CN102585485B - 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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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 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
Thermoplastic starch plastic fully biodegradable, and have cheap, source is abundant, the easy advantage such as modification and receiving much attention.Since the eighties in 20th century, flourish along with biodegradable starch-plastics research-and-development activity, people obtain larger breakthrough to the research of the physical chemical modification of starch, thermoplastic behavior, mechanical property.Existing polytype starch biodegradation plastics come out both at home and abroad, but its mechanical property presents fragility and affected greatly by ambient moisture, has seriously limited the application of thermoplastic starch plastic.Employing is carried out physical modification with other macromolecular materials and is prepared matrix material, can effectively improve mechanical property and the water tolerance of thermoplastic starch plastic.
The physicals of the existing rubber of thermoplastic polyurethane (TPU) is as good springiness, wear-resisting, oil resistant, resistance to ozone, the low temperature resistant processing characteristics that has again plastics, and range of application is very extensive.But the shortcoming that the while also has, and ageing resistance is poor, accumulation of heat is higher, wet surperficial coefficient of friction is low, easily skid, cost is higher.The type of at present TPU being carried out to alloy modification comprises TPU/ composite polyolefine material, its principle is to utilize polyolefine to have good mechanical property, thermotolerance, chemical stability, electrical property and excellent processibility, TPU and polyolefine are made to alloy, can significantly reduce the cost of TPU and improve its thermostability polyolefinic adding on the one hand, TPU can improve polyolefinic anti-impact, bonding and coating performance on the other hand.In addition, also have the alloy of other types, as TPU/PVC alloy, TPU/PS alloy, can further improve its mechanical property and resistance toheat, and to a certain degree can reduce costs.At present the research and the technological invention that adopt the preparation of nanoparticle enhancing TPU material to have well behaved film are also had to certain report, patent KR20090117917 (A) has set forth 10 ~ 20 parts of nano silicons has been prepared to the thin-film material with high adhesive force with TPU blend.Patent JP2007186617 (A) has reported the silicic acid of the highest 50 parts and TPU blend has been prepared to TPU elastic particle, can effectively keep TPU high elastic coefficient and have good elongation at break.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 substantially constant basis of flexural strength, impelling strength and thermotolerance are significantly improved.Patent CN02139341.9 discloses a kind of rectorite/thermoplastic polyurethane elastomer nano composite material that adopts melt-blending process to prepare.This invention adopts simple, free of contamination melt-blending process compound organic rectorite clay 1-10 part of different sorts thermoplastic polyurethane elastomer R100-150 part (by weight) and different demands and remover 1-5 part, makes nano composite material.This material has 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, first carbon nanotube being carried out to early stage processes, then the carboxylic carbon nano-tube of corresponding TPU quality 0.1%-5% is added to ultrasonic dispersion 0.5-2 hour in corresponding TPU quality 2-2.2 solvent doubly, add again TPU to continue to obtain the CNTs/TPU composite solution of homogeneous after certain hour, and obtain membranoid substance by the method for electrostatic spinning.The method can be significantly improved the specific mechanical property of thermoplastic polyurethane film matrix material.Patent CN01129719.0 provides the formula of a kind of full environment protection thermoplastic polyurethane (TPU) film, in order to produce colourless and colored polyurethane film (0.05mm-5.00mm), formula composition is counted with part by weight: 50 ~ 90 parts of TPU, the special acrylic acid trimer of 0 ~ 20 part, the polyol derivative softening agent of 0 ~ 20 part, polyacrylic acid modified dose and other auxiliary agents of 0 ~ 20 part.
Although the TPU composite modification system kind that the TPU of take is base material is more, and also have and have many good qualities, but TPU and starch carry out blend prepares matrix material, starch content yet there are no play-by-play higher than more than 15% invention, T.Seidenst ü cker studies discovery, utilize twin screw extruder by TPU and thermoplastic starch (TPS) blending extrusion, add TPS can obviously improve the biodegradation rate of system, the advantage that sums up TPU and TPS blend comprises: renewable resources utilization ratio is high (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 property can meet different application requiring, and price is comparatively cheap, and the film of being prepared by this mixture has higher ventilation property and suitable oxygen-permeable and good wear resistance.(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 declines, cannot be for the field of TPU routine.
Summary of the invention
The object of the invention is the problem existing for prior art: starch is owing to existing stronger Hyarogen-bonding, and molecular structure presents polar behavior, with thermoplastic polyurethane structurally, cannot mate in polarity, therefore matrix material consistency is poor, along with the raising of starch content, its mechanical property obviously declines.The invention provides high-mechanical property starch/thermoplastic polyurethane matrix material and preparation method, adopt toughner system to carry out toughening modifying to starch/TPU matrix material, improve the interfacial thickness between two-phase, thereby improve the mechanical property of material.In addition, under the effect by interfacial compatibilizer, reduce the surface energy between starch and TPU molecule, also effectively improve the consistency between starch and TPU two-phase, thereby obtain starch/TPU matrix material of satisfactory mechanical property.
Object of the present invention is achieved through the following technical solutions:
High-mechanical property starch/thermoplastic polyurethane matrix material, by following component, according to mass fraction, counted:
10 ~ 35 parts of starch;
65 ~ 90 parts of thermoplastic polyurethanes;
0.1 ~ 20 part, 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 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 industrialized thermoplastic polyurethane more than 75A.
Described softening agent is one or several the combination in methane amide, urea, ethylene glycol, glycerol, sorbyl alcohol, poly-penta tetrol and other poly-hydroxy small molecules polarity plasticizer, softening agent of the present invention also comprise epoxy soybean oil with and derivative citric acid three ester class in one or several combinations.
Described toughner comprises paracril, styrene-butadiene rubber(SBR), isoprene-isobutylene rubber, ethylene-propylene rubber(EPR), ethylene-acrylic acid copolymer, acrylic polymer, styrene butadiene thermoplasticelastomer, MBS terpolymer, vinylbenzene and isoprene-styrene block copolymer, thermoplastic elastomer (TPE), polyolefin elastomer (POE), one or several combinations in the toughner of the thermoplastic elastomer types such as rubber/polythene thermoplastic elastomer (TPO).
Described toughener comprises the material of fiber-like, as one or several the combination in roving glass fiber, short glass fiber, Mierocrystalline cellulose; Also comprise inorganic nano-particle, as nano silicon, nano-calcium carbonate, nano titanium oxide, the combination of one or several in nanometer calcium sulfate; Also comprise nano whisker, as 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 nano aluminum borate crystal whisker palpus.
Described interfacial compatibilizer comprises silane coupling agent, titanate coupling agent, Sodium dodecylbenzene sulfonate, tween 20 0, trimethyl-glycine; stearic acid, oleic acid, lauric acid; 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 lipid acid Sorbic Acid; in order to reduce the interface activation energy of starch and TPU, improve the infiltration degree of two-phase, to 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: by starch and thermoplastic polyurethane (TPU), softening agent, toughner, toughener and interfacial compatibilizer according to formula metering after, after after above-mentioned material fully mixes, adopt mechanical stirring blend 1 ~ 15 minute; Then adopt common plastics plasticator and Screw Extrusion granulating equipment separately or the coupling granulation of plasticating, processing temperature is 100 ℃ ~ 190 ℃.
Described common plastics plasticator and Screw Extrusion granulating equipment comprise a kind of in Banbury mixer, mill, kneader, twin-roll plastic mixing mill, single screw extrusion machine and 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 unit, described second order Screw Extrusion unit comprises following any in unit extruded: single order is twin screw extruder, and second order is single screw extrusion machine; Single order and second order forcing machine are all single screw extrusion machine.
Relative prior art, tool of the present invention has the following advantages and beneficial effect:
1. starch/thermoplastic polyurethane matrix material has good mechanical property and wear resisting property:
The present invention adopts toughner, interfacial compatibilizer etc. to carry out interface enhancing to TPU and starch, improve melting mutually of two-phase, starch/thermoplastic polyurethane matrix material the tensile strength, elongation at break, notched Izod impact strength and the low temperature complications that obtain are compared with pure TPU, all without obvious, decline, and have more good wear resisting property than TPU.
2. starch/thermoplastic polyurethane matrix material has biodegradable performance:
Owing to containing starch, therefore starch/thermoplastic polyurethane matrix material has good biodegradability, after it is for goods such as automobile, electric wire, sports goods, building materials, electron device, leather, sealing member, power tool, IT industry, toys, after once current goods are discarded, in environment, can carry out biological degradation, there is green, environmental protection.
3. starch/thermoplastic polyurethane matrix material is cheap:
The mechanical property of starch/thermoplastic polyurethane matrix material and pure TPU approach, but price is only 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, in preparation process, does not produce any poisonous and hazardous material, and preparation process only need to adopt the plastics common plastics unit of plasticating to combine, and Production Flow Chart is short, and output is high.
Specific embodiment
Below by embodiment, the present invention is specifically described; be necessary to be pointed out that at this following examples are only for the invention will be further described; can not be interpreted as limiting the scope of the 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 in the following manner:
In invention, various samples carry out injection moulding at 150 ~ 180 ℃, obtain the standard batten of test, abrasion loss is tested according to ISO-4649, get the mean value of five experiments, tensile strength and elongation at break are tested according to ASTM D-412, socle girder notched Izod impact strength is tested according to ASTM D-256, more than the mean value of 5 experimental results is all got in experiment, bending and unbending test is to test according to ASTM D-1052, and three specimen test temperature are assessed its damaged degree for after-20 ℃ of complications 40000 times.
The pure TPU of comparative example 1, shore hardness 95A was dried after 4 hours at 80 ℃, at injection temperature, was at 180 ~ 190 ℃, to be injection molded into various standard battens, then tested, and data as a comparison.
After the TPU of the shore hardness 95A that comparative example is 2,90 parts mixes with the W-Gum of 10 parts, via twin screw extruder, extrusion temperature is respectively 175 ~ 190 ℃, after sample is cooling, at 80 ℃, dry 4 hours, at injection temperature, be at 180 ~ 190 ℃, to be injection molded into various standard battens, then test.
After the TPU of the shore hardness 95A that comparative example is 3,80 parts mixes with the W-Gum of 20 parts, via twin screw extruder, extrusion temperature is respectively 175 ~ 190 ℃, after sample is cooling, at 80 ℃, dry 4 hours, at injection temperature, be at 180 ~ 190 ℃, to be injection molded into various standard battens, then test.
After the TPU of the shore hardness 95A that comparative example is 4,70 parts mixes with the W-Gum of 30 parts, via twin screw extruder, extrusion temperature is respectively 175 ~ 190 ℃, after sample is cooling, at 80 ℃, dry 4 hours, at injection temperature, be at 180 ~ 190 ℃, to be injection molded into various standard battens, then test.
After the TPU of the shore hardness 95A that comparative example is 5,65 parts mixes with the W-Gum of 35 parts, via twin screw extruder, extrusion temperature is respectively 175 ~ 190 ℃, after sample is cooling, at 80 ℃, dry 4 hours, at injection temperature, be at 180 ~ 190 ℃, to be injection molded into various standard battens, then test.
Embodiment 1, by 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, 1 part of trimethyl-glycine is after mixing, join in two roller mills, at 160 ~ 170 ℃ after mixing 8 minutes, melting sheet material, through single screw extrusion machine granulation, is made to 1# starch/thermoplastic polyurethane matrix material, and the length-to-diameter ratio of the single screw extrusion machine adopting is 35:1, extrusion temperature is 135 ~ 160 ℃, screw speed 80r/min.
Embodiment 2, by 20 parts of W-Gums, 80 parts of TPU, 5 parts of glycerine, 3 parts, 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 MBS terpolymers, 0 0.5 parts of tween 20s, after mixing, join on twin-screw extrusion, 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, by 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 silane coupling agent adds respectively diameter (Ф) 25 with 70 parts of TPU after mixing, the twin screw extruder of length-to-diameter ratio (L/D) 35 and diameter (Ф) 45, in the second order forcing machine of length-to-diameter ratio (L/D) 30 single screw extrusion machine combinations, continuous plastication is extruded, make 3# starch/thermoplastic polyurethane matrix material, wherein single order twin screw extruder 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, by 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, 1 part of titanate coupling agent is after mixing, by twin screw extruder the first spout, added, 65 parts of TPU are added by the second spout, screw diameter (Ф) 25, length-to-diameter ratio (L/D) 45, twin screw extruder barrel temperature is 80 ~ 175 ℃, screw speed 150r/min.
Embodiment 5, by 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 palpus (particle diameter order number is more than 5000 orders) 2 parts, 2 parts, ethylene-propylene rubber(EPR), 6 parts of POE, 1 part of amino acid type surfactant is after mixing, adopt single screw extrusion machine to prepare 5# starch/thermoplastic polyurethane matrix material, the length-to-diameter ratio of the single screw extrusion machine adopting is 35:1, and extrusion temperature is 100 ~ 165 ℃, screw speed 150r/min.
Embodiment 6, by 25 parts of the sweet potato starch of gelatinization modification, 75 parts of TPU, 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 ethylene-acrylic acid copolymers, 1 part of acrylic polymer, 2 parts of styrene butadiene thermoplasticelastomers, 3 parts of MBS terpolymers, 2 parts of TPE, 0.5 part of amino acid type surfactant, 01 parts of tween 20s are after mixing, adopt twin screw extruder to prepare 6# starch/thermoplastic polyurethane matrix material, the length-to-diameter ratio of the single screw extrusion machine adopting is 40:1, extrusion temperature is 100 ~ 165 ℃, screw speed 250r/min.
Embodiment 7, by 18 parts of the W-Gums of oxidation modification, 82 parts of TPU, 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, 1 part of amino acid type surfactant is after mixing, adopt twin screw extruder to prepare 7# starch/thermoplastic polyurethane matrix material, the length-to-diameter ratio of the single screw extrusion machine adopting is 40:1, extrusion temperature is 100 ~ 165 ℃, screw speed 250r/min.
Embodiment 8, by 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, 1 part of titanate coupling agent is after mixing, by the first spout, added, 80 parts of TPU add diameter (Ф) 25 to by the second spout, in the twin-screw extrusion of two rank screw extrusion press of length-to-diameter ratio (L/D) 35, again through diameter (Ф) 45, in the second order forcing machine of length-to-diameter ratio (L/D) 30 single screw extrusion machine combinations, continuous plastication is extruded, make 8# starch/thermoplastic polyurethane matrix material, wherein single order twin screw extruder 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, by 30 parts of yam starchs, 6 parts of citric acid 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, after mixing, by the first spout, added, 70 parts of TPU add diameter (Ф) 25 to by the second spout, in the twin-screw extrusion of two rank screw extrusion press of length-to-diameter ratio (L/D) 35, again through diameter (Ф) 45, in the second order forcing machine of length-to-diameter ratio (L/D) 30 single screw extrusion machine combinations, continuous plastication is extruded, make 9# starch/thermoplastic polyurethane matrix material, wherein single order twin screw extruder 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 example gathers, high-mechanical property starch/thermoplastic polyurethane the matrix material that adopts method disclosed by the invention to prepare, compare with current material, its tensile strength, elongation at break, notched Izod impact strength are without obvious decline, but wear resisting property is more excellent.
table 1the mechanical property of starch/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 example 1 | 32.6 | 675 | 425.2 | 33 | > 40000 times |
| Comparative example 2 | 29.3 | 625 | 451.4 | 28 | > 40000 times |
| Comparative example 3 | 24.1 | 210 | 383.3 | 25 | 1000 times |
| Comparative example 4 | 14.5 | 118 | 321.5 | 22 | < 800 times |
| Comparative example 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 (3)
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;
Described starch comprises one or several the combination in green starch, Rhizoma Nelumbinis starch, water caltrop starch, yam starch, W-Gum, tapioca (flour), sweet potato starch, wheat starch, rice starch and pea starch, or comprises that above-mentioned starch is through the derivative of gelatinization, esterification or oxidation modification; Described thermoplastic polyurethane is one or several combination of more than shore hardness 75A thermoplastic polyurethane; Described softening agent comprises one or several the combination in methane amide, urea, ethylene glycol, glycerol, sorbyl alcohol, or comprises one or several the combination in epoxy soybean oil and derivative and citric acid three ester class; Described toughner comprises one or several the combination in paracril, styrene-butadiene rubber(SBR), isoprene-isobutylene rubber, ethylene-propylene rubber(EPR), ethylene-acrylic acid copolymer, acrylic polymer, styrene butadiene thermoplasticelastomer, MBS terpolymer; Described toughener comprises one or several the combination in roving glass fiber, short glass fiber, cellulosic fiber-like material, or comprise one or several the combination in the inorganic nano-particle of nano silicon, nano-calcium carbonate, nano titanium oxide and nanometer calcium sulfate, or 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; Described interfacial compatibilizer comprises one or several the combination in silane coupling agent, titanate coupling agent, Sodium dodecylbenzene sulfonate, tween 20 0, trimethyl-glycine, stearic acid, oleic acid, lauric acid, sodium lauryl sulphate, N-acyl amino acid type tensio-active agent, alanine type tensio-active agent and glycine type tensio-active agent.
2. prepare the method for starch/thermoplastic polyurethane matrix material claimed in claim 1, it is characterized in that comprising the following steps:
(1) by starch and thermoplastic polyurethane, softening agent, toughner, toughener and interfacial compatibilizer according to formula metering, adopt mechanical stirring blend 1 ~ 15 minute;
(2) adopt the independent or coupling of common plastics plasticator and the Screw Extrusion granulating equipment granulation of plasticating, processing temperature is 100 ℃ ~ 190 ℃.
3. the preparation method of starch/thermoplastic polyurethane matrix material according to claim 2, it is characterized in that described common plastics plasticator comprises a kind of in Banbury mixer, mill, kneader, twin-roll plastic mixing mill, described Screw Extrusion granulating equipment comprises a kind of in single screw extrusion machine and twin screw extruder, second order Screw Extrusion unit, described second order Screw Extrusion unit comprises following any in unit extruded: single order is twin screw extruder, and second order is single screw extrusion machine; Or single order and second order forcing machine are all single screw extrusion machine.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101007881A (en) * | 2007-01-08 | 2007-08-01 | 华南理工大学 | Starch and polyvinyl alcohol thermoplastic material preparation method |
| CN101367986A (en) * | 2007-08-14 | 2009-02-18 | 袁明龙 | Coupling and capacity increasing technique for coblended interface of biodegradation polylactic acid/starch composite material |
| WO2009095622A3 (en) * | 2008-02-01 | 2009-09-24 | Roquette Freres | Method for preparing thermoplastic compositions based on plasticized starch and resulting compositions |
| EP2247662A2 (en) * | 2008-02-01 | 2010-11-10 | Roquette Freres | Thermoplastic compositions based on soluble starch and method for preparing such compositions |
| EP2310447A1 (en) * | 2008-07-24 | 2011-04-20 | Roquette Freres | Process for preparing compositions based on a starchy component and on a synthetic polymer |
| CN102153985A (en) * | 2011-02-26 | 2011-08-17 | 浙江万和高分子材料有限公司 | Modified polyurethane hot melt adhesive using plants as raw materials and production process thereof |
-
2012
- 2012-01-06 CN CN201210002336.2A patent/CN102585485B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101007881A (en) * | 2007-01-08 | 2007-08-01 | 华南理工大学 | Starch and polyvinyl alcohol thermoplastic material preparation method |
| CN101367986A (en) * | 2007-08-14 | 2009-02-18 | 袁明龙 | Coupling and capacity increasing technique for coblended interface of biodegradation polylactic acid/starch composite material |
| WO2009095622A3 (en) * | 2008-02-01 | 2009-09-24 | Roquette Freres | Method for preparing thermoplastic compositions based on plasticized starch and resulting compositions |
| EP2247662A2 (en) * | 2008-02-01 | 2010-11-10 | Roquette Freres | Thermoplastic compositions based on soluble starch and method for preparing such compositions |
| EP2310447A1 (en) * | 2008-07-24 | 2011-04-20 | Roquette Freres | Process for preparing compositions based on a starchy component and on a synthetic polymer |
| CN102153985A (en) * | 2011-02-26 | 2011-08-17 | 浙江万和高分子材料有限公司 | Modified polyurethane hot melt adhesive using plants as raw materials and production process thereof |
Non-Patent Citations (6)
| Title |
|---|
| Seidenstücker T,Fritz H.G..Compounding procedure, processing behaviour and property profiles of polymeric blends based on thermoplastic poly(ester-urethanes) and destructurized starch.《starch》.1999,第51卷93-102. * |
| SeidenstückerT，FritzH.G..Compoundingprocedure processing behaviour and property profiles of polymeric blends based on thermoplastic poly(ester-urethanes) and destructurized starch.《starch》.1999 |
| 张美洁等.淀粉改性可生物降解聚氨酯材料研究进展.《塑料科技》.2002,(第05期), |
| 李绍雄，刘益军.聚氨酯树脂及其应用.《聚氨酯树脂及其应用》.化学工业出版社,2002,(第一版), * |
| 淀粉改性可生物降解聚氨酯材料研究进展;张美洁等;《塑料科技》;20021006(第05期);全文 * |
| 邱威扬,邱贤华等.淀粉塑料——降解塑料研究与应用.《淀粉塑料——降解塑料研究与应用》.化学工业出版社,2002,(第一版), * |
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