KR20150034890A - Polyurethane having alkane-based polyesterpolyol and method for preparing the same - Google Patents

Abstract

Provided is a polyurethane including alkane-based polyesterpolyol comprising reaction products of: alkane-based polyesterpolyol represented by chemical formula 1; and a diisocyanate-based compound. Accordingly, the polyurethane of the present invention can be applied to various fields and utilized as a coating material.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyurethane containing an alkane-based polyester polyol,

More particularly, the present invention relates to a polyurethane comprising an alkane-based polyester polyol produced by the reaction of an alkane-based polyester polyol with a polyol, and a process for producing the polyurethane.

Polyurethane is a general term for a polymer compound bonded by a urethane bond formed by a combination of an alcohol group and an isocyanate group, and a typical example is a spandex made of a synthetic fiber. Urethane-based synthetic rubber is also widely used. Urethane foam containing bubbles in polyurethane is also used in bedding mattresses.

Urethane-based synthetic rubbers include polyester-based and polyether-based rubbers. The polyester system is made by reacting propylene glycol and ethylene glycol with adipic acid to make a polyester, and a polyester having an OH group at both ends and having a molecular weight of up to 3,000 with an isocyanate compound such as naphthalene-1, 5-diisocyanate At the same time, it is made of polymer. In addition, the polyether system is made from a high molecular weight polyurethane by reacting propylene oxide with some ethylene oxide to make polyether first, and reacting the OH groups at both ends with an isocyanate compound such as toluylene diisocyanate.

BACKGROUND ART Conventionally, polyurethane has been used in a wide range of fields such as paints, adhesives, rolls, tubes, and binders for magnetic recording media. In addition, polyurethane is widely used as synthetic leather, film, and molding sheet utilizing such properties because it has excellent low temperature characteristics, excellent flexibility and durability as compared with other polymer resins. The polyurethane can also be used as a coating material for various products.

Such polyurethanes require the development of polyurethane technology capable of realizing properties suitable for the intended use, and their application fields are very diverse.

The object of the present invention is to prepare polyurethanes which can be applied to various fields, and in particular to produce polyester polyurethanes suitable for application as a coating material.

According to an aspect of the present invention, there is provided an alkane-based polyester polyol represented by the following general formula (1): And a diisocyanate compound; and a polyurethane comprising an alkane-based polyester polyol.

[Chemical Formula 1]

In Formula 1,

R ¹ and R ² may be the same or different from each other, R ¹ and R ² are each independently a C 1 to C 20 alkylene group,

n is an integer of 1 to 10;

According to an embodiment of the present invention, preferably,

R ¹ and R ² may be the same or different from each other, and R ¹ and R ² may each independently be a linear C 2 to C 18 alkylene group.

Wherein the diisocyanate compound is selected from the group consisting of 4,4'-Methylene dicyclohexyl diisocyanate, methylene diphenyl diisocyanate, 2,4-toluene diisocyanate (2,4 -Toluene diisocyanate, naphthalene diisocyanate, xylene diisocyanate, isophorone diisocyanate, p-phenylene diisocyanate, 3,3'-toluene, (3,3'-toluene-4,4'-diisocyanate), 1,4-cyclohexane diisocyanate, 2,4,4-trimethylhexa Methylene bis (4-cyclohexyl isocyanate), 1,6-hexamethylene diisocyanate, and methylene-bis (4-cyclohexyl isocyanate) During It may be more than one kind selected.

The number-average molecular weight (Mn) of the alkane-based polyester polyol represented by Formula 1 may be 500 to 20,000.

The weight average molecular weight (Mw) of the polyurethane containing the alkane-based polyester polyol may be 10,000 to 250,000.

The polyurethane containing the alkane-based polyester polyol may have a melting point of 110 to 140 ° C.

According to another aspect of the present invention,

A coating material comprising a polyurethane comprising the alkane-based polyester polyol may be provided.

According to another aspect of the present invention,

Reacting an alkanedioic acid represented by the following formula (2) with an alkane diol represented by the following formula (3) to produce an alkane-based polyester polyol represented by the following formula (1) (step a); And

[Chemical Formula 1]

In Formula 1,

R ¹ and R ² may be the same or different from each other, R ¹ and R ² are each independently a C 1 to C 20 alkylene group,

n is an integer of 1 to 10;

Reacting the alkane-based polyester polyol represented by Formula 1 with a diisocyanate-based compound to prepare a polyurethane (Step b);

A method for producing a polyurethane comprising an alkane-based polyester polyol including the above-mentioned alkane-based polyester polyol can be provided.

(2)

In Formula 2,

R ¹ is an alkylene group of C1 to C20.

(3)

HO-R ² -OH

In Formula 3,

R ² is an alkylene group of C1 to C20.

According to an embodiment of the present invention, preferably,

R ¹ and R ² may be the same or different from each other, and R ¹ and R ² may each independently be a linear C 2 to C 18 alkylene group.

In step a, the alkane dianionic acid and the alkane diol may be reacted at a molar ratio of 1: 1.1 to 1: 2.

In the step (b), the alkane-based polyester polyol and the diisocyanate-based compound may be reacted at a molar ratio of 1: 1.1 to 1: 6.

The reaction of step a) may be carried out at a temperature of 80 to 220 캜.

The reaction of step b may be carried out at a temperature of 70 to 120 < 0 > C.

The alkane-based polyester polyol may be a biomass-derived compound.

The polyurethane comprising the alkane-based polyester polyol according to the present invention can be applied to various fields, and is particularly suitable for use as a coating material.

Fig. 1 shows the results of NMR analysis according to Test Example 1. Fig.
Fig. 2 shows the result of DSC analysis according to Test Example 2. Fig.
Fig. 3 shows the results of GPC analysis according to Test Example 3. Fig.
4 shows FT-IR analysis results according to Test Example 4. FIG.

Hereinafter, embodiments and examples of the present invention will be described in detail so that those skilled in the art can easily carry out the present invention.

It is to be understood, however, that the following description is not intended to limit the invention to the particular embodiments, but includes all modifications, equivalents, and alternatives falling within the spirit and scope of the invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described in detail with reference to the accompanying drawings.

The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The singular expressions include plural expressions unless the context clearly dictates otherwise. In the present application, the terms "comprises ", or" having ", and the like, specify that the presence of stated features, integers, steps, operations, elements, or combinations thereof, But do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, or combinations thereof.

Hereinafter, embodiments of the present invention will be described in detail. However, it should be understood that the present invention is not limited thereto, and the present invention is only defined by the scope of the following claims.

As used herein, unless otherwise defined, the term "alkyl group" means a straight, branched or cyclic aliphatic hydrocarbon group. The alkyl group may be a "saturated alkyl group" which does not contain any double or triple bonds.

The alkyl group may be an "unsaturated alkyl group" comprising at least one double bond or triple bond.

The alkyl group may be a C1 to C6 alkyl group, preferably a C1 to C3 alkyl group.

For example, the C1 to C4 alkyl groups may have 1 to 4 carbon atoms in the alkyl chain, i.e., the alkyl chain may be optionally substituted with one or more substituents selected from the group consisting of methyl, ethyl, propyl, iso-propyl, n-butyl, Indicating that they are selected from the group.

Specific examples of the alkyl group include a methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, pentyl group, hexyl group, ethenyl group, Butyl group, cyclopentyl group, cyclohexyl group, and the like.

Hereinafter, the polyurethane containing the alkane-based polyester polyol of the present invention will be described.

The polyurethane comprising the alkane-based polyester polyol of the present invention comprises a reaction product of an alkane-based polyester polyol represented by the following formula (1) and a diisocyanate-based compound.

[Chemical Formula 1]

In Formula 1,

R ¹ and R ² may be the same or different from each other, R ¹ and R ² are each independently a C 1 to C 20 alkylene group,

n is an integer of 1 to 10;

Preferably, R ¹ and R ² may be the same or different from each other, and R ¹ and R ² may each independently be a linear C 2 to C 18 alkylene group.

Examples of the diisocyanate compound include 4,4'-methylene dicyclohexyl diisocyanate, methylene diphenyl diisocyanate, 2,4-toluene diisocyanate (2,4 -Toluene diisocyanate, naphthalene diisocyanate, xylene diisocyanate, isophorone diisocyanate, p-phenylene diisocyanate, 3,3'-toluene, (3,3'-toluene-4,4'-diisocyanate), 1,4-cyclohexane diisocyanate, 2,4,4-trimethylhexa Methylene diisocyanate, 2,4-trimethylhexamethylene diisocyanate, 1,6-hexamethylene diisocyanate, methylene-bis (4-cyclohexyl isocyanate) My back It can be used.

More preferably, the above-mentioned 4,4'-methylenedicyclohexyl diisocyanate can be used.

The number average molecular weight (Mn) of the alkane-based polyester polyol represented by Formula 1 is preferably 500 to 20,000.

The weight average molecular weight (Mw) of the polyurethane containing the alkane-based polyester polyol is preferably 10,000 to 250,000.

The polyurethane containing the alkane-based polyester polyol may have a melting point of 110 to 140 캜 and is suitable for use as a coating material.

Hereinafter, a method for producing a polyurethane comprising the alkane-based polyester polyol of the present invention will be described.

First, an alkane-based polyester polyol represented by Formula 1 is prepared by reacting an alkanedioic acid represented by Formula 2 and an alkane diol represented by Formula 3 (Step a).

(2)

In Formula 2,

R ¹ is an alkylene group of C1 to C20.

(3)

HO-R ² -OH

In Formula 3,

R ² is an alkylene group of C1 to C20.

Preferably, R ¹ and R ² may be the same or different from each other, and R ¹ and R ² may each independently be a linear C 2 to C 16 alkylene group.

The alkane dianionic acid and the alkane diol are preferably reacted at a molar ratio of 1: 1.1 to 1: 2.

The reaction of step (a) is preferably carried out at a temperature of 80 to 220 ° C.

If the reaction temperature in step a is less than 80 ° C, the reaction rate may be lowered, and if the reaction temperature is higher than 220 ° C, by-product production may be increased.

The reaction time may vary depending on the reaction temperature. The reaction time is long when the reaction temperature is low, and the reaction time is relatively short when the reaction temperature is high.

The reaction pressure can be easily and economically advantageous because the reaction can proceed at atmospheric pressure at the reaction temperature below the boiling point of the reactant. The boiling point of the reactant is higher than the boiling point of the reactant, and the pressure in the reactor increases due to the vapor pressure. Therefore, a reaction device capable of withstanding the pressurized condition is required, but the reaction time can be reduced as described above. Therefore, the reaction pressure, the reaction time, and the reaction temperature can be appropriately adjusted according to the situation.

Next, the polyurethane is prepared by reacting the alkane-based polyester polyol represented by Formula 1 with a diisocyanate-based compound (Step b).

Here, the alkane-based polyester polyol and the diisocyanate compound are preferably reacted at a molar ratio of 1: 1.1 to 1: 6.

The reaction of step (b) is preferably carried out at a temperature of 70 to 120 ° C.

If the reaction temperature of step b is less than 70 ° C, the reaction rate may be lowered, and if the reaction temperature is higher than 120 ° C, the production of by-products may be increased.

The alkane-based polyester polyol may be a biomass-derived compound.

Hereinafter, preferred embodiments of the present invention will be described in order to facilitate understanding of the present invention. However, the following examples are provided to further understand the present invention, and the present invention is not limited by the examples.

[Example]

Example  One

Manufacturing example  1-1: Alkane series Of polyester polyol  Produce

5 g (0.0217 mol) of dodecanedioic acid and 8.79 g (0.0434 mol) of dodecanediol were charged into a three-necked flask with DBTO 1 wt% (50 mg) catalyst. The reaction was carried out at 100 DEG C and 100 rpm for 30 minutes, and then further reacted at 190 DEG C and 150 rpm for 180 minutes.

Manufacturing example  1-2: Preparation of polyurethane

The alkane-based polyester polyol obtained in Preparation Example 1-1 and H ₁₂ MDI (4,4'-Methylene dicyclohexyl diisocyanate) were added in a molar ratio of 1: 5 and reacted at 80 ° C and 100 rpm for 1 hour to synthesize polyurethane Respectively.

Example  2

A polyurethane was synthesized in the same manner as in Example 1, except that the reaction time was changed from 2 hours to 1 hour instead of 1 hour.

Example  3

The polyurethane was synthesized in the same manner as in Example 1, except that the reaction time was changed to 3 hours instead of 1 hour.

Test Example  One: ^One H- NMR  analysis

The alkane-based polyester polyol prepared in Preparation Example 1 was dissolved in CDCl ₃ and subjected to ¹ H-NMR analysis. The results are shown in FIG.

Referring to Figure _{1, -COO- CH 2 - (CH} 2) 10 - CH 2 -O- (4H, 4.2ppm), -COO-CH 2 - (CH 2) 10 -CH 2 -O- (20H, 1.2 ~ 1.75ppm), -O-CO- CH 2 - (CH 2) 10 - CH 2 -CO-O- (4H, 2.3ppm), -O-CO-CH 2 - (CH 2) 10 -CH 2 - CO-O- (20H, 1.2 ~ 1.75ppm), and it was confirmed that the alkane-based polyester polyol was synthesized.

Test Example  2: DSC ( Differential Scanning Calorimetry )analysis

DSC analysis was performed to determine the melting point ( _Tm ) of each polymer, and the results are shown in FIG. The analysis was performed twice at a rate of 10 [deg.] C / min from 50 [deg.] C to 230 [deg.] C, and the second obtained data is shown in Fig.

2, the melting points of the polyester polyols prepared in Preparation Example 1 were 78.77 ° C and the melting points of the polyurethanes obtained in Examples 1 to 3 polymerized at different times from H ₁₂ MDI were 117 ° C .

Test Example  3: GPC ( Come Permeation Chromatography ) analysis

The alkane-based polyester polyol prepared according to Preparation Example 1 and the polyurethane prepared according to Examples 1 to 3 were subjected to high-temperature GPC analysis at 100 ° C using m-Cresol, respectively, Table 1 shows the results.

division Mn Mw PDI Production Example 1 10,800 19,700 1.81 Example 1 53,300 230,900 4.32 Example 2 61,300 171,800 2.80 Example 3 47,800 253,600 5.29

Test Example  4: FT - IR ( ATR ) analysis

FT-IR (ATR) analysis was performed to confirm the polymerization of the polyurethane, and the results are shown in FIG.

According to Fig. 4, the Wavenumber was observed in the range of 700-4000 cm ^-1 . At 2900cm ^-1 in the sp3 CH streching, 1720cm ^-1 was confirmed ester peak. -NH streching vibration 3350cm ^-1, it was found in the polyurethane -NH bending vibration 1530cm ^-1 of urethane.

The scope of the present invention is defined by the appended claims rather than the detailed description and all changes or modifications derived from the meaning and scope of the claims and their equivalents are to be construed as being included within the scope of the present invention do.

Claims (14)

An alkane-based polyester polyol represented by the following formula (1); And
A polyisocyanate compound, and a diisocyanate compound; and a polyurethane comprising an alkane-based polyester polyol.
[Chemical Formula 1]

In Formula 1,
R ¹ and R ² may be the same or different from each other, R ¹ and R ² are each independently a C 1 to C 20 alkylene group,
n is an integer of 1 to 10; The method according to claim 1,
R ¹ and R ² may be the same or different from each other, and R ¹ and R ² are each independently a linear C 2 to C 18 alkylene group. The method according to claim 1,
Wherein the diisocyanate compound is selected from the group consisting of 4,4'-Methylene dicyclohexyl diisocyanate, methylene diphenyl diisocyanate, 2,4-toluene diisocyanate (2,4 -Toluene diisocyanate, naphthalene diisocyanate, xylene diisocyanate, isophorone diisocyanate, p-phenylene diisocyanate, 3,3'-toluene, (3,3'-toluene-4,4'-diisocyanate), 1,4-cyclohexane diisocyanate, 2,4,4-trimethylhexa Methylene bis (4-cyclohexyl isocyanate), 1,6-hexamethylene diisocyanate, and methylene-bis (4-cyclohexyl isocyanate) In line The alkane-based polyurethane comprising a polyester polyol, characterized in that at least one member. The method according to claim 1,
Wherein the alkane-based polyester polyol represented by the formula (1) has a number average molecular weight (Mn) of 500 to 20,000. The method according to claim 1,
Wherein the polyurethane comprising the alkane-based polyester polyol has a weight average molecular weight (Mw) of 10,000 to 250,000. The method according to claim 1,
Wherein the polyurethane containing the alkane-based polyester polyol has a melting point of 110 to 140 ° C. A coating material comprising a polyurethane comprising the alkane-based polyester polyol of claim 1. Reacting an alkanedioic acid represented by the following formula (2) with an alkane diol represented by the following formula (3) to produce an alkane-based polyester polyol represented by the following formula (1) (step a); And
[Chemical Formula 1]

In Formula 1,
R ¹ and R ² may be the same or different from each other, R ¹ and R ² are each independently a C 1 to C 20 alkylene group,
n is an integer of 1 to 10;

Reacting the alkane-based polyester polyol represented by Formula 1 with a diisocyanate-based compound to prepare a polyurethane (Step b);
≪ / RTI > wherein the polyol comprises an alkane-based polyester polyol.
(2)

In Formula 2,
R ¹ is an alkylene group of C1 to C20.
(3)
HO-R ² -OH
In Formula 3,
R ² is an alkylene group of C1 to C20. 9. The method of claim 8,
Wherein R ¹ and R ² may be the same or different from each other, and R ¹ and R ² are each independently a linear C 2 to C 18 alkylene group. 9. The method of claim 8,
Wherein the alkanedioic acid is reacted with the alkane diol in a molar ratio of 1: 1.1 to 1: 2 in the step (a). 9. The method of claim 8,
Wherein the alkane-based polyester polyol and the diisocyanate-based compound are reacted at a molar ratio of 1: 1.1 to 1: 6 in the step (b). 9. The method of claim 8,
Wherein the reaction of step (a) is carried out at a temperature of 80 to 220 ° C. 9. The method of claim 8,
Wherein the reaction of step b) is carried out at a temperature of from 70 to 120 < RTI ID = 0.0 > C. < / RTI > 9. The method of claim 8,
Wherein the alkane-based polyester polyol is a biomass-derived compound. 2. The polyurethane according to claim 1, wherein the alkane-based polyester polyol is a biomass-derived compound.

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