WO2004104089A1 - Long fiber reinforced polypropylene/polyphenyleteher alloy material and its preparation and application - Google Patents

Abstract

The present invention discloses a long fiber reinforced polyproplyene/ployphenylether alloy material, its preparation and application. The fiber in the material of the present invention is oriented in one direction, and its length may be more than 3mm in the final particles, after being produced by injection moulding or extruding, its length may retain 4mm or more, and with reticulate array, thereby it improves the impact resistance, rigidity, creep resistance and dimensional stability of the material. And it is more important that the material may be used in company with other materials, thus extends its application field greatly. The products of the present invention may be prepared by powder impregnated process, melts impregnated process, etc. The long fiber reinforced polypropylene/polyphenylether alloy material of the present invention has excellent tensile property, flexural property and impact resistance, and is used for production of automobile parts, pipes fittings, valves, electric tools, commodities, batteries and storage battery’s shells and parts.

Description

 Long fiber reinforced polypropylene / polyphenylene ether alloy material, preparation method and application thereof

 The invention relates to a continuous long-fiber reinforced thermoplastic material, in particular a continuous long-fiber reinforced polypropylene / polyphenylene ether alloy material.

Background technique

 Polypropylene has the characteristics of high heat resistance temperature, good electrical insulation performance, low water absorption, good fluidity, easy molding, good fatigue resistance, good chemical stability, etc., but it has poor rigidity, large molding shrinkage, unstable dimensions, and Because polypropylene is non-polar, it is incompatible with materials such as ABS and PBT, and it is prone to delamination when mixed, which limits its wide application and is not conducive to the recycling of materials. Polyphenylene ether has the characteristics of stable size, good electrical properties, and excellent mechanical strength. It is polar and can be mixed with ABS, PS, PA, PBT and other materials, but it is easy to swell and stress crack, and has poor melt fluidity. difficult. If polypropylene and polyphenylene ether can be made into alloy materials, it will greatly provide their application fields and reduce costs. The existing polypropylene / polyether ether reinforced alloy material is prepared by adding a compatibilizer, and melting and kneading the fibers with polypropylene, polyphenylene ether and the compatibilizer through a screw extruder. The fibers in this material Destroyed by strong shear, the fiber length is short, about 0.2-0.4 mm. The technology disclosed in WO02 / 28971A1 does not improve the mechanical properties of the material sufficiently, and reduces the application field.

Summary of the Invention

The technical problem to be solved by the present invention is to provide a long-fiber-reinforced polypropylene / polyphenylene ether alloy material and a preparation method and application thereof to overcome the low mechanical properties existing in the prior art, So that limits its application defects.

 The technical idea of the present invention is this-the fibers in the material of the present invention are oriented in the same direction, the length of the fibers can be arbitrary, and the fiber length of the final pellet product is equal to the pellet length. After injection molding or extrusion into a product, The fiber length in the product can be kept to more than 4mm, and arranged in a network, so that the

To improve the impact resistance, rigidity, creep resistance and dimensional stability of the material, more importantly, the material can be mixed with many materials (such as pp, PA, ABS, PS, PBT / PET, PPO, etc.) Has very excellent properties, which can greatly increase the application range of this material.

 The long-fiber-reinforced polypropylene / polyphenylene ether alloy material of the present invention includes a polypropylene resin, a polyphenylene ether or / and a modified polyphenylene ether resin and a continuous long-fiber reinforcing agent, and the continuous long-fiber reinforcing agent mentioned above is finally The average fiber length in the material is 3-20mm, the length of the continuous long fiber reinforcement is the same as the length of the final material body, and it is arranged in parallel along the central axis. The average diameter of the continuous long fiber reinforcement is 3-30um.

 The preferred components and parts by weight of the present invention include:

 Polypropylene resin 200 ~ 600

 Polyphenylene ether / modified polyphenylene ether resin 200 ~ 600

 Continuous long fiber reinforcement 200 ~ 500

 Surface treatment agent 0 ~ 100

 Antioxidant 0 ~ 10

 Compatibilizer 1 ~ 100

Other 0 ~ 300 The modified polyphenylene ether resin is a conventional polyphenylene ether resin modified in whole or in part by an unsaturated carboxylic acid or a functional derivative thereof. The modified polyphenylene ether resin can be prepared by the following method: In the presence of a radical initiator such as an organic peroxide, an azo compound, etc., the polyphenylene ether resin and an unsaturated carboxylic acid or a functional derivative thereof are kneaded in a molten state and reacted. Unsaturated carboxylic acids and their functional derivatives include maleic acid, fumaric acid, itaconic acid, halomaleic acid, cis-4-cyclohexane-1,2-dicarboxylic acid, endo-cis-bicyclo ( 2, 2, 1) -5-heptene-2, 3-dicarboxylic acid; anhydrides, esters, amides or imides of these dicarboxylic acids mentioned; acrylic acid, methacrylic acid; mentioned Esters or amides of these monobasic acids. The method has been reported in the patent CN1101837C, which will not be described in detail in the present invention.

 The continuous long fiber reinforcing agent mentioned may be selected from alkali-free or alkali-containing glass fibers, carbon fibers, metal fibers, and synthetic resin fibers. If extremely high strength is required, carbon fiber may be preferred. If there is no special requirement, alkali-free glass fiber is preferred in terms of cost performance.

 The surface treatment agents mentioned include silane coupling agents, titanate coupling agents, aluminate coupling agents or sulfonyl azide coupling agents, such as KH-550 (γ-aminopropyltriethoxysilane ).

 The antioxidants mentioned are hindered phenol (amine), phosphite antioxidants, or halides of metals from Group I of the periodic table, such as antioxidant 1098 (3,5-di-tert-butyl-4 -Hydroxyphenylpropionyl-hexanediamine), antioxidant 168 (tris (2,4-di-tert-butylphenol ester) phosphite), antioxidant DLTP (dilauryl thiodipropionate), antioxidant 1010 (Tetra [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid] pentaerythritol ester), copper chloride, copper bromide, etc.

The compatibilizers mentioned include maleic anhydride (maleic anhydride), SBS (styrene-butadiene-styrene block copolymer), SMA (styrene-maleic anhydride random copolymer), SEBS (styrene-ethylene-butene-styrene block copolymer) or PP-g-MAH (polypropylene malay One of the anhydride grafts), and its main role is to make polypropylene and polyphenylene ether can be better combined.

 Other components mentioned include flame retardants (halogen-containing flame retardants, red phosphorus, antimony trioxide, etc.), antistatic agents, light stabilizers, colorants, lubricants, release agents and other conventional additives. In addition, various types of commonly used short fibers and particulate inorganic compounds such as talc, calcium carbonate, mica, etc. can also be added. In addition, other thermoplastic resins, including styrene resin, nylon, polyethylene terephthalate, polybutylene terephthalate, acrylonitrile / butadiene, which will not seriously affect the performance of the long fiber reinforced resin can be added. Olefin / styrene copolymer and the like.

 The preparation method of this kind of material can be prepared by powder impregnation method, which includes the following steps: after drying the continuous long fiber reinforcing agent, impregnation through an impregnation tank containing the above resin powder mixture, drying, and then spiral coating The die is covered, then cooled and shaped, and pelletized to obtain the alloy material of the present invention.

 Or it is prepared by the melt impregnation method, including the following steps:

 After the continuous long fiber reinforcing agent is dried, it is immersed in a melt immersion tank containing the above-mentioned resin molten mixture, cooled and shaped, and pelletized to obtain the alloy material of the present invention.

 The long-fiber-reinforced polypropylene / polyphenylene ether alloy material of the present invention has excellent tensile, bending, and impact resistance properties. The material can replace fiber-reinforced PA, ABS, PP, PS, PPO and other materials, and can be widely applied to the following Field:

Auto parts: At present, automobiles mainly use PP, ABS, PA and other materials, which must be sorted and recycled during material recycling. The use of this material can replace existing fiber-reinforced PP, ABS, PA, PVC and other materials, greatly reducing material costs. And can save the trouble of recycling. This material can be used to make car bumpers and wing panels, front modules, dashboards, engine parts T N2004 / 00 475

Fittings: Because this material has chemical resistance, low water absorption, stable dimensions, and good heat resistance, it can replace existing fiber-reinforced PP, PVC, and PA materials, and is used to make valves, pumps, and pipes for fluid transportation. Roads, connectors, water filters, irrigation, components for pools and fountains;

 Power tools, daily necessities, battery cases: Because this material has good rigidity and impact resistance, high heat resistance, good dimensional stability, and chemical resistance, it can replace the existing PP, PVC, ABS, PA , PC, PET / PBT. TPO and other materials, used to make power tools and daily necessities, battery casings and parts.

 The long-fiber-reinforced polypropylene / polyphenylene ether alloy material of the present invention has excellent tensile, bending, and impact resistance (excellent impact resistance in a large temperature range), good chemical resistance, and low water absorption. , Has good dimensional stability, is not easy to warp, has high thermal performance and excellent high temperature creep resistance, and has paintability-when used in automotive and non-automotive applications, use most paint systems on the market A grade surface finish can be obtained. What's more important, this material has good compatibility with other materials (PP, ABS, PA, PBT, PET, PS, PPO, etc.), it can make complicated materials to be used together. The classification work of reducing the use and recycling of materials has been greatly improved.

Brief description of the drawings.

 Figure 1 is a flow chart of the powder impregnation method.

 Fig. 2 is a flow chart of the melt dipping method.

detailed description

Referring to FIG. 1, the powder impregnation method includes the following steps − 04 000475 Continuous long fiber reinforcing agent is pulled out from the creel 1 and the fiber is dried by the oven 2. After drying, the fiber is impregnated by an impregnation tank 3 containing 30 ~ 80 mesh of the above resin powder mixture, and the tank is filled with 3 -9 sets of tension guide rollers 5, the angle between the tension guide rollers is controlled at 30-60 degrees, which is conducive to fiber squeezing and dispersion, and an ultrasonic generator 4 is installed to disperse the fibers, so that the powder is fully uniformly impregnated and the electrostatic generator 6. Make the powder easily adsorbed on the fiber, and then heat-melt and adhere through the infrared heating drying tunnel 7. Use infrared heating to be uniform and stable enough to generate less air flow. It is also confined to prevent oxidation when the resin is heated. The type coating die 8 adopts the spiral type to facilitate uniform and stable resin coating, and then is cooled and shaped by the cooling setting device 9 and finally pulled by the tractor 10 and then pelletized by the pelletizer 11 to obtain a particle length of 3-20mm, the fiber length is consistent with the product particle length, and is dispersed parallel to the center axis of the product.

 The above method uses ultrasonic waves in the powder impregnation tank to disperse the fibers well, so that the resin powder is fully and uniformly impregnated into the fibers. This process uses closed-type infrared heating in the heating method, which can block the oxygen prevention material. It oxidizes, reduces heat energy loss, and heats evenly and stably. It generates less air flow, which helps the powder adhere to the fiber. This process uses a spiral coating die on the coating die, which can make the resin Spiral advances in the die, making the coating uniform and stable.

 The mentioned melt impregnation method includes the following steps:

The fibers are pulled out of the creel 1 and the fibers are dried by an oven 2. After drying, the fibers pass through a melt impregnation tank 3 in which the above-mentioned resin molten mixture is placed. This tank is equipped with 2-12 sets of tension guide rollers 5, which are adjacently guided. The angle between the rollers is controlled at 30-60 degrees. The tension guide rollers are helpful for squeezing and dispersing the fibers, and it is also beneficial for the molten resin to be fully and uniformly impregnated into the fibers. N2004 / 000475 An ultrasonic generator 4 is also installed in the body to disperse the fibers, so that the resin can be fully and uniformly and stably impregnated into the fibers and the stirring device 17, and the molten resin is stirred to prevent dead spots and prevent oxidative decomposition. Fibers After passing through the melt-impregnation tank 3, cooling and setting is performed by the cooling and setting device 9 and then pulled by the tractor 10 and pelletizing by the pelletizer 11 to obtain the final product. The particle length of the product is 6-20mm, and the fiber length and particle in the product are The length is consistent and dispersed parallel to the central axis. This process installs 2-12 sets of pressure rollers 5 in the melt immersion tank, and the angle is controlled at 30-60 degrees, which is conducive to the resin being fully and uniformly impregnated into the fiber; this process is equipped with an ultrasonic device in the melt immersion tank. The fibers are sufficiently dispersed, so that the resin impregnation is sufficiently uniform and stable.

 Example 1

 The glass fiber is made into a polyphenylene ether prepreg through a powder impregnation process, and is heated and cured at 230 ° F. Then, the prepared prepreg is directly passed through a spiral coating die of a single screw extruder. The melt inside is polypropylene resin, mixed with antioxidant 1010 (tetra [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionic acid] pentaerythritol ester) and compatibilizer maleic anhydride Finally, use a pelletizer to cut the extruded continuous glass fiber reinforced polypropylene / polyphenylene ether alloy material into 9 mm pellets.

 The specific components are as follows:

 Polypropylene resin 400

 Polyphenylene ether resin 200

 Continuous fiberglass 400

Antioxidant 1010 5 0475 Its properties are listed in Table 1.

 Example 2

 The continuous glass fiber was passed through a melt-impregnation tank, and the melt in the tank was polypropylene and polyphenylene ether resin, and was mixed with an antioxidant 1010 (tetra [3- (3,5-di-tert-butyl-4-hydroxyphenyl) ) Propionic acid] pentaerythritol ester) and compatibilizer SMA (styrene-maleic anhydride random copolymer), and finally cut the extruded continuous glass fiber reinforced polypropylene / polyphenylene ether alloy material into 9mm with a pelletizer Pellets.

 The specific components are as follows:

 Polypropylene resin 400

 Polyphenylene ether resin 200

 Continuous fiberglass 400

 Antioxidant 1010 5

 SMA (styrene-maleic anhydride random copolymer) 20

 Its performance is listed in Table 1.

 Example 3

 The continuous glass fiber was passed through a molten impregnation tank. The melt in the tank was polypropylene and polyphenylene ether resin, and was mixed with an antioxidant 1010 (tetra [3- (3, 5-di-tert-butyl-4-hydroxyphenyl). ) Propionic acid)] Pentaerythritol ester) and compatibilizer SEBS (styrene-ethylene-butene-styrene block copolymer), and finally a continuous glass fiber reinforced polypropylene / polyphenylene ether drawn by a pelletizer The alloy material was cut into 9mm pellets. The glass fiber content is controlled at about 30%.

 The specific components are as follows:

Polypropylene resin 200 Polyphenylene ether resin

 Continuous glass fiber

 Antioxidant 1010

 SEBS

 Its performance is listed in Table 1.

 Example 4

 The continuous glass fiber was passed through a molten impregnation tank, and the melt in the tank was polypropylene and polyphenylene ether resin, and was mixed with a surface treatment agent KH-550 (γ-aminopropyltriethoxysilane) and PP-g-MAH (Polypropylene maleic anhydride graft). Finally, the continuous glass fiber reinforced polypropylene / polyphenylene ether alloy material that was pulled and extruded was cut into 9 mm pellets by a pelletizer.

 The specific components are as follows-polypropylene resin 300

 Polyphenylene ether resin 200

 Continuous fiberglass 400

 Surface treatment agent KH-550 20

 PP-g-MAH 100

 Its performance is listed in Table 1. The performance data of the mixing test are shown in Table 2.

 Example 5

The continuous glass fiber was passed through a molten impregnation tank, and the melt in the tank was polypropylene and polyphenylene ether resin, and mixed with a surface treatment agent KH-550 (γ-aminopropyltriethoxysilicon) and PP-g- MAH (polypropylene maleic anhydride graft) and ABS (acrylonitrile-butadiene-styrene) resin, and finally the extruded continuous glass fiber reinforced polypropylene / polyphenylene ether alloy was cut with a pelletizer. The material was cut into 9mm pellets.

 The specific components are as follows:

 Polypropylene resin 200

 Polyphenylene ether resin 200

 Continuous fiberglass 300

 Surface treatment agent KH-550 20

 PP-g-MAH 100

 ABS (acrylonitrile-butadiene-styrene) 200

 Its performance is listed in Table 1.

 Example 6

 The continuous glass fiber was passed through a molten impregnation tank, and the melt in the tank was polypropylene and polyphenylene ether resin, and was mixed with a surface treatment agent KH-550 (γ-aminopropyltriethoxysilane) and PP-g-MAH (Polypropylene maleic anhydride graft) and nylon 6 resin, and finally the drawn glass fiber reinforced polypropylene / polyphenylene ether alloy material was cut into 9 mm pellets with a pelletizer.

 The specific components are as follows:

 Polypropylene resin 200

 Polyphenylene ether resin 200

 Continuous fiberglass 300

 Surface treatment agent KH-550 20

 PP-g-MAH 100

 Nylon 6 resin 200

Its performance is listed in Table 1. Comparative Example 1

 According to the component ratio of Example 4, the conventional fiber-reinforced thermoplastic manufacturing process was used to directly enter the glass fibers and other components into a twin-screw extruder with an aspect ratio of 36: 1, and the pellet length was 3mm. , The diameter is lmm. Its performance is listed in Table 1.

 Comparative Example 2

 According to the component ratio of Example 5, the conventional fiber-reinforced thermoplastic manufacturing process was used to directly enter glass fiber and other components into a 36: 1 aspect ratio twin-screw extruder for pelletization, and the pellet length was 3 mm. , The diameter is lmm. Its performance is listed in Table 1.

 Comparative Example 3

 According to the component ratio of Example 6, the conventional fiber-reinforced thermoplastic manufacturing process was used to directly enter the glass fiber and other components into a 36: 1 aspect ratio twin-screw extruder for pelletization, and the pellet length was 3 mm. , The diameter is lmm. Its performance is listed in Table 1.

According to the data in Table 1, it is not difficult to see that the long-fiber-reinforced polypropylene / polyphenylene ether alloy material has significantly better tensile, bending, and impact resistance than the chopped fiber-reinforced polypropylene / polyphenylene ether alloy material, and has shrinkage. Smaller rate means better dimensional stability and smaller vertical and horizontal shrinkage gap. The resulting product is less prone to warp. Compared with long fiber reinforced polypropylene materials, it has the advantages of slower burning speed and lower smoke density. It is more important that long fiber reinforced polypropylene / polypropylene The phenyl ether alloy material has good compatibility with other resins, and can be mixed with many commonly used materials, such as ABS, PP, _PA, etc. (see Table 2 for mixing test performance data). It can replace many engineering plastics and be applied to multiple Field, and it is easy to recycle and reuse the materials of the whole machine (such as automobiles, electrical appliances). Table 2 shows that when the materials of the present invention are used in the whole machine, the materials can be recycled and reused without re-classifying the materials. The longer the glass fiber length in the material of the present invention, the better the performance The more excellent, but too long fibers will affect the post-processing molding of the material, so we recommend glass fiber length of 6-20mm. In addition, processing conditions have a great impact on the properties of the final material.

合试验性能数据表（测试标准 ASTM) 测试项目 混合 1 混合 2 混合 3 实施例 4材料 75% 75% 75%

Test Performance Data Sheet (Test Standard ASTM) Test Items Mix 1 Mix 2 Mix 3 Example 4 Material 75% 75% 75%

ABS resin 25%

PA resin 25%

PP resin 25% tensile strength 85 100 95 elongation at break 5 8 7

Izod impact strength KJ / m ² 46 50 65

Izod notched impact strength KJ / m ² 21 25 30 Bending strength Mpa 145 150 155 Bending modulus Mpa 6800 7100 8000

 0.47 /

 Shrinkage% 0.18 / 0.23 0.16 / 0.25

 0.55

 Deformation temperature ° C 150 163 152

Claims

Rights request 1. A long-fiber reinforced polypropylene / polyphenylene ether alloy material, comprising: a polypropylene resin, a polyphenylene ether or / and a modified polyphenylene ether resin and a continuous long-fiber reinforcing agent; The average fiber length of the fiber reinforcement in the final material is 3-20 mm.  The alloy material according to claim 1, wherein the length of the continuous long-fiber reinforcing agent is the same as the length of the final material body, and is arranged in parallel along the central principal axis.  3. The alloy material according to claim 1, wherein the continuous long-fiber reinforcing agent has an average diameter of 3-30um.  The alloy material according to claim 1, 2 or 3, characterized in that the components and parts include:  Polypropylene resin 200 ~ 600

200 ~ 600  Continuous long fiber reinforcement 200 ~ 500  Surface treatment agent 0 ~  Antioxidant 0 ~ 10  Compatibilizer Bu 100  Other 0 ~ 300  The alloy material according to claim 4, wherein the modified polyphenylene ether resin is a conventional polyphenylene ether resin which is modified in whole or in part by an unsaturated carboxylic acid or a functional derivative thereof. Product. The alloy material according to claim 5, wherein the unsaturated carboxylic acid and Its functional derivatives include maleic acid, fumaric acid, itaconic acid, halogenated maleic acid, cis-4-cyclohexane-1,2-dicarboxylic acid, and endo-cis-bicyclo (2, 2, 1 ) -5-heptene-2,3-dicarboxylic acid, anhydrides, esters, amides or imides of said dicarboxylic acids; acrylic acid, methacrylic acid; esters or amides of said monobasic acids .  The alloy material according to claim 4, wherein the continuous long-fiber reinforcement is selected from alkali-free or alkali-containing glass fibers, carbon fibers, metal fibers, and synthetic resin fibers.  The alloy material according to claim 4, wherein the surface treatment agent includes a silane coupling agent, a titanate coupling agent, an aluminate coupling agent, or a sulfonyl azide coupling agent. .  9. The alloy material according to claim 4, wherein the antioxidant is a hindered phenol (amine) -based, phosphite-based antioxidant, or a halide of a Group I metal of the Periodic Table, Copper chloride or copper bromide.  The alloy material according to claim 4, wherein the compatibilizing agent comprises one of maleic anhydride, SBS, SMA, SEBS, or PP-g-MAY.  The alloy material according to claim 4, wherein the other components include a flame retardant, an antistatic agent, a light stabilizer, a colorant, a lubricant or a release agent, and talc, carbonic acid. Calcium, mica and / or other thermoplastic resins. The method for preparing an alloy material according to any one of claims 1 to 11, further comprising the steps of: after drying the continuous long-fiber reinforcing agent, passing through the impregnation tank (3) in which the resin powder mixture is placed ) Dipping, drying, and covering with a coating die (8), then cooling and shaping, and pelletizing, to obtain the alloy material of the present invention. The method for preparing an alloy material according to claim 12, characterized in that the fibers and the powder are dispersed by ultrasonic waves, the powder is adsorbed on the fibers by static electricity, and melt adhesion is performed by infrared heating.  The method for preparing an alloy material according to any one of claims 1 to 11, further comprising the steps of: after drying the continuous long-fiber reinforcing agent, passing the molten dipping tank (3 ) Dipping, cooling and sizing, to obtain the alloy material of the present invention.  The method for preparing an alloy material according to claim 14, characterized in that the dispersed fibers are squeezed in a melt-impregnation tank by 2-12 sets of pressure rollers (5).  16. The application of the alloy material according to any one of claims 1 to 11, characterized in that it is used for manufacturing automobile parts, pipe fittings, valve fittings, electric tools, daily necessities, batteries, battery casings and parts.