KR100651339B1 - Styrene derivative plasticizer composition for polyvinyl chloride resin, preparing method thereof, and polyvinyl chloride resin including the same - Google Patents

Abstract

The present invention relates to a styrene derivative plasticizer composition for polyvinyl chloride resin, a method for preparing the same, and a polyvinyl chloride resin including the same, and more particularly, to a styrene polyvinyl chloride resin comprising at least one styrene derivative. The present invention relates to a lene derivative plasticizer composition, a method for preparing the same, and a polyvinyl chloride resin including the same. The styrene derivative plasticizer composition according to the present invention is used as a secondary plasticizer when processing a polyvinyl chloride resin, especially a plastisol of a paste resin, so that the surface of the polyvinyl chloride resin having excellent viscosity stability without stickiness of the surface (sol) may be provided.

Polyvinyl chloride, secondary, plasticizer, styrene derivative, paste resin, plastisol

Description

Styrene derivative plasticizer composition for polyvinyl chloride resin, preparing method, and polyvinyl chloride resin including the same}

The present invention relates to a styrene derivative plasticizer composition for polyvinyl chloride resin, a method for preparing the same, and a polyvinyl chloride resin including the same. More specifically, the present invention relates to a second plasticizer in the processing of a paste polyvinyl chloride resin. The present invention relates to a styrene derivative plasticizer composition for polyvinyl chloride resin capable of providing a sol of a polyvinyl chloride resin having no viscosity and excellent viscosity stability, a method for preparing the same, and a polyvinyl chloride resin including the same.

Polyvinyl chloride resin (PVC) is suitable for a variety of applications by mixing various primary and secondary plasticizers with various additives such as ultraviolet and thermal stabilizers, fillers, and internal releasing agents. It is a general purpose resin using the product. Various applications of polyvinyl chloride include metal coatings, artificial leather, wallpaper, and gloves. In particular, the plasticizer added during the processing of the polyvinyl chloride resin is an essential additive for imparting various physical properties and functions such as processability, flexibility, surface tackiness to the polyvinyl chloride resin.

In particular, the plastisol of polyvinyl chloride is a sol used when manufacturing a film using a paste resin, and has an advantage of being easier to process than the case of using a straight resin. However, in the case of plastisols, it is important to add stable additives such as primary and secondary plasticizers and viscosity modifiers used to make the sol, which are processed according to the selection of the primary and secondary plasticizers used. The surface of a film etc. shows stickiness in many cases.

The plasticizer has the function of lowering the viscosity in the working process to give workability and the control of physical properties as a finished product after processing. Representative plasticizers used in the processing of the polyvinyl chloride resin include phthalates, adipates, trimellitates, and the like and most widely used plasticizers are phthalates. Dioctylphthalate (DOP) and dinonylphthalate (DINP) are also classified as primary plasticizers.

On the other hand, unlike primary plasticizers that remain in the product after processing to control their physical properties, they lower the viscosity during processing and do not remain after processing, so that they do not affect the properties such as tensile strength or elasticity in the product. It can be classified as a secondary plasticizer. Secondary plasticizers generally have lower plasticity than primary plasticizers, but have excellent properties of viscosity lowering ability and viscosity retention performance. In addition, the secondary plasticizer does not remain after the end of the processing can reduce the stickiness of the surface of the workpiece by reducing the amount of plasticizer in the workpiece.

In the prior art, mineral oil or hydrotreated hydrocarbon is often mixed with the primary plasticizer to prevent the above-mentioned viscosity decrease and stickiness of the processed product. (sol) has a disadvantage in that the workability is lowered. In addition, mineral oils have residual odor after processing due to impurities and aromatic hydrocarbons, and hydrogenated hydrocarbons can make the workpiece brittle. In addition, the phase separation may occur when the sol is left after the sol is prepared to have low compatibility with the polyvinyl chloride resin. Therefore, when the mineral oil or hydrogenated hydrocarbon is added to the primary plasticizer in order to reduce stickiness, dispersion stability is difficult, and thus long-term storage is difficult.

Accordingly, in the present invention, various studies have been conducted to solve the above-described problems of the prior art, and as a result, processing of a styrene derivative plasticizer composition including at least one styrene derivative is performed on polyvinyl chloride resin, in particular, plastisol. When used as a secondary plasticizer composition, a polyvinyl chloride resin product having excellent viscosity stability and no stickiness of the surface was obtained, and the present invention was completed based on this.

Accordingly, an object of the present invention is a styrene derivative plasticizer composition for polyvinyl chloride resin that can be added as a secondary plasticizer during processing of polyvinyl chloride resin to ensure stability of viscosity and to remove dispersibility and surface stickiness of the finished product. To provide.

Another object of the present invention is to provide a method for preparing a styrene derivative plasticizer composition for polyvinyl chloride resin that does not affect the physical properties of the plastisol without removing the catalyst separately.

Still another object of the present invention is to provide a polyvinyl chloride resin including the styrene derivative plasticizer composition, wherein the viscosity stabilization of the plastisol and the surface properties of the processed product are improved.

The styrene derivative plasticizer composition for polyvinyl chloride resin according to the present invention for achieving the above object, in the secondary plasticizer composition for polyvinyl chloride resin, comprises at least one compound of the styrene derivative represented by the following formula (1) do:

Wherein R ₁ and R ₂ are the same as or different from each other, or hydrogen or an alkyl group having 1 to 4 carbon atoms.

Method for producing a styrene derivative plasticizer composition for polyvinyl chloride resin according to the present invention for achieving the above another object is (a) 55 to 65% by weight of toluene or toluene / xylene mixture, 30 to 40% by weight of styrene, And 5-10% by weight of an N-N, N'-dialkylpyridinium-aluminum complex compound to react for 10 to 15 hours at a temperature of 0 to 20 ° C. to produce a styrene derivative. And (b) adding 10 to 20 parts by weight of polyoxyethylene to 100 parts by weight of the final reaction product and reacting at a temperature of 20 to 30 ° C. for 2 to 4 hours to form an aluminum-polyoxyethylene complex. do.

Polyvinyl chloride resin according to the present invention for achieving the above another object comprises the styrene derivative plasticizer composition.

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

As described above, in the present invention, it is used as a secondary plasticizer in the processing of the plastisol of the polyvinyl chloride resin, especially the paste resin, thereby providing a sol of the polyvinyl chloride resin having no viscosity and excellent viscosity stability. Provided are a styrene derivative plasticizer composition for polyvinyl chloride resin, a preparation method thereof, and a polyvinyl chloride resin including the same.

In the processing of plastisols of polyvinyl chloride resins, especially paste resins, the initial viscosity of the sol and the viscosity stability of the sol over time are important. For example, a plastisol processed product such as gloves and tarpaulins requires viscosity properties and appropriate viscosity control because the viscosity properties are different for each product.

The styrene derivative plasticizer composition for polyvinyl chloride resin of the present invention is added as a secondary plasticizer in order to secure stability of viscosity during processing of the polyvinyl chloride resin and to eliminate dispersibility and surface stickiness of the finished product, represented by the following Chemical Formula 1 At least one compound of the styrene derivatives                     

Formula 1

Wherein R ₁ and R ₂ are the same as or different from each other, hydrogen, methyl or an alkyl group having 2 to 4 carbon atoms.

Preferably, the plasticizer composition of the present invention comprises phenyl tolyl ethane, or a phenyl tolylethane / phenyl xylyl ethane mixture. More preferably, the plasticizer composition is 50 to 100% by weight of phenyltolylethane, and 0 to 50% by weight of phenylxylylethane.

In addition, the styrene derivative plasticizer composition of the present invention may further include -N, N'-dialkylpyridinium chloride and aluminum chloride-polyoxyethylene complex which are stable to heat and ultraviolet rays. At this time, the content of the chloride -N, N'-dialkylpyridinium is preferably 2 to 15 parts by weight based on 100 parts by weight of the styrene derivative, if the content is less than 2 parts by weight, the reaction rate is too slow during the synthesis of plasticizer If it exceeds 15 parts by weight, blooming by these catalyst reactants remaining in the plasticizer composition occurs. In addition, the content of the aluminum-polyoxyethylene complex compound is preferably 3 to 30 parts by weight based on 100 parts by weight of the styrene derivative, and when the content is less than 3 parts by weight, the catalyst is N-N, N'-dialkylpyridinium chloride. When the aluminum concentration in the aluminum complex is low, the reaction rate during synthesis is too slow, and when it exceeds 30 parts by weight, the concentration of the aluminum-polyoxyethylene complex remaining in the plasticizer is too high after the completion of the reaction, and blooming occurs.

Phenyltolylethane used in the present invention has excellent compatibility with polyvinyl chloride resins compared to hydrogenated hydrocarbons and mineral oils, and thus, even when a plastisol is prepared using a secondary plasticizer, phase separation does not occur, and is usually used as a primary plasticizer. Compared to dioctyl phthalate, it is excellent in viscosity lowering effect and viscosity stability. In particular, in the case of the mixture with phenylxylylethane and polyoxyethylene, phenylxylylethane is evaporated gradually even after evaporation of phenyltolylethane during gelation, and thus excellent foaming stability is also achieved.

When the styrene derivative plasticizer composition of the present invention is processed with the primary plasticizer commonly used in the art by adding to the polyvinyl chloride resin as a secondary plasticizer, only the primary plasticizer is used and mineral oil or hydrogenation in the primary plasticizer. Polyvinyl chloride resin having excellent physical properties in terms of viscosity stability and stickiness can be obtained as compared with the case where the hydrocarbon is further added.

The styrene derivative plasticizer composition of the present invention described above uses styrene and toluene or toluene / xylene as a raw material, -N, N'-dialkylpyridinium chloride as a catalyst, and polyoxyethylene for terminating the reaction. It is prepared according to the following method.

First, in a flask with a stirrer and a condenser, i) 55 to 65% by weight of toluene or toluene / xylene mixture, ii) 30 to 40% by weight of styrene, and i) -N, N'-dialkylpyridinium chloride. -5 to 10% by weight of the aluminum complex compound is added to react at 0 to 20 ℃ for 10 to 15 hours to produce a styrene derivative represented by the formula (1).

In this case, the amount of the N-N, N'-dialkylpyridinium-aluminum complex compound used is preferably 5 to 10% by weight, and if the amount is less than 5% by weight, the synthesis rate is too slow. Blooming shape by the catalyst conversion material in the inside occurs.

In addition, when the reaction temperature and the reaction time is out of the range, the production of oligomers by-products increases.

Then, unreacted toluene or toluene / xylene mixture in the reaction was removed by a vacuum pump, iv) 10 to 20 parts by weight of polyoxyethylene was added, and 20 to 30 to 100 parts by weight of the final reaction product. The reaction is carried out at a temperature of 2 hours for 2 to 4 hours to form an aluminum-polyoxyethylene complex.

The polyoxyethylene used in the present invention is further reacted for conversion of the catalyst and termination of the reaction. At this time, the weight average molecular weight of the polyoxyethylene is preferably from 60 to 600, if the molecular weight is less than 60, the storage stability by phase separation after the plastisol preparation is low, and if it exceeds 600, bleeding occurs in the gelling process do. In addition, the amount of the polyoxyethylene is preferably 10 to 20 parts by weight with respect to 100 parts by weight of the reaction product obtained in the final styrene derivative production reaction, when the amount is less than 10 parts by weight, the termination reaction of the catalyst is slow, 20 weight Exceeding the portion lowers the viscosity retention of the plastisol prepared using the plasticizer.

In the above process, the chloride-N, N'-dialkylpyridinium-aluminum of iii) serves as a catalyst, and the polyoxyethylene of iv) is used as a reaction terminator. Therefore, the polyoxyethylene is added to convert the -N, N'-dialkylpyridinium-aluminum catalyst used in the preparation of the plasticizer composition into a complex of polyoxyethylene to convert it into a stable material that does not affect the resin. There is an advantage that a plasticizer composition can be obtained that does not affect the physical properties of the plastisol without separately removing the catalyst after the preparation of the plasticizer composition.

On the other hand, the plasticizer composition comprising the aluminum-polyoxyethylene complex compound can be obtained by using only a styrene derivative through a purification process, for example, purification such as fractional distillation according to the purpose of use.

As described above, the styrene derivative plasticizer composition according to the present invention can be used as a secondary plasticizer when processing a polyvinyl chloride resin without a separate catalyst removal process, thereby providing a polyvinyl chloride resin having excellent viscosity stability without stickiness. have.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the scope of the present invention is not limited thereto.

Example 1

(a) Preparation of Styrene Derivative Plasticizer Composition

Toluene 60g, 6g of N-N, N'-dialkylpyridinium trichloride, 6g of styrene was added dropwise to a 3-neck 1L round flask equipped with a stirrer and a condenser. After synthesizing phenylethane, unreacted toluene was removed by decompression to 10mmHg, polyoxyethylene was added to 15 parts by weight with respect to 100 parts by weight of the reaction product, and the reaction was performed at room temperature for 3 hours to produce aluminum-polyoxyethylene The plasticizer composition containing a complex compound was obtained.

The composition ratio of this reaction product was 80 weight% of tolylphenylethane, 3-5 weight% of -N, N'- dialkylpyridinium chloride, and 15-18 weight% of the aluminum polyoxyethylene complex compound.

(b) Preparation of sol and film of polyvinyl chloride resin

In order to measure the physical properties of the styrene derivative mixture obtained in (a) as a plasticizer, standard specimens were prepared as follows.

That is, 50 parts by weight of dioctylphthalate and 15 parts by weight of the styrene derivative mixture obtained in (a) were added to 100 parts by weight of polyvinyl chloride resin (manufactured by LG Chemical Co., Ltd., product name LP090) as a plasticizer, and butyl tin maleate was stabilized. After adding 3 parts by weight of the furnace, the mixture was stirred at 2000 rpm for 15 minutes using a high speed mixer, and then degassed until a bubble was completely removed using a vacuum defoaming machine to prepare a sol. After applying the sol to the release paper or glass plate with a thickness of 50㎛ uniformly and then gelling for 3 minutes at 200 ℃, 5cm × 5cm square film specimen and 1cm Specimens of size square × 1 cm were prepared.

(c) property test

Initial variation of viscosity and viscosity over time was measured using the plastisol prepared in (b). Viscosities were compared using spindle 5 of the Brookfield viscometer (spindle No. 5) and measured at 10 rpm. The change in viscosity over time was measured at daily intervals while kept in a constant temperature bath at 25 ℃.

Discoloration test and stickiness were tested using square specimens. Discoloration after 500 hours left in the Weather-O-Meter, the degree of discoloration was analyzed by HunterLab's ColorQuest-II (ColorQuest-II).                     

The stickyness was expressed in mg / cm 2 by measuring the maximum load when the square specimen of 1 cm × 1 cm size was attached to the rectangular specimen stage and the upper probe bar using double-sided tape, stuck together, and detached.

The experimental results are shown in Table 1 below.

Example 2

(a) Preparation of Styrene Derivative Plasticizer Composition

The reaction raw material was carried out in the same manner as in Example 1 (a) except that a mixture of toluene and xylene (toluene / xylene = 3/1 weight ratio) was used instead of toluene.

(b) Preparation of sol and film of polyvinyl chloride resin

Except for using the styrene derivative plasticizer composition obtained in the above (a) was carried out in the same manner as in Example 1 (b).

(c) property test

Physical properties were tested in the same manner as in Example 1 (c), and the results are shown in Table 1 below.

Example 3

(a) Preparation of Styrene Derivative Plasticizer Composition

In the same manner as in Example 1 (a) to prepare a plasticizer composition, and then washed five times with water and fractional distillation to prepare a plasticizer composition containing only phenyltolylethane.

(b) Preparation of sol and film of polyvinyl chloride resin

Except for using the styrene derivative plasticizer composition obtained in the above (a) was carried out in the same manner as in Example 1 (b).

(c) property test

Physical properties were tested in the same manner as in Example 1 (c), and the results are shown in Table 1 below.

Example 4

(a) Preparation of Styrene Derivative Plasticizer Composition

Example 2 (a) was carried out in the same manner to prepare a plasticizer composition, and then washed five times with water and fractional distillation to prepare a plasticizer composition in which phenyltolylethane and phenylxylylethane were mixed in a weight ratio of 3: 1.

(b) Preparation of sol and film of polyvinyl chloride resin

Except for using the styrene derivative plasticizer composition obtained in the above (a) was carried out in the same manner as in Example 1 (b).

(c) property test

Physical properties were tested in the same manner as in Example 1 (c), and the results are shown in Table 1 below.

Comparative Example 1

(a) Preparation of sol and film of polyvinyl chloride resin

The same procedure as in Example 1 (b) was carried out except that 50 parts by weight of dioctylphthalate and 65 parts by weight of dioctylphthalate were used instead of 15 parts by weight of the styrene derivative mixture obtained in Example 1 (a).                     

(b) Property test

Physical properties were tested in the same manner as in Example 1 (c), and the results are shown in Table 1 below.

Comparative Example 2

(a) Preparation of sol and film of polyvinyl chloride resin

The same procedure as in Example 1 (b) was carried out except that 15 parts by weight of hydrogenated hydrocarbon (trade name YK-D100) was used instead of 15 parts by weight of the styrene derivative mixture obtained in Example 1 (a).

(b) Property test

Physical properties were tested in the same manner as in Example 1 (c), and the results are shown in Table 1 below.

Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Initial viscosity (cp) 4139 3922 3892 3542 6954 4319 Viscosity after 3 days (cp) 5821 4979 4531 4316 10318 7862 Discoloration (500 hours, YI) 10 10 10 10 10 15 Stickiness (mg / ㎠) <0.1 <0.1 0.1 0.3 12.1 0.5 Hardness B B B B 3B HB

* The stickiness was measured by putting two specimens of 1 cm x 1 cm into one another and measuring the force for removing them.

* Viscosity was measured at 25 rpm using spindle No. 4.

Color fading was tested using a weatherometer and the yellowness index was measured.                     

As shown in Table 1, it can be seen that the initial viscosity lowering ability of the sol prepared according to the method of Examples 1 to 4 of the present invention is excellent compared to the results of Comparative Examples 1 to 2, and particularly excellent in change over time Even if it stored for a long time in a sol state, it was confirmed that there was little viscosity change and showed easy workability. In addition, the plasticizer composition prepared according to the method of Examples 1 to 4 has good compatibility with the resin, so that phase separation does not occur during storage of the sol, such as kerosene or hydrogenated petroleum oil. there was.

In addition, it can be seen that the films produced according to the methods of Examples 1 to 4 had excellent flexibility and no discoloration without surface stickiness of the films prepared compared to Comparative Examples 1 to 2.

Therefore, when styrene derivatives prepared according to the method of the present invention are used in-istu or purified to be used as secondary plasticizers in the processing of polyvinyl chloride resins, only the first plasticizer, dioctylphthalate, is used. Compared with the case where the primary plasticizer is used by further adding mineral oil or hydrogenated hydrocarbon, it is possible to obtain a film having excellent initial viscosity reducing ability, viscosity stability, and non-sticky physical properties.

The styrene derivative plasticizer composition according to the present invention may be used as a secondary plasticizer when processing polyvinyl chloride resin, thereby providing a low polyvinyl chloride resin product having low initial viscosity, excellent viscosity stability, and no color change.

Claims (8)

In the secondary plasticizer composition for polyvinyl chloride resin, Styrene derivative plasticizer composition for polyvinyl chloride resin, characterized in that it comprises at least one compound of the styrene derivative represented by the formula (1): Formula 1

Wherein R ₁ and R ₂ are the same as or different from each other, or hydrogen or an alkyl group having 1 to 4 carbon atoms. The composition of claim 1 wherein the plasticizer composition comprises phenyltolylethane or a phenyltolylethane / phenylxylylethane mixture. The composition of claim 2, wherein the plasticizer composition comprises 50 to 100% by weight of phenyltolylethane and 0 to 50% by weight of phenylxylylethane. According to claim 1, wherein the plasticizer composition is 2 to 15 parts by weight of -N, N'- dialkylpyridinium chloride and 3 to 30 parts by weight of the aluminum-polyoxyethylene complex with respect to 100 parts by weight of the styrene derivative. A composition comprising a. (a) 55 to 65% by weight of toluene or toluene / xylene mixture, 30 to 40% by weight of styrene, and 5 to 10% by weight of -N, N'-dialkylpyridinium-aluminum complex; Reacting at a temperature of 20 ° C. for 10 to 15 hours to produce a styrene derivative; And (b) adding 10 to 20 parts by weight of polyoxyethylene to 100 parts by weight of the final reaction product and reacting at a temperature of 20 to 30 ° C. for 2 to 4 hours to form an aluminum-polyoxyethylene complex; Method for producing a styrene derivative plasticizer composition for polyvinyl chloride resin according to any one of claims 1 to 4, characterized in that it comprises a. The method of claim 5, wherein the method further comprises the step of removing the unreacted toluene or the toluene / xylene mixture under reduced pressure with a vacuum pump in step (a). The method according to claim 5, wherein the polyoxyethylene has a weight average molecular weight of 60 to 600. Polyvinyl chloride resin containing the plasticizer composition of any one of Claims 1-4.