CN104861604B - A kind of environment-friendly composite material and preparation method thereof - Google Patents
A kind of environment-friendly composite material and preparation method thereof Download PDFInfo
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- CN104861604B CN104861604B CN201510319861.0A CN201510319861A CN104861604B CN 104861604 B CN104861604 B CN 104861604B CN 201510319861 A CN201510319861 A CN 201510319861A CN 104861604 B CN104861604 B CN 104861604B
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Abstract
A kind of environment-friendly composite material and preparation method thereof.Composition and parts by weight are as follows: polylactic acid: 100 parts；5-30 parts of sesbania gum；Modified Nano TiO20.2-5 parts；1-6 parts of plasticizer A；2-15 parts of plasticizer B；0.1-0.5 parts of lubricant.Its preparation process includes: first to nano-TiO2It is modified to carry out surface; then it is mixed with triacetyl glycerine or epoxidized soybean oil; and after further being mixed with polylactic acid, sesbania gum, polyethylene glycol or tributyl citrate, stearic acid etc., squeeze out and be granulated by double-screw extruding pelletizing machine, obtains polylactic acid/sesbania gum/nano-TiO2Composite material.Polylactic acid/sesbania gum/nano-TiO of the invention2Composite material has good processing rheological property and mechanical property, and environmentally protective, at low cost, and the plastic products of different shape can be prepared by forming methods such as molding, extrusion, injection molding, calenderings.
Description
Technical field
The invention belongs to the processing and forming fields of environment-friendly polymers, and in particular to be a kind of environmentally protective poly-
Lactic acid/sesbania gum/nano-TiO2Composite material and preparation method.
Background technique
Polylactic acid (PLA) is the green of nontoxic, nonirritant, the good biocompatibility of one kind and fully biodegradable
High molecular material, it under the action of microorganism can degradable generation water and carbon dioxide, environment not will cause any
Harm, can substitute traditional polymer material, therefore receive the great attention and further investigation of numerous researchers.In addition,
PLA can carry out polymerization by the lactic acid that corn stover is fermented and be made, and can reduce disappearing for non-renewable petroleum chemicals
Consumption, and then alleviate human resource crisis.But there is also some disadvantages by PLA, and such as: it is linear polymer, keeps its intensity past
It is past to meet the requirements；Brittleness is high；Price is high.In addition, its melting viscosity and melt strength are lower, lead to processing performance not
It is good.This all promotes people mainly to have copolymerization to the modification of polylactic acid at present, be blended the modified expansion in-depth study of polylactic acid
With it is the methods of compound.
Summary of the invention
For defect present in PLA proposed in background technique, the present invention one is to provide a kind of nontoxic, inexpensive, tool
There is environmentally protective polylactic acid/sesbania gum/nano-TiO of preferable processing rheological property and mechanical property2Composite material, second is that mentioning
For the preparation method of this composite material.
In order to achieve the above-mentioned object of the invention, the technical solution used in the present invention is:
A kind of environment-friendly composite material, the component of the composite material and the parts by weight of each component are as follows: 100 parts of polylactic acid, field
5-30 parts of cyanines glue, modified Nano TiO20.2-5 parts, 1-6 parts of plasticizer A, 2-15 parts of plasticizer B, 0.1-0.5 parts of lubricant.
Polylactic acid weight average molecular weight is 100,000-30 ten thousand.
Sesbania gum weight average molecular weight is 150,000-32 ten thousand.
Modified Nano TiO2The preparation method comprises the following steps: in 40-80oC, by silane coupling agent KH560, hydrochloric acid or glacial acetic acid, anhydrous
Ethyl alcohol and high purity water, the mechanical stirring 60-240min under ultrasonication, are cooled to room temperature, and wash, centrifugation, 25-50oVacuum under C
It is dry, centrifuge speed 8000-20000rpm, nano-TiO used2Partial size be 5-100nm.
Plasticizer A is one or both of triacetyl glycerine or epoxidized soybean oil mixture.
Plasticizer B is one or both of polyethylene glycol or tributyl citrate mixture；Wherein polyethylene glycol
Weight average molecular weight is 2000-20000.
Lubricant is any one of stearic acid, calcium stearate.
The preparation method of environment-friendly composite material, specific step is as follows for preparation method:
(1) in 30-80oUnder C, by modified Nano TiO2, plasticizer A mixing and mechanical stirring 120-240min, blender
Revolving speed is 1000-2000rpm；
(2) in 40-90oUnder C, by polylactic acid, sesbania gum, plasticizer B, step (1) resulting material mixes and mechanical stirring
60-180 min, blender revolving speed is 1000-2000 rpm, after material is cooled to room temperature, is squeezed on double-screw extruding pelletizing machine
Out and it is granulated；
In extruding pelletization process, twin-screw extruder section temperature are as follows: one area 140-160 of heatingoC heats 2nd area
150-170oC heats three area 165-185oC heats four area 165-185oC heats five area 170-185oC heats six area 165-
180oC, head temperature 160-175oC, engine speed 80-150rpm, feeding revolving speed are 7-15rpm.
Sesbania gum (SG) is a kind of natural plant gum of galactomannans class, from the endosperm of Sesbania seed.Sesbania exists
The plantation of the ground large area such as China Jiangsu and Zhejiang Provinces, Henan, abundance is nontoxic, cheap.In addition, its a critically important characteristic
It is exactly increasing stick.Therefore, blending and modifying is carried out by SG and PLA, can not only reduces the cost of composite material, but also can be with
The melt strength and melting viscosity of increase system, finally improve its processing performance.
Nano-TiO2With small-size effect and macro quanta tunnel effect, can produce based on inorganic nano-particle
The molecular chain movement of Percolation network, this network constraint can show significant shear shinning behavior.In certain shear
Under, inorganic nano-particle is orientated strongly, and polymeric matrix macromolecular chain is made to generate strain inducing hardening.Therefore, in polymer
Inorganic nano-particle is added, can effectively improve the processing performance and mechanical property of polymer.
Each component raw material in this composite material disclosed in this invention is easy to get, is cheap, asepsis environment-protecting；Because of sesbania
The introducing of glue reduces the processing cost of composite material；Because of nano-TiO2It is height-oriented, macromolecular strain inducing can be influenced
Orientation, can further improve the processing performance and rheological property of composite material；It can be formed by molding, extrusion, injection molding, calendering etc.
Method prepares the plastic products of different shape.
Specific embodiment
Embodiment 1
Configure ethanol/water (volume ratio 80/1) dispersion liquid 2500mL of the nano-titanium dioxide of 3.0wt%, ultrasonic disperse
30min, adjusting pH with glacial acetic acid is 3.5-4.5, the KH560 of 30mL is then added, in 70oC, under ultrasonic cleaning machine effect, machine
Tool stirs 180min, it is then cooled to room temperature, with ethanol washing, is centrifuged under 12000rpm, in triplicate, 40oC
Lower vacuum drying.
Weigh 0.1kg triacetyl glycerine and 0.06kg modified Nano TiO2, 60oC, ultrasonic cleaner act on lower machine
Tool stirs 180min, and material is then cooled to 50oC。
Weigh 3kg polylactic acid, 0.45kg sesbania gum, 0.25 kg polyethylene glycol 10000,0.05kg tributyl citrate,
0.009kg stearic acid is mixed with above-mentioned material, 50oC, under the conditions of blender revolving speed is 1000 ± 20rpm, mechanical stirring
100min.It after material is cooled to room temperature, squeezes out and is granulated on double-screw extruding pelletizing machine, polylactic acid/sesbania can be obtained
Glue/nano-TiO2Composite material.Twin-screw extruder section temperature are as follows: one area 150 of heatingoC heats two areas 165oC, heating
Three areas 175oC heats four areas 178oC heats five areas 180oC heats six areas 177oC, head temperature 172oC, engine speed are
100rpm, feeding revolving speed are 9.5rpm.
Above-mentioned gained polylactic acid/sesbania gum/nano-TiO2The impact strength of composite material is 5.7 kJ/m2, bending strength is
53.6MPa, tensile strength 57.0MPa, 40.7 % of elongation at break.
Embodiment 2
Configure ethanol/water (volume ratio 80/1) dispersion liquid 2500mL of the nano-titanium dioxide of 3.5 wt%, ultrasonic disperse
30min, adjusting pH with glacial acetic acid is 3.5-4.5, the KH560 of 33mL is then added, in 60oC, under ultrasonic cleaning machine effect, machine
Tool stirs 240 min, it is then cooled to room temperature, with ethanol washing, is centrifuged under 12000rpm, in triplicate, 25oC
Lower vacuum drying.
Weigh 0.12kg epoxidized soybean oil and 0.06kg modified Nano TiO2, 50oC, the lower machinery of ultrasonic cleaner effect
It is spare after stirring 180min.
Weigh 4kg polylactic acid, 0.4kg sesbania gum, 0.25kg polyethylene glycol 10000,0.05 kg tributyl citrate,
0.008kg stearic acid is mixed with above-mentioned material, 70oC, under the conditions of blender revolving speed is 1000 ± 20rpm, mechanical stirring
80min.It after material is cooled to room temperature, squeezes out and is granulated on double-screw extruding pelletizing machine, polylactic acid/sesbania can be obtained
Glue/nano-TiO2Composite material.Twin-screw extruder section temperature are as follows: one area 152 of heatingoC heats two areas 165oC, heating
Three areas 172oC heats four areas 175oC heats five areas 178oC heats six areas 180oC, head temperature 175oC, engine speed are
105rpm, feeding revolving speed are 10.3rpm.
Above-mentioned gained polylactic acid/sesbania gum/nano-TiO2The impact strength of composite material is 6.0 kJ/m2, bending strength is
49.8MPa, tensile strength 60.7MPa, 46.1 % of elongation at break.
Embodiment 3
Configure ethanol/water (volume ratio 80/1) dispersion liquid 2500mL of the nano-titanium dioxide of 3.2wt%, ultrasonic disperse
30min, adjusting pH with glacial acetic acid is 3.5-4.5, the KH560 of 30mL is then added, in 50oC, under ultrasonic cleaning machine effect, machine
Tool stirs 200min, it is then cooled to room temperature, with ethanol washing, is centrifuged under 12000rpm, in triplicate, 30oC
Lower vacuum drying.
Weigh 0.05kg triacetyl glycerine, 0.06kg epoxidized soybean oil and 0.1kg modified Nano TiO2, 80oC, ultrasound
Wave washer acts on lower mechanical stirring 220min, and material is then cooled to 50oC。
Weigh 2.5kg polylactic acid, 0.45kg sesbania gum, 0.25kg PEG 20000,0.005kg calcium stearate with it is upper
Material mixing is stated, 55oC, under the conditions of blender revolving speed is 1500 ± 20 rpm, mechanical stirring 150min.Material is cooled to
It after room temperature, squeezes out and is granulated on double-screw extruding pelletizing machine, polylactic acid/sesbania gum/nano-TiO can be obtained2Composite material.
Twin-screw extruder section temperature are as follows: one area 160 of heatingoC heats two areas 155oC heats three areas 170oC heats 4th area
175oC heats five areas 170oC heats six areas 178oC, head temperature 175oC, engine speed 120rpm, feeding revolving speed are
12rpm。
Above-mentioned gained polylactic acid/sesbania gum/nano-TiO2The impact strength of composite material is 5.1 kJ/m2, bending strength is
56.0MPa, tensile strength 53.8MPa, 41.2 % of elongation at break.
Embodiment 4
Configure ethanol/water (volume ratio 80/1) dispersion liquid 2500mL of the nano-titanium dioxide of 3.0 wt%, ultrasonic disperse 30
Min, adjusting pH with glacial acetic acid is 3.5-4.5, the KH560 of 30mL is then added, in 40oC, it is mechanical under ultrasonic cleaning machine effect
160min is stirred, it is then cooled to room temperature, with ethanol washing, is centrifuged under 12000rpm, in triplicate, 25oUnder C
Vacuum drying.
Weigh 0.1kg triacetyl glycerine, 0.06kg epoxidized soybean oil and 0.06kg modified Nano TiO2, 60oC, ultrasound
Wave washer acts on lower mechanical stirring 180min, and material is then cooled to 50oC。
Weigh 6kg polylactic acid, 0.5kg sesbania gum, 0.25kg PEG 20000,0.1kg tributyl citrate,
0.01kg stearic acid is mixed with above-mentioned material, 50oC, under the conditions of blender revolving speed is 1600 ± 20rpm, mechanical stirring
200min.It after material is cooled to room temperature, squeezes out and is granulated on double-screw extruding pelletizing machine, polylactic acid/sesbania can be obtained
Glue/nano-TiO2Composite material.Twin-screw extruder section temperature are as follows: one area 155 of heatingoC heats two areas 167oC, heating
Three areas 178oC heats four areas 182oC heats five areas 180oC heats six areas 175oC, head temperature 175oC, engine speed are
115rpm, feeding revolving speed are 11rpm.
Above-mentioned gained polylactic acid/sesbania gum/nano-TiO2The impact strength of composite material is 6.3 kJ/m2, bending strength is
48.2MPa, tensile strength 62.4MPa, 50.7 % of elongation at break.
Composite material of the present invention, because using triacetyl glycerine or epoxidized soybean oil pretreatment modification nanometer
TiO2, polylactic acid, sesbania gum and nano-TiO2Between have good compatibility performance and good processing rheological property, torque rheology
Instrument milling device platform, each area's temperature are 160-190o C, rotor speed 20-40rpm, polylactic acid/sesbania gum/nano-TiO2It is multiple
The fusion time of condensation material is 80-200s, and counter balance torque is 5-8 Nm；Also there is good mechanical property simultaneously, impact is strong
Degree is 4.8-7.2kJ/m2, bending strength 40.2-62.1MPa, tensile strength 46.9-71.6MPa, elongation at break
27.1-58.5%。
Claims (1)
1. a kind of environment-friendly composite material, which is characterized in that weigh 0.1kg triacetyl glycerine and 0.06kg modified Nano TiO2,
60 DEG C, ultrasonic cleaner acts on lower mechanical stirring 180min, and material is then cooled to 50 DEG C；Wherein, modified Nano TiO2
The preparation method comprises the following steps: configuration 3.0wt% nano-titanium dioxide ethanol/water dispersion liquid 2500mL, wherein the body of ethyl alcohol and water
For product than being 80/1, ultrasonic disperse 30min, adjusting pH with glacial acetic acid is 3.5-4.5, and the KH560 of 30mL is then added, in 70 DEG C,
Under ultrasonic cleaning machine effect, mechanical stirring 180min with ethanol washing, is centrifuged it is then cooled to room temperature under 12000rpm
Separation, in triplicate, is dried in vacuo at 40 DEG C；
Weigh 3kg polylactic acid, 0.45kg sesbania gum, 0.25kg polyethylene glycol 10000,0.05kg tributyl citrate, 0.009kg
Stearic acid is mixed with above-mentioned material, at 50 DEG C, under the conditions of blender revolving speed is 1000 ± 20rpm, and mechanical stirring 100min, by object
After material is cooled to room temperature, squeezes out and be granulated on double-screw extruding pelletizing machine, polylactic acid/sesbania gum/nano-TiO can be obtained2
Composite material, wherein twin-screw extruder section temperature are as follows: 150 DEG C of one area of heating heats 165 DEG C of 2nd area, heats 3rd area
175 DEG C, 178 DEG C of 4th area is heated, heats 180 DEG C of 5th area, heats 177 DEG C of 6th area, 172 DEG C of head temperature, engine speed is
100rpm, feeding revolving speed are 9.5rpm.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103059530A (en) * | 2013-01-30 | 2013-04-24 | 唐山师范学院 | Composite material for producing disposable plastic products and preparation method of composite material |
| CN103588996A (en) * | 2013-10-24 | 2014-02-19 | 岳阳立诚食品科技有限公司 | Degradable starch toothpick and manufacturing method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103059530A (en) * | 2013-01-30 | 2013-04-24 | 唐山师范学院 | Composite material for producing disposable plastic products and preparation method of composite material |
| CN103588996A (en) * | 2013-10-24 | 2014-02-19 | 岳阳立诚食品科技有限公司 | Degradable starch toothpick and manufacturing method thereof |
Non-Patent Citations (2)
| Title |
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| 熔融聚合法制备聚乳酸/田菁胶复合材料;张青;《塑料工业》;20140131;第42卷(第1期);全文 |
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Inventor after: Zhang Qing Inventor after: Li Deling Inventor after: Li Guanghui Inventor after: Su Guixian Inventor before: Zhang Qing Inventor before: He Qin Inventor before: Li Guanghui Inventor before: Su Guixian Inventor before: Yang Xiaochun Inventor before: Li Deling |
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Effective date of registration: 20201019 Address after: No. n793, floor 3, xingguangyingjing, No. 117, Shuiyin Road, Yuexiu District, Guangzhou City, Guangdong Province Patentee after: Guangzhou haokezhi Technology Development Co.,Ltd. Address before: 063000 No. 156 Jianshe North Road, Hebei, Tangshan City Patentee before: Tangshan Normal University |
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Effective date of registration: 20201201 Address after: No. 797, Renmin East Road, Jieshou City, Fuyang City, Anhui Province Patentee after: ANHUI DINGYANG BIO-BASED MATERIALS Co.,Ltd. Address before: No. n793, floor 3, xingguangyingjing, No. 117, Shuiyin Road, Yuexiu District, Guangzhou City, Guangdong Province Patentee before: Guangzhou haokezhi Technology Development Co.,Ltd. |