阅读说明：本技术 基于环己烷二甲醇沥青的增塑剂及包含该增塑剂的树脂组合物 (Plasticizer based on cyclohexanedimethanol asphalt and resin composition comprising same ) 是由 李东权 裵真莹 卢庚显 金赫峻 于 2018-09-28 设计创作，主要内容包括：本发明提供基于环己烷二甲醇沥青的增塑剂及包含该增塑剂的树脂组合物,上述增塑剂的特征在于,包含在借助对苯二甲酸二甲酯(dimethyl terephthalate,DMT)的氢化(hydrogenation)反应来制备环己烷二甲醇(cyclohexanedimethanol,CHDM)的过程中产生的环己烷二甲醇沥青和羧酸化合物的酯化(esterification)反应物。(The present invention provides a plasticizer based on cyclohexanedimethanol asphalt and a resin composition comprising the plasticizer, wherein the plasticizer is characterized by comprising an esterification (esterification) reactant of cyclohexanedimethanol asphalt and a carboxylic acid compound generated in the process of producing Cyclohexanedimethanol (CHDM) by a hydrogenation (hydrogenation) reaction of dimethyl terephthalate (DMT).)

1. A plasticizer characterized by comprising esterification reactants of cyclohexanedimethanol pitch and a carboxylic acid compound produced in the production of cyclohexanedimethanol by hydrogenation of dimethyl terephthalate.

2. A plasticizer according to claim 1, wherein said cyclohexanedimethanol pitch comprises the composition shown in the following Table,

﹡ GC%: analytical content of gas chromatograph.

3. The plasticizer according to claim 1, wherein the carboxylic acid compound is a compound of the following chemical formula (1),

RCO₂H (1)

in the above formula, R is substituted or unsubstituted C₂-C₂₀Aliphatic alkyl, or substituted or unsubstituted C₄-C₁₀A cycloalkyl group.

4. The plasticizer according to claim 3, wherein said R is substituted C₄-C₁₀Aliphatic alkyl, and 1 ethyl is substituted in the alkyl backbone portion adjacent to the carboxylic acid structure (HO (C ═ O) -).

5. The plasticizer according to claim 3, wherein the carboxylic acid compound is a compound of the following chemical formula (2)

6. The plasticizer according to claim 1, wherein the plasticizer comprises 5 to 10% of the compound of the following chemical formula (3), 25 to 35% of the compound of the following chemical formula (4), and 55 to 65% of the compound of the following chemical formula (5),

in the chemical formula, R₁And R₂Each independently of the other is as defined for R in said formula (1).

7. The plasticizer according to claim 6, wherein the plasticizer is a compound of the following chemical formula (3a), a compound of the following chemical formula (4a), and a mixture of compounds of the following chemical formula (5a),

8. a resin composition comprising the plasticizer of claim 1 and a polymer resin.

Technical Field

The present invention relates to a plasticizer based on cyclohexanedimethanol asphalt and a resin composition comprising the same.

Background

Plasticizers (plastisizers) are substances that affect the thermal and mechanical properties of polymer resins by being added to various consumer products, medical supplies, packaging materials, automobile parts, toys, and the like.

A typical plasticizer in the past is a phthalate-based compound obtained by an esterification (esterification) reaction, which has the effect of being added to various plastic materials to lower the melting temperature or viscosity of the materials, facilitate molding and processing, and lower the softening temperature of the plastic, thereby imparting flexibility to the plastic.

As such a plasticizer, phthalate plasticizers have been widely used in products. However, phthalate-based plasticizers have a side effect of being released from products based on polymer resins, adversely affecting human tissues. That is, it is reported that metabolites of phthalate plasticizers are potential carcinogenic substances and have an influence on the liver, pituitary gland, and the like. Thus, some countries are implementing or enforcing regulations that restrict the use of products containing phthalate plasticizers for medical and pediatric products.

For this reason, in 2004, DINCH (1,2-Cyclohexane dicarboxylic acid diisononyl ester, 1, 2-Cyclohexane-dicarboxylic acid diisononyl ester) was developed by BASF as a plasticizer of non-phthalate series and is suitable for medical devices or toys for children or food packaging materials. When 1, 2-cyclohexane-dicarboxylic acid diisononyl ester forms a plastisol, low viscosity is exhibited, and mechanical properties such as elongation, tensile strength, and hardness also show data similar to that of conventional DEHP.

However, in the DINCH production process, diisononyl phthalate undergoes hydrogenation at high temperature and high pressure, and it is reported that a trace amount of phthalate remains in the process and affects the human body. Therefore, there is a need for alternative plasticizers that are not at all harmful to the human body.

In addition, most of the plasticizers currently available on the market are expensive materials, including DINCH and the like. The reason why the price of the plasticizer is high is mainly because the price of the production raw material is high. The expensive plasticizer causes an increase in manufacturing cost for products to which these are added.

As a result, there is a high necessity for a novel plasticizer that is harmless to the human body and can be prepared at low cost.

Disclosure of Invention

The present invention has been made to solve the above-mentioned problems occurring in the prior art and the problems required in the past.

As a result of intensive studies and various experiments, the inventors of the present invention have developed a non-phthalate plasticizer using, as a raw material, pitch produced when Cyclohexanedimethanol (CHDM) is produced, and have confirmed that such a plasticizer can sufficiently exhibit physical properties required for a general plasticizer without adversely affecting the human body at all and can be produced at low cost, thereby completing the present invention.

Therefore, the plasticizer according to the present invention is characterized by comprising an esterification (esterification) reactant of CHDM pitch and a carboxylic acid compound, which are generated as byproducts in the preparation of Cyclohexanedimethanol (CHDM) by a hydrogenation reaction of dimethyl terephthalate (DMT).

CHDM is a compound mostly used as a raw material for synthesis of polyesters, and is generally produced by hydrogenation of DMT, and pitch including CHDM and other diol compounds is produced during the production of such CHDM, that is, CHDM pitch is produced. Such CHDM bitumen is very inexpensive compared to CHDM and is used primarily as a combustion fuel.

The inventors of the present invention confirmed that: by using the CHDM asphalt as a raw material, an extremely inexpensive plasticizer can be produced, which is not only excellent in physical properties comparable to those of conventional commercially available plasticizers, but also harmless to the human body because it is based on a non-phthalate compound.

More specifically, in the process for preparing CHDM, first, DMT is subjected to a primary hydrogenation reaction to be converted into dimethyl 1,4-cyclohexanedicarboxylate (DMCD), and DMCD is converted into CHDM by a secondary hydrogenation reaction. The cis/trans (cis/trans) ratio of CHDM varies depending on the catalyst, and is prepared at a ratio of 30:70 (cis: trans)) using a copper chromite (copper chromite) catalyst in a process suitable for industrial use. This hydrogenation reaction can be roughly represented by the following reaction formula.

Since the higher the trans-cyclohexanedimethanol (trans-CHDM) ratio, the higher the melting point of the produced polyester resin, thereby improving the heat resistance, the trans (trans) ratio is generally increased to about 90% by the isomerization reaction and the dissolution recrystallization step using a metal alkoxide catalyst.

In the preparation of such CHDM, pitch is formed which has a diol compound in the form of dimer (dimer) in which CHDM is bonded to each other as a main component. CHDM asphalt is a liquid having a viscosity of 300cps to 500cps at normal temperature.

The main components of CHDM bitumen are as follows, and other diol compounds or metal catalysts may also be included in the range of about 5% (GC%).

﹡ GC%: analysis content of gas chromatograph (gas chromatograph)

In one embodiment, the carboxylic acid compound reacted with CHDM asphalt to prepare the plasticizer of the present invention may be a compound of the following chemical formula (1).

RCO₂H (1)

In the above formula, R is substituted or unsubstituted C₂-C₂₀Aliphatic alkyl, or substituted or unsubstituted C₄-C₁₀A cycloalkyl group.

In the case of the above substitution, for example, the substituent may be selected from the group consisting of C₁-C₆Alkyl radical, C₄-C₁₀Cycloalkyl, halogen, amino, nitro, sulfone, sulfate and hydroxyPreferably, may be C₁-C₆An alkyl group.

In a preferred embodiment, R is substituted C₄-C₁₀Aliphatic alkyl groups, and 1 ethyl group is substituted at an alkyl main chain portion (moiety) adjacent to a carboxylic acid structure (HO (C ═ O) -), and particularly, a compound of the following chemical formula (2) is preferable.

The 2-ethylhexyl (2-ethylhexyl) structure of the above carboxylic acid compound is considered to be the optimal alkyl group because the above structure can improve characteristics as a plasticizer by increasing disorder, decreasing polymer filling efficiency, and increasing amorphous compared to other alkyl groups.

Various carboxylic acid compounds are currently commercially available for use in the present invention.

In one example, the plasticizer of the present invention may include 5% to 10% of the compound of the following chemical formula (3), 25% to 35% of the compound of the following chemical formula (4), and 55% to 65% of the compound of the following chemical formula (5) (based on the content of gas chromatography).

In the above chemical formula, R₁And R₂Each independently of the other, is the same as the definition of R in the formula (1).

Preferably, the plasticizer of the present invention may be a mixture of the compound of the following chemical formula (3a), the compound of the following chemical formula (4a), and the compound of the following chemical formula (5 a).

In the present invention, the esterification reaction between CHDM asphalt and a carboxylic acid compound can be carried out, for example, by adding CHDM asphalt and a carboxylic acid compound to an organic solvent such as toluene, and adding a catalyst such as p-toluenesulfonic acid (p-toluene sulfonic acid), and then gradually heating to the boiling point of the organic solvent at a temperature of 100 ℃ or higher, which is the boiling point of water.

The present invention also provides a resin composition obtained by mixing the plasticizer with a polymer resin.

The kind of the polymer resin is not particularly limited, but preferably, polyvinyl chloride may be used.

In the resin composition, the plasticizer may be contained in an amount of 5 parts by weight to 100 parts by weight, specifically, 10 parts by weight to 30 parts by weight, relative to 100 parts by weight of the polymer resin.

In some cases, known nontoxic plasticizer compounds other than the plasticizer of the present invention may be used together, and in this case, the content ranges from each other may be determined according to the desired physical properties.

In one embodiment, additives such as fillers, stabilizers, etc. may be further included in the resin composition, and the content of the additives may be 1 to 350 parts by weight with respect to 100 parts by weight of the polymer resin.

The filler is not particularly limited as long as it is a material known in the art to which the present invention pertains, and examples thereof include barium sulfate, calcium hydroxide, aluminum hydroxide, magnesium hydroxide, aluminum silicate, magnesium silicate, calcium carbonate, magnesium carbonate, titanium dioxide, magnesium oxide, silica, talc, and the like.

The stabilizer is not particularly limited as long as it is a material known in the field of the present invention, and may be, for example, a stearate.

Effects of the invention

As described above, the plasticizer of the present invention is very inexpensive because it is produced using the pitch produced in the production of CHDM as a raw material, does not adversely affect the human body because it is a non-phthalate plasticizer, and has the effect of sufficiently exhibiting physical properties required for general plasticizers.

Detailed Description

The present invention will be described below with reference to examples thereof for better understanding, and the scope of the present invention is not limited thereto.

Preparation of the plasticizer