JP2010084029A - Polyether polyol - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyether polyol liquid at a normal temperature, exhibiting good handleability, and providing a resin having good resin properties such as elongation properties. <P>SOLUTION: The polyether polyol contains a polyether polyol satisfying the following (1) to (4): (1) one or more kinds of constituent units represented by formula (a) (wherein, n is 1 or 2; and x is an integer of 2-7) and one or more kinds of constituent units represented by formula (b); (2) one or more constituent units represented by formula (b) terminated by -(CH<SB>2</SB>)<SB>x</SB>-O-H at the terminal of the polyol; (3) the constituent unit represented by formula (b) at the polyol terminal may be one or more kinds wherein at least one of x is ≥3; and (4): 40-100 mol% and 0-60 mol% of the polyol terminal have structures represented by specific chemical formulas. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a polyether polyol and a polyurethane resin obtained by reacting the polyether polyol.

Polyether polyol is used as a soft segment component of a polyurethane resin, and in particular, polytetramethylene glycol (hereinafter abbreviated as PTMG) is excellent in elastic properties and widely used for applications such as spandex and elastomer.
However, PTMG in the molecular weight range normally used (number average molecular weight = 600 to 3000) has a high melting point of 20 to 35 ° C. and is a solid at room temperature, and requires heating during use, and therefore has handling and workability. bad. Further, due to its high crystallinity, the obtained resin has insufficient stretch properties.
Therefore, a method is known in which a structural unit having a side chain is introduced into the PTMG main chain to obtain a polyether that is difficult to crystallize (Patent Document 1).
Japanese Patent Publication No.7-116276

  However, in the method of the patent document, the polyol is liquid at room temperature, but there is a problem that the elongation property of the obtained resin is still insufficient.

As a result of intensive studies, the present inventors have reached the present invention.
That is, the present invention includes the following (I) and (II).
(I) A polyether polyol containing a polyether polyol (A) that satisfies the following (1) to (4).
(1) It has one or more structural units represented by the following chemical formula (a) and one or more structural units represented by the following chemical formula (b).

[N is 1 or 2]

[X is an integer of 2 to 7]
(2) One or more structural units represented by the chemical formula (b) are present at the polyol terminal, and the molecular terminal is — (CH ₂ ) _x —O—H ₂ .
(3) The structural unit represented by the chemical formula (b) at the end of the polyol may be one type or two or more types, and at least one type of x is 3 or more.
(4) 40 to 100 mol% of the polyol terminal is a structure represented by the following chemical formula (c), and 0 to 60 mol% is a structure represented by the following chemical formula (d).

[In the chemical formulas (c) and (d), n is 1 or 2, x is an integer of 2 to 7, p is an average of 1 to 49, and q is an average of 1 to 10]
(II) A polyurethane resin obtained by reacting a polyol component and an organic polyisocyanate, if necessary, in the presence of an additive, and containing the polyether polyol of the above (I) as at least a part of the polyol component.

  By using the polyether polyol of the present invention, it is possible to obtain a resin, particularly a polyurethane resin, which is liquid at room temperature, has good handling properties, and has good elongation properties.

The polyether polyol (A) in the polyether polyol of the present invention has one or more structural units represented by the chemical formula (a), and n in the chemical formula (a) is 1 or 2, Is 1.
When n is 0, the hydrophilicity of the polyol increases, the water resistance of the resulting resin decreases, and when it exceeds 2, the strength of the resulting resin decreases.

(A) has 1 or more types of structural units further represented by said chemical formula (b), and x in chemical formula (b) is an integer of 2-7, Preferably it is 2-4.
When x is 1, the hydrophilicity of the polyol increases and the water resistance of the resulting resin decreases. When it exceeds 7, the compatibility with other components in producing the resin decreases and a good resin is obtained. It becomes difficult.

The polyether polyol (A) in the polyether polyol of the present invention has one or more structural units represented by the chemical formula (b) at its terminal, and the molecular terminal is — (CH ₂ ) _x —O—. H. The structural unit represented by the chemical formula (b) at the end of the polyol may be one kind or two or more kinds, preferably one kind or two kinds. Further, at least one kind of x is 3 or more. At least one x is preferably 3 to 5, more preferably 4. The content of x in the structural unit represented by (b) is preferably 3 to 90 mol%.
When x of all the structural units is 2, the strength of the obtained resin is lowered.

In (A), 40 to 100 mol% of the polyol terminal is a structure represented by the following chemical formula (c), and 0 to 60 mol% is a structure represented by the following chemical formula (d). The structure of the chemical formula (c) is preferably 45 to 100 mol%, more preferably 60 to 100 mol%.
When the structure of the chemical formula (c) is less than 40 mol%, the activity of the polyol (reactivity with isocyanate, etc.) is lowered.
In chemical formula (c) and chemical formula (d), p is an average number of 1 to 49, preferably 1 to 40. When p is less than 1, the resulting polyol has high crystallinity, resulting in poor handling, and when it exceeds 49, the strength of the resulting resin is insufficient. q is an average number of 1 to 10, preferably 2 to 10, and more preferably 5 to 10. If q is less than 1, the strength of the resin will be insufficient, and if it exceeds 10, the crystallinity of the resulting polyol will be high, and handling will be reduced.

The number average molecular weight per functional group of the polyether polyol (A) is preferably 300 to 3000, more preferably 350 to 2500, and particularly preferably 400 to 2000.
The number average molecular weight per functional group in the present invention is calculated by the following formula (A).
Number average molecular weight = 56100 ÷ Hydroxyl value Formula (A)
[Hydroxyl value: Value measured by the method defined in JIS K0070 (1992 edition)]
When the number average molecular weight per functional group is 300 or more, the elongation property of the obtained resin is improved, and when it is 3000 or less, the strength of the obtained resin is sufficient.

  The method for synthesizing the polyether polyol of the present invention is not particularly limited. For example, an alkylene oxide (hereinafter referred to as AO) is used in the presence of an alkali catalyst or an acid catalyst, starting from a divalent or higher active hydrogen-containing compound. A method of ring-opening polymerization may be used, and dehydration condensation of two types of terminal hydroxyl group-containing compounds of a polyol having the chemical formula (a) as a structural unit and a polyol having the chemical formula (b) as a structural unit may be used. Polymerization.

The catalyst used during the ring-opening polymerization of AO may be an alkali catalyst or an acid catalyst.
Alkali catalysts include alkali metal hydroxides (potassium hydroxide, sodium hydroxide, cesium hydroxide, etc.), alkali metal alcoholates (potassium methylate, sodium methylate, etc.), alkali metals alone (metal potassium, metal sodium, etc.), etc. 2 or more may be used in combination.
Acid catalysts include Lewis acids [specifically, boron trifluoride, triphenylborane, diphenyl-t-butylborane, tri (t-butyl) borane, triphenylaluminum, diphenyl-t-butylaluminum, tri (t- Butyl) aluminum, tris (pentafluorophenyl) borane, bis (pentafluorophenyl) -t-butylborane, tris (pentafluorophenyl) aluminum, bis (pentafluorophenyl) -t-butylaluminum, bis (pentafluorophenyl) fluorine Borane, di (t-butyl) fluoroborane, (pentafluorophenyl) difluoroborane, (t-butyl) difluoroborane, bis (pentafluorophenyl) aluminum fluoride, di (t-butyl) fluoride Aluminum fluoride, (pentafluorofe Le) 2 aluminum fluoride, (t-butyl) 2 aluminum fluoride], and the like, may be used in combination of two or more thereof.
Of these, preferred are alkali metal hydroxides and alkali metal alcoholates, and boron-containing Lewis acids, and more preferred are alkali metal hydroxides, boron trifluoride, and tris (pentafluorophenyl) borane. .
In addition, although an alkali catalyst and an acid catalyst cannot be used at the same time, an alkali catalyst may be used until the middle of the target molecular weight, and after removing the alkali catalyst, an acid catalyst may be used up to the target molecular weight, or vice versa.

Examples of the active hydrogen-containing compound used as a starting material in the ring-opening polymerization include a hydroxyl group-containing compound, an amino group-containing compound, a carboxyl group-containing compound, a thiol group-containing compound, and a phosphate compound.
As the hydroxyl group-containing compound, for example, a compound having a structure in which AO described later is added to a compound having polyhydric alcohol, alkanolamine, and active hydrogen (polyhydric alcohol, amino group-containing compound, carboxylic acid, phosphoric acid, etc.) (Polyether polyol) may be mentioned, and two or more kinds may be used in combination. The catalyst used for the production of the polyether polyol as the starting material is not particularly limited.

Polyhydric alcohols include ethylene glycol, propylene glycol, 1,3-butylene glycol, 1,4-butanediol, 1,6-hexanediol, 3-methylpentanediol, diethylene glycol, neopentyl glycol, 1,4-bis Dihydric alcohols such as (hydroxymethyl) cyclohexane, 1,4-bis (hydroxyethyl) benzene, 2,2-bis (4,4′-hydroxycyclohexyl) propane; trihydric alcohols such as glycerin and trimethylolpropane; penta Erythritol, diglycerin, α-methyl glucoside, sorbitol, xylit, mannitol, dipentaerythritol, glucose, fructose, sucrose, etc .; 4-phenols such as phenol, cresol; Polyphenols such as bisphenol A, bisphenol F and bisphenol S; polybutadiene alcohols; castor oil alcohols, hydroxyalkyl (meth) acrylate (co) polymers, and polyfunctional alcohols such as polyvinyl alcohol ( 2-100) alcohol etc. are mentioned, A C1-C20 thing is preferable.
Examples of polyvinyl alcohol include those having a 1,2-vinyl structure, those having a 1,2-vinyl structure and a 1,4-trans structure, and those having a 1,4-trans structure. The ratio of the 1,2-vinyl structure and the 1,4-trans structure can be variously changed, and for example, the molar ratio is 100: 0 to 0: 100. Polybutadiene glycol includes homopolymers and copolymers (styrene butadiene copolymer, acrylonitrile butadiene copolymer, etc.), and hydrogenated products thereof (hydrogenation rate: for example, 20 to 100%).
Further, as castor oil alcohol, castor oil and modified castor oil (castor oil modified with polyhydric alcohol such as trimethylolpropane and pentaerythritol) can be mentioned.

Examples of amino group-containing compounds include mono- or polyamines and amino alcohols.
Specific examples of mono- or polyamines include monoamines such as ammonia, alkylamines (butylamine, etc.) and anilines; aliphatic polyamines such as ethylenediamine, trimethylenediamine, hexamethylenediamine, diethylenetriamine; piperazine, N-aminoethylpiperazine and others Heterocyclic polyamines described in Japanese Patent Publication No. 55-21044; alicyclic polyamines such as dichloromethanediamine and isophoronediamine; phenylenediamine, tolylenediamine, diethyltolylenediamine, xylylenediamine, diphenylmethanediamine, diphenyletherdiamine, Aromatic polyamines such as polyphenylmethane polyamines; polyamide polyamines such as dicarboxylic acids (eg dimer acids) and excess (2 moles per mole of acid) Low molecular weight polyamide polyamine obtained by condensation with polyamine (the above alkylene diamine, polyalkylene polyamine, etc.); polyether polyamine [hydride of cyanoethylated polyether alcohol (polyalkylene glycol, etc.)]; cyanoethylated polyamine [For example, cyanoethylated polyamine obtained by addition reaction of acrylonitrile and polyamine (the above alkylene diamine, polyalkylene polyamine, etc.), such as biscyanoethyldiethylenetriamine, etc.]; Adipic acid dihydragit, isophthalic acid dihydragit, terephthalic acid dihydragit, etc.), guanidines (butyl guanidine, 1- Ano guanidine etc.); and dicyandiamide; and mixtures of two or more thereof, with preferably from 1 to 20 carbon atoms.
Amino alcohols include alkanolamines such as mono-, di- and tri-alkanolamines (monoethanolamine, monoisopropanolamine, monobutanolamine, triethanolamine, tripropanolamine, etc.); these alkyls (C1 to C4). ) Substituents [N, N-dialkylmonoalkanolamine (N, N-dimethylethanolamine, N, N-diethylethanolamine, etc.), N-alkyldialkanolamine (N-methyldiethanolamine, N-butyldiethanolamine, etc.)] And quaternized nitrogen atoms by quaternizing agents such as dimethyl sulfate or benzyl chloride, and those having 1 to 20 carbon atoms are preferred.

Examples of the carboxy group-containing compound include C1-C20 carvone, aliphatic monocarboxylic acids such as acetic acid and propionic acid; aromatic monocarboxylic acids such as benzoic acid; aliphatics such as succinic acid and adipic acid Polycarboxylic acid; aromatic polycarboxylic acid such as phthalic acid, terephthalic acid, trimellitic acid; polycarboxylic acid polymer (functional number 2 to 100) such as (co) polymer of acrylic acid.
Examples of the polythiol compound of the thiol group-containing compound include divalent to octavalent polyvalent thiols. Specific examples include ethylenedithiol, propylenedithiol, 1,3-butylenedithiol, 1,4-butanedithiol, 1,6-hexanedithiol, 3-methylpentanedithiol, and the like.
Examples of the phosphoric acid compound include phosphoric acid, phosphorous acid, and phosphonic acid.

  Among these active hydrogen-containing compounds, preferred are hydroxyl-containing compounds, and more preferred are polyhydric alcohols and AO adducts of polyhydric alcohols.

  AO to be added to the active hydrogen-containing compound is preferably one having 1 to 7 carbon atoms. As a specific example, as the constituent unit represented by the chemical formula (a), propylene oxide (hereinafter referred to as PO and PO) is used. And 1,2-butylene oxide, and examples of the structural unit represented by the chemical formula (b) include ethylene oxide (hereinafter referred to as EO), trimethylene oxide (that is, oxetane). ), Tetrahydrofuran, and tetrahydropyran.

  In the polyether polyol (A), the weight ratio of the structural unit of the chemical formula (a) to the structural unit of the chemical formula (b) (the total is 100) is such that (a) :( b) is 3:97 to 98. : 2 is preferable, and more preferably 5:95 to 95: 5.

Regarding the addition conditions of AO, a method usually performed may be used, for example, preferably 0.00001 to 10%, more preferably 0.0001 to 1% of the catalyst with respect to the polyoxyalkylene polyol to be produced, The reaction is carried out at 0 to 250 ° C, more preferably 20 to 180 ° C.
In the above and the following, “%” means “% by weight” unless otherwise specified.

The above-mentioned catalyst for ring-opening polymerization of AO may be removed by neutralization, adsorption or the like, if necessary, after completion of the ring-opening polymerization of AO. The polyether polyol obtained by the present invention is preferably used as various raw materials after removing the ring-opening polymerization catalyst.
The removal method may be a commonly used method, which is a method of neutralizing the catalyst and filtering off the generated salt; in the case of an alkali catalyst, an alkali adsorbent [synthetic magnesium silicate (for example, Kyoward 600: manufactured by Kyowa Chemical Industry Co., Ltd.) ), Synthetic aluminum silicate, etc.]; when an acid catalyst is used, a hydrotalcite-based adsorbent (for example, Kyoward 500, Kyoward 1000, Kyoward 2000 <all manufactured by Kyowa Chemical Industry Co., Ltd.>) is used. There are a method; a method of dissolving in a solvent (such as methanol) and washing with water; a method of using an ion exchange resin; a method of removing neutralized salts, and a method of using an alkali or acid adsorbent.

  The adsorbent may be removed as necessary. The removal method may be carried out by any known method, and if necessary, filter aids such as diatomaceous earth (for example, Radiolite 600, Radiolite 800, Radiolite 900 <all manufactured by Showa Chemical Industry Co., Ltd.> ) Etc. can be used. The filtration may be either pressure filtration or vacuum filtration, but pressure filtration is preferred because it is easy to prevent oxygen contamination. The material of the filter is not particularly limited. For example, paper, polypropylene, polytetrafluoroethylene, polyester, polyphenylene sulfide, acrylic, meta-aramid and the like can be mentioned, but paper is preferable.

  In any step, it is preferably carried out in the absence of oxygen, and the oxygen concentration is preferably 1000 ppm or less, more preferably 500 ppm or less. When it is 1000 ppm or less, the polyether polyol is hardly oxidized, and as a result, it is difficult to be colored. It is desirable to reduce the oxygen concentration by passing an inert gas such as nitrogen gas or argon gas into the filtration device.

When the polyether polyol (A) in the polyether polyol of the present invention is produced by ring-opening polymerization, those satisfying the conditions (1) to (3) can be selected by selecting the composition of raw materials and the addition form of AO. What is carried out and satisfies the condition (4) is a compound represented by the chemical formula in the presence of an acid catalyst [preferably a Lewis acid catalyst, more preferably a boron-containing Lewis acid, particularly preferably boron trifluoride and tris (pentafluorophenyl) borane]. This is performed by adding AO forming the structural unit represented by (a) and then adding AO forming (b).
The structure represented by the chemical formula (c) is obtained by adding AO forming (b) to the terminal after the addition of AO forming the structural unit represented by chemical formula (a) is a primary hydroxyl group. The structure represented by the chemical formula (d) is obtained by adding AO forming (b) to the terminal after addition of AO forming the structural unit of chemical formula (a) is a secondary hydroxyl group. That is, the terminal primary hydroxyl value (mol%) after addition of AO forming the structural unit of the chemical formula (a) is equal to the mol% of the structure whose terminal is represented by the chemical formula (c). Accordingly, the condition (4) is satisfied if the terminal primary hydroxyl value after addition of AO forming the structural unit (a) is 40 mol% or more. By using an acid catalyst, the terminal primary hydroxyl value becomes 40 mol% or more.

  As a method for obtaining a polyether polyol by dehydration condensation, a polyol having the chemical formula (a) as a structural unit and a polyol having the chemical formula (b) as a structural unit are dehydrated in the presence of a protonic acid such as sulfuric acid or sodium hydrogensulfate. It may be carried out by any generally known method such as condensation.

In the polyether polyol of this invention, you may contain other polyether polyol which exists as a by-product at the time of manufacture of (A) other than polyether polyol (A). Other polyether polyols include those in which q is all 0 in chemical formula (d).
The content of the polyether polyol other than (A) in the polyether polyol of the present invention is preferably 40 mol% or less, more preferably 30 mol% or less, and particularly preferably 20 mol% or less.

  The terminal primary hydroxyl value of the polyether polyol of the present invention is preferably 60 to 100 mol%, more preferably 70 to 100 mol%, and particularly preferably 80 to 100 mol%. Moreover, the range of a preferable functional group is 2-6, More preferably, it is 2-4.

The polyether polyol obtained by the production method of the present invention (especially 2 to 6 or more polyether polyol) can be used for various applications, but is suitable for producing a foamed or non-foamed polyurethane resin. Used.
The polyurethane resin is produced by reacting a polyol component containing at least a part of the polyether polyol of the present invention with an organic polyisocyanate in the presence of an additive as necessary.
As those used in the polyol component other than the polyether polyol of the present invention, those conventionally used for polyurethane production can be used. Examples of such polyols include polyether polyols obtained by adding PO and / or EO to the above active hydrogen-containing compounds such as propylene glycol and glycerin, and the above hydroxyl group-containing compounds. The proportion of the polyether polyol of the present invention in the polyol component is preferably 90% or more, more preferably 92% or more.

  The polyurethane resin may be produced by any generally known method. As an example of the production method, in the case of a foamed polyurethane resin (polyurethane foam), a polyol component and, if necessary, a predetermined amount of additives are first mixed. The mixture is then rapidly mixed with the organic polyisocyanate using a polyurethane low pressure or high pressure injection foamer or stirrer. The obtained mixed liquid is poured into a sealed mold or an open mold (made of metal or resin), subjected to urethanization reaction, cured for a predetermined time, and demolded to obtain a polyurethane resin.

  In the case of a non-foaming polyurethane resin, a polyol component and an organic polyisocyanate are reacted in advance to obtain a urethane prepolymer, and then a prepolymer method for increasing the molecular weight using a chain extender, and a polyol component containing a chain extender; There is a one-shot method in which an organic polyisocyanate is reacted. Any method may be carried out using a solvent as required.

  Among the polyol components, those used as chain extenders include water, ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, xylylene glycol, glycerin, trimethylolpropane, ethylenediamine, and propylene. Examples thereof include diamine, phenylenediamine, diaminodiphenylmethane, and methylene bis (2-chloroaniline).

  As said organic polyisocyanate, what was conventionally used for polyurethane manufacture can be used. Examples of such isocyanates include aromatic polyisocyanates, aliphatic polyisocyanates, alicyclic polyisocyanates, araliphatic polyisocyanates, and modified products thereof (for example, urethane groups, carbodiimide groups, allophanate groups, urea groups, burette groups). , Isocyanurate group or oxazolidone group-containing modified product) and a mixture of two or more of these.

Examples of aromatic polyisocyanates include 6 to 16 aromatic diisocyanates, 6 to 20 aromatic triisocyanates, and crude products of these isocyanates (excluding carbon in the NCO group; the following isocyanates are also the same). Can be mentioned. Specific examples include 1,3- and / or 1,4-phenylene diisocyanate, 2,4- and / or 2,6-tolylene diisocyanate (TDI), crude TDI, 2,4- and / or 4,4. -Diphenylmethane diisocyanate (MDI), polymethylene polyphenyl isocyanate (crude MDI), and the like.
Examples of the aliphatic polyisocyanate include aliphatic diisocyanates having 6 to 10 carbon atoms. Specific examples include 1,6-hexamethylene diisocyanate and lysine diisocyanate.

Examples of the alicyclic polyisocyanate include alicyclic diisocyanates having 6 to 16 carbon atoms. Specific examples include isophorone diisocyanate (IPDI), 4,4-dicyclohexylmethane diisocyanate, and norbornene diisocyanate.
Examples of the aromatic polyisocyanate include aromatic diisocyanates having 8 to 12 carbon atoms. Specific examples include xylene diisocyanate, α, α, α′α′-tetramethylxylene diisocyanate.
Specific examples of the modified polyisocyanate include urethane-modified MDI and carbodiimide-modified MDI.

In the method for producing a polyurethane resin of the present invention, if necessary, the reaction may be carried out in the presence of an additive described below.
When producing polyurethane foam, a foaming agent is used.
As the foaming agent, water, hydrogen atom-containing halogenated hydrocarbon, low boiling point hydrocarbon, liquefied carbon dioxide gas or the like is used, and two or more kinds may be used in combination.
Specific examples of hydrogen atom-containing halogenated hydrocarbons include HCFC (hydrochlorofluorocarbon) type (for example, HCFC-123 and HCFC-141b); HFC (hydrofluorocarbon) type (for example, HFC-245fa and HFC-365mfc). Etc.
The low boiling point hydrocarbon is a hydrocarbon having a boiling point of −5 to 70 ° C., and specific examples thereof include butane, pentane and cyclopentane.

The amount of the foaming agent used relative to 100 parts of the polyol component when producing the polyurethane foam is preferably 0.1 to 30 parts, more preferably 1 to 20 parts, of water. The hydrogen atom-containing halogenated hydrocarbon is preferably 50 parts or less, more preferably 10 to 45 parts. The low boiling point hydrocarbon is preferably 40 parts or less, more preferably 10 to 30 parts. The amount of liquefied carbon dioxide is preferably 30 parts or less, more preferably 1 to 25 parts.
Above and below parts refer to parts by weight.

  Further, for example, foam stabilizers (dimethylsiloxane, polyether dimethylsiloxane, etc.), urethanization catalysts (tertiary amine catalysts such as triethylenediamine, N-ethylmorpholine, diethylethanolamine, N, N, N ′, N '-Tetramethylhexamethylenediamine, tetramethylethylenediamine, diaminobicyclooctane, 1,2-methylimidazole, 1,8-diazabicyclo [5,4,0] -undecene-7, and / or metal catalysts such as octylic acid Stannous dilauric acid dibutyl stannic acid, lead octylate, etc.), colorant (dye, pigment), plasticizer (phthalate ester, adipic acid ester, etc.), organic filler (synthetic short fiber, thermoplastic or thermosetting) Resin hollow microspheres), flame retardants (phosphate esters, Such as halogenated phosphoric acid ester), antioxidant (triazole, benzophenone, etc.), an antioxidant (a hindered phenol, can be reacted in the presence of a hindered amine, etc.) known additives.

  Regarding the usage-amount of these additives with respect to 100 parts of polyol components, a foam stabilizer becomes like this. Preferably it is 10 parts or less, More preferably, it is 0.5-5 parts. The urethanization catalyst is preferably 10 parts or less, more preferably 0.2 to 5 parts. The colorant is preferably 1 part or less. The plasticizer is preferably 10 parts or less, more preferably 5 parts or less. The organic filler is preferably 50 parts or less, more preferably 30 parts or less. The flame retardant is preferably 30 parts or less, more preferably 5 to 20 parts. The antioxidant is preferably 1 part or less, more preferably 0.01 to 0.5 part. The total amount of additives used is preferably 50 parts or less, more preferably 0.2 to 30 parts.

  The isocyanate index (NCO INDEX) [(NCO group / active hydrogen atom-containing group) equivalent ratio × 100] in producing the polyurethane resin of the present invention is preferably 80 to 150, more preferably 85 to 135, particularly preferably. Is 90-130.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further, this invention is not limited by this.

<Example 1>
A stainless steel autoclave equipped with a 300 ml stirrer and temperature controller was charged with 7.6 parts of propylene glycol and 0.33 parts of potassium hydroxide, and 125.0 parts of PO was added at a reaction temperature of 90 to 110 ° C. for 12 hours. And then aged for 6 hours. Next, 3.0 parts of synthetic silicate (KYOWARD 600, manufactured by Kyowa Chemical) and 2 parts of water were added and treated at 60 ° C. for 3 hours. After taking out from the autoclave, it was filtered through a 1 micron filter and dehydrated to obtain 125.3 parts of a liquid propylene glycol PO adduct (hydroxyl value = 86.1, primary hydroxyl value = 2%).
Subsequently, 0.008 part of tris (pentafluorophenyl) borane was added, and 43.3 parts of PO was added dropwise over 10 hours while controlling the reaction temperature to be 65 to 75 ° C., and then aged at 70 ° C. for 5 hours. did. After adding water and distilling at 105 to 110 ° C. for 4 hours under normal pressure, the temperature was kept at 90 to 100 ° C. and the pressure was kept at 30 to 50 torr. After stopping the introduction of water vapor, the temperature was further raised to 130 ° C. for 3 hours, and the pressure was kept at 50 torr or less for dehydration. This product had a hydroxyl value of 66.1 and a terminal hydroxyl group primary conversion of 71%.
Subsequently, 20.85 parts of THF and 1.14 parts of boron trifluoride were charged, and 16.56 parts of EO were added dropwise over 3 hours while controlling the reaction temperature to be maintained at 50 to 60 ° C., followed by aging for 2 hours. did. Next, after neutralizing boron trifluoride with 0.64 parts of KOH, 3.0 parts of synthetic silicate (Kyoward 600, manufactured by Kyowa Chemical) and 2 parts of water were added and treated at 60 ° C. for 3 hours. After taking out from the autoclave, it was filtered through a 1 micron filter and dehydrated. Liquid propylene glycol (1.0 mol) PO (28.0 mol) .THF (1.8 mol) / EO (3.8 mol) 191.3 parts of polyether polyol A1 (yield: 96%, hydroxyl value = 56.3 (number average molecular weight per functional group: 996), primary hydroxyl value = 94%)) as an adduct It was.

<Example 2>
A stainless steel autoclave equipped with a 300 ml stirring device and temperature controller was charged with 7.6 parts of propylene glycol and 0.26 parts of potassium hydroxide, and 100.0 parts of PO was added at a reaction temperature of 90 to 110 ° C. for 12 hours. And then aged for 6 hours. Next, 3.0 parts of synthetic silicate (KYOWARD 600, manufactured by Kyowa Chemical) and 2 parts of water were added and treated at 60 ° C. for 3 hours. After taking out from the autoclave, it was filtered through a 1-micron filter and dehydrated to obtain 105.0 parts of a liquid propylene glycol PO adduct (hydroxyl value = 107.9, primary hydroxyl value = 2%).
Subsequently, 0.007 part of tris (pentafluorophenyl) borane was added, and 45.0 parts of PO was added dropwise over 10 hours while controlling the reaction temperature to be 65 to 75 ° C., followed by aging at 70 ° C. for 5 hours. did. After adding water and distilling at 105 to 110 ° C. for 4 hours under normal pressure, the temperature was kept at 90 to 100 ° C. and the pressure was kept at 30 to 50 torr. After stopping the introduction of water vapor, the temperature was further raised to 130 ° C. for 3 hours, and the pressure was kept at 50 torr or less for dehydration. This product had a hydroxyl value of 83.1 and a terminal hydroxyl group primary conversion of 71%.
Subsequently, 83.22 parts of THF and 1.17 parts of boron trifluoride were added, and 22.10 parts of EO were added dropwise over 3 hours while controlling the reaction temperature to be maintained at 50 to 60 ° C., followed by aging for 2 hours. did. Next, after neutralizing boron trifluoride with 0.66 parts of KOH, 3.0 parts of synthetic silicate (Kyoward 600, manufactured by Kyowa Chemical) and 2 parts of water were added and treated at 60 ° C. for 3 hours. After taking out from the autoclave, it was filtered through a 1 micron filter and dehydrated. Liquid propylene glycol (1.0 mol) PO (22.0 mol) .THF (5.9 mol) / EO (4.1 mol) Polyether polyol A2 which is an adduct [yield is 96%, hydroxyl value = 57.5 (number average molecular weight per functional group: 976), primary hydroxyl value = 92%] is obtained 247.4 parts. It was.

<Comparative Example 1>
A stainless steel autoclave equipped with a 300 ml stirring device and temperature controller was charged with 7.6 parts of propylene glycol and 0.30 parts of potassium hydroxide, and 120.0 parts of PO was added at a reaction temperature of 90 to 110 ° C. for 12 hours. And then aged for 6 hours. Next, 3.0 parts of synthetic silicate (KYOWARD 600, manufactured by Kyowa Chemical) and 2 parts of water were added and treated at 60 ° C. for 3 hours. After taking out from the autoclave, it was filtered through a 1 micron filter and then dehydrated to obtain 108.0 parts of liquid propylene glycol PO adduct (hydroxyl value = 92.9, primary hydroxyl value = 2%).
Subsequently, 0.007 part of tris (pentafluorophenyl) borane was added, and 38.0 parts of PO was added dropwise over 10 hours while controlling the reaction temperature to be 65 to 75 ° C., followed by aging at 70 ° C. for 5 hours. did. After adding water and distilling at 105 to 110 ° C. for 4 hours under normal pressure, the temperature was kept at 90 to 100 ° C. and the pressure was kept at 30 to 50 torr. After stopping the introduction of water vapor, 0.1 part of potassium hydroxide was added, and the temperature was further raised to 130 ° C. for 3 hours, and the pressure was kept at 50 torr or less for dehydration. This product had a hydroxyl value of 72.4 and a terminal hydroxyl group primary conversion of 70%.
Subsequently, 1.19 parts of boron trifluoride was charged, and 44.0 parts of EO was added dropwise over 3 hours while controlling the reaction temperature to be kept at 50 to 60 ° C., followed by aging for 2 hours. Next, after neutralizing boron trifluoride with 0.66 parts of KOH, 3.0 parts of synthetic silicate (Kyoward 600, manufactured by Kyowa Chemical) and 2 parts of water were added and treated at 60 ° C. for 3 hours. After taking out from the autoclave, it was filtered through a 1 micron filter, dehydrated, and a polyether polyol b1 which is a liquid propylene glycol (1.0 mol) PO (25.5 mol) · EO (10.0 mol) adduct. [Yield: 96%, hydroxyl value = 56.1 (number average molecular weight per functional group: 1000), primary hydroxyl value rate = 92%] 200.2 parts were obtained.

In the following Table 1, the composition of raw materials other than the above used for the production of the polyurethane resin is as follows.
(1) Polyether polyol b2: Polyol [THF (80.0 mol) / methyl THF (20.0 mol) polymer obtained in the same manner as in Example 4 of JP-B-7-116276, hydroxyl value = 57.5 (number average molecular weight per functional group: 976)]
(2) Polyether polyol b3: PTMG [Hydroxyl value = 56.1 (Number average molecular weight per functional group: 1000)] (“PTMG2000” manufactured by Mitsubishi Chemical)
(3) Polyhydric alcohol c: Ethylene glycol (4) Solvent d: Dimethylformamide (5) Organic polyisocyanate e: Monomeric MDI (“Millionate MT” manufactured by Nippon Polyurethane)

<Examples 3-4 and Comparative Examples 2-4>
The components M and N shown in Table 1 were reacted for 12 hours at 70 ° C. under a nitrogen atmosphere with stirring to obtain a polyurethane resin solution.
The obtained polyurethane resin solution was stretched into a film using a 1 mm thick spacer, and then the solvent was evaporated under reduced pressure in a 60 ° C. oven to obtain a 200 μm thick polyurethane resin film. The results of measuring the physical properties of this polyurethane resin film are shown in Table 1.

  The measuring method of the tensile strength, tear strength, and breaking elongation of the obtained film was in accordance with JIS K-7311. As a procedure of the measuring method, the obtained film was punched with a predetermined punching blade, and then it was carried out with an autograph “AGS-500D” manufactured by Shimadzu at a pulling speed of 300 mm / min.

  From the above results, it can be seen that the polyurethane resin of the present invention using the polyether polyol of the present invention is excellent in elongation physical properties when compared with those of equivalent resin strength (tensile strength, tear strength).

  The polyether polyol of the present invention is liquid at room temperature and has good handling properties. Further, it is particularly useful as a raw material for a polyurethane resin obtained by reacting with a polyisocyanate.

Claims (5)

A polyether polyol containing a polyether polyol (A) that satisfies the following (1) to (4).
(1) It has one or more structural units represented by the following chemical formula (a) and one or more structural units represented by the following chemical formula (b).

[N is 1 or 2]

[X is an integer of 2 to 7]
(2) One or more structural units represented by the chemical formula (b) are present at the polyol terminal, and the molecular terminal is — (CH ₂ ) _x —O—H ₂ .
(3) The structural unit represented by the chemical formula (b) at the end of the polyol may be one type or two or more types, and at least one type of x is 3 or more.
(4) 40 to 100 mol% of the polyol terminal is a structure represented by the following chemical formula (c), and 0 to 60 mol% is a structure represented by the following chemical formula (d).

[In the chemical formulas (c) and (d), n is 1 or 2, x is an integer of 2 to 7, p is an average of 1 to 49, and q is an average of 1 to 10]   The polyether polyol according to claim 1, wherein one of the structural units represented by the chemical formula (b) at the end of the polyol is x = 4.   The polyether polyol according to claim 1 or 2, wherein the number average molecular weight per functional group is 300 to 3,000.   The polyether polyol according to any one of claims 1 to 3, which is used for producing a polyurethane resin.   The polyurethane resin containing the polyether polyol according to claim 4, wherein the polyol component and the organic polyisocyanate are reacted in the presence of an additive as necessary, and at least part of the polyol component.