JPH026954B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention is based on polyphenylene sulfide (hereinafter referred to as polyphenylene sulfide).
The core material is a pipe made of fiber-reinforced thermosetting resin (abbreviated as PPS), and the outer layer is a fiber-reinforced thermosetting resin (hereinafter referred to as
This relates to composite resin pipes coated with FRP (abbreviated as FRP) that have excellent corrosion resistance, chemical resistance, heat resistance, strength, rigidity, etc. Conventionally, PPS has been applied to various automobile parts and electronic and electrical equipment parts by injection molding, and has been used as a powder by taking advantage of its excellent corrosion resistance, chemical resistance, and heat resistance comparable to polytetrafluoroethylene (Teflon) resin.
PPS is used in fields such as coating metals. When pipes are manufactured using extrusion molding using PPS for piping in chemical plants, etc., they have the disadvantage of low strength and rigidity, and cannot withstand the pressure of the fluid passing through the pipes, causing them to break. To prevent this, it is possible to strengthen PPS with glass fiber, carbon fiber, etc., but in the process of forming pipes by extrusion molding using compounds containing glass fibers, carbon fibers, etc. Since it is oriented in the axial direction, it has almost no reinforcing effect in the circumferential direction of the pipe and has the disadvantage of not being able to withstand internal pressure.
On the other hand, FRP pipes are manufactured by impregnating glass fibers, carbon fibers, or other rovings with resin and forming them into a tubular shape by winding them around a mandrel or drawing them with a die.
However, the resins used in FRP are mainly thermosetting resins such as unsaturated polyester and epoxy resins, and although pipes made of these resins have better corrosion resistance than steel pipes, PPS
It does not match the corrosion resistance, solvent resistance, and heat resistance of resin at all. Furthermore, since a mandrel is used during tube forming, a process of attaching and detaching the mandrel is required, resulting in poor process efficiency. The present inventor found that PPS has particularly excellent chemical resistance, solvent resistance, heat resistance, and long-term dimensional stability compared to other thermoplastic resins, and has a temperature of 260°C momentarily and 220-240°C over a long period of time. It can withstand use at high temperatures of ℃, and even in such a high temperature atmosphere, it can withstand almost all kinds of chemicals.
It has the characteristic of not being attacked by solvents, and we focused on the fact that there are almost no plastic materials other than PPS that have this characteristic, and as a result of intensive research to improve the above disadvantages, we developed each individual material. We have completed a unique resin composite pipe that takes advantage of the features and overcomes the drawbacks. That is, the present invention provides a composite resin pipe having excellent corrosion resistance, chemical resistance, heat resistance, strength, rigidity, etc., which is made of a PPS pipe as a core material and whose surface is coated with a fiber-reinforced thermosetting resin. be. The composite resin pipe of the present invention has an integral structure by coating the outer surface of a PPS pipe extruded with a filament winding device with an FRP winding layer, and has excellent corrosion resistance, chemical resistance, heat resistance, strength, It has excellent rigidity. The feature of the present invention is that by using PPS pipe as the core material, which has extremely excellent chemical resistance and heat resistance, it compensates for the low chemical resistance, especially solvent resistance, of the FRP layer, which is the reinforcing layer. . Furthermore, compared to FRP pipes, there is no need to use a mandrel during manufacturing.
There is an additional effect that the PPS pipe also serves this purpose. The composite resin pipe of the present invention is manufactured by using, for example, a PPS pipe obtained by extrusion molding as a core material and a reinforcing material impregnated with a thermosetting resin, such as several hundred glass fibers with a diameter of 5 to 20 microns, bundled together. After winding glass roving or the like with a filament winding device, preferably in the circumferential direction of the core material at a desired winding angle, it is heated, exposed to light, ultraviolet rays, etc.
It is obtained by curing by irradiation with far infrared rays or the like. The PPS used in the present invention has the general formula

Those containing 90 mol% or more of the structural unit represented by the formula are preferable, and those containing less than 90 mol% have poor physical properties. Polymerization methods for this polymer include a method in which p-dichlorobenzene is polymerized in the presence of sulfur and sodium carbonate, a method in which p-dichlorobenzene is polymerized in the presence of sulfur and sodium carbonate, and a method in which p-dichlorobenzene is polymerized in the presence of sodium sulfide, sodium bisulfide and sodium hydroxide, or hydrogen sulfide and sodium hydroxide in a polar solvent. Examples include polymerization with p-chlorothiophenol, self-condensation of p-chlorothiophenol, etc., but the reaction of sodium sulfide with p-dichlorobenzene in an amide solvent such as N-methylpyrrolidone or dimethylacetamide, or a sulfonic solvent such as sulfolane may be used. An appropriate method is to 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. If it is less than 10 mol% as a copolymer component, a meta bond (

[Formula]), ether bond If (

[Formula]), sulfone bond If (

[Formula]), bihueni le join (

[expression]), replacement enyl sulfide bond (

[Formula] Here, R represents an alkyl, nitro, phenyl, or alkoxy group), a trifunctional phenyl sulfide bond (

[Formula]) may be contained as long as it does not significantly affect the crystallinity of the polymer, but preferably the copolymerization component is 5 mol % or less. Especially trifunctional or higher functional phenyl, biphenyl,
When a naphthyl sulfide bond or the like is selected for copolymerization, the amount is preferably 3 mol% or less, more preferably 1 mol% or less. Such PPS can be produced by common manufacturing methods, such as (1) reaction of a halogen-substituted aromatic compound with an alkali sulfide (see U.S. Pat. No. 2,513,188, Japanese Patent Publication No. 44-27671 and Japanese Patent Publication No. 45-3368) (2) ) Condensation reaction of thiophenols in the presence of an alkali catalyst or copper salt (US Patent No. 3274165, British Patent No. 1160660)
(3) Condensation reaction of aromatic compounds with sulfur chloride in the coexistence of a Lewis acid catalyst (Special Publication No. 46-27255)
(see Belgian Patent No. 29437), and can be arbitrarily selected depending on the purpose. Furthermore, in a proportion of 50% by weight or less of PPS, Teflon resin, polyamide, polycarbonate, polysulfone, polyallylsulfone, polyethersulfone, polyimide, polyamideimide, epoxy resin, polyethylene, polypropylene, PET,
Various resins such as PBT can be added. In addition, fibrous reinforcing agents such as glass fiber, carbon fiber, metal fiber, potassium titanate, asbestos, silicon carbide, ceramic fiber, and silicon nitride are added to PPS; barium sulfate, calcium sulfate, kaolin, clay, pyrofluorite, and bentonite. , sericite, zeolite, mica, mica, nephelinsinite, talc, attalpalgite, wollastonite, processed mineral fiber (PMF), ferrite, calcium silicate, calcium carbonate, magnesium carbonate, dolomite, trioxide Ammonium, zinc oxide, titanium oxide, magnesium oxide, iron oxide, molybdenum disulfide, graphite, gypsum, glass beads,
Inorganic fillers such as glass balloons and quartz powder can be contained in the composition in an amount of 0.1 to 70% by weight. When adding these reinforcing agents or fillers, known silane coupling agents or titanate coupling agents can be used. Next, the thermosetting resin used for FRP is:
Unsaturated polyester resins, unsaturated monocarboxylic acid-modified vinyl ester resins, epoxy resins, and the like are useful. In addition, reinforcing materials include glass fiber, carbon fiber, Kepra fiber, nylon, polyester,
Rovings of rayon, metal, etc. are useful, and woven fabrics thereof can also be used, but glass rovings are particularly preferred. In the FRP layer constituting the pipe of the present invention, in addition to the filament winding layer having a constant intersecting angle, there may be a drawn layer of FRP arranged in the axial direction of the pipe. In addition, the outer layer of FRP has chemical resistance,
To improve lubricity, various thermoplastic resins such as PPS resin, polyethylene, polypropylene,
PBT, polybutene resin, polystyrene type (e.g. AS, ABS, etc.), polyamide type, polyvinyl chloride type, fluororesin (e.g. polyvinyl fluoride,
Various thermoplastic resins such as poly(ethylene trifluoride), polyurethane, etc. can be melted and coated using an extruder, flow coater, etc., coated by dissolving them in a solvent, or coated in powder form. Next, the composite pipe of the present invention will be explained based on examples. Examples Linear high molecular weight PPS (according to ASTMD 1238)
Melt flow was measured at 315.5℃ and 5000g load.
A pipe with an inner diameter of 25 mm and an outer diameter of 28 mm is extruded at a speed of 1 to 2 m/min at an extruder barrel temperature of 290°C. After being continuously obtained and water-cooled while sizing, the outer surface was roughened with 100-grit sandpaper. This extruded pipe was used as the core material 1, and then Polylite NS-260 (Dainippon Ink & Chemicals Co., Ltd. Co., Ltd.'s unsaturated polyester resin) is wrapped around the outer circumferential surface of the core material 1 at a helical angle of ±52° with respect to the axial direction of the pipe, and the temperature is raised to 80 to 120°C by far infrared heating. The FRP layer was completely cured by passing through the air stream for 2 to 10 minutes. The resulting composite pipe had a cross-sectional shape as shown in Figure 1, an outer diameter of 32 mm, and a glass volume content of 50% in FRP. This pipe had approximately 4 times the strength in an internal fracture test compared to an extruded PPS pipe with the same inner and outer diameters.
In addition, hot concentrated sulfuric acid at 80℃ was added to the composite pipe at 1.5 atm for 20 minutes.
I passed the test for a while, but no change was observed.
In addition, the pipe was cut and observed, but no abnormality was found in the PPS layer. Comparative example Epoxy resin (manufactured by Ciel Chemical Co., Ltd., Epicoat
828) 100 parts by weight, liquid acid anhydride as curing agent (manufactured by Dainippon Ink Chemical Co., Ltd., Epicron P-570) 85
parts by weight and 1 part by weight of dimethylbenzylamine as a curing accelerator, impregnated with glass roving, and wound around a mandrel with an outer diameter of 25 mm at a helical angle of ±52°, and then heated at 150°C for 30 minutes. Epoxy-GF cured in oven with outer diameter φ28 and inner diameter φ25
Obtained a filament winding pipe. Furthermore, a double pipe with polyester-GF as the outer layer was obtained in the same manner as in the example using the above pipe as the core material. When heated concentrated sulfuric acid at 80°C was passed through this pipe at 1.5 atm, the load pressure disappeared after about 5 hours, and sulfuric acid was confirmed to leak from the outside of the pipe. When the pipe was cut and the inner surface was observed, it was observed that the epoxy pipe layer had whitened, swelled, and deteriorated.

[Brief explanation of drawings]

FIG. 1 is a partially peeled perspective view of a composite pipe obtained in an example, in which 1 is a PPS core material and 2 is an FRP filament winding layer.

Claims (1)

[Claims] 1. A composite resin pipe with excellent corrosion resistance, chemical resistance, heat resistance, strength, rigidity, etc., which is made by using a polyphenylene sulfide pipe as a core material and coating the surface with fiber-reinforced thermosetting resin.