CN102250452A - PHA (Polyhydroxyalkanoate) rigid sheet and preparation method thereof - Google Patents
PHA (Polyhydroxyalkanoate) rigid sheet and preparation method thereof Download PDFInfo
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- CN102250452A CN102250452A CN2011101409341A CN201110140934A CN102250452A CN 102250452 A CN102250452 A CN 102250452A CN 2011101409341 A CN2011101409341 A CN 2011101409341A CN 201110140934 A CN201110140934 A CN 201110140934A CN 102250452 A CN102250452 A CN 102250452A
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- 239000005014 poly(hydroxyalkanoate) Substances 0.000 title claims abstract description 61
- 229920000903 polyhydroxyalkanoate Polymers 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000011347 resin Substances 0.000 claims abstract description 25
- 229920005989 resin Polymers 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 17
- 239000000314 lubricant Substances 0.000 claims abstract description 11
- 239000000463 material Substances 0.000 claims description 37
- 238000002156 mixing Methods 0.000 claims description 33
- 230000015572 biosynthetic process Effects 0.000 claims description 22
- 238000003490 calendering Methods 0.000 claims description 22
- 239000003112 inhibitor Substances 0.000 claims description 22
- 238000001816 cooling Methods 0.000 claims description 19
- 230000003068 static effect Effects 0.000 claims description 13
- 230000006698 induction Effects 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 238000003851 corona treatment Methods 0.000 claims description 11
- 230000003647 oxidation Effects 0.000 claims description 11
- 238000007254 oxidation reaction Methods 0.000 claims description 11
- 239000004902 Softening Agent Substances 0.000 claims description 10
- QUAMTGJKVDWJEQ-UHFFFAOYSA-N octabenzone Chemical group OC1=CC(OCCCCCCCC)=CC=C1C(=O)C1=CC=CC=C1 QUAMTGJKVDWJEQ-UHFFFAOYSA-N 0.000 claims description 10
- 238000012545 processing Methods 0.000 claims description 10
- 239000006096 absorbing agent Substances 0.000 claims description 9
- 230000004927 fusion Effects 0.000 claims description 9
- 238000007872 degassing Methods 0.000 claims description 8
- 238000005096 rolling process Methods 0.000 claims description 7
- -1 citric acid ester Chemical class 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 150000002148 esters Chemical class 0.000 claims description 5
- 238000007046 ethoxylation reaction Methods 0.000 claims description 5
- 229950002083 octabenzone Drugs 0.000 claims description 5
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical class OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 5
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 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
- 238000002844 melting Methods 0.000 claims description 3
- 230000008018 melting Effects 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- 150000003973 alkyl amines Chemical class 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
- 229910052799 carbon Inorganic materials 0.000 abstract description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 3
- 229920000728 polyester Polymers 0.000 abstract description 3
- 229920001169 thermoplastic Polymers 0.000 abstract description 3
- 239000004416 thermosoftening plastic Substances 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 230000002745 absorbent Effects 0.000 abstract 1
- 239000002250 absorbent Substances 0.000 abstract 1
- 239000003963 antioxidant agent Substances 0.000 abstract 1
- 230000003078 antioxidant effect Effects 0.000 abstract 1
- 239000002216 antistatic agent Substances 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 239000011159 matrix material Substances 0.000 abstract 1
- 239000004014 plasticizer Substances 0.000 abstract 1
- 229920000642 polymer Polymers 0.000 abstract 1
- 238000005516 engineering process Methods 0.000 description 15
- 239000007858 starting material Substances 0.000 description 11
- 229920005644 polyethylene terephthalate glycol copolymer Polymers 0.000 description 7
- ZFOZVQLOBQUTQQ-UHFFFAOYSA-N Tributyl citrate Chemical compound CCCCOC(=O)CC(O)(C(=O)OCCCC)CC(=O)OCCCC ZFOZVQLOBQUTQQ-UHFFFAOYSA-N 0.000 description 6
- 239000004744 fabric Substances 0.000 description 5
- 230000002035 prolonged effect Effects 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 238000003672 processing method Methods 0.000 description 4
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 description 3
- 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 3
- 239000006057 Non-nutritive feed additive Substances 0.000 description 3
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- RFVNOJDQRGSOEL-UHFFFAOYSA-N 2-hydroxyethyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCCO RFVNOJDQRGSOEL-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 102100024348 Beta-adducin Human genes 0.000 description 2
- 101000689619 Homo sapiens Beta-adducin Proteins 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-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
- 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
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 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
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 229920006238 degradable plastic Polymers 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000013213 extrapolation 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
- 238000001746 injection moulding Methods 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000000203 mixture Substances 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
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000012815 thermoplastic material Substances 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000005491 wire drawing Methods 0.000 description 1
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- Casting Or Compression Moulding Of Plastics Or The Like (AREA)
Abstract
The invention belongs to the technical field of thermoplastic polyester, and discloses a PHA (Polyhydroxyalkanoate) rigid sheet and a preparation method thereof. The sheet is processed by using the following formula in percentage by weight: 87.5-98.75 percent of PHA resin, 0.5-4.5 percent of plasticizer, 0.5-4.5 percent of lubricant, 0.25-1.5 percent of antioxidant, 0-1 percent of ultraviolet absorbent and 0-1 percent of antistatic agent. In the invention, the biologically synthesizable and completely degradable PHA resin is used as a polymer matrix, so that low carbon and environmental protection are guaranteed, and the application field of the PHA resin is obviously expanded. The rigid sheet has the advantages of superior ductility and heat resistance, high product yield, readily available raw materials, simple and feasible process, easiness for industrial production and high industrial application value.
Description
Technical field
The invention belongs to the thermoplastic polyester technical field, be specifically related to a kind of PHA hard sheet and preparation method thereof.
Background technology
Polyhydroxyalkanoate (PHA) is a prokaryotic micro-organisms under carbon, situation that nitrogen nutrition is unbalance, stores and the biological polyester of synthetic one analog thermoplastic aliphatics as the carbon source and the energy.Because the mechanical property of PHA and some thermoplastic material such as polyethylene, polypropylene-base are seemingly, enter natural ecological circulation but can degrade fully, thus be considered to a kind of may substitute traditional nondegradable, by the biodegradable plastic of petroleum path synthetic plastics.
As a kind of degradable plastics kind that may substitute traditional petroleum path, existing lot of documents in aspect and patent reports such as present biosynthesizing, bio-modification, chemical modification about the PHA material, and for method for processing forming and the technology of PHA, also only limit to injection moulding at present, squeeze sheet, technologies such as wire drawing, mold pressing, yet there are no report and adopt the method for calendering formation to prepare the PHA hard sheet.
The same with other aliphatic polyester, the PHA material also exists the many shortcomings on processing and the performance, as poor heat stability, easily hydrolysis, process window relative narrower, machine-shaping difficulty, 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 just become inevitable choice.In the molding process of PHA, also must the PHA material be carried out modification handle at the needs of product performance characteristics and method for processing forming.
Do not have as yet at present and adopt the calendering formation method to prepare the report of hard sheet the PHA resin.
Summary of the invention
The purpose of this invention is to provide a kind of PHA hard sheet.
Another object of the present invention provides the preparation method of above-mentioned PHA hard sheet.
Purpose of the present invention realizes by following technical measures:
A kind of polyhydroxyalkanoate (PHA) hard sheet, this sheet material adopt following prescription to process: PHA resin 87.5-98.75wt%, softening agent 0.5-4.5wt%, lubricant 0.5-4.5wt%, oxidation inhibitor 0.25-1.5wt%, UV light absorber 0-1wt%, static inhibitor 0-1wt%.Each composition sum is 100wt% in the actual prescription.
Described hard sheet, wherein the density of PHA resin is 1.23-1.26g/cm
3, melting index is 3-4g/10min.
Described hard sheet, wherein the PHA resin is that EM40010 or EM40000 type (are Shenzhen Yi Keman bio tech ltd product, density 1.23-1.26g/cm
3, melting index 3-4g/10min) in a kind of; 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, UV light absorber is an Octabenzone, and static inhibitor is one or more in the ethoxylated alkylamine.
Described hard sheet, wherein static inhibitor is the ethoxylation oleyl amine.
The preparation method of described hard sheet comprises the following steps:
To pulverize behind the PHA resin drying, behind softening agent, lubricant, oxidation inhibitor, UV light absorber, static inhibitor thorough mixing, the fusion plastification extruded material, through rolling out film, deflect from, stretch, cool off, draw, batch, cut, promptly get PHA hard sheet (0.3mm≤thickness≤1.5mm).
Described preparation method, wherein the PHA resin-oatmeal is broken to the 40-200 order; The rolling out film processing condition are: 120-160 ℃ of roller temperature, and roller speed 5-25m/ minute, speed ratio is 1.05-1.2; Deflect from, stretching condition is: temperature 60-120 ℃; Cooling conditions is: temperature is 30-60 ℃ recirculated water cooling; Carry out corona treatment and eliminostatic processing in the traction operation, mode and condition that eliminostatic is handled 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 polymkeric substance hard sheet and the needs of calendering formation working method, adopt commercial PHA resin, select suitable processing aid and functional aid for use, obtained to be applicable to the prescription and the calendering formation processing method of the PHA hard sheet of calendering formation method.The present invention compared with prior art has following positively effect:
1. the present invention provides a kind of PHA hard sheet that is suitable for the rolling process moulding first.PHA be a kind of can be biosynthetic, the thermoplasticity aliphatic polyester of Wholly-degradable, the expansion of its Application Areas meets the low-carbon (LC) that the novel material exploitation pursued, the target and the development trend of environmental protection.Form by material provided by the present invention, can expand the Application Areas of PHA.Hard sheet provided by the present invention can be used as fields such as Decorative panel, thermoset sheet material.
2. the invention provides a kind of calendering formation processing method of PHA hard sheet.Adopt calendering formation processing method provided by the invention, prepared PHA hard sheet ductility, Good Heat-resistance;
3. the various starting material in the PHA hard sheet prescription provided by the present invention are commercial prod, and raw material obtains easily, have excellent industrial application value.
4. the calendering formation processing method of PHA hard sheet provided by the present invention, technical process is simple, realizes suitability for industrialized production easily.
Embodiment
Embodiment given below is to specific descriptions of the present invention; be necessary to be pointed out that at this following examples only are used for that 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 the Italian RODOLFO F of company type five roll-ins prolonging shaper (an axle interior extrapolation), 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 a kind of of Shenzhen Yi Keman bio tech ltd EM40010 or EM40000 type among the embodiment.The thickness of sheet material is by the control of stack roller spacing.A kind of production formula, processing technology routine and processing condition of commercial PETG hard sheet for the ease of performance relatively, are provided simultaneously.Simultaneously, all controlling sheet thickness in following examples and the comparative example is 0.33mm.
Embodiment 1:PHA hard sheet prescription 1 and calendering formation technology thereof
Material prescription: PHA resin 87.5wt%, softening agent citric acid tri butyl ester 3wt%, tributyl acetylcitrate 1.5wt%, lubricant stearic acid glyceryl ester 3wt%, ethylene glycol monostearate 1.5wt%, the different monooctyl ester 1.5wt% of oxidation inhibitor tricresyl phosphite, UV light absorber Octabenzone 1wt%, static inhibitor ethoxylation oleyl amine 1wt%.
Calendering formation technology:
A. starting material preparation: take by weighing starting material 10Kg by prescription, PHA resin drying to disintegrating apparatus such as the following back employing abrasive disk type pulverizer of moisture content 0.5% (wt, down together) 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 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 5.5,6.1,6.7,7.3,8.6m/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 the recirculated water cooling, circulating water temperature is controlled to be: first group 60 ℃, and second group 50 ℃, the 3rd group 40 ℃; The cooling back adopts ES-2025 induction type electrostatic rod to carry out eliminostatic (operating voltage AC220V, output voltage 1.5-5.0V, length 1800mm);
G. draw, batch: carry out corona treatment (AX308 type corona processor, operating voltage AC380V, frequency 18-30kHz in the traction operation, fabric width 1800mm) and eliminostatic handle (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 hard sheet prescription 2 and calendering formation technology thereof
Material prescription: PHA resin 90wt%, softening agent citric acid tri butyl ester 2wt%, tributyl acetylcitrate 1.5wt%, lubricant stearic acid glyceryl ester 4.5wt%, the different monooctyl ester of oxidation inhibitor tricresyl phosphite, phosphorous acid two each 0.5wt% of isodecyl ester, UV light absorber Octabenzone 0.5wt%, static inhibitor ethoxylation Stearyl Amine 0.5wt%.
Calendering formation technology:
A. starting material are prepared: take by weighing starting material 10Kg by prescription, PHA resin drying to disintegrating apparatus such as the moisture content employing of back below 0.5% abrasive disk type pulverizer 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 5.3,5.8,6.4,7.1,8.4m/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 the recirculated water cooling, circulating water temperature is controlled to be: first group 60 ℃, and second group 50 ℃, the 3rd group 40 ℃; The cooling back adopts ES-2025 induction type electrostatic rod to carry out eliminostatic (operating voltage AC220V, output voltage 1.5-5.0V, length 1800mm);
G. draw, batch: carry out corona treatment (AX308 type corona processor, operating voltage AC380V, frequency 18-30kHz in the traction operation, fabric width 1800mm) and eliminostatic handle (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 3:PHA hard sheet prescription 3 and calendering formation technology thereof
Material prescription: PHA resin 94.5wt%, softening agent citric acid tri butyl ester 1.5wt%, lubricant stearic acid glyceryl ester 3wt%, oxidation inhibitor phosphorous acid two isodecyl ester 0.5wt%, UV light absorber Octabenzone 0.25wt%, static inhibitor ethoxylation oleyl amine 0.25wt%.
Calendering formation technology:
A. starting material are prepared: take by weighing starting material 10Kg by prescription, PHA resin drying to disintegrating apparatus such as the moisture content employing of back below 0.5% abrasive disk type pulverizer 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 5.5,6.1,6.7,7.3,8.6m/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 the recirculated water cooling, circulating water temperature is controlled to be: first group 60 ℃, and second group 50 ℃, the 3rd group 40 ℃; The cooling back adopts ES-2025 induction type electrostatic rod to carry out eliminostatic (operating voltage AC220V, output voltage 1.5-5.0V, length 1800mm;
G. draw, batch: carry out corona treatment (AX308 type corona processor, operating voltage AC380V, frequency 18-30kHz in the traction operation, fabric width 1800mm) and eliminostatic handle (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 4:PHA hard sheet prescription 4 and calendering formation technology thereof
Material prescription: PHA resin 98.75wt%, softening agent tributyl acetylcitrate 0.5wt%, lubricant ethylene glycol monostearate 0.5wt%, oxidation inhibitor phosphorous acid two isodecyl ester 0.25wt%.
Calendering formation technology:
A. starting material are prepared: take by weighing starting material 10Kg by prescription, PHA resin drying to disintegrating apparatus such as the moisture content employing of back below 0.5% abrasive disk type pulverizer 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 5.3,5.8,6.4,7.1,8.4m/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 the recirculated water cooling, circulating water temperature is controlled to be: first group 60 ℃, and second group 50 ℃, the 3rd group 40 ℃; The cooling back adopts ES-2025 induction type electrostatic rod to carry out eliminostatic (operating voltage AC220V, output voltage 1.5-5.0V, length 1800mm);
G. draw, batch: carry out corona treatment (AX308 type corona processor, operating voltage AC380V, frequency 18-30kHz in the traction operation, fabric width 1800mm) and eliminostatic handle (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.
Comparative example: PETG hard sheet prescription and calendering formation technology thereof
Material prescription: PETG resin (U.S. Yi Shiman GS2 type resin) 85.43wt%, PETG processing aid (U.S. ADD2 of Yi Shi Man type) 5.98wt%, the different monooctyl ester of oxidation inhibitor tricresyl phosphite (Switzerland vapour crust I1010: Switzerland vapour crust I168=2: 0.37wt% 1 (wt)), titanium dioxide (the Shandong Dong Jia SR240 of group type) 8.22wt%.
Calendering formation technology:
A. starting material are prepared: take by weighing starting material 10Kg by prescription, PETG resin and processing aid ADD2 be dried to moisture content 0.5% below afterwards disintegrating apparatus such as employing abrasive disk type pulverizer be 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: 80 ℃ 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 120-160 ℃, screw speed 45rpm;
D. slice is prolonged in five roll-ins: stack temperature (1-5 roller) is respectively 162 ℃, and 162 ℃, 183 ℃, 192 ℃, 153 ℃, 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 110 ℃, the 3rd group 100 ℃, the 4th group 90 ℃, the 5th group 70 ℃;
F. cooling: adopt three groups of rollers to carry out the recirculated water cooling, circulating water temperature is controlled to be: first group 60 ℃, and second group 50 ℃, the 3rd group 40 ℃; The cooling back adopts ES-2025 induction type electrostatic rod to carry out eliminostatic (operating voltage AC220V, output voltage 1.5-5.0V, length 1800mm);
G. draw, batch: carry out corona treatment (AX308 type corona processor, operating voltage AC380V, frequency 18-30kHz in the traction operation, fabric width 1800mm) and eliminostatic handle (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.
The product performance test:
Above-mentioned 4 PHA hard sheets that embodiment obtained and a kind of commercial PETG hard sheet of the same thickness of equipment of the same race and similar processing technology routine production that adopts are carried out performance test.Testing method: 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.Test result sees Table 1.
The performance of table 1 calendering formation PHA hard sheet
Test result shows, the PHA hard sheet that obtains according to prescription provided by the invention and preparation method, and except tensile strength and modulus were lower slightly, the ductility of sheet material (elongation at break) and thermotolerance (dimension is blocked heat resisting temperature) all were higher than commercial PETG hard sheet.
Claims (8)
1. a polyhydroxyalkanoate (PHA) hard sheet, it is characterized in that this sheet material adopts following prescription to process: PHA resin 87.5-98.75wt%, softening agent 0.5-4.5wt%, lubricant 0.5-4.5wt%, oxidation inhibitor 0.25-1.5wt%, UV light absorber 0-1wt%, static inhibitor 0-1wt%.
2. hard sheet according to claim 1, the density that it is characterized in that the PHA resin is 1.23-1.26g/cm
3, melting index is 3-4g/10min.
3. hard sheet according to claim 1 is characterized in that the PHA resin is a kind of in EM40010 or the EM40000 type; 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, UV light absorber is an Octabenzone, and static inhibitor is one or more in the ethoxylated alkylamine.
4. hard sheet according to claim 1 is characterized in that static inhibitor is the ethoxylation oleyl amine.
5. the preparation method of the described hard sheet of claim 1 is characterized in that comprising the following steps:
To pulverize behind the PHA resin drying, behind softening agent, lubricant, oxidation inhibitor, UV light absorber, static inhibitor thorough mixing, the fusion plastification extruded material through rolling out film, deflect from, stretch, cool off, draw, batch, cut, promptly gets the PHA hard sheet.
6. preparation method according to claim 5 is characterized in that the thickness of PHA hard sheet is: 0.3mm≤thickness≤1.5mm.
7. preparation method according to claim 5 is characterized in that the PHA resin-oatmeal is broken to the 40-200 order; The rolling out film processing condition are: 120-160 ℃ of roller temperature, and roller speed 5-25m/ minute, speed ratio is 1.05-1.2; Deflect from, stretching condition is: temperature 60-120 ℃; Cooling conditions is: temperature is 30-60 ℃ recirculated water cooling; Carry out corona treatment and eliminostatic processing in the traction operation, mode and condition that eliminostatic is handled 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.
8. preparation method according to claim 5 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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| CN2011101409341A CN102250452A (en) | 2011-05-29 | 2011-05-29 | PHA (Polyhydroxyalkanoate) rigid sheet and preparation method thereof |
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| CN2011101409341A CN102250452A (en) | 2011-05-29 | 2011-05-29 | PHA (Polyhydroxyalkanoate) rigid sheet and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102977566A (en) * | 2012-12-31 | 2013-03-20 | 江苏华信塑业发展有限公司 | Degradable PHA/PBS (Polyhydroxyalkanoates/Polybutylene Succinate) blend sheet and preparation method thereof |
| CN104530660A (en) * | 2014-12-26 | 2015-04-22 | 江苏华信新材料股份有限公司 | PHA base material for smart card and preparation method of PHA base material |
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| US6569990B1 (en) * | 1998-12-21 | 2003-05-27 | The Procter & Gamble Company | Plastic articles comprising biodegradable PHA copolymers |
| CN1640918A (en) * | 2004-12-20 | 2005-07-20 | 陈明忠 | Biological degradatable plastic sheet material and its preparation method |
| WO2010013483A1 (en) * | 2008-08-01 | 2010-02-04 | 株式会社カネカ | Resin composition and sheet |
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| US6569990B1 (en) * | 1998-12-21 | 2003-05-27 | The Procter & Gamble Company | Plastic articles comprising biodegradable PHA copolymers |
| CN1640918A (en) * | 2004-12-20 | 2005-07-20 | 陈明忠 | Biological degradatable plastic sheet material and its preparation method |
| WO2010013483A1 (en) * | 2008-08-01 | 2010-02-04 | 株式会社カネカ | Resin composition and sheet |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102977566A (en) * | 2012-12-31 | 2013-03-20 | 江苏华信塑业发展有限公司 | Degradable PHA/PBS (Polyhydroxyalkanoates/Polybutylene Succinate) blend sheet and preparation method thereof |
| CN104530660A (en) * | 2014-12-26 | 2015-04-22 | 江苏华信新材料股份有限公司 | PHA base material for smart card and preparation method of PHA base material |
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Application publication date: 20111123 |