CN110080493A - A kind of preparation method of elastic flame stone plastic floor - Google Patents

A kind of preparation method of elastic flame stone plastic floor Download PDF

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Publication number
CN110080493A
CN110080493A CN201910228523.4A CN201910228523A CN110080493A CN 110080493 A CN110080493 A CN 110080493A CN 201910228523 A CN201910228523 A CN 201910228523A CN 110080493 A CN110080493 A CN 110080493A
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parts
flax fiber
plastic floor
stone plastic
elastic
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吕贻秀
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B26/00—Compositions of mortars, concrete or artificial stone, containing only organic binders, e.g. polymer or resin concrete
    • C04B26/02—Macromolecular compounds
    • C04B26/04—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3203—Polyhydroxy compounds
    • C08G18/3206—Polyhydroxy compounds aliphatic
    • C—CHEMISTRY; METALLURGY
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
    • C08G18/348—Hydroxycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/64—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63
    • C08G18/6484—Polysaccharides and derivatives thereof
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
    • C08G18/6692—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/34
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/675—Low-molecular-weight compounds
    • C08G18/6755—Unsaturated carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C08L27/06—Homopolymers or copolymers of vinyl chloride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C08L63/10—Epoxy resins modified by unsaturated compounds
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/38—Oxides or hydroxides of elements of Groups 1 or 11 of the Periodic System
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/50—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with hydrogen peroxide or peroxides of metals; with persulfuric, permanganic, pernitric, percarbonic acids or their salts
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/51—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with sulfur, selenium, tellurium, polonium or compounds thereof
    • D06M11/55—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with sulfur, selenium, tellurium, polonium or compounds thereof with sulfur trioxide; with sulfuric acid or thiosulfuric acid or their salts
    • D06M11/56—Sulfates or thiosulfates other than of elements of Groups 3 or 13 of the Periodic System
    • 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
    • E04F15/107—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 composed of several layers, e.g. sandwich panels
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/304—Insulating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/306—Resistant to heat
    • B32B2307/3065—Flame resistant or retardant, fire resistant or retardant
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2471/00—Floor coverings
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
    • C04B2111/00612—Uses not provided for elsewhere in C04B2111/00 as one or more layers of a layered structure
    • 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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
    • C08L2205/16—Fibres; Fibrils
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/02—Natural fibres, other than mineral fibres
    • D06M2101/04—Vegetal fibres
    • D06M2101/06—Vegetal fibres cellulosic

Abstract

The invention belongs to construction material preparation technical fields, and in particular to a kind of preparation method of elastic flame stone plastic floor.The present invention is with polyetherdiol, rosin, di-isocyanate etc. is that raw material obtains polyurethane elastomer, elastic ground is prepared using modified polyurethane foaming, the present invention utilizes maleic anhydride, glycerol successively reacts with rosin in the generating process of polyurethane, and rosin is modified, generate maleic rosin, modified rosin resin is generated using maleic rosin and glycerine reaction, improve its softening point, and possess preferable barrier performance as stone plastic floor ground, aoxidize flax fiber, plasticising lamina rara externa cure shrinkage can be reduced, so that the compatibility of modified oxidized flax fiber and epoxidized soybean oil is improved, epoxy soybean oil meter face covers one layer of netted layer of charcoal of expansion, play the role of heat-insulated oxygen-impermeable, epoxidized soybean oil has plasticization to polyvinyl chloride simultaneously, block the continuous decomposition of polyvinyl chloride, before wide application Scape.

Description

A kind of preparation method of elastic flame stone plastic floor
Technical field
The invention belongs to construction material preparation technical fields, and in particular to a kind of preparation side of elastic flame stone plastic floor Method.
Background technique
Currently, house decoration generally uses solid wooden floor board, solid wooden floor board due to its natural timber quality become reconciled see it is outer It sees and is liked by everybody.But since timber resources is more and more nervous, the raw material for manufacturing solid wooden floor board increasingly cannot Meets the needs of market.
Stone plastic floor is also referred to as stone modeling floor tile, is the new terrestrial dress that a kind of high-quality, high-tech research developed Exterior material.It uses the marble powder of purification for main raw material(s), constitutes the solid base of high density, high microsteping reticular structure, table Face is process coated with polyvinyl chloride resin through procedures up to a hundred.Product lines beautiful, superpower wear-resistant true to nature, surface-brightening without cunning, And environment-protecting and non-poisonous, wear-resisting, scratch-resistant, moreover it is possible to anti-skidding, waterproof, fire prevention etc..Compared with other ground, decorative material for wall surface, stone Moulding floor has clear advantage, for example, the primary raw material of stone plastic floor is natural stone-powder, is free of radioactive element, Er Qieke It is more environmentally friendly to recycle and reuse completely；Stone plastic floor is more frivolous, and building body load-bearing and space are saved in skyscraper About, there is big advantage；In addition, stone plastic floor has superpower wear-resistant, high resiliency and superpower shock resistance, also have excellent The performances such as different anti-skidding, fire-retardant, waterproof, noise control, fire prevention, waterproof, insect-pest, antibacterial, whens construction and installation, are also more convenient.Cause This, has obtained quick application.
But existing stone plastic floor has the following disadvantages: that current stone plastic floor ground adds increasing generally in its raw material Agent is moulded to increase the flexibility of product, but this substance has the hidden danger of environmental protection aspect, and there can be injury to exist to human body Many industries are prohibited from using；Since the hot contraction ratio of PVC material and mountain flour (such as calcium carbonate) both materials differs greatly, very Gap not of uniform size, bubble or gas chamber easy to form, thus obtained stone plastic floor intensity is not high, and properties of product are unstable； Containing foaming agent, be unable to high temperature resistant, hardness is low, and stability is poor, can soften in the case of a high temperature, cannot mat formation in direct sunlight or Above high-temperature geothermal.In addition, a bigger problem existing for stone plastic floor is, when being subjected to bigger cold and hot variation, It amplifies shrinking percentage can be bigger, is easy to happen the deformation on stone plastic floor floor or decorative panel and arches upward.
Therefore, design that a kind of intensity is high, heat-resisting quantity is good, the stone plastic floor that percent thermal shrinkage is small and preparation method thereof is very It is necessary to.
Summary of the invention
Present invention mainly solves the technical issues of, generally add plasticizer in its raw material for current stone plastic floor ground Increase the flexibility of product, but elasticity is still poor when low temperature, and plasticizer is harmful to the human body, the outer layer of stone plastic floor Usually polyvinyl chloride resin, poor fire and the defect for being easy aging, provide a kind of preparation side of elastic flame stone plastic floor Method.
In order to solve the above-mentioned technical problem, the technical scheme adopted by the invention is that:
The specific preparation step of elastic flame stone plastic floor are as follows:
According to parts by weight, oxidized starch, epoxidized soybean oil, PVC powder, acetone is taken to be fitted into high speed disperser, with 4000~ The revolving speed of 4200r/min disperses 10~15min and obtains emulsified suspension, and oxidation flax fiber is put into emulsified suspension, is added Heat is warming up to 50~55 DEG C, heats 3~4h, drying obtains PVC plasticising lamina rara externa after filtering removal filtrate, by elastic bottom Material, intermediate slabstone, successively alignment stacks PVC plasticising lamina rara externa from top to bottom, is put into stack and rolls and scrape Burr removal and obtain Elastic flame stone plastic floor；
Aoxidize the specific preparation step of flax fiber are as follows:
(1) take 95~100g flax fiber, in beaker with 200~230mL sodium hydroxide solution impregnate flax fiber 18~ 20h, filtering removal filtrate, obtains softening flax fiber, rinses softening flax fiber with deionized water until cleaning solution is in neutrality；
(2) the softening flax fiber after washing is placed in 1500~1700mL distilled water, 10~12mL is added into distilled water Copper-bath and 70~75mL hydrogen peroxide, normal-temperature reaction 2~4 days, decompression filtered removal oxidation solution and obtains oxidation flax fiber；
The specific preparation step of intermediate slabstone are as follows:
In mass ratio it is that 1 ︰ 3 is mixed by 70~80g acrylonitrile-butadiene rubber powder and 210~240g marble powder, is placed in double roll mill, It plasticates 2~3 times, then 30~40g bentonite, 20~25g nanometer calcium carbonate is added into double roll mill, mixing plasticates 2~3 Secondary, discharging squeezes out to obtain intermediate slabstone by extruder, spare；
The specific preparation step of elastic ground are as follows:
According to parts by weight, 60~70 parts of modified polyurethanes, 78~80 parts of vinyl ester resins are taken to be put into reaction kettle, heating rises Temperature is kneaded 3~5h, obtains polyurethane elastomer, polyurethane elastomer is placed in sheet former and is suppressed to 230~250 DEG C Dicing obtains the elastic ground of 0.3~0.5mm.
PVC plasticising lamina rara externa prepares raw material, according to parts by weight, including 20~30 parts of oxidized starch, epoxidized soybean oil 10 ~20 parts, 70~80 parts of PVC powder, 40~50 parts of acetone, 40~50 parts of flax fiber of oxidation.
Aoxidizing sodium hydroxide solution mass fraction in the specific preparation step (1) of flax fiber is 20%.
The mass fraction of copper-bath and hydrogen peroxide in the specific preparation step (2) of flax fiber is aoxidized to be respectively preferably 10%、30%。
In the specific preparation step of intermediate slabstone the granularity of acrylonitrile-butadiene rubber powder and marble powder be respectively preferably 100 mesh and 200 mesh, acrylonitrile-butadiene rubber powder and marble powder mixing mass ratio are 1 ︰ 3.
It is 45~55 DEG C that preliminary roller temperature is controlled when plasticating in the specific preparation step of intermediate slabstone, and rear roll temperature is 40~50 DEG C, roll spacing is 8~10mm.
The specific preparation step of modified polyurethane in the elastic specific preparation step of ground are as follows:
Hexamethylene diisocyanate, polyetherdiol, rosin are added into three-necked flask, is heated to 80~85 DEG C, insulation reaction 2~ After 3h, 50~60 DEG C are cooled to, dihydromethyl propionic acid, glycerol and maleic anhydride are successively added into three-necked flask, by two laurels After sour dibutyl tin is dissolved in acetone, instilled in three-necked flask with constant pressure funnel with the drop rate of 2~3mL/min, side drop Edged heating, control heating rate are 3~5 DEG C/min, are warming up to 80~82 DEG C, and the reaction was continued 3~4h obtains being modified poly- ammonia Ester.
Modified polyurethane preparation process is raw materials used, according to parts by weight, including 80~90 parts of hexamethylene diisocyanate, polyethers 30~40 parts of glycol, 20~30 parts of rosin, 10~15 parts of dihydromethyl propionic acid, 20~30 parts of glycerol, 20~25 parts of maleic anhydride, 3~5 parts of dibutyl tin dilaurate, 35~40 parts of acetone.
The beneficial effects of the present invention are:
(1) present invention reacts polyetherdiol, rosin, di-isocyanate heat temperature raising, and hydroxymethyl propionic acid, sweet is added after cooling The raw materials such as oil and maleic anhydride obtain polyurethane elastomer with dibutyltindilaurate catalyzed reaction, utilize modified polyurethane Elastic ground is prepared in foaming, and the present invention is successively sent out with rosin in the generating process of polyurethane using maleic anhydride, glycerol Raw reaction, and the rosin with plasticization effect is modified, since there are two electrophilic carbonyls on the double key carbon of maleic anhydride Base, therefore maleic anhydride can go on smoothly under heating conditions with rosin and react, and generate maleic rosin, utilize maleic rosin Modified rosin resin is generated with glycerine reaction, reaction belongs to polyesterification reaction, can reduce maleic rosin by polyesterification reaction Acid value, improve its softening point, reduce the glass transition temperature of polyurethane elastomer, make the polyurethane with foaming structure Elastomer keeps preferable viscoelastic property, and polyurethane is made to be influenced to become smaller by expanding with heat and contract with cold, and receives the heat of itself and marble powder Contracting is reduced than difference, and possesses preferable barrier performance as stone plastic floor ground；
(2) PVC prepared by the present invention is plasticized lamina rara externa, and flax fiber hydrogen peroxide dipping is made its oxidation, gained is aoxidized sub- Flaxen fiber, which is immersed in the emulsion of oxidized starch, to be modified and disperses, and oxidized starch can be such that starch gelatinization temperature reduces, and heat paste is viscous Degree becomes smaller and thermal stability enhances, and can reduce plasticising lamina rara externa cure shrinkage, by the polyhydroxy structure of oxidized starch, so that The compatibility of modified oxidized flax fiber and epoxidized soybean oil is improved, to interpenetrate bonding polyvinyl chloride resin, reaches raising The purpose of PVC plastic, in terms of flame retardant property, aoxidizing flax fiber and oxidized starch has rejection to oxygen, in combustion process The oxygen concentration of middle combustion centre can reduce, oxidized starch and oxidation flax fiber under the catalytic action of acid source ammonium polyphosphate, Before resin base material decomposition, charcoal is resolved into advance, so that one layer of netted layer of charcoal of expansion is covered in epoxy soybean oil meter face, it is netted Layer of charcoal is continuously fine and close, plays the role of heat-insulated oxygen-impermeable, is conducive to prevent substrate and further burns, to improve plasticising lamina rara externa resistance Performance is fired, while epoxidized soybean oil low temperature flexibility is preferable, has plasticization to polyvinyl chloride, and can make in polyvinyl chloride chain Active chlorine atom is stablized, and the hydrogen chloride for degrading out because of light and heat can be absorbed rapidly, to block the company of polyvinyl chloride It is continuous to decompose, make the more stable environmental protection of PVC, has broad application prospects.
Specific embodiment
According to parts by weight, 80~90 parts of hexamethylene diisocyanates, 30~40 parts of polyetherdiol, 20 are added into three-necked flask ~30 parts of rosin, are heated to 80~85 DEG C, after 2~3h of insulation reaction, 50~60 DEG C are cooled to, successively into three-necked flask 10~15 parts of dihydromethyl propionic acids, 20~30 parts of glycerol and 20~25 parts of maleic anhydrides are added, by 3~5 parts of two fourths of tin dilaurate After Ji Xi is dissolved in 35~40 parts of acetone, instilled in three-necked flask with constant pressure funnel with the drop rate of 2~3mL/min, side Side heating is added dropwise, control heating rate is 3~5 DEG C/min, is warming up to 80~82 DEG C, and the reaction was continued 3~4h obtains being modified poly- ammonia Ester；According to parts by weight, 60~70 parts of modified polyurethanes, 78~80 parts of vinyl ester resins are taken to be put into reaction kettle, heating rises Temperature is kneaded 3~5h, obtains polyurethane elastomer, polyurethane elastomer is placed in sheet former and is suppressed to 230~250 DEG C Dicing obtains the elastic ground of 0.3~0.5mm, spare；By 70~80g100 mesh acrylonitrile-butadiene rubber powder and 400~500g200 Mesh marble powder is 1 ︰ 3 mixing in mass ratio, is placed in double roll mill, is 45~55 DEG C in preceding roll temperature, rear roll temperature is 40~50 DEG C, roll spacing is plasticated 2~3 times under conditions of being 8~10mm, then 30~40g bentonite, 20 are added into double roll mill ~25g nanometer calcium carbonate, mixing are plasticated 2~3 times, are discharged, are squeezed out to obtain intermediate slabstone by extruder, spare；Take 95~ 100g flax fiber, in beaker with 200~230mL mass fraction be 20% sodium hydroxide solution impregnate flax fiber 18~ 20h, filtering removal filtrate, obtains softening flax fiber, rinses softening flax fiber with deionized water until cleaning solution is in neutrality； Softening flax fiber after washing is placed in 1500~1700mL distilled water, 10~12mL mass fraction is added into distilled water The hydrogen peroxide that copper-bath and 70~75mL mass fraction for 10% are 30%, normal-temperature reaction 2~4 days, decompression filtered removal Oxidation solution obtains oxidation flax fiber；According to parts by weight, 20~30 parts of oxidized starch, 10~20 parts of epoxidized soybean oils, 70 are taken ~80 parts of PVC powders, 40~50 parts of acetone are fitted into high speed disperser, disperse 10~15min with the revolving speed of 4000~4200r/min Emulsified suspension is obtained, 40~50 parts of oxidation flax fibers are put into emulsified suspension, is heated to 50~55 DEG C, heating 3~4h is handled, drying obtains PVC plasticising lamina rara externa after filtering removal filtrate, and elastic ground, intermediate slabstone, PVC are plasticized outer layer Successively alignment stacks plate from top to bottom, is put into stack and rolls and scrape Burr removal and obtain elastic flame stone plastic floor.
The preparation of modified polyurethane: according to parts by weight, be added into three-necked flask 80 parts of hexamethylene diisocyanates, 30 parts it is poly- Ether glycol, 20 parts of rosin, are heated to 80 DEG C, after insulation reaction 2h, are cooled to 50 DEG C, 10 are successively added into three-necked flask Part dihydromethyl propionic acid, 20 parts of glycerol and 20 parts of maleic anhydrides after 3 parts of dibutyl tin dilaurates are dissolved in 35 parts of acetone, are used Constant pressure funnel is instilled in three-necked flask with the drop rate of 2mL/min, heat up when being added dropwise, control heating rate for 3 DEG C/ Min is warming up to 80 DEG C, the reaction was continued 3h, obtains modified polyurethane.
The preparation of intermediate slabstone: according to parts by weight, 60 parts of modified polyurethanes, 78 parts of vinyl ester resins is taken to be put into reaction In kettle, 230 DEG C are heated to, 3h is kneaded, obtains polyurethane elastomer, polyurethane elastomer is placed in sheet former and is pressed Dicing processed obtains the elastic ground of 0.3mm, spare；70g100 mesh acrylonitrile-butadiene rubber powder and 400g200 mesh marble powder are pressed Mass ratio is 1 ︰ 3 mixing, is placed in double roll mill, is 45 DEG C in preceding roll temperature, and rear roll temperature is 40 DEG C, and roll spacing is 8mm's Under the conditions of plasticate 2 times, then into double roll mill be added 30g bentonite, 20g nanometer calcium carbonate, mixing plasticate 2 times, discharge, lead to Extruder is crossed to squeeze out to obtain intermediate slabstone, it is spare.
It aoxidizes the preparation of flax fiber: taking 95g flax fiber, the hydroxide for being 20% with 200mL mass fraction in beaker Sodium solution impregnates flax fiber 18h, and filtering removal filtrate obtains softening flax fiber, and it is fine to rinse softening flax with deionized water Dimension is until cleaning solution is in neutrality；Softening flax fiber after washing is placed in 1500mL distilled water, is added into distilled water The hydrogen peroxide that the copper-bath and 70mL mass fraction that 10mL mass fraction is 10% are 30%, normal-temperature reaction 2 days, decompression filtered Removal oxidation solution obtains oxidation flax fiber.
The preparation of elastic flame stone plastic floor: according to parts by weight, 20 parts of oxidized starch, 10 parts of epoxidized soybean oils, 70 are taken Part PVC powder, 40 parts of acetone are fitted into high speed disperser, obtain emulsified suspension with the revolving speed dispersion 10min of 4000r/min, will 40 parts of oxidation flax fibers are put into emulsified suspension, are heated to 50 DEG C, are heated 3h, are dried after filtering removal filtrate PVC plasticising lamina rara externa is obtained, successively alignment stacks from top to bottom by elastic ground, intermediate slabstone, PVC plasticising lamina rara externa, is put into Roll in stack and scrape Burr removal and obtains elastic flame stone plastic floor.
The preparation of modified polyurethane: according to parts by weight, be added into three-necked flask 85 parts of hexamethylene diisocyanates, 35 parts it is poly- Ether glycol, 25 parts of rosin, are heated to 83 DEG C, after insulation reaction 2h, are cooled to 55 DEG C, 13 are successively added into three-necked flask Part dihydromethyl propionic acid, 25 parts of glycerol and 23 parts of maleic anhydrides after 4 parts of dibutyl tin dilaurates are dissolved in 37 parts of acetone, are used Constant pressure funnel is instilled in three-necked flask with the drop rate of 2mL/min, heat up when being added dropwise, control heating rate for 4 DEG C/ Min is warming up to 81 DEG C, the reaction was continued 3h, obtains modified polyurethane.
The preparation of intermediate slabstone: according to parts by weight, 65 parts of modified polyurethanes, 79 parts of vinyl ester resins is taken to be put into reaction In kettle, 240 DEG C are heated to, 4h is kneaded, obtains polyurethane elastomer, polyurethane elastomer is placed in sheet former and is pressed Dicing processed obtains the elastic ground of 0.4mm, spare；75g100 mesh acrylonitrile-butadiene rubber powder and 450g200 mesh marble powder are pressed Mass ratio is 1 ︰ 3 mixing, is placed in double roll mill, is 50 DEG C in preceding roll temperature, and rear roll temperature is 45 DEG C, and roll spacing is 9mm's Under the conditions of plasticate 2 times, then into double roll mill be added 35g bentonite, 23g nanometer calcium carbonate, mixing plasticate 2 times, discharge, lead to Extruder is crossed to squeeze out to obtain intermediate slabstone, it is spare.
It aoxidizes the preparation of flax fiber: taking 97g flax fiber, the hydroxide for being 20% with 220mL mass fraction in beaker Sodium solution impregnates flax fiber 19h, and filtering removal filtrate obtains softening flax fiber, and it is fine to rinse softening flax with deionized water Dimension is until cleaning solution is in neutrality；Softening flax fiber after washing is placed in 1600mL distilled water, is added into distilled water The hydrogen peroxide that the copper-bath and 73mL mass fraction that 11mL mass fraction is 10% are 30%, normal-temperature reaction 3 days, decompression filtered Removal oxidation solution obtains oxidation flax fiber.
The preparation of elastic flame stone plastic floor: according to parts by weight, 25 parts of oxidized starch, 15 parts of epoxidized soybean oils, 75 are taken Part PVC powder, 45 parts of acetone are fitted into high speed disperser, obtain emulsified suspension with the revolving speed dispersion 13min of 4100r/min, will 45 parts of oxidation flax fibers are put into emulsified suspension, are heated to 53 DEG C, are heated 3h, are dried after filtering removal filtrate PVC plasticising lamina rara externa is obtained, successively alignment stacks from top to bottom by elastic ground, intermediate slabstone, PVC plasticising lamina rara externa, is put into Roll in stack and scrape Burr removal and obtains elastic flame stone plastic floor.
The preparation of modified polyurethane: according to parts by weight, be added into three-necked flask 90 parts of hexamethylene diisocyanates, 40 parts it is poly- Ether glycol, 30 parts of rosin, are heated to 85 DEG C, after insulation reaction 3h, are cooled to 60 DEG C, 15 are successively added into three-necked flask Part dihydromethyl propionic acid, 30 parts of glycerol and 25 parts of maleic anhydrides after 5 parts of dibutyl tin dilaurates are dissolved in 40 parts of acetone, are used Constant pressure funnel is instilled in three-necked flask with the drop rate of 3mL/min, heat up when being added dropwise, control heating rate for 5 DEG C/ Min is warming up to 82 DEG C, the reaction was continued 4h, obtains modified polyurethane.
The preparation of intermediate slabstone: according to parts by weight, 70 parts of modified polyurethanes, 10 parts of vinyl ester resins is taken to be put into reaction In kettle, 250 DEG C are heated to, 5h is kneaded, obtains polyurethane elastomer, polyurethane elastomer is placed in sheet former and is pressed Dicing processed obtains the elastic ground of 0.5mm, spare；80g100 mesh acrylonitrile-butadiene rubber powder and 500g200 mesh marble powder are pressed Mass ratio is 1 ︰ 3 mixing, is placed in double roll mill, is 55 DEG C in preceding roll temperature, and rear roll temperature is 50 DEG C, and roll spacing is 10mm's Under the conditions of plasticate 3 times, then into double roll mill be added 40g bentonite, 25g nanometer calcium carbonate, mixing plasticate 3 times, discharge, lead to Extruder is crossed to squeeze out to obtain intermediate slabstone, it is spare.
It aoxidizes the preparation of flax fiber: taking 100g flax fiber, the hydrogen-oxygen for being 20% with 230mL mass fraction in beaker Change sodium solution and impregnate flax fiber 20h, filtering removal filtrate obtains softening flax fiber, rinses softening flax with deionized water Fiber is until cleaning solution is in neutrality；Softening flax fiber after washing is placed in 1700mL distilled water, is added into distilled water The hydrogen peroxide that the copper-bath and 75mL mass fraction that 12mL mass fraction is 10% are 30%, normal-temperature reaction 4 days, decompression filtered Removal oxidation solution obtains oxidation flax fiber.
The preparation of elastic flame stone plastic floor: according to parts by weight, 30 parts of oxidized starch, 20 parts of epoxidized soybean oils, 80 are taken Part PVC powder, 50 parts of acetone are fitted into high speed disperser, obtain emulsified suspension with the revolving speed dispersion 15min of 4200r/min, will 50 parts of oxidation flax fibers are put into emulsified suspension, are heated to 55 DEG C, are heated 4h, are dried after filtering removal filtrate PVC plasticising lamina rara externa is obtained, successively alignment stacks from top to bottom by elastic ground, intermediate slabstone, PVC plasticising lamina rara externa, is put into Roll in stack and scrape Burr removal and obtains elastic flame stone plastic floor.
Comparative example 1: it is essentially identical with the preparation method of embodiment 1, it has only the difference is that modified polyurethane is not added.
Comparative example 2: it is essentially identical with the preparation method of embodiment 2, it has only the difference is that oxidation flax fiber is not added.
Comparative example 3: the stone plastic floor of company, Suzhou City production.
Stone plastic floor in elastic flame stone plastic floor produced by the present invention and comparative example is detected, testing result is such as Shown in table 1:
Tensile property test
Reference standard GB/T1040.2-2006 is measured, tensile speed 50mm/min.
Room temperature ball falling impact, falling ball impact test at low temperature test reference standard GB/T11982.1-2005 are measured.
Heat-resistant aging test reference standard GB/T11982.1-2015 is examined and determine, and every kind of heat treatment process tests 3 Sample is averaged.
1 performance measurement result of table
From the data in table 1, it can be seen that elastic flame stone plastic floor produced by the present invention, has excellent mechanical property, thermal stability And flame retardant property, preparation method simple process, high production efficiency can be applied widely than common stone plastic floor long service life In various laying places, with good economic efficiency and social benefit.

Claims (8)

1. a kind of preparation method of elastic flame stone plastic floor, it is characterised in that specific preparation step are as follows:
According to parts by weight, oxidized starch, epoxidized soybean oil, PVC powder, acetone is taken to be fitted into high speed disperser, with 4000~ The revolving speed of 4200r/min disperses 10~15min and obtains emulsified suspension, and oxidation flax fiber is put into emulsified suspension, is added Heat is warming up to 50~55 DEG C, heats 3~4h, drying obtains PVC plasticising lamina rara externa after filtering removal filtrate, by elastic bottom Material, intermediate slabstone, successively alignment stacks PVC plasticising lamina rara externa from top to bottom, is put into stack and rolls and scrape Burr removal and obtain Elastic flame stone plastic floor；
The specific preparation step of the oxidation flax fiber are as follows:
(1) take 95~100g flax fiber, in beaker with 200~230mL sodium hydroxide solution impregnate flax fiber 18~ 20h, filtering removal filtrate, obtains softening flax fiber, rinses softening flax fiber with deionized water until cleaning solution is in neutrality；
(2) the softening flax fiber after washing is placed in 1500~1700mL distilled water, 10~12mL is added into distilled water Copper-bath and 70~75mL hydrogen peroxide, normal-temperature reaction 2~4 days, decompression filtered removal oxidation solution and obtains oxidation flax fiber；
The specific preparation step of the intermediate slabstone are as follows:
In mass ratio it is that 1 ︰ 3 is mixed by 70~80g acrylonitrile-butadiene rubber powder and 210~240g marble powder, is placed in double roll mill, It plasticates 2~3 times, then 30~40g bentonite, 20~25g nanometer calcium carbonate is added into double roll mill, mixing plasticates 2~3 Secondary, discharging squeezes out to obtain intermediate slabstone by extruder, spare；
The specific preparation step of the elastic ground are as follows:
According to parts by weight, 60~70 parts of modified polyurethanes, 78~80 parts of vinyl ester resins are taken to be put into reaction kettle, heating rises Temperature is kneaded 3~5h, obtains polyurethane elastomer, polyurethane elastomer is placed in sheet former and is suppressed to 230~250 DEG C Dicing obtains the elastic ground of 0.3~0.5mm.
2. a kind of preparation method of elastic flame stone plastic floor according to claim 1, it is characterised in that: the PVC Plasticising lamina rara externa prepares raw material, according to parts by weight, including 20~30 parts of oxidized starch, 10~20 parts of epoxidized soybean oil, PVC powder 70~80 parts, 40~50 parts of acetone, 40~50 parts of flax fiber of oxidation.
3. a kind of preparation method of elastic flame stone plastic floor according to claim 1, it is characterised in that: the oxidation Sodium hydroxide solution mass fraction is 20% in the specific preparation step (1) of flax fiber.
4. a kind of preparation method of elastic flame stone plastic floor according to claim 1, it is characterised in that: the oxidation The mass fraction of copper-bath and hydrogen peroxide is respectively preferably 10%, 30% in the specific preparation step (2) of flax fiber.
5. a kind of preparation method of elastic flame stone plastic floor according to claim 1, it is characterised in that: the centre The granularity of acrylonitrile-butadiene rubber powder and marble powder is respectively preferably 100 mesh and 200 mesh, nitrile rubber in the specific preparation step of slabstone Powder and marble powder mixing mass ratio are 1 ︰ 3.
6. a kind of preparation method of elastic flame stone plastic floor according to claim 1, it is characterised in that: the centre When plasticating in the specific preparation step of slabstone control preliminary roller temperature be 45~55 DEG C, rear roll temperature be 40~50 DEG C, roll spacing be 8~ 10mm。
7. a kind of preparation method of elastic flame stone plastic floor according to claim 1, it is characterised in that: the elasticity The specific preparation step of modified polyurethane in the specific preparation step of ground are as follows:
Hexamethylene diisocyanate, polyetherdiol, rosin are added into three-necked flask, is heated to 80~85 DEG C, insulation reaction 2~ After 3h, 50~60 DEG C are cooled to, dihydromethyl propionic acid, glycerol and maleic anhydride are successively added into three-necked flask, by two laurels After sour dibutyl tin is dissolved in acetone, instilled in three-necked flask with constant pressure funnel with the drop rate of 2~3mL/min, side drop Edged heating, control heating rate are 3~5 DEG C/min, are warming up to 80~82 DEG C, and the reaction was continued 3~4h obtains being modified poly- ammonia Ester.
8. a kind of preparation method of elastic flame stone plastic floor according to claim 7, it is characterised in that: the modification Polyurethane preparation process is raw materials used, according to parts by weight, including 80~90 parts of hexamethylene diisocyanate, polyetherdiol 30~40 Part, 20~30 parts of rosin, 10~15 parts of dihydromethyl propionic acid, 20~30 parts of glycerol, 20~25 parts of maleic anhydride, tin dilaurate two 3~5 parts of butyl tin, 35~40 parts of acetone.
CN201910228523.4A 2019-03-25 2019-03-25 A kind of preparation method of elastic flame stone plastic floor Withdrawn CN110080493A (en)

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