WO2007080929A1 - Polyoxalate urethane - Google Patents

Polyoxalate urethane Download PDF

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Publication number
WO2007080929A1
WO2007080929A1 PCT/JP2007/050259 JP2007050259W WO2007080929A1 WO 2007080929 A1 WO2007080929 A1 WO 2007080929A1 JP 2007050259 W JP2007050259 W JP 2007050259W WO 2007080929 A1 WO2007080929 A1 WO 2007080929A1
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Prior art keywords
component
polyoxalate
urethane
formula
reaction
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PCT/JP2007/050259
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English (en)
Japanese (ja)
Inventor
Hiroshi Okushita
Kouichiro Kurachi
Fumio Adachi
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Ube Industries, Ltd.
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Priority to JP2007553932A priority Critical patent/JP5380841B2/ja
Publication of WO2007080929A1 publication Critical patent/WO2007080929A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2230/00—Compositions for preparing biodegradable polymers

Definitions

  • the present invention relates to a novel polyoxalate urethane, and more particularly to a polyoxalate urethane excellent in hydrolysis characteristics and biodegradation characteristics.
  • Patent Document 1 proposes polyoxalate urethane as a polyester urethane having excellent biodegradability.
  • 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
  • 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.
  • the present invention relates to the following items.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • Oxalate urethane can be provided.
  • 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.
  • 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.
  • 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.
  • 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.
  • the polyol is preferably an aliphatic polyol such as an aliphatic diol, an aliphatic triol, or an aliphatic tetraol.
  • 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.
  • 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.
  • the polycondensation reaction can be performed by a known method with an excess of polyol such that the terminal is a hydroxyl group.
  • 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.
  • the reaction temperature is 120 ° C to 350 ° C
  • the reaction pressure is 1 mmHg (133 Pa) to 760 mmHg (l. 01 X 10 5 Pa) or less.
  • inert gas nitrogen, helium, Argon, etc.
  • a known catalyst that can be reacted under a flow or the temperature or pressure can be varied.
  • a transesterification catalyst is preferred.
  • tetraalkoxytitanium tetra- n -butoxytitanium, etc.
  • the amount and timing of addition of the catalyst are not particularly limited as long as the conditions can promote the reaction.
  • 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.
  • Component B comprises at least one of polyester polyol, polyalkylene ether polyol, and polyhydroxycarboxylic acid polyol.
  • the polyester polyol is a compound having a structure obtained by subjecting a dicarboxylic acid source and a polyol to a polycondensation reaction.
  • a dicarboxylic acid source an aliphatic dicarboxylic acid represented by the formula (6) is preferred.
  • 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.
  • the diester of aliphatic dicarboxylic acid can also be mentioned preferably.
  • aliphatic dicarboxylic acid examples include succinic acid, gnoretaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, and dodecanedioic acid.
  • aliphatic polyols such as aliphatic diols, aliphatic triols, and aliphatic tetraols are preferable.
  • the aliphatic diol represented by the formula (7) is more preferable.
  • R 2 includes a branched structure or an alicyclic structure.
  • 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).
  • the polycondensation reaction can be performed by a known method with an excess of polyol such that the terminal is a hydroxyl group.
  • the aliphatic dicarboxylic acid and the aliphatic diol are necessary.
  • 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.
  • m is the degree of polymerization of the polyester diol (structural unit “—R 2 ⁇ C ⁇ R 3 C ⁇ 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.
  • polyalkylene ether polyol is a compound having a structure obtained by subjecting an ether source and polyol to a polymerization reaction.
  • an alkylene oxide represented by the formula (8) is preferred.
  • 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.
  • the alkylene oxide include ethylene oxide, propylene oxide, 1,2-butylene oxide, 2,3 butylene oxide, 1,3 butylene oxide, tetrahydrofuran, and 3-methyltetrahydrofuran.
  • the polyol is preferably an aliphatic polyol such as an aliphatic diol, an aliphatic triol, or an aliphatic tetraol.
  • the aliphatic diol represented by formula (9) is more preferred.
  • 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.
  • the polymerization reaction can be carried out by a known method.
  • 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.).
  • 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.
  • the polyhydroxycarboxylic acid polyol is a compound having a structure obtained by subjecting a hydroxycarboxylic acid source and polyol to a polymerization reaction.
  • an aliphatic cyclic ester represented by the formula (10) is preferred as the hydroxycanolenic acid source.
  • 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, ⁇ -propiolatathone, ⁇ -butyrolatathone, ⁇ -valerolatatone, and ⁇ -force prolatathone.
  • the polyol is preferably an aliphatic polyol such as an aliphatic diol, an aliphatic triol, or an aliphatic tetraol.
  • 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).
  • a trivalent or higher polyol such as aliphatic triol or aliphatic tetraol
  • a branched structure is introduced into the molecule. You may use it independently suitably.
  • the polymerization reaction can be carried out by a known method.
  • 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.
  • polyhydroxycarboxylic acid diol represented by the above formula (4) is preferred.
  • 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.
  • component C chain extender examples 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-dihydroxyethy
  • 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.
  • chain extenders 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.
  • 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.
  • diisocyanate compounds are preferred, and examples thereof include aliphatic and aromatic diisocyanates. D component polyisocyanate used alone or in combination it can.
  • aliphatic diisocyanate for example, 1, 3 trimethylene diisocyanate, 1, 4
  • aromatic diisocyanate examples 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
  • diisocyanates 4,4′-diphenylmethane diisocyanate, 1,6-hexamethylene diisocyanate, and isophorone diisocyanate are particularly preferred.
  • 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.
  • 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.
  • D component so that it will be set to :: 1: 1.2, Furthermore, it is 1: 0.9.95-: 1: 1.05.
  • 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.
  • the A component and the B component may have different aliphatic hydrocarbon groups or different number average molecular weights.
  • 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.
  • 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
  • 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.
  • 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.
  • 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.
  • 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.
  • a known amine-based or tin-based catalyst may be used to promote the reaction.
  • 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.
  • 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.
  • 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.
  • thermoplastic polyurethanes such as adipate, ratatone, and ether are preferably used.
  • 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.
  • 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.
  • 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.
  • 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.
  • SBS block copolymers
  • 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.
  • 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. .
  • 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.
  • S is the integral value of the proton of methylene adjacent to the terminal hydroxyl group
  • M is the polyoxalene
  • M is the raw material of polyoxalate diol
  • the measurement was performed in the atmosphere under the condition of a temperature increase rate of 10 ° CZ.
  • Viscosity (Pa 'sec): Measured using an E-type viscometer (manufactured by Tokyo Keiki).
  • 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.
  • 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.
  • DMO dimethyl oxalate
  • HDL 1, 6-hexanedi-nore
  • TBT tetra-n-butoxytitanium
  • 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 ⁇ 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.
  • 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.
  • 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.
  • 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.
  • PHMOD— 1 feed amount is changed to 25 g (0.0120 monole)
  • Example 2 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 ⁇ m 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.
  • PHMOD— 1 feed amount is changed to 5 g (0.0024 monole)
  • Example 2 After completion of the reaction, a film of about 200 ⁇ m 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.
  • Example 2 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.
  • PDA dissolved in 10 g of DMF
  • PC D Polycube ⁇ -lactone diol
  • 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.
  • PMOD-2 polyoxalate diol
  • 359.3 g (l.436 monole) of MDI manufactured by Nippon Polyurethane was added and reacted at the same temperature for 3 hours.
  • 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.
  • 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.
  • 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).
  • 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).
  • Oxalate urethane can be provided.
  • 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.

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  • Health & Medical Sciences (AREA)
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Abstract

La présente invention concerne un polyoxalate-uréthane ayant une excellente longévité (résistance à l'hydrolyse) et biodégradabilité, lequel est obtenu par la réaction d’un polyoxalate-polyol (composant A), d’au moins un élément parmi des polyester-polyols, des polyalkylène-éther-polyols et des polyhydroxycarboxylate-polyols (composant B), d’un allongeur de chaîne (composant C) et d’un composé polyisocyanate (composant D).
PCT/JP2007/050259 2006-01-12 2007-01-11 Polyoxalate urethane WO2007080929A1 (fr)

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JP2006-004713 2006-01-12

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JP2009203404A (ja) * 2008-02-29 2009-09-10 National Institute Of Advanced Industrial & Technology 柔軟性に富む生分解性材料とその製造方法
US20140058011A1 (en) * 2008-02-13 2014-02-27 Jotun A/S Antifouling composition
JP2015204353A (ja) * 2014-04-14 2015-11-16 株式会社オートネットワーク技術研究所 リアクトルおよび注型樹脂
JP2019034385A (ja) * 2017-08-18 2019-03-07 富士紡ホールディングス株式会社 研磨パッド

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JPH06145283A (ja) * 1992-11-09 1994-05-24 Unitika Ltd 生分解性ポリマー
JPH06157703A (ja) * 1992-11-17 1994-06-07 Nippon Kayaku Co Ltd 熱可塑性脂肪族ポリエステル及び改質物
WO2003064497A1 (fr) * 2002-01-30 2003-08-07 Kyowa Hakko Chemical Co., Ltd. Polyester
JP2003335838A (ja) * 2002-05-22 2003-11-28 Ube Ind Ltd ポリエステルカーボネートウレタン
JP2003335837A (ja) * 2002-05-22 2003-11-28 Ube Ind Ltd ポリエステルウレタン

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JPH06145283A (ja) * 1992-11-09 1994-05-24 Unitika Ltd 生分解性ポリマー
JPH06157703A (ja) * 1992-11-17 1994-06-07 Nippon Kayaku Co Ltd 熱可塑性脂肪族ポリエステル及び改質物
WO2003064497A1 (fr) * 2002-01-30 2003-08-07 Kyowa Hakko Chemical Co., Ltd. Polyester
JP2003335838A (ja) * 2002-05-22 2003-11-28 Ube Ind Ltd ポリエステルカーボネートウレタン
JP2003335837A (ja) * 2002-05-22 2003-11-28 Ube Ind Ltd ポリエステルウレタン

Cited By (5)

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Publication number Priority date Publication date Assignee Title
US20140058011A1 (en) * 2008-02-13 2014-02-27 Jotun A/S Antifouling composition
US9546283B2 (en) * 2008-02-13 2017-01-17 Jotun A/S Antifouling composition
JP2009203404A (ja) * 2008-02-29 2009-09-10 National Institute Of Advanced Industrial & Technology 柔軟性に富む生分解性材料とその製造方法
JP2015204353A (ja) * 2014-04-14 2015-11-16 株式会社オートネットワーク技術研究所 リアクトルおよび注型樹脂
JP2019034385A (ja) * 2017-08-18 2019-03-07 富士紡ホールディングス株式会社 研磨パッド

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