WO2018151057A1 - Copolyéther polyol, polyuréthane et procédé de production de copolyéther polyol - Google Patents

Copolyéther polyol, polyuréthane et procédé de production de copolyéther polyol Download PDF

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Publication number
WO2018151057A1
WO2018151057A1 PCT/JP2018/004735 JP2018004735W WO2018151057A1 WO 2018151057 A1 WO2018151057 A1 WO 2018151057A1 JP 2018004735 W JP2018004735 W JP 2018004735W WO 2018151057 A1 WO2018151057 A1 WO 2018151057A1
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WIPO (PCT)
Prior art keywords
copolyether polyol
unit derived
polyurethane
copolyether
monomer unit
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PCT/JP2018/004735
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English (en)
Japanese (ja)
Inventor
明展 竹田
浩介 千田
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株式会社クラレ
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Priority to CN201880009990.1A priority Critical patent/CN110291132B/zh
Priority to JP2018568503A priority patent/JPWO2018151057A1/ja
Publication of WO2018151057A1 publication Critical patent/WO2018151057A1/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
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • 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
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/04—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers only
    • C08G65/06—Cyclic ethers having no atoms other than carbon and hydrogen outside the ring
    • C08G65/16—Cyclic ethers having four or more ring atoms
    • C08G65/20—Tetrahydrofuran

Definitions

  • the present invention relates to a copolyether polyol, a polyurethane containing a unit derived from the copolyether polyol, and a method for producing the copolyether polyol.
  • Polyether polyol is often used as a soft segment component of polyurethane.
  • polyurethane resins using polytetramethylene ether glycol (PTMG) which is a polymer of tetrahydrofuran (THF)
  • PTMG polytetramethylene ether glycol
  • THF tetrahydrofuran
  • PTMG has a molecular weight of 500 to 4,000, which is usually used as a component of polyurethane, has a melting point in the range of 20 to 40 ° C., and crystallizes at normal temperature and below, so handling and workability There is a problem.
  • a copolyether polyol which is a copolymer of THF and alkyltetrahydrofuran (alkyl THF) such as 3-methyltetrahydrofuran (MTHF), is known as an improved product that solves the above problems of PTMG.
  • This copolyether polyol has a low melting point, and those having a molecular weight that is usually used maintain a liquid state at room temperature (Patent Document 1, Non-Patent Documents 1, 2, etc.).
  • An object of the present invention is to provide a copolyether polyol having excellent strength, elongation and low-temperature elastic recovery property when used as a raw material for polyurethane and suppressing bleeding out, and a unit derived from the copolyether polyol. It is in providing the manufacturing method of the polyurethane containing and the said copolyether polyol.
  • copolyether polyols containing conventional THF-derived monomer units and alkyl THF-derived monomer units have a large molecular weight distribution (Mw / Mn) and low terminal hydroxyl group purity,
  • Mw / Mn molecular weight distribution
  • terminal hydroxyl group purity low terminal hydroxyl group purity
  • the present invention relates to the following [1] to [5].
  • a copolyether polyol comprising a monomer unit derived from THF and a monomer unit derived from alkyl THF, having a terminal hydroxyl group purity of 97.0 to 100.0% and a molecular weight distribution (Mw / Mn) Is a copolyether polyol having a ratio of 1.05 to 2.5.
  • Mw / Mn molecular weight distribution
  • copolyether polyol according to any one of [1] to [3], which comprises cationic ring-opening polymerization of THF and alkyl THF in the presence of acetic acid, acetic anhydride and a cation exchange resin, followed by deacetylation
  • a manufacturing method of A method for producing a copolyether polyol, wherein a mass ratio of acetic acid and acetic anhydride used in the cationic ring-opening polymerization is acetic acid / acetic anhydride 30/70 to 70/30.
  • the resulting polyurethane when used as a polyurethane raw material, the resulting polyurethane has excellent strength, elongation and elastic recovery at low temperatures, and suppresses bleeding out, a unit derived from the copolyether polyol. And a method for producing the copolyether polyol.
  • the copolyether polyol of the present invention includes a monomer unit derived from THF and a monomer unit derived from alkyl THF, the terminal hydroxyl group purity is 97.0 to 100.0%, and the molecular weight distribution (Mw / Mn) is 1.05 to 2.5.
  • Alkyl THF is one in which one or more hydrogen atoms of THF are substituted with an alkyl group.
  • the alkyl group is preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms, still more preferably an alkyl group having 1 to 2 carbon atoms, and particularly preferably a methyl group.
  • the number of alkyl groups is not particularly limited, but is preferably 2 or less, more preferably 1.
  • the position of the alkyl group is not particularly limited, but the 3-position is preferred.
  • alkyl THF examples include 2-methyltetrahydrofuran, 3-methyltetrahydrofuran (MTHF), 2-ethyltetrahydrofuran, 3-ethyltetrahydrofuran, 2-n-propyltetrahydrofuran, 3-n-propyltetrahydrofuran, 2,3-dimethyltetrahydrofuran, etc. Is mentioned. From the viewpoints of economy and polymerizability, MTHF or 2-methyltetrahydrofuran is preferable, and MTHF is more preferable. These may be used alone or in combination of two or more.
  • the number average molecular weight (Mn) of the copolyether polyol of the present invention is preferably 500 or more, more preferably 800 or more, 1,500 or more, 2,000 or more, and further 2,100 or more. Moreover, it is preferable that it is 10,000 or less, and it is more preferable that it is 4,500 or less.
  • the number average molecular weight (Mn) and the weight average molecular weight (Mw) of the copolyether polyol can be determined by gel permeation chromatography (GPC) analysis, and specifically determined by the method described later in the examples. be able to.
  • the copolyether polyol of the present invention has a terminal hydroxyl group purity of 97.0 to 100.0%, preferably 98.0 to 100.0%, more preferably 99.0 to 100.0%, More preferably, it is 99.5 to 100.0%.
  • a terminal hydroxyl group purity 97.0 to 100.0%, preferably 98.0 to 100.0%, more preferably 99.0 to 100.0%, More preferably, it is 99.5 to 100.0%.
  • a macrocyclic polyether in which terminal hydroxyl groups are ether-bonded is by-produced. According to the study by the present inventors, this tendency becomes particularly prominent when copolymerizing with alkyl THF. Therefore, conventional copolyether polyols containing monomer units derived from THF and monomer units derived from alkyl THF are It was found that the terminal hydroxyl group purity was low.
  • the macrocyclic polyether does not have a hydroxyl group, it cannot be urethaned and remains unreacted in the polyurethane, which causes a decrease in the strength and elongation of the polyurethane and a bleed-out.
  • the copolyether polyol having the terminal hydroxyl group purity can be obtained by a production method described later.
  • “terminal hydroxyl group purity” refers to “ ⁇ copolyetherpolyol mass / (copolyetherpolyol mass + macrocyclic polyether mass) ⁇ ⁇ 100 (%)”, and matrix-assisted laser desorption / ionization flight. It can be measured by time-type mass spectrometry (MALDI-TOFMS analysis), and specifically by the method described later in the examples.
  • the copolyether polyol of the present invention has a molecular weight distribution (Mw / Mn) of 1.05 to 2.5, preferably 1.05 to 2.3, more preferably 1.05 to 2.1. .
  • Mw / Mn molecular weight distribution
  • the copolyether polyol having the above molecular weight distribution (Mw / Mn) can be obtained by a production method described later.
  • the molar ratio of the monomer unit derived from THF and the monomer unit derived from alkyl THF is from the viewpoint of melting point and ease of polymerization.
  • Monomer unit 88/12 to 50/50 is preferable, and 86/14 to 70/30 is more preferable.
  • the method for producing a copolyether polyol according to the present invention comprises a step of deacetylating THF and alkyl THF in the presence of acetic acid, acetic anhydride and a cation exchange resin, followed by deacetylation.
  • the copolyether polyol of the present invention can be produced by the above production method.
  • the cation exchange resin functions as an acid catalyst.
  • the cation exchange resin that can be used is not particularly limited, but those having a sulfo group are preferred, and those composed of a tetrafluoroethylene skeleton and a perfluoro side chain having a sulfo group (such as Nafion (registered trademark) NR50). More preferred. These may be used alone or in combination of two or more.
  • the amount of the cation exchange resin used is not particularly limited, but is preferably 0.01 to 30% by mass, more preferably 0.05 to 15% by mass, and further preferably 0.1 to 10% by mass of the reaction mixture.
  • acetic acid / acetic anhydride 30/70 to 70/30, preferably 40/60 to 60/40, more preferably 45 / It is 55 to 55/45, more preferably 47/53 to 53/47, and particularly preferably 48/52 to 52/48.
  • the amount of acetic acid used is not particularly limited, but is preferably 0.01 to 30% by mass, more preferably 0.05 to 15% by mass, and 0.1 to 10% by mass with respect to the total amount of THF and alkyl THF used. Is more preferable.
  • a solvent may be used.
  • the solvent is not particularly limited as long as it does not inhibit the reaction.
  • aliphatic hydrocarbons such as hexane, heptane and octane; aromatic hydrocarbons such as benzene, toluene, xylene and mesitylene; halogenated aromatic hydrocarbons such as chlorobenzene and fluorobenzene; diethyl ether, diisopropyl ether, dibutyl ether and dioxane 1,2-dimethoxyethane, diglyme, triglyme, tetraglyme and other ethers; dichloromethane, chloroform, 1,2-dichloroethane and other halogenated aliphatic hydrocarbons; acetonitrile and the like. These may be used alone or in combination of two or more.
  • the reaction temperature in the cationic ring-opening polymerization is preferably ⁇ 30 to 120 ° C., more preferably ⁇ 10 to 100 ° C., and further preferably 0 to 80 ° C.
  • the cation exchange resin is preferably separated and removed, and unreacted THF, alkyl THF, acetic acid and acetic anhydride are removed under reduced pressure.
  • THF and alkyl THF are subjected to cationic ring-opening polymerization and then deacetylated.
  • the deacetylation is preferably performed using a basic substance.
  • Examples of basic substances used for deacetylation include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide; alkali metal alcoholates such as lithium methoxide, sodium methoxide, and potassium methoxide; Examples thereof include hydroxides of alkaline earth metals such as magnesium hydroxide, calcium hydroxide and barium hydroxide; organic basic compounds such as triethylamine and pyridine. Of these, alkali metal hydroxides or alkali metal alcoholates are preferred.
  • the amount of the basic substance used is not particularly limited, but is preferably 0.01 to 20% by mass, more preferably 0.05 to 10% by mass, and more preferably 0.1% to 0.1% by mass with respect to the diacetate obtained by cationic ring-opening polymerization. More preferably, it is ⁇ 5% by mass.
  • Deacetylation is preferably performed in the presence of an alcohol such as methanol, ethanol or isopropyl alcohol while distilling off the generated alkyl acetate.
  • an alcohol such as methanol, ethanol or isopropyl alcohol while distilling off the generated alkyl acetate.
  • a solvent may be used.
  • the solvent is not particularly limited as long as it does not inhibit the reaction.
  • aliphatic hydrocarbons such as hexane, heptane and octane
  • aromatic hydrocarbons such as benzene, toluene, xylene and mesitylene
  • halogenated aromatic hydrocarbons such as chlorobenzene and fluorobenzene
  • diethyl ether, diisopropyl ether, dibutyl ether and tetrahydrofuran Ethers such as dioxane, 1,2-dimethoxyethane, diglyme, triglyme, and tetraglyme
  • halogenated aliphatic hydrocarbons such as dichloromethane, chloroform, 1,2-dichloroethane, and the like. These may be used alone or in combination of two or more.
  • the reaction temperature at the time of deacetylation is preferably 0 to 150 ° C, more preferably 10 to 130 ° C, and further preferably 20 to 120 ° C.
  • Deacetylation can be carried out under normal pressure or reduced pressure.
  • Copolyether polyols can be obtained.
  • the polyurethane of the present invention contains units derived from the copolyether polyol of the present invention.
  • the polyurethane of the present invention can be prepared, for example, by a method of reacting the copolyether polyol of the present invention with a polyisocyanate to synthesize a prepolymer containing an isocyanate group and then reacting with an active hydrogen atom-containing compound, It can be obtained by a one-shot method in which ether polyol, polyisocyanate, and active hydrogen atom-containing compound are simultaneously reacted. Known conditions may be applied mutatis mutandis for various conditions during the reaction.
  • the polyisocyanate that can be used is not particularly limited, but generally polyurethanes such as tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate, naphthylene diisocyanate, hydrogenated diphenylmethane diisocyanate, and the like.
  • Polyisocyanate used for the synthesis of These may be used alone or in combination of two or more.
  • the active hydrogen atom-containing compound that can be used is a compound having two or more hydroxyl groups or amino groups.
  • examples of such compounds include ethylenediamine, propylenediamine, butylenediamine, hexamethylenediamine, cyclohexylenediamine, piperazine, 2-methylpiperazine, phenylenediamine, tolylenediamine, xylenediamine, and 3,3′-dichloro-4.
  • KF-802.5 and KF-803L manufactured by Showa Denko KK were connected in series as measurement columns, and the analysis was performed under the conditions of THF as the solvent, 0.9 ml / min as the flow rate, and 40 ° C. as the column temperature.
  • polystyrene standard type: PS-oligomer kit manufactured by Tosoh Corporation was used.
  • Example 1 In a reaction vessel equipped with a stirrer, a thermometer and a nitrogen seal tube, 281.4 g (3.90 mol) of THF, 105.7 g (1.23 mol) of MTHF, 7.6 g (0.07 mol) of acetic anhydride, 7.3 g (0.12 mol) of acetic acid and 20 g of Nafion (registered trademark) NR50 were added and stirred at 23 ° C. for 29 hours. After the reaction, Nafion (registered trademark) NR50 was filtered off and concentrated under reduced pressure to distill off unreacted monomers, acetic acid and acetic anhydride.
  • Nafion (registered trademark) NR50 was filtered off and concentrated under reduced pressure to distill off unreacted monomers, acetic acid and acetic anhydride.
  • 30 g of methanol and 0.03 g (0.75 mmol) of sodium hydroxide were added to the obtained residue, and the reaction was carried out for 4 hours while distilling off methanol and generated methyl acetate while heating under reflux.
  • 0.045 g (0.75 mmol) of acetic acid and 100 g of toluene were added, the organic layer was washed 5 times with 20 g of distilled water, and the organic layer was concentrated under reduced pressure to obtain 42.2 g of a copolyether polyol.
  • the obtained polyol had a number average molecular weight (Mn) of 3,169 and a molecular weight distribution (Mw / Mn) of 3.08.
  • Mn number average molecular weight
  • Mw / Mn molecular weight distribution
  • Example 2 In a reaction vessel equipped with a stirrer, a thermometer, and a nitrogen seal tube, 79.2 g (25.5 mmol) of the copolyether polyol obtained in Example 1 and 10.2 g of 40,4′-diphenylmethane diisocyanate (MDI) (40 8 mmol), and a prepolymerization reaction was performed at 60 ° C. for 5 hours.
  • MDI 40,4′-diphenylmethane diisocyanate
  • DMAc dimethylacetamide
  • Example 2 it replaced with the copolyether polyol obtained in Example 1, and performed the same operation as Example 2 except having used the copolyether polyol obtained in Comparative Example 1, and obtained the polyurethane solution. It was.
  • Example 2 In Example 2, it replaced with the copolyether polyol obtained in Example 1, and performed the same operation as Example 2 except having used the copolyether polyol of the comparative example 2, and obtained the polyurethane solution.
  • Example 2 The polyurethane solutions obtained in Example 2 and Comparative Examples 3 and 4 were coated on a polypropylene sheet using a bar coater and dried with hot air at 80 ° C. for 24 hours to obtain a polyurethane film having a thickness of 100 ⁇ m. From this film, a JIS No. 4 dumbbell-shaped test piece and a 5 cm ⁇ 5 mm strip-shaped test piece were prepared. This test piece was subjected to various tensile tests using an Instron 5566 type tensile tester. The breaking strength and breaking elongation were JIS No.
  • the polyurethane obtained in Example 2 has improved elastic recovery at low temperatures as compared with the polyurethane obtained in Comparative Example 3. This is because, in Comparative Example 3, since the molecular weight distribution (Mw / Mn) in the used copolyether polyol is large, the high molecular weight polyurethane based on the copolyether polyol having a molecular weight considerably higher than the number average molecular weight (Mn). This is thought to be due to the relatively large amount. In addition, the polyurethane obtained in Example 2 has improved strength and elongation, and further suppressed bleed out, compared with the polyurethane obtained in Comparative Example 4.
  • the polyurethane using the copolyether polyol of the present invention is useful as a raw material for elastic fibers, for example, because it is superior in strength, elongation, and elastic recovery at low temperatures and suppresses bleed out as compared with conventional products.
  • the copolyether polyol of the present invention can be suitably used for various uses such as industrial chemicals and raw materials in addition to the use of polyurethane raw materials.

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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)
  • Polyurethanes Or Polyureas (AREA)
  • Polyethers (AREA)

Abstract

La présente invention concerne : un copolyéther polyol qui contient une unité monomère dérivée de tétrahydrofurane et une unité monomère dérivée d'un alkyltétrahydrofurane, et qui présente une pureté en groupements hydroxyle terminaux de 97,0 % à 100,0 % et une distribution de masse moléculaire (Mw/Mn) de 1,05 à 2,5 ; un polyuréthane qui contient une unité dérivée de ce copolyéther polyol ; ainsi qu'un procédé de production de ce copolyéther polyol.
PCT/JP2018/004735 2017-02-16 2018-02-09 Copolyéther polyol, polyuréthane et procédé de production de copolyéther polyol WO2018151057A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CN201880009990.1A CN110291132B (zh) 2017-02-16 2018-02-09 共聚聚醚多元醇、聚氨基甲酸酯和共聚聚醚多元醇的制造方法
JP2018568503A JPWO2018151057A1 (ja) 2017-02-16 2018-02-09 コポリエーテルポリオール、ポリウレタンおよびコポリエーテルポリオールの製造方法

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JP2017026953 2017-02-16
JP2017-026953 2017-02-16

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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS52138598A (en) * 1976-03-31 1977-11-18 Du Pont Process for preparing poly*tetramethylene ether*glycol
JPS61291624A (ja) * 1985-06-18 1986-12-22 Sanyo Chem Ind Ltd ポリテトラメチレングリコ−ルの製造法
JPH0117486B2 (fr) * 1980-04-11 1989-03-30 Bee Aa Esu Efu Ag
JPH11269261A (ja) * 1998-03-23 1999-10-05 Mitsubishi Chemical Corp ポリテトラメチレンエーテルグリコールの製造方法
JP2001220439A (ja) * 1999-11-29 2001-08-14 Mitsubishi Chemicals Corp ポリアルキレンエーテルグリコールジエステルの連続製造法
JP2001302785A (ja) * 2000-04-18 2001-10-31 Mitsubishi Chemicals Corp 環状オリゴマーの少ないポリテトラメチレンエーテルグリコール及びその製造方法
JP2005036047A (ja) * 2003-07-16 2005-02-10 Mitsubishi Chemicals Corp 共重合ポリエーテルポリオールの製造方法
JP2012524149A (ja) * 2009-04-15 2012-10-11 インビスタ テクノロジーズ エス エイ アール エル テトラヒドロフランの重合体を製造するための改良された触媒

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4163115A (en) * 1976-03-31 1979-07-31 E. I. Du Pont De Nemours And Company Preparation of esters of poly-(tetramethylene ether) glycol

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS52138598A (en) * 1976-03-31 1977-11-18 Du Pont Process for preparing poly*tetramethylene ether*glycol
JPH0117486B2 (fr) * 1980-04-11 1989-03-30 Bee Aa Esu Efu Ag
JPS61291624A (ja) * 1985-06-18 1986-12-22 Sanyo Chem Ind Ltd ポリテトラメチレングリコ−ルの製造法
JPH11269261A (ja) * 1998-03-23 1999-10-05 Mitsubishi Chemical Corp ポリテトラメチレンエーテルグリコールの製造方法
JP2001220439A (ja) * 1999-11-29 2001-08-14 Mitsubishi Chemicals Corp ポリアルキレンエーテルグリコールジエステルの連続製造法
JP2001302785A (ja) * 2000-04-18 2001-10-31 Mitsubishi Chemicals Corp 環状オリゴマーの少ないポリテトラメチレンエーテルグリコール及びその製造方法
JP2005036047A (ja) * 2003-07-16 2005-02-10 Mitsubishi Chemicals Corp 共重合ポリエーテルポリオールの製造方法
JP2012524149A (ja) * 2009-04-15 2012-10-11 インビスタ テクノロジーズ エス エイ アール エル テトラヒドロフランの重合体を製造するための改良された触媒

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CN110291132A (zh) 2019-09-27
TW201835156A (zh) 2018-10-01
JPWO2018151057A1 (ja) 2019-12-12

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