CN105670246A - High-performance PLA alloy material and preparation method thereof - Google Patents
High-performance PLA alloy material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a high-performance PLA alloy material and a preparation method thereof. The high-performance PLA alloy material is composed of 70-90 parts of polylactic acid, 10-30 parts of an ethylene-octylene random copolymer, 0.4-0.8 parts of an ethylene-glycidyl methacrylate copolymer, 8-14 parts of modified nano silicon dioxide and 0.3-0.7 parts of an antioxidant. The material is prepared by mixing and extruding the components hereinabove. The POE is used for improving the flexibility of the PLA, wherein a compatibilizer EGMA is added for improving compatibility of the PLA/POD mixture, thereby increasing the interface bonding force between the two phases and improving the performance of the mixture. The modified nano silicon dioxide can improve the strength, rigidity and toughness of the polymer. The PLA alloy material is high in strength, is good in toughness and is environment-friendly, and can be widely used in the fields of package materials, toys, electronic appliance and household article.
Description
Technical field
The present invention relates to technical field of polymer composite materials, particularly relate to a kind of PLA alloy material and preparation method thereof.
Background technology
Polylactic acid (PLA) obtains the extensive concern of industrial quarters with its good biological degradability and higher mechanical performance. But compared with current industrial wide variety of petroleum base engineering plastics, the fragility of PLA, relatively low crystallizing power but greatly limit its extensive use. And ethylene-octene random copolymer (POE) has good toughness, simultaneously also have the excellent properties such as ozone ageing-resistant, resistance to, resistant to chemical media concurrently, be all applied widely in making them in automobile industry, electric wire and cable jacket, plastics toughening agent etc. just because of the excellent properties of POE.
As adopted POE to strengthen the toughness of PLA, but the alternate interface binding power of PLA/POE two is poor, does not reach toughness reinforcing purpose. Further, since POE is thermoplastic elastomer (TPE), the intensity of self and modulus are relatively low, make the modulus of composite and intensity all decline after joining PLA.
Summary of the invention
It is an object of the invention to provide a kind of PLA alloy material and preparation method thereof, adopting this composite prepared in this way and have high intensity, high tenacity and environmental friendliness concurrently, this composite can be widely applied to the fields such as packaging material, toy, electrical equipment and household supplies.
The purpose of the present invention can be achieved through the following technical solutions, a kind of high-performance PLA alloy material, each component following be prepared from by weight:
Polylactic acid (PLA) 70-90 part
Ethylene-octene random copolymer (POE) 10-30 part
Ethylene-methyl methacrylate glycidyl ester copolymer (EGMA) 0.4-0.8 part
Modified manometer silicon dioxide 8-14 part
Antioxidant 0.3-0.7 part;
Described improved silica is formed by L-lactide ring-opening polymerisation engrafted nanometer silicon dioxide.
Further, in described polylactic acid, the mass percent of L-type PLA is the mass percent of 92-96%, D type PLA is 4-8%.
In described ethylene-methyl methacrylate glycidyl ester copolymer (EGMA) mass percent of glycidyl methacrylate be 8%, the mass percent of acrylic acid methyl ester. be 25%.
Described nano silicon is hydrophilic, and its mean diameter is 12-40nm.
Described antioxidant is four (β-(3,5-di-tert-butyl-hydroxy phenyl) propanoic acid) pentaerythritol ester (antioxidant 1010) and 1,3,5-trimethyl-2,4,6-(3,5-di-t-butyl-4-hydroxyphenylmethyl) benzene (antioxidant 1330) is by weight composite for 1:1.
Another goal of the invention of the present invention is to provide its preparation method of above-mentioned a kind of high-performance PLA alloy material, and step is as follows:
(1) modified manometer silicon dioxide is prepared
By nano silicon elder generation at vacuum drying oven in 60-80 DEG C of dry 10-14h, to remove the moisture on its surface; Then dry nano silicon and solvent toluene are added in the device of condensing tube, in a nitrogen atmosphere, be stirred preheating under 90 DEG C of oil bath heating states; Being eventually adding L-lactide and octoate catalyst Asia stannum, wherein the mass ratio of nano silicon and L-lactide, stannous octoate is 1:(0.1-0.4): (0.01-0.03), constant temperature stirring after being warming up to 100-120 DEG C; Reaction is cooled to room temperature after terminating and is centrifuged processing to obtain modified manometer silicon dioxide;
(2) by proportioning, by dry polylactic acid, ethylene-octene random copolymer, ethylene-methyl methacrylate glycidyl ester copolymer, modified manometer silicon dioxide and antioxidant, stirred 5～10 minutes by high-speed mixer, form mixed material;
(3) mixed material is put in the hopper of double screw extruder, obtain PLA alloy material through melted, extrusion, pelletize.
Further, in described step (1) prepare modified manometer silicon dioxide chloroform to its clean with removes surface because physical action adsorb and unreacted L-lactide.
In described step (3), double screw extruder comprises six districts, wherein each district temperature and screw speed are respectively as follows: district's temperature 70～100 DEG C, two district's temperature 120～220 DEG C, three district's temperature 130～230 DEG C, four district's temperature 140～230 DEG C, five district's temperature 140～230 DEG C, six district's temperature 140～240 DEG C, head temperature 130～200 DEG C; Screw speed 120～300r/min.
So, beneficial effects of the present invention has:
1, the present invention adopts POE to improve the toughness of PLA, and adds bulking agent EGMA to improve the compatibility of PLA/POE blend, improves two alternate interface binding powers, improves the performance of blend. This is because the epoxy radicals of the terminal hydroxy group of PLA or carboxyl and EGMA there occurs reaction when reactive blending, and the graft polymers generated improves the biphase compatibility.
2, owing to POE is thermoplastic elastomer (TPE), the intensity of self and modulus are low, reduce modulus and the decrease in strength of composite after joining PLA. The present invention, in order to improve modulus and the intensity of PLA/POE blend, adds modified manometer silicon dioxide as modifying agent, can make the intensity of polymer, rigidity, toughness be improved significantly.
3, the employing L-lactide that this patent is also innovated comes nano Si 02Powder body carries out surface modification treatment, makes nano Si 02Powder surface grafted polylactic acid, so modified nano silicon is not easily reunited, is uniformly dispersed and has the better compatibility with polymer, the effect that simultaneously can also play heterogeneous nucleation improves the crystal property of PLA, not only increase the mechanical property of PLA alloy material, also make performance more stable.
4, the PLA alloy material that prepared by the present invention has high intensity, high tenacity and environmental friendliness concurrently, and this composite can be widely applied to the fields such as packaging material, toy, electrical equipment and household supplies.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention done a detailed elaboration.
Embodiment 1
(1) modified manometer silicon dioxide is prepared
By nano silicon elder generation at vacuum drying oven in 60 DEG C of dry 14h, to remove the moisture on its surface;
Then dry nano silicon and solvent toluene are added in the device of condensing tube, in a nitrogen atmosphere, be stirred preheating under 90 DEG C of oil bath heating states;
Being eventually adding octoate catalyst Asia stannum, L-lactide, wherein the mass ratio of nano silicon and L-lactide, stannous octoate is 1:0.1:0.01, constant temperature stirring after being warming up to 100 DEG C;
Reaction is cooled to room temperature and is centrifuged processing after terminating, finally with chloroform precipitate repeatedly cleans to remove the unreacted L-lactide that powder surface adsorb because of physical action, then dries and to obtain modified manometer silicon dioxide;
(2) by proportioning, the modified manometer silicon dioxide 8 parts prepared in dry PLA70 part, POE10 part, EGMA0.4 part, (1) and antioxidant 1010 0.15 part, 13300.15 parts of antioxidant, stirred 5 minutes by high-speed mixer, form mixed material;
(3) mixed material is put in the hopper of double screw extruder, obtain PLA alloy material through melted, extrusion, pelletize. Wherein double screw extruder each district temperature and screw speed are respectively as follows: district's temperature 70 C, two district's temperature 120 DEG C, three district's temperature 130 DEG C, four district's temperature 140 DEG C, five district's temperature 140 DEG C, six district's temperature 140 DEG C, head temperature 130 DEG C; Screw speed 120r/min.
Embodiment 2
(1) modified manometer silicon dioxide is prepared
By nano silicon elder generation at vacuum drying oven in 80 DEG C of dry 10h, to remove the moisture on its surface;
Then dry nano silicon and toluene are added in the device of condensing tube, in a nitrogen atmosphere, be stirred preheating under 90 DEG C of oil bath heating states;
Being eventually adding octoate catalyst Asia stannum, L-lactide, wherein the mass ratio of nano silicon and L-lactide, stannous octoate is 1:0.4:0.03, constant temperature stirring after being warming up to 120 DEG C;
Reaction is cooled to after room temperature is centrifuged processing and with chloroform precipitate repeatedly cleans to remove the unreacted L-lactide that powder surface adsorb because of physical action after terminating, then dries and to obtain modified manometer silicon dioxide;
(2) by proportioning, by dry PLA90 part, POE30 part, EGMA0.8 part, modified manometer silicon dioxide 14 parts and antioxidant 1010 0.35 part, 13300.35 parts of antioxidant, stirred 10 minutes by high-speed mixer, form mixed material;
(3) mixed material is put in the hopper of double screw extruder, obtain PLA alloy material through melted, extrusion, pelletize. Wherein double screw extruder each district temperature and screw speed are respectively as follows: district's temperature 100 DEG C, two district's temperature 220 DEG C, three district's temperature 230 DEG C, four district's temperature 230 DEG C, five district's temperature 230 DEG C, six district's temperature 240 DEG C, head temperature 200 DEG C; Screw speed 300r/min.
Embodiment 3
(1) modified manometer silicon dioxide is prepared
By nano silicon elder generation at vacuum drying oven in 70 DEG C of dry 12h, to remove the moisture on its surface;
Then dry nano silicon and toluene are added in the device of condensing tube, in a nitrogen atmosphere, be stirred preheating under 90 DEG C of oil bath heating states;
Being eventually adding octoate catalyst Asia stannum, L-lactide, wherein the mass ratio of nano silicon and L-lactide, stannous octoate is 1:0.1:0.03, constant temperature stirring after being warming up to 110 DEG C;
Reaction is cooled to after room temperature is centrifuged processing and with chloroform precipitate repeatedly cleans to remove the unreacted L-lactide that powder surface adsorb because of physical action after terminating, then dries and to obtain modified manometer silicon dioxide;
(2) by proportioning, by dry PLA80 part, POE20 part, EGMA0.6 part, modified manometer silicon dioxide 11 parts and antioxidant 1010 0.25 part, 13300.25 parts of antioxidant, stirred 7 minutes by high-speed mixer, form mixed material;
(3) mixed material is put in the hopper of double screw extruder, obtain PLA alloy material through melted, extrusion, pelletize. Wherein double screw extruder each district temperature and screw speed are respectively as follows: district's temperature 85 DEG C, two district's temperature 170 DEG C, three district's temperature 180 DEG C, four district's temperature 185 DEG C, five district's temperature 185 DEG C, six district's temperature 190 DEG C, head temperature 165 DEG C; Screw speed 210r/min.
Embodiment 4
(1) modified manometer silicon dioxide is prepared
By nano silicon elder generation at vacuum drying oven in 70 DEG C of dry 12h, to remove the moisture on its surface;
Then dry nano silicon and toluene are added in the device of condensing tube, in a nitrogen atmosphere, be stirred preheating under 90 DEG C of oil bath heating states;
Be eventually adding octoate catalyst Asia stannum, L-third hands over the mass ratio of wherein nano silicon and L-lactide, stannous octoate to be 1:0.2:0.02, constant temperature stirring after being warming up to 110 DEG C;
Reaction is cooled to after room temperature is centrifuged processing and with chloroform precipitate repeatedly cleans to remove the unreacted L-lactide that powder surface adsorb because of physical action after terminating, then dries and to obtain modified manometer silicon dioxide;
(2) by proportioning, by dry PLA75 part, POE20 part, EGMA0.5 part, modified manometer silicon dioxide 11 parts and antioxidant 1010 0.2 part, 13300.2 parts of antioxidant, stirred 9 minutes by high-speed mixer, form mixed material;
(3) mixed material is put in the hopper of double screw extruder, obtain PLA alloy material through melted, extrusion, pelletize. Wherein double screw extruder each district temperature and screw speed are respectively as follows: district's temperature 90 DEG C, two district's temperature 180 DEG C, three district's temperature 190 DEG C, four district's temperature 220 DEG C, five district's temperature 210 DEG C, six district's temperature 220 DEG C, head temperature 185 DEG C; Screw speed 200r/min.
Embodiment 5
(1) modified manometer silicon dioxide is prepared
By nano silicon elder generation at vacuum drying oven in 75 DEG C of dry 13h, to remove the moisture on its surface;
Then dry nano silicon and toluene are added in the device of condensing tube, in a nitrogen atmosphere, be stirred preheating under 90 DEG C of oil bath heating states;
Being eventually adding octoate catalyst Asia stannum, L-lactide, wherein the mass ratio of nano silicon and L-lactide, stannous octoate is 1:0.4:0.01, constant temperature stirring after being warming up to 115 DEG C;
Reaction is cooled to after room temperature is centrifuged processing and with chloroform precipitate repeatedly cleans to remove the unreacted L-lactide that powder surface adsorb because of physical action after terminating, then dries and to obtain modified manometer silicon dioxide;
(2) by proportioning, by dry PLA85 part, POE20 part, EGMA0.5 part, modified manometer silicon dioxide 10 parts and antioxidant 1010 0.3 part, 13300.3 parts of antioxidant, stirred 6 minutes by high-speed mixer, form mixed material;
(3) mixed material is put in the hopper of double screw extruder, obtain PLA alloy material through melted, extrusion, pelletize.Wherein double screw extruder each district temperature and screw speed are respectively as follows: district's temperature 100 DEG C, two district's temperature 190 DEG C, three district's temperature 185 DEG C, four district's temperature 220 DEG C, five district's temperature 210 DEG C, six district's temperature 220 DEG C, head temperature 185 DEG C; Screw speed 190r/min.
Comparative example 1
1, polylactic acid (PLA) 85 parts, ethylene-octene random copolymer (POE) 20 parts, anti-oxidant Irganox 10100.3 parts, anti-oxidant Irganox 13300.3 parts are weighed,
2, PLA, POE of weighing up are dried 24 hours in 60 DEG C of vacuum drying ovens;
3, by PLA, the POE after dried and antioxidant, stirred 8 minutes by high-speed mixer, form mixed material;
4, the mixed material mixed is put in the hopper of double screw extruder, through frit reaction, then extrusion, pelletize.
Wherein double screw extruder each district temperature and screw speed are respectively as follows: district's temperature 110 DEG C, two district's temperature 160 DEG C, three district's temperature 190 DEG C, four district's temperature 190 DEG C, five district's temperature 200 DEG C, six district's temperature 200 DEG C, head temperature 185 DEG C; Screw speed 290r/min.
Lactic acid composite material prepared by the PLA alloy material prepared by embodiment 1-5 and comparative example 1 is respectively prepared batten and contrasts, according to standard ISO527-1:2012, it is carried out hot strength, bending strength, Izod notched impact strength test by ISO178:2010 and ISO180:2010 respectively, tests data such as following table:
| Test event | Unit | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Comparative example 1 |
| Bending modulus | MPa | 2810 | 2850 | 2920 | 2670 | 2790 | 1790 |
| Hot strength | MPa | 74 | 66 | 72 | 71 | 69 | 37 |
| Izod notched impact strength | kJ/m2 | 7.5 | 8.5 | 7.8 | 5.7 | 8.2 | 2.6 |
Being can be seen that by the contrast of upper table, in the PLA alloy material relatively comparative example that the present invention prepares, PLA composite is compared, and its hot strength, bending strength, Izod notched impact strength all obtain raising in various degree. Thus being greatly expanded the application of PLA alloy material.
The several specific embodiments being only the application disclosed above, but the application is not limited to this, the changes that any person skilled in the art can think of, all should drop in the protection domain of the application.
Claims (8)
1. a high-performance PLA alloy material, it is characterised in that: it is prepared from by weight by each component following:
Polylactic acid 70-90 part
Ethylene-octene random copolymer 10-30 part
Ethylene-methyl methacrylate glycidyl ester copolymer 0.4-0.8 part
Modified manometer silicon dioxide 8-14 part
Antioxidant 0.3-0.7 part;
Described improved silica is formed by L-lactide ring-opening polymerisation engrafted nanometer silicon dioxide.
2. a kind of high-performance PLA alloy material according to claim 1, it is characterised in that: in described polylactic acid, the mass percent of L-type PLA is the mass percent of 92-96%, D type PLA is 4-8%.
3. a kind of high-performance PLA alloy material according to claim 1, it is characterised in that: in described ethylene-methyl methacrylate glycidyl ester copolymer the mass percent of glycidyl methacrylate be 8%, the mass percent of acrylic acid methyl ester. be 25%.
4. a kind of high-performance PLA alloy material according to claim 1, it is characterised in that: described nano silicon is hydrophilic, and its mean diameter is 12-40nm.
5. a kind of high-performance PLA alloy material according to claim 1, it is characterized in that: described antioxidant is four (β-(3,5-di-tert-butyl-hydroxy phenyl) propanoic acid) pentaerythritol ester and 1,3,5-trimethyl-2,4,6-(3,5-di-t-butyl-4-hydroxyphenylmethyl) benzene is by weight composite for 1:1.
6. the preparation method of a kind of high-performance PLA alloy material as claimed in claim 1, step is as follows:
(1) modified manometer silicon dioxide is prepared
By nano silicon elder generation at vacuum drying oven in 60-80 DEG C of dry 10-14h, to remove the moisture on its surface;
Then dry nano silicon and solvent toluene are added in the device of condensing tube, under nitrogen atmosphere, 90 DEG C of oil bath heating states, be stirred preheating;
Being eventually adding L-lactide and octoate catalyst Asia stannum, wherein the mass ratio of nano silicon and L-lactide, stannous octoate is 1:(0.1-0.4): (0.01-0.03), constant temperature stirring after being warming up to 100-120 DEG C;
Reaction is cooled to room temperature after terminating and is centrifuged processing to obtain modified manometer silicon dioxide;
(2) by proportioning, by dry polylactic acid, ethylene-octene random copolymer, ethylene-methyl methacrylate glycidyl ester copolymer, modified manometer silicon dioxide and antioxidant, stirred 5～10 minutes by high-speed mixer, form mixed material;
(3) mixed material is put in the hopper of double screw extruder, obtain PLA alloy material through melted, extrusion, pelletize.
7. preparation method according to claim 6, it is characterised in that: in described step (1) prepare modified manometer silicon dioxide chloroform to its clean with removes surface because physical action adsorb and unreacted L-lactide.
8. preparation method according to claim 6, it is characterized in that: in described step (3), double screw extruder comprises six districts, wherein each district temperature and screw speed are respectively as follows: district's temperature 70～100 DEG C, two district's temperature 120～220 DEG C, three district's temperature 130～230 DEG C, four district's temperature 140～230 DEG C, five district's temperature 140～230 DEG C, six district's temperature 140～240 DEG C, head temperature 130～200 DEG C; Screw speed 120～300r/min.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109651779A (en) * | 2018-11-27 | 2019-04-19 | 包惠芳 | A kind of PLA-POE composite material |
| CN113801449A (en) * | 2021-11-05 | 2021-12-17 | 江苏中恒宠物用品股份有限公司 | Thermoplastic elastomer toy material and preparation method thereof |
| CN114539568A (en) * | 2022-03-15 | 2022-05-27 | 福建长泰万泰矿物制品有限公司 | Biodegradable plastic, preparation method and application thereof |
| CN115093684A (en) * | 2022-06-08 | 2022-09-23 | 青岛普诺恩生物科技有限公司 | Modified degradable material for improving melt strength and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1876711A (en) * | 2006-07-12 | 2006-12-13 | 哈尔滨工业大学 | Process for microwave radiation in-situ preparation of poly-lactic acid/montmorillonite nano composite materials |
| CN101519526A (en) * | 2008-10-10 | 2009-09-02 | 兰州理工大学 | Method for preparing polylactic acid/nanometer silicon dioxide composite material |
| CN102702705A (en) * | 2012-07-04 | 2012-10-03 | 华东理工大学 | Toughened polylactic acid/polyolefin elastomer composite material and preparation method thereof |
| CN103602048A (en) * | 2013-11-28 | 2014-02-26 | 四川大学 | Polylactic acid film blowing processing aid and preparation method and application thereof |
-
2014
- 2014-11-21 CN CN201410673585.3A patent/CN105670246A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1876711A (en) * | 2006-07-12 | 2006-12-13 | 哈尔滨工业大学 | Process for microwave radiation in-situ preparation of poly-lactic acid/montmorillonite nano composite materials |
| CN101519526A (en) * | 2008-10-10 | 2009-09-02 | 兰州理工大学 | Method for preparing polylactic acid/nanometer silicon dioxide composite material |
| CN102702705A (en) * | 2012-07-04 | 2012-10-03 | 华东理工大学 | Toughened polylactic acid/polyolefin elastomer composite material and preparation method thereof |
| CN103602048A (en) * | 2013-11-28 | 2014-02-26 | 四川大学 | Polylactic acid film blowing processing aid and preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| 张越等: "聚乳酸/纳米SiO2熔纺纤维的制备及其力学性能", 《合成纤维工业》 * |
| 李冬冬: "聚乳酸/POE/纳米二氧化硅复合材料的制备与性能", 《中国优秀硕士学位论文全文数据库 (工程科技Ⅰ辑)》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109651779A (en) * | 2018-11-27 | 2019-04-19 | 包惠芳 | A kind of PLA-POE composite material |
| CN113801449A (en) * | 2021-11-05 | 2021-12-17 | 江苏中恒宠物用品股份有限公司 | Thermoplastic elastomer toy material and preparation method thereof |
| CN114539568A (en) * | 2022-03-15 | 2022-05-27 | 福建长泰万泰矿物制品有限公司 | Biodegradable plastic, preparation method and application thereof |
| CN114539568B (en) * | 2022-03-15 | 2024-03-22 | 福建长泰万泰矿物制品有限公司 | Biodegradable plastic, preparation method and application thereof |
| CN115093684A (en) * | 2022-06-08 | 2022-09-23 | 青岛普诺恩生物科技有限公司 | Modified degradable material for improving melt strength and preparation method thereof |
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Application publication date: 20160615 |