JPH05105757A - Production of polyarylene sulfide containing amino group - Google Patents

Abstract

PURPOSE:To obtain the subject polyarylene sulfide having arbitrary molecular weight with narrow molecular weight distribution by carrying out thermal ring-opening polymerization of a specific cyclic arylene sulfide oligomer in the presence of a ring-opening polymerization catalyst containing amino group. CONSTITUTION:The objective polyarylene sulfide suitable for film, sheet, pipe, fiber, etc., is produced by the thermal ring-opening polymerization of a cyclic arylene sulfide oligomer of formula I (Ar is 6-24C arylene; R is 1-12C alkyl or 1-12C alkoxy; (n) is 2-50; (m) is 0-15) in the presence of a ring-opening polymerization catalyst containing amino group and expressed by formula II (X is alkali metal; A is 1-24C organic group or 6-24C arylene; R' is 1-6C hydrocarbon group or H; (p) is 1-6; (q) is 1-15) such as beta-diethylaminoethyl mercaptan. The ring-opening polymerization is carried out preferably in the presence of a solvent which does not eliminate the polymerization activity of the catalyst.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a highly reactive poly (arylene sulfide) having an amino group. More specifically, the ring-opening polymerization of a cyclic arylene sulfide oligomer is carried out by amino group-containing opening. The present invention relates to a method for producing an amino group-containing polyarylene sulfide, which is characterized in that it is carried out using a ring polymerization catalyst.

Polyarylene sulfide has been attracting attention as a member for electric / electronic equipment and a member for automobile equipment due to its excellent heat resistance and chemical resistance. Also injection molding,
It can be molded into various molded parts, films, sheets, fibers, etc. by extrusion molding and is widely used in fields where heat resistance and chemical resistance are required.

[0003]

2. Description of the Related Art As a method for producing polyarylene sulfide, as disclosed in JP-B-45-3368, a dihaloaromatic compound and sodium sulfide and the like in an organic amide solvent such as N-methylpyrrolidone are disclosed. Desalting polycondensation by a nucleophilic substitution reaction with an alkali metal compound is common.

However, since this production method uses a nucleophilic aromatic nucleophilic substitution reaction having low reactivity, it requires a reaction under high temperature and high pressure, and in addition, an expensive high boiling point polar solvent such as N-methylpyrrolidone is used. This is energy-intensive and requires a great deal of process cost because it requires a great deal of cost for solvent recovery. Furthermore, since a large amount of by-produced salt such as sodium chloride is produced, a step of washing and removing the by-produced salt is required, which complicates the process and leaves an alkali metal salt in the produced polymer, which causes electrical properties It has a problem that the physical properties are deteriorated.

Further, it is described in the above-mentioned patent that an amino group can be introduced into polyphenylene sulfide by copolymerization with 2,5-dichloroaniline or 2-chloroaniline. However, since 2,5-dichloroaniline and 2-chloroaniline have an electron-donating amino group at the ortho position of chlorine, they are inferior in reactivity to dichlorobenzene, and as a result, the amino group to polyphenylene sulfide is reduced. There were problems that the amount introduced was too small, the chloranilines remained in the system in a large amount even after the completion of the polymerization, and the recovered solvent was contaminated when the solvent was recovered.

On the other hand, a method for producing a polyphenylene sulfide having a terminal functional group is disclosed in JP-A-61-2748 and JP-A-61-2249. However, in this method, since a disulfide-containing polymer was produced and then the disulfide bond was cleaved to introduce a functional group, only a low molecular weight polyphenylene sulfide was obtained.

A method for producing a polyphenylene sulfide having functional groups at both ends is described in Polymer Bull.
etin, 4 459 (1981), which gives polyphenylene sulfide oligomers in this case, but has not been successful in introducing functional groups into relatively high molecular weight polyphenylene sulfides.

[0008]

SUMMARY OF THE INVENTION The present invention is a polyary
When introducing an amino group into a lensulfide, an amino group is introduced without performing a special copolymerization operation or control of reaction conditions, and a novel method for producing a polyarylene sulfide having various molecular weights with a narrow molecular weight distribution is provided. Is provided.

[0009]

That is, the present invention is based on the general formula (1)

[0010]

[Chemical 3] (S represents a sulfur atom, and Ar is an ant having 6 to 24 carbon atoms.
It is a len group, and R represents an alkyl group having 1 to 12 carbon atoms and an alkoxy group having 1 to 12 carbon atoms. Also, n is 2 to 50
And m is an integer of 0 to 15. ) In the ring-opening polymerization of the cyclic arylene sulfide oligomer represented by the general formula (2)

[0011]

[Chemical 4] (S is a sulfur atom, N is a nitrogen atom, X is an alkali metal, A is an organic group having 1 to 24 carbon atoms or 6 to 24 carbon atoms.
R'is a hydrocarbon group having 1 to 6 carbon atoms or hydrogen, p is an integer of 1 to 6, and q is an integer of 1 to 15. The method for producing an amino group-containing poly (arylene sulfide) is characterized in that the ring-opening polymerization is carried out in the presence of the amino group-containing ring-opening polymerization catalyst.

The details will be described below.

Ar in the cyclic arylene sulfide oligomer of the formula (1) used in the present invention is an arylene group having 6 to 24 carbon atoms and at least one aromatic ring, and is phenylene. , Biphenylene, naphthalene ring,
Examples thereof include a benzimidazole ring, a benzothiazole ring, a benzoxazole ring, a benzotriazole ring and a phthalimide ring. Among them, the preferred arylene group is phenylene, biphenylene, naphthalene ring or benzimidazole ring.

R in the above formula (1) is an alkyl group having 1 to 12 carbon atoms such as methyl group, ethyl group, propyl group, butyl group; methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group. , Sec-butoxy group, ter
Examples thereof include alkoxy groups having 1 to 12 carbon atoms such as t-butoxy group. Among these, a cyclic arylene sulfide oligomer having a lower alkyl group such as a methyl group and an ethyl group; a lower alkoxy group such as a methoxy group and an ethoxy group, and an unsubstituted cyclic arylene sulfide oligomer. It is preferably used.

In the above formula (1), n is an integer of 2 to 50, but is preferably 3 or more and 35 or less, more preferably 3 or more and 25 or less for the purpose of solubility in a solvent or lowering the melting point. ..

The polymerizable cyclic arylene sulfide oligomer may be either a single compound having a single degree of polymerization or a mixture of cyclic oligomers having different degrees of polymerization, and a cyclic oligomer having different repeating units. However, since a mixture of oligomers having various degrees of polymerization has a lower melting point than a single compound having a single degree of polymerization, it is preferable to use a mixture of cyclic oligomers.

The cyclic oligomer mixture may contain a small amount of a linear oligomer or a compound having a very small amount of arylene sulfide units. Further, these oligomers may contain a linear or cyclic polymer having a low viscosity at a temperature at which they are liquid.

The ring-opening polymerization catalyst that can be used in the present invention is a compound represented by the above formula (2).

A in the general formula (2) is an organic group having 1 to 24 carbon atoms or an arylene group having 6 to 24 carbon atoms, which contains a ketone, amide, sulfone and the like which are inactive during polymerization. However, it means that pyridine ring, pyrimidine ring, imidazole ring, benzimidazole ring, benzoxazol ring, benzothiazole ring, etc. can be used even if A is a heterocyclic compound. To do.
Further, these ring-opening polymerization catalysts may be produced in the reaction system from a mercapto group-containing amine compound and an alkali metal hydroxide.

Examples of the ring-opening polymerization catalyst used in the present invention include β-diethylaminoethyl mercaptan, γ-diethylaminopropyl mercaptan, 2-aminothiophenol, 3-aminothiophenol and 4-aminothio. Phenol, 3-mercapto-4-aminotoluene, 2
-Mercapto-4-aminotoluene, 2,5-diaminothiophenol, 4-mercapto-2,6-dimethylpyridine, 6-amino-2-mercaptobenzothiazo-
And alkali metal salts such as 4-amino-6-hydroxy-2-mercaptopyrimidine.

These ring-opening polymerization catalysts may be used alone or in combination of two or more.

The concentration of the ring-opening polymerization catalyst to be used varies depending on the molecular weight of the target polyarylene sulfide and the type of the ring-opening polymerization catalyst, but is usually a cyclic oligomer (the number of moles per unit of the polyarylene sulfide). To 0.001 to 20 mol%, preferably 0.005 to
It is 15 mol%, more preferably 0.01 to 10 mol%.

When the ring-opening polymerization catalyst is added, it may be added as it is, or after the cyclic oligomer is dissolved in an appropriate solvent, preferably methylene chloride, a predetermined amount of the ring-opening polymerization catalyst is added thereto. Alternatively, the solvent may be removed.

It is essential that the temperature used in the ring-opening polymerization of the present invention is not higher than the melting temperature of the cyclic oligomer mixture and the decomposition temperature of the ring-opening polymerization catalyst and cyclic oligomer used. Furthermore, if the polymerization temperature is too high, the possibility of side reactions such as curing reaction of the cyclic oligomer increases. Usually 1
It is in the range of 50 to 400 ° C, preferably in the range of 180 to 370 ° C, and more preferably in the range of 200 to 350 ° C.

The reaction time varies depending on conditions such as the type of ring-opening polymerization catalyst used and the polymerization temperature, but it should be set to conditions that suppress the curing reaction as much as possible. Usually, the range of 0.1 to 100 hours is preferable.

The above-mentioned polymerization may be carried out not only in an ordinary polymerization reaction tank but also in a mold for producing a molded article, or for producing a polyarylene sulfide as an extrudate. The polymerization may be carried out in the extruder.

This polymerization is usually carried out in the absence of a solvent, but it can also be carried out in the presence of a solvent. The solvent may be any one that does not lose the polymerization activity,
Usually, a compound that dissolves the cyclic oligomer and the ring-opening polymerization catalyst and does not deactivate the ring-opening polymerization catalyst is preferable.

As a suitable solvent when using the ring-opening polymerization catalyst represented by the above formula (2), 1,3-dimethyl-2-
Imidazolidinone, hexamethylphosphoric triamide, diphenyl sulfone, diphenyl ether, benzophenone, dimethylacetamide, N-methyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, m-
Examples thereof include cresol and N-methyl-ε-caprolactam. In addition, a solvent generally used in anionic polymerization can also be used.

These solvents may be used alone or in combination of two or more.

The polymerization temperature when using these solvents is
Although it varies depending on the solvent used, it is in the range of -78 to 400 ° C, and is in the range of -20 to 35 from the viewpoint of solubility of the cyclic oligomer and the like.
It is preferably in the range of 0 ° C.

Amino group-containing polyary obtained in the present invention
Ren sulfide has excellent heat resistance, chemical resistance, various mechanical properties, and electrical properties. In particular, the existing amount of the alkali metal salt, which has been a problem in the prior art, is much smaller than that in the conventional method, so that the electrical characteristics are remarkably excellent. In addition, since the proportion of the crosslinked polymer present is extremely low and the polymer is essentially linear, it has the advantage of excellent processability.
Further, in the present invention, by adjusting the amount of the ring-opening polymerization catalyst used, it becomes possible to control the molecular weight of the polyarylene sulfide, which is usually higher in molecular weight and molecular weight than the polyarylene sulfide obtained by polycondensation. A polyarylene sulfide having a narrow distribution can be easily obtained.

The polyarylene sulfide obtained as described above has a highly reactive amino group, and when it is melt-mixed with various polymers, a block-graft polymer acting as a compatibilizer is produced. Can be made By using it, the compatibility as a polymer alloy is expected to be improved.

Specific examples of the blendable polymers include polyethylene, polybutadiene, polyisoprene,
Polychloroprene, polystyrene, polybutene, poly α
-Methyl styrene, polyvinyl acetate, polyvinyl chloride,
Polyacrylic acid ester, polymethacrylic acid ester,
Polyacrylonitrile, nylon 6, nylon 66, nylon 610, nylon 12, nylon 11, nylon 46 and other polyamides, polyethylene terephthalate,
Polybutylene terephthalate, polyarylate, etc. polyester, polyurethane, polyacetate, polycarbonate
Carbonate, polyphenylene oxide, polysulfone, polyethersulfone, polyallylsulfone, polyphenylene sulfide sulfone, polyetheretherketone, polyetheretherketone, polyphenylene sulfide ketone, polyimide, polyamideimide, silicone resin,
Examples include homopolymers such as phenoxy resin and fluororesin, random or block, graft copolymers and mixtures thereof.

If desired, glass fiber, carbon fiber, ceramic fiber such as alumina fiber, aramid fiber, wholly aromatic polyester fiber, metal fiber, reinforcing filler such as potassium titanate whisker, calcium carbonate, and mica. , Talc, silica, barium sulfate, calcium sulfate, kaolin, clay, pyroferrite, bentonite, sericite, zeolite, nepheline sinite, attapulgite, wollastonite, ferrite, calcium silicate, magnesium carbonate, dolomite, antimony trioxide. , Zinc oxide, titanium oxide, magnesium oxide, iron oxide, molybdenum disulfide, graphite, gypsum, glass beads, glass powder, glass balloon,
Inorganic fillers such as quartz and quartz glass and organic and inorganic pigments can also be blended.

Further, a plasticizer such as an aromatic hydroxy derivative, a mold release agent, a silane-based or titanate-based coupling agent, a lubricant, a heat resistance stabilizer, a weather resistance stabilizer, a crystal nucleating agent, a foaming agent, and a rust preventive agent. Agents, ion trap agents, flame retardants, flame retardant aids, etc. may be added as necessary.

The amino group-containing polyphenylene sulfide thus obtained is used alone or in combination with the above-mentioned polymers, reinforcing fillers, inorganic fillers and the like, and various molded articles, films and sheets are obtained by injection molding and extrusion molding. It can be molded into gut, pipe, fiber, etc.

[0037]

The present invention will be described below with reference to examples. These examples are illustrative and not limiting.

The cyclic oligomer mixture used in each of the examples was a cyclic phenylene sulfide oligomer having a polymerization degree of 7 to 15 and substantially no linear phenylene sulfide oligomer. The molecular weight was calculated in terms of polystyrene by gel permeation chromatography (GPC). The measurement conditions of GPC are shown below.

Eluent: 1-chloronaphthalene Temperature: 210 ° C. Detector: UV detector 360 nm Flow rate: 1.0 ml / min. Injection amount: 200 μl (slurry-like: 0.2% by weight) Further, analysis of amino groups introduced into polyphenylene sulfide was carried out by using FT-IR, and the C-H out-of-plane bending vibration of the benzene ring was 1900 cm ^−1. Internal absorption of
It was used for relative evaluation of the amount of introduced amino groups by comparing the absorption at 3387 cm ^-1 , which is the NH stretching vibration of amino groups.

Reference Example 1 (Method for recovering cyclic phenylene sulfide oligomer) The cyclic phenylene sulfide oligomer used in each Example was recovered by the following procedure.

A 15 l reactor equipped with a stirrer, a dehydration tower and a jacket was charged with N-methyl-2-pyrrolidone (N
MP) 5 l and sodium sulfide (purity: Na ₂ S 6
0.4%) 1872.5 g was charged, and the mixture was heated with a jacket while stirring and dehydrated through a dehydration tower until the internal temperature reached about 205 ° C. At this time, 420 g of effluent mainly consisting of water was distilled off.

Then, 2153 g of p-dichlorobenzene
Was added, the temperature was raised to 250 ° C., and the mixture was reacted for 3 hours. After the reaction was completed, the reaction mixture was cooled to about 100 ° C., the pressure inside the reactor was reduced, and then the mixture was reheated to distill off 5200 g of an effluent mainly composed of NMP through the dehydration tower. The pressure inside the reactor system was returned to normal pressure, 8 l of water was added to make a water slurry, and the mixture was heated and stirred at 80 ° C for 15 minutes, and then the water slurry was extracted from the outlet at the bottom of the reactor and centrifuged to separate the polymer. Was recovered.

Further, the polymer was returned to the reactor, and 8 l of water was added.
Was added, the mixture was heated and stirred at 180 ° C. for 30 minutes, and after cooling, a water slurry was extracted from the outlet at the bottom of the reactor and centrifuged to recover the polymer.
Was transferred to a ribbon blender with a jacket and dried.

The polymer obtained was 1450 g and had a melt viscosity of 240 poise. Furthermore, FT-IR of this polymer was measured. The result is shown in FIG.
No absorption of the amino group at 87 cm ^-1 was observed.

Next, this polyphenylene sulfide 20
Soxhlet extraction was performed using 0 g of methylene chloride as a solvent. Then, the saturated methylene chloride extract was put into methanol, and the precipitate was filtered and dried to obtain 1.2 g of a cyclic phenylene sulfide oligomer mixture. From the results of mass spectrum and high performance liquid chromatography, it was confirmed that this cyclic oligomer mixture was a 7 to 15-mer cyclic phenylene sulfide oligomer. The melting point was 260 ° C.

Example 1 540 mg of the cyclic phenylene sulfide oligomer obtained in Reference Example 1 and 3.2 mg of the sodium salt of p-aminothiophenol were placed in a 10 ml polymerization test tube and, after purging with nitrogen, under reduced pressure. The tube was sealed and immersed in a molten salt bath at 300 ° C. for 30 minutes. The obtained off-white product was cooled to room temperature and then pulverized to give 250 ml of 1-chloronaphthalene at 230 ° C.
Redissolved in. A white precipitate was obtained upon cooling to room temperature. The precipitate is filtered, washed (methylene chloride, methanol),
It was dried to obtain a white powder (291 mg). Yield 54
%, Melting point 282 ° C. The weight average molecular weight (Mw) of the obtained polymer was 70,000 and the molecular weight distribution (Mw / number average molecular weight (Mn)) was 2.3.

As a result of elemental analysis, the Na content was 120 ppm.
It can be seen that the Na content is lower than that of the polyphenylene sulfide obtained by conventional polycondensation.

The FT-IR of the obtained polymer was measured. The results are shown in FIG. 2. Absorption of an amino group appears at 3387 cm ⁻¹ , and it can be confirmed that the amino group was introduced into the obtained polymer.

Furthermore, 3387 cm obtained from FT-IR
The absorbance ratio between ⁻¹ and 1900 cm ⁻¹ (correlation with the amount of amino group introduced) was 0.02.

Examples 2 and 3 The amount of sodium salt of p-aminothiophenol used as the ring-opening polymerization catalyst in Example 1 was changed to 1.23 and 2.38 mol% based on the cyclic phenylene sulfide oligomer. Other conditions were the same as in Example 1 for the polymerization. In each case, a white powder was obtained with a yield of about 55%. The results are shown in Table 1.

Example 4 540 mg of the cyclic phenylene sulfide oligomer obtained in Reference Example 1 was dissolved in 10 ml of 1,3-dimethyl-2-imidazolidinone, and then the sodium salt of p-aminothiophenol 36. 5 mg was added, and under a nitrogen stream, 25
The reaction was carried out at 0 ° C for 6 hours. Then, it was cooled to room temperature, and the deposited precipitate was filtered and washed (methylene chloride, methanol-
And dried to obtain a white powder. Yield 41%, melting point 2
It was 80 ° C. The results are shown in Table 1.

Example 5 The amount of the sodium salt of p-aminothiophenol used as the ring-opening polymerization catalyst in Example 4 was changed to 6.89 mol% based on the cyclic phenylene sulfide oligomer, and other conditions were changed. Polymerization was carried out under the same conditions as in Example 4. Yield is 5
2%, melting point 280 ° C. The results are shown in Table 1.

[0053]

[Table 1] Comparative Example 1 Polyphenylene sulfide was obtained in the same manner as in Reference Example 1. The obtained polyphenylene sulfide has a melting point of 280.
Although the polymer had a weight average molecular weight of 28,000 at ℃, it was a polymer having a wide molecular weight distribution of 6.8. As a result of elemental analysis, the Na content was 1300 ppm, indicating that a large amount of Na was present as compared with the above examples. Further, absorption of amino group was not recognized from FT-IR.

Comparative Example 2 540 mg of the cyclic phenylene sulfide oligomer obtained in Reference Example 1 was placed under the same conditions as in Example 1 in the absence of a ring-opening polymerization catalyst. The black product obtained was a crosslinked polymer partially insoluble in 1-chloronaphthalene at 230 ° C. Further, absorption of amino group was not recognized from FT-IR.

[0055]

As is clear from the above description, according to the present invention, the proportion of the cross-linked polymer is low, the polymer is essentially linear, and the amount of alkali metal salt present is higher than that in the conventional method. With a small amount, it is possible to obtain amino group-containing polyarylene sulfides having various molecular weights and having a narrow molecular weight distribution. Furthermore, since the polyarylene sulfide of the present invention contains a large amount of highly reactive amino groups, it can be expected to be applied to various applications such as polymer blends utilizing the reactivity.

[Brief description of drawings]

FIG. 1 is a diagram showing an IR spectrum of polyphenylene sulfide obtained in Reference Example 1.

FIG. 2 is a view showing an IR spectrum of polyphenylene sulfide obtained in Example 1.

Claims (2)

[Claims] 1. A general formula (1): (S represents a sulfur atom, and Ar is an ant having 6 to 24 carbon atoms.
It is a len group, and R represents an alkyl group having 1 to 12 carbon atoms and an alkoxy group having 1 to 12 carbon atoms. Also, n is 2 to 50
And m is an integer of 0 to 15. ) A cyclic arylene sulfide oligomer represented by the general formula (2) (S is a sulfur atom, N is a nitrogen atom, X is an alkali metal, A is an organic group having 1 to 24 carbon atoms or 6 to 24 carbon atoms.
R'is a hydrocarbon group having 1 to 6 carbon atoms or hydrogen, p is an integer of 1 to 6, and q is an integer of 1 to 15. ) The method for producing an amino group-containing poly (arylene sulfide), which comprises heating and ring-opening polymerization in the presence of an amino group-containing ring-opening polymerization catalyst represented by 2. The amino group-containing polyaryl according to claim 1, wherein the ring-opening polymerization of the cyclic arylene sulfide oligomer represented by the general formula (1) is carried out in the presence of a solvent that does not eliminate the polymerization activity. -Method for producing len sulfide.