JP2012007184A - Vinyl chloride resin plasticizer containing phthalate diester - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a vinyl chloride resin plasticizer having excellent low temperature resistance, heat resistance, and flexibility.SOLUTION: A phthalate diester used for the vinyl chloride resin plasticizer is obtained by an esterification reaction of an aliphatic saturated alcohol and a phthalic acid or its anhydride. The aliphatic saturated alcohol is prepared by a production process comprising: a process (1) for producing a 9C aldehyde by a hydroformylation reaction of 1-octene, carbon monoxide and hydrogen; and a process (2) for hydrogenating the 9C aldehyde to reduce it to the alcohol.

Description

The present invention relates to a plasticizer for a vinyl chloride resin containing a phthalic acid diester.

The vinyl chloride resin gives various performances including flexibility and lowers the processing temperature at the time of molding such as extrusion and calendering, and a plasticizer is added for the purpose of facilitating the processing. It is usually used as a vinyl resin composition.

The performance required for the plasticizer used in such a vinyl chloride resin composition includes various properties such as flexibility, cold resistance, heat resistance, and electrical characteristics when the composition is used as a molded product. Typical plasticizers used in such vinyl chloride resin compositions include higher alkyl esters of dibasic acids such as phthalic acid esters and adipic acid esters, among which di-2-ethylhexyl phthalate (hereinafter, "DOP") and diisononyl phthalate (hereinafter referred to as "DINP") are widely used because they have a good balance of physical properties such as flexibility, but there are further demands for cold resistance and heat resistance. When it was high, it was difficult to respond.

An object of the present invention is to provide a plasticizer for a vinyl chloride resin, which can solve the above-described problems, has excellent cold resistance and heat resistance, and has good flexibility.

In view of the present situation, the present inventors have conducted extensive studies to solve the above problems, and as a result, a phthalic acid diester obtained by esterifying a specific aliphatic saturated alcohol and phthalic acid or an anhydride thereof, The present inventors have found that it is a plasticizer for vinyl chloride resin having excellent cold resistance and heat resistance and good flexibility, and has completed the present invention.

That is, the present invention provides the following plasticizer for vinyl chloride resin.

[Claim 1]
A phthalic acid diester obtained by esterifying phthalic acid or an anhydride thereof and an aliphatic saturated alcohol having 9 carbon atoms,
The aliphatic saturated alcohol comprises (1) 1-octene, a step of producing a aldehyde having 9 carbon atoms by a hydroformylation reaction of carbon monoxide and hydrogen, and (2) hydrogenation of the aldehyde having 9 carbon atoms into an alcohol. A plasticizer for vinyl chloride resin containing a phthalic acid diester, which is an aliphatic saturated alcohol produced by a production process comprising a reduction step.

The plasticizer for a vinyl chloride resin of the present invention can be used as a plasticizer for a vinyl chloride resin having excellent cold resistance and heat resistance and good flexibility.

<Plasticizer for vinyl chloride resin>
The phthalic acid diester (hereinafter referred to as “the present ester”) obtained by esterifying the phthalic acid or anhydride thereof according to the present invention with a specific aliphatic saturated alcohol having 9 carbon atoms is a predetermined acid component. And an alcohol component are obtained by esterification according to a conventional method, preferably in an inert gas atmosphere such as nitrogen, in the absence of a catalyst or in the presence of a catalyst.

[C9 aliphatic saturated alcohol]
The aliphatic saturated alcohol having 9 carbon atoms used in the present invention includes (1) 1-octene, a step of producing an aldehyde having 9 carbons by hydroformylation reaction of carbon monoxide and hydrogen, and (2) an aldehyde having 9 carbon atoms. It is manufactured by a manufacturing process comprising a step of hydrogenating and reducing to alcohol.

In the hydroformylation reaction which is the step (1), for example, an aldehyde having 9 carbon atoms can be produced by reacting 1-octene, carbon monoxide and hydrogen in the presence of a cobalt catalyst or a rhodium catalyst.

The hydrogenation in the step (2) can be reduced to an alcohol by hydrogenating an aldehyde having 9 carbon atoms by hydrogen pressurization in the presence of a noble metal catalyst such as a nickel catalyst or a palladium catalyst. .

Specific examples of the aliphatic saturated alcohol having 9 carbon atoms obtained in the above process include lineball 9 (trade name, manufactured by Shell Chemicals).

Linebol 9 is a mixture of about 70% or more of n-nonanol and about 30% or less of 2-methyloctanol.

[Esterification reaction]
In the esterification reaction of the alcohol with phthalic acid or its anhydride, the alcohol is, for example, 2.00 equivalents to 5.00 equivalents, preferably 2.01 with respect to 1 equivalent of phthalic acid or its anhydride. It is preferable to use about 2.02 equivalents to 2.50 equivalents, particularly about 2.02 equivalents to 2.50 equivalents.

Examples of the catalyst used in the esterification reaction include mineral acids, organic acids, Lewis acids, and alkali metals. More specifically, examples of the mineral acid include sulfuric acid, hydrochloric acid, and phosphoric acid, examples of the organic acid include p-toluenesulfonic acid and methanesulfonic acid, and examples of the Lewis acid include aluminum derivatives, tin derivatives, and titanium. Derivatives, lead derivatives, and zinc derivatives are exemplified. Examples of alkali metals include sodium alkoxide, potassium alkoxide, sodium hydroxide, potassium hydroxide, and the like, and one or more of these can be used in combination. .

Among them, p-toluenesulfonic acid, tetraalkyl titanate having 3 to 8 carbon atoms, titanium oxide, titanium hydroxide, sodium alkoxide having 1 to 4 carbon atoms, sodium hydroxide, tin oxide having 3 to 12 carbon atoms, tin oxide, Tin hydroxide, zinc oxide, zinc hydroxide, lead oxide, lead hydroxide, aluminum oxide and aluminum hydroxide are particularly preferred. The amount used thereof is, for example, 0.01 wt% to 5.0 wt%, preferably 0.02 wt% to 4.0 wt%, particularly with respect to the total weight of the acid component and alcohol component that are raw materials for ester synthesis. It is preferable to use 0.03% to 3.0% by weight.

Examples of the esterification temperature include 100 ° C to 230 ° C, and the reaction is usually completed in 3 hours to 30 hours.

In esterification, it is possible to use water entraining agents such as benzene, toluene, xylene and cyclohexane in order to promote distillation of water produced by the reaction.

  Also, when oxygenated organic compounds such as oxides, peroxides, and carbonyl compounds are produced by oxidative degradation of raw materials, produced esters and organic solvents (water entraining agents) during the esterification reaction, the heat resistance, weather resistance, etc. are adversely affected. For this reason, it is desirable to carry out the reaction under normal or reduced pressure in an inert gas atmosphere such as nitrogen gas or in an inert gas stream. After completion of the esterification reaction, excess raw material is distilled off under reduced pressure or normal pressure.

The present ester obtained by the above esterification method may be subsequently purified by liquid-liquid extraction, vacuum distillation, adsorption purification, or the like, if necessary.

Examples of the adsorbent used for the adsorption purification include activated carbon, activated clay, activated alumina, hydrotalcite, silica gel, silica alumina, zeolite, magnesia, calcia, and diatomaceous earth.

The ester obtained by the above method can be blended with a vinyl chloride resin as a plasticizer to form a resin composition.

[Vinyl chloride resin]
The vinyl chloride resin used in the present invention is a homopolymer of vinyl chloride or vinylidene chloride and a copolymer of vinyl chloride or vinylidene chloride, and its production method is carried out by a conventionally known polymerization method. In the case of a vinyl resin, a suspension polymerization method can be mentioned in the presence of an oil-soluble polymerization catalyst, and in the case of a vinyl chloride paste resin, an emulsion polymerization method can be mentioned in an aqueous medium in the presence of a water-soluble polymerization catalyst. The degree of polymerization of these vinyl chloride resins is usually 700 to 5000, preferably 800 to 3500, and more preferably 900 to 3000. If the degree of polymerization is too low, heat resistance and the like are lowered, and if it is too high, moldability tends to be lowered.

In the case of a copolymer, for example, ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1- C2-C30 α-olefins such as tridecene, 1-tetradecene, acrylic acid and its esters, methacrylic acid and its esters, maleic acid and its esters, vinyl acetate, vinyl propionate, alkyl vinyl ether, etc. Copolymers of vinyl compounds, polyfunctional monomers such as diallyl phthalate, and mixtures thereof with vinyl chloride monomers, ethylene-acrylate copolymers such as ethylene-ethyl acrylate copolymers, ethylene-methacrylate esters Polymer, ethylene-vinyl acetate copolymer (EVA), chlorinated polyester Rene, butyl rubber, cross-linked acrylic rubber, polyurethane, butadiene-styrene-methyl methacrylate copolymer (MBS), butadiene-acrylonitrile- (α-methyl) styrene copolymer (ABS), styrene-butadiene copolymer, polyethylene, poly Examples thereof include a graft copolymer obtained by grafting a vinyl chloride monomer onto methyl methacrylate and a mixture thereof.

[Vinyl chloride resin composition]
The content of the present ester in the vinyl chloride resin composition is appropriately selected according to its use, but is usually 1 to 100 parts by weight, preferably 5 to 100 parts by weight of the vinyl chloride resin. 50 parts by weight. If it is less than 1 part by weight, it is difficult to obtain a predetermined plasticizing effect, and if it exceeds 100 parts by weight, bleeding on the surface of the molded product is severe, which is not preferable in either case. However, when adding a filler etc. with respect to said vinyl chloride resin composition, since the filler itself absorbs oil, the said plasticizer can be mix | blended exceeding said range. For example, when 100 parts by weight of calcium carbonate as a filler is blended with 100 parts by weight of a vinyl chloride resin, about 1 to 500 parts by weight of the plasticizer can be blended.

In the vinyl chloride resin composition, other known esters can be used in combination with the present ester. If necessary, additives such as a colorant, a processing aid, a filler, an antioxidant (anti-aging agent), an ultraviolet absorber, or an antistatic agent can be blended.

Known esters that can be used in combination with the present ester include, for example, dibutyl phthalate (DBP), di-2-ethylhexyl phthalate (DOP), diisononyl phthalate (DINP), diisodecyl phthalate (DIDP), and phthalic acid. Phthalic acid esters such as diundecyl (DUP), di-2-ethylhexyl adipate (DOA), diisononyl adipate (DINA), adipic acid esters such as diisodecyl adipate (DIDA), and trimellitic acid tri-2-ethylhexyl (TOTM), trimellitic acid esters such as triisodecyl trimellitic acid (TITM), and phosphoric acid esters such as tri-2-ethylhexyl phosphate (TOP) and tricresyl phosphate (TCP). The amount of the plasticizer used is preferably within 5% by weight of the total amount of the plasticizer.

Examples of the colorant include carbon black, lead sulfide, white carbon, titanium white, lithopone, benigara, antimony sulfide, chrome yellow, chrome green, cobalt blue, and molybdenum orange. Further, the blending amount of the colorant with respect to 100 parts by weight of the vinyl chloride resin is about 1 to 100 parts by weight.

Examples of the processing aid include liquid paraffin, polyethylene wax, stearic acid, stearic acid amide, ethylene bis stearic acid amide, butyl stearate, calcium stearate and the like. The blending amount of the processing aid with respect to 100 parts by weight of the vinyl chloride resin is about 0.1 to 20 parts by weight.

Fillers include metal oxides such as calcium carbonate, silica, alumina, clay, talc, diatomaceous earth, ferrite, fibers and powders such as glass, carbon, metal, glass spheres, graphite, aluminum hydroxide, barium sulfate, oxidation Examples include magnesium, magnesium carbonate, magnesium silicate, calcium silicate, and the like. Moreover, the compounding quantity of the filler with respect to 100 weight part of vinyl chloride-type resin is about 1-100 weight part.

Antioxidants include 2,6-di-tert-butylphenol, tetrakis [methylene-3- (3,5-tert-butyl-4-hydroxyphenol) propionate] methane, 2-hydroxy-4-methoxybenzophenone, and the like. Sulfur compounds such as phenolic compounds, alkyl disulfides, thiodipropionic acid esters, benzothiazoles, trisnonylphenyl phosphite, diphenylisodecyl phosphite, triphenyl phosphite, tris (2,4-di-tert-butylphenyl) ) Phosphite compounds such as phosphite, organometallic compounds such as zinc dialkyldithiophosphate and zinc diaryldithiophosphate. The blending amount of the antioxidant with respect to 100 parts by weight of the vinyl chloride resin is about 0.2 to 20 parts by weight.

Examples of ultraviolet absorbers include salicylate compounds such as phenyl salicylate and p-tert-butylphenyl salicylate, benzophenone compounds such as 2-hydroxy-4-n-octoxybenzophenone and 2-hydroxy-4-n-methoxybenzophenone, In addition to benzotriazole compounds such as 5-methyl-1H-benzotriazole and 1-dioctylaminomethylbenzotriazole, cyanoacrylate compounds are exemplified. Moreover, the compounding quantity of the ultraviolet absorber with respect to 100 weight part of vinyl chloride-type resin is about 0.1-10 weight part.

Antistatic agents include alkylsulfonate type, alkyl ether carboxylic acid type or dialkyl sulfosuccinate type anionic antistatic agents, non-ionic antistatic agents such as polyethylene glycol derivatives, sorbitan derivatives, diethanolamine derivatives, and alkylamide amine types. And quaternary ammonium salts such as alkyldimethylbenzyl type, cationic antistatic agents such as alkylpyridinium type organic acid salt or hydrochloride, and amphoteric antistatic agents such as alkylbetaine type and alkylimidazoline type. The blending amount of the antistatic agent with respect to 100 parts by weight of the vinyl chloride resin is about 0.1 to 10 parts by weight.

The vinyl chloride resin composition is prepared by mixing the ester, vinyl chloride resin, and various additives as necessary with a stirrer such as a mortar mixer, Henschel mixer, Banbury mixer, ribbon blender, etc. It can be a mixed powder of products.

On the other hand, the present ester, vinyl chloride resin and various additives as required are mixed with a kneader such as a conical twin screw extruder, a parallel twin screw extruder, a single screw extruder, a kneader type kneader, or a roll kneader. A pellet-like vinyl chloride resin composition can also be obtained by melt molding.

Furthermore, kneading machines such as the present ester, vinyl chloride paste resin and various additives as necessary, for example, conical twin screw extruder, parallel twin screw extruder, single screw extruder, kneader type kneader, roll kneader A paste-like vinyl chloride resin composition can also be obtained by melt molding.

[Vinyl chloride resin molding]
The compounded powder or pellet of the vinyl chloride resin composition obtained by the above method is melt-molded using a conventionally known method such as extrusion molding, injection molding, calendar molding, press molding, blow molding, etc. Can be formed into a shape.

On the other hand, the vinyl chloride paste resin composition can be molded into a desired shape by molding using a conventionally known method such as spread molding, dipping molding, gravure molding, or screen processing.

The shape of the molded body is not particularly limited, but, for example, rod-shaped, sheet-shaped, film-shaped, plate-shaped, cylindrical, circular, elliptical, etc., or special shapes such as toys, ornaments, such as stars, A polygonal shape is illustrated.

The molded body thus obtained includes pipes such as water pipes, automobile underbody coats, various leathers, agricultural transparent films, food packaging films, electric wire coatings, various foamed products, general transparent hoses, refrigerator gaskets, packings. It is useful for wallpaper, flooring, boots, toys, erasers, etc.

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. In addition, the symbol of the compound in an Example and a comparative example, and the measurement of each characteristic are as follows.

(1) Preparation of vinyl chloride press sheet 100 parts by weight of vinyl chloride resin (straight, degree of polymerization 1050, trade name “Zest1000Z”, manufactured by Shin Daiichi PVC Co., Ltd.), calcium stearate (manufactured by Nacalai Tesque) Zinc stearate (manufactured by Nacalai Tesque) was blended in 0.3 and 0.2 parts by weight, stirred and mixed with a mortar mixer, added with 50 parts by weight of a plasticizer, and mixed and handled until uniform. It was set as the composition. This resin composition is melt-kneaded for 4 minutes at 160 to 166 ° C. using two 5 × 12 inch rolls, followed by press molding at 162 to 168 ° C. for 10 minutes to produce a press sheet having a thickness of about 1 mm. did.

(2) Evaluation of physical properties of ester The ester obtained in the production example was analyzed by the following method.
Ester value: Measured according to JIS K-0070 (1992).
Acid value: measured in accordance with JIS K-0070 (1992).
Hue: Measured according to JIS K-4101 (Hazen) (1995).

[Evaluation of physical properties of resin]
(3) Tensile test: Based on JIS K-6723 (1995), 100% modulus, breaking strength, and breaking elongation of a press sheet are measured. The smaller the value of 100% modulus, the better the flexibility.

(4) Cold resistance test: Measured according to JIS K-6773 (1999) using a Crushberg tester. The higher the absolute value, the higher the cold resistance.

(5) Heat resistance test: Based on evaluation of volatile loss and sheet coloring.
a) Volatilization loss: The weight change after heating the press sheet at 170 ° C. for 60 minutes and 120 minutes in a gear oven is measured. The smaller the number, the higher the heat resistance.
b) Sheet coloring: The degree of coloring after heating the press sheet at 170 ° C. for 30 minutes and 60 minutes in a gear oven is visually evaluated in four stages.
A: Not colored, B: Slightly colored, B: Colored, X: Strongly colored.

[Production Example 1]
Into a 2 L four-necked flask equipped with a thermometer, decanter, stirring blade and reflux condenser, 493 g (3.3 mol) of phthalic dianhydride, 1112 g of aliphatic saturated alcohol (manufactured by Shell Chemicals: Lineball 9) (7 0.7 mol), 140 g of xylene, and 3.7 g of p-toluenesulfonic acid as an esterification catalyst were added, and the esterification reaction was carried out at a reaction temperature of 130 ° C. The reaction was carried out until the acid value of the reaction solution reached 0.5 mgKOH / g while refluxing xylene and alcohol under reduced pressure to remove the produced water out of the system. After completion of the reaction, unreacted alcohol was distilled out of the system under reduced pressure, and then neutralized, washed with water and dehydrated according to a conventional method to obtain 1223 g of the desired phthalic acid diester.
The obtained DL9P had an ester value of 267 mgKOH / g, an acid value of 0.01 mgKOH / g, and a hue of 10.

[Example 1]
A vinyl chloride press sheet was prepared using the phthalic acid diester obtained in Production Example 1, and a tensile test, a cold resistance test, and a heat resistance test were measured. The obtained results are shown in Table 1.

[Comparative Example 1]
A vinyl chloride press sheet was prepared using di-2-ethylhexyl phthalate (manufactured by Shin Nippon Chemical Co., Ltd .: Sunsizer DOP), and a tensile test, a cold resistance test, and a heat resistance test were measured. The obtained results are shown in Table 1.

[Comparative Example 2]
A vinyl chloride press sheet was prepared using diisononyl phthalate (manufactured by Shin Nippon Rika Co., Ltd .: Sansosizer DINP), and a tensile test, a cold resistance test, and a heat resistance test were measured. The obtained results are shown in Table 1.

The phthalic acid diester of the present invention can be used as a plasticizer for a vinyl chloride resin having excellent cold resistance and heat resistance and good flexibility.

Claims (1)

A phthalic acid diester obtained by esterifying phthalic acid or an anhydride thereof and an aliphatic saturated alcohol having 9 carbon atoms,
The aliphatic saturated alcohol comprises (1) 1-octene, a step of producing a aldehyde having 9 carbon atoms by a hydroformylation reaction of carbon monoxide and hydrogen, and (2) hydrogenation of the aldehyde having 9 carbon atoms into an alcohol. A plasticizer for vinyl chloride resin containing a phthalic acid diester, which is an aliphatic saturated alcohol produced by a production process comprising a reduction step.