CN105348777A - A polyurethane composite material modified by recycled electronic waste plastic - Google Patents
A polyurethane composite material modified by recycled electronic waste plastic Download PDFInfo
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- CN105348777A CN105348777A CN201510780627.8A CN201510780627A CN105348777A CN 105348777 A CN105348777 A CN 105348777A CN 201510780627 A CN201510780627 A CN 201510780627A CN 105348777 A CN105348777 A CN 105348777A
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Abstract
A polyurethane composite material modified by recycled electronic waste plastic is disclosed. The composite material comprises following raw materials: polyurethane elastomer, recycled polyvinyl chloride, recycled epoxy resin, acrylate copolymers, stearic acid, zinc stearate, calcium stearate, recycled polyethylene, recycled phenolic resin, a modified nanofiller, expanded graphite, ammonium polyphosphate, a silane coupling agent, epoxidized soybean oil, dioctyl adipate, dimethyl methylphosphonate, and 2,2-bis(chloromethyl)-1,3-propylidene-tetra(2-chloroethyl) diphosphate. The composite material is good in heat resistance and excellent in flame retardance. The recycled electronic waste plastic is added, so that the cost is saved and the composite material is environmental friendly.
Description
Technical field
The present invention relates to compound polyurethane material technical field, particularly relate to a kind of electron wastes recycled plastics polymers modified polyurethane matrix material.
Background technology
In electron wastes, plastics proportion is about 30%, wherein have polypropylene, polyethylene, polystyrene, acrylonitrile-butadiene-styrene copolymer, polyvinyl chloride etc. as the kind that housing plastic usage quantity is larger, in different electronic product, all types of plastic usage quantity difference is very large.At present, in China's electron wastes, plastics only have a small amount of regeneration, so not only contaminate environment, and cause the wasting of resources.
Polyurethane elastomer be it is believed that as epoch-making novel high polymer material, it is one of synthetic materials of current most development prospect, it has good physicals, just be widely used in electric wire, automobile and other industries now, due to the singularity of industry, it is fire-retardant, heat-resisting and water tolerance requirement is also more and more higher.
Summary of the invention
Based on the technical problem that background technology exists, the present invention proposes a kind of electron wastes recycled plastics polymers modified polyurethane matrix material, its good heat resistance, excellent fireproof performance, and with the addition of electron wastes recycled plastics polymers, saved cost, the feature of environmental protection is good.
A kind of electron wastes recycled plastics polymers modified polyurethane matrix material that the present invention proposes, its raw material comprises following component by weight: polyurethane elastomer 100 parts, polyvinyl chloride reworked material 15-30 part, epoxy resin reworked material 5-12 part, acrylic acid esters co-polymer 1-3 part, stearic acid 0.3-1.2 part, Zinic stearas 0.5-1 part, calcium stearate 0.2-1 part, recycled polyethylene 1-3.5 part, resol reworked material 2-5 part, modified Nano filling 5-12 part, expanded graphite 3-15 part, ammonium polyphosphate 2-12 part, silane coupling agent 3-5 part, epoxy soybean oil 1-2.5 part, Octyl adipate 0.3-1 part, dimethyl methyl phosphonate 2-5 part, 2, 2-bis-(chloromethyl)-1, 3-propylidene-four (2-chloroethyl) bisphosphate 1-4 part.
Preferably, in its raw material, the weight ratio of polyurethane elastomer, polyvinyl chloride reworked material, epoxy resin reworked material, recycled polyethylene, resol reworked material is 100:20-28:7-11:1.7-3:2.6-4.
Preferably, its raw material comprises following component by weight: polyurethane elastomer 100 parts, polyvinyl chloride reworked material 22-26 part, epoxy resin reworked material 9-11 part, acrylic acid esters co-polymer 2.1-2.6 part, stearic acid 0.7-1.1 part, Zinic stearas 0.6-0.8 part, calcium stearate 0.6-0.8 part, recycled polyethylene 2.1-2.6 part, resol reworked material 3.3-3.6 part, modified Nano filling 7-9 part, expanded graphite 8-10 part, ammonium polyphosphate 7-9 part, silane coupling agent 3.8-4.3 part, epoxy soybean oil 1.8-2.1 part, Octyl adipate 0.8-1 part, dimethyl methyl phosphonate 3.6-4.1 part, 2, 2-bis-(chloromethyl)-1, 3-propylidene-four (2-chloroethyl) bisphosphate 2.9-3.5 part.
Preferably, its raw material comprises following component by weight: polyurethane elastomer 100 parts, polyvinyl chloride reworked material 25 parts, epoxy resin reworked material 10 parts, acrylic acid esters co-polymer 2.5 parts, stearic acid 1 part, Zinic stearas 0.65 part, calcium stearate 0.7 part, recycled polyethylene 2.5 parts, resol reworked material 3.4 parts, modified Nano filling 8 parts, expanded graphite 9.2 parts, ammonium polyphosphate 8.5 parts, silane coupling agent 4 parts, epoxy soybean oil 1.9 parts, Octyl adipate 0.9 part, dimethyl methyl phosphonate 4 parts, 2, 2-bis-(chloromethyl)-1, 3-propylidene-four (2-chloroethyl) bisphosphate 3.2 parts.
Preferably, described polyvinyl chloride reworked material is rolled into powder by after the fragmentation of electron wastes igelite, obtains after crossing 300 mesh sieves; Described recycled polyethylene is rolled into powder by after the fragmentation of electron wastes vinyon, obtains after crossing 300 mesh sieves.
Preferably, described modified Nano filling is prepared according to following technique: by weight by 20-50 part nano-cerium oxide, 10-25 part nano-calcium carbonate, 3-10 part nano-aluminum hydroxide and 2-10 part nano-zinc borate mix, then plasma deposition stove is placed in, add 3-15 part vinylformic acid-3-(perfluor-3-methyl butyl)-2-hydroxypropyl acrylate again, 2-10 part vinyltriethoxysilane and 1-5 part hydroxyethyl meth acrylate phosphoric acid ester, adopt the argon plasma process 10-25min of 20-30W, then 10-20min oxygen is passed into, after vacuum chamber being warming up to 140-150 DEG C, 5-20min is processed under 65-75W, through washing after end, drying obtains described modified Nano filling.
Preferably, described modified Nano filling is prepared according to following technique: by weight by 40 parts of nano-cerium oxides, 20 parts of nano-calcium carbonates, 8 parts of nano-aluminum hydroxides and 7 parts of nano-zinc borates mix, then plasma deposition stove is placed in, add 12 parts of vinylformic acid-3-(perfluor-3-methyl butyl)-2-hydroxypropyl acrylate again, 8 parts of vinyltriethoxysilanes and 3.2 parts of hydroxyethyl meth acrylate phosphoric acid ester, adopt the argon plasma process 20min of 26W, then 15min oxygen is passed into, after vacuum chamber being warming up to 145 DEG C, 15min is processed under 70W, through washing after end, drying obtains described modified Nano filling, in the preparation process of modified Nano filling, have selected nano-cerium oxide, nano-calcium carbonate, nano-aluminum hydroxide and nano-zinc borate are as inorganic nano material, the ageing resistance of modified Nano filling excellence is given after coordinating, thermotolerance and flame retardant resistance, modified Nano filling is added in system, improve the ageing resistance of matrix material, thermotolerance and flame retardant resistance, significantly improve the tear strength of matrix material simultaneously, hardness and elongation at break, vinylformic acid-3-(perfluor-3-the methyl butyl)-2-hydroxypropyl acrylate added afterwards, vinyltriethoxysilane and hydroxyethyl meth acrylate phosphoric acid ester, under the process of plasma body, when keeping inorganic nano material structure, be aggregated to the surface of inorganic nano material, thus it is simultaneously fluorine-containing at the surface grafting of inorganic nano material, siliceous and phosphorous superpolymer, give the water tolerance of its excellence, thermotolerance and flame retardant resistance, modified Nano filling is added in system, substantially increase the water tolerance of matrix material, thermotolerance and flame retardant resistance, simultaneously because the surface of modified Nano filling introduces a large amount of hydroxyls, it is in system, can with isocyanic ester generation chemical reaction, effectively inhibit the reunion of modified Nano filling in system, improve the dispersiveness in system, it can share part bearing capacity in system, be conducive to the transmission of stress and the consumption of energy, improve toughness and the intensity of matrix material.
Preferably, the median size of described nano-cerium oxide is 10-25nm; The median size of described nano-calcium carbonate is 25-40nm; The median size of described nano-aluminum hydroxide is 20-50nm; The median size of described nano-zinc borate is 30-60nm.
In the present invention, take polyurethane elastomer as major ingredient, give wear resistance and the ageing resistance of matrix material excellence, the polyvinyl chloride reworked material added, epoxy resin reworked material and acrylic acid esters co-polymer have good consistency with polyurethane elastomer in system, improve the toughness of matrix material, improve erosion resistance and the flame retardant resistance of matrix material, make use of waste plastics simultaneously, saved cost, environment friendly is good; The cooperation of Zinic stearas, calcium stearate adds in system, avoids the defect adding the poor stability of introducing because of polyvinyl chloride reworked material, improves the package stability of matrix material; Recycled polyethylene adds in system and has synergy with stearic acid, improves the processing characteristics of system, has saved cost simultaneously; Modified Nano filling, expanded graphite, ammonium polyphosphate, dimethyl methyl phosphonate, 2,2-bis-(chloromethyl)-1, the cooperation of 3-propylidene-four (2-chloroethyl) bisphosphate adds in system, there is synergy, while improving the flame retardant resistance of matrix material and thermotolerance, improve the intensity of matrix material.
Embodiment
Below, by specific embodiment, technical scheme of the present invention is described in detail.
Embodiment 1
A kind of electron wastes recycled plastics polymers modified polyurethane matrix material that the present invention proposes, its raw material comprises following component by weight: polyurethane elastomer 100 parts, polyvinyl chloride reworked material 15 parts, epoxy resin reworked material 12 parts, acrylic acid esters co-polymer 1 part, stearic acid 1.2 parts, Zinic stearas 0.5 part, calcium stearate 1 part, recycled polyethylene 1 part, resol reworked material 5 parts, modified Nano filling 5 parts, expanded graphite 15 parts, ammonium polyphosphate 2 parts, silane coupling agent 5 parts, epoxy soybean oil 1 part, Octyl adipate 1 part, dimethyl methyl phosphonate 2 parts, 2, 2-bis-(chloromethyl)-1, 3-propylidene-four (2-chloroethyl) bisphosphate 4 parts,
Wherein, described modified Nano filling is prepared according to following technique: by weight by 20 parts of nano-cerium oxides, 25 parts of nano-calcium carbonates, 3 parts of nano-aluminum hydroxides and 10 parts of nano-zinc borates mix, then plasma deposition stove is placed in, add 3 parts of vinylformic acid-3-(perfluor-3-methyl butyl)-2-hydroxypropyl acrylate again, 10 parts of vinyltriethoxysilanes and 1 part of hydroxyethyl meth acrylate phosphoric acid ester, adopt the argon plasma process 10min of 30W, then 20min oxygen is passed into, after vacuum chamber being warming up to 140 DEG C, 5min is processed under 75W, through washing after end, drying obtains described modified Nano filling, the median size of described nano-cerium oxide is 25nm, the median size of described nano-calcium carbonate is 25nm, the median size of described nano-aluminum hydroxide is 50nm, the median size of described nano-zinc borate is 30nm.
Embodiment 2
A kind of electron wastes recycled plastics polymers modified polyurethane matrix material that the present invention proposes, its raw material comprises following component by weight: polyurethane elastomer 100 parts, polyvinyl chloride reworked material 30 parts, epoxy resin reworked material 5 parts, acrylic acid esters co-polymer 3 parts, stearic acid 0.3 part, Zinic stearas 1 part, calcium stearate 0.2 part, recycled polyethylene 3.5 parts, resol reworked material 2 parts, modified Nano filling 12 parts, expanded graphite 3 parts, ammonium polyphosphate 12 parts, silane coupling agent 3 parts, epoxy soybean oil 2.5 parts, Octyl adipate 0.3 part, dimethyl methyl phosphonate 5 parts, 2, 2-bis-(chloromethyl)-1, 3-propylidene-four (2-chloroethyl) bisphosphate 1 part,
Wherein, described modified Nano filling is prepared according to following technique: by weight by 50 parts of nano-cerium oxides, 10 parts of nano-calcium carbonates, 10 parts of nano-aluminum hydroxides and 2 parts of nano-zinc borates mix, then plasma deposition stove is placed in, add 15 parts of vinylformic acid-3-(perfluor-3-methyl butyl)-2-hydroxypropyl acrylate again, 2 parts of vinyltriethoxysilanes and 5 parts of hydroxyethyl meth acrylate phosphoric acid ester, adopt the argon plasma process 25min of 20W, then 10min oxygen is passed into, after vacuum chamber being warming up to 150 DEG C, 20min is processed under 65W, through washing after end, drying obtains described modified Nano filling, the median size of described nano-cerium oxide is 10nm, the median size of described nano-calcium carbonate is 40nm, the median size of described nano-aluminum hydroxide is 20nm, the median size of described nano-zinc borate is 60nm.
Embodiment 3
A kind of electron wastes recycled plastics polymers modified polyurethane matrix material that the present invention proposes, its raw material comprises following component by weight: polyurethane elastomer 100 parts, polyvinyl chloride reworked material 25 parts, epoxy resin reworked material 10 parts, acrylic acid esters co-polymer 2.5 parts, stearic acid 1 part, Zinic stearas 0.65 part, calcium stearate 0.7 part, recycled polyethylene 2.5 parts, resol reworked material 3.4 parts, modified Nano filling 8 parts, expanded graphite 9.2 parts, ammonium polyphosphate 8.5 parts, silane coupling agent 4 parts, epoxy soybean oil 1.9 parts, Octyl adipate 0.9 part, dimethyl methyl phosphonate 4 parts, 2, 2-bis-(chloromethyl)-1, 3-propylidene-four (2-chloroethyl) bisphosphate 3.2 parts,
Wherein, described polyvinyl chloride reworked material is rolled into powder by after the fragmentation of electron wastes igelite, obtains after crossing 300 mesh sieves; Described recycled polyethylene is rolled into powder by after the fragmentation of electron wastes vinyon, obtains after crossing 300 mesh sieves;
Described modified Nano filling is prepared according to following technique: by weight by 40 parts of nano-cerium oxides, 20 parts of nano-calcium carbonates, 8 parts of nano-aluminum hydroxides and 7 parts of nano-zinc borates mix, then plasma deposition stove is placed in, add 12 parts of vinylformic acid-3-(perfluor-3-methyl butyl)-2-hydroxypropyl acrylate again, 8 parts of vinyltriethoxysilanes and 3.2 parts of hydroxyethyl meth acrylate phosphoric acid ester, adopt the argon plasma process 20min of 26W, then 15min oxygen is passed into, after vacuum chamber being warming up to 145 DEG C, 15min is processed under 70W, through washing after end, drying obtains described modified Nano filling, the median size of described nano-cerium oxide is 18nm, the median size of described nano-calcium carbonate is 30nm, the median size of described nano-aluminum hydroxide is 35nm, the median size of described nano-zinc borate is 40nm.
Embodiment 4
A kind of electron wastes recycled plastics polymers modified polyurethane matrix material that the present invention proposes, its raw material comprises following component by weight: polyurethane elastomer 100 parts, polyvinyl chloride reworked material 22 parts, epoxy resin reworked material 11 parts, acrylic acid esters co-polymer 2.1 parts, stearic acid 1.1 parts, Zinic stearas 0.6 part, calcium stearate 0.8 part, recycled polyethylene 2.1 parts, resol reworked material 3.6 parts, modified Nano filling 7 parts, expanded graphite 10 parts, ammonium polyphosphate 7 parts, silane coupling agent 4.3 parts, epoxy soybean oil 1.8 parts, Octyl adipate 1 part, dimethyl methyl phosphonate 3.6 parts, 2, 2-bis-(chloromethyl)-1, 3-propylidene-four (2-chloroethyl) bisphosphate 3.5 parts,
Wherein, described modified Nano filling is prepared according to following technique: by weight by 28 parts of nano-cerium oxides, 22 parts of nano-calcium carbonates, 6 parts of nano-aluminum hydroxides and 8 parts of nano-zinc borates mix, then plasma deposition stove is placed in, add 9 parts of vinylformic acid-3-(perfluor-3-methyl butyl)-2-hydroxypropyl acrylate again, 8.5 parts of vinyltriethoxysilanes and 3.2 parts of hydroxyethyl meth acrylate phosphoric acid ester, adopt the argon plasma process 18min of 28W, then 18min oxygen is passed into, after vacuum chamber being warming up to 145 DEG C, 10min is processed under 72W, through washing after end, drying obtains described modified Nano filling, the median size of described nano-cerium oxide is 18nm, the median size of described nano-calcium carbonate is 30nm, the median size of described nano-aluminum hydroxide is 35nm, the median size of described nano-zinc borate is 50nm.
Embodiment 5
A kind of electron wastes recycled plastics polymers modified polyurethane matrix material that the present invention proposes, its raw material comprises following component by weight: polyurethane elastomer 100 parts, polyvinyl chloride reworked material 26 parts, epoxy resin reworked material 9 parts, acrylic acid esters co-polymer 2.6 parts, stearic acid 0.7 part, Zinic stearas 0.8 part, calcium stearate 0.6 part, recycled polyethylene 2.6 parts, resol reworked material 3.3 parts, modified Nano filling 9 parts, expanded graphite 8 parts, ammonium polyphosphate 9 parts, silane coupling agent 3.8 parts, epoxy soybean oil 2.1 parts, Octyl adipate 0.8 part, dimethyl methyl phosphonate 4.1 parts, 2, 2-bis-(chloromethyl)-1, 3-propylidene-four (2-chloroethyl) bisphosphate 2.9 parts,
Wherein, described modified Nano filling is prepared according to following technique: by weight by 45 parts of nano-cerium oxides, 17 parts of nano-calcium carbonates, 8.5 parts of nano-aluminum hydroxides and 5 parts of nano-zinc borates mix, then plasma deposition stove is placed in, add 12 parts of vinylformic acid-3-(perfluor-3-methyl butyl)-2-hydroxypropyl acrylate again, 5.5 parts of vinyltriethoxysilanes and 2.5 parts of hydroxyethyl meth acrylate phosphoric acid ester, adopt the argon plasma process 22min of 23W, then 15min oxygen is passed into, after vacuum chamber being warming up to 148 DEG C, 18min is processed under 68W, through washing after end, drying obtains described modified Nano filling, the median size of described nano-cerium oxide is 20nm, the median size of described nano-calcium carbonate is 35nm, the median size of described nano-aluminum hydroxide is 40nm, the median size of described nano-zinc borate is 45nm.
The above; be only the present invention's preferably embodiment; but protection scope of the present invention is not limited thereto; anyly be familiar with those skilled in the art in the technical scope that the present invention discloses; be equal to according to technical scheme of the present invention and inventive concept thereof and replace or change, all should be encompassed within protection scope of the present invention.
Claims (8)
1. an electron wastes recycled plastics polymers modified polyurethane matrix material, it is characterized in that, its raw material comprises following component by weight: polyurethane elastomer 100 parts, polyvinyl chloride reworked material 15-30 part, epoxy resin reworked material 5-12 part, acrylic acid esters co-polymer 1-3 part, stearic acid 0.3-1.2 part, Zinic stearas 0.5-1 part, calcium stearate 0.2-1 part, recycled polyethylene 1-3.5 part, resol reworked material 2-5 part, modified Nano filling 5-12 part, expanded graphite 3-15 part, ammonium polyphosphate 2-12 part, silane coupling agent 3-5 part, epoxy soybean oil 1-2.5 part, Octyl adipate 0.3-1 part, dimethyl methyl phosphonate 2-5 part, 2, 2-bis-(chloromethyl)-1, 3-propylidene-four (2-chloroethyl) bisphosphate 1-4 part.
2. electron wastes recycled plastics polymers modified polyurethane matrix material according to claim 1, it is characterized in that, in its raw material, the weight ratio of polyurethane elastomer, polyvinyl chloride reworked material, epoxy resin reworked material, recycled polyethylene, resol reworked material is 100:20-28:7-11:1.7-3:2.6-4.
3. electron wastes recycled plastics polymers modified polyurethane matrix material according to claim 1 or 2, it is characterized in that, its raw material comprises following component by weight: polyurethane elastomer 100 parts, polyvinyl chloride reworked material 22-26 part, epoxy resin reworked material 9-11 part, acrylic acid esters co-polymer 2.1-2.6 part, stearic acid 0.7-1.1 part, Zinic stearas 0.6-0.8 part, calcium stearate 0.6-0.8 part, recycled polyethylene 2.1-2.6 part, resol reworked material 3.3-3.6 part, modified Nano filling 7-9 part, expanded graphite 8-10 part, ammonium polyphosphate 7-9 part, silane coupling agent 3.8-4.3 part, epoxy soybean oil 1.8-2.1 part, Octyl adipate 0.8-1 part, dimethyl methyl phosphonate 3.6-4.1 part, 2, 2-bis-(chloromethyl)-1, 3-propylidene-four (2-chloroethyl) bisphosphate 2.9-3.5 part.
4. electron wastes recycled plastics polymers modified polyurethane matrix material according to any one of claim 1-3, it is characterized in that, its raw material comprises following component by weight: polyurethane elastomer 100 parts, polyvinyl chloride reworked material 25 parts, epoxy resin reworked material 10 parts, acrylic acid esters co-polymer 2.5 parts, stearic acid 1 part, Zinic stearas 0.65 part, calcium stearate 0.7 part, recycled polyethylene 2.5 parts, resol reworked material 3.4 parts, modified Nano filling 8 parts, expanded graphite 9.2 parts, ammonium polyphosphate 8.5 parts, silane coupling agent 4 parts, epoxy soybean oil 1.9 parts, Octyl adipate 0.9 part, dimethyl methyl phosphonate 4 parts, 2, 2-bis-(chloromethyl)-1, 3-propylidene-four (2-chloroethyl) bisphosphate 3.2 parts.
5. electron wastes recycled plastics polymers modified polyurethane matrix material according to any one of claim 1-4, it is characterized in that, described polyvinyl chloride reworked material is rolled into powder by after the fragmentation of electron wastes igelite, obtains after crossing 300 mesh sieves; Described recycled polyethylene is rolled into powder by after the fragmentation of electron wastes vinyon, obtains after crossing 300 mesh sieves.
6. electron wastes recycled plastics polymers modified polyurethane matrix material according to any one of claim 1-5, it is characterized in that, described modified Nano filling is prepared according to following technique: by weight by 20-50 part nano-cerium oxide, 10-25 part nano-calcium carbonate, 3-10 part nano-aluminum hydroxide and 2-10 part nano-zinc borate mix, then plasma deposition stove is placed in, add 3-15 part vinylformic acid-3-(perfluor-3-methyl butyl)-2-hydroxypropyl acrylate again, 2-10 part vinyltriethoxysilane and 1-5 part hydroxyethyl meth acrylate phosphoric acid ester, adopt the argon plasma process 10-25min of 20-30W, then 10-20min oxygen is passed into, after vacuum chamber being warming up to 140-150 DEG C, 5-20min is processed under 65-75W, through washing after end, drying obtains described modified Nano filling.
7. electron wastes recycled plastics polymers modified polyurethane matrix material according to any one of claim 1-6, it is characterized in that, described modified Nano filling is prepared according to following technique: by weight by 40 parts of nano-cerium oxides, 20 parts of nano-calcium carbonates, 8 parts of nano-aluminum hydroxides and 7 parts of nano-zinc borates mix, then plasma deposition stove is placed in, add 12 parts of vinylformic acid-3-(perfluor-3-methyl butyl)-2-hydroxypropyl acrylate again, 8 parts of vinyltriethoxysilanes and 3.2 parts of hydroxyethyl meth acrylate phosphoric acid ester, adopt the argon plasma process 20min of 26W, then 15min oxygen is passed into, after vacuum chamber being warming up to 145 DEG C, 15min is processed under 70W, through washing after end, drying obtains described modified Nano filling.
8. electron wastes recycled plastics polymers modified polyurethane matrix material according to claim 6 or 7, is characterized in that, the median size of described nano-cerium oxide is 10-25nm; The median size of described nano-calcium carbonate is 25-40nm; The median size of described nano-aluminum hydroxide is 20-50nm; The median size of described nano-zinc borate is 30-60nm.
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Application publication date: 20160224 |