CN105602162B - A kind of nano layered silicate/fluorubber rubber master batch and preparation method thereof - Google Patents
A kind of nano layered silicate/fluorubber rubber master batch and preparation method thereof Download PDFInfo
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- CN105602162B CN105602162B CN201610200232.0A CN201610200232A CN105602162B CN 105602162 B CN105602162 B CN 105602162B CN 201610200232 A CN201610200232 A CN 201610200232A CN 105602162 B CN105602162 B CN 105602162B
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- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000004594 Masterbatch (MB) Substances 0.000 title claims abstract description 21
- 239000000725 suspension Substances 0.000 claims abstract description 56
- 239000012074 organic phase Substances 0.000 claims abstract description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000003960 organic solvent Substances 0.000 claims abstract description 21
- 238000000926 separation method Methods 0.000 claims abstract description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000007787 solid Substances 0.000 claims abstract description 7
- 239000012071 phase Substances 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims abstract description 5
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 4
- 239000002270 dispersing agent Substances 0.000 claims abstract description 4
- 238000013019 agitation Methods 0.000 claims abstract description 3
- 238000009835 boiling Methods 0.000 claims abstract description 3
- 150000004760 silicates Chemical class 0.000 claims abstract description 3
- 239000007788 liquid Substances 0.000 claims description 22
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 18
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 15
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 12
- 229910052615 phyllosilicate Inorganic materials 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 239000008346 aqueous phase Substances 0.000 claims description 8
- 239000007822 coupling agent Substances 0.000 claims description 6
- 235000019353 potassium silicate Nutrition 0.000 claims description 4
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical group [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
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 claims description 3
- 235000019818 tetrasodium diphosphate Nutrition 0.000 claims description 3
- 229940048086 sodium pyrophosphate Drugs 0.000 claims description 2
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims 1
- 229910052731 fluorine Inorganic materials 0.000 claims 1
- 239000011737 fluorine Substances 0.000 claims 1
- 229910000077 silane Inorganic materials 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 11
- 239000011159 matrix material Substances 0.000 abstract description 9
- 239000002105 nanoparticle Substances 0.000 abstract description 9
- 239000012467 final product Substances 0.000 abstract 1
- 239000000376 reactant Substances 0.000 abstract 1
- 239000004113 Sepiolite Substances 0.000 description 15
- 229910052624 sepiolite Inorganic materials 0.000 description 15
- 235000019355 sepiolite Nutrition 0.000 description 15
- 238000010992 reflux Methods 0.000 description 9
- 229910052901 montmorillonite Inorganic materials 0.000 description 8
- 239000002131 composite material Substances 0.000 description 6
- 238000009833 condensation Methods 0.000 description 6
- 230000005494 condensation Effects 0.000 description 6
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000003643 water by type Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 125000005909 ethyl alcohol group Chemical group 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000006228 supernatant Substances 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000002500 effect on skin Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000006210 lotion Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000002121 nanofiber Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000013339 polymer-based nanocomposite Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 229910052903 pyrophyllite Inorganic materials 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000013517 stratification Methods 0.000 description 1
Classifications
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- 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
- 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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/10—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
- C08K9/02—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
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
The invention discloses a kind of nano layered silicate/fluorubber rubber master batch and preparation method thereof.The rubber master batch is to contain 25~50g nano layered silicates per 100g fluorubber, and its preparation method includes：1) nano layered silicate suspension and dispersant, silane coupling agent and absolute ethyl alcohol back flow reaction, gained reactant are subjected to the separation of organic phase and water phase, collect organic phase suspension, obtain organic phase suspension I；2) fluorubber solid is taken to be dissolved in organic solvent, resulting solution is slowly added into above-mentioned organic phase suspension I, obtains organic phase suspension II；3) a certain amount of water is taken to be placed in container, the temperature for being heated to system is higher than the boiling point of above-mentioned selected organic solvent, above-mentioned organic phase suspension II is slowly added into water under agitation, while recycle organic solvent；After being added dropwise, filter, it is dry, to obtain the final product.It can make nano-particle is dispersed to be wrapped in fluorubber matrix using rubber master batch made from the method for the invention.
Description
Technical field
The present invention relates to rubber masterbatch, and in particular to a kind of nano layered silicate/fluorubber rubber master batch and preparation method thereof.
Background technology
Since the appearance of twentieth century end nanometer technology, the special performance of nano material causes the extensive pass of researchers
Note, it shows unique small size and skin effect because average grain diameter is small, specific surface area is big and surface energy is high, has conventional
The unrivaled performance of sized materials.Because its (particle filled composite characteristic size be less than 100 nanometers) surface atom number sharply increases
It is very unstable in upper state, so that the research of its composite material focuses primarily upon dispersiveness and surface/interface characteristic,
As one of its field of polymer-base composite material research hotspot.
The method that domestic and international researcher prepares polymer based nanocomposites mainly has sol-gal process, situ aggregation method
With blending method etc..In rubber industry, for its preparation method generally used for blending method, this method includes solution blending, lotion
Blending and mechanical blending etc., its advantage is prepared for nano-particle and rubber composite material prepares substep and carries out, and can control nanoparticle
The form and size of son, but the strong agglomeration tendency of nano-particle, is difficult to make the uniform particle be scattered in matrix in Blending Processes
In, so that there are sub-micron or micron order soft aggregate, the boundary defect of filler and matrix is added, reduces its mechanicalness
Energy.At present, the widely used inorganic filler of rubber industry has white carbon, carbon black, pyrophyllite, kaolin, talcum powder and sepiolite
Deng, and traditional blending technology can only make up to micron order and disperse, the reinforcement to rubber matrix is limited.Therefore, how will be inorganic
Material, which is dispersed on nanoscale in rubber matrix, forms novel high-performance, multifunctional nanocomposites as urgently
Problem to be solved.
The content of the invention
During the technical problem to be solved in the present invention is for currently with nanometer particle-modified rubber-base composite material, nanometer
Particle is reunited because of high-ratio surface energy, and then reduces the deficiency of rubber composite material mechanical performance, there is provided one kind is beneficial to rubber machine
Nano layered silicate/fluorubber rubber master batch that tool is kneaded and preparation method thereof, this method can make the dispersed bag of nano-particle
It is wrapped in fluorubber matrix.
Nano layered silicate of the present invention/fluorubber rubber master batch, contains 25~50g nano lamellars per 100g fluorubber
Silicate.
In above-mentioned technical proposal, the fluorubber can be 26 type fluorubber or 246 type fluorubber or 26 types
The rubber matrix that fluorubber and 246 type fluorubber are mixed to get with arbitrary proportion.
In above-mentioned technical proposal, the phyllosilicate can be that nanometer fibrous sepiolite and/or nano lamellar cover
De- soil；When the combination of the above-mentioned sepiolite of the selected as of nano layered silicate and montmorillonite, between sepiolite and montmorillonite
Proportioning can be any proportioning.
The present invention also provides the preparation method of above-mentioned nano layered silicate/fluorubber rubber master batch, comprise the following steps：
1) take nano layered silicate to add water to form nano layered silicate suspension, be placed in container, add and divide
Powder, silane coupling agent and absolute ethyl alcohol, stir evenly rear back flow reaction, obtain the water phase of organic modified nano phyllosilicate
The suspension liquid of aqueous phase and organic solvent, are carried out the separation of organic phase and water phase by suspension after mixing, are collected organic phase and are hanged
Supernatant liquid, is the organic phase suspension I of organic modified nano phyllosilicate；
2) take fluorubber solid to be dissolved in organic solvent, obtain the organic solution of fluorubber, the organic solution is slow
It is added in the organic phase suspension I of above-mentioned organic modified nano phyllosilicate, obtains organic phase suspension II；
3) a certain amount of water is taken to be placed in container, the temperature for being heated to system is higher than the boiling of above-mentioned selected organic solvent
Above-mentioned organic phase suspension II, is slowly added into water by point under agitation, while recycles organic solvent；It is added dropwise
Afterwards, filter, it is dry, that is, obtain nano layered silicate/fluorubber rubber master batch particulate.
Above-mentioned preparation method, the organic solvent can be with butanone, ethyl acetate or methyl acrylates.In step 1),
On the basis of 1g nano layered silicates, the dosage of organic solvent is usually 25~50mL, by the suspension liquid of aqueous phase and organic
Solvent is uniformly mixed, after stratification, the separation of generally use separatory funnel or liquid separation kettle progress organic phase and water phase.In step
2) in, on the basis of 1g fluorubber contents, the usual 13~15mL of dosage of organic solvent.
In the step 1) of above-mentioned preparation method, the nano layered silicate, dispersant, the weight of coupling agent and absolute ethyl alcohol
Amount is than being usually 2~15：1~5：1~5：50~200, it is preferably 5~10：2~3：2~4：100~150.Disperse in the step
The selection of agent is same as the prior art, usually can be calgon, waterglass or sodium pyrophosphate.
In the step 1) of above-mentioned preparation method, the selection of the silane coupling agent is same as the prior art, is preferably coupled
Agent KH570 and/or coupling agent Si69.
In the step 1) of above-mentioned preparation method, the dosage of water is preferably to make nano lamellar in nano layered silicate suspension
The density of silicate is 10~20g/L.
In the step 1) of above-mentioned preparation method, back flow reaction usually carries out under the conditions of 80~90 DEG C, can use thin layer
Whether complete chromatograph tracing detection back flow reaction, under above-mentioned qualifications, react to the time for taking around 2~4h completely.
, can be by condensation reflux unit to organic solvent reflux condensation mode, with recycling in the step 2) of above-mentioned preparation method
Organic solvent.
In the step 3) of above-mentioned preparation method, when the selected as butanone of organic solvent, >=90 DEG C are preferably heated to again
Add organic phase suspension II；When the selected as methyl acrylate of organic solvent, preferably it is heated to 85 DEG C of ＞ and has added
Machine phase suspension II；When the selected as ethyl acetate of organic solvent, preferably it is heated to 80 DEG C of ＞ and adds organic phase suspension
Liquid II.
In the step 3) of above-mentioned preparation method, dry usually to be carried out in 90~110 DEG C of conditions, the dry time is usually 1
~2h.
Compared with prior art, the present invention is provided before by nano-particle Blending Processes mechanical dispersion, utilizes co-agglomeration
Method is wrapped in nano-particle is dispersed in fluorubber matrix, is formed the compound rubber master batch of Nano filling/fluorubber, is realized at the same time
Uniformly dispersed and interface coupling characteristic of the nano-particle in rubber matrix, so as to more fully play nano-particle pair
The regulation and control of rubber manufacturing machinery performance.
Brief description of the drawings
Fig. 1 is the microscopic appearance figure (SEM figures) of the nanometer fibrous sepiolite used in the embodiment of the present invention 1；
Fig. 2 is the type fluorubber rubber master batch particulate of nanometer fibrous sepiolite made from the embodiment of the present invention 1/26；
Fig. 3 is the microscopic appearance (SEM of the type fluorubber particulate of nanometer fibrous sepiolite made from the embodiment of the present invention 1/26
Figure).
Embodiment
With reference to specific embodiment, the present invention is described in further detail, to more fully understand present disclosure, but
The present invention is not limited to following embodiments.
Embodiment 1
1) take nanometer fibrous sepiolite (its SEM figures are as shown in Figure 1) plus water to form the suspension that density is 20g/L, take
The nanometer fibrous sepiolite suspension (20g/L) of 500ml are placed in beaker, 3g calgons, the anhydrous second of 4g K570 and 150g
Alcohol, stirs evenly, and the pH of system is 3 at this time, is then heated to 90 DEG C of reflux 2h, obtains organic modified nano phyllosilicate
Suspension liquid of aqueous phase, repeats above step 1 time；The suspension and 500ml butanone are inserted in separatory funnel, shaken, is stood, point
Liquid, takes the organic phase suspension I of upper liquid, i.e. organic modified nano fibrous sepiolite.
2) 26 type fluorubber solids of 40g are dissolved in butanone 520ml, the organic solution of 26 type fluorubber are obtained, by it
Insert in separatory funnel, be added dropwise under stirring at room temperature in organic phase suspension I, form organic phase suspension II.
3) 500ml deionized waters are taken to be placed in three-necked flask, it is 90 DEG C to control its temperature, and organic phase suspension II is stirred
Under be added dropwise in the deionized water, be carried out at the same time butanone reflux condensation mode, collect；After being added dropwise, filtering, 100 DEG C of dryings, when
Between 1h, that is, obtain the type fluorubber rubber master batch particulate (as shown in Figure 2) of nanometer fibrous sepiolite/26, yield 90%.Gained particulate
SEM figures are as shown in Figure 3.
Embodiment 2
1) take nanometer fibrous sepiolite to add water to form the suspension that density is 15g/L, take the nanometer fibrous Hai Pao of 500ml
Stone suspension (15g/L) is placed in beaker, and 2.5g waterglass, 3.5g Si69 and 100g absolute ethyl alcohols, stir evenly, at this time body
The pH of system is 2, is then heated to 90 DEG C of reflux 2h, obtains the suspension liquid of aqueous phase of organic modified nano phyllosilicate, repeat with
Upper step 1 time；The suspension and 500ml ethyl acetate are inserted in separatory funnel, shaken, is stood, liquid separation, takes upper liquid, i.e.,
The organic phase suspension I of organic modified nano fibrous sepiolite.
2) 246 type fluorubber solids of 60g are swollen in ethyl acetate 9000ml, obtains the organic molten of 246 type fluorubber
Liquid, is put into separatory funnel, is added dropwise under stirring at room temperature in organic phase suspension I, forms organic phase suspension II.
3) 500ml deionized waters are taken to be placed in three-necked flask, it is 80 DEG C to control its temperature, and organic phase suspension II is stirred
Under be added dropwise in the deionized water, be carried out at the same time ethyl acetate backflow condensation, collect；After being added dropwise, filtering, 90 DEG C dry
Dry, time 2h, that is, obtain the type fluorubber rubber master batch particulate of nanometer fibrous sepiolite/246, yield 87%.
Embodiment 3
1) take nano lamellar montmorillonite to add water to form the suspension that density is 10g/L, take 500ml nano lamellar montmorillonites to hang
Supernatant liquid (10g/L) is placed in beaker, and 2.5g waterglass, 4g KH570 and 120g absolute ethyl alcohols, stir evenly, at this time the pH of system
For 2.5, be then heated to 90 DEG C of reflux 4h, obtain the suspension liquid of aqueous phase of organic modified nano phyllosilicate, repeat more than walk
Rapid 2 times；The suspension and 500ml methyl acrylates are inserted in separatory funnel, shaken, is stood, liquid separation, takes upper liquid, that is, have
The organic phase suspension I of machine modified nano fiber shape sepiolite.
2) 26 type fluorubber solids of 37.5g are swollen in methyl acrylate 520ml, obtains the organic of 26 type fluorubber
Solution, is put into separatory funnel, is added dropwise under stirring at room temperature in organic phase suspension I, forms organic phase suspension
Ⅱ。
3) 500ml deionized waters are taken to be placed in three-necked flask, it is 85 DEG C to control its temperature, and organic phase suspension II is stirred
Under be added dropwise in the deionized water, be carried out at the same time methyl acrylate reflux condensation mode, collect；After being added dropwise, filtering, 110 DEG C
Dry, time 1h, that is, obtain the type fluorubber rubber master batch particulate of nano lamellar montmorillonite/26, yield 85%.
Embodiment 4
1) take nano lamellar montmorillonite to add water to form the suspension that density is 20g/L, take 500ml nano lamellar montmorillonites to hang
Supernatant liquid (20g/L) is placed in beaker, and 2g sodium pyrophosphates, 2g Si69 and 120g absolute ethyl alcohols, stir evenly, at this time the pH of system
For 4,90 DEG C of reflux 4h are then heated to, obtain the suspension liquid of aqueous phase of organic modified nano phyllosilicate；By the suspension and
500ml methyl acrylates are inserted in separatory funnel, are shaken, and are stood, liquid separation, take upper liquid, i.e. organic modified nano threadiness sea
The organic phase suspension I of afrodite.
2) 246 type fluorubber solids of 28g are swollen in methyl acrylate 400ml, obtains the organic of 246 type fluorubber
Solution, is put into separatory funnel, is added dropwise under stirring at room temperature in organic phase suspension I, forms organic phase suspension
Ⅱ。
3) 500ml deionized waters are taken to be placed in three-necked flask, it is 90 DEG C to control its temperature, and organic phase suspension II is stirred
Under be added dropwise in the deionized water, be carried out at the same time methyl acrylate reflux condensation mode, collect；After being added dropwise, filtering, 110 DEG C
Dry, time 1h, that is, obtain the type fluorubber rubber master batch particulate of nano lamellar montmorillonite/246, yield 86.5%.
Claims (7)
- A kind of 1. preparation method of nano layered silicate/fluorubber rubber master batch, it is characterised in that：Nano layered silicate/the fluorine Rubber masterbatch is to contain 25~50g nano layered silicates per 100g fluorubber, the nano layered silicate/fluorubber rubber master batch Preparation method comprises the following steps：1) take nano layered silicate to add water to form nano layered silicate suspension, be placed in container, addition dispersant, Silane coupling agent and absolute ethyl alcohol, stir evenly rear back flow reaction, obtain the aqueous-phase suspending of organic modified nano phyllosilicate The suspension liquid of aqueous phase and organic solvent, are carried out the separation of organic phase and water phase by liquid after mixing, collect organic phase suspension, The as organic phase suspension I of organic modified nano phyllosilicate；2) take fluorubber solid to be dissolved in organic solvent, obtain the organic solution of fluorubber, which is slowly added to Into the organic phase suspension I of above-mentioned organic modified nano phyllosilicate, organic phase suspension II is obtained；3) a certain amount of water is taken to be placed in container, the temperature for being heated to system is higher than the boiling point of above-mentioned selected organic solvent, Above-mentioned organic phase suspension II is slowly added into water under agitation, while recycles organic solvent；After being added dropwise, mistake Filter, it is dry, that is, obtain nano layered silicate/fluorubber rubber master batch particulate.
- 2. preparation method according to claim 1, it is characterised in that：The organic solvent for butanone, ethyl acetate or Methyl acrylate.
- 3. preparation method according to claim 1, it is characterised in that：The dispersant is calgon, waterglass Or sodium pyrophosphate.
- 4. according to preparation method according to any one of claims 1 to 3, it is characterised in that：In step 1), the nano lamellar Silicate, calgon, the weight ratio of coupling agent and absolute ethyl alcohol are 2~15：1~5：1~5：50~200.
- 5. according to preparation method according to any one of claims 1 to 3, it is characterised in that：In step 1), the nano lamellar Silicate, calgon, the weight ratio of coupling agent and absolute ethyl alcohol are 5~10：2~3：2~4：100~150.
- 6. according to preparation method according to any one of claims 1 to 3, it is characterised in that：In step 1), the silane is even Connection agent is coupling agent KH570 and/or coupling agent Si69.
- 7. according to preparation method according to any one of claims 1 to 3, it is characterised in that：In step 1), the dosage of water is to make The density of nano layered silicate is 10~20g/L in nano layered silicate suspension.
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| CN201610200232.0A CN105602162B (en) | 2016-04-01 | 2016-04-01 | A kind of nano layered silicate/fluorubber rubber master batch and preparation method thereof |
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