JP2545205B2 - Aromatic sulfide amide polymer - Google Patents

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel crystalline sulfidamide polymer. The polymer of the present invention has a chemical structure in which a phenylene group and an alkylene group are linked via an amide group and a thioether group, and has excellent heat resistance, flame retardancy, solvent resistance, mechanical properties, etc. It is useful as a raw material.

[0002]

2. Description of the Related Art Polyphenylene sulfide is well known as a polymer compound having a structure in which phenylene groups are linked via a thioether group.

It has characteristics such as excellent flame retardancy, low hygroscopicity, and high dimensional stability. However,
Since the heat distortion temperature (HDT) is 260 ° C. (GF40%) and the crystal melting point (Tm) is 281 ° C., there is an unavoidable restriction on the use in fields requiring high heat resistance. Therefore, it has been desired to develop a polymer of this type having a higher crystal melting point.

Further, a polymer having a thioether group, a phenylene group and an amide group, that is, a polymer of so-called aromatic polythioether amide and a method for producing the same are disclosed in JP-A-60-2.
No. 26528, it has a slightly low softening point, is soluble in organic solvents such as dimethyl sulfoxide and N-methyl-2-pyrrolidone, and has poor chemical resistance. A monomer having a thioether group is synthesized. There is a problem in that it is not useful in terms of cost.

[0005]

DISCLOSURE OF INVENTION Problems to be Solved by the Invention The present invention has been earnestly studied in order to meet these demands, and as a result, it is industrially easily available,
Moreover, it is intended to provide a novel aromatic sulfide amide polymer containing an inexpensive aliphatic component and excellent in heat resistance, solvent resistance and mechanical properties.

[0006]

DISCLOSURE OF THE INVENTION In the present invention, the constitutional unit of the polymer comprises repeating units of the general formulas (I) and (II) or (II), and the logarithmic viscosity [η] is 0.02 to 2. .00
Of aromatic sulfide amide polymer.

(Here, the logarithmic viscosity [η] is a value measured at 30 ° C. in concentrated sulfuric acid at a concentration of 0.5 g / 100 ml and calculated according to the logarithmic viscosity [η] = ln relative viscosity / polymer concentration.)

[0008]

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[In the formula, Ar ¹ , Ar ² , Ar ³ and Ar ⁴ represent an aromatic ring, and R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are alkyl having 1 to 20 carbon atoms. Group, cycloalkyl group having 3 to 20 carbon atoms, aryl group having 6 to 20 carbon atoms, alkoxy group having 1 to 20 carbon atoms, acyl group having 2 to 20 carbon atoms, or carbon number 7
To 20 arylalkyl groups, which may be the same or different. a, b, c, d are the same or different from each other and represent an integer of 0-4. Further, R ⁵ and R ⁶ may be hydrogen. R ⁷ , R ⁸ and R ⁹ represent an alkylene group having 1 to 20 carbon atoms and may be the same or different. The present invention will be described in detail below.

Amide group containing dihalogen compounds (III) and (IV) used to synthesize the polymers of the present invention
Is given by

[0011]

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The Ar ¹ , Ar ² , Ar ³ and Ar ⁴ are

[0013]

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And the like, which may be the same or different. Specific examples of preferred (III) and (IV) include the following.

[0015]

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[0016]

[Chemical 6]

[0017]

[Chemical 7]

These amide group-containing compounds are preferably composed of a para-position bond in terms of heat resistance, but in order to improve the solubility and moldability of the resulting sulfide amide polymer, the meta-position and / or ortho It may contain a bond at the position, and may have a branched structure.

As a method for synthesizing these amide group-containing dihalogen compounds, a general amide-forming bond reaction can be used. For example, a method of synthesizing by reacting a corresponding halogen-containing carboxylic acid chloride and an aliphatic diamine can be mentioned.

The organic polar solvent is preferably an aprotic solvent which is stable to alkali at high temperature. For example,
N, N-dimethylacetamide (DMA), N-ethyl-2-pyrrolidone, hexamethylphosphortriamide (HMPA), dimethylsulfoxide (DMSO), N
-Methyl-2-pyrrolidone (NMP), 1,3-dimethylimidazolidinone and the like can be mentioned.

As the sulfidizing agent used for synthesizing the polymer of the present invention, alkali metal sulfide, alkali metal hydrosulfide and alkali metal base, hydrogen sulfide and alkali metal base can be used. The alkali metal hydrosulfide may be used in the form of a hydrate (0.5 to 10 molar equivalent). Further, these sulfidizing agents may be those prepared in the system prior to the addition of the dihalogen compound represented by the general formula (III) and / or (IV) into the polymerization system. Before adding a dihalogen compound to carry out polymerization, it is preferable to remove water in the system by distillation or the like so that the amount is 2.5 molar equivalents or less based on the sulfidizing agent.

Preferred sulfidizing agents include sodium sulfide, a combination of sodium hydrosulfide and sodium hydroxide, and a combination of hydrogen sulfide and sodium hydroxide.

At the time of polymerization, the use of a crown ether compound, a phosphorus salt or an ammonium salt compound known as a phase transfer catalyst, and the use of an auxiliary agent such as an alkali metal carboxylate are effective for improving the molecular weight of the obtained polymer. In some cases, it is preferable.

Polymerization is carried out at 150 to 300 ° C., preferably 18
0.5 to 24 hours at 0 to 280 ° C., preferably 1 to 12
It is carried out with stirring for an hour.

The general formula (II used in the present invention
The ratio of the dihalogen compound represented by I) or (IV) to the sulfidizing agent is preferably in the range of 0.9 to 1.1: 1.0, and the amount of the solvent is the amount of the polymer produced during the polymerization in the system 7.
It can be used by adjusting to 50 to 50% by weight, preferably 10 to 40% by weight.

The obtained polymer can be isolated by a known recovery method, for example, isolation by vacuum distillation, flash method or reprecipitation with water or an organic solvent, washing with water or an organic solvent, and drying.

The aromatic sulfide amide polymer of the present invention generally has an inherent viscosity of 0.02 to 2.00 measured at a concentration of 0.5 g / 100 ml of concentrated sulfuric acid at 30 ° C., and 0.05 to 2 Those with an inherent viscosity in the range of 0.000 are preferred.

The aromatic sulfide amide polymer in the present invention can be caused to undergo chain extension, crosslinking, branching, etc. by heating in an oxidizing atmosphere such as air.

When the polymer of the present invention is molded and processed, various known filler components may be contained. Typical examples of the filler component are a) fibrous filler; glass fiber, carbon fiber, boron fiber, aramid fiber, alumina fiber, b).
Inorganic fillers; mica, talc, clay, graphite,
Examples thereof include carbon black, silica, asbestos, molybdenum sulfide, magnesium oxide, calcium oxide and the like.

The polymer of the present invention has its absorption spectrum (10
Absorption derived from thioether bond near 90 cm ^-1
Absorption derived from amide group carbonyl group near 640 cm ^−1, absorption derived from amide bond amino group near 3320 cm ¹ , 1540 cm ⁻¹ ) to the above formula (I) and (II) or (II) It is confirmed that the polymer has a repeating unit of.

[0031]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

Most of the polymers of the present invention are concentrated sulfuric acid or N-methyl-2-pyrrolidone / lithium chloride (9
It is only soluble in a special solvent such as (5/5 weight ratio), but is insoluble in general organic solvents, so it is difficult to determine the average molecular weight. Therefore, the logarithmic viscosity [η] is used as a measure of the molecular weight.

The logarithmic viscosity [η] here is a value measured at a concentration of 0.5 g / 100 ml in concentrated sulfuric acid at 30 ° C. and calculated according to the logarithmic viscosity [η] = ln relative viscosity / polymer concentration.

Example 1 A 500 ml autoclave was charged with Na ₂ S.2.7.
0.04 mol of H ₂ O and 150 ml of N-methyl-2-pyrrolidone (NMP) were added, and the temperature was raised to 200 ° C. with stirring for dehydration. 1.26 g of distilled water containing 4.31% of NMP was obtained. After cooling the reaction system to 100 ° C,

[0035]

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0.04 mol was added together with 50 ml of NMP, the system was sealed, the temperature was raised, and polymerization was carried out at 250 ° C. for 6 hours.

After completion of the reaction, the system was cooled and methanol was added to precipitate a polymer. After filtration, wash with warm water,
Filtration was repeated, washed with methanol and dried to obtain 10.4 g (yield 80.1%) of a light gray powdery polymer.

The inherent viscosity of this polymer was 0.10 (concentrated sulfuric acid, 0.5 g / 100 ml, 30 ° C.).

The polymer is concentrated sulfuric acid, NMP / LiC
It was soluble in 1, etc., but methanol, DMF, DMS
It was insoluble in O and the like.

When the infrared absorption (IR) spectrum of this polymer was measured, an absorption derived from a thioether bond was found at 1075 cm ⁻¹ and an absorption derived from a carbonyl group of an amide bond was found at 1642 cm ⁻¹ .

The elemental analysis results are as follows.

[0042]

[Table 1]

This sulfide amide polymer was confirmed to be crystalline by X-ray diffraction.

The decomposition temperature was 432 ° C. and no melting point was observed.

Example 2 As dihalogen compound

[0046]

[Chemical 9]

(0.02 mol)

[0048]

[Chemical 10]

Polymerization was carried out in the same manner as in Example 1 except that (0.02 mol) was used.

As a result, 11.2 g (yield 82.3%)
A polymer of

The logarithmic viscosity of this polymer was 0.11 (concentrated sulfuric acid, 0.5 g / 100 ml, 30 ° C.).

The polymer is concentrated sulfuric acid, NMP / LiC
However, it was insoluble in methanol, DMF and the like.

[0053] absorption derived from 1080cm ^-1 was measured infrared absorption (IR) spectrum of the polymer in a thioether bond, 3350cm ^-1, 1642cm ^-1,
Absorption derived from an amide bond was observed at 1545 cm ^-1 .

The results of elemental analysis are as follows.

[0055]

[Table 2]

This sulfide amide polymer was confirmed to be crystalline by X-ray diffraction.

The decomposition temperature was 427 ° C. and no melting point was observed.

[0058]

As is clear from the above description, the aromatic sulfide amide polymer of the present invention has excellent heat resistance and processability, and is expected to be applied to a wide range of fields as an engineering plastic.

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Claims (1)

(57) [Claims] 1. A polymer having structural units of general formulas (I) and (I
An aromatic sulfide amide polymer having a repeating unit of I) or (II) and having an inherent viscosity [η] of 0.02 to 2.00. (Here, the logarithmic viscosity [η] was measured at a concentration of 0.5 g / 100 ml in concentrated sulfuric acid at 30 ° C., and the logarithmic viscosity [η] was measured.
= Ln is a value calculated according to relative viscosity / polymer concentration. ) [Chemical 1] [In the formula, Ar ¹ , Ar ² , Ar ³ and Ar ^{4 each} represent an aromatic ring, and R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ represent an alkyl group having 1 to 20 carbon atoms or a carbon atom. Represents a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an acyl group having 2 to 20 carbon atoms, or an arylalkyl group having 7 to 20 carbon atoms, each being the same. Or it may be different. a, b, c, d are the same or different from each other, 0
Indicates an integer of ˜4. Further, R ⁵ and R ⁶ may be hydrogen. R ⁷ , R ⁸ and R ⁹ represent an alkylene group having 1 to 20 carbon atoms and may be the same or different. ]