JP2009120761A - Manufacturing method of functional vinyl halide polymer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a manufacturing method of a functional vinyl halide polymer resin, that is, a vinyl halide polymer which is excellent in workability, gel lubrication and transparency without using no processing adjuvant. <P>SOLUTION: The manufacturing method of a functional vinyl halide polymer includes adding various kinds of alkyl acrylic acid esters alone or the polymer emulsion or the dried product of various kinds of the alkyl acrylic acid esters or the acrylic acid esters to a vinyl halide alone or various kinds of mixtures containing mainly the vinyl halide at a ratio of about 10-0.1 wt.% to 90-99.9 wt.% relative to the total weight, and then subjecting the resultant mixture to copolymerization or graft reaction, to produce the vinyl halide polymer. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

The present invention relates to a functional vinyl halide polymer resin, and more specifically, a functional vinyl having excellent processability and excellent gelation slipperiness and high meltability without adding a processing aid. The present invention relates to a halide polymer and a method for producing the same.

For the past several years, the processing technology of polyvinyl chloride polymer resin (abbreviated PVC) has evolved day by day, and high transparency and mechanical properties are required for the quality of processed products. In order to make this polyvinyl chloride resin even better, the resin must be made into a good gel, which is the main goal and problem pursued by contractors. The modified polyvinyl chloride resin powder basically improves the gelation characteristics, thereby determining the quality of the processed product. That is, polyvinyl chloride resin powder having better processing characteristics is evaluated as having high value.

Polyvinyl chloride resin has excellent physicochemical properties, but as a potential drawback it has poor processing properties and requires high temperatures. This high processing temperature is close to the cracking temperature, which can lead to product degradation, limits the scope of application, and modern PVC processors can be accommodated over a wide range of hard or soft materials. Processing aids have been added to polyvinyl chloride resin to improve the gelling properties and overcome the processing degradation themes.

  Conventionally, processing aids have always been added to polyvinyl chloride resins for the problem of gelation and processing degradation. Accordingly, an object of the present invention is to provide a method for producing a functional vinyl halide polymer resin having excellent processability, gelation lubricity and transparency without adding a processing aid, that is, a vinyl halide polymer. There is.

  In order to achieve the above-mentioned object, the present inventors have made many years of research and experiment for modification of polyvinyl chloride resin, and various kinds of alkyl group acrylates by aqueous solution method, bulk polymerization method or suspension polymerization method. A vinyl halide polymer resin produced by adding a single polymer or various alkyl acrylate polymers to a vinyl halide alone or various mixed polymerization monomers mainly composed of vinyl halide and subjecting it to grafting or copolymerization is a processing aid. Excellent gelation, lubricity and transparency even without the addition of agent, the processed product has few flow marks and flow errors, and has excellent processing characteristics with high meltability during the processing process. The present inventors have found that it can be applied to various processing of halide polymer resins. For example, processing processes such as roll, extrusion, film blowing, foaming, etc., products are transparent, translucent and opaque soft, semi-soft and semi-rigid and hard products, etc., especially hard transparent products have very good transparency and gloss, This brings about effects such as a low haze value.

  The functional vinyl halide polymer of the present invention comprises (1) various alkyl group acrylate esters alone or various alkyl group acrylate ester / acrylate ester polymer emulsions or about 10 to 0.1 wt% of the total weight. (2) Vinyl produced by copolymerization or graft reaction by adding (2) vinyl halide alone or various mixed polymerization monomers mainly composed of vinyl halide to account for about 90-99.9 wt% of the total weight It is a halide polymer resin or a vinyl halide polymer copolymer resin.

  In the copolymerization or grafting reaction of the present invention, the vinyl halide alone or various mixed monomers mainly composed of vinyl halide may be added in a primary or stepwise manner, the first stage before the polymerization reaction, and the proportion of addition is the total amount The second stage is 50-30 wt% of the total amount with continuous addition. The weight percentage of the various mixed polymerization monomers mainly composed of vinyl halide and the main vinyl halide alone is 55% or more, and various alkyl acrylate esters alone or various alkyl acrylate esters or acrylic acid. The ester polymer emulsion or dried product may be added continuously during the reaction or before the polymerization reaction. The polymer emulsion is added to the polymerization tank before the reaction, or is added until the amount of use is completed continuously from the start of the reaction. Addition of the polymer dried product is performed in the polymerization tank before the reaction.

  Various alkyl group acrylic acid esters used in the polymerization reaction of the present invention are methyl methacrylate (abbreviation MMA), ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, stearyl methacrylate, phenyl methacrylate. , Benzyl methacrylate, and substituents thereof; for example, substituents such as halogen, hydroxy, aralkyl, alkylthio, and miano groups.

  The above-mentioned various alkyl acrylate esters or acrylate polymer emulsions or dried products of the present invention are composed of a single core single layer shell or single core in a graft or core structure or a shell structure. It consists of a multi-layer shell, multi-core single-layer shell and multi-core multi-layer shell, and the emulsion is a core-hard core acrylic acid ester polymer emulsion or dried product of two different structures, depending on the physical properties. Mix in proportions.

An emulsion is a polymer having a core or shell structure, and is produced by aqueous solution polymerization or emulsion polymerization. The polymerization method is batch, semi-batch or continuous.
The emulsion is formed into a dried product by salting out or spray drying. During the polymerization reaction, the copolymerization or graft reaction may be carried out by continuously charging or charging the polymerization tank before the polymerization reaction.

  The weight percentage of the amount of the emulsion added to vinyl halide alone or various mixed polymers mainly composed of vinyl halide is 10 to 0.01 wt%, and 4 to 0.02 wt% is the best. The dry substance is better 10 to 0.1 wt%, 8.0 to 0.2 wt%.

  The above-mentioned powdered body formed by polymerizing the vinyl halide alone or various mixed polymerization monomers mainly composed of the vinyl halide of the present invention is a polyvinyl halide homopolymer and copolymer, for example, polychlorinated It is a vinyl resin or a copolymer of vinyl chloride and other simple substances.

   Among them, the copolymer is mainly composed of 50% or more of vinyl halide alone and copolymerized with other monomers, and the copolymer that can be copolymerized with this is ethylene group alkyl group oxide such as vinyl acetate, vinylidene halide such as vinylidene. Chlorides, alkyl esters of carboxylic acids such as acrylic acid, acrylic esters, 2-ethylhexyl acrylate and the like, and unsaturated hydrocarbon compounds such as acrylic esters.

  When producing the functional vinyl halide polymer of the present invention, the initiator in the course of the polymerization reaction is a water-soluble or oil-soluble organic peroxide. Free radicals are pyrolyzed. For example, hydroperoxides, dialkylperoxides, peroxyketals, diacyl peroxides, peroxyesters, peroxymonocarbonates, peroxydicarbonates, etc., or widely known photodegradation techniques are also used in the polymerization of the present invention.

Dispersants are also widely known and can be used in combination with, for example, polyvinyl alcohol (abbreviated as PVA) having different water solubility and hydroxypropyl methylcellulose (abbreviated as HpMc) having different viscosities.
The functional vinyl halide polymer of the present invention may also be blended with other heat stabilizers, lubricants, colorants, plasticizers, fillers, etc., if necessary.

  That is, in order to achieve the above-mentioned object, the method for producing the functional vinyl halide polymer of the present invention comprises a variety of alkyl group acrylate esters alone or various alkyl group acrylate esters occupying about 10 to 0.1 wt% of the total amount. Or acrylic acid ester polymer emulsion or dried product is added to vinyl halide alone or various mixed objects mainly composed of vinyl halide to occupy 90 to 99.9 wt% of the total amount, and copolymerization or graft reaction is carried out. Forming a vinyl halide polymer.

  Further, it is preferable to produce a vinyl halide polymer by copolymerization or graft reaction of solution method, bulk polymerization method or suspension polymerization method.

  In addition, the main component of vinyl halide is vinyl chloride alone, and various mixed objects mainly composed of vinyl halide are vinyl alkanoate, bilidene halide, alkyl ester of carboxylic acid, or unsaturated hydrocarbon. Thus, the proportion of the main vinyl halide alone is preferably 55% or more.

  Further, it is preferable that the addition of various alkyl group acrylates alone is continuously performed from the beginning of the polymerization reaction until the reaction is completed.

  Also, the addition of various alkyl group acrylate esters or acrylate ester polymer emulsions to the polymerization tank before the reaction or until the addition of the emulsion continuously from the beginning of the polymerization reaction is continued. The addition of the dried polymer product is preferably carried out by introducing the whole into the polymerization tank before starting the reaction.

  In addition, various alkyl group acrylic acid esters include methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, stearyl methacrylate, phenyl methacrylate, and benzil. It is preferably a methacrylate or a substituent thereof.

  In addition, the substituent is preferably a halogeni group, a hydroxy group, an alkoxy group, an alkali dio group, or a Shan group.

  In addition, the proportion of the addition amount of various alkyl group acrylic acid esters or acrylic acid ester polymer emulsions in vinyl halide simple substance or various mixed polymerization simple substances is 4.0 to 0.02 wt%, and acrylic acid ester polymer dried product It is preferable that the amount of addition is 8.0 to 0.2 wt%.

  In addition, vinyl halide alone or various kinds of polymerized monomers mainly composed of vinyl halide are added in one or two stages, the addition before the reaction is the first stage, and the ratio of the added amount to the total amount is 50 to 70%, continuous addition during the reaction is the second stage, and the ratio of the addition amount is preferably 50-30%.

  In addition, various types of alkyl acrylates or acrylate polymer emulsions or dried acrylate polymer polymers may be grafted or core-shell single core single layer shells, single core multilayer shells, It is preferable to consist of a core single layer shell and a multi-core multilayer shell.

  The present invention will be described in detail in the following examples. The examples merely illustrate the features of the present invention and do not limit the technology and scope of the present invention.

Comparative example
After adding 70 kg of deionized water in a 200 liter polymerization tank and 56 g of dispersant polyvinyl alcohol (water solubility 78 mol%), close the lid and hold it for 10 minutes to a vacuum of -740 mmHg. Add 0.7 g of catalyst terbutyl peroxyneodecane (abbreviated as BND) peroxide, stir at a speed of 380 rpm and raise the temperature to 64 ° C. to cause a polymerization reaction, and after 5 hours of reaction, the pressure difference is −1.5 kg or When it becomes cm ² , an anti-peroxidant is added to stop the reaction and unreacted vinyl chloride alone in the polymerization tank is recovered, and the residue is dried to obtain a sample powder for physical property testing.

Example 1
After adding 70 kg of deionized water in a 200 L polymerization tank and 56 g of dispersant PVA (water solubility 78 mol%), close the lid, hold it for 10 minutes to vacuum -740 mmHg, 70 kg of vinyl chloride alone and catalyst Add 0.56 g of BND peroxide and perform the polymerization reaction by raising the temperature to 64 ° C. 90 minutes after the reaction, methylmethacrylate and butyl acrylate (abbreviation BA) simple substance mixture are continuously added in 30 minutes. After the addition, the polymerization reaction is allowed to proceed for 3 hours to obtain a sample powder for physical property testing. The liquid mixture used for continuous charging is a mixture of 140 g of MMA and 28 g of BA.

Example 2
After adding 70 kg of ion-free water, 56 g of dispersant PVA (water solubility 78 mol%), 140 g of MMA alone, 28 g of BA alone in a 200 L polymerization tank, the lid is hardened and held for 10 minutes until the vacuum reaches -740 mmHg. 70 kg of vinyl chloride alone and 0.5 g of catalyst BND peroxide are added, and the temperature is raised to 64 ° C. and a polymerization reaction is carried out for 5 hours to obtain a sample powder for physical property testing.

The sample powder for physical property test obtained in Example 1 and Example 2 of the comparative example was measured by the following physical property test method.

1. The composition of the roll sheet test example is: PVC: 100 parts, organic tin stabilizer: 1.1 parts, lubricant: 0.6 parts, operating temperature: 190 ° C., time: 3 minutes, sheet thickness: 0.3 mm.
The composition of the comparative example was: PVC: 100 parts, organic tin stabilizer: 1.1 parts, processing aid: 1.2 parts, lubricant: 0.6 parts, operating temperature: 190 ° C., time: 3 minutes, sheet thickness: 0.3 mm.

2. Gelation test:
The formulation of the examples is: PVC: 100 parts, organotin tin qualifier: 1.1 parts, lubricant: 0.6 parts, Brabender plastograph: HAAKE BUCHLER SYSTEM 40, set temperature: 140 ° C., rotation speed: 45 rpm.
The composition of the comparative example was: PVC: 100 parts, organic tin stabilizer: 1.1 parts, processing aid: 0.6 parts, Brabender Plastograph: HAAKE BUCHLER SYSTEM 40, set temperature: 140 ° C., rotation speed: 45 rpm.

3. Sheet Flow Mark and Flow Air Test Example formulation is: PVC: 100 parts, organic tin stabilizer: 1.1 parts, lubricant: 0.6 parts, operating temperature: 190 ° C, time: 3 minutes, sheet thickness : 0.3 mm, the flow mark status of the sheet and the amount of flow air were observed.
The composition of the comparative example is: PVC: 100 parts, organic tin stabilizer: 1.1 parts, processing aid: 1.2 parts, lubricant: 0.6 parts, operating temperature: 190 ° C., time: 3 minutes, sheet thickness: 0.3 mm The flow mark and the flow air were observed.

4. Folding sheet transparency and haze (%):
The formulation of the examples is: PVC: 100 parts, organic tin stabilizer: 1.1 parts, lubricant: 0.6 parts, operating temperature: 190 ° C., time: 3 minutes, sheet thickness: 0.3 mm, tatami sheet thickness: 0.5 cm , Integrating sphere spectrometer: HunterLab ColarquestXE.
The formulation of the comparative example is the same as the formulation of the above example, except that 1.2 parts of processing aid is added.

（注2）粒径分布42meshから-200meshの数字は塩化ビニル樹脂がふるい上の重量％で、-200meshの重量％は200meshを通過したのちの重量％総和である。 Table 1

(Note 2) The particle size distribution from 42mesh to -200mesh is the weight percent of vinyl chloride resin on the sieve, and the weight percent of -200mesh is the total weight percent after passing through 200mesh.

  Explanation: It can be seen from Table 1 that the processed physical properties of Example 1 are better than Example 2 and the gelation is clearly faster. Although the best manufacturing method is to continuously add various alkyl group acrylic acid ester mixture liquids during the polymerization reaction, the situation of the reaction tanks of Example 1 and Example 2 is worse than that of the comparative example.

Production of various polymers when various alkyl acrylates or acrylate polymer emulsions or dried products are grafted or copolymerized with vinyl chloride alone to produce a functional polyvinyl chloride resin. Is as follows.

(1) Production of polymer (A):
In a 1L polymerization tank, 720 parts of purified water without ions, 2 parts of potesmuolate, 0.005 parts of ethylenediamine tetraacetic acyl tersolium salt (abbreviated EDTA) and 0.005 parts of ferrous sulfate (FeSO4, 7H ₂ O) The lid is squeezed and held for 10 minutes at a vacuum of -740 mmHg, then returned to 1 kg or cm ² with helium, stirred and warmed to 40 ° C., again 0.25 parts of sodium formaldehydesulfoxy Lat (abbreviated as SFS) was added to the tank, and after 3 minutes, 80 parts of methyl methacrylate, 10 parts of ethyl acrylate, 10 parts of butyl methacrylate and 0.5 parts of cumer hydroperoxide (abbreviated as CHP) were added simultaneously for 1 hour. A core layer emulsion (A) having an average particle size of 128 nm is obtained by reaction.

(2) Production of polymer (B):
In a 1 L polymerization tank, 720 parts of purified water without ion, 2 parts of potesmoorate, 0.055 parts of EDTA, 0.005 parts of ferrous sulfate, 0.25 parts of SFS, 45 parts of butyl acrylate, 55 parts of sterian and 0.5 parts of CHP. In addition, a core layer emulsion (B) having an average particle diameter of 113 nm is obtained by reaction.

(3) Production of polymer (C) Take 20-90 parts of core layer emulsion (A) or (B) as seed emulsion, place in 1 L polymerization tank, 0.01 parts EDTA and 0.01 parts sulfuric acid first. After adding iron, close the lid, hold the vacuum up to -740 mmHg for 10 minutes, return to 1 kg or cm ^{2 with} helium, add 0.35 parts SFS, and after 10 minutes 0.3 parts CHP In addition, 80 parts of MMA, 20 parts of EA and 4 parts of potato oleate are added over 1 hour, and then the reaction is continued for 1 hour to obtain a seed milk (C) having an average particle size of 120 to 140 nm. .

(4) Production of polymer (D):
A seed emulsion is made from 0-100 parts of core layer emulsion (A) and 100-0 parts of core layer emulsion (B) and mixed with different proportional core layer emulsions. The seed milk occupies 20 to 90 parts of the total amount.
Place this seed emulsion in a 1 L polymerization tank, add 0.01 part of EDTA and 0.01 part of ferrous sulfate, close the lid, keep the vacuum up to -740 mmHg, hold for 10 minutes, then helium with 1 kg or cm ² After adding pressure, add 0.35 parts SFS, add 0.3 parts CHP 10 minutes later, inject another 80 parts MMA, 20 parts EA, and 4 parts potassium oleate for 1 hour, then continue For 1 hour to obtain a seed milk (D) having an average particle size of 130 to 150 nm.

  Description: The polymer (A) is a hard core single core emulsion, the polymer (B) is a soft core single core milk, the polymer (C) is a single core double layer emulsion, a polymer ( D) is a double core double layer emulsion. These polymer (A), polymer (B), polymer (C) and polymer (D) can be polymerized by mixing with vinyl chloride alone in proportions different depending on the physical properties.

Example 3
After adding 70 kg of deionized water and PVA (water solubility 78 mol%) dispersant in a 200 L polymerization tank, crush the lid, vacuum up to 740 mmHg, hold for 10 minutes, 70 kg of vinyl chloride and catalyst BND excess Add 0.56g of oxide, raise the temperature to 64 ° C, polymerization reaction, continuously mix polymer (A) and (C) for 2 hours (mixing ratio is as shown in Table 2) in 30 minutes Input 5 times and continue the reaction for 2 hours to obtain sample powder.

Table 2

Table 3

Explanation: From Table 3, it can be seen that the processed physical properties 1 to 5 of Example 3 are better than the comparative example. The copolymerization reaction between the acrylic ester polymer and vinyl chloride alone clearly makes the polyvinyl chloride resin a functional resin. Among them, 4 of Example 3 is the best. This indicates that the addition amount of the polymer (A) and the polymer (C) is appropriate. When comparing 4 and 5 in Example 3, the polymer (C) is greatly added to the flow air of the sheet. I understand that it is a role.

Example 4
After pouring 70 kg of ion-free water, 56 g of PVA (water solubility 78 mol%) dispersant and a mixture of polymer (B) and (D) (mixing ratio is as shown in Table 4) into a 200 L polymerization tank Tighten and hold for 10 minutes until vacuum -740mmHg, add 70kg polycrudeethylene alone and 0.56g of catalyst BND peroxide, raise the temperature to 64 ° C, let the polymerization reaction continue for 5 hours and collect as sample powder To do.

Table 4

Table 5

Explanation: The processed physical properties 1 to 5 of Example 4 in Table 5 are better than the comparative example. As in Example 3, the copolymerization reaction between the acrylate ester polymer and Kudroethylene alone makes polycrudroethylene resin a functional resin. From the processed properties, it can be seen that the polymer (B) is useful for the flow air of the sheet, and the polymer (D) is also useful for the flow mark of the sheet.

Example 5
In a 200 L polymerization tank, add 70 kg of ion-free water, 36 g of PVA (water solubility 78 mol%) dispersant and 35 g of polymer (A), close the lid, hold the vacuum up to -740 mmHg and hold for 10 minutes. In one stage, add Kudroethylene alone and 0.56g of catalyst BND peroxide. The temperature is raised to 64 ° C. and the polymerization reaction is carried out. After the reaction for 30 minutes, as a second stage, Kudrohethylene alone is added and the reaction is continued for 4.5 hours to obtain a sample powder. Table 6 shows the proportion of Kudroethylene alone added to the first stage and the second stage and the weight ratio of the polymerized emulsion.

Table 6

Table 7

  Explanation: From Table 7 to Example 5, Example 5 is a stepwise addition of vinyl chloride, and the processed physical properties of Examples 1 to 5 are better than those of Comparative Example. The polymer emulsion (A) is most useful when the ratio of the simple substance to the second stage vinyl chloride is 3 or 7, and clearly from the processed physical properties.

Example 6
After adding 70 kg of ion-free purified water and 36 g of PVA dispersant (water solubility 78 mol%) in a 200 L polymerization tank, the lid is swamped and held for 10 minutes to -740 mmHg, 70 kg of vinyl chloride alone and peroxide Add 0.56 g of catalyst BND, raise the temperature to 64 ° C. to allow polymerization reaction, react for 60 minutes, then continuously add 140 g of polymer (B) for 30 minutes and react for 4.5 hours to obtain sample powder .

Example 7
After adding 70 kg of ion-free purified water and 36 g of PVA dispersant (water solubility 78 mol%) in a 200 L polymerization tank, the lid is swamped and held for 10 minutes to -740 mmHg, 70 kg of vinyl chloride alone and peroxide 0.56 g of catalyst BND is added, the temperature is raised to 64 ° C. for polymerization reaction, and after reaction for 60 minutes, 140 g of polymer (C) is continuously added for 30 minutes and reacted for 4 hours to obtain a sample powder.

Example 8
After adding 70 kg of ion-free water and 36 g of PVA dispersant (water solubility 78 mol%) in a 200 L polymerization tank, the lid is tightly held and held for 10 minutes to -740 mmHg, 70 kg of vinyl chloride alone and peroxide Add 0.56 g of catalyst BND, raise the temperature to 64 ° C. and allow the polymerization reaction to occur. After reacting for 90 minutes, add 140 g of polymer (D) and 140 g of polymer (A) continuously for 30 minutes and react for 3.5 hours. Sample powder.

Example 9
After adding 70 kg of ion-free purified water, PVA dispersant (water solubility 78 mol%) and polymer (A) dry matter in a 200 L polymerization tank, close the lid, hold it for 10 minutes to a vacuum of -740 mmHg, 70 kg Add vinyl chloride alone and 0.56 g of peroxide catalyst BND, raise the temperature to 64 ° C. to cause a polymerization reaction, and react for 5 hours to obtain a sample powder.

Table 8

  Description: Table 8 shows the properties of the resulting powder and its processed physical properties when the polymers (B), (C), (D) and (A) are added to Examples 6, 7, 8 and 9 in order. . The processed physical properties of Examples 7 to 9 are better than the comparative examples. Example 9 was added before the reaction, and the processing properties when various polymers were mixed and added were better than when the sheet flow air and the sheet flow mark were added alone.

Claims (10)

Various types of alkyl acrylate esters alone or various types of alkyl acrylate esters or acrylate esters polymer emulsions or dried products occupying about 10 to 0.1 wt% of the total amount,
For vinyl halide simple substance or 90% to 99.9 wt% of the total amount, or various mixed objects mainly composed of vinyl halide,
A method for producing a functional vinyl halide polymer, comprising adding and copolymerizing or grafting to produce a vinyl halide polymer. 2. The method for producing a functional vinyl halide polymer according to claim 1, wherein the vinyl halide polymer is produced by a copolymerization or graft reaction of a solution method, a bulk polymerization method or a suspension polymerization method. The main component of vinyl halide alone is vinyl chloride alone, and various mixed bodies mainly composed of vinyl halide are vinyl alkanote, bilidene halide, alkyl ester of carboxylic acid, or unsaturated hydrocarbon, 2. The method for producing a functional vinyl halide polymer according to claim 1, wherein the proportion of the main vinyl halide alone is 55% or more. 2. The method for producing a functional vinyl halide polymer according to claim 1, wherein the addition of various kinds of alkyl group acrylic acid esters is continuously performed from the beginning of the polymerization reaction until the reaction is completed. Addition of various kinds of alkyl group acrylic acid esters or acrylic acid ester polymer emulsion is added to the polymerization tank before the reaction, or until the addition of the emulsion continuously from the beginning of the polymerization reaction,
2. The method for producing a functional vinyl halide polymer according to claim 1, wherein the addition of the acrylic ester polymer dry product is performed by introducing the whole into a polymerization tank before the reaction is started. A variety of alkyl group acrylates are methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, stearyl methacrylate, phenyl methacrylate, and benidine methacrylate. 2. The method for producing a functional vinyl halide polymer according to claim 1, wherein the functional vinyl halide polymer is a substituent thereof. The method for producing a functional vinyl halide polymer according to claim 6, wherein the substituent is a halogeni group, a hydroxy group, an alkoxy group, an alkali dio group, or a Shan group. The proportion of the added amount of various alkyl group acrylic acid esters or acrylic acid ester polymer emulsions in vinyl halide alone or in various mixed polymerizations is 4.0 to 0.02 wt%,
2. The method for producing a functional vinyl halide polymer according to claim 1, wherein the amount of the acrylate ester polymer dry product added is 8.0 to 0.2 wt%. Vinyl halide alone or various polymer monomers consisting mainly of vinyl halide are added in one or two stages, and the addition before the reaction is the first stage, and the proportion of the added amount in the total amount is 50 to 70%. 2. The method for producing a functional vinyl halide polymer according to claim 1, wherein the continuous addition during the reaction is the second stage, and the ratio of the addition amount is 50 to 30%. Various types of alkyl acrylate esters or acrylate ester polymer emulsions or acrylate ester polymer dry polymers are grafted or core-shell single core single layer shells, single core multilayer shells, 2. The method for producing a functional vinyl halide polymer according to claim 1, comprising a layer shell and a multi-core multilayer shell.