CN118388699A

CN118388699A - Preparation method of beaded solid acrylic resin particles

Info

Publication number: CN118388699A
Application number: CN202410641169.9A
Authority: CN
Inventors: 夏维; 王宁宁; 裴锦辉; 张正风
Original assignee: BOLIER CHEMICAL (YANGZHOU) CO LTD
Current assignee: BOLIER CHEMICAL (YANGZHOU) CO LTD
Priority date: 2024-05-22
Filing date: 2024-05-22
Publication date: 2024-07-26

Abstract

The invention discloses a preparation method of beaded solid acrylic resin particles, which adopts a suspension polymerization method, wherein a polymerization system contains monomers, an initiator, a chain transfer agent, a dispersing agent and medium water, the dispersing agent is a compound composition of hydroxyethyl cellulose and methyl cellulose, wherein the dosage of the hydroxyethyl cellulose accounts for 0.1-0.5% of the total mass of the monomers, and the dosage of the methyl cellulose accounts for 0.005-0.04% of the total mass of the monomers. Experiments prove that: according to the invention, the compound composition of hydroxyethyl cellulose and methyl cellulose is used as a dispersing agent, so that the prepared solid acrylic resin particles can be in a regular bead shape, and the preparation method has the advantages of fine average particle size, low residual monomer content, difficulty in caking, good solubility, good glass transition temperature, good molecular weight controllability and the like, and the preparation method does not need to change the existing suspension polymerization production equipment, is simple and convenient to operate, has universality and repeatability, and is easy to realize large-scale production.

Description

Preparation method of beaded solid acrylic resin particles

Technical Field

The invention relates to a preparation method of beaded solid acrylic resin particles, and belongs to the technical field of solid acrylic resin preparation.

Background

Compared with solvent-type, emulsion-type and solvent-to-water-type acrylic resins, the solid acrylic resin has unique performance advantages, and has the advantages of safer storage, transportation and use, more economy and the like, so the solid acrylic resin has been applied to the fields of paint, printing ink, packaging materials, dental materials, cosmetics, nail art care materials and the like.

The current methods for preparing solid acrylic resin are mainly bulk polymerization, suspension polymerization, solution polymerization and emulsion polymerization. Although the solid acrylic resin prepared by the bulk polymerization method has higher purity and good transparency, the bulk polymerization method can only prepare powdery solid acrylic resin, the granular solid acrylic resin can be prepared by a further extrusion granulation process, dust pollution exists in powdery products, and the dissolution speed of the granular products is slower; the solution polymerization method can obtain solid acrylic resin through devolatilization treatment, the form of the devolatilized solid acrylic resin is mostly powder or random form particles, the downstream field with strict requirements on the resin form cannot be met, and the solution polymerization method also has the problems of solvent residue, solvent pollution and the like; the emulsion polymerization method needs to be subjected to spray drying treatment to obtain the solid acrylic resin, the spray drying cost is high, and the emulsifying agent and other auxiliary agents used in the emulsion polymerization process cannot be removed, so that the downstream application performance of the resin can be influenced.

Since suspension polymerization refers to a radical polymerization process in which monomers in which an initiator is dissolved are dispersed in medium water in the form of small droplets, the prepared resin can be made to have advantages in appearance and usability as compared with bulk polymerization, for example: the suspension polymerization method can prepare bead resin particles, and compared with powder or extrusion pelletization resin particles, the bead resin particles have the advantages of higher dissolution speed and no dust emission problem of the powder resin during dissolution; in addition, the suspension polymerization method is also particularly suitable for preparing resin with certain crosslinking degree, and the crosslinked product is difficult to be suitable for subsequent granulation treatment processes such as a bulk polymerization method, a complex crushing extrusion method in a solution polymerization method and the like. Therefore, for special application fields, such as industries of dental materials, cosmetics, nail art, and the like, the suspension polymerization method is more preferred to prepare the solid acrylic resin.

However, the existing suspension polymerization process for preparing solid acrylic resin is easy to cause the problems of difficult control of product quality such as over-coarse particle size of prepared resin particles, higher content of resin residual monomers, easy caking of resin, poor solubility and the like. Therefore, there is a need for a process for preparing beaded solid acrylic resin particles having a relatively fine average particle size, a low residual monomer content, a regular particle morphology, less agglomeration, good solubility, and versatility and repeatability.

Disclosure of Invention

In view of the foregoing problems and needs in the prior art, it is an object of the present invention to provide a process for preparing beaded solid acrylic resin particles.

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

A preparation method of beaded solid acrylic resin particles adopts a suspension polymerization method, and a polymerization system contains monomers, an initiator, a chain transfer agent, a dispersing agent and medium water, and is characterized in that: the dispersing agent is a compound composition of hydroxyethyl cellulose (HEC) and Methyl Cellulose (MC), wherein the dosage of the hydroxyethyl cellulose accounts for 0.1-0.5% of the total mass of the monomer, and the dosage of the methyl cellulose accounts for 0.005-0.04% of the total mass of the monomer.

In one embodiment, the preparation method comprises the following specific steps:

a) Uniformly mixing a monomer, an initiator and a chain transfer agent according to a proportion, and preparing in advance to obtain an oil phase;

b) Adding a certain volume of deionized water and a proportioning amount of dispersing agent into a batch reaction vessel, stirring and heating to 40-60 ℃ to obtain a water phase;

c) Adding the oil phase formulated in step a) to the aqueous phase prepared in step b) and controlling the oil phase: the volume ratio of the water phase is (1:4) - (1:2), and then stirring is carried out for 20-40 minutes at the temperature of 40-60 ℃;

d) Heating to 65-90 ℃, preserving heat, stirring and reacting for 2-8 hours; then heating to 90-100 ℃, and then preserving heat and stirring for reaction for 1-4 hours;

e) The reaction was ended, and the solid product was collected by settling and filtration, and then washed and dried.

In one embodiment, the monomer is selected from at least one of methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, isobornyl methacrylate, isooctyl methacrylate, lauryl methacrylate, methacrylic acid, beta-carboxyethyl methacrylate, styrene, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, isobornyl acrylate, isooctyl acrylate, lauryl acrylate, acrylic acid, beta-carboxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxyethyl acrylate.

In a preferred embodiment, the initiator is selected from peroxide-based or azo-based free radical initiators.

In a preferred scheme, the initiator is used in an amount of 0.1 to 1.0 percent of the total mass of the monomers.

In a preferred scheme, the chain transfer agent is selected from a mercaptan compound, a mercapto ester compound or a linear dimer of alpha-methylstyrene.

In a preferred scheme, the chain transfer agent is used in an amount of 0.1 to 5.0 percent of the total mass of the monomers.

In a preferred embodiment, in step e), the drying means baking at 40-90 ℃ for 6-12 hours.

Compared with the prior art, the invention has the following remarkable beneficial effects:

Experiments prove that: the invention adopts the compound composition of hydroxyethyl cellulose (HEC) and Methyl Cellulose (MC) as the dispersing agent for preparing solid acrylic resin by suspension polymerization, which not only ensures the smooth proceeding of suspension polymerization reaction, but also ensures that the prepared solid acrylic resin particles are in regular bead shape, and has the advantages of fine average particle diameter, low residual monomer content, difficult caking, good solubility, good glass transition temperature, good molecular weight controllability and the like, and the invention does not need to change the existing suspension polymerization production equipment, has simple operation, universality and repeatability and is easy to realize large-scale production; therefore, compared with the prior art, the invention not only has unexpected technical effects, but also has remarkable industrial application value.

Drawings

FIG. 1 is a graph showing the comparison of particle size distribution of bead-like solid acrylic resin particles obtained in examples 1 to 3 and comparative example 2;

FIG. 2 is a graph showing the comparison of particle size distribution of bead-like solid acrylic resin particles obtained in examples 4 to 6;

FIG. 3 is a photograph of a product of the solid acrylic resin prepared in comparative example 5;

FIG. 4 is a photograph of a product of beaded solid acrylic resin particle prepared in example 6;

FIG. 5 is a comparative photograph showing the solubility test of the solid acrylic resin products prepared in comparative example 6 and example 7.

Detailed Description

The technical scheme of the invention is further and fully described in the following by combining examples. It is to be understood that these examples are illustrative of the present invention and are not intended to limit the scope of the present invention. The experimental procedures, which do not address the specific conditions in the examples below, are generally carried out under conventional conditions or under conditions recommended by the manufacturer.

The measurement methods for the molecular weight in the following examples and comparative examples are as follows:

The molecular weight of the resulting solid acrylic resin was measured by Gel Permeation Chromatography (GPC), PS of different molecular weights were used as a calibrator, tetrahydrofuran was used as a mobile phase, and a flow rate of 1mL/min was set, using an RI detector; the sample was dissolved using tetrahydrofuran.

The measurement methods for the residual monomer ratios in the following examples and comparative examples are as follows:

Accurately weighing 15g of a resin sample, dissolving the resin sample in 100-150 ml of dichloromethane, and then adding 1% (W/W) of EMA relative to the resin sample as an internal standard; setting GC conditions to be 200 ℃ of a sample inlet; the column temperature is raised from 100 ℃ to 230 ℃ in 15 minutes and kept for 15 minutes; the detector temperature is 200 ℃; a filter cotton is arranged at the GC sample inlet to filter out non-volatile components; and testing the ratio of the total peak area of the residual monomers to the peak area of the internal standard, and multiplying the ratio by a percentage number to obtain the monomer residual rate in the resin.

The measurement methods for the glass transition temperature (Tg) in the following examples and comparative examples are as follows:

The Tg of the resulting solid acrylic resin was determined by Differential Scanning Calorimeter (DSC), namely: weighing about 0.15 gram of resin sample in a metal crucible, and accurately recording a weighing value; inputting a scanning temperature interval and other necessary parameters into an instrument; after the scan is completed, the midpoint value of the second scan is selected as the Tg value of the sample.

The morphology of the solid acrylic resin in the following examples and comparative examples was evaluated comprehensively based on an optical microscope, visual inspection, and hand touch.

The particle size distribution of the solid acrylic resin in the following examples and comparative examples was evaluated by sieving with different mesh sieves.

The test methods for resin solubility in the following examples and comparative examples are as follows:

The prepared solid acrylic resin particles were dispersed in tetrahydrofuran at 30% solids using a glass bottle with a cap, then the cap was closed, magnetically stirred for 24 hours in an oil bath at 50 degrees celsius, and then taken out of the oil bath to visually confirm dissolution.

Examples 1 to 3

A preparation method of beaded solid acrylic resin particles comprises the following specific steps:

a) Uniformly mixing 69 parts by mass of methyl methacrylate, 29 parts by mass of n-butyl methacrylate, 1 part by mass of hydroxyethyl methacrylate, 1 part by mass of methacrylic acid, 1 part by mass of benzoyl peroxide and 2 parts by mass of dodecyl mercaptan in advance to obtain an oil phase in advance;

b) Adding a certain volume (taking 3L as an example) of deionized water and a proportioning amount of dispersing agent (see table 1 for specific) into a batch reaction vessel, stirring and heating to 50 ℃ to obtain a water phase;

c) Adding the oil phase prepared in the step a) into the water phase prepared in the step b) (controlling the volume ratio of the oil phase to the water phase to be approximately equal to 1:3, namely adding the oil phase to be 1L, ignoring the influence of a dispersing agent in the water phase on the volume of the water phase, directly taking the added deionized water volume as the volume of the water phase), and stirring for 30 minutes at 50 ℃;

d) Heating to 80 ℃, preserving heat, stirring and reacting for 4 hours; then heating to 95 ℃, and then preserving heat and stirring for reaction for 2 hours;

e) And (3) finishing the reaction, collecting a solid product through standing, settling and filtering, and then washing and drying the obtained solid product (baking at 50 ℃ for 12 hours) to obtain the beaded solid acrylic resin particles.

The purpose of this experiment was to compare in parallel the effect of dispersants of different formulations on monomer residue ratio, particle size distribution, glass transition temperature, weight average molecular weight, product morphology and solubility properties of the prepared bead-like solid acrylic resin particles, as shown in Table 1.

Table 1 experimental results for examples 1 to 3

	Example 1	Example 2	Example 3
				Dispersing agent	0.1 Part by mass of hydroxyethylcellulose+0.01 part by mass of methylcellulose	0.1 Part by mass of hydroxyethylcellulose+0.02 part by mass of methylcellulose	0.1 Part by mass of hydroxyethylcellulose+0.03 part by mass of methylcellulose
Residual monomer (%)	1.12%	0.97%	0.83%
				Particle size distribution	<60 Mesh: 49.4%;60-120 mesh: 46.5%; 120 mesh: 4.1% (as shown in FIG. 1)	<60 Mesh: 43.7%;60-120 mesh: 51.6%; 120 mesh: 4.7% (as shown in FIG. 1)	<60 Mesh: 40.8%;60-120 mesh: 54.1%; 120 mesh: 5.1% (as shown in FIG. 1)
Tg(℃)	75	75	76
				Weight average molecular weight (Da)	36,500	36,300	35,400
Product morphology	Beaded particles; no obvious caking	Beaded particles; no obvious caking	Beaded particles; no obvious caking
				Solubility of	Completely dissolve, the solution is clear and transparent	Completely dissolve, the solution is clear and transparent	Completely dissolve, the solution is clear and transparent

From the experimental results of examples 1 to 3 in table 1, it can be seen that: the compound composition of the hydroxyethyl cellulose and the methyl cellulose (the mass ratio of the hydroxyethyl cellulose to the methyl cellulose is 3:1-10:1) is used as a dispersing agent, so that the beaded solid acrylic resin particles with low monomer residue rate, smaller average particle size, regular morphology, no obvious caking, good dissolution performance and controllable glass transition temperature and molecular weight can be obtained.

Comparative examples 1 to 3

Comparative examples 1 to 3 differ from examples 1 to 3 only in that:

the dispersant used in comparative example 1 was 0.1 part by mass of methylcellulose;

The dispersant used in comparative example 2 was 0.1 part by mass of hydroxyethyl cellulose;

The dispersant used in comparative example 3 was 0.15 parts by mass of hydroxyethyl cellulose;

And the remainder are the same as those described in examples 1 to 3.

The purpose of this comparative experiment was to examine: under the same conditions, single methyl cellulose or hydroxyethyl cellulose is adopted as a dispersing agent in a polymerization system, and the difference between the compound compositions of the hydroxyethyl cellulose and the methyl cellulose adopted in the examples 1-3 is adopted as the dispersing agent. The experimental results of comparative examples 1 to 3 are shown in Table 2.

Table 2 results of experiments of comparative examples 1 to 3

	Comparative example 1	Comparative example 2	Comparative example 3
				Dispersing agent	0.1 Part by mass of methylcellulose	0.1 Part by mass of hydroxyethyl cellulose	0.15 Part by mass of hydroxyethyl cellulose
Residual monomer (%)	/	2.5%	2.3%
				Particle size distribution	/	<60 Mesh: 56.4%;60-120 mesh: 42.7%; 120 mesh: 0.9% (as shown in FIG. 1)	<60 Mesh: 60.2%;60-120 mesh: 38.8%; 120 mesh: 1%
Tg(℃)		73	73
				Weight average molecular weight (Da)	/	33,800	34,300
Product morphology	Polymerization failed and no solid product was obtained	Beaded particles; slightly caking	Beaded particles; slightly caking
				Solubility of	/	Completely dissolve, but the solution is slightly turbid	Completely dissolve, but the solution is slightly turbid

From the experimental results of examples 1 to 3 shown in Table 1 and the experimental results of comparative examples 1 to 3 shown in Table 2, it can be seen that: if methyl cellulose is used alone as a dispersing agent under the same conditions, polymerization failure will be caused (as in comparative example 1), and if hydroxyethyl cellulose is used as a dispersing agent, even if polymerization can be completed, the obtained resin has the defects of high monomer residue rate, coarse average particle size, irregular morphology, obvious caking, poor solubility and the like (as in comparative example 2 and comparative example 3), so that the invention further proves that the compound composition of hydroxyethyl cellulose and methyl cellulose is used as the dispersing agent, and unexpected technical effects and obvious progress are generated.

Examples 4 to 6

Examples 4 to 6 differ from examples 1 to 3 only in the oil phase composition formulation in step a), in particular: uniformly mixing 90 parts by mass of methyl methacrylate, 10 parts by mass of n-butyl acrylate, 0.5 part by mass of tert-butyl peroxy-2-ethylhexanoate and 1 part by mass of dodecyl mercaptan in advance to obtain an oil phase in advance;

The rest is the same as that of examples 1-3, and the experimental results are shown in Table 3.

Table 3 experimental results of examples 4 to 6

	Example 4	Example 5	Example 6
				Dispersing agent	0.1 Part by mass of hydroxyethylcellulose+0.01 part by mass of methylcellulose	0.1 Part by mass of hydroxyethylcellulose+0.02 part by mass of methylcellulose	0.1 Part by mass of hydroxyethylcellulose+0.03 part by mass of methylcellulose
Residual monomer (%)	1.27%	1.43%	1.90%
				Particle size distribution	<60 Mesh: 30.8%;60-120 mesh: 64.9%; 120 mesh: 4.3% (as shown in FIG. 2)	<60 Mesh: 21.4%;60-120 mesh: 62.5%; 120 mesh: 16.1% (as shown in FIG. 2)	<60 Mesh: 11.3%;60-120 mesh: 61.0%; 120 mesh: 27.7% (as shown in FIG. 2)
Tg(℃)	85	85	84
				Weight average molecular weight (Da)	60,300	60,100	59,300
Product morphology	Beaded particles; no obvious caking	Beaded particles; no obvious caking	Beaded particles; no obvious caking (as shown in figure 4)
				Solubility of	Completely dissolve, the solution is clear and transparent	Completely dissolve, the solution is clear and transparent	Completely dissolve, the solution is clear and transparent

It can be seen that the experimental results of examples 1 to 3 shown in table 1 and the experimental results of examples 4 to 6 shown in table 3 are combined: the method disclosed by the invention can be suitable for suspension polymerization systems of different acrylic resins, and can be used for obtaining bead-shaped solid acrylic resin particles which are low in monomer residue rate, small in average particle size, regular in morphology, free of obvious caking, good in solubility, controllable in glass transition temperature and molecular weight, so that the method disclosed by the invention has universality and repeatability.

Comparative examples 4 to 5

Comparative examples 4 to 5 differ from examples 4 to 6 only in that:

the dispersant used in comparative example 4 was 0.1 part by mass of methylcellulose;

the dispersant used in comparative example 5 was 0.1 part by mass of hydroxyethyl cellulose;

the rest of the contents are the same as those in examples 4 to 6, and the experimental results are shown in Table 4.

Table 4 Experimental results for comparative examples 4 to 5

	Comparative example 4	Comparative example 5
			Dispersing agent	0.1 Part by mass of methylcellulose	0.1 Part by mass of hydroxyethyl cellulose
Residual monomer (%)	/	2.8%
			Particle size distribution	/	Has obvious caking
Tg(℃)		82
			Weight average molecular weight (Da)	/	55,000
Product morphology	Polymerization failed and no solid product was obtained	Obvious caking (as shown in FIG. 3)
			Solubility of	/	Completely dissolve, but the solution is slightly turbid

From the experimental results of examples 4 to 6 shown in Table 3 and the experimental results of comparative examples 4 to 5 shown in Table 4, it can be further confirmed that: if methyl cellulose is used alone as a dispersing agent under the same conditions, polymerization failure will be caused (as in comparative example 4), and if hydroxyethyl cellulose is used as a dispersing agent, even if polymerization can be completed, the obtained resin has the defects of high monomer residue rate, coarse average particle size, irregular morphology, obvious caking, poor solubility and the like (as in comparative example 5), so that further explanation is provided that the invention adopts a compound composition of hydroxyethyl cellulose and methyl cellulose as the dispersing agent, and unexpected technical effects and obvious progress are generated.

Examples 7 to 8

Examples 7 to 8 differ from examples 1 to 3 only in that:

The composition of the oil phase in step a) and the dispersant in step b) are different (see Table 5 for details);

the rest is the same as that of examples 1-3, and the experimental results are shown in Table 5.

Table 5 Experimental results for examples 7-8

	Example 7	Example 8
			Monomer(s)	45 Parts by mass of methyl methacrylate +20 parts by mass of styrene +15 parts by mass of isooctyl methacrylate +8 parts by mass of ethyl acrylate +3 parts by mass of methacrylic acid +9 parts by mass of hydroxybutyl acrylate	65 Parts by mass of isobutyl methacrylate +15 parts by mass of methyl acrylate +10 parts by mass of glycidyl methacrylate +10 parts by mass of t-butyl methacrylate
Initiator(s)	0.1 Part by mass of azobisisobutyronitrile +0.3 part by mass of lauroyl peroxide	0.15 Part by mass of tert-butyl peroxy-2-ethylhexanoate
			Chain transfer agent	2.8 Parts by mass of n-octanethiol	1.1 Parts by mass of n-butyl mercaptopropionate
Dispersing agent	0.5 Part by mass of hydroxyethylcellulose+0.005 part by mass of methylcellulose	0.1 Part by mass of hydroxyethylcellulose+0.04 part by mass of methylcellulose
			Residual monomer (%)	1.46%	1.78%
Particle size distribution	<60 Mesh: 15.5%;60-120 mesh: 79.8%; 120 mesh: 4.7%	<60 Mesh: 12.7%;60-120 mesh: 70.5%; 120 mesh: 16.8%
			Tg(℃)	54	42
Weight average molecular weight (Da)	12,500	44,300
			Product morphology	Beaded particles; no obvious caking	Beaded particles; no obvious caking
Solubility of	Complete dissolution, clear and transparent solution (as shown in right bottle in FIG. 5)	Completely dissolve, the solution is clear and transparent

It can be seen that the experimental results of examples 1 to 3 shown in table 1 and the experimental results of examples 7 to 8 shown in table 5 are combined: the method disclosed by the invention can be suitable for suspension polymerization systems of different acrylic resins, and can be used for obtaining bead-shaped solid acrylic resin particles which are low in monomer residue rate, small in average particle size, regular in morphology, free of obvious caking, good in solubility, controllable in glass transition temperature and molecular weight, so that the method disclosed by the invention has universality and repeatability.

Comparative examples 6 to 7

Comparative example 6 differs from example 7 in that: comparative example 6 uses 0.5 parts by mass of hydroxyethyl cellulose as the dispersant, the remainder being the same as described in example 7; comparative example 7 differs from example 8 in that: comparative example 7 uses 0.1 part by mass of hydroxyethyl cellulose as the dispersant, and the rest is the same as that described in example 8; the experimental results are shown in Table 6.

TABLE 6 Experimental results for comparative examples 6 to 7

	Comparative example 6	Comparative example 7
			Dispersing agent	0.5 Part by mass of hydroxyethyl cellulose	0.1 Part by mass of hydroxyethyl cellulose
Residual monomer (%)	3.12%	2.53%
			Particle size distribution	<60 Mesh: 28.1%;60-120 mesh: 70.8%; 120 mesh: 1.1%	<60 Mesh: 43.7%;60-120 mesh: 55.5%; 120 mesh: 0.8%
Tg(℃)	50	38
			Weight average molecular weight (Da)	10,600	39,400
Product morphology	Beaded particles; slightly caking	Beaded particles; slightly caking
			Solubility of	Complete dissolution, but slightly cloudy solution (as shown in the left bottle of FIG. 5)	Completely dissolve, but the solution is slightly turbid

From the experimental results of examples 7 to 8 shown in Table 5 and the experimental results of comparative examples 6 to 7 shown in Table 6, it can be further confirmed that: if the other conditions are the same, and the hydroxyethyl cellulose is singly used as a dispersing agent, even if the polymerization can be completed, the obtained resin has the defects of high monomer residue rate, coarse average particle size of products, irregular morphology, obvious caking, poor solubility and the like.

Finally, it is pointed out here that: the above is only a part of the preferred embodiments of the present invention and should not be construed as limiting the scope of the present invention, and some insubstantial modifications and adaptations of the present invention based on the foregoing are within the scope of the present invention.

Claims

1. A preparation method of beaded solid acrylic resin particles adopts a suspension polymerization method, and a polymerization system contains monomers, an initiator, a chain transfer agent, a dispersing agent and medium water, and is characterized in that: the dispersing agent is a compound composition of hydroxyethyl cellulose and methyl cellulose, wherein the dosage of the hydroxyethyl cellulose accounts for 0.1-0.5% of the total mass of the monomer, and the dosage of the methyl cellulose accounts for 0.005-0.04% of the total mass of the monomer.

2. The method for producing bead-like solid acrylic resin particles according to claim 1, wherein the method comprises the specific steps of:

3. The method for producing bead-like solid acrylic resin particles according to claim 1 or 2, wherein: the monomer is at least one selected from methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, isobornyl methacrylate, isooctyl methacrylate, lauryl methacrylate, methacrylic acid, beta-carboxyethyl methacrylate, styrene, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, isobornyl acrylate, isooctyl acrylate, lauryl acrylate, acrylic acid, beta-carboxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate.

4. The method for producing bead-like solid acrylic resin particles according to claim 1 or 2, wherein: the initiator is selected from peroxide or azo radical initiator.

5. The method for producing bead-like solid acrylic resin particles according to claim 1 or 2, wherein: the dosage of the initiator is 0.1 to 1.0 percent of the total mass of the monomers.

6. The method for producing bead-like solid acrylic resin particles according to claim 1 or 2, wherein: the chain transfer agent is selected from a mercaptan compound, a mercapto ester compound or a linear dimer of alpha-methyl styrene.

7. The method for producing bead-like solid acrylic resin particles according to claim 1 or 2, wherein: the use amount of the chain transfer agent is 0.1-5.0% of the total mass of the monomer.

8. The method for producing bead-like solid acrylic resin particles according to claim 2, wherein: in the step e), the drying refers to baking at 40-90 ℃ for 6-12 hours.