CN101712780A - Low-density, high-rigidity and high-tenacity polypropylene nano composite material and preparation method thereof - Google Patents
Low-density, high-rigidity and high-tenacity polypropylene nano composite material and preparation method thereof Download PDFInfo
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- CN101712780A CN101712780A CN200910194556A CN200910194556A CN101712780A CN 101712780 A CN101712780 A CN 101712780A CN 200910194556 A CN200910194556 A CN 200910194556A CN 200910194556 A CN200910194556 A CN 200910194556A CN 101712780 A CN101712780 A CN 101712780A
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- polypropylene
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- -1 polypropylene Polymers 0.000 title claims abstract description 81
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 73
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 73
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 33
- 239000000463 material Substances 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title abstract description 6
- 239000004927 clay Substances 0.000 claims abstract description 15
- 239000011256 inorganic filler Substances 0.000 claims abstract description 14
- 229910003475 inorganic filler Inorganic materials 0.000 claims abstract description 14
- 239000012802 nanoclay Substances 0.000 claims abstract description 14
- 239000002131 composite material Substances 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 13
- 239000012745 toughening agent Substances 0.000 claims abstract description 11
- 239000000654 additive Substances 0.000 claims abstract description 10
- 239000003381 stabilizer Substances 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims description 21
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 20
- 238000007580 dry-mixing Methods 0.000 claims description 20
- 238000005303 weighing Methods 0.000 claims description 17
- 238000001125 extrusion Methods 0.000 claims description 16
- 239000003963 antioxidant agent Substances 0.000 claims description 15
- 230000003078 antioxidant effect Effects 0.000 claims description 15
- PWWSSIYVTQUJQQ-UHFFFAOYSA-N distearyl thiodipropionate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCCCCCCCC PWWSSIYVTQUJQQ-UHFFFAOYSA-N 0.000 claims description 15
- 229920001911 maleic anhydride grafted polypropylene Polymers 0.000 claims description 13
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 9
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 9
- 239000000155 melt Substances 0.000 claims description 7
- 238000012360 testing method Methods 0.000 claims description 7
- 229920001112 grafted polyolefin Polymers 0.000 claims description 6
- 238000012986 modification Methods 0.000 claims description 6
- 230000004048 modification Effects 0.000 claims description 6
- 229920001971 elastomer Polymers 0.000 claims description 5
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 5
- 238000002844 melting Methods 0.000 claims description 5
- 230000008018 melting Effects 0.000 claims description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 4
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 4
- 239000000806 elastomer Substances 0.000 claims description 4
- 239000003063 flame retardant Substances 0.000 claims description 4
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 4
- 239000004604 Blowing Agent Substances 0.000 claims description 3
- 229920002943 EPDM rubber Polymers 0.000 claims description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 3
- 239000005977 Ethylene Substances 0.000 claims description 3
- 239000006057 Non-nutritive feed additive Substances 0.000 claims description 3
- 230000000845 anti-microbial effect Effects 0.000 claims description 3
- 239000003086 colorant Substances 0.000 claims description 3
- 229920001577 copolymer Polymers 0.000 claims description 3
- 239000007822 coupling agent Substances 0.000 claims description 3
- 239000004611 light stabiliser Substances 0.000 claims description 3
- 239000000314 lubricant Substances 0.000 claims description 3
- 239000002667 nucleating agent Substances 0.000 claims description 3
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical group OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 3
- 239000004014 plasticizer Substances 0.000 claims description 3
- 239000004094 surface-active agent Substances 0.000 claims description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- 239000005995 Aluminium silicate Substances 0.000 claims description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 claims description 2
- 239000004793 Polystyrene Substances 0.000 claims description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 2
- 235000012211 aluminium silicate Nutrition 0.000 claims description 2
- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 claims description 2
- 229960000892 attapulgite Drugs 0.000 claims description 2
- 239000000440 bentonite Substances 0.000 claims description 2
- 229910000278 bentonite Inorganic materials 0.000 claims description 2
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- VNSBYDPZHCQWNB-UHFFFAOYSA-N calcium;aluminum;dioxido(oxo)silane;sodium;hydrate Chemical compound O.[Na].[Al].[Ca+2].[O-][Si]([O-])=O VNSBYDPZHCQWNB-UHFFFAOYSA-N 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 229910052621 halloysite Inorganic materials 0.000 claims description 2
- 239000011229 interlayer Substances 0.000 claims description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000010445 mica Substances 0.000 claims description 2
- 229910052618 mica group Inorganic materials 0.000 claims description 2
- 229910000273 nontronite Inorganic materials 0.000 claims description 2
- 229910052625 palygorskite Inorganic materials 0.000 claims description 2
- 229920002401 polyacrylamide Polymers 0.000 claims description 2
- 229920002857 polybutadiene Polymers 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- 229920002223 polystyrene Polymers 0.000 claims description 2
- 229910000077 silane Inorganic materials 0.000 claims description 2
- 150000007970 thio esters Chemical class 0.000 claims description 2
- 229910052902 vermiculite Inorganic materials 0.000 claims description 2
- 239000010455 vermiculite Substances 0.000 claims description 2
- 235000019354 vermiculite Nutrition 0.000 claims description 2
- 230000008569 process Effects 0.000 abstract description 7
- 239000006185 dispersion Substances 0.000 abstract description 3
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 238000005520 cutting process Methods 0.000 abstract 1
- 238000001746 injection moulding Methods 0.000 description 24
- 230000000052 comparative effect Effects 0.000 description 18
- 239000002245 particle Substances 0.000 description 16
- 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 description 13
- 238000001035 drying Methods 0.000 description 12
- 238000005469 granulation Methods 0.000 description 9
- 230000003179 granulation Effects 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- 239000000945 filler Substances 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 8
- 229920006124 polyolefin elastomer Polymers 0.000 description 8
- 238000011056 performance test Methods 0.000 description 5
- 238000009472 formulation Methods 0.000 description 4
- 238000005452 bending Methods 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 238000012661 block copolymerization Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- VNQNXQYZMPJLQX-UHFFFAOYSA-N 1,3,5-tris[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]-1,3,5-triazinane-2,4,6-trione Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CN2C(N(CC=3C=C(C(O)=C(C=3)C(C)(C)C)C(C)(C)C)C(=O)N(CC=3C=C(C(O)=C(C=3)C(C)(C)C)C(C)(C)C)C2=O)=O)=C1 VNQNXQYZMPJLQX-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- PZRWFKGUFWPFID-UHFFFAOYSA-N 3,9-dioctadecoxy-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound C1OP(OCCCCCCCCCCCCCCCCCC)OCC21COP(OCCCCCCCCCCCCCCCCCC)OC2 PZRWFKGUFWPFID-UHFFFAOYSA-N 0.000 description 1
- WPMYUUITDBHVQZ-UHFFFAOYSA-N 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoic acid Chemical compound CC(C)(C)C1=CC(CCC(O)=O)=CC(C(C)(C)C)=C1O WPMYUUITDBHVQZ-UHFFFAOYSA-N 0.000 description 1
- VKJLYEDTHCTCOH-UHFFFAOYSA-N 3-(3-octadecoxy-3-oxopropyl)sulfanylpropanoic acid Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCSCCC(O)=O VKJLYEDTHCTCOH-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000010094 polymer processing Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920005629 polypropylene homopolymer Polymers 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 235000012222 talc Nutrition 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/88—Thermal treatment of the stream of extruded material, e.g. cooling
- B29C48/918—Thermal treatment of the stream of extruded material, e.g. cooling characterized by differential heating or cooling
- B29C48/9185—Thermal treatment of the stream of extruded material, e.g. cooling characterized by differential heating or cooling in the direction of the stream of the material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/04—Particle-shaped
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/09—Articles with cross-sections having partially or fully enclosed cavities, e.g. pipes or channels
- B29C48/10—Articles with cross-sections having partially or fully enclosed cavities, e.g. pipes or channels flexible, e.g. blown foils
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
- B29C48/397—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using a single screw
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/9258—Velocity
- B29C2948/9259—Angular velocity
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92723—Content, e.g. percentage of humidity, volatiles, contaminants or degassing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92819—Location or phase of control
- B29C2948/92857—Extrusion unit
- B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
- B29C2948/92895—Barrel or housing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92819—Location or phase of control
- B29C2948/92857—Extrusion unit
- B29C2948/92904—Die; Nozzle zone
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a low-density, high-rigidity and high-tenacity polypropylene nano composite material and a preparation method thereof. The low-density, high-rigidity and high-tenacity polypropylene nano composite material consists of the following raw materials in percentage by weight: 55 to 98 percent of polypropylene, 1 to 15 percent of organic clay, 0 to 30 percent of inorganic filler, 0.1 to 10 percent of compatilizer, 0 to 20 percent of toughening agent, 0.2 to 2 percent of stabilizing agent, and 0 to 5 percent of other additives. The low-density, high-rigidity and high-tenacity polypropylene nano composite material and the preparation method have the following advantages that: 1, the density and the weight of a product are reduced for the help of reducing the weight and the energy consumption of a finished product; 2, the rigidity and the tenacity are higher; 3, the process flow is simplified and the production cost is reduced effectively; and 4, the influences on the cutting of nano clay and the dispersion process caused by other components are avoided to the utmost extent to further improve the performance of the composite material.
Description
Technical Field
The invention relates to a polypropylene nano composite material, in particular to a polypropylene nano composite material with low density, high rigidity and high toughness and a preparation method of the composite material, belonging to the field of polymer modification and processing.
Background
The polypropylene has good processing performance, physical and chemical properties, so that the polypropylene can be widely applied to internal and external ornaments of automobiles, shells of electronic and household electrical appliances and the like, and is a universal thermoplastic plastic with the highest growth speed at present. However, polypropylene has disadvantages of low rigidity, poor heat resistance, and large shrinkage, and the rigidity of polypropylene is generally improved by adding glass fiber or talc. However, the addition of the glass fiber can affect the molding processability and the surface quality of the product, and the increase of the talcum powder can also increase the density of the polypropylene, thereby increasing the weight of parts of the product. How to increase the rigidity of the material as high as possible while reducing the weight of the product as much as possible has become an interesting research direction in the field of polymer processing modification.
Nanocomposites are a new field of rapid development in material science in recent years. Generally, it refers to a composite material having at least one dimension of the dispersed phase size less than 100 nanometers. The special functions of the nano composite material mainly come from the small-size effect and numerous interfacial composite effects of the particles, and the mechanical property, the barrier property and the flame retardant property of the polymer can be greatly improved by only adding a small amount of nano particles into the polymer through melt mixing or in-situ polymerization, and the heat resistance, the size stability and the electrical conductivity which are much higher than those of the polymer material reinforced by the conventional filler can be obtained.
Since the advent of layered nanoclay and nylon nanocomposites from toyota in the nineties of the last century (as described in japanese patent publication JP1011157 to this company), the excellent properties have rapidly attracted attention, and a number of polymer-based nanoclay composites have been studied, wherein important patents relating to polypropylene-based nanoclay composites include japanese patent publication JP3014854 to toyota, US6632868 to Amcol, US20070299185 to general motors, US20090117393 to Polyone, and the like, and the advent of commercial polymer nanocomposites including polypropylene/nanoclay. However, because the nano filler is difficult to disperse after being added in a large amount, the nano filler is usually premixed with resin to prepare master batches and then is blended with a polymer matrix, the process is complex, the price is expensive, and the upper limit of the addition amount of the nano filler in the polymer matrix is limited. Although a small amount of nano particles can be added alone to obtain considerable performance improvement, the final use performance index and the cost requirement of the product are often not met. Therefore, on the basis of adding a small amount of nano-filler and ensuring good dispersion of the nano-filler, a proper amount of conventional talcum powder filler and toughening elastomer are added simultaneously, so that the composite material with comprehensive performance meeting the actual use requirement can be obtained under the conditions of relatively low material density and cost.
Disclosure of Invention
The invention aims to develop a polypropylene nano composite material with low density, high rigidity and high toughness so as to overcome the limitation of the traditional talcum powder filled polypropylene material or nano clay modified polypropylene material.
It is another object of the present invention to provide a method for preparing such a polypropylene nanocomposite.
The purpose of the invention can be realized by the following technical scheme:
a polypropylene nano composite material with low density, high rigidity and high toughness is prepared from the following raw materials in percentage by weight:
55-98% of polypropylene
1 to 15 percent of organic clay
0 to 30 percent of inorganic filler
0.1 to 10 percent of compatilizer
0 to 20 percent of toughening agent
0.2 to 2 percent of stabilizer
0 to 5 percent of other additives
Wherein,
the polypropylene is homopolymerized propylene or block copolymerization propylene with the melt flow rate (230 ℃ C.. times.2.16 kg) of 0.5-60g/10min, wherein the comonomer of the block copolymerization propylene is ethylene, and the content of the comonomer is in the range of 4-10 mol%.
The organic clay is organized nano clay, the nano clay is one or a composition of more than two of soapstone, halloysite, bentonite, attapulgite, montmorillonite, kaolin, mica, nontronite, beidellite and vermiculite, and the organic clay is subjected to surface modification by an ion exchange method through an organic compound; preferred nanomontmorillonites are amine-based organic compound-treated nanomontmorillonites with an interlayer spacing of 1-20nm, an average particle size of 1-10 μm, and a density of 1-3g/cm3, and alternative nanomontmorillonites include, but are not limited to, Cloisite10A, 15A, 20A, 25A, 93A from Southern Clay products, U.S., Nanocor I.30P, I.44P, DK1 from Zhejiang Fenghong, DK2, DK4, DK1N, and the like.
The inorganic filler is one or more of talcum powder, calcium carbonate and barium sulfate, and the average grain diameter of the inorganic filler is 1-20 mu m; talc powder having an average particle diameter of 1 to 10 μm is preferable.
The compatilizer is grafted polyolefin, and the grafted polyolefin is one or more of grafted polypropylene, grafted polyethylene, grafted polystyrene, grafted ABS and grafted POE; the grafting group is one or more of maleic anhydride, silane, acrylic acid and polyacrylamide; preferably maleic anhydride grafted polypropylene, with a density of 0.89-0.91g/cm3, a melting point of 170-190 ℃, a melt flow rate (230 ℃ C.. times.2.16 kg) of 10-50g/10min and a grafting rate of 0.5-1.0%, obtained by melt extrusion modification of any homo-or block-copolymerized propylene with maleic anhydride.
The toughening agent is any suitable polyolefin elastomer, including but not limited to one or a combination of more than two of polybutadiene rubber, ethylene-propylene-diene rubber (EPDM), ethylene-octene copolymer (POE), etc., preferably POE elastomer, with a melt flow rate (230 ℃ C. x 2.16kg) of 0.5-50g/10 min.
The stabilizer comprises a primary antioxidant and a secondary antioxidant, wherein the primary antioxidant is a hindered phenol or thioester antioxidant, and comprises but is not limited to one or more of 3114 (with the chemical name of 1, 3, 5-tri (3, 5-di-tert-butyl-4-hydroxybenzyl) -1, 3, 5-triazine-2, 4, 6[1H, 3H, 5H ] trione), 1010 (with the chemical name of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester), DSTP (with the chemical name of thiodipropionate stearyl ester); the auxiliary antioxidant is phosphite or ester antioxidant, including but not limited to one or two of 618 (chemical name: dioctadecyl pentaerythritol diphosphite), 168 (chemical name: tris (2, 4-di-tert-butyl) phosphite).
The other additives include one or more of colorants, nucleating agents, blowing agents, surfactants, plasticizers, coupling agents, flame retardants, light stabilizers, processing aids, antistatic aids, antimicrobial aids, lubricants, combinations thereof, as deemed desirable by one skilled in the art.
The preparation method of the polypropylene nano composite material comprises the following steps:
1) weighing the raw materials according to the weight ratio;
2) dry-mixing polypropylene, organic clay, inorganic filler, compatilizer, toughening agent, stabilizer and other additives in a high-speed mixer for 3-15 minutes, adding the mixed raw materials into a double-screw extruder, and cooling and granulating after melt extrusion;
3) another preferred method is: dry-mixing organic clay, a compatilizer, a stabilizer, part of polypropylene and other additives in a high-speed mixer for 3-15 minutes to prepare a mixture A, dry-mixing inorganic filler, a toughening agent and the rest of polypropylene in the high-speed mixer for 3-15 minutes to prepare a mixture B, adding the mixture A into a double-screw extruder from a main feeding port at the tail part of a screw, adding the mixture B into the double-screw extruder from the middle side of the screw to a feeding port, and cooling and granulating after melt extrusion; wherein the temperature in the screw cylinder is as follows: the first zone is 180 ℃ minus 190 ℃, the second zone is 185 ℃ minus 195 ℃, the third zone is 185 ℃ minus 195 ℃, the fourth zone is 185 ℃ minus 195 ℃, the head is 190 ℃ minus 200 ℃, and the rotating speed of the double-screw extruder is 100 ℃ minus 1000 rpm.
The invention has the advantages that:
1. compared with the traditional talcum powder reinforced polypropylene, the composite material prepared by the invention has lower inorganic component content, thereby improving the molding processability, obviously reducing the density and weight of products, being beneficial to reducing the weight of finished products and reducing the energy consumption when the products are used in automobiles and other related industries, and having obvious economic significance.
2. Compared with polypropylene which is only filled and reinforced by nano clay, the composite material prepared by the invention has higher rigidity and toughness, the density is only slightly increased, and the product has better practicability and wider application range.
3. The modified nano clay and the resin matrix are directly melted and blended, so that the process of premixing the nano clay and the polymer to prepare master batches is omitted, the process flow is effectively simplified, and the production cost is reduced.
4. The components such as inorganic filler, elastomer and the like are added into the extruder at the downstream of the screw in a segmented feeding mode, so that the influence of the components on the shearing and dispersing process of the nano clay is avoided to the maximum extent, and the performance of the composite material is further improved.
Detailed Description
The present invention will be described in further detail with reference to examples. The scope of the invention is set forth in the claims and is not limited by these examples.
In the composite formulations of the examples and comparative examples, the polypropylene used was homopolypropylene and block copolypropylene having a melt flow rate (230 ℃ C. times.2.16 kg) of 3 to 40g/10min, wherein the comonomer of the block copolypropylene was usually ethylene and the content thereof was in the range of 4 to 10 mol%.
The organoclay is nano montmorillonite treated with quaternary ammonium salt, and Cloisite 20A from Southern Clay Product is selected.
The inorganic filler is sheet-structured talcum powder with average particle size of 1-10 μm.
The compatilizer is self-made maleic anhydride grafted polypropylene, the grafting rate is 0.5 percent, and the compatilizer is obtained by melt extrusion modification of random homopolymerized or block copolymerized propylene by maleic anhydride.
The toughening agent is ethylene-octene copolymer POE8180 from DOW.
The stabilizers used were Negonox DSTP (chemical name stearyl thiodipropionate) from ICE, British, Irganox1010 (chemical name pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ]) from Ciba, and Igrafos168 (chemical name tris (2, 4-di-tert-butylphenyl) phosphite) from Ciba.
Other additives used are one or more of a combination of colorants, nucleating agents, blowing agents, surfactants, plasticizers, coupling agents, flame retardants, light stabilizers, processing aids, antistatic aids, antimicrobial aids, lubricants as deemed desirable by one skilled in the art.
Example 1
Weighing 96% of polypropylene, 2.5% of Cloisite 20A, 1% of maleic anhydride grafted polypropylene, 0.1% of Irganox1010, 0.1% of Igrafos168 and 0.3% of Negonox DSTP according to weight percentage, dry mixing for 5 minutes in a high-speed mixer, adding into a double-screw extruder, and carrying out melt extrusion granulation, wherein the temperature in a screw cylinder is as follows: the first zone is 180 ℃, the second zone is 190 ℃, the third zone is 190 ℃, the fourth zone is 190 ℃, the head is 200 ℃, and the rotating speed of the double-screw extruder is 500 r/min. Drying the particles, and performing injection molding on an injection molding machine to prepare a sample.
Example 2
Weighing 92.5 percent of polypropylene, 5 percent of Cloi site 20A, 2 percent of maleic anhydride grafted polypropylene, 0.1 percent of Irganox1010, 0.1 percent of Igrafos168 and 0.3 percent of Negonox DSTP according to weight percentage, dry mixing for 5 minutes in a high-speed mixer, adding into a double-screw extruder, and carrying out melt extrusion granulation, wherein the temperature in a screw cylinder is as follows: the first zone is 180 ℃, the second zone is 190 ℃, the third zone is 190 ℃, the fourth zone is 190 ℃, the head is 200 ℃, and the rotating speed of the double-screw extruder is 500 r/min. Drying the particles, and performing injection molding on an injection molding machine to prepare a sample.
Example 3
Weighing 85.5% of polypropylene, 10% of Cloisite 20A, 4% of maleic anhydride grafted polypropylene, 0.1% of Irganox1010, 0.1% of Igrafos168 and 0.3% of Negonox DSTP according to weight percentage, dry mixing for 5 minutes in a high-speed mixer, adding into a double-screw extruder, and carrying out melt extrusion granulation, wherein the temperature in a screw cylinder is as follows: the first zone is 180 ℃, the second zone is 190 ℃, the third zone is 190 ℃, the fourth zone is 190 ℃, the head is 200 ℃, and the rotating speed of the double-screw extruder is 500 r/min. Drying the particles, and performing injection molding on an injection molding machine to prepare a sample.
Example 4
Weighing 87.5 percent of polypropylene, 5 percent of Cloi site 20A, 5 percent of talcum powder, 2 percent of maleic anhydride grafted polypropylene, 0.1 percent of Irganox1010, 0.1 percent of Igrafos168 and 0.3 percent of Negonox DSTP according to weight percentage, dry mixing for 5 minutes in a high-speed mixer, adding into a double-screw extruder, melting, extruding and granulating, wherein the temperature in a screw cylinder is as follows: the first zone is 180 ℃, the second zone is 190 ℃, the third zone is 190 ℃, the fourth zone is 190 ℃, the head is 200 ℃, and the rotating speed of the double-screw extruder is 500 r/min. Drying the particles, and performing injection molding on an injection molding machine to prepare a sample.
Example 5
Weighing 77.5% of polypropylene, 5% of Cloisite 20A, 15% of talcum powder, 2% of maleic anhydride grafted polypropylene, 0.1% of Irganox1010, 0.1% of Igrafos168 and 0.3% of Negonox DSTP according to weight percentage, dry-mixing for 5 minutes in a high-speed mixer, adding into a double-screw extruder, and carrying out melt extrusion granulation, wherein the temperature in a screw cylinder is as follows: the first zone is 180 ℃, the second zone is 190 ℃, the third zone is 190 ℃, the fourth zone is 190 ℃, the head is 200 ℃, and the rotating speed of the double-screw extruder is 500 r/min. Drying the particles, and performing injection molding on an injection molding machine to prepare a sample.
Example 6
Weighing 82.5% of polypropylene, 10% of talcum powder, 5% of Cloisite 20A, 2% of maleic anhydride grafted polypropylene, 0.1% of Irganox1010, 0.1% of Igrafos168 and 0.3% of Negonox DSTP according to weight percentage, dry-mixing for 5 minutes in a high-speed mixer, adding into a double-screw extruder, and carrying out melt extrusion granulation, wherein the temperature in a screw cylinder is as follows: the first zone is 180 ℃, the second zone is 190 ℃, the third zone is 190 ℃, the fourth zone is 190 ℃, the head is 200 ℃, and the rotating speed of the double-screw extruder is 500 r/min. Drying the particles, and performing injection molding on an injection molding machine to prepare a sample.
Example 7
Weighing 67.5% of polypropylene, 10% of talcum powder, 5% of Cloisite 20A, 2% of maleic anhydride grafted polypropylene, 15% of POE, 0.1% of Irganox1010, 0.1% of Igrafos168 and 0.3% of Negonox DSTP according to weight percentage, dry-mixing for 5 minutes in a high-speed mixer, adding into a double-screw extruder, and carrying out melt extrusion granulation, wherein the temperature in a screw cylinder is as follows: the first zone is 180 ℃, the second zone is 190 ℃, the third zone is 190 ℃, the fourth zone is 190 ℃, the head is 200 ℃, and the rotating speed of the double-screw extruder is 500 r/min. Drying the particles, and performing injection molding on an injection molding machine to prepare a sample.
Example 8
Weighing 52.5% of polypropylene, 5% of Cloisite 20A, 2% of maleic anhydride grafted polypropylene, 0.1% of Irganox1010, 0.1% of Igrafos168 and 0.3% of Negonox DSTP according to weight percentage, and dry-mixing for 5 minutes in a high-speed mixer to prepare a mixture A; weighing 30% of polypropylene and 10% of talcum powder according to the weight percentage, and dry-mixing for 5 minutes in a high-speed mixer to prepare a mixture B; respectively adding the mixture A into a double-screw extruder from a main feeding port at the tail part of the screw and the mixture B from a lateral feeding port in the middle part of the screw for melt extrusion granulation; wherein the temperature in the screw cylinder is as follows: the first zone is 180 ℃, the second zone is 190 ℃, the third zone is 190 ℃, the fourth zone is 190 ℃, the head is 200 ℃, and the rotating speed of the double-screw extruder is 500 r/min. Drying the particles, and performing injection molding on an injection molding machine to prepare a sample.
Example 9
Weighing 52.5% of polypropylene, 5% of Cloisite 20A, 2% of maleic anhydride grafted polypropylene, 0.1% of Irganox1010, 0.1% of Igrafos168 and 0.3% of Negonox DSTP according to weight percentage, and dry-mixing for 5 minutes in a high-speed mixer to prepare a mixture A; weighing 15% of polypropylene, 10% of talcum powder and 15% of POE (polyolefin elastomer) according to the weight percentage, and dry-mixing for 5 minutes in a high-speed mixer to obtain a mixture B; respectively adding the mixture A into a double-screw extruder from a main feeding port at the tail part of the screw and the mixture B from a lateral feeding port in the middle part of the screw for melt extrusion granulation; wherein the temperature in the screw cylinder is as follows: the first zone is 180 ℃, the second zone is 190 ℃, the third zone is 190 ℃, the fourth zone is 190 ℃, the head is 200 ℃, and the rotating speed of the double-screw extruder is 500 r/min. Drying the particles, and performing injection molding on an injection molding machine to prepare a sample.
Comparative example 1
Weighing 99.5 percent of polypropylene, 0.1 percent of Irganox1010, 0.1 percent of Igrafos168 and 0.3 percent of NegonoxDTP according to the weight percentage, dry-mixing in a high-speed mixer for 5 minutes, adding into a double-screw extruder, melting, extruding and granulating, wherein the temperature in a screw cylinder is as follows: the first zone is 180 ℃, the second zone is 190 ℃, the third zone is 190 ℃, the fourth zone is 190 ℃, the head is 200 ℃, and the rotating speed of the double-screw extruder is 500 r/min. Drying the particles, and performing injection molding on an injection molding machine to prepare a sample.
Comparative example 2
Weighing 79.5 percent of polypropylene, 20 percent of talcum powder, 0.1 percent of Irganox1010, 0.1 percent of Igrafos168 and 0.3 percent of Negonox DSTP according to weight percentage, dry mixing for 5 minutes in a high-speed mixer, adding into a double-screw extruder, melting, extruding and granulating, wherein the temperature in a screw cylinder is as follows: the first zone is 180 ℃, the second zone is 190 ℃, the third zone is 190 ℃, the fourth zone is 190 ℃, the head is 200 ℃, and the rotating speed of the double-screw extruder is 500 r/min. Drying the particles, and performing injection molding on an injection molding machine to prepare a sample.
Comparative example 3
Weighing 59.5 percent of polypropylene, 25 percent of talcum powder, 15 percent of POE, 0.1 percent of Irganox1010, 0.1 percent of Igrafos168 and 0.3 percent of Negonox DSTP according to weight percentage, dry-mixing for 5 minutes in a high-speed mixer, adding into a double-screw extruder, and carrying out melt extrusion granulation, wherein the temperature in a screw cylinder is as follows: the first zone is 180 ℃, the second zone is 190 ℃, the third zone is 190 ℃, the fourth zone is 190 ℃, the head is 200 ℃, and the rotating speed of the double-screw extruder is 500 r/min. Drying the particles, and performing injection molding on an injection molding machine to prepare a sample.
Performance evaluation method:
the sample density test was performed according to ISO1183A standard; the tensile property test of the sample is carried out according to ISO527-2 standard, the size of the sample is 170 multiplied by 10 multiplied by 4mm, and the tensile speed is 50 mm/min; the bending performance test is carried out according to ISO178 standard, the size of a test sample is 80 multiplied by 10 multiplied by 4mm, the span is 64mm, and the bending speed is 2 mm/min; the impact performance test of the simply supported beam is carried out according to the ISO179 standard, the size of a sample is 80 multiplied by 10 multiplied by 4mm, and the depth of a notch is one third of the thickness of the sample; the heat distortion temperature test was carried out according to ISO75 standard, with specimen dimensions of 120X 10X 4mm and a load of 0.45 MPa.
The formulations and performance test results for the examples and comparative examples are shown in the following tables:
TABLE 1 Material formulations (wt.%) for examples 1-5 and comparative examples 1-2
| Comparative example 1 | Comparative example 2 | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | |
| Polypropylene | 99.5 | 79.5 | 96 | 92.5 | 85.5 | 87.5 | 77.5 |
| Organic clay | - | - | 2.5 | 5 | 10 | 5 | 5 |
| Talcum powder | - | 20 | - | - | - | 5 | 15 |
| Maleic anhydride grafted polypropylene | - | - | 1 | 2 | 4 | 2 | 2 |
| 1010 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 |
| 168 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 |
| DSTP | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 |
TABLE 2 results of Performance test of examples 1-5 and comparative examples 1-2
| Comparative example 1 | Comparative example 2 | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | |
| Density (g/cm3) | 0.898 | 1.039 | 0.912 | 0.923 | 0.949 | 0.957 | 1.027 |
| Tensile Strength (MPa) | 23.1 | 22.7 | 25.2 | 26.8 | 28.6 | 27.3 | 27.7 |
| Flexural Strength (MPa) | 31.6 | 35.4 | 33.9 | 34.8 | 37.6 | 35.8 | 38.0 |
| Flexural modulus (MPa) | 1070 | 1710 | 1340 | 1560 | 1860 | 1740 | 2030 |
| Notched impact strength | 12.1 | 7.8 | 11.3 | 10.7 | 8.6 | 9.6 | 7.9 |
| Heat distortion temperature | 97 | 112 | 108 | 114 | 121 | 117 | 123 |
Table 3 materials formulations (wt%) of examples 6-9 and comparative example 3
Table 4 results of performance tests of examples 6 to 9 and comparative example 3
| Comparative example 3 | Example 6 | Example 7 | Example 8 | Example 9 | |
| Density (g/cm)3) | 1.083 | 0.994 | 0.993 | 0.995 | 0.992 |
| Tensile Strength (MPa) | 20.1 | 27.6 | 22.5 | 27.9 | 23.0 |
| Flexural Strength (MPa) | 29.2 | 36.9 | 31.6 | 37.4 | 32.3 |
| Flexural modulus (MPa) | 1630 | 1880 | 1600 | 1960 | 1670 |
| Notched impact strength (kJ/m)2) | 22.5 | 8.8 | 20.9 | 9.0 | 25.6 |
| Heat distortion temperature (. degree. C.) | 109 | 120 | 114 | 121 | 116 |
From the comparison of comparative example 1 and examples 1-3, it can be seen that the stiffness of the polypropylene composite increases significantly with increasing amounts of organoclay, while the material density increases slowly. Comparing the comparative example 2 with the example 4, it can be seen that, compared with the traditional talcum powder reinforced polypropylene, the material density is obviously reduced and the tensile strength is obviously improved by adopting the mode of synergistically reinforcing the nano-organic clay and the micro-talcum powder under the condition of approximately equivalent bending resistance. Example 5 achieved significantly higher stiffness performance at similar total filler levels (about 20%) and lower densities than comparative example 2, which was difficult to achieve with nanoclay-only reinforced polypropylene due to high cost and dispersion process limitations.
As can be seen from the comparison of examples 6-7 with examples 8-9, better material rigidity and toughness can be obtained by using the way that the main feeding opening and the side feeding openings are fed in a segmented manner. Comparison between the comparative example 3 and the example 9 shows that, compared with the traditional talcum powder and rubber reinforced and toughened polypropylene material, the polypropylene nano composite material of the invention has obviously reduced material density on the premise that all performances are better than those of the former, and the weight of a finished product with the same volume can be reduced by nearly 10%.
Claims (17)
1. A polypropylene nano composite material with low density, high rigidity and high toughness is characterized in that: the composite material consists of the following raw materials in percentage by weight:
55-98% of polypropylene
1 to 15 percent of organic clay
0 to 30 percent of inorganic filler
0.1 to 10 percent of compatilizer
0 to 20 percent of toughening agent
0.2 to 2 percent of stabilizer
0-5% of other additives.
2. The low density, high stiffness, high toughness polypropylene nanocomposite according to claim 1 wherein: under the test condition of 230 ℃ multiplied by 2.16kg, the polypropylene has the melt flow rate of 0.5 to 60g/10min of homopolymerized propylene or block copolymerized propylene, wherein the comonomer of the block copolymerized propylene is ethylene, and the content of the comonomer is 4 to 10mol percent.
3. The low density, high stiffness, high toughness polypropylene nanocomposite according to claim 1 wherein: the organic clay is organized nano clay; it is selected from one or more of soapstone, halloysite, bentonite, attapulgite, montmorillonite, kaolin, mica, nontronite, beidellite and vermiculite.
4. The low density, high stiffness, high toughness polypropylene nanocomposite according to claim 3 wherein: the organic clay is nano montmorillonite treated by amine organic compound, the interlayer distance is 1-20nm, the average grain diameter is 1-10 μm, and the density is 1-3g/cm 3.
5. The low density, high stiffness, high toughness polypropylene nanocomposite according to claim 1 wherein: the inorganic filler is one or the combination of more than two of talcum powder, calcium carbonate and barium sulfate, and the average grain diameter of the inorganic filler is 1-20 mu m.
6. The low density, high stiffness, high toughness polypropylene nanocomposite according to claim 5 wherein: the inorganic filler is talcum powder with the average grain diameter of 1-10 mu m.
7. The low density, high stiffness, high toughness polypropylene nanocomposite according to claim 1 wherein: the compatilizer is grafted polyolefin.
8. The low density, high stiffness, high toughness polypropylene nanocomposite according to claim 7 wherein: the grafted polyolefin is one or the combination of more than two of grafted polypropylene, grafted polyethylene, grafted polystyrene, grafted ABS and grafted POE.
9. The low density, high stiffness, high toughness polypropylene nanocomposite according to claim 7 wherein: the grafting group of the grafted polyolefin is one or the combination of more than two of maleic anhydride, silane, acrylic acid and polyacrylamide.
10. The low density, high stiffness, high toughness polypropylene nanocomposite according to claim 7 wherein: the method is characterized in that: the grafted polyolefin is preferably maleic anhydride grafted polypropylene, has the density of 0.89-0.91g/cm3, the melting point of 170-190 ℃, the melt flow rate of 10-50g/10min and the grafting rate of 0.5-1.0 percent under the test condition of 230 ℃ multiplied by 2.16kg, and is obtained by melt extrusion modification of random homopolymerized or block copolymerized propylene by maleic anhydride.
11. The low density, high stiffness, high toughness polypropylene nanocomposite according to claim 1 wherein: the toughening agent is one or the combination of more than two of polybutadiene rubber, ethylene-propylene-diene rubber and ethylene-octene copolymer.
12. The low density, high stiffness, high toughness polypropylene nanocomposite according to claim 11 wherein: the toughening agent is POE elastomer, and the melt flow rate is 0.5-50g/10min under the test condition of 230 ℃ multiplied by 2.16 kg.
13. The low density, high stiffness, high toughness polypropylene nanocomposite according to claim 1 wherein: the stabilizer comprises a main antioxidant and an auxiliary antioxidant, wherein the main antioxidant is a hindered phenol antioxidant or a thioester antioxidant; the auxiliary antioxidant is phosphite or ester antioxidant.
14. The low density, high stiffness, high toughness polypropylene nanocomposite of claim 13 wherein: the main antioxidant is one or the combination of more than two of 3114, 1010 and DSTP; the auxiliary antioxidant is one or two of 618 and 168.
15. The low density, high stiffness, high toughness polypropylene nanocomposite according to claim 1 wherein: such other additives include one or a combination of two or more of colorants, nucleating agents, blowing agents, surfactants, plasticizers, coupling agents, flame retardants, light stabilizers, processing aids, antistatic aids, antimicrobial aids, and lubricants as deemed desirable by one skilled in the art.
16. A method of preparing the low density, high stiffness, high toughness polypropylene nanocomposite of claim 1 comprising the steps of:
1) weighing the raw materials according to the weight ratio;
2) dry-mixing polypropylene, organic clay, inorganic filler, compatilizer, toughening agent, stabilizer and other additives in a high-speed mixer for 3-15 minutes, adding the mixed raw materials into a double-screw extruder, and cooling and granulating after melt extrusion; wherein the temperature in the screw cylinder is as follows: the first zone is 180 ℃ minus 190 ℃, the second zone is 185 ℃ minus 195 ℃, the third zone is 185 ℃ minus 195 ℃, the fourth zone is 185 ℃ minus 195 ℃, the head is 190 ℃ minus 200 ℃, and the rotating speed of the double-screw extruder is 100 ℃ minus 1000 rpm.
17. A method of preparing the low density, high stiffness, high toughness polypropylene nanocomposite of claim 1 comprising the steps of:
1) weighing the raw materials according to the weight ratio;
2) dry-mixing organic clay, a compatilizer, a stabilizer, part of polypropylene and other additives in a high-speed mixer for 3-15 minutes to prepare a mixture A, dry-mixing inorganic filler, a toughening agent and the rest of polypropylene in the high-speed mixer for 3-15 minutes to prepare a mixture B, adding the mixture A into a double-screw extruder from a main feeding port at the tail part of a screw, adding the mixture B into the double-screw extruder from the middle side of the screw to a feeding port, and cooling and granulating after melt extrusion; wherein the temperature in the screw cylinder is as follows: the first zone is 180 ℃ minus 190 ℃, the second zone is 185 ℃ minus 195 ℃, the third zone is 185 ℃ minus 195 ℃, the fourth zone is 185 ℃ minus 195 ℃, the head is 190 ℃ minus 200 ℃, and the rotating speed of the double-screw extruder is 100 ℃ minus 1000 rpm.
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Application publication date: 20100526 |