阅读说明：本技术 环保增塑剂以及包含该环保增塑剂的树脂组合物 (Environment-friendly plasticizer and resin composition containing same ) 是由 李东权 裵真莹 金导玄 金荣云 卢庚显 金赫峻 于 2018-09-28 设计创作，主要内容包括：本发明提供包含具有以下化学式的结构的化合物的环保增塑剂以及包含该环保增塑剂的树脂组合物。<Image he="162" wi="480" file="1.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>在上述化学式中,R<Sub>1</Sub>及R<Sub>2</Sub>分别独立地表示取代或未取代的C<Sub>2</Sub>-C<Sub>20</Sub>脂肪族烷基,或者取代或未取代的C<Sub>4</Sub>-C<Sub>10</Sub>环烷基。(in the above chemical formula, R 1 and R 2 each independently represent a substituted or unsubstituted C 2 -C 20 aliphatic alkyl group, or a substituted or unsubstituted C 4 -C 10 cycloalkyl group.)

1. A plasticizer characterized by comprising a compound having a structure represented by the following chemical formula (1),

In the above chemical formula, R₁And R₂Each independently represents substituted or unsubstituted C₂-C₂₀Aliphatic alkyl, or substituted or unsubstituted C₄-C₁₀A cycloalkyl group.

2. The plasticizer according to claim 1, wherein said-CH₂-O(C＝O)-R₁And the above-mentioned-CH₂-O(C＝O)-R₂Bonded at the opposite para position centered on the cyclohexane ring.

3. The plasticizer according to claim 1, wherein the compound of formula (1) is a compound of formula (2) or a compound of formula (3),

4. A plasticizer according to claim 1, wherein R is₁And said R₂In (C)₂-C₂₀When the aliphatic alkyl group is substituted and when C₄-C₁₀When the cycloalkyl group is substituted, the substituent is selected from the group consisting of₁-C₆Alkyl radical, C₄-C₁₀Cycloalkyl, halogen, amino, nitro, sulfone, sulfate and hydroxyl.

5. A plasticizer according to claim 1, wherein R is₁And said R₂Each being substituted C₄-C₁₀An aliphatic alkyl group, and 1 ethyl group is substituted in the main chain portion of the alkyl group adjacent to the ester structure.

6. The plasticizer according to claim 1, wherein the compound of the formula (1) is a compound of the following formula (4)

7. A resin composition comprising the compound of formula (1) according to claim 1 as a plasticizer and a polymer resin.

8. The resin composition of claim 7, wherein the polymer resin is polyvinyl chloride.

9. Resin composition according to claim 7, characterized in that it further comprises fillers and/or stabilizers.

Technical Field

The present invention relates to an environmentally friendly plasticizer 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, a phthalate-based product is mainly used, but since phthalate-series plasticizers are suspected to have endocrine disruptors or potential carcinogenic factors, isophthalate-series or terephthalate-series plasticizers and adipic acid (adipate) -series plasticizers containing no aromatic compound have been recently developed and used.

However, the isophthalate series or the terephthalate series are still based on the phthalate (phthalate) structure, and thus it is difficult to judge that the potential hazard is completely removed.

Therefore, although a product in which a benzene ring is hydrogenated from a phthalate ester structure into a cyclohexane ring and a product based on a non-cyclic compound are developed and used, there are problems in that the production cost is high and physical properties are deteriorated as compared with conventional plasticizers.

Disclosure of Invention

The present invention has been made to solve the problems of the prior art and the technical problems required in the past as described above.

As a result of intensive studies and various experiments, the inventors of the present invention have developed a novel ester compound as a plasticizer by reacting a cyclohexane-based diol with a carboxylic acid as described below, and have confirmed that such an ester compound not only sufficiently exhibits physical properties required for a plasticizer but also does not adversely affect the human body at all, thereby completing the present invention.

the environment-friendly plasticizer according to the present invention comprises a compound having a structure represented by the following chemical formula (1).

In the above chemical formula, R₁And R₂Each independently represents substituted or unsubstituted C₂-C₂₀Aliphatic alkyl, or substituted or unsubstituted C₄-C₁₀A cycloalkyl group.

In the plasticizer according to the present invention, the basic structure of the compound of the above chemical formula (1) is formed of a ring structure of cyclohexane, and thus, the plasticizer is not harmful to not only the human body but also the environment, and has better physical properties than conventional plasticizers.

In one embodiment, -CH₂-O(C＝O)-R₁Can be reacted with-CH₂-O(C＝O)-R₂Bonded to the opposite para (para) position centered on the cyclohexane ring. such-CH₂-O(C＝O)-R₁and-CH₂-O(C＝O)-R₂May be the same or different.

In one embodiment, the compound of formula (1) may be a compound of formula (2) or a compound of formula (3).

In the above-mentioned R₁And the above R₂Are respectively C₂-C₂₀In the case of an aliphatic alkyl group having 3 or more carbon atoms, the alkyl group is a linear alkyl groupAnd also contains branched alkyl groups. And may be C₄-C₁₀A substituted cycloalkyl structure.

In the above-mentioned R₁and the above R₂In (C)₂-C₂₀When the aliphatic alkyl group is substituted and when C₄-C₁₀When cycloalkyl is substituted, the substituents may be selected from the group consisting of C₁-C₆Alkyl radical, C₄-C₁₀Cycloalkyl, halogen, amino, nitro, sulfone, sulfate and hydroxyl.

In a preferred embodiment, when C₂-C₂₀When the aliphatic alkyl group is substituted and when C₄-C₁₀The substituent when the cycloalkyl group is substituted may be C₁-C₆An alkyl group. More preferably, R₁And R₂May be C which may be substituted respectively₄-C₁₀Aliphatic alkyl groups, and 1 ethyl group may be substituted at an alkyl main chain portion (moiey) adjacent to an ester structure (-O (C ═ O) -), and in particular, a compound of the following chemical formula (4) is preferable.

As a result of experimental confirmation by the inventors of the present invention, when the compound of the above chemical formula (4) is used as a plasticizer, surprisingly, the cold-resistant property (cool-resistance property) of the material to which the plasticizer is added is remarkably excellent and shows a low softening temperature (softening temperature) as compared with the case where the compound of the following chemical formula (5) having a similar structure is used as a plasticizer, and it is confirmed that the physical properties of the material can be sufficiently exerted even at a low temperature. The material having low cold resistance property has soft property at normal temperature and becomes hard in physical property at low temperature, thereby losing the originally desired soft property and being easily broken even with a small impact. Therefore, among the plasticizers added to the material in order to impart plastic properties, the plasticizer provides the material with excellent cold resistance properties, which may be a great advantage.

Without limiting the scope of protection for interpreting the claims of the invention, it can be surmised that: the reason why the compound of formula (4) can exert the above-described special effects is that the inclusion of a substituted ethyl group in the alkyl main chain portion adjacent to the ester structure increases the disorder of the arrangement of the polymer in the plasticizer-added material, and can impart high flexibility and elongation even at low temperatures.

Thus, when the plasticizer of the present invention is synthesized by a reaction between a cyclohexane-based diol and a carboxylic acid as described below, the compound of formula (4) uses 2-ethylhexanoic acid (2-ethyl hexanoic acid) as the carboxylic acid, and the 2-ethylhexyl (2-ethyl hexyl) structure of this carboxylic acid is considered to be the most preferable alkyl group in terms of improvement of disorder, reduction of polymer filling efficiency, increase of amorphous properties, and the like for the purpose of improving cold-resistant characteristics, as compared to other alkyl groups.

Therefore, although the present invention proposes the compound of formula (4) as the most preferable plasticizer, even at the above C₂-C₂₀Aliphatic alkyl group by C₁-C₆In the case of alkyl substitution, for example, a compound of the formula (5) or the like in which a plurality of methyl groups are substituted at adjacent sites is not included in the present invention in terms of cold resistance characteristics.

For example, as shown in the following reaction formula, the compound of the above chemical formula (1) may be synthesized by a dehydration esterification reaction of a cyclohexane-based diol and a carboxylic acid.

In the above reaction formula, in order to simplify the expression of the reaction formula, in the chemical formula (1), R corresponds to₁And R₂In the same manner, the site of (A) is represented by R.

The conditions for the above reaction were as follows: adding a diol and a carboxylic acid to an organic solvent such as toluene, and after adding a catalyst such as p-toluenesulfonic acid (p-toluene sulfonic acid), gradually heating to the boiling point of the above organic solvent at a temperature of 100 ℃ or higher, which is the boiling point of water.

Diols based on the above cyclohexane are well known in the art, and for example, as shown in the following reaction formula, various types of the above carboxylic acids are currently commercially available, and can be produced by oxidizing para-xylene (para-xylene) separated in a crude oil distillation process to obtain terephthalic acid (terephthalic acid) or dimethyl terephthalate (dimethyl terephthalate), and reducing these.

Further, the present invention provides a resin composition in which the above plasticizer is mixed 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 a preferred embodiment, the resin composition may include a compound of formula (4) as a plasticizer.

In some cases, known non-toxic plasticizer compounds other than the compound of the above chemical formula (1) may be used together, and in this case, the content range between each other may be determined according to the desired physical properties.

In one example, additives such as fillers, stabilizers, etc. may be further included in the resin composition, and may be included in an amount of 1 to 350 parts by weight, relative to 100 parts by weight of the polymer resin.

The above filler is not particularly limited as long as it is a material known in the art to which the present invention pertains, and for example, 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 may be mentioned.

The stabilizer is not particularly limited as long as it is a material known in the art to which the present invention pertains, and may be, for example, a stearate or the like.

Effects of the invention

As described above, the plasticizer of the present invention has physical properties higher than those of conventional plasticizers, and has an effect of being harmless to both human body and environment because it does not contain an aromatic ring in its basic structure. In particular, the compound of formula (4) can significantly improve the cold-resistant property of the material it contains as a plasticizer.

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 and preparation of plasticizers