CN114621565B - Processing technology for producing packing belt from nano modified PET bottle reclaimed materials - Google Patents
Processing technology for producing packing belt from nano modified PET bottle reclaimed materials Download PDFInfo
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- CN114621565B CN114621565B CN202210329016.1A CN202210329016A CN114621565B CN 114621565 B CN114621565 B CN 114621565B CN 202210329016 A CN202210329016 A CN 202210329016A CN 114621565 B CN114621565 B CN 114621565B
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- pet bottle
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- titanium silicate
- silicon dioxide
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- 239000000463 material Substances 0.000 title claims abstract description 57
- 238000012856 packing Methods 0.000 title claims abstract description 40
- 238000005516 engineering process Methods 0.000 title claims abstract description 13
- 238000012545 processing Methods 0.000 title claims abstract description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 177
- QAIPRVGONGVQAS-DUXPYHPUSA-N trans-caffeic acid Chemical compound OC(=O)\C=C\C1=CC=C(O)C(O)=C1 QAIPRVGONGVQAS-DUXPYHPUSA-N 0.000 claims abstract description 86
- GNKTZDSRQHMHLZ-UHFFFAOYSA-N [Si].[Si].[Si].[Ti].[Ti].[Ti].[Ti].[Ti] Chemical compound [Si].[Si].[Si].[Ti].[Ti].[Ti].[Ti].[Ti] GNKTZDSRQHMHLZ-UHFFFAOYSA-N 0.000 claims abstract description 78
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 74
- 239000004005 microsphere Substances 0.000 claims abstract description 60
- 239000002131 composite material Substances 0.000 claims abstract description 58
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 57
- 229940074360 caffeic acid Drugs 0.000 claims abstract description 50
- 239000002245 particle Substances 0.000 claims abstract description 44
- 238000002156 mixing Methods 0.000 claims abstract description 41
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 32
- 230000008929 regeneration Effects 0.000 claims abstract description 17
- 238000011069 regeneration method Methods 0.000 claims abstract description 17
- 238000001816 cooling Methods 0.000 claims abstract description 12
- 238000007493 shaping process Methods 0.000 claims abstract description 9
- 238000001125 extrusion Methods 0.000 claims abstract description 6
- 238000002844 melting Methods 0.000 claims abstract description 6
- 230000008018 melting Effects 0.000 claims abstract description 6
- 238000005096 rolling process Methods 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 106
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 70
- 238000003756 stirring Methods 0.000 claims description 53
- ACEAELOMUCBPJP-UHFFFAOYSA-N (E)-3,4,5-trihydroxycinnamic acid Natural products OC(=O)C=CC1=CC(O)=C(O)C(O)=C1 ACEAELOMUCBPJP-UHFFFAOYSA-N 0.000 claims description 36
- 235000004883 caffeic acid Nutrition 0.000 claims description 36
- QAIPRVGONGVQAS-UHFFFAOYSA-N cis-caffeic acid Natural products OC(=O)C=CC1=CC=C(O)C(O)=C1 QAIPRVGONGVQAS-UHFFFAOYSA-N 0.000 claims description 36
- 238000001035 drying Methods 0.000 claims description 26
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 25
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 25
- 238000001914 filtration Methods 0.000 claims description 23
- 238000005406 washing Methods 0.000 claims description 21
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 claims description 21
- QKNYBSVHEMOAJP-UHFFFAOYSA-N 2-amino-2-(hydroxymethyl)propane-1,3-diol;hydron;chloride Chemical compound Cl.OCC(N)(CO)CO QKNYBSVHEMOAJP-UHFFFAOYSA-N 0.000 claims description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- 239000007853 buffer solution Substances 0.000 claims description 20
- 238000004140 cleaning Methods 0.000 claims description 20
- 235000019441 ethanol Nutrition 0.000 claims description 20
- 238000010438 heat treatment Methods 0.000 claims description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 17
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 15
- 239000012153 distilled water Substances 0.000 claims description 15
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 15
- 239000011259 mixed solution Substances 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 15
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 12
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 10
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 10
- 239000002202 Polyethylene glycol Substances 0.000 claims description 10
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 10
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 10
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 10
- 229910017604 nitric acid Inorganic materials 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 229920001223 polyethylene glycol Polymers 0.000 claims description 10
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 10
- 238000004806 packaging method and process Methods 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 7
- 239000012634 fragment Substances 0.000 claims description 6
- 230000032683 aging Effects 0.000 claims description 5
- 239000011248 coating agent Substances 0.000 claims description 5
- 238000000576 coating method Methods 0.000 claims description 5
- 229960003280 cupric chloride Drugs 0.000 claims description 5
- 239000005457 ice water Substances 0.000 claims description 5
- 230000007935 neutral effect Effects 0.000 claims description 5
- 239000002244 precipitate Substances 0.000 claims description 5
- 238000007789 sealing Methods 0.000 claims description 5
- 238000010008 shearing Methods 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- 238000004321 preservation Methods 0.000 claims description 4
- 238000012650 click reaction Methods 0.000 claims description 3
- QDXBVEACAWKSFL-UHFFFAOYSA-N ethenethiol Chemical group SC=C QDXBVEACAWKSFL-UHFFFAOYSA-N 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 2
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical compound [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 claims description 2
- 238000004064 recycling Methods 0.000 abstract description 16
- 239000002699 waste material Substances 0.000 abstract description 13
- 229920003023 plastic Polymers 0.000 abstract description 12
- 239000004033 plastic Substances 0.000 abstract description 12
- 230000007547 defect Effects 0.000 abstract description 4
- 229920000139 polyethylene terephthalate Polymers 0.000 description 69
- 239000005020 polyethylene terephthalate Substances 0.000 description 69
- 239000003513 alkali Substances 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 235000013361 beverage Nutrition 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- -1 Polyethylene terephthalate Polymers 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 238000001514 detection method Methods 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 229920001225 polyester resin Polymers 0.000 description 3
- 239000004645 polyester resin Substances 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000010292 electrical insulation Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 238000005554 pickling Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
- 239000004416 thermosoftening plastic Substances 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 1
- 235000021059 hard food Nutrition 0.000 description 1
- 229920001903 high density polyethylene Polymers 0.000 description 1
- 239000004700 high-density polyethylene Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
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- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/10—Encapsulated ingredients
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/001—Combinations of extrusion moulding with other shaping operations
- B29C48/0018—Combinations of extrusion moulding with other shaping operations combined with shaping by orienting, stretching or shrinking, e.g. film blowing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/022—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the choice of material
- B29C48/023—Extruding materials comprising incompatible ingredients
-
- 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
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
- C08K7/26—Silicon- containing compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/0081—Composite particulate pigments or fillers, i.e. containing at least two solid phases, except those consisting of coated particles of one compound
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/28—Compounds of silicon
- C09C1/30—Silicic acid
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/28—Compounds of silicon
- C09C1/30—Silicic acid
- C09C1/3045—Treatment with inorganic compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/28—Compounds of silicon
- C09C1/30—Silicic acid
- C09C1/3072—Treatment with macro-molecular organic compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/28—Compounds of silicon
- C09C1/30—Silicic acid
- C09C1/309—Combinations of treatments provided for in groups C09C1/3009 - C09C1/3081
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/36—Compounds of titanium
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/36—Compounds of titanium
- C09C1/3607—Titanium dioxide
- C09C1/3653—Treatment with inorganic compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/36—Compounds of titanium
- C09C1/3607—Titanium dioxide
- C09C1/3676—Treatment with macro-molecular organic compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/36—Compounds of titanium
- C09C1/3692—Combinations of treatments provided for in groups C09C1/3615 - C09C1/3684
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/006—Combinations of treatments provided for in groups C09C3/04 - C09C3/12
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/06—Treatment with inorganic compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/10—Treatment with macromolecular organic compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
- B29L2029/00—Belts or bands
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Composite Materials (AREA)
- Silicon Compounds (AREA)
Abstract
The invention discloses a processing technology for producing packing belts from nano modified PET bottle reclaimed materials, which comprises the following steps: step 1, preparing a poly-caffeic acid coated porous titanium silicate/silicon dioxide composite microsphere; step 2, melting and granulating the PET bottle to obtain PET bottle reclaimed material particles; step 3, fully mixing the PET bottle regeneration material particles with the poly-caffeic acid coated porous titanium silicate/silicon dioxide composite microspheres; step 4, melt extrusion is carried out to obtain a strip-shaped packing strip blank; and 5, rapidly cooling through a cold water tank, then carrying out preheating treatment, and then carrying out stretching, shaping and rolling to obtain the nano modified PET bottle reclaimed material for producing the packing belt. The invention not only completes the recycling of the waste materials, but also overcomes the defects of the waste materials, improves the recycling performance of the waste materials, exploits the application field of proper marketing to roads, ensures the quality of regenerated plastic products, and finally completes the 'green' concept of recycling the waste plastics.
Description
Technical Field
The invention belongs to the field of PET materials, and particularly relates to a processing technology for producing packing belts from nano modified PET bottle reclaimed materials.
Background
PET (Polyethylene terephthalate), polyethylene terephthalate, commonly known as polyester resin, is the most important species in thermoplastic polyesters. The Chinese name of PET is poly (p-benzoate), which is a polyester resin, and is commonly called thermoplastic polyester with PBT. The PET plastic has a highly symmetrical molecular structure and a certain crystallization orientation capability, so that the PET plastic has higher film forming property and formability. The PET plastic has good optical property and weather resistance, and the amorphous PET plastic has good optical transparency. In addition, the PET plastic has excellent wear resistance, friction resistance, dimensional stability and electrical insulation. The PET bottle has the advantages of high strength, good transparency, no toxicity, permeation resistance, light weight, high production efficiency and the like, and is widely applied, thus being the most commonly used plastic in beverage and hard food packaging. About 2,700 ten thousand tons of PET are used worldwide, most of which are used to make bottles.
PET is an environment-friendly material which can be recycled and reused by 100 percent, and the physical recycling method is relatively simple, and mainly comprises the steps of drying and granulating the clean waste PET plastic bottle. Cutting waste into pieces, separating HDPE, aluminum, paper and binder from PET, washing the PET pieces, drying, granulating, or depolymerizing the waste PRT plastic bottle under certain reaction conditions to form useful chemicals. For the green recycling economy, recycling and utilization of high-value resin PET are increasingly important, such as PET strapping bands and the like. However, the performance of the recycled PET is reduced compared to virgin PET, and the defect of the PET material itself results in a lower performance of the resulting strapping tape, which also becomes a bottleneck in the production of PET strapping tape.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a processing technology for producing packing belts from nano modified PET bottle reclaimed materials with low energy consumption and strong reproducibility.
The aim of the invention is realized by adopting the following technical scheme:
a processing technology for producing packing belts from nano modified PET bottle reclaimed materials comprises the following steps:
step 1, preparing nano activated silica by utilizing vinyl silane through a mercapto-ethylene click reaction, then compositing titanium silicate and the nano activated silica to form porous titanium silicate/silica composite microspheres, and then performing coating treatment of caffeic acid to obtain the caffeic acid coated porous titanium silicate/silica composite microspheres;
step 2, shearing the PET bottle into pieces, sequentially cleaning and drying, then extruding and granulating after melting in a screw extruder, and crushing by using airflow impact to obtain PET bottle reclaimed material particles;
step 3, mixing PET bottle regeneration material particles and the poly caffeic acid coated porous titanium silicate/silicon dioxide composite microspheres in a stirrer, and fully mixing under the protection of nitrogen to form a regeneration mixture;
step 4, placing the regenerated mixture into a screw extruder, and performing melt extrusion in the screw extruder to obtain a strip-shaped packing strip body;
and 5, rapidly cooling the banded packing belt blank through a cold water tank, then placing the banded packing belt blank in an oven for preheating treatment, and then stretching, shaping and rolling to obtain the nano modified PET bottle reclaimed materials for producing packing belts.
Preferably, in the step 1, the preparation process of the nanoscale activated silica specifically includes:
(1) Sequentially adding vinyltriethoxysilane and sodium dodecyl benzene sulfonate into distilled water, stirring for 1-2 h at the speed of 400-600 rpm, then dropwise adding ammonia water, heating to 45-55 ℃ at the same time, stirring for 36-48 h at the speed of 200-300 rpm, filtering, cleaning, drying and crushing to obtain nano-scale vinylated silicon dioxide;
wherein, the mass ratio of the vinyl triethoxysilane, the sodium dodecyl benzene sulfonate and the distilled water is 1.8-2.0:0.02-0.04:20-30, the concentration of the ammonia water is 25%, and the mass ratio of the ammonia water and the vinyl triethoxysilane is 1:4-6;
(2) Sequentially adding nano-grade vinylated silicon dioxide, azodiisobutyronitrile and 2-mercaptoethanol into absolute ethyl alcohol, heating to 70-80 ℃ under the protection of nitrogen, stirring for 18-24 h at the speed of 200-300 rpm, filtering, cleaning and drying to obtain nano-grade activated silicon dioxide;
wherein the mass ratio of the nano-grade vinylated silicon dioxide, the azodiisobutyronitrile, the 2-mercaptoethanol and the absolute ethanol is 1:0.4-0.6:1.6-1.8:10-15.
Preferably, in the step 1, the preparation process of the porous titanium silicate/silicon dioxide composite microsphere specifically comprises the following steps:
(1) Mixing tetraethoxysilane and ethanol to form a solution A, mixing tetrabutyl titanate and ethanol to form a solution B, dropwise adding a 0.05mol/L nitric acid solution into the solution A, stirring for 0.5-1 h under ice water bath, continuously dropwise adding the solution B into the mixed solution, heating to 40-50 ℃, stirring for 1-2 h, dropwise adding polyethylene glycol into the mixed solution again, keeping the temperature and stirring for 0.5-1 h, cooling to room temperature, and sealing and aging for at least 5 days at room temperature to obtain titanium silicate sol;
wherein the mass ratio of the tetraethoxysilane to the ethanol in the solution A is 3-5:10, the mass ratio of the tetrabutyl titanate to the ethanol in the solution B is 3-5:10, and the mass ratio of the nitric acid solution, the polyethylene glycol, the solution A and the solution B is 1.56-1.88:0.04-0.06:7-8:1;
(2) Mixing nano-scale activated silica with titanium silicate sol, stirring at a speed of 400-600 rpm, simultaneously dropwise adding ammonia water until the pH value of the mixed solution is 8.0-9.0, stopping dropwise adding ammonia water, continuously stirring for 0.5-1 h, standing for 0.5h, filtering out precipitate, washing with hot water at 80-100 ℃ until the pH value of the washing solution is 7, vacuum drying, and crushing to obtain porous titanium silicate/silica composite microspheres;
wherein the mass ratio of the nano-scale activated silica to the titanium silicate sol is 1:10-20.
Preferably, in the step 1, the process of coating treatment of the caffeic acid specifically includes:
mixing caffeic acid with Tris-HCl buffer solution with pH of 8.2 and concentration of 1g/L, and stirring at room temperature to obtain solution C; copper chloride is mixed with Tris-HCl buffer solution with pH of 8.2 and concentration of 1g/L, and stirred uniformly at room temperature to obtain solution D; mixing the solution C with the solution D, adding porous titanium silicate/silicon dioxide composite microspheres, then dropwise adding hydrogen peroxide solution with the mass fraction of 20% -40%, stirring for 0.5-1 h at room temperature, and sequentially filtering, cleaning, drying and crushing to obtain the caffeic acid coated porous titanium silicate/silicon dioxide composite microspheres;
wherein, the mass ratio of the caffeic acid in the solution C to the Tris-HCl buffer solution is 1-3:10-15, the mass ratio of the cupric chloride in the solution D to the Tris-HCl buffer solution is 0.6-1.2:10-15, and the mass ratio of the porous titanium silicate/silicon dioxide composite microsphere, the hydrogen peroxide solution and the solution C to the solution D is 1:0.02-0.06:10-20:10-20.
Preferably, in the step 1, the particle size of the nano-scale activated silica is 300-500 nm, the particle size of the porous titanium silicate/silica composite microsphere is 5-10 μm, and the particle size of the caffeic acid coated porous titanium silicate/silica composite microsphere is 10-20 μm.
Preferably, in the step 2, the PET bottle is obtained by recycling a transparent PET beverage bottle commercially available, and has been subjected to label removal, bottle cap removal and surface impurity removal.
Preferably, in the step 2, the PET bottle fragments are firstly placed in a sodium hydroxide solution with the concentration of 0.05mol/L, heated and stirred for 0.5-1 h, the PET bottle fragments are filtered out, and then distilled water is used for washing until the pH of the washing liquid is neutral.
Preferably, in the step 2, the temperature of the screw extruder is 285 to 295 ℃.
Preferably, in the step 2, the drying temperature is 110-120 ℃ and the drying time is 2-4 h.
Preferably, in the step 2, the particle size of the PET bottle reclaimed material particles is 50-100 μm.
Preferably, in the step 3, the temperature of the stirrer is 150-170 ℃, the rotation speed is 50-100 rpm, and the mixing time is 0.5-1 h.
Preferably, in the step 3, the mass ratio of the PET bottle regeneration material particles to the poly caffeic acid coated porous titanium silicate/silicon dioxide composite microspheres is 10-15:1.
Preferably, in the step 4, the screw extruder is six-stage temperature controlled heating, including: the first stage temperature is 185-195 ℃, the second stage temperature is 200-210 ℃, the third stage temperature is 220-230 ℃, the fourth stage temperature is 240-255 ℃, the fifth stage temperature is 260-280 ℃, and the sixth stage temperature is 285-295 ℃.
Preferably, in the step 5, the temperature of the cold water tank is 10-15 ℃ and the treatment time is 5-10 s; the temperature of the oven is 170-180 ℃ and the treatment time is 10-15 s; the stretching temperature is 80-90 ℃ and the stretching multiple is 2.7-3.8 times; the setting temperature is 110-120 ℃, the treatment time is 20-40 s, and then the mixture is naturally cooled to room temperature.
The beneficial effects of the invention are as follows:
(1) According to the invention, the recycled waste PET bottles are used as raw materials, and after the waste PET bottles are melted and granulated into recycled material particles, the recycled material particles are subjected to composite modification by adding the poly-caffeic acid coated porous titanium silicate/silicon dioxide composite microspheres to obtain a recycled mixture, so that the recycling performance of the PET recycled material is improved, the mechanical strength is improved, the defects of hot water soaking intolerance and alkali intolerance are overcome, and then the nano modified PET bottle recycled material is extruded by a screw extruder to obtain the packing belt. The invention not only completes the recycling of the waste materials, but also overcomes the defects of the waste materials, improves the recycling performance of the waste materials, exploits the application field of proper marketing to roads, ensures the quality of regenerated plastic products, and finally completes the 'green' concept of recycling the waste plastics.
(2) In order to improve the performance of the PET reclaimed material, the invention adds the poly-caffeic acid coated porous titanium silicate/silicon dioxide composite microsphere in the recycling process of the PET reclaimed material. The preparation process of the caffeic acid coated porous titanium silicate/silicon dioxide composite microsphere comprises three processes: firstly, preparing nano-scale activated silica, compared with the conventional preparation method, the preparation method utilizes the click reaction of mercapto-ethylene to prepare vinyl silica, and then the vinyl silica reacts with mercaptoethanol, so that the activated silica has higher surface activity and stronger crosslinking property; preparing titanium silicate sol and compositing the titanium silicate sol with nano-scale activated silica to form porous microspheres, wherein the porous of the process is a large number of gaps generated by volatilizing a solvent of the titanium silicate sol in the curing process; and thirdly, coating the microspheres with caffeic acid, wherein the caffeic acid is obtained by in-situ oxidative polymerization of caffeic acid on the surfaces of the microspheres under the initiation of copper ions and hydrogen peroxide.
(3) The process is simple and convenient to operate, and the nano modified PET bottle reclaimed material prepared from the reclaimed PET material has the advantages of high tensile strength, good toughness and high temperature resistance, also has the advantage of acid and alkali resistance, and can be used as a packing belt material in various severe environments. The packaging belt prepared by the invention has recycling value, and the added modified components are components which are pollution-free to the environment, so that the sustainable development strategy of environmental protection and resource regeneration is promoted.
Detailed Description
The technical features, objects and advantages of the present invention will be more clearly understood from the following detailed description of the technical aspects of the present invention, but should not be construed as limiting the scope of the invention.
PET material, commonly called polyester resin, belongs to crystalline saturated polyester, is a milky or pale yellow and highly crystalline polymer, has smooth and glossy surface, and has good creep resistance, fatigue resistance, abrasion resistance and dimensional stability; the electrical insulation performance is good; weak acid and organic solvent resistance, but insufficient heat resistance and alkali resistance.
The invention is further described with reference to the following examples.
Example 1
A processing technology for producing packing belts from nano modified PET bottle reclaimed materials comprises the following steps:
step 1, preparing a poly caffeic acid coated porous titanium silicate/silicon dioxide composite microsphere:
s1, preparing nanoscale activated silicon dioxide:
(1) Sequentially adding vinyl triethoxysilane and sodium dodecyl benzene sulfonate into distilled water, stirring for 1h at the speed of 500rpm, then adding ammonia water dropwise, heating to 50 ℃, stirring for 36-48 h at the speed of 250rpm, filtering, cleaning, drying and crushing to obtain nanoscale vinylated silicon dioxide;
wherein, the mass ratio of vinyl triethoxysilane, sodium dodecyl benzene sulfonate and distilled water is 1.8:0.03:25, the concentration of ammonia water is 25%, and the mass ratio of ammonia water and vinyl triethoxysilane is 1:5;
(2) Sequentially adding nano-grade vinylated silicon dioxide, azodiisobutyronitrile and 2-mercaptoethanol into absolute ethyl alcohol, heating to 75 ℃ under the protection of nitrogen, stirring for 20 hours at the speed of 250rpm, filtering, cleaning, drying and crushing to obtain nano-grade activated silicon dioxide with the particle size of 300-500 nm;
wherein the mass ratio of the nano-grade vinylated silicon dioxide, the azodiisobutyronitrile and the 2-mercaptoethanol to the absolute ethyl alcohol is 1:0.5:1.7:10.
S2, preparing porous titanium silicate/silicon dioxide composite microspheres:
(1) Mixing tetraethoxysilane with ethanol to form a solution A, mixing tetrabutyl titanate with ethanol to form a solution B, dropwise adding a 0.05mol/L nitric acid solution into the solution A, stirring for 0.5h under ice water bath, continuously dropwise adding the solution B into the mixed solution, heating to 40 ℃, stirring for 1h, dropwise adding polyethylene glycol into the mixed solution again, stirring for 0.5h under heat preservation, cooling to room temperature, and sealing and ageing at room temperature for at least 5 days to obtain titanium silicate sol;
wherein the mass ratio of the tetraethoxysilane to the ethanol in the solution A is 4:10, the mass ratio of the tetrabutyl titanate to the ethanol in the solution B is 4:10, and the mass ratio of the nitric acid solution, the polyethylene glycol, the solution A and the solution B is 1.72:0.05:7.5:1;
(2) Mixing nano-scale activated silica with titanium silicate sol, stirring at a speed of 500rpm, simultaneously dropwise adding ammonia water until the pH value of the mixed solution is 8.0-9.0, stopping dropwise adding ammonia water, continuously stirring for 0.5h, standing for 0.5h, filtering out precipitate, washing with hot water at 80-100 ℃ until the pH value of the washing solution is 7, vacuum drying, and crushing to obtain porous titanium silicate/silica composite microspheres with a particle size of 5-10 mu m;
wherein the mass ratio of the nano-scale activated silica to the titanium silicate sol is 1:15.
S3, preparing a caffeic acid coated porous titanium silicate/silicon dioxide composite microsphere:
mixing caffeic acid with Tris-HCl buffer solution with pH of 8.2 and concentration of 1g/L, and stirring at room temperature to obtain solution C; copper chloride is mixed with Tris-HCl buffer solution with pH of 8.2 and concentration of 1g/L, and stirred uniformly at room temperature to obtain solution D; mixing the solution C with the solution D, adding porous titanium silicate/silicon dioxide composite microspheres, then dropwise adding 30% hydrogen peroxide solution, stirring for 1h at room temperature, and sequentially filtering, cleaning, drying and crushing to obtain the poly caffeic acid coated porous titanium silicate/silicon dioxide composite microspheres with the particle size of 10-20 mu m;
wherein, the mass ratio of caffeic acid to Tris-HCl buffer solution in the solution C is 2:12, the mass ratio of cupric chloride to Tris-HCl buffer solution in the solution D is 1:12, and the mass ratio of porous titanium silicate/silicon dioxide composite microsphere, hydrogen peroxide solution and solution C to solution D is 1:0.04:15:15.
Step 2, recycling a commercially available transparent PET beverage bottle, removing labels, removing bottle caps and removing surface impurities, shearing the treated PET bottle into pieces, cleaning in a sodium hydroxide solution with the concentration of 0.05mol/L, heating and stirring for 0.5h, filtering out PET bottle fragments, washing with distilled water until the pH of a washing solution is neutral, drying at 110 ℃ for 3h, melting in a screw extruder with the temperature of 290 ℃, extruding and granulating, and crushing by using airflow impact to obtain PET bottle reclaimed material particles with the particle size of 50-100 mu m;
step 3, mixing PET bottle regeneration material particles with the poly-caffeic acid coated porous titanium silicate/silicon dioxide composite microspheres, wherein the mass ratio of the PET bottle regeneration material particles to the poly-caffeic acid coated porous titanium silicate/silicon dioxide composite microspheres is 12:1, and mixing for 0.5h in a stirrer with the temperature of 160 ℃ and the rotation speed of 50-100 rpm, and fully mixing to form a regeneration mixture under the protection of nitrogen;
step 4, placing the regenerated mixture into a screw extruder, wherein the screw extruder is heated by six sections of temperature control, and the step comprises the following steps: the first stage temperature is 190 ℃, the second stage temperature is 205 ℃, the third stage temperature is 225 ℃, the fourth stage temperature is 250 ℃, the fifth stage temperature is 270 ℃, and the sixth stage temperature is 290 ℃, and the melt extrusion is carried out to obtain a strip-shaped packing strip body;
step 5, rapidly cooling the banded packing belt blank through a cold water tank, wherein the temperature of the cold water tank is 10 ℃, the treatment time is 10s, then placing the banded packing belt blank in an oven for preheating treatment, the temperature of the oven is 170 ℃, the treatment time is 10s, and then stretching, shaping and rolling, wherein the stretching temperature is 80 ℃, and the stretching multiple is 3.2 times; the shaping temperature is 110 ℃, the treatment time is 30s, and then the mixture is naturally cooled to room temperature, so that the nano modified PET bottle reclaimed material is obtained to produce the packing belt.
Example 2
A processing technology for producing packing belts from nano modified PET bottle reclaimed materials comprises the following steps:
step 1, preparing a poly caffeic acid coated porous titanium silicate/silicon dioxide composite microsphere:
s1, preparing nanoscale activated silicon dioxide:
(1) Sequentially adding vinyltriethoxysilane and sodium dodecyl benzene sulfonate into distilled water, stirring for 1h at the speed of 400rpm, then adding ammonia water dropwise, heating to 45 ℃, stirring for 36h at the speed of 200rpm, filtering, cleaning, drying and crushing to obtain nanoscale vinylated silicon dioxide;
wherein, the mass ratio of the vinyl triethoxysilane, the sodium dodecyl benzene sulfonate and the distilled water is 1.8:0.02:20, the concentration of the ammonia water is 25%, and the mass ratio of the ammonia water to the vinyl triethoxysilane is 1:4;
(2) Sequentially adding nano-grade vinylated silicon dioxide, azodiisobutyronitrile and 2-mercaptoethanol into absolute ethyl alcohol, heating to 70 ℃ under the protection of nitrogen, stirring for 18h under the speed condition of 200rpm, filtering, cleaning, drying and crushing to obtain nano-grade activated silicon dioxide with the particle size of 300-500 nm;
wherein the mass ratio of the nano-grade vinylated silicon dioxide, the azodiisobutyronitrile and the 2-mercaptoethanol to the absolute ethyl alcohol is 1:0.4:1.6:10.
S2, preparing porous titanium silicate/silicon dioxide composite microspheres:
(1) Mixing tetraethoxysilane with ethanol to form a solution A, mixing tetrabutyl titanate with ethanol to form a solution B, dropwise adding a 0.05mol/L nitric acid solution into the solution A, stirring for 0.5h under ice water bath, continuously dropwise adding the solution B into the mixed solution, heating to 40 ℃, stirring for 1h, dropwise adding polyethylene glycol into the mixed solution again, stirring for 0.5h under heat preservation, cooling to room temperature, and sealing and ageing at room temperature for at least 5 days to obtain titanium silicate sol;
wherein the mass ratio of the tetraethoxysilane to the ethanol in the solution A is 3:10, the mass ratio of the tetrabutyl titanate to the ethanol in the solution B is 3:10, and the mass ratio of the nitric acid solution, the polyethylene glycol, the solution A and the solution B is 1.56:0.04:7:1;
(2) Mixing nano-scale activated silica with titanium silicate sol, stirring at a speed of 400-600 rpm, simultaneously dropwise adding ammonia water until the pH value of the mixed solution is 8.0-9.0, stopping dropwise adding ammonia water, continuously stirring for 1h, standing for 0.5h, filtering out precipitate, washing with hot water at 80-100 ℃ until the pH value of the washing solution is 7, vacuum drying, and crushing to obtain porous titanium silicate/silica composite microspheres with a particle size of 5-10 mu m;
wherein the mass ratio of the nano-scale activated silica to the titanium silicate sol is 1:10.
S3, preparing a caffeic acid coated porous titanium silicate/silicon dioxide composite microsphere:
mixing caffeic acid with Tris-HCl buffer solution with pH of 8.2 and concentration of 1g/L, and stirring at room temperature to obtain solution C; copper chloride is mixed with Tris-HCl buffer solution with pH of 8.2 and concentration of 1g/L, and stirred uniformly at room temperature to obtain solution D; mixing the solution C with the solution D, adding porous titanium silicate/silicon dioxide composite microspheres, then dropwise adding a hydrogen peroxide solution with the mass fraction of 20%, stirring for 0.5h at room temperature, and sequentially filtering, cleaning, drying and crushing to obtain the caffeic acid coated porous titanium silicate/silicon dioxide composite microspheres with the particle size of 10-20 mu m;
wherein, the mass ratio of caffeic acid to Tris-HCl buffer solution in the solution C is 1:10, the mass ratio of cupric chloride to Tris-HCl buffer solution in the solution D is 0.6:10, and the mass ratio of porous titanium silicate/silicon dioxide composite microsphere, hydrogen peroxide solution and the mass ratio of the solution C to the solution D is 1:0.02:10:10.
Step 2, recycling a commercially available transparent PET beverage bottle, removing labels, removing bottle caps and removing surface impurities, shearing the treated PET bottle into pieces, placing the pieces in a sodium hydroxide solution with the concentration of 0.05mol/L for cleaning, heating and stirring for 0.5h, filtering out PET bottle fragments, washing with distilled water until the pH of a washing solution is neutral, drying for 2h at 110 ℃, melting in a screw extruder with the temperature of 285 ℃, extruding and granulating, and crushing by using airflow impact to obtain PET bottle reclaimed material particles with the particle size of 50-100 mu m;
step 3, mixing PET bottle regeneration material particles with the poly-caffeic acid coated porous titanium silicate/silicon dioxide composite microspheres, wherein the mass ratio of the PET bottle regeneration material particles to the poly-caffeic acid coated porous titanium silicate/silicon dioxide composite microspheres is 10:1, mixing for 0.5h in a stirrer with the temperature of 150 ℃ and the rotation speed of 50rpm, and fully mixing to form a regeneration mixture under the protection of nitrogen;
step 4, placing the regenerated mixture into a screw extruder, wherein the screw extruder is heated by six sections of temperature control, and the step comprises the following steps: the first stage temperature is 185 ℃, the second stage temperature is 200 ℃, the third stage temperature is 220 ℃, the fourth stage temperature is 240 ℃, the fifth stage temperature is 260 ℃, the sixth stage temperature is 285 ℃, and the melt extrusion is carried out to obtain a strip-shaped packing strip body;
step 5, rapidly cooling the banded packing belt blank through a cold water tank, wherein the temperature of the cold water tank is 10 ℃, the treatment time is 5s, then placing the banded packing belt blank in an oven for preheating treatment, the temperature of the oven is 170 ℃, the treatment time is 10s, and then stretching, shaping and rolling, wherein the stretching temperature is 80 ℃, and the stretching multiple is 2.7 times; the shaping temperature is 110 ℃, the treatment time is 20s, and then the mixture is naturally cooled to room temperature, so that the nano modified PET bottle reclaimed material is obtained to produce the packing belt.
Example 3
A processing technology for producing packing belts from nano modified PET bottle reclaimed materials comprises the following steps:
step 1, preparing a poly caffeic acid coated porous titanium silicate/silicon dioxide composite microsphere:
s1, preparing nanoscale activated silicon dioxide:
(1) Sequentially adding vinyltriethoxysilane and sodium dodecyl benzene sulfonate into distilled water, stirring for 2 hours at the speed of 600rpm, then adding ammonia water dropwise, heating to 55 ℃, stirring for 48 hours at the speed of 300rpm, filtering, cleaning, drying and crushing to obtain nanoscale vinylated silicon dioxide;
wherein, the mass ratio of the vinyl triethoxysilane, the sodium dodecyl benzene sulfonate and the distilled water is 2.0:0.04:30, the concentration of the ammonia water is 25%, and the mass ratio of the ammonia water to the vinyl triethoxysilane is 1:6;
(2) Sequentially adding nano-grade vinylated silicon dioxide, azodiisobutyronitrile and 2-mercaptoethanol into absolute ethyl alcohol, heating to 80 ℃ under the protection of nitrogen, stirring for 24 hours at the speed of 300rpm, filtering, cleaning, drying and crushing to obtain nano-grade activated silicon dioxide with the particle size of 500 nm;
wherein the mass ratio of the nano-grade vinylated silicon dioxide, the azodiisobutyronitrile and the 2-mercaptoethanol to the absolute ethyl alcohol is 1:0.6:1.8:15.
S2, preparing porous titanium silicate/silicon dioxide composite microspheres:
(1) Mixing tetraethoxysilane with ethanol to form a solution A, mixing tetrabutyl titanate with ethanol to form a solution B, dropwise adding a 0.05mol/L nitric acid solution into the solution A, stirring for 1h under ice water bath, continuously dropwise adding the solution B into the mixed solution, heating to 50 ℃, stirring for 2h, dropwise adding polyethylene glycol into the mixed solution again, stirring for 1h under heat preservation, cooling to room temperature, and sealing and ageing at room temperature for at least 5 days to obtain titanium silicate sol;
wherein the mass ratio of the tetraethoxysilane to the ethanol in the solution A is 3-5:10, the mass ratio of the tetrabutyl titanate to the ethanol in the solution B is 5:10, and the mass ratio of the nitric acid solution, the polyethylene glycol, the solution A and the solution B is 1.88:0.06:8:1;
(2) Mixing nano-scale activated silica with titanium silicate sol, stirring at a speed of 600rpm, simultaneously dropwise adding ammonia water until the pH value of the mixed solution is 8.0-9.0, stopping dropwise adding ammonia water, continuously stirring for 1h, standing for 0.5h, filtering out precipitate, washing with hot water at 80-100 ℃ until the pH value of the washing solution is 7, vacuum drying, and crushing to obtain porous titanium silicate/silica composite microspheres with a particle size of 5-10 mu m;
wherein the mass ratio of the nano-scale activated silica to the titanium silicate sol is 1:20.
S3, preparing a caffeic acid coated porous titanium silicate/silicon dioxide composite microsphere:
mixing caffeic acid with Tris-HCl buffer solution with pH of 8.2 and concentration of 1g/L, and stirring at room temperature to obtain solution C; copper chloride is mixed with Tris-HCl buffer solution with pH of 8.2 and concentration of 1g/L, and stirred uniformly at room temperature to obtain solution D; mixing the solution C with the solution D, adding porous titanium silicate/silicon dioxide composite microspheres, then dropwise adding 40% hydrogen peroxide solution, stirring for 1h at room temperature, and sequentially filtering, cleaning, drying and crushing to obtain the poly caffeic acid coated porous titanium silicate/silicon dioxide composite microspheres with the particle size of 10-20 mu m;
wherein, the mass ratio of caffeic acid to Tris-HCl buffer solution in the solution C is 3:15, the mass ratio of cupric chloride to Tris-HCl buffer solution in the solution D is 1.2:15, and the mass ratio of porous titanium silicate/silicon dioxide composite microsphere, hydrogen peroxide solution and solution C to solution D is 1:0.06:20:20.
Step 2, recycling a commercially available transparent PET beverage bottle, removing labels, removing bottle caps and removing surface impurities, shearing the treated PET bottle into pieces, cleaning in a sodium hydroxide solution with the concentration of 0.05mol/L, heating and stirring for 1h, filtering out PET bottle pieces, washing with distilled water until the pH of a washing solution is neutral, drying for 4h at 120 ℃, melting in a screw extruder with the temperature of 295 ℃, extruding and granulating, and performing impact crushing with air flow to obtain PET bottle reclaimed material particles with the particle size of 50-100 mu m;
step 3, mixing PET bottle regeneration material particles with the poly-caffeic acid coated porous titanium silicate/silicon dioxide composite microspheres, wherein the mass ratio of the PET bottle regeneration material particles to the poly-caffeic acid coated porous titanium silicate/silicon dioxide composite microspheres is 15:1, mixing for 1h in a stirrer with the temperature of 170 ℃ and the rotation speed of 100rpm, and fully mixing to form a regeneration mixture under the protection of nitrogen;
step 4, placing the regenerated mixture into a screw extruder, wherein the screw extruder is heated by six sections of temperature control, and the step comprises the following steps: the first temperature is 195 ℃, the second temperature is 210 ℃, the third temperature is 230 ℃, the fourth temperature is 255 ℃, the fifth temperature is 280 ℃, and the sixth temperature is 295 ℃, and the strip-shaped packaging strip body is obtained through melt extrusion;
step 5, rapidly cooling the banded packing belt blank through a cold water tank, wherein the temperature of the cold water tank is 15 ℃, the treatment time is 10s, then placing the banded packing belt blank in an oven for preheating treatment, the temperature of the oven is 180 ℃, the treatment time is 15s, and then stretching, shaping and rolling, wherein the stretching temperature is 90 ℃, and the stretching multiple is 3.8 times; the shaping temperature is 120 ℃, the treatment time is 40s, and then the mixture is naturally cooled to room temperature, so that the nano modified PET bottle reclaimed material is obtained to produce the packing belt.
Comparative example 1
The process for producing a packing tape was the same as in example 1, except that the caffeic acid coated porous titanium silicate/silica composite microspheres in step 1 were replaced with silica microspheres having a particle size of 10 to 20. Mu.m.
Comparative example 2
A process for producing a packing belt is the same as in example 1 except that the poly-caffeic acid coated porous titanium silicate/silica composite microspheres in step 1 are replaced with porous titanium silicate/silica microspheres having a particle size of 10 to 20 μm (i.e., step S3 is omitted and the crushed particle size is enlarged to 10 to 20 μm).
Comparative example 3
The process for producing a packing tape was the same as in example 1, except that step 1 was omitted and steps 2 to 5 were directly carried out without adding the poly-caffeic acid-coated porous titanium silicate/silica composite microspheres, i.e., without modifying the reclaimed materials.
Application example
The packing sheets (each having a thickness of 1 mm.+ -. 0.05 mm) prepared in example 1 and comparative examples 1 to 3 were subjected to performance measurement as follows:
(1) Tensile strength: detection standard GB/T1040.1-2018;
(2) Elongation at break: detection standard GB/T1040.1-2018;
(3) Impact strength: detection standard GB/T1843-2008;
(4) Heat distortion temperature: detecting by using a thermal deformation Vicat temperature measuring instrument with the model of HWK-300 according to the standard GB/T1633-2000;
(5) Acid resistance: soaking in sulfuric acid with mass fraction of 5% for 120h, and detecting the retention rate (%) of tensile strength to judge the strength of acid resistance.
(6) Alkali resistance: soaking in sodium hydroxide with mass fraction of 5% for 120h, and detecting the retention rate (%) of tensile strength to judge the alkali resistance.
The results of the measurements are shown in Table 1 below:
TABLE 1 comparison of the results of the tests of inventive example 1 and comparative examples 1 to 3
As can be seen from table 1 above, the tensile strength, elongation at break and impact strength of example 1 all perform better, indicating that it has better mechanical properties and toughness; the heat distortion temperature is higher, which indicates that the heat resistance is better and the heat distortion is not easy to occur under the high temperature condition; the retention rate of tensile strength after pickling is up to 93%, and the retention rate of tensile strength after pickling is up to 87%, which indicates that the steel has higher acid and alkali resistance and can be suitable for being used in complex environments with more chemical products.
Finally, it should be noted that the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made to the technical solution of the present invention without departing from the spirit and scope of the technical solution of the present invention.
Claims (9)
1. The processing technology for producing the packing belt by using the nano modified PET bottle reclaimed materials is characterized by comprising the following steps of:
step 1, preparing nano activated silica by utilizing vinyl silane through a mercapto-ethylene click reaction, then compositing titanium silicate and the nano activated silica to form porous titanium silicate/silica composite microspheres, and then performing coating treatment of caffeic acid to obtain the caffeic acid coated porous titanium silicate/silica composite microspheres;
step 2, shearing the PET bottle into pieces, sequentially cleaning and drying, then extruding and granulating after melting in a screw extruder, and crushing by using airflow impact to obtain PET bottle reclaimed material particles;
step 3, mixing PET bottle regeneration material particles and the poly caffeic acid coated porous titanium silicate/silicon dioxide composite microspheres in a stirrer, and fully mixing under the protection of nitrogen to form a regeneration mixture;
step 4, placing the regenerated mixture into a screw extruder, and performing melt extrusion in the screw extruder to obtain a strip-shaped packing strip body;
step 5, rapidly cooling the banded packing belt blank through a cold water tank, then placing the banded packing belt blank in an oven for preheating treatment, and then stretching, shaping and rolling to obtain a nano modified PET bottle reclaimed material for producing packing belts;
in the step 1, the process of coating treatment of the caffeic acid specifically comprises the following steps:
mixing caffeic acid with Tris-HCl buffer solution with pH of 8.2 and concentration of 1g/L, and stirring at room temperature to obtain solution C; copper chloride is mixed with Tris-HCl buffer solution with pH of 8.2 and concentration of 1g/L, and stirred uniformly at room temperature to obtain solution D; mixing the solution C and the solution D, adding porous titanium silicate/silicon dioxide composite microspheres, then dropwise adding hydrogen peroxide solution with the mass fraction of 20% -40%, stirring for 0.5-1 h at room temperature, and sequentially filtering, cleaning, drying and crushing to obtain the poly-caffeic acid coated porous titanium silicate/silicon dioxide composite microspheres;
wherein the mass ratio of caffeic acid to Tris-HCl buffer solution in the solution C is 1-3:10-15, the mass ratio of cupric chloride to Tris-HCl buffer solution in the solution D is 0.6-1.2:10-15, and the mass ratio of porous titanium silicate/silicon dioxide composite microsphere, hydrogen peroxide solution, solution C and solution D is 1:0.02-0.06:10-20:10-20.
2. The process for producing packaging tape from nano-modified PET bottle reclaimed materials according to claim 1, wherein in the step 1, the preparation process of nano-scale activated silica is specifically as follows:
(1) Sequentially adding vinyl triethoxysilane and sodium dodecyl benzene sulfonate into distilled water, stirring for 1-2 hours at the speed of 400-600 rpm, then dropwise adding ammonia water, heating to 45-55 ℃, stirring for 36-48 hours at the speed of 200-300 rpm, filtering, cleaning, drying and crushing to obtain nano-grade vinylated silicon dioxide;
wherein the mass ratio of vinyl triethoxysilane, sodium dodecyl benzene sulfonate and distilled water is 1.8-2.0:0.02-0.04:20-30, the concentration of ammonia water is 25%, and the mass ratio of ammonia water to vinyl triethoxysilane is 1:4-6;
(2) Sequentially adding nano-grade vinylated silicon dioxide, azodiisobutyronitrile and 2-mercaptoethanol into absolute ethyl alcohol, heating to 70-80 ℃ under the protection of nitrogen, stirring for 18-24 hours at the speed of 200-300 rpm, filtering, cleaning and drying to obtain nano-grade activated silicon dioxide;
the mass ratio of the nanoscale vinylated silicon dioxide to the azodiisobutyronitrile to the 2-mercaptoethanol to the absolute ethyl alcohol is 1:0.4-0.6:1.6-1.8:10-15.
3. The processing technology for producing packaging tape from nano-modified PET bottle reclaimed materials according to claim 1, wherein in the step 1, the preparation process of the porous titanium silicate/silicon dioxide composite microsphere is specifically as follows:
(1) Mixing tetraethoxysilane and ethanol to form a solution A, mixing tetrabutyl titanate and ethanol to form a solution B, dropwise adding a 0.05mol/L nitric acid solution into the solution A, stirring for 0.5-1 h under ice water bath, continuously dropwise adding the solution B into the mixed solution, heating to 40-50 ℃, stirring for 1-2 h, dropwise adding polyethylene glycol into the mixed solution again, stirring for 0.5-1 h under heat preservation, cooling to room temperature, and sealing and ageing for at least 5 days at room temperature to obtain titanium silicate sol;
the mass ratio of the tetraethoxysilane to the ethanol in the solution A is 3-5:10, the mass ratio of the tetrabutyl titanate to the ethanol in the solution B is 3-5:10, and the mass ratio of the nitric acid solution, the polyethylene glycol, the solution A and the solution B is 1.56-1.88:0.04-0.06:7-8:1;
(2) Mixing nanoscale activated silicon dioxide with titanium silicate sol, stirring at a speed of 400-600 rpm, simultaneously dropwise adding ammonia water until the pH value of the mixed solution is 8.0-9.0, stopping dropwise adding ammonia water, continuously stirring for 0.5-1 h, standing for 0.5h, filtering out precipitate, washing with hot water at 80-100 ℃ until the pH value of the washing solution is 7, vacuum drying, and crushing to obtain porous titanium silicate/silicon dioxide composite microspheres;
wherein the mass ratio of the nanoscale activated silica to the titanium silicate sol is 1:10-20.
4. The process for producing the packing belt from the nano-modified PET bottle reclaimed materials according to claim 1, wherein in the step 1, the particle size of nano-scale activated silica is 300-500 nm, the particle size of porous titanium silicate/silica composite microspheres is 5-10 μm, and the particle size of the caffeic acid coated porous titanium silicate/silica composite microspheres is 10-20 μm.
5. The process for producing the packing belt by using the nano modified PET bottle reclaimed materials according to claim 1, wherein in the step 2, the PET bottle fragments are firstly placed in a sodium hydroxide solution with the concentration of 0.05mol/L, heated and stirred for 0.5-1 h, the PET bottle fragments are filtered out, and distilled water is used for washing until the pH of a washing liquid is neutral.
6. The processing technology for producing packaging belts from nano-modified PET bottle reclaimed materials according to claim 1, wherein in the step 2, the temperature of a screw extruder is 285-295 ℃; the drying temperature is 110-120 ℃, and the drying time is 2-4 hours; the particle size of the PET bottle reclaimed material particles is 50-100 mu m.
7. The process for producing the packing belt by using the nano modified PET bottle reclaimed materials according to claim 1, wherein in the step 3, the temperature of a stirrer is 150-170 ℃, the rotation speed is 50-100 rpm, and the mixing time is 0.5-1 h; the mass ratio of the PET bottle regeneration material particles to the poly-caffeic acid coated porous titanium silicate/silicon dioxide composite microspheres is 10-15:1.
8. The process for producing packaging tape from nano-modified PET bottle reclaimed materials according to claim 1, wherein in the step 4, the screw extruder is six-stage temperature controlled heating, and the process comprises the following steps: 185-195 ℃ for one section, 200-210 ℃ for two sections, 220-230 ℃ for three sections, 240-255 ℃ for four sections, 260-280 ℃ for five sections, and 285-295 ℃ for six sections.
9. The processing technology for producing packaging belts from nano-modified PET bottle reclaimed materials according to claim 1, wherein in the step 5, the temperature of a cold water tank is 10-15 ℃ and the treatment time is 5-10 s; the temperature of the oven is 170-180 ℃, and the treatment time is 10-15 s; the stretching temperature is 80-90 ℃, and the stretching multiple is 2.7-3.8 times; setting the temperature at 110-120 ℃, treating for 20-40 s, and naturally cooling to room temperature.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102399421A (en) * | 2011-09-05 | 2012-04-04 | 谢志江 | Processing technology for producing ultrahigh-strength packing tape by using low-cost nano modified polyethylene terephthalate (PET) bottle regenerated material |
| CN106009967A (en) * | 2016-06-23 | 2016-10-12 | 黄作鹏 | Composite heat-insulating paint for exterior walls and preparation method of composite heat-insulating paint |
| CN107459782A (en) * | 2016-06-06 | 2017-12-12 | 天津芳菲塑料制品有限公司 | A kind of processing technology of nano modification PET bottle reworked material production strap |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102399421A (en) * | 2011-09-05 | 2012-04-04 | 谢志江 | Processing technology for producing ultrahigh-strength packing tape by using low-cost nano modified polyethylene terephthalate (PET) bottle regenerated material |
| CN107459782A (en) * | 2016-06-06 | 2017-12-12 | 天津芳菲塑料制品有限公司 | A kind of processing technology of nano modification PET bottle reworked material production strap |
| CN106009967A (en) * | 2016-06-23 | 2016-10-12 | 黄作鹏 | Composite heat-insulating paint for exterior walls and preparation method of composite heat-insulating paint |
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