CN105367944A - High strength anti-corrosion floor and preparation method thereof - Google Patents

High strength anti-corrosion floor and preparation method thereof Download PDF

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Publication number
CN105367944A
CN105367944A CN201510735825.2A CN201510735825A CN105367944A CN 105367944 A CN105367944 A CN 105367944A CN 201510735825 A CN201510735825 A CN 201510735825A CN 105367944 A CN105367944 A CN 105367944A
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add
minute
mentioned
zirconium phosphate
stir
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张文勇
王林
夏广志
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CHUZHOU YONGTONG TRAFFIC EQUIPMENT CO LTD
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CHUZHOU YONGTONG TRAFFIC EQUIPMENT CO LTD
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00Use of pretreated ingredients
    • C08K9/02Ingredients treated with inorganic substances
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/32Phosphorus-containing compounds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00Use of pretreated ingredients
    • C08K9/04Ingredients treated with organic substances
    • EFIXED CONSTRUCTIONS
    • E04BUILDING
    • E04FFINISHING WORK ON BUILDINGS, e.g. STAIRS, FLOORS
    • E04F15/00Flooring
    • E04F15/02Flooring or floor layers composed of a number of similar elements
    • E04F15/10Flooring or floor layers composed of a number of similar elements of other materials, e.g. fibrous or chipped materials, organic plastics, magnesite tiles, hardboard, or with a top layer of other materials
    • E04F15/105Flooring or floor layers composed of a number of similar elements of other materials, e.g. fibrous or chipped materials, organic plastics, magnesite tiles, hardboard, or with a top layer of other materials of organic plastics with or without reinforcements or filling materials
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/32Phosphorus-containing compounds
    • C08K2003/321Phosphates
    • C08K2003/328Phosphates of heavy metals
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00Specific properties of additives
    • C08K2201/011Nanostructured additives
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00Properties
    • C08L2201/02Flame or fire retardant/resistant
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00Properties
    • C08L2201/08Stabilised against heat, light or radiation or oxydation
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00Applications
    • C08L2203/14Applications used for foams

Abstract

The invention discloses a high strength anti-corrosion floor, which comprises raw materials with parts by weight: bauxite 6-10, hydrolytic polymaleic anhydride 1-2, glycolic acids 0.7-1, zirconium oxychloride octahydrate 17-20, 40-47% hydrochloric acids 10-15, 80-85% phosphoric acids 90-100, tetrakis hydroxymethyl phosphonium sulfate 3-4, 25-30% methylamine water solution 4-7, t rifluoroethyl methacrylate 5-7, 2-Octyl-4-isothiazolin-3-one 0.2-0.4, ammonium persulfate 0.06-0.1, divinyl benzene 0.01-0.02, azodicarbonamide 1-2, polyvinyl chloride 130-200, aluminium dihydrogen phosphate 2-4, tributyl citrate 4-6, potassium hydrogen sulfate 0.7-1 and polybenzimidazole 0.4-1. The high strength anti-corrosion floor is high in surface strength, excellent in bearing capacity, superior in comprehensive performance and strong in anti-corrosion performance.

Description

A kind of high-strength anti-corrosion floor and preparation method thereof
Technical field
The present invention relates to technical field of floor, particularly relate to a kind of high-strength anti-corrosion floor and preparation method thereof.
Background technology
PVC, as world's second largest general-purpose plastics, has good over-all properties, and cheap, raw material sources are extensive etc., and advantage has given play to vital role in all trades and professions.PVC foam material not only inherits above all advantages, and there is defect or the deficiency of some performances, as intensity, rigidity and thermomechanical property etc. do not reach the expectation of people, especially PVC foam material can discharge poisonous dense smoke when burning, and these all seriously hinder development and the application of PVC foam materials.Along with nanometer in recent years in the material shown by the great potential that goes out, make to form by modifications such as laminated inorganic matters the focus that over-all properties that nano composite material improves material becomes Recent study.Laminated inorganic matter makes the thermal stability of polymer composites after organically-modified, mechanical property significantly improves, particularly alpha zirconium phosphate is as a kind of novel nano particle with unique texture and character, there is purity high, loading capacity greatly easily realizes intercalation or lift-off structure, easily form nanostructure with polymkeric substance compound, this not only gives the excellent mechanical property of polymer materials, barrier property but also laminar nano particle is applied to the effect that can also play foaming nucleation agent in foam material to such an extent as to reaches the object optimizing foaming quality.On the other hand, PVC foam material, in inferior position that is fire-retardant and that press down in cigarette, also counteracts that it is further applied.And add anti-flaming smoke-inhibiting agent and just can well address this problem, the research of forefathers is for we have laid a good foundation, organic tin anti-flaming smoke-inhibiting agent and molybdenum class anti-flaming smoke-inhibiting agent have all shown outstanding flame-retardant smoke inhibition effect, the anti-flaming smoke-inhibiting agent of special organic is that same polymkeric substance has good consistency, this is that other fire retardants are unapproachable, therefore for other fire retardants, have suitable DEVELOPMENT PROSPECT, both conbined usage has no report in the flame-retardant smoke inhibition research of PVC at present.So this paper is intended to introduce organically-modified alpha zirconium phosphate Nano filling, improve foaming quality and mechanical property, the thermal stability etc. of PVC foam material.
Summary of the invention
The object of the invention is exactly the defect in order to make up prior art, provides a kind of high-strength anti-corrosion floor and preparation method thereof.
The present invention is achieved by the following technical solutions:
A kind of high-strength anti-corrosion floor, it is made up of the raw material of following weight parts:
Bauxitic clay 6-10, hydrolytic polymaleic anhydride 1-2, oxyacetic acid 0.7-1, eight water zirconium oxychloride 17-20, the hydrochloric acid 10-15 of 40-47%, the phosphatase 79 0-100 of 80-85%, tetrakis hydroxymetyl phosphonium sulfuric 3-4, 25-30% aqueous methylamine solution 4-7, trifluoroethyl methacrylate 5-7, octylisothiazolinone 0.2-0.4, ammonium persulphate 0.06-0.1, Vinylstyrene 0.01-0.02, Cellmic C 121 1-2, polyvinyl chloride 130-200, aluminium dihydrogen phosphate 2-4, tributyl citrate 4-6, sal enixum 0.7-1, polybenzimidazole 0.4-1.
The preparation method on described high-strength anti-corrosion floor, comprises the following steps:
(1) eight water zirconium oxychlorides are joined in 15-18 times of distilled water, stir, add the hydrochloric acid of above-mentioned 40-47%, the phosphoric acid of 80-85% successively, induction stirring 3-4 days under room temperature, filters, and is 5 with deionized water wash to PH, vacuum-drying at 60-65 DEG C, grinding, obtains alpha zirconium phosphate;
(2) above-mentioned bauxitic clay is calcined 1-2 hour at 700-800 DEG C, cooling, mix with aluminium dihydrogen phosphate, ball milling is even, joins in compound weight 1.5-1 times water, send in process furnace, heat 10-15 minute at 170-200 DEG C, discharging cools, and mixes with above-mentioned alpha zirconium phosphate, ball milling is even, obtains enhancing alpha zirconium phosphate;
(3) said hydrolyzed polymaleic anhydride joined in 4-6 times of deionized water, stir, add sal enixum, raised temperature is 60-70 DEG C, adds octylisothiazolinone, and insulated and stirred 10-17 minute obtains anticorrosion aqueous solution;
(4) above-mentioned polybenzimidazole is joined in the ethanolic soln of 16-20 times of 20-30%, stir, add trifluoroethyl methacrylate, raised temperature is 70-75 DEG C, adds Vinylstyrene, anticorrosion aqueous solution, stirs, insulation reaction 3-4 hour, obtains anticorrosion monomer;
(5) above-mentioned enhancing alpha zirconium phosphate is joined in 90-100 times of deionized water, stir, add aqueous methylamine solution, ultrasonic 30-35 minute, add tetrakis hydroxymetyl phosphonium sulfuric, dispersed with stirring 10-16 minute, add above-mentioned anticorrosion monomer, ultrasonic 3-5 minute, add ammonium persulphate, insulation reaction 6-10 hour at 75-80 DEG C, centrifugation, throw out is washed, dries, obtain organically-modified zirconium phosphate;
(6) above-mentioned organically-modified zirconium phosphate is mixed with polyvinyl chloride, send in homogenizer, 1000-1200r/min stirs 20-30 minute, and slow raised temperature is 120-130 DEG C, reduction rotating speed is 300-400r/min, be stirred to 46-50 DEG C, then raised temperature is 130-140 DEG C, adds each raw material of residue, heat-insulation preheating 50-60 minute, melt extruded by forcing machine, through traction cutting, plucking, to obtain final product.
Advantage of the present invention is:
(1) floor of the present invention has good heat-resistant stability:
Adopt tetrakis hydroxymetyl phosphonium sulfuric as properties-correcting agent, interlayer do not have can catalysis polyvinyl chloride decompose the factor, obtain the laminate structure of organically-modified zirconium phosphate, effectively can play the iris action of energy and material; On the other hand, organically-modified alpha zirconium phosphate add the foaming quality improving polyvinyl-chloride foam material, make uniform foam cell, obvious boundary has been there is between abscess, namely closed pore quantity is increasing, open-celled structure reduces, and this unicellular structure absorbs a large amount of heat in the process of heat transmission, stops the propagation of heat; In addition, adding organically-modified alpha zirconium phosphate can make polyvinyl chloride composite foam material be can be good at keeping the shape of abscess when impacting, abscess is made to keep original rigidity and toughness, therefore improve the thickness of polyvinyl chloride walls, enhance the outer position of its opposing and the ability destroyed is produced to it;
(2) floor of the present invention has good water resisting property:
Through organically-modified alpha zirconium phosphate, due to the H+ between organic cation substituted layer or organic anion the adsorption at alpha zirconium phosphate interlayer and modified hydrophobicity is improved comparatively significantly;
(3) floor of the present invention has good shock resistance:
The present invention adopts tetrakis hydroxymetyl phosphonium sulfuric to significantly improve the foaming quality of polyvinyl-chloride foam material as properties-correcting agent, and abscess is comparatively even, and cell wall presents spherical, and complete cell wall absorbs energy by there is deformation, then toughness increases;
(4) floor of the present invention has good flame retardant properties:
Alpha zirconium phosphate self is laminate structure, and through the lift-off structure that modified formation is certain, no matter be laminate structure or lift-off structure, the existence of these structures, matter and energy iris action can be played when polymer combustion, and can HCl be discharged during polyvinyl chloride burning, HCL gas self has obvious flame retardant resistance;
(5) first the present invention makes alpha zirconium phosphate gelatinizing with methylamine, then using trifluoroethyl methacrylate as anticorrosion monomer, embed in the course of the polymerization process and stable existence between modified alpha-zirconium phosphate layer, ensure heat-resisting, the water resistant of modification alpha zirconium phosphate, shock resistance, fire-retardant while improve antiseptic property;
Floor surface intensity of the present invention is high, and bearing is good, and over-all properties is superior, and preservative property are strong.
Embodiment
A kind of high-strength anti-corrosion floor, it is made up of the raw material of following weight parts:
The phosphatase 79 0 of the hydrochloric acid 10,80% of bauxitic clay 6, hydrolytic polymaleic anhydride 1, oxyacetic acid 0.7, eight water zirconium oxychloride 17,40%, tetrakis hydroxymetyl phosphonium sulfuric 3,25% aqueous methylamine solution 4, trifluoroethyl methacrylate 5, octylisothiazolinone 0.2, ammonium persulphate 0.06, Vinylstyrene 0.01, Cellmic C 121 1, polyvinyl chloride 130, aluminium dihydrogen phosphate 2, tributyl citrate 4, sal enixum 0.7, polybenzimidazole 0.4.
The preparation method on described high-strength anti-corrosion floor, comprises the following steps:
(1) being joined in 15 times of distilled water by eight water zirconium oxychlorides, stir, add the hydrochloric acid of above-mentioned 40%, the phosphoric acid of 80% successively, induction stirring 3 days under room temperature, filter, is 5 with deionized water wash to PH, vacuum-drying at 60 DEG C, and grinding, obtains α zirconium phosphate;
(2) calcined 1 hour at 700 DEG C by above-mentioned bauxitic clay, cooling, mix with aluminium dihydrogen phosphate, ball milling is even, join in compound weight 1.5 times of water, send in process furnace, heat 10 minutes at 170 DEG C, discharging cools, mix with above-mentioned α zirconium phosphate, ball milling is even, obtains reinforcing alpha zirconium phosphate;
(3) said hydrolyzed polymaleic anhydride joined in 4 times of deionized waters, stir, add sal enixum, raised temperature is 60 DEG C, adds octylisothiazolinone, and insulated and stirred 10 minutes, obtains anticorrosion aqueous solution;
(4) joined in the ethanolic soln of 16 times 20% by above-mentioned polybenzimidazole, stir, add trifluoroethyl methacrylate, raised temperature is 70 DEG C, adds Vinylstyrene, anticorrosion aqueous solution, stirs, and insulation reaction 3 hours, obtains anticorrosion monomer;
(5) above-mentioned reinforcing alpha zirconium phosphate is joined in 90 times of deionized waters, stir, add aqueous methylamine solution, ultrasonic 30 minutes, add tetrakis hydroxymetyl phosphonium sulfuric, dispersed with stirring 10 minutes, add above-mentioned anticorrosion monomer, ultrasonic 3 minutes, add ammonium persulphate, insulation reaction 6 hours at 75 DEG C, centrifugation, throw out is washed, dries, obtain organically-modified zirconium phosphate;
(6) above-mentioned organically-modified zirconium phosphate is mixed with polyvinyl chloride, send in homogenizer, 1000r/min stirs 20 minutes, and slow raised temperature is 120 DEG C, reduction rotating speed is 300r/min, be stirred to 46 DEG C, then raised temperature is 130 DEG C, adds each raw material of residue, heat-insulation preheating 50 minutes, melt extruded by forcing machine, through traction cutting, plucking, to obtain final product.
Performance test:
Density: 0.9g/cm 3;
Shore D hardness: 73 degree;
Camber intensity: 25.1MPa;
Unnotched impact strength: 75kJ/m 2;
Water-intake rate: 0.484%;
Shock resistance: flawless;
Oxygen index: 37.1%;
Miter angle burns: difficult combustion;
Nail-holding ability: 2.2kN;
Environmental-protecting performance (methyl alcohol burst size, condensed steam water 9-11L): 0.2mg/L.

Claims (2)

1. a high-strength anti-corrosion floor, is characterized in that, it is made up of the raw material of following weight parts:
Bauxitic clay 6-10, hydrolytic polymaleic anhydride 1-2, oxyacetic acid 0.7-1, eight water zirconium oxychloride 17-20, the hydrochloric acid 10-15 of 40-47%, the phosphatase 79 0-100 of 80-85%, tetrakis hydroxymetyl phosphonium sulfuric 3-4, 25-30% aqueous methylamine solution 4-7, trifluoroethyl methacrylate 5-7, octylisothiazolinone 0.2-0.4, ammonium persulphate 0.06-0.1, Vinylstyrene 0.01-0.02, Cellmic C 121 1-2, polyvinyl chloride 130-200, aluminium dihydrogen phosphate 2-4, tributyl citrate 4-6, sal enixum 0.7-1, polybenzimidazole 0.4-1.
2. the preparation method on high-strength anti-corrosion floor as claimed in claim 1, is characterized in that, comprise the following steps:
(1) eight water zirconium oxychlorides are joined in 15-18 times of distilled water, stir, add the hydrochloric acid of above-mentioned 40-47%, the phosphoric acid of 80-85% successively, induction stirring 3-4 days under room temperature, filters, and is 5 with deionized water wash to PH, vacuum-drying at 60-65 DEG C, grinding, obtains alpha zirconium phosphate;
(2) above-mentioned bauxitic clay is calcined 1-2 hour at 700-800 DEG C, cooling, mix with aluminium dihydrogen phosphate, ball milling is even, joins in compound weight 1.5-1 times water, send in process furnace, heat 10-15 minute at 170-200 DEG C, discharging cools, and mixes with above-mentioned alpha zirconium phosphate, ball milling is even, obtains enhancing alpha zirconium phosphate;
(3) said hydrolyzed polymaleic anhydride joined in 4-6 times of deionized water, stir, add sal enixum, raised temperature is 60-70 DEG C, adds octylisothiazolinone, and insulated and stirred 10-17 minute obtains anticorrosion aqueous solution;
(4) above-mentioned polybenzimidazole is joined in the ethanolic soln of 16-20 times of 20-30%, stir, add trifluoroethyl methacrylate, raised temperature is 70-75 DEG C, adds Vinylstyrene, anticorrosion aqueous solution, stirs, insulation reaction 3-4 hour, obtains anticorrosion monomer;
(5) above-mentioned enhancing alpha zirconium phosphate is joined in 90-100 times of deionized water, stir, add aqueous methylamine solution, ultrasonic 30-35 minute, add tetrakis hydroxymetyl phosphonium sulfuric, dispersed with stirring 10-16 minute, add above-mentioned anticorrosion monomer, ultrasonic 3-5 minute, add ammonium persulphate, insulation reaction 6-10 hour at 75-80 DEG C, centrifugation, throw out is washed, dries, obtain organically-modified zirconium phosphate;
(6) above-mentioned organically-modified zirconium phosphate is mixed with polyvinyl chloride, send in homogenizer, 1000-1200r/min stirs 20-30 minute, and slow raised temperature is 120-130 DEG C, reduction rotating speed is 300-400r/min, be stirred to 46-50 DEG C, then raised temperature is 130-140 DEG C, adds each raw material of residue, heat-insulation preheating 50-60 minute, melt extruded by forcing machine, through traction cutting, plucking, to obtain final product.
CN201510735825.2A 2015-11-03 2015-11-03 High strength anti-corrosion floor and preparation method thereof Pending CN105367944A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105733134A (en) * 2016-04-26 2016-07-06 安徽悦尔伟塑料机械有限公司 Anti-mildew plastic and preparation method thereof

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* Cited by examiner, † Cited by third party
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CN102558758A (en) * 2012-01-04 2012-07-11 上海柯瑞冶金炉料有限公司 Phenolic resin foam material and preparing method thereof
CN104631775A (en) * 2013-11-12 2015-05-20 江阴华诚汽车内饰件有限公司 Coiled material floor having bacteria resistant function

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102558758A (en) * 2012-01-04 2012-07-11 上海柯瑞冶金炉料有限公司 Phenolic resin foam material and preparing method thereof
CN104631775A (en) * 2013-11-12 2015-05-20 江阴华诚汽车内饰件有限公司 Coiled material floor having bacteria resistant function

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
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施增楷: "磷酸锆剥离悬浮液的制备及其剪切变稀效应", 《广东化工》 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105733134A (en) * 2016-04-26 2016-07-06 安徽悦尔伟塑料机械有限公司 Anti-mildew plastic and preparation method thereof

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Application publication date: 20160302