KR101211231B1 - Antioxidant dispersion composition, method of preparing thereof and vinyl chloride-based resins comprising the same - Google Patents

Abstract

The present invention comprises at least one antioxidant selected from phenolic antioxidants and thioester antioxidants, monovalent alcohols or polyhydric alcohols having 1 to 18 carbon atoms, and at least one dispersion medium selected from epoxidized fatty acids or fatty acid esters. The present invention relates to an antioxidant oil dispersion, a method for preparing the same, and a vinyl chloride resin polymer prepared therefrom, wherein the vinyl chloride resin prepared from the antioxidant oil dispersion according to the present invention is reduced in residual radicals and residual monomers. The thermal stability is improved, and the stripping time is shortened, thereby improving the overall productivity.

Vinyl chloride * Antioxidant * Dispersion * High temperature stripping * Whiteness

Description

Antioxidant oily dispersion, preparation method thereof and vinyl chloride-based resin prepared therefrom {Antioxidant dispersion composition, method of preparing pretty and vinyl chloride-based resins comprising the same}

The present invention relates to an oil-based dispersion of antioxidants useful for the production of vinyl chloride-based resins, which can shorten production time and have improved thermal stability, a method for preparing the same, and a vinyl chloride-based resin polymer prepared therefrom.

Generally, vinyl chloride-based resins such as polyvinyl chloride are widely used in the field of piping materials, building materials, etc. because of their excellent mechanical strength, weather resistance, chemical resistance, and the like.

However, vinyl chloride-based resins have problems of poor thermal stability through oxidation, decomposition, and structural change due to heat or light. In order to solve this problem, there have been efforts to compensate for the lack of physical properties by using antioxidants, processing aids, ultraviolet absorbers in the production of vinyl chloride resin.

In addition, in order to increase the effectiveness of these additives, many attempts have been made to improve the physical properties in small amounts by adding them during polymerization rather than during mixing or processing of workpieces.

Looking at the related arts related to this, in Korea Patent Publication No. 2004-0106427, a chain growth inhibitor is added at the end of the polymerization of PVC using suspension polymerization to prevent free monomers from being absorbed on the surface of the particles, thereby reducing the porosity. It was possible to prevent the decrease in water absorption to improve the processability during extrusion or calendering. Used as chain growth inhibitors are stable free nitroxyl radicals and screened phenolic antioxidants, but also alkylated monophenols, alkylated thiomethyl phenols, hydroquinones, tocopherols, hydroxyated thiodiphenyl ethers, alkylidene combiphenols, triazines. It has various forms, such as a compound, and these chain growth inhibitors are known.

The masked phenolic antioxidant used as the chain growth inhibitor has the function of removing the remaining unused radicals during the polymerization process in addition to the effect of inhibiting chain growth to improve the thermal stability of the final resin.

In order to increase the effectiveness of these antioxidants, their particle size should be 0.1 to 10 μm, particularly about 5 μm. However, when the shielded phenolic antioxidant in the solid state is added during the polymerization, its effectiveness is lowered due to the difficulty of dispersion.

Therefore, efforts have been made to increase the effectiveness by crushing the particles small. Among them, according to Korean Patent 2004-0094825, the problem of low dispersibility caused by the conventional dry and wet grinding method is emulsified by using a polyvinyl alcohol, which is a nonionic surfactant, to increase the effectiveness of the antioxidant.

However, these aqueous dispersions of antioxidants cannot be used for bulk polymerization of vinyl chloride resins that do not have an aqueous phase. The antioxidant must be distributed evenly in a small size in the resin in order to achieve the intended effect. When the aqueous dispersion meets the vinyl chloride monomer and the vinyl chloride resin, it loses stability and increases in viscosity, resulting in a large resin. Unite in blocks.

Therefore, there is a need for a method in which the additives added in preparing the vinyl chloride-based resin using the bulk polymerization can be uniformly dispersed to have intended effects.

Therefore, the present invention is to solve the problems in the prior art according to the use of additives in producing a vinyl chloride-based resin having excellent thermal stability.

In the present invention, a polyhydric alcohol or a polyhydric alcohol having 1 to 18 carbon atoms so as to disperse one or more antioxidants selected from phenolic antioxidants and thioester antioxidants to a size of 0.1 to 10 μm or less when producing a vinyl chloride resin. The above-mentioned problems can be solved by preparing an antioxidant oily dispersion composition dispersed in at least one dispersion medium selected from among epoxidized fatty acids or fatty acid esters.

Accordingly, an object of the present invention is to provide an antioxidant oil-based dispersion composition capable of producing a vinyl chloride-based resin having excellent thermal stability by improving dispersibility when manufacturing a vinyl chloride-based resin, thereby exhibiting inherent characteristics of the antioxidant. .

Another object of the present invention is to provide a method for preparing the antioxidant oily dispersion having excellent dispersibility.

Further, another object of the present invention is to provide a vinyl chloride-based resin polymer prepared from the antioxidant oil-based dispersion composition having the above characteristics.

The antioxidant oil-based dispersion composition according to the present invention can maintain not only the dispersibility of the antioxidant itself, but also the dispersibility at this time until it is mixed with the vinyl chloride monomer and introduced into the reactor. Excellent processing whiteness can also be achieved.

The antioxidant oil-based dispersion composition of the present invention comprises at least one antioxidant selected from phenolic antioxidants and thioester antioxidants, monohydric alcohols or polyhydric alcohols having 1 to 18 carbon atoms, and one selected from epoxidized fatty acids or fatty acid esters. It is characterized by including a dispersion medium or more of species.

In addition, the antioxidant oil-based dispersion production method of the present invention is at least one antioxidant selected from phenolic antioxidant and thio ester antioxidant, and monohydric alcohol or polyhydric alcohol having 1 to 18 carbon atoms, and epoxidized fatty acid or fatty acid ester Characterized in that it comprises the step of mixing at least one dispersion medium selected from among the temperature of 80 to 150 ℃.

In addition, the present invention is also characterized by a vinyl chloride-based resin polymer prepared from the antioxidant oil-based dispersion.

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

The antioxidant according to the present invention is a phenolic antioxidant selected from alkylated monophenolic compounds represented by the following formula (1) and compounds represented by the formula (2).

Wherein R1 is a C ₁ to C ₂₀ alkyl group,

이고, 여기서 n은 1~4의 정수이고, R3는 다음 화학식 3의 구조를 갖는 물질이다.In Formula 2, R2 is C ₁ to C ₂₀ Alkyl group, or

Wherein n is an integer of 1 to 4, and R3 is a material having a structure of Formula 3 below.

In addition, the antioxidant according to the present invention is a thioester-based antioxidant represented by the following formula (4).

In Formula 4, x is an integer of 12 to 18.

The antioxidant according to the present invention preferably has a particle size of 0.1 ~ 10㎛, which is to increase the effectiveness of the antioxidant by the dispersion is effective, more preferably about 5㎛ size.

In addition to the antioxidant described above, an amine compound, a sulfur compound, or the like, which is usually used for producing a vinyl chloride resin, may be included.

The dispersion medium for dispersing such an antioxidant is selected from polyhydric alcohols such as monohydric alcohols having 1 to 18 carbon atoms or trihydric alcohols represented by glycerol, and epoxidized fatty acids or fatty acid esters. 1 or more types.

Specific examples of the monohydric alcohol or polyhydric alcohol having 1 to 18 carbon atoms include methanol, ethanol, propanol, butanol, butanediol, pentanol, heptanol, hexanol, 1,6-hexanediol, n-octanol, 1 , 9-nonanediol, ethylene glycol, 1,2-propanediol, cetyl alcohol, lauryl alcohol (n-dodecyl alcohol), stearyl alcohol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, pentaerythritol , Dipentaerythritol, tripentaerythritol, bistrimethylolpropane, trimethylolethane, bistrimethylolethane, trimethylolpropane, bistrimethylolpropane, sorbitol, maltite, isomaltite, lactite, lysine, Mannitol, xylite, inosite, lactose, leucross, paltinite, tetramethylolcyclohexanol, tetramethylolcyclopentanol, tetramethylolcyclopyranol, glycerol, diglycerol, polyglycerol, thio At least one member selected from the group consisting of glycerol and their condensates or the, and the like.

Specific examples of the epoxidized fatty acids or fatty acid esters include epoxidized soybean oil, rapeseed oil, epoxidized polybutadiene, epoxidized linseed oil, epoxidized fish oil, epoxidized castor oil, epoxidized sunflower seed oil and carbon number. It is preferably one or more selected from the group consisting of oleate of 1 to 8, stearate of 1 to 8 carbon atoms, and diglycidyl ether of bisphenol A, but is not limited thereto.

Antioxidant oily dispersion according to the present invention is preferably prepared by the step of mixing the antioxidant at a temperature of 80 ~ 150 ℃ using at least one dispersion medium, which must be above the melting point of the material for even dispersion. This is because the decomposition temperature should not be exceeded.

In addition, it is preferable that the ratio of antioxidant and a dispersion medium is 1: 100-5: 1 weight ratio in consideration of dispersibility. If the content of the dispersion medium exceeds the above range, there is a difficulty in adding such a large-capacity pump, and if less than the above range, the dispersion medium must be heated to a temperature higher than the decomposition temperature.

The present invention also provides a vinyl chloride-based resin polymer prepared from the antioxidant oil-based dispersion composition having excellent whiteness.

The vinyl chloride resin is a polymer of vinyl chloride; A vinyl resin having a vinyl chloride unit in its structure selected from the group consisting of copolymers of vinyl chloride and vinyl acetate, copolymers of vinyl chloride and (meth) acrylic acid ester, and vinyl chloride and acrylonitrile copolymer; Copolymers of vinyl chloride with diene compounds and unsaturated dicarboxylic acids or anhydrides thereof selected from the group consisting of copolymers of vinyl chloride and diethyl maleate, diethyl fumarate and maleic anhydride; Postchlorinated polymers and copolymers of vinyl chloride; Copolymers of vinyl chloride or vinylidene chloride with at least one member selected from the group consisting of unsaturated aldehydes, ketones, acrolein, crotonaldehydes, vinyl methyl ketones, vinyl methyl ethers, vinyl isobutyl ethers and similar compounds; Polymers of vinylidene chloride and vinyl chloride and other polymerizable compounds and copolymers thereof; Polymers of vinyl chloroacetate and dichlorodivinyl ether; Chlorinated polymers of chlorinated polymerizable esters of vinyl acetate, acrylic acid and α-substituted acrylic acid; Polymers of dichlorostyrene; Chlorinated rubber; Chlorinated polymers of ethylene; Polymers of chlorobutadiene and postchlorinated polymers; And vinyl chloride and copolymers thereof, but is not limited thereto.

The antioxidant oil dispersion is preferably 0.01 to 1.0 parts by weight based on 100 parts by weight of the vinyl chloride monomer in terms of improving the physical properties of the product and the efficiency of the antioxidant.

Hereinafter, the structure and effects of the present invention will be described in more detail with specific examples and comparative examples, but these examples are only intended to more clearly understand the present invention and are not intended to limit the scope of the present invention.

Example 1

An antioxidant oily dispersion was prepared by adding 200 g of Irganox 245 (C ₃₄ H ₅₀ O ₈ ) as an antioxidant to 200 g of cetyl alcohol as a dispersion medium, followed by stirring at a temperature of 120 ° C. for uniform mixing. The particle size of the antioxidant in the dispersion was 5 μm.

Example 2

An antioxidant oily dispersion was prepared in the same manner as in Example 1, except that 150 g and 50 g of Irganox 245 and DSTDP (Dilauryl thiodipropionate) represented by Chemical Formula 5 were used as antioxidants. The particle size of the antioxidant in the dispersion was 5 μm.

Example 3

An antioxidant oily dispersion was prepared in the same manner as in Example 2, except that Irganox 2450 (C ₃₄ H ₅₀ O ₈ ) was used instead of Irganox 245 represented by Chemical Formula 5. The particle size of the antioxidant in the dispersion was 5 μm.

Examples 4 to 6

Examples 4 to 6 in the same manner as in Examples 1 to 3, except that glycerol, lauryl alcohol, and epoxidized soybean oil were used instead of cetyl alcohol as the dispersion medium of Examples 1 to 3, respectively. Was prepared.

The particle size of the antioxidant in the dispersion liquid according to Examples 4 to 6 was 5 µm, 5 µm and 10 µm, respectively.

Examples 7-12

The polyvinyl chloride polymer was prepared by adding 0.04 parts by weight of each antioxidant oil-based dispersion prepared according to Examples 1 to 6 with respect to 100 parts by weight of the vinyl chloride monomer, and other additives.

Comparative Example 1

Polyvinyl chloride was prepared by adding 0.04 parts by weight of an antioxidant Irganox 2450 (C ₃₄ H ₅₀ O ₈ ) represented by Formula 6 and other additives based on 100 parts by weight of vinyl chloride monomer.

Comparative Example 2

Polyvinyl chloride was prepared by adding 0.03 parts by weight, 0.01 parts by weight, and other additives of the antioxidants Irganox 2450 and DSTDP represented by Formula 6 to 100 parts by weight of the vinyl chloride monomer, respectively.

Comparative Example 3

Polyvinyl chloride was prepared by adding 0.04 part by weight of cetyl alcohol, and other additives based on 100 parts by weight of vinyl chloride monomer.

The physical properties of the polyvinyl chloride polymer prepared in Examples and Comparative Examples were evaluated in the following manner.

Processing whiteness

5 parts by weight of a compound stabilizer (WPS-60) was added to 100 parts by weight of the produced vinyl chloride resin, 1.5 parts by weight of a processing aid (PA-822), 2 parts by weight of titanium oxide were added, and an organic tin acid-based thermal stabilizer (MT800) was added. A weight part was charged and roll-milled at 180 ° C. for 3 minutes to obtain a sheet. Thereafter, the Nippon Denshoku's NR-3000 instrument measured the whiteness (W.I) value at this time.

Whiteness Example 7 65 Example 8 72 Example 9 71 Example 10 69 Example 11 71 Example 12 73 Comparative Example 1 50 Comparative Example 2 55 Comparative Example 3 48

As shown in the results of Table 1 above, the comparative example in which the whiteness of the embodiment using the antioxidant type oil dispersion, in which the phenolic antioxidant or the thioester antioxidant was mixed alone or mixed and dispersed in the dispersion medium, the antioxidant and the dispersion were separately added. It can be seen that compared to the improvement. Therefore, when using the antioxidant oil-based dispersion as in the present invention it can be confirmed that the dispersibility is maintained until the end of the reaction.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is clearly understood that the same is by way of illustration and example only and is not to be taken by way of limitation, The present invention may be modified in various ways. Therefore, modifications of the embodiments of the present invention will not depart from the scope of the present invention.

Claims (12)

The at least one antioxidant selected from a phenolic antioxidant and a thioester antioxidant is a monohydric alcohol or a polyhydric alcohol having 1 to 18 carbon atoms, and at least one oily dispersion medium selected from epoxidized fatty acids or fatty acid esters. Antioxidant oil-based dispersion, characterized in that the dispersion medium is dispersed in a weight ratio of 1: 100 to 5: 1. delete The antioxidant oily dispersion according to claim 1, wherein the particle size of the antioxidant is 0.1 to 10 mu m. The antioxidant oily dispersion according to claim 1, wherein the phenolic antioxidant is selected from compounds represented by the following Chemical Formulas 1-2. Formula 1

In Formula 1, R 1 is an alkyl group of C ₁ to C ₂₀ , (2)

In Formula 2, R2 is C ₁ to C ₂₀ Alkyl group, or

Wherein n is an integer of 1 to 4, and R3 is a material having a structure of Formula 3 below. (3)

The antioxidant oily dispersion according to claim 1, wherein the thioester-based antioxidant is selected from compounds represented by the following Chemical Formula 4. Formula 4

Wherein x is an integer of 12-18. According to claim 1, wherein the monohydric alcohol or polyhydric alcohol having 1 to 18 carbon atoms is methanol, ethanol, propanol, butanol, butanediol, pentanol, heptanol, hexanol, 1,6-hexanediol, n-octanol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, cetyl alcohol, lauryl alcohol (n-dodecyl alcohol), stearyl alcohol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, pentaerythrite Lithol, dipentaerythritol, tripentaerythritol, bistrimethylolpropane, trimethylolethane, bistrimethylolethane, trimethylolpropane, bistrimethylolpropane, sorbitol, maltite, isomaltite, lactite, lysine , Mannitol, xylite, inosite, lactose, leucross, paltinite, tetramethylolcyclohexanol, tetramethylolcyclopentanol, tetramethylolcyclopyranol, glycerol, diglycerol, polyglycerol, thiodiggle Antioxidant oily dispersion, characterized in that at least one selected from the group consisting of riserol and condensates thereof. The method of claim 1, wherein the epoxidized fatty acid or fatty acid ester is epoxidized soybean oil, rapeseed oil, epoxidized polybutadiene, epoxidized linseed oil, epoxidized fish oil, epoxidized castor oil, epoxidized sunflower seed oil, carbon number 1 Antioxidant oily dispersion, characterized in that at least one member selected from the group consisting of oleate of 8 to 8, stearate of 1 to 8 carbon atoms, and diglycidyl ether of bisphenol A. One or more antioxidants selected from phenolic antioxidants and thioester antioxidants, monohydric alcohols or polyhydric alcohols having 1 to 18 carbon atoms, and at least one oily dispersion medium selected from epoxidized fatty acids or fatty acid esters are used at 80 to 150 ° C. Process for producing an antioxidant oily dispersion comprising the step of mixing at a temperature of. 9. The method of claim 8, wherein the antioxidant: dispersion medium is mixed in a weight ratio of 1: 100 to 5: 1. A vinyl chloride-based resin polymer prepared from the antioxidant oily dispersion according to any one of claims 1 and 3. The vinyl chloride-based resin polymer according to claim 10, wherein the vinyl chloride-based resin polymer is prepared from a composition containing 0.01 to 1.0 parts by weight of an antioxidant oily dispersion based on 100 parts by weight of a vinyl chloride-based monomer. The method of claim 10, wherein the vinyl chloride resin is a polymer of vinyl chloride; A vinyl resin having a vinyl chloride unit in its structure selected from the group consisting of copolymers of vinyl chloride and vinyl acetate, copolymers of vinyl chloride and (meth) acrylic acid ester, and vinyl chloride and acrylonitrile copolymer; Copolymers of vinyl chloride with diene compounds and unsaturated dicarboxylic acids or anhydrides thereof selected from the group consisting of copolymers of vinyl chloride and diethyl maleate, diethyl fumarate and maleic anhydride; Postchlorinated polymers and copolymers of vinyl chloride; Copolymers of vinyl chloride or vinylidene chloride with at least one member selected from the group consisting of unsaturated aldehydes, ketones, acrolein, crotonaldehydes, vinyl methyl ketones, vinyl methyl ethers, vinyl isobutyl ethers and similar compounds; Polymers of vinylidene chloride and vinyl chloride and other polymerizable compounds and copolymers thereof; Polymers of vinyl chloroacetate and dichlorodivinyl ether; Chlorinated polymers of chlorinated polymerizable esters of vinyl acetate, acrylic acid and α-substituted acrylic acid; Polymers of dichlorostyrene; Chlorinated rubber; Chlorinated polymers of ethylene; Polymers of chlorobutadiene and postchlorinated polymers; And at least one member selected from the group consisting of vinyl chloride and copolymers thereof.