CN104693706B - A kind of heat-resisting enhancing shock resistance modified polylactic acid material and preparation method thereof - Google Patents
A kind of heat-resisting enhancing shock resistance modified polylactic acid material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of modified polylactic acid material, is made up of the component comprising following parts by weight：100 parts of PLA, 20~30 parts of modified calcium carbonate, 10~20 parts of plasticizer, 1.0~2.0 parts of ultra-violet absorber, 0.5~1.0 part of antioxidant, 8~15 parts of anti-impact modifier, 4~8 parts of processing aid.Preparation method is as follows：By 100 parts of PLAs, 8~15 parts of anti-impact modifiers and 4~8 parts of processing aids in high-speed mixer and mixing 3~5 minutes, then 20~30 parts of modified calcium carbonates, 10~20 parts of plasticizer, 1.0~2.0 parts of ultra-violet absorbers are added to high mixer with 0.5~1.0 part of antioxidant and mixed 5~8 minutes, the wherein mixing temperature of high mixer is 80~90 DEG C；Said mixture is cooled to less than 50 DEG C, is added to by main charge door in double screw extruder, extrusion temperature is 180~220 DEG C, and modified polylactic acid material is obtained after extrusion, water cooled, pelletizing, then dries, pack.The modified polylactic acid material of the present invention improves mechanical strength, and improves heat resistance, greatly improves the shock resistance of PLA.
Description
Technical field
The present invention relates to field of high polymer material modification and processing technique field, and in particular to a kind of heat-resisting enhancing is anti-
Impact modified polylactic acid material and preparation method thereof.
Background technology
With the development of industrial production and science and technology, plastic products are essential, base in people's daily life
In our population base, China is plastics consumption big country in the whole world.But conventional plastic product is to bring people convenient
Also pollute environment simultaneously, general plastics needed the upper century-old even more long time could degradable, result in it is serious " in vain
Color pollutes ".Meanwhile traditional plastic raw materials derive from the non-renewable resources such as oil, with the exhaustion tradition of fossil resources
Plastics industry also receive threat.Therefore, the environment-friendly biodegradable polymer of Devoting Major Efforts To Developing substitutes petroleum base modeling
Expect product, it has also become the focus of current research exploitation.
In the biodegradable plastics developed at present, PLA is a kind of bio-based modeling that can be degradable
Material.Generated because PLA can be fermented by renewable resources such as cornstarch, there is excellent biodegradability again, make
Its in petrochemical industry high polymer material is substituted by more and more extensive concern, available for biomedicine, packaging, clothes, agriculture and forestry,
The fields such as catering trade.Although PLA has excellent degradability and biocompatibility, the crisp poor toughness of PLA matter, lack
Flexible and elasticity, easily flexural deformation, heat resisting temperature is excessively low, strongly limit its development and use range, so needing
PLA is modified.
Traditional polylactic acid modified method is that PLA and other high polymers either are added into inorganic filler, by simple
It is kneaded, processing technology can only improve some performances of PLA, it is difficult to improve the shock resistance of PLA simultaneously without specific requirement
Property, heat-resisting and mechanical performance etc., therefore common PLA is difficult the application requirement for meeting various industries, such as automobile, household electrical appliances, building
Industry, there are some higher requirements to plastic material, in the mechanical performance of material, or even to reach or close to engineering plastics
Level, and in the engineering process of poly-lactic acid material, it is most difficult to solve the problems, such as be that there is higher shock resistance in guarantee material
Higher heat resistance is also needed to while toughness, excellent mechanical stretching performance, therefore is also needed to constantly to PLA
Material is modified to improve combination property.
The content of the invention
The defects of in order to overcome prior art, it is an object of the invention to provide one kind to have heat-resisting enhancing shock resistance PLA
It is material modified.
It is a further object of the present invention to provide a kind of preparation method of above-mentioned heat-resisting enhancing shock resistance modified polylactic acid material.
To achieve these goals, technical scheme is as follows：
The invention provides a kind of heat-resisting enhancing shock resistance modified polylactic acid material, by the component system for including following parts by weight
Into：
It is 4 that the PLA, which includes mass ratio,:1~4:2 PLLA and dextrorotation PLA.
The modified calcium carbonate is made up of the component of following parts by weight：100 parts of calcium carbonate, 3~5 parts of accelerator, stearic acid 5
~8 parts, 10~20 parts of calcium oxide.
It is 1 that the accelerator, which includes mass ratio,:1 carboxylated polyethylene wax and polyacrylamide.
The plasticizer is selected from hexamethylene -1,2- dicarboxyl dinonyl, diphenyl phthalate or the fourth of SA two
One or more in ester.
The ultra-violet absorber is selected from 4 benzoyloxy 2,2,6,6 tetramethyl piperidine, phosphorous acid three（1,2,2,6,
6- pentamethvls）One or more in ester or salicylic acid -4- tert-butyl group phenyl esters.
The antioxidant be selected from thio-2 acid octadecyl ester, [β-（3,5 di-t-butyl 4- hydroxy-phenies）Propionic acid] Ji Wusi
One or more in alcohol ester or dilauryl thiodipropionate.
The anti-impact modifier is selected from maleic anhydride grafted ethene/propylene copolymer, maleic anhydride grafted ethene-the third
One kind in alkene-diene terpolymer, the copolymer of styrene and butadiene or ethene and acrylonitrile copolymer or it is a kind of with
On.
One or more of the processing aid in stearic acid, zinc stearate, calcium stearate or erucyl amide.
It is including following present invention also offers a kind of preparation method of above-mentioned heat-resisting enhancing shock resistance modified polylactic acid material
Step：
By 100 parts of PLAs, 8~15 parts of anti-impact modifiers and 4~8 parts of processing aids in 3~5 points of high-speed mixer and mixing
Clock, then by 20~30 parts of modified calcium carbonates, 10~20 parts of plasticizer, 1.0~2.0 parts of ultra-violet absorbers and 0.5~1.0 part
Antioxidant is added to high mixer and mixed 5~8 minutes, and the wherein mixing temperature of high mixer is 80~90 DEG C；Said mixture is cold
But to less than 50 DEG C, it is added to by main charge door in double screw extruder, extrusion temperature is 180~220 DEG C, is gathered after extrusion
Lactic modified material, water cooled, pelletizing, then dry, pack.
The PLA is using mass ratio as 4 by PLLA and dextrorotation PLA:1~4:2 ratio blending composition
PLA matrix, crushed 500 mesh sieves, obtain polylactic acid powder.
The preparation method of the modified calcium carbonate comprises the following steps：First 100 parts of calcium carbonate are added in high-speed mixer,
In 100~110 DEG C of dry 30min, 5~8 parts of stearic acid, 3~5 parts of accelerator and 10~20 parts of calcium oxide are added, it is mixed at a high speed
Modified calcium carbonate is obtained after closing 10~15min, it is 1 that the accelerator, which includes mass ratio,:1 carboxylated polyethylene wax and polyacrylamide
Amine.
The screw slenderness ratio of the double screw extruder is 30:1, screw speed is 80~120r/min.
Compared with prior art, beneficial effects of the present invention are as follows：
The heat-resisting enhancing shock resistance modified polylactic acid material of the present invention improves common pole using addition modified calcium carbonate
Interaction between property inorganic filler and nonpolar PLA matrix, makes inorganic carbonate calcium uniformly divide in organic PLA matrix
Dissipate, greatly improve the heat resistance and mechanical strength of poly-lactic acid material.The anti-impact modifier of addition improves PLA
Impact flexibility, and reduce the intensity of material without the crystal structure for destroying PLA in process；Ultraviolet radiation absorption
The efficient combination of agent and antioxidant adds, and enhances the weather resistance of PLA, extends the service life of polylactic acid article.Cause
And the present invention is not only obviously improved the heat resistance of poly-lactic acid material, toughness and mechanical strength are also drastically increased,
The field that combination property requires higher is can be widely used in, and preparation is simple, is adapted to industrialized production.
Embodiment
With reference to embodiment, the present invention is further detailed explanation.
GB is used in following examples（National standard）The properties of material are determined, unless otherwise instructed, the number of component is equal
For parts by weight.
Embodiment 1
（1）Carbonic acid Calcium preconditioning：First by 100 parts of addition high-speed mixers of calcium carbonate, in 100~110 DEG C of dryings
30min, 6 parts of stearic acid, 5 parts of accelerator, 15 parts of calcium oxide are added, mixed at high speed 10min, obtains modified calcium carbonate；Promote
It is 1 that agent, which includes mass ratio,:1 carboxylated polyethylene wax and polyacrylamide.
（2）75 parts of PLA matrixes formed with the 25 parts of blendings of dextrorotation PLA of PLLA be crushed into 500 mesh sieves,
Obtain polylactic acid powder；
（3）By 100 parts of polylactic acid powder, maleic anhydride grafted ethene -10 parts of propylenediene terpolymer and stearic acid
4 parts of zinc in high-speed mixer and mixing 3 minutes, then by 20 parts of modified calcium carbonate, 15 parts of hexamethylene -1,2- dicarboxyl dinonyl,
Phosphorous acid three（1,2,2,6,6- pentamethvls）1.0 parts of 1.2 parts of ester and dilauryl thiodipropionate is added to high mixer and mixed
Close 5 minutes, wherein the mixing temperature of high mixer is at 90 DEG C；
（4）After mixing, said mixture is cooled to less than 50 DEG C, double screw extruder is added to by main charge door, is squeezed
It is 190~210 DEG C to go out temperature, screw slenderness ratio 30:1, screw speed 100r/min, polylactic acid modified material is obtained after extrusion
Material, water cooled, pelletizing, then dry, pack.
Modified polylactic acid material is molded into sample, its correlated performance is tested, the results are shown in Table 1.
Embodiment 2
（1）Modified calcium carbonate pre-processes：First by 100 parts of addition high-speed mixers of calcium carbonate, in 100~110 DEG C of dryings
30min, 5 parts of stearic acid, 3 parts of accelerator, 10 parts of calcium oxide are added, mixed at high speed 12min, obtains modified calcium carbonate；Promote
It is 1 that agent, which includes mass ratio,:1 carboxylated polyethylene wax and polyacrylamide.
（2）80 parts of PLA matrixes formed with the 20 parts of blendings of dextrorotation PLA of PLLA be crushed into 500 mesh sieves,
Obtain polylactic acid powder；
（3）By 6 parts of 8 parts of the copolymer and erucyl amide of 100 parts of polylactic acid powder, styrene and butadiene in high mixer
Mixing 4 minutes, then by 22 parts of modified calcium carbonate, 12 parts of SA dibutyl ester, 1.0 parts of salicylic acid -4- tert-butyl groups phenyl ester with [β -
（3,5 di-t-butyl 4- hydroxy-phenies）Propionic acid] 0.8 part of pentaerythritol ester is added to high mixer and mixes 6 minutes, wherein high mixer
Mixing temperature at 80 DEG C；
（4）After mixing, said mixture is cooled to less than 50 DEG C, double screw extruder is added to by main charge door, is squeezed
It is 180~200 DEG C to go out temperature, screw slenderness ratio 30:1, screw speed 120r/min, polylactic acid modified material is obtained after extrusion
Material, water cooled, pelletizing, then dry, pack.
Modified polylactic acid material is molded into sample, its correlated performance is tested, the results are shown in Table 1.
Embodiment 3
（1）Modified calcium carbonate pre-processes：First by 100 parts of addition high-speed mixers of calcium carbonate, in 100~110 DEG C of dryings
30min, 8 parts of stearic acid, 4 parts of accelerator, 15 parts of calcium oxide are added, mixed at high speed 15min, obtains modified calcium carbonate；Promote
It is 1 that agent, which includes mass ratio,:1 carboxylated polyethylene wax and polyacrylamide.
（2）67 parts of PLA matrixes formed with the 33 parts of blendings of dextrorotation PLA of PLLA be crushed into 500 mesh sieves,
Obtain polylactic acid powder；
（3）15 parts of 100 parts of polylactic acid powder, ethene and acrylonitrile copolymer and 8 parts of calcium stearate are mixed in high mixer
Close 5 minutes, then by 25 parts of modified calcium carbonate, 10 parts of hexamethylene -1,2- dicarboxyl dinonyl, phosphorous acid three（1,2,2,6,
6- pentamethvls）0.5 part of 1.5 parts of ester and dilauryl thiodipropionate is added to high mixer and mixes 8 minutes, wherein high mixer
Mixing temperature at 80 DEG C；
（4）After mixing, said mixture is cooled to less than 50 DEG C, double screw extruder is added to by main charge door, is squeezed
It is 190~210 DEG C to go out temperature, screw slenderness ratio 30:1, screw speed 100r/min, polylactic acid modified material is obtained after extrusion
Material, water cooled, pelletizing, then dry, pack.
Modified polylactic acid material is molded into sample, its correlated performance is tested, the results are shown in Table 1.
Embodiment 4
（1）Modified calcium carbonate pre-processes：First by 100 parts of addition high-speed mixers of calcium carbonate, in 100~110 DEG C of dryings
30min, 6 parts of stearic acid, 5 parts of accelerator, 15 parts of calcium oxide are added, mixed at high speed 15min, obtains modified calcium carbonate；Promote
It is 1 that agent, which includes mass ratio,:1 carboxylated polyethylene wax and polyacrylamide.
（2）72 parts of PLA matrixes formed with the 28 parts of blendings of dextrorotation PLA of PLLA be crushed into 500 mesh sieves,
Obtain polylactic acid powder；
（3）By 100 parts of polylactic acid powder, maleic anhydride grafted ethene -10 parts of propylenediene terpolymer and stearic acid
6 parts of zinc in high-speed mixer and mixing 4 minutes, then by 30 parts of modified calcium carbonate, 20 parts of hexamethylene -1,2- dicarboxyl dinonyl,
2.0 parts of salicylic acid -4- tert-butyl groups phenyl ester with [β -（3,5 di-t-butyl 4- hydroxy-phenies）Propionic acid] 0.8 part of addition of pentaerythritol ester
Mixed 8 minutes to high mixer, wherein the mixing temperature of high mixer is at 85 DEG C；
（4）After mixing, said mixture is cooled to less than 50 DEG C, double screw extruder is added to by main charge door, is squeezed
It is 200~220 DEG C to go out temperature, screw slenderness ratio 30:1, screw speed 80r/min, polylactic acid modified material is obtained after extrusion
Material, water cooled, pelletizing, then dry, pack.
Modified polylactic acid material is molded into sample, its correlated performance is tested, the results are shown in Table 1.
Embodiment 5
（1）Modified calcium carbonate pre-processes：First by 100 parts of addition high-speed mixers of calcium carbonate, in 100~110 DEG C of dryings
30min, 8 parts of stearic acid, 4 parts of accelerator, 20 parts of calcium oxide are added, mixed at high speed 12min, obtains modified calcium carbonate；Promote
It is 1 that agent, which includes mass ratio,:1 carboxylated polyethylene wax and polyacrylamide.
（2）70 parts of PLA matrixes formed with the 30 parts of blendings of dextrorotation PLA of PLLA be crushed into 500 mesh sieves,
Obtain polylactic acid powder；
（3）By 2 parts of the copolymer 1 of 100 parts of polylactic acid powder, styrene and butadiene with 8 parts of calcium stearate in high mixer
Middle mixing 5 minutes, then by 28 parts of modified calcium carbonate, 18 parts of SA dibutyl ester, phosphorous acid three（1,2,2,6,6- pentamethyl piperazines
Pyridine）0.6 part of 1.5 parts of ester and dilauryl thiodipropionate is added to high mixer and mixes 5 minutes, the wherein mixing temperature of high mixer
At 90 DEG C；
（4）After mixing, said mixture is cooled to less than 50 DEG C, double screw extruder is added to by main charge door, is squeezed
It is 190~210 DEG C to go out temperature, screw slenderness ratio 30:1, screw speed 90r/min, polylactic acid modified material is obtained after extrusion
Material, water cooled, pelletizing, then dry, pack.
Modified polylactic acid material is molded into sample, its correlated performance is tested, the results are shown in Table 1.
Comparative example 1
The comparative example does not add anti-impact modifier with being in place of the difference of embodiment 3 in the preparation of mixed material.
Remaining component, reaction temperature, time and step all same.The properties for the modified polylactic acid material that the comparative example obtains are shown in Table
1。
Comparative example 2
The comparative example does not add modified calcium carbonate with being in place of the difference of embodiment 4 in the preparation of mixed material.Its
Remaining component, reaction temperature, time and step all same.The properties for the modified polylactic acid material that the comparative example obtains are shown in Table 1.
Table 1
Can be seen that by each item data in table 1, embodiment 4 and 5 keep the good toughness of modified polylactic acid material,
Mechanics mechanical strength and higher vicat softening temperature, combination property reach optimal.Pass through comparative example 1 and pair of embodiment 3
Than its notch impact strength of the modified polylactic acid material of anti-impact modifier is not added in discovery and elongation declines to a great extent；Pass through
The contrast of comparative example 2 and embodiment 4, discovery are not added the modified polylactic acid material of modified calcium carbonate its tensile strength and significantly declined
Subtract, vicat softening temperature also decreases.
Embodiment 6
（1）Modified calcium carbonate pre-processes：First by 100 parts of addition high-speed mixers of calcium carbonate, in 100~110 DEG C of dryings
30min, 7 parts of stearic acid, 4 parts of accelerator, 18 parts of calcium oxide are added, mixed at high speed 12min, obtains modified calcium carbonate；Promote
It is 1 that agent, which includes mass ratio,:1 carboxylated polyethylene wax and polyacrylamide.
（2）70 parts of PLA matrixes formed with the 30 parts of blendings of dextrorotation PLA of PLLA be crushed into 500 mesh sieves,
Obtain polylactic acid powder；
（3）100 parts of polylactic acid powder, 13 parts of maleic anhydride grafted ethene/propylene copolymer is mixed in height with 7 parts of stearic acid
Mix 5 minutes in machine, then by 26 parts of modified calcium carbonate, 16 parts of diphenyl phthalate, 4- benzoyloxys -2,2,6,6-
0.7 part of 1.8 parts of tetramethyl piperidine and thio-2 acid octadecyl ester is added to high mixer and mixes 5 minutes, the wherein mixing of high mixer
Temperature is at 90 DEG C；
（4）After mixing, said mixture is cooled to less than 50 DEG C, double screw extruder is added to by main charge door, is squeezed
It is 190~210 DEG C to go out temperature, screw slenderness ratio 30:1, screw speed 90r/min, polylactic acid modified material is obtained after extrusion
Material, water cooled, pelletizing, then dry, pack.
The above-mentioned description to embodiment is understood that for ease of those skilled in the art and using this hair
It is bright.Person skilled in the art obviously easily can make various modifications to these embodiments, and described herein
General Principle is applied in other embodiment without by performing creative labour.Therefore, the invention is not restricted to implementation here
Example, for those skilled in the art according to the announcement of the present invention, not departing from improvement that scope made and modification all should be
Within protection scope of the present invention.
Claims (6)
- A kind of 1. heat-resisting enhancing shock resistance modified polylactic acid material, it is characterised in that：It is made up of the component of following parts by weight：It is 4 that the PLA, which includes mass ratio,:1~4:2 PLLA and dextrorotation PLA；The modified calcium carbonate is made up of the component of following parts by weight：100 parts of calcium carbonate, 3~5 parts of accelerator, stearic acid 5~8 Part, 10~20 parts of calcium oxide；It is 1 that the accelerator, which includes mass ratio,:1 carboxylated polyethylene wax and polyacrylamide；The ultra-violet absorber is selected from the 4 benzoyloxy 2,2,6,6 tetramethyl piperidine, (1,2,2,6,6- five of phosphorous acid three Methyl piperidine) one or more of ester or salicylic acid -4- tert-butyl group phenyl esters；The antioxidant is selected from one or more of thio-2 acid octadecyl ester or dilauryl thiodipropionate；The anti-impact modifier is the copolymer of ethene and acrylonitrile；The preparation method of described heat-resisting enhancing shock resistance modified polylactic acid material comprises the following steps：100 parts of PLAs, 8~15 parts of anti-impact modifiers are mixed 3~5 points with 4~8 parts of processing aids in high-speed mixer Clock, then by 20~30 parts of modified calcium carbonates, 10~20 parts of plasticizer, 1.0~2.0 parts of ultra-violet absorbers and 0.5~1.0 part Antioxidant is added to high-speed mixer and mixed 5~8 minutes, and the wherein mixing temperature of high-speed mixer is 80~90 DEG C, is mixed Compound；The mixture is cooled to less than 50 DEG C, is added to by main charge door in double screw extruder, extrusion temperature 180 ~220 DEG C, heat-resisting enhancing shock resistance modified polylactic acid material is obtained after extrusion, water cooled, pelletizing, then dries, pack；The preparation method of the modified calcium carbonate comprises the following steps：First 100 parts of calcium carbonate are added in high-speed mixer, 100~110 DEG C of dry 30min, add 5~8 parts of stearic acid, 3~5 parts of accelerator and 10~20 parts of calcium oxide, mixed at high speed Modified calcium carbonate is obtained after 10~15min, it is 1 that the accelerator, which includes mass ratio,:1 carboxylated polyethylene wax and polyacrylamide Amine.
- 2. heat-resisting enhancing shock resistance modified polylactic acid material according to claim 1, it is characterised in that：The plasticizer choosing From one or more of hexamethylene -1,2- dicarboxyl dinonyl, diphenyl phthalate or dibutyl sebacate.
- 3. heat-resisting enhancing shock resistance modified polylactic acid material according to claim 1, it is characterised in that：The processing aid Selected from one or more of stearic acid, zinc stearate, calcium stearate or erucyl amide.
- 4. a kind of preparation method of heat-resisting enhancing shock resistance modified polylactic acid material according to claim any one of 1-3, It is characterized in that：Comprise the following steps：100 parts of PLAs, 8~15 parts of anti-impact modifiers are mixed 3~5 points with 4~8 parts of processing aids in high-speed mixer Clock, then by 20~30 parts of modified calcium carbonates, 10~20 parts of plasticizer, 1.0~2.0 parts of ultra-violet absorbers and 0.5~1.0 part Antioxidant is added to high-speed mixer and mixed 5~8 minutes, and the wherein mixing temperature of high-speed mixer is 80~90 DEG C, is mixed Compound；The mixture is cooled to less than 50 DEG C, is added to by main charge door in double screw extruder, extrusion temperature 180 ~220 DEG C, heat-resisting enhancing shock resistance modified polylactic acid material is obtained after extrusion, water cooled, pelletizing, then dries, pack；The preparation method of the modified calcium carbonate comprises the following steps：First 100 parts of calcium carbonate are added in high-speed mixer, 100~110 DEG C of dry 30min, add 5~8 parts of stearic acid, 3~5 parts of accelerator and 10~20 parts of calcium oxide, mixed at high speed Modified calcium carbonate is obtained after 10~15min, it is 1 that the accelerator, which includes mass ratio,:1 carboxylated polyethylene wax and polyacrylamide Amine.
- 5. the preparation method of heat-resisting enhancing shock resistance modified polylactic acid material according to claim 4, it is characterised in that：Institute It is using mass ratio as 4 by PLLA and dextrorotation PLA to state PLA:1~4:The PLA base of 2 ratio blending composition Body, 500 mesh sieves are crushed, obtain PLA.
- 6. the preparation method of heat-resisting enhancing shock resistance modified polylactic acid material according to claim 4, it is characterised in that：Institute The screw slenderness ratio for stating double screw extruder is 30:1, screw speed is 80~120r/min.
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| CN105907060A (en) * | 2016-05-06 | 2016-08-31 | 金宝丽科技（苏州）有限公司 | Heat-resistant PLA (Polylactic Acid) anti-electrostatic composite material and preparation method thereof |
| CN106280335B (en) * | 2016-08-25 | 2018-06-29 | 中国电子科技集团公司第四十六研究所 | The 3D printing poly-lactic acid material and its dyeing of a kind of easy coloring |
| CN108164940A (en) * | 2016-12-07 | 2018-06-15 | 黑龙江鑫达企业集团有限公司 | A kind of preparation method of shock resistance poly-lactic acid material |
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Effective date of registration: 20190621 Address after: 200000 No. 275 Dongye Road, Dongjing Town, Songjiang District, Shanghai Patentee after: Rich packaging technology (Shanghai) Co. Ltd. Address before: 239000 Chuzhou Economic and Technological Development Zone, Chuzhou City, Anhui Province Patentee before: Chuzhou Gemeite Technology Co.,Ltd. |