CN112852088A - Bio-based polylactic acid composite material - Google Patents
Bio-based polylactic acid composite material Download PDFInfo
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- CN112852088A CN112852088A CN202110043182.0A CN202110043182A CN112852088A CN 112852088 A CN112852088 A CN 112852088A CN 202110043182 A CN202110043182 A CN 202110043182A CN 112852088 A CN112852088 A CN 112852088A
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- polylactic acid
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- acid composite
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- 229920000747 poly(lactic acid) Polymers 0.000 title claims abstract description 62
- 239000004626 polylactic acid Substances 0.000 title claims abstract description 62
- 239000002131 composite material Substances 0.000 title claims abstract description 28
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 18
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229920002678 cellulose Polymers 0.000 claims abstract description 16
- 239000001913 cellulose Substances 0.000 claims abstract description 16
- 239000000945 filler Substances 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 11
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 9
- 229920001577 copolymer Polymers 0.000 claims abstract description 9
- 239000008367 deionised water Substances 0.000 claims abstract description 9
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000002791 soaking Methods 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 5
- 239000003999 initiator Substances 0.000 claims abstract description 4
- 239000000376 reactant Substances 0.000 claims abstract description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 239000000843 powder Substances 0.000 claims description 13
- 240000003183 Manihot esculenta Species 0.000 claims description 10
- 235000016735 Manihot esculenta subsp esculenta Nutrition 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 9
- 240000008042 Zea mays Species 0.000 claims description 8
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 claims description 8
- 235000002017 Zea mays subsp mays Nutrition 0.000 claims description 8
- 235000005822 corn Nutrition 0.000 claims description 8
- 238000002844 melting Methods 0.000 claims description 7
- 230000008018 melting Effects 0.000 claims description 7
- 239000010902 straw Substances 0.000 claims description 7
- 229920000168 Microcrystalline cellulose Polymers 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 235000019813 microcrystalline cellulose Nutrition 0.000 claims description 5
- 239000008108 microcrystalline cellulose Substances 0.000 claims description 5
- 229940016286 microcrystalline cellulose Drugs 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 150000002148 esters Chemical class 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 238000002386 leaching Methods 0.000 claims description 4
- 238000007873 sieving Methods 0.000 claims description 4
- 229920001046 Nanocellulose Polymers 0.000 claims description 3
- 238000010411 cooking Methods 0.000 claims description 3
- 235000013312 flour Nutrition 0.000 claims description 3
- 229920002472 Starch Polymers 0.000 claims description 2
- 239000008107 starch Substances 0.000 claims description 2
- 235000019698 starch Nutrition 0.000 claims description 2
- -1 itaconic acid ester Chemical class 0.000 abstract description 2
- 238000012360 testing method Methods 0.000 description 9
- 238000001125 extrusion Methods 0.000 description 3
- 238000005469 granulation Methods 0.000 description 3
- 230000003179 granulation Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000007857 degradation product Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000011846 petroleum-based material Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- 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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/06—Biodegradable
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Biological Depolymerization Polymers (AREA)
Abstract
The invention discloses a bio-based polylactic acid composite material which is prepared from the following components in parts by weight: 81.0-92.0 parts of graft modified polylactic acid, 34.0-55.0 parts of bio-based filler, 12.0-16.0 parts of modified nano-cellulose and 2.0-5.0 parts of calcium carbonate. The graft modified polylactic acid is prepared from itaconic acid ester and polylactic acid according to the mass ratio of 1-1.5: 3-5 is prepared by grafting according to the following method: dispersing itaconate and polylactic acid in deionized water of 2-3 times, adding an initiator of 0.05-0.1 time of the weight of the polylactic acid, and reacting at 20-35 ℃ for 10-20 hours. Soaking the obtained reactant in 35% ethanol solution for 10-15 h, and drying in a forced air oven at 50 ℃ for 24 h to obtain the copolymer of itaconate and polylactic acid.
Description
Technical Field
The invention relates to the technical field of bio-based composite materials, in particular to a bio-based polylactic acid composite material.
Background
Polylactic acid is a thermoplastic polyester with good biocompatibility, biodegradability and processability, is greatly researched and developed due to the fact that the polylactic acid is derived from biomass and degradation products are non-toxic and harmless, and is used as an environment-friendly material to replace a traditional petroleum-based material.
However, the tensile property test and the impact resistance of the existing polylactic acid-based composite material are mostly not ideal, and therefore, the application range of the composite material is greatly limited. At present, the mechanical property of the polylactic acid-based composite material is improved mostly by compounding organic high molecular polymers, however, the degradation property and the use safety performance of the material are adversely affected.
Disclosure of Invention
In order to overcome the defects, the invention aims to provide a bio-based polylactic acid composite material which is prepared from the following components in parts by weight:
81.0 to 92.0 portions of graft modified polylactic acid,
34.0 to 55.0 portions of bio-based filler,
12.0 to 16.0 portions of modified nano-cellulose,
2.0-5.0 parts of calcium carbonate.
Further, the modified nanocellulose is prepared according to the following method: mixing microcrystalline cellulose in a ratio of 1: 5, soaking in 5 percent NaOH solution at 60-80 ℃ for 3-5 h, homogenizing at 1000-5000 rpm for 10-30 min, centrifuging, repeatedly centrifuging and washing for 2-3 times, adding deionized water for dispersing, and homogenizing at 4000-7000 rpm for 20-40 min to obtain the modified nano-cellulose.
Further, the bio-based filler comprises 22.0-35.0 parts of cassava flour and 12.0-20.0 parts of corn straw powder.
Furthermore, the polylactic acid is itaconic ester graft modified polylactic acid, and the mass ratio of the itaconic ester to the polylactic acid is 1-1.5: 3-5, and connecting according to the following method: dispersing itaconate and polylactic acid in deionized water of 2-3 times, adding an initiator of 0.05-0.1 time of the weight of the polylactic acid, and reacting at 20-35 ℃ for 10-20 hours.
Further, the obtained reactant is soaked in 35% ethanol solution for 10-15 h, and then dried in a forced air oven at 50 ℃ for 24 h to obtain the copolymer of the itaconate and the polylactic acid.
Further, the preparation method comprises the following steps:
pretreatment of bio-based filler: and (3) cooking the cassava powder and the corn straw powder for 2-4 h, leaching in a 50% ethanol solution for 1-2 d, filtering, drying, crushing, and sieving with a 40-100-mesh sieve to obtain the cassava starch.
And secondly, uniformly mixing the pretreated bio-based filler, the copolymer of the itaconate and the polylactic acid, the modified nano-cellulose and the calcium carbonate.
Melting, extruding, bracing, air cooling and granulating by using a double-screw extruder to obtain the bio-based polylactic acid composite material, wherein the length-diameter ratio of screws of the double-screw extruder is 29: 1-35: 1, the melting temperature of the double-screw extruder is 180-230 ℃.
The invention has the following beneficial effects: the bio-based polylactic acid composite material is prepared from bio-based raw materials, is environment-friendly, high in use safety, good in tensile property and impact resistance, and high in tensile toughness up to 80MJ/m3Above, the notch impact strength is as high as 81kJ/m2The above.
Detailed Description
The present invention is described in detail below with reference to examples so that the advantages and features of the present invention can be more easily understood by those skilled in the art, and thus the scope of the present invention can be clearly and clearly defined.
The bio-based polylactic acid composite material is prepared from the following components in parts by weight:
81.0 to 92.0 portions of graft modified polylactic acid,
34.0 to 55.0 portions of bio-based filler,
12.0 to 16.0 portions of modified nano-cellulose,
2.0 to 5.0 portions of calcium carbonate,
the graft modified polylactic acid is prepared from itaconic acid ester and polylactic acid according to the mass ratio of 1-1.5: 3-5 is prepared by grafting according to the following method: dispersing itaconate and polylactic acid in deionized water of 2-3 times, adding an initiator of 0.05-0.1 time of the weight of the polylactic acid, and reacting at 20-35 ℃ for 10-20 hours. Soaking the obtained reactant in 35% ethanol solution for 10-15 h, and drying in a forced air oven at 50 ℃ for 24 h to obtain the copolymer of itaconate and polylactic acid.
The modified nanocellulose is prepared according to the following method: mixing microcrystalline cellulose in a ratio of 1: 5, soaking in 5 percent NaOH solution at 60-80 ℃ for 3-5 h, homogenizing at 1000-5000 rpm for 10-30 min, centrifuging, repeatedly centrifuging and washing for 2-3 times, adding deionized water for dispersing, and homogenizing at 4000-7000 rpm for 20-40 min to obtain the modified nano-cellulose.
The bio-based filler comprises 22.0-35.0 parts of cassava flour and 12.0-20.0 parts of corn straw powder.
The bio-based polylactic acid composite material is prepared by the following method:
step one, pretreatment of bio-based filler: steaming cassava powder and corn stalk powder for 2-4 h, leaching in 50% ethanol solution for 1-2 d, filtering, oven drying, pulverizing, and sieving with 40-100 mesh sieve.
Step two, uniformly mixing the pretreated bio-based filler, the copolymer of itaconate and polylactic acid, the modified nano-cellulose and calcium carbonate;
and step three, carrying out melt extrusion, bracing, air cooling and granulation by using a double-screw extruder to prepare the bio-based polylactic acid composite material, wherein the length-diameter ratio of screws of the double-screw extruder is 29: 1-35: 1, the melting temperature of the double-screw extruder is 180-230 ℃.
The following will explain the preparation process of the bio-based polylactic acid composite material of the present invention with reference to the specific examples:
the first embodiment is as follows:
preparing graft modified polylactic acid: the mass ratio of the itaconate to the polylactic acid is 1: 3 was prepared according to the method described previously.
Preparing modified nano-cellulose: mixing microcrystalline cellulose in a ratio of 1: 5, soaking in 5 percent NaOH solution at 60-80 ℃ for 3-5 h, homogenizing at 1000-5000 rpm for 10-30 min, centrifuging, repeatedly centrifuging and washing for 2-3 times, adding deionized water for dispersing, and homogenizing at 4000-7000 rpm for 20-40 min to obtain the modified nano-cellulose.
Thirdly, after cooking 22.0 parts of cassava powder and 12.0 parts of corn straw powder for 2-4 hours, leaching in 50% ethanol solution for 1-2 days, filtering, drying and crushing, and sieving with a 40-100 mesh sieve.
81 parts of copolymer of the itaconate and the polylactic acid in the step I, 12 parts of the modified nano-cellulose in the step II, and 2 parts of the pretreated bio-based filler and the calcium carbonate in the step III are uniformly mixed;
utilizing a double-screw extruder to perform melt extrusion, bracing, air cooling and granulation to prepare the bio-based polylactic acid composite material, wherein the length-diameter ratio of screws of the double-screw extruder is 29: 1-35: 1, the melting temperature of the double-screw extruder is 180-230 ℃.
The bio-based polylactic acid composite material of the present example was subjected to a tensile property test and an impact resistance test.
And (3) testing tensile property:
first, the sample was hot-pressed at 200 ℃ into a sheet of 0.5mm thickness and cut into a specific shape as a test sample, and a tensile test was conducted at a tensile rate of 5 mm/min.
And (3) testing the impact resistance:
the composite material of this example was hot-pressed into a 5mm x 8mm x 50mm sample strip, and a V-shaped notch was made in the middle of the sample strip as a test sample. An impact force was applied to the V-notch region of each sample strip at 25 ℃, and the magnitude of the impact force at which the sample was crushed was recorded.
Example two:
preparing graft modified polylactic acid: the mass ratio of the itaconate to the polylactic acid is 1: 4 prepared according to the method described previously.
Preparing modified nano-cellulose: mixing microcrystalline cellulose in a ratio of 1: 5, soaking in 5 percent NaOH solution at 60-80 ℃ for 3-5 h, homogenizing at 1000-5000 rpm for 10-30 min, centrifuging, repeatedly centrifuging and washing for 2-3 times, adding deionized water for dispersing, and homogenizing at 4000-7000 rpm for 20-40 min to obtain the modified nano-cellulose.
Thirdly, 28 parts of the cassava powder and 15 parts of the corn straw powder are steamed and boiled for 2 to 4 hours, then are leached in 50 percent ethanol solution for 1 to 2 days, and are filtered, dried and crushed, and then are sieved by a sieve with 40 to 100 meshes.
Fourthly, uniformly mixing 88 parts of copolymer of the itaconate and the polylactic acid in the first step, 15 parts of modified nano-cellulose in the second step, and 5 parts of pretreated bio-based filler and calcium carbonate in the third step;
utilizing a double-screw extruder to perform melt extrusion, bracing, air cooling and granulation to prepare the bio-based polylactic acid composite material, wherein the length-diameter ratio of screws of the double-screw extruder is 29: 1-35: 1, the melting temperature of the double-screw extruder is 180-230 ℃.
The bio-based polylactic acid composite material of the present example was subjected to tensile property test and impact resistance test, and the test methods were performed with reference to example one.
The results of the performance test on the bio-based polylactic acid composite materials D of the first embodiment and the second embodiment are as follows:
| tensile toughness (MJ/m)3) | Notched impact strength (kJ/m)2) | |
| Example one | 82.3 | 81.0 |
| Example two | 85.6 | 86.3 |
The above embodiments are merely illustrative of the technical concept and features of the present invention, and the present invention is not limited thereto, and any equivalent changes or modifications made according to the spirit of the present invention should be included in the scope of the present invention.
Claims (6)
1. The bio-based polylactic acid composite material is characterized by being prepared from the following components in parts by weight:
81.0 to 92.0 portions of graft modified polylactic acid,
34.0 to 55.0 portions of bio-based filler,
12.0 to 16.0 portions of modified nano-cellulose,
2.0-5.0 parts of calcium carbonate.
2. The bio-based polylactic acid composite material according to claim 1, wherein the modified nanocellulose is prepared by the following method: mixing microcrystalline cellulose in a ratio of 1: 5, soaking in 5 percent NaOH solution at 60-80 ℃ for 3-5 h, homogenizing at 1000-5000 rpm for 10-30 min, centrifuging, repeatedly centrifuging and washing for 2-3 times, adding deionized water for dispersing, and homogenizing at 4000-7000 rpm for 20-40 min to obtain the modified nano-cellulose.
3. The bio-based polylactic acid composite material according to claim 1, wherein the bio-based filler comprises 22.0 to 35.0 parts of tapioca flour and 12.0 to 20.0 parts of corn straw powder.
4. The bio-based polylactic acid composite material according to any one of claims 1 to 3, wherein the polylactic acid is itaconic ester graft-modified polylactic acid, and the mass ratio of itaconic ester to polylactic acid is 1-1.5: 3-5, and connecting according to the following method: dispersing itaconate and polylactic acid in deionized water of 2-3 times, adding an initiator of 0.05-0.1 time of the weight of the polylactic acid, and reacting at 20-35 ℃ for 10-20 hours.
5. The bio-based polylactic acid composite material according to claim 4, wherein the obtained reactant is soaked in 35% ethanol solution for 10-15 h, and then dried in a 50 ℃ forced air oven for 24 h to obtain the copolymer of itaconate and polylactic acid.
6. The bio-based polylactic acid composite material according to claim 5, which is prepared by the following method:
pretreatment of bio-based filler: and (3) cooking the cassava powder and the corn straw powder for 2-4 h, leaching in a 50% ethanol solution for 1-2 d, filtering, drying, crushing, and sieving with a 40-100-mesh sieve to obtain the cassava starch.
And secondly, uniformly mixing the pretreated bio-based filler, the copolymer of the itaconate and the polylactic acid, the modified nano-cellulose and the calcium carbonate.
Melting, extruding, bracing, air cooling and granulating by using a double-screw extruder to obtain the bio-based polylactic acid composite material, wherein the length-diameter ratio of screws of the double-screw extruder is 29: 1-35: 1, the melting temperature of the double-screw extruder is 180-230 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110043182.0A CN112852088A (en) | 2021-01-13 | 2021-01-13 | Bio-based polylactic acid composite material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110043182.0A CN112852088A (en) | 2021-01-13 | 2021-01-13 | Bio-based polylactic acid composite material |
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| Publication Number | Publication Date |
|---|---|
| CN112852088A true CN112852088A (en) | 2021-05-28 |
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| CN202110043182.0A Pending CN112852088A (en) | 2021-01-13 | 2021-01-13 | Bio-based polylactic acid composite material |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107698714A (en) * | 2017-11-01 | 2018-02-16 | 宁波家联科技股份有限公司 | A kind of itaconic anhydride grafted polylactic acid copolymer and its preparation method and application |
| CN107759990A (en) * | 2017-11-01 | 2018-03-06 | 宁波家联科技股份有限公司 | A kind of full biological poly lactic acid composite and preparation method thereof |
-
2021
- 2021-01-13 CN CN202110043182.0A patent/CN112852088A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107698714A (en) * | 2017-11-01 | 2018-02-16 | 宁波家联科技股份有限公司 | A kind of itaconic anhydride grafted polylactic acid copolymer and its preparation method and application |
| CN107759990A (en) * | 2017-11-01 | 2018-03-06 | 宁波家联科技股份有限公司 | A kind of full biological poly lactic acid composite and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| K.I.KU ET AL.: "Modification of poly(lactic acid) using itaconic anhydride by reactive extrusion", 《EUROPEAN POLYMER JOURNAL》 * |
| 鲁婷菊: "纤维素增强聚合物复合材料的制备与力学性能研究", 《中国优秀博硕士学位论文全文数据库（硕士） 工程科技I辑》 * |
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