JPH01236233A - Production of azo polycarbonate - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing a polycarbonate having an azo group in its main chain.

[Conventional technology]

Generally, azo compounds are used as polymerization initiators because they decompose due to heat and generate radicals. As a method for synthesizing easily decomposable polymers having azo groups, there is a method for producing polymers having azo groups in side chains by copolymerizing vinyl monomers having azo groups in side chains with other nonhinyl monomers (Makromo Co., Ltd.). l.

Chem,, /lr0 60? (/ri7ri))
(2) A method for producing a polymer having an azo group in its side chain by reacting a hydroxyl group-containing polymer with a carboxyl group-containing azo compound (Makromol, Chem.

Jg /7 (/96ri)) ■ A method for producing a polyurethane containing an azo group in its main chain by reacting a glycol having an azo group with a diisocyanate compound.

(Angew, Makromol, Chem, /9
2 (/ri67)) ■ Method for synthesizing an azo group-containing polyamide or polyester from an azo group-containing dicarboxylic acid chloride and a diamine or glycol (Kobunshi Ronshu 33 (3) /3/ (/ri”), J, Polym
.

Sci, A Polym, Chem,, 2414t0
6 (/P♂1))■ Method for synthesizing polycarbonate having an azo group in the main chain from an azo group-containing dicarboxylic acid chloride and bisphenol A (JP-A-Shojter 2770
♂) etc. have been proposed.

Any azo group-containing polymer is useful in making block copolymers and graft copolymers.

However, in the method (2), the synthesis of the azo group-containing vinyl monomer is complicated, and in the method (2), it is difficult to completely react the azo compound because it involves a polymer reaction. In addition, methods (1) and (2) require the separate synthesis of the azo group-containing dicarboxylic acid chloride, which has drawbacks such as being complicated. Furthermore, there is a description that an azo group-containing polycarbonate resin can be produced using the method (2) using an azo group-containing diacid halide, a diol, a dialkylene halide, and a dicarboxylic acid, but it is difficult to produce azo group-containing polycarbonate resin by interfacial polymerization with other than diacid halides. There are drawbacks.

[Purpose of the invention]

The present inventors have intensively investigated a method for producing a polycarbonate having an azo group in its main chain without the above-mentioned drawbacks, and as a result, have arrived at the present invention.

That is, the present invention relates to a compound containing seven azo groups in the molecular main chain and having a phenolic hydroxyl group, imino group, or amine group at both ends, and an azo group. An azo group in the main chain, which is characterized by polycondensation of a stable bisphenol compound and a carbonate pre-1°C form? This is a method for producing polycarbonate having the following properties.

[Structure of the invention]

The compound used in the present invention having one azo group in the molecular main chain and having phenolic hydroxyl groups at both ends (hereinafter referred to as azobisphenol) has the general formula (herein, R1 and R2 are hydrogen, lower (representing an alkyl group or an aromatic group), salts and hydrates thereof. For example.

Also general formula (Here, R1 and R2 are the same as above a) Salts and hydrates of the following:

for example etc.

HR' containing 7 azo groups in the molecular main chain used in the present invention
R'H (where R is two organic groups, R3 and R4 are hydrogen, lower alkyl group, nitrile group, or aromatic group), salts and hydrates thereof.

for example etc.

A compound containing seven azo groups in the molecular main chain and having amine groups at both ends (hereinafter referred to as azobisamine) used in the present invention is a compound of the general formula (where R5 and R6 are hydrogen, a lower alkyl group, or an aromatic group, and Ar is a divalent aromatic group), their salts, and hydrates;
For example, etc.

Also included are those represented by the general formula (85.R' and Ar have the same meanings as above), and salts and hydrates thereof.

These can be used alone or in combination of two or more.

Other azobisamines having seven azo groups in the molecular main chain used in the present invention have the general formula (where B7,
R8 is hydrogen, a lower alkyl group, or an aromatic group), salts and hydrates thereof, and examples thereof include the following.

As the azo group-free bisphenol compound used in the present invention, those represented by the following general formula are used.

y2 Y4 Specific examples of bisphenol compounds that can be used in the present invention include bis-(Hiro-hydroxyphenyl)methane, /, I-bis-(lIL-hydroxyphenyl)ethane, /, /-bis-(≠- Hydroxyphenyl)furopane, 2,2-bis-(Hiro-hydroxyphenyl)propane (
Bisphenol A),! , 2-upper 2-(Hiro-hydroxyphenyl)butane, 2.2-bis-(Hiro-hydroxyphenyl)pentane, 2.2-bis-(Hiro-hydroxyphenyl)-3-methylbutane, x,z-his -(4L-hydroxyphenyl)hexane, ! , 2-upper 2-(Hiro-hydroxyphenyl)-μm methylpentane, /, I-bis-(Hiro-hydroxyphenyl)phenylmethane, /, I-bis-(lIL-hydroxyphenyl)cyclopentane, /, / -bis-(lL-hydroxyphenyl)cyclohexane, 2.2-bis-(Hiro-hydroxy-3-chlorophenyl)propane, 2.2-bis-(Hiro-hydroxy-31!-dimethylphenyl)propane, p, Bisphenol compounds such as 4t'-dihydroxydiphenyl ether, Hiro, Hiro'-dihydroxydiphenyl sulfone, and Hiro, Hiro'-dihydroxydiphenyl sulfide can be mentioned.

The bisphenol compound is necessary when the carbonate precursor described below is phosgene, but it does not necessarily need to be present when the precursor is a polycarbonate oligomer.

The carbonate precursors used in the present invention are those that react with bisphenol compounds to produce polycarbonate, and polycarbonate oligomers, and specifically include phosgene, bischloroformates such as bisphenol A and hydroquinone, and their oligomers, and ethylene. Examples include bischloroformates of glycol and neopentyl glycol. Preferred carbonate precursor materials are phosgene, bischloroformates of bisphenols and oligomers thereof.

The polycarbonate of the present invention is preferably produced by an interfacial polymerization method or a pyridine method among conventional well-known methods.

In the interfacial polymerization method, an aqueous sodium hydroxide solution, a water-insoluble organic solvent such as methylene chloride, bisphenol, azobisimine, azobisamine or azobisphenol, a carbonate precursor, and, if necessary, a catalyst and a molecular weight regulator are used.

The catalyst may be any of the known catalysts that promote polycarbonate formation reactions.

These catalysts include, but are not limited to, tertiary amines such as triethylamine, ≠-grade ammonium salts, and ≠-grade phosphonium salts.

Either of these may be used.

These compounds are phenol, chlorophenol, I)
Examples include, but are not limited to, -tert-butylphenol.

In the pyridine method, an organic base such as pyridine, a water-insoluble organic solvent such as methylene chloride, bisphenol, azobisimine, azobisamine or azobisphenol, a carbonate precursor and, if necessary, a molecular weight regulator are used.

The amount of azobisimine, azobisphenol, or azobisamine used in the present invention is 0.000% based on the bisphenol unit in the polymer. It is necessary to use a molar proportion or more of O. This is because if it is less than θ, or mol, the meaning of 7 as a polymer having an azo group is lost. That is, when an azo group-containing polycarbonate is used as a radical polymerization initiator, its ability to initiate polymerization is extremely poor.

In both the interfacial polymerization and pyridine methods, the reaction must be carried out at a relatively low temperature that does not decompose the azo group, and is generally carried out at -10-≠0°C, preferably from 0 to 30°C.

The polycarbonate having an azo group in the main chain of the present invention is used for producing various block copolymers (a) Production of oligomers Bisphenol A IOO part Sodium hydroxide 37 parts Water
670 parts of the above mixture was charged into a reactor equipped with a stirrer, and 36 parts of methylene chloride was added while stirring at ♂00 rpm.
Added 0 parts. Next, while cooling the mixed solution to below 20°C, add phosgene. was blown into the solution for 60 minutes to effect oligomerization. After the reaction was completed, only the methylene chloride solution containing the polycarbonate oligomer was collected.

The analysis results of the obtained oligomer solution in methylene chloride are as follows.
It was as follows.

Oligomer concentration:,'7% (Note/) Terminal chloroformate group concentration 0. Yo0 regulation (Note 2)
Terminal phenolic hydroxyl group concentration 0.0λ standard (Note 3)
(Note) Measured after evaporation to dryness.

(Note 2) Neutralization titration of aniline hydrochloride obtained by reacting with aniline with 0.2N aqueous sodium hydroxide solution.

(Note 3) Colorimetric determination of the color developed when titanium tetrachloride is dissolved in acetic acid solution using j g 4 nm.

The oligomer solution obtained by the above method is hereinafter abbreviated as oligomer solution A.

Middle) Polymer production oligomer solution A 177y11p te
rt-Butylphenol 0.1 Hiroyo? 300 methylene chloride The above mixture was charged into a reactor equipped with a stirrer and stirred at 1100 rpm. Furthermore, an aqueous solution λ,2'-azobis(N,N'dimethyleneisobutyramidine) dihydrochloride/, 2933? with the following composition: Aqueous solution of triethylamine dissolved in 36 ml of water 0.2 me water
Za3
After addition, interfacial polymerization was carried out at room temperature for 3 hours.

After separating the polymerization solution into an aqueous layer and a methylene chloride layer containing polycarbonate, the methylene chloride layer was sequentially washed with an aqueous sodium hydroxide solution, an aqueous hydrochloric acid solution, and demineralized water.Finally, the methylene chloride was poured into a large amount of methanol to separate the polymer. It precipitated. After filtering the precipitated polymer, it was vacuum dried at room temperature for 2 hours to obtain a white powdery polymer. The yield of the polymer is 1], and ηinh ((1) J t/d
i, in methylene chloride, 30°C) is OJ Od
It was i/f.

Differential thermal analysis (DSC) of this polymer showed that the beam was 0, /
A broad exothermic peak was expected at 0°C. When this polymer was heat-treated at 130°C for 5 hours, the exothermic peak in the above temperature range was no longer observed. Moreover, the ultraviolet absorption spectrum (U
V) showed maximum absorption at 3 j Onm. In addition, 2
．． In polycarbonate obtained by polymerization without using λ'-azobis(N,N'-dimethyleneisobutyramidine) dihydrochloride, the exothermic peak in DSC and the J
No maximum absorption at j Onm was observed. Further, DSC and UV of 2.2'-azobis(N,N-dimethyleneimbutyramidine) dihydrochloride showed an exothermic peak in the above temperature range and maximum absorption at 3 j Onm.

Example 2 Oligomer solution A /77@1p-te
rt-Butylphenol o,t sy Methylene chloride t O,111
! The above mixture was charged into a reactor equipped with a stirrer and stirred at 1100 rpm. Furthermore, an aqueous solution having the following composition, namely 2% by weight triethylamine aqueous solution 0.9meλ,
2'-azobis[N-(Hiro-hydroxyphenyl)-2
- Meherpropionamidine fudihydrochloride 8972? Aqueous solution 2! dissolved in water rty! Add ml of weight% caustic soda aqueous solution to moss
After stirring for 30 minutes, 700 ml of methylene chloride was added to the mixture and polymerized for 2.5 hours at room temperature.

The polymerization solution was treated in the same manner as in Example to obtain a white powdery polymer.

The yield of the polymer was 77% and ηinh was O4 Hiro! di
/f. A broad exothermic peak was observed at 60 to 70°C by DSC, and a maximum absorption at 3jOnm was observed by UV. Quantitative determination of azo groups by UV revealed that the polymer contained almost as many azo groups as originally prepared.

Example 3 Oligomer solution A/ 77 @1 p-tert-butylphenol 0.1rj? Methylene chloride 60% The above mixture was charged into a reactor equipped with a stirrer and stirred at 600 rpm. Furthermore, an aqueous solution having the following composition, ie, a 2% by weight triethylamine aqueous solution 0.7me2.
2'-Azobis(2-methylpropionamidine) dihydrochloride/0za? Aqueous solution 2! After adding 4 ml of aqueous sodium hydroxide solution (wt%) and stirring for 30 minutes, 700 ml of methylene chloride was added to the mixture and polymerized at room temperature for 2 hours.

The polymerization solution was treated in the same manner as in Example 1 to obtain a white powdery polymer.

The yield of polymer is 75%, ηinh is o, 4'3
dll? There was a time. DSC Te, S' 0~/A
A broad exothermic peak was observed at 0°C, and UV was 3!
Maximum absorption was observed at Onm.

When this polymer was heat-treated at 130°C for 5 hours, it showed an exothermic peak in DSC and 3! in UV. The maximum absorption at Onm had disappeared.

Example ≠ Oligomer solution A /77 punishment p-tert-
Butylphenol 0.64LS? Methylene chloride! r00 ml of the above mixture was charged into a reactor equipped with a stirrer and stirred at 1100 rpm. Furthermore, an aqueous solution having the following composition, that is, a 2 weight ratio triethylamine aqueous solution 0.7g2.
2'-azobis[N-(≠-aminopher≠tomi)-2
-Methylpropionamidine cotetrahydrochloride2. ／ ／ 9 on Wednesday♂0rnl! Aqueous solution dissolved in 2j weight of caustic soda aqueous solution 2! ml was added and polymerized for 3 hours at room temperature.

The polymerization solution was treated in the same manner as in Example to obtain a white powdery polymer.

The yield of the polymer is 2, and ηinh is 0j2dt.
/? ”'Cht o DSCf, r o～y 6゜°C
A broad exothermic peak was observed under UV light, and a maximum absorption was observed at 30 Onm.

Example to Example/In 2,2'-azobis(N,N'-dimethylinobutyramidine) dihydrochloride/, 23
3? 2.27-azobis(N,N'-dimethylisobutyramidine) instead of 2. o OJ? Polymerization was carried out in exactly the same manner as in Example 1, except that a white powdery polymer was obtained in a yield of 9'1%. ηinh is 0. ! /di
/ ? Met. From DSC and UV 90~/Evening o'
An exothermic peak was observed at c and a maximum absorption at 3 j Onm.

Example in Example Hiroshi! , 2'-azobisCN-(Hiro-aminophenyl)-λ-methylpropionamidine]tetrahydrochloride u, //9 instead of 2,2'-azobis(N-(3-aminophenyl)-2-methyl l Robionamidine] Tetrahydrochloride λ, 10? Polymerization was carried out in exactly the same manner as in Example ≠, except that tetrahydrochloride λ, 10? was used to obtain a white powdery polymer in a yield of 93%.η
inh is O0 Hirotdll? Met. An exothermic peak and large absorption were observed by DSC and UV.

Example 7 In Example 2, 2,2'-azobis(N-(4'-hydroxyphenyl)-2-metelglobionamidine)dihydrochloride/,2,2'-azobisCN- instead of 7-2 ('
7-hydroxyphenyl)-1-methylpropionamide]/! Polymerization was carried out in the same manner as in Example λ except that 319 was used.

Yield! A white powdery polymer with ηinh O,≠dl/9 was obtained. From DSC, is.

An exothermic peak was observed at °C, and maximum absorption was observed at 3 j Onm from UV.

Example ♂ In Example/2.2'-azobis(N,N'-dimethylisobutyramidine) dihydrochloride/,! ri33? 2 instead of
, 2'-azobis(,2-(3, Hiroshi, Ta, Otsu--tetrahydrobyrimidine-coyl)propank dihydrochloride 1. Polymerization was carried out in the same manner as in Example, except that θ was used. .

A white powdery polymer with ηinh O, 4t≠di/f/ was obtained in 2 hours. 90~/evening o with DSC and UV
An exothermic peak was observed at °C and a maximum absorption at 3 j Onm.

Reference Example 1 Azo group-containing polycarbonate obtained in Example 3.0
? , N-methyl-corbyrolidone (NMP) 37y and styrene 7.0? was placed in a 300 m/4-hole flask and purged with nitrogen under stirring, and then heated at 7 J'C for j hours, 13
Polymerization was carried out at 0°C for 7 hours.

The polymerization solution was poured into a large amount of methanol, washed several times with methanol, and then vacuum dried at 100° C. for 2 hours to obtain a white powdery polymer.

The polymerization rate of styrene is 2%, and the polymer ηinh is o, 3tdl/y (θ, j weight ratio, in NMP, J O'
C). The styrene homopolymer was extracted from this polymer using Soxhlet using cyclohexane as the extraction solvent. ■R spectrum and 'H-N M of the remaining polymer
In R there are styrene units and carbonate bonds,
It was confirmed that it was a block polymer.

Met. In addition, in an experiment in which styrene was thermally polymerized under the above conditions without using an azo group-containing polycarbonate, the weight percentage of styrene was measured.

Reference Example 2 Azo group-containing polycarbonate obtained in Example 2 3.0
9NMp37f and 7.02ml of styrene were placed in a 300-gallon flask and polymerized and post-treated in the same manner as in Reference Example 1. The polymerization rate of styrene is i co, and the polymer η1nh
130. Hiro2dl/? There was a time. Moreover, the blocking efficiency was 61%.

〔Effect of the invention〕

According to the method of the present invention, an azo group-containing polycarbonate resin can be obtained relatively easily, and by using it as an initiator, a block copolymer can be obtained at a high polymerization rate.

Claims (1)

[Claims] (1) A compound containing one azo group in the molecular main chain and a phenolic hydroxyl group, imino group, or amino group at both ends, a carbonate precursor, and, if necessary, a bisphenol compound that does not contain an azo group. A method for producing an azo group-containing polycarbonate, which comprises polycondensing.