CN103205021A - Thermoplastic and PBAT blend and preparation method thereof - Google Patents
Thermoplastic and PBAT blend and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a thermoplastic starch and PBAT blend. The thermoplastic starch and PBAT blend is prepared by using 30-60 parts by weight of natural starch, 10-20 parts by weight of a plasticizer, 10-30 parts by weight of PBAT, 5-10 parts by weight of a compatibilizer, 0.4-5 parts by weight of a strengthening agent, and 0.25-5 parts by weight of a lubricant. The invention also discloses a preparation method of the thermoplastic starch and PBAT blend. The invention provides a novel degradable material having a use value. The novel degradable material which is the PBAT guarantees the complete biodegradability of the blend, obviously improves the mechanical performances and the regenerative resistance of the blend, and reduces the cost of the blend. The blend has the advantages of good tensile property, good toughness, and control of the degradation time of the blend in a reasonable range, is in favor of the storage and the application, and has a very wide application prospect.
Description
Technical field
The present invention relates to technical field of polymer materials, relate in particular to a kind of thermoplastic starch and PBAT blend and preparation method thereof.
Background technology
The plastics that with the petrochemical complex are raw material production rely on characteristics such as it is light, durable, good processability to be widely used in human lives's every field; but compare with other materials; they almost can not be degraded at nature, have brought huge pressure to environment protection.On the other hand, oil is non-renewable resource, and by present consumption speed, global explored reserves only can satisfy 40 years.Therefore, exploitation is not that the degradable plastics of raw material is to alleviating " white pollution ", reducing consumption of petroleum and have very important meaning with the oil.
Along with the aggravation and " white pollution " havoc to environment of world energy sources crisis, the substitute of seeking general-purpose plastics has become the research emphasis of various countries, and research " green polymer " comes into one's own gradually.At present, though the industrialization of degradation material product is still immature, need constantly improve performance, reduce cost and widen application market.In the application process of reality, should solve the high stability of degradable material goods in moulding, storage and use, can degrade fast after guaranteeing again to discard, this is the maximum characteristics that degradative plastics is different from conventional plastic, also is the emphasis problem of research.
Starch has various in style, originate abundant and low-cost characteristics, and be subject to microbial attack again, and can provide nutrient for microorganism, biodegradable final product is carbonic acid gas and water, can not pollute environment.Therefore starch receives much attention in the research of biodegradable material, provides a good approach for solving white pollution.Because native starch is polyol, many complete particles that form microlitic structure with interaction of hydrogen bond between its neighboring molecule, its poly-hydroxy structure makes it have extremely strong wetting ability, very responsive to ambient moisture, hang down the embrittlement of dewatering under the wet environment, the intrinsic mechanical property of suction forfeiture lacks stable nerve and certain elasticity under the high humidity environment.Compare with most of common plasticses of present use, there are shortcomings such as mechanical strength is low, water tolerance is bad in thermoplastic starch (TPS) plastics, and this has limited its practical application.Can improve its performance and thermoplastic starch is carried out various modifications, expand the use range of thermoplastic starch.Chinese patent CN101942118A discloses a kind of made from plant fiber starch Biodegradable Materials and preparation method thereof, by the thermoplasticity W-Gum, 50-60 purpose needle-leaved wood fibre, poly(lactic acid), mineral filler, linking agent, the solubilizing agent mixing is extruded by the twin screw extruder melt blending and is made, this method has improved water tolerance and the physical strength of gained material, but because starch and poly(lactic acid) all are the higher macromole of degree of crystallinity, its blend exists elasticity big, the characteristics of structural fragile, especially in the middle of the process of sheet preparation, can't satisfy present production requirement.Chinese patent CN101805499A discloses a kind of full-degradable thermoplastic composite material and sheet material thereof, mainly adopt starch, poly(lactic acid), poly (propylene carbonate) polyvalent alcohol (PPC), polybutylene terephthalate (PBAT) and some auxiliary materials to melt extrude through twin screw extruder and obtain the full-degradable thermoplastic matrix material, this materials processing performance and use properties are near similar conventional plastic, and fully biodegradable, but because PPC and the suitable addition of PBAT are very little, its use properties is restricted, and this material is mainly used in packaging industry.
Poly-hexanodioic acid/butylene terephthalate (PBAT) is the three-element copolymerized ester that is polymerized by terephthalic acid, hexanodioic acid and 1,4-butyleneglycol, for studying maximum a kind of novel full-biodegradable materials in recent years both at home and abroad.Contain flexible aliphatic chain and the aromatic gp of rigidity among the PBAT, thereby have high tenacity and high thermal resistance, and because the existence of aliphatics ester bond impel it to have biodegradability simultaneously, but its cost is higher.PBAT and thermoplastic starch are carried out blend, both can improve the mechanical property of material, reduce equilibrium water absorption effect, reduce cost, also can improve the degradation property of material, change into water fully after the degraded and carbonic acid gas circulates.Therefore, how to control cost, make processing characteristics and use properties and can both satisfy existing requirement, and the material of fully biodegradable, have important practical significance.
Summary of the invention
The present invention provides a kind of thermoplastic starch (TPS) and PBAT blend and preparation method thereof for the problem that solves above-mentioned prior art existence, thermoplastic starch of the present invention and PBAT blend are a kind of completely biodegradable starch materials, and are greatly improved than the ordinary hot plastic starch mechanical property of materials.
Purpose of the present invention is achieved through the following technical solutions:
A kind of thermoplastic starch and PBAT blend, made by the component that comprises following weight part:
Native starch 30-60 part,
Softening agent 10-20 part,
PBAT 10-30 part,
Expanding material 5-10 part,
Strengthening agent 0.4-5 part,
Lubricant 0.25-5 part.
Preferably, the weight part of described PBAT is 20-30 part.
Preferably, described native starch is selected from one or more in W-Gum, wheat starch, sweet potato starch, the yam starch.
Preferably, described softening agent is selected from one or more in ethylene glycol, tirethylene glycol, propylene glycol, glycerol, sorbyl alcohol, sorbitol ester, methane amide, ethanamide, the urea.
Preferably, described expanding material is selected from one or more in vinylformic acid, acrylate, acrylamide, methacrylic acid, ethylene-methyl methacrylate ionic polymer resin, maleic anhydride, the maleic anhydride grafted ethene-octene copolymer (POE-g-MAH).
Further, the preferred maleic anhydride grafted ethene-octene copolymer of described expanding material (POE-g-MAH).
Preferably, described strengthening agent is super-fine active calcium carbide, and its particle diameter is 0.001-0.1 μ m.
Preferably, described lubricant is selected from one or more in whiteruss, polyethylene wax, stearic acid, stearic amide, the epoxy soybean oil.
The preparation method of a kind of thermoplastic starch and PBAT blend may further comprise the steps:
(1) takes by weighing each component raw material by following weight part: native starch 30-60 part, softening agent 10-20 part, PBAT 10-30 part, expanding material 5-10 part, strengthening agent 0.4-5 part, lubricant 0.25-5 part;
(2) native starch and PBAT are dried processing, drying temperature 75-85 ℃, 5-8 hour time of drying;
(3) native starch, softening agent and lubricant are added blend 5-10min in the mixer, extrude through twin screw extruder then, make the thermoplastic starch powder particles, extrusion temperature 60-120 ℃;
(4) the thermoplastic starch powder particles with preparation in the step (3) places mixer mixing 5-10min with PBAT, expanding material and strengthening agent, then compound is sent into twin screw extruder and is carried out melt blending and extrude extrusion temperature 150-170 ℃;
(5) mixture is extruded tie rod, water-cooled, pelletizing, obtained compound particles and placed the dry 4-6 of baking oven hour, oven temperature 35-65 ℃, obtain described thermoplastic starch and PBAT blend.
Preferably, preferred 20-30 part of weight part of PBAT in the described step (1); Native starch and the withering temperature of PBAT are preferably 80 ℃ in the described step (2).
Compared with prior art, the present invention has following beneficial effect:
1, the present invention has expanded the non-food use of starch, and a kind of novel degradable material that has use value is provided.By the plasticization and modification to starch, add expanding material, improve the consistency between starch and the PBAT, improved contents of starch in starch/PBAT intermingling material on the basis that guarantees material property, reduce the usage quantity of PBAT, thereby reduced the cost of material; Then use screw extrusion press melt blending, forming process, use conventional device of plastic processing to realize the serialization production of TPS/PBAT intermingling material.
2, the present invention has improved starch plastic and has had shortcomings such as mechanical strength is low, water tolerance is bad in the completely biodegradable that guarantees intermingling material.By with native starch plasticizing back and the polymer PBAT blend of synthesizing, can significantly improve mechanical property and anti-the bringing back to life property of material, reduce the cost of material.Because the TPS/PBAT intermingling material had both had tensile property and snappiness preferably, had kept the completely biodegradable of material again.The plastics that this Biodegradable material is made are a kind of environmentally friendly materials, and its degradation process green, cleaning are conducive to make up the benign cycle of soil and environmental system, have very wide application prospect.
3, improved the processing characteristics of starch.The present invention is main raw material with the native starch, prepares plasticising type thermoplastic starch by the twin screw extrusion molding.After plasticizing, the hydrogen bond between starch molecule is done weakened destruction, and the diffusibility of molecular chain improves, and the second-order transition temperature of material reduces.Therefore having realized the fusion of crystallite before decomposition, is the random coil conformation by the duplex conformation transition, thereby makes starch possess the possibility of thermoplasticity processing.
4, the present invention can control the degradation time of intermingling material in reasonable range, is conducive to storage and the application of material.The decomposition rate of existing high-content of starch Biodegradable material is very fast, and the film that has only just can be degraded under the condition of compost in 4 weeks fully, was unfavorable for storing and application.Film by thermoplastic starch of the present invention and the production of PBAT blend can be preserved in air for a long time, more than degraded needs half a year fully under the condition of compost.The degradability that can keep material like this, the while can also prolong the work-ing life of material, promotes use value.Production technique of the present invention is simple, is easy to control, is fit to suitability for industrialized production, and production unit adopts the common plastics processing units to get final product, and need not to buy other novel apptss, and investment and production cost are lower, the economic benefit height.In intermingling material, add the strengthening agent calcium carbonate superfine powder simultaneously, both kept the completely biodegradable energy of material, also improved tensile strength, toughness and the hardness etc. of material, make it can apply to industry widely.
Embodiment
Describe the present invention in detail below in conjunction with each embodiment.
The component of embodiment 1-6 and proportioning (weight part) see Table 1.
Table 1(weight part)
The preparation method is as follows:
(1) takes by weighing each component raw material by the component in the table 1 and proportioning.
(2) native starch and PBAT are put into loft drier and carry out drying, drying temperature 75-85 ℃, 5-8 hour time of drying.
Wherein, 85 ℃ of embodiment 1 drying temperatures, drying 5 hours, embodiment 2,80 ℃ of 3 drying temperatures, drying 6 hours, 80 ℃ of embodiment 4 drying temperatures, drying 7 hours, embodiment 5,75 ℃ of 6 drying temperatures, drying 8 hours.
(3) with native starch, softening agent and lubricant blend 5-10min in mixer, then compound is extruded through twin screw extruder, made the thermoplastic starch powder particles, extrusion temperature 60-120 ℃.
Wherein, embodiment 1 blend 5min, 120 ℃ of extrusion temperatures; Embodiment 2 blend 8min, 100 ℃ of extrusion temperatures; Embodiment 3 blend 10min, 90 ℃ of extrusion temperatures; Embodiment 4 blend 10min, 60 ℃ of extrusion temperatures; Embodiment 5 blend 5min, 80 ℃ of extrusion temperatures; Embodiment 6 blend 7min, 80 ℃ of extrusion temperatures.
(4) the thermoplastic starch powder particles with preparation in the step (3) places mixer mixing 5-10min with PBAT, expanding material and strengthening agent super-fine active calcium carbide, then the compound for preparing being sent into twin screw extruder carries out melt blending and extrudes extrusion temperature 150-170 ℃.
Wherein, embodiment 1 blend 5min, 170 ℃ of extrusion temperatures; Embodiment 2 blend 8min, 165 ℃ of extrusion temperatures; Embodiment 3 blend 10min, 160 ℃ of extrusion temperatures; Embodiment 4 blend 10min, 150 ℃ of extrusion temperatures; Embodiment 5 blend 5min, 155 ℃ of extrusion temperatures; Embodiment 6 blend 7min, 160 ℃ of extrusion temperatures.
In addition, the particle diameter of embodiment 1 super-fine active calcium carbide is 0.001 μ m, the particle diameter of embodiment 2 super-fine active calcium carbides is 0.085 μ m, and the particle diameter of embodiment 3,4 super-fine active calcium carbides is 0.015 μ m, and the particle diameter of embodiment 5,6 super-fine active calcium carbides is 0.1 μ m.
(5) mixture is extruded tie rod, water-cooled, pelletizing, obtained compound particles and placed the dry 4-6 of baking oven hour, oven temperature 35-65 ℃, obtain described thermoplastic starch (TPS) and PBAT blend.
Wherein, 35 ℃ of embodiment 1-3 drying temperatures, 6 hours time of drying, 65 ℃ of embodiment 4-6 drying temperatures, 4 hours time of drying.
Thermoplastic starch and PBAT blend that embodiment 1-6 is prepared carry out sample preparation and tensile property test according to the requirement of ASTM D638-2003, and with behind the pellet blown film by the requirement compost of ASTM D5988-2003, record its complete biodegradable time, test result sees Table 2.
Table 2
The thermoplastic starch of the present invention's production and PBAT blend thin films have good tensile, elongation at break and suitable degradation time as can be seen from Table 2, in normal environment for use, can substitute traditional plastics film, can in the relatively short time, degrade again after discarded, be a kind of environmentally friendly material, have broad application prospects.
More than disclosed only be several specific embodiments of the application, but the application is not limited thereto, any those skilled in the art can think variation, all should drop in the application's the protection domain.
Claims (10)
1. a thermoplastic starch and PBAT blend is characterized in that, are made by the component that comprises following weight part:
Native starch 30-60 part,
Softening agent 10-20 part,
PBAT 10-30 part,
Expanding material 5-10 part,
Strengthening agent 0.4-5 part,
Lubricant 0.25-5 part.
2. thermoplastic starch as claimed in claim 1 and PBAT blend is characterized in that, the preferred 20-30 part of the weight part of described PBAT.
3. thermoplastic starch as claimed in claim 1 and PBAT blend is characterized in that, described native starch is selected from one or more in W-Gum, wheat starch, sweet potato starch, the yam starch.
4. thermoplastic starch as claimed in claim 1 and PBAT blend is characterized in that, described softening agent is selected from one or more in ethylene glycol, tirethylene glycol, propylene glycol, glycerol, sorbyl alcohol, sorbitol ester, methane amide, ethanamide, the urea.
5. thermoplastic starch as claimed in claim 1 and PBAT blend, it is characterized in that described expanding material is selected from one or more in vinylformic acid, acrylate, acrylamide, methacrylic acid, ethylene-methyl methacrylate ionic polymer resin, maleic anhydride, the maleic anhydride grafted ethene-octene copolymer.
6. thermoplastic starch as claimed in claim 5 and PBAT blend is characterized in that, the preferred maleic anhydride grafted ethene-octene copolymer of described expanding material.
7. thermoplastic starch as claimed in claim 1 and PBAT blend is characterized in that, described strengthening agent is super-fine active calcium carbide, and its particle diameter is 0.001-0.1 μ m.
8. thermoplastic starch as claimed in claim 1 and PBAT blend is characterized in that, described lubricant is selected from one or more in whiteruss, polyethylene wax, stearic acid, stearic amide, the epoxy soybean oil.
9. the preparation method as each described thermoplastic starch and PBAT blend in the claim 1 to 8 is characterized in that, may further comprise the steps:
(1) takes by weighing each component raw material by following weight part: native starch 30-60 part, softening agent 10-20 part, PBAT 10-30 part, expanding material 5-10 part, strengthening agent 0.4-5 part, lubricant 0.25-5 part;
(2) native starch and PBAT are dried processing, drying temperature 75-85 ℃, 5-8 hour time of drying;
(3) native starch, softening agent and lubricant are added blend 5-10min in the mixer, extrude through twin screw extruder then, make the thermoplastic starch powder particles, extrusion temperature 60-120 ℃;
(4) the thermoplastic starch powder particles with preparation in the step (3) places mixer mixing 5-10min with PBAT, expanding material and strengthening agent, then compound is sent into twin screw extruder and is carried out melt blending and extrude extrusion temperature 150-170 ℃;
(5) mixture is extruded tie rod, water-cooled, pelletizing, obtained compound particles and placed the dry 4-6 of baking oven hour, oven temperature 35-65 ℃, obtain described thermoplastic starch and PBAT blend.
10. the preparation method of thermoplastic starch as claimed in claim 9 and PBAT blend is characterized in that, preferred 20-30 part of weight part of PBAT in the described step (1); Native starch and the withering temperature of PBAT are preferably 80 ℃ in the described step (2).
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