JPS6032825A - Production of aromatic polyformal resin - Google Patents

Abstract

PURPOSE:To obtain an aromatic polyformal resin in a short time, in high productivity, by reacting an alkali metal salt of an aromatic dihydric phenol with methylene chloride or methylene bromide at a specific rate of feeding, in the presence of a solvent at a specific temperature. CONSTITUTION:The aromatic polyformal resin having the recurring unit of formula IV is produced by the polycondensation reaction of the compound of formula I (R<1>-R<4> are H, CH3, Cl or Br; M is alkali metal; X is group of formula II, CH2, group of formula III, SO2 or S) with methylene chloride or methylene bromide. The reaction is carried out by dissolving the compound of formula I in a solvent (e.g. dimethylsulfoxide, N-methylpyrrolidone, etc.), and introducing the methylene chloride, etc. at 120-200 deg.C, preferably 150-160 deg.C in gaseous state at a rate of 0.02-0.15mol%/min, preferably 0.05-0.08mol%/min.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing aromatic polyformal resin,
More specifically, the present invention relates to a method for producing aromatic polyformal resin in a short time.

Aromatic polyformal resin has excellent heat resistance and transparency.
It is also known as a resin with good electrical properties.

Regarding the manufacture of this resin, U.S. Patent No. 3,069°3
No. 86 discloses a method for polycondensing aromatic dihydric phenol and methylene chloride.

However, in this method, the time required for the polycondensation reaction is extremely long, 20 hours or more, and the solution viscosity of the polymer obtained as a result of the reaction is 0.07 to 0.17 (
Since the reduced viscosity (expressed as η8p/e) is low, it cannot be said to be a method suitable for industrialization.

Also, Ni Sea Varnish Polymer Preprints, 2
Volume 3, No. 2, Page 117, 1982 (AC8poly
mer Preprints 23(2)117 (1
982)) proposes a method in which N-methylpyrrolidone is used as a solvent and the reaction temperature is 75C.
However, even with this method, the time required for the polycondensation reaction is 5 hours, and it is still not suitable for industrialization.

For these reasons, there is a strong demand for a method for producing aromatic polyformal resins in a shorter time and increasing productivity.

In order to satisfy this demand, the present inventor conducted a detailed investigation regarding the reaction conditions during polycondensation, and found that the temperature of the reaction system 9 The amount of methylene chloride or methylene bromide supplied to the reaction system The present inventors have discovered that by controlling the polycondensation reaction, the polycondensation reaction can proceed in a short time and its productivity can be significantly improved, and the present invention has been completed.

The objective of Kinoe and Akira is to provide a method for producing aromatic polyformal resins that can carry out polycondensation reactions in a short period of time.

The method of the present invention has the following formula: (wherein R', R2, R3, R' may be the same or different, H, C'Ks, C
Q represents Br; M represents an alkali metal; X
teeth? Represents either IL+ h -8-. ) an alkali metal salt of an aromatic dihydric phenol, and
methylene chloride or methylene bromide in the presence of a solvent,
The temperature is 120-200t? The method is characterized in that the methylene chloride or methylene bromide is reacted in an amount of 0.02 to 0.15 moles per minute with respect to the alkali metal ja of the aromatic dihydric phenol.

In the method of the present invention, the starting materials are an alkali metal salt of an aromatic dihydric phenol represented by the above formula and methylene chloride or methylene bromide.

In the above alkali metal salt, M is Na+K+Li
Any alkali metal may be used as long as it is an alkali metal such as, but Na is preferably Na, and Na is particularly preferable.

Alkali metal salts can be used independently, but two or more different types of alkali metal salts may be used in combination as appropriate.

In the method of the present invention, first, an alkali metal salt of an aromatic dihydric phenol is dissolved in a solvent.

As the solvent, an organic solvent is used, preferably dimethyl sulfoxide, N-methylpyrrolidone, sulporan, dimethylformamide, or the like. The amount of solvent used is
There is no particular limitation as long as the amount is sufficient to dissolve the alkali metal salt.

Next, this reaction system is controlled at a temperature of 120 to 200 C, and the next raw material, methylene chloride or methylene bromide, is added to the alkali metal salt in the system at a rate of 0.02 to 1 0/min.
The polycondensation reaction is carried out by feeding at a feed rate of 5 mol. As a supply method, a method is adopted in which gaseous methylene chloride or methylene bromide is blown into the system.

If the temperature is less than 1,000 degrees Celsius, the reaction will not proceed smoothly and the time required to complete the polycondensation reaction will be long; if the temperature exceeds 200 degrees Celsius, the molecular chains will be severed by free alkali. causing inconveniences such as Preferably 140-1800°, particularly preferably 150-160°
It is C.

If the supply rate of methylene chloride or methylene bromide is less than 0.02 molti/min, the time required for the polycondensation reaction becomes long, resulting in a decrease in productivity; if it exceeds 0.015 molti/min, the molecular weight This is not preferable because it causes problems such as an insufficient increase in . Preferably ll-to04~0
．． 1 molti/min.

Particularly preferably 0.05 to 0.08 mol %/min.

In the method of the present invention, the time required for the condensation reaction, that is, the time for blowing methylene chloride or methylene bromide, is 1
~2 hours is sufficient.

Then, the whole is cooled to room temperature, the precipitated solid is separated by D, and then dissolved in, for example, methylene chloride to remove by-product salts such as sodium chloride, and reprecipitated with, for example, methanol. A polymer is obtained.

The polymer thus produced has a repeating unit represented by the following formula: (wherein I, R2, R'', R4, and X each have the same meaning as above) death,
The molecular weight of the polymer is 302? The polymer has a reduced viscosity (η8p/.) of 0.3 to 0.6.

According to the method of the present invention, aromatic polyformal resin can be produced in a short time of 1 to 2 hours, so its productivity can be significantly improved, and it is extremely important to contribute to its industrial usefulness. It is.

The aromatic polyformal resin obtained by the method of the present invention takes advantage of its transparency and is used for electrical and electronic equipment materials such as optical disk memories, film-retaining plates for lighting equipment, IC printed circuit boards, and mechanical materials such as automobile parts. It is useful.

The present invention will be explained in more detail below based on examples.

Example 1 A 300 ml separable flask IC12 equipped with an argon gas blowing head, a stirrer, a rectifier and a thermometer.
45.69 (0.2 mol) of 2'-bis(4,4'-dihydroxydiphenyl)propane, 100 mg of dimethyl sulfoxide as a solvent, and 50 ml of chlorobenzene were added and dissolved at room temperature. Next, 16.8 g (0.4 mol) of sodium hydroxide (purity 97%) and 2 ml of distilled water were added thereto and heated to 70C in an oil bath. Thereafter, the temperature of the oil bath was raised to 170C, water and chlorobenzene were azeotropically distilled off, and the sodium salt of 2,2'-bis(4,4'-dihydroxydiphenyl)propane, which was a raw material, was prepared.

After completely distilling off water and chlorobenzene, the temperature was lowered to 150°C.
The temperature was lowered to C. and gaseous methylene chloride was blown therein at a rate of 149/min for 2 hours. The total feed 1- is 140 g, and the feed amount per minute is 2, which is generated in the reaction system.
The amount is 0,085 mole per mole of sodium salt of 2'-bis(4,4'-dihydroxydiphenyl)propane.

Thereafter, the whole is cooled to room temperature, the precipitated solid is separated, and this is dissolved in methylene chloride (IQ) to convert the by-produced chloride)
IJum was removed. Furthermore, add 0.5RKffl of this solution.
After shrinking, reprecipitation treatment was performed with methanol 4Q. The produced solid was separated and dried under reduced pressure at 1'20 tl' for 16 hours. 37 g of white polymer was obtained. Yield 78%.

When this polymer was subjected to NMR analysis, δ5,6P
Absorption due to the -OCH2- bond was observed in Pm, and -O-CI- was observed at the 1210 an-' position in the IR spectrum.
Absorption due to h-0-bonds was observed.

Using methylene chloride as a solvent, the concentration was 0.59/ltt.
.

The reduced viscosity (ηSp/c) at 25C was 0.43. In addition, the glass transition temperature is 92c, the melting point is 145C9
The thermal decomposition initiation flow rate was 424C.

Example 2 The same separable flask Vc used in Example 1, 4
．． 4'-dihydroxybisphenol sulfone 509
(0.2 mol), dimethyl sulfoxide 15 as solvent
0rnl and 6 omlf of chlorobenzene were added and dissolved at room temperature. Next, add 16.89 (o, 4 mol) of sodium hydroxide (purity 97%).

2 ml of distilled water was added and heated to 70C in an oil bath.

Thereafter, the temperature of the oil bath was raised to 170 DEG C., water and chlorobenzene were azeotropically distilled off, and the sodium salt of 4,4'-dihydroxybisphenylsulfone as a raw material was prepared.

After completely distilling off water and chlorobenzene, the temperature was lowered to 150°C.
The temperature was lowered to 0.degree. C., and gaseous methylene chloride was blown into the reactor at a rate of 1.4 f/min for 2 hours. The total feed rate is 140f, and the feed rate per minute is 4,4
The ratio is 1 mol to 0.085 mol of the sodium salt of '-dihydroxybisphenyl sulfone.

Thereafter, the whole was cooled to room temperature and mixed with 500ml of methylene chloride! After diluting with water to remove by-product sodium chloride, reprecipitation treatment was performed with methanol 41. The produced solid was filtered and dried under reduced pressure at 130°C for 10 hours. A white polymer 42.7f was obtained. Yield: 82 cm.

When this polymer was subjected to NMR analysis, δ5.6pp
Absorption due to 10-CI (, -0- bond is observed in m,
In the IR spectrum, 10- is located at 1210 cm-1.
Absorption due to CH, -0- bond sister was observed.

Using N-methylpyrrolidone as a solvent, concentration 0.2
f/dl, reduced viscosity at 30°C (η8p/c)
was 0.42. Moreover, the glass transition temperature is 167°C.

The melting point was 220°C, and the thermal decomposition onset temperature was 441°C.

Claims (1)

[Claims] (In the formula, R', R2, R3, and R' may be the same or different, and each represents H, CH3, and CQ. Br represents an alkali metal; Hs ■ An alkali metal salt of an aromatic dihydric phenol represented by
methylene chloride or methylene bromide in the presence of a solvent at a temperature of 120 to 200 t:' and a feed rate of methylene chloride or methylene bromide of 0.5 m/min relative to the alkali metal salt of aromatic dihydric phenol. (In the formula, R1, R2, R3, R', and X each have the same meaning as above.) A method for producing an aromatic polyformal resin having units.