CN108623938A - A kind of cross-linked polrvinyl chloride plank and preparation method thereof - Google Patents

A kind of cross-linked polrvinyl chloride plank and preparation method thereof Download PDF

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Publication number
CN108623938A
CN108623938A CN201810450129.0A CN201810450129A CN108623938A CN 108623938 A CN108623938 A CN 108623938A CN 201810450129 A CN201810450129 A CN 201810450129A CN 108623938 A CN108623938 A CN 108623938A
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Prior art keywords
plank
cross
polrvinyl chloride
linked polrvinyl
protective layer
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Chinese (zh)
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黄子伟
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Foshan Gaoming Chuangqi Decoration Material Co Ltd
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Foshan Gaoming Chuangqi Decoration Material Co Ltd
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Priority to CN201810450129.0A priority Critical patent/CN108623938A/en
Publication of CN108623938A publication Critical patent/CN108623938A/en
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D7/00—Producing flat articles, e.g. films or sheets
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/065—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of foam
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/22—Layered products comprising a layer of synthetic resin characterised by the use of special additives using plasticisers
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/24—Layered products comprising a layer of synthetic resin characterised by the use of special additives using solvents or swelling agents
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/304—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl halide (co)polymers, e.g. PVC, PVDC, PVF, PVDF
    • 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
    • B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0066—Use of inorganic compounding ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0095—Mixtures of at least two compounding ingredients belonging to different one-dot groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
    • C08J9/08—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing carbon dioxide
    • C—CHEMISTRY; METALLURGY
    • 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
    • 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
    • B32B2266/00—Composition of foam
    • B32B2266/02—Organic
    • B32B2266/0214—Materials belonging to B32B27/00
    • B32B2266/0221—Vinyl resin
    • B32B2266/0235—Vinyl halide, e.g. PVC, PVDC, PVF, PVDF
    • 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
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/406—Bright, glossy, shiny surface
    • 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
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/536—Hardness
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/02—CO2-releasing, e.g. NaHCO3 and citric acid
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2327/00—Characterised by the use 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; Derivatives of such polymers
    • C08J2327/02—Characterised by the use 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; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2327/04—Characterised by the use 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; Derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C08J2327/06—Homopolymers or copolymers of vinyl chloride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2423/10—Homopolymers or copolymers of propene
    • C08J2423/14—Copolymers of propene
    • 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
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C08K2003/262—Alkali metal carbonates
    • 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
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C08K2003/265—Calcium, strontium or barium carbonate
    • 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
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • 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

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  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Extrusion Moulding Of Plastics Or The Like (AREA)

Abstract

The invention discloses a kind of cross-linked polrvinyl chloride plank, which includes sandwich layer and is covered in the protective layer of core layer surface, and sandwich layer is Foamed polyvinyl chloride material, can effectively reduce the density of plank, cost-effective；Protective layer is the pvc material not foamed, and has the advantages that hardness is high, good weatherability, surface is smooth, glossiness is high.The present invention also provides a kind of methods preparing the polyvinyl-chloride plate material; using the method for coextrusion mold; after sandwich layer melt and protective layer melt are squeezed out respectively; shaper is inputted by distributor; cool down, shapes, draws; then it cuts to required size, cross-linked polrvinyl chloride plank is made.Polyvinyl-chloride plate material good weatherability of the present invention, hardness is high, and surface is smooth, glossiness is high.Cross-linked polrvinyl chloride plank mature preparation process in the present invention, operation is simple, is suitable for industrialized production.

Description

A kind of cross-linked polrvinyl chloride plank and preparation method thereof
Technical field
The invention belongs to polyvinyl-chloride plate material technical fields, and in particular to a kind of cross-linked polrvinyl chloride plank and its preparation side Method.
Background technology
Polyvinyl chloride is a kind of high molecular material containing chlorine atom, is the unformed polymerization containing a small amount of crystalline texture Object, molecular structure are [- CH2-CHCl-]n.Polyvinyl chloride has abundant raw material, manufacturing process ripe, cheap, widely used Etc. outstanding features, become second-biggest-in-the-world resins for universal use, accounted for the 29% of World Synthetic Resin aggregate consumption.Polyvinyl chloride holds Easy processing can be processed by molding, laminated, injection molding, extrusion molding, calendering, the blowing modes such as hollow, mainly for the production of artificial The plastics soft goods such as leather, film, trunking can also produce the plastics boardy product such as plank, door and window, pipeline and valve, be timber, The ideal substitute of aluminium, composite board, promote the use of polyvinyl chloride product be economize on resources, reduce energy consumption, " mould Dai Mu ", The important measures of " mould Dai Gang ".
In the prior art, usually using foaming, squeeze out, cooling, molding method prepares polyvinyl-chloride plate material product, with poly- Vinyl chloride is raw material, adds other auxiliary agents to enhance the performances such as its heat resistance, toughness, ductility, has waterproof, fire-retardant, acidproof Alkali, mothproof, light, heat preservation, sound insulation, damping, convenient storage, it is easy for construction the features such as, meanwhile, the polyvinyl-chloride plate material prepared With can be sawed as timber, can dig, can glue that viscous, the processing performances such as can drill.
Crosslinking is that a kind of important method that pvc material is modified processing forms three-dimensional by crosslinking in material internal Network structure can improve the performance of heat-resisting property of softening, suppression cigarette fire resistance, weatherability of pvc material etc., improve poly- The processing performance of vinyl chloride material expands the use scope of pvc material.Optimize the property of polyvinyl-chloride plate material by crosslinking It can, it is intended to prepare the requirement for taking into account properties of product, production cost, material appearance, processing conditions etc..
Invention content
In order to solve the deficiencies in the prior art, the present invention provides a kind of cross-linked polrvinyl chloride plank, the plank packets Sandwich layer and the protective layer for being covered in core layer surface are included, sandwich layer is Foamed polyvinyl chloride material, can effectively reduce the density of plank, It is cost-effective；Protective layer is the pvc material not foamed, high with hardness, good weatherability, and surface is smooth, glossiness is high etc. Advantage.The present invention also provides a kind of methods preparing the polyvinyl-chloride plate material, using the method for coextrusion mold, by sandwich layer melt After being squeezed out respectively with protective layer melt, shaper is inputted by distributor, cool down, shapes, draws, then cut to institute Cross-linked polrvinyl chloride plank is made in the size needed.Polyvinyl-chloride plate material good weatherability of the present invention, hardness are high, and surface is smooth, gloss Degree is high.Cross-linked polrvinyl chloride plank mature preparation process in the present invention, operation is simple, is suitable for industrialized production.
Institute of the invention technique effect to be achieved is realized by following scheme：
The present invention provides a kind of cross-linked polrvinyl chloride planks, including sandwich layer, and are covered in the protective layer of core layer surface；
Wherein, the raw material for preparing of sandwich layer is respectively with mass percent：Corvic 40%-60%, stabilizer 3%-12%, changes Property crosslinking agent 5%-10%, foaming agent 5%-10%, lubricant 2%-6%, filler 25%-35%；
The raw material for preparing of protective layer is respectively with mass percent：Corvic 50%-60%, modified crosslinking agent 2%-12%, Stabilizer 5%-10%, plasticizer 5%-15%, filler 20%-35%；
The preparation method of the modified crosslinking agent is：By the soft list of epoxy resin, 10%-25% that mass percent is 30%-40% The coupling agent addition microwave radiation reactor of body, the diisocyanate of 20%-30%, the Corvic of 10%-20%, 5%-15% Interior, control mixing speed is 500-650r/min, reacts 0.5-1.5h at 90-110 DEG C, and modified crosslinking agent is made.
The preparation method of the filler is：It is respectively random polypropylene, the 10%-20% of 50%-60% by mass percent Calcium carbonate, the silica of 5%-10%, the lithium carbonate of 2%-7%, 10%-20% deionized water be added ceramic ball mill in, ball milling After 1-1.5h, the compound modifier that mass percent is 8%-16% is added, continues ball milling 2.5-5h, is sieved after the completion of ball milling, system Obtain the filler；
Polyvinyl-chloride plate material includes sandwich layer and is covered in the protective layer of core layer surface in the present invention.Foaming agent is added in sandwich layer to be made Polyvinyl-chloride foam material advantageously reduces the global density of plank, improves the execution conditions of plank, reduces transportation cost.It protects Sheath is the pvc material not foamed, and plank hardness obtained is high, and good weatherability, surface is smooth, glossiness is high.
In modified crosslinking agent, epoxy resin is added can introduce epoxy group in crosslinking agent, improve raw material in crosslinking agent In dispersion stabilization, moreover it is possible to improve the crosslink density and mechanical strength of material；Soft monomer glass transition temperature is low, not only contributes to The abundant melting mixing of each raw material in melt preparation process, additionally it is possible to the toughness of reinforced polyvinyl chloride plank.The addition of coupling agent The viscosity that melt can be improved improves the dispersion degree of raw material, improves processing performance.
Filler is using random polypropylene, calcium carbonate, silica, lithium carbonate, compound modifier as raw material, by ball milling system .Bead size ratio is big in mechanical milling process:In:Small=1:1:3, after the completion of ball milling, starched using 250 mesh reciprocating sieves filtering water mill, The filler is made.Filler hardness height, the good toughness.Random polypropylene is generated in industrial production polypropylene process A kind of waste material, mechanical strength and heat resistance are poor, are mixed into made of a certain amount of calcium carbonate and fill out in this random polypropylene Filling agent can play the role of good in polyvinyl-chloride plate material processing, and the toughness of plank can be remarkably reinforced, and solve random Polyacrylic recycling problem, reduces production cost.Meanwhile the addition of silica can improve grinding efficiency, lithium carbonate has rush The effect of solidifying agent contributes to being mutually mixed for each raw material in filler in mechanical milling process.
Further, the PVC resin polymerization degree is 800-1000.The degree of polymerization increases, and the basic performance of resin becomes It is good, but fusion time extends therewith, fusion factor becomes larger, poor processability, and the degree of polymerization is the polyvinyl chloride of 800-1000 Resin, basic performance is excellent, and processing performance is good.
Further, the stabilizer is one in Ca Zn composite object, carboxylic acid organotin, aluminum stearate, rare-earth stabilizer Kind is several.Stabilizer can prevent from deviating from hydrogen chloride in Corvic strand, or prevent this reaction, terminate and divide Solution acts on, and improves the decomposition temperature of Corvic, meanwhile, stabilizer can reduce the decomposition temperature of foaming agent so that foaming Process carries out at a lower temperature, improves bubbling efficiency, reduces the energy consumption needed for foamable reaction.
Further, the foaming agent is sodium bicarbonate, ammonium hydrogen carbonate, azido compound, azodicarbonamide, azo two One or more of isobutyronitrile.Gas release is big, and foaming is stablized.
Further, the lubricant is stearic acid, stearate, Solsperse 2000, stearic amide, paraffin, aoxidizes and gather One or more of ethylene, polyethylene wax.Lubricant can promote the plasticizing of Corvic；Improve the strong of sandwich layer melt Degree, prevents the merging of bubble, to obtain the product of even foaming.
Further, the plasticizer is epoxidized soybean oil, ethyl hexyl ester of epoxidized soybean oil, epoxy acetyl linolenic acid first One or more of ester, epoxyfuoic-oleic.Plasticizer is the important recipe ingredient of polrvinyl chloride product, to polyvinyl chloride Product influence is very big, can be effectively improved the processing performance of polrvinyl chloride product, and plasticizer is nontoxic plasticizer selected by the present invention, Be conducive to improve the working environment of operating personnel.
Further, in the preparation method of the modified crosslinking agent, the soft monomer is cyclohexyl methacrylate, methyl One or more of n-butyl acrylate, isooctyl methacrylate；The coupling agent is silane coupling agent.The coupling agent Preferably one or more of KH550, KH560, KH570, KH792.
Further, in the preparation method of the filler, the compound modifier is by methacrylic acid and monoalkoxy Unsaturated fatty acid titanate esters are (2-4) in mass ratio:1 mixes.
The present invention also provides a kind of methods preparing above-mentioned cross-linked polrvinyl chloride plank, it is characterised in that：Including as follows Step：
S01, the raw material of protective layer is weighed according to the mass percent of each component respectively, and the mixed built-in temperature of heat rises to 95-105 DEG C Afterwards, it adds raw materials into the mixed machine of heat, control mixing speed is 900-1100r/min, after being stirred 8-15min, by mixture It is sent into cold mixer, control mixing speed is 200-300r/min, is cooled to 20-40 DEG C, and protective layer melt is made；
S02 weighs the raw material of sandwich layer according to the mass percent of each component respectively, after the mixed built-in temperature of heat rises to 95-105 DEG C, It adds raw materials into the mixed machine of heat, control mixing speed is 900-1100r/min, and after being stirred 8-15min, mixture is sent into In cold mixer, control mixing speed is 200-300r/min, is cooled to 20-40 DEG C, and sandwich layer melt is made；
The sandwich layer melt prepared in S02 is added in conical double screw extruder, the protective layer melt prepared in S01 is added by S03 Enter in an other conical double screw extruder, carry out while squeezing out；
The protective layer melt of the sandwich layer melt squeezed out in S03, extrusion is delivered to by distributor in shaper by S04, is carried out Cooling, sizing, traction, then cut to required size, and cross-linked polrvinyl chloride plank is made.
Further, conical double screw extruder screw speed described in S03 is 20-30r/min, processing temperature 150- 180℃；Shaper described in S04 is vacuum water-cooled shaping mold；Cooling velocity described in S04 is 60-80 DEG C/min, cooling Temperature is 30-40 DEG C afterwards.
It is high-speed stirred in the mixed machine of heat in sandwich layer melt, protective layer melt preparation process, is conducive to the abundant mixed of raw material It closes；It is stirring at low speed in cold mixer, is conducive to the structure of melt composition stabilization.The mixed built-in temperature of heat is added after rising to 95-105 DEG C Raw material is conducive to that the moisture and volatile matter carried secretly in raw material is discharged, eliminate in foaming process because moisture and volatile matter there are due to Plank is set the problem of pinprick, layering occur.Melt is cooled to 20-40 DEG C after the completion of preparing, and melt maintains in the temperature range Certain viscosity and mobility, and melt property is stablized at this temperature, convenient for storage and transport, facilitates S03 extrusions Material is taken.
Conical double screw extruder has good charging performance, mixing plasticizing capacity, exhaust performance, extrusion stability etc. Feature selects the screw speed of 20-30r/min according to the viscosity of melt, selects processing temperature for 150- according to the composition of melt 180℃.Temperature is too low, and melt less and is disperseed uneven and form air pocket due to mixing unevenness, nucleation；When the temperature is excessively high, object Material viscosity reduces, and melt strength becomes larger, and abscess, which can be combined with each other, to become larger, and gas is to external diffusion into the surface, causing to send out in melt Bubble is excessive, and abscess is uneven, there is holes；150-180 DEG C of moderate temperature, material are uniformly mixed, and plasticizing is good, and gas is molten in melt Xie Du increases and nucleation quantity increases, and foams fine and smooth uniform.
Sandwich layer melt, protective layer melt are squeezed out with conical double screw extruder simultaneously respectively, and protective layer is covered in sandwich layer table Face will not fall off, and the sandwich layer of foaming can reduce the global density of plank, reduce transportation cost, and the protective layer not foamed makes Plank has good hardness and weather resistance, and plate surface is smooth, glossiness is high.
Vacuum water-cooled shaping mould shape is efficient, and cooling velocity is fast, cooling temperature stablize, melt once it is extruded by Cooling, surface is rapidly forced to form sclerderm, plank hardness obtained is high, surface is smooth.
The present invention has the following advantages：
1. polyvinyl chloride billboard includes sandwich layer and protective layer in the present invention.Sandwich layer is Foamed polyvinyl chloride material, can be effective The density of billboard is reduced, it is cost-effective；Protective layer is the pvc material not foamed, and has hardness high, and surface is smooth, light The advantages that Ze Dugao.
2. the mature preparation process of polyvinyl chloride billboard in the present invention, operation is simple, is suitable for industrialized production.
Specific implementation mode
With reference to embodiment, the present invention will be described in detail.
Embodiment 1
S01, the preparation of protective layer melt：
It is respectively 59% Corvic by mass percent after the mixed built-in temperature of heat rises to 100 DEG C（The degree of polymerization is 800）、 10% modified crosslinking agent, 6% aluminum stearate, 5% epoxidized soybean oil, 20% filler are added in the mixed machine of heat, control stirring Speed is 1000r/min, after stirring 10min, mixture is sent into cold mixer, control mixing speed is 200r/min, is cooled to 25 DEG C, protective layer melt is made.
S02, the preparation of sandwich layer melt：
It is respectively 57% Corvic by mass percent after the mixed built-in temperature of heat rises to 100 DEG C（The degree of polymerization is 800）、 5% aluminum stearate, 5% modified crosslinking agent, 6% ammonium hydrogen carbonate, 2% oxidic polyethylene, 25% filler the mixed machine of heat is added Interior, control mixing speed is 1000r/min, and after stirring 10min, mixture is sent into cold mixer, and control mixing speed is 200r/min is cooled to 25 DEG C, and sandwich layer melt is made.
The preparation method of the modified crosslinking agent is：It is 35% epoxy resin, 20% metering system by mass percent Sour cyclohexyl, 25% diisocyanate, 10% Corvic, 10% KH550 be added microwave radiation reactor in, control Mixing speed processed is 500r/min, reacts 1h at 100 DEG C, and modified crosslinking agent is made.
The preparation method of the filler is：By mass percent be respectively 54% random polypropylene, 10% calcium carbonate, 8% silica, 2% lithium carbonate, 18% deionized water be added ceramic ball mill in, after ball milling 1h, be added mass percent be 8% compound modifier continues ball milling 3h, is sieved after the completion of ball milling, the filler is made；The compound modifier is by methyl Acrylic acid is 2 in mass ratio with monoalkoxy unsaturated fatty acid titanate esters:1 mixes.Pearl is big in the mechanical milling process It is small than being big:In:Small=1:1:3, after the completion of ball milling, use 250 mesh reciprocating sieves filtering water mill slurry.
S03, the extrusion of melt：
The sandwich layer melt prepared in S02 is added in conical double screw extruder, the protective layer melt prepared in S01 is added another It in an outer conical double screw extruder, carries out while squeezing out, conical double screw extruder screw speed is 25r/min, processing Temperature is 160 DEG C.
S04, the preparation of cross-linked polrvinyl chloride plank：
The protective layer melt of the sandwich layer melt squeezed out in S03, extrusion is delivered to by distributor in vacuum water-cooled shaping mold, It is cooled down（Cooling velocity is 65 DEG C/min, and temperature is 30 DEG C after cooling）, sizing, traction, then cut to required size, Cross-linked polrvinyl chloride plank is made.
Embodiment 2
S01, the preparation of protective layer melt：
It is respectively 52% Corvic by mass percent after the mixed built-in temperature of heat rises to 100 DEG C（The degree of polymerization is 800）、 5% modified crosslinking agent, 8% aluminum stearate, 10% epoxidized soybean oil, 25% filler be added in the mixed machine of heat, control stirring speed Degree is 1000r/min, after stirring 10min, mixture is sent into cold mixer, control mixing speed is 200r/min, is cooled to 25 DEG C, protective layer melt is made.
S02, the preparation of sandwich layer melt：
It is respectively 42% Corvic by mass percent after the mixed built-in temperature of heat rises to 100 DEG C（The degree of polymerization is 800）、 10% aluminum stearate, 7% modified crosslinking agent, 6% ammonium hydrogen carbonate, 5% oxidic polyethylene, 30% filler that heat is added is mixed In machine, control mixing speed is 1000r/min, and after stirring 10min, mixture is sent into cold mixer, and control mixing speed is 200r/min is cooled to 25 DEG C, and sandwich layer melt is made.
The preparation method of the modified crosslinking agent is：It is 37% epoxy resin, 10% metering system by mass percent Sour cyclohexyl, 30% diisocyanate, 15% Corvic, 8% KH550 be added microwave radiation reactor in, control Mixing speed is 500r/min, reacts 1h at 100 DEG C, and modified crosslinking agent is made.
The preparation method of the filler is：By mass percent be respectively 59% random polypropylene, 11% calcium carbonate, 5% silica, 5% lithium carbonate, 10% deionized water be added ceramic ball mill in, after ball milling 1h, be added mass percent be 10% compound modifier continues ball milling 3h, is sieved after the completion of ball milling, the filler is made；The compound modifier is by methyl Acrylic acid is 2 in mass ratio with monoalkoxy unsaturated fatty acid titanate esters:1 mixes.Pearl is big in the mechanical milling process It is small than being big:In:Small=1:1:3, after the completion of ball milling, use 250 mesh reciprocating sieves filtering water mill slurry.
S03, the extrusion of melt：
The sandwich layer melt prepared in S02 is added in conical double screw extruder, the protective layer melt prepared in S01 is added another It in an outer conical double screw extruder, carries out while squeezing out, conical double screw extruder screw speed is 25r/min, processing Temperature is 160 DEG C.
S04, the preparation of cross-linked polrvinyl chloride plank：
The protective layer melt of the sandwich layer melt squeezed out in S03, extrusion is delivered to by distributor in vacuum water-cooled shaping mold, It is cooled down（Cooling velocity is 65 DEG C/min, and temperature is 30 DEG C after cooling）, sizing, traction, then cut to required size, Cross-linked polrvinyl chloride plank is made.
Embodiment 3
S01, the preparation of protective layer melt：
It is respectively 52% Corvic by mass percent after the mixed built-in temperature of heat rises to 100 DEG C（The degree of polymerization is 800）、 8% modified crosslinking agent, 6% aluminum stearate, 12% epoxidized soybean oil, 22% filler be added in the mixed machine of heat, control stirring speed Degree is 1000r/min, after stirring 10min, mixture is sent into cold mixer, control mixing speed is 200r/min, is cooled to 25 DEG C, protective layer melt is made.
S02, the preparation of sandwich layer melt：
It is respectively 43% Corvic by mass percent after the mixed built-in temperature of heat rises to 100 DEG C（The degree of polymerization is 800）、 8% aluminum stearate, 7% modified crosslinking agent, 8% ammonium hydrogen carbonate, 2% oxidic polyethylene, 32% filler the mixed machine of heat is added Interior, control mixing speed is 1000r/min, and after stirring 10min, mixture is sent into cold mixer, and control mixing speed is 200r/min is cooled to 25 DEG C, and sandwich layer melt is made.
The preparation method of the modified crosslinking agent is：It is 35% epoxy resin, 25% metering system by mass percent Sour cyclohexyl, 25% diisocyanate, 10% Corvic, 5% KH550 be added microwave radiation reactor in, control Mixing speed is 500r/min, reacts 1h at 100 DEG C, and modified crosslinking agent is made.
The preparation method of the filler is：By mass percent be respectively 51% random polypropylene, 15% calcium carbonate, 5% silica, 5% lithium carbonate, 10% deionized water be added ceramic ball mill in, after ball milling 1h, be added mass percent be 14% compound modifier continues ball milling 3h, is sieved after the completion of ball milling, the filler is made；The compound modifier is by methyl Acrylic acid is 2 in mass ratio with monoalkoxy unsaturated fatty acid titanate esters:1 mixes.Pearl is big in the mechanical milling process It is small than being big:In:Small=1:1:3, after the completion of ball milling, use 250 mesh reciprocating sieves filtering water mill slurry.
S03, the extrusion of melt：
The sandwich layer melt prepared in S02 is added in conical double screw extruder, the protective layer melt prepared in S01 is added another It in an outer conical double screw extruder, carries out while squeezing out, conical double screw extruder screw speed is 25r/min, processing Temperature is 160 DEG C.
S04, the preparation of cross-linked polrvinyl chloride plank：
The protective layer melt of the sandwich layer melt squeezed out in S03, extrusion is delivered to by distributor in vacuum water-cooled shaping mold, It is cooled down（Cooling velocity is 65 DEG C/min, and temperature is 30 DEG C after cooling）, sizing, traction, then cut to required size, Cross-linked polrvinyl chloride plank is made.
Finally, it should be noted that above example be only to illustrate the embodiment of the present invention technical solution rather than to its into Row limitation, although the embodiment of the present invention is described in detail with reference to preferred embodiment, those skilled in the art It should be understood that the technical solution of the embodiment of the present invention can be still modified or replaced equivalently, and these are changed or wait The range of modified technical solution disengaging technical solution of the embodiment of the present invention cannot also be made with replacement.

Claims (10)

1. a kind of cross-linked polrvinyl chloride plank, it is characterised in that：Including sandwich layer, and it is covered in the protective layer of core layer surface；
Wherein, the raw material for preparing of sandwich layer is respectively with mass percent：Corvic 40%-60%, stabilizer 3%-12%, changes Property crosslinking agent 5%-10%, foaming agent 5%-10%, lubricant 2%-6%, filler 25%-35%；
The raw material for preparing of protective layer is respectively with mass percent：Corvic 50%-60%, modified crosslinking agent 2%-12%, Stabilizer 5%-10%, plasticizer 5%-15%, filler 20%-35%；
The preparation method of the modified crosslinking agent is：By the soft list of epoxy resin, 10%-25% that mass percent is 30%-40% The coupling agent addition microwave radiation reactor of body, the diisocyanate of 20%-30%, the Corvic of 10%-20%, 5%-15% Interior, control mixing speed is 500-650r/min, reacts 0.5-1.5h at 90-110 DEG C, and modified crosslinking agent is made；
The preparation method of the filler is：It is respectively the random polypropylene of 50%-60%, the carbon of 10%-20% by mass percent Sour calcium, the silica of 5%-10%, the lithium carbonate of 2%-7%, 10%-20% deionized water be added ceramic ball mill in, ball milling 1- After 1.5h, the compound modifier that mass percent is 8%-16% is added, continues ball milling 2.5-5h, is sieved, is made after the completion of ball milling The filler.
2. cross-linked polrvinyl chloride plank as described in claim 1, it is characterised in that：The PVC resin polymerization degree is 800- 1000。
3. cross-linked polrvinyl chloride plank as described in claim 1, it is characterised in that：The stabilizer is Ca Zn composite object, carboxylic acid One or more of organotin, aluminum stearate, rare-earth stabilizer.
4. cross-linked polrvinyl chloride plank as described in claim 1, it is characterised in that：The foaming agent is sodium bicarbonate, bicarbonate One or more of ammonium, azido compound, azodicarbonamide, azodiisobutyronitrile.
5. cross-linked polrvinyl chloride plank as described in claim 1, it is characterised in that：The lubricant be stearic acid, stearate, One or more of Solsperse 2000, stearic amide, paraffin, oxidic polyethylene, polyethylene wax.
6. cross-linked polrvinyl chloride plank as described in claim 1, it is characterised in that：The plasticizer is epoxidized soybean oil, epoxy One or more of the misery ester of soybean oil, epoxy acetyl linolenic acid methyl esters, epoxyfuoic-oleic.
7. cross-linked polrvinyl chloride plank as described in claim 1, it is characterised in that：In the preparation method of the modified crosslinking agent, The soft monomer is one or more of cyclohexyl methacrylate, n-BMA, isooctyl methacrylate； The coupling agent is silane coupling agent.
8. cross-linked polrvinyl chloride plank as described in claim 1, it is characterised in that：It is described in the preparation method of the filler Compound modifier is (2-4) in mass ratio by methacrylic acid and monoalkoxy unsaturated fatty acid titanate esters:1 mixes.
9. a kind of method preparing the cross-linked polrvinyl chloride plank as described in claim 1-8 is any, it is characterised in that：Including as follows Step：
S01, the raw material of protective layer is weighed according to the mass percent of each component respectively, and the mixed built-in temperature of heat rises to 95-105 DEG C Afterwards, it adds raw materials into the mixed machine of heat, control mixing speed is 900-1100r/min, after being stirred 8-15min, by mixture It is sent into cold mixer, control mixing speed is 200-300r/min, is cooled to 20-40 DEG C, and protective layer melt is made；
S02 weighs the raw material of sandwich layer according to the mass percent of each component respectively, after the mixed built-in temperature of heat rises to 95-105 DEG C, It adds raw materials into the mixed machine of heat, control mixing speed is 900-1100r/min, and after being stirred 8-15min, mixture is sent into In cold mixer, control mixing speed is 200-300r/min, is cooled to 20-40 DEG C, and sandwich layer melt is made；
The sandwich layer melt prepared in S02 is added in conical double screw extruder, the protective layer melt prepared in S01 is added by S03 Enter in an other conical double screw extruder, carry out while squeezing out；
The protective layer melt of the sandwich layer melt squeezed out in S03, extrusion is delivered to by distributor in shaper by S04, is carried out Cooling, sizing, traction, then cut to required size, and cross-linked polrvinyl chloride plank is made.
10. the method for preparing cross-linked polrvinyl chloride plank as claimed in claim 9, it is characterised in that：Conical double ribbon described in S03 Bar extruder screw rotating speed is 20-30r/min, and processing temperature is 150-180 DEG C；Shaper described in S04 is vacuum water cooling Shaper；Cooling velocity described in S04 is 60-80 DEG C/min, and temperature is 30-40 DEG C after cooling.
CN201810450129.0A 2018-05-11 2018-05-11 A kind of cross-linked polrvinyl chloride plank and preparation method thereof Withdrawn CN108623938A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110466222A (en) * 2019-07-12 2019-11-19 安徽绿谷新材料有限公司 A kind of radiation-resistant environment-friendly type mixing plastic floor tile pad and its processing method

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110466222A (en) * 2019-07-12 2019-11-19 安徽绿谷新材料有限公司 A kind of radiation-resistant environment-friendly type mixing plastic floor tile pad and its processing method

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Application publication date: 20181009