JPH0243217A - Preparation of lactone polyol - Google Patents

Abstract

PURPOSE:To shorten a required reaction time, to lower an acid value and to improve resistance to hydrolysis by performing a ring-opening polymn. of lactones in the presence of an initiator under a condition where a water content is below a specified value. CONSTITUTION:A polylactone polyol of the formula (wherein Y is a residue obtd. by the ring-opening polymn. of a component A; R is a residue obtd. by removing the terminal OH group from a component B; n is the mole number of addition and n>=1; m is the number of substituents and m=1-6) is obtd. by dehydrating pref. one of 4-8C lactones (A) (e.g., epsilon-caprolactone) and an initiator (B) (e.g., ethylene glycol) filled and sealed in a reactor at 60-100 deg.C under a required pressure of 50mmHg or lower, pref. 20mmHg or lower to adjust the water content of the component A and/or the component B to 100ppm or lower, pref. 50ppm or lower and performing the ring-opening polymn. of the component A in the pressure of the component B under an ordinary pressure at 50-230 deg.C, pref. 80-220 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing polylactone polyols. More specifically, the present invention relates to a method for producing a polylactone polyol that can shorten the reaction time, has a low acid value, and has high hydrolysis resistance.

Polylactone polyols are very useful as raw materials for polyurethane polymers and paints such as elastomers, adhesives, synthetic leathers, ink binders, and fibers.

It is also used as a modifier for imparting toughness and processability to polyester resins, polycarbonate resins, polyvinyl chloride resins, acrylonitrile-styrene resins, epoxy resins, etc., or as raw materials for urethane acrylate resins.

[Conventional technology]

A polylactone polyol that is very useful as a raw material for polyurethane polymers and paints is disclosed in JP-A-57-15.
No. 5230, No. 58-8251, No. 62-1
Generally, polyhydric alcohols mainly containing diols as disclosed in Japanese Patent No. 67320 are used as initiators.

Also, JP-A-57-155231, JP-A No. 60-234
There is an example in which a vinyl resin oligomer having a hydroxyl group is modified with lactone as disclosed in Japanese Patent Publication No. 18, and an example in which an epoxy resin is modified with lactone is disclosed in Japanese Patent Application Laid-open No. 16416/1983.

Furthermore, there are also hydroxyalkyl acrylic esters and hydroxyalkyl methacrylic esters whose terminal OH groups are modified with lactone, as disclosed in JP-A-57-185236.

[Problems to be Solved by the Invention] However, conventionally produced polylactone polyols generally have a higher acid value than expected.

It is known that when the acid value of a polylactone polyol is generally high, hydrolysis of the ester groups of the polylactone polyol is promoted. That is, when the acid value is high, the hydrolysis resistance of the polylactone polyol tends to decrease.

Furthermore, the water resistance of elastomers, adhesives, synthetic leathers, ink binders, polyurethane polymers such as fibers, and paints made from this lactone polyol is also reduced.

In addition, if the acid value of the polylactone polyol is high,
The urethane reaction between the polylactone polyol and the incyanate is accelerated, causing rapid heat generation and making it impossible to control the reaction.

To overcome this drawback, additives such as carbodiimide and epoxy compounds are generally used as substances that impart hydrolysis resistance.

However, additives such as carbodiimide in particular have toxicity such as skin irritation, and cannot be used in applications where they come into direct contact with the human body.

Furthermore, in order to suppress the blooming phenomenon that occurs on the surface of the product, it is necessary to reduce the amount of additives used as much as possible.

In addition, to produce such polylactone polyols, lactones are ring-opened and polymerized in the presence of a catalyst using an organic compound having active hydrogen as an initiator, but this method has disadvantages such as a significantly longer reaction time. Ta.

Therefore, for example, when ring-opening polymerization of lactone is performed using an initiator having a heat-sensitive reactive substituent such as an unsaturated double-viscous initiator, side reactions of the initiator itself may occur due to a long heating history. was there.

Under the above circumstances, when producing a polylactone polyol by ring-opening polymerization of lactones using an initiator, it is possible to shorten the time required for the ring-opening polymerization reaction of lactones,
Moreover, it was necessary to reduce the acid value of the resulting polyol.

Therefore, the present inventors conducted intensive studies to solve the above two problems, and found that it is possible to achieve this by reducing the water content in the initiator and/or lactone, shortening the lactone ring-opening polymerization reaction time, and The present inventors have discovered that a polylactone polyol with a low acid value can be obtained without using the above-mentioned additives, and have completed the present invention.

[Structure of the invention]

That is, the present invention is characterized in that "when producing a polylactone polyol by ring-opening polymerization of lactones using an initiator, the starting uJ and/or the water power contained in the lactones is <1100 pp or less ( I) Process for producing a polylactone polyol having an addendum of the formula" (
I) R-[-0-(-C-Y-0-). -]l-H [where, Y is the lactone group having 4 to 8 carbon atoms (the ring-opening polymerized residue, R is the initiator minus the terminal @OH group ν), n is the number of moles added, n ≧l, m is the number of substituents and m=1 to 6].

In the present invention, specific methods for reducing the water content in the initiator and/or lactones to below iooppm include: ■ Separation using a distillation column ■ Dehydration under reduced pressure ■ Bubbling nitrogen or rare gas, etc. Method ■ Dehydration methods using water absorbing agents such as silica gel and Molecular Ravens may be used. Any one of the above dehydration methods or a combination of two or more methods may be used. Also, initiators or lactones may be used. Sufficient dehydration is possible either alone or in a mixed state.For example, after filling the reaction container with the initiator and lactones and sealing the container, 60 to 1
50 mg + using a vacuum pump while heating to 00℃
Hg or less, preferably 20 nm Hg or less, by dehydration for several hours to reduce the water content in the initiator and/or lactones to toppm or less, preferably 50 ppm.
It is necessary to do the following.

After dehydrating the initiator and/or lactones under the above conditions until the water content reaches a predetermined amount, a ring-opening polymerization catalyst is added, and the reaction is proceeded by heating to a predetermined reaction temperature.

The polymerization catalyst used in the present invention is a conventional organic titanium compound such as tetrabutyl titanate, tetrapropyl titanate, or tetraethyl titanate, which has been used in polymerization without dehydration treatment. , organic tin compounds such as tin octylate, dibutyltin oxide, di-n-butyltin dilaurate, stannous halides such as stannous chloride, stannous bromide, stannous iodide, etc. are similarly used. . The amount of catalyst added is 1 to 11000 pp, preferably 5
~1100pp.

If the amount of catalyst added exceeds 11,000 pp, the product will be significantly colored, and the product obtained using this as a raw material will contain a large amount of metal content, which may affect the storage stability and durability of the product. It often has a negative impact on

Further, when the amount of catalyst added is less than ippm, the above-mentioned problems are less likely, but the reaction rate becomes extremely slow, which is not preferable.

Initiators applicable to the production method of the present invention include, for example, monohydric alcohols including aliphatic alcohols such as methanol, ethanol, and butanol, and glycol monoethers such as cellosolve and calpitol, ethylene glycol, propylene glycol, diethylene glycol,
Dipropylene glycol, 1,4-butanediol, 1
．． 3-butanediol, neopentyl glycol, hexanediol, 1.6-hexanediol, 2.2.4
- and 2.4.4-trimethylhexanediol, 2
．． 2.4-trimethyl-1,3-bentanediol, 1
．． Dihydric alcohols such as 10-decanediol, 1,12-dodecanediol, and 1,4-cyclohexane dimetatool; trihydric or higher polyhydric alcohols such as glycerin, trimethylolethane, trimethylolpropane, and pentaerythritol; hydroxyalkyl Examples include reactive monomers containing hydroxyl groups such as acrylic acid esters, hydroxyalkyl methacrylic acid esters, and allyl alcohol, or polymers thereof, and compounds having active OH groups such as epi-bis type epoxy resins.

Next, lactones (cyclic ester compounds), which are another component of the polylactone polyol produced by the production method of the present invention, will be explained in detail.

Examples of the lactones used in the present invention include γ-butyrolactone, δ-valerolactone, ε-caprolactone, ξ-enantholactone, η-cabrirolactone, and ring-substituted products thereof, and particularly preferred cyclic esters. The compound has 4 to 8 carbon atoms.

Among these, ε-caprolactone is a preferred monomer for various reasons.

The reaction ratio between the initiator and the lactones is appropriately selected depending on the grade of the desired polylactone polyol.

For example, when polymerizing a high-molecular-weight material that can be used as a molded product, the polymerization is carried out using the small amount of water present in the lactone monomer as an initiator, so it is not necessary to use an initiator. No need to add.

Rather, a high molecular weight grade may be produced by further dehydration treatment.

Further, in order to carry out the ring-opening polymerization between the initiator and the lactone, the temperature should be 50°C to 230°C, preferably 80°C to 230°C, at normal pressure.
Perform at 20°C.

Below 50°C, the reaction rate is extremely slow, and above 230°C, depolymerization and thermal decomposition occur, resulting in a high acid value, which is not preferred.

1 For example, when ring-opening polymerization of lactone is performed using an initiator with a heat-sensitive reactive substituent such as an unsaturated double bond, a stabilizer or the like is added in advance to prevent side reactions of the initiator itself. It can also be prevented.

The reaction is stopped after confirming by gas chromatography analysis that the amount of unreacted lactone is 1% or less.

The obtained polylactone polyol is white at room temperature.
It is either a solid or liquid substance.

〔Effect of the invention〕

In the polylactone polyol obtained by the production method of the present invention, water contained in the initiator and lactone is to
The acid value is low because it is dehydrated and polymerized to below oppm.

Therefore, there is no need to use additives to lower the acid value as in the past.

Furthermore, it has become clear that the time required for ring-opening polymerization of lactone can be greatly shortened by reducing the water content in the initiator and/or lactones to 1100 pp or less.

In addition, since the acid value of the polylactone polyol obtained by the method of the present invention is low, hydrolysis is not accelerated.
As a result, the water resistance of the polylactone polyol was improved.

Furthermore, when producing polyurethane using a polylactone polyol,9 the polylactone polyol obtained by the method of the present invention has a low acid value, so it is possible to control rapid heat generation in the urethanization reaction with an organic isocyanate. It has now become possible to produce a urethane polymer with certain properties.

By the way, it is not clear why the polymerization reaction rate slows down when there is a large amount of water contained in the initiator and/or lactones, but it is believed that the catalyst used for ring-opening polymerization of lactones is inactivated by the presence of water. It would be Runame.

Next, the content of the present invention will be specifically explained with reference to Examples and Comparative Examples, but the present invention is not limited by these.

The hydroxyl values shown in Examples and Comparative Examples are JIS
This is a value measured by the phthalic anhydride-pyridine method based on the method specified in K-1557.

Similarly, the acid value is the value obtained by neutralization titration using an acetone solvent.

Note that all parts in the examples represent parts by weight.

"Example-1" 32 parts of ethylene glycol, ε-
970 parts of caprolactone was charged, and vacuum dehydration treatment was performed for 4 hours under a nitrogen stream to remove ethylene glycol and ε.
-Total amount of water contained in caprolactone (20001)
l) Reduced from Im to 50 ppm.

Tetrabutyl titanate) 0 as a polymerization catalyst in the reaction solution
．． After adding 0.005 parts, a ring-opening polymerization reaction was carried out at 150''C, and the content of ε-caprolactone monomer became less than 1% by gas chromatography analysis in about 3 hours, yielding polycabrolactone diol.

The acid value of the obtained product was 0.20 OH/r, and the hydroxyl value was 56.8 OH/r.

"Example-2 Into the same equipment as in Example-1, trimethylolpropane 13
6 parts and 870 parts of ε-caprolactone were charged and subjected to vacuum dehydration treatment under a nitrogen stream for 3 hours to reduce the total water content contained in trimethylolpropane and ε-caprolactone from 20001) plm to 141) l) 11. Ta.

0 tetrabutyl titanate as a polymerization catalyst in the reaction solution
．． After adding 0.005 parts, a ring-opening polymerization reaction was carried out at 150°C, and in about 6 hours, the content of ε-caprolactone monomer became less than 1% by gas chromatography analysis, and polycaprolactone triol was not obtained.

The acid value of the obtained product was 0.10 ■OH/K, and the hydroxyl value was 169.7 ■KOH/t.

"Example-3J 32 parts of ethylene glycol was added to the same apparatus as in Example-1.
970 parts of ε-caprolactone was charged and subjected to vacuum dehydration treatment under a nitrogen stream for 3 hours to reduce the total amount of water contained in ethylene glycol and ε-caprolactone to 2100 parts.
It was reduced from pIll to 20ppn.

After adding 0.01 part of stannous bromide as a polymerization catalyst to the reaction solution and carrying out a ring-opening polymerization reaction at 130°C, the content of ε-caprolactone monomer decreased to 1% by gas chromatography analysis in about 4 hours. polycaprolactone diol was obtained.

The acid value of the obtained product was 0.06 7 g, and the hydroxyl value was 55.9 OH/.

"Example-4" Into the same apparatus as in Example-1, 468 parts of 2-hydroxyethyl methacrylate, 410 parts of ε-caprolactone, and 4.3 parts of hydroquinone monomethyl ether as a polymerization inhibitor were added.
9 parts of 2-hydroxyethyl methacrylate and ε-caprolactone were charged, and vacuum dehydration was carried out for 3 hours while introducing air to reduce the total amount of water contained in 2-hydroxyethyl methacrylate and ε-caprolactone to 1500.
It was reduced from pp11 to 7201116.

After adding 0.1 part of stannous bromide as a polymerization catalyst to the reaction solution and conducting a ring-opening polymerization reaction at 130°C, the content of ε-caprolactone monomer decreased to 1% by gas chromatography analysis in about 7 hours. %, and polycaprolactone-modified 2-droxyethyl methacrylate was obtained.

The obtained product had an acid value of 2.84 μm/1 and a hydroxyl value of 221 INKOH/r.

"Comparative Example-1" In a device similar to Example-1, 32 parts of ethylene glycol,
970 parts of ε-caprolactone and 0.005 parts of tetrabutyl titanium as a polymerization catalyst were charged, and a ring-opening polymerization reaction was carried out at 150°C under a nitrogen stream.
In time, the content of ε-caprolactone monomer as determined by gas chromatographic analysis became less than 1%, and polycaprolactone diol was obtained.

The acid value of the obtained product was 0.64 ■KOH/g, and the hydroxyl value was 56.7 ■OH/t.

"Comparative Example-2" Trimethylolpropane 13 was added to the same equipment as in Example-1.
6 parts, 870 parts of ε-caprolactone, and 0.005 parts of tetrabutyl titanate, and heated at 150°C under a nitrogen stream.
When ring-opening polymerization reaction was carried out, the content of ε-caprolactone monomer became less than 1% as determined by gas chromatography analysis in about 18 hours, and polycaprolactone triol was obtained.

The acid value of the obtained product was 0.64 .087 g, and the hydroxyl value was 170.2 OH/g.

"Comparative Example-3" 32 parts of ethylene glycol was added to the same apparatus as in Example-1.
When 970 parts of ε-caprolactone and 0.01 part of stannous bromide were charged as a polymerization catalyst and a ring-opening polymerization reaction was carried out at 130°C under a nitrogen stream, the content of ε-caprolactone monomer was determined by gas chromatographic analysis in about 25 hours. The ratio was less than 1%, and polycaprolactone diol was obtained.

The acid value of the obtained product was 0.62 KOH/r, and the hydroxyl value was 57.1 mKOH/r.

"Comparative Example-4" 468 parts of 2-hydroxyethyl methacrylate, 410 parts of ε-caprolactone, 4.39 parts of hydroquinone monomethyl ether were placed in the same apparatus as in Example-1, and 0 stannous bromide was added as a polymerization catalyst in the reaction solution. When 1 part of ε-caprolactone was charged and subjected to ring-opening polymerization reaction at 130°C in the presence of oxygen, the content of ε-caprolactone monomer as determined by gas chromatographic analysis became less than 1% in about 25 hours, indicating that the polycaprolactone modified 2-caprolactone monomer content was less than 1%. Roxyethyl methacrylate was obtained.

The obtained product had an acid value of 4.1811 Ir/g and a hydroxyl value of 224.1 E/g.

The compounding ratio 1 reaction conditions employed in the above Examples and Comparative Examples and the properties of the obtained polymers are summarized in Table 1.

Claims (1)

[Claims] When manufacturing a polylactone polyol by ring-opening polymerization of lactones using an initiator, water contained in the initiator and/or lactones is 100 ppm or less (I ) Production method of polylactone polyol having the structure of the formula ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ (I) [However, Y is the residue of ring-opening polymerization of lactones having 4 to 8 carbon atoms, R is the initiator , n is the number of added moles, n≧1, and m is the number of substituents, m=1 to 6].