JPH0859778A - Polydioxorane and its production - Google Patents

Abstract

PURPOSE: To obtain a polydioxorane with controlled molecular weight, excellent in heat resistance, useful as e.g. a resin additive, by reaction of an isocyanate with a polymer produced by polymerizing a dioxorane ring-contg. compound in the presence of a monohydric alcohol. CONSTITUTION: This polydioxorane having a structure of formula I [R<1> and R<2> are each a 1-24C hydrocarbon; R<3> is a 1-10C hydrocarbon; X is a 1,3- dioxorane ring-opened product of formula II or III (R<4> and R<5> are each H or a hydrocarbon); (m) and (n) are each >=1] is obtained by reaction of a polymer produced by polymerizing a 1,3-dioxorane ring-contg. compound such as 1,3- dioxorane in the presence of a monohydric alcohol such as methanol using a polymerization initiator such as a heteropoly-acid with pref. 0.05-40 pts.wt. (based on 100 pts.wt. of the polymer) of an lsocyanate such as hexamethylene diisocyanate. It is preferable that this polydioxorane have a number-average molecular weight (in terms of PS) of 400-150000.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to polydioxolane and a method for producing the same. More specifically, the present invention relates to a polydioxolane having a controlled molecular weight and excellent heat resistance, and a method for producing the same.

[0002]

2. Description of the Related Art Polydioxolane obtained by ring-opening polymerization of 1,3-dioxolane is disclosed, for example, in Japanese Examined Patent Publication No. 48-17
It is publicly known as disclosed in Japanese Patent Publication No. 390. The ring-opening polymerization of 1,3-dioxolane is, for example, a cationic polymerization usually carried out using a cationic polymerization catalyst as disclosed in the above-mentioned publications and the like. Usually, in cationic polymerization, the molecular weight of the obtained polymer is controlled by adjusting the amount of a polymerization initiator.

However, the ring-opening polymerization reaction of 1,3-dioxolane is very susceptible to impurities, and it is difficult to control the molecular weight by the amount of the polymerization initiator because it is accompanied by chain transfer. Furthermore, when trying to obtain a polydioxolane having a number average molecular weight of several thousand to several tens of thousands by using a large amount of a polymerization initiator, the polymerization reaction becomes extremely vigorous and dangerous, which is industrially difficult. Was impossible to implement.

Therefore, there has been no industrially feasible method for producing polydioxolane having a controlled molecular weight. In addition, there has been no polydioxolane with controlled molecular weight.

Further, the polydioxolane produced by the conventionally known method also has a problem of low heat resistance. That is, the heat resistant temperature of the conventional polydioxolane is about 200 ° C. at most even in a nitrogen atmosphere. Therefore, polyethylene, polypropylene, polyethylene terephthalate, polyvinyl chloride, polymethylmethacrylate, even when trying to blend with a general-purpose resin such as polystyrene, usually the mixing of additives to these general-purpose resins, the temperature at which the blending is performed, that is, 100 ° C late half-300
There is a problem in that the quality of the resulting blend is not stable because the polydioxolane is decomposed at ℃.

[0006]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above circumstances, and it is an industrially safe solution of polydioxolane having a controlled molecular weight and excellent heat resistance to solve the above problems. It is intended to provide a practicable manufacturing method.

Another object of the present invention is to provide a polydioxolane having a controlled molecular weight and excellent heat resistance.

[0008]

According to the present invention, a polymer obtained by polymerizing a 1,3-dioxolane ring-containing compound in the presence of a monohydric alcohol with a polymerization initiator is reacted with an isocyanate. And a method for producing polydioxolane having a structure represented by the following general formula (I).

[0009]

[Chemical 3]

(In the formula, R ¹ and R ² have 1 carbon atoms.
To 24 hydrocarbon groups or hydrocarbon groups optionally having an ether bond, which may be the same or different, R ³ is a hydrocarbon residue having 1 to 10 carbon atoms, X
Is 1,3 represented by the following general formula (II) or (III)
Represents a ring-opened product of dioxolane, and m and n represent an integer of 1 or more. ) —CHR ⁴ —O—CHR ⁵ —CH ₂ —O— (II) or —CHR ⁵ —CH ₂ —O—CHR ⁴ —O— (III) (provided that in the formulas (II) and (III), R ³ and R ⁴
Each independently represent hydrogen or a hydrocarbon group. Another invention of the present invention is a polydioxolane having a structure represented by the following general formula (I) and having a polystyrene reduced number average molecular weight of 400 to 150,000.

[0011]

[Chemical 4]

(In the formula, R ¹ and R ² have 1 carbon atoms.
To 24 hydrocarbon groups or hydrocarbon groups optionally having an ether bond, which may be the same or different, R ³ is a hydrocarbon residue having 1 to 10 carbon atoms, X
Is 1,3 represented by the following general formula (II) or (III)
Represents a ring-opened product of dioxolane, and m and n represent an integer of 1 or more. ) —CHR ⁴ —O—CHR ⁵ —CH ₂ —O— (II) or —CHR ⁵ —CH ₂ —O—CHR ⁴ —O— (III) (provided that in the formulas (II) and (III), R ⁴ and R ⁵
Each independently represent hydrogen or a hydrocarbon group. )

[0013]

First, in the method for producing polydioxolane of the present invention, a step of polymerizing a 1,3-dioxolane ring-containing compound in the presence of a monohydric alcohol by adding a polymerization initiator will be described.

The 1,3-dioxolane ring-containing compound which gives a structure corresponding to X in the general formula (I) is 1,3
-Dioxolane, 2-methyl-1,3-dioxolane,
2-phenyl-1,3-dioxolane, 4-methyl-
1,3-dioxolane, 4-ethyl-1,3-dioxolane and the like can be mentioned, and one kind or a mixture of two or more kinds thereof can be used. Also, these 1,3-
Among the dioxolane ring-containing compounds, 1,3-dioxolane has particularly high reactivity. On the other hand, other 1,3-dioxolane ring-containing compounds are inferior to 1,3-dioxolane in terms of reactivity, but are polymers having a high melting point and a slightly low hydrophilicity, which cannot be obtained by polymerization of 1,3-dioxolane. It has the feature of giving.

The alcohol used in the polymerization of the polydioxolane of the present invention is not particularly limited as long as it is a monohydric alcohol, and either aliphatic or aromatic alcohol can be used, and it has an ether bond in the molecule. Good. For example, as the aliphatic alcohol, methanol, ethanol, n-propanol, iso-propanol, n-butanol, iso-butanol, n-pentanol,
Examples thereof include ethylene glycol monomethyl ether and ethylene glycol monoethyl ether. Among them, monohydric alcohols having 1 to 24 carbon atoms are preferable because they have good compatibility with 1,3-dioxolane-containing compounds. Examples of aromatic alcohols include phenol and benzyl alcohol.

The amount of the alcohol used in the present invention is 0.0002 to 1 mol, preferably 0.0005 to 0.1 mol, based on 1 mol of the monomer. Usage is 0.
When the amount is less than 0002 mol, the molecular weight of the obtained polydioxolane tends to be dominated by the amount of the polymerization initiator, and it may be difficult to control the molecular weight by alcohol. On the other hand, when the amount used is more than 1 mol, a large amount of polymerization initiator is required for polymerization,
The reaction may not proceed at all.

There is no particular limitation on the method of adding the alcohol, and the method of adding 1, 2
Examples thereof include a method of mixing with a 3-dioxolane ring-containing compound and a method of mixing with a polymerization initiator and then adding to a 1,3-dioxolane ring-containing compound.

The polymerization initiator used in the present invention is not particularly limited, and a conventionally known polymerization initiator capable of ring-opening polymerization of 1,3-dioxolane ring can be used. Specific examples thereof include heteropolyacid, etherate of boron trifluoride, oxonium tetrafluoride compound such as triethyloxonium tetrafluoroborate, aluminoxane / sulfuric acid mixture, tin chloride, etc., and one selected from these Alternatively, two or more kinds are used. Examples of the heteropolyacid include phosphotungstic acid, silicotungstic acid, and phosphomolybdic acid. Among the above-mentioned polymerization initiators, heteropolyacid, triethyloxonium tetrafluoroborate and aluminoxane / sulfuric acid mixture are preferable because they have high activity, and among the heteropolyacid, phosphotungstic acid is an impurity contained in the 1,3-dioxolane-containing compound. It is preferable that it is hardly affected by moisture and that the obtained polydioxolane is non-coloring.

The polymerization of the present invention may be carried out without solvent or in a solvent having no active hydrogen. As the solvent preferably having no active hydrogen, for example, methyl ethyl ketone, acetone, ketones such as methyl isobutyl ketone, cyclic ethers such as dioxane, chloroform,
Examples thereof include halogen-containing hydrocarbons such as dichloromethane and trichloro-trifluoro-ethane, aromatic hydrocarbons such as toluene and xylene, and one kind or a mixture of two or more kinds thereof can be used.

The reaction temperature for producing the polydioxolane of the present invention is not particularly limited, but it is usually 0 ° C to 10 ° C.
It is preferable to carry out the reaction at 0 ° C, preferably 25 ° C to 80 ° C. When the reaction temperature is lower than 0 ° C, the reaction rate is very slow, and the productivity may be significantly reduced. On the other hand, when the reaction temperature is higher than 100 ° C, the reaction rate is so fast that it is difficult to remove the heat generated by the polymerization reaction and control the reaction, which is not only dangerous but also chain transfer reaction. In some cases, the molecular weight cannot be controlled because it is accelerated.

The apparatus for producing the polydioxolane of the present invention is also not particularly limited, and in addition to a conventional tank-type reactor equipped with a paddle-type or anchor-type stirring blade, a Maxblend blade manufactured by Sumitomo Heavy Industries, Ltd. Tank type reactor with a super blend blade, Noritake static mixer, Sumitomo Heavy Industries Co., Ltd. Sulzer mixer, piston flow type continuous reactor without a drive unit, Co., Ltd. KRC Kneader manufactured by Kurimoto Iron Works, Vivolac manufactured by Sumitomo Heavy Industries, Ltd., SCR kneader manufactured by Mitsubishi Heavy Industries, Ltd., TEX-K manufactured by Japan Steel Works, NEX-T manufactured by Kobe Steel, Ltd.
A uniaxial or biaxial continuous reactor such as MIXTRON or HYPERKTX can be used.

Since the polymer obtained in the polymerization step in the present invention may be decomposed if left as it is while the activity of the polymerization initiator is maintained, the polymerization initiator may be lost for stabilization after the polymerization. It is preferable to activate it. Examples of the deactivator of the polymerization initiator include amines such as ammonia, triethylamine, ethylenediamine, aniline, pyridine and piperidine, and basic compounds such as ammonia and sodium methylate. One or more of them are used. be able to. Among the above-mentioned deactivators, amines are particularly preferably used because they have good diffusivity in the polymer and can rapidly deactivate the polymerization initiator.

The deactivation of the polymerization initiator is preferably carried out within 2 to 300 minutes, preferably within 5 to 60 minutes from the time when the polymerization initiator is added. If the time from the addition of the polymerization initiator to the deactivation of the polymerization initiator is longer than 300 minutes, the decomposition of the polymer will proceed, so that polydioxolane having a desired molecular weight may not be obtained.

The method of deactivating the polymerization initiator is not particularly limited, and it may be carried out in a polymerization apparatus, or after the polymer is taken out from the polymerization apparatus, it is subsequently operated in a batch system or continuously as described in the polymerization apparatus. It may be carried out using another mixing device of the formula.

Next, in the method for producing polydioxolane of the present invention, the step of reacting the polymer obtained in the above-mentioned polymerization step with isocyanate will be described.

The polymer obtained in the polymerization step is mainly composed of polyoxolane having a structure represented by the following general formula (IV), and usually has a polystyrene reduced number average molecular weight in the range of 150 to 100,000.

R ′ ¹ —O— (X ′) pH (IV) (In the formula, R ′ ¹ may have a hydrocarbon group having 1 to 24 carbon atoms or an ether bond, R ^'2 is a hydrocarbon residue having 1 to 10 carbon atoms, X' is represented by the following general formula (V)
Alternatively, it represents a 1,3-dioxolane ring opened product represented by (VI), and p represents an integer of 1 or more. ) —CHR ′ ³ —O—CHR ′ ⁴ —CH ₂ —O— (V) or —CHR ′ ⁴ —CH ₂ —O—CHR ′ ³ —O— (VI) (provided that (V) and (VI ) In the formula, R ′ ³ and R ′ ⁴
Each independently represent hydrogen or a hydrocarbon group. ) The polymer may be subjected to a reaction with an isocyanate as it is without any particular purification, or a volatile matter may be distilled off under reduced pressure, or after purification such as reprecipitation purification, a reaction with an isocyanate may be performed. It may be used for the reaction.

The isocyanate used in the present invention is not particularly limited, and either aliphatic or aromatic isocyanate can be used. Specifically, for example, hexamethylene diisocyanate, 4,4′-methylenebis (cyclohexyl isocyanate), isophorone diisocyanate, trimethylhexamethylene diisocyanate, lysine isocyanate, tolylene diisocyanate, paraphenylene diisocyanate. , Naphthylene-1,5-diisocyanate and the like, and one or more of these can be used. Aliphatic isocyanates are superior to aromatic isocyanates in that they are non-coloring, but they have the drawback of low reactivity. Therefore, when the obtained polydioxolane is required to be non-coloring, it is preferable to use an aliphatic isocyanate.

The amount of the isocyanate used in the present invention is 0.005 to 200 per 100 parts by weight of the polymer.
Parts by weight, preferably 0.05 to 40 parts by weight. When the amount used is less than 0.005 parts by weight, sufficient heat resistance improving effect cannot be obtained. On the other hand, when the amount used is more than 200 parts by weight, not only the amount of isocyanate used may not be further improved in heat resistance, but it is economically disadvantageous. .

In the reaction of the isocyanate of the present invention, a conventionally known isocyanate reaction catalyst may be used. Specifically, organic metal catalysts such as octyl tin, dibutyl tin dilaurate and dibutyl tin oxide, alkali (earth) metal salts such as calcium acetate, sodium carbonate and calcium carbonate, triethylamine, ethylenediamine, aniline, pyridine, piperidine and the like. Examples thereof include amines, and one or more of these can be used.

There are no particular restrictions on the timing and the number of times the isocyanate of the present invention is added, but it is preferable to add it all at once after deactivating the polymerization initiator. As an advantage of adding after the polymerization initiator has been deactivated, a basic substance such as an amine used as a deactivator acts as a reaction catalyst for the isocyanate, so that it is not necessary to add an isocyanate reaction catalyst. Can be raised.

The reaction of the isocyanate of the present invention may be carried out without a solvent or in a solvent having no active hydrogen. As the solvent preferably having no active hydrogen, for example, ketones such as methyl ethyl ketone, acetone and methyl isobutyl ketone, cyclic ethers such as dioxane, chloroform, dichloromethane and trichloro-
Examples thereof include halogen-containing hydrocarbons such as trifluoro-ethane, aromatic hydrocarbons such as toluene and xylene,
These 1 type, or 2 or more types can be mixed and used.

The reaction temperature of the isocyanate of the present invention is not particularly limited, but the reaction is usually carried out at 30 ° C to 200 ° C, preferably 50 ° C to 150 ° C. When the reaction temperature is lower than 30 ° C, the reaction rate is very slow,
Productivity may be significantly reduced. On the other hand, when the reaction temperature exceeds 200 ° C., polydioxolane may decompose.

The reaction time of the isocyanate of the present invention is not particularly limited, but is usually 5 minutes to 100 hours, preferably 10 minutes to 48 hours. If the reaction time is less than 5 minutes, the reaction of the isocyanate may be incomplete and sufficient heat resistance may not be obtained. On the other hand, the reaction time is 10
When it exceeds 0 hours, not only the productivity is remarkably lowered, but also polydioxolane may be decomposed or the polydioxolane may be crosslinked due to a side reaction at the urethane bond.

Further, there is no particular limitation on the reaction method of the isocyanate, and it may be carried out in the polymerization apparatus, or after the polymerized product is taken out from the polymerization apparatus, it is subsequently operated in a batch system or continuously as described in the polymerization apparatus. It may be carried out using another mixing device of the formula. Further, volatile components such as alcohols, monomers and solvents remaining before the addition of isocyanate may be removed.

The molecular weight range of the polydioxolane controlled by the production method of the present invention is usually in the range of 400 to 150,000 in terms of polystyrene-equivalent number average molecular weight.
In particular, the molecular weight is in the range of 1000 to 150,000, especially 500.
It can be easily controlled in the range of 0 to 100,000.

The polydioxolane of the present invention is a polydioxolane having a structure represented by the above general formula (I) and having a polystyrene reduced number average molecular weight of 400 to 150,000. In particular, the molecular weight is in the range of 1000 to 100,000, especially 5000 to 5
It is useful in that it can be easily produced and handled easily.
Further, polydioxolane in which R ¹ and R ² in the general formula (I) are an alkyl group having 1 to 5 carbon atoms is useful in that it can be easily produced and handled easily. Examples of the method for producing polydioxolane include the above-described method for producing polydioxolane. Furthermore, various additives such as fillers, dyes, pigments, stabilizers, lubricants and crystal nucleating agents may be added to the polydioxolane of the present invention.

[0038]

EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited thereto.

Example 1 200.00 g of 1,3-dioxolane and 2.86 g of n-butanol were placed in a four-necked flask having a capacity of 300 ml equipped with a stirrer, a cooler, a thermometer and a nitrogen introducing tube, and placed in a water bath. To 30 ° C. To this, 1.0 ml of a 5 wt% solution of phosphotungstic acid in methyl ethyl ketone was added as a polymerization initiator with stirring. A temperature rise due to the heat generation of the polymerization reaction was observed 3 minutes after the polymerization initiator was charged, and the exothermic peak reached 78 ° C. 45 minutes after the polymerization initiator was charged. After further aging for 15 minutes, 5 ml of a 1,3-dioxolane solution of triethylamine having a concentration of 0.1% by weight was added to stop the reaction. In order to remove 1,3-dioxolane, n-butanol, triethylamine, methyl ethyl ketone, etc. remaining in the obtained polydioxolane, volatile components were removed at 80 ° C.-1 mmHg for 5 hours.

To the obtained polymer was added 3.57 g of hexamethylene diisocyanate and 0.5 ml of a 1,3-dioxolane solution of triethylamine having a concentration of 0.1% by weight, and the mixture was reacted at 120 ° C. for 24 hours. .

The obtained polydioxolane was made into a 50% by weight aqueous solution, which was then reprecipitated and purified with saturated saline. afterwards,
Purified polydioxolane at 100 ° C-1mmHg 4
As a result of drying for 8 hours, the polystyrene reduced number average molecular weight measured by size exclusion chromatography was 13
000 polydioxolanes (1) were obtained.

The Fourier transform infrared absorption spectrum of the obtained polydioxolane (1) is shown in FIG. 1, and the Fourier transform nuclear magnetic resonance spectrum is shown in FIG.

The Fourier transform infrared absorption spectrum of polydioxolane (1) shows that the absorption due to the NH group is 3
Absorption due to urethane bond near ^{1 at} 500 cm ^-1
Found at 539 cm ^-1 and 1720 cm ^-1 .

On the other hand, in the Fourier transform nuclear magnetic resonance spectrum of polydioxolane (1), 1.2 ppm, 1.4
A peak based on the hexamethylene group of the isocyanate added at ppm and 3.0 ppm is observed.

From the above results, polydioxolane (1)
The structure of R ¹ and R ² in the general formula (I) is n
A butyl group, R ³ is a hexamethylene group, the above general formula (I
It is specified that in I) or (III) R ⁴ and R ⁵ are hydrogen.

Example 2 200.00 g of 1,3-dioxolane and 1.43 g of n-butanol were placed in a four-necked flask having a capacity of 300 ml equipped with a stirrer, a cooler, a thermometer and a nitrogen introducing tube, and placed in a water bath. To 30 ° C. To this, 0.5 ml of a 5 wt% methyl ethyl ketone solution of phosphotungstic acid as a polymerization initiator was added with stirring. One minute after the addition of the polymerization initiator, a temperature rise due to the heat generation of the polymerization reaction was observed, and the exothermic peak reached 82 ° C. 15 minutes after the addition of the polymerization initiator. After further aging for 15 minutes, 5 ml of a 1,3-dioxolane solution of triethylamine having a concentration of 0.1% by weight was added to stop the reaction.

Next, 1.79 g of hexamethylene diisocyanate was added, and the mixture was reacted at 150 ° C. for 4 hours.

The obtained polydioxolane was made into a 50% by weight aqueous solution, which was then reprecipitated and purified with saturated saline. afterwards,
Purified polydioxolane at 100 ° C-1mmHg 4
As a result of drying for 8 hours, the polystyrene reduced number average molecular weight measured by size exclusion chromatography was 25.
000 polydioxolanes (2) were obtained.

In Example 2, by halving the amount of n-butanol used in Example 1, polydioxolane having a molecular weight twice that of the polydioxolane obtained in Example 1 was obtained. From this, it is clear that the molecular weight of the obtained polydioxolane is controlled by polymerizing the 1,3-dioxolane ring-containing compound in the presence of alcohol.

Example 3 60.00 g of 1,3-dioxolane and 0.552 g of ethanol were placed in a four-necked flask having a capacity of 100 ml equipped with a stirrer, a cooler, a thermometer and a nitrogen introducing tube, and the mixture was placed in a water bath for 30 minutes. ℃. to this,
1.0 ml of a 5 wt% methyl ethyl ketone solution of phosphotungstic acid was added as a polymerization initiator with stirring. A temperature rise due to the heat generation of the polymerization reaction was observed 20 minutes after the addition of the polymerization initiator, and an exothermic peak of 35 ° C. was reached 90 minutes after the addition of the polymerization initiator. After further aging for 90 minutes, 5 ml of a 1,3-dioxolane solution of triethylamine having a concentration of 0.1% by weight was added to stop the reaction. In order to remove 1,3-dioxolane, ethanol, triethylamine, methyl ethyl ketone and the like remaining in the obtained polydioxolane, volatile components were removed at 80 ° C.-1 mmHg for 5 hours.

2.35 g of hexamethylene diisocyanate and 0.5 ml of a 1,3-dioxolane solution of triethylamine having a concentration of 0.1% by weight were added to the obtained polymer, and the mixture was reacted at 120 ° C. for 24 hours. .

The obtained polydioxolane was made into a 50% by weight aqueous solution, which was then reprecipitated and purified with saturated saline. afterwards,
Purified polydioxolane at 100 ° C-1mmHg 4
As a result of drying for 8 hours, the polystyrene reduced number average molecular weight measured by size exclusion chromatography was 14
000 polydioxolanes (3) were obtained.

The Fourier transform infrared absorption spectrum and the Fourier transform nuclear magnetic resonance spectrum of the obtained polydioxolane (3) are shown in FIG. 3 and FIG. 4, respectively.

The Fourier transform infrared absorption spectrum of polydioxolane (3) shows that the absorption due to the NH group is 3
Absorption due to urethane bond near 500 cm ^-1
It is recognized at 1720 cm ^-1 .

On the other hand, in the Fourier transform nuclear magnetic resonance spectrum of polydioxolane (3), 1.3 ppm and 1.5
Peaks based on the hexamethylene group of the isocyanate added at ppm and 3.15 ppm are observed.

From the above results, polydioxolane (1)
In the general formula (I), R ¹ and R ² are ethyl groups, R ³ is a hexamethylene group, and the general formula (II)
Or in (III) it is specified that R ⁴ and R ⁵ are hydrogen.

<Example 4> 200.00 g of 1,3-dioxolane and 4.17 g of benzyl alcohol were placed in a four-necked flask having a capacity of 300 ml equipped with a stirrer, a condenser, a thermometer and a nitrogen introducing tube, and the mixture was placed in a water bath. The temperature was set to 30 ° C. In addition, 5% by weight of phosphotungstic acid as a polymerization initiator
0.5 ml of methyl ethyl ketone solution was added with stirring.
A temperature rise due to the heat generation of the polymerization reaction was observed 1 minute after the addition of the initiator, and the exothermic peak reached 75 ° C. 15 minutes after the addition of the initiator. After further aging for 15 minutes, 5 ml of a 1,3-dioxolane solution of triethylamine having a concentration of 0.1% by weight was added to stop the reaction.

Next, 3.57 g of hexamethylene diisocyanate and 5 ml of a 1,3-dioxolane solution of triethylamine having a concentration of 0.1% by weight were added, and the mixture was heated at 120 ° C.
And reacted for 24 hours.

The polydioxolane thus obtained was made into a 50% by weight aqueous solution, which was then reprecipitated and purified with saturated saline. afterwards,
Purified polydioxolane at 100 ° C-1mmHg 4
As a result of drying for 8 hours, the polystyrene reduced number average molecular weight measured by size exclusion chromatography was 14
000 polydioxolanes (4) were obtained.

The heat resistance evaluation results of the obtained polydioxolane (4) are shown in Table 1.

<Comparative Example 1> 60.00 g of 1,3-dioxolane was placed in a four-necked flask having a capacity of 100 ml equipped with a stirrer, a cooler, a thermometer, and a nitrogen introducing tube, and the inside was cooled in an ice water bath at 0 ° C. The temperature was 3 ° C. To this, 0.3 ml of a 5 wt% methyl ethyl ketone solution of phosphotungstic acid as a polymerization initiator was added with stirring. The polymerization started immediately after the addition of the polymerization initiator, and reached an exothermic peak of 45 ° C. in about 6 minutes. After that, the ice water bath was replaced with a hot water bath at 50 ° C., the reactor was kept warm, and the polymer was aged for 15 minutes. Then, 1,3-dioxolane solution of triethylamine having a concentration of 0.1% by weight was added.
The reaction was stopped by adding ml.

The obtained polydioxolane was made into a 50% by weight aqueous solution, which was then reprecipitated and purified with saturated saline. afterwards,
Purified polydioxolane at 100 ° C-1mmHg 4
As a result of drying for 8 hours, the polystyrene reduced number average molecular weight measured by size exclusion chromatography was 23.
Many polydioxolanes (5) were obtained.

The heat resistance evaluation results of the obtained polydioxolane (5) are shown in Table 1.

<Comparative Example 2> 200.00 g of 1,3-dioxolane and 1.43 g of n-butanol were placed in a four-necked flask having a capacity of 300 ml equipped with a stirrer, a cooler, a thermometer and a nitrogen introducing tube, and placed in a water bath. To 30 ° C. To this, 0.5 ml of a 5 wt% methyl ethyl ketone solution of phosphotungstic acid as a polymerization initiator was added with stirring. One minute after the addition of the polymerization initiator, a temperature rise due to the heat generation of the polymerization reaction was observed, and the exothermic peak reached 82 ° C. 15 minutes after the addition of the polymerization initiator. After further aging for 15 minutes, 5 ml of a 1,3-dioxolane solution of triethylamine having a concentration of 0.1% by weight was added to stop the reaction.

The obtained polydioxolane was made into a 50% by weight aqueous solution, which was then reprecipitated and purified with saturated saline. afterwards,
Purified polydioxolane at 100 ° C-1mmHg 4
As a result of drying for 8 hours, the polystyrene reduced number average molecular weight measured by size exclusion chromatography was 13
000 polydioxolane (6) was obtained.

The heat resistance evaluation results of the obtained polydioxolane (6) are shown in Table 1.

[0067]

[Table 1]

<Evaluation of Heat Resistance of Polydioxolane> The heat resistance of the polydioxolane obtained in Examples and Comparative Examples was
It was evaluated by "DTG-50" manufactured by Shimadzu Corporation. The heat resistance measurement results of the polydioxolanes obtained in Example 1 and Comparative Example 2 are shown in FIGS. 5 and 6, respectively. Table 1 shows the temperatures at which a 1% weight loss of polydioxolane was observed by this heat resistance evaluation method.

As is clear from FIGS. 5 and 6 and Table 1,
The polydioxolanes (1) to (4) obtained in Examples 1 to 4 of the present invention show almost no weight loss due to decomposition up to around 230 ° C., and the weight loss thereafter is gradual. On the other hand, the polydioxolanes (5) and (6) obtained in Comparative Examples 1 and 2 rapidly decomposed at around 200 ° C.
Almost completely decomposed at around 0 ° C. From this, it is clear that the polydioxolane of the present invention has superior heat resistance to conventional polydioxolane.

[0070]

By using the production method of the present invention,
It has become possible to safely and industrially produce polydioxolane having a controlled molecular weight and excellent heat resistance, which has been difficult in the past.

The polydioxolane of the present invention is a polydioxolane having a controlled molecular weight and excellent heat resistance. The polydioxolane is extremely useful as a resin additive, and when added to a resin such as polyethylene, polypropylene, polyethylene terephthalate, polyvinyl chloride, polymethylmethacrylate, or polystyrene, the resin has antistatic properties, hydrophilicity, and surface slippage. It is possible to impart sex.

[Brief description of drawings]

FIG. 1 is a Fourier transform infrared absorption spectrum of polydioxolane (1) obtained in Example 1 of the present invention.

FIG. 2 is a Fourier transform nuclear magnetic resonance spectrum of polydioxolane (1) obtained in Example 1 of the present invention.

FIG. 3 is a Fourier transform infrared absorption spectrum of polydioxolane (3) obtained in Example 3 of the present invention.

FIG. 4 is a Fourier transform nuclear magnetic resonance spectrum of polydioxolane (3) obtained in Example 3 of the present invention.

FIG. 5 is a temperature-weight reduction curve of the polydioxolane (1) obtained in Example 1 of the present invention by “DTG-50” manufactured by Shimadzu Corporation, in which the vertical axis represents the weight change (mg).
And the horizontal axis represents temperature (° C.).

FIG. 6 is a temperature-weight reduction curve of polydioxolane (6) obtained in Comparative Example 2 according to the present invention by “DTG-50” manufactured by Shimadzu Corporation, in which the vertical axis represents weight change (mg).
And the horizontal axis represents temperature (° C.).

Claims (3)

[Claims] 1. A 1,3-dioxolane ring-containing compound
Production of polydioxolane having a structure represented by the following general formula (I), characterized in that a polymer obtained by polymerizing by adding a polymerization initiator in the presence of a dihydric alcohol is reacted with an isocyanate. Method. Embedded image (In the formula, R ¹ and R ² are a hydrocarbon group having 1 to 24 carbon atoms or a hydrocarbon group which may have an ether bond, and may be the same or different, respectively.
R ³ represents a hydrocarbon residue having 1 to 10 carbon atoms, X represents a 1,3-dioxolane ring opened product represented by the following general formula (II) or (III), and m and n are integers of 1 or more. Represents ) —CHR ⁴ —O—CHR ⁵ —CH ₂ —O— (II) or —CHR ⁵ —CH ₂ —O—CHR ⁴ —O— (III) (provided that in the formulas (II) and (III), R ³ and R ⁴
Each independently represent hydrogen or a hydrocarbon group. ) 2. A polydioxolane having a polystyrene-reduced number average molecular weight of 400 to 150,000 and having a structure represented by the following general formula (I). Embedded image (In the formula, R ¹ and R ² are a hydrocarbon group having 1 to 24 carbon atoms or a hydrocarbon group which may have an ether bond, and may be the same or different, respectively.
R ³ represents a hydrocarbon residue having 1 to 10 carbon atoms, X represents a 1,3-dioxolane ring opened product represented by the following general formula (II) or (III), and m and n are integers of 1 or more. Represents ) —CHR ⁴ —O—CHR ⁵ —CH ₂ —O— (II) or —CHR ⁵ —CH ₂ —O—CHR ⁴ —O— (III) (provided that in the formulas (II) and (III), R ⁴ and R ⁵
Each independently represent hydrogen or a hydrocarbon group. ) 3. R ¹ and R ² in the general formula (I) are
The polydioxolane according to claim 2, which is an alkyl group having 1 to 5 carbon atoms.