mixed solution containing the solvent, preserving heat for 1.5-2.5 hours, finally cooling to below 75 ℃, and filtering to obtain the hydroxyl acrylic resin.

Raising the reaction temperature to some extent is advantageous in reducing the molecular weight of the polymer and reducing the viscosity of the resin, thereby obtaining a hydroxy acrylic resin having a higher solid content and enabling a reduction in the reaction time. However, although the reaction time can be shortened by raising the reaction temperature, the dropping speed is controlled to prolong the dropping time in order to avoid runaway reaction. CN106084143B discloses a preparation process of low VOC hydroxy acrylic resin, which comprises the following steps: adding a part of mixed solution containing a solvent in advance into a high-pressure reaction kettle, heating to 150-170 ℃, controlling the pressure to be 0.1-0.3 MPa, stabilizing for 10-30 min, dropwise adding the mixed solution of a monomer and an initiator for 3-6 h, dropwise adding a mixture of the initiator and the solvent twice, respectively keeping the temperature for 30-90 min and 3-5 h after dropwise adding, finally cooling to below 70 ℃, and filtering to obtain the hydroxyl acrylic resin. Although the high-pressure reaction kettle can be used for obtaining the hydroxy acrylic resin with higher solid content at higher temperature, the high-temperature and high-pressure operation is high in danger and the reaction is not easy to control due to the larger volume of the reaction kettle in the production process, and the obtained hydroxy acrylic resin is often required to be filtered. CN106009454B discloses a preparation method of a high-solid-content low-viscosity hydroxy acrylic resin, which comprises the following steps: adding a part of solvent and monoglycidyl ether into a reaction kettle in advance, stirring and heating to 140-180 ℃, dropwise adding a mixture of an initiator, a chain transfer agent and a monomer for 3-6 h, then preserving heat for 0.5-1 h, dropwise adding the rest of initiator and solvent for 20-40 min, and continuously preserving heat for reacting for 1-2 h to obtain the hydroxyl acrylic resin. However, in order to increase the solid content of the resin, more substances with stronger hydrophilicity and viscosity reduction, such as monoglycidyl ether, vinyl versatate and hydroxyl oligomer, are added in the formula, and although the obtained hydroxyl acrylic resin achieves the effects of high solid content and low viscosity, the cost of resin raw materials is increased, and a coating film prepared by the resin is softer and has poor corrosion resistance and water resistance.

Although the reaction temperature is continuously improved in the synthesis research of the hydroxyl acrylic resin, and the temperature and the time of the dropping reaction and the heat preservation reaction are adjusted, the highest reaction temperature does not exceed 180 ℃, the time of the dropping reaction and the heat preservation reaction is longer as a whole, and a great amplification effect exists from a small test to industrialization. The reason is that the heat is released in the synthesis process of the hydroxyl acrylic resin, the polymerization monomer is initiated by an initiator and reacts violently, if the reaction temperature is too high, the heat generated in the reaction process cannot be removed in time, the product quality is reduced if the reaction temperature is too high, implosion occurs if the reaction temperature is too low, and the risk of explosion during high-temperature and high-pressure operation is high, so that the high-temperature reaction is difficult to realize in the production of the existing hydroxyl acrylic resin. Therefore, the batch kettle type process has the problems of complicated operation process, low production efficiency and poor safety.

Disclosure of Invention

Problems to be solved by the invention

As analyzed in the background technology of the invention, the existing production of hydroxyl acrylic resin has the problems of complicated operation process, low production efficiency and poor safety. In order to solve the problems in the prior art, the invention adopts a continuous production device of the hydroxyl acrylic resin, realizes the continuous production of the hydroxyl acrylic resin on the basis of not increasing the cost of raw materials, stably obtains high-quality hydroxyl acrylic resin products, and improves the production efficiency and the safety of the production process.

Means for solving the problems

[1] A continuous production method of hydroxyl acrylic resin, wherein the continuous production method is carried out in a continuous production device, the continuous production device comprises a material mixing system 1, a material conveying system 2, a polymerization reaction unit 3, a receiving unit 4 and a heat exchange system,

wherein the outlet of the mixing system 1 is connected with the inlet of the material conveying system 2, the outlet of the material conveying system 2 is connected with the inlet of the polymerization reaction unit 3, the outlet of the polymerization reaction unit 3 is connected with the inlet of the receiving unit 4,

the heat exchange system comprises a reaction temperature control system 5 and a material heat exchange system, the material heat exchange system comprises a first material heat exchange system 6-1 and a second material heat exchange system 6-2, and the solid content of the hydroxyl acrylic resin is 50-90%.

[2] The continuous production method according to [1], wherein the mixing system 1 comprises at least a first mixer 1-1, a second mixer 1-2 and optionally a third mixer 1-3, the first mixer 1-1, the second mixer 1-2 and the third mixer 1-3 are used for mixing a first mixed solution, a second mixed solution and a third mixed solution respectively, the first mixed solution contains part or all of the monomers, the second mixed solution contains part or all of the initiators, and the third mixed solution contains one or more of the monomers, the solvents and the initiators.

[3] The continuous production process according to [1] or [2], wherein the polymerization reaction unit 3 is a continuous channel reactor in which a microchannel reactor and a tubular reactor are arbitrarily combined.

[4] The continuous production method according to the item [2], wherein the first material heat exchange system 6-1 is used for primary temperature reduction of the hydroxyl acrylic resin and preheating of the first mixed solution, and the second material heat exchange system 6-2 is used for secondary temperature reduction of the hydroxyl acrylic resin and preheating of the second mixed solution; the temperature of the hydroxyl acrylic resin is reduced to 70-100 ℃ through the first stage, the first mixed solution is preheated to 110-200 ℃, the temperature of the hydroxyl acrylic resin is reduced to 55-75 ℃ through the second stage, and the second mixed solution is preheated to 70-100 ℃.

[5] The continuous production method according to [1], wherein an outlet of the mixing system 1 is connected with an inlet of the material conveying system 2, an outlet of the material conveying system 2 is connected with a mixed liquid inlet of the material heat exchange system, a mixed liquid outlet of the material heat exchange system is connected with an inlet of the polymerization reaction unit 3, an outlet of the polymerization reaction unit 3 is connected with a resin inlet of the material heat exchange system, and a resin outlet of the material heat exchange system is connected with an inlet of the receiving unit 4.

[6] The continuous production method according to [1] or [2], wherein the mixing system 1 comprises at least a first mixer 1-1, a second mixer 1-2 and optionally a third mixer 1-3, the continuous production method comprising the steps of:

step 1: respectively feeding a monomer to be mixed, a solvent and an initiator into a first mixer 1-1, a second mixer 1-2 and an optional third mixer 1-3 for premixing to obtain a first mixed solution, a second mixed solution and an optional third mixed solution; the first mixed solution comprises a part or all of monomers, the second mixed solution comprises a part or all of initiators, and the third mixed solution comprises one or more of monomers, solvents and initiators;

step 2: continuously conveying the first mixed solution and the second mixed solution to the material heat exchange system through the material conveying system 2, preheating the first mixed solution and the second mixed solution in the material heat exchange system, then feeding the first mixed solution and the second mixed solution into the polymerization reaction unit 3, continuously conveying an optional third mixed solution to the polymerization reaction unit 3 through the material conveying system (2), and reacting the first mixed solution, the second mixed solution and the optional third mixed solution at the temperature of 160-230 ℃ and the pressure of 1-5 MPa for a total residence time of 1-20 min to obtain hydroxyl acrylic resin;

and step 3: and hydroxyl acrylic resin flowing out of the polymerization reaction unit 3 enters the material heat exchange system to be cooled and then enters the receiving unit 4.

[7] The continuous production method according to [6], wherein the first mixed liquid and the second mixed liquid are respectively and continuously conveyed to a first material heat exchange system 6-1 and a second material heat exchange system 6-2 through the material conveying system 2, and enter the polymerization reaction unit 3 after the first material heat exchange system 6-1 and the second material heat exchange system 6-2 are preheated respectively;

the temperature of the hydroxyl acrylic resin is reduced to 70-100 ℃ through the first stage of the material heat exchange system, and the temperature of the hydroxyl acrylic resin is reduced to 55-75 ℃ through the second stage of the material heat exchange system; the first mixed liquid is preheated to 110-200 ℃ through the material heat exchange system, and the second mixed liquid is preheated to 70-100 ℃ through the material heat exchange system.

[8] The continuous production process according to [2], wherein the monomers comprise a hydroxyl monomer, a carboxyl monomer, a hard monomer and a soft monomer,

the hydroxyl monomer is one or more of hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate and hydroxybutyl acrylate,

the carboxyl monomer is at least one of acrylic acid and methacrylic acid,

the hard monomer is one or more of styrene, methyl acrylate, methyl methacrylate, ethyl methacrylate and isobornyl acrylate,

the soft monomer is one or more of ethyl acrylate, isooctyl methacrylate, butyl acrylate, butyl methacrylate and lauryl acrylate,

the mass of the hydroxyl monomer accounts for 12-40% of the total mass of the monomers, the mass of the carboxyl monomer accounts for 0.1-3.8% of the total mass of the monomers, and the mass of the hard monomer and the mass of the soft monomer both account for 20-60% of the total mass of the monomers.

[9] The continuous production method according to [2], wherein the mass ratio of the monomer to the solvent to the initiator is 45-89: 10-50: 1-5.

[10] The continuous production process according to [2], wherein the solvent is one or more selected from propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol butyl ether, propylene glycol methyl ether acetate, ethylene glycol ethyl ether acetate, toluene, xylene, No. 100 solvent oil, butyl acetate, isobutyl acetate, n-butanol and isobutanol;

the initiator is at least one of di-tert-butyl peroxide, di-tert-amyl peroxide, diisopropyl peroxide, tert-butyl peroxyacetate, tert-butyl cumyl peroxide and di-tert-butyl diisopropylperoxide.

ADVANTAGEOUS EFFECTS OF INVENTION

1. Compared with the existing intermittent kettle type production method, the continuous production method of the hydroxy acrylic resin provided by the invention not only realizes continuous automatic production and obtains the hydroxy acrylic resin with stable quality, but also obviously improves the production efficiency by adopting a continuous production device and a high-temperature reaction mode. In addition, the continuous automatic production saves the feeding and discharging process of an intermittent kettle type process and the filtering process added before the product is collected due to poor or unstable product quality, simplifies the operation procedure, ensures higher safety by remote precise control, and can realize the continuous production of the hydroxyl acrylic resin with the solid content of 50-90%.

2. Compared with the prior art, the continuous production method of the hydroxyl acrylic resin provided by the invention is additionally provided with a material heat exchange system, realizes the preheating of the mixed liquid in the process of cooling the hot hydroxyl acrylic resin obtained by reaction, realizes the comprehensive utilization of energy, and reduces the waste of energy compared with the direct cooling of the hydroxyl acrylic resin.

Drawings

FIG. 1 is a schematic view of one embodiment of the continuous production process of a hydroxyacrylic resin according to the present invention.

FIG. 2 is a schematic view of another embodiment of the continuous production process of a hydroxyacrylic resin according to the present invention.

Description of the reference numerals

1. The system comprises a material mixing system, 1-1 parts of a first material mixer, 1-2 parts of a second material mixer, 1-3 parts of a third material mixer, 2 parts of a material conveying system, 3 parts of a polymerization reaction unit, 4 parts of a receiving unit, 5 parts of a reaction temperature control system, 6-1 parts of a first material heat exchange system and 6-2 parts of a second material heat exchange system

Detailed Description

The present invention will be described in detail below with reference to the accompanying drawings. It should be understood that the drawings described herein are not to be construed as limiting the scope of the invention.

The invention provides a continuous production method of hydroxyl acrylic resin, which is characterized in that the continuous production method is carried out in a continuous production device, the continuous production device comprises a mixing system 1, a material conveying system 2, a polymerization reaction unit 3, a receiving unit 4 and a heat exchange system, wherein an outlet of the mixing system 1 is connected with an inlet of the material conveying system 2, an outlet of the material conveying system 2 is connected with an inlet of the polymerization reaction unit 3, an outlet of the polymerization reaction unit 3 is connected with an inlet of the receiving unit 4, the heat exchange system comprises a reaction temperature control system 5 and a material heat exchange system, the material heat exchange system comprises a first material heat exchange system 6-1 and a second material heat exchange system 6-2, and the solid content of the hydroxyl acrylic resin is 50-90%.

In the invention, each system and unit in the continuous production device for producing the hydroxyl acrylic resin are connected with the automatic control system, and the continuous automatic production of the hydroxyl acrylic resin can be realized by adopting automatic operation.

In the present invention, it should be noted that, unless explicitly stated or limited, the connection between each system and the unit should be understood in a broad sense, for example, it may be a direct pipe connection, a pipe connection connected with a pipe valve, an indirect connection through an intermediate medium, a fixed connection, or a detachable connection. The specific meaning of the above terms in the present invention can be understood by those skilled in the art according to specific situations.

The mixing system 1 at least comprises a first mixer 1-1, a second mixer 1-2 and an optional third mixer 1-3, wherein the first mixer 1-1, the second mixer 1-2 and the third mixer 1-3 are respectively used for mixing a first mixed solution, a second mixed solution and a third mixed solution, the first mixed solution contains part or all of monomers, the second mixed solution contains part or all of initiators, and the third mixed solution contains one or more of monomers, solvents and initiators.

The first blender 1-1, the second blender 1-2 and the third blender 1-3 are preferably stirred tanks.

In the invention, the mixer is used for premixing materials which do not react with each other at normal temperature, and a plurality of strands of materials are formed into a strand of material which is then conveyed to the polymerization reaction unit 3 through the material conveying system 2, thereby achieving the purpose of saving the input cost of equipment. The first material mixer 1-1 is used for mixing the monomers or mixing the monomers and the solvent, and the second material mixer 1-2 is used for mixing the solvent and the initiator or mixing the monomers and the solvent and the initiator. Accordingly, the first mixed solution may include a monomer or a monomer and a solvent, and the second mixed solution may include an initiator or an initiator and a solvent or an initiator and a monomer or an initiator, a solvent and a monomer. In one embodiment of the present invention, the third mixer 1-3 is configured to pre-mix the third mixed liquid, and the third mixed liquid is configured to convey the materials to the polymerization reaction unit 3 in stages, so as to increase the conversion rate of the monomers, reduce the viscosity of the resin, avoid the concentrated heat release of the reaction to a certain extent, and reduce the workload of the reaction temperature control system. In the present invention, the third mixers 1 to 3 are optionally used, and accordingly, the third mixed liquor is also optionally present.

In the present invention, the material conveying system 2 is used for realizing the continuous conveying of the materials and providing power for the flowing of the materials in the continuous production device. Because the polymerization reaction unit 3 in the continuous production device adopts a plug flow continuous channel reactor, the only power source is the material conveying system 2, and because the material generates certain resistance in the flowing process, certain pressure drop is generated; in addition, because the temperature in the reaction process is higher than the boiling point of the solvent and part of the monomers, a certain pressure needs to be provided in order to prevent the materials from vaporizing. Therefore, in order to realize smooth passage of the material to the receiving unit 4 after entering the polymerization reaction unit 3, the material conveying system 2 preferably comprises at least two feed pumps having a pressure-resistant range, and the upper pressure-resistant limit of the feed pumps is not lower than 2 MPa. If the upper limit of the pressure resistance of the feed pump is lower than 2MPa, the power provided during the material conveying process is limited, which may result in that the product cannot smoothly enter the receiving unit 4, or the feeding is stopped because the pressure of the entire continuous production apparatus is higher than the upper limit of the pressure of the feed pump.

In the present invention, the polymerization reaction unit 3 of the apparatus for continuously producing a hydroxyacrylic resin is a continuous channel reactor, which is preferably any combination of a microchannel reactor and a tubular reactor.

The tubular reactor comprises a static tubular reactor and a dynamic tubular reactor, the static tubular reactor comprises a static tubular reactor (also called static mixer) with a mixing unit in a tubular cavity and a static tubular reactor without the mixing unit in the tubular cavity, and the dynamic tubular reactor is a tubular reactor with a moving part in the tubular cavity.

Both microchannel reactors and tubular reactors referred to in the present invention are commercially available. According to the general knowledge of the technical personnel in the field, the continuous channel reactor has excellent mass transfer and heat transfer effects and is practically applied in the field of chemical production, and the heat release quantity in the reaction process and the effective volume of the reactor can be calculated by simulation calculation according to the yield of the hydroxyl acrylic resin, so that the suitable reactor can be selected on the market.

The conventional batch kettle type reaction mostly adopts the method that a solvent is added into a reaction kettle in advance and preheated to a certain temperature, and then the monomer and the initiator are dripped for many times, and in order to ensure the controllable reaction and the product quality, a starvation method for reducing the dripping speed is adopted, so that the initiator with higher concentration is always kept in the monomer. However, in order to realize mass production, the reaction kettle adopted in general industrial production has a large volume, and although the stirring form is continuously improved, the phenomena of uneven mixing and severe back mixing always exist in the reaction kettle, which easily causes the phenomena of large difference of the polymerization degree of the resin, wide molecular weight distribution, and large viscosity and poor quality of the finally obtained resin product.

According to the invention, a large amount of experimental researches are carried out on the synthesis of the hydroxyl acrylic resin, and the purpose that a process of forced mass transfer is needed in the early stage of the reaction of the polymerization monomer and the initiator is found, so that the free radicals generated by the rapid decomposition of the initiator at high temperature can be uniformly contacted with the monomer, the monomer is uniformly subjected to polymerization reaction in the process of flowing in a reaction channel, a molecular chain with more concentrated molecular weight is formed, and the branching degree is reduced.

The invention adopts a micro-channel reactor with mixing function or a static mixer or a dynamic tubular reactor as a front-end reactor of a continuous channel reactor, so that mixed liquid containing one or more of monomers, solvents and initiators is quickly mixed and uniformly reacted after entering the front-end reactor of the continuous channel reactor. Preferably, the microchannel reactor or static mixer serves as a front-end reactor of the continuous channel reactor, more preferably, the microchannel reactor serves as a front-end reactor of the continuous channel reactor. In order to realize industrial mass production of the hydroxyacrylic resin and to reduce the equipment investment cost, a tubular reactor is preferable as the rear end reactor of the continuous channel reactor. The mixed liquid inlet of the polymerization reaction unit 3 is positioned on the front-end reactor of the continuous channel reactor, and the resin outlet of the polymerization reaction unit 3 is positioned on the rear-end reactor of the continuous channel reactor.

In one embodiment of the invention, the inlet for the third mixed liquor is located on a microchannel reactor or a static mixer or a dynamic tube reactor having a mixing function in a continuous channel reactor. In the present invention, the third mixed liquid may be introduced into the polymerization reaction unit 3 simultaneously with or after the first mixed liquid and the second mixed liquid are introduced into the polymerization reaction unit 3.

In the invention, the monomer polymerization is carried out at a higher temperature, the monomer polymerization process is an exothermic process, the polymerization reaction rate is higher at the higher reaction temperature, more heat is released in the reaction, and the reaction heat is timely removed while the temperature required by the reaction is provided by the reaction temperature control system 5. The reaction temperature control system 5 employed in the present invention controls at least one reaction temperature region of the polymerization reaction unit 3.

In addition, since the reaction temperature of the polymerization reaction unit 3 is high, the temperature of the hydroxy acrylic resin flowing out through the polymerization reaction unit 3 is high, and if the resin is directly cooled by an external cooling system, energy cannot be fully utilized. The main components in the first mixed solution are monomer or monomer and solvent, the stability of the first mixed solution is not influenced by the rising temperature, the first mixed solution can be preheated to a higher temperature, the second mixed solution contains initiator, and if the preheating temperature of the initiator is higher, the initiator can be decomposed, so the preheating temperature of the second mixed solution is not high. Therefore, in one embodiment of the present invention, the first material heat exchange system 6-1 is adopted to simultaneously implement the first-stage temperature reduction of the hydroxyl acrylic resin and the preheating of the first mixed solution, and the second material heat exchange system 6-2 is adopted to simultaneously implement the second-stage temperature reduction of the hydroxyl acrylic resin after the first-stage temperature reduction and the preheating of the second mixed solution, so as to implement the comprehensive utilization of energy and achieve the effect of energy saving.

The first material heat exchange system 6-1 comprises a resin inlet, a resin outlet after the first-stage cooling, a first mixed liquid inlet and a first mixed liquid outlet after the preheating. The second material heat exchange system comprises a first-stage cooled resin inlet, a second-stage cooled resin outlet, a second mixed liquid inlet and a preheated second mixed liquid outlet. The material heat exchange system adopts a dividing wall type heat exchanger, preferably a tubular heat exchanger, an inlet and an outlet of the resin are positioned at two ends of a tube pass of the tubular heat exchanger, and an inlet and an outlet of the mixed liquid are positioned at two ends of a shell pass of the tubular heat exchanger.

Hydroxyl acrylic resin flowing out of the polymerization reaction unit 3 enters a first material heat exchange system 6-1 to be subjected to first-stage cooling, the temperature is reduced to 70-100 ℃, and in the process, a first mixed solution is preheated to 110-200 ℃ through the first material heat exchange system 6-1; and the hydroxyl acrylic resin subjected to primary cooling enters a second material heat exchange system 6-2 to be subjected to secondary cooling, the temperature is reduced to 55-75 ℃, and meanwhile, a second mixed solution is preheated to 70-100 ℃ by the second material heat exchange system 6-2.

As a non-limiting example, in the present invention, the outlet of the mixing system 1 is connected to the inlet of the material conveying system 2, the outlet of the material conveying system 2 is connected to the mixed liquid inlet of the material heat exchanging system, the mixed liquid outlet of the material heat exchanging system is connected to the inlet of the polymerization reaction unit 3, the outlet of the polymerization reaction unit 3 is connected to the resin inlet of the material heat exchanging system, and the resin outlet of the material heat exchanging system is connected to the inlet of the receiving unit 4.

In the invention, because of the adoption of higher reaction temperature, if the reaction is carried out under normal pressure, low boiling point substances are easy to vaporize, so that the loss of materials, the unbalance of material proportion, the influence on the quality of products and the harm to the environment and the health of people are caused. According to the invention, a backpressure system is adopted to carry out backpressure on the reaction system, a pressure regulating valve is arranged on a connecting pipeline between the resin outlet of the second material heat exchange system 6-2 after secondary cooling and the receiving unit 4, and the pressure of the system is fed back in real time through pressure sensing, so that the pressure regulation and control of the reaction system and the material heat exchange system are realized. In the invention, the pressure of the polymerization reaction unit 3 and the material heat exchange system is controlled to be 1-5 MPa.

In the invention, each system and unit in the continuous production device for producing the hydroxyl acrylic resin are connected with the automatic control system for automatic operation, so that the continuous automatic production of the hydroxyl acrylic resin can be realized. In the invention, the continuous production device of the hydroxyl acrylic resin is provided with the detection and control of flow, pressure and temperature and the safety interlock of overpressure and overtemperature. The overpressure safety interlock is characterized in that a pressure alarm and a flow alarm interlock (a high-pressure alarm value is 6MPa, a low-pressure alarm value is 0.1MPa, a high-flow alarm value is 1.5 times of a flow value corresponding to the throughput of a production system, and a low-flow alarm value is one third of the flow value corresponding to the throughput of the production system) are arranged in the material conveying system 2, when any one parameter reaches a set value, an ESD emergency stop system is executed, a protection interlock signal is sent, a feeding pump is closed, safety protection is carried out on equipment, and serious loss caused by danger diffusion is avoided. The over-temperature safety interlock is characterized in that a temperature alarm interlock (high-temperature alarm value: 250 ℃) is arranged on the reactor, when the temperature exceeds the high-temperature alarm value, the system increases the public work consumption through an adjusting valve, and simultaneously executes an ESD emergency shutdown system to send out a protection interlock signal, close a feed pump, perform safety protection on equipment and avoid serious loss caused by dangerous diffusion. In addition, the continuous production device has four working modes: the production mode, the cleaning mode, the trial run mode and the shutdown mode are controlled by remote operation, so that the safety of automation and production is greatly improved.

By way of non-limiting example, in one embodiment of the present invention, the mixing system 1 comprises at least a first mixer 1-1, a second mixer 1-2 and optionally a third mixer 1-3, and the continuous production process comprises the steps of:

step 1: respectively feeding a monomer to be mixed, a solvent and an initiator into a first mixer 1-1, a second mixer 1-2 and an optional third mixer 1-3 for premixing to obtain a first mixed solution, a second mixed solution and an optional third mixed solution; the first mixed solution comprises a part or all of monomers, the second mixed solution comprises a part or all of initiators, and the third mixed solution comprises one or more of monomers, solvents and initiators;

step 2: continuously conveying the first mixed solution and the second mixed solution to the material heat exchange system through the material conveying system 2, preheating the first mixed solution and the second mixed solution in the material heat exchange system, then feeding the first mixed solution and the second mixed solution into the polymerization reaction unit 3, continuously conveying an optional third mixed solution to the polymerization reaction unit 3 through the material conveying system 2, reacting the first mixed solution, the second mixed solution and the optional third mixed solution at the temperature of 160-230 ℃ and the pressure of 1-5 MPa, and allowing the first mixed solution, the second mixed solution and the optional third mixed solution to stay for 1-20 min to obtain hydroxyl acrylic resin;

and step 3: and hydroxyl acrylic resin flowing out of the polymerization reaction unit 3 enters the material heat exchange system to be cooled and then enters the receiving unit 4.

More specifically, the first mixed solution and the second mixed solution are respectively and continuously conveyed to a first material heat exchange system 6-1 and a second material heat exchange system 6-2 through the material conveying system 2, and enter the polymerization reaction unit 3 after the first material heat exchange system 6-1 and the second material heat exchange system 6-2 are preheated respectively;

the temperature of the hydroxyl acrylic resin is reduced to 70-100 ℃ through the first stage of the material heat exchange system (such as the first material heat exchange system 6-1), and the temperature of the hydroxyl acrylic resin is reduced to 55-75 ℃ through the second stage of the material heat exchange system (such as the second material heat exchange system 6-2); the first mixed solution is preheated to 110-200 ℃ through the material heat exchange system (such as the first material heat exchange system 6-1), and the second mixed solution is preheated to 70-100 ℃ through the material heat exchange system (such as the second material heat exchange system 6-2).

In the present invention, the monomer includes a hydroxyl monomer, a carboxyl monomer, a hard monomer and a soft monomer. The hydroxyl monomer is one or more of hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate and hydroxybutyl acrylate, the carboxyl monomer is at least one of acrylic acid and methacrylic acid, the hard monomer is one or more of styrene, methyl acrylate, methyl methacrylate, ethyl methacrylate and isobornyl acrylate, and the soft monomer is one or more of ethyl acrylate, isooctyl methacrylate, butyl acrylate, butyl methacrylate and lauryl acrylate.

The mass of the hydroxyl monomer accounts for 12-40% of the total mass of the monomers, the mass of the carboxyl monomer accounts for 0.1-3.8% of the total mass of the monomers, and the mass of the hard monomer and the mass of the soft monomer both account for 20-60% of the total mass of the monomers. The mass ratio of the monomer to the solvent to the initiator is 45-89: 10-50: 1-5.

According to the general knowledge of the skilled person, increasing the reaction temperature accelerates the decomposition of the initiator, thereby increasing the rate at which the monomers undergo polymerization and shortening the molecular weight of the polymerized molecules. Therefore, the reaction temperature can be raised by virtue of the excellent heat exchange effect of the continuous channel reactor, high-temperature reaction is realized, the retention time of materials in the reactor is shortened, and the quality of resin is improved. Through a large amount of experimental researches, the invention discovers that the hydroxy acrylic resin with lower polymerization degree and concentrated molecular weight distribution can be obtained in shorter reaction time under the condition of high-temperature reaction by adopting a continuous production mode. If the reaction temperature is too low, in order to ensure the conversion rate of the monomer, the retention time of the material in the continuous channel reactor is prolonged, so that the production efficiency is reduced, and the quality of the finally obtained hydroxyl acrylic resin is poor; if the reaction temperature is too high, the pressure of a reaction system is higher, the reaction process is too violent, the heat exchange requirement on the continuous channel reactor is strict, the reaction is difficult to control, and the reaction temperature is too high, so that the branching condition of the resin is aggravated, gel is easy to generate, and the quality of the resin is influenced. Therefore, the reaction temperature adopted by the invention is 160-230 ℃.

The retention time of the materials in the polymerization reaction unit 3 is adjusted along with the reaction temperature, if the retention time is too long, the generated hydroxyl acrylic resin can continue to undergo polymerization reaction at high temperature, so that the molecular chain of the resin is lengthened, the molecular weight of the resin is increased, the viscosity of the finally obtained resin is increased, and the use of the resin is influenced; if the residence time is too short, a large amount of monomer remains, and the solid content of the resin is reduced. Therefore, the retention time of the materials adopted by the invention is 1-20 min.

In the invention, the pressure control of the polymerization reaction unit 3 and the material heat exchange system is adjusted along with the reaction temperature, if the pressure is too low, the mixed liquid is vaporized when entering the material heat exchange system for preheating, so that the loss of the low-boiling-point material and the change of the proportion of the material entering the polymerization reaction unit 3 are caused, thereby affecting the quality of the resin; if the pressure is too high, the work load of the feed pump in the material conveying system 2 will increase. Therefore, the pressure of the polymerization reaction unit 3 and the material heat exchange system is controlled to be 1-5 MPa.

In the invention, the mass of the hydroxyl monomer accounts for 12-40% of the total mass of the monomers, the hydroxyl value of the hydroxyl acrylic acid aqueous dispersion can be ensured to be 60-155 mg KOH/g, and the adhesive force, wetting dispersibility, chemical and mechanical properties of the paint film are good in the range. If the hydroxyl monomer is too little, the condition of chain scission blocking is easily caused when the hydroxyl acrylic resin and the curing agent are crosslinked, and a spatial network structure is not easily formed; too much hydroxyl monomer increases the crosslinking density of the radical, the contact between the hydroxyl and isocyanate becomes difficult, and residual hydroxyl exists in the system, thereby reducing the water resistance of the paint film and increasing the cost of the curing agent.

In the invention, the mass of the carboxyl monomer accounts for 0.1-3.8% of the total mass of the monomers, and correspondingly, the acid value of the hydroxy acrylic resin is 1-25 mg KOH/g. The carboxyl monomer is too low in dosage, the adhesive force and wetting dispersibility of the paint film are poor, and the carboxyl monomer is too high in dosage, so that the hydrophilicity of the resin is increased, and the water resistance and the storage stability of the paint film are reduced.

The solvent adopted in the invention is one or more of propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol butyl ether, propylene glycol methyl ether acetate, ethylene glycol ethyl ether acetate, toluene, xylene, No. 100 solvent naphtha, butyl acetate, isobutyl acetate, n-butyl alcohol and isobutyl alcohol. For the production of the hydroxy acrylic resin with high solid content for preparing the hydroxy acrylic resin aqueous dispersion, solvents with low boiling point and hydrophilicity and lipophilicity are preferred, such as propylene glycol methyl ether, propylene glycol ethyl ether and propylene glycol monomethyl ether acetate, so as to avoid the problem that the residual time is too long due to too slow volatilization of the solvents in the product application process, and the product application is influenced; for the production of solvent-based hydroxy acrylic resins, solvents with better compatibility, such as toluene, xylene and butyl acetate, are preferred.

The initiator adopted by the invention is at least one of di-tert-butyl peroxide, di-tert-amyl peroxide, diisopropyl peroxide, tert-butyl peroxyacetate, tert-butyl cumyl peroxide and di-tert-butylperoxy diisopropylbenzene. The decomposition temperature of the initiator is 160-200 ℃ when the half-life period of the initiator is 1min, so that the initiator can be rapidly decomposed to generate free radicals at the reaction temperature, the chain initiation process is shortened, and the polymeric molecules with shorter molecular chains are obtained.

In the invention, the materials for producing the hydroxyl acrylic resin are all industrial grade materials which are all commercially available; the various components of the continuous production apparatus employed, such as, for example, piping, valves, controllers, feed pumps, microchannel reactors, static tubular reactors, static mixers, dynamic tubular reactors, receiving tanks, etc., are commercially available from commercial sources, but the entire continuous production apparatus is not commercially available or known to those skilled in the art.

In one embodiment of the present invention, as shown in fig. 1, the apparatus for continuously producing hydroxyacrylic resin comprises a mixing system 1, a material conveying system 2, a polymerization reaction unit 3, a receiving unit 4, and a heat exchange system, wherein a mixed liquid outlet of the mixing system 1 is connected to a mixed liquid inlet of the material conveying system 2, a mixed liquid outlet of the material conveying system 2 is connected to a mixed liquid inlet of the polymerization reaction unit 3, and a resin outlet of the polymerization reaction unit 3 is connected to a resin inlet of the receiving unit 4.

The mixing system 1 comprises a first mixer 1-1 and a second mixer 1-2, which are respectively used for mixing the first mixed liquid and the second mixed liquid, and the first mixer 1-1 and the second mixer 1-2 both adopt conventional stirred tanks. The material conveying system 2 comprises two feeding pumps which are respectively used for conveying the first mixed liquid and the second mixed liquid. The polymerization reaction unit 3 employs a continuous channel reactor in which a microchannel reactor and a tubular reactor are arbitrarily combined.

The heat exchange system comprises a reaction temperature control system 5 and a material heat exchange system, wherein the material heat exchange system comprises a first material heat exchange system 6-1 and a second material heat exchange system 6-2. The material heat exchange system adopts a tubular heat exchanger, hydroxy acrylic resin obtained by reaction sequentially enters a first tubular heat exchanger in a first material heat exchange system 6-1 and a second tubular heat exchanger in a second material heat exchange system 6-2, the tube pass of the second tubular heat exchanger is cooled in two stages and then enters a receiving tank of a receiving unit 4, the first mixed liquid enters the shell pass of the first tubular heat exchanger in the first material heat exchange system 6-1 to realize preheating, and the second mixed liquid enters the shell pass of the second tubular heat exchanger in the second material heat exchange system 6-2 to realize preheating. The reaction temperature control system 5 sets a reactor temperature zone for the continuous channel reactor.

The mass ratio of the monomer to the solvent in the first mixed solution is 45-89: 0-20, and the mass ratio of the initiator to the solvent and the monomer in the second mixed solution is 1-5: 0-30: 0-20.

The monomer comprises a hydroxyl monomer, a carboxyl monomer, a hard monomer and a soft monomer, wherein the hydroxyl monomer is one or more of hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate and hydroxybutyl acrylate, and the mass of the hydroxyl monomer accounts for 12-40% of the total mass of the monomer. The carboxyl monomer is at least one of acrylic acid and methacrylic acid, and the mass of the carboxyl monomer accounts for 0.1-3.8% of the total mass of the monomers. The hard monomer is one or more of styrene, methyl acrylate, methyl methacrylate, ethyl methacrylate and isobornyl acrylate. The soft monomer is one or more of ethyl acrylate, isooctyl methacrylate, butyl acrylate, butyl methacrylate and lauryl acrylate. The mass of the hard monomer and the mass of the soft monomer are both 20-60% of the total mass of the monomers. The mass ratio of the monomer to the solvent to the initiator is 45-89: 10-50: 1-5.

The solvent is one or more of propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol butyl ether, propylene glycol monomethyl ether acetate, ethylene glycol ethyl ether acetate, toluene, xylene, No. 100 solvent naphtha, butyl acetate, isobutyl acetate, n-butanol and isobutanol. The initiator is at least one of di-tert-butyl peroxide, di-tert-amyl peroxide, diisopropyl peroxide, tert-butyl peroxyacetate, tert-butyl cumyl peroxide and di-tert-butyl diisopropylperoxide.

Specifically, a monomer or a monomer and a solvent are introduced into the first material mixer 1-1 and mixed uniformly to obtain a first mixed solution, and an initiator or an initiator and a solvent are introduced into the second material mixer 1-2 and mixed uniformly to obtain a second mixed solution. The first mixed liquid and the second mixed liquid are respectively conveyed to a material heat exchange system 6-1 and a material heat exchange system 6-2 through a material conveying system 2, are respectively preheated to 110-200 ℃ and 70-100 ℃, the preheated mixed liquid enters a continuous channel reactor of a polymerization reaction unit 3, rapidly reacts for 1-20 min at 160-230 ℃ and 1-5 MPa, and the obtained hydroxy acrylic resin enters the material heat exchange system, is cooled to 55-75 ℃ after two-stage cooling, and enters a receiving tank of a receiving unit 4.

In one embodiment of the present invention, as shown in fig. 2, the apparatus for continuously producing hydroxyacrylic resin comprises a mixing system 1, a material conveying system 2, a polymerization reaction unit 3, a receiving unit 4, and a heat exchange system, wherein a mixed liquid outlet of the mixing system 1 is connected to a mixed liquid inlet of the material conveying system 2, a mixed liquid outlet of the material conveying system 2 is connected to a mixed liquid inlet of the polymerization reaction unit 3, and a resin outlet of the polymerization reaction unit 3 is connected to a resin inlet of the receiving unit 4.

The mixing system 1 comprises a first mixer 1-1, a second mixer 1-2 and a third mixer 1-3, which are respectively used for mixing a first mixed solution, a second mixed solution and a third mixed solution, wherein the first mixer 1-1, the second mixer 1-2 and the third mixer 1-3 adopt conventional stirred tanks. The material conveying system 2 comprises three feeding pumps which are respectively used for conveying the first mixed liquid, the second mixed liquid and the third mixed liquid. The polymerization reaction unit 3 employs a continuous channel reactor in which a microchannel reactor and a tubular reactor are arbitrarily combined.

The heat exchange system comprises a reaction temperature control system 5 and a material heat exchange system, wherein the material heat exchange system comprises a first material heat exchange system 6-1 and a second material heat exchange system 6-2. The material heat exchange system adopts a tubular heat exchanger, hydroxy acrylic resin obtained by reaction sequentially enters a first tubular heat exchanger in a first material heat exchange system 6-1 and a second tubular heat exchanger in a second material heat exchange system 6-2, the tube pass of the second tubular heat exchanger is cooled in two stages and then enters a receiving tank of a receiving unit 4, the first mixed liquid enters the shell pass of the first tubular heat exchanger in the first material heat exchange system 6-1 to realize preheating, and the second mixed liquid enters the shell pass of the second tubular heat exchanger in the second material heat exchange system 6-2 to realize preheating. The reaction temperature control system 5 sets two reactor temperature zones for the continuous channel reactor.

The mass ratio of the monomer to the solvent in the first mixed solution is 45-89: 0-20, the mass ratio of the initiator to the solvent and the monomer in the second mixed solution is 1-5: 0-30: 0-20, and the mass ratio of the initiator to the solvent to the monomer in the third mixed solution is 1-5: 0-50: 0: 89.

The monomer comprises a hydroxyl monomer, a carboxyl monomer, a hard monomer and a soft monomer, wherein the hydroxyl monomer is one or more of hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate and hydroxybutyl acrylate, and the mass of the hydroxyl monomer accounts for 12-40% of the total mass of the monomer. The carboxyl monomer is at least one of acrylic acid and methacrylic acid, and the mass of the carboxyl monomer accounts for 0.1-3.8% of the total mass of the monomers. The hard monomer is one or more of styrene, methyl acrylate, methyl methacrylate, ethyl methacrylate and isobornyl acrylate. The soft monomer is one or more of ethyl acrylate, isooctyl methacrylate, butyl acrylate, butyl methacrylate and lauryl acrylate. The mass of the hard monomer and the mass of the soft monomer account for 20-60% of the total mass of the monomers. The mass ratio of the monomer to the solvent to the initiator is 45-89: 10-50: 1-5.

The solvent is one or more of propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol butyl ether, propylene glycol monomethyl ether acetate, ethylene glycol ethyl ether acetate, toluene, xylene, No. 100 solvent naphtha, butyl acetate, isobutyl acetate, n-butanol and isobutanol. The initiator is at least one of di-tert-butyl peroxide, di-tert-amyl peroxide, diisopropyl peroxide, tert-butyl peroxyacetate, tert-butyl cumyl peroxide and di-tert-butyl diisopropylperoxide.

Specifically, a monomer or a monomer and a solvent are introduced into a first material mixer 1-1 and mixed uniformly to obtain a first mixed solution, an initiator or an initiator and a solvent are introduced into a second material mixer 1-2 and mixed uniformly to obtain a second mixed solution, an initiator and a solvent or an initiator, a solvent and a monomer are introduced into a third material mixer 1-3 and mixed uniformly to obtain a third mixed solution. The first mixed liquid and the second mixed liquid are respectively conveyed to a material heat exchange system 6-1 and a material heat exchange system 6-2 through a material conveying system 2, are respectively preheated to 110-200 ℃ and 70-100 ℃, enter a continuous channel reactor of a polymerization reaction unit 3 for rapid reaction at 160-230 ℃ and 1-5 MPa, and then enter a third mixed liquid of the continuous channel reactor for continuous reaction, the total residence time of the first mixed liquid, the second mixed liquid and the third mixed liquid is 1-20 min, and the obtained hydroxy acrylic resin enters the material heat exchange system, is cooled to 55-75 ℃ after two-stage cooling, and then enters a receiving tank of a receiving unit 4.

The present invention will be described in further detail with reference to specific examples, which include but are not limited to the following examples, and any modifications in the details and form of the technical solution of the present invention may be made without departing from the meaning and scope of the present invention.

Wherein, the determination of the solid content is carried out according to GB/T1725-2007; the viscosity is measured by adopting an NDJ-1 type rotary viscometer according to GB/T2794-2013; the acid value is measured according to GB/T2895-2008; the hydroxyl value was measured with reference to GB/T12008.3-2009.

In the present invention, the solid content is in mass% unless otherwise specified.

Comparative example 1

The hydroxyl acrylic resin is produced under the optimal kettle type production condition, and the specific operation is as follows: 15 parts (by weight, the same applies hereinafter) of xylene and 20 parts of butyl acetate are added into a reaction kettle, preheated to 120 ℃, and a mixed solution of 20.5 parts of styrene, 16.1 parts of methyl methacrylate, 17.6 parts of butyl acrylate, 26.3 parts of isooctyl methacrylate, 8 parts of hydroxypropyl acrylate, 11 parts of hydroxyethyl methacrylate, 0.5 part of acrylic acid and 1.5 parts of di-tert-amyl peroxide is added dropwise, and the reaction temperature is maintained at 150 ℃, and the dropwise addition is finished within 6 hours. And then continuously dropwise adding a mixed solution of 5 parts of dimethylbenzene and 1 part of di-tert-amyl peroxide, after dropwise adding is finished within 1 hour, heating to 160 ℃, continuously preserving heat for 3 hours, and then cooling to 70 ℃ to obtain the hydroxy acrylic resin, wherein the solid content of the obtained hydroxy acrylic resin is 59.5%, and the viscosity is 3400 cP.

In the industrial production process of the batch kettle type process, in order to realize the capacity of 5000 tons per year, two sets of 10 cubic meter reaction kettles need to be set, 450 batches are intermittently produced per year, the operation is complex, and the production efficiency is not high.

Example 1

12.85 parts (by weight, the same applies hereinafter) of methyl methacrylate, 11.4 parts of butyl acrylate, 18.6 parts of butyl methacrylate, 6.1 parts of hydroxyethyl acrylate, 0.06 part of acrylic acid, 10 parts of xylene and 10 parts of butyl acetate are introduced into the first mixer 1-1, and a first mixed solution is obtained by mixing uniformly. And (3) introducing 1 part of tert-butyl peroxyacetate and 30 parts of butyl acetate into the second mixer 1-2, and uniformly mixing to obtain a second mixed solution.

The first mixed solution is conveyed to the first material heat exchange system 6-1 through the material conveying system 2 to be preheated to 110 ℃, and the second mixed solution is conveyed to the second material system 6-2 through the material conveying system 2 to be preheated to 100 ℃. And continuously conveying the preheated first mixed solution and the preheated second mixed solution into a continuous channel reactor serving as a polymerization reaction unit 3 and sequentially connected in series by a micro-channel reactor and a static tubular reactor by a feed pump, and reacting for 10min at the temperature of 160 ℃ and the pressure of 1MPa to obtain the hydroxyl acrylic resin. The hydroxyl acrylic resin sequentially enters a first material heat exchange system 6-1 (cooled to 100 ℃) and a second material heat exchange system 6-2, and enters a receiving tank serving as a receiving unit 4 after being cooled to 75 ℃.

The obtained hydroxyacrylic resin had a solid content of 50%, an acid value of 1mgKOH/g, a hydroxyl value of 60mgKOH/g, and a viscosity of 2200 cP.

According to a set of continuous channel reactor with liquid holdup of 200L in example 1, the annual output can reach 8000 tons, compared with two sets of 10 cubic meters of reaction kettles in comparative example 1, the production efficiency is improved by 0.6 times, and energy is saved by 9.6 kilocalories/h.

Example 2

18.43 parts of styrene, 14.58 parts of methyl acrylate, 5.23 parts of ethyl acrylate, 6.05 parts of isooctyl methacrylate, 4.6 parts of hydroxyethyl methacrylate, 4 parts of hydroxypropyl acrylate, 0.14 part of acrylic acid, 10 parts of xylene and 5 parts of butyl acetate are fed into the first mixer 1-1 and uniformly mixed to obtain a first mixed solution. And (3) introducing 2 parts of tert-butyl cumyl peroxide, 10 parts of dimethylbenzene and 20 parts of butyl acetate into the second mixer 1-2, and uniformly mixing to obtain a second mixed solution.

The first mixed solution is conveyed to the first material heat exchange system 6-1 through the material conveying system 2 to be preheated to 163 ℃, and the second mixed solution is conveyed to the second material system 6-2 through the material conveying system 2 to be preheated to 92 ℃. And continuously conveying the preheated first mixed solution and the preheated second mixed solution into a continuous channel reactor serving as a polymerization reaction unit 3 and sequentially connected in series by a micro-channel reactor and a static mixer by a feed pump, and reacting for 1min at 195 ℃ and 3.5MPa to obtain the hydroxyl acrylic resin. The hydroxyl acrylic resin sequentially enters a first material heat exchange system 6-1 (cooled to 98 ℃) and a second material heat exchange system 6-2, and enters a receiving tank serving as a receiving unit 4 after being cooled to 75 ℃.

The obtained hydroxy acrylic resin has a solid content of 55%, an acid value of 2mgKOH/g, a hydroxyl value of 70mgKOH/g, and a viscosity of 2000 cP.

According to a set of continuous channel reactor with liquid holdup of 50L in example 2, the annual output can reach 20000 tons, the production efficiency is improved by 3 times compared with two sets of 10 cubic meters of reaction kettles in comparative example 1, and 24 ten thousand kilocalories per hour can be saved.

Example 3

12.3 parts of styrene, 9.66 parts of methyl methacrylate, 10.56 parts of butyl acrylate, 14.04 parts of isooctyl methacrylate, 4.7 parts of hydroxypropyl acrylate, 6 parts of hydroxyethyl methacrylate, 0.3 part of acrylic acid and 15 parts of xylene are fed into the first mixer 1-1 and uniformly mixed to obtain a first mixed solution. And (3) introducing 2.5 parts of diisopropyl peroxide and 25 parts of butyl acetate into the second mixer 1-2, and uniformly mixing to obtain a second mixed solution.

The first mixed solution is conveyed to the first material heat exchange system 6-1 through the material conveying system 2 to be preheated to 179 ℃, and the second mixed solution is conveyed to the second material system 6-2 through the material conveying system 2 to be preheated to 74 ℃. And continuously conveying the preheated first mixed solution and the preheated second mixed solution into a continuous channel reactor serving as a polymerization reaction unit 3 and sequentially connected in series by a static mixer and a static tubular reactor by a feed pump, and reacting for 4min at 185 ℃ and 2.6MPa to obtain the hydroxyl acrylic resin. The hydroxyl acrylic resin sequentially enters a first material heat exchange system 6-1 (cooled to 70 ℃) and a second material heat exchange system 6-2, and enters a receiving tank serving as a receiving unit 4 after being cooled to 55 ℃.

The obtained hydroxyl acrylic resin has a solid content of 60%, an acid value of 4mgKOH/g, a hydroxyl value of 80mgKOH/g and a viscosity of 1500 cP.

According to a set of continuous channel reactor with the liquid holdup of 100L in the example 3, the annual output can reach 10000 tons, compared with two sets of 10 cubic meters of reaction kettles in the comparative example 1, the production efficiency is improved by 1 time, and 12 ten thousand kilocalories per hour can be saved.

Example 4

15.73 parts of styrene, 11.7 parts of ethyl methacrylate, 8.78 parts of isooctyl acrylate, 11.5 parts of butyl methacrylate, 6.3 parts of hydroxypropyl methacrylate, 8 parts of hydroxybutyl acrylate, 0.8 part of acrylic acid and 10 parts of xylene are introduced into the first mixer 1-1 and uniformly mixed to obtain a first mixed solution. And (3) introducing 3 parts of di-tert-amyl peroxide and 25 parts of butyl acetate into the second mixer 1-2, and uniformly mixing to obtain a second mixed solution.

The first mixed solution is conveyed to the first material heat exchange system 6-1 through the material conveying system 2 to be preheated to 162 ℃, and the second mixed solution is conveyed to the second material system 6-2 through the material conveying system 2 to be preheated to 80 ℃. And continuously conveying the preheated first mixed solution and the preheated second mixed solution into a continuous channel reactor serving as a polymerization reaction unit 3 and sequentially connected in series by a dynamic tubular reactor and a static tubular reactor by a feed pump, and reacting for 4min at the temperature of 182 ℃ and the pressure of 2.4MPa to obtain the hydroxyl acrylic resin. The hydroxyl acrylic resin sequentially enters a first material heat exchange system 6-1 (cooled to 82 ℃) and a second material heat exchange system 6-2, and enters a receiving tank serving as a receiving unit 4 after being cooled to 65 ℃.

The obtained hydroxy acrylic resin has a solid content of 65%, an acid value of 6mgKOH/g, a hydroxyl value of 90mgKOH/g, and a viscosity of 1800 cP.

According to the continuous channel reactor with the liquid holdup of 250L in the example 4, the annual output can reach 7500 tons, the production efficiency is improved by 0.5 times compared with the two sets of 10 cubic meters of reaction kettles in the comparative example 1, and the energy is saved by 8.5 ten thousand kilocalories per hour.

Example 5

13.3 parts of styrene, 9.6 parts of isobornyl acrylate, 11.2 parts of butyl acrylate, 14.7 parts of isooctyl methacrylate, 7.1 parts of hydroxypropyl methacrylate, 10 parts of hydroxybutyl acrylate, 0.68 part of acrylic acid and 15 parts of xylene are fed into the first mixer 1-1 and uniformly mixed to obtain a first mixed solution. And (3) introducing 3.5 parts of di-tert-butylperoxy diisopropylbenzene and 15 parts of butyl acetate into the second mixer 1-2, and uniformly mixing to obtain a second mixed solution.

The first mixed solution is conveyed to the first material heat exchange system 6-1 through the material conveying system 2 to be preheated to 134 ℃, and the second mixed solution is conveyed to the second material system 6-2 through the material conveying system 2 to be preheated to 74 ℃. And continuously conveying the preheated first mixed solution and the preheated second mixed solution into a continuous channel reactor serving as a polymerization reaction unit 3 and sequentially connected in series by a static mixer and a static tubular reactor by a feed pump, and reacting for 20min at the temperature of 170 ℃ and the pressure of 1.8MPa to obtain the hydroxyl acrylic resin. The hydroxyl acrylic resin sequentially enters a first material heat exchange system 6-1 (cooled to 77 ℃) and a second material heat exchange system 6-2, and enters a receiving tank serving as a receiving unit 4 after being cooled to 67 ℃.

The obtained hydroxyacrylic resin had a solid content of 70%, an acid value of 8mgKOH/g, a hydroxyl value of 100mgKOH/g, and a viscosity of 2200 cP.

According to a set of continuous channel reactor with 350L liquid holdup in example 5, the annual output can reach 7500 tons, compared with two sets of 10 cubic meters of reaction kettles in comparative example 1, the production efficiency is improved by 0.5 times, and 9 ten thousand kilocalories per hour can be saved.

Example 6

16.95 parts of styrene, 12 parts of lauryl acrylate, 14.25 parts of butyl methacrylate, 16.4 parts of hydroxyethyl acrylate, 1.11 parts of methacrylic acid and 22.25 parts of xylene are introduced into the first mixer 1-1 and uniformly mixed to obtain a first mixed solution. And 3 parts of di-tert-amyl peroxide, 3.75 parts of butyl acetate and 11.25 parts of methyl acrylate are introduced into the second mixer and uniformly mixed to obtain a second mixed solution.

The first mixed solution is conveyed to the first material heat exchange system 6-1 through the material conveying system 2 to be preheated to 166 ℃, and the second mixed solution is conveyed to the second material system 6-2 through the material conveying system 2 to be preheated to 81 ℃. And continuously conveying the preheated first mixed solution and the preheated second mixed solution into a continuous channel reactor serving as a polymerization reaction unit 3 and sequentially connected in series by a micro-channel reactor and a dynamic tubular reactor by a feed pump, and reacting for 5min at 200 ℃ and 3.6MPa to obtain the hydroxyl acrylic resin. The hydroxyl acrylic resin sequentially enters a first material heat exchange system 6-1 (cooled to 85 ℃) and a second material heat exchange system 6-2, and enters a receiving tank serving as a receiving unit 4 after being cooled to 74 ℃.

The obtained hydroxyacrylic resin had a solid content of 75%, an acid value of 10mgKOH/g, a hydroxyl value of 110mgKOH/g, and a viscosity of 2700 cP.

According to a set of continuous channel reactor with the liquid holdup of 180L in example 6, the annual output can reach 15000 tons, the production efficiency is improved by 2 times compared with two sets of 10 cubic meters of reaction kettles in comparative example 1, and 18 ten thousand kilocalories per hour can be saved.

Example 7

20.08 parts of styrene, 10.72 parts of butyl acrylate, 18.4 parts of butyl methacrylate, 13.2 parts of hydroxyethyl methacrylate, 9 parts of hydroxypropyl acrylate, 0.67 part of methacrylic acid, 0.6 part of acrylic acid, 10 parts of butyl acetate and 10 parts of xylene are introduced into the first mixer 1-1 and uniformly mixed to obtain a first mixed solution. 3.5 parts of di-tert-butyl peroxide and 10 parts of methyl acrylate are introduced into the second mixer 1-2 and mixed uniformly to obtain a second mixed solution.

The first mixed solution is conveyed to the first material heat exchange system 6-1 through the material conveying system 2 to be preheated to 170 ℃, and the second mixed solution is conveyed to the second material system 6-2 through the material conveying system 2 to be preheated to 78 ℃. And continuously conveying the preheated first mixed solution and the preheated second mixed solution into a continuous channel reactor serving as a polymerization reaction unit 3 and sequentially connected in series by a micro-channel reactor and a static tubular reactor by a feed pump, and reacting for 9min at 210 ℃ and 4MPa to obtain the hydroxyl acrylic resin. The hydroxyl acrylic resin sequentially enters a first material heat exchange system 6-1 (cooled to 80 ℃) and a second material heat exchange system 6-2, and enters a receiving tank serving as a receiving unit 4 after being cooled to 72 ℃.

The obtained hydroxyacrylic resin had a solid content of 80%, an acid value of 10mgKOH/g, a hydroxyl value of 125mgKOH/g, and a viscosity of 4200 cP.

According to a set of continuous channel reactors with the liquid holdup of 200L in the example 7, the annual output can reach 9000 tons, the production efficiency is improved by 0.8 times compared with two sets of 10 cubic meters of reaction kettles in the comparative example 1, and 10.8 ten thousand kilocalories per hour can be saved.

Example 8

21.85 parts of styrene, 14.88 parts of ethyl methacrylate, 7.31 parts of isooctyl acrylate, 9.78 parts of butyl methacrylate, 11.4 parts of hydroxypropyl acrylate, 14 parts of hydroxyethyl methacrylate and 1.86 parts of methacrylic acid are introduced into the first mixer 1-1 and uniformly mixed to obtain a first mixed solution. And (3) introducing 3 parts of di-tert-butyl peroxide and 15 parts of propylene glycol dimethyl ether into the second mixer 1-2, and uniformly mixing to obtain a second mixed solution. And (3) introducing 1 part of di-tert-butyl peroxide into the third mixer 1-3 to obtain a third mixed solution.

The first mixed solution is conveyed to the first material heat exchange system 6-1 through the material conveying system 2 to be preheated to 200 ℃, and the second mixed solution is conveyed to the second material heat exchange system 6-2 through the material conveying system 2 to be preheated to 70 ℃. The preheated first mixed liquor and the preheated second mixed liquor are continuously conveyed by a feed pump, and enter a continuous channel reactor serving as a polymerization reaction unit 3 and sequentially connected in series by a microchannel reactor, a first static tubular reactor, a static mixer and a second static tubular reactor from a material inlet of the microchannel reactor, wherein the temperature of the microchannel reactor, the first static tubular reactor and the static mixer is controlled to be 180 ℃ by a reaction temperature control system 5, and the temperature of the second static tubular reactor is controlled to be 230 ℃ by the reaction temperature control system 5. The materials react for 2min at 180 ℃ and 5MPa in the continuous flow mixing process in the continuous channel reactor, then the reaction materials and the third mixed solution entering the continuous channel reactor from the material inlet of the static mixer continuously react for 1min, and then the third mixed solution reacts for 3min at 230 ℃ and 5MPa to obtain the hydroxyl acrylic resin. The hydroxyl acrylic resin sequentially enters a first material heat exchange system 6-1 (cooled to 72 ℃) and a second material heat exchange system 6-2, and enters a receiving tank serving as a receiving unit 4 after being cooled to 65 ℃.

The obtained hydroxyl acrylic resin has a solid content of 85%, an acid value of 15mgKOH/g, a hydroxyl value of 135mgKOH/g and a viscosity of 5500 cP.

According to a set of continuous channel reactor with the liquid holdup of 180L in the example 8, the annual output can reach 13000 tons, the production efficiency is improved by 1.6 times compared with two sets of 10 cubic meters of reaction kettles in the comparative example 1, and the energy is saved by 15.5 ten thousand kilocalories per hour.

Example 9

7.38 parts of styrene, 10.6 parts of methyl acrylate, 13.14 parts of butyl acrylate, 16.83 parts of isooctyl methacrylate, 11.4 parts of hydroxypropyl methacrylate, 12.5 parts of hydroxybutyl acrylate and 3.26 parts of methacrylic acid are introduced into the first mixer 1-1 and uniformly mixed to obtain a first mixed solution. And 4.5 parts of di-tert-butyl peroxide and 9 parts of propylene glycol dibutyl ether are introduced into the second mixer 1-2 and uniformly mixed to obtain a second mixed solution. And (3) introducing 1.6 parts of styrene, 1.2 parts of methyl acrylate, 1.2 parts of butyl acrylate, 1.6 parts of isooctyl methacrylate, 2.7 parts of hydroxypropyl methacrylate, 1.3 parts of hydroxybutyl acrylate, 1 part of methacrylic acid, 0.5 part of di-tert-butyl peroxide and 1 part of propylene glycol dimethyl ether into a third mixer 1-3, and uniformly mixing to obtain a third mixed solution.

The first mixed solution is conveyed to the first material heat exchange system 6-1 through the material conveying system 2 to be preheated to 187 ℃, and the second mixed solution is conveyed to the second material heat exchange system 6-2 through the material conveying system 2 to be preheated to 73 ℃. The preheated first mixed liquor and the preheated second mixed liquor are continuously conveyed by a feed pump, and enter a continuous channel reactor serving as a polymerization reaction unit 3 and sequentially connected in series by a microchannel reactor, a first static tubular reactor, a dynamic tubular reactor and a second static tubular reactor from a material inlet of the microchannel reactor, wherein the temperature of the microchannel reactor, the first static tubular reactor and the dynamic tubular reactor is controlled to be 180 ℃ by a reaction temperature control system 5, and the temperature of the second static tubular reactor is controlled to be 220 ℃ by the reaction temperature control system 5. The materials react for 2min under the conditions of 180 ℃ and 4.3MPa in the continuous flow mixing process in the continuous channel reactor, then the reaction materials and the third mixed solution entering the continuous channel reactor from the material inlet of the dynamic tubular reactor continuously react for 1min, and then the third mixed solution reacts for 4min under the conditions of 230 ℃ and 4.3MPa to obtain the hydroxyl acrylic resin. The hydroxyl acrylic resin sequentially enters a first material heat exchange system 6-1 (cooled to 78 ℃) and a second material heat exchange system 6-2, and enters a receiving tank serving as a receiving unit 4 after being cooled to 70 ℃.

The obtained hydroxyl acrylic resin has a solid content of 90%, an acid value of 25mgKOH/g, a hydroxyl value of 150mgKOH/g and a viscosity of 7200 cP.

According to a set of continuous channel reactor with the liquid holdup of 180L in example 9, the annual output can reach 11000 tons, compared with two sets of 10 cubic meters of reaction kettles in comparative example 1, the production efficiency is improved by 1.2 times, and the energy is saved by 13.1 ten thousand kilocalories per hour.

Example 10

13.6 parts of styrene, 10.48 parts of methyl methacrylate, 10.72 parts of butyl acrylate, 18.4 parts of butyl methacrylate, 13.2 parts of hydroxyethyl methacrylate, 7.7 parts of hydroxypropyl acrylate, 1.15 parts of methacrylic acid and 10 parts of butyl acetate are introduced into the first mixer 1-1 and uniformly mixed to obtain a first mixed solution. And 5 parts of di-tert-butyl peroxide is introduced into the second mixer 1-2 to obtain a second mixed solution.

The first mixed solution is conveyed to the first material heat exchange system 6-1 through the material conveying system 2 to be preheated to 146 ℃, and the second mixed solution is conveyed to the second material system 6-2 through the material conveying system 2 to be preheated to 70 ℃. And continuously conveying the preheated first mixed solution and the preheated second mixed solution into a continuous channel reactor serving as a polymerization reaction unit 3 and sequentially connected in series by a micro-channel reactor and a static tubular reactor by a feed pump, and reacting for 13min at 190 ℃ under the pressure of 2.9MPa to obtain the hydroxyl acrylic resin. The hydroxyl acrylic resin sequentially enters a first material heat exchange system 6-1 (cooled to 70 ℃) and a second material heat exchange system 6-2, and enters a receiving tank serving as a receiving unit 4 after being cooled to 67.5 ℃.

The obtained hydroxyacrylic resin had a solid content of 80%, an acid value of 10mgKOH/g, a hydroxyl value of 120mgKOH/g, and a viscosity of 3700 cP.

According to a set of continuous channel reactors with the liquid holdup of 250L in the example 10, the annual output can reach 8000 tons, the production efficiency is improved by 0.6 times compared with two sets of 10 cubic meters of reaction kettles in the comparative example 1, and the energy is saved by 9.6 ten thousand kilocalories per hour.