JPS5951945A - Polyphenylene sulfide composition - Google Patents

Abstract

PURPOSE:To provide a polyphenylene sulfide compsn. having excellent moldability and stable melt viscosity which can be readily adjusted, by blending a novolak type epoxy resin with polyphenylene sulfide having specified properties. CONSTITUTION:Polyphenylene sulfide satisfying the relationship (wherein N is non-Newtonian coefficient and V is melt viscosity) under a condition such that melt viscosity V is 10 to 100,000 P at 300 deg.C and a shearing rate of 200sec<-1>, is prepd. by reacting sodium sulfide with p-dichlorobenzene in a solvent such as N- methylpyrrolidone in the presence of an alkali metal carboxylate which is used for adjusting the degree of polymn. 0.01-40pts.wt. movolak type epoxy resin is blended with 100pts.wt. said polyphenylene sulfide to obtain the desired polyphenylene sulfide compsn.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a bowl-filled nylene sulfide composition with excellent moldability.

Polyethylene sulfide (hereinafter abbreviated as PPS) has excellent properties for engineering plastics, such as excellent chemical resistance, heat resistance, and electrical insulation, and is used mainly for injection molding. Used for various purposes.

However, various improvements are required before PPS can be used in a wider range of applications. □ That is, firstly, the melt viscosity of PPS is extremely low.

For this reason, since it is made of pellets, it is difficult to obtain good strands during extrusion molding, which causes problems in terms of stability of supply of pellets to the feeder during injection molding.

Furthermore, as a matter of course, it is not possible to obtain so-called extrusion-molded products such as sheets, sheets, and pipes that require higher extrusion moldability. One possible way to increase the melt viscosity of PPS is to increase the degree of crosslinking, but as the degree of crosslinking increases, the viscosity stability during extrusion molding decreases, making it difficult to obtain stable and good molded products. .

The second problem is the presence of pores in the molded product due to gas generated when PPS is melted. Although the cause of this is not very clear, it is presumed that the main cause is volatilization or decomposition of low molecular weight components present in the polymer. The presence of such pores deteriorates the mechanical properties and electrical properties of the PPS molded product. Furthermore, the gaseous components are mainly organic substances, and a small amount of "02, II?S" is also present, which causes corrosion of metal materials.

゛First: Dry PS for injection molding has a high degree of brown coloring, and if you want to create various colors at once for the purpose, a large amount of white filler is required, and therefore the mechanical strength of PPS This results in the loss of □.

The present inventors conducted various research studies to improve these drawbacks of PPS, and as a result, they discovered that a composition of a specific PPS with a low degree of crosslinking and an epoxy resin could eliminate the above-mentioned drawbacks, and the present invention reached.

The present invention is characterized in that: - The melt viscosity (V) at the original 300 °C at a shear rate of 200 (sec)-1 is 10 or more and 100,000 voise or less, and the non-Newtonian coefficient (
This is a polyphenylene sulfide composition containing PPS and 0.01 to 40 parts of an epoxy resin as essential components, characterized in that the relationship between N) and (1) does not satisfy the following formula (1).

Formula (]) 0.8≦N≦1.33+01000047
It is best to contain the XV structure at position 11'L in an amount of 70 T nyl% or more, and when the amount is less than 70 T nyl%, the composition of the present invention having outstanding properties is generally obtained. The polymerization method for this polymer is as follows:
A method of polymerizing p-dichlorobenzene in the presence of sulfur and sodium carbonate, polymerizing it in the presence of thorium sulfide in a polar solvent, or sodium bisulfide and sodium hydroxide, or hydrogen sulfide and thorium hydroxide. N-
A suitable method is to react sodium sulfide with p=nidichlorobenzene in an amide thread solvent such as methylpyrrolidone or dimethylacetamide or a sulfonic solvent such as sulfolane. At this time, in order to adjust the degree of polymerization, it is a preferable method to add an alkali metal salt of carboxylic acid or sulfonic acid, or to add alkali hydroxide. It is permissible to contain typical synthetic tetragroups, phenyl groups, alkoxy groups, carboxylic acid groups, etc., as long as they do not significantly affect the crystallinity of the polymer, but preferably the copolymerization component is 10 mol % or less. In particular, when trifunctional or more functional phenyl, biphenyl, naphdyl sulfide bonds, etc. are selected for copolymerization, the amount is preferably 3 mol% or less, more preferably 1 mol% or less.

Kakaru PPS can be produced using general manufacturing methods, such as (1) reaction of a halogen-substituted aromatic compound with an alkali sulfide (see U.S. Patent No. 2,513,188, Japanese Patent Publication No. 4.1-27671 and Japanese Patent Publication No. 45-3368). ) (2) Condensation reaction of thiophenols in the presence of an alkali catalyst or copper salt, etc. (US Pat. No. 32741 (i5, UK Pat. FF)
No. 111i 0 fi 6 (Refer to No. 1) (3) Condensation reaction of aromatic compounds with sulfur chloride in the presence of a Lewis acid catalyst (2) Iko No. 46-27255, Belgian Patent No. 2! M37 (see II<1), etc., and can be arbitrarily selected depending on the purpose.

As for PPS, an almost white uncrosslinked product is obtained by the polycondensation reaction as described above. However, because of its low molecular weight and low viscosity, it cannot be used for molding applications such as extrusion molding or injection molding. Therefore, conventionally, light-colored, low-molecular-weight PPS with a melt viscosity of 100 voids or less was heated in air below its melting point (285°C) to increase its molecular weight through oxidative crosslinking to produce high-viscosity products suitable for injection molding. . These are from Philisopuspe I/IJ Liam [Rydon P-4JI-Rydon I? Although it is available on the market as -6-l, it is colored brown due to oxidative crosslinking and has a three-dimensional crosslinked structure, so the viscosity stability during molding is poor.

In the present invention, PriS is epoxy 4! l Jl
Since the molecular weight is increased by the reaction with 1, unlike conventional PPs for injection molding, there is no need for hot bridging. However, since 171', it could not be used for injection molding due to its low viscosity, but PPs that do not have an oxidized crosslinking structure and do not undergo an oxidation step and have a low degree of coloring can be suitably used. On the other hand, highly oxidatively crosslinked 71 Telimer is not only colored brown but also has poor reactivity with novolac type epoxy resins and has a lower melt viscosity, making it unsuitable for the present invention.

The degree of crosslinking can be expressed by the relationship between the melt viscosity of the polymer and the non-22-tonian coefficient, and generally, at the same viscosity, N
The larger the value, the higher the degree of crosslinking. However, the circle used in the present invention) S is obtained when measuring the viscosity. Plot the respective logarithmic values of the shear rate and the shear center force, and calculate 300 "c, 2
If the slope of the tangent at the point 00 (seconds) - 1 is defined as a non-Newtonian coefficient N, then N is (1, 8, 4:1...
33+0.000047XV (melt viscosity). If N is outside this range, especially if it exceeds the upper limit, the polymer will be colored brown due to advanced oxidative crosslinking, and even if epoxy 4U fat is added, the melt viscosity will not increase sufficiently, and molding will be difficult. Due to insufficient stability, compositions having the characteristics of the present invention cannot be obtained. In the present invention, PPS that does not have an oxidized crosslinked structure is particularly preferred, but N
It can be used in the present invention as long as the degree of crosslinking is within the range of "double".

Melt viscosity (V), shear rate (D) in the present invention,
υ shearing stress (T) is measured using a convex flow tester or a melt indexer. The melt viscosity is 4 = 1 - apparent melt viscosity. These values are entered into the following three equations and 17 are output.

T= P R/ 2 L (dyne/cJ) D=
4Q/πR3'<17 seconds) V=T/D (Boys) In addition, the non-new 1-nian coefficient N is calculated by the following equation.

d (log'r) The melt viscosity and non-Newian coefficient in the present invention are all values at a temperature of 300° C. and a shear rate of 200 (1/sec).

The novolak type epoxy resin, which is another essential component of the present invention, contains two or more 3I epoxy groups and is obtained by reacting novolak 1 (Fuenol lit Mn with epichlorohydrin.As the novolak type phenol resin, Preferably, those obtained by the condensation reaction of phenols and formaldehyde are used.The phenols used as raw materials are not particularly limited, but include) T-nol, 0-cresol, m-cresol, p-cresol,
Bisphenol A rsorcinol, p-tert-butylphenol, bisphenol F1 bisphenol S
and mixtures thereof are particularly preferably used. Furthermore, epoxidized products of poly-p-vinylphenol and halogenated products of the above-mentioned epoxy resins can also be used in the same manner as the novola-7-type epoxy resin.

In the present invention, epoxy resins other than novolac type epoxy resins can also be used in combination within the range that does not detract from the effects of the present invention. Other epoxy resins such as bisphenol A sorcinol, hydroquinone, pyrocanal:1-l, bisphenol F1 saligenin, 1,3.5 °C
-l-lyhydroxybenzene, bisphenol S,) lyhydroxy-diphenyldimethylmethane, 4,4'-dihydroxybiphenyl, 1,5-dihydro-4-silyphthalene, kashij, -phynol, dihydroxy-diphenyl sulfone, 2 .2.5.Glycidyl ethers of bisphenols such as 5-tetrakis(4-hydroxyphenyl)hexane, halogenated bisphenols instead of bisphenols, glycidyl ethers such as diglycidyl ether of butanediol, and glycidyl esters such as phthalic acid glycidyl esters. glycidyl epoxy resins such as glycidyl amine threads such as N-glycidylaniline, linear systems such as epoxidized polyolefins and epoxidized soybean oil, and cyclic non-glycidyl epoxy resins such as vinyl cyclohexene dioxide and dicyclopentadiene dioxide. An example is 4δLJil. These epoxy resins may be used alone or as a mixture of two or more.

The additive science of the novolac type epoxy resin is P P S
10 (0.1 to 40 parts by weight, preferably 0.5 to 20 parts by weight per 1 part by weight). The preferred amount of the epoxy resin to be added varies depending on the molecular weight and purpose of PPS,
Generally, a large amount of epoxy resin is required for a low molecular weight of 1 pps or for an extrusion molding composition that requires high viscosity. If the amount is less than 0.1 parts by weight, the effect will be small, and if it exceeds 40 parts by weight, mechanical properties may be lost.
Depending on the epoxy resin added, it is undesirable because it may bleed onto the surface of the molded product or significantly reduce the melt flow stability of the composition.

Novolak-type epoxy resins are generally molded by blending curing agents such as amines, acid anhydrides, polysulfides, and phenolic resins, but in the present invention, no curing agents are used at all, or even if they are used. It is desirable that the amount of active hydrogen is less than half the molar ratio of the epoxy group component.

If a normal amount of curing agent is used together, not only will the reaction between the novolak epoxy resin and PPS be inhibited, but
This is because a stable increase in melt viscosity, such as the formation of a crosslinked network due to the reaction between the epoxy resin and the curing agent, cannot be expected.

The effect of using a hardener in combination with epoxy is 4! ! It can be expected to prevent deterioration of bleedability and thermal properties due to the addition of I fat.

rlIl of the composition of the present invention can be prepared in various known ways.

For example, 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, and kneaded at 230 to 400°C, and then prepared as pellets 7). There is a way to do it. It is also preferable to divide the epoxy resin into two or more times and perform the extrusion operation two or more times in order to promote the reaction between PPS and the epoxy resin.

It is also possible to tri-blend PPS and novolac type epoxy resin and melt-knead the mixture in an injection molding machine.

The composition of the present invention includes glass fiber, carbon fiber, potassium titanate, asbestos, silicon carbide, ceramic fiber, metal #
I&F, fibrous reinforcing agents such as silicon nitride, and barium sulfate, calcium sulfate, kaolin, clay, pyrophyllite, bentonite, sericite, zeolite, mica, mica, nephelin cipitate, tar, atalpulgite, and wollast. Knight, PMF (processed mineral fiber), ferrite, calcium silicate, calcium carbonate, magnesium carbonate, dolomite, antimony dioxide, zinc oxide, titanium oxide, magnesium oxide, iron oxide, molybdenum disulfide, graphite, gypsum, glass beads, glass Contains up to 80% of inorganic fillers such as balloons, quartz, and quartz glass, and organic reinforcing fillers such as aramid fibers in the composite acid -1! It can be reduced. These things! When adding a chemical agent or a chemical agent to the reaction mixture, a known silane coupling agent can be used. , also fluororesin,
Ill'llt:1 compounds such as molybdenum compounds can also be used.

In addition, the composition of the present invention may contain additives such as R (14) q, colorants, heat stabilizers, ultraviolet stabilizers, weather stabilizers, blowing agents, flammable agents, etc. without departing from the purpose of the present invention. bright combustion aid,
Contains a rust preventive agent (can be used as a sealant).Furthermore, the following polymers can be mixed and used in the same way.These polymers include ethylene, propylene, phthylene, pentene, butadiene, C-soprene, chloroprene, styrene. , α−
Memetis'f-L・n, vinyl acetate, vinyl chloride, acrylic i! ! Ester, methacrylic ester, (meth)
Φ-truncated homopolymers such as acrylonitrile or ζ;I
I-II, polymers, polyurethanes, polyamides, polyesters, polycarbonates, polyacetals, polysulfones, polyarylcarbons, 11-ether sulfones, polyarylates, polymer nylenes, 44゛cyto, poly, phenylene ethers , polyneegle, [-thylketone, polyimide 1. I! Examples include 411 homopolymers, copolymers or block and graph copolymers such as lyamimide, silicone resin, )L resin, fluororesin, and polyaryl needle.

The composition of the present invention has a stable melt viscosity and is easy to cut. Although unexpected, there is no generation of pores, which is seen in conventional oxidation-crosslinked products. In addition, it has excellent strength and bleedability compared to those mixed with epoxy resins other than novolac type epoxy resins. Therefore, it can be used in a wide variety of applications. Of course, the composition obtained according to the present invention can be used not only for injection molding and compression molding, but also for extrusion molding, blow molding, and foam molding, and can be processed into films, sheets, monofilaments, and fibers. Further, after the molding process, the WfI thermal properties can be further improved by heating at 200 to 300°C under vacuum or in the presence of oxygen scum.

Next, the present invention will be explained with reference to the n'(+) phase using examples and the like.

Note that % and parts in the examples are based on weight.

[Reference Example 1] Sodium sulfide (60% purity) 98.4g, sulfur hydroxide
Add 47 g of lithium to 73,080 g of N-meg rubirolide, heat up to 205°C while dehydrating, and then add 1,113 g of baladichlorobenzene and 510 g of N-methylpyrrolidone.
was added and heated at 260° C. for 5 hours under pressure. After cooling, the mixture was washed with water and dried.

The obtained I) PS had a melt viscosity of 37 Bois and a non-Newtonian coefficient of (1.95). This is referred to as Polymer 8.

The melt viscosity and non-Newtonian coefficient of Polymer 8 thermally crosslinked in air at a temperature of 270°C for 3 hours, 4 hours, 5 hours, and 6 hours, respectively, were 1800 Boyes and 1.1'? (Polymer 13), 3600 voids and 1.42 (Polymer C), 4300 voids and 1.63 (Polymer D), 5500 voids and 1.8
0 (Polymer E). In addition, Polymer 8 was heated to 260°C.
The melt viscosity and non-Newtonian coefficient of those thermally crosslinked in air for 5 hours, '1 hour and 9 hours were 300 Boyes and 1.13 (Polymer F), 1010, respectively.
poise and 1.31 (Polymer G), 2000 voices and 1.54 (Polymer H).

[Reference Example 2] Add 984 g of thorium sulfide (60% purity), 47 g of thorium hydroxide, and 765 t+ of lithium acetate dihydrate to 1811 g of N-meg rubirolidone 3 +
After increasing γ while dehydrating at ℃it', 510 g of p-dichlorobenzene 113H,N-methylpyrroline was added, heated under pressure at 230℃ for 2 hours and at 265℃ for 3 hours, and after cooling, Washing with water 1. Dry. The obtained PPS has a melt viscosity of 3980 Bois and a non-Newtonian coefficient of 1.2.
It was 1. This is called Polymer ■.

Heat Polymer 1 at 270°C in air for 3 and 4 hours, respectively! The melt viscosity and non-Newtonian coefficients of the bridged ones are 6800 Boise and 1.57 (Polymer J), 7800 Boise and 1.73 (Polymer K)
Met.

[Reference Example 3] 984 g of sodium sulfide (60% purity), 47 g of sodium hydroxide, and 765 g of acetic acid dihydroxide
- Added to 3080 g of methylpyrrolidone, heated to 205°C while dehydrating, and then p-dichlorobenzene 111
3g, 1.2゜4-trichlorobenzene 2.2g, N-
Add 510g of methyl vinyl noriton and heat for 230' under pressure.
After heating at 55°C for 3 hours and cooling, the obtained PPS had a melt viscosity of 13,500.
Boys, non-knees 1. It was 84 at 7th grade. This will be referred to as Polymer L.

[Example IJ Polymers A, B, C, D, E, prepared in Reference Example 1
F, G, 11 and Rydon P~4, Rydon R-6,
Novolac type epoxy 4 manufactured by Dainippon Ink Chemical Industry 01
^1 Fat Epicron N-695 was uniformly mixed in the proportions shown in Table 1.
After preliminary mixing, the mixture was melt-kneaded at 290 to 300° C. in a co-rotating 501-inch twin-screw Hent type extruder to obtain pellets. Table 1 also shows the change in melt viscosity before and after melt blending.

This pellet was put into a 40cm single-screw extruder and extruded at a cylinder temperature of 290 to 300°C to form a sheet-like molded product with a thickness of 2.5** and a medium size of 150I11. The surface condition and internal condition of the sheet are shown in Table 1. Various test pieces were cut out from this sheet and their physical properties were measured.

The results are also listed in Table 1. As is clear from Table 1,
By using the composition of the present invention, the melt viscosity of PPS increases,
It is also clear that a molded product with a smooth surface, no bubbles inside, and excellent mechanical strength can be obtained.

[Example 2] Polymers 8, D and ■ prepared from Reference Examples 1 and 2
and resin Ebikuron N-6!15, Asahi Glass ++1 i!
Glass fiber Glassron C5-03M^497 and talc were premixed in a tumbler for 5 minutes at the blending ratio shown in Table 2, and melt-kneaded at 280 to 290°C in a 40 Dragon single screw extruder to obtain Beresol. . This pellet was molded using a 3-ounce injection molding machine to prepare a test piece for measuring physical properties. At the same time, spiral flow was measured. Table 2 shows the results.
Also listed in From this, it is clear that the composition of the present invention increases the melt viscosity of PPS, exhibits less coloring, and provides injection molded products with excellent mechanical strength.

[Example 3] Polymer I J, L obtained in Reference Example 1 and Reference Example 2
and epoxy resin Ebicuron N-670 manufactured by Daij Hon Ink Kagaku Kogyo 01 in the proportions shown in Table 3 in a tumbler.
The mixture was mixed for a minute and extruded in a 40I single-screw extruder at a cylinder temperature and a die temperature of 300-310°C to obtain pellets. Next, the pellets were processed using a single-screw extruder of 1 $30 vs.
A sheet with a thickness of 300 microns and a medium size of 10 cn+ was produced by extrusion at a temperature of ~295° C. and a screw rotation speed of 30 to 40 r. All of the obtained sheets were pale yellow and transparent, had no air bubbles, and did not break even when folded. For comparison, Polymer E, and Rydon R-6 were melt-kneaded with the composition shown in Table 3 and extruded under the same conditions, but in both cases, the film had many small holes and uneven striped patterns. seen on the surface. In addition, this sheet was dark brown and had poor flexibility and easily cracked when bent.

1-Continued amendment (self-motivated) June 1980 Review by the Patent Office J-Kan Sai 1 Sugi Kazu Daidono 1, 1977 1+3 Patent Application No. 162977-2, Name of the invention Polysoenylene sulfide composition 3, ?iIi correction case, relationship between the two Patent applicant No. 58, 35 Sakashita 2-chome, Karuhashi-ku, Tokyo 174 (28
11> Human Russia Wood Ink Chemical 1 Industry 41 Near U Company Representative Ministry
Shigeru Kuni Kawamura 4, Agent 17-20, Kiso 3-chome, 11, Chuo-ku, Tokyo 103 1 Ink Chemical T-Gyo Co., Ltd. Telephone: Tokyo (03) 272-4F+l 1 (main representative) Invention of the specification Column 6 for explanation that corresponds to 4', content of amendment (1) Specification FF tn 9 rt No. 44j (Dlo
, 1~110 vehicle instantaneous parts'' is corrected to r (1,01~4 (l weight parts, I).

(2) 1 Librarian No. 9 Sada No. 841 r
- to do.

(3) Ibid. No. 121 (Lines 14-15, 1-hydroxide sodium 4,'/r<, 1 is r-hydroxide)
Correct to −4,71<J.

(hereinafter -1-)

Claims (1)

[Claims] The melt viscosity (V) at 300°C at a shear rate of 200 (sec)-1 is 10 or more and 100,000 voise or less.
Therefore, 100 parts by weight of polyphenylene sulfide and a novolak-type epoxy tree N O, characterized in that the relationship between the non-Newtonian coefficient (N) and V satisfies the following formula (1),
A polyphenylene sulfide composition containing 01 to 40 parts by weight as essential components. Notation (1) % formula %