CN109721977B - High-impact PLA/PBAT composite material and preparation method thereof - Google Patents
High-impact PLA/PBAT composite material and preparation method thereof Download PDFInfo
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- CN109721977B CN109721977B CN201811568603.6A CN201811568603A CN109721977B CN 109721977 B CN109721977 B CN 109721977B CN 201811568603 A CN201811568603 A CN 201811568603A CN 109721977 B CN109721977 B CN 109721977B
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Abstract
The invention discloses a high-impact PLA/PBAT composite material and a preparation method thereof, wherein the high-impact PLA/PBAT composite material is prepared by blending polylactic acid and chemically grafted and modified polybutylene adipate-terephthalate, wherein the content of the chemically grafted and modified polybutylene adipate-terephthalate is more than 20%, the compatibility between the polybutylene adipate-terephthalate and the polybutylene terephthalate can be improved by carrying out chemical grafting modification on the polybutylene adipate-terephthalate, the toughness of the PLA/PBAT composite material is improved, other additives are not needed in the preparation method, and the preparation method has the advantages of simple preparation process, low preparation cost and the like.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a high-impact PLA/PBAT composite material and a preparation method thereof.
Background
With the increasing severity of environmental pollution and energy consumption, environmental friendly polymer materials have attracted extensive attention in academia and industry. Polylactic Acid (PLA) as a thermoplastic aliphatic polyester derived from renewable resources has good biodegradability and biocompatibility, and also has very excellent mechanical strength and processability, so that the PLA has a wide application prospect in the fields of general plastics and biomedical materials.
However, the toughness of PLA is very poor, which greatly limits the range of applications. Currently, in order to improve the toughness of PLA, technicians mainly blend Poly (butylene-co-terephthalate) (PBAT) with PLA, and the PBAT is used to improve the toughness of PLA. For example: chinese patent 201210289135.5 discloses a fully biodegradable PLA/PBAT composite film and a preparation method thereof, the scheme is that when PLA and PBAT are blended, a bisoxazoline chain extender and an isocyanate chain extender with the functionality of more than or equal to 2 are added as compatilizers, so that the interfacial compatibility of PLA/PBAT is improved, the tensile toughness of the PLA/PBAT composite film is improved, and the film can be manufactured; chinese patent 201110404499.9 discloses a fully biodegradable polylactic acid composition and a preparation method thereof, in the scheme, a bisoxazoline chain extender is added into a PLA and PBAT blending system to improve the interface compatibility of two components in the blending system, thereby improving the elongation at break of the composition. Therefore, although the tensile toughness of the PLA is improved by adding the PBAT, the PLA/PBAT composite material prepared by the existing method still has weak impact toughness, so that the PLA/PBAT composite material cannot be used as a structural material, and the application range is small.
Therefore, how to develop a novel PLA/PBAT composite material to improve impact toughness is a problem to be solved.
Disclosure of Invention
In view of the above, the invention discloses a high impact-resistant PLA/PBAT composite material and a preparation method thereof, so as to at least solve the problems that the PLA/PBAT composite material prepared in the prior art cannot be used as a structural material due to low impact toughness, has a small application range and the like.
The invention provides a high-impact PLA/PBAT composite material, which is prepared from polylactic acid and polybutylene adipate-terephthalate after chemical grafting modification, wherein the content of the polybutylene adipate-terephthalate after chemical grafting modification is more than 20%.
Preferably, the content of the polybutylene adipate-terephthalate after the chemical grafting modification is more than 30%.
More preferably, the polybutylene adipate-terephthalate after chemical grafting modification is: the modified polybutylene adipate-terephthalate is obtained by chemically grafting and modifying the polybutylene adipate-terephthalate by glycidyl methacrylate, N-vinyl pyrrolidone and dicumyl peroxide.
Further preferably, the adhesive composition comprises 100 parts by weight of polybutylene adipate-terephthalate, 2-3 parts by weight of glycidyl methacrylate, 2-3 parts by weight of N-vinyl pyrrolidone and 0.2-0.3 part by weight of dicumyl peroxide.
Further preferably, the preparation method of the polybutylene adipate-terephthalate after chemical grafting modification specifically comprises the following steps:
the preparation method comprises the following steps of carrying out melt blending on polybutylene adipate-terephthalate, glycidyl methacrylate, N-vinyl pyrrolidone and dicumyl peroxide to obtain the polybutylene adipate-terephthalate after chemical grafting modification.
The invention also provides a preparation method of the high impact PLA/PBAT composite material, which comprises the following steps:
1) carrying out melt blending on polybutylene adipate-terephthalate, glycidyl methacrylate, N-vinyl pyrrolidone and dicumyl peroxide to obtain chemically grafted and modified polybutylene adipate-terephthalate for later use;
2) and (2) carrying out melt blending on polylactic acid and the polybutylene adipate-terephthalate subjected to chemical grafting modification in the step 1) to obtain the composite material.
The high-impact PLA/PBAT composite material provided by the invention is obtained by melt blending polylactic acid and polybutylene adipate-terephthalate subjected to chemical grafting modification, and the composite material can improve the compatibility between the polylactic acid and the polybutylene terephthalate by carrying out chemical grafting modification on the polybutylene adipate-terephthalate and realizes the improvement of the toughness of the PLA/PBAT composite material.
The method for preparing the high-impact PLA/PBAT composite material provided by the invention has the advantages that in the whole preparation link, only before the polylactic acid is blended with the poly (butylene adipate-terephthalate), the poly (butylene adipate-terephthalate) is subjected to chemical grafting modification in advance, other additives are not needed, the preparation process is simple, the preparation cost is low, and the like.
It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the disclosure.
Detailed Description
The invention is further illustrated by the following specific embodiments, which are not intended to limit the scope of the invention.
In view of the weak impact toughness of the PLA/PBAT composite material prepared in the prior art, the PLA/PBAT composite material cannot be used as a structural material, and has the problems of small application range and the like. The embodiment provides a novel PLA/PBAT composite material which has high impact resistance and can be used as a structural material, such as an automobile bumper and the like.
The PLA/PBAT composite material is prepared from polylactic acid and polybutylene adipate-terephthalate after chemical grafting modification, wherein the content of the polybutylene adipate-terephthalate after chemical grafting modification is more than 20%, and preferably, the content of the polybutylene adipate-terephthalate after chemical grafting modification is more than 30%.
Wherein, the poly adipic acid-butylene terephthalate after chemical grafting modification is as follows: the modified polybutylene adipate-terephthalate is obtained by chemically grafting and modifying the polybutylene adipate-terephthalate by glycidyl methacrylate, N-vinyl pyrrolidone and dicumyl peroxide.
Specifically, the chemical grafting modification process of the polybutylene adipate-terephthalate comprises the following steps:
respectively weighing 100 parts of poly (butylene adipate-terephthalate), 2-3 parts of glycidyl methacrylate, 2-3 parts of N-vinyl pyrrolidone and 0.2-0.3 part of dicumyl peroxide by weight, putting the components into an internal mixer for melt blending, wherein the rotating speed is 80rpm, the mixing temperature is 180 ℃, and mixing for 5min to obtain the poly (butylene adipate-terephthalate) after chemical grafting modification.
The specific preparation method of the high impact PLA/PBAT composite material comprises the following steps:
1) carrying out chemical grafting modification on polybutylene adipate-terephthalate:
weighing polybutylene adipate-terephthalate, glycidyl methacrylate, N-vinyl pyrrolidone and dicumyl peroxide according to a proportion, putting the weighed materials into an internal mixer for melt blending, wherein the rotating speed is 80rpm, the mixing temperature is 180 ℃, and after mixing for 5min, the polybutylene adipate-terephthalate after chemical grafting modification is obtained for later use;
2) blending polylactic acid and polybutylene adipate-terephthalate:
and (2) weighing polylactic acid and the chemical grafting modified polybutylene adipate-terephthalate according to the proportion, putting the polylactic acid and the chemical grafting modified polybutylene terephthalate into an internal mixer for melt blending, wherein the rotating speed is 80rpm, the mixing temperature is 180 ℃, and mixing for 5min to obtain the composite material.
The overall reaction mechanism of the preparation method is as follows:
the melt blending mode of the chemical grafting modification of the polybutylene adipate-terephthalate and the melt blending mode of the polylactic acid and the polybutylene adipate-terephthalate are not limited to the listed modes, and any suitable melt processing technology can be adopted, such as blending by a double-screw extruder, as long as the same toughening effect can be achieved.
The invention is further illustrated by the following specific examples.
Example 1
Mixing poly (butylene adipate-terephthalate) (PBAT)/Glycidyl Methacrylate (GMA)/N-vinyl pyrrolidone (NVP)/dicumyl peroxide (DCP) according to the mass ratio of 100/3/0/0.3, 100/1/1/0.1, 100/2/2/0.2 and 100/3/3/0.3 respectively, sequentially naming the products as poly (butylene adipate-terephthalate) No. 0 (A0-PBAT), poly (butylene adipate-terephthalate) No. 1 (A1-PBAT), poly (butylene adipate-terephthalate) No. 2 (A2-PBAT) and poly (butylene adipate-terephthalate) No. 3 (A3-PBAT), respectively putting the products into an internal mixer for melt blending, wherein the rotation speed is 80rpm, the mixing temperature is 180 ℃, and the mixing time is 5 min.
And the unmodified polybutylene adipate-terephthalate was named pure polybutylene adipate-terephthalate (pure PBAT).
Example 2
And (2) putting the modified polybutylene adipate-terephthalate No. 2 (A2-PBAT) and polylactic acid into an internal mixer according to the proportion of 30/70(w/w) for melt blending, wherein the rotating speed is 80rpm, the mixing temperature is 180 ℃, and the mixing time is 5min, so as to prepare the PLA/PBAT composite material.
The prepared PLA/PBAT composite material is subjected to a notch impact test at the temperature of 23 ℃, and the notch impact test strength is 49.06 KJ/M2.
Example 3
And (2) putting the modified poly (butylene adipate-terephthalate) No. 3 (A3-PBAT) and the polylactic acid into an internal mixer according to the proportion of 30/70(w/w) for melt blending, wherein the rotating speed is 80rpm, the mixing temperature is 180 ℃, and the mixing time is 5min, so as to prepare the PLA/PBAT composite material.
The prepared PLA/PBAT composite material is subjected to notch impact test at the temperature of 23 ℃, and the notch impact test strength is 54.49 KJ/M2.
Example 4
And (2) putting the modified polybutylene adipate-terephthalate No. 2 (A2-PBAT) and polylactic acid into an internal mixer according to the proportion of 20/80(w/w) for melt blending, wherein the rotating speed is 80rpm, the mixing temperature is 180 ℃, and the mixing time is 5min, so as to prepare the PLA/PBAT composite material.
And (3) carrying out a notch impact test on the prepared PLA/PBAT composite material at the temperature of 23 ℃, wherein the notch impact test strength is 25.14 KJ/M2.
Example 5
And (2) putting the modified poly (butylene adipate-terephthalate) No. 3 (A3-PBAT) and the polylactic acid into an internal mixer according to the proportion of 20/80(w/w) for melt blending, wherein the rotating speed is 80rpm, the mixing temperature is 180 ℃, and the mixing time is 5min, so as to prepare the PLA/PBAT composite material.
And (3) carrying out a notch impact test on the prepared PLA/PBAT composite material at the temperature of 23 ℃, wherein the notch impact test strength is 25.42 KJ/M2.
Example 6
And (2) putting the modified poly (butylene adipate-terephthalate) No. 1 (A1-PBAT) and the polylactic acid into an internal mixer according to the proportion of 30/70(w/w) for melt blending, wherein the rotating speed is 80rpm, the mixing temperature is 180 ℃, and the mixing time is 5min, so as to prepare the PLA/PBAT composite material.
And (3) carrying out a notched impact test on the prepared PLA/PBAT composite material at the temperature of 23 ℃, wherein the notched impact test strength is 20.13 KJ/M2.
Example 7
And (2) putting the modified poly (butylene adipate-terephthalate) No. 0 (A0-PBAT) and the polylactic acid into an internal mixer according to the proportion of 30/70(w/w) for melt blending, wherein the rotating speed is 80rpm, the mixing temperature is 180 ℃, and the mixing time is 5min, so as to prepare the PLA/PBAT composite material.
And (3) carrying out a notch impact test on the prepared PLA/PBAT composite material at the temperature of 23 ℃, wherein the notch impact test strength is 13.64 KJ/M2.
Example 8
The unmodified pure poly (butylene adipate-terephthalate) (pure PBAT) and the polylactic acid are put into an internal mixer according to the proportion of 30/70(w/w) for melt blending, wherein the rotating speed is 80rpm, the mixing temperature is 180 ℃, and the mixing time is 5min, so that the PLA/PBAT composite material is prepared.
And (3) carrying out notch impact test on the prepared PLA/PBAT composite material at the temperature of 23 ℃, wherein the notch impact test strength is 9.6 KJ/M2.
Example 9
PLA is used as a contrast, and the PLA/PBAT composite materials prepared according to different proportions are respectively subjected to notch impact strength and elongation at break tests at the temperature of 23 ℃, and the specific results are shown in the following table:
performance display meter
| Sample proportioning | Notched impact strength KJ/M2 | Elongation at Break (%) |
| PLA | 4 | 7.9 |
| PLA: pure PBAT 70:30 | 9.6 | 14.3 |
| PLA:A2-PBAT＝70:30 | 49.1 | 211.1 |
| PLA:A3-PBAT＝70:30 | 54.5 | 215.1 |
As can be seen from the table, the notched impact strength of the PLA/PBAT composite material made by the present invention is ten times that of the pure PLA material and three times that of the PLA/PBAT composite material, and the elongation at break is 27 times that of the pure PLA material and 11 times that of the PLA/PBAT composite material.
Other embodiments of the invention will be apparent to those skilled in the art from consideration of the specification and practice of the invention disclosed herein. This application is intended to cover any variations, uses, or adaptations of the invention following, in general, the principles of the invention and including such departures from the present disclosure as come within known or customary practice within the art to which the invention pertains. It is intended that the specification and examples be considered as exemplary only, with a true scope and spirit of the invention being indicated by the following claims.
It is to be understood that the present invention is not limited to what has been described above, and that various modifications and changes may be made without departing from the scope thereof. The scope of the invention is limited only by the appended claims.
Claims (5)
1. A high impact PLA/PBAT composite material is characterized by being prepared from polylactic acid and polybutylene adipate-terephthalate which is chemically grafted and modified, wherein the polybutylene adipate-terephthalate which is chemically grafted and modified is as follows: the modified polybutylene adipate-terephthalate is obtained by chemically grafting and modifying polybutylene adipate-terephthalate by using glycidyl methacrylate, N-vinyl pyrrolidone and dicumyl peroxide, wherein the content of the polybutylene adipate-terephthalate after the chemical grafting modification is more than 20%.
2. The high impact PLA/PBAT composite of claim 1 wherein the content of the chemically graft modified polybutylene adipate terephthalate is 30% or more.
3. The high impact PLA/PBAT composite material according to claim 2, characterized in that 100 parts by weight of polybutylene adipate-terephthalate, 2 to 3 parts by weight of glycidyl methacrylate, 2 to 3 parts by weight of N-vinylpyrrolidone and 0.2 to 0.3 parts by weight of dicumyl peroxide.
4. The high impact PLA/PBAT composite material according to claim 3, wherein the preparation method of the polybutylene adipate-terephthalate after chemical grafting modification is specifically as follows:
the preparation method comprises the following steps of carrying out melt blending on polybutylene adipate-terephthalate, glycidyl methacrylate, N-vinyl pyrrolidone and dicumyl peroxide to obtain the polybutylene adipate-terephthalate after chemical grafting modification.
5. A method for preparing the high impact PLA/PBAT composite of claim 1, comprising the steps of:
1) carrying out melt blending on polybutylene adipate-terephthalate, glycidyl methacrylate, N-vinyl pyrrolidone and dicumyl peroxide to obtain chemically grafted and modified polybutylene adipate-terephthalate for later use;
2) and (2) carrying out melt blending on polylactic acid and the polybutylene adipate-terephthalate subjected to chemical grafting modification in the step 1) to obtain the composite material.
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| CN110358275A (en) * | 2019-08-21 | 2019-10-22 | 安徽恒鑫环保新材料有限公司 | A kind of PLA composite material and preparation method |
| CN114316538A (en) * | 2022-03-16 | 2022-04-12 | 中化学科学技术研究有限公司 | Modified PBAT-PLA material and preparation method thereof |
| CN115260717B (en) * | 2022-05-17 | 2023-12-19 | 万华化学（宁波）有限公司 | Polylactic acid foam material, preparation method thereof and method for preparing polylactic acid foam beads |
| CN115073900A (en) * | 2022-06-09 | 2022-09-20 | 合肥工业大学 | High-strength high-toughness long-acting antibacterial polylactic acid blending composite material, and preparation method and application thereof |
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