WO2010001898A1 - Procédé de fabrication de polyester hyper-ramifié, procédé de fabrication de polyuréthane et polyuréthane - Google Patents

Procédé de fabrication de polyester hyper-ramifié, procédé de fabrication de polyuréthane et polyuréthane Download PDF

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Publication number
WO2010001898A1
WO2010001898A1 PCT/JP2009/061971 JP2009061971W WO2010001898A1 WO 2010001898 A1 WO2010001898 A1 WO 2010001898A1 JP 2009061971 W JP2009061971 W JP 2009061971W WO 2010001898 A1 WO2010001898 A1 WO 2010001898A1
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Prior art keywords
polyurethane
measurement
hbpe
polyester
producing
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PCT/JP2009/061971
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English (en)
Japanese (ja)
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卓 本九町
睦久 古川
謙 小椎尾
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国立大学法人長崎大学
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Priority to JP2010519078A priority Critical patent/JPWO2010001898A1/ja
Publication of WO2010001898A1 publication Critical patent/WO2010001898A1/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
    • C08G63/40—Polyesters derived from ester-forming derivatives of polycarboxylic acids or of polyhydroxy compounds, other than from esters thereof
    • C08G63/42—Cyclic ethers; Cyclic carbonates; Cyclic sulfites; Cyclic orthoesters
    • 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
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4291—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from polyester forming components containing monoepoxy 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
    • C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
    • C08G83/002—Dendritic macromolecules
    • C08G83/005—Hyperbranched macromolecules
    • 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 method for producing a highly branched highly branched polyester, a method for producing a highly biodegradable polyurethane using this highly branched polyester, and a highly biodegradable polyurethane.
  • Plastic products containing polyurethane which do not corrode, exist for a long time and have an adverse effect on the environment.
  • agricultural polymer films are used to protect seedlings from wind and rain, but recovery of these polymer films after growth requires a great deal of effort.
  • this polymer film is incinerated or illegally dumped because it is difficult to reuse, and it is not only an environmental problem but also a social problem.
  • biodegradable plastics Focusing on biodegradable plastics, they are decomposed with the growth of agricultural products, so they do not need to be recovered. Therefore, agricultural polymers can be created by creating new materials containing ester groups that have oil resistance, physical properties excellent in mechanical and thermal properties, and biodegradability and hydrolyzability among polymers. It is considered that the problem of film recovery can be improved (see, for example, Patent Document 1).
  • preparation methods of biodegradable copolymers, biodegradation methods and their application to fibers, films, pots for planting, multi films for agriculture are proposed, and degradation of polycaprolactone and polytetramethylene adipate is also reported. .
  • Hyperbranched polyester for example, Boltorn (registered trademark) of Perstorp Corporation having a branched structure in a dendritic shape is proposed.
  • polyurethane can not be produced well only by using hyperbranched polyesters, and even when producing polyurethane from Boltron (registered trademark) described above, linear polyester was mixed. As a result of incorporating the poorly biodegradable linear polyester, the biodegradability of the resulting polyurethane was not necessarily good.
  • a method for producing a multi-branched polyester which makes it possible to easily produce a multi-branched polyester at low cost, and biodegradation using this multi-branched polyester
  • the present invention provides a method for producing a polyurethane excellent in properties and a polyurethane excellent in biodegradability.
  • the method for producing a multi-branched polyester of the present invention is to react glycidol with a cyclic acid anhydride to synthesize a multi-branched polyester.
  • the method for producing the polyurethane of the present invention comprises the steps of synthesizing the multi-branched polyester by the above-mentioned method for producing the multi-branched polyester of the present invention, and reacting the multi-branched polyester with diisocyanate to synthesize the polyurethane.
  • the hyperbranched polyester excellent in biodegradability is used by this, the hyperbranched polyurethane excellent in biodegradability can be manufactured easily.
  • the polyurethane of the present invention can be obtained by reacting glycidol with a cyclic acid anhydride to synthesize a hyperbranched polyester, and reacting the hyperbranched polyester with a diisocyanate. Since the polyurethane of the present invention can be obtained by reacting a hyperbranched polyester with a diisocyanate, it has properties not found in general linear polyurethanes and is excellent in biodegradability. .
  • the multi-branching polyester can be produced at low cost because it is not necessary to use an excessive amount of monomers.
  • the gelation does not occur with the progress of the reaction, the multi-branched polyester can be produced easily at low cost with a good yield.
  • polyurethane of the present invention it is possible to easily produce multi-branched polyurethane, and therefore, it has characteristics not found in general linear polyurethanes and is excellent in biodegradability. Can be realized.
  • polyurethane of the present invention it is possible to realize a polyurethane which has characteristics not found in general linear polyurethanes and is excellent in biodegradability.
  • glycidol is reacted with a cyclic acid anhydride to produce a multi-branched polyester (HBPE).
  • Glycidol has a three-membered cyclic ether at one end of the chain molecule and has a primary alcohol at the other end of the chain molecule, as shown in the chemical formula below.
  • cyclic acid anhydrides examples include glutaric anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, and adipic anhydride.
  • a multi-branching polyester can be manufactured by using one or more sorts of materials chosen from these materials, for example.
  • the chemical structure of these cyclic acid anhydrides is as the following chemical formula.
  • these raw materials are mixed in a solvent, and a catalyst is added as needed.
  • a solvent for example, tetrahydrofuran (THF) can be used.
  • a catalyst for example, triethylamine (TEA) can be used.
  • the reaction is carried out using these raw materials (glycidol and cyclic acid anhydride), a solvent and a catalyst to obtain a hyperbranched polyester (HBPE).
  • HBPE hyperbranched polyester
  • the above-described Boltorn (registered trademark) and the like are limited to one type of raw material, and in Patent Document 1 and Patent Document 2, the ratio of two types of monomers is 1: 1.
  • the mixing ratio of the two types of cyclic monomers (glycidol and cyclic acid anhydride) of the raw material is not limited to 1: 1, and other ratios are possible.
  • the structure of the multi-branched polyester to be produced can be changed by changing the mixing ratio of the two types of cyclic monomers (glycidol and cyclic acid anhydride) of the raw materials. This makes it possible to produce multi-branched polyesters of various structures. For example, a hyperbranched polyester of the following structure is obtained.
  • the hyperbranched polyester and diisocyanate are reacted to synthesize polyurethane by using the hyperbranched polyester obtained by the above-mentioned production method.
  • hyperbranched polyester is used, hyperbranched polyurethane can be easily manufactured.
  • multi-branching polyurethane which has the characteristic which is not in general linear polyurethane and is excellent in biodegradability.
  • the polyurethane of the present invention can be obtained by reacting a hyperbranched polyester with a diisocyanate using the hyperbranched polyester obtained by the above-mentioned production method.
  • a highly biodegradable polyurethane that has characteristics not found in general linear polyurethanes.
  • hexamethylene diisocyanate can be used, for example.
  • hexamethylene diisocyanate can be used, for example.
  • other diisocyanates may be used.
  • these raw materials are mixed in a solvent.
  • a solvent for example, tetrahydrofuran (THF) can be used.
  • the reaction is carried out using these raw materials (multibranched polyester and diisocyanate) and a solvent to obtain a polyurethane.
  • hyperbranched polyesters were actually produced by the production method of the present invention, and polyurethanes were further produced from the hyperbranched polyesters, and the properties of the resulting hyperbranched polyesters and polyurethanes were investigated.
  • Raw material> Glycidol (2,3-epoxy-1-propanol) and glutaric anhydride were used without purification. For these, tetrahydrofuran (THF; boiling point 66 ° C.) as a solvent and triethylamine (TEA; boiling point 89.7 ° C .; all manufactured by Wako Pure Chemical Industries, Ltd.) as a catalyst were distilled and used. The chemical structures of these raw materials are shown below.
  • glycidol and cyclic acid anhydride react one by one to form the compound of (I). Furthermore, the terminal carboxyl group of the compound of (I) attacks either the ⁇ carbon or ⁇ carbon of the glycidyl group of another glycidol to open the glycidyl group.
  • the structure is (II)
  • the structure is (III). Three structures are obtained from the structure of (II). Two structures are obtained from the structure of (III). There are cases of straight connection and cases of branching. These processes are repeated to obtain a dendritic branched multi-branched polyester as shown at the end.
  • a sample of the reaction process was taken at arbitrary time intervals, and proton nuclear magnetic resonance ( 1 H-NMR) measurement was performed.
  • the sampling time was 0 hour (when the raw materials were mixed), 1 hour, 2 hours, 6 hours, 12 hours, 24 hours, 36 hours, 48 hours, 60 hours and 72 hours.
  • 0.09 g of the collected sample was dissolved in 0.6 ml of deuterated dimethyl sulfoxide (DMSO-d 6 ) to obtain a measurement sample.
  • DMSO-d 6 deuterated dimethyl sulfoxide
  • the number of integrations was eight using a superconducting multi-nuclide magnetic resonance apparatus JNM-GX400 (400 MHz, manufactured by Nippon Denshi Co., Ltd.).
  • the chemical shift of the A 'proton is expected to shift to a lower magnetic field due to the ring-opening addition of the carboxyl group to the glycidyl group, since the signal expected to be D', D '' methine proton appears It is from. However, detailed structural identification has not been possible. In addition, the signal exhibited by D ′, D ′ ′ methine proton appears in a wide range of 3.9 to 4.1 ppm. The reason for this is considered that the carboxyl group attacked either the ⁇ carbon or the ⁇ carbon of the glycidyl group shown in the above chemical reaction formula, and the molecular skeleton became very complicated, and the spectrum also became broad overall. Be
  • Carbon nuclear magnetic resonance spectrum ( 13 C-NMR) measurement Carbon nuclear magnetic resonance spectrum ( 13 C-NMR) measurement of the reaction product was performed. About 0.1 g of the reaction product was dissolved in 0.6 ml of deuterated dimethyl sulfoxide (DMSO-d 6 ) to prepare a measurement sample. The measurement was performed using a superconducting multinuclide magnetic resonance apparatus JNM-GX400 (400 MHz, manufactured by Nippon Denshi Co., Ltd.), and the number of integrations was 512.
  • JNM-GX400 400 MHz, manufactured by Nippon Denshi Co., Ltd.
  • GPC Gel permeation chromatography
  • THF is used for the dissociation solution
  • Shodex GPC KF 804 (separation range 500 to 4.0 ⁇ 10 5 Da) is used for the column
  • a differential refractive index (RI) detector is used for the detector, with a column temperature of 40 .2 at a flow rate of 1.0 ml / min.
  • the analysis was performed according to the following procedure using the GPC curve obtained by the measurement.
  • (1) The obtained GPC curve is divided every elution time.
  • (2) A baseline is drawn at the rising and the end of the peak of the obtained GPC curve to determine the height (hi) to the curve.
  • M n number average molecular weight
  • M w weight average molecular weight
  • M w / M n molecular weight distribution
  • Monodispersed polystyrene was used as a standard sample.
  • the relationship between the molecular weight of polystyrene and the elution time (Elution time) is shown in Table 1, and the prepared calibration curve is shown in FIG.
  • each unit shown in the chemical formula and the 13 C-NMR spectrum of the obtained product are shown in FIG.
  • Each spectrum obtained was assigned by a known method.
  • a signal of d 1 ′ ′ carbon of 1,3 -linear unit (L 1, 3 ) was observed.
  • the carbon signal was observed at 75.9 ppm and the T 1,3 m carbon signal was observed.
  • a carbon signal of the ester group was observed at 172.8 ppm and a carbon signal of the terminal carboxyl group at 174.6 ppm.
  • the GPC elution curve of the reaction product is shown in FIG. 4, and the number average molecular weight (M n ), weight average molecular weight (M w ) and molecular weight distribution (M w / M n ) of the obtained HBPE were estimated from the GPC elution curve. And Table 4 respectively.
  • the molecular weight and molecular weight distribution of the product were 1900, 2800 and 1.47, respectively.
  • the actual molecular weight of the multi-branched polymer may be larger than the actual molecular weight, as the hydroxyl group of the branched polymer rarely forms an aggregate, so the value estimated in terms of standard polystyrene may be larger. For this reason, it is considered that gel permeation chromatography-multi-angle laser light scattering (GPC-MALLS) measurement needs to be performed in order to obtain an accurate molecular weight value of the product.
  • GPC-MALLS gel permeation chromatography-multi-angle laser light scattering
  • polyurethane was produced using hyperbranched polyester (HBPE).
  • HBPE hyperbranched polyester
  • HDI hexamethylene diisocyanate
  • THF Waako Pure Chemical Industries, Ltd.
  • the property of the obtained product was a sheet having a high elastic modulus as compared to a yellow transparent common polyurethane (PU).
  • sample name was defined as HBPE-HDI using HBPE which is an abbreviation of polyol which is a raw material, and HDI which is an abbreviation of isocyanate.
  • the weight of each sample was measured in air and water, and the density was calculated from the measured weight. The weight measurement was performed 5 times for each sample, and the average value of the remaining 3 measurements excluding the maximum value and the minimum value was taken as the density.
  • the density (d p ) of the sample was determined by the following equation (1).
  • W is the weight of the unswollen sample
  • W b is the weight of the dry sample.
  • swelling degree q was calculated
  • Q is the volume ratio of the sample at equilibrium swelling of the following formula (5)
  • W a is the weight of the equilibrium swelling sample
  • d s DMA density in the density of the solvent (60 °C d s 0. 940 g / cm 3
  • density d s of toluene 0.864 g / cm 3
  • d p is the density of the sample.
  • FT-IR Fast Fourier transform infrared spectroscopy
  • DSC Differential scanning calorimetry
  • the measurement was performed by cooling the sample to about -140 ° C with liquid nitrogen, under the conditions of a temperature range -140 to 250 ° C, a nitrogen flow rate of 20 ml / min, and a temperature rising rate of 10 ° C / min.
  • Thermogravimetric analysis (TGA) measurement was performed. About 15 mg of the obtained sample was weighed, placed in an open aluminum cell, and measured using a Thermo Plus Station (manufactured by Rigaku Denki Co., Ltd.) and a thermobalance (TG8120). The measurement conditions were a temperature rise rate of 10 ° C./min, a temperature range of 25 ° C. to 550 ° C., and the measurement atmosphere was an air atmosphere.
  • Test test A 5 mm wide strip-like test piece was cut out from the HBPE-HDI sheet and used for measurement. The width and thickness of the test piece were measured at three places with a micrometer, and the initial cross-sectional area was calculated using their average value. Then, a tensile test was performed using a Tensilon universal tester (RTE-1210) manufactured by Orientec Co., Ltd. to measure a stress-strain relationship. The measurement was performed indoors using a camera using a 5 kgf load cell, an initial sample length of 20 mm, and a crosshead speed of 5 mm / min. The following formulas (6) and (7) were used to calculate the Young's modulus.
  • HBPE-HDI Hydrolyzability of HBPE-HDI was investigated. After the weight of the obtained HBPE-HDI was measured, the HBPE-HDI was immersed in a 1 mmol / L aqueous solution of sodium hydroxide and kept as it is for 77 days. After 77 days, the weight was measured to check for weight change.
  • FIG. 1A shows the spectrum of both 4000 ⁇ 3000 cm -1
  • Figure 5B shows the spectrum of both 2000 ⁇ 1400 cm -1.
  • the density of the obtained HBPE-HDI (multi-branched polyurethane) was almost the same as the density obtained with the linear polyester.
  • the obtained HBPE-HDI was sufficiently polymerized because the gel fraction value was sufficiently high.
  • thermograms of HBPE used as a polyol and the obtained HBPE-HDI as a result of differential scanning calorimetry (DSC) measurement are shown in FIG.
  • T g glass transition temperatures
  • HBPE-HDI glass transition temperatures
  • the T g of HBPE-HDI is compared to the T g of HBPE, it shifted to the high temperature side. This is considered to be due to the decrease in molecular mobility due to the chemical bonding of HBPE by the reaction and the increase in molecular weight. Also, the melting peak due to the crystalline component was not observed.
  • thermogravimetric analysis (TGA) measurement temperature dependence of mass loss in thermogravimetric analysis measurement of the obtained HBPE-HDI is shown in FIG. As shown in FIG. 7, HBPE-HDI thermally decomposed at about 250 ° C. and weight loss started.
  • TGA thermogravimetric analysis
  • HBPE-HDI hyperbranched polyurethane
  • the result of the measurement of hydrolyzability was a weight loss of 31% at 77 days. It is about 2 months when planting seeds of crops and the need for protection by vinyl is about 2 months after sprouting and weight loss of 31% means that the polyurethane is in a shabby state, so when the crops germinate. There is no need to peel off the protected vinyl.
  • polyurethane obtained from linear polyester does not decompose at all in a 1 mmol / L aqueous solution of sodium hydroxide.
  • the 1 mmol / L aqueous sodium hydroxide solution is a weakly basic environment, and that HBPE-HDI decomposes in such a weak basic environment and has sufficient degradability. Therefore, this HBPE-HDI (multi-branched polyurethane) can realize a polyurethane having excellent biodegradability.

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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)
  • Polyesters Or Polycarbonates (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Biological Depolymerization Polymers (AREA)

Abstract

L'invention porte sur un procédé de fabrication d'un polyester hyper-ramifié par lequel un polyester hyper-ramifié peut être facilement obtenu à faible coût. Un polyester hyper-ramifié est obtenu par réaction de glycidol avec un anhydride d'acide cyclique, permettant ainsi de synthétiser un polyester hyper-ramifié.
PCT/JP2009/061971 2008-07-04 2009-06-30 Procédé de fabrication de polyester hyper-ramifié, procédé de fabrication de polyuréthane et polyuréthane WO2010001898A1 (fr)

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Cited By (5)

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WO2014030253A1 (fr) * 2012-08-24 2014-02-27 Kohiyama Noboru Composé durcissable de type ester, composition contenant ledit composé, produit durci et procédé de production d'un composé durcissable de type ester
JP2014098160A (ja) * 2014-01-20 2014-05-29 Noboru Kobiyama エステル型硬化性化合物、それを含有する組成物及び硬化物、並びにエステル型硬化性化合物の製造方法
CN105418887A (zh) * 2015-12-14 2016-03-23 厦门大邦瑞达印染材料有限公司 一种用于酸性染料的阴离子型聚氨酯固色剂、其制备方法及应用
CN107266687A (zh) * 2017-07-11 2017-10-20 上海维凯光电新材料有限公司 用于紫外光固化涂料的抗污助剂
CN107337800A (zh) * 2017-07-11 2017-11-10 上海乘鹰新材料有限公司 抗污助剂及其在紫外光固化涂料中的应用

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WO2014030253A1 (fr) * 2012-08-24 2014-02-27 Kohiyama Noboru Composé durcissable de type ester, composition contenant ledit composé, produit durci et procédé de production d'un composé durcissable de type ester
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JP5581458B2 (ja) * 2012-08-24 2014-08-27 登 小檜山 エステル型硬化性化合物、それを含有する組成物及び硬化物、並びにエステル型硬化性化合物の製造方法
KR101490091B1 (ko) 2012-08-24 2015-02-04 노보루 고히야마 에스테르형 경화성 화합물, 그것을 함유하는 조성물 및 경화물, 및 에스테르형 경화성 화합물의 제조 방법
CN103764705B (zh) * 2012-08-24 2015-12-02 小桧山登 酯型固化性化合物、含有其的组合物及固化物、以及酯型固化性化合物的制造方法
JP2014098160A (ja) * 2014-01-20 2014-05-29 Noboru Kobiyama エステル型硬化性化合物、それを含有する組成物及び硬化物、並びにエステル型硬化性化合物の製造方法
CN105418887A (zh) * 2015-12-14 2016-03-23 厦门大邦瑞达印染材料有限公司 一种用于酸性染料的阴离子型聚氨酯固色剂、其制备方法及应用
CN107266687A (zh) * 2017-07-11 2017-10-20 上海维凯光电新材料有限公司 用于紫外光固化涂料的抗污助剂
CN107337800A (zh) * 2017-07-11 2017-11-10 上海乘鹰新材料有限公司 抗污助剂及其在紫外光固化涂料中的应用
CN107337800B (zh) * 2017-07-11 2019-10-15 上海乘鹰新材料有限公司 抗污助剂及其在紫外光固化涂料中的应用
CN107266687B (zh) * 2017-07-11 2019-11-22 上海维凯光电新材料有限公司 用于紫外光固化涂料的抗污助剂

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