CN1643039A - Method for the production of polyamide nanocomposites, corresponding packaging materials and moulded bodies - Google Patents
Method for the production of polyamide nanocomposites, corresponding packaging materials and moulded bodies Download PDFInfo
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- CN1643039A CN1643039A CNA038069504A CN03806950A CN1643039A CN 1643039 A CN1643039 A CN 1643039A CN A038069504 A CNA038069504 A CN A038069504A CN 03806950 A CN03806950 A CN 03806950A CN 1643039 A CN1643039 A CN 1643039A
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- China
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- base material
- material polymer
- feeder
- phyllosilicate
- composite
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- Granted
Links
- 238000000034 method Methods 0.000 title claims abstract description 55
- 239000004952 Polyamide Substances 0.000 title claims abstract description 34
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 34
- 229920002647 polyamide Polymers 0.000 title claims abstract description 34
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 11
- 239000005022 packaging material Substances 0.000 title claims abstract 3
- 229910052615 phyllosilicate Inorganic materials 0.000 claims abstract description 50
- 230000004888 barrier function Effects 0.000 claims abstract description 22
- 239000000155 melt Substances 0.000 claims abstract description 9
- 125000003118 aryl group Chemical group 0.000 claims abstract description 8
- 239000000463 material Substances 0.000 claims description 68
- 229920000642 polymer Polymers 0.000 claims description 37
- 238000012856 packing Methods 0.000 claims description 23
- 238000012986 modification Methods 0.000 claims description 19
- 230000004048 modification Effects 0.000 claims description 19
- 239000008188 pellet Substances 0.000 claims description 18
- 238000000465 moulding Methods 0.000 claims description 12
- 229920006123 polyhexamethylene isophthalamide Polymers 0.000 claims description 11
- 235000013305 food Nutrition 0.000 claims description 10
- 230000009471 action Effects 0.000 claims description 9
- 239000011159 matrix material Substances 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 238000007600 charging Methods 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 239000003205 fragrance Substances 0.000 claims description 5
- 239000004615 ingredient Substances 0.000 claims description 5
- 238000001125 extrusion Methods 0.000 claims description 4
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 4
- 229920006121 Polyxylylene adipamide Polymers 0.000 claims description 3
- 125000001931 aliphatic group Chemical group 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 2
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 claims description 2
- 235000013361 beverage Nutrition 0.000 claims description 2
- 235000013351 cheese Nutrition 0.000 claims description 2
- 230000005484 gravity Effects 0.000 claims description 2
- 235000013622 meat product Nutrition 0.000 claims description 2
- 239000003973 paint Substances 0.000 claims description 2
- 150000004760 silicates Chemical class 0.000 claims description 2
- 239000000606 toothpaste Substances 0.000 claims description 2
- 229940034610 toothpaste Drugs 0.000 claims description 2
- 239000002966 varnish Substances 0.000 claims description 2
- 229920006374 copolyamide PA6I/6T Polymers 0.000 claims 1
- 238000004806 packaging method and process Methods 0.000 abstract description 13
- 238000010521 absorption reaction Methods 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 10
- 239000008187 granular material Substances 0.000 abstract description 4
- 229920005601 base polymer Polymers 0.000 abstract 4
- 150000001408 amides Chemical class 0.000 description 16
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 11
- 239000001301 oxygen Substances 0.000 description 11
- 229910052760 oxygen Inorganic materials 0.000 description 11
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 10
- 239000003795 chemical substances by application Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- -1 hexane amine Chemical class 0.000 description 7
- 230000006872 improvement Effects 0.000 description 7
- 238000007664 blowing Methods 0.000 description 6
- 230000002349 favourable effect Effects 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 239000012528 membrane Substances 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 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 description 5
- 229910052500 inorganic mineral Inorganic materials 0.000 description 5
- 239000011707 mineral Substances 0.000 description 5
- 229910052901 montmorillonite Inorganic materials 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 229910002092 carbon dioxide Inorganic materials 0.000 description 4
- 239000001569 carbon dioxide Substances 0.000 description 4
- 239000002734 clay mineral Substances 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 230000008961 swelling Effects 0.000 description 4
- 229920003620 Grilon® Polymers 0.000 description 3
- 229920006060 Grivory® Polymers 0.000 description 3
- 150000003863 ammonium salts Chemical class 0.000 description 3
- 235000014121 butter Nutrition 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 235000011089 carbon dioxide Nutrition 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 230000004927 fusion Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N methyl pentane Natural products CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- ZCILGMFPJBRCNO-UHFFFAOYSA-N 4-phenyl-2H-benzotriazol-5-ol Chemical compound OC1=CC=C2NN=NC2=C1C1=CC=CC=C1 ZCILGMFPJBRCNO-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 241000370738 Chlorion Species 0.000 description 1
- 239000004278 EU approved seasoning Substances 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910004283 SiO 4 Inorganic materials 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- WYTGDNHDOZPMIW-RCBQFDQVSA-N alstonine Natural products C1=CC2=C3C=CC=CC3=NC2=C2N1C[C@H]1[C@H](C)OC=C(C(=O)OC)[C@H]1C2 WYTGDNHDOZPMIW-RCBQFDQVSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- DLIJPAHLBJIQHE-UHFFFAOYSA-N butylphosphane Chemical compound CCCCP DLIJPAHLBJIQHE-UHFFFAOYSA-N 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- 239000000551 dentifrice Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 235000011194 food seasoning agent Nutrition 0.000 description 1
- 210000003918 fraction a Anatomy 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
- 229910000271 hectorite Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 229910052900 illite Inorganic materials 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical group O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 235000013372 meat Nutrition 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- DIOQZVSQGTUSAI-UHFFFAOYSA-N n-butylhexane Natural products CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- VGIBGUSAECPPNB-UHFFFAOYSA-L nonaaluminum;magnesium;tripotassium;1,3-dioxido-2,4,5-trioxa-1,3-disilabicyclo[1.1.1]pentane;iron(2+);oxygen(2-);fluoride;hydroxide Chemical compound [OH-].[O-2].[O-2].[O-2].[O-2].[O-2].[F-].[Mg+2].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[K+].[K+].[K+].[Fe+2].O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2 VGIBGUSAECPPNB-UHFFFAOYSA-L 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 150000004714 phosphonium salts Chemical class 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 229910052990 silicon hydride Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000005482 strain hardening 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
- 239000003760 tallow Substances 0.000 description 1
- 239000012815 thermoplastic material Substances 0.000 description 1
- 210000001364 upper extremity Anatomy 0.000 description 1
- 229910052902 vermiculite Inorganic materials 0.000 description 1
- 239000010455 vermiculite Substances 0.000 description 1
- 235000019354 vermiculite Nutrition 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
- 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
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82B—NANOSTRUCTURES FORMED BY MANIPULATION OF INDIVIDUAL ATOMS, MOLECULES, OR LIMITED COLLECTIONS OF ATOMS OR MOLECULES AS DISCRETE UNITS; MANUFACTURE OR TREATMENT THEREOF
- B82B3/00—Manufacture or treatment of nanostructures by manipulation of individual atoms or molecules, or limited collections of atoms or molecules as discrete units
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/48—Polymers modified by chemical after-treatment
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
-
- 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
- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
-
- 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
- C08J2477/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Crystallography & Structural Chemistry (AREA)
- Nanotechnology (AREA)
- Manufacturing & Machinery (AREA)
- General Chemical & Material Sciences (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Wrappers (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
The invention relates to a method for the production of polyamide nanocomposites made from base polymers comprising aromatic components and organically-modified phyllosilicates in a double-screw extruder with a front-feeder and a side-feeder. Said method is characterised in that a portion (A) from 8 to 15 wt. % of a granulate of the base polymer is introduced in the front-feeder of the double-screw extruder and the main portion (B) of said granulate of the base polymer is introduced by means of the side feeder of the double-screw extruder and that 2 to 8 wt. % of the modified phyllosilicate is introduced into the melt of the granulate portion (A) of the base polymer, whereby the wt. % proportions relate to the finished polyamide nanocomposite. According to the invention, packaging materials with high UV absorption and improved gas and aroma barrier effect can be produced by said method. Furthermore, the corresponding packagings and moulded bodies produced by means of said method and the use thereof are disclosed.
Description
Technical field
The present invention relates to from polymeric amide and phyllosilicate production method by the described polyamide nano-composite of claim 1 preamble.The polyamide nano-composite of producing according to the inventive method can be used to make transparent packing or encapsulates apparatus, and particularly the UV absorption reaches the packing appliance that gas and fragrance barrier effect are improved by force.And the polyamide nano-composite of producing according to the present invention also provides the possibility of making moulding bodies, ducted body, semi-finishing product, sheet material, tubing etc., even these objects have bigger thickness or wall thickness.
Background technology
In the plastics field, nano composite material is understood to be in and comprises the finely divided phyllosilicate such as the polymer formulators of clay mineral in the polymeric matrix.Related aspect is, phyllosilicate is stripped from into individual layer, and promptly they are disperseed then by strip off.The character of this nano composite material is narrated in many patent specifications and special publication.Known, finely divided clay mineral or phyllosilicate can provide and have improved properties (strengthen, the barrier of oxygen and carbonic acid gas is improved as physical strength, or the like matrix material).Character by finely divided clay mineral improvement polymeric matrix is at for example U.S. Pat 4,739,007 and US4, narration in more detail in 810,734.
Nano composite material has also entered packaging field.Exfoliate clay mineral has guaranteed gas molecule (as oxygen, carbonic acid gas or aromatic compound) is seen through the inhibition of wrapping material diffusion in packing film.
For many years, polymeric amide has been established status as the preferred thermoplastic material at packaging field.Its one of the main reasons is the performance characteristics of this class material, as the packing film made by polymeric amide to the outstanding barrier action of oxygen and carbon dioxide and outstanding mechanical property.When using fatty polyamide as the matrix of nano composite material, may observe the reduction of the transparency, because these nano composite material stopping composition can increase the crystallization of fatty polyamide, it can damage the transparency of this product consumingly.
An ideal target is in packaging field, and polyamide nano-composite makes up with other polymkeric substance (as polyolefine) as the part of multilayer film.The multilayer film that is made of the dissimilar polymkeric substance with mutual disadvantageous bounding force can connect each other securely by suitable bonding coat.Such multilayer film can be used to make various wrapped products, as container, bottle, bag, hot-moulding products, tubing, or the like.These products can be painted, printing opacity or transparent.For these various products can successfully be appeared on the market, they are in the face of human consumer's the big effect of performance play more and more.For what allow the human consumer can see packing the inside bag is what, and the transparency just has conclusive importance.Many suitable barrier materials are made of aliphatic polymer.These compounds are crystallization in the cold working process usually, causes the transparency of wrapping material to descend.The transparency that is caused by crystallisation process descends and can make up by the polymeric amide that uses unbodied part aromatize.
The perishable foods of packing and the quality guaranteed period of other products are mainly determined by the oxygen barrier ability of packing.The UV barrier also plays conclusive effect in many other packaging application, because UV light can damage responsive food as oxygen.When on the goods not much in demands frame that responsive food (as meat) is stored at warehouse, they usually can be subjected to deleterious UV ray, because many UV light of also launching in the light source that uses.
The UV absorption agent such as the Tinuvin 234 of special-purpose costliness, be the hydroxy phenyl benzotriazole UV absorbers, by Ciba Specialty Chemicals Inc., Basel, Swizerland produces, and can be introduced in the material of the component that constitutes described multilayer materials.Because these UV absorption agents can move under application conditions, the use of these compounds usually needs multilayer materials is increased other one deck, so that stop this UV absorption agent to move to enter in the packaged products or enter in the atmosphere.It all is impossible in all cases that multilayer film is added other one deck, because the number of issuable layer is by the structure decision of film extrusion system.
The packaging Problems that extends the shelf life of special perishable foods can not solve by packaging system and available in the market additive easily.Particularly, and the performance that all are following to be combined in the individual packaging, also need to do further improvement.These performances are:
● the packing of highly transparent
● high mechanical strength
● to the high gas shield effect of oxygen and carbon dioxide
● high fragrance barrier effect
● high UV protective effect
● the extra quality guaranteed period that prolongs in the goods not much in demands frame
● official approval can be used as food product pack
Summary of the invention
Therefore, the present invention is based on the purpose that the method for producing polyamide nano-composite is provided, use this matrix material, possible manufacturing machine performance height, transparent clarifying wrapping material or the packing appliance strong the barrier action of oxygen and carbon dioxide.This matrix material also provides the protective effect of enhanced to the UV ray simultaneously.
About producing the method for polyamide nano-composite, can reach this purpose according to the feature of independent claim 1.High UV absorbs and the packing appliance of the barrier action of the gas of improvement and fragrance about having, and can reach this purpose according to the feature of claim 13.Other inventive features can obtain from appended claims.
Embodiment
According to the present invention, by with twin screw extruder (as " WP ZSK 25 ", Werner﹠amp; Pfleiderer makes) the organically-modified phyllosilicate of mixing is produced polyamide nano-composite in mixing process.In order to carry out test of the present invention, use following screw geometry, consider the percentage ratio of the screw element of every screw rod area:
Table 1: the screw geometry of application
| Screw rod D screw rod district | Screw rod E screw rod district | Screw rod F screw rod district | |||||||
| The scroll bar element | ??K | ??L | ??M | ??K | ??L | ????M | ??K | ????L | ????M |
| The transfer roller element | ??86 | ??40 | ??85 | ??53 | ??100 | ????72 | ??70 | ????50 | ????70 |
| Left side transfer roller element (retardance) | ??- | ??20 | ??4 | ??7 | ??- | ????- | ??- | ????- | ????- |
| Mediate piece | ??14 | ??20 | ??7 | ??20 | ??- | ????8 | ??24 | ????- | ????9 |
| Mediate piece (not carrying) | ??- | ??- | ??- | ??20 | ??- | ????- | ??- | ????- | ????- |
| Mediate piece (carry on a left side) | ??- | ??20 | ??4 | ??- | ??- | ????3 | ??6 | ????- | ????3 |
| Hybrid element (carry on a left side) | ??- | ??- | ??- | ??- | ??- | ????6 | ??- | ????17 | ????6 |
| Space disc 1mm | ??- | ??- | ??- | ??- | ??- | ????11 | ??- | ????23 | ????12 |
Table 1 explanation:
Feeder is to the floor mineral charging of modification before screw rod district: the K
The layer mineral of L modification are fed to the side feeder
M side feeder is to die head
Under the situation of screw rod D, it is impossible that the layer mineral of modification are fed to melt.
Quote (FN) (film quote) as proof in order to measure film, for example " Plasti-Corder " that produces with Brabender Co. extrudes flat film from pellet.During 20 minutes, make this film move through an optical system, detect the impurity in the film, their are counted (being expressed as m2) and measure its size.The such optical system that has assessment process is sold with the trade mark of " Folientest FT4 " (Film Test FT 4) by OCS GmbH Witten.
Impurity is subdivided into 10 order of magnitude (seeing Table 2).These grades are with different weighting factor weightings.
Table 2:
| Order of magnitude | Weighting factor | Order of magnitude | Weighting factor |
| ????[μm] | ????(fi) | ????[μm] | ????(fi) |
| ????＜100 | ????0.1 | ????500-600 | ????40 |
| ????100-200 | ????1 | ????600-700 | ????55 |
| ????200-300 | ????10 | ????700-800 | ????100 |
| ????300-400 | ????20 | ????800-900 | ????200 |
| ????400-500 | ????30 | ????＞900 | ????350 |
According to following formula, the total impurities addition of every order of magnitude weighting is calculated film divided by 1000 again quote as proof.
In the formula: xi=impurity number/m2/ order of magnitude
The fi=weighting factor
In the present invention, the term phyllosilicate is interpreted as the phyllosilicate of 1: 1 and 2: 1.In such system, SiO
4Tetrahedral each layer with by M (O, OH)
6The octahedron that constitutes connects regularly.M representation metal ion (as Al, Mg, Fe).A tetrahedrallayer and an octahedral layer are connected to each other in 1: 1 phyllosilicate.Example is kaolin and serpentine ore.
Under the situation of 2: 1 three layer silicates, two tetrahedrallayer respectively combine with an octahedral layer.All occupied if not all octahedral positions, to offset SIO by the positively charged ion of required electric charge
4The negative charge of tetrahedron and hydroxide ion then will produce charged layer.This negative charge is offset by the space that univalent cation (as potassium, sodium, lithium) or divalent cation (as calcium) are inserted between each layer.The example of 2: 1 phyllosilicate has talcum, mica, vermiculite, illite and wilkinite, wherein expands with water-soluble easily owing to its layer charge with wilkinite (it comprises montmorillonite and hectorite etc.).And positively charged ion enters the generation exchange process easily.
Before swelling, the layer thickness of phyllosilicate is generally 0.5nm-2.0nm, preferred especially 0.8nm-1.5nm (upper limb of layer is to the distance of the lower edge of adjacent layers).It is possible further increasing layer distance, and Here it is, and phyllosilicate transforms (swelling) with monomer of polyamide, and as the temperature between 25 ℃-300 ℃, preferred 80 ℃-280 ℃, preferred 80-160 ℃ especially, the residence time is generally 5-120 minute, preferred 10-60 minute.Depend on the residence time and selected monomeric type, layer distance will increase 1nm-15nm in addition, preferred 1nm-5nm.The common 800nm of the length of platelet, preferred 400nm.Prepolymer any existence or that constitute is also contributed the swelling of phyllosilicate usually.
The phyllosilicate of swellable is with its loading capacity CEC (meq/g) and layer distance (d thereof
L) be feature.The value of CEC is generally 0.7-0.8meq/g.Layer distance is 1nm at the untreated montmorillonite of exsiccant, the water swelling or use organic compound after this value increase to 5nm.
The cationic example that can be used for permutoid reaction have at least with the ammonium salt of the primary amine (as hexane amine, decane amine, n-Laurylamine, stearic amine, hydrogenant fatty acid amine) of 6 carbon atoms or even quarternary ammonium salt compound, as have the α of at least 6 carbon atoms-, the ammonium salt of omega-amino acid.
Suitable negatively charged ion is chlorion, sulfate ion or or even phosphate anion.Except ammonium salt, also can use sulfosalt Huo phosphonium salt, as tetraphenyl or 4-butyl-phosphonium halogenide.
Because polymkeric substance has very different surface tension with mineral substance, except cationic exchange, also can use linking agent to handle mineral substance according to the present invention.Titanate or even silicon hydride such as γ-An Jibingjisanyiyangjiguiwan.
Explain the present invention in detail referring now to following embodiment and result.
As embodiments of the invention, produce two kinds of polyamide nano-composite prescriptions by the organically-modified phyllosilicate that adds 5 weight % and 8 weight %.The amorphous copolyamide 6I/6T (m-phthalic acid/terephthalic acid=2/1) that uses the part aromatize is as polyamide matrix, and it can Grivory G21, and the trade(brand)name of EMS-CHEMIE AG is buied from the market.
Embodiment as a comparison produces PA6 with the modification phyllosilicate of 5 weight %, and it can be buied with the trade(brand)name of " Grilon F 40 NL " (EMS-CHEMIE AG) in market.Produced polyamide nano-composite by adding specific modification phyllosilicate.
According to the present invention, can use the phyllosilicate of using ion modification as mentioned above now.The phyllosilicate of this modification can obtain from several trading companies on market, Suedchemie (D) for example, Southern ClayProducts (USA), Nanocor (USA), CO-OP (J).The modification phyllosilicate that is used for comparing embodiment of the present invention and embodiment relates to the montmorillonite of handling with quaternary ammonium ion.The part of nitrogen is methyl, hydroxyethyl and hydrogenant butter or unhydrided butter.
Then mixed material is granulated, drying is 24 hours in 90 ℃ vacuum.Mixed polymeric amide phyllosilicate material is processed into film as follows on the casting film unit of Dr.Collin GmbH, the forcing machine model is " 3300 D30 * 25D ", and the discharging type is " 136/350 ".Pellet fusion in single screw rod three hot-zone forcing machines of routine, temperature range is 250 ℃-260 ℃.Melt is that the sheet material of 0.5mm extrudes plate and pulls out by extruding the plate slit, directly moves on the cooling roller, and discharging speed is per minute 8m, and design temperature is 130 ℃.
Made the film that thickness is about 50 μ m with top setting.：
In comparing embodiment I (fatty polyamide) and III (part aromatize polymeric amide), do not add phyllosilicate.EXAMPLE IV and V represent the combination of part aromatize polymeric amide of the present invention and phyllosilicate.
Comparing embodiment I PA6 " Grilon F40 NL "
Comparing embodiment II PA6+5 weight % phyllosilicate
Comparing embodiment III PA 6I/6T " Grilon G21 "
Embodiment of the invention IV PA 6I/6T+5 weight % phyllosilicate
Embodiment of the invention V PA 6I/6T+8 weight % phyllosilicate
Carry out following measurement to the material of embodiment relatively with according to the film of inventive embodiments manufacturing:
Measure oxygen permeability (OTR) at 23 ℃ in 0% relative humidity and 85% relative humidity (seeing Table 3: " r.h. ") with Mocon surveying instrument (model is " Oxtrans 100 ").
UV absorption value Perkin-Elmer-Lambda " 15UV/VIS spectrometer mensuration.The wavelength region that is determined at 200nm-400nm is carried out.The wavelength region record transmittance that yardstick between 0%-100% is being measured.The UV barrier is improved the evaluation of degree and undertaken, comparing embodiment III (it only contains Grivory G21, does not add phyllosilicate) is set at 100 by the surface of comparing below the absorption curve of different films.
In addition, transmittance is also measured at visible wavelength district 550nm, obtains the indication of the film transparency.The numerical value that obtains is collected in the following Table 3.
Table 3
| Oxygen permeability | The % transmitance | |||
| 23 ℃/0%r. of cm3/m2 days crust h. | 23 ℃/85%r of cm3/m2 days crust .h. | Compare 200-400nm UV with Grivory G21 | 550nm light | |
| Comparing embodiment I | ????25 | ????70 | ????63 | ????70 |
| Comparing embodiment II | ????12 | ????30 | ????55 | ????65 |
| Comparing embodiment III | ????30 | ????10 | ????100 | ????92 |
| EXAMPLE IV | ????14 | ????5 | ????79 | ????85 |
| EXAMPLE V | ????13 | ????4 | ????63 | ????82 |
Shown in the measuring result of two EXAMPLE IV of the present invention and V, to compare with comparing embodiment, these films have shown the numerical value that absorbs relevant very big improvement with oxygen diffusion and UV.Being shown in the relative good UV absorption with PA 6 film samples under the II item of table 3 comparing embodiment 1 numerical value can explain with respect to the reduction of the 6I/6T variant transparency.Clearly illustrated the reduction of this light transmission ability in the printing opacity value measurement of 550nm.
The employed polymeric amide that contains aromatic group also has favourable UV barrier action, though these polymeric amide also have high transparent.Phyllosilicate added to further strengthened favourable UV barrier in these specific polymeric amide, and do not damage the transparency of these product fine basically.
Following table compares the exemplary parameter of the inventive method and the parameter of comparing embodiment:
Base material polymer A (table 4):
| Test number | The feed point of base material polymer A | The modification phyllosilicate | Through-put [kg/h] | Vacuum tightness [mbar] | Screw rod | The film grade | ||
| Type | Amount [wt%] | Feed points | ||||||
| Comparing embodiment 1 | Preceding feeder | ??G | ??5 | Preceding feeder | ????10 | ????150 | ??D | ????* |
| Comparing embodiment 2 | Preceding feeder | ??G | ??5 | ??SF | ????15 | ????150 | ??D | ????* |
| Comparing embodiment 3 | Preceding feeder | ??G | ??5 | ??MB | ????20 | ????150 | ??D | ????* |
| Comparing embodiment 4 | Preceding feeder+SF | ??G | ??5 | Preceding feeder | ????20 | ????150 | ??D | ????* |
| Comparing embodiment 5 | Preceding feeder+SF | ??G | ??5 | Preceding feeder | ????20 | ????150 | ??E | ????9.19 |
| Embodiment 1 | Preceding feeder+SF | ??G | ??5 | Melt | ????20 | ????150 | ??E | ????0.67 |
| Embodiment 2 | Preceding feeder+SF | ??H | ??4.5 | Melt | ????20 | ????150 | ??E | ????0.21 |
| Embodiment 3 | Preceding feeder+SF | ??G | ??5 | Melt | ????20 | ????50 | ??F | ????1.80 |
| Embodiment 4 | Preceding feeder+SF | ??H | ??4.5 | Melt | ????20 | ????50 | ??F | ????0.80 |
All use PA 6I/6T as base material polymer each time.In comparing embodiment 5, change to another screw rod and membrane quality can be improved to the degree that the film grade can be determined.Yet about 10 film grade is not enough.Have only the measure that the present invention is all to combine and just can make the film grade have intensive to improve (seeing embodiment 1-4).
Base material polymer B (table 5)
| Test number | Base material polymer B feed point | The modification phyllosilicate | Through-put [kg/h] | Vacuum tightness [mbar] | Screw rod | The film grade | ||
| Type | Amount [wt%] | Feed point | ||||||
| Comparing embodiment 6 | Preceding feeder | ??G | ????5 | SF | ????15 | ????150 | ??D | ??* |
| Comparing embodiment 7 | Preceding feeder+SF | ??G | ????5 | Preceding feeder | ????20 | ????150 | ??D | ??** |
| Comparing embodiment 8 | Preceding feeder+SF | ??G | ????5 | Preceding feeder | ????20 | ????150 | ??E | ??11.62 |
| Embodiment 5 | Preceding feeder+SF | ??G | ????5 | Melt | ????20 | ????150 | ??E | ??0.37 |
| Embodiment 6 | Preceding feeder+SF | ??H | ????4.5 | Melt | ????20 | ????150 | ??E | ??0.62 |
| Embodiment 7 | Preceding feeder+SF | ??G | ????5 | Melt | ????20 | ????50 | ??F | ??1.43 |
Under each situation, all use PA 6/PA 6I/6T blend as base material polymer B.In comparing embodiment 7, base material polymer B separated into two parts, and in different local chargings, do like this membrane quality has been produced improvement.The film grade only could be measured when screw geometry is also done to change.Just reach extremely strong improving (seeing embodiment 5-7) when having only the measure that the present invention is all to combine.
Base material polymer C (table 6):
| Test number | Base material polymer C feed point | The modification phyllosilicate | Through-put [kg/h] | Vacuum tightness [mbar] | Screw rod | The film grade | ||
| Type | Amount [wt%] | Feed point | ||||||
| Comparing embodiment 9 | Preceding feeder | ??G | ????5 | Preceding feeder | ??10 | ??150 | ??D | ??* |
| Comparing embodiment 10 | Preceding feeder | ??G | ????5 | ??SF | ??15 | ??150 | ??D | ??* |
| Comparing embodiment 11 | Preceding feeder+SF | ??G | ????5 | Preceding feeder | ??20 | ??150 | ??D | ??** |
| Comparing embodiment 12 | Preceding feeder+SF | ??G | ????5 | Preceding feeder | ??20 | ??150 | ??E | ??21.02 |
| Embodiment 8 | Preceding feeder+SF | ??H | ????4.5 | Melt | ??20 | ??150 | ??E | ??3.40 |
| Embodiment 9 | Preceding feeder+SF | ??G | ????5 | Melt | ??20 | ??50 | ??F | ??4.40 |
| Embodiment 10 | Preceding feeder+SF | ??G | ????3.2 | Melt | ??29 | ??50 | ??F | ??5.61 |
Under each situation, all use PA MXD6/MXDI as base material polymer C.Base material polymer separated into two parts and in the result of the different positions charging of forcing machine has also reached the improvement of membrane quality in comparing embodiment 11.Only when the geometry of screw rod changes, could measure the grade of film.Depend on used phyllosilicate, only, just can reach the strong improvement of film grade when by screw geometry being changed again and the measure that the present invention is all when all combining.
The note of table 4-6
SF: side feeder
MB: masterbatch: extrude for the first time: the preparation of MB (pellet: the ratio of modification phyllosilicate is about 70/30).
All in preceding feeder.
Extrude for the second time: MB is admixed in the remaining pellet.All at preceding feeder.
The phyllosilicate of modification: G montmorillonite, modification body;
The quarternary ammonium salt compound that has methyl, two-hydroxyethyl, h-tallow;
The H montmorillonite, the modification body;
The quarternary ammonium salt compound that has methyl, two-hydroxyethyl, butter;
Screw rod: D can not add the phyllosilicate of modification in the melt;
E does not have favourable mixing to do between phyllosilicate interpolation and side feeder
With;
F is favourable mixing effect between phyllosilicate interpolation and side feeder;
The film grade:
*Extremely bad membrane quality: the mensuration of film grade is impossible;
*Bad membrane quality: the mensuration of film grade is impossible.
Be surprisingly found out that, when the base material polymer pellet of small portion A (preferred 8-15 weight %, preferred especially 10-12 weight %) in preceding feeder charging, and major portion B adds by side feeder after a while, can obtain the base-material membrane quality.Simply by gravity, the phyllosilicate (preferred 2-8 weight %, preferred especially 2.5-5 weight %) of modification is added in the melt of pellet A part, preferably do not use side feeder.All data of representing with weight % all are the summations with respect to 100 weight % recipe ingredients.
Extrude the mode that parameter (low temperature curve, high speed, high through-put) and screw geometry preferably can reach high-shear.The preferred per minute 200 of the speed of screw rod changes more than (rpm).Preferred speed is 300rpm, and particularly preferred speed is 400rpm.
Screw geometry also is related.Before adding phyllosilicate, need guarantee the favourable fusion of granulate fraction A, for example by mediating the material piece.After it adds and before side feeder, need provide favourable mixing effect again.After side feeder, need provide sufficient kneading and mixing effect.The measure that can increase the residence time also has positive effect to the result, but should not cause the excessive degradation of base material polymer.Employed screw geometry is summarised in the table 1.And screw rod should preferably constitute by this way, make for the purpose that outgases can be before extruding plate application of vacuum.Preferred pressure or vacuum tightness are for being lower than 200mbar; Especially preferably be lower than 50mbar.
Also preferred high through-put.Constituted the possible maximum amount of used twin screw extruder (WP ZSK 25) with the through-put of the 20kg/h of these formula combination.Generally, should be on this through-put 1/4th and the velocity range of used forcing machine in operate, preferably operate in the upper limit and the velocity limit of through-put.Throughput limit is decided by the torque in required low temperature maximum possible.
The temperature of setting on forcing machine is necessary selected must be much lower with respect to the fusing point and the melt viscosity of polymkeric substance.Than the temperature of hanging down 10 ℃-20 ℃ when being blended into other packing material is preferred.Under the situation of amorphous base material polymer, 10 ℃-40 ℃ is only, and preferred temperature is than common low 20 ℃-40 ℃ (distributing with respect to the whole T-on forcing machine).
Following temperature distribution is set for processing PA 6I/6T, PA 6/PA 6I/6T-batch mixing and PA MXD6/MXDI: 10 ℃ of preceding feeders, temperature rise to 240 ℃, extrude 240 ℃ of plate temperatures from 220 ℃.Screw speed with 400rpm is operated.
The polyamide nano-composite of producing according to the present invention can be processed into different objects with the plastic working method of routine, as film, tubing, bag, bottle and container.Their available singly extruding or the manufacturing of coextrusion method.The suitable plastic working method is blowing mould or mold film, extrudes blowing moulding, shifts stretching-blowing mould, injects blowing mould, tubular type extrusion molding and laminating.
And, use the production polyamide nano-composite of the inventive method that the possibility of making moulding bodies, ducted body, work in-process, sheet material, tubing or the like is provided, even have big wall thickness.Preferred working method generally is known, comprise inject moulding method, internal gas pressure method and profile extrusion molding and the blowing moulding of extruding with standard, 3D extrudes and the vacuum blowing moulding.Moulding bodies comprises radiating pipe for example, water coolant container, compensation storage tank and guides the pipe and the container of other medium (the particularly higher medium of temperature), as use in production and transport instrument (as automobile, aircraft, boats and ships etc.).
Packaged devices can be made into the single or multiple lift packing.Under the situation of multi-layer packaging, the innermost layer that polyamide nano-composite can be used as skin, middle layer or directly contact with product.
Another embodiment of the invention also relates to described polyamide nano-composite and multilayer materials combination.The barrier action of this layer further improves by use phyllosilicate in barrier layer.The layer thickness that so just can reduce barrier layer reaches certain required barrier effect simultaneously.Because the barrier material in multilayer materials in most cases is a component the most expensive in the packing, therefore can make that so whole packaging system becomes more cheap.Another possibility that reduces packing cost is the UV barrier action of part aromatize polyamide nano-composite excellence.By using these polymer formulators, can reduce the use of expensive special organic UV absorption agent or needn't use fully, therefore further reduced the cost of required packaging system.Certain migration also can take place in organic UV absorption agent, can cause influencing the problem of wrapping material food stability.
The present invention is possible example application (to the scope of validity of the present invention without any restriction) in packaging field.It is the packing that is used for work in-process and finished product such as food, meat products, cheese and milk-product, toothpaste, makeup, beverage, paint, varnish or washing composition.Such packing comprises dentifrice tube, makeup and food pipe, and the packing of makeup, skin care product, washing composition, drink and food, or the like.
We are surprised to find, and are used as the matrix polymeric amide by selecting specific polymeric amide, and by special blending means, can solve complicated packaging Problems.The potential polymeric amide is those polymeric amide that contain aromatic components.The suitable polymeric amide of the type can comprise PA 6I/6T, PA 6/PA 6I/6T blend or by the copolyamide of HMDA and/or MXDA and aliphatics and/or aromatic dicarboxylic acid preparation.And, also can process based on polymeric amide or other polymkeric substance of lactan (lactan-6 ,-11,12) according to the inventive method.
Provide the quality guaranteed period that prolongs with packing of producing of the inventive method to perishable especially package goods, these commodity are responsive for gas (particularly oxygen and carbon dioxide) to the perviousness of packing bag.Such packing shows that also the barrier action to seasonings and spices (as distillatory oil) improves.This packing also demonstrates the reduction of beyond thought UV light transmission.
Claims (20)
1. method of producing polyamide nano-composite, make in the twin screw extruder of this matrix material by base material polymer and organically-modified phyllosilicate feeder and side feeder before having, it is characterized in that, add 8-15 weight % base material polymer pellet (A) part in the preceding feeder of twin screw extruder with metering method, the major portion (B) of described base material polymer pellet is passed through the side feeder charging of twin screw extruder, the phyllosilicate that 2-8 weight % is organically-modified joins in the melt of base material polymer pellet (A) part with metering method, makes each recipe ingredient add to summation and reaches 100 weight %.
2. the method for claim 1, it is characterized in that, add 10-12 weight % base material polymer pellet (A) part in the preceding feeder of twin screw extruder with metering method, the phyllosilicate that 2-5 weight % is organically-modified joins in the melt of base material polymer pellet (A) part with metering method, makes each recipe ingredient add to summation and reaches 100 weight %.
3. method as claimed in claim 1 or 2 is characterized in that, organically-modified phyllosilicate does not use side feeder to join in the melt of pellet (A) part with metering method by gravity.
4. one or several described method of claim as described above is characterized in that the extruder screw of type of service E or F.
5. the one or more of described method in the claim as the aforementioned is characterized in that, before the extrusion plate of twin screw extruder polyamide nano-composite is applied the pressure that is lower than 200mbar.
6. the one or more of described method in the claim as described above is characterized in that described base material polymer contains aromatic components.
7. the one or more of described method in the claim as described above is characterized in that, described base material polymer is made by HMDA and/or MXDA and aliphatic and/or aromatic dicarboxylic acid.
8. as described method wherein among the claim 1-5, it is characterized in that described base material polymer is made by lactan.
9. as the one or more of described method among the claim 1-7, it is characterized in that, use PA 6, PA 6I/6T or PA 6/PA 6I/6T blending body or PA MXD6/MXDI to be base material polymer.
10. method as claimed in claim 9 is characterized in that, uses the copolyamide PA 6I/6T of unbodied part aromatize to be base material polymer.
11. the one or more of described method in the claim is characterized in that as described above, three layer silicates that use modification are as organically-modified phyllosilicate.
12. produce the method that the UV absorptivity reaches the transparent packaging material of gas and fragrance barrier action raising by force, it is characterized in that this method comprises the method steps as the one or more of described production polyamide nano-composite among the claim 1-11 for one kind.
13. one kind has the wrapping material that high UV absorptivity reaches gas and fragrance barrier action raising by force, these wrapping material are to produce with comprising the method for making polyamide nano-composite, this method is included in and produces the polyamide nano-composite of being made by base material polymer that contains aromatic components and organically-modified phyllosilicate in the twin screw extruder with preceding feeder and side feeder, it is characterized in that, in order to produce this polyamide nano-composite, add 8-15 weight % base material polymer pellet (A) part in the preceding feeder of twin screw extruder with metering method, the major portion of described base material polymer pellet (B) is by the side feeder charging of twin screw extruder, 2-weight % modification phyllosilicate is joined in the melt of base material polymer pellet (A) part, make each recipe ingredient add to summation and reach 100 weight %.
14. wrapping material as claimed in claim 13 is characterized in that, it comprises the single or multiple lift structure.
15. wrapping material as claimed in claim 13 is characterized in that, polyamide nano-composite forms skin, middle layer or innermost layer under the situation of multilayered structure, and innermost layer is arranged to wanting packaged products and directly contacts.
16. packing container is characterized in that, it comprises the described wrapping material as one of claim 13-15, and its form is film, bag, bottle, pipe or conduit.
17. as claim 13-15 wrapping material or be used for packaged semi-finished or finished product as described in wherein, as the purposes of food, meat product, cheese or milk-product, toothpaste, makeup, beverage, paint, varnish or washing composition as packing container as described in the claim 16.
18. a method of producing moulding bodies, ducted body, work in-process, sheet material, tubing etc. is characterized in that it comprises the method steps as the one or more of described production polyamide nano-composite among the claim 1-11.
19. moulding bodies, it is to produce with comprising the method for making polyamide nano-composite, make polyamide nano-composite from base material polymer and organically-modified phyllosilicate in the twin screw extruder of this method feeder and side feeder before having, it is characterized in that, in order to produce this polyamide nano-composite, add 8-1 weight % base material polymer pellet (A) part in the preceding feeder of twin screw extruder with metering method, the major portion (B) of described base material polymer pellet is passed through the side feeder charging of twin screw extruder, the phyllosilicate that 2-8 weight % is organically-modified joins in the melt of base material polymer pellet (A) part with metering method, makes each recipe ingredient add to summation and reaches 100 weight %.
20. moulding bodies as claimed in claim 19 is characterized in that, described base material polymer contains aromatic composition or is made by lactan.
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| CH695687A5 (en) * | 2002-09-06 | 2006-07-31 | Ems Chemie Ag | Polyamide molding materials with ultrafine fillers and produced therefrom Lichtreflektier components. |
| JP2008518076A (en) * | 2004-12-03 | 2008-05-29 | エルジー・ケム・リミテッド | Barrier tube container |
| EP1717264A1 (en) * | 2005-04-29 | 2006-11-02 | Campine | Process for producing a polyamide and/or polyester composition comprising nanoclay |
| KR100896401B1 (en) * | 2007-12-31 | 2009-05-08 | 주식회사 효성 | Nanocomposite composition for multilayer containers with excellent peel resistance |
| WO2009131904A2 (en) | 2008-04-22 | 2009-10-29 | Polyone Corporation | Thermoplastic elastomers exhibiting superior barrier properties |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6376591B1 (en) * | 1998-12-07 | 2002-04-23 | Amcol International Corporation | High barrier amorphous polyamide-clay intercalates, exfoliates, and nanocomposite and a process for preparing same |
| EP1156073B1 (en) | 2000-05-19 | 2003-08-20 | Mitsubishi Gas Chemical Company, Inc. | Shaped article of polyamide resin and production thereof |
-
2003
- 2003-01-30 WO PCT/CH2003/000077 patent/WO2003064503A1/en not_active Ceased
- 2003-01-30 CN CNB038069504A patent/CN1300224C/en not_active Expired - Fee Related
- 2003-01-30 EP EP20030700793 patent/EP1470179A1/en not_active Withdrawn
- 2003-01-30 KR KR1020047011764A patent/KR100909924B1/en not_active Expired - Fee Related
- 2003-01-30 CA CA2474604A patent/CA2474604C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CA2474604A1 (en) | 2003-08-07 |
| KR20040089129A (en) | 2004-10-20 |
| WO2003064503A1 (en) | 2003-08-07 |
| EP1470179A1 (en) | 2004-10-27 |
| CN1300224C (en) | 2007-02-14 |
| KR100909924B1 (en) | 2009-07-29 |
| CA2474604C (en) | 2011-04-26 |
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