CN110498954A - A kind of property of modified rectorite/Heveatex composite foam material and preparation method thereof - Google Patents
A kind of property of modified rectorite/Heveatex composite foam material and preparation method thereof Download PDFInfo
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- CN110498954A CN110498954A CN201910643733.XA CN201910643733A CN110498954A CN 110498954 A CN110498954 A CN 110498954A CN 201910643733 A CN201910643733 A CN 201910643733A CN 110498954 A CN110498954 A CN 110498954A
- Authority
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- China
- Prior art keywords
- property
- rectorite
- modified
- heveatex
- modified rectorite
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- 239000002131 composite material Substances 0.000 title claims abstract description 60
- 239000006261 foam material Substances 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 51
- 229920000126 latex Polymers 0.000 claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000004816 latex Substances 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 20
- 229920000459 Nitrile rubber Polymers 0.000 claims abstract description 19
- 230000003712 anti-aging effect Effects 0.000 claims abstract description 18
- 239000007788 liquid Substances 0.000 claims abstract description 18
- 239000002243 precursor Substances 0.000 claims abstract description 16
- 239000002994 raw material Substances 0.000 claims abstract description 16
- 239000003607 modifier Substances 0.000 claims abstract description 14
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 5
- 239000000463 material Substances 0.000 claims description 62
- 239000011248 coating agent Substances 0.000 claims description 30
- 238000000576 coating method Methods 0.000 claims description 30
- 238000002156 mixing Methods 0.000 claims description 23
- 238000012545 processing Methods 0.000 claims description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 238000010411 cooking Methods 0.000 claims description 12
- 239000003963 antioxidant agent Substances 0.000 claims description 9
- 230000003078 antioxidant effect Effects 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 238000000227 grinding Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 238000010792 warming Methods 0.000 claims description 7
- 238000004073 vulcanization Methods 0.000 claims description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 5
- 239000005864 Sulphur Substances 0.000 claims description 5
- 125000002091 cationic group Chemical group 0.000 claims description 5
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 4
- 229920001661 Chitosan Polymers 0.000 claims description 4
- RVGRUAULSDPKGF-UHFFFAOYSA-N Poloxamer Chemical compound C1CO1.CC1CO1 RVGRUAULSDPKGF-UHFFFAOYSA-N 0.000 claims description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 4
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 claims description 4
- 229960000502 poloxamer Drugs 0.000 claims description 4
- 229920001983 poloxamer Polymers 0.000 claims description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 4
- 235000010413 sodium alginate Nutrition 0.000 claims description 4
- 239000000661 sodium alginate Substances 0.000 claims description 4
- 229940005550 sodium alginate Drugs 0.000 claims description 4
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 3
- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical compound C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 claims description 3
- ZRMMVODKVLXCBB-UHFFFAOYSA-N 1-n-cyclohexyl-4-n-phenylbenzene-1,4-diamine Chemical compound C1CCCCC1NC(C=C1)=CC=C1NC1=CC=CC=C1 ZRMMVODKVLXCBB-UHFFFAOYSA-N 0.000 claims description 3
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 3
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 3
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 3
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 3
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-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
- 229920001206 natural gum Polymers 0.000 claims description 2
- ZZVUWRFHKOJYTH-UHFFFAOYSA-N diphenhydramine Chemical compound C=1C=CC=CC=1C(OCCN(C)C)C1=CC=CC=C1 ZZVUWRFHKOJYTH-UHFFFAOYSA-N 0.000 claims 1
- TVACALAUIQMRDF-UHFFFAOYSA-N dodecyl dihydrogen phosphate Chemical compound CCCCCCCCCCCCOP(O)(O)=O TVACALAUIQMRDF-UHFFFAOYSA-N 0.000 claims 1
- 244000043261 Hevea brasiliensis Species 0.000 abstract description 16
- 229920003052 natural elastomer Polymers 0.000 abstract description 16
- 229920001194 natural rubber Polymers 0.000 abstract description 16
- 238000005245 sintering Methods 0.000 abstract 1
- 229920001971 elastomer Polymers 0.000 description 10
- 239000005060 rubber Substances 0.000 description 10
- 239000004927 clay Substances 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000012779 reinforcing material Substances 0.000 description 5
- 230000004044 response Effects 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 230000002708 enhancing effect Effects 0.000 description 4
- 229910021389 graphene Inorganic materials 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- BIHQJMSIEXRWPS-UHFFFAOYSA-N 2-[bis(2-hydroxyethyl)amino]ethanol;dodecyl dihydrogen phosphate Chemical compound OCCN(CCO)CCO.CCCCCCCCCCCCOP(O)(O)=O BIHQJMSIEXRWPS-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000004575 stone Substances 0.000 description 3
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002114 nanocomposite Substances 0.000 description 2
- 238000003672 processing method Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000003943 catecholamines Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 229920003049 isoprene rubber Polymers 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229910052615 phyllosilicate Inorganic materials 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000747 poly(lactic acid) Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 239000004626 polylactic acid Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 229910021647 smectite Inorganic materials 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A43—FOOTWEAR
- A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
- A43B13/00—Soles; Sole-and-heel integral units
- A43B13/02—Soles; Sole-and-heel integral units characterised by the material
- A43B13/04—Plastics, rubber or vulcanised fibre
-
- 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
-
- 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
- C08J9/009—Use of pretreated 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
- C08J2307/00—Characterised by the use of natural rubber
- C08J2307/02—Latex
-
- 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
- C08J2413/00—Characterised by the use of rubbers containing carboxyl groups
- C08J2413/02—Latex
-
- 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
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/06—Pretreated ingredients and ingredients covered by the main groups C08K3/00 - C08K7/00
-
- 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
- C08K3/34—Silicon-containing compounds
-
- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
-
- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
-
- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/08—Ingredients agglomerated by treatment with a binding agent
Landscapes
- 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)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a kind of property of modified rectorite/Heveatex composite foam materials and preparation method thereof, and preparing raw material includes: Heveatex, carboxylic acrylonitrile butadiene rubber latex, property of modified rectorite, vulcanizing agent, promotor, anti-aging agent；The method of modifying of property of modified rectorite, comprising: organic modifiers plus water are obtained into organically-modified agent solution；Rectorite plus water are obtained into rectorite solution；Rectorite solution is added dropwise in organically-modified agent solution, property of modified rectorite precursor liquid is obtained；By property of modified rectorite precursor liquid through hydro-thermal reaction, property of modified rectorite predecessor is obtained；Property of modified rectorite predecessor is obtained into property of modified rectorite through sintering.Property of modified rectorite produced by the present invention/Heveatex composite foam material mechanical performance and in terms of have compared to conventional Natural rubber foam material and significantly promoted.
Description
Technical field
The present invention relates to the technical field of compositions of high-molecular compound, and in particular to a kind of property of modified rectorite/natural gum
Newborn composite foam material and preparation method thereof.
Background technique
Natural rubber has many advantages, such as that flexibility is good, elasticity is good, comfort level is high as sole material, the disadvantage is that wearability
Difference, therefore, it is necessary to carry out mechanical performance enhancing processing to natural rubber sole material.
Currently, the method for carrying out enhancing processing to natural rubber material includes but is not limited to: (one) filler enhances: clay/
The preparation of natural rubber nano composite material and performance [J] China Synthetic Rubber Industry, 2015,28 (2): 135-139；Carbon nanotube/
The preparation of native rubber composite material and performance [J] composite material journal, 2005,22 (5): 72-77；Redox graphene/
The preparation of natural rubber-nitile-butadiene rubber composite material and performance [J] composite material journal, 2018,5 (5): 1253-1259；
(2) enhancing is blended in polymer: microporous foam prepares polylactic acid/natural rubber porous material [J] plastics, 2018,47 (2): 50-
53；Application [J] high molecular material section of the natural rubber/trans- butadiene-isoprene rubber blend in all-steel radial tyre tread rubber
And engineering, 2018,34 (9): 89-95.Since natural rubber polarity is poor, and reinforcing material is mostly polar material, therefore, institute
Enhancing processing method be required to be in face of solving the problems, such as: while improving natural rubber mechanical strength, solution enhances
The consistency problem of material and natural rubber.
Carboxylic acrylonitrile butadiene rubber latex is anionic emulsion polymerization, with good oil resistant, corrosion resistance, with
And good mechanical performance.And due to introducing highly polar carboxyl on the macromolecular chain of carboxylic acrylonitrile butadiene rubber latex, improve work
Property and adhesive strength, be blended the mechanical strength and polarity that can improve Heveatex with Heveatex, improve and reinforcing material
Compatibility.
Rectorite is the 1:1 regularly interstratified mineral of dioctahedron mica and dioctahedron smectite composition, is had good
The property such as high temperature resistant, plasticity, dispersibility, dilatancy, adsorptivity, hydrability, cationic exchangeability, colloid bilayer and electro kinetic potential
Matter has good affinity with polymer, can be used as the mechanical performance that reinforcing material improves polymer.But it is specific to tired
Stone is ask to enhance natural rubber material, the consistency problem for both needing to solve improves rectorite material in the polymer uniform
Property, to improve reinforcing effect.Therefore, it is necessary to be modified processing to rectorite material.Currently, rectorite modified latex is sent out
Foam material is more rare for making sole material.
Chinese patent CN201410361107.9 discloses a kind of preparation of the rubber/clay composite material of heat oxygen aging resistance
Method is removed in pretreated clay water slurry by ultrasound, and catecholamine monomer is added under the aerobic alkaline condition of room temperature,
Autohemagglutination is deposited on clay layer surface；It is compound with rubber matrix in a manner of emulsion blending again, flocculate, washing, drying, be kneaded,
Rubber/clay nanocomposite is obtained after vulcanization.But the patent clay water slurry is directly blended with rubber latex material
Modified, mixed uniformity is affected by contingency, and product property is unstable, and the rubber composite material prepared is main
What is improved is the anti-aging property of rubber, the mechanical performance of rubber is improved limited.
It is multiple that Chinese patent CN201611120022.7 discloses a kind of graphene natural rubber for conveyer belt coating rubber
Condensation material and preparation method, using graphene, phyllosilicate, white carbon black, Heveatex as raw material, using wet process mixing technology system
It is standby to obtain；Then graphene native rubber composite material is plasticated, successively adds zinc oxide, stearic acid, anti-aging agent, silane coupled
It is once kneaded after agent, reinforcing agent, aromatic naphtha；Secondary mixing after sulphur, promotor is added again, obtains this product.But the patent
The consistency problem of reinforcing material and natural occurring latex materials is not improved, mechanical performance improves limited.
Therefore, in view of the above-mentioned problems, needing to provide a kind of increasing of mechanical strength that can effectively improve natural rubber material
Strong processing method, while the consistency problem of natural occurring latex materials and reinforcing material is solved, so that Heveatex obtained is compound
Material has good behaviour in sole material field.
Summary of the invention
The present invention is in view of the above-mentioned problems, provide a kind of property of modified rectorite/Heveatex composite foam material and its preparation side
Method.
Technical solution used by the present invention solves the above problems is: a kind of property of modified rectorite/Heveatex is composite foamed
Material, prepares the property of modified rectorite/Heveatex composite foam material raw material and its parts by weight include: Heveatex 100
Part, 5 parts~15 parts of carboxylic acrylonitrile butadiene rubber latex, 5 parts~20 parts of property of modified rectorite, 2 parts~4 parts of vulcanizing agent, 1 part~2 parts of promotor,
0.5 part~1.5 parts of anti-aging agent；
The present invention uses Heveatex for primary raw material, adds appropriate carboxylic acrylonitrile butadiene rubber latex, to improve the machine of Heveatex
Tool intensity and corrosion resistance, improve the application range of foamed material, and improve the nonpolarity and activity of Heveatex, increase
With the compatibility of property of modified rectorite；The property of modified rectorite for adding layer structure, increases the mechanical strength and product of foamed material, with
Heveatex and carboxylic acrylonitrile butadiene rubber latex coordination plasticizing composite foam material；Rationally, collective effect improves shoes for each raw material composition cooperation
The properties of product of bottom material increase the market competitiveness of natural rubber sole material；
Wherein, the method for modifying of the property of modified rectorite, comprising the following steps:
Organic modifiers plus water are mixed evenly step A1, and obtaining mass fraction is 0.5%~2% organic to change
Property agent solution；
Rectorite plus water are mixed evenly step A2, obtain the rectorite solution that mass fraction is 1%~10%；
The rectorite solution that step A2 is obtained is added dropwise to step with 60 drops/minute~120 drops/minute speed by step A3
In the organically-modified agent solution that rapid A1 is obtained, it is mixed evenly, obtains property of modified rectorite precursor liquid；This operation helps to make
The rectorite modified uniform and stable generation of process, avoids agglomeration；
Step A4 pours into the property of modified rectorite precursor liquid that step A3 is obtained in water heating kettle, in 120 DEG C~180 DEG C of temperature
Hydro-thermal reaction under the conditions of degree, products therefrom is washed, dry, grinding, obtains property of modified rectorite predecessor；This operation makes tired support
Stone modifying process uniformly effectively occurs, and reaction process is mild, and products therefrom crystallization effect is good, impurity is few, good dispersion, property are steady
It is fixed uniform；
The property of modified rectorite predecessor that step A4 is obtained is transferred in Muffle furnace, is warming up to 400 DEG C~650 by step A5
DEG C, 1h~2h is kept the temperature, products therefrom is ground, obtains property of modified rectorite；This operation is burning property of modified rectorite predecessor
The ingredients such as unstable water constituent and lower melting-point small molecular weight impurity are lost during knot, so that property of modified rectorite obtained
The properties of product for having more stable uniform.
Further, vulcanizing agent includes: sulphur or cumyl peroxide.
Further, the promotor are as follows: the mixing that captax and promotor TS are formed with mass ratio for 1:0.5~1.5
Object.
Further, anti-aging agent includes: antioxidant SP, antioxidant A, anti-aging agent RD, antioxidant D NP, antioxidant 4010, prevents
One or more of old agent AW, antioxidant MB, antioxidant D.
Further, in step A1, organic modifiers include: cationic polyvinyl alcohol, sodium alginate, carboxymethyl chitosan
In sugar, Monododecylphosphate triethanolamine, poloxamer, sodium carboxymethylcellulose, gamma-aminopropyl-triethoxy-silane
It is any；The application uses above-mentioned organic modifiers property of modified rectorite material, further increases the rectorite material of layer structure
Interface layer polarity and surface-active, improve with the product compatibility of latex material, be conducive to the tired support of polymer material insertion
Stone deck structure forms composite material.
Further, in step A2, the mass ratio of rectorite and organic modifiers described in step A1 is 100:0.5~5.
Further, in step A4, the time of hydro-thermal reaction is 12h~36h.
Another goal of the invention of the invention is to provide a kind of above-mentioned property of modified rectorite/Heveatex composite foam material
Preparation method, comprising the following steps:
Step S1 mixes the Heveatex of the parts by weight and carboxylic acrylonitrile butadiene rubber latex in the case where revolving speed is 300rpm~500rpm
2min~4min is closed, the property of modified rectorite of the parts by weight is then added, is mixed in the case where revolving speed is 1000rpm~2000rpm
8min~12min adds the vulcanizing agent, promotor, anti-aging agent of the parts by weight, is uniformly mixed, is filled with nitrogen or air, obtains
To mixing；Mixing is sprayed into coating surface, forms coating material；
The coating material that step S1 is obtained is carried out cooking processing by step S2 under the conditions of 160 DEG C~170 DEG C of temperature,
Then progress thermal finalization processing under the conditions of 60 DEG C~70 DEG C of temperature, placement 12h~for 24 hours, obtain the property of modified rectorite/day
Right latex composite foam material.
Further, in step S2, the time for cooking processing is 15s~90s.
Further, in step S2, the time of thermal finalization processing is 20min~40min.
The invention has the advantages that
1. the present invention uses Heveatex for primary raw material, appropriate carboxylic acrylonitrile butadiene rubber latex is added, to improve Heveatex
Mechanical strength and corrosion resistance, improve the application range of foamed material, and improve the nonpolarity and activity of Heveatex, increase
Add the compatibility with property of modified rectorite；The property of modified rectorite for adding layer structure, increases the mechanical strength and product of foamed material,
With Heveatex and carboxylic acrylonitrile butadiene rubber latex coordination plasticizing composite foam material；Rationally, collective effect improves sole for each raw material cooperation
The properties of product of material increase the market competitiveness of natural rubber sole material；
2. the present invention uses organic modifiers property of modified rectorite material, to improve the surface-active of rectorite, increase and glue
The compatibility of newborn material, the method for modifying of rectorite are easy, easily operated；
3. property of modified rectorite of the present invention/Heveatex composite foam material preparation method is suitble to scale volume production, favorably
In reducing production cost, the market competitiveness is improved.
Specific embodiment
The embodiment of the present invention is described in detail below, but what the present invention can be defined by the claims and cover
Multitude of different ways is implemented.
The formula of the application specific implementation are as follows: (kg)
Embodiment 1
A kind of property of modified rectorite/Heveatex composite foam material
Raw material is prepared using formula 1
The method of modifying of property of modified rectorite, comprising the following steps:
Cationic polyvinyl alcohol plus water are mixed evenly a, and it is molten to obtain the organic modifiers that mass fraction is 0.5%
Liquid；
Rectorite plus water are mixed evenly b, obtain the rectorite solution that mass fraction is 1%；In rectorite and a
The mass ratio of cationic polyvinyl alcohol is 100:0.5；
The rectorite solution that b is obtained is added dropwise in the organically-modified agent solution that a is obtained by c with 60 drops/minute speed,
It is mixed evenly, obtains property of modified rectorite precursor liquid；
D pours into the property of modified rectorite precursor liquid that c is obtained in water heating kettle, is lauched thermal response in 120 DEG C of temperature conditions
12h, products therefrom is washed, dry, grinding, obtains property of modified rectorite predecessor；
The property of modified rectorite predecessor that d is obtained is transferred in Muffle furnace by e, is warming up to 400 DEG C, keeps the temperature 1h, products therefrom
It is ground, obtain property of modified rectorite.
Above-mentioned property of modified rectorite/Heveatex composite foam material preparation method, comprising the following steps:
(1), the Heveatex of the parts by weight and carboxylic acrylonitrile butadiene rubber latex are mixed into 2min in the case where revolving speed is 300rpm, then
The property of modified rectorite of the parts by weight is added, mixes 8min in the case where revolving speed is 1000rpm, adds the vulcanization of the parts by weight
Agent, promotor, anti-aging agent are uniformly mixed, are filled with nitrogen, obtain mixing；Mixing is sprayed into coating surface, forms coating material
Material；
(2), the coating material that (1) obtains is carried out cooking processing 15s under the conditions of 160 DEG C of temperature, then at 60 DEG C
Temperature under the conditions of carry out thermal finalization handle 20min, place 12h, obtain property of modified rectorite/Heveatex composite foam material.
Embodiment 2
A kind of property of modified rectorite/Heveatex composite foam material
Raw material is prepared using formula 2
The method of modifying of property of modified rectorite, comprising the following steps:
Sodium alginate plus water are mixed evenly a, obtain the organically-modified agent solution that mass fraction is 2%；
Rectorite plus water are mixed evenly b, obtain the rectorite solution that mass fraction is 10%；Rectorite and a
The mass ratio of middle sodium alginate is 100:5；
The rectorite solution that b is obtained is added dropwise in the organically-modified agent solution that a is obtained by c with 120 drops/minute speed,
It is mixed evenly, obtains property of modified rectorite precursor liquid；
D pours into the property of modified rectorite precursor liquid that c is obtained in water heating kettle, is lauched thermal response in 180 DEG C of temperature conditions
36h, products therefrom is washed, dry, grinding, obtains property of modified rectorite predecessor；
The property of modified rectorite predecessor that d is obtained is transferred in Muffle furnace by e, is warming up to 650 DEG C, keeps the temperature 2h, products therefrom
It is ground, obtain property of modified rectorite.
Above-mentioned property of modified rectorite/Heveatex composite foam material preparation method, comprising the following steps:
(1), the Heveatex of the parts by weight and carboxylic acrylonitrile butadiene rubber latex are mixed into 4min in the case where revolving speed is 500rpm, then
The property of modified rectorite of the parts by weight is added, mixes 12min in the case where revolving speed is 2000rpm, adds the vulcanization of the parts by weight
Agent, promotor, anti-aging agent are uniformly mixed, are filled with air, obtain mixing；Mixing is sprayed into coating surface, forms coating material
Material；
(2), the coating material that (1) obtains is carried out cooking processing 90s under the conditions of 170 DEG C of temperature, then at 70 DEG C
Temperature under the conditions of carry out thermal finalization handle 40min, place for 24 hours, obtain property of modified rectorite/Heveatex composite foam material.
Embodiment 3
A kind of property of modified rectorite/Heveatex composite foam material
Raw material is prepared using formula 3
The method of modifying of property of modified rectorite, comprising the following steps:
Carboxymethyl chitosan plus water are mixed evenly a, and it is molten to obtain the organic modifiers that mass fraction is 1.25%
Liquid；
Rectorite plus water are mixed evenly b, obtain the rectorite solution that mass fraction is 5.5%；Rectorite and a
The mass ratio of middle carboxymethyl chitosan is 100:2.75；
The rectorite solution that b is obtained is added dropwise in the organically-modified agent solution that a is obtained by c with 90 drops/minute speed,
It is mixed evenly, obtains property of modified rectorite precursor liquid；
D pours into the property of modified rectorite precursor liquid that c is obtained in water heating kettle, is lauched thermal response in 150 DEG C of temperature conditions
For 24 hours, products therefrom it is washed, it is dry, grinding, obtain property of modified rectorite predecessor；
The property of modified rectorite predecessor that d is obtained is transferred in Muffle furnace by e, is warming up to 525 DEG C, keeps the temperature 1.5h, and gained produces
Object is ground, obtains property of modified rectorite.
Above-mentioned property of modified rectorite/Heveatex composite foam material preparation method, comprising the following steps:
(1), the Heveatex of the parts by weight and carboxylic acrylonitrile butadiene rubber latex are mixed into 3min in the case where revolving speed is 400rpm, then
The property of modified rectorite of the parts by weight is added, mixes 10min in the case where revolving speed is 1500rpm, adds the vulcanization of the parts by weight
Agent, promotor, anti-aging agent are uniformly mixed, are filled with nitrogen, obtain mixing；Mixing is sprayed into coating surface, forms coating material
Material；
(2), the coating material that (1) obtains is carried out cooking processing 50s under the conditions of 165 DEG C of temperature, then at 65 DEG C
Temperature under the conditions of carry out thermal finalization handle 30min, place 18h, obtain property of modified rectorite/Heveatex composite foam material.
Embodiment 4
A kind of property of modified rectorite/Heveatex composite foam material
Raw material is prepared using formula 4
The method of modifying of property of modified rectorite, comprising the following steps:
Monododecylphosphate triethanolamine is added water, is mixed evenly by a, and obtaining mass fraction is 0.875%
Organically-modified agent solution；
Rectorite plus water are mixed evenly b, obtain the rectorite solution that mass fraction is 3.75%；Rectorite with
The mass ratio of Monododecylphosphate triethanolamine is 100:1.625 in a；
The rectorite solution that b is obtained is added dropwise in the organically-modified agent solution that a is obtained by c with 75 drops/minute speed,
It is mixed evenly, obtains property of modified rectorite precursor liquid；
D pours into the property of modified rectorite precursor liquid that c is obtained in water heating kettle, is lauched thermal response in 135 DEG C of temperature conditions
18h, products therefrom is washed, dry, grinding, obtains property of modified rectorite predecessor；
The property of modified rectorite predecessor that d is obtained is transferred in Muffle furnace by e, is warming up to 463 DEG C, keeps the temperature 1.5h, and gained produces
Object is ground, obtains property of modified rectorite.
Above-mentioned property of modified rectorite/Heveatex composite foam material preparation method, comprising the following steps:
(1), the Heveatex of the parts by weight and carboxylic acrylonitrile butadiene rubber latex are mixed into 3.5min in the case where revolving speed is 350rpm, so
The property of modified rectorite of the parts by weight is added afterwards, mixes 11min in the case where revolving speed is 1200rpm, adds the sulphur of the parts by weight
Agent, promotor, anti-aging agent are uniformly mixed, are filled with air, obtain mixing；Mixing is sprayed into coating surface, forms coating material
Material；
(2), the coating material that (1) obtains is carried out cooking processing 78s under the conditions of 162 DEG C of temperature, then at 62 DEG C
Temperature under the conditions of carry out thermal finalization handle 35min, place 22h, obtain property of modified rectorite/Heveatex composite foam material.
Embodiment 5
A kind of property of modified rectorite/Heveatex composite foam material
Raw material is prepared using formula 5
The method of modifying of property of modified rectorite, comprising the following steps:
Poloxamer plus water are mixed evenly a, obtain the organically-modified agent solution that mass fraction is 1.625%；
Rectorite plus water are mixed evenly b, obtain the rectorite solution that mass fraction is 7.75%；Rectorite with
The mass ratio of poloxamer is 100:3.875 in a；
The rectorite solution that b is obtained is added dropwise in the organically-modified agent solution that a is obtained by c with 105 drops/minute speed,
It is mixed evenly, obtains property of modified rectorite precursor liquid；
D pours into the property of modified rectorite precursor liquid that c is obtained in water heating kettle, is lauched thermal response in 165 DEG C of temperature conditions
30h, products therefrom is washed, dry, grinding, obtains property of modified rectorite predecessor；
The property of modified rectorite predecessor that d is obtained is transferred in Muffle furnace by e, is warming up to 588 DEG C, keeps the temperature 1.75h, gained
Product is ground, obtains property of modified rectorite.
Above-mentioned property of modified rectorite/Heveatex composite foam material preparation method, comprising the following steps:
(1), the Heveatex of the parts by weight and carboxylic acrylonitrile butadiene rubber latex are mixed into 2.5min in the case where revolving speed is 450rpm, so
The property of modified rectorite of the parts by weight is added afterwards, mixes 9min in the case where revolving speed is 1800rpm, adds the vulcanization of the parts by weight
Agent, promotor, anti-aging agent are uniformly mixed, are filled with nitrogen, obtain mixing；Mixing is sprayed into coating surface, forms coating material
Material；
(2), the coating material that (1) obtains is carried out cooking processing 25s under the conditions of 168 DEG C of temperature, then at 68 DEG C
Temperature under the conditions of carry out thermal finalization handle 25min, place 14h, obtain property of modified rectorite/Heveatex composite foam material.
Embodiment 6
The difference of itself and embodiment 3 be only that organic modifiers using sodium carboxymethylcellulose, other include formulation data,
It is each in all data, property of modified rectorite/Heveatex composite foam material preparation method in the method for modifying of property of modified rectorite
Item data is same as Example 3.
Embodiment 7
The difference of itself and embodiment 3 is only that organic modifiers using gamma-aminopropyl-triethoxy-silane, other include matching
Number formulary is according to all data, property of modified rectorite/Heveatex composite foam material preparation side in the method for modifying of, property of modified rectorite
All data is same as Example 3 in method.
Comparative example 1
A kind of Heveatex composite foam material
Raw material is prepared using formula 6
The preparation method of above-mentioned Heveatex composite foam material, comprising the following steps:
(1), the Heveatex of the parts by weight and carboxylic acrylonitrile butadiene rubber latex are mixed into 3min in the case where revolving speed is 400rpm, then plus
Enter the vulcanizing agent, promotor, anti-aging agent of the parts by weight, is uniformly mixed, is filled with nitrogen, obtains mixing；Mixing is sprayed into painting
Cloth surface forms coating material；
(2), the coating material that (1) obtains is carried out cooking processing 50s under the conditions of 165 DEG C of temperature, then at 65 DEG C
Temperature under the conditions of carry out thermal finalization handle 30min, place 18h, obtain Heveatex composite foam material.
Comparative example 2
A kind of Heveatex foamed material
Raw material is prepared using formula 7
The preparation method of above-mentioned Heveatex foamed material, comprising the following steps:
(1), the Heveatex of the parts by weight is mixed into 3min in the case where revolving speed is 400rpm, adds the parts by weight
Vulcanizing agent, promotor, anti-aging agent are uniformly mixed, are filled with nitrogen, obtain mixing；Mixing is sprayed into coating surface, forms coating
Material；
(2), the coating material that (1) obtains is carried out cooking processing 50s under the conditions of 165 DEG C of temperature, then at 65 DEG C
Temperature under the conditions of carry out thermal finalization handle 30min, place 18h, obtain Heveatex foamed material.
Comparative example 3
A kind of rectorite/Heveatex composite foam material, prepares the rectorite/Heveatex composite foam material
Raw material and its parts by weight include: Heveatex 50kg, carboxylic acrylonitrile butadiene rubber latex 5kg, rectorite 6.25kg, sulphur 1.5kg, promotor
M0.375kg, promotor TS0.375kg, antioxidant 4010 0.2kg, antioxidant A W0.2kg, antioxidant MB 0.1kg.
Above-mentioned rectorite/Heveatex composite foam material preparation method, comprising the following steps:
(1), the Heveatex of the parts by weight and carboxylic acrylonitrile butadiene rubber latex are mixed into 3min in the case where revolving speed is 400rpm, then
The rectorite of the parts by weight is added, mixes 10min in the case where revolving speed is 1500rpm, adds the vulcanizing agent of the parts by weight, promote
Into agent, anti-aging agent, it is uniformly mixed, is filled with nitrogen, obtains mixing；Mixing is sprayed into coating surface, forms coating material；
(2), the coating material that (1) obtains is carried out cooking processing 50s under the conditions of 165 DEG C of temperature, then at 65 DEG C
Temperature under the conditions of carry out thermal finalization handle 30min, place 18h, obtain rectorite/Heveatex composite foam material.
Experimental example 1
Y1~Y7, comparative example 1 are labeled as to property of modified rectorite made from Examples 1 to 7/Heveatex composite foam material
Heveatex composite foam material obtained is labeled as D1, and Heveatex foamed material made from comparative example 2 is labeled as D2, comparison
Rectorite made from example 3/Heveatex composite foam material is labeled as D3, and to Y1~Y7, the performance of D1~D3 is tested, and surveys
Test result is as shown in table 1.Wherein, resistance to acid and alkali is tested according to GB/12019-1989.Ageing-resistant performance is according to GB/T9871-
2008 method C test, test temperature are 125 DEG C ± 2 DEG C, testing time 72h.
Property of modified rectorite made from 1 Examples 1 to 7 of table/Heveatex composite foam material the performance test results
Table 1 show property of modified rectorite made from the embodiment of the present application/Heveatex composite foam material in mechanical performance and
Corrosion resistance etc., which has compared to conventional Natural rubber foam material, significantly to be promoted.
These are only the preferred embodiment of the present invention, is not intended to restrict the invention, for those skilled in the art
For member, the invention may be variously modified and varied.All within the spirits and principles of the present invention, it is made it is any modification,
Equivalent replacement, improvement etc., should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of property of modified rectorite/Heveatex composite foam material, which is characterized in that prepare the property of modified rectorite/natural
The raw material and its parts by weight of latex composite foam material include: 100 parts of Heveatex, 5 parts~15 parts of carboxylic acrylonitrile butadiene rubber latex, modified
5 parts~20 parts of rectorite, 2 parts~4 parts of vulcanizing agent, 1 part~2 parts of promotor, 0.5 part~1.5 parts of anti-aging agent；
Wherein, the method for modifying of the property of modified rectorite, comprising the following steps:
Organic modifiers plus water are mixed evenly step A1, obtain the organic modifiers that mass fraction is 0.5%~2%
Solution；
Rectorite plus water are mixed evenly step A2, obtain the rectorite solution that mass fraction is 1%~10%；
The rectorite solution that step A2 is obtained is added dropwise to step A1 with 60 drops/minute~120 drops/minute speed by step A3
It in obtained organically-modified agent solution, is mixed evenly, obtains property of modified rectorite precursor liquid；
Step A4 pours into the property of modified rectorite precursor liquid that step A3 is obtained in water heating kettle, in 120 DEG C~180 DEG C of temperature strip
Hydro-thermal reaction under part, products therefrom is washed, dry, grinding, obtains property of modified rectorite predecessor；
The property of modified rectorite predecessor that step A4 is obtained is transferred in Muffle furnace by step A5, is warming up to 400 DEG C~650 DEG C, is protected
Warm 1h~2h, products therefrom is ground, obtains property of modified rectorite.
2. property of modified rectorite according to claim 1/Heveatex composite foam material, which is characterized in that the vulcanization
Agent includes: sulphur or cumyl peroxide.
3. property of modified rectorite according to claim 1/Heveatex composite foam material, which is characterized in that the promotion
Agent are as follows: the mixture that captax and promotor TS are formed with mass ratio for 1:0.5~1.5.
4. property of modified rectorite according to claim 1/Heveatex composite foam material, which is characterized in that described anti-old
Agent includes: antioxidant SP, antioxidant A, anti-aging agent RD, antioxidant D NP, antioxidant 4010, antioxidant A W, antioxidant MB, prevents always
One or more of agent D.
5. property of modified rectorite according to claim 1/Heveatex composite foam material, which is characterized in that in step A1,
The organic modifiers include: cationic polyvinyl alcohol, sodium alginate, carboxymethyl chitosan, three second of Monododecylphosphate
Any one of hydramine, poloxamer, sodium carboxymethylcellulose, gamma-aminopropyl-triethoxy-silane.
6. property of modified rectorite according to claim 1/Heveatex composite foam material, which is characterized in that in step A2,
The mass ratio of the rectorite and organic modifiers described in step A1 is 100:0.5~5.
7. property of modified rectorite according to claim 1/Heveatex composite foam material, which is characterized in that in step A4,
The time of the hydro-thermal reaction is 12h~36h.
8. it is a kind of according to claim 1~7 in any property of modified rectorite/Heveatex composite foam material preparation
Method, which comprises the following steps:
Step S1 mixes the Heveatex of the parts by weight and carboxylic acrylonitrile butadiene rubber latex in the case where revolving speed is 300rpm~500rpm
Then the property of modified rectorite of the parts by weight is added in 2min~4min, mix 8min in the case where revolving speed is 1000rpm~2000rpm
~12min adds the vulcanizing agent, promotor, anti-aging agent of the parts by weight, is uniformly mixed, is filled with nitrogen or air, is mixed
Material；Mixing is sprayed into coating surface, forms coating material；
The coating material that step S1 is obtained is carried out cooking processing, then by step S2 under the conditions of 160 DEG C~170 DEG C of temperature
Progress thermal finalization processing under the conditions of 60 DEG C~70 DEG C of temperature, placement 12h~for 24 hours, obtain the property of modified rectorite/natural gum
Newborn composite foam material.
9. preparation method according to claim 8, which is characterized in that in step S2, the time for cooking processing is 15s
~90s.
10. preparation method according to claim 8, which is characterized in that in step S2, the time of the thermal finalization processing is
20min~40min.
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