CN101602884A - A kind of heat-resistance polylactic acid composite material and preparation method thereof - Google Patents
A kind of heat-resistance polylactic acid composite material and preparation method thereof Download PDFInfo
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Abstract
The invention provides a kind of heat-resistance polylactic acid composite material and preparation method thereof, belong to technical field of polymer materials.It has solved that the biodegradability of the goods that exist in existing method for preparing the poly(lactic acid) cross-linked material and the crosslinked polymer material is poor, cost is higher and technical problem such as mechanical property is relatively poor.This heat-resistance polylactic acid composite material comprises the composition of following weight part: polylactic resin 50-99 part of oligomeric-D lactic acid content; Nucleator 0.1-15 part; Starch or treated starch 1-50 part; Wherein said oligomeric-polylactic resin of D lactic acid content in poly--D lactic acid content be lower than 5wt%.The preparation method of this matrix material may further comprise the steps: a. batch mixing, granulation; B. injection moulding; C. thermal treatment.Mechanical property excellence, the resistance toheat of this matrix material are good.The preparation method's of this matrix material technical process is simple, processing characteristics is strong, cost is low can realize large-scale industrial production.
Description
Technical field
The present invention relates to a kind of poly-lactic acid material and preparation method thereof, relate in particular to a kind of heat-resistance polylactic acid composite material and preparation method thereof; Belong to technical field of polymer materials.
Background technology
Resource and environment is the human significant problem that realizes that Sustainable development faced, along with the mankind's continually developing to Mineral resources such as oil, the energy in the whole world presents depleted gradually situation, and the waste by the oil synthetic polymeric material has caused people's extensive concern to the negative impacts such as " white pollutions " that environment brings in addition.
For solving " white pollution " problem that waste plastic causes, each state has all proposed many practical way, and wherein the most effective also is that method just is to use biodegradable polymeric material to replace the oil synthetic polymeric material the most completely.Compare with the oil synthetic polymeric material, biodegradable polymeric material produces less heat when incinerating, and can keep natural degradation and resynthesis circulation, thereby can not comprise the ecological harmful effect that produces to global environment.And in numerous biodegradable polymeric materials, poly(lactic acid) is considered to most possibly replace the biomaterial of oil synthetic polymeric material owing to fully biodegradable and plant origin.But the second-order transition temperature of pure poly-lactic acid material is lower, and degree of crystallinity is not high, makes it promptly begin to soften about these 60 ℃, loses use properties, has greatly limited the range of application of poly(lactic acid).
In order to improve the resistance toheat of poly(lactic acid), proposed several different methods, as made poly(lactic acid) crosslinked, with fiber composite, improve crystallization rate etc.At Chinese patent application (publication number: CN101142260A) be used for preparing the method and the crosslinked polymer material of poly(lactic acid) cross-linked material, disclose by poly(lactic acid) is mixed with at least a softening agent and the cross-linking monomer that comprise rosin derivative or dicarboxylic acid derivatives and/or glycerol derivative, the gained mixture of kneading then, thus make poly (lactic acid) composition; Prepare the poly(lactic acid) moulded work by composite mold being moulded desired shape; Make moulded work crosslinked by ionization radiation irradiation then.Though the sample that makes has toughness preferably below 60 ℃, and at also tangible softening transform not more than 60 ℃.But crosslinked for it can be produced after strengthening radiation, material need contain the vinyl polyfunctional monomer in forming, and this will influence the biodegradability of goods.Chinese patent application (publication number: CN101333331A) introduced in a kind of high thermotolerance polylactic acid composite material filled by french chalk and preparation method thereof with poly(lactic acid), modified talc powder, after mix lubricant was also hot-forming, annealing obtained lactic acid composite material under 100-120 ℃.Though the resistance toheat of lactic acid composite material after heat treatment obviously improves; But the packing material that adopts is a modified talc powder, and cost is higher and mechanical property is relatively poor.
Summary of the invention
The present invention is directed to existing in prior technology the problems referred to above, a kind of have high heat resistance, cost is low and mechanical property is good lactic acid composite material are provided.
Another object of the present invention is to provide the preparation method of above-mentioned lactic acid composite material.
First purpose of the present invention can be implemented by the following technical programs: a kind of heat-resistance polylactic acid composite material, and this matrix material comprises the composition of following weight part:
The polylactic resin of oligomeric-D lactic acid content: 50-99 part; Nucleator: 0.1-15 part; Mineral filler: 1-50 part; Starch or treated starch: 1-50 part; Vegetable fibre: 1-30 part; Silane coupling agent: 0.01-5 part; Plasticized modifier: 0.1-10 part; Lubricant: 0.05-1.0 part; Wherein said oligomeric-polylactic resin of D lactic acid content in poly--D lactic acid content be lower than 5wt%.The polylactic resin of the oligomeric-D lactic acid content of heat-resistance polylactic acid composite material employing of the present invention is main raw material and derives from natural mineral filler, vegetable fibre and starch or treated starch carry out melt blending and make, the inventor is by for a long time to the research of the promotion crystallization of the crystallization of the polylactic resin self of oligomeric-D lactic acid content and nucleator, reasonable compatibility mineral filler again, vegetable fibre, silane coupling agent, the lactic acid composite material that plasticized modifier and lubricant make has excellent heat resisting, vicat softening temperature is higher than 80 ℃, overcome because starch or treated starch contain a large amount of wetting ability hydroxyls, the defective that its ageing resistance is relatively poor; The mechanics and the use properties of lactic acid composite material have been improved.Can satisfy of the requirement of fields such as disposable tableware fully to aspects such as thermotolerance and other performances.Be mainly poly--L lactic acid in the polylactic resin of oligomeric-D lactic acid content that the present invention adopts, wherein poly--D lactic acid content is lower than 5wt%.The content of the poly(lactic acid) of D configuration has remarkably influenced to the crystallization behavior of product in poly--L lactic acid, and the content of D configuration lactic acid is low more in poly--L lactic acid, and the crystallization rate of poly(lactic acid) under uniform temp is fast more.And when the D configuration content in poly--L lactic acid surpassed 15%, poly(lactic acid) goes up did not substantially possess crystallizing power.
In above-mentioned heat-resistance polylactic acid composite material, described oligomeric-weight-average molecular weight of the polylactic resin of D lactic acid content is 10-30 ten thousand, glass temperature range is 55-65 ℃, melt flow rate (MFR) is 4-35g/10min at 190 ℃ * 2.16Kg.
In above-mentioned heat-resistance polylactic acid composite material, described nucleator is by silicon-dioxide, 4, one or more compositions in 6-di-tert-butyl-phenyl sodium phosphate, phosphenylic acid zinc, phenyl zinc phosphite, the phenyl phosphinic acid zinc.Wherein be preferably 4,6-di-tert-butyl-phenyl sodium phosphate, phosphenylic acid zinc, one or more compositions in phenyl zinc phosphite, the phenyl phosphinic acid zinc, more preferably phenyl zinc phosphite.The weight part of the nucleator that the present invention adopts is: 0.1-15 part; Preferred weight part is: 1-12 part; Further preferred weight part is: 1-5 part.The adding of nucleator can increase the crystallization rate of poly(lactic acid) greatly, shorten the moulding and the subsequent disposal time of poly(lactic acid), the consumption of nucleator is big more, the crystallization rate of poly(lactic acid) is fast more, but the fragility of material reason is big more, cost is high more, therefore by anatomizing contrast, the consumption of nucleator can be controlled in the rational weight range.
In above-mentioned heat-resistance polylactic acid composite material, described treated starch is made up of in starch acetate, starch laurate, vinyl cyanide starch, carboxymethyl starch, the cross-linking starch one or more, wherein be preferably one or both compositions in starch acetate, the cross-linking starch, more preferably starch acetate.
In above-mentioned heat-resistance polylactic acid composite material, described vegetable fibre is by xylon, bamboo fibers, flax fiber, sisal fibers, one or more compositions in the kenaf, wherein be preferably flax fiber, sisal fibers, one or more compositions in the kenaf, more preferably flax fiber.
The starch that the present invention adopts or the weight part of treated starch are: 1-50 part, and preferred weight part is: 10-40 part, further preferred weight part is: 20-30 part, preferably adopt treated starch.The weight part of the vegetable fibre that adopts is: 1-30 part, preferred weight part is: 5-25 part, further preferred weight part is: 10-20 part.The present invention uses starch, and treated starch and vegetable fibre and poly(lactic acid) are compound, can reduce cost on the one hand, also can increase the performance of some aspect of poly(lactic acid) on the other hand, and for example vegetable fibre can strengthen the toughness of poly(lactic acid).Though the consumption that increases starch or vegetable fibre can improve some performance of matrix material, consumption too much can influence its flowability.
In the compound employing of above-mentioned heat-proof polylactic acid, described silane coupling agent is by γ-(2,3-epoxy third oxygen) propyl trimethoxy silicane, γ-An Jibingjisanyiyangjiguiwan, γ-(the rare acyloxy of methyl-prop) propyl trimethoxy silicane, γ-thiopropyl front three Red copper oxide base silane, vinyltriethoxysilane, one or more compositions in the vinyltrimethoxy silane, wherein be preferably γ-(2,3-epoxy third oxygen) propyl trimethoxy silicane, γ-An Jibingjisanyiyangjiguiwan, in γ-(the rare acyloxy of methyl-prop) propyl trimethoxy silicane one or more are formed Jin Yi Walk and are preferably γ-(2,3-epoxy third oxygen) propyl trimethoxy silicane; Described plasticized modifier is by polycaprolactone, and one or both compositions in polybutene-hexanodioic acid-terephthalic acid, the polyoxyethylene glycol wherein are preferably polycaprolactone and polyoxyethylene glycol, further preferred polyoxyethylene glycol; Described lubricant is made up of in aluminum stearate, the calcium stearate one or both, wherein is preferably aluminum stearate.
Second purpose of the present invention can be implemented by the following technical programs: a kind of preparation method of heat-resistance polylactic acid composite material, and this method may further comprise the steps:
A, batch mixing, granulation: polylactic resin, nucleator, mineral filler, starch or treated starch, vegetable fibre, silane coupling agent, plasticized modifier and the lubricant of choosing oligomeric-D lactic acid content in proportion carry out mix, batching back is stirred to make and is mixed, and is to be extruding pelletization in the forcing machine of 20-100rpm at rotating speed under 150-230 ℃ the condition in temperature then;
B, injection moulding: is 150-250 ℃ with the particle behind the above-mentioned extruding pelletization in temperature, and pressure is injection moulding in injection moulding machine under the condition of 60-160Mpa;
C, thermal treatment: be to obtain the heat-resistance polylactic acid composite material finished product after thermal treatment 0.5-180 minute under 60-150 ℃ the condition with the work in-process of above-mentioned injection moulding in injection moulding machine in temperature.
In the preparation method of above-mentioned heat-resistance polylactic acid composite material, the mineral filler described in the composition of step a is made up of in talcum powder, the lime carbonate one or both; The particle diameter of mineral filler is 1250 orders-12500 orders, and preferable particle size is the 2500-5500 order, and further preferable particle size is the 3000-4000 order.Mineral filler can reduce cost on the one hand, also goods is had the effect of reinforcement on the other hand.
In the preparation method of above-mentioned heat-resistance polylactic acid composite material, as preferably, the forcing machine described in the step a is a twin screw or single screw extruder, and described extrusion temperature is 160-190 ℃, and the rotating speed of described forcing machine is 40-70rpm.
In the preparation method of above-mentioned heat-resistance polylactic acid composite material, as preferably, the injection temperature described in the step b is 170-210 ℃, and injection pressure is 70-110Mpa; Thermal treatment temp described in the step c is 80-120 ℃, and heat treatment time is 10-50 minute.Wherein heat treated temperature is lower than 60 ℃ or when being higher than 150 ℃, poly(lactic acid) all is difficult to crystallization, and heat treatment time is when too short, and poly(lactic acid) is can't crystallization complete, the treatment time is long then do not possess practical application may.
In sum, the present invention has the following advantages:
(1) to adopt poly(lactic acid) be main raw material for biodegradable composite of the present invention, and derives from natural mineral filler, and vegetable fibre and starch carry out melt blending and makes; Poly(lactic acid) can satisfy the requirement of field such as disposable tableware to aspects such as thermotolerance and other performances fully because the crystallization of himself and the promotion crystallization of nucleator make goods have excellent heat resisting, and vicat softening temperature is higher than 80 ℃.
(2) it is reasonably combined that heat-resistance polylactic acid composite material of the present invention adopts multiple composition, under the prerequisite that has guaranteed the matrix material degradability, and the mechanical property excellence, wherein tensile strength can reach 20-70MPa, and Young's modulus can reach 1800-3500MPa.
(3) mineral filler adopted of the present invention, material prices such as starch and vegetable fibre are low, and the content in matrix material can increase the resistance toheat of goods up to 40wt%, greatly reduce the cost of lactic acid composite material.
(4) preparation method of the heat-resisting level of the present invention lactic acid composite material, technical process is simple, and the thermal treatment time is short, and processing characteristics is strong, and cost is low can realize large-scale industrial production.
Embodiment
Below by embodiment, technical scheme of the present invention is described in further detail; But the present invention is not limited to these embodiment.
Embodiment 1
99 parts of vacuum drying low D (poly-D-lactic acid) content poly (l-lactic acid)s, 1 part of nucleator phenyl zinc phosphite, particle diameter is 20 parts of 1250 orders-12500 purpose mineral filler talcum powder, 10 parts of starch acetates, 20 parts of xylons, silane coupling agent γ-(2,3-epoxy third oxygen) propyl trimethoxy silicane is 0.1 part, 1 part of plasticized modifier polycaprolactone, the 0.3 part of even back of melt blending extruding pelletization in twin screw extruder of lubricant stearic acid aluminium, the screw zones temperature is set and is respectively: 190 ℃, 200 ℃, 210 ℃, 220 ℃, 210 ℃, rotating speed is: 50rpm.Injection moulding in injection moulding machine after the granulation, injection temperature is: 210 ℃, injection pressure 100MPa, the residence time is about 40 seconds.The sample that injection moulding is obtained 80 ℃ of constant temperature thermal treatment 180 minutes in baking oven.Its mechanical property and resistance toheat see Table 1.
Embodiment 2
89 parts of vacuum drying low D (poly-D-lactic acid) content poly (l-lactic acid)s, 1 part on nucleator phenyl phosphinic acid zinc, particle diameter is 10 parts of 1250 orders-12500 purpose mineral filler talcum powder, 20 parts of starch laurates, 10 parts of bamboo fiberss, 1 part of silane coupling agent γ-An Bingjisanyiyangjiguiwan, 5 parts of plasticized modifier polybutene-hexanodioic acids-terephthalic acid, the 0.5 part of even back of melt blending extruding pelletization in twin screw extruder of lubricant stearic acid calcium, the screw zones temperature is set and is respectively: 180 ℃, 190 ℃, 200 ℃, 210 ℃, 200 ℃, rotating speed is: 30rpm.Injection moulding in injection moulding machine after the granulation, injection temperature is: 180 ℃, injection pressure 80MPa, the residence time is about 40 seconds.The sample that injection moulding is obtained 80 ℃ of constant temperature 30 minutes in baking oven.Its mechanical property and resistance toheat see Table 1.
Embodiment 3
69 parts of vacuum drying low D (poly-D-lactic acid) content poly (l-lactic acid)s, 1 part on nucleator phosphenylic acid zinc, particle diameter is 40 parts in 1250 orders-12500 a purpose mineral filler lime carbonate, 30 parts of starch, 5 parts of flax fibers, silane coupling agent γ-(2,3-epoxy third oxygen) propyl trimethoxy silicane is 0.1 part, 1 part of plasticized modifier polycaprolactone, the 0.8 part of even back of melt blending extruding pelletization in twin screw extruder of lubricant stearic acid aluminium, the screw zones temperature is set and is respectively: 160 ℃, 170 ℃, 180 ℃, 190 ℃, 180 ℃, rotating speed is: 50rpm.Injection moulding in injection moulding machine after the granulation, injection temperature is: 210 ℃, injection pressure 90MPa, the residence time is about 45 seconds.The sample that injection moulding is obtained 90 ℃ of constant temperature 30 minutes in baking oven.Its mechanical property and resistance toheat see Table 1.
Embodiment 4
58 parts of vacuum drying low D (poly-D-lactic acid) content poly (l-lactic acid)s, 30 parts of starch, 2 parts of nucleator silicon-dioxide, 0.3 part in lubricant stearic acid aluminium, particle diameter is 10 parts of 1250 orders-12500 purpose mineral filler talcum powder, 10 parts of starch acetates, 5 parts of sisal fiberss, 2 parts of silane coupling agent γ-(the rare acyloxy of methyl-prop) propyl trimethoxy silicane, 5 parts of plasticized modifier polybutene-hexanodioic acids-terephthalic acid be the even back extruding pelletizations of melt blending in twin screw extruder, the screw zones temperature is set and is respectively: 170 ℃, 180 ℃, 190 ℃, 200 ℃, 190 ℃, rotating speed is: 70rpm.Injection moulding in injection moulding machine after the granulation, injection temperature is: 190 ℃, injection pressure 80MPa, the residence time is about 40 seconds.The sample that injection moulding is obtained 110 ℃ of constant temperature 15 minutes in baking oven.Its mechanical property and resistance toheat see Table 1.
Embodiment 5
54 parts of vacuum drying low D (poly-D-lactic acid) content poly (l-lactic acid)s, 34 parts of cross-linking starchs, 10 parts of kenaves, nucleator silica 1 part, 0.3 part in lubricant stearic acid aluminium, particle diameter is 40 parts of 1250 orders-12500 purpose mineral filler talcum powder, 3 parts of silane coupling agent γ-thiopropyl front three Red copper oxide base silane, the 10 parts of even back of melt blending extruding pelletizations in twin screw extruder of plasticized modifier polycaprolactone, the screw zones temperature is set and is respectively: 170 ℃, 180 ℃, 190 ℃, 200 ℃, 190 ℃, rotating speed is: 80rpm.Injection moulding in injection moulding machine after the granulation, injection temperature is: 190 ℃, injection pressure 80MPa, the residence time is about 40 seconds.The sample that injection moulding is obtained 110 ℃ of constant temperature 15 minutes in baking oven.Its mechanical property and resistance toheat see Table 1.
Embodiment 6
54 parts of vacuum drying low D (poly-D-lactic acid) content poly (l-lactic acid)s, 34 parts of carboxymethyl starch, particle diameter is 30 parts in 1250 orders-12500 a purpose mineral filler lime carbonate, 10 parts of plasticized modifier polybutene-hexanodioic acids-terephthalic acid, nucleator 4,1 part of 6-di-tert-butyl-phenyl sodium phosphate, 0.3 part in lubricant stearic acid aluminium, the 2 parts of even back of melt blending extruding pelletizations in twin screw extruder of silane coupling agent vinyl triethoxyl silane, the screw zones temperature is set and is respectively: 180 ℃, 190,200 ℃, 210 ℃, 200 ℃, rotating speed is: 50rpm.Injection moulding in injection moulding machine after the granulation, injection temperature is: 200 ℃, injection pressure 70MPa, the residence time is about 50 seconds.The sample that injection moulding is obtained 110 ℃ of constant temperature 15 minutes in baking oven.Its mechanical property and resistance toheat see Table 1.
Embodiment 7
54 parts of vacuum drying low D (poly-D-lactic acid) content poly (l-lactic acid)s, particle diameter is 10 parts of 1250 orders-12500 purpose mineral filler talcum powder, 43 parts of cross-linking starchs, 5 parts of xylons, 2 parts of plasticized modifier polyoxyethylene glycol, nucleator silica 1 part, 0.3 part in lubricant stearic acid aluminium, the silane coupling agent γ-0.05 part of even back of melt blending extruding pelletization in twin screw extruder of (2,3-epoxy third oxygen) propyl trimethoxy silicane, the screw zones temperature is set and is respectively: 160 ℃, 170 ℃, 180 ℃, 190 ℃, 180 ℃, rotating speed is: 50rpm.Injection moulding in injection moulding machine after the granulation, injection temperature is: 180 ℃, injection pressure 80MPa, the residence time is about 40 seconds.The sample that injection moulding is obtained 120 ℃ of constant temperature 10 minutes in baking oven.Its mechanical property and resistance toheat see Table 1.
Embodiment 8
54 parts of vacuum drying low D (poly-D-lactic acid) content poly (l-lactic acid)s, 35 parts of vinyl cyanide starch, particle diameter is 5 parts of 1250 orders-12500 purpose mineral filler talcum powder, 10 parts of bamboo fiberss, 1 part on nucleator phosphenylic acid zinc, 0.3 part in lubricant stearic acid aluminium, 5 parts of silane coupling agent vinyl Trimethoxy silanes, the 1 part of even back of melt blending extruding pelletization in twin screw extruder of plasticized modifier polycaprolactone, the screw zones temperature is set and is respectively: 160 ℃, 170 ℃, 180 ℃, 190 ℃, 180 ℃, rotating speed is: 50rpm.Injection moulding in injection moulding machine after the granulation, injection temperature is: 180 ℃, injection pressure 110MPa, the residence time is about 40 seconds.The sample that injection moulding is obtained 120 ℃ of constant temperature 10 minutes in baking oven.Its mechanical property and resistance toheat see Table 1.
Embodiment 9
74 parts of vacuum drying low D (poly-D-lactic acid) content poly (l-lactic acid)s, particle diameter is 15 parts in 1250 orders-12500 a purpose mineral filler lime carbonate, 40 parts of vinyl cyanide starch, 10 parts of flax fibers, nucleator 4,1 part of 6-di-tert-butyl-phenyl sodium phosphate, 0.3 part in lubricant stearic acid aluminium, silane coupling agent γ-(2,3-epoxy third oxygen) propyl trimethoxy silicane is 0.5 part, plasticized modifier polybutene-hexanodioic acid-10 parts of even the back of melt blending extruding pelletizations in twin screw extruder of terephthalic acid, the screw zones temperature is set and is respectively: 170 ℃, 180 ℃, 190 ℃, 200 ℃, 190 ℃, rotating speed is: 50rpm.Injection moulding in injection moulding machine after the granulation, injection temperature is: 190 ℃, injection pressure 90MPa, the residence time is about 40 seconds.The sample that injection moulding is obtained 120 ℃ of constant temperature 10 minutes in baking oven.Its mechanical property and resistance toheat see Table 1.
Embodiment 10
54 parts of vacuum drying low D (poly-D-lactic acid) content poly (l-lactic acid)s, particle diameter is 1 part of 1250 orders-12500 a purpose mineral filler talcum powder, 26 parts of starch laurates, 15 parts of sisal fiberss, nucleator 4,5 parts of 6-di-tert-butyl-phenyl sodium phosphates, 0.3 part in lubricant stearic acid aluminium, 0.2 part of silane coupling agent γ-An Bingjisanyiyangjiguiwan, the 0.1 part of even back of melt blending extruding pelletization in twin screw extruder of plasticized modifier polyoxyethylene glycol, the screw zones temperature is set and is respectively: 160 ℃, 170 ℃, 180 ℃, 190 ℃, 180 ℃, rotating speed is: 50rpm.Injection moulding in injection moulding machine after the granulation, injection temperature is: 180 ℃, injection pressure 90MPa, the residence time is about 40 seconds.The sample that injection moulding is obtained 120 ℃ of constant temperature 10 minutes in baking oven.Its mechanical property and resistance toheat see Table 1.
Embodiment 11
54 parts of vacuum drying low D (poly-D-lactic acid) content poly (l-lactic acid)s, particle diameter is 5 parts in 1250 orders-12500 a purpose mineral filler lime carbonate, 30 parts of starch acetates, 15 parts of kenaves, nucleator silica 1 part, 0.3 part in lubricant stearic acid aluminium, 0.5 part of silane coupling agent γ-(the rare acyloxy of methyl-prop) propyl trimethoxy silicane, the 1 part of even back of melt blending extruding pelletization in twin screw extruder of plasticized modifier polycaprolactone, the screw zones temperature is set and is respectively: 160 ℃, 170 ℃, 180 ℃, 190 ℃, 180 ℃, rotating speed is: 50rpm.Injection moulding in injection moulding machine after the granulation, injection temperature is: 180 ℃, injection pressure 80MPa, the residence time is about 40 seconds.The sample that injection moulding is obtained 120 ℃ of constant temperature 10 minutes in baking oven.Its mechanical property and resistance toheat see Table 1.
Table 1: the performance of the polylactic acid composition that embodiment 1-11 is prepared
As can be seen from Table 1: the lactic acid composite material of the present invention preparation has excellent heat resisting, and vicat softening temperature is higher than 80 ℃, can satisfy the requirement of field such as disposable tableware to aspects such as thermotolerance and other performances fully; Under this external prerequisite that guarantees the lactic acid composite material degradability, the mechanical property excellence, wherein tensile strength can reach 20-70MPa, and Young's modulus can reach 1800-3500MPa.
Specific embodiment described in the present invention only is that the present invention's spirit is illustrated.The technician of the technical field of the invention can make various modifications or replenishes or adopt similar mode to substitute described specific embodiment, but can't depart from spirit of the present invention or surmount the defined scope of appended claims.
Although the present invention has been made detailed explanation and has quoted some specific exampless as proof, to those skilled in the art, only otherwise leave that the spirit and scope of the present invention can be done various variations or correction is obvious.
Claims (10)
1, a kind of heat-resistance polylactic acid composite material, this matrix material comprises the composition of following weight part:
The polylactic resin of oligomeric-D lactic acid content: 50-99 part; Nucleator: 0.1-15 part; Mineral filler: 1-50 part; Starch or treated starch: 1-50 part; Vegetable fibre: 1-30 part; Silane coupling agent: 0.01-5 part; Plasticized modifier: 0.1-10 part; Lubricant: 0.05-1.0 part; Wherein said oligomeric-polylactic resin of D lactic acid content in poly--D lactic acid content be lower than 5wt%.
2, heat-resistance polylactic acid composite material according to claim 1, it is characterized in that: described oligomeric-weight-average molecular weight of the polylactic resin of D lactic acid content is 10-30 ten thousand, glass temperature range is 55-65 ℃, and melt flow rate (MFR) is 4-35g/10min at 190 ℃ * 2.16Kg.
3, heat-resistance polylactic acid composite material according to claim 1 and 2, it is characterized in that: described nucleator is by silicon-dioxide, 4, one or more compositions in 6-di-tert-butyl-phenyl sodium phosphate, phosphenylic acid zinc, phenyl zinc phosphite, the phenyl phosphinic acid zinc.
4, heat-resistance polylactic acid composite material according to claim 1 and 2 is characterized in that: described treated starch is made up of in starch acetate, starch laurate, vinyl cyanide starch, carboxymethyl starch, the cross-linking starch one or more.
5, heat-resistance polylactic acid composite material according to claim 1 and 2 is characterized in that: described vegetable fibre is by xylon, bamboo fibers, flax fiber, sisal fibers, one or more compositions in the kenaf.
6, heat-resistance polylactic acid composite material according to claim 1 and 2, it is characterized in that: described silane coupling agent is by γ-(2,3-epoxy third oxygen) propyl trimethoxy silicane, γ-An Jibingjisanyiyangjiguiwan, γ-(the rare acyloxy of methyl-prop) propyl trimethoxy silicane, γ-thiopropyl front three Red copper oxide base silane, vinyltriethoxysilane, one or more compositions in the vinyltrimethoxy silane.
7, a kind of preparation method of heat-resistance polylactic acid composite material, this method may further comprise the steps:
A, batch mixing, granulation: polylactic resin, nucleator, mineral filler, starch or treated starch, vegetable fibre, silane coupling agent, plasticized modifier and the lubricant of choosing oligomeric-D lactic acid content in proportion carry out mix, batching back is stirred to make and is mixed, and is to be extruding pelletization in the forcing machine of 20-100rpm at rotating speed under 150-230 ℃ the condition in temperature then;
B, injection moulding: is 150-250 ℃ with the particle behind the above-mentioned extruding pelletization in temperature, and pressure is injection moulding in injection moulding machine under the condition of 60-160Mpa;
C, thermal treatment: be to obtain the heat-resistance polylactic acid composite material finished product after thermal treatment 0.5-180 minute under 60-150 ℃ the condition with the work in-process of above-mentioned injection moulding in injection moulding machine in temperature.
8, the preparation method of heat-resistance polylactic acid composite material according to claim 7 is characterized in that: the mineral filler described in the composition of step a is made up of in talcum powder, the lime carbonate one or both; The particle diameter of mineral filler is 1250 orders-12500 orders.
9, according to the preparation method of claim 7 or 8 described heat-resistance polylactic acid composite materials, it is characterized in that; Forcing machine described in the step a is a twin screw or single screw extruder, and described extrusion temperature is 160-190 ℃, and the rotating speed of described forcing machine is 40-70rpm.
10, the preparation method of heat-resistance polylactic acid composite material according to claim 7 is characterized in that: the injection temperature described in the step b is 170-210 ℃, and injection pressure is 70-110Mpa; Thermal treatment temp described in the step c is 80-120 ℃, and heat treatment time is 10-50 minute.
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