JP2002037867A - Polyol obtained from biomass and biodegradative polyurethane - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyol obtained from biomass as starting raw material, and is excellent in reactivity and also in miscibility with other polyols and polyisocyanates, etc., and capable of freely designating the molecular weight over a wide range because of easiness of a molecular weight control, and to provide a biodegradable polyurethane using this polyol. SOLUTION: The polyol is obtained by modifying a hydroxy group of liquefied biomass obtained by reacting biomass and a compound having the hydroxy group in the presence of acid catalyst, with a specified esterification agent or a specified etherification agent. The polyol, and polyisocyanates are reacted to form the biodegradable polyurethane.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a biomass-derived polyol useful as a raw material for various resins used for applications such as molded articles, foams, adhesives, paints, etc. It relates to degradable polyurethane.

[0002]

2. Description of the Related Art Wood flour, wood chips, lignocellulosic substances such as veneer chips and processing residues from various foods and agricultural products, which are generated in large quantities in the lumbering process in the wood industry, can be used effectively. Very few, most of them are incinerated as industrial waste, but in recent years the demand for global environmental conservation has led to the need for the development of methods for effectively utilizing such biomass materials in order to make effective use of resources. .

[0003] As one approach for the effective utilization of such biomass substances, it has been studied to liquefy these biomass substances and to produce various resins using the liquefied substances. For example, a biomass material such as a lignocellulosic material or starch is heated at a high temperature (200-250 ° C.) in the presence of phenols, or at a medium temperature (100-2 ° C.) in the presence of phenols and an acid catalyst.
(00 ° C.), a technique has been developed in which biomass substances are liquefied by using the biomass substances and the liquefied biomass substances are used as resin raw materials. For example, utilizing the fact that a biomass substance has many hydroxyl groups, producing a kind of polyol by liquefying it in the presence of a polyhydric alcohol, and using this as a raw material for producing resins such as polyurethane foams Has been proposed.

[0004]

However, the liquefied biomass obtained by the above-described method is liquefied, and at the same time, a reaction such as dehydration / condensation occurs and a reactive group such as a hydroxyl group is consumed. There was a problem that the reactivity was low. If the reactivity is low as described above, for example, when a polyurethane foam is produced using this liquefied biomass (polyol), the foamability is poor, and good physical properties as a molded article cannot be obtained.

Accordingly, a method has been proposed in which a hydrophilic low-molecular-weight polyhydric alcohol (eg, glycerin, ethylene glycol, or the like) having a high solvating ability is partially used as a liquefied solvent. Thereby, a polyol having high reactivity and useful as a resin raw material can be obtained. However, this polyol has a problem that its hydrophilicity is high and its compatibility with ordinary polyols and polyisocyanates is poor. If the compatibility is poor as described above, separation or precipitation often occurs at the time of preparation and reaction molding, and good physical properties as a molded article cannot be obtained.

Therefore, it has been proposed to use, as a liquefied solvent, a mixture of a polycaprolactone oligomer or ε-caprolactone having good compatibility with polyisocyanate and a hydrophilic low-molecular-weight polyhydric alcohol (Japanese Patent Laid-Open No. Hei 6 (1994)).
-226711, JP-A-8-225653). Thereby, the problem of the reactivity and the compatibility is solved to some extent. However, on the other hand, polycaprolactone oligomers or ε-caprolactone are quite expensive, and the polyols that are inevitably obtained are also expensive, so that there is a problem that the cost is not justified as a polyurethane raw material. Furthermore, in order to maintain the function as a liquefied solvent, the molecular weight and composition of polycaprolactone oligomer or ε-caprolactone are naturally limited, and as a result, the molecular weight, hydroxyl value, etc. of the produced polyol vary widely. However, there is a problem that the degree of freedom in molecular design is small.

The present invention has been made in view of such a technical background, and is a polyol produced from biomass as a starting material. The polyol has excellent reactivity and can be used with other polyols and polyisocyanates. To provide a biomass-derived polyol that has excellent compatibility, is easy to control the molecular weight, and can freely design the molecular weight in a wide range, and further provides a biodegradable resin such as a biodegradable polyurethane using the polyol. The purpose is to:

[0008]

Means for Solving the Problems In order to achieve the above object, the present inventors have made intensive studies and found that liquefaction obtained by reacting a biomass substance with a compound having a hydroxyl group in the presence of an acid catalyst. By modifying the hydroxyl group of biomass with a specific esterifying agent or a specific etherifying agent, the desired biomass-derived polyol can be obtained,
Furthermore, they have found that a polyurethane and a polyurethane foam excellent in biodegradability can be obtained by reacting this with a polyisocyanate, thereby completing the present invention.

That is, the biomass-derived polyol according to the present invention is obtained by reacting a biomass substance with a compound having a hydroxyl group in the presence of an acid catalyst, represented by the following general formula (I):

[0010]

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(Wherein R represents the skeleton of the liquefied biomass and n represents the average number of hydroxyl groups in the liquefied biomass molecule) and the hydroxyl group in the general formula (I) The following general formula (II) obtained by reacting an esterification agent capable of undergoing an esterification reaction with the esterification agent capable of introducing a new hydroxyl group.

[0012]

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(Where R represents a skeleton of liquefied biomass, A represents a skeleton of an alkylene group or the like introduced from an esterifying agent, x represents an integer of 1 or more, and n represents a liquefied biomass molecule. And m represents the average number of esterified hydroxyl groups in the liquefied biomass molecule, and is a polyol represented by 0 <m ≦ n).

Another biomass-derived polyol of the present invention is a polyol represented by the following general formula (I) obtained by reacting a biomass substance with a compound having a hydroxyl group in the presence of an acid catalyst:

[0015]

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(Where R represents the skeleton of the liquefied biomass and n represents the average number of hydroxyl groups in the liquefied biomass molecule), and the liquefied biomass substance represented by the general formula (I) The following general formula (III) obtained by reacting a hydroxylating group with an etherifying agent capable of performing an etherification reaction and accompanying the introduction of a new hydroxyl group;

[0017]

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(Where R represents a skeleton of liquefied biomass, A represents a skeleton of an alkylene group or the like introduced from an etherifying agent, x represents an integer of 1 or more, and n represents a liquefied biomass molecule. And m represents the average number of etherified hydroxyl groups in the liquefied biomass molecule, and is a polyol represented by 0 <m ≦ n).

In any of the above, since a new hydroxyl group is introduced in accordance with the esterification reaction or the etherification reaction, the resulting biomass-derived polyol is excellent in reactivity, and at the same time as other polyols and polyisocyanates. And excellent compatibility. In addition, since the type and amount of the esterifying agent or etherifying agent to be introduced can be freely changed, it is easy to control the viscosity and molecular weight of the obtained biomass-derived polyol, and the viscosity and molecular weight can be freely adjusted over a wide range. Can be changed to

It is preferable to use cyclic esters as the esterifying agent, since it is easy to achieve esterification by the ring-opening addition polymerization reaction and to control the amount of the esterifying agent to be introduced.

The use of epoxides as the etherifying agent is preferred in that the etherification can be achieved by the ring-opening addition polymerization reaction and the amount of the etherifying agent introduced can be easily controlled.

As the biomass substance, one or more kinds selected from the group consisting of lignocelluloses and saccharides are used, because of their abundance and availability, and their suitability for liquefaction. (E.g., easy to liquefy).

The compound having a hydroxyl group includes a compound having a molecular weight of 20 or more having at least two hydroxyl groups in at least a part thereof.
It is preferable to use a polyhydric alcohol having a molecular weight of 00 or less in that a biomass-derived polyol having particularly excellent solvolysis ability and further excellent reactivity can be obtained.

Among them, the number of hydroxyl groups of the polyhydric alcohol is preferably 2 or 3, and the molecular weight is preferably 150 or less. In this case, there is an advantage that the rate of the solvolysis reaction of the biomass substance and the ratio of the solvolysis can be further increased, so that a polyol having more excellent reactivity can be obtained.

The biodegradable polyurethane according to the present invention comprises:
It is a biodegradable polyurethane (including a foam) obtained by reacting any of the above biomass-derived polyols with a polyisocyanate. Since the biomass-derived polyol has excellent reactivity and compatibility, the reaction with the polyisocyanate proceeds well, and a polyurethane having excellent physical properties can be obtained. In addition, since the molecular weight of the biomass-derived polyol can be easily controlled and the molecular weight can be set in a wide range, various molecular designs can be made as the resulting polyurethane. Furthermore, the biomass-derived polyol is obtained by graft polymerization of polyester or polyether to liquefied biomass, and in the former, both biomass component and polyester show excellent biodegradability, and in the latter, biomass component Shows excellent biodegradability, so that the obtained polyurethane is excellent in biodegradability.

Another biodegradable polyurethane according to the present invention is a biodegradable polyurethane obtained by reacting a mixed polyol of any of the above-mentioned polyols derived from biomass with another polyol, and a polyisocyanate. Foams are also included). Since the biomass-derived polyol is also excellent in compatibility with other polyols (especially excellent in compatibility with hydrophilic polyols), the reaction with polyisocyanates is favorable even in a mixed system with other polyols. And a polyurethane having excellent physical properties is obtained. In addition, by using such other polyols in combination, polyurethane characteristics can be further improved, and the range of molecular design of the obtained polyurethane can be further expanded. Furthermore, since the biomass-derived polyol of the present invention is used as a part of the polyol, a polyol having excellent biodegradability can be obtained.

[0027]

BEST MODE FOR CARRYING OUT THE INVENTION The polyol derived from biomass according to the present invention is obtained by reacting a biomass substance with a compound having a hydroxyl group in the presence of an acid catalyst, represented by the following general formula (I):

[0028]

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(Where R represents the skeleton of the liquefied biomass and n represents the average number of hydroxyl groups in the liquefied biomass molecule), and the hydroxyl group in the general formula (I) An esterification agent capable of undergoing an esterification reaction with the esterification agent and capable of introducing a new hydroxyl group with the esterification agent, thereby reacting a part or all of the hydroxyl groups to obtain an esterified compound represented by the following general formula: (II);

[0030]

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(Where R represents a skeleton of liquefied biomass, A represents a skeleton of an alkylene group or the like introduced from an esterifying agent, x represents an integer of 1 or more, and n represents a liquefied biomass molecule. And m represents the average number of esterified hydroxyl groups in the liquefied biomass molecule, and is a polyol represented by 0 <m ≦ n).

Another biomass-derived polyol of the present invention is a polyol represented by the following general formula (I) obtained by reacting a biomass substance with a compound having a hydroxyl group in the presence of an acid catalyst:

[0033]

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(Where R represents the skeleton of the liquefied biomass and n represents the average number of hydroxyl groups in the liquefied biomass molecule), and the liquefied biomass substance represented by the general formula (I) An etherification reaction can be performed on a hydroxyl group, and an etherifying agent capable of introducing a new hydroxyl group with the reaction, and reacting a part or all of the hydroxyl group to obtain the following. General formula (III
);

[0035]

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(Where R represents a skeleton of liquefied biomass, A represents a skeleton of an alkylene group or the like introduced from an etherifying agent, x represents an integer of 1 or more, and n represents a liquefied biomass molecule. And m represents the average number of etherified hydroxyl groups in the liquefied biomass molecule, and is a polyol represented by 0 <m ≦ n).

In any of the above, "nm"
Indicates the average number of hydroxyl groups in the remaining liquefied biomass molecule that has not been esterified or etherified, and is the product of x and m.
Indicates the average number of molecules of the esterifying agent or the etherifying agent introduced into the liquefied biomass molecule.

In the former invention, a part of the esterifying agent is replaced by an etherifying agent as a denaturing agent, and the reaction is carried out. In the latter invention, a part of the etherifying agent is used as a denaturing agent. It includes those reacted by replacing with an esterifying agent. That is, it includes those reacted by using both an esterifying agent and an etherifying agent as a modifying agent.

Examples of the biomass material include, but are not particularly limited to, lignocelluloses, saccharides, and processing residues of various foods and agricultural products.

The lignocelluloses include, for example, wood sawdust, various wooden plywood scraps, wood fiber waste,
Examples include bamboo, kenaf, straw, rice hull, waste paper, pulp and the like.

The saccharides include cellulose, starch, glycogen, caronine, laminaran, dextran, inulin, levan, mannan, xylan, pectic acid, alginic acid, chitin, guaran, heparin, chondroitin sulfate, hyaluronic acid, meskit gum, Examples include polysaccharides such as gatch gum and gum arabic; monosaccharides such as glucose, fructose, mannose, arabinose, xylose, and galactose; disaccharides such as sucrose, cellobiose, and maltose; and oligosaccharides such as cellotriose.

The particle size of the biomass material used as a starting material is not particularly limited, but the liquefaction method, apparatus,
An arbitrary particle size may be appropriately selected in a range that allows sufficient liquefaction and dissolution in consideration of equipment and the like. In addition, one kind of these biomass substances may be used, or a mixture of two or more kinds may be used.

The compound having a hydroxyl group used for liquefaction of the biomass material is not particularly limited. For example, ethylene glycol, propylene glycol, trimethylene glycol, 1,4-butanediol, 1,5- Pentanediol, 1,6-hexanediol, 1,2-hexanediol, 2,4-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decane Dihydric alcohols such as diol, pinacol, cyclopentane 1,2-diol, cyclohexane 1,4-diol, bisphenol A, polyoxypropylene glycol, polyoxypropylene-polyoxyethylene glycol, polyethylene glycol, phenol, cresol, and polyethylene Recall monoethyl ether, monohydric alcohols such as polyethylene glycol monomethyl ether, glycerol, trimethylolpropane, triethanolamine, 1,2,6-hexanetriol, pentaerythritol, methyl glucoside, sorbitol,
Examples thereof include polyhydric alcohols having two or more hydroxyl groups, such as mannitol, sucrose, and polyether polyols or polyester polyols using these as starting materials. Further, as the compound having a hydroxyl group, a substance having a latent hydroxyl group and capable of generating a polyhydric alcohol by releasing these hydroxyl groups during a liquefaction reaction, or a substance composition thereof (for example, a mixture of a cyclic ester and a polyhydric alcohol) and the like Can also be used. As the compound having a hydroxyl group, one of these compounds may be used, or a mixture of two or more compounds may be used.

The liquefaction reaction of a biomass material in the presence of an acid catalyst and a compound having a hydroxyl group is carried out by solvolysis, hydrolysis, and thermal decomposition of the biomass material, and further, dehydration of the solvolysis / hydrolysis product. It is a complicated reaction system such as condensation. Reactions other than solvolysis and hydrolysis deplete the hydroxyl groups, thereby reducing the reactivity of the resulting polyol. Therefore, it is preferable to use a compound having a hydroxyl group (such as a polyhydric alcohol) that sufficiently contributes to the solvolysis of a biomass substance. As the compound having a hydroxyl group, it is preferable to use a polyhydric alcohol having a molecular weight of 2,000 or less and having two or more hydroxyl groups in view of particularly excellent solvolysis ability.
Among them, it is more preferable to use a polyhydric alcohol having a molecular weight of 1,000 or less and having two or more hydroxyl groups, and particularly preferable is a polyhydric alcohol having a molecular weight of 500 or less. Among them, the most preferable is a configuration in which a polyhydric alcohol having 2 or 3 hydroxyl groups and a molecular weight of 150 or less is used as at least a part of the compound having a hydroxyl group. There is an advantage that the rate of the solvolysis reaction and the rate of solvolysis can be further increased, so that a polyol having more excellent reactivity can be obtained. The number of such hydroxyl groups is 2 or 3
The proportion of the polyhydric alcohol having a molecular weight of 150 or less is preferably 50% by weight or less based on the total amount of the compound having a hydroxyl group.

When the biomass substance is reacted with a compound having a hydroxyl group to liquefy biomass, the mixing ratio thereof is preferably 20 to 400 parts by weight of the biomass substance with respect to 100 parts by weight of the compound having the hydroxyl group. .
If the amount is less than 20 parts by weight, the amount of the biomass-derived substance becomes small with respect to the total reaction volume, that is, the amount of the biomass-derived substance in the obtained polyol becomes small, and thus the productivity is undesirably reduced. On the other hand, if the amount exceeds 400 parts by weight, the viscosity of the reaction system becomes large and the progress of the liquefaction reaction becomes difficult, and the liquefaction becomes insufficient or the reaction becomes non-uniform, which is not preferable. Among them, biomass substance 25 per 100 parts by weight of a compound having a hydroxyl group
More preferably, it is set to 200 parts by weight.

The acid catalyst is not particularly restricted but includes, for example, inorganic acids, organic acids, Lewis acids and the like. Among them, mineral acids such as sulfuric acid, hydrochloric acid, nitric acid and phosphoric acid, or toluenesulfonic acid and phenolsulfonic acid Is preferably used. The amount of the acid catalyst used is 0.01 to 10 with respect to the whole reaction product (the total amount of the biomass substance and the compound having a hydroxyl group).
% By weight, and more preferably 0.1 to 5% by weight.
More preferably,

As a specific method and apparatus of a liquefaction reaction for liquefying biomass by reacting a biomass substance with a compound having a hydroxyl group in the presence of an acid catalyst, conventionally known methods and apparatuses can be applied. . For example, Japanese Patent Application Laid-Open No.
The method and apparatus described in JP-A-6128, JP-A-8-225653, and JP-A-11-130873 can be applied. Specifically, for example, using a continuous extrusion liquefaction apparatus or a batch liquefaction apparatus using a single-screw extruder or a twin-screw extruder, the biomass is converted into a polyhydric alcohol and an acid catalyst under a temperature condition of 80 to 200 ° C. By reacting in the presence, a liquefied biomass substance (liquefied biomass) can be produced. In addition, the efficiency of the esterification or etherification reaction after liquefaction, enhance the selectivity,
From the viewpoint of suppressing side reactions such as hydrolysis, it is desirable to use a liquefaction apparatus that is provided with a dehydration unit such as a reduced pressure and that can efficiently remove water generated during liquefaction. The liquefaction reaction time is 1 to 6 when using a continuous extrusion liquefaction apparatus.
It is generally 10 minutes to 300 minutes when using a batch liquefaction apparatus for 0 minutes. The liquefied biomass obtained is usually a mixture of many types of hydroxyl group-containing compounds.

In the present invention, as the esterifying agent used for the denaturation reaction of the liquefied biomass substance, an esterification reaction can be carried out on the hydroxyl group of the liquefied biomass substance, and a new hydroxyl group is thereby added. There is no particular limitation as long as it can be introduced. Among them, cyclic esters are preferably used as the esterifying agent in that the esterification can be easily achieved by the ring-opening addition polymerization reaction and the amount of the esterifying agent to be introduced can be changed over a wide range. Examples of the cyclic esters include propiolactone, β-butyrolactone, α, α′-bischloromethylpropiolactone, α, α-dimethyl-β-propiolactone, δ-valerolactone, and β-ethyl-δ. Valerolactone, 3,4,5-trimethoxy-δ-valerolactone, 1,4-dioxan-2-one, glycolide,
Trimethyl carbonate, neopentyl carbonate,
Ethylene oxalate, propylene oxalate, ε-
Caprolactone, α-methyl-ε-caprolactone, β
-Methyl-ε-caprolactone, γ-methyl-ε-caprolactone, 4-methyl-7-isopropyl-ε-caprolactone, 3,3,5-trimethyl-ε-caprolactone, cis-disalicylide, trisalicylide, lactide and the like. . Among the cyclic esters, ε-caprolactone, which is inexpensive, easily available industrially, and easy to handle, is particularly preferably used. As the esterifying agent, only one kind may be used, or two or more kinds may be appropriately selected and used by mixing.

In the present invention, the etherifying agent used for the denaturation reaction of the liquefied biomass substance can carry out an etherification reaction on the hydroxyl groups of the liquefied biomass substance, and accordingly, a new hydroxyl group is formed. There is no particular limitation as long as it can be introduced. Among them, the use of epoxides as the etherifying agent is inexpensive, easy to achieve esterification by ring-opening addition polymerization reaction, and in that the amount of esterifying agent introduced can be varied over a wide range. preferable. Examples of the epoxides include alkylene oxides capable of undergoing a ring-opening addition reaction such as ethylene oxide and propylene oxide. As the etherifying agent, only one kind may be used, or two or more kinds may be appropriately selected and mixed. Further, both the modification with the esterifying agent and the modification with the etherifying agent may be performed. In this case, the esterification reaction and the etherification reaction may be performed simultaneously, or either of them may be performed first. The reaction may be performed sequentially.

In the modification reaction, it is not always necessary to introduce an esterifying agent or an etherifying agent into all of the liquefied biomass molecules, and only a part thereof may be modified. Polyols obtained by these modifications (polyols derived from biomass)
Is sufficiently effective as a compatibilizer for other unmodified molecules. When a biomass-derived polyol having a high molecular weight is obtained, it is necessary to introduce a large amount of an esterifying agent or an etherifying agent.

In the reaction (denaturation reaction) between the liquefied biomass and the esterifying agent or the etherifying agent, the amount of the esterifying agent or the etherifying agent introduced is 0.05 to 1 mol of the hydroxyl group of the liquefied biomass. It is preferably set in the range of ５０50 mol. If the amount is less than 0.05 mol, the modification is not sufficiently performed, so that it becomes difficult to sufficiently exert the effects of the present invention. On the other hand, if the amount exceeds 50 mol, the ratio of biomass in the obtained polyol (polyol derived from biomass) becomes low,
It is not preferable because biomass cannot be used effectively and efficiently.

In the esterification or etherification reaction, for example, an esterification agent or an etherification agent is added to liquefied biomass, and the mixture is added at room temperature to 180 ° C. for 10 minutes to 10 minutes.
It should be done for about an hour. The liquefied biomass obtained in the presence of an acid catalyst usually has an acidity of pH 1 to 2, which also serves as a catalyst for an esterification reaction or an etherification reaction.
Usually, it is not necessary to add another catalyst. of course,
It may be performed by adding another catalyst, in the case of an esterification reaction, for example, a metal alcoholate such as tin, lead, manganese, and aluminum, a metal carboxylate, an alkyl metal, a catalyst such as a chelate metal, and more specifically. For example, a catalyst such as di-n-butyltin dilaurate, tin di (2-ethyl n-hexanoate), titanium tetraisopropoxide, aluminum triisopropoxide or the like may be added. For example, the reaction may be performed by adding an acid, adjusting the alkalinity, or adding an amine catalyst such as trimethylamine or triethylamine.

The liquefied biomass usually contains water, but the water reacts with the esterifying agent or the etherifying agent to form a homopolymer, so that the denaturing effect may be reduced. Therefore, in such a case, it is preferable to remove the water in the liquefied biomass under reduced pressure before or simultaneously with the reaction (denaturation reaction) with the esterifying agent or the etherifying agent, thereby reducing the denaturing effect. Can be further enhanced.

The apparatus for performing the above-mentioned modification reaction (esterification reaction or etherification reaction) is not particularly limited.
For example, when liquefying biomass using a continuous extrusion liquefaction device, when liquefaction is completed, the esterification agent or etherification agent is continuously and quantitatively injected at the site,
Subsequently, a denaturation reaction can be performed. Also, when liquefying biomass using a batch type liquefaction device,
After the liquefaction is completed, the esterification agent or the etherification agent is injected in a fixed amount, and the denaturation reaction can be subsequently performed. Needless to say, the modification reaction may be performed in another device or place separately from the liquefaction reaction.

The modified polyol derived from biomass obtained by the above modification reaction is used as a raw material for producing a resin such as polyurethane after adjusting the pH with a neutralizing agent or the like, if necessary, in the same manner as a general polyol. it can. For example, by appropriately setting the hydroxyl value and molecular weight of the biomass-derived modified polyol, a wide variety of biodegradable polyurethanes from soft to hard can be produced by reaction with polyisocyanate. Further, the biomass-derived modified polyol, polyisocyanate, foaming agent, foam stabilizer,
Further, if necessary, a biodegradable polyurethane foam can be produced by reacting in the presence of a foaming catalyst, an inorganic or organic additive, or the like. Of course, resins other than polyurethane can also be produced using the biomass-derived modified polyol of the present invention. For example, an epoxy resin can be produced by reacting with epichlorohydrin or the like, or an unsaturated polyester resin can be produced by reacting with an unsaturated dibasic acid. In addition, since this biomass-derived modified polyol has excellent compatibility with other polyols, it is used as a compatibilizer and mixed with other biomass-derived modified polyols or biomass-derived unmodified polyols and the like to form the polyurethane and the like. It can also be used as a raw material for producing resins.

The neutralizing agent is not particularly restricted but includes, for example, alkali metal or alkaline earth metal hydroxides, Lewis bases and the like. Examples thereof include inorganic alkalis such as sodium hydroxide and potassium hydroxide, and organic alkalis such as amines.

The polyisocyanate is not particularly limited, and those used in general production of polyurethane can be used. For example, aliphatic isocyanate, aromatic isocyanate, or a modified product thereof can be used. Examples of the aliphatic isocyanate include hexamethylene diisocyanate, and examples of the aromatic isocyanate include diphenylmethane diisocyanate (MDI), polymeric diphenyl isocyanate, and tolylene diisocyanate (TD).
I), xylene diisocyanate, naphthalene diisocyanate, triphenylmethane triisocyanate, and the like. Examples of the isocyanate-modified product include urethane prepolymer. Of course, these may be mixed and used.

In the production of the polyurethane (including the foam), in addition to the biomass-derived modified polyol and polyisocyanate, a reaction catalyst for controlling the reaction / foaming rate, a foaming agent for foaming, and a mixture of the components An active hydrogen compound may be added in accordance with the foam stabilizer for improving the properties and foaming stability, and further, depending on the desired material hardness, brittleness, flexibility and the like.

As the reaction / foaming catalyst, for example, a catalyst used for a urethane-forming reaction can be used, and it is not particularly limited. For example, tertiary amine compounds such as triethylenediamine and tetramethylhexamethylenediamine, dibutyltin dilaurate And the like. The addition amount of this reaction / foaming catalyst is usually 5 parts by weight or less based on 100 parts by weight of all polyol components.

The foaming agent is not particularly limited. For example, a foaming agent conventionally used for urethane foaming (soft / hard) can be used. For example, water, methylene chloride, ethylene chloride, H
CFC141b and the like. It is preferable to use water as the foaming agent, in that the environment can be sufficiently considered and the compatibility with the biomass-derived polyol is excellent. The amount of water as a foaming agent may be an ordinary amount when a general polyurethane foam is produced, and is preferably 1 to 20 parts by weight, particularly preferably 2 to 15 parts by weight, based on 100 parts by weight of the total polyol. Department.

The foam stabilizer is not particularly restricted but includes, for example, silicone-based foam stabilizers conventionally used for urethane foaming (soft and hard). Examples of the silicone-based foam stabilizer include a dimethylpolysiloxane-polyether copolymer-based foam stabilizer. Examples of commercially available products include “SH192” and “SH19”.
3 "(all manufactured by Toray Dow Corning Silicone),
"L-5420" (manufactured by Nippon Unicar) "SZ-112
7 "(manufactured by Nippon Unicar)," F-242T "(manufactured by Shin-Etsu Chemical Co., Ltd.) and the like. The amount of the foam stabilizer is preferably 0.2 to 5 parts by weight based on 100 parts by weight of the polyol component.

The active hydrogen compound is not particularly limited. For example, those which are conventionally used in the production of polyurethane foams can be used. Examples thereof include ethylene glycol, propylene glycol, butylene glycol, and the like.
Diethylene glycol, trimethylolpropane, hexanetriol, glycerin, trimethylolethane,
Low molecular weight polyols such as pentaerythritol, polyoxyethylene glycol, polyoxypropylene glycol, poly (oxypropylene) poly (oxyethylene)
Examples thereof include polyether polyols such as glycol, poly (oxybutylene) glycol, and poly (oxytetramethylene) glycol, as well as polycaprolactone, and polyester polyols produced from polybasic acids and hydroxyl compounds. In addition, acrylic polyols, castor oil, and tall oil derivatives can also be used. The amount of these active hydrogen compounds to be added is preferably 100 parts by weight or less based on 100 parts by weight of the biomass-derived modified polyol. If it exceeds 100 parts by weight, it is difficult to obtain sufficient biodegradability in the obtained polyurethane foam, which is not preferable. Particularly preferred addition amount of the active hydrogen compound is 80 parts by weight or less based on 100 parts by weight of the biomass-derived modified polyol.

Polyurethanes (including foams) obtained by reacting the biomass-derived modified polyol according to the present invention with polyisocyanates include, for example, a biodegradation accelerator, a photolysis accelerator, an oxidation accelerator, and an ultraviolet absorber. Various additives such as an agent, an antioxidant, a heat resistance improver, a flame retardant, a colorant, an inorganic filler, an organic filler, and a reinforcing material can also be compounded. In addition, in agricultural and horticultural applications, fertilizers may be added and used.

[0064]

EXAMPLES Next, specific examples of the present invention will be described, but the present invention is not limited to these examples.

Example 1 240 g of polyethylene glycol (PEG 400, molecular weight 400) preliminarily mixed with 9 g of 98% sulfuric acid, 60 g of glycerin (Gly),
150 g of dried red pine wood flour was placed in a 500 ml glass flask and reacted for 60 minutes while stirring in a 150 ° C. oil bath. The unliquefied residue ratio of the obtained liquefied product (liquefied biomass) (based on the input wood powder) is 8%
And the hydroxyl value was 410 mg KOH / g. 225 g of a liquefied product (liquefied biomass) is taken out and used as a polyol for foaming in Comparative Example 1 described later.

Next, to the 225 g of liquefied biomass remaining in the flask, after lowering the temperature of the oil bath to 120 ° C., 45 g of ε-caprolactone (CPL) was added.
The reaction was performed for 20 minutes. Thereafter, the flask was placed in cold water and cooled to room temperature to stop the reaction. HPLC of the reaction product,
According to GPC analysis, ε-caprolactone reacted 100%, of which 2% became 6-hydroxy-n-hexanoic acid, and 95% or more reacted with liquefied biomass. The product-modified biomass-derived modified polyol is a uniform black-brown mucus having a hydroxyl value of 335 mg KO.
H / g.

<Example 2> A liquefied wastepaper (liquefied biomass) was obtained in the same manner as in Example 1, except that used newspaper was used instead of red pine wood flour as biomass. Unliquefied residue ratio of this liquefied biomass (based on the used waste paper)
Is 12.4%, and the hydroxyl value is 432 mgKOH / g.
Met. 225 g of liquefied product (liquefied biomass)
The temperature of the oil bath was lowered to 120 ° C., and 45 g of ε-caprolactone was added to 225 g of the remaining 225 g of the flask, followed by reaction for 20 minutes. Thereafter, the flask was immersed in cold water and cooled to room temperature. HPL of reaction product
C, According to GPC analysis, ε-caprolactone was 100
% Of which 2% is 6-hydroxy-n-
It became hexanoic acid and more than 95% reacted with liquefied biomass. The modified biomass-derived polyol as a product is a uniform black-brown mucus having a hydroxyl value of 360 mg KO.
H / g.

Example 3 Polyethylene glycol (PEG 400) 210 previously mixed with 6 g of 98% sulfuric acid
g, 90 g of glycerin, and 200 g of dried corn starch were weighed into a 500 ml glass flask, and reacted for 40 minutes while stirring in a 140 ° C. oil bath. The liquefied product (liquefied biomass) obtained had a non-liquefied residue ratio (based on the amount of starch) of 1% and a hydroxyl value of 490 mgKOH / g. 250 g of a liquefied product (liquefied biomass) is taken out and used in a comparative example to be described later.

Next, for 300 g remaining in the flask,
After lowering the temperature of the oil bath to 120 ° C., 30 g of ε-caprolactone was added and reacted for 40 minutes. Thereafter, the flask was immersed in cold water and cooled to room temperature. According to HPLC and GPC analysis of the reaction product, ε-caprolactone reacted 100%, of which 4% was 6-hydroxy-n-
It became hexanoic acid and more than 90% reacted with liquefied biomass. The biomass-derived modified polyol, which is a product, is a uniform brown translucent liquid and has a hydroxyl value of 442 mg.
KOH / g.

Example 4 A liquefied biomass was obtained in the same manner as in Example 3, except that dried glucose was used instead of starch as the biomass. The liquefied biomass had a non-liquefied residue ratio (based on the charged glucose) of 0% and a hydroxyl value of 542 mgKOH / g. 300 g of the liquefied biomass was taken out, and the temperature of the oil bath was lowered to 120 ° C., and 90 g of ε-caprolactone was added to the remaining 300 g in the flask, followed by a reaction for 40 minutes. Thereafter, the flask was cooled with cold water to room temperature. H
According to PLC and GPC analysis, ε-caprolactone was 1
00% reacted, 9% of which became 6-hydroxy-n-hexanoic acid, and 88% or more reacted with liquefied biomass. The resulting biomass-derived modified polyol is a uniform brown translucent mucus having a hydroxyl value of 410 mg KOH.
/ G. The amount of 6-hydroxy-n-hexanoic acid derived from the hydrolysis reaction between caprolactone and water reached 9% of the total amount of caprolactone added because the amount of water in the liquefied product was 2-3 of Examples 1-3
It is considered that this is due to 6% in the present embodiment compared to about%. As described above, it is considered that the reason why the amount of water in the liquefied product was increased in the present example is that a large amount of water was generated due to dehydration during the etherification reaction between glucose and the liquefied solvent.

Example 5 In order to reduce the amount of 6-hydroxy-n-hexanoic acid produced in Example 4, liquefied glucose was obtained under the same conditions as in Example 4 and then dried at 120 ° C.
Vacuum dehydrated for 0 minutes. As a result, the moisture content of the liquefied product is 6%
To 2%. Next, 90 g of ε-caprolactone was added to 300 g of the liquefied product and reacted for 40 minutes. Thereafter, the flask was cooled with cold water to room temperature. HP
According to LC and GPC analysis, ε-caprolactone was 10
0% reacted, of which 2% became 6-hydroxy-n-hexanoic acid, and 95% or more reacted with liquefied biomass. The biomass-derived modified polyol as a product is a uniform brown translucent liquid having a hydroxyl value of 402 mgK.
OH / g. From these results, it was confirmed that by removing water in the reaction system, the graft ratio of caprolactone was increased, and the amount of 6-hydroxy-n-hexanoic acid produced as a hydrolysis product could be reduced.

<Examples 6 to 10> Liquefied starch (liquefied biomass) was prepared under the same conditions as in Example 3 and
The mixture was divided into five portions of 00 g each and placed in separate flasks. Ε-caprolactone was added to them for 5
0, 100, 300, 500 and 1000 g were added, and an esterification reaction was carried out in the same manner as in Example 3. Table 1 shows the results.

As is evident from Table 1, liquefied biomass, which is usually highly hydrophilic and insoluble in tetrahydrofuran (THF), can be completely dissolved in THF by a certain degree of esterification and modification, and the molecular weight can be measured. Was. The results of the molecular weight measurement also show that caprolactone undergoes a ring-opening polymerization reaction with liquefied starch with high selectivity to obtain a polyester polyol having a molecular weight almost as calculated. This phenomenon also sufficiently supports that the uniformity of the esterification reaction on the liquefied biomass and that the affinity of the reaction product polyol for the fat-soluble substance can be greatly improved by the esterification modification.

[0074]

[Table 1]

<Examples 11 to 14> The conditions shown in Table 2, ie, 100 g of dry starch, ethylene glycol (EG) / PEG 400 = 1/1, glycerin, glycerin + ε-caprolactone, polycaprolactone (Placcel 303) And 100 g, 100 g, 150 g, and 150 g, respectively, were used for liquefaction and dissolution in the same manner as in Example 3, and then a predetermined weight part of ε-caprolactone was added to the liquefaction product. The esterification reaction was performed under the same conditions as in Example 3. All of the biomass-derived modified polyols were uniform brown translucent liquids. Table 2 shows the results. Table 2
As is clear from these, in these liquefied solvent systems,
Both liquefaction and esterification (denaturation) of starch were performed smoothly, and a uniform biomass-derived modified polyol was obtained.

[0076]

[Table 2]

Example 15 70 parts by weight of polyethylene glycol (PEG400), 30 parts by weight of glycerin,
A liquefied solvent mixed with 2 weight of sulfuric acid and a corn starch having a water content of 10 wt% as a biomass substance were mixed in a weight ratio of liquefied solvent: starch = 15:10. Next, the obtained mixture was subjected to a continuous extrusion type liquefaction apparatus (manufactured by Fuji Carbon Co., single screw extruder: L / D = 30, screw diameter 1).
00 mm), the barrel temperature was set to 175 ° C., and the number of revolutions of the screw was set to 40 rpm, and the mixture was continuously charged from the raw material charging port at a rate of 30 kg / hr using a metering pump. Ε-Caprolactone was introduced at a rate of 6 kg / hr from a vent port in front of the outlet of the liquefaction apparatus by a metering pump. The liquefied material continuously discharged from the outlet of the liquefaction apparatus was cooled while being continuously passed through a screw conveyor type cooling apparatus and cooled to obtain a biomass-derived modified polyol (liquefied starch esterified polyol). H
According to PLC and GPC analysis, ε-caprolactone was 1
00%, 1% of which became 6-hydroxy-n-hexanoic acid, and 95% or more reacted with liquefied biomass. The biomass-derived modified polyol as a product is a uniform brown transparent liquid having a hydroxyl value of 372 mgKOH /
g.

Example 16 100 g of liquefied starch produced under the same conditions as in Example 3 was subjected to a reflux condenser, a dropping funnel,
Transfer to a flask equipped with a stirrer and bring the temperature of the
After the temperature was adjusted to 30 ° C, 30 g of propylene oxide was added dropwise from the dropping funnel over 15 minutes, and after the completion of the addition, the reaction was further performed at 100 ° C for 60 minutes. The weight of the reaction product increased by 28 g. The biomass-derived modified (etherified modified) polyol as a product was a uniform brown transparent liquid, and had a hydroxyl value of 395 mgKOH / g.

<Example 17> 100 g of liquefied starch prepared under the same conditions as in Example 3 was weighed in a pressure vessel, and 100 g of propylene oxide was added at room temperature. After the temperature was raised to 100 ° C., the reaction was performed for 2 hours. The biomass-derived modified (etherified modified) polyol as the product was a uniform brown transparent liquid, and had a hydroxyl value of 285 mgKOH / g.

<Example 18> 100 g of the biomass-derived polyol obtained in Example 1 was weighed into a 500-ml polycup, and a 48% aqueous sodium hydroxide solution 3 was used.
g, and after sufficiently stirring, L-5421 was used as a foam stabilizer.
(Manufactured by Nippon Unicar Co., Ltd.) as a foaming catalyst. 1 g of 31 (manufactured by Kao Corporation) and 0.2 g of U-100 (manufactured by Nitto Kasei) were added. Water generated during the neutralization and water contained in a liquefied product (modified polyol derived from biomass) were used as a foaming agent. After thoroughly mixing and stirring the above-mentioned mixture, a polyisocyanate, Millionate M
164 g of R-100 (diphenylmethane diisocyanate, manufactured by Nippon Polyurethane Co., NCO content: 31.1%) was added (isocyanate index 105), and the mixture was stirred for 10 seconds at a stirring rotation speed of 7000 rpm, and polyethylene was placed in an 18 cm square cardboard box. It was thrown into a plastic bag and was freely foamed to obtain a foam. The polyurethane foam thus obtained has a good appearance, a smooth and glossy skin layer, uniform cells, and a specific gravity of 0.028 g /
In cm ³ , there was no defect and the strength was good.

<Example 19> 90 g of a foaming raw material mixed and stirred in the same manner as in Example 18 was weighed 300 x 130 x 70.
mm in an aluminum box mold. The polyurethane foam taken out after 10 minutes had a good skin layer and uniform cells and a specific gravity of 0.033 g / cm ³ .
No deformation was observed when the polyurethane foam was left standing at room temperature for two days and nights.

<Examples 20 to 35> 100 g (40 g in Example 35) of the biomass-derived modified polyol obtained in Examples 2 to 6, 9 to 11, and 13 to 17 was weighed into a 500 ml polycup. Take each concentration 4
Neutralization was performed to the vicinity of the neutralization point with an 8% aqueous sodium hydroxide solution, and a polyurethane foam was obtained in the same manner as in Example 18 using the formulation shown in Table 3. Table 4 shows the foaming results.

In Example 20, foaming of the ester-modified polyol of waste paper liquefaction showed good foaming suitability, compatibility and reactivity, and a uniform polyurethane foam was obtained.

Examples 21 to 23 examine the compatibility and foamability of the liquefied starch ester-modified polyol obtained in Example 3 with other polyols. In contrast to Example 21 without other polyol addition, Example 22 had MN30
0 (PPG-based trifunctional rigid urethane foaming polyol, hydroxyl value 550 mg KOH / g, manufactured by Mitsui Chemicals, Inc.) 10 g,
In Example 23, PE450 (PPG-based polyfunctional rigid urethane foaming polyol, hydroxyl value 450 mgKOH / g,
30 g (manufactured by Mitsui Chemicals, Inc.) was added and foamed.
The compatibility between the liquefied starch ester-modified polyol and the polyol added above was good, and no precipitation or separation occurred during the mixing stage. All three formulations had good compatibility and reactivity with MR-100 (diphenylmethane diisocyanate) during foaming, and uniform polyurethane foams were obtained.

In Examples 24 and 25, an ester-modified polyol derived from glucose was used. In both cases, good compatibility and foamability were obtained as in the case of the liquefied starch ester-modified polyol of the above example. A polyurethane foam having an excellent structure was obtained.

In Examples 26 to 28, biomass-derived modified polyols having different molecular weights prepared by changing the amount of caprolactone added were converted into urethane foams. Example 26 is a hard formulation, but Examples 27 and 2
8 was a soft formulation. The high-molecular-weight liquefied starch ester-modified polyol used in Examples 27 and 28 was waxy at room temperature (obtained in Examples 9 and 10).
Therefore, it is heated to 50 ° C. and dissolved, and then MR-
100 and foamed. All three formulations exhibited good compatibility, reactivity, and foamability, and a good polyurethane foam as expected was obtained.

Examples 29 to 32 show foaming of a biomass-derived modified polyol obtained after changing the liquefaction solvent used for liquefying biomass. As is clear from Table 4, as in the case of the liquefied starch ester-modified polyol of the above example, good compatibility and foamability were obtained, and a uniform polyurethane foam was obtained.

Examples 33 and 34 show foaming examples of a modified polyol derived from liquefied biomass obtained by modifying liquefied starch with ether using propylene oxide in a usual hard formulation. Similar to the liquefied starch ester-modified polyol, good compatibility and foamability were obtained, and a uniform polyurethane foam was obtained.

In Example 35, the modified polyol derived from biomass obtained in Example 6 was mixed with the liquefied starch (unmodified polyol derived from biomass) obtained in Example 3, followed by foaming. By mixing the biomass-derived modified polyol, a liquefied starch (see Comparative Example 3), which usually has poor compatibility with MDI (diphenylmethane diisocyanate) and separates during foaming, does not separate, and a good polyurethane foam is obtained. Was done.

[0090]

[Table 3]

[0091]

[Table 4]

Comparative Example 1 Liquefied wood 100 before being modified with caprolactone through the first-stage liquefaction reaction in Example 1
g was weighed into a 500 ml capacity polycup,
A foam was prepared in the same manner as described above. With this formulation, the mixture was seen to phase separate from the surface during foaming, and the cure rate was slow. The obtained foam had a two-colored skin layer and was slightly sticky. There were also non-uniform cells inside and small spots. Specific gravity is 0.031 g / cm
³ , the whole structure was loose. (See Table 5) <Comparative Example 2> 90 g of a foaming raw material mixed and stirred in the same manner as in Comparative Example 1 was filled in an aluminum box mold of 300 x 130 x 70 mm. In the polyurethane foam taken out after 10 minutes, the skin layer is sticky by two-color separation,
Since the curing reaction was not completely completed yet, it deformed during removal.

Comparative Example 3 Liquefied starch 1 before being modified with caprolactone through the liquefaction of the first stage in Example 3
00 g was weighed into a 500 ml polycup, and a foam was prepared in the same manner as in Example 18 using the formulation shown in Table 5. During the foaming process, phase separation occurred between the liquefied starch and the isocyanate, and the resulting foam had a two-color surface and was sticky. There were also many brown spots inside.

<Comparative Example 4> 100 g of liquefied glucose before caprolactone modification through the first-stage liquefaction reaction in Example 4 was weighed into a 500 ml polycop.
A foam was prepared in the same manner as in Example 18 using the formulation shown in (1). A clear phase separation occurred between the liquefied starch and the isocyanate during the foaming process, and the resulting foam appeared bicolor on the surface and was noticeably sticky. There were also many brown spots inside.

<Comparative Examples 5 and 6> The liquefied starch before the caprolactone modification through the first-stage liquefaction reaction in Example 3 was treated with MN30 in the same manner as in Examples 22 and 23.
0 or 30% of PE450 was added and mixed.
When these polyols were added, solids precipitated from the liquefied starch. In Comparative Example 6 in which a larger amount was added, the liquid portion also separated into two layers. The precipitated solid did not dissolve even when stirred. The foam was prepared as it was, but phase separation occurred between the liquefied starch and the isocyanate during the foaming process, and the resulting foam appeared bicolor, sticky, and black spots inside the foam (See Table 6).

[0096]

[Table 5]

[0097]

[Table 6]

The unliquefied residue rate of the liquefied biomass is a value measured as follows.

(Unliquefied residue ratio) A 10 g liquefied material sample was
A mixed solvent of 1,4-dioxane / water = 7/3 (weight ratio) was added to dilute the mixture, sufficiently stirred and dissolved, and then dried in advance to obtain a glass fiber filter whose weight was measured. Then, filtration was performed, and an insoluble residue (unliquefied residue) was separated by filtration. The insoluble residue was further washed several times with a 1,4-dioxane / water mixed solvent, washed sufficiently, filtered, dried at 105 ° C. to a constant weight at 105 ° C., and weighed. Then, the unliquefied residue rate (%) was calculated. Unliquefied residue ratio (%) = residue weight (g) / prepared biomass weight (g) × 100

The density of the obtained polyurethane foam was measured according to JIS K6401.

[0101]

Industrial Applicability The biomass-derived polyol according to the present invention is characterized in that a hydroxyl group of a liquefied biomass obtained by reacting a biomass substance with a compound having a hydroxyl group in the presence of an acid catalyst is converted into a specific esterifying agent or It is obtained by denaturation with a specific etherifying agent, and a new hydroxyl group is introduced in accordance with the esterification reaction or etherification reaction, so that the resulting biomass-derived modified polyol has excellent reactivity and other properties. And has excellent compatibility with polyols and polyisocyanates. In addition, the biomass-derived modified polyol is easy to control in viscosity and molecular weight, and its molecular weight can be freely changed in a wide range, so that the degree of freedom is large and various molecular designs can be performed. Therefore, it is suitable as a raw material for producing resins such as polyurethane, epoxy resin and unsaturated polyester resin.

The conventional liquefied biomass-derived polyol is:
The application (use) range was narrow, the foaming aptitude was poor, the curing speed was low, the appearance of the molded product was not good, and the physical properties were poor, but the biomass-derived polyol of the present invention had these problems. Can be used at once with a sense and formula similar to those of conventional synthetic polyols, and its quality characteristics can be controlled over a wide range. Conventionally, only a low-molecular-weight liquefied biomass was obtained, so that polyurethane foams produced using the same were almost limited to rigid ones. Can be freely controlled, so that a wide variety of polyurethanes from hard to soft can be manufactured.

Thus, the biomass-derived polyol of the present invention is very suitable for industrialization because a high-quality biomass-derived polyol can be obtained very easily, and is extremely practical as a polyol raw material for urethane and the like. Very useful for utilization.

When cyclic esters are used as the esterifying agent, the esterification can be easily achieved by the ring-opening addition polymerization reaction, and the amount of the esterifying agent introduced can be easily controlled.

When epoxides are used as the etherifying agent, the etherification can be easily achieved by the ring-opening addition polymerization reaction, and the amount of the etherifying agent can be easily controlled.

When one or more selected from the group consisting of lignocelluloses and sugars is used as the biomass substance, the cost can be reduced and the liquefaction reaction can be easily performed. is there.

When a polyhydric alcohol having two or more hydroxyl groups and a molecular weight of 2,000 or less is used as at least a part of the compound having a hydroxyl group, the solvolytic ability is particularly excellent, and thus the reactivity is further improved. The biomass-derived polyol can be obtained.

When a polyhydric alcohol having 2 or 3 hydroxyl groups and a molecular weight of 150 or less is used as at least a part of the compound having a hydroxyl group, the rate of the solvolysis reaction of the biomass substance is reduced. And the rate of solvolysis can be further increased, and as a result, a polyol having further excellent reactivity can be obtained.

The biodegradable polyurethane according to the present invention comprises:
The biomass-derived polyol is obtained by reacting a polyisocyanate with a polyisocyanate.Since this biomass-derived polyol is excellent in reactivity and compatibility,
The reaction with the polyisocyanate proceeds favorably, resulting in a polyurethane having excellent physical properties. Further, since the molecular weight of the biomass-derived polyol as the starting material can be easily controlled and the molecular weight can be set in a wide range, various molecular designs can be performed as the polyurethane obtained. Further, the biomass-derived polyol is obtained by graft polymerization of polyester or polyether to liquefied biomass,
In the former, both the biomass component and the polyester exhibit excellent biodegradability, and in the latter, the biomass component exhibits excellent biodegradability, so that the polyurethane is excellent in biodegradability.

Further, another biodegradable polyurethane according to the present invention is obtained by reacting a mixed polyol of the above-mentioned biomass-derived polyol with another polyol and a polyisocyanate. Is also excellent in compatibility with other polyols, so that the reaction with polyisocyanates proceeds well even in a mixed system with other polyols, and a polyurethane having excellent physical properties can be obtained. In addition, by using such other polyols in combination, it is possible to further improve the properties of the polyurethane and to further expand the variety of molecular designs as the polyurethane. Furthermore, since the biomass-derived polyol of the present invention is partially used, this polyol has excellent biodegradability.

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Kaoru Fujimori 1340 Iwamuro, Koka-cho, Koka-gun, Shiga Prefecture Inside Fuji Carbon Co., Ltd. 4J005 AA13 BD03 4J029 AA01 AC01 AE17 EG02 EG07 EG09 EH01 4J034 CA03 CB07 DA01 DF11 DF12 DG03 DG04 DG14 EA08 EA09 HA01 HA02 HA07 HA08 HC12 HC13 HC64 HC65 HC67 HC71 HC73 KB05

Claims (9)

[Claims] 1. A compound represented by the following general formula (I) obtained by reacting a biomass substance with a compound having a hydroxyl group in the presence of an acid catalyst: (Where R represents the skeleton of the liquefied biomass and n represents the average number of hydroxyl groups in the liquefied biomass molecule), and an ester with respect to the hydroxyl group in the general formula (I). And an esterifying agent capable of carrying out an oxidation reaction and introducing a new hydroxyl group with the reaction, and the following general formula (II) obtained by reacting: (Where R represents the skeleton of the liquefied biomass, A represents the skeleton of an alkylene group or the like introduced from the esterifying agent, x represents an integer of 1 or more, and n represents the average in the liquefied biomass molecule. Indicate the number of hydroxyl groups, m indicates the average number of esterified hydroxyl groups in the liquefied biomass molecule, and 0 <m ≦
A biomass-derived polyol represented by n). 2. The biomass-derived polyol according to claim 1, wherein a cyclic ester is used as the esterifying agent. 3. The following general formula (I) obtained by reacting a biomass substance with a compound having a hydroxyl group in the presence of an acid catalyst: (Where R represents the skeleton of the liquefied biomass and n represents the average number of hydroxyl groups in the liquefied biomass molecule) and the liquefied biomass substance represented by the formula (I): And an etherifying agent which can carry out an etherification reaction by introducing a new hydroxyl group with the reaction, and the following general formula (III) obtained by reacting: (Where R represents the skeleton of the liquefied biomass, A represents the skeleton of an alkylene group or the like introduced from the etherifying agent, x represents an integer of 1 or more, and n represents the average in the liquefied biomass molecule. Shows the number of hydroxyl groups, m shows the average number of etherified hydroxyl groups in the liquefied biomass molecule, and 0 <m ≦
A biomass-derived polyol represented by n). 4. The biomass-derived polyol according to claim 3, wherein an epoxide is used as the etherifying agent. 5. The polyol derived from biomass according to claim 1, wherein one or more kinds selected from the group consisting of lignocelluloses and saccharides are used as the biomass substance. 6. The compound having a hydroxyl group having a molecular weight of 20 or more having at least two hydroxyl groups in at least a part thereof.
The biomass-derived polyol according to any one of claims 1 to 5, wherein a polyhydric alcohol of 00 or less is used. 7. The polyhydric alcohol has 2 or 3 hydroxyl groups and a molecular weight of 150 or less.
The polyol derived from biomass according to 1. 8. A biodegradable polyurethane obtained by reacting the biomass-derived polyol according to any one of claims 1 to 7 with a polyisocyanate. 9. A biodegradable polyurethane obtained by reacting a mixed polyol of the polyol derived from biomass according to any one of claims 1 to 7 with another polyol, and a polyisocyanate.