JPH01201331A - Production of azo group-containing polymer - 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 polyesters, polyamides and polyesteramides containing an azo group in the polymer main chain.

Generally, azo compounds decompose due to heat and generate radicals, so they serve as polymerization initiators. It is also useful as a modifier and compatibilizer for various resins.

[Conventional technology]

As a method for synthesizing a polymer having an easily decomposable azo group, (1) A method for producing a polymer having an azo group in the side chain by copolymerizing a vinyl monomer with another vinyl monomer (Makromol).

Chem, 2EOAc1 (/97?))■ Method for producing a polymer having an azo group in the side chain by reaction of a hydroxyl group-containing polymer and a carboxyl group-containing azo compound (Nlak
romo1. Chem.

yb tq (lqsq)) ■ A method for producing polyurethane containing an azo group in the main chain by reacting a glycol containing an azo group with a diincyanate compound (Angew, Ma-kromol, Che
m, / 9 (z967)) ■ Method for synthesizing azo group-containing polyamide or polyester from azo group-containing dicarboxylic acid chloride and diamine or glycol (
Collection of Polymer Papers L-31131c/qqt, ), J.

Polym, Sci, A Polym, Chem,
2 tl tx O& (/ 9 g A l■ A method for synthesizing a polycarbonate having an azo group in the main chain from an azo group-containing dicarboxylic acid chloride and bisphenol A (Japanese Patent Application Laid-Open No. 1983-7QOG) has been proposed.

[Problem to be solved by the invention]

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 hexamer is complicated, and in the method (2), since it is a polymer reaction, it is difficult to completely react the azo compound.

In addition, the methods (1) and (2) have drawbacks such as the necessity of separately synthesizing the azo group-containing dicarboxylic acid chloride, which is complicated.

The present invention provides a method for producing polyesters, polyamides, and polyesteramides having an azo group in the main chain, without the above-mentioned drawbacks.

[Means to solve the problem of poor section]

The present invention relates to a compound containing one azo group in the molecular main chain and having a phenolic hydroxyl group, imino group, or amine group at both ends, and if necessary, other diols and/or diamines and dicarboxylic acids. This is a method for producing an azo group-containing polymer having an azo group in the main chain, which is characterized by polycondensing the polymer with chloride.

The compound (hereinafter referred to as azobisphenol) having seven azo groups in the molecular main chain and phenolic hydroxyl groups at both ends used in the present invention is of the form - (where R1-R2 are hydrogen, lower alkyl group, nitrile group, or aromatic group), and their salts.

for example and so on.

In addition, there are compounds of the form - (where R1 and R2 have the same meanings as above), and salts thereof.

(Here, R is a divalent organic group -R1-R2 has the same meaning as above), and salts thereof.

for example and so on.

Compounds having one azo group in the molecular main chain and amino groups at both ends (hereinafter referred to as azobisamine) used in the present invention include general (here, R3 and H4 are hydrogen,
(a lower alkyl group or an aromatic group, where Ar is a divalent aromatic group), and salts thereof, such as:

There are also those represented by the form - (where R3-Ft', Ar has the same meaning as above), and salts thereof, such as:

In the present invention, these compounds having an azo group in the main chain can be used alone or in combination of two or more.

The dicarboxylic acid halides used in the present invention are cybarides, especially dichlorides, of aliphatic, cycloaliphatic or aromatic dicarboxylic acids. For example, terephthalic acid, isophthalic acid, diphenylmethane dicarboxylic acid, /, 4-naphthalene dicarboxylic acid, co, 6-naphthalene dicarboxylic acid, da,
q'-diphenyldicarboxylic acid, a,J-diphenyldicarboxylic acid, 2,2'-diphenyldicarboxylic acid.

<z, tI'-diphenyl ether dicarboxylic acid-4'
, 4”-diphenylketone dicarboxylic acid + 3.3’-
Diphenylketone dicarboxylic acid + <<, 4('-diphenylthioether dicarboxylic acid, da, μ'-diphenylsulfone dicarboxylic acid and other aromatic dicarboxylic acids and their derivative dichlorides, cyclohexanedicarboxylic acid, cyclopentanedicarboxylic acid and other alicyclic acids dichlorides of group carboxylic acids and their derivatives; dichlorides of saturated aliphatic dicarboxylic acids such as succinic acid, adipic acid, azelaic acid, and sebacic acid; unsaturated aliphatic acids such as maleic acid, fumaric acid, citraconic acid, itaconic acid, and dimer acid; Examples include dichloride of dicarboxylic acid.

In the present invention, in addition to azobisphenol, azobisimine, or azobisamine, other diol and/or diamine compounds may be used for polycondensation. These diol or diamine compounds are substantially free of azo groups.

These diols used in the present invention include aliphatic,
It is an alicyclic and aromatic diol compound. For example, ethylene glycol, propylene glycol, diethylene glycol, phethylene glycol, 6-hexane glycol, neopentyl glycol, 2,3-dimethyl-/,
Low molecular aliphatic diols such as 3-propylene diol, 9-cyclohexane dimetatool, polyethylene glycol, polypropylene glycol.

Polymeric aliphatic diols such as polycaprolactone diol, polyvalerolactone diol, and polyester diol obtained by polycondensation of the aliphatic dicarboxylic acid and low molecular weight aliphatic diol.

/, tI-cyclohexanediol, alicyclic diols such as 1,3-cyclohexanediol, bisphenol A, hydroquinone, resorcinol, /, tl-diphenyl dihydroxide, co, 7-naphthalene cyclohexide,
Examples include diphenol compounds such as 1,6-naphthalenedihydroxyto and 1,S-naphthalenedihydroxyto.

Further, as the diamine used in the present invention, any aromatic diamine, aliphatic diamine, and heterocyclic diamine can be used, and specific examples thereof include meta-phenylene diamine, para-phenylene diamine, ta,
u'-diaminodiphenylpropane, <z, v'-diaminodiphenylmethane, benzidine+! , 4('-
Diaminodiphenylsulfide, +, u'-diaminodiphenylsulfone 1. ? ,,7'-diaminodiphenylsulfone.

S, q'-diaminodiphenyl ether, co,6-diamitupyridine, bis-(deraminophenyl)diethylsilane, bis-(tI-aminophenyl)phosphine oxide, bis-(deraminophenyl)-N-methylamine, l, s-diaminonaphthalene, 3,3'-dimethyl-benzidine.

3.31-dimethoxy-benzene, 2. Derpis (β
-amine-t-7'thyl)toluene, bis-(hala-β)
-amino-t-butylphenyl)ether, rose-bis(2-methyl-q-aminobenzyl)benzene, rose-
Bis(/,/-dimethyl-5-aminopentyl)benzene, m-xylylenediamine, p-xylylenediamine,
Bis(hala-amino-cyclohexyl)methane, hexamethylene diamine, heptamethylene diamine, octamethylene diamine, nonamethylene diamine, decamethylene diamine, 3-methyl-heptamethylene diamine + Q
, Q'-dimethylhbutamethylenediamine+2. /
/-diaminododecane+/, copisu(3-aminopropoxy)-ethane, 2,2-dimethylpropylene diamine.

3-methoxy-hexamethylene diamine, 2,5-dimethylhexamethylene diamine, 2. S-dimethylhebutamethylenediamine, S-methylnonamethylenediamine+
/, 41-diamino-cyclohexane, /, l 2-
Diaminooctadecane, U,5-diamino-/,J
, 9-oxadiazole, etc., and these may be used alone or as a mixture.

In addition, piperazine, 2,5-dimethylpiperazine, and S
-Diimines such as diethylpiperazine can also be used.

Regarding the amounts of azobisphenol, azobisimine, or azobisamine, diol and/or diamine, and dicarboxylic acid chloride used in the present invention, the ratio of hydroxyl group, imino group, and amino group to acid chloride group is generally used in a substantial equivalent amount. Azobisphenol, azobisimine, or azobisamine can be polycondensed alone with dicarboxylic acid chloride in an equivalent amount, or can be used in combination with an azo group-containing compound and other diols and/or diamines. In this case, it is necessary that the azo group-containing compound be used in an amount of O,OS or more relative to the diol and/or diamine. This is because if the amount is less than the O,OS molar ratio, it will be meaningless as an azo group-containing polymer. That is, when an azo group-containing polymer is used as a radical polymerization initiator.

This is because their starting ability will be extremely poor.

The polycondensation in the present invention is generally carried out by solution polycondensation or interfacial polycondensation in an aprotic organic medium.

Aprotic organic media include toluene, acetone,
Acetonitrile, ethyl acetate, carbon tetrachloride, methylene chloride, 2-dichloroethane, N-methyl-cobyrolidone, pyridine, etc. are used, and if necessary, a dehydrochlorination agent such as triethylamine, morpholine, etc. is used.

These solution polycondensation methods and interfacial polycondensation methods are P and W.

Morgan; 'Condensation Pol
ymers by Interf-acial and
5solution Methods”, (/9A5)
.

The reaction temperature detailed in Interscience must in any case be carried out at a relatively low temperature such that the azo group does not decompose, and is usually carried out at -io to qO<0>C, preferably from [theta]<0>C to 30C.

The polymer having an azo group in the main chain of the present invention is useful as a polymerization initiator for producing various block copolymers.

〔Example〕

The present invention will be explained in more detail below using Examples.

Example 1 Bisphenol As, 2g in 300-fourth flask
xi o y (2,7,/s mnol)-2, co'-azobis(N-(!-hydroxyphenyl)-comethylglobionamidine] dihydrochloride o,
, t 277! ? (o, so o rrmol) and 40% N-methyl-copyrrolidone (NMP) were added to form a homogeneous solution. Next, after cooling the container with ice, 24 g to 9 of isophthalic acid chloride was added under stirring while flowing nitrogen gas.
- (Noda, )9 rrmol) and 92/oy (q, q b rrmol) were added to terephthalic acid chloride in -degrees for polycondensation. The mixture was stirred under water cooling for 30 minutes, and further stirred at room temperature for 5 hours. After the reaction, the mixture was poured into a large amount of water to precipitate the polymer. After washing with methanol several times, it was vacuum dried at room temperature for 2 hours to obtain a white powdery polymer. What is the yield? It was Q%. The ηinh of this polymer is 0. da/dl/p (0,!; wt% -'+'+2+2-tetrachloroethane/phenol at 30°C).

Differential thermal analysis of this polymer revealed a broad exothermic peak at go~/30°C. In addition, this polymer /
When heat treated at 30C for 5 hours, exothermic peaks in the above temperature range were no longer observed.

Example Colo 00 ml Isophthalic acid chloride e, o/, 2? in 3 flasks? (19,76/5mno
1) and methylene chlorite coθ01 were added to form a homogeneous solution. Next, separately prepared bisphenol A da, da 229
(/9.37 da plate m1) -ko, 2'-azobis [x
-(J-hydroxyphenyl)-11 methylpropionamidine] dihydrochloride o, tqbsl (o, 3
gqrrmol), caustic soda/, 7.7 q li'
, trioctylmethylammonium chloride Q, l
9 f and demineralized water 160? The Karanaro aqueous solution was added all at once to the above methylene chloride solution and stirred at high speed at room temperature to effect interfacial polymerization. After 1 hour, the reaction solution was poured into a large amount of acetone to precipitate the product. It was washed several times with water and methanol and dried under vacuum at room temperature for 2 hours to obtain a white powdery polymer. The yield was qO,g%.

was recognized. Note that when this polymer was heat-treated at 130°C for S hours, no exothermic peak in the above temperature range was observed.

Example 3 Into a 300 ml four-loaf flask, 3-bis(teraminophenoxy)benzene g, q q y (3o, qsr
rmol), 2. x'-Azobis[: N-(y
-Hydroxyphenyl)-11 methylpropionamide]0.6'I2f (1,1,7rrmol) and NMP7sf were added to form a homogeneous solution. Next, add isophthalic acid chloride 6, s g f (,72, da/
Orrmol) was added to the solution and polymerized for S hours at room temperature. The polymerization solution was poured into a large amount of water to precipitate the polymer.

After washing with methanol several times, it was vacuum dried at room temperature for 21 hours to obtain a white powdery polymer. The yield was 95%. The ηinh of this polymer is 0.76 di/5
4 (0.3wt%-3oc in NMP), and in differential thermal analysis, an exothermic peak was observed at //(7-/sa℃).When this polymer was heat-treated at 100℃ for S hours, the above temperature The exothermic peak in the region was no longer observed.

Example: In a 300-meter four-hole flask, isophthalic acid chloride, θ, ? f (/Orrmol) and methylene chloride/θ0? was added to make a homogeneous solution. Next, separately prepared co,2'-azobis(:N-(3-hydroxyphenyl)-comethylprobionamidine) dihydrochloride ta, 5sttf (l).

rrmol), caustic soda 871, trioctylmethylammonium chloride 0. /? and demineralized water gore
An aqueous solution consisting of was added all at once to the above methylene chloride solution and polymerized by stirring at high speed at room temperature. After 7 hours, the reaction solution was poured into a large amount of acetone to precipitate a polymer. The polymer was washed several times with water and methanol, and dried under vacuum at room temperature for 2 hours to obtain a white powdery polymer. The yield was 92%. The ηinh of this polymer is 0.77 di/51
'(0,!; wt, i, i, co, 1.?OC in 2-tetrachloroethane/phenol).

Example 5 Bisphenol AS, 25θ in a 300-four-loop flask
? f (23, Orrmol) -12'-azobis(N,N'-dimethyleneisobutyramidine) dihydrochloride o, i A/7 g-(o, so o
rrmol) and NMP&Of were added to form a homogeneous solution. Next, after cooling the container with ice, isophthalic acid chloride a, g s o t Iy (l
da, 0'A rrmol) and terephthalic acid chloride/ , 92/o y (q-tl4 rrmot)
was added twice to carry out one polycondensation.

Thereafter, the same treatment as in Example 1 was carried out to obtain a white powdery polymer. The yield was 92.0%. ηinh of this polymer
is 0.3 s di/P (0,!; wt'%,
i, i, 2. in s-tetrachloroethane/phenol,
30°C). In differential thermal analysis of this polymer, 10
A broad exothermic peak was observed at ~1 soc. Furthermore, when this polymer was heat-treated at 130°C for S hours,
The exothermic peak in the above temperature range was no longer observed.

Example 6 Isophthalic acid chloride q in Sθ0 Go 3 black flask,
oxo1 (tq, grrrmot) and methylene chloride 20θ1 were added to form a homogeneous solution. Next, separately prepared bisphenol A≠, 4130'i (/9
．． tIOjrrmol), ''''λ,
2'-azobis[co(3,da,S,6-titranohydrobyrimidine-coyl)propane fudihydrochloride 0. / 3 gr P(0,39!; rrmo
l).

Caustic soda 8739? , trioctylmethylammonium chloride θ, /95L and demineralized water /601 are added at once to the above methylene chloride solution,
Interfacial polymerization was carried out by stirring at high speed at room temperature. After 1 hour, the reaction solution was poured into a large amount of acetone to precipitate the product. It was washed several times with water and methanol and dried under vacuum at room temperature for 21 hours to obtain a white powdery polymer. The yield was 9L2%. The ηinh of this polymer was 0.57, and a broad exothermic peak at go-iso°C was observed in differential thermal analysis. Note that when this polymer was heat-treated at 730°C for 5 hours, no exothermic peak in the above temperature range was observed.

Example 7 1.3-bis(<=-aminophenoxy)benzene 9.00 Li-(30.7 g!
;rrmol) -2,2'-azobisC2-(3-mefk-coimidazoline-coyl)propane fudihydrochloride 0.39 ? a f (/, 7 rI
mol) and NWiP7Sf were added to form a homogeneous solution. Then under stirring isophthalic acid chloride ij 9 S 4%
Add (32, tl g !r rrmol) to -degrees,
Polymerization was carried out at room temperature for 5 hours. After polymerization, the reaction solution was poured into a large amount of water to precipitate a polymer. After washing with methanol several times, it was vacuum dried at room temperature for 2 q hours to obtain a white powdery polymer. The yield was 96.2%. ηi of this polymer
nh is o, b g dt/f (o, swt, N
30℃ in MP) and 30~/sO℃ in differential thermal analysis.
An exothermic peak was observed.

Note that when this polymer was heat treated at 130° C. for 5 hours, no exothermic peak in the above temperature range was observed.

Example g Isophthalic acid chloride 2.035' (/Orrmol) and methylene chloride 1001 were added to a 300 ml four-necked flask to form a homogeneous solution. Next, separately prepared co,2'-azobis(N,N'-dimethyleneisobutyramidine) 2. s o u f (/Orrmol
), caustic soda huff 1, trioctylmethylammonium chloride o, iy and demineralized water gQ? An aqueous solution consisting of was added all at once to the above methylene chloride solution and polymerized by stirring at high speed at room temperature. After 1 hour, the reaction solution was poured into a large amount of acetone to precipitate a polymer. The polymer was washed several times with water and methanol, and dried under vacuum at room temperature for 29 hours to obtain a white powdery polymer. The yield was 90.5%.

ηinh of this polymer is θ, 7'I di/
P (0,3 wtJ −/, /, 2,2-tetrachloroethane/phenol, 30° C.).

Example 9 Isophthalic acid chlorite co-03? (/Orrmol) and methylene chloride 100? was added to make a homogeneous solution. Next, separately prepared co,co′-azobis(N-(ta-aminophenyl)-
Comethylglobionamidinecotetrahydrochloride! ;, 26% (/Orrmol).

Caustic soda 3.3? An aqueous solution consisting of 0.04 jil of triethylbenzylammonium chloride and demineralized water was added all at once to the above methylene chloride solution and stirred at high speed at room temperature to perform one polymerization. After 1 hour, the resulting solution was poured into a large amount of acetone to precipitate a polymer. The mixture was washed several times with water and methanol, and vacuum dried at room temperature for 2 q hours to obtain a white powdery polymer. The yield was 93 cm. 77inh of this polymer is 1.2dl/f (0,3
wtJ in NMP at 30°C). From IR, 7.
Absorption based on amide groups was observed in 30 Q Cm-'' and / A g Q Cm-'.

Example 10 9.00 ml of l,3-bis(4L-aminophenoxy)benzene in a 3OO-four-bottle flask. [30.7g! r
rmol), co, 2'-azobis(N-(q-aminophenyl)-2-methylpropionamidine]o,
t, ta 71 (/, 7 rrmol) and NMP
7sf was added to make a homogeneous solution. Next, isophthalic acid chloride b, s q s y (,72,lIg
srrmol) was added to the solution at a temperature of -100 ml, and the mixture was polymerized at room temperature for 5 hours. After polymerization, the reaction solution was poured into a large amount of water to precipitate a polymer.

After washing with methanol several times, vacuum drying was performed at room temperature for 2 hours to obtain a white powdery polymer. The yield was 97%. The ηinh of this polymer is 0. G? dt/y
(o, swtJ, 3OC in NMP), and a broad exothermic peak was observed at go~/1.0°C in differential thermal analysis. When this polymer was heat treated at /30C for S hours, no exothermic peak in the above temperature range was observed.

Example // In a 30θ-4-hole flask, isophthalic acid chlorite co, 03P (/Orrmol) and methylene chloride 700? was added to make a homogeneous solution. Next, separately prepared =,2'-azobis(N-(J-aminophenyl)
-Comethylprobionamidine]tetrahydrochloride o,s2t,y (1 mmol) /,6-hexamethylenediamine 1.0'll.

? (9rrmol), caustic soda 2.3f, trioctylmethylammonium chloride 0. l? An aqueous solution consisting of demineralized water goy and demineralized water goy was added all at once to the methylene chloride solution, and polymerized by stirring at high speed at room temperature. After several hours, the reaction solution was poured into a large amount of acetone to precipitate a polymer. The mixture was washed several times with water and methanol, and vacuum dried at room temperature for 2 q hours to obtain a white powdery polymer. Yield is 92
%Met. of this polymer η1nbJ58Jdl/f(
o, s wtJ in NMP at 30°C). Differential thermal analysis revealed a broad exothermic peak at gO~/40°C. Note that when this polymer was heat-treated at 730° C. for 5 hours, no exothermic peak in the above temperature range was observed.

Example 12 In Example 7, isophorone diamine was substituted for 6-hexamethylene diamine! ;J39-(9rrmo
A white powdery polymer was obtained in a yield of 9% in exactly the same manner as in Example 1 except that 1) was used.

ηi,,'h of this polymer is 0.9dllP(θ, r
wt% in NMP at 30°C). 1 by differential thermal analysis
A broad exothermic peak was observed at 0-/AOC. When this polymer was heat-treated at 130° C. for 5 hours, the exothermic peak in the above temperature range was no longer observed.

Example 13 Adipic acid chloride (
/o mmol) and methylene chloride god were added to form a homogeneous solution. Next, separately adjust f, :, 2.2'-
Asohis[N-(tt-aminophenyl)-2-methylpropionamidine cotetrahydrochloride 0.2
b 3 f (0,3 rrmol), inphorondiamine 8t, i g f (q, s rrmol)
, caustic octopus, 0? An aqueous solution consisting of cetyltrimethylammomelam chloride o, o g y and demineralized water goy was added to the above methylene chloride, and sludge was observed at room temperature.

Example/4 (Sebacic acid chloride 2 in a 300 ml four-bottle flask)
．． 3 q f (/Orrmol) and carbon tetrachloride l
Oθ1 was added to make a homogeneous solution. Next, an aqueous solution consisting of separately prepared rochloride "-331i' (/Orrmol), caustic soda 87?, tributylbenzylammonium chloride θ, θg?, and demineralized water toy was added all at once to the above carbon tetrachloride solution, and the mixture was stirred at high speed at room temperature. After 2 hours, the reaction solution was poured into a large amount of acetone to precipitate a polymer. It was washed several times with water and methanol, and vacuum-dried at room temperature for 2 q hours to obtain a white powdery polymer. The yield was 92 cm.The ηinh of this polymerization was 1.0
di/f (o, swt'J, in NMP, 30°C). J from IR,,7 Q Q cr
Absorption based on amide groups was observed at n-' and 14g0cm''1.

Example/3 Isophthalic acid chloride u in a 500-tri-neck flask,
02 fP (/9.g rrmol) and methylene chloride 2QO? was added to make a homogeneous solution. Next, separately prepared bisphenol A11.1I30f (i q, a
03 rrmol) -co,2'-azobis[:N-(
deraminophenyl)-2-methylpropionamidine cotetrahydrochloride θ, 20 g? (0,39
srrmol), 8g of caustic soda? , trioctylmethylammonium chloride 0.19 ? and demineralized water/1. The aqueous solution consisting of Of was added all at once to the above methylene chloride solution and polymerized by stirring at high speed at room temperature. After 1 hour, the reaction solution was poured into a large amount of acetone to precipitate a polymer. It was washed several times with water and methanol and dried under vacuum at room temperature for 2 hours to obtain a white powdery polymer. Yield is 93
It was Chi. ηinh of this polymer is Q, dt
/ f (o, s wt%, / , / , 2, .2
- in tetrachloroethane/phenol at 30°C). Differential thermal analysis showed a broad exothermic peak at gO~1soc. When this polymer was heat-treated at 130° C. for 5 hours, the exothermic peak in the temperature range mentioned above was no longer observed.

Reference Example 1 Azo group-containing polyester obtained in Example 1 3.0? ,
NMPJ? fF, styrene 7, and Of were placed in a 300-meter four-hole flask, and the flask was purged with nitrogen while stirring, and then polymerized at 75° C. for 5 hours and at 1 soc for 1 hour. The polymerization solution was poured into a large amount of methanol to precipitate a polymer. Washed several times with methanol, the concentration was 7%, and the ηinh of the polymer was o,
6g (o, swt%, NMP, 7<7°C).

The styrene homopolymer was extracted from this polymer using a Nexhlet extractor using cyclohexane as the extraction solvent, and the remaining I
It was confirmed from the R spectrum and H-NMR that styrene units and amide bonds were present and that it was a block copolymer. The proportion of block copolymerized styrene among monopolymerized styrene was 5 g, or 2%. Further, in an experiment in which styrene was thermally polymerized under the above conditions without using an azo group-containing polyester, the polymerization rate of styrene was 9.

Reference Example Azo group-containing polymer obtained in Example q 2.0? , N.M.
P, 70p and butyl acrylate 50? The mixture was placed in a 300-meter round flask and purged with nitrogen while stirring, and then polymerized at 70C for a period of time. The polymerization solution was poured into a large amount of methanol to precipitate a polymer. After washing several times with methanol, a transparent rubbery polymer was obtained by vacuum drying at room temperature for several hours.

The polymerization rate of butyl acrylate was US, S%.

Next, the above rubbery polymer ion, NMP/0? and styrene 20? was added and polymerized at 70° C. for an hour in the same manner as above, and then further polymerized at 730° C. for 1 hour to obtain a white powdery polymer. The polymerization rate of styrene was 0%.

Reference Example 3 Azo group-containing polymer obtained in Example 5 3.0? , NMP
J? LiL and styrene 7.01 were placed in a 300-liter four-bottle flask, replaced with nitrogen under stirring, and then heated at 73°C for S hours.
Polymerization was carried out at 130°C for 1 hour.

The polymerization solution was poured into a large amount of methanol to precipitate the polymer, and the polymer was washed several times with methanol.

At 100℃! After vacuum drying for + hours, a white powdery polymer was obtained. The polymerization rate of styrene is q3. tr %,
ηinh of the polymer is o, q b (o, s wt%
.

NMP 30°C). IR spectrum and H-NMR of the remaining styrene homopolymer extracted from this polymer using a Soxter extractor using cyclohexane as an extraction solvent
It was confirmed that styrene units and amide bonds were present and that it was a block copolymer. Furthermore, the proportion of block copolymerized styrene among the polymerized styrene was 53. It was Schi. Further, in an experiment in which styrene was thermally polymerized under the above conditions without using an azo group-containing polymer, the polymerization rate of styrene was 9.

Azo group-containing polymer obtained in Reference Example d Example g 3. Of-NMP
30ff and butyl acrylate soP were placed in a 300-four-bottle flask, and the flask was purged with nitrogen while stirring, and then polymerized at 70° C. for 9 hours. The polymerization solution was poured into a large amount of methanol to precipitate a polymer, washed several times with methanol, and then vacuum dried at room temperature for 2 q hours to obtain a transparent rubbery polymer. The polymerization rate of butyl acrylate was 5θ, 1%.

Next, the above rubbery polymer ioy-1NMP/0? and styrene 201! ? Add 70 c in the same manner as above.
After polymerization for 9 hours at 130° C., the mixture was further polymerized for 1 hour at 130° C. to obtain a white powdery polymer. The polymerization rate of styrene is 3g, 9
It was Chi.

Reference Example 5 Azo group-containing polyamide J, 01 N obtained in Example 9
MPda 01 and butyl acrylate! Off 300-
Place in a four-bottomed flask and heat to 70°C after purging with nitrogen while stirring.
Polymerization was carried out at 130° C. for 1 hour. The polymerization solution was poured into a large amount of methanol to precipitate a polymer, washed several times with methanol, and then dried under vacuum at room temperature for 11 hours to obtain a rubbery polymer. The polymerization rate of butyl acrylate was 7.

Next, the above rubbery polymer 10f, NMP/OP and styrene 20? was added and polymerized for 1 hour at 70°C in the same manner as above, and then further polymerized for 1 hour at 130°C to obtain a white powdery polymer. The polymerization rate of styrene was lI.

Reference Example 6 Azo group-containing polyamide 3 obtained in Example 1O, Of/
, NMP j Of, and styrene/Qf were placed in a 300-meter-four-hole flask, and the flask was purged with nitrogen while stirring, and then polymerized at 7jC for S hours and at 100° C. for 1 hour. The polymerization solution was poured into a large amount of methanol to precipitate a polymer, which was washed several times with methanol and vacuum dried at 700° C. for a few hours to obtain a white powdery polymer. The polymerization rate of styrene was 7%.

〔Effect of the invention〕

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

Applicant: Mitsubishi Chemical Industries, Ltd. Agent: Patent Attorney Hase - 1 other person

Claims (5)

[Claims] (1) A main compound characterized by polycondensing a compound containing one azo group in the molecular main chain and having a phenolic hydroxyl group, an imino group, or an amino group at both ends and a dicarboxylic acid chloride. A method for producing an azo group-containing polymer having an azo group in its chain. (2) 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 diamine compound and/or diol compound that does not contain an azo group, and a dicarboxylic compound. 1. A method for producing an azo group-containing polymer having an azo group in its main chain, the method comprising polycondensing an azo group with an acid chloride. (3) In the manufacturing method according to claim 1 or 2, the azo Method for producing group-containing polymer. (4) In the production method according to claim 1 or 2, the azo group is characterized in that both ends of the compound containing one azo group in the molecular main chain are imino groups. Method for producing containing polymer. (5) In the production method according to claim 1 or 2, the azo group is characterized in that both ends of the compound containing one azo group in the molecular main chain are amino groups. Method for producing containing polymer.