JP3449883B2 - Ester-based polymer polyol composition and method for producing the same - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an ester polymer polyol composition containing a specific phosphorus compound and a method for producing the same. When the ester-based polymer polyol composition of the present invention is used as a raw material for producing urethane, an excessive urethanization reaction is suppressed during urethane formation, the urethanization reaction proceeds smoothly, and heat resistance, hot water resistance, and hydrolysis resistance It is possible to obtain polyurethane having various properties such as.

[0002]

2. Description of the Related Art In the production of thermoplastic polyurethane, various polymer polyols such as polyester polyol, polyester polycarbonate polyol, polycarbonate polyol and polyether polyol are used as a raw material for forming a soft segment. Among them, polyester polyols are widely used because the resulting thermoplastic polyurethane has excellent mechanical properties.

Ester type polymer polyols such as polyester polyols, polyester polycarbonate polyols and polycarbonate polyols (polycarbonate ester polyols) are usually direct esters of a polycarboxylic acid or its ester, an ester forming derivative such as an anhydride and a polyol. It is produced by a polycondensation reaction by a compounding reaction or a transesterification reaction, or a ring-opening polymerization reaction of a lactone. Titanium-based compounds are widely used as catalysts for esterification reactions (esterification catalysts) that give these ester-based polymer polyols because of their high activity. However, the thermoplastic polyurethane produced by using the ester-based polymer polyol produced using the titanium-based esterification catalyst without sufficiently reducing the activity of the titanium-based esterification catalyst is Molding obtained from such thermoplastic polyurethanes because the ester-urethane exchange reaction between the hard segment and the soft segment occurs during melt molding, and the block property in the polyurethane molecular chain is reduced (that is, partially randomized). Products and elastic fibers are inferior in various performances such as heat resistance, hot water resistance and hydrolysis resistance.

In order to improve such a problem, water is added to an ester polymer polyol prepared by using a titanium esterification catalyst, and the mixture is heated to deactivate the titanium esterification catalyst. Method (WO92 /
19800 and WO94 / 25529), after adding water to the polymer polyol and heating it,
A phosphorus compound represented by the formula: (RO) _n P (O) _m (OH) _3-n (wherein m represents 0 or 1, n represents 0, 1 or 2, and R represents a hydrocarbon group) is added. Method (Japanese Patent Laid-Open No. 5-2392)
No. 01) is proposed.

[0005]

However, in the method according to the above, the deactivation of the titanium-based esterification catalyst is incomplete, and the deactivated catalytic activity tends to be recovered during the melt molding of polyurethane. . For example, when it is necessary to perform melt molding at a high temperature such as high hardness polyurethane or polyurethane having a cross-linked bond, or when using a large extruder for which the melt residence time becomes as long as about 20 to 50 minutes. In the case of melt molding, in the thermoplastic polyurethane produced by using the polymer polyol obtained by the above method, randomization of the hard segment and the soft segment proceeds during the melt molding, and the obtained molded product is heat-resistant. It is inferior in sex. Furthermore, the activity of the titanium-based esterification catalyst that was once deactivated is restored during melt retention during molding and acts as a hydrolysis catalyst, so that the resulting molded article also has poor hydrolysis resistance. For this reason, there is a limitation in expanding the application to applications that require high heat resistance and hydrolysis resistance. Further, a thermoplastic polyurethane produced by using the polymer polyol obtained by the above method of adding a phosphorus compound containing active hydrogen,
Since the phosphorus compound is acidic, hydrolysis is likely to occur, resulting in poor hydrolysis resistance.

An object of the present invention is to suppress excessive urethanization reaction when used as a raw material for producing urethane,
It is an object of the present invention to provide an ester-based polymer polyol composition that enables a polyurethane having excellent properties such as heat resistance, hot water resistance, and hydrolysis resistance to be obtained while the urethanization reaction proceeds smoothly.

[0007]

Means for Solving the Problems As a result of repeated studies by the present inventors in order to achieve the above object, after the polymerization reaction was carried out using a titanium-based esterification catalyst, the titanium-based esterification catalyst It was found that the above object can be achieved by adding a specific phosphorus compound to the ester polymer polyol obtained by reducing the activity, and the present invention was completed based on these findings.

That is, according to the present invention, at least one kind of phosphorus compound represented by the following general formulas (1) to (3) is added to the ester type polymer polyol produced by using the titanium type esterification catalyst. An ester-based polymer polyol composition, which is prepared by blending 1 mol of titanium atom in the titanium-based esterification catalyst such that the ratio of phosphorus atom in the phosphorus compound is 1 mol or more. The urethanization reaction rate constant with 4,4′-diphenylmethane diisocyanate measured at 0 ° C. was 0.15 (liter / mol · min) or less, and the ester-based polymer polyol composition was heated at 200 ° C. for 1 hour. The subsequent urethanization reaction rate constant with 4,4′-diphenylmethane diisocyanate measured at 90 ° C. was 0.4 (liter / mol.
Min) is less than or equal to the following.

[0009]

[Chemical 7] (In the formula, a and j each represent 0 or 1, and R ¹
To R ³ each represent a hydrocarbon group. However, when a is 1, at least one of R ^{1 to} R ³ is an aliphatic hydrocarbon group or an alicyclic hydrocarbon group. )

[0010]

[Chemical 8] (In the formula, b, c, k and l each represent 0 or 1, and R ⁴ and R ⁵ each represent a hydrocarbon group.)

[0011]

[Chemical 9] (In the formula, d, e, m, and n each represent 0 or 1, R ^{6 to} R ⁹ each represent a hydrocarbon group, and R ¹⁰ represents a divalent hydrocarbon group. When both are 1, at least one of R ^{6 to} R ¹⁰ is an aliphatic hydrocarbon group or an alicyclic hydrocarbon group.)

Further, the present invention provides an ester polymer polyol obtained by carrying out a polymerization reaction using a titanium-based esterification catalyst and then decreasing the activity of the titanium-based esterification catalyst. At least one selected from the phosphorus compounds represented by the general formulas (1) to (3) has a ratio of phosphorus atoms in the phosphorus compound of 1 mole or more to 1 mole of titanium atoms in the titanium-based esterification catalyst. The present invention relates to a method for producing the above ester-based polymer polyol composition, which is compounded in such a ratio.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION The ester-based polymer polyol used in the present invention is a polymer having an ester bond in the molecule and a hydroxyl group at the end of the molecular chain.
Examples thereof include polyester polyol, polyester polycarbonate polyol, and polycarbonate polyol (polycarbonate ester polyol). The number average molecular weight of the ester-based polymer polyol is 1,000 to
It is preferably 8000, more preferably 1200 to 6000. The number average molecular weights of the high molecular weight polyols referred to in this specification are all JIS K - 157.
It is the number average molecular weight calculated based on the hydroxyl value measured according to 7.

The above polyester polyol is, for example,
It can be obtained by subjecting an ester-forming derivative such as polycarboxylic acid or its ester or anhydride and a polyol to direct esterification reaction or transesterification reaction according to a conventional method.

Examples of the polycarboxylic acid used as a raw material for producing the polyester polyol include glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, 2-methylsuccinic acid and 2-methyladipine. C5-C12 aliphatic dicarboxylic acids such as acid, 3-methyladipic acid, 3-methylpentanedioic acid, 2-methyloctanedioic acid, 3,8-dimethyldecanedioic acid, and 3,7-dimethyldecanedioic acid acid;
Aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, orthophthalic acid, and naphthalenedicarboxylic acid; alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid, and the like can be used, and one or more of these can be used. . Among these, carbon number is 5 to 1
It is preferable to use the aliphatic dicarboxylic acid of 2, and more preferable to use adipic acid, azelaic acid, or sebacic acid. Furthermore, a small amount of trifunctional or higher polycarboxylic acid can be used together with the dicarboxylic acid as described above. Examples of the trifunctional or higher polycarboxylic acid include tricarboxylic acid such as trimellitic acid and trimesic acid, and one or more of them can be used.

Examples of the polyol component used as a raw material for producing the polyester polyol include ethylene glycol, 1,3-propanediol and 2-methyl-
1,3-propanediol, 1,4-butanediol,
Neopentyl glycol, 1,5-pentanediol,
3-methyl-1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 2-methyl-1,8-octanediol, 1,9-nonanediol, Examples thereof include aliphatic diols such as 1,10-decanediol; alicyclic diols such as cyclohexanedimethanol and cyclohexanediol, and one or more of these can be used. Among these, branched chain aliphatic diols having 5 to 12 carbon atoms such as 3-methyl-1,5-pentanediol and 2-methyl-1,8-octanediol are preferably used. Furthermore, a small amount of trifunctional or higher functional polyol can be used in combination with the above-mentioned diol. Examples of trifunctional or higher functional polyols include glycerin, trimethylolpropane,
Examples thereof include butanetriol, hexanetriol, trimethylolbutane, trimethylolpentane, and pentaerythritol, and one or more of these can be used. Of these, it is preferable to use trimethylolpropane.

The above-mentioned polycarbonate polyol is
For example, it can be obtained by reacting a polyol with a carbonate compound such as dialkyl carbonate, dialkylene carbonate or diaryl carbonate. As the polyol which is a raw material for producing a polycarbonate polyol, the polyols exemplified above as a raw material for producing a polyester polyol can be used. Examples of the dialkyl carbonate include dimethyl carbonate and diethyl carbonate, examples of the dialkylene carbonate include diethylene carbonate, and examples of the diaryl carbonate include diphenyl carbonate.

The above-mentioned polyester polycarbonate polyol is obtained, for example, by reacting a polyol, a polycarboxylic acid and a carbonate compound at the same time. Alternatively, it is obtained by synthesizing a polyester polyol by the above-mentioned method and then reacting with a carbonate compound, or synthesizing a polycarbonate polyol and then reacting them with a polyol and a polycarboxylic acid.

The ester-based polymer polyol is produced by using a titanium-based esterification catalyst. Examples of titanium-based esterification catalysts include titanic acid, tetraalkoxytitanium compounds, titanium acylate compounds, and titanium chelate compounds. More specifically, tetraalkoxytitanium compounds such as tetraisopropyl titanate, tetra-n-butyl titanate, tetra-2-ethylhexyl titanate and tetrastearyl titanate; polyhydroxytitanium stearate,
Titanium acylate compounds such as poly-isopropoxy titanium stearate; titanium acetyl acetate TONNAY over preparative can include triethanolamine titanate, titanium ammonium lactate, titanium ethyl lactate, and titanium chelate compounds such as titanium octylene glycolate.

The titanium-based esterification catalyst may be used in an amount appropriately selected for use in the production of the target ester-based polymer polyol and the subsequent production of the thermoplastic polyurethane. But not limited to
Generally, it is preferably in the range of about 0.1 to 50 ppm, and more preferably in the range of about 1 to 40 ppm, based on the total weight of the raw material components for forming the ester polymer polyol. If the amount of the titanium-based esterification catalyst used is too small, it takes an extremely long time to produce the ester-based polymer polyol, and the obtained ester-based polymer polyol may be colored.
On the other hand, if the amount of titanium esterification catalyst used is too large,
Not only is the excess catalyst not contributing to the promotion of the production of the ester-based polymer polyol, but it is rather difficult to sufficiently reduce the activity of the titanium-based esterification catalyst after the ester-based polymer polyol is synthesized, which is not preferable.

The removal of the titanium-based esterification catalyst from the ester-based polymer polyol product usually involves complicated steps.
Generally, the titanium-based esterification catalyst is often used as it is for the production of polyurethane without separation. Therefore, the "ester-based polymer polyol produced using a titanium-based esterification catalyst" in the present invention generally means an ester which is contained as it is without separating and removing the titanium-based esterification catalyst used in the reaction. The term “polymer high-molecular polyol” includes ester high-polymer polyols in which the content of the titanium-based esterification catalyst is reduced by purification.

It is important that the activity of the titanium-based esterification catalyst contained in the ester-based polymer polyol produced using the titanium-based esterification catalyst is sufficiently reduced. The activity-reducing treatment of the titanium-based esterification catalyst contained in the ester-based polymer polyol may be such that the catalytic activity of the titanium-based esterification catalyst is completely lost, or it is reduced to a desired degree. May be The activity of the titanium-based esterification catalyst is preferably lowered by a method of bringing the titanium-based esterification catalyst-containing ester-based polymer polyol into contact with water under heating conditions. This deactivating treatment may be performed as it is after the reaction for forming the ester-based polymer polyol, or may be performed for a predetermined period of time with respect to the ester-based polymer polyol produced in advance.

The amount of water added when water reduces the activity of the titanium esterification catalyst depends on the type of ester polymer polyol to be treated, the type of titanium esterification catalyst used, and the concentration. It can be appropriately selected, but from the viewpoint of sufficiently reducing the activity of the titanium-based esterification catalyst, it is preferably 1% by weight or more based on the weight of the ester-based polymer polyol. On the other hand, the upper limit of the amount of water added is not particularly limited, and even if a large amount of water is added, the large amount of water does not adversely affect the activity of lowering the activity of the titanium-based esterification catalyst. . However, if the amount of water added is too large, the removal of the added water becomes complicated, so it is preferable to limit the amount of water added to 7% by weight or less based on the weight of the ester polymer polyol. The heating temperature when contacting with water is 70 to 150.
Within the range of 0 ° C, particularly within the range of 80 to 130 ° C is preferable.
If the heating temperature is lower than 70 ° C., the activity of the titanium-based esterification catalyst may be insufficiently reduced, while the heating temperature of 150
If the temperature is higher than ° C, the ester polymer polyol may be decomposed. When heating to 100 ° C or higher,
It may be carried out under pressure, or the water may be contacted in the form of steam. This heat treatment time is not particularly limited,
Usually, about 1 to 5 hours is sufficient. After reducing the activity of the titanium-based esterification catalyst by adding water and performing heat treatment, water can be removed from the ester-based polymer polyol by any method such as heat drying under reduced pressure. .

In the ester-based polymer polyol composition of the present invention, at least one selected from the phosphorus compounds represented by the above general formulas (1) to (3) is added to 1 mol of titanium atom in the titanium-based esterification catalyst. On the other hand, the phosphorus compound is contained in a proportion such that the proportion of phosphorus atoms in the phosphorus compound is 1 mol or more. When the ratio of phosphorus atoms in the phosphorus compound is less than 1 mol with respect to 1 mol of titanium atoms in the titanium esterification catalyst, deactivation of the titanium esterification catalyst contained in the ester polymer polyol. Is incomplete, and the heat resistance and hot water resistance of the thermoplastic polyurethane obtained by using this deteriorate. When the content of the phosphorus compound is very large, the hydrolysis resistance of the thermoplastic polyurethane obtained using the phosphorus compound tends to decrease, or the bleed-out of the phosphorus compound tends to occur, and the cost is low. Since it is expensive, it is appropriate to contain the phosphorus compound in a ratio such that the ratio of phosphorus atoms is 500 mol or less with respect to 1 mol of titanium atoms.

In the above general formulas (1) to (3), R
^The hydrocarbon group represented by ^{1 to} R ⁹ is preferably a hydrocarbon group having 1 to 30 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an octyl group and an isooctyl group. , 2-ethylhexyl group, nonyl group, decyl group, dodecyl group, isodecyl group, octadecyl group and other aliphatic hydrocarbon groups; cyclohexyl and other alicyclic hydrocarbon groups; phenyl group, nonylphenyl group, cresyl group, 2 , 4-di-t-butylphenyl group, 2,6
Examples thereof include aromatic hydrocarbon groups such as a di-t-butyl-4-methylphenyl group, a naphthyl group, a benzyl group, and a 3,5-di-t-butyl-4-hydroxybenzyl group. The aromatic hydrocarbon group is a halogen atom, an alkyl group,
The aromatic ring may have a substituent such as an alkoxy group, a phenoxy group or a hydroxyl group. In the general formula (3), the divalent hydrocarbon group represented by R ¹⁰ has 1 carbon atom.
It is preferably a divalent hydrocarbon group of 50 to 50, such as a methylene group, an ethylene group, a propylene group or a butylene group.
Divalent aliphatic hydrocarbon group; divalent alicyclic hydrocarbon group such as cyclohexylene group; phenylene group, biphenylene group,
Examples thereof include divalent aromatic hydrocarbon groups such as 4,4′-butylidene-bis (3-methyl-6-t-butylphenyl) group and 4,4′-isopropylidenediphenyl group. The divalent aromatic hydrocarbon group may have a substituent such as a halogen atom, an alkyl group, an alkoxy group, a phenoxy group or a hydroxyl group on the aromatic ring.

Examples of the phosphorus compound represented by the above general formula (1) include trimethyl phosphite, triethyl phosphite, tributyl phosphite, trioctyl phosphite, tris (2-ethylhexyl) phosphite and trinonyl phosphite. , Tris (decyl) phosphite, tridodecylphosphite, tris (octadecyl) phosphite, tricyclohexylphosphite, diphenylisooctylphosphite, phenyldiisooctylphosphite, diphenylisodecylphosphite, phenyldiisodecylphosphite, etc. Phosphite triester; trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tris (2-ethylhexyl) phosphate, tri (Decyl) phosphate, tridodecyl phosphate, tris (octadecyl) phosphate, phosphoric acid triesters such as tri-cyclohexyl phosphate; phenyl phosphonous acid dimethyl, phenyl phosphonous acid diethyl, phenyl phosphonous acid dibutyl,
Phenyl phosphonous acid dioctyl, phenyl phosphonous acid didodecyl, Fe two Le phosphonous acid bis (octadecyl), phenyl phosphonous acid dicyclohexyl, diester of phosphonous acid derivative such as phenyl phosphonous acid diphenyl; dimethylphenyl phosphonic acid, phenylphosphonic Diethyl acid, dibutyl phenylphosphonate, dioctyl phenylphosphonate, didodecyl phenylphosphonate, bis (octadecyl) phenylphosphonate, dicyclohexyl phenylphosphonate, diphenyl phenylphosphonate, 3,5-di-t-butyl-4-hydroxybenzyl Examples thereof include diesters of phosphonic acid derivatives such as diethyl phosphonate, and examples of the phosphorus compound represented by the general formula (2) include didodecyl pentaerythritol diphohate. Fight, bis (octadecyl) pentaerythritol diphosphite, bis (nonylphenyl) pentaerythritol diphosphite, bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite, bis (2,6-di- t-butyl-
4-methylphenyl) pentaerythritol diphosphite and other phosphite triesters; bis (octadecyl) pentaerythritol diphosphate and other phosphate triesters, and the like, and examples of the phosphorus compound represented by the above general formula (3) Are, for example, phosphite triesters such as 4,4′-butylidene-bis (3-methyl-6-t-butylphenylditridecyl) phosphite and 4,4′-isopropylidene diphenol tetrakis (tridecyl) diphosphite. A diester of a phosphonous acid derivative such as tetrakis (2,4-di-t-butylphenyl) -4,4′-biphenylenephosphonite, and the like, and one or more of these can be used. . Among the above phosphorus compounds, bis (octadecyl) pentaerythritol diphosphite, bis (nonylphenyl) pentaerythritol diphosphite, bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite, bis (2 , 6-di-t-
Butyl-4-methylphenyl) pentaerythritol diphosphite, tris (decyl) phosphite, tris (2-ethylhexyl) phosphate, bis (octadecyl) pentaerythritol diphosphate, tetrakis (2,4-di-t-butylphenyl) Particularly preferred are -4,4'-biphenylenephosphonite, diethyl phenylphosphonate, diethyl 3,5-di-t-butyl-4-hydroxybenzylphosphonate and the like.

The phosphorus compound may be added continuously after the activity of the titanium esterification catalyst contained in the ester polymer polyol is reduced by the above-mentioned method,
It may be added any time after the activity of the catalyst is reduced. Furthermore, the activity of the titanium-based esterification catalyst can be more completely deactivated by adding the phosphorus compound to the ester-based polymer polyol and then heating at 50 to 200 ° C. for 0.5 to 5 hours.

The degree of activity decrease of the titanium-based esterification catalyst contained in the ester-based polymer polyol composition of the present invention was measured at 90 ° C. to obtain the ester-based polymer polyol composition and 4,4′- It can be evaluated by the urethane formation reaction rate constant with diphenylmethane diisocyanate (MDI). In the ester-based polymer polyol composition of the present invention, the activity of the titanium-based esterification catalyst is reduced to such an extent that the urethanization reaction rate constant is 0.15 (liter / mol · min) or less, (liter/
It is preferable that the activity of the titanium-based esterification catalyst is reduced to such an extent that it becomes less than or equal to mol. Furthermore, the ratio of the degree to which the activity of the once deactivated titanium-based esterification catalyst is recovered when heated at a high temperature is such that the above-mentioned urethanization reaction rate after heating the ester-based polymer polyol composition at 200 ° C. for 1 hour. It can be evaluated by measuring a constant. In the case of the ester polymer polyol composition of the present invention, the urethanization reaction rate constant after heating at 200 ° C. for 1 hour is 0.40 (liter / mol · minute) or less and 0.30 (liter / mol / minute). -It is preferably less than or equal to minutes. The activity of the titanium-based esterification catalyst contained in the ester-based polymer polyol composition of the present invention is not only almost completely deactivated, but also the activity is hardly recovered by heating at a high temperature. When an ester-based polymer polyol composition having a urethanization reaction rate constant within such a range is used as a raw material for producing urethane,
Excessive urethanization reaction is suppressed, the urethanization reaction proceeds smoothly, and polyurethane having excellent properties such as heat resistance, hot water resistance, and hydrolysis resistance can be obtained.

The ester polymer polyol composition of the present invention may optionally contain additives such as a light stabilizer, a heat stabilizer, an antioxidant, an ultraviolet absorber and a hydrolysis inhibitor. . Further, dialkyltin diacylates such as dibutyltin diacetate and dibutyltin dilaurate, which have catalytic activity for urethanization reaction; dialkyltin bismercaptocarboxylic acid esters such as dibutyltin bis (3-mercaptopropionic acid ethoxybutyl ester) salts. It may contain a tin-based urethane-forming catalyst such as salt. The content of the tin-based urethane-forming catalyst is preferably 0.1 to 15 ppm with respect to the ester-based polymer polyol.

The ester polymer polyol composition of the present invention comprises a thermoplastic polyurethane, a thermosetting polyurethane,
It is useful as a raw material for producing various polyurethanes such as polyurethane foams, urethane-based paints, and urethane-based adhesives. In particular, ester-based polymer polyol component,
When used as a raw material for producing a thermoplastic polyurethane composed of an organic diisocyanate component such as 4,4′-diphenylmethane diisocyanate and a chain extender component such as 1,4-butanediol, heat resistance and hydrolysis resistance during melt molding The above properties are not deteriorated and a thermoplastic polyurethane excellent in melt moldability can be obtained, which is preferable.

[0031]

EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples. In Examples and Comparative Examples, the urethane-forming reaction rate constant (k) of the ester polymer polyol composition; the logarithmic viscosity, heat resistance, and hydrolysis resistance of polyurethane were measured or evaluated by the following methods.

[Urethane Reaction Rate Constant (k)] The ester polymer polyol composition dehydrated under reduced pressure and the composition obtained by heating the composition at 200 ° C. for 1 hour were measured for reactivity with isocyanate groups. . An ester-based polymer polyol composition and 4,4′-diphenylmethane diisocyanate were charged into a reaction vessel at a molar ratio of 3: 1 and the temperature was maintained at 90 ° C. with stirring, and a part of the reaction product was added at regular intervals. Sampled. To this, a fixed amount of 0.01N di-n-butylamine dimethylformamide solution was added and dissolved, and then neutralized titration was performed with 0.01N hydrochloric acid in methanol using bromphenol blue as an indicator to obtain each sampling time. The residual amount of the isocyanate group was obtained for each, and the concentration of the urethane bond [-NHCOO-] at each sampling time was calculated from the residual amount. Since the urethanization reaction rate is linearly proportional to the respective concentrations of the hydroxyl group and the isocyanate group, the concentration of the urethane bond [-NHCOO-] obtained above is substituted into the following formula to obtain the urethanization reaction rate constant ( k) (liter / mol.min) was calculated.

{1 / (a-b)} ln {b (a-x) /
a (b−x)} = kt [wherein, k is a reaction rate constant (liter / mol · minute), t
Is the reaction time (sampling time) (minutes), a is the initial concentration of the hydroxyl group [—OH] (mol / liter), b is the initial concentration of the isocyanate group [—NCO] (mol / liter), x
Represents the concentration (mol / liter) of the urethane bond [-NHCOO-] at t. ]

[Logarithmic viscosity of polyurethane] Thickness 100μ
The polyurethane film of m was dissolved in a N, N-dimethylformamide solution containing 1% by weight of n-butylamine so that the concentration of polyurethane was 0.5 g / dl, and the mixture was allowed to stand at 20 ° C. for 24 hours. The flowing time of the solution at 30 ° C. was measured using a type viscometer, and the logarithmic viscosity was determined by the following formula.

Logarithmic viscosity = {ln (t / t ₀ )} / c [where t is the flow-down time (seconds) of the polyurethane solution, t
_o represents the flow-down time (second) of the solvent, and c represents the concentration (g / dl) of the polyurethane solution. ]

[Heat resistance of polyurethane] D manufactured by Rheology Co.
Using VE-V4 Rheospectr, thickness 100 μm
The dynamic viscoelasticity of the test piece collected from the polyurethane film of No. 1 was measured by automatic static load, frequency 11 Hz, displacement amplitude 10 μ,
The temperature was raised at a temperature of 3 ° C./min and the flow starting temperature was used as an index of heat resistance.

[Hydrolysis resistance of polyurethane] Thickness 10
A dumbbell-shaped test piece prepared from a 0 μm polyurethane film was left at 70 ° C. and a relative humidity of 95% RH for 6 weeks, and the breaking strength before and after standing was measured according to JISK 7311. The breaking strength retention was calculated and used as an index of hydrolysis resistance.

Abbreviations for the compounds used in the following Examples and the like are shown in Table 1 below.

[0039]

[Table 1]

Reference Example 1 [Polyester diol (PMA
Production of Z)] 3-Methyl-1,5-pentanediol (3000 g) and azelaic acid (4058 g) were charged into a reactor, and under normal pressure,
The esterification reaction was carried out while distilling the water generated at 200 ° C. out of the system. When the acid value of the reaction product became 20 or less, 120 mg of tetraisopropyl titanate (20 ppm based on the product) was added as a titanium-based esterification catalyst, and the reaction was continued while gradually reducing the pressure from 200 mmHg to 100 mmHg. It was condensed. When the acid value of the reaction product became 1.0 or less, the degree of vacuum was gradually raised by a vacuum pump to complete the polycondensation reaction. As a result, a polyester diol having a number average molecular weight of 2000 (hereinafter referred to as P
6210 g of MAZ) was obtained.

Example 1 PMAZ obtained in Reference Example 1
500 g was heated to 100 ° C., 10 g (2% by weight) of water was added thereto, and the mixture was heated with stirring for 2 hours, and then water was distilled off under reduced pressure. Next, 0.5 g of bis (octadecyl) pentaerythritol diphosphite (titanium atom:
A phosphorus atom = 1: 52 (molar ratio)) was added and the mixture was heated for 1 hour with stirring to obtain an ester polymer polyol composition. The urethanization reaction rate constant (k) of this ester-based polymer polyol composition was measured by the above method and was found to be 0.07 (liter / mol.min).
The urethanization reaction rate constant after heating this ester-based polymer polyol composition at 200 ° C. for 1 hour in a nitrogen atmosphere was 0.12 (liter / mol · minute), and the titanium-based reaction was continued even after heating. The deactivated state of the esterification catalyst was almost maintained.

Examples 2 to 7 PM obtained in Reference Example 1
An ester polymer polyol composition was produced in the same manner as in Example 1 except that AZ was used and the type and addition amount of the phosphorus compound were changed as shown in Table 2 below. The urethanization reaction rate constant (k) of the obtained ester-based polymer polyol composition was evaluated by the above method. The results obtained are shown in Table 2 below.

Comparative Example 1 PMAZ obtained in Reference Example 1
500 g was heated to 100 ° C., 10 g (2% by weight) of water was added thereto, and the mixture was heated for 2 hours while stirring. Then, water was distilled off under reduced pressure to obtain an ester polymer polyol. Regarding the obtained ester-based polymer polyol,
The urethanization reaction rate constant (k) was evaluated by the above method. The results obtained are shown in Table 2 below.

Comparative Example 2 PMAZ obtained in Reference Example 1
Was used, and an ester-based polymer polyol composition was produced in the same manner as in Example 1 except that water was not added and heat treatment was not performed. The urethanization reaction rate constant (k) of the obtained ester-based polymer polyol composition was evaluated by the above method. The results obtained are shown in Table 2 below.
Shown in.

<< Comparative Examples 3 and 4 >> PM obtained in Reference Example 1
An ester-based polymer polyol composition was produced in the same manner as in Example 1 except that AZ was used and the type and addition amount of the phosphorus compound were changed as shown in Table 2 below. The urethanization reaction rate constant (k) of the obtained ester-based polymer polyol composition was evaluated by the above method. The results obtained are shown in Table 2 below.

[0046]

[Table 2]

<< Test Example 1 >> Diameter (φ) = 30 mm, L /
The ester-based polymer polyol composition obtained in Example 1 was heated to 80 ° C. in a twin-screw extruder rotating in the coaxial direction with D = 36, 1,4-butanediol and 4,4 heated to 80 ° C. '-Diphenylmethane diisocyanate,
After continuously supplying it with a metering pump in a molar ratio of 1: 3.82: 4.87 and maintaining the cylinder temperature of the extruder at 260 ° C. to perform continuous melt polymerization to produce polyurethane. A polyurethane pellet was produced by extruding it into water from a die in a strand shape and cutting it, and the polyurethane pellet was dried at 80 ° C. for 10 hours in a low dew point atmosphere (dew point = −30 ° C.). The obtained polyurethane pellets are formed into a film at 240 ° C, and the thickness is 100 μm.
The polyurethane film of was prepared and aged at 80 ° C. for 24 hours. This polyurethane film was evaluated for logarithmic viscosity, heat resistance and hydrolysis resistance by the methods described above. The results obtained are shown in Table 3 below.

<Test Examples 2 to 7> As shown in Table 3 below, a polyurethane film was prepared in the same manner as in Test Example 1 except that the ester-based polymer polyol compositions obtained in Examples 2 to 7 were used. Was manufactured. This polyurethane film was evaluated for logarithmic viscosity, heat resistance and hydrolysis resistance by the methods described above. The results obtained are shown in Table 3 below.

<Test Examples 8 to 11> As shown in Table 3 below, polyurethane films were prepared in the same manner as in Test Example 1 except that the ester-based polymer polyol compositions obtained in Comparative Examples 1 to 4 were used. Manufactured. This polyurethane film was evaluated for logarithmic viscosity, heat resistance and hydrolysis resistance by the methods described above. The results obtained are shown in Table 3 below.

[0050]

[Table 3]

[0051]

EFFECTS OF THE INVENTION The ester-based polymer polyol composition of the present invention, when used as a raw material for producing urethane, suppresses an excessive urethanization reaction at the time of urethane formation, promotes the urethanization reaction smoothly, and has heat resistance. , Hot water resistance,
A polyurethane excellent in various properties such as hydrolysis resistance can be obtained.

─────────────────────────────────────────────────── ─── Continued Front Page (58) Fields surveyed (Int.Cl. ⁷ , DB name) C08G 18/42 C08L 67/00-67/02

Claims (2)

(57) [Claims] 1. An ester-based polymer polyol produced using a titanium-based esterification catalyst is added to the following general formulas (1) to (3); (In the formula, a and j each represent 0 or 1, and R ¹
To R ³ each represent a hydrocarbon group. However, when a is 1, at least one of R ^{1 to} R ³ is an aliphatic hydrocarbon group or an alicyclic hydrocarbon group. ) [Chemical 2] (In the formula, b, c, k and l each represent 0 or 1, and R ⁴ and R ⁵ each represent a hydrocarbon group.) (In the formula, d, e, m, and n each represent 0 or 1, R ^{6 to} R ⁹ each represent a hydrocarbon group, and R ¹⁰ represents a divalent hydrocarbon group. When both are 1, at least one of R ^{6 to} R ¹⁰ is an aliphatic hydrocarbon group or an alicyclic hydrocarbon group), and at least one selected from the phosphorus compounds represented by An ester-based polymer polyol composition, which is compounded in such a ratio that the ratio of phosphorus atoms in the phosphorus compound is 1 mol or more with respect to 1 mol of titanium atoms in the oxidization catalyst,
The urethanization reaction rate constant with 4,4′-diphenylmethane diisocyanate measured at 0 ° C. was 0.15 (liter / mol · min) or less, and the ester-based polymer polyol composition was heated at 200 ° C. for 1 hour. After 90 ℃
An ester polymer polyol composition having a urethanization reaction rate constant with 4,4′-diphenylmethane diisocyanate of 0.4 (liter / mol · minute) or less as measured in 1. 2. An ester-based polymer polyol obtained by performing a polymerization reaction using a titanium-based esterification catalyst and then decreasing the activity of the titanium-based esterification catalyst, has the following general formula (1): )-(3); (In the formula, a and j each represent 0 or 1, and R ¹
To R ³ each represent a hydrocarbon group. However, when a is 1, at least one of R ^{1 to} R ³ is an aliphatic hydrocarbon group or an alicyclic hydrocarbon group. ) [Chemical 5] (In the formula, b, c, k and l each represent 0 or 1, and R ⁴ and R ⁵ each represent a hydrocarbon group.) (In the formula, d, e, m, and n each represent 0 or 1, R ^{6 to} R ⁹ each represent a hydrocarbon group, and R ¹⁰ represents a divalent hydrocarbon group. When both are 1, at least one of R ^{6 to} R ¹⁰ is an aliphatic hydrocarbon group or an alicyclic hydrocarbon group), and at least one selected from the phosphorus compounds represented by 2. The ester-based polymer polyol composition according to claim 1, wherein the compound is added in a proportion such that the ratio of phosphorus atoms in the phosphorus compound is 1 mol or more with respect to 1 mol of titanium atoms in the oxidation catalyst. Method.