KR100455692B1 - Polyester plasticizer for vinyl resin - Google Patents

Abstract

The present invention provides a vinyl resin containing a polyvinyl chloride resin and a halogen element in order to provide excellent processability and flexibility, as well as excellent migration resistance to ABS resin, spill resistance to water and oil, volatility, and the like. It relates to the polyester plasticizer used, it is a polyester plasticizer represented by the following formula (1) and (2);

Formula 1

Formula 2

In the above formulas, D ₁ is an alkyl group having 4 to 20 carbon atoms, D ₂ is an alkyl group having 3 to 19 carbon atoms, R ₁ is an alkyl group having 3 to 10 carbon atoms, and R ₂ is 1,3-butylene glycol, 2- Alkyl groups derived from glycols having 4 carbon atoms such as methyl-1,3-propylene glycol, 1,4-butylene glycol, and the like.

Description

Polyester plasticizer for vinyl resins {Polyester plasticizer for vinyl resin}

The present invention relates to a polyester plasticizer for vinyl resins. More specifically, the present invention is a migration resistance to a vinyl resin containing a polyvinyl chloride resin (PVC resin) and a halogen element to ABS resin (acrylonitrile-butadien-styrene resin), oil and water outflow into oil The present invention relates to a polyester plasticizer which is used for imparting excellent workability, volatility, and the like, as well as processability and flexibility.

Phthalic acid-based plasticizers used to give flexibility and processability to polyvinyl chloride resins have disadvantages of migration resistance, oil resistance and volatility, so they are made of resins similar to those of polyvinyl chloride resins and polyvinyl chloride resins. There was a problem of promoting the phenomenon of aging.

U.S. Pat. ) Is a plasticizer to prevent shrinkage due to the spill resistance of the plasticizer when dry cleaning with a solvent containing chlorine.

U.S. Pat.

U.S. Patent No. 4,876,304 describes a polymeric plasticizer having properties suitable for gaskets made of polyvinyl chloride resins by varying acid and alcohol as the main raw materials.

U. S. Patent No. 5,576, 367 also describes a polymeric plasticizer that does not damage the metal alkyd coating by altering the main raw materials, acids and alcohols.

That is, the progress of the development of the polymeric plasticizer is based on the change of the main raw materials according to the purpose of using the plasticizer.

Accordingly, the present inventors improve not only the properties of the conventional polymer plasticizers such as the resistance to migration, the oil resistance and the volatility, but also the disadvantages of the processability and the flexibility provided by the conventional polymer plasticizers, and the polymer plasticizers are mainly used. The present invention has been completed to develop a polyester plasticizer for vinyl resins suitable for application to polyvinyl chloride resin gaskets as well as to other products made of vinyl resins containing polyvinyl chloride resins and halogen elements. It was.

An object of the present invention is to provide a polyvinyl chloride resin and a vinyl-based resin containing a halogen element not only excellent in migration resistance to ABS resin, outflow resistance to water and oil, resistance to volatility, but also to processability and flexibility. It is to provide a polyester plasticizer for vinyl-based resin used to.

Polyester plasticizer for vinyl resins according to the present invention is a polyester plasticizer represented by the following formula (1) and (2);

In the above formulas, D ₁ is an alkyl group having 4 to 20 carbon atoms, D ₂ is an alkyl group having 3 to 19 carbon atoms, R ₁ is an alkyl group having 3 to 10 carbon atoms, and R ₂ is 1,3-butylene glycol, 2- Alkyl groups derived from glycols having 4 carbon atoms such as methyl-1,3-propylene glycol, 1,4-butylene glycol, and the like.

Hereinafter, the present invention will be described in detail with reference to specific examples.

Polyester plasticizer for vinyl resins according to the present invention is a polyester plasticizer represented by the following formula (1) and (2);

Formula 1

Formula 2

In the above formulas, D ₁ is an alkyl group having 4 to 20 carbon atoms, D ₂ is an alkyl group having 3 to 19 carbon atoms, R ₁ is an alkyl group having 3 to 10 carbon atoms, and R ₂ is 1,3-butylene glycol, 2- Alkyl groups derived from glycols having 4 carbon atoms such as methyl-1,3-propylene glycol, 1,4-butylene glycol, and the like. Among the glycols corresponding to R ₂ , 1,3-butylene glycol and 2-methyl-1,3-propylene glycol are branched glycols (branched glycols), which may occupy 80 to 100 mol% of all glycols. . The use ratio of 1,3-butylene glycol and 2-methyl-1,3-propylene glycol in the side chain glycol is in a molar ratio of 0.5: 0.5 to 0.9: 0.1. 1,4-butylene glycol is a straight chain glycol (unbranched glycol), and the straight chain glycol is used to improve the hardness of the plasticizer. In the present invention, the hardness of the plasticizer can be improved by using up to 20 mol% in total glycol. In the prior art, linear glycols were used to make the polyester reaction smoother.

The use of saturated monoacid and saturated monoalcohol was used by introducing the concept of solubility parameter. Organic matters are more compatible as the value of the hydrogen solubility parameter of the solubility parameter is closer. When saturated monoacid and saturated monoalcohol are used, the compatibility can be theoretically improved by approaching the hydrogen bond solubility parameter value of the polyvinyl chloride resin than when not used.

The polyester plasticizer according to the present invention has a molecular weight (GPC; gel permeation chromatography measurement) of 1,000 to 8,000 and an acid value of 2 mgKOH / g or less.

The dicarboxylic acid used in the synthesis of the polyester plasticizer according to the present invention may be selected from the group consisting of aliphatic or aromatic dicarboxylic acids having 3 to 10 carbon atoms or anhydrides thereof. In addition, the fatty acids used in the synthesis of the polyester plasticizer according to the present invention may be selected from the group consisting of branched or straight chain fatty acids as saturated fatty acids. Preferably, the fatty acid may be adipic acid, azelic acid, sebacic acid, glutaric acid, sbelic acid, dodecandioic acid. , Phthalic acid, isophthalic acid, terephthalic acid, anhydrides of these acids, or mixtures of two or more thereof.

The terminal stopper introduced into the terminal during the synthesis of the polyester plasticizer according to the present invention may be selected from the group consisting of saturated monoacid having 4 to 20 carbon atoms, or saturated monoalcohol having 4 to 20 carbon atoms. Preferred saturated monoacids include 2-ethylhexanoic acid, lauric acid, palmitic acid, stearic acid, fatty acid or two or more of them. It may be selected from the group consisting of a mixture. Preferred saturated monoalcohols are 2-ethylhexanol, isooctanol, n-octanol, isodecyl alcohol and n-decanol. ) Or a mixture of two or more thereof.

In the reaction of the polyester plasticizer, the process of using the terminal blocker, saturated monoacid and saturated monoalcohol is as follows. Saturated monoacid and saturated monoalcohol are not used, and only dicarboxylic acid and diol are put into a reactor and reacted to obtain a desired molecular weight. When the acid value of the reactor becomes 2 mgKOH / g or less, the reaction is stopped and the molecular weight by the hydroxyl value (OH value) is calculated. Saturated monoacid or saturated monoalcohol corresponding to about 1 mole of the number of moles corresponding to the molecular weight calculated by the hydroxyl value is added to the reactor together with dicarboxylic acid and diol and a second reaction is performed. Saturated monoacids and saturated monoalcohols are terminal blockers. The molecular weight of the reaction product containing the saturated monoacid and the saturated monoalcohol is less than that of the reaction product consisting of only dicarboxylic acid and diol. That is, in order to prepare a reaction product corresponding to the desired molecular weight, the reaction ratio of dicarboxylic acid and diol should be adjusted to a reduced amount of diol input compared to the existing input amount.

The preparation of the polyester plasticizer is carried out according to the typical ester reaction. Dicarboxylic acids, diols and terminal terminators (saturated monoacids or saturated monoalcohols) are introduced into a reactor equipped with a nitrogen tube and a refluxable distillation trap under a nitrogen atmosphere. After slowly raising the internal temperature of the reactor to about 150 ℃, the ester reaction proceeds for 2 to 9 hours in the temperature range of 150 to 240 ℃ to remove the water produced in the refluxable distillation trap. The ester reaction can be promoted by using an appropriate catalyst.

Catalysts for promoting the ester reaction include phosphoric acid, sulfuric acid, p-toluene sulfonic acid, antimony oxide, dibutyltin acetate, dibutyltin oxide, It may be selected from the group consisting of monobutyltin oxide (monobutyltin oxide) or a mixture of two or more thereof.

If the reaction no longer proceeds, the reaction proceeds while removing water remaining in the reactor while refluxing by adding an inert solvent such as toluene or xylene. When the acid value of the reactor is 2 mgKOH / g or less, the polyester plasticizer according to the present invention can be obtained by stopping the reaction and vacuum drying the reaction product for about 10 to 14 hours.

The polyester plasticizer according to the present invention can be used for a vinyl resin containing a polyvinyl chloride resin and a halogen element. Typical examples thereof include vinyl chloride including vinyl acetate, vinyl chloride including vinyl butyrate, vinyl chloride including vinyl propionate, and methyl methacrylate. vinyl chloride comprising (methylmethacrylate), vinyl chloride comprising vinylidene chloride, vinyl chloride copolymer comprising two or more other monomers, or a mixture of two or more thereof. have.

The polyester plasticizer of the present invention may be used in an amount of 20 to 110 phr, more preferably 30 to 80 phr, based on 100 phr of a polyvinyl chloride resin and a part of hundred resin (part per hundred resin) containing a halogen element. Can be.

The polyester plasticizer according to the present invention can be used together with other conventional additives added during the processing of polyvinyl chloride resin. Other conventional additives added during the processing of polyvinyl chloride resins include oxidative stabilizers, thermal stabilizers, light stabilizers, lubricants, flame retardants, fillers, pigments, and the like, which are well known to those skilled in the art to be commercially available. It can be understood that.

Hereinafter, preferred embodiments and comparative examples of the present invention will be described.

The following examples are intended to illustrate the invention and should not be understood as limiting the scope of the invention.

Example 1

Into a 2 L flask equipped with a nitrogen tube and a refluxable distillation trap, 660 g of adipic acid, 331.5 g of 1,3-butylene glycol, 110.5 g of 2-methyl-1,3-propanediol, and 170 g of saturated fatty acid were added thereto. As the catalyst, 0.01 g of dibutyltin oxide was added, and the temperature was primarily raised from room temperature to 150 ° C, and the reaction proceeded while gradually raising the temperature from 150 ° C to 240 ° C. The reaction proceeded for 7 hours while removing the water produced during the reaction from the nitrogen tube and the refluxable distillation trap. If the reaction does not proceed at 240 ° C., the reaction proceeds for about 15 hours while introducing an inert solvent such as toluene and xylene to reflux. The reaction was stopped when the acid value became 2 mgKOH / g, and the inert solvent was removed by vacuum drying at a pressure of 160 mmHg or less for at least 12 hours at room temperature.

Example 2

Example 1 except adding 660 g of adipic acid, 265.2 g of 1,3-butylene glycol, 88.4 g of 2-methyl-1,3-propanediol, 88.4 g of 1,4-butanediol, and 170 g of saturated fatty acid Was performed in the same manner.

Example 3

Aside from adding 660 g of adipic acid, 265.2 g of 1,3-butylene glycol, 88.4 g of 2-methyl-1,3-propanediol, 88.4 g of 1,4-butanediol, and 56 g of 2-ethylhexanol, It carried out similarly to Example 1.

Comparative Example 1

Adipic acid was carried out in the same manner as in Example 1 except adding 660g, 1,2-propylene glycol 374g.

Comparative Example 2

As a commercialized plasticizer known to those skilled in the art, commercially available plasticizers of phthalate series, trioctyltrimellitate, a trade name of LG Chem, was used.

Experimental Example

100 phr of polyvinyl chloride resin, 50 phr of the polymerized polyester plasticizers in the above examples and comparative examples, 2 phr of Ba-Zn-based stabilizer (trade name 'KBZ-381P', manufactured by Kolon Emulsion Co., Ltd., Korea) as a heat stabilizer After mixing and extrusion process between 100 to 110 ℃ to produce a pellet, and then injection molding at an average temperature of 150 ℃ to obtain a specimen having a thickness of about 2㎜ to tensile strength, elongation, hardness, water outflow, oil outflow And the test resistance to ABS resins, and the results are shown in Table 1 below.

Tensile strength and elongation were measured according to ASTM D 412 and ASTM D 638, and hardness was measured according to ASTM D 2240. The oil and water resistance test for water and oil prepared a specimen of 2.5 * 5.1 cm, and the oil and water resistance test for water was maintained for about 48 hours in water at a temperature of 70 ° C., and the weight deviation of the test specimen before and after the test was measured. The oil resistance test for the oil was carried out by maintaining the oil at room temperature for about 24 hours, and then calculating the weight deviation of the specimen before and after the test. In the resistance test of ABS resin, four specimens of size 2.5 * 2.5㎝ were prepared and laminated in the form of sandwich on the ABS resin plate, and then the weight of about 4㎏ was put on and kept in the oven at 80 ℃ for 240 hours. After the test, the weight deviation of the test piece before and after the test was also performed.

division Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 ¹⁾ Tensile Strength (㎏f / ㎠) 185 176 177 207.6 170 % Elongation 295 275 277 250 304 Shore A 95 94 94 98 95 Water runoff (loss%) 0.53 0.5 0.51 1.78 0.14 Oil spillability (% loss) 0 0 0 0 7.41 ABS performance (loss%) 0.54 0.6 0.55 0.84 1.3 * 1) TOTM: trioctyltrimellitate (phthalate type plasticizer)

As shown in Table 1, the polyester plasticizer according to the present invention has a water outflow, oil outflow compared to the conventional polyester plasticizer as shown in Comparative Example 1 and the conventional phthalate plasticizers as shown in Comparative Example 2 It was found to be excellent in the resistance and ABS resistance, and the hardness and the like were improved.

Therefore, according to the present invention, the basic physical properties such as tensile strength and elongation are not lowered while improving the hardness flexibility of the conventional polyester plasticizer, and in particular, water outflow, oil outflow and ABS migration resistance are excellent. It is effective to provide a polyester plasticizer suitable for use in vinyl resins containing polyvinyl chloride resins and halogen elements.

Although the present invention has been described in detail only with respect to the described embodiments, it will be apparent to those skilled in the art that various modifications and variations are possible within the technical scope of the present invention, and such modifications and modifications are within the scope of the appended claims.

Claims (3)

Polyester plasticizer represented by the following formula (1) and formula (2); Formula 1 Formula 2 In the above formulas, D ₁ is an alkyl group having 4 to 20 carbon atoms, D ₂ is an alkyl group having 3 to 19 carbon atoms, R ₁ is an alkyl group having 3 to 10 carbon atoms, and R ₂ is 1,3-butylene glycol, 2- Alkyl groups derived from glycols having 4 carbon atoms such as methyl-1,3-propylene glycol, 1,4-butylene glycol, and the like. The method of claim 1, Among the glycols corresponding to R ₂ , side chain glycols (eg, branched glycols) such as 1,3-butylene glycol and 2-methyl-1,3-propylene glycol are composed of 80 to 100 mol% of all glycols. The said polyester plasticizer. The method of claim 1, Among the glycols corresponding to R ₂ , the side chain glycol (branched glycol) such as 1,3-butylene glycol and 2-methyl-1,3-propylene glycol is used in a molar ratio of 0.5: 0.5 to 0.9: 0.1. The polyester plasticizer, characterized in that consisting of.