CN109401033A - A kind of high resiliency foamed material and the preparation method and application thereof based on ethylene vinyl acetate elastomer - Google Patents
A kind of high resiliency foamed material and the preparation method and application thereof based on ethylene vinyl acetate elastomer Download PDFInfo
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- CN109401033A CN109401033A CN201811215808.6A CN201811215808A CN109401033A CN 109401033 A CN109401033 A CN 109401033A CN 201811215808 A CN201811215808 A CN 201811215808A CN 109401033 A CN109401033 A CN 109401033A
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- vinyl acetate
- elastomer
- foamed material
- ethylene vinyl
- high resiliency
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- 239000000463 material Substances 0.000 title claims abstract description 64
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 239000002994 raw material Substances 0.000 claims abstract description 12
- 230000003647 oxidation Effects 0.000 claims abstract description 5
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 5
- 229920001971 elastomer Polymers 0.000 claims description 35
- 239000000806 elastomer Substances 0.000 claims description 25
- 229920001577 copolymer Polymers 0.000 claims description 18
- 229920000642 polymer Polymers 0.000 claims description 15
- 239000004156 Azodicarbonamide Substances 0.000 claims description 12
- XOZUGNYVDXMRKW-AATRIKPKSA-N azodicarbonamide Chemical compound NC(=O)\N=N\C(N)=O XOZUGNYVDXMRKW-AATRIKPKSA-N 0.000 claims description 12
- 235000019399 azodicarbonamide Nutrition 0.000 claims description 12
- 229920001684 low density polyethylene Polymers 0.000 claims description 8
- 239000004702 low-density polyethylene Substances 0.000 claims description 8
- 235000021355 Stearic acid Nutrition 0.000 claims description 7
- 150000002148 esters Chemical class 0.000 claims description 7
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 7
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 7
- 239000008117 stearic acid Substances 0.000 claims description 7
- LCJHLOJKAAQLQW-UHFFFAOYSA-N acetic acid;ethane Chemical compound CC.CC(O)=O LCJHLOJKAAQLQW-UHFFFAOYSA-N 0.000 claims description 6
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 238000005187 foaming Methods 0.000 claims description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 4
- 239000003431 cross linking reagent Substances 0.000 claims description 4
- 239000000945 filler Substances 0.000 claims description 4
- 239000004088 foaming agent Substances 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000012545 processing Methods 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- OKIRBHVFJGXOIS-UHFFFAOYSA-N 1,2-di(propan-2-yl)benzene Chemical compound CC(C)C1=CC=CC=C1C(C)C OKIRBHVFJGXOIS-UHFFFAOYSA-N 0.000 claims description 2
- YKTNISGZEGZHIS-UHFFFAOYSA-N 2-$l^{1}-oxidanyloxy-2-methylpropane Chemical group CC(C)(C)O[O] YKTNISGZEGZHIS-UHFFFAOYSA-N 0.000 claims description 2
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 2
- 101000648997 Homo sapiens Tripartite motif-containing protein 44 Proteins 0.000 claims description 2
- 102100028017 Tripartite motif-containing protein 44 Human genes 0.000 claims description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- 229920000092 linear low density polyethylene Polymers 0.000 claims description 2
- 239000004707 linear low-density polyethylene Substances 0.000 claims description 2
- 229920001179 medium density polyethylene Polymers 0.000 claims description 2
- 239000004701 medium-density polyethylene Substances 0.000 claims description 2
- 229920001526 metallocene linear low density polyethylene Polymers 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 9
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- HGUFODBRKLSHSI-UHFFFAOYSA-N 2,3,7,8-tetrachloro-dibenzo-p-dioxin Chemical compound O1C2=CC(Cl)=C(Cl)C=C2OC2=C1C=C(Cl)C(Cl)=C2 HGUFODBRKLSHSI-UHFFFAOYSA-N 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 3
- 239000004014 plasticizer Substances 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 abstract description 2
- 230000003712 anti-aging effect Effects 0.000 abstract description 2
- 230000002929 anti-fatigue Effects 0.000 abstract description 2
- 229910052799 carbon Inorganic materials 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 abstract description 2
- 229920000891 common polymer Polymers 0.000 abstract 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical group CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 42
- 239000006260 foam Substances 0.000 description 18
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 12
- -1 polyethylene Polymers 0.000 description 9
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 8
- 229920003023 plastic Polymers 0.000 description 8
- 239000004033 plastic Substances 0.000 description 8
- 239000004698 Polyethylene Substances 0.000 description 7
- 239000004800 polyvinyl chloride Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 229920000573 polyethylene Polymers 0.000 description 6
- 229920000915 polyvinyl chloride Polymers 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 230000008901 benefit Effects 0.000 description 5
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 4
- 239000011787 zinc oxide Substances 0.000 description 4
- JTXMVXSTHSMVQF-UHFFFAOYSA-N 2-acetyloxyethyl acetate Chemical compound CC(=O)OCCOC(C)=O JTXMVXSTHSMVQF-UHFFFAOYSA-N 0.000 description 3
- 238000009413 insulation Methods 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 239000004814 polyurethane Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 229920002725 thermoplastic elastomer Polymers 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- LQYDVZGVUPXQRB-UHFFFAOYSA-N C(C)(C)C1=CC=CC=C1.[O] Chemical compound C(C)(C)C1=CC=CC=C1.[O] LQYDVZGVUPXQRB-UHFFFAOYSA-N 0.000 description 1
- 239000004803 Di-2ethylhexylphthalate Substances 0.000 description 1
- 229920005830 Polyurethane Foam Polymers 0.000 description 1
- 229920006311 Urethane elastomer Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 239000003183 carcinogenic agent Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000013013 elastic material Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 235000013312 flour Nutrition 0.000 description 1
- 239000006261 foam material Substances 0.000 description 1
- 229920001821 foam rubber Polymers 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- WORCCYVLMMTGFR-UHFFFAOYSA-M loxoprofen sodium Chemical compound [Na+].C1=CC(C(C([O-])=O)C)=CC=C1CC1C(=O)CCC1 WORCCYVLMMTGFR-UHFFFAOYSA-M 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 239000011496 polyurethane foam Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- 238000004056 waste incineration Methods 0.000 description 1
Classifications
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
- 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
- C08J2323/06—Polyethene
-
- 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
- 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
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—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
- C08J2423/04—Homopolymers or copolymers of ethene
- C08J2423/06—Polyethene
-
- 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
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—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
- C08J2423/04—Homopolymers or copolymers of ethene
- C08J2423/08—Copolymers of ethene
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Emergency Medicine (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a kind of high resiliency foamed material and the preparation method and application thereof based on ethylene vinyl acetate elastomer, common polymer raw material is partly or entirely substituted using the ethylene vinyl acetate elastomer of VA content >=25% and is prepared into elastomeric foamed material, it is not only soft to prepare finished product, Shore A hardness is less than 25, hence it is evident that better than 30 or more of traditional material；And resilience is good, and elongation at break is high, and has antifatigue and anti-slip effect；Furthermore without containing the carbon-to-carbon double bond to oxidation-sensitive in the molecule of ethylene vinyl acetate elastomer, so finished product has superior anti-aging property；Material is prepared without harmful substances such as formaldehyde, plasticizer, more leads to the problem of dioxin without chloride, safety and environmental protection performance is high；Preparation method can be used directly in primary producing line, not increase process flow, be suitble to industrialized production；Reduce production improving cost.
Description
Technical field
The present invention relates to foam material field more particularly to a kind of high resiliency based on ethylene vinyl acetate elastomer
Foamed material and the preparation method and application thereof.
Background technique
Foamed material, which refers to, generates the substance that bubble makes the foaming of porous mass in substance internal gasifier, has weight
Light, specific strength height, excellent insulation performance, the advantage that buffer capacity is significant and adsorption capacity is strong are measured, has been widely used
In fields such as auto industry, building industry, packaging industry, agricultural, water process and air filtrations；Such as manufacture foamed plastics, bubble
Foam rubber, foamed resin etc..
Main spy applied to Crawl mat for children and polyolefin (mainly polyethylene or EVA) foam ground cushion of fitment material for family
Property is to have certain flexibility and rigidity concurrently, that is, the combination of elasticity and plasticity.But generally speaking, resilience is inadequate, and foot steps on
Go comfort level inadequate.The Shore A hardness of general polyethylene or eva foam ground cushion is greater than 30 °, and normal condition is 38 ° or so.
And greater demand is higher for the aeroelastic requirements of foam ground cushion at present, it is desirable that foam ground cushion is made more flexible, more
Softness, comfortable foot feeling are not easy to fatigue.And it requires to be not easy between instep and foam ground cushion and between foam ground cushion and ground
Sliding, that is, have certain anti-sliding function, prevent child old man from falling down.
Flexible foam ground cushion is essentially all polyvinyl chloride (PVC) foam ground cushion on the market at present.Polyvinyl chloride resin itself is nothing
Poison, but its additive such as plasticizer, stabilizer etc., it may cause some toxic actions.What wherein report was most is plasticising
Agent DEHP.In addition there are stabilizer the problem of containing heavy metal.
PVC bigger problem also resides in the harm of its rubbish.Waste incineration can generate universally acknowledged most malicious carcinogenic substance
Dioxin, and the Production conditions of dioxin are chlorine-containing compounds to be had, and could be formed at high temperature.PVC provides chlorine
Source, the chlorinity in the solid-state castoff of city have 38%~66% from PVC, it can be considered that PVC is dioxin now
The largest source of generation.Thus the environmental issue of PVC flexible foam ground cushion is bigger.
Another common flex foam is polyurethane.Linear polyurethane is used as thermoplastic elastomer (TPE) (urethane
Rubber, UR；Or Thermoplastic PU, TPU) it is widely used in production foamed plastics, there are the function such as heat preservation, insulation, sound insulation
Energy.This soft foam is used as packaging material and Sofa cushion etc. like sponge.But polyurethane foam plastics is not suitable for doing ground cushion,
The reason is that its major defect is to meet water to be easy to happen hydrolysis, it is easy to change by action of ultraviolet radiation, and residual monomer toluene diisocyanate
Acid esters is more toxic, and has related record in " polymer science concise course (second edition) ".
How foamed material worth research that suitable material prepare high resiliency that is, shore hardness≤25 is chosen.
Summary of the invention
Goal of the invention: In order to solve the problems of in the prior art, the invention proposes one kind to be based on ethylene-acetate
High resiliency foamed material of ethylene ester elastomer and the preparation method and application thereof, the shore for the high resiliency foamed material being prepared
Hardness is reduced to 10-25, is changed into elastomer, the whole elasticity and flexibility for promoting foamed material from plastic body.
Technical solution: to achieve these objectives, the present invention takes following technical scheme:
A kind of high resiliency foamed material based on ethylene vinyl acetate elastomer, including system as follows by weight
Standby raw material: 1-5 parts of 8-12 parts of 100 parts of polymer, foaming agent, zinc oxide containing vinyl-vinyl acetate copolymer elastomer,
1-2 parts of stearic acid, 0.5-1.0 parts of crosslinking agent, 0-80 parts of filler；Containing at least one VA content >=25% in the polymer
Vinyl-vinyl acetate copolymer elastomer；The vinyl-vinyl acetate copolymer bullet of VA content >=25% in the polymer
Property body mass percent be 45%-100%.
The performance of ethene-vinyl acetate copolymer (EVA) and the content of vinyl acetate (VA) have very big relationship, and VA is got over
It is few, closer to LDPE；VA is more, reduces or inhibit the generation of crystallization, performance is closer to rubber.When melt index is certain
When, VA content reduces, and rigidity improves；VA content increases, and elasticity, flexibility improve.Commonly it is used as expanded polyolefin ground cushion
EVA VA be 14%~18%, the EVA of this VA% is plastics, and performance is similar with LDPE；And high-elastic ground cushion (Shao of the application
Family name hardness≤25), application be VA% >=25% ethylene vinyl acetate elastomer (also referred to as rubber-type EVA), at this time it
It is elastomer, has fundamental difference with common plastics EVA (VA% < 25%).Common plastics EVA only with polyethylene kind seemingly
The common basic resin for doing foam ground cushion.And rubber-type EVA (VA% >=25%) performance of the invention has essential distinction.
More preferably, the vinyl-vinyl acetate copolymer elastomer melt index MI value range is 1.0-9.0g/
10min。
More preferably, when in the vinyl-vinyl acetate copolymer elastomer VA content be 25%-29%, ethylene-
The dosage of vinyl acetate copolymer elastomer is 45%-100%.
More preferably, when in the vinyl-vinyl acetate copolymer elastomer VA content be 30%-40%, ethylene-
The dosage of vinyl acetate copolymer elastomer is 1%-50%.
Further, further include in the polymer melt index MI value range be 1.0-6.0g/10min low-density
The ethane-acetic acid ethyenyl ester of polyethylene, linear low density polyethylene, medium density polyethylene, metallocene PE, VA < 25% is total
At least one of polymers.
Further, the foaming agent is azodicarbonamide, 4, at least one of 4 '-oxobenzenesulfonyl hydrazide.
Further, the crosslinking agent is two tert-butyl peroxy base diisopropylbenzene (DIPB)s, at least one in cumyl peroxide
Kind.
Further, the filler is at least one of talcum powder, calcium carbonate.
The preparation side of disclosed herein as well is a kind of high resiliency foamed material based on ethylene vinyl acetate elastomer
Method includes the following steps:
Required raw material is got ready on demand, is placed in internal rubber mixer and carries out mixing and plasticate processing, wherein closed refining glue
Built-in temperature is discharged after being the 130-140 DEG C of 10-30min that plasticates；The material of internal rubber mixer discharge is sent into open mill to carry out
The thin logical 10-20min of mill；It is cut after cooling in flakes, the foaming in 165-185 DEG C and cavity pressure 5-20MPa of press,
Obtain the high resiliency foamed material for being desired based on ethylene vinyl acetate elastomer.
The invention also discloses the applications of the high resiliency foamed material of above-mentioned preparation method preparation, especially by chemical blowing
It is prepared into one of ground cushion, coiled material.It is specifically as follows polyethylene ground cushion, eva foam ground cushion, LDPE foam ground cushion, PE
Foam ground cushion, mosaic floor, polyethylene coiled material, the products such as eva foam coiled material；It is mainly used for the sports such as Yoga field
Institute, infant creeping and playground, the elderly playground etc. is to ground cushion coiled material elasticity and the higher application of flexibility requirements；
It can also be used for the increasing bullet effect of the building material ground cushion product of house ornamentation.
The utility model has the advantages that a kind of high resiliency foamed material based on ethylene vinyl acetate elastomer provided by the invention and
Preparation method and application, have following advantages compared with prior art:
(1) foamed material finished product Shore A hardness of the invention is less than 25, specifically between 10~25, hence it is evident that better than tradition
30 or more of material.
(2) foamed material finished product of the invention is not only soft, but also resilience is good, and elongation at break is high, wherein ethylene-second
The content of vinyl acetate elastomer is higher, and above-mentioned performance is better.
(3) foamed material finished product soft comfortable of the invention, antifatigue, there is anti-slip effect.
(4) without containing the carbon-to-carbon double bond to oxidation-sensitive in the molecule of ethylene vinyl acetate elastomer, so at
Product have superior anti-aging property.
(5) material is prepared without harmful substances such as formaldehyde, plasticizer, more leads to the problem of dioxin without chloride, is pacified
Loopful guaranteed cost is high.
(6) preparation method can be used directly in primary producing line, not increase process flow, be suitble to industrialized production；It reduces
Produce improving cost.
Detailed description of the invention:
Fig. 1 is the strain-stress relation contrast schematic diagram of foamed material finished product prepared by embodiment 1 and comparative example 1.
Specific embodiment
Embodiment 1-7 and comparative example 1 are set: to the ethane-acetic acid ethyenyl ester elasticity of VA content >=25% in polymer
The foamed material of the different quality percentage preparation of body carries out preparation test comparison, specific as follows:
Embodiment 1:
A kind of high resiliency foamed material based on ethylene vinyl acetate elastomer, including system as follows by weight
Standby raw material: the polymer for ethylene vinyl acetate elastomer and low density polyethylene the mixing composition that VA content is 28%
3kg, azodicarbonamide (AC) 300g, di-t-butyl peroxy isopropyl base benzene (BIPB) 22g, stearic acid 30g, zinc oxide 40g are sliding
Mountain flour 2kg.The ethylene vinyl acetate elastomer that wherein VA content is 28% specifically selects Du Pont 265, matter in the polymer
Measuring percentage is 100%；And its melt index is 3.0g/10min.
Preparation method is as follows: required raw material got ready on demand, is placed in internal rubber mixer and is carried out mixing and plasticate processing,
Wherein temperature is 135 DEG C of 15min discharges of plasticating in internal rubber mixer；The material of internal rubber mixer discharge is sent into open mill
Carry out the thin logical 15min of mill；It is cut after cooling in flakes, the foaming in 175 DEG C of press obtains being desired based on ethylene-acetate
The high resiliency foamed material of ethylene ester elastomer.
Embodiment 2- embodiment 7:
Remove that the mass percentage content in the polymer of Du Pont 265 is different, other prepare the type dosage of raw material with
Embodiment 1 is identical；And preparation method is also same as Example 1, the specific quality hundred in the polymer of Du Pont 265 in embodiment 2-7
Ratio is divided to be followed successively by 90%, 80%, 75%, 70%, 60%, 50%.
Comparative example 1:
A kind of common foamed material, including as follows by weight prepare raw material: low density polyethylene (Yangtze bar
This husband 2426H, melt index 2.3g/10min) 3kg, azodicarbonamide (AC) 300g, di-t-butyl peroxy isopropyl base benzene
(BIPB) 22g, stearic acid 30g, zinc oxide 40g, talcum powder 2kg.Difference with embodiment 1-7 is and is not added with VA content
28% ethylene vinyl acetate elastomer Du Pont 265.
Another setting embodiment 8-9: the foamed material of the ethylene vinyl acetate elastomer preparation of different VA contents is carried out
Test comparison is prepared, and is compared with embodiment 1；It is specific as follows:
Embodiment 8:
A kind of high resiliency foamed material based on ethylene vinyl acetate elastomer, including system as follows by weight
Standby raw material: the ethylene vinyl acetate elastomer 3kg that VA content is 25%, azodicarbonamide (AC) 380g, di-t-butyl mistake
Oxygen cumene (BIPB) 25g, stearic acid 30g, zinc oxide 40g, talcum powder 1.75kg.The wherein ethylene-that VA content is 25%
Vinyl acetate ester elastomer specifically selects Du Pont 265, and its melt index is 8.1g/10min.
Preparation method is same as Example 1.
Embodiment 9:
Basic embodiment mode and preparation method are same as Example 8, the difference is that the ethylene-acetate second used
Enester elastomer VA content is different, is 28%, specific to select Du Pont 40W, melt index 6.0g/10min.
In addition embodiment 10-11 is set, mixed and carried out using the ethylene vinyl acetate elastomer of two kinds of difference VA contents
The preparation of foamed material, specific as follows:
Embodiment 10:
A kind of high resiliency foamed material based on ethylene vinyl acetate elastomer, including system as follows by weight
Standby raw material: the ethane-acetic acid ethyenyl ester that ethylene vinyl acetate elastomer 2.7kg, the VA content that VA content is 28% is 40%
Elastomer 300g；Azodicarbonamide (AC) 300g, di-t-butyl peroxy isopropyl base benzene (BIPB) 22g, stearic acid 30g, oxidation
Zinc 40g, talcum powder 3kg.The ethylene vinyl acetate elastomer that wherein VA content is 28% specifically selects Du Pont 265, and it is molten
Melting index is 3.0g/10min；The ethylene vinyl acetate elastomer that VA content is 40% specifically selects Du Pont 40W, and it is molten
Melting index is 6.5g/10min.
Preparation method is same as Example 1.
Embodiment 11:
A kind of high resiliency foamed material based on ethylene vinyl acetate elastomer, including system as follows by weight
Standby raw material: the ethane-acetic acid ethyenyl ester that ethylene vinyl acetate elastomer 1.5kg, the VA content that VA content is 28% is 18%
Elastomer 1.5kg；Azodicarbonamide (AC) 300g, di-t-butyl peroxy isopropyl base benzene (BIPB) 22g, stearic acid 30g, oxidation
Zinc 40g, talcum powder 3kg.The ethylene vinyl acetate elastomer that wherein VA content is 28% specifically selects Du Pont 265, and it is molten
Melting index is 3.0g/10min；The ethylene vinyl acetate elastomer that VA content is 18% specifically selects Yangtze BASF
V5110J, and its melt index is 3.5g/10min.
Preparation method is same as Example 1.
Finished product test comparison:
1) test method:
The measuring method of Shore A hardness:
According to GB/T530-1999 " the pocket hardometer penetration hardness test method of rubber ", international standard ISO7619:1986
It is tested, hardometer model are as follows: LX-A Shore durometer.
The measuring method of elongation at break:
Instrument is used according to GB/T6344-2008 " measurement of flexible foam polymeric material tensile strength and elongation at break "
Electronic universal tester model: Japanese Shimadzu AGS-X5KN.Specimen size is 152mm × 13mm × 10mm, and cross section is rectangle；
Tensile speed is 500mm/min ± 50mm/min；23 DEG C ± 2 DEG C of measuring temperature, relative humidity 50% ± 5%.
The measuring method of the coefficient of resilience:
According to GB/T6670-2008 " measurement of flexible foam polymeric material falling ball method resilience performance "；Corresponding international standard
ISO8307:2007.Steel ball falls height: 500mm after rise；Steel ball size: 16mm.Instrument model: (Dongguan City benefit opens up detector to KY-C
Device Co., Ltd).
Embodiment 1- embodiment 7 and comparative example 1 add the test data of the product of the Du Pont 265 of different quality percentage
It is as shown in table 1:
Properties of product comparison prepared by the Du Pont 265 of different quality percentage is added in table 1:LDPE
From table 1 it follows that 1-7 of the embodiment of the present invention is added to the ethane-acetic acid ethyenyl ester bullet that VA content is 28%
The hardness of foamed material finished product made of Xing Ti Du Pont 265 is prepared is lower than 25 °, and additive amount is more, and hardness is lower, minimum
16.4 ° of embodiment 1；And elongation at break be not added with compared with comparative example 1 it is more excellent for the foamed material of Du Pont 265；Have more
The excellent coefficient of resilience, up to 57%.Therefore foamed material prepared by the present invention is not only soft, but also resilience is good, breaks
Split elongation height.
Furthermore please as shown in Figure 1 to the strain-stress relation contrast schematic diagram of embodiment 1 and comparative example 1.A is pair in figure
Ratio 1, B are embodiment 1.It can be seen that A is the load-deformation curve of typical plastic material, and B is typical elastic material
Load-deformation curve.The elongation at break of B ratio A is much bigger when stretching.
Prepared by embodiment 8-9 and the ethylene vinyl acetate elastomer of 1 difference VA content of embodiment and melt index
The test data of product is as shown in table 2:
Table 2: the properties of product comparison of the ethylene vinyl acetate elastomer of different VA contents and melt index preparation
From Table 2, it can be seen that the embodiment of the present invention 1 and 8-9 are added to different VA contents 25%, 28% and difference
The hardness of foamed material finished product made of the ethylene vinyl acetate elastomer of melt index is prepared is below 25 °, and has
Higher elongation at break and the excellent coefficient of resilience, up to 61%.As can be seen that foamed material prepared by the present invention is not
It is only soft, and resilience is good, and elongation at break is high.
Embodiment 10-11 carries out foamed material using the ethylene vinyl acetate elastomer mixing of two kinds of difference VA contents
The test data for preparing product it is as shown in table 3:
Table 3: it is compared using the properties of product that the ethylene vinyl acetate elastomer of two kinds of difference VA contents is mixed with
From table 3 it is observed that the embodiment of the present invention 10 and 11 is by the second of two kinds of difference VA contents (>=25%)
Foamed material made of alkene-vinyl acetate ester elastomer mixing application is prepared, the hardness of finished product is below 25 °, and has
Higher elongation at break and the excellent coefficient of resilience, up to 61%.As can be seen that two kinds of difference VA contents (equal >=
25%) ethylene vinyl acetate elastomer is used in mixed way prepared foamed material and also has not only softness, but also resilience
It is good, the high advantage of elongation at break.
It should be pointed out that for those skilled in the art, without departing from the principle of the present invention,
It can also make several improvements, these improvement also should be regarded as protection scope of the present invention.
Claims (10)
1. a kind of high resiliency foamed material based on ethylene vinyl acetate elastomer, it is characterised in that including as follows with weight
What is calculated prepares raw material: 8-12 parts of 100 parts of polymer, foaming agent containing vinyl-vinyl acetate copolymer elastomer, oxidation
1-5 parts of zinc, 1-2 parts of stearic acid, 0.5-1.0 parts of crosslinking agent, 0-80 parts of filler；Contain at least one VA content in the polymer
>=25% vinyl-vinyl acetate copolymer elastomer；The ethane-acetic acid ethyenyl ester of VA content >=25% in the polymer
The mass percent of copolymer elastomer is 45%-100%.
2. the high resiliency foamed material according to claim 1 based on ethylene vinyl acetate elastomer, feature exist
In: the vinyl-vinyl acetate copolymer elastomer melt index MI value range is 1.0-9.0g/10min.
3. the high resiliency foamed material according to claim 1 or 2 based on ethylene vinyl acetate elastomer, feature
Be: VA content is 25%-29%, vinyl-vinyl acetate copolymer in the vinyl-vinyl acetate copolymer elastomer
The dosage of elastomer is 45%-100%.
4. the high resiliency foamed material according to claim 1 or 2 based on ethylene vinyl acetate elastomer, feature
Be: VA content is 30%-40%, vinyl-vinyl acetate copolymer in the vinyl-vinyl acetate copolymer elastomer
The dosage of elastomer is 1%-50%.
5. the high resiliency foamed material according to claim 1 or 2 based on ethylene vinyl acetate elastomer, feature
It is: further includes the low density polyethylene (LDPE) that melt index MI value range is 1.0-6.0g/10min in the polymer, it is linear low
Density polyethylene, medium density polyethylene, metallocene PE, in the vinyl-vinyl acetate copolymer of VA < 25% at least
It is a kind of.
6. the high resiliency foamed material according to claim 1 based on ethylene vinyl acetate elastomer, feature exist
In: the foaming agent is at least one of azodicarbonamide, 4,4 '-oxobenzenesulfonyl hydrazide.
7. the high resiliency foamed material according to claim 1 based on ethylene vinyl acetate elastomer, feature exist
In: the crosslinking agent is at least one of two tert-butyl peroxy base diisopropylbenzene (DIPB)s, cumyl peroxide.
8. the high resiliency foamed material according to claim 1 based on ethylene vinyl acetate elastomer, feature exist
In: the filler is at least one of talcum powder, calcium carbonate.
9. the preparation method of the high resiliency foamed material based on ethylene vinyl acetate elastomer as described in claim 1,
It is characterized in that including the following steps:
Required raw material is got ready on demand, is placed in internal rubber mixer and carries out mixing and plasticate processing, wherein in internal rubber mixer
Temperature is discharged after being the 130-140 DEG C of 10-30min that plasticates；The material of internal rubber mixer discharge is sent into open mill and carries out mill
Thin logical 10-20min；It is cut after cooling in flakes, the foaming in 165-185 DEG C and cavity pressure 5-20MPa of press obtains
It is desired based on the high resiliency foamed material of ethylene vinyl acetate elastomer.
10. the application of the high resiliency foamed material of preparation method preparation as claimed in claim 9, it is characterised in that pass through chemistry
Foaming is prepared into one of ground cushion, coiled material.
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