JPH01234421A - Polyphenylene ether copolymer - Google Patents

Abstract

PURPOSE:To obtain the title copolymer suppressed in discoloration and viscosity increase when molded on heating, suitable for compositions with polystyrene, etc., by copolymerization of a component having aniline structure in its side chain methylene and by bonding at the terminal an aliphatic amine-linked component. CONSTITUTION:(A) A phenol of formula I (R1 is H, 1-4C alkyl, etc.), (B) an aniline of formula II (R2 and R3 are each 1-20C-alkyl, etc.; l is 1-5) and (C) a secondary aliphatic amine of formula III (R5 is 1-20C-alkyl, etc.) are dissolved in a solvent (e.g., mixed xylene) followed by addition of a catalyst (e.g., copper- amine complex) and then carrying out polymerization while stirring, thus obtaining the objective copolymer with a polymerization degree of 10-5,000, containing 0.02-20% (based on unit of formula V) of unit of formula IV, 0.02-1.0% (based on unit of formula V) of terminal group of formula VI, and 0-10% (based on unit of formula V) of a second terminal group of formula VII.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a novel polyphenylene ether copolymer. More specifically, the polyphenylene ether has a structural unit in which an aromatic amine is bonded to the side chain methylene group at the 2-position of a phenol, and a head end group in which an aliphatic amine is bonded, and it has coloration and resistance during heat molding. This invention relates to a novel polyphenylene ether copolymer having characteristics such as suppressed increase in viscosity.

[Conventional technology and problems]

Polyphenylene ether is widely used as an engineering resin with excellent heat resistance, mechanical properties, and electrical properties. However, this resin has a low softening point and is difficult to process.
There are problems with poor impact resistance, poor color tone, etc. In order to solve these problems, attempts have been made to blend polyphenylene ether with various resins and use additives, as well as to modify polyphenylene ether itself through modification reactions and copolymerization. For example, as one such attempt, the Japanese Patent Publication Publication No. 60-5 introduced anilines into the main chain of polyphenylene ether.
The method proposed in No. 0373 is one of them. However, even with this method, it cannot be said that sufficient modification has been achieved. Furthermore, a structure in which an aliphatic amine is bonded to an alkyl group at the ortho position of 11 mEi of water at the end of the head has also been proposed. (Unexamined Japanese Patent Publication No. 52-892). However, although polyphenylene ether with this structure has improved compatibility with polystyrene etc. and has excellent impact resistance when made into a composition, it has poor fluidity and the amine component decomposes when heated. It has the disadvantage of emitting a bad odor.

[Means for solving problems]

Under these circumstances, the present inventors have conducted extensive research into the modification of polyphenylene ether as described above, and have found that the main chain of the polymer contains substantially no aniline structure, and only anilines are present in the side chain methylene. It has a repeating unit represented by the following general formulas (1) and (2) in which are bonded, and a part or all of the head end has a general formula (3) in which an aliphatic amine is bonded to the methylene group at the ortho position of the hydroxyl group. Compared to conventional polyphenylene ether, the new polyphenylene ether copolymer with the structure shown above has greatly improved coloring and viscosity increase during heat molding, and has improved impact resistance when formed into a composition with polystyrene etc. The present invention was achieved based on the discovery that the processability and processability were improved at the same time.

That is, the present invention has a repeating unit represented by the following general formula (1) and a repeating unit represented by the general formula (2), and the degree of polymerization of (1) and (2) is 10 to 5000,
(1) is present in the polymer in an amount of 0.02 to 20% of (2), and the head end group represented by general formula (3) is present in (2).
A polyphenylene ether copolymer in which 0.02 to i,o% of the head terminal group represented by the general formula (4) is present, and 0 to 10% of the head end group represented by the general formula (4).

(In the formula, R1 is hydrogen, an alkyl group or an aryl group having 1 to 4 carbon atoms, R2 is an alkyl group having 1 to 20 carbon atoms, a substituted alkyl group, an aryl group, a substituted aryl group, p is 1 to 5,
R3 is the same or different alkyl group, substituted alkyl group, aryl group or substituted aryl group having 1 to 20 carbon atoms, R4
and R5 represents an alkyl group or substituted alkyl group having 1 to 20 carbon atoms, providing V).

In the polyphenylene ether copolymer of the present invention,
The repeating unit represented by general formula (1) is present in the porin main chain in an amount of 0.02 to 20% of (2), that is, 0.02 to 20 of (1) per 100 repeating units of (2). The unit must exist. Note that the repeating units (1) and (2) of the copolymer exist randomly, and therefore the general formula (5) in which anilines are bonded to the head end
) structure may exist stochastically, but in extremely small amounts;
Virtually negligible.

Further, the head end group represented by general formula (3) must also be present in the polymer in an amount of 0.02 to 20% of (2).

The general head end group represented by the general formula (4) may be present or absent, and the structure of the general formula (6) in which the aliphatic amine is bonded to the benzyl position in the main chain is the structure of the general formula (3). Smaller products may coexist.

Furthermore, it may contain the tiller bond structure of general formula (7).

The molecular weight is not particularly limited, and ranges from low molecular weight to higher molecular weight than the conventional polyphenylene ether that is generally used for general purposes. When this is expressed as the degree of polymerization (number average degree of polymerization) of repeating units (1) and (2), the degree of polymerization is 10 or more, and the upper limit is 500.
It is 0 or less, but preferably 50 to 300. The number average degree of polymerization of the present invention is determined by calculating the number average molecular weight of the main repeating unit (2) in terms of polystyrene determined by gel permeation chromatography, as specifically shown in the [Example] section below. It is the value divided by the formula @ (120, 2>).

That is, the copolymer of the present invention ranges from high molecular weight for engineering resin applications to heat resistance and! It can be used in a wide range of applications, including those with low molecular weights that are blended with other resins for the purpose of improving physical properties such as XIvj and physical properties.

The preferred degree of polymerization for engineering resin applications is 50.
The proportion of repeating unit (1) is preferably 0.1 to 10% of (2), more preferably 0.1 to 2%.

The number of terminal groups is usually 2% or less of (2), and the preferable abundance ratio of head terminals (3) to which aliphatic amine is bonded is (2).
of 0.01 to 0.5%. This amount is sufficient for improving impact resistance, etc., but if it exceeds 1%, problems such as strong odor and increased viscosity occur during melt-kneading.

The repeating unit (2) preferably has a methyl group at the 2nd and/or 6th position. Typical examples of monomers corresponding to these include 0-cresol, 2,6-dimethylphenol, 2.3.6-drimethylphenol,
Examples include 2-methyl-6-phenylphenol, and in the present invention, these may be used together or with a small amount of 2,6-phenylphenol.
- It does not prevent the coexistence of diphenylphenol, etc. Among these, 2,6-dimethylphenol is particularly preferred.

Preferred embodiments of R2, R3 and ρ of the repeating unit (1) are as follows. That is, when R2 and R3 are an alkyl group or a substituted alkyl group, they have 1 to 4 carbon atoms, and when they are an aryl group or a substituted aryl group, they are phenyl, naphthyl, or an alkyl substituted product thereof, and 9 is 3 to 5 carbon atoms. In this case, R3 is preferably a lower alkyl group.

Typical examples of substituted aniline groups attached to repeating unit (1), that is, substituted aniline groups represented by the general formula, include N
-Methylaniline, N-ethylaniline, N-propylaniline, N-butylaniline, N-methyl-2-methylaniline, N-methyl-2゜6-dimethylamine, N
-Methyl-2,4,6=trimethylaniline, N-naphthylaniline, diphenylaniline groups, etc. Further, in the general formula (3), when is a substituted alkyl group or a substituted aryl group, the substituent preferably has a functional group such as a hydrated group or a halogen group, and specifically, N-phenylethanolamine, N-(m-methyl)
Phenylethanolamine, N-(P-methyl)phenylethanolamine, N-(2',6'-dimethyl)phenylethanolamine, N-(2',4',6
'l-dimethyl)phenylethanolamine, N-
(m-methoxy>phenylethanolamine, N-(P
-chloro)phenylethanolamine, N-(m-chloro)phenylethanolamine, N-(0-chloro)phenylethanolamine, N-(0-ethyl)phenylethanolamine, N-(m-ethyl)phenylethanolamine , and N-(D-ethyl>phenylethanolamine).

These 13 g of water and functional groups such as halogen groups can be used not only to improve the adhesion of the interface when blending fibers and fillers to improve mechanical properties, but also to roughly modify the polymer.

The secondary aliphatic amine corresponding to the disubstituted amine group in the terminal group (3) has the formula: %Formula % (9) [In the formula, R4 and R5 are each independently or both an acyclic or cyclic organic group. ].

Preferred secondary aliphatic amines have R4 and R5 each having 1 to 20 carbon atoms, more preferably 1 to 20 carbon atoms.
It is an amine with 10 atoms. Particularly in view of the fact that R4 and R5 are each an alkyl group of C, preferably C, and preferably C, the second aliphatic amines are preferred because they are easily commercially available at present. is preferred.

Specific examples of secondary amines include the following.

Dimethylamine, diethylamine, di-n-propylamine, di-2@propylamine, di-0-butylamine, di-secondary-butylamine, di-tertiary-butylamine, dibenzylamines, diethylamines, diethylamines, dioctyl Amines, dinonylamines,
didecylamines, dioctylamines, dibenzylamines, methylethylamine, methylbutylamines,
Methylcyclohexylamine, heptylcyclohexylamine, octadecylcyclohexylamine, etc.

The method for producing the polyphenylene ether copolymer of the present invention is not particularly limited, but for example, in the presence of an aniline represented by general formula (10) and a secondary aliphatic amine represented by general formula (11), known It can be produced using a method substantially similar to oxidative coupling polymerization. That is, a catalyst and, if necessary, a co-catalyst are added to a solution containing a phenol represented by general formula (12), an aniline represented by general formula (10), and a secondary aliphatic amine represented by general formula (11). and polymerization by supplying an oxygen-containing gas while stirring vigorously.

As the catalyst, copper-amine complexes, manganese-amine complexes, cobalt-amine complexes, manganese-alkoxide complexes, and other catalysts commonly used in the oxidative power roughening polymerization of phenols can all be used. As a promoter,
Various amines, alkalis, alkoxides, and their derivatives can be used. The usage amounts of anilines (10) and secondary aliphatic amines (11) are based on general formula (1) and general formula (3).
) is not particularly limited as long as the amount is sufficient to produce the desired amount of the structure, but usually the amount of 4 of the arch to be bonded to the polymer is
It is best to keep it within double. Among these polymerization methods,
The method detailed in Japanese Patent Application No. 62-80733 previously filed by the present inventors is based on the properties of the obtained polymer and the Φ
This is a suitable example with excellent oil-retaining properties.

There are no particular restrictions on the post-treatment method after the reaction is completed.

Usually, after deactivating the catalyst by adding an acid such as hydrochloric acid or acetic acid to the reaction solution, the resulting polymer is separated, washed with a solvent that does not dissolve the polymer such as methanol, and then dried. Polyphenylene ether can be recovered by operation.

〔Effect of the invention〕

Compared to conventional polyphenylene ether, the polyphenylene ether copolymer of the present invention has greatly improved coloration and viscosity increase during heat molding, and has improved impact resistance and processability when formed into a composition with polystyrene etc. At the same time, it is a copolymer with improved soaking properties.

〔Example〕

EXAMPLES Hereinafter, the present invention will be specifically explained with reference to Examples, but the present invention is not limited to these Examples. In addition, each measurement was performed under the following conditions.

■The viscosity of the polymer is 0.5% chloroform solution at 30°
It was measured using an Ubbelohde viscosity tube under the conditions of C. ηS
Expressed as p/C.

■For the molded product, 310% of the powder obtained in the examples and comparative examples was used.
It refers to a test piece that was heated and pressed at 'C, 180'j/cti for 10 minutes.

■Δη/η is the value obtained by dividing the difference in ηSp/C between the powder and the molded product by ηSt)/C of the powder, and is used as an index of the increase in viscosity during hot molding.

■The degree of coloring is determined by dissolving 0.5g of the molded product in chloroform, making the total amount 10m(!), measuring the absorbance at 480°C at 25°C, and calculating the color index (
Evaluation was made using a colored finger (@).

Here: 1゜ Intensity of two people's light 1: Intensity of transmitted light a: Cell length Ccm) b: Solution 5jii degrees (g/cm) ■The total nitrogen bond amount of polyphenylene ether is determined by the JIS K 2609 microkercool Measured according to the law.

■1H-Nuclear magnetic resonance vector is JEOL (G made by Il)
Measurement was carried out with X-270 using CDCN3 as a solvent.

■The infrared absorption spectrum is Jυ made by JASCO Corporation fII.
Measurements were made on a film cast using 5COA3.

■Gel permeation chromatography (GP)
C) was measured with Toyo Sodatsu Kogyo (Taisei Ika-802RTS) and calibrated with standard polystyrene.

Example 1 Polymerization was carried out using a continuous polymerization reactor consisting of three complete mixing tanks. The first reactor has a capacity of 1. FM and comes with a circulation pump. The second and third reactors each have a stirrer and have a capacity of 3.7.1! , 1. It is.

The catalyst solution was prepared by dissolving sensitized cupric acid in 35% hydrochloric acid, adding methanol, and adding N-phenylethanolamine and di-n-
Adjustments were made by adding butylamine, N,N,N',N'-tetramethyl-1,3-diaminopropane and methanol. A monomer liquid was prepared by dissolving 2,6-dimethylphenol in mixed xylene and n-butanol. Each was prepared under air.

The catalyst liquid and monomer liquid were fed to the first reactor at a constant rate.

Based on the amounts of the catalyst liquid and monomer liquid fed, the composition of the reaction raw material liquid is as follows.

2.6-dimedylphenol concentration: 20% by weight The weight ratio of the solvents used was mixed xylene:n-butanol:methanol=60:20:20.

2.6-dimethylphenol per 100 moles, copper is 0.
08 gram atom, C, Q ion is 0.55 gram atom,
N-phenylethanolamine is 0.5 mol, di-n-
The ratio of butylamine was 0.5 mol, and the ratio of N,N,N',N'-tetramethyl-1,3-diaminopropane was 2 mol. Also, 2,6-dimethylphenol is 208g
/Hr.

In the first reactor, the reaction solution was vigorously circulated using a circulation pump, and oxygen was passed through the reactor. The internal temperature was controlled to be 30'C. The reaction liquid sent from the first reactor to the second reactor under head pressure was homogeneous.

While stirring vigorously in the second reactor, oxygen gas was pumped for 500 m
It was kept at 25°C by flowing at a rate of 1/min. The polymer begins to precipitate, but is distributed uniformly throughout the reactor by stirring. As an overflow from the second reactor, the reaction solution containing polymer particles enters the third reactor.

While controlling the temperature of the third reactor at 25°C, oxygen gas was flowed at a rate of 200 I/min while stirring with a stirrer.

A reaction solution containing a polymer was continuously taken out from the third reactor as an overflow.

Methanol was added to the yellow-white reaction liquid containing the slurry, and the mixture was filtered. It was thoroughly purified and washed using a mixed solvent (mixed xylene, butanol, and methanol) and diluted hydrochloric acid. The viscosity (ηsp/c) of the polymer obtained after drying was 0.62.
±0.03 was within the range and stable operation was possible for a long time.

The results of structural analysis and physical property evaluation of the obtained copolymer are shown in Table 1.

Example 2 Same as Example 1 except that the amounts of copper and 0-layer ions were changed to 0.05 gram atom and 0.46 gram atom, and N-ethylaniline was used instead of N-phenylethanolamine. The same procedure as in Example 1 was carried out, and the results shown in Table 1 were obtained.

Comparative Example 1 In Example 1, the amounts of copper and hydrochloric acid were changed to 0.05 gram atom and 0.46 gram atom, di-n-butylamine was not added, and 2,6-dimethylphenol was fed. The same procedure as in Example 1 was carried out except that the amount was changed to 1729/Hr, and the results shown in Table 1 were obtained.

Comparative Example 2 In Example 1, N-phenylethanol was not added, the amount of di-n-butylamine was changed to 0.95 mol, and 2
, 6-dimethylphenol liquid feeding amount to 160g/llr.
The same procedure as in Example 1 was carried out except for the following changes, and the results shown in Table 1 were obtained.

(Confirmation of Polymer Structure) The structures of the copolymers of Examples 1 and 2 and Comparative Examples 1 and 2 were determined mainly by nitrogen elemental analysis, infrared absorption spectroscopy, and nuclear magnetic resonance spectroscopy.

First, the presence of the repeating unit (1) was confirmed and quantified by the same method as in Japanese Patent Application No. 134933/1988, which the present inventors previously filed. That is, in the copolymers of Examples 1 and 2, 0.15 mol% and 0.17 mol% of monosubstituted benzene ring skeletons formed by bonding N-phenylethanolamine or N-ethylaniline were present, respectively. This was revealed by the absorption at 695 cm1 in the infrared absorption spectrum. Furthermore, in the 1-1 nuclear magnetic resonance spectrum of the copolymer of Example 1, a signal of the methylene group of formula (1) was observed at 4.41 ppm, and the signal of the methylene group corresponding to R2 was observed at 4.41 ppm.
Two methylene group signals of the +2-ct-+20H group were observed at 3.42 and 3.65 ppm. These three sets of signals have equal areal intensities, and a comparison with the areal intensities of the signals of the 1H nucleus on the bempine ring of the main repeating unit (2) indicates that this structure is 0.15% of that of (2). It was confirmed. Similarly, on the 1-day nuclear magnetic resonance spectrum of the copolymer of Example 2, the signal corresponding to the methylene group of formula (1) was 4.33 ppm, and the signal of the ethyl group corresponding to R2 was 3.30 ppm and i,
Observed O4ppm. These three sets of signals all had equal area intensity, and it was confirmed that the abundance of this structure was 0.17% of (2).

The copolymer of Comparative Example 1 contained the formula (
It was confirmed that the same structure as 1) existed in 0.26% of (2), but it was not observed at all in the polymer of Comparative Example 2.

The terminal group (3) to which the secondary aliphatic amine was bonded was confirmed and quantified by 1 day and 13C nuclear magnetic resonance spectroscopy. That is,
On the 1H nuclear magnetic resonance spectra of Examples 1 and 2, the formula (
Dig pull of methylene group in 3) was observed at 3.63 ppm, and n-butyl group -CI-1 corresponding to R4 and R5
The signals corresponding to the four types of 111 nuclei of 2-CI-42-CH2-Cl-13 are 2.47.1.50°1.29
．． and 0.88 ppm, and the area intensity ratio was also consistent with the structure of formula (3). The structure of formula (3) was quantified based on this area intensity, and 0.16% and 0.15% of (2) were determined for the polymers of Examples 1 and 2, respectively.
I confirmed. These signals were also detected as R2 on the spectrum of the copolymer of Comparative Example 2, and were determined to be 0.24% of (2), but on the spectrum of the copolymer of Comparative Example 1,
It was not recognized at all.

In addition, on the 13c-nuclear magnetic resonance spectra of the copolymers of Example 1 and Comparative Example 2, the 4-butylene base of R4 and R5 was
The signal for the species 13C4' was observed between 13 and 53 ppm.

Structure (6) in which a lipid if/J group secondary amine is bonded to the benzyl position in the main chain gives a 1H nuclear magnetic resonance spectrum very similar to the structure of formula (3), but the chemical shift values of each signal are It can be clearly distinguished from that of formula (3), with the methylene group signal at 3.36 ppm, and the two terminal signals of n-butyl group at 1.17 ppm and 0 and 80 ppm.
observed. This structure is present in the polymer of Example 1.
．． 03 mol %, but it may be present for as long as the structure of formula (3) or not at all.

The difference in the bonding position of these two types of aliphatic amine bonds (M3) was clarified as follows.

When the low molecular weight was removed from the polymer of Example 1 by reprecipitation and recovery with methanol from a toluene solution,
The signal assigned to formula (3) is 0.1% from 16 mol%.
While the signal decreased to 2 mol%, the signal assigned to formula (6) hardly decreased. In the low molecular weight region of 5%, 0.8 mol% of jigpules assigned to formula (3) were unevenly distributed, but the signal assigned to formula (6) was hardly concentrated.

It is a typical feature of the terminal group that it is unevenly distributed in the low molecular weight region, and based on this, the structures of formula (3) and formula (6) were determined. In addition, the bonding position of the aniline skeleton and the main chain, ie, the structure of formula (1), were determined using the same method.

Through detailed examinations as described above, the structure of the copolymer of the present invention was determined. In addition, the presence of normal repeating unit (2) is
It was confirmed by infrared absorption spectrum and 1°13c-nuclear magnetic resonance spectrum.

(Composition) The composition was polymerized and purified as described above, and the structure was determined. Example 1. Comparative example 1. The copolymers of Comparative Example 2 and Comparative Example 2 were prepared into compositions as described below, and the impact strength was evaluated. That is,
55 parts by weight of the above copolymer and 45 liters of rubber-reinforced polystyrene (manufactured by Asahi Kasei viJ, trade name Nistyron 492)
1 part of ff, triphenylphosphate-1-4 base, octadecyl-3-(3,5-ditertiary-butyl-4-
A formulation consisting of 0.5 parts by weight of hydroxyphenyl) propionate (Irganox 107B)
The composition was melt-kneaded at ℃ and the Izot impact strength of the resulting composition was measured. The results are listed in Table-1.

(Margin below)

Claims (1)

[Claims] 1. A repeating unit represented by the following general formula (1) and a repeating unit represented by the general formula (2), (1)
The polymerization degree of ) of 0.02 to 1.
0%, and a polyphenylene ether copolymer in which terminal groups represented by general formula (4) are present in an amount of 0 to 10% of (2). ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(1) ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(2) ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(3) ) ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(4) (In the formula, R_1 is hydrogen, an alkyl group or aryl group having 1 to 4 carbon atoms, and R_2 is an alkyl group having 1 to 20 carbon atoms, a substituted Alkyl group, aryl group, substituted aryl group, l is 1-
5, R_3 is the same or different alkyl group, substituted alkyl group, aryl group or substituted aryl group having 1 to 20 carbon atoms, R_4 and R_5 are alkyl groups having 1 to 20 carbon atoms,
(represents a substituted alkyl group). 2. The polyphenylene ether copolymer according to claim 1, wherein R_2 in general formula (1) is a 2-hydroxyethyl group (-CH_2CH_2OH).