CN108384173B - A kind of high molecular weight height founds the preparation method of structure lactic acid composite material - Google Patents

A kind of high molecular weight height founds the preparation method of structure lactic acid composite material Download PDF

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CN108384173B
CN108384173B CN201810318395.8A CN201810318395A CN108384173B CN 108384173 B CN108384173 B CN 108384173B CN 201810318395 A CN201810318395 A CN 201810318395A CN 108384173 B CN108384173 B CN 108384173B
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杨其
赵中国
吴萍萍
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Sichuan University
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    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/08—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/02—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polycarbonates or saturated polyesters

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Abstract

The present invention relates to technical field of polymer materials, are related to a kind of preparation method of vertical structure lactic acid composite material of high molecular weight height.The present invention provides a kind of preparation method of vertical structure lactic acid composite material of high molecular weight height, specifically: modified Poly L-lactic acid is obtained with poly- L-lactic acid in 100~200 DEG C of 1~6min of melt blending；The ratio of modified Poly L-lactic acid and poly- L-lactic acid are as follows: 90~70:10~30；Modified Poly L-lactic acid is made using linear Poly L-lactic acid, peroxidating diisopropyl ammonia, pentaerythritol triacrylate and tetraethylthiuram disulfide as raw material by melt blending.Extrusion molding process can be used in method of the invention, and time 5min is blended, is conducive to industrialized production；And the method for the present invention is realized just has been completely formed Stereocomplex crystalline substance in the case that Poly L-lactic acid and poly- L-lactic acid ratio are 70:30, that is, further reduced the dosage of poly- L-lactic acid.

Description

A kind of high molecular weight height founds the preparation method of structure lactic acid composite material
Technical field
The present invention relates to technical field of polymer materials, and in particular to a kind of vertical structure lactic acid composite material of high molecular weight height Preparation method.
Background technique
Polylactic acid (PLA) is a kind of important synthesis high molecular material of fully biodegradable, there is good bio-compatible Property, preferable mechanical strength and hot formability are nontoxic, nonirritant, thus are considered as that most promising biodegradable is high Molecular material.Being for polylactic acid biggest advantage can be from carbohydrate be decomposed into inside of human body, as metabolism is arranged It is external out.Plastics result in the focus that the problem of environmental pollution has become world's extensive concern, this sustainable development at present The Biodegradable polymer material of exhibition has become the research and development direction paid close attention to jointly in the world.Although polylactic acid has very More advantages, however some performances of polylactic acid itself are there is still a need for improving, with lower melt strength and crystal property, Therefore it is not able to satisfy the processing of requirement to polylactic acid performance, such as blown film, wire drawing etc. at present.Its heat resistance is poor, only about There are 58 DEG C or so.These disadvantages are serious to limit the application range of polylactic acid, exists to further expand polylactic acid Commercial and industrial application value, it is necessary for being modified to it.
It is largely poly- using poly- l-lactic acid (PLA) and poly- dextrorotation to improve its heat resistance and crystal property Lactic acid (PDLA) is blended to improve its heat resistance, while can improve its crystal property to a certain extent.PLA/ PDLA blending is capable of forming one kind, and special crystal structure is called Stereocomplex crystalline substance, with special crystal structure, fusing point ratio Respective polymer is higher by 50 DEG C or so, and the heat resistance of polylactic acid, Mechanics of Machinery can be improved in this special Stereocomplex crystalline substance Performance, anti-hydrolytic performance etc..
However the formation of this Stereocomplex crystalline substance receives the influence of PLA Yu PDLA component, the different of component ratio can shape It is brilliant at the Stereocomplex of different content.Vertical structure can be completely formed in the case where ratio is 1:1 (weight ratio) under normal circumstances Composite crystal.The main machining method for currently forming Stereocomplex crystalline substance is solution casting method and melt blended method, research work Show that solution casting method is more advantageous to form stereoscopic composite compared with melt blending method, and on the molecular weight of obtained polylactic acid Limit is higher, and this method is easy to operate, but post-processing is complex, and higher cost, yield is lower, is not easy to large-scale industry Production.
In view of the foregoing drawbacks, the Chinese patent application of Publication No. CN102532837A discloses a kind of high-molecular-weight poly cream The preparation method of sour stereoscopic composite, method particularly includes: by poly- l-lactic acid and poly- dextrorotation polylactic acid by weight 80:20~ 20:80 is mixed, and mixed material is mixed at 140~210 DEG C in torque rheometer, that is, completes high-molecular-weight poly The preparation of lactic acid stereoscopic composite；But in the documents only when Poly L-lactic acid and poly- L-lactic acid ratio be 50~ When 60:40~50, it can just be completely formed Stereocomplex crystalline substance；It and is to be blended in torque rheometer in documents, altogether Doing time is 15min, i.e. the method for documents is only applicable to laboratory applications, and it is longer that the time is blended；In view of the poly- right side It is more expensive to revolve lactic acid price, although documents realize Poly L-lactic acid: just obtaining in the case where poly- L-lactic acid=60:40 Full Stereocomplex is brilliant, but if the dosage of poly- L-lactic acid can be further decreased, then entire production cost is just lower；In addition, The formation of this Stereocomplex crystalline substance, can directly form powdered product in PDLA high-content, be unfavorable for mechanical property and each side The raising of face performance.
Summary of the invention
In view of the foregoing drawbacks, the present invention provides the preparation method of a kind of high vertical structure, poly-lactic acid in high molecular weight composite material, this Extrusion molding process can be used in the method for invention, and time 5min is blended, is more conducive to industrialized production；And the present invention Method is realized just has been completely formed Stereocomplex crystalline substance in the case that Poly L-lactic acid and poly- L-lactic acid ratio are 70:30, The dosage that further reduced poly- L-lactic acid further reduced entire production cost.
Technical solution of the present invention:
The present invention provides the preparation method of a kind of high vertical structure, poly-lactic acid in high molecular weight composite material, the preparation methods Are as follows: modified Poly L-lactic acid and poly- L-lactic acid are obtained into high molecular weight height in 100~200 DEG C of 1~6min of melt blending and found structure Lactic acid composite material；Wherein, the ratio of modified Poly L-lactic acid and poly- L-lactic acid are as follows: modified poly- l-lactic acid 90~70 Parts by weight, poly- 10~30 parts by weight of dextrorotation polylactic acid；
Also, the modified Poly L-lactic acid is prepared using following methods:
By linear Poly L-lactic acid, peroxidating diisopropyl ammonia, pentaerythritol triacrylate and tetraethyl Ji Qiulan Nurse obtains modified Poly L-lactic acid in 180~200 DEG C of 3~5min of melt blending；The ratio of each raw material are as follows: linear Poly L-lactic acid (PLA) 100 parts by weight, 0.6 parts by weight of peroxidating diisopropyl ammonia (DCP), pentaerythritol triacrylate (PETA) 0.1~0.4 Parts by weight, 0.05~0.12 parts by weight of tetraethylthiuram disulfide (TETDS).
Further, in the above method, modified Poly L-lactic acid and poly- L-lactic acid melt altogether using screw extruder Mixed, screw speed is 20~80rpm (preferably 50rpm).
Further, before modified poly- l-lactic acid is mixed with poly- dextrorotation polylactic acid, using vacuum drying, drying time be for 8~48h, makes its equal water content lower than 250ppm by 60~80 DEG C of drying temperature.
Preferably, in the preparation method of the modified Poly L-lactic acid, each raw material proportioning are as follows: 100 weight of polylactic acid (PLA) Part, 0.6 parts by weight of peroxidating diisopropyl ammonia (DCP), 0.4 parts by weight of pentaerythritol triacrylate (PETA), tetraethyl 0.12 parts by weight of base thiuram (TETDS).
Further, in the above method, in the preparation method of the modified Poly L-lactic acid, melt blending uses Screw Extrusion Machine, screw speed are 30~150rpm (preferably 50rpm).
Beneficial effects of the present invention:
1) using the preparation method of the high Stereocomplex crystalline substance of high molecular weight of the present invention, molecular weight can be made to be higher than 105The Stereocomplex that the even whole contents of high-content are formed in the poly- l-lactic acid of g/mol is brilliant.
It 2), can be in poly- l-lactic acid and the poly- right side using the preparation method of high molecular weight Stereocomplex crystalline substance of the present invention Rotation polylactic acid is non-equal than (70:30), and the time is only the crystal that all Stereocomplexes are formed under conditions of 5 minutes, is compared In current research, ratio, the limitation of long duration such as breach.
3) present invention can use extrusion molding, be conducive to industrialized production.
4) the present invention provides a kind of new preparation high molecular weight, the preparation method of high vertical structure lactic acid composite material, energy Blocky poly-lactic acid material is accessed, the mechanical property and crystal property of composite material can be further significantly improved.
Detailed description of the invention
Fig. 1 is polydactyl acid point in unmodified linear Poly L-lactic acid used in the embodiment of the present invention and embodiment 2~4 The curve of son amount distribution.Polylactic acid molecule amount it can be seen from the molecular weight distribution curve of Fig. 1 after modification has occurred Significant change, weight average molecular weight is by 1.6 × 105G/mol has been increased to 3.9 × 105g/mol.And molecular weight distribution obviously becomes Width, this explanation is by having obtained long-chain branch polylactic acid after extrusion reaction of the present invention.
Fig. 2 is the DSC melting curve of the embodiment of the present invention 1~4 and comparative example 1~2.By the data of Fig. 2 and table 1 it is found that Under conditions of the weight ratios such as the poly- l-lactic acid of long-chain branch and poly- dextrorotation polylactic acid be non-, using method of the invention, it is possible to making The standby Stereocomplex crystalline substance compound with high-content, and the fusing point of obtained Stereocomplex crystalline substance material is up to 223.9 DEG C；It is special Under conditions of the weight ratio for not being the poly- l-lactic acid of long-chain branch and poly- dextrorotation polylactic acid is 70:30, using preparation of the invention Method can be completely formed Stereocomplex crystalline substance product；And it is found by comparative example 1~2, in the content of poly- dextrorotation polylactic acid When being 30%, the stereoscopic composite of higher amount can be obtained by extrusion reaction.
Specific embodiment:
A specific embodiment of the invention is further described below with reference to embodiment, is not therefore limited the present invention System is among the embodiment described range.
Embodiment 1
The preparation method of lactic acid composite material includes the following steps:
1) by polylactic acid, dry 48h, temperature are 80 DEG C in vacuum drying oven；
2) 90 parts by weight of poly- l-lactic acid being dried and poly- 10 parts by weight of dextrorotation polylactic acid are blended uniformly, so Blending granulation is carried out with extruder afterwards, temperature of the temperature of extruder from mouth mold to barrel is 200,200,200,200, 200,200,200,200,200,160,100 DEG C, screw speed 50rpm, the time from barrel to mouth mold is 6min；
3) resulting sample uses DSC to be heated to 240 DEG C, isothermal 5min from 40 DEG C with 10 DEG C/min, then with 10 DEG C/ Min cools to 40 DEG C from 240 DEG C, and the result is shown in table 1 and Fig. 2.
Embodiment 2
The preparation method that high molecular weight height founds structure lactic acid composite material includes the following steps:
1) by polylactic acid, dry 48h, temperature are 80 DEG C in vacuum drying oven；
2) by 0.6 parts by weight of 100 parts by weight of poly- l-lactic acid and peroxidating diisopropyl ammonia being dried, Ji Wusi 0.4 parts by weight of alcohol triacrylate, 0.12 parts by weight of tetraethylthiuram disulfide be blended uniformly, then with extruder into Row, which is blended, to be granulated, and the poly- l-lactic acid of modified long-chain branch is obtained；Temperature of the temperature of extruder from mouth mold to barrel is 200, 200,200,200,200,200,200,200,200,160,100 DEG C, screw speed 50rpm, the time from barrel to mouth mold For 6min；
3) poly- 90 parts by weight of l-lactic acid of long-chain branch and poly- 10 parts by weight of dextrorotation polylactic acid are blended uniformly, then with reaction Extruder carries out blending granulation, and temperature of the temperature of extruder from mouth mold to barrel is 200,200,200,200,200,200, 200,200,200,160,100 DEG C, screw speed 50rpm, the time from barrel to mouth mold is 6min；
4) resulting sample uses DSC to be heated to 240 DEG C, isothermal 5min from 40 DEG C with 10 DEG C/min, then with 10 DEG C/ Min cools to 40 DEG C from 240 DEG C, and the result is shown in table 1 and Fig. 2.
Embodiment 3
The preparation method that high molecular weight height founds structure lactic acid composite material includes the following steps:
1) by polylactic acid, dry 48h, temperature are 80 degree in vacuum drying oven；
2) by 0.6 parts by weight of 100 parts by weight of poly- l-lactic acid and peroxidating diisopropyl ammonia being dried, Ji Wusi 0.4 parts by weight of alcohol triacrylate, 0.12 parts by weight of tetraethylthiuram disulfide be blended uniformly, then with extruder into Row, which is blended, to be granulated, and the poly- l-lactic acid of modified long-chain branch is obtained；Temperature of the temperature of extruder from mouth mold to barrel is 200, 200,200,200,200,200,200,200,200,160,100 DEG C, screw speed 50rpm, the time from barrel to mouth mold For 6min；
3) poly- 80 parts by weight of l-lactic acid of long-chain branch and poly- 20 parts by weight of dextrorotation polylactic acid are blended uniformly, then with reaction Extruder carries out blending granulation, and temperature of the temperature of extruder from mouth mold to barrel is 200,200,200,200,200,200, 200,200,200,160,100 DEG C, screw speed 50rpm, the time from barrel to mouth mold is 6min；
4) resulting sample uses DSC to be heated to 240 DEG C, isothermal 5min from 40 DEG C with 10 DEG C/min, then with 10 DEG C/ Min cools to 40 DEG C from 240 DEG C, and the result is shown in table 1 and Fig. 2.
Embodiment 4
The preparation method that high molecular weight height founds structure lactic acid composite material includes the following steps:
1) by polylactic acid, dry 48h, temperature are 80 degree in vacuum drying oven；
2) by 0.6 parts by weight of 100 parts by weight of poly- l-lactic acid and peroxidating diisopropyl ammonia being dried, Ji Wusi 0.4 parts by weight of alcohol triacrylate, 0.12 parts by weight of tetraethylthiuram disulfide be blended uniformly, then with extruder into Row, which is blended, to be granulated, and the poly- l-lactic acid of modified long-chain branch is obtained；Temperature of the temperature of extruder from mouth mold to barrel is 200, 200,200,200,200,200,200,200,200,160,100 DEG C, screw speed 50rpm, the time from barrel to mouth mold For 6min；
3) poly- 70 parts by weight of l-lactic acid of long-chain branch and poly- 30 parts by weight of dextrorotation polylactic acid are blended uniformly, then with reaction Extruder carries out blending granulation, and temperature of the temperature of extruder from mouth mold to barrel is 200,200,200,200,200,200, 200,200,200,160,100 DEG C, screw speed 50rpm, the time from barrel to mouth mold is 6min；
4) resulting sample uses DSC to be heated to 240 DEG C, isothermal 5min from 40 DEG C with 10 DEG C/min, then with 10 DEG C/ Min cools to 40 DEG C from 240 DEG C, and the result is shown in table 1 and Fig. 2.
Comparative example 1
The preparation method of lactic acid composite material includes the following steps:
1) by polylactic acid, dry 48h, temperature are 80 DEG C in vacuum drying oven；
2) by 0.6 parts by weight of 100 parts by weight of poly- l-lactic acid and peroxidating diisopropyl ammonia being dried, Ji Wusi 0.4 parts by weight of alcohol triacrylate, 0.12 parts by weight of tetraethylthiuram disulfide be blended uniformly, then with extruder into Row, which is blended, to be granulated, and the poly- l-lactic acid of modified long-chain branch is obtained；Temperature of the temperature of extruder from mouth mold to barrel is 200, 200,200,200,200,200,200,200,200,160,100 DEG C, screw speed 50rpm, the time from barrel to mouth mold For 6min；
3) poly- 70 parts by weight of l-lactic acid of long-chain branch and poly- 30 parts by weight of dextrorotation polylactic acid are blended uniformly, then use two Chloromethanes solution, churned mechanically method are completely dissolved mixture, and experimental temperature is 25 DEG C, and mixing time is for 24 hours.
4) it is finally put into ancient customs baking oven, solvent is volatilized, and product is dried in vacuo for 24 hours, drying temperature 60 ℃.Resulting sample uses DSC to be heated to 240 DEG C, isothermal 5min from 40 DEG C with 10 DEG C/min, then with 10 DEG C/min from 240 DEG C 40 DEG C are cooled to, the result is shown in table 1 and Fig. 2.
Comparative example 2
The preparation method of lactic acid composite material includes the following steps:
1) by polylactic acid, dry 48h, temperature are 80 DEG C in vacuum drying oven；
2) 70 parts by weight of poly- l-lactic acid that will be dried, poly- 30 parts by weight of dextrorotation polylactic acid and peroxidating two are different Third ammonia, 0.6 parts by weight, 0.4 parts by weight of pentaerythritol triacrylate, 0.12 parts by weight of tetraethylthiuram disulfide are blended equal It is even, blending granulation then is carried out with extruder, obtains the poly- l-lactic acid of modified long-chain branch；The temperature of extruder is from mouth The temperature of mould to barrel is 200,200,200,200,200,200,200,200,200,160,100 DEG C, and screw speed is 50rpm, the time from barrel to mouth mold are 6min；
3) resulting sample uses DSC to be heated to 240 DEG C, isothermal 5min from 40 DEG C with 10 DEG C/min, then with 10 DEG C/ Min cools to 40 DEG C from 240 DEG C, and the result is shown in table 1 and Fig. 2.
The resulting parameter of DSC melting curve in 1 Examples 1 to 4 of table and comparative example 1~2
Note: TccFor the temperature at cold crystallization peak, Δ HccFor cold crystallization heat content, TmFor melting peak temperature, Δ HmFor melting enthalpy, xcFor total crystallinity.1 represents homopolymer crystal, and 2 represent Stereocomplex Jingjing body.

Claims (11)

1. the preparation method that high molecular weight height founds structure lactic acid composite material, which is characterized in that the preparation method is that: it will be modified Poly L-lactic acid and poly- L-lactic acid in 100~200 DEG C of 1~6min of melt blending obtain high molecular weight height, and to found structure polylactic acid compound Material；Wherein, the ratio of modified Poly L-lactic acid and poly- L-lactic acid are as follows: modified 90~70 parts by weight of Poly L-lactic acid gather the right side Revolve 10~30 parts by weight of lactic acid；
Also, the modified Poly L-lactic acid is prepared using following methods:
By linear Poly L-lactic acid, cumyl peroxide, pentaerythritol triacrylate and tetraethylthiuram disulfide in 180~200 DEG C of 3~5min of melt blending obtain modified Poly L-lactic acid；The ratio of each raw material are as follows: linear Poly L-lactic acid 100 Parts by weight, 0.6 parts by weight of cumyl peroxide, 0.1~0.4 parts by weight of pentaerythritol triacrylate, tetraethyl base 0.05~0.12 parts by weight of thiuram.
2. the preparation method that high molecular weight height according to claim 1 founds structure lactic acid composite material, which is characterized in that change Property Poly L-lactic acid and poly- L-lactic acid using screw extruder carry out melt blending, screw speed be 20~80rpm.
3. high molecular weight height according to claim 1 or 2 founds the preparation method of structure lactic acid composite material, feature exists In making its water content be below 250ppm using vacuum drying before modified Poly L-lactic acid is mixed with poly- L-lactic acid.
4. the preparation method that high molecular weight height according to claim 3 founds structure lactic acid composite material, which is characterized in that dry The dry time be 8~48h, 60~80 DEG C of drying temperature.
5. high molecular weight height according to claim 1 or 2 founds the preparation method of structure lactic acid composite material, feature exists In, in the preparation method of the modified Poly L-lactic acid, each raw material proportioning are as follows: 100 parts by weight of linear Poly L-lactic acid, peroxidating 0.6 parts by weight of diisopropylbenzene (DIPB), 0.4 parts by weight of pentaerythritol triacrylate, 0.12 parts by weight of tetraethylthiuram disulfide.
6. the preparation method that high molecular weight height according to claim 3 founds structure lactic acid composite material, which is characterized in that institute In the preparation method for stating modified Poly L-lactic acid, each raw material proportioning are as follows: 100 parts by weight of linear Poly L-lactic acid, peroxidating two are different 0.6 parts by weight of propyl benzene, 0.4 parts by weight of pentaerythritol triacrylate, 0.12 parts by weight of tetraethylthiuram disulfide.
7. the preparation method that high molecular weight height according to claim 4 founds structure lactic acid composite material, which is characterized in that institute In the preparation method for stating modified Poly L-lactic acid, each raw material proportioning are as follows: 100 parts by weight of linear Poly L-lactic acid, peroxidating two are different 0.6 parts by weight of propyl benzene, 0.4 parts by weight of pentaerythritol triacrylate, 0.12 parts by weight of tetraethylthiuram disulfide.
8. high molecular weight height according to claim 1 or 2 founds the preparation method of structure lactic acid composite material, feature exists In, in the preparation method of the modified Poly L-lactic acid, melt blending use screw extruder, screw speed be 30~ 150rpm。
9. the preparation method that high molecular weight height according to claim 3 founds structure lactic acid composite material, which is characterized in that institute In the preparation method for stating modified Poly L-lactic acid, melt blending uses screw extruder, and screw speed is 30~150rpm.
10. the preparation method that high molecular weight height according to claim 4 founds structure lactic acid composite material, which is characterized in that In the preparation method of the modified Poly L-lactic acid, melt blending uses screw extruder, and screw speed is 30~150rpm.
11. the preparation method that high molecular weight height according to claim 5 founds structure lactic acid composite material, which is characterized in that In the preparation method of the modified Poly L-lactic acid, melt blending uses screw extruder, and screw speed is 30~150rpm.
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