CN113334881A - Integrally-formed high-weather-resistance toughened mineral bamboo-wood composite co-extruded sheet and preparation method thereof - Google Patents

Integrally-formed high-weather-resistance toughened mineral bamboo-wood composite co-extruded sheet and preparation method thereof Download PDF

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CN113334881A
CN113334881A CN202110559691.9A CN202110559691A CN113334881A CN 113334881 A CN113334881 A CN 113334881A CN 202110559691 A CN202110559691 A CN 202110559691A CN 113334881 A CN113334881 A CN 113334881A
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bamboo
powder
composite
extruded sheet
weather
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马健
孙锋
苗伟
杨国庆
苗祥成
陆涛
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Shandong Botuo New Material Technology Co ltd
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Shandong Botuo New Material Technology Co ltd
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    • 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
    • B32B27/08—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 synthetic resin
    • 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
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
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    • 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
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    • B32B2307/00—Properties of the layers or laminate
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    • B32B2307/00—Properties of the layers or laminate
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    • 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
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    • 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
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    • 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
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Abstract

The invention belongs to the technical field of PVC (polyvinyl chloride) foamed plates, and particularly relates to an integrally-formed high-weather-resistance toughened mineral bamboo-wood composite co-extruded plate and a preparation method thereof. The plate comprises a core layer and a skin layer, wherein the core layer is made of PVC resin powder, iron tailing powder, active nano calcium carbonate, bamboo fibers, a coupling agent, a foaming regulator, a composite foaming agent, a calcium-zinc stabilizer, a plasticizer, stearic acid, polyethylene wax, oxidized polyethylene and an impact modifier, and the skin layer is made of PVC resin powder + ASA particles and EVA particles + POE particles. The plate is prepared by adopting an integral forming method, the processing cost is low, and the plate prepared by adopting the method has the characteristics of strong rigidity, good toughness, good weather resistance and cold resistance, and high thermal stability and wear resistance.

Description

Integrally-formed high-weather-resistance toughened mineral bamboo-wood composite co-extruded sheet and preparation method thereof
Technical Field
The invention belongs to the technical field of PVC (polyvinyl chloride) foamed plates, and particularly relates to an integrally-formed high-weather-resistance toughened mineral bamboo-wood composite co-extruded plate and a preparation method thereof.
Background
PVC foam material is actively applied in the aspects of landscape garden plank road laying, floor laying, wall boards, fence guardrails, outdoor landscape building, replacement of anticorrosive wood and the like. However, the existing outdoor PVC foaming material generally has the performance and application defects of low weather resistance, poor wear resistance, short service life, fading of plates, material deformation, low-temperature embrittlement and the like. The PVC wood-plastic foam board has high wood powder content and complex process, and a part of products need to be thermally coated with a high-wear-resistant material layer, so that the production cost is high.
Chinese patent CN 102344622A discloses an outdoor polymer co-extrusion floor and a preparation method thereof, wherein a non-environment-friendly o-benzene plasticizer DOP is used for a product surface layer, anti-aging agent components are relatively few, and engineering plastic ABS with poor weather resistance is added, so that the floor is easy to degrade under the action of ultraviolet light, and the outdoor application performance of the product is greatly reduced.
Chinese patent CN 108442642A discloses an outdoor floor and a preparation process method thereof, wherein the product is prepared by preparing a PVC substrate, pressing lines and patterns and then performing thermal lamination on a modified high-molecular weather-resistant film. The following disadvantages mainly exist: 1. the production process is complex, three processing steps are required, and the production and manpower processing cost is increased; 2. the operation cost of pattern pressing is high, and the environmental protection is reduced because affinity treatment is required before pattern printing; 3. compared with a weather-resistant co-extruded hard non-foaming surface layer, the modified high-molecular weather-resistant film has relatively low wear resistance and weather resistance.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide an integrally-formed high-weather-resistance toughened mineral bamboo-wood composite co-extruded sheet material which has the characteristics of strong rigidity, good toughness, good weather resistance and cold resistance, and high thermal stability and wear resistance; the invention also provides a preparation method of the composite material, which adopts integral molding and has low processing cost.
The integrally formed high weather-resistant toughened mineral bamboo-wood composite co-extruded sheet material comprises a core layer and a skin layer, wherein,
the core layer is prepared from the following raw materials in parts by weight:
Figure BDA0003078480780000011
Figure BDA0003078480780000021
the cortex is prepared from the following raw materials in parts by weight:
65-80 parts of PVC resin powder and ASA particles
20-35 parts of EVA particles and POE particles;
wherein the mass ratio of the PVC resin powder to the ASA particles is 50-70: 30-50, preferably 60: 40; the mass ratio of EVA to POE is 50-80: 20-50, preferably 50: 50.
the PVC resin powder is a compound of SG-5 and SG-8, the PVC resin powder SG-5 is a powder with the average polymerization degree of 981-1135, the PVC resin powder SG-8 is a powder with the average polymerization degree of 650-740, and the mass ratio of SG-5 to SG-8 is 1: 1-1: 3.
The granularity of the iron tailing powder is 300-1250 meshes.
The particle size of the active nano calcium carbonate is 3000-5000 meshes.
The bamboo and wood fiber granularity is 80-200 meshes.
The coupling agent is one or a mixture of two of piperazinylsilane and chloro-silane.
The foaming regulator is a polymer of high-viscosity methacrylate and styrene, the mass ratio is 1:1, and the intrinsic viscosity is 11-16 eta.
The composite foaming agent is a compound of a yellow foaming agent and a white foaming agent, the yellow foaming agent is azodiisobutyronitrile, the white foaming agent is ammonium bicarbonate, and the mass ratio of the yellow foaming agent to the white foaming agent is 1: 1-1: 3.
The calcium-zinc stabilizer is a calcium-zinc composite heat stabilizer which is synthesized by taking calcium stearate, zinc stearate and hydrotalcite as main bodies.
The plasticizer is a composite plant ester, synthetic plant ester and cyclohexane 1, 2-diisononyl phthalate composite plasticizer, has good compatibility with PVC, excellent processing performance, low volatility and excellent low-temperature performance, and has particularly outstanding low-temperature resistance.
The stearic acid is octadecanoic acid.
The polyethylene wax is low-density polyethylene wax with the number average molecular weight of 3500-5000.
The oxidized polyethylene wax is high-density oxidized polyethylene wax with the number average molecular weight of 15000-20000, has good heat resistance and cold resistance, good chemical stability, higher rigidity and toughness and good mechanical strength.
The impact modifier is synthesized by methyl methacrylate, butadiene and styrene, has good compatibility with PVC, and has excellent high-temperature and low-temperature resistance and impact resistance.
The ASA particles are graft copolymer of acrylate rubber bodies, acrylonitrile and styrene.
The EVA is an ethylene-vinyl acetate copolymer, and has good compatibility with PVC and a VA content of more than 40%. It features good flexibility, rubber elasticity, good flexibility, transparency and surface gloss at-50 deg.C, good chemical stability, ageing resistance, ozone resistance and no toxicity. Good mixing property with the filler and good coloring and forming processability.
The POE is a high polymer of ethylene and octene. The continuous phase and the dispersed phase present a two phase separated polymer blend. The soft chain of the octene curls and the crystalline ethylene chain is used as a physical crosslinking point, so that the octene has excellent toughness and good processability; the POE molecular structure has no unsaturated bond, and has excellent aging resistance; the POE has narrow molecular weight distribution and better fluidity, and the good fluidity can improve the dispersion effect of the filler and simultaneously improve the weld mark strength of the product. The relative density is small, so the volume and the price are low. Excellent heat resistance and cold resistance, wide application range, and good weather resistance and aging resistance.
The preparation method of the integrally formed high-weather-resistance toughened mineral bamboo-wood composite co-extruded sheet comprises the following steps:
1) preparation of modified iron tailings and bamboo fiber powder
Putting the coupling agent, the iron tailing powder and the bamboo fiber into a high-speed mixer according to the formula proportion, mixing at the mixing speed of 950r/min to 80 ℃, taking out the mixed powder, putting the powder into a drying oven, and drying for 0.5h at the temperature of 80 ℃ to obtain modified iron tailing and bamboo fiber powder for later use;
2) mixed core layer raw material
Adding modified iron tailings, bamboo and wood fiber powder, PVC resin powder, active nano calcium carbonate, a foaming regulator, a composite foaming agent, a calcium-zinc stabilizer, a plasticizer, stearic acid, polyethylene wax, oxidized polyethylene and an impact modifier into a high-speed mixer according to a formula proportion, mixing at a mixing speed of 950r/min until the temperature is 115 ℃, adding the mixture into a low-speed mixer for mixing at a mixing speed of 75r/min, cooling to below 45 ℃, placing the mixture into a storage bin, standing and aging to obtain a uniformly mixed core layer raw material;
3) raw material of skin layer
The first step is as follows: placing EVA and POE into an oven, drying for 1h at 80 ℃, performing high-speed hot mixing at a mixing speed of 950r/min to 115 ℃, adding into a low-speed mixer, performing cold mixing at a mixing speed of 75r/min, cooling to below 45 ℃, and granulating by an extrusion granulator to obtain POE-g-EVA copolymer granules for later use; through modification granulation, the two are fully fused to form a mixed graft copolymer, and an elastomer with excellent toughening effect is obtained;
the second step is that: carrying out high-speed hot mixing on PVC resin powder, ASA particles and POE-g-EVA graft copolymer particles at a mixing speed of 950r/min to 115 ℃, adding the mixture into a low-speed mixer for mixing at a mixing speed of 75r/min, cooling to below 45 ℃, and granulating by an extrusion granulator to obtain a skin layer raw material; fully thermally fusing PVC resin powder, ASA particles and POE-g-EVA mixed graft copolymer through hot mixing granulation;
4) coextruded sheet
Adding the uniformly mixed core layer raw materials into a main hopper of a co-extrusion production line; adding a granulation cortex raw material into a co-extrusion production line auxiliary hopper by using a feeding device; a coextrusion production line is utilized, a main extruder and an auxiliary extruder simultaneously melt and plasticize the core layer raw material and the skin layer raw material, and the core layer raw material and the skin layer raw material are extruded into a die through a combined flow core to extrude a plate; wherein the main machine adopts an SJSZ-80 conical double-screw extruder, the rotating speed is 12-16 rpm/min, the current is 90-120A, the temperature of the screw cylinder is 160 ℃ in a 1 region, 165 ℃ in a 2 region, 170 ℃ in a 3 region and 170 ℃ in a 4 region, the temperature of the confluence core is 155 ℃, and the temperature of the machine head is 180 ℃; the auxiliary machine adopts an SJSZ-65 conical double-screw extruder: the rotating speed is 6-8 rpm/min, and the temperature of the screw cylinder is 1 region 180 ℃,2 region 185 ℃ and 3 region 185 ℃;
5) shaping
Pressing and shaping the extruded sheet by an upper shaping plate and a lower shaping plate to realize the shaping of the sheet;
6) cooling down
Cooling the shaped plates by water, reducing the temperature, arranging heat exchangers in the upper and lower shaped plates, and keeping the temperature of the upper and lower shaped plates at 20 ℃;
7) drawing, embossing and drawing
Carrying out embossing and wire drawing treatment on an extruded plate through an upper embossing roller and a lower drawing roller simultaneously by a traction roller, wherein the temperature of the upper roller and the temperature of the lower roller are 140-145 ℃;
8) cutting
And cutting by using a cutter according to a preset specification to obtain the integrally-formed high-weather-resistance toughened mineral bamboo-wood composite co-extruded sheet.
Compared with the prior art, the invention has the following beneficial effects:
1. the integrally formed high-weather-resistance toughened mineral bamboo-wood composite co-extruded sheet material prepared by the invention has good toughness: by the graft copolymerization of EVA and POE, an elastomer with better compatibility with PVC and ASA can be formed, and the tensile strength, elastic modulus and impact strength of the product are greatly improved.
2. The integrally formed high-weather-resistance toughened mineral bamboo-wood composite co-extruded sheet prepared by the invention has excellent weather resistance: the skin material is obtained by graft copolymerization of EVA and POE and blending of ASA and PVC, so that the product has good aging resistance and excellent heat resistance and cold resistance.
3. The invention adopts integral forming, reduces the processing cost: by utilizing a coextrusion method, wire drawing and embossing are carried out in the traction process, and secondary hot laminating processing is not needed; and the product has stereoscopic impression, the quality of the product is improved, and the application range of the product is widened.
4. The product is highly filled by using iron tailings and bamboo fibers, so that the recycling of solid waste of minerals is fully realized, the purchasing cost of raw materials can be reduced, waste can be changed into valuable, the national environmental protection policy is responded, and the sustainable development is realized.
5. The prepared plate can be used for a plank road, a floor, a wallboard and a fence guardrail of a landscape garden; building an outdoor landscape; a substitute for wood.
Drawings
FIG. 1 is a diagram showing the analysis of the main components of iron ore tailings powder used in the present invention.
Detailed Description
The present invention is further illustrated by, but is not limited to, the following examples.
All the starting materials used in the examples are commercially available, except where otherwise indicated.
Example 1
The integrally formed high weather-resistant toughened mineral bamboo-wood composite co-extruded sheet comprises a core layer and a skin layer, wherein,
the core layer raw material is prepared from the following raw materials in parts by weight:
PVC resin powder SG-8: 25 portions of
PVC resin powder SG-5: 15 portions of
Iron tailing powder: 50 portions of
Active nano calcium carbonate: 5 portions of
Bamboo fiber: 20 portions of
Coupling agent: 0.6 part
Foaming regulator: 10 portions of
A composite foaming agent: 3.5 parts of
Calcium zinc stabilizer: 5.5 parts of
Plasticizer: 4.8 parts of
Stearic acid: 0.5 portion
Polyethylene wax: 0.5 portion
Oxidized polyethylene: 0.3 part
Impact modifier: 6 portions of
The cortex raw material is prepared from the following raw materials in parts by weight:
PVC resin powder SG-5+ ASA particle: 80 parts (PVC/ASA: 60/40)
EVA granular material: 20 portions of
Wherein:
the PVC resin powder is SG-8 and SG-5 produced by Yuan chemical group limited company in northwest of Shanxi province.
The particle size of the iron tailing powder is 300-1250 meshes, and the main components are shown in figure 1.
The active nano calcium carbonate has the granularity of 3000-5000 meshes, and the main component is calcium carbonate.
The bamboo and wood fiber has the granularity of 80-200 meshes, and the main components of the bamboo and wood fiber are low-plant biomass fibers such as sawdust and bamboo dust.
The coupling agent is a mixture of N- (piperazinylethyl) -3-aminopropyl methyl dimethoxy silane coupling agent CAS 128644-51-9 and chloro silane coupling agent SCA-C1CG which are produced by Nanjing Needt new material technology company Limited and have the mass ratio of 1: 1.
The foaming regulator is a polymer with the mass ratio of HL-92 to HL-801 produced by Nikoku chemical Co., Ltd being 1:1, and the intrinsic viscosity of the foaming regulator is 11-16 eta.
The composite foaming agent is a compound of a yellow foaming agent and a white foaming agent, the yellow foaming agent is azodiisobutyronitrile, the white foaming agent is ammonium bicarbonate, and the mass ratio of the yellow foaming agent to the white foaming agent is 1: 2.
The calcium-zinc stabilizer is a calcium-zinc composite heat stabilizer R502PLS/C produced by Halroche plastic additive (Jiangsu) Co.
The plasticizer is an environment-friendly plasticizer T60 produced by double hong chemical engineering science and technology limited in salt cities and a cyclohexane 1, 2-diisononyl diformate Hexamoll DINCH composite plasticizer produced by Dutch Pasteur, and the mass ratio of the plasticizer to the plasticizer is 1: 1.
The stearic acid is stearic acid 18 acid CAS 57-11-14 produced by Indonesian gold company.
The polyethylene wax is polyethylene wax AC-6A produced by the United states Honeywell company.
The oxidized polyethylene wax is high-density oxidized polyethylene wax AC316A produced by Hounsfield company.
The impact modifier is a toughening modifier MBS produced by Guangzhou Baotai new material science and technology limited company.
The ASA particles are prepared by new material science and technology limited of the Welsu Chuangkeke.
The EVA granular material is EVA produced by DuPont in America, and has good compatibility with PVC and the VA content is more than 40%.
The preparation method of the integrally-formed high-weather-resistance toughened mineral bamboo-wood composite co-extruded sheet comprises the following specific steps:
1) preparation of modified iron tailings and bamboo fiber powder
Putting the coupling agent, the iron tailing powder and the bamboo fiber into a high-speed mixer according to a formula ratio, wherein the mixing speed is 950r/min, mixing to 80 ℃, taking out the mixed powder, putting the powder into an oven, and drying for 0.5h at 80 ℃ to obtain modified iron tailing and bamboo fiber powder for later use;
2) mixed core layer raw material
Adding modified iron tailings, bamboo and wood fiber powder, PVC resin powder, active nano calcium carbonate, a foaming regulator, a composite foaming agent, a calcium-zinc stabilizer, a plasticizer, stearic acid, polyethylene wax, oxidized polyethylene and an impact modifier into a high-speed mixer according to a formula proportion, mixing at a mixing speed of 950r/min until the temperature is 115 ℃, adding the mixture into a low-speed mixer for mixing at a mixing speed of 75r/min, cooling to below 45 ℃, placing the mixture into a storage bin, standing and aging to obtain a uniformly mixed core layer raw material;
3) raw material of skin layer
Drying EVA in an oven at 80 ℃ for 1h, then carrying out high-speed hot mixing on PVC resin powder, ASA particles and EVA particles at a mixing speed of 950r/min to 115 ℃, adding the mixture into a low-speed mixer for mixing at a mixing speed of 75r/min, cooling to below 45 ℃, and granulating by an extrusion granulator to obtain a skin layer raw material;
4) coextruded sheet
Adding the uniformly mixed core layer raw materials into a main hopper of a co-extrusion production line; adding a granulation cortex raw material into a co-extrusion production line auxiliary hopper by using a feeding device; a coextrusion production line is utilized, a main extruder and an auxiliary extruder simultaneously melt and plasticize the core layer raw material and the skin layer raw material, and the core layer raw material and the skin layer raw material are extruded into a die through a combined flow core to extrude a plate; wherein the main machine adopts an SJSZ-80 conical double-screw extruder, the rotating speed is 12-16 rpm/min, the current is 90-120A, the temperature of the screw cylinder is 160 ℃ in a 1 region, 165 ℃ in a 2 region, 170 ℃ in a 3 region and 170 ℃ in a 4 region, the temperature of the confluence core is 155 ℃, and the temperature of the machine head is 180 ℃; the auxiliary machine adopts an SJSZ-65 conical double-screw extruder: the rotating speed is 6-8 rpm/min, and the temperature of the screw cylinder is 1 region 180 ℃,2 region 185 ℃ and 3 region 185 ℃;
5) shaping
Pressing and shaping the extruded sheet by an upper shaping plate and a lower shaping plate to realize the shaping of the sheet;
6) cooling down
Cooling the shaped plates by water, reducing the temperature, arranging heat exchangers in the upper and lower shaped plates, and keeping the temperature of the upper and lower shaped plates at 20 ℃;
7) drawing, embossing and drawing
Carrying out embossing and wire drawing treatment on an extruded plate through an upper embossing roller and a lower drawing roller simultaneously by a traction roller, wherein the temperature of the upper roller and the temperature of the lower roller are 140-145 ℃;
8) cutting
And cutting by using a cutter according to a preset specification to obtain the integrally formed high-weather-resistance toughened mineral bamboo-wood composite co-extruded sheet material in the embodiment 1.
Example 2
The integrally formed high weather-resistant toughened mineral bamboo-wood composite co-extruded sheet comprises a core layer and a skin layer, wherein,
the core layer raw material is prepared from the following raw materials in parts by weight:
PVC resin powder SG-8: 25 portions of
PVC resin powder SG-5: 15 portions of
Iron tailing powder: 50 portions of
Active nano calcium carbonate: 5 portions of
Bamboo fiber: 20 portions of
Coupling agent: 0.6 part
Foaming regulator: 10 portions of
A composite foaming agent: 3.5 parts of
Calcium zinc stabilizer: 5.5 parts of
Plasticizer: 4.8 parts of
Stearic acid: 0.5 portion
Polyethylene wax: 0.5 portion
Oxidized polyethylene: 0.3 part
Impact modifier: 6 portions of
The cortex raw material is prepared from the following raw materials in parts by weight:
PVC resin powder SG-5+ ASA particle: 80 parts (PVC/ASA: 60/40)
POE granular material: 20 portions of
Wherein:
the PVC resin powder is SG-8 and SG-5 produced by Yuan chemical group limited company in northwest of Shanxi province.
The particle size of the iron tailing powder is 300-1250 meshes, and the main components are shown in figure 1.
The active nano calcium carbonate has the granularity of 3000-5000 meshes, and the main component is calcium carbonate.
The bamboo and wood fiber has the granularity of 80-200 meshes, and the main components of the bamboo and wood fiber are low-plant biomass fibers such as sawdust and bamboo dust.
The coupling agent is a mixture of N- (piperazinylethyl) -3-aminopropyl methyl dimethoxy silane coupling agent CAS 128644-51-9 and chloro silane coupling agent SCA-C1CG which are produced by Nanjing Needt new material technology company Limited and have the mass ratio of 1: 1.
The foaming regulator is a polymer with the mass ratio of HL-92 to HL-801 produced by Nikoku chemical Co., Ltd being 1:1, and the intrinsic viscosity of the foaming regulator is 11-16 eta.
The composite foaming agent is a compound of a yellow foaming agent and a white foaming agent, the yellow foaming agent is azodiisobutyronitrile, the white foaming agent is ammonium bicarbonate, and the mass ratio of the yellow foaming agent to the white foaming agent is 1: 2.
The calcium-zinc stabilizer is a calcium-zinc composite heat stabilizer R502PLS/C produced by Halroche plastic additive (Jiangsu) Co.
The plasticizer is an environment-friendly plasticizer T60 produced by double hong chemical engineering science and technology limited in salt cities and a cyclohexane 1, 2-diisononyl diformate Hexamoll DINCH composite plasticizer produced by Dutch Pasteur, and the mass ratio of the plasticizer to the plasticizer is 1: 1.
The stearic acid is stearic acid 18 acid CAS 57-11-14 produced by Indonesian gold company.
The polyethylene wax is polyethylene wax AC-6A produced by the United states Honeywell company.
The oxidized polyethylene wax is high-density oxidized polyethylene wax AC316A produced by Hounsfield company.
The impact modifier is a toughening modifier MBS produced by Guangzhou Baotai new material science and technology limited company.
The ASA particles are prepared by new material science and technology limited of the Welsu Chuangkeke.
The POE granular material is DF-940 produced by Sanjing chemical company of Singapore.
The preparation method of the integrally-formed high-weather-resistance toughened mineral bamboo-wood composite co-extruded sheet comprises the following specific steps:
1) preparation of modified iron tailings and bamboo fiber powder
Putting the coupling agent, the iron tailing powder and the bamboo fiber into a high-speed mixer according to a formula ratio, wherein the mixing speed is 950r/min, mixing to 80 ℃, taking out the mixed powder, putting the powder into an oven, and drying for 0.5h at 80 ℃ to obtain modified iron tailing and bamboo fiber powder for later use;
2) mixed core layer raw material
Adding modified iron tailings, bamboo and wood fiber powder, PVC resin powder, active nano calcium carbonate, a foaming regulator, a composite foaming agent, a calcium-zinc stabilizer, a plasticizer, stearic acid, polyethylene wax, oxidized polyethylene and an impact modifier into a high-speed mixer according to a formula proportion, mixing at a mixing speed of 950r/min until the temperature is 115 ℃, adding the mixture into a low-speed mixer for mixing at a mixing speed of 75r/min, cooling to below 45 ℃, placing the mixture into a storage bin, standing and aging to obtain a uniformly mixed core layer raw material;
3) raw material of skin layer
Putting POE into an oven, drying for 1h at 80 ℃, carrying out high-speed hot mixing on PVC resin powder, ASA particles and POE particles at a mixing speed of 950r/min, mixing to 115 ℃, adding into a low-speed mixer, mixing at a mixing speed of 75r/min, cooling to below 45 ℃, and granulating by using an extrusion granulator to obtain a skin layer raw material;
4) coextruded sheet
Adding the uniformly mixed core layer raw materials into a main hopper of a co-extrusion production line; adding a granulation cortex raw material into a co-extrusion production line auxiliary hopper by using a feeding device; a coextrusion production line is utilized, a main extruder and an auxiliary extruder simultaneously melt and plasticize the core layer raw material and the skin layer raw material, and the core layer raw material and the skin layer raw material are extruded into a die through a combined flow core to extrude a plate; wherein the main machine adopts an SJSZ-80 conical double-screw extruder, the rotating speed is 12-16 rpm/min, the current is 90-120A, the temperature of the screw cylinder is 160 ℃ in a 1 region, 165 ℃ in a 2 region, 170 ℃ in a 3 region and 170 ℃ in a 4 region, the temperature of the confluence core is 155 ℃, and the temperature of the machine head is 180 ℃; the auxiliary machine adopts an SJSZ-65 conical double-screw extruder: the rotating speed is 6-8 rpm/min, and the temperature of the screw cylinder is 1 region 180 ℃,2 region 185 ℃ and 3 region 185 ℃;
5) shaping
Pressing and shaping the extruded sheet by an upper shaping plate and a lower shaping plate to realize the shaping of the sheet;
6) cooling down
Cooling the shaped plates by water, reducing the temperature, arranging heat exchangers in the upper and lower shaped plates, and keeping the temperature of the upper and lower shaped plates at 20 ℃;
7) drawing, embossing and drawing
Carrying out embossing and wire drawing treatment on an extruded plate through an upper embossing roller and a lower drawing roller simultaneously by a traction roller, wherein the temperature of the upper roller and the temperature of the lower roller are 140-145 ℃;
8) cutting
And cutting by using a cutter according to a preset specification to obtain the integrally formed high-weather-resistance toughened mineral bamboo-wood composite co-extruded sheet material in the embodiment 2.
Example 3
The integrally formed high weather-resistant toughened mineral bamboo-wood composite co-extruded sheet comprises a core layer and a skin layer, wherein,
the core layer raw material is prepared from the following raw materials in parts by weight:
PVC resin powder SG-8: 25 portions of
PVC resin powder SG-5: 15 portions of
Iron tailing powder: 50 portions of
Active nano calcium carbonate: 5 portions of
Bamboo fiber: 20 portions of
Coupling agent: 0.6 part
Foaming regulator: 10 portions of
A composite foaming agent: 3.5 parts of
Calcium zinc stabilizer: 5.5 parts of
Plasticizer: 4.8 parts of
Stearic acid: 0.5 portion
Polyethylene wax: 0.5 portion
Oxidized polyethylene: 0.3 part
Impact modifier: 6 portions of
The cortex raw material is prepared from the following raw materials in parts by weight:
PVC resin powder SG-5+ ASA particle: 80 parts (PVC/ASA: 60/40)
EVA + POE granules: 20 parts (EVA/POE: 50/50)
Wherein:
the PVC resin powder is SG-8 and SG-5 produced by Yuan chemical group limited company in northwest of Shanxi province.
The particle size of the iron tailing powder is 300-1250 meshes, and the main components are shown in figure 1.
The active nano calcium carbonate has the granularity of 3000-5000 meshes, and the main component is calcium carbonate.
The bamboo and wood fiber has the granularity of 80-200 meshes, and the main components of the bamboo and wood fiber are low-plant biomass fibers such as sawdust and bamboo dust.
The coupling agent is a mixture of N- (piperazinylethyl) -3-aminopropyl methyl dimethoxy silane coupling agent CAS 128644-51-9 and chloro silane coupling agent SCA-C1CG which are produced by Nanjing Needt new material technology company Limited and have the mass ratio of 1: 1.
The foaming regulator is a polymer with the mass ratio of HL-92 to HL-801 produced by Nikoku chemical Co., Ltd being 1:1, and the intrinsic viscosity of the foaming regulator is 11-16 eta.
The composite foaming agent is a compound of a yellow foaming agent and a white foaming agent, the yellow foaming agent is azodiisobutyronitrile, the white foaming agent is ammonium bicarbonate, and the mass ratio of the yellow foaming agent to the white foaming agent is 1: 2.
The calcium-zinc stabilizer is a calcium-zinc composite heat stabilizer R502PLS/C produced by Halroche plastic additive (Jiangsu) Co.
The plasticizer is an environment-friendly plasticizer T60 produced by double hong chemical engineering science and technology limited in salt cities and a cyclohexane 1, 2-diisononyl diformate Hexamoll DINCH composite plasticizer produced by Dutch Pasteur, and the mass ratio of the plasticizer to the plasticizer is 1: 1.
The stearic acid is stearic acid 18 acid CAS 57-11-14 produced by Indonesian gold company.
The polyethylene wax is polyethylene wax AC-6A produced by the United states Honeywell company.
The oxidized polyethylene wax is high-density oxidized polyethylene wax AC316A produced by Hounsfield company.
The impact modifier is a toughening modifier MBS produced by Guangzhou Baotai new material science and technology limited company.
The ASA particles are prepared by new material science and technology limited of the Welsu Chuangkeke.
The EVA granular material is EVA produced by DuPont in America, and has good compatibility with PVC and the VA content is more than 40%.
The POE granular material is DF-940 produced by Sanjing chemical company of Singapore.
The preparation method of the integrally-formed high-weather-resistance toughened mineral bamboo-wood composite co-extruded sheet comprises the following specific steps:
1) preparation of modified iron tailings and bamboo fiber powder
Putting the coupling agent, the iron tailing powder and the bamboo fiber into a high-speed mixer according to the formula proportion, mixing at the mixing speed of 950r/min to 80 ℃, taking out the mixed powder, putting the powder into a drying oven, and drying for 0.5h at the temperature of 80 ℃ to obtain modified iron tailing and bamboo fiber powder for later use;
2) mixed core layer raw material
Adding modified iron tailings, bamboo and wood fiber powder, PVC resin powder, active nano calcium carbonate, a foaming regulator, a composite foaming agent, a calcium-zinc stabilizer, a plasticizer, stearic acid, polyethylene wax, oxidized polyethylene and an impact modifier into a high-speed mixer according to a formula proportion, mixing at a mixing speed of 950r/min until the temperature is 115 ℃, adding the mixture into a low-speed mixer for mixing at a mixing speed of 75r/min, cooling to below 45 ℃, placing the mixture into a storage bin, standing and aging to obtain a uniformly mixed core layer raw material;
3) raw material of skin layer
The first step is as follows: placing EVA and POE into an oven, drying for 1h at 80 ℃, performing high-speed hot mixing at a mixing speed of 950r/min to 115 ℃, adding into a low-speed mixer, performing cold mixing at a mixing speed of 75r/min, cooling to below 45 ℃, and granulating by an extrusion granulator to obtain POE-g-EVA copolymer granules for later use;
the second step is that: carrying out high-speed hot mixing on PVC resin powder, ASA particles and POE-g-EVA graft copolymer particles at a mixing speed of 950r/min to 115 ℃, adding the mixture into a low-speed mixer for mixing at a mixing speed of 75r/min, cooling to below 45 ℃, and granulating by an extrusion granulator to obtain a skin layer raw material;
4) coextruded sheet
Adding the uniformly mixed core layer raw materials into a main hopper of a co-extrusion production line; adding a granulation cortex raw material into a co-extrusion production line auxiliary hopper by using a feeding device; a coextrusion production line is utilized, a main extruder and an auxiliary extruder simultaneously melt and plasticize the core layer raw material and the skin layer raw material, and the core layer raw material and the skin layer raw material are extruded into a die through a combined flow core to extrude a plate; wherein the main machine adopts an SJSZ-80 conical double-screw extruder, the rotating speed is 12-16 rpm/min, the current is 90-120A, the temperature of the screw cylinder is 160 ℃ in a 1 region, 165 ℃ in a 2 region, 170 ℃ in a 3 region and 170 ℃ in a 4 region, the temperature of the confluence core is 155 ℃, and the temperature of the machine head is 180 ℃; the auxiliary machine adopts an SJSZ-65 conical double-screw extruder: the rotating speed is 6-8 rpm/min, and the temperature of the screw cylinder is 1 region 180 ℃,2 region 185 ℃ and 3 region 185 ℃;
5) shaping
Pressing and shaping the extruded sheet by an upper shaping plate and a lower shaping plate to realize the shaping of the sheet;
6) cooling down
Cooling the shaped plates by water, reducing the temperature, arranging heat exchangers in the upper and lower shaped plates, and keeping the temperature of the upper and lower shaped plates at 20 ℃;
7) drawing, embossing and drawing
Carrying out embossing and wire drawing treatment on an extruded plate through an upper embossing roller and a lower drawing roller simultaneously by a traction roller, wherein the temperature of the upper roller and the temperature of the lower roller are 140-145 ℃;
8) cutting
And cutting by using a cutter according to a preset specification to obtain the integrally formed high-weather-resistance toughened mineral bamboo-wood composite co-extruded sheet material in the embodiment 3.
Example 4
The integrally formed high weather-resistant toughened mineral bamboo-wood composite co-extruded sheet comprises a core layer and a skin layer, wherein,
the core layer raw material is prepared from the following raw materials in parts by weight:
PVC resin powder SG-8: 25 portions of
PVC resin powder SG-5: 15 portions of
Iron tailing powder: 50 portions of
Active nano calcium carbonate: 5 portions of
Bamboo fiber: 20 portions of
Coupling agent: 0.6 part
Foaming regulator: 10 portions of
A composite foaming agent: 3.5 parts of
Calcium zinc stabilizer: 5.5 parts of
Plasticizer: 4.8 parts of
Stearic acid: 0.5 portion
Polyethylene wax: 0.5 portion
Oxidized polyethylene: 0.3 part
Impact modifier: 6 portions of
The cortex raw material is prepared from the following raw materials in parts by weight:
PVC resin powder SG-5+ ASA particle: 70 parts (PVC/ASA: 60/40)
EVA + POE granules: 30 parts (EVA/POE: 50/50)
Wherein:
the PVC resin powder is SG-8 and SG-5 produced by Yuan chemical group limited company in northwest of Shanxi province.
The particle size of the iron tailing powder is 300-1250 meshes, and the main components are shown in figure 1.
The active nano calcium carbonate has the granularity of 3000-5000 meshes, and the main component is calcium carbonate.
The bamboo and wood fiber has the granularity of 80-200 meshes, and the main components of the bamboo and wood fiber are low-plant biomass fibers such as sawdust and bamboo dust.
The coupling agent is a mixture of N- (piperazinylethyl) -3-aminopropyl methyl dimethoxy silane coupling agent CAS 128644-51-9 and chloro silane coupling agent SCA-C1CG which are produced by Nanjing Needt new material technology company Limited and have the mass ratio of 1: 1.
The foaming regulator is a polymer with the mass ratio of HL-92 to HL-801 produced by Nikoku chemical Co., Ltd being 1:1, and the intrinsic viscosity of the foaming regulator is 11-16 eta.
The composite foaming agent is a compound of a yellow foaming agent and a white foaming agent, the yellow foaming agent is azodiisobutyronitrile, the white foaming agent is ammonium bicarbonate, and the mass ratio of the yellow foaming agent to the white foaming agent is 1: 2.
The calcium-zinc stabilizer is a calcium-zinc composite heat stabilizer R502PLS/C produced by Halroche plastic additive (Jiangsu) Co.
The plasticizer is an environment-friendly plasticizer T60 produced by double hong chemical engineering science and technology limited in salt cities and a cyclohexane 1, 2-diisononyl diformate Hexamoll DINCH composite plasticizer produced by Dutch Pasteur, and the mass ratio of the plasticizer to the plasticizer is 1: 1.
The stearic acid is stearic acid 18 acid CAS 57-11-14 produced by Indonesian gold company.
The polyethylene wax is polyethylene wax AC-6A produced by the United states Honeywell company.
The oxidized polyethylene wax is high-density oxidized polyethylene wax AC316A produced by Hounsfield company.
The impact modifier is a toughening modifier MBS produced by Guangzhou Baotai new material science and technology limited company.
The ASA particles are prepared by new material science and technology limited of the Welsu Chuangkeke.
The EVA granular material is EVA produced by DuPont in America, and has good compatibility with PVC and the VA content is more than 40%.
The POE granular material is DF-940 produced by Sanjing chemical company of Singapore.
The preparation method of the integrally-formed high-weather-resistance toughened mineral bamboo-wood composite co-extruded sheet comprises the following specific steps:
1) preparation of modified iron tailings and bamboo fiber powder
Putting the coupling agent, the iron tailing powder and the bamboo fiber into a high-speed mixer according to the formula proportion, mixing at the mixing speed of 950r/min to 80 ℃, taking out the mixed powder, putting the powder into a drying oven, and drying for 0.5h at the temperature of 80 ℃ to obtain modified iron tailing and bamboo fiber powder for later use;
2) mixed core layer raw material
Adding modified iron tailings, bamboo and wood fiber powder, PVC resin powder, active nano calcium carbonate, a foaming regulator, a composite foaming agent, a calcium-zinc stabilizer, a plasticizer, stearic acid, polyethylene wax, oxidized polyethylene and an impact modifier into a high-speed mixer according to a formula proportion, mixing at a mixing speed of 950r/min until the temperature is 115 ℃, adding the mixture into a low-speed mixer for mixing at a mixing speed of 75r/min, cooling to below 45 ℃, placing the mixture into a storage bin, standing and aging to obtain a uniformly mixed core layer raw material;
3) raw material of skin layer
The first step is as follows: placing EVA and POE into an oven, drying for 1h at 80 ℃, performing high-speed hot mixing at a mixing speed of 950r/min to 115 ℃, adding into a low-speed mixer, performing cold mixing at a mixing speed of 75r/min, cooling to below 45 ℃, and granulating by an extrusion granulator to obtain POE-g-EVA copolymer granules for later use;
the second step is that: carrying out high-speed hot mixing on PVC resin powder, ASA particles and POE-g-EVA graft copolymer particles at a mixing speed of 950r/min to 115 ℃, adding the mixture into a low-speed mixer for mixing at a mixing speed of 75r/min, cooling to below 45 ℃, and granulating by an extrusion granulator to obtain a skin layer raw material;
4) coextruded sheet
Adding the uniformly mixed core layer raw materials into a main hopper of a co-extrusion production line; adding a granulation cortex raw material into a co-extrusion production line auxiliary hopper by using a feeding device; a coextrusion production line is utilized, a main extruder and an auxiliary extruder simultaneously melt and plasticize the core layer raw material and the skin layer raw material, and the core layer raw material and the skin layer raw material are extruded into a die through a combined flow core to extrude a plate; wherein the main machine adopts an SJSZ-80 conical double-screw extruder, the rotating speed is 12-16 rpm/min, the current is 90-120A, the temperature of the screw cylinder is 160 ℃ in a 1 region, 165 ℃ in a 2 region, 170 ℃ in a 3 region and 170 ℃ in a 4 region, the temperature of the confluence core is 155 ℃, and the temperature of the machine head is 180 ℃; the auxiliary machine adopts an SJSZ-65 conical double-screw extruder: the rotating speed is 6-8 rpm/min, and the temperature of the screw cylinder is 1 region 180 ℃,2 region 185 ℃ and 3 region 185 ℃;
5) shaping
Pressing and shaping the extruded sheet by an upper shaping plate and a lower shaping plate to realize the shaping of the sheet;
6) cooling down
Cooling the shaped plates by water, reducing the temperature, arranging heat exchangers in the upper and lower shaped plates, and keeping the temperature of the upper and lower shaped plates at 20 ℃;
7) drawing, embossing and drawing
Carrying out embossing and wire drawing treatment on an extruded plate through an upper embossing roller and a lower drawing roller simultaneously by a traction roller, wherein the temperature of the upper roller and the temperature of the lower roller are 140-145 ℃;
8) cutting
And cutting by using a cutter according to a preset specification to obtain the integrally formed high-weather-resistance toughened mineral bamboo-wood composite co-extruded sheet material in the embodiment 4.
Comparative example 1
Commercially available co-extruded sheets.
Comparative example 2
A common co-extruded sheet material comprises a core layer and a skin layer, wherein,
the core layer raw material is prepared from the following raw materials in parts by weight:
PVC resin powder SG-8: 25 portions of
PVC resin powder SG-5: 15 portions of
Active nano calcium carbonate: 75 portions of
Foaming regulator: 10 portions of
A composite foaming agent: 3.5 parts of
Calcium zinc stabilizer: 5.5 parts of
Plasticizer: 4.8 parts of
Stearic acid: 0.5 portion
Polyethylene wax: 0.5 portion
Oxidized polyethylene: 0.3 part
Impact modifier: 6 portions of
The cortex raw material is prepared from the following raw materials in parts by weight:
PVC resin powder SG-5: 70 portions of
Active nano calcium carbonate: 30 portions of
Calcium zinc stabilizer: 5.5 parts of
Stearic acid: 0.5 portion
Polyethylene wax: 0.5 portion
Impact modifier: 20 portions of
Wherein:
the PVC resin powder is SG-8 and SG-5 produced by Yuan chemical group limited company in northwest of Shanxi province.
The active nano calcium carbonate has the granularity of 3000-5000 meshes, and the main component is calcium carbonate.
The foaming regulator is a polymer with the mass ratio of HL-92 to HL-801 produced by Nikoku chemical Co., Ltd being 1:1, and the intrinsic viscosity of the foaming regulator is 11-16 eta.
The composite foaming agent is a compound of a yellow foaming agent and a white foaming agent, the yellow foaming agent is azodiisobutyronitrile, the white foaming agent is ammonium bicarbonate, and the mass ratio of the yellow foaming agent to the white foaming agent is 1: 2.
The calcium-zinc stabilizer is a calcium-zinc composite heat stabilizer R502PLS/C produced by Halroche plastic additive (Jiangsu) Co.
The plasticizer is an environment-friendly plasticizer T60 produced by double hong chemical engineering science and technology limited in salt cities and a cyclohexane 1, 2-diisononyl diformate Hexamoll DINCH composite plasticizer produced by Dutch Pasteur, and the mass ratio of the plasticizer to the plasticizer is 1: 1.
The stearic acid is stearic acid 18 acid CAS 57-11-14 produced by Indonesian gold company.
The polyethylene wax is polyethylene wax AC-6A produced by the United states Honeywell company.
The oxidized polyethylene wax is high-density oxidized polyethylene wax AC316A produced by Hounsfield company.
The impact modifier is a toughening modifier MBS produced by Guangzhou Baotai new material science and technology limited company.
The invention relates to a preparation method of an integrally-formed high-weather-resistance toughened mineral bamboo-wood composite co-extruded sheet material, which comprises the following specific steps:
1) mixed core layer raw material
Adding PVC resin powder, active nano calcium carbonate, a foaming regulator, a composite foaming agent, a calcium-zinc stabilizer, a plasticizer, stearic acid, polyethylene wax, oxidized polyethylene and an impact modifier into a high-speed mixer according to a formula proportion, mixing at a mixing speed of 950r/min, mixing to 115 ℃, adding into a low-speed mixer for mixing at a mixing speed of 75r/min, cooling to below 45 ℃, placing into a storage bin, standing and aging to obtain a uniformly mixed core layer raw material;
2) raw material of skin layer
Adding PVC resin powder, active nano calcium carbonate, a calcium-zinc stabilizer, stearic acid, polyethylene wax and an impact modifier into a high-speed mixer according to a formula proportion, mixing at a mixing speed of 950r/min to 115 ℃, adding into a low-speed mixer for mixing at a mixing speed of 75r/min, cooling to below 45 ℃, placing into a storage bin, standing and aging to obtain a uniformly mixed skin layer raw material;
4) coextruded sheet
Adding the uniformly mixed core layer raw materials into a main hopper of a co-extrusion production line; adding a granulation cortex raw material into a co-extrusion production line auxiliary hopper by using a feeding device; a coextrusion production line is utilized, a main extruder and an auxiliary extruder simultaneously melt and plasticize the core layer raw material and the skin layer raw material, and the core layer raw material and the skin layer raw material are extruded into a die through a combined flow core to extrude a plate; wherein the main machine adopts an SJSZ-80 conical twin-screw extruder, the rotating speed is 12-16 rpm/min, the current is 90-120A, the temperature of the screw cylinder is 160 ℃ in a 1 region, 165 ℃ in a 2 region, 170 ℃ in a 3 region and 170 ℃ in a 4 region, the temperature of the confluence core is 155 ℃, and the temperature of the machine head is 175 ℃; the auxiliary machine adopts an SJSZ-65 conical double-screw extruder: the rotating speed is 6-8 rpm/min, and the temperature of the screw cylinder is 170 ℃ in a 1 region, 170 ℃ in a 2 region and 170 ℃ in a 3 region;
5) shaping
Pressing and shaping the extruded sheet by an upper shaping plate and a lower shaping plate to realize the shaping of the sheet;
6) cooling down
Cooling the shaped plates by water, reducing the temperature, arranging heat exchangers in the upper and lower shaped plates, and keeping the temperature of the upper and lower shaped plates at 20 ℃;
7) drawing, embossing and drawing
Carrying out embossing and wire drawing treatment on an extruded plate through an upper embossing roller and a lower drawing roller simultaneously by a traction roller, wherein the temperature of the upper roller and the temperature of the lower roller are 140-145 ℃;
8) cutting
And cutting according to a preset specification by using a cutter to obtain the common co-extruded sheet material of the comparative example 2.
The boards prepared in the above examples 1 to 4 and comparative examples 1 to 2 were subjected to performance tests, and the results of the performance tests are shown in table 1.
Table 1 results of performance testing
Figure BDA0003078480780000171

Claims (10)

1. The utility model provides an integrated into one piece height resistant is able to bear or endure to increase tough mineral bamboo wood composite coextruding panel which characterized in that: comprises a core layer and a skin layer, wherein,
the core layer is prepared from the following raw materials in parts by weight:
Figure FDA0003078480770000011
the cortex is prepared from the following raw materials in parts by weight:
65-80 parts of PVC resin powder and ASA particles
20-35 parts of EVA particles and POE particles;
wherein the mass ratio of the PVC resin powder to the ASA particles is 50-70: 30-50; the mass ratio of the EVA particles to the POE particles is 50-80: 20 to 50.
2. The integrally formed high weather-resistant toughened mineral bamboo-wood composite co-extruded sheet material as claimed in claim 1, wherein: the PVC resin powder is a compound of SG-5 and SG-8, and the mass ratio of SG-5 to SG-8 is 1: 1-1: 3.
3. The integrally formed high weather-resistant toughened mineral bamboo-wood composite co-extruded sheet material as claimed in claim 1, wherein: the granularity of the iron tailing powder is 300-1250 meshes; the particle size of the active nano calcium carbonate is 3000-5000 meshes; the bamboo and wood fiber granularity is 80-200 meshes.
4. The integrally formed high weather-resistant toughened mineral bamboo-wood composite co-extruded sheet material as claimed in claim 1, wherein: the coupling agent is one or a mixture of two of piperazinylsilane and chloro-silane.
5. The integrally formed high weather-resistant toughened mineral bamboo-wood composite co-extruded sheet material as claimed in claim 1, wherein: the foaming regulator is a polymer of high-viscosity methacrylate and styrene, and the intrinsic viscosity is 11-16 eta.
6. The integrally formed high weather-resistant toughened mineral bamboo-wood composite co-extruded sheet material as claimed in claim 1, wherein: the composite foaming agent is a compound of a yellow foaming agent and a white foaming agent, the yellow foaming agent is azodiisobutyronitrile, the white foaming agent is ammonium bicarbonate, and the mass ratio of the yellow foaming agent to the white foaming agent is 1: 1-1: 3.
7. The integrally formed high weather-resistant toughened mineral bamboo-wood composite co-extruded sheet material as claimed in claim 1, wherein: the calcium-zinc stabilizer is a calcium-zinc composite heat stabilizer which is synthesized by taking calcium stearate, zinc stearate and hydrotalcite as main bodies; the plasticizer is a composite plasticizer of composite plant ester, synthetic plant ester and cyclohexane 1, 2-diisononyl diformate.
8. The integrally formed high weather-resistant toughened mineral bamboo-wood composite co-extruded sheet material as claimed in claim 1, wherein: the stearic acid is octadecanoic acid; the polyethylene wax is low-density polyethylene wax with the number average molecular weight of 3500-5000; the oxidized polyethylene wax is high-density oxidized polyethylene wax with the number average molecular weight of 15000-20000; the impact modifier is synthesized by methyl methacrylate, butadiene and styrene.
9. The integrally formed high weather-resistant toughened mineral bamboo-wood composite co-extruded sheet material as claimed in claim 1, wherein: the ASA particles are graft copolymers of acrylate rubber bodies, acrylonitrile and styrene; the EVA particles are ethylene-vinyl acetate copolymer, wherein the VA content is more than 40%; the POE particles are high polymers of ethylene and octene.
10. The preparation method of the integrally formed high-weather-resistance toughened mineral bamboo-wood composite co-extruded sheet material as claimed in any one of claims 1 to 9, which is characterized by comprising the following steps: the method comprises the following steps:
1) preparation of modified iron tailings and bamboo fiber powder
Putting the coupling agent, the iron tailing powder and the bamboo fiber into a high-speed mixer according to the formula proportion, mixing at high speed, taking out the mixed powder, and putting the powder into an oven for drying to obtain modified iron tailing powder and bamboo fiber powder;
2) mixed core layer raw material
Adding modified iron tailings, bamboo and wood fiber powder, PVC resin powder, active nano calcium carbonate, a foaming regulator, a composite foaming agent, a calcium-zinc stabilizer, a plasticizer, stearic acid, polyethylene wax, oxidized polyethylene and an impact modifier into a high-speed mixer according to a formula proportion, mixing, adding into a low-speed mixer, and mixing to obtain a uniformly mixed core layer raw material;
3) raw material of skin layer
Drying EVA and POE, then carrying out high-speed hot mixing, and granulating for later use by an extrusion granulator; carrying out high-speed hot mixing on PVC resin powder, ASA granules, EVA and POE granules, and granulating for later use by an extrusion granulator;
4) coextruded sheet
Adding the uniformly mixed core layer raw materials into a main hopper of a co-extrusion production line; adding a granulation cortex raw material into a co-extrusion production line auxiliary hopper by using a feeding device; extruding the core layer raw material and the skin layer raw material into a die by using a co-extrusion production line and a main extruder and an auxiliary extruder simultaneously to extrude a plate;
5) shaping
Guiding the co-extruded sheet into a shaping roller to realize sheet shaping;
6) cooling down
Cooling the shaped plate by water;
7) drawing, embossing and drawing
Carrying out embossing and wire drawing treatment on an extruded plate through an upper embossing roller and a lower drawing roller simultaneously by a traction roller, wherein the temperature of the upper roller and the temperature of the lower roller are 140-145 ℃;
8) cutting
And cutting by using a cutter according to a preset specification to obtain the integrally-formed high-weather-resistance toughened mineral bamboo-wood composite co-extruded sheet.
CN202110559691.9A 2021-05-21 2021-05-21 Integrally-formed high-weather-resistance toughened mineral bamboo-wood composite co-extruded sheet and preparation method thereof Pending CN113334881A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114276629A (en) * 2021-11-19 2022-04-05 东台市豪威节能科技有限公司 Preparation method of bamboo-wood fiber heat-insulation composite decorative plate

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102501506A (en) * 2011-10-20 2012-06-20 北京欧尼克环保技术有限公司 PVC (Poly Vinyl Chloride) wood-plastic foaming composite and preparation method thereof
CN102922838A (en) * 2012-11-17 2013-02-13 中国化学工程第十四建设有限公司 Three-layer coextruded PVC (polyvinylchloride) wood-plastic composite foam board and preparation method thereof
CN105131413A (en) * 2015-09-01 2015-12-09 江阴市海江高分子材料有限公司 Semiconductive shielding material for high-strength and high-temperature-resistant silane cross-linked cable and preparing method thereof
CN105462245A (en) * 2015-12-30 2016-04-06 广东国立科技股份有限公司 Ultralow-temperature-resistant glass-fiber-reinforced PA6/EVA (polyamide 6/ethylene-vinyl acetate) alloy material and preparation method thereof
CN106832684A (en) * 2017-03-20 2017-06-13 福建剑源木塑科技有限公司 Compound bamboo plastic section bar of a kind of high durable and preparation method thereof
CN109401174A (en) * 2018-10-08 2019-03-01 东莞市创之源新材料科技有限公司 A kind of PBT toughener and preparation method thereof
CN110283399A (en) * 2019-05-06 2019-09-27 浙江中财管道科技股份有限公司 A kind of bamboo and woods fiber wallboard and preparation method thereof
US20200123380A1 (en) * 2017-01-23 2020-04-23 Miracll Chemicals Co., Ltd. A process for the preparation of tpu alloy by in-situ reactive compatibility technology

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102501506A (en) * 2011-10-20 2012-06-20 北京欧尼克环保技术有限公司 PVC (Poly Vinyl Chloride) wood-plastic foaming composite and preparation method thereof
CN102922838A (en) * 2012-11-17 2013-02-13 中国化学工程第十四建设有限公司 Three-layer coextruded PVC (polyvinylchloride) wood-plastic composite foam board and preparation method thereof
CN105131413A (en) * 2015-09-01 2015-12-09 江阴市海江高分子材料有限公司 Semiconductive shielding material for high-strength and high-temperature-resistant silane cross-linked cable and preparing method thereof
CN105462245A (en) * 2015-12-30 2016-04-06 广东国立科技股份有限公司 Ultralow-temperature-resistant glass-fiber-reinforced PA6/EVA (polyamide 6/ethylene-vinyl acetate) alloy material and preparation method thereof
US20200123380A1 (en) * 2017-01-23 2020-04-23 Miracll Chemicals Co., Ltd. A process for the preparation of tpu alloy by in-situ reactive compatibility technology
CN106832684A (en) * 2017-03-20 2017-06-13 福建剑源木塑科技有限公司 Compound bamboo plastic section bar of a kind of high durable and preparation method thereof
CN109401174A (en) * 2018-10-08 2019-03-01 东莞市创之源新材料科技有限公司 A kind of PBT toughener and preparation method thereof
CN110283399A (en) * 2019-05-06 2019-09-27 浙江中财管道科技股份有限公司 A kind of bamboo and woods fiber wallboard and preparation method thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
杨华明，欧阳静: "《尾矿废渣的材料化加工与应用》", 30 September 2017, 北京：冶金工业出版社, pages: 98 *
王福元，吴正严: "《粉煤灰利用手册 第2版》", 中国轻工业出版社, pages: 577 - 323 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114276629A (en) * 2021-11-19 2022-04-05 东台市豪威节能科技有限公司 Preparation method of bamboo-wood fiber heat-insulation composite decorative plate

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