CN112759857B - ASA (acrylonitrile styrene acrylate) resin co-extrusion PVC (polyvinyl chloride) -based wood-plastic composite material as well as preparation method and application thereof - Google Patents
ASA (acrylonitrile styrene acrylate) resin co-extrusion PVC (polyvinyl chloride) -based wood-plastic composite material as well as preparation method and application thereof Download PDFInfo
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- 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
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- 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
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- 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
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- 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
- C08J2423/26—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers modified by chemical after-treatment
- C08J2423/28—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers modified by chemical after-treatment by reaction with halogens or halogen-containing compounds
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- C08J2425/00—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 an aromatic carbocyclic ring; Derivatives of such polymers
- C08J2425/02—Homopolymers or copolymers of hydrocarbons
- C08J2425/04—Homopolymers or copolymers of styrene
- C08J2425/08—Copolymers of styrene
- C08J2425/12—Copolymers of styrene with unsaturated nitriles
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- C08J2433/00—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 only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2433/04—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 only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
- C08J2433/06—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 only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C08J2433/10—Homopolymers or copolymers of methacrylic acid esters
- C08J2433/12—Homopolymers or copolymers of methyl methacrylate
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- 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
- C08J2451/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2451/04—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to rubbers
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- C—CHEMISTRY; METALLURGY
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- C08J2497/00—Characterised by the use of lignin-containing materials
- C08J2497/02—Lignocellulosic material, e.g. wood, straw or bagasse
Abstract
The invention provides an ASA resin co-extrusion PVC-based wood-plastic composite material, which contains an ASA co-extrusion fabric and a PVC-based wood-plastic composite material, wherein the co-extrusion fabric comprises the following components in parts by weight: SAN: 30-80 parts of PMMA: 5-50 parts of a first toughening agent: 5-30 parts of lubricant: 0.1-5 parts of antioxidant: 0.1 to 1 portion. The composite material not only improves the bonding property between the PVC-based wood-plastic composite material and the ASA resin, but also improves the thermal stability shrinkage deformation property of the composite material, and can be applied to products with higher requirements on the thermal stability shrinkage deformation property.
Description
Technical Field
The invention relates to a wood-plastic composite material, in particular to an ASA resin co-extrusion PVC-based wood-plastic composite material and a preparation method and application thereof.
Background
The wood-plastic composite material is a novel product which is developed at a high speed in recent years, and is a plate or a section which is produced by mixing low-processing-temperature high polymer materials such as polyethylene, polypropylene or polyvinyl chloride (PVC) and more than 30-70% of waste plant fibers such as wood flour, rice husks and straws into a new wood material and then carrying out plastic processing technologies such as melt extrusion, mould pressing and injection molding, and is mainly applied to industries such as building materials, furniture, gardens and the like. The wood-plastic composite material can be drilled, planed, nailed, painted and the like wood, can be molded and processed like plastic, and integrates the advantages of high polymer materials and wood. The PVC-based wood-plastic material is deeply favored by consumers due to the flame retardant property and the natural wood-like texture after the forming processing technology, but due to the alpha-CI existing in the PVC molecular structure, molecular chain breakage is easy to occur under the ultraviolet light condition, the phenomena of product surface pulverization, fading and the like are easy to occur, and the application of the PVC-based wood-plastic material in the open air is severely limited. The ASA resin is a graft copolymer of an acrylate rubber body, acrylonitrile and styrene, and can effectively solve the weather resistance problems of ultraviolet light aging, sunlight solarization, outdoor day and night temperature difference and the like by being co-extruded on the PVC wood-plastic surface. However, new problems occur after the ASA resin is added, and on one hand, the ASA is brittle and easily causes poor appearance problems such as corner collapse in the profile cutting process; the ASA co-extrusion fabric and the PVC wood-plastic composite material have poor adhesion, so that delamination is easy to occur in the using process, the profile has the problems of water absorption, swelling, cracking and the like, and the application of the profile is greatly limited; on the other hand, the composite material is also poor in heat-stable shrinkage deformation properties.
For the problem of easy delamination of the surface-core layer, the chinese patent (CN 105150644A) discloses a method for improving the adhesive force of the surface-core layer by adding a high-polarity thermoplastic resin between the surface layer resin and the core layer wood-plastic composite material, wherein the high-polarity thermoplastic resin is generally an ethylene acrylic acid copolymer, an ethylene-ethyl acrylate copolymer, an ethylene-vinyl acetate-vinyl alcohol copolymer, a maleic anhydride grafted ethylene-vinyl acetate copolymer, but the thermal stability shrinkage deformation performance of the wood-plastic composite material is not good, and the application of the wood-plastic composite material is limited.
Disclosure of Invention
The invention provides an ASA resin co-extrusion PVC-based wood-plastic composite material, aiming at overcoming the defects of poor cohesiveness and poor thermal stability shrinkage deformation performance of the PVC-based wood-plastic composite material and ASA resin in the prior art.
The invention also aims to provide a preparation method of the ASA resin co-extruded PVC-based wood-plastic composite material.
The invention also aims to provide application of the ASA resin co-extruded PVC-based wood-plastic composite material.
In order to realize the purpose, the invention adopts the technical scheme that:
an ASA resin co-extrusion PVC-based wood-plastic composite material comprises an ASA co-extrusion fabric and a PVC-based wood-plastic composite material, wherein the co-extrusion fabric comprises the following components in parts by weight:
according to the invention, the weather resistance of the PVC-based wood-plastic composite material is improved by co-extruding the ASA resin with the PVC-based wood-plastic composite material, and aiming at the defects that the ASA resin and the PVC-based wood-plastic composite material are easy to delaminate and the thermal stability and shrinkage deformation performance are poor, the invention adopts the blending of the SAN resin, the PMMA resin and the first toughening agent, so that the ASA resin and the PVC-based wood-plastic composite material have higher cohesive force and the thermal stability and shrinkage deformation performance are greatly improved.
Preferably, the PVC-based wood-plastic composite material comprises the following components in parts by weight:
preferably, the first toughening agent is one or more of SAN high rubber powder, ABS high rubber powder, ASA high rubber powder, ABS, SEBS, POE, ABS-g-MAH, ABSHR-g-MA, ABSHR-OXA, SEBS-GMA, ABS-GMA and SEBS-g-MAH.
Preferably, the second toughening agent of the PVC-based wood-plastic composite material is one or more of chlorinated polyethylene or acrylate core-shell copolymer.
Preferably, the lubricant is one of polysiloxane, calcium stearate, magnesium stearate, zinc stearate, or PE wax.
Preferably, the antioxidant is one of hindered phenol antioxidants, phosphites and thiol antioxidants.
Preferably, the heat stabilizer is one or more of calcium zinc stabilizer, stearic acid, epoxy soybean oil and the like.
Preferably, the foaming agent is one or more of sodium bicarbonate or azodicarbonamide.
The invention also provides a preparation method of the ASA resin co-extrusion PVC-based wood-plastic composite material, which comprises the following steps:
s1, mixing SAN resin, PMMA resin, a first toughening agent, a lubricant and an antioxidant, and then carrying out melt blending extrusion, cooling and granulation by a double-screw extruder to obtain an ASA co-extrusion fabric;
s2, mixing PVC resin, plant fiber, a foaming agent, a heat stabilizer, a second toughening agent, a lubricant and an antioxidant, and then extruding, melting, mixing, extruding, cutting and granulating by a single screw to obtain the PVC-based wood-plastic composite material;
s3, adding the ASA co-extrusion fabric prepared in the step S1 into a side extruder hopper of a co-extrusion extruder, and adding the PVC-based wood-plastic composite material prepared in the step S2 into the extruder into a main feeding hopper; the ASA fabric and the PVC wood-plastic composite material are co-extruded by an extruder and then are extruded and shaped through a neck mold to form the ASA co-extrusion PVC-based wood-plastic composite material.
The processing temperature of the extruder is 160-180 ℃.
The ASA resin co-extrusion PVC-based wood-plastic composite material is applied to the preparation of plates.
Compared with the prior art, the invention has the beneficial effects that:
according to the invention, the toughening agent and the binder are added into the ASA resin and are matched with each other, so that the bonding performance between the PVC-based wood-plastic composite and the ASA resin is improved, the thermal stability shrinkage deformation performance of the composite is also improved, and the composite can be applied to products with higher requirements on the thermal stability shrinkage deformation performance.
Drawings
In FIG. 1, the left image shows the plate prepared in comparative example 1, and the right image shows the effect of the plate prepared in example 1 after being soaked in boiling water for 48 h;
fig. 2 is a graph showing the effects of the plates prepared in comparative example 1, comparative example 2 and example 3 after high and low temperature cycles, respectively, from top to bottom.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, but the embodiments of the present invention are not limited thereto.
The reagents, methods and equipment adopted by the invention are conventional in the technical field if no special description is given.
The following examples and comparative examples employ the following starting materials:
SAN resin: SAN 320NA resin was purchased from kumho petrochemical co.ltd;
PMMA resin: PMMA LG2 was purchased from sumitomo chemical asia ptd;
first toughening agent A: ASA high-gel powder Q350, available from Tohai plastics Co., ltd, anqiu;
first toughening agent B: ABS POW HR181 available from kumho petrochemical co.ltd;
first toughening agent C: EPDM 3745P, available from dupont;
a second toughening agent: chlorinated polyethylene CPE 135A, shandong Gao Xin chemical Co., ltd
Lubricant: CALCIUM STEARATE (BS-3818), available from BELIKE Chemical co., ltd. Licowax PE 520P, available from Clariant Specialty Chemicals;
antioxidant: y-001, available from wind-light chemical Co., ltd, yingkou City; y-002, available from Yingkou City wind and light chemical Co., ltd;
PVC: DG-700, tianjin Staphylea chemical Co., ltd;
plant fiber: DQ100, deqinglin Wood flour, inc.;
foaming agent: LD703S, shanghai jie shangjie chemical ltd;
thermal stabilizer: DA-90391, zhenzhong plastics, inc. of Dongguan;
the present invention will be described in detail with reference to examples and comparative examples.
In the following examples and comparative examples, ASA resin co-extrusion PVC-based wood-plastic composite material was prepared by the following method, and the components were weighed according to the weight ratios in tables 1-2; the method comprises the following specific steps:
s1, mixing SAN resin, PMMA resin, a first toughening agent, a lubricant and an antioxidant to obtain an ASA co-extrusion fabric;
s2, mixing PVC resin, plant fiber, a foaming agent, a heat stabilizer, a second toughening agent, a lubricant and an antioxidant to obtain a PVC-based wood-plastic composite material;
s3, adding the ASA co-extrusion fabric prepared in the step S1 into a side extruder hopper of a co-extrusion extruder, and adding the PVC-based wood-plastic composite material prepared in the step S2 into the extruder into a main feeding hopper; the ASA fabric and the PVC wood-plastic composite material are co-extruded by an extruder and then are extruded and shaped through a neck mold to form the ASA co-extrusion PVC-based wood-plastic composite material.
The processing temperature of the extruder is 160-180 ℃.
Examples 1 to 8
TABLE 1 formulations (parts) of examples 1 to 8
Examples 9 to 13 and comparative examples 1 to 2
TABLE 2 formulations (parts) of examples 9 to 13 and comparative examples 1 to 2
The ASA resin co-extruded PVC-based wood-plastic composite materials prepared in the above examples 1-14 and comparative examples 1-2 are subjected to the following performance tests, and the reference standards and methods for the tests are as follows:
adhesion performance and toughness testing: after the produced section bar is cut, whether the ASA surface layer and the PVC base layer are layered or not is judged to be not bonded.
Heat stable shrinkage deformation performance: after the section with fixed length is subjected to high and low temperature cycle test, the appearance is good if the section is obviously deformed and does not have obvious bending and shrinkage;
boiling water immersion experiment: putting a sample into boiling water for boiling, and then observing the bonding state of the fabric and the core material;
high-low temperature circulation: the sample is placed in a high-low temperature circulating box, the temperature is circularly increased and decreased between minus 30 ℃ and 80 ℃, the temperature is decreased to minus 30 ℃ and is preserved for 4 hours, and then the temperature is increased to 80 ℃ and is preserved for 4 hours to form a cycle;
TABLE 3 data for examples and comparative examples
From examples 1 to 8, the bonding property between the ASA fabric and the PVC wood-plastic base fabric is better along with the increase of the PMMA resin content;
from examples 4 and 9 to 12, with the increase of the toughening agent, the section is more regular during production cutting and construction cutting of the section, and the conditions of flash, unfilled corner and debonding are not easy to form;
from examples 4 and 13 to 14, the effect of ABS POW HR181 is best when different types of tougheners are used, and the other two grades of tougheners also meet the requirements of good appearance and strong bonding performance.
From comparative examples 1 and 2, it can be seen that the desired effect is not achieved without the addition of a toughening agent, which is extremely liable to come off and delaminate upon poaching and which collapses and debonds upon cutting.
As shown in fig. 1 and fig. 2, in fig. 1, after being boiled in boiling water for 48 hours, the sample corner ASA co-extruded fabric of comparative example 1 was already debonded from the PVC-based wood-plastic core layer material, while example 1 was completely undamaged, and the ASA co-extruded fabric and the PVC-based wood-plastic core layer material were very good in adhesion and did not have any debonding phenomenon.
After the high and low temperature cycles of fig. 2, the samples of comparative examples 1 and 2 have been bent and the center of the profile is arched toward the ASA surface, however, the appearance dimension of example 3 is kept good and no significant deformation occurs after the high and low temperature cycles.
It should be understood that the above-described embodiments of the present invention are merely examples for clearly illustrating the present invention and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the claims of the present invention.
Claims (7)
1. The ASA resin co-extrusion PVC-based wood-plastic composite material is characterized by comprising an ASA co-extrusion fabric and a PVC-based wood-plastic composite material, wherein the ASA co-extrusion fabric comprises the following components in parts by weight:
the first toughening agent is ASA high rubber powder and/or ABS;
the PVC-based wood-plastic composite material comprises the following components in parts by weight:
the second toughening agent is one or more of chlorinated polyethylene or acrylate core-shell copolymer.
2. An ASA resin co-extruded PVC-based wood plastic composite as claimed in claim 1, wherein the lubricant is one or more of polysiloxane, calcium stearate, magnesium stearate, zinc stearate or PE wax.
3. The ASA resin co-extruded PVC-based wood-plastic composite material as claimed in claim 1, wherein the antioxidant is one or more of hindered phenol antioxidants or phosphite and thiol antioxidants.
4. The ASA resin co-extruded PVC-based wood-plastic composite material as claimed in claim 1, wherein the heat stabilizer is one or more of calcium zinc stabilizer, stearic acid, and epoxidized soybean oil.
5. The ASA resin co-extruded PVC-based wood-plastic composite according to claim 1, wherein the blowing agent is one or both of sodium bicarbonate or azodicarbonamide.
6. A method for preparing ASA resin co-extruded PVC-based wood-plastic composite material according to any one of claims 1 to 5, which comprises the following steps:
s1, mixing SAN resin, PMMA resin, a first toughening agent, a lubricant and an antioxidant, and then carrying out melt blending extrusion, cooling and granulation by a double-screw extruder to obtain an ASA co-extrusion fabric;
s2, mixing PVC resin, plant fiber, a foaming agent, a heat stabilizer, a second toughening agent, a lubricant and an antioxidant, and then extruding, melting, mixing, extruding, cutting and granulating by a single screw to obtain the PVC-based wood-plastic composite material;
s3, adding the ASA co-extrusion fabric prepared in the step S1 into a side extruder hopper of a co-extrusion extruder, and adding the PVC-based wood-plastic composite material prepared in the step S2 into the extruder into a main feeding hopper; the ASA fabric and the PVC wood-plastic composite material are co-extruded by an extruder and then are extruded and shaped through a neck mold to form the ASA co-extrusion PVC-based wood-plastic composite material.
7. Use of an ASA resin co-extruded PVC-based wood-plastic composite as described in any one of claims 1 to 5 for the preparation of a panel.
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| CN202011551900.7A CN112759857B (en) | 2020-12-24 | 2020-12-24 | ASA (acrylonitrile styrene acrylate) resin co-extrusion PVC (polyvinyl chloride) -based wood-plastic composite material as well as preparation method and application thereof |
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| CN114685926B (en) * | 2022-04-19 | 2023-05-26 | 安徽科居新材料科技有限公司 | ASA coated PVC wood-plastic co-extrusion section bar |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106188927A (en) * | 2016-08-10 | 2016-12-07 | 深圳毅彩鸿翔新材料科技有限公司 | Uvioresistant weatherability ASA resin, coextruded plastic goods, thin film and goods |
| CN109263206A (en) * | 2018-07-31 | 2019-01-25 | 山东霞光集团有限公司 | A kind of co-extrusion wood plastic composite and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106188927A (en) * | 2016-08-10 | 2016-12-07 | 深圳毅彩鸿翔新材料科技有限公司 | Uvioresistant weatherability ASA resin, coextruded plastic goods, thin film and goods |
| CN109263206A (en) * | 2018-07-31 | 2019-01-25 | 山东霞光集团有限公司 | A kind of co-extrusion wood plastic composite and preparation method thereof |
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