JP4962085B2 - Polyoxalate polyol and polyoxalate urethane derived therefrom - Google Patents

Description

The present invention relates to a polyoxalate urethane having good tension and a polyoxalate polyol which is a raw material for obtaining a polyoxalate urethane.

Polyoxalate urethanes obtained from polyoxalate diols are attracting attention as having hydrolyzability and biodegradability. For example, Patent Document 1 discloses that a polyurethane produced from a polyoxalate diol, a chain extender, and a diisocyanate has hydrolyzability and biodegradability.

However, the above polyoxalate urethane has a problem that it does not have good tension based on the rubber elasticity characteristic of polyurethane. Here, the term “tension” refers to the degree of return from the bent state to the original state by bending the polyoxalate urethane by hand. Good tension means that the bent state quickly returns to the original state.
JP 2003-335837 A

An object of the present invention is to provide a polyoxalate urethane having a good tension by solving the above-described problems and a polyoxalate polyol which is a raw material for obtaining the polyoxalate urethane.

  The present invention is a polyoxalate polyol having an ether bond represented by the general formula (1).

（式中、Rは炭素数2〜12のアルキレン基を表し、分岐構造又は脂環式構造を含んでいても良く、nはポリオキサレートの重合度を表し1から32であり、mはポリエーテルの重合度を表し2から60である。）
また、別の発明としては、一般式(1)で表されるポリオキサレートポリオールとジイソシアネートから反応させて得られるエーテル結合を有するポリオキサレートウレタンである。鎖延長剤又は熱硬化剤さらに加えて反応させることが好ましい。また、エーテル結合を有するポリオキサレートポリオール：鎖延長剤又は熱硬化剤：ジイソシアネート（モル比）が1:0.5:1.5〜1：6：7の範囲であることが好ましい。さらに、エーテル結合を有するポリオキサレートポリオールの数平均分子量が500〜5000であることが好ましい。

(In the formula, R represents an alkylene group having 2 to 12 carbon atoms and may contain a branched structure or an alicyclic structure, n represents the degree of polymerization of polyoxalate and is 1 to 32, and m represents poly Represents the degree of polymerization of ether and is 2 to 60.)
Another invention is a polyoxalate urethane having an ether bond obtained by reacting a polyoxalate polyol represented by the general formula (1) with a diisocyanate. It is preferable to add a chain extender or a thermosetting agent and react. The polyoxalate polyol having an ether bond: the chain extender or the thermosetting agent: the diisocyanate (molar ratio) is preferably in the range of 1: 0.5: 1.5 to 1: 6: 7. Furthermore, the number average molecular weight of the polyoxalate polyol having an ether bond is preferably 500 to 5,000.

  According to the present invention, the polyoxalate urethane having an ether bond has an effect of having good tension. The polyoxalate urethane having an ether bond of the present invention is composed of a polyoxalate polyol having both an oxalate bond and an ether bond in one molecular chain, and has good compatibility. Therefore, the polyoxalate urethane having an ether bond of the present invention is very useful as a raw material for molded articles, biodegradable materials such as films, sheets and fibers, and precision polishing pads.

The diol compound having an ether bond used as a raw material for the polyoxalate polyol having an ether bond of the present invention is a compound in which both terminal groups represented by the following general formula (2) are hydroxyl groups. The alkylene group R has 2 to 12 carbon atoms (even or odd) and is not limited to a linear structure but may include a branched structure or an alicyclic structure. Further, the alkylene group R may be of one type or two or more types. m represents the degree of polymerization of the polyether, and is preferably 2 or more and 60 or less. The number average molecular weight of the diol compound is preferably 100 to 3000, particularly preferably 100 to 1000.

Examples of the diol compound having an ether bond include diethylene glycol, triethylene glycol (TEG), poly (oxyethylene) glycol (PEG), poly (oxypropylene) glycol (PPG), polytetramethylene ether glycol (PTMEG), poly (Oxyhexamethylene) glycol (PHMG), linear structure such as ethylene oxide / propylene oxide (EO / PO) copolymer, tetrahydrofuran (THF) / 3-methyl-THF random copolymer (PTG-L), THF Examples thereof include those having a branched structure such as PTMG (PTG-X) to which neopentyl glycol is added following the polymerization of.

The polyoxalate polyol having an ether bond of the present invention is a polyoxalate diol having hydroxyl groups at both ends represented by the formula (1). The alkylene group R has 2 to 12 carbon atoms (even or odd) and is not limited to a linear structure but may include a branched structure or an alicyclic structure. Further, the alkylene group R may be of one type or two or more types. n represents the degree of polymerization of the polyoxalate (the number of repeating alkylene oxalate units) and corresponds to the number average molecular weight. n is 1 to 32. M represents the degree of polymerization of the polyether. m is 2 to 60. The number average molecular weight of the polyoxalate polyol is preferably 500 to 5000, particularly 500 to 1500.

The polyoxalate polyol having an ether bond is preferably obtained by melt polymerization involving a transesterification reaction between an oxalic acid diester and a diol compound having an ether bond. As the diol compound, one represented by the formula (2) is used singly or in plural, and among them, the TEG and PTMEG are preferable. As the oxalic acid diester, dimethyl oxalate, diethyl oxalate, dipropyl oxalate, dialkyl oxalate such as dibutyl oxalate, and diaryl oxalate such as diphenyl oxalate are used singly or in plural, and dimethyl oxalate is particularly preferable. The diol compound is preferably used in an amount of 1.07 to 2.36 times mol, particularly 1.41 to 2.36 times mol, relative to dimethyl oxalate.

In the melt polymerization, the reaction temperature and reaction pressure are not particularly limited as long as the desired product can be obtained, but preferably the reaction temperature is 130 to 200 ° C. and the reaction pressure is 1 to 760 torr. Moreover, it is preferable to extract the alcohol produced | generated by transesterification out of the system, in order to accelerate reaction. For this purpose, it is preferable to provide a distillation column in the reactor, and further the reaction may be carried out under the flow of an inert gas (nitrogen, helium, argon, etc.). Further, the temperature and pressure may be varied, and a known transesterification catalyst may be added. Examples of the catalyst include acidic catalysts such as p-toluenesulfonic acid, basic catalysts such as 1,8-diazabicyclo [5.4.0] undec-7-ene, and metal catalysts such as titanium, zinc, germanium, iron and tin. Can be mentioned. Among these, titanium tetraalkoxide (particularly titanium tetrabutoxide) is preferable. The addition amount and addition timing of the catalyst are not particularly limited as long as the conditions can promote the reaction.

The polyoxalate urethane of the present invention is obtained by reacting the polyoxalate polyol and diisocyanate (by polyurethane reaction). Examples of the diisocyanate used in the present invention include various aliphatic or aromatic diisocyanates. The aliphatic diisocyanate 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 diisocyanate is not particularly limited as long as it contains a divalent aromatic hydrocarbon group in the molecule.

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, hexamethylene diisocyanate-biuret, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, isophorone diisocyanate, 1,4-cyclohexane diisocyanate, 4,4 Examples include '-dicyclohexylmethane diisocyanate, hydrogenated xylylene diisocyanate, and 2,2'-diethyl ether diisocyanate.

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 the diisocyanates, tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 1,6-hexamethylene diisocyanate, and isophorone diisocyanate are preferable, and among them, tolylene diisocyanate and 4,4'-diphenylmethane diisocyanate are particularly preferable. The diisosocyanate is used alone or in combination.

When the polyoxalate polyol and the diisocyanate are reacted, it is preferable that a chain extender or a thermosetting agent is further added and reacted.
Examples of the chain extender used in the present invention include low molecular compounds having at least two hydrogen atoms that react with an isocyanate group. Such compounds include polyols, polyamines, etc., specifically, ethylene glycol, 1,2-propylene glycol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, Linear structure such as 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, neo Pentyl glycol, 2,4-diethyl-1,5-pentanediol, 3-methyl-1,5-pentanediol, 2-ethyl-2-butyl-1,3-propanediol, 2,2,4-trimethyl- Contains a branched structure such as 1,3-propanediol, 2,2-diethyl-1,3-propanediol, 2-ethyl-1,3-hexanediol, 1,4-cyclohexanediol, trans-1,4 -Containing alicyclic structures such as cyclohexanedimethanol and cis-1,4-cyclohexanedimethanol Etc., and the like.

Aliphatic or aromatic diamines such as ethylenediamine, 1,2-propylenediamine, 1,6-hexamethylenediamine, isophoronediamine, bis (4-aminocyclohexyl) methane, piperazine, meta (or para) xylenediamine and the like can be mentioned. Furthermore, aliphatic or aromatic amino alcohols such as 2-ethanolamine, N-methyldiethanolamine, N-phenyldipropanolamine, hydroxyalkylsulfamides such as hydroxyethylsulfamide, hydroxyethylaminoethylsulfamide, and Urea, water, etc. are also examples of chain extenders. Of these chain extenders, 1,4-butanediol is particularly preferred. One or more chain extenders can be used.

Examples of the thermosetting agent used in the present invention include linear aliphatic compounds such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine, and diethylaminopropylamine, mensendiamine, isophoronediamine, N-aminoethylpiperazine, 3, 9-bis (3-aminopropyl) -2,4,8,10-tetraoxyspiro (5,5) -undecane adduct, bis (4-amino-3-methylcyclohexyl) methane, bis (4-aminocyclohexyl) Examples include alicyclic groups such as methane, and aromatic groups such as m-xylenediamine, diaminodiphenylmethane, 3,3′-dichloro-4,4′-diaminodiphenylmethane, m-phenylenediamine, and diaminodiphenylsulfone. Among these thermosetting agents, 3,3′-dichloro-4,4′-diaminodiphenylmethane is particularly preferable. One or more thermosetting agents can be used.

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, a polyoxalate polyol and a chain extender or a thermosetting agent are mixed, and this is mixed with a diisocyanate to react all at once, or a polyoxalate polyol and a diisocyanate are reacted. After obtaining a prepolymer having an isocyanate group, a chain extender or a thermosetting agent is mixed and reacted with the prepolymer, or a polyoxalate polyol and a chain extender or a thermosetting agent are mixed, and this is mixed with a diisocyanate. After a part is mixed and reacted to obtain a prepolymer having a hydroxyl group, the remaining diisocyanate is further mixed and reacted to carry out the polyurethane reaction. A preferable reaction temperature in the absence of a solvent is 90 to 60 ° C.

In the case of a reaction in the presence of a solvent, the polyoxalate polyol is dissolved in a solvent and a chain extender is further mixed, and then diisocyanate is mixed to react all at once, or the polyoxalate polyol is After dissolving in a solvent and mixing and reacting with diisocyanate to obtain a prepolymer having an isocyanate group, this is mixed with a chain extender and reacted, or a polyoxalate polyol and a chain extender are used as a solvent. After mixing, a part of diisocyanate is mixed and reacted to obtain a prepolymer having a hydroxyl group, and then the remaining diisocyanate is further mixed and reacted to carry out the polyurethane reaction. A preferred reaction temperature in the case of a solvent is 100 to 20 ° C. Typical examples of the solvent include methyl ethyl ketone, ethyl acetate, toluene, dioxane, dimethylformamide, dimethyl sulfoxide and the like.

In the polyurethane-forming reaction, the ratio of the polyoxalate polyol and the chain extender or thermosetting agent used is generally preferably in the range of 6 to 0.5 mol of the latter with respect to 1 mol of the former. These amounts used are appropriately determined depending on the physical properties of the target polyester urethane. The amount of diisocyanate used is preferably approximately equimolar to the total amount of polyoxalate polyol and chain extender or thermosetting agent. Specifically, the total amount of active hydrogen contained in the polyoxalate polyol, the chain extender or the thermosetting agent: the isocyanate group has an equivalent ratio of 1: 0.8 to 1: 1.2, more preferably 1: 0.9 5 to 1: It is preferable to use diisocyanate so as to be 1.05. In the polyoxalate urethane of the present invention, polyoxalate polyol: chain extender or thermosetting agent: diisocyanate (molar ratio) is 1: 0.5: 1.5-1: 6: 7, preferably 1: 0.9: 2-1 : 3: 4). In the polyurethane reaction, a known amine-based or tin-based catalyst may be used to accelerate the reaction.

The polyoxalate urethane of the present invention obtained by using a chain extender preferably has a number average molecular weight of about 20000 to 10,000, and the molecular terminal is not particularly limited. Moreover, the polyoxalate urethane of the present invention obtained by using a thermosetting agent can also take a crosslinked structure.

Furthermore, the polyoxalate urethane of the present invention may be blended with various known additives and other polymers as long as the effects of the present invention are not impaired. Additives that can be blended include crystal nucleating agents, pigments, dyes, heat-resistant agents, anti-coloring agents, antioxidants, weathering agents, lubricants, antistatic agents, stabilizers, coupling agents, antibacterial and antifungal agents, foaming Agent, filler (talc, clay, zeolite, zonotlite, calcium carbonate, carbon black, silica powder, alumina powder, titanium oxide powder, etc.), reinforcing agent (glass fiber, carbon fiber, silica fiber, etc.), flame retardant, plasticizer , Mold release agents, waterproofing agents (wax, silicone oil, higher alcohol, lanolin, etc.), resin-type microballoons, inorganic-type microballoons, and the like.

Other polymers that can be blended may be natural or synthetic polymer materials such as polycaprolactone, polylactic acid, polyglycolic acid, polysuccinic acid ester, poly (3-hydroxybutanoic acid), (3-hydroxybutane). 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 rubber, polyamide rubber And rubber or elastomer such as styrene-butadiene-styrene block copolymer (SBS) and hydrogenated SBS. These can be blended alone or in combination.

  Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples. The physical properties of polyoxalate diol were measured by the following method 1, and the physical properties of polyoxalate urethane were measured by the following methods 2-7.

1. Average molecular weight (Mn)
¹ H-NMR measurement was performed under the following conditions and calculated according to the following formula. In the formula, 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, and M (unit) is the repeating structure in the polyoxalate polyol. The molecular weight of the unit, M (diol), represents the molecular weight of the diol compound having a polyether bond of the polyoxalate polyol raw material.
Model used: JEOL JNM-EX400WB, solvent: CDCl ₃ , integration count: 32 times, sample concentration: 5 wt%, calculation formula: Mn = (S (OCOCOO) / S (OH)) x M (unit) + M (diol)

2. Melt viscosity (Pa · sec)
Using an E-type viscometer (TV-20 viscometer manufactured by Toki Sangyo Co., Ltd.), the temperature was measured at 25 ° C.

3. Reduced viscosity (dL / g)
Using an Ubbelohde viscometer (water for 300 sec at 25 ° C.), the measurement was performed with a dimethyl sulfoxide solution at a temperature of 25 ° C.

4. Hot press molding Thermoplastic polyoxalate urethane sample is sandwiched between polytetrafluoroethylene (PTFE) cloth sheets, hot press machine (Shinfuji Metal Industry Co., Ltd., compression molding machine NF-37, cylinder diameter 150 mm Clamping was 37 tons). The sample was held at a temperature of 200 ° C. for 4 minutes with no pressure applied. Next, the sample was pressed for 2 minutes at a pressure of 50 kg / cm ² while keeping the temperature at 200 ° C., and hot-pressed. Finally, it was cooled by pressing for 2 minutes at a temperature of 30 ° C. and a pressure of 50 kg / cm ² to obtain a molded body of 50 mm length × 50 mm width × 2 mm thickness.

5. The Shore D hardness tester was measured at a temperature of 25 ° C. using a Shore D hardness tester (manufactured by Kobunshi Keiki Co., Ltd., Asker rubber hardness tester JISK7215 JISK6235).

6. Tension evaluation method for polyoxalate urethane (qualitative method)
Actually, the thermoplastic polyoxalate urethane sample and the thermosetting polyoxalate urethane sample were bent by hand, and the return from the bent state to the original state was observed. In addition, tension (good) means that the return from the bent state to the original state is quick, and conversely, poor tension (x) means that the bent state is restored to the original state. It was defined as a slow return.

7. Tension evaluation method for polyoxalate urethane (quantitative method)
One end of a thermoplastic polyoxalate urethane molded body (length 46 mm × width 46 mm × thickness 2 mm) was fixed at a width of 10 mm. Next, one end opposite to the fixed portion of the molded body was bent, and the lower surface of the molded body was placed so as to be 90 ° from the initially fixed angle. Finally, the time required for the lower surface of the molded body to return to 30 ° from the initially fixed angle was measured at a temperature of 25 ° C. This operation was performed 4 or 5 times, and the average value thereof was taken as the measured value. In this measurement, the smaller measured value was defined as a molded article with good tension.

[Example 1] (Thermoplastic polyoxalate urethane)
(Production of polyoxalate diol)
Into a glass reactor with an internal volume of 500 ml equipped with a stirrer, thermometer, and distillation column (with a fractionation tube, reflux head, and condenser at the top), dimethyl oxalate (DMO) (41.3 g; 0.350 mol), Triethylene glycol (TEG) represented by formula (3) (75.0 g; 0.499 mol) and tetra-n-butoxytitanium (TBT; 6 mg; 51.6 ppm by weight based on the total amount of DMO and TEG) are charged. It is. The mixture was reacted at 130 ° C. for 1 hour under normal pressure, then reacted at 160 ° C. for 1 hour under normal pressure, and further reacted at 180 ° C. for 1 hour under normal pressure to distill methanol. The reaction was further carried out at 300 torr and 180 ° C. for 1 hour, and then methanol was further distilled off under reduced pressure at 100 torr and 180 ° C. for 4 hours. Next, the temperature was raised to 200 ° C. and the pressure was reduced to 1 torr, and a polycondensation reaction was carried out for 2 hours to distill TEG. 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 number average molecular weight (Mn) of the obtained polyoxalate diol (TEG type POD) was 983.

(Manufacture of polyoxalate urethane)
Place the TEG-type POD (20 g; 0.020 mol) obtained above in a glass reactor equipped with a stirrer, thermometer, and cooling tube with an internal volume of 300 ml in a reaction vessel under a nitrogen atmosphere, and add 15 torr. And dehydrated under reduced pressure at 110 ° C. for 2 hours. Next, p-phenylene diisocyanate (MDI) (10.4 g; 0.042 mol) was added to the reaction vessel and reacted at normal pressure and 90 ° C. for 3 hours. Thereafter, 1,4-butanediol (1.83 g; 0.020 mol) was reacted in the reaction vessel at normal pressure and the same temperature for 5 minutes with vigorous stirring. The obtained polyoxalate urethane (TEG type POU) was taken out of the reactor and cured under vacuum at 100 ° C. for 24 hours. Table 1 shows the physical property values of TEG type POU.

[Example 2] (Thermoplastic polyoxalate urethane)
(Production of polyoxalate diol)
To a 500 ml 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) (41.3 g; 0.350 mol), Polytetramethylene ether glycol 250 (PTMEG250; molecular weight 250) (125 g; 0.5 mol) and tetra-n-butoxytitanium (TBT; 6 mg; 36.1 ppm by weight based on the total amount of DMO and PTMEG250) were charged . The mixture was reacted at 130 ° C. for 1 hour under normal pressure, then reacted at 160 ° C. for 1 hour under normal pressure, and further reacted at 180 ° C. for 1 hour under normal pressure to distill methanol. The reaction was further carried out at 300 torr and 180 ° C. for 1 hour, and then methanol was further distilled off under reduced pressure at 100 torr and 180 ° C. for 4 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 number average molecular weight (Mn) of the obtained polyoxalate diol (PTMEG250 type POD) was 1053.

(Manufacture of polyoxalate urethane)
PTMEG250-type POD (20 g; 0.019 mol) obtained above was placed in a glass reactor equipped with a stirrer, thermometer, and cooling tube with an internal volume of 300 ml. And dehydrated under reduced pressure at 110 ° C. for 2 hours. Next, MDI (9.73 g; 0.039 mol) was added to the reaction vessel, and reacted at normal pressure and 90 ° C. for 3 hours. Thereafter, 1,4-butanediol (1.71 g; 0.019 mol) was reacted in the reaction vessel at normal pressure and the same temperature for 5 minutes with vigorous stirring. The obtained polyoxalate urethane (PTMEG250 type POU) was taken out from the reaction vessel and cured under vacuum at 100 ° C. for 24 hours. Table 1 shows the physical properties of PTMEG250 POU.

[Comparative Example 1] (Thermoplastic polyoxalate urethane)
(Production of polyoxalate diol)
Into a 500 ml glass reactor equipped with a stirrer, thermometer, and distillation column (equipped with fractionation tube, reflux head, condenser at the top), dimethyl oxalate (DMO) (41.3 g; 0.350 mol), Propane-1,3-diol (19.0 g; 0.250 mol), 3-methylpentanediol (3MPD) (29.5 g; 0.250 mol), and tetra-n-butoxytitanium (TBT; 6 mg; DMO, and 3MPD) 66.8 ppm by weight based on the amount), reacted at 130 ° C under normal pressure for 1 hour, then reacted at normal pressure at 160 ° C for 1 hour, and further reacted at normal pressure at 180 ° C for 1 hour. Distilled. The reaction was further carried out at 300 torr and 180 ° C. for 1 hour, and then methanol was further distilled off under reduced pressure at 100 torr and 180 ° C. for 4 hours. Next, the temperature was raised to 200 ° C. and the pressure was reduced to 1 torr and a polycondensation reaction was performed for 2 hours to distill the diol. Finally, TBT and an equimolar amount of dibutyl phosphate were added to the reaction product, and stirred at 120 ° C. for 2 hours under normal pressure to deactivate the catalyst. The number average molecular weight (Mn) of the obtained polyoxalate diol (propane-1,3-diol-3MPD type POD) was 950.

(Manufacture of polyoxalate urethane)
Place a 1,3-PD-3MPD type POD (50 g; 0.053 mol) in a reaction vessel under a nitrogen atmosphere in a glass reactor with an internal volume of 300 ml equipped with a stirrer, thermometer, and condenser. It was dehydrated under reduced pressure at torr and 110 ° C. for 2 hours. Next, MDI (27 g; 0.108 mol) was added to the reaction vessel, and reacted at normal pressure and 90 ° C. for 3 hours. Thereafter, 1,4-butanediol (4.74 g; 0.0526 mol) was reacted in the reaction vessel at normal pressure and the same temperature for 5 minutes with vigorous stirring. The obtained polyoxalate polyoxalate urethane (propane-1,3-diol-3MPD type POU) was taken out from the reaction vessel and cured under vacuum at 100 ° C. for 24 hours. Table 1 shows the physical properties of propane-1,3-diol-3MPD type POU.

[Example 3] (Thermosetting polyoxalate urethane)
(Production of polyoxalate diol)
Into a 20 L glass reactor equipped with a stirrer, thermometer, and distillation column (equipped with fractionation tube, reflux head, condenser at the top), dimethyl oxalate (DMO) (7194 g; 60.9 mol), Polytetramethylene ether glycol 250 (PTMEG250) (30476 g; 121.9 mol) and tetra-n-butoxytitanium (TBT; 1.524 g; 4.48 mmol; 40.5 ppm by weight based on the total amount of DMO and PTMEG250) The reaction was carried out at 130 ° C. for 1 hour under pressure, and then the reaction was carried out at 150 ° C. for 3 hours under normal pressure to distill methanol. Further, react at 300 torr and 150 ° C. for 2 hours, then react at 100 torr and 150 ° C. for 2.5 hours, further react at 100 torr and 150 ° C. for 2 hours, further react at 90 torr and 150 ° C. for 1 hour, and further The mixture was reacted at 80 torr and 150 ° C. for 1 hour, further reacted at 40 torr and 150 ° C. for 0.5 hour, and methanol was further distilled off under reduced pressure. Finally, TBT and an equimolar amount of dibutyl phosphate were added to the reaction product, and stirred at 120 ° C. for 2 hours under normal pressure to deactivate the catalyst. The number average molecular weight (Mn) of the obtained polyoxalate diol (PTMEG250 type POD) was 599.

(Manufacture of polyoxalate urethane urethane)
PTMEG250-type POD (17.6 kg; 29.4 mol) is placed in a 100 L stainless steel reactor equipped with a stirrer, thermometer, and condenser, and tolylene diisocyanate (TDI) (30 kg). 172.4 mol) was added over 1 hour and allowed to react slowly. Next, the reaction was carried out for 2 hours while stirring at normal pressure and 60 ° C. The obtained oxalate urethane prepolymer was defoamed by repeating a reduced pressure of about 10 torr and a normal pressure 5-6 times. Thereafter, 3,3′-dichloro-4,4′-diaminodiphenylmethane (MOCA) (4.05 g; melted at 130 ° C.) in a PTMEG250 type urethane prepolymer (16.0 g; 0.017 mol) kept at 60 ° C. 0.015 mol) was added and cured. Table 2 shows the melt viscosity of the PTMEG250 type urethane prepolymer and the tension of the PTMEG250 type POU obtained by thermosetting this with MOCA.

[Example 4] (Thermosetting polyoxalate urethane)
(Production of polyoxalate diol)
A glass reactor having an internal volume of 500 ml equipped with a stirrer, a thermometer, and a distillation column (equipped with a fractionation tube, a reflux head, and a condenser at the top) was charged with dimethyl oxalate (DMO) (26.6 g; 0.225 mol), Polytetramethylene ether glycol 250 (PTMEG250) (125 g; 0.5 mol) and tetra-n-butoxytitanium (TBT; 4 mg; 11.8 μmol; 26.4 ppm by weight based on the total amount of DMO and PTMEG250) The mixture was reacted at 130 ° C. for 1 hour under normal pressure, further reacted at 160 ° C. for 1 hour under normal pressure, and then reacted at 180 ° C. for 1 hour under normal pressure to distill methanol. Further, the mixture was reacted at 300 torr and 180 ° C. for 1 hour, and then reacted at 100 torr and 180 ° C. for 4 hours, and methanol was further distilled off under reduced pressure. Finally, TBT and an equimolar amount of dibutyl phosphate were added to the reaction product, and stirred at 120 ° C. for 2 hours under normal pressure to deactivate the catalyst. The number average molecular weight (Mn) of the obtained polyoxalate diol (PTMEG250 type POD) was 1053.

(Manufacture of polyoxalate urethane)
PTMEG250-type POD (50 g; 0.047 mol) was placed in a reaction vessel under a nitrogen atmosphere in a 300 mL glass reactor equipped with a stirrer, thermometer, and condenser, and TDI (16.5 g; 0.095 mol) Was slowly added to react. Next, the mixture was stirred at normal pressure and room temperature for 1 hour, and further reacted at normal pressure and 60 ° C. for 2 hours. Thereafter, the resulting polyoxalate urethane was degassed by reducing the pressure to about 10 torr. Thereafter, MOCA (11.41 g; 0.043 mol) was added and heat-cured. Table 2 shows the viscosity of the PTMEG250 type urethane prepolymer and the tension of the PTMEG250 type POU obtained by thermosetting this with MOCA.

[Example 5] (Thermosetting oxalate polyurethane)
(Production of polyoxalate diol)
Into a 500 ml glass reactor equipped with a stirrer, thermometer, and distillation column (equipped with fractionation tube, reflux head, condenser at the top), dimethyl oxalate (DMO) (41.3 g; 0.350 mol), TEG (75.0 g; 0.499 mol) represented by formula (4) and tetra-n-butoxytitanium (TBT; 6 mg; 17.6 μmol; 51.6 ppm by weight based on the total amount of DMO and TEG) The mixture was reacted at 130 ° C. for 1 hour under normal pressure, further reacted at 160 ° C. for 1 hour under normal pressure, and then reacted at 180 ° C. for 1 hour under normal pressure to distill methanol. Further, the mixture was reacted at 300 torr and 180 ° C. for 1 hour, and then reacted at 100 torr and 180 ° C. for 4 hours, and methanol was further distilled off under reduced pressure. Next, the temperature was raised to 200 ° C. and the pressure was reduced to 1 torr, and a polycondensation reaction was carried out for 2 hours to distill TEG. Finally, TBT and an equimolar amount of dibutyl phosphate were added to the reaction product, and stirred at 120 ° C. for 2 hours under normal pressure to deactivate the catalyst. The number average molecular weight (Mn) of the obtained polyoxalate diol (TEG type POD) was 396.

(Manufacture of polyoxalate urethane)
A TEG type POD (50 g; 0.126 mol) was placed in a reaction vessel under a nitrogen atmosphere in a glass reactor having an internal volume of 300 ml equipped with a stirrer, thermometer, and cooling tube, and TDI (44 g; 0.253 mol) Was slowly added to react. Next, the mixture was stirred at normal pressure and room temperature for 1 hour, and further reacted at normal pressure and 60 ° C. for 2 hours. Thereafter, the resulting polyoxalate urethane was degassed by reducing the pressure to about 10 torr. Thereafter, MOCA (30.4 g; 0.114 mol) was added and heat-cured. Table 2 shows the viscosity of the TEG type urethane prepolymer and the tension of the TEG type POU obtained by thermosetting this with MOCA.

[Comparative Example 2] (Thermosetting oxalate polyurethane)
(Production of polyoxalate diol)
Into a 500 ml glass reactor equipped with a stirrer, thermometer, and distillation column (equipped with fractionation tube, reflux head, condenser at the top), dimethyl oxalate (DMO) (41.3 g; 0.350 mol), 1,5-pentanediol (1,5-PD) (52.1 g; 0.500 mol) and tetra-n-butoxytitanium (TBT; 6 mg; 17.6 μmol; 64.2 ppm by weight relative to the total amount of DMO and TEG) ), And reacted at 130 ° C. for 1 hour under normal pressure, further reacted at 160 ° C. for 1 hour under normal pressure, and then reacted at 180 ° C. for 1 hour under normal pressure to distill methanol. Further, the mixture was reacted at 300 torr and 180 ° C. for 1 hour, and then reacted at 100 torr and 180 ° C. for 4 hours, and methanol was further distilled off under reduced pressure. Subsequently, the temperature was raised to 200 ° C. and the pressure was reduced to 1 torr, and a polycondensation reaction was performed for 2 hours to distill 1,5-PD. Finally, TBT and an equimolar amount of dibutyl phosphate were added to the reaction product, and stirred at 120 ° C. for 2 hours under normal pressure to deactivate the catalyst. The number average molecular weight (Mn) of the obtained polyoxalate diol (1,5-PD type POD) was 514.

(Manufacture of polyoxalate urethane urethane)
A TEG-type POD (50 g; 0.126 mol) was placed in a reaction vessel under a nitrogen atmosphere in a 300-ml glass reactor equipped with a stirrer, thermometer, and cooling tube, and a 1,5-PD-type POD ( 50 g; 0.973 mol) was placed in a reaction vessel under a nitrogen atmosphere, and TDI (33.9 g; 0.195 mol) was slowly added to react. Next, the mixture was stirred at normal pressure and room temperature for 1 hour, and further reacted at normal pressure and 60 ° C. for 2 hours. Thereafter, the obtained 1,5-PD type urethane prepolymer was degassed by reducing the pressure to about 10 torr. Thereafter, MOCA (23.3 g; 0.087 mol) was added and heat-cured. Table 2 shows the viscosity of 1,5-PD type urethane prepolymer and the tension of 1,5-PD type POU obtained by thermosetting this with MOCA.

The polyoxalate urethane and the polyoxalate urethane composition of the present invention are applied to a known melt processing method such as injection molding, extrusion molding, press molding, hollow molding, thermoforming, etc., to form a film, sheet, fiber, nonwoven fabric, It can be used for molded products such as containers, paints, medical materials, automobile materials, various agricultural / industrial materials and members.

Claims (5)

A polyoxalate polyol having an ether bond represented by the following general formula (1).

(In the formula, R represents an alkylene group having 2 to 12 carbon atoms and may contain a branched structure or an alicyclic structure, n represents the degree of polymerization of polyoxalate and is 1 to 32, and m represents poly Represents the degree of polymerization of ether and is 2 to 60.) A polyoxalate urethane having an ether bond obtained by reacting the polyoxalate polyol according to claim 1 with diisocyanate. The polyoxalate urethane having an ether bond according to claim 2, which is obtained by further adding a chain extender or a thermosetting agent to cause a reaction. The polyoxalate urethane having an ether bond according to claim 3, wherein the molar ratio of polyoxalate polyol having an ether bond: chain extender or thermosetting agent: diisocyanate is in the range of 1: 0.5: 1.5 to 1: 6: 7. . 5. The polyoxalate urethane having an ether bond according to any one of claims 2 to 4, wherein the number average molecular weight of the polyoxalate polyol having an ether bond is 500 to 5,000.