JP2008156626A - Method for producing polyalkylene polyol - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyalkylene polyol to be used for a polyurethane resin used for a water-swellable sealing material excellent in moldability. <P>SOLUTION: The polyalkylene polyol (A1) is produced by adding an epoxide comprised of ethylene oxide and allylglycidyl ether to an active hydrogen-containing compound in the presence of an alkali metal hydroxide, then dehydrating the product after removing the alkali metal hydroxide using an adsorbent in an atmosphere containing less than 1.0 volume% gas phase oxygen, and the resulted polyol (A1) contains a 0-0.3 wt.% by-product comprised of an allylglycidyl ether polymer. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a method for producing a polyalkylene polyol. More specifically, the present invention relates to a method for producing a polyalkylene polyol having a very low content of by-products composed of allyl glycidyl ether multimers.

Conventionally, it is known that a polyurethane resin having an ethylenically unsaturated bond in a molecule is added to rubber and vulcanized and used as a water-swellable sealing material (see, for example, Patent Document 1). The polyurethane resin is obtained by reacting a polyol component composed of a polyalkylene polyol having an ethylenically unsaturated bond in the molecule with an isocyanate component composed of a polyisocyanate.
As a method for producing the polyalkylene polyol, a metal complex obtained by reacting organoaluminum-water-acetylacetone as a catalyst (for example, see Patent Document 2) or an alkali metal hydroxide (for example, see Patent Document 3) is used. A method of adding an alkylene oxide and allyl glycidyl ether to an active hydrogen-containing compound is known.

JP 57-119972 A Japanese Examined Patent Publication No. 45-12866 JP-A-8-193128

  However, in any of the production methods using a metal complex or an alkali metal hydroxide, there is a problem that a by-product content composed of a multimer of allyl glycidyl ether is increased and the resulting polyalkylene polyol becomes a crosslinked product. As a result, the polyurethane resin formed from the polyalkylene polyol becomes a cross-linked product, and the dispersion to a polymer elastic body such as rubber is remarkably deteriorated. In particular, the shape is not stable when extruded, and the water expandability When molded as a sealing material, there has been a problem that uniform water expansibility cannot be obtained.

  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, in the present invention, after adding an epoxide composed of ethylene oxide and allyl glycidyl ether to an active hydrogen-containing compound in the presence of an alkali metal hydroxide, the gas phase oxygen concentration is 1.0 vol% or less in an atmosphere. The alkali metal hydroxide is removed using an adsorbent and dehydrated, and the content of the by-product consisting of a multimer of allyl glycidyl ether is 0 to 0.3% by weight. It is a manufacturing method of a polyalkylene polyol (A1).

The method for producing the polyalkylene polyol (A1) of the present invention, the water-swellable polyurethane resin formed from the (A1), and the water-swellable sealing material formed by molding the water-swellable polyurethane resin have the following effects. Play.
(1) Low by-product content consisting of multimers of allyl glycidyl ether.
(2) The water-swellable polyurethane resin formed from the polyol component and the isocyanate component consisting of (A1) has good dispersibility in the polymer elastic body and excellent moldability.
(3) A water-swellable sealing material formed by molding the water-swellable polyurethane resin is less susceptible to strength reduction after water swelling and has excellent long-term water stopping properties.

  In the production method of the present invention, the epoxide to be added to the active hydrogen-containing compound includes ethylene oxide (hereinafter abbreviated as EO) and allyl glycidyl ether (hereinafter abbreviated as AGE), and if necessary, the number of carbon atoms (hereinafter abbreviated as C). You may add 3-4 alkylene oxide (it abbreviates as AO below). The addition type of these different types of epoxides may be either random addition and / or block addition, but block addition is preferred from the viewpoint of water-stopping property of the water-swellable sealing material.

  The content (% by weight) of the EO unit constituting (A1) is preferably 15 to 99 from the viewpoint of the volumetric water expansion ratio of the water-expandable polyurethane resin described later and the strength after water expansion of the water-expandable sealing material described later. %, More preferably 20 to 95%, particularly preferably 25 to 90%.

  The content (% by weight) of the AGE unit constituting (A1) is preferably 1 to 65% from the viewpoint of the strength after water expansion of the water-expandable sealing material described later and the moldability of the water-expandable polyurethane resin described later. More preferably, it is 3 to 60%, and particularly preferably 5 to 50%.

Examples of the C3-4 AO include propylene oxide (hereinafter abbreviated as PO), 1,2-, 1,3-, 1,4- and 2,3-butylene oxide, and combinations of two or more thereof. Is mentioned.
If necessary, the content (% by weight) of the C3-4 AO unit constituting (A1) is preferably 25% or less, more preferably 22% or less from the viewpoint of the volumetric water expansion ratio of the water-swellable polyurethane resin described later. Particularly preferably, it is 20% or less, and most preferably 15% or less.

Examples of the active hydrogen-containing compound include water and C2 or more and a number average molecular weight [hereinafter abbreviated as Mn. The measurement is based on a gel permeation chromatography (GPC) method. The following (i) low molecular polyols, (ii) polyhydric phenols and (iii) low molecular amines, and their AO (C2-12) adducts, etc., of 400 or less.
Examples of C2-12 AO include EO, PO, 1,2-, 1,3-, 1,4- and 2,3-butylene oxide, and mixtures of two or more thereof. AO and substituted AO may be used in combination. Examples of other AO and substituted AO include epoxidized products of C5-12 α-olefin, styrene oxide and epihalohydrin (such as epichlorohydrin and epibromohydrin).

(I) Low molecular polyol C2-20 or more dihydric alcohols such as C2-12 aliphatic dihydric alcohols [(di) alkylene glycols such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1
, 2-, 2,3-, 1,3- and 1,4-butanediol, 1,6-hexanediol, neopentyl glycol and 3-methylpentanediol (hereinafter referred to as EG, DEG, PG, DPG, BD, respectively) HD, NPG and MPD), dodecanediol, etc.], C6-10 alicyclic dihydric alcohol [1,4-cyclohexanediol, cyclohexanedimethanol, etc.], C8-20 araliphatic dihydric alcohol [xyl Lenglycol, bis (hydroxyethyl) benzene, etc.]; trihydric to octahydric or higher polyhydric alcohols such as (cyclo) alkane polyols and their intramolecular or intermolecular dehydrates [glycerin, trimethylolpropane, pentaerythritol Sorbitol and dipentaerythritol (hereinafter each GR, TMP, PE, SO and DPE), 1,2,6-hexanetriol, erythritol, cyclohexanetriol, mannitol, xylitol, sorbitan, diglycerin and other polyglycerins, etc.], sugars and their derivatives [for example, sucrose, Glucose, fructose, mannose, lactose, and glycoside (such as methylglucoside)].

(Ii) Polyhydric phenol C6-18 dihydric phenol such as monocyclic dihydric phenol (hydroquinone, catechol, resorcinol, urushiol, etc.), bisphenol (bisphenol A, -F, -C, -B, -AD) And -S, dihydroxybiphenyl, 4,4′-dihydroxydiphenyl-2,2-butane, etc.), and condensed polycyclic dihydric phenols [dihydroxynaphthalene (1,5-dihydroxynaphthalene, etc.), binaphthol, etc.]; and trivalent -8 or higher polyhydric phenols such as monocyclic polyphenols (pyrogallol, phloroglucinol, and mono- or dihydric phenols (phenol, cresol, xylenol, resorcinol, etc.) aldehydes or ketones (formaldehyde, glutar) Aldehyde, glio Saar, acetone) Teichijimigobutsu (phenol or cresol novolak resins, intermediates resol, polyphenols obtained by condensation reaction of phenol with glyoxal or glutaraldehyde, and polyphenols obtained by condensation reaction of resorcin and acetone) and the like.

(Iii) Low molecular amine Ammonia; C2-20 aliphatic mono- or polyamine [C2-20 alkanolamine (mono-, di- and triethanolamine, isopropanolamine, etc.), C1-20 alkylamine (n-butylamine) , Octylamine, etc.), C2-6 alkylenediamine (ethylenediamine, propylenediamine, hexamethylenediamine, etc.), C4-20 polyalkylene polyamine (alkylene group C having 6-6 dialkylenetriamine to hexaalkyleneheptamine, For example, diethylenetriamine and triethylenetetramine)]; C6-20 aromatic mono- or polyamines (aniline, phenylenediamine, tolylenediamine, xylylenediamine, diethyltoluenediamine, methylenedianil , Diphenyl ether diamine, etc.), C4-20 alicyclic mono- or polyamines (cyclohexylamine, isophoronediamine, cyclohexylenediamine, dicyclohexylmethanediamine, etc.), C4-20 heterocycle-containing amines (piperazine, aminoethylpiperazine, etc.), etc. .
Among these (i) to (iii), from the viewpoint of the strength after water expansion of the water-swellable polyurethane resin described later, (i) and (ii) are preferable, and more preferable are divalent to trivalent alcohols. Bisphenols, their AO adducts, and combinations thereof.

  Among the active hydrogen-containing compounds, Mn of the AO adducts (i) to (iii) is preferably 500 to 6,000, more preferably 1 from the viewpoint of easy handling before reaction and improvement of the reaction rate of epoxide. , 5,000 to 5,000.

The polyalkylene polyol of the present invention (hereinafter abbreviated as PAP) (A1) is an epoxide composed of EO and AGE (if necessary, C3-4 AO is added to the active hydrogen-containing compound in the presence of an alkali metal hydroxide). After adding the added epoxide, the same shall apply hereinafter), and then adsorbing the alkali metal hydroxide in an atmosphere having a gas phase oxygen concentration of 1.0 (preferably 0.5, more preferably 0.3) volume% or less. It is manufactured by removing using an agent and dehydrating. If the gas phase oxygen concentration exceeds 1.0% by volume, the by-product consisting of AGE multimers due to oxygen exceeds 0.3% based on the weight of the reaction product, resulting in water expandability. Since the moldability of a polyurethane resin deteriorates, it is not preferable. The content of by-products composed of AGE multimers in (A1) can be measured by the GPC method.
Specifically, the production method of (A1) includes an [I] reaction step in which an epoxide composed of EO and AGE is added to an active hydrogen-containing compound in the presence of an alkali metal hydroxide, and the alkali metal hydroxide is adsorbed. [II] A filtration step of adsorbing with a filter and filtering off, and [III] dehydration step of dehydrating the filtrate under reduced pressure.

  In the reaction step [I], the reaction temperature is preferably 80 to 120 ° C., more preferably 90 to 110 ° C., from the viewpoint of improving the reaction rate of epoxide and suppressing isomerization of the allylic group (propenyl rearrangement). From the same viewpoint, the reaction pressure is preferably 0.5 MPa or less, more preferably 0.4 MPa or less.

  The alkali metal hydroxide used as a catalyst is usually added to a low molecular active hydrogen compound and dehydrated (preferably water in the low molecular active hydrogen compound is 0.1 wt% or less), and then consists of EO and AGE. Addition polymerization of epoxide. Alkali metal hydroxides include lithium, sodium, potassium, rubidium, and cesium hydroxides.

  The amount of alkali metal hydroxide used is preferably from the viewpoint of improving the reaction rate of the epoxide and suppressing the isomerization of the allylic group (propenyl rearrangement) based on the weight of PAP (A1) at the end of the reaction. 01 to 0.3%, more preferably 0.05 to 0.2%.

  In the filtration step [II], while introducing an inert gas (nitrogen, argon, etc.) into the reaction vessel from which the reaction product was obtained, the gas phase oxygen concentration in the reaction vessel was set to 1.0 (preferably 0.8. 5, more preferably 0.3) after volume percent or less, preferably 0.1-3, more preferably 0.5-2% water is added based on the weight of the reaction product, 70-80 After raising the temperature to 0 ° C. and immediately adding an adsorbent of alkali metal hydroxide, the mixture is stirred and mixed for about 30 minutes and then filtered.

As the adsorbent, one or more selected from the group consisting of synthetic silicate, hydrotalcite, magnesia-alumina, activated clay, activated alumina, synthetic zeolite and ion exchange resin can be used.
Synthetic silicates include synthetic magnesium silicate [Kyoward 600 [trade name, manufactured by Kyowa Chemical Industry Co., Ltd.], Tomita AD600 [trade name, manufactured by Tomita Pharmaceutical Co., Ltd.], etc.], synthetic aluminum silicate [silica alumina [commodity] Name, Catalyst Kasei Kogyo Co., Ltd.], Kyoto Word 700 [trade name, manufactured by Kyowa Chemical Industry Co., Ltd.], Tomita AD700 [trade name, manufactured by Tomita Pharmaceutical Co., Ltd.], etc.]; Natural hydrotalcite, synthetic hydrotalcite [KYOWARD 500, KYOWARD 1000 [Brand name, both are manufactured by Kyowa Chemical Industry Co., Ltd.]]; As magnesia-alumina, KYOWARD 2000 [trade name, Kyowa Chemical Industry] Manufactured by Co., Ltd.]; Galeon Earth [trade name, manufactured by Mizusawa Chemical Co., Ltd.] as activated clay, Neobead [trade] Name, manufactured by Mizusawa Chemical Co., Ltd.], etc .; as synthetic zeolite, Mizuka Sieves [trade name, manufactured by Mizusawa Chemical Co., Ltd.], etc .; as an ion exchange resin, cation exchange resin [Urban Light IR120B [trade name, Rohm and Haas Co., Ltd.]], anion exchange resin [Urban Light IR900A [trade name, produced by Rohm and Haas Co., Ltd.], etc.].
Among these, synthetic magnesium silicate and synthetic aluminum silicate are preferable from the viewpoint of the amount of alkali metal adsorbed.
The use amount of the adsorbent is preferably 0.1 to 2%, more preferably 0.5 to 0.5% from the viewpoint of suppressing the amount of alkali metal adsorbed and oxygen from the adsorbent based on the weight of the PAP (A1) reaction product. 1%.

The dehydration step [III] is performed at a gas phase oxygen concentration of 1.0% by volume or less by passing an inert gas (nitrogen, argon, etc.) from the gas phase or liquid. The dehydration method is preferably a continuous or batch (batch) type dehydration method from the viewpoint of AGE decomposition or suppression of by-products consisting of multimers. In the continuous type, the filtrate after filtration is sprayed from the top of the vertically long evaporator under reduced pressure, and the filtrate is continuously sent to the top of the evaporator through a separate line until the filtrate reaches a certain water level. The method of repeating dehydration is a method in which the filtrate is stored in a dehydration tank and dehydrated with stirring under reduced pressure.
The dehydration temperature is preferably from 80 to 120 ° C., more preferably from 90 to 110 ° C., from the viewpoint of shortening the dehydration time and inhibiting by-products consisting of AGE decomposition or multimers.

Mn of (A1) is preferably 220 to 8,000, more preferably 260 from the viewpoint of mechanical properties of a water-expandable sealing material described later formed from (A1) and strength after water expansion of the sealing material. ˜7,000, particularly preferably 300 to 6,000.
The number of functional groups (A1) is preferably 2 to 3, more preferably 2, from the viewpoint of moldability of the water-swellable polyurethane resin.

  Based on the weight of (A1), the content of by-products composed of AGE multimers is 0 to 0.3%, and preferably 0 to 0.1% from the viewpoint of moldability of the water-swellable polyurethane resin.

If necessary, an antioxidant may be added to the PAP (A1) of the present invention as long as the effects of the present invention are not inhibited.
Examples of the antioxidant include tocopherol compounds (such as vitamin E) and the following phenol compounds (such as hindered phenol compounds).
Hindered phenol compounds:
(1) Monocyclic hindered phenol 2,6-di-t-butyl-4-methylphenol, 2-t-butyl-4-methoxyphenol, 6-t-butyl-2,4-methylphenol, 2, 6-di-t-butylphenol, 2-t-butyl-4-ethylphenol, 2,6-di-t-butyl-4-ethylphenol, n-octadecyl-3- (4-hydroxy-3,5-di -T-butylphenyl) propionate, dioctadecyl-4-hydroxy-3,5-di-t-butylbenzylphosphonate, diethyl-4-hydroxy-3,5-di-t-butylbenzylphosphonate, 6- (4- Oxy-3,5-di-t-butylanilino) -2,4-bis- (n-octylthio) -1,3,5-triazine and the like;
(2) Bicyclic hindered phenol 4,4′-thiobis (6-tert-butyl-3-methylphenol, 4,4′-butylidenebis (6-tert-butyl-3-methylphenol), 4,4′- Methylene bis (6-t-butylphenol), 4,4-bis (2,6-di-t-butylphenol), 4,4′-thiobis (6-t-butyl-o-cresol), 2,2′-methylene bis (4-methyl-6-tert-butylphenol), 2,2′-thiobis (6-butyl-4-methylphenol), 1,6-bis (3,5-di-tert-butyl-4-hydroxy-2) -Methylphenyl) butane and the like;
(3) Polycyclic (tricyclic or higher) hindered phenol 1,1,3-tris (5-t-butyl-4-hydroxy-2-methylphenyl) butane, 2,4,6-tris (3 5-di-t-butyl-4-hydroxybenzyl) isocyanurate, tetrakis [β- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxymethyl] methane and the like.

The amount of the antioxidant used is preferably from 0.01 to 0.5%, more preferably from 0.05 to 0.3%, from the viewpoint of antioxidant and industrial use, based on the weight of (A1).
A method for adding and mixing the antioxidant is not particularly limited, and a conventionally known mixing apparatus can be used. Also, the timing of addition is not particularly limited, but is added to and mixed with the raw material before production of (A1), added or mixed in the production process of (A1), or added after production of (A1), You may carry out by any method of mixing.

The water-swellable polyurethane resin of the present invention is formed from a polyol component (A) and an isocyanate component (B).
The polyol component (A) includes a high molecular polyol (A2) and a low molecular polyol (A3) containing 99% by weight or less of EO units other than the PAP (A1) and (A1).
Examples of (A2) include (i) low molecular polyol, (ii) polyhydric phenol, and (iii) polyol of Mn 1,000 to 8,000 obtained by adding AO (C2-12) to low molecular amine. It is done. These polymer polyols can be used alone or in combination.

  Examples of the low molecular polyol (A3) include polyols such as the above (i) and the AO (C2-12) adduct (Mn less than 1,000) of the above (i), (ii) and (iii). These low molecular polyols can be used alone or in combination.

  The proportion of (A1) in the polyol component (A) is preferably from 5 to 98% by weight, more preferably from the viewpoint of the water-expandable strength of the water-expandable sealing material described later and the moldability of the water-expandable polyurethane resin. 10 to 90% by weight.

Poly (n = 2 to 3, preferably 2) isocyanate constituting the isocyanate component (B) is a non-aromatic polyisocyanate, for example, C (excluding carbon in the isocyanate group, the same shall apply hereinafter) 2 to 18 fat. Group polyisocyanate [ethylene diisocyanate (diisocyanate is abbreviated as DI hereinafter), 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, etc.]; C8-15 alicyclic polyisocyanate [isophorone DI (IPDI), dicyclohexylmethane DI (hydrogenated MDI) , Cyclohexylene DI, methylcyclohex Len DI (hydrogenated TDI), bis (2-isocyanatoethyl) 4-cyclohexene-1,2-dicarboxylate, etc.]; C8-15 aromatic aliphatic polyisocyanate [xylylene DI (XDI), tetramethylxylylene DI (TMXDI), etc.]; and modified products of these polyisocyanates (carbodiimide modification, uretdione modification, uretoimine modification, urea modification, burette modification, isocyanurate modification, etc.) and the like.
Of these, aliphatic or alicyclic polyisocyanates (particularly DI) are preferred from the viewpoint of chemical resistance and weather resistance, and HDI, IPDI and hydrogenated MDI are more preferred.

  In the production of the water-swellable polyurethane resin, the reaction ratio [NCO / OH equivalent ratio] of the isocyanate component (B) and the polyol component (A) is determined by the strength and water expansion of the water-swellable sealing material described later after water swelling. From the viewpoint of moldability of the conductive polyurethane resin, it is preferably 0.8 / 1 to 1/1, and more preferably 0.9 / 1 to 0.98 / 1. The reaction rate is a final reaction rate, and usually does not change depending on the production method (one-shot method or prepolymer method) described later.

Examples of the method for producing the water-swellable polyurethane resin include commonly used methods (one-shot method, prepolymer method, etc.). Among these, the prepolymer is preferred from the viewpoint of less variation in the quality of the obtained polyurethane resin. Is the law. Next, the manufacturing method by a prepolymer method is illustrated.
First, the terminal isocyanate group-containing prepolymer as an intermediate comprises a part of the polyol component (A) and the isocyanate component (B) [NCO / OH equivalent ratio is preferably 1.2 / 1 to 10/1] It is obtained by reacting at 70 to 150 ° C. by a conventional method. The isocyanate group content [NCO content (% by weight)] in the obtained prepolymer is preferably 2 to 15%, more preferably 3 to 10%.
Next, the prepolymer and the remainder of the above (A) are mixed and reacted [reaction is performed so that the reaction ratio becomes the final reaction ratio. ] After pouring into a metal mold | die etc., Preferably it is 70-120 degreeC, More preferably, it is made to react at 80-110 degreeC for 0.5 to 10 hours, and a water-swellable polyurethane resin is obtained.

In producing the water-swellable polyurethane resin, 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. Of these, metal salts of carboxylic acids are preferred, and lead octylate and bismuth octylate are more preferred.
The amount of the urethanization catalyst used is usually 5% or less, preferably 0.001 to 3%, based on the weight of (A).

The water-swellable sealing material of the present invention is obtained by adding a polymer elastic body to the water-swellable polyurethane resin and vulcanizing agent, or the water-swelling polyurethane resin and vulcanizing agent, if necessary.
As the vulcanizing 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, such as p-quinone dioxime, p, p'-dibenzoylquinonedioxime), metal oxides (magnesia, risurge, etc.), alkylphenol resins [Tacquirol 201 [trade name, manufactured by Taoka Chemical Co., Ltd.], etc.], polythiol compounds [TMP trithioglycolate , TMP tri (3-mercaptop Lopionate), 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 vulcanizing agents can be used alone or in combination of two or more.
Among these, from the viewpoint of ease of handling and the like, sulfur and a combination of sulfur and another vulcanizing agent, particularly sulfur is preferable.

  Examples of the polymer elastic body include natural rubber, synthetic rubber [styrene butadiene rubber (SBR), butadiene rubber, isoprene rubber, butyl rubber, chloroprene rubber (CR), acrylonitrile-butadiene rubber (NBR), ethylene-propylene-diene rubber, butyl rubber, etc. And their reclaimed rubber, and non-water-swellable polyurethane rubber (PU) having an ethylenically unsaturated bond in the side chain.

  Non-water-swellable polyurethane rubber (PU) includes polyether polyurethane rubber [Miracene CM [trade name, manufactured by TSE Ltd.] and the like] and polyester polyurethane rubber [Miracene 76 [trade name, manufactured by TSE Ltd.], etc.] Is mentioned.

Among the above polymer elastic bodies, a synthetic rubber having a solubility parameter (solubility parameter by the Fedors method, hereinafter abbreviated as SP value) is preferably 8.4 or more from the viewpoint of compatibility with the water-swellable polyurethane resin. Further preferred are SBR, CR, NBR, and PU.
Here, the SP value is represented by the square root of the ratio between the cohesive energy density and the molecular volume as described below.

[SP] = (ΔE / V) ^1/2

In the formula, ΔE represents the cohesive energy density, and V represents the molecular volume. Robert F. The SP value calculated by Fedors et al. Is, for example, Polymer engineering and
science, Vol. 14, pp. 147-154.

  The water-swellable sealing material of the present invention includes a filler, a pigment, a softening agent, a vulcanization accelerator, a vulcanization acceleration aid, a factice, an antiaging agent, and a dehydration as necessary, as long as the effects of the present invention are not impaired. One or two or more rubber additives selected from the group consisting of additives can be contained.

Examples of the filler include carbon black, talc, calcium carbonate, anhydrous silicic acid, hydrous silicic acid, and clay;
Examples of the pigment include inorganic pigments (titanium oxide, bengara, yellow lead, cadmium sulfide, ultramarine, etc.), and organic pigments (azo, phthalocyanine, quinacridone, dioxazine, etc.);
Softeners include lubricating oil, fatty acid oil, mineral oil (paraffinic oil, naphthenic oil, aromatic oil, petroleum asphalt, etc.), tar softener (tar, coumarone-indene resin, etc.), ester softener (Phthalic acid derivative oil, adipic acid derivative oil, benzoic acid derivative oil, sebacic acid derivative oil, maleic acid derivative oil, fumaric acid derivative oil, trimellitic acid derivative oil, citric acid derivative oil, oleic acid derivative oil, ricinoleic acid derivative Oil, stearic acid derivative oil, phosphoric acid derivative oil, glycolic acid derivative oil, etc.), synthetic resin softeners (phenol-formaldehyde resin, xylene-formaldehyde resin, polyester resin, epoxy resin, etc.), etc .;

Vulcanization accelerators include guanidine compounds (diphenylguanidine, diorthotolylguanidine, etc.), thiazole compounds (2-mercaptobenzothiazole, dibenzothiazyl disulfide, etc.), thiuram compounds (tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetramethyl). Thiuram monosulfide, dipentamethylene thiuram tetrasulfide, etc.), sulfenamide compounds (N-cyclohexyl-2-benzothiazole sulfenamide, Nt-butyl-2-benzothiazole sulfenamide, etc.), metal compounds (dibutyl) Zinc dithiocarbamate, 2-mercaptobenzothiazole zinc salt, dibenzothiazyl disulfide zinc chloride complex, etc.);
Examples of vulcanization accelerators include C8-24 fatty acids and derivatives thereof (stearic acid, oleic acid, lauric acid, zinc stearate, etc.), metal oxides (zinc oxide, etc.), metal salts (zinc carbonate, etc.), etc .;

The factices include black sub, white sub, candy sub and sulfur-free factis;
Anti-aging agents include amines (N-phenyl-α-naphthylamine, N-phenyl-β-naphthylamine, N-phenyl-N′-isopropyl-p-phenylenediamine, 2,2,4-trimethyl-1,2- Dihydroquinoline, etc.), amine ketone (reaction product of diphenylamine and acetone, etc.), the hindered phenol compound, dithiocarbamate (such as nickel dibutyldithiocarbamate), etc .;
Examples of the dehydrating agent include calcium oxide, calcium sulfate (hemihydrate gypsum), calcium chloride, molecular sieve, and the like.

The amount of the rubber additive used based on the total weight of the water-swellable sealing material is usually 100% or less, preferably 0.01 to 60%.
The amount of each rubber additive used is usually 60% or less, preferably 5 to 50% for fillers; usually 5% or less, preferably 0.1 to 2% for pigments; In the following, preferably 3 to 10%; vulcanization accelerator, vulcanization acceleration aid, factice, anti-aging agent and dehydrating agent are each usually 5% or less, preferably 0.1 to 3%.

The water-swellable sealing material of the present invention is prepared by using, for example, a Banbury mixer or a kneader, a polyurethane resin, a vulcanizing agent, and, if necessary, a polymer elastic body, a part of the rubber additive (softening agent, vulcanization acceleration aid) Kneading agent, anti-aging agent, etc.) such that the temperature after kneading is 80 to 120 ° C., and then vulcanizing agent and other additives (vulcanization accelerator, dehydrating agent, etc.) on the roll if necessary. It is obtained by kneading until the appearance becomes uniform, and extrusion molding or press molding.
The molding temperature is set according to the type of vulcanizing agent, but is preferably 140 to 200 ° C. from the viewpoint of the strength of the water-expandable sealing material after water expansion and the mechanical properties of the water-expandable sealing material.

The water-swellable sealing material of the present invention usually has a saturated volumetric water expansion ratio of 1.2 to 5 times in purified water at 23 ° C. (distilled water or deionized water, the same shall apply hereinafter). The saturated volumetric water expansion ratio is preferably 1.4 to 4 times, more preferably 1.5 to 3 times, from the viewpoint of the water stop effect after water expansion and the tensile strength after water expansion. Here, the saturated volumetric water expansion ratio is obtained by the following method.
(Saturated volumetric water expansion ratio)
A 20 × 20 × 2 mm test piece is taken from the strip of the water-swellable sealing material, and the volume when this test piece is immersed in purified water at 23 ° C. is measured every fixed period (daily unit). To calculate the volumetric water expansion ratio.

Volumetric water expansion ratio (times) = volume after expansion / volume before expansion

The magnification at the time when the increase rate of the volumetric water expansion ratio per day becomes 0.01% or less (the magnification when the ratio of the previous day's magnification becomes 1.0001 times or less) is the saturated volumetric water expansion ratio of the test piece. And

  Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited thereto. In the following, “part” means “part by weight” and “%” means “% by weight”.

The composition and symbols of the raw materials used in the following examples and comparative examples are as follows.
Polyether polyol (1): EO / PO of bisphenol A (weight ratio 80/20)
Random adduct (Mn 4,000)
Polyether polyol (2): PO adduct of bisphenol A (Mn 2,000)
Polyether polyol (3): PO adduct of bisphenol A (Mn600)
Polyether polyol (4): Polypropylene glycol (Mn 1,000)
Catalyst (1): Lead octylate polymer elastic body (1): SBR [trade name “JSR SL552”, manufactured by JSR Corporation]
Filler (1): Carbon black [trade name “Asahi # 50”, manufactured by Asahi Carbon Co., Ltd.]
(2): Calcium carbonate [Brand name "Softon 1500", Bihoku powdering industry
Manufactured by]
Vulcanization accelerator (1): stearic acid
(2): Zinc oxide softener (1): Aromatic mineral oil [trade name “Dyna Process Oil AC-460”,
Idemitsu Kosan Co., Ltd.]
(2): Dipropylene glycol dibenzoate [trade name "Adekasizer
PN6120 ", manufactured by Asahi Denka Kogyo Co., Ltd.]
Factis (1): Black Sub [Product name “Black Sub Pure”, manufactured by Tenma Sub Chemical Co., Ltd.]
Vulcanizing agent (1): Sulfur vulcanization accelerator (1): Dibenzothiazyl disulfide
(2): 2-mercaptobenzothiazole dehydrating agent (1): calcium oxide

Example 1
A fully dried pressure-resistant reaction vessel was charged with 53.4 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 836.6 parts of EO was introduced from the bottom of the kettle in the range of 90 to 100 ° C. and reacted at 90 to 100 ° C. for 2 hours. After reducing the pressure in the reaction vessel, 110 parts of AGE was introduced from the bottom of the kettle 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 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 under nitrogen pressure (gas phase oxygen concentration 0%). 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 a temperature range of 95 to 105 ° C., followed by dehydration under reduced pressure. When the moisture content reached 0.05%, the mixture was immediately cooled to obtain PAP (A1-1) having a hydroxyl value of 56.1 mgKOH / g (hereinafter, only numerical values are shown). The content of by-products composed of AGE multimers in (A1-1) was 0% by GPC measurement.

Example 2
A fully dried pressure-resistant reaction vessel was charged with 53.4 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 is cooled to 95 ° C., EO 896.6 parts and AGE 50 parts are mixed in advance and introduced from the bottom of the kettle in the range of 90 to 100 ° C. and reacted at 90 to 100 ° C. for 2 hours. (Random addition). After cooling to 70 ° C., the same procedure as in Example 1 was performed to obtain PAP (A1-2) having a hydroxyl value of 56.1. In (A1-2), the content of by-products composed of AGE multimers was 0% by GPC measurement.

Example 3
Into a fully dry pressure-resistant reaction vessel, 114 parts of bisphenol A and 2 parts of potassium hydroxide were charged and sealed, and then 776 parts of EO was introduced from the bottom of the kettle in the range of 90-100 ° C and reacted at 90-100 ° C for 2 hours. It was. After reducing the pressure in the reaction vessel, 110 parts of AGE was introduced from the bottom of the kettle 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., the same procedure as in Example 1 was performed to obtain PAP (A1-3) having a hydroxyl value of 56.1. In (A1-3), the content of by-products composed of multimers of AGE was 0% by GPC measurement.

Example 4
In Example 2, in place of DEG 53.4 parts, EO 896.6 parts, and AGE 50 parts, except that DEG 101.6 parts, EO 298.4 parts, PO 100 parts, and AGE 500 parts were used ( Random addition), PAP (A1-4) having a hydroxyl value of 112.2 was obtained. In (A1-4), the content of by-products composed of multimers of AGE was 0% by GPC measurement.

Example 5
In Example 1, from the completion of the reaction to the start of vacuum dehydration, the same procedure as in Example 1 was performed (block addition), except that nitrogen was blown in and the gas phase oxygen concentration was 0.5%. .1 PAP (A1-5) was obtained. In (A1-5), the content of by-products composed of AGE multimers was 0.1% by GPC measurement.

Example 6
In Example 1, from the completion of the reaction to the start of vacuum dehydration, the same procedure as in Example 1 was performed (block addition), except that nitrogen was blown in and the gas phase oxygen concentration was 1.0%. 0.1 PAP (A1-6) was obtained. In (A1-6), the content of by-products composed of multimers of AGE was 0.3% by GPC measurement.

Example 7
Example 2 was carried out in the same manner as in Example 2 except that EG20 part, EO950 part, and AGE30 part were used instead of DEG 53.4 parts, EO896.6 parts, and AGE50 parts (random addition). .2 PAP (A1-7) was obtained. In (A1-7), the content of by-products composed of multimers of AGE was 0% by GPC measurement.

Example 8
In Example 2, in place of DEG 53.4 parts, EO 896.6 parts and AGE 50 parts, except that EG 10 parts, EO 980 parts and AGE 10 parts were used (random addition), hydroxyl value 18 .1 PAP (A1-8) was obtained. In (A1-8), the content of by-products composed of multimers of AGE was 0% by GPC measurement.

Example 9
In Example 2, in place of DEG 53.4 parts, EO 896.6 parts, and AGE 50 parts, polyether polyol (4) 200 parts, EO 250 parts, PO 250 parts, and AGE 300 parts were used in the same manner as in Example 2. Performing (random addition), PAP (A1-9) having a hydroxyl value of 22.4 was obtained. In (A1-9), the content of by-products composed of AGE multimers was 0% by GPC measurement.

Example 10
In Example 2, in place of DEG 53.4 parts, EO 896.6 parts, and AGE 50 parts, the procedure was the same as Example 2 except that DEG 101.6 parts, EO 200 parts, PO 98.4 parts, and AGE 600 parts were used ( Random addition), PAP (A1-10) having a hydroxyl value of 112.2 was obtained. In (A1-10), the content of by-products composed of multimers of AGE was 0% by GPC measurement.

Example 11
In Example 2, in place of EO 896.6 parts and AGE 50 parts, except that EO 150 parts, PO 146.6 parts and AGE 650 parts were used (random addition), the hydroxyl value of 56.1 PAP (A1-11) was obtained. The content of by-products composed of AGE multimers in (A1-11) was 0% by GPC measurement.

Comparative Example 1
In Example 1, the filtration under nitrogen pressurization was replaced with the filtration under air pressurization, except that it was performed in the atmosphere (gas phase oxygen concentration 21%) from the end of the reaction until the start of vacuum dehydration. 1 (block addition), PAP (ratio A1-1) having a hydroxyl value of 56.1 was obtained. In (ratio A1-1), the content of by-products consisting of AGE multimers was 10.0% by GPC measurement.

Comparative Example 2
In Example 1, from the completion of the reaction until the start of vacuum dehydration, the same procedure as in Example 1 was performed (block addition), except that nitrogen was blown in and the gas phase oxygen concentration was 3.0%. 0.1 PAP (ratio A1-2) was obtained. In (Ratio A1-2), the content of by-products consisting of AGE multimers was 1.0% by GPC measurement.

The methods for measuring the hydroxyl value and by-product content in Examples 1 to 11 and Comparative Examples 1 and 2 are as follows. The results are shown in Table 1.
(1) Hydroxyl value According to “Polyurethane polyether test method” described in JIS K7117-1: 1999.
(2) Measuring method of by-product content by GPC Model: HLC-8120 [manufactured by Tosoh Corporation]
Column: TSK gel SuperH4000
TSK gel SuperH3000
TSK gel SuperH2000 [all manufactured by Tosoh Corporation]
Column temperature: 40 ° C
Detector: RI
Solvent: Tetrahydrofuran flow rate: 0.6 ml / min Sample concentration: 0.25 to 0.50%
Injection volume: 10 μl
Standard substance: Polyethylene glycol [TSK STANDARD POLYETHYL
ENE OXIDE, manufactured by Tosoh Corporation]

Production Example 1
822 parts of polyether polyol (1) and 178 parts of isophorone diisocyanate were reacted at 120 ° C. for 3 hours to obtain a prepolymer (1) having an NCO content of 5.0%.

Production Example 2
781 parts of PAP (A1-2) and 219 parts of isophorone diisocyanate were reacted at 120 ° C. for 3 hours to obtain a prepolymer (2) having an NCO content of 5.0%.

Production Example 3
807 parts of polyether polyol (1) and 193 parts of hydrogenated MDI were reacted at 120 ° C. for 3 hours to obtain a prepolymer (3) having an NCO content of 4.5%.

Production Example 4
844 parts of polyether polyol (1) and 156 parts of HDI were reacted at 120 ° C. for 3 hours to obtain a prepolymer (4) having an NCO content of 6.0%.

Production Examples 5 to 18
It mix | blended with the composition (part) of Table 2, and it was made to react at 100 degreeC for 10 hours, and water-swellable polyurethane resin (1)-(14) was obtained. About this polyurethane resin, the Mooney viscosity was measured according to the following test method. The results are shown in Table 2.

Examples 12-23
According to the composition of Table 3, <Kneading component 1> of the blending components was kneaded for 10 minutes with a Banbury mixer. Next, <kneading component 2> was added and kneaded with two rolls for 30 minutes. The kneaded product was extruded into a rod shape having a cross section of 20 mm × width 2 mm using an extrusion molding machine, and then heated at 160 ° C. for 10 minutes to obtain a water-expandable sealing material molded product.

Comparative Examples 3-4
According to the composition of Table 3, a water-swellable sealing material molded product was obtained in the same manner as in Examples 12-23.

About each molded article of Examples 12-23 and Comparative Examples 3-4, extrusion moldability, tensile strength, elongation, saturated volumetric water expansion ratio, tensile strength after one month of water immersion, and elongation were measured. The results are shown in Table 3. The test method is as follows.
<Test method>
(1) Mooney viscosity The Mooney viscosity was measured according to JIS K6300-1: 2001 “Unvulcanized rubber—physical properties—Part 1: Determination of viscosity and scorch time using Mooney viscometer”.
(2) Extrudability In accordance with ASTM D2230-96 (2002) e1 (B evaluation), the extrusion moldability of a garbage die extrusion molded product was evaluated according to the following criteria.
<Evaluation criteria>
The following criteria [1] and [2] were evaluated according to the evaluation criteria described in the ASTM.
That is, the evaluation result of [1] and the evaluation result of [2] are described in order. For example, if both [1] and [2] are excellent, the evaluation is “10A”, [1] and [2] If both are poor, the evaluation is described as “1E”.
[1] Sharpness and continuity of 30 ° edge portion. Evaluated in 10 grades of 1 (bad) to 10 (good).
[2] Surface smoothness: Evaluated in 5 stages from A (good) to E (bad).
(3) Tensile strength and elongation According to “Vulcanized rubber and thermoplastic rubber—How to obtain tensile properties” described in JIS K6251: 2004, a No. 3 dumbbell specimen was punched from a sheet press-formed to a thickness of 2 mm and measured. The measurement after water expansion was performed after the test piece was immersed in purified water at 23 ° C. for 1 month.
(4) Saturation volume water expansion ratio A test piece of 20 × 20 × 2 mm was taken from the molded product, and the volume when this test piece was immersed in purified water at 23 ° C. was measured at regular intervals. The volumetric water expansion ratio was calculated.

Volumetric water expansion ratio (times) = Volume during expansion / Volume before expansion

Moreover, the volume expansion ratio when the increase amount of the volume expansion ratio per day became 0.01% or less was defined as the saturated volumetric water expansion ratio of the test piece.

（注＊１）膨張により形状が維持できなかった。

(* 1) The shape could not be maintained due to expansion.

  From the results of the examples, the PAP obtained by the production method of the present invention has a low content of by-products consisting of AGE multimers, and the water-swellable polyurethane resin formed from the PAP has excellent moldability and the water-swellability. It can be seen that a water-swellable sealing material formed by molding a polyurethane resin is less susceptible to strength reduction after water swelling and has excellent long-term water stopping properties.

  The PAP obtained by the production method of the present invention has an effect that the content of by-products consisting of a multimer of allyl glycidyl ether (AGE) is small. (1) Extrusion molding or various cross-section segment sealing materials formed by coextrusion molding with non-expandable rubber, (2) Architectural gaskets formed into a hollow shape or a plate shape, etc. (3) Cross section It can be suitably used for a wide range of applications such as a water-expandable packing such as a grout hole formed into a circular ring shape.

Claims (6)

In the presence of an alkali metal hydroxide, an epoxide composed of ethylene oxide and allyl glycidyl ether is added to the active hydrogen-containing compound, and then an alkali metal hydroxide is added in an atmosphere having a gas phase oxygen concentration of 1.0% by volume or less. The polyalkylene polyol (A1) is characterized in that the product is removed using an adsorbent and dehydrated, and the content of by-products consisting of multimers of allyl glycidyl ether is 0 to 0.3% by weight. Manufacturing method. The process according to claim 1, wherein (A1) is a polyalkylene polyol comprising 15 to 99% by weight of ethylene oxide units and 1 to 65% by weight of allyl glycidyl ether units. A polyalkylene polyol (A1) obtained by the production method according to claim 1 or 2. A water-swellable sealing material comprising a water-swellable polyurethane resin formed from a polyol component containing (A1) according to claim 3 and an isocyanate component. The sealing material according to claim 4, wherein the content of (A1) is 5 to 98% based on the weight of the polyol component. Furthermore, the sealing material of Claim 4 or 5 formed by adding a polymeric elastic body.