CN108948689B - Polylactic acid-lignin composite material modified by reactive extrusion method and preparation method thereof - Google Patents
Polylactic acid-lignin composite material modified by reactive extrusion method and preparation method thereof Download PDFInfo
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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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- 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
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F289/00—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds not provided for in groups C08F251/00 - C08F287/00
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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
- 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
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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
- 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
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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
- C08L97/00—Compositions of lignin-containing materials
- C08L97/005—Lignin
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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
- C08L2201/00—Properties
- C08L2201/06—Biodegradable
Abstract
The invention discloses a reaction extrusion modified polylactic acid-lignin composite material and a preparation method thereof, wherein the composite material comprises the following components in parts by weight: 100 parts of polylactic acid, 40-100 parts of lignin, 0.01-5 parts of initiator, 0.01-15 parts of reaction monomer and 0.1-1 part of antioxidant. The preparation method of the composite material comprises the following steps: firstly, the ingredients are mixed according to the composition of the composite material, the ingredients are uniformly mixed according to the proportion, and then the blend is placed in a reaction device for reaction, so that the polylactic acid-lignin composite material is prepared. Compared with the prior art, the invention can effectively enhance the compatibility of the polylactic acid-lignin composite material, endow the material with good performance and reduce the cost.
Description
Technical Field
The invention belongs to the field of high polymer materials, particularly relates to a preparation method of a grafting modified and bio-based material composite material, and particularly relates to a polylactic acid-lignin composite material modified by a reactive extrusion method and a preparation method thereof.
Background
Polylactic acid (PLA) is an important lactic acid derivative, is a polymer material synthesized by using lactic acid as a raw material, has good biodegradability, no toxicity, no pungent smell, excellent biocompatibility, high strength and strong plasticity, and is popular in the polymer material industry. But PLA has the performance characteristics of poor brittleness, easy bending deformation and the like; further, the chemical structure of PLA lacks reactive functional groups and is not hydrophilic, and therefore further modification is required. The polylactic acid is generally modified by chemical modification or physical modification. The chemical modification is to change the chemical structure of PLA by introducing various functional side groups through grafting, crosslinking and other ways; the physical modification is to change the mechanical property, thermal property and the like of the PLA by adding a plasticizer, various inorganic and organic materials and the like.
Lignin is a three-dimensional network structure natural aromatic compound which takes phenylpropane as a structural unit and is highly crosslinked through carbon-carbon bonds and ether bonds. At present, lignin is a byproduct of paper making industry, has good biodegradability, a PLA-lignin composite material has complete degradability and is a completely environment-friendly material, and the PLA-lignin is undoubtedly a promising high-molecular composite material under the environment of environment protection which is vigorously advocated in various countries in the world. The rigidity of PLA can be increased by adding lignin into the PLA, and the toughness can meet daily use conditions after grafting modification.
Currently, methods of PLA-modified manufacturing processes have been reported to improve their overall performance, such as Robertson et al [ Robertson M l.toughening of polylactic with polymerized soybean oil [ J ]. Macromolecules, 2010, 43 (4): 1807-; hijiang [ hijiang, lvxinming, luxiahua ] hexamethylenediamine grafted polylactic acid hydrophilic modification study [ J ] shihezi university report (nature science edition) 2009, 27 (6): 755-758- ] taking lactic acid, maleic anhydride and ethylenediamine as raw materials to synthesize the ethylenediamine modified PLA, and determining the optimal process conditions: the reaction is carried out for 2 hours at 10 ℃, and the yield and the product purity are highest when the ethylenediamine is excessive by 20 percent.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides a PLA-lignin composite material modified by a reactive extrusion method and a preparation method thereof, and the PLA-lignin composite material is simple to operate and has good comprehensive performance.
In order to achieve the purpose, the invention adopts the following technical scheme:
on one hand, the invention provides a reaction extrusion method modified polylactic acid-lignin composite material, which comprises the following components in parts by weight:
in order to further optimize the above technical solution, the technical measures taken by the present invention further include:
preferably, the lignin is an aromatic high polymer containing structural units of the oxo-phenylpropanol or the derivative thereof in a molecular structure, and the particle size of the aromatic high polymer is 50-500 meshes.
Preferably, the initiator is a peroxide initiator; more preferably, the initiator is one or more of dicumyl peroxide, di-tert-butylperoxyisopropyl benzene, tert-butyl peroxybenzoate, tert-butyl peroxydicarbonate, tert-butyl hydroperoxide, 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) hexane and benzoyl peroxide.
Preferably, the reactive monomer is one or more of maleic anhydride, acrylic acid and glycidyl methacrylate.
Preferably, the antioxidant is a phenolic antioxidant, such as 1010.
On the other hand, the invention also provides a preparation method of the polylactic acid-lignin composite material modified by the reactive extrusion method, which comprises the following steps:
firstly, weighing 100 parts of PLA and 40-100 parts of lignin in proportion, and uniformly mixing at normal temperature;
and (2) uniformly mixing 0.01-5 parts by weight of initiator, 0.01-15 parts by weight of reaction monomer and 0.1-1 part by weight of antioxidant, adding the mixture and the polylactic acid/lignin mixture obtained in the step (1) into a reaction device, and blending at a preset reaction temperature to obtain the polylactic acid-lignin composite material.
Preferably, the reaction equipment is at least one of an internal mixer and a reaction type extruder, the reaction temperature is 150-190 ℃, the rotor speed of the internal mixer is 50-200rpm, and the screw speed of the reaction type extruder is 100-600 rpm.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the polylactic acid-lignin composite material prepared by the invention has good comprehensive mechanical property;
(2) compared with other preparation methods, the preparation method is simple to operate and good in effect;
(3) the invention organically combines the biodegradable paper making byproduct, namely lignin, and the biodegradable plastic polylactic acid to manufacture the completely biodegradable plastic, thereby not only fully utilizing the paper making byproduct, namely lignin, but also improving the comprehensive mechanical property of the polylactic acid;
(4) the preparation method does not involve the use of a solvent at all in the preparation process of the polylactic acid-lignin composite material, and all the used components are directly physically mixed by a stirrer without further treatment;
(5) the polylactic acid-lignin composite material is prepared by melt blending of an internal mixer or an extruder, and the method has the possibility of industrial large-scale production.
Detailed Description
The following further describes embodiments of the present invention with reference to examples. The following examples are only for illustrating the technical solutions of the present invention more clearly, and the protection scope of the present invention is not limited thereby.
Example 1
A preparation method of a PLA-lignin composite material modified by a reactive extrusion method comprises the following steps of:
wherein the lignin is aromatic high polymer containing structural unit of oxyphenbutamol or its derivatives in molecular structure, and has particle size of 50-500 mesh.
The above formula is reacted according to the following steps:
firstly, weighing PLA and lignin in proportion, and uniformly mixing at normal temperature;
and (2) uniformly mixing the weighed DCP, GMA and 1010, adding the mixture of the weighed DCP, GMA and 1010 and a mixture of PLA and lignin into a reaction type extruder, setting the temperature of the extruder to be 150 ℃, setting the rotating speed of a screw to be 400RPM, and extruding and granulating to obtain the PLA-lignin composite material particles.
And (3) performing injection molding on the composite material particles (the injection molding temperature is 160-180 ℃, the injection molding pressure is 40-80MPa, the injection molding speed is 50-150mm/S, the pressure maintaining pressure is 40-50MPa, the pressure maintaining time is 5S, and the cooling time is 15S) to prepare a standard test sample strip for later use.
Example 2
A preparation method of a PLA-lignin composite material modified by a reactive extrusion method comprises the following steps of:
wherein the lignin is aromatic high polymer containing structural unit of oxyphenbutamol or its derivatives in molecular structure, and has particle size of 50-500 mesh.
The above formula is reacted according to the following steps:
firstly, weighing PLA and lignin in proportion, and uniformly mixing at normal temperature;
and (2) uniformly mixing the weighed DCP, GMA and 1010, adding the mixture of the weighed DCP, GMA and 1010 and a mixture of PLA and lignin into a reaction type extruder, setting the temperature of the extruder to be 190 ℃ and the rotating speed of a screw to be 300RPM, and extruding and granulating to obtain the PLA-lignin composite material particles.
The composite particles were injection molded (same injection molding process as in example 1) to prepare a standard test specimen for use.
Example 3
A preparation method of a PLA-lignin composite material modified by a reactive extrusion method comprises the following steps of:
wherein the lignin is aromatic high polymer containing structural unit of oxyphenbutamol or its derivatives in molecular structure, and has particle size of 50-500 mesh.
The above formula is reacted according to the following steps:
firstly, weighing PLA and lignin in proportion, and uniformly mixing at normal temperature;
and (2) uniformly mixing the weighed DCP, GMA and 1010, adding the mixture of the weighed DCP, GMA and 1010 and a mixture of PLA and lignin into a reaction type extruder, setting the temperature of the extruder to be 160 ℃, setting the rotating speed of a screw to be 100RPM, and extruding and granulating to obtain the PLA-lignin composite material particles.
The composite particles were injection molded (same injection molding process as in example 1) to prepare a standard test specimen for use.
Example 4
A preparation method of a PLA-lignin composite material modified by a reactive extrusion method comprises the following steps of:
wherein the lignin is aromatic high polymer containing structural unit of oxyphenbutamol or its derivatives in molecular structure, and has particle size of 50-500 mesh.
The above formula is reacted according to the following steps:
firstly, weighing PLA and lignin in proportion, and uniformly mixing at normal temperature;
and (2) uniformly mixing the weighed DCP, GMA and 1010, adding the mixture of the weighed DCP, GMA and 1010 and a mixture of PLA and lignin into a reaction type extruder, setting the temperature of the extruder at 180 ℃, setting the rotating speed of a screw at 600RPM, and extruding and granulating to obtain the PLA-lignin composite material particles.
The composite particles were injection molded (same injection molding process as in example 1) to prepare a standard test specimen for use.
Example 5
A preparation method of a PLA-lignin composite material modified by a reactive extrusion method comprises the following steps of:
wherein the lignin is aromatic high polymer containing structural unit of oxyphenbutamol or its derivatives in molecular structure, and has particle size of 50-500 mesh.
The above formula is reacted according to the following steps:
firstly, weighing PLA and lignin in proportion, and uniformly mixing at normal temperature;
and (2) uniformly mixing the weighed DCP, GMA and 1010, adding the mixture of the weighed DCP, GMA and 1010 and a mixture of PLA and lignin into a reaction type extruder, setting the temperature of the extruder to be 170 ℃, setting the rotating speed of a screw to be 300RPM, and extruding and granulating to obtain the PLA lignin composite material particles.
The composite particles were injection molded (same injection molding process as in example 1) to prepare a standard test specimen for use.
Tensile strength, elongation at break and impact strength of the samples finally prepared in examples 1 to 5 were measured using an all-purpose electronic tensile testing machine (KY800C, manufactured by kayaku-shi koku corporation) and an electronic impact testing machine (manufactured by shandong anniemai instruments ltd.) using unmodified polylactic acid and unmodified polylactic acid/lignin (simply blended by polylactic acid and lignin) as comparative examples, and the results are shown in table 1:
TABLE 1
The result shows that the PLA-lignin composite material modified by the reactive extrusion method has obviously improved performance.
Example 6
A preparation method of a PLA-lignin composite material modified by a reactive extrusion method comprises the following steps of:
wherein the lignin is aromatic high polymer containing structural unit of oxyphenbutamol or its derivatives in molecular structure, and has particle size of 50-500 mesh.
The reaction procedure for the above formulation and the preparation of standard test bars were the same as in example 1.
Example 7
A preparation method of a PLA-lignin composite material modified by a reactive extrusion method comprises the following steps of:
wherein the lignin is aromatic high polymer containing structural unit of oxyphenbutamol or its derivatives in molecular structure, and has particle size of 50-500 mesh.
The reaction procedure for the above formulation and the preparation of standard test bars were the same as in example 5.
Example 8
A preparation method of a PLA-lignin composite material modified by a reactive extrusion method comprises the following steps of:
wherein the lignin is aromatic high polymer containing structural unit of oxyphenbutamol or its derivatives in molecular structure, and has particle size of 50-500 mesh.
The reaction procedure for the above formulation and the preparation of standard test bars were the same as in example 4.
The performance of the finally prepared samples in the above embodiments 6 to 8 is superior to that of the prior art.
The embodiments of the present invention have been described in detail, but the embodiments are merely examples, and the present invention is not limited to the embodiments described above. Any equivalent modifications and substitutions to those skilled in the art are also within the scope of the present invention. Accordingly, equivalent changes and modifications made without departing from the spirit and scope of the present invention should be covered by the present invention.
Claims (6)
1. A polylactic acid-lignin composite material modified by a reactive extrusion method is characterized by comprising the following components in parts by weight:
the preparation method of the polylactic acid-lignin composite material modified by the reactive extrusion method comprises the following steps:
firstly, weighing 100 parts of polylactic acid and 40-100 parts of lignin according to a proportion, and uniformly mixing at normal temperature;
step (2) uniformly mixing 0.01-5 parts by weight of initiator, 0.01-15 parts by weight of reaction monomer and 0.1-1 part by weight of antioxidant, adding the mixture and the polylactic acid/lignin mixture obtained in the step (1) into a reaction device, and blending at the preset reaction temperature of 150-190 ℃ to obtain the polylactic acid-lignin composite material;
the reaction monomer is one or two of acrylic acid and glycidyl methacrylate.
2. The polylactic acid-lignin composite material modified by the reaction extrusion method according to claim 1, wherein the lignin is an aromatic high polymer containing structural units of oxyphenbutamol or derivatives thereof in a molecular structure, and the particle size is 50-500 meshes.
3. The reactive extrusion modified polylactic acid-lignin composite material according to claim 1, wherein the initiator is a peroxide initiator.
4. The reactive extrusion modified polylactic acid-lignin composite material according to claim 1, wherein the initiator is one or more of dicumyl peroxide, di-tert-butylperoxyisopropyl benzene, tert-butyl peroxybenzoate, tert-butyl peroxydicarbonate, tert-butyl hydroperoxide, 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) hexane and benzoyl peroxide.
5. The reactive extrusion modified polylactic acid-lignin composite material as claimed in claim 1, wherein the antioxidant is phenolic antioxidant.
6. The reactive extrusion modified polylactic acid-lignin composite material as claimed in claim 1, wherein the reaction equipment is at least one of an internal mixer and a reactive extruder, wherein the rotor speed of the internal mixer is 50-200rpm, and the screw speed of the reactive extruder is 100-600 rpm.
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| CN110734631B (en) * | 2019-11-15 | 2022-02-18 | 湖南骏泰新材料科技有限责任公司 | Lignin-based biodegradable polybutylene succinate film and preparation method thereof |
| CN110938291A (en) * | 2019-12-12 | 2020-03-31 | 湖南绿燊环保科技有限公司 | Polylactic acid composite material and preparation method thereof |
| CN110903626B (en) * | 2019-12-12 | 2022-10-14 | 湖南绿燊环保科技有限公司 | Polycarbonate composite material and preparation method thereof |
| CN114685961B (en) * | 2020-12-29 | 2024-04-05 | 中国石油化工股份有限公司 | Modified polylactic acid film material |
| CN114874446A (en) * | 2022-06-22 | 2022-08-09 | 南京塑净新材料科技有限公司 | Special efficient nucleating agent for lignin grafted polylactic acid and preparation method and application thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102093681A (en) * | 2010-12-24 | 2011-06-15 | 中科院广州化学有限公司 | Toughness-increasing polylactic acid composite material and preparation method thereof |
| CN104861599A (en) * | 2015-05-13 | 2015-08-26 | 常州龙骏天纯环保科技有限公司 | Degradable polylactic acid compound and preparation method thereof |
| CN104893008A (en) * | 2015-05-08 | 2015-09-09 | 常州龙骏天纯环保科技有限公司 | Preparation method for esterified starch/polylactic acid composite material |
| CN106589855A (en) * | 2016-12-21 | 2017-04-26 | 济宁明升新材料有限公司 | Lignin modified whole bio-based PBAT biodegradable plastic and preparation method thereof |
| CN106589854A (en) * | 2016-12-21 | 2017-04-26 | 济宁明升新材料有限公司 | Lignin-modified whole bio-based PBSA biodegradable plastic and preparation method thereof |
| CN106589871A (en) * | 2016-12-21 | 2017-04-26 | 济宁明升新材料有限公司 | Lignin modified PHA biodegradable plastic and preparing method thereof |
-
2017
- 2017-05-17 CN CN201710349779.1A patent/CN108948689B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102093681A (en) * | 2010-12-24 | 2011-06-15 | 中科院广州化学有限公司 | Toughness-increasing polylactic acid composite material and preparation method thereof |
| CN104893008A (en) * | 2015-05-08 | 2015-09-09 | 常州龙骏天纯环保科技有限公司 | Preparation method for esterified starch/polylactic acid composite material |
| CN104861599A (en) * | 2015-05-13 | 2015-08-26 | 常州龙骏天纯环保科技有限公司 | Degradable polylactic acid compound and preparation method thereof |
| CN106589855A (en) * | 2016-12-21 | 2017-04-26 | 济宁明升新材料有限公司 | Lignin modified whole bio-based PBAT biodegradable plastic and preparation method thereof |
| CN106589854A (en) * | 2016-12-21 | 2017-04-26 | 济宁明升新材料有限公司 | Lignin-modified whole bio-based PBSA biodegradable plastic and preparation method thereof |
| CN106589871A (en) * | 2016-12-21 | 2017-04-26 | 济宁明升新材料有限公司 | Lignin modified PHA biodegradable plastic and preparing method thereof |
Non-Patent Citations (1)
| Title |
|---|
| ＭＡＨ对干法酯化淀粉／ＰＬＡ复合材料性能的影响;左迎峰，顾继友，杨龙，谭海彦，张彦华;《复合材料学报》;20141231;第31卷(第6期);第1436-1445页 * |
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