CN109575196A - A kind of polylactic acid chain extender and preparation method thereof and polydactyl acid - Google Patents
A kind of polylactic acid chain extender and preparation method thereof and polydactyl acid Download PDFInfo
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- CN109575196A CN109575196A CN201811517424.XA CN201811517424A CN109575196A CN 109575196 A CN109575196 A CN 109575196A CN 201811517424 A CN201811517424 A CN 201811517424A CN 109575196 A CN109575196 A CN 109575196A
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- polylactic acid
- chain extender
- acid chain
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- electron beam
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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
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- 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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- 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 present invention relates to a kind of polylactic acid chain extender and preparation method thereof and polydactyl acids.The structural formula of polylactic acid chain extender of the present invention isPolylactic acid chain extender of the invention, fast, the finely dispersed technical effect with the rate of dispersion in polylactic acid matrix.
Description
Technical field
The present invention relates to a kind of polylactic acid chain extender and preparation method thereof and polydactyl acids.
Background technique
Polylactic acid (PLA, Polylactic acid) is used as most typical biology base high molecular material, from not only can
Regenerated plant resources, and biodegradable under field conditions (factors) is nontoxic carbon dioxide and water.However, polylactic acid
Belong to linear polyester, branch and its entanglement point are few in molecular structure, and melt strength is low, and hot-working character and expandability are poor.It mentions
The method of high polylactic acid melt intensity mainly has the physical modifications such as blending, nucleation, nano combined and fiber composite and copolymerization, branch
The chemical modifications such as change, chain extension, crosslinking.Wherein, chain extension is the effective ways for improving polylactic acid melt intensity.But existing expansion
Rate of dispersion of the chain agent in polylactic acid matrix is slow, dispersion is uneven, causes molecular weight distribution after chain extension uneven.
Summary of the invention
Based on the above issues, the present invention provides that a kind of rate of dispersion in polylactic acid matrix is fast, finely dispersed chain extension
The preparation method and applications of agent.
To achieve the above object, the present invention provides the following technical scheme that a kind of polylactic acid chain extender, structural formula are
A kind of preparation method of polylactic acid chain extender, comprising the following steps:
Firstly, will match by mass fraction, prepare raw material:
The good polymer with polylactic acid compatibility: 100；
Glycidyl acrylate class monomer: 1~30；
Stabilizer: 0.1~1；
Secondly, mixture is uniform in high speed mixer by above-mentioned three kinds of raw materials；
Again, the good said mixture of mixture squeezed out using double screw extruder, be granulated；
Finally, above-mentioned particulate matter is grafted to glycidyl acrylate class monomer therein and polylactic acid by radiation
On the good polymer of compatibility, polylactic acid chain extender is made.
The present invention is further arranged: the described and good polymer of polylactic acid compatibility is polylactic acid.With polylactic acid compatibility
Good polymer can also be with polyacrylic acid, polyacrylic acid, polyhydroxyalkanoate etc..
The present invention is further arranged: the glycidyl acrylate class monomer is glycidyl methacrylate
(GMA,Glycidyl Methacrylate).Glycidyl acrylate class monomer is also possible to glycidyl acrylate
(GA,Glycidyl Acrylate)。
The present invention is further arranged: the stabilizer is antioxidant 1010 { four [β-(3,5- di-t-butyl -4- hydroxy benzenes
Base) propionic acid] pentaerythritol ester }.Stabilizer is also possible to N- phenyl-N '-isopropyl-p-phenylenediamine；Hydrogenated quinoline mixture；
N, N '-two (Isosorbide-5-Nitrae-dimethyl amyl group)-p-phenylenediamine；N- phenyl-N '-(ptoluene-sulfonyl)-p-phenylenediamine, three (2,6-
At least one of two-uncles are to butyl phenyl) phosphite ester.
The present invention is further arranged: it is described radiation be using high-energy ray gamma-rays (60The source Co) or electron beam (electronics acceleration
Device) irradiation.
The present invention is further arranged: the radiation is electron beam irradiation, the absorbed dose of the electron beam irradiation is 1~
300kGy。
The present invention is further arranged: the absorbed dose of the electron beam irradiation is 5~100kGy.
A kind of polylactic acid that the polylactic acid chain extender of technical solution of the present invention is modified.
The present invention has the effect that the backbone structure of chain extender and matrix polylactic acid compatibility are good, improves the chain extender
Rate of dispersion and dispersed homogeneous degree in matrix polylactic acid obtain the polydactyl acid of even molecular weight distribution after chain extension；Together
When, the branch of chain extender contains epoxy-functional, it is easier to react with the carboxyl of matrix polylactic acid end generation esterification by ring opening,
Obtain the modified polylactic acid of chain extension.In addition, method for radio-grafting is not affected by temperature, can carry out at normal temperature, and ingredient
In do not need generally addition catalyst, initiator, maintain the cleanliness of material；Product quality is easy to control, and is suitable for continuous raw
It produces, high production efficiency.
Detailed description of the invention
Fig. 1 is that chain extender of the present invention prepares embodiment schematic diagram.
Specific embodiment
This specific embodiment is only explanation of the invention, is not limitation of the present invention, those skilled in the art
Member can according to need the modification that not creative contribution is made to the present embodiment after reading this specification, but as long as at this
All by the protection of Patent Law in the scope of the claims of invention.
Embodiment 1
1) formula of polylactic acid chain extender is (pressing mass fraction):
Polylactic acid (2003D, U.S. NatureWorks): 100；
Glycidyl methacrylate: 10；
Antioxidant 1010: 0.2；
2) preparation process of polylactic acid chain extender
Polylactic acid is first dried into 10h in 80 DEG C of driers, then by polylactic acid, glycidyl methacrylate and anti-
Oxygen agent 1010 is added to mixture in high speed mixer by above-mentioned mass fraction and uniformly, is made using general double screw extruder extrusion
Grain.Finally, the particulate matter is 20kGy electron beam irradiation by absorbed dose, polylactic acid chain extender-methyl-prop of the invention is prepared
Olefin(e) acid ethylene oxidic ester grafted polylactic acid copolymer (PLA-g-GMA), preparation reaction schematic diagram are shown in attached drawing 1.
Embodiment 2
1) formula of polylactic acid chain extender is (pressing mass fraction):
Polylactic acid (2003D, U.S. NatureWorks): 100；
Glycidyl methacrylate: 1；
Antioxidant 1010: 0.1；
2) preparation process of polylactic acid chain extender
Polylactic acid is first dried into 10h in 80 DEG C of driers, then by polylactic acid, glycidyl methacrylate and anti-
Oxygen agent 1010 is added to mixture in high speed mixer by above-mentioned mass fraction and uniformly, is made using general double screw extruder extrusion
Grain.Finally, the particulate matter is 10kGy electron beam irradiation by absorbed dose, polylactic acid chain extender-methyl-prop of the invention is prepared
Olefin(e) acid ethylene oxidic ester grafted polylactic acid copolymer (PLA-g-GMA).
Embodiment 3
1) formula of polylactic acid chain extender is (pressing mass fraction):
Polylactic acid (2003D, U.S. NatureWorks): 100；
Glycidyl methacrylate: 30；
Antioxidant 1010: 0.5；
2) preparation process of polylactic acid chain extender
Polylactic acid is first dried into 10h in 80 DEG C of driers, then by polylactic acid, glycidyl methacrylate and anti-
Oxygen agent 1010 is added to mixture in high speed mixer by above-mentioned mass fraction and uniformly, is made using general double screw extruder extrusion
Grain.Finally, the particulate matter is 30kGy electron beam irradiation by absorbed dose, polylactic acid chain extender-methyl-prop of the invention is prepared
Olefin(e) acid ethylene oxidic ester grafted polylactic acid copolymer (PLA-g-GMA).
Aptitude test
Chain extender is compared to the chain extension effect of polylactic acid using torque rheometer.
Experiment condition: temperature=180 DEG C, revolving speed=60rpm, time=10min
Main location parameter: peak torque reaches the time of peak torque
1) comparative example: 0.5% chain extender [ADR4370 (BASF Corp. of Germany, cinnamic acrylic ester-methacrylic acid
Ethylene oxidic ester terpolymer can be commercially available from market)] and 99.5% polylactic acid (2003D, NatureWorks)
2) embodiment: 0.5% chain extender (being obtained from embodiment 1-3) and 99.5% polylactic acid (2003D,
NatureWorks)。
3) experimental result
| Peak torque, Nm | Reach the time of peak torque, min | |
| Pure polylactic acid | 11.6 | 3.6 |
| Comparative example chain extender polydactyl acid | 22.2 | 7.2 |
| 1 chain extender polydactyl acid of embodiment | 28.6 | 5.2 |
| 2 chain extender polydactyl acid of embodiment | 24.1 | 6.8 |
| 3 chain extender polydactyl acid of embodiment | 35.7 | 8.2 |
Claims (9)
1. a kind of polylactic acid chain extender, it is characterised in that its structural formula is
2. a kind of preparation method of polylactic acid chain extender, it is characterised in that:
The following steps are included:
Firstly, will match by mass fraction, prepare raw material:
The good polymer with polylactic acid compatibility: 100；
Glycidyl acrylate class monomer: 1~30；
Stabilizer: 0.1~1；
Secondly, mixture is uniform in high speed mixer by above-mentioned three kinds of raw materials；
Again, the good said mixture of mixture squeezed out using double screw extruder, be granulated；
Finally, above-mentioned particulate matter is grafted to glycidyl acrylate class monomer therein compatible with polylactic acid by radiation
Property good polymer on, polylactic acid chain extender is made.
3. the preparation method of polylactic acid chain extender according to claim 2, it is characterised in that: described and polylactic acid compatibility
Good polymer is polylactic acid.
4. the preparation method of polylactic acid chain extender according to claim 2, it is characterised in that: the glycidyl
Esters monomer is glycidyl methacrylate.
5. the preparation method of polylactic acid chain extender according to claim 2, it is characterised in that: the stabilizer is antioxidant
1010。
6. the preparation method of polylactic acid chain extender according to claim 2, it is characterised in that: the radiation is to utilize high energy
Ray gamma-rays or electron beam irradiation.
7. the preparation method of polylactic acid chain extender according to claim 6, it is characterised in that: the radiation is that electron beam shines
It penetrates, the absorbed dose of the electron beam irradiation is 1~300kGy.
8. the preparation method of polylactic acid chain extender according to claim 7, it is characterised in that: the suction of the electron beam irradiation
Receipts dosage is 5~100kGy.
9. a kind of polylactic acid modified with polylactic acid chain extender described in claim 1.
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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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| CN109575196B CN109575196B (en) | 2022-04-05 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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) |
| CN113402678A (en) * | 2021-06-17 | 2021-09-17 | 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 |
-
2018
- 2018-12-12 CN CN201811517424.XA patent/CN109575196B/en active Active
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 (2)
| Title |
|---|
| SAJNA VPA ET AL.: "Effect of poly (lactic acid)-graft-glycidyl methacrylate as a compatibilizer on properties of poly (lactic acid)/banana fiber biocomposites", 《POLYM. ADV. TECHNOL》 * |
| 黄光琳等: "《高分子辐射化学基础》", 30 September 1993, 四川大学出版社 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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) |
| CN113402678A (en) * | 2021-06-17 | 2021-09-17 | 华南理工大学 | Method for preparing high-melt-strength polylactic resin through two-step reaction |
| 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 |
| US11505646B1 (en) | 2021-06-17 | 2022-11-22 | South China University Of Technology | Method for producing high-melt-strength polylactide resin |
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