CN103044839A - Polylactic acid composite material and preparation method thereof - Google Patents
Polylactic acid composite material and preparation method thereof Download PDFInfo
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- CN103044839A CN103044839A CN2012105664283A CN201210566428A CN103044839A CN 103044839 A CN103044839 A CN 103044839A CN 2012105664283 A CN2012105664283 A CN 2012105664283A CN 201210566428 A CN201210566428 A CN 201210566428A CN 103044839 A CN103044839 A CN 103044839A
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- lactic acid
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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
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/04—Particle-shaped
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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
- B29C48/78—Thermal treatment of the extrusion moulding material or of preformed parts or layers, e.g. by heating or cooling
- B29C48/875—Thermal treatment of the extrusion moulding material or of preformed parts or layers, e.g. by heating or cooling for achieving a non-uniform temperature distribution, e.g. using barrels having both cooling and heating zones
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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
- B29C2948/92514—Pressure
-
- 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
Abstract
The invention discloses a polylactic acid composite material and a preparation method thereof. The polylactic acid composite material comprises the formula components in parts by weight as follows: 60-90 parts of polylactic acid of maleic anhydride stem grafting, 10-30 parts of plant fibers, 0.2-0.6 part of an antioxidant agent and 0.5-1 part of a lubricating agent. According to the polylactic acid composite material, polylactic acid of the maleic anhydride stem grafting is taken as a base material, the plant fibers and other components are utilized to generate a synergistic effect during the melt extrusion process, so that the interfacial compatibility between polylactic acid and the fibers is improved, therefore, the excellent mechanical property of the polylactic acid composite material is achieved. Simultaneously, polylactic acid of the maleic anhydride stem grafting and the plant fibers can be completely biologically degraded, so that the polylactic acid composite material is environment-friendly. Besides, the process is simple, the conditions are easy to control, the cost is low, the requirements for equipment are small, and therefore, the polylactic acid composite material and the preparation method thereof are suitable for industrial production.
Description
Technical field
The invention belongs to technical field of polymer materials, particularly a kind of lactic acid composite material and preparation method thereof.
Background technology
Along with the continuous increase of automobile volume of production and marketing, in order to obtain the good matrix material of environmental protection and mechanical property, occurred at present adopting the matrix material of vegetable fibre modification to replace conventional plastic, and prepared the automotive trim component with the matrix material of this vegetable fibre modification.
Matrix material such as sisal fibers reinforced polypropylene compound material and the composite material of poly lacltic acid enhanced by ramie fiber etc. of existing vegetable fibre modification.Wherein, polypropylene in sisal fibers reinforced polypropylene compound material part can't be degraded, and fiber and polyacrylic interface compatibility are to be improved.Though composite material of poly lacltic acid enhanced by ramie fiber is biodegradable matrix material, this composite material of poly lacltic acid enhanced by ramie fiber adopts the chemical modification means of in-situ polymerization, and solvent recuperation is difficult, easily cause environmental pollution, and the scale operation difficulty is large.
Summary of the invention
The object of the invention is to overcome the above-mentioned deficiency of prior art, the lactic acid composite material that interface compatibility is good, mechanical property is excellent between a kind of poly(lactic acid) and the fiber is provided.
Another object of the present invention provides that a kind of environmental protection, technique are simple, the easy lactic acid composite material preparation method of control of condition.
In order to realize the foregoing invention purpose, technical scheme of the present invention is as follows:
A kind of lactic acid composite material comprises the recipe ingredient of following weight percent:
And a kind of preparation method of lactic acid composite material may further comprise the steps:
Take by weighing respectively each component according to above-mentioned lactic acid composite material prescription;
Described each component that takes by weighing is carried out mixing treatment, obtain mixture;
Described mixture is melt extruded, and granulation obtains described lactic acid composite material; Wherein, the processing condition that melt extrude are:
170～180 ℃ of one district's temperature, 170～180 ℃ of two district's temperature, 180～190 ℃ of three district's temperature, 190～200 ℃ of four district's temperature, 180～190 ℃ of heads, each distinguishes the residence time 1～2min, and pressure is 10～20MPa.
Above-mentioned lactic acid composite material is take the poly(lactic acid) of maleic anhydride graft as body material, adopt vegetable fibre and other components in melt extruding process, to act synergistically, so that the anhydride group in the polylactic acid molecule of this maleic anhydride graft forms chemically crosslinked with the hydroxyl reaction on vegetable fibre surface in melt extruding process, thereby improved the interface compatibility between poly(lactic acid) and the fiber, thereby given this lactic acid composite material excellent mechanical property.Simultaneously, the equal fully biodegradable of the poly(lactic acid) of this maleic anhydride graft and vegetable fibre, therefore, this lactic acid composite material environmental protection.
Above-mentioned lactic acid composite material preparation method only need mix each component to be incorporated in to melt extrude under the suitable temperature by prescription and can obtain product, and its preparation method technique is simple, and condition is easily controlled, and is with low cost, and characteristics low for equipment requirements are suitable for suitability for industrialized production.In addition, this preparation method's environmental protection has effectively been avoided such as chemical modification means such as in-situ polymerizations, has avoided the use to solvent.
Description of drawings
The invention will be further described below in conjunction with drawings and Examples, in the accompanying drawing:
Fig. 1 is embodiment of the invention lactic acid composite material preparation method's process flow diagram.
Embodiment
In order to make the technical problem to be solved in the present invention, technical scheme and beneficial effect clearer, below in conjunction with embodiment and accompanying drawing, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explain the present invention, is not intended to limit the present invention.
The embodiment of the invention provides the interface compatibility between a kind of poly(lactic acid) and the fiber good, and mechanical property has excellent lactic acid composite material.This lactic acid composite material comprises the recipe ingredient of following weight percent:
Particularly, the poly(lactic acid) of above-mentioned maleic anhydride graft is matrix composition, in melt extruding process, its molecule and other components be the vegetable fibre synergy particularly, anhydride group in the polylactic acid molecule of concrete is this maleic anhydride graft forms chemically crosslinked with the hydroxyl reaction on vegetable fibre surface in melt extruding process, thereby improved the interface compatibility between poly(lactic acid) and the fiber, thereby realize the modification to poly(lactic acid), significantly improve the interface problem between poly(lactic acid) and the vegetable fibre.In order further to improve interface compatibility between poly(lactic acid) and the vegetable fibre, in a preferred embodiment, the percentage of grafting of the poly(lactic acid) of this maleic anhydride graft is 0.4% ~ 0.7%, and in more preferred embodiment, the percentage of grafting of the poly(lactic acid) of this maleic anhydride graft is 0.5%.
In addition, the poly(lactic acid) of maleic anhydride graft can prepare according to the poly(lactic acid) preparation method of hereinafter described maleic anhydride graft in the various embodiments described above.
Above-mentioned vegetable fibre is preferably one or both in bamboo fibers, the flaxen fiber.Certainly can also be the other plant fiber.For so that lactic acid composite material has more excellent mechanical property, in a preferred embodiment, the size order number of this vegetable fibre is the 100-200 order.
In further preferred embodiment, above-mentioned vegetable fibre is preferably with the vegetable fibre after the coupling agent treatment.The method of this coupling agent treatment vegetable fibre can prepare according to coupling agent treatment vegetable fibre preparation method hereinafter described.Wherein, coupling agent is preferably amino coupling agent, and such as KH-550 or KBM-602 etc., vegetable fibre is one or both in bamboo fibers, the flaxen fiber.Select the vegetable fibre after the coupling agent treatment can further improve the consistency at the poly(lactic acid) interface of vegetable fibre and maleic anhydride graft.
Above-mentioned lubricant composition can be attached on other component surfaces in melt extruding process, so that each component is fully disperseed, thereby so that each component fully reacts or acts on, stablizing of lactic acid composite material performance in the raising the various embodiments described above is convenient to the conveying in each component melts extrusion simultaneously.In a preferred embodiment, this lubricant is interior lubricated and outer lubricated compound system, wherein, and interior lubricating with outer lubricated weight (or other unit) than being 1:1～3.。Wherein, interiorly lubricated be preferably PE wax or/and OP wax, external lubricant is preferably stearate, such as calcium stearate, Zinic stearas etc.
The antioxidant property of lactic acid composite material prolongs its work-ing life in the above-mentioned antioxidant component energy Effective Raise the various embodiments described above.In a preferred embodiment, the composite antioxidant that described oxidation inhibitor is made of primary antioxidant and auxiliary antioxidant, wherein, the weight of primary antioxidant and auxiliary antioxidant (or other unit) is than being 1:1～2.Primary antioxidant is preferably four, and [3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, β-(3, the 5-di-tert-butyl-hydroxy phenyl) positive octadecanol ester of propionic acid etc., auxiliary antioxidant is tricresyl phosphite (2,4-di-t-butyl phenyl ester), two (2,4-DTBP) pentaerythritol diphosphites etc.
From the above mentioned, above-mentioned lactic acid composite material adopts vegetable fibre to strengthen poly(lactic acid), namely take the poly(lactic acid) of maleic anhydride graft as body material, adopt vegetable fibre and other components in melt extruding process, to act synergistically, improve the interface compatibility between poly(lactic acid) and the fiber, thereby given this lactic acid composite material excellent mechanical property.Simultaneously, the equal fully biodegradable of the poly(lactic acid) of this maleic anhydride graft and vegetable fibre, therefore, this lactic acid composite material environmental protection.In addition, by to the content of each component and the adjustment of kind, improved further interface compatibility and the mechanical property of this lactic acid composite material.Have excellent mechanical property and the environmental protection characteristic of fully biodegradable just because of this lactic acid composite material, can be widely used in the component such as the interior exterior trim of automobile, such as door inner panel, column, storage tank etc., trend and the developing trend of the energy-conserving and environment-protective of responsive motor component.
Correspondingly, the embodiment of the invention also provides the preparation method of above-mentioned lactic acid composite material, and its technical process as shown in Figure 1.The method comprises the steps:
S01. take by weighing recipe ingredient: the prescription according to above-mentioned lactic acid composite material takes by weighing each component;
S02. prepare mixture: carry out mixing treatment with taking by weighing each component among the step S01, obtain mixture;
S03. melt extruding of mixture: the mixture among the step S02 is melt extruded, obtain described lactic acid composite material.
Particularly, each component preferred content and kind in the prescription of the lactic acid composite material among the above-mentioned steps S01 and the prescription are as indicated above, in order to save length, do not repeat them here.
Wherein, the poly(lactic acid) preparation method of maleic anhydride graft is preferably as follows in the lactic acid composite material prescription:
Take the poly(lactic acid) consumption of maleic anhydride graft as 100%, under 170～180 ℃, melt extrude after the initiator of the maleic anhydride of 1～2wt%, 0.1～0.2wt% mixed with poly(lactic acid), obtain the poly(lactic acid) of this maleic anhydride graft.Through recording, the poly(lactic acid) percentage of grafting of this maleic anhydride graft is 0.4～0.7%, and wherein, this percentage of grafting calculates according to the industry ordinary method, adopts weighting method to calculate such as this percentage of grafting.
In the poly(lactic acid) preparation method's of above-mentioned maleic anhydride graft preferred embodiment, this maleic anhydride content is 2wt%, and initiator content is 0.2wt%, and poly(lactic acid) content is 97.8wt%.In the preferred embodiment, maleic anhydride, initiator, poly(lactic acid) are mixed the rear poly(lactic acid) that melt extrudes the maleic anhydride graft that obtains under 170～180 ℃, the percentage of grafting that records the poly(lactic acid) of this maleic anhydride graft is 0.5%.
In further preferred embodiment, this initiator is preferably initiator DCP.Certainly, this initiator can also be selected this area other initiators commonly used.
In this step S01, plant fibre components is preferably the vegetable fibre after the coupling agent treatment in the prescription of lactic acid composite material, and its preparation method is preferably as follows:
Bamboo fibers is lower dry 4 ~ 6 hours at 70 ~ 80 ℃, dry good bamboo fibers (mass percent of coupling agent is preferably 2 ~ 4%) in the amino silicane coupling agent of solvent cut soaked 4 ~ 5 hours, then in baking oven, be dried to constant weight, obtain the vegetable fibre that coupling agent treatment is crossed.
Among the above-mentioned steps S02, each component is carried out the time of mixing treatment and can be adjusted flexibly according to actual production conditions, as long as each component premix fully, can be mixing machine etc. such as the equipment of mixing.
Among the above-mentioned steps S03, the temperature that melt extrudes of mixture can be made as 5 temperature sections or humidity province, and wherein concrete to melt extrude technique as follows:
170～180 ℃ of one district's temperature, 170～180 ℃ of two district's temperature, 180～190 ℃ of three district's temperature, 190～200 ℃ of four district's temperature, 180～190 ℃ of heads, the residence time 1～2min, pressure are 10～20MPa.
Above-mentioned lactic acid composite material preparation method only need mix each component to be incorporated in to melt extrude under the suitable temperature by prescription and can obtain product.The control that only needs to control the processing parameters such as temperature, time and pressure that melt extrude in melt extruding process gets final product, and its preparation method technique is simple, and condition is easily controlled, and is with low cost, and characteristics low for equipment requirements are suitable for suitability for industrialized production.In addition, this preparation method's environmental protection has effectively been avoided such as chemical modification means such as in-situ polymerizations, has avoided the use to solvent.
Now take the prescription of concrete lactic acid composite material and preparation method as example, the present invention is further elaborated.
Embodiment 1
A kind of lactic acid composite material and preparation method thereof.The weight percent recipe ingredient of this lactic acid composite material is referring to following table 1, and wherein, vegetable fibre is 150 order bamboo fiberss, and the percentage of grafting of the poly(lactic acid) of maleic anhydride graft is 0.5%; Oxidation inhibitor is that weight ratio is the primary antioxidant of 1:2 and the composite antioxidant that auxiliary antioxidant consists of, primary antioxidant is that [3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, auxiliary antioxidant is tricresyl phosphite (2,4-di-t-butyl phenyl ester), select Ciba company to produce, trade names are respectively Irganox1010 and Irganox168; Lubricant is that weight ratio is the interior lubricated and outer lubricated compound system of 1:3, and internal lubricant is PE wax, and external lubricant is calcium stearate.
Its preparation method is as follows:
S11: take by weighing 10 parts of bamboo fiberss, 89.3 parts of the poly(lactic acid) of maleic anhydride graft, 0.5 part of lubricant, 0.2 part in oxidation inhibitor according to 1 prescription of embodiment in the table 1 hereinafter;
S12: carry out mixing treatment with taking by weighing each component among the step S11, obtain mixture;
S13: the mixture that obtains among the step S12 is joined in the hopper of twin screw extruder, through melt blending, extruding pelletization becomes matrix material; Wherein, screw rod is respectively distinguished the temperature setting and is respectively: 170 ℃ of twin screw extruder one district's design temperatures, and 175 ℃ of two district's temperature, 180 ℃ of three district's temperature, 190 ℃ of four district's temperature, 185 ℃ of heads, residence time 1.5min, pressure are 10MPa.
Embodiment 2
A kind of lactic acid composite material and preparation method thereof.The weight percent recipe ingredient of this lactic acid composite material is referring to following table 1, and wherein, vegetable fibre is 150 order bamboo fiberss, and the percentage of grafting of the poly(lactic acid) of maleic anhydride graft is 0.5%; Oxidation inhibitor is that weight ratio is the primary antioxidant of 1:2 and the composite antioxidant that auxiliary antioxidant consists of, primary antioxidant is that [3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, auxiliary antioxidant is tricresyl phosphite (2,4-di-t-butyl phenyl ester), select Ciba company to produce, trade names are respectively Irganox1010 and Irganox168; Lubricant is that weight ratio is the interior lubricated and outer lubricated compound system of 1:3, and internal lubricant is PE wax, and external lubricant is calcium stearate.
Its preparation method is as follows:
S21: take by weighing 15 parts of bamboo fiberss, 84.1 parts of poly(lactic acid), 0.6 part of lubricant, 0.3 part in oxidation inhibitor according to 2 prescriptions of embodiment in the table 1 hereinafter;
S22: carry out mixing treatment with taking by weighing each component among the step S21, obtain mixture;
S23: the mixture that obtains among the step S22 is joined in the hopper of twin screw extruder, through melt blending, extruding pelletization becomes matrix material; Wherein, screw rod is respectively distinguished the temperature setting and is respectively: 170 ℃ of twin screw extruder one district's temperature, and 175 ℃ of two district's temperature, 180 ℃ of three district's temperature, 190 ℃ of four district's temperature, 185 ℃ of heads, residence time 1.5min, pressure are 10MPa.
Embodiment 3
A kind of lactic acid composite material and preparation method thereof.The weight percent recipe ingredient of this lactic acid composite material is referring to following table 1, and wherein, vegetable fibre is 150 order bamboo fiberss, and the percentage of grafting of the poly(lactic acid) of maleic anhydride graft is 0.5%; Oxidation inhibitor is that weight ratio is the primary antioxidant of 1:2 and the composite antioxidant that auxiliary antioxidant consists of, primary antioxidant is that [3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, auxiliary antioxidant is tricresyl phosphite (2,4-di-t-butyl phenyl ester), select Ciba company to produce, trade names are respectively Irganox1010 and Irganox168; Lubricant is that weight ratio is the interior lubricated and outer lubricated compound system of 1:3, and internal lubricant is PE wax, and external lubricant is calcium stearate.
Its preparation method is as follows:
S31: take by weighing 20 parts of bamboo fiberss, 78.8 parts of poly(lactic acid), 0.8 part of lubricant, 0.4 part in oxidation inhibitor according to 3 prescriptions of embodiment in the table 1 hereinafter;
S32: carry out mixing treatment with taking by weighing each component among the step S31, obtain mixture;
S33: the mixture that obtains among the step S32 is joined in the hopper of twin screw extruder, through melt blending, extruding pelletization becomes matrix material; Wherein, screw rod is respectively distinguished the temperature setting and is respectively: 175 ℃ of twin screw extruder one district's temperature, and 178 ℃ of two district's temperature, 185 ℃ of three district's temperature, 195 ℃ of four district's temperature, 185 ℃ of heads, residence time 1.5min, pressure are 10MPa.
Embodiment 4
A kind of lactic acid composite material and preparation method thereof.The weight percent recipe ingredient of this lactic acid composite material is referring to following table 1, and wherein, vegetable fibre 200 orders are flaxen fiber, and the percentage of grafting of the poly(lactic acid) of maleic anhydride graft is 0.5%; Oxidation inhibitor is that weight ratio is the primary antioxidant of 1:2 and the composite antioxidant that auxiliary antioxidant consists of, primary antioxidant is that [3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, auxiliary antioxidant is tricresyl phosphite (2,4-di-t-butyl phenyl ester), select Ciba company to produce, trade names are respectively Irganox1010 and Irganox168; Lubricant is that weight ratio is the interior lubricated and outer lubricated compound system of 1:3, and internal lubricant is PE wax, and external lubricant is calcium stearate.
Its preparation method is as follows:
S41: take by weighing 25 parts in flaxen fiber, 73.7 parts of poly(lactic acid), 0.8 part of lubricant, 0.5 part in oxidation inhibitor according to 4 prescriptions of embodiment in the table 1 hereinafter;
S42: carry out mixing treatment with taking by weighing each component among the step S41, obtain mixture;
S43: the mixture that obtains among the step S42 is joined in the hopper of twin screw extruder, through melt blending, extruding pelletization becomes matrix material; Wherein, screw rod is respectively distinguished the temperature setting and is respectively: 175 ℃ of twin screw extruder one district's temperature, and 178 ℃ of two district's temperature, 185 ℃ of three district's temperature, 195 ℃ of four district's temperature, 185 ℃ of heads, residence time 1.5min, pressure are 10MPa.
Embodiment 5
A kind of lactic acid composite material and preparation method thereof.The weight percent recipe ingredient of this lactic acid composite material is referring to following table 1, and wherein, vegetable fibre is 100 order flaxen fibers, and the percentage of grafting of the poly(lactic acid) of maleic anhydride graft is 0.5%; Oxidation inhibitor is that weight ratio is the primary antioxidant of 1:2 and the composite antioxidant that auxiliary antioxidant consists of, primary antioxidant is that [3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, auxiliary antioxidant is tricresyl phosphite (2,4-di-t-butyl phenyl ester), select Ciba company to produce, trade names are respectively Irganox1010 and Irganox168; Lubricant is that weight ratio is the interior lubricated and outer lubricated compound system of 1:3, and internal lubricant is PE wax, and external lubricant is calcium stearate.
Its preparation method is as follows:
S51: take by weighing 30 parts in flaxen fiber, 68.4 parts of poly(lactic acid), 1 part of lubricant, 0.6 part in oxidation inhibitor according to 5 prescriptions of embodiment in the table 1 hereinafter;
S52: carry out mixing treatment with taking by weighing each component among the step S51, obtain mixture;
S53: the mixture that obtains among the step S52 is joined in the hopper of twin screw extruder, through melt blending, extruding pelletization becomes matrix material; Wherein, screw rod is respectively distinguished the temperature setting and is respectively: 178 ℃ of twin screw extruder one district's temperature, and 180 ℃ of two district's temperature, 189 ℃ of three district's temperature, 195 ℃ of four district's temperature, 185 ℃ of heads, residence time 1.5min, pressure are 10MPa.
Performance test:
The lactic acid composite material of above-described embodiment 1 to embodiment 5 preparation is carried out the correlated performance test.Wherein, each correlated performance testing method is as follows:
Tensile strength: test by ASTM D-638 standard.Specimen types is the I type, batten size (mm): (176 ± 2) (length) * (12.6 ± 0.2) (end width) * (3.05 ± 0.2) (thickness), and draw speed is 50mm/min;
Flexural strength and modulus in flexure: test by ASTM D-790 standard.Specimen types is specimen size (mm): (128 ± 2) * (12.67 ± 0.2) * (3.11 ± 0.2), rate of bending are 20mm/min;
Socle girder notched Izod impact strength: test by ASTM D-256 standard.Specimen types is the I type, specimen size (mm): (63 ± 2) * (12.45 ± 0.2) * (3.1 ± 0.2); The breach type is category-A, and the breach residual thickness is 1.9mm;
Melting index: test by ASTM D-1238, probe temperature is 200 ℃, and load is 5 kilograms, and be 5min warm up time;
Heat-drawn wire: test specimen size (mm) by ASTM D-648: (128 ± 2) * (12.45 ± 0.2) * (3.1 ± 0.2), load are 1.82MPa;
Flame retardant properties: test test size (mm): (128 ± 2) * (12.67 ± 0.2) * (3.11 ± 0.2), flame height 20mm by UL94.
After tested, the lactic acid composite material correlated performance test result of above-described embodiment 1 to embodiment 5 preparation is as shown in table 1 respectively.
Table 1
By finding out in the above-mentioned table 1, lactic acid composite material reacts by the hydroxyl on vegetable fibre surface and the anhydride group on maleic anhydride graft poly(lactic acid) surface, form chemically crosslinked, improved the interface compatibility between poly(lactic acid) and the fiber, give the lactic acid composite material excellent mechanical performances.In addition, be it can also be seen that the particularly intensity corresponding increase along with the increase of vegetable fibre fiber of the mechanical property of lactic acid composite material by above-mentioned table 1.
The above only is preferred embodiment of the present invention, not in order to limiting the present invention, all any modifications of doing within the spirit and principles in the present invention, is equal to and replaces and improvement etc., all should be included within protection scope of the present invention.
Claims (10)
1. lactic acid composite material comprises the recipe ingredient of following parts by weight:
2. lactic acid composite material according to claim 1, it is characterized in that: the percentage of grafting of the poly(lactic acid) of described maleic anhydride graft is 0.4% ~ 0.7%.
3. lactic acid composite material according to claim 1, it is characterized in that: described vegetable fibre is the vegetable fibre after the coupling agent treatment.
4. lactic acid composite material according to claim 2 is characterized in that: described coupling agent is to contain amino silane coupling agent.
5. arbitrary described lactic acid composite material according to claim 1～4, it is characterized in that: described vegetable fibre is one or both in bamboo fibers, the flaxen fiber.
6. arbitrary described lactic acid composite material according to claim 1～3 is characterized in that: described lubricant is interior lubricated and outer lubricated compound system, and wherein, interior lubricated and outer lubricated weight ratio are 1:1～3.
7. lactic acid composite material according to claim 6 is characterized in that: described internal lubricant is PE wax or/and OP wax, and external lubricant is calcium stearate.
8. the preparation method of a lactic acid composite material may further comprise the steps:
Take by weighing respectively each component according to the arbitrary described lactic acid composite material prescription of claim 1～7;
Described each component that takes by weighing is carried out mixing treatment, obtain mixture;
Described mixture is melt extruded, and granulation obtains described lactic acid composite material; Wherein, the processing condition that melt extrude are:
170～180 ℃ of one district's temperature, 170～180 ℃ of two district's temperature, 180～190 ℃ of three district's temperature, 190～200 ℃ of four district's temperature, 180～190 ℃ of heads, the residence time 1～2min, pressure are 10～20MPa.
9. the preparation method of lactic acid composite material according to claim 8, it is characterized in that: the preparation method of the poly(lactic acid) of described maleic anhydride graft is as follows:
Take the poly(lactic acid) consumption of maleic anhydride graft as 100%, under 170～180 ℃, melt extrude after the initiator of the maleic anhydride of 1～2wt%, 0.1～0.2wt% mixed with poly(lactic acid), obtain the poly(lactic acid) of described maleic anhydride graft.
10. according to claim 8 or the preparation method of 9 described lactic acid composite materials, it is characterized in that: described vegetable fibre is the vegetable fibre of coupling agent treatment, and the method for described coupling agent treatment vegetable fibre is:
Bamboo fibers was descended dry 4 ~ 6 hours at 70 ~ 80 ℃, and dry good described bamboo fibers soaked in the amino silicane coupling agent of solvent cut 4 ~ 5 hours, then was dried to constant weight in baking oven, obtained the vegetable fibre that described coupling agent treatment is crossed.
Priority Applications (1)
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105237977A (en) * | 2015-11-06 | 2016-01-13 | 福州市福塑科学技术研究所有限公司 | Bamboo fiber reinforced degradable PLA material and preparation method thereof |
| CN107698714A (en) * | 2017-11-01 | 2018-02-16 | 宁波家联科技股份有限公司 | A kind of itaconic anhydride grafted polylactic acid copolymer and its preparation method and application |
| CN107759990A (en) * | 2017-11-01 | 2018-03-06 | 宁波家联科技股份有限公司 | A kind of full biological poly lactic acid composite and preparation method thereof |
| CN109897327A (en) * | 2019-03-06 | 2019-06-18 | 盐城市涌泉排水板有限公司 | A kind of biodegradable drain bar and its preparation process |
| CN113603910A (en) * | 2021-07-30 | 2021-11-05 | 西南交通大学 | Fully-degradable bamboo fiber and polylactic acid composite material as well as preparation method and application thereof |
| CN114621569A (en) * | 2022-03-17 | 2022-06-14 | 安徽森泰木塑集团股份有限公司 | Preparation method of high-strength bamboo fiber/polylactic acid weather-resistant fully-degradable composite material and composite material |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101200579A (en) * | 2007-11-26 | 2008-06-18 | 同济大学 | Natural fibre reinforced polylactic acid composite material and method for making same |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101200579A (en) * | 2007-11-26 | 2008-06-18 | 同济大学 | Natural fibre reinforced polylactic acid composite material and method for making same |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105237977A (en) * | 2015-11-06 | 2016-01-13 | 福州市福塑科学技术研究所有限公司 | Bamboo fiber reinforced degradable PLA material and preparation method thereof |
| CN107698714A (en) * | 2017-11-01 | 2018-02-16 | 宁波家联科技股份有限公司 | A kind of itaconic anhydride grafted polylactic acid copolymer and its preparation method and application |
| CN107759990A (en) * | 2017-11-01 | 2018-03-06 | 宁波家联科技股份有限公司 | A kind of full biological poly lactic acid composite and preparation method thereof |
| CN107698714B (en) * | 2017-11-01 | 2020-10-16 | 宁波家联科技股份有限公司 | Itaconic anhydride grafted polylactic acid copolymer and preparation method and application thereof |
| CN107759990B (en) * | 2017-11-01 | 2020-10-16 | 宁波家联科技股份有限公司 | Full-bio-based polylactic acid composite material and preparation method thereof |
| CN109897327A (en) * | 2019-03-06 | 2019-06-18 | 盐城市涌泉排水板有限公司 | A kind of biodegradable drain bar and its preparation process |
| CN113603910A (en) * | 2021-07-30 | 2021-11-05 | 西南交通大学 | Fully-degradable bamboo fiber and polylactic acid composite material as well as preparation method and application thereof |
| CN114621569A (en) * | 2022-03-17 | 2022-06-14 | 安徽森泰木塑集团股份有限公司 | Preparation method of high-strength bamboo fiber/polylactic acid weather-resistant fully-degradable composite material and composite material |
| CN114621569B (en) * | 2022-03-17 | 2023-05-12 | 安徽森泰木塑集团股份有限公司 | Preparation method of high-strength bamboo fiber/polylactic acid weather-resistant type full-degradable composite material and composite material |
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