CN110746635A - Composite starch foaming micro-bead and preparation method thereof - Google Patents
Composite starch foaming micro-bead and preparation method thereof Download PDFInfo
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- CN110746635A CN110746635A CN201911139433.4A CN201911139433A CN110746635A CN 110746635 A CN110746635 A CN 110746635A CN 201911139433 A CN201911139433 A CN 201911139433A CN 110746635 A CN110746635 A CN 110746635A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/22—After-treatment of expandable particles; Forming foamed products
- C08J9/228—Forming foamed products
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
- C08J9/10—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
- C08J9/102—Azo-compounds
- C08J9/103—Azodicarbonamide
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
- C08J9/10—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
- C08J9/104—Hydrazines; Hydrazides; Semicarbazides; Semicarbazones; Hydrazones; Derivatives thereof
- C08J9/105—Hydrazines; Hydrazides; Semicarbazides; Semicarbazones; Hydrazones; Derivatives thereof containing sulfur
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/04—N2 releasing, ex azodicarbonamide or nitroso compound
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2303/00—Characterised by the use of starch, amylose or amylopectin or of their derivatives or degradation products
- C08J2303/02—Starch; Degradation products thereof, e.g. dextrin
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2403/00—Characterised by the use of starch, amylose or amylopectin or of their derivatives or degradation products
- C08J2403/02—Starch; Degradation products thereof, e.g. dextrin
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2467/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2467/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
Abstract
The invention discloses a composite starch foaming microbead and a preparation method thereof. According to the invention, the chemical foaming agent is added into the thermoplastic starch material and prepared into micro-particles, and then a layer of fully-degradable plastic film is coated outside the thermoplastic starch material to form the controllable foaming micro-beads, so that the preparation method can be widely applied to preparation of the full-starch or starch-based foaming composite material, and the production process is stable and controllable.
Description
Technical Field
The invention relates to the technical field of foaming materials, in particular to a composite starch foaming microbead and a manufacturing method thereof.
Background
Starch is a renewable recyclable green material from natural plants, can be used as grain for human eating, and is widely applied to the fields of chemical industry and new materials for preparing various composite materials. Due to the excellent biodegradability, starch is generally used as filling to prepare thermoplastic high-biochar-content bio-based composite materials, is widely applied to disposable products, and is more and more valued by people in the large environment that petrochemical resources are increasingly in shortage and white pollution is increasingly serious at present. The starch is used as a raw material to prepare the thermoplastic composite material, and the density of the starch is high, so that the comprehensive density of the plasticized and compacted composite material can reach about 1.4g/cm3, and the thermoplastic composite material has no advantages in the aspects of transportation and material cost accounting compared with a plastic material. The starch-based composite material is necessary to be foamed, and the composite foamed material with the density similar to or lower than that of the traditional plastic is prepared, so that the application of the starch-based composite material can be greatly expanded, the traditional plastic can be replaced in more fields, and the method has very important significance for relieving plastic pollution.
At present, two methods for foam design of starch-based composite materials are generally available, one method is to add a chemical foaming agent, namely, the chemical foaming agent such as AC is added into the formula of the homogenized starch-based composite material, and the chemical foaming agent is heated and decomposed to release gas and uniformly disperse the gas in the composite material in the forming process, the gas is developed into bubbles under the action of a nucleating agent, and pores are formed in the composite material, so that the foam material with a cell structure is formed, and the technology is mainly applied to an injection molding process. The other process is physical foaming, namely, supercritical carbon dioxide or other types of gases are forced into the melt in the forming process of the molten starch-based composite material, the gases are uniformly distributed in the composite material melt under the shearing or stirring action of external force and rapidly developed into bubbles, and cells are formed in the composite material. However, the two processes have very high requirements on the blending of molding equipment and material formulas, the production process is not easy to control, and the method cannot be realized for materials with low matrix melt strength. It is necessary to design a simpler and more controllable foaming process and method to prepare the low-density starch-based composite material.
Disclosure of Invention
The invention aims to provide the composite starch foaming micro-bead which is low in density and can replace the traditional plastic aiming at the defects in the prior art.
The invention also aims to provide a preparation method of the composite starch foaming micro-bead.
The purpose of the invention is realized by the following technical scheme:
the composite starch foaming micro-bead comprises a starch foaming matrix and a fully degradable plastic film, wherein a starch foaming organism is positioned in the center of the micro-bead, and the fully degradable plastic film is coated outside the foaming matrix.
Further, the starch foaming matrix comprises thermoplastic starch and a foaming agent.
Further, the foaming agent is at least one of tosylhydrazide and azoformamide.
Further, the fully degradable plastic film is at least one of PLA, PBAT or PBS.
The preparation method of the composite starch foaming micro-beads comprises the following steps:
s1, mixing thermoplastic starch and a foaming agent at a high speed, and then uniformly mixing to obtain a starch foaming matrix;
s2, kneading and granulating the mixed starch foaming matrix in a granulator to form spherical particles to obtain foaming matrix particles;
and S3, spraying the molten degradable plastic film melt to the foaming matrix, and stirring at a high speed until the surface of the foaming matrix is uniformly coated with a layer of fully degradable plastic film to obtain the composite starch foaming microbeads.
Further, the kneading temperature in step S1 is 100 to 140 ℃.
Further, the particle diameter of the foaming base particles in the step S2 is 0.2-0.3 mm.
Compared with the prior art, the invention has the following beneficial effects:
the invention is realized by adding the thermoplastic starch materialThe chemical foaming agent is prepared into micro-particles, and then a layer of fully degradable plastic film is coated outside the micro-particles to form controllable foaming micro-beads, so that the micro-beads can be widely applied to the preparation of full starch or starch-based foaming composite materials, the diameter of the micro-beads is 0.3-0.8mm, and the density of the prepared foaming composite materials can reach 0.8-1.1g/cm3。
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 composite starch foaming microbeads, which comprises the following steps:
s1, mixing thermoplastic starch and toluenesulfonyl hydrazide at high speed, wherein the dosage of the toluenesulfonyl hydrazide is 2% of that of the thermoplastic starch, and uniformly mixing at 120 ℃ to obtain a starch foaming matrix;
s2, kneading and granulating the mixed starch foaming matrix in a granulator into spherical particles of 0.3mm to obtain foaming matrix particles;
and S3, spraying the melted PLA melt to the foaming matrix, and stirring at a high speed until the surface of the foaming matrix is uniformly coated with a layer of fully-degradable plastic film to obtain the composite starch foaming microbeads.
The microbeads prepared in this example had a particle size of 0.6mm and a density of 1.0g/cm3。
Example 2
The embodiment provides a preparation method of composite starch foaming microbeads, which comprises the following steps:
s1, mixing thermoplastic starch and toluenesulfonyl hydrazide at a high speed, wherein the dosage of the toluenesulfonyl hydrazide is 4% of that of the thermoplastic starch, and uniformly mixing at 140 ℃ to obtain a starch foaming matrix;
s2, kneading and granulating the mixed starch foaming matrix in a granulator into spherical particles of 0.2mm to obtain foaming matrix particles;
and S3, spraying the molten PBS melt to the foaming matrix, and stirring at a high speed until the surface of the foaming matrix is uniformly coated with a layer of fully-degradable plastic film to obtain the composite starch foaming microbeads.
The microbeads prepared in this example had a particle size of 0.8mm and a density of 1.0g/cm3。
Example 3
The embodiment provides a preparation method of composite starch foaming microbeads, which comprises the following steps:
s1, mixing thermoplastic starch, azodicarbonamide and toluene sulfonyl hydrazide at a high speed, wherein the dosage of the azodicarbonamide is 2% of that of the thermoplastic starch, the dosage of the toluene sulfonyl hydrazide is 1% of that of the thermoplastic starch, and uniformly mixing at 100 ℃ to obtain a starch foaming matrix;
s2, kneading and granulating the mixed starch foaming matrix in a granulator into spherical particles of 0.2mm to obtain foaming matrix particles;
and S3, spraying the molten PBAT melt to the foaming substrate, and stirring at a high speed until the surface of the foaming substrate is uniformly coated with a layer of fully-degradable plastic film to obtain the composite starch foaming microspheres.
The microbeads prepared in this example had a particle size of 0.3mm and a density of 0.8g/cm3。
Example 4
The embodiment provides a preparation method of composite starch foaming microbeads, which comprises the following steps:
s1, mixing thermoplastic starch and azodicarbonamide at a high speed, wherein the dosage of the azodicarbonamide is 5% of that of the thermoplastic starch, and uniformly mixing at 115 ℃ to obtain a starch foaming matrix;
s2, kneading and granulating the mixed starch foaming matrix in a granulator into spherical particles of 0.3mm to obtain foaming matrix particles;
and S3, spraying the melted PLA and PBAT melt to the foaming substrate, and stirring at a high speed until the surface of the foaming substrate is uniformly coated with a layer of fully-degradable plastic film to obtain the composite starch foaming microbead.
The microbeads prepared in this example had a particle size of 0.5mm and a density of 1.1g/cm3。
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 (7)
1. The composite starch foaming microbead is characterized by comprising a starch foaming matrix and a fully degradable plastic film, wherein a starch foaming organism is positioned in the center of the microbead, and the fully degradable plastic film is coated outside the foaming matrix.
2. The composite starch foamed microbead according to claim 1, wherein the starch foamed matrix comprises thermoplastic starch and a foaming agent.
3. The composite starch foamed micro bead according to claim 2, wherein the foaming agent is at least one of tosylhydrazide and azoformamide.
4. The composite starch foaming microbead according to claim 1, wherein the fully degradable plastic film is at least one of PLA, PBAT or PBS.
5. The preparation method of the composite starch foaming microbead as claimed in any one of claims 1 to 4, which is characterized by comprising the following steps:
s1, uniformly mixing thermoplastic starch and a foaming agent at a high speed, and uniformly mixing to obtain a starch foaming matrix;
s2, kneading and granulating the mixed starch foaming matrix in a granulator to form spherical particles to obtain foaming matrix particles;
and S3, spraying the molten degradable plastic film melt to the foaming matrix, and stirring at a high speed until the surface of the foaming matrix is uniformly coated with a layer of fully degradable plastic film to obtain the composite starch foaming microbeads.
6. The method according to claim 5, wherein the kneading temperature in step S1 is 100 to 140 ℃.
7. The method according to claim 5, wherein the particle diameter of the foamed base particles in step S2 is 0.2 to 0.3 mm.
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| CN201911139433.4A CN110746635A (en) | 2019-11-20 | 2019-11-20 | Composite starch foaming micro-bead and preparation method thereof |
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| CN201911139433.4A CN110746635A (en) | 2019-11-20 | 2019-11-20 | Composite starch foaming micro-bead and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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| CN1800249A (en) * | 2005-01-05 | 2006-07-12 | 项爱民 | Biodegradable starch-base foaming composition and foaming product containing same |
| CN101522768A (en) * | 2006-10-11 | 2009-09-02 | 巴斯夫欧洲公司 | Coated foam beads and process for producing halogen-free, fire-resistant bead foam moldings |
| CN101668798A (en) * | 2007-04-19 | 2010-03-10 | 辛伯拉技术有限公司 | The inflatable particulate poly(lactic acid) that applies |
| CN102206361A (en) * | 2011-04-27 | 2011-10-05 | 广东益德环保科技有限公司 | Fully-degradable foam material using starch as base material and preparation method for fully-degradable foam material |
| WO2012008784A2 (en) * | 2010-07-15 | 2012-01-19 | 대상 주식회사 | Expandable starch bead and method for preparing same |
| CN102702562A (en) * | 2012-05-24 | 2012-10-03 | 中国科学院宁波材料技术与工程研究所 | Preparation method for thermoplastic polyimide foaming particle and formed body thereof |
-
2019
- 2019-11-20 CN CN201911139433.4A patent/CN110746635A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1112143A (en) * | 1994-02-09 | 1995-11-22 | 诺瓦蒙特股份公司 | Expanded articles of biodegradable plastic material and a process for the preparation thereof |
| CN1800249A (en) * | 2005-01-05 | 2006-07-12 | 项爱民 | Biodegradable starch-base foaming composition and foaming product containing same |
| CN101522768A (en) * | 2006-10-11 | 2009-09-02 | 巴斯夫欧洲公司 | Coated foam beads and process for producing halogen-free, fire-resistant bead foam moldings |
| CN101668798A (en) * | 2007-04-19 | 2010-03-10 | 辛伯拉技术有限公司 | The inflatable particulate poly(lactic acid) that applies |
| WO2012008784A2 (en) * | 2010-07-15 | 2012-01-19 | 대상 주식회사 | Expandable starch bead and method for preparing same |
| CN102206361A (en) * | 2011-04-27 | 2011-10-05 | 广东益德环保科技有限公司 | Fully-degradable foam material using starch as base material and preparation method for fully-degradable foam material |
| CN102702562A (en) * | 2012-05-24 | 2012-10-03 | 中国科学院宁波材料技术与工程研究所 | Preparation method for thermoplastic polyimide foaming particle and formed body thereof |
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