TW201520268A - Polymer composite material and products and manufacturing method thereof - Google Patents

Abstract

A kind of polymer composite material includes at least two kinds of polymer matrix and a polymer filler dispersed in the matrix, wherein the polymer matrix comprises rubber substrate, and the filler accordingly mixed with the rubber substrate is dispersed in the polymer matrix. In addition, the present invention also provides a kind of manufacturing method for the polymer composite material, and polymer products prepared from said polymer composite material.

Description

Polymer composite material, product thereof and preparation method

The invention relates to a polymer material; in particular to a polymer composite material, a product thereof and a preparation method.

In recent years, polymer technology has flourished, and because of its excellent physical and chemical properties and excellent processing properties, polymer materials have been widely used in clothing, food, housing, transportation, electronics, biomedical and aerospace industries. For example, plastics, rubber, fiber, tires, painting, adhesive, synthetic leather, etc. in the traditional industry are examples.

With the development of modern science and technology, people's requirements for the performance of polymer materials are increasingly diversified. Single homopolymers or copolymers have often been difficult to meet a variety of different requirements. People began to use existing polymer materials and blended to prepare composites with new functions to meet the new requirements of polymer materials for various industrial applications, thus improving the performance of original polymers or forming new products. The performance of polymer blends has become a fast-growing field in polymer science.

However, there are still many places for further improvement in the preparation of the above polymer composite materials, such as increasing the physicochemical properties of the polymer composite material, sometimes at the expense of processability, such as difficulty in granulation and uneven dispersion. , can not be hot melted out and so on. Therefore, the prior art has no improvement and needs to be improved.

One of the main objects of the present invention is to provide a polymer composite material which can have both characteristics and workability.

One of the main objects of the present invention is to provide a polymer product obtained by a polymer composite material having good properties and processability.

In order to achieve the above object, a preferred embodiment of the present invention provides a polymer composite material comprising at least two polymer substrates and a filler dispersed in the polymer matrix, wherein the polymer matrix comprises a rubber substrate .

In order to achieve the above object, a further preferred embodiment of the present invention provides a polymer composite material comprising at least two polymer substrates and a filler, wherein the polymer matrix comprises a rubber substrate, and the filler is The rubber substrate is mixed to disperse it in the polymer matrix.

In order to achieve the above object, another preferred embodiment of the present invention provides a polymer product obtained from a polymer composite material, wherein the polymer composite material comprises at least two polymer matrix bodies and is dispersed at the same height. A filler in a molecular matrix, wherein the polymer matrix comprises a rubber substrate, and the filler is mixed with the rubber substrate to be dispersed in the polymer matrix.

In order to achieve the above object, a further preferred embodiment of the present invention provides a method for preparing a polymer composite material comprising mixing a filler material with a rubber substrate to disperse the filler material into the polymer matrix.

The polymer composite material of the present invention is capable of uniformly adhering the filler to the rubber by at least the rubber therein, or it can be said that the rubber is used as a tackifying dispersant, so that the filler can be uniformly dispersed or blended at the end. In the molecular matrix, the polymer composite material can have both characteristics and processability to facilitate the preparation of the polymer composite material and its products.

The present invention will be further understood by the following detailed description of the preferred embodiments of the invention.

Example 1: A lightweight polyurethane-based polymer composite material and a process for preparing the same.

The raw materials required in this embodiment include ethylene propylene diene rubber, cork stopper and polyurethane resin, and take 1,193 g, 1,193 g, and 1,590 g, respectively; wherein, for example, the polyurethane has a hardness of 85 A ( Shore Hardness) with a specific gravity of 1.3. After preparing the raw materials, first add EPDM rubber and cork to the compounding machine, and continue stirring at 150 rpm for one hour at room temperature to make the cork evenly adhere to the natural rubber; then, add the polyamino group. The formate resin is continuously stirred at 150 rpm for one hour to prepare a preliminary product; finally, the preliminary product is subjected to granulation by a single screw extruder, and the process conditions can be controlled, for example, at a temperature of 180 ° C. The screw rotation speed is 70 rpm, so that a lightweight polyurethane polymer composite material can be obtained, and the hardness can be reduced to 65 A, and the specific gravity can be reduced to 1.0.

It can be seen from the above that in the present embodiment, the rubber (here, EPDM rubber) is used to finally uniformly disperse the filler (cork) in the polymer matrix (polyurethane) to make the final polymer. Composite materials can combine the required properties (lightweight) and processability, and contribute to the preparation of polymer composites and their products.

Example 2: A lightweight polyurethane-based polymer composite and a process for preparing the same.

This embodiment is basically the same as the material prepared in the above embodiment 1. The main difference is that in the process of the preparation, the polymer matrix itself which is not polymerized is involved, but the corresponding matrix of the polymer matrix Body and corresponding starter. For example, this example selects the corresponding monomer of the polyurethane and the corresponding initiator, namely diphenylmethane diisocyanate, and polybutylene adipate and butanediol, respectively. It should be noted that the above monomers and initiators are not limited, and monomers including isocyanate, such as toluene diisocyanate, hexamethylene diisocyanate, and initiators including polyols, such as common ones, are not limited. Various polyether polyols or polyester polyols can be used to synthesize polyurethane. The preparation method of this embodiment will be described below.

First, 1,000 grams of polybutylene adipate, 90 grams of butanediol, 500 grams of diphenylmethane diisocyanate, 1,193 grams of EPDM rubber, and 1,193 grams of cork were prepared.

Next, the ingredients other than diphenylmethane diisocyanate were first added to the mixer and continuously stirred at 150 rpm for one hour. After stirring evenly, diphenylmethane diisocyanate was added and continued at 150 rpm. After stirring for thirty seconds, it is taken out and allowed to stand for one day to prepare a preliminary product. Finally, after the shaped product is pulverized, the product is extruded and granulated by a single screw extruder, and the process conditions are, for example, the same. In the first embodiment, a polyurethane-based polymer composite material was obtained in such a manner that its characteristics were close to those of the above-described first embodiment, that is, it was also lightweight, and the workability was good. It is to be noted that, in this embodiment, the polymer matrix is simultaneously polymerized in the process of preparing the composite material. Therefore, the polymer composite material of the present embodiment may contain not only the polymer matrix but also the polymer matrix. The corresponding monomer or/and prepolymer of the reaction or unreacted polymer matrix, and the corresponding initiator of the polymer matrix or/and its prepolymer.

Example 3: Lightweight polyurethane-based polymer composite material and a preparation method thereof.

This embodiment is basically the same as the materials prepared in the above embodiments 1 and 2. The main difference is that the present embodiment further changes the polybutylene adipate of Example 2 to its monomer. Alternatively, adipic acid, and in the process of preparing the composite material of the present embodiment, simultaneously synthesize polybutylene adipate, for example, during the preparation, adding dibutyltin oxide, phosphorous acid and optionally The chain extender (for example, hexamethylenedihexylamine) is combined with the existing butanediol to synthesize polybutylene adipate. The preparation method of this embodiment will be described below.

First, 658 grams of polyadipate, 495 grams of butanediol, and 1,193 grams of cork are mixed, and at the same time, for example, the polybutyl adipate is synthesized by the above polymerization method, so that the cork is uniformly dispersed in the polyhexan In the dibutyl acid ester; then, 1,193 g of ethylene propylene diene monomer and 500 g of diphenylmethane diisocyanate are added to the blender for mixing, and subsequently the same steps as in the second embodiment can be used. A lightweight polyurethane-based polymer composite material. Similarly, the polymer composite material obtained in the present embodiment may also contain a corresponding monomer or/and a prepolymer of a polymer resin initiator, such as adipic acid or polybutylene adipate oligomerization. Things.

Example 4: A free-flowing polyurethane-based polymer composite material and a process for preparing the same.

This embodiment is substantially the same as the above-described Embodiment 1, and the main difference is that the material of the filler is replaced with a waste tire rubber powder from a cork stopper. The preparation method thereof will be described below.

First, 795 grams of EPDM rubber and 795 grams of waste tire rubber powder were placed in the blender and continuously stirred at room temperature and 150 rpm for one hour to uniformly attach the waste tire rubber powder to the natural rubber. Then, add 1,590 grams of polyurethane, and polyaminocarbamide The ester selection melt flow index (Melt Flow Index, hereinafter referred to as MI index) is 2.6 g/10 min at 190 ° C and 8.7 kg and the hardness is 85 A; then, stirring is continued for one hour at a rotation speed of 150 rpm, and finally The single-screw extruder performs the extrusion granulation operation, and the process conditions can be controlled, for example, at a temperature of 180 ° C and a screw rotation speed of 70 rpm, so that a flowable polyurethane-based polymer composite material can be obtained. The MI index of the present example was measured to be raised to 12.0 g/10 min under the same measurement conditions. Therefore, the polyurethane-based polymer composite material of the present example was improved in fluidity due to a decrease in viscosity. Incidentally, the hardness is also slightly reduced to 75A.

Therefore, in the present embodiment, the rubber (ethylene propylene diene monomer) is used to finally uniformly disperse the filler (waste tire rubber powder) in the polymer matrix (polyurethane) to complete the final polymer compound. The material has both the required properties (high fluidity) and processability. In addition, the hardness can also be moderately reduced. Similarly, in other embodiments, the corresponding monomer of the polymer matrix and the initiator may be added instead.

Example 5: A slip-resistant, easy-to-form and wear-resistant polyurethane-based polymer composite material and a preparation method thereof.

This embodiment is substantially the same as the above-described Embodiment 4, and the main difference is that the material of the filler material further increases the natural graphite powder. The preparation method of this embodiment will be described below.

First, add 84 grams of natural rubber, 84 grams of waste tire rubber powder and 795 grams of natural graphite powder to the blender, and continue stirring at 150 rpm for one hour at room temperature to make waste tire rubber powder and natural graphite. The powder was evenly attached to the rubber. After stirring evenly, 1,590 g of polyurethane was added, and stirring was continued for one hour at a rotation speed of 150 rpm. Finally, the granulation was carried out by a single screw extruder at 180 ° C / 70 rpm. Thus, a flowable polyurethane-based polymer composite material can be obtained. After measurement, compared to the molding time of a single polyurethane (36 seconds), The molding time of the polyurethane-based polymer composite material of the present embodiment was further shortened to 22 seconds. In addition, the addition of the waste tire rubber powder can also improve the anti-slip effect of the composite material. For example, in the subsequent injection molding operation of the embodiment, the driving force can be increased from 0.75 to 1.2 kg. As for the addition of the natural graphite powder, the wear resistance of the present embodiment can be improved from 62.3 to 52.0 mm3.

The polymer matrix described in the above examples is exemplified by a polyurethane. However, it should be understood that the polymer matrix can be adjusted according to the requirements of the polymer product. In this regard, the polymer matrix of the present invention may be selected from a thermoplastic resin or a thermosetting resin, for example, polyethylene, polypropylene, polyvinyl chloride, polystyrene, ABS resin, polymethyl methacrylate. And a thermoplastic polyurethane (TPU) or the like, and the latter includes, for example, a phenol resin, a urethane resin, an epoxy resin, an unsaturated polyester resin, or the like. If the polymer matrix structure is classified according to the polymer main chain structure, a polyolefin resin, a styrene resin, a vinyl resin, a urethane resin, an anthracene resin, a fluororesin or the like can be used. Therefore, the polymer matrix of the present invention is not limited, and corresponding monomers and initiators can also be used. The following is another description of another polymer matrix material.

Example 6: A lightweight polymethyl methacrylate polymer composite and a preparation method thereof.

This embodiment is substantially the same as the above-described first embodiment, and the main difference is that the material of the polymer matrix is replaced by polyurethane to polymethyl methacrylate, and the type of the rubber substrate is also replaced. The preparation method of this embodiment will be described below.

First, similar to the first embodiment, that is, the same weight parts of styrene isoprene rubber and cork are firstly stirred in a mixer to stir the cork stopper uniformly on the natural rubber, and then, Add 1,590 grams of polymethyl methacrylate and selected polymethacrylic acid The hardness of the methyl ester is 64D and the specific gravity is 1.2; then the stirring is continued for one hour at 150 rpm; finally, the granulation operation is carried out by a single screw extruder at 140 ° C / 70 rpm, so that a lightweight can be obtained. A polymethyl methacrylate-based polymer composite material having a hardness of 98 A and a specific gravity of 0.95. It can be seen that the embodiment can also achieve the requirements of light weight and processability.

Example 7: A lightweight polymethyl methacrylate-based polymer composite material and a process for preparing the same.

This embodiment is basically the same as the material prepared in the above embodiment 6, the main difference is that in the process of the preparation, the polymer matrix itself which is not polymerized is involved, but the corresponding monomer and Corresponding starter. For example, the present embodiment selects the corresponding monomer of polymethyl methacrylate and the corresponding initiator, that is, methyl methacrylate and a common polymerization initiator, respectively. In addition, the rubber substrate is replaced here with natural rubber. The preparation method of this embodiment will be described below.

First, 1,590 grams of methyl methacrylate, 1,193 grams of natural rubber, 1,193 grams of cork and 3 grams of polymerization initiator were continuously stirred in a blender at room temperature and 150 rpm for one hour. Then, using a single-screw extruder, the granulation operation is carried out at 140 ° C / 70 rpm, so that a lightweight polymethyl methacrylate polymer material can be obtained, and its characteristics are close to those of the above-mentioned Example 6, It is also lightweight.

Example 8: A lightweight, easy-to-process, wear-resistant polymethyl methacrylate polymer composite and a preparation method thereof.

This embodiment is substantially the same as the above-mentioned Embodiment 6. The main difference is that the present embodiment further adds two other filler materials, namely tire rubber powder and graphite powder, to improve the fluidity and wear resistance of the final composite material. . In addition, the type of rubber substrate is also replaced. The preparation method will be described below.

First, 80 g of styrene butadiene rubber, 160 g of tire rubber powder, 320 g cork stopper and 80 g of graphite powder were continuously stirred in a blender at room temperature and 150 rpm for one hour. The filler was uniformly attached to the rubber; then, 1,590 g of polymethyl methacrylate was added, and the hardness was 64 D, the specific gravity was 1.2, and stirring was continued for one hour at a rotation speed of 150 rpm, and then a single screw extruder was used. The extrusion granulation operation was carried out at 140 ° C / 70 rpm, so that a lightweight, easy-to-process, wear-resistant polymethyl methacrylate polymer composite material was obtained, and its hardness was reduced to 55 D, and the specific gravity was lowered. 1.1. As for the fluidity, the MI index was increased from 4.8 g/10 min to 25.6 g/10 min under the same measurement conditions for processing. As for wear resistance, it can be increased by 58.7mm3 from 62.3.

Example 9: A lightweight, easy-to-process, wear-resistant polymethyl methacrylate polymer composite and a preparation method thereof.

This embodiment differs from the above-described embodiment 8 only in that the filler material further increases the inorganic foaming agent. Further, the rubber substrate is further subjected to hydrogenation. In detail, in the present embodiment, 10 grams of the inorganic foaming agent is first mixed with the hydrogenated styrene/butadiene rubber together with other filler materials to uniformly adhere the filler to the rubber, and then through the same After the process of Example 8, a polymethyl methacrylate polymer composite material which is lighter, easier to process and wear-resistant can be obtained. It is worth mentioning that because of the addition of inorganic blowing agent, the specific gravity is greatly reduced to 0.5. Secondly, the hardness is also reduced to 85A, and the wear resistance is increased to 23.6mm3.

Example 10: UV-resistant polymethyl methacrylate-based polymer composite material and a preparation method thereof.

This embodiment is substantially the same as the above-described embodiment 6, and the main difference is that the material of the filler material is replaced by a cork stopper into montmorillonite. The preparation method thereof will be described below.

First, put 80 grams of natural rubber with 80 grams of montmorillon The soil was continuously stirred in a mixer for 150 hours at room temperature and 150 rpm to uniformly adhere the montmorillonite to the rubber; then, 1,590 g of polymethyl methacrylate was added, and the hardness was 64 D, and the specific gravity was 1.2. And further stirring at 150 rpm for one hour, and finally, using a single screw extruder to perform the granulation operation at 140 ° C / 70 rpm, so that a UV-resistant polymethyl methacrylate system can be obtained. Molecular composites. It is worth mentioning that due to the addition of montmorillonite, the UV resistance of the composite material can be improved. Specifically, the test piece of the present example was slightly yellowed after being irradiated for four days at a normal temperature at an ultraviolet ray having a wavelength of 240 to 300 nm. Another mention is that the hardness is also slightly increased to 66D, and the specific gravity is slightly increased to 1.3.

Although the above embodiments are exemplified by only a few kinds of fillers, it is understood that the selection and matching of the fillers are related to the properties required for the polymer composite. Therefore, according to the required characteristics, the filler material can be at least freely recovered from polymer materials, recycled fibers, cork, rubber particles, bamboo charcoal, zeolite, foaming agent, wood powder, clay, clam shell, bagasse, coffee grounds, At least one of the group consisting of tea leaves, waste newspaper, diatomaceous earth, ceramic powder, graphite powder, limestone, and metal powder, but is not limited thereto. Wherein, the recycled polymer material may be selected from the group consisting of waste tire rubber powder, polyethylene, polyvinyl chloride, polypropylene, polystyrene, polyethylene terephthalate, acrylic, fluoroplastic, polyphthalamide. At least one of the group consisting of amine, polycarbonate, nylon, and ABS plastic is not limited thereto.

In addition, the above embodiments are exemplified by natural and synthetic rubbers, and the scope thereof includes, in addition to the generally common synthetic rubber, a modified rubber, for example, a rubber grafted with malic anhydride; Synthetic rubber such as free butadiene rubber, styrene butadiene rubber, nitrile rubber, neoprene, butadiene rubber, ethylene propylene rubber, polysulfide rubber, acrylate rubber, fluororubber, silicone rubber, butyl rubber, isoprene Rubber, EPDM rubber, styrene butadiene rubber, hydrogenated styrene/butadiene rubber, styrene ethylene/butyl At least one of the group consisting of an styrene rubber and a styrene isoprene copolymer is not limited thereto.

Further, if the polymer composite material of the above embodiments is used to form a polymer product, it can be achieved by a usual injection molding process, but is not limited thereto; other molding processes such as press molding may be employed. Since the polymer molding process has been a well-known technique, it will not be repeated here.

In summary, the polymer composite material of the present invention is capable of uniformly adhering the filler to the rubber by at least the rubber therein, or it can be said that the rubber is used as a viscosity-increasing dispersant, so that the filler material can be uniformly dispersed or It is incorporated into the polymer matrix so that the polymer composite material can have both characteristics and processability, thereby contributing to the preparation of the polymer composite material and its products. At the same time, the invention can also realize the recycling and recycling of the filler material to protect the ecology. surroundings.

The above is only a preferred embodiment of the present invention, and equivalent changes to the scope of the present invention and the scope of the patent application are intended to be included in the scope of the present invention.

Claims (28)

A polymer composite material comprising at least two polymer substrates and a filler dispersed in the polymer matrix, wherein the polymer matrix comprises a rubber substrate. The polymer composite according to claim 1, wherein the polymer matrix comprises at least one resin and the rubber substrate. The polymer composite according to claim 2, wherein the resin comprises polyurethane, or polymethyl methacrylate. The polymer composite according to claim 3, wherein the polyurethane is a thermoplastic polyurethane. The polymer composite material according to claim 2, further comprising a corresponding monomer or/and a prepolymer of the resin, and a corresponding initiator or/and a prepolymer thereof. The polymer composite according to claim 5, wherein the resin is a thermoplastic resin. The polymer composite material according to claim 5, wherein the resin is a thermosetting resin. The polymer composite material according to claim 5, wherein the resin is selected from the group consisting of a polyolefin resin, a styrene resin, a vinyl resin, a polyurethane resin, an unsaturated polyester resin, an epoxy resin, a phenol resin, a urea resin, and At least one of the group consisting of polymethacrylates. The polymer composite according to claim 5, wherein the resin comprises a polyurethane, and the monomer comprises an isocyanate, and the initiator comprises a polyol. The polymer composite according to claim 9, wherein the monomer comprises diphenylmethane diisocyanate. The polymer composite according to claim 9, wherein the initiator comprises polybutylene adipate, and butylene glycol. The polymer composite material according to claim 11 further comprising adipic acid. The polymer composite according to claim 5, wherein the resin comprises polymethyl methacrylate, and the polymer composite further comprises a methyl methacrylate monomer. The polymer composite material according to claim 1, wherein the rubber substrate is a natural rubber. The polymer composite material according to claim 1, wherein the rubber substrate is a synthetic rubber. The polymer composite according to claim 1 or 3, wherein the rubber substrate comprises ethylene propylene rubber, styrene isoprene rubber, styrene butadiene rubber or hydrogenated styrene/butadiene rubber. The polymer composite material according to claim 16, wherein the ethylene propylene rubber is ethylene propylene diene monomer. The polymer composite material according to claim 1, wherein the filler is selected from the group consisting of recycled polymer materials, recycled fibers, cork stoppers, rubber particles, bamboo charcoal, zeolite, wood flour, clay, clam shell, bagasse, At least one of the group consisting of coffee grounds, tea leaves, waste newspaper, diatomaceous earth, ceramic powder, graphite powder, limestone, and metal powder. The polymer composite material according to claim 18, wherein the recycled polymer material is selected from the group consisting of tire rubber powder, polyethylene, polyvinyl chloride, and polypropylene. At least one of the group consisting of olefin, polystyrene, polyethylene terephthalate, acryl, fluoroplastic, polyimine, polycarbonate, nylon, and ABS plastic. A polymer composite material comprising at least two polymer matrixes and a filler material, wherein the polymer matrix comprises a rubber substrate, and the filler material is mixed with the rubber substrate to be dispersed in the same height Molecular matrix. The polymer composite according to claim 20, wherein the polymer matrix comprises at least one resin and the rubber substrate. The polymer composite material according to claim 21, further comprising a corresponding monomer or/and a prepolymer of the resin, and a corresponding initiator or/and a prepolymer thereof, the filler material being After the corresponding monomer or/and the prepolymer are mixed first, and then mixed with the rubber substrate and the corresponding initiator of the resin or/and its prepolymer, so that the filler together with the rubber substrate is dispersed The monomer or/and the prepolymer are polymerized with a corresponding initiator or/and a prepolymer thereof. The polymer composite according to claim 22, wherein the resin comprises polymethyl methacrylate, and the corresponding monomer is methyl methacrylate. The polymer composite material according to claim 21, further comprising a corresponding monomer or/and a prepolymer of the resin, and a corresponding initiator or/and a prepolymer thereof, the filler material being Corresponding to the starting agent or / and its prepolymer, and then mixing with the rubber substrate and the corresponding monomer or / and prepolymer of the resin, so that the filler together with the rubber substrate is dispersed The monomer or/and the prepolymer are polymerized with a corresponding initiator or/and a prepolymer thereof. The polymer composite of claim 24, wherein the resin comprises a polyurethane, and the monomer comprises an isocyanate, the initiator comprising a polyol. The polymer composite of claim 25, wherein the polyurethane is a thermoplastic polyurethane. A polymer product comprising the polymer composite of any one of claims 1 to 26. A process for producing a polymer composite material according to any one of claims 1 to 19, which comprises mixing a filler with a rubber substrate to disperse the filler into the polymer matrix.