CN106366387A - Preparing method of epoxidized natural rubber organic/inorganic hybrid material - Google Patents
Preparing method of epoxidized natural rubber organic/inorganic hybrid material Download PDFInfo
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- CN106366387A CN106366387A CN201610822734.7A CN201610822734A CN106366387A CN 106366387 A CN106366387 A CN 106366387A CN 201610822734 A CN201610822734 A CN 201610822734A CN 106366387 A CN106366387 A CN 106366387A
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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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
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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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
- C08K7/26—Silicon- containing compounds
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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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
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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
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
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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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Abstract
The invention discloses a preparing method of an epoxidized natural rubber organic/inorganic hybrid material. The epoxidized natural rubber (ENR for short) is a special high natural rubber obtained by oxidation treatment of a natural emulsion by oxyacid, while on a basis that properties of tensile strength and tensile strain crystallization of part of a natural rubber are kept, excellent organic solvent resistance, gas barrier property and wet-skid resistance are obtained. Study finds that a polar epoxy group of ENR (epoxidized natural rubber) can interact with inorganic fillers drastically, which makes the fillers play a role of a crosslinking-like point and a fortifier, thus the hybrid material is endowed with a certain practical application property and material can be prepared with a traditional rubber processing technology. The prepared epoxidized natural rubber organic/inorganic hybrid material can be applied to vulcanized rubber products of special requirements.
Description
Technical field
The invention belongs to rubber materials are and in particular to a kind of preparation of epoxy natural rubber organic/inorganic hybridization material
Method.
Background technology
In traditional rubber processing, inorganic filler is applied to rubber-base composite material usually as a kind of reinforced additive
In, by the cooperation with auxiliary agents such as sulfuration, anti-old, plasticising, make elastomeric material obtain high resiliency, high stretcher strain and high intensity etc.
Application performance.As a rule, the excellent physical and mechanical propertiess of material in terms of meeting its use requirement hundred profit and none evil, but
Some special applications, composite there is also certain performance surplus, in addition, during traditional rubber processing, sulfur
Change the part noxious substances such as auxiliary agent, age resistor and there is volatilization, pollution, be unfavorable for environmental protection technique and green product reason
The practice read.Most inorganic filler, such as silicon dioxide, white carbon black, galapectite etc., its surface is rich in carboxyl, hydroxyl, ester group
Deng polar organic group, with the rubber of polarity strong interaction can occur, such as covalent bond, ionic bond and hydrogen bond etc.,
By the effective process to inorganic filler, its surface functional group can be activated, make filler grain play crosslinking in rubber matrix
Agent and the effect of reinforcing agent, in the case of without other vulcanization aids, prepare the rubber of possible favorable elasticity and intensity
Glue organic/inorganic hybridization material.For traditional rubber composite, the cost of material of hybrid material is lower.
Epoxy natural rubber (enr) is the oxidation processes through peroxyformic acid or peracetic acid for the natural rubber latex and obtains,
Due to introducing the epoxide group of polarity, its outside the performance of member-retaining portion natural rubber, with more excellent air-tightness, oil resistant
Property and high glass transition temperature.Meanwhile, the high activity of epoxy radicals can make its hydroxyl with inorganic filler surface, carboxyl, ester
There is strong interaction in base etc..Jae ok jo etc. is processed to multi-walled carbon nano-tubes using amino silane, then will locate
Inorganic filler after reason is blended with epoxy natural rubber/chlorinated scoline, is prepared for multi-walled carbon nano-tubes filling
Rubber-base composite material.Research finds, the hydroxyl of epoxy radicals and modified carbon nano tube pipe surface, amino etc. there occurs chemical bonding,
Enhance the network structure between CNT and enr, finally improve heat conduction and the gas barrier property of composite.(jae
o., prosenjit s., nam g., et al. development of nanocomposite with epoxidized
natural rubber and functionalized multiwalled carbon nanotubes for enhanced
thermal conductivity and gas barrier property[j]. materials & design, 2015,
83:777-785).Tiwen xu etc. adopts enr as interface modifier, and the natural rubber applying it to white carbon filling is multiple
In condensation material system, it was found that the interface compatibility of inorganic filler and rubber matrix be improved significantly, and improve compound
The multinomial physical and mechanical propertiess of material.The research of interface interaction shows, the silicone hydroxyl on white carbon surface is occurred with the epoxy radicals of enr
The interaction of covalent bond and hydrogen bond, enhances the network structure of rubber/inorganic filler.(t. xu, z. jia, y.
luo, d. jia, z. peng, interfacial interaction between the epoxidized natural
rubber and silica in natural rubber/silica composites, applied surface
Science, 2015,328:306-313).
Inventors noted that for enr, the high activity of its epoxy radicals can be used to carry out chemistry with inorganic filler
Reaction.By suitable method (for example controlling specific surface area and surface energy, activation energy of reduction reaction etc. of inorganic filler), have
Good being bonded may be formed between enr and inorganic filler two, in the case of without other conventional vulcanized auxiliary agents, system
Hybrid material for the epoxy natural rubber/inorganic filler going out certain serviceability.The preparation of this hybrid material is than biography
For the vulcanization of rubber processing of system, more environmentally-friendly low cost, there are certain economic results in society.
Content of the invention
In order to overcome the deficiencies in the prior art, it is an object of the invention to provide a kind of epoxy natural rubber organic/no
The preparation method of machine hybrid material, this hybrid material environmental protection, low cost.
The purpose of the present invention is achieved through the following technical solutions.
A kind of preparation method of epoxy natural rubber organic/inorganic hybridization material, comprises the following steps:
(1) inorganic filler is added to and in solvent, is made into the suspension that mass concentration is 10 ~ 25%；
(2) modifying agent is added in suspension, stirring reaction 6 ~ 24h at 40 ~ 100 DEG C, filters, rinse, be centrifuged, 30 ~ 80
DEG C drying, to constant weight, obtains the inorganic filler of modification；
(3) by obtain after the blending of modified inorganic filler and epoxy natural rubber, co-vulcanization epoxy natural rubber organic/no
Machine hybrid material；
The interpolation of described modifying agent can be added in the suspension of inorganic filler, also can be in inorganic filler and the natural rubber of epoxidation
The stage of glue blending adds.
A kind of another kind of preparation method of epoxy natural rubber organic/inorganic hybridization material, comprises the following steps:
(1) inorganic filler is added to and in solvent, is made into the suspension that mass concentration is 10 ~ 25%；
(2) modifying agent is added in suspension, stirring reaction 6 ~ 24h at 40 ~ 100 DEG C, filters, rinse, be centrifuged, 30 ~ 80
DEG C drying, to constant weight, obtains the inorganic filler of modification；
(3) modified inorganic filler is mixed with epoxy natural rubber latex, at 30 ~ 80 DEG C, stir 0.5 ~ 24h；
(4) by step (3) gained mixed emulsion in acid or cacl2Solidified in the case of spray solution, and be dehydrated, crush,
It is dried to constant weight in 50 ~ 110 DEG C of convection oven, obtain the coprecipitated glue of epoxy natural rubber of Inorganic Fillers Filled；
(5) the coprecipitated glue of epoxy natural rubber obtaining step (4) is blended, obtains epoxy natural rubber after co-vulcanization and have
Machine/inorganic hybrid material.
Preferably, the described inorganic filler of step (1) including but not limited to precipitated silica, aerosil, angstrom
One or more of Lip river stone, white carbon black, CNT and montmorillonite, the particle diameter of described inorganic filler is 5nm ~ 20um；Described
Solvent is ethanol, acetone, pure water or tap water.
Preferably, the described modifying agent of step (2) is silane coupling agent, epoxy hardener or catalyst, surfactant
One or more of.
It is further preferred that described silane coupling agent is γ-amine propyl-triethoxysilicane, γ-glycidoxy third
Base trimethoxy silane, γ-methacryloxypropyl trimethoxy silane, γ mercaptopropyitrimethoxy silane, γ-
One of mercapto propyldimethoxy-silane, VTES and tetra-sulfurized pair (triethoxy propyl group) silane with
On；Described epoxy hardener or catalyst are triethanolamine, ethylenediamine, hexamethylene diamine, triethylene tetramine, diethylaminopropylamine,
Phenylenediamine, diaminodiphenyl-methane, m-xylene diamine, diamino-pyridine, benzyldimethylamine, 2,4, maleic anhydride, adjacent benzene
One or more of dicarboxylic acid anhydride, organic acid, boron trifluoride and boron trifluoride complex, polyamide and polyamide modified amine mixes
Close；Described surfactant is the alkyl phenol of ethoxylation, methylene sodium dinaphthalenesulfonate, nekal, methylene diisopropyl
Base sodium naphthalene sulfonate, methylene potassium diisopropyl naphthalene sulfonate, sodium pyrophosphate, cetyl trimethylammonium bromide (ctab), cetyl
One or more of trimethyl ammonium chloride (ctac), dodecylbenzene sodium sulfonate (sdbs) and dodecyl sodium sulfate mix.
Preferably, the described epoxy natural rubber of step (3) is solid epoxidation natural rubber；Described epoxidation is natural
The epoxy content of rubber is 20 ~ 50%.
Preferably, described amount of modifier is the 0.5%～15% of inorganic filler quality；Described inorganic filler consumption is epoxy
Change the 10～100% of natural rubber quality.
Preferably, described blending using banburying, mill one or two, mechanical blending temperature be 30 ~ 100 DEG C, the time
For 5 ~ 30min；The temperature of described co-vulcanization is 140 ~ 180 DEG C, and the time is 15 ~ 60min.
Preferably, the epoxy content of the described epoxy natural rubber latex of step (3) be 20 ~ 50%, mass concentration be 10 ~
40%；The mass concentration of the described acid of step (4) is 1 ~ 10%；cacl2The mass concentration of solution is 1 ~ 15%.Consumption is epoxy latex
The 0.5 ~ 2.0% of solid dry rubber content.
Preferably, the described acid of step (4) is one or more of organic acid and mineral acid；It is further preferred that described have
Machine acid is formic acid, acetic acid, Palmic acid, stearic acid, Oleic acid, linoleic acid, linolenic acid, benzenesulfonic acid, aminoacid, malic acid, ethanedioic acid
One or more of；Described mineral acid be hydrochloric acid, sulphuric acid, phosphoric acid, carbonic acid, hypochlorous acid, silicic acid, metasilicic acid, boric acid, Metaphosphoric acid,
One or more of triphosphoric acid, chlorosulfonic acid, sulfurous acid.
Modifying agent used by the present invention, its effect on the one hand occur with the hydroxyl of inorganic filler surface, carboxyl etc. covalent bond,
Hydrogen bond or the combination of ionic bond, weaken the reunion of filler grain itself, strengthen the interaction of inorganic filler and epoxy glue；Another
Aspect, as modifying agent itself, both can be catalyzed the ring-opening reaction of epoxy radicals and inorganic filler surface organic group it is also possible to replace
Change the active function groups of inorganic filler surface, be instead more easy to the group with epoxy reaction, the crosslinking improving hybrid material is close
Degree, reaches the purpose being obviously improved hybrid material serviceability.
The present invention is that inorganic filler surface is modified, and may also be employed the epoxide group in enr is modified simultaneously.
Modified inorganic filler, on the one hand can reduce the reunion of particle itself, increase filler contact with the rubber matrix of polarity itself
Area, the interaction between both liftings, the inorganic filler and rubber matrix compatibility of itself is also improved；Modified epoxy
The purpose of group is to increase the intermolecular distance of polar rubber, the flexibility of reinforced epoxy glue, replaces more to react simultaneously
The group of activity, such as amino, strengthen the reactivity of rubber molecule and inorganic filler surface functional group, the friendship of lifting hybrid material
Connection density.
The epoxy natural rubber organic/inorganic hybridization material of the present invention, as a kind of hybrid material of epoxiess, permissible
It is prepared using traditional rubber processing, and the course of processing does not have the pollution problem of small powder auxiliary agent, reduces simultaneously
Use cost.Serviceability aspect, part formulations possess high hardness, high-moduluss and low tensile set, can apply
Special rubber field.
The present invention, compared with existing technology, has the advantage that and beneficial effect:
1st, by epoxy natural rubber and modified inorganic filler direct hybridization mechanism, and do not change the traditional diamond-making technique of rubber, letter
Single easy, with low cost.
2nd, in the complex prepared by the present invention, inorganic filler serves the effect of reinforcing agent and vulcanizing agent, than tradition
Sulfuration process, raw material is more environmentally-friendly and cheap.
3rd, the modified inorganic filler being prepared by the method for the present invention can be used for epoxy natural rubber latex product, and energy
For solids epoxy glue product.
4th, the epoxy natural rubber/gas-phase silica organic/inorganic hybridization material of present invention preparation, white carbon filling
Number can be up to 100 parts, and 100% stress at definite elongation of the hybrid material of preparation can reach 8.0mpa, tensile strength up to
20.0mpa, up to 400%, tearing strength is up to 50kn m for elongation at break-1, Shao's a hardness is up to 90.
Brief description
Fig. 1 is the Dynamic Thermal of the material after the enr-20/pre-silica hybrid material sulfuration of different ratio in embodiment 1
Mechanical Property Analysis figure (dma).
Fig. 2 is that in embodiment 3, galapectite (hnts) filling number is that when 40 parts, enr-50/hnts hybrid material vulcanizate draws
The stereoscan photograph (sem) in the brittle failure face of stretching.
Fig. 3 is that in embodiment 3, galapectite (hnts) filling number is that when 60 parts, enr-50/hnts hybrid material vulcanizate draws
The stereoscan photograph (sem) in the brittle failure face of stretching.
Fig. 4 is the transmission electron microscope photo (tem) of unmodified galapectite (hnts) in embodiment 3.
Fig. 5 is the transmission electron microscope photo (tem) of the product after enr-50/hnts hydridization blend extracting in embodiment 3.
Specific embodiment
With reference to embodiment, the present invention is described in more detail.
Embodiment 1
The first step 30g precipitated silica (pre-silica, particle diameter is 5nm) is added in tap water and is configured to quality
Concentration is 10% suspension, stirring；
The methylene sodium dinaphthalenesulfonate of precipitated silica consumption 0.5wt% is added drop-wise in the first step gained suspension second step,
24h is stirred under the conditions of 40 DEG C；Take out modified white carbon slurry, after rinsing, centrifugation 3 times, 30 DEG C of freeze-day with constant temperature are to constant weight；
3rd step will be common in 30 DEG C of mill according to different proportionings from solid enr-20 for the modified silicon dioxide of second step
Mixed, mill 30min, obtain enr/pre-silica hydridization blend；
The enr/pre-silica hydridization blend of the 3rd step is vulcanized on purl machine by the 4th step, 180 DEG C of curing temperature, when
Between 15min, obtain vulcanize enr-20/pre-silica hybrid material.The mechanical property of enr-20/pre-silica hybrid material
Can be as shown in table 1.
Table 1
As shown in Table 1, with being continuously increased of white carbon content in hybrid material, the stress at definite elongation of material, tensile strength, tear
The mechanical property parameters such as intensity, hardness all constantly increase, and show epoxy glue and the interface interaction of white carbon with filler in system
The increase of proportioning and strengthen, mutually crosslinked to rubber and reinforcement the effect of Linesless charcoal black track producing particle becomes apparent from.Fig. 1 is different ratio
The dynamic thermomechanical analysis chart (dma) of the material after the sulfuration of enr/pre-silica hybrid material.As shown in Figure 1, hybrid material
The glass transition temperature tg of vulcanizate first reduces and increases afterwards with the increase of amount of filler, illustrates to exceed when silica-filled amount
During 20phr, the elasticity of good fortune material is remarkably reinforced, and tg increases.Meanwhile, the fissipation factor of the vulcanizate of high temperature section is with titanium dioxide
Increasing of silicone content has the trend successively decreased, and further demonstrates that the elasticity of hybrid material becomes big.
Embodiment 2
The first step 30g precipitated silica (pre-silica, particle diameter be 20um) is added in ethanol to be configured to quality dense
Spend the suspension for 25%, stirring；
The triethanolamine of precipitated silica consumption 15wt% is added drop-wise in the first step gained suspension second step, 100 DEG C of bars
6h is stirred under part；Take out modified white carbon slurry, after rinsing, centrifugation 3 times, 80 DEG C of freeze-day with constant temperature are to constant weight；
3rd step by silicon dioxide modified for second step and solid enr-35 according to mass ratio 1:1 proportioning in 65 DEG C of mill
It is blended on machine, be simultaneously added dropwise the maleic anhydride of enr-35 consumption 7.75wt%, mill 5min, obtain enr/pre-silica
Hydridization blend；
The enr/pre-silica hydridization blend of the 3rd step is vulcanized on purl machine by the 4th step, 140 DEG C of curing temperature, when
Between 60min, obtain vulcanize enr-35/pre-silica hybrid material.The physical machine of enr-35/pre-silica hybrid material
Tool performance is as shown in table 2.
Table 2
As shown in Table 2, in the case of enr/pre-silica constant 1:1 proportioning, the hydridization material of same proportioning in contrast table 1
Material, after epoxide number improves, the mechanical performance index of hybrid material is all obviously improved.The increasing of this explanation epoxy group content
Many, white carbon and epoxy glue occur the probability of chemical reaction to rise, and improve the overall mechanical properties of hybrid material.
Embodiment 3
The first step 30g galapectite (hnts, particle diameter is 50nm) is added in tap water and is configured to mass concentration is 17.5%
Suspension, stirring；
The methylene diisopropyl sodium naphthalene sulfonate of hnts consumption 7.75 wt% is added drop-wise in the first step gained suspension second step,
15h is stirred under the conditions of 70 DEG C；Take out modified hnts, after rinsing, centrifugation 3 times, 55 DEG C of freeze-day with constant temperature are to constant weight；
The modified hnts of second step is blended in 100 DEG C of mill according to different proportionings by the 3rd step from solid enr-50,
It is simultaneously added dropwise the boron trifluoride of hnts consumption 2 wt%, mill 17.5min, obtain enr/hnts hydridization blend；
The enr/hnts hydridization blend of the 3rd step is vulcanized on purl machine by the 4th step, 160 DEG C of curing temperature, the time
37.5min, obtains the enr-50/hnts hybrid material vulcanizing.The mechanical property of enr-50/hnts is as shown in table 3.
Table 3
As shown in Table 3, with the increasing of galapectite content in hybrid material, the stress at definite elongation of material, tensile strength, extension at break
The mechanical performance index parameter such as rate, tearing strength, hardness number all increases.Activity group content due to galapectite surface is less than in vain
White carbon black, therefore, in the crosslinking degree of this system or the severity of reaction not as good as white carbon system, shows low mechanical property
Parameter.Simultaneously as the special nano tubular structure of galapectite, with enr hybridisation process in, can showing with filler orientation
As shown in Figure 2 and Figure 3.Galapectite is orientated substantially in elastomeric material drawing process, the lifting to hybrid material mechanical property
Have and definitely act on.In addition, Fig. 4, Fig. 5 compared for galapectite and enr is blended the nanotube transmission electron microscope photo before and after hydridization.From
In figure can be seen that and processes through hydridization, and the outside dimension of part galapectite pipe significantly increases, edge blurry.This explanation, enr
It has been grafted to galapectite surface, the effect of the similar crosslinked and reinforcement that galapectite is played has been confirmed in side.
Embodiment 4
The first step 30g aerosil (f-silica, particle diameter be 10um) is added in tap water to be configured to quality dense
Spend the suspension for 15%, stirring；
Double-[γ-(triethoxysilicane) propyl group] tetrasulfide of aerosil consumption 10 wt% is added drop-wise to by second step
In first step gained suspension, under the conditions of 70 DEG C, stir 8h；Take out modified silicon dioxide slurry, after rinsing, centrifugation 3 times,
30 DEG C of freeze-day with constant temperature are to constant weight；
3rd step is by the epoxidized natural latex (epoxy admittedly containing 10 wt% of silicon dioxide modified for second step and appropriate proportioning
Degree 40%) mixing, stir 0.5h, 80 DEG C of temperature；
4th step adopts the cacl of mass concentration 15%2Spray solution carries out solidification process in the 3rd step gained mixed liquor, and
The coprecipitated glue of enr/f-silica is obtained after dehydration, broken, 110 DEG C of dryings；
The coprecipitated glue of enr/f-silica of the 4th step is blended by the 5th step on a mill, 80 DEG C of temperature, and time 15min obtains
Blend.
The blend of the 5th step is vulcanized on purl machine by the 6th step, 160 DEG C of curing temperature, and time 30min obtains sulfur
The enr-40/f-silica hybrid material changed.The physical and mechanical propertiess of enr-40/f-silica are as shown in table 4.
Table 4
As shown in Table 4, with being continuously increased of aerosil content in hybrid material, the stress at definite elongation of material, stretching are strong
The mechanical property parameters such as degree, tearing strength, hardness all constantly increase, show the interface interaction of epoxy glue and aerosil with
The increase of filling mixture ratio in system and strengthen, mutually crosslinked and reinforcement effect becomes apparent from silicon dioxide granule to rubber.
Embodiment 5
The first step 30g aerosil (f-silica, particle diameter be 8nm) is added in tap water to be configured to quality dense
Spend the suspension for 17%, stirring；
Double-[γ-(triethoxysilicane) propyl group] tetrasulfide of aerosil consumption 10 wt% is added drop-wise to by second step
In first step gained suspension, under the conditions of 70 DEG C, stir 8h；Take out modified silicon dioxide slurry, after rinsing, centrifugation 3 times,
80 DEG C of freeze-day with constant temperature are to constant weight；
3rd step is by the epoxidized natural latex (epoxy admittedly containing 40 wt% of silicon dioxide modified for second step and appropriate proportioning
Degree 40%) mixing, stir 24h, 30 DEG C of temperature；
4th step is sprayed in the 3rd step gained mixed liquor using the formic acid solution of mass concentration 10% and carries out solidification process, and takes off
The coprecipitated glue of enr/f-silica is obtained after water, broken, 50 DEG C of dryings；
The coprecipitated glue of enr/f-silica of the 4th step is blended by the 5th step on a mill, and adds between enr consumption 1 wt%
Benzene dimethylamine, temperature 60 C, time 15min, obtain blend.
The blend of the 5th step is vulcanized on purl machine by the 6th step, 160 DEG C of curing temperature, and time 30min obtains sulfur
The enr-40/f-silica hybrid material changed.The mechanical property of enr-40/f-silica hybrid material is as shown in table 5.
Table 5
As shown in Table 5, with being continuously increased of aerosil content in hybrid material, the stress at definite elongation of material, stretching are strong
The mechanical property parameters such as degree, tearing strength, hardness all constantly increase, and show epoxy glue and the interface interaction of silicon dioxide with body
The increase of filling mixture ratio in system and strengthen, mutually crosslinked to rubber and reinforcement the effect of silicon dioxide granule becomes apparent from.Contrast table 4
Middle data is it can be seen that the selection of the solidification mode of coprecipitated glue and modifying agent is apparent to the performance impact of final hybrid material.
Embodiment 6
The first step 30g aerosil (f-silica, particle diameter be 15nm) is added in tap water to be configured to quality dense
Spend the suspension for 17%, stirring；
γ-the methacryloxypropyl trimethoxy silane of aerosil consumption 10 wt% is added drop-wise to by second step
In first step gained suspension, under the conditions of 70 DEG C, stir 8h；Take out modified silicon dioxide slurry, after rinsing, centrifugation 3 times,
80 DEG C of freeze-day with constant temperature are to constant weight；
3rd step is by the epoxidized natural latex (epoxy admittedly containing 25 wt% of silicon dioxide modified for second step and appropriate proportioning
Degree 50%) mixing, stir 12.5h, 55 DEG C of temperature；
4th step adopts the acetum of mass concentration 1% and 8% cacl2Spray solution enters in the 3rd step gained mixed liquor
Row solidification is processed, and is dehydrated, crushes, obtaining the coprecipitated glue of enr/f-silica after 80 DEG C of dryings；
The coprecipitated glue of enr/f-silica of the 4th step is blended by the 5th step on a mill, and adds the two of enr consumption 2 wt%
Ethylamino propylamine, 80 DEG C of temperature, time 20min, obtain blend.
The blend of the 5th step is vulcanized on purl machine by the 6th step, 170 DEG C of curing temperature, and time 30min obtains sulfur
The enr-50/f-silica hybrid material changed.The mechanical property of enr-50/f-silica hybrid material is as shown in table 6.
Table 6
As shown in Table 6, with being continuously increased of aerosil content in hybrid material, the stress at definite elongation of material, stretching are strong
The mechanical property parameters such as degree, tearing strength, hardness all constantly increase, and show epoxy glue and the interface interaction of silicon dioxide with body
The increase of filling mixture ratio in system and strengthen, mutually crosslinked to rubber and reinforcement the effect of silicon dioxide granule becomes apparent from.This system
Under, the final tensile strength of hybrid material is up to 22.84mpa.
Claims (10)
1. a kind of preparation method of epoxy natural rubber organic/inorganic hybridization material is it is characterised in that comprise the following steps:
(1) inorganic filler is added to and in solvent, is made into the suspension that mass concentration is 10 ~ 25%；
(2) modifying agent is added in suspension, stirring reaction 6 ~ 24h at 40 ~ 100 DEG C, filters, rinse, be centrifuged, 30 ~ 80
DEG C drying, to constant weight, obtains the inorganic filler of modification；
(3) by obtain after the blending of modified inorganic filler and epoxy natural rubber, co-vulcanization epoxy natural rubber organic/no
Machine hybrid material；
The interpolation of described modifying agent can be added in the suspension of inorganic filler, also can be in inorganic filler and the natural rubber of epoxidation
The stage of glue blending adds.
2. a kind of preparation method of epoxy natural rubber organic/inorganic hybridization material is it is characterised in that comprise the following steps:
(1) inorganic filler is added to and in solvent, is made into the suspension that mass concentration is 10 ~ 25%；
(2) modifying agent is added in suspension, stirring reaction 6 ~ 24h at 40 ~ 100 DEG C, filters, rinse, be centrifuged, 30 ~ 80
DEG C drying, to constant weight, obtains the inorganic filler of modification；
(3) modified inorganic filler is mixed with epoxy natural rubber latex, at 30 ~ 80 DEG C, stir 0.5 ~ 24h；
(4) by step (3) gained mixed emulsion in acid or cacl2Solidified in the case of spray solution, and be dehydrated, crush,
It is dried to constant weight in 50 ~ 110 DEG C of convection oven, obtain the coprecipitated glue of epoxy natural rubber of Inorganic Fillers Filled；
(5) the coprecipitated glue of epoxy natural rubber obtaining step (4) is blended, obtains epoxy natural rubber after co-vulcanization and have
Machine/inorganic hybrid material.
3. the preparation method according to claim 1,2 any one is it is characterised in that the described inorganic filler of step (1) is heavy
One or more of shallow lake method silicon dioxide, aerosil, galapectite, white carbon black, CNT and montmorillonite, described inorganic fill out
The particle diameter of material is 5nm ~ 20um；Described solvent is ethanol, acetone, pure water or tap water.
4. the preparation method according to claim 1,2 any one is it is characterised in that the described modifying agent of step (2) is silane
One or more of class coupling agent, epoxy hardener or catalyst, surfactant.
5. preparation method according to claim 4 is it is characterised in that described silane coupling agent is γ-amine propyl group three second
TMOS, γ-glycidoxypropyltrime,hoxysilane, γ-methacryloxypropyl trimethoxy silane, γ-
Mercaptopropyi trimethoxy silane, γ-mercapto propyldimethoxy-silane, VTES and tetra-sulfurized pair (three second
One or more of epoxide propyl group) silane；Described epoxy hardener or catalyst are triethanolamine, ethylenediamine, hexamethylene diamine, three second
Alkene tetramine, diethylaminopropylamine, m-diaminobenzene., diaminodiphenyl-methane, m-xylene diamine, diamino-pyridine, benzyl diformazan
Base amine, maleic anhydride, phthalic anhydride, organic acid, boron trifluoride and boron trifluoride complex, polyamide and polyamide
One or more mixing of modified amine；Described surfactant is the alkyl phenol of ethoxylation, methylene sodium dinaphthalenesulfonate, two
Sodium butylnaphthalenesulfonate, methylene diisopropyl sodium naphthalene sulfonate, methylene potassium diisopropyl naphthalene sulfonate, sodium pyrophosphate, cetyl front three
One or more of base ammonium bromide, hexadecyltrimethylammonium chloride, dodecylbenzene sodium sulfonate and dodecyl sodium sulfate
Mixing.
6. preparation method according to claim 1 is it is characterised in that the described epoxy natural rubber of step (3) is solid
Epoxy natural rubber；The epoxy content of described epoxy natural rubber is 20 ~ 50%.
7. the preparation method according to claim 1,2 any one is it is characterised in that described amount of modifier is inorganic filler
The 0.5%～15% of quality；Described inorganic filler consumption is the 10～100% of epoxy natural rubber quality.
8. preparation method according to claim 1,2 any one is it is characterised in that described blending adopts banburying, mill
One or two, mechanical blending temperature is 30 ~ 100 DEG C, and the time is 5 ~ 30min；The temperature of described co-vulcanization is 140 ~ 180 DEG C,
Time is 15 ~ 60min.
9. preparation method according to claim 2 is it is characterised in that step (3) described epoxy natural rubber latex
Epoxy content is 20 ~ 50%, and mass concentration is 10 ~ 40%；The mass concentration of the described acid of step (4) is 1 ~ 10%；cacl2The matter of solution
Amount concentration is 1 ~ 15%.
10. preparation method according to claim 2 is it is characterised in that the described acid of step (4) is in organic acid and mineral acid
More than one；Described organic acid is formic acid, acetic acid, Palmic acid, stearic acid, Oleic acid, linoleic acid, linolenic acid, benzenesulfonic acid, amino
One or more of acid, malic acid, ethanedioic acid；Described mineral acid is hydrochloric acid, sulphuric acid, phosphoric acid, carbonic acid, hypochlorous acid, silicic acid, inclined silicon
One or more of acid, boric acid, Metaphosphoric acid, triphosphoric acid, chlorosulfonic acid, sulfurous acid.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109021329A (en) * | 2018-07-06 | 2018-12-18 | 佛山皖阳生物科技有限公司 | A kind of preparation method of Heveatex composite sponge |
| CN114286751A (en) * | 2019-07-01 | 2022-04-05 | 天然纤维焊接股份有限公司 | Curing agent and method |
| CN116496557A (en) * | 2023-05-15 | 2023-07-28 | 江苏海洋大学 | Low-filling high-heat-conductivity natural rubber nanocomposite and preparation method thereof |
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| JP2008308601A (en) * | 2007-06-15 | 2008-12-25 | Sumitomo Rubber Ind Ltd | Rubber composition for tire and tire having tire member using the composition |
| CN102108144A (en) * | 2010-12-24 | 2011-06-29 | 中国热带农业科学院农产品加工研究所 | Preparation method of epoxidized natural rubber masterbatch with highly dispersed nano-silicon dioxide/carbon black |
| CN103102549A (en) * | 2013-03-07 | 2013-05-15 | 中国热带农业科学院农产品加工研究所 | Castaway phosphorus slag-epoxidized natural rubber composite and preparation method thereof |
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2016
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008308601A (en) * | 2007-06-15 | 2008-12-25 | Sumitomo Rubber Ind Ltd | Rubber composition for tire and tire having tire member using the composition |
| CN102108144A (en) * | 2010-12-24 | 2011-06-29 | 中国热带农业科学院农产品加工研究所 | Preparation method of epoxidized natural rubber masterbatch with highly dispersed nano-silicon dioxide/carbon black |
| CN103102549A (en) * | 2013-03-07 | 2013-05-15 | 中国热带农业科学院农产品加工研究所 | Castaway phosphorus slag-epoxidized natural rubber composite and preparation method thereof |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109021329A (en) * | 2018-07-06 | 2018-12-18 | 佛山皖阳生物科技有限公司 | A kind of preparation method of Heveatex composite sponge |
| CN114286751A (en) * | 2019-07-01 | 2022-04-05 | 天然纤维焊接股份有限公司 | Curing agent and method |
| CN114286751B (en) * | 2019-07-01 | 2023-06-20 | 天然纤维焊接股份有限公司 | Curing agent and method |
| CN116496557A (en) * | 2023-05-15 | 2023-07-28 | 江苏海洋大学 | Low-filling high-heat-conductivity natural rubber nanocomposite and preparation method thereof |
| CN116496557B (en) * | 2023-05-15 | 2024-04-05 | 江苏海洋大学 | Low-filling high-heat-conductivity natural rubber nanocomposite and preparation method thereof |
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| CN106366387B (en) | 2018-06-22 |
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