JP2017141359A - Polyalkylene oxide composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyalkylene oxide composition that has a low viscosity and excellent handling ability, although it is polyalkylene oxide with a low degree of unsaturation.SOLUTION: The present invention provides a polyalkylene oxide composition comprising polyalkylene oxide (A) and polyisocyanate (B). In the polyalkylene oxide (A), a molecular weight distribution (Mw/Mn) obtained by gel permeation chromatography (GPC) with polystyrene as a standard substance is 1.029 or less, and a degree of unsaturation is 0.010 meq/g or less.SELECTED DRAWING: None

Description

  The present invention relates to a polyalkylene oxide composition.

  It is industrially known that polyalkylene oxide is produced by addition polymerization of alkylene oxides such as propylene oxide and ethylene oxide using an alkali metal such as potassium hydroxide as a catalyst. However, when polyalkylene oxide is produced by this method, the resulting polyalkylene oxide has a problem that it is difficult to increase the molecular weight because many monools are by-produced and the degree of unsaturation is high.

  A polyalkylene oxide composition containing such a highly unsaturated polyalkylene oxide uses a large amount of a urethanization catalyst to improve productivity and problems such as time-consuming curing and prepolymerization and poor productivity. There is a problem that it is inferior in storage stability when used as a urethane prepolymer. Moreover, the polyurethane obtained by using such polyalkylene oxide having a high degree of unsaturation has a problem that the mechanical properties are lowered.

  As polyalkylene oxides having a low degree of unsaturation, polyalkylene oxides obtained by using specific phosphazenium salts, boron compounds, and cesium hydroxide as catalysts are known (for example, see Patent Documents 1 and 2). However, the degree of unsaturation of the polyalkylene oxides described in Patent Documents 1 and 2 is still high, and further reduction is required.

  Furthermore, as a polyalkylene oxide having a low degree of unsaturation, a polyalkylene oxide obtained by using a double metal cyanide complex as a catalyst is known (for example, see Patent Document 3). However, the polyalkylene oxide described in Patent Document 3 has problems such as poor handling due to the wide molecular weight distribution of about 1.1 and high viscosity, and the polyalkylene oxide composition using the polyalkylene oxide has a viscosity. There exists a subject that it rises and it is inferior to handling property and curability. Furthermore, since the urethane cured product obtained using the same is likely to be non-uniform, there is a large variation in mechanical properties and the usage is limited.

JP 2007-131845 A Japanese Patent No. 3905638 (Japanese Patent Laid-Open No. 11-106500) Japanese Patent Laid-Open No. 4-59825

  The present invention has been made in view of the above-described background art, and an object of the present invention is to provide a polyalkylene oxide composition having low viscosity and excellent handleability despite being a low-unsaturation polyalkylene oxide. There is to do.

  As a result of intensive studies to solve the above problems, the present inventors have found that a composition of polyalkylene oxide and polyisocyanate having a specific molecular weight distribution with a specific degree of unsaturation can solve the above problems, and the present invention. It came to complete.

  That is, this invention relates to the polyalkylene oxide composition shown below.

  [1] A composition comprising a polyalkylene oxide (A) and a polyisocyanate (B), wherein the polyalkylene oxide (A) is obtained by gel permeation chromatography (GPC) using polystyrene as a standard substance. A polyalkylene oxide composition having a distribution (Mw / Mn) of 1.029 or less and an unsaturation value of 0.010 meq / g or less.

  [2] The polyalkylene oxide composition according to the above [1], wherein the polyalkylene oxide (A) is represented by the following general formula (1).

[In general formula (1), R represents an m-valent group obtained by removing m active hydrogens from an active hydrogen-containing compound (R [—H] m); Z represents an alkylene group or cycloalkylene having 2 to 12 carbon atoms; And A is an alkylene group having 3 carbon atoms. When there are a plurality of Z or A, each may be the same or different; m is an integer of 1 or 2 to 100; p is an integer of 0 or 1 to 500, q is an integer of 1 to 1000; r is 0 Or it is an integer of 1-500. ]
[3] Number average molecular weight (M) calculated from molecular weight distribution (Mw / Mn) and hydroxyl value (OHV) determined by gel permeation chromatography (GPC) using polystyrene of polyalkylene oxide (A) as a standard substance ) Is the following formula (1):

The polyalkylene oxide composition according to the above [1] or [2], wherein the polyalkylene oxide (A) is 50 to 99.9% by weight and the polyisocyanate (B) is 0.1%. The polyalkylene oxide composition according to any one of the above [1] to [3], which is contained in a range of ˜50% by weight.

  [5] The polyalkylene oxide composition according to any one of the above [1] to [4], wherein the polyalkylene oxide composition has a viscosity in the range of 100 to 100,000 mPa · s.

  [6] A molecular weight distribution (Mw / Mn) obtained by a gel permeation chromatography (GPC) method using polystyrene as a standard substance is connected in series to four columns packed with a 3 μm particle size filler in a separation column, The polyalkylene oxide composition as described in any one of [1] to [5] above, wherein the composition is a molecular weight distribution analyzed under the condition that a resistance tube is connected to the reference side and tetrahydrofuran is used as a developing solvent.

  [7] A urethane prepolymer comprising a reaction product of polyalkylene oxide (A) and polyisocyanate (B) contained in the polyalkylene oxide composition according to any one of [1] to [6].

  [8] A urethane prepolymer characterized by reacting the polyalkylene oxide (A) and the polyisocyanate (B) contained in the polyalkylene oxide composition according to any one of [1] to [6] above Production method.

  [9] The polyalkylene oxide composition according to any one of [1] to [6] above or the urethane cured product of the urethane prepolymer according to [7] above.

  [10] A method for producing a urethane cured product comprising curing the polyalkylene oxide composition according to any one of [1] to [6] or the urethane prepolymer according to [7].

  The polyalkylene oxide composition of the present invention is a polyurethane-forming composition and has a low viscosity, excellent handling properties and good curability despite being a low-unsaturation polyalkylene oxide.

  Moreover, since the urethane cured product of the present invention has small variations in mechanical properties, it can be suitably used for a wide range of applications.

  The present invention is described in detail below.

  The polyalkylene oxide composition of the present invention is a composition comprising a polyalkylene oxide (A) and a polyisocyanate (B). The polyalkylene oxide (A) is gel permeation chromatography (polystyrene as a standard substance). The molecular weight distribution (Mw / Mn) obtained by the GPC method is 1.029 or less and the degree of unsaturation is 0.010 meq / g or less.

<Chemical composition of polyalkylene oxide (A)>
As the polyalkylene oxide (A) used in the polyalkylene oxide composition of the present invention, one or more active hydrogen compounds R [—H] m are used, and one kind of alkylene oxide having 2 to 12 carbon atoms is used. Or it is preferable that it is the alkylene oxide addition product which added 2 or more types, and it is preferable that it is a polyalkylene oxide represented by following General formula (1).

[In general formula (1), R represents an m-valent group obtained by removing m active hydrogens from an active hydrogen-containing compound (R [—H] m); Z represents an alkylene group or cycloalkylene having 2 to 12 carbon atoms; And A is an alkylene group having 3 carbon atoms. When there are a plurality of Z or A, each may be the same or different; m is an integer of 1 or 2 to 100; p is an integer of 0 or 1 to 500, q is an integer of 1 to 1000; r is 0 Or it is an integer of 1-500. ]
Of these, compounds having an oxyalkylene group and having at least one active hydrogen group per molecule in any molecule such as a polymer end or a branched chain end, that is, a monool (when m = 1) ) Or polyol (when m is an integer of 2 to 100).

  The active hydrogen-containing compound (R [—H] m) is not particularly limited as long as it has an active hydrogen group. For example, water, propylene glycol, ethylene glycol, diethylene glycol, dipropylene glycol, butylene glycol, 1, Bifunctional diols such as 6-hexanediol, tripropylene glycol, triethylene glycol, polyoxyalkylene diol, bisphenols such as bisphenol A, bisphenol F, bisphenol AD, dihydroxybenzenes such as catechol, resorcin, hydroquinone, methyl Examples thereof include compounds having two active hydrogen groups such as amines such as amine, ethylamine, propylamine and butylamine. In addition, glycerin, trimethylolpropane, 1,2,6-hexanetriol, a trifunctional low molecular weight polyol such as Sanyox GP-250, GP-400, GP-600, GP-1000 manufactured by Sanyo Chemical Industries, etc. Examples thereof include compounds having three or more active hydrogen groups such as tetraols such as triol, pentaerythritol, and diglycerin, hexol, ammonia, ethanolamine, diethanolamine, and amines such as triethanolamine. Furthermore, the compound which has one or more active hydrogens, such as a compound which has one active hydrogen group, such as polyoxyalkylene monool of molecular weight 1000 or less, is mentioned. As the active hydrogen-containing compound (R [—H] m), one or a mixture of two or more selected from these can be used.

  Among these, an active hydrogen-containing compound having a boiling point of 150 ° C. or higher is preferable and an active hydrogen having a boiling point of 200 ° C. or higher because a by-product during catalyst preparation is easily removed and a polyalkylene oxide having a narrow molecular weight distribution is easily obtained. More preferred are contained compounds. For example, trifunctional low polyols such as tripropylene glycol, triethylene glycol, polyoxyalkylene diol, etc., and trifunctional low grades such as Sanix GP-250, GP-400, GP-600, GP-1000 manufactured by Sanyo Kasei Co., Ltd. One kind or a mixture of two or more kinds such as triols such as molecular weight polyol and polyoxyalkylene monool having a molecular weight of 1000 or less can be mentioned.

  The alkylene oxide to be added to the active hydrogen-containing compound (R [—H] m) is not particularly limited as long as it is a compound having one or more epoxy rings in the molecule. For example, ethylene oxide, propylene oxide C2-C12 alkylene oxides such as butylene oxide and styrene oxide can be used, and one or more alkylene oxides may be used.

  Among these, one or two or more alkylene oxides containing an alkylene oxide having 2 to 3 carbon atoms such as propylene oxide and ethylene oxide, which are easily available industrially, are preferable, and one or two or more kinds containing propylene oxide are preferable. More preferred are alkylene oxides.

  Further, the water content in the alkylene oxide is preferably 200 ppm or less because it acts as an initiator during the reaction to easily obtain a polyalkylene oxide having a narrow molecular weight distribution that is difficult to spread. More preferably, it is 100 ppm or less, Most preferably, it is 60 ppm or less. It is easy to obtain an alkylene oxide of 200 ppm or less by dehydrating a commercially available alkylene oxide using an adsorbent such as zeolite.

  As ZO in the above general formula (1), the viscosity tends to be low and it is easy to show good urethane moldability, so that the polyoxide derived from alkylene oxide having 2 to 12 carbon atoms such as ethylene oxide, propylene oxide, butylene oxide, styrene oxide, etc. It preferably has an ether structure. A polyether structure derived from one or more alkylene oxides selected from ethylene oxide and propylene oxide is more preferable, and a polyether structure selected from ethylene oxide and propylene oxide is most preferable.

  P in the general formula (1) is 0 or an integer of 1 to 500, preferably p = 0 or an integer of 1 to 100, and more preferably p = 0.

  Examples of Z in the general formula (1) include a structure represented by the following general formula (2).

[In General Formula (2), R ₂ , R ₃ , R ₄ , and R ₅ each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a cycloalkyl having 3 to 10 carbon atoms. However, the total carbon number of R _{2 to} R ₅ does not exceed 10. Further, any _two of R _{2 to} R ₅ may be bonded to form a cycloalkyl group. ]
In addition, the AO in the general formula (1) is a polyether structure derived from an alkylene oxide having 3 carbon atoms such as propylene oxide because the viscosity tends to be low and the urethane is likely to exhibit good mechanical properties. It is preferable.

  As A in the said General formula (1), the structure shown by a following formula is mentioned, for example.

  Q in the said General formula (1) is an integer of 1-1000, Preferably it is an integer of q = 30-500, More preferably, it is an integer of q = 50-250.

  R in the general formula (1) is 0 or an integer of 1 to 500. Since it is hard to solidify at low temperature and easy to handle, it is preferably r = 0 or an integer of 1-90, more preferably r = 0.

  Regarding the relationship between p, q and r in the general formula (1), since viscosity tends to be low and good mechanical properties are easily obtained when urethane is used, p + q> r (where p + q is 10 to 1000, q 10 to 1000 and r is preferably 0 or 1 to 90). More preferably, p + q> 5r (where p + q is 30 to 600, q is 30 to 500, r is 0 or 1 to 90), and most preferably p + q> 10r (where p + q is 50 to 600, q 50 to 500 and r is 0 or 1 to 90).

  M in the said General formula (1) is an integer of 1 or 2-100. Since the molecular weight distribution tends to be narrow and easy to handle, it is preferably 1, 2, or 3, and most preferably 2.

<Molecular weight distribution of polyalkylene oxide (A)>
The polyalkylene oxide (A) used in the polyalkylene oxide composition of the present invention has a molecular weight distribution (Mw / Mn) of 1.029 or less determined by gel permeation chromatography (GPC) using polystyrene as a standard substance. . Preferably it is the range of 1.003-1.026, More preferably, it is the range of 1.005-1.019, Most preferably, it is the range of 1.006-1.016. When the molecular weight distribution (Mw / Mn) obtained by the gel permeation chromatography (GPC) method using polyalkylene oxide polystyrene as the standard substance exceeds 1.029, a significant viscosity reduction effect cannot be obtained. It is difficult to use because of poor handling and further deterioration of dispersibility in a solvent. As a raw material of polyurethane, the mixing property with each raw material is poor, and the reaction and composition are not uniform, making it difficult to use.

  When the molecular weight distribution (Mw / Mn) obtained by the gel permeation chromatography (GPC) method using polyalkylene oxide (A) polystyrene as a standard substance exceeds 1.029, a significant viscosity reduction effect cannot be obtained. The handling property in bulk is poor, and further, the dispersibility in a solvent is also deteriorated, so that it may be difficult to use. Even as a raw material of polyurethane, the mixing property with each raw material is poor, and there is a possibility that the reaction and composition become non-uniform, making it difficult to use.

  Molecular weight distribution (Mw / Mn) determined by gel permeation chromatography (GPC) method using polystyrene of polyalkylene oxide (A) used in the polyalkylene oxide composition of the present invention as a standard substance, and hydroxyl value (OHV) described later ) And the number average molecular weight (M) calculated from the following formula (1):

Is more preferable, and more preferably the following mathematical formula (2):

Most preferably, the following formula (3):

Is to satisfy.

  The molecular weight distribution (Mw / Mn) determined by gel permeation chromatography (GPC) method using polystyrene as a standard substance is a series connection of four columns packed with a 3 μm particle size filler in a separation column for the reason described later. It is preferably a molecular weight distribution measured and analyzed under the condition that a resistance tube is connected to the reference side and tetrahydrofuran is used as a developing solvent, and a molecular weight distribution calculated using a cubic approximate curve calibration curve using standard polystyrene. (Mw / Mn) is desirable.

  The number of separation columns is preferably 3 to 5, particularly preferably 3 to 5 because the resolution (theoretical plate number) is high and it is easy to suppress the spread of molecular weight due to fluctuations in the baseline and minute peaks of impurities in the liquid. There are four.

  The particle size of the filler of the separation column is preferably 1 to 4.5 μm because the measurement time is appropriate, and it is easy to suppress the molecular weight distribution from spreading due to fluctuations in the baseline and minute peaks of impurities in the liquid. Particularly preferably, it is 3 μm.

  The exclusion limit of the separation column is preferably 50,000 to 3 million, more preferably 60,000 to 400,000. The inner diameter of the separation column is preferably 5 to 7.5 mmφ, more preferably 6 mmφ. The length of the separation column is preferably 10 to 25 cm, more preferably 15 cm.

  Examples of such a separation column include Tskel SuperH4000 and Tskel SuperH3000 manufactured by Tosoh Corporation. The most preferable configuration of the separation column is a configuration in which a total of four Tskel SuperH4000 × 2 and Tskel SuperH3000 × 2 manufactured by Tosoh are connected in series.

  The flow rate on the separation column side is preferably 0.5 to 0.9 ml / min, more preferably 0.6 ml / min. The column temperature is preferably 30 ° C to 50 ° C, more preferably 40 ° C.

  In addition, it is preferable to connect 2 to 6 resistance tubes, more preferably 5 resistance tubes, and most preferably, since it is easy to suppress the molecular weight distribution from spreading due to pump pulsation on the reference side. This is a connection of five resistance tubes and one separation column.

  As the resistance tube, a tube having a length of 2 m and an inner diameter of 0.1 mmφ is preferable.

  The flow rate on the reference side is preferably 0.1 to 0.1 in the state of five resistance tubes because the pulsation cycle of the pump is short and the fluctuation of the baseline is easily suppressed and the molecular weight distribution is easily prevented from spreading due to the pulsation of the pump. 6 ml / min, more preferably 0.15 ml / min.

  The polystyrene used for the standard material of the cubic approximate curve calibration curve is preferably 6 to 10 points, more preferably 8 points. The molecular weight of polystyrene used for the standard substance having a known molecular weight is preferably selected from the range of 300 to 3000000, and more preferably selected from the range of 450 to 1100000. Specifically, for example, 8-point selection of 500, 1010, 2630, 10200, 37900, 96400, 427000, 1090000, etc. can be mentioned, and the measurement of the standard substance is 4 points of 500, 2630, 37900, 427000 and 1010, 10200, The measurement may be performed in two steps, such as 96400 and 1090000.

  The developing solvent is preferably dimethylformamide or tetrahydrofuran, and more preferably BHT stabilizer-containing special grade tetrahydrofuran manufactured by Wako Pure Chemical Industries.

  The sample concentration is preferably 0.5 to 2 mg / ml, more preferably 1 mg / ml. The injection amount of the sample solution is preferably 10 to 90 μl, more preferably 20 μl, in which the peak is difficult to broaden and the molecular weight distribution is difficult to spread.

  The area ratio of the low molecular weight component in the gel permeation chromatography (GPC) method is preferably 4.5% or less of the entire peak, and more preferably 2% or less. The viscosity is likely to increase with a decrease in the area ratio of the low molecular weight component, but it is preferable because polyurethane has few migration components and is easy to handle and mechanical properties.

  In the present invention, the “area ratio of low molecular weight components” in the gel permeation chromatography (GPC) method is calculated when the molecular weight distribution is measured by the gel permeation chromatography (GPC) method using polystyrene as a standard substance. This refers to a low molecular weight component having a number average molecular weight of 1/3 or less of the number average molecular weight (Mn), and is 1/3 of the number average molecular weight (Mn) calculated when measuring the baseline and molecular weight distribution. The area% of the low molecular weight component can be obtained by dividing the peak.

<Properties of polyalkylene oxide (A)>
The degree of unsaturation of the polyalkylene oxide (A) used in the polyalkylene oxide composition of the present invention is 0.010 meq / g or less. Preferably, it is the range of 0.002-0.009 meq / g, More preferably, it is the range of 0.004-0.008 meq / g.

  Polyurethane obtained by using polyalkylene oxide having a high degree of unsaturation exceeding 0.010 meq / g is difficult to use due to deterioration of mechanical properties and handling properties due to generation of many migration components without being cured well. . Furthermore, a large amount of low molecular weight monools are produced as a by-product, resulting in a decrease in the number average molecular weight, making it difficult to increase the molecular weight of the polyalkylene oxide and obtaining a polyalkylene oxide having a narrow molecular weight distribution itself. .

In the present invention, the “unsaturation degree (meq / g)” of the polyalkylene oxide (A) is the total amount of unsaturated groups contained in 1 g of the polyalkylene oxide (A), and is defined in JIS K1557. 7 is a value measured according to the method defined in 7. The degree of unsaturation of polyalkylene oxide is an indicator of the amount of monool present in the polyalkylene oxide. Increasing the viscosity decreases the viscosity, but the average number of functional groups of the polyalkylene oxide may decrease. When this occurs, it may cause a termination reaction, leading to a decrease in the molecular weight of the polyurethane and an increase in uncrosslinked low molecular weight components, or mechanical properties may decrease due to acting as a dangling chain in the polyurethane.
The number average molecular weight of the polyalkylene oxide (A) used in the polyalkylene oxide composition of the present invention is preferably 500 or more, more preferably in the range of 1000 to 30000, and most preferably in the range of 1000 to 5000. is there. When the number average molecular weight is less than 500, there is no remarkable viscosity reduction effect, and the polyurethane obtained from such a polyalkylene oxide (A) tends to have large variations in mechanical properties.
In the present invention, the number average molecular weight of the polyalkylene oxide (A) refers to the number average molecular weight calculated from the hydroxyl value, and the following formula (4) is based on the hydroxyl value (OHV, unit is mgKOH / g) of the polyalkylene oxide. :

The value calculated using.

  Here, “OHV” is a value measured according to JIS K1557 6.4. The “number of hydroxyl groups per molecule” refers to the number of active hydrogen atoms per molecule of the active hydrogen compound that is an initiator used as a raw material when the polyalkylene oxide (A) is produced. If the number of active hydrogen atoms in the initiator cannot be specified with a commercial product, the nominal functional group number is used.

  The viscosity in 25 degreeC conditions of the polyalkylene oxide (A) used for the polyalkylene oxide composition of this invention is not specifically limited, Although it is suitably selected by a use, Preferably it is the range of 1-2000 Pa.s (25 degreeC). More preferably, it is the range of 2-1000 Pa.s (25 degreeC). A viscosity of the polyalkylene oxide (A) in the range of 1 to 2000 Pa · s (25 ° C.) is preferable because the physical properties of the polyurethane can be easily controlled.

  In the present invention, “viscosity” at 25 ° C. refers to a value measured with a cone plate rotational viscometer of JIS K1557-5, section 6.2.3. Specifically, it refers to the viscosity at a shear rate of 0.1 (1 / s), but when the viscosity does not fall within the measurement range, the shear rate range is set to 0.01 to 10 (1 / s to enter the measurement range. ) May be adjusted within the range.

<Production of polyalkylene oxide (A)>
The method for producing the polyalkylene oxide (A) used in the polyalkylene oxide composition of the present invention is not particularly limited. For example, in the presence of an active hydrogen-containing compound and an iminophosphazenium salt catalyst, It can be produced by ring-opening polymerization of oxide.

For example, when an active hydrogen-containing compound and an iminophosphazenium salt catalyst are mixed and subjected to reduced pressure treatment to prepare a catalytically active species precursor, it is sufficient for 2 hours or more under severe pressure reduction conditions of 100 ° C. or more and 0.3 kPa or less. Inhibiting polyalkylene oxides other than those derived from active hydrogen-containing compounds in the initiator, which is a factor that broadens the molecular weight distribution by removing water and solvents,
Further, when adjusting the catalytically active species by mixing a Lewis acid and reducing the pressure, the by-product is sufficiently removed for 2 hours or more under conditions of 100 ° C. or more and 0.3 kPa or less, and a by-product having a low boiling point is specified. Inhibiting Lewis acid-derived polyalkylene oxide, which is a factor that broadens the molecular weight distribution by selecting the Lewis acid of
Through a production process of adding alkylene oxide as a catalyst combining a specific Lewis acid and an iminophosphazenium salt catalyst with few side reactions,
Using an alkylene oxide having a moisture value of 100 ppm or less,
It is preferable because the polyalkylene oxide (A) is more easily obtained by the above, but is not particularly limited.

  Although it is not particularly limited as an iminophosphazenium salt catalyst, iminophosphazenium salt and Lewis acid are used in combination because of the wide range of application of alkylene oxide, high polymerization activity, and low degree of unsaturation. It is preferable to use a catalyst system prepared.

  Here, the Lewis acid is not particularly limited, and examples thereof include an aluminum compound, a zinc compound, and a boron compound. Of these, organoaluminum, aluminoxane, and organozinc are preferable, and organoaluminum is more preferable because it becomes an alkylene oxide polymerization catalyst having excellent catalytic performance.

  Examples of the aluminum compound include trimethylaluminum, triethylaluminum, triisobutylaluminum, trinormalhexylaluminum, triethoxyaluminum, triisopropoxyaluminum, triisobutoxyaluminum, triphenylaluminum, diphenylmonoisobutylaluminum, monophenyldiisobutylaluminum, etc. Organic aluminum; an aluminoxane such as methylaluminoxane, isobutylaluminoxane, and methyl-isobutylaluminoxane; and inorganic aluminum such as aluminum chloride, aluminum hydroxide, and aluminum oxide.

  Among these, trimethylaluminum, triethylaluminum, which are easy to remove because the boiling point of by-products during the preparation of the catalytically active species is as low as 100 ° C. or less, and are easy to suppress the polyalkylene oxide derived from Lewis acid, which causes the molecular weight distribution to be broadened. Triisobutyl aluminum, trinormal hexyl aluminum, triethoxy aluminum, triisopropoxy aluminum and the like are preferable. The compound produced as a by-product in the preparation of the catalytically active species can be judged from the structure of Lewis acid. For example, trimethylaluminum has H added to the methyl group of the substituent on aluminum, and triisobutylaluminum has the isobutyl substituent on aluminum. In the case of isobutane in which H is added to the group, triisopropoxyaluminum is isopropanol in which H is added to the isopropoxy group.

  Examples of the zinc compound include organic zinc such as dimethyl zinc, diethyl zinc and diphenyl zinc; and inorganic zinc such as zinc chloride and zinc oxide.

  Examples of the boron compound include triethylborane, trimethoxyborane, triethoxyborane, triisopropoxyborane, triphenylborane, tris (pentafluorophenyl) borane, and trifluoroborane.

  The iminophosphazenium salt is not particularly limited as long as it is a compound having an imino group and a PN bond, and examples thereof include compounds represented by the following general formula (3) (for example, JP 2011-132179 A). No. publication).

[In said general formula, R < ₁ > and R < ₂ > respectively independently represents a hydrogen atom or a C1-C20 hydrocarbon group. Incidentally, the R ₁ and R ₂ may be bonded to form a ring structure, R ₁ s or R ₂ together may form a ring structure together. X ⁻ represents a hydroxy anion, an alkoxy anion having 1 to 4 carbon atoms, a carboxy anion, an alkyl carboxy anion having 2 to 5 carbon atoms, or a hydrogen carbonate anion. ]
The ratio of the iminophosphazenium salt to the Lewis acid is not particularly limited, and may be any as long as the action as an alkylene oxide polymerization catalyst is exhibited. For example, iminophosphazenium salt: Lewis acid = 1 : It is the range of 0.002-500 (molar ratio).

  The polymerization temperature at the time of producing the polyalkylene oxide of the present invention is not particularly limited, but the range of 70 to 150 ° C. is preferable because the polyalkylene oxide is decomposed and the molecular weight distribution is difficult to spread and the catalytic activity is easily expressed. More preferably, it is the range of 90-110 degreeC.

  Although the polymerization pressure at the time of producing the polyalkylene oxide of the present invention is not particularly limited, it is in the range of 0.05 to 1.0 MPa, preferably in the range of 0.1 to 0.6 MPa.

  The stirring speed at the time of producing the polyalkylene oxide of the present invention is not particularly limited, and depends on the shape and inner volume of the polymerization vessel, the shape of the stirring blade, and the like. In this case, it is preferable to sufficiently stir at 300 rpm or more.

  When adding an alkylene oxide to an active hydrogen-containing compound using a catalyst that combines an iminophosphazenium salt and a Lewis acid, the iminophosphazenium salt (including its precursor), Lewis acid, and active hydrogen are added. A method of preparing catalytically active species by mixing the contained compounds at the same time and preparing a catalytically active species by performing heating / depressurization treatment, etc. A method of preparing a catalytically active species by mixing another component with two of these components and performing heating / depressurizing treatment, etc., mixing two of these components and performing heating / depressurizing treatment, etc. Any method such as a method of preparing a catalytically active species after preparing a catalytically active species precursor and mixing other one component and further performing heating / depressurization treatment, etc. may be used, but by-products and impurities are removed. Easy and narrow molecular weight Since it is easy to obtain the polyalkylene oxide of the cloth, preferably the iminophosphazenium salt and the active hydrogen-containing compound are mixed and then subjected to heating and decompression treatment, and then Lewis acid is mixed and further subjected to heating and decompression treatment, etc. It is preferred to go through a manufacturing process to prepare the catalytically active species and add the alkylene oxide.

  In this case, the temperature of the heating / depressurizing treatment is preferably 100 ° C. or more, more preferably in the range of 100 to 130 ° C., because by-products and impurities are easily removed and polyalkylene oxide having a narrow molecular weight distribution is easily obtained. The pressure during the heating / decompression treatment is preferably less than 0.5 kPa, more preferably in the range of 0.001 to 0.2 kPa, because by-products and impurities are easily removed and polyalkylene oxide having a narrow molecular weight distribution is easily obtained. is there. The heating / decompression treatment time at that time varies depending on the shape of the reaction vessel and the like, but it may be 2 hours or more after mixing the iminophosphazenium salt and / or its precursor, Lewis acid, and active hydrogen-containing compound. More preferably, the iminophosphazenium salt and / or its precursor and the active hydrogen-containing compound are added to the heated / reduced distillation for 2 hours or more after mixing, and the heating / reduced distillation is further performed for 2 hours or more after mixing with the Lewis acid. Preferably it is done. Further, a low-boiling dehydrated solvent may be added to remove impurities, and azeotropic operation may be performed to remove impurities.

  The polyalkylene oxide (A) used in the polyalkylene oxide composition of the present invention is not particularly limited, but it is preferable to remove the catalyst after polymerization because the viscosity may increase when the catalyst remains. More preferably, the amount of catalyst residue is 200 ppm or less, and most preferably 100 ppm or less. Here, the catalyst residue amount refers to the combined catalyst residue amount when two or more types of catalysts are used in combination.

<Polyisocyanate (B)>
Although it does not specifically limit as polyisocyanate (B) used for the polyalkylene oxide composition of this invention, For example, the compound which has at least 2 isocyanate group is mentioned.

  Specifically, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 2,4′-diphenylmethane diisocyanate, 4,4′-diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, tolidine diisocyanate, xylylene diisocyanate 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, lysine diisocyanate, triphenylmethane triisocyanate, tetramethylxylene diisocyanate, 1,6-hexamethylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, isophorone diisocyanate, 1 , 4-cyclohexane diisocyanate, norbornane diisocyanate, lysine ester triisocyanate, 1,6,11- Ndecane triisocyanate, 1,8-diisocyanate-4-isocyanate methyloctane, 1,3,6-hexamethylene triisocyanate, bicycloheptane triisocyanate, trimethylhexamethylene diisocyanate, isocyanate-containing prepolymers by reaction of them with polyols, And a mixture of two or more of these. Furthermore, modified products of these isocyanates (urethane group, carbodiimide group, allophanate group, urea group, burette group, isocyanurate group, amide group, imide group, uretonimine group, uretdione group or oxazolidone group-containing modified product) and polymethylene Condensates (sometimes referred to as polynuclear bodies) such as polyphenylene polyisocyanate (polymeric MDI) are also included.

  Among these, aromatic isocyanates, alicyclic isocyanates, and modified products thereof are preferable because it is easy to obtain a polyalkylene oxide composition having excellent productivity and excellent curability.

  Specifically, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 2,4′-diphenylmethane diisocyanate, 4,4′-diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, tolidine diisocyanate, xylylene diisocyanate , Aromatic isocyanate-containing prepolymers, alicyclic isocyanate-containing prepolymers, modified products of these isocyanates (urethane groups, carbodiimide groups, allophanate groups, urea groups, burette groups, isocyanurate groups, amide groups, imide groups, uretonimines Group, uretdione group or oxazolidone group-containing modified product) and the like. These isocyanates may be used alone or in combination.

  Examples of the isocyanate-containing prepolymer include polyoxyalkylene monoalkyl ethers, isotridecanols, hexyldecanols, monools such as ethylhexanol and butyltetraglycol, polyols, monoamines, polyamines, and the like, and reaction products of isocyanates. It is done.

<Additives>
The polyalkylene oxide composition of the present invention may contain a urethanization catalyst, an antifoaming material, a foam stabilizer, and other additives as necessary.

  The content of the additive in the polyalkylene oxide composition of the present invention is not particularly limited, but is preferably in the range of 5% by weight or less, more preferably in the range of 0.1% by weight or less. .

<Polyalkylene oxide composition>
Although it does not specifically limit as content of polyalkylene oxide (A) in the polyalkylene oxide composition of this invention, Usually, it is the range of 50-99.9 weight%, Preferably it is 60-99.8. It is the range of weight%, More preferably, it is the range of 70-99.5 weight%. When the content of the polyalkylene oxide (A) is in the range of 50 to 99.9% by weight, it is easy to handle because it is difficult to become a paste or a solid and easily maintain a liquid state. Moreover, if it is in said range, it will become a uniform composition easily, and when it is set as a urethane prepolymer, it will become low viscosity and will be easy to handle.

  In addition, the molar ratio (NCO / OH) of the total amount of OH groups in the polyalkylene oxide (A) and the total amount of NCO groups in the polyisocyanate (B) in the polyalkylene oxide composition depends on the use of the obtained urethane cured product. Although it is different and is not particularly limited, it is usually in the range of NCO / OH = 0.001-20.

  Especially, in order to obtain the urethane prepolymer of the isocyanate group terminal mentioned later, the range of NCO / OH = 1.3-10 is preferable, More preferably, it is the range of NCO / OH = 1.5-3.9. If it is in the range of NCO / OH = 1.3 to 10, it depends on the application, but the viscosity is too low and the possibility of deterioration of the handling property due to the liquid flow becomes low, and the viscosity becomes too high and the handling property is deteriorated. The possibility is also low, which is preferable.

  The polyisocyanate (B) content in the polyalkylene oxide composition of the present invention is usually in the range of 0.1 to 50% by weight, preferably in the range of 0.2 to 40% by weight, and more preferably. Is in the range of 0.5-30% by weight. When the content of the polyisocyanate (B) is in the range of 0.1 to 50% by weight, it is easy to handle because it is difficult to become a paste or solid and easily maintain a liquid state. Moreover, if it is in said range, it will become easy to become a uniform composition, and since it becomes low viscosity when it is set as the urethane prepolymer mentioned later, it is preferable.

  The viscosity of the polyalkylene oxide composition of the present invention is not particularly limited because it varies depending on the properties required for the urethane prepolymer, urethane cured product, and the like, and the NCO / OH ratio that expresses the use, but is usually 100 to 100%. The range is 100,000 mPa · s, preferably 200 to 30,000 mPa · s, and more preferably 300 to 3000 mPa · s. If it is in the range of 100 to 100,000 mPa · s, handling such as stirring and molding is easy although it varies depending on the application.

<Urethane prepolymer>
The urethane prepolymer of the present invention comprises a reaction product of polyalkylene oxide (A) and polyisocyanate (B) contained in the polyalkylene oxide composition of the present invention.

  The urethane prepolymer of the present invention has a low viscosity, excellent handling properties, and fast curability. Further, the urethane prepolymer of the present invention has a lower viscosity than a urethane prepolymer synthesized using a low-monool polypropylene glycol (PPG) having the same molecular weight, and thus is easily cured uniformly. Furthermore, since the urethane prepolymer of the present invention has a shorter curing period than the urethane prepolymer obtained by using general-purpose PPG or low-monool PPG having the same molecular weight, the period of tackiness is shortened and dust is mixed in. Therefore, variation in mechanical properties of the obtained urethane cured product is remarkably reduced.

  The method for producing the urethane prepolymer of the present invention is not particularly limited. For example, by reacting the polyalkylene oxide (A) and polyisocyanate (B) contained in the polyalkylene oxide composition of the present invention, for example. Can be manufactured. If necessary, the polyalkylene oxide (A) and the polyisocyanate (B) may be subjected to a urethanization reaction (prepolymerization) in the presence of a urethanization catalyst, a solvent, an antifoaming material, and other additives. Therefore, the obtained urethane prepolymer may contain a urethanization catalyst, an antifoaming material, an additive and the like.

  Here, although it does not specifically limit as temperature of a urethanation reaction, Usually, it is 120 degrees C or less, Preferably it is 50-110 degreeC. If it is 120 degrees C or less, it will be easy to obtain the urethane prepolymer of reaction rate control or a predetermined number average molecular weight and structure.

  The reaction time for the urethanization reaction is not particularly limited, but it is preferably 1 to 20 hours at 120 ° C. or lower. The end point of the reaction can be determined by measuring the residual amount of isocyanate by titration or disappearance of the isocyanate peak by IR measurement.

  In the urethanization reaction, although not particularly limited, a solvent may be used in order to facilitate reaction control. Examples of the solvent include methyl ethyl ketone, ethyl acetate, toluene, xylene, acetone, benzene, dioxane, acetonitrile, tetrahydrofuran, diglyme, dimethyl sulfoxide, N-methylpyrrolidone, dimethylformamide and the like. In view of the solubility of the urethane prepolymer, the boiling point of the solvent, etc., ethyl acetate, toluene, methyl ethyl ketone or a mixed solvent thereof is particularly preferable. These solvents may be added at an arbitrary timing such as the initial stage of the reaction, the middle of the reaction, or after the completion of the reaction.

  When a solvent is used during the urethanization reaction, the urethane prepolymer concentration in the urethane prepolymer solution (including unreacted raw materials excluding the solvent) is selected depending on the application and is not particularly limited, but preferably It is in the range of 10 to 90% by weight, and more preferably in the range of 20 to 55% by weight. When the urethane prepolymer concentration in the urethane prepolymer solution is in the range of 10 to 90% by weight, a decrease in the reactivity of urethanization is small, and an improvement in handling properties can be expected.

  A known urethanization catalyst may be used for the production of the urethane prepolymer of the present invention. For example, a tertiary amine compound, an organometallic compound, etc. are mentioned.

  The tertiary amine compound is not particularly limited, but includes triethylamine, triethylenediamine, N, N-dimethylbenzylamine, N-methylmorpholine, diazabicycloundecene (also known as DBU), and the like. Or in combination of two or more.

  Although it does not specifically limit as an organometallic compound, A tin type compound and a non-tin type compound can be mentioned.

  Although it does not specifically limit as a tin-type compound, For example, dibutyltin dichloride, dibutyltin oxide, dibutyltin dibromide, dibutyltin dimaleate, dibutyltin dilaurate (alias: DBTDL), dibutyltin diacetate, dibutyltin sulfide , Tributyltin sulfide, tributyltin oxide, tributyltin acetate, triethyltin ethoxide, tributyltin ethoxide, dioctyltin oxide, tributyltin chloride, tributyltin trichloroacetate, dioctyltin dilaurate (also known as DOTDL), tin 2-ethylhexanoate, etc. Is mentioned.

  The non-tin compound is not particularly limited. For example, titanium compounds such as dibutyltitanium dichloride, tetrabutyltitanate, butoxytitanium trichloride, lead oleate, lead 2-ethylhexanoate, lead benzoate, naphthene Lead type such as lead acid, iron type such as iron 2-ethylhexanoate, iron acetylacetonate, cobalt type such as cobalt benzoate, cobalt 2-ethylhexanoate, zinc naphthenate, zinc 2-ethylhexanoate, etc. Examples thereof include zinc-based and zirconium naphthenate.

  Among the urethanization catalysts, dibutyltin dilaurate (also known as DBTDL), dioctyltin dilaurate (also known as DOTDL), tin 2-ethylhexanoate and the like are preferable in terms of reactivity and hygiene.

  Catalysts such as tertiary amine compounds and organometallic compounds can be used alone or in combination.

  The amount of the urethanization catalyst added during the production of the urethane prepolymer of the present invention is not particularly limited, but if the amount used is too small, the productivity may decrease, and if it is too large, the reaction becomes uneven. Since the physical properties may become unstable, the above-mentioned tertiary amine compound is 0.01 to 15% by weight, and the above organometallic compound is 0.0001 to 5% by weight with respect to the polyalkylene oxide composition. The range of is preferable. After the synthesis, these catalysts may be removed or may remain.

  The urethane prepolymer of the present invention can be chain extended using a chain extender in order to promote high molecular weight. The chain extender is not particularly limited. For example, ethylene glycol, 1,4-butanediol, neopentyl glycol, butylethylpentanediol, glycerin, trimethylolpropane, pentaerythritol and other glycols, ethylenediamine, And polyvalent amines such as N-aminoethylethanolamine, piperazine, isophoronediamine, and xylylenediamine.

  The property of the urethane prepolymer of the present invention is desirably liquid. Coating may be difficult in gel or solid form, and insoluble matter may be generated even when dissolved in a solvent.

  The urethane prepolymer of the present invention preferably has a reactive group in the molecule. The reactive group is not particularly limited, but preferably contains a reactive group that reacts with an isocyanate group such as an active hydrogen group, and a reactive group that reacts with an active hydrogen group such as an isocyanate group. Particularly preferred is a hydroxyl group-terminated urethane prepolymer containing a hydroxyl group. When the molar ratio (NCO / OH) of the total amount of OH groups of the polyisocyanate (B) and NCO groups of the polyalkylene oxide (A) is 1.00 or less, the hydroxyl group is a terminal structure. In addition, in the range exceeding 1.00, many isocyanate groups have a terminal structure. Although it does not specifically limit as terminal structure of the urethane prepolymer of this invention, For example, 1 type, or 2 or more types, such as a hydroxyl group, an amino group, an isocyanate group, and an allyl group, is mentioned.

  The number average molecular weight in terms of standard polystyrene of the urethane prepolymer of the present invention is not particularly limited, but is preferably in the range of 1000 to 30000, and more preferably in the range of 2000 to 10,000. If the number average molecular weight of the urethane prepolymer is in the range of 1000 to 30000, the viscosity of the urethane prepolymer does not become too high and is easy to use for the curing reaction. The number average molecular weight in terms of standard polystyrene is measured by GPC (gel permeation chromatography) under the conditions of a column temperature of 40 ° C., a flow rate of 1.0 ml / min, and a solvent THF, and a cubic approximate curve calibration curve using standard polystyrene. Can be calculated as

  The viscosity of the urethane prepolymer of the present invention is particularly limited because it varies depending on the NCO / OH ratio in the polyalkylene oxide composition and the molecular weight of the polyalkylene oxide selected depending on the physical properties required for the obtained urethane cured product and applications. Although it does not do, it is the range of 100-500,000 mPa * s normally, Preferably it is the range of 1000-200,000 mPa * s, More preferably, it is the range of 2000-100,000 mPa * s. If it is in the range of 100 to 500,000 mPa · s, it is easy to handle although it depends on the application.

In particular, when the NCO / OH ratio in the polyalkylene oxide composition is away from 1, the viscosity of the urethane prepolymer tends to decrease, and when the NCO / OH ratio approaches 1, the viscosity tends to increase. When the NCO / OH ratio is in the range of 1.3 to 3.9 and the polyalkylene oxide molecular weight is 1000 to 5000, the viscosity of the urethane prepolymer is 5500 to 100,000 mPa · s. The use of the urethane prepolymer of the present invention is preferably not limited, and can be used for various urethane uses. For example, adhesives such as elastic adhesives for construction, surface protective films, paints, elastomers, waterproofing coatings, flooring materials, sealing materials for construction and civil engineering, plasticizers, flexible polyurethane foams, semi-rigid polyurethane foams, rigid polyurethane foams Etc. are mentioned.

<Hardened urethane>
The urethane cured product of the present invention comprises the polyalkylene oxide composition of the present invention or the urethane cured product of the pretan prepolymer of the present invention.

  Since the urethane cured product of the present invention is easily cured uniformly and has a short curing period, the period of tackiness is shortened, and contamination of dust and the like is easily suppressed. Therefore, the variation in mechanical properties is remarkably small.

  The urethane cured product of the present invention can be provided in any shape such as a film shape, a sheet shape, a plate shape, or a block shape.

  Although it does not specifically limit as a manufacturing method of the urethane hardened | cured material of this invention, For example, it can manufacture by hardening the polyalkylene oxide composition of this invention description, or the urethane prepolymer of this invention. . If necessary, it can be produced by advancing a urethanization reaction and a ureaization reaction in a predetermined shape in the presence of a urethanization catalyst, solvent, antifoaming material, cross-linking agent, and other additives. Depending on the condition, it can be defoamed and dried to produce a predetermined shape.

  For example, a production method of curing the polyalkylene oxide of the present invention as it is in a predetermined shape, and a production method of a one-component moisture curing type in which the urethane prepolymer of the present invention is cured in a predetermined shape by the advance of urea formation by moisture in the air. The urethane prepolymer of the present invention is mixed with a crosslinking agent having reactivity with an active hydrogen group or an isocyanate group, and includes a production method in which the urethane prepolymer is cured in a predetermined shape. It can be formed into a film shape, and can be formed into an arbitrary shape such as a plate shape or a block shape by molding in a mold.

  The use of the urethane cured product of the present invention is not particularly limited, and examples thereof include a urethane use with small variations in mechanical properties. Specifically, adhesives such as elastic adhesives for construction, surface protective films, paints, elastomers, waterproof coatings, flooring materials, sealing materials for construction and civil engineering, plasticizers, flexible polyurethane foams, semi-rigid polyurethane foams, Applications such as rigid polyurethane foam are exemplified.

  The crosslinking agent that can be used in the production of the urethane cured product of the present invention is not particularly limited as long as it is a compound having reactivity with an active hydrogen group or a compound having reactivity with an isocyanate group. For example, isocyanate crosslinking agent, aziridine crosslinking agent, epoxy crosslinking agent, melamine resin, urea resin, metal chelate crosslinking agent, polyol crosslinking agent, amine crosslinking agent, moisture and the like can be mentioned. Since these crosslinking agents are generally liquid, they can be used as they are, but if necessary, they may be diluted with an organic solvent.

  The molar ratio of the total amount of NCO groups derived from the polyisocyanate (B) in the polyalkylene oxide composition to the total amount of OH groups derived from the polyalkylene oxide (NCO / OH) is 1.00 or less, and OH group-terminated urethane. In the prepolymer, the cross-linking agent is preferably a compound having reactivity with active hydrogen groups. Examples of such a crosslinking agent include isocyanate-based crosslinking agents, aziridine-based crosslinking agents, epoxy crosslinking agents, melamine resins, urea resins, metal chelate-based crosslinking agents, and the like. Among these, an isocyanate-based crosslinking agent and an epoxy crosslinking agent are preferable because they easily exhibit performance such as heat resistance.

  On the other hand, in the polyalkylene oxide composition, the molar ratio of the total amount of NCO groups derived from the polyisocyanate (B) to the total amount of OH groups derived from the polyalkylene oxide exceeds 1.00 or the NCO group-terminated urethane prepolymer. The crosslinking agent is preferably a compound having reactivity with an isocyanate group. Examples of such a crosslinking agent include a polyol crosslinking agent, an amine-based crosslinking agent, and moisture.

  The amount of the crosslinking agent that can be used in the production of the urethane cured product of the present invention is 0.0001 based on the excess active hydrogen groups or isocyanate groups in the polyalkylene oxide composition and the reactive groups of the urethane prepolymer. The range of equivalent to 20 equivalents (molar ratio) is preferred, the range of 0.01 to 2 equivalents is more preferred, and the range of 0.1 to 1.5 equivalents is particularly preferred. The addition amount of the crosslinking agent is 0.0001 equivalent to 20 equivalents with respect to the excess active hydrogen groups or isocyanate groups in the polyalkylene oxide composition and the reactive groups (including moisture in the system) of the urethane prepolymer. If it is in the range of (molar ratio), since it is easy to cure uniformly, the variation in mechanical properties is small and preferable.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not construed as being limited to the following examples unless it exceeds the gist. The raw materials and evaluation methods used in the following examples and comparative examples are as shown below.

(material)
As propylene oxide, Wako Co., Ltd. special grade propylene oxide was dehydrated with zeolite and used as 50 ppm or less. Other raw materials were purchased as reagents and used as they were.

(Evaluation method)
<Hydroxyl value, number average molecular weight>
The hydroxyl value (OHV) of the polyalkylene oxide was measured according to the method of JIS-K1557-1. The number average molecular weight of the polyalkylene oxide is a value calculated by using the above formula (1) based on the hydroxyl value of the polyalkylene oxide.

<Unsaturation>
It measured according to the method of JIS-K1557-6.

<Molecular weight distribution (Mw / Mn)>
To the sample bottle, 10 mg of polyol and 10 ml of THF were added, dissolved by allowing to stand overnight, and then filtered through a PTFE cartridge filter (0.5 μm) to obtain a sample. Two detectors, RI detector RI8020, and two Tskel SuperH3000 × 2 manufactured by Tosoh, whose separation column is packed with 3 μm particle size packing material, are connected in series. The reference side is a resistor. Connected 5 tubes, using special grade tetrahydrofuran containing BHT stabilizer manufactured by Wako Co., Ltd. as developing solvent, separation column side flow rate 0.6 ml / min, reference side flow rate 0.15 ml / min, column temperature 40 ° C. Analyzed with The molecular weight distribution (Mw / Mn) was analyzed using a cubic approximate curve using 8 standard polystyrenes manufactured by Tosoh Corporation with known molecular weight as a calibration curve. Tosoh HLC-8320GPC was used for the measuring device, and Tosoh HLC-8320GPC-ECOSEC-WorkStation was used for the analysis.

<Viscosity>
About polyalkylene oxide, it measured according to the method of JIS-K1557-5. Specifically, the measurement temperature is 25 ° C., and the shear rate is 0.1 (1 / s) measured at a shear rate of 0.1 to 10 (1 / s) by a method using a cone-plate rotational viscometer. The value was taken as the viscosity. An MCR-300 manufactured by Anton-Paar was used as the measuring device.

  Moreover, about the polyalkylene oxide composition and the urethane prepolymer, it measured according to the method of JIS-K1557-5. Specifically, the measurement temperature was 25 ° C., and the measurement was performed immediately after production by a method using a B-type viscometer.

<NCO content>
It was determined by a back titration method using dibutylamine.

<Quick curing>
As an index of fast curability, the following curing time and tack free time were evaluated.

<Curing time>
Evaluate transition of NCO content when polyalkylene oxide composition or urethane prepolymer is coated on polyethylene film to a thickness of 100μm and urethanization reaction and urea reaction are advanced by moisture in the air. The time for reaching a conversion rate of 90% was taken as the curing time. In addition, since the reaction rate changed by the circulation of air, it left still and evaluated in the same place with the flow of air.
<Tack-free time>
When a polyalkylene oxide composition or a urethane prepolymer obtained using the composition is coated on a polyethylene film so as to have a thickness of 100 μm, and the urethanization reaction and the ureaization reaction are advanced by moisture in the air. The presence or absence of tack over time was evaluated by finger touch, and the time when tack disappeared (no longer attached to the fingertip) was defined as tack free time. In addition, since the reaction rate changed with the circulation of air, it left still in the same place and evaluated.

<Handling>
The viscosity of the polyalkylene oxide was measured according to the method of JIS-K1557-5. Specifically, the measurement temperature is 25 ° C., and the shear rate is 0.1 (1 / s) measured at a shear rate of 0.1 to 10 (1 / s) by a method using a cone-plate rotational viscometer. The value was taken as the viscosity. An MCR-300 manufactured by Anton-Paar was used as the measuring device.

  Moreover, the viscosity of the polyalkylene oxide composition and the urethane prepolymer was measured according to the method of JIS-K1557-5. Specifically, the measurement temperature was 25 ° C., and the measurement was performed immediately after production by a method using a B-type viscometer.

  When the viscosity [mPa · s] of the polyalkylene oxide composition was less than 500, ◎, 500 or more and less than 1400 were evaluated as ◯, and 1400 or more were evaluated as Δ.

  Further, the viscosity [mPa · s] of the urethane prepolymer was evaluated as ○ when the viscosity was less than 15000, Δ when the viscosity was 15000 or more and less than 22000, and × when the viscosity was 22000 or more.

<Tensile strength>
A release film is lightly bonded to the obtained urethane cured product, punched using a No. 3 dumbbell type punch, the release film is peeled off, and the thickness of the cured product is measured. Before the test, the base polyethylene film was peeled off to prepare 7 or more test pieces. Using Tensilon RTG-1210 manufactured by Orientec Co., Ltd., measurement was performed at a distance between chucks of 5 cm and a tensile speed of 200 mm / min, and the number of samples with a variation in tensile strength within the first 7 samples was determined within 10%. .

Catalyst synthesis example 1 (synthesis of iminophosphazenium salt A).
A 2 liter four-necked flask equipped with a stirring blade was placed in a nitrogen atmosphere, 96 g (0.46 mol) of phosphorus pentachloride and 800 ml of dehydrated toluene were added, and the mixture was stirred at 20 ° C. While maintaining stirring, 345 g (2.99 mol) of 1,1,3,3-tetramethylguanidine was added dropwise, and then the temperature was raised to 100 ° C., and 107 g of 1,1,3,3-tetramethylguanidine (0 .92 mol) was added dropwise. The resulting white slurry solution was stirred at 100 ° C. for 14 hours, cooled to 80 ° C., added with 250 ml of ion-exchanged water, and stirred for 30 minutes. When the stirring was stopped, all the slurry was dissolved and a two-phase solution was obtained. The obtained two-phase solution was subjected to oil / water separation, and the aqueous phase was recovered. 100 ml of dichloromethane was added to the obtained aqueous phase, oil / water separation was performed, and the dichloromethane phase was recovered. The obtained dichloromethane solution was washed with 100 ml of ion exchange water.

The obtained dichloromethane solution was transferred to a 2 liter four-necked flask equipped with a stirring blade, and after adding 900 g of 2-propanol, the temperature was raised to 80 to 100 ° C. under normal pressure to remove dichloromethane. did. The resulting 2-propanol solution was allowed to cool to 60 ° C. while stirring, and 31 g (0.47 mol) of 85% by weight potassium hydroxide was added and reacted at 60 ° C. for 2 hours. By cooling the temperature to 25 ° C. and removing the precipitated by-product salt by filtration, the target iminophosphazenium salt A [R ¹ in the above general formula (3) is a methyl group, R ² is a methyl group , 860 g of a 2-propanol solution of an iminophosphazenium salt in which X ⁻ corresponds to a hydroxy anion] was obtained at a concentration of 25% by weight and a yield of 92%.

<Polyalkylene oxide>
Production Example 1
A 2 liter autoclave with a stirring blade was placed in a nitrogen atmosphere, 224.2 g of polyether polyol (Sanix PP400, manufactured by Sanyo Chemical Industries, Ltd.) (active hydrogen content 1121 mmol), and iminophosphaze obtained in Synthesis Example 1. 11.58 g (5.4 mmol) of a 25 wt% 2-propanol solution of the nium salt A was added. The internal temperature was set to 100 ° C., and a pressure reduction treatment was performed at less than 0.3 kPa for 2 hours while stirring at 180 rpm to obtain a catalyst precursor. Thereafter, 12.34 g (17.3 mmol) of a 29 wt% hexane solution of triisopropoxyaluminum was added, the internal temperature was adjusted to 100 ° C., and the mixture was subjected to reduced pressure treatment at less than 0.3 kPa for 3 hours while stirring at 310 rpm, and alkylene oxide polymerization was performed. A catalyst was obtained.

  In the presence of the obtained alkylene oxide polymerization catalyst, the internal temperature of the autoclave was adjusted to 110 ° C., and 1230 ml of propylene oxide was reacted while being intermittently supplied so as to maintain a stirring speed of 380 rpm and a reaction pressure of 0.3 MPa or less. After completion of the reaction, residual propylene oxide was removed under reduced pressure of 0.5 kPa to obtain 1230 g of polyalkylene oxide. The catalyst of the obtained polyalkylene oxide was removed, and the obtained polyalkylene oxide had a viscosity of 359 mPa · s, a number average molecular weight calculated from OHV of 2040, an unsaturation of 0.006 meq / g, and a molecular weight distribution of 1 .011. The area ratio of the low molecular weight component was 0.12%.

Production Examples 2-3.
A polyalkylene oxide was obtained in the same manner as in Synthesis Example 2 except that the ratio of polyether polyol (manufactured by Sanyo Chemical Industries, Sannix PP400) and propylene oxide was changed. Table 1 shows the properties of the polyalkylene oxide obtained by removing the catalyst.

Production Example 4, 5.
A polyalkylene oxide was obtained in the same manner as in Example 1 except that a commercially available DMC catalyst made in China was used as a catalyst and the catalyst was produced by a conventional method. The input amount of the catalyst was appropriately adjusted according to the input amount of propylene oxide.

  Although the degree of unsaturation of the obtained polyalkylene oxide was low, the molecular weight distribution was broader than that of Examples, and the viscosity was higher than that of Production Examples having the same molecular weight.

  Table 1 shows the properties of the polyalkylene oxides obtained in the production examples.

<Production of polyalkylene oxide composition>
Examples 1 and 2.
The polyalkylene oxide synthesized in Production Examples 1 and 2 was put into a four-necked separable flask equipped with a stirring blade, dehydrated under reduced pressure at 100 ° C. for 2 hours, cooled to room temperature, and then manufactured by Aldrich under nitrogen. The flake-like 4,4′-MDI is put into a separable flask so that the ratio of polyalkylene oxide and 4,4′-MDI is 2 in the NCO / OH ratio, and mixed by stirring under nitrogen. An alkylene oxide composition was obtained.

  Table 2 shows the results of extracting a small amount of the obtained polyalkylene oxide composition and measuring the viscosity. Compared with comparative examples having the same molecular weight, the viscosity was low and the handling property was excellent. Moreover, although a use is selected by the molecular weight of a polyalkylene oxide, the polyalkylene oxide composition of an Example was judged to be used for the use normally used by sensory evaluation.

Example 3 FIG.
A polyalkylene oxide composition was obtained in the same manner as in Examples 1 and 2, except that the ratio of polyalkylene oxide to 4,4′-MDI was changed to 3 in the NCO / OH ratio. Table 2 shows the results of extracting a small amount of the obtained polyalkylene oxide composition and measuring the viscosity. Compared with comparative examples having the same molecular weight, the viscosity was low and the handling property was excellent. Moreover, although a use is selected by the molecular weight of a polyalkylene oxide, it was judged that the polyalkylene oxide composition of an Example can be used for the use normally used by sensory evaluation.

Comparative Examples 1 and 2.
Using the polyalkylene oxide synthesized in Production Examples 4 and 5, a polyalkylene oxide composition was obtained in the same manner as in Examples 1 and 2. Table 2 shows the results of extracting a small amount of the obtained polyalkylene oxide composition and measuring the viscosity. Compared with comparative examples having the same molecular weight, the viscosity was high and the handleability was poor.

  Further, the use is selected depending on the molecular weight of the polyalkylene oxide, but the polyalkylene oxide composition of the comparative example was judged to be difficult to use in the use corresponding to the molecular weight in the sensory evaluation.

<Manufacture of urethane prepolymer>
Examples 4-5.
The polyalkylene oxide composition contained in the four-necked separable flask obtained in Examples 1 and 2 was quickly heated to an internal temperature of 80 ° C. while stirring so as not to overshoot by inserting a thermocouple thermometer, and the reaction. The start. The NCO groups in the reactor contents were tracked by dibutylamine back titration, and reached the theoretical NCO content calculated from the charged amounts of polyalkylene oxide (A) and polyisocyanate (B) in the polyalkylene oxide composition. The reaction was terminated. A small amount of the obtained urethane prepolymer was extracted and the viscosity was measured. The results are shown in the table. The obtained urethane prepolymer had a low viscosity and excellent handling properties compared to the urethane prepolymer of Comparative Example synthesized using a polyalkylene oxide having an equivalent molecular weight.

  Moreover, although a use is selected by the molecular weight of polyalkylene oxide, it was judged that the urethane prepolymer of an Example can be used for the use normally used by sensory evaluation.

Comparative Examples 3 and 4.
A urethane prepolymer was produced in the same manner except that the polyalkylene oxide compositions obtained in Comparative Examples 1 and 2 were used. Compared with the polyalkylene oxide compositions of Examples 1 and 2, prepolymerization took time and the productivity was poor.

  Table 3 shows the results of extracting a small amount of the obtained urethane prepolymer and measuring the viscosity.

  The urethane prepolymers obtained in Comparative Examples 3 and 4 were higher in viscosity and inferior in handling properties than the urethane prepolymers of Examples 3 and 4 synthesized using polyalkylene oxide having the same molecular weight. It was.

  In addition, the use is selected depending on the molecular weight of the polyalkylene oxide, but the urethane prepolymer of the comparative example was judged to be difficult to use in the use corresponding to the molecular weight in the sensory evaluation.

Reference Example 1
A polyalkylene oxide composition similar to that of Example 1 was synthesized using a commercially available polyalkylene oxide (manufactured by Sanyo Kasei Co., Ltd., PP-2000: degree of unsaturation 0.043 meq / g, molecular weight 2000). A urethane prepolymer was synthesized by the method described above.

  Compared with the polyalkylene oxide composition of Example 1, it took time for prepolymerization and was inferior in productivity.

  A urethane cured product was obtained by the same method as in Example 6 using the obtained urethane prepolymer. Compared to the urethane prepolymers of the examples, the curing rate was slow and the tack-free time was long. In addition, the appearance of the obtained cured product was such that very little dust was taken in depending on the sample.

Reference Example 2
A polyalkylene oxide composition similar to that of Example 1 was synthesized using a commercially available polyalkylene oxide (manufactured by Sanyo Kasei Co., Ltd., PP-4000: degree of unsaturation 0.093 meq / g, molecular weight 4000). The urethane prepolymer was synthesized by the method described above. A urethane cured product was obtained by the same method as in Example 6 using the obtained urethane prepolymer.

<Manufacture of urethane cured products>
Example 6,7.
The urethane prepolymer obtained in Examples 4 and 5 was heated to 50 ° C. under nitrogen and degassed under reduced pressure, and then applied to a sheet of 100 μm thickness made of polyethylene using an applicator at a coating speed of 1.5 m / Coating was performed so that the thickness was 100 μm as min.

  After coating, the sample was allowed to stand in a place where the air circulation in a constant temperature room at 23 ° 55% RH was sufficient, and the NCO content and tack change with time were evaluated. The film obtained after one week was measured using transmission IR, and it was confirmed that the NCO group was less than the trace amount, and the reaction was completed.

  The obtained urethane cured product had a fast curing time and a short tack-free time. Moreover, the external appearance of the obtained hardened | cured material was also favorable.

  Next, variation in tensile strength of the obtained urethane cured product (film) was evaluated. Of the 7 samples, 5 or more samples had less than 10% variation, and mechanical property variation was small.

Comparative Examples 5 and 6.
A urethane cured product was obtained by the same method as in Examples 6 and 7, except that the urethane prepolymer obtained in Comparative Examples 3 and 4 was used.

  The obtained urethane cured product was slower in curing time and longer in tack-free time than the urethane cured product of the examples. Further, the appearance of the obtained cured product was very small in some samples in which dust was taken into the resin or where the appearance was not uniform.

  Next, variation in tensile strength of the obtained urethane cured product (film) was evaluated. Three or more of the seven samples broke before sufficient elongation, and the variation in tensile strength was as large as 10% or more. In many of these samples, the broken portion is not at the center of the dumbbell, and there is a possibility that the taken-in dust or a non-uniform portion becomes a break point.

Example 8 FIG.
The polyalkylene oxide composition obtained in Example 3 was degassed under reduced pressure, and then applied to a 100 μm-thick polyethylene sheet using an applicator so that the coating speed was 1.5 m / min to a thickness of 100 μm. .

  After coating, the sample was allowed to stand in a place where the air circulation in a constant temperature room at 23 ° 55% RH was sufficient, and the NCO content and tack change with time were evaluated. The film obtained after one week was measured using transmission IR, and it was confirmed that the NCO group was less than the trace amount, and the reaction was completed.

  Next, variation in tensile strength of the obtained urethane cured product (film) was evaluated. Of the 7 samples, 5 or more samples had less than 10% variation, and mechanical property variation was small.

Reference Example 3.
Except for using the urethane prepolymer obtained in Reference Example 1, a urethane cured product was obtained in the same manner as in Examples 6 and 7, and variations in tensile strength of the obtained urethane cured product (film) were evaluated. Compared to the urethane cured products of Example 4 and Comparative Example 5 obtained using a polyalkylene oxide having a low monool amount, the tensile strength was inferior to 2/3 or less. Further, 3 or more samples out of 7 samples were broken before sufficient elongation, and the variation in tensile strength was as large as 10% or more. In many of these samples, the broken part is not the center of the dumbbell, and the taken-in dust may have become the breaking point.

  The evaluation results of the urethane cured product are shown in Table 4.

  The polyalkylene oxide composition of the present invention is useful for polyurethane raw materials, polyester raw materials, surfactant raw materials, lubricant raw materials and the like. Specifically, urethanes with small variations in mechanical properties are required. Adhesives such as elastic adhesives for construction, surface protection films, paints, elastomers, waterproof coatings, flooring materials, sealing materials for construction and civil engineering, plastics Expansion to applications such as agents, flexible polyurethane foams, semi-rigid polyurethane foams and rigid polyurethane foams is expected.

Claims (10)

A composition comprising a polyalkylene oxide (A) and a polyisocyanate (B), wherein the polyalkylene oxide (A) has a molecular weight distribution (Mw) determined by gel permeation chromatography (GPC) using polystyrene as a standard substance. / Mn) is 1.029 or less and the degree of unsaturation is 0.010 meq / g or less. 2. The polyalkylene oxide composition according to claim 1, wherein the polyalkylene oxide (A) is represented by the following general formula (1).

[In general formula (1), R represents an m-valent group obtained by removing m active hydrogens from an active hydrogen-containing compound (R [—H] m); Z represents an alkylene group or cycloalkylene having 2 to 12 carbon atoms; And A is an alkylene group having 3 carbon atoms. When there are a plurality of Z or A, each may be the same or different; m is an integer of 1 or 2 to 100; p is an integer of 0 or 1 to 500, q is an integer of 1 to 1000; r is 0 Or it is an integer of 1-500. ] The number average molecular weight (M) calculated from the molecular weight distribution (Mw / Mn) determined by gel permeation chromatography (GPC) using the polyalkylene oxide (A) polystyrene as a standard substance and the hydroxyl value (OHV). The following mathematical formula (1):

The polyalkylene oxide composition according to claim 1 or 2, wherein The polyalkylene oxide (A) is contained in an amount of 50 to 99.9% by weight, and the polyisocyanate (B) is contained in an amount of 0.1 to 50% by weight. Polyalkylene oxide composition. The polyalkylene oxide composition according to any one of claims 1 to 4, wherein the polyalkylene oxide composition has a viscosity in a range of 100 to 100,000 mPa · s. A molecular weight distribution (Mw / Mn) determined by gel permeation chromatography (GPC) using polystyrene as a standard substance was connected in series to four columns packed with a 3 μm particle size filler in a separation column, and the reference side was 6. The polyalkylene oxide composition according to claim 1, wherein the polyalkylene oxide composition is a molecular weight distribution analyzed under conditions using a resistance tube connected and tetrahydrofuran as a developing solvent. A urethane prepolymer comprising a reaction product of a polyalkylene oxide (A) and a polyisocyanate (B) contained in the polyalkylene oxide composition according to any one of claims 1 to 6. A method for producing a urethane prepolymer, comprising reacting a polyalkylene oxide (A) and a polyisocyanate (B) contained in the polyalkylene oxide composition according to any one of claims 1 to 6. The urethane hardened | cured material of the polyalkylene oxide composition in any one of Claim 1 thru | or 6, or the urethane prepolymer of Claim 7. A method for producing a urethane cured product comprising curing the polyalkylene oxide composition according to any one of claims 1 to 6 or the urethane prepolymer according to claim 7.