JP5380841B2 - Polyoxalate urethane - Google Patents

Description

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

Polyoxalate urethane is proposed in Patent Document 1 as a polyester urethane having excellent biodegradability. However, this product has excellent biodegradability, but has a room for improvement in terms of fast hydrolysis rate and durability (hydrolysis resistance). This document describes that various known additives and other polymers can be blended with polyoxalate urethane, but no method capable of solving such problems has been described.
JP 2003-335837 A

  An object of the present invention is to solve the problems of known polyoxalate urethanes and to provide a polyoxalate urethane that is excellent in durability (hydrolysis resistance) and excellent in biodegradability.

  The present invention relates to the following matters.

  1. Reaction of at least one of polyoxalate polyol (component A), polyester polyol, polyalkylene ether polyol, polyhydroxycarboxylic acid polyol (component B), chain extender (component C), and polyisocyanate compound (component D) Polyoxalate urethane obtained.

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

（式中、Ｒ^１は分岐構造又は脂環式構造を含んでいてもよい炭素数３〜１２の二価の脂肪族炭化水素基を表し、ｎは重合度を表す正の整数である。）

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

（式中、Ｒ^２及びＲ^３は分岐構造又は脂環式構造を含んでいてもよい炭素数２〜１２の二価の脂肪族炭化水素基を表し、ｍは重合度を表す正の整数である。）

(Wherein R ² and R ³ represent a divalent aliphatic hydrocarbon group having 2 to 12 carbon atoms which may contain a branched structure or an alicyclic structure, and m is a positive integer representing the degree of polymerization. is there.)

（式中、Ｒ^４及びＲ^５は、分岐構造を含んでいてもよい、炭素数２〜６の二価の脂肪族炭化水素基を表し、ｋは重合度を表す正の整数である。）

(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.)

（式中、Ｒ^６及びＲ^７は分岐構造を含んでいてもよい炭素数２〜６の二価の脂肪族炭化水素基を表し、ｊは重合度を表す正の整数である。）
３． Ａ成分及びＢ成分の合計とＣ成分とＤ成分の比「（Ａ＋Ｂ）：Ｃ：Ｄ」がモル基準で１：０．５：１．５〜１：６：７である、上記１又は２記載のポリオキサレートウレタン。

(In the formula, 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. 1 or 2 above, wherein 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. The polyoxalate urethane described.

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

  5. The polyoxalate urethane according to 1 or 2 above, wherein the number average molecular weights of the A component and the B component are each in the range of 500 to 5,000.

  According to the present invention, the polyoxalate urethane has excellent durability (hydrolysis resistance), excellent biodegradability, and sufficient mechanical and thermal properties to be used as a general thermoplastic polyurethane. 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.

[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 a transesterification reaction. As the oxalate source, oxalic acid diester is preferable. For example, dialkyl oxalate such as dimethyl oxalate, diethyl oxalate, dipropyl oxalate and dibutyl oxalate, and diaryl oxalate such as diphenyl oxalate can be used alone or in combination. . Of these, dimethyl oxalate is most preferred.

Moreover, as a polyol, aliphatic polyols, such as aliphatic diol, an aliphatic triol, an aliphatic tetraol, are mentioned preferably. Among these, an aliphatic diol represented by the formula (5) is more preferable. In the formula (5), R ¹ is a divalent aliphatic hydrocarbon group having 3 to 12 carbon atoms, Not only the structure but also a branched structure or an alicyclic structure may be included. Moreover, you may have a substituent which does not participate in the said polycondensation reaction or the below-mentioned polyurethane-ized reaction.

  Examples of the aliphatic diol include 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, and 1,8-octanediol. , 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, and the like, neopentyl glycol, 2,4-diethyl-1,5- Pentanediol, 3-methyl-1,5-pentanediol, 2-ethyl-2-butyl-1,3-propanediol, 2,2,4-trimethyl-1,3-propanediol, 2,2-diethyl- Those containing a branched structure such as 1,3-propanediol and 2-ethyl-1,3-hexanediol, trans-1,4-cyclohexanedimethano Le, such as those containing an alicyclic structure such as cis-1,4-cyclohexanedimethanol.

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

The polycondensation reaction can be carried out by a known method with an excess of polyol so 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 is obtained, but the reaction temperature is 120 ° C. or higher and 350 ° C. or lower, and the reaction pressure is 1 mmHg (133 Pa) or higher and 760 mmHg (1.01 × 10 ^5). Pa) or less is preferable. In order to accelerate the reaction, it is preferable to extract the alcohol produced by the reaction out of the reaction system. For this purpose, it is preferable to provide a distillation column in the reactor, and further under the flow of an inert gas (nitrogen, helium, argon, etc.). The reaction may be carried out, the temperature or pressure may be varied, and a known catalyst may be added. As the catalyst, a transesterification catalyst is preferable, and examples thereof include compounds of metals such as titanium, zinc, germanium, iron, tin, etc. Among them, tetraalkoxy titanium (tetra-n-butoxy titanium, etc.) is preferable. The addition amount and addition timing of the catalyst are not particularly limited as long as the conditions can promote the reaction.

Among the polyoxalate polyols of component A, the polyoxalate diol represented by the above formula (1) is preferable. In the formula (1), n represents the polymerization degree of the polyoxalate diol (repeating structural unit “—R ¹ ”). Represents the number of repetitions of “OCOCOO-” and is related to the number average molecular weight. R ¹ may be ^one kind or two or more kinds. The number average molecular weight of the polyoxalate polyol is preferably in the range of 500 to 5000, particularly 1000 to 3000.

[B component]
B component consists of at least one of polyester polyol, polyalkylene ether polyol, and polyhydroxycarboxylic acid polyol.

Among these, a polyester polyol is a compound having a structure obtained by subjecting a dicarboxylic acid source and a polyol to a polycondensation reaction. The dicarboxylic acid source is preferably an aliphatic dicarboxylic acid represented by the formula (6). In the formula (6), R ³ has 2 to 12 carbon atoms which may contain a branched structure or an alicyclic structure. And may have a substituent that 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, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid and the like.

Moreover, as a polyol, aliphatic polyols, such as aliphatic diol, an aliphatic triol, an aliphatic tetraol, are mentioned preferably. Among these, aliphatic diols are more preferably represented by the formula (7), in equation (7), R ² is a branched structure or a cycloaliphatic divalent 2-12 carbon atoms which may structurally comprise And may have a substituent that does not participate in the polycondensation reaction or the later-described polyurethane-forming reaction. As this aliphatic diol, the same thing as the aliphatic diol represented by Formula (5) other than ethylene glycol is mentioned.

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

  The polycondensation reaction can be performed by a known method with an excess of polyol so that the terminal is a hydroxyl group. For example, two or more of the aliphatic dicarboxylic acid and the aliphatic diol are used as necessary. The dehydration polycondensation reaction may be performed at a charged molar ratio of 1.01 mol or more, further 1.05 mol or more and 2 mol or less, and further 1.2 mol or less with respect to 1 mol of the former. 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.

Among the polyester polyols of component B, the polyester diol represented by the formula (2) is preferable. In the formula (2), m is the degree of polymerization of the polyester diol (repeating the structural unit “—R ² OCOR ³ COO—” Number) and is related to the number average molecular weight. R ² and R ³ may be one kind or two or more kinds. The number average molecular weight of the polyester polyol is preferably in the range of 500 to 5,000, particularly 1,000 to 3,000.

Among the B components, the polyalkylene ether polyol is a compound having a structure obtained by subjecting an ether source and a polyol to a polymerization reaction. As the ether source, an alkylene oxide represented by the formula (8) is preferable, and in the formula (8), R ⁴ is a divalent aliphatic hydrocarbon having 2 to 6 carbon atoms that may contain a branched structure. And may have a substituent that does not participate in the polymerization reaction or the polyurethane-forming reaction described below. 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.

Moreover, as a polyol, aliphatic polyols, such as aliphatic diol, an aliphatic triol, an aliphatic tetraol, are mentioned preferably. Among these, an aliphatic diol represented by the formula (9) is more preferable, and in the formula (9), R ⁵ is a divalent aliphatic hydrocarbon having 2 to 6 carbon atoms which may contain a branched structure. 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 ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,3-butylene glycol, Neopentyl glycol, 3-methyl-1,5-pentanediol and the like can be mentioned.

  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. May be used.

  The polymerization reaction can be performed by a known method. For example, the alkylene oxide and the aliphatic diol may be 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.).

Among the polyalkylene ether polyol of the B component, a polyalkylene ether diol is preferably represented by the formula (3), wherein (3), k is poly polymerization degree of the alkylene ether diol (structural unit "-R ⁴ O -"Repeat number") and is related to the number average molecular weight. R ⁴ and R ⁵ may be one kind or two or more kinds. The number average molecular weight of the polyalkylene ether polyol is preferably in the range of 500 to 5000, particularly 1000 to 3000.

Among the B components, the polyhydroxycarboxylic acid polyol is a compound having a structure obtained by subjecting a hydroxycarboxylic acid source and a polyol to a polymerization reaction. As the hydroxycarboxylic acid source, an aliphatic cyclic ester represented by the formula (10) is preferable. In the formula (10), R ⁶ is a divalent divalent having 2 to 6 carbon atoms which may contain a branched structure. It is an 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-propiolactone, γ-butyrolactone, δ-valerolactone, ε-caprolactone, and the like.

Moreover, as a polyol, aliphatic polyols, such as aliphatic diol, an aliphatic triol, an aliphatic tetraol, are mentioned preferably. Among these, an aliphatic diol represented by the formula (11) is more preferable, and in the formula (11), R ⁷ is a divalent aliphatic hydrocarbon having 2 to 6 carbon atoms which may contain a branched structure. And may have a substituent that does not participate in the polymerization reaction or the polyurethane-forming reaction described below. As this aliphatic diol, the thing similar to the aliphatic diol represented by Formula (9) is mentioned.

  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. May be used.

  The polymerization reaction can be performed 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 ordinary conditions, and can be carried out at normal pressure or reduced pressure in the presence of a catalyst such as a metal compound such as antimony, titanium, zinc, germanium, iron, tin or the like.

Among the polyhydroxycarboxylic acid polyols of component B, the polyhydroxycarboxylic acid diol represented by the above formula (4) is preferable. In the formula (4), j represents the degree of polymerization of the polyhydroxycarboxylic acid diol (the structural unit “−” 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. In addition, it is preferable that the number average molecular weights of polyhydroxycarboxylic acid polyol are the range of 500-5000, especially 1000-3000.

[C component]
Examples of the component C chain extender include low molecular weight compounds having at least two hydrogen atoms that react with isocyanate groups. Such compounds include polyols and polyamines. Examples of polyols include ethylene glycol, 1,2-propylene glycol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, , 6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-dodecanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 3 , 3-Dimethylolheptane, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 1,4-dihydroxyethylcyclohexane and the like, which may contain a branched structure or alicyclic structure such as C2-C12 Aliphatic diols are preferred.

  The polyamine may contain a branched structure or alicyclic structure such as ethylenediamine, 1,2-propylenediamine, 1,6-hexamethylenediamine, isophoronediamine, bis (4-aminocyclohexyl) methane, and piperazine. Preferred examples include aliphatic diamines having 2 to 12 carbon atoms, and aromatic diamines having 6 to 18 carbon atoms such as m- (or p-) xylylenediamine and 4,4′-methylenebis (o-chloroaniline). .

  Furthermore, aliphatic aminoalcohol (2-ethanolamine, N-methyldiethanolamine, etc.), aromatic aminoalcohol (N-phenyldipropanolamine, etc.), hydroxyalkylsulfamide (hydroxyethylsulfamide, hydroxyethylaminoethylsulfate) Famide, etc.), urea, water and the like can also be mentioned as chain extenders. These chain extenders can be used alone or in combination.

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

  Examples of the aliphatic diisocyanate include 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-biuret, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, isophorone diisocyanate, 1,4-cyclohexane diisocyanate, 4, 4'-dicyclohexylmethane diisocyanate, hydrogenated xylylene diisocyanate, 2,2'-diethyl ether diisocyanate, etc.

  Examples of the aromatic diisocyanate include p-phenylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate, 4,4′-diphenyl diisocyanate, 1,5-naphthalene diisocyanate, 4,4′-diphenylmethane diisocyanate (MDI), 3,3. '-Methylene ditolylene-4,4'-diisocyanate, tolylene diisocyanate trimethylolpropane adduct, triphenylmethane triisocyanate, 4,4'-diphenyl ether diisocyanate, tetrachlorophenylene diisocyanate, 3,3'-dichloro-4, Examples thereof include 4′-diphenylmethane diisocyanate and triisocyanate phenylthiophosphate.

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

[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), and It is obtained by reacting a polyisocyanate compound (component D) (polyurethane reaction), and its number average molecular weight is preferably in the range of 10,000 to 200,000.

  Here, the ratio “(A + B): C: D” of the sum of the A and B components and the C and D components is in the range of 1: 0.5: 1.5 to 1: 6: 7 on a molar basis. It is preferable. However, the total amount of active hydrogen contained in the mixture of component A and component B and component C: isocyanate group is 1: 0.8 to 1: 1.2, more preferably 1: 0.95 to 1: It is preferable to use D component so that it may become 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. preferable. In addition, the A component and the B component may have different aliphatic hydrocarbon groups and may have different number average molecular weights.

  The polyurethane-forming 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 isocyanate groups. In the case of a reaction in the absence of a solvent, the mixture of component A and component B and component C are mixed, and component D is mixed with this to react all at once, or the mixture of component A and component B and component D Is reacted to obtain a prepolymer having an isocyanate group, and then mixed and reacted with the C component, or a mixture of the A and B components and the C component are mixed, and a part of the D component is mixed therewith. 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.

  In the case of the reaction in the presence of a solvent, the mixture of the A component and the B component is dissolved in the solvent and the C component is further mixed, and then the D component is mixed with this to react the whole amount at once. The mixture of B component is dissolved in a solvent, and D component is mixed and reacted therewith to obtain a prepolymer having an isocyanate group, and then mixed and reacted with C component, or the components A and B are mixed. After dissolving the mixture in a solvent and mixing and reacting a part of the C component and the D component to obtain a prepolymer having a hydroxyl group, the remaining D component is further mixed and reacted to perform the polyurethane reaction. Can be done. 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, chloroform and the like. In the polyurethane reaction, a known amine-based or tin-based catalyst may be used for promoting the reaction.

  The polyoxalate urethane of the present invention can be made high molecular weight or reticulated 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. Moreover, a crosslinked structure can also be introduce | transduced by making it react with the compound which has at least 3 hydrogen atom which reacts with the compound or isocyanate group which has a urethane bond and / or a urea bond.

  Moreover, the polyoxalate urethane of this invention can also be made into a polyoxalate urethane composition by blending with another polyurethane. Other polyurethanes may be known thermoplastic polyurethanes, and for example, adipate-based, lactone-based and ether-based thermoplastic polyurethanes 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 to 95: 5, further 10:90 to 90:10, particularly 20:80. It is preferable to be in the range of ˜80: 20. The polyoxalate urethane and other polyurethanes of the present invention can be used alone or in combination. In addition, the polyoxalate urethane obtained from A component, C component, and D component can also be made into the same composition by blending with another polyurethane.

  The most common method of blending is to use a known continuous kneader (single screw extruder, twin screw extruder, twin screw rotor kneader, etc.) or batch kneader (open roll, kneader, Banbury mixer, etc.). There is no particular limitation on the kneading method and kneading conditions. A solution blending method using a solvent may also be used.

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

  Other blendable polymers may include natural or synthetic polymeric materials such as polycaprolactone, polylactic acid, polyglycolic acid, polysuccinic acid ester, poly (3-hydroxybutanoic acid), (3 -Hydroxybutanoic acid / 4-hydroxybutanoic acid) copolymer, polyvinyl alcohol, polyethylene, polyvinyl acetate, polyvinyl chloride, polystyrene, polyglutamic acid ester, cellulose acetate, alginic acid, chitosan, starch and other plastic materials, natural rubber, polyester Examples thereof include rubbers, polyamide rubbers, styrene-butadiene-styrene block copolymers (SBS), rubbers such as hydrogenated SBS, and elastomers.

  In addition, the polyoxalate urethane and the composition thereof according to the present invention may be applied to a known melt processing method (injection molding, extrusion molding, press molding, hollow molding, thermoforming, etc.) to form a film, sheet, fiber, nonwoven fabric, It can be formed into a molded product such as a container, various agricultural / industrial materials or members. Among these, injection molding products include 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. It is done. 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 coverings, various ropes, etc. It is done.

  Next, the present invention will be specifically described with reference to examples and comparative examples. In addition, the physical property of the polyoxalate diol was measured by the method of the following 1-2, and the physical property of the polyoxalate urethane and the polyoxalate urethane composition was measured by the method of the following 3-7, respectively.

1. Number average molecular weight (M _n ): ¹ H-NMR measurement was performed under the following conditions, and the following calculation formula was used. _Where S _OCOCOO is the integral value of the methylene proton adjacent to the oxalate bond, S _OH is the integral value of the methylene proton adjacent to the terminal hydroxyl group, M _unit is the molecular weight of the repeating structural unit in the _{polyoxalate diol} , M _diol Represents the molecular weight of the aliphatic diol of the polyoxalate diol raw material.

・ Model used: JEOL JNM-EX400WB
Solvent: CDCl ₃
・ Number of integration: 32 times ・ Sample concentration: 5% by weight
Calculation formula: M _n = S _OCOCOO / S _OH × M _unit + M _diol

2. Melting point (T _m ): Measured using a differential scanning calorimeter (DSC-50; manufactured by Shimadzu Corporation) in a nitrogen gas atmosphere at a temperature rising rate of 10 ° C./min.

3. Glass transition temperature (T _g ): measured in the same manner as the melting point.

  4). Viscosity (Pa · sec): Measured using an E-type viscometer (manufactured by Tokyo Keiki).

  5. Tensile properties: measured in accordance with JIS-K7311 using a tensile tester (Tensilon UCT-5T; manufactured by Orientec) under conditions of 23 ° C. and 50% RH to determine tensile modulus, tensile strength, and elongation at break. .

  6). Hydrolysis resistance: After JIS No. 2 tensile test pieces were immersed in pure water at 23 ° C., the tensile properties were measured as described above and evaluated from the retention of elongation at break.

  7). Biodegradation characteristics: A test piece (1 cm × 1 cm) was embedded in compost (Hochikon (manufactured by JA) pulverized to 5 mesh or less; 30 ° C.), taken out every week, and its weight residual ratio was measured.

[Reference Example 1] <Production of polyoxalate diol>
A glass reactor having an internal volume of 1 L (liter) equipped with a stirrer, a thermometer, and a distillation column (equipped with a fractionation tube, a reflux head, and a condenser at the top of the column) was charged with 372.0 g of dimethyl oxalate (DMO) (3. 15 mol), 1,6-hexanediol (HDL) 531.8 g (4.508 mol), and tetra-n-butoxytitanium (TBT) 0.027 g (30 ppm by weight based on the total amount of DMO and HDL) ) And distilled for 3 hours at 160 ° C. under atmospheric pressure, and further at 170 ° C. for 1 hour under 300 mmHg (4 × 10 ⁴ Pa). Next, the temperature was raised to 180 ° C. and the pressure was reduced to 100 mmHg (1.33 × 10 ⁴ Pa) for 5 hours, and the reaction was further carried out at 5 mmHg (666 Pa) for 2 hours. Finally, TBT and an equimolar amount of dibutyl phosphate were added to the reaction product, and the mixture was stirred at 95 ° C. under normal pressure for 3 hours to deactivate the catalyst. The obtained polyoxalate diol (PHMOD-1; polyhexamethylene oxalate diol) had an _Mn of 2089 and a _Tm of 72 ° C.

[Reference Example 2] <Production of polyoxalate diol>
A 3 L glass reactor equipped with a stirrer, a thermometer and a distillation column (equipped with a fractionation tube, a reflux head, and a condenser at the top of the column) was charged with DMO 1116 g (9.45 mol) and HDL 1595 g (13.50 mol). And 0.081 g of TBT (30 ppm by weight based on the total amount of DMO and HDL) were charged, and the reaction was carried out at 170 ° C. for 3 hours at 170 ° C. under atmospheric pressure and further for 1 hour at 170 ° C. under 300 mmHg. Next, the temperature was raised to 180 ° C. and the pressure was reduced to 100 mmHg for 4 hours. The temperature was raised to 200 ° C. and the pressure was reduced to 1 mmHg (133 Pa) for 2.5 hours. Finally, TBT and an equimolar amount of dibutyl phosphate were added to the reaction product, and the mixture was stirred at 120 ° C. under normal pressure for 2 hours to deactivate the catalyst. The obtained polyoxalate diol (PHMOD-2; polyhexamethylene oxalate diol) had M _n of 1963 and T _m of 72 ° C.

[Example 1]
In a glass reactor having an internal volume of 1 L equipped with a stirrer, a thermometer and a cooling tube, 25 g (0.0120 mol) of polyoxalate diol (PHMOD-1) obtained in Reference Example 1 and polyethylene adipate diol (PEAD; Nippon Polyurethane Nipponporan 4040; M _n = 2047, T _m = 46 ° C.) 25 g (0.0122 mol) was charged and stirred and mixed at 100 ° C. for 1 hour in a nitrogen atmosphere, and then 4,4-diphenylmethane diisocyanate (MDI; Japan) (Made of polyurethane) 12.1 g (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., 1.79 g (0.0241 mol) of 1,2-propylenediamine (PDA; dissolved in 10 g of DMF) was added and reacted for 5 minutes with vigorous stirring, followed by The temperature was raised to 50 ° C. and the reaction was carried out while adding MDI little by little, and the reaction was terminated when the viscosity (50 ° C.) reached 11.6 Pa · sec.

  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, then at 70 ° C. for 1 hour, then at 120 ° C. And dried for 2 hours to obtain a film of about 200 μm. The results of evaluating the physical properties of polyoxalate urethane using this film are shown in Tables 1 and 2.

[Example 2]
The PHMOD-1 charge was changed to 15 g (0.0072 mol), the PEAD charge was changed to 35 g (0.0171 mol), the MDI usage was changed to 12.2 g (0.0486 mol), and the PDA usage was 1.80 g ( 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 completion of the reaction, a film 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 3
The PHMOD-1 charge was changed to 5 g (0.0024 mol), the PEAD charge was changed to 45 g (0.220 mol), the MDI usage was changed to 12.2 g (0.0486 mol), and the PDA usage was 1.81 g ( The reaction was performed in the same manner as in Example 1 except that the reaction was terminated when the viscosity (50 ° C.) reached 12.4 Pa · sec. After completion of the reaction, a film 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 4
PHMOD-1 charge was changed to 25 g (0.0120 mol), and PEAD was polyhexamethylene sebacate diol (PHSD; Ube Industries Etanacol 3020; M _n = 3643, T _m = 65 ° C.) 44 g (0.0121 mol) The reaction was carried out in the same manner as in Example 1 except that the above was changed. After completion of the reaction, a film 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 charge was changed to 5 g (0.0024 mol), and PEAD was polytetramethylene ether glycol (PTMG; PTG2000SN manufactured by Hodogaya Chemical; M _n = 1993, T _m = 34 ° C.) 45 g (0.0226 mol) The reaction solution was completely dissolved in 140 g of DMF in the same manner as in Example 1 except that the amount of MDI used was changed to 12.5 g (0.050 mol). Next, the reaction was performed in the same manner as in Example 1 except that the amount of PDA used was changed to 1.85 g (0.0250 mol) and the reaction was terminated when the viscosity (50 ° C.) reached 26.8 Pa · sec. I did it. After 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. The results are shown in Tables 1 and 2.

Example 6
In the same reactor as in Example 1, 6 g (0.0029 mol) of polyoxalate diol (PHMOD-1), polycaprolactone diol (PCLD; Plaxel-220 manufactured by Toa Gosei); M _n = 1986, T _m = 54 ° C. ) 54 g (0.0272 mol), 2.73 g (0.030 mol) 1,4-butanediol (BDL) and 170 g DMF were stirred and mixed at 100 ° C. for 1 hour in a nitrogen atmosphere, and then hexamethylene diisocyanate (HDI). Manufactured by Nippon Polyurethane) and 0.025 g of dibutyltin dilaurate were added and reacted with vigorous stirring. Further, the reaction was carried out while adding HDI little by little, and the reaction was terminated when the viscosity (50 ° C.) reached 47.2 Pa · sec. After the reaction was completed, except that the polyoxalate urethane concentration was adjusted to 25% 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. The results are shown in Tables 1 and 2.

[Comparative Example 1]
A reactor similar to Example 1 was charged with 40 g (0.0191 mol) of polyoxalate diol (PHMOD-1), stirred and mixed at 100 ° C. for 1 hour in a nitrogen atmosphere, and then 9.58 g of MDI (manufactured by Nippon Polyurethane). (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., 1.42 g (0.0191 mol) of PDA (dissolved in 10 g of DMF) was added and reacted for 5 minutes with vigorous stirring, and then the temperature was raised to 60 ° C. 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 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 30.3% by weight, and the physical properties of polyoxalate urethane were evaluated. The results are shown in Tables 1 and 2.

[Reference Example 3]
500 g (0.255 mol) of the polyoxalate diol (PHMOD-2) obtained in Reference Example 2 was charged into a 5 L glass reactor equipped with a stirrer, a thermometer, and a cooling tube, and the temperature was 90 ° C. under a nitrogen atmosphere. Then, 359.3 g (1.436 mol) of MDI (Nippon Polyurethane) was added and reacted at the same temperature for 3 hours. Next, 107.5 g (1.193 mol) of BDL was added and reacted for 1 minute with vigorous stirring. The reaction solution was immediately poured into a stainless steel vat (with a release film made of Teflon (registered trademark)) and vacuumed as it was. It was cured at 90 ° C. for 2 hours.

  The resulting polyoxalate urethane lump was crushed and dry blended with 12.5 g of the crushed material and 37.5 g of adipate-based thermoplastic polyurethane (Pandex T-1195; manufactured by Dainippon Ink & Chemicals, Inc.) The mixture was melt-kneaded at 210 ° C. for 5 minutes with a Brabender type twin-screw kneader (rotation speed: 60 revolutions / minute). The obtained polyoxalate urethane composition was melt-molded by a compression molding machine manufactured by Shinto Metal Industry, and a film of about 100 μm was obtained at 210 ° C. under 4.9 MPa to evaluate the physical properties of the polyoxalate urethane composition.

As a result, _{T g} is -33 ° C., a tensile modulus of 55.2MPa, tensile strength 31.9MPa, elongation at break was 300%. Further, the hydrolysis resistance (breaking elongation retention) is 101% (1 week), 105% (2 weeks), 40% (3 weeks), and the biodegradation characteristics (weight residual ratio) are 99.0. % (1 week), 97.3% (2 weeks), 92.8% (3 weeks), and 93.5% (4 weeks).

[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.), and the physical properties of the polyoxalate urethane composition were obtained. evaluated. As a result, _{T g} is -48 ° C., a tensile modulus of 40.0MPa, tensile strength 21.0MPa, 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 (weight residual ratio) are 98.9. % (1 week), 97.1% (2 weeks), 92.6% (3 weeks), and 93.3% (4 weeks).

  According to the present invention, the polyoxalate urethane has excellent durability (hydrolysis resistance), excellent biodegradability, and sufficient mechanical and thermal properties to be used as a general thermoplastic polyurethane. Can be provided. For this reason, the polyoxalate urethane and 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 (4)

A component: a polyoxalate polyol component containing a polyoxalate diol represented by the formula (1) ,
Component B: a component comprising at least one selected from polyester polyols, polyalkylene ether polyols and polyhydroxycarboxylic acid polyols , polyester diol represented by formula (2), polyalkylene represented by formula (3) A component containing at least one of an ether diol and a polyhydroxycarboxylic acid diol represented by the formula (4) :
Component C: chain extender , and
D component: Polyoxalate urethane obtained by reacting a polyisocyanate compound component containing a diisocyanate compound .

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

(Wherein R ² and R ³ represent a divalent aliphatic hydrocarbon group having 2 to 12 carbon atoms which may contain a branched structure or an alicyclic structure, and m is a positive integer representing the degree of polymerization. is there.)

(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.)

(In the formula, 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.) The ratio “(A + B): C: D” of the sum of the A component and the B component and the C component and the D component is 1: 0.5: 1.5 to 1: 6: 7 on a molar basis. the total amount of active hydrogen contained in the mixture and component C component: isocyanate groups, 1 equivalent ratio: 0.8 to 1: 1.2, polyoxalate urethane of claim 1 wherein. The polyoxalate urethane according to claim 2 , wherein the ratio "A: B" of the A component and the B component is 5:95 to 95: 5 on a weight basis. The polyoxalate urethane according to any one of claims 1 to 3 , wherein the number average molecular weights of the A component and the B component are in the range of 500 to 5,000, respectively.