JP4596772B2 - Method for producing vinyl chloride copolymer resin - Google Patents

Description

  The present invention relates to a method for producing a vinyl chloride copolymer resin. More specifically, the present invention relates to a vinyl chloride monomer and an ethylenically unsaturated monomer containing a double bond, which has little generation of scale and excellent polymerization stability. The present invention relates to a method for producing a vinyl chloride copolymer resin obtained by copolymerizing a macromonomer having a polymer with a main chain.

Vinyl chloride resins are inexpensive and have excellent mechanical properties and chemical properties, and are excellent in quality balance. By using plasticizers, molded products ranging from hard to soft can be obtained. Is a thermoplastic resin used in various fields. There are various uses, and various characteristics are required in terms of performance according to each use. In order to improve the required characteristics, not only vinyl chloride homopolymer resins but also vinyl chloride copolymer resins have been studied. For example, in order to improve gelation as a plastisol in which a resin is dispersed in a plasticizer to give fluidity, the co-polymerization of a vinyl chloride monomer and a vinyl monomer that gives a vinyl polymer having a low glass transition temperature. There exists a method (patent document 1) which manufactures coalescence. However, in this method, the polymerization reaction rates of the two monomers are often different, and there are problems such as forming a homopolymer or increasing the scale inside the polymerization reactor.
Japanese Unexamined Patent Publication No. 63-23947

  The present invention is obtained by copolymerizing a vinyl chloride monomer and a macromonomer having a polymer composed of an ethylenically unsaturated monomer containing a double bond in the main chain, with little generation of scale and excellent polymerization stability. It is an object of the present invention to provide a method for producing a vinyl chloride copolymer resin.

  As a result of diligent research, the present inventors started a copolymerization reaction after predispersing and mixing a macromonomer having a polymer composed of an ethylenically unsaturated monomer containing a double bond in the main chain with a vinyl chloride monomer. As a result, the present inventors have found that the above-mentioned problems can be solved and completed the present invention.

That is, the present invention
(1) In producing a vinyl chloride copolymer resin by copolymerizing a vinyl chloride monomer and a macromonomer having a polymer composed of an ethylenically unsaturated monomer containing a double bond in the main chain, vinyl chloride is used. the macromonomer chromatography having an ethylenically unsaturated comprising a monomer polymers containing system monomer with double bonds in the main chain was dispersed mixture over 1 minute at a temperature of 60 ° C. 20 ° C. or more, to initiate the copolymerization reaction A method for producing a vinyl chloride copolymer resin (claim 1),
(2) The macromonomer having a polymer consisting of a vinyl chloride monomer and an ethylenically unsaturated monomer containing a double bond in the main chain is introduced into the dispersion mixing tank and then dispersed and mixed. A method for producing a vinyl chloride copolymer resin according to claim 1 (claim 2),
(3) The ratio of the vinyl chloride monomer to the total amount of monomer components constituting the vinyl chloride copolymer resin is not less than 50% by weight and less than 100% by weight. A method for producing the vinyl chloride copolymer resin according to claim 3 (claim 3),
(4) A vinyl chloride monomer and a macromonomer having a polymer composed of an ethylenically unsaturated monomer containing a double bond in the main chain are copolymerized in an aqueous medium. A method for producing a vinyl chloride copolymer resin according to any one of claims 4 to 8,
About.

  According to the present invention, a vinyl chloride copolymer resin obtained by copolymerizing a vinyl chloride monomer and a macromonomer having a polymer composed of an ethylenically unsaturated monomer containing a double bond in the main chain, It can be obtained with reduced occurrence.

  The vinyl chloride monomer used in the present invention is not particularly limited. For example, vinyl chloride monomer, vinylidene chloride monomer, vinyl acetate monomer, or a mixture thereof, or other copolymerizable with these, preferably after polymerization. A monomer having no reactive functional group in the polymer main chain, for example, one or a mixture of two or more selected from α-olefins such as ethylene and propylene may be used. When using 2 or more types of mixtures, it is preferable that the content rate of the vinyl chloride monomer which occupies for the whole vinyl chloride monomer is 50 weight% or more, especially 70 weight% or more. Among these, from the physical properties of the copolymer resin obtained, it is preferable to use only one of vinyl chloride monomer or vinylidene chloride monomer, and it is more preferable to use vinyl chloride monomer.

In general, a macromonomer is an oligomer molecule having a reactive functional group at the end of a polymer. The macromonomer having, in the main chain, a polymer composed of an ethylenically unsaturated monomer containing a double bond used in the present invention is an allyl group, a vinylsilyl group, a vinyl ether group, dicyclopentadienyl as a reactive functional group. It is produced by radical polymerization having at least one group having a polymerizable carbon-carbon double bond selected from the following general formula (1) at the molecular end.
In particular, since the reactivity with the vinyl chloride monomer is good, the group having a polymerizable carbon-carbon double bond is represented by the following general formula:
—OC (O) C (R) ═CH ₂
The group represented by these is preferable.

In the formula, specific examples of R are not particularly limited. For example, —H, —CH ₃ , —CH ₂ CH ₃ , — (CH ₂ ) _n CH ₃ (n represents an integer of 2 to 19), — A group selected from C ₆ H ₅ , —CH ₂ OH and —CN is preferred, and —H and —CH ₃ are more preferred.

  A polymer composed of an ethylenically unsaturated monomer containing a double bond, which is the main chain of the macromonomer used in the present invention, is produced by radical polymerization. The radical polymerization method uses “a general radical polymerization method” in which a monomer having a specific functional group and a vinyl monomer are simply copolymerized using an azo compound or a peroxide as a polymerization initiator, It is possible to classify into a “controlled radical polymerization method” in which a specific functional group can be introduced at a controlled position.

  In the “general radical polymerization method”, a monomer having a specific functional group is introduced into the polymer only in a probabilistic manner. Must be used in large quantities. Moreover, since it is free radical polymerization, it is difficult to obtain a polymer having a wide molecular weight distribution and a low viscosity.

  “Controlled radical polymerization method” further includes a “chain transfer agent method” in which a vinyl polymer having a functional group at a terminal is obtained by polymerization using a chain transfer agent having a specific functional group, It can be classified as a “living radical polymerization method” in which a polymer having a molecular weight almost as designed can be obtained by growing a growth terminal without causing a termination reaction or the like.

  The “chain transfer agent method” can obtain a polymer having a high functionalization rate, but requires a chain transfer agent having a specific functional group with respect to the initiator. Further, like the above-mentioned “general radical polymerization method”, since it is free radical polymerization, it is difficult to obtain a polymer having a wide molecular weight distribution and a low viscosity.

  Unlike these polymerization methods, the “living radical polymerization method” has a high polymerization rate due to coupling between radicals and the like as described in International Publication WO99 / 65963 relating to the applicant's own invention. Although radical polymerization is considered to be difficult to control because it is easy to cause a termination reaction, the termination reaction is difficult to occur and the molecular weight distribution is narrow. For example, the ratio of the weight average molecular weight Mw to the number average molecular weight Mn (Mw / Mn) is 1. While a polymer of about 1 to 1.5 is obtained, the molecular weight can be freely controlled by the charging ratio of the monomer and the initiator.

  Accordingly, the “living radical polymerization method” can obtain a polymer having a narrow molecular weight distribution and a low viscosity, and a monomer having a specific functional group can be introduced at almost any position of the polymer. In the present invention, the method for producing a vinyl polymer having a specific functional group as described above is a more preferable polymerization method.

  Among “Living Radical Polymerization Methods”, “Atom Transfer Radical Polymerization (ATRP)” is a method in which vinyl halide monomers are polymerized using an organic halide or a sulfonyl halide compound as an initiator and a transition metal complex as a catalyst. In addition to the above-mentioned characteristics of the “living radical polymerization method”, it has a halogen which is relatively advantageous for functional group conversion reaction at the terminal, and has a large degree of freedom in designing initiators and catalysts. It is further preferable as a method for producing a vinyl-based polymer having Examples of this atom transfer radical polymerization method include Matyjaszewski et al., Journal of American Chemical Society (J. Am. Chem. Soc.) 1995, 117, 5614.

  There is no particular limitation as to which of these methods is used as a method for producing a macromonomer in the present invention, but usually a controlled radical polymerization method is used, and a living radical polymerization method is preferably used because of ease of control. In particular, the atom transfer radical polymerization method is most preferable.

  In addition, there is no particular limitation on the polymer composed of an ethylenically unsaturated monomer containing a double bond, which the macromonomer main chain used in the present invention has, and ethylene containing a double bond constituting the polymer. Various kinds of unsaturated unsaturated monomers can be used. For example, (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, (meth) acrylic acid-n-propyl, (meth) acrylic acid isopropyl, (meth) acrylic acid-n-butyl, (meth ) Isobutyl acrylate, (meth) acrylic acid-tert-butyl, (meth) acrylic acid-n-pentyl, (meth) acrylic acid-n-hexyl, (meth) acrylic acid cyclohexyl, (meth) acrylic acid-n- Heptyl, (n-octyl) (meth) acrylate, (2-ethylhexyl) (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, phenyl (meth) acrylate, Toluyl (meth) acrylate, benzyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, (meth) 3-methoxybutyl crylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, stearyl (meth) acrylate, glycidyl (meth) acrylate, (meth) acrylic acid 2 -Aminoethyl, γ- (methacryloyloxypropyl) trimethoxysilane, ethylene oxide adduct of (meth) acrylic acid, trifluoromethylmethyl (meth) acrylate, 2-trifluoromethylethyl (meth) acrylate, (meth ) 2-perfluoroethylethyl acrylate, 2-perfluoroethyl-2-perfluorobutylethyl (meth) acrylate, 2-perfluoroethyl (meth) acrylate, perfluoromethyl (meth) acrylate, (meta ) Diperfluoromethyl methyl acrylate, (meth) acrylic 2-perfluoromethyl-2-perfluoroethyl methyl phosphate, 2-perfluorohexylethyl (meth) acrylate, 2-perfluorodecylethyl (meth) acrylate, 2-perfluorohexadecyl (meth) acrylate (Meth) acrylic acid monomers such as ethyl; styrene monomers such as styrene, vinyltoluene, α-methylstyrene, chlorostyrene, styrenesulfonic acid and salts thereof; fluorine such as perfluoroethylene, perfluoropropylene, vinylidene fluoride -Containing vinyl monomers; silicon-containing vinyl monomers such as vinyltrimethoxysilane and vinyltriethoxysilane; maleic anhydride, maleic acid, monoalkyl esters and dialkyl esters of maleic acid; fumaric acid, monoalkyl esters of fumaric acid and dia Kill esters; maleimide monomers such as maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide, cyclohexylmaleimide; nitrile groups such as acrylonitrile and methacrylonitrile Vinyl monomers; amide group-containing vinyl monomers such as acrylamide and methacrylamide; vinyl esters such as vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate and vinyl cinnamate; alkenes such as ethylene and propylene; butadiene And conjugated dienes such as isoprene; allyl chloride, allyl alcohol and the like. These may be used alone or two or more of them may be copolymerized. Of these, a styrene monomer or a (meth) acrylic acid monomer is preferred from the viewpoint of physical properties of the product. An acrylate monomer or a methacrylic acid ester monomer is more preferable, an acrylate monomer is more preferable, and butyl acrylate is most preferable. In the present invention, these preferable monomers may be copolymerized with other monomers, and in this case, it is preferable that these preferable monomers are contained in an amount of 40% or more by weight. Here, for example, “(meth) acrylic acid” means acrylic acid or methacrylic acid.

  The macromonomer used in the present invention has a polymer composed of an ethylenically unsaturated monomer containing these double bonds in the main chain, and further has at least one reactive functional group per molecule at the molecular end. It is characterized by having.

  Furthermore, only one type of macromonomer copolymerizable with the vinyl chloride monomer of the present invention may be used, or two or more types of macromonomers having different ethylenically unsaturated monomers may be used in combination.

  The ratio of the vinyl chloride monomer to the total amount of the monomer components constituting the vinyl chloride copolymer resin of the present invention is not particularly limited as long as the effect of the present invention is exhibited, but is 50 wt% or more and less than 100 wt%. It is preferable that it is 50 wt% or more and 99.95 wt% or less. If the ratio of the vinyl chloride monomer is in the range of 50% by weight or more and less than 100% by weight, the copolymerization reaction is stable and the resulting vinyl chloride copolymer resin becomes a granular material, so that the processing method is free. The effect of increasing the degree can be expected.

  The average degree of polymerization or the average molecular weight of the vinyl chloride copolymer resin of the present invention is not particularly limited, and the K value measured according to JIS K 7367-2 is 50 to 95 as in the case of a vinyl chloride resin usually produced and used. Range. Moreover, as an average particle diameter, it is the range of 0.01-500 micrometers normally.

  The method for producing the vinyl chloride copolymer resin of the present invention is not particularly limited, but copolymerization in an aqueous medium is preferable from the viewpoint of simplicity of polymerization control such as removal of polymerization reaction heat and suppression of runaway reaction, For example, production methods such as a suspension polymerization method, a fine suspension polymerization method, and an emulsion polymerization method can be mentioned, and any of these production methods may be used. At that time, a macromonomer having a polymer composed of an ethylenically unsaturated monomer containing a double bond in the vinyl chloride monomer in the main chain is previously dispersed and mixed in a dispersion mixing tank. The dispersion mixing tank is not particularly limited as long as it is an apparatus capable of performing dispersion mixing. For example, a polymerization reactor may be used, or a container other than the polymerization reactor equipped with a jacket and a stirrer may be used.

  The temperature at which the macromonomer having a polymer composed of an ethylenically unsaturated monomer containing a double bond in the vinyl chloride monomer in the main chain is preferably 20 ° C. or higher and 60 ° C. or lower, preferably 30 ° C. More preferably, it is 50 degrees C or less. A polymer composed of an ethylenically unsaturated monomer containing a double bond in a vinyl chloride monomer is maintained in the main chain while maintaining the pressure of the dispersion mixing vessel at a temperature suitable for dispersion mixing as being 20 ° C or more and 60 ° C or less. The macromonomer which has can be disperse-mixed uniformly.

  Further, the time for dispersing and mixing the macromonomer having a polymer composed of an ethylenically unsaturated monomer containing a double bond in the vinyl chloride monomer in the main chain is not particularly limited as long as it can be sufficiently dispersed and mixed. Is preferably 1 minute or longer. When it is 1 minute or longer, a macromonomer having a polymer composed of an ethylenically unsaturated monomer containing a double bond in the vinyl chloride monomer as a main chain can be uniformly dispersed and mixed.

  Here, “dispersion mixing” means that both a vinyl chloride monomer and a macromonomer having a polymer composed of an ethylenically unsaturated monomer containing a double bond in the main chain are uniformly mixed without boundary, Apparently it is impossible to distinguish between the two.

  In addition, “dispersed and mixed in advance” means a suspension dispersant, a polymerization initiator, a surfactant, a dispersion aid used in a suspension polymerization method, a fine suspension polymerization method, an emulsion polymerization method, etc. Before introducing an antioxidant, a polymerization degree adjusting agent, a chain transfer agent, a particle size adjusting agent, a pH adjusting agent, a gelling property improving agent, an antistatic agent, a stabilizer, a scale preventing agent, etc., a vinyl chloride monomer, It means that a macromonomer having a polymer composed of an ethylenically unsaturated monomer containing a double bond in the main chain is dispersed and mixed.

  Further, when the vinyl chloride monomer and the macromonomer having a polymer composed of an ethylenically unsaturated monomer containing a double bond in the main chain are dispersed and mixed, if both are uniformly dispersed and mixed, the method Although there are no particular restrictions, the entire amount of a macromonomer having a polymer consisting of a vinyl chloride monomer and an ethylenically unsaturated monomer containing a double bond in the main chain in a predetermined charge amount is added to the dispersion mixing tank, and then dispersed and mixed. It is one preferable form to perform. As the method, for example, after a vinyl chloride monomer is charged into a previously degassed polymerization reactor, a macromonomer having a polymer composed of an ethylenically unsaturated monomer containing a double bond in the main chain is charged, A method of dispersing and mixing for a predetermined time at a temperature, a macro having a polymer composed of an ethylenically unsaturated monomer containing a double bond in the main chain after charging a part of a vinyl chloride monomer into a pre-degasified polymerization reactor. A method in which a monomer is charged, and the remaining vinyl chloride monomer is further charged and then dispersed and mixed at a predetermined temperature for a predetermined time. A polymer composed of an ethylenically unsaturated monomer containing a double bond in the polymerization reactor is added to the main chain. A method of mixing a macromonomer having a pre-degassing method and then adding a vinyl chloride monomer after deaeration and dispersing and mixing at a predetermined temperature for a predetermined time; A method in which a macromonomer having a main chain of a polymer composed of a vinyl chloride monomer and an ethylenically unsaturated monomer containing a double bond is charged in the machine and dispersed and mixed at a predetermined temperature for a predetermined time. Then, a mixture in which a macromonomer having a polymer consisting of an ethylenically unsaturated monomer containing a double bond in a vinyl chloride monomer in the main chain is dispersed and mixed at a predetermined temperature for a predetermined time is placed in a pre-degassed polymerization reactor. A method of charging, etc. may be mentioned, and any of these dispersion mixing methods may be used.

  By these methods, a macromonomer having a polymer composed of an ethylenically unsaturated monomer containing a double bond in a vinyl chloride monomer is uniformly dispersed and mixed, for example, “copolymerization is abnormal polymerization”. And normal particles cannot be obtained ”,“ the heat removal from the polymerization exotherm is insufficient even before abnormal polymerization ”, and“ a lot of scale is generated even when normal particles are obtained ”. It is expected that the polymerization stability can be improved.

  In the present invention, after dispersing and mixing a macromonomer having a polymer composed of an ethylenically unsaturated monomer containing a double bond in the main chain with a vinyl chloride monomer, if necessary, suspension polymerization, fine suspension Suspension dispersant, polymerization initiator, surfactant, dispersion aid, antioxidant, polymerization degree regulator, chain transfer agent, particle size regulator, pH regulator, used in polymerization method, emulsion polymerization method, etc. Gelling property improvers, antistatic agents, stabilizers, scale inhibitors, etc. are charged all at once, divided or continuously, and a copolymerization reaction is carried out at a predetermined polymerization temperature.

  The suspension dispersant can be used without particular limitation as long as it does not impair the object of the present invention. Examples of such suspending and dispersing agents include partially saponified polyvinyl acetate; water-soluble cellulose ethers such as methylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, and carboxymethylcellulose; polyethylene oxide; polyvinylpyrrolidone; polyacrylic acid; Organic polymer dispersants such as vinyl acetate-maleic acid copolymer; styrene-maleic acid copolymer; gelatin; starch and the like can be used, and these can be used alone or in combination of two or more.

  The polymerization initiator is not particularly limited in the suspension polymerization method or the fine suspension polymerization method, and an oil-soluble polymerization initiator within a range that does not impair the object of the present invention may be added. Among them, it is preferable to use one or more of those having a 10-hour half-life temperature of 30 to 65 ° C. Examples of such polymerization initiators include acetylcyclohexylsulfonyl peroxide, 2,4,4 trimethylpentyl-2-peroxyneodecanoate, diisopropyl peroxydicarbonate, di (2-ethylhexyl) peroxydicarbonate. , T-butyl peroxypivalate, t-butyl peroxyneodecanoate, 1,1,3,3-tetramethylbutylperoxyneodecanoate, dilauroyl peroxide, 3,5,5-trimethylhexa Organic peroxide polymerization initiators such as noyl peroxide; 2,2′-azobisisobutyronitrile, 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2 ′ -Azo polymerization initiators such as azobis- (2,4-dimethylvaleronitrile) These may be used alone or in combination of two or more. These oil-soluble polymerization initiators can be added without any particular restrictions. For example, when used by dissolving in an organic solvent, examples of the organic solvent include aromatics such as toluene, xylene, and benzene. Hydrocarbons; Aliphatic hydrocarbons such as hexane and isoparaffin; Ketones such as acetone and methyl ethyl ketone; Esters such as ethyl acetate, butyl acetate and dioctyl phthalate are used, and these should be used alone or in combination of two or more. Can do.

  In the emulsion polymerization method, a water-soluble polymerization initiator within a range that does not impair the object of the present invention is not particularly limited, and such a water-soluble polymerization initiator may be added. Examples include potassium sulfate, sodium persulfate, and hydrogen peroxide water. If necessary, a reducing agent such as sodium sulfite, sodium thiosulfate, sodium formaldehyde sulfoxylate dihydrate, ascorbic acid, sodium ascorbate is used in combination. be able to. These can be used alone or in combination of two or more.

  Further, the surfactant is not particularly limited and may be added within a range that does not impair the object of the present invention. Examples of such surfactants include alkyl sulfate esters and alkylaryl sulfonates. , Anionic surfactants such as alkyl sulfosuccinates, fatty acid salts, α-olefin sulfonates, alkyl ether phosphates, polyoxyethylene alkylaryl sulfates, polyoxyethylene alkyl sulfates (where , “Salts” include potassium salts, sodium salts, ammonium salts, etc.), sorbitan esters, polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyoxyethylene alkyl esters, etc. Hydrophilic Anion surfactants such, and these may be used alone or in combination of two or more.

  Further, the dispersion aid is not particularly limited and may be added within a range that does not impair the object of the present invention. Examples of such dispersion aid include lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl. Higher alcohols such as alcohol; higher fatty acids such as lauric acid, myristic acid, palmitic acid and stearic acid; esters of higher fatty acids; higher aliphatic hydrocarbons; halogenated hydrocarbons; These may be used alone or in combination of two or more.

  In addition, antioxidants, polymerization degree regulators, chain transfer agents, particle size regulators, pH regulators, gelling modifiers, antistatic agents, stabilizers, scale inhibitors, etc. are generally used in the production of vinyl chloride resins. What is used for can be used arbitrarily as needed, and the amount charged is not particularly limited.

  In general, vinyl chloride resins are used for various purposes, and a resin manufactured by a manufacturing method suitable for the application is used. For example, vinyl chloride resin produced mainly by suspension polymerization is used for hard applications such as pipes, joints, and plates, and soft applications such as sheets, films, and wire coatings. Wallpaper, flooring, gloves, etc. For use in molding from the state of plastisol, a vinyl chloride resin produced mainly by a fine suspension polymerization method or an emulsion polymerization method is used. The vinyl chloride resin production method of the present invention can be suitably used for any of these production methods, and according to the present invention, vinyl chloride copolymer resins suitable for various applications can be obtained.

  EXAMPLES Next, although this invention is demonstrated in detail based on an Example, this invention is not limited to a following example. Here, unless otherwise specified, “parts” in the examples means “parts by weight” and “%” means “% by weight”.

<Evaluation of polymerization stability>
The polymerization stability was determined based on the following criteria by visually observing the state of the scale in the polymerization reactor after the contents were discharged.

    ○: Almost no scale adheres to the inner wall of the reactor and / or the stirrer.

    Δ: A small amount of scale adhered to the inner wall of the reactor and / or the stirrer.

X: Significant scale adhesion to the inner wall of the reactor and / or the stirrer is observed.
<Manufacture of a macromonomer having a polymer composed of an ethylenically unsaturated monomer containing a double bond in the main chain>
Production of a macromonomer having a polymer composed of an ethylenically unsaturated monomer containing a double bond in the main chain was carried out according to the procedure shown in the following production examples.

(Production example)
CuBr (5.54 g) was charged into a 2 L separable flask equipped with a reflux tube and a stirrer, and the inside of the reaction vessel was purged with nitrogen. Acetonitrile (73.8 ml) was added, and the mixture was stirred in an oil bath at 70 ° C. for 30 minutes. To this, n-butyl acrylate (132 g), methyl 2-bromopropionate (7.2 ml) and pentamethyldiethylenetriamine (4.69 ml) were added to initiate the reaction. While heating and stirring at 70 ° C., acrylate-n-butyl (528 g) was continuously added dropwise over 90 minutes, and the mixture was further heated and stirred for 80 minutes.

  The reaction mixture was diluted with toluene, passed through an activated alumina column, and then the volatile component was distilled off under reduced pressure to obtain one-terminal Br group poly (acrylic acid-n-butyl).

The flask was charged with methanol (800 ml) and cooled to 0 ° C. Thereto, t-butoxypotassium (130 g) was added in several portions. The reaction solution was kept at 0 ° C., and a methanol solution of acrylic acid (100 g) was added dropwise. After completion of the dropwise addition, the temperature of the reaction solution was returned from 0 ° C. to room temperature, and then the volatile content of the reaction solution was distilled off under reduced pressure to obtain potassium acrylate (CH ₂ = CHCO ₂ K).

  A 500 mL flask equipped with a reflux tube was charged with the obtained one-terminal Br group poly (acrylic acid-n-butyl) (150 g), potassium acrylate (7.45 g), dimethylacetamide (150 ml), and heated at 70 ° C. for 3 hours. Stir. Dimethylacetamide was distilled off from the reaction mixture, dissolved in toluene, passed through an activated alumina column, and then toluene was distilled off to obtain a one-terminal acryloyl group poly (acrylic acid-n-butyl) macromonomer.

(Example 1) Method for producing vinyl chloride copolymer resin by fine suspension polymerization method After degassing a 15 liter stainless steel polymerization reactor equipped with a jacket and a stirrer, 99.95 parts of vinyl chloride monomer was added. First, 0.05 part of acryloyl group poly (acrylic acid-n-butyl) macromonomer in Preparation Example was charged, and then polymerized through warm water in the jacket to disperse and mix the macromonomer with the vinyl chloride monomer. The temperature inside the reactor was raised to 30 ° C., and the mixture was stirred for 1 minute at a rotation speed of 200 revolutions per minute. After cooling the internal temperature of the polymerization reactor to 20 ° C. or less through water through the jacket, 0.07 part of 2,2′-azobis- (2,4-dimethylvaleronitrile) and 1.4 parts of stearyl alcohol are added for 2 minutes. After homogenization, an aqueous solution (300 parts) in which 1.16 parts of sodium lauryl sulfate was previously dissolved was added to the polymerization reactor and homogenized again for 3 minutes to obtain a monomer dispersion. Next, polymerization was carried out at a polymerization temperature of 50 ° C. for about 6 hours. Unreacted vinyl chloride monomer in the polymerization reactor was recovered, the interior of the polymerization reactor was cooled, and latex was discharged. Table 1 shows the evaluation results of the polymerization stability.

Example 2 Production Method of Vinyl Chloride Copolymer Resin by Fine Suspension Polymerization Method One-terminal acryloyl group poly (acrylic acid-) in a 15 liter stainless steel polymerization reactor equipped with a jacket and a stirrer n-Butyl) Macromonomer 50 parts are charged and degassed, then vinyl chloride monomer 50 parts is added, and in order to disperse and mix the macromonomer in the vinyl chloride monomer, the temperature inside the polymerization reactor is set to 40 ° C. through warm water in the jacket. The mixture was heated up to 200 rpm and stirred for 60 minutes at a rotation speed of 200 revolutions per minute. After cooling the internal temperature of the polymerization reactor to 20 ° C. or less through water through the jacket, 0.07 part of 2,2′-azobis- (2,4-dimethylvaleronitrile) and 1.4 parts of stearyl alcohol are added for 2 minutes. After homogenization, an aqueous solution (300 parts) in which 1.16 parts of sodium lauryl sulfate was previously dissolved was added to the polymerization reactor and homogenized again for 3 minutes to obtain a monomer dispersion. Next, polymerization was carried out at a polymerization temperature of 50 ° C. for about 6 hours. Unreacted vinyl chloride monomer in the polymerization reactor was recovered, the interior of the polymerization reactor was cooled, and latex was discharged. Table 1 shows the evaluation results of the polymerization stability.

(Example 3) Production method of vinyl chloride copolymer resin by fine suspension polymerization method After degassing a 15 liter stainless steel polymerization reactor equipped with a jacket and a stirrer, 50 parts of vinyl chloride monomer and production In order to simultaneously charge 50 parts of the one-terminal acryloyl group poly (n-butyl acrylate) macromonomer and disperse and mix the macromonomer with the vinyl chloride monomer, the temperature inside the polymerization reactor was increased to 40 ° C. through warm water in the jacket. The temperature was raised and the mixture was stirred for 30 minutes at a rotation speed of 200 revolutions per minute. After cooling the internal temperature of the polymerization reactor to 20 ° C. or less through water through the jacket, 0.07 part of 2,2′-azobis- (2,4-dimethylvaleronitrile) and 1.4 parts of stearyl alcohol are added for 2 minutes. After homogenization, an aqueous solution (300 parts) in which 1.16 parts of sodium lauryl sulfate was previously dissolved was added to the polymerization reactor and homogenized again for 3 minutes to obtain a monomer dispersion. Next, polymerization was carried out at a polymerization temperature of 50 ° C. for about 6 hours. Unreacted vinyl chloride monomer in the polymerization reactor was recovered, the interior of the polymerization reactor was cooled, and latex was discharged. Table 1 shows the evaluation results of the polymerization stability.

Example 4 Production Method of Vinyl Chloride Copolymer Resin by Suspension Polymerization Method One-terminal acryloyl group poly (acrylic acid-n) produced in a stainless steel polymerization reactor with an internal volume of 25 liters equipped with a jacket and a stirrer -Butyl) After adding 0.05 parts of macromonomer and degassing, 99.95 parts of vinyl chloride monomer was added, and in order to disperse and mix the macromonomer in the vinyl chloride monomer, the temperature inside the polymerization reactor was passed through warm water in the jacket. The mixture was heated to 30 ° C. and stirred for 1 minute at a rotation speed of 900 revolutions per minute. After cooling the internal temperature of the polymerization reactor to 20 ° C. or less through water through the jacket, 0.3 part of partially saponified polyvinyl acetate having a degree of saponification of about 88 mol% and an average degree of polymerization of about 3,500, a degree of saponification of about 78 mol% and an average degree of polymerization Hydroxypropyl methylcellulose having a viscosity of about 30000 mPa · s at 20 ° C. in an aqueous solution of 0.15 parts of partially saponified polyvinyl acetate of about 900, methoxyl group content of about 20 mol%, hydroxypropoxyl group content of about 8 mol%, and 2% 0.02 part of stearic acid-n-butyl, 0.02 part of t-butylperoxyneodecanoate and 0.02 part of 3,5,5-trimethylhexanoyl peroxide were charged. Subsequently, 200 parts of warm water at 60 ° C. was charged and polymerized at a polymerization temperature of 64 ° C. for about 6 hours. After recovering unreacted vinyl chloride monomer in the polymerization reactor, the polymerization reactor was cooled and the latex was discharged. Table 1 shows the evaluation results of the polymerization stability.

(Example 5) Production method of vinyl chloride copolymer resin by suspension polymerization method After degassing a stainless steel polymerization reactor having an internal volume of 25 liters equipped with a jacket and a stirrer, 50 parts of vinyl chloride monomer was charged, and then After preparing 50 parts of acryloyl group poly (acrylic acid-n-butyl) macromonomer of the production example and dispersing and mixing the macromonomer in the vinyl chloride monomer, the inner temperature of the polymerization reactor was set to 40 through warm water in the jacket. The temperature was raised to 0 ° C., and the mixture was stirred for 60 minutes at a rotation speed of 900 revolutions per minute. After cooling the internal temperature of the polymerization reactor to 20 ° C. or less through water through the jacket, 0.3 part of partially saponified polyvinyl acetate having a degree of saponification of about 88 mol% and an average degree of polymerization of about 3,500, a degree of saponification of about 78 mol% and an average degree of polymerization Hydroxypropyl methylcellulose having a viscosity of about 30000 mPa · s at 20 ° C. in an aqueous solution of 0.15 parts of partially saponified polyvinyl acetate of about 900, methoxyl group content of about 20 mol%, hydroxypropoxyl group content of about 8 mol%, and 2% 0.02 part of stearic acid-n-butyl, 0.02 part of t-butylperoxyneodecanoate and 0.02 part of 3,5,5-trimethylhexanoyl peroxide were charged. Subsequently, 200 parts of warm water at 60 ° C. was charged and polymerized at a polymerization temperature of 64 ° C. for about 6 hours. After recovering unreacted vinyl chloride monomer in the polymerization reactor, the polymerization reactor was cooled and the latex was discharged. Table 1 shows the evaluation results of the polymerization stability.

Example 6 Production Method of Vinyl Chloride Copolymer Resin by Suspension Polymerization Method After degassing a stainless steel polymerization reactor having an internal volume of 25 liters equipped with a jacket and a stirrer, 50 parts of vinyl chloride monomer and production example In order to disperse and mix the macromonomer with the vinyl chloride monomer at the same time, the temperature inside the polymerization reactor was raised to 40 ° C. through warm water in the jacket. The mixture was warmed and stirred for 30 minutes at a rotation speed of 900 revolutions per minute. After cooling the internal temperature of the polymerization reactor to 20 ° C. or less through water through the jacket, 0.3 part of partially saponified polyvinyl acetate having a degree of saponification of about 88 mol% and an average degree of polymerization of about 3,500, a degree of saponification of about 78 mol% and an average degree of polymerization Hydroxypropyl methylcellulose having a viscosity of about 30000 mPa · s at 20 ° C. in an aqueous solution of 0.15 parts of partially saponified polyvinyl acetate of about 900, methoxyl group content of about 20 mol%, hydroxypropoxyl group content of about 8 mol%, and 2% 0.02 part of stearic acid-n-butyl, 0.02 part of t-butylperoxyneodecanoate and 0.02 part of 3,5,5-trimethylhexanoyl peroxide were charged. Subsequently, 200 parts of warm water at 60 ° C. was charged and polymerized at a polymerization temperature of 64 ° C. for about 6 hours. After recovering unreacted vinyl chloride monomer in the polymerization reactor, the polymerization reactor was cooled and the latex was discharged. Table 1 shows the evaluation results of the polymerization stability.

Example 7 Production Method of Vinyl Chloride Copolymer Resin by Suspension Polymerization Method One-terminal acryloyl group poly (acrylic acid-n) produced in a stainless steel polymerization reactor having an internal volume of 25 liters equipped with a jacket and a stirrer -Butyl) After adding 0.05 parts of macromonomer and degassing, 99.95 parts of vinyl chloride monomer was added, and in order to disperse and mix the macromonomer in the vinyl chloride monomer, the temperature inside the polymerization reactor was passed through warm water in the jacket. The mixture was heated to 30 ° C. and stirred for 1 minute at a rotation speed of 900 revolutions per minute. After cooling the temperature of the polymerization reactor to 20 ° C. or less through water through the jacket, 0.05 part of partially saponified polyvinyl acetate having a degree of saponification of about 80 mol%, an average degree of polymerization of about 2000, and an average molecular weight of about 4.5 million polyethylene oxide. 005 parts, t-butyl peroxyneodecanoate 0.03 part, 1,1,3,3-tetramethylbutylperoxyneodecanoate 0.01 part were charged. Subsequently, 150 parts of warm water at 60 ° C. was charged, and polymerization was carried out at a polymerization temperature of 57 ° C. for about 6 hours. After recovering unreacted vinyl chloride monomer in the polymerization reactor, the polymerization reactor was cooled and the slurry was discharged. Table 1 shows the evaluation results of the polymerization stability.

Example 8 Production Method of Vinyl Chloride Copolymer Resin by Suspension Polymerization Method One-terminal acryloyl group poly (acrylic acid-n) produced in a stainless steel polymerization reactor having an internal volume of 25 liters equipped with a jacket and a stirrer -Butyl) After adding 50 parts of macromonomer and degassing, 50 parts of vinyl chloride monomer is added, and in order to disperse and mix the macromonomer in the vinyl chloride monomer, the temperature inside the polymerization reactor is increased to 40 ° C. through warm water in the jacket. The temperature was raised, and the mixture was stirred for 60 minutes at a rotation speed of 900 rotations per minute. After cooling the temperature of the polymerization reactor to 20 ° C. or less through water through the jacket, 0.05 part of partially saponified polyvinyl acetate having a degree of saponification of about 80 mol%, an average degree of polymerization of about 2000, and an average molecular weight of about 4.5 million polyethylene oxide. 005 parts, t-butyl peroxyneodecanoate 0.03 part, 1,1,3,3-tetramethylbutylperoxyneodecanoate 0.01 part were charged. Subsequently, 150 parts of warm water at 60 ° C. was charged, and polymerization was carried out at a polymerization temperature of 57 ° C. for about 6 hours. After recovering unreacted vinyl chloride monomer in the polymerization reactor, the polymerization reactor was cooled and the slurry was discharged. Table 1 shows the evaluation results of the polymerization stability.

(Example 9) Production method of vinyl chloride copolymer resin by suspension polymerization method After degassing a 25 liter stainless steel polymerization reactor equipped with a jacket and a stirrer, 50 parts of vinyl chloride monomer and production example In order to disperse and mix the macromonomer with the vinyl chloride monomer at the same time, the temperature inside the polymerization reactor was raised to 40 ° C. through warm water in the jacket. The mixture was warmed and stirred for 30 minutes at a rotation speed of 900 revolutions per minute. After cooling the temperature of the polymerization reactor to 20 ° C. or less through water through the jacket, 0.05 part of partially saponified polyvinyl acetate having a degree of saponification of about 80 mol%, an average degree of polymerization of about 2000, and an average molecular weight of about 4.5 million polyethylene oxide. 005 parts, t-butyl peroxyneodecanoate 0.03 part, 1,1,3,3-tetramethylbutylperoxyneodecanoate 0.01 part were charged. Subsequently, 150 parts of warm water at 60 ° C. was charged, and polymerization was carried out at a polymerization temperature of 57 ° C. for about 6 hours. After recovering unreacted vinyl chloride monomer in the polymerization reactor, the polymerization reactor was cooled and the slurry was discharged. Table 1 shows the evaluation results of the polymerization stability.

Example 10 Production Method of Vinyl Chloride Copolymer Resin by Suspension Polymerization Method One-terminal acryloyl group poly (acrylic acid-n) was prepared in a stainless steel pressure vessel having an internal volume of 15 liters equipped with a jacket and a stirrer. -Butyl) After adding 50 parts of macromonomer and degassing, 50 parts of vinyl chloride monomer is added, and in order to disperse and mix the macromonomer in the vinyl chloride monomer, the temperature inside the pressure vessel is increased to 40 ° C. through warm water in the jacket. The temperature was raised, and the mixture was stirred for 60 minutes at a rotation speed of 450 revolutions per minute. After cooling the internal pressure of the pressure vessel to 20 ° C. or less through water through the jacket, the entire contents were transferred to a stainless steel polymerization reactor having an inner volume of 25 liters equipped with a jacket and a stirrer. Next, the polymerization reactor was charged with 0.05 part of partially saponified polyvinyl acetate having a degree of saponification of about 80 mol% and an average degree of polymerization of about 2000, 0.005 part of polyethylene oxide having an average molecular weight of about 4.5 million, and t-butylperoxyneodeca After charging 0.03 part of Noate and 0.01 part of 1,1,3,3-tetramethylbutylperoxyneodecanoate, 150 parts of hot water at 60 ° C. was added, and the polymerization temperature was 57 ° C. for about 6 hours. Polymerized. After recovering unreacted vinyl chloride monomer in the polymerization reactor, the polymerization reactor was cooled and the slurry was discharged. Table 1 shows the evaluation results of the polymerization stability.

Comparative Example 1 Production Method of Vinyl Chloride Copolymer Resin by Fine Suspension Polymerization In Example 1, after charging the vinyl chloride monomer and the one-end acryloyl group poly (acrylic acid-n-butyl) macromonomer of Production Example The polymerization was conducted in the same manner as in Example 1 except that the polymerization reactor internal temperature for dispersing and mixing the macromonomer with the vinyl chloride monomer was not stirred, and the latex was discharged. Table 1 shows the evaluation results of the polymerization stability. The internal temperature of the polymerization reactor after the preparation of the vinyl chloride monomer and the one-end acryloyl group poly (n-butyl acrylate) macromonomer in Production Example was about 17 ° C.

  Scale was observed in the polymerization reactor.

(Comparative Example 2) Production Method of Vinyl Chloride Copolymer Resin by Fine Suspension Polymerization In Example 2, after preparation of one-end acryloyl group poly (acrylic acid-n-butyl) macromonomer and vinyl chloride monomer in Production Example In the same manner as in Example 2, except that the polymerization reactor internal temperature for dispersing and mixing the macromonomer with the vinyl chloride monomer was not stirred and was stirred for 60 minutes at a rotation speed of 200 revolutions per minute. Polymerized and the latex was dispensed. Table 1 shows the evaluation results of the polymerization stability. The polymerization reactor internal temperature when stirring for 60 minutes at a rotation speed of 200 revolutions per minute was about 18 ° C.

  Significant scale was observed in the polymerization reactor. In addition, one-end acryloyl group poly (n-butyl acrylate) macromonomer that was not dispersed and mixed with the vinyl chloride monomer was found in the inner wall of the polymerization reactor and in the latex.

(Comparative Example 3) Production Method of Vinyl Chloride Copolymer Resin by Fine Suspension Polymerization In Example 2, after the preparation of one-end acryloyl group poly (acrylic acid-n-butyl) macromonomer and vinyl chloride monomer in Production Example In order to disperse and mix the macromonomer with the vinyl chloride monomer, the temperature inside the polymerization reactor was raised to 40 ° C. through warm water in the jacket, and the stirring was performed for 30 seconds at a rotation speed of 200 revolutions per minute. Polymerization was conducted in the same manner as in Example 2, and the latex was discharged. Table 1 shows the evaluation results of the polymerization stability.

  Significant scale was observed in the polymerization reactor. In addition, one-end acryloyl group poly (n-butyl acrylate) macromonomer that was not dispersed and mixed with the vinyl chloride monomer was found in the inner wall of the polymerization reactor and in the latex.

Comparative Example 4 Production Method of Vinyl Chloride Copolymer Resin by Fine Suspension Polymerization In Example 3, after charging the vinyl chloride monomer and the one-end acryloyl group poly (acrylic acid-n-butyl) macromonomer of Production Example In the same manner as in Example 3, except that the temperature inside the polymerization reactor for dispersing and mixing the macromonomer with the vinyl chloride monomer was not increased and stirred for 30 minutes at a rotation speed of 200 revolutions per minute. Polymerized and the latex was dispensed. Table 1 shows the evaluation results of the polymerization stability. The polymerization reactor internal temperature when stirring for 30 minutes at a rotation speed of 200 revolutions per minute was about 17 ° C.

  Significant scale was observed in the polymerization reactor. In addition, one-end acryloyl group poly (n-butyl acrylate) macromonomer that was not dispersed and mixed with the vinyl chloride monomer was found in the inner wall of the polymerization reactor and in the latex.

Comparative Example 5 Production Method of Vinyl Chloride Copolymer Resin by Fine Suspension Polymerization In Example 3, after charging the vinyl chloride monomer and the one-end acryloyl group poly (acrylic acid-n-butyl) macromonomer of Production Example In order to disperse and mix the macromonomer with the vinyl chloride monomer, the temperature inside the polymerization reactor was raised to 40 ° C. through warm water in the jacket, and the stirring was performed for 30 seconds at a rotation speed of 200 revolutions per minute. Polymerization was conducted in the same manner as in Example 3, and the latex was discharged. Table 1 shows the evaluation results of the polymerization stability.

  Significant scale was observed in the polymerization reactor. In addition, one-end acryloyl group poly (n-butyl acrylate) macromonomer that was not dispersed and mixed with the vinyl chloride monomer was found in the inner wall of the polymerization reactor and in the latex.

(Comparative Example 6) Production Method of Vinyl Chloride Copolymer Resin by Suspension Polymerization In Example 4, after the preparation of one-end acryloyl group poly (acrylic acid-n-butyl) macromonomer and vinyl chloride monomer in Production Example, Polymerization was carried out in the same manner as in Example 4 except that the polymerization reactor internal temperature for dispersing and mixing the macromonomer with the vinyl chloride monomer was not stirred, and the latex was discharged. Table 1 shows the evaluation results of the polymerization stability. The internal temperature of the polymerization reactor after the preparation of the one-terminal acryloyl group poly (n-butyl acrylate) macromonomer and vinyl chloride monomer in the production example was about 15 ° C.

  Scale was observed in the polymerization reactor.

Comparative Example 7 Production Method of Vinyl Chloride Copolymer Resin by Suspension Polymerization In Example 5, after charging the vinyl chloride monomer and the one-end acryloyl group poly (acrylic acid-n-butyl) macromonomer of Production Example, Polymerization was carried out in the same manner as in Example 5, except that the polymerization reactor internal temperature for dispersing and mixing the macromonomer with the vinyl chloride monomer was not stirred for 60 minutes at a rotation speed of 900 revolutions per minute. And latex was paid out. Table 1 shows the evaluation results of the polymerization stability. The polymerization reactor internal temperature when stirring for 60 minutes at a rotation speed of 900 revolutions per minute was about 16 ° C.

  Significant scale was observed in the polymerization reactor. In addition, one-end acryloyl group poly (n-butyl acrylate) macromonomer that was not dispersed and mixed with the vinyl chloride monomer was found in the inner wall of the polymerization reactor and in the latex.

Comparative Example 8 Production Method of Vinyl Chloride Copolymer Resin by Suspension Polymerization In Example 5, after charging the vinyl chloride monomer and the one-end acryloyl group poly (acrylic acid-n-butyl) macromonomer of Production Example, In order to disperse and mix the macromonomer with the vinyl chloride monomer, the temperature inside the polymerization reactor was raised to 40 ° C. through warm water in a jacket and stirred for 30 seconds at a rotation speed of 900 revolutions per minute. Polymerization was conducted in the same manner as in No. 5, and the latex was discharged. Table 1 shows the evaluation results of the polymerization stability.

  Significant scale was observed in the polymerization reactor. In addition, one-end acryloyl group poly (n-butyl acrylate) macromonomer that was not dispersed and mixed with the vinyl chloride monomer was found in the inner wall of the polymerization reactor and in the latex.

Comparative Example 9 Production Method of Vinyl Chloride Copolymer Resin by Suspension Polymerization In Example 6, after charging the vinyl chloride monomer and the one-end acryloyl group poly (acrylic acid-n-butyl) macromonomer of Production Example, Polymerization was conducted in the same manner as in Example 6 except that the polymerization reactor internal temperature for dispersing and mixing the macromonomer with the vinyl chloride monomer was not stirred and stirred for 30 minutes at a rotation speed of 900 revolutions per minute. And latex was paid out. Table 1 shows the evaluation results of the polymerization stability. The polymerization reactor internal temperature when stirring for 30 minutes at a rotation speed of 200 revolutions per minute was about 15 ° C.

  Significant scale was observed in the polymerization reactor. In addition, one-end acryloyl group poly (n-butyl acrylate) macromonomer that was not dispersed and mixed with the vinyl chloride monomer was found in the inner wall of the polymerization reactor and in the latex.

Comparative Example 10 Production Method of Vinyl Chloride Copolymer Resin by Suspension Polymerization In Example 6, after charging the vinyl chloride monomer and the one-end acryloyl group poly (acrylic acid-n-butyl) macromonomer of Production Example, In order to disperse and mix the macromonomer with the vinyl chloride monomer, the temperature inside the polymerization reactor was raised to 40 ° C. through warm water in a jacket and stirred for 30 seconds at a rotation speed of 900 revolutions per minute. Polymerization was carried out in the same manner as in No. 6, and the latex was discharged. Table 1 shows the evaluation results of the polymerization stability.

  Significant scale was observed in the polymerization reactor. In addition, one-end acryloyl group poly (n-butyl acrylate) macromonomer that was not dispersed and mixed with the vinyl chloride monomer was found in the inner wall of the polymerization reactor and in the latex.

(Comparative Example 11) Production Method of Vinyl Chloride Copolymer Resin by Suspension Polymerization In Example 7, after preparation of the one-end acryloyl group poly (n-butyl acrylate) macromonomer and vinyl chloride monomer in Production Example, Polymerization was carried out in the same manner as in Example 7 except that the polymerization reactor internal temperature for dispersing and mixing the macromonomer with the vinyl chloride monomer was not stirred, and the slurry was discharged. Table 1 shows the evaluation results of the polymerization stability. The internal temperature of the polymerization reactor after the preparation of the one-end acryloyl group poly (n-butyl acrylate) macromonomer and vinyl chloride monomer in the production example was about 13 ° C.

  Scale was observed in the polymerization reactor.

(Comparative Example 12) Production Method of Vinyl Chloride Copolymer Resin by Suspension Polymerization In Example 8, after the preparation of one-end acryloyl group poly (acrylic acid-n-butyl) macromonomer and vinyl chloride monomer in Production Example, Polymerization was carried out in the same manner as in Example 8 except that the polymerization reactor internal temperature for dispersing and mixing the macromonomer with the vinyl chloride monomer was not stirred for 60 minutes at a rotation speed of 900 revolutions per minute. And the slurry was discharged. Table 1 shows the evaluation results of the polymerization stability. The polymerization reactor internal temperature when stirring for 60 minutes at a rotation speed of 900 revolutions per minute was about 14 ° C.

  Significant scale was observed in the polymerization reactor. In addition, one-end acryloyl group poly (n-butyl acrylate) macromonomer that was not dispersed and mixed with the vinyl chloride monomer was found in the inner wall of the polymerization reactor and in the slurry.

(Comparative Example 13) Production Method of Vinyl Chloride Copolymer Resin by Suspension Polymerization In Example 8, after the preparation of the one-end acryloyl group poly (acrylic acid-n-butyl) macromonomer and vinyl chloride monomer in Production Example, In order to disperse and mix the macromonomer with the vinyl chloride monomer, the temperature inside the polymerization reactor was raised to 40 ° C. through warm water in a jacket and stirred for 30 seconds at a rotation speed of 900 revolutions per minute. Polymerization was carried out in the same manner as in No. 8, and the slurry was discharged. Table 1 shows the evaluation results of the polymerization stability.

  Significant scale was observed in the polymerization reactor. In addition, one-end acryloyl group poly (n-butyl acrylate) macromonomer that was not dispersed and mixed with the vinyl chloride monomer was found in the inner wall of the polymerization reactor and in the slurry.

Comparative Example 14 Production Method of Vinyl Chloride Copolymer Resin by Suspension Polymerization In Example 9, after charging the vinyl chloride monomer and the one-end acryloyl group poly (acrylic acid-n-butyl) macromonomer of Production Example, Polymerization was carried out in the same manner as in Example 9 except that the polymerization reactor for dispersing and mixing the macromonomer with the vinyl chloride monomer was stirred for 30 minutes at a rotation speed of 900 revolutions per minute without increasing the temperature of the polymerization reactor. However, abnormal polymerization occurred. In addition, a single-end acryloyl group poly (n-butyl acrylate) macromonomer that was not dispersed and mixed with the vinyl chloride monomer was observed in the polymerization reactor. The polymerization reactor internal temperature when stirring for 30 minutes at a rotation speed of 900 revolutions per minute was about 13 ° C.

(Comparative Example 15) Production Method of Vinyl Chloride Copolymer Resin by Suspension Polymerization In Example 9, after charging the vinyl chloride monomer and the one-end acryloyl group poly (acrylic acid-n-butyl) macromonomer of Production Example, In order to disperse and mix the macromonomer with the vinyl chloride monomer, the temperature inside the polymerization reactor was raised to 40 ° C. through warm water in a jacket and stirred for 30 seconds at a rotation speed of 900 revolutions per minute. Polymerization was attempted in the same manner as in Example 9, but abnormal polymerization was obtained. Moreover, the one terminal acryloyl group poly (acrylic acid-n-butyl) macromonomer which was not disperse-mixed with the vinyl chloride monomer was recognized in the polymerization reactor.

(Comparative Example 16) Production Method of Vinyl Chloride Copolymer Resin by Suspension Polymerization In Example 10, to one-terminal acryloyl group poly (n-butyl acrylate) macromonomer and vinyl chloride monomer pressure vessel in Production Example Example 10 and Example 10 except that the polymerization reactor was not stirred at a rotational speed of 450 revolutions per minute without increasing the internal temperature of the polymerization reactor for dispersing and mixing the macromonomer with the vinyl chloride monomer. Polymerization was conducted in the same manner, and the slurry was discharged. Table 1 shows the evaluation results of the polymerization stability. The temperature inside the polymerization reactor when stirring for 60 minutes at a rotation speed of 450 revolutions per minute was about 12 ° C.

  Scale was observed in the polymerization reactor. Further, one-end acryloyl group poly (n-butyl acrylate) macromonomer that was not dispersed and mixed with the vinyl chloride monomer was found in the inner wall of the pressure vessel and the slurry.

Claims (8)

In producing a vinyl chloride copolymer resin by copolymerizing a vinyl chloride monomer and a macromonomer having a polymer composed of an ethylenically unsaturated monomer containing a double bond in the main chain, a vinyl chloride monomer and the macromonomer chromatography having a polymer consisting of ethylenically unsaturated monomers containing a double bond in the main chain was dispersed mixture over 1 minute at a temperature of 60 ° C. 20 ° C. or higher, and characterized in that to start the copolymerization reaction A method for producing a vinyl chloride copolymer resin. 2. A macromonomer having, as a main chain, a polymer composed of a vinyl chloride monomer and an ethylenically unsaturated monomer containing a double bond in a main chain is added to a dispersion mixing tank and then dispersed and mixed. A method for producing a vinyl chloride copolymer resin as described in 1 above. The ratio of vinyl chloride monomer to the total amount of monomer components constituting the vinyl chloride copolymer resin is 50 wt% or more and less than 100 wt%, chlorination according to any one of claims 1-2. A method for producing a vinyl copolymer resin. The copolymerization of a vinyl chloride monomer and a macromonomer having a polymer composed of an ethylenically unsaturated monomer containing a double bond in the main chain in an aqueous medium. A method for producing a vinyl chloride copolymer resin as described in 1 above. The macromonomer having a polymer composed of an ethylenically unsaturated monomer containing a double bond in the main chain has at least one reactive functional group per molecule at the molecular end, and the reactive functional group is The manufacturing method of the vinyl chloride type copolymer resin in any one of Claims 1-4 which has the polymerizable carbon-carbon double bond shown by the following general formula.
-OC (0) C (R) = CH ₂
  Where R is -H, -CH _Three , -CH ₂ CH _Three ,-(CH ₂ ) _n CH _Three (N represents an integer of 2 to 19), -C ₆ H _Five , -CH ₂ It is a group selected from OH and -CN. The vinyl chloride copolymer resin according to any one of claims 1 to 5, wherein a macromonomer having a polymer composed of an ethylenically unsaturated monomer containing a double bond in the main chain is produced by living radical polymerization. Production method. The macromonomer having a polymer composed of an ethylenically unsaturated monomer containing a double bond in the main chain, wherein the ethylenically unsaturated monomer containing a double bond is an acrylate monomer. The manufacturing method of the vinyl chloride type copolymer resin in any one. A macromonomer having a polymer composed of a vinyl chloride monomer and an ethylenically unsaturated monomer containing a double bond in the main chain is shared by at least one method selected from emulsion polymerization, suspension polymerization, and fine suspension polymerization. The method for producing a vinyl chloride copolymer resin according to any one of claims 1 to 7.