JP2011057919A - Polyurethane gel - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a gel which contains a large amount of an ionic liquid and causes no leakage of the liquid. <P>SOLUTION: The polyurethane-gel molded material is characterized in that a molded material from polyurethane resin (A) having a content of an oxyethylene group of 20-90 wt.% is impregnated with ionic liquid (B), wherein the molded material contains 150-300 wt.% of ionic liquid (B). Preferably, the polyurethane-gel molded material has ionic liquid (B) of an imidazolium salt. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

The present invention relates to a polyurethane gel. More particularly, the present invention relates to a polyurethane gel made of a polyurethane resin impregnated with an ionic liquid.

  Conventionally, in order to create a gel by stably storing an ionic liquid in a solid state, a method of hardening using a gelling agent of polyvinylidene fluoride-hexafluoropropylene copolymer is known (Patent Document 1). ing.

JP 2007-28148 A

However, the above method is time consuming, has a complicated process, and has a problem that the content of the ionic liquid is small. What is a method for stably and abundantly containing a high functionality low molecular weight ionic liquid? It's hard to say.
An object of the present invention is to provide a gel containing a large amount of an ionic liquid without leakage.

  The inventors of the present invention have arrived at the present invention as a result of intensive studies to solve the above problems. That is, the present invention is a polyurethane gel molded article obtained by impregnating an ionic liquid (B) into a molded article of a polyurethane resin (A) having an oxyethylene group content of 20 to 90% by weight. is there.

The polyurethane gel molded product of the present invention has the following effects.
(1) Contains a large amount of ionic liquid and does not leak.
(2) Excellent mechanical strength.

Polyurethane resin (A)
(A) contains 20 to 90% by weight of an oxyethylene group (hereinafter sometimes referred to as OE group).
When the content (x) of the oxyethylene group in (A) is less than 20% by weight, the saturated volume expansion coefficient of the ionic liquid of the polyurethane gel molded product is lowered.
When (x) exceeds 90% by weight, the mechanical strength of the polyurethane gel molded product is lowered.
(X) is preferably 30 to 80% by weight, more preferably 40 to 70% by weight.
Here, the saturated volume expansion coefficient of an ionic liquid means what was described in the following Example.

The oxyethylene group-containing polymer polyol (a) preferably has an oxyethylene group content of 15 to 100% by weight. Here, the content of oxyethylene groups in (a) is calculated assuming that the content of oxyethylene groups in polyoxyethylene (polyethylene glycol) is 100% by weight.
The number average molecular weight of (a) is preferably Mn 300 to 6,000, more preferably Mn 500 to 5,000 from the viewpoint of water resistance of the polyurethane gel molded product and reactivity with the isocyanate component (b).
As (a), a polymer polyol (a1) having at least one ethylenically unsaturated group in the molecular side chain, and a polymer polyol (a2) having no ethylenically unsaturated group in the molecular side chain , (A1) and (a2).

The number of hydroxyl groups in the oxyethylene group-containing polymer polyol (a) is 2 to 3 or more, preferably 2 to 3.
The number of the ethylenically unsaturated groups in the molecular side chain in (a1) is preferably 1 to 10 from the viewpoint of the mechanical strength and saturated volume expansion ratio of the polyurethane gel described later. Examples of the ethylenically unsaturated group include an allyl group and / or a (meth) acryloyl group, and an allyl group is preferred from the viewpoint of water resistance.

(A1): (a11) Ethylene oxide unsaturated group-containing low molecular polyol (c1) [carbon number (hereinafter abbreviated as C) 6-20] ethylene oxide (hereinafter abbreviated as EO) [or EO and allyl glycidyl Ether (hereinafter abbreviated as AGE)] adduct, (a12) EO of a compound containing two or more active hydrogen atoms, or AGE (or AGE and EO) adduct, and mixtures thereof.

Examples of the ethylenically unsaturated group-containing low molecular polyol (c1) include C6-20 (poly) allyl ether [glycerin (hereinafter abbreviated as GR) monoallyl ether, trimethylolpropane (hereinafter abbreviated as TMP). Monoallyl ether, pentaerythritol (hereinafter abbreviated as PE) monoallyl ether, PE diallyl ether, etc.], (poly) (meth) acrylate [GR mono (meth) acrylate, TMP mono (meth) Acrylate, PE di (meth) acrylate, etc.]. Of these, GR- and TMP monoallyl ether are preferred from the viewpoint of water resistance.

Examples of the high molecular polyol (a2) having no ethylenically unsaturated group in the molecular side chain include the following (c2) EO adduct of low molecular polyol not containing ethylenically unsaturated group.

The low molecular polyol (c) refers to those having a number average molecular weight (hereinafter referred to as Mn) of less than 300. Examples of (c) include the following.
(C1) Ethylenically unsaturated group-containing low molecular polyol [carbon number (hereinafter abbreviated as C) 6-20] is as described above.
(C2) The low molecular polyol [carbon number (hereinafter abbreviated as C) 6-20] which does not contain an ethylenically unsaturated group is as described below.

(C21) Non-phenolic low molecular weight polyols C2-20 or more divalent alcohols such as C2-12 aliphatic divalent alcohols [(di) alkylene glycols such as ethylene glycol -Diol, diethylene glycol, propylene glycol, dipropylene glycol, 1,2-, 2,3-, 1,3- and 1,4-butanediol, 1,6-hexanediol, neo Pentyl glycol and 3-methylpentanediol (hereinafter abbreviated as EG, DEG, PG, DPG, BD, HD, NPG and MPD, etc.), dodecandiol, etc.], C6-10 alicyclic divalent alcohol -L [1,4-cyclohexanediol, cyclohexanedimethanol, etc.], C8-20 araliphatic alcohol [xylylene glycol, bis (hydroxyethyl) Benzene etc.]; trivalent to octavalent or higher polyhydric alcohols such as (cyclo) alkane polyols and their intramolecular or intermolecular dehydrates [GR, TMP, PE, sorbitol ( Hereinafter abbreviated as SO) and dipentaerythritol (hereinafter abbreviated as DPE), 1,2,6-hexanetriol, erythritol, cyclohexanetriol, mannitol, xylitol, sorbitan, di GR and other poly-GR, etc.], saccharides and derivatives thereof [for example, sucrose, glucose, fructose, mannose, lactose, and glycosides (methyl glucoside, etc.)] and the like.

(C22) Multivalent phenols C6-18 divalent phenols such as monocyclic divalent phenols (hydroquinone, catechol, resorcinol, urciool, etc.), bisphenols (bisphenols) A, -F, -C, -B, -AD and -S, dihydroxybiphenyl, 4,4'-dihydroxydiphenyl-2,2-butane and the like), and condensed polycyclic divalent phenol [dihydroxynaphthalene (1 , 5-dihydroxynaphthalene, etc.), binaphthol, etc.]; and trivalent to octavalent or higher polyhydric phenols, such as monocyclic polyhydric phenols (pyrogallol, phloroglucinol, and monovalent) Or an aldehyde or ketone (formaldehyde, glutaraldehyde, glycerin) of divalent phenol (phenol, cresol, xylenol, resorcinol, etc.) Axal, acetone) low condensate (phenol or cresol novolak resin, intermediate of resole, polyphenol obtained by condensation reaction of phenol and glyoxal or glutaraldehyde, and resorcin Polyphenol obtained by condensation reaction between acetone and acetone)

  The oxyethylene group-containing form in the polymer polyol molecule constituting the oxyethylene group-containing polymer polyol (a) may be either a block form and / or a random form. A block shape is preferable from the viewpoint of rate.

The isocyanate (b) includes the following poly (n = 2 to 3, preferably 2) isocyanates.
(B1) Aromatic polyisocyanate C (excluding carbon in the NCO group, the same shall apply hereinafter) 6 to 20, such as tolylene diisocyanate (diisocyanate is abbreviated as DI in the following) (TDI), 4,4′- and / or 2,4′-diphenylmethane DI (MDI), naphthylene DI (NDI);
(B2) araliphatic polyisocyanates C8-15, such as diethylbenzene DI, m- and / or p-xylylene DI (XDI), α, α, α ′, α′-tetramethylxylylene DI (TMXDI);
(B3) Aliphatic polyisocyanate C2-18, such as ethylene DI, tetramethylene DI, hexamethylene DI (HDI), dodecamethylene DI, 2,2,4-trimethylhexane DI, lysine DI, 2,6-diisocyanatome Tilcaproate, bis (2-isocyanatoethyl) fumarate, bis (2-isocyanatoethyl) carbonate;
(B4) Cycloaliphatic polyisocyanate C4-15, such as isophorone DI (IPDI), dicyclohexylmethane-4,4′-DI (hydrogenated MDI), cyclohexane DI, methylcyclohexane DI (hydrogenated TDI), bis (2- Isocyanatoethyl) 4-cyclohexene-1,2-dicarboxylate;
(B5) Modified products (carbodiimide modification, uretdione modification, uretoimine modification, urea modification, burette modification, isocyanurate modification, etc.) of the polyisocyanates of (b1) to (b4) above.
Of these, (b4) is preferable from the viewpoint of water resistance, alicyclic DI is more preferable, and IPDI and hydrogenated MDI are particularly preferable.

    The ethylenically unsaturated group concentration based on the total weight of the polyol components [high molecular polyol (a) and low molecular polyol (c)] in the polyurethane resin (A) is determined by the mechanical strength of the polyurethane gel molded product described later and From the viewpoint of the ionic liquid storage rate of the molded polyurethane gel, it is preferably 0 to 1 equivalent / 1000 g, more preferably 0.1 to 0.5 equivalent / 1000 g.

The polyurethane resin (A) can be obtained by reacting a low molecular weight polyol (c) as required, using the oxyethylene group-containing high molecular weight polyol (a) and the polyisocyanate (b) as components.
Examples of the production method (A) include the following methods.
(1) A method in which (a) is obtained by reacting (a) and (b), and if necessary, charging (c) all at once.
(2) (a) and (b) are reacted to produce a urethane prepolymer having an isocyanate group, and (a), (c), or a mixture of (a) and (c) and the urethane prepolymer To obtain (A).
(3) A method in which (a) is obtained by reacting (a) and (b) to produce a urethane prepolymer having an isocyanate group, and subjecting the urethane prepolymer to an elongation reaction in (c).
Among these, the method (2) is preferable.
The method (2) will be described in detail. A prepolymer is produced by a known method using oxyethylene group-containing polymer polyol (a) and polyisocyanate (b) as components, and this is used as the main component. A mixture of (a), (c), or a mixture of (a) and (c) with an additive such as a catalyst or an antioxidant is used as a curing agent component. The said main ingredient component and a hardening | curing agent component are mixed with a two-component mixing and casting machine, and both components are cast into a mold to obtain a molded product of polyurethane gel. The equivalent ratio of the active hydrogen-containing group of the curing agent to the isocyanate group of the main agent is usually 0.7 to 1.5, preferably 0.9 to 1.3.
When the polyurethane resin (A) is crosslinked, it is preferable that (a) and / or (c) have an ethylenically unsaturated group and a crosslinking agent is added to the curing agent component.

  In the production of the polyurethane resin (A), the reaction ratio [NCO / OH equivalent ratio] of the isocyanate (b) and the polyol is from the viewpoint of the mechanical strength of the polyurethane gel described later and the extrusion moldability during the production of the water-swellable sealing material. Preferably it is 0.8 / 1-1.0 / 1, More preferably, it is 0.9 / 1-0.98 / 1. The reaction ratio is a polyol for finally obtaining the polyurethane resin (A), and (b) is a total reaction ratio of each component, and usually varies depending on a production method (one-shot method or prepolymer method) described later. There is nothing.

  Examples of the production method of (A) include methods (one-shot method, prepolymer method, etc.) usually used for producing a polyurethane resin, and among these, from the viewpoint of less variation in quality of (A). Preferred is the prepolymer method. Next, (A) by the prepolymer method and a method for producing a polyurethane gel comprising (A) and (B) will be exemplified.

First, a part of the polyol and the isocyanate component (b) are preferably urethanated at 70 to 150 ° C. by an ordinary method at an NCO / OH equivalent ratio of 1.2 / 1 to 10/1. A terminal prepolymer is obtained. The NCO group content (% by weight) in the prepolymer is preferably 2 to 15%, more preferably 3 to 10%, from the viewpoint of sharpening the molecular weight distribution and increasing the molecular weight of the polyurethane resin.
Next, two pressure-resistant reaction tanks (I) with pumps that can continuously feed liquid, mixer section (II) that continuously mixes each component fed from two reaction tanks (I), and ( II) Using the continuous mixing device provided with the discharge part (III) for discharging the liquid mixed in (II), one of the pressure-resistant reaction tanks in (I) is charged with the prepolymer, and the other reaction tank is filled with the above-mentioned prepolymer. The remainder of the polyol is charged, and after reducing the pressure, further purging with nitrogen, the temperature is adjusted to a desired temperature.

The adjusted two liquids are continuously supplied to the mixer section (II) and mixed. The liquid feed ratio [NCO / OH equivalent ratio] between the prepolymer and the remainder of the polyol is preferably the polyol for finally obtaining the polyurethane resin (A) as described above, and (b) the total reaction ratio of each component. Is a ratio of 0.8 / 1 to 1.0 / 1, more preferably 0.9 / 1 to 0.98 / 1, and the liquid feeding speed is the reaction speed of urethanization and the mixing property in the mixer section. From the viewpoint of the above, it is preferably carried out at 1 to 50 kg / min, more preferably 5 to 20 kg / min.
Since the liquid mixed in the mixer part (II) is continuously supplied to the discharge part (III), a metal mold is attached to the discharge port in advance and the supplied mixed liquid is received. The received mixed liquid is sealed, and then cured in a curing furnace, preferably at 50 to 100 ° C., more preferably at 60 to 90 ° C., for 0.5 to 10 hours to obtain a polyurethane resin (A) molded product. .

  The Mooney viscosity [unit: ML (1 + 4) 100 ° C.] of the polyurethane resin (A) is preferably 30 to 70 from the viewpoint of mechanical strength after water expansion of the water-expandable sealing material described later and extrusion moldability at the time of production. More preferably, it is 35-65. Here, the Mooney viscosity is a value obtained by measurement according to a test method described later.

In producing the polyurethane resin (A), various urethanization reaction catalysts can be used as necessary.
Examples of the catalyst include tertiary amines [C6-20, such as triethylamine, triethylenediamine, bis (dimethylaminoethyl) ether, N-methylmorpholine, dimethylaminomethylphenol, N-methyl-N-dimethylaminoethylpiperazine, pyridine and the like. ] And these acid block compounds, metal salts of carboxylic acids (C2-20) (sodium acetate, lead octylate, zinc octylate, iron octylate, bismuth octylate, iron naphthenate, cobalt naphthenate, stannous octoate , Dibutyltin dilaurate, etc.), alkali metal or alkaline earth metal alkoxide or phenoxide (C1-12, such as sodium methoxide, sodium phenoxide), quaternary ammonium salt (C4-12, such as tetraethylhydroxyl) Nmonium), imidazole compounds (C3-12, such as imidazole, 2-ethyl-4-methylimidazole), chelate metal salts (C5-20, such as acetylacetone zinc, acetylacetone iron), and organic compounds containing metals such as tin and antimony Examples thereof include metal compounds (C3-30, such as tetraphenyltin and tributylantimony oxide). These catalysts can be used alone or in combination.
The amount of the urethanization catalyst used is usually 5% or less, preferably 0.001 to 3%, based on the weight of (A).

As the crosslinking agent, those usually used for rubber vulcanization may be used. Sulfur, sulfur chloride, organic peroxides (C4-24, such as benzoyl peroxide, dicumyl peroxide, methyl ethyl ketone peroxide, lauryl peroxide, cyclohexanone) Peroxide, t-butyl perbenzoate, t-butyl hydroperoxide, t-butylbenzene peroxide, cumene hydroperoxide, t-butyl peroctoate), oxime (C6-20, eg p-quinone dioxime, p , P′-dibenzoylquinonedioxime), metal oxides (magnesia, risurge, etc.), alkylphenol resins [trade name “Tacquirol 201” [manufactured by Taoka Chemical Co., Ltd.], etc.], polythiol compounds [TMP trithioglycolate , TMP tri (3-mercap Propionate), glycol dimercaptopropionate, glycol dimercaptoacetate, PE tetrathioglycolate, diPE hexa (3-mercaptopropionate), etc.], polyamine compounds (aldehyde-amine condensates, guanidine compounds, etc.), azo Examples thereof include azobisisobutyronitrile, 2-t-butylazo-2-cyano-4-methylpentane, 4-t-butylazo-4-cyano-valeric acid, and the like. These crosslinking agents can be used alone or in combination of two or more. Of these cross-linking agents, sulfur, combined use of sulfur with other cross-linking agents and peroxides are preferred from the industrial viewpoint such as ease of handling, and sulfur is more preferred.

The polyurethane resin molded product of the present invention can be obtained by kneading the polyurethane resin (A) with a crosslinking agent using, for example, a Banbury mixer or a kneader, and extrusion molding or press molding.
The molding temperature is set according to the type of the crosslinking agent, and is preferably 140 to 200 ° C. from the viewpoint of shortening the crosslinking time and the mechanical strength of the polyurethane resin molded product.

Ionic liquid (B)
The ionic liquid (B) used in the present invention refers to a substance that becomes liquid at a temperature of 100 ° C. or lower, and is preferably a liquid that becomes liquid at a temperature of 50 ° C. or lower.

The ionic liquid (B) is formed from a cation component and an anion component. Although there is no restriction | limiting in particular as a cation component which forms this ionic liquid (B), It is preferable to use the cation containing various quaternary nitrogen from a viewpoint of improving the chemical stability and electroconductivity of an ionic liquid. For example, ammonium and its derivatives, imidazolium and its derivatives, imidazolinium and its derivatives, pyridinium and its derivatives, pyrrolidinium and its derivatives, pyrrolinium and its derivatives, pyrazinium and its derivatives, pyrimidinium and its derivatives, triazonium and its derivatives, Triazinium and its derivatives, triazine derivative cations, quinolinium and its derivatives, isoquinolinium and its derivatives, indolinium and its derivatives, quinoxalinium and its derivatives, piperazinium and its derivatives, oxazolinium and its derivatives, thiazolinium and its derivatives, morpholinium and its derivatives Selected from the group consisting of derivatives and piperazine and its derivatives It is preferable to use one kind even without. Other cationic components include phosphonium (tetraalkylphosphonium, tetraarylphosphonium, etc.) sulfonium (trialkylsulfonium, triarylsulfonium, etc.) and the like.
Of the above cationic components, imidazolium and its derivatives are more preferred.
Here, the derivative means that at least one hydrogen atom that can be substituted in the basic compound is an aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group, hydroxyl group, carbonyl group, carboxyl group. A compound substituted with a substituent such as a group, an ether group, an ester group, an acyl group or an amino group.

Examples of anionic components forming this ionic liquid (B) include BF ₄ ⁻ , PF ₆ ⁻ , PCl ₆ ⁻ , BCl ₄ ⁻ , AsF ₆ ⁻ , SbF ₆ ⁻ , AlF ₄ ⁻ , AlCl ₄ ⁻ , NbF ₆ ^−. , HSO ₄ ⁻ , ClO ₄ ⁻ , CH ₃ SO ₃ ⁻ , FeCl ₄ ⁻ , FeBr ₄ ⁻ , CH ₃ COO ⁻ , Ph (COOH) COO ⁻ , (C ₂ H ₅ ) ₂ PO ₄ ⁻ , HC (NH ₂ ) (R) COO ⁻ (R is an alkyl group having 1 to 6 carbon atoms, hydroxyl group, carboxyl group, amino group, imino group, aromatic group, amide group, hydrogen atom), N (CN) ₂ ⁻ , N (SO ₂ F ₂ ) ⁻ , C (CN) ₃ ⁻ , Cl ⁻ , Br ⁻ , I ⁻ , F (HF) _n ⁻ (wherein n represents a numerical value of 1 or more and 4 or less), N (RfSO ₂ ) ₂ ⁻ , C (RfSO ₂ ) ₃ ⁻ , RfSO ₃ ⁻ , RfCO ₂ ⁻ , ROSO ₃ ^{− and the} like Nion can be used. Rf contained in the anion represented by N (RfSO ₂ ) ₂ ⁻ , C (RfSO ₂ ) ₃ ⁻ , RfSO ₃ ⁻ , or RfCO ₂ ⁻ represents a C 1-12 fluoroalkyl group, trifluoromethyl, Examples include pentafluoroethyl, heptafluoropropyl, and nanofluorobutyl. ROSO ₃ ^- R contained in represents an alkyl group having 1 to 12 carbon atoms.
Among these, BF ₄ ⁻ , PF ₆ ⁻ , ROSO ₃ ⁻ and AlCl ₄ ⁻ are preferable.

Examples of preferred ionic liquid (B) include the following ionic liquids.
1-ethyl-3-methylimidazolium tetrafluoroborate, 1-propyl-3-methylimidazolium tetrafluoroborate, 1-butyl-3-methylimidazolium tetrafluoroborate, 1-hexyl-3 -Methylimidazolium tetrafluoroborate, 1-butyl-3-methylimidazolium hexafluorophosphonate, 1-hexyl-3-methylimidazolium hexafluorophosphonate, 1-ethyl-3-methylimidazole Lithium methyl sulfate, 1-butyl-3-methylimidazolium methyl sulfate, 1-ethyl-3-methylimidazolium ethyl sulfate, 1-butyl-3-methylimidazolium ethyl sulfate 1-ethyl-3-methylimidazolium tetrachloroaluminate, 1-butyl -3-methylimidazolium tetrachloro aluminate - but DOO and the like, but are not limited to. Of these, 1-ethyl-3-methylimidazolium tetrafluoroborate and 1-butyl-3-methylimidazolium tetrafluoroborate are particularly preferred.

  The ionic liquid (B) is preferably contained in an amount of 100 to 500% by weight, more preferably 150 to 300% by weight, based on the weight of the polyurethane resin molded product.

  The method of obtaining the polyurethane gel by impregnating the polyurethane resin (A) with the ionic liquid (B) is particularly limited as long as (A) and (B) are brought into contact with each other and (A) is impregnated with (B). However, there is a method of impregnating the urethane resin with the ionic liquid by immersing the whole or part of the molded product of the polyurethane resin (A) in the ionic liquid (B) and immersing it. The immersion temperature is preferably 0 to 50 ° C., more preferably normal temperature (10 to 40 ° C.). The immersion time is preferably 1 day to 7 days, more preferably 1 day to 3 days. The pressure of the atmosphere to immerse is 0.1 MPa under atmospheric pressure.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these. In addition, the part in an Example represents a weight part and% represents weight%.

The composition and symbols of the raw materials used in Examples and Comparative Examples are as follows.
Polymer polyol (a2-1): EO / PO (weight ratio 30/70) random adduct of bisphenol A (Mn5,100) Oxyethylene group content 20% Hydroxyl value is 22 mgKOH / g
Polymer polyol (a2-2): bis / phenol A EO / PO (weight ratio 70/30) random adduct (Mn 4,000) Oxyethylene group content 60% Hydroxyl value is 28 mgKOH / g
Polymer polyol (a2-3): EO / PO of bisphenol A (weight ratio 80/20) random adduct (Mn 4,000) Oxyethylene group content 80% Hydroxyl value is 28 mgKOH / g
Polymer polyol (a2-4): Polyethylene glycol (Mn 1,500) oxyethylene group content: 100% Hydroxyl value: 75 mgKOH / g
Polyisocyanate (b-1): 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl = isocyanate (isophorone diisocyanate, abbreviated as IPDI)
Catalyst (1): Lead octylate crosslinking agent (1): Sulfur ionic liquid (B-1): 1-ethyl-3-methylimidazolium tetrafluoroborate melting point 14.6 ° C. [manufactured by Kanto Chemical Co., Inc. ]
Ionic liquid (B-2): 1-ethyl-3-methylimidazolium trifluoromethyl sulfonate melting point-10.0 ° C. [manufactured by Kanto Chemical Co., Inc.]
Ionic liquid (B-3): Trihexyl tetradecylphosphonium tetrafluoroborate melting point 17.0 ° C. [manufactured by Kanto Chemical Co., Inc.]

Production Example 1
A fully dry pressure-resistant reaction vessel was charged with 53 parts of DEG and 2 parts of potassium hydroxide, sealed, and then dehydrated under reduced pressure at 120 ° C. to confirm that the water content was 0.05% or less. Under reduced pressure, the temperature in the container was cooled to 95 ° C., and then 500 parts of EO was introduced from the bottom of the container in the range of 90 to 100 ° C. and reacted at 90 to 100 ° C. for 2 hours. After reducing the pressure inside the vessel, 114 parts of AGE were introduced from the bottom of the vessel in the range of 90 to 100 ° C. and reacted at 90 to 100 ° C. for 2 hours. After depressurizing the inside of the container, PO333 parts were further introduced from the bottom of the container in the range of 90 to 100 ° C. and reacted at 90 to 100 ° C. for 2 hours (block addition). After cooling to 70 ° C., nitrogen was blown from the top of the reaction vessel, and 1% water of the reaction product was added and stirred and mixed in an atmosphere with a gas phase oxygen concentration of 0%. Next, Kyodo word 600 [trade name, manufactured by Kyowa Chemical Industry Co., Ltd. same as below. 5 parts were added and stirred and mixed at 70 to 80 ° C. to adsorb the potassium hydroxide catalyst, followed by filtration and removal under nitrogen pressure (gas phase oxygen concentration 0%). To the filtrate, 0.5 part of 2,6-di-t-butyl-4-methylphenol (antioxidant) was added and heated at a gas phase oxygen concentration of 0% to 95-105 ° C. and then dehydrated under reduced pressure. . When the water content became 0.05%, the mixture was immediately cooled to obtain a polymer polyol (a1-1) having two ethylenically unsaturated groups in the molecular side chain. The hydroxyl value of (a1-1) was 60 mgKOH / g (hereinafter, only numerical values are shown).

Production Example 2
A fully dry pressure-resistant reaction vessel was charged with 53 parts of DEG and 2 parts of potassium hydroxide, sealed, and then dehydrated under reduced pressure at 120 ° C. to confirm that the water content was 0.05% or less. Under reduced pressure, the temperature in the container was cooled to 95 ° C., and then a premixed mixture of 750 parts of EO, 83 parts of PO, and 114 parts of AGE was introduced from the bottom of the container in the range of 90 to 100 ° C. for 2 hours, 90 to 100 ° C. (Random addition). After cooling to 70 ° C., the same procedure as in Production Example 1 was performed to obtain a polymer polyol (a1-2) having two ethylenically unsaturated groups in the molecular side chain. The hydroxyl value of (a1-2) was 70.

The raw materials (polymer polyol, isocyanate) shown in Table 1 were reacted at 120 ° C. for 3 hours in a nitrogen atmosphere to obtain a prepolymer component (main component). Subsequently, the raw materials (polymer polyol, catalyst, crosslinking agent) shown in Table 1 were mixed to obtain a curing agent component.
The main ingredient component and the curing agent component are mixed with a two-component mixing and casting machine (Hyojin Equipment Co., Ltd.), both components are poured into a mold, and a polyurethane resin molded product (dimension 200 × 200 × 20 mm) is obtained. Obtained. The equivalent ratio of the active hydrogen-containing group of the curing agent to the isocyanate group of the main agent was 0.98.

Examples 1-10
(Impregnation of ionic liquid into polyurethane substrate)
The ionic liquid (B) stored in a glass container by cutting the urethane resin molded product 5 produced as described above into a sheet [Vertical × Horizontal × Thickness = 100 × 100 × 2 mm] with a slicer (Leader) The polyurethane resin was impregnated with an ionic liquid by being immersed in 1000 ml and immersed at room temperature (25 ° C.) for 3 days to obtain a polyurethane gel molded product.

Comparative Example 1
1-ethyl-3-methylimidazolium tetrafluoroborate was gelled using a tetrahydrofuran solution in which a polyvinylidene fluoride-hexafluoropropylene copolymer was dissolved as a gelling agent to obtain a gel-like composition. . The gelation conditions were 1-ethyl-3-methylimidazolium tetrafluoroborate, the mass concentration of the gelling agent with respect to 10 ml was 1.2 g, and at 60 ° C. in a reactor equipped with a reflux condenser. Heated for 3 hours to obtain a homogeneous solution. Tetrahydrofuran was evaporated to obtain a molded product comprising a gel composition.

Comparative Example 2
First, after adding 100 ppm of dibutyltin dilauric acid catalyst to 10 ml of 1-ethyl-3-methylimidazolium tetrafluoroborate, polyoxyethylene glycerin (molecular weight 1200) is mixed, and then in a molar ratio of 1: 1. A mixed solution was prepared by adding tolylene diisocyanate. Mixing was performed so that the total amount of polyoxyethylene glycerin and tolylene diisocyanate was 6 wt% with respect to the liquid. And the gel-like molding was obtained by leaving the said liquid mixture for 30 minutes at the temperature of 80 degreeC.
Evaluation was performed. The results are shown in Table 1.

From the results of Table 1, the polyurethane gel of the present invention has no liquid leakage compared with the comparative one, exhibits a high saturated volume expansion ratio, mechanical strength (A hardness) and electrical conductivity (AC impedance method), and is an excellent substrate. It can be seen that it is.

<Performance evaluation method>
<1. A hardness measurement method>
In accordance with “Method for testing hardness of vulcanized rubber and thermoplastic rubber” described in JISK6253, four 2 mm thick sheets obtained above were stacked and measured with a type A durometer.

<2. Conductivity measurement method>
Polyurethane gel molding [Vertical x Horizontal x Thickness = 100 x 100 x 2.0 mm], according to JIS 7204, "High Resistivity Meter High Lester UP" or "Low Resistivity Meter Low Lester GP" [Equipment Name, Any Were also manufactured by Mitsubishi Chemical Co., Ltd.], and the surface resistivity was measured under the conditions of an applied voltage of 500 V and 1 minute for “High Lester UP” and an applied voltage of 90 V and 15 seconds for “Low Lester GP”.

<3. Method for measuring saturated volume expansion ratio>
A 20 × 20 × 2 mm test piece was taken from the polyurethane resin, and the volume when this test piece was immersed in an ionic liquid at 25 ° C. was measured at regular intervals (immersion method). The expansion ratio was calculated, and the volume expansion ratio when the amount of increase in the volume expansion ratio per day was 0.01% or less was defined as the saturated volume expansion ratio of the test piece.
Volume expansion ratio (times) = volume after immersion in ionic liquid / volume before immersion in ionic liquid

<4. Test Method for Liquid Leakage Test>
A pressure of 5 MPa was applied to a test piece of polyurethane gel 20 × 20 × 2 mm in which an ionic liquid was immersed using a vise, and it was confirmed that there was no change in weight before and after the pressure was applied.

The polyurethane gel of the present invention can be widely applied in the heat dissipation sheet, electromagnetic wave shield, actuator base material, shock absorbing element, battery material, various materials fields requiring conductivity, and for fuel cells, etc. It can be applied to other proton conducting media and is extremely useful.

Claims (5)

A polyurethane gel molded article obtained by impregnating an ionic liquid (B) into a molded article of a polyurethane resin (A) having an oxyethylene group content of 20 to 90% by weight. The polyurethane gel molded product according to claim 1, comprising 150 to 300% by weight of the ionic liquid (B). The polyurethane gel molded product according to claim 1 or 2, wherein the ionic liquid (B) is an imidazolium salt. It comprises a polyurethane resin (A) having a content of oxyethylene groups of 20 to 90% by weight by reaction and molding using oxyethylene group-containing polymer polyol (a) and polyisocyanate (b) as essential components. A method for producing a polyurethane gel molded article, which comprises producing a molded article and impregnating the polyurethane resin (A) molded article with an ionic liquid (B) to obtain a polyurethane gel molded article. The method for producing a polyurethane gel molded product according to claim 4, wherein the polyol component has an ethylenically unsaturated group and a crosslinking reaction is carried out when producing a molded product comprising the polyurethane resin (A).