KR101935938B1 - Polyurethane elastomer compositions comprising dimer acid alkyl ester from vegetable oil, preparation method thereof, and adhesive containing the same - Google Patents

Abstract

The present invention relates to a polyurethane elastomer composition using a vegetable oil-derived dimeric acid alkyl ester, a process for producing the same, and a pressure-sensitive adhesive containing the same, wherein the polyurethane elastomer according to the present invention is produced using a dimer acid alkyl ester derived from a vegetable oil, It is more environmentally friendly than polyurethane elastomers based on petroleum raw materials. In addition, it is more economical to reduce the cost of raw materials than a polyurethane elastomer based on petroleum raw materials. Further, the polyurethane elastomer produced according to the present invention exhibits excellent tensile strength and tensile elongation, so that it can serve not only as an elastic body but also as a dentifrice composition, a paint composition and a coating composition.

Description

[0001] The present invention relates to a polyurethane elastomer composition comprising a vegetable oil-derived dimeric acid alkyl ester, a process for producing the same, and an adhesive containing the same,

The present invention relates to a polyurethane elastomer composition using a vegetable oil-derived dimeric acid alkyl ester, a process for producing the same, and a pressure-sensitive adhesive containing the same.

Adhesive materials such as adhesives, adhesives, sealants, coatings, and paints are used in various industrial fields such as civil engineering and construction, packing, bookbinding, automotive, electronics, precision, optical products, woodworking, plywood, And it is widely used in various fields including wood, metal, rubber, plastic, leather, ceramics, etc. Recently, it can be applied to concrete, and its use is spreading throughout the industry. Particularly, among the adhesives, the polyurethane-based adhesives are excellent in weather resistance, oil resistance, and cold resistance and are usefully used for structural materials such as metals, ceramics, plastics and the like or for bonding laminate films for food packaging.

The polyurethane-based adhesive is a general term for an adhesive having a urethane group -NHCOO-, and broadly includes all the adhesives having a component of a compound synthesized from an isocyanate group (NCO-) and a hydroxyl group (OH-). Polyurethanes are formed under the conditions of hydroxyl group catalysts or ultraviolet activation by reaction between polyol and isocyanate complexes (R- (N = C = O)). Polyurethanes depend on the type of isocyanate and polyol reactant, the long bonds contained in the polyol help to be a soft elastomer, and the large amount of bonding helps to become a hard polymer. Maintaining a medium length between the two bonds can maintain a rigid but moderately rigid physical property.

When the polyurethane is burned, the individual units are not melted and cured and their properties are changed. This means that when the other additives are reacted to the monomer, a new polymer can be made, which can give various properties through additives. On the other hand, interest in biodegradable additives such as aliphatic polyesters is also increasing from the viewpoint of environmental protection. Among the biodegradable additions, the polylactide has a high melting point of 130 to 180 DEG C and is excellent in transparency. Lactide, which is a raw material of polylactide, can be obtained from renewable resources such as plants and is economical. Recently, studies on poly (L-lactide) -poly (lactone) -poly (L-lactide) triblock copolymers produced by using polylactide have been reported (Patent Document 1) .

Nonetheless, most of the polyurethane resins currently in use are manufactured from petroleum-based raw materials and have the problem of causing severe environmental pollution. Thus, the present inventors have found that when a plant-derived material is used as a polyurethane monomer and a hard polymer is added thereto to enhance the physical properties, not only the quality of the polymer is improved but also the environmental pollution caused by the conventional petroleum- It was found that polyurethane elastomer containing polylactide added to the dimer acid derived from vegetable oil was not only environmentally friendly but also had excellent mechanical properties, and completed the present invention Respectively.

Korean Patent No. 10-1634103

An object of the present invention is to provide a polyurethane elastomer.

Another object of the present invention is to provide a process for producing a polyurethane elastomer.

It is still another object of the present invention to provide an adhesive composition comprising a polyurethane elastomer.

In order to achieve the above object,

The present invention relates to a polyether polyol ester-bonded with a dimer acid or a C ₁ -C ₆ alkyl ester thereof;

And a polylactic acid ester-bonded to the polyether polyol,

Wherein the ends of the polylactic acid between the units are crosslinked by diisocyanate.

The present invention also relates to a process for esterifying a dimer acid or a C ₁ -C ₆ alkyl ester thereof with a polyether polyol (step 1);

Esterifying polylactic acid with the polyether polyol of step 1 (step 2); And

And reacting the polylactic acid terminal of the product prepared in step 2 with a diisocyanate compound to prepare a polyurethane elastomer (step 3).

Further, the present invention provides an adhesive, paint and coating composition comprising the polyurethane elastomer.

The polyurethane elastomer according to the present invention is more environmentally friendly than conventional petroleum raw material-based polyurethane elastomers since it is produced using a dimer acid alkyl ester derived from vegetable oil. In addition, it is more economical to reduce the cost of raw materials than a polyurethane elastomer based on petroleum raw materials. Further, the polyurethane elastomer produced according to the present invention exhibits excellent tensile strength and tensile elongation, so that it can serve not only as an elastic body but also as a dentifrice composition, a paint composition and a coating composition.

Figure 1 and Figure 3 is an embodiment of step 11, step 2, the poly (DAME- co -PPG400_1.1), PLLA- poly (DAME- co -PPG400_1.1) prepared in Step 3 -PLLA, [PLLA- ≪ ¹ > H-NMR spectra of poly (DAME- co- PPG400_1.1)] _n .
4 to 6 are graphs showing the results of the measurement of the poly (DAME- co- PPG400_1.2), PLLA-poly (DAME- co- PPG400_1.2) -PLLA, [PLLA- ≪ ¹ > H-NMR spectra of poly (DAME- co- PPG400_1.2)] _n .
7 to 9 are carried out steps in Example 31, Step 2, the poly (DAME- co -PPG700_1.1), PLLA- poly (DAME- co -PPG700_1.1) prepared in Step 3 -PLLA, [PLLA- poly (DAME- co -PPG700_1.1)] is the ¹ H-NMR spectra analysis of _n.
10 to 12 are graphs showing the results of the measurement of the poly (DAME- co- PPG700_1.2), PLLA-poly (DAME- co- PPG700_1.2) -PLLA, [PLLA- poly (DAME- co -PPG700_1.2)] is the ¹ H-NMR spectra analysis of _n.
Figure 13 to Figure 15 in Example 5 Step 1, Step 2, the poly (DAME- co -PPG1000_1.1), PLLA- poly (DAME- co -PPG1000_1.1) prepared in Step 3 -PLLA, [PLLA- ≪ ¹ > H-NMR spectra of poly (DAME- co- PPG1000_1.1)] _n .
16 to 18 are graphs showing the effect of the poly (DAME- co- PPG1000_1.2), PLLA-poly (DAME- co- PPG1000_1.2) -PLLA, [PLLA- ≪ ¹ > H-NMR spectra of poly (DAME- co- PPG1000_1.2)] _n .
Figure 19 is an embodiment 61 steps in the step 2, the poly (DAME- co -PPG1000_1.2), PLLA- poly (DAME- co -PPG1000_1.2) prepared in Step 3 -PLLA, [PLLA- poly (DAME - co- PPG1000_1.2)] _n .
20 is a graph showing the results of DSC analysis for Example 5. Fig.
21 is a graph showing the SS Curve (tensile strength-tensile elongation curve) of polyurethane finally produced in Examples 1 to 6. Fig.

Hereinafter, the present invention will be described in detail.

The present invention relates to a polyether polyol ester-bonded with a dimer acid or a C ₁ -C ₆ alkyl ester thereof;

And a polylactic acid ester-bonded to the polyether polyol,

Wherein the ends of the polylactic acid between the units are crosslinked by diisocyanate.

Hereinafter, the polyurethane elastomer according to the present invention will be described in detail.

First, the polyurethane elastomer according to the present invention may be a block copolymer comprising at least one hard segment block and at least one soft segment block.

At this time, the hard segment block may be a structural unit derived from a polyester polyol compound,

The soft segment block may be a structural unit derived from a polyether polyol compound.

By including the hard segment block, the impact strength can be remarkably improved, and compatibility with the thermoplastic resin composition and crystallinity of the polyurethane can be increased through the hard segment block.

Since the soft segment block can be mixed well with the polylactic acid, compatibility between the polylactic acid and the polyurethane elastomer can be increased.

Next, in the polyurethane elastomer according to the present invention, the dimeric acid or the C ₁ -C ₆ alkyl ester thereof may be characterized by being a dimer acid or an ester thereof derived from vegetable or animal fatty acids.

The vegetable fatty acids may be soybean fatty acid, soybean fatty acid, canola oil fatty acid, safflower seed oil fatty acid, sunflower oil fatty acid, flax oil fatty acid, cottonseed fatty acid, oxal fatty acid, Examples of animal fatty acids include, but are not limited to, tallow fatty acid, lard fatty acid, fish oil fatty acid, and the like.

In the present invention, the dimeric acid derivative derived from vegetable oil may be a dimeric acid, which is a saturated or unsaturated fatty acid or an ester thereof, which can be obtained from resources generated in waste cooking oil, safflower oil, tall oil, fish oil, , For example, in the form of a mixture of dimeric acid or non-conjugated dimeric acid by thermal polymerization of diene fatty acids in the components of vegetable oils.

For example, C ₁₈ -linolenic acid in vegetable oil can be produced by thermal polymerization in the presence of a catalyst to form a non-aromatic cyclic dimer such as acyclic dimer acid, monocyclic dimer acid and bicyclic dimer acid having a carbon number of 36 Acid, and aromatic dimer acid having a benzene ring. Since the vegetable oil contains saturated or unsaturated fatty acids, the dimeric acid composition prepared from vegetable oil contains not only C ₃₆ dimer acid derived from the C ₁₈ -linolenic acid but also various cyclic (or cyclic) and acyclic (or non-cyclic) Cyclic) dimer acids.

On the other hand, the dimeric acid alkyl ester can be derived from the above-mentioned dimeric acid and can be obtained by esterifying a raw material of dimeric acid derived from vegetable oil purified from resources generated from waste cooking oil, safflower oil, tall oil, fish oil, May be synthesized and used.

Further, the dimer acid may be selected from one or more fatty acids selected from the group consisting of lauric fatty acid, myristic fatty acid, palmitic fatty acid, stearic fatty acid, oleic fatty acid, linoleic fatty acid, linolenic fatty acid, vegetable oil, And the like.

Further, the dimer acid may be a compound represented by the following formula (1).

[Chemical Formula 1]

In this case, in Formula 1,

R ¹ , R ² , R ³ and R ⁴ may each independently be a C ₁ to C ₁₀ straight chain alkyl.

The dimer acid may be a polyurethane elastomer which is a compound represented by the following formula (4).

[Chemical Formula 4]

In the polyurethane elastomer according to the present invention, the polyether polyol compound may be a compound represented by the following formula (2).

(2)

In Formula 2,

R ⁵ may be a straight or branched alkyl of methyl, or C ₂ -C ₅

n may be an integer of 1-30.

The equivalent ratio of the polyether polyol to the dimeric acid or the C ₁ -C ₆ alkyl ester thereof may be 1.0 to 1.1, may be 0.9 to 1.2, may be 0.8 to 1.3, and may be 0.7 to 1.4.

Further, the polyether polyol compound may be polypropylene glycol or polyethylene glycol.

At this time, the polypropylene glycol or polyethylene glycol may have a molecular weight of 400 to 1000, may be 300 to 1100, may be 200 to 1200, and may be 100 to 1300.

In the polyurethane elastomer according to the present invention, the polylactic acid may be characterized in that the polylactic acid is polymerized from lactide, lactic acid, lactic acid ester or the L- or D-isomer thereof, and the tacticity of the polylactic acid, May be atatic, and may be syndiotatic or isotatic.

Further, in the polyurethane elastomer according to the present invention, the polylactic acid may be replaced with a polyester polyol compound represented by the following formula (5).

[Chemical Formula 5]

In Formula 5,

R ⁶ is a linear or branched alkyl of methyl, or C ₂ ~ C _5.

In the polyurethane elastomer according to the present invention, the diisocyanate compound is at least one compound selected from the group consisting of toluene diisocyanate (TDI), 4,4-methylenediphenyl diisocyanate (MDI), 1,5-naphthylene diisocyanate (NDI) Can be selected from among hexamethylene diisocyanate (HMDI), isophorone diisocyanate (IPDI), xylene diisocyanate (XDI), tetramethyl xylene diisocyanate (TMXDI), and 1,8-diisocyanate methyl octane, May be any diisocyanate compound commonly used in polyurethane synthesis.

The diisocyanate serves to connect the copolymer chains formed from the dimeric acid alkyl ester, the polyether polyol and the polylactic acid in the polyurethane elastomer according to the present invention, thereby extending the chain length of the polyurethane, Thereby increasing the molecular weight.

In the polyurethane elastomer according to the present invention, the polyurethane elastomer may be a polymer represented by the following formula (3).

(3)

In Formula 3,

n can be an integer from 1-30;

m may be an integer of 1-100;

X may be an integer of 1-20;

Y may be an integer from 1-10;

R ¹ and R ² may each independently be a C ₁ -C ₁₀ linear alkylene;

R ³ and R ⁴ may each independently be a straight chain alkyl of C ₁ -C ₁₀ ;

R ⁵ can be methylene, or C ₂ -C ₅ straight or branched chain alkylene; And

일 수 있다.R ⁶ is methylene, C ₂ -C ₁₀ linear or branched alkylene, cyclo C ₆ -C ₂₀ alkylene or C ₆ -C ₂₀ arylene substituted with unsubstituted or C ₁ -C ₃ alkyl, or

Lt; / RTI >

The present invention also relates to a process for esterifying a dimer acid or a C ₁ -C ₆ alkyl ester thereof with a polyether polyol (step 1);

Esterifying polylactic acid with the polyether polyol of step 1 (step 2); And

And reacting the polylactic acid terminal of the product prepared in step 2 with a diisocyanate compound to prepare a polyurethane elastomer (step 3).

Hereinafter, the production method of the present invention will be described step by step. The following description is provided to aid understanding of the present invention, but the present invention is not limited thereto.

First, in the process for producing a polyurethane elastomer according to the present invention, step 1 is a step of dehydrating condensation polymerization of a terminal carbonyl group of a dimer acid or a C ₁ -C ₆ alkyl ester thereof with a terminal hydroxyl group of a polyether polyol, And a step of preparing a polymer copolymer.

The dimer acid or the C ₁ -C ₆ alkyl ester thereof may be a dimer acid or an ester thereof obtained from vegetable or animal fatty acids.

Further, the dimeric acid or its C ₁ -C ₆ alkyl ester may be used in combination with a fatty acid such as lauric fatty acid, myristic fatty acid, palmitic fatty acid, stearic fatty acid, oleic fatty acid, linoleic fatty acid, linolenic fatty acid, vegetable oil, And at least one fatty acid selected from the group consisting of

Further, the dimer acid may be a compound represented by the following formula (1).

[Chemical Formula 1]

In Formula 1,

R ¹ , R ² , R ³ and R ⁴ may each independently be a C ₁ to C ₁₀ straight chain alkyl.

The dimer acid may be a compound represented by the following formula (4).

[Chemical Formula 4]

In the step 1, the polyether polyol compound may be a compound represented by the following formula (2).

(2)

In Formula 2,

R ⁵ may be a straight or branched alkyl of methyl, or C ₂ -C _5; And

n may be an integer of 1-30.

The equivalent ratio of the polyether polyol used to the dimeric acid or its C ₁ -C ₆ alkyl ester may be 1.0 to 1.1, may be 0.9 to 1.2, may be 0.8 to 1.3, and may be 0.7 to 1.4 .

The polyether polyol compound used may be polypropylene glycol or polyethylene glycol, and the polypropylene glycol or polyethylene glycol may have a molecular weight of 400 to 1000, may be 300 to 1100, may be 200 to 1200, 100 to 1300. < / RTI >

In the above step, the dimer acid or its C ₁ -C ₆ with a catalyst used for synthesis of esters and polyether polyols are _{Ti (OBu) 4, Ti (} Oi-Pr) 4, SnO (Bu) 2, Sb ₂ O ₃ , Zn (OAc) ₂ , Mn (OAc), etc.,

The reaction temperature may be 160 ° C to 200 ° C, 150 ° C to 210 ° C, or 140 ° C to 220 ° C.

Next, in the process for producing an elastomeric polyurethane according to the present invention, Step 2 is a step of dehydrating condensation polymerization of the terminal hydroxy group of the polyether polyol segment of the polymer copolymer produced in Step 1 and the terminal carbonyl group of the polylactic acid, Linking of the block copolymer.

The polylactic acid may be lactide, lactic acid, lactic acid ester, or polylactic acid polymerized from the L- or D-type isomer thereof. The tacticity of the polylactic acid may be atatic And may be syndiotatic or isotatic.

Further, the polylactic acid may be used in place of the polyester polyol compound represented by the following formula (5).

[Chemical Formula 5]

In Formula 5,

R ⁶ is a linear or branched alkyl of methyl, or C ₂ ~ C _5.

In the step 2, Sn (Oct) ₂ , Al (Oi-Pr) ₃ , Sn (OTf) ₂ , HOTf, DBU, and the like are used as catalysts for synthesizing the poly- MTBD, Zn Lactate, Ti (OBu) ₄ , Ti (Oi-Pr) ₄ ,

The reaction temperature may be 100 ° C to 120 ° C, and may be 90 ° C to 100 ° C.

In step 2, an organic solvent may be used to purify the product after the polymerization reaction. Examples of the organic solvent that can be used include chloroform and methanol, but not limited thereto, and conventionally used polymeric refining Any organic solvent may be used.

Finally, in the process for producing an elastomeric polyurethane according to the present invention, in Step 3, the terminal hydroxy group of the polylactic acid segment of the block copolymer prepared in Step 2 and the cyanate group of the diisocyanate are subjected to a dehydration condensation reaction to obtain a polyurethane elastomer It is a process of forming.

The diisocyanate compound may be at least one selected from the group consisting of toluene diisocyanate (TDI), 4,4-methylenediphenyl diisocyanate (MDI), 1,5-naphthylene diisocyanate (NDI), 1,6-hexamethylene diisocyanate , Isophorone diisocyanate (IPDI), xylene diisocyanate (XDI), tetramethylxylylene diisocyanate (TMXDI), and 1,8-diisocyanate methyloctane can be used and are commonly used in polyurethane synthesis Any diisocyanate compound used may be used without limitation.

The diisocyanate serves to connect the copolymer chains formed from the dimeric acid alkyl ester, the polyether polyol and the polylactic acid in the process for producing the polyurethane elastomer according to the present invention, whereby the chain length of the polyurethane is extended, And the molecular weight of the urethane elastomer is increased.

In step 3, Sn (Oct) ₂ , NMe ₃ , NMe ₂ Et, NEt ₃ , Ferric acetylacetonate, Cobalt Naphthenate, Dibutyltin dilaurate, and the like are used as catalysts for synthesizing the polylactic acid and the polymer copolymer prepared in step 1 Lt; / RTI >

The reaction temperature may be 100 ° C to 120 ° C, and may be 90 ° C to 100 ° C.

In step 3, an organic solvent may be used to purify the product after the polymerization reaction. Examples of the organic solvent that may be used include chloroform and methanol, but not limited thereto. For example, Any organic solvent may be used.

The present invention provides an adhesive composition comprising the polyurethane elastomer.

The present invention also relates to a substrate; And

And a pressure-sensitive adhesive layer comprising the pressure-sensitive adhesive composition formed on the surface of the substrate.

In the pressure-sensitive adhesive composition using the above-described multiple thermoplastic polymer compounds, the tackifier may include a rosin ester tackifier, a terephene-based tackifier, a petroleum resin tackifier (aliphatic Acid-modified aliphatic, alicyclic, aromatic), coal-based tackifiers, alkylphenol-based tackifiers, and the like.

Examples of the plasticizer include epoxidized soybean oil plic acid, citric acid, citric acid ester, fatty acid ester, polyethylene glycol, polyethylene propylene glycol, glycerol ester, phthalate type, phosphate type, aliphatic diester type (aliphatic diester type), polyester type plasticizer, and the like, but the present invention is not limited thereto.

The present invention also provides a paint composition comprising the polyurethane elastomer.

Furthermore, the present invention provides a coating composition comprising said polyurethane elastomer.

Hereinafter, the present invention will be described in detail with reference to the following examples and experimental examples.

It should be noted, however, that the following examples and experimental examples are illustrative of the present invention, but the scope of the invention is not limited by the examples and the experimental examples.

≪ Example 1 > Preparation of a polyurethane elastomer according to the present invention 1

Step 1: Poly (DAME- co -PPG400_1.1)  Produce

First, 4 is installed with a thermometer, a stirrer, a distiller, a nitrogen tube reactor to obtain the following dimer acid methyl ester (. DAME, 1eq, 51.0g, 86.0mmol) and polypropylene glycol _{(PPG, M W: 400,} 1.0 eq,. 38.03 g, 95.0 mmol) were charged into the four-necked reactor and purged with nitrogen for 30 minutes.

Next, titanium (IV) butoxide (TBT, 0.1 eq., 2.94 g, 9.0 mmol) was further added to the four-necked reactor and then reacted at 160 ° C for 2 hours under nitrogen purge.

Then, the nitrogen purge was stopped, and the mixture was reacted with a poly (DAME- co- PPG400_1.) Under a low vacuum (200 torr) at 180 ° C. for 2 hours and a high vacuum (1 torr or less) at 180 ° C. for 16 hours and at 200 ° C. for 4 hours. 1).

Step 2: PLLA - Poly (DAME-- PPG400 _1.1) - PLLA's  Produce

(DAME- co- PPG400_1.1), 1 eq., 18.16 g), L-lactide (49 eq., 8.19 g, 56.8 mmol) prepared in the above step 1, Tin (II) 2-ethylhexanoate (Sn (Oct) ₂ , 0.01 eq., 5 mg, 0.011 mmol) and toluene (18 mL) were placed and reacted at 110 ° C for 5 hours.

After the reaction, 30 mL of chloroform was added to dissolve and precipitated in methanol to obtain PLLA-poly (DAME- co- PPG400_1.1) -PLLA as a pale brown solid.

step 3: [PLLA-poly (DAME- co - PPG400 _1.1)] _n Manufacturing

A pressure reactor was charged with the dimer acid methyl ester polyester / lactide block polyester PLLA-poly (DAME- co- PPG400_1.1) -PLLA (1 eq., 10.0 g), diisocyanate (MDI, 1 eq. (II) 2-ethylhexanoate (Sn (Oct) ₂ , 10 mg) and toluene (30 mL) were placed and reacted at 80 ° C. for 8 hours.

After the reaction, 10 mL of chloroform was added to dissolve and precipitated in methanol to give [PLLA-poly (DAME- co- PPG400_1.1)] _n as a pale brown solid.

< Example  2> Production of a polyurethane elastomer according to the present invention 2

Step 1: Poly (DAME- co -PPG400_1.2)  Produce

First, 4 is installed with a thermometer, a stirrer, a distiller, a nitrogen tube reactor to obtain the following dimer acid methyl ester (. DAME, 1eq, 40.0g, 68.0mmol) and polypropylene glycol _{(PPG, M W: 400,} 1.2eq,. 47.19 g, 118.0 mmol) were placed in the four-necked reactor and purged with nitrogen for 30 minutes.

Next, titanium (IV) butoxide (TBT, 0.1 eq., 3.35 g, 10.0 mmol) was further added to the four-necked reactor, followed by reaction at 160 ° C for 2 hours under nitrogen purge.

Then, the nitrogen purge was stopped, and the mixture was reacted with a poly (DAME- co- PPG400_1.) Under a low vacuum (200 torr) at 180 ° C. for 2 hours and a high vacuum (1 torr or less) at 180 ° C. for 16 hours and at 200 ° C. for 4 hours. 2).

Step 2: PLLA - Poly (DAME- co - PPG400 _1.2) - PLLA's  Produce

(DAME- co- PPG400_1.2), 1 eq., 18.85 g), L-lactide (29 eq., 8.50 g, 59.0 mmol) prepared in the above step 1, Tin (II) 2-ethylhexanoate (Sn (Oct) ₂ , 0.1 eq., 8 mg, 0.020 mmol) and toluene (18 mL) were placed and reacted at 110 ° C for 5 hours.

After the reaction, 30 mL of chloroform was added to dissolve and precipitated in methanol to obtain PLLA-poly (DAME- co- PPG400_1.2) -PLLA as a pale brown solid.

step 3: [PLLA-poly (DAME- co - PPG400 _1.2)] _n Manufacturing

A pressure reactor was charged with the dimer acid methyl ester polyester / lactide block polyester PLLA-poly (DAME- co- PPG400_1.2) -PLLA (1 eq., 10.0 g), diisocyanate (MDI, 1 eq. , 0.185 g, 74.1 mmol), tin (II) 2-ethylhexanoate (Sn (Oct) ₂ , 10 mg) and toluene (10 mL) were placed and reacted at 80 ° C. for 8 hours.

After the reaction, 10 mL of chloroform was added to dissolve, and the precipitate was precipitated in methanol to give [PLLA-poly (DAME- co- PPG400_1.2)] _n as a pale brown solid.

< Example  3> Production of polyurethane elastomer according to the present invention 3

Step 1: Poly (DAME- co -PPG700_1.1)  Produce

First, 4 is installed with a thermometer, a stirrer, a distiller, a nitrogen tube reactor to obtain the following dimer acid methyl ester (. DAME, 1eq, 40.0g, 68.0mmol) and polypropylene glycol _{(PPG, M W: 700,} 1.0eq,. 52.2 g, 75.0 mmol) were charged into the four-necked reactor and purged with nitrogen for 30 minutes.

Next, titanium (IV) butoxide (TBT, 0.1 eq., 2.31 g, 7.0 mmol) was further added to the four-necked reactor and reacted at 160 ° C for 2 hours under nitrogen purge.

Then, the nitrogen purge was stopped, and the mixture was reacted at 180 ° C. for 16 hours and at 200 ° C. for 4 hours under high vacuum (200 torr) and 180 ° C. for 2 hours and under high vacuum (1 torr or less), respectively, to obtain poly (DAME- co- PPG700_1. 1).

Step 2: PLLA - Poly (DAME- co - PPG700 _1.1) - PLLA's  Produce

(DAME- co- PPG700_1.1), 1 eq., 20.0 g), L-lactide (44 eq., 9.02 g, 62.6 mmol) prepared in the above step 1, (II) 2-ethylhexanoate (Sn (Oct) ₂ , 0.01 eq., 6 mg, 0.014 mmol) and toluene (20 mL) were added and reacted at 110 ° C for 5 hours.

After the reaction, 30 mL of chloroform was added to dissolve and precipitated in methanol to obtain PLLA-poly (DAME- co- PPG700_1.1) -PLLA as a pale brown solid.

step 3: [PLLA-poly (DAME- co - PPG700 _1.1)] _n Manufacturing

A pressure reactor was charged with the dimeric acid methyl ester polyester / lactide block polyester PLLA-poly (DAME- co- PPG700_1.1) -PLLA (1 eq., 20.0 g), diisocyanate (MDI, 1 eq. (II) 2-ethylhexanoate (Sn (Oct) ₂ , 10 mg) and toluene (20 mL) were placed and reacted at 80 ° C. for 8 hours.

After the reaction, 10 mL of chloroform was added to dissolve and precipitated in methanol to give [PLLA-poly (DAME- co- PPG700_1.1)] _n as a pale brown solid.

< Example  4> Preparation of polyurethane elastomer according to the present invention 4

Step 1: Poly (DAME- co -PPG700_1.2)  Produce

First, 4 is installed with a thermometer, a stirrer, a distiller, a nitrogen tube reactor to obtain the following dimer acid methyl ester (. DAME, 1eq, 40.0g, 68.0mmol) and polypropylene glycol _{(PPG, M W: 700,} 1.1eq,. 56.0 g, 81.0 mmol) were placed in the four-necked reactor, followed by nitrogen purge for 30 minutes.

Next, titanium (IV) butoxide (TBT, 0.1 eq., 2.31 g, 7.0 mmol) was further added to the four-necked reactor and reacted at 160 ° C for 2 hours under nitrogen purge.

Then, the nitrogen purge was stopped, and the mixture was reacted at 180 ° C. for 16 hours and at 200 ° C. for 4 hours under high vacuum (200 torr) and 180 ° C. for 2 hours and under high vacuum (1 torr or less), respectively, to obtain poly (DAME- co- PPG700_1. 2).

Step 2: PLLA - Poly (DAME- co - PPG700 _1.2) - PLLA's  Produce

(DAME- co- PPG700_1.2), 1 eq., 20.0 g), L-lactide (39 eq., 8.57 g, 59.5 mmol) prepared in the above step 1, Tin (II) 2-ethylhexanoate (Sn (Oct) ₂ , 0.01 eq., 6 mg, 0.015 mmol) and toluene (20 mL) were placed and reacted at 110 ° C for 5 hours.

After the reaction, 30 mL of chloroform was added to dissolve and precipitated in methanol to obtain PLLA-poly (DAME- co- PPG700_1.1) -PLLA as a pale brown solid.

step 3: [PLLA-poly (DAME- co - PPG700 _1.2)] _n Manufacturing

A pressure reactor was charged with the dimer acid methyl ester polyester / lactide block polyester PLLA-poly (DAME- co- PPG700_1.2) -PLLA (1 eq., 32.0 g), diisocyanate (MDI, 1 eq. (II) 2-ethylhexanoate (Sn (Oct) ₂ , 10 mg) and toluene (30 mL) were placed and reacted at 80 ° C. for 8 hours.

After the reaction, 10 mL of chloroform was added to dissolve and precipitated in methanol to give [PLLA-poly (DAME- co- PPG700_1.2)] _n as a pale brown solid.

< Example  5> Production of polyurethane elastomer according to the present invention 5

Step 1: Poly (DAME- co -PPG1000_1.1)  Produce

(DAME, 1 eq., 30.0 g, 51.0 mmol) and polypropylene glycol (PPG, M _w : 1000, 1.0 eq. 55.9 g, 556.0 mmol) were placed in the four-necked reactor and purged with nitrogen for 30 minutes.

Next, titanium (IV) butoxide (TBT, 0.1 eq., 1.73 g, 5.0 mmol) was further added to the four-necked reactor and reacted at 160 ° C for 2 hours under nitrogen purge.

Then, the nitrogen purge was stopped, and the mixture was reacted at 180 ° C. for 16 hours and at 200 ° C. for 4 hours under high vacuum (200 torr) and 180 ° C. for 2 hours and under high vacuum (1 torr or less), respectively, to obtain poly (DAME- co- PPG1000_1. 1).

Step 2: PLLA - Poly (DAME-co- PPG1000 _1.1) - PLLA's  Produce

(DAME- co- PPG1000_1.1), 1 eq., 10.0 g), L-lactide (38 eq., 4.29 g, 29.7 mmol) prepared in the above step 1, Tin (II) 2-ethylhexanoate (Sn (Oct) ₂ , 0.01 eq., 3 mg, 0.008 mmol) and toluene (10 mL) were placed and reacted at 110 ° C for 5 hours.

After the reaction, 30 mL of chloroform was added to dissolve and precipitated in methanol to obtain PLLA-poly (DAME- co- PPG1000_1.1) -PLLA as a pale brown solid.

step 3: [PLLA-poly (DAME- co - PPG1000 _1.1)] _n Manufacturing

A pressure reactor was charged with the dimer acid methylester polyester / lactide block polyester PLLA-poly (DAME- co- PPG1000_1.1) -PLLA (1 eq., 10.0 g), diisocyanate (MDI, 1 eq. (II) 2-ethylhexanoate (Sn (Oct) ₂ , 10 mg) and toluene (30 mL) were placed and reacted at 80 ° C. for 8 hours.

After the reaction, 10 mL of chloroform was added to dissolve and precipitated in methanol to give [PLLA-poly (DAME- co- PPG1000_1.1)] _n as a pale brown solid.

< Example  6> Production of a polyurethane elastomer according to the present invention 6

Step 1: Poly (DAME- co -PPG1000_1.2)  Produce

(DAME, 1 eq., 30.0 g, 51.0 mmol) and polypropylene glycol (PPG, M _w : 1000, 1.1 eq. 61.0 g, 61.0 mmol) were placed in the four-necked reactor and purged with nitrogen for 30 minutes.

Next, titanium (IV) butoxide (TBT, 0.1 eq., 2.31 g, 7.0 mmol) was further added to the four-necked reactor and reacted at 160 ° C for 2 hours under nitrogen purge.

Then, the nitrogen purge was stopped, and the mixture was reacted at 180 ° C. for 16 hours and at 200 ° C. for 4 hours under high vacuum (200 torr) and 180 ° C. for 2 hours and under high vacuum (1 torr or less), respectively, to obtain poly (DAME- co- PPG1000_1. 2).

Step 2: PLLA - Poly (DAME- co - PPG1000 _1.2) - PLLA's  Produce

(DAME- co- PPG1000_1.2), 1 eq., 10.0 g), L-lactide (23 eq., 4.29 g, 29.7 mmol) prepared in the above step 1, Tin (II) 2-ethylhexanoate (Sn (Oct) ₂ , 0.01 eq., 5 mg, 0.013 mmol) and toluene (10 mL) were placed and reacted at 110 ° C for 5 hours.

After the reaction, 30 mL of chloroform was added to dissolve and precipitated in methanol to obtain PLLA-poly (DAME- co- PPG1000_1.2) -PLLA as a pale brown solid.

step 3: [PLLA-poly (DAME- co - PPG1000 _1.2)] _n Manufacturing

A pressure reactor was charged with the dimer acid methylester polyester / lactide block polyester PLLA-poly (DAME- co- PPG1000_1.1) -PLLA (1 eq., 10.0 g), diisocyanate (MDI, 1 eq. (II) 2-ethylhexanoate (Sn (Oct) ₂ , 10 mg) and toluene (30 mL) were charged and reacted at 80 ° C. for 8 hours.

After the reaction, 10 mL of chloroform was added to dissolve and precipitated in methanol to give [PLLA-poly (DAME- co- PPG1000_1.2) -PLLA] _n as a pale brown solid.

< Experimental Example  1> Example  1 &lt; / RTI &gt; ^One H-NMR analysis

(DAME- co- PPG400_1.1), PLLA-poly (DAME- co- PPG400_1.1) -PLLA, and [PLLA-poly (DAME- co- PPG400_1.1)) prepared in each step in Example 1 according to the present invention. 1)] it was carried out in ¹ H-NMR analysis _n.

One. Poly (DAME- co -PPG400_1.1) ^One H-NMR analysis

1 is a ¹ H-NMR spectroscopy of poly (DAME- co- PPG400_1.1) prepared in step 1 of Example 1. Fig.

As can be seen from FIG. 1, ¹ H-NMR analysis revealed that the terminal group of the polyester remained in the form of alcohol.

2. PLLA - Poly (DAME- co - PPG400 _1.1) - PLLA's ^One H-NMR analysis

2 is a ¹ H-NMR spectroscopy of PLLA-poly (DAME- co- PPG400_1.1) -PLLA prepared in step 2 of Example 1. Fig.

3. [ PLLA - Poly (DAME- co - PPG400 _1.1)] _n of ^One H-NMR analysis

3 is a ¹ H-NMR spectroscopy of [PLLA-poly (DAME- co- PPG)] _n prepared in step 3 of Example 1.

< Experimental Example  2> Example  2 &lt; / RTI &gt; ^One H-NMR analysis

(DAME- co- PPG400_1.2), PLLA-poly (DAME- co- PPG400_1.2) -PLLA and [PLLA-poly (DAME- co- PPG400_1. 2)] it was carried out in ¹ H-NMR analysis _n.

One. Poly (DAME- co -PPG400_1.2) ^One H-NMR analysis

4 is a ¹ H-NMR spectroscopy of poly (DAME- co- PPG400_1.2) prepared in step 1 of Example 2. Fig.

As can be seen from FIG. 4, ¹ H-NMR analysis showed that the terminal group of the polyester remained in the form of alcohol.

2. PLLA - Poly (DAME- co - PPG400 _1.2) - PLLA's ^One H-NMR analysis

5 is a ¹ H-NMR spectroscopy of PLLA-poly (DAME- co- PPG400_1.2) -PLLA prepared in step 2 of Example 2. Fig.

3. [ PLLA - Poly (DAME- co - PPG400 _1.2)] _n of ^One H-NMR analysis

6 is a ¹ H-NMR spectroscopy of [PLLA-poly (DAME- co- PPG400_1.2)] _n prepared in step 3 of Example 2. Fig.

< Experimental Example  3> Example  3 &lt; / RTI &gt; ^One H-NMR analysis

(DAME- co- PPG700_1.1), PLLA-poly (DAME- co- PPG700_1.1) -PLLA and [PLLA-poly (DAME- co- PPG700_1.1)) prepared in each step in Example 3 according to the present invention. 1)] it was carried out in ¹ H-NMR analysis _n.

One. Poly (DAME- co -PPG700_1.1) ^One H-NMR analysis

7 is a ¹ H-NMR spectroscopy of poly (DAME- co- PPG700_1.1) prepared in step 1 of Example 3. Fig.

As can be seen from FIG. 7, ¹ H-NMR analysis showed that the terminal group of the polyester remained in the form of alcohol.

2. PLLA - Poly (DAME- co - PPG700 _1.1) - PLLA's ^One H-NMR analysis

8 is a ¹ H-NMR spectroscopy of PLLA-poly (DAME- co- PPG700_1.1) -PLLA prepared in step 2 of Example 3. Fig.

3. [ PLLA - Poly (DAME- co - PPG700 _1.1)] _n of ^One H-NMR analysis

9 is a ¹ H-NMR spectroscopy of [PLLA-poly (DAME- co- PPG700_1.1)] _n prepared in step 3 of Example 3. Fig.

< Experimental Example  4> Example  4 ^One H-NMR analysis

(DAME- co- PPG700_1.2), PLLA-poly (DAME- co- PPG700_1.2) -PLLA and [PLLA-poly (DAME- co- PPG700_1. 2)] it was carried out in ¹ H-NMR analysis _n.

One. Poly (DAME- co -PPG700_1.2) ^One H-NMR analysis

10 is a ¹ H-NMR spectroscopy of poly (DAME- co- PPG700_1.2) prepared in step 1 of Example 4. Fig.

As can be seen from FIG. 10, ¹ H-NMR analysis confirmed that the terminal group of the polyester remained in the form of alcohol.

2. PLLA - Poly (DAME- co - PPG700 _1.2) - PLLA's ^One H-NMR analysis

11 is a ¹ H-NMR spectroscopy of PLLA-poly (DAME- co- PPG700_1.2) -PLLA prepared in step 2 of Example 4. Fig.

3. [ PLLA - Poly (DAME- co - PPG700 _1.2)] _n of ^One H-NMR analysis

12 is a ¹ H-NMR spectroscopy of [PLLA-poly (DAME- co- PPG700_1.2)] _n prepared in step 3 of Example 4. Fig.

< Experimental Example  5> Example  Step-5 ^One H-NMR analysis

(DAME- co- PPG1000_1.1), PLLA-poly (DAME- co- PPG1000_1.1) -PLLA, and [PLLA-poly (DAME- co- PPG1000_1.1)) prepared in each step in Example 5 according to the present invention. 1)] it was carried out in ¹ H-NMR analysis _n.

One. Poly (DAME- co -PPG1000_1.1) ^One H-NMR analysis

13 is a ¹ H-NMR spectroscopy of poly (DAME- co- PPG1000_1.1) prepared in step 1 of Example 5. Fig.

As can be seen from FIG. 13, ¹ H-NMR analysis showed that the terminal group of the polyester remained in the form of alcohol.

2. PLLA - Poly (DAME- co - PPG1000 _1.1) - PLLA's ^One H-NMR analysis

14 is a ¹ H-NMR spectroscopy of PLLA-poly (DAME- co- PPG1000_1.1) -PLLA prepared in step 2 of Example 5. Fig.

3. [ PLLA - Poly (DAME- co - PPG1000 _1.1)] _n of ^One H-NMR analysis

15 is a ¹ H-NMR spectroscopy of [PLLA-poly (DAME- co- PPG1000_1.1)] _n prepared in step 3 of Example 5.

< Experimental Example  6> Example  6 ^One H-NMR analysis

(DAME- co- PPG1000_1.2), PLLA-poly (DAME- co- PPG1000_1.2) -PLLA and [PLLA-poly (DAME- co- PPG1000_1.2)) prepared in each step in Example 6 according to the present invention. 2)] it was carried out in ¹ H-NMR analysis _n.

One. Poly (DAME- co -PPG1000_1.2) ^One H-NMR analysis

16 is a ¹ H-NMR spectroscopy of poly (DAME- co- PPG1000_1.2) prepared in step 1 of Example 6. Fig.

As can be seen from FIG. 16, ¹ H-NMR analysis showed that the terminal group of the polyester remained in the form of alcohol.

2. PLLA - Poly (DAME- co - PPG1000 _1.2) - PLLA's ^One H-NMR analysis

17 is a ¹ H-NMR spectroscopy of PLLA-poly (DAME- co- PPG1000_1.2) -PLLA prepared in step 2 of Example 6. Fig.

3. [ PLLA - Poly (DAME- co - PPG1000 _1.2)] _n of ^One H-NMR analysis

18 is a ¹ H-NMR spectroscopy of [PLLA-poly (DAME- co- PPG1000_1.2)] _n prepared in step 3 of Example 6.

< Experimental Example  7> Example  FT-IR analysis of the step-wise products according to Scheme 6

Poly (DAME- co -PPG) is made at each step in the sixth embodiment according to the present invention, PLLA- poly (DAME- co -PPG) -PLLA and [PLLA- poly (DAME- co -PPG) -PLLA] _n FT-IR &lt; / RTI &gt;

One. Poly (DAME- co -PPG1000_1.2)  FT-IR analysis

19 (a) is an FT-IR analysis spectrum of poly (DAME- co- PPG1000_1.2) prepared in step 1 of Example 6. Fig.

19 (a), a strong C = O stretch vibration peak of the ester is observed at 1736 cm &lt; ¹ &gt;.

2. PLLA - Poly (DAME- co - PPG1000 _1.2) - PLLA's  analysis

19 (b) is an FT-IR spectroscopy of PLLA-poly (DAME- co- PPG1000_1.2) -PLLA prepared in step 2 of Example 6. Fig.

As can be seen in (b) of Figure 19, FT-IR analysis results 1736cm ^- in the number of ¹ and 1760cm ^-1 C = O stretching vibration wave strong peak of PLLA ester was observed.

3. [ PLLA - Poly (DAME- co - PPG ) - PLLA ] _n FT-IR analysis of

19 (c) is an FT-IR analysis spectrum of [PLLA-poly (DAME- co- PPG) -PLLA] _n prepared in step 3 of Example 6.

NH bending (bending) of the directional (aromatic) CC peak and urethane bond of MDI in the number of 1536cm ^-1 and ¹ wave (- ^- the result of FT-IR analysis, Fig 19 (c) 1600cm as shown in (NH) - ( C = O) -O-) and a CN stretching peak were observed.

< Experimental Example  8> Example  1 ~ Example  Analysis of the physical properties of the step-by-step products

(DAME- co- PPG), PLLA-poly (DAME- co- PPG) -PLLA and [PLLA-poly (DAME- co- PPG)) prepared in Examples 1 to 6 according to the present invention, -PLLA] _n were analyzed.

One. Poly (DAME- co -PPG)  Material characterization

The physical properties of poly (DAME- co- PPG) prepared according to Step 1 in Examples 1 to 6 were analyzed and are shown in Table 1 below.

Copolymer [PPG] /
[DAME] M _n
(kg / mol) DP _n [-CH _3]
(%) M _n
(kg / mol) M _w
(kg / mol) Ð Poly (DAME- co- PPG400_1.1) 1.1 15.8 16.5 7.4 7.0 33.0 4.74 Poly (DAME- co- PPG400_1.2) 1.2 9.2 9.1 3.8 6.0 25.0 4.14 Poly (DAME- co- PPG700_1.1) 1.1 14.0 10.5 6.3 6.2 18.6 2.99 Poly (DAME- co- PPG700_1.2) 1.2 9.3 6.8 3.7 6.8 20.5 3.02 Poly (DAME- co- PPG1000_1.1) 1.1 12.9 7.6 13.3 9.6 26.4 2.75 Poly (DAME- co- PPG1000_1.2) 1.2 7.7 4.3 3.9 8.0 22.7 2.83

2. PLLA - Poly (DAME- co - PPG ) - PLLA's  Material characterization

The physical properties of PLLA-poly (DAME- co- PPG) -PLLA prepared according to Step 2 in Examples 1 to 6 were analyzed and shown in Table 2 below.

Triblock copolymer M _{n, PLLA}
(kg / mol) M _n
(kg / mol) w _PLLA M _n
(kg / mol) M _w
(kg / mol) Ð NMR TGA PLLA-poly (DAME- co-
PPG400_1.1) -PLLA 7.5 23.3 0.322 0.305 19.5 39.9 2.04 PLLA-poly (DAME- co-
PPG400_1.2) -PLLA 4.3 13.5 0.319 0.310 15.0 29.4 1.96 PLLA-poly (DAME- co-
PPG700_1.1) -PLLA 5.4 19.4 0.28 0.319 17.2 28.6 1.66 PLLA-poly (DAME- co-
PPG700_1.2) -PLLA 3.8 13.1 0.292 0.302 19.7 29.7 1.51 PLLA-poly (DAME- co-
PPG1000_1.1) -PLLA 4.8 17.7 0.271 0.301 19.5 31.3 1.61 PLLA-poly (DAME- co-
PPG1000_1.2) -PLLA 3.6 11.3 0.319 0.291 19.0 29.1 1.54

3. [ PLLA - Poly (DAME- co - PPG )] _n Analysis of material properties

The physical properties of PLLA-poly (DAME- co- PPG) -PLLA prepared according to Step 3 in Examples 1 to 6 were analyzed and shown in Table 3 below.

Polyurethane M _n
(kg / mol) M _n
(kg / mol) M _w
(kg / mol) Ð n [PLLA-poly (DAME- co-
PPG400_1.1)] _n 29.6 24.8 67.4 2.72 1.27 PLLA-poly (DAME- co-
PPG400_1.2)] _n 25.5 28.3 76.8 2.71 1.89 PLLA-poly (DAME- co-
PPG700_1.1)] _n 27.4 24.2 49.7 2.05 1.41 PLLA-poly (DAME- co-
PPG700_1.2)] _n 37.5 56.3 118.0 2.10 2.86 PLLA-poly (DAME- co-
PPG1000_1.1)] _n 44.3 48.8 94.0 1.93 2.50 PLLA-poly (DAME- co-
PPG1000_1.2)] _n 30.7 51.6 101.7 1.97 2.72

< Experimental Example  9> Example  Thermal characterization of the step-by-step 5 product

(DAME- co- PPG1000_1.1), PLLA-poly (DAME- co- PPG1000_1.1) -PLLA and [PLLA - poly (DAME- co- PPG1000_1.1) -PLLA] _n .

20 is a graph showing the results of DSC analysis for Example 5. Fig.

As can be seen in Fig. 20, the glass transition temperature caused by the rubber-like nature of poly (DAME- co- PPG1000_1.1), the product of step 1, was found at -55 deg.

The product of step 2, PLLA-poly (DAME- co- PPG1000_1.1) -PLLA, had two glass transition temperatures and one melting point. At this time, one of the two glass transition temperatures is the glass transition temperature of the rubber phase region due to the dimer acid polyester, and the glass transition temperature appearing near 55 ° C is the glass transition temperature that is different from that of the polylactide.

The melting point of the polylactide was confirmed to appear at 135 ° C, and the area of the melting point peak means the heat of fusion of the crystal, and the larger the heat of fusion, the greater the degree of crystallinity.

In the case of the product of step 3 [PLLA-poly (DAME- co- PPG1000_1.1) -PLLA] _n polyurethane elastomer, the area of the rubber phase was not significantly different from the products of the previous step but the melting point of the polylactide was about 95 Deg.] C, and the area of the peak was found to be very small. As a result, it was confirmed that the crystallinity of the polylactide was lowered.

< Experimental Example  10> Example  1 ~ Example  6 Analysis of Mechanical Properties of Polyurethane Elastomers According to

The mechanical properties of the polyurethane finally prepared in Examples 1 to 6 according to the present invention were analyzed. Mechanical properties analysis was performed by measuring the Young 's modulus, tensile strength and tensile elongation of polyurethane.

The Young's modulus, tensile strength and tensile elongation of the polyurethane are shown in Table 4 below.

Polyurethane elastomer Young's modulus, E
(MPa) Tensile strength, σ
(MPa) Tensile elongation, ε
(%) Example 1 1.23 + - 0.1 2.83 ± 0.1 618 ± 11 Example 2 3.84 ± 0.1 1.49 ± 0.1 289 ± 7 Example 3 5.38 + 0.1 2.39 ± 0.1 300 ± 24 Example 4 3.56 ± 0.1 5.09 ± 0.2 2221 ± 86 Example 5 7.89 ± 0.1 5.08 ± 0.1 1576 ± 106 Example 6 3.90 ± 0.1 3.86 ± 0.1 1918 ± 225

21 is a graph showing the S-S Curve (tensile strength-tensile elongation curve) of the polyurethane finally prepared in Examples 1 to 6. Fig.

As shown in FIG. 21, tensile elongation was about 2000% in Examples 4 and 6, and tensile strengths in Examples 4, 5 and 6 were more than 3 MPa.

Therefore, it can be confirmed that the polyurethane elastomer according to the present invention has excellent tensile strength and tensile elongation, and thus can be effectively used as a material for a pressure-sensitive adhesive, an elastic body, a paint composition, and a coating composition.

Claims (14)

A polyether polyol ester-bonded with a dimer acid or a C ₁ -C ₆ alkyl ester thereof, which is a compound represented by the following formula (1);
And a polylactic acid ester-bonded to the polyether polyol,
Wherein the ends of the polylactic acid between the units are crosslinked by diisocyanate.
[Chemical Formula 1]

In Formula 1,
R ¹ and R ² are each independently a straight chain alkylene group of C ₁ to C ₁₀ ,
R ³ and R ⁴ are each independently straight chain alkyl of C ₁ to C ₁₀ .
The method according to claim 1,
Wherein the dimer acid is obtained from oleic fatty acid and linoleic acid.
delete delete The method according to claim 1,
Wherein the polyether polyol compound is a polyurethane elastomer which is a compound represented by the following formula (2): &lt; EMI ID =
(2)

In Formula 2,
R ⁵ is a methylene group, a C ₂ -C ₅ straight-chain alkylene group or a C ₃ -C ₅ branched-chain alkylene group; And
n is an integer of 1-30.
The method according to claim 1,
Wherein the polyether polyol compound is polypropylene glycol or polyethylene glycol.
The method according to claim 6,
Wherein said polypropylene glycol or polyethylene glycol is a polyurethane elastomer having a number average molecular weight of 400 to 1000.
The method according to claim 1,
An equivalent ratio of the polyether polyol to a dimer acid or a C ₁ -C ₆ alkyl ester thereof is 1.0 to 1.1.
The method according to claim 1,
Wherein the diisocyanate compound is at least one compound selected from the group consisting of toluene diisocyanate (TDI), 4,4-methylenediphenyl diisocyanate (MDI), 1,5-naphthylene diisocyanate (NDI), 1,6-hexamethylene diisocyanate Wherein the polyurethane elastomer is at least one selected from the group consisting of phthalic anhydride, perylene diisocyanate (IPDI), xylene diisocyanate (XDI), tetramethyl xylene diisocyanate (TMXDI), and 1,8-diisocyanate methyl octane.
The method according to claim 1,
Wherein the polyurethane elastomer is a polymer represented by the following formula (3): &lt; EMI ID =
(3)

In Formula 3,
n is an integer from 1-30;
m is an integer from 1 to 100;
X is an integer of 1-20;
Y is an integer of 1-10;
R ¹ and R ² are each independently C ₁ -C ₁₀ straight chain alkylene;
R ³ and R ⁴ are each independently C ₁ -C ₁₀ straight chain alkyl;
R ⁵ is methylene, or C ₂ -C ₅ linear or branched alkylene; And
R ⁶ is methylene, C ₂ -C ₁₀ linear or branched alkylene, cyclo C ₆ -C ₂₀ alkylene or C ₆ -C ₂₀ arylene substituted with unsubstituted or C ₁ -C ₃ alkyl, or

to be.
Esterifying a polyether polyol with a dimer acid or a C ₁ -C ₆ alkyl ester thereof (step 1);
Esterifying polylactic acid with the polyether polyol of step 1 (step 2); And
A process for producing a polyurethane elastomer according to claim 1, comprising the step of reacting a polylactic acid terminal of the product prepared in step 2 with a diisocyanate compound to prepare a polyurethane elastomer (step 3).
An adhesive composition comprising the polyurethane elastomer according to Claim 1.
A paint composition comprising the polyurethane elastomer according to claim 1.
A coating composition comprising a polyurethane elastomer according to claim 1.

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