CN103059530B - Composite material for producing disposable plastic products and preparation method of composite material - Google Patents
Composite material for producing disposable plastic products and preparation method of composite material Download PDFInfo
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- CN103059530B CN103059530B CN201310035723.0A CN201310035723A CN103059530B CN 103059530 B CN103059530 B CN 103059530B CN 201310035723 A CN201310035723 A CN 201310035723A CN 103059530 B CN103059530 B CN 103059530B
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Abstract
The invention provides a composite material for producing disposable plastic products. The composite material comprises the following components in parts by weight: 100 parts of poly-lactic acid, 10-50 parts of starch, 0.5-6 parts of nano SiO2, 3-15 parts of dihydric alcohol or polyhydric alcohol, 3-5 parts of polyethylene glycol and 1-3 parts of glycerin monostearate. With the adoption of the starch-based nano-silicon dioxide master batch, the poly-lactic acid/starch/SiO2 composite material has excellent mechanical property and molding processing property, thus the composite material has excellent molding processing property; the shearing rate of a torque rheometer extrusion machine platform is 50-900s<-1>, the melt shear viscosity of the poly-lactic acid/starch/SiO2 composite material is 700-3500Pa*s; and the poly-lactic acid/starch/SiO2 composite material can be used for preparing packaging thin film, big-opening or small-opening plastic containers on universal plastic processing equipment through extrusion-blown molding and extrusion stretching.
Description
Technical field
The present invention relates to the forming process field of environment-friendly polymers, specifically, relate to a kind of matrix material for the production of Phthalates and preparation method.
Background technology
Poly(lactic acid) is environment-friendly material, can be carbonic acid gas and water through biological decomposition, not pollute environment.Poly(lactic acid) substitutes petrochemical-based plastics, particularly Phthalates, not only can alleviate the petroleum resources problem of growing tension, and environment " white " pollution problem caused after fundamentally can solving Phthalates consumption.
But polylactic acid-based Phthalates, Costco Wholesale is very high, far above the like product such as polyethylene, polypropylene.Except outside price factor, polylactic acid melt intensity is low, and film bubble is unstable, is easy to break, and makes it prepare Phthalates at apparatus for blow moulding such as employing blown film, extrusion-blown modling and stretch-blows and is restricted.Polylactic acid melt presents shear shinning character, and to temperature, there is dependency, but very little to shearing rate dependency under low shear conditions, even show as Newtonian fuid behavior, the moulding process of poly(lactic acid) can only be carried out in narrow range of shear rate and narrow temperature range.
Starch comes from renewable biomass resource, is natural macromolecular compound, wide material sources and cheap.Poly(lactic acid) and starch blending can reduce the production cost of polylactic acid based plastics.But the hydrogen bond of starch polymer interchain makes its melt temperature higher than decomposition temperature, and moulding processability is very poor.And poly(lactic acid) and starch poor compatibility, toughness is not enough, and be difficult to strain hardening, tension fracture elongation rate is low.Therefore, the consistency of polylactic acid/starch blend is another key factor solving its forming process problem.
Polymer/inorganic nanometer particle compesite is because of the small-size effect of inorganic nano-particle and macro quanta tunnel effect, can produce the Percolation network based on inorganic nano-particle, the macromolecular chain motion of this network constraint can show significant shear shinning behavior.Under certain shear, the strong orientation of inorganic nano-particle, and make polymeric matrix macromolecular chain produce strain inducing sclerosis.Therefore, add inorganic nano-particle in polymkeric substance, effectively can improve processing characteristics and the mechanical property of polymkeric substance.
Summary of the invention
For above-mentioned deficiency of the prior art, the invention provides a kind of matrix material for the production of Phthalates and the preparation method with good mechanical property and good moulding processability.
The technical solution used in the present invention is:
For the production of a matrix material for Phthalates, according to weight fraction meter, formula consists of:
Poly(lactic acid): 100 parts;
Starch: 10-50 part;
Nano-meter SiO_2
2: 0.5-6 part;
Binary or polyvalent alcohol: 3-15 part;
Polyoxyethylene glycol: 3-5 part;
Glyceryl monostearate: 1-3 part.
Poly(lactic acid) weight-average molecular weight is 100,000-30 ten thousand.
Described starch is W-Gum, wheat starch, yam starch, tapioca (flour) or sweet potato starch.
Described Nano-meter SiO_2
2particle diameter is 200-500 nanometer.
Described dibasic alcohol or polyvalent alcohol are at least the one in ethylene glycol, 1,2-PD, glycerine, Xylitol or polyether glycol.
Described polyoxyethylene glycol weight-average molecular weight is 2 000-20000.
For the production of a composite material and preparation method thereof for Phthalates, preparation method comprises the following steps:
(1) Nano-meter SiO_2
2, binary or polyvalent alcohol, in 60-90
oc mechanical stirring 180-240 minute, stirrer rotating speed is 1000-2000 rev/min, and material is cooled to 40-50
oc;
(2) starch, glyceryl monostearate and step (1) gained material, in 40-60
oc mechanical stirring 60-90 minute, stirrer rotating speed is 1000-2000 rev/min, after material is cooled to room temperature, extrudes on the twin screw extruder, granulation, and twin screw extruder zone temperatures is 110-145
oc;
(3) poly(lactic acid) and polyoxyethylene glycol are 90-120 in temperature
oc, under the condition that stirrer rotating speed is 1000-2000 rev/min, mechanical stirring 120-150 minute, material is cooled to room temperature;
(4) take step (2) and step (3) material, mixed at room temperature is even, extrudes on the twin screw extruder, granulation, and twin screw extruder zone temperatures is 130-175
oc.
The beneficial effect of hinge structure of the present invention:
Polylactic acid/starch/SiO of the present invention
2matrix material, because of the introducing of binary or polyvalent alcohol, starch has good processability; Because of binary or polyvalent alcohol pre-treatment Nano-meter SiO_2
2, starch and Nano-meter SiO_2
2between there is good compatibility performance; Further, poly(lactic acid), starch and Nano-meter SiO_2
2between there is good compatibility performance.
Polylactic acid/starch/SiO of the present invention
2matrix material, because of starch base nanometer titanium dioxide silicon original material, polylactic acid/starch/SiO
2matrix material has good mechanical property and moulding processability.
The present invention is for the production of the matrix material of Phthalates and preparation method, and composite material exhibits is white or oyster white pellet, has following characteristics:
(1) good mechanical property.Shock strength is 3.1-5.4 kJ/m
2, flexural strength is 54.8-80.6 MPa, and tensile strength is 36.3-57.1 MPa, elongation at break 15.4-64.5%.
(2) good moulding processability.Torque rheometer forcing machine platform, shearing rate is 50-900 s
-1, polylactic acid/starch/SiO
2the melt shear viscosity of matrix material is 700-3500 Pa × s.Polylactic acid/starch/SiO
2matrix material can on general device of plastic processing by extrusion-blown modling, extrude stretching and prepare packaging film, large mouth or osculum plastic containers.
Embodiment
Embodiment 1
Take 0.4 Kg glycerine and 0.08 Kg Nano-meter SiO_2
2, 70
oc, stirrer rotating speed are that under 1200 ± 20 revs/min of conditions, mechanical stirring is after 200 minutes, and material is cooled to 45
oc.
Take 1 Kg W-Gum and 0.08 Kg glyceryl monostearate, with above-mentioned mixing of materials, 50
oc, stirrer rotating speed are that under 1200 ± 20 revs/min of conditions, mechanical stirring is after 80 minutes, and material is cooled to room temperature.
Above-mentioned material is extruded by twin screw extruder, granulation, obtains starch base Nano-meter SiO_2
2masterbatch.The each zone temperatures of twin screw extruder is respectively 115
oc, 120
oc, 130
oc, 125
oc, 120
oc, 120
oc, head temperature is 120
oc.Screw speed is 250 revs/min.
Take 4 Kg poly(lactic acid) and 0.16 Kg relative average molecular mass is the polyoxyethylene glycol of 10000,100
oc, stirrer rotating speed are under 1200 ± 20 revs/min of conditions, mechanical stirring 150 minutes.After material is cooled to room temperature, with starch base Nano-meter SiO_2
2masterbatch mixes, and is extruded, granulation by twin screw extruder, can obtain white polylactic acid/starch/SiO
2matrix material.The each zone temperatures of twin screw extruder is respectively 155
oc, 165
oc, 155
oc, 145
oc, 145
oc, 140
oc, head temperature is 140
oc.Screw speed is 300 revs/min.
Above-mentioned gained polylactic acid/starch/SiO
2the shock strength of matrix material is 5.3 kJ/m
2, flexural strength is 67.0 MPa, and tensile strength is 48.8 MPa, elongation at break 38.7 %.This matrix material can on general device of plastic processing by extrusion-blown modling, extrude stretching and prepare packaging film, large mouth or osculum plastic containers.
Embodiment 2
Take 0.4 Kg glycerine and 0.08 Kg Nano-meter SiO_2
2, 70
oc, stirrer rotating speed are that under 1200 ± 20 revs/min of conditions, mechanical stirring is after 200 minutes, and material is cooled to 45
oc.
Take 1.6 Kg W-Gums and 0.08 Kg glyceryl monostearate, with above-mentioned mixing of materials, 50
oc, stirrer rotating speed are that under 1200 ± 20 revs/min of conditions, mechanical stirring is after 80 minutes, and material is cooled to room temperature.
Above-mentioned material is extruded by twin screw extruder, granulation, obtains starch base Nano-meter SiO_2
2masterbatch.The each zone temperatures of twin screw extruder is respectively 115
oc, 120
oc, 130
oc, 125
oc, 120
oc, 120
oc, head temperature is 120
oc.Screw speed is 250 revs/min.
Take 4 Kg poly(lactic acid) and 0.16 Kg relative average molecular mass is the polyoxyethylene glycol of 10 000,100
oc, stirrer rotating speed are under 1200 ± 20 revs/min of conditions, mechanical stirring 150 minutes.After material is cooled to room temperature, with starch base Nano-meter SiO_2
2masterbatch mixes, and is extruded, granulation by twin screw extruder, can obtain white polylactic acid/starch/SiO
2matrix material.The each zone temperatures of twin screw extruder is respectively 155
oc, 165
oc, 155
oc, 145
oc, 145
oc, 140
oc, head temperature is 140
oc.Screw speed is 300 revs/min.
Above-mentioned gained polylactic acid/starch/SiO
2the shock strength of matrix material is 4.5 kJ/m
2, flexural strength is 72.3MPa, and tensile strength is 53.9 MPa, elongation at break 61.2 %.This matrix material can on general device of plastic processing by extrusion-blown modling, extrude stretching and prepare packaging film, large mouth or osculum plastic containers.
Embodiment 3
Take 0.3 Kg Xylitol, 0.1 Kg ethylene glycol and 0.08 Kg Nano-meter SiO_2
2, 70
oc, stirrer rotating speed are that under 1200 ± 20 revs/min of conditions, mechanical stirring is after 180 minutes, and material is cooled to 45
oc.
Take 1 Kg W-Gum and 0.08 Kg glyceryl monostearate, with above-mentioned mixing of materials, 50
oc, stirrer rotating speed are that under 1200 ± 20 revs/min of conditions, mechanical stirring is after 90 minutes, and material is cooled to room temperature.
Above-mentioned material is extruded by twin screw extruder, granulation, obtains starch base Nano-meter SiO_2
2masterbatch.The each zone temperatures of twin screw extruder is respectively 120
oc, 125
oc, 135
oc, 125
oc, 120
oc, 120
oc, head temperature is 120
oc.Screw speed is 250 revs/min.
Take 4 Kg poly(lactic acid) and 0.16 Kg relative average molecular mass is the polyoxyethylene glycol of 10 000,100
oc, stirrer rotating speed are under 1200 ± 20 revs/min of conditions, mechanical stirring 150 minutes.After material is cooled to room temperature, with starch base Nano-meter SiO_2
2masterbatch mixes, and is extruded, granulation by twin screw extruder, can obtain white polylactic acid/starch/SiO
2matrix material.The each zone temperatures of twin screw extruder is respectively 155
oc, 165
oc, 155
oc, 145
oc, 145
oc, 140
oc, head temperature is 140
oc.Screw speed is 300 revs/min.
Above-mentioned gained polylactic acid/starch/SiO
2the shock strength of matrix material is 4.9 kJ/m
2, flexural strength is 58.7 MPa, and tensile strength is 43.8 Mpa, elongation at break 31.6 %.This matrix material can on general device of plastic processing by extrusion-blown modling, extrude stretching and prepare packaging film, large mouth or osculum plastic containers.
Embodiment 4
Take 0.2 Kg glycerine, 0.2Kg polyether glycol and 0.08 Kg Nano-meter SiO_2
2, 90
oc, stirrer rotating speed are that under 1200 ± 20 revs/min of conditions, mechanical stirring is after 240 minutes, and material is cooled to 50
oc.
Take 1 Kg W-Gum and 0.08 Kg glyceryl monostearate, with above-mentioned mixing of materials, 50
oc, stirrer rotating speed are that under 1200 ± 20 revs/min of conditions, mechanical stirring is after 90 minutes, and material is cooled to room temperature.
Above-mentioned material is extruded by twin screw extruder, granulation, obtains starch base Nano-meter SiO_2
2masterbatch.The each zone temperatures of twin screw extruder is respectively 120
oc, 125
oc, 135
oc, 130
oc, 125
oc, 120
oc, head temperature is 120
oc.Screw speed is 250 revs/min.
Take 4 Kg poly(lactic acid) and 0.16 Kg relative average molecular mass is the polyoxyethylene glycol of 10 000,100
oc, stirrer rotating speed are under 1200 ± 20 revs/min of conditions, mechanical stirring 150 minutes.After material is cooled to room temperature, with starch base Nano-meter SiO_2
2masterbatch mixes, and is extruded, granulation by twin screw extruder, can obtain white polylactic acid/starch/SiO
2matrix material.The each zone temperatures of twin screw extruder is respectively 155
oc, 165
oc, 155
oc, 145
oc, 145
oc, 140
oc, head temperature is 140
oc.Screw speed is 300 revs/min.
Above-mentioned gained polylactic acid/starch/SiO
2the shock strength of matrix material is 4.8 kJ/m
2, flexural strength is 59.1 MPa, and tensile strength is 41.8 MPa, elongation at break 25.4%.This matrix material can on general device of plastic processing by extrusion-blown modling, extrude stretching and prepare packaging film, large mouth or osculum plastic containers.
Embodiment 5
Take 0.4 Kg ethylene glycol and 0.08 Kg Nano-meter SiO_2
2, 70
oc, stirrer rotating speed are that under 1200 ± 20 revs/min of conditions, mechanical stirring is after 200 minutes, and material is cooled to 45
oc.
Take 1 Kg W-Gum and 0.08 Kg glyceryl monostearate, with above-mentioned mixing of materials, 50
oc, stirrer rotating speed are that under 1200 ± 20 revs/min of conditions, mechanical stirring is after 80 minutes, and material is cooled to room temperature.
Above-mentioned material is extruded by twin screw extruder, granulation, obtains starch base Nano-meter SiO_2
2masterbatch.The each zone temperatures of twin screw extruder is respectively 125
oc, 130
oc, 140
oc, 135
oc, 130
oc, 130
oc, head temperature is 130
oc.Screw speed is 250 revs/min.
Take 4 Kg poly(lactic acid) and 0.16Kg relative average molecular mass is the polyoxyethylene glycol of 10 000,100
oc, stirrer rotating speed are under 1200 ± 20 revs/min of conditions, mechanical stirring 150 minutes.After material is cooled to room temperature, with starch base Nano-meter SiO_2
2masterbatch mixes, and is extruded, granulation by twin screw extruder, can obtain white polylactic acid/starch/SiO
2matrix material.The each zone temperatures of twin screw extruder is respectively 160
oc, 170
oc, 160
oc, 155
oc, 150
oc, 145
oc, head temperature is 145
oc.Screw speed is 300 revs/min.
Above-mentioned gained polylactic acid/starch/SiO
2the shock strength of matrix material is 5.1 kJ/m
2, flexural strength is 79.7 MPa, and tensile strength is 49.3 MPa, elongation at break 59.4%.This matrix material can on general device of plastic processing by extrusion-blown modling, extrude stretching and prepare packaging film, large mouth or osculum plastic containers.
Embodiment 6
Take 0.3 Kg 1,2-PD, 0.1 Kg Xylitol and 0.08 Kg Nano-meter SiO_2
2, 70
oc, stirrer rotating speed are that under 1200 ± 20 revs/min of conditions, mechanical stirring is after 200 minutes, and material is cooled to 45
oc.
Take 1 Kg W-Gum and 0.08 Kg glyceryl monostearate, with above-mentioned mixing of materials, 50
oc, stirrer rotating speed are that under 1200 ± 20 revs/min of conditions, mechanical stirring is after 80 minutes, and material is cooled to room temperature.
Above-mentioned material is extruded by twin screw extruder, granulation, obtains starch base Nano-meter SiO_2
2masterbatch.The each zone temperatures of twin screw extruder is respectively 125
oc, 130
oc, 140
oc, 135
oc, 130
oc, 130
oc, head temperature is 130
oc.Screw speed is 250 revs/min.
Take 4 Kg poly(lactic acid) and 0.16 Kg relative average molecular mass is the polyoxyethylene glycol of 10 000,100
oc, stirrer rotating speed are under 1200 ± 20 revs/min of conditions, mechanical stirring 150 minutes.After material is cooled to room temperature, with starch base Nano-meter SiO_2
2masterbatch mixes, and is extruded, granulation by twin screw extruder, can obtain white polylactic acid/starch/SiO
2matrix material.The each zone temperatures of twin screw extruder is respectively 165
oc, 175
oc, 165
oc, 155
oc, 145
oc, 145
oc, head temperature is 145
oc.Screw speed is 300 revs/min.
Above-mentioned gained polylactic acid/starch/SiO
2the shock strength of matrix material is 4.8 kJ/m
2, flexural strength is 59.9 MPa, and tensile strength is 44.5 MPa, elongation at break 43.2 %.This matrix material can on general device of plastic processing by extrusion-blown modling, extrude stretching and prepare packaging film, large mouth or osculum plastic containers.
The present invention is for the production of the matrix material of Phthalates and preparation method, and composite material exhibits is white or oyster white pellet, has following characteristics:
(1) good mechanical property.Shock strength is 3.1-5.4 kJ/m
2, flexural strength is 54.8-80.6 MPa, and tensile strength is 36.3-57.1 MPa, elongation at break 15.4-64.5%.
(2) good moulding processability.Torque rheometer forcing machine platform, shearing rate is 50-900 s
-1, polylactic acid/starch/SiO
2the melt shear viscosity of matrix material is 700-3500 Pa × s.Polylactic acid/starch/SiO
2matrix material can on general device of plastic processing by extrusion-blown modling, extrude stretching and prepare packaging film, large mouth or osculum plastic containers.
Claims (6)
1. for the production of a matrix material for Phthalates, it is characterized in that: according to weight fraction meter, formula consists of:
Poly(lactic acid): 100 parts;
Starch: 10-50 part;
Nano-meter SiO_2
2: 0.5-6 part;
Binary or polyvalent alcohol: 3-15 part;
Polyoxyethylene glycol: 3-5 part;
Glyceryl monostearate: 1-3 part;
Described Nano-meter SiO_2
2particle diameter is 200-500 nanometer.
2. according to claims 1 for the production of the matrix material of Phthalates, it is characterized in that: poly(lactic acid) weight-average molecular weight is 100,000-30 ten thousand.
3. according to claim 1 for the production of the matrix material of Phthalates, it is characterized in that, described starch is W-Gum, wheat starch, yam starch, tapioca (flour) or sweet potato starch.
4. according to claim 1 for the production of the matrix material of Phthalates, it is characterized in that, described dibasic alcohol or polyvalent alcohol are at least the one in ethylene glycol, 1,2-PD, glycerine, Xylitol or polyether glycol.
5. according to claim 1 for the production of the matrix material of Phthalates, it is characterized in that, described polyoxyethylene glycol weight-average molecular weight is 2 000-20000.
6., as claimed in claim 1 for the production of a composite material and preparation method thereof for Phthalates, it is characterized in that, preparation method comprises the following steps:
(1) Nano-meter SiO_2
2, binary or polyvalent alcohol, in 60-90
oc mechanical stirring 180-240 minute, stirrer rotating speed is 1000-2000 rev/min, and material is cooled to 40-50
oc;
(2) starch, glyceryl monostearate and step (1) gained material, in 40-60
oc mechanical stirring 60-90 minute, stirrer rotating speed is 1000-2000 rev/min, after material is cooled to room temperature, extrudes on the twin screw extruder, granulation, and twin screw extruder zone temperatures is 110-145
oc;
(3) poly(lactic acid) and polyoxyethylene glycol are 90-120 in temperature
oc, under the condition that stirrer rotating speed is 1000-2000 rev/min, mechanical stirring 120-150 minute, material is cooled to room temperature;
(4) take step (2) and step (3) material, mixed at room temperature is even, extrudes on the twin screw extruder, granulation, and twin screw extruder zone temperatures is 130-175
oc.
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| CN104861604B (en) * | 2015-06-12 | 2019-03-19 | 唐山师范学院 | A kind of environment-friendly composite material and preparation method thereof |
| CN111057350B (en) * | 2018-10-16 | 2022-08-23 | 湖南工业大学 | Full-biodegradable composite material with excellent mechanical property and preparation method thereof |
| CN111218034A (en) * | 2019-06-04 | 2020-06-02 | 湖南工业大学 | Thermoplastic starch film and preparation method thereof |
| CN115139424A (en) * | 2022-07-05 | 2022-10-04 | 普立思生物科技有限公司 | Synthesis and forming process of thin-wall injection molding lactic acid resin |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101805499A (en) * | 2010-03-15 | 2010-08-18 | 任伟 | Full-degradable thermoplastic composite material and sheet thereof |
| CN102408588A (en) * | 2011-09-20 | 2012-04-11 | 苏州汉丰新材料有限公司 | Completely biodegradable resin made of non-staple grain plant modified starch and its preparation method |
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2013
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101805499A (en) * | 2010-03-15 | 2010-08-18 | 任伟 | Full-degradable thermoplastic composite material and sheet thereof |
| CN102408588A (en) * | 2011-09-20 | 2012-04-11 | 苏州汉丰新材料有限公司 | Completely biodegradable resin made of non-staple grain plant modified starch and its preparation method |
Non-Patent Citations (1)
| Title |
|---|
| 热塑性淀粉/聚乳酸共混材料的制备、表征及性能研究;和平生;《中国优秀硕士学位论文全文数据库 工程科技I辑》;20120515(第5期);15、30、49、50、60 * |
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