CN112940414A - Modified beanstalk powder-POE-PVC composite material and preparation method thereof - Google Patents
Modified beanstalk powder-POE-PVC composite material and preparation method thereof Download PDFInfo
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- CN112940414A CN112940414A CN202110230782.8A CN202110230782A CN112940414A CN 112940414 A CN112940414 A CN 112940414A CN 202110230782 A CN202110230782 A CN 202110230782A CN 112940414 A CN112940414 A CN 112940414A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000000843 powder Substances 0.000 claims abstract description 92
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- 238000000034 method Methods 0.000 claims abstract description 20
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- 238000000227 grinding Methods 0.000 claims description 11
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- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 9
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- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 claims description 6
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- JNXDCMUUZNIWPQ-UHFFFAOYSA-N trioctyl benzene-1,2,4-tricarboxylate Chemical compound CCCCCCCCOC(=O)C1=CC=C(C(=O)OCCCCCCCC)C(C(=O)OCCCCCCCC)=C1 JNXDCMUUZNIWPQ-UHFFFAOYSA-N 0.000 claims description 6
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical group CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 claims description 5
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims description 4
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims description 4
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 claims description 4
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- 239000004711 α-olefin Substances 0.000 claims description 4
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical group CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 claims description 3
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 3
- 235000010354 butylated hydroxytoluene Nutrition 0.000 claims description 3
- OEIWPNWSDYFMIL-UHFFFAOYSA-N dioctyl benzene-1,4-dicarboxylate Chemical compound CCCCCCCCOC(=O)C1=CC=C(C(=O)OCCCCCCCC)C=C1 OEIWPNWSDYFMIL-UHFFFAOYSA-N 0.000 claims description 3
- MIMDHDXOBDPUQW-UHFFFAOYSA-N dioctyl decanedioate Chemical compound CCCCCCCCOC(=O)CCCCCCCCC(=O)OCCCCCCCC MIMDHDXOBDPUQW-UHFFFAOYSA-N 0.000 claims description 3
- JQCXWCOOWVGKMT-UHFFFAOYSA-N phthalic acid diheptyl ester Natural products CCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC JQCXWCOOWVGKMT-UHFFFAOYSA-N 0.000 claims description 3
- VETPHHXZEJAYOB-UHFFFAOYSA-N 1-n,4-n-dinaphthalen-2-ylbenzene-1,4-diamine Chemical compound C1=CC=CC2=CC(NC=3C=CC(NC=4C=C5C=CC=CC5=CC=4)=CC=3)=CC=C21 VETPHHXZEJAYOB-UHFFFAOYSA-N 0.000 claims description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 2
- 239000005977 Ethylene Substances 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims description 2
- IHBCFWWEZXPPLG-UHFFFAOYSA-N [Ca].[Zn] Chemical group [Ca].[Zn] IHBCFWWEZXPPLG-UHFFFAOYSA-N 0.000 claims description 2
- SLETZFVTVXVPLS-UHFFFAOYSA-N [Zn].[Cd].[Ba] Chemical compound [Zn].[Cd].[Ba] SLETZFVTVXVPLS-UHFFFAOYSA-N 0.000 claims description 2
- 150000004645 aluminates Chemical class 0.000 claims description 2
- 229920001577 copolymer Polymers 0.000 claims description 2
- PWWSSIYVTQUJQQ-UHFFFAOYSA-N distearyl thiodipropionate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCCCCCCCC PWWSSIYVTQUJQQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000010687 lubricating oil Substances 0.000 claims description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 2
- 150000008301 phosphite esters Chemical class 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 4
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- 125000004122 cyclic group Chemical group 0.000 abstract description 3
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- 239000000463 material Substances 0.000 description 12
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 229920001587 Wood-plastic composite Polymers 0.000 description 8
- 239000011155 wood-plastic composite Substances 0.000 description 8
- 239000000835 fiber Substances 0.000 description 7
- 238000012545 processing Methods 0.000 description 7
- 238000009700 powder processing Methods 0.000 description 6
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- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 229920002522 Wood fibre Polymers 0.000 description 2
- 240000008042 Zea mays Species 0.000 description 2
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 2
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000002154 agricultural waste Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 235000005822 corn Nutrition 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002025 wood fiber Substances 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
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- 125000001931 aliphatic group Chemical group 0.000 description 1
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- 239000000945 filler Substances 0.000 description 1
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- 239000008273 gelatin Substances 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
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- 231100000956 nontoxicity Toxicity 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 229920000747 poly(lactic acid) Polymers 0.000 description 1
- 239000004626 polylactic acid Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
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- 235000019698 starch Nutrition 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- 239000012745 toughening agent Substances 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
- 235000021419 vinegar Nutrition 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
- C08H8/00—Macromolecular compounds derived from lignocellulosic materials
-
- 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
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
-
- 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
- C08J2423/04—Homopolymers or copolymers of ethene
- C08J2423/08—Copolymers of ethene
-
- 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
- C08J2497/00—Characterised by the use of lignin-containing materials
- C08J2497/02—Lignocellulosic material, e.g. wood, straw or bagasse
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Biochemistry (AREA)
- Materials Engineering (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a modified beanstalk powder-POE-PVC composite material and a preparation method thereof, wherein the modified beanstalk powder-POE-PVC composite material is prepared from the following raw materials in parts by weight: 100 parts of PVC resin, 5-25 parts of plasticizer, 2-5 parts of heat stabilizer, 1-5 parts of co-stabilizer, 0.1-2 parts of lubricant, 0.3-1 part of antioxidant, 10-50 parts of POE and 11-52.5 parts of modified beanstalk powder; the modified beanstalk powder is prepared by modifying beanstalk powder by a wet method by using a coupling agent, wherein the mass of the coupling agent is 1-5% of that of the beanstalk powder. According to the modified beanstalk powder-POE-PVC composite material, the beanstalk powder is modified by the coupling agent and the POE, so that the flexibility of the composite material is greatly improved while the carbon emission is reduced (the cyclic utilization of the soybean stalks is realized), the production cost is reduced; the preparation process is simple, the production cost is low, and the application prospect is good.
Description
Technical Field
The invention belongs to the technical field of composite materials, and relates to a modified beanstalk powder-POE-PVC composite material and a preparation method thereof.
Background
With the worldwide annual depletion of forest resources, forest deforestation has been severely limited. However, as a world-spotlighted agricultural big country, the yield of agricultural wastes in China is in the forefront of the world, and especially soybean straws are the main agricultural wastes next to corn straws. The composition and structure of soybean straw has many unique features compared to wood and other crops. Compared with wood, the ash content is high, and the main components of the ash content are carbonate and silicate, which are needed for improving the mechanical properties of the PVC composite material. From the view of the content of lignin and cellulose, the content of the cellulose in the soybean straws is similar to that of wood, the content of the lignin is similar to that of hardwood, and the content of the brown fiber is higher than that of other straws, so that the soybean straw is very suitable for replacing wood in the PVC wood-plastic composite material.
With the rapid development of national economy in China, a large number of plates are needed for improvement of the living environment of people and infrastructure construction, and plastic replacing wood is a main development trend in recent years. The wood-plastic board is produced by taking Polyethylene (PE), polypropylene (PP) and PVC as a matrix, taking wood powder such as wood, agricultural straw and crop shell powder as a filler and adopting a convenient extrusion molding process, and compared with artificial boards such as density boards, shaving boards, laminated boards and the like, the PVC wood-plastic board does not need to use an adhesive which seriously pollutes the environment (the solvent is mostly formaldehyde), and the PVC wood-plastic board is combined with the characteristics of PVC, so that the wood-plastic board has the characteristics of no toxicity, flame retardance and environmental protection, and has very wide use amount. If the beanstalk powder is used for replacing wood, the method has important significance of saving resources and protecting environment.
Chinese straw resources are very rich, nearly 7 hundred million t of various crop straws are produced in China every year, and the crop straws account for 20-30% of the total amount of the straws in the world. Taking Jilin province as an example, the planting area of soybeans is about 1000 million mu, the total amount of the discarded beanstalks is about 260 million t per mu calculated according to the beanstalk yield of 0.26t per mu, and the huge resource is used as a life energy source in rural areas, and most of the huge resource is abandoned in the land or is burnt on the spot, so that the resource is wasted and the environment is polluted.
Therefore, many researches are carried out in the field aiming at the beanstalk composite material, for example, CN 201410268888.7 discloses a preparation method of a crop beanstalk fiber composite material, which comprises the steps of cleaning beanstalk, treating with acid, and reacting with a silane coupling agent and an acrylic acid modifier to prepare the crop beanstalk fiber composite material; CN 201610614703.2 discloses a soybean straw plant fiber synthetic resin and a preparation method thereof, which is characterized in that soybean powder is mixed with rice bran vinegar, caprolactone, aliphatic dicarboxylic acid, pentaerythritol, starch, gelatin and the like to prepare soybean fiber powder, and then the soybean fiber powder is blended with polylactic acid fiber to be extruded and is molded by injection; in the document 1 (test research on processing characteristics of a corn straw mixed beanstalk board material [ A ]. the third scientific forum introduction, 2011, 11, 20-24, Beijing: 1090-; the research results show that the impact strength and the elongation at break are obviously reduced along with the increase of the filling part of the cotton stalk powder, and the research shows that although the chemical components of the beanstalk are close to wood, the surface activity of the beanstalk is lower than that of wood fiber, the strength of the beanstalk is lower than that of the wood fiber, and the mechanical property of the composite material is seriously reduced due to the increase of the filling amount.
Therefore, the development of the beanstalk powder-PVC composite material with good mechanical properties has practical significance.
Disclosure of Invention
The invention aims to overcome the defect of poor mechanical property of the existing beanstalk powder-PVC composite material, and provides the beanstalk powder-PVC composite material with good mechanical property.
In order to achieve the purpose, the invention provides the following technical scheme:
a modified beanstalk powder-POE-PVC composite material is prepared from the following raw materials in parts by weight: 100 parts of PVC resin, 5-25 parts of plasticizer, 2-5 parts of heat stabilizer, 1-5 parts of co-stabilizer, 0.1-2 parts of lubricant, 0.3-1 part of antioxidant, 10-50 parts of POE and 11-52.5 parts of modified beanstalk powder;
the modified beanstalk powder is prepared by modifying beanstalk powder by a wet method by using a coupling agent, wherein the mass of the coupling agent is 1-5% of that of the beanstalk powder.
The impact strength of the modified beanstalk powder-POE-PVC composite material is 3.0-5.54 KJ/m2The tensile strength is 18.39-26.50 MPa, the elongation at break is 15-19%, and the thermal conductivity is 0.21-0.22W/(m.K).
The modified beanstalk powder-POE-PVC composite material adopts the coupling agent to modify beanstalk powder by a wet method, is used for bonding nonpolar groups on the surface of the beanstalk powder to improve the compatibility of the beanstalk powder and POE or PVC, takes the POE in the raw materials as a compatibilizer and toughener (the POE is a thermoplastic elastomer with a unique crab claw-shaped structure and a soft and hard segment structure, and has good compatibility with lignin powder or mineral substance powder), improves the filling part of the beanstalk powder in the composite material by modifying the beanstalk powder by the POE, improves the flexibility of the composite material, reduces carbon emission (realizes the recycling of the beanstalk), reduces the production cost, improves the impact strength and the elongation at break of the composite material, and has the advantages of high impact strength, higher elongation at break and small heat conductivity coefficient compared with the existing similar PVC wood-plastic composite material, provides a beanstalk-PVC composite material with excellent mechanical property, greatly expands the application range of the existing PVC wood-plastic composite material, and has great application prospect.
As a preferred technical scheme:
the modified beanstalk powder-POE-PVC composite material is prepared by drying and mechanically crushing soybean stalks and then grinding the dried and mechanically crushed beanstalk powder by using an ultra-fine grinding machine, wherein the particle size of the beanstalk powder is 200-400 meshes. If the particle size is too large, which is higher than 200 meshes, the mechanical property of the composite material is affected because the particle size is too large, if the particle size is too small, on one hand, the energy consumption is large during grinding, the yield of the beanstalk powder is low, so that the production cost of the powder is improved, and on the other hand, if the particle size is too small, the powder is easy to agglomerate and is difficult to disperse in the composite material.
The modified beanstalk powder-POE-PVC composite material is prepared by the following steps:
dissolving a coupling agent in an organic solvent such as ethanol, acetone or trichloromethane, adding the solution into a powder modifying machine through a feed port, mixing the solution with the beanstalk powder, treating the mixture at the temperature of between 60 and 80 ℃ for 0.5 to 1 hour, uniformly mixing the mixture, keeping the temperature at the temperature of between 50 and 100 ℃ for 6 to 10 hours, and drying the mixture to obtain the modified beanstalk powder.
The modified beanstalk powder-POE-PVC composite material is characterized in that the PVC resin is SG-5, S700, SR-800, SE-700, WS-1000S or P1069;
the plasticizer is dioctyl phthalate (DOP), di-n-octyl phthalate (DNOP), di-n-butyl phthalate (DBP), dioctyl sebacate (DOS), trioctyl trimellitate (TOTM) or dioctyl terephthalate (DOTP);
the heat stabilizer is calcium-zinc composite heat stabilizer, barium-zinc-cadmium composite heat stabilizer or organic tin and other environment-friendly heat stabilizers;
the co-stabilizer is epoxidized soybean oil, phosphite ester or beta-diketone;
the lubricant is stearic acid, zinc stearate or polyethylene glycol lubricating oil GOS;
the antioxidant is 2, 6-di-tert-butyl-4-methylphenol BHT, bisphenol A, antioxidant 1010, antioxidant 300#, antioxidant 1076, antioxidant DNP or antioxidant DSTP;
the POE is a copolymer of ethylene and alpha-olefin;
the coupling agent is stearic acid coupling agent, titanate coupling agent, silane coupling agent, silicate coupling agent or aluminate coupling agent. The specific types of the PVC resin, plasticizer, heat stabilizer, co-stabilizer, lubricant, antioxidant, POE and coupling agent of the present invention are not limited thereto, and only some usable types are given herein, and those skilled in the art can select the specific types according to actual needs.
The modified beanstalk powder-POE-PVC composite material is characterized in that the alpha-olefin is 1-hexene or 1-octene.
The invention provides a preparation method of modified beanstalk powder-POE-PVC composite material, which comprises the steps of adding PVC resin, a plasticizer, a heat stabilizer, a stabilizer aid, a lubricant, an antioxidant, POE and modified beanstalk powder into a high-speed mixer, mixing and dispersing at 80-120 ℃ for 20-60 min, then feeding the mixture into an extruder, and carrying out extrusion granulation to obtain the modified beanstalk powder-POE-PVC composite material. The process flow is simple, the degree of mechanization and automation is high, the production cost is low, and the method has a great application prospect.
As a preferred technical scheme:
according to the preparation method, the extruder is a double-stage extruder set, wherein the three-section temperature and the head temperature of the double-screw extruder are respectively controlled to be 160-175 ℃, 165-180 ℃, 170-185 ℃ and 165-180 ℃, and the body temperature and the head temperature of the single-screw extruder are respectively controlled to be 165-180 ℃ and 170-185 ℃. The extrusion temperature is determined according to the melting temperature of the main resin in the composite material, and too low can not realize the mixing of the composite material into a molten state, and too high can degrade PVC resin or POE, thereby deteriorating the performance of the composite material. The double-stage extruder unit is specifically SHJS twin-screw double-stage extruder unit (model 75/180 or 65/150) or SJS single-screw double-stage extruder unit (model 75/180 or 65/150), although the extruder of the present invention is not limited thereto, and other extruders such as SHJ twin-screw extruder or SJS single-screw extruder (model 120 or 170) may be applied to the present invention.
In addition, the invention also provides another preparation method of the modified beanstalk powder-POE-PVC composite material, which comprises the steps of adding PVC resin, a plasticizer, a heat stabilizer, a lubricant, an antioxidant and modified beanstalk powder/POE master batches into a high-speed mixer, mixing and dispersing for 20-60 min at the temperature of 80-120 ℃, then putting the mixture into an extruder, and carrying out extrusion granulation to obtain the modified beanstalk powder-POE-PVC composite material, wherein the modified beanstalk powder/POE master batches comprise modified beanstalk powder and POE. The modified beanstalk powder/POE master batch is used as an additive for production, so that on one hand, dust pollution can be reduced, the production environment is improved, on the other hand, the beanstalk powder processing process and the composite material processing process can be separated more conveniently, the beanstalk powder is processed into the master batch form at the beanstalk powder processing place, the transportation is convenient, and the subsequent addition is convenient when the composite material is processed.
As a preferred technical scheme:
the preparation method of the modified beanstalk powder/POE master batch comprises the following steps:
mixing the modified beanstalk powder and POE in a high-speed mixer at 50-80 ℃ for 20-60 min, putting the mixture into a double-screw extruder (65, 95, 120 or 150 type), and extruding and granulating the mixture at 70-140 ℃ to obtain modified beanstalk powder/POE master batch, wherein the mass ratio of the modified beanstalk powder to the POE is (3-1): 1. the modified beanstalk powder cannot be filled into the material too much, so that the material cannot be prepared into master batches, and the cost of the composite material is too high due to too little material.
According to the preparation method, the extruder is a double-stage extruder set, wherein the three-section temperature and the head temperature of the double-screw extruder are respectively controlled to be 160-175 ℃, 165-180 ℃, 170-185 ℃ and 165-180 ℃, and the body temperature and the head temperature of the single-screw extruder are respectively controlled to be 165-180 ℃ and 170-185 ℃. The extrusion temperature is determined according to the melting temperature of the main resin in the composite material, and too low can not realize the mixing of the composite system into a molten state, and too high can degrade PVC resin or POE, thereby causing the performance deterioration of the composite material. The scope of protection of the present invention is not limited to this, the extruder may be a single or twin screw extruder, the present invention only provides a feasible technical solution, and the present invention recommends the use of a twin-stage extruder set relatively.
Has the advantages that:
(1) one of the methods for preparing the modified beanstalk powder-POE-PVC composite material provided by the invention is that the beanstalk powder is modified by the coupling agent and the POE, so that the filling part of the beanstalk powder in the composite material can be improved, the flexibility of the composite material is greatly improved while the carbon emission is reduced (the cyclic utilization of the beanstalk is realized), the production cost is reduced, and compared with the existing similar PVC wood-plastic composite material, the modified beanstalk powder-POE-PVC composite material has the advantages of high impact strength, high elongation at break and small heat conductivity coefficient, the application range of the existing PVC wood-plastic composite material is greatly expanded, and the application prospect is wide;
(2) the second preparation method for preparing the modified beanstalk powder-POE-PVC composite material provided by the invention is to produce the modified beanstalk powder/POE master batch as an additive, so that on one hand, dust pollution can be reduced, the production environment is improved, on the other hand, the beanstalk powder processing process and the composite material processing process can be separated more conveniently, the beanstalk powder is processed into the master batch form at the beanstalk powder processing place, the transportation is convenient, and the subsequent addition is convenient during the composite material processing.
(3) The preparation methods of the two modified beanstalk powder-POE-PVC composite materials provided by the invention have the characteristics of simple process flow, high degree of mechanization and automation and low production cost.
Detailed Description
The present invention will be described in more detail with reference to the following embodiments, which are illustrative only of some embodiments of the invention and not all embodiments of the invention.
Example 1
A preparation method of a modified beanstalk powder-POE-PVC composite material comprises the following steps:
(1) preparing modified beanstalk powder:
drying and mechanically crushing soybean straws, and grinding the soybean straws by using an ultra-fine grinding machine to obtain soybean straw powder with the granularity of 200-400 meshes;
dissolving 0.81kg of silane coupling agent KH550 in 5L of ethanol, uniformly mixing, adding the mixture into a powder modifying machine through a feed inlet, mixing with 12.0kg of beanstalk powder, treating at 60-80 ℃ for 0.5-1 h, uniformly mixing, preserving heat at 50-100 ℃ for 6-10 h, and drying to obtain modified beanstalk powder;
(2) fully mixing 30kg of PVC resin (SG-5), 6kg of plasticizer DOP, 0.03kg of lubricant stearic acid, 1.5kg of Ca/Zn composite heat stabilizer, 1.2kg of co-stabilizer epoxidized soybean oil and 0.09kg of antioxidant 1076 in a high-speed mixer, controlling the temperature at 80-120 ℃, mixing for 10-20 min, then adding 4.5kg of POE from a feed inlet, mixing for 5-10 min, finally adding the modified beanstalk powder prepared in the step (1) from the feed inlet, and mixing for 10-20 min;
(3) and putting the mixture into a double-stage extruder set, and performing extrusion granulation to obtain the modified beanstalk powder-POE-PVC composite material, wherein the three-stage temperature and the head temperature of a double-screw extruder in the double-stage extruder set are respectively controlled to be 160-175 ℃, 165-180 ℃, 170-185 ℃ and 165-180 ℃, and the body temperature and the head temperature of a single-screw extruder are respectively controlled to be 165-180 ℃ and 170-185 ℃.
The impact strength of the prepared modified beanstalk powder-POE-PVC composite material is 5.54KJ/m2The tensile strength was 20.70MPa, the elongation at break was 15%, and the thermal conductivity was 0.22W/(mK).
Example 2
A preparation method of a modified beanstalk powder-POE-PVC composite material comprises the following steps:
(1) preparing modified beanstalk powder:
drying and mechanically crushing soybean straws, and grinding the soybean straws by using an ultra-fine grinding machine to obtain soybean straw powder with the granularity of 200-400 meshes;
dissolving 0.61kg of silane coupling agent KH550 in 3L of ethanol, uniformly mixing, mixing with 8.39kg of beanstalk powder through a feed port, treating for 0.5-1 h at 60-80 ℃ in a powder modifying machine, uniformly mixing, preserving heat for 6-10 h at 50-100 ℃, and drying to obtain 9kg of modified beanstalk powder;
(2) preparing modified beanstalk powder/POE master batch:
mixing 9kg of modified beanstalk powder prepared in the step (1) and 9kg of POE in a high-speed mixer at 50-80 ℃ for 20-60 min, and putting the mixture into a double-screw extruder for extrusion granulation at 70-140 ℃ to prepare 18kg of modified beanstalk powder/POE master batch;
(3) fully mixing 30kg of PVC paste resin P1650, 6kg of plasticizer DOP, 0.03kg of lubricant stearic acid, 1.5kg of Ca/Zn composite heat stabilizer, 1.2kg of co-stabilizer epoxidized soybean oil and 0.09kg of antioxidant 1076 in a high-speed mixer, controlling the temperature at 80-120 ℃, mixing for 10-20 min, adding the modified beanstalk powder/POE master batch prepared in the step (2) from a feed inlet, and mixing for 5-10 min;
(4) and putting the mixture into a double-stage extruder set, and extruding to obtain the modified beanstalk powder-POE-PVC composite material, wherein the three-stage temperature and the head temperature of a double-screw extruder in the double-stage extruder set are respectively controlled to be 160-175 ℃, 165-180 ℃, 170-185 ℃ and 165-180 ℃, and the body temperature and the head temperature of a single-screw extruder are respectively controlled to be 165-180 ℃ and 170-185 ℃.
The impact strength of the prepared modified beanstalk powder-POE-PVC composite material is 3.0KJ/m2The tensile strength was 18.40MPa, the elongation at break was 19%, and the thermal conductivity was 0.21W/(mK). Compared with example 1, the impact strength of this example is lower, and the main reason is that the loading of POE is higher (POE: 1), which results in the decrease of the impact strength of the composite material, but the elongation at break is also relatively higher.
Example 3
A preparation method of a modified beanstalk powder-POE-PVC composite material comprises the following steps:
(1) preparing modified beanstalk powder:
drying and mechanically crushing soybean straws, and grinding the soybean straws by using an ultra-fine grinding machine to obtain soybean straw powder with the granularity of 200-400 meshes;
dissolving 0.61kg of silane coupling agent KH550 in ethanol, mixing uniformly, mixing with 8.39kg of beanstalk powder through a feed port, treating for 0.5-1 h at 60-80 ℃ in a powder modifying machine, uniformly mixing, and drying to obtain 9kg of modified beanstalk powder;
(2) preparing modified beanstalk powder/POE master batch:
mixing 9kg of modified beanstalk powder prepared in the step (1) and 3kg of POE in a high-speed mixer at 50-80 ℃ for 20-60 min, putting the mixture into a 65-type double-screw extruder, and extruding and granulating the mixture at 70-140 ℃ to prepare 12kg of modified beanstalk powder/POE master batch;
(3) fully mixing 30kg of PVC resin SG-5, 6kg of plasticizer TOTM, 0.03kg of lubricant stearic acid, 1.5kg of Ca/Zn composite heat stabilizer, 1.2kg of co-stabilizer epoxidized soybean oil and 0.09kg of antioxidant bisphenol A in a high-speed mixer, controlling the temperature at 80-120 ℃, mixing for 10-20 min, adding 12kg of modified beanstalk powder/POE master batch prepared in the step (2) from a feed inlet, and mixing for 5-10 min;
(4) and putting the mixture into a double-stage extruder set, and extruding to obtain the modified beanstalk powder-POE-PVC composite material, wherein the three-stage temperature and the head temperature of a double-screw extruder in the double-stage extruder are respectively controlled to be 160-175 ℃, 165-180 ℃, 170-185 ℃ and 165-180 ℃, and the body temperature and the head temperature of a single-screw extruder are respectively controlled to be 165-180 ℃ and 170-185 ℃.
The impact strength of the prepared modified beanstalk powder-POE-PVC composite material is 5.20KJ/m2The tensile strength was 26.50MPa, the elongation at break was 16.5%, and the thermal conductivity was 0.22W/(mK).
Comparative example 1
A preparation method of a modified beanstalk-PVC composite material comprises the following steps:
(1) same as in example 3, step (1);
(2) fully mixing 30kg of PVC paste resin P1650, 6kg of plasticizer TOTM, 0.03kg of lubricant stearic acid, 1.5kg of Ca/Zn composite heat stabilizer, 1.2kg of co-stabilizer epoxidized soybean oil and 0.09kg of antioxidant bisphenol A in a high-speed mixer, controlling the temperature at 80-120 ℃, mixing for 10-20 min, adding 9kg of modified beanstalk powder prepared in the step (1) from a feed inlet, and mixing for 5-10 min;
(3) and putting the mixture into a double-stage extruder set, and extruding to obtain the modified beanstalk powder-PVC composite material, wherein the three-stage temperature and the head temperature of a double-screw extruder in the double-stage extruder are respectively controlled at 160-175 ℃, 165-180 ℃, 170-185 ℃ and 165-180 ℃, and the body temperature and the head temperature of a single-screw extruder are respectively controlled at 165-180 ℃ and 170-185 ℃.
The impact strength of the prepared modified beanstalk-PVC composite material is 4.40KJ/m2The tensile strength was 31.70MPa, the elongation at break was 10.3%, and the thermal conductivity was 0.24W/(mK).
Comparative example 2
A preparation method of POE-PVC composite material comprises the following steps:
(1) fully mixing 30kg of PVC paste resin P1650, 3kg of plasticizer TOTM, 0.03kg of lubricant stearic acid, 1.5kg of Ca/Zn composite heat stabilizer, 1.2kg of co-stabilizer epoxidized soybean oil, 0.09kg of antioxidant bisphenol A and 15kg of POE in a high-speed mixer, controlling the temperature at 80-120 ℃, and mixing for 10-20 min;
(2) and putting the mixture into a double-stage extruder set, extruding to obtain the POE-PVC composite material, wherein the three-stage temperature and the head temperature of a double-screw extruder in the double-stage extruder are respectively controlled at 160-175 ℃, 165-180 ℃, 170-185 ℃ and 165-180 ℃, and the body temperature and the head temperature of a single-screw extruder are respectively controlled at 165-180 ℃ and 170-185 ℃.
The prepared POE-PVC composite material has the tensile strength of 13.2MPa, the elongation at break of 13.4 percent and the thermal conductivity coefficient of 0.22W/(m.K).
It can be found by comparing example 3 with comparative examples 1 and 2 that only by adding the coupling agent modified beanstalk and POE simultaneously, the composite material can realize high impact strength, high tensile strength and high elongation at break, i.e. the mechanical properties of the composite material are good, and in addition, the mechanical properties of the composite material of the invention are compared with those of the prior art (the impact strength of the PVC wood-plastic composite material recorded in document 2 is 1.90 KJ/m)2Tensile strength of 45.0MPa and elongation at break of 1.5%) are greatly improved.
Proved by verification, the modified beanstalk powder-POE-PVC composite material disclosed by the invention has the advantages that the beanstalk powder is modified by adopting the coupling agent and POE, the filling part of the beanstalk powder in the composite material can be improved, the flexibility of the composite material is greatly improved while the carbon emission is reduced (the cyclic utilization of the beanstalk is realized), the production cost is reduced, and compared with the existing similar PVC wood-plastic composite material, the modified beanstalk powder-POE-PVC composite material has the advantages of high impact strength, higher elongation at break and small heat conductivity coefficient, the beanstalk-PVC composite material with excellent mechanical properties is provided, the application range of the existing PVC wood-plastic composite material is greatly expanded, and the application prospect is very good; the preparation method has the advantages of simple process flow, low process conditions, high processing speed and low production cost, and can also produce the modified beanstalk powder/POE master batch in the form of additives, so that the dust pollution can be reduced, the production environment is improved, the beanstalk powder processing process and the composite material processing process can be separated more conveniently, the beanstalk powder is processed into the master batch form at the beanstalk powder processing place, the transportation is convenient, and the subsequent addition is convenient during the composite material processing.
Although specific embodiments of the present invention have been described above, it will be appreciated by those skilled in the art that these embodiments are merely illustrative and various changes or modifications may be made without departing from the principles and spirit of the invention.
Claims (10)
1. The modified beanstalk powder-POE-PVC composite material is characterized by being prepared from the following raw materials in parts by weight: 100 parts of PVC resin, 5-25 parts of plasticizer, 2-5 parts of heat stabilizer, 1-5 parts of co-stabilizer, 0.1-2 parts of lubricant, 0.3-1 part of antioxidant, 10-50 parts of POE and 11-52.5 parts of modified beanstalk powder;
the modified beanstalk powder is prepared by modifying beanstalk powder by a wet method by using a coupling agent, wherein the mass of the coupling agent is 1-5% of that of the beanstalk powder.
2. The modified beanstalk powder-POE-PVC composite material of claim 1, wherein the beanstalk powder has a particle size of 200-400 meshes and is obtained by drying, mechanically crushing and grinding soybean stalks with an ultra-fine grinding machine.
3. The modified beanstalk powder-POE-PVC composite material of claim 2, wherein the preparation method of the modified beanstalk powder comprises the following steps:
dissolving a coupling agent in an organic solvent, adding the organic solvent into a powder modifying machine through a feeding port, mixing the organic solvent and the beanstalk powder, treating the mixture at the temperature of between 60 and 80 ℃ for 0.5 to 1 hour, uniformly mixing the mixture, keeping the temperature at the temperature of between 50 and 100 ℃ for 6 to 10 hours, and drying the mixture to obtain the modified beanstalk powder.
4. The modified beanstalk powder-POE-PVC composite material of claim 1, wherein the type of the PVC resin is SG-5, S700, SR-800, SE-700, WS-1000S or P1069;
the plasticizer is dioctyl phthalate, di-n-octyl phthalate, di-n-butyl phthalate, dioctyl sebacate, trioctyl trimellitate or dioctyl terephthalate;
the heat stabilizer is a calcium-zinc composite heat stabilizer, a barium-zinc-cadmium composite heat stabilizer or an organic tin heat stabilizer;
the co-stabilizer is epoxidized soybean oil, phosphite ester or beta-diketone;
the lubricant is stearic acid, zinc stearate or polyethylene glycol lubricating oil;
the antioxidant is 2, 6-di-tert-butyl-4-methylphenol, bisphenol A, antioxidant 1010, antioxidant 300#, antioxidant 1076, antioxidant DNP or antioxidant DSTP;
the POE is a copolymer of ethylene and alpha-olefin;
the coupling agent is stearic acid coupling agent, titanate coupling agent, silane coupling agent, silicate coupling agent or aluminate coupling agent.
5. The modified beanstalk powder-POE-PVC composite material of claim 4, wherein the alpha-olefin is 1-hexene or 1-octene.
6. The method for preparing modified beanstalk powder-POE-PVC composite material according to any one of claims 1 to 5, wherein the PVC resin, the plasticizer, the heat stabilizer, the co-stabilizer, the lubricant, the antioxidant, the POE and the modified beanstalk powder are added into a high-speed mixer, mixed and dispersed at 80-120 ℃ for 20-60 min, and then the mixture is fed into an extruder for extrusion and granulation to obtain the modified beanstalk powder-POE-PVC composite material.
7. The preparation method of claim 6, wherein the extruder is a double-stage extruder set, wherein the three-stage temperature and the head temperature of the double-screw extruder are respectively controlled to be 160-175 ℃, 165-180 ℃, 170-185 ℃ and 165-180 ℃, and the body temperature and the head temperature of the single-screw extruder are respectively controlled to be 165-180 ℃ and 170-185 ℃.
8. The method for preparing modified beanstalk powder-POE-PVC composite material according to any one of claims 1 to 5, wherein the PVC resin, the plasticizer, the heat stabilizer, the co-stabilizer, the lubricant, the antioxidant, the modified beanstalk powder/POE master batch are added into a high-speed mixer, mixed and dispersed at 80-120 ℃ for 20-60 min, the mixture is fed into an extruder, and extrusion granulation is carried out to obtain the modified beanstalk powder-POE-PVC composite material, wherein the modified beanstalk powder/POE master batch comprises the modified beanstalk powder and POE.
9. The preparation method of claim 8, wherein the modified beanstalk powder/POE master batch is prepared by the following steps:
mixing the modified beanstalk powder and POE in a high-speed mixer at 50-80 ℃ for 20-60 min, putting the mixture into a double-screw extruder, and extruding and granulating the mixture at 70-140 ℃ to obtain modified beanstalk powder/POE master batch, wherein the mass ratio of the modified beanstalk powder to the POE is (3-1): 1.
10. the preparation method of claim 8, wherein the extruder is a double-stage extruder set, wherein the three-stage temperature and the head temperature of the double-screw extruder are respectively controlled to be 160-175 ℃, 165-180 ℃, 170-185 ℃ and 165-180 ℃, and the body temperature and the head temperature of the single-screw extruder are respectively controlled to be 165-180 ℃ and 170-185 ℃.
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