KR20240104938A - Non-Isocyanate Polyhydroxyurethane Based on Biomass-Derived Vegetable Oil and Isosorbide and Method of Preparing the Same - Google Patents

Abstract

The present invention relates to a non-isocyanate polyhydroxyurethane using biomass-derived vegetable oil and isosorbide and a method for producing the same, which has soft properties manufactured using biomass-derived vegetable oil and isosorbide. Non-isocyanate polyhydroxyurethane manufactured using a 5-membered ring carbonate compound and a 5-membered ring carbonate compound having hard properties has excellent thermal stability, hardness, and elongation properties.

Description

Non-Isocyanate Polyhydroxyurethane Based on Biomass-Derived Vegetable Oil and Isosorbide and Method of Preparing the Same}

The present invention relates to a non-isocyanate polyhydroxyurethane based on biomass-derived vegetable oil and isosorbide and a method for producing the same, and more specifically, to polyhydroxyurethane having soft properties manufactured using biomass-derived vegetable oil and isosorbide. It relates to a non-isocyanate polyhydroxyurethane having excellent thermal stability, hardness, and elongation manufactured using a ring carbonate compound and a five-member ring carbonate compound having hard properties, and a method for producing the same.

Polyurethane contains a certain amount of urethane bonds formed by the addition reaction of polyol with a chemically active hydrogen group (-OH) and diisocyanate with an isocyanate group (-NCO), and more than 1000 mol/L of molecules are bonded. It is a high molecular compound. In addition, since the urethane group is generally small compared to other structural units and the structure of parts other than the urethane group are diverse, it can be selected according to the type and combination of polyol and isocyanate and can be used in polymer materials such as foams, elastomers, adhesives, paints, fibers, and synthetic leather. It is widely applicable to almost all fields.

Polyurethane is a segmented block copolymer that is divided into a soft segment and a hard segment, and the polyol belonging to the soft segment is polyester with a molecular weight of 400 to 3000 mol/L. Or it is composed of polyether-based polyol. Polyester-based polyol has excellent tensile strength, thermal stability, and chemical resistance in polyurethane properties due to the strong interaction of ester bonds. It also exhibits good elasticity even at low temperatures, so it is used in synthetic leather and artificial leather and as a textile coating agent. Available. In addition, diisocyanates belonging to the hard part are largely divided into aromatic and aliphatic, and aromatic is mainly used because aromatic has a much faster reactivity than aliphatic in reaction with polyol and its price is relatively low. However, because it has yellowing properties, aliphatic isocyanates are sometimes used for aesthetic reasons and have the advantages of solvent resistance and light stability. In addition, aliphatic isocyanates exhibit excellent elasticity because they are superior in flexibility to aromatic isocyanates. However, diisocyanate is a highly toxic and irritating substance that penetrates the human body through skin contact and the respiratory tract and is exposed to workers. Exposure causes contact dermatitis, respiratory tract irritation, and asthma. Long-term exposure to diisocyanate at low concentrations can cause respiratory diseases such as difficulty breathing, chest tightness, decreased lung function, bronchitis, and asthma, while short-term exposure to diisocyanates at high concentrations can cause bronchitis, bronchospasm, pulmonary edema, and asthma. They say it can be done. Meanwhile, TDI (toluene diisocyanate), one of the diisocyanates, is classified as a potential carcinogen by the National Institute for Occupational Safety and Health (NIOSH).

In the polyurethane synthesis process, various diisocyanates (TDI, MDI: methylene diisocyanate, HDI: hexamethylene diisocyanate, etc.) are used, and these diisocyanates are substances that cause asthma or are suspected to be carcinogenic even at extremely low concentrations, so from an occupational health perspective, It is a process that requires a lot of attention.

Recently, the production of bio-based polyurethane without isocyanate has received considerable attention. As an example, polyhydroxyurethane is produced using cyclic carbonate and polyamine through a spontaneous reaction. Unlike existing products, cross-linked polyurethane can be recycled and reused through a dynamic transcarbaamylase reaction.

Accordingly, there is a need for a method of manufacturing polyurethane foam that has excellent physical properties and is environmentally friendly without using the previously used diisocyanate.

Accordingly, the present inventors made diligent efforts to solve the above problem, and as a result, a 5-membered ring carbonate compound with soft properties and a 5-membered ring carbonate compound with hard properties prepared using biomass-derived vegetable oil and isosorbide were mixed with amines. When reacted, it was confirmed that non-isocyanate polyhydroxyurethane with excellent thermal stability, hardness, and elongation could be produced, and the present invention was completed.

Republic of Korea Patent No. 10-1319684 US Patent Publication No. 20170218124 A1 Japanese Registered Patent No. 634188 B2

Jeong Ji-yeon and 4 others, "Evaluation of diisocyanate exposure level of workers according to urethane foam manufacturing method", Journal of the Korean Society of Industrial Hygiene, Vol. 22, No. 3 (2012) 209-216 Seon-mi Kim and 5 others, "Synthesis and physical properties study of polycaprolactone-based polyurethane using aliphatic and aromatic isocyanates", Polymer (Korea), Vo. 29, No. 3, pp. 253-259, 2005

The purpose of the present invention is to produce polyhydroxyurethane using eco-friendly materials and carbon dioxide without using toxic isocyanate. In particular, the synthesis is possible in a low-pressure reaction rather than a high-pressure reaction with carbon dioxide, and at the same time, it has excellent thermal stability, hardness, and elongation. The aim is to provide a non-isocyanate polyhydroxyurethane and a method for producing the same.

In order to achieve the above object, the present invention provides a 5-membered ring carbonate compound of formula C; A 5-membered ring carbonate compound of formula D; and reacting an amine. It provides a method for producing non-isocyanate polyhydroxyurethane.

[Formula C]

In the formula C, n is an integer of 7, and R is CH ₃ -(CH ₂ ) _16-2m , where m is an integer of 0 to 8.

[Formula D]

In Formula D, n is an integer from 0 to 300.

The present invention also provides a biomass-derived vegetable oil and isosorbide-based non-isocyanate polyhydroxyurethane prepared by the above method and containing a 5-membered ring carbonate compound with soft properties and a 5-membered ring carbonate compound with hard properties. provides.

The present invention also provides a foam comprising biomass derived vegetable oil and isosorbide based non-isocyanate polyhydroxyurethane.

The non-isocyanate polyhydroxyurethane and its manufacturing method according to the present invention can produce polyhydroxyurethane using carbon dioxide without using toxic isocyanate, and in particular, excellent thermal stability even in low-pressure reaction rather than high-pressure reaction of carbon dioxide. It has the effect of producing non-isocyanate polyhydroxyurethane having hardness and elongation.

Figure 1 is a ¹ H NMR spectrum of epoxidized soybean oil and cyclic carbonate soybean oil.
Figure 2 is ¹ H NMR spectra of epoxidized isosorbide and cyclic carbonate isosorbide.

Unless otherwise defined, all technical and scientific terms used in this specification have the same meaning as commonly understood by a person skilled in the art to which the present invention pertains. In general, the nomenclature used herein is well known and commonly used in the art.

In the present invention, when a 5-membered ring carbonate compound with soft properties and a 5-membered ring carbonate compound with hard properties prepared using biomass-derived vegetable oil and isosorbide are contained in a certain ratio and reacted with an amine, toxic isocyanate is produced. It was confirmed that non-isocyanate polyhydroxyurethane with excellent thermal stability, hardness, and elongation could be manufactured using carbon dioxide without using .

Accordingly, in one aspect, the present invention provides a 5-membered ring carbonate compound of formula C; A 5-membered ring carbonate compound of formula D; and a method for producing non-isocyanate polyhydroxyurethane comprising reacting an amine.

[Formula C]

In the formula C, n is an integer of 7, and R is CH ₃ -(CH ₂ ) _16-2m , where m is an integer of 0 to 8.

[Formula D]

In Formula D, n is an integer from 0 to 300.

Hereinafter, the method for producing non-isocyanate polyhydroxyurethane according to the present invention will be described in detail.

In the method for producing non-isocyanate polyhydroxyurethane according to the present invention, the added amounts of the 5-membered ring carbonate compound of the formula D and the amine are 1 to 100 parts by weight, respectively, based on 100 parts by weight of the 5-membered ring carbonate compound of the formula C. It may be 15 to 35 parts by weight. Preferably, the added amounts of the 5-membered ring carbonate compound of Formula D and the amine may be 25 to 75 parts by weight and 20 to 30 parts by weight, respectively, based on 100 parts by weight of the 5-membered ring carbonate compound of Formula C. When the weight part is within the above range, non-isocyanate polyhydroxyurethane with excellent thermal stability, elongation, and strength can be manufactured.

At this time, the amine is selected from one or more types of hexamethylenediamine, 1,3-diaminopropane, isophoronediamine, jeffamine, and triamine. It can be used, and hexamethylenediamine is preferably used, but it is not limited to this, and any amine having two or more amino groups and various molecular weights or structures may be used.

In the present invention, the 5-membered ring carbonate compound of Formula C may be obtained by carbonating an epoxy compound of Formula A in a carbon dioxide atmosphere of 1 atm or more, preferably 1 to 50 atm.

[Formula A]

In Formula A, n is an integer of 7, and R is CH ₃ -(CH ₂ ) _16-2m , where m is an integer of 0 to 8.

After the carbonation reaction, washing and reduced pressure distillation steps may be additionally performed.

Additionally, in the present invention, the 5-membered ring carbonate compound of Formula D may be obtained by carbonating an epoxy compound of Formula B in a carbon dioxide atmosphere of 1 atm or more, preferably 1 to 50 atm.

[Formula B]

In Formula B, n is an integer from 0 to 300.

In the present invention, the epoxy compound of Formula A may be derived from vegetable oil. At this time, the vegetable oil may be one or more selected from the group consisting of soybean oil, castor oil, palm oil, and sunflower seed oil, but is not limited thereto.

Additionally, in the present invention, the epoxy compound of Formula B may be derived from isosorbide. Preferably, it can be obtained by reacting isosorbide and epichlorohydrin.

A preferred embodiment of the method for producing non-isocyanate polyhydroxyurethane according to the present invention is (a) carbonating epoxidized vegetable oil in a carbon dioxide atmosphere of 1 atm or more for 24 to 80 hours to produce a 5-membered ring carbonate of formula C. Preparing a compound; (b) An epoxy compound of formula B is prepared by reacting carbohydrate-based isosorbide (ISB) with epichlorohydrin (ECH), and the epoxy compound is incubated in a carbon dioxide atmosphere of 1 atm or more for 6 to 10 hours. , preferably performing a carbonation reaction for 8 hours to prepare a 5-membered ring carbonate compound of Formula D; and (c) reacting 100 parts by weight of a 5-membered ring carbonate compound containing 25 to 75% by weight of the 5-membered ring carbonate compound of the formula C and 25 to 75% by weight of the 5-membered ring carbonate compound of the formula D with 20 to 30 parts by weight of an amine. Includes steps.

From another point of view, the present invention relates to a biomass-derived vegetable oil and an isosorbide-based non-isocyanate polyhydroxy produced by the above method and containing a 5-membered ring carbonate compound with soft properties and a 5-membered ring carbonate compound with hard properties. It's about urethane.

In the present invention, the biomass-derived vegetable oil and isosorbide-based non-isocyanate polyhydroxyurethane have T _{d20% of} 220 to 350 ℃, Tg of -40 to 50 ℃, elongation of 10 to 300%, and tear strength of 10 to 120 MPa. and intensity (shore A) may be 10 to 100 A.

The non-isocyanate polyhydroxyurethane is a non-isocyanate polyhydroxyurethane having excellent thermal stability, hardness and elongation by combining an appropriate mass ratio of a 5-membered ring carbonate compound of formula C, which has soft properties, and a 5-membered ring carbonate compound of formula D, which has hard properties. Isocyanate polyhydroxyurethane can be produced.

In another aspect, the present invention relates to a foam comprising the biomass-derived vegetable oil and isosorbide-based non-isocyanate polyhydroxyurethane.

In the present invention, non-isocyanate polyhydroxyurethane is produced using chemical foaming agents such as H ₂ O, azodicarbonamide, hydrazide, and poly(methylhydrogenosiloxane). Foam (NIPU foam) can be manufactured.

Hereinafter, the present invention will be described in more detail through examples. These examples are only for illustrating the present invention, and it will be apparent to those skilled in the art that the scope of the present invention is not limited by these examples.

[Example]

Preparation Example 1: Preparation of 5-membered ring carbonate compound C

Five-membered ring carbonate compound C was prepared by reacting epoxidized soybean oil (ESBO) under a carbon dioxide atmosphere at 1 atm.

500 g of ESBO and 75 g of tetrabutylammonium bromide (TBAB) were added to a 1000 ml four-neck round bottom flask, and the flask was mounted on a mechanical stirrer and heating mantle to dissolve at 110°C. The completely mixed and dissolved reactants were carbonated for 40 to 80 hours under 1 atm pressure of high-purity CO ₂ (99.99%). After the reaction was completed, ethyl acetate (EA) and distilled water were added to remove the remaining catalyst in the reactants. Washed three times. After washing, reduced pressure distillation was performed to remove residual EA and distilled water, and a dark brown, viscous liquid was obtained as the final product.

The ¹ H NMR spectrum of epoxidized soybean oil (ESBO) and 5-membered ring carbonate compound C is shown in Figure 1.

Preparation Example 2: Preparation of 5-membered ring carbonate compound D

Preparation of epoxy compound B

Epoxidized compound B was prepared by reacting carbohydrate-based isosorbide (ISB) with epichlorohydrin (ECH).

100 g of ISB and 633 g of ECH were added to a 1000 ml four-neck round bottom flask, placed on a mechanical stirrer, and dissolved at 60°C with a heating mantle. The reaction was carried out by adding 82 g of NaOH dropwise to the mixture at a rate of 3 drops per minute. The yellow liquid after the addition of NaOH was filtered to remove NaCl generated during the reaction, and the remaining ECH was removed through reduced pressure distillation to obtain the final product. The value of n is a natural number between 0 and 300.

Preparation of 5-membered ring carbonate compound D

Epoxidized compound B was reacted under a 1 atm carbon dioxide atmosphere to prepare a 5-membered ring carbonate compound D.

Add 150 g of epoxidized compound B and 7.5 g of TBAB to a 1000 ml four-neck round bottom flask, attach the flask to a mechanical stirrer and heating mantle, dissolve at 100°C for a certain period of time, and carbonate for 8 hours under 1 atmosphere of CO ₂ was carried out to obtain a dark yellow or brown high viscosity liquid.

The ¹ H NMR spectrum of epoxidized isosorbide and 5-membered ring carbonate compound D is shown in Figure 2.

Example 1: Preparation of non-isocyanate polyhydroxyurethane

25 g of 5-membered ring carbonate compound C, 25 g of 5-membered ring carbonate compound D, and 11.3 g of hexamethylenediamine (HMD) obtained through carbonation reaction were added to a 250 ml tall beaker equipped with a stirrer and thermometer. The mixture was dissolved by stirring uniformly at 70°C for 10 minutes, then transferred to a mold and dried in an oven at 100°C for 12 hours to obtain non-isocyanate polyhydroxyurethane (mass ratio C0.5D0.5).

The synthesis of non-isocyanate polyhydroxyurethane can be confirmed from Figures 1 and 2. Figure 1 shows the results of synthesizing 5-membered ring carbonate compound C using epoxy compound A, and Figure 2 shows the results of synthesizing 5-membered ring carbonate compound D using epoxy compound B. Since polyhydroxyurethane production involves mixing compounds C and D, the synthesis can be confirmed using the above drawing.

Example 2: Preparation of non-isocyanate polyhydroxyurethane

Non-isocyanate polyhydroxyurethane was obtained in the same manner as in Example 1, except that 37.5 g of 5-membered ring carbonate compound C, 12.5 g of 5-membered ring carbonate D, and 9.7 g of HMD were used (mass ratio C0. 75D0.25).

Example 3: Preparation of non-isocyanate polyhydroxyurethane

Non-isocyanate polyhydroxyurethane was obtained in the same manner as in Example 1, except that 12.5 g of 5-membered ring carbonate compound C, 37.5 g of 5-membered ring carbonate compound D, and 11.7 g of HMD were used (mass ratio C0) .25D0.75).

Example 4: Preparation of non-isocyanate polyhydroxyurethane

Non-isocyanate polyhydroxyurethane was obtained in the same manner as in Example 1, except that 50 g of the 5-membered ring carbonate compound C and 10.7 g of HMD were used (mass ratio C1D0).

Example 5: Preparation of non-isocyanate polyhydroxyurethane

Non-isocyanate polyhydroxyurethane was obtained in the same manner as in Example 1, except that 50 g of the 5-membered ring carbonate compound D and 14.5 g of HMD were used (mass ratio C0D1).

The T _d20% , T _g , elongation, tear strength, and strength of the non-isocyanate polyhydroxyurethanes prepared in Examples 1 to 5 were measured and shown in Table 1.

T _d20% was measured up to 800°C at a temperature increase rate of 10°C min ^-1 under nitrogen supply using thermogravimetric analysis, and Tg was measured at 10°C min ^-1 under nitrogen supply using differential scanning calorimetry. The temperature increase rate was measured from -80℃ to 220℃. Elongation and tear strength were measured using UTM (Universal testing machine) according to ASTM D 638, and shore hardness was measured using a Durometer.

_Td20% (℃) T _g (°C) Elongation (%) Tear strength (MPa) Strength (shore A) Example 1 312 -5.81 125 11 65 Example 2 310 -6.55 170 15 56 Example 3 295 0.61 - - 97 Example 4 338 -33.1 - - 15 Example 5 274 8.53 - - 100

By way of example, non-isocyanate polyhydroxyurethanes of various hardnesses and elongations can be manufactured by combining the appropriate mass ratio of the 5-membered ring carbonate compound C, which has soft properties, and the 5-membered ring carbonate compound D, which has hard properties.

According to Table 1, it was confirmed that Example 2 had the best thermal stability, elongation, and strength. From the results of Example 4, the non-isocyanate polyhydroxyurethane made solely from the 5-membered ring carbonate compound C showed a high thermal decomposition temperature but low strength due to its strong soft nature. From the results of Example 5, it was confirmed that the non-isocyanate polyhydroxyurethane made solely from the 5-membered ring carbonate compound D had a lower thermal decomposition temperature than D but had high strength.

The above example confirmed that polyhydroxyurethane can be produced using carbon dioxide without using toxic isocyanate, and in particular, it can be synthesized in a low-pressure reaction rather than a high-pressure reaction with carbon dioxide.

The non-isocyanate polyhydroxyurethane resin can be formed into foam using a chemical foaming agent.

As the specific parts of the present invention have been described in detail above, it is clear to those skilled in the art that these specific techniques are merely preferred embodiments and do not limit the scope of the present invention. will be. Accordingly, the actual scope of the present invention will be defined by the claims and their equivalents.

Claims (12)

A 5-membered ring carbonate compound of formula C; A 5-membered ring carbonate compound of formula D; and a method for producing non-isocyanate polyhydroxyurethane comprising reacting an amine:
[Formula C]

In the formula C, n is an integer of 7, and R is CH ₃ -(CH ₂ ) _16-2m , where m is an integer of 0 to 8.
[Formula D]

In Formula D, n is an integer from 0 to 300.
The method of claim 1, wherein the added amounts of the 5-membered ring carbonate compound of Formula D and the amine are 1 to 100 parts by weight and 15 to 35 parts by weight, respectively, based on 100 parts by weight of the 5-membered ring carbonate compound of Formula C. Method for producing isocyanate polyhydroxyurethane.
The method of claim 1, wherein the amine contains two or more primary amino groups and is selected from the group consisting of hexamethylenediamine, 1,3-diaminopropane, isophoronediamine, and zefamine ( A method for producing non-isocyanate polyhydroxyurethane, characterized in that one or more types of jeffamine and triamine are selected.
The method for producing non-isocyanate polyhydroxyurethane according to claim 1, wherein the 5-membered ring carbonate compound of Formula C is obtained by carbonating an epoxy compound of Formula A under a carbon dioxide atmosphere of 1 to 50 atmospheres. :
[Formula A]

In Formula A, n is an integer of 7, and R is CH ₃ -(CH ₂ ) _16-2m , where m is an integer of 0 to 8.
The method for producing non-isocyanate polyhydroxyurethane according to claim 1, wherein the 5-membered ring carbonate compound of Formula D is obtained by carbonating an epoxy compound of Formula B under a carbon dioxide atmosphere of 1 to 50 atmospheres. .
[Formula B]

In Formula B, n is an integer from 0 to 300.
The method for producing non-isocyanate polyhydroxyurethane according to claim 1, wherein the epoxy compound of Formula A is derived from vegetable oil.
The method of claim 6, wherein the vegetable oil is a non-isocyanate polyhydroxy oil, characterized in that at least one selected from the group consisting of soybean oil, caster oil, palm oil, and sunflower seed oil. Method for producing urethane.
The method for producing non-isocyanate polyhydroxyurethane according to claim 1, wherein the epoxy compound of formula B is derived from isosorbide.
The method for producing non-isocyanate polyhydroxyurethane according to claim 5, wherein the epoxy compound of Formula B is obtained by reacting isosorbide and epichlorohydrin.
A biomass-derived vegetable oil produced by the method of any one of claims 1 to 9 and containing a 5-membered ring carbonate compound with soft properties and a 5-membered ring carbonate compound with hard properties and an isosorbide-based non- Isocyanate polyhydroxyurethane.
The biomass-derived product according to claim 10, wherein T _{d20% is} 220 to 350°C, Tg is -40 to 50°C, elongation is 10 to 300%, tear strength is 10 to 120 MPa, and strength (shore A) is 10 to 100 A. Non-isocyanate polyhydroxyurethane based on vegetable oil and isosorbide.
A foam comprising the biomass-derived vegetable oil of claim 10 and the isosorbide-based non-isocyanate polyhydroxyurethane.