KR20080065829A - Polymer plasticizer having migration-resistant property, preparation method thereof and polymer resin composition containing the same - Google Patents

Abstract

A polymer plasticizer is provided to ensure a small heating loss, good viscosity and extraction resistance, and excellent migration resistance without deteriorating mechanical properties such as hardness, elongation, and tensile strength of polymer resins. A polymer plasticizer includes at least one selected from the group comprising linear polyester compounds represented by the following formula 1 and linear polyester compounds represented by the following formula 2. In the formulae, each of R1, R1', R2, and R2' is a C3-18 alkyl group, R3s are a C2-12 alkylene group or arylene group and are different from one another within one molecule, R4s are a C3-18 branched alkylene group and are different from one another within one molecule, and R5s are a C3-28 branched alkylene group containing an ester group and are different from one another in one molecule.

Description

Polymeric plasticizer with excellent migration resistance, a method for producing the same, and a polymer resin composition comprising the same {POLYMER PLASTICIZER HAVING MIGRATION-RESISTANT PROPERTY, PREPARATION METHOD THEREOF AND POLYMER RESIN COMPOSITION CONTAINING THE SAME}

The present invention relates to a polymer plasticizer having excellent migration resistance, a manufacturing method thereof, and a polymer resin composition comprising the same, and more particularly, when used as an additive in various polymer resins, the amount of heating loss is low, and the viscosity and extraction resistance are excellent. , A polymer plasticizer which does not lower the mechanical properties such as hardness, elongation and tensile strength of the polymer resin, and particularly provides a polymer resin having excellent migration resistance and excellent heat resistance and chemical resistance, and a method of preparing the polymer resin and a polymer resin composition comprising the same. It is about.

Plastics, which are used in various fields of modern life and provide convenience of life, are applied to various household goods or industrial goods by molding by various processing methods.

Among the plastics, in particular, polyvinyl chloride resin is a general-purpose resin that can be molded by various processing methods such as extrusion molding, injection molding, calendering, and the like. Pipes, electric wires, electric machine products, toys, films, sheets It is widely used as a material for a variety of products ranging from artificial leather, tape, food packaging materials, and medical supplies.

Various additives such as plasticizers, stabilizers, fillers, and pigments may be appropriately added to such polyvinyl chloride resins to impart various processing properties.

Among them, plasticizers are additives that play a role of improving the processability by reducing the friction coefficient between polymer resins. Representative examples include phthalate-based, adipate-based, phosphate-based and trimellitate-based plasticizers, which are mostly used as general-purpose plasticizers.

Low molecular plasticizers, which are general purpose plasticizers, are processed with resins due to their low molecular weight and monotony of structural changes, and then the plasticizers themselves depart from the resins due to transferability, volatility and extractability, leading to deterioration of the essential properties of the resins and aging. In addition to facilitating, current environmental issues are becoming social issues.

In order to overcome the above problems, many studies have been conducted, and various developments have been proposed.

The polymer plasticizer, which is one of them, is easy to change in molecular weight, and has various advantages of structural design and modeling, and thus, there are advantages in that it is possible to compensate problems such as the implementation of plasticizer by adjusting various molecular weights and molecular shapes.

However, in the case of the conventionally proposed polymeric plasticizers, various polyhydric alcohols and acids, monoalcohols and acids are prepared in suitable combinations suitable for their properties, but still have problems that are difficult to overcome the performance resistance required by the end consumer.

 Therefore, in order to improve the migration resistance such as polyvinyl chloride resin, it is urgent to develop a polymer plasticizer having a different structure from the previous products.

In order to solve the problems of the prior art as described above, the present invention has a low heating loss, excellent viscosity and extraction resistance, does not lower the mechanical properties such as hardness, elongation and tensile strength of the polymer resin, in particular, An object of the present invention is to provide a polymer plasticizer that provides a polymer resin excellent in heat resistance and chemical resistance, a method for preparing the same, and a polymer resin composition including the same.

The above and other objects of the present invention can be achieved by the present invention described below.

In order to achieve the above object, the present invention provides a polymer plasticizer consisting of at least one member selected from the group consisting of linear polyester compounds represented by the following formulas (1) and (2).

[Formula 1]

[Formula 2]

In Formulas 1 and 2, R _{1 ,} R ₁ ′, R _2, and R ₂ ′ each represent an alkyl group having 3 to 18 carbon atoms, and R ₃ is an alkylene group or arylene group having 2 to 12 carbon atoms in one molecule. R ₄ may be different in one molecule as a branched alkylene group of 3 to 18 carbon atoms, and R ₅ is a branched alkylene group of 3 to 28 carbon atoms including an ester group in a molecule Can be different.

The present invention also provides a method for producing the polymer plasticizer.

In addition, the present invention provides a polymer resin composition comprising the polymer plasticizer.

Hereinafter, the present invention will be described in detail.

The polymer plasticizer of the present invention is characterized by consisting of at least one member selected from the group consisting of linear polyester compounds represented by the following formulas (1) and (2).

[Formula 1]

[Formula 2]

In Formulas 1 and 2, R _{1 ,} R ₁ ′, R _2, and R ₂ ′ each represent an alkyl group having 3 to 18 carbon atoms, and R ₃ is an alkylene group or arylene group having 2 to 12 carbon atoms in one molecule. R ₄ may be different in one molecule as a branched alkylene group of 3 to 18 carbon atoms, and R ₅ is a branched alkylene group of 3 to 28 carbon atoms including an ester group in a molecule Can be different.

R ₁ And R ₁ ′ may each be a straight chain alkyl group or a branched alkyl group.

R ₁ and R ₁ ′ may be derived from a monohydric alcohol having an alkyl group having 3 to 18 carbon atoms, preferably derived from a monohydric alcohol having an alkyl group having 4 to 14 carbon atoms.

When the carbon number of the monohydric alcohol is less than 3, a lot of low-molecular plasticizers are generated on the molecular weight distribution to increase the transferability of the plasticizer when applied to a polyvinyl chloride resin or the like. There is a problem that can not control the molecular weight.

R ₂ And R ₂ ′ may each be a straight chain alkyl group or a branched alkyl group.

R ₂ And R ₂ ′ may be derived from a monovalent carboxylic acid having an alkyl group having 3 to 18 carbon atoms, and is preferably derived from a monovalent carboxylic acid having an alkyl group having 4 to 14 carbon atoms.

When the number of carbon atoms of the monovalent carboxylic acid is less than 3, a lot of low molecular weight plasticizers are generated on the molecular weight distribution, and thus, when applied to a polyvinyl chloride resin or the like, there is a problem of increasing the plasticizer's transferability. There is a problem in that the molecular weight is not adjusted.

The R ₃ may be one or more selected from the group consisting of an alkylene group and an arylene group having 2 to 12 carbon atoms, and preferably one or more selected from the group consisting of an alkylene group and an arylene group having 4 to 8 carbon atoms. In the polyester compound represented by Formula 1 or 2, several R ₃ may be the same or different.

If the carbon number of the R ₃ is less than 2, there is a problem that the transition from the polymer resin due to the small molecular weight is too easy, and if it exceeds 12, the molecular size is too large, there is a problem that the bonding force is lowered.

The alkylene group may be derived from an aliphatic dicarboxylic acid having a straight or branched alkylene group having 2 to 12 carbon atoms, preferably derived from an aliphatic dicarboxylic acid having an alkylene group having 4 to 8 carbon atoms. will be.

The arylene group may be derived from an aromatic dicarboxylic acid having an arylene group having 2 to 12 carbon atoms, and is preferably derived from an aromatic dicarboxylic acid having an arylene group having 4 to 8 carbon atoms.

R ₄ may be a branched alkylene group having 3 to 12 carbon atoms, preferably a branched alkylene group having 4 to 8 carbon atoms. Several R ₄ in one polyester compound represented by Formula 1 or 2 may be the same or different.

If the carbon number of R ₄ is less than 2, it is difficult to implement a branched characteristic, so that there is a problem that the transition is too easy.

R ₄ may be derived from a polyhydric alcohol having a branched alkylene group having 3 to 18 carbon atoms, and preferably derived from a polyhydric alcohol having a branched alkylene group having 4 to 8 carbon atoms.

In the present invention, "polyhydric alcohol" is used in the concept containing a dihydric alcohol, such as glycol.

R ₅ may be a branched alkylene group having 3 to 28 carbon atoms including an ester group, preferably a branched alkylene group having 3 to 10 carbon atoms including an ester group. Several R ₅ in the specific polyester compound represented by Formula 1 or 2 may be the same or different.

When the carbon number of R ₅ is less than 3, it is difficult to prepare a polymer plasticizer, and when it exceeds 10, the polymer plasticizer has a problem that it is difficult to maintain suitable processability.

R ₅ may be derived from a polyhydric alcohol having a branched alkylene group having 3 to 28 carbon atoms including an ester group, preferably derived from a polyhydric alcohol having a branched alkylene group having 3 to 10 carbon atoms including an ester group will be.

R ₁ of the polyester compound represented by Formula ₁ + R ₁ ', molar ratio of R ₃ and R ₄ + R ₅ (R ₁ + R ₁ ': R ₃ R ₄ + R ₅ ) is preferably 5 to 20 mol%: 20 to 80 mol%: 15 to 75 mol%, and both R ₄ and R ₅ should be included, but each range is not particularly limited. The most excellent effect as a plasticizer can be exhibited within the said molar ratio range.

The molar ratio (R ₂ + R ₂ ': R ₃ : R ₄ + R ₅ ) of R ₂ + R ₂ ′, R ₃ and R ₄ + R ₅ of the polyester compound represented by Formula 2 is 5 to 20 mol% : 20 to 80 mol%: 15 to 75 mol% is preferable, and both R ₄ and R ₅ should be included, but each range is not particularly limited. The most excellent effect as a plasticizer can be exhibited within the said molar ratio range.

The weight average molecular weights of the polyester compounds represented by Formulas 1 and 2 are preferably 200 to 10,000, respectively. If the weight average molecular weight is less than 200, the molecular weight is too low, there is a problem that the transition from the polymer resin is too easy, and if it exceeds 10,000, the viscosity is too large, there is a problem that workability is lowered.

It is preferable that the acid value of the said polymeric plasticizer is five or less. The lower the acid value is, the better and it is preferable to have a value of at least 5 or less. The high acid value means that unreacted acid remains in the polymer plasticizer, which adversely affects the purity of the product itself.

The acid value may be calculated by Equation 1 below.

Acid value = (titration × 5.6 × factor) / sample volume

In Equation 1, the titration amount is the consumption amount (mL) of 0.1 N KOH aqueous solution used for titration of the polymer plasticizer, and the factor is the correction coefficient of the KOH aqueous solution (the factor is 1 in the case of 0.1N KOH aqueous solution). Sample amount represents the weight of the sample.

It is preferable that the viscosity of the said polymeric plasticizer is 50-100,000 cps. If the viscosity is less than 50 cps, there is a problem that the transition from the polymer resin is too low, the viscosity is too low, and if it exceeds 100,000 cps there is a problem that the processability of the resin due to high viscosity is lowered.

Method for producing a polymer plasticizer composition of the present invention,

a) 10 to 70% by weight of at least one compound selected from the group consisting of an aliphatic dicarboxylic acid having an alkylene group having 2 to 12 carbon atoms and an aromatic dicarboxylic acid having an arylene group having 2 to 12 carbon atoms;

Ii) 10 to 70% by weight of a mixture of a polyhydric alcohol having a branched alkylene group having 3 to 18 carbon atoms and a polyhydric alcohol having a branched alkylene group having 3 to 28 carbon atoms including an ester group; And

Iii) 10 to 50% by weight of at least one compound selected from the group consisting of monohydric alcohols having 3 to 18 carbon atoms or monovalent carboxylic acids having 3 to 18 carbon atoms; Making;

b) adding 0.02 to 1 part by weight of catalyst to 100 parts by weight of the reaction mixture and reacting at 130 to 280 ° C. for 3 to 24 hours; And

c) removing unreacted and byproduct water after the reaction and neutralizing, washing and filtering the residue;

Characterized in that it comprises a.

Specific examples of the aliphatic dicarboxylic acid include adipic acid, azelaic acid, sebacic acid, and the like.

Specific examples of the aromatic dicarboxylic acid include phthalic anhydride, maleic anhydride, trimellitic anhydride, and the like.

Specific examples of the polyhydric alcohol having a branched alkylene group having 3 to 18 carbon atoms include neopentyl glycol, 1,2-propanediol, 1,3-butanediol, 2-butyl-2-ethyl-1,3-propanediol, and the like. Can be mentioned.

Examples of the polyhydric alcohol having a branched alkylene group having 3 to 28 carbon atoms including the ester group include 2-hydroxypropan-2-yl 2-hydroxy-2-methyl propanoate (2-hydroxypropane-2-yl 2 2-hydroxy-2-methyl propanoate, 2-hydroxy-2-methylpropyl 2-hydroxy-2-methyl propanoate, 3-hydroxy 3-hydroxy-2,2-dimethylpropyl 2-hydroxy-2-methyl propanoate, 3-tert-butoxy-2,2- Dimethylpropyl 3-tert-butoxy-2,2-dimethyl propanoate and the like.

Specific examples of the monohydric alcohol include isononyl alcohol, 2-ethyl hexanol, isodecyl alcohol, and the like.

Specific examples of the monovalent carboxylic acid include 2-ethylhexanoic acid, hexanoic acid and the like.

The catalyst serves to increase the reaction rate of the reaction mixture, and may be at least one selected from the group consisting of tetraisobutyl titanate, tetraisopropyl titanate, dibutyl tin oxide and paratoluene sulfonic acid, It is not limited to this. It is preferable that the usage-amount is 0.02-1 weight part with respect to 100 weight part of reaction mixtures. If the amount is less than 0.02 parts by weight, the reaction efficiency is lowered. If the amount is more than 1 part by weight, the reaction rate is too fast, and there is a problem that the molecular weight is lowered.

The unreacted product and by-product water are removed under reduced pressure with a vacuum pump.

The residue is neutralized with 5-50% sodium hydroxide solution and washed with 5-50% sodium sulfate aqueous solution.

After washing with water, the residue may be dehydrated under a reduced pressure with a vacuum pump. Then, the adsorbent may be added and filtered to finally obtain a polymer plasticizer.

The prepared polymeric plasticizer has various excellent properties. In particular, by controlling the structure of the repeating main chain in a branched form, the polymer plasticizer has excellent resistance to migration, which is not common to general-purpose low-molecular-weight plasticizers and conventional polymer plasticizers, and is associated with resistance to migration. It also has excellent properties in deep heat resistance, extraction resistance and chemical resistance.

The polymer resin composition of the present invention is characterized by comprising the polymer plasticizer and the polymer resin.

The polymer resin may be a polyvinyl chloride resin, an acrylic resin, an ABS resin, a urethane resin, or a polyester resin, but is not limited thereto.

The polymer plasticizer is preferably used in 20 to 150 parts by weight based on 100 parts by weight of the polymer resin. If the content is less than 20 parts by weight, there is a problem that the processability of the polymer resin is lowered. If the content is more than 150 parts by weight, the transfer from the polymer resin is increased, thereby deteriorating the physical properties.

Hereinafter, preferred examples are provided to help understanding of the present invention, but the following examples are merely to illustrate the present invention, and the scope of the present invention is not limited to the following examples. It will be apparent to those skilled in the art that various modifications and variations are possible within the scope of the present invention, and such modifications and variations belong to the appended claims.

EXAMPLES

Example  One

In a four-necked two-liter flask equipped with a stirrer and a condenser, 551.55 g of adipic acid, 278.76 g of neopentylglycol, 136.70 g of 3-hydroxy-2,2-dimethylpropyl 2-hydroxy-2-methylpropanoate, And 219.99 g of isononyl alcohol were added to the reaction mixture prepared by adding 0.45 g of tetraisopropyl titanate as a catalyst to uniformly mix the mixture, and then heated to 220 ° C. under a nitrogen atmosphere for 9 hours. After the reaction, the unreacted product and the by-product water were removed by a vacuum pump at 150 to 220 ° C. The residue was neutralized with 3-10% aqueous sodium hydroxide solution and washed with 3-10% sodium sulfate. After dehydration using a vacuum pump, and filtered in a filter to prepare a polymer plasticizer.

Example  2

A reaction mixture was prepared by adding 551.55 g of adipic acid, 243.92 g of neopentyl glycol, 205.05 g of 3-hydroxy-2,2-dimethylpropyl 2-hydroxy-2-methylpropanoate, and 219.99 g of isononyl alcohol. The same procedure as in Example 1 was conducted except for the one.

Example  3

551.55 g of adipic acid, 174.23 g of neopentyl glycol, 341.75 g of 3-hydroxy-2,2-dimethylpropyl 2-hydroxy-2-methylpropanoate, and 219.99 g of isononyl alcohol were added to the reaction mixture. The same procedure as in Example 1 was carried out except for the preparation.

Example  4

518.21 g of adipic acid, 225.43 g of neopentylglycol, 110.55 g of 3-hydroxy-2,2-dimethylpropyl 2-hydroxy-2-methylpropanoate, and 434.40 g of isononyl alcohol were added to prepare a reaction mixture. In the same manner as in Example 1, except that 0.49 g of tetraisopropyl titanate as a catalyst was used.

Example  5

A reaction mixture was prepared by adding 518.21 g of adipic acid, 197.25 g of neopentyl glycol, 165.82 g of 3-hydroxy-2,2-dimethylpropyl 2-hydroxy-2-methylpropanoate, and 434.40 g of isononyl alcohol. In the same manner as in Example 1, except that 0.49 g of tetraisopropyl titanate as a catalyst was used.

Example  6

518.21 g of adipic acid, 140.89 g of neopentyl glycol, 276.37 g of 3-hydroxy-2,2-dimethylpropyl 2-hydroxy-2-methylpropanoate, and 434.40 g of isononyl alcohol were prepared to prepare a reaction mixture. In the same manner as in Example 1, except that 0.49 g of tetraisopropyl titanate as a catalyst was used.

Comparative example  One

The reaction mixture was prepared in the same manner as in Example 1 except that 551.55 g of adipic acid, 174.23 g of neopentyl glycol, 177.28 g of diethylene glycol, and 219.99 g of isononyl alcohol were prepared.

Comparative example  2

The reaction mixture was prepared in the same manner as in Example 1 except that 551.55 g of adipic acid, 174.23 g of neopentyl glycol, 224.28 g of dipropylene glycol, and 219.99 g of isononyl alcohol were prepared.

Comparative example  3

The reaction mixture was prepared in the same manner as in Example 1 except that 551.55 g of adipic acid, 177.78 g of diethylene glycol, 224.78 g of dipropylene glycol, and 219.99 g of isononyl alcohol were prepared.

Comparative example  4

Examples were prepared by adding 518.21 g of adipic acid, 140.89 g of neopentyl glycol, 143.77 g of diethylene glycol, and 434.40 g of isononyl alcohol, except that 0.49 g of tetraisopropyl titanate as a catalyst was used. It carried out similarly to 1.

Comparative example  5

Examples were prepared by adding 518.21 g of adipic acid, 140.89 g of neopentyl glycol, 181.78 g of dipropylene glycol, and 434.40 g of isononyl alcohol, except that 0.49 g of tetraisopropyl titanate as a catalyst was used. It carried out similarly to 1.

Comparative example  6

Example mixture was prepared by adding 518.21 g of adipic acid, 143.77 g of diethylene glycol, 181.78 g of dipropylene glycol, and 434.40 g of isononyl alcohol, except that 0.49 g of tetraisopropyl titanate as a catalyst was used. It carried out similarly to 1.

The compositions and amounts of the reaction mixtures and catalysts of Examples 1 to 6 and Comparative Examples 1 to 6 were summarized and described in Tables 1 and 2 below.

Raw material (g) Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Adipic acid 551.55 551.55 551.55 518.21 518.21 518.21 Neopentyl glycol 278.76 243.92 174.23 225.43 197.25 140.89 3-hydroxy-2,2-dimethylpropyl 2-hydroxy-2-methylpropanoate 136.70 205.05 341.75 110.55 165.82 276.37 Diethylene glycol Dipropylene glycol Isononyl alcohol 219.99 219.99 219.99 434.40 434.40 434.40 catalyst 0.45 0.45 0.45 0.49 0..49 0.49

Raw material (g) Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Adipic acid 551.55 551.55 551.55 518.21 518.21 518.21 Neopentyl glycol 174.23 174.23 140.89 140.89 3-hydroxy-2,2-dimethylpropyl 2-hydroxy-2-methylpropanoate Diethylene glycol 177.78 177.78 143.77 143.77 Dipropylene glycol 224.28 224.78 181.78 181.78 Isononyl alcohol 219.99 219.99 219.99 434.40 434.40 434.40 catalyst 0.45 0.45 0.45 0.49 0.49 0.49

The physical properties of the polymeric plasticizers prepared according to Examples 1 to 6 and Comparative Examples 1 to 6 were measured by the following methods, and the results are shown in Tables 3 and 4.

* Viscosity-Using the Brookfield viscometer, the viscosity was measured at rpm 12 to 20 for 1 minute at 25 ℃ under the condition that the torque value was maintained more than 50% by using spindle 3 and 4, and the viscosity reference material was measured every time. The error value was minimized.

* Molecular weight-measured using GPC (Gel Permeation Chromatography), specific specifications are as follows. The Detector is a Waters 2414, RID (Refractive IndexetDetector) method, the pump is waters 1525 for HPLC, and the column uses HR 1,2,4 which can measure the mass average molecular weight from 100 to 500,000. The injection volume was injected at 50 μl per minute, the time was 50 minutes, and the solvent was THF.

* Tensile strength-By using the ASTM D638 method, the cross head speed (200 mm / min) was pulled by using a test device UTM, and then measured the point where the specimen is cut, calculated by the following equation (2) .

Tensile strength (kgf / mm 2) = load value (kgf) / {thickness (mm) x width (mm)}

* Elongation-By pulling the crosshead speed (200 mm / min) using a test instrument, U.T.M by the ASTM D638 method, the point at which the specimen is cut was measured by the following equation (3).

Elongation (%) = Length after elongation (mm) / Initial length (mm) × 100

* Hardness-The hardness was measured as an indicator of plasticization efficiency, and the needle of A type was completely lowered to one of the specimens according to ASTM D2240 method, and the hardness value was read after 5 seconds. After testing five locations for, the average value was calculated. The hardness was measured once immediately after preparing the specimen, and once again after one day after the specimen was prepared.

* Loss of heating-the composition was worked at 165 ° C. for 3 minutes using a roll mill to produce a 0.8 mm thick sheet, which was then taken 60 g at 185 ° C. for 10 minutes using a roll mill. To prepare a specimen with a thickness of 0.4 mm. Then, after 24 hours, the weight of the specimen was measured, and calculated by the following equation (4).

Loss on heating (% by weight) = {1-(weight after 10 min at 185 ° C) / 60 g} × 100

* Improving resistance-For each specimen prepared, the initial weight (Wi) was measured to 4 decimal places, and a sheet (3 cm × 3 cm) was put between the ABS resin plates in an oven at 70 ° C and a load of 1 kg was applied. After leaving for 72 hours in the state, the specimen was taken out and stored in a thermostat for 4 hours or more, the weight (Wo) of the specimen was measured, and calculated by the following equation (5).

Transfer Amount (wt%) = {(Wi-Wo) / Wi} X 100

division Example One 2 3 4 5 6 Molecular Weight 3560 3620 3512 2564 2543 2648 Viscosity 2362 2460 2382 756 785 766 The tensile strength 3.12 3.11 3.14 2.34 2.34 2.43 Elongation 488 484 489 610 612 611 Implosion 0.0453 0.0312 0.0215 0.0845 0.0810 0.0756 Heating loss 0.0545 0.0426 0.0245 0.1021 0.1011 0.0839 Hardness 85 86 86 77 77 78

division Comparative example One 2 3 4 5 6 Molecular Weight 3425 3490 3512 2456 2586 3480 Viscosity 2256 2240 2390 689 677 680 The tensile strength 2.87 2.88 2.90 2.11 2.08 2.40 Elongation 540 547 553 710 725 730 Implosion 0.0686 0.0651 0.0510 0.1089 0.0978 0.0912 Heating loss 0.0756 0.0685 0.0581 0.1232 0.1186 0.0986 Hardness 84 85 85 75 75 76

Since the molecular weight and viscosity of the polymer plasticizer can be adjusted according to the conditions to be applied, the results of Tables 3 and 4, when the average molecular weight of the polymer plasticizer is 3,400 to 3,700 or the viscosity is in the range of 2,200 to 2,500 cps (Examples 1 to 3) And Comparative Examples 1 to 3) and an average molecular weight of 2,400 to 2,700 or when the viscosity is in the range of 650 to 800 cps (Examples 4 to 6 and Comparative Examples 4 to 6).

As can be seen from the results of Tables 3 and 4, the polymeric plasticizer (Examples 1 to 6) having a branched alkylene group including the ester group according to the present invention (Examples 1 to 6) is linear alkyl corresponding thereto in molecular weight or viscosity. Compared with the polymeric plasticizers having comparative group (Comparative Examples 1 to 6), the mechanical properties such as tensile strength, elongation, hardness, etc. are maintained at the same level, the heating loss is less, and the value is 10% or more in the transition resistance. By confirming the increase, it was confirmed that the heat resistance, chemical resistance, and the like were improved.

As described above, the polymeric plasticizer according to the present invention by controlling the structure of the repeating main chain in a branched form, when used as an additive of various polymer resins, less heating loss, excellent viscosity and extraction resistance, The mechanical properties such as hardness, elongation and tensile strength of the resin are not lowered, and in particular, there is an effect of providing a polymer resin having excellent heat resistance and excellent heat resistance and chemical resistance.

Claims (12)

A polymeric plasticizer comprising at least one member selected from the group consisting of a linear polyester compound represented by the following general formula (1) and a linear polyester compound represented by the following general formula (2); [Formula 1]

[Formula 2]

In Chemical Formulas 1 and 2, R _{1 ,} R ₁ ′, R ₂ And R ₂ 'is each an alkyl group having 3 to 18 carbon atoms, and R ₃ is an alkylene group or arylene group having 2 to 12 carbon atoms, which may be different from each other in one molecule, and R ₄ is a branched alkylene group having 3 to 18 carbon atoms. And may be different from each other in one molecule, and R ₅ may be a branched alkylene group having 3 to 28 carbon atoms including an ester group, and may be different from each other in one molecule. The method of claim 1, The linear polyester compounds represented by Formulas 1 and 2, characterized in that the weight average molecular weight is 200 to 10,000, respectively Polymeric plasticizers. The method of claim 1, Polyester compound represented by the formula (1) is R ₁ + Molar ratio of R ₁ ′, R ₃ and R ₄ + R ₅ (R ₁ + R ₁ ′: R ₃ : R ₄ + R ₅ ) is from 5 to 20 mol%: 20 to 80 mol%: 15 to 75 mol% Characterized by Polymeric plasticizers. The method of claim 1, The polyester compound represented by the formula (2) is R ₂ + Molar ratio of R ₂ ′, R ₃ and R ₄ + R ₅ (R ₂ + R ₂ ′: R ₃ : R ₄ + R ₅ ) is from 5 to 20 mol%: 20 to 80 mol%: 15 to 75 mol% Characterized by Polymeric plasticizers. The method of claim 1, The polymer plasticizer is a polymer plasticizer, characterized in that the acid value is 5 or less. The method of claim 1, The polymer plasticizer is a polymer plasticizer, characterized in that the viscosity is 50 to 100,000 cps. a) 10 to 70% by weight of at least one compound selected from the group consisting of an aliphatic dicarboxylic acid having an alkylene group having 2 to 12 carbon atoms and an aromatic dicarboxylic acid having an arylene group having 2 to 12 carbon atoms; Ii) 10 to 70% by weight of a mixture of a polyhydric alcohol having a branched alkylene group having 3 to 18 carbon atoms and a polyhydric alcohol having a branched alkylene group having 3 to 28 carbon atoms including an ester group; And Iii) 10 to 50% by weight of at least one compound selected from the group consisting of monohydric alcohols having 3 to 18 carbon atoms or monovalent carboxylic acids having 3 to 18 carbon atoms; Making; b) adding 0.02 to 1 part by weight of catalyst based on 100 parts by weight of the reaction mixture and reacting at 130 to 280 ° C. for 3 to 24 hours; And c) removing unreacted and by-product water after the reaction and neutralizing, washing and filtering the residue; Characterized in that it comprises Method for producing a polymeric plasticizer. The method of claim 7, wherein The mixture of ii) is a mixture of a polyhydric alcohol having a branched alkylene group having 2 to 8 carbon atoms and a polyhydric alcohol having a branched alkylene group having 3 to 10 carbon atoms including an ester group. Method for producing a polymeric plasticizer. The method of claim 7, wherein The catalyst is at least one member selected from the group consisting of tetraisobutyl titanate, tetraisopropyl titanate, dibutyl tin oxide and paratoluene sulfonic acid. Method for producing a polymeric plasticizer. A polymer plasticizer and a polymer resin according to claim 1 are included. By Polymer resin composition. The method of claim 10, The polymer plasticizer is characterized in that it comprises 20 to 150 parts by weight based on 100 parts by weight of the polymer resin. Polymer resin composition. The method of claim 10, The polymer resin is polyvinyl chloride resin, acrylic resin, ABS resin, urethane resin or polyester resin, characterized in that Polymer resin composition.