CN102143994A - 平面模件或膜的制备方法 - Google Patents
平面模件或膜的制备方法 Download PDFInfo
- Publication number
- CN102143994A CN102143994A CN2009801349604A CN200980134960A CN102143994A CN 102143994 A CN102143994 A CN 102143994A CN 2009801349604 A CN2009801349604 A CN 2009801349604A CN 200980134960 A CN200980134960 A CN 200980134960A CN 102143994 A CN102143994 A CN 102143994A
- Authority
- CN
- China
- Prior art keywords
- paper tinsel
- thermoplastic polymer
- moulded product
- phyllosilicate
- moulding compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000000034 method Methods 0.000 title claims description 31
- 238000004519 manufacturing process Methods 0.000 title abstract description 5
- 229920001169 thermoplastic Polymers 0.000 claims abstract description 26
- 229910052615 phyllosilicate Inorganic materials 0.000 claims description 36
- 239000000203 mixture Substances 0.000 claims description 19
- 239000000206 moulding compound Substances 0.000 claims description 15
- 238000003475 lamination Methods 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 10
- 238000001125 extrusion Methods 0.000 claims description 9
- 239000011888 foil Substances 0.000 claims description 9
- -1 polyoxymethylene Polymers 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 7
- 238000007664 blowing Methods 0.000 claims description 6
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 4
- 150000001408 amides Chemical class 0.000 claims description 4
- 239000011256 inorganic filler Substances 0.000 claims description 4
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 4
- 239000004416 thermosoftening plastic Substances 0.000 claims description 4
- 229930040373 Paraformaldehyde Natural products 0.000 claims description 2
- 229920001283 Polyalkylene terephthalate Polymers 0.000 claims description 2
- 239000004793 Polystyrene Substances 0.000 claims description 2
- 239000000178 monomer Substances 0.000 claims description 2
- 229920002492 poly(sulfone) Polymers 0.000 claims description 2
- 229920000728 polyester Polymers 0.000 claims description 2
- 229920000570 polyether Polymers 0.000 claims description 2
- 229920000098 polyolefin Polymers 0.000 claims description 2
- 229920006324 polyoxymethylene Polymers 0.000 claims description 2
- 229920002223 polystyrene Polymers 0.000 claims description 2
- 239000005060 rubber Substances 0.000 claims description 2
- 238000003856 thermoforming Methods 0.000 claims description 2
- 239000012778 molding material Substances 0.000 abstract 3
- 150000004760 silicates Chemical class 0.000 abstract 1
- 239000000463 material Substances 0.000 description 25
- 238000002360 preparation method Methods 0.000 description 14
- 229920000642 polymer Polymers 0.000 description 10
- 229920002292 Nylon 6 Polymers 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 7
- 239000006185 dispersion Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 5
- 238000001746 injection moulding Methods 0.000 description 5
- 239000011159 matrix material Substances 0.000 description 5
- 238000000465 moulding Methods 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 238000005469 granulation Methods 0.000 description 4
- 230000003179 granulation Effects 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 239000002114 nanocomposite Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical class 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 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Chemical class C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000012856 packing Methods 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 3
- 239000000454 talc Substances 0.000 description 3
- 229910052623 talc Inorganic materials 0.000 description 3
- 235000012222 talc Nutrition 0.000 description 3
- 229910052902 vermiculite Inorganic materials 0.000 description 3
- 239000010455 vermiculite Substances 0.000 description 3
- 235000019354 vermiculite Nutrition 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 150000001413 amino acids Chemical class 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 230000004927 fusion Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000003760 tallow Substances 0.000 description 2
- 238000009757 thermoplastic moulding Methods 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 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
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 241000871495 Heeria argentea Species 0.000 description 1
- 241000446313 Lamella Species 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- PZZYQPZGQPZBDN-UHFFFAOYSA-N aluminium silicate Chemical compound O=[Al]O[Si](=O)O[Al]=O PZZYQPZGQPZBDN-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000000712 assembly Effects 0.000 description 1
- 238000000429 assembly Methods 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 238000003490 calendering Methods 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000007766 curtain coating Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 229910000271 hectorite Inorganic materials 0.000 description 1
- KWLMIXQRALPRBC-UHFFFAOYSA-L hectorite Chemical compound [Li+].[OH-].[OH-].[Na+].[Mg+2].O1[Si]2([O-])O[Si]1([O-])O[Si]([O-])(O1)O[Si]1([O-])O2 KWLMIXQRALPRBC-UHFFFAOYSA-L 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910000273 nontronite Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 150000004714 phosphonium salts Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 229910000275 saponite Inorganic materials 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003809 water extraction Methods 0.000 description 1
Classifications
-
- 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
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- 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
-
- 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
- B29C48/07—Flat, e.g. panels
- B29C48/08—Flat, e.g. panels flexible, e.g. films
-
- 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
- B29C48/16—Articles comprising two or more components, e.g. co-extruded layers
- B29C48/18—Articles comprising two or more components, e.g. co-extruded layers the components being layers
- B29C48/21—Articles comprising two or more components, e.g. co-extruded layers the components being layers the layers being joined at their surfaces
-
- 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
- B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
- B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
- B29C55/04—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets uniaxial, e.g. oblique
- B29C55/06—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets uniaxial, e.g. oblique parallel with the direction of feed
-
- 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
- B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
- B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
- B29C55/10—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial
- B29C55/12—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial
-
- 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
- B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
- B29C55/28—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of blown tubular films, e.g. by inflation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D7/00—Producing flat articles, e.g. films or sheets
- B29D7/01—Films or sheets
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B25/00—Layered products comprising a layer of natural or synthetic rubber
- B32B25/04—Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B25/042—Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material of natural rubber or synthetic rubber
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B25/00—Layered products comprising a layer of natural or synthetic rubber
- B32B25/04—Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B25/08—Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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- B32B27/00—Layered products comprising a layer of synthetic resin
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- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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- B32—LAYERED PRODUCTS
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- B32B27/00—Layered products comprising a layer of synthetic resin
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- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
- B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
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- B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
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- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
- B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
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Abstract
从可挤出的热塑性聚合物模制组合物制备具有各向异性的热膨胀系数的片状模制品或箔,所述制备是通过以直径为10-1000nm且纵横比为1∶5-1∶10000的片状页硅酸盐填充所述热塑性聚合物模制组合物,挤出被填充的热塑性聚合物模制组合物,然后对所述挤出物进行单轴或双轴拉伸以得到片状模制品或箔而完成。
Description
本发明涉及具有各向异性的热膨胀系数的片状模制品或箔的制备方法,所述片状模制品或箔由可挤出的热塑性聚合物模制组合物组成。
热塑性塑料组成的组件相对于由金属制造的部件具有许多优势,但也有明显缺陷。优势有密度较低,这可显著降低重量;容易通过注射成型加工,使得有较高水平的设计灵活性;内在的耐蚀性,意味着不需要任何专门的防腐蚀措施;以及易于将塑料组件整合至金属结构中。在缺陷方面,尤其是尺寸稳定性较低,这是由于聚合物的通常较高水平的吸水性、低耐热性(劲度的温度依赖性)和高热膨胀系数(CTE);以及源于此的制造问题。具体地,在汽车制造中,塑料组成的车体组件充其量只能在线内(inline)加工,而不能根据需要在线上(online)加工,并且实际上一般仅能够离线加工,这意味着这些组件不得不在涂漆线结束时装配。这不但会带来另外的花费,而且会有配色的问题。
金属的CTE的数量级是10×10-6K-1,而低于玻璃化转变温度(Tg)的聚合物的CTE是100×10-6K-1,即升高10倍。相对于金属的CTE基本不依赖于温度,聚合物的CTE一旦超过Tg会进一步升高2倍或3倍。
已经知道片状无机填充物,例如页硅酸盐,可用作聚合物模制组合物中的填充物。
WO 2006/029138涉及可进一步加工为膜或箔的水溶性聚酰胺组合物的制备。这里可以伴随使用页硅酸盐。对于该制备过程,将所述聚合物的醇溶液与页硅酸盐混合并流延以得到膜或箔。所述箔可用于包装工业中。
JP-A-57083551涉及蛭石填充的聚酰胺树脂组合物,所述聚合物具有硬度和长度增加相关的改良性质。为此目的,将纵横比>5的蛭石引入尼龙-6,6并注射成型。在挤出方向和其垂直方向上测量多个热膨胀系数。
Polymer 43(2002),第6727-6741页描述了尼龙-6纳米复合材料的热膨胀特征。为此目的,将页硅酸盐加入尼龙-6,并将所述模制组合物挤出。所述挤出过程得到在三个空间方向上具有不同的热膨胀系数的模制品。由此得出以下结论:分层页硅酸盐非统计性地取向。
然而,在以前的页硅酸盐方法中得到的偶然且因此不确定的取向,以及相关的热膨胀系数的各向异性,对于需要在2个空间方向上降低热膨胀系数的应用是不够的。适用这一点的产品特别包括通过注射成型产生的壁厚小于1mm的产品。
本发明的目标是在包括高于玻璃化转变温度的温度下分别大大降低聚合材料以及模制品的热膨胀。由于所关注的三维组件要经受长和宽的紧容限(tight tolerance),必须在两个维度中降低CTE。第三维——所述组件的厚度——的变化关系不大或者无关。为此目的必须对材料进行的改良或者对其存在其中的混合物或复合材料进行的改良,优选预计不伴随有任何韧度降低,即所述材料的任何脆变。
本发明通过一种具有各向异性的热膨胀系数的片状模制品或箔的制备方法实现了该目标,所述片状模制品或箔由可挤出的热塑性聚合物模制组合物组成,所述方法是通过以直径为10-1000nm且纵横比(aspect ratio)为1∶5-1∶10000的片状页硅酸盐填充所述热塑性聚合物模制组合物,挤出被填充的热塑性聚合物模制组合物,然后对所述挤出物进行单轴取向或双轴取向以得到片状模制品或箔而进行。
根据本发明已经发现,利用所述挤出物——其在该阶段已经通过挤出模具的剪切和拉紧预取向——的单轴取向或双轴取向,得到片状模制品或箔,可达到足够高水平的页硅酸盐的取向,结果是主表面的平面中的热膨胀系数较小,而在垂直于所述主表面的方向上的热膨胀系数较高。这使得可得到CTE在两个维度上降低的模制品或箔。
原则上,CTE降低在此处可以通过使用热膨胀小于聚合物的热膨胀的无机化合物实现。如果这些化合物以粉末的形式均质复合至聚合物中,那么CTE的降低符合混合规则,与所述填充物的浓度成线性并各向同性。由于填充物的CTE约为10×10-6K-1,如果使用已知的方法,那么达到显著效应所需的填充物浓度很高,并且这些浓度对机械特性(即所述材料的韧度)有不利影响。本发明人已经出人意料地发现,如果所使用的颗粒优选很细并且是片层的(即“二维”),当这些材料在聚合物基质中具有最大分散均质性并且具有最大平面取向的情况下,那么甚至低浓度也能实现CTE大大降低。另外,在这些材料中观察到劲度(弹性模量)和耐热性显著增加,但几乎没有任何韧度降低。所使用的片状填充物优选包括有机改性蒙脱石(MMT),其可在脱落和分散方面得到良好结果。
任何所需的合适方法可用于实现所述挤出物的单轴取向或双轴取向,以得到片状模制品或箔。根据本发明的一个实施方案,所述挤出过程优选自缝形模头(slot die)进行,随后进行挤出箔的单轴取向或双轴取向。根据本发明的另一个实施方案,所述挤出过程优选自环形模头(annular die)进行,随后经吹制或吹塑进行双轴取向。本领域技术人员知晓合适的方法、合适的装置和模具几何形状。
为了得到更厚的层厚度,可以将所述挤出并取向的模制品或箔成叠(例如在加热时成叠)或层压。该加工步骤不会不利地影响所述填充物的分散或取向。如果在共挤出过程中产生的熔化亚层相互重叠,那么可以省略层压过程。随后可以进行压延阶段以校准所述层厚度;或者随后可以在展开架中处理以提高取向。
此处,箔技术的一个优势是材料相结合的灵活性。低CTE的膜可以与功能性能(例如扩散屏障、韧度、阻燃性、光学性质等)对成品来说重要的膜结合。
可通过将至少一个页硅酸盐填充的箔与至少一个其他热塑性箔结合产生复合物,所述其他热塑性箔起到例如性质改良的作用,如有关扩散屏障或抗冲击性。箔堆叠体可以经共挤出产生,此处可经层压加入另外的膜亚层或膜堆叠体。
随后可以经冲击挤压过程或者经热成形将所述模制品或箔用于产生模制品。这些模制品特别用于汽车结构中。此处特别相关的有外部车体部件,例如轮胎、发动机罩、门和汽车后背箱盖,还有汽车内饰。
就本发明而言,表述“片状模制品”是指主要在两个维度中伸展并仅向第三维伸展很少的模制品。例如,所述模制品的长和宽均可以是所述模制品厚度的至少10倍,优选至少20倍。
表述“各向异性的热膨胀系数”是指模制品在3个空间方向的至少一个上具有不同于其他空间方向上的热膨胀系数。优选的本发明的模制品或箔,与未填充的聚合物相比,在垂直于主表面上具有增大的热膨胀系数,并且在主表面内具有降低的热膨胀系数。
对页硅酸盐的表述“片状”是指直径是10nm-1000nm,其纵横比是1∶5-1∶10000。
在所述方法中随后单轴取向或双轴取向所述挤出物优选导致1∶1-1∶20、特别优选1∶2-1∶8的取向比。
任何所需的合适的片状页硅酸盐可用于本发明的方法中。优选的页硅酸盐的直径是15nm-500nm,特别是20nm-500nm。此处纵横比优选是1∶5-1∶1000,特别是1∶10-1∶100。层厚度优选小于50nm,特别优选小于10nm,特别是小于2nm。
所述页硅酸盐可以基于任何所需的硅酸盐,例如基于蒙脱石、硅酸铝、硅酸镁、膨润土、蛭石等。其他合适的页硅酸盐有锂蒙脱石、皂石、贝得石和绿脱石。
合适的页硅酸盐描述于引言中列出的文献中。其他的合适页硅酸盐描述于WO 2008/063198和US 5,747,560中。
所述页硅酸盐可以是未处理的或者有机改性的页硅酸盐。优选使用有机改性的页硅酸盐。这种类型的有机改性描述于例如WO 2008/063198中。为此目的,使所述页硅酸盐与下述有机化合物反应,所述有机化合物具有与所述热塑性模制组合物中的聚合物相容的末端基团,并且还具有用于结合所述页硅酸盐的锚固基团。
优选通过与合适的有机盐——例如季铵盐、鏻盐或咪唑鎓盐——的阳离子交换反应将所述页硅酸盐改性。合适的季铵盐优选符合通式R1R2R3R4N+,其中R1-R4彼此独立地为直链烃基、支化烃基或芳族烃基。磷还可以代替氮存在于所述阳离子中。WO 2008/063198描述了合适的改性。
此外,烃基可以被羟基或者被酸基改性。
例如,季铵抗衡离子可具有甲基、两个羟甲基和一个衍生自牛脂(tallow)的基团(C14-18基)。
此外,质子化形式的氨基酸也可用作阳离子,实例有C6-14氨基酸。合适的页硅酸盐可从例如Rockwood Additives(Southern ClayProducts)获得。还可以使用例如来自B+MGesellschaftfür Bergbau und Mineralstoffe mbH und Go.KG.的Arginotech页硅酸盐。
可以根据实际需要调节所述页硅酸盐的量。在热塑性聚合物模制组合物中的比例以全部聚合物模制组合物为基准计通常为0.1重量%-10重量%,优选1重量%-5重量%。
所述量取决于页硅酸盐在聚合物模制组合物中的分散水平。如果将所述页硅酸盐加入最终的聚合物模制组合物中并且例如在挤出机中混合,所选择的量将必须高于在所述聚合物制备结束之前进行混合以将所述页硅酸盐掺入单体混合物中的量。
这可归因于如下事实,即在挤出机中例如在双螺杆挤出机中掺合无法达到与原位聚合过程中一样均质的分散。所述页硅酸盐的分散和脱落越好,所使用的量越少。
根据本发明,还可另外将其他无机填充物加入所述热塑性聚合物模制组合物。这些填充物特别包括颗粒状填充物,特别包括滑石。所使用的其他填充物的量优选是0.1重量%-10重量%,特别优选0.5重量%-5重量%。
同时使用的其他无机填充物的量以所述聚合物模制组合物为基准计优选可以多达5重量%。
所述热塑性聚合物模制组合物可选自任何所需的合适的热塑性聚合物模制组合物。潜在的热塑性聚合物优选选自聚酰胺、聚甲醛、聚对苯二甲酸亚烷基酯例如聚对苯二甲酸乙二醇酯或聚对苯二甲酸丁二醇酯、聚砜、聚烯烃例如聚乙烯或聚丙烯、聚苯乙烯、聚醚、聚酯、或聚(甲基)丙烯酸甲酯;或者选自共聚物或它们的混合物,其还可包括橡胶。所述聚合物可为抗冲击改性的。特别优选使用聚酰胺和它们与PC、ABS等的混合物。
所述热塑性聚合物的制备是公知的。所述聚合物还可包含其他成分,实例有光稳定剂和热稳定剂、染料、脱模剂、阻燃剂等。还可伴随使用纤维状填充物,实例有玻璃纤维或碳纤维。
优选使用的热塑性聚合物的熔体粘度优选是50Pa-3500Pa。
在制备过程中,挤出过程优选在220℃-280℃的温度下进行。在取向过程中,所述聚合物箔或膜优选保持在70℃-200℃的温度。
本发明还提供了可通过上述方法中的一种得到的模制品或箔。
就箔而言,层厚度优选为50μm-300μm。对于由多个箔组成的层压制品或模制品,厚度优选1mm-4mm。
本发明的模制品或箔特别可用于汽车制造中。
以下的实施例进一步说明本发明。
实施例
使用了基于聚酰胺和有机改性蒙脱石(MMT)的热塑性模制组合物。
均质分散
使用两种途径将MMT均质分散。经直接在双螺杆挤出机中复合可以将MMT良好地分散在热塑性聚合物中(一个实例是PA6/MMT-1)。在与己内酰胺原位聚合的产品(例如PA6/MMT-2)中观察到更好的MMT分散以及因此更有效的颗粒效果。
填充物的取向
在注射成型产生的厚度小于1mm的薄壁产品中,所述MMT的取向被证明是不足的并且不能以确定的方式调整。相反,在经缝形模头挤出且随后进行单轴取向或双轴取向制备的箔中可实现所需的平面取向。这还适用于吹制箔,制备吹制箔的一般方法为利用从环形模头挤出熔化物并随后进行双轴取向(吹塑)。所述箔的厚度通常小于300μm。
由于实际组件的壁厚在数毫米的范围,将堆叠的各个箔亚层热层压或通过共挤出过程产生。该过程步骤对所述填充物的分散或取向无任何不利影响。在发明实施例中引用的CTE测量值在由该方式产生的稳固熔合的箔堆叠体所构成的半成品上确定。
起始材料
组分A
A1:尼龙-6,其固有粘度IV是150ml/g,根据ISO 307在25℃下以96重量%浓度的硫酸中0.5重量%浓度的溶液的形式测量
A2:原位聚合的尼龙-6,如下制备:
(在组分B存在下制备组分A)
将1kg页硅酸盐B2溶解或悬浮于19kg己内酰胺和0.2kg水中。在加入10g丙酸和5l水后,将所述混合物在搅拌罐中加热至270℃,所述罐中的内部压力是17巴。
在1小时的预缩合后,将所使用的容器降压2小时,然后将所述混合物后缩合1小时。使所述熔化物从所述罐中排出并粒化。将颗粒用热水提取24小时,干燥,然后在180℃下热调节22小时。
所述起始材料具有如下性质:
IV=163ml/g
AEG=32mmol/kg
CEG=104mmol/kg
组分B
组分C
组分D
发明实施例1(P1)
与5重量%的组分B1结合使用组分A1。将组分D1以0.2重量%的浓度加入。在250℃下,借助Werner & Pfleiderer ZSK 25双螺杆挤出机将所述PA6纳米复合材料复合。此处将所有组分都预混合,并且将所述预混合物装入所述挤出机入口。将所获得的复合材料粒化。
在吹膜装置(Weber)中经挤出制备箔。所述挤出机的螺杆直径是50mm。在240℃(区域1)至260℃(区域3)下,以50rpm操作所述挤出机,挤出量是5.4kg/h。
吹胀比是1∶2,引出速度是4.8m/min。所形成的箔的厚度是约50μm。该箔可用于制备厚的试样。将多个箔成叠以得到6mm的总厚度,并且在225℃下以3巴层压9分钟。所生成的产物(称为P1)具有5mm的厚度,被进一步用于特征测试。
发明实施例2(P2)
用组分A1稀释组分A2,直至组分B2的浓度为2重量%浓度,并与2重量%的组分C1和0.2重量%组分D1进一步混合。在250℃下,借助ZSK25双螺杆挤出机将所述PA6纳米复合材料复合。此处将所有组分都预混合,并且将所述预混合物装入所述挤出机入口。将所获得的复合材料(称为P2)粒化。
在吹膜装置(Weber)中经挤出制备箔。所述挤出机的螺杆直径是50mm。在240℃(区域1)至260℃(区域3)下,以50rpm操作所述挤出机,挤出量是5.4kg/h。吹胀比是1∶2,引出速度是5m/min。所形成的箔的厚度是约50μm。该箔可用于制备厚部件。将多个箔成叠以得到6mm的总厚度,并且在225℃下以3巴层压9分钟。所生成的产物(称为P2)具有约5mm的厚度,被进一步用于特征测试。
发明实施例3(P3)
以纯产物形式使用组分A2。在平箔装置(Weber,ZE30)中经挤出制备箔。在从230℃(第一桶区的温度)、240℃(模具的温度)、然后至250℃(挤出机中央)下,以75rpm操作所述挤出机。引出速度是4.2m/min。所形成的箔的厚度是约200μm。该箔可用于制备厚的试样。将多个箔成叠以得到6mm的总厚度,并且在225℃下以3巴层压9分钟。所生成的产物(称为P3)具有5mm的厚度,被进一步用于特征测试。
比较例1(P4)
以纯产物形式使用组分A1。在平箔装置(Weber,ZE30)中经挤出制备箔。在从230℃(第一桶区和模具的温度)、然后至250℃(挤出机中央)下,以75rpm操作所述挤出机。引出速度是4.2m/min。所形成的箔的厚度是约250μm。该箔可用于制备厚的试样。将多个箔成叠以得到6mm的总厚度,并且在225℃下以3巴层压9分钟。所生成的产物(称为P4)具有5mm的厚度,被进一步用于特征测试。
比较例2(P5)
与5重量%的组分B1结合使用组分A1。将组分D1以0.2重量%的浓度加入。在250℃下,借助ZSK 25双螺杆挤出机将所述PA6纳米复合材料复合。此处将所有组分都预混合,并且将所述预混合物装入所述挤出机入口。将所获得的复合材料粒化。在260℃的熔化温度下在注射成型机中加工干燥颗粒,以得到测量尺寸60mm×10mm×0.8mm的抗张样本,此处模具温度是35℃。
确定CTE(热膨胀系数)
在来自Seiko的TMA-SS6000装置中,在三个方向(流向、横向和厚度方向)确定CTE。首先打磨样本的表面,以得到光滑表面。将所述样本插入测量孔中,并在测量之前加热至140℃以保证其干燥。然后各自在-40℃至120℃的温度范围内,在20mN的负载下使用1K/min的加热速率测量CTE。
当结果基于温度范围时表述为平均值。区分两个温度范围:低于Tg的温度(-40℃至约40℃)和高于Tg的温度(约40℃至120℃)。还确定了120℃下的CTE。
F 表示在流向测量的CTE,
T 表示在横向(相对于流向的横向,在箔的平面内)测量的CTE,
P 表示垂直于箔平面(箔的厚度方向)测量的CTE。
Claims (14)
1.一种制备具有各向异性的热膨胀系数的片状模制品或箔的方法,所述片状模制品或箔由可挤出的热塑性聚合物模制组合物组成,所述方法是通过以直径为10-1000nm且纵横比为1∶5-1∶10000的片状页硅酸盐填充所述热塑性聚合物模制组合物,挤出被填充的热塑性聚合物模制组合物,然后对所述挤出物进行单轴取向或双轴取向以得到片状模制品或箔而进行。
2.权利要求1的方法,其中所述挤出自缝形模头进行,随后进行单轴取向或双轴取向。
3.权利要求1的方法,其中所述挤出自环形模头进行,随后经吹制进行双轴取向。
4.权利要求1-3中任一项的方法,其中所述挤出且取向的模制品或箔被成叠或层压以增加层厚度。
5.权利要求1-4中任一项的方法,其中随后经冲击挤压过程或者经热成形制备模制品。
6.权利要求1-5中任一项的方法,其中所述片状页硅酸盐已被有机改性。
7.权利要求1-6中任一项的方法,其中所述热塑性聚合物模制组合物在从单体制备所述聚合物之前或过程中用所述片状页硅酸盐填充。
8.权利要求1-7中任一项的方法,其中所述热塑性聚合物模制组合物的热塑性聚合物选自聚酰胺、聚甲醛、聚对苯二甲酸亚烷基酯、聚砜、聚烯烃、聚苯乙烯、聚醚、聚酯、或聚(甲基)丙烯酸甲酯;或者选自共聚物或它们的混合物,其还可包括橡胶。
9.权利要求1-8中任一项的方法,其中所述热塑性聚合物模制组合物还包含其他无机填充物。
10.权利要求1-9中任一项的方法,其中将至少一个页硅酸盐填充的箔与至少一个其他热塑性箔结合,以得到一种复合物。
11.权利要求1-10中任一项的方法,其中箔堆叠体经共挤出产生。
12.权利要求10或11的方法,其中其他箔亚层或箔堆叠体经层压加入所述箔堆叠体。
13.一种可通过权利要求1-12中任一项的方法得到的模制品或箔。
14.权利要求13的模制品或箔在汽车结构中的用途。
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CN (1) | CN102143994B (zh) |
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MY152811A (en) | 2009-06-08 | 2014-11-28 | Basf Se | Method for producing poly(arylene ether) block copolymers |
WO2010142548A1 (de) | 2009-06-08 | 2010-12-16 | Basf Se | Segmentierte polyarylenether-blockcopolymere |
DE102009025537A1 (de) | 2009-06-19 | 2010-12-30 | Basf Se | Copolyamide |
MY161454A (en) | 2009-07-08 | 2017-04-14 | Basf Se | Method for producing fiber-reinforced composite materials from polyamide 6 and copolyamides made of polyamide 6 and polyamide 12 |
KR101778812B1 (ko) | 2009-08-20 | 2017-09-14 | 바스프 에스이 | 저-할로겐 폴리비페닐술폰 중합체의 제조 방법 |
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MX2011002342A (es) | 2011-04-04 |
ATE545676T1 (de) | 2012-03-15 |
EP2331611A1 (de) | 2011-06-15 |
CN102143994B (zh) | 2016-11-16 |
KR101627383B1 (ko) | 2016-06-03 |
WO2010026160A1 (de) | 2010-03-11 |
JP2012501875A (ja) | 2012-01-26 |
US20110155309A1 (en) | 2011-06-30 |
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ES2378641T3 (es) | 2012-04-16 |
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