JP2006273990A - Method for producing vinyl chloride copolymer resin - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a vinyl chloride copolymer resin excellent in polymerization stability and with a scarce scale formation which comprises a copolymerization product of a vinyl chloride monomer and a macromonomer having a polymer of ethylenic unsaturated monomer with double bonds as a main chain and contains little residue of the macromonomer. <P>SOLUTION: The vinyl chloride copolymer resin is produced by copolymerizing the vinyl chloride monomer and the macromonomer. When producing the vinyl chloride copolymer, the ratio of the vinyl chloride monomer to the total amount of monomer components is ≥50 wt.% and <100 wt.%, and the gross weight (M) of the macromonomer and the vinyl chloride monomer and the initial water weight (H) are within a range of 0<H/M≤3.0 (1). After a dispersing agent and an emulsifier are dissolved in initial water, the macromonomer is added to and is dispersed in the initial water. The vinyl chloride is then added to the mixture to produce the vinyl chloride copolymer resin. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

    The present invention relates to a method for producing a vinyl chloride copolymer resin, and more specifically, there is no residue after polymerization of a macromonomer having a polymer composed of an ethylenically unsaturated monomer containing a double bond in the main chain. Copolymerizing a vinyl monomer and a macromonomer having a polymer consisting of an ethylenically unsaturated monomer containing a double bond in the main chain with less scale generation in the can and excellent polymerization stability. The present invention relates to a method for producing a vinyl chloride copolymer resin.

    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 is a problem that a homopolymer is formed or the scale inside the polymerization reactor is increased.

In the case of producing a copolymer resin, if the vinyl chloride monomer and copolymerizable monomer or polymer are not uniformly dissolved, it is difficult to obtain a uniform polymer as a copolymer. In addition, when the copolymerizable monomer or polymer has a high viscosity, if the copolymerizable monomer or polymer enters the recesses such as the can wall, stirring shaft, discharge port, and sampling port, the influence of shear flow due to stirring is reduced. There is a problem that causes contamination due to unreacted residues of scale, copolymerizable monomer or polymer.
Japanese Unexamined Patent Publication No. 63-23947

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

  As a result of diligent research, the present inventors dispersed a macromonomer having a polymer composed of an ethylenically unsaturated monomer containing a double bond in water in the main chain, and then added a vinyl chloride monomer. The inventors have found that the above-mentioned problems can be solved by mixing and dissolving with a macromonomer, and then starting a copolymerization reaction, thereby completing the present invention.

That is, the present invention
When 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, The ratio of the vinyl chloride monomer to the total amount is 50% by weight or more and less than 100% by weight, and the macromonomer having a polymer composed of an ethylenically unsaturated monomer containing a double bond in the main chain and the vinyl chloride monomer The total weight (M) and the initial water weight (H) are in the range of the following formula (1):
0 <H / M ≦ 3.0 (1)
After dissolving the dispersant and / or emulsifier in the initial water, a macromonomer having a polymer composed of an ethylenically unsaturated monomer containing a double bond in the main chain is added and dispersed in the initial water. A method for producing a vinyl chloride copolymer resin, wherein a monomer is added;
About.

  According to the present invention, there is no macromonomer residue having a polymer composed of an ethylenically unsaturated monomer containing a double bond in the resin after the completion of polymerization in the main chain, and generation of scale is suppressed, and vinyl chloride is obtained. A vinyl chloride copolymer resin obtained by copolymerizing a macromonomer having a polymer composed of an ethylenically unsaturated monomer containing a double bond and a double bond in the main chain can be obtained.

  Regarding the method for producing the vinyl chloride copolymer resin of the present invention, a polymer comprising an ethylenically unsaturated monomer containing a double bond in the initial water in which initial water is previously charged into a polymerization machine or a dispersion mixing tank or the like. A macromonomer having a polymer composed of an ethylenically unsaturated monomer containing a double bond, with a vinyl chloride monomer added thereto, or after being dispersed after the macromonomer having a main chain is added. It is preferable to start the copolymerization reaction by dispersing and mixing vinyl chloride monomers. Here, 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. In addition, “dispersed 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 any boundary. It means that it is impossible to distinguish between the two.

  "Initial water" used in the method for producing a vinyl chloride copolymer resin of the present invention comprises a vinyl chloride monomer or an ethylenically unsaturated monomer containing a double bond to a polymerization machine or a dispersion mixing tank. This is a part or the whole amount of the polymerization charge water that is added before introducing the macromonomer having the polymer in the main chain. The initial water amount is not particularly limited and may be any amount in which the macromonomer having a polymer composed of a vinyl chloride monomer or an ethylenically unsaturated monomer containing a double bond in the main chain is dispersed and mixed in the initial water. The initial water is preferably 1% to 100% of the total weight of water, more preferably in the range of 1% to 50% of the total weight of the feed water, more preferably 1% to 30% of the total weight of the feed water. This amount is particularly preferable because the time for dispersing and mixing is shortened.

  The total weight (M) and initial water weight (H) of the macromonomer and vinyl chloride monomer having a polymer composed of an ethylenically unsaturated monomer containing a double bond in the main chain are 0 <H / M. ≦ 3.0 is preferable because a macromonomer having a polymer composed of an ethylenically unsaturated monomer containing a double bond in the main chain and a vinyl chloride monomer are easily dispersed and mixed, and 0 <H / M ≦ When the macromonomer having a polymer composed of an ethylenically unsaturated monomer containing a double bond dispersed in the initial water in the main chain is added to the initial water, the vinyl chloride monomer is added. Phase transformation occurs in the dispersion, the vinyl chloride monomer becomes a continuous phase, and the macromonomer having a polymer composed of an ethylenically unsaturated monomer containing a double bond in the main chain and the vinyl chloride monomer Further preferred the dispersion mixing time is shortened and over.

  Further, after dissolving the dispersant and / or emulsifier in the initial water in advance, a macromonomer having a polymer composed of an ethylenically unsaturated monomer containing a double bond in the main chain is added and dispersed in the initial water. Even when the macromonomer having a polymer composed of an ethylenically unsaturated monomer containing a heavy bond in the main chain has a high viscosity, it forms droplets in the initial water and adheres to the inside of the can, the stirring blade, and the stirring shaft. This is preferable because it can be reduced and the intrusion into the recess in the reactor can be reduced.

  In the present invention, the dispersant and emulsifier previously charged in the initial water are preferably charged in a predetermined dispersant, 1/10 to the total amount of the emulsifier formulation, and contain ethylenic double bonds dispersed in the initial water. Since a macromonomer having a polymer composed of an unsaturated monomer in the main chain is dispersed and mixed with a vinyl chloride monomer, the dispersion mixing time can be shortened. It is more preferable to add the whole amount.

  The dispersion temperature (internal temperature) when dispersing and mixing a macromonomer having a polymer composed of an ethylenically unsaturated monomer containing a double bond in a vinyl chloride monomer in the main chain is 10 ° C. or higher and 60 ° C. or lower. It is preferably 20 ° C. or higher and 50 ° C. or lower. 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 10 ° C or more and 60 ° C or less. The macromonomer which has can be disperse-mixed uniformly.

  The rate at which the macromonomer having a polymer composed of an ethylenically unsaturated monomer containing a double bond in the main chain is introduced into the initial water is not particularly limited as long as it is in a dispersed state after the addition, and is continuously added. Any of a method, a method of batch loading, and a method of batch loading may be used. For example, when introducing a macromonomer having a polymer composed of an ethylenically unsaturated monomer containing a high-viscosity double bond in the main chain, in order to disperse it in the initial water, it can be added in small portions continuously. In addition, undispersed deposits are less likely to remain on the inner wall of a polymerization machine or a dispersion mixing tank.

  In the method for producing a vinyl chloride copolymer of the present invention, the rotational speed and dispersion time when dispersing a macromonomer having a polymer composed of an ethylenically unsaturated monomer containing a double bond in initial water in the main chain are as follows: There are no particular restrictions because it varies depending on the shape of the stirrer and the gap from the stirrer to the inner wall of the polymerization apparatus or dispersion mixing tank, but for example, the ratio of the paddle type stirrer diameter (d) to the polymerization apparatus diameter (D) (d / When D) is 3.0, the number of rotations is preferably 50 rpm or more.

  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.

By these methods, by uniformly 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,
For example, problems such as “copolymerization becomes abnormal polymerization and normal particles cannot be obtained” and “a large amount of scale occurs even when normal particles are obtained” can be suppressed.

  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-perfluorohexyl ethyl (meth) acrylate, 2-perfluorodecylethyl (meth) acrylate, 2-perfluorohexadecyl (meth) acrylate (Meth) acrylic acid monomers such as ethyl; styrene monomers such as styrene, vinyl toluene, α-methyl styrene, chlorostyrene, styrene sulfonic 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; containing 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, styrenic monomers or (meth) acrylic acid monomers are preferred in view of the physical properties of the product. More preferred are acrylate monomers or methacrylate monomers, more preferred are acrylate monomers, and most preferred is butyl acrylate. 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 a weight ratio of 40% or more. 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%. Preferably, it is 50 to 99.95% by weight, more preferably 50 to 97% by weight. 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.

  In the present invention, a vinyl chloride monomer is dispersed and mixed in a macromonomer having a polymer composed of an ethylenically unsaturated monomer containing a double bond in the main chain, and if necessary, suspension polymerization, fine suspension weight Dispersants, polymerization initiators, surfactants, dispersion aids, antioxidants, polymerization degree regulators, chain transfer agents, particle size regulators, pH regulators, gelling properties used in combination methods, emulsion polymerization methods, etc. An improver, an antistatic agent, a stabilizer, an antiscale agent, etc. are charged all at once, divided or continuously, and a copolymerization reaction is carried out at a predetermined polymerization temperature.

  The dispersant used in the suspension polymerization method is not particularly limited as long as it does not impair the object of the present invention. Examples of such a dispersant include partially saponified polyvinyl acetate; water-soluble cellulose ethers such as methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, and carboxymethyl cellulose; polyethylene oxide; polyvinyl pyrrolidone; polyacrylic acid; -Maleic acid copolymer; Styrene-maleic acid copolymer; Gelatin; Starch and other organic polymer dispersants 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.

  The surfactant used in the fine suspension polymerization method and the emulsion polymerization method is not particularly limited, and may be added in a range that does not impair the purpose of the present invention. For example, alkyl sulfate salts, alkyl aryl sulfonates, alkyl sulfosuccinate salts, fatty acid salts, α-olefin sulfonate salts, alkyl ether phosphate ester salts, polyoxyethylene alkyl aryl sulfate salts, polyoxyethylene alkyl sulfates Anionic surfactants such as ester salts (herein, “salts” include potassium salts, sodium salts, ammonium salts, etc.), sorbitan esters, polyoxyethylene alkyl ethers, polyoxyethylene alkyls Phenyl ethers, polyoxyethylene Hydrophilic nonionic surfactants such as alkyl ester compounds and the like, which may be used alone or in combination of two or more.

  The dispersion aid used in the fine suspension polymerization method is not particularly limited, and a dispersion aid that does not impair the object of the present invention may be added. Examples of such dispersion aid include lauryl alcohol. , Myristyl alcohol, cetyl alcohol, stearyl alcohol, etc .; higher fatty acids such as lauric acid, myristic acid, palmitic acid, stearic acid; esters of higher fatty acids; higher aliphatic hydrocarbons; halogenated hydrocarbons Preferred are water-soluble polymers, and these can be used alone or in combination of two or more thereof.

  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 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.

<Evaluation of macromonomer undissolved residue>
While confirming the macromonomer undissolved residue by visual observation of the obtained slurry and latex, 100 g of powder resin obtained by drying the slurry and latex was put in 900 g of methanol / water (50/50 volume ratio), The mixture is stirred for 1 hour under conditions of 25 ° C. × 50% RH, and the resin is filtered using an aspirator. After drying the filtrate, the dry weight was measured, and the dry solid weight in the resin was measured.

Moreover, applying a portion of the filtrate in KBr plate, taking the absorption of the 400 cm ^-1 from 4000 cm ^-1 in dried IR measuring instrument (Perkin Elmer Fourier transform infrared spectrophotometer SPECRUM1000), from a carbonyl group the signal (peak top in the vicinity of 1730 cm ^-1) is confirmed, carbon - if a peak was confirmed chlorine from the signal (peak top in the vicinity of 615 cm ^-1), was identified as a macromonomer undissolved residue.
<Visual observation of macromonomer residue in slurry and latex>
○: Macromonomer undissolved residue cannot be visually confirmed in the discharged slurry and latex.

    Δ: A small amount of undissolved macromonomer residue is observed in the discharged slurry and latex (sticky to sticky macromonomer when put in the slurry and latex).

×: Macromonomer residue undissolved in the discharged slurry and latex can be visually confirmed.
<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 example.

(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.
The viscosity of the one-end acryloyl group poly (acrylic acid-n-butyl) macromonomer at 25 ° C. was about 40 Pa · s.

(Example 1)
In an aqueous solution (300 parts) in which 1.16 parts of sodium lauryl sulfate was dissolved in advance as initial water in a stainless steel polymerization reactor having a volume of 25 liters equipped with a jacket and a stirrer, equivalent to 20 parts of the total monomers. Water was charged in advance. The internal temperature of the polymerization reactor was controlled at 20 ° C., and 40 parts of the one-end acryloyl group poly (n-butyl acrylate) macromonomer of Production Example was added while stirring at a rotation speed of 200 revolutions per minute. After degassing the inside of the polymerization reactor, 60 parts of vinyl chloride monomer was charged, and the macromonomer was dispersed and mixed in the vinyl chloride monomer by stirring for 60 minutes after the completion of the addition of the vinyl chloride monomer. 0.07 part of 2,2′-azobis- (2,4-dimethylvaleronitrile) and 1.4 part of stearyl alcohol were added to the polymerization reactor and homogenized for 2 minutes, and then 1.16 parts of sodium lauryl sulfate was added in advance. 280 parts of the dissolved aqueous solution was added 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)
A stainless steel polymerization reactor having an internal volume of 25 liters equipped with a jacket and a stirrer was charged with a total amount of an aqueous solution (300 parts) in which 1.16 parts of sodium lauryl sulfate had been previously dissolved as initial water. The internal temperature of the polymerization reactor was controlled at 20 ° C., and 20 parts of acryloyl group poly (n-butyl acrylate) macromonomer at one end in Production Example was added while stirring at a rotation speed of 200 revolutions per minute. After degassing the inside of the polymerization reactor, 80 parts of vinyl chloride monomer was charged, and the macromonomer was dispersed and mixed in the vinyl chloride monomer by stirring for 100 minutes after the addition. 0.07 part of 2,2′-azobis- (2,4-dimethylvaleronitrile) and 1.4 part of stearyl alcohol were added to the polymerization reactor and homogenized 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)
A stainless steel polymerization reactor having a volume of 25 liters equipped with a jacket and a stirrer is charged with 40 parts of water as the initial water in advance, and partially saponified with a degree of saponification of about 80 mol% and an average degree of polymerization of about 2000. 0.05 part of polyvinyl acetate and 0.005 part of polyethylene oxide having an average molecular weight of about 4.5 million were dissolved with stirring at a rotation speed of 900 revolutions per minute while controlling the internal temperature of the polymerization reactor at 20 ° C. While stirring, 40 parts of acryloyl group poly (acrylic acid-n-butyl) macromonomer of Production Example was charged and degassed, and then 60 parts of vinyl chloride monomer was charged and stirred for 10 minutes after charging. The macromonomer was dispersed and mixed in the vinyl chloride monomer. After charging 0.03 part of t-butylperoxyneodecanoate and 0.01 part of 1,1,3,3-tetramethylbutylperoxyneodecanoate, 110 parts of hot water at 60 ° C. 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 4)
A stainless steel polymerization reactor having a volume of 25 liters equipped with a jacket and a stirrer is charged with 100 parts of water in advance as the initial water, and partially saponified with a degree of saponification of about 80 mol% and an average degree of polymerization of about 2000. 0.05 part of polyvinyl acetate and 0.005 part of polyethylene oxide having an average molecular weight of about 4.5 million were dissolved while stirring at a rotational speed of 450 revolutions per minute while controlling the internal temperature of the polymerization reactor at 40 ° C. While stirring, 6 parts of acryloyl group poly (acrylic acid-n-butyl) macromonomer of Production Example was charged and degassed, and then 94 parts of vinyl chloride monomer was charged and stirred for 15 minutes after the addition. The macromonomer was dispersed and mixed in the vinyl chloride monomer. After charging 0.03 part of t-butylperoxyneodecanoate and 0.01 part of 1,1,3,3-tetramethylbutylperoxyneodecanoate, 50 parts of hot water at 60 ° C. were then added, 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 5)
A stainless steel polymerization reactor with a capacity of 1500 liters equipped with a jacket and a stirrer is charged with 300 parts of water in advance as the initial water, and partially saponified with a degree of saponification of about 80 mol% and an average degree of polymerization of about 2000. 0.05 part of polyvinyl acetate and 0.005 part of polyethylene oxide having an average molecular weight of about 4.5 million were dissolved with stirring at a rotational speed of 560 revolutions per minute while controlling the internal temperature of the polymerization reactor at 25 ° C. While stirring, 3 parts of acryloyl group poly (acrylic acid-n-butyl) macromonomer of Production Example was charged and degassed, and then 97 parts of vinyl chloride monomer was charged and stirred for 20 minutes after the addition. The macromonomer was dispersed and mixed in the vinyl chloride monomer. After charging 0.03 part of t-butylperoxyneodecanoate and 0.01 part of 1,1,3,3-tetramethylbutylperoxyneodecanoate, 50 parts of hot water at 60 ° C. were then added, 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 6)
A stainless steel polymerization reactor having a capacity of 1500 liters equipped with a jacket and a stirrer is preliminarily charged with 20 parts of water as the initial water, and partially saponified with a degree of saponification of about 80 mol% and an average degree of polymerization of about 2000. 0.05 part of polyvinyl acetate and 0.005 part of polyethylene oxide having an average molecular weight of about 4.5 million were dissolved with stirring at a rotational speed of 560 revolutions per minute while controlling the internal temperature of the polymerization reactor at 25 ° C. While stirring, 10 parts of acryloyl group poly (acrylic acid-n-butyl) macromonomer of Production Example was charged and degassed. Then, 90 parts of vinyl chloride monomer was charged and stirred for 30 minutes after charging. The macromonomer was dispersed and mixed in the vinyl chloride monomer. After charging 0.03 part of t-butylperoxyneodecanoate and 0.01 part of 1,1,3,3-tetramethylbutylperoxyneodecanoate, then charging 130 parts of hot water at 60 ° C., 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.

(Comparative Example 1)
The initial amount of water in Example 1 was set to 0, and 40 parts of the acryloyl group poly (n-butyl acrylate) macromonomer of Production Example was charged into an empty reactor, and the inside of the reactor was deaerated. By controlling the internal temperature of the polymerization reactor to 20 ° C. and stirring at a rotation speed of 200 revolutions per minute, 60 parts of vinyl chloride monomer was added, and the vinyl chloride monomer was stirred for 60 minutes after completion of the addition of the vinyl chloride monomer. Was mixed with the macromonomer. 0.07 part of 2,2′-azobis- (2,4-dimethylvaleronitrile) and 1.4 part of stearyl alcohol were added to the polymerization reactor and homogenized for 2 minutes, and then 1.16 parts of sodium lauryl sulfate was added in advance. 300 parts of the dissolved aqueous solution was added 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.

  When the latex was discharged from the reactor, the macromonomer that had first entered the discharge port reservoir in the reactor was discharged as a residue, and the macromonomer residue was also confirmed in a recess such as a sample port in the reactor.

(Comparative Example 2)
Polymerization was carried out in the same manner as in Example 1 except that 20 parts of water corresponding to the total amount of monomers that did not contain sodium lauryl sulfate was charged in advance as the initial water of Example 1. Table 1 shows the evaluation results of the polymerization stability.

  When the macromonomer is added to water while stirring, the macromonomer is difficult to disperse, and an aggregate is formed at the bottom of the stirring blade. When the latex is discharged from the reactor, it is first placed in the discharge outlet in the reactor. A macromonomer residue that had infiltrated was confirmed.

(Comparative Example 3)
Polymerization was carried out in the same manner as in Example 1 except that the amount of the macromonomer used in Example 1 was changed from 40 parts to 55 parts and the vinyl chloride monomer was changed from 60 parts to 45 parts. Table 1 shows the evaluation results of the polymerization stability.

  Since the latex during the reaction was unstable, it was confirmed that the scale was remarkably adhered to the inner wall of the reactor after the discharge, and that there were many coarse particles in the latex.

(Comparative Example 4)
Polymerization was carried out in the same manner as in Example 2 except that 400 parts of an aqueous solution in which 1.16 parts of sodium lauryl sulfate was previously dissolved was used as the initial water of Example 2 with respect to the total monomers. Table 1 shows the evaluation results of the polymerization stability.

  A large amount of water is used as the initial water, in which the macromonomer and the vinyl chloride monomer are not dispersed and mixed for a set time in order to dissolve the macromonomer and the vinyl chloride monomer, and the presence of the macromonomer residue is visually observed in the discharged latex. confirmed.

(Comparative Example 5)
The initial water in Example 3 was set to 0, 40 parts of the macromonomer was charged into an empty reactor, and the inside of the reactor was deaerated. While stirring at a rotational speed of 900 revolutions per minute, 60 parts of vinyl chloride monomer was charged, and after the addition, the macromonomer was dispersed and mixed in the vinyl chloride monomer by stirring for 10 minutes. 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, 0.005 part of polyethylene oxide having an average molecular weight of about 4.5 million, 0.03 part of t-butylperoxyneodecanoate, After adding 0.01 part of 1,1,3,3-tetramethylbutylperoxyneodecanoate, 150 parts of hot water at 60 ° C. was added, 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.

  When the slurry was discharged from the reactor, the macromonomer that had first entered the discharge port reservoir in the reactor was discharged as a residue, and the macromonomer residue was also confirmed in a recess such as a sample port in the reactor.

(Comparative Example 6)
After charging 40 parts of the initial water of Example 3, the polymerization reactor internal temperature was controlled at 20 ° C. without dissolving the dispersant, and the mixture was stirred at a rotational speed of 900 revolutions per minute. Was added, degassed, 60 parts of vinyl chloride monomer was added, and the macromonomer was dispersed and mixed in the vinyl chloride monomer by stirring for 10 minutes after the addition.

  Thereafter, 0.05 part of partially saponified polyvinyl acetate having a saponification degree 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-butyl peroxyneodecanoate 0.03 Then, 0.01 part of 1,1,3,3-tetramethylbutylperoxyneodecanoate was added, and 110 parts of hot water at 60 ° C. was added, 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.

    When the macromonomer is added to water while stirring, the macromonomer is difficult to disperse and an aggregate is formed at the bottom of the stirring blade. When the slurry is discharged from the reactor, A macromonomer residue that had infiltrated was confirmed.

(Comparative Example 7)
Polymerization was carried out in the same manner as in Example 1 except that the amount of the macromonomer used in Example 3 was changed from 40 parts to 55 parts and the vinyl chloride monomer was changed from 60 parts to 45 parts. Table 1 shows the evaluation results of the polymerization stability.

  Since the slurry during the reaction was unstable, it was confirmed that the scale was remarkably adhered to the inner wall of the reactor after being dispensed, and there were many coarse particles in the slurry.

(Comparative Example 8)
Polymerization was performed in the same manner as in Example 5 except that the initial water in Example 5 was changed to 400 parts, and the slurry was discharged. Table 1 shows the evaluation results of the polymerization stability.

  A large amount of water is used as the initial water, in which the macromonomer and the vinyl chloride monomer are not dispersed and mixed for a set time in order to dissolve the macromonomer and the vinyl chloride monomer, and the presence of the macromonomer residue is visually observed in the discharged latex. confirmed.

Claims (1)

When 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, The ratio of the vinyl chloride monomer to the total amount is 50% by weight or more and less than 100% by weight, and the macromonomer having a polymer composed of an ethylenically unsaturated monomer containing a double bond in the main chain and the vinyl chloride monomer The total weight (M) and the initial water weight (H) are in the range of the following formula (1):
0 <H / M ≦ 3.0 (1)
After dissolving the dispersant and / or emulsifier in the initial water, a macromonomer having a polymer composed of an ethylenically unsaturated monomer containing a double bond in the main chain is added and dispersed in the initial water. A method for producing a vinyl chloride copolymer resin, comprising introducing a monomer.