WO2018086159A1 - High strength nano plastic and preparation method therefor - Google Patents

Abstract

Disclosed are a high strength nano plastic and preparation method therefor. The raw materials are PVC, nano calcium carbonate, nano titanium dioxide, a coupling agent, a plasticizer, ferrocene, a UV absorber of UV-9, a lubricant, a flame retardant, carbon black, an impact modifier, an antioxidant, a heat stabilizer and a magnesium salt whisker; the nano plastic has good oil resistance, corrosion resistance, low costs, has a bending strength of 90-130 MPa, an oxygen index of 40-44%, a tensile strength of 60-100 MPa, a heat distortion temperature of 140-180ºC, a flexural modulus of 2000-4000 MPa; an elastic modulus of 300-700 MPa, a retention of 99% under UV irradiation for 2500-4500 h, an impact strength of 40-80 kJ/m2, and an elongation at break of 400-600%, can be widely used in various extreme environments, and has a cold resistance of -50ºC without cracking.

Description

High-strength nano plastic and preparation method thereof Technical field

The invention relates to the technical field of nano plastics, in particular to a high-strength nano plastic and a preparation method thereof.

Background technique

Nanomaterials is a completely new field of science that has just emerged in recent years. It involves knowledge of many fields such as physics, chemistry, materials, and biology.

"Nano" is a unit of measure of length, which is 1 billion meters (10-9 m). In general, a nanomaterial refers to a one-dimensional scale of at least one phase of a two-phase microstructure reaching a nanometer scale. Nanoparticles have a small particle size, a large surface energy, and are easily agglomerated. Therefore, how to prepare nanoparticles is a very complicated technical problem. At present, most of the nanoparticles that can be produced and utilized are inorganic nanoparticles, and the nanoparticles that can effectively modify the plastic are SiO2, TiO2, CaCO3, and MMT.

The core content of "nanotechnology" is how to solve the agglomeration problem of nanoparticles. Since the nanoparticles themselves are very easy to agglomerate, it is very difficult to obtain a single dispersed nanoparticle. How to make the nanoparticles uniformly dispersed into the matrix is "nanotechnology" The key technology. At present, from the application research report of "nanotechnology", there are two methods that can be industrialized: 1. Nano-intercalation technology, that is, n-MMT processed by intercalation, has a certain degree of compactness, size The uniform masterbatch is then mixed and granulated by the masterbatch to solve the problem of uneven dispersion of the nanomaterial in the matrix, and the nanocomposite is prepared. 2. The vibration grinding dispersion method can make the nanoparticles uniformly dispersed in the matrix, and basically does not generate agglomeration, and truly achieve nano-scale dispersion.

"Nano-plastic" means that the matrix is a high-molecular polymer, and the nano-particles are sufficiently dispersed in the plastic resin to effectively improve the heat resistance, weather resistance and wear resistance of the plastic. "Nano-Plastic" enables ordinary plastics to have the same rigidity and heat resistance as ceramic materials, while retaining the toughness, impact resistance and ease of processing of the plastic itself. At present, NPE, NPET and NPA6 (ie, nano-polyethylene, nano-PET polyester, nano-nylon 6) modified by nanoparticles can be industrialized, and silver (Ag+) is designed to be microporous on the surface of particles. In the middle and stable, it can be made into nano-silver antibacterial materials. Adding this material to plastics can make plastics have excellent properties such as antibacterial, mildewproof and self-cleaning, making them green products. At present, it has been applied in ABS, SPVC, HIPS, PP plastics.

“Nano-Plastic” is a high-tech new material with good development prospects. Due to the lack of understanding of this new material in China, there is no complete quality assurance system and strict production management. And up" The situation, the eyes of the fish, the true and false is difficult to argue, so that "nanoplastics" is at the beginning of the danger of "dead", so I urgently hope that the relevant state departments can protect this new material through the corresponding standards and regulations, and promote its health. growing up.

Polyvinyl chloride, referred to as PVC (Polyvinyl chloride), is a vinyl chloride monomer (VCM) in the initiator of peroxides, azo compounds, or free radical polymerization under the action of light and heat. Polymerized polymer. The vinyl chloride homopolymer and the vinyl chloride copolymer are collectively referred to as vinyl chloride resins.

PVC is a white powder with amorphous structure, with a small degree of branching, a relative density of about 1.4, a glass transition temperature of 77-90 ° C, and a decomposition of about 170 ° C [1], poor stability to light and heat, above 100 ° C or After prolonged exposure to sunlight, it will decompose to produce hydrogen chloride, and further autocatalytic decomposition, causing discoloration, and physical and mechanical properties are also rapidly declining. In practical applications, stabilizers must be added to improve the stability to heat and light.

Industrial production of PVC molecular weight is generally in the range of 50,000 to 110,000, with greater polydispersity, molecular weight increases with the decrease of polymerization temperature; no fixed melting point, 80-85 ° C begins to soften, 130 ° C becomes viscoelastic state , 160 ~ 180 ° C began to transform into a viscous flow state; has good mechanical properties, tensile strength of about 60MPa, impact strength of 5 ~ 10kJ / m2; has excellent dielectric properties.

PVC was once the world's largest production of general-purpose plastics, and it is widely used. It is widely used in building materials, industrial products, daily necessities, floor leather, floor tiles, artificial leather, pipes, wires and cables, packaging films, bottles, foam materials, sealing materials, fibers, etc.

Summary of the invention

The invention provides a high-strength nano plastic with high heat distortion temperature, high tensile strength, high notched impact strength and high elongation, and a preparation method thereof, and solves the problems of low strength, low elongation, low oxygen index and the existing plastic materials. Technical problems such as heat resistance.

The invention adopts the following technical scheme: a high-strength nano plastic, the raw materials of which are matched according to the mass fraction: 100 parts of PVC, 5-25 parts of nano calcium carbonate, 4-8 parts of nano titanium dioxide, 10-30 parts of coupling agent, 45-65 parts of plasticizer, 0.4-0.8 parts of ferrocene, 1-5 parts of UV absorber UV, 0.5-2.5 parts of lubricant, 12-16 parts of flame retardant, 0.5-4.5 parts of carbon black, 3-7 parts of impact modifier, 1-20 parts of antioxidant, 6-10 parts of heat stabilizer, 1-20 parts of magnesium salt whisker.

As a preferred technical solution of the present invention, the raw materials of the high-strength nano plastic are matched in parts by mass: 100 parts of PVC, 10-20 parts of nano calcium carbonate, 5-7 parts of nano titanium dioxide, coupling agent 15-25 Parts, plasticizer 50-60 parts, ferrocene 0.5-0.7 parts, UV absorber UV-9 is 2-4 parts, lubricant 1-2 parts, flame retardant 13-15 parts, 1.5-3.5 parts of carbon black, 4-6 parts of impact modifier, 5-15 parts of antioxidant, 7-9 parts of heat stabilizer, 5-15 parts of magnesium salt whisker.

As a preferred technical solution of the present invention, the coupling agent is a silane coupling agent, a titanate coupling agent or an aluminate coupling agent.

As a preferred technical solution of the present invention, the plasticizer is DOP, DBP, DOS, dioctyl sebacate, DIDP, trioctyl trimellitate, epoxidized soybean oil or tricresyl phosphate.

As a preferred technical solution of the present invention, the lubricant is made of polyethylene wax, paraffin or glyceryl monostearate.

As a preferred technical solution of the present invention, the flame retardant uses antimony trioxide, zinc borate, aluminum hydroxide or ammonium polyphosphate.

As a preferred technical solution of the present invention, the impact modifier is ACR, MBS or CPE.

As a preferred technical solution of the present invention, the antioxidant is an antioxidant 1010, an antioxidant DLTP or an antioxidant 168.

As a preferred technical solution of the present invention, the heat stabilizer uses barium stearate, lead stearate, cadmium stearate, zinc stearate, tribasic lead sulfate, dibasic lead phosphite, sulfur Alcohol methyl tin or calcium stearate.

A method for preparing the high strength nano plastic, the steps are:

The first step: weigh PVC, nano calcium carbonate, nano titanium dioxide, coupling agent, plasticizer, ferrocene, UV absorber UV-9, lubricant, flame retardant, carbon black, according to the proportion of mass parts. Impact modifiers, antioxidants, heat stabilizers and magnesium salt whiskers;

The second step: the PVC, nano-calcium carbonate, nano-titanium dioxide, ferrocene, ferrocene and magnesium salt whiskers are put into a high-speed mixer, the temperature is raised to 120-130 ° C, the remaining raw materials are added, and the temperature is raised to 150-160 ° C. Mixing speed 900-1000r/min, mixing 50-60min, cooling to 45-50 °C discharge;

The third step: melt-plasticizing granulation in a twin-screw extruder with a length to diameter ratio of 20:1. The temperature of the extruder is 190-200 °C in one zone, 200-210 °C in the second zone, 210-220 °C in the third zone, and four in the third zone. Zone 220-230 ° C, five zones 210-220 ° C, six zones 200-210 ° C, die temperature 220-230 ° C, screw speed 130-150r / min.

Beneficial effect

The high-strength nano plastic according to the present invention and the preparation method thereof have the following technical effects compared with the prior art by the above technical solution: 1. good oil resistance, corrosion resistance, low cost, bending strength 90-130 MPa, oxygen index 40-44%; 2, tensile strength 60-100MPa, heat distortion temperature 140-180 ° C, excellent wear resistance and elasticity, flexural modulus 2000-4000MPa; 3, elastic modulus 300-700MPa, no dripping, raw materials Rich in resources, UV light irradiation 2500-4500h retention rate 99%, impact strength 40-80kJ / m ² ; 4, elongation at break 400-600%, can be widely used in various extreme environments, cold resistance -50 ° C Cracking, long-term work in high temperature environment is not easy to aging, meet environmental requirements, can be widely produced and continuously replace existing materials.

detailed description

The invention is further described in the following examples, which are intended to be illustrative only and not to limit the scope of the claims, and other alternatives that are apparent to those skilled in the art are within the scope of the appended claims.

Example 1:

The first step: weigh 100 parts of PVC, 5 parts of nano calcium carbonate, 4 parts of nano titanium dioxide, 10 parts of silane coupling agent, 45 parts of epoxy soybean oil, 0.4 parts of ferrocene, UV absorber UV according to the proportion of mass parts. -9 is 1 part, 0.5 parts of polyethylene wax, 12 parts of ammonium polyphosphate, 0.5 part of carbon black, 3 parts of CPE, 1 part of antioxidant 168, 6 parts of barium stearate, and 1 part of magnesium salt whisker.

The second step: the PVC, nano-calcium carbonate, nano-titanium dioxide, ferrocene, ferrocene and magnesium salt whiskers are put into a high-speed mixer, the temperature is raised to 120 ° C, the remaining raw materials are added, the temperature is raised to 150 ° C, and the mixing speed is 900 r / Min, mixed for 50 min, cooled to 45 ° C discharge.

Melt plasticizing granulation in a twin-screw extruder with a length to diameter ratio of 20:1. The temperature of the extruder is 190 °C in one zone, 200 °C in the second zone, 210 °C in the third zone, 220 °C in the four zones, 210 °C in the five zones, and six zones. The area is 200 ° C, the die temperature is 220 ° C, and the screw speed is 130 r / min.

Good oil resistance, corrosion resistance, low cost, bending strength 90MPa, oxygen index 40%; tensile strength 60MPa, heat distortion temperature 140°C, excellent wear resistance and elasticity, flexural modulus 2000MPa; elastic modulus 300MPa, no dripping Rich in raw materials, UV light 2500h retention rate 99%, impact strength 40kJ/m ² ; elongation at break 400%, can be widely used in various extreme environments, cold resistance -50 °C without cracking, in high temperature environment Long-term work is not easy to age, meet environmental requirements, and can be widely produced and continuously replaced with existing materials.

Example 2:

The first step: weigh 100 parts of PVC according to the mass fraction, 25 parts of nano calcium carbonate, 8 parts of nano titanium dioxide, 30 parts of titanate coupling agent, 65 parts of DIDP, 0.8 parts of ferrocene, UV absorber UV- 9 is 5 parts, 2.5 parts of polyethylene wax, 16 parts of aluminum hydroxide, 4.5 parts of carbon black, 7 parts of MBS, 20 parts of antioxidant DLTP, 10 parts of lead stearate, and 20 parts of magnesium salt whiskers.

Step 2: Put PVC, nano-calcium carbonate, nano-titanium dioxide, ferrocene, ferrocene and magnesium salt whiskers into a high-speed mixer, raise the temperature to 130 ° C, add the remaining raw materials, raise the temperature to 160 ° C, and mix the speed 1000 r / Min, mixed for 60 min, cooled to 50 ° C discharge.

The melt-plasticizing granulation is carried out in a twin-screw extruder with a length to diameter ratio of 20:1. The temperature of the extruder is 200 ° C in one zone, 210 ° C in the second zone, 220 ° C in the third zone, 230 ° C in the four zones, 220 ° C in the five zones, and six zones. The zone is 210 ° C, the die temperature is 230 ° C, and the screw speed is 150 r/min.

Good oil resistance, corrosion resistance, low cost, bending strength 100MPa, oxygen index 40%; tensile strength 70MPa, heat distortion temperature 150°C, excellent wear resistance and elasticity, flexural modulus 2500MPa; elastic modulus 400MPa, no dripping Rich in raw material resources, UV light irradiation 3000h retention rate 99%, impact strength 50kJ/m ² ; elongation at break 450%, can be widely used in various extreme environments, cold resistance -50 °C without cracking, in high temperature environment Long-term work is not easy to age, meet environmental requirements, and can be widely produced and continuously replaced with existing materials.

Example 3:

The first step: weigh 100 parts of PVC according to the mass fraction, 10 parts of nano calcium carbonate, 5 parts of nano titanium dioxide, 15 parts of aluminate coupling agent, 50 parts of DOS, 0.5 parts of ferrocene, UV absorber UV- 9 is 2 parts, 1 part of paraffin, 13 parts of zinc borate, 1.5 parts of carbon black, 4 parts of MBS, 5 parts of antioxidant DLTP, 7 parts of cadmium stearate, and 5 parts of magnesium salt whisker.

The second step: the PVC, nano-calcium carbonate, nano-titanium dioxide, ferrocene, ferrocene and magnesium salt whiskers are put into a high-speed mixer, the temperature is raised to 120 ° C, the remaining raw materials are added, the temperature is raised to 150 ° C, and the mixing speed is 900 r / Min, mixed for 50 min, cooled to 45 ° C discharge.

Melt plasticizing granulation in a twin-screw extruder with a length to diameter ratio of 20:1. The temperature of the extruder is 190 °C in one zone, 200 °C in the second zone, 210 °C in the third zone, 220 °C in the four zones, 210 °C in the five zones, and six zones. The area is 200 ° C, the die temperature is 220 ° C, and the screw speed is 130 / min.

Good oil resistance, corrosion resistance, low cost, bending strength 110MPa, oxygen index 42%; tensile strength 80MPa, heat distortion temperature 160°C, excellent wear resistance and elasticity, flexural modulus 3000MPa; elastic modulus 500MPa, no dripping Rich in raw material resources, UV light irradiation 3500h retention rate 99%, impact strength 60kJ/m ² ; elongation at break 500%, can be widely used in various extreme environments, cold resistance -50 °C without cracking, in high temperature environment Long-term work is not easy to age, meet environmental requirements, and can be widely produced and continuously replaced with existing materials.

Example 4:

The first step: weigh 100 parts of PVC according to the proportion of mass parts, 20 parts of nano calcium carbonate, nano titanium dioxide 7 Parts, 25 parts of silane coupling agent, 60 parts of DBP, 0.7 parts of ferrocene, 4 parts of UV absorber UV-9, 2 parts of paraffin, 15 parts of antimony trioxide, 3.5 parts of carbon black, 6 parts of ACR, anti-oxidation 15 parts of DLTP, 9 parts of zinc stearate and 15 parts of magnesium salt whiskers.

Step 2: Put PVC, nano-calcium carbonate, nano-titanium dioxide, ferrocene, ferrocene and magnesium salt whiskers into a high-speed mixer, raise the temperature to 130 ° C, add the remaining raw materials, raise the temperature to 160 ° C, and mix the speed 1000 r / Min, mixed for 60 min, cooled to 50 ° C discharge.

The melt-plasticizing granulation is carried out in a twin-screw extruder with a length to diameter ratio of 20:1. The temperature of the extruder is 200 ° C in one zone, 210 ° C in the second zone, 220 ° C in the third zone, 230 ° C in the four zones, 220 ° C in the five zones, and six zones. The zone is 210 ° C, the die temperature is 230 ° C, and the screw speed is 150 r/min.

Good oil resistance, corrosion resistance, low cost, bending strength 120MPa, oxygen index 43%; tensile strength 90MPa, heat distortion temperature 170°C, excellent wear resistance and elasticity, flexural modulus 3500MPa; elastic modulus 600MPa, no dripping Rich in raw material resources, UV light irradiation 4000h retention rate 99%, impact strength 70kJ/m ² ; elongation at break 550%, can be widely used in various extreme environments, cold resistance -50 °C without cracking, in high temperature environment Long-term work is not easy to age, meet environmental requirements, and can be widely produced and continuously replaced with existing materials.

Example 5:

The first step: weigh 100 parts of PVC according to the mass fraction, 15 parts of nano calcium carbonate, 6 parts of nano titanium dioxide, 20 parts of titanate coupling agent, 55 parts of DOP, 0.6 parts of ferrocene, UV absorber UV-9 3 parts, 1.5 parts of glyceryl monostearate, 14 parts of antimony trioxide, 2.5 parts of carbon black, 5 parts of ACR, 10 parts of antioxidant 1010, 8 parts of tribasic lead sulfate, 10 parts of magnesium salt whisker .

Step 2: Put PVC, nano-calcium carbonate, nano-titanium dioxide, ferrocene, ferrocene and magnesium salt whiskers into a high-speed mixer, raise the temperature to 125 ° C, add the remaining raw materials, raise the temperature to 155 ° C, and mix the speed 950 r / Min, mixed for 55 min, cooled to 48 ° C discharge.

The melt-plastic granulation was carried out in a twin-screw extruder with a length to diameter ratio of 20:1. The temperature of the extruder was 195 ° C in one zone, 205 ° C in the second zone, 215 ° C in the third zone, 225 ° C in the four zones, and 215 ° C in the five zones. The area is 205 ° C, the die temperature is 225 ° C, and the screw speed is 140 r / min.

Good oil resistance, corrosion resistance, low cost, bending strength 130MPa, oxygen index 44%; tensile strength 100MPa, heat distortion temperature 180°C, excellent wear resistance and elasticity, flexural modulus 4000MPa; elastic modulus 700MPa, no dripping Rich in raw materials, UV light irradiation 4500h retention rate 99%, impact strength 80kJ / m ² ; elongation at break 600%, can be widely used in various extreme environments, cold resistance -50 °C without cracking, in high temperature environment Long-term work is not easy to age, meet environmental requirements, and can be widely produced and continuously replaced with existing materials.

Claims (10)

The invention relates to a high-strength nano plastic, characterized in that the raw material of the high-strength nano plastic is matched according to the mass fraction: 100 parts of PVC, 5-25 parts of nano calcium carbonate, 4-8 parts of nano titanium dioxide, coupling agent 10- 30 parts, plasticizer 45-65 parts, ferrocene 0.4-0.8 parts, UV absorber UV-9 is 1-5 parts, lubricant 0.5-2.5 parts, flame retardant 12-16 parts, carbon black 0.5- 4.5 parts, 3-7 parts of impact modifier, 1-20 parts of antioxidant, 6-10 parts of heat stabilizer, 1-20 parts of magnesium salt whisker. The high-strength nano plastic according to claim 1, wherein the raw material of the high-strength nano plastic is matched in parts by mass: 100 parts of PVC, 10-20 parts of nano calcium carbonate, and 5-7 of nano titanium dioxide. Parts, coupling agent 15-25 parts, plasticizer 50-60 parts, ferrocene 0.5-0.7 parts, UV absorber UV-9 is 2-4 parts, lubricant 1-2 parts, flame retardant 13- 15 parts, carbon black 1.5-3.5 parts, impact modifier 4-6 parts, antioxidant 5-15 parts, heat stabilizer 7-9 parts, magnesium salt whiskers 5-15 parts. A high-strength nanoplastic according to claim 1, wherein the coupling agent is a silane coupling agent, a titanate coupling agent or an aluminate coupling agent. The high-strength nano plastic according to claim 1, wherein the plasticizer is DOP, DBP, DOS, dioctyl sebacate, DIDP, trioctyl trimellitate, and epoxy. Soybean oil or tricresyl phosphate. A high-strength nanoplastic according to claim 1, wherein the lubricant is polyethylene wax, paraffin wax or glyceryl monostearate. A high-strength nanoplastic according to claim 1, wherein the flame retardant is antimony trioxide, zinc borate, aluminum hydroxide or ammonium polyphosphate. A high-strength nanoplastic according to claim 1, wherein the impact modifier is ACR, MBS or CPE. A high-strength nanoplastic according to claim 1, wherein the antioxidant is an antioxidant 1010, an antioxidant DLTP or an antioxidant 168. The high-strength nano plastic according to claim 1, wherein the heat stabilizer uses barium stearate, lead stearate, cadmium stearate, zinc stearate, and tribasic lead sulfate. Dibasic lead phosphite, methyl mercaptan or calcium stearate. A method for preparing the high-strength nano plastic according to claim 1, comprising the steps of: first step: weighing PVC, nano calcium carbonate, nano titanium dioxide, coupling agent, and increasing according to the mass fraction Plasticizer, ferrocene, UV absorber UV-9, lubricant, flame retardant, ferrocene, impact modifier, antioxidant, Heat stabilizer and magnesium salt whisker; The second step: the PVC, nano-calcium carbonate, nano-titanium dioxide, ferrocene, ferrocene and magnesium salt whiskers are put into a high-speed mixer, the temperature is raised to 120-130 ° C, the remaining raw materials are added, and the temperature is raised to 150-160 ° C. Mixing speed 900-1000r/min, mixing 50-60min, cooling to 45-50 °C discharge; The third step: melt-plasticizing granulation in a twin-screw extruder with a length to diameter ratio of 20:1. The temperature of the extruder is 190-200 °C in one zone, 200-210 °C in the second zone, 210-220 °C in the third zone, and four in the third zone. Zone 220-230 ° C, five zones 210-220 ° C, six zones 200-210 ° C, die temperature 220-230 ° C, screw speed 130-150r / min.