KR101251727B1

KR101251727B1 - A method for preparing PVC with homogeneous particle morphology and high thermal stability

Info

Publication number: KR101251727B1
Application number: KR1020100067875A
Authority: KR
Inventors: 김용진; 김경현
Original assignee: 주식회사 엘지화학
Priority date: 2010-07-14
Filing date: 2010-07-14
Publication date: 2013-04-05
Also published as: KR20120007227A; WO2012008654A1; CN103038262A; CN103038262B

Abstract

The present invention relates to a method for producing a vinyl chloride-based resin having excellent particle uniformity and thermal stability, by applying an inorganic dispersion capable of removing hydrogen chloride while having a specific crystal structure in the step of preparing a vinyl chloride resin, particle size uniformity and In addition to preparing a vinyl chloride resin having excellent thermal stability, the thermal decomposition temperature of the resin may be improved, thereby improving the whiteness and physical properties of the product during processing.

Description

A method for preparing PVC with homogeneous particle morphology and high thermal stability}

The present invention relates to a method for producing a vinyl chloride-based resin having excellent particle uniformity and thermal stability, and to uniform particle size by applying an inorganic dispersion capable of removing hydrogen chloride while having a specific crystal structure in the step of preparing a vinyl chloride-based resin. And a method of providing a vinyl chloride resin having excellent thermal stability as well as providing an improvement in the whiteness and physical properties of the product during processing by improving the thermal decomposition temperature of the resin.

Particle size and internal structure of the vinyl chloride resin is a very important factor that affects the handling of the resin, the degree of blending with the subsidiary materials, and the processing characteristics of the product. The development techniques of vinyl chloride resins developed to date include mass polymerization and suspension polymerization techniques used to obtain particles having a size of 100 to 200 μm, depending on the size of the particles to be obtained. There is an emulsion polymerization technique used to obtain particles of 50 micrometers or less.

In the case of the suspension polymerization, a high molecular weight dispersant or a suspending agent or a protective colloid having a moderately controlled hydrophobicity and hydrophilicity with physical agitation is used. Adjust the size and internal shape of the monomer droplets. Related technologies are being developed by various companies such as Shin-etsu, Dow Chemical, Synthomer, and Nippon Goshei. Currently used materials include poly (vinyl acetate-alcohol copolymer) and modified cellulose ( cellulose, poly acrylate, etc. However, the techniques so far have been achieved by controlling the interfacial properties between water and vinyl chloride monomer, and little is known about the growth of basic particles of vinyl chloride resin. none.

In addition, in the bulk polymerization, since the shape of the particles is adjusted depending on the stirring force without using water, there are many problems in generating abnormal particles. There is no known technique for controlling particles in bulk polymerization, and Korean Patent 2007-0077246 discloses poly (ethylene oxide) and poly (propylene oxide) as dispersants to disperse nano calcium carbonate on resins. polyether series such as (poly (propylene oxide)), poly (methyl methacrylate) or poly (n-hexyl methacrylate) Methacrylate series, polyacrylate series including poly (n-propyl acrylate) and poly (n-butyl acrylate) , Polyester (polyester) including poly (ε-caprolactone) is used, but this is used for dispersing the inorganic material, not used to control the particle size of the resin itself.

On the other hand, the thermal stability deterioration of the vinyl chloride-based resin has been developed a lot of techniques to solve this problem because it limits the processing conditions of the resin and causes physical properties such as discoloration and tensile strength. The root cause of the thermal stability deterioration is known to be due to the low binding force between carbon and chlorine in the molecule. Especially, hydrogen chloride released from the molecular chain accelerates new side reactions by auto-catalyst reaction and continuously generates hydrogen chloride. It is known to make. In addition, a double bond remains at the position where the hydrogen chloride is released. When several of these double bond structures overlap, discoloration occurs and product properties are also deteriorated.

To solve this problem, most vinyl chloride resin manufacturers are neutralizing and removing hydrogen chloride generated by using various basic materials as disclosed in Japanese Patent 1997-059327. In this case, alkali metal hydroxides such as sodium hydroxide, potassium hydroxide and calcium hydroxide were used as neutralizing agents, and water-soluble bases such as ammonia were further used.

In this case, the polymerization of the vinyl chloride-based resin using the suspension polymerization, since the water is present in excess as a dispersed phase, it is easy to disperse using the above-mentioned neutralizing agent, it has the advantage of evenly adjusting the pH throughout the reactor, Since the neutralizing agent is distributed in the aqueous phase, there is a disadvantage in that the use efficiency of the dispersing agent is inhibited to generate a change in particle size and there is a limit in improving thermal stability.

In addition, in the case of the bulk polymerization of the vinyl chloride resin without using water, it is impossible to use the above water-soluble neutralizing agent alone. In order to use the water-soluble neutralizing agent, it must be mixed with water and added after the reaction. In this case, it is not only difficult to distribute the neutralizing agent evenly in the particles, but when the water is used a lot, a problem of cost occurs, such as a drying operation of the resin. It is a problem of technology.

In this regard, U.S. Patent No. 3,899,473 describes a method of uniformly dispersing an additive of an inorganic substance in a bulk polymerized PVC during the reaction, but does not show any effect other than even mixing of the inorganic substance.

U.S. Patent No. 4,460,754 claims that the whiteness was improved by adding an organometallic compound-based heat stabilizer to the resin between 30 and 80% of the mass conversion rate of the final product during the bulk polymerization, but there was no effect on the particle size distribution. . Similarly, in Japanese Patent 55,056,108, an inorganic suspending agent was added at a step between 30 and 80%, but the purpose is only to improve the flowability of the final particles.

Therefore, the present inventors continue to study how to increase the uniformity and thermal stability of particle size distribution regardless of polymerization method. Since the growth of the particles can be controlled, the uniformity of the particle size distribution can be increased regardless of the polymerization method, and thus the problem of abnormal particle generation and the degradation of the processed product due to thermal decomposition can be prevented. .

That is, the technical problem to be achieved by the present invention is to provide a method of preventing degradation of quality due to heating by increasing the thermal decomposition temperature of the resin while having a uniform particle size distribution by controlling the formation of internal particles of the resin during the resin production process I'm trying to.

According to the present invention, a vinyl chloride-based polymer is prepared by polymerizing a vinyl chloride monomer, and a method of preparing vinyl chloride resin having excellent particle uniformity and thermal stability is characterized by including an inorganic dispersion having the following formula (1). to provide.

(Wherein M (II) is at least one selected from divalent ions consisting of magnesium, nickel and zinc, M (III) is one selected from trivalent metal ions consisting of aluminum, iron, chromium and cobalt), and A ^m ⁻ is one selected from carbonate, hydroxide, nitrite, sulfate and halogen ions, x is a number between 0 and 1, m is a number between 1 and 2, and n is a number between 0 and 4 .)

Hereinafter, the present invention will be described in more detail.

First, the polymerization method used to prepare the vinyl chloride-based resin in the present invention is not particularly limited, but the bulk polymerization and suspension polymerization methods in terms of the characteristics involved in the process of forming the primary particles in the inside of the monomer droplets are used to control aspects of particle control. It is preferable in view of.

The vinyl chloride resin is a homopolymer of vinyl chloride, a copolymer with other monomers copolymerizable with vinyl chloride, olefin compounds such as ethylene and propylene, vinyl esters such as vinyl acetate and vinyl propionate, and unsaturated such as acrylonitrile. Vinyl alkyl ethers such as nitriles, vinyl methyl ethyl ether, unsaturated fatty acids such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, and monomers such as anhydrides of these fatty acids, or a copolymer of two or more kinds thereof may be used. . As the inorganic substance introduced during polymerization of such vinyl chloride-based resin, it is preferable to have formula (1) because hydrogen chloride generated during polymerization can be effectively removed.

[Formula 1]

Examples of the inorganic substance obtained from the above formula include Mg ₄ Al ₂ (OH) ₁₂ CO ₃ · 3H ₂ O, Mg ₂ Zn ₂ Al ₂ (OH) ₁₂ CO ₃ · 3H ₂ O, Mg (OH) ₂ · nH ₂ O, etc., and excellent in double to the effect of improving the thermal stability of the vinyl resin _{Mg 4 Al 2 (OH) 12} CO 3 · a portion of the hydrotalcite or magnesium having the structure: 3H ₂ O is substituted with zinc Mg _{More preferably, 2} Zn ₂ Al ₂ (OH) ₁₂ CO ₃ .3H ₂ O is used. At this time, excessive zinc ratio causes long-term thermal stability, so zinc is preferably not more than 50% of magnesium.

On the other hand, the particle diameter of the inorganic material is preferably 10 μm or less, and more preferably 0.5 μm or less so that dispersibility can be maintained. In consideration of the transparency lowering side, it is most preferable that it is 0.2 micrometer (micrometer) or less.

In consideration of particle size uniformity and thermal stability, the inorganic material is preferably added at the beginning or the middle of the polymerization, and more preferably at a time when the conversion rate does not exceed 10% based on the mass of the finally produced vinyl chloride resin. Do. This is because, if the conversion rate is exceeded, even when the inorganic material is added, the particles do not participate in the initial generation of particles, and thus the control and uniformity of the particle shape are not increased. It is more preferable at this point to add during seed production in order to participate in initial particle formation and to increase the particle size uniformity of a final product.

On the other hand, the inorganic material is preferably subjected to an organic treatment on the surface before the addition can improve the dispersibility to the vinyl chloride monomer, such organic treatment, such an anionic surfactant, fatty acid, silane, polyorganosiloxane, poly Surface by coating one or more of organohydrogensiloxanes, higher fatty acid esters, more particularly stearic acid, or by heating with a polyhydric alcohol to a polyhydric alcohol ester, more specifically glycol monostearate Can be used. It is most preferable that the polyhydric alcohol ester is prepared by reacting the surface of the inorganic substance in view of compatibility with the vinyl chloride resin.

On the other hand, the amount of the organic treatment agent is preferably used in an amount of 1 to 10 parts by weight based on 100 parts by weight of the inorganic material to be treated. If the value is exceeded, even if the inorganic material is added during the polymerization of the vinyl chloride resin, thermal stability may be reduced. It can be undesirable.

The amount of the organicated inorganic material used in the present invention is in the range of 0.01 to 0.2 parts by weight based on 100 parts by weight of the vinyl chloride monomer in the bulk polymerization, and 0.01 to 0.4 parts by weight based on the total 100 parts by weight of vinyl chloride in the suspension polymerization. It is preferable to inject | pour into, and it can change an injection quantity according to the target particle diameter within the said range. For example, when the inorganic material is added at a level of 0.01 parts by weight based on the total weight of the initial monomer, particles having a particle diameter of 150 μm (micrometer) may be obtained in the bulk polymerization. On the other hand, if the input amount exceeds the above range it is not preferable because it generates small particles and inorganic substances that do not combine with the monomer to form a scale. In addition, it is not preferable to add less than the above range because the size of the particles increases and the effect of improving uniformity is lowered.

In the case of the use of double hard extrusion and injection molded products, specifically for building profiles, the average particle diameter of the vinyl chloride resin is preferably 100 to 250 μm (micrometer), and is used for soft calender products, specifically for food wraps and sheets. When used for manufacturing purposes, the average particle diameter of the vinyl chloride-based resin is preferably 50 to 200 μm (micrometer), and the vinyl chloride-based resin is used for the production of plastisol-processed products, specifically wallpaper or undercoat, and flooring. It is preferable that the average particle diameter of is 1-50 micrometers (micrometer).

Specifically, for example, the preparation method of the present invention using the bulk polymerization method, the first vinyl chloride monomer is adjusted to the first reaction pressure, the first reaction initiator is added, and then under the first reaction temperature, the second reaction pressure Polymerize for the first reaction time (first step). Before the initial conversion or during the first step, the organic conversion surface-treated inorganic material of the formula 1 is added and the seed is generated before the polymerization conversion exceeds 10% (second step). Then, a second vinyl chloride monomer and a second reaction initiator were added to the resultant seed, reacted under a second reaction temperature and under a third reaction pressure for a second reaction time, and then the temperature was lowered to remove the unreacted monomer to obtain a resin. (The third step).

As described above, the vinyl chloride monomer content for seed production in the first step is used 10 to 90 parts by weight of the total 100 parts by weight, the remaining amount is preferably added separately when preparing the resin as the third step.

In addition, the first reaction pressure is 4.5 to 8.5 K / G, the second reaction pressure is 9 to 13 K / G, the third reaction pressure is preferably adjusted in three stages of 7 to 8 K / G.

In addition, the first reaction temperature is preferably 60 to 75 ℃, and the second reaction temperature is adjusted to 50 to 55 ℃ in two stages.

In this case, as the first reaction initiator used in the preparation of the seed, one or more selected from the group consisting of t-butylperoxy neodecanoate, octyl peroxydicarbonate, and hexyl peroxy pivalate may be used in an amount of 0.01 to 0.2 parts by weight, As the second reaction initiator used in the preparation of the resin, tetramethyl butyl peroxy decanoate or cumyl peroxy pivalate may be used in an amount of 0.01 to 0.4 parts by weight.

At this time, the polymerization time required to generate the seed is 15 to 25 minutes is sufficient to obtain a uniformly dispersed particle nucleus, and the polymerization time required to prepare the resin can produce a resin having a conversion rate of 60% or more in 160 to 200 minutes desirable.

In addition, the inorganic material of Formula 1 added in the second step is added before the polymerization conversion rate is more than 10% at the beginning of the reaction or during the first step, the particle diameter is 0.05 to 10 ㎛ (micrometer), a total of 100 vinyl chloride monomer 0.01 to 0.2 parts by weight, based on parts by weight. At this time, it is preferable to administer the inorganic substance which was organically processed previously.

On the other hand, the production method using the suspension polymerization method, for example, a protective colloid, a vinyl chloride monomer, an inorganic substance, and an initiator are added and stirred to polymerize during the first reaction time at the first reaction temperature. Then, to protect the plant by neutralizing the reactants, sodium bicarbonate was added and the resin was obtained by removing the remaining unreacted monomer while lowering the temperature. In this case, the inorganic material of Formula 1, which is added to the initial reaction or before the polymerization conversion exceeds 10%, has a particle diameter of 0.05 to 10 μm (micrometer) and is administered at 0.01 to 0.4 parts by weight based on 100 parts by weight of the vinyl chloride monomer. At this time, it is preferable to administer the inorganic substance which was organically processed previously.

In addition, the protective colloid includes, but is not limited to, a primary dispersant composed of polyvinyl (acetate-alcohol) having a degree of hydration of 80% and a polydispersant composed of polyvinyl (acetate-alcohol) having a degree of hydration of 40%. 0.01 to 0.2 parts by weight based on 100 parts by weight of the vinyl monomer, and t-butylperoxy neodecanoate, octylperoxydicarbonate, hexyl peroxypivalate, tetramethyl butyl peroxy decanoate, cumyl peroxy as an initiator It is preferable to add 0.02 to 0.2 parts by weight of at least one selected from the group consisting of pivalate.

The primary reaction temperature is 55 to 60 ℃, the reaction time is preferably 4 to 6 hours can be produced a resin with a conversion rate of 75% or more.

According to the above-described method of the present invention, in addition to preparing a vinyl chloride resin having excellent particle size uniformity and thermal stability by applying an inorganic dispersion capable of removing hydrogen chloride while having a specific crystal structure in the step of preparing the vinyl chloride resin By improving the thermal decomposition temperature of the resin can be provided to improve the whiteness and physical properties of the product during processing.

1 is an optical micrograph taken for the purpose of confirming the particle shape and distribution of each vinyl chloride-based resin prepared by the bulk polymerization method of the present invention and the conventional bulk polymerization method. FIG. 1A shows an optical micrograph (x200 ×) of a seed according to Comparative Example 1, FIG. 1B is a 200 times magnification of the shape of the final particle prepared from the seed of FIG. 1A, and FIG. 1C shows An optical micrograph (x200x) of the seed according to Example 1 is shown and FIG. 1D is a 200x magnification of the shape of the final particles prepared from the seed of FIG. 1C.

Hereinafter, the constitution and effects of the present invention will be described in more detail with reference to examples and comparative examples. However, these examples are merely intended to clearly understand the present invention and are not intended to limit the scope of the present invention.

Comparative example 1 (block polymerization method)

As a general bulk polymerization method, the internal pressure of the reactor was degassed at a high vacuum of less than 70 torr to remove oxygen and other impurities. 60 parts by weight of the first vinyl chloride monomer was added thereto. When the reaction pressure is 4.5 to 8.5 K / G by heating while stirring is maintained, 0.02 parts by weight of t-butylperoxy neodecanoate of the first reaction initiator is added and the reaction temperature is 60 to 75 ° C. and the reaction pressure is 9 to Particle nuclei were formed by polymerization for 15-25 minutes until 13 K / G.

40 parts by weight of the second vinyl chloride monomer and 0.03 parts by weight of tetramethyl butyl peroxy decanoate as the second reaction initiator were added to the particle nucleus to 160 to 200 at a reaction temperature of 50 to 55 ° C. and a reaction pressure of 7 to 8 K / G. Reacted for minutes. At this time, the stirring speed was lower than that of the particle nucleation process.

The remaining resin was then removed while lowering the temperature to obtain a final resin. The optical micrograph of the seed obtained at this time is shown as FIG. 1A, and the optical microscope picture of the final particle is shown as FIG. 1B.

Comparative example 2 ( suspension Polymerization method)

As a general method of suspension polymerization, 0.06 parts by weight of a dispersing agent having a degree of hydration of 80% and a dispersing degree of 40% of hydration as a protective colloid agent and a degree of hydration of 40% were added to the reactor at a ratio of 3: 1, respectively, and t-butyl peroxy neodecano as an initiator. Eight was added 0.03 parts by weight relative to the monomer. Then the internal pressure of the reactor Less than 70 torr Degassing in vacuo to remove oxygen and other impurities. 100 parts by weight of vinyl chloride monomer was added thereto. It was stirred at a rate of 180 times per minute and reacted at a temperature of 58 ° C. for 5 hours. Thereafter, 0.008 parts by weight of sodium hydrogen carbonate was added to the obtained reactant based on 100 parts by weight of the monomer. The remaining unreacted monomer was then removed while lowering the temperature to obtain a slurry, which was dried to obtain a final resin.

Manufacturing example One( Organicization Preparation of Surface Treated Minerals Example 1 )

Mg ₄ Al ₂ (OH) ₁₂ CO ₃ · 3H ₂ O structure or Mg ₄ Zn ₂ Al ₂ (OH) ₁₂ CO ₃ · 3H ₂ O, respectively, the size of 0.5 ㎛ (micrometer) or 10 ㎛ (micrometer) respectively Glycerin monostearate was added to 10 parts by weight based on 100 parts by weight of the inorganic substance to hydrotalcite, and heated at 180 ° C. to prepare the organic surface-treated inorganic substances.

Manufacturing example 2( Organicization Preparation of Surface Treated Minerals Example 2 )

Mg ₄ Al ₂ having a size of 0.5 μm (micrometer) or 10 μm (micrometer) which was organicized in the same manner except for using 1 part by weight of stearic acid based on 100 parts by weight of inorganic material instead of glycerin monostearate in Preparation Example ₂ An organically treated inorganic substance having a structure of (OH) ₁₂ CO ₃ · 3H ₂ O or Mg ₄ Zn ₂ Al ₂ (OH) ₁₂ CO ₃ · 3H ₂ O was respectively prepared.

Example 1 (block polymerization + Organicization Surface treated minerals 1)

In Comparative Example 1, when the polymerization conversion rate was 10% or less, the organic surface-treated hydrotalcite having a Mg ₄ Al ₂ (OH) ₁₂ CO ₃ .3H ₂ O structure having a size of 0.5 μm (micrometer) prepared in Preparation Example 1 was prepared. 0.01 parts by weight The same procedure as in Comparative Example 1 was repeated except that it was added. The optical micrograph of the seed obtained at this time is shown as FIG. 1C, and the optical microscope picture of the final particle is shown as FIG. 1D.

Example 2 ( suspension Polymerization method Organicization Surface treated minerals)

When the polymerization conversion rate in Comparative Example 2 is 10% or less Comparative Example except that 0.01 parts by weight of the organic surface-treated hydrotalcite having a Mg ₄ Al ₂ (OH) ₁₂ CO ₃ 3H ₂ O structure of 0.5 ㎛ (micrometer) size prepared in Preparation Example 2 The same method as 2 was repeated.

Example 3 (Block polymerization method + Organicization Unsurfaced minerals)

Example 1 except that 0.01 parts by weight of hydrotalcite having an Mg ₄ Al ₂ (OH) ₁₂ CO ₃ · 3H ₂ O structure of 0.5 μm (micrometer) unorganized treatment was added to The same method was repeated.

Example 4 (Block polymerization method + Organicization Surface treated minerals 2)

Except that 0.01 parts by weight of an organically treated hydrotalcite having a structure of Mg ₄ Al ₂ (OH) ₁₂ CO ₃ 3H ₂ O having a size of 10 μm (micrometer) prepared in Preparation Example 2 was added to Comparative Example 1. The same method as in Comparative Example 1 was repeated.

Example 5 (Block polymerization method + Organicization Surface treated minerals 3)

0.1 part by weight of an organically treated hydrotalcite having a structure of Mg ₄ Al ₂ (OH) ₁₂ CO ₃ .3H ₂ O having a size of 0.5 μm (micrometer) prepared in Preparation Example 2 The same method as in Comparative Example 1 was repeated except that it was added.

Example 6 (Block polymerization method + Organicization Surface treated minerals 4)

Except that 1 part by weight of an organically treated hydrotalcite having a structure of Mg ₄ Al ₂ (OH) ₁₂ CO ₃ 3H ₂ O having a size of 0.5 μm (micrometer) prepared in Preparation Example 2 was added to Comparative Example 1. The same method as in Comparative Example 1 was repeated.

Example 7 ( Block polymerization + Organicization Surface treated minerals 5)

In Comparative Example 1, when the polymerization conversion rate was 10% or less, the organic surface-treated inorganic material having a 0.5 μm (micrometer) sized Mg ₄ Zn ₂ Al ₂ (OH) ₁₂ CO ₃ · 3H ₂ O structure prepared in Preparation Example 1 was prepared. 0.01 parts by weight The same procedure as in Comparative Example 1 was repeated except that it was added.

Example 8 ( Suspension polymerization + Organicization Surface treated minerals 2)

When the polymerization conversion rate in Comparative Example 2 is 10% or less Comparative Example 1 except that 0.01 parts by weight of an organic surface-treated inorganic material having a 0.5 μm (micrometer) size of Mg ₄ Zn ₂ Al ₂ (OH) ₁₂ CO ₃ · 3H ₂ O structure was prepared. The same method as 2 was repeated.

Example 9 ( Suspension polymerization + Organicization Untreated minerals)

0.01 part by weight of hydrotalcite having an Mg ₄ Zn ₂ Al ₂ (OH) ₁₂ CO ₃ .3H ₂ O structure of 0.5 μm (micrometer) size that was not organicized at a polymerization conversion rate of 10% or less in Comparative Example 2 Input.

Comparative example 3 ( Block polymerization + Mineral Input Conversion Rate Change )

In Comparative Example 1, when the polymerization conversion was 10 to 20%, an organic surface treatment having a 0.5 μm sized Mg ₄ Zn ₂ Al ₂ (OH) ₁₂ CO ₃ · 3H ₂ O structure prepared in Preparation Example 1 The same procedure as in Comparative Example 1 was repeated except that 0.01 part by weight of inorganic material was added.

Comparative example 4 ( Suspension polymerization + Inorganic input conversion rate Change )

In Comparative Example 2, when the polymerization conversion rate was 10 to 20%, an organic surface treatment having a 0.5 μm sized Mg ₄ Zn ₂ Al ₂ (OH) ₁₂ CO ₃ · 3H ₂ O structure prepared in Preparation Example 1 The same procedure as in Comparative Example 2 was repeated except that 0.01 part by weight of inorganic material was added.

Comparative example 5 ( Block polymerization + Other minerals Example of input )

0.01 part by weight of 0.5 µm (micrometer) sized titanium dioxide prepared in the same manner as in Preparation Example 1 when the polymerization conversion rate was 10% or less in Comparative Example 1 The same procedure as in Comparative Example 1 was repeated except that it was added.

Comparative example 6 ( Suspension polymerization + Other minerals Example of input )

0.01 part by weight of 0.5 µm (micrometer) sized titanium dioxide prepared in the same manner as in Preparation Example 1 when the polymerization conversion rate was 10% or less in Comparative Example 2. The same procedure as in Comparative Example 2 was repeated except that it was added.

Comparative example 7 ( Block polymerization + Input mineral content Change One)

The same process as in Example 1 was repeated except that 0.001 parts by weight of the amount of the organicated inorganic substance added in Example 1 was added.

Comparative example 8 ( Block polymerization + Input mineral content Change 2)

The same process as in Example 1 was repeated except that 0.5 parts by weight of the amount of the organicated inorganic material added in Example 1 was added.

Comparative example 9 ( Suspension polymerization + Input mineral content Change One)

The same process as in Example 1 was repeated except that 0.001 parts by weight of the amount of the organicated inorganic substance added in Example 2 was added.

Comparative example 10 ( Suspension polymerization + Input mineral content Change 2)

The same process as in Example 1 was repeated except that 0.5 parts by weight of the amount of the organicated inorganic material added in Example 2 was added.

Comparative example 11 ( Block polymerization + Excessive Organicization Surface treated minerals Example of input )

Mg ₄ Al ₂ (OH) ₁₂ CO ₃ · 3H having a size of 0.5 μm (micrometer) obtained by adding 20 parts by weight of stearic acid to 100 parts by weight of inorganic material in Preparation Example 2 when the polymerization conversion rate was 10% or less in Comparative Example 1. 0.01 part by weight of hydrotalcite having a ₂ O structure The same procedure as in Comparative Example 1 was repeated except that it was added.

Comparative example 12 ( Suspension polymerization + Excessive Organicization Surface treated minerals Example of input )

Mg ₄ Al ₂ (OH) ₁₂ CO ₃ · 3H having a size of 0.5 μm (micrometer) obtained by adding 20 parts by weight of stearic acid to 100 parts by weight of an inorganic substance in Preparation Example 2 when the polymerization conversion rate was 10% or less in Comparative Example 2. 0.01 part by weight of hydrotalcite having a ₂ O structure The same procedure as in Comparative Example 2 was repeated except that it was added.

Test Items :

* Process whiteness measurement :

To 100 parts by weight of the vinyl chloride resins obtained in Examples and Comparative Examples, 3 parts by weight of a lead-based stabilizer, 0.3 parts by weight of barium stearate, and 0.1 parts by weight of titanium dioxide were added at a temperature of 185 ° C. using a roll mill. After kneading for 5 minutes, a 0.5 mm thick sheet was obtained. After that, the whiteness (WI) value was measured using Nippon Denshoku's NR-3000, and the results are shown. Thermal stability can be measured from the whiteness value, and the higher the value, the better the thermal stability.

* Pyrolysis Temperature Measurement:

The mass change at that time was measured by Q50 model of TA instrument, heating from 40 degreeC to 400 degreeC in nitrogen atmosphere at a speed | rate of 10 degrees per minute. The temperature at which the decomposition rate reaches 70% was defined as the pyrolysis temperature.

* Measurement of particle size and particle size distribution :

The obtained resin was measured for particle size using a HELOS particle size analyzer manufactured by Sumpatec, and the value of the span at that time was defined as a particle size distribution. Lower Span value means less deviation.

division Processing whiteness Pyrolysis temperature (℃) Particle size uniformity Particle diameter (㎛ (micrometer)) Example One 67 296 0.65 152 Example 2 74 308 0.54 147 Example 3 64 295 0.69 150 Example 4 66 296 0.70 165 Example 5 69 296 0.65 151 Example 6 69 296 0.64 134 Example 7 68 297 0.65 153 Example 8 75 310 0.54 147 Example 9 72 302 0.57 145 Comparative Example 1 62 285 0.78 151 Comparative Example 2 70 298 0.57 143 Comparative Example 3 63 286 0.78 151 Comparative Example 4 70 300 0.57 143 Comparative Example 5 63 283 0.78 151 Comparative Example 6 71 295 0.57 143 Comparative Example 7 63 288 0.74 151 Comparative Example 8 69 298 0.60 112 Comparative Example 9 71 300 0.60 143 Comparative Example 10 75 310 0.52 180 Comparative Example 11 61 285 0.66 152 Comparative Example 12 69 298 0.56 147

As shown in Table 1 above, in the case of Examples 1,3,4,5,6 prepared by the bulk polymerization method with the addition of the inorganic material, compared to the case of Comparative Example 1 prepared by the bulk polymerization method without adding the inorganic material, In terms of thermal decomposition temperature, particle size uniformity, and particle size, all were improved. In addition, in Examples 1, 4, 5, and 6, in which the organic surface treatment was carried out, compared to the case of Example 3 without the organic surface treatment, it was confirmed that the whiteness and the thermal decomposition temperature and the particle diameter were further improved.

On the other hand, in the case of Example 2 prepared by the suspension polymerization method prepared by the suspension polymerization method, not the bulk polymerization method, but the inorganic material was added, the uniformity of the particle size is somewhat poor, but the degree of processing whiteness It was confirmed that both the pyrolysis temperature and the particle diameter were excellently improved.

In addition, as shown in Figure 1 summarized the optical micrograph, the seed and the final particles prepared in Example 1 of the present invention (Fig. 1c, d) is prepared by Comparative Example 1 and the final particles (Fig. 1a, b) It was confirmed that both in terms of particle shape and distribution more uniform.

Furthermore, in the case of Comparative Examples 3 and 4, where the time of mineral input was too late, the processing whiteness and the particle size uniformity were poor, and in Comparative Examples 5 and 6, in which titanium dioxide was applied as the inorganic material, the processing whiteness and the pyrolysis temperature were poor. I could confirm it. In addition, in the case of Comparative Examples 7 to 10 where the input inorganic content is not preferable, there was a problem that the particle diameter was too large or too small, and in Comparative Examples 11 and 12, in which the surface organicization of the inorganic material was excessively processed, it was confirmed that the processed whiteness was poor. Could.

Claims

In preparing the vinyl chloride-based resin by bulk polymerization or suspension polymerization of the vinyl chloride monomer, it is polymerized including the inorganic dispersion of the following formula 1,
The inorganic dispersion is an inorganic substance organically treated using an organic treatment agent, and the organic treatment agent is an anionic surfactant, fatty acid, silane, polyorganosiloxane, polyorganohydrogensiloxane, higher fatty acid ester or polyhydric alcohol or polyhydric alcohol. At least one selected from the group consisting of esters used in the range of 1 to 10 parts by weight based on 100 parts by weight of the inorganic dispersion, characterized in that the vinyl chloride resin having excellent particle uniformity and thermal stability
[Formula 1]

(Wherein M (II) is at least one selected from divalent ions consisting of magnesium, nickel and zinc, M (III) is one selected from trivalent metal ions consisting of aluminum, iron, chromium and cobalt), and A ^m- is one selected from carbonate ion, hydroxide ion, nitrite ion, sulfate ion and halogen ion, x is a number between 0 and 1, m is a number between 1 and 2, n is a number between 0 and 4 .)

delete

The particle uniformity and thermal stability of claim 1, wherein the inorganic material is Mg ₄ Al ₂ (OH) ₁₂ CO ₃ · 3H ₂ O or Mg ₂ Zn ₂ Al ₂ (OH) ₁₂ CO ₃ · 3H ₂ O. Method for producing this excellent vinyl chloride resin.

The method for producing a vinyl chloride resin having excellent particle uniformity and thermal stability according to claim 1, wherein the inorganic particles have a particle diameter of 0.05 to 10 µm.

The method of claim 1, wherein the inorganic material is introduced into the reaction system at the initial polymerization stage or at a polymerization conversion rate of 10% or less.

The method of claim 1, wherein the organically treated inorganic material is coated with a surface of the inorganic material using an organic treatment agent or reacted to the surface by heating with an organic treatment agent before use, the surface uniformity, characterized in that Process for producing vinyl chloride resin with excellent performance and thermal stability.

delete

[Claim 2] The preparation of the vinyl chloride resin having excellent particle uniformity and thermal stability according to claim 1, wherein the amount of the organically treated inorganic material is added at 0.01 to 0.2 parts by weight based on 100 parts by weight of the vinyl chloride monomer. Way.

[Claim 2] The vinyl chloride resin having excellent particle uniformity and thermal stability according to claim 1, wherein the amount of the organically treated inorganic material is added at 0.01 to 0.4 parts by weight based on 100 parts by weight of the vinyl chloride monomer. Manufacturing method.

The method according to claim 1, wherein the bulk polymerization,
a) controlling a first vinyl chloride monomer to a first reaction pressure, adding a first reaction initiator, and then polymerizing for a first reaction time under a first reaction temperature and a second reaction pressure;
b) a second step of introducing an organically treated inorganic material and generating a seed before the polymerization conversion rate exceeds 10% during the initial stage or during the first step; And
c) adding a second vinyl chloride monomer and a second reaction initiator to the resulting seed and reacting for a second reaction time under a second reaction temperature and a third reaction pressure, and then lowering the temperature to remove unreacted monomer to obtain a resin. The third step; method of producing a vinyl chloride resin excellent in particle uniformity and thermal stability, characterized in that consisting of.

The method of claim 10, wherein in the first step, the content of the first vinyl chloride monomer is 10 to 90 parts by weight based on 100 parts by weight, and the remaining content is added separately when the resin is prepared as the third step. A method for producing a vinyl chloride resin having excellent particle uniformity and thermal stability.

The particle of claim 10, wherein the first reaction pressure is 4.5 to 8.5 K / G, the second reaction pressure is 9 to 13 K / G, and the third reaction pressure is 7 to 8 K / G. Method for producing vinyl chloride resin with excellent uniformity and thermal stability.

The method of claim 10, wherein the first reaction temperature is 60 to 75 ° C., the second reaction temperature is 50 to 55 ° C., the first reaction time is 15 to 25 minutes, and the second reaction time is 160 to 200 minutes. A method for producing a vinyl chloride resin having excellent particle uniformity and thermal stability.

The method of claim 10, wherein the first reaction initiator is used in 0.01 to 0.2 parts by weight of one or more selected from t-butyl peroxy neodecanoate, octyl peroxy dicarbonate, hexyl peroxy pivalate, and the second Tetramethyl butyl peroxy decanoate or cumylperoxy pivalate is used as a reaction initiator in an amount of 0.01 to 0.4 parts by weight.

The method of claim 1, wherein the suspension polymerization is obtained by adding a protective colloid, a vinyl chloride monomer, an inorganic substance, and an initiator and stirring to polymerize at a first reaction temperature for a first reaction time followed by adding sodium hydrogen carbonate. The inorganic material has a particle uniformity and thermal stability of 0.01 to 0.4 parts by weight based on 100 parts by weight of the total amount of vinyl chloride monomer before the initial reaction or the polymerization conversion exceeds 10%. Excellent method for producing vinyl chloride resin.

The method of claim 15, wherein the protective colloid is 0.01 to 0.2 based on 100 parts by weight of polyvinyl chloride (acetate-alcohol) having a degree of hydration of 80% and polyvinyl (acetate-alcohol) having a degree of hydration of 40% by weight. Part by weight, the initiator is selected from the group consisting of t-butyl peroxy neodecanoate, octyl peroxy dicarbonate, hexyl peroxy pivalate, tetramethyl butyl peroxy decanoate, cumyl peroxy pivalate A method for producing a vinyl chloride resin excellent in particle uniformity and thermal stability, characterized in that at least 0.02 to 0.2 parts by weight based on 100 parts by weight of the vinyl chloride monomer content.

The method of claim 15, wherein the primary reaction temperature is 55 to 60 ° C. and the reaction time is 4 to 6 hours.