CN102585485A - Starch/thermoplastic polyurethane (TPU) composite material with high mechanical property and preparation method thereof - Google Patents
Starch/thermoplastic polyurethane (TPU) composite material with high mechanical property and preparation method thereof Download PDFInfo
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- CN102585485A CN102585485A CN2012100023362A CN201210002336A CN102585485A CN 102585485 A CN102585485 A CN 102585485A CN 2012100023362 A CN2012100023362 A CN 2012100023362A CN 201210002336 A CN201210002336 A CN 201210002336A CN 102585485 A CN102585485 A CN 102585485A
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Abstract
The invention relates to a starch/thermoplastic polyurethane (TPU) composite material with high mechanical property and a preparation method thereof. The method comprises the following steps of: weighing starch, TPU, a plasticizer, a toughening agent, a reinforcing agent and an interface compatilizer according to a formula, fully mixing the materials, performing mixing molding, extrusion molding and calendering molding by using a double screw extruder, a single screw extruder, a double-step screw extruder, a kneading machine, an open mill and the like with the capacity of applying shearing force, and processing at the temperature of between 100 and 190 DEG C to prepare the starch/TPU composite material. The composite material has the advantages of high mechanical property, low cost, biodegradability, simple preparation process and the like.
Description
Technical field
The invention belongs to the biodegradable plastic technical field, be specifically related to a kind of starch/thermoplastic polyurethane matrix material and preparation method with high-mechanical property.
Background technology
The thermoplastic starch plastic fully biodegradable, and have cheap, the source is abundant, be prone to advantage such as modification processing and receive much attention.Since the eighties in 20th century, flourish along with the biodegradable starch-plastics research-and-development activity, people obtain bigger breakthrough to physics and chemistry modification, thermoplastic behavior, the Study on mechanical properties of starch.Existing polytype both at home and abroad starch biodegradation plastics come out, but its mechanical property presents fragility and influenced greatly by ambient moisture, has seriously limited the application of thermoplastic starch plastic.Employing is carried out the physical blending modification with other macromolecular materials and is prepared matrix material, can effectively improve the mechanical property and the water tolerance of thermoplastic starch plastic.
The physicals of the existing rubber of thermoplastic polyurethane (TPU) such as good springiness, wear-resisting, oil resistant, anti-ozone, low temperature resistant the processing of plastic performance arranged again, range of application very extensively.But the shortcoming that the while also has, and stability to aging is poor, accumulation of heat property is higher, wet surperficial coefficient of friction is low, skid easily, cost is higher.The type of at present TPU being carried out alloy modification comprises the TPU/ composite polyolefine material; Its principle is to utilize polyolefine to have excellent mechanical property; Thermotolerance, chemicalstability, electrical property and excellent processibility are processed alloy to TPU and polyolefine; Polyolefinic adding can significantly reduce the cost and its thermostability of raising of TPU on the one hand, and TPU can improve polyolefinic anti-impact, bonding and coating performance on the other hand.In addition, also have the alloy of other types, like the TPU/PVC alloy, the TPU/PS alloy can further improve its mechanical property and resistance toheat, and to a certain degree can reduce cost.At present to adopting nanoparticle to strengthen research and the technological invention that the TPU material prepn has well behaved film certain report is arranged also, patent KR20090117917 (A) has set forth 10 ~ 20 parts of nano silicons has been prepared the thin-film material with high adhesive force with the TPU blend.Patent JP2007186617 (A) has then reported the highest 50 parts silicic acid and TPU blend has been prepared the TPU elastic particle, can effectively keep the TPU high elastic coefficient and good elongation at break is arranged.Patent CN200610040170.8 discloses the anion in situ preparation method of a kind of thermoplastic polyurethane (TPU)/MC nylon 6 composite material.With the matrix material of this invention preparation, on its tensile strength and the basic basis of invariable of flexural strength, impelling strength and thermotolerance are significantly improved.Patent CN02139341.9 discloses a kind of rectorite leng/TPUE nano composite material that adopts the melt-blending process preparation.This invention adopts simple, free of contamination melt-blending process compound organic rectorite clay 1-10 part and remover 1-5 part of different sorts thermoplastic polyurethane elastomer R100-150 part (by weight) and different demands, promptly makes nano composite material.This material has the thermotolerance and the heat-resistant aging of good intensity, excellence, thereby has extensive use.Patent CN200910213529.0 discloses a kind of preparation method of thermoplastic polyurethane film of loading multi-wall carbon nanotubes; At first carbon nanotube being carried out early stage handles; Then the carboxylic carbon nano-tube of corresponding TPU quality 0.1%-5% was added in the corresponding TPU quality 2-2.2 solvent doubly ultra-sonic dispersion 0.5-2 hour; Add TPU again and continue to obtain behind the certain hour CNTs/TPU composite solution of homogeneous, and obtain membranoid substance through the method for electrostatic spinning.This method can be significantly improved the specific mechanical property of thermoplastic polyurethane film matrix material.Patent CN01129719.0 provides the prescription of a kind of full environment protection thermoplastic polyurethane (TPU) film; In order to produce colourless and colored polyurethane film (0.05mm-5.00mm); The prescription composition is counted with part by weight: 50 ~ 90 parts of TPU; 0 ~ 20 part extraordinary vinylformic acid trimer, 0 ~ 20 part polyol derivative softening agent, polyacrylic acid modified dose and other auxiliary agents of 0 ~ 20 part.
Though the TPU composite modification system kind that with TPU is base material is more; And also have and have many good qualities; But TPU and starch carry out blend prepares matrix material, and play-by-play is not also seen in the invention that starch content is higher than more than 15%, and T.Seidenst ü cker discovers; Utilize twin screw extruder that TPU and thermoplastic starch (TPS) blend are extruded; Adding TPS can obviously improve the biodegradation rate of system, and the advantage that sums up TPU and TPS blend comprises: the renewable resources utilization ratio is high, and (when polyvalent alcohol also can adopt renewable resources, its content can reach (80 ~ 85) wt%; Compare with other most of Biodegradable materials, it has good mechanical performance and can satisfy different application requiring, and price is comparatively cheap, has higher ventilation property and suitable oxygen-permeable and good wear resistance by the film of this mixture preparation.(Seidenst ü cker T; Fritz H.-G. Compounding Procedure; Processing Behaviour and Property Profiles of Polymeric Blends Based on TPU and Destructurized Starch .Starch, 1999,51:93 ~ 102.) but along with the raising of starch content; The mechanical property of starch/TPU matrix material obviously descends, and can't be used for the conventional field of TPU.
Summary of the invention
The objective of the invention is the problem to the prior art existence: promptly starch is owing to exist stronger hydrogen bond action power; And molecular structure presents polar behavior; With thermoplastic polyurethane structurally, can't mate on the polarity; Therefore the matrix material consistency is relatively poor, and along with the raising of starch content, its mechanical property obviously descends.The present invention provides high-mechanical property starch/thermoplastic polyurethane matrix material and preparation method, adopts the toughner system that starch/TPU matrix material is carried out toughening modifying, improves the interfacial thickness between two phases, thereby improves the mechanical property of material.In addition, under the effect through interfacial compatibilizer, reduce the surface energy between starch and the TPU molecule, also effectively improve starch and TPU two consistency between mutually, thus the starch/TPU matrix material of acquisition satisfactory mechanical property.
The object of the invention is realized through following technical scheme:
A kind of high-mechanical property starch/thermoplastic polyurethane matrix material, count according to mass fraction by following component:
10 ~ 35 parts of starch;
65 ~ 90 parts of thermoplastic polyurethanes;
0.1 ~ 20 part in softening agent;
0.1 ~ 35 part of toughner;
0.05 ~ 10 part of toughener;
0.05 ~ 8 part of interfacial compatibilizer.
Described starch comprises one or several the combination in green starch, Rhizoma Nelumbinis starch, water caltrop starch, yam starch, W-Gum, waxy corn starch, tapioca(flour), sweet potato starch, wheat starch, rice starch and the pea starch; Or one or several the combination in the following starch of gelatinization: yam starch, W-Gum, waxy corn starch, tapioca(flour), sweet potato starch, wheat starch, rice starch or pea starch; Or through one or several the combination in the following starch of esterification modification: green starch, Rhizoma Nelumbinis starch, water caltrop starch, yam starch, W-Gum, waxy corn starch, tapioca(flour), sweet potato starch, wheat starch, rice starch and pea starch; Or through one or several the combination in the following starch of oxidation modification: green starch, Rhizoma Nelumbinis starch, water caltrop starch, yam starch, W-Gum, waxy corn starch, tapioca(flour), sweet potato starch, wheat starch, rice starch or pea starch.
Described thermoplastic polyurethane (TPU) shore hardness is one or several the combination in the above industrialized thermoplastic polyurethane of 75A.
Described softening agent is methane amide, urea, terepthaloyl moietie, USP Kosher, sorbyl alcohol, gather one or several the combination in penta tetrol and other poly-hydroxy small molecules polarity plasticizer, the softening agent that the present invention adopted also comprise epoxy soybean oil with and verivate citric acid three ester class in one or several combinations.
Described toughner comprises paracril; styrene-butadiene rubber(SBR); butyl rubber; ethylene-propylene rubber(EPR); ethylene-acrylic acid copolymer; acrylic polymer; styrene butadiene thermoplasticelastomer; TEB 3K-butadiene-styrene terpolymer; vinylbenzene and isoprene-styrene block copolymer; thermoplastic elastomer (TPE); polyolefin elastomer (POE); one or several combinations in the toughner of rubber/polythene thermoplastic elastomer thermoplastic elastomer types such as (TPO).
Described toughener comprises the material of fiber-like, like one or several the combination in roving glass fiber, short glass fiber, the Mierocrystalline cellulose; Also comprise inorganic nano-particle, like nano silicon, nano-calcium carbonate, nano titanium oxide, the combination of one or several in the nanometer calcium sulfate; Also comprise nano whisker, like nanometer silicon carbide whiskers, nanometer magnesium sulfate crystal whisker, nanometer calcium sulfate whisker, nano boric acid magnesium whisker, nano zinc oxide crystal whisker, the combination of one or several in the nano aluminum borate crystal whisker palpus.
Described interfacial compatibilizer comprises silane coupling agent, titanate coupling agent, X 2073, tween 20 0, trimethyl-glycine; Triple Pressed Stearic Acid, oleic acid, LAURIC ACID 99 MIN, sodium lauryl sulphate, N-acyl amino acid type tensio-active agent, alanine type tensio-active agent and glycine type tensio-active agent; The combination of one or several in the lipid acid Sorbic Acid; In order to reduce the interface activation ability of starch and TPU, improve the biphase infiltration degree, so that improve its mechanical property.
For reaching the object of the invention; The present invention also provides the preparation method of high-mechanical property starch/thermoplastic polyurethane matrix material: with starch and thermoplastic polyurethane (TPU), softening agent, toughner, toughener and interfacial compatibilizer according to the prescription metering after; After behind the above-mentioned material thorough mixing, adopt mechanical stirring blend 1 ~ 15 minute; Adopt common plastics plasticator and screw rod extruding and granulating equipment separately or the coupling granulation of plasticating then, processing temperature is 100 ℃ ~ 190 ℃.
Said common plastics plasticator and screw rod extruding and granulating equipment comprise a kind of in Banbury mixer, mill, kneader, twin-roll plastic mixing mill, single screw extrusion machine and the twin screw extruder; Also comprise Banbury mixer and single screw extrusion machine coupling, twin-roll plastic mixing mill and single screw extrusion machine coupling; Also comprise second order screw extrusion press group, said second order screw extrusion press group comprises following any in the unit extruded: single order is a twin screw extruder, and second order is a single screw extrusion machine; Single order and second order forcing machine are all single screw extrusion machine.
Relative prior art, the present invention has following advantage and beneficial effect:
1. starch/thermoplastic polyurethane matrix material has favorable mechanical performance and wear resisting property:
The present invention adopts toughner, interfacial compatibilizer etc. that TPU and starch are carried out the interface enhancing; Improving biphase melts mutually; The starch that obtains/thermoplastic polyurethane matrix material tensile strength, elongation at break, notched Izod impact strength and low temperature complications are compared with pure TPU; All do not have obviously decline, and have more good abrasion resistance than TPU.
2. starch/thermoplastic polyurethane matrix material has biodegradable performance:
Owing to contain starch; Therefore starch/thermoplastic polyurethane matrix material has the favorable biological degradability ability; Be used for goods such as automobile, electric wire, sports goods, building materials, electron device, leather, sealing member, power tool, IT industry, toy when it after; After in case current goods are discarded, can biodegrade in environment, have the advantage of green, environmental protection.
3. starch/thermoplastic polyurethane matrix material is cheap:
The mechanical property and the pure TPU of starch/thermoplastic polyurethane matrix material are approaching, but price only is 60% ~ 80% of TPU, therefore have low cost and other advantages.
4, starch/thermoplastic polyurethane composite material and preparation method thereof is simple, environmental protection:
Content of the present invention is not added any poisonous and hazardous material, does not produce any poisonous and hazardous material in the preparation process, and the preparation process only need adopt the plastics common plastics unit of plasticating to make up and get final product, and Production Flow Chart is short, and output is high.
Specific embodiment
Through embodiment the present invention is specifically described below; Be necessary to be pointed out that at this following examples only are used for the present invention is described further; Can not be interpreted as restriction to protection domain of the present invention; The person skilled in the art in this field makes some nonessential improvement and adjustment according to the content of the invention described above to the present invention, still belongs to protection scope of the present invention.
The content measurement that patent of the present invention is done is tested according to following mode:
Various samples carry out injection moulding in the invention under 150 ~ 180 ℃; The standard batten that obtains testing; Abrasion loss is tested according to ISO-4649, gets the MV of five experiments, and tensile strength and elongation at break are tested according to ASTM D-412; The socle girder notched Izod impact strength is tested according to ASTM D-256; More than the MV of 5 experimental results is all got in experiment, and bending and unbending test is to test according to ASTM D-1052, and three specimen test temperature be to assess its damaged degree after-20 ℃ of complications 40000 times.
The pure TPU of Comparative Examples 1, shore hardness 95A is 180 ~ 190 ℃ under to be injection molded into various standard battens at injection temperature in oven dry under 80 ℃ after 4 hours, tests then, and data as a comparison.
After the TPU of the shore hardness 95A that Comparative Examples is 2,90 parts and 10 parts W-Gum mix; Via twin screw extruder; Extrusion temperature is respectively 175 ~ 190 ℃; Dried 4 hours down at 80 ℃ sample cooling back, is to be injection molded into various standard battens under 180 ~ 190 ℃ at injection temperature, tests then.
After the TPU of the shore hardness 95A that Comparative Examples is 3,80 parts and 20 parts W-Gum mix; Via twin screw extruder; Extrusion temperature is respectively 175 ~ 190 ℃; Dried 4 hours down at 80 ℃ sample cooling back, is to be injection molded into various standard battens under 180 ~ 190 ℃ at injection temperature, tests then.
After the TPU of the shore hardness 95A that Comparative Examples is 4,70 parts and 30 parts W-Gum mix; Via twin screw extruder; Extrusion temperature is respectively 175 ~ 190 ℃; Dried 4 hours down at 80 ℃ sample cooling back, is to be injection molded into various standard battens under 180 ~ 190 ℃ at injection temperature, tests then.
After the TPU of the shore hardness 95A that Comparative Examples is 5,65 parts and 35 parts W-Gum mix; Via twin screw extruder; Extrusion temperature is respectively 175 ~ 190 ℃; Dried 4 hours down at 80 ℃ sample cooling back, is to be injection molded into various standard battens under 180 ~ 190 ℃ at injection temperature, tests then.
Embodiment 1, with 10 parts of W-Gums, 90 parts of TPU, 8 parts of glycerine, 0.5 part of nano silicon (particle diameter order number is more than 5000 orders); 4 parts of paracrils, 3 parts of POE are after 1 part of process of trimethyl-glycine mixes; Join in two roller mills, after under 160 ~ 170 ℃ mixing 8 minutes, the granulation of fusion sheet material process single screw extrusion machine; Make 1# starch/thermoplastic polyurethane matrix material; The length-to-diameter ratio of the single screw extrusion machine that is adopted is 35:1, and extrusion temperature is 135 ~ 160 ℃, screw speed 80r/min.
Embodiment 2, with 20 parts of W-Gums, 80 parts of TPU, 5 parts of glycerine, 3 parts in urea; 1 part of nano-calcium carbonate (particle diameter order number is more than 5000 orders), 5 parts of styrene butadiene thermoplasticelastomers, 5 parts of TEB 3Ks-butadiene-styrene terpolymer; After 0 0.5 parts of processes of tween 20 mix, join twin screw and extrude, the length-to-diameter ratio of forcing machine is 40:1; Extrusion temperature is 135 ~ 175 ℃, and screw speed 200r/min makes 2# starch/thermoplastic polyurethane matrix material.
Embodiment 3, with 30 parts of W-Gums; 10 parts of sorbyl alcohols, 2 parts of methane amides, 1 part of nano titanium oxide (particle diameter order number is more than 5000 orders); 8 parts of styrene butadiene thermoplasticelastomers; 9 parts of vinylbenzene and isoprene-styrene block copolymers, 1 part of process of silane coupling agent mix in the second order forcing machine that twin screw extruder that back and 70 parts of TPU add diameter (Ф) 25, length-to-diameter ratio (L/D) 35 respectively and diameter (Ф) 45, length-to-diameter ratio (L/D) 30 single screw extrusion machines make up continuous plastication and extrude, and make 3# starch/thermoplastic polyurethane matrix material; Wherein first double screw extrusion press barrel temperature is 80 ~ 175 ℃; Screw speed 300r/min, 175 ~ 185 ℃ of second order screw extrusion press barrel temperatures, screw speed 150r/min.
Embodiment 4, with 35 parts of W-Gums, 12 parts of glycerine, 2 parts of methane amides, 2 parts of nanometer silicon carbide whiskers (particle diameter order number is more than 5000 orders); 10 parts of styrene butadiene thermoplasticelastomers, 5 parts of TPE things are after 1 part of process of titanate coupling agent mixes; Added by twin screw extruder first spout, 65 parts of TPU are added by second spout, screw diameter (Ф) 25, length-to-diameter ratio (L/D) 45; The twin screw extruder barrel temperature is 80 ~ 175 ℃, screw speed 150r/min.
Embodiment 5, with 25 parts of tapioca(flour)s, 8 parts of 75 parts of glycerine of TPU, 1 part of methane amide, nano aluminum borate crystal whisker must (particle diameter order number be more than 5000 orders) 2 parts; 2 parts in ethylene-propylene rubber(EPR), 6 parts of POE are after 1 part of process of amino acid type surfactant mixes; Adopt single screw extrusion machine to prepare 5# starch/thermoplastic polyurethane matrix material; The length-to-diameter ratio of the single screw extrusion machine that is adopted is 35:1, and extrusion temperature is 100 ~ 165 ℃, screw speed 150r/min.
Embodiment 6,25 parts of sweet potato starch, 75 parts of TPU with the gelatinization modification; 9 parts of methane amides, 1 part of Mierocrystalline cellulose, 1 part of nano boric acid magnesium whisker (particle diameter order number is more than 5000 orders); 3 parts of 3 parts of ethylene-acrylic acid copolymers, 1 part of acrylic polymer, 2 parts of styrene butadiene thermoplasticelastomers, TEB 3K-butadiene-styrene terpolymer; 2 parts of TPE, 0.5 part of amino acid type surfactant is after 01 parts of processes of tween 20 mix; Adopt prepared in twin-screw extruder 6# starch/thermoplastic polyurethane matrix material; The length-to-diameter ratio of the single screw extrusion machine that is adopted is 40:1, and extrusion temperature is 100 ~ 165 ℃, screw speed 250r/min.
Embodiment 7,18 parts of W-Gums, 82 parts of TPU with oxidation modification, 6 parts of glycerine, 3 parts of methane amides; 1 part of nano silicon, 2 parts of nano boric acid magnesium whiskers (particle diameter order number is more than 5000 orders), 3 parts of acrylic polymers, 8 parts of styrene butadiene thermoplasticelastomers; 3 parts of POE, 0.5 part of betaine type amphoteric surfactant is after 1 part of process of amino acid type surfactant mixes; Adopt prepared in twin-screw extruder 7# starch/thermoplastic polyurethane matrix material; The length-to-diameter ratio of the single screw extrusion machine that is adopted is 40:1, and extrusion temperature is 100 ~ 165 ℃, screw speed 250r/min.
Embodiment 8, with 20 parts of the yam starchs of esterification modification, 6 parts of sorbyl alcohols, 3 parts of methane amides; 2 parts of nano silicons (particle diameter order number is more than 5000 orders), 3 parts of styrene butadiene thermoplasticelastomers, 5 parts of vinylbenzene and isoprene-styrene block copolymers; 1 part of betaine type amphoteric surfactant; After 1 part of process of titanate coupling agent mixes, add, during the twin screw that 80 parts of TPU add two rank screw extrusion press of diameter (Ф) 25, length-to-diameter ratio (L/D) 35 to by second spout is extruded by first spout; Continuous plastication is extruded in the second order forcing machine of diameter (Ф) 45, the combination of length-to-diameter ratio (L/D) 30 single screw extrusion machines again; Make 8# starch/thermoplastic polyurethane matrix material, wherein first double screw extrusion press barrel temperature is 80 ~ 175 ℃, screw speed 200r/min; 175 ~ 185 ℃ of second order screw extrusion press barrel temperatures, screw speed 150r/min.
Embodiment 9, with 30 parts of yam starchs, 6 parts of Hydrocerol A triphenylmethyl methacrylates, 6 parts of methane amides; 2 parts of glycerine, 1 part of nano silicon (particle diameter order number is more than 5000 orders), 2 parts of nano zine oxides; 4 parts of ethylene-acrylic acid resin copolymers, 10 parts of vinylbenzene and isoprene-styrene block copolymers, 10 parts of POE; 1 part of betaine type amphoteric surfactant through after mixing, is added by first spout; During the twin screw that 70 parts of TPU add two rank screw extrusion press of diameter (Ф) 25, length-to-diameter ratio (L/D) 35 to by second spout was extruded, continuous plastication was extruded in the second order forcing machine of diameter (Ф) 45, the combination of length-to-diameter ratio (L/D) 30 single screw extrusion machines again, makes 9# starch/thermoplastic polyurethane matrix material; Wherein first double screw extrusion press barrel temperature is 80 ~ 175 ℃; Screw speed 200r/min, 175 ~ 185 ℃ of second order screw extrusion press barrel temperatures, screw speed 150r/min.
As shown in table 1; For the test data of embodiments of the invention and Comparative Examples gathers; Adopt the high-mechanical property starch/thermoplastic polyurethane matrix material of method preparation disclosed by the invention; Compare with current material, its tensile strength, elongation at break, notched Izod impact strength do not have obvious decline, but wear resisting property is more excellent.
Table 1Starch/the mechanical property of thermoplastic polyurethane matrix material and the data of abrasion loss
| Sample number into spectrum | Tensile strength (MPa) | Elongation at break (%) | Notched Izod impact strength (J/M) | Abrasion loss (mm 3） | -20 ℃ of tortuous experiments |
| Comparative Examples 1 | 32.6 | 675 | 425.2 | 33 | ＞40000 times |
| Comparative Examples 2 | 29.3 | 625 | 451.4 | 28 | ＞40000 times |
| Comparative Examples 3 | 24.1 | 210 | 383.3 | 25 | 1000 times |
| Comparative Examples 4 | 14.5 | 118 | 321.5 | 22 | ＜800 times |
| Comparative Examples 5 | 13.8 | 87 | 298.5 | 21 | ＜800 times |
| Embodiment 1 | 31.8 | 665 | 475.1 | 26.7 | ＞40000 times |
| Embodiment 2 | 30.2 | 638 | 525.4 | 25.7 | ＞40000 times |
| Embodiment 3 | 28.7 | 614 | 622.4 | 22.8 | ＞40000 times |
| Embodiment 4 | 27.4 | 593 | 651.8 | 21.5 | ＜36000 times |
| Embodiment 5 | 29.2 | 625 | 550.4 | 25.3 | ＞40000 times |
| Embodiment 6 | 29.8 | 631 | 555.4 | 25.4 | ＞40000 times |
| Embodiment 7 | 30.4 | 648 | 535.4 | 25.1 | ＞40000 times |
| Embodiment 8 | 31.2 | 660 | 543.5 | 24.2 | ＞40000 times |
| Embodiment 9 | 29.4 | 610 | 593.8 | 22.5 | ＞40000 times |
Claims (10)
1. high-mechanical property starch/thermoplastic polyurethane matrix material is characterized in that its component and content counts with mass fraction:
Starch 10 ~ 35;
Thermoplastic polyurethane 65 ~ 90;
Softening agent 0.1 ~ 20;
Toughner 0.1 ~ 35;
Toughener 0.05 ~ 10;
Interfacial compatibilizer 0.05 ~ 8.
2. starch according to claim 1/thermoplastic polyurethane matrix material is characterized in that said starch comprises one or several the combination in green starch, Rhizoma Nelumbinis starch, water caltrop starch, yam starch, W-Gum, waxy corn starch, tapioca(flour), sweet potato starch, wheat starch, rice starch and the pea starch; Also comprise the verivate of above-mentioned starch through gelatinization, esterification or oxidation modification.
3. starch according to claim 1/thermoplastic polyurethane matrix material is characterized in that said thermoplastic polyurethane is one or several combination of the above thermoplastic polyurethane of shore hardness 75A.
4. starch according to claim 1/thermoplastic polyurethane matrix material is characterized in that said softening agent comprises methane amide, urea, terepthaloyl moietie, USP Kosher, sorbyl alcohol, gathers one or several the combination in penta tetrol and other poly-hydroxy small molecules polarity plasticizer.
5. starch according to claim 4/thermoplastic polyurethane matrix material is characterized in that said softening agent also comprises one or several the combination in epoxy soybean oil and the verivate citric acid three ester class thereof.
6. starch according to claim 1/thermoplastic polyurethane matrix material is characterized in that said toughner comprises one or several the combination in the toughner of thermoplastic elastomer type of paracril, styrene-butadiene rubber(SBR), butyl rubber, ethylene-propylene rubber(EPR), ethylene-acrylic acid copolymer, acrylic polymer, styrene butadiene thermoplasticelastomer, TEB 3K-butadiene-styrene terpolymer, vinylbenzene and isoprene-styrene block copolymer, thermoplastic elastomer (TPE), polyolefin elastomer (POE), rubber/polythene thermoplastic elastomer (TPO).
7. starch according to claim 1/thermoplastic polyurethane matrix material is characterized in that said toughener comprises one or several the combination in roving glass fiber, short glass fiber, the cellulosic fiber-like material; Also comprise one or several the combination in the inorganic nano-particle of nano silicon, nano-calcium carbonate, nano titanium oxide and nanometer calcium sulfate; Also comprise nanometer silicon carbide whiskers, nanometer magnesium sulfate crystal whisker, nanometer calcium sulfate whisker, nano boric acid magnesium whisker, nano zinc oxide crystal whisker and nano aluminum borate crystal whisker must nano whisker in one or several combination.
8. starch according to claim 1/thermoplastic polyurethane matrix material is characterized in that said interfacial compatibilizer comprises one or several the combination in silane coupling agent, titanate coupling agent, X 2073, tween 20 0, trimethyl-glycine, Triple Pressed Stearic Acid, oleic acid, LAURIC ACID 99 MIN, sodium lauryl sulphate, N-acyl amino acid type tensio-active agent, alanine type tensio-active agent and glycine type tensio-active agent, the lipid acid Sorbic Acid.
9. prepare the method for the described starch of one of claim 1 ~ 8/thermoplastic polyurethane matrix material, it is characterized in that may further comprise the steps:
(1) starch and thermoplastic polyurethane, softening agent, toughner, toughener and interfacial compatibilizer are measured according to prescription, adopt mechanical stirring blend 1 ~ 15 minute;
(2) adopt the independent or coupling of common plastics plasticator and the screw rod extruding and granulating equipment granulation of plasticating, processing temperature is 100 ℃ ~ 190 ℃.
10. the preparation method of starch according to claim 9/thermoplastic polyurethane matrix material is characterized in that said common plastics plasticator and screw rod extruding and granulating equipment comprise a kind of in Banbury mixer, mill, kneader, twin-roll plastic mixing mill, single screw extrusion machine and the twin screw extruder; Also comprise Banbury mixer and single screw extrusion machine coupling, twin-roll plastic mixing mill and single screw extrusion machine coupling; Also comprise second order screw extrusion press group, said second order screw extrusion press group comprises following any in the unit extruded: single order is a twin screw extruder, and second order is a single screw extrusion machine; Single order and second order forcing machine are all single screw extrusion machine.
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