RU2767551C1 - Polyphenylene sulphide composite materials with finished glass fibres and method for production thereof - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: invention relates to polyphenylene sulphide composite materials and a method for production thereof, intended as structural polymer materials, including polyphenylene sulphide and glass fibres, finished with an organic finishing agent - 4,4'-bis-([(4-phenyl)sulphonyl]phenyl)sulphide.

EFFECT: improving the physical and mechanical properties of the created composite materials due to introduction of finishing agent, which increases wettability of filler and increases intermolecular adhesive interaction between glass fibre and polyphenylene sulphide matrix.

2 cl, 1 tbl, 7 ex

Description

The invention relates to polyphenylene sulfide composite materials with finished glass fibers and a method for their production, intended as structural polymeric materials.

The use of coupling agents in the creation of polymer composite materials (PCMs) makes it possible to modify the structure of the interfacial layer and increase intermolecular interactions at the matrix/filler interface. The development of sizing compositions for the production of polymer composite materials based on superstructural thermoplastics by increasing the adhesion between the polymer, for example, polyphenylene sulfide, and the filler, in particular, glass fiber, in some cases, will increase the performance properties of the composite, which will lead to an increase in the service life of products .

From the prior art, various types of sizing additives used in the creation of polymer composite materials are known. So, the USSR author's certificate for the invention No. 345249 (publ. 07/14/1972, bull. No. 22) describes a method for finishing glass fiber (GF) with organosilicon phosphorus ethers. The main disadvantage of the proposed solution is the use of highly toxic xylene for applying a mixture of monomers to a glass canvas. To remove xylene, it is necessary to raise the temperature to 120°C. The presence of aliphatic groups in the sizing structure will worsen the heat resistance and heat resistance of the composite.

Known composition for processing fiberglass - author's certificate of the USSR No. 1669883, IPC C03C 25.02.1991. The composition contains epoxypropoxypropyltriethoxysilane, γ-aminopropyltriethoxysilane, glycerin or ethylene glycol, acetic acid and distilled water. This composition gives rigidity after sizing, which leads to the formation of a pile of destroyed filaments on the surface of the fiberglass. In the process of fiberglass processing by impregnation with epoxy, phenolic, melamine binders, relief, inhomogeneous areas are formed on the fabric in place of the destroyed filaments, which are difficult to process by pressing. In addition, this sizing has insufficiently high wetting rates of fiberglass.

Known composition for finishing glass fiber materials - patent of Belarus No. 11045, 08.30.2008, IPC C03C 25/00. The composition contains polyfunctional silane brand Z-6224 - 0.5-2.0 wt.%, acetic or formic acid 0.5-2.0 wt.%, wetting agent sandocline PCJ 0.1-0.7 wt.%, the rest - distilled water. The composition is unsuitable for high-temperature 3-D technologies, as it contains acids that will lead to the accumulation of ions, resulting in corrosion of metal surfaces and deterioration of the dielectric properties of composite materials.

A known method for producing a composite material based on a fibrous material finished with a thermoplastic dressing (patent for the invention of the Russian Federation No. 2536969). The invention relates to polymer composite materials used in aircraft, helicopter and automotive industries. The objective of the present invention is to obtain a composite material based on polysulfone, reinforced with carbon or glass fiber fillers with improved compressive strength, and to develop a method for its production. EFFECT: invention makes it possible to increase the compressive strength of polysulfone carbon fiber by 40-50% due to the introduction of a thermoplastic coupling agent - polyhydroxy ether, which increases the wettability of the filler and increases the interaction between the filler and the polysulfone matrix.

The closest analogues are polymer compositions according to RF patent No. 2201423, obtained on the basis of a polymer binder (sizing) and fiberglass or carbon filler. A binder, an oligomer, is preliminarily obtained by reacting aromatic tetracarboxylic acid tetranitrile and aromatic bis-o-cyanamine at a temperature of 170-180°C. The binder is obtained in powder form. The main disadvantage of the above solution is the complexity of the binder synthesis process. An incomplete degree of conversion of monomers during synthesis can lead to the release of side low-molecular reaction products when the binder is combined with the filler at an elevated temperature, and, consequently, to the formation of voids in the composite material, which will lead to a deterioration in the strength characteristics of the material. In addition, powdered finishes may not cover the surface of the filler evenly enough.

The objective of the present invention is to obtain composite materials with improved physical, mechanical and rheological properties based on the matrix polymer polyphenylene sulfide (PPS _D ) reinforced with sized glass fiber (GF) filler.

The task is achieved by the fact that composite materials reinforced with glass fillers are obtained by preliminary treatment of glass fiber with an organic sizing compound - 4,4'-bis-([(4-phenyl)sulfonyl]phenyl)sulfide (FSS) of the following formula:

moreover, the amount of sizing agent to the glass fiber corresponds to 1-4 wt.%, while the amount of sizing glass fiber in the composite material corresponds to 20 wt.%. Processing with such a coupling agent increases the wettability of the filler with polyphenylene sulfide, and makes it possible to repeatedly heat treat the resulting product, if necessary, without changing the properties of the coupling agent.

Composite materials of the present invention are obtained by pre-mixing the polymer matrix and sized glass fiber using a high-speed homogenizer Multi function disintegrator VLM-40B. Then the polymer mixture is subjected to extrusion on a PJSZ twin-screw microextruder from Haitai Machinery (China) with L/D=30, at a maximum temperature of 320°C. Test samples were obtained by injection molding on an SZS-20 injection molding machine from Haitai Machinery (China) at a material cylinder temperature of 330–350°C and a mold temperature of 80°C.

RK-306 glass fiber (IFI Technical Production) and PPS Z-200 grade polyphenylene sulfide from DIC Corporation were used.

Mechanical tests for uniaxial tension were performed on samples in the form of a double-sided blade with dimensions according to GOST 11262-80. The tests were carried out on a universal testing machine Gotech Testing Machine CT-TCS 2000, made in Taiwan, at a temperature of 23°C. Impact tests were carried out according to the Izod method according to GOST 19109-84 on the Gotech Testing Machine, model GT-7045-MD, made in Taiwan, with a pendulum energy of 11 J.

The melt flow index (MFR) was determined on an IIRT-5 device (Russia) at a temperature of 320°C and a load of 5 kgf.

Below are examples illustrating the production of sized glass fibers using FSS.

Example 1. Preparation of finished SV with 1 wt.% FSS

In a three-necked round-bottom flask equipped with a direct condenser, heater and stirrer, 25 g of discrete CB with a fiber length of 0.2 mm is placed and a solution obtained by dissolving 0.25 g of FSS in 60 ml of N,N-dimethylacetamide (DMAA) (0.44 % solution). Turn on the stirrer and stir for 15 minutes at 27°C. Next, the contents of the flask are heated according to the regime: 37°C - 35 min; 57°C -45 min; 77°C - 45 min; 90°C - 45 min.

Then, the contents of the flask are cooled to 20°C and precipitated in 100 ml of distilled water. The finished glass fiber is filtered off and dried in a vacuum oven at 100-110°C for 3 hours, the liquid part is sent for DMAA regeneration. Finished fiberglass yield - 98.7%.

Example 2. Preparation of finished SV with 1.5 wt.% FSS

According to example 1, only the amount of FSS is 0.38 g (0.67% solution). Finished fiberglass yield - 98.3%.

Example 3. Preparation of finished SV with 2 wt.% FSS

According to example 1, only the amount of FSS is 0.51 g (0.9% solution). Finished fiberglass yield - 98.5%.

Example 4. Preparation of finished SV with 2.5 wt.% FSS

According to example 1, only the amount of FSS is 0.64 g (1.13% solution). Finished fiberglass yield - 99.2%.

Example 5. Preparation of finished SV with 3 wt.% FSS

According to example 1, only the amount of FSS is 0.77 g (1.36% solution). Finished fiberglass yield - 99%.

Example 6. Preparation of finished SV with 3.5 wt.% FSS

According to example 1, only the amount of FSS is 0.9 g (1.58% solution). Finished fiberglass yield - 99.3%.

Example 7. Preparation of finished SV with 4 wt.% FSS

According to example 1, only the amount of FSS is 1 g (1.75% solution). Finished fiberglass yield - 98.4%.

From finished SV and PPS _D , PCMs containing 20 wt.% of glass fibers treated with FSS were obtained.

Table 1 presents the compositions, physico-mechanical and rheological properties of composites containing various masses of sizing additives according to examples 1-7.

As can be seen from the data presented, the polymer compositions containing sized glass fibers (Nos. 1-7) are comparable in terms of physicomechanical and rheological characteristics, or exhibit better properties compared to an unfinished sample.

The technical result of the invention is to improve the physical and mechanical properties of the created composite materials due to the introduction of an organic coupling agent - 4,4'-bis-([(4-phenyl)sulfonyl]phenyl) sulfide, which increases the wettability of the filler and increases the boundary interactions between glass fibers and polyphenylene sulfide matrix.

Claims (4)

1. A polyphenylene sulfide composite material intended for use as structural polymeric materials with sized glass fibers, characterized in that an organic compound is used as a coupling agent - 4,4'-bis-([(4-phenyl)sulfonyl]phenyl) sulfide of reduced below formula:

in an organic solvent N,N-dimethylacetamide, and the amount of sizing agent to the glass fiber is 1-4 wt.%, while the amount of sizing glass fiber in the composite material is 20 wt.%. 2. A method for producing polyphenylene sulfide composite materials with glass fibers according to claim 1, including sizing glass fibers by applying a sizing material from a solution followed by drying, characterized in that the sizing is applied from solutions with a mass fraction of 0.44-1.75% in organic solvent and carry out a stepwise rise in temperature according to the regime: 27 ° C - 15 min, 37 ° C - 35 min; 57°C - 45 min; 77°C - 45 min; 90°C - 45 min.