WO2007080929A1

WO2007080929A1 - Polyoxalate urethane

Info

Publication number: WO2007080929A1
Application number: PCT/JP2007/050259
Authority: WO
Inventors: Hiroshi Okushita; Kouichiro Kurachi; Fumio Adachi
Original assignee: Ube Industries, Ltd.
Priority date: 2006-01-12
Filing date: 2007-01-11
Publication date: 2007-07-19
Also published as: JPWO2007080929A1; JP5380841B2; TW200738768A

Abstract

Disclosed is a polyoxalate urethane having excellent durability (hydrolysis resistance) and biodegradability, which is obtained by reacting a polyoxalate polyol (component A), at least one of polyester polyols, polyalkylene ether polyols and polyhydroxycarboxylate polyols (component B), a chain extender (component C) and a polyisocyanate compound (component D).

Description

Specification

Polyoxalate urethane

Technical field

[0001] The present invention relates to a novel polyoxalate urethane, and more particularly to a polyoxalate urethane excellent in hydrolysis characteristics and biodegradation characteristics.

Background art

[0002] Patent Document 1 proposes polyoxalate urethane as a polyester urethane having excellent biodegradability. However, this product has excellent biodegradability, but has a room for improvement in terms of durability (hydrolysis resistance) due to its high hydrolysis rate. This document describes that various known additives and other polymers can be blended with polyoxalate urethane, but no method capable of solving such a problem has been described.

Patent Document 1: Japanese Patent Laid-Open No. 2003-335837

Disclosure of the invention

Problems to be solved by the invention

[0003] The present invention solves the problems of known polyoxalate urethanes and provides a polyoxalate urethane that is excellent in durability (hydrolysis resistance) and biodegradability. Let it be an issue.

Means for solving the problem

[0004] The present invention relates to the following items.

[0005] 1. At least one of polyoxalate polyol (component A), polyester polyol, polyalkylene ether polyol, polyhydroxycarboxylic acid polyol (component B), chain extender (component C), and polyisocyanate Polyxylated urethane obtained by reacting a compound (component D).

[0006] 2. A component is a polyoxalate diol represented by the formula (1), B component strength S, polyester diol represented by the formula (2), polyalkylene ether represented by the formula (3) Diol is at least one of polyhydroxycarboxylic acid diols represented by formula (4), and D component 2. The polyoxalate urethane according to 1 above, wherein is a diisocyanate compound.

[0007] [Chemical 1]

H_〇 ten R ¹ 〇_C_〇_COO- R ¹ OH

n

(In the formula, R ¹ represents a divalent aliphatic hydrocarbon group having 3 to 12 carbon atoms which may contain a branched structure or an alicyclic structure, and n is a positive integer representing the degree of polymerization. )

[0008] [Chemical 2]

(Wherein R ² and R ³ represent a divalent aliphatic hydrocarbon group having 2 carbon atoms which may contain a branched structure or an alicyclic structure, and m is a positive integer representing the degree of polymerization.)

[0009] [Chemical 3]

(In the formula, R ⁴ and R ⁵ represent a divalent aliphatic hydrocarbon group having 2 to 6 carbon atoms, which may include a branched structure, and k is a positive integer representing the degree of polymerization. )

[0010] [Chemical 4]

HO-hR ⁶ COO 〇H

J

(In the formula, R ⁷ represents a divalent aliphatic hydrocarbon group having 2 to 6 carbon atoms which may contain a branched structure, and j is a positive integer representing the degree of polymerization.)

3. The above 1 or the ratio of the sum of the A component and the B component and the ratio of the C component and the D component “(A + B): C: D” is 1: 0.5: 1.5 to 1: 6: 7 on a molar basis 2. Polyoxalate urethane according to 2.

[0011] 4. The polyxylated urethane as described in 3 above, wherein the ratio of the eight components to the eight components “8: 8” is 5:95 to 95: 5 on a weight basis. [0012] 5. The polyoxalate urethane according to 1 or 2 above, wherein the number average molecular weight of each of the component A and the component B is in the range of 500 to 5,000.

The invention's effect

[0013] According to the present invention, a polyester having excellent durability (hydrolysis resistance), excellent biodegradability, and sufficient mechanical and thermal properties to be used as a general thermoplastic polyurethane. Oxalate urethane can be provided. For this reason, the polyoxalate urethane of the present invention can be widely used as an excellent biodegradable material such as a molded product, a film, and a sheet, and is very useful.

BEST MODE FOR CARRYING OUT THE INVENTION

[0014] [Component A]

The polyoxalate polyol of component A is a compound having a structure obtained by subjecting an oxalate source and a polyol to a polycondensation reaction. Examples of the oxalate source include oxalic acid diester and oxalic acid. When oxalic acid diester is used, it becomes a polycondensation reaction accompanied by an ester exchange reaction. As the oxalate source, oxalic acid diesters are preferred, for example, dialkyl oxalate such as dimethyl oxalate, decyl oxalate, dipropyl oxalate, dibutyl oxalate, and oxalic acid diaryl such as diphenyl oxalate alone. Or it can be used in plural. Of these, dimethyl oxalate is the most preferred.

[0015] The polyol is preferably an aliphatic polyol such as an aliphatic diol, an aliphatic triol, or an aliphatic tetraol. Among these, in the formula (5) in which the aliphatic diol represented by the formula (5) is more preferable, R ¹ is a divalent aliphatic hydrocarbon group having 3 to 12 carbon atoms, It may include a branched structure or an alicyclic structure without being limited to a linear structure. Also, it may have a ray substituent that does not participate in the polycondensation reaction or the polyurethane-forming reaction described later.

[0016] [Chemical 5

^{HO - 1 - 0 H (5} )

Examples of the aliphatic diol include 1,3_propanediol, 1,4_butanediol, 1,5_pentanediol, 1,6-hexanediol, and 1,7_heptanediol. Nore, 1,8_octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11_undecanediol, 1,12-dodecanediol, etc. , 2, 4-Dethyl-1,5_pentanediol, 3_Methyl-1,5, -pentanediol, 2_Ethyl _ 2_Butyl _ 1,3 _Propanediol, 2, 2, 4_Trimethyl _ 1, 3_propanediol, 2, 2_jetyl-1,3_propanediol, those containing a branched structure such as 2-ethyl_1,3-hexanediol, trans-1,4-cyclohexanedimethanol, cis _ l, 4-cyclohexanedimethanol and other alicyclic structures.

[0018] When a trivalent or higher polyol such as aliphatic triol or aliphatic tetraol is used as the polyol, a branched structure is introduced into the molecule. Therefore, when used, the obtained physical properties are taken into consideration. Thus, it is preferable to use it together with a diol.

[0019] The polycondensation reaction can be performed by a known method with an excess of polyol such that the terminal is a hydroxyl group. At that time, the reaction temperature and pressure are not particularly limited as long as the target product can be obtained, but the reaction temperature is 120 ° C to 350 ° C, and the reaction pressure is 1 mmHg (133 Pa) to 760 mmHg (l. 01 X 10 ⁵ Pa) or less. In order to accelerate the reaction, it is preferable to extract the alcohol etc. produced in the reaction out of the reaction system. To this end, it is preferable to provide a distillation column in the reactor. Further, inert gas (nitrogen, helium, Argon, etc.) It is also possible to add a known catalyst that can be reacted under a flow or the temperature or pressure can be varied. As the catalyst, a transesterification catalyst is preferred. For example, tetraalkoxytitanium (tetra- _n -butoxytitanium, etc.) is preferred among the powers including compounds of metals such as titanium, zinc, germanium, iron, and tin. The amount and timing of addition of the catalyst are not particularly limited as long as the conditions can promote the reaction.

[0020] Among the polyoxalate polyols of component A, in the formula (1) in which the polyoxalate diol represented by the formula (1) is preferred, n is the degree of polymerization of the polyoxalate diol (repeating structural unit "- I ^ OCOCOO ^ represents a repetition number) of the number average molecular weight in association et. R ¹ is also a type such safely be contained two or more les. the number average molecular weight of Poriokisa rate polyol A range of 500 to 5000, particularly 1000 to 3000 is preferable. [0021] [Component B]

Component B comprises at least one of polyester polyol, polyalkylene ether polyol, and polyhydroxycarboxylic acid polyol.

Of these, the polyester polyol is a compound having a structure obtained by subjecting a dicarboxylic acid source and a polyol to a polycondensation reaction. As the dicarboxylic acid source, an aliphatic dicarboxylic acid represented by the formula (6) is preferred. In the formula (6), R ³ has 2 carbon atoms which may contain a branched structure or an alicyclic structure. To: 12 is a divalent aliphatic hydrocarbon group which may have a substituent which does not participate in the polycondensation reaction or the polyurethane-forming reaction described below. Moreover, the diester of aliphatic dicarboxylic acid can also be mentioned preferably. Examples of the aliphatic dicarboxylic acid include succinic acid, gnoretaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, and dodecanedioic acid.

[0023] [Chemical 6]

HOOC— R ³ -COOH (6)

[0024] As the polyol, aliphatic polyols such as aliphatic diols, aliphatic triols, and aliphatic tetraols are preferable. Among them, in the formula (7), the aliphatic diol represented by the formula (7) is more preferable. In the formula (7), R ² includes a branched structure or an alicyclic structure. To 12 divalent aliphatic hydrocarbon groups, which may have a substituent that does not participate in the polycondensation reaction or the polyurethane-forming reaction described later. Examples of the aliphatic diol include ethylene glycol and the same aliphatic diol represented by the formula (5).

[0025] [Chemical 7]

^{H 0 - R 2 - 0 H} (7)

[0026] In addition, when a trivalent or higher polyol such as aliphatic triol or aliphatic tetraol is used as the polyol, a branched structure is introduced into the molecule. Thus, it is preferable to use it together with the diol as appropriate.

[0027] The polycondensation reaction can be performed by a known method with an excess of polyol such that the terminal is a hydroxyl group. For example, the aliphatic dicarboxylic acid and the aliphatic diol are necessary. Depending on the conditions, two or more types are used, and the former is 1 mol or more, and the latter is 1.01 mol or more, more preferably 1.05 mol or more and 2 mol or less, further 1.2 mol or less. Dehydration polycondensation reaction may be performed. At this time, the reaction temperature, reaction pressure, various methods for promoting the reaction, and the like are the same as in the case of obtaining the polyoxalate polyol.

[0028] Among the polyester polyols of component B, in the formula (2) in which the polyester diol represented by the formula (2) is preferred, m is the degree of polymerization of the polyester diol (structural unit “—R ² 〇C 〇R ³ C〇0— ”), and is related to the number average molecular weight. R ² and R ³ may be one type or two or more types. The number average molecular weight of polyester polyol is preferably in the range of 500 to 5000, particularly 1000 to 3000.

[0029] Among the B components, polyalkylene ether polyol is a compound having a structure obtained by subjecting an ether source and polyol to a polymerization reaction. As the ether source, an alkylene oxide represented by the formula (8) is preferred. In the formula (8), R ⁴ is a divalent aliphatic having 2 to 6 carbon atoms which may contain a branched structure. It may be a hydrocarbon group and may have a substituent that does not participate in the polymerization reaction or the later-described polyurethane-forming reaction. Examples of the alkylene oxide include ethylene oxide, propylene oxide, 1,2-butylene oxide, 2,3 butylene oxide, 1,3 butylene oxide, tetrahydrofuran, and 3-methyltetrahydrofuran.

[0030] [Chemical 8]

[0031] The polyol is preferably an aliphatic polyol such as an aliphatic diol, an aliphatic triol, or an aliphatic tetraol. Among these, in formula (9), the aliphatic diol represented by formula (9) is more preferred. In formula (9), R ⁵ is a divalent aliphatic carbon atom having 2 to 6 carbon atoms which may contain a branched structure. It may be a hydrogen group and may have a substituent that does not participate in the polymerization reaction or the polyurethane-forming reaction described later. Examples of the aliphatic diol include ethylene glycol, propylene glycol, 1,3-propanediol, and 1,4 butanediol. All, 1,5_pentanediol, 1,6-hexanediol, 1,3-butylene glycol, neopentyl glycol, 3_methyl_1,5_pentanediol, and the like.

[0032] [Chemical 9]

^{HO - R 5 - 0 H (} 9)

[0033] When a trivalent or higher polyol such as aliphatic triol or aliphatic tetraol is used as the polyol, a branched structure is introduced into the molecule. You may use it independently suitably.

[0034] The polymerization reaction can be carried out by a known method. For example, the alkylene oxide and the aliphatic diol are subjected to a ring-opening addition polymerization reaction. This reaction can be carried out under ordinary conditions, and can be carried out in one step or in multiple steps at normal pressure or under pressure in the presence of no catalyst or catalyst (alkali catalyst, amine catalyst, acidic catalyst, etc.).

[0035] Among the polyalkylene ether polyols of component B, in the formula (3) in which the polyalkylene ether diol represented by the formula (3) is preferred, k is the degree of polymerization of the polyalkylene ether diol. represents - (structural unit "R ⁴ 0-" repetition number of), it is associated with a number average molecular weight. R ⁴ and R ⁵ may be one type or two or more types. The number average molecular weight of the polyalkylene ether polyol is preferably in the range of 500 to 5000, particularly 1000 to 300,000.

[0036] Among the B components, the polyhydroxycarboxylic acid polyol is a compound having a structure obtained by subjecting a hydroxycarboxylic acid source and polyol to a polymerization reaction. In the formula (10), an aliphatic cyclic ester represented by the formula (10) is preferred as the hydroxycanolenic acid source. In the formula (10), R 6 has 2 to 6 carbon atoms which may contain a branched structure. It is a divalent aliphatic hydrocarbon group, and may have a substituent that does not participate in the polymerization reaction or the polyurethane-forming reaction described later. Examples of the aliphatic cyclic ester include L-lactide, D-lactide, D, L-lactide, β-propiolatathone, γ-butyrolatathone, δ-valerolatatone, and ε-force prolatathone.

[0037] [Chemical 10]

[0038] The polyol is preferably an aliphatic polyol such as an aliphatic diol, an aliphatic triol, or an aliphatic tetraol. In this, in the formula (11) in which the aliphatic diol represented by the formula (11) is more preferable, R ⁷ is a divalent aliphatic carbonization having 2 to 6 carbon atoms which may contain a branched structure. It may be a hydrogen group and may have a substituent that does not participate in the polymerization reaction or the polyurethane-forming reaction described below. Examples of the aliphatic diol include the same aliphatic diols represented by the formula (9).

[0039] [Chemical 11]

^{H 0 - R 7 - 0 H} (1 1)

[0040] When a trivalent or higher polyol such as aliphatic triol or aliphatic tetraol is used as the polyol, a branched structure is introduced into the molecule. You may use it independently suitably.

[0041] The polymerization reaction can be carried out by a known method. For example, the aliphatic cyclic ester may be subjected to a ring-opening polymerization reaction using the aliphatic diol as an initiator. This reaction can be carried out under normal conditions, and can be carried out at normal pressure or reduced pressure in the presence of a catalyst such as a compound of a metal such as antimony, titanium, zinc, germanium, iron, tin or the like.

[0042] Among the polyhydroxycarboxylic acid polyols of component B, polyhydroxycarboxylic acid diol represented by the above formula (4) is preferred. In formula (4), j is a polyhydroxycarboxylic acid diol. Is the degree of polymerization (repeated number of structural units “one R ⁶ COO—”) and is related to the number average molecular weight. R ⁶ and R ⁷ may be one type or two or more types. The number average molecular weight of the polyhydroxycarboxylic acid polyol is preferably in the range of 500 to 5,000, particularly in the range of 1,000 to 3,000.

[0043] [Component C] Examples of the component C chain extender include low molecular weight compounds having at least two hydrogen atoms that react with an isocyanate group. Such compounds include polyols and polyamines such as ethylene glycol, 1,2_propylene glycol, 1,3_butanediol, 1,4_butanediol, 1,5_pentanediol, 1 , 6_Hexanediol, 1,8_octanediol, 1,9 nonanediol, 1,10 decanediol, 1,12-dodecanediol, neopentyl glycol, 3_methyl_1,5-pentanediol, 3, 3_Carbon which may contain a branched structure or alicyclic structure such as dimethylolheptane, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 1,4-dihydroxyethylcyclohexane An aliphatic diol having a number of 2 to 12 is preferred.

[0044] As polyamines, ethylenediamine, 1,2 propylenediamine, 1,6hexamethylenediamine, isophoronediamine, bis (4 aminocyclohexyl) methane, piperazine and the like are branched. Structure or cycloaliphatic structure, aliphatic diamines having 2 to 12 carbon atoms, m (or p) xylylenediamine, 4,4'-methylenebis (o chloroaniline) Preferred examples thereof include aromatic diamines having 6 to 18 carbon atoms such as.

[0045] Furthermore, aliphatic amino alcohols (2 ethanolamine, N-methyljetanolamine, etc.), aromatic amino alcohols (N phenyldipropanolamine, etc.), hydroxyalkylsulfamides (hydroxyethylsulfamide). Amide, hydroxyethylaminoethylsulfamide, etc.), urea, water and the like can also be mentioned as chain extenders. These chain extenders can be used alone or in combination.

[0046] [Component D]

Examples of the D component polyisocyanate compound include various aliphatic or aromatic polyisocyanates. The aliphatic polyisocyanate contains an oxygen atom whose polyvalent aliphatic hydrocarbon group is not limited to one having a straight chain structure but may contain a branched structure or an alicyclic structure. It may be a thing. The aromatic polyisocyanate is not particularly limited as long as it contains a polyvalent aromatic hydrocarbon group in the molecule. Of the polyisocyanate compounds, diisocyanate compounds are preferred, and examples thereof include aliphatic and aromatic diisocyanates. D component polyisocyanate used alone or in combination it can.

[0047] As the aliphatic diisocyanate, for example, 1, 3 trimethylene diisocyanate, 1, 4

—Tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,9 nonamethylene diisocyanate, 1,10-decamethylene diisocyanate, 1,12-dodecamethylene diisocyanate Lysine diisocyanate, hexamethylene diisocyanate monobiuret, 2, 2, 4_trimethinorehexamethylene diisocyanate, 2, 4, 4_trimethinore hexamethylene diisocyanate , Isophorone diisocyanate, 1,4-cyclohexane diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, hydrogenated xylylene diisocyanate, 2,2'-jetyl ether diisocyanate, etc. Can be mentioned.

[0048] Examples of the aromatic diisocyanate include p-phenylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate, 4,4'-diphenyl diisocyanate, 1,5-naphthalenediisocyanate, 4,4'-diphenylmethane diisocyanate (MDI), 3,3'-methyleneditolylene 4,4'-diisocyanate, tolylene sulfonate trimethylolpropane adduct, triphenylmethane Triisocyanate, 4,4'-Diphenyl ether diisocyanate, Tetrachlorodiphenyl diisocyanate, 3, 3'-Dichloro-4,4, -Diphenylmethane diisocyanate, Triisocyanate Examples include phenylthiophosphate.

Among these diisocyanates, 4,4′-diphenylmethane diisocyanate, 1,6-hexamethylene diisocyanate, and isophorone diisocyanate are particularly preferred.

[0050] [Polyoxalate urethane]

The polyoxalate urethane of the present invention comprises at least one of polyoxalate polyol (component A), polyester polyol, polyalkylene ether polyol, polyhydroxycarboxylic acid polyol (component B), chain extender (component C), The polyisocyanate compound (component D) is reacted (polyurethane reaction), and the number average molecular weight is preferably in the range of 10,000 to 200,000.

[0051] Here, the sum of the A component and the B component and the ratio of the C component and the D component “(A + B): C: D” is 1: 0.5: 1.5 to 1: 1: 6: 7, preferably in the range. However, the total amount of active hydrogen contained in the mixture of component A and component B and component C: isocyanate ratio 1: 0.8 It is preferable to use D component so that it will be set to :: 1: 1.2, Furthermore, it is 1: 0.9.95-: 1: 1.05. In addition, the ratio “A: B” of the A component and the B component may be in the range of 5:95 to 95: 5, further 10:90 to 70:30, particularly 20:80 to 50:50 on a weight basis. I like it. In addition, the A component and the B component may have different aliphatic hydrocarbon groups or different number average molecular weights.

[0052] The polyurethane reaction can be carried out in the absence of a solvent, and can also be carried out in the presence of a solvent inert to the isocyanate group. In the case of a reaction in the absence of a solvent, a mixture of component A and component B and component C are mixed, and then component D is mixed with this to react all at once, or a mixture of component A and component B After reacting the D component to obtain a prepolymer having an isocyanate group, the C component is mixed and reacted with this, or the mixture of the A component and the B component is mixed with the C component, and this is part of the D component. After obtaining a prepolymer having a hydroxyl group by mixing and reacting, a polyurethane reaction can be carried out by further mixing and reacting the remaining D component. The reaction temperature in the absence of a solvent is preferably 80 to 180 ° C.

[0053] In the case of the reaction in the presence of a solvent, the mixture of the component A and the component B is dissolved in the solvent and the component C is further mixed, and then the component D is mixed with the mixture to react all at once. A mixture of component A and component B is dissolved in a solvent, and component D is mixed and reacted to obtain a prepolymer having an isocyanate group, and then mixed with component C and reacted. Dissolve the mixture of component A and component B in a solvent, mix and react a part of component C and component D to obtain a prepolymer having a hydroxyl group, and then mix and react the remaining component D. Thus, the polyurethane reaction can be carried out. The reaction temperature in the presence of a solvent is preferably 20 to 100 ° C. Typical examples of the solvent include methyl ethyl ketone, ethyl acetate, toluene, dioxane, dimethylformamide, dimethyl sulfoxide, dimethylacetamide, and chloroform. In the polyurethane reaction, a known amine-based or tin-based catalyst may be used to promote the reaction.

[0054] The polyoxalate urethane of the present invention has a high molecular weight or a reticulated structure by further reacting with a compound having at least two hydrogen atoms that react with an isocyanate group or a compound having at least two isocyanate groups. can do. Also urethane bond A crosslinked structure can also be introduced by reacting with a compound having z or urea bond or a compound having at least three hydrogen atoms that react with isocyanate groups.

[0055] The polyoxalate urethane of the present invention can also be made into a polyoxalate urethane composition by blending with other polyurethanes. The other polyurethane may be a known thermoplastic polyurethane. For example, thermoplastic polyurethanes such as adipate, ratatone, and ether are preferably used. In this composition, the ratio of the polyoxalate urethane of the present invention to the other polyurethane is such that the former: the latter (weight ratio) is 5: 95-95: 5, further 10:90 to 90:10, especially 20:80. It is preferably in the range of ˜80: 20. The polyoxalate urethane and other polyurethanes of the present invention can be used alone or in combination. The polyoxalate urethane obtained from the A component, the C component, and the D component can be blended with other polyuretans to obtain a similar composition.

[0056] The most common method of blending is a known continuous kneader (single screw extruder, twin screw extruder, twin screw rotor kneader, etc.) or a notch type kneader (open roll, kneader, And a kneading method and kneading conditions are not particularly limited. A solution blending method using a solvent is also acceptable.

[0057] The polyoxalate urethane and the composition thereof according to the present invention may be blended with various known additives and other polymers singly or in a range that does not impair the effects of the present invention. . Additives that can be added include crystal nucleating agents, pigments, dyes, heat-resistant agents, anti-coloring agents, antioxidants, weathering agents, lubricants, antistatic agents, stabilizers, and fillers (talc, clay, zeolite, zonotlite. , Calcium carbonate, carbon black, silica powder, alumina powder, titanium oxide powder, resin-type microballoon, inorganic-type microballoon, etc.), reinforcing materials (glass fiber, carbon fiber, silica fiber, etc.), flame retardant, plasticizer, waterproofing Agents (wax, silicone oil, higher alcohol, lanolin, etc.).

[0058] Examples of other compoundable polymers include natural or synthetic polymer materials, such as polystrength prolatatone, polylactic acid, polydaricholic acid, polysuccinic acid ester, poly (3-hydroxybutanoic acid). , (3-hydroxybutanoic acid / 4-hydroxybutanoic acid) copolymer , Plastic materials such as polybulol alcohol, polyethylene, polyacetic acid butyl, polychlorinated butyl, polystyrene, polyglutamic acid ester, cellulose acetate, alginic acid, chitosan, starch, natural rubber, polyester rubber, polyamide rubber, styrene-butadiene-styrene Examples include rubbers or elastomers such as block copolymers (SBS) and hydrogenated SBS.

[0059] In addition, the polyoxalate urethane and the composition thereof according to the present invention are applied with a known melt processing method (injection molding, extrusion molding, press molding, hollow molding, thermoforming, etc.) to form a film, a sheet, It can be formed into molded products such as fibers, non-woven fabrics, containers, various agricultural / industrial materials or components. Of these, injection moldings are used for sealing materials, gears, connectors, sports shoes, marine sports equipment, watch bands, casters, rollers, heel tops for women's shoes, precision polishing pads, wet filters, sponge rolls, etc. Is mentioned. Extruded products can be used for various hoses, tubes, Envelope belts, air mats, tarpaulins (for field sheets, leisure bags, civil engineering sheets, machine covers, etc.), cable covers, various ropes, etc. .

Example

Next, the present invention will be specifically described with reference to examples and comparative examples. The physical properties of the polyoxalate diol were measured by the methods 1 and 2 below, and the physical properties of the polyoxalate urethane and the polyoxalate urethane composition were measured by the methods 3 to 7 below.

[0061] 1. Number average molecular weight (M) ^ H—NMR measurement was carried out under the following conditions, and was calculated by the following formula. Where S is the integral of the methylene proton adjacent to the oxalate bond

OCOCOO

Value, S is the integral value of the proton of methylene adjacent to the terminal hydroxyl group, M is the polyoxalene

OH unit Molecular weight of repeating structural unit in the diol, M is the raw material of polyoxalate diol

diol

Represents the molecular weight of the aliphatic diol.

[0062] · Model used: JEOL MJNM—EX400WB

'Solvent: CDC1

Three

• Integration count: 32 times

'Sample concentration: 5% by weight

'Calculation formula: M = S / S X M + M

n OCOCOO OH unit diol [0063] 2. Melting point (T): Nitrogen gas atmosphere using a differential scanning calorimeter (DSC-50; manufactured by Shimadzu Corporation)

The measurement was performed in the atmosphere under the condition of a temperature increase rate of 10 ° CZ.

[0064] 3. Glass transition temperature (T): Measured in the same manner as the melting point.

g

[0065] 4. Viscosity (Pa 'sec): Measured using an E-type viscometer (manufactured by Tokyo Keiki).

[0066] 5. Tensile properties: Tensile elasticity measured at 23 ° C and 50% RH using a tensile tester (Tensilon UCT-5T; manufactured by Orientec) according to JIS—K7311 The rate, tensile strength, and elongation at break were determined.

[0067] 6. Hydrolysis resistance: JIS No. 2 tensile test specimens were immersed in pure water at 23 ° C, and then the tensile characteristics were measured as described above and evaluated from the retention of elongation at break.

[0068] 7. Biodegradation characteristics: Specimens (lcm XI cm) composted (Hochicon CJA) ground to 5 mesh or less; placed in 30 ° C), taken out every week and weighed The residual rate was measured.

[0069] [Reference Example 1] <Production of polyoxalate diol>

Into a 1 L (liter) glass reactor equipped with a stirrer, thermometer, and distillation column (with a fractionation tube, reflux head, and condenser at the top of the column), dimethyl oxalate (DMO) 372.0 g (3. 15 monole), 1, 6-hexanedi-nore (HDL) 531.8 g (4.508 monole), and tetra-n-butoxytitanium (TBT) O. 027 g (weight based on total amount of DMO and HDL) 30 ppm), and methanol was distilled off, and the reaction was carried out at 160 ° C for 3 hours under atmospheric pressure and further for 1 hour at 170 ° C under 300 mmHg (4 X 10 ⁴ Pa). Then, 180 ° C to NoboriAtsushisu Rutotomoni ^{lOOmmfig d. 33 X 10 4 Pa} ) vacuum to between 5B temple was reacted for 2 hours further at 5mnLHg (666Pa). Finally, TBT and an equimolar amount of dibutyl phosphate were added to the reaction product and stirred at 95 ° C for 3 hours under normal pressure to deactivate the catalyst. The resulting polyoxalate diol (PH MOD-1; polyhexamethyleneoxalate diol) has an M force of 2089 and a repulsive force of 72 ° C.

n m

there were.

[Reference Example 2] <Production of polyoxalate diol>

A glass reactor with an internal volume of 3 L equipped with a stirrer, thermometer and distillation column (with a fractionation tube, reflux head, and condenser at the top of the column) was added DM 1116 g (9.45 monolayer), HDL159 5 g (13. 50 mol), and TBTO. 081 g (weight basis for the total amount of DM〇 and HDL) The reaction was carried out at 170 ° C under normal pressure for 3 hours and further at 170 ° C under 30 OmmHg for 1 hour while distilling methanol. Next, the temperature was raised to 180 ° C and reduced to lOOmmHg for 4 hours, and the temperature was raised to 200 ° C and reduced to lmmHg (133Pa) for 2.5 hours. Finally, TBT and an equimolar amount of dibutyl phosphate were added to the reaction product, and the catalyst was deactivated by stirring at 120 ° C for 2 hours under normal pressure. The resulting polyoxalate diol (PHM ○ D_ 2; polyhexamethylene oxalate diol) has an M force of 1963 and a repulsion force of 72 ° C.

n m

I got it.

[Example 1]

Into a 1 L glass reactor equipped with a stirrer, thermometer and condenser, 25 g (0.0120 mol) of polyoxalate diol (PHMOD-1) obtained in Reference Example 1 and polyethylene adipate diol (PEAD) ; Nippon polyurethane made of Japanese polyurethane 4040; M = 2047, T

n m

= 46 ° C) 25 g (0.0122 mol) was charged and mixed with stirring at 100 ° C for 1 hour in a nitrogen atmosphere. Then, 4,4-diphenylmethane diisocyanate (MDI; made by Nippon Polyurethane) 12. lg (0.0484 mol) was added and reacted at the same temperature for 2 hours. Thereafter, the reaction solution was allowed to cool to room temperature and completely dissolved in 139 g of dimethylformamide (DMF). The solution was then cooled to 3 ° C and 1,2-propylenediamine (PDA; dissolved in 10 g DMF) 1. 79 g (0.0 241 mol) was added and stirred vigorously for 5 min. The reaction was continued, and the temperature was raised to 50 ° C and the reaction was carried out while adding MDI little by little. The reaction was terminated when the viscosity (50 ° C) reached 11.6 Pa'sec.

[0072] After completion of the reaction, DMF was added to the reaction solution to adjust the polyoxalate urethane concentration to 31% by weight, and the resulting solution was cast on a releasable glass plate at 70 ° C for 1 hour. Then, it was dried at 120 ° C. for 2 hours to obtain a film of about 200 μm. Tables 1 and 2 show the results of evaluating the physical properties of polyoxalate urethane using this film.

[Example 2]

PHMOD— 1 charge 15g (0.0072 monole), PEAD charge 35g (0.0171 monole), MDI usage 12.2g (0.0486 monole) (this change, PDA usage 1. The reaction was carried out in the same manner as in Example 1 except that the reaction was terminated when the viscosity (50 ° C) reached 11.3 Pa'sec after changing to 80 g (0.02 43 mol). After that, about 200 xm as in Example 1. The film was obtained to evaluate the physical properties of polyoxalate urethane. The results are shown in Tables 1 and 2.

[Example 3]

^ 11 ^ 〇0_1 Feeding amount is 5§ (0.0024 monole), PEAD feeding amount is 45g (0.220 monole), MDI usage is 12.2g (0.0486 monole) (changed, PDA usage is 1.81g (0.0244mol) The reaction was carried out in the same manner as in Example 1 except that the reaction was terminated when the viscosity (50 ° C) reached 12.4 Pa'sec, and after the reaction, about 200 An xm film was obtained to evaluate the physical properties of polyoxalate urethane, and the results are shown in Tables 1 and 2.

[Example 4]

PHMOD— 1 feed amount is changed to 25 g (0.0120 monole), PEAD is polyhexamethylene sebacate diol (PHSD; Ube Industries Etanacol 3020; M = 3643

n, T = 65

m

The reaction was conducted in the same manner as in Example 1 except that the temperature was changed to 44 g (0.0121 mol). After completion of the reaction, a film having a thickness of about 200 μm was obtained in the same manner as in Example 1, and the physical properties of polyoxalate urethane were evaluated. The results are shown in Tables 1 and 2.

[Example 5]

PHMOD— 1 feed amount is changed to 5 g (0.0024 monole), PEAD is polytetramethylene monoterglycol (PTMG; Hodogaya Chemical PTG2000SN; M = 1993

n, T = 34 ° C)

m

45 g (0.0226 monole) ί This change was made and the amount of MDI used was 12.5 g (0.050 monole) (other than this change ¾; the reaction was carried out in the same manner as in Example 1 to completely dissolve the reaction solution in 140 g of DMF. Next, the reaction was completed in the same manner as in Example 1 except that the amount of PDA used was changed to 1.85 g (0.0250 mono) and the reaction was terminated when the rice occupancy (50 ° C) force reached 26.8 Pa'sec. After completion of the reaction, except that the polyoxalate urethane concentration was adjusted to 30% by weight, a film of about 200 μm was obtained in the same manner as in Example 1 to evaluate the physical properties of the polyoxalate urethane. Are shown in Tables 1 and 2.

[Example 6]

In the same reactor as in Example 1, 6 g (0.002 9 mol) of polyoxalate diol (PHM 0 D_l), poly-force prolatatone diol (PCLD; Plaxel 220 manufactured by Toa Gosei); M = 19 86, T = 54 ° C) 54g (0.0272 monole), 1, 4_butangi-nore (BDL) 2. 73g (0.03 m

0 mol) and 170 g of DMF, and after stirring and mixing at 100 ° C for 1 hour under a nitrogen atmosphere, hexamethylene diisocyanate (HDI; made by Nippon Polyurethane) 10.6 g (0.063 monore) and dilauric acid Dibutyltin (0.025 g) was added and reacted with vigorous stirring. The reaction was continued while adding HDI little by little, and the reaction was terminated when the viscosity (50 ° C) reached 47.2 Pa'sec. After completion of the reaction, a film of about 200 μm was obtained in the same manner as in Example 1 except that the polyoxalate urethane concentration was adjusted to 25% by weight, and the physical properties of the polyoxalate urethane were evaluated. The results are shown in Tables 1 and 2.

[Comparative Example 1]

A reactor similar to Example 1 was charged with 40 g (0.019 1 mol) of polyoxalate diol (PHMOD-1), stirred and mixed at 100 ° C for 1 hour in a nitrogen atmosphere, and then MDI (manufactured by Nippon Polyuretan). 9. 58 g (0.0383 mol) was added and reacted at the same temperature for 2 hours. Thereafter, the reaction solution was allowed to cool to room temperature and completely dissolved in 109 g of dimethylformamide (DMF). Next, this solution was cooled to 3 ° C, PDA (dissolved in 10 g of DMF) 1 · 42 g (0.0191 mol) was added, and the mixture was allowed to react for 5 minutes with vigorous stirring. The reaction was carried out while adding MDI little by little, and the reaction was terminated when the viscosity (40 ° C) reached 69.8 Pa 'sec. After the reaction was completed, a film of about 200 μm was obtained in the same manner as in Example 1 except that the polyoxalate urethane concentration was adjusted to 30.3 wt%, and the physical properties of the polyoxalate urethane were evaluated. The results are shown in Tables 1 and 2.

[0079] [Table 1]

T2 Pull ¾ Elastic modulus Pull ¾ Strength Breaking elongation

Α component * B component *

CO (MPa) (MPa) (%) Implementation Ml PHMOD-1 (0.01 20) PEAD (0.0122) -39 5.61 6.4 845 Example 2 PHMOD-1 <H 0072> PEAD (0.01 71) -39 3.81 39.5 670 Example 3 PH OD-1 <0.0024> PEA0 (0.0220) -41 4.76 5 .3 724 Actually 4 PH OD-1 (0.01 20) PHSD (0.01 21) -58 4.50 49.0 600 Example 5 PHM0D-1 (0.0024) PTMG ( 0.0226) -81 5.1 6 40.7 825 Example 6 PHMOD-1 (0.0029) FOLD (0.0027) -64 8.90 51.8 830 Comparative example 1 PH OD-1 (0.01 91) ― -29 2.20 32.7 460

* Summary ?! The number in the figure represents the number of moles charged. * Ie of each component is as follows.

PH OD-1: Polyhexamethyleneoxalate diol

PEAD: Polyethylene Adi'Patediol

PHSD: Polyhexamethylene Sebake "" Todiol

PT G: Polyderamethylene ether glycol

PC D: Polycube α-lactone diol

[0080] [Table 2]

[0081] [Reference Example 3]

A 5 L glass reactor equipped with a stirrer, thermometer and cooling tube was charged with 500 g (0.255 mol) of polyoxalate diol (PHMOD-2) obtained in Reference Example 2 in a nitrogen atmosphere, and 90 ° under a nitrogen atmosphere. After melting with C, 359.3 g (l.436 monole) of MDI (manufactured by Nippon Polyurethane) was added and reacted at the same temperature for 3 hours. Next, BDL107.5 g (l.193 monole) was added and reacted for 1 minute with vigorous stirring. The reaction solution was immediately poured into a stainless steel vat (with a Teflon (registered trademark) release film), 90 under vacuum. Cured with C for 2 hours.

[0082] The obtained polyoxalate urethane block was crushed, and 12.5 g of the crushed product and 37.5 g of adipate-based thermoplastic polyurethane (Pandettas T-1195; manufactured by Dainippon Ink and Chemicals, Inc.) Next, the mixture was melt kneaded at 210 ° C. for 5 minutes using a batch Brabender type twin-screw kneader (rotation speed: 60 rotations Z minutes). The resulting polyoxalate urethane composition was melt-molded using a compression molding machine manufactured by Shinfuji Metal Industry Co., Ltd. to obtain a film of about 100 zm at 210 ° C under 4.9 MPa to evaluate the physical properties of the polyoxalate urethane composition. did.

[0083] As a result, T was -33 ° C, tensile modulus was 55.2 MPa, tensile strength was 31.9 MPa, rupture g

The growth is 300. /. Met. The hydrolysis resistance (breaking elongation retention) is 101. /. (1 week), 105% (2 weeks), 40% (3 weeks), and biodegradation characteristics (weight survival rate) are 99.0% (1 week), 97.3% (2 weeks), 92. 8% (3 weeks) and 93.5% (4 weeks).

[0084] [Reference Example 4]

A film was obtained in the same manner as in Reference Example 3 except that the adipate-based thermoplastic polyurethane was replaced with an ether-based thermoplastic polyurethane (Pandex T-8190; manufactured by Dainippon Ink & Chemicals, Inc.). evaluated. As a result, T is -48 ° C, g

The tensile modulus was 40.0 MPa, the tensile strength was 21 OMPa, and the elongation at break was 350%. The hydrolysis resistance (breaking elongation retention) is 101% (1 week), 105% (2 weeks), 38% (3 weeks), and the biodegradation characteristics (residual weight) are 98. They were 9% (1 week), 97.1% (2 weeks), 92.6% (3 weeks), and 93.3% (4 weeks).

Industrial applicability

[0085] According to the present invention, a polyester having excellent durability (hydrolysis resistance) and excellent biodegradability, as well as mechanical properties and thermal properties sufficient for use as a general thermoplastic polyurethane. Oxalate urethane can be provided. For this reason, the polyoxalate urethane and the polyoxalate urethane composition of the present invention can be widely used as excellent biodegradable materials such as molded articles, films and sheets, and are very useful.

Claims

Claims [1] Polyoxalate polyol (component A), polyester polyol, polyalkylene ether polyol, at least one of polyhydroxycarboxylic acid polyol (component B), chain extender (component C), and poly Polyoxalate urethane obtained by reacting isocyanate compound (component D). [2] The A component is a polyoxalate diol represented by the formula (1), the B component is a polyester diol represented by the formula (2), a polyalkylene ether diol represented by the formula (3), a formula 2. The polyoxalate urethane according to claim 1, wherein the polyoxalate urethane is at least one of the polyhydroxycarboxylic acid diols represented by (4), and the D component is a disocene H compound.

[Chemical 1]

H〇 + R ¹ OCOCOO- R ¹ OH

n

[Chemical 2]

(In the formula, R ² and R ³ each have 2 carbon atoms which may contain a branched structure or an alicyclic structure.

It represents a divalent aliphatic hydrocarbon group, and m is a positive integer representing the degree of polymerization. )

[Chemical 3]

[Chemical 4]

(Wherein R ⁶ and R ⁷ represent a divalent aliphatic hydrocarbon group having 2 to 6 carbon atoms which may contain a branched structure, and j is a positive integer representing the degree of polymerization.)

[3] The sum of the A and B components and the ratio of the C and D components “(A + B): C: D” is 1: 0 on a molar basis.

The polyoxalate urethane according to claim 1 or 2, wherein .5: 1.5 to 1: 6: 7.

4. The polyxalate urethane according to claim 3, wherein the ratio “A: B” of the A component to the B component is 5:95 to 95: 5 on a weight basis.

[5] The number average molecular weight of each of component A and component B is in the range of 500 to 5,000.

The polyoxalate urethane according to 1 or 2.