CN111763431A - Method for preparing foamed plastic by using waste leather leftover materials - Google Patents
Method for preparing foamed plastic by using waste leather leftover materials Download PDFInfo
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- CN111763431A CN111763431A CN201910262697.2A CN201910262697A CN111763431A CN 111763431 A CN111763431 A CN 111763431A CN 201910262697 A CN201910262697 A CN 201910262697A CN 111763431 A CN111763431 A CN 111763431A
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- collagen
- foam plastic
- dialdehyde
- leftover materials
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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
- C08J9/08—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 carbon dioxide
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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
- C08J9/0014—Use of organic additives
- C08J9/0023—Use of organic additives containing oxygen
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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
- C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
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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
- C08J9/0066—Use of inorganic compounding ingredients
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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
- C08J9/0095—Mixtures of at least two compounding ingredients belonging to different one-dot groups
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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
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/02—CO2-releasing, e.g. NaHCO3 and citric acid
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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
- C08J2389/00—Characterised by the use of proteins; Derivatives thereof
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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
- C08J2403/00—Characterised by the use of starch, amylose or amylopectin or of their derivatives or degradation products
- C08J2403/04—Starch derivatives
- C08J2403/10—Oxidised starch
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- 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
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- 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
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/05—Alcohols; Metal alcoholates
- C08K5/053—Polyhydroxylic alcohols
Abstract
The invention provides a method for preparing foam plastic by using waste leather leftover materials. The preparation method comprises extracting collagen from waste material of leather edge and corner generated in tannery; then uniformly mixing the collagen, the cross-linking agent, the foaming agent, the nucleating agent and the plasticizer in water according to a certain proportion, and drying to remove water; and finally, carrying out hot-press molding under proper process conditions to obtain the protein foam plastic. Dialdehyde macromolecules such as dialdehyde starch, dialdehyde cellulose, dialdehyde pranluke and the like are selected as cross-linking agents to carry out cross-linking modification on the collagen so as to improve the strength of the collagen. The collagen is plasticized and modified by using micromolecular reagents such as glycerol, urea and the like as plasticizers so as to reduce the melting temperature of the collagen, and the collagen can be directly hot-pressed by using a conventional processing and forming method. The invention utilizes the leather leftover materials as raw materials to prepare the biodegradable foam plastic with good mechanical property, can be used as the thermal insulation foam plastic and has good application prospect.
Description
Technical Field
The invention relates to the field of resource material preparation, in particular to biodegradable foam plastic with good mechanical property.
Background
Foam is an important synthetic polymer material and is an important component of the plastic industry at present. The foam plastic has the characteristics of light weight, heat insulation, sound absorption, shock absorption and the like, so the foam plastic is widely applied to the fields of packaging, heat preservation, sound insulation and the like. At present, most of the foamed plastic products are prepared from petrochemical cracking products, and the products also generate a large amount of white pollution due to the defect of difficult degradation. Therefore, the search for degradable materials to process the foam plastic is a research hotspot. The leather industry generates a large amount of leather waste each year, which is one of the important pollutions of the leather industry. The solid wastes contain abundant collagen, and if the collagen can be used as a matrix to be plasticized to prepare a plastic product, the white pollution generated by the plastic product prepared by the existing petrochemical industry can be reduced, the environmental pressure is relieved, and a new thought can be provided for recycling the collagen of the leather wastes.
Many researchers have conducted much research work on the utilization of waste leather scraps as materials. Originally, a small amount of skin scraps were added to a polymer material to prepare a novel composite material by blending. But because chromium and collagen form stable complex bonds and a large number of hydrogen bonds exist between protein molecules and molecules, the tolerance of the chromium and the collagen is relative to that of a high polymer material, so that the mechanical property of the prepared composite material is reduced; the introduction amount of the leather leftover materials in the composite material is limited, so that the utilization rate of the leather leftover materials is limited, and the composite material is not suitable for large-scale resource utilization of the leather leftover materials. In recent years, researchers also prepare foams by utilizing collagen extracted from the leftover bits and pieces in a freeze drying mode, the method can effectively improve the utilization rate of the waste leftover bits and pieces, but the production mode of freeze drying is low in efficiency, high in production cost and difficult to popularize on a large scale.
The invention aims to overcome the defects of the prior art, the collagen extracted by the conventional method is directly used as a matrix, and the green nontoxic plasticizer is used for destroying hydrogen bonds between protein molecules. And carrying out crosslinking modification on the collagen by using a green degradable crosslinking agent. The collagen-based material with excellent mechanical property is prepared by adopting the conventional hot-press molding process for molding, and foam plastics with different strengths can be obtained by changing the amount of the plasticizer so as to meet different requirements. So far, no literature and patent reports on the preparation of universal foams by conventional thermal processing methods directly using collagen as a matrix have been found.
Disclosure of Invention
1. A method for preparing foam plastic by using waste leather leftover materials is characterized by comprising the following steps:
(1) washing and dedusting leftovers of a tannery by using deionized water, and extracting collagen from the unttanned leather leftovers by adopting an enzyme method; extracting collagen from the tanned skin leftover materials by adopting an alkali-enzyme method; then placing the collagen powder in a forced air drying oven at 20-40 ℃ for drying for 24-64h, further crushing by a crusher after drying to prepare collagen particles, and drying and storing;
(2) mixing collagen, cross-linking agent, foaming agent, nucleating agent and plasticizer in water in certain proportion. Wherein the collagen: a crosslinking agent: foaming agent: nucleating agent: the mass ratio of the plasticizer is 1.0: (0.05-0.20): (0.05-0.20): (0.05-0.20): (0.1-0.8), uniformly mixing, placing in an air-blast drying oven at the temperature of 20-50 ℃, drying for 48-96 h, and removing water to obtain a dry mixture;
(3) directly processing the dried mixture under proper pressure by using a hot-press molding process, wherein the processing temperature is 100-180 ℃, and the hot-press time is 5-30min, so as to obtain the foam plastic.
The collagen used in the present invention is extracted from leather scraps produced in tanneries.
The cross-linking agent used in the invention is one of dialdehyde starch, dialdehyde cellulose and dialdehyde pluronic dialdehyde macromolecules.
The plasticizer used in the invention is one of glycerol and urea.
The nucleating agent is one of calcium carbonate and silicon dioxide.
The hot pressing pressure used in the invention is 0.2-1.0 MPa.
Compared with the prior art, the method provided by the invention has the following advantages:
(1) the raw material used in the invention is collagen extracted from the leather leftover materials generated in a tannery, thereby not only solving the problem of environmental pollution caused by the leather leftover materials in the tanning production, but also expanding the non-tanning utilization method of the leather leftover materials and realizing the resource utilization of the leather leftover materials.
(2) The cross-linking agent used in the invention is a green nontoxic macromolecular dialdehyde cross-linking agent. Compared with other cross-linking agents, the cross-linking agent has the advantages of greenness, no toxicity, stable cross-linking, controllable cross-linking degree and the like.
(3) The plasticizer used in the invention is glycerol and urea. Compared with other plasticizers, the plasticizer has the advantages of good plasticizing effect, greenness, safety, low price and the like.
(4) Compared with the prior art that the foam is prepared by collagen through a freeze-drying method, the method has the advantages of low production cost, simple operation, high production efficiency, good industrialization prospect and the like.
The specific implementation scheme is as follows:
three examples of the present invention are given below, and the present invention will be specifically described by way of examples. Has a certain effect
It is to be noted that the examples are given solely for the purpose of illustration and are not to be construed as limitations on the scope of the invention, as many insubstantial modifications and variations of the invention may be made by those skilled in the art in light of the above teachings.
The invention is realized by the following technical scheme, except for special description, the parts are parts by weight, and the percentages are weight percentages.
Example 1:
washing leftover materials of leather-making factories with deionized water for dedusting, extracting collagen, then placing the leather leftover materials in a blast drying oven at 40 ℃ for drying for 48 hours, further crushing the collagen by a crusher after drying to prepare collagen particles, and drying and storing the collagen particles. Respectively weighing 17.0g of collagen, 1.2 g of glycerol, 0.4 g of dialdehyde starch, 0.4 g of baking soda and 1.0 g of calcium carbonate, placing the materials into a beaker filled with a proper amount of water, stirring and uniformly mixing the materials in a water bath kettle at 50 ℃, placing the mixture into an air-blast drying oven, and drying and dewatering the mixture for 64 hours at 45 ℃ to obtain a dry mixture. Taking a proper amount of dry mixture, placing the dry mixture in a foaming mold, carrying out hot-pressing foaming molding under a flat vulcanizing instrument, and setting a foaming temperature: 130 ℃, foaming time: 10 min, pressure: 0.5MPa, and obtaining the foamed plastic after the mixture is fully melted.
Example 2:
washing leftover materials of leather-making factories with deionized water for dedusting, extracting collagen, then placing the leather leftover materials in a blast drying oven at 40 ℃ for drying for 48 hours, further crushing the collagen by a crusher after drying to prepare collagen particles, and drying and storing the collagen particles. Respectively weighing 16.0g of collagen, 2.2 g of glycerol, 0.4 g of dialdehyde starch, 0.4 g of baking soda and 1.0 g of calcium carbonate, placing the materials into a beaker filled with a proper amount of water, stirring and uniformly mixing the materials in a water bath kettle at 50 ℃, placing the mixture into an air-blast drying oven, and drying and dewatering the mixture for 64 hours at 45 ℃ to obtain a dry mixture. Taking a proper amount of dry mixture, placing the dry mixture in a foaming mold, carrying out hot-pressing foaming molding under a flat vulcanizing instrument, and setting a foaming temperature: 130 ℃, foaming time: 10 min, pressure: 0.5MPa, and obtaining the foamed plastic after the mixture is fully melted.
Example 3:
washing leftover materials of leather-making factories with deionized water for dedusting, extracting collagen, then placing the leather leftover materials in a blast drying oven at 40 ℃ for drying for 48 hours, further crushing the collagen by a crusher after drying to prepare collagen particles, and drying and storing the collagen particles. Respectively weighing 17.0g of collagen, 1.2 g of glycerol, 0.4 g of dialdehyde starch, 0.4 g of baking soda and 1.0 g of calcium carbonate, placing the materials into a beaker filled with a proper amount of water, stirring and uniformly mixing the materials in a water bath kettle at 50 ℃, placing the mixture into an air-blast drying oven, and drying and dewatering the mixture for 64 hours at 45 ℃ to obtain a dry mixture. Taking a proper amount of dry mixture, placing the dry mixture in a foaming mold, carrying out hot-pressing foaming molding under a flat vulcanizing instrument, and setting a foaming temperature: 160 ℃, foaming time: 7 min, pressure: 0.5MPa, and obtaining the foamed plastic after the mixture is fully melted.
Claims (8)
1. A method for preparing foam plastic by using waste leather leftover materials is characterized by comprising the following steps:
washing and dedusting leftover materials of leather making factories by using deionized water, extracting collagen from untanned leftover materials by adopting an enzyme method, extracting the collagen from tanned leftover materials by adopting an alkali-enzyme method, then drying the extracted protein in a blast drying oven at 20-40 ℃ for 24-64h, further crushing by adopting a crusher after drying to prepare collagen particles, and drying and storing;
mixing collagen, cross-linking agent, foaming agent, nucleating agent and plasticizer in water in certain proportion.
2. Wherein the collagen: a crosslinking agent: foaming agent: nucleating agent: the mass ratio of the plasticizer is 1.0: (0.05-0.20): (0.05-0.20): (0.05-0.20): (0.1-0.8), uniformly mixing, placing in an air-blast drying oven at the temperature of 20-50 ℃, standing for 48-96 h, drying and removing water to obtain a dry mixture;
directly processing the dried mixture under proper pressure by using a hot-press molding process, wherein the processing temperature is 100-180 ℃, and the hot-press time is 5-30min, so as to obtain the foam plastic.
3. The method for preparing foam using waste offal as claimed in claim 1, wherein said collagen is extracted from offal produced in tannery.
4. The method for preparing foam plastic by using waste leather scraps as claimed in claim 1, wherein the cross-linking agent is one of three dialdehyde macromolecules comprising dialdehyde starch, dialdehyde cellulose and dialdehyde pluronic.
5. The method for preparing foam plastic using waste leather scraps as claimed in claim 1, wherein the plasticizer is one of glycerin and urea.
6. The method for preparing foam plastic by using waste skin leftover material as claimed in claim 1, wherein the foaming agent is one of baking soda and azodicarbonamide.
7. The method for preparing foam plastic using waste leather scraps as claimed in claim 1, wherein the nucleating agent is one of calcium carbonate and silica.
8. The method for preparing foam plastic using waste leather scraps as claimed in claim 1, wherein the suitable processing pressure is 0.2 to 1.0 MPa.
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| CN201910262697.2A CN111763431B (en) | 2019-04-02 | 2019-04-02 | Method for preparing foamed plastic by using waste leather leftover materials |
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| CN201910262697.2A CN111763431B (en) | 2019-04-02 | 2019-04-02 | Method for preparing foamed plastic by using waste leather leftover materials |
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| CN111763431B CN111763431B (en) | 2021-09-21 |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101775168A (en) * | 2010-01-12 | 2010-07-14 | 浙江理工大学 | Collagen-modified biodegradable plastic and preparation method thereof |
| CN101851421A (en) * | 2009-03-31 | 2010-10-06 | 西南科技大学 | Thermoplastic plant protein/fiber blend material and preparation method thereof |
| CN104109396A (en) * | 2014-07-04 | 2014-10-22 | 四川大学 | Collagen plastic and preparation method thereof |
| CN104262648A (en) * | 2014-09-18 | 2015-01-07 | 四川大学 | Collagen-based biomedical material by taking dialdehyde polyethylene glycol as cross-linking agent and preparation method thereof |
| CN106075576A (en) * | 2016-07-13 | 2016-11-09 | 烟台正海生物科技股份有限公司 | A kind of collagen protein sponge and preparation method and application |
| CN106543745A (en) * | 2016-11-07 | 2017-03-29 | 四川大学 | A kind of method for preparing biological based elastomeric using discarded collagen |
-
2019
- 2019-04-02 CN CN201910262697.2A patent/CN111763431B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101851421A (en) * | 2009-03-31 | 2010-10-06 | 西南科技大学 | Thermoplastic plant protein/fiber blend material and preparation method thereof |
| CN101775168A (en) * | 2010-01-12 | 2010-07-14 | 浙江理工大学 | Collagen-modified biodegradable plastic and preparation method thereof |
| CN104109396A (en) * | 2014-07-04 | 2014-10-22 | 四川大学 | Collagen plastic and preparation method thereof |
| CN104262648A (en) * | 2014-09-18 | 2015-01-07 | 四川大学 | Collagen-based biomedical material by taking dialdehyde polyethylene glycol as cross-linking agent and preparation method thereof |
| CN106075576A (en) * | 2016-07-13 | 2016-11-09 | 烟台正海生物科技股份有限公司 | A kind of collagen protein sponge and preparation method and application |
| CN106543745A (en) * | 2016-11-07 | 2017-03-29 | 四川大学 | A kind of method for preparing biological based elastomeric using discarded collagen |
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Effective date of registration: 20230511 Address after: 2nd Floor, Building 1, No. 1616 Nanhua Road, High tech Zone, Chengdu, Sichuan, 610041 Patentee after: Sichuan Chuangzhi Weiye Technology Co.,Ltd. Address before: 610020 No. 2, Section 2, Chuanda Road, Shuangliu County, Chengdu, Sichuan Patentee before: SICHUAN University |