CN111019404A - Modified attapulgite for rubber reinforcement and preparation method thereof - Google Patents
Modified attapulgite for rubber reinforcement and preparation method thereof Download PDFInfo
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- CN111019404A CN111019404A CN201911200441.5A CN201911200441A CN111019404A CN 111019404 A CN111019404 A CN 111019404A CN 201911200441 A CN201911200441 A CN 201911200441A CN 111019404 A CN111019404 A CN 111019404A
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- 229960000892 attapulgite Drugs 0.000 title claims abstract description 175
- 229910052625 palygorskite Inorganic materials 0.000 title claims abstract description 175
- 229920001971 elastomer Polymers 0.000 title claims abstract description 80
- 239000005060 rubber Substances 0.000 title claims abstract description 80
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- 230000002787 reinforcement Effects 0.000 title claims description 29
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 96
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 59
- 238000003756 stirring Methods 0.000 claims abstract description 56
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 55
- 238000000034 method Methods 0.000 claims abstract description 39
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 37
- 238000002390 rotary evaporation Methods 0.000 claims abstract description 34
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 33
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229910052796 boron Inorganic materials 0.000 claims abstract description 33
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 33
- 239000011574 phosphorus Substances 0.000 claims abstract description 33
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000011737 fluorine Substances 0.000 claims abstract description 31
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 31
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims abstract description 24
- 230000003014 reinforcing effect Effects 0.000 claims abstract description 24
- 239000003599 detergent Substances 0.000 claims abstract description 23
- 239000002270 dispersing agent Substances 0.000 claims abstract description 23
- -1 tri-n-butylphosphonium tetrafluoroborate Chemical compound 0.000 claims abstract description 23
- 238000001291 vacuum drying Methods 0.000 claims abstract description 23
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 22
- BONNPLTURUUHRQ-UHFFFAOYSA-K trisodium;n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine;triacetate Chemical compound [Na+].[Na+].[Na+].CC([O-])=O.CC([O-])=O.CC([O-])=O.CO[Si](OC)(OC)CCCNCCN BONNPLTURUUHRQ-UHFFFAOYSA-K 0.000 claims abstract description 22
- 239000000203 mixture Substances 0.000 claims abstract description 21
- KRIUTXYABPSKPN-UHFFFAOYSA-N trimethoxy-[3-[2-[2-(2-methoxyethoxy)ethoxy]ethoxy]propyl]silane Chemical compound COCCOCCOCCOCCC[Si](OC)(OC)OC KRIUTXYABPSKPN-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000000227 grinding Methods 0.000 claims abstract description 19
- 238000007873 sieving Methods 0.000 claims abstract description 19
- 238000005406 washing Methods 0.000 claims abstract description 19
- 238000010438 heat treatment Methods 0.000 claims abstract description 17
- 238000001816 cooling Methods 0.000 claims abstract description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 66
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 62
- 229920001503 Glucan Polymers 0.000 claims description 37
- 239000003960 organic solvent Substances 0.000 claims description 33
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 31
- 239000013067 intermediate product Substances 0.000 claims description 27
- 239000000047 product Substances 0.000 claims description 23
- AJTVSSFTXWNIRG-UHFFFAOYSA-N 2-[bis(2-hydroxyethyl)amino]ethanesulfonic acid Chemical compound OCC[NH+](CCO)CCS([O-])(=O)=O AJTVSSFTXWNIRG-UHFFFAOYSA-N 0.000 claims description 18
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 18
- 239000011261 inert gas Substances 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 17
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 12
- 238000012986 modification Methods 0.000 claims description 12
- 239000012298 atmosphere Substances 0.000 claims description 11
- 238000009210 therapy by ultrasound Methods 0.000 claims description 11
- IIZPXYDJLKNOIY-JXPKJXOSSA-N 1-palmitoyl-2-arachidonoyl-sn-glycero-3-phosphocholine Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@H](COP([O-])(=O)OCC[N+](C)(C)C)OC(=O)CCC\C=C/C\C=C/C\C=C/C\C=C/CCCCC IIZPXYDJLKNOIY-JXPKJXOSSA-N 0.000 claims description 10
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- 229940067606 lecithin Drugs 0.000 claims description 10
- 235000010445 lecithin Nutrition 0.000 claims description 10
- 239000000787 lecithin Substances 0.000 claims description 10
- RNXPZVYZVHJVHM-UHFFFAOYSA-N 1,12-dichlorododecane Chemical compound ClCCCCCCCCCCCCCl RNXPZVYZVHJVHM-UHFFFAOYSA-N 0.000 claims description 9
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 claims description 7
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 claims description 7
- 229910052786 argon Inorganic materials 0.000 claims description 5
- 229920000142 Sodium polycarboxylate Polymers 0.000 claims description 4
- 239000001307 helium Substances 0.000 claims description 4
- 229910052734 helium Inorganic materials 0.000 claims description 4
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 4
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 claims description 4
- 235000019982 sodium hexametaphosphate Nutrition 0.000 claims description 4
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims description 4
- 238000005119 centrifugation Methods 0.000 claims description 3
- 229910052754 neon Inorganic materials 0.000 claims description 3
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 claims description 3
- 239000004927 clay Substances 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 3
- 238000010304 firing Methods 0.000 abstract description 2
- 230000000694 effects Effects 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 10
- 238000011049 filling Methods 0.000 description 7
- 238000000746 purification Methods 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 244000043261 Hevea brasiliensis Species 0.000 description 5
- 239000002131 composite material Substances 0.000 description 5
- 229920003052 natural elastomer Polymers 0.000 description 5
- 229920001194 natural rubber Polymers 0.000 description 5
- 238000001704 evaporation Methods 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 239000002689 soil Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000012744 reinforcing agent Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000012454 non-polar solvent Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000000527 sonication Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/40—Compounds of aluminium
- C09C1/42—Clays
-
- 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
- C08K3/346—Clay
-
- 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
- C08K9/02—Ingredients treated with inorganic 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
- C08K9/10—Encapsulated ingredients
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/006—Combinations of treatments provided for in groups C09C3/04 - C09C3/12
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/06—Treatment with inorganic compounds
- C09C3/063—Coating
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/08—Treatment with low-molecular-weight non-polymer organic compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/12—Treatment with organosilicon compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
Abstract
A modified attapulgite for reinforcing rubber and a preparation method thereof are disclosed, wherein the method comprises the following steps: dispersing attapulgite in chloroform, adding a dispersing agent and a detergent, heating, dispersing, washing, vacuum drying, grinding and sieving to obtain purified attapulgite; dissolving tri-n-butylphosphonium tetrafluoroborate in water, adding purified attapulgite, stirring, vacuum drying, firing, cooling to room temperature, grinding, and sieving; dispersing the sieved phosphorus/boron/fluorine co-doped carbon-coated attapulgite and graphene oxide in ethanol, adding 3, 3-dimethoxy-2, 7,10,13, 16-pentaoxa-3-silaheptadecane and N- (trimethoxysilylpropyl) ethylenediamine triacetic acid sodium salt into the mixture, stirring the mixture for reaction, and then performing rotary evaporation to remove the ethanol. The method is simple and easy to implement, low in cost and suitable for continuous large-scale production, and the prepared product is excellent in comprehensive performance and can greatly improve the mechanical property, the high-temperature resistance, the flame retardance and the stability of the rubber.
Description
Technical Field
The invention belongs to the technical field of mineral materials, and particularly relates to modified attapulgite for rubber reinforcement and a preparation method thereof.
Background
The attapulgite is a water-containing magnesium-rich aluminosilicate clay mineral with a chain layer structure, crystals of the attapulgite are fibrous aggregates, multiple pore canals are arranged in the structure, concave-convex parts are arranged alternately, negative charges are carried on the inner surface and the outer surface of the attapulgite, the attapulgite can adsorb cations, the diameter of single fiber crystal of the attapulgite is about 20 nm, the length of the single fiber crystal of the attapulgite can reach 1 mu m, and the attapulgite belongs to a one-dimensional nano material and is known as 'the king of thousands of soils and ten thousands of soils'. The unique structure of the attapulgite enables the attapulgite to have excellent adsorption, colloid, filling and salt resistance. The method is widely applied to the fields of petroleum, chemical industry, metallurgy, environmental protection, papermaking, food, medicine, feed, fertilizer, textile, building materials, geological exploration, atomic energy industry and the like, and has the reputations of king of thousand soils, universal soils and the like.
The rubber is a common high polymer material, has high elasticity and slight plasticity at normal temperature, is easy to plasticate, mix, roll, extrude, form and the like, and is widely used for daily necessities and industrial products. However, the prior art natural rubber also has some drawbacks, such as: the material has the problems of poor strong acid resistance, swelling in a nonpolar solvent, poor oil resistance and solvent resistance, low conductivity, low air permeability resistance and the like. In addition, because the free volume of the rubber is larger and the intermolecular force is small, most of the rubbers, especially the non-self-reinforcing rubber, have no application value without being reinforced. Therefore, it is necessary to modify the conventional rubber for reinforcement. Carbon black and white carbon black are common reinforcing agents in the market, and the reinforcing agents have poor dispersibility in rubber and influence tensile strength, elongation at break, stress at definite elongation and hardness.
Due to its excellent filling performance, attapulgite is widely used for rubber reinforcement. However, since attapulgite has a large specific surface area, a high surface activity, and is easily agglomerated, and the surface contains polar hydroxyl groups, it has a poor affinity with nonpolar rubbers, and is more difficult to disperse in a rubber matrix when used as a filler-reinforcing material. Therefore, when it is used as a rubber filler, it is usually necessary to modify the surface of the rubber filler to improve its compatibility and filler effect in rubber, and to improve its dispersibility and affinity in a rubber matrix.
There are many methods for modifying attapulgite at present, including a heat treatment method, an ultrasonic treatment method, an acid treatment method, a surfactant treatment method, and the like, and the heat treatment method is a commonly used modification method at present. The attapulgite is subjected to heat treatment within a certain temperature range, four types of water in the attapulgite are continuously removed along with the increase of the temperature, the activity of the attapulgite is continuously increased, the specific surface area and the porosity are improved, the compatibility with nonpolar substances such as rubber is improved, and the adsorption property of the attapulgite can also be improved by the heat treatment at proper temperature. However, the requirement for temperature during heat treatment is high, the temperature condition needs to be strictly controlled, the structure, the appearance and the property of the attapulgite can be greatly changed when the heat treatment is carried out at different temperatures, and if the temperature is improperly controlled, the attapulgite can play a bad role.
The Chinese patent with the application number of 2014103897146 discloses a preparation method of modified attapulgite for reinforcing rubber, and particularly discloses that natural attapulgite subjected to sedimentation, centrifugal purification is soaked and coated by a soluble carbon source solution, and is dried, ground, sieved and placed in a reducing atmosphere for high-temperature carbonization to obtain the surface carbon-coated nano attapulgite. The process sequentially comprises the following steps of A: purifying attapulgite; b: pre-coating the attapulgite; c: charring the surface of attapulgite. The method has the advantages that after the natural attapulgite is simply treated, the polarity of the surface of the natural attapulgite can be changed, the compatibility of the natural attapulgite and non-polar rubber is enhanced, the filling amount of the attapulgite in a rubber matrix is increased, and the attapulgite/rubber composite material with excellent chemical properties is prepared. However, when the modified attapulgite for reinforcing rubber prepared by the method is used for filling rubber, the mechanical property is poor, and the high temperature resistance and the flame retardant property are to be improved.
Therefore, it is necessary to develop a novel method for modifying attapulgite to prepare a modified attapulgite for reinforcing rubber having excellent overall properties.
Disclosure of Invention
The technical problem to be solved is as follows: aiming at the technical problems, the invention provides the modified attapulgite for rubber reinforcement and the preparation method thereof, the preparation method is simple and easy to implement, has small dependence on equipment, low preparation cost and high efficiency, and is suitable for continuous large-scale production, the prepared modified attapulgite for rubber reinforcement has excellent comprehensive performance, and the mechanical property, high temperature resistance, flame retardance and stability of rubber can be greatly improved after the rubber is filled.
The technical scheme is as follows: a preparation method of modified attapulgite for reinforcing rubber comprises the following steps:
step one, purifying attapulgite: dispersing attapulgite in chloroform, stirring for 15-25 minutes at 40-60 ℃, then adding a dispersing agent and a detergent, heating in a water bath at 60-100 ℃, stirring for 20-40 minutes, then carrying out ultrasonic treatment for 8-14 minutes under ultrasonic waves, then centrifuging, washing for 3-7 times by using water for centrifugation, then placing in a vacuum drying oven for drying at 70-80 ℃ to constant weight, and then grinding and sieving by using a 200-mesh 400-mesh sieve for later use;
step two, phosphorus/boron/fluorine co-doped carbon-coated attapulgite: dissolving tri-n-butyl phosphorus tetrafluoroborate in water, adding the attapulgite purified in the step one, uniformly stirring, placing the product in a vacuum drying box, drying at 70-80 ℃ to constant weight, then burning for 3-5 hours in an inert gas atmosphere at 600 ℃ under 500-5 ℃, cooling to room temperature, grinding, and sieving with a 200-400-mesh sieve, wherein the mass ratio of the tri-n-butyl phosphorus tetrafluoroborate to the water to the attapulgite is 1 (15-25) to (3-5);
step three, organic and inorganic co-modification: dispersing the phosphorus/boron/fluorine co-doped carbon-coated attapulgite prepared in the second step and graphene oxide in ethanol, then 3, 3-dimethoxy-2, 7,10,13, 16-pentaoxa-3-silaheptadecane and N- (trimethoxysilylpropyl) ethylenediamine triacetic acid sodium salt are added into the mixture, stirring and reacting for 3-5 hours at 60-80 ℃, then removing ethanol by rotary evaporation to obtain modified attapulgite for reinforcing rubber, wherein the mass ratio of phosphorus/boron/fluorine co-doped carbon-coated attapulgite, graphene oxide, ethanol, 3-dimethoxy-2, 7,10,13, 16-pentaoxa-3-silaheptadecane and N- (trimethoxysilylpropyl) ethylenediamine triacetic acid sodium salt is 1: (0.3-0.5): 0.2:0.1.
Preferably, in the first step, the attapulgite is dispersed in chloroform, stirred at 60 ℃ for 25 minutes, then a dispersing agent and a detergent are added into the attapulgite, the attapulgite is heated in a water bath at 100 ℃, stirred for 40 minutes, then ultrasonically treated for 14 minutes under ultrasonic waves, centrifuged, washed 7 times by water centrifugation, then dried in a vacuum drying oven at 80 ℃ to constant weight, and milled and sieved by a 400-mesh sieve for standby.
Preferably, the tri-n-butyl phosphorus tetrafluoroborate is dissolved in water in the second step, then the attapulgite purified in the first step is added, the mixture is uniformly stirred, the product is placed in a vacuum drying oven to be dried to constant weight at 80 ℃, then the product is burned for 5 hours in an inert gas atmosphere at 600 ℃, then the product is cooled to room temperature, and is milled and sieved by a 400-mesh sieve, wherein the mass ratio of the tri-n-butyl phosphorus tetrafluoroborate to the water to the attapulgite is 1:25: 5.
Preferably, in the third step, the phosphorus/boron/fluorine co-doped carbon-coated attapulgite prepared in the second step and graphene oxide are dispersed in ethanol, then 3, 3-dimethoxy-2, 7,10,13, 16-pentaoxa-3-silaheptadecane and N- (trimethoxysilylpropyl) ethylenediamine triacetic acid sodium salt are added into the mixture, stirring and reacting for 5 hours at the temperature of 80 ℃, then removing ethanol by rotary evaporation to obtain the modified attapulgite for reinforcing the rubber, wherein the mass ratio of the phosphorus/boron/fluorine co-doped carbon-coated attapulgite, the graphene oxide, the ethanol, the 3, 3-dimethoxy-2, 7,10,13, 16-pentaoxa-3-silaheptadecane and the N- (trimethoxysilylpropyl) ethylenediamine triacetic acid sodium salt is 1:0.5:0.2: 0.1.
Preferably, the dispersant in the first step is at least one of sodium polyacrylate, sodium hexametaphosphate and sodium polycarboxylate.
Preferably, the detergent in the first step consists of the following components in parts by mass: 3-6 parts of lecithin, 10-15 parts of N, N-bis (2-hydroxyethyl) -2-aminoethanesulfonic acid modified amino modified glucan, 80-100 parts of water and 10-20 parts of ethanol, wherein the preparation method of the N, N-bis (2-hydroxyethyl) -2-aminoethanesulfonic acid modified amino modified glucan comprises the following steps: s1, adding N, N-bis (2-hydroxyethyl) -2-aminoethanesulfonic acid and dichloroalkane into an organic solvent, stirring and reacting for 3-6 hours at 70-80 ℃, then performing rotary evaporation to remove the solvent, washing the product for 3-5 times by using diethyl ether, and finally performing rotary evaporation to remove the diethyl ether to obtain an intermediate product; s2, adding the intermediate product obtained in the step S1 and the amino-modified glucan into tetrahydrofuran, stirring for 4-6 hours at 40-60 ℃, and then performing rotary evaporation to remove the tetrahydrofuran.
Preferably, the dichloroalkane in S1 is 1, 12-dichlorododecane, the organic solvent is tetrahydrofuran, diethyl ether, ethyl acetate or acetone, and the molar ratio of the N, N-bis (2-hydroxyethyl) -2-aminoethanesulfonic acid to the dichloroalkane to the organic solvent is 1:1 (6-10).
Preferably, the molar ratio of the intermediate product prepared by S1 in S2, the amino-modified glucan and the tetrahydrofuran is 1:1 (6-10).
Preferably, the inert gas in the second step is helium, neon or argon.
The modified attapulgite for rubber reinforcement prepared by the method.
Has the advantages that: 1. the method is simple and easy to implement, low in cost and suitable for continuous large-scale production; the prepared modified attapulgite for rubber reinforcement has excellent comprehensive performance, the surface polarity of the traditional attapulgite is further changed and the compatibility with non-polar rubber is enhanced by phosphorus/boron/fluorine co-doped carbon-coated attapulgite and organic and inorganic modification treatment on the premise of ensuring that the fibrous structure of the traditional attapulgite is not damaged, the purification effect and the surface wettability of the attapulgite treated by a dispersant and a detergent are enhanced, and the filling amount of the modified attapulgite in a rubber matrix can be greatly increased.
2. According to the invention, the attapulgite is coated with phosphorus/boron/fluorine co-doped carbon, the surface activity of the attapulgite can be improved by tri-n-butylphosphonium tetrafluoroborate, and the surface of the purified attapulgite can be covered with a non-polar carbon layer by combining the doped carbon, so that the nano-scale compounding of the attapulgite and non-polar rubber can be more easily realized, and the comprehensive performance of the rubber can be further improved;
3. the method also comprises the step of carrying out organic and inorganic co-modification on the phosphorus/boron/fluorine co-doped carbon-coated attapulgite, wherein firstly, the addition of the graphene oxide can be used for further improving the comprehensive performance of the rubber in cooperation with the attapulgite, and then the surface of the attapulgite is modified by 3, 3-dimethoxy-2, 7,10,13, 16-pentaoxa-3-silaheptadecane and N- (trimethoxysilylpropyl) ethylenediamine triacetic acid sodium salt, so that the surface activity of the attapulgite is improved, the compatibility of the attapulgite and the rubber to be filled is improved, the performance stability of the rubber is improved, and the service life of the rubber is prolonged;
4. according to the preparation method, the attapulgite is purified at first, and then a mode of combining ultrasound, heating and stirring is adopted, so that the purification effect is better, the purification efficiency is higher, the added dispersing agent is beneficial to the attapulgite to be dispersed more uniformly, and the purification is more thorough;
5. the detergent adopts a mixture of lecithin, N-bis (2-hydroxyethyl) -2-aminoethanesulfonic acid modified amino modified glucan, water and ethanol, and all components have synergistic effect, so that the surface wettability and the surface activity of the attapulgite can be improved, and the purification efficiency and the purification effect can be improved.
Detailed Description
The following description is presented to disclose the invention so as to enable any person skilled in the art to practice the invention. The preferred embodiments in the following description are given by way of example only, and other obvious variations will occur to those skilled in the art.
Example 1
A preparation method of modified attapulgite for reinforcing rubber comprises the following steps:
step one, purifying attapulgite: the method comprises the following steps of dispersing attapulgite in chloroform, stirring at 40 ℃ for 15 minutes, adding a dispersing agent and a detergent, heating in a water bath at 60 ℃, stirring for 20 minutes, performing ultrasonic treatment for 8 minutes under ultrasonic waves, centrifuging, washing for 3 times by using water in a centrifugal manner, drying in a vacuum drying oven at 70 ℃ to constant weight, grinding, and sieving with a 200-mesh sieve, wherein the dispersing agent is sodium polyacrylate, and the detergent is prepared from the following raw materials in parts by mass: 3 parts of lecithin, 10 parts of N, N-bis (2-hydroxyethyl) -2-aminoethanesulfonic acid modified amino modified glucan, 80 parts of water and 10 parts of ethanol, wherein the preparation method of the N, N-bis (2-hydroxyethyl) -2-aminoethanesulfonic acid modified amino modified glucan comprises the following steps: s1, adding N, N-bis (2-hydroxyethyl) -2-aminoethanesulfonic acid and dichloroalkane into an organic solvent, stirring and reacting for 3 hours at 70 ℃, then performing rotary evaporation to remove the solvent, washing the product for 3 times by using diethyl ether, and finally performing rotary evaporation to remove the diethyl ether to obtain an intermediate product, wherein the molar ratio of the N, N-bis (2-hydroxyethyl) -2-aminoethanesulfonic acid to the dichloroalkane to the organic solvent is 1:1:6, the dichloroalkane is 1, 12-dichlorododecane, and the organic solvent is tetrahydrofuran; s2, adding the intermediate product obtained in the step S1 and the amino-modified glucan into tetrahydrofuran, stirring for 4 hours at 40 ℃, and then removing the tetrahydrofuran by rotary evaporation, wherein the molar ratio of the intermediate product to the amino-modified glucan to the tetrahydrofuran is 1:1: 6.
Step two, phosphorus/boron/fluorine co-doped carbon-coated attapulgite: dissolving tri-n-butyl phosphorus tetrafluoroborate in water, gradually adding the attapulgite purified in the first step, uniformly stirring, placing the product in a vacuum drying oven, drying at 70 ℃ to constant weight, then firing for 3 hours at 500 ℃ in an inert gas atmosphere, cooling to room temperature, grinding, and sieving with a 200-mesh sieve, wherein the mass ratio of the tri-n-butyl phosphorus tetrafluoroborate to the water to the attapulgite is 1:15:3, and the inert gas is helium.
Step three, organic and inorganic co-modification: dispersing the phosphorus/boron/fluorine co-doped carbon-coated attapulgite and graphene oxide prepared in the second step into ethanol, adding 3, 3-dimethoxy-2, 7,10,13, 16-pentaoxa-3-silaheptadecane and N- (trimethoxysilylpropyl) ethylenediamine triacetic acid sodium salt into the ethanol, stirring the mixture for reaction for 3 hours at the temperature of 60 ℃, and then rotationally evaporating the mixture to remove the ethanol to obtain the modified attapulgite for reinforcing the rubber, wherein the mass ratio of the phosphorus/boron/fluorine co-doped carbon-coated attapulgite, the graphene oxide, the ethanol, the 3, 3-dimethoxy-2, 7,10,13, 16-pentaoxa-3-silaheptadecane and the N- (trimethoxysilylpropyl) ethylenediamine triacetic acid sodium salt is 1:0.3:0.2: 0.1.
The modified attapulgite for rubber reinforcement prepared by the method.
Example 2
A preparation method of modified attapulgite for reinforcing rubber comprises the following steps:
step one, purifying attapulgite: the method comprises the following steps of dispersing attapulgite in chloroform, stirring for 17 minutes at 45 ℃, adding a dispersing agent and a detergent, heating in a water bath at 70 ℃, stirring for 25 minutes, performing ultrasonic treatment for 9 minutes under ultrasonic waves, centrifuging, washing for 4 times by using water in a centrifugal manner, drying in a vacuum drying oven at 73 ℃ to constant weight, grinding, and sieving with a 250-mesh sieve for later use, wherein the dispersing agent is sodium hexametaphosphate, and the detergent is prepared from the following raw materials in parts by mass: 4 parts of lecithin, 11 parts of N, N-bis (2-hydroxyethyl) -2-aminoethanesulfonic acid modified amino modified glucan, 85 parts of water and 13 parts of ethanol, wherein the preparation method of the N, N-bis (2-hydroxyethyl) -2-aminoethanesulfonic acid modified amino modified glucan comprises the following steps: s1, adding N, N-bis (2-hydroxyethyl) -2-aminoethanesulfonic acid and dichloroalkane into an organic solvent, stirring and reacting for 4 hours at 73 ℃, then performing rotary evaporation to remove the solvent, washing the product for 4 times by using diethyl ether, and finally performing rotary evaporation to remove the diethyl ether to obtain an intermediate product, wherein the molar ratio of the N, N-bis (2-hydroxyethyl) -2-aminoethanesulfonic acid to the dichloroalkane to the organic solvent is 1:1:7, the dichloroalkane is 1, 12-dichlorododecane, and the organic solvent is diethyl ether; s2, adding the intermediate product obtained in the step S1 and the amino-modified glucan into tetrahydrofuran, stirring for 4.5 hours at 45 ℃, and then performing rotary evaporation to remove the tetrahydrofuran, wherein the molar ratio of the intermediate product to the amino-modified glucan to the tetrahydrofuran is 1:1: 7.
Step two, phosphorus/boron/fluorine co-doped carbon-coated attapulgite: dissolving tri-n-butyl phosphorus tetrafluoroborate in water, gradually adding the attapulgite purified in the first step, uniformly stirring, placing the product in a vacuum drying oven, drying at 73 ℃ to constant weight, then burning for 3.5 hours at 520 ℃ in an inert gas atmosphere, cooling to room temperature, grinding, and sieving with a 250-mesh sieve, wherein the mass ratio of the tri-n-butyl phosphorus tetrafluoroborate to the water to the attapulgite is 1:18:3.5, and the inert gas is neon.
Step three, organic and inorganic co-modification: dispersing the phosphorus/boron/fluorine co-doped carbon-coated attapulgite and graphene oxide prepared in the second step into ethanol, adding 3, 3-dimethoxy-2, 7,10,13, 16-pentaoxa-3-silaheptadecane and N- (trimethoxysilylpropyl) ethylenediamine triacetic acid sodium salt into the ethanol, stirring the mixture to react for 3.5 hours at 65 ℃, and then rotationally evaporating the mixture to remove the ethanol to obtain the modified attapulgite for reinforcing the rubber, wherein the mass ratio of the phosphorus/boron/fluorine co-doped carbon-coated attapulgite, the graphene oxide, the ethanol, the 3, 3-dimethoxy-2, 7,10,13, 16-pentaoxa-3-silaheptadecane and the N- (trimethoxysilylpropyl) ethylenediamine triacetic acid sodium salt is 1:0.5:0.2: 0.1.
The modified attapulgite for rubber reinforcement prepared by the method.
Example 3
A preparation method of modified attapulgite for reinforcing rubber comprises the following steps:
step one, purifying attapulgite: the method comprises the following steps of dispersing attapulgite in chloroform, stirring at 50 ℃ for 20 minutes, adding a dispersant and a detergent, heating in a water bath at 80 ℃, stirring for 30 minutes, performing ultrasonic treatment for 11 minutes under ultrasonic waves, centrifuging, washing for 5 times by using water in a centrifugal manner, drying in a vacuum drying oven at 75 ℃ to constant weight, grinding, and sieving with a 300-mesh sieve to obtain the dispersant, namely a sodium polycarboxylate, wherein the detergent is prepared from the following raw materials in parts by mass: 5 parts of lecithin, 13 parts of N, N-bis (2-hydroxyethyl) -2-aminoethanesulfonic acid modified amino modified glucan, 90 parts of water and 15 parts of ethanol, wherein the preparation method of the N, N-bis (2-hydroxyethyl) -2-aminoethanesulfonic acid modified amino modified glucan comprises the following steps: s1, adding N, N-bis (2-hydroxyethyl) -2-aminoethanesulfonic acid and dichloroalkane into an organic solvent, stirring and reacting for 4.5 hours at 75 ℃, then carrying out rotary evaporation to remove the organic solvent, washing the product for 4 times by using diethyl ether, and finally carrying out rotary evaporation to remove the diethyl ether to obtain an intermediate product, wherein the molar ratio of the N, N-bis (2-hydroxyethyl) -2-aminoethanesulfonic acid to the dichloroalkane to the organic solvent is 1:1:8, the dichloroalkane is 1, 12-dichlorododecane, and the organic solvent is ethyl acetate; s2, adding the intermediate product obtained in the step S1 and the amino-modified glucan into tetrahydrofuran, stirring at 50 ℃ for 5 hours, and then performing rotary evaporation to remove the tetrahydrofuran, wherein the molar ratio of the intermediate product to the amino-modified glucan to the tetrahydrofuran is 1:1: 8. Step two, phosphorus/boron/fluorine co-doped carbon-coated attapulgite: dissolving tri-n-butyl phosphorus tetrafluoroborate in water, gradually adding the attapulgite purified in the first step, uniformly stirring, placing the product in a vacuum drying oven, drying at 75 ℃ to constant weight, then burning for 4 hours at 550 ℃ in an inert gas atmosphere, cooling to room temperature, grinding, and sieving with a 300-mesh sieve, wherein the mass ratio of the tri-n-butyl phosphorus tetrafluoroborate to the water to the attapulgite is 1:20:4, and the inert gas is argon.
Step three, organic and inorganic co-modification: dispersing the phosphorus/boron/fluorine co-doped carbon-coated attapulgite and graphene oxide prepared in the second step into ethanol, adding 3, 3-dimethoxy-2, 7,10,13, 16-pentaoxa-3-silaheptadecane and N- (trimethoxysilylpropyl) ethylenediamine triacetic acid sodium salt into the ethanol, stirring the mixture for reaction for 4 hours at 70 ℃, and then rotationally evaporating the mixture to remove the ethanol to obtain the modified attapulgite for reinforcing the rubber, wherein the mass ratio of the phosphorus/boron/fluorine co-doped carbon-coated attapulgite, the graphene oxide, the ethanol, the 3, 3-dimethoxy-2, 7,10,13, 16-pentaoxa-3-silaheptadecane and the N- (trimethoxysilylpropyl) ethylenediamine triacetic acid sodium salt is 1:0.5:0.2: 0.1.
The modified attapulgite for rubber reinforcement prepared by the method.
Example 4
A preparation method of modified attapulgite for reinforcing rubber comprises the following steps:
step one, purifying attapulgite: dispersing attapulgite in chloroform, stirring for 24 minutes at 55 ℃, adding a dispersing agent and a detergent, heating in a water bath at 95 ℃, stirring for 38 minutes, performing ultrasonic treatment for 13 minutes under ultrasonic waves, centrifuging, washing for 3-7 times by using water in a centrifugal manner, drying in a vacuum drying oven at 78 ℃ to constant weight, grinding and sieving with a 380-mesh sieve for later use, wherein the dispersing agent is prepared by mixing sodium polyacrylate, sodium hexametaphosphate and sodium polycarboxylate in a mass ratio of 1:3:2, and the detergent is prepared from the following raw materials in parts by mass: 5 parts of lecithin, 14 parts of N, N-bis (2-hydroxyethyl) -2-aminoethanesulfonic acid modified amino modified glucan, 98 parts of water and 19 parts of ethanol, wherein the preparation method of the N, N-bis (2-hydroxyethyl) -2-aminoethanesulfonic acid modified amino modified glucan comprises the following steps: s1, adding N, N-bis (2-hydroxyethyl) -2-aminoethanesulfonic acid and dichloroalkane into an organic solvent, stirring and reacting for 5.5 hours at 79 ℃, then carrying out rotary evaporation to remove the organic solvent, washing the product for 5 times by using diethyl ether, and finally carrying out rotary evaporation to remove the diethyl ether to obtain an intermediate product, wherein the molar ratio of the N, N-bis (2-hydroxyethyl) -2-aminoethanesulfonic acid to the dichloroalkane to the organic solvent is 1:1:9.5, the dichloroalkane is 1, 12-dichlorododecane, and the organic solvent is tetrahydrofuran, diethyl ether, ethyl acetate and acetone which are mixed according to the mass ratio of 1:1:3: 5; s2, adding the intermediate product obtained in the step S1 and the amino-modified glucan into tetrahydrofuran, stirring at 59 ℃ for 5.8 hours, and then performing rotary evaporation to remove the tetrahydrofuran, wherein the molar ratio of the intermediate product to the amino-modified glucan to the tetrahydrofuran is 1:1:9. Step two, phosphorus/boron/fluorine co-doped carbon-coated attapulgite: dissolving tri-n-butyl phosphorus tetrafluoroborate in water, gradually adding purified attapulgite, uniformly stirring, placing a product in a vacuum drying oven at 79 ℃ for drying to constant weight, then burning for 4.8 hours at 590 ℃ in an inert gas atmosphere, cooling to room temperature, grinding, and sieving with a 380-mesh sieve, wherein the mass ratio of the tri-n-butyl phosphorus tetrafluoroborate to the water to the attapulgite is 1:23:4.8, and the inert gas is helium;
step three, organic and inorganic co-modification: dispersing the phosphorus/boron/fluorine co-doped carbon-coated attapulgite and graphene oxide prepared in the second step into ethanol, adding 3, 3-dimethoxy-2, 7,10,13, 16-pentaoxa-3-silaheptadecane and N- (trimethoxysilylpropyl) ethylenediamine triacetic acid sodium salt into the ethanol, stirring the mixture to react for 4.7 hours at 78 ℃, and then performing rotary evaporation to remove the ethanol to obtain the modified attapulgite for reinforcing the rubber, wherein the phosphorus/boron/fluorine co-doped carbon-coated attapulgite, the graphene oxide, the ethanol, the 3, 3-dimethoxy-2, 7,10,13, 16-pentaoxa-3-silaheptadecane and the N- (trimethoxysilylpropyl) ethylenediamine triacetic acid sodium salt have a mass ratio of 1:0.5:0.2: 0.1.
The modified attapulgite for rubber reinforcement prepared by the method.
Example 5
A preparation method of modified attapulgite for reinforcing rubber comprises the following steps:
step one, purifying attapulgite: the method comprises the following steps of dispersing attapulgite in chloroform, stirring at 60 ℃ for 25 minutes, adding a dispersing agent and a detergent, heating in a water bath at 100 ℃, stirring for 40 minutes, performing ultrasonic treatment for 14 minutes under ultrasonic waves, centrifuging, washing for 7 times by using water in a centrifugal manner, drying in a vacuum drying oven at 80 ℃ to constant weight, grinding, and sieving with a 400-mesh sieve for later use, wherein the dispersing agent is sodium polyacrylate, and the detergent is prepared from the following raw materials in parts by mass: 6 parts of lecithin, 15 parts of N, N-bis (2-hydroxyethyl) -2-aminoethanesulfonic acid modified amino modified glucan, 100 parts of water and 20 parts of ethanol, wherein the preparation method of the N, N-bis (2-hydroxyethyl) -2-aminoethanesulfonic acid modified amino modified glucan comprises the following steps: s1, adding N, N-bis (2-hydroxyethyl) -2-aminoethanesulfonic acid and dichloroalkane into an organic solvent, stirring and reacting for 6 hours at 80 ℃, then performing rotary evaporation to remove the organic solvent, washing the product for 3-5 times by using diethyl ether, and finally performing rotary evaporation to remove the diethyl ether to obtain an intermediate product, wherein the molar ratio of the N, N-bis (2-hydroxyethyl) -2-aminoethanesulfonic acid to the dichloroalkane to the organic solvent is 1:1:10, the dichloroalkane is 1, 12-dichlorododecane, and the organic solvent is acetone; s2, adding the intermediate product obtained in the step S1 and the amino-modified glucan into tetrahydrofuran, stirring for 6 hours at 60 ℃, and then removing the tetrahydrofuran by rotary evaporation, wherein the molar ratio of the intermediate product to the amino-modified glucan to the tetrahydrofuran is 1:1: 10.
Step two, phosphorus/boron/fluorine co-doped carbon-coated attapulgite: dissolving tri-n-butyl phosphorus tetrafluoroborate in water, gradually adding the attapulgite purified in the first step, uniformly stirring, placing the product in a vacuum drying oven, drying at 80 ℃ to constant weight, then burning for 5 hours at 600 ℃ in an inert gas atmosphere, cooling to room temperature, grinding, and sieving with a 400-mesh sieve, wherein the mass ratio of the tri-n-butyl phosphorus tetrafluoroborate to the water to the attapulgite is 1:25:5, and the inert gas is argon.
Step three, organic and inorganic co-modification: dispersing the phosphorus/boron/fluorine co-doped carbon-coated attapulgite and graphene oxide prepared in the second step into ethanol, adding 3, 3-dimethoxy-2, 7,10,13, 16-pentaoxa-3-silaheptadecane and N- (trimethoxysilylpropyl) ethylenediamine triacetic acid sodium salt into the ethanol, stirring the mixture for reaction for 5 hours at the temperature of 80 ℃, and then rotationally evaporating the mixture to remove the ethanol to obtain the modified attapulgite for reinforcing the rubber, wherein the mass ratio of the phosphorus/boron/fluorine co-doped carbon-coated attapulgite, the graphene oxide, the ethanol, the 3, 3-dimethoxy-2, 7,10,13, 16-pentaoxa-3-silaheptadecane and the N- (trimethoxysilylpropyl) ethylenediamine triacetic acid sodium salt is 1:0.5:0.2: 0.1.
The modified attapulgite for rubber reinforcement prepared by the method.
Comparative example 1
This comparative example provides a modified attapulgite for rubber reinforcement, the formulation and preparation method of which are the same as those of example 5, except that ultrasonic sonication was not used in the first step.
Comparative example 2
The comparative example provides modified attapulgite for rubber reinforcement, and the formula and the preparation method of the modified attapulgite are different from those in the same example 5 in that the original step two is not adopted, namely phosphorus/boron/fluorine co-doped carbon-coated attapulgite is not adopted, and the specific preparation process is as follows: a preparation method of modified attapulgite for reinforcing rubber comprises the following steps:
step one, purifying attapulgite: the method comprises the following steps of dispersing attapulgite in chloroform, stirring at 60 ℃ for 25 minutes, adding a dispersing agent and a detergent, heating in a water bath at 100 ℃, stirring for 40 minutes, performing ultrasonic treatment for 14 minutes under ultrasonic waves, centrifuging, washing for 7 times by using water in a centrifugal manner, drying in a vacuum drying oven at 80 ℃ to constant weight, grinding, and sieving with a 400-mesh sieve for later use, wherein the dispersing agent is sodium polyacrylate, and the detergent is prepared from the following raw materials in parts by mass: 6 parts of lecithin, 15 parts of N, N-bis (2-hydroxyethyl) -2-aminoethanesulfonic acid modified amino modified glucan, 100 parts of water and 20 parts of ethanol, wherein the preparation method of the N, N-bis (2-hydroxyethyl) -2-aminoethanesulfonic acid modified amino modified glucan comprises the following steps: s1, adding N, N-bis (2-hydroxyethyl) -2-aminoethanesulfonic acid and dichloroalkane into an organic solvent, stirring and reacting for 6 hours at 80 ℃, then performing rotary evaporation to remove the organic solvent, washing the product for 3-5 times by using diethyl ether, and finally performing rotary evaporation to remove the diethyl ether to obtain an intermediate product, wherein the molar ratio of the N, N-bis (2-hydroxyethyl) -2-aminoethanesulfonic acid to the dichloroalkane to the organic solvent is 1:1:10, the dichloroalkane is 1, 12-dichlorododecane, and the organic solvent is acetone; s2, adding the intermediate product obtained in the step S1 and the amino-modified glucan into tetrahydrofuran, stirring for 6 hours at 60 ℃, and then removing the tetrahydrofuran by rotary evaporation, wherein the molar ratio of the intermediate product to the amino-modified glucan to the tetrahydrofuran is 1:1: 10.
Step two, organic and inorganic co-modification: dispersing the attapulgite and graphene oxide purified in the first step into ethanol, adding 3, 3-dimethoxy-2, 7,10,13, 16-pentaoxa-3-silaheptadecane and N- (trimethoxysilylpropyl) ethylenediamine triacetic acid sodium salt into the ethanol, stirring the mixture for reaction for 5 hours at the temperature of 80 ℃, and then performing rotary evaporation to remove the ethanol to obtain the modified attapulgite for reinforcing the rubber, wherein the mass ratio of the phosphorus/boron/fluorine co-doped carbon-coated attapulgite, the graphene oxide, the ethanol, the 3, 3-dimethoxy-2, 7,10,13, 16-pentaoxa-3-silaheptadecane and the N- (trimethoxysilylpropyl) ethylenediamine triacetic acid sodium salt is 1:0.5:0.2: 0.1.
The modified attapulgite for rubber reinforcement prepared by the method.
Comparative example 3
The comparative example provides modified attapulgite for rubber reinforcement, and the formula and the preparation method of the modified attapulgite are the same as those in example 5, except that the original step three is omitted, namely, organic and inorganic co-modification is not adopted, and the specific preparation process is as follows: a preparation method of modified attapulgite for reinforcing rubber comprises the following steps:
step one, purifying attapulgite: the method comprises the following steps of dispersing attapulgite in chloroform, stirring at 60 ℃ for 25 minutes, adding a dispersing agent and a detergent, heating in a water bath at 100 ℃, stirring for 40 minutes, performing ultrasonic treatment for 14 minutes under ultrasonic waves, centrifuging, washing for 7 times by using water in a centrifugal manner, drying in a vacuum drying oven at 80 ℃ to constant weight, grinding, and sieving with a 400-mesh sieve for later use, wherein the dispersing agent is sodium polyacrylate, and the detergent is prepared from the following raw materials in parts by mass: 6 parts of lecithin, 15 parts of N, N-bis (2-hydroxyethyl) -2-aminoethanesulfonic acid modified amino modified glucan, 100 parts of water and 20 parts of ethanol, wherein the preparation method of the N, N-bis (2-hydroxyethyl) -2-aminoethanesulfonic acid modified amino modified glucan comprises the following steps: s1, adding N, N-bis (2-hydroxyethyl) -2-aminoethanesulfonic acid and dichloroalkane into an organic solvent, stirring and reacting for 6 hours at 80 ℃, then performing rotary evaporation to remove the organic solvent, washing the product for 3-5 times by using diethyl ether, and finally performing rotary evaporation to remove the diethyl ether to obtain an intermediate product, wherein the molar ratio of the N, N-bis (2-hydroxyethyl) -2-aminoethanesulfonic acid to the dichloroalkane to the organic solvent is 1:1:10, the dichloroalkane is 1, 12-dichlorododecane, and the organic solvent is acetone; s2, adding the intermediate product obtained in the step S1 and the amino-modified glucan into tetrahydrofuran, stirring for 6 hours at 60 ℃, and then removing the tetrahydrofuran by rotary evaporation, wherein the molar ratio of the intermediate product to the amino-modified glucan to the tetrahydrofuran is 1:1: 10.
Step two, phosphorus/boron/fluorine co-doped carbon-coated attapulgite: dissolving tri-n-butyl phosphorus tetrafluoroborate in water, gradually adding the attapulgite purified in the first step, uniformly stirring, placing the product in a vacuum drying oven, drying at 80 ℃ to constant weight, then burning for 5 hours at 600 ℃ in an inert gas atmosphere, cooling to room temperature, grinding, and sieving with a 400-mesh sieve, wherein the mass ratio of the tri-n-butyl phosphorus tetrafluoroborate to the water to the attapulgite is 1:25:5, and the inert gas is argon.
The modified attapulgite for rubber reinforcement prepared by the method.
Comparative example 4
The comparative example provides a modified attapulgite for rubber reinforcement, the formulation and preparation method of which are the same as those of example 1 disclosed in chinese patent 201410389714.6.
In order to further illustrate the beneficial technical effects of the modified attapulgite for rubber reinforcement in the examples of the present invention, the modified attapulgite for rubber reinforcement described in the examples 1 to 5 and the comparative examples 1 to 4 was filled with natural rubber at a filling mass ratio of 5:100, and the obtained composite material was subjected to performance tests, and the test results and the test methods are shown in the following table.
The tensile strength in the above table is tested according to GB/T1040-2006, the impact resistance is tested according to ASTM D256, the limiting oxygen index is tested according to GB5454-85, and the Vicat softening point is tested according to GB 1633-1979.
As can be seen from the data in the table, the composite materials obtained by filling the natural rubber with the modified attapulgite for rubber reinforcement prepared in the examples 1 to 5 of the invention have the tensile strength of more than or equal to 35.5MPa, the impact resistance of more than or equal to 350J/M, the limiting oxygen index of more than or equal to 36.2 percent and the Vicat softening point of more than or equal to 122 ℃; the modified attapulgite clay filled natural rubber composite materials for rubber reinforcement prepared in the comparative examples 1 to 4 have tensile strength of less than or equal to 24.6MPa, impact resistance of less than or equal to 314J/M, limiting oxygen index of less than or equal to 32.8 percent and Vicat softening point of less than or equal to 110 ℃. It can be seen that ultrasound, phosphorus/boron/fluorine co-doped carbon-coated attapulgite and organic-inorganic co-modification under ultrasonic waves all have an improvement effect on the mechanical property, high temperature resistance and flame retardance of the material, but the modified attapulgite filled natural rubber composite material for rubber reinforcement prepared in examples 1-5 of the present invention has better mechanical property, better high temperature resistance and flame retardance than the product in the prior art, which is the result of the synergistic effect of the components, wherein the modified attapulgite for rubber reinforcement prepared in example 5 has the best effect.
The foregoing is directed to embodiments of the present invention and, more particularly, to a method and apparatus for controlling a power converter in a power converter, including a power converter, a power.
Claims (10)
1. A preparation method of modified attapulgite for reinforcing rubber is characterized by comprising the following steps:
step one, purifying attapulgite: dispersing attapulgite in chloroform, stirring for 15-25 minutes at 40-60 ℃, then adding a dispersing agent and a detergent, heating in a water bath at 60-100 ℃, stirring for 20-40 minutes, then carrying out ultrasonic treatment for 8-14 minutes under ultrasonic waves, then centrifuging, washing for 3-7 times by using water for centrifugation, then placing in a vacuum drying oven for drying at 70-80 ℃ to constant weight, and then grinding and sieving by using a 200-mesh 400-mesh sieve for later use;
step two, phosphorus/boron/fluorine co-doped carbon-coated attapulgite: dissolving tri-n-butyl phosphorus tetrafluoroborate in water, adding the attapulgite purified in the step one, uniformly stirring, placing the product in a vacuum drying box, drying at 70-80 ℃ to constant weight, then burning for 3-5 hours in an inert gas atmosphere at 600 ℃ under 500-5 ℃, cooling to room temperature, grinding, and sieving with a 200-400-mesh sieve, wherein the mass ratio of the tri-n-butyl phosphorus tetrafluoroborate to the water to the attapulgite is 1 (15-25) to (3-5);
step three, organic and inorganic co-modification: dispersing the phosphorus/boron/fluorine co-doped carbon-coated attapulgite prepared in the second step and graphene oxide in ethanol, then 3, 3-dimethoxy-2, 7,10,13, 16-pentaoxa-3-silaheptadecane and N- (trimethoxysilylpropyl) ethylenediamine triacetic acid sodium salt are added into the mixture, stirring and reacting for 3-5 hours at 60-80 ℃, then removing ethanol by rotary evaporation to obtain modified attapulgite for reinforcing rubber, wherein the mass ratio of phosphorus/boron/fluorine co-doped carbon-coated attapulgite, graphene oxide, ethanol, 3-dimethoxy-2, 7,10,13, 16-pentaoxa-3-silaheptadecane and N- (trimethoxysilylpropyl) ethylenediamine triacetic acid sodium salt is 1: (0.3-0.5): 0.2:0.1.
2. The process for producing a modified attapulgite for rubber reinforcement according to claim 1, wherein the attapulgite is dispersed in chloroform, stirred at 60 ℃ for 25 minutes, then added with a dispersant and a detergent, heated in a water bath at 100 ℃ and stirred for 40 minutes, then subjected to ultrasonic treatment for 14 minutes under ultrasonic waves, centrifuged, washed 7 times with water, then dried in a vacuum drying oven at 80 ℃ to constant weight, and milled through a 400-mesh sieve for use.
3. The method for preparing modified attapulgite for reinforcing rubber according to claim 1, wherein tri-n-butylphosphonium tetrafluoroborate is dissolved in water in the second step, then the attapulgite purified in the first step is added and stirred uniformly, the product is dried in a vacuum drying oven at 80 ℃ to constant weight, then burned for 5 hours in an inert gas atmosphere at 600 ℃, cooled to room temperature, milled and sieved by a 400-mesh sieve, wherein the mass ratio of tri-n-butylphosphonium tetrafluoroborate to water to attapulgite is 1:25: 5.
4. The method according to claim 1, wherein the phosphorus/boron/fluorine-codoped carbon-coated attapulgite and the graphene oxide prepared in the second step are dispersed in ethanol, and then 3, 3-dimethoxy-2, 7,10,13, 16-pentaoxa-3-silaheptadecane and N- (trimethoxysilylpropyl) ethylenediamine triacetic acid sodium salt are added into the mixture, stirred and reacted at 80 ℃ for 5 hours, and then the ethanol is removed by rotary evaporation to obtain the modified attapulgite for rubber reinforcement, wherein the phosphorus/boron/fluorine-codoped carbon-coated attapulgite, the graphene oxide, the ethanol, the 3, 3-dimethoxy-2, 7,10,13, 16-pentaoxa-3-silaheptadecane, The mass ratio of the N- (trimethoxysilylpropyl) ethylenediamine triacetic acid sodium salt is 1:0.5:0.2: 0.1.
5. The method of claim 1, wherein the dispersant in the first step is at least one selected from the group consisting of sodium polyacrylate, sodium hexametaphosphate, and sodium polycarboxylate.
6. The method for preparing a modified attapulgite for reinforcing rubber according to claim 1, wherein the detergent in the first step comprises the following components in parts by mass: 3-6 parts of lecithin, 10-15 parts of N, N-bis (2-hydroxyethyl) -2-aminoethanesulfonic acid modified amino modified glucan, 80-100 parts of water and 10-20 parts of ethanol, wherein the preparation method of the N, N-bis (2-hydroxyethyl) -2-aminoethanesulfonic acid modified amino modified glucan comprises the following steps: s1, adding N, N-bis (2-hydroxyethyl) -2-aminoethanesulfonic acid and dichloroalkane into an organic solvent, stirring and reacting for 3-6 hours at 70-80 ℃, then performing rotary evaporation to remove the organic solvent, washing the product with diethyl ether for 3-5 times, and finally performing rotary evaporation to remove the diethyl ether to obtain an intermediate product; s2, adding the intermediate product obtained in the step S1 and the amino-modified glucan into tetrahydrofuran, stirring for 4-6 hours at 40-60 ℃, and then removing the tetrahydrofuran by rotary evaporation.
7. The method of claim 6, wherein the dichloroalkane in S1 is 1, 12-dichlorododecane, the organic solvent is tetrahydrofuran, diethyl ether, ethyl acetate or acetone, and the molar ratio of N, N-bis (2-hydroxyethyl) -2-aminoethanesulfonic acid, dichloroalkane and organic solvent is 1:1 (6-10).
8. The method of claim 6, wherein the molar ratio of the intermediate product obtained in S1 of S2, the amino-modified glucan and the tetrahydrofuran is 1:1 (6-10).
9. The method of claim 1, wherein the inert gas in step two is helium, neon or argon.
10. A modified attapulgite clay for rubber reinforcement prepared by the method of any one of claims 1 to 9.
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