CN102964636A - Thermoplastic starch-sepiolite composite material and preparation method thereof - Google Patents
Thermoplastic starch-sepiolite composite material and preparation method thereof Download PDFInfo
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- CN102964636A CN102964636A CN201210526116XA CN201210526116A CN102964636A CN 102964636 A CN102964636 A CN 102964636A CN 201210526116X A CN201210526116X A CN 201210526116XA CN 201210526116 A CN201210526116 A CN 201210526116A CN 102964636 A CN102964636 A CN 102964636A
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- sepiolite
- thermoplastic starch
- starch
- matrix material
- fluidizer
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92819—Location or phase of control
- B29C2948/92857—Extrusion unit
- B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
- B29C2948/92895—Barrel or housing
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- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides a thermoplastic starch-sepiolite composite material which has a base material of thermoplastic starch and a filler of sepiolite, wherein the mass percent of the thermoplastic starch is 66.7-79.4 percent, the mass percent of a plasticizer is 19.8-26.6 percent, the mass percent of the sepiolite is 0.8-6.7 percent, and the fiber length of the sepiolite is not more than 80mu m and the fiber diameter of the sepiolite is not more than 1mu m. The invention also provides a preparation method which comprises the following steps of: uniformly mixing the thermoplastic starch, the plasticizer and the sepiolite, then placing for 8-12 hours in a closed environment, transferring the mixture to a screw plastic extruder, extruding and forming at a temperature of 110-135 DEG C, and finally cooling to a normal temperature to obtain the thermoplastic starch-sepiolite composite material. The thermoplastic starch-sepiolite composite material has the characteristics of no toxicity, degradability, low cost and simple process, and has the advantages of improving the breaking strength and reducing the water vapor penetration rate compared with the thermoplastic starch.
Description
Technical field
The invention belongs to technical field of composite materials, particularly a kind of thermoplastic starch-sepiolite matrix material and preparation method thereof.
Background technology
Under the existing situation, existing resource and environment are carried out the development and utilization of environmental protection, Sustainable development, become general common recognition.Traditional plastic material has the shortcomings such as the degraded of being difficult to, poisonous and harmful, dependence petroleum-based energy; And natural macromolecular material has the advantages such as degradable, renewable, environmental friendliness, can be used for replacing conventional plastic to address the above problem.
Starch (Starch) is a kind of wide material sources, short natural macromolecular material of cheap, regeneration period, contain the great amount of hydroxy group group in its molecular chain, these groups are interior and intermolecular hydrogen bond action by molecule, the aggregated structure that forms crystal form and amorphous state and deposit; Because second-order transition temperature near decomposition temperature, does not therefore have plasticity-.Contain the groups such as hydroxyl, amino, amide group in the fluidizer such as glycerine, the ethylene glycol small molecules, can with starch molecular chain in hydroxyl form stronger hydrogen bond action, thereby destroy its original structure, reduce second-order transition temperature, make it show thermoplasticity.After starch and fluidizer blend, under hot conditions by shear, extrude, the forming method such as mold pressing, injection moulding can make thermoplastic starch (Thermoplastic Starch).
Compare with conventional plastic, thermoplastic starch is Shortcomings aspect mechanical property, water absorbability, thermostability, and this is restricted its application.Find that after deliberation by add the matrix material of the high layered silicate microparticle made of compatible degree in thermoplastic starch, its above-mentioned various aspects of performance all can be improved and improve.In correlation technique, polynite, kaolin etc. has the silicate mineral of laminated structure, as the making of applying filler in thermoplastic starch-based composite material.
Sepiolite (Sepiolite) be a kind of have a layer chain-like structure contain Shuifu County's magnesium silicate clay mineral, its chemical ingredients is silicon and magnesium, the standard crystal chemical formula is Mg
8(H
2O)
4[Si
6O
16]
2(OH)
48H
2O belongs to rhombic system or oblique system.Sepiolite has adsorptivity, can keep rock steady structure below 1500 ~ 1700 ℃, is the most widely one of raw mineral materials of present Application Areas.
Thermoplastic starch and sepiolite all are to have hydrophilic natural materials.Through retrieval, in existing disclosed document, there is not to find to make take sepiolite as filler the technical scheme of thermoplastic starch-based composite material.
Summary of the invention
The object of the present invention is to provide a kind of thermoplastic starch-sepiolite matrix material, this material has improved mechanical property and the anti-water absorbability of thermoplastic starch material take the sepiolite microparticle of different size as filler.The present invention proposes corresponding preparation method, the method technique is simple, easy controlled operation, with low cost, has practical value.
In order to achieve the above object, the invention provides following technical scheme: a kind of thermoplastic starch-sepiolite matrix material, it is characterized in that the base-material of described matrix material is thermoplastic starch, filler is sepiolite; Wherein the mass percent of starch is 66.7% ~ 79.4%, and the mass percent of fluidizer is 19.8% ~ 26.6%, and the mass percent of sepiolite is 0.8% ~ 6.7%; The staple length of described sepiolite is not more than 80 μ m, and Fibre diameter is not more than 1 μ m.
The technique scheme of doing preferred, described fluidizer is glycerine.Described sepiolite is sepiolite powder, sepiolite fibre or sepiolite cashmere; The staple length of described sepiolite powder is not more than 5 μ m, and Fibre diameter is not more than 0.5 μ m; The staple length of described sepiolite fibre is not more than 50 μ m, and Fibre diameter is not more than 0.5 μ m; The staple length of described sepiolite cashmere is not more than 80 μ m, and Fibre diameter is not more than 1 μ m.
The present invention also provides a kind of thermoplastic starch-sepiolite composite manufacture method, it is characterized in that, contains successively following steps:
Q1: respectively starch, fluidizer are added high-speed mixer, mixed 2 ~ 3 minutes;
Q2: sepiolite is added high-speed mixer, mixed 1 ~ 2 minute;
Q3: the mixture that starch, fluidizer, sepiolite are formed is transferred in the sealing bag, and airtight placement is 8 ~ 12 hours at ambient temperature;
Q4: described mixture is taken out from sealing bag, be transferred to the opening for feed of screw rod plastic forcing machine;
Q5: under 110 ℃ ~ 135 ℃ temperature condition, described mixture through described screw rod plastic extruder for shaping, is then naturally cooled to normal temperature, prepare thermoplastic starch-sepiolite matrix material.
Preferred as above-mentioned preparation method, in the process by described screw rod plastic forcing machine, altogether through four zones, its corresponding temperature range is followed successively by 120 ℃, 130 ℃ ~ 135 ℃, 130 ℃ ~ 135 ℃, 110 ℃ ~ 120 ℃ to described mixture in order from opening for feed to discharge port.
Starch of the present invention and sepiolite are natural materials, nontoxic, degradable, with low cost.Utilize the hydrophilic radical of sepiolite and the hydrogen bond action between the oh group in the starch molecular chain, by extruding-out process, prepare thermoplastic starch-sepiolite matrix material.Through evidence, after sepiolite-filled strengthened, the breaking tenacity of thermoplastic starch improved, water vapour permeability descends.
Embodiment
Below in conjunction with embodiments of the invention, the technical scheme of invention is carried out clear, complete description, obviously, described embodiment only is the present invention's part embodiment, rather than whole embodiment.Based on the embodiment among the present invention, those of ordinary skills belong to the scope of protection of the invention not making the every other embodiment that obtains under the creative work prerequisite.
The invention provides a kind of thermoplastic starch-sepiolite matrix material, the base-material of described matrix material is thermoplastic starch, and filler is sepiolite; Wherein the mass percent of starch is 66.7% ~ 79.4%, and the mass percent of fluidizer is 19.8% ~ 26.6%, and the mass percent of sepiolite is 0.8% ~ 6.7%; The staple length of described sepiolite is not more than 80 μ m, and Fibre diameter is not more than 1 μ m.
Described fluidizer is glycerine.Described sepiolite is sepiolite powder, sepiolite fibre or sepiolite cashmere; The staple length of described sepiolite powder is not more than 5 μ m, and Fibre diameter is not more than 0.5 μ m; The staple length of described sepiolite fibre is not more than 50 μ m, and Fibre diameter is not more than 0.5 μ m; The staple length of described sepiolite cashmere is not more than 80 μ m, and Fibre diameter is not more than 1 μ m.
The present invention also provides corresponding preparation method, contains successively following steps:
Respectively starch, fluidizer are added high-speed mixer, mixed 2 ~ 3 minutes; Sepiolite is added high-speed mixer, mixed 1 ~ 2 minute; The mixture that starch, fluidizer, sepiolite are formed is transferred in the sealing bag, and airtight placement is 8 ~ 12 hours at ambient temperature; Described mixture is taken out from sealing bag, be transferred to the opening for feed of screw rod plastic forcing machine; Under 110 ℃ ~ 135 ℃ temperature condition, described mixture through described screw rod plastic extruder for shaping, is then naturally cooled to normal temperature, prepare thermoplastic starch-sepiolite matrix material.
In the process by described screw rod plastic forcing machine, altogether through four zones, its corresponding temperature range is followed successively by 120 ℃, 130 ℃ ~ 135 ℃, 130 ℃ ~ 135 ℃, 110 ℃ ~ 120 ℃ to described mixture in order from opening for feed to discharge port.
Through evidence, there is impact in the microparticle size difference of sepiolite for mechanical property and the anti-water absorbability of thermoplastic starch-sepiolite matrix material.
The below introduces embodiments of the invention:
The sepiolite that the embodiment of the invention adopts, buying is from the grand sharp sepiolite cashmere of Hebei China company limited.
As the contrast standard of following each embodiment, the present invention at first is provided at the test result of thermoplastic starch material prepared in the situation that does not contain sepiolite and breaking tenacity thereof, water vapour permeability.
Take by weighing 1000g starch, 300g glycerine, add high-speed mixer, mixed 3 minutes with 1000 ~ 1500r/min rotating speed; The mixture that starch, glycerine are formed is transferred in the sealing bag, and airtight placement is 12 hours at ambient temperature; Described mixture is taken out and is transferred to the opening for feed of screw rod plastic forcing machine; With four zones of described mixture from opening for feed to discharge port, then the temperature extrusion moulding according to 120 ℃, 130 ℃, 130 ℃, 110 ℃ naturally cools to normal temperature, prepares the described thermoplastic starch material that does not contain sepiolite.After tested, the breaking tenacity of this material is 6.05MPa ~ 7.11MPa, and water vapour permeability is 6.8 * 10
-11Gm
-1s
-1Pa
-1
Embodiment one. and take by weighing 1000g starch, 300g glycerine, add high-speed mixer, mixed 3 minutes with the rotating speed of 1000 ~ 1500r/min; Take by weighing the 5g sepiolite powder, add high-speed mixer, mixed 2 minutes with the rotating speed of 1000 ~ 1500r/min; The mixture that starch, glycerine, sepiolite powder are formed is transferred in the sealing bag, and airtight placement is 8 hours at ambient temperature; Described mixture is taken out and is transferred to the opening for feed of screw rod plastic forcing machine; With four zones of described mixture from opening for feed to discharge port, then the temperature extrusion moulding according to 120 ℃, 130 ℃, 130 ℃, 120 ℃ naturally cools to normal temperature, prepares thermoplastic starch described in the invention-sepiolite matrix material.The staple length of used sepiolite powder is not more than 5 μ m, and Fibre diameter is not more than 0.5 μ m.After tested, compare with the thermoplastic starch material that does not contain sepiolite, the breaking tenacity of this matrix material is increased to 15.08MPa ~ 18.42MPa by 6.05MPa ~ 7.11MPa, and water vapour permeability is by 6.8 * 10
-11Gm
-1s
-1Pa
-1Be reduced to 4.5 * 10
-11Gm
-1s
-1Pa
-1
Embodiment two. and take by weighing 1000g starch, 350g glycerine, add high-speed mixer, mixed 2 minutes with the rotating speed of 1000 ~ 1500r/min; Take by weighing the 10g sepiolite fibre, add high-speed mixer, mixed 1 minute with the rotating speed of 1000 ~ 1500r/min; The mixture that starch, glycerine, sepiolite fibre are formed is transferred in the sealing bag, and airtight placement is 12 hours at ambient temperature; Described mixture is taken out and is transferred to the opening for feed of screw rod plastic forcing machine; With four zones of described mixture from described opening for feed to discharge port, then the temperature extrusion moulding according to 120 ℃, 135 ℃, 135 ℃, 120 ℃ naturally cools to normal temperature, prepares thermoplastic starch described in the invention-sepiolite matrix material.The staple length of used sepiolite fibre is not more than 50 μ m, and Fibre diameter is not more than 0.5 μ m.After tested, compare with the thermoplastic starch material that does not contain sepiolite, the breaking tenacity of this matrix material is increased to 19.84MPa ~ 22.86MPa by 6.05MPa ~ 7.11MPa, and water vapour permeability is by 6.8 * 10
-11Gm
-1s
-1Pa
-1Be reduced to 3.7 * 10
-11Gm
-1s
-1Pa
-1
Embodiment three. and take by weighing 1000g starch, 300g glycerine, add high-speed mixer, mixed 2.5 minutes with the rotating speed of 1000 ~ 1500r/min; Take by weighing the 8g sepiolite cashmere, add high-speed mixer, mixed 1.5 minutes with the rotating speed of 1000 ~ 1500r/min; The mixture that starch, glycerine, sepiolite cashmere are formed is transferred in the sealing bag, and airtight placement is 9 hours at ambient temperature; Described mixture is taken out and is transferred to the opening for feed of screw rod plastic forcing machine; With four zones of described mixture from described opening for feed to discharge port, then the temperature extrusion moulding according to 120 ℃, 130 ℃, 130 ℃, 115 ℃ naturally cools to normal temperature, prepares thermoplastic starch described in the invention-sepiolite matrix material.The staple length of used sepiolite cashmere is not more than 80 μ m, and Fibre diameter is not more than 1 μ m.After tested, compare with the thermoplastic starch material that does not contain sepiolite, the breaking tenacity of this matrix material is increased to 14.01MPa ~ 19.79MPa by 6.05MPa ~ 7.11MPa, and water vapour permeability is by 6.8 * 10
-11Gm
-1s
-1Pa
-1Be reduced to 4.2 * 10
-11Gm
-1s
-1Pa
-1
Embodiment four. and take by weighing 1000g starch, 250g glycerine, add high-speed mixer, mixed 2.5 minutes with the rotating speed of 1000 ~ 1500r/min; Take by weighing the 2g sepiolite fibre, add high-speed mixer, mixed 1.5 minutes with the rotating speed of 1000 ~ 1500r/min; The mixture that starch, glycerine, sepiolite fibre are formed is transferred in the sealing bag, and airtight placement is 10.5 hours at ambient temperature; Described mixture is taken out and is transferred to the opening for feed of screw rod plastic forcing machine; With four zones of described mixture from described opening for feed to discharge port, then the temperature extrusion moulding according to 120 ℃, 130 ℃, 130 ℃, 115 ℃ naturally cools to normal temperature, prepares thermoplastic starch described in the invention-sepiolite matrix material.The staple length of used sepiolite fibre is not more than 50 μ m, and Fibre diameter is not more than 0.5 μ m.After tested, compare with the thermoplastic starch material that does not contain sepiolite, the breaking tenacity of this matrix material is increased to 14.00MPa ~ 18.20MPa by 6.05MPa ~ 7.11MPa, and water vapour permeability is by 6.8 * 10
-11Gm
-1s
-1Pa
-1Be reduced to 4.8 * 10
-11Gm
-1s
-1Pa
-1
According to preparation method of the present invention, be dispersed in the thermoplastic starch matrix to the sepiolite uniform filling.Because sepiolite has iris action to steam by starch film, therefore reduced the water vapour permeability of thermoplastic starch; And stronger hydrogen bond action between sepiolite and the thermoplastic starch has then improved the breaking tenacity of thermoplastic starch.Starch of the present invention and sepiolite are renewable, degradable natural materials, rely on the improvement on mechanical property and anti-water absorbability, can make thermoplastic starch be more suitable for substituting the conventional plastic material.
The above; be the specific embodiment of the present invention only, but protection scope of the present invention is not limited to this, anyly is familiar with those skilled in the art in the technical scope that the present invention discloses; can expect easily changing or replacing, all should be encompassed within protection scope of the present invention.Therefore, protection scope of the present invention should be as the criterion by described protection domain with claim.
Claims (5)
1. thermoplastic starch-sepiolite matrix material is characterized in that the base-material of described matrix material is thermoplastic starch, and filler is sepiolite; Wherein the mass percent of starch is 66.7% ~ 79.4%, and the mass percent of fluidizer is 19.8% ~ 26.6%, and the mass percent of sepiolite is 0.8% ~ 6.7%; The staple length of described sepiolite is not more than 80 μ m, and Fibre diameter is not more than 1 μ m.
2. a kind of thermoplastic starch according to claim 1-sepiolite matrix material is characterized in that described fluidizer is glycerine.
3. a kind of thermoplastic starch according to claim 1-sepiolite matrix material is characterized in that, described sepiolite is sepiolite powder, sepiolite fibre or sepiolite cashmere; The staple length of described sepiolite powder is not more than 5 μ m, and Fibre diameter is not more than 0.5 μ m; The staple length of described sepiolite fibre is not more than 50 μ m, and Fibre diameter is not more than 0.5 μ m; The staple length of described sepiolite cashmere is not more than 80 μ m, and Fibre diameter is not more than 1 μ m.
4. thermoplastic starch-sepiolite composite manufacture method is characterized in that, contains successively following steps:
Q1: respectively starch, fluidizer are added high-speed mixer, mixed 2 ~ 3 minutes;
Q2: sepiolite is added high-speed mixer, mixed 1 ~ 2 minute;
Q3: the mixture that starch, fluidizer, sepiolite are formed is transferred in the sealing bag, and airtight placement is 8 ~ 12 hours at ambient temperature;
Q4: described mixture is taken out from sealing bag, be transferred to the opening for feed of screw rod plastic forcing machine;
Q5: under 110 ℃ ~ 135 ℃ temperature condition, described mixture through described screw rod plastic extruder for shaping, is then naturally cooled to normal temperature, prepare thermoplastic starch-sepiolite matrix material.
5. a kind of thermoplastic starch according to claim 4-sepiolite composite manufacture method, it is characterized in that, in the process by described screw rod plastic forcing machine, altogether through four zones, its corresponding temperature range is followed successively by 120 ℃, 130 ℃ ~ 135 ℃, 130 ℃ ~ 135 ℃, 110 ℃ ~ 120 ℃ to described mixture in order from opening for feed to discharge port.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210526116XA CN102964636A (en) | 2012-12-07 | 2012-12-07 | Thermoplastic starch-sepiolite composite material and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201210526116XA CN102964636A (en) | 2012-12-07 | 2012-12-07 | Thermoplastic starch-sepiolite composite material and preparation method thereof |
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| CN102964636A true CN102964636A (en) | 2013-03-13 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105076082A (en) * | 2015-08-04 | 2015-11-25 | 安徽宏飞钓具有限公司 | Treatment method for injection-molded bionic bait matrix |
| CN111793251A (en) * | 2020-07-30 | 2020-10-20 | 华南理工大学 | Starch-based plastic tableware and preparation method thereof |
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| CN1618851A (en) * | 2004-10-15 | 2005-05-25 | 天津大学 | Preparation method of thermoplastic starch material |
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2012
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| CN1618851A (en) * | 2004-10-15 | 2005-05-25 | 天津大学 | Preparation method of thermoplastic starch material |
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| CN101544785A (en) * | 2009-04-25 | 2009-09-30 | 西北师范大学 | Starch based nanocomposite degradable material and preparation method thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105076082A (en) * | 2015-08-04 | 2015-11-25 | 安徽宏飞钓具有限公司 | Treatment method for injection-molded bionic bait matrix |
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| CN111793251A (en) * | 2020-07-30 | 2020-10-20 | 华南理工大学 | Starch-based plastic tableware and preparation method thereof |
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Application publication date: 20130313 |