JPH0687955A - Polymerization of cyclohexene oxide - Google Patents

Abstract

PURPOSE:To polymerize cyclohexene oxide under a mild condition (at a low reaction temperature) in a good yield. CONSTITUTION:Cyclohexene oxide is polymerized in the presence of at least one phosphoric acid compound selected from a group consisting of phosphoric anhydride, orthophosphoric acid, pyrophosphoric acid and polyphosphoric acid at 40-80 deg.C.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for polymerizing cyclohexene oxide, and more particularly to a method for heating and polymerizing cyclohexene oxide in the presence of a specific phosphoric acid compound. The obtained polymer is a lubricant, a release agent,
It is a compound useful as a raw material for paints, surfactants and plastics.

[0002]

2. Description of the Related Art Cyclohexene oxide (hereinafter referred to as "HX
Abbreviated as "O"), a method of using an organometallic compound such as trialkylaluminum, or a Lewis acid such as aluminum chloride, stannic chloride, ferric chloride, etc. alone or in combination is known. Has been. Further, a method of heating HXO in the presence of tetraboric acid and / or boric anhydride is known. (Japanese Patent Laid-Open No. 64-1
(1130 publication)

[0003]

DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention
Alternatively, the method using a Lewis acid has drawbacks in that the catalyst itself is expensive and special handling is required. According to the method using tetraboric acid and / or boric anhydride, the reaction temperature is as high as 130 to 140 ° C., and the catalyst to be used is complicated to adjust by heating or dehydrating orthoboric acid or anhydrous boric acid. There are drawbacks.

The present inventors have conducted extensive studies to find a method in which the reaction proceeds under mild reaction conditions (low reaction temperature) and a cyclohexene oxide polymer is obtained in a high yield. Was completed.

[0005]

That is, the present invention is to heat cyclohexene oxide in the presence of at least one phosphoric acid compound selected from the group consisting of phosphoric anhydride, orthophosphoric acid, pyrophosphoric acid and polyphosphoric acid. The method is a method for polymerizing cyclohexene oxide, characterized in that it is polymerized.

The phosphoric acid compound used in the present invention is phosphoric anhydride, orthophosphoric acid, pyrophosphoric acid, polyphosphoric acid, etc., which may be used alone or in combination. still,
The polyphosphoric acid includes tripolyphosphoric acid, tetratriphosphoric acid, trimetaphosphoric acid, hexametaphosphoric acid and the like.
These phosphoric acid compounds act as a polymerization catalyst, and the addition amount thereof is required to be 0.1% by weight or more with respect to the cyclohexene as a raw material, but the reaction rate and the degree of polymerization of the product are taken into consideration. In this case, 1.0 to 25% by weight is preferable.

The polymerization reaction of the present invention proceeds even at room temperature, but in order to obtain an appropriate reaction rate, the reaction temperature is 40 ° C.
It is preferably in the range of -80 ° C. If desired, it may be heated to a temperature higher than this. The reaction time is closely related to the reaction temperature and cannot be determined unconditionally, but can be arbitrarily determined within the range of 1 to 6 hours. When the reaction is carried out at 40 to 80 ° C, the reaction is completed within 2 hours.

When the above phosphoric acid compound is added to HXO and heated while stirring, the HXO is exothermicly dissolved to form a uniform solution. When the stirring is further continued, the viscosity of the reaction solution gradually increases as the polymerization reaction progresses, and the reaction is completed. In this reaction, in addition to the method of directly heating HXO in the presence of a phosphoric acid compound, HXO is converted to benzene, toluene,
It can also be performed after once dissolving in an inert aromatic solvent such as xylene.

The obtained polymer contains the phosphoric acid compound used as a catalyst as an impurity, and these phosphoric acid components can be removed by washing with hot water.
The average molecular weight of the HXO polymer thus obtained is
It is 900-1500.

[0010]

【Example】

Example 1 HXO (50 grams; 0.51 mol), phosphoric anhydride (8.
(9 g; 0.05 mol) was kept at 50 ° C. for 1.5 hours in a water bath while stirring with a mechanical stirrer in a glass reactor equipped with a reflux condenser. Then, unreacted HXO was distilled off under reduced pressure, the obtained polymer was stirred with hot water, and liquid separation was repeated several times to separate the phosphoric acid catalyst. When water is removed again under reduced pressure, colorless transparent H
XO polymer (glassy polymer) 36.8 g (74
%)was gotten. The average molecular weight was 1130 as a result of analysis by GPC method (gel permeation chromatography analysis (standard: polystyrene)).

Example 2 HXO (50 grams; 0.51 mol), toluene (50
(300 g) containing 300 g of a glass reactor was stirred with a mechanical stirrer to dissolve HXO, and then pyrophosphoric acid (12.5 g, 0.1 g) was added while maintaining the temperature at 50 ° C. in a water bath.
(07 mol) was added dropwise over 1.0 hour. 1.5 hours later
The phosphoric acid catalyst dissolved in the water phase is separated by stirring with pure water. Then, under reduced pressure, when toluene is distilled off,
49.4 g (9%) of colorless and transparent HXO polymer.
8.8%) was obtained. The average molecular weight was 1100.

Example 3 HXO (50 grams; 0.51 mole) and 99% orthophosphoric acid (8.2 grams; 0.1 mole) were placed in a glass reactor equipped with a reflux condenser and stirred at 80 It was kept at ℃.
After 2 hours, unreacted HXO was distilled off under reduced pressure,
The obtained polymer was stirred with hot water, and liquid separation was repeated several times to separate the phosphoric acid catalyst. When water is removed again under reduced pressure, a colorless transparent HXO polymer (glassy polymer)
39.3 grams (78.6%) were obtained. The average molecular weight by GPC method was 990.

[0013]

INDUSTRIAL APPLICABILITY According to the present invention, a polymer of cyclohexene oxide can be obtained in a high yield under mild reaction conditions (low reaction temperature), and the catalyst used is inexpensive and easy. The present invention is an industrially extremely advantageous method because it is available to the public.

Claims (1)

[Claims] 1. Cyclohexene oxide characterized by heating and polymerizing cyclohexene oxide in the presence of at least one phosphoric acid compound selected from the group consisting of phosphoric anhydride, orthophosphoric acid, pyrophosphoric acid and polyphosphoric acid. Polymerization method.