WO2018235600A1 - Composition de polymère - Google Patents

Composition de polymère Download PDF

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Publication number
WO2018235600A1
WO2018235600A1 PCT/JP2018/021704 JP2018021704W WO2018235600A1 WO 2018235600 A1 WO2018235600 A1 WO 2018235600A1 JP 2018021704 W JP2018021704 W JP 2018021704W WO 2018235600 A1 WO2018235600 A1 WO 2018235600A1
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Prior art keywords
polyoxalate
polymer composition
diol
polymer
carboxyl group
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PCT/JP2018/021704
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English (en)
Japanese (ja)
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成 川原
成志 吉川
傳喜 片山
幸樹 柴田
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東洋製罐グループホールディングス株式会社
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Publication of WO2018235600A1 publication Critical patent/WO2018235600A1/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
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • 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
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/91—Polymers modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/16—Compositions of unspecified macromolecular compounds the macromolecular compounds being biodegradable

Definitions

  • the present invention relates to a polymer composition comprising polyoxalate as polymer component.
  • the polyoxalate is a polyester comprising an acid structural unit derived from oxalic acid and a diol structural unit derived from a diol.
  • Polyoxalate has excellent hydrolyzability, and its use in various applications is being considered. For example, in the field of agriculture, use in the form of films, sheets, trays, pots, etc. is being considered. In the environmental field, use as a water purification material or a soil purification material in the form of powder or pellet is being studied. In the field of resource mining such as shale gas, use in the form of powder, spherical particles, fibers or the like in addition to fracturing fluid, finishing fluid, etc. is being studied.
  • polyoxalate is an environmentally friendly biodegradable resin, and it is difficult to perform post-treatment work in wells and the like, and it is necessary to have water even in a low temperature (100 ° C. or less) environment Because it can be expected to hydrolyze with nature, studies are actively conducted.
  • polyoxalate is low in heat resistance and has a problem that it is easily thermally decomposed at the time of melt molding such as spinning, extrusion molding, injection molding and the like.
  • melt molding such as spinning, extrusion molding, injection molding and the like.
  • polyoxalate has a disadvantage that the molecular weight is reduced. There is.
  • Patent Document 1 proposes a polyester polymer having a number average molecular weight of 10,000 or more in terms of polystyrene measured by GPC, and such a polyester polymer Polyoxalate is disclosed.
  • This polyoxalate has a high thermal decomposition temperature and is excellent in heat resistance.
  • the present applicant previously proposed a polyoxalate copolymer using a total of two or more of ethylene glycol and other diols as a diol in Japanese Patent Application No. 2016-035585 (Japanese Patent Laid-Open No. 201-149892). doing.
  • Such a polyoxalate copolymer has heat resistance, and the reduction in molecular weight at the time of thermoforming is suppressed.
  • hydrolysis starts within several days from the start of use, and hydrolysis is thereafter rapidly.
  • the polyoxalate copolymers of the prior application also possess adequate hydrolytic properties.
  • the polyoxalate copolymer of the prior application is limited in the type of diol to be used, and the degree of freedom in designing the structure of polyoxalate is low depending on the application, use environment, etc. is necessary.
  • an object of the present invention is a polymer composition containing polyoxalate as a polymer component, in which the reduction in molecular weight during molding of polyoxalate is effectively suppressed and the hydrolyzability of polyoxalate is maintained.
  • a polymer composition comprising, as polymer component, a polyoxalate having a diol constituent unit derived from a diol and an acid constituent unit derived from oxalic acid
  • a polymer composition comprising a terminal carboxyl group capping agent as a molding stabilizer and having a 5% weight loss temperature by TG-DTA of 300 ° C. or less.
  • the terminal carboxyl group capping agent is a carbodiimide compound or a polycarbodiimide.
  • the diol is butanediol or ethylene glycol.
  • the diol is butanediol.
  • the 5% weight loss temperature is 220 to 300 ° C.
  • a molded article obtained by thermoforming the above-mentioned polymer composition. It is preferred that the above-mentioned molded body has a fiber or granular form.
  • the polymer composition of the present invention contains polyoxalate as a polymer component, and is an important feature in that a terminal carboxyl group capping agent is blended as a molding stabilizer. That is, when polyoxalate is held for a long time at a certain temperature or higher, decomposition of the terminal carboxyl group occurs. In addition, hydrolysis occurs when high temperature polyoxalate is introduced into water due to underwater cutting and the like, and a carboxyl group is present at the end of the molecule generated by hydrolysis. Thus, degradation of the polyoxalate results in a reduction in molecular weight during molding of the polyoxalate.
  • a terminal carboxyl group capping agent is blended, and the terminal of the carboxyl group is protected by this capping agent, thermal decomposition of polyoxalate is suppressed, and further polyoxalate accompanied by hydrolysis. Chain decomposition is effectively suppressed.
  • the 5% weight loss temperature by TG-DTA is in the range of 300 ° C. or less (preferably 220 to 300 ° C.).
  • the 5% weight loss temperature is prepared by the compounding amount of the terminal carboxyl group capping agent, and when the compounding amount of the sealant is increased, the 5% weight loss temperature becomes high, and when the compounding amount is decreased, the 5% weight component is reduced. The reduced temperature is lower.
  • the amount of the terminal carboxyl group capping agent is adjusted so that the 5% weight loss temperature is in the above range, the initial hydrolysis of polyoxalate in a water-containing environment at high temperature is although it is suppressed, once hydrolysis occurs, hydrolysis proceeds rapidly, as with normal polyoxalate. That is, at the time of molding such as under water cutting, hydrolysis is suppressed and the lowering of the molecular weight is prevented, but the obtained molded product is a molded product of polyoxalate in which the terminal carboxyl group capping agent is not blended. It will exhibit the same hydrolyzability. For example, when the terminal carboxyl group capping agent is blended so that the 5% weight loss temperature is higher than the above range, the polyoxalate is excessively stabilized and the hydrolyzability of the polyoxalate is impaired. It will be
  • the polyoxalate used in the present invention is a polyester having a diol constituent unit derived from a diol and an acid constituent unit derived from oxalic acid, and an esterification polymerization reaction by reacting a diol and oxalic acid, or an alkyl oxalate Obtained by a polymerization reaction involving transesterification using
  • This polyoxalate has an oxalate repeating unit represented by the following formula.
  • n is a positive number representing the degree of polymerization
  • A is an organic group derived from a diol, and a plurality of organic groups A may be identical to one another or may be different from one another.
  • the alkyl oxalate is preferably a dialkyl oxalate, more preferably a dialkyl oxalate consisting of an alkyl group having 1 to 4 carbon atoms such as dimethyl oxalate, diethyl oxalate, propyl oxalate, dimethyl oxalate and diethyl oxalate Particularly preferred.
  • diols examples include ethylene glycol, propylene glycol, butanediol, hexanediol, octanediol, dodecanediol, neopentyl glycol, bisphenol A, cyclohexane dimethanol and the like, but it is easy to obtain appropriate hydrolyzability.
  • linear dihydric alcohols such as ethylene glycol, propylene glycol, butanediol, hexanediol, octanediol, dodecanediol are preferred, butanediol or ethylene glycol is more preferred, and butanediol is particularly preferred.
  • the polyoxalate used in the present invention may be a copolymer containing other ester units as long as it has the above-mentioned oxalate repeating unit, but preferably, 80 mol% or more of the above-mentioned oxalate repeating unit Particularly, it is preferable that 90 mol% or more is contained.
  • the weight average molecular weight (Mw) of the polyoxalate described above is preferably 30,000 to 200,000, more preferably 50,000 to 150,000, and still more preferably 50,000 to 100,000, from the viewpoint of facilitating acquisition of appropriate hydrolysability and molding processability. It is. Even if the molecular weight exceeds the above upper limit value, the performance is not affected at all, but since the polymerization time becomes long, there is a concern that the productivity may be lowered.
  • Terminal carboxyl group capping agent used together with the above polyoxalate in the polymer composition of the present invention is a compound or polymer having a functional group which can be bonded to a carboxyl group to function as a protective group.
  • carbodiimide compound monocarbodiimide having one carbodiimide group in the molecule, for example, N, N'-diisopropylcarbodiimide, N, N'-di-tert-butylcarbodiimide, N- (3-dimethylaminopropyl) -N Aliphatic monocarbodiimides such as' -ethylcarbodiimide, N, N'-dicyclohexylcarbodiimide; N, N'-diphenylcarbodiimide, N, N'-di-p-tolylcarbodiimide, N, N'-bis (dimethylphenyl) carbodiimide N, N'-bis (methoxyphenyl) carbodiimide, N, N'-bis (nitrophenyl) carbodiimide, N, N'-bis (2,6-diisopropylphenyl) carbodiimide, N, N'-bis (tri
  • polycarbodiimides having two or more carbodiimide groups in the molecule for example, aliphatic polycarbodiimides such as poly (4,4'-dicyclohexylmethanecarbodiimide); poly (p -Phenylene carbodiimide), poly (m-phenylene carbodiimide), poly (methyl phenylene carbodiimide), poly (diisopropyl phenylene carbodiimide), poly (methyl diisopropyl phenylene carbodiimide), poly (1, 3, 5- triisopropyl phenylene carbodiimide), poly Aromatic polycarbodiimides such as (1,3,5-triisopropylphenylene-co-1,5-diisopropylphenylene carbodiimide), poly (4,4'-diphenylmethane carbodiimide), etc.
  • aliphatic polycarbodiimides such as poly (4,4'-dicyclohexylmethan
  • polycarbodiimides aliphatic polycarbodiimides are preferable because they can efficiently protect carboxyl groups.
  • Various types of polycarbodiimides such as those described above are marketed by Nisshinbo Chemical Co., Ltd. under the trade name of Carbodilite. This carbodiimide is a polymer obtained by decarboxylative condensation of diisocyanate.
  • such terminal carboxyl group capping agent is determined such that the 5% weight loss temperature (Td 5%) by TG-DTA of the polymer composition is 300 ° C. or less, more preferably 220 to 300 ° C. Be done.
  • Td 5% 5% weight loss temperature
  • the higher the Td 5% value the more stable the polyoxalate, but the lower the hydrolyzability.
  • Td5% becomes high, so that the compounding quantity of terminal carboxyl group blocking agent increases.
  • a polymer composition having a Td of 5% in the above-mentioned range has the adequate hydrolyzability required for polyoxalate while having sufficient stability to withstand molding.
  • the blending amount of the terminal carboxyl group capping agent for securing a value of 5% of Td as described above varies depending on the type of the sealant, the structure of polyoxalate, etc. It is 1,000 to 50,000 ppm, in particular 1,000 to 20,000 ppm, relative to polyoxalate.
  • additives of terminal carboxyl group capping agent such as plasticizer, light stabilizer, antioxidant, UV absorber, flame retardant, colorant, pigment, filler, filler And mold release agents, antistatic agents, perfumes, lubricants, foaming agents, antibacterial and antifungal agents, nucleation agents, layered borates, crosslinkers, enzymes and the like.
  • biodegradable resin compositions other than polyoxalate for example, aliphatic polyester, polyvinyl alcohol, and celluloses may be blended together as required.
  • the polymer composition of the present invention is subjected to an esterification polymerization reaction such as dehydration reaction or transesterification reaction by a known method to polymerize the polyoxalate, and the terminal carboxyl group capping agent is stirred in the obtained polyoxalate. It is manufactured by mixing.
  • known catalysts can be used, if necessary.
  • known catalysts include titanium alkoxides such as titanium tetrabutoxide, antimony compounds such as antimony trioxide, and tin compounds such as dibutyltin oxide and butyltin dilaurate, but in addition to this, P, Ge, Examples thereof include Zn, Fe, Mn, Co, Zr, V and compounds of various rare earth metals.
  • Organic solvents include aromatic hydrocarbon-based organic solvents such as benzene, toluene and xylene; aliphatic hydrocarbon-based organic solvents such as pentane, hexane, cyclohexane, heptane, decalin and tetralin; ether-based organic solvents such as ethyl ether and tetrahydrofuran Solvents; Chlorinated hydrocarbon-based organic solvents such as chloroform, chlorobenzene, carbon tetrachloride, etc .;
  • polystyrene resin As a specific polymerization method of polyoxalate, for example, there is a method of proceeding an esterification polymerization reaction in two steps of normal pressure polymerization and reduced pressure polymerization using a diol and an alkyl oxalate. Such a two-step polymerization method can be carried out without using an organic solvent and in the absence of a solvent. The implementation without solvent is advantageous in terms of production cost and the like.
  • the two-stage polymerization method may be carried out using a batch-type polymerization reactor shown in FIG.
  • the polymerization reactor 1 is provided with a stirrer 3 and a distillation pipe 5.
  • the distillation pipe 5 has a top A, and also has a reflux portion 5a in the region from the polymerization reactor 1 to the top A and a distillation 5b downstream of the top A.
  • the distillation section 5b is provided with a cooling pipe 5c such as a heat exchanger so that the liquid to be distilled is condensed and discharged quickly.
  • a heating pipe or a cooling pipe may be appropriately attached to the reflux portion 5a so that the temperature of the top A can be adjusted.
  • the reaction liquid 10 (alkyl oxalate, diol and optionally used catalyst and organic solvent) is supplied into the polymerization reactor 1, and alcohol, unreacted diol, oligomer and the like by-produced in the esterification polymerization reaction are distilled off.
  • the distillation portion 5 b is distilled off as a distillate 15 through the reflux portion 5 a of the last tube 5.
  • the two-step polymerization method is carried out while adjusting the distillation conditions.
  • the amount of diol charged in the reaction solution is 0.8 to 1.2 moles, preferably 1.0 to 1.2 moles, per mole of alkyl oxalate, from the viewpoint of rapidly advancing an atmospheric pressure polymerization reaction.
  • Atmospheric pressure polymerization is carried out by displacing the inside of the polymerization reactor 1 to a nitrogen gas atmosphere, charging the reaction solution and heating it to a range of 110 to 200 ° C. while stirring, whereby the low polymerization degree
  • the distillation of the alcohol stops the normal pressure polymerization is stopped and the next reduced pressure polymerization is performed.
  • Low pressure polymerization The low pressure polymerization is to maintain the reaction liquid 10 containing low polymerization degree polyoxalate generated by atmospheric pressure polymerization at 180 to 210 ° C. while maintaining the pressure in the polymerization reactor 1 at 0.1 to 1 kPa under reduced pressure. It is done by The polymerization is allowed to proceed further while removing the diol remaining in the reaction liquid 10 by the reduced pressure polymerization, to obtain a further polymerized polyoxalate.
  • the reflux portion 5a of the distillation pipe 5 in order to accelerate the removal of the residual diol, it is preferable to keep the reflux portion 5a of the distillation pipe 5 at 90 to 140 ° C.
  • the reduced pressure polymerization step may be ended when removal of the residual diol is stopped.
  • the termination of removal of the residual diol can be confirmed by monitoring the temperature at the top of the head A of the distillation pipe 5, for example.
  • the reduced pressure polymerization following the normal pressure polymerization the content of impurities such as by-product alcohol and unreacted diol is suppressed, and a polyoxalate having a higher molecular weight than at the time of normal pressure polymerization can be obtained.
  • the above description does not limit the polymerization method of polyoxalate in the present invention, and the polymerization may be performed by other methods.
  • the terminal carboxyl group capping agent is charged into the molten polyoxalate, and the mixture is stirred and mixed.
  • the stirring and mixing may be performed according to known conditions and means, but when stirring and mixing is performed under a reduced pressure of 10 kPa or more and less than 1000 kPa, impurities such as residual diol and by-product alcohol can be removed. ,preferable.
  • the terminal carboxyl group capping agent is uniformly mixed in the polyoxalate, whereby a part of the capping agent reacts with the terminal carboxyl group of the polyoxalate to seal the carboxyl group. Be done.
  • the mixing time is generally about 0.5 to 3 hours.
  • the capping of the terminal carboxyl group by the polyoxalate can be confirmed by the decrease in the acid value of the polyoxalate, the decrease in initial hydrolyzability, and the like.
  • the terminal carboxyl group capping agent can also be mixed with the polyoxalate as a liquid dissolved or dispersed in a blend, a solvent, or the like, which is melt mixed with another polymer.
  • polyoxalate may be reduced in molecular weight in the stirring and mixing step of the carboxyl group-binding compound, in that case, it is preferable to polymerize the polyoxalate in advance assuming the lowering of molecular weight in the stirring and mixing step. .
  • the terminal carboxyl group capping agent can also be mixed with the polyoxalate in the kneading section of the extruder.
  • the polio chelate and the terminal carboxyl group capping agent may be simultaneously supplied from the hopper to the kneading section of the extruder, or the polyoxalate is first supplied from the hopper and melted, and the terminal carboxyl is added to the middle of the extruder A base sealant may be supplied.
  • the polymer composition of the present invention has heat resistance, and hydrolysis in water is suppressed if it is a short time as in a molding process. This means that the polymer composition is held at 150 ° C. for 5 minutes, and the weight average molecular weight when immersed in water at 25 ° C. for 1 minute is measured, and the molecular weight retention is calculated, the polymer composition of the present invention In this case, it is clear from showing 90% or more, especially 92% or more.
  • the polymer composition of the present invention has moderate hydrolyzability after molding, similar to known polyoxalate.
  • the appropriate hydrolyzability can be confirmed from the hydrolysis behavior of the polymer composition of the present invention even if the hydrolysis behavior of the molded body is not confirmed. That is, a sample obtained by pulverizing the polymer composition is put into distilled water at 90 ° C. and hydrolyzed for one week, and then the weight (weight after hydrolysis) of the remaining sample is measured, and the residual ratio is determined by the following equation.
  • the residual ratio of the polymer composition of the present invention is 10% or less, 8% or less in a preferred embodiment, and 5% or less in a particularly preferred embodiment.
  • Residual rate (%) W2 (weight g after hydrolysis) / W1 (initial input amount g) ⁇ 100
  • the polymer composition of the present invention having the characteristics as described above is applied to applications such as extrusion molding, injection molding, and the like which are required to be hydrolyzable as a thermoformed product obtained by molding the melt into a predetermined shape. Be done.
  • those thermoformed in the form of fibers or pellets are suitably applied to mining dispersions represented by fracturing fluids and finishing fluids.
  • the hydrolyzability of the polymer composition (polyoxalate composition) it is suitably formed into a film, sheet, tray, container, etc. form by thermoforming mixed with other polymers, It is degradable and can be used as an environmentally friendly molding.
  • fibers of 0.1 to 5 cm in length obtained from the polymer composition of the present invention are dispersed in water to prepare a dispersion for drilling and the dispersion for drilling is pressed into the ground, such fibrous
  • the shaped bodies are hydrolyzed after a suitable period of time at a temperature of 40-80.degree. Therefore, it is possible to mine underground resources such as shale gas by hydraulic fracturing using such a dispersion as a fracturing fluid.
  • the polymer compositions of the present invention are illustrated by the following examples. In addition, various measurements were performed by the following methods.
  • Td 5% ⁇ 5% weight loss temperature (Td 5%)>
  • Device TG / DTA7220 manufactured by Hitachi High-Tech Science Co., Ltd.
  • Sample preparation sample amount 5 to 10 mg Measurement conditions: Measured in a range of 40 to 300 ° C. at a temperature rising rate of 10 ° C./min in a nitrogen atmosphere. The temperature at which 5% weight decreased relative to the initial weight was taken as Td 5%.
  • Example 1 The following polycarbodiimide was prepared as a terminal carboxyl group capping agent. Nisshinbo Chemical Co., Ltd. Carbodilight HMV-15CA; Softening temperature 70 ° C, 5% weight loss temperature 350 ° C. Dibutyl oxalate 354 g (3 mol), 1,4-butanediol 270 g (3 mol), dibutyltin oxide 0 in a 1 L separable flask equipped with a mantle heater, liquid temperature thermometer, stirrer, nitrogen inlet tube and distillation column The solution temperature in the flask was heated to 120 ° C. under nitrogen flow to carry out atmospheric pressure polymerization.
  • Example 2 Polymer 2 was obtained in the same manner as in Example 1 except that the amount of carbodilite added was changed to 1.75 g (0.5% by weight).
  • Example 3 Polymer 3 was obtained in the same manner as in Example 1 except that the amount of carbodilite added was changed to 3.5 g (1.0% by weight).
  • Example 4 Polymer 4 was obtained in the same manner as in Example 1 except that the amount of carbodilite added was changed to 17.5 g (5.0% by weight).
  • Example 5 Polymer 5 was obtained in the same manner as in Example 1 except that the amount of carbodilite added was changed to 35 g (10.0% by weight).
  • Example 6 295 g (2.5 mol) of dimethyl oxalate, 171 g (2.76 mol) of ethylene glycol, 0 g of dibutyl tin oxide in a 1 L separable flask equipped with a mantle heater, liquid temperature thermometer, stirrer, nitrogen inlet tube and distillation column The solution temperature in the flask was gradually raised to 180 ° C. under a nitrogen stream, and polymerization was carried out under normal pressure. Thereafter, the liquid temperature in the flask was raised to 190 ° C., and polymerization was performed under reduced pressure at a reduced pressure of 0.1 to 0.8 kPa for 6 hours.
  • Comparative Example 1 Polymer 7 was obtained in the same manner as in Example 1 except that carbodilite was not used. That is, atmospheric pressure polymerization and reduced pressure polymerization were performed in the same manner as in Example 1 to obtain polymer 7.
  • Comparative Example 2 Polymer 8 was obtained in the same manner as in Example 6, except that carbodilite was not used. That is, atmospheric pressure polymerization and reduced pressure polymerization were performed in the same manner as in Example 6, to obtain polymer 8.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Polyesters Or Polycarbonates (AREA)
  • Biological Depolymerization Polymers (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne une composition de polymère qui contient, en tant que composant polymère, un polyoxalate possédant une unité structurale diol dérivée d'un diol et une unité structurale acide dérivée d'un acide oxalique. Cette composition de polymère est caractéristique en ce qu'elle contient, avec ledit polyoxalate, un agent de blocage de groupe carboxyle terminal, en tant qu'agent de stabilisation de moulage, et en ce qu'elle présente une température de perte de poids de 5 % selon TG-ATD inférieure ou égale à 300°C.
PCT/JP2018/021704 2017-06-20 2018-06-06 Composition de polymère WO2018235600A1 (fr)

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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004143400A (ja) * 2002-03-25 2004-05-20 Ube Ind Ltd 高分子量ポリオキサレート及びその製造方法
JP2005097606A (ja) * 2003-09-05 2005-04-14 Ube Ind Ltd 生分解性射出成形物
JP2006290937A (ja) * 2005-04-06 2006-10-26 Yamaguchi Univ セルロース系廃棄物−ポリオキサレートコンポジット
WO2015098926A1 (fr) * 2013-12-24 2015-07-02 東洋製罐グループホールディングス株式会社 Polyoxalate et procédé de production associé
WO2016080142A1 (fr) * 2014-11-19 2016-05-26 東洋製罐グループホールディングス株式会社 Procédé d'exploitation de ressources souterraines, et agant de blocage hydrolysable destiné à être utilisé dans ledit procédé
WO2016129501A1 (fr) * 2015-02-12 2016-08-18 東洋製罐グループホールディングス株式会社 Procédé pour l'exploitation minière de ressources souterraines à l'aide de particules hydrolysables
JP2016190950A (ja) * 2015-03-31 2016-11-10 富士ゼロックス株式会社 樹脂組成物および樹脂成形体
WO2017145539A1 (fr) * 2016-02-26 2017-08-31 東洋製罐グループホールディングス株式会社 Copolymère de polyoxalate et son procédé de production

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004143400A (ja) * 2002-03-25 2004-05-20 Ube Ind Ltd 高分子量ポリオキサレート及びその製造方法
JP2005097606A (ja) * 2003-09-05 2005-04-14 Ube Ind Ltd 生分解性射出成形物
JP2006290937A (ja) * 2005-04-06 2006-10-26 Yamaguchi Univ セルロース系廃棄物−ポリオキサレートコンポジット
WO2015098926A1 (fr) * 2013-12-24 2015-07-02 東洋製罐グループホールディングス株式会社 Polyoxalate et procédé de production associé
WO2016080142A1 (fr) * 2014-11-19 2016-05-26 東洋製罐グループホールディングス株式会社 Procédé d'exploitation de ressources souterraines, et agant de blocage hydrolysable destiné à être utilisé dans ledit procédé
WO2016129501A1 (fr) * 2015-02-12 2016-08-18 東洋製罐グループホールディングス株式会社 Procédé pour l'exploitation minière de ressources souterraines à l'aide de particules hydrolysables
JP2016190950A (ja) * 2015-03-31 2016-11-10 富士ゼロックス株式会社 樹脂組成物および樹脂成形体
WO2017145539A1 (fr) * 2016-02-26 2017-08-31 東洋製罐グループホールディングス株式会社 Copolymère de polyoxalate et son procédé de production

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