阅读说明：本技术 生物聚醚多元醇的制备方法、生物聚醚多元醇及生物聚氨酯树脂 (Preparation method of biological polyether polyol, biological polyether polyol and biological polyurethane resin ) 是由 后藤洋平 佐藤刚 丸山由布生 于 2018-03-29 设计创作，主要内容包括：本发明涉及生物聚醚多元醇的制备方法、生物聚醚多元醇及生物聚氨酯树脂,生物聚醚多元醇是四氢呋喃和2-甲基四氢呋喃以单体比(质量)为85/15至50/50进行共聚反应的生物聚醚多元醇,并且是获得的数均分子量为500～5000的100％植物来源聚醚多元醇。另外,将所述100％植物来源聚醚多元醇、聚异氰酸酯化合物、以及与异氰酸酯基反应的扩链剂作为主要反应物的合成反应生成物的聚氨酯树脂在相对于常温(20℃)的低温区域(0℃)下的储能模量(E′)变化在0％～15％以内。(The invention relates to a preparation method of biological polyether polyol, the biological polyether polyol and biological polyurethane resin, wherein the biological polyether polyol is obtained by carrying out copolymerization reaction on tetrahydrofuran and 2-methyltetrahydrofuran according to a monomer ratio (mass) of 85/15-50/50, and is 100% plant-derived polyether polyol with the number average molecular weight of 500-5000. Further, the storage modulus (E') of a polyurethane resin obtained by a synthesis reaction product comprising 100% of the plant-derived polyether polyol, the polyisocyanate compound, and the chain extender reactive with the isocyanate group as main reactants is changed within a range of 0% to 15% at a low temperature region (0 ℃) to room temperature (20 ℃).)

1. A method for producing a biopolyether polyol, characterized in that the biopolyether polyol is a plant-derived polyether polyol obtained by copolymerization of tetrahydrofuran and 2-methyltetrahydrofuran, and the monomer ratio (mass) of tetrahydrofuran and 2-methyltetrahydrofuran is 85/15 to 50/50.

2. The method of producing a biopolyether polyol as claimed in claim 1, wherein 15 to 40 mass% of the strong acid catalyst is added to the total mass of tetrahydrofuran and 2-methyltetrahydrofuran in the copolymerization reaction.

3. The method of producing a biopolyether polyol as claimed in claim 1 or 2, wherein the tetrahydrofuran and 2-methyltetrahydrofuran are 100% of a plant-derived monomer, and the copolymerization is carried out by mixing them at a monomer ratio (by mass) in the range of 85/15 to 50/50 and adding a strong acid catalyst while maintaining a temperature in the range of 0 ℃ to 50 ℃.

4. The method of producing a biopolyether polyol as claimed in any one of claims 1 to 3, characterized in that the strong acid catalyst is acetic anhydride, perchloric acid, fluorosulfonic acid or oleum.

5. A100% plant-derived polyether polyol, characterized in that the 100% plant-derived polyether polyol is a copolymerization product in which the monomer ratio (mass) of 100% plant-derived tetrahydrofuran and 2-methyltetrahydrofuran is 85/15 to 50/50, and the number average molecular weight is 500 to 5000.

6. A biopolyurethane resin which is a polyurethane resin obtained by a synthesis reaction product of a main reaction product comprising a polyether polyol which is a copolymerization reaction product having a monomer ratio (mass) of tetrahydrofuran and 2-methyltetrahydrofuran of 85/15 to 50/50, a polyisocyanate compound, and a chain extender which reacts with an isocyanate group of the polyisocyanate compound, wherein the content of a plant-derived component is 50 to 80 mass% relative to 100 mass% of the polyurethane resin.

7. The biopolyurethane resin according to claim 6, wherein the polyether polyol is 100% plant-derived polyether polyol and has a number average molecular weight of 500 to 5000.

8. The biopolyurethane resin according to claim 6 or 7, wherein the storage modulus (E ') in a low temperature region at 0 ℃ is increased by 0% to 15% relative to the storage modulus (E') at ordinary temperature (20 ℃).

Technical Field

The present invention relates to a biopolyether polyol obtained by copolymerization of tetrahydrofuran and 2-methyltetrahydrofuran and a method for preparing the same. Further, it relates to a biopolyurethane resin which is a reaction product with an organic polyisocyanate component using the polyether polyol.

Background

As the soft segment component of the polyurethane resin, polyether is often used. Among them, polyurethane resins using polytetramethylene ether glycol, which is a polymer of tetrahydrofuran, are very drawing attention in elastic fibers and CASE applications because of their excellent elastic properties, low temperature properties, hydrolysis resistance, and the like.

However, the polyurethane resin using polytetramethylene ether glycol has reduced flexibility in a low-temperature region due to the crystallinity of the soft segment. As a method for solving this problem, there is a polyol in which a monomer having a side chain (for example, 3-alkyltetrahydrofuran or neopentyl glycol) is introduced into polytetramethylene ether glycol to improve amorphousness (see patent documents 1 and 2). In the polyurethane resin using these polyols, the alkyl side chain of the polyol suppresses crystallinity of the soft segment and provides good flexibility also in a low temperature region.

In recent years, development of a product of a montmorillonite oil using a raw material derived from a plant has been demanded in society as a measure for realizing a recycling society and for depleting fossil resources. The polyol to be used as a raw material for polyurethane includes biopolyols prepared from vegetable oils, but in the use of elastic fibers and CASEOptimization ofThe bio-polyol of (a) is limited.

Among the biopolyols, polytetramethylene ether glycol using bio-butanediol and bio-tetrahydrofuran as raw materials has attracted attention as a plant-derived polyol having properties equivalent to those of petroleum series. However, since the copolymer has crystallinity as a soft segment as described above, it is not preferable to introduce a petroleum-derived monomer having a side chain (for example, 3-alkyltetrahydrofuran) because the biological concentration decreases in order to improve the crystallinity.

Disclosure of Invention

The present invention addresses the problem of providing a method for producing a biopolyether polyol derived from a plant-derived raw material, a biopolyether polyol, and a biopolyurethane resin having excellent elastic properties and low-temperature properties.

The present inventors have made extensive studies to solve the above problems, and as a result, the present invention has been completed. That is, the present invention is a method for producing a biopolyether polyol, and a biopolyurethane resin using the biopolyether polyol.

[1] A method for producing a biopolyether polyol, characterized in that the biopolyether polyol is a plant-derived polyether polyol obtained by copolymerization of tetrahydrofuran and 2-methyltetrahydrofuran, and the monomer ratio (mass) of tetrahydrofuran and 2-methyltetrahydrofuran is 85/15 to 50/50.

[2] The method for producing a biopolyether polyol as set forth in [1], wherein 15 to 40 mass% of the strong acid catalyst is added to the total mass of tetrahydrofuran and 2-methyltetrahydrofuran in the copolymerization reaction.

[3] The method of producing a biopolyether polyol as set forth in claim 1 or 2, wherein the tetrahydrofuran and 2-methyltetrahydrofuran are 100% of a plant-derived monomer, and the copolymerization is carried out by mixing the monomers at a monomer ratio (by mass) in the range of 85/15 to 50/50 and adding a strong acid catalyst while maintaining a temperature in the range of 0 ℃ to 50 ℃.

[4] The method for producing a biopolyether polyol according to any one of [1] to [3], characterized in that the strong acid catalyst is acetic anhydride, perchloric acid, fluorosulfonic acid or fuming sulfuric acid.

[5] A100% plant-derived polyether polyol, characterized in that the 100% plant-derived polyether polyol is a copolymerization product in which the monomer ratio (mass) of 100% plant-derived tetrahydrofuran and 2-methyltetrahydrofuran is 85/15 to 50/50, and the number average molecular weight is 500 to 5000.

[6] A biopolyurethane resin which is a polyurethane resin obtained by a synthesis reaction product of a main reaction product comprising a polyether polyol which is a copolymerization reaction product having a monomer ratio (mass) of tetrahydrofuran and 2-methyltetrahydrofuran of 85/15 to 50/50, a polyisocyanate compound, and a chain extender which reacts with an isocyanate group of the polyisocyanate compound, wherein the content of a plant-derived component is 50 to 80 mass% relative to 100 mass% of the polyurethane resin.

[7] The biopolyurethane resin according to item [6], wherein the polyether polyol is 100% plant-derived polyether polyol and has a number average molecular weight of 500 to 5000.

[8] The biopolyurethane resin according to [6] or [7], wherein the storage modulus (E ') in a low-temperature region at 0 ℃ is increased by 0% to 15% relative to the storage modulus (E') at normal temperature (20 ℃).

In the polyether polyol of the present invention, both tetrahydrofuran (or 1, 4-butanediol) and 2-methyltetrahydrofuran as raw materials may be of plant origin, and thus 100% of the plant-derived polyether polyol can be provided. The biopolyurethane resin obtained by reacting the organic isocyanate compound and the chain extender with the polyether polyol of the present invention is a material having excellent elastic properties and low-temperature properties.

Drawings

FIG. 1 shows the results of evaluation of the tensile strength and elongation of the polyurethane resins of example 7, comparative example 1 and comparative example 2.

Fig. 2 shows the results of evaluation of the storage modulus (E') of the polyurethane resins of example 7, comparative example 1, and comparative example 2.

FIG. 3 shows the results of the tensile strength and elongation of the polyurethane resins of example 8, comparative example 3 and comparative example 4.

Fig. 4 shows the results of evaluating the storage modulus (E') of the polyurethane resins of example 8, comparative example 3, and comparative example 4.

Detailed Description

The present invention will be described in further detail below with reference to preferred embodiments. In the present specification, the term "bio-butanediol", "bio-tetrahydrofuran", "bio-polyol", "bio-polyether polyol" and the like means a low-molecular or high-molecular compound derived from a plant and having physical properties equivalent to those of petroleum series. In the present specification, the term "100% plant-derived polyether polyol" means that the whole of the main chain is derived from a plant-derived compound. In the present specification, the term "biopolyurethane resin" means that a component derived from a plant-derived compound accounts for at least 50% by mass or more of the raw materials.

The method for producing a biopolyether polyol of the present invention is a method for producing a plant-derived polyether polyol obtained by copolymerization of tetrahydrofuran and 2-methyltetrahydrofuran. In the polyether polyol of the present invention, the monomer ratio (mass) of tetrahydrofuran and 2-methyltetrahydrofuran is from 85/15 to 50/50. Preferably, the polyether polyol is obtained with a tetrahydrofuran/2-methyltetrahydrofuran monomer ratio (by mass) of from 80/20 to 60/40. When the weight ratio is 50/50 or less, the reaction of 2-methyltetrahydrofuran is not sufficient and the yield is low, which is not preferable. On the other hand, when the weight ratio is 85/15 or more, the crystallinity increases, and the object of improving the crystallinity of the soft segment by the alkyl side chain of the polyol is not satisfied.

In the copolymerization reaction of tetrahydrofuran and 2-methyltetrahydrofuran according to the present invention, a strong acid for ring-opening tetrahydrofuran is added in an amount of 15 to 40 mass%, preferably 18 to 36 mass%, based on the total mass of tetrahydrofuran and 2-methyltetrahydrofuran. When 15 mass% or less of a strong acid is added, the reaction conversion rate becomes low and the yield is lowered. When 40 mass% or more of a strong acid is added, there is a risk that reactive species increase and the molecular weight decreases at the time of reaction equilibrium.

In addition, in the method for producing a biopolyether polyol of the present invention, the tetrahydrofuran and 2-methyltetrahydrofuran are 100% of a plant-derived monomer, the monomer ratio (mass) is mixed in the range of 85/15 to 50/50, the temperature range of 0 ℃ to 50 ℃ is maintained and copolymerization is performed by adding a strong acid catalyst.

In the copolymerization reaction of tetrahydrofuran and 2-methyltetrahydrofuran of the present invention, examples of the strong acid capable of ring-opening tetrahydrofuran include acetic anhydride, fluorosulfonic acid, fuming sulfuric acid, perchloric acid, and the like. The strong acid catalyst may be used in a single kind of strong acid, or two or more kinds of strong acids may be used in combination. When two or more strong acids are used, the temperature range of usually 0 to 50 ℃ may be divided into a plurality of stages and used separately.

The 100% plant-derived polyether polyol has a molecular weight of 500-5000. When the molecular weight is 500 or less, the polyurethane resin becomes hard, the rubber modulus and the tensile strength decrease, and when the molecular weight is 5000 or more, the elongation becomes too large, and the properties as a resin deteriorate.

Further, the biopolyurethane resin of the present invention is a polyurethane resin which is a synthetic reaction product of polyether polyol which is a copolymerization reaction product in which the monomer ratio (mass) of tetrahydrofuran and 2-methyltetrahydrofuran is 85/15 to 50/50, a polyisocyanate compound, and a chain extender which reacts with an isocyanate group as main reactants, and is characterized in that the content of a plant-derived component is 50 to 80 mass% relative to 100 mass% of the polyurethane resin.

In the above-mentioned synthesis reaction, the polyisocyanate compound has two or more isocyanate groups in the molecule, and examples thereof include polyisocyanates such as Tolylene Diisocyanate (TDI), diphenylmethane diisocyanate (MDI), m-xylylene isocyanate (XDI), isophorone diisocyanate (IP DI), Hexamethylene Diisocyanate (HDI), Naphthalene Diisocyanate (NDI), and hydrogenated diphenylmethane diisocyanate, and these may be used alone or in combination of two or more.

In the above-mentioned synthesis reaction, the chain extender which reacts with an isocyanate group is a compound having two or more hydroxyl groups and amino groups, and examples thereof include ethylene glycol, 1, 3-propanediol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, glycerin, trimethylolpropane, ethylenediamine, propylenediamine, phenylenediamine, diaminodiphenylmethane and the like.

In the synthesis reaction, the polyether polyol which is a copolymerization reaction product of tetrahydrofuran and 2-methyltetrahydrofuran with a monomer ratio (mass) of 85/15-50/50 is 100% of plant-derived polyether polyol, and the number average molecular weight of the polyether polyol is 500-5000. Such tetrahydrofuran can be obtained, for example, by obtaining furfural from corncobs and waste wood, obtaining furan from which carbon monoxide is removed, hydrogenating it. In addition, 2-methyltetrahydrofuran is typically synthesized by catalytic hydrogenation of furfural. Furfural can be synthesized from polysaccharides by using an acid catalyst. That is, 2-methyltetrahydrofuran is a compound that can be synthesized from biomass raw materials such as cellulose, hemicellulose and lignin, and can be synthesized by an environmentally friendly process such as recovery from agricultural waste including gas of corn cob and bagasse.

The biopolyurethane resin obtained by the synthesis reaction contains 50 to 80 mass% of a polyol component. That is, the content of the plant-derived component is 50 to 80% by mass based on 100% by mass of the polyurethane resin. Generally, the higher the content of the plant-derived component, the more environmentally friendly it is, but in order to achieve 80 mass% or more, in addition to the polyether polyol which is a copolymerization product having a monomer ratio (mass) of tetrahydrofuran and 2-methyltetrahydrofuran of 85/15 to 50/50, the main reactants such as the polyisocyanate compound and the chain extender which reacts with the isocyanate group need to be plant-derived as much as possible, which is difficult in the state of the art and is not economically advantageous.

The biopolyurethane resin of the present invention has excellent elastic properties and low-temperature properties, and can maintain the storage modulus (E ') at normal temperature even in a low-temperature region where the storage modulus (E') is-20 to 0 ℃. Specifically, the storage modulus (E ') at 0 ℃ is increased by 0% to 15% relative to the storage modulus (E') at room temperature (20 ℃). This is an elastic characteristic having almost the same level as that at ordinary temperature even at low temperature. Further, the biopolyurethane resin of the present invention has the same elastic properties, low temperature properties, hydrolysis resistance and the like as those of a polyurethane resin obtained using a tetrahydrofuran/3-alkyltetrahydrofuran polymer, and is an excellent elastic resin.

The method for producing the polyurethane resin of the present invention is not particularly limited, and the polyurethane resin can be produced by a known method or the like. For example, the polyisocyanate compound may be added together with the polyol and the chain extender to carry out the reaction, or the chain extender may be added to carry out the chain extension reaction after the polyol and the polyisocyanate compound are reacted to obtain an isocyanate group-terminated prepolymer.

In the above reaction, an organometallic catalyst or the like may be added as necessary. The organic metal catalyst is not particularly limited, and specific examples thereof include organic tin catalysts such as dibutyltin oxide, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dichloride and dioctyltin dilaurate, and nickel octylate, nickel naphthenate, cobalt octylate, cobalt naphthenate, bismuth octylate and bismuth naphthenate.

The following describes the measurement method used in the present invention.

[ method for measuring number average molecular weight (Mn) of polyol ]

The hydroxyl value of the polyol was measured in accordance with JIS K1557-1 and the Mn was calculated.

[ method for measuring hardness ]

Hardness was measured according to JIS K7312 using type A.

[ methods for evaluating tensile Strength and elongation ]

The tensile test was carried out using a precision universal tester (autograph AG-1 manufactured by Shimadzu corporation) and a 3 rd dumbbell piece as a test piece in accordance with JIS K7312 at a temperature of 23 ℃ and a humidity of 50%. The tensile strength, elongation at break, 100% modulus and 300% modulus were determined.

[ evaluation method of storage modulus (E') ]

E' was measured by a pulling mode using a dynamic viscoelasticity measuring apparatus (DMA 7100 manufactured by Hitachi Kagaku K.K.) under the conditions of a temperature range of-100 to +200 ℃, a temperature rise rate of 2 ℃/min, and a frequency of 10 Hz.