CN102250453B - Polyhydroxyalkanoate (PHA) and poly(ethylene terephthalate)glycol (PETG) blend film and preparation method thereof - Google Patents
Polyhydroxyalkanoate (PHA) and poly(ethylene terephthalate)glycol (PETG) blend film and preparation method thereof Download PDFInfo
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- 239000005014 poly(hydroxyalkanoate) Substances 0.000 title claims abstract description 76
- 239000000203 mixture Substances 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- -1 poly(ethylene terephthalate) Polymers 0.000 title claims abstract description 11
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 title abstract description 13
- 229920000139 polyethylene terephthalate Polymers 0.000 title abstract description 5
- 239000005020 polyethylene terephthalate Substances 0.000 title abstract description 5
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 title abstract 2
- 229920000903 polyhydroxyalkanoate Polymers 0.000 claims abstract description 71
- 239000000463 material Substances 0.000 claims abstract description 66
- 239000011347 resin Substances 0.000 claims abstract description 63
- 229920005989 resin Polymers 0.000 claims abstract description 63
- 238000000034 method Methods 0.000 claims abstract description 46
- 230000008569 process Effects 0.000 claims abstract description 22
- 239000000314 lubricant Substances 0.000 claims abstract description 14
- 229920005644 polyethylene terephthalate glycol copolymer Polymers 0.000 claims description 81
- 238000002156 mixing Methods 0.000 claims description 50
- 239000010409 thin film Substances 0.000 claims description 34
- 230000015572 biosynthetic process Effects 0.000 claims description 28
- 238000003490 calendering Methods 0.000 claims description 28
- 239000003112 inhibitor Substances 0.000 claims description 28
- 239000010408 film Substances 0.000 claims description 20
- 238000001816 cooling Methods 0.000 claims description 18
- 230000006698 induction Effects 0.000 claims description 18
- QUAMTGJKVDWJEQ-UHFFFAOYSA-N octabenzone Chemical group OC1=CC(OCCCCCCCC)=CC=C1C(=O)C1=CC=CC=C1 QUAMTGJKVDWJEQ-UHFFFAOYSA-N 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 230000003068 static effect Effects 0.000 claims description 17
- 238000003851 corona treatment Methods 0.000 claims description 14
- 239000004902 Softening Agent Substances 0.000 claims description 13
- 239000006096 absorbing agent Substances 0.000 claims description 13
- 230000003647 oxidation Effects 0.000 claims description 13
- 238000007254 oxidation reaction Methods 0.000 claims description 13
- 239000012752 auxiliary agent Substances 0.000 claims description 12
- 230000004927 fusion Effects 0.000 claims description 12
- 238000007872 degassing Methods 0.000 claims description 11
- 238000012545 processing Methods 0.000 claims description 10
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 150000002148 esters Chemical class 0.000 claims description 9
- 238000007046 ethoxylation reaction Methods 0.000 claims description 9
- 229950002083 octabenzone Drugs 0.000 claims description 9
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical class OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 9
- 238000005096 rolling process Methods 0.000 claims description 7
- 239000004698 Polyethylene Substances 0.000 claims description 4
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Natural products OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 4
- 229920000573 polyethylene Polymers 0.000 claims description 4
- 102100024348 Beta-adducin Human genes 0.000 claims description 3
- 101000689619 Homo sapiens Beta-adducin Proteins 0.000 claims description 3
- 230000000694 effects Effects 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- 150000003973 alkyl amines Chemical class 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 150000002191 fatty alcohols Chemical class 0.000 claims description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 2
- 239000006057 Non-nutritive feed additive Substances 0.000 abstract description 6
- 229910052799 carbon Inorganic materials 0.000 abstract description 4
- 229920000728 polyester Polymers 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 229920001169 thermoplastic Polymers 0.000 abstract description 3
- 239000004416 thermosoftening plastic Substances 0.000 abstract description 3
- 239000003963 antioxidant agent Substances 0.000 abstract 1
- 230000003078 antioxidant effect Effects 0.000 abstract 1
- 239000002216 antistatic agent Substances 0.000 abstract 1
- 239000004067 bulking agent Substances 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 239000004014 plasticizer Substances 0.000 abstract 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 abstract 1
- 239000007858 starting material Substances 0.000 description 17
- ZFOZVQLOBQUTQQ-UHFFFAOYSA-N Tributyl citrate Chemical compound CCCCOC(=O)CC(O)(C(=O)OCCCC)CC(=O)OCCCC ZFOZVQLOBQUTQQ-UHFFFAOYSA-N 0.000 description 12
- 230000002035 prolonged effect Effects 0.000 description 9
- 239000004744 fabric Substances 0.000 description 8
- 238000005303 weighing Methods 0.000 description 8
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 description 5
- QZCLKYGREBVARF-UHFFFAOYSA-N Acetyl tributyl citrate Chemical compound CCCCOC(=O)CC(C(=O)OCCCC)(OC(C)=O)CC(=O)OCCCC QZCLKYGREBVARF-UHFFFAOYSA-N 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 238000012986 modification Methods 0.000 description 4
- 238000003672 processing method Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- RFVNOJDQRGSOEL-UHFFFAOYSA-N 2-hydroxyethyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCCO RFVNOJDQRGSOEL-UHFFFAOYSA-N 0.000 description 3
- 229920001634 Copolyester Polymers 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 description 2
- 229920003232 aliphatic polyester Polymers 0.000 description 2
- 238000007385 chemical modification Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical group C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 239000004609 Impact Modifier Substances 0.000 description 1
- 102220530816 Transcription factor SOX-9_P90E_mutation Human genes 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229920000704 biodegradable plastic Polymers 0.000 description 1
- 230000003570 biosynthesizing effect Effects 0.000 description 1
- 230000001851 biosynthetic effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- HGAZMNJKRQFZKS-UHFFFAOYSA-N chloroethene;ethenyl acetate Chemical compound ClC=C.CC(=O)OC=C HGAZMNJKRQFZKS-UHFFFAOYSA-N 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 229920006238 degradable plastic Polymers 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000013213 extrapolation Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 235000016709 nutrition Nutrition 0.000 description 1
- 230000035764 nutrition Effects 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000012815 thermoplastic material Substances 0.000 description 1
- 238000005491 wire drawing Methods 0.000 description 1
Landscapes
- Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
- Treatments Of Macromolecular Shaped Articles (AREA)
- Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
The invention belongs to the technical field of thermoplastic polyester, and discloses a polyhydroxyalkanoate (PHA) and poly(ethylene terephthalate)glycol (PETG) blend film and a preparation method thereof. The film is prepared from the following raw materials in percentage by weight: 20 to 80 percent of PHA resin, 10 to 70 percent of PETG resin, 0.3 to 2.1 percent of PETG resin processing aid, 5 to 8 percent of plasticizer, 0.1 to 0.7 percent of lubricant, 0.1 to 0.5 percent of antioxidant, 0 to 2.2 percent of bulking agent, 0 to 0.5 percent of ultraviolet absorber and 0 to 0.5 percent of antistatic agent. A blend of the PHA resin capable of being biosynthesized and degraded completely and the PETG resin capable of being degraded is taken as a main body material, the blend film is low-carbon and environment-friendly, and the application fields of the PHA and PETG resin are widened. The film has excellent heat resistance and good ductility; the product yield is high; the raw materials are readily available; and the process is simple and practicable, is suitable for industrial production, and has excellent industrial application value.
Description
Technical field
The invention belongs to the thermoplastic polyester technical field, be specifically related to a kind of PHA and PETG blend thin films and preparation method thereof.
Background technology
Polyhydroxyalkanoate (PHA) is prokaryotic micro-organisms in the unbalance situation of Carbon and nitrogen nutrition, stores and the synthetic biological polyester of an analog thermoplastic aliphatics as carbon source and the energy.Because the mechanical property of PHA and some thermoplastic material such as polyethylene, polypropylene-base are seemingly, but can degradablely enter natural ecological circulation, thereby be considered to a kind of may substitute traditional nondegradable, by the biodegradable plastic of the synthetic plastics of petroleum path.
As a kind of degradable plastics kind that may substitute traditional petroleum path, the existing lot of documents in aspect and the patent reports such as present biosynthesizing about the PHA material, bio-modification, chemical modification, and for method for processing forming and the technology of PHA, also only limit at present injection moulding, squeeze sheet, the techniques such as wire drawing, mold pressing, yet there are no report and adopt the method for calendering formation to prepare the PHA film.
The same with other aliphatic polyester, the PHA material also exists the many shortcomings on processing and the performance, such as poor heat stability, easily hydrolysis, process window relative narrower, machine-shaping is difficult, crystallization velocity is slow, shaping cycle is long, toughness is relatively poor, the while production cost is also higher.In order to solve these difficult problems that face in the PHA application, it is carried out various forms of modifications, comprise bio-modification, chemical modification and physically modified have just become inevitable choice.In the molding process of PHA, also must for the needs of product property and method for processing forming, carry out modification to the PHA material.
Polyethylene terephthalate-Isosorbide-5-Nitrae-cyclohexanedimethanol (PETG) is the copolyesters that is formed by terephthalic acid (DMT), ethylene glycol (EG) and Isosorbide-5-Nitrae-cyclohexanedimethanol (CHDM) copolymerization, has degradability.Under certain EG/CHDM ratio, owing to the introducing of hexanaphthene unit in the molecular chain, reduced the regularity of whole molecular chain, PETG is a kind of complete unbodied transparent copolyester.The transparency of PETG, tint permanence and resistance to air loss etc. have overcome general engineering plastic polyethylene terephthalate (PET) defective in this respect, so at food product pack, daily necessities and Container for cosmetics, photochemistry and medical field good application prospect is arranged.Simultaneously, PETG has good processing characteristics.At present, the PETG resin has obtained successful application on the card matrix material of the goods such as identity card.
But up to now, a kind of means that widely adopt as the exploitation of polymkeric substance novel material, the method of polymer blending also is not applied in the exploitation of these two kinds of degradable resins for the novel material on basis, PHA and PETG blend have no any type of report so far, adopt film and the calendering formation method of the preparation of PHA and PETG blend also to have no report.
Summary of the invention
The purpose of this invention is to provide a kind of PHA and PETG blend thin films.
The preparation method who the purpose of this invention is to provide above-mentioned PHA and PETG blend thin films.
The objective of the invention is to realize by following technical measures:
A kind of polyhydroxyalkanoate (PHA) and polyethylene terephthalate-1,4 cyclohexane dimethanol ester (PETG) blend thin films, this film adopts following prescription to process:
PHA resin 20-80wt%, PETG resin 10-70wt%, PETG resin treatment auxiliary agent 0.3-2.1wt%, softening agent 5-8wt%, lubricant 0.1-0.7wt%, oxidation inhibitor 0.1-0.5wt%, expanding material 0-2.2wt%, UV light absorber 0-0.5wt%, static inhibitor 0-0.5wt%.Each composition sum is 100wt% in the actual prescription.
Described PHA and PETG blend thin films, wherein the density of PHA resin is 1.23-1.26g/cm
3, melting index is 2-3g/10min; The density of PETG resin is 1.26-1.30g/cm
3, second-order transition temperature 80-82 ℃.
Described PHA and PETG blend thin films, wherein the PHA resin is that (be Shenzhen Yi Keman bio tech ltd product, density is 1.23-1.26g/cm for EM10000, EM10010 or EM10020 type
3, melting index is 2-3g/10min) in a kind of; The PETG resin is GS1, GS2, GS3, GS4, (be U.S. Yi Shi Man product, density is 1.26-1.30g/cm to the GS5 type
3, second-order transition temperature 80-82 ℃) in a kind of; PETG resin treatment auxiliary agent is ADD2 type (U.S. Yi Shi Man product); Softening agent is one or more in the citric acid ester type, lubricant is one or more in stearate, Fatty Alcohol(C12-C14 and C12-C18) two acid esters, oxidation inhibitor is one or more in the phosphorous acid esters, expanding material is the styrenic reactive resin with the epoxy-functional of high reaction activity, UV light absorber is Octabenzone, and static inhibitor is one or more in the ethoxylated alkylamine.
Described PHA and PETG blend thin films, wherein expanding material is SAG005 type (Rizhisheng New Technology Development Co., Ltd., Shanghai's product), static inhibitor is the ethoxylation oleyl amine.
The preparation method of described PHA and PETG blend thin films comprises the following steps:
To pulverize behind PHA, the PETG resin drying, after PETG resin treatment auxiliary agent, softening agent, lubricant, oxidation inhibitor, expanding material, UV light absorber, static inhibitor fully mix, the fusion plastification extruded material, through rolling out film, deflect from, stretch, cool off, draw, batch, cut, obtain PHA and PETG blend thin films (0.05mm≤thickness＜0.3mm).
Described preparation method, wherein PHA, PETG resin-oatmeal are broken to the 40-200 order; The processing condition of rolling out film are: 120-160 ℃ of roller temperature, and roller speed 5-30m/ minute, speed ratio is 1.05-1.2; Deflect from, stretching condition is: temperature 60-120 ℃; The type of cooling and condition are: temperature is 30-60 ℃ circulating water; Carry out corona treatment and eliminostatic processing in the traction operation, mode and condition that eliminostatic is processed are: the induction type electrostatic rod is eliminated static, operating voltage AC220V, output voltage 1.5-5.0V; The mode of corona treatment and condition are: adopt corona processor to carry out corona treatment, corona processor operating voltage AC380V, frequency 18-30kHz.
Described preparation method wherein mixes and adopts high-speed mixer; Fusion plastification adopts planetary degassing extruder; Rolling out film adopts the calendering formation machine.
Beneficial effect of the present invention:
The present invention is directed to the performance characteristics requirement of polymeric film and the needs of calendering formation working method, adopt commercial PHA, PETG resin, select suitable processing aid and functional aid, obtained to be applicable to prescription and the calendering formation processing method of PHA and the PETG blend thin films of calendering formation method.
The present invention compared with prior art has following positively effect:
1. the present invention provides a kind of PHA and PETG blend thin films that is suitable for the rolling process moulding first.PHA be a kind of can be biosynthetic, the thermoplasticity aliphatic polyester of Wholly-degradable, PETG is that a kind of transparency, tint permanence and resistance to air loss etc. are with respect to the improved degradable copolyester of PET.The expansion of the Application Areas of these two kinds of polymkeric substance meets the low-carbon (LC) that novel material exploitation pursues, target and the development trend of environmental protection.Form by material provided by the present invention, can expand the Application Areas of PHA and two kinds of degradable resins of PETG, blend thin films provided by the present invention can be used as the fields such as industrial or agricultural packing, decoration and daily necessities.
2. the invention provides the calendering formation processing method of a kind of PHA and PETG blend thin films.Adopt calendering formation processing method provided by the invention, prepared PHA and PETG blend thin films Good Heat-resistance, ductility are good;
3. the various starting material in the prescription of PHA provided by the present invention and PETG blend thin films are commercial prod, and raw material obtains easily, have excellent industrial application value.
4. the calendering formation processing method of PHA provided by the present invention and PETG blend thin films, technical process is simple, realizes easily suitability for industrialized production.
Embodiment
Embodiment given below is to specific descriptions of the present invention; be necessary to be pointed out that at this following examples are only for the present invention is described further; can not be interpreted as limiting the scope of the invention; this art skilled person makes some nonessential improvement and adjustment according to the invention described above content to the present invention, still belongs to protection scope of the present invention.
The calendering formation machine that adopts in following examples is that forming machine (axle interior extrapolation) is prolonged in five roll-ins of the Italian RODOLFO F of company type, No. three stacks have installed additional and have cut bubble assembly, forcing machine adopts the planetary degassing extruder of German bass holder husband, and type of heating is electrically heated.
Used PHA resin is Shenzhen Yi Keman bio tech ltd EM10010 type among the embodiment, the PETG resin is the U.S. GS-2 of Yi Shi Man type, PETG resin treatment auxiliary agent is the U.S. ADD2 of Yi Shi Man type, and expanding material is the SAG005 of Rizhisheng New Technology Development Co., Ltd., Shanghai type.The thickness of film for the ease of Performance Ratio, provides a kind of composition and engineering technological line and processing condition of commercial PVC film simultaneously by stack roller spacing control, and all to control film thickness in embodiment and the comparative example be 0.08mm.
Embodiment 1:PHA and PETG blend thin films prescription 1 and calendering formation technique thereof
Material prescription: PHA resin 80wt%, PETG resin 10wt%, PETG resin treatment auxiliary agent A DD20.3wt%, softening agent citric acid tri butyl ester 5wt%, tributyl acetylcitrate 3wt%, lubricant stearic acid glyceryl ester 0.5wt%, ethylene glycol monostearate 0.2wt%, the different monooctyl ester 0.5wt% of oxidation inhibitor tricresyl phosphite, expanding material SAG0050wt%, UV light absorber Octabenzone 0wt%, static inhibitor ethoxylation oleyl amine 0.5wt%.
Calendering formation technique:
A. starting material are prepared: take by weighing starting material 10Kg by prescription, adopt the disintegrating apparatus such as abrasive disk type pulverizer to be crushed to the 40-200 order after PHA, PETG resin drying are following to moisture content 0.5% (wt, lower with);
B. mixing of materials: adopt high-speed mixer that material is carried out two sections mixing processes.High-speed mixing section: 70 ℃ of temperature of charge, speed of mainshaft 1500rpm, mixing time 30min; Low speed mixing section: 40 ℃ of temperature of charge, speed of mainshaft 80rpm, mixing time 15min;
C. material fusion plastification: adopt planetary degassing extruder that material is melt extruded plasticizing, the forcing machine working temperature is distributed as 125-175 ℃, screw speed 45rpm;
D. slice is prolonged in five roll-ins: stack temperature (1-5 roller) is respectively 145 ℃, and 145 ℃, 146 ℃, 147 ℃, 139 ℃, roller speed (1-5 roller) is respectively 6.3,6.9,7.5,8.2,9.6m/min; Speed ratio is 1.05-1.2;
E. deflect from stretching: adopt five groups of rollers to deflect from stretching, its temperature control is respectively: first group 120 ℃, and second group 115 ℃, the 3rd group 105 ℃, the 4th group 90 ℃, the 5th group 70 ℃;
F. cooling: adopt three groups of rollers to carry out circulating water, circulating water temperature is controlled to be: first group 60 ℃, and second group 50 ℃, the 3rd group 40 ℃; Adopt ES-2025 induction type electrostatic rod to carry out eliminostatic (operating voltage AC220V, output voltage 1.5-5.0V, length 1800mm) after the cooling;
G. draw, batch: carry out corona treatment (AX308 type corona processor in the traction operation, operating voltage AC380V, frequency 18-30kHz, fabric width 1800mm) and eliminostatic process (ES-2025 induction type electrostatic rod, operating voltage AC220V, output voltage 1.5-5.0V, length 1800mm);
H. cut: cut into needed length and width.
Embodiment 2:PHA and PETG blend thin films prescription 2 and calendering formation technique thereof
Material prescription: PHA resin 70wt%, PETG resin 20wt%, PETG resin treatment auxiliary agent A DD2 0.6wt%, softening agent citric acid tri butyl ester 4.5wt%, tributyl acetylcitrate 3wt%, lubricant stearic acid glyceryl ester 0.5wt%, the different monooctyl ester 0.4wt% of oxidation inhibitor tricresyl phosphite, expanding material SAG0050.5wt%, UV light absorber Octabenzone 0wt%, static inhibitor ethoxylation oleyl amine 0.5wt%.
Calendering formation technique:
A. starting material are prepared: take by weighing starting material 10Kg by prescription, PHA, PETG resin drying to the disintegrating apparatus such as moisture content rear employing abrasive disk type pulverizer below 0.5% are crushed to the 40-200 order;
B. mixing of materials: adopt high-speed mixer that material is carried out two sections mixing processes.High-speed mixing section: 70 ℃ of temperature of charge, speed of mainshaft 1500rpm, mixing time 30min; Low speed mixing section: 40 ℃ of temperature of charge, speed of mainshaft 80rpm, mixing time 15min;
C. material fusion plastification: adopt planetary degassing extruder that material is melt extruded plasticizing, the forcing machine working temperature is distributed as 125-175 ℃, screw speed 40rpm;
D. slice is prolonged in five roll-ins: stack temperature (1-5 roller) is respectively 148 ℃, and 148 ℃, 150 ℃, 151 ℃, 142 ℃, roller speed (1-5 roller) is respectively 6.4,7.0,7.6,8.2,9.6m/min; Speed ratio is 1.05-1.2;
E. deflect from stretching: adopt five groups of rollers to deflect from stretching, its temperature control is respectively: first group 120 ℃, and second group 115 ℃, the 3rd group 105 ℃, the 4th group 90 ℃, the 5th group 70 ℃;
F. cooling: adopt three groups of rollers to carry out circulating water, circulating water temperature is controlled to be: first group 60 ℃, and second group 50 ℃, the 3rd group 40 ℃; Adopt ES-2025 induction type electrostatic rod to carry out eliminostatic (operating voltage AC220V, output voltage 1.5-5.0V, length 1800mm after the cooling;
G. draw, batch: carry out corona treatment (AX308 type corona processor in the traction operation, operating voltage AC380V, frequency 18-30kHz, fabric width 1800mm) and eliminostatic process (ES-2025 induction type electrostatic rod, operating voltage AC220V, output voltage 1.5-5.0V, length 1800mm);
H. cut and cut into needed length and width.
Embodiment 3:PHA and PETG blend thin films prescription 3 and calendering formation technique thereof
Material prescription: PHA resin 60wt%, PETG resin 30wt%, PETG resin treatment auxiliary agent A DD2 0.9wt%, softening agent citric acid tri butyl ester 3.5wt%, tributyl acetylcitrate 3.5wt%, lubricant ethylene glycol monostearate 0.5wt%, the different monooctyl ester 0.35wt% of oxidation inhibitor tricresyl phosphite, expanding material SAG0050.75wt%, UV light absorber Octabenzone 0.25wt%, static inhibitor ethoxylation oleyl amine 0.25wt%.
Calendering formation technique:
A. starting material are prepared: take by weighing starting material 10Kg by prescription, PHA, PETG resin drying to the disintegrating apparatus such as moisture content rear employing abrasive disk type pulverizer below 0.5% are crushed to the 40-200 order;
B. mixing of materials: adopt high-speed mixer that material is carried out two sections mixing processes.High-speed mixing section: 70 ℃ of temperature of charge, speed of mainshaft 1500rpm, mixing time 30min; Low speed mixing section: 40 ℃ of temperature of charge, speed of mainshaft 80rpm, mixing time 15min;
C. material fusion plastification: adopt planetary degassing extruder that material is melt extruded plasticizing, the forcing machine working temperature is distributed as 125-175 ℃, screw speed 37rpm;
D. slice is prolonged in five roll-ins: stack temperature (1-5 roller) is respectively 150 ℃, and 150 ℃, 152 ℃, 152 ℃, 144 ℃, roller speed (1-5 roller) is respectively 6.2,6.7,7.3,8.0,9.4m/min; Speed ratio is 1.05-1.2;
E. deflect from stretching: adopt five groups of rollers to deflect from stretching, its temperature control is respectively: first group 120 ℃, and second group 115 ℃, the 3rd group 105 ℃, the 4th group 90 ℃, the 5th group 70 ℃;
F. cooling: adopt three groups of rollers to carry out circulating water, circulating water temperature is controlled to be: first group 60 ℃, and second group 50 ℃, the 3rd group 40 ℃; Adopt ES-2025 induction type electrostatic rod to carry out eliminostatic (operating voltage AC220V, output voltage 1.5-5.0V, length 1800mm) after the cooling;
G. draw, batch: carry out corona treatment (AX308 type corona processor in the traction operation, operating voltage AC380V, frequency 18-30kHz, fabric width 1800mm) and eliminostatic process (ES-2025 induction type electrostatic rod, operating voltage AC220V, output voltage 1.5-5.0V, length 1800mm);
H. cut and cut into needed length and width.
Embodiment 4:PHA and PETG blend thin films prescription 4 and calendering formation technique thereof
Material prescription: PHA resin 50wt%, PETG resin 40wt%, PETG resin treatment auxiliary agent A DD2 1.2wt%, softening agent citric acid tri butyl ester 2.5wt%, tributyl acetylcitrate 4wt%, lubricant stearic acid glyceryl ester 0.4wt%, the different monooctyl ester 0.25wt% of oxidation inhibitor tricresyl phosphite, expanding material SAG005 1.15wt%, UV light absorber Octabenzone 0.25wt%, static inhibitor ethoxylation oleyl amine 0.25wt%.
Calendering formation technique:
A. starting material are prepared: take by weighing starting material 10Kg by prescription, PHA, PETG resin drying to the disintegrating apparatus such as moisture content rear employing abrasive disk type pulverizer below 0.5% are crushed to the 40-200 order;
B. mixing of materials: adopt high-speed mixer that material is carried out two sections mixing processes.High-speed mixing section: 70 ℃ of temperature of charge, speed of mainshaft 1500rpm, mixing time 30min; Low speed mixing section: 40 ℃ of temperature of charge, speed of mainshaft 80rpm, mixing time 15min;
C. material fusion plastification: adopt planetary degassing extruder that material is melt extruded plasticizing, the forcing machine working temperature is distributed as 125-175 ℃, screw speed 32rpm;
D. slice is prolonged in five roll-ins: stack temperature (1-5 roller) is respectively 152 ℃, and 152 ℃, 155 ℃, 155 ℃, 146 ℃, roller speed (1-5 roller) is respectively 6.3,6.9,7.5,8.2,9.6m/min; Speed ratio is 1.05-1.2;
E. deflect from stretching: adopt five groups of rollers to deflect from stretching, its temperature control is respectively: first group 120 ℃, and second group 115 ℃, the 3rd group 105 ℃, the 4th group 90 ℃, the 5th group 70 ℃;
F. cooling: adopt three groups of rollers to carry out circulating water, circulating water temperature is controlled to be: first group 60 ℃, and second group 50 ℃, the 3rd group 40 ℃; Adopt ES-2025 induction type electrostatic rod to carry out eliminostatic (operating voltage AC220V, output voltage 1.5-5.0V, length 1800mm) after the cooling;
G. draw, batch: carry out corona treatment (AX308 type corona processor in the traction operation, operating voltage AC380V, frequency 18-30kHz, fabric width 1800mm) and eliminostatic process (ES-2025 induction type electrostatic rod, operating voltage AC220V, output voltage 1.5-5.0V, length 1800mm);
H. cut and cut into needed length and width.
Embodiment 5:PHA and PETG blend thin films prescription 5 and calendering formation technique thereof
Material prescription: PHA resin 40wt%, PETG resin 50wt%, the special-purpose processing aid ADD21.5wt% of PETG resin, softening agent tributyl acetylcitrate 6wt%, lubricant ethylene glycol monostearate 0.3wt%, the different monooctyl ester 0.2wt% of oxidation inhibitor tricresyl phosphite, expanding material SAG0051.5wt%, UV light absorber Octabenzone 0.25wt%, static inhibitor ethoxylation oleyl amine 0.25wt%.
Calendering formation technique:
A. starting material are prepared: take by weighing starting material 10Kg by prescription, PHA, PETG resin drying to the disintegrating apparatus such as moisture content rear employing abrasive disk type pulverizer below 0.5% are crushed to the 40-200 order;
B. mixing of materials: adopt high-speed mixer that material is carried out two sections mixing processes.High-speed mixing section: 70 ℃ of temperature of charge, speed of mainshaft 1500rpm, mixing time 30min; Low speed mixing section: 40 ℃ of temperature of charge, speed of mainshaft 80rpm, mixing time 15min;
C. material fusion plastification: adopt planetary degassing extruder that material is melt extruded plasticizing, the forcing machine working temperature is distributed as 125-175 ℃, screw speed 32rpm;
D. slice is prolonged in five roll-ins: stack temperature (1-5 roller) is respectively 152 ℃, and 152 ℃, 155 ℃, 155 ℃, 146 ℃, roller speed (1-5 roller) is respectively 6.4,7.0,7.6,8.2,9.6m/min; Speed ratio is 1.05-1.2;
E. deflect from stretching: adopt five groups of rollers to deflect from stretching, its temperature control is respectively: first group 120 ℃, and second group 115 ℃, the 3rd group 105 ℃, the 4th group 90 ℃, the 5th group 70 ℃;
F. cooling: adopt three groups of rollers to carry out circulating water, circulating water temperature is controlled to be: first group 60 ℃, and second group 50 ℃, the 3rd group 40 ℃; Adopt ES-2025 induction type electrostatic rod to carry out eliminostatic (operating voltage AC220V, output voltage 1.5-5.0V, length 1800mm) after the cooling;
G. draw, batch: carry out corona treatment (AX308 type corona processor in the traction operation, operating voltage AC380V, frequency 18-30kHz, fabric width 1800mm) and eliminostatic process (ES-2025 induction type electrostatic rod, operating voltage AC220V, output voltage 1.5-5.0V, length 1800mm);
H. cut and cut into needed length and width.
Embodiment 6:PHA and PETG blend thin films prescription 6 and calendering formation technique thereof
Material prescription: PHA resin 30wt%, PETG resin 60wt%, the special-purpose processing aid ADD21.8wt% of PETG resin, softening agent citric acid tri butyl ester 5.5wt%, lubricant stearic acid glyceryl ester 0.2wt%, the different monooctyl ester 0.15wt% of oxidation inhibitor tricresyl phosphite, expanding material SAG005 1.85wt%, UV light absorber Octabenzone 0.5wt%, static inhibitor ethoxylation oleyl amine 0wt%.
Calendering formation technique:
A. starting material are prepared: take by weighing starting material 10Kg by prescription, PHA, PETG resin drying to the disintegrating apparatus such as moisture content rear employing abrasive disk type pulverizer below 0.5% are crushed to the 40-200 order;
B. mixing of materials: adopt high-speed mixer that material is carried out two sections mixing processes.High-speed mixing section: 70 ℃ of temperature of charge, speed of mainshaft 1500rpm, mixing time 30min; Low speed mixing section: 40 ℃ of temperature of charge, speed of mainshaft 80rpm, mixing time 15min;
C. material fusion plastification: adopt planetary degassing extruder that material is melt extruded plasticizing, the forcing machine working temperature is distributed as 125-175 ℃, screw speed 32rpm;
D. slice is prolonged in five roll-ins: stack temperature (1-5 roller) is respectively 152 ℃, and 152 ℃, 155 ℃, 155 ℃, 146 ℃, roller speed (1-5 roller) is respectively 6.2,6.7,7.3,8.0,9.4m/min; Speed ratio is 1.05-1.2;
E. deflect from stretching: adopt five groups of rollers to deflect from stretching, its temperature control is respectively: first group 120 ℃, and second group 115 ℃, the 3rd group 105 ℃, the 4th group 90 ℃, the 5th group 70 ℃;
F. cooling: adopt three groups of rollers to carry out circulating water, circulating water temperature is controlled to be: first group 60 ℃, and second group 50 ℃, the 3rd group 40 ℃; Adopt ES-2025 induction type electrostatic rod to carry out eliminostatic (operating voltage AC220V, output voltage 1.5-5.0V, length 1800mm after the cooling;
G. draw, batch: carry out corona treatment (AX308 type corona processor in the traction operation, operating voltage AC380V, frequency 18-30kHz, fabric width 1800mm) and eliminostatic process (ES-2025 induction type electrostatic rod, operating voltage AC220V, output voltage 1.5-5.0V, length 1800mm);
H. cut and cut into needed length and width.
Embodiment 7:PHA and PETG blend thin films prescription 7 and calendering formation technique thereof
Material prescription: PHA resin 20wt%, PETG resin 70wt%, the special-purpose processing aid ADD22.1wt% of PETG resin, softening agent citric acid tri butyl ester 5wt%, lubricant stearic acid glyceryl ester 0.1wt%, the different monooctyl ester 0.1wt% of oxidation inhibitor tricresyl phosphite, expanding material SAG0052.2wt%, UV light absorber Octabenzone 0.5wt%, static inhibitor ethoxylation oleyl amine 0wt%.
Calendering formation technique:
A. starting material are prepared: take by weighing starting material 10Kg by prescription, PHA, PETG resin drying to the disintegrating apparatus such as moisture content rear employing abrasive disk type pulverizer below 0.5% are crushed to the 40-200 order;
B. mixing of materials: adopt high-speed mixer that material is carried out two sections mixing processes.High-speed mixing section: 70 ℃ of temperature of charge, speed of mainshaft 1500rpm, mixing time 30min; Low speed mixing section: 40 ℃ of temperature of charge, speed of mainshaft 80rpm, mixing time 15min;
C. material fusion plastification: adopt planetary degassing extruder that material is melt extruded plasticizing, the forcing machine working temperature is distributed as 125-175 ℃, screw speed 32rpm;
D. slice is prolonged in five roll-ins: stack temperature (1-5 roller) is respectively 152 ℃, and 152 ℃, 155 ℃, 155 ℃, 146 ℃, roller speed (1-5 roller) is respectively 6.2,6.7,7.3,8.0,9.4m/min; Speed ratio is 1.05-1.2;
E. deflect from stretching: adopt five groups of rollers to deflect from stretching, its temperature control is respectively: first group 120 ℃, and second group 115 ℃, the 3rd group 105 ℃, the 4th group 90 ℃, the 5th group 70 ℃;
F. cooling: adopt three groups of rollers to carry out circulating water, circulating water temperature is controlled to be: first group 60 ℃, and second group 50 ℃, the 3rd group 40 ℃; Adopt ES-2025 induction type electrostatic rod to carry out eliminostatic (operating voltage AC220V, output voltage 1.5-5.0V, length 1800mm after the cooling;
G. draw, batch: carry out corona treatment (AX308 type corona processor in the traction operation, operating voltage AC380V, frequency 18-30kHz, fabric width 1800mm) and eliminostatic process (ES-2025 induction type electrostatic rod, operating voltage AC220V, output voltage 1.5-5.0V, length 1800mm);
H. cut and cut into needed length and width.
Comparative example: PVC film formulation and calendering formation technique thereof
Material prescription: PVC (Qilu Petrochemical S-700 type) resin 49.25wt%, vinyl chloride-vinyl acetate resin (the large magnificent chemical industry BL-1 of the company limited type in Jiangyin) 38.38wt%, anti-impact modifier (U.S. ROHM AND HAAS B522 type) 6.57wt%, organotin stabilizer (east, the Hangzhou rising sun auxiliary agent DX980 of company limited type) 2.14wt%, (German bear board LPL type: Italy sends out chemical Ca-St basic to inside and outside lubrication prescription: German bear board FTA type=1: 5: 1 (wt)) 1.25wt%, processing aid (the Shandong Ri Ke LP-20 of group type: U.S. ROHM AND HAAS K175P type=3: 1 (wt)) 1.06wt%, releasing agent (the German Vinnolit P90E of company type) 1.35wt%.
Calendering formation technique:
A. starting material are prepared: take by weighing starting material 10Kg by prescription, adopt the full-automatic electronic metering, guarantee Measuring Precision;
B. mixing of materials: adopt high-speed mixer that material is carried out two sections mixing processes.High-speed mixing section: 98 ℃ of temperature of charge, speed of mainshaft 1500rpm, mixing time 10min; Low speed mixing section: 53 ℃ of temperature of charge, speed of mainshaft 80rpm, mixing time 15min;
C. material fusion plastification: adopt planetary degassing extruder that material is melt extruded plasticizing, the forcing machine working temperature is distributed as 125-175 ℃, screw speed 45rpm;
D. slice is prolonged in five roll-ins: stack temperature (1-5 roller) is respectively 141 ℃, and 143 ℃, 178 ℃, 190 ℃, 138 ℃, roller speed (1-5 roller) is respectively 6.3,6.9,7.5,8.2,9.6m/min; Speed ratio is 1.05-1.2;
E. deflect from stretching: adopt five groups of rollers to deflect from stretching, its temperature control is respectively: first group 120 ℃, and second group 115 ℃, the 3rd group 105 ℃, the 4th group 90 ℃, the 5th group 70 ℃;
F. cooling: adopt three groups of rollers to carry out circulating water, circulating water temperature is controlled to be: first group 60 ℃, and second group 50 ℃, the 3rd group 40 ℃; Adopt ES-2025 induction type electrostatic rod to carry out eliminostatic (operating voltage AC220V, output voltage 1.5-5.0V, length 1800mm) after the cooling;
G. draw, batch: carry out corona treatment (AX308 type corona processor in the traction operation, operating voltage AC380V, frequency 18-30kHz, fabric width 1800mm) and eliminostatic process (ES-2025 induction type electrostatic rod, operating voltage AC220V, output voltage 1.5-5.0V, length 1800mm);
H. cut and cut into needed length and width.
The product performance test:
The PHA that above-mentioned 7 embodiment are obtained and PETG blend thin films and a kind of performance test of adopting the commercial PVC film of the same thickness that equipment of the same race and similar processing technology routine produce.Testing method is: tensile strength, tensile modulus, tension fracture elongation rate are measured according to GB/T1040.3, and dimension card heat resisting temperature is tested according to GB/T1633, and test result sees Table 1.
The performance of table 1 calendering formation PHA/PETG blend thin films
Test result shows, PHA and PETG blend thin films according to prescription provided by the invention and preparation method's acquisition, tensile strength and tensile modulus are a little less than commercial PVC film, but the transverse breakage elongation can be compared with commercial PVC film, and longitudinal fracture elongation and Wei Ka heat resisting temperature are far above commercial PVC film.Simultaneously, PHA and PETG blend thin films film performance is adjusted in relative broad range as required.
Claims (7)
1. a polyhydroxyalkanoate (PHA) and polyethylene terephthalate-1,4 cyclohexane dimethanol ester (PETG) blend thin films is characterized in that this film adopts following prescription to process:
PHA resin 20-80wt%, PETG resin 10-70wt%, PETG resin treatment auxiliary agent 0.3-2.1wt%, softening agent 5-8wt%, lubricant 0.1-0.7wt%, oxidation inhibitor 0.1-0.5wt%, expanding material 0-2.2wt%, UV light absorber 0-0.5wt%, static inhibitor 0-0.5wt%;
Wherein: the PHA resin is the EM10010 type, is Shenzhen Yi Keman bio tech ltd product; The PETG resin is the GS-2 type, is U.S. Yi Shi Man product; PETG resin treatment auxiliary agent is the ADD2 type, is U.S. Yi Shi Man product.
2. PHA according to claim 1 and PETG blend thin films, it is characterized in that softening agent is one or more in the citric acid ester type, lubricant is one or more in stearate, Fatty Alcohol(C12-C14 and C12-C18) two acid esters, oxidation inhibitor is one or more in the phosphorous acid esters, expanding material is the styrenic reactive resin with the epoxy-functional of high reaction activity, UV light absorber is Octabenzone, and static inhibitor is one or more in the ethoxylated alkylamine.
3. PHA according to claim 1 and PETG blend thin films is characterized in that expanding material is the SAG005 type, and static inhibitor is the ethoxylation oleyl amine.
4. the preparation method of the described PHA of claim 1 and PETG blend thin films is characterized in that comprising the following steps:
To pulverize behind PHA, the PETG resin drying, after PETG resin treatment auxiliary agent, softening agent, lubricant, oxidation inhibitor, expanding material, UV light absorber, static inhibitor fully mix, the fusion plastification extruded material, through rolling out film, deflect from, stretch, cool off, draw, batch, cut, obtain PHA and PETG blend thin films.
5. preparation method according to claim 4 is characterized in that the thickness of PHA and PETG blend thin films is: 0.05mm≤thickness＜0.3mm.
6. preparation method according to claim 4 is characterized in that PHA, PETG resin-oatmeal are broken to the 40-200 order; The processing condition of rolling out film are: 120-160 ℃ of roller temperature, and roller speed 5-30m/ minute, speed ratio is 1.05-1.2; Deflect from, stretching condition is: temperature 60-120 ℃; The type of cooling and condition are: temperature is 30-60 ℃ circulating water; Carry out corona treatment and eliminostatic processing in the traction operation, mode and condition that eliminostatic is processed are: the induction type electrostatic rod is eliminated static, operating voltage AC220V, output voltage 1.5-5.0V; The mode of corona treatment and condition are: adopt corona processor to carry out corona treatment, corona processor operating voltage AC380V, frequency 18-30kHz.
7. preparation method according to claim 4 is characterized in that mixing the employing high-speed mixer; Fusion plastification adopts planetary degassing extruder; Rolling out film adopts the calendering formation machine.
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| CN104497505B (en) * | 2014-12-26 | 2016-04-13 | 江苏华信新材料股份有限公司 | A kind of PHA for smart card protects diaphragm and preparation method thereof |
| CN104530660B (en) * | 2014-12-26 | 2016-06-01 | 江苏华信新材料股份有限公司 | A kind of PHA base material for smart card and its preparation method |
| CN104497506B (en) * | 2014-12-26 | 2016-04-13 | 江苏华信新材料股份有限公司 | A kind of PHA for smart card prints diaphragm and preparation method thereof |
| CN105802159B (en) * | 2014-12-29 | 2018-01-12 | 江苏华信新材料股份有限公司 | A kind of degradable PHA/PLA blend thin filmses and preparation method thereof |
| CN104875404A (en) * | 2015-04-25 | 2015-09-02 | 安徽松泰包装材料有限公司 | PETG membrane production technology |
| CN112757730B (en) * | 2021-02-05 | 2023-06-23 | 河南银金达新材料股份有限公司 | PETG multilayer composite film for packaging and preparation method thereof |
| CN112778930B (en) * | 2021-02-09 | 2022-04-22 | 河南银金达新材料股份有限公司 | PHA/PETG adhesive tape film and preparation method thereof |
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