Patent Description:
The application of degradable plastic masterbatch has become more and more common in foreign countries for injection and blow molding applications. Foreign masterbatches are often expensive and unaffordable for domestic manufacturers. Due to the domestic technology and economic constraints, the development is relatively lagging behind. Especially in large-area injection molding, poor or not enough good dispersion performance leads to poor product quality, or easy to fade and ooze, etc., where there are also methods to add color masterbatch, but domestic color masterbatch generally has heavy metals exceeding the standard due to raw materials, pigments and additives, which is not applicable to products with high environmental requirements. And there are also problems of environmental pollution in the production process. In addition, the degradation rate of degradable plastic masterbatches in the existing process is generally not high. At present, the widely used degradable plastics include photodegradable plastics, biodegradable plastics, photo/biodegradable plastics and fully degradable plastics. Among them, photodegradable plastics are mainly irradiated by ultraviolet light and other light, and the electron activity of polymer molecular chains in these plastics is excited and photochemical reactions occur, then with oxygen in the air participating in the chemical reactions, the nature of the plastic is changed, and finally a photo-oxidative degradation is realized. Photodegraded plastics become brittle due to light, and with the aid of natural factors such as wind and rain, the material becomes further brittle and eventually forms a powder and is incorporated into the soil to enter a new biological cycle. Biodegradation refers to the process of degradation by microbial erosion and decomposition. Biodegradable materials are biodegraded by adding plasticizers, antioxidants and other additives to the polymers to change their properties and reduce their resistance to biological erosion. Currently, biodegradable plastics are very common, such as starch-based degradable plastics and cellulose-based degradable plastics. Photo/biodegradable plastics combine the advantages of both, however, the cost is high, the product is uncontrollable, and it may cause secondary pollution due to incomplete degradation. Fully degradable plastics are represented by starch plastics with starch content of more than <NUM>%, but their performance has certain shortcomings, especially in mechanical properties and stability, and the price is more than <NUM>-<NUM> times higher than that of traditional plastics. Therefore, there is a need for a degradable plastic masterbatch with high degradation rate, complete degradation, low toxicity, good mechanical properties and low cost. <CIT> discloses a toughening master batch for a polypropylene buried corrugated pipe. <CIT> discloses a preparation method of PE preservative film master batch. <CIT> discloses a high fill polyolefin composite film masterbatch.

Patent <CIT> provides a laminate structure that improves the heat transfer and bonding strength of a hot melt adhesive to a laminate substrate at a lower temperature than the polyolefin alone by adding an inorganic filler to the polyolefin material, thereby improving the heat seal of the structure to the hot melt adhesive, resulting in improved bonding properties over common materials using hot melt adhesives. However, this adhesive structure is not conducive to adequate contact and reaction of the degradable material with the environment, resulting in a reduced rate of material degradation. Chinese patent with application No. <CIT> provides a method for preparing degradable mulch by reusing organic waste residues of biomass, by treating the waste with a low concentration of alkali, neutralizing the material with nitric acid, hydrochloric acid, sulfuric acid, ammonium sulfate, ammonium phosphate, ammonium chloride, and humic acid, and adding N, P, and K needed for plant growth, and then adding film-forming agents and plasticizers to produce the mulch material. The degradation cycle of this material is moderate, almost completely degraded in about <NUM> months, but its mechanical strength is low and the preparation method is environmentally dependent, so it is not suitable for other products such as toys and tableware, and the degradation products are more polluting to the environment. Chinese patent application with application No. <CIT> discloses nano particle/polyamide composite material, preparing polymer masterbatch with unique properties of nanomaterials and mechanical properties of polymer matrix by hydrolysis polymerization method or anion homogenization method. Based on its low production cost and simple production equipment, it is suitable for large-scale industrial production, but the degradation rate of the material and final degradability need to be improved.

The purpose of the present invention is to provide an inorganic degradable plastic masterbatch material, so that the product prepared meets the degradation requirements and has higher mechanical strength and faster degradation rate than ordinary plastic products.

The technical solution of the present invention is specified as follows.

An inorganic degradable plastic masterbatch material, which is used to prepare various environmentally friendly degradable products, comprising the following components:.

Preferably, the glass fibers with mass percentage of <NUM>-<NUM>% are composite glass fibers obtained by compositing very fine glass fibers, water glass, jute fibers and carbon nanotubes.

Preferably, a mass ratio of the very fine glass fibers, water glass, jute fibers and carbon nanotubes is <NUM>: <NUM>-<NUM> : <NUM>-<NUM> : <NUM>-<NUM>.

Preferably, the glass fibers have a diameter of <NUM>-<NUM> and a length of <NUM>. <NUM>-<NUM>.

Preferably, the additives include one of or a mixture of several of the following: surface modifier PN-<NUM>, heat stabilizer BASF25, lubricant zinc stearate L-<NUM>, lubricant PP wax, surface modifier stearic acid180, synergist and antioxidant.

Preferably, the synergist comprises component I and component II, the mass ratio between component I and component II being <NUM>-<NUM>:<NUM>-<NUM>; wherein the component I is one or more of zirconate coupling agent, aluminate coupling agent, titanate coupling agent, silane coupling agent; the component II is one or more of polypropylene graft maleic anhydride, styrene graft maleic anhydride, ethylene-ethyl acrylic acid copolymer grafted with maleic anhydride, vinyl-ethylene-acetate-carbon monoxide terpolymer grafted with maleic anhydride, styrene-butadiene-styrene block copolymer graft maleic anhydride.

Preferably, the antioxidant is selected from one or a mixture of <NUM>, <NUM>-tertiary butyl-<NUM>-methylphenol and bis(<NUM>, <NUM>-tertiary butyl-<NUM>-hydroxyphenyl) sulfide.

Preferably, a mass relationship of the additives satisfies that: a mass ratio of surface modifier PN-<NUM>, heat stabilizer BASF25, lubricant zinc stearate L-<NUM>, lubricant PP wax, surface modifier stearic acid180, synergist, and antioxidant is <NUM>-<NUM>:<NUM>-<NUM>:<NUM>-<NUM>:<NUM>-<NUM>:<NUM>-<NUM>:<NUM>-<NUM>:<NUM>-<NUM>.

Preferably, the aluminate coupling agent is selected from one or more of DL-<NUM>, DL-411AF, ASA, DL-411D, DL-411DF. The zirconate coupling agent is tetra-n-propyl zirconate. The titanate coupling agent is triisostearyl isopropyl carbonate, tri(<NUM>-dodecylbenzenesulfonyl) isopropyl titanate, tri(dioctyl pyrophosphoryl) isopropyl titanate, di(dioctyl phosphoryl) ethylene titanate, di(dioctyl pyrophosphoryl) ethylene titanate, tetraisopropyl titanate di(dodecyl phosphite), tri(diphenylpropyl)-isopropyl titanate, di(methacryloyl)-isostearyl titanate. The silane coupling agent is one or more of chloropropyl silane coupling agent, epoxy silane coupling agent, methacrylate-based silane coupling agent, vinyltriethoxysilane, silylated polybutadiene compound, N-<NUM> (aminoethyl) <NUM>-aminopropyltrimethoxysilane, N-<NUM> (aminoethyl) <NUM>-aminopropyldiethoxysilane, <NUM>-aminopropyldimethoxysilane, <NUM>-aminopropyldiethoxysilane, <NUM>-glycidopropyltrimethoxysilane.

Further, the present invention relates to a preparation method of inorganic degradable plastic masterbatch material, comprising the following steps: step <NUM>: weighing and preparing calcium carbonate mixed powder meeting ratio requirement; step <NUM>: weighing and sequentially adding calcium carbonate mineral powder with mass percentage of <NUM>-<NUM>%, glass fibers with mass percentage of <NUM>-<NUM>% into a mixer to mix for <NUM> minutes, then adding polyethylene with mass percentage of <NUM>-<NUM>%, polypropylene with mass percentage of <NUM>-<NUM>% and additives with mass percentage of <NUM>-<NUM>% into the mixer to mix for <NUM>-<NUM> minutes to obtain a raw material mixture, while using ultrasonic vibration to tamp exhaust; step <NUM>: melting and mixing the raw material mixture came from the mixer in an extruder, having the raw material mixture melted and extruded into strips as the temperature increases sequentially from an inlet to an outlet, then entering into ice water for rapid cooling quickly after extrusion, and passing it through a cutter for underwater high-speed dicing, then dehydrating and drying to produce a granular material of inorganic degradable plastic masterbatch.

In the method, a preferred speed of the mixer is <NUM>-<NUM> r/min, a ultrasonic vibration frequency is <NUM>-<NUM>, and a further ultrasonic vibration frequency is <NUM>.

In the method, in the step <NUM>, the temperature for melting and mixing the raw material mixture in the extruder is preferably <NUM>-<NUM>.

Further, the present invention provides an application of inorganic degradable plastic masterbatch material, the material can be used in many traditional plastic processes such as blow molding, blister molding, injection molding, tube drawing, calendering, film blowing, etc., and the products made by the processes meet the degradation requirements and have higher mechanical strength and faster degradation rate than ordinary plastic products.

The present invention has the following outstanding advantages.

preparation of inorganic degradable plastic masterbatch material:.

In the step <NUM>, the temperature for melting and mixing the raw material mixture in the extruder is <NUM>.

The mass ratio of surface modifier PN-<NUM>, heat stabilizer BASF25, lubricant zinc stearate L-<NUM>, lubricant PP wax, surface modifier stearic180 acid, synergist and antioxidant is <NUM>:<NUM>:<NUM>:<NUM>:<NUM>:<NUM>:<NUM>; synergist includes silane coupling agent and vinyl-ethylene-acetate-carbon monoxide terpolymer grafted with maleic anhydride, with a mass ratio of <NUM>:<NUM>. The silane coupling agent is <NUM>-aminopropyltrimethoxysilane.

The antioxidant is selected from <NUM>, <NUM>-tertiary butyl-<NUM>-methylphenol.

The glass fibers are composite glass fibers obtained by compositing very fine glass fibers, water glass, jute fibers and carbon nanotubes; the glass fibers have a diameter of <NUM> and a length of <NUM>; the very fine glass fibers, water glass, jute fiber and carbon nanotubes have a mass ratio of <NUM>: <NUM>:<NUM>:<NUM>.

In the above step <NUM>, the temperature for melting and mixing the raw material mixture in the extruder is <NUM>.

The mass ratio of surface modifier PN-<NUM>, heat stabilizer BASF25, lubricant zinc stearate L-<NUM>, lubricant PP wax, surface modifier stearic180 acid, synergist and antioxidant is <NUM>:<NUM>:<NUM>:<NUM>:<NUM>:<NUM>:<NUM>; synergist includes silane coupling agent and vinyl-ethylene-acetate-carbon monoxide terpolymer grafted with maleic anhydride, with a mass ratio of <NUM>:<NUM>. The silane coupling agent is <NUM>-aminopropyltriethoxysilane.

The antioxidant is bis(<NUM>, <NUM>-tertiary butyl-<NUM>-hydroxyphenyl) sulfide.

The glass fibers are composite glass fibers obtained by compositing very fine glass fibers, water glass, jute fibers and carbon nanotubes; the glass fibers have a diameter of <NUM> and a length of <NUM>; the very fine glass fibers, water glass, jute fiber and carbon nanotubes have a mass ratio of <NUM>:<NUM>:<NUM>:<NUM>.

The mass ratio of surface modifier PN-<NUM>, heat stabilizer BASF25, lubricant zinc stearate L-<NUM>, lubricant PP wax, surface modifier stearic180 acid, synergist and antioxidant is <NUM>:<NUM>:<NUM>:<NUM>:<NUM>:<NUM>:<NUM>; synergist includes silane coupling agent and styrene-butadiene-styrene block copolymer graft maleic anhydride, with a mass ratio of <NUM>:<NUM>. The silane coupling agent is <NUM>-aminopropyltriethoxysilane.

The mass ratio of surface modifier PN-<NUM>, heat stabilizer BASF25, lubricant zinc stearate L-<NUM>, lubricant PP wax, surface modifier stearic180 acid, synergist and antioxidant is <NUM>:<NUM>:<NUM>:<NUM>:<NUM>:<NUM>:<NUM>; synergist includes zirconate coupling agent and styrene-butadiene-styrene block copolymer graft maleic anhydride, with a mass ratio of <NUM>:<NUM>. The zirconate coupling agent is tetra-n-propyl zirconate.

The mass ratio of surface modifier PN-<NUM>, heat stabilizer BASF25, lubricant zinc stearate L-<NUM>, lubricant PP wax, surface modifier stearic180 acid, synergist and antioxidant is <NUM>:<NUM>:<NUM>:<NUM>:<NUM>:<NUM>:<NUM>; synergist includes titanate coupling agent and styrene-butadiene-styrene block copolymer graft maleic anhydride. The titanate coupling agent is tri(<NUM>-dodecylbenzenesulfonyl) isopropyl titanate, with a mass ratio of <NUM>:<NUM>.

The antioxidant is <NUM>, <NUM>-tertiary butyl-<NUM>-methylphenol.

The mass ratio of surface modifier PN-<NUM>, heat stabilizer BASF25, lubricant zinc stearate L-<NUM>, lubricant PP wax, surface modifier stearic180 acid, synergist and antioxidant is <NUM>:<NUM>:<NUM>:<NUM>:<NUM>:<NUM>:<NUM>; synergist includes of silane coupling agent and ethylene-ethyl acrylic acid copolymer grafted with maleic anhydride, with a mass ratio of <NUM>:<NUM>. The silane coupling agent is N-<NUM> (aminoethyl)<NUM>-aminopropyldiethoxysilane.

The mass ratio of surface modifier PN-<NUM>, heat stabilizer BASF25, lubricant zinc stearate L-<NUM>, lubricant PP wax, surface modifier stearic180 acid, synergist and antioxidant is <NUM>:<NUM>:<NUM>:<NUM>:<NUM>:<NUM>:<NUM>; synergist includes component I and component II with a mass ratio of <NUM>:<NUM>, wherein the component I is aluminate coupling agent; the component II is a mixture of ethylene-ethyl acrylic acid copolymer grafted with maleic anhydride and polypropylene graft maleic anhydride. The aluminate coupling agent is DL-411AF.

The mass ratio of surface modifier PN-<NUM>, heat stabilizer BASF25, lubricant zinc stearate L-<NUM>, lubricant PP wax, surface modifier stearic180 acid, synergist and antioxidant is <NUM>:<NUM>:<NUM>:<NUM>:<NUM>:<NUM>:<NUM>; synergist includes component I and component II with a mass ratio of <NUM>:<NUM>, wherein the component I is silane coupling agent; the component II is a mixture of styrene-butadiene-styrene block copolymer graft maleic anhydride and styrene graft maleic anhydride. The silane coupling agent is methacrylate-based silane coupling agent.

The antioxidant is obtained by preparing <NUM>, <NUM>-tertiary butyl-<NUM>-methylphenol and bis(<NUM>, <NUM>-tertiary butyl-<NUM>-hydroxyphenyl) sulfide in a mass ratio of <NUM>:<NUM>.

The inorganic degradable plastic masterbatch material prepared by the preparation method as described in Embodiment <NUM>, with the difference that no glass fiber was added.

The inorganic degradable plastic masterbatch material prepared by the preparation method as described in Embodiment <NUM>, with the difference that the auxiliary synergist contains only one component, i.e., silane coupling agent.

The inorganic degradable plastic masterbatch material prepared by the preparation method as described in Embodiment <NUM>, with the difference that the auxiliary synergist is zirconate coupling agent and polypropylene graft maleic anhydride with a mass ratio of <NUM>:<NUM>.

The inorganic degradable plastic masterbatch material prepared by the preparation method as described in Embodiment <NUM>, with the difference that compositions of the auxiliary synergist are aluminate coupling agent and styrene graft maleic anhydride with a mass ratio of <NUM>:<NUM>.

The inorganic degradable plastic masterbatch material prepared by the preparation method as described in Embodiment <NUM>, with the difference that compositions of the auxiliary synergist are titanate coupling agent and styrene-butadiene-styrene block copolymer graft maleic anhydride with a mass ratio of <NUM>:<NUM>.

The inorganic degradable plastic masterbatch material prepared by the preparation method as described in Embodiment <NUM>, with the difference that compositions of the auxiliary synergist are silane coupling agent and polypropylene graft maleic anhydride with a mass ratio of <NUM>:<NUM>.

The inorganic degradable plastic masterbatch material prepared by the preparation method as described in Embodiment <NUM>, with the difference that the synergist in the masterbatch consists only of styrene graft maleic anhydride.

The inorganic degradable plastic masterbatch material prepared by the preparation method as described in Embodiment <NUM>, with the difference that the glass fibers are common glass fibers.

The inorganic degradable plastic masterbatch material prepared by the preparation method as described in Embodiment <NUM>, with the difference that no carbon nanotubes were added to the glass fibers.

The inorganic degradable plastic masterbatch material prepared by the preparation method as described in Embodiment <NUM>, with the difference that no jute fibers were added to the glass fibers.

The inorganic degradable plastic masterbatch material prepared by the preparation method as described in Embodiment <NUM>, with the difference that no water glass was added to the glass fibers.

The inorganic degradable plastic masterbatch material prepared by the preparation method as described in Embodiment <NUM>, with the difference that the composite glass fibers have a diameter of <NUM> and a length of <NUM>.

The inorganic degradable plastic masterbatch material prepared by the preparation method as described in Embodiment <NUM>, with the difference that the mass ratio of very fine glass fibers, water glass, jute fibers and carbon nanotubes in the composite glass fibers is <NUM>:<NUM>:<NUM>:<NUM>.

The inorganic degradable plastic masterbatch material prepared by the preparation method as described in Embodiment <NUM>, with the difference that the average particle size of the calcium carbonate mineral powder is <NUM> microns.

Table <NUM> and Table <NUM> show the tensile strength, flexural strength, flexural modulus of embodiments and comparative examples measured with reference to relevant standards , and data after <NUM> months, after <NUM> months and after <NUM> year (after <NUM> months) in a degradable environment.

Toxicity detection results of degradation products after degradation of masterbatch materials are shown in Table <NUM>.

Test method: determination by reference to USEPA5021A:<NUM> method, analysis by using HS-GC-MS.

Claim 1:
An inorganic degradable plastic masterbatch material, used to prepare various environmentally friendly degradable products, comprising the following components:
calcium carbonate mineral powder with mass percentage of <NUM>-<NUM>%;
polyethylene with mass percentage of <NUM>-<NUM>%;
polypropylene with mass percentage of <NUM>-<NUM>%;
glass fibers with mass percentage of <NUM>-<NUM>%; and
additives with mass percentage of <NUM>-<NUM>%;
proportions of calcium carbonate mineral powder of different particle sizes in the above mentioned calcium carbonate mineral powder with mass percentage of <NUM>-<NUM>% are:
<NUM>-<NUM>% for <NUM> mesh with particle diameter being controlled at <NUM>-<NUM> microns;
<NUM>-<NUM>% for <NUM> mesh with particle diameter being controlled at <NUM>-<NUM> microns;
<NUM>-<NUM>% for <NUM> mesh with particle diameter being controlled at <NUM>-<NUM> microns;
<NUM>-<NUM>% for <NUM> mesh with particle diameter being controlled at <NUM>-<NUM> microns;
<NUM>-<NUM>% for <NUM> mesh with particle diameter being controlled at <NUM>-<NUM> microns;
<NUM>-<NUM>% for <NUM> mesh with particle diameter being controlled at <NUM>-<NUM> microns;
wherein, an average particle size for the calcium carbonate mineral powder as a whole must be in a range between <NUM> microns and <NUM> microns.