JPH01132601A - Production of macromonomer - Google Patents

Abstract

PURPOSE:To produce a highly pure macromonomer, by reacting a linear polymer having a functional group on one end with a vinyl compound in a specified solvent in the presence of a polymerization inhibitor, while blowing a gas containing molecular oxygen into the reaction mixture. CONSTITUTION:A vinyl monomer (e.g., styrene) is polymerized at 50-90 deg.C for several hr in the presence of water, a dispersant and a surfactant. The formed polymer is reacted with 0.8-5.0mol, per mol of said functional group, of a vinyl compound having a group reactive with said functional group [e.g., glycidyl (meth)acrylate] at room temperature to 150 deg.C in the presence of 10-2000ppm of a polymerization inhibitor (e.g., phenothiazine) and 0.1-3wt.%, based on the reaction solution, catalyst (e.g., tert. amine) while blowing a gas containing molecular oxygen into the reaction mixture.

Description

[Detailed Description of the Invention] (a) Purpose of the Invention [Field of Industrial Application] The present invention provides that the present invention itself or the graft polymer obtained therefrom becomes a powerful material for improving the functionality of various polymeric materials. This invention relates to a method for producing macromonomers.

[Conventional technology and its problems]

Attempts have been made to use block polymers and graft polymers for a long time to improve the functionality of various polymeric materials, and the block polymers and graft polymers used for this purpose are manufactured by ionic polymerization. Graft polymers obtained by radical polymerization of monomers in the presence of a block polymer or a backbone polymer to form a technical polymer composed of monomer units different from the backbone polymer are known.

However, with block polymers produced by ionic polymerization, the types of polymers that can be produced, that is, their chemical structures, are limited to a relatively narrow range, and it is difficult to meet the actual demand for block polymers with diverse polymer structures. There was a problem. In addition, the graft polymer produced by the above method has problems such as: (1) high content of homopolymer in the branch and trunk components, and (2) difficulty in controlling the molecular weight and composition of both the branch and trunk components. .

On the other hand, graft polymers obtained by a method using macromonomers as researched by Milkovich et al. have recently attracted attention. Macromonomer refers to an oligomer or polymer having a polymerizable functional group at the end of the molecule, for example, a process for producing a linear polymer having a functional group at the end (polymerization reaction), and a reaction capable of reacting with the functional group. It can be obtained by a manufacturing method comprising a step of manufacturing a macromonomer by a reaction between a compound having both a vinyl polymerizable group and a vinyl polymerizable group in the molecule and the linear polymer (hereinafter referred to as macromonomerization reaction). They proposed a method for producing a graft polymer by copolymerizing this and other copolymerizable monomers (for example, Japanese Patent Publication No. 116586/1986).

Regarding macromonomers, many other proposals have been made; for example, British company ICI has developed a terminal carboxylic acid type monomer obtained by polymerizing radically polymerizable monomers such as methyl methacrylate in the presence of mercaptoacetic acid as a chain transfer agent. proposed to produce a macromonomer by reacting an oligomer with glycidyl methacrylate (Japanese Patent Publication No. 43-11224,
-16147, etc.).

Graft polymers produced by methods using such macromonomers (hereinafter referred to as graft polymers produced by macromonomer methods) have clearly regulated structures, and the production method itself is easy, so they are not suitable for industrial use. is beginning to be considered important.

However, in the conventional method for producing a graft polymer using the macromonomer method, in the production stage of the macromonomer and the production stage of the graft polymer by polymerizing the macromonomer and other copolymerizable monomers,
Organic solvents are used as reaction solvents, and there are concerns about fires and poisoning due to the toxicity caused by the organic solvents. Since operations such as removal of the solvent are required and manufacturing costs are high, this method is unsatisfactory as an industrial manufacturing method, and improvements in the manufacturing process have been desired.

(B) Structure of the Invention [Means for Solving the Problems] As a result of intensive study in view of the above-mentioned problems, the present inventors have determined that the macromonomerization reaction during the production of macromonomers can be carried out in the production of graft polymers in the subsequent process. The macromonomerization reaction itself was carried out smoothly in a solvent consisting of vinyl monomers, based on the idea that problems with conventional methods could be solved by copolymerizing vinyl monomers with vinyl monomers. However, under conditions suitable for macromonomerization reactions, we encountered a new problem: the undesirable polymerization of vinyl monomers. As a result of further investigation, we found that even if the macromonomerization reaction was carried out at an appropriate temperature, for example, at a high temperature close to the polymerization temperature of the vinyl monomer, the vinyl monomer did not polymerize, whereas the macromonomerization reaction was completely inhibited. The present invention was completed by finding a technical means that could not be solved.

That is, the present invention combines a linear polymer having a functional group at one end (hereinafter referred to as a prepolymer) and a vinyl compound having a group reactive with the functional group, and a macromonomer produced by the reaction of these. A macro characterized by using a vinyl monomer that is copolymerizable and soluble in the macromonomer as a solvent, and reacting in the solvent in the presence of a polymerization inhibitor while blowing a molecular oxygen-containing gas. This is a method for producing monomers.

In addition, the macromonomer in the present invention refers to a prepolymer having a number average molecular weight of 1,000 to 50,000, a reactive group that can react with a functional group at one end of its molecular chain, and a vinyl polymerizable group. It refers to a macromonomer produced by reaction with a compound contained in the macromonomer (macromonomerization reaction).

The present invention will be explained in more detail below.

[Prepolymer]

The prepolymer used in the present invention is a linear polymer consisting of vinyl monomer units, having a functional group at one end, and having a number average molecular weight of about 1,000 to 50,000. Vinyl monomers that can be used include vinyl esters of organic acids such as vinyl acetate, styrene, styrene substitutes, vinyl aromatic compounds such as vinylpyridine and vinylnaphthalene, (meth)acrylic acid esters, (meth)acrylonitrile, and acrolein. , N-vinyl compounds such as N-vinylpyrrolidone and N-vinylcaprolactam, unsaturated acid anhydrides such as maleic anhydride, N-substituted maleimides such as N-phenylmaleimide, unsaturated halides such as vinyl chloride and vinylidene chloride. These monomers can be used alone or in combination of two or more.

Preferred monomers include styrene, styrene substitutes, (meth)acrylic acid esters, and (meth)acrylonitrile, since the functional groups in the prepolymer are unlikely to cause side reactions in the macromonomerization reaction of the prepolymer. It will be done.

The functional groups that should be present at the molecular ends of the prepolymer are:
Carboxyl groups are preferred, and their introduction into the prepolymer can be carried out during the production of the prepolymer, for example by adding mercaptoacetic acid,
This can be easily carried out by using a mercaptan chain transfer agent such as 2-mercaptopropionic acid and 3-mercaptopropionic acid.

The molecular weight of the prepolymer in the present invention may be within a range that does not impair the polymerizability of the macromonomer produced using the prepolymer as a raw material, and the number average molecular weight is 1000 to 50.
000, preferably 2000 to 40000. If the molecular weight is less than 1000, the degree of polymerization as a polymer unit is too low, and when a graft polymer is produced, the physical properties of the macromonomer will not be reflected in the physical properties of the graft polymer. is low, and tends to cause problems such as phase separation of the reaction system.

The number average molecular weight of the macromonomer is a polystyrene equivalent molecular weight determined by gel permeation chromatography (hereinafter referred to as GPC), and the measurement conditions are as follows.

Apparatus: High performance liquid chromatography (e.g. Toyo Soda Kogyo ■Product name 11LC-802UR) Column: Polystyrene gel (e.g. Toyo Soda Kogyo ■Product name G4000)
H8 and G3000H8) Elution solvent: Tetrahydrofuran Eflux rate: 1.0 ml/lll1n Ram temperature: 4
0°C Detector: R ■ Methods for producing detector prepolymers include radical polymerization and ionic polymerization, but radical polymerization is preferred because it does not require strict purification operations and is industrially advantageous. Preferably legal.

In the method for producing a prepolymer by a radical polymerization method, any of the known solution polymerization methods, bulk polymerization methods, suspension polymerization methods, or emulsion polymerization methods can be employed in the presence or absence of a radical polymerization initiator. The bulk polymerization method and the suspension polymerization method are preferable because there is a high probability that the chain transfer agent that contributes to the introduction of groups will be bonded to the molecular terminal of the prepolymer and there is no need to use an organic solvent.

To explain the prepolymer manufacturing method using suspension polymerization, which is a preferred polymerization method, as an example, a small amount of a polymerization initiator is added to a polymerization vessel containing a predetermined amount of water, a dispersant, and a surfactant under stirring. After dropping the vinyl monomer consisting of 5
The temperature is raised to 0 to 90"C and polymerization is carried out for several hours. The obtained prepolymer can be isolated in powder form through operations such as filtration and water washing.

Examples of the dispersant include polyvinyl alcohol, partially saponified polyvinyl alcohol, methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose,
Synthetic polymer substances such as hydroxypropyl methylcellulose, acrylic acid polymer, polyvinylpyrrolidone, maleic anhydride-vinyl acetate copolymer, starch, gelatin,
One type of natural polymeric substances such as gum arabic, sparingly soluble phosphate metal salts such as phosphates of calcium, barium, strontium, magnesium, aluminum, iron or cobalt (including polyphosphoric acid condensed with two or more components); Mixtures of two or more types may be mentioned. Preferably used dispersants include polyvinyl alcohol, partially saponified polyvinyl alcohol, methyl cellulose, and sparingly soluble phosphate metal salts.

Examples of surfactants include anionic surfactants such as sodium dodecylbenzenesulfonate, sodium octyl sulfate, dioctyl ester of sodium sulfosuccinate, alkali lauryl sulfate, or alkali salts of fatty acids, and cationic and nonionic surfactants. Active agents can be mentioned, and one type or a mixture of two or more types of these can be used. Preferably sodium dodecylbenzenesulfonate is used.

Examples of polymerization initiators include water-insoluble azo initiators and peroxide initiators, which are radical polymerization initiators used in suspension polymerization methods, but mercaptan chain transfer agents and An azo initiator that does not cause this reaction is preferred. As the azo initiator, 2.2-azobisisobutyronitrile (hereinafter abbreviated as AIBN), 4.4
-Azobis-4-cyanovaleric acid (ACV)
A), 1-azobis-1-cyclohexanecarbonitrile (hereinafter abbreviated as ACIN), and the like.

[Macromonomerization reaction] As the vinyl compound having a reactive group capable of reacting with one end functional group of the prepolymer, which is used in the macromonomerization reaction of the present invention, when the end functional group of the prepolymer is a carboxyl group, Typical examples include compounds that have both an epoxy group that is highly reactive with carboxyl groups and a vinyl polymerizable group. Specifically, glycidyl (
Examples include meth)acrylate, allyl glycidyl ether, and chloromethylvinylbenzene.

The above-mentioned vinyl compound is reacted with the prepolymer at a ratio of preferably 0.8 to 5.0 times the mole, more preferably 0.9 to 3.0 times the mole of the functional group at one end of the prepolymer. If this ratio is less than 0.8 times the mole, it is not preferable because a large amount of unreacted prepolymer tends to remain in the obtained macromonomer, and if it is more than 5.0 times the mole, the graft polymer produced from the obtained macromonomer This is not preferable because the amount of vinyl compound units mixed in as an impurity in the main component increases.

In the macromonomerization reaction, the vinyl monomer used as a solvent is one that can dissolve the produced macromonomer and has copolymerizability with the macromonomer. More specifically, from among the monomers exemplified above as raw materials for prepolymer production, vinyl monomers that meet the above requirements and that are desired to be copolymerized with the macromonomer during the subsequent production of graft polymers are selected. Just use your body.

The quantitative ratio of the prepolymer to the vinyl monomer is such that the amount of the prepolymer is preferably 5 to 70% by weight, more preferably 10 to 60% by weight, based on the total amount of the prepolymer and the vinyl monomer. If the amount of preparation is less than 5% by weight,
When a graft polymer is produced, there is a shortage of macromonomer components that become branch components of the graft polymer, so the physical properties of the macromonomer are not reflected in the graft polymer, which is undesirable. If the solution viscosity becomes too high, the free molecular movement of the macromonomer in the solution is inhibited, making it difficult to obtain a graft polymer in which the macromonomer is uniformly copolymerized, which is not preferable.

The macromonomerization reaction in the present invention needs to be carried out in the presence of a polymerization inhibitor while blowing molecular oxygen or a gas containing it into the reaction solution.

As the polymerization inhibitor, known polymerization inhibitors such as phenothiazine, hydroquinone, hydroquinone monomethyl ether, etc. can be used, and the preferred amount used is 20
00ppm+ to 10pp+m, more preferably 1
000ppa+ to 10ppm, particularly preferably 1
00 to 500pp.

If the amount of the polymerization inhibitor used exceeds 2000 ppm,
It becomes difficult to initiate polymerization when producing a graft polymer, and on the other hand, if it is less than 10 pp+s, polymerization of the vinyl monomer, which is a solvent, tends to occur in the macromonomerization reaction.

A typical example of a gas containing molecular oxygen is air, but nitrogen gas containing several percent oxygen can also be used, and the optimum amount of these gases to be blown depends on the amount of polymerization inhibitor used and the reaction. It varies depending on the temperature, etc., and can be appropriately determined depending on the specific reaction conditions so that polymerization does not occur within the reaction system.

In a macromonomerization reaction, for example, in the case of a reaction between a prepolymer having a terminal carboxyl group and an epoxy group-containing vinyl compound, a tertiary amine, quaternary ammonium salt, etc. is added as a reaction catalyst to the entire reaction solution. .1
It is preferred to use ~3% by weight. If the catalyst amount is less than 0.1% by weight, the reaction rate is slow, and if it is more than 3% by weight, the obtained macromonomer is likely to cause problems as an impurity when used as a graft polymer or as a polymer material, so both are not preferred.

The reaction temperature is preferably room temperature to 150°C, and 50 to 1
00°C is more preferred. When the reaction temperature is below room temperature, the reaction rate is slow, and when it exceeds 150°C, the nyl monomer boils and polymerization reaction tends to occur.

[Usage of macromonomer]

The macromonomer in the present invention is obtained as a vinyl monomer solution. This product can be used industrially as a curable composition as it is, or as an intermediate product for obtaining a graft polymer by subsequent polymerization as it is.

When producing a graft polymer from a macromonomer according to the present invention, bulk polymerization, suspension polymerization, and emulsion polymerization are preferred because they do not use organic solvents, but macromonomers have poor emulsion stability. Bulk polymerization method and suspension polymerization method are more suitable.
The suspension polymerization method is optimal because the catalyst such as an amine compound used in the macromonomerization reaction is dissolved in water and the amount remaining in the graft polymer is reduced.

Using the macromonomer produced by the method of the present invention,
The case where a graft polymer is produced by suspension polymerization, which is the most suitable method, will be explained below.

Polymerization is performed by charging a predetermined amount of water, a dispersant, and a surfactant into a polymerization vessel with stirring, and adding a vinyl monomer solution of a macromonomer or a vinyl monomer and a polymerization initiator as necessary to this solution. After dropping the solution, it is heated to a predetermined temperature to cause radical polymerization.

When adding a vinyl monomer, it may be of the same type or different type from the vinyl monomer used during the macromonomerization reaction, and since it has a reactive functional group, it is difficult to add a vinyl monomer. Vinyl monomers that cannot be used during the reaction can be added at this point.

As the dispersant and surfactant used in the suspension polymerization method described above, the specific compounds exemplified in the suspension polymerization method of the prepolymer can be used. As a polymerization initiator, benzoyl peroxide, lauroyl peroxide, t
- Peroxides such as butyl perbenzoate and t-butyl peroctoate, and azo compounds such as AIBN and ACVASACHN can be used, but there is no possibility of oxidative decomposition of the chain transfer agent bond in the macromonomer. in,
Preferred are azo compounds.

Suitable polymerization temperature is 30°C to 100°C, and 50°C to 100°C.
It is more preferable that the temperature is from 0°C to 90°C. If the degree of reaction is less than 30°C, the polymerization rate is too low, while at 100°C
Exceeding this is not preferable because the dispersion medium tends to boil and the suspension stability decreases.

After filtering the obtained polymer-containing aqueous liquid, the graft polymer can be isolated by, for example, washing the filtered powder with water.

A macromonomer is produced by the method of the present invention using a prepolymer produced by a suspension polymerization method or a bulk polymerization method, and a graft polymer is produced by a suspension polymerization method using a vinyl monomer solution of the obtained macromonomer. If so, there is no need to use organic solvents in the entire series of steps, so the manufacturing process can be simplified and manufacturing costs can be reduced compared to conventional manufacturing methods that use organic solvents. The value of the present invention is great in that the quality of the polymer itself is at least equivalent, and usually superior.

The graft polymer produced as described above can be used by itself as an adhesive, paint, molding material, elastomer, or other polymeric material. It can also be used as a modifier and as a means to improve the functionality and performance of polymeric materials used in boats.

Examples of use as modifiers include surface and interface modifiers for various polymeric materials, polymer blend compatibilizers, dispersants,
Applications that utilize the surface activity and multiphase structure of graft polymers include functional materials such as emulsifiers, biocompatible materials, and selectively permeable membrane materials.

[Reference examples, working examples and application examples]

The present invention will be described in more detail below with reference to reference examples, examples, and application examples. In addition, all the percentages written on each side represent % by weight, and the parts represent parts by weight.

Reference Example 1 Production of a prepolymer consisting of methyl methacrylate units (hereinafter referred to as MMA prepolymer) ■ In a glass flask equipped with a stirring group, a reflux condenser, nine dropping funnels, and a thermometer, 400 parts of distilled water, polyvinyl alcohol (manufactured by Kuraray ■), 4 parts of a 5% aqueous solution of Poval 420), 10 parts of a calcium phosphate suspension (Supertite 10, manufactured by Nihon Kagaku Kogyo ■), and 0.2 parts of a 5χ aqueous solution of sodium dodecylbenzenesulfonate (Emar 2F, manufactured by Kao ■) were prepared. . A mixed solution containing 98 parts of methyl methacrylate (hereinafter abbreviated as MMA), 4.24 parts of 3-mercaptopropionic acid, and 0.05 parts of AIBN O was placed in a dropping funnel. Heat the flask to raise the temperature of the internal liquid to 80°C.
After setting the temperature, the monomer mixture was added dropwise from the dropping funnel over a period of 1 minute. The temperature was maintained at 80° C. for 10 hours to complete the polymerization. During this time, the rotation speed of the stirrer was maintained at 300 rpm.

No problems such as blocking occurred during the reaction. After the reaction, it was filtered, washed with water, and dried under reduced pressure to obtain 91 parts of solid MMA prepolymer. The polystyrene equivalent molecular weight determined by GPC was Mn=9,400 and Mw=20,000. Further, the acid value of this MMA prepolymer, determined by titration using a 0.1N ethanol solution of KOI, was 0.169 meq/g.

Reference Example 2 Production of MMA Prepolymer ■ 90 parts of a solid MMA prepolymer was obtained in exactly the same manner as in Reference Example 1 except that 2.12 parts of 3-mercaptopropionic acid was used. The polystyrene equivalent molecular weight by GPC is Mn=22. OOOMw=43°000.

Moreover, the acid value was 0.0855+meq/g.

Reference Example 3 Production of MMA Prepolymer ■ 91 parts of a solid MMA prepolymer was obtained in the same manner as in Reference Example 1 except that 1.06 parts of 3-mercaptopropionic acid was used. The polystyrene equivalent molecular weight determined by GPC was Mn=46.000 and Mw=102.000. Moreover, the acid value was 0.0420 meq/g.

Reference Example 4 Production of MMA prepolymer - Into a glass flask equipped with a stirrer, a reflux condenser, two dropping funnels, a gas inlet and a thermometer, 30 parts of MMA and 1.06 parts of 3-mercaptopropionic acid were charged. Add 70 parts of MMA to one dropping funnel (referred to as dropping funnel A), and 1 part of AIBN to the other dropping funnel (referred to as dropping funnel B).
and 70 parts of toluene were added. After introducing nitrogen gas, the temperature of the flask was increased to keep the reaction solution at 90° C., and the mixture was added dropwise through dropping funnel A over 2 hours and dropping funnel B over 5 hours. The reaction system was further heated for 2 hours to decompose the AIBN present in the reaction system. The reaction solution was dried under reduced pressure at 80°C to form solid M.
96 parts of MA prepolymer were obtained. The polystyrene equivalent molecular weight by GPC is Mn・11,000 Mw=22.
It was 200.

Example 1 Production of a macromonomer consisting of methyl methacrylate units (hereinafter referred to as MMA macromonomer) I MMA prepolymer 80 produced in Reference Example 1 was placed in a glass flask equipped with a stirrer, a reflux condenser, an air introduction tube, and a thermometer. After charging 187 parts of styrene monomer, 1.34 parts of tetrabutylammonium bromide, 2.32 parts of 0MA, and 0.05 parts of hydroquinone methyl ether, the flask was heated to raise the temperature of the internal liquid to 90°C.
The temperature was set to 1, and the reaction was carried out at this temperature for 6 hours. During the reaction, air was bubbled to prevent polymerization. After reaction, KOH
The acid value was measured by titration with a 0.1N ethanol solution, and the reaction conversion rate was found to be 98.8%. No particular change was observed in the GPC chart of the reaction solution, indicating that the macromonomer was stably produced.

Example 2 Production of MMA macromonomer ■ 80 parts of the prepolymer produced in Reference Example 2, 1 part of GMA
．． The procedure was carried out in exactly the same manner as in Example 1 except that 46 parts were used. The reaction conversion rate was 98.7%, and the G of the reaction solution was
No particular change was observed in the PC chart, indicating that the macromonomer was stably produced.

Example 3 Production of MMA macromonomer■ 80 parts of the prepolymer produced in Reference Example 3 and 0 GMA
．． The procedure was carried out in exactly the same manner as in Example 1 except that 96 parts were used. The reaction conversion rate was 97.9%, and the G of the reaction solution was
No particular change was observed in the PC chart, indicating that the macromonomer was stably produced.

Example 4 Production of MMA macromonomer■, 80 parts of the prepolymer produced in Reference Example 4, GMA
Example 1 was carried out in exactly the same manner as in Example 1, except that 1.46 parts of . The reaction conversion rate was 97.5%, and no particular change was observed in the GPC chart of the reaction solution, indicating that the macromonomer was stably produced.

Example 5 Production of MMA' micromonomer ■N-butyl acrylate was used instead of styrene monomer.
The procedure was exactly the same as in Example 1, except that the same amount was used. The reaction conversion rate was 98.5%, and the GP of the reaction solution
No particular change was observed in the C chart, indicating that the macromonomer was stably produced.

Application example 1 Production of styrene-MMA graft polymer■ In a glass flask equipped with a stirring group, reflux condenser, dropping funnel, and thermometer, 400 parts of distilled water and 4 parts of a 5% aqueous solution of polyvinyl alcohol (Poval 420 manufactured by Kuraray ■) were added. , 10 parts of calcium phosphate suspension (Super Tie, manufactured by Nihon Kagaku Kogyo ■), 0.0 parts of a 5x aqueous solution of thorium dodecylbenzenesulfonate (Emeru 2F, manufactured by Kao ■).
I prepared the second part. In Example 2, aJ
100 parts of styrene monomer solution of macromonomer, A
A solution containing 0.5 parts of IBN was placed in the dropping funnel. After heating the flask to set the temperature of the internal liquid at 80°C, the monomer mixture was added dropwise from the dropping funnel over 1 minute. The temperature was maintained at 80° C. for 10 hours to complete the polymerization. During this time, the rotation speed of the stirrer was maintained at 300 rpm. No problems such as blocking occurred during the reaction. After the reaction, the mixture was filtered, pickled, and dried under reduced pressure to obtain 93 parts of a solid styrene-MMA graft polymer. Polystyrene equivalent molecular weight by GPC is Mn=84,000 Mw=400.0
It was 00. Furthermore, no macromonomer peak was observed in the GPC chart, indicating that the graft polymer was efficiently produced.

Application example 2 Manufacture of styrene-MMA graft polymer■ Into a glass flask equipped with a stirring base, a reflux condenser, 9 dropping funnels, and a thermometer, 400 parts of distilled water and 4 parts of a 5% aqueous solution of polyvinyl alcohol (Poval 420 manufactured by Kuraray ■) were added. , calcium phosphate suspension (Super Thai manufactured by Nihon Kagaku Kogyo ■) 10) 10 parts, 5χ aqueous solution of sodium dodecylbenzenesulfonate (Emar 2F manufactured by Kao ■) 0.2
I prepared a section. A solution containing 66.7 parts of the styrene monomer solution of the MMA macromonomer prepared in Example 2, an additional 33.3 parts of styrene monomer, and 5 parts of AIBN O was placed in the dropping funnel.

After heating the flask to set the temperature of the internal liquid at 80°C, the monomer mixture was added dropwise from the dropping funnel over a period of 1 minute. The temperature was maintained at 80'C for 10 hours to complete the polymerization. During this time, the rotation speed of the stirrer was maintained at 300 rpm.

No problems such as blocking occurred during the reaction.

After the reaction, the mixture was filtered, pickled, and dried under reduced pressure to obtain 94 parts of a solid styrene-MMA graft polymer. The polystyrene equivalent molecular weight by GPC is Mn=75.000
M% was 1-311.000. Furthermore, no macromonomer peak was observed in the GPC chart, indicating that the graft polymer was efficiently produced.

Application example 3 Production of styrene-MMA graft polymer ■ In a glass flask equipped with a stirring group, reflux condenser, two dropping funnels, and a thermometer, 400 parts of distilled water and a 5% aqueous solution of volivinyl alcohol (Poval 220B manufactured by Kuraray ■) were added.
10 parts, calcium phosphate suspension (Super Thai manufactured by Nihon Kagaku Kogyo ■) 10 parts, 5x aqueous solution of sodium dodecylbenzenesulfonate (Emar 2F manufactured by Kao ■) 0.
I prepared the second part. A solution containing 66.7 parts of the styrene monomer solution of the MMA macromonomer produced in Example 3, an additional 33.3 parts of styrene monomer, and 0.5 parts of ACIN was placed in the dropping funnel. After heating the flask to raise the temperature of the internal liquid to 90"C, the monomer mixture was added dropwise from the dropping funnel over 1 minute. The temperature was maintained at 90"C for 20 hours to complete the polymerization. During this time, the rotation speed of the stirrer was 30.
It was kept at 0 rpn+. No problems such as blocking occurred during the reaction. After the reaction, it is filtered, pickled, and dried under reduced pressure to obtain a solid styrene-MMA graft polymer 88.
I got the department. The polystyrene equivalent molecular weight by GPC is M
n=150,000 M%1=494.000 Furthermore, no macromonomer peak was observed in the GPC chart, indicating that the graft polymer was efficiently produced.

(c) Effects of the Invention According to the present invention, it is possible to produce high-purity macromonomers and graft polymers by a production method that does not require organic solvents, and there are risks during production that are caused by organic solvents, such as fire and poisoning. As a result, special drying equipment is not required, and the manufacturing process can be simplified in other respects, which is extremely advantageous in terms of manufacturing costs.

Claims (1)

[Claims] 1. A linear polymer having a functional group at one end and a vinyl compound having a group reactive with the functional group are copolymerizable with the macromonomer produced by these reactions, and the macromonomer is copolymerizable with the macromonomer produced by the reaction. A method for producing a macromonomer, which comprises using a vinyl monomer in which is soluble as a solvent, and carrying out a reaction in the solvent in the presence of a polymerization inhibitor while blowing a molecular oxygen-containing gas.