CN104817754A - High hardness, high elasticity and wear resistance composite foam material and preparation method thereof - Google Patents
High hardness, high elasticity and wear resistance composite foam material and preparation method thereof Download PDFInfo
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
- C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
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- 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
- C08J9/04—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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- 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
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/04—N2 releasing, ex azodicarbonamide or nitroso compound
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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
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised 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
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/08—Copolymers of ethene
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- C—CHEMISTRY; METALLURGY
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C—CHEMISTRY; METALLURGY
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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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
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/06—Properties of polyethylene
- C08L2207/062—HDPE
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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
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/06—Properties of polyethylene
- C08L2207/068—Ultra high molecular weight polyethylene
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- General Chemical & Material Sciences (AREA)
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- Materials Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Footwear And Its Accessory, Manufacturing Method And Apparatuses (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
The invention provides a high hardness, high elasticity and wear resistance composite foam material and a preparation method thereof, and belongs to the field of polymer material processing. The composite foam material comprises, by mass, 20-80 parts of thermoplastic elastomer, 0-50 parts of ethylene-vinyl acetate copolymer, 0-30 parts of polyethylene, 5-30 parts of a viscosity reducer, 0.5-6 parts of cross-linking agent, 1-5 parts of a foaming agent, 2-6 parts of a foaming assistant, 0.5-10 parts of a wear resistance agent, 10-30 parts of a filler, and 1-4 parts of other assistants. The material has the texture of rubber, also has the characteristics of high elasticity, wear resistance, low compression set, folding resistance and wrinkle resistance, can be widely applied to the field of manufacturing of beach shoes, slippers, sports shoes, and other shoes, and can also be applied to children picture mosaic cards, foam floors, and packaging materials of precise electronic apparatuses, electric appliances and medical apparatuses.
Description
Technical field
The invention belongs to field of high polymer material processing, relate to the preparation method of a kind of high rigidity-snappiness-wear-resisting composite foam material, refer in particular to the elasticity utilizing elastomerics to improve foam material, utilize paraffin oil, aromatic hydrocarbon oil, reactive plasticizer for viscosity-depression agent, complex abrasion-proof agent is utilized to improve composite foam material wear resistance, preparation high rigidity-snappiness-wear-resisting composite foam material.
Background technology
Along with the raising of human living standard, the demand of footwear also increases day by day, and meanwhile, the footwear art of the mankind is also more and more meticulousr, and therefore, to the foot-fitting of footwear, have higher requirement in the aspects such as comfortableness, exterior quality, environmental friendliness.At present, at the bottom of common LDPE, EVA shoe there is the contradiction between rebound resilience and hardness in foamed material, and usual hardness is low, rebound resilience is high, or hardness is high, and rebound resilience is low, and compression set comparatively large (being greater than 50%), wear resistance and folding resistance are not good, wrinkle resistant undesirable with texture yet.Therefore, develop a kind of there is rubber texture and have high rigidity-snappiness-wear-resisting composite foam material be enterprise pursue target.The present invention utilizes elastomerics to improve the elasticity of foam material, utilizes paraffin oil, aromatic hydrocarbon oil, response type monomer to be viscosity-depression agent, utilizes complex abrasion-proof agent to improve composite foam material wear resistance and prepares high rigidity-snappiness-wear-resisting composite foam material.This material not only has rubber texture, and there is high rigidity, snappiness, the feature such as wear-resisting, low compression is askew, folding is wrinkle resistant.Can be widely used in manufacturing the footwear material field such as beach shoes, slippers, sports shoes, also can be applicable to o, foam floor, and precision electronic device, electrical equipment, medicine equipment wrapping material.
Summary of the invention
The invention provides a kind of high rigidity-snappiness-wear-resisting composite foam material, there is rubber texture, and there is the features such as low compression is askew, folding is wrinkle resistant.
The technical solution used in the present invention is:
High rigidity-snappiness-wear-resisting composite foam material, is grouped into by the one-tenth of following massfraction:
Thermoplastic elastomer: 20-80 part;
Ethylene-vinyl acetate copolymer: 0-50 part;
Polyethylene: 0-30 part;
Viscosity-depression agent: 5-30 part;
Linking agent: 0.5-6 part;
Whipping agent: 1-5 part;
Frothing aid: 2-6 part;
Anti-wear agent: 0.5-10 part;
Weighting agent: 10-30 part;
Other auxiliary agent: 1-4 part.
Described thermoplastic elastomer is one or both mixing in POE (POE), SEBS (styrene-ethylene/butylene-styrene multipolymer), SBS (styrene butadiene) multipolymer, SIS (styrene-isoprene-phenylethene) multipolymer.
Described ethylene-vinyl acetate copolymer (EVA) is vinyl acetate content 16-26%, melt flow rate (MFR) (MFI) 1-8 gram/10 minutes.
Described polyethylene is one or more in Low Density Polyethylene, linear low density of polyethylene, ultrahigh molecular weight polyethylene(UHMWPE), ethylene copolymer.
Described viscosity-depression agent is paraffin oil, aromatic hydrocarbon oil and reactive plasticizer mixture.Reactive plasticizer is: one or more mixtures in Phthalic acid, diallyl ester (DAP), maleic acid ester, fumarate and itaconic ester, vinylformic acid (methacrylic acid) ester.
Described linking agent is: dicumyl peroxide (DCP), dual-tert-butyl dicumyl peroxide (BIBP), Vinylstyrene (DVB), Ethylene glycol dimethacrylate (EGDM), trimethylolpropane trimethacrylate (TMPTMA), triallyl isocyanurate (TAIC).One or more mixtures.
Described whipping agent is Cellmic C 121 (AC), sodium bicarbonate, 4,4 '-bis oxide benzsulfamide (OBSH), N, N ' one or more mixtures in-dinitroso five methyne four ammonium (DPT) whipping agent.
Described anti-wear agent is: ultra-high molecular weight polysiloxane, molybdenumdisulphide, organic fluorine (one or more mixtures in ethylene-tetrafluoroethylene copolymer (ETFE), ethylene-chlorotrifluoro-ethylene copolymer (ECTFE), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA).
Described frothing aid is zinc oxide and Zinic stearas, and its mass ratio is 2:1.
Described weighting agent: calcium carbonate, talcum powder, aluminium hydroxide, magnesium hydroxide, flyash, one or more mixtures in attapulgite.
Other auxiliary agent described: refer to ultraviolet absorbers, oxidation inhibitor, one or more mixtures in tinting material.
Except linking agent, poured into by above composition and carry out mixing in Banbury mixer, preferred mixing time is 7-10 minute, and temperature is 105-115 DEG C.In the material after mixing, add linking agent carries out mixing, and preferred mixing time is 3-6 minute, and temperature is 115-120 DEG C; By the mixture that obtains through extruding granulator granulation, then foam, moulded from foam or foam-injection can be adopted, obtain high rigidity-snappiness-wear-resisting composite foam material.
Advantage of the present invention: high rigidity-snappiness prepared by the present invention-wear-resisting composite foam material, not only has rubber texture, and there is high rigidity, snappiness, the feature such as wear-resisting, low compression is askew, folding is wrinkle resistant.Can be widely used in manufacturing the footwear material field such as beach shoes, slippers, sports shoes, also can be applicable to o, foam floor, and precision electronic device, electrical equipment, medicine equipment wrapping material.
Embodiment
Embodiment 1-3
Table 1 high rigidity-snappiness-wear-resisting composite foam material formula composition (quality %)
According to the raw material in table 1, first the raw material such as thermoplastic elastomer and ethylene-vinyl acetate copolymer is joined in Banbury mixer, drop into weighting agent more respectively, viscosity-depression agent, anti-wear agent, whipping agent, other auxiliary agent carry out mixing, mixing time is 8 minutes, and temperature is 105 ~ 115 DEG C.
In the above-mentioned material mixed, add linking agent, continue mixing 3 minutes, temperature is 115 ~ 120 DEG C; The material mixed is poured into the granulation of extruding pelletization unit, pellet, through moulded from foam or shot foaming, namely obtains high-elastic wear-resistant proof composite foaming material.
Wherein thermoplastic elastomer is POE and SEBS mixture, and its blending ratio is preferred Mitsui DF-840 or DF-810 of 2:1, POE; SEBS preferred Sinopec Ba Ling petrochemical complex company limited, YH-502; YH-604; Ethylene-vinyl acetate copolymer (EVA) is Taiwan plastic cement limited-liability company (TAISOX) EVA-7358M; Weighting agent is talcum powder; Linking agent is dicumyl peroxide (DCP) and iso-cyanuric acid triallyl ester mixture, and its mass ratio is 1:2; Anti-wear agent is ultra-high molecular weight polysiloxane; Whipping agent is Cellmic C 121 (AC) and sodium bicarbonate mixture, and its mass ratio is 2:1; Frothing aid is zinc oxide and Zinic stearas, and its mass ratio is 2:1; Viscosity-depression agent is paraffin oil and vinylformic acid (methacrylic acid) ester mixture, and its mass ratio is 1:4; Other auxiliary agent is: antioxidant 1010: 0.5%, oxidation inhibitor DLPT:1.5% and tinting material carbon black: 1% 3 kind of mixture.
Embodiment 4-6
Get each raw material weight by the material composition composition in table 2, procedure of processing and processing parameter, with embodiment 1, obtain a kind of high rigidity-snappiness-wear-resisting composite foam material.
Table 2 high rigidity-snappiness-wear-resisting composite foam material formula composition (quality %)
Wherein thermoplastic elastomer is POE and SEBS mixture, and its blending ratio is preferred Mitsui DF-840 or DF-810 of 2:1, POE; SEBS preferred Sinopec Ba Ling petrochemical complex company limited, YH-502; YH-604; The preferred BASF AG of polyethylene: LDPE2426H; Linking agent is dicumyl peroxide (DCP) and iso-cyanuric acid triallyl ester mixture, and its mass ratio is 1:2; Anti-wear agent is ultra-high molecular weight polysiloxane; Whipping agent is Cellmic C 121 (AC) and sodium bicarbonate mixture, and its mass ratio is 2:1; Frothing aid is zinc oxide and Zinic stearas, and its mass ratio is 2:1; Viscosity-depression agent is aromatic hydrocarbon oil and Phthalic acid, diallyl ester (DAP) mixture, and its mass ratio is 1:4; Other auxiliary agent is: antioxidant 1010: 0.5%, oxidation inhibitor DLPT:1.5% and tinting material carbon black: 1% 3 kind of mixture.
Embodiment 7-9
Get each raw material weight by the material composition composition in table 3, procedure of processing and processing parameter, with embodiment 1, obtain a kind of high-elastic wear-resistant proof composite foaming material.
Table 3 high rigidity-snappiness-wear-resisting composite foam material formula composition (quality %)
Wherein thermoplastic elastomer is POE and SEBS mixture, and its blending ratio is preferred Mitsui DF-840 or DF-810 of 2:1, POE; SEBS preferred Sinopec Ba Ling petrochemical complex company limited, YH-502; YH-604; Ethylene-vinyl acetate copolymer (EVA) is Taiwan plastic cement limited-liability company (TAISOX) EVA-7358M; The preferred BASF AG of polyethylene: LDPE2426H; Linking agent is dicumyl peroxide (DCP) and iso-cyanuric acid triallyl ester mixture, and its mass ratio is 1:2; Anti-wear agent is ultra-high molecular weight polysiloxane; Whipping agent is 4,4 '-bis oxide benzsulfamide (OBSH) and sodium bicarbonate mixture, and its mass ratio is 2:1; Frothing aid is zinc oxide and Zinic stearas, and its mass ratio is 2:1; Viscosity-depression agent is aromatic hydrocarbon oil and maleic acid ester mixture; Other auxiliary agent is: antioxidant 1010: 0.5%, oxidation inhibitor DLPT:1.5% and tinting material carbon black: 1% 3 kind of mixture.
Carry out quantitative measurement to the foam material product that embodiment 1-9 obtains, result is as following table 4, and testing conditions is: room temperature 23 ± 3 DEG C, humidity 60 ± 5%.
The product performance of table 4 embodiment 1 ~ 9
Table 4 high rigidity-snappiness-wear-resisting composite foam material performance
There are above data known, high rigidity-snappiness that the present invention obtains-wear-resisting composite foam material, desirable rubber texture can be obtained, hardness, elasticity, wear resistance, low compression is askew waits footwear materials functional performance, the shortcoming such as overcome currently available products hardness and rebound resilience contradictory problems and wear no resistance, and meets national related physical performance.
Above a kind of high rigidity-snappiness-wear-resisting composite foam material provided by the present invention and preparation method are described in detail.Apply specific case herein to set forth principle of the present invention and embodiment, the explanation of above embodiment just understands method of the present invention and its core concept for helping.It should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention, can also carry out some improvement and modification to the present invention, these improve and modify the protection domain also falling into the claims in the present invention.
Claims (9)
1. high rigidity-snappiness-wear-resisting composite foam material, is characterized in that being grouped into by the one-tenth of following massfraction:
Thermoplastic elastomer: 20-80 part;
Ethylene-vinyl acetate copolymer: 0-50 part;
Polyethylene: 0-30 part;
Viscosity-depression agent: 5-30 part;
Linking agent: 0.5-6 part;
Whipping agent: 1-5 part;
Frothing aid: 2-6 part;
Anti-wear agent: 0.5-10 part;
Weighting agent: 10-30 part;
Other auxiliary agent: 1-4 part.
2. high rigidity-the snappiness according to claim-wear-resisting composite foam material, is characterized in that described thermoplastic elastomer is POE(POE), SEBS(styrene-ethylene/butylene-styrene multipolymer), SBS(styrene butadiene) multipolymer, SIS(styrene-isoprene-phenylethene) one or both mixing in multipolymer.
3. high rigidity-the snappiness according to claim-wear-resisting composite foam material, it is characterized in that described ethylene-vinyl acetate copolymer (EVA) is vinyl acetate content 16-26%, melt flow rate (MFR) (MFI) 1-8 gram/10 minutes.
4. high rigidity-the snappiness according to claim-wear-resisting composite foam material, is characterized in that described polyethylene is one or more in Low Density Polyethylene, linear low density of polyethylene, ultrahigh molecular weight polyethylene(UHMWPE), ethylene copolymer.
5. high rigidity-the snappiness according to claim-wear-resisting composite foam material, is characterized in that described viscosity-depression agent is paraffin oil, aromatic hydrocarbon oil and reactive plasticizer mixture; Reactive plasticizer is: one or more mixtures in Phthalic acid, diallyl ester (DAP), maleic acid ester, fumarate and itaconic ester, vinylformic acid (methacrylic acid) ester.
6. high rigidity-the snappiness according to claim-wear-resisting composite foam material, it is characterized in that described linking agent is: dicumyl peroxide (DCP), dual-tert-butyl dicumyl peroxide (BIBP), Vinylstyrene (DVB), Ethylene glycol dimethacrylate (EGDM), trimethylolpropane trimethacrylate (TMPTMA), triallyl isocyanurate (TAIC); One or more mixtures.
7. high rigidity-the snappiness according to claim-wear-resisting composite foam material, it is characterized in that described whipping agent is Cellmic C 121 (AC), sodium bicarbonate, 4,4 '-bis oxide benzsulfamide (OBSH), N, N ' one or more mixtures in-dinitroso five methyne four ammonium (DPT) whipping agent.
8. high rigidity-the snappiness according to claim-wear-resisting composite foam material, it is characterized in that described anti-wear agent is: ultra-high molecular weight polysiloxane, molybdenumdisulphide, organic fluorine (one or more mixtures in ethylene-tetrafluoroethylene copolymer (ETFE), ethylene-chlorotrifluoro-ethylene copolymer (ECTFE), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA);
High rigidity-snappiness according to claim-wear-resisting composite foam material, it is characterized in that described frothing aid is zinc oxide and Zinic stearas, its mass ratio is 2:1;
Described weighting agent: calcium carbonate, talcum powder, aluminium hydroxide, magnesium hydroxide, flyash, one or more mixtures in attapulgite;
Other auxiliary agent described: refer to ultraviolet absorbers, oxidation inhibitor, one or more mixtures in tinting material.
9. the preparation method of a kind of high rigidity-snappiness-wear-resisting composite foam material according to claim 1, is characterized in that, carry out according to following step:
A) following composition is taken by massfraction:
Thermoplastic elastomer: 20-80 part;
Ethylene-vinyl acetate copolymer: 0-50 part;
Polyethylene: 0-30 part;
Viscosity-depression agent: 5-30 part;
Linking agent: 0.5-6 part;
Whipping agent: 1-5 part;
Frothing aid: 2-6 part;
Anti-wear agent: 0.5-10 part;
Weighting agent: 10-30 part;
Other auxiliary agent: 1-4 part;
B) except linking agent, above composition is poured into carry out in Banbury mixer mixing; Preferred mixing time is 7-10 minute, and temperature is 105-115 DEG C;
C) in the material after mixing, adding linking agent continues mixing, and preferred mixing time is 3-6 minute, and temperature is 115-120 DEG C;
The mixture obtained is poured into the granulation of granulation unit, pellet foams, and can adopt moulded from foam or foam-injection, obtains high rigidity-snappiness-wear-resisting composite foam material.
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| CN108976583A (en) * | 2018-06-28 | 2018-12-11 | 黎明职业大学 | A kind of footwear material ultralight foam composite material and preparation method thereof |
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Application publication date: 20150805 |