TW200808837A - Dispersion stabilizer for suspension polymerization of a vinyl compound - Google Patents

Abstract

The present invention aims at providing a dispersion stabilizer for suspension polymerization of a vinyl compound, which gives vinyl chloride polymer particles having a sharp particle size distribution and a high bulk density owing to excellent dispersion stability during polymerization, and which can produce vinyl chloride polymer particles with few wet foams, hardly accompanied with formation of polymer scales and foamy polymers attributable to dry foams, with less coloring, and having excellent heat resistance. The dispersion stabilizer of the present invention comprises a PVA-based resin having a 1, 2-diol component at a side chain and a saponification degree of 65 to 87 mol%.

Description

200808837 IX. OBJECTS OF THE INVENTION: TECHNICAL FIELD The present invention relates to a dispersion stabilizer for suspension polymerization of a vinyl compound, and more particularly to a dispersion stabilizer for suspension polymerization of vinyl chloride, and more particularly, to a polymerization. When the dispersion stabilizer is excellent, the obtained vinyl chloride polymer particles have a narrow particle size distribution, a large bulk density, and a low foaming of the aqueous solution, thereby inhibiting the occurrence of wet foam during polymerization, which also reduces the occurrence of dry bubbles in summer. It is possible to suppress the occurrence of a polymer scale (SCale) and a bubble polymer which are causes of fish eyes, and further, it is possible to produce vinyl chloride polymer particles having less coloration and excellent heat resistance. [Prior Art] The industrial potential of chloroacetic acid resin, i, 糸 般 以 以 以 以 批次 批次 批次 批次 批次 批次 批次 批次 批次 批次 批次 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 氯; λ media, the use of oil-soluble (four) into the twisted private ... early basket knife in the water-based I tf of the starter polymerization. The main reason for the quality of the 氦 系 树脂 树脂 树脂 树脂 舨 5 5 5 5 5 5 取 取 取 取 取 取 取 取 取 取 取 取 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 取 取The effect of mixing is the biggest. In the eighth, the dispersing stabilizer is used as the performance for the vinyl chloride resin. For example, the following can be exemplified: (4): The dispersing agent for the dispersing agent should be used to protect the colloidal force and dispersive force, and have a sufficient particle size distribution. The effect of the stenosis is on the use of the oxyethylene-based polymer particles, (b) the shape processing property is changed to a different size, and the absorption rate of the plasticizer is increased by 9%, and the animal is porous, or Inhibition of the formation of the anti-layer opening of the micro-polymer particles of the Mole B; (c) in order to remove the porous 312XP / invention instructions (supplement) / 95 · 11 / 9512812 〇 200808837

= the residual vinyl chloride monomer in the sub-group or the prevention of the fisheye in the molded article, etc., and the effect of the void ratio of the vinyl chloride-based polymer particles; (4) the polymerization efficiency is improved, and the polymerization is improved. The effect of the body density of the body; # U 季述刀政女疋's generally used alone or in combination with polyvinyl alcohol = month 曰 ^ under the polyethylene (referred to as (5), cellulose derivatives, Ming: L: rpvA resin is widely used , but still can not fully fully describe the required performance, and in order to improve its performance, is carrying out various

In addition, in order to improve the productivity, it is required to shorten the polymerization requirements. I, '_, ... In order to increase the heat removal rate of the polymerization heat, use the polymerization tank with the second ^ or to shorten the heating time. The method of pre-filling the aqueous medium (heat feed method, h〇t charge) is filled. However, in the case of using a polymerization tank equipped with a reflux condenser, the pressure near the reflux condenser is lowered due to the condensation of the vinyl chloride monomer, so that the occurrence of wet and dry bubbles becomes serious. . The wet foam is mainly caused by the foaming of the main knives caused by the interfacial activity energy of the PVA-based resin, which is a cause of a decrease in the productivity of the polymerization tank. In addition, the term "dry foam" mainly refers to foaming which is mainly composed of vinyl chloride resin particles and chloroethylene monomer in the middle to late stages of polymerization, and is formed into a foamy polymer and adhered in a form of polymer scales. ^ Poly:: The inner wall and the reflux condenser prevent the heat removal during polymerization or the reason for mixing into the product to become a fisheye. As a countermeasure against related problems, the following ones have been proposed: 〇1% by weight 312XP/invention specification (supplement)/95-11/95128120 6 200808837 In the ultraviolet absorption spectrum of an aqueous solution, the absorbance at 280 nm (a) is greater than ^, The absorbance at 32〇nm (1)) is 〇·3 or more, and (a)/(b) is less than 〇3, embedded.

A dispersion stabilizer for suspension polymerization of a vinyl compound composed of a PVA-based polymer having a segmental property of 0.4 or more (for example, referring to the patent document, the degree of chemical resistance is 60 mol% or more, and the block property is 〇·3~) p·6 pVA-based polymer: a vinyl compound composed of a pvA-based polymer obtained by heat-treating at ～5 to 2 hrs at 90 to 180 C under an atmosphere of an oxygen concentration of 800 〇ppm or less. Dispersion stabilizer for suspension polymerization (for example, refer to Patent Document 2), in the ultraviolet absorption spectrum of 〇·丨 wt% aqueous solution, the absorbance (c) of 28 〇 ship is greater than 吸·1,32 〇nm absorbance (d) 〇· 〇7 or more, (c) 曰/(d) is 〇·7 or more, γι of 1% by weight aqueous solution is 4 〇 or less, 〇·工重里/^水, and the wavelength of 30 C of the combined liquid is 5〇 The suspension at a 〇nm ratio of 8〇% is a suspension of a vinyl compound composed of a PVA water and a body having a Mw/Mn of ··35 or more and a Mw/Mn of 2·1 to 4·9. A dispersion stabilizer for polymerization (for example, refer to Patent Document 3). (Patent Document 1) Japanese Laid-Open Patent Publication No. Hei 8-283313 (Patent Document 2) Japanese Patent Laid-Open Publication No. JP-A No. 2004-489889 (Patent Document 3). SUMMARY OF THE INVENTION PROBLEMS TO BE SOLVED BY THE INVENTION However, the dispersion polymerization for suspension polymerization described in Patent Document 1 Although the agent can suppress foaming during polymerization, it is not sufficient in terms of dispersion stability, and there are cases in which coarse particles of a vinyl chloride resin are formed; and in the patent documents 2 and 3, the dispersion of m is used in (4). If the double 312XP/invention specification (supplement)/95-11/95128120 7 200808837 bond is introduced into the pVA resin by heat treatment, the heat resistance is less than the resistance of the milk of the A. However, there is still room for improvement when using the lock _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ Less, water: the amount of inhibition of the occurrence of wet foam, and because it also reduces the wall of dry bulbs: inhibition = the formation of polymer scales for the eyes of the fish eye attached to the formation of the bubble in the polymerization tank, and then the formation of bubble-like polymer, and then Can make a hot grain = more F-color and zinc-burning polymers with less zinc burning and higher bulk density (means for solving problems) Side = people with tr-months have been concentrating on research related issues

季季二礼礼""成*, and 4 degrees of PVA 65 of 65~87 mol%;:: Dispersion stabilizer for suspension polymerization of banquet compounds" /, the above purpose is consistent, 遂 completed the present invention The most characteristic feature of the invention is that the PVA resin having a ruthenium 1,2-diol component in the side chain and the agent can be applied to the dispersion stability d for suspension polymerization, and the specificity of the present invention can be obtained. The pVA-based resin containing 19, 1, 2, or more ethylene glycol bonds as described in Japanese Patent Laid-Open No. 233905 is called a polymerization process in the manufacturing step. 2-Glycol bond refers to the bond of the primary bond J into =

ί = di(tetra)yl, and by the above point, is a foreign matter with the PVA resin of the present invention. 312xp / invention manual (supplement) / 95·11/95 muo . 200808837. In addition, such an m-type resin containing a component of u and a diol in the side chain is preferably a resin containing 丨2-— ” which is not contained in the general formula (1).

R——c——X 1R——c——2R ΓΟΗ

6R 5R——C丨OH (wherein R, R2, and R3 each independently represent a single bond or a bond chain, R4, R5, and Rrm organic groups, and an organic group.) W is independently represented by a hydrogen atom ( Advantageous Effects of Invention In the suspension polymerization of the vinyl compound of the invention, the dispersion stability of the dispersion stabilizer a is excellent, so that the ethylene-based polymer particles having a narrow particle size distribution and having a bulk density have less wet bubbles and are caused by dry foam. The case where the polymerized scales are attached to the inner wall of the polymerization tank and the amount of the foamed polymer produced 再', and the ethylene-based polymer particles having a small amount of mis-burning and having a good calorific property which is common in the soft-mixing formulation can be obtained. Therefore, it is extremely industrial; effective. In addition, the PVA-based resin used in the dispersion stabilization of suspension polymerization used in the prior art must be heat-treated in the course of its manufacture.

The pVA-based resin used in the present invention does not require heat treatment, and is therefore advantageous from the viewpoint of the present invention. X

312XP@_(Supplement)/95-11/95128120 Q 200808837 [Embodiment] The description of the constituent elements described below is the present invention (representative example), and is not limited thereto. The following is a detailed description of the present invention. The PVA-based resin used in the present invention is generally a PVA-based resin having a 1,2-diol structural unit, and the hydrogen atom or the organic group is independently represented by R 2 and R, respectively. Two? Key chain, do not independently represent hydrogen::::, "(Chemical 2) ^ Baiji base.

3 · R-c——X1 Plant R—C—R •C——ο 4 - Η R——c——ο Still, the diol diol structural unit of the general formula (1) of this PVA resin The content is preferably about 0.3 to 20 mol%, and the remainder is the same as the resin of the saponification, and is composed of a vinyl alcohol structural unit equivalent to a saponification degree and a vinyl acetate structural unit other than the saponification degree. . In the 1,2-diol structural unit represented by the general formula (1), all of r1 to R3 and R4 to r6 are preferably a hydrogen atom, but if it is an amount which does not greatly impair the resin property, it may be substituted with an organic group. The organic group is not particularly limited, and is preferably a group having 1 to 4 carbon atoms such as a mercapto group, an ethyl group, a n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group or a t-butyl group. If necessary, it may have a substituent such as a halogen group, a smoke base, a 312XP/invention ugly book (supplement)/95-11/95128120 1〇200808837 base, a carboxylic acid group, a carboxylic acid group or the like. In addition, the oxime in the structural unit of the 丨'2-diol shown by the general formula (1) is representative of the early bond', but may be a bond chain if it does not hinder the effect of the present invention. The chain is not particularly limited, and examples thereof include an alkyl group, an alkenyl group, a stretching group, a phenyl group, a naphthyl group, and the like. (These gases can also be replaced by halogens such as chlorin, chlorin, and molybdenum. ;_G_...((10))m_, -(CH2〇)mCH2-> -C0-. -COCO-^ -C〇(CH2)mC〇^ -C〇(CeH4)CO- ^ -s-, -cs- , -S0_, _s〇2_, _NR_, _C0NR__, _NRc〇, _csnb, -S-, -NRNR-, _HP〇4—, _Si(10))2_ ...〇si(〇R)2, -0Si(0R)20- -Ti(0R)2-, -〇Ti(10))2-, _〇Ti(()R)2〇_, -AK0R)-, etc. (d is independently an arbitrary substituent, preferably a hydrogen atom, The base is burned, and m is a natural number. In the pot, from the viewpoint of the technical point of manufacture or the material, it is preferable that the number of the bases is 6 or less, or -CH2〇CH2_. The method for producing the PVA-based resin to be used in the present invention is not particularly limited, and a method of saponifying the copolymer of the vinyl vinegar-based monomer and the compound represented by the following formula (2) can be suitably used. (3)

11 3 ΠΧΡ / invention manual (supplement) / 95-11/95128120 200808837 (wherein, R1, R2, and R3 are independently dried * shop 7 feeding table is not atomic or organic, χ means single bond or The bond chain 'R4, R5, and Ar6 each independently represent a ruthenium atom or an organic group, and R7 and R8 each independently represent a ruthenium atom or R9_c〇_ (wherein, R9 is an alkyl group).) Further, as (i) In the production method, the following method may be used: (ii) a method of saponifying and decarbonating a copolymer of a vinyl ester monomer and a compound of the following general formula rh _ 奴 3 3); (Chemical 4)

Wherein R 1 , R 2 and R 3 each independently represent a hydrogen atom or an organic group, and 乂 represents a single bond or a bonded chain ' R 4 , R 5 , and 卩 6 , and represents a hydrogen atom or an organic group.

(iii) a method of saponifying and deketalizing a copolymer of a vinyl vinegar monomer and a compound represented by the following general formula (4);

(Chemical 5) 312XP/Invention Manual (Supplement)/95-11/95128120 12 (4) 200808837 (wherein, R1, R2, and R3 each independently represent a hydrogen atom or an organic group, and χ represents a single bond or bond. The chain, R4, R5, and independently represent a hydrogen atom or an organic group, and γ and R" each independently represent a hydrogen atom or an organic group. Further, as the vinyl ester monomer used in the present invention, for example, formic acid vinegar is exemplified. , Vinyl acetate vinegar, Ethyl propionate, Ethyl valerate, Ethyl butyrate, Vinyl isobutyrate, Trimethyl vinyl acetate, Vinyl citrate, Vinyl guar, Stearic acid Vinyl ester, vinyl benzoate, vinyl pentoxide, etc., are preferably acetic acid in terms of economy. (11) and (iii), the method of (i), [(i), (1) is carried out by using the ethylene s-type monomer and the above-described formula (2). A method of producing a PVA-based resin having the above-described general formula 1'2-diol structural unit after the copolymerization is further carried out. In the compound represented by the general formula (2), 'R1 to R3m X: R9:, r. f is the same as the general formula 9 (1), and R8 is independently hydrogen or i. (wherein R9 is an alkyl group, preferably a methyl group, a propyl group, a butyl group, or the like The polymerization reactivity and the range in the subsequent step may also have a substituent of a functional group, a hydrocarbon group, an ester group, a (tetra) group and an acid group. 3:-: ΓΓ 之 化合物 化合物 化合物 化合物 化合物 化合物 化合物 化合物 化合物 化合物 化合物 化合物 化合物 化合物 化合物 化合物 化合物 化合物 化合物 ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; , base + Ding, 3,4~ dimethoxyl-2: two ''Χ' is 4,5_di-diyl+pentyl, 4,5-di-diyl-3-methyl 13 200808837 Oxy-3-mercapto-p-pentene, 5,6-dihydroxy-p-hexene, 5,6-dimethoxyl-1-hexene; X is _CH2〇CH2_ or _0CH2_ Glycerol monoallyl ether, 2,3-di, etidyloxyl-1-allyloxypropane, 2_ethyloxyl-1-enyloxy=3·^ stem propane, 3_ Ethyloxy_丨-allyloxy-2-hydroxypropane, glycerin monovinyl ether, glycerol monoisopropenyl ether, and the like. In terms of /, reactivity, and industrial operability, =1^, 1^3, 1^, 1^, 1^ is hydrogen, but also a single bond, and 1^18 is 1^^ Further, R9 is a base of 3,4-: alkoxy+butene is preferred, and particularly preferred is a 3,4-diethyloxy+butylene group wherein r9 is a methyl group. Further, the reactivity ratio of each monomer in the copolymerization of ethylene acetonate with 3,4-diethoxycarbonyl+butylene is r (vinyl acetate) = 〇. 71 〇, r (3, 4) _Diethoxycarbonyl 1-butene) = 0.701, which is compared with vinyl acetonate in the case of ethyl vinyl carbonate described later) = 0.85, r (vinyl carbonate vinegar) = 5 4,3,4_Diethoxycarbonyl+butene shows superior co-reaction with vinyl acetate.尚 Furthermore, the industrial production of 3, 4-diethoxydecene can be broken into the market by EASTMAN C:_I (:AL company's products, grades can be introduced into ACROSS products. Also, can also be used in 3, 4_diethoxycarbonyl_丨_butene obtained as a by-product in the -but-forming step: Further, it is also possible to use the one described in Japanese Patent Laid-Open No. Hei. A method in which oxy-2-butene is converted to 3,4-diethyloxyl, and W_/2 is described as a succinimide by monoepoxy: 3, 4-diethyl oxime A well-known technique such as a method of base-oxime-butene. The ethylene vinegar monomer is compounded with the compound of the general formula (2), and the wrist is 812g 14 200808837. The solution may be carried out by a known method such as bulk polymerization, solution polymerization, county, dispersion polymerization, or emulsion polymerization. As a method of filling the monomer component in the copolymerization, any method such as - sub-filling, fractional filling, continuous filling, or the like can be used: 1 > 2 of the compound represented by the general formula (7) In view of the fact that the diol structure is monolithic in the molecular chain of the polyvinyl vinegar-based polymer, it is preferred to use 2, preferably a polymerization according to the HANNA method using the ruthenium ratio of the above-mentioned ethyl acetate vinegar. method. ▲ As a solvent to be used in such a copolymerization, for example, a lower alcohol such as methyl alcohol, isopropanol, n-propanol or butanol, or a ketone such as acetone ketone may be used. Industrially, methanol is suitably used. The amount of the earth-ethyl solvent to be used may be appropriately selected in accordance with the chain transfer constant of the polymerization medium of the intended copolymer. For example, the solvent is from S (solvent) / M (monomer) = 〇〇 1 to 1 〇 (weight /, 〇 · 〇 5 ~ 3 (weight ratio) range is selected. 乂 better copolymerization using a polymerization catalyst, as such a polymerization catalyst, such as azobisisobutyronitrile, peroxidation a known free-filament catalyst for acetamidine, benzoyl peroxide, peroxygen = cassia, etc.; and a low-temperature active radical susceptibility of azobisazodimethoxy dimethyl hydrazine The amount of use depends on the type of the copolymer and the type of the product, and can be arbitrarily selected in accordance with the polymerization rate. For example, 312XP/invention specification (supplement)/95-11/95128120 for azo In the case of isobutyronitrile and acetamidine, it is preferably 0.01 to 0.7 mol% relative to the ethylene sulfonium precursor, and particularly preferably 〇〇2 〇5 mo 15 200808837, further, copolymerization The reaction temperature is carried out depending on the solvent to be used, and is preferably about c, preferably 40. The copolymer obtained by π is further subjected to crystallization, which is carried out by dissolving the copolymerized polymer in a solvent towel of the material, using a test medium or an acid catalyst. Representative solvents can be exemplified. For example, methanol, ethanol, propanol, second butane, alcohol, etc. are particularly preferred. The concentration of the copolymer in the alcohol is appropriately selected depending on the degree of the system, and is usually selected from the range of 1 G to 6 G% by weight. The saponification catalyst may, for example, be a metal hydroxide of sodium hydroxide, potassium hydroxide, methanol steel, sodium ethoxide, potassium methoxide or methanol, and a catalyst such as an alcoholate; sulfuric acid, hydrochloric acid, nitric acid, A An acid catalyst such as a saponification catalyst, a saponification catalyst, etc. The amount of the saponification catalyst used is appropriately selected according to the saponification method, the target saponification degree, etc., in the case of using a catalyst. The total amount of the 2-diol structural unit is 1 mole, usually 0.^0 millimolar, preferably 217 millimolar, relative to the oxime of the vinyl lanthanide precursor and the compound of formula (4). 0. In addition, the reaction temperature of the saponification reaction is not particularly limited. It is preferably 1 〇 to 6 〇, preferably 20 to 50 ° C. [(ii) Method] (Π) The method is to copolymerize a vinyl ester monomer with the above general formula (the compound is copolymerized) In the case of the PVA-based resin of the 1,2-diol structural unit represented by the general formula (1), the 312XP/invention specification (supplement)/95-11/95128120 200808837 The above general (10) used in the present invention is exemplified by the compound of 6 and X, and the m phase (4) having good silkiness is obtained, wherein acetoacetate is used as the oxime and x is a single bond. When the vinyl ester-based monomer is copolymerized with the above-mentioned general and saponified, it is carried out in the same manner as the compound of the above (1) () = AB. Further, it is not necessary to carry out decarbonation specifically for decarbonation, and the ethyl carbonate is bonded to a condensed diol structure. Do not hunt by the opening and closing of the ring and turn into u - under high temperature, this situation can also be carried out under a certain dust (normal pressure ~ lxl 〇 7Pa) (50 ~ 200 c) to make the vinyl ester partial saponification knife 7 1G Under carbonic acid, the above-mentioned addition can also be carried out after decarbonation. [Method of (iii)] ((1)) A method in which a vinyl ester monomer is copolymerized with a compound of the above general formula (4), followed by saponification and deketalization to produce a hydrazine and is represented by the formula (1). In the compound represented by the above general formula (4) used in the invention, R1 to R3, R4 to R6 and X may be the same as those of the above general formula (1), and R1. And ru are each independently hydrogen or an alkyl group; the alkyl group is not particularly limited, and is preferably a carbon such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or t-butyl. Number 1 to 4 alkyl groups. Such an alkyl group may have a halogen group, a hydrocarbon group, a vine group, a decanoic acid group, or a tartaric acid group in the range of 312XP/invention specification (supplement)/95-11/95128120 17 200808837 which does not inhibit copolymerization reactivity and the like. Substituting substituents. Among them, from the viewpoint of ease of availability and good copolymerization, it is preferable to use a ruthenium ^^^ as a hydrogen and a single bond =, Rl °, R " 2, 2-dioxane which is an alkyl group. Further, the group is a vinyl group of 2,2-dimethyl-4-vinyl-u-dioxolane. When the vinyl ester monomer is copolymerized and saponified with the compound represented by the above general formula (4), it is carried out in the same manner as in the above (i). Further, when the saponification reaction is carried out using an alkali catalyst, the ketation is further carried out by using an acid catalyst in an aqueous solvent (water, water/acetone, water/methanol, or the like, a lower alcohol mixed solvent, etc.). The ketal is subjected to conversion to a 1,2-diol structure. The acid catalyst in this case may, for example, be acetic acid, hydrochloric acid, sulfuric acid, nitric acid, mercapto acid, zeolite or cation resin. Further, when the saponification reaction is carried out using an acid catalyst, the special treatment is not performed, and the ketal is simultaneously subjected to deketalization, and converted into a 1,2-diol structure. The m-based resin used in the present invention is not hindered. For the purpose of the present invention, it is possible to use a copolymerization of various unsaturated monomers. The amount of the unsaturated monomer is not uniform - but it is not good if it is too large to cause water solubility or to reduce gas barrier properties. Examples of such an unsaturated monomer include stilbene such as ethylene m α-octene, α-pinene, and α+octaene; propionic acid, methyl methacrylate, and crotonic acid Alenic acid, maleic acid needle, itaconic acid, etc. 3ηχρ/Invention Manual (supplement)/95_ιι/9512812〇18 200808837 = saturated acid, its salt m silk s purpose; acrylonitrile, methacrylonitrile, etc. Nitrile; diacetone acrylamide, acrylamide, methacryl ife, etc., such as ethylene acid, allylic acid, decyl olefinic acid, etc. a vinyl compound; a vinyl compound such as dimethylallyl ketene, polyvinyl vinylpyrrolidone or vinyl chloride; a vinyl acetate substituted with isopropene S?, 1-methoxyvinyl acetate; Vinyl chloride, 1,4-diethoxycarbonyl-2-butene, ethyl carbonate, and a monomer containing an ethyl oxime group. Further, for example, a polyoxyethylene (meth)allyl bond, polyoxyethylene (meth) acrylamide, polyoxypropylene (meth) acrylamide, polyoxyethylene (fluorenyl) acrylate, Polyoxypropylene (meth) acrylate, polyoxyethylene (1-(methyl) acrylamide-1, bis dimethyl propyl) ester, polyoxyethylene vinyl sulfonate, polyoxypropylene vinyl _ a polyoxyalkylene-containing monomer such as polyoxyethylene propylamine, polyoxypropylene allylamine, polyoxyethylene vinylamine, polyoxypropylene vinylamine or the like; N-acrylamide Methyltrimethylammonium chloride, N-propyleneamine ethyl dimethyl ammonium chloride, N-propylene decyl propyl trimethyl ammonium chloride, 2 propylene sulfonium ethyl trimethyl ammonium chloride, 2_Methyl propylene oxime ethyl trimethyl chlorinated clock, 2 hydroxy-3-methyl propylene methoxypropyl trimethyl ammonium chloride, allyl trimethyl ammonium chloride, f allylic three A cationic group-containing monomer such as methylammonium chloride, 3-butenetrimethylphosphonium chloride, monomethyldiallylammonium chloride or diethyldiallylammonium chloride. In addition, by setting the polymerization temperature to 10 〇 (KC or more, it is possible to use a 1,2-diol bond for the pVA main chain application of about 1.6 to 3.9 mol%. The saponification degree of the resin is 65 to 87 mol%, more preferably 312XP/invention specification (supplement)/95-11/95128120 19 200808837 68 to 83 mol% 'extra good 69 to 81 mol%. When the degree of saponification is too low, when 3,4-monooxy-oxime-butene is used as the copolymer, the saponification of the dioxane moiety of the side chain may be insufficient, or the water solubility may be lowered. In addition, when the degree of saponification is too high or too low, the vinyl chloride resin becomes coarse particles or the particle size distribution becomes large, which is not preferable. Further, the degree of saponification in the present invention The present invention is defined as the molar number of the hydroxyl group of the total (mole) of the vinyl ester of the vinyl ester of vinylidene acetate or the like with respect to (iv) 3,4-dimethoxy-1-butene. The average degree of polymerization of the PVA-based resin (measured according to JIS κ 6726) is 400 to 850, more preferably 5 to 850, and particularly preferably 600 to 830, and the average = degree is too small. When the protective colloidal force is insufficient, if it is too large, the plasticizer absorbability of the vinyl chloride-based resin is lowered, which is not preferable. Further, the 12-diol in the PVA-based resin of the present invention is not preferable. The content of the component is 1 20 mol%, more preferably 1 to 8 mol%, especially good ^ mol%, and most preferably 2 to 6 mol%. If the content is too small, it will be in the initial stage of suspension polymerization of vinyl chloride. The occurrence of wet bubbles or the occurrence of dry bubbles after the middle of the polymerization period causes the scales to adhere to the inner wall of the polymerization tank. The scales will hinder the heat removal of the polymerization reaction, and the productivity will be lowered. Further, the scales peeled off from the inner wall of the polymerization tank will be mixed. In the vinyl chloride resin product, it is a cause of the fisheye at the time of molding, and it is not preferable. If the amount is too large, the polymerization will become unstable depending on the conditions of the suspension polymerization. In the case where the quality of the coarse particles or the plasticizer absorbability of vinyl chloride is lowered, it is not preferable. Further, the means for introducing the 1,2-diol component into the pVA-based resin may be 312XP/invention specification (supplement)/ 95-11/95128120 20 200808837 〇 For example (4) The silk yarn combination, and the like, the combination of the side = increase, Moer 7 or more, there is a limit in the mouth into the mouth, it is impossible to import 3

The St m-based resin is subjected to the above method, and the content of the U-diol component can be arbitrarily controlled within the above range. In addition, the lanthanide resin used in the present invention may be a mixture with a different PVA-based resin as the child-v rn^ - ^ 1 〇心日]ha 糸树月曰, which may be bis, 2-diol In the case where the structural unit content is different, the J degree is different, the degree of polymerization is different, and the other copolymerization components are different, the m-based resin of the present invention is preferably a molecule=system resin. The PVA-based resin having a plurality of groups in the related molecule is not particularly limited, and examples thereof include a method of oxidizing a state enamel resin obtained by the above method with an oxidizing agent such as hydrogen peroxide; and containing M in acid or drying. a method in which the above-mentioned polymerization is carried out in the coexistence of a chain transfer agent, followed by a method of saponification; a method in which the above polymerization is carried out in the coexistence of methoxyacetic acid ethylene, and the saponification is carried out; A method in which saponification is carried out after obtaining a polyvinyl acetate in the air. Industrially, it is particularly advantageous to carry out polymerization by coexisting a carbonyl group-containing chain transfer agent such as an aldehyde or a ketone, and saponifying the obtained polyvinyl acetate to obtain a carbonyl group-containing PVA oxime resin. The chain transfer agent may, for example, be an aldehyde such as acetaldehyde, propionaldehyde, n-butyraldehyde, benzaldehyde or crotonaldehyde; or a ketone such as acetone, mercaptoethyl ketone, hexanone or cyclohexanone. Among these, in terms of the ease of shifting the vinyl acetate carbonyl compound control chain to 312XP/invention specification (supplement)/95-11/95128120 21 200808837, acetaldehyde, benzaldehyde, propionaldehyde, positive The bond transfer agent may be used alone or in combination of two or more. - Preferably, the amount of the chain transfer agent to be added may be adjusted depending on the degree of polymerization of the added chain transfer agent and the target PVA resin, and the fatty acid ethyl ester monomer such as the acid s Good for "5 mesh ^ vinegar%, better " ~ 3 wt%. Further, the chain transfer agent can be packed in a poly-weight, or can be charged in the middle of polymerization. The molecular weight distribution of the PVA resin can be controlled by filling the following: The chain amount of the PVA-based resin of the present invention is better than that of the U-mail. The UH.2 mole % 'Special 〇·〇3~〇. If the content of such a base is too small, it is used as a dispersing agent. The protective colloidal force is lowered. Right f: If a few bases are introduced in excess, the ground of the resin is lowered, which is not preferable. The mouth will be extremely erect and the amount of covalent double bonds generated by the dehydration/deacetation of the early position of the ethyl ethoxylate and the succinic acid adjacent to such a group is controlled to be used as a suspension. The protective colloidal force in the case of a stabilizer for polymerization is generally used as a standard for the use of a PVA-based resin. The composition of the absorption spectrum of 215 nm [the structure belonging to -C0_CH=CH_] The two liquids: Bu: the structure of -co-(ch=ch)2-, and the absorbance of 320 nm [made of nm], and in the present invention, the absorbance of the resin is preferably 0. or more, more preferably _ above luminosity. When the amount is too low, the polymerization stability during suspension polymerization is insufficient, and coarse particles are formed or the particle size distribution is increased, which is not preferable. Further, in the production of the PVA-based resin of the present invention, in the presence of a solvent having a dielectric constant of 32 or less, in the polyvinyl acetate vinegar 312XP/invention specification (supplement)/95-11/95128120 22 200808837. The better dielectric constant is 6, and the dielectric constant is excellent. When the dielectric constant exceeds 32 ′, the acidity of the residual acetic acid group in the PVA-based resin is lowered, and the protective colloidal force which is the stabilizer for the polymerization of the ethylene-based resin (4) is not sufficient. It is not preferable that the coarse particles of the gas-containing fine resin are refined or the particle size distribution is increased. The solvent having a dielectric constant of 32 or less may, for example, be methanol (31 2), western: acid methyl vinegar / methyl (tetra) / 3 m"), acetic acid brewing / methanol = 1 / 1 (21 G), (iv) (methylene glycol: 3/1!13.9), methyl acetate (7.03), isopropyl acetate, "Wing (3.42), xylene (2.37), toluene (2.38), Ben (: (8), acetone (2).4), etc. In the case of the above, it is preferred to use a mixed solution of methyl acetonate/methyl intoxication. Next, a method for suspending polymerization of an ethylene-based compound having the gas stabilizer of the present invention will be described by taking a vinyl chloride monomer as an example. 'A gas-ethylene system is a suspension system in which a dispersion stabilizer of the present invention is used in addition to a gas oxime system alone, and a mixture of 50% by weight or more and other monomers obtained by the copolymerization. The method is also any method used in the general suspension polymerization of the ethylenic monomer. In the suspension, the polymerization system is added to the method of dispersing the stabilized PVA resin of the present invention, and the PVA resin can be directly used as a powder or a liquid. It is added once in the initial stage of polymerization, or added in the middle of the polymerization. '=The amount of dispersant used is not special. The system is usually 100 parts by weight, preferably 5 parts by weight or less, more preferably 〇 312XP / invention specification (supplement) / 95 7 / 9512812 〇 23 200808837 parts by weight, more preferably 0. 02~0 2 parts by weight. In the suspension polymerization, the dispersion stabilizer of the present invention may be used in combination with various known dispersing assistants. As the dispersing aid, it is suitable to use a low saponification degree of saponification degree of less than 65 mol% and an average degree of polymerization of 100 to 750. The PVA-based resin is particularly preferably a low-saponification PVA-based resin having a degree of saponification of 30 to 60 mol% and an average degree of polymerization of 180 to 900. Further, the dispersing aid is water-soluble or water-dispersible, and may be An ionic group such as a carboxylic acid or a sulfonic acid is introduced into a side lock or a terminal of a PV A resin having a low degree of tempering to impart a self-emulsifiable dispersing aid. Specifically, for example, "GOHSEFIMER LL-02" , "GOHSEFIMER L-5407", "GOHSEFIMER L-7514", "GOHSEFIMER LW100", "GOHSEFIMER LW200", "GOHSEFIMER LW300", "GOHSEFIMER LS210", etc. (dispersed by the Synthetic Chemical Industry Co., Ltd.) And "LM-20", "LM-2 5", "LM-10HD" (KURARAY company), "Alcotex 55-002H", "Alcotex-WD100", "Alcotex WD200", "Alcotex 55-002P" (made by SYNTHOMER), "Sigma404W", "Sigma202" (Manufactured by Sigma), various dispersing additives manufactured by CIRS. The weight ratio of the PVA-based dispersion stabilizer to the amount of the dispersing aid added in the present invention cannot be generalized by the type of the dispersing agent, etc., but it is preferably in the range of 90/10 to 30/70, and 80/20 to 50. /50 is especially good. By using a dispersing aid in combination, it is possible to prevent the formation of a thick skin layer on the surface of the obtained vinyl chloride resin particles, and to control the inside of the particles by 1 to 312 XP / invention specification (supplement) / 95-11/95128120 24 200808837 = etc. = agglutination of the basic (_cut), = B = (4) porosity (sity) distribution (four) = physical properties such as sex, pre-early body, etc. (4) and received as a suspension polymerization catalyst, if it is oil soluble = use = peroxide, wake up, peroxide, laurel: over = propylene: ― 2 "曰, ..., - azobisisoisobutyronitrile, ... ,-Azo: Mixed character one J base: valeronitrile? A cyclylcyclohexylperoxysulfonyl group or the like used in the general suspension polymerization of a vinyl monomer. The catalyst may be used singly or in combination of two or more. Further, the dispersion stabilizer of the present invention may be used in combination with other known dispersion squeegees, for example, a polymer material which is a dispersion stabilizer for suspension polymerization of a vinyl compound. The m-type resin other than the PVA-based resin of the present invention, such as an PVA-based resin having an average polymerization degree of 100 to 4,500, and a saponification degree of 65 to 1% by mol%, or a derivative thereof, may be exemplified. The derivative of the PVA-based resin may, for example, be a furfural of pvA, an acetal, a butyralate, an ethyl decanoate, an esterified product with a sulfonic acid or a carboxylic acid, or the like. Further, for example, a copolymer saponified product of a vinyl ester and a dimer copolymerizable therewith may be mentioned, and examples of the copolymerizable monomer include ethylene, propylene, isobutylene, a-octene, a dodecene, and a ten. An olefin such as octaene; an unsaturated acid such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, maleic anhydride or itaconic acid or a salt thereof or a mono- or dialkyl hydrazine a nitrile such as acrylonitrile or methacrylonitrile; an amide such as acrylamide or mercapto acrylamide; an ethyl ester of tarnish, an allyl methacrylate, and a methyl propylene vinegar Sulfonic acid olefins or salts thereof; alkyl vinyl ethers, ethylene_, 12XP/invention specification (supplement)/95-11/95128120 25 200808837 N-vinylpyrrolidone, vinyl chloride, vinylidene chloride and the like. However, the PVA dispersion stabilizer is not limited thereto. In addition, examples of the polymer material other than the PVA-based resin known as a dispersant include methyl cellulose, ethyl cellulose, hydroxymethyl cellulose, hydroxypropyl methyl cellulose, and hydroxybutyl methyl group. Cellulose, hydroxyethyl cellulose, m methyl cellulose, amine methyl propyl cellulose, amine ethyl propyl cellulose and other cellulose derivatives; starch, tragacanth, pectin, glue (glue), alginic acid or its salt, gelatin, polyvinylpyrrolidone, polyacrylic acid or its salt, polymethacrylic acid or its salt, polyacrylamide, polymethacrylamide, vinyl acetate and maleic acid a copolymer of an unsaturated acid such as an acid, a maleic anhydride, a dibasic acid, a methacrylic acid, an itaconic acid, a crotonic acid or a crotonic acid; a copolymer of styrene and the above unsaturated acid; The copolymer of the above unsaturated acid and the salt or the like of the above-mentioned copolymer: In the suspension polymerization, various surfactants, inorganic dispersants, and the like may be used in combination as an auxiliary. Further, in the case where the degree of saponification is not less than 65 mol%, the PVA-based resin of the present invention can also be used as an auxiliary. Further, in the suspension polymerization, a chain transfer agent used in a conventional suspension polymerization of a vinyl chloride monomer can be, for example, a county: carbonized or the like. The temperature of the aqueous medium used for the suspension polymerization of the ethylene-based monomer is not particularly limited. It is also possible to use hot water of about 97 C based on normal temperature water of about (10), but in order to shorten the temperature rise time during polymerization, Preferably, the method of using preheated water instead of normal temperature water during the polymerization (heat feed method 'h〇tcharge) is preferred, and in the case of adopting the method, the 312XP/invention specification (supplement)/95·11 /9512812() 200808837 The water is preheated to 40 to 97 ° C, preferably 4 to 85 ° C. The polymerization temperature in the suspension polymerization can be arbitrarily selected in accordance with the degree of polymerization of the intended ethylene-based resin within a range known to the practitioner, and is usually preferably 3 Torr to 8 Torr C. The suspension polymerization is carried out in a range in which the weight ratio of the monomer to water is generally 0.5 to 1.2, but it is also possible to carry out the chasing of water during the polymerization to compensate for the liquid level reduction caused by the volume shrinkage accompanying the polymerization. It is preferred because it inhibits the formation of fish eyes. Further, the polymerization pressure at the time of the suspension polymerization can be arbitrarily selected by the degree of polymerization of the ethylene-based resin and the polymerization temperature in the range known to the practitioner. (4) in the case of suspension polymerization is not particularly special, and a known stirring device generally used in the suspension polymerization method of a conventional vinyl chloride monomer can be used to feed the wings, and the Federer wing, the gather wing, the turbine wing, and the blade can be used. Turbine wings, turbine wings and the like are widely used, especially Federer wings are preferred. The combination of the & and the choke is not particularly limited, and examples of the choke include a type, a type D, a tube type, and a finger type. In the suspension polymerization of the sulphate monomer, it is not only the individual chloroethene, but also the copolymerization with the copolymerizable monomer. The copolymerizable single limb can be "listed as ethylene, vinyl ether, vinyl acetate, benzoic acid vinegar, propylene, methyl propyl ketone and its ester, maleic acid or its anhydride, ethylene , propylene, styrene, etc. —

In addition, in the suspension polymerization of a vinyl chloride monomer, a polymerization regulator which is suitably used, a chemical modification agent, and the like may be arbitrarily used. f 4 312 Χ ρ / 发明 发明 发明 发明 发明 发明#, particle size distribution, plasticizer absorption, etc.) are not affected by the temperature of the hot water in the polymerization, and a vinyl chloride resin having excellent characteristics is obtained. In the above, the suspension polymerization of the dispersion stabilizer using the PVA resin of the present invention is mainly described, and the polymerization of the vinyl chloride monomer is described. However, the pvA system stabilizer of the present invention is not necessarily limited to the vinyl chloride monomer. For use, it may be used in an aromatic vinyl compound such as styrene, a vinyl acrylate or a derivative thereof, a vinyl ester compound such as vinyl acetate, or an ethylene compound such as ethylene-vinyl acetate or the like. For suspension polymerization. Further, the dispersion stabilizer for suspension polymerization of the present invention can be used as a dispersion stabilizer in fine suspension polymerization, and in this case, a foaming inhibiting effect can be obtained in the same manner. The monomer to be used in the fine suspension polymerization is not particularly limited as long as it is an ethylenic compound, and examples thereof include a toothed vinylated product such as vinyl chloride, an aromatic vinyl compound such as styrene, vinyl acetate, and ethylene. A vinyl ester compound such as monovinyl acetate or a polymer thereof, acrylic acid, methacrylic acid, and derivatives thereof. (Examples) Hereinafter, the present invention will be described by way of examples, but it is not limited to the description of the examples. In addition, the "parts" and "%" in the examples are not specifically limited and refer to the weight basis. (Example 1) In a reaction tank equipped with a reflux condenser, a dropping funnel, and a stirrer, 312XP/Invention Manual (Supplement)/95-11/95128120 28 200808837 Filled with vinyl acetate l〇〇〇g 'Methanol 100g 3, private diethoxy methoxy- 1 monobutene 80g (4 mole%), acetaldehyde 58g, and put azobisisobutyronitrile 〇〇5 mol% (relative to the filling of vinyl acetate), The polymerization was started by raising the temperature under a nitrogen stream while stirring. When the polymerization rate of vinyl acetate is 90.5%, a certain amount of m-dinitrobenzene is added to complete the polymerization, and the unreacted vinyl acetate monomer is removed by the method of P human methanol vapor. Outside the system, a methanol solution of the copolymer was obtained. Next, the solution was diluted with methanol (dielectric coefficient 31·2) and methyl acetate (dielectric coefficient 7.03) to adjust the concentration to 45% (the dielectric constant of the saponification solvent 24·0) to the kneading. In the machine, while maintaining the temperature of the solution below C, the 2% methanol solution of sodium hydroxide is based on the structural unit of vinyl acetate in the copolymer and the structure of 3,4-diethyloxy+butene. The total amount of 1 mol, which is 5 mmol, is added: the saponified product is precipitated at the same time as the saponification, and when it is in the form of particles, the 仃 filter is carefully washed with methanol and hot air. Drying in a dryer to obtain a PVA-based resin. Various characteristic values of the obtained resin were obtained by the following methods. The results are shown in Table 1. 10 [Saponification degree] The degree of chemistry of the bit ^ t /VA resin was determined from the amount of alkali consumed for the hydrolysis of the residual ethyl acetate structure. [Average degree of polymerization] The average degree of polymerization of the m_b is determined according to K 6726. [Content of L2-diol structural unit] ^仟12XP/inventive manual lion)/95 seven/95128120 29 200808837 The 1,2-diol structural unit of the PVA-based resin known to be complete in such a resin After saponification, it was calculated by 1 H_NMR measurement. Further, the nmr measurement system was "AVANCE Dpx4" manufactured by BRUKER, Japan. [Carbon content] According to the method of Almolecular Chemistry, Vol. 15, No. 156, and ρ·249 to 254 (the method described in 958), the obtained PVA-based resin was completely saponified, and PVA-based ρ_ 表After the steroid, the absorbance of the aqueous solution was calculated by 4 〇 5 nm. [Absorbance] P· of the PVA resin to be served; [% by weight absorbance at 28 〇 nm, using UV-visible near 分本分光公司The infrared spectrophotometer v-56 〇 was obtained by using a sample container (unit) having a thickness of 1 cm. The following evaluation was performed on the obtained PVA-based resin. <Foamability of aqueous solution> 1% aqueous solution of PVA-based resin 2〇〇ml was placed in a measuring cylinder with a capacity of 1L. After the temperature was adjusted to 40 °C, the diffusion stone was placed in the bottom of the liquid, and the air was ventilated for 2 minutes at 2 L/min to foam. After the ventilation was stopped, the measurement was carried out until The time until the foaming completely disappeared was evaluated as follows. The results are shown in Table 1. ◎ ··· disappeared within 8 minutes. 〇: More than 8 minutes, disappeared within 1 minute. △: more than 10 minutes, It disappeared within 3 minutes. X ·· did not disappear within 30 minutes. <suspension polymerization of gas and unloading> 312XP/invention manual (supplement)/95-11/95128120 30 200808837 In the polymerization tank with a reflux condenser of 2000L, the PVA resin to be charged is filled with 450g, two - Ethylhexyl peroxydicarbonate 26Og of scorpion water 9 〇〇 kg, vinyl chloride monomer 6 〇〇 kg, under stirring, heated in a jacket (jacket) to 57t, the polymerization begins. : The pressure in the polymerization tank started at 7 〇 kg/cm 2 G. When the pressure in the polymerization tank is as low as 6.0 kg/cm 2 G, unreacted monomers are recovered, and the polymer slurry is taken out of the vessel to be dehydrated. The obtained vinyl chloride-based resin was used to evaluate the following characteristics. The results are not shown in Table 2. [Particle size distribution] The obtained vinyl chloride-based resin was used in a JIS standard sieve (jIS). z 8801), the content (% by weight) of the fine particles on the 42 mesh and the fine particles under the 25 mesh. [Scale attached state (state of occurrence of dry bubbles)] Observed the attached state of the scale to the reflux condenser , the dry bubble generation state in the polymerization tank is as follows Evaluation: No adhesion of scales was observed. △: Adhesion of a small amount of scales was observed. X: Adhesion of a large number of scales was observed. [Amount of blister polymer] Gas ethylene resin after particle size distribution measurement 〇kg Using JIS standard sieve (JIS Z 8801), the content of coarse particles on the 48 mesh (= %) 〇 [body specific gravity] 312xp / invention specification (supplement) / 95-11/95128120 31 200808837 according to JIS K 6 7 21 Determination of the body - "The specific gravity of the ethylene resin of the gas." L color and heat resistance in the early stage] 1 part of the obtained vinyl chloride tree, 35 parts of D〇P (dioctyl phthalate), and epoxidized soybean oil n ^ - 1 / ln〇r, ^ + 1 know, and 钡-zinc stabilizer 2 parts with 140 C for roll mixing 1 〇 min 徭ΰ., ^ After the 'extruder made 0.65mm thick eight _ people' will be 8 pieces of the sheet The layers were superposed and heat-compressed at 18 ° C to form a (four) plate, and the surface of the compression plate was visually observed (4) for coloring, and evaluated as follows. (Initial coloring property) Again, the compression plate is placed still! The presence or absence of coloration (heat resistance) was evaluated in the same manner for 50 minutes in a 9-inch * wheel oven (tear). Ο : No coloring at all. △: Only a little coloration. X · There is coloring. (Example 2) In a reaction tank equipped with a reflux condenser, a dropping funnel, and a stirrer, vinyl acetate 100 g, methanol 100 g, and 3,4-diethyloxy-p-butyl butyl 164 g (8.2 g) were charged. Mol%), Ug acetic acid, and azobisisobutyronitrile 〇〇5 mol% (relative to the loaded ethyl acetate), the temperature was raised while stirring under a nitrogen stream, and polymerization was started. When the polymerization rate of vinyl acetate is 91.5%, a certain amount of m-dinitrobenzene is added to complete the polymerization, and the unreacted vinyl acetate monomer is removed to the crucible by blowing methanol vapor. A mixture of methanol and a methanol solution of the copolymer. Next, 'the solution was diluted with methanol (dielectric coefficient 31 · 2) and acetic acid methyl (dielectric coefficient 7. 03) to adjust the concentration to 45% (saponification solvent dielectric 312XP / invention manual (supplement) /95-11/95128120 32 200808837 t:Under 24, Dt: in the kneading machine, the acetic acid in which the temperature of the solution is maintained at 40: = and 4 alcohol, the total amount of the Ϊ; ΓΓΓ + butylene structure single ^, When the ear becomes 6 moles, the proportion is added to the rod, and (4) when the grain is formed, the compound precipitates. When it becomes a particle, it is carefully washed with the nail and dried in a hot air dryer. π to the resin. The characteristic values of the PVA resin to be obtained by the company are shown in Table 2. The results of the evaluations in the examples are shown in Table 2. The mouth (Example 3) is provided with reflux cooling H, In the reaction tank of the dropping funnel and (4) machine, 1 000 g of vinyl acetate, 1 〇〇 of sterol, and 3 g of 3,4-diethyl methoxy-(ene), 8.6 g of acetaldehyde were added. Add azobisisobutyronitrile 〇〇5 = ear% (relative to the vinyl acetate vinegar loaded), and increase the /JDL degree under nitrogen/grace while stirring, and open Polymerization: When the polymerization rate of vinyl acetate is 1,=〇%, a certain amount of dinitrobenzene is added to complete the polymerization, and the unreacted vinyl acetate monomer is obtained by the method of introducing methanol vapor into the person. The solution was removed to the outside of the system to obtain a methanol solution of the copolymer. Next, the solution was diluted with methanol (dielectric coefficient 31·2) and methyl acetate (dielectric coefficient 7.03) to adjust the concentration to 45% (saponification). The dielectric constant of the solvent is 24·0) and loaded into the kneader to keep the temperature of the solution below 4 〇L, and the 2% methanol solution of sodium hydroxide is relative to the ethyl acetoacetate in the copolymer. The total amount of the structural unit and the 3,4-diethyloxy-1-butane structural unit is 1 1 mol, and the ratio is 5 mmol. 312XP/invention specification (supplement)/95-11/ 95128120 33 200808837 Saponification. When saponification is carried out, the saponified product is precipitated, and when it is in the form of particles, it is filtered, carefully washed with methanol, and dried in a hot air dryer to a PVA-based resin. "In the obtained PVA-based resin The characteristic values are shown in the table and the results of the evaluation. The results are shown in Table 2. ° (Example 4) In a reaction tank equipped with a reflux cooling H, a dropping material, and a (four) machine, a vinyl acetate of 1,000 g, a sterol of 4 〇〇g, and a 3,4 _ Oxygen is a ^ ^ diluted 90g (4.5 mole%), azobisisobutyronitrile 〇〇 8 mole% (phase soil for the ointment of vinyl acetate vinegar), while stirring, under the nitrogen flow to make the temperature rise When polymerization is started, when the polymerization rate of vinyl acetate is 94 7%, the amount of m-Schottylbenzene is added to complete the polymerization, and second, the unreacted vinyl acetate monomer is removed by blowing methanol vapor. To the outside of the system, a methanol solution of the copolymer was obtained. Next, the solution was diluted with methanol (dielectric coefficient 312) and acetic acid acetate coefficient 7. 03), adjusted to a concentration of 45% (the saponification medium has a median coefficient of 24.0) and loaded into a kneader to adjust the solution temperature. Maintained below the °C, the 2%f alcohol of hydrogen (4) is based on the total amount of the vinyl acetate vinegar structural unit and the 3'4-diethyloxy+ butyl structural unit in the copolymer! Mohr was added to a ratio of 5 mmol to be saponified. When the saponification is carried out, the compound is precipitated, and when it is in the form of particles, it is filtered, carefully washed with f-ol and then subjected to a PVA-based resin in a hot air dryer. The property values of the obtained PVA-based resin are shown in Table 2, and the results of the evaluation were as shown in Table 312, 312 XP/Invention Manual (Supplement)/95-11/95128120 34 200808837. (Example 5) In a reaction tank equipped with a reflux cooling crucible, a dropping funnel, and a (four) machine, charged with acetic acid ethyl acetate 1 000 g, methanol 5 〇〇 g, 3, 4-diethoxyoxy q-butene 7 〇 g (3.5 mol %), acetaldehyde 12 · lg, and put azobisisobutyronitrile Q. jf ear % (= for vinyl acetate vinegar filled), while stirring, increase the degree of boiling under nitrogen μ And start to aggregate. The polymerization rate of vinyl acetate is 99^.2/g呤, the addition of a certain amount of dinitrobenzene is added to complete the polymerization, and the unreacted vinyl acetate monomer is obtained by the method of methanol in the presence of methanol. The solution was removed to the outside of the system to obtain a methanol solution of the copolymer. "Secondly, the solution was diluted with methanol (dielectric coefficient 31·2) and methyl acetate (dielectric coefficient 7.03) to adjust the concentration to 5〇% (the dielectric constant of the dielectric solvent 24·〇). Filled into the kneader, keeping the temperature of the solution below, the 2% methanol solution of sodium hydroxide relative to the vinyl acetate vinegar structural unit in the copolymer and the 3, 4 di ethoxycarbonyl + butyl structure The saponification is carried out by adding 1 mole to the ratio of 5 millimoles in the mouth of the t, and saponification is precipitated when saponification is carried out in the saponification of the t, and when it is in the form of particles, it is carefully washed with methanol and dried in a hot air dryer. To PVA resin.

The results of the evaluation of the plots are shown in Table 2. J (Example 6) In the first embodiment, in the saponification of the copolymer, in addition to the oxidized surface/methylate solution, the 312XP/invention specification (supplement) is constructed with respect to the acetic acid in the copolymer. ) / 95-11/95128120 35 200808837 ' j — B & oxy - 1 - the total amount of butene structural units 1 m, :,,: the proportion of the house Moer is added, the rest and implementation... The PVA resin was obtained in the same manner. Suspect! The characteristic value of the PVA-based resin is shown in *1, and the results of evaluation in the same manner as in Example 1 are shown in Table 2. (Example 7) In the case of the saponification of the copolymer in the first embodiment of the present invention, except that the 2% methanol solution of sodium hydroxide was used in relation to the vinyl acetate vinegar structural unit and the 3,4-diethyl oxyhydroxide in the copolymer. The total amount of the structural units of the base butene was changed to a ratio of 4 mmol, and the same procedure as in Example i was carried out to obtain a PVA-based resin. The characteristic values of the PVA-based resin shown in the table are shown in Table 2. The results of evaluation in the same manner as in Example i are shown in Table 2. (Example 8) In a reaction tank equipped with a refluxing cold*, a dropping funnel, and a mixer, 12 〇〇g of vinyl acetate vinegar, 6 〇g of methanol, and 117 g of glycerol monoallyl ether (6. And the azobisisobutyronitrile 〇1 mol% (relative to the vinyl acetate charged) was stirred while stirring under a nitrogen stream to raise the temperature, and the polymerization was started. The polymerization rate of vinyl acetate was 74 2%. At the same time, a predetermined amount of m-dinitrobenzene is added to complete the polymerization, and secondly, the unreacted vinyl acetate monomer is removed to the outside of the system by blowing methanol vapor to obtain a sterol solution of the copolymer. The solution was diluted with methanol (dielectric coefficient 31·2) to adjust the concentration to 50% (the dielectric constant of the saponification solvent was 3ΐ·2) and charged to the kneaded 312XP/invention specification (supplement)/95·11 /95128120 200808837 (4) The temperature of the solution is kept below the enthalpy, and the total amount of the oxidized sodium hydride solution is determined by the unit of the ethyl acetate in the copolymer and the unit of the = 2 ethyl group = τ (4). The ear and the object It are added by the addition. When the interest is made, it is saponified: In the case of the particles, the mixture was filtered, and washed with methanol in a hot air dryer to obtain a PVA resin. The characteristic values of the PVA resin are shown in Table i, and in the example β I. The results of the evaluation are shown in Table 2. (Example 9) In a reaction tank equipped with a reflux condenser, a dropping funnel, and a mixer, 1 000 g of ethylene sulphuric acid vinegar, 450 g of methanol, and ethylene carbonate The purpose is to use Um. aldehyde 3.3g 'and put azobisisobutyronitrile 〇·05,,,,,,,,,,,,,,,,,,,,,,,,,,,,,, 'Starting polymerization. When the polymerization rate of vinyl acetate is: j.8%, the addition of a certain amount of m-dinitrobenzene is added to complete the polymerization, and the unreacted method is adopted by the method of human gastroenterology. The acetic acid ethyl vinegar was removed to the outside of the system to obtain a methanol solution of the copolymer. Next, the solution was diluted with methanol (dielectric coefficient 312) and acetic acid electric coefficient 7. 03), and adjusted to a concentration of 45%. The median coefficient of the solvent is 24. 0) sub-loaded into the kneader, keeping the solution temperature below C, A The 2% methanol solution of sodium is based on the ethyl acetate structural unit of the copolymer and the δ10-mole of the 3, 4-diethyloxy+ butyl structure, which is 7 mm. The saponification is carried out by adding it. When saponification is carried out, the saponified product is precipitated, and when it is in the form of granules, it is filtered, washed with methanol and dried by hot air in the form of 312 ΧΡ / invention specification (supplement) / 95 7 / 95 ΐ 28 ΐ 2 〇 ^ 200808837 The PVA-based resin was obtained by drying in a machine. The characteristic values of the obtained PVA-based resin are shown in Table, and the results of evaluation in the same manner as in the examples are shown in Table 2. (Example 10) In a reaction tank equipped with a reflux condenser, a dropping funnel, and a stirrer, 1200 g of vinyl acetate, 6 〇g of sterol, and 2,2-didecylvinyl-1,3-dioxane were charged. The alkane was 98 g (5 5 mol%), and azobisisobutyronitrile (1 mol%) was added (with respect to the charged vinyl acetate), and the temperature was raised under a nitrogen gas while stirring to start polymerization. When the polymerization f of vinyl acetate is 70%, 'the addition of a certain amount of m-dinitrobenzene is completed to complete the polymerization, and secondly, the unreacted vinyl acetate monomer is removed outside the system by blowing in the sterol vapor. And a methanol solution of the copolymer was obtained. Next, the solution was diluted with methanol (dielectric coefficient 31.2), and adjusted to a value of 5 (U (saponification solvent dielectric constant 31. Magic and loaded to pinch two = two to keep the solution temperature at 4) Under the generation, 'the two kinds of bismuth oxides are combined, and the liquid phase is combined with each other. The vinyl acetate vinegar structural unit in the copolymer is added to the ratio of a few ears of 1 to 4 house moles, and is forgotten. The precipitate was precipitated, and the ruthenium was in the form of particles. The hydrochloric acid (water/methanol = 1/1 mixed solvent) in which the saponified product was dispersed was subjected to _ sample ====:: shown in Table 1 and Example 312XP / 曰月月手册(补件)/95-11/95128120 38 200808837 (Comparative Example 1) In Example 1, in it _ human μ. In the saponification of /, 1 combination, in addition to sodium hydroxide / f ☆ The liquid is added in the same manner as in the first embodiment except that the liquid is added to the total amount of the monoethyl methoxy group and the butene structural unit of the vinyl acetate structure in the copolymer. PVA-based resin = The characteristic value of the PVA-based resin is shown in Table 1, and the results of evaluation in the examples are shown in Table 2. (Comparative Example 2) In J2 In the specialization of the copolymer, in addition to the total amount of vinyl oxyhydroxide in the copolymer, the total amount of vinyl acetate = 3, 4 = ethoxylated + butyl structural unit in the copolymer, The PVA-based resin was obtained in the same manner as in Example 1 except that the ratio of the molars was added. The characteristic values of the PVA-based resin are shown in Table 1, and the results were evaluated in the same manner as in Example 1. Table 2. (Comparative Example 3) In a reaction tank equipped with a reflux cooler, a dropping funnel, and a scrambling machine, filled:: Ethyl acetate, 160 g of methanol, B..., and put into the even nitrile G. G4 mol% (Compared to the charged acetic acid vinegar), the polymerization is started while the temperature is raised under the nitrogen flow, and when the polymerization rate of the acetic acid is 96.3%, the predetermined (tetra) dinitron beam is added, and secondly, by The method of blowing methanol vapor removes the unreacted acetoacetate monomer to the outside of the system, and (4) the alcoholic solution of the copolymer. 31" month specification (supplement) / 95-11/9512812 〇 39 200808837 Diqi-human, the solution is methanol (dielectric coefficient 31· and methyl acetate (dielectric coefficient 7·) 03) Diluted into a sputum, adjusted to a concentration of 45% (the dielectric constant of the catalyst) (24% 喜) sub-packaged into the kneader, the solution temperature is maintained below μ C, the bismuth emulsified sodium 2% methanol solution According to the structural unit of vinyl acetate vinegar, it is added by adding it. The cardia 1 is 5 when the ratio of the ear is sub-formed, and the compound is precipitated as a grain nr &lt; After carefully washing and drying in a hot air dryer, a pva-based resin was obtained. The characteristic values of the PVA-based resin obtained in the singularity of the money are shown in Table 1, and the results of the evaluation were shown in Table 2. /, only ❿ 1 with 312 ΧΡ / invention manual (supplement) / 95-11/95128120 40 200808837 ± 1, 顼龠 "±1 绂 ^ (% ton 祧) (% ton 婶) (% ton 饨)絮¥杷♦砩譃驷杷衅? Ϊ 谥 谥 U-CV3 制 铋 ^ ◎ ◎ 〇〇〇 〇 〇 〇〇〇 〇〇〇 &lt;&gt;&lt; 900 so 00 &lt; XI Bu 0 0060 682 0000 991 zs 9000

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LOCOCOeQLO — — COO LOLOLOLOLOLOLOLjOLOLO

Inch LOCD 卜 OC^CDOOCDO Cl^ 【—】t—h L〇l 3 h C3 t—^ i—HVV 〇〇〇〇〇V 〇〇οοο zo 10 10zo inch 0εο 0000 ΙΜ m 600 061 ii inch 00ο 01¥资和6苳碧驷oof香碧驷卜蓁驷9苳碧驷9苳餐驷〇0蓁海驷I 驷雀驷XXXx&lt;x CO CO oo LO ^ ^

XXX OCXDoe oco 006 ii (Ν οποοπ s/u/6/ffsi)_Kfi§ss/dtxz:le 200808837 (Example 11) Packed with vinyl acetate in a reaction tank equipped with a reflux cooler, a dropping funnel, and a (4) machine L200g, methanol 6〇g, 3,4_2B = Moxuan, E money lg, and cast azo double is ^ = == filled with acetic acid B (four), while mixing the side in the nitrogen flow / dish and ^ F ^fl ^ ^ ^ ^ II,6 ^ 嶋 ' 'Addition of a quantitative amount of disulfobenzene to complete the polymerization, 2 to remove unreacted ethyl acetate vinegar monomer by the method of σ human into T private gas Outside the system, a methanol solution of the copolymer was obtained. Next, 'the solution is diluted with methanol (dielectric pure 312) and methyl acetate (diluted by medium = 7. (9) to adjust the dielectric = ratio of the concentration of the solvent to 2) and loaded into the kneader. Keep the temperature of the solution below 4 ° C, and the 2% f alcohol solution of the steel hydroxide is based on the relative structural unit and 3, 4 - diethoxylated to dilute structure. When the ratio is added, the saponification of the saponification is carried out, and when the granules are precipitated, when they are in the form of granules, the granules are carefully washed and dried in a hot air to obtain a PVA-based resin. The characteristic values of the PVA-based resin obtained from the retreat islands are shown in Table 3, and the m-type resin was used to carry out the fine kneading of the acetic acid as follows, and the foaming state at this time was evaluated. In a 5 〇〇mL glass separation flask, 9 parts of pv 5.9 parts of ion-exchanged water ι25 and 74.5 parts of lyophilized vinyl ester of eucalyptus were dissolved in a homogeneous laurel. Homogenetic mixing to become 312XP / invention manual (supplement) / 95-11/95128120 43 200808837 After a slight suspension state, a reflux condenser and a scrambler were installed on the separation flask, and the temperature was raised to 70 ° C under stirring to cause polymerization. Start. The foaming state after the end of the temperature rise was visually observed, and as a result, the foaming occurred only at the gas-liquid interface. (Comparative Example 4) In a reaction tank equipped with a reflux condenser, a dropping funnel, and a stirrer, 12 g of vinyl acetate, 60 g of decyl alcohol, and 18 g of acetaldehyde were charged, and azobisisobutyronitrile was introduced. 005 mol% (relative to the charged vinyl acetate), the temperature was raised under a nitrogen stream while stirring, and polymerization was started. When the polymerization rate of vinyl acetate is 79.5%, a certain amount of m-dinitrobenzene is added to complete the polymerization, and secondly, the unreacted vinyl acetate monomer is removed to the system by blowing methanol vapor. Further, a sterol solution of the copolymer was obtained. The human-diluted solution was diluted with methanol (dielectric coefficient 31 · 2 ) and methyl acetate (dielectric coefficient 7. 03) to adjust the concentration to 45% (the saponification solvent has a dielectric constant of 2 2 · 2 ) and Filled into the kneader, keeping the temperature of the solution below 4 〇t, and the 2% decyl alcohol solution of sodium hydroxide becomes 6 millimolar relative to the vinyl acetate structural unit in the copolymer. The ratio was added to 1 for saponification. The saponified product was precipitated in a granulated form, filtered, washed with methanol and dried in a hot air dryer to obtain a PVA-based resin. The characteristic values of the obtained PVA-based resin are shown in Table 3. In the same manner as in Example n, the fine suspension polymerization of vinyl acetate was carried out in the same manner as in Example n, and the evaluation was carried out in the same manner. As a result, it was foamed to the uppermost portion of the separation flask. 312#/__书(补件)/95-11/95128120 44 200808837 (Table 3)

While the invention has been described with reference to the preferred embodiments of the present invention, it is understood that various changes and modifications can be made without departing from the spirit and scope of the invention. This application is a Japanese patent application (Japanese Patent Application No. 2006-02521 9) filed on Feb. 2, 2005, filed on Feb. 2, 2005, to the present patent application (Japanese Patent Application No. 2〇05-026793), filed on Feb. 2, 2006. Its content is used for reference. (Industrial Applicability) The dispersion stabilizer for suspension polymerization of the vinyl compound of the present invention is excellent in dispersion stability during suspension polymerization of vinyl chloride, so that vinyl chloride having a narrow particle size distribution and high bulk density can be obtained. Since the polymer particles have a low foaming property, the amount of wet foam during polymerization is small, and the amount of dry foam is also reduced. Therefore, the occurrence of polymer scales and blister polymers which are causes of fish eyes can be suppressed. Further, it is industrially very useful because it can produce vinyl chloride polymer particles having less coloring and excellent heat resistance. 312ΧΡ/Invention Manual (supplement)/95-11/95128120 45

Claims (1)

200808837 X. Patent application scope: 1. Dispersion polymerization (4) for suspension polymerization of an ethylene compound, characterized in that it contains a bismuth, 2-diol component in the side chain, and the degree of saponification is 65 to 87 mol%. It is composed of a polyvinyl alcohol resin. 2. A dispersion stabilizer for suspension polymerization of a B-based compound according to the scope of the patent application, wherein the polyvinyl alcohol-based resin contains a 1,2-diol structural unit of the general formula; 1) R——c ''L R. X 4R—C-IOH - Η C——ο R6 [wherein, R1, R2 and R3 each independently represent a hydrogen atom or an organic group, and χ represents a single bond or bond. The chain, R4, R5 and R6 each independently represent a hydrogen atom or an organic group]. 3. A dispersion stabilizer for suspension polymerization of a vinyl compound according to claim 1 or 2, wherein the polyvinyl alcohol resin is ethylene. A saponification of an ester monomer and a copolymer of a compound represented by the general formula (2); (Chemical 2) R\c=c R4 R&quot; C —— C——R 0R/ 0R° 312XP/Invention Manual ( Supplement)/95-11/95128120 46 (2) X 200808837 H 中^ β μ R and R3 each independently represent hydrogen or an organic group, and x represents a single bond R8, and R, ^ and V independently represent a hydrogen atom or an organic group. Base, 4 4 : I independently represents a hydrogen atom or R9—(3)—(wherein, R9 is an alkyl group)]. Divided into two = Li: the suspension of the third wide ethylene compound in the middle circumference The polymerized acid oxy group + butyl group, the compound represented by the formula (2) is a suspension of the vinyl compound of the first or second item of the 3, 4-difluorene range, and i ^' The 'polyvinyl alcohol-based resin is obtained by saponifying a copolymer of ethylene vinegar mono-I, early, and propyl. VIII: Use: suspension of polyethylated compound of the first or second range of 5 Female sputum, pot Φ, take / body and - general (3); chemistry::: every 糸 resin is a vinyl ester series ^ ... · mouth of the &quot;, the polymer is saponified and decarbonated付, R4 R5 (化3) r1\ /R3 (3) c = c r2/ c-R6 AC II o [wherein, R, R2 and r3 respectively 猸 ☆ 〆 〆 、 、 J J 、 、 、 The organic group, X represents a soap bond or a bond chain, R4, V and r6 a ^ Ί knife independently of the atom or organic storm "0 7 · as claimed in the scope of the sixth paragraph ^ 4 with a dispersion stabilizer, Among them, the suspension compound of the general compound is carbonated with ethylene glycol. The compound represented by the general formula (3) is ethylene 312XP/invention specification (supplement)/95-11/95128120 200808837 into 8.::: patent The saponification and deketalization of the vinyl ester monomer f of the general formula (4) is carried out by using a knife-based stabilizer for the suspension of the vinyl compound of the first or second term, and a polyvinyl alcohol-based resin. Yes, (4) R2〆 (4) R1〆 11 ^, R and R3 each independently represent a ruthenium atom or an organic group, X represents a single bond/go bond | a chain, and R4, R5 and R6 each independently represent a hydrogen atom or an organic group, and R and R11 independently represent a hydrogen atom or Organic base]. 9. The dispersion stabilizer for suspension polymerization of a vinyl compound according to item 8 of the patent application, wherein the compound represented by the general formula (4) is 2,2-dialkyl-4-vinyl- ι,3- Dioxolane. I 〇····················································································· Adult. II. A dispersion stabilizer for the suspension polymerization of a vinyl compound according to the second or second aspect of the patent application, wherein the polyvinyl alcohol-based resin is one in which a carbonyl group is contained in the molecule. 12. The dispersion stabilizer for suspension polymerization of a vinyl compound according to claim 1 or 2, wherein the degree of saponification of the polyvinyl alcohol resin is 312XP / invention specification (supplement) / 95-11/95128120 200808837 68 ~83 moles / 〇. 13. The dispersion stabilizer for suspension polymerization of a vinyl compound according to claim 1 or 2, wherein the polyethylene resin is 400 to 850. The degree of the mouth, 14. The suspension of the vinyl compound of the first or second patent range, the dispersion stabilizer for polymerization, wherein the content of the U-diol component in the polyvinyl alcohol resin is 1~ 8 moles %. 312XP/Inventive Manual (Replenishment)/95-11/95128120 49 200808837 VII. Designation of representative drawings: (1) The representative representative of the case is: No (2) Simple description of the symbol of the representative figure: No. 8. If there is any In the chemical formula, please reveal the chemical formula that best shows the characteristics of the invention: (Chemical 1) R - CR - c - X 4 ΓΟΗ cIOH 312XP / invention manual (supplement) / 95-11/95128120 4