JPH05170915A - Production of graft copolymer of polyarylene sulfide and polyamide - Google Patents

Abstract

PURPOSE:To obtain a graft copolymer having extremely improved mechanical properties and excellent compatibility with other polymers while maintaining characteristics such as heat resistance by copolymerizing an imidated PPS having a specific structure with a polyamide. CONSTITUTION:A polyarylene sulfide containing an amino group at a side chain and/or end is reacted with a carboxylic acid anhydride of the formula (R1 is tetrafunctional organic group containing at least two carbon atoms; <=two carbonyl groups are bonded to any one carbon atom of the tetrafunctional organic group) in a polar organic solvent to give an acid anhydride-containing modified polyarylene sulfide, which is reacted with a polyamide containing an amino group at the end in a polar organic solvent.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a process for producing a graft copolymer of a polyarylenylene sulfide and a polyamide, and more specifically, a graft of an imidized polyarylenene sulfide having a carboxylic acid anhydride structure introduced into the molecule. It relates to a method for producing a copolymer.

[0002]

2. Description of the Related Art Polyarylensulfide (hereinafter referred to as P
Sometimes called PS. ) Resin has excellent properties such as heat resistance, but its disadvantages are (1) low impact resistance (2) insufficient adhesion to inorganic materials such as metals, (3) other The low compatibility with the polymer may be mentioned. Improve the impact resistance of PPS resin,
For the purpose of imparting other properties, many polymer blends of PPS resin and other plastics have been proposed in the past. For example, blending with polyamide (Japanese Patent Laid-Open No. 53-
69255, 59-155462) and blends with polycarbonate (Japanese Patent Laid-Open No. 51-59952).
59-155461), blends with polyester (JP-A-59-64657), and blends with thermoplastic elastomers (JP-A-61-207462). However, in each case, the blend is a simple blend, and the compatibility and mechanical properties are obviously inferior to those of the copolymer chemically bound with another kind of polymer.

[0003]

DISCLOSURE OF THE INVENTION The present invention eliminates the drawbacks of the prior art, improves mechanical properties while maintaining excellent properties such as heat resistance of PPS, and at the same time, improves the mechanical properties of other polymers. It is an object of the present invention to provide a technique capable of improving compatibility with. Other objects and novel features of the present invention will be apparent from the following description.

[0004]

The present invention comprises a side chain and / or
Alternatively, a polyarylene sulfide (I) having an amino group at the terminal and a carboxylic acid anhydride (I
Modified poly (arylene sulfide) having an anhydride group obtained by reaction with I) in a polar organic solvent (II)
I) and a polyamide (IV) having an amino group at the end are reacted in a polar organic solvent to prepare a graft copolymer of a polyarylene sulfide and a polyamide,

[Chemical 1] (However, in Chemical formula 1, R ₁ is a tetravalent organic group containing at least 2 carbon atoms, and 2 or less of the carbonyl group in Chemical formula ₁ is any one carbon atom of the tetravalent organic group. Bonded to an atom), and a polyarylene sulfide (I) having an amino group at a side chain and / or a terminal.
And a carboxylic acid anhydride (II) represented by the following chemical formula 1 and a polyamide (IV) having an amino group at a terminal are reacted in a polar organic solvent. Graft copolymerization of polyarylene sulfide and polyamide It relates to the manufacturing method of the united body.

[Chemical 1] (However, in Chemical formula 1, R ₁ is a tetravalent organic group containing at least 2 carbon atoms, and 2 or less of the carbonyl group in Chemical formula ₁ is any one carbon atom of the tetravalent organic group. It is bound to an atom.)

In the present invention, PPS (I) having an amino group at the side chain and / or terminal and carboxylic acid anhydride (II) represented by the above chemical formula 1 are once reacted in a polar organic solvent to imidize. Imidized PPS having acid anhydride group
(III) is obtained, and then, the imidized PPS (III) having the acid anhydride group is reacted with the polyamide (IV) having an amino group at a terminal in a polar organic solvent, or a side chain and / or PPS having amino group at the terminal
A method for producing a graft copolymer in which (I) and a polyamide (IV) having an amino group at a terminal are reacted in the presence of a carboxylic acid anhydride (II) represented by the above chemical formula 1 in a polar organic solvent. is there.

An example of the reaction is shown below. (1) PPS (III) having an acid anhydride group in the side chain and aliphatic polyamide (PA) having an amino group at the molecular end
A method for producing a graft reaction with (IV) in a polar organic solvent. (2) PPS (I) having an amino group in the side chain, tetracarboxylic dianhydride (II) and an aliphatic polyamide (PA) (IV) having an amino group at the molecular end are graft-reacted in a polar organic solvent. Manufacturing method.

The present invention is a grafting reaction carried out in a polar organic solvent, a grafting reaction product with an imidized polyamide having an acid anhydride group, and the grafting reaction product has a heat resistance of PPS. While maintaining excellent properties, the mechanical properties can be improved, and the compatibility with other polymers can be improved.

PP having the above amino group in the present invention
The method of synthesizing S (I) can be performed, for example, by reacting the following components (a) and (b). (A) Alkali metal sulfide (typically sulfurized sulfide
(D) (b) Mixture of dihalide and halide having amino group as a substituent In the above production method, an example of the dihalide used as a raw material is a dihalogenated benzene represented by the following chemical formula 2. ..

[Chemical 2] (In the formula of Chemical formula 2, R represents an alkyl or alkoxy group having 1 to 3 carbon atoms, n represents an integer of 0 to 3, and X represents a halogen atom.) The compound represented by Chemical formula 13 is mentioned. However, chemical formula 3 to chemical formula 1
Examples of X ₁ in 3 include Cl and Br.

[Chemical 3]

[Chemical 4]

[Chemical 5]

[Chemical 6]

[Chemical 7]

[Chemical 8]

[Chemical 9]

[Chemical 10]

[Chemical 11]

[Chemical 12]

[Chemical 13] Further, in the above, as an example of the halide having an amino group as a substituent used as a raw material, a halogenated aminobenzene represented by the following Chemical formula 14 is cited.

[Chemical 14] (Wherein R and n have the same meanings as described above, R3 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, Y represents a halogen atom, and m represents 1 or 2). Specific examples thereof include the following chemical formulas 15 to 22.
A halogenated aminobenzene compound represented by the formula: However, in Chemical formulas 15 to 22, as an example of Y ₁ ,
Cl or Br may be mentioned.

[Chemical 15]

[Chemical 16]

[Chemical 17]

[Chemical 18]

[Chemical 19]

[Chemical 20]

[Chemical 21]

[Chemical formula 22]

In the above, in order to achieve the desired object of the present invention, for example, by improving the compatibility with other polymers,
The halide having an amino group as a substituent is preferably contained in the mixture in an amount of 0.2 to 25 mol%. Further, it is preferable that the mixture contains para dihalide in an amount of 85 mol% or more.

In the present invention, in the above reaction, if necessary, a trihalide such as trichlorobenzene may be added within the range of 5 mol% or less based on the dihalide. The polymerization reaction may be carried out in a polar solvent, preferably an amide solvent such as N-methylpyrrolidone (NMP) or dimethylacetamide, or a sulfone solvent such as sulfolane. At this time, in order to control the degree of polymerization, it is desirable to add an alkali metal salt of carboxylic acid or sulfonic acid, alkali hydroxide or the like. The preferable temperature and time for the polymerization reaction are approximately 120 to 300 ° C. and 2
~ 10 hours. It is desirable to carry out the reaction in an inert gas atmosphere. After the reaction was completed, the solid product was separated by filtration, thoroughly washed with deionized water, and dried to obtain a PPS having an amino group.
Resin (I) is obtained. The amino group-containing PPS resin (I) and the carboxylic acid anhydride (II) represented by Chemical Formula 1 above.
When and are reacted in a polar solvent, for example, an amide-based solvent such as N-methylpyrrolidone or dimethylacetamide, PPS (III) having an acid anhydride group in the side chain can be obtained. The reaction temperature at this time is room temperature to 300 ° C., preferably 150 to 280 ° C., and usually 30 minutes to 50 hours. The ratio of PPS (I) and acid anhydride (II) used is such that PPS (II) having an acid anhydride group in the obtained side chain.
Both may be used so that the acid anhydride group unit in I) is 0.1 to 25 mol%, and the range is PPS (I) 1
The amount of the acid anhydride (II) is usually 0.5 parts by weight or more, and preferably 1 to 70 parts by weight, based on 00 parts by weight. After completion of the reaction, the reaction product is filtered and washed with acetone or the like,
Poly (arylene sulfide) (III) which is dried by heating and has a carboxylic acid anhydride structure introduced into a desired PPS molecular chain
To get

Specific examples of the carboxylic acid anhydride (II) represented by the formula 1 used in the present invention include pyromellitic dianhydride and 3,4,3 ', 4'-diphenylsulfone tetracarboxylic acid dianhydride. Anhydrous, 3,4,3 ', 4'-
Benzophenone tetracarboxylic dianhydride, 3,4,3
′, 4′-Diphenyldimethylmethanetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,4,3 ′, 4′-diphenyltetracarboxylic dianhydride, 3 , 4,3 ', 4'-Diphenylethertetracarboxylic dianhydride, 3,4,3', 4 '
-Diphenylmethane tetracarboxylic dianhydride.

The PPS (III) having an acid anhydride group in the side chain in the present invention is a polyarylic compound represented by the following chemical formula 23:
In addition to the lensulfide bond, an ether bond represented by the following chemical formula 24, a sulfone bond represented by the following chemical formula 25, a biphenyl bond represented by the following chemical formula 26, a substituted phenyl sulfide bond represented by the following chemical formula 27 (provided that In the formula, R represents an alkyl group, a nitro group, a phenyl group, an alkoxy group, or a carboxyl group.), And a copolymerization component as exemplified by the trifunctional bond represented by the following Chemical formula 28 may be contained. However, the copolymerization component is preferably less than 30 mol%.

[Chemical formula 23]

[Chemical formula 24]

[Chemical 25]

[Chemical formula 26]

[Chemical 27]

[Chemical 28]

A polyamide having an amino group at the terminal (I
Examples of V) include aliphatic polyamides and aromatic polyamides, and aliphatic polyamides are preferable. Polyamides having an amino group at the terminal include, for example, dicarboxylic acids such as terephthalic acid, isophthalic acid, oxalic acid, adipic acid, sebacic acid and 1,4-cyclohexyldicarboxylic acid, and ethylenediamine, pentamethylenediamine,
Hexamethylenediamine, decamethylenediamine, 1,
Polycondensation of diamines such as 4-cyclohexyldiamine and m-xylylenediamine: Polymerization of cyclic lactams such as caprolactam and laurolactam: Polycondensation of aminocarboxylic acids such as aminoenanthic acid, aminononanoic acid and aminoundecanoic acid, or the above cyclics It can be obtained by copolymerization of lactam, dicarboxylic acid and diamine. Specific examples of the polyamide having an amino group at the terminal include nylon 6 and nylon 6 as aliphatic polyamides.
6, nylon 610, nylon 612, nylon 11,
Nylon 12 may be mentioned, and those exemplified here are preferably used, but amorphous nylon, copolymerized nylon, etc. may also be used. The polyamide (IV) needs to have an amino group at its terminal.

Examples of the polar solvent used in the present invention include N-methyl-2-pyrrolidone (NMP), N, N
-Dimethylacetamide (DMAC), N, N-dimethylformamide (DMF), dimethylsulfoxide (D
Organic polar solvents such as MSO). The reaction of PPS (III) having an acid anhydride group and polyamide (IV), which is the first method of the present invention, is carried out at 150 to 300 ° C, preferably 230 to 280 ° C, usually for 30 minutes to 10 hours. .. The use ratio of PPS (III) and polyamide (IV) can be arbitrarily set, but PPS (III) is usually 1 to 99% by weight, preferably 5 to 95% by weight, and polyamide (IV) is usually 99 to 1% by weight. %, Preferably 95-
It is 5% by weight. Next, the reaction with PPS (I) having an amino group, tetracarboxylic acid anhydride (II) and polyamide (IV), which is the second method of the present invention, is carried out at room temperature to 3
It is carried out at 00 ° C, preferably 230 to 280 ° C, usually for 30 minutes to 50 hours. Regarding the usage ratio of those three parties,
The proportion of PPS (I) and tetracarboxylic acid anhydride (II) used is 0.5 parts by weight or more, preferably 1 to 70 parts by weight of tetracarboxylic acid anhydride (II) per 100 parts by weight of PPS (I). Parts by weight. In addition, polyamide (IV)
Is usually 1 to 99% by weight of PPS (I), preferably 5
-95 wt%, polyamide (IV) 99-1 wt%,
It is preferably used in an amount of 95 to 5% by weight. By doing so, the PPS unit has a polyamide unit of 0.
A copolymer having a graft ratio of 5 mol% or more can be obtained, but a graft ratio of 1 to 70 mol% is preferable. If the graft ratio is less than 0.5 mol%, it is difficult to achieve the intended purpose of the present invention. The graft copolymer obtained by the method of the present invention is, for the purpose of imparting various properties, glass fiber, carbon fiber, metal fiber, aramid fiber, fibrous potassium titanate, asbestos and silicon carbide or silicon nitride, if necessary. Fibrous inorganic fillers such as various whiskers including graphite, graphite, calcium carbonate, mica, silica, boron nitride, barium sulfate, calcium sulfate, kaolin,
Clay, bilophyllite, bentonite, sericite, zeolite, mica, nepheline sinite, ferrite, atarupulgite, wollastonite, calcium silicate, magnesium carbonate, dolomite, antimony trioxide, magnesium oxide, zinc oxide, titanium oxide , One or more inorganic fillers such as iron oxide, molybdenum disulfide, graphite, gypsum, glass powder, glass beads, quartz, quartz glass, metal powder such as iron, zinc, copper, aluminum and nickel. Is also possible.

[0015]

EXAMPLES Next, the present invention will be further explained based on examples. Synthesis example 1. (Synthesis example of PPS having amino group) NM was added to an autoclave with a stirrer having a capacity of 1 liter.
250 cc of P and 12 of Na ₂ S (water content 40 wt%)
Charge 7 g (0.98 mol) and 0.31 gr of NaOH and stir in a nitrogen atmosphere for about 2 hours 205
It was dehydrated by gradually raising the temperature to ℃. Then, the reaction system was cooled to 150 ° C., and 140 gr of paradichlorobenzene (0.95 mol), 8 gr of P-dichloroaniline (0.05 mol) and 0.5 gr of 1,2,4 were added to the reaction system. −
Trichlorobenzene (0.003 mol) was added to 80 gr of N
Add the solution dissolved in MP and add 250 for another hour
The temperature was raised to ℃ and the reaction was carried out for 2 hours. After the reaction was completed, the autoclave was cooled to room temperature, the contents were separated by filtration, and the reaction product, the roque cake, was washed 3 times with deionized water at 50 ° C. 100 excluding other unreacted materials
It was dried at ℃ and a PPS resin having an amino group was obtained.

Synthesis example 2. (P having an acid anhydride group in the side chain
Synthesis example of PS) 15 gr of the above PPS resin and pyromellitic dianhydride 2.
0 gr was added to 100 ml of NMP, and 180
The reaction was carried out while stirring at 1 ° C for 1 hour. The cake obtained by filtering the reaction slurry after cooling to room temperature was thoroughly washed with acetone and then dried at 150 ° C. overnight to obtain a reaction product. The infrared absorption spectrum of the product was measured by the film method. As a result, the infrared absorption attributed to the amino group near 3400 cm ⁻¹ found in the PPS having an amino group before the reaction was decreased, and the acid anhydride Absorption based on groups and imide groups was seen near 1780, 1730 cm ^-1 .
Then, the amount of acid anhydride groups in the obtained product was calculated by the following method. That is, a film was prepared by hot pressing from a powder obtained by mixing a PPS homopolymer and phthalic anhydride in several proportions, and the infrared spectroscopy (IR) analysis method revealed that the benzene ring C = C stretching vibration was 1400 cm ^-1 . analyzing the IR acid anhydride group C = O stretching vibration of 1780 cm ^-1, a calibration curve seeking absorbance ratio of 1400 cm ^-1 and 1780 cm ^-1, modified PPS obtained from the calibration curve
The amount of acid anhydride group was calculated and found to be 0.8 mol%.

Examples 1-6. PPS having an acid anhydride group in the side chain obtained in Synthesis Example 2 and nylon 6 resin (A2 manufactured by EMS)
8: PMMA-equivalent molecular weight Mn obtained from GPC = 3.
63 × 10 ⁴ , Mw = 6.25 × 10 ⁴ ; terminal amino group concentration: 0.039 mmol / g) was charged in 100 ml of NMP in an amount shown in Table 1, and a heating reaction was carried out under the conditions shown in Table 1. After completion of the reaction, the contents were separated by filtration, the filtration cake was thoroughly washed with acetone, and then the pressure was reduced to 150 ° C.
Dried overnight. The powder after drying is subjected to Soxhlet extraction with 1,1,1,3,3,3, -hexafluoro-2-propanol (HFIP), which is a selective solvent for nylon, and IR measurement of the insoluble matter is carried out. The graft ratio was calculated with. Further, the reaction product after drying was formed into a film shape (thickness: 50 μm) by hot pressing, and a tensile test was performed to determine the tensile strength and the tensile elongation. In addition, the measurement of the graft ratio and the tensile test in the following examples were performed by the following methods. Graft ratio measurement Graft ratio (weight of grafted polyamide / PP of trunk)
The weight of S × 100) was determined by using a calibration curve prepared by blending unmodified PPS and nylon 6 at various ratios in advance, and the absorbance at 3300 cm ⁻¹ and PPS based on the NH stretching vibration of nylon 6 were used. Was calculated from the ratio of the absorbance at 1400 cm ⁻¹ based on the C = C stretching vibration. Tensile test Length created by hot pressing: 80 mm, width: 10
A test piece having a thickness of 50 mm and a thickness of 50 μm was subjected to a tensile test at a distance between chucks of 40 mm and a tensile speed of 20 mm / min to determine the tensile speed and the tensile elongation. The results are shown in Table 1.

Examples 7-9. NMP10 in which PPS having an amino group obtained in Synthesis Example 1, nylon 6 resin used in Examples 1 to 6 and pyromellitic dianhydride are dissolved.
The graft ratio was calculated in the same manner as in Examples 1 to 6 except that the amount shown in Table 2 was added to 0 ml, heated and dissolved, and reacted, and the reaction product after drying was formed into a film by hot pressing. Molded into, and subjected to a tensile test to determine tensile strength and tensile elongation. The results are shown in Table 2.

Comparative Example 1 PPS having an amino group obtained in Synthesis Example 1 and Examples 1 to 6
Only the Nylon 6 resin used in Step 2 is put into NMP, and 240
Heated at ° C for 3 hours. Others were the same as in Examples 1 to 6 and the reaction product after drying was formed into a film by hot pressing and subjected to a tensile test to determine the tensile strength and the tensile elongation.
When the graft ratio was calculated, the IR absorption spectrum of nylon was not found in the insoluble matter of HFIP extraction, and it is presumed that the graft copolymerization reaction did not occur. The results are shown in Table 1.

[0020]

[Table 1]

[0021]

[Table 2]

Example 10 PPS having an acid anhydride group obtained in the same manner as in Synthesis Example 2
0.5 kg and nylon 6 resin used in Example 1 0.5 k
g was added to 10 l of NMP, and the reaction was carried out by stirring at 260 ° C for 3 hours. Next, the slurry was filtered, the obtained cake was thoroughly washed with acetone, and then dried under reduced pressure at 150 ° C. overnight. 2.8 kg of PPS (manufactured by Topren Co., Ltd., trade name: T-4AG) was added to the nylon graft P obtained above.
After adding 0.7 kg of PS and thoroughly dry blending,
Using a 20 mm twin-screw extruder rotating in different directions, 300 ° C, 1
400r. p. Melt kneading with m 2 to obtain pellets. The pellet was formed into a film and subjected to a tensile test in the same manner as in Example 1. The tensile strength was 5.0 kgf / mm ^2.
The elongation was 27%.

Comparative Example 2 2.8 kg of PPS used above, 0.35 kg of PPS having an amino group obtained in the same manner as in Synthesis Example 1, 0.05 kg of pyromellitic dianhydride, and nylon 6 used in Example 1
After sufficiently dry blending 0.35 kg of the resin, the mixture was melt-kneaded in the same manner as in Example 10 to obtain a pellet. Then, when a tensile test was conducted in the same manner as in Example 1, the tensile strength was 5.2 kgf / mm ² and the elongation was 4%. From the results of these Example 10 and Comparative Examples, it can be seen that the PPS copolymer obtained by the method of the present invention has a good elongation, and thus the brittleness is significantly improved.

[0024]

As described above, according to the present invention, the mechanical properties can be improved and the solvent resistance can be improved while eliminating the drawbacks of the prior art and maintaining the heat resistance of PPS. , Can be added as a compatibilizer by adding a small amount when blending PPS and nylon or other resins,
That is, it was possible to obtain a graft copolymer that can be an effective compatibilizer during the production of polymer alloys.

Continued Front Page (72) Inventor Tadao Ikeda 1-3-1 Nishitsurugaoka, Oi-cho, Iruma-gun, Saitama Tonen Research Institute

Claims (2)

[Claims] 1. A modification having an acid anhydride group obtained by a reaction of a polyarylene sulfide having an amino group at a side chain and / or a terminal with a carboxylic acid anhydride represented by the following chemical formula 1 in a polar organic solvent. A method for producing a graft copolymer of poly (arylene sulfide) and polyamide, which comprises reacting poly (arylene sulfide) with a polyamide having an amino group at a terminal in a polar organic solvent. [Chemical 1] (However, in Chemical formula 1, R ₁ is a tetravalent organic group containing at least 2 carbon atoms, and 2 or less of the carbonyl group in Chemical formula ₁ is any one carbon atom of the tetravalent organic group. It is bound to an atom.) 2. A polyarylene sulfide having an amino group at a side chain and / or a terminal, a carboxylic acid anhydride represented by the following chemical formula 1 and a polyamide having an amino group at the terminal are reacted in a polar organic solvent. A method for producing a graft copolymer of a poly (arylene sulfide) and a polyamide, which is characterized. [Chemical 1] (However, in Chemical formula 1, R ₁ is a tetravalent organic group containing at least 2 carbon atoms, and 2 or less of the carbonyl group in Chemical formula ₁ is any one carbon atom of the tetravalent organic group. It is bound to an atom.)