CN106479143A - A kind of attapulgite/poly lactic acid nano composite material and preparation method thereof - Google Patents
A kind of attapulgite/poly lactic acid nano composite material and preparation method thereof Download PDFInfo
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- CN106479143A CN106479143A CN201610931603.2A CN201610931603A CN106479143A CN 106479143 A CN106479143 A CN 106479143A CN 201610931603 A CN201610931603 A CN 201610931603A CN 106479143 A CN106479143 A CN 106479143A
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- attapulgite
- lactic acid
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/06—Biodegradable
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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Abstract
The present invention relates to a kind of attapulgite/poly lactic acid nano composite material and preparation method thereof；Described attapulgite/poly lactic acid nano composite material includes polylactic acid 65 70, attapulgite 28, starch 5 10, environment-friendly plasticizer 5 15, silane coupler 0.4 0.6, and composition described above raw material is weight part ratio；After said components are mixed extrusion, cooling, pelletize and be obtained.The attapulgite that the present invention is obtained/poly lactic acid nano composite material performance is greatly improved.In biodegradation membrane material, sheet material, injection, packaging material field, there is wide application prospect.
Description
Technical field
The present invention relates to biodegradation material field and in particular to a kind of attapulgite/poly lactic acid nano composite material and
Its preparation method.
Background technology
In recent years, going from bad to worse with environment for human survival, people increasingly pay close attention to development environment friendly material and
Using renewable raw material.Oil, as non-renewable resources, is most important industrial chemicals, but due in use with
And in final waste procedures, have the discharge of a large amount of CO2, a series of problems, such as lead to global warming, and directly threaten mankind's life
Deposit.
The raw material of polylactic acid is from annual plant Zea mays, and is easy to be dropped by biology under the regulation of aerobic and water
Solution becomes CO2 and H2O, completely solves the two fatefulue greatly problems that plastic industry runs into, and the renewable, degradable of polylactic acid is special
Property just progressively replace petroleum-based plastics application.
Polylactic acid is a kind of biodegradable polymer of biomass source.But polylactic acid matter is hard and toughness is poor, lack
Weary flexible and elastic, impact resilience is also poor, which has limited the application of polylactic acid.
A kind of poly (lactic acid) composition disclosed in Chinese patent CN102924892A, using poly-L-lactic acid homopolymer, and Gao Rong
The poly- D lactic acid copolymer of point is obtaining high-fire resistance and high tenacity.Said composition is due to a lack of good elongation, and can not use
In film article.
At present, attapulgite is used for the report of polyester (polyethylene terephthalate, PET) engineering plastic modification
Road, for example, Wang Haiyang etc. has carried out nano-attapulgite masterbatch and PET/ nano-attapulgite masterbatch for modified engineered plastic
The research of composite is (referring to Wang Haiyang etc., PET/ nano-attapulgite masterbatch composite property and structural research, engineering
Plastic applications, the 1st phase of volume 36,2008；Chinese patent literature CN200610118680.2, for modified engineered plastic
Nano attapulgite clay composition), can be applicable to various rubber-plastics materials, improve the intensity of resin, toughness, resistance to some extent
Mill, heat-resisting and processing and forming characteristic.
Attapulgite is a kind of porous chain layered hydrous richness alumina magnesia silicate, and Main Ingredients and Appearance is silicon dioxide, oxygen
Change magnesium and aluminium sesquioxide, there is good physical property and certain plasticity such as unique dispersion, heatproof, Salt And Alkali Tolerance.Recessed
Convex rod soil, as natural monodimension nanometer material, has the nano stick crystal structure of uniqueness so as to can fill and nanometer in micron
Strengthen and be combined with poly-lactic acid material in two levels, wherein contain substantial amounts of hydroxyl, and there is certain reactivity, can
With remaining carboxyl reaction in polylactic acid molecule, the above characteristic contributes to being formed between matrix polylactic acid and stratiform attapulgite hybrid
Strong interface interaction power, made nano composite material has good tensile strength, heat stability improves, gas percent of pass
The features such as reduction.
Content of the invention
The purpose of the present invention is by preparing attapulgite clay nano composite polylactic acid material, obtain good tensile strength,
Heat stability improves.
A kind of attapulgite/poly lactic acid nano composite material of the present invention；Described attapulgite/poly lactic acid nano composite material
Including polylactic acid 65-70, attapulgite 2-8, starch 5-10, environment-friendly plasticizer 5-15, silane coupler 0.4-0.6, above
Constitutive material is weight part ratio；After said components are mixed extrusion, cooling, pelletize and be obtained.
Described polylactic acid weight average molecular weight is in 60000-150000.
Described starch for native starch adopt one of corn starch, wheaten starch, potato starch and cereal starch or
Multiple combinations.
Described environment-friendly plasticizer is water, glycerol, polypropylene glycol, ethylene glycol, propylene glycol, butanediol, acetic acid sorbitol ester, sweet
Dew sugar alcohol monosubstituted ethoxy compound, one or more of carboxymethyl Sorbitol sodium salt of combination.
Described silane coupler is the siloxanes containing alkoxy-functional；The described siloxanes containing alkoxy-functional is second
In thiazolinyl chloropropyl siloxanes, epoxy radical siloxane, methacryl radical siloxane, amido siloxanes and sulfydryl siloxanes one
Plant or multiple combination.
A kind of preparation method of attapulgite/poly lactic acid nano composite material, comprises the following steps：
The first step, by above-mentioned composition attapulgite soil, starch, environment-friendly plasticizer and silane coupler mix and blend in batch mixer；
Second step, adds the common mix and blend of polylactic acid of section；
3rd step, by the raw material after second step mix and blend, through screw extruder extrusion molten, cooling, pelletize and be obtained.
In the described first step, in 50-60 degree, mixing time is 10-30 minute to batch mixer mixing temperature.
In described second step, the mixing time of batch mixer is 10-15 minute.
In described 3rd step, the melt temperature of extruder is 165-175 DEG C, and the rotating speed of extruder is 80-100r/min
, 175-180 DEG C of die head temperature.
Beneficial effect：
Present invention process is simple, and technology maturation is reliable, can carry out attapulgite/poly- using existing polylactic acid modifier equipment
Lactic acid nano composite material produces, and need not increase new equipment, has the characteristics that low production cost and added value of product is high；The present invention
The poly lactic acid nano composite material performance that preparation method is obtained is greatly improved.In biodegradation membrane material, sheet material, injection, packing timber
Material field has wide application prospect.
Specific embodiment
In order that the objects, technical solutions and advantages of the present invention become more apparent, with reference to embodiments, to the present invention
It is further elaborated.It should be appreciated that specific embodiment described herein, only in order to explain the present invention, is not used to
Limit the present invention.
A kind of attapulgite/poly lactic acid nano composite material；Described attapulgite/poly lactic acid nano composite material includes it
The weight portion of constitutive material is：Polylactic acid 65-70, attapulgite 2-8, starch 5-10, environment-friendly plasticizer 5-15, silane coupled
Agent 0.4-0.6, and extrusion after said components are mixed, cooling, pelletize and be obtained.
Preferably, described polylactic acid weight average molecular weight is in 60000-150000.
Preferably, described starch adopts in corn starch, wheaten starch, potato starch and cereal starch for native starch
One or more of combination.
Preferably, described environment-friendly plasticizer is water, glycerol, polypropylene glycol, ethylene glycol, propylene glycol, butanediol, acetic acid Pyrusussuriensiss
Alcohol ester, mannitol monosubstituted ethoxy compound, one or more of carboxymethyl Sorbitol sodium salt of combination.
Preferably, described silane coupler is the siloxanes containing alkoxy-functional；The described silicon containing alkoxy-functional
Oxygen alkane is vinyl chloride propyl-siloxane, epoxy radical siloxane, methacryl radical siloxane, amido siloxanes and sulfydryl silica
One or more of alkane combines.
A kind of preparation method of attapulgite/poly lactic acid nano composite material, comprises the following steps：
The first step, by above-mentioned composition attapulgite soil, starch, environment-friendly plasticizer and silane coupler mix and blend in batch mixer；
Second step, adds the common mix and blend of polylactic acid of section；3rd step, the raw material after second step mix and blend squeezes through screw rod
Go out machine extrusion molten, cooling, pelletize and be obtained.
Preferably, in the described first step batch mixer mixing temperature in 50-60 degree, mixing time be 10-30 minute.Excellent
Choosing, in described second step, the mixing time of batch mixer is 10-15 minute.Preferably, extruder in described 3rd step
Melt temperature is 165-175 DEG C, and the rotating speed of extruder is 80-100r/min, 175-180 DEG C of die head temperature.
Embodiment one
By 2 parts of attapulgite, 5 parts of corn starch, 8 parts of glycerol, 0.4 part of MTES coupling agent；Mix homogeneously 50
Stir 10 minutes at DEG C, add 65 parts of polylactic acid, stirring is uniformly sent into extruder for 15 minutes afterwards and melt extruded pelletize, melting
Temperature is 165 DEG C, and the rotating speed of extruder controls in 80r/min, and 175 DEG C of die head temperature obtains attapulgite/polylactic acid nano
Composite.
Embodiment two
By 4.5 parts of attapulgite, 6 parts of corn starch, 6 parts of propylene glycol, 0.5 part of epoxy radicals trimethoxysilane coupling agent；Mixing
Stir 30 minutes at uniform 60 DEG C, add 70 parts of polylactic acid, stirring is uniformly sent into extruder for 15 minutes afterwards and melt extruded and make
Grain, melt temperature is 175 DEG C, and the rotating speed of extruder controls in 90r/min, 180 DEG C of die head temperature, obtains attapulgite/poly-
Lactic acid nano composite material；
Embodiment three
By 8.5 parts of attapulgite, 4 parts of corn starch, 8 parts of glycerol, 0.6 part of MTES coupling agent；Mix homogeneously
Stir 20 minutes at 60 DEG C, add 70 points of polylactic acid, stirring is uniformly sent into extruder for 15 minutes afterwards and melt extruded pelletize, melt
Melt temperature and be 170 DEG C, the rotating speed of extruder controls in 100r/min, and 175 DEG C of die head temperature obtains attapulgite/polylactic acid
Nano composite material；
Chart
The material performance table of attapulgite/poly lactic acid nano composite material
| Project | PLA | Embodiment one | Embodiment two | Embodiment three |
| Tensile strength MPA | 18 | 29 | 32 | 24 |
| Elastic modelling quantity MPA | 200 | 223 | 254 | 265 |
| Fracture productivity ratio % | 830 | 1100 | 1050 | 1000 |
| Thermal distorsion temperature | 58 | 74 | 80 | 86 |
The foregoing is only presently preferred embodiments of the present invention, not in order to limit the present invention, all spirit in the present invention and
Any modification, equivalent and improvement of being made within principle etc., should be included within the scope of the present invention.
Claims (9)
1. a kind of attapulgite/poly lactic acid nano composite material；It is characterized in that：Described attapulgite/polylactic acid nano is combined
Material includes polylactic acid 65-70, attapulgite 2-8, starch 5-10, environment-friendly plasticizer 5-15, silane coupler 0.4-
0.6, composition described above raw material is weight part ratio；After said components are mixed extrusion, cooling, pelletize and be obtained.
2. attapulgite/poly lactic acid nano composite material according to claim 1 it is characterised in that：Described polylactic acid weight
Average molecular weight is in 60000-150000.
3. attapulgite/poly lactic acid nano composite material according to claim 1 it is characterised in that：Described starch is sky
So starch adopts the combination of one or more of corn starch, wheaten starch, potato starch and cereal starch.
4. attapulgite/poly lactic acid nano composite material according to claim 1 it is characterised in that：Described environmental protection plasticising
Agent be water, glycerol, polypropylene glycol, ethylene glycol, propylene glycol, butanediol, acetic acid sorbitol ester, mannitol monosubstituted ethoxy compound,
The combination of one or more of carboxymethyl Sorbitol sodium salt.
5. attapulgite/poly lactic acid nano composite material according to claim 1 it is characterised in that：Described silane coupled
Agent is the siloxanes containing alkoxy-functional；The described siloxanes containing alkoxy-functional is vinyl chloride propyl-siloxane, ring
One or more of epoxide siloxanes, methacryl radical siloxane, amido siloxanes and sulfydryl siloxanes combine.
6. a kind of preparation method required attapulgite/poly lactic acid nano composite material as described in 1, comprises the following steps：
The first step, above-mentioned composition attapulgite soil, starch, environment-friendly plasticizer and silane coupler is mixed in batch mixer and stirs
Mix；
Second step, adds the common mix and blend of polylactic acid of section；
3rd step, by the raw material after second step mix and blend, through screw extruder extrusion molten, cooling, pelletize and be obtained.
7. preparation method according to claim 6 it is characterised in that：In the described first step, batch mixer mixing temperature exists
In 50-60 degree, mixing time is 10-30 minute.
8. preparation method according to claim 6 it is characterised in that：In described second step, the mixing time of batch mixer is
10-15 minute.
9. preparation method according to claim 6 it is characterised in that：In described 3rd step, the melt temperature of extruder is
165-175 DEG C, the rotating speed of extruder is 80-100r/min, 175-180 DEG C of die head temperature.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108841153A (en) * | 2018-07-02 | 2018-11-20 | 江南大学 | A kind of high-ductility, high heat distortion temperature poly (lactic acid) composition and preparation method thereof |
| CN108948703A (en) * | 2018-08-07 | 2018-12-07 | 万卓（武汉）新材料有限公司 | A kind of weather-proof degradation plastic bottle and preparation method thereof |
| CN109385031A (en) * | 2018-10-29 | 2019-02-26 | 安徽精乐塑业有限公司 | A kind of Degradable environment protection packaging bag |
| CN109504010A (en) * | 2018-10-29 | 2019-03-22 | 安徽精乐塑业有限公司 | A kind of preparation method of environmental protection food package film |
| CN115772322A (en) * | 2021-09-06 | 2023-03-10 | 大禾科技发展(南京)有限公司 | Preparation method of degradable preservative film |
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| CN101875765A (en) * | 2010-07-14 | 2010-11-03 | 华东理工大学 | Plasticized polylactic acid/inorganic nano composite material and preparation method thereof |
| CN102120841A (en) * | 2010-12-27 | 2011-07-13 | 华东理工大学 | Degradable synthetic paper material and preparation method thereof |
| CN102453319A (en) * | 2010-10-25 | 2012-05-16 | 中国石油化工股份有限公司 | Polylactic resin composition film and preparation method thereof |
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2016
- 2016-10-31 CN CN201610931603.2A patent/CN106479143A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101875765A (en) * | 2010-07-14 | 2010-11-03 | 华东理工大学 | Plasticized polylactic acid/inorganic nano composite material and preparation method thereof |
| CN102453319A (en) * | 2010-10-25 | 2012-05-16 | 中国石油化工股份有限公司 | Polylactic resin composition film and preparation method thereof |
| CN102120841A (en) * | 2010-12-27 | 2011-07-13 | 华东理工大学 | Degradable synthetic paper material and preparation method thereof |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108841153A (en) * | 2018-07-02 | 2018-11-20 | 江南大学 | A kind of high-ductility, high heat distortion temperature poly (lactic acid) composition and preparation method thereof |
| CN108841153B (en) * | 2018-07-02 | 2020-10-30 | 江南大学 | High-toughness and high-heat-deformation-temperature polylactic acid composition and preparation method thereof |
| CN108948703A (en) * | 2018-08-07 | 2018-12-07 | 万卓（武汉）新材料有限公司 | A kind of weather-proof degradation plastic bottle and preparation method thereof |
| CN108948703B (en) * | 2018-08-07 | 2021-04-13 | 万卓（武汉）新材料有限公司 | Weather-resistant degradable plastic bottle and preparation method thereof |
| CN109385031A (en) * | 2018-10-29 | 2019-02-26 | 安徽精乐塑业有限公司 | A kind of Degradable environment protection packaging bag |
| CN109504010A (en) * | 2018-10-29 | 2019-03-22 | 安徽精乐塑业有限公司 | A kind of preparation method of environmental protection food package film |
| CN115772322A (en) * | 2021-09-06 | 2023-03-10 | 大禾科技发展(南京)有限公司 | Preparation method of degradable preservative film |
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Application publication date: 20170308 |