CN86101424A - The production method of articles of fractional crystallised polyester - Google Patents
The production method of articles of fractional crystallised polyester Download PDFInfo
- Publication number
- CN86101424A CN86101424A CN86101424.3A CN86101424A CN86101424A CN 86101424 A CN86101424 A CN 86101424A CN 86101424 A CN86101424 A CN 86101424A CN 86101424 A CN86101424 A CN 86101424A
- Authority
- CN
- China
- Prior art keywords
- sheet stock
- polyethylene terephthalate
- thermo
- stabilizer
- polyolefine
- 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.)
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- 238000004519 manufacturing process Methods 0.000 title claims description 17
- 229920000728 polyester Polymers 0.000 title description 12
- 229920000139 polyethylene terephthalate Polymers 0.000 claims abstract description 99
- 239000005020 polyethylene terephthalate Substances 0.000 claims abstract description 98
- 229920000098 polyolefin Polymers 0.000 claims abstract description 78
- -1 polyethylene terephthalate Polymers 0.000 claims abstract description 71
- 239000000203 mixture Substances 0.000 claims abstract description 68
- 238000000034 method Methods 0.000 claims abstract description 66
- 239000000463 material Substances 0.000 claims abstract description 51
- 238000002156 mixing Methods 0.000 claims abstract description 33
- 239000003381 stabilizer Substances 0.000 claims abstract description 33
- 229920000092 linear low density polyethylene Polymers 0.000 claims description 29
- 239000004707 linear low-density polyethylene Substances 0.000 claims description 29
- 238000003856 thermoforming Methods 0.000 claims description 26
- 238000002425 crystallisation Methods 0.000 claims description 19
- 230000008025 crystallization Effects 0.000 claims description 19
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 15
- 239000004698 Polyethylene Substances 0.000 claims description 13
- 229920000573 polyethylene Polymers 0.000 claims description 13
- 238000009998 heat setting Methods 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000000155 melt Substances 0.000 claims description 9
- 235000013824 polyphenols Nutrition 0.000 claims description 9
- 239000012298 atmosphere Substances 0.000 claims description 8
- 229920001169 thermoplastic Polymers 0.000 claims description 8
- 239000004416 thermosoftening plastic Substances 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 239000000178 monomer Substances 0.000 claims description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 4
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 claims description 4
- 150000001336 alkenes Chemical class 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- 230000004927 fusion Effects 0.000 claims description 3
- 230000006641 stabilisation Effects 0.000 claims description 3
- 238000011105 stabilization Methods 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 230000008439 repair process Effects 0.000 claims description 2
- 125000004402 polyphenol group Chemical group 0.000 claims 3
- DJNWYFARZKDJEE-UHFFFAOYSA-N benzene;methane Chemical compound C.C1=CC=CC=C1 DJNWYFARZKDJEE-UHFFFAOYSA-N 0.000 claims 2
- 239000003112 inhibitor Substances 0.000 description 40
- 230000003647 oxidation Effects 0.000 description 40
- 238000007254 oxidation reaction Methods 0.000 description 40
- 239000011347 resin Substances 0.000 description 17
- 229920005989 resin Polymers 0.000 description 17
- 230000032683 aging Effects 0.000 description 13
- 230000008569 process Effects 0.000 description 12
- 235000013305 food Nutrition 0.000 description 10
- 238000001125 extrusion Methods 0.000 description 9
- 238000000465 moulding Methods 0.000 description 9
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 238000003483 aging Methods 0.000 description 7
- 238000005562 fading Methods 0.000 description 7
- 150000008442 polyphenolic compounds Chemical class 0.000 description 6
- 239000004594 Masterbatch (MB) Substances 0.000 description 5
- 239000003963 antioxidant agent Substances 0.000 description 5
- 230000003078 antioxidant effect Effects 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 230000035939 shock Effects 0.000 description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 238000005266 casting Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000001665 trituration Methods 0.000 description 3
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229930185605 Bisphenol Natural products 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 150000004982 aromatic amines Chemical class 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000007859 condensation product Substances 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 125000005266 diarylamine group Chemical group 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 229920001903 high density polyethylene Polymers 0.000 description 2
- 239000004700 high-density polyethylene Substances 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 230000000171 quenching effect Effects 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- JIEWQZNTUPWNMX-UHFFFAOYSA-N 2,6-ditert-butyl-4-phenylphenol Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(C=2C=CC=CC=2)=C1 JIEWQZNTUPWNMX-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- VSAWBBYYMBQKIK-UHFFFAOYSA-N 4-[[3,5-bis[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]-2,4,6-trimethylphenyl]methyl]-2,6-ditert-butylphenol Chemical compound CC1=C(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)C(C)=C(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)C(C)=C1CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 VSAWBBYYMBQKIK-UHFFFAOYSA-N 0.000 description 1
- ADFVYWCDAKWKPH-UHFFFAOYSA-N 4-ethoxycarbonylbenzoic acid Chemical class CCOC(=O)C1=CC=C(C(O)=O)C=C1 ADFVYWCDAKWKPH-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- NEAPKZHDYMQZCB-UHFFFAOYSA-N N-[2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]ethyl]-2-oxo-3H-1,3-benzoxazole-6-carboxamide Chemical compound C1CN(CCN1CCNC(=O)C2=CC3=C(C=C2)NC(=O)O3)C4=CN=C(N=C4)NC5CC6=CC=CC=C6C5 NEAPKZHDYMQZCB-UHFFFAOYSA-N 0.000 description 1
- 229920002367 Polyisobutene Polymers 0.000 description 1
- 230000003679 aging effect Effects 0.000 description 1
- 150000004705 aldimines Chemical class 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 230000003666 anti-fingerprint Effects 0.000 description 1
- 239000012296 anti-solvent Substances 0.000 description 1
- 229920005601 base polymer Polymers 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000007791 dehumidification Methods 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- 208000002925 dental caries Diseases 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- UREBDLICKHMUKA-CXSFZGCWSA-N dexamethasone Chemical compound C1CC2=CC(=O)C=C[C@]2(C)[C@]2(F)[C@@H]1[C@@H]1C[C@@H](C)[C@@](C(=O)CO)(O)[C@@]1(C)C[C@@H]2O UREBDLICKHMUKA-CXSFZGCWSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 235000012204 lemonade/lime carbonate Nutrition 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
- 239000004702 low-density polyethylene Substances 0.000 description 1
- 235000012054 meals Nutrition 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000005461 organic phosphorous group Chemical group 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- 229920000306 polymethylpentene Polymers 0.000 description 1
- 239000011116 polymethylpentene Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000012958 reprocessing Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 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
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical class C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 238000001291 vacuum drying 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
- 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
-
- 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
- B29C51/00—Shaping by thermoforming, i.e. shaping sheets or sheet like preforms after heating, e.g. shaping sheets in matched moulds or by deep-drawing; Apparatus therefor
- B29C51/002—Shaping by thermoforming, i.e. shaping sheets or sheet like preforms after heating, e.g. shaping sheets in matched moulds or by deep-drawing; Apparatus therefor characterised by the choice of material
-
- 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
- C08J11/00—Recovery or working-up of waste materials
- C08J11/04—Recovery or working-up of waste materials of polymers
- C08J11/06—Recovery or working-up of waste materials of polymers without chemical reactions
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2067/00—Use of polyesters or derivatives thereof, as moulding material
-
- 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
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/10—Greenhouse gas [GHG] capture, material saving, heat recovery or other energy efficient measures, e.g. motor control, characterised by manufacturing processes, e.g. for rolling metal or metal working
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
Landscapes
- Chemical & Material Sciences (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Organic Chemistry (AREA)
- Sustainable Development (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Blow-Moulding Or Thermoforming Of Plastics Or The Like (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
Make a kind of method of sheet stock and thermoformed articles with polyethylene terephthalate/polyolefin blend material, these goods have improved colour stability and can repeatedly recycle repeatedly.Thermo-stabilizer is before sneaking into polyethylene terephthalate, earlier with the polyolefine melt blending.PET and polyolefin blend and be extruded into sheet stock are thermoformed into the goods as tray of microwave oven immediately then.
Description
The present invention is about preparing the method for polyethylene terephthalate/polyolefin blend tablet material, and this sheet stock is used in the heat setting type goods of thermoforming partial crystallization.Particularly described in the present invention with the polyethylene terephthalate blend before only in polyolefine, add the method for oxidation inhibitor.
Along with the progressively popularization of microwave oven, the arbitrarily used food container of people's energy generally low to production cost, microwave thoroughly is interested.The food that bakes in advance can exist carry out then in the container freezing.The human consumer can reprocessing have baked in microwave oven or general convection heat stove before edible the frozen product bag.The pallet application form that this two sides can be toasted is a lot of to the requirement of used container, and is various.At first, container must can be stood secular high temperature exposure, and shock strength or dimensional stability do not have obvious decline.The second, container must maintain even constant color and can resist the signs of degradation that color is changed under the long-time high temperature exposure in microwave oven or versatible furnace.United States Patent (USP) 4,463,121 have described a kind of method of producing articles of fractional crystallised polyester, and the major ingredient of these goods is polyethylene terephthalate (PET), and auxiliary composition is a polyolefine, and the goods crystallization content of producing with this method is about 10% to about 30%.This goods are for using as container and presenting stable shock strength and dimensional stability owing to reached certain degree of crystallinity in thermoforming.This patent also points out in order to reach the purpose that goods have stable properties viscosity, needs to become to add about 0.05% to about 2%(weight in polyethylene terephthalate/polyolefin blend material) thermo-stabilizer.
United States Patent (USP) 3,960,807 point out that a kind of composition that contains three base stocks becomes to be thermoformed into method (1) the energy crystalline polyester of goods; (2) crack inhibitor, preferably polyolefine; (3) nucleator.The described method improvement of this patent in the thermoforming process shock resistance and the crystallization rate of goods.
In order to produce the pallet that can toast in thin-gage goods such as microwave two sides or without the container of oxidation inhibitor, with United States Patent (USP) 4,463, in the pallet thermal ageing of 121 or 3,960,807 method preparation, run into three the different problems relevant with high temperature exposure, the limiting viscosity of (1) pallet descends always; (2) have and become brown or yellow colors trend; (3) on the surface of pallet (pallet that particularly catches and touched) irregular yellow or brown spot are arranged.This this last phenomenon is called fingerprint (finger printing) at this.Method of the present invention has been eliminated the phenomenon of above-mentioned three thermal destructions effectively, and present method is by before polyethylene terephthalate and polyolefin blend, sneaks into a kind of effective thermo-stabilizer or oxidation inhibitor in the polyolefine and reaches.Present method also provides in polyester or polyester/polyolefin blend material and to have added required 1/10 to 1/100 oxidation inhibitor and material is effectively protected.
One of purpose of the present invention provides a kind of method with polyethylene terephthalate and polyolefine manufacturing sheet stock, is heat-staple in the thermoforming afterwards of this sheet stock.Utilizing the thin-gage goods of method production of the present invention or the advantage of pallet is during high temperature ageing, and they can resist fades or anti-fingerprint.Advantage of the present invention is to utilize microwave oven that method of the present invention produces or the furnace tray commonly used can be under 200 ℃ of temperature, put more than 1 hour and do not have fade, a large amount of decline phenomenons of fingerprint or limiting viscosity.Another advantage of the present invention is that the used deal of oxidation inhibitor is suitable with the protection pallet.
Advantages more of the present invention and purpose can obtain by using the method for producing amorphous, heat-staple polyolefin modified polyethylene terephthalate sheet stock, and production method may further comprise the steps:
(1) the thermo-stabilizer of significant quantity with carry out melt blending to form a kind of stable polyolefine by containing 2 to 6 polyolefine that the carbon atom olefinic monomer is produced;
(2) be about one section time enough of polyethylene terephthalate of 0.65 to about 1.2 at dry gas atmosphere and at least 150 ℃ of following heat characteristic viscosity, arrive 0.02%(weight with the water content that reduces polyethylene terephthalate) below, a kind of exsiccant polyethylene terephthalate formed;
(3) a small amount of described stable polyolefine mixes mutually with a large amount of exsiccant polyethylene terephthalates, with the melt blending material that forms uniformly, melts;
(4) make sheet stock with described uniform melt blending material;
(5) the described sheet stock of cooling mainly is unbodied sheet stock to form.
Another aspect of the present invention is to show to produce in the production of articles method heat-staple, partial crystallization heat setting type, non-orientation that this method may further comprise the steps;
(1) thermo-stabilizer of significant quantity and the polyolefine of being produced by the olefinic monomer that contains 2 to 6 carbon atoms are carried out melt blending to form a kind of stable polyolefine;
(2) be about one section time enough of polyethylene terephthalate of 0.65 to about 1.2 at dry gas atmosphere and at least 150 ℃ of following heat characteristic viscosity, arrive 0.02%(weight with the water content that reduces polyethylene terephthalate) below, a kind of exsiccant polyethylene terephthalate formed;
(3) described dry polyethylene terephthalate and described stable polyolefine are together sent in the device that is used for melt blending;
(4) a spot of described stable polyolefine and a large amount of exsiccant polyethylene terephthalate are mixed melt blending material uniform to form, fusing;
(5) make sheet stock with described uniform melt blending material;
(6) described amorphous sheet stock is put on the mould of plastics;
(7) described sheet stock thermoformed articles, it is placed in the thermoplastic mould one section time enough so that goods reach 15%～35% degree of crystallinity;
(8) from described thermoplastic mould, take out described goods;
(9) repair described goods.
The method of the polyolefin modified polyethylene terephthalate sheet stock that but another aspect of the present invention is a kind of production recirculation to be used, its step is as follows:
(1) the thermo-stabilizer of significant quantity with carry out melt blending to form a kind of stable polyolefine by containing 2 to 6 polyolefine that carbon atom alkene is produced;
(2) be about one section time enough of polyethylene terephthalate of 0.65 to about 1.2 at dry gas atmosphere and at least 150 ℃ of following heat characteristic viscosity, arrive 0.02%(weight with the water content that reduces polyethylene terephthalate) below, a kind of exsiccant polyethylene terephthalate formed;
(3) together sending described exsiccant polyethylene terephthalate and described stable polyolefine to one is used for carrying out in the device of melt blending;
(4) a spot of described stable polyolefine and a large amount of exsiccant polyethylene terephthalate are mixed to form a kind of mixture;
(5) dissolve the melt blending material of the described mixture of blend to form uniformly, to melt;
(6) make sheet stock with described even melt blending material;
(7) the described sheet stock of cooling mainly is unbodied sheet stock to form;
(8) described amorphous sheet stock is put into a mold;
(9) the described sheet stock of thermoforming in the thermoplastic mould, the described amorphous sheet stock of chien shih reached partial crystallization when one section of hot pressing was enough.
(10) sheet stock with partial crystallization takes out from described thermoplastic mould;
(11) trim the part sheet stock that contacts the mould surface, stay the base-material of amorphous sheet stock.
(12) grinding described base-material becomes trituration, according to step (2) trituration is heated again, uses the formed mixture of step (4) to mix with described trituration then, repeats step (5) at least to (12).
For produce the goods that can under hot environment, use or container, polyester should be crystalline state rather than separate the crystalloid attitude.Known thermoplasticity, energy crystalline polyester, polyethylene terephthalate (PET hereinafter referred to as) have desired character, as good dimensional stability is at high temperature arranged, the performance of chemical proof, anti-oil and anti-solvent and can see through microwave radiation and do not have and absorb or performances such as reflection.These performances make them become the polymkeric substance of manufacturing the high temperature food container.
The polyethylene terephthalate polymkeric substance is with known polymerization technique preparation by terephthalic acid or its lower alkyl esters (dimethyl terephthalate (DMT)) and 1.2-ethylidene glycol.Terephthalic acid or dimethyl terephthalate (DMT) be through esterification or transesterification, thereby obtain high molecular weight product with 1,2 ethylene glycol generation polycondensation then.Should have an appointment 0.65 to about 1.2 limiting viscosity of the polyester that uses among the present invention is preferably about 0.80 to about 1.05, (under 30 ℃, measuring in order to 60/40 volume ratio phenol/tetrachloroethane mixing solutions).Obtain high limiting viscosity and can use known method for solid phase polymerization.
In order to use polyethylene terephthalate in feasible Industrial processes (as thermoforming), major requirement can obtain desired degree of crystallinity in the very short cycle.The cycle of general requirement is about 5 to 7 seconds.Usually, the polyethylene terephthalate polymer crystallization speed of non-modified is too low can not reach the required time cycle.Low in order to overcome crystallization velocity, can add nucleator and form the crystalline number to increase.The nucleator of knowing most is that to have mean particle size be 2 to 10 several meters inorganics.Other known nucleator is the carbon containing thing, as: carbon black and graphite.Common nucleator can be talcum, gypsum, silica, lime carbonate, aluminum oxide, titanium dioxide, metal smalls, glass powder, carbon black and graphite.The common feature of known nucleator listed earlier is to have part at 100 ℃ to 300 ℃ temperature range internal solid nucleator, makes polyester form crystalline texture.Though these specific nucleators still stable degree of crystallinity can occur after reducing or cancelling, use the specific nucleator of any of these to be good.
Second major ingredient of the present invention is polyolefine, and it must be with polyethylene terephthalate-existence.Polyolefine is to be produced by the chain alkene monomer that 2 to 6 carbon atoms are arranged as used herein.Resulting polymers is the repeating unit of used monomeric unit.These repeating units are different with monomer, and they no longer contain carbon-to-carbon double bond.This base polymer comprises new LDPE (film grade), high density polyethylene(HDPE), LLDPE, polypropylene, polyisobutylene, polybutene, polypenthylene, polymethylpentene.Polyolefine content should reach 0.5～15%(weight of polymkeric substance total amount).Be preferably 1～5%(weight).2～4%(weight preferably).A class polyolefine is a polyethylene preferably, LLDPE (LLDPE) preferably, as: the commodity DOWLEX2045 of Dow Chemical Company and 2035 that sells on the market.Compare with unmodified polyethylene terephthalate, all polyolefine make the shock strength of finished product that improvement be arranged and improved release property in the thermoforming processes.Polyethylene and polypropylene have very wide operating temperature range, faster crystallization velocity and lower crystallization onset temperature.The cost that these improvement cause that the short crystallizing cycle time is arranged, per minute can be produced more parts and fabricated product is lower.
Found to use crystallization velocity that the polyolefins of PET has at least with contain polyolefine and a kind of other PET composition crystallization velocity of nucleator (for example at United States Patent (USP) 3,960, described in 807) is equally fast.
Though known can being added to thermo-stabilizer or oxidation inhibitor in the polyethylene terephthalate.Then, the protection problem of PET/ polyolefine batch mixing becomes very difficult under 200 ℃ of about environment of 1 hour.Obviously, must wish that it reduces stablizer or antioxygen dosage exists when will be with Food Contact with the goods of PET/ polyolefin blend material preparation.Not found before the preparation of PET/ polyolefin blend material with expecting, directly in the polyolefine component, add quite a spot of oxidation inhibitor or stablizer, can make PET/ polyolefin blend material be subjected to best protection.Guaranteed time routine character (1) limiting viscosity small loss very in the course of processing and thermal ageing process thereafter in this method that adds thermo-stabilizer before PET and the polyolefin blend; (2) expansion of fingerprint or variable color mottling face has been got rid of in the variable color (2) of getting rid of blend composition in high temperature exposure during high temperature ageing.Thermo-stabilizer is the compound that oxidation inhibitor character is arranged as used herein, wherein the most important thing is to prevent oxidation.The net heat stablizer that uses in the invention process must can be protected thermoforming, heat setting type polyester article, United States Patent (USP) 3,987 during high temperature exposure; 004, United States Patent (USP) 3,904, and 578 and United States Patent (USP) 3; 644,482 have all delivered the example of many thermo-stabilizers of knowing.Below these compounds are representatives of the thermo-stabilizer that uses in the invention process: the alkyl-substituted phenols class, bisphenols, the bisphenols of replacement, thiobis phenols, Polyphenols, thiobis esters of acrylic acid, aromatic amine, organic phosphorous acid salt and poly-phosphorous acid salt.Test shows that the main aromatic amine with extreme heat stability comprises: uncle's polyamine class, diarylamines, two diarylamines, alkyl diarylamines, ketone-diarylamines condensation product, aldimine condensation product and aldehyde amines.It is abominable that the heat setting type goods of thinking thermoforming in the invention process are exposed to nearly 200 ℃ of conditions that surpass 30 minutes.This abominable high temperature is used down and is not wished to have any contamination that is caused by thermo-stabilizer or fade, and best thermo-stabilizer is to use Polyphenols, and this Polyphenols is the compound with two above phenol ring structures.Used Polyphenols comprises (but being not limited only to this): methane and 1,3 four (methylene radical 3-(3,5-di-t-butyl-4-acrinyl)-propionic esters), 5-trimethylammonium-2,4,6-three (3,5-di-t-butyl-4-hydroxyphenyl) benzene.The polyphenol of back is best.The more favourable add-on of thermo-stabilizer is PET/ polyolefine/stabiliser composition total amount 2%(weight) below, and be preferably weight at 0.5%() below.Preferably in 0.005% to 0.03%(weight) between.
Oxidation inhibitor directly is added in the polyolefine component of polymer blends by melt blending.Therefore can understand and contain great percent by weight oxidation inhibitor (than PET and the last ratio of polyethylene) in the polyolefine component; the actual usage quantity of oxidation inhibitor depends on the degree of required protection, abominable degree that selected stablizer characteristic heat exposes and the dissolution degree in polyolefine.When used food trays is when producing with the inventive method, must consider so, to controlling, generally control oxidation inhibitor and can join the neutralization of each component and add upper limit amount in the blend composition of polymkeric substance to the end with the contacted relevant material of food.
The production method of polyolefin modified polyethylene terephthalate sheet stock may further comprise the steps (1) suitable thermo-stabilizer with by have 1～4 carbon atom once the polyolefine produced of alkene carry out melt blending to form a kind of stable polyolefine.(2) in dry air or nitrogen atmosphere, be heated to more than its second-order transition temperature and remain under such condition that water content is low the hydrolytic deterioration effect to occur to unlikely in step in succession up to making the polyethylene terephthalate with limiting viscosity 0.65 to 1.2.(3) stable polyolefine and exsiccant polyethylene terephthalate resin are so that suitable ratio-with being transported in the extrusion machine, two component melt blendings form a kind of even melt blending material in extrusion machine.(4) make sheet stock with even melt blending material.(5) the quenching sheet stock is essentially unbodied method material with formation.
The melt blending of thermo-stabilizer can be finished to being equipped with polyolefinic polyreaction latter stage, perhaps utilizes any common thermoplasticity to mix in the forcing machine and carries out, and oxidation inhibitor will be fully distributed in is melted in the whole polyolefine of extruding anti-cylindrical shell.It is the necessary operation steps of limiting viscosity that keeps resin that the polyethylene terephthalate resin is heated in exsiccant nitrogen or air atmosphere.In all the other procedure of processings of present method moisture content being required is to want to have kept to be enough to high inherent viscosity.It is favourable that minimum actual water content can be arranged certainly.General water content requires to be lower than 0.02%.Should be lower than 0.005% for the optimum water content of high inherent viscosity PET.For the close utensil that makes made of the present invention has high shock resistance and dimensional stability, should carefully handle PET to keep its high inherent viscosity.The polyolefine that contains oxidation inhibitor mixes with exsiccant PET and can finish by well-known film expressing technique.Be heated at this polyolefine and PET more than their second-order transition temperature and the shear blend by melting charge forms the even blend composition of being made up of two kinds of different plastics.Can think that polyolefine is distributed among the whole PET but in separating mutually, preserve its characteristic.The moulding of sheet stock can be finished by the general thin moulding process.The sheet stock of using among the embodiment is produced with Prdex film forcing machine below, and the fusion sheet stock is squeezed on a cold casting roller, cools off the degree of crystallinity that generates to reduce then immediately.Explanation is used for the extrusion condition of the amorphous sheet material of manufacturer's instructions embodiment pallet in the table I.
The table I
The sheet extrusion condition
1.75 inches Pralex of extrusion machine specification
288 ℃ of extrusion machine sections
The neck cooling is
The screw rod cooling is not
94 rev/mins of extrusion machine speed
Extrusion machine pressure 19 MPas
Extrusion machine magnification 10.5
296 ℃ of polymer temperatures
Notes are chewed 277 ℃ of junctions
Die head section 1,2,3 is 288 ℃
1 75 ℃ of casting rollers
2 63 ℃ of casting rollers
1.2 millimeters/minute of discharging speeds
0.76 millimeter * 0.4 meter of sheet stock area
Material PET 97%/LLDPE3%
The thin-walled pallet of being made sheet material heat production in next life typing by stable polyolefine/PET can utilize all known thermoforming process, comprises vacuum pressed, air pressurized, the pressurization of mechanical formpiston or matched-mold forming etc.Mould should be preheating to enough temperature to obtain desirable degree of crystallinity.Suitable die temperature select to depend on thermal forming device type, want pressing structure and wall thickness and other factor.Practical die temperature scope is 150～215 ℃, and scope is 170～190 ℃ preferably.
Heat setting type is to describe the polyester article of making partial crystallization and not having significantly orientation existence, the term of thermal process, in the invention process, heat setting type closely contacts with the heated die surface by film or sheet stock and reaches, it keeps one section time enough to obtain certain degree of crystallinity, makes the product of making that satisfied physicals is arranged under this degree of crystallinity.The degree of crystallinity of known hope is about 10% to about 35%.For the container in the high temperature food applications, for satisfying the requirement of dimensional stability in the demoulding and baking oven exposure, goods degree of crystallinity must be greater than 15%.
The heat setting type parts can take out from die cavity with known demoulding means.A kind of method is exactly the vacuum of being set up between compressed-air actuated destruction mould and made sheet stock by importing.In case the heat setting type parts take out, will be trimmed the rim charge part to obtain pallet from mould.Owing in most of industrial hot forming tools many die cavitys are arranged all, so that can produce many pallets, therefore, stay planar sheet stock base-material beyond the pallet mouth with a slice sheet stock, generally always stay 10～60% original sheet base-material.For making thermoforming operation economical rationality then must utilize these base-materials once more.Using repeatedly of these base-materials means the heat affecting process (hcat history) that exists in the sheet stock clearly.Sheet stock when 40% is when utilizing again, and polyolefine/PET blend composition of estimating considerable part will stand full cycle step 5 time.This multiple step comprises: (1) grinds; (2) in dry atmosphere, heat; (3) put in the system and unworn raw materials melt blend; (4) make sheet stock; (5) quenching; (6) heating once more before entering hot forming tool; (7) in thermoforming machine, stretch and heat setting type; (8) cool off these parts then; (9) demoulding.Repeat all these step 5 time, therefore, the time ratio that resin is under the high-temperature of sheet stock preparation and thermoforming is much longer when prepare the first time.So abominable high temperature exposure is disadvantageous for the limiting viscosity of PET and the stability of polyolefine component, and recognizes just that until the present invention the guard method of PET polyolefin blend material is very harsh, and particularly work in-process utilizes material to reach again at about 40% o'clock.Among the embodiment, the independent use of 1.04 limiting viscosity poly terephthalic acid ethyl esters also can be used (LLDPE has bought from Dow Chemical Company, and trade mark is DowLex 2045.) with LLDPE (LLDPE) is common below.Have the PET of LLDPE to be dried and extrude according to the condition of table I, then height being made in the thermoforming on Comet Labmaster thermoforming machine of the sheet stock of 0.76 mm thick is 2.5 centimetres, the pallet of 13 cm x, 13 centimeter square.All percentage ratios are represented with the percentage ratio of the gross weight of total composition weight polymeric sheet material or pallet.
Unsettled food trays
Embodiment 1-2
Polyethylene terephthalate sheet stock with 1.04 limiting viscosities is made pallet.Measure limiting viscosity after the pallet thermoforming is finished, these pallets wore out 1 hour under 200 ℃ in circulated air oven then.Test primary characteristic viscosity again.The results are shown in table 2.What embodiment 1 and embodiment 2 used is the 97%PET/3%LLDPE sheet stock that does not add oxidation inhibitor.Obviously see independent PET or PET and polyolefine (for example LLDPE) blend composition from the result of table II, when not adding oxidation inhibitor or stabiliser system and protect, the bigger decline during high temperature ageing of its limiting viscosity.The loss of limiting viscosity is to be unallowed fully in food trays is used, and (as embodiment 3) do not have oxidation inhibitor goods (comprising United States Patent (USP) 4,463, the technology of 121 inventions) infeasible at all.
Comparing result:
Embodiment 3-7:
All embodiment are prepared by the PET/LLDPE sheet stock in this group embodiment, sheet stock contains the best polyphenol antioxidant of various ratios, particularly 1,3,5-trimethylammonium-2,4,6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene, (buy from Ethel company, trade mark is Ethauox330).The percentage ratio of oxidation inhibitor is the oxidation inhibitor percentage composition that calculates with whole sheet stock composition total weight in the blend composition shown in the table II is formed.The purpose of this serial experiment is to estimate 200 ℃ of following thermal ageings following three Effect on Performance, and these three performances are important for the pallet that uses in microwave and general stove.These performances are: (1) fingerprint: a kind of like this phenomenon represented in this term, promptly has irregular significantly on aged pallet sample and be to fade large stretch ofly.This tray surface that typically appearing at catches touched that fades.In the aging effect hurdle, fingerprint " has " with scattered mottling and " nothing " represented in the table II.Clearly, if record is " having ", there is fingerprint to occur after expression is aging.If record is " nothing ", then pallet has kept its original uniform appearance.(2) color: colour terminology shows that 200 ℃ are worn out after 1 hour down, and original color of pallet is constant or has become.The phenomenon of fading is meant the color even variation of pallet.If record is " constant " under listed color, show that then aging back color does not change.If record is " fading ", show that then the result of thermal ageing makes color that recognizable fading be arranged.(3) limiting viscosity: when PET is in high temperature following time, limiting viscosity trends towards reducing.Measured initial intrinsic viscosity and compared with the limiting viscosity of being surveyed after following 1 hour at 200 ℃.Variable factor also comprises the ratio of oxidation inhibitor in embodiment 3-7, adds the mode of the component and the adding oxidation inhibitor of oxidation inhibitor.
Embodiment 3
In embodiment 3, oxidation inhibitor 0.1% is added to and dissolves mutually during produce the polyethylene terephthalate polymkeric substance, the limiting viscosity that remains unchanged that the result is satisfied, but the pet polymer that higher relatively antioxidant content can cause being used for blend composition in PET fades.Generally fade is to become Huang to brown by primary PET resin creamy white.Maintenance all can cause all fading under the long term high temperature during high temperature in PET produces becomes high inherent viscosity (1.04) with resin solidification by inference.This fading is being very deleterious as the meal tray time spent.In addition, fingerprint to occur also be not satisfied to aging back sample.
Embodiment 4
Example 4 usefulness and example 3 the same polymeric components are carried out blend but are wherein added 0.19% oxidation inhibitor.Oxidation inhibitor be in the PET that is added in the reactor and the LLDPE masterbatch in.Under oxidation inhibitor adding method one hurdle, indicate it is " masterbatch ", show that then the PET/LLDPE with 77/23 weight phenol ratio carries out the masterbatch that the machine blend has bullet to form especially.
Then the masterbatch of this PET and LLDPE with 13～87%(weight) the PET production of resins of ratio go out final LLDPE be 3% and PET be 97% blend composition.This master batch method makes the deployment conditions of polyolefine in PET be improved, especially when the funnel on the film forcing machine and when having accurate scale to be lower than 3% situation with control resin percentage ratio.Fruiting characteristic viscosity remains unchanged and does not have obvious fingerprint, but because higher antioxidant content is arranged, fading of pallet is tangible.Oxidation inhibitor trends towards flavescence significantly when very high-content oxidation inhibitor joins in the PET/ polyolefin blend material.
Example 5-7
Utilize the film sheet stock of the oxidation inhibitor preparation of the PET/LLDPE of 97/3 weight phenol ratio and percentage.Use method of the present invention, with the PET blend before the time, first oxidation inhibitor joins in the LLDPE.Oxidation inhibitor is not added among the PET, in the table III, this addition is described as being directly in the oxidation inhibitor adding method hurdle and is added among the LLDPE.Use this method,, then molten resin is made required one and be shaped as (for example bullet, shot or other desired shape) by melting specific polyolefine again and the homogeneous phase blend joins a certain amount of oxidation inhibitor in the polyolefine.Blend mixes (Sterling transfcrmir) forcing machine with the Stirling conversion to be carried out, and the extruder barrel temperature maintenance is maintained at 175 ℃ in about 195 ℃ of die temperature, and screw speed is 84 rev/mins.Then, LLDPE enters the film forcing machine with the PET that does from narrow orifice (ttrroat entrance) and carries out blend.The film forcing machine is equably with the melt blending material of the synthetic homogeneous of PET and stable LLDPE blend.List the aging resistance of stablizing the pallet that blend composition makes with polyolefine in the II at table.The result shows at 200 ℃ and down promptly uses extremely low antioxidant content after aging 1 hour that its limiting viscosity color constant and pallet is also constant; Example 5 0.09%(weight) oxidation inhibitor, showing has tangible fingerprint; And the antioxidant content of example 6 usefulness is higher a little, and the result shows the vestige that does not almost have fingerprint.Example 7 is used 0.24%(weight) oxidation inhibitor, there is not tangible fingerprint yet.Obviously different with example 3, used in the example 3 almost and eliminated fingerprint than this big 8 times oxidation inhibitor.And resin also presents bad yellow after aging.
Circulation experiment:
Embodiment 8～22.
When producing pallet, in the general moulding process, generation there is 40% corner sheet stock in moulding each time and all after dates of finishing with single crowded sheet stock thermoforming.In order to utilize, these sheet stocks will be through grinding and mixing with original PET/ polyolefine material more again.Reuse like this and in the polymerization blend composition, produced very big heat affecting process, thereby cause fading, fingerprint, limiting viscosity reduces and problem such as degree of crystallinity change.In order to produce the thermoforming pallet that can be used for food, must keep above-mentioned characteristic (perhaps eliminating these problems) during materials again with a kind of industrial method with containing big per-cent.Utilize material amount as many as 40% again in the typical thermoforming process.By the typical stable operation of this moulding system, refacing to utilize means that same resin will be through making sheet stock and being pallet, about 5 times of processes such as thermoforming again.Therefore, following experimental program imitation utilizes material through 5 round-robin systems, with assess thermal stability with 40% again.Used resin is a 97%PET(limiting viscosity 1.04), 3% LLDPE and 0.15%Ethanox330(Ethel Corporation be on sale).Oxidation inhibitor mixes the forcing machine fusion with the Stirling conversion sneaks among the LLDPE, makes particle then so that enter 1.75 English inch (45 millimeters) Prodex film forcing machine with PET later on and carries out blend.This process production stage is as follows:
(1) in having the Conair dehumidification hopper of dry nitrogen atmosphere, resin/utilization material blend composition is following dry 4 hours at 170 ℃ again.
(2) after the drying, each sample is placed in 100 ℃ of vacuum drying ovens and keeps dry, and is issued to balance at 100 ℃.
(3) 100 ℃ resin put into the forcing machine hopper and with mix with the stable LLDPE of oxidation inhibitor, to obtain the blend composition of appropriate per-cent.
(4) the blend composition explanation of giving according to the previous table I is extruded into amorphous sheet stock.
(5) under following condition, the Comet Labgnarter thermoforming machine thermoforming of the pallet of test.
Giving 12 seconds hot time in the baking oven dashes
315 ℃ of oven temperatures (top)
225 ℃ (bottom)
8 seconds of molding cycle
160 ℃ of molding temperatures
Sheet stock unnecessary and not moulding section trim from pallet, these are the base-materials that are used for recirculation processing that produced by thermoforming.
(6) last not moulding base-material is 150 ℃ of following crystallizations, cools off and wears into powder by 6 mm sieve, adds new 97/3PET/LLDPE resin again, with 60/40 new resin/utilize again thing mixed.This resin and utilize the blend composition of material to carry out drying and 5 experimental procedure 1-6 of repetition again according to step 1.The following character of pallet is all given mensuration in five round-robin circulate each time: (1) limiting viscosity; (2) Hunter color value " B "; (3) the crystallization percentage ratio of calculating by the pallet densometer.Above-mentioned all the results are shown in the table III.
Listed data show that pallet that the polyolefine component film that is added with oxidation inhibitor is made has and keep keeping to the limiting viscosity performance, well color well and crystallization control degree etc. well after five recirculation in the table III.This stable degree shows and adds before the PET, but with this quadrat method stabilization of polyolefins gained material recycled for multiple times, do not descend and made pallet intensity and performance characteristic are obvious.This recycle ability is crucial in the corner base-material is operated greater than 40% industrial thermoforming.
Revisal: 86101424 errata CPCH866005
Claims (21)
1, a kind of production method that can utilize again, polyolefin modified polyethylene terephthalate sheet stock is characterized in that the step that comprises has:
(a) thermo-stabilizer of melt blending significant quantity with by containing 2 to 6 polyolefine that the carbon atom chain alkene monomer is produced, K-is to form stable polyolefine;
(b) dry gas atmosphere and at least 150 ℃ of following heat characteristic viscosity be about one enough period of polyethylene terephthalate of 0.65 to about 1.2 with the water content to 0.02% (weight) that reduces polyethylene terephthalate below, thereby form a kind of exsiccant polyethylene terephthalate;
(C) together send described exsiccant polyethylene terephthalate and described stable polyolefine to a device that is used for melt blending;
(d) a spot of described stabilization of polyolefins and a large amount of exsiccant polyethylene terephthalate are mixed to form a kind of mixture.
(e) dissolve the melt blending material of the described mixture of blend to form uniformly, to have melted;
(f) make sheet stock with described even melt blending material;
(g) the described sheet stock formation of cooling is unbodied sheet stock basically;
(h) described amorphous sheet stock is put into a mold;
(i) one enough period of the described sheet stock of thermoforming in the thermoplastic mould, make described amorphous sheet stock reach partly crystallization;
(j) the partial crystallization sheet stock is taken out from described thermoplastic mould;
(k) repair the part sheet stock of attitude contact mold surfaces and stay base-material.
(l) grind the described base-material material that becomes to reface, again according to step
(b) the heating material of refacing, then with it with mix with the formed mixture of step (d), repeating step (e) to (l) is more than at least one time.
2, according to the described method of claim 1, wherein said polyolefine is a polyethylene.
3, according to the described method of claim 1, wherein said polyethylene is a LLDPE.
4, according to the described method of claim 1, wherein said polyethylene is a LLDPE, described thermo-stabilizer is a polyphenol, it is selected from 1,3,5-trimethylammonium-2,4,6-three (3,5-di-t-butyl-4-acrinyl) methane benzene, four (methylene radical 3-(3,5-di-t-butyl-4-hydroxyphenyl)-propionic ester).
5, by the described method of claim 1, wherein the significant quantity of thermo-stabilizer is less than 0.05%(weight).
6, by the described method of claim 1, wherein the significant quantity of thermo-stabilizer is about 0.05%～about 0.3%(weight),
7, by the described method of claim 1, wherein said thermo-stabilizer is 1,3,5-trimethylammonium-2,4,6-three (3,5-di-t-butyl-4-acrinyl) benzene,
8, a kind ofly produce method noncrystalline, the olefin-modified polyethylene terephthalate sheet stock of heat-stabilised poly, comprise that step is as follows:
(a) thermo-stabilizer of melt blending significant quantity with by containing 2 to 6 polyolefine that the carbon atom alkene is produced, to form a kind of stable polyolefine;
(b) be about 0.65 to about 1.2 polyethylene terephthalate one enough period with the water content that reduces polyethylene terephthalate to 0.02%(weight in dry gas atmosphere and at least 150 ℃ of following heat characteristic viscosity) below, thereby the exsiccant polyethylene terephthalate formed;
(c) a spot of described stable polyolefine and a large amount of polyethylene terephthalate of doing are mixed the melt blending material that has melted uniformly to form;
(d) described even fusion batch mixing is made sheet stock,
(e) the described sheet stock of cooling is unbodied sheet stock to form basically;
9, by the described method of claim 8, wherein polyolefine is a polyethylene.
10, by the described method of claim 8, wherein polyethylene is a LLDPE.
11, by the described method of claim 8, wherein said polyethylene is a LLDPE, described thermo-stabilizer is a polyphenol, and it is selected from 1,3,5-trimethylammonium-2,4,6-three (3,5-di-t-butyl-4-acrinyl) benzene, four (methylene radical 3-(3,5-di-t-butyl-4-hydroxyphenyl)-propionic esters) methane.
12, by the described method of claim 8, wherein the significant quantity of thermo-stabilizer is lower than 0.05%(weight).
13, by the described method of claim 8, the wherein about 0.005%～about 0.03%(weight of the significant quantity of thermo-stabilizer).
14, by the described method of claim 8, wherein said thermo-stabilizer is 1,3,5-trimethylammonium-2,4,6-three (3,5-di-t-butyl-4-acrinyl) benzene.
15, a kind of preparation is heat-staple, and method partial crystallization heat setting type, non-orientation products comprises that step is as follows:
(a) thermo-stabilizer of melt blending significant quantity and the polyolefine of being produced by the alkene that contains 2 to 6 carbon atoms are to form a kind of stable polyolefine;
(b) in dry gas atmosphere and at least 150 ℃ of following heat characteristic viscosity be one enough period of polyethylene terephthalate of about 0.65 to about 1.2, arrive 0.02%(weight with the water content that reduces polyethylene terephthalate) below, thereby the exsiccant polyethylene terephthalate formed;
(c) together send described dried polyethylene terephthalate and described stable polyolefine to one and be used for the melt blending device;
(d) a spot of described stabilization of polyolefins and a large amount of polyethylene terephthalate of doing are mixed to form the melt blending material of uniform hexaneization;
(e) described even melt blending material is made sheet stock;
(f) described unformed sheet stock is put into a mold;
(g) in the thermoplastic mould, one enough period of the described sheet stock of thermoforming, make goods that 15%～35% degree of crystallinity be arranged;
(h) from described thermoplastic mould, take out described goods;
(i) described goods are come out from described finishing.
16, by the described method of claim 15, wherein said polyolefine is a polyethylene.
17, by the described method of claim 15, wherein said polyethylene is a LLDPE.
18, by the described method of claim 15, wherein said polyethylene is a LLDPE, described thermo-stabilizer is a polyphenol, it is selected from 1,3,5-trimethylammonium-2,4,6-three (3,5-di-t-butyl-4-acrinyl) methane benzene, four (methylene radical 3-(3,5-di-t-butyl-4-hydroxyphenyl)-propionic ester).
19, by the described method of claim 15, wherein the thermo-stabilizer significant quantity is lower than 0.05%(weight less).
20, by the described method of claim 15, wherein the thermo-stabilizer significant quantity is 0.005%～0.03%(weight).
21, by the described method of claim 15, wherein said thermo-stabilizer is 1,3,5-trimethylammonium-2,4,6-three (3,5-di-t-butyl-4-acrinyl) benzene.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US71077485A | 1985-03-11 | 1985-03-11 | |
| US710,774 | 1985-03-11 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN86101424A true CN86101424A (en) | 1986-09-17 |
| CN1013450B CN1013450B (en) | 1991-08-07 |
Family
ID=24855475
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN86101424A Expired CN1013450B (en) | 1985-03-11 | 1986-03-11 | Process for the production of articles of fractional crystallised polyester |
Country Status (15)
| Country | Link |
|---|---|
| US (1) | USH2169H1 (en) |
| JP (1) | JPH0651810B2 (en) |
| KR (1) | KR940002281B1 (en) |
| CN (1) | CN1013450B (en) |
| BE (1) | BE904379A (en) |
| BR (1) | BR8600935A (en) |
| CA (1) | CA1266361A (en) |
| DE (1) | DE3607412C2 (en) |
| DK (1) | DK108486A (en) |
| FR (1) | FR2578547B1 (en) |
| GB (1) | GB2172601B (en) |
| IN (1) | IN169503B (en) |
| IT (1) | IT1209973B (en) |
| NL (1) | NL193378C (en) |
| SE (1) | SE468854B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1117122C (en) * | 1998-05-18 | 2003-08-06 | 四川联合大学 | Polyethylene polyethylene terephthalate alloy type single layer separated packaging material |
| CN109196032A (en) * | 2016-05-19 | 2019-01-11 | 卡比奥斯公司 | A kind of method of degradative plastics product |
| CN110229378A (en) * | 2019-05-20 | 2019-09-13 | 安徽东锦资源再生科技有限公司 | A kind of crystallizing and drying technique of Pillar recovery bottle chips |
Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62227947A (en) * | 1986-03-31 | 1987-10-06 | Teijin Ltd | Polyester sheet |
| US4981631A (en) * | 1989-03-31 | 1991-01-01 | The Goodyear Tire & Rubber Company | Process for making lightweight polyester articles |
| JP2615284B2 (en) * | 1991-08-19 | 1997-05-28 | 三菱重工業 株式会社 | Manufacturing method of aluminum composite products |
| DE4201845A1 (en) * | 1992-01-24 | 1993-07-29 | Basf Ag | THERMOPLASTIC RECYCLING MOLDS |
| IL110514A0 (en) * | 1993-10-04 | 1994-10-21 | Eastman Chem Co | Concentrates for improving polyester compositions and a method for preparing such compositions |
| FR2727123A1 (en) * | 1994-11-18 | 1996-05-24 | Rohm & Haas France | REDUCTION OF CHEMICAL DEPOSIT IN MIXTURES OF POLY (ETHYLENETEREPHTHALATE) |
| DE19630599A1 (en) * | 1996-07-31 | 1998-02-05 | Hoechst Ag | Polyethylene terephthalate sheet with improved hydrolysis stability, process for its manufacture and use |
| US6020421A (en) * | 1998-09-01 | 2000-02-01 | Unitika Ltd. | Polyester composition and method for producing the same |
| DE10149474A1 (en) | 2001-10-08 | 2003-04-17 | Buehler Ag | Control of thermoplastic polymer crystallization by moisture level control useful for controlling the crystallization of polyesters, e.g. polyethylene terephthalate, polyethylene napthalate, or polybutyene terephthalate |
| EP1437377B1 (en) | 2001-10-16 | 2007-10-03 | Teijin Limited | Method for recycling pet bottle |
| JP2005307141A (en) * | 2004-03-25 | 2005-11-04 | Nippon Steel Corp | Resin composition for metal coating film excellent in impact resistance and production process therefor |
| US8044169B2 (en) | 2008-03-03 | 2011-10-25 | Grupo Petrotemex, S.A. De C.V. | Dryer configuration for production of polyester particles |
| DK2727724T3 (en) | 2012-10-25 | 2021-03-08 | Buergofol GmbH | SINGLE OR MULTI-LAYER FILM |
| WO2014142887A1 (en) * | 2013-03-14 | 2014-09-18 | Graphic Packaging International, Inc. | Low crystallinity susceptor films |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3644482A (en) * | 1961-10-30 | 1972-02-22 | Geigy Ag J R | (4-hydroxy-5-alkylphenyl) alkanoic acid esters of polyols |
| US3201506A (en) * | 1962-08-09 | 1965-08-17 | Du Pont | Addition of magnesium silicate to a polyester in the manufacture of oriented film |
| US3720732A (en) * | 1968-09-23 | 1973-03-13 | Minnesota Mining & Mfg | Biaxially oriented polycarbonate modified polyester film |
| US3579609A (en) * | 1968-09-23 | 1971-05-18 | Minnesota Mining & Mfg | Flex-resistant polyester film containing olefin or polytetramethylene oxide additive polymer |
| US3627625A (en) * | 1970-05-27 | 1971-12-14 | Ici Ltd | Biaxially oriented sheet |
| GB1411564A (en) * | 1972-04-27 | 1975-10-29 | Impeial Chemical Ind Ltd | Coated polyester films |
| GB1415686A (en) * | 1972-10-24 | 1975-11-26 | Ici Ltd | Voided films |
| JPS4975661A (en) * | 1972-11-24 | 1974-07-22 | ||
| US3987004A (en) * | 1973-04-05 | 1976-10-19 | National Starch And Chemical Corporation | Stabilized polyester compositions |
| US3907926A (en) * | 1973-12-19 | 1975-09-23 | Du Pont | Blends of thermoplastic copolyetherester with poly-butylene terephthalate |
| US4048128A (en) * | 1974-02-20 | 1977-09-13 | E. I. Du Pont De Nemours And Company | Thermally stabilized segmented copolyester adhesive |
| US3975485A (en) * | 1974-07-16 | 1976-08-17 | Allied Chemical Corporation | Production of films and sheets of polyester-polycarbonate blends |
| US3960807A (en) * | 1974-09-30 | 1976-06-01 | Minnesota Mining And Manufacturing Company | Thermoformed polyester articles having impact resistance and high temperature dimensional stability |
| US4070342A (en) * | 1976-12-20 | 1978-01-24 | Allied Chemical Corporation | Manufacture of polyesters |
| JPS5399268A (en) * | 1977-02-12 | 1978-08-30 | Shiyouki Chiyou | Low temperature fabrication process of polyethylene telephthalate |
| JPS55154130A (en) * | 1979-04-27 | 1980-12-01 | Toyobo Co Ltd | Preparation of polyester film |
| US4572852A (en) * | 1982-08-18 | 1986-02-25 | The Goodyear Tire & Rubber Company | Thermoforming partially crystalline polyester articles |
| BR8304203A (en) * | 1982-08-18 | 1984-04-24 | Goodyear Tire & Rubber | PROCESS OF MANUFACTURING ARTICLES MOLDED BY INJECTION, MOLDED ARTICLE PREPARED BY THE PROCESS |
| US4463121A (en) * | 1982-08-18 | 1984-07-31 | The Goodyear Tire & Rubber Company | Thermoforming partially crystalline polyester articles |
| DE3380669D1 (en) * | 1982-12-28 | 1989-11-09 | Gen Electric | Additive concentrate for polyester compositions and method of addition |
-
1986
- 1986-01-07 IN IN21/DEL/86A patent/IN169503B/en unknown
- 1986-02-25 CA CA000502602A patent/CA1266361A/en not_active Expired - Fee Related
- 1986-03-04 BR BR8600935A patent/BR8600935A/en not_active IP Right Cessation
- 1986-03-04 FR FR8602984A patent/FR2578547B1/en not_active Expired
- 1986-03-05 SE SE8601012A patent/SE468854B/en not_active IP Right Cessation
- 1986-03-06 DE DE3607412A patent/DE3607412C2/en not_active Expired - Fee Related
- 1986-03-06 GB GB8605510A patent/GB2172601B/en not_active Expired
- 1986-03-06 IT IT4772386A patent/IT1209973B/en active
- 1986-03-10 KR KR1019860001668A patent/KR940002281B1/en not_active IP Right Cessation
- 1986-03-10 DK DK108486A patent/DK108486A/en unknown
- 1986-03-10 BE BE0/216386A patent/BE904379A/en not_active IP Right Cessation
- 1986-03-11 JP JP5351086A patent/JPH0651810B2/en not_active Expired - Lifetime
- 1986-03-11 NL NL8600635A patent/NL193378C/en not_active IP Right Cessation
- 1986-03-11 CN CN86101424A patent/CN1013450B/en not_active Expired
-
1991
- 1991-04-16 US US07/686,088 patent/USH2169H1/en not_active Abandoned
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1117122C (en) * | 1998-05-18 | 2003-08-06 | 四川联合大学 | Polyethylene polyethylene terephthalate alloy type single layer separated packaging material |
| CN109196032A (en) * | 2016-05-19 | 2019-01-11 | 卡比奥斯公司 | A kind of method of degradative plastics product |
| CN110229378A (en) * | 2019-05-20 | 2019-09-13 | 安徽东锦资源再生科技有限公司 | A kind of crystallizing and drying technique of Pillar recovery bottle chips |
Also Published As
| Publication number | Publication date |
|---|---|
| DE3607412C2 (en) | 1995-04-13 |
| NL8600635A (en) | 1986-10-01 |
| KR860007323A (en) | 1986-10-10 |
| FR2578547B1 (en) | 1988-11-25 |
| SE468854B (en) | 1993-03-29 |
| SE8601012L (en) | 1986-09-12 |
| NL193378B (en) | 1999-04-01 |
| NL193378C (en) | 1999-08-03 |
| IN169503B (en) | 1991-10-26 |
| BR8600935A (en) | 1986-11-11 |
| IT1209973B (en) | 1989-08-30 |
| DE3607412A1 (en) | 1986-09-18 |
| JPH0651810B2 (en) | 1994-07-06 |
| JPS61218638A (en) | 1986-09-29 |
| GB2172601B (en) | 1989-06-14 |
| GB2172601A (en) | 1986-09-24 |
| KR940002281B1 (en) | 1994-03-21 |
| CA1266361A (en) | 1990-03-06 |
| FR2578547A1 (en) | 1986-09-12 |
| DK108486D0 (en) | 1986-03-10 |
| IT8647723A0 (en) | 1986-03-06 |
| SE8601012D0 (en) | 1986-03-05 |
| DK108486A (en) | 1986-09-12 |
| USH2169H1 (en) | 2006-09-05 |
| CN1013450B (en) | 1991-08-07 |
| GB8605510D0 (en) | 1986-04-09 |
| BE904379A (en) | 1986-06-30 |
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Address after: Holland Hague Agency after: Patent and Trademark Office of China Council For The Promotion Of International Trade Agent after: Zhou Zhongqi Applicant after: Shell Internationale Research Maatschappij B. V. Address before: Ohio, USA Agency before: China Patent Agent (H.K.) Ltd. Agent before: Wu Xiaonan Applicant before: Goodyear Tire & Rubber Co. |
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Free format text: CORRECT: APPLICANT; FROM: GOODYEAR TIRE + RUBBER CO. TO: SHELL INTERNATIONALE RESEARCH MAATSCHAPPIJB.V.; AGENCY; FROM: CHINA PATENT AGENT(XIANG GANG)LTD. TO: CCPIT PATENT + TRADEMARK LAW OFFICE; AGENT; FROM: WU XIAONAN TO: ZHOU ZHONGQI |
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