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CN111057355A - A kind of porous cellulose PLA composite material and preparation method thereof - Google Patents

A kind of porous cellulose PLA composite material and preparation method thereof Download PDF

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Publication number
CN111057355A
CN111057355A CN201911139436.8A CN201911139436A CN111057355A CN 111057355 A CN111057355 A CN 111057355A CN 201911139436 A CN201911139436 A CN 201911139436A CN 111057355 A CN111057355 A CN 111057355A
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China
Prior art keywords
porous cellulose
composite material
pla
preparation
parts
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CN201911139436.8A
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Chinese (zh)
Inventor
曾广胜
江太君
孟聪
胡灿
陈一
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Hunan Lingyue New Material Co ltd
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Hunan University of Technology
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Priority to CN201911139436.8A priority Critical patent/CN111057355A/en
Publication of CN111057355A publication Critical patent/CN111057355A/en
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/04Polyesters derived from hydroxycarboxylic acids, e.g. lactones
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00Properties
    • C08L2201/06Biodegradable
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/03Polymer mixtures characterised by other features containing three or more polymers in a blend

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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)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

本发明公开了一种多孔纤维素PLA复合材料及其制备方法,以多孔纤维素、PLA、PBAT和抗氧剂为原材料制备而成。本发明将植物纤维通过碱液处理后形的多孔纤维素与PLA及PBAT进行共混造粒制备全降解复合材料,复合材料因多孔纤维的存在,树脂基体可以渗透入多孔纤维素的微孔内形成异型微观结构增强复合材料的物理机械性能。The invention discloses a porous cellulose PLA composite material and a preparation method thereof, which are prepared by using porous cellulose, PLA, PBAT and antioxidants as raw materials. In the present invention, the porous cellulose formed by the alkaline solution is mixed with PLA and PBAT for granulation to prepare a fully degradable composite material. Due to the existence of the porous fiber, the resin matrix can penetrate into the micropores of the porous cellulose. Formation of heteromorphic microstructures enhances the physical and mechanical properties of composites.

Description

Porous cellulose PLA composite material and preparation method thereof
Technical Field
The invention relates to the technical field of composite materials, and particularly relates to a porous cellulose PLA composite material and a preparation method thereof.
Background
Plant fiber is a natural renewable resource, widely exists in agricultural and forestry resources and processing wastes thereof, is often not fully utilized and is abandoned as garbage in the nature. However, the plant fiber contains a large amount of hemicellulose, pectin, lignin and minerals besides a large amount of natural cellulose components, and the components can affect the performance of the composite material, so that the performance of the wood-plastic composite material is limited and difficult to be improved continuously. The cellulose has higher strength as a main component in the plant fiber, and can be used for preparing a composite material with more excellent performance. Meanwhile, the natural cellulose can be used for preparing cellulose derivatives such as methylcellulose, hydroxypropyl methylcellulose, hydroxyethyl cellulose and the like, and can be further applied to the fields of medical treatment, building materials, high-strength composite materials and the like to improve the application value again.
The plant fiber and the thermoplastic composite material are blended to prepare the environment-friendly composite material with certain biochar content, and then the plant fiber in the material contains a large amount of lignin and other components which have negative effects on the improvement of mechanical properties. If the cellulose in the plant fiber can be extracted and compounded with thermoplastic composite material, especially PLA which can be degraded by full biomass, the composite material with higher physical and mechanical properties can be prepared.
Disclosure of Invention
The invention aims to provide a porous cellulose PLA composite material aiming at the defects in the prior art, the purity of plant fibers is high, and the physical and mechanical properties of the composite material are improved.
Another object of the present invention is to provide a method for preparing the above porous cellulose PLA composite material.
The purpose of the invention is realized by the following technical scheme:
a porous cellulose PLA composite comprising the following components: porous cellulose: 20-50 parts of PLA: 40-70 parts of PBAT: 20-40 parts of antioxidant 1010.25-0.3 part, and 0.25-0.3 part of antioxidant 1076.
Further, the porous cellulose is at least one of straw fiber, wood fiber or bamboo fiber.
A preparation method of the porous cellulose PLA composite material comprises the following steps:
s1, placing plant fibers into an alkali solution for treatment, then ultrasonically cleaning the plant fibers with clear water, and drying the plant fibers to obtain porous cellulose;
s2, placing the porous cellulose, PLA, PBAT and antioxidant into a high-speed mixer to be mixed uniformly;
s3, putting the mixture obtained in the step S2 into a co-rotating parallel twin-screw extruder for extrusion and granulation to obtain the porous cellulose PLA composite material.
Further, in the step S1, the alkali solution is a NaOH solution with a pH of 10-12.
Further, the treatment time of the alkali solution in the step S1 is 4-12 hours.
Further, the temperature setting of the co-rotating parallel twin-screw extruder in step S3 is from blanking to die: 155-160-165-175-185-190 ℃.
Compared with the prior art, the invention has the following beneficial effects:
the invention mixes and granulates the porous cellulose processed by alkali liquor with PLA and PBAT to prepare the fully-degradable composite material, and the resin matrix can penetrate into the micropores of the porous cellulose to form the physical and mechanical properties of the special-shaped microstructure reinforced composite material due to the existence of the porous fiber.
Detailed Description
In order to facilitate understanding of the present invention, the present invention will be described in more detail with reference to the following examples, but the scope of the present invention is not limited to the following specific examples.
Unless otherwise defined, all terms of art used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention.
Unless otherwise specifically stated, various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or can be prepared by existing methods.
Example 1
The embodiment provides a preparation method of a porous cellulose PLA composite material, which comprises the following steps:
s1, placing 30-mesh bamboo fibers into a NaOH solution with the pH value of 10 to be treated for 4 hours, and then ultrasonically cleaning the bamboo fibers with clear water and drying the bamboo fibers to obtain porous cellulose;
s2, placing the porous cellulose, PLA, PBAT and the antioxidant into a high-speed mixer to be uniformly mixed, wherein the dosage of each component is as follows: porous cellulose: 30 parts and PLA: 50 parts of PBAT: 25 parts of antioxidant 1010: 0.3 part of antioxidant: 1076:0.3 parts;
s3, putting the mixture obtained in the step S2 into a co-rotating parallel double-screw extruder for extrusion granulation, wherein the temperature is set from blanking to a die: 155-160-165-175-190 ℃ to obtain the porous cellulose PLA composite material.
The tensile strength of the composite material prepared in this example was 28.6MPa, and the flexural strength was 39.2 MPa.
Example 2
The embodiment provides a preparation method of a porous cellulose PLA composite material, which comprises the following steps:
s1, putting 30-mesh straw fibers into a NaOH solution with the pH value of 12 for treatment for 10 hours, and then ultrasonically cleaning the straw fibers with clear water and drying the straw fibers to obtain porous cellulose;
s2, placing the porous cellulose, PLA, PBAT and the antioxidant into a high-speed mixer to be uniformly mixed, wherein the dosage of each component is as follows: porous cellulose: 40 parts of PLA: 60 parts, PBAT: 30 parts of antioxidant 1010:0.25 part of antioxidant: 1076:0.25 parts;
s3, putting the mixture obtained in the step S2 into a co-rotating parallel double-screw extruder for extrusion granulation, wherein the temperature is set from blanking to a die: 155-160-165-175-190 ℃ to obtain the porous cellulose PLA composite material.
The tensile strength of the composite material prepared in this example was 27.3MPa, and the flexural strength was 42.8 MPa.
Example 3
The embodiment provides a preparation method of a porous cellulose PLA composite material, which comprises the following steps:
s1, placing 30-mesh straw fibers and wood fibers into a NaOH solution with the pH value of 12 for treatment for 12 hours, wherein the ratio of the two fibers is 1:1, and then ultrasonically cleaning the two fibers with clear water and drying the two fibers to obtain porous cellulose;
s2, placing the porous cellulose, PLA, PBAT and the antioxidant into a high-speed mixer to be uniformly mixed, wherein the dosage of each component is as follows: porous cellulose: 20 parts of PLA: 70 parts, PBAT: 20 parts of antioxidant 1010: 0.3 part of antioxidant: 1076:0.25 parts;
s3, putting the mixture obtained in the step S2 into a co-rotating parallel double-screw extruder for extrusion granulation, wherein the temperature is set from blanking to a die: 155-160-165-175-190 ℃ to obtain the porous cellulose PLA composite material.
The tensile strength of the composite material prepared in this example was 26.5MPa, and the flexural strength was 44.7 MPa.
It should be understood that the above examples are only for clearly illustrating the technical solutions of the present invention, and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the claims of the present invention.

Claims (6)

1.一种多孔纤维素PLA复合材料,其特征在于,包括以下组分:多孔纤维素:20~50份、PLA:40~70份、PBAT:20~40份、抗氧化剂1010:0.25~0.3份、抗氧剂1076:0.25~0.3份。1. a porous cellulose PLA composite material, is characterized in that, comprises the following components: porous cellulose: 20~50 parts, PLA: 40~70 parts, PBAT: 20~40 parts, antioxidant 1010: 0.25~0.3 parts, antioxidant 1076: 0.25~0.3 parts. 2.根据权利要求1所述的多孔纤维素PLA复合材料,其特征在于,所述多孔纤维为秸秆纤维、木纤维或竹纤维的至少一种。2 . The porous cellulose PLA composite material according to claim 1 , wherein the porous fibers are at least one of straw fibers, wood fibers or bamboo fibers. 3 . 3.一种权利要求1或2所述的多孔纤维素PLA复合材料的制备方法,其特征在于,包括以下步骤:3. a preparation method of the described porous cellulose PLA composite material of claim 1 or 2, is characterized in that, comprises the following steps: S1.将植物纤维放入碱溶液中处理,然后用清水超声清洗后烘干;S1. Put the plant fiber into an alkaline solution for treatment, then ultrasonically clean it with clean water and dry it; S2.将处理后植物纤维和PLA、PBAT、抗氧化剂放入高混机内混合均匀;S2. Put the treated plant fibers, PLA, PBAT and antioxidants into the high mixer and mix them evenly; S3.将步骤S2中的混合物放入同向平行双螺杆挤出机挤出造粒,得多孔纤维素PLA复合材料。S3. Put the mixture in step S2 into a co-rotating parallel twin-screw extruder for extrusion and granulation to obtain a porous cellulose PLA composite material. 4.根据权利要求3所述的制备方法,其特征在于,步骤S1中所述碱溶液为PH为10~12的NaOH溶液。4. preparation method according to claim 3 is characterized in that, the alkaline solution described in step S1 is the NaOH solution that pH is 10~12. 5.根据权利要求3所述的制备方法,其特征在于,步骤S1中所述碱溶液的处理时间为4~12小时。5. The preparation method according to claim 3, wherein the treatment time of the alkaline solution in step S1 is 4 to 12 hours. 6.根据权利要求3所述的制备方法,其特征在于,步骤S3中所述同向平行双螺杆挤出机的温度设置从下料到模具:155℃~160℃~160℃~165℃~175℃~185℃~190℃~190℃~190℃~190℃~190℃。6. preparation method according to claim 3 is characterized in that, the temperature of the co-rotating parallel twin-screw extruder described in step S3 is set from blanking to die: 155 ℃~160 ℃~160 ℃~165 ℃~ 175℃~185℃~190℃~190℃~190℃~190℃~190℃.
CN201911139436.8A 2019-11-20 2019-11-20 A kind of porous cellulose PLA composite material and preparation method thereof Pending CN111057355A (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111621162A (en) * 2020-06-19 2020-09-04 杭实科技发展(杭州)有限公司 Full-biodegradable bamboo fiber high-filling polylactic acid material and preparation method thereof
CN113150521A (en) * 2021-05-08 2021-07-23 汕头市春叶新材料环保有限公司 High-toughness biodegradable composite material, and preparation device and method thereof
WO2023044959A1 (en) * 2021-09-24 2023-03-30 南京五瑞生物降解新材料研究院有限公司 All biomass, fully degradable material, preparation method therefor and application thereof
EP4477703A1 (en) * 2023-06-13 2024-12-18 FUJIFILM Business Innovation Corp. Resin composition
EP4477704A1 (en) * 2023-06-13 2024-12-18 FUJIFILM Business Innovation Corp. Porous cellulose structure and resin composition

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102618000A (en) * 2012-03-23 2012-08-01 天津大学 Crop straw and fibrilia hybrid-reinforced polylactic acid composite material and preparation method thereof
CN103421286A (en) * 2013-08-08 2013-12-04 华南理工大学 High temperature resistant and degradable polylactic acid wood plastic material and preparation method thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102618000A (en) * 2012-03-23 2012-08-01 天津大学 Crop straw and fibrilia hybrid-reinforced polylactic acid composite material and preparation method thereof
CN103421286A (en) * 2013-08-08 2013-12-04 华南理工大学 High temperature resistant and degradable polylactic acid wood plastic material and preparation method thereof

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111621162A (en) * 2020-06-19 2020-09-04 杭实科技发展(杭州)有限公司 Full-biodegradable bamboo fiber high-filling polylactic acid material and preparation method thereof
CN111621162B (en) * 2020-06-19 2022-09-27 杭实科技发展(杭州)有限公司 Full-biodegradable bamboo fiber high-filling polylactic acid material and preparation method thereof
CN113150521A (en) * 2021-05-08 2021-07-23 汕头市春叶新材料环保有限公司 High-toughness biodegradable composite material, and preparation device and method thereof
CN113150521B (en) * 2021-05-08 2022-01-25 江西昕禾生态科技有限公司 High-toughness biodegradable composite material, and preparation device and method thereof
WO2023044959A1 (en) * 2021-09-24 2023-03-30 南京五瑞生物降解新材料研究院有限公司 All biomass, fully degradable material, preparation method therefor and application thereof
EP4477703A1 (en) * 2023-06-13 2024-12-18 FUJIFILM Business Innovation Corp. Resin composition
EP4477704A1 (en) * 2023-06-13 2024-12-18 FUJIFILM Business Innovation Corp. Porous cellulose structure and resin composition

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Effective date of registration: 20211018

Address after: 410000 room 25004, phase II business complex building, Yunda Central Plaza, No. 567, Changsha Avenue, Lituo street, Yuhua District, Changsha City, Hunan Province

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Application publication date: 20200424