CN105367945A - Low-cost anti-corrosion floor and preparation method thereof - Google Patents

Low-cost anti-corrosion floor and preparation method thereof Download PDF

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Publication number
CN105367945A
CN105367945A CN201510735867.6A CN201510735867A CN105367945A CN 105367945 A CN105367945 A CN 105367945A CN 201510735867 A CN201510735867 A CN 201510735867A CN 105367945 A CN105367945 A CN 105367945A
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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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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
    • C08K13/06—Pretreated ingredients and ingredients covered by the main groups C08K3/00 - C08K7/00
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/32—Phosphorus-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/098—Metal salts of carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/20—Carboxylic acid amides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • E—FIXED CONSTRUCTIONS
    • E04—BUILDING
    • E04F—FINISHING WORK ON BUILDINGS, e.g. STAIRS, FLOORS
    • E04F15/00—Flooring
    • E04F15/02—Flooring or floor layers composed of a number of similar elements
    • E04F15/10—Flooring 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
    • E04F15/105—Flooring 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/32—Phosphorus-containing compounds
    • C08K2003/321—Phosphates
    • C08K2003/328—Phosphates of heavy metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/14—Applications used for foams

Abstract

The invention discloses a low-cost anti-corrosion floor which is prepared from, by weight, 3-5 parts of tar residues, 2-4 parts of calcium stearate, 3-5 parts of polyisobutene, 17-20 parts of zirconium oxychloride octahydrate, 10-15 parts of 40-47% hydrochloric acid, 90-100 parts of 80-85% phosphoric acid, 3-4 parts of tetrakis hydroxymethyl phosphonium sulfate, 4-7 parts of a 25-30% methylamine aqueous solution, 5-7 parts of trifluoroethyl methacrylate, 0.2-0.4 part of octyl-isothiazolinone, 0.06-0.1 part of ammonium persulfate, 0.01-0.02 part of divinyl benzene, 1-2 parts of azodicarbonamide, 130-200 parts of polyvinyl chloride, 1-2 parts of oleic diethanolamine, 6-8 parts of tetradecanol oleate, 0.3-1 part of phytosterol and 1-2 parts of potassium citrate. Raw material cost is low, the preparation technology is simple, energy consumption is small, all indexes of the floor are in a high level, and comprehensive quality is good.

Description

A kind of low cost anticorrosive floor board and preparation method thereof
Technical field
The present invention relates to technical field of floor, particularly relate to a kind of low cost anticorrosive floor board 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 low cost anticorrosive floor board and preparation method thereof.
The present invention is achieved by the following technical solutions:
A kind of low cost anticorrosive floor board, it is made up of the raw material of following weight parts:
Coke tar refuse 3-5, calcium stearate 2-4, polyisobutene 3-5, 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, oleic acid diethyl amide 1-2, tetradecyl alcohol oleic acid ester 6-8, plant sterol 0.3-1, Tripotassium Citrate 1-2.
A preparation method for described low cost anticorrosive floor board, 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) joined in 12-17 times of deionized water by above-mentioned oleic acid diethyl amide, add calcium stearate under agitation condition, raised temperature is 60-70 DEG C, adds soda, and adjustment PH is 10-13, insulated and stirred 20-30 minute, obtains calcium stearate emulsion;
(3) joined by above-mentioned octylisothiazolinone in the ethanolic soln of 30-40 times of 20-30%, stir, add trifluoroethyl methacrylate, raised temperature is 70-75 DEG C, adds Vinylstyrene, insulation reaction 3-4 hour, obtains anticorrosion monomer;
(4) joined in 7-10 times of dehydrated alcohol by above-mentioned tetradecyl alcohol oleic acid ester, stir, add coke tar refuse, raised temperature is 70-80 DEG C, insulated and stirred 6-8 minute, obtains alcoholic solution;
(5) mixed with alcoholic solution by above-mentioned anticorrosion monomer, add plant sterol, 100-200 rev/min is stirred 30-40 minute, obtains anticorrosion monomer emulsion;
(6) above-mentioned 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 emulsion, 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;
(7) by above-mentioned organically-modified zirconium phosphate, the mixing of calcium stearate emulsion, be heated to boiling, keep boiling to water and do, dry 3-4 minute at 100-105 DEG C;
(8) each raw material after above-mentioned process 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;
Raw materials cost of the present invention is low, and preparation technology is simple, and consumed energy is less, and product indices all has higher level, and overall quality is good.
Embodiment
A kind of low cost anticorrosive floor board, it is made up of the raw material of following weight parts:
The phosphatase 79 0 of the hydrochloric acid 10,80% of coke tar refuse 3, calcium stearate 2, polyisobutene 3, 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, oleic acid diethyl amide 1, tetradecyl alcohol oleic acid ester 6, plant sterol 0.3, Tripotassium Citrate 1.
A preparation method for described low cost anticorrosive floor board, 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) joined in 12 times of deionized waters by above-mentioned oleic acid diethyl amide, add calcium stearate under agitation condition, raised temperature is 60 DEG C, adds soda, and regulate PH to be 10, insulated and stirred 20 minutes, obtains calcium stearate emulsion;
(3) joined in the ethanolic soln of 30 times 20% by above-mentioned octylisothiazolinone, stir, add trifluoroethyl methacrylate, raised temperature is 70 DEG C, adds Vinylstyrene, and insulation reaction 3 hours, obtains anticorrosion monomer;
(4) joined in 7 times of dehydrated alcohols by above-mentioned tetradecyl alcohol oleic acid ester, stir, add coke tar refuse, raised temperature is 70 DEG C, and insulated and stirred 6 minutes, obtains alcoholic solution;
(5) mixed with alcoholic solution by above-mentioned anticorrosion monomer, add plant sterol, 100 revs/min are stirred 30 minutes, obtain anticorrosion monomer emulsion;
(6) above-mentioned α 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 emulsion, 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;
(7) by above-mentioned organically-modified zirconium phosphate, the mixing of calcium stearate emulsion, be heated to boiling, keep boiling to water and do, drying 3 minutes at 100 DEG C;
(8) each raw material after above-mentioned process 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: 79 degree;
Camber intensity: 24.9MPa;
Unnotched impact strength: 72kJ/m 2;
Water-intake rate: 0.454%;
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 low cost anticorrosive floor board, is characterized in that, it is made up of the raw material of following weight parts:
Coke tar refuse 3-5, calcium stearate 2-4, polyisobutene 3-5, 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, oleic acid diethyl amide 1-2, tetradecyl alcohol oleic acid ester 6-8, plant sterol 0.3-1, Tripotassium Citrate 1-2.
2. a preparation method for low cost anticorrosive floor board 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) joined in 12-17 times of deionized water by above-mentioned oleic acid diethyl amide, add calcium stearate under agitation condition, raised temperature is 60-70 DEG C, adds soda, and adjustment PH is 10-13, insulated and stirred 20-30 minute, obtains calcium stearate emulsion;
(3) joined by above-mentioned octylisothiazolinone in the ethanolic soln of 30-40 times of 20-30%, stir, add trifluoroethyl methacrylate, raised temperature is 70-75 DEG C, adds Vinylstyrene, insulation reaction 3-4 hour, obtains anticorrosion monomer;
(4) joined in 7-10 times of dehydrated alcohol by above-mentioned tetradecyl alcohol oleic acid ester, stir, add coke tar refuse, raised temperature is 70-80 DEG C, insulated and stirred 6-8 minute, obtains alcoholic solution;
(5) mixed with alcoholic solution by above-mentioned anticorrosion monomer, add plant sterol, 100-200 rev/min is stirred 30-40 minute, obtains anticorrosion monomer emulsion;
(6) above-mentioned 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 emulsion, 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;
(7) by above-mentioned organically-modified zirconium phosphate, the mixing of calcium stearate emulsion, be heated to boiling, keep boiling to water and do, dry 3-4 minute at 100-105 DEG C;
(8) each raw material after above-mentioned process 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.
CN201510735867.6A 2015-11-03 2015-11-03 Low-cost anti-corrosion floor and preparation method thereof Pending CN105367945A (en)

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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

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
Title
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》 *

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