JP2002256069A - Liquid polyether carbonate diol - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a liquid polyether carbonate diol having a low viscosity (easy in treatment) and also a low glass-transition temperature (capable of producing a resin satisfying a flexibility and properties at a low temperature). SOLUTION: This liquid polyethercarbonate diol is obtained by reacting a polyether diol, which is composed of a structural unit (a)-(CH2 )6 O-, a structural unit (b)-(CH2 )2 O-, and/or (c) -CH2 CH(CH3 )O-, with compounds (an average molar number (n) of the structural unit (b) and the average molar number (m) are numbers simultaneously satisfying 0<=n<=5, 0<=m<=5 and 1<n+m<=5, respectively.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a liquid polyether carbonate diol. The liquid polyether carbonate diol can be used as a raw material such as polyurethane and polyester, as a polymer modifier, a polymer plasticizer, and the like.

[0002]

2. Description of the Related Art Polyols used as raw materials for resins such as polyurethanes and polyesters have been mainly polyether diols and polyester diols in the past, but have excellent heat resistance, hydrolysis resistance and weather resistance. Since resins can be obtained, attention has been paid to polycarbonate diol. However, on the other hand, it has been pointed out that polycarbonate-based resins have high rigidity and low elongation, and therefore lack flexibility as compared with conventional resins (particularly, polyether-based resins). Another problem is that the glass transition temperature is high and the low-temperature properties are inferior. Therefore, as the polyol, a polycarbonate diol having an ether group inserted in the molecule (that is, a polyether carbonate diol) has been proposed to solve the problem.

The diol component of these polyether carbonate diols is, for example, a diol having a polycarbonate chain as a main component (particularly 1,6-hexanediol polycarbonate glycol) and a mixed diol containing an ethylene oxide structural unit, or in the same molecule. A polymer diol which is a block copolymer having a polycarbonate chain and an ethylene oxide structural unit as main components (JP-A-59-66577)
And

A polyether diol obtained by etherifying 1,6-hexanediol (JP-A-63-305)
No. 127), polyether polyols (diethylene glycol, triethylene glycol, tetraethylene glycol, tripropylene glycol, polypropylene glycol, polytetramethylene glycol and the like) and polyhydric alcohols (ethylene glycol, 1,2-propanediol, 1, Mixtures of 3-butanediol, 1,6-hexanediol and the like (JP-A-2-255822) are used.

However, polyether carbonate diols using the above-mentioned polyether diols are difficult to handle because they solidify gradually at room temperature or are highly viscous liquids with high viscosity. Further, since their glass transition temperatures are not sufficiently low, the flexibility and low-temperature properties of the obtained resin have not been satisfactory.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a liquid polyether carbonate diol which can solve the problems of the prior art as described above. That is, an object of the present invention is to provide a liquid polyether carbonate diol having a low viscosity (easy handling) and a low glass transition temperature (a resin capable of satisfying flexibility and low-temperature properties is obtained).

[0007]

The object of the present invention is to provide a polyether diol comprising the following structural unit (a) and the following structural units (b) and / or (c) (provided that the structural unit (b) And the average number of moles (m) of the structural unit (c) is 0 ≦ n ≦ 5, 0 ≦ m ≦ 5, and 1 <n + m with respect to 1 mole of the structural unit (a), respectively. .Ltoreq.5) and a liquid polyether carbonate diol obtained by reacting a carbonate compound.

(A)-(CH ₂ ) ₆ O- (b)-(CH ₂ ) ₂ O- (c) -CH ₂ CH (CH ₃ ) O-

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The liquid polycarbonate diol of the present invention is a polyether diol comprising the structural unit (a) and the structural units (b) and / or (c) (where n and m are Each represents the average number of moles of the structural units (b) and (c) relative to 1 mole of the structural unit (a),
It is a numerical value that simultaneously satisfies 0 ≦ n ≦ 5, 0 ≦ m ≦ 5, and 1 <n + m ≦ 5. ) And a carbonate compound. In the present invention, “liquid” means a state having fluidity at normal temperature.

The polyether diol used in the present invention is, for example, a compound comprising a structural unit (a) and a structural unit (b) or (c) and having a general formula (I)
And those represented by (VII). Further, assuming that the structural unit (a) and the structural units (b) and (c) are included, the structural units (b) and (c) are added to the structural unit (b) or (c) in these general formulas. ).

HO- (b) _n- (a)-(c) _m -OH (I) HO- (b) _n1- (a)-(b) _n2- OH (II) HO- (c) _{m1- (a) - (c) m2} -OH (III) HO- (a) - (b) n - (c) m -OH (IV) HO- (a) - (c) m - (b) n -OH (V) HO- (a)-(b) _n- OH (VI) HO- (a)-(c) _m- OH (VII) (wherein a, b, c, n, and m are the same as described above) Where n1, n
2, m1 and m2 are numerical values that satisfy n = n1 + n2 and m = m1 + m2. )

Such polyether diols are known in the art.
Method (e.g., ethylene oxide to 1,6-hexanediol)
For the addition reaction of side and / or propylene oxide
Method), but commercially available products can also be used.
it can. This manufacturing method is described in, for example,
No. 36499 and JP-A-10-204171.
And the methods described in the above. That is, used in the present invention
Polyether diol is, for example, 1,6-hexane
Diol and basic alkali metal compound catalyst (alkali gold
Reactor) containing ethylene oxide and ethylene oxide.
And / or propylene oxide continuously
80-150 ° C, 0.5-5kg / cm ^Two(49-49
0 kPa), a predetermined molecular weight (corresponding to n and m) is obtained.
Until neutralized, then neutralized, dehydrated, dried, filtered
Such post-processing can be performed. After this
In some cases, only washing and drying may be required.
It does not matter if adsorption and distillation are combined to remove the medium.
I can't.

In the polyether diol used in the present invention, a part of 1,6-hexanediol (50 mol% or less) may be substituted with one or more other diols. Such diols include 1,4-butanediol, 1,5-pentanediol, 1.7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 12-dodecanediol, 2-methyl-1,3-propanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 2-methyl-1,8-octanediol, 1,4-cyclohexanedimethanol, etc. Aliphatic diols.

The polyether diol used in the present invention has a number average molecular weight of 150 to 450, more preferably 170 to 41.
It is preferably 0. Further, among the polyether diols used in the present invention, a structural unit (a) and a structural unit (b) are included (the structural unit (c) is not contained; m = 0, 1 <n ≦ 5). Is more preferred. (For example, those represented by the above general formula (II) or (VI)). That is, the polyether diol used in the present invention comprises the structural unit (a) and the structural unit (b) (does not contain the structural unit (c);
m = 0, 1 <n ≦ 5) polyether diol (for example, those represented by the above general formula (II) or (VI))
And the number average molecular weight is 150 to 450, further 170 to 4
A value of 10 is particularly preferred.

Examples of the carbonate compound used in the present invention include aliphatic or aromatic carbonates (carbonate esters) such as dialkyl carbonate, diaryl carbonate, alkylene carbonate and alkylaryl carbonate. Specifically, dimethyl carbonate, diethyl carbonate, di-n-butyl carbonate, diisobutyl carbonate, diphenyl carbonate, methyl phenyl carbonate, ethylene carbonate, propylene carbonate and the like can be mentioned.

The reaction between the polyether diol and the carbonate compound can be carried out according to a known method for producing a polycarbonate diol. That is, the liquid polyether of the present invention is obtained by subjecting the above-mentioned polyether diol and carbonate compound to a transesterification reaction while continuously extracting an by-produced aliphatic or aromatic alcohol out of the system in the presence of a transesterification catalyst. Carbonate diols can be produced.

At this time, the amount of the polyether diol to be used is not particularly limited as long as the desired product can be produced. However, both ends of the liquid polyether carbonate diol molecular main chain obtained are substantially hydroxyl groups. It is preferably 0.8 to 3.0 times, more preferably 0.85 to 2.0 times, especially 0.9 to 1.5 times the mol of the carbonate compound. In addition, the carbonate compound can be used alone or in combination. The amount of the transesterification catalyst used is 1 to 1 based on the weight of the polyether diol.
It is preferably 5000 ppm, more preferably 10 to 1000 ppm.

The conditions for the transesterification reaction are not particularly limited as long as the desired product can be produced, but at 110 to 200 ° C. for 1 to 24 hours under normal pressure so that the desired product can be produced efficiently. Degree, then under reduced pressure at 110-240 ° C (especially 140-240 ° C)
The reaction was allowed to proceed for about 20 hours, and while the degree of vacuum was gradually increased at the same temperature, the pressure was reduced to 0.1 mmHg or less at a final pressure of 20 mmHg or less.
The reaction is preferably performed for about 1 to 20 hours. Further, in order to extract the by-product alcohol, it is preferable to provide a distillation column in the reactor, and the reaction may be further performed under a flow of an inert gas (nitrogen, helium, argon, or the like).

The transesterification catalyst is not particularly limited as long as it is a compound that catalyzes the transesterification reaction. For example, titanium compounds such as titanium tetrachloride, tetraalkoxytitanium (tetra-n-butoxytitanium, tetraisopropoxytitanium, etc.), metal tin, tin hydroxide, tin chloride, dibutyltin laurate, dibutyltin oxide, butyltin Tin compounds such as tris (ethylhexanoate) are preferred. Among these, tetraalkoxy titanium (tetra-n-butoxy titanium,
Tetraisopropoxytitanium, etc.), dibutyltin laurate, dibutyltin oxide, and butyltin tris (ethylhexanoate) are preferred, with tetraalkoxytitanium (tetra-n-butoxytitanium, tetraisopropoxytitanium, etc.) being particularly preferred. .

The liquid polycarbonate diol of the present invention has a number average molecular weight of 500 to 5,000, more preferably 500 to 5,000.
Those having about 3000 are preferred. Therefore, when the hydroxyl value (molecular weight) of the reaction product is out of the target range,
That is, if the molecular weight is small, the reaction is performed while further distilling out the polyether diol under reduced pressure. Is preferred. If necessary, after adjusting the molecular weight,
It is preferable to inactivate the transesterification catalyst remaining in the liquid polyether carbonate diol with a phosphorus compound (phosphoric acid, butyl phosphate, dibutyl phosphate, etc.).

As described above, the liquid polyether carbonate diol of the present invention can be obtained. Such a liquid polyether carbonate diol of the present invention has a number average molecular weight of 500 to 5000, more preferably 500 to 30.
00 is preferred. In the liquid polyether carbonate diol of the present invention, the structural unit (a)
And a structural unit (b) (containing no structural unit (c); m = 0, 1 <n ≦ 5), and a liquid polyether carbonate obtained by reacting a carbonate compound with a polyether diol. Diols are preferred. That is, in the present invention, the structural unit (a) and the structural unit (b) are contained (the structural unit (c) is not contained; m = 0, 1
A liquid polyether carbonate diol obtained by reacting a polyether diol with a carbonate compound, wherein the number average molecular weight is 500 to 5000;
Further, those having a molecular weight of 500 to 3000 are particularly preferable. As the polyether diol, those having a suitable number average molecular weight as described above are used.

[0022]

The present invention will be specifically described below with reference to examples and comparative examples. The physical properties of the polyether diol and the liquid polyether carbonate diol were measured by the following methods.

1. Hydroxyl value (OH value (mgKOH /
g)): Analyzed according to JIS-K-1557 and calculated by the following equation. Here, in the formula, S is the sampled amount (g),
A is the amount (ml) of the 0.5N sodium hydroxide solution required for titration of the sample, B is the amount (ml) of the 0.5N sodium hydroxide solution required for the blank test, and f is the 0.5N sodium hydroxide solution. Represents the factor of OH value (mgKOH / g) = 28.05 (BA) f /
S

2. Number average molecular weight (Mn): calculated by the following equation. Mn = 112200 / OH number

3. Average addition mole number (n, m): The average addition mole number n of ethylene oxide and the average addition mole number m of propylene oxide were calculated by the following formula. Here, in the formula, Mn represents a number average molecular weight. Mn = 44n + 58m + 118

4. Acid value (mgKOH / g): Calculated by the following equation. In the formula, S ′ is the amount of sample collected (g), C is the amount of 0.1 N sodium hydroxide solution required for titration of the sample (ml), and D is the 0.1 N sodium hydroxide solution required for blank test. (Ml), f ′ represents a factor of 0.1N sodium hydroxide solution. Acid value (mgKOH / g) = 5.61 (CD) f ′ /
S '

5. Glass transition temperature (Tg (° C.)): Using a differential scanning calorimeter (manufactured by Shimadzu Corporation; DSC-50),
The measurement was carried out in a nitrogen gas atmosphere at a heating rate of 10 ° C./min. 6. Viscosity (Pa · sec): Measured at 75 ° C. using an E-type rotational viscometer (manufactured by Tokyo Keiki).

Example 1 [Production of polyether diol] Polyether diol (manufactured by Lion Corporation; 2.03 mol of ethylene oxide added on average to 1 mol of 1,6-hexanediol) was used. Distillation was performed under reduced pressure of 5 to 2.0 mmHg to obtain a distillate at 148 to 195 ° C as polyether diol (I). Table 1 shows the physical properties of the polyether diol (I).

[Production of Liquid Polyether Carbonate Diol] A 1 L (liter) glass reactor equipped with a stirrer, a thermometer, and a distillation column (provided with a fractionating tube, a reflux head, and a condenser at the top) was placed 2.30 mol of the polyether diol (I), 2.06 mol of dimethyl carbonate (manufactured by Ube Industries, Ltd.), and tetra-n-
0.507 mmol of butoxytitanium (catalyst) was charged,
It was kept at 170 ° C. for 2 hours under reflux. Then, while distilling the mixture of methanol and dimethyl carbonate,
Gradually raise the temperature to 190 ° C over 6.5 hours,
While maintaining the temperature at 190 ° C., a mixture of methanol and dimethyl carbonate was distilled off at 100 mmHg for 3 hours. Subsequently, the reaction was carried out while distilling the polyether diol at 5.2 to 0.7 mmHg for 9 hours to obtain a liquid polyether carbonate diol having a hydroxyl value of 49.8 mgKOH / g.

To this polyether carbonate diol, 0.024 mol of polyether diol (I) was added, and 2
The molecular weight was adjusted by stirring at 00 mmHg and 185 ° C. for 2 hours. The resulting liquid polyether carbonate diol was further added with an equimolar amount of dibutyl phosphate with the catalyst,
The catalyst was deactivated by stirring at 100 mmHg and 130 ° C. for 2 hours. Table 2 shows the physical properties of the liquid polyether carbonate diol (A) finally obtained.

Example 2 [Production of polyether diol] 5 parts of polyether diol (manufactured by Lion Corporation; an average of 2.07 mol of propylene oxide added to 1 mol of 1,6-hexanediol) was used. Distillation was performed under reduced pressure of 0.0 to 0.5 mmHg to obtain a distillate at 170 to 175 ° C as polyether diol (IV). Table 1 shows the physical properties of the polyether diol (IV).

[Production of Liquid Polyether Carbonate Diol] In the same reactor as in Example 1, 2.00 mol of the above polyether diol (IV), 2.06 mol of dimethyl carbonate (manufactured by Ube Industries, Ltd.), and Tetra-n-
0.259 mmol of butoxytitanium (catalyst) was charged,
It was kept at 160 ° C. for 3 hours under reflux. Then, while distilling the mixture of methanol and dimethyl carbonate, 1
The temperature was gradually raised to 190 ° C. over 3 hours (0.259 mmol of the catalyst was added at 10 hours on the way), and then
While maintaining the temperature at 190 ° C., a mixture of methanol and dimethyl carbonate was distilled off at 100 mmHg for 3 hours. Subsequently, the reaction was carried out while distilling out the polyether diol over 11 hours at 4.4 to 3.7 mmHg to obtain a liquid polyether carbonate diol having a hydroxyl value of 56.6 mgKOH / g.

The obtained liquid polyether carbonate diol inactivated the catalyst in the same manner as in Example 1. Table 2 shows the physical properties of the liquid polyether carbonate diol (B) finally obtained.

Comparative Example 1 [Production of liquid polyether carbonate diol] In a glass reactor having an internal volume of 2 L similar to that in Example 1, 0.85 mol of diethylene glycol and 0.81 mol of dimethyl carbonate (manufactured by Ube Industries, Ltd.) were added. Mole, and 100 ppm (by weight) of tetra-n- based on diethylene glycol
Butoxytitanium (catalyst) was charged and kept at 130 ° C. for 3 hours under reflux. Then, while distilling the mixture of methanol and dimethyl carbonate, 190 ° C.
Then, while maintaining the temperature at 190 ° C., the mixture of methanol and dimethyl carbonate was distilled off over 2 hours at 20 mmHg. In addition, 20mmH
The pressure was reduced to 4 g over 4 hours.

The obtained liquid polyether carbonate diol was added with an equimolar amount of dibutyl phosphate to the above catalyst,
The catalyst was deactivated by stirring at 110 ° C. for 2 hours. Table 2 shows the physical properties of the finally obtained liquid polyether carbonate diol (C).

Comparative Example 2 [Production of liquid polyether carbonate diol] A liquid polyether carbonate diol was obtained in the same manner as in Comparative Example 1, except that diethylene glycol was changed to 0.85 mol of triethylene glycol. Table 2 shows the physical properties of the liquid polyether carbonate diol (D) finally obtained.

Example 3 [Production of polyether diol] Polyether diol (manufactured by Lion Corporation; 1.04 mol of ethylene oxide added on average to 1 mol of 1,6-hexanediol) was used. Distillation was performed under reduced pressure of 0 to 0.5 mmHg to obtain a distillate at 150 to 185 ° C as polyether diol (II). Table 1 shows the physical properties of the polyether diol (II).

[Production of Liquid Polyether Carbonate Diol] In the same reactor as in Example 1, 2.30 mol of the above polyether diol (II), 2.51 mol of dimethyl carbonate (manufactured by Ube Industries, Ltd.), and Tetra-n-
0.232 mmol of butoxytitanium (catalyst) was charged,
It was kept at 160 ° C. for 2 hours under reflux. Then, while distilling the mixture of methanol and dimethyl carbonate,
Gradually raise the temperature to 190 ° C over 6.5 hours,
While maintaining the temperature at 190 ° C., 0.5 mm at 300 mmHg.
The mixture of methanol and dimethyl carbonate was distilled out over a period of time and further at 100 mmHg for 3 hours. Subsequently, the reaction was carried out while distilling out the polyether diol at 1.9 to 0.2 mmHg over 4.5 hours to obtain a liquid polyether carbonate diol having a hydroxyl value of 47.2 mgKOH / g.

To this polyether carbonate diol was added 0.023 mol of polyether diol (II),
The molecular weight was adjusted in the same manner as in Example 1. The obtained liquid polyether carbonate diol further inactivated the catalyst in the same manner as in Example 1. Table 2 shows the physical properties of the finally obtained liquid polyether carbonate diol (E).

Example 4 [Production of polyether diol] Polyether diol (manufactured by Lion Corporation; an average of 3.02 mol of ethylene oxide added to 1 mol of 1,6-hexanediol) was added to 5. Distillation was performed under reduced pressure of 0 to 0.2 mmHg to obtain a distillate at 155 to 196 ° C as polyether diol (III). Table 1 shows the physical properties of the polyether diol (III).

[Production of Liquid Polyether Carbonate Diol] In the same reactor as in Example 1, 1.40 mol of the above polyether diol (III), 1.47 mol of dimethyl carbonate (manufactured by Ube Industries, Ltd.), and Tetra-n-
0.182 mmol of butoxytitanium (catalyst) was charged,
It was kept at 160 ° C. for 2 hours under reflux. Then, while distilling the mixture of methanol and dimethyl carbonate,
Gradually raise the temperature to 190 ° C over 6.5 hours,
While maintaining the temperature at 190 ° C., 0.5 mm at 300 mmHg.
The mixture of methanol and dimethyl carbonate was distilled off over a period of 4 hours at 100 mmHg. Subsequently, the reaction was carried out at 1.3 to 0.2 mmHg for 4 hours while distilling out the polyether diol to obtain a liquid polyether carbonate diol.

The obtained liquid polyether carbonate diol inactivated the catalyst in the same manner as in Example 1. Table 2 shows the physical properties of the liquid polyether carbonate diol (F) finally obtained.

[0043]

[Table 1]

[0044]

[Table 2]

As can be seen from the above Examples and Comparative Examples, the liquid polyether carbonate diol of the present invention has a clearly lower viscosity and glass transition temperature than the conventional liquid polyether carbonate diol when compared at the same molecular weight.

[0046]

According to the present invention, a liquid polyether carbonate diol which can solve the problems of the prior art, that is, has a low viscosity (easy to handle) and a low glass transition temperature (satisfies flexibility and low temperature properties) A liquid polyether carbonate diol (where the resin is obtained) can be provided. For this reason, the liquid polyether carbonate diol of the present invention is useful as a resin raw material or a polymer modifier due to its low viscosity, and further, casting, RIM (reaction injection molding), RTM (resin transfer molding). ), Emulsions (especially suitable for polyurethane casting, RIM elastomers, emulsion water-based paints, etc.). And, since the glass transition temperature is low, it becomes possible to produce a resin having excellent low-temperature properties and to use it as a polymer plasticizer having an excellent plasticizing effect. Further, since it is excellent in impregnation into a fiber reinforcement, it can be suitably used in the field of composite materials such as filament winding, pultrusion molding, and prepreg lamination molding.

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Takayoshi Kaneko Inventor, Ube Chemical Plant, Ube Chemical Plant, Ube Chemical Plant, 1978 Kobe, Ube City, Yamaguchi Prefecture F term (reference) 4J029 AA09 AB01 AC03 AD01 AE15 AE17 AE18 BF23 BF27 HA05 HC03 HC04A HC05A JE182 JF321 JF371

Claims (7)

[Claims] 1. A polyether diol comprising the following structural unit (a) and the following structural units (b) and / or (c) (provided that the average number of moles (n) of the structural unit (b) and the structural unit) The average number of moles (m) of (c) is the structural unit (a)
0 ≦ n ≦ 5, 0 ≦ m ≦ 5,
It is a numerical value that simultaneously satisfies 1 <n + m ≦ 5. ) And a carbonate compound, thereby obtaining a liquid polyether carbonate diol. _{(A) - (CH 2)} 6 O- (b) - (CH 2) 2 O- (c) -CH 2 CH (CH 3) O- 2. The liquid polyether carbonate diol according to claim 1, wherein the polyether diol is a polyether diol obtained by adding ethylene oxide and / or propylene oxide to 1,6-hexanediol. 3. The liquid polyether carbonate diol according to claim 1, wherein the polyether diol has a number average molecular weight of 150 to 450. 4. The liquid polyether carbonate diol according to claim 1, wherein the number average molecular weight is from 500 to 5,000. 5. A polyether diol comprising the structural unit (a) and the structural unit (b) (provided that the average molar number (n) of the structural unit (b) is 1)
It is a numerical value that satisfies 1 <n ≦ 5 based on mole. ) And a carbonate compound, thereby obtaining a liquid polyether carbonate diol. 6. The liquid polyether carbonate diol according to claim 5, wherein the polyether diol has a number average molecular weight of 150 to 450. 7. The liquid polyether carbonate diol according to claim 5, wherein the number average molecular weight is from 500 to 5,000.