CN103965516A - Fully biodegradable masterbatch and preparation method thereof - Google Patents
Fully biodegradable masterbatch and preparation method thereof Download PDFInfo
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- CN103965516A CN103965516A CN201310042024.9A CN201310042024A CN103965516A CN 103965516 A CN103965516 A CN 103965516A CN 201310042024 A CN201310042024 A CN 201310042024A CN 103965516 A CN103965516 A CN 103965516A
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- 239000004594 Masterbatch (MB) Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 229920002472 Starch Polymers 0.000 claims abstract description 28
- 239000008107 starch Substances 0.000 claims abstract description 24
- 235000019698 starch Nutrition 0.000 claims abstract description 24
- 239000003999 initiator Substances 0.000 claims abstract description 7
- 239000000314 lubricant Substances 0.000 claims abstract description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 30
- -1 methane amide Chemical class 0.000 claims description 27
- 238000001035 drying Methods 0.000 claims description 25
- 238000002156 mixing Methods 0.000 claims description 13
- 239000004902 Softening Agent Substances 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 12
- 150000002148 esters Chemical class 0.000 claims description 11
- KKEYFWRCBNTPAC-UHFFFAOYSA-N benzene-dicarboxylic acid Natural products OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 10
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 9
- 239000000945 filler Substances 0.000 claims description 9
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 9
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 8
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 8
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 7
- 150000008065 acid anhydrides Chemical class 0.000 claims description 6
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 6
- IKEHOXWJQXIQAG-UHFFFAOYSA-N 2-tert-butyl-4-methylphenol Chemical compound CC1=CC=C(O)C(C(C)(C)C)=C1 IKEHOXWJQXIQAG-UHFFFAOYSA-N 0.000 claims description 5
- 239000004698 Polyethylene Substances 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 239000003112 inhibitor Substances 0.000 claims description 5
- 230000003647 oxidation Effects 0.000 claims description 5
- 238000007254 oxidation reaction Methods 0.000 claims description 5
- 229920000573 polyethylene Polymers 0.000 claims description 5
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 4
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 4
- 239000005995 Aluminium silicate Substances 0.000 claims description 4
- 235000021355 Stearic acid Nutrition 0.000 claims description 4
- 235000012211 aluminium silicate Nutrition 0.000 claims description 4
- 150000001412 amines Chemical class 0.000 claims description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 4
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 4
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 4
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 4
- 229960003742 phenol Drugs 0.000 claims description 4
- 229920001592 potato starch Polymers 0.000 claims description 4
- 235000012239 silicon dioxide Nutrition 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 229960001866 silicon dioxide Drugs 0.000 claims description 4
- 239000008117 stearic acid Substances 0.000 claims description 4
- 239000004408 titanium dioxide Substances 0.000 claims description 4
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 3
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 3
- FVWQVDPNRUAXBQ-UHFFFAOYSA-N C(CCCCCCCCCCCCCCCCC)O.C(C)(C)(C)C=1C(=C(C=C(C1)C(C)(C)C)CCC(=O)O)O Chemical compound C(CCCCCCCCCCCCCCCCC)O.C(C)(C)(C)C=1C(=C(C=C(C1)C(C)(C)C)CCC(=O)O)O FVWQVDPNRUAXBQ-UHFFFAOYSA-N 0.000 claims description 3
- 241000196324 Embryophyta Species 0.000 claims description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 3
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 3
- 239000004202 carbamide Substances 0.000 claims description 3
- UAUDZVJPLUQNMU-KTKRTIGZSA-N erucamide Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-KTKRTIGZSA-N 0.000 claims description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 3
- 239000000178 monomer Substances 0.000 claims description 3
- 239000012188 paraffin wax Substances 0.000 claims description 3
- 235000019260 propionic acid Nutrition 0.000 claims description 3
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 3
- 239000001993 wax Substances 0.000 claims description 3
- 229940100445 wheat starch Drugs 0.000 claims description 3
- MEIRRNXMZYDVDW-MQQKCMAXSA-N (2E,4E)-2,4-hexadien-1-ol Chemical compound C\C=C\C=C\CO MEIRRNXMZYDVDW-MQQKCMAXSA-N 0.000 claims description 2
- 239000004215 Carbon black (E152) Substances 0.000 claims description 2
- 240000003183 Manihot esculenta Species 0.000 claims description 2
- 235000016735 Manihot esculenta subsp esculenta Nutrition 0.000 claims description 2
- 235000010216 calcium carbonate Nutrition 0.000 claims description 2
- 235000013539 calcium stearate Nutrition 0.000 claims description 2
- 239000008116 calcium stearate Substances 0.000 claims description 2
- 239000004927 clay Substances 0.000 claims description 2
- 229910052570 clay Inorganic materials 0.000 claims description 2
- 229920001577 copolymer Polymers 0.000 claims description 2
- 238000001125 extrusion Methods 0.000 claims description 2
- 235000013312 flour Nutrition 0.000 claims description 2
- 238000005469 granulation Methods 0.000 claims description 2
- 230000003179 granulation Effects 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- 150000002430 hydrocarbons Chemical class 0.000 claims description 2
- 239000010445 mica Substances 0.000 claims description 2
- 229910052618 mica group Inorganic materials 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 abstract description 19
- 239000000463 material Substances 0.000 abstract description 8
- 229920000229 biodegradable polyester Polymers 0.000 abstract description 4
- 239000004622 biodegradable polyester Substances 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 3
- 239000006185 dispersion Substances 0.000 abstract description 2
- 230000002209 hydrophobic effect Effects 0.000 abstract description 2
- 239000011159 matrix material Substances 0.000 abstract description 2
- 239000002861 polymer material Substances 0.000 abstract description 2
- 238000010521 absorption reaction Methods 0.000 abstract 1
- 239000003963 antioxidant agent Substances 0.000 abstract 1
- 230000003078 antioxidant effect Effects 0.000 abstract 1
- 230000007774 longterm Effects 0.000 abstract 1
- 239000003607 modifier Substances 0.000 abstract 1
- 238000012856 packing Methods 0.000 abstract 1
- 239000004014 plasticizer Substances 0.000 abstract 1
- 229920001896 polybutyrate Polymers 0.000 abstract 1
- 229920000642 polymer Polymers 0.000 abstract 1
- 238000005453 pelletization Methods 0.000 description 9
- 229920000728 polyester Polymers 0.000 description 7
- 229920002261 Corn starch Polymers 0.000 description 6
- 239000008120 corn starch Substances 0.000 description 6
- 239000010408 film Substances 0.000 description 6
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 4
- 229920008262 Thermoplastic starch Polymers 0.000 description 3
- 239000002250 absorbent Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000004628 starch-based polymer Substances 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 229920000747 poly(lactic acid) Polymers 0.000 description 2
- 229920002961 polybutylene succinate Polymers 0.000 description 2
- 239000004631 polybutylene succinate Substances 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- 101000873780 Homo sapiens m7GpppN-mRNA hydrolase Chemical group 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 102100035860 m7GpppN-mRNA hydrolase Human genes 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Biological Depolymerization Polymers (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
Belonging to the technical field of high polymer materials, the invention relates to a fully biodegradable masterbatch and a preparation method thereof. The fully biodegradable masterbatch is prepared from the following components by weight: 70-95 parts of starch, 5-30 parts of PBAT, 30-50 parts of a plasticizer, 0.5-3 parts of a compatilizer, 0.05-2 parts of an initiator, 0.5-5 parts of a hydrophobic modifier, 0.1-0.6 part of a lubricant, 0.1-0.5 part of an antioxidant, and 0-20 parts of a packing. The fully biodegradable masterbatch provided by the invention not only has good thermoplasticity, good processability, and good dispersion effect in a polymer matrix, but also has low water absorption capacity, can ensure the mechanical properties of materials during long-term storage, and can greatly reduce the preparation cost of blends after being added into biodegradable polyester.
Description
Technical field
The invention belongs to technical field of polymer materials, relate to a kind of complete biodegradable master batch and preparation method thereof.
Background technology
The use of plastics film has been penetrated into the every field of people's life, is widely used as food product pack, electric equipment products packaging and market shopping bag, refuse bag etc.Traditional plastic film material, if the starting material of polypropylene (PP) film, polyethylene (PE) film etc. are oil, uses and is discarded into hard degradation in nature, has caused huge harm to environment.Be accompanied by the day by day exhausted and continuous enhancing of people to environmental consciousness of petroleum resources, the environmentally friendly macromolecular material of exploitation degradable is applied to thin-film material field has become following Developing mainstream.
Poly(lactic acid) (PLA), poly butylene succinate (PBS), poly-(terephthalic acid butyleneglycol-co-hexanodioic acid butyleneglycol) ester (PBAT), PHA (PHA) etc. can both complete biodegradables, after using, be discarded in the Nature, can degradable be water and carbonic acid gas under the effect of microorganism.Therefore, can be widely used in plastics film field, the pollution that the use of minimizing conventional films brings environment.But above these biodegradable material prices are higher, the film being prepared into compared with traditional in price competitive power very weak.
Starch is extensively present in the middle of natural plant, and aboundresources and cheap is simultaneously biodegradable.So, starch is added in above-mentioned Biodegradable polyester, the blend of preparation not only can be realized complete biodegradable, but also can reduce the preparation cost of blend, increases its market competitiveness.
Starch add a kind of method in high molecular weight polyesters be by starch and softening agent, various processing aid directly with polyester after high-speed mixer and mixing is even, add extruding pelletization in screw machine to obtain blend, as described in patent CN1315927.Because undressed starch thermoplastic is poor, be difficult to processing, when therefore starch adds, all need to add softening agent to carry out plasticising processing to it, to improve the processing characteristics of starch.But above-mentioned working method, because the polyester that has a large amount of high molecular exists, easily makes starch plasticizing uneven, causes its dispersed variation in polyester.For improving the workability of starch and the dispersiveness in polyester, starch can be prepared into thermoplastic starch master batch, and then extrude with the polyester blend of high molecular the blend that obtains complete biodegradable.Therefore, the quality of thermoplastic starch master batch performance is very large to the blend performance impact of final preparation.The water-absorbent that topmost problem is exactly starch is large, and in order to improve the plasticity of starch, the polyalcohols softening agent adding makes the thermoplastic starch water-absorbent of preparation larger, and this can make the mechanical property of amyloid Biodegradable polyester blend can decline along with the prolongation in storage time obviously.Patent CN101328285 and patent CN101225117 have adopted two kinds of monomers with reactive terminal group and hydrophobic alkyl chain and starch storage crop to carry out hydrophobization processing, can reduce significantly the water-intake rate of treated starch, but the starch plasticity obtaining is poor.
Summary of the invention
The object of the invention is that the defect for overcoming prior art provides a kind of complete biodegradable master batch and preparation method thereof.
For achieving the above object, the present invention is by the following technical solutions:
A kind of complete biodegradable master batch, made by the component that comprises following weight part:
Described starch is one or more in potato starch, W-Gum, tapioca (flour) or wheat starch.
The weight-average molecular weight of described poly-(terephthalic acid butyleneglycol-co-hexanodioic acid butyleneglycol) ester (PBAT) is 20000-130000, obtains taking terephthalic acid or dimethyl terephthalate (DMT), butyleneglycol, hexanodioic acid as polymerizable raw material.
Described softening agent is one or more in ethylene glycol, propylene glycol, glycerol, sorbyl alcohol, urea, methane amide or ethanamide.
Described compatilizer is one or more in maleic anhydride, maleic anhydride grafted ethene-octene copolymer (POE-g-MAH).
Described initiator is one or more in dicumyl peroxide (DCP) or benzoyl peroxide (BPO).
Described hydrophobically modified agent is the monomer with long-chain fat hydrocarbon and reactive functionality, more preferably one or more in enetutanedioic acid anhydride and alkyl ketene dimer.
Described lubricant is one or more in stearic acid, calcium stearate, amine hydroxybenzene, erucicamide, paraffin, polyethylene wax.
Described oxidation inhibitor is four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] one or more in pentaerythritol ester, β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid octadecanol acid esters, 2-methylene-bis (4-methyl-6-tert-butylphenol) or three (2.4-di-tert-butyl-phenyl) phosphorous acid ester.
Described filler is one or more in calcium carbonate, kaolin, silicon-dioxide, mica, polynite, clay, titanium dioxide, talcum powder etc., preferably 1250 order-8000 orders of particle diameter, further preferred 2000-3000 order.
A preparation method for above-mentioned complete biodegradable master batch, comprises the steps:
(1) starch, poly-(terephthalic acid butyleneglycol-co-hexanodioic acid butyleneglycol) ester (PBAT), filler are carried out to drying treatment;
(2) take each component raw material of following weight part by said ratio: starch 70-95 part, PBAT5-30 part, softening agent 30-50 part, compatilizer 0.5-3 part, initiator 0.05-2 part, hydrophobically modified agent 0.5-5 part, lubricant 0.1-0.6 part, oxidation inhibitor 0.1-0.5 part, filler 0-20 part; Above-mentioned raw materials is even in high-speed mixer and mixing;
(3) raw material step (2) being mixed joins melt blending in twin screw extruder, extrudes, tie rod, granulation;
In described step (1), starch, PBAT, drying temperature are 60-80 DEG C, and be 6-24h time of drying; The drying temperature of filler is 100-120 DEG C, and the time is 5-10h; Drying plant is vacuum drying oven or convection oven.
In described step (3), twin screw extruder is in the same way or out-phase twin screw extruder, and extrusion temperature is 90-160 DEG C, screw speed 60-300rpm, and screw slenderness ratio L/D is 40-50:1.
The present invention has following beneficial effect:
Complete biodegradable master batch provided by the present invention not only has good thermoplasticity, good processability, and in polymeric matrix, dispersion effect is good, and water absorbing properties is low, can ensure the mechanical property of material in long-time storage process; Can greatly reduce the preparation cost of blend for adding Biodegradable polyester to.
Embodiment
Below in conjunction with embodiment, the present invention is further illustrated.
Mechanics Performance Testing: tensile property testing standard is ASTM D638, draw speed 50mm/min.
Water-absorbent testing standard: GB/T1034-2008, batten is placed 2h in 23 DEG C of waters bath with thermostatic control.Wherein, in the following example, the weight-average molecular weight of poly-(terephthalic acid butyleneglycol-co-hexanodioic acid butyleneglycol) ester is 20000-130000.
Embodiment 1
(1) by W-Gum, PBAT(weight-average molecular weight 12.5 ten thousand) drying treatment 6h in 80 DEG C of convection oven, titanium dioxide (2000 order) drying treatment 5h in 105 DEG C of convection oven.
(2) then 90 parts of extracting corn starch, PBAT10 part, 40 parts of softening agent glycerol, 0.5 part of compatilizer maleic anhydride, 0.05 part of initiator DCP, 0.5 part of hydrophobically modified agent enetutanedioic acid anhydride, 0.2 part of lubricant stearic acid calcium, oxidation inhibitor are four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] 0.2 part of pentaerythritol ester, 5 parts of normal temperature mixing 10min in high mixer of filler titanium dioxide.
(3) mixture obtaining is joined to extruding pelletization in twin screw extruder, the each district of twin screw extruder temperature is: 90 DEG C, a district, 110 DEG C, 2nd district, 120 DEG C, 3rd district, 130 DEG C, 4th district, 140 DEG C, 5th district, 150 DEG C, 6th district, 155 DEG C of heads; Screw speed 200rpm, length-to-diameter ratio 40/1.
Embodiment 2
(1) by W-Gum, PBAT(weight-average molecular weight 2.8 ten thousand) drying treatment 24h in 60 DEG C of convection oven, calcium carbonate (2500 order) drying treatment 8h in 105 DEG C of convection oven.
(2) then 70 parts of extracting corn starch, PBAT30 part, 20 parts of softening agent glycerol, 10 parts of softening agent methane amides, compatilizer POE-g-MAH1.5 part, initiator B PO1 part, 2 parts of alkyl ketene dimers, 0.5 part of erucicamide, 0.4 part of three (2.4-di-tert-butyl-phenyl) phosphorous acid ester, 10 parts of normal temperature mixing 10min in high mixer of calcium carbonate.
(3) mixture obtaining is joined to extruding pelletization in twin screw extruder, the each district of twin screw extruder temperature is: 90 DEG C, a district, 110 DEG C, 2nd district, 120 DEG C, 3rd district, 130 DEG C, 4th district, 140 DEG C, 5th district, 150 DEG C, 6th district, 155 DEG C of heads; Screw speed 250rpm, length-to-diameter ratio 40/1.
Embodiment 3
(1) by W-Gum, PBAT(weight-average molecular weight 100,000) drying treatment 10h in 80 DEG C of convection oven, talcum powder (3000 order) drying treatment 10h in 105 DEG C of convection oven.
(2) then 80 parts of extracting corn starch, PBAT20 part, 20 parts of softening agent glycerol, 10 parts, softening agent urea, POE-g-MAH3 part, BPO1.5 part, 4 parts of alkyl ketene dimers, 0.6 part of polyethylene wax, 0.5 part of β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid octadecanol acid esters, 2 parts of normal temperature mixing 10min in high mixer of talcum powder.
(3) mixture obtaining is joined to extruding pelletization in twin screw extruder, the each district of twin screw extruder temperature is: 90 DEG C, a district, 110 DEG C, 2nd district, 120 DEG C, 3rd district, 130 DEG C, 4th district, 140 DEG C, 5th district, 150 DEG C, 6th district, 155 DEG C of heads; Screw speed 250rpm, length-to-diameter ratio 40/1.
Embodiment 4
(1) by W-Gum, PBAT(weight-average molecular weight 12.5 ten thousand) drying treatment 10h in 80 DEG C of convection oven, talcum powder (3000 order) drying treatment 10h in 105 DEG C of convection oven.
(2) then 80 parts of extracting corn starch, PBAT20 part, 40 parts of glycerol, 10 parts of sorbyl alcohols, POE-g-MAH3 part, BPO1.5 part, 5 parts of alkyl ketene dimers, 0.6 part, paraffin, 0.5 part of 2-methylene-bis (4-methyl-6-tert-butylphenol), 2 parts of normal temperature mixing 10min in high mixer of talcum powder.
(3) mixture obtaining is joined to extruding pelletization in twin screw extruder, the each district of twin screw extruder temperature is: 90 DEG C, a district, 110 DEG C, 2nd district, 120 DEG C, 3rd district, 130 DEG C, 4th district, 140 DEG C, 5th district, 150 DEG C, 6th district, 155 DEG C of heads; Screw speed 250rpm, length-to-diameter ratio 40/1.
Embodiment 5
(1) by W-Gum, PBAT(weight-average molecular weight 12.5 ten thousand) drying treatment 10h in 80 DEG C of convection oven, talcum powder (1250 order) drying treatment 10h in 105 DEG C of convection oven.
(2) then 75 parts of extracting corn starch, PBAT25 part, 25 parts of glycerol, 5 parts of ethanamides, 2 parts of maleic anhydrides, DCP1.5 part, 1 part of enetutanedioic acid anhydride, 0.3 part of stearic acid, 0.5 part of 2-methylene-bis (4-methyl-6-tert-butylphenol), 20 parts of normal temperature mixing 10min in high mixer of talcum powder.
(3) mixture obtaining is joined to extruding pelletization in twin screw extruder, the each district of twin screw extruder temperature is: 90 DEG C, a district, 110 DEG C, 2nd district, 120 DEG C, 3rd district, 130 DEG C, 4th district, 140 DEG C, 5th district, 150 DEG C, 6th district, 155 DEG C of heads; Screw speed 300rpm, length-to-diameter ratio 40/1.
Comparative example 1
(1) by W-Gum, PBAT(weight-average molecular weight 12.5 ten thousand) drying treatment 10h in 80 DEG C of convection oven.
(2) then 75 parts of extracting corn starch, PBAT25 part, 25 parts of glycerol, 5 parts of ethanamides, 2 parts of maleic anhydrides, DCP1.5 part, 0.3 part of stearic acid, 0.5 part of normal temperature mixing 10min in high mixer of 2-methylene-bis (4-methyl-6-tert-butylphenol).
(3) mixture obtaining is joined to extruding pelletization in twin screw extruder, the each district of twin screw extruder temperature is: 90 DEG C, a district, 110 DEG C, 2nd district, 120 DEG C, 3rd district, 130 DEG C, 4th district, 140 DEG C, 5th district, 150 DEG C, 6th district, 155 DEG C of heads; Screw speed 300rpm, length-to-diameter ratio 40/1.Each embodiment material property is as table 1
Embodiment 6
(1) by potato starch, PBAT(weight-average molecular weight 20,000) drying treatment 24h in 60 DEG C of convection oven, kaolin (1250 order) drying treatment 5h in 120 DEG C of convection oven.
(2) then get 95 parts of potato starches, PBAT5 part, 25 parts of glycerol, 10 parts of propylene glycol, 1 part of maleic anhydride, DCP2 part, 3 parts of enetutanedioic acid anhydrides, 0.1 part of amine hydroxybenzene, 0.1 part of three (2.4-di-tert-butyl-phenyl) phosphorous acid ester, 15 parts of normal temperature mixing 10min in high mixer of kaolin.
(3) mixture obtaining is joined to extruding pelletization in twin screw extruder, the each district of twin screw extruder temperature is: 90 DEG C, a district, 110 DEG C, 2nd district, 120 DEG C, 3rd district, 130 DEG C, 4th district, 140 DEG C, 5th district, 150 DEG C, 6th district, 155 DEG C of heads; Screw speed 300rpm, length-to-diameter ratio 50/1.
Embodiment 7
(1) by wheat starch, PBAT(weight-average molecular weight 60,000) drying treatment 18h in 70 DEG C of convection oven, silicon-dioxide (4000 order) drying treatment 7h in 110 DEG C of convection oven.
(2) then get 85 parts of wheat starches, PBAT15 part, 25 parts of glycerol, 20 parts of ethylene glycol, 2.5 parts of maleic anhydrides, DCP0.5 part, 5 parts of enetutanedioic acid anhydrides, 0.4 part of amine hydroxybenzene, 0.3 part of three (2.4-di-tert-butyl-phenyl) phosphorous acid ester, 8 parts of normal temperature mixing 10min in high mixer of silicon-dioxide.
(3) mixture obtaining is joined to extruding pelletization in twin screw extruder, the each district of twin screw extruder temperature is: 90 DEG C, a district, 110 DEG C, 2nd district, 120 DEG C, 3rd district, 130 DEG C, 4th district, 140 DEG C, 5th district, 150 DEG C, 6th district, 155 DEG C of heads; Screw speed 300rpm, length-to-diameter ratio 50/1
As can be seen from Table 1, master batch after modification not only has good mechanical property and good kindliness, and water-intake rate declines greatly, can be directly used in and prepare the consumer's goods such as wrapping material and disposable tableware with composition prepared by this master batch and polyester blend, to reduce environmental pollution.
The above-mentioned description to embodiment is can understand and apply the invention for ease of those skilled in the art.Person skilled in the art obviously can easily make various amendments to these embodiment, and General Principle described herein is applied in other embodiment and needn't passes through performing creative labour.Therefore, the invention is not restricted to the embodiment here, those skilled in the art are according to announcement of the present invention, and not departing from improvement and the amendment that category of the present invention makes all should be within protection scope of the present invention.
Claims (10)
1. a complete biodegradable master batch, is characterized in that: be made up of the component that comprises following weight part:
2. complete biodegradable master batch according to claim 1, is characterized in that: described starch is one or more in potato starch, W-Gum, tapioca (flour) or wheat starch.
3. complete biodegradable master batch according to claim 1, is characterized in that: the weight-average molecular weight of described poly-(terephthalic acid butyleneglycol-co-hexanodioic acid butyleneglycol) ester is 20000-130000.
4. complete biodegradable master batch according to claim 1, is characterized in that: described softening agent is one or more in ethylene glycol, propylene glycol, glycerol, sorbyl alcohol, urea, methane amide or ethanamide.
5. complete biodegradable master batch according to claim 1, is characterized in that: described compatilizer is one or more in maleic anhydride, maleic anhydride grafted ethene-octene copolymer.
6. complete biodegradable master batch according to claim 1, is characterized in that: described initiator is one or more in dicumyl peroxide or benzoyl peroxide;
Or described hydrophobically modified agent is the monomer with long-chain fat hydrocarbon and reactive functionality, more preferably one or more in enetutanedioic acid anhydride and alkyl ketene dimer.
7. complete biodegradable master batch according to claim 1, is characterized in that: described lubricant is one or more in stearic acid, calcium stearate, amine hydroxybenzene, erucicamide, paraffin or polyethylene wax.
8. complete biodegradable master batch according to claim 1, it is characterized in that: described oxidation inhibitor is four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] one or more in pentaerythritol ester, β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid octadecanol acid esters, 2-methylene-bis (4-methyl-6-tert-butylphenol) or three (2.4-di-tert-butyl-phenyl) phosphorous acid ester;
Or described filler is one or more in calcium carbonate, kaolin, silicon-dioxide, mica, polynite, clay, titanium dioxide, talcum powder etc., preferably 1250 order-8000 orders of particle diameter, further preferred 2000-3000 order.
9. a preparation method for arbitrary described complete biodegradable master batch in claim 1-8, is characterized in that: comprise the steps:
(1) starch, poly-(terephthalic acid butyleneglycol-co-hexanodioic acid butyleneglycol) ester, filler are carried out to drying treatment;
(2) take each component raw material of following weight part by said ratio: starch 70-95 part, poly-(terephthalic acid butyleneglycol-co-hexanodioic acid butyleneglycol) ester 5-30 part, softening agent 30-50 part, compatilizer 0.5-3 part, initiator 0.05-2 part, hydrophobically modified agent 0.5-5 part, lubricant 0.1-0.6 part, oxidation inhibitor 0.1-0.5 part, filler 0-20 part; Above-mentioned raw materials is even in high-speed mixer and mixing;
(3) raw material step (2) being mixed joins melt blending in twin screw extruder, extrudes, tie rod, granulation.
10. preparation method according to claim 9, is characterized in that: in described step (1), starch, poly-(terephthalic acid butyleneglycol-co-hexanodioic acid butyleneglycol) ester, drying temperature are 60-80 DEG C, and be 6-24h time of drying; The drying temperature of filler is 100-120 DEG C, and the time is 5-10h; Drying plant is vacuum drying oven or convection oven;
Or twin screw extruder is in the same way or out-phase twin screw extruder in described step (3), extrusion temperature is 90-160 DEG C, screw speed 60-300rpm, and screw slenderness ratio L/D is 40-50:1.
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