JP2000336140A - Polycarbonate diol for polyurethane - Google Patents

Abstract

(57) [Problem] To provide a polycarbonate diol having good liquid properties for polyurethane. SOLUTION: 2,2-dialkyl-substituted-1,3-propanediol or 2,4-dialkyl-substituted-1,5
-A polycarbonate diol for polyurethane obtained by reacting a carbonate with pentanediol and at least one selected from alkylene oxide derivatives thereof.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel polycarbonate diol for polyurethane.

[0002]

2. Description of the Related Art Polycarbonate polyurethanes are used for various applications because of their excellent mechanical properties and heat resistance. However, common polycarbonate diols are
In many cases, linear aliphatic diol residues such as 1,6-hexanediol and 1,9-nonanediol are used as the basic skeleton of the polymer. Polycarbonate diols having such an aliphatic diol residue as a basic skeleton are inherently high in crystallinity, and thus polyurethanes obtained from such polycarbonate diols tend to lose elasticity. It is also known that the solubility in organic solvents is poor.
Conventionally, a diol having a side chain, for example, 2-methyl-1,8-octanediol or the like is added to reduce crystallinity,
Liquid properties have been improved. However, even when such a diol was used, the liquid properties at low temperatures were not sufficient.

[0003]

DISCLOSURE OF THE INVENTION The present invention has been made to solve the above problems of the polycarbonate diol, and an object of the present invention is to provide a novel polycarbonate diol having good liquid properties for polyurethane. .

[0004]

Means for Solving the Problems The present inventors have studied to solve the above problems, and as a result, have found that 2,2-dialkyl-substituted-
A polycarbonate diol obtained by using a compound to which an alkylene oxide of 1,3-propanediol and / or 2,2-dialkyl-substituted-1,3-propanediol has been added, and subjecting this to a carbonate reaction with a carbonate, solves the above problem. They have found that they can be solved and have completed the present invention. Also, 2,4-dialkyl-substituted-
A polycarbonate diol obtained by using a compound to which an alkylene oxide of 1,5-pentanediol and / or 2,4-dialkyl-substituted-1,5-pentanediol has been added, and subjecting this to a carbonate reaction with a carbonate, solves the above problem. They have found that they can be solved and have completed the present invention.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the polycarbonate diol of the present invention will be described in detail. The 2,2-dialkyl-substituted-1,3-propanediol used in the present invention is preferably a dialkyl group having the same or different alkyl group having 1 to 6 carbon atoms, and is a linear or branched alkyl group. That is, it is selected from a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group or a hexyl group. Among them, 2,2-diethyl-1,3-propanediol, 2-butyl, 2-ethyl, 1,3-propanediol, 2-pentyl-2-propyl-1,3-propanediol, 2-pentyl- 2-propyl-1,3-propanediol is particularly preferred. One or more of these can be arbitrarily selected.

The 2,4-dialkyl-substituted-1,5-pentanediol used in the present invention is preferably a dialkyl group having the same or different alkyl group having 1 to 6 carbon atoms, and a linear or branched alkyl group. It is. That is,
It is selected from a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group or a hexyl group. Of these, 2,4-
Diethyl-1,5-pentanediol, 2,4-dipropyl-1,5-pentanediol, 2,4-dibutyl-
1,5-pentanediol and the like are particularly preferred. These mixtures may be used.

Next, the 2,2-dialkyl-substituted-1,3-propanediol alkylene oxide derivative and the 2,4-dialkyl-substituted 1,5-pentanediol alkylene oxide derivative used in the present invention are 2,2-dialkyl A derivative obtained by adding an alkylene oxide to substituted-1,3-propanediol and / or 2,4-dialkyl-substituted-1,5-pentanediol, and is produced, for example, as follows. That is, 2,2
To the dialkyl-substituted-1,3-propanediol and / or 2,4-dialkyl-substituted-1,5-pentanediol, 0.001 to 5.0% of a basic catalyst is added, and an inert gas is added. Substitution and addition reaction of alkylene oxide in the range of 60 to 200 ° C. Furthermore, in order to remove the basic catalyst, an alkali adsorbent (for example, Kyoward 600S manufactured by Kyowa Chemical Industry Co., Ltd.) is added, and after the adsorption treatment at 80 to 120 ° C., the alkali adsorbent is removed by filtration.
It is desirable that the CPR, which is an index of the alkali residual ratio, is 10 or less, more preferably 5 or less.

In the alkylene oxide derivative of the present invention, the alkylene oxide is ethylene oxide,
Propylene oxide, 1,2-butylene oxide,
One or more compounds selected from 2,3-butylene oxide and other alkylene oxides having 3 or more carbon atoms can be used. Among these, ethylene oxide and propylene oxide are preferred. The average addition mole number of the alkylene oxide is preferably in the range of 1 to 10 mol. When the average number of moles added is less than 1 mole, there is no effect of adding an alkylene oxide such as improvement in handling properties and 10
If the amount exceeds the molar ratio, the proportion of carbonate bonds in the polycarbonate diol will decrease, and the effect of the polycarbonate will decrease.

Of the above 2,2-dialkyl-substituted-1,3-propanediol and / or its alkylene oxide derivative, 2,4-dialkyl-substituted-1,5-pentanediol and / or its alkylene oxide derivative , Preferably 2,2-dialkyl-substituted-1,
3-propanediol alkylene oxide derivative and 2,4-dialkyl-substituted-1,5-pentanediol.

In combination with the above-mentioned 2,2-dialkyl-substituted-1,3-propanediol and / or its alkylene oxide derivative, 2,4-dialkyl-substituted-1,5-pentanediol and / or its alkylene oxide derivative The aliphatic diol having 2 to 10 carbon atoms and the alicyclic diol having 6 to 10 carbon atoms are not particularly limited. For example, ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,4-pentanediol, 1,5-pentanediol, neopentyl glycol, 1,5-hexanediol, 1,6 -Hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-
Nonanediol, 1,10-decanediol, 2-methyl-1,3-propanediol, 3-methyl-1,5-
Examples thereof include aliphatic diols such as pentanediol and 2-methyl-1,8-octanediol, and alicyclic diols such as cyclohexanediol and cyclohexanedimethanol. Among them, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, cyclohexanediol, 3- Methyl-1,5-pentanediol, 2-methyl-1,8-octanediol, and mixtures thereof are preferred. If necessary, trimethylolethane, trimethylolpropane, glycerin, 1,2,2
3 such as 6-hexanetriol and pentaerythritol
It may contain a unit derived from a polyhydric alcohol having a valency or higher.

One selected from 2,2-dialkyl-substituted-1,3-propanediol and / or its alkylene oxide derivative, 2,4-dialkyl-substituted-1,5-pentanediol and / or its alkylene oxide derivative The mixing ratio of the above (A) and one or more (B) selected from aliphatic diols having 2 to 10 carbon atoms and alicyclic diols having 6 to 10 carbon atoms is represented by weight ratio (A).
/ (B) = 100/0 to 2/98 is preferable,
(A) / (B) = 80/20 to 5/95 is more preferable. This is because when the blending ratio of the component (A) is less than 2% by weight, the improvement of the liquid properties becomes insufficient. In addition,
By using the component (B) in combination as a diol, the mechanical properties of the urethane can be arbitrarily controlled.

The raw material carbonate used when the above-mentioned diols are carbonated is not specified, and any carbonate can be used as long as it is usually used when polycarbonate is formed. For example,
Examples thereof include dialkyl carbonate, diaryl carbonate, and alkylene carbonate, and specific examples include dimethyl carbonate, diethyl carbonate, diphenyl carbonate, ethylene carbonate, and propylene carbonate. Among these, alkylene carbonate, diaryl carbonate and the like are preferable, and ethylene carbonate, propylene carbonate, diphenyl carbonate and the like are particularly preferable. The polycarbonate diol can be synthesized by condensation polymerization of a diol component and a carbonate component by a known production method. The polycondensation reaction can be carried out in the presence of a titanium or tin catalyst as required.

As the titanium-based catalyst used in the present invention, a known catalyst used in the production of polycarbonate diol can be used, and it is not particularly limited. Examples thereof include tetraisopropyl titanate, tetra-n-butyl titanate, and tetra-titanium.
Tetraalkoxytitanium compounds such as 2-ethylhexyl titanate and tetrastearyl titanate; titanium acylate compounds such as polypidroxytitanium stearate and polyisopropoxytitanium stearate; titanium acetyl acetate; triethanolamine titanate; titanium ammonium lactate; titanium ethyl Raclates,
Titanium chelate compounds such as titanium octyl glucoxylate can be mentioned. Although the amount of the titanium catalyst is not particularly specified, it is generally 1 to 5000 ppm, more preferably 10 to 200 ppm based on the total weight of the reaction components.
The range is 0 ppm.

The tin catalyst used in the present invention may be a known catalyst used in the production of polycarbonate diol, and is not particularly limited. For example, monobutyltin trichloride, monobutyltin oxide, di-n-butyltin dilaurate, di-n -Butyltin oxide, dibutyltin diacetate and the like. Although the amount of the tin catalyst is not particularly specified, it is generally in the range of 1 to 5000 ppm, more preferably 10 to 2000 ppm, based on the total weight of the reaction components.

The production method of the polycarbonate diol is as follows.
1 selected from 2,2-dialkyl-substituted-1,3-propanediol and derivatives thereof, and 2,4-dialkyl-substituted-1,5-pentanediol and / or derivatives thereof
The diol, raw material carbonate, and, if necessary, the condensation catalyst are mixed at a predetermined ratio. The mixing ratio of the diols and the carbonates is not specified, but the amount of the carbonates is about 0.5 to 5 moles, more preferably 0.8 to 3 moles per mole of the diols. Reaction is 100-35
The reaction can be carried out at 0 ° C. under normal pressure or under any reduced pressure depending on the progress of the reaction. The reaction time varies depending on the presence or absence of the catalyst and the amount used, but is generally 5 to 40 hours.

When a titanium catalyst is used, it is desirable to deactivate the catalyst after the completion of the reaction. Examples of the method of deactivating the catalyst include, for example, a method of deactivating the catalyst by contacting it with water at the end of the reaction, a method of treating with a phosphorus compound such as phosphoric acid, a phosphoric ester, a phosphorous acid, or a phosphorous ester. No. When treating the titanium-based catalyst by contacting with water, water is added to the polycarbonate diol obtained by the reaction in an amount of 1% by weight or more and heated at 70 to 150 ° C, preferably 90 to 130 ° C for 1 to 3 hours. . This treatment may be performed at normal temperature or under pressure. It is preferable to reduce the pressure of the system after deactivating the catalyst since water used for deactivation can be removed.

Thus, the polycarbonate of the present invention comprising the 2,2-dialkyl-substituted-1,3-propanediol and / or a derivative thereof, and the 2,4-dialkyl-substituted-1,5-pentanediol and / or a derivative thereof A diol can be obtained. The number average molecular weight of this polycarbonate diol measured according to JIS-K1557 is 500 to 10,000, more preferably 10 to 10,000.
00 to 7000. If the molecular weight is less than 500, only a fragile polyurethane having a small mechanical strength can be obtained, and a molecular weight of 100
If it exceeds 00, the synthesis reaction takes a long time and monofunctional impurities are generated.

The polycarbonate diol of the present invention is useful as a raw material for producing polyurethane. That is, when a polyurethane is produced by reacting a polymer diol, an organic isocyanate, and a chain extender as needed, by using the polycarbonate diol of the present invention for at least a part of the polymer diol, Each one of the hydroxyl groups located at the terminal
Polyurethane containing a structural unit in a main chain excluding a single hydrogen atom is produced. The polycarbonate diol of the present invention is preferably at least 20% by weight, more preferably at least 40% by weight of the polymer diol.

As the polymer diol which can be used in combination with the polycarbonate diol of the present invention, those which can be used for producing ordinary polyurethane can be used. For example, polytetramethylene adipate diol, polyethylene adipate diol, polyhexamethylene adipate diol,
Known polyester diols such as polycaprolactane diol, known polycarbonate diols such as polyalkylene carbonate diol having 1,9-nonanediol or 1,6-hexanediol as an alkylene glycol component, and known polyester diols such as polyethylene glycol and polypropylene glycol. And the like.

As the organic isocyanate used for producing the polyurethane, known organic isocyanates used for producing the polyurethane can be used. For example, 4,
Examples thereof include aromatic isocyanates such as 4'-diphenylmethane diisocyanate, p-phenylene diisocyanate, tolylene diisocyanate, and xylene diisocyanate; aliphatic diisocyanates such as hexamethylene diisocyanate; and alicyclic diisocyanates such as isophorone diisocyanate.

The chain extender optionally used in the production of polyurethane is preferably a compound having a molecular weight of 400 or less and having two or more active hydrogen atoms in the molecule,
Compounds used as chain extenders in ordinary polyurethane production are used. For example, diols such as ethylene glycol, propanediol, 1,4-butanediol, 3-methyl-1,5-pentanediol, and 1,6-hexanediol, 4,4-diaminodiphenylmethane,
And diamines such as ethylenediamine. In addition,
An active hydrogen atom means a hydrogen atom that can react with an isocyanate group.

The proportions of the diol compound and the polyisocyanate used in the production of the polyurethane may be those generally used in the production of the polyurethane. That is, based on the equivalent ratio between active hydrogen and isocyanate groups in the molecule,
Active hydrogen / isocyanate group in the molecule = 1 / 0.5-1
/ 2, preferably 1 / 0.8 to 1 / 1.2. As a reaction condition for producing the polyurethane, a known polyurethane production method is applied. For example, the polycarbonate diol of the present invention and, if necessary, other polymer diol and / or a chain extender are added in an amount of about 50 to 230.
The polyurethane is obtained by reacting with an organic diisocyanate at ° C. In the urethanization reaction, a normal urethanization catalyst, for example, an organic tin compound, an organic titanium compound, a tertiary amine, or the like may be used as necessary.

[0023]

EXAMPLES Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto. Example 1 2-butyl-2-ethyl-1,3-propanediol 7
55 g and 2 g of potassium hydroxide were placed in a reactor having a content of 4 liters. After replacing the reactor with dry nitrogen, the temperature was raised from normal pressure to 120 ° C., and 1,245 g of ethylene oxide was added. After that, until no change in internal pressure is observed
Stir for 4 hours. After completion of the reaction, the remaining ethylene oxide was removed under reduced pressure, and the internal temperature was cooled to 50 ° C. Thereafter, the catalyst was removed using an adsorbent (Kyowad 600S, manufactured by Kyowa Chemical Industry Co., Ltd.). The obtained reaction product (abbreviated as BEPEO) was a transparent liquid, and had a hydroxyl value of 264 mgKOH / g and a CPR of 4.
Then, BEPEO 63 was placed in a 2000 ml four-necked flask equipped with a stirrer, thermometer, fractionating tube and nitrogen gas introducing tube.
7 g, 132 g of ethylene carbonate and 0.77 g of tetraisopropyl titanate as a catalyst were charged. The raw material was dissolved and stirred under normal pressure while introducing nitrogen gas into the flask, and the temperature was raised to 180 ° C. Gradually reduce the pressure
After reaching 500 Pa in 0 hour, the temperature was further raised to 220 ° C., and the reaction was continued for 2 hours to completely remove ethylene glycol produced. After completion of the reaction, the mixture was cooled to 100 ° C., and 3% by weight of water was added to the obtained reaction product. After heating for 2 hours with stirring to deactivate the titanium-based catalyst,
Water was removed under reduced pressure. The obtained product is a brown viscous liquid at room temperature, has no acid value, and has a hydroxyl value of 156 mg.
KOH / g.

Example 2 A stirrer, a thermometer, a fractionating tube and a nitrogen gas introducing tube were installed.
In a 000 ml four-necked flask, BEPEO 320 g,
320 g of 1,6-hexanediol, 455 g of ethylene carbonate and 0.94 g of tetraisopropyl titanate as a catalyst were charged. The raw material was dissolved and stirred under normal pressure while introducing nitrogen gas into the flask, and the temperature was raised to 180 ° C. The pressure was gradually reduced, and after reaching 500 Pa in 10 hours, the temperature was further raised to 220 ° C., and the reaction was continued for 2 hours to completely remove generated ethylene glycol. After completion of the reaction, the mixture was cooled to 100 ° C., and 3% by weight of water was added to the obtained reaction product. Heat for 2 hours with stirring,
After deactivating the titanium-based catalyst, water was removed under reduced pressure.
The obtained product was a pale yellow viscous liquid at normal temperature, no acid value remained, and the hydroxyl value was 64.3 mgKOH / g.

Example 3 2 equipped with a stirrer, a thermometer, a fractionating tube and a nitrogen gas introducing tube
In a 2,000 ml four-necked flask, 2,4-diethyl-1,1
480 g of 5-pentanediol, 264 g of ethylene carbonate and 0.74 g of tetraisopropyl titanate as a catalyst were charged. The raw material was dissolved and stirred under normal pressure while introducing nitrogen gas into the flask, and the temperature was raised to 180 ° C. The pressure was gradually reduced, and after reaching 500 Pa in 10 hours, the temperature was further raised to 220 ° C., and the reaction was continued for 2 hours to completely remove generated ethylene glycol. After completion of the reaction, the mixture was cooled to 100 ° C., and 3% by weight of water was added to the obtained reaction product. After heating for 2 hours with stirring to deactivate the titanium-based catalyst, water was removed under reduced pressure. The obtained product was a pale yellow cloudy liquid at room temperature, had no acid value, and had a hydroxyl value of 70.0 mgKOH / g.

Comparative Example 1 A stirrer, a thermometer, a fractionating pipe and a nitrogen gas introducing pipe were attached.
A 000 ml four-necked flask was charged with 473 g of 1,6-hexanediol, 352 g of ethylene carbonate, and 0.82 g of tetraisopropyl titanate as a catalyst. The raw material was dissolved and stirred under normal pressure while introducing nitrogen gas into the flask, and the temperature was raised to 180 ° C. After gradually reducing the pressure and reaching 500 Pa in 10 hours, further 220 ° C.
Then, the reaction was continued for 2 hours to completely remove ethylene glycol produced. After completion of the reaction, the mixture was cooled to 100 ° C., and 3% by weight of water was added to the obtained reaction product. After heating for 2 hours with stirring to deactivate the titanium-based catalyst, water was removed under reduced pressure. The obtained product is a white solid at room temperature, has no acid value, and has a hydroxyl value of 80.8.
mg KOH / g.

[0027]

The polycarbonate diol of the present invention comprises:
The liquid properties are good, and the polyurethane obtained from this diol is excellent in elasticity. Therefore, the polycarbonate diol of the present invention is useful as a raw material for a high-molecular-weight polyurethane resin that can be used in a wide range of fields such as paints, adhesives and molded articles.

Continued on the front page F term (reference) 4J029 AA09 AB01 AC02 BA02 BA03 BA04 BA05 BA07 BA08 BA10 BC05A BD06A BF24 HA01 HC04A HC05A JB131 JB171 JC751 JE182 JF321 JF371 4J034 CA04 CA15 CB03 CB07 CC03 DF12 DF03 DB01 DB04 DG03 DG04 HA01 HA07 HC03 HC12 HC17 HC22 HC46 HC52 HC61 HC64 HC67 HC71 HC73 QB15 RA07 RA08

Claims (2)

[Claims] 1. A 2,2-dialkyl-substituted-1,3-propanediol and / or a 2,2-dialkyl-substituted compound.
A polycarbonate diol for polyurethane obtained by reacting one or more selected from alkylene oxide derivatives of 1,3-propanediol with a carbonate. 2. A 2,4-dialkyl-substituted-1,5-pentanediol and / or a 2,4-dialkyl-substituted compound.
A polycarbonate diol for polyurethane obtained by reacting at least one selected from alkylene oxide derivatives of 1,5-pentanediol with a carbonate.