KR20160065360A - Polyurethane having acrylic polyol and method for preparing the same - Google Patents

Abstract

Provided is a polyurethane comprising acrylic polyol. The polyurethane comprising acrylic polyol includes a reaction product of furan polyester polyol, acrylic polyol, and a ring-shaped aliphatic diisocyante-based compound. The polyurethane of the present invention can be used to various fields, particularly as a coating material. Also, a preparation method of the polyurethane can reduce environment contamination by obtaining furan-based polyester polyol from a biomass, and can enhance efficiency of biological resources.

Description

TECHNICAL FIELD [0001] The present invention relates to a polyurethane containing an acrylic polyol and a process for producing the same. BACKGROUND ART < RTI ID = 0.0 > POLYURETHANE HAVING ACRYLIC POLYOL AND METHOD FOR PREPARATION THE SAME &

More particularly, the present invention relates to a polyurethane comprising a furan-based polyester polyol, an acrylic polyol and a cyclic aliphatic diisocyanate, 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. In addition, there is a need to reduce environmental pollution by using raw materials of polyurethane polymerization from biomass.

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.

Another object of the present invention is to obtain a furan-based polyester polyol as a raw material for polyurethane polymerization from biomass, thereby reducing environmental pollution and efficiently using biomass.

In order to accomplish the above object of the present invention, there is provided a furan-based polyester polyol represented by the following formula (1); An acrylic polyol represented by the following formula (2); And

And a cyclic aliphatic diisocyanate-based compound represented by the following formula (3): < EMI ID = 1.0 >

[Chemical Formula 1]

In Formula 1,

R is independently an alkylene group of C1 to C20,

n is an integer of 1 to 10;

(2)

In Formula 2,

The molar ratio of a, b, c, and d,

c is from 5 to 30 moles and d is from 5 to 30 moles per 100 moles of a + b,

the molar ratio of a: b is from 0: 100 to 20: 80,

Each * is independently a hydrogen atom or a C1 to C6 alkyl group.

 (3)

In Formula 3,

R ¹ to R ¹⁰ are the same or different and each of R ¹ to R ¹⁰ is independently a hydrogen atom, a methyl group or an ethyl group.

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

The cyclic aliphatic diisocyanate may be IPDI (Isophorone diisocyanate).

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

The weight average molecular weight (Mw) of the acrylic polyol may be 5,000 to 100,000.

The weight average molecular weight (Mw) of the polyurethane containing the acrylic polyol may be 10,000 to 500,000.

According to another aspect of the present invention, there is provided a coating material comprising a polyurethane comprising the acrylic polyol.

According to another aspect of the present invention, there is provided a process for preparing a furan-based compound represented by the following formula (1) by reacting a furandicarboxylic acid represented by the following formula (4) with an alkane diol represented by the following formula Preparing a polyester polyol (step a); A step of reacting acrylic acid, methacrylic acid, methyl methacrylate, hydroxyethyl methacrylate and ethyl alcohol to prepare an acrylic polyol represented by the following formula (2) (Step b); And a step (c) of reacting the furan-based polyester polyol, the acrylic polyol and the cyclic aliphatic diisocyanate-based compound represented by the following formula (3) (step c) to prepare a polyurethane comprising an acrylic polyol Method is provided.

[Chemical Formula 1]

In Formula 1,

R is independently an alkylene group of C1 to C20,

n is an integer of 1 to 10;

(2)

In Formula 2,

The molar ratio of a, b, c, and d,

c is from 5 to 30 moles and d is from 5 to 30 moles per 100 moles of a + b,

the molar ratio of a: b is from 0: 100 to 20: 80,

Each * is independently a hydrogen atom or a C1 to C6 alkyl group.

 (3)

In Formula 3,

R ¹ to R ¹⁰ are the same or different and each of R ¹ to R ¹⁰ is independently a hydrogen atom, a methyl group or an ethyl group.

[Chemical Formula 4]

[Formula 5]

In Formula 5,

And R is an alkylene group of C1 to C20.

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 step (b), the reaction may be carried out by sequentially introducing methacrylic acid, methyl methacrylate, hydroxyethyl methacrylate and ethyl acrylate.

In step (b), the reaction is carried out in a molar ratio of 12 to 20 moles of the hydroxyethyl methacrylate and 12 to 20 moles of the methyl methacrylate per 100 moles of the total of the methacrylic acid and the methyl methacrylate. .

In the step (c), 10 to 30 parts by mol of the acrylic polyol and 150 to 550 parts by mol of the cyclic aliphatic diisocyanate compound may be reacted with 100 parts by mol of the furan-based polyester polyol.

In step c, the acrylic polyol may be used in a diluted state in at least one solvent selected from toluene and ethyl acetate.

In step c, a DBTDL (dibutyltin dilaurate) catalyst may be further added to react.

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 from 30 to 70 < 0 > C.

The reaction of step c) can be carried out at a temperature of from 120 to 150 < 0 > C.

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

The polyurethane comprising an acrylic polyol according to the present invention can be applied to various fields, and is particularly suitable for use as a coating material. In addition, furan-based polyester polyol as a raw material for polyurethane polymerization can be obtained from biomass, thereby reducing environmental pollution and effectively utilizing biological resources.

1 shows the results of GPC analysis of the acrylic polyol prepared according to Preparation Example 1-2.
Fig. 2 shows the results of GPC analysis according to Test Example 1. Fig.
3 shows the results of FT-IR analysis according to Test Example 2. Fig.
4 shows the results of DSC analysis according to Test Example 3. Fig.
5 is a photograph showing the physical properties of polyurethane according to Test Example 4 in comparison.

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 acrylic polyol of the present invention will be described.

The polyurethane comprising an acrylic polyol of the present invention is a polyurethane comprising a furan-based polyester polyol represented by the following formula (1), an acrylic polyol represented by the following formula (2) and a cyclic aliphatic diisocyanate compound represented by the following formula Reaction products.

[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.

(2)

In Formula 2,

The molar ratio of a, b, c, and d,

c is from 5 to 30 moles and d is from 5 to 30 moles per 100 moles of a + b,

Each * is independently a hydrogen atom or a C1 to C6 alkyl group.

(3)

In Formula 3,

R ¹ to R ¹⁰ are the same or different and each of R ¹ to R ¹⁰ is independently a hydrogen atom, a methyl group or an ethyl group.

Specifically, the cyclic aliphatic diisocyanate may be IPDI (Isophorone diisocyanate).

The weight average molecular weight (Mw) of the furan-based polyester polyol represented by Formula 1 may be 500 to 20,000, and preferably 1,000 to 5,000.

The weight average molecular weight (Mw) of the acrylic polyol may be 5,000 to 100,000, and preferably 10,000 to 50,000.

The weight average molecular weight (Mw) of the polyurethane containing the acrylic polyol may be 10,000 to 500,000, preferably 50,000 to 20,000.

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

Hereinafter, a method for producing a polyurethane containing an acrylic 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 4 and an alkane diol represented by Formula 5 (Step a ).

[Chemical Formula 4]

[Chemical Formula 5]

In Formula 5,

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, the acrylic polyol represented by Formula 2 is reacted with methacrylic acid, methyl methacrylate, hydroxyethyl methacrylate, and ethyl acrylate, (Step b).

Here, steps a and b may be performed in reverse order or simultaneously.

In step (b), the reaction is preferably carried out by sequentially charging the methacrylic acid, methyl methacrylate, hydroxyethyl methacrylate and ethyl acrylate.

It is preferable that in the step b), the reaction is carried out in a molar ratio of 12 to 20 mol parts of the hydroxyethyl methacrylate and 12 to 20 mol% of the methyl methacrylate to the total of 100 mol parts of the methacrylic acid and the methyl methacrylate desirable.

The reaction of step b is preferably carried out at a temperature of 70 ° C or less, more preferably 40 to 70 ° C.

Next, the furan-based polyester polyol, the acrylic polyol and the cyclic aliphatic diisocyanate-based compound represented by the formula (3) are reacted to prepare a polyurethane (step c).

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 is preferably carried out in a molar ratio of 10 to 30 parts by mol of the acrylic polyol and 150 to 550 parts by mol of the cyclic aliphatic diisocyanate compound per 100 parts by mol of the furan-based polyester polyol.

The acrylic polyol is preferably used in a diluted state in a solvent such as toluene or ethyl acetate.

Step c can be carried out by additionally containing a DBTDL (dibutyltin dilaurate) catalyst.

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

If the reaction temperature in step c 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.

The furan-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: 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 캜, and the resulting solution was dissolved in toluene for 5 hours or more. The solution was precipitated in methanol and dried by filtration to prepare a furan-based polyester polyol represented by the following formula. The prepared furan-based polyester polyol had a number average molecular weight (Mn) of 2600, a weight average molecular weight (Mw) of 3300 and a polydispersity index (PDI) of 1.3.

Manufacturing example  1-2: Acrylic Of polyol  Produce

Methacrylic acid, methyl methacrylate, hydroxyethyl methacrylate, and ethyl acrylate were sequentially added in a molar ratio of 1: 79: 10: 10 , And benzoyl peroxide were added together and reacted at 60 ° C for 3 hours to prepare an acrylic polyol.

The acrylic polyol thus prepared had a glass transition temperature (Tg) of 90 ° C, a number average molecular weight (Mn) of 9400 according to gel permeation chromatography (GPC) analysis, a weight average molecular weight (Mw) of 30,000, a polydispersity index , PDI).

FIG. 1 shows the results of GPC analysis of the acrylic polyol prepared according to Preparation Example 1-2.

Manufacturing example  1-3: Preparation of polyurethane

5 g (1.67 × 10 ^-3 mol) of the furan-based polyester polyol obtained in Production Example 1-1, 20 g of the acrylic polyol toluene solution prepared in Production Example 1-2, 6 ml (2.86 × 10 ^-2 mol) of IPDI and DBTDL dibutyl tin dilaurate) catalyst at 100 DEG C for 2 hours and 30 minutes to prepare 15.9 g of polyurethane.

Example  2

Polyurethane was prepared in the same manner as in Example 1 except that 10 g was used instead of 5 g of polyester polyol and 10 g was used instead of 20 g of the acrylic polyol toluene solution to obtain 16.4 g.

Example  3

Except that 15 g was used instead of 5 g of the polyester polyol and 30 g was used instead of 20 g of the acrylic polyol toluene solution and 12 mL (5.72 x 10 ^-2 mol) of IPDI was used instead of 6 ml (2.86 x 10 ^-2 mol) To obtain 16.4 g of a polyurethane.

[Test Example]

Test Example  One: GPC ( Come Permeation Chromatography ) analysis

The polyurethane containing the acrylic polyol prepared according to Examples 1 to 3 was subjected to a high temperature GPC (Gel Permeation Chromatography) analysis using m-Cresol at 100 ° C and the results are shown in FIG. 2 and the following Table 1 .

division Furan-based polyester polyol Cyclic aliphatic diisocyanate
(IPDI) Acrylic polyol catalyst Reaction time Mn Mw PDI Example 1 5g (1.67X10 ^-3 mol) 6 mL
(2.86 x 10 < ^{-2 &} gt ^; mol) 20g (3.34 x 10 ^-4 mol) DBTDL 2h 30min 13138 132884 9.2 Example 2 10g (3.34X10 ^-3 mol 6 mL
(2.86 x 10 < ^{-2 &} gt ^; mol) 10 g (1.67 x 10 < ^-4 > mol) DBTDL 2h 30min 13529 142369 10.5 Example 3 15 g (5.01 × 10 ^-3 mol 12 mL
(5.72 x 10 < ^{-2 &} gt ^; mol) 30 g (5.01 × 10 ^-4 mol) DBTDL 2h 30min 11956 132595 11

Test Example  2: FT - IR ( ATR ) analysis

Fig. 3 shows FT-IR analysis results for the polyurethanes prepared according to Examples 1 to 3. Fig.

Referring to Figure 3, Wavenumber 700 ~ 4000cm ^-1, make a transmission of the range to result in finding the -OH steching vibration 3400cm ^-1, 1720cm ^-1 ester peak of the polyester polyol. Further, the urethane -NH streching vibration 3350cm ^-1, it was confirmed in the polyurethane -NH bending vibration 1530cm ^-1. Thus, it can be confirmed that the polymerization of polyurethane was carried out by the method according to the embodiment of the present invention.

Test Example  3: DSC ( Differential Scanning Calorimetry ) analysis

DSC analysis was conducted to determine the melting point (T _m ) of the polyurethane prepared according to Examples 1 to 3 of the present invention, and the results are shown in FIG.

The analysis was carried out twice at a rate of 10 [deg.] C / min from 35 [deg.] C to 170 [deg.] C and data obtained secondly .

According to Fig. 4, the melting point of the polyurethane prepared according to Examples 1 to 3 was confirmed to be about 80 캜.

Test Example  4: Polyurethane Coating performance  evaluation

In order to evaluate the coating performance of the polyurethane of the present invention, 3 g of the polyurethane prepared according to Examples 1 to 3 was dissolved in 10 ml of toluene and coated on an ABS sheet to form a coating film, and the adhesion and abrasion resistance were measured. The results and photographs are shown in Fig.

According to Fig. 5, the polyurethane coating film of the present invention exhibited adhesiveness when the coating surfaces of Examples 2 and 3 were peeled off with M-2.0, M-2.5 (M-2.0: Of the coatings were left on the surface but the coatings were completely left on M-2.5: 100 coatings when the coating surface was peeled off). Further, in the case of Example 2, the abrasion resistance was not exposed at all after 5000 times of abrasion resistance test using a weight of 500 g.

Therefore, it can be seen that the characteristics of the coating film can be controlled by adjusting the composition ratio of the furan-based polyester polyol and the acrylic polyol depending on the application site and application of the coating film.

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 (18)

A furan-based polyester polyol represented by the following formula (1);
An acrylic polyol represented by the following formula (2); And
And a cyclic aliphatic diisocyanate-based compound represented by the following formula (3).
[Chemical Formula 1]

In Formula 1,
R is independently an alkylene group of C1 to C20,
n is an integer of 1 to 10;
(2)

In Formula 2,
The molar ratio of a, b, c, and d,
c is from 5 to 30 moles and d is from 5 to 30 moles per 100 moles of a + b,
The molar ratio of a: b is from 0: 100 to 20: 80.
(3)

In Formula 3,
R ¹ to R ¹⁰ are the same or different and each of R ¹ to R ¹⁰ is independently a hydrogen atom, a methyl group or an ethyl group. The method according to claim 1,
And R are each independently a linear C2 to C18 alkylene group. The method according to claim 1,
Wherein the cyclic aliphatic diisocyanate is IPDI (Isophorone diisocyanate). The method according to claim 1,
Wherein the furan-based polyester polyol represented by Formula 1 has a weight average molecular weight (Mw) of 500 to 20,000. The method according to claim 1,
Wherein the acrylic polyol has a weight average molecular weight (Mw) of 5,000 to 100,000. The method according to claim 1,
Wherein the polyurethane containing the acrylic polyol has a weight average molecular weight (Mw) of 10,000 to 500,000. A coating material comprising a polyurethane comprising the acrylic polyol of claim 1. Reacting a furandicarboxylic acid represented by the following formula (4) with an alkane diol represented by the following formula (5) to produce a furan-based polyester polyol represented by the following formula (1) (step a) ;
A step of reacting acrylic acid, methacrylic acid, methyl methacrylate, hydroxyethyl methacrylate and ethyl alcohol to prepare an acrylic polyol represented by the following formula (2) (Step b); And
Reacting the furan-based polyester polyol, the acrylic polyol, and the cyclic aliphatic diisocyanate-based compound represented by the following formula (3) to prepare a polyurethane (step c);
≪ / RTI > wherein the polyurethane comprises an acrylic 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;
(2)

In Formula 2,
The molar ratio of a, b, c, and d,
c is from 5 to 30 moles and d is from 5 to 30 moles per 100 moles of a + b,
The molar ratio of a: b is from 0: 100 to 20: 80.
(3)

In Formula 3,
R ¹ to R ¹⁰ are the same or different and each of R ¹ to R ¹⁰ is independently a hydrogen atom, a methyl group or an ethyl group.
[Chemical Formula 4]

[Formula 5]

In Formula 5,
And R is an alkylene group of C1 to C20. 9. The method of claim 8,
Wherein in step (a), the furandicarboxylic acid and the alkane diol are reacted at a molar ratio of 1: 1.1 to 1: 2. 9. The method of claim 8,
Wherein said step (b) comprises reacting methacrylic acid, said methyl methacrylate, hydroxyethyl methacrylate and ethyl acrylate in succession to effect reaction. 9. The method of claim 8,
In the step (b), 12 to 20 parts by mol of the hydroxyethyl methacrylate and 12 to 20 parts by mol of the methyl methacrylate are reacted with 100 parts by mol of the sum of the methacrylic acid and the methyl methacrylate By weight based on the total weight of the polyurethane. 9. The method of claim 8,
Wherein the acrylic polyol is reacted in a ratio of 10 to 30 parts by mol of the acrylic polyol and 150 to 550 parts by mol of the cyclic aliphatic diisocyanate compound per 100 parts by mol of the furan-based polyester polyol in the step c) ≪ / RTI > 9. The method of claim 8,
Wherein in step c), the acrylic polyol is used in a diluted state in at least one solvent selected from toluene and ethyl acetate. 9. The method of claim 8,
And further comprising a DBTDL (dibutyltin dilaurate) catalyst in the step (c), and reacting the acrylic polyol. 9. The method of claim 8,
Wherein the reaction of step (a) is carried out at a temperature of 180-220 < 0 > C. 9. The method of claim 8,
Wherein the reaction of step b) is carried out at a temperature of from 40 to 70 < RTI ID = 0.0 > C. < / RTI > 9. The method of claim 8,
Wherein the reaction of step c) is carried out at a temperature of from 120 to 150 < RTI ID = 0.0 > C. < / RTI > 9. The method of claim 8,
Wherein the furan-based polyester polyol is a biomass-derived compound.

Images