CN109575196B - Polylactic acid chain extender, preparation method thereof and modified polylactic acid - Google Patents
Polylactic acid chain extender, preparation method thereof and modified polylactic acid Download PDFInfo
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- CN109575196B CN109575196B CN201811517424.XA CN201811517424A CN109575196B CN 109575196 B CN109575196 B CN 109575196B CN 201811517424 A CN201811517424 A CN 201811517424A CN 109575196 B CN109575196 B CN 109575196B
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- polylactic acid
- chain extender
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- glycidyl methacrylate
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- 239000004626 polylactic acid Substances 0.000 title claims abstract description 66
- 229920000747 poly(lactic acid) Polymers 0.000 title claims abstract description 65
- 239000004970 Chain extender Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical group CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 9
- 238000010894 electron beam technology Methods 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 4
- 231100000987 absorbed dose Toxicity 0.000 claims description 2
- 239000003963 antioxidant agent Substances 0.000 claims 1
- 230000003078 antioxidant effect Effects 0.000 claims 1
- 239000008187 granular material Substances 0.000 claims 1
- 239000006185 dispersion Substances 0.000 abstract description 7
- 239000011159 matrix material Substances 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 3
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical group CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 7
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 6
- 230000005855 radiation Effects 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000003381 stabilizer Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- ZJNLYGOUHDJHMG-UHFFFAOYSA-N 1-n,4-n-bis(5-methylhexan-2-yl)benzene-1,4-diamine Chemical compound CC(C)CCC(C)NC1=CC=C(NC(C)CCC(C)C)C=C1 ZJNLYGOUHDJHMG-UHFFFAOYSA-N 0.000 description 1
- WPMYUUITDBHVQZ-UHFFFAOYSA-N 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoic acid Chemical compound CC(C)(C)C1=CC(CCC(O)=O)=CC(C(C)(C)C)=C1O WPMYUUITDBHVQZ-UHFFFAOYSA-N 0.000 description 1
- QDGXHPFKUOZLBV-UHFFFAOYSA-N C(C(=C)C)(=O)OCC1CO1.C(=CC1=CC=CC=C1)C=CC(=O)O Chemical compound C(C(=C)C)(=O)OCC1CO1.C(=CC1=CC=CC=C1)C=CC(=O)O QDGXHPFKUOZLBV-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- OUBMGJOQLXMSNT-UHFFFAOYSA-N N-isopropyl-N'-phenyl-p-phenylenediamine Chemical compound C1=CC(NC(C)C)=CC=C1NC1=CC=CC=C1 OUBMGJOQLXMSNT-UHFFFAOYSA-N 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 229920013724 bio-based polymer Polymers 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- KEZPMZSDLBJCHH-UHFFFAOYSA-N n-(4-anilinophenyl)-4-methylbenzenesulfonamide Chemical compound C1=CC(C)=CC=C1S(=O)(=O)NC(C=C1)=CC=C1NC1=CC=CC=C1 KEZPMZSDLBJCHH-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- -1 pentaerythritol ester Chemical class 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000005014 poly(hydroxyalkanoate) Substances 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000903 polyhydroxyalkanoate Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- AJHKJOCIGPIJFZ-UHFFFAOYSA-N tris(2,6-ditert-butylphenyl) phosphite Chemical compound CC(C)(C)C1=CC=CC(C(C)(C)C)=C1OP(OC=1C(=CC=CC=1C(C)(C)C)C(C)(C)C)OC1=C(C(C)(C)C)C=CC=C1C(C)(C)C AJHKJOCIGPIJFZ-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
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- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Graft Or Block Polymers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polyesters Or Polycarbonates (AREA)
- Biological Depolymerization Polymers (AREA)
Abstract
The invention relates to a polylactic acid chain extender, a preparation method thereof and modified polylactic acid. The structural formula of the polylactic acid chain extender is shown as
The polylactic acid chain extender has the technical effects of high dispersion speed and uniform dispersion in a polylactic acid matrix.
Description
Technical Field
The invention relates to a polylactic acid chain extender, a preparation method thereof and modified polylactic acid.
Background
Polylactic acid (PLA), the most typical bio-based polymer material, is not only derived from renewable plant resources, but also is biodegradable into non-toxic and harmless carbon dioxide and water under natural conditions. However, polylactic acid is a linear polyester, and has a molecular structure with few branched chains and entanglement points, low melt strength, and poor hot workability and expandability. The method for improving the melt strength of the polylactic acid mainly comprises physical modification such as blending, nucleation, nano-compounding and fiber compounding and chemical modification such as copolymerization, branching, chain extension and crosslinking. Among them, chain extension is an effective method for improving melt strength of polylactic acid. However, the conventional chain extenders are slow in dispersion speed in the polylactic acid matrix and are not uniformly dispersed, resulting in non-uniform molecular weight distribution after chain extension.
Disclosure of Invention
Based on the problems, the invention provides a preparation method and application of a chain extender which has high dispersion speed and uniform dispersion in a polylactic acid matrix.
In order to achieve the purpose, the invention provides the following technical scheme: a polylactic acid chain extender has a structural formula of
A preparation method of a polylactic acid chain extender comprises the following steps:
firstly, preparing the following raw materials in parts by weight:
polymer with good compatibility with polylactic acid: 100, respectively;
glycidyl acrylate monomer: 1-30;
a stabilizer: 0.1 to 1;
secondly, uniformly mixing the three raw materials in a high-speed mixer;
thirdly, extruding and granulating the mixed mixture by using a double-screw extruder;
and finally, radiating the particles to graft the glycidyl acrylate monomer onto a polymer with good compatibility with polylactic acid, thereby preparing the polylactic acid chain extender.
The invention further provides that: the polymer with good compatibility with polylactic acid is polylactic acid. The polymer having good compatibility with polylactic acid may be polyacrylic acid, polyhydroxyalkanoate, or the like.
The invention further provides that: the Glycidyl acrylate monomer is Glycidyl Methacrylate (GMA). The Glycidyl Acrylate monomer may also be Glycidyl Acrylate (GA).
The invention further provides that: the stabilizer is antioxidant 1010{ tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester }. The stabilizer may also be N-phenyl-N' -isopropyl-p-phenylenediamine; hydrogenating the quinoline mixture; n, N' -bis (1, 4-dimethylpentyl) -p-phenylenediamine; N-phenyl-N' - (p-toluenesulfonyl) -p-phenylenediamine, tris (2, 6-di-tert-butylphenyl) phosphite.
The invention further provides that: the radiation is gamma rays (a) using high-energy rays60Co source) or electron beam (electron accelerator).
The invention further provides that: the radiation is electron beam radiation, and the absorption dose of the electron beam radiation is 1-300 kGy.
The invention further provides that: the absorbed dose of the electron beam radiation is 5-100 kGy.
The invention relates to polylactic acid modified by a polylactic acid chain extender.
The invention has the following effects: the main chain structure of the chain extender has good compatibility with the matrix polylactic acid, the dispersion speed and the dispersion uniformity of the chain extender in the matrix polylactic acid are improved, and the modified polylactic acid with uniform molecular weight distribution is obtained after chain extension; meanwhile, the branched chain of the chain extender contains epoxy functional groups, and the chain extender is relatively easy to perform ring-opening esterification reaction with carboxyl at the tail end of the polylactic acid of a matrix, so that the chain-extended modified polylactic acid is obtained. In addition, the radiation grafting method is not influenced by temperature, can be carried out at normal temperature, and generally does not need to add a catalyst and an initiator in the ingredients, so that the cleanness of the material is kept; the product quality is easy to control, and the method is suitable for continuous production and has high production efficiency.
Drawings
FIG. 1 is a schematic diagram of an embodiment of the preparation of the chain extender of the present invention.
Detailed Description
The present embodiment is only for explaining the present invention, and it is not limited to the present invention, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present invention.
Example 1
1) The formula of the polylactic acid chain extender comprises the following components in parts by weight:
polylactic acid (2003D, usa NatureWorks): 100, respectively;
glycidyl methacrylate: 10;
antioxidant 1010: 0.2;
2) process for preparing polylactic acid chain extender
Firstly, drying polylactic acid in a dryer at 80 ℃ for 10 hours, then adding the polylactic acid, glycidyl methacrylate and antioxidant 1010 into a high-speed mixer according to the mass fraction, mixing uniformly, and extruding and granulating by adopting a common double-screw extruder. Finally, the particles are irradiated by electron beams with the absorption dose of 20kGy to prepare the polylactic acid chain extender-glycidyl methacrylate grafted polylactic acid copolymer (PLA-g-GMA), and the preparation reaction diagram is shown in figure 1.
Example 2
1) The formula of the polylactic acid chain extender comprises the following components in parts by weight:
polylactic acid (2003D, usa NatureWorks): 100, respectively;
glycidyl methacrylate: 1;
antioxidant 1010: 0.1;
2) process for preparing polylactic acid chain extender
Firstly, drying polylactic acid in a dryer at 80 ℃ for 10 hours, then adding the polylactic acid, glycidyl methacrylate and antioxidant 1010 into a high-speed mixer according to the mass fraction, mixing uniformly, and extruding and granulating by adopting a common double-screw extruder. Finally, the particles are irradiated by an electron beam with the absorption dose of 10kGy to prepare the polylactic acid chain extender-glycidyl methacrylate grafted polylactic acid copolymer (PLA-g-GMA).
Example 3
1) The formula of the polylactic acid chain extender comprises the following components in parts by weight:
polylactic acid (2003D, usa NatureWorks): 100, respectively;
glycidyl methacrylate: 30, of a nitrogen-containing gas;
antioxidant 1010: 0.5;
2) process for preparing polylactic acid chain extender
Firstly, drying polylactic acid in a dryer at 80 ℃ for 10 hours, then adding the polylactic acid, glycidyl methacrylate and antioxidant 1010 into a high-speed mixer according to the mass fraction, mixing uniformly, and extruding and granulating by adopting a common double-screw extruder. Finally, the particles are irradiated by electron beams with the absorption dose of 30kGy to prepare the polylactic acid chain extender-glycidyl methacrylate grafted polylactic acid copolymer (PLA-g-GMA).
Performance test
And comparing the chain extension effect of the chain extender on the polylactic acid by adopting a torque rheometer.
The experimental conditions are as follows: the temperature is 180 ℃, the rotating speed is 60rpm, and the time is 10min
The main measurement parameters are as follows: maximum torque, time to reach maximum torque
1) Comparative example: 0.5% chain extender [ ADR4370 (BASF, Germany, styrene-acrylate-glycidyl methacrylate terpolymer, commercially available) ] and 99.5% polylactic acid (2003D, NatureWorks)
2) Example (b): 0.5% chain extender (from examples 1-3) and 99.5% polylactic acid (2003D, NatureWorks).
3) Results of the experiment
| Maximum torque, N.m | Time to maximum torque, min | |
| Pure polylactic acid | 11.6 | 3.6 |
| Comparative example chain extender modified polylactic acid | 22.2 | 7.2 |
| Example 1 chain extender modified polylactic acid | 28.6 | 5.2 |
| Example 2 chain extender modified polylactic acid | 24.1 | 6.8 |
| Example 3 chain extender modified polylactic acid | 35.7 | 8.2 |
Claims (1)
1. A preparation method of modified polylactic acid is characterized in that 0.5 percent of chain extender and 99.5 percent of polylactic acid are reacted for 10min by a torque rheometer under the conditions of 180 ℃ of temperature and 60rpm of rotating speed;
the chain extender is a glycidyl methacrylate grafted polylactic acid copolymer, and the preparation method comprises the following steps:
firstly, drying polylactic acid in a dryer at 80 ℃ for 10 h; then adding 100 parts by weight of polylactic acid, 30 parts by weight of glycidyl methacrylate and 10100.5 parts by weight of antioxidant into a high-speed mixer for uniform mixing, and extruding and granulating by adopting a double-screw extruder; finally, the granules were treated by electron beam irradiation at an absorbed dose of 30 kGy.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201811517424.XA CN109575196B (en) | 2018-12-12 | 2018-12-12 | Polylactic acid chain extender, preparation method thereof and modified polylactic acid |
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| CN201811517424.XA CN109575196B (en) | 2018-12-12 | 2018-12-12 | Polylactic acid chain extender, preparation method thereof and modified polylactic acid |
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| CN109575196A CN109575196A (en) | 2019-04-05 |
| CN109575196B true CN109575196B (en) | 2022-04-05 |
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| CN110483829A (en) * | 2019-08-22 | 2019-11-22 | 中国科学院青岛生物能源与过程研究所 | A kind of low irradiation intensity prepares the preparation method of high-strength polypropylene expanded bead (EPP) |
| CN113402678B (en) * | 2021-06-17 | 2022-04-22 | 华南理工大学 | Method for preparing high-melt-strength polylactic resin through two-step reaction |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102199257A (en) * | 2011-03-16 | 2011-09-28 | 中国科学院长春应用化学研究所 | Preparation method of modified polylactic acid |
| CN102603994A (en) * | 2012-03-09 | 2012-07-25 | 中国科学院宁波材料技术与工程研究所 | Glycidyl methacrylate grafted polylactic acid copolymer material, preparation method for same and application thereof |
| CN102936307A (en) * | 2012-11-27 | 2013-02-20 | 山西省化工研究所 | Epoxy functionalized chain extender, and preparation method and application thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102199257A (en) * | 2011-03-16 | 2011-09-28 | 中国科学院长春应用化学研究所 | Preparation method of modified polylactic acid |
| CN102603994A (en) * | 2012-03-09 | 2012-07-25 | 中国科学院宁波材料技术与工程研究所 | Glycidyl methacrylate grafted polylactic acid copolymer material, preparation method for same and application thereof |
| CN102936307A (en) * | 2012-11-27 | 2013-02-20 | 山西省化工研究所 | Epoxy functionalized chain extender, and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| Effect of poly (lactic acid)-graft-glycidyl methacrylate as a compatibilizer on properties of poly (lactic acid)/banana fiber biocomposites;Sajna VPa et al.;《Polym. Adv. Technol》;20151105;第27卷;第515–524页 * |
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