JPH04100826A - Block copolymer and its resin composition - Google Patents

Abstract

PURPOSE:To obtain a block copolymer having a crystalline polymer structure, a high melting point and excellent heat resistance by copolymerizing polyphenylene sulfide sulfone with polyphenylene sulfide ketone. CONSTITUTION:Polyphenylene sulfide sulfone (PPSS) is copolymerized with polyphenylene sulfide ketone (PPSK) to obtain a block copolymer composed of a PPSS part and a PPSK part and having a melt flow rate of 1-900g/10min at 370 deg.C under a load of 5kg. Unlike a simple blend of PPSS with PPSK, this block copolymer has a crystalline polymer structure, a high melting point and excellent heat resistance.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a block copolymer with improved heat resistance consisting of a polyphenylene sulfide sulfone moiety and a polyphenylene sulfide ketone moiety, and a resin composition containing the same. The block copolymer and resin composition of the present invention can be molded into various shapes by injection molding, compression molding, extrusion molding, etc., and can be used for electrical/electronic parts, automobile parts, sliding parts, or architectural parts.・Used for various parts in the civil engineering field, aerospace, marine field, etc.

(Prior art) Polyphenylene sulfide sulfone (hereinafter abbreviated as PP5S) resin is a non-grade thermoplastic with excellent mechanical properties, moldability, electrical properties, etc. at relatively high temperatures around 1506 C to 200 C. It is a resin and has attracted attention as a high-performance engineering plastic. This resin is, for example,
It is described in Japanese Patent Publication No. 53-25880 that it can be obtained by the reaction of a dihaloaromatic sulfone with an alkali metal sulfide. However, this resin has poor high-temperature fluidity (and has problems with moldability). Also, although it has a relatively high glass transition point due to its poor quality, it has poor mechanical strength at high temperatures of 220°C or higher. This has the drawback of limiting its use in applications that require higher heat resistance.In order to compensate for this drawback, we attempted a method of blending a resin with further heat resistance, but the compatibility was not practical due to insufficient heat resistance.On the other hand, P
As block copolymers of P5S resin, for example, a block copolymer with non-quality aromatic sulfone is disclosed in JP-A-61-72020, and a block copolymer with polyphenylene sulfide is disclosed in JP-A-62-205157. Polymers are disclosed. However, these methods
This is an attempt to improve the mechanical properties of the resin, especially the impact strength, but it is not necessarily sufficient to improve the heat resistance.
There is a problem in that the applications of the molded product are restricted.

On the other hand, polyphenylene sulfide ketone (hereinafter PP5K)
) has high heat resistance but a low Tg of 140°C.
There was a problem in maintaining rigidity at high temperatures.

(Problems to be Solved by the Invention) An object of the present invention is to obtain a block copolymer that does not impair the characteristics of conventional PP5S resins and also has heat resistance.

(Means for Solving the Problems) The present inventors focused on polymers that can be block copolymerized with ppss and have excellent heat resistance, and as a result of intensive studies, the present inventors discovered that block copolymerization can be achieved by copolymerizing PP5K and ppss. It was discovered that coalescence could be obtained, and the present invention was completed.

That is, the present invention is a PRO-TSUKU copolymer with improved heat resistance, which is composed of a PP5S part and a PPS part, and has a melt flow rate in the range of 1 to 900 g and 710 minutes at 370°C and a load of 5 kg. , and a resin composition containing the same.

It is defined as a polymer having the PP5S position constituting the block copolymer of the present invention. The molecular weight of this polymer is the logarithmic viscosity η1nh (where ηinh is 0.5g/1
At a polymer concentration of 00 mL of solution, phenol/1. 1. 2. 2-tetrachloroethane (3:2
Weight ratio) The value was measured at 30°C in a mixed solvent and calculated according to the following formula: η1nh=Qn (relative viscosity)/polymer concentration. ) is preferably in the range of 0.05 to 1°0. A method for polymerizing this polymer includes, for example, a method in which a dihaloaromatic sulfone and an alkali metal sulfide are reacted in an organic amide solvent (see US Pat. No. 4,102,875).

PP5 used when synthesizing the block copolymer of the present invention
For example, S can be added to the end of the polymer, for example, by reacting the dihaloaromatic sulfone in a 5 mol% excess amount relative to the amount of the alkali or metal sulfide during the polymer synthesis reaction (US Pat. No. 4,301,274). ).

On the other hand, the PP5K portion constituting the block copolymer of the present invention is defined as a polymer. Such PP5K has a reduced viscosity ηred (here, ηred is 0°5 g/10
It was measured at 25°C in 98% sulfuric acid at a polymer concentration of 0 mQ solution, and the following formula ηred = (relative viscosity - 1) /
This is a value calculated according to the polymer concentration. ) is 0.2 to 2
Preferably, the range is . As a polymerization method for this polymer, for example, a method in which dihalobenzophenone and an alkali metal sulfide are reacted in an organic amide solvent (JP-A-63
-113020 and JP-A-64-54031).

The block copolymer of the present invention is obtained by, for example, reacting the terminal group of PP5S with the terminal group of PP5K. It is necessary to keep it gender-based. A method for obtaining such PP5K includes a method in which the sodium sulfide component of the monomer is reacted in advance in an amount of 1 to 20 mol % in excess of the cyhalopenzophenone component during the polymerization reaction.

When carrying out the copolymerization reaction of ppss and PP5K in the method of the present invention, it is also possible to use a method of adding a binder such as dihaloaromatic sulfone or sodium sulfide as a third component. In addition, PP5S and PP may be used as block copolymers without departing from the object of the present invention.
It is also possible to use a method in which the other monomer component is polymerized in the presence of one of the 5K polymers to finally obtain a copolymer.

Furthermore, when carrying out the copolymerization reaction, it is most preferable to make the number of terminal reactive groups of PP5S and PP5K the same because a block copolymer can be obtained in good yield. On the other hand, when the number of terminal groups of either component is excessive, only the block copolymer can be recovered by fractionating or extracting only the unreacted homopolymer component after the reaction is completed.

Among the dihaloaromatic compounds used in the production of the block copolymer of the present invention, examples of the dihalodiphenylsulfone constituting the pps s moiety include bis(4-chlorophenyl)sulfone, bis(4-fromophenyl)sulfone, and bis(4-chlorophenyl)sulfone.
-fluorophenyl) sulfone and the like are suitable.

On the other hand, as the dihalobenzophenone constituting the PP5K moiety, 4,4-1 dichlorobenzophenone, 4,4-1 difluorobenzophenone, 4°4-dibromobenzophenone, etc. are suitable.

Further, as the alkali metal sulfide, lithium sulfide, sodium sulfide, etc. are preferable, and these alkali metal sulfides may be those obtained by a reaction between an alkali metal hydrosulfide and an alkali metal hydroxide.

The solvent used in the copolymerization reaction is preferably an organic polar solvent that is substantially liquid at that temperature and pressure. Specifically, formamide, acetamide, N-methylformamide, N,N-dimethylformamide, N
, N-dimethylacetamide, 2-pyrrolidone, N
-Methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, ε-caprolactam, N-methyl-ε-caprolactam, hexamethylphosphoramide, tetramethylurea, 1,3-dimethyl-2-imidazolidinone amides, ureas and lactams such as; sulfones such as sulfolane and dimethylsulfolane; nitriles such as benzonitrile;
Examples include ketones such as methyl phenyl ketone; polyethylene glycols and mixtures thereof. Among these solvents, it is particularly preferable to use aprotic organic polar solvents such as amides, lactams, or sulfones. The amount of the organic polar solvent to be used is in the range of 2 to 20 times, preferably 3 to 10 times, in weight ratio to the amount of the polymer component.

The copolymerization reaction product obtained by the method of the present invention is a block copolymer of chemically bonded ppss and PP5K. ) Extraction is performed using a mixed solvent and 98% sulfuric acid, which is a good solvent for PP5K, and the presence or absence of homopolymers in each extract can be confirmed.

In addition, when performing a copolymerization reaction, the ratio of PP5S and PP5K may vary depending on the desired properties, or the PP5S component and P5K may differ depending on the desired properties.
The molar ratio with the P5K component is generally 1 to 99799 to 1.
, preferably 5-90/95-10, more preferably,
The range is 30-70770-30. The above molar ratio is 1
If it is less than /99, 150 will be given by ppss.
- Effects such as maintaining rigidity at around 200°C cannot be achieved.
Moreover, if it exceeds 99/1, the heat resistance and mechanical properties brought about by PP5K will not be exhibited, so the effects aimed at in this patent cannot be obtained, which is not preferable.

In addition, the block copolymer of the present invention was heated at 370°C and under a load of 5 kg.
The melt flow rate is in the range of 1 to 900 g/10 minutes. Especially the melt flow rate is 100g.
Those of less than 10 minutes are suitable for molding, and others can be used depending on the purpose.

In the resin composition of the present invention, for example, when PP5K is used in combination with 3 to 100 parts by weight, more preferably 10 to 100 parts by weight, of the block copolymer, preferably 1 to 97 parts by weight, or more Preferably 10 to 90 parts by weight; when PP5S is used in combination, the content of PP5S is preferably 1 to 60 parts by weight, more preferably 10 to 40 parts by weight. The resin composition of the present invention can have even better compatibility by containing 3 to 100 parts by weight of the block copolymer. Furthermore, the resin composition of the present invention can also be obtained by reacting an excess amount of either the PP5K component or the PP5S component when producing the block copolymer.

In order to improve the performance as an engineering plastic such as strength, heat resistance, and dimensional stability, the composition of the present invention may contain an arbitrary filler of up to 70% by weight. Specifically, the fillers include glass fibers, carbon fibers, potassium titanate, asbestos, silicon carbide, ceramic fibers, metal fibers, fibrous reinforcements such as silicon nitride, barium sulfate, calcium sulfate, kaolin, crebairofilite, bentonite, sericite, zeolite, mica, mica, nephelinsinite, talc,
atalvargite, wollastonite, PMF,
Ferrite, calcium silicate, calcium carbonate, magnesium carbonate, dolomite, ammonium trioxide, zinc oxide,
Examples include inorganic fillers such as titanium oxide, magnesium oxide, iron oxide, molybdenum dioxide, graphite, lithium carbonate, gypsum, glass beads, glass balloon quartz powder, and organic reinforcing agents such as aramid fibers. When adding these reinforcing agents or fillers, known silane coupling agents can be used.

In addition, additives having an effect on thermal stability, such as a compound having a benzotriazole group or an imidazole group, or a carposiimide compound, can be added to the composition of the present invention.

In addition, the composition of the present invention may include polyphenylene oxide, polyarylate, polyamide, polybutylene terephthalate, polyphenylene sulfide, polyetheretherketone, polyetherketone, phenoxy resin, polyimide, polyamideimide, Liquid crystal polymers such as polyetherimide, polysulfone, polyethersulfone, polycarbonate, or fully aromatic polyester; Polyolefins such as polyethylene and polypropylene; thermoplastic resins such as α-olefin copolymers such as maleic acid-modified polypropylene; and novolac type epoxy. It may contain an epoxy resin 1 such as a resin, or a thermoplastic elastomer such as a nylon 11/polyether polyamide elastomer or a hydrogenated conjugated diene/styrene copolymer.

The composition of the invention can be prepared in various known ways. For example, according to the old invention, the raw materials are mixed uniformly in advance using a mixer such as a tumbler or Henschel mixer, then fed to a single-screw or twin-screw extruder, melt-kneaded at 230 to 400°C, and then pelletized. Block copolymers and their resin compositions are used not only for injection molded or compression molded products such as electrical and electronic parts, but also for fibers, sheets, films, etc.
It can be used for extrusion molded products such as tubes, blow molded products, transfer molded products, etc.

(Examples) Next, the present invention will be specifically explained using Examples, but the present invention is not limited thereto.

Example 1 (A) Synthesis of terminal chlorophenyl group-type ppss In a 50Q autoclave, 9.90 kg of N-methylpyrrolidone, 3.28 kg (25.0 mol) of sodium sulfide heptahydrate, 10 g of sodium hydroxide, and bis(p- 7.18 kg (25.0 mol) of (chlorophenyl) sulfone was charged, the temperature was raised to 200°C under a nitrogen atmosphere, and the reaction was carried out at that temperature for 6 hours with stirring.

Next, 360 g (1.25 mol) of bis(p-chlorophenyl)sulfone was added to this system and 1 k of N-methylpyrrolidone was added.
A solution dissolved in g was added to the mixture, and the reaction was further continued for 1 hour. After cooling the reaction vessel, the contents were taken out, washed several times with hot water and acetone, and the polymer cake was filtered off. This cake is 80-1
5.89 kg of light brown polymer dried under vacuum at 50°C
(yield J9s%). Logarithmic viscosity η1n of this polymer
h (where ηinh is phenol/1.l at a polymer concentration of 0.5 g/100 mQ solution.

The value was measured at 30°C in a mixed solvent of 2.2-tetrachloroethane (3:2 weight ratio) and calculated according to the following formula η1nh=Qn (relative viscosity)/polymer and concentration. ) was 0.25.

(B) Synthesis of terminal sodium sulfide group type PP5K 14.7 N-methylpyrrolidone in a 50Q autoclave
0 kg and sodium sulfide 2.7 hydrate 4.82 kg (3
6,8 mol) and 18 g (0,45 mol) of sodium hydroxide
mol) was charged, and the temperature was raised to 190° C. over about 2 hours with stirring under a nitrogen atmosphere, and 800 mH of water was distilled out. After cooling the reaction system to 100°C, 8.75 kg (35.0 mol) of 4,4-dichlorobenzophenone, N
- 3.50 kg of methylpyrrolidone was added, and the reaction was carried out at 240°C for 3 hours. After cooling the reaction vessel, a part of the contents was sampled and filtered, and the cake was boiled and washed three times with hot water and further washed twice with acetone.
Drying at °C gave a pale gray-brown powdery polymer (yield 94%). The reduced viscosity of this polymer ηred (here, ηred is the polymer concentration 0.5g/100mQ, 9
Measured at 25 °C in 8% sulfuric acid, ηred = (relative viscosity -
1)/value calculated according to polymer concentration) is 0.4
It was 5.

(C) Synthesis of block copolymer 3.80 kg of the above PP5K polymerization mixture, 1.50 kg of the above-mentioned chlorophenyl-terminated PP5s and 6,00 kg of N-methylpyrrolidone were added, and after nitrogen purging, the mixture was sealed and heated to 205°C. The temperature was raised to 100.degree. C., and the reaction was continued at this temperature for 3 hours. After cooling the reaction vessel, the contents were filtered and the solid content was removed with N
- Washed twice with methylpyrrolidone and then boiled three times with hot water. The resulting cake was dried at 120° C. for 5 hours to obtain 2.38 kg of light brown powdery polymer.

Next, when 10 g of this polymer was dispersed in 100 mQ of 98% sulfuric acid and an extraction experiment of a PP5K homopolymer was attempted, PP5K was not present in the extract. On the other hand, 2.38 kg of the above product was washed and extracted twice with 10 kg of a mixed solvent of phenol/tetrachloroethane (3:2 weight ratio), and as a result of replacing the solvent with acetone, the homopolymer of PP5S was completely separated in the second extraction. In the end, only 30g of PP5S homopolymer was extracted.

In addition, PP5S and P used in the production of the block copolymer
When a simple blend of P5K was fractionated using the above method, each was quantitatively recovered.

From these results, it was determined that the polymer obtained by extraction using the above method was a reaction product of PP5S and PP5K, that is, a block copolymer. The melt flow rate of this polymer (370°C, load 15kg) is 72g71
It was 0 minutes.

When the infrared absorption spectrum of this polymer was measured, no peaks other than the characteristic absorption of ppss and PP5K were observed. Furthermore, from the characteristic absorption intensities of PP5S and PP5K observed at 620 cm-' and 920 cm-' in the infrared absorption spectrum of the mixture of both, the peak intensity ratio at 920 cm-', that is, 920 cm-'
absorption intensity/(absorption intensity of 920cm-'+620cm
-' absorption intensity) and the PP5K mixing ratio. Using this, the absorption intensity ratio at 920 cm-' was determined from the infrared and line absorption spectra of the produced polymer,
The content of the PP5K moiety in the block copolymer was calculated to be 40 mol%.

Further, elemental analysis of this polymer was conducted, and the sulfur content was determined to be 21.51%. Since the theoretical composition value of sulfur calculated from the following structural formula was 21.52%, it was confirmed that the content of PP5K was 40 mol%.

In addition, a differential scanning calorimeter (manufactured by Seiko Electronics Co., Ltd., DS
As a result of analyzing the cooling crystallization behavior of this copolymer under a nitrogen atmosphere using minutes) was observed at 280°C.

From these results, it can be seen that the copolymerization reaction product of this example is P
It was confirmed that P5S and PP5K are chemically bonded block copolymers.

Furthermore, the glass transition temperature Tg and melting point Tm of the amorphous sample that had been rapidly cooled from the molten state were heated at 20°C/min under a nitrogen atmosphere and were found to be 205°C and 340°C, respectively. Table 1) The copolymer obtained in this example was heated at 320 to 380° using a 30 mm twin screw extruder.
C was heated and kneaded to form pellets. This pellet is injection molded at a set temperature of 320 to 380°C, and the mold temperature is 150°.
A test piece was prepared under conditions C.

The melt flow rate was measured by the method of ASTM D-1238 (370° C., 5 kg load), the bending strength was measured by the method of ASTM D-790, and the molding shrinkage rate was measured by the method of ASTM D955. The results were as shown in Table 1.

Comparative Example 1 Using the homopolymer of ppss and PP5K synthesized in Example 1, a test piece was prepared by mixing the PP5K content to 40 mol% according to the method of Example 1, and the physical properties were measured. . The results were as shown in Table 1.

Comparative Examples 2-3 PP5S and PP5 obtained by the same method as Example 1
Similar test pieces were prepared for each single polymer of K, and the physical properties were measured. The results were as shown in Table 1.

In the case of block copolymers, compared to PP5S alone, PP5K alone, or a simple mixture of PP5S and PP5K,
The resin had a high Tg and/or Tm and improved bending strength, indicating that it was a resin with improved heat resistance and mechanical strength. Furthermore, this block copolymer had a small mold shrinkage rate and excellent dimensional stability.

Example 2 5.30 kg of sodium benzoate with sodium sulfide
A terminal sodium sulfide group type PP5K polymerization mixture was synthesized in the same manner as in Example 1 except that (36.8 mol) was added. When some samples were taken and ηrecl was measured, it was 0.70.

Next, 1.65 kg of lithium acetate was added at the time of monomer preparation.
PP5S (77
1nh=0.38) 1.50kg and the above PP5K weight 1
A portion of the mixture (14.01 kg) and 4.00 kg of N-methylpyrrolidone were mixed, and after nitrogen purging, the mixture was sealed and heated at 210°C.
The reaction was carried out for 5 hours. The same treatment as in Example 1 was carried out to separate and remove unreacted ppss and PP5K, and finally 4
．． 13 kg of grayish brown polymer was obtained.

The PP5K content was calculated from the infrared absorption spectrum and was 72 mol%. A test piece was prepared from this block copolymer in the same manner as in Example 1, and its physical properties were measured. The results were as shown in Table 1.

Example 3 During the synthesis of a block copolymer, 1.73 kg of polymer was obtained in the same manner as in Example 2 except that a portion of 1.50 kg of the PP5K polymerization mixture obtained in Example 2 was used.Infrared absorption spectrum When the PP5K content was calculated from
It was mol%. A test piece was prepared from this block copolymer in the same manner as in Example 1, and its physical properties were measured. The results were as shown in Table 1.

Example 4 Using 3.00 kg of PP5S obtained by the method of Example 1 and 11.41 kg of the PP5K polymerization mixture, a copolymerization reaction was carried out in exactly the same manner as in Example 1, and a copolymerization reaction was carried out in exactly the same manner as in Example 1. %, melt flow rate is 63g/1
A block copolymer of 0 minutes was obtained.

P synthesized in Example 1 for 80 parts by weight of this copolymer
A test piece was prepared by mixing a mixture containing 20 parts by weight of P5S using a 30 mm extruder in the same manner as in Example 1, pelletizing the mixture, and injection molding the mixture. ASTM
The heat distortion temperature was measured by the method of D-648 (18.6 kg/cm 2 load), and the bending strength was measured by the method of ASTM D-790.

The results were as shown in Table 2.

Examples 5 to 8 Using the block copolymer obtained in Example 4, each pomopolymer of PP5S and PP5K was prepared in Example 1.
Polyphenylene sulfy)” (PP
Rydon P-4 (manufactured by Phillips Petroleum), commercially available as S) 41 resin, and C as glass fiber.
5-03MA419 (manufactured by Asahi Fiberglass Co., Ltd.) as the second
After tri-blending according to the blending ratios shown in the table, test pieces were prepared in the same manner as in Example 4, and their physical properties were measured.

The results were as shown in Table 2.

Comparative Example 4 The PP5S, PP5K and glass fibers used in Example 4 were blended in the proportions shown in Table 2, and the physical properties were measured in the same manner as in Example 4.

The copolymer composition according to the present invention had a high heat deformation temperature even when compounded with glass fiber, and especially improved bending strength at high temperatures, and was excellent in both heat resistance and mechanical strength.

Example 9 Physical properties were measured in the same manner as in Example 4, except that 40 parts by weight of the glass fiber used in Example 6 was blended with 60 parts by weight of the block copolymer obtained in Example 2. The results shown in Table 2 were obtained.

50 parts by weight of the block copolymer obtained in Example 3, 10 parts by weight of the PP5K powder obtained in Example 2, and commercially available polyethersulfone Pictrex 20
The physical properties were measured in the same manner as in Example 4, except that 10 parts by weight of 0P (manufactured by ICI Japan) and 30 parts by weight of the above-mentioned glass fiber were blended, and the results shown in Table 2 were obtained.

Example 11 Melt viscosity ηi, nh was 0.1 using the same method as Example 1.
Synthesize PP5S of 8, then rlred is 0.30
A block copolymer having a PP5K content of 56 mol% was finally made into a block copolymer containing 80 mol% of PP5K.
% by weight, and a composition containing 20ji1% of PP5K homopolymer was obtained. Melt flow rate of this composition
It was 40.

For 40 parts by weight of the above composition as a block copolymer, 30 parts by weight of the glass fiber, 3 parts by weight of commercially available calcium carbonate,
0 parts by weight were mixed and the physical properties were measured in the same manner as in Example 4, and the results shown in Table 2 were obtained.

Example 12 Terminated chlorophenyl group type PP5S (η1n
h=0.18) and terminal sodium sulfide group type PP5K (ηred=0.26) synthesized in the same manner as in Example 1 except that the reaction temperature was 230°C, the PP5K content was reduced. A block copolymer containing 45 mol% was obtained.

The melt flow rate of this polymer is 43,0g710
minutes, and its Tg and Tm were 203°C and 342°C, respectively.

Example 13 Terminal chlorophenyl group type PP5S (77i
nh=0. A copolymerization reaction between 13) and 11 with terminal sodium sulfide group type PP5K (ηred=0.22) synthesized in the same manner as in Example 12 except that the reaction time was 1°5 hours resulted in a PP5K content of 38 mol. % block copolymer was obtained. The melt flow rate of this polymer was 740 g/lo min, and its Tg and Tm were 208°C and 33,6°C, respectively.

(Effect of the invention) The block copolymer of the present invention can be used as PP5S alone or as PP5S.
Unlike the composition of a simple blend of ss and PP5K,
Since it is a block copolymer of the ppss part and the PP5K part, it has a crystalline polymer structure, has a high melting point, and has excellent heat resistance. Further, since the resin composition of the present invention contains the above block copolymer, it has excellent heat resistance and mechanical properties. Furthermore, surprisingly, it becomes possible to provide a molding material with extremely high dimensional accuracy and low mold shrinkage rate.

substitute Patent attorney Katsutoshi Takahashi

Claims (1)

[Claims] 1. Consisting of a polyphenylene sulfide sulfone part and a polyphenylene sulfide ketone part, 3700°C,
Metol flow rate at 5kg load is 1 to 900g
block copolymer in the range of /10 minutes. 2. A resin composition comprising a block copolymer consisting of a polyphenylene sulfide sulfone moiety and a polyphenylene sulfide ketone moiety, and polyphenylene sulfide sulfone and/or polyphenylene sulfide ketone, and optionally containing a filler.