KR101737326B1 - Polyurethane having furan-based polyesterpolyol and method for preparing the same - Google Patents

Abstract

A furan-based polyester polyol represented by the following formula (1); And a diisocyanate-based compound; and a polyurethane containing a furan-based polyester polyol. Accordingly, the polyurethane of the present invention can be applied to various fields, and particularly, it can be utilized as a coating material.
[Chemical Formula 1]

Description

FIELD OF THE INVENTION [0001] The present invention relates to a polyurethane containing a furan-based polyester polyol, and a process for producing the same. BACKGROUND ART [0002]

More particularly, the present invention relates to a polyurethane comprising a furan-based polyester polyol and a process for producing the same.

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 a furan-based polyester polyol represented by the following formula (1): And a diisocyanate-based compound; and a polyurethane containing a furan-based polyester polyol.

[Chemical Formula 1]

In Formula 1,

R is independently an alkylene group of C1 to C20,

n is an integer of 1 to 10;

According to an embodiment of the present invention, preferably,

Each R may independently be a linear C2 to C18 alkylene group.

Wherein the diisocyanate compound is selected from the group consisting of methylene diphenyl diisocyanate, 4,4'-methylene dicyclohexyl 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 furan-based polyester polyol represented by Formula 1 may be 500 to 5,000.

The weight average molecular weight (Mw) of the polyurethane containing the furan-based polyester polyol may be 5,000 to 70,000.

According to another aspect of the present invention,

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

According to another aspect of the present invention,

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

[Chemical Formula 1]

In Formula 1,

R is independently an alkylene group of C1 to C20,

n is an integer of 1 to 10;

Reacting the furan-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 a furan-based polyester polyol containing a polyisocyanate compound can be provided.

(2)

(3)

HO-R-OH

In Formula 3,

And R is an alkylene group of C1 to C20.

According to an embodiment of the present invention, preferably,

The R may be a linear C2 to C18 alkylene group.

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

In the step (b), the furan-based polyester polyol and the diisocyanate compound may be reacted at a molar ratio of 1: 1.1 to 1: 2.5.

The reaction of step (a) may be carried out at a temperature of 180 to 220 ° C.

The reaction of step b may be carried out at a temperature of 120-150 < 0 > C.

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

The polyurethane comprising the furan-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 results of GPC 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 including the furan-based polyester polyol of the present invention will be described.

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

[Chemical Formula 1]

In Formula 1,

R is independently an alkylene group of C1 to C20,

and n is an integer of 1 to 10.

Preferably, R may be a linear C2 to C18 alkylene group.

The diisocyanate compound may be selected from the group consisting of methylene diphenyl diisocyanate, 4,4'-methylene dicyclohexyl 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 Available, but can be used more preferably, the diphenylmethane diisocyanate or 4,4'-methylene dicyclohexyl diisocyanate.

The number average molecular weight (Mn) of the furan-based polyester polyol represented by Formula 1 is preferably 500 to 5,000.

The weight average molecular weight (Mw) of the polyurethane containing the furan-based polyester polyol is preferably 5,000 to 70,000.

The furan-based polyester polyol may be used as a coating material, but is not limited thereto and may be used in various fields.

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

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

(2)

(3)

HO-R-OH

In Formula 3,

And R is an alkylene group of C1 to C20. Preferably, R may be a linear C2 to C18 alkylene group.

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

In addition, the reaction of step (a) is preferably carried out at a temperature of 180 to 220 ° C.

If the reaction temperature of step a is less than 180 ° 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.

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

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

Here, the furan-based polyester polyol and the diisocyanate compound are preferably reacted at a molar ratio of 1: 1.1 to 1: 2.5.

The reaction of step (b) is preferably carried out at a temperature of 120 to 150 ° C.

If the reaction temperature in step b is less than 120 ° C, the reaction rate may be lowered, and if the reaction temperature is higher than 150 ° C, by-product production may be increased.

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: Furan system Of polyester polyol  Produce

5 g (0.032 mol) of FDCA (furandicarboxylic acid) and 12.95 g (0.064 mol) of Dodecanediol were placed in a 250 mL three-necked flask. And 350 ppm (3.82 ml) of titanium butoxide were put together and reacted for 5 hours under a nitrogen atmosphere at 180 ° C. After the completion of the reaction, the temperature was lowered to 50 ° C and dissolved in chloroform for 5 hours or longer, then precipitated in methanol and filtered.

Manufacturing example  1-2: Preparation of polyurethane

5 g (0.0015 mol) of the furan-based polyester polyol obtained in Production Example 1-1 was dissolved in a nitrogen atmosphere at 130 ° C. 0.95 g (0.0038 mol) of MDI (methylene diphenyl diisocyanate) and 2 mol% of the catalyst dibutyltindiaurate were added to the polyester polyol for 1 hour. After completion of the reaction, the reaction product was dissolved in chloroform at 50 DEG C, precipitated in methanol, and then filter-dried to prepare a polyurethane.

Example  2

5 g (0.0015 mol) of the furan-based polyester polyol obtained in Production Example 1-1 was dissolved in a nitrogen atmosphere at 130 ° C. 0.99 g (0.0038 mol) of H ₁₂ MDI (4,4'-Methylene dicyclohexyl diisocyanate) and 2 mol% of the catalyst Dibutyltindiaurate with respect to the number of moles of the polyester polyol were reacted for 5 hours. After completion of the reaction, the reaction mixture was dissolved in chloroform at 50 ° C, precipitated in methanol, and then dried.

Test Example  One: NMR  analysis

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

Referring to Figure 1, furan ring 2H (7.1ppm) , Dodecanediol -O- CH 2 - (CH 2) 10 - CH 2 -O- 4H (4.4ppm), Dodecandiol -O-CH 2 - (CH 2) 10 - CH ₂ -O-, 20H (1.2 ~ 2.0ppm), it was confirmed that the furan-based polyester polyol was synthesized.

Test Example  2: Furan system Polyester polyol  GPC for Come Permeation  Chromatography

The furan-based polyester polyol prepared in Preparation Example 1 was subjected to a high-temperature gel permeation chromatography (GPC) analysis using m-Cresol at 100 ° C, and the results are shown in FIG.

2, the number average molecular weight (Mn) was 2600, the weight average molecular weight (Mw) was 3300, and the polydispersity index (PDI) was 1.3.

Test Example  3: for polyurethane GPC ( Come Permeation Chromatography ) analysis

The furan-based polyester polyol prepared according to Preparation Example 1, the polyurethane prepared according to Example 1 and the polyurethane prepared according to Example 2 were subjected to high-temperature GPC (Gel Permeation Chromatography) using m-Cresol at 100 ° C, And the results are shown in Fig. Here, the blue curve represents the results of the furan-based polyester polyol of Production Example 1, the red curve represents the polyurethane of Example 1, and the green curve represents the results of the polyurethane of Example 2, respectively.

3, the polyester polyol of Production Example 1 had a number average molecular weight (Mn) of 2600 and a weight average molecular weight (Mw) of 3300, whereas the polyurethane of Example 1 had a number average molecular weight of 17600, a weight average molecular weight of 29200, And the polyurethane of Example 2 was measured to have a number average molecular weight of 8600, a weight average molecular weight of 13,600 and a PDI of 1.6.

Test Example  4: FT - IR ( ATR ) analysis

FT-IR (ATR) analysis was also performed on the furan-based polyester polyol prepared according to Preparation Example 1, the polyurethane prepared according to Example 1, and the polyurethane prepared according to Example 2, 4. Here, the black curve represents the results of the furan-based polyester polyol of Preparation Example 1, the red curve represents the polyurethane of Example 1, and the blue curve represents the results of the polyurethane of Example 2, respectively.

According to FIG. 4, Wavenumber permeability in the range of 700 to 4000 cm ^-1 was confirmed, and -OH steching vibration of 3400 cm ^-1 and 1720 cm ^-1 ester peak of polyester polyol was confirmed. Further, the urethane -NH streching vibration 3350cm ^-1, it was confirmed in the polyurethane -NH bending vibration 1530cm ^-1. Thus, polymerization of the polyurethane was confirmed.

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 (13)

A furan-based polyester polyol represented by the following formula (1); And
A diisocyanate compound; and a reaction product of
The diisocyanate compound is H12 MDI (4,4'-Methylenedicyclohexyldiisocyanate)
Polyurethanes containing furan-based polyester polyols.
[Chemical Formula 1]

In Formula 1,
R is independently an alkylene group of C1 to C20,
n is an integer of 1 to 10; The method according to claim 1,
And R are each independently a linear C2 to C18 alkylene group. delete The method according to claim 1,
The polyurethane according to claim 1, wherein the number average molecular weight (Mn) of the furan-based polyester polyol represented by the formula (1) is 500 to 5,000. The method according to claim 1,
Wherein the polyurethane comprising the furan-based polyester polyol has a weight average molecular weight (Mw) of 5,000 to 70,000. A coating material comprising a polyurethane comprising the furan-based polyester polyol of claim 1. Reacting a furandicarboxylic acid represented by the following formula (2) with an alkane diol represented by the following formula (3) to produce a furan-based polyester polyol represented by the following formula (1) (step a) ; And
[Chemical Formula 1]

In Formula 1,
R is independently an alkylene group of C1 to C20,
n is an integer of 1 to 10;

Reacting the furan-based polyester polyol represented by Formula 1 with a diisocyanate-based compound to prepare a polyurethane (Step b)
The diisocyanate compound is H12 MDI (4,4'-Methylenedicyclohexyldiisocyanate)
≪ / RTI > furan-based polyester polyol.
(2)

(3)
HO-R-OH
In Formula 3,
And R is an alkylene group of C1 to C20. 8. The method of claim 7,
Wherein R is a linear C2 to C18 alkylene group. ≪ RTI ID = 0.0 > 21. < / RTI > 8. The method of claim 7,
Wherein the reaction of the furan dicarboxylic acid and the alkane diol is carried out in a molar ratio of 1: 1.1 to 1: 2 in the step (a). 8. The method of claim 7,
Wherein the furan-based polyester polyol and the diisocyanate-based compound are reacted at a molar ratio of 1: 1.1 to 1: 2.5 in the step (b). 8. The method of claim 7,
Wherein the reaction of step (a) is carried out at a temperature of 180 to 220 占 폚. 8. The method of claim 7,
Wherein the reaction of step (b) is carried out at a temperature of from 120 to 150 < 0 > C. 8. The method of claim 7,
Wherein the furan-based polyester polyol is a biomass-derived compound. ≪ RTI ID = 0.0 > 21. < / RTI >

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