CN112812398A - Green environment-friendly foam material based on renewable resources and manufacturing method thereof - Google Patents

Green environment-friendly foam material based on renewable resources and manufacturing method thereof Download PDF

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Publication number
CN112812398A
CN112812398A CN202011617346.8A CN202011617346A CN112812398A CN 112812398 A CN112812398 A CN 112812398A CN 202011617346 A CN202011617346 A CN 202011617346A CN 112812398 A CN112812398 A CN 112812398A
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China
Prior art keywords
foam material
green
environment
renewable resources
bio
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CN202011617346.8A
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Chinese (zh)
Inventor
杨超
魏琼
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Guangde Xiangyuan New Material Technology Co ltd
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Guangde Xiangyuan New Material Technology Co ltd
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Priority to CN202011617346.8A priority Critical patent/CN112812398A/en
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/06Working-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
    • C08J9/10Working-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
    • C08J9/102Azo-compounds
    • C08J9/103Azodicarbonamide
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0061Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00Foams characterized by the expanding agent
    • C08J2203/04N2 releasing, ex azodicarbonamide or nitroso compound
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/04Homopolymers or copolymers of ethene
    • C08J2323/06Polyethene
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2403/00Characterised by the use of starch, amylose or amylopectin or of their derivatives or degradation products
    • C08J2403/04Starch derivatives
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2423/00Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2423/04Homopolymers or copolymers of ethene
    • C08J2423/06Polyethene
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2423/00Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2423/04Homopolymers or copolymers of ethene
    • C08J2423/08Copolymers of ethene
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2423/00Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2423/10Homopolymers or copolymers of propene
    • C08J2423/12Polypropene

Abstract

The invention discloses a green environmental protection type foam material based on renewable resources and a manufacturing method thereof, which is formed by at least blending, crosslinking and foaming bio-based resin and fossil energy-based plastic resin through a foaming agent, wherein the fossil energy-based plastic resin is any one or more of polyethylene, polypropylene, thermoplastic elastomer and ethylene-vinyl acetate copolymer; the green environment-friendly polyolefin foam material based on renewable resources belongs to environment-friendly type, and compared with the common petroleum-based polyolefin foam material on the market at present, the green environment-friendly polyolefin foam material can greatly reduce the emission of greenhouse gas carbon dioxide and relieve the environmental problems of global warming and the like; it has wide prospect in the fields of medical treatment and health, human body protection, package buffering, automotive interior and electronic sealing.

Description

Green environment-friendly foam material based on renewable resources and manufacturing method thereof
Technical Field
The invention relates to the field of green environment-friendly polyolefin foam materials, in particular to a green environment-friendly foam material based on renewable resources and a manufacturing method thereof.
Background
As an important material basis for human survival and development, fossil raw materials support the progress of human civilization and the development of economic society. However, the non-renewable nature of fossil energy and the enormous human consumption thereof are making fossil energy gradually going to exhaustion.
The utilization of fossil energy is also a key factor causing environmental changes and pollution. The large amount of fossil energy consumption causes the emission of greenhouse gases, increases the concentration of the greenhouse gases in the atmosphere, enhances the greenhouse effect and causes global warming. With the gradual reduction of fossil energy reserves, the global energy crisis is also increasingly approaching. The energy structure mainly based on fossil energy has obvious unsustainability.
The currently developed bioplastics on the market mainly comprise three types, namely PHA, polylactic acid and thermoplastic starch-based polymers. The raw material of the thermoplastic starch-based polymer is derived from biological crops such as corn, potato, wheat and cassava, is low in cost and renewable, can be subjected to compost biodegradation, but is poor in water resistance and transparency and difficult to use in complex environmental conditions; PLA is prepared by extracting lactic acid produced by glycogen fermentation from crops such as sugar beet, corn and potato, and can be processed in various ways, but PLA is poor in toughness, barrier property, melt strength and crystallization speed.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a green environment-friendly foam material based on renewable resources and a manufacturing method thereof. Its advantages include the following:
(1) low-carbon emission: the biomass material can absorb a large amount of carbon dioxide gas in the growth process, so that the biomass material has a carbon neutralization effect; therefore, the carbon dioxide emission of the bioplastic is only 20% of that of petrochemical plastic, and the bioplastic is also called low-carbon plastic, so that the emission of greenhouse gas carbon dioxide can be reduced by using the low-carbon plastic, and the temperature rise speed of the earth can be favorably reduced.
(2) And (3) cyclic regeneration: the biomass naturally grows year after year and is inexhaustible, and is the only abundant resource on the earth which is not well utilized at present
In order to achieve the purpose, the invention designs a green environment-friendly foam material based on renewable resources, which is prepared by at least blending, crosslinking and foaming a bio-based resin and a fossil energy-based plastic resin through a foaming agent, wherein the fossil energy-based plastic resin is any one or more of polyethylene, polypropylene, a thermoplastic elastomer and an ethylene-vinyl acetate copolymer;
the content of the resin in the bio-based resin is more than or equal to 30 percent of that of the green environment-friendly foam material; in the bio-based resin, the content of the biomass derived carbon is 60 to 100 percent of the total amount of the organic carbon;
the biomass-derived carbon content in the foam is 30% to 100% of the total organic carbon (biomass-derived carbon content determined based on ASTM D6866 method).
Furthermore, the content of the resin in the bio-based resin is more than or equal to 70 percent of that of the green environment-friendly foam material;
in the bio-based resin, the content of the biomass derived carbon is 70-100% of the total amount of the organic carbon;
in the foam material, the content of biomass-derived carbon is 60-100% of the total amount of organic carbon.
Still further, the bio-based resin is any one or more of low-density polyethylene, low-density linear polyethylene, high-density polyethylene, elastomer POE, ethylene-vinyl acetate copolymer and modified thermoplastic starch.
Still further, the melt index of the bio-based resin is 0.2-10 g/10min, and the density is 0.89-0.96 g/cm3
Still further, the blowing agent is an AC blowing agent
Still further, the raw materials of the green environment-friendly foam material also comprise modified starch and a catalyst.
The invention also provides a method for manufacturing the green and environment-friendly foam material based on renewable resources, the green and environment-friendly foam material is formed by blending, molding, crosslinking and foaming of bio-based resin and fossil energy-based plastic resin, the crosslinking mode is electron irradiation crosslinking, and the gel content of the foam material is 25-70 wt%.
Preferably, the blending mode is banburying granulation (aiming at blending and dispersing the materials uniformly), and the forming mode is extrusion forming or compression forming; the foaming mode is free foaming or other modes.
The invention has the beneficial effects that:
the environment-friendly polyolefin foaming material based on renewable resources provided by the invention belongs to environment-friendly type, accords with international sustainable development and European Union RED carbon certification (ISCC EU) and European Union RED sustainable biological material round-table conference certification, and can greatly reduce the emission of greenhouse gas carbon dioxide and relieve the environmental problems of global warming and the like compared with the common petroleum-based polyolefin foaming material on the market at present. It has wide prospect in the fields of medical treatment and health, human body protection, package buffering, automotive interior and electronic sealing.
Detailed Description
The present invention is described in further detail below with reference to specific examples so as to be understood by those skilled in the art.
Example 1
The preparation method of the green environment-friendly foam material 1 based on renewable resources comprises the following steps:
(1) the materials are prepared according to the following proportion:
5 parts of modified starch, wherein the content of biomass-derived carbon in the bio-based LDPE and the bio-based LLDPE accounts for 70% of the total organic carbon content, and the contents of the bio-based LDPE, the bio-based LLDPE and the bio-based LLDPE account for 65 parts of the bio-based LDPE, 15 parts of the bio-based LLDPE, 15 parts of petroleum-based POE and 6 parts of AC foaming agent.
(2) And (2) mixing the materials in the step (1) by using an internal mixer, wherein the internal mixing temperature is 120-140 ℃, and the internal mixing time is 5-25 minutes. And adding the mixture into a single-screw extruder for extrusion granulation after banburying.
(3) And (3) putting the master batch in the step (2) into a double-screw extruder to be extruded and formed into a sheet, preferably carrying out irradiation crosslinking on the formed sheet by using an electron accelerator, and controlling the gel content of the sheet after irradiation crosslinking to be between 40 and 55 percent.
(4) And (4) adding the sheet subjected to irradiation crosslinking in the step (3) into a vertical foaming furnace for continuous foaming and rolling to obtain the foamed sheet based on renewable resources.
The green environmental protection type foam material prepared by the embodiment has the density of 1 kg/m3. The proportion of the biomass-derived carbon content in the total organic carbon content is up to 77%.
Example 2
The raw materials are prepared according to the proportion of 30 parts of bio-based LDPE, 50 parts of petroleum-based LDPE resin, 10 parts of petroleum-based LLDPE resin, 5 parts of ethylene-vinyl acetate and 4 parts of AC foaming agent, wherein the content of biomass derived carbon in the bio-based LDPE accounts for 60% of the total organic carbon content, and the rest steps are consistent with those in the example 1, so that the foaming sheet 2 based on renewable resources can be obtained.
The prepared foaming sheet material 2 based on renewable resources has the density of 130kg/m3The biomass-derived carbon content of the biomass-derived carbon-based biomass fuel accounts for 30% of the total organic carbon content.
Example 3
The raw materials are prepared according to the proportion of 10 parts of modified starch, 80 parts of bio-based LDPE, 5 parts of petroleum-based PP, 8 parts of AC foaming agent and 0.1 part of catalyst, the content of biomass derived carbon in the bio-based LDPE accounts for 100% of the total organic carbon content, and the rest steps are consistent with those in the embodiment 1, so that the foamed sheet 3 based on renewable resources can be obtained. The density of the prepared foaming sheet based on renewable resources is 66kg/m3The proportion of the biomass-derived carbon content in the total organic carbon content is up to 95%.
Comparative example 1
The raw materials are prepared according to the proportion of 5 parts of talcum powder, 80 parts of petroleum-based LDPE resin, 15 parts of LLDPE resin, 7.5 parts of AC foaming agent and 0.1 part of catalyst, and the rest steps are consistent with those in the example 1, so that the common foaming sheet based on non-renewable resources can be obtained. Made based on non-renewable resourcesThe foamed sheet of (2) has a density of 100kg/m3The ratio of the biomass-derived carbon content to the total organic carbon content was 0.
Comparative example 2
The raw materials are prepared according to the proportion of 80 parts of petroleum-based LDPE resin, 10 parts of bio-based LLDPE, 5 parts of bio-based ethylene-vinyl acetate copolymer, 4 parts of AC foaming agent and 0.1 part of catalyst, the content of biomass derived carbon in the bio-based LLDPE and the bio-based ethylene-vinyl acetate copolymer accounts for 70 percent of the total organic carbon content, and the rest steps are consistent with those in the embodiment 1, so that the foamed sheet can be obtained. The foamed sheet had a density of 133kg/m3The proportion of biomass-derived carbon content to the total organic carbon content is 13%.
Comparative example 3
The raw materials are prepared according to the proportion of 10 parts of talcum powder, 80 parts of petroleum-based LDPE, 8 parts of AC foaming agent and 0.1 part of catalyst, and the rest steps are consistent with those in the embodiment 1, so that the foaming sheet based on renewable resources can be obtained. The density of the prepared foaming sheet based on renewable resources is 66kg/m3The proportion of the biomass-derived carbon content to the total organic carbon content of the biomass-derived carbon material is up to 0.
TABLE 1
Note: the content of the biomass derived carbon is the proportion of the total organic carbon in the foam material;
"MD" refers to the Machine Direction (Machine Direction), which refers to the Direction that is aligned with the Direction of extrusion of the foam;
"TD" refers to the Transverse Direction (Transverse Direction), which refers to the Direction perpendicular to the MD and parallel to the foam.
The thermal conductivity is measured according to GB/T10294 at 23 ℃.
The results show that the invention can provide a green environment-friendly foam material based on renewable resources, and compared with the common petroleum-based polyolefin foam material on the market at present, the invention can greatly reduce the emission of greenhouse gas carbon dioxide and alleviate the environmental problems of global warming and the like.
Other parts not described in detail are prior art. Although the present invention has been described in detail with reference to the above embodiments, it is only a part of the embodiments of the present invention, not all of the embodiments, and other embodiments can be obtained without inventive step according to the embodiments, and the embodiments are within the scope of the present invention.

Claims (8)

1. A green environmental protection type foam material based on renewable resources is characterized in that: the foaming agent is formed by at least blending, crosslinking and foaming bio-based resin and fossil energy-based plastic resin through a foaming agent, wherein the fossil energy-based plastic resin is any one or more of polyethylene, polypropylene, thermoplastic elastomer and ethylene-vinyl acetate copolymer;
in the bio-based resin, the content of the resin is more than or equal to 30 percent of that of the green environment-friendly foam material; and the content of the biomass derived carbon in the bio-based resin is 60 to 100 percent of the total amount of the organic carbon;
in the foam material, the content of biomass-derived carbon is 30-100% of the total amount of organic carbon.
2. The green and environment-friendly foam material based on renewable resources according to claim 1, wherein: the content of the resin in the bio-based resin is more than or equal to 70 percent of that of the green environment-friendly foam material; the content of biomass derived carbon in the bio-based resin is 70-100% of the total amount of organic carbon;
in the foam material, the content of biomass-derived carbon is 60-100% of the total amount of organic carbon.
3. The green and environment-friendly foam material based on renewable resources according to claim 1, wherein: the bio-based resin is any one or more of low-density polyethylene, low-density linear polyethylene, high-density polyethylene, elastomer POE, ethylene-vinyl acetate copolymer and modified thermoplastic starch.
4. The green and environment-friendly foam material based on renewable resources according to claim 1, wherein: the melt index of the bio-based resin is 0.2-10 g/10min, and the density is 0.89-0.96 g/cm3
5. The green and environment-friendly foam material based on renewable resources according to claim 1, wherein: the foaming agent is an AC foaming agent.
6. The green and environment-friendly foam material based on renewable resources according to claim 1, wherein: the raw materials of the green environment-friendly foam material also comprise modified starch and a catalyst.
7. A method for manufacturing the green and environment-friendly foam material based on renewable resources according to claim 1, which is characterized in that: the green environment-friendly foam material is prepared by blending, molding, crosslinking and foaming bio-based resin and fossil energy-based plastic resin, the crosslinking mode is electron irradiation crosslinking, and the gel content in the foam material is 25-70%.
8. The method for manufacturing green and environment-friendly foam material based on renewable resources according to claim 7, wherein: the blending mode is banburying granulation, and the molding mode is extrusion molding or compression molding; the foaming mode is free foaming or other modes.
CN202011617346.8A 2020-12-31 2020-12-31 Green environment-friendly foam material based on renewable resources and manufacturing method thereof Pending CN112812398A (en)

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Application Number Priority Date Filing Date Title
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1491271A (en) * 2001-10-25 2004-04-21 ������������ʽ���� Exothermic composition and exothermic article using composition, and method for producing exothermic article
CN108822378A (en) * 2018-05-25 2018-11-16 湖北祥源新材科技股份有限公司 Cross-linked foam polyolefin material and preparation method thereof with antibacterial functions
CN109824972A (en) * 2019-03-08 2019-05-31 安踏(中国)有限公司 Bottom material and preparation method thereof in a kind of environment-friendly foaming
CN110869425A (en) * 2017-03-22 2020-03-06 希悦尔公司 Methods and formulations for renewable polyethylene foams

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1491271A (en) * 2001-10-25 2004-04-21 ������������ʽ���� Exothermic composition and exothermic article using composition, and method for producing exothermic article
CN110869425A (en) * 2017-03-22 2020-03-06 希悦尔公司 Methods and formulations for renewable polyethylene foams
CN108822378A (en) * 2018-05-25 2018-11-16 湖北祥源新材科技股份有限公司 Cross-linked foam polyolefin material and preparation method thereof with antibacterial functions
CN109824972A (en) * 2019-03-08 2019-05-31 安踏(中国)有限公司 Bottom material and preparation method thereof in a kind of environment-friendly foaming

Non-Patent Citations (1)

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Title
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