CN106366387B - A kind of preparation method of epoxy natural rubber organic/inorganic hybridization material - Google Patents

A kind of preparation method of epoxy natural rubber organic/inorganic hybridization material Download PDF

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CN106366387B
CN106366387B CN201610822734.7A CN201610822734A CN106366387B CN 106366387 B CN106366387 B CN 106366387B CN 201610822734 A CN201610822734 A CN 201610822734A CN 106366387 B CN106366387 B CN 106366387B
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acid
natural rubber
epoxy
inorganic filler
epoxy natural
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CN106366387A (en
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贾志欣
许体文
罗远芳
吴良辉
贾德民
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South China University of Technology SCUT
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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
    • 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
    • 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
    • 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
    • C08K2201/002—Physical properties
    • C08K2201/003—Additives being defined by their diameter
    • 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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Abstract

The invention discloses a kind of preparation methods of epoxy natural rubber organic/inorganic hybridization material.Epoxy natural rubber (Epoxidized Natural Rubber, abbreviation ENR) it is Heveatex through special type natural rubber a kind of obtained from the oxidation processes of peroxy acid, remaining part natural rubber high tensile, on the basis of the performances such as elongation strain crystallization, excellent organic solvent resistance, barrier properties for gases and wet-sliding resistant performance are more obtained.With inorganic filler strong interaction can occur for the polarity epoxy group for finding ENR by research, filler is made to play the role of class crosslinking points and reinforcing agent in itself, so as to assign hybrid material certain practical application performance, and traditional rubber processing can be taken to prepare material.Epoxy natural rubber organic/inorganic hybridization material prepared by this method can be applied to the vulcanized rubber article of manufacture particular/special requirement.

Description

A kind of preparation method of epoxy natural rubber organic/inorganic hybridization material
Technical field
The invention belongs to rubber materials, 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 vulcanizing, preventing the auxiliary agents such as old, plasticising, rubber material is made to obtain high resiliency, high stretcher strain and high intensity etc. Application performance.Usually, the excellent physical mechanical property of material in terms of its requirement is met hundred profit and none do harm to, but Certain special application fields, composite material is superfluous there is also certain performance, in addition, during traditional rubber processing, sulphur Change the parts noxious materials such as auxiliary agent, anti-aging agent and there are problems that volatilization, pollution, be unfavorable for environmentally protective technique and green product reason The practice of thought.Most of inorganic filler, such as silica, carbon black, galapectite etc., surface is rich in carboxyl, hydroxyl, ester group Polar organics group is waited, strong interaction, such as covalent bond, ionic bond and hydrogen bond etc. can occur with the rubber of polarity, By the way that inorganic filler is effectively treated, its surface functional group can be activated, filler grain is made to play crosslinking in rubber matrix Agent and the effect of reinforcing agent in the case where not adding other vulcanization aids, prepare the rubber of possible favorable elasticity and intensity Glue organic/inorganic hybridization material.Meanwhile for traditional rubber composite material, the cost of material of hybrid material is lower.
Epoxy natural rubber（ENR）It is oxidation processes of the natural rubber latex through peroxyformic acid or Peracetic acid and obtains, Due to introducing the epoxy group of polarity, 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 group can make its hydroxyl with inorganic filler surface, carboxyl, ester The strong interaction of the generations such as base.Jae Ok Jo etc. are handled multi-walled carbon nanotube using amino silane, then will place Inorganic filler after reason is blended with epoxy natural rubber/chlorinated scoline, is prepared for multi-walled carbon nanotube filling Rubber-base composite material.The study found that epoxy group and hydroxyl, the amino of modified carbon nano tube pipe surface etc. are chemically bonded, The network structure between carbon nanotube and ENR is enhanced, finally improves heat conduction and the gas barrier property of composite material.（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. using ENR as interface modifier, answer by the natural rubber for applying it to white carbon filling In condensation material system, as a result, it has been found that, the interface compatibility of inorganic filler and rubber matrix be improved significantly, and improve compound The multinomial physical mechanical property of material.Interface interaction research shows that, the epoxy group of the silicone hydroxyl on white carbon surface and ENR occur 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 epoxy group can be used to carry out chemistry with inorganic filler Reaction.Pass through suitable method（Such as control the specific surface area of inorganic filler and surface that can, reduce activation energy reacted etc.）, have May be formed between ENR and inorganic filler two it is good be bonded in the case where not adding other conventional vulcanized auxiliary agents, make For the hybrid material for the epoxy natural rubber/inorganic filler for going out certain performance.The preparation of this hybrid material is compared with biography For the vulcanization of rubber processing of system, more environmentally-friendly low cost has certain economic results in society.
Invention content
For overcome the deficiencies in the prior art, the purpose of the present invention is to provide a kind of epoxy natural rubber it is organic/nothing The preparation method of machine hybrid material, 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, includes the following steps：
（1）Inorganic filler is added to the suspension for being made into that mass concentration is 10 ~ 25% in solvent；
（2）Modifying agent is added in suspension, it is stirred to react 6 at 40 ~ 100 DEG C ~ for 24 hours, and filtering, rinsing, centrifugation, 30 ~ 80 DEG C of dryings obtain modified inorganic filler to constant weight；
（3）Have epoxy natural rubber is obtained after modified inorganic filler and epoxy natural rubber blending, co-vulcanization Machine/inorganic hybrid material；
The addition of the modifying agent can be added in the suspension of inorganic filler, also can be in inorganic filler and epoxidation day The stage of T PNR blending adds in.
A kind of another preparation method of epoxy natural rubber organic/inorganic hybridization material, includes the following steps：
（1）Inorganic filler is added to the suspension for being made into that mass concentration is 10 ~ 25% in solvent；
（2）Modifying agent is added in suspension, it is stirred to react 6 at 40 ~ 100 DEG C ~ for 24 hours, and filtering, rinsing, centrifugation, 30 ~ 80 DEG C of dryings obtain modified inorganic filler to constant weight；
（3）Modified inorganic filler is mixed with epoxy natural rubber latex, at 30 ~ 80 DEG C stir 0.5 ~ for 24 hours；
（4）By step（3）Gained mixed emulsion is in acid or CaCl2It is solidified in the case of spray solution, and is dehydrated, breaks It is broken, it is dried in 50 ~ 110 DEG C of convection oven to constant weight, obtains the coprecipitated glue of epoxy natural rubber of Inorganic Fillers Filled；
（5）By step（4）The obtained coprecipitated glue of epoxy natural rubber is blended, obtains epoxy natural rubber after co-vulcanization Organic/inorganic hybridization material.
Preferably, step（1）The inorganic filler including but not limited to precipitated silica, aerosil, angstrom One or more of Lip river stone, carbon black, carbon nanotube and montmorillonite, the particle diameter of the inorganic filler is 5nm ~ 20um；It is described Solvent is ethyl alcohol, acetone, pure water or tap water.
Preferably, step（2）The modifying agent is silane coupling agent, epoxy hardener or catalyst, surfactant One or more of.
It is further preferred that the silane coupling agent is γ-amine propyl-triethoxysilicane, γ-glycidoxy third Base trimethoxy silane, γ-methacryloxypropyl trimethoxy silane, γ mercaptopropyitrimethoxy silane, γ- Mercapto propyldimethoxy-silane, vinyltriethoxysilane and tetra-sulfurized pair（Triethoxy propyl）In silane it is a kind of with On；The 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 Dicarboxylic acid anhydride, organic acid, boron trifluoride and boron trifluoride complex, polyamide and the one or more of polyamide modified amine mix It closes；The surfactant is alkyl phenol, methylene sodium dinaphthalenesulfonate, nekal, the methylene diisopropyl of ethoxylation Base sodium naphthalene sulfonate, methylene potassium diisopropyl naphthalene sulfonate, sodium pyrophosphate, cetyl trimethylammonium bromide（CTAB）, cetyl Trimethyl ammonium chloride（CTAC）, neopelex（SDBS）With one or more mixing in dodecyl sodium sulfate.
Preferably, step（3）The epoxy natural rubber is solid epoxidation natural rubber；The epoxidation is natural The epoxy content of rubber is 20 ~ 50%.
Preferably, the amount of modifier is the 0.5%~15% of inorganic filler quality；The inorganic filler dosage is epoxy Change the 10~100% of natural rubber quality.
Preferably, using mixing, the one or two of mill, mechanical blending temperature is 30 ~ 100 DEG C for the blending, the time For 5 ~ 30min；The temperature of the co-vulcanization is 140 ~ 180 DEG C, and the time is 15 ~ 60min.
Preferably, step（3）The epoxy content of the epoxy natural rubber latex is 20 ~ 50%, mass concentration for 10 ~ 40%；Step（4）The mass concentration of the acid is 1 ~ 10%；CaCl2The mass concentration of solution is 1 ~ 15%.Dosage is epoxy latex The 0.5 ~ 2.0% of solid dry rubber content.
Preferably, step（4）The acid is one or more of organic acid and inorganic acid；It is further preferred that described have Machine acid is formic acid, acetic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, leukotrienes, benzene sulfonic acid, amino acid, malic acid, ethanedioic acid One or more of；The inorganic acid for hydrochloric acid, sulfuric 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 in the present invention, the generation such as effect one side and hydroxyl, the carboxyl of inorganic filler surface covalent bond, The combination of hydrogen bond or ionic bond weakens the reunion of filler grain itself, enhances inorganic filler and the interaction of epoxy glue；It is another Aspect as modifying agent in itself, can both be catalyzed the ring-opening reaction of epoxy group and inorganic filler surface organic group, can also replace The active function groups of inorganic filler surface are changed, are instead more easy to the group with epoxy reaction, the crosslinking for improving hybrid material is close Degree, achievees the purpose that be obviously improved hybrid material performance.
The present invention is that inorganic filler surface is modified, while can also be used and the epoxy group in ENR is modified. On the one hand modified inorganic filler can reduce the reunion of particle itself, increase the filler contact with the rubber matrix of polarity in itself Area, promotes the interaction between the two, and inorganic filler is also improved with the compatibility of rubber matrix in itself；Modified epoxy The purpose of group is to increase the intermolecular distance of polar rubber, the flexibility of reinforced epoxy glue, while replaces more to react The group of activity, such as amino, enhancing rubber molecule and the reactivity of inorganic filler surface functional group, promote the friendship of hybrid material Join density.
The epoxy natural rubber organic/inorganic hybridization material of the present invention, can be with as a kind of hybrid material of epoxies It is prepared using traditional rubber processing, and the pollution problem of small powder auxiliary agent is not present in process, reduces simultaneously Use cost.In terms of performance, part formulations have high hardness, high-modulus and low tensile set, can apply Special rubber field.
It is of the invention compared with existing technology, have the following advantages that and advantageous effect：
1st, by epoxy natural rubber and modified inorganic filler direct hybridization mechanism, and the traditional processing side of rubber is not changed Method, it is simple and practicable, it is of low cost.
2nd, in the compound prepared by the present invention, inorganic filler plays the role of reinforcing agent and vulcanizing agent, compared with 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 For solids epoxy glue product.
4th, epoxy natural rubber/gas-phase silica organic/inorganic hybridization material prepared by the present invention, 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, and tensile strength is reachable 20.0Mpa, elongation at break is up to 400%, and tearing strength is up to 50KN m-1, Shao's A hardness is up to 90.
Description of the drawings
Fig. 1 is the Dynamic Thermal of the material after the ENR-20/pre-silica hybrid materials vulcanization of different ratio in embodiment 1 Mechanical Property Analysis figure（DMA）.
Fig. 2 is galapectite in embodiment 3（HNTs）ENR-50/HNTs hybrid materials vulcanizate when number is 40 parts is filled to draw The stereoscan photograph in the brittle failure face of stretching（SEM）.
Fig. 3 is galapectite in embodiment 3（HNTs）ENR-50/HNTs hybrid materials vulcanizate when number is 60 parts is filled to draw The stereoscan photograph in the brittle failure face of stretching（SEM）.
Fig. 4 is unmodified galapectite in embodiment 3（HNTs）Transmission electron microscope photo（TEM）.
Fig. 5 is the transmission electron microscope photo of the product after the extracting of ENR-50/HNTs hydridization blend in embodiment 3（TEM）.
Specific embodiment
With reference to embodiment, the present invention is described in more detail.
Embodiment 1
The first step is by 30g precipitated silicas（Pre-silica, particle diameter 5nm）It is added in tap water and is configured to Mass concentration is 10% suspension, is stirred；
The methylene sodium dinaphthalenesulfonate of precipitated silica dosage 0.5wt% is added drop-wise to suspension obtained by the first step by second step In, it is stirred for 24 hours 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 to perseverance Weight；
Third step is by the silica that second step is modified from solid ENR-20 according to open mill of the different proportionings at 30 DEG C Upper blending, mill 30min obtain ENR/pre-silica hydridization blends；
4th step vulcanizes the ENR/pre-silica hydridization blends that third walks on purl machine, curing temperature 180 DEG C, time 15min, the ENR-20/pre-silica hybrid materials vulcanized.ENR-20/pre-silica hybrid materials Mechanical property is as shown in table 1.
Table 1
As shown in Table 1, in hybrid material white carbon content be continuously increased, the stress at definite elongation of material, tensile strength, The mechanical property parameters such as tearing strength, hardness constantly increase, and show the interface interaction of epoxy glue and white carbon in system The increase of filling mixture ratio and enhance, hard charcoal black track producing particle to rubber phase be crosslinked and reinforcement effect it is more obvious.Fig. 1 is different ratio ENR/pre-silica hybrid materials vulcanization after material dynamic thermomechanical analysis chart（DMA）.As shown in Figure 1, hydridization material The glass transition temperature Tg of material vulcanizate increases afterwards as the increase of amount of filler first reduces, and illustrates to surpass when silica-filled amount When crossing 20phr, the elasticity of good fortune material is remarkably reinforced, Tg increases.Meanwhile the fissipation factor of the vulcanizate of high temperature section is with dioxy Increasing for SiClx content has the tendency that successively decreasing, and further demonstrates that the elasticity of hybrid material becomes larger.
Embodiment 2
The first step is by 30g precipitated silicas（Pre-silica, particle diameter 20um）It is added in ethyl alcohol and is configured to matter A concentration of 25% suspension is measured, is stirred；
The triethanolamine of precipitated silica dosage 15wt% is added drop-wise in suspension obtained by the first step by second step, and 100 6h is stirred under the conditions of DEG C；Take out modified white carbon slurry, after rinsing, centrifugation 3 times, 80 DEG C of freeze-day with constant temperature to constant weight；
The silica that second step is modified by third step is with solid ENR-35 according to mass ratio 1:1 proportioning is at 65 DEG C It is blended on open mill, while the maleic anhydride of ENR-35 dosages 7.75wt% is added dropwise, mill 5min obtains ENR/pre- Silica hydridization blends；
4th step vulcanizes the ENR/pre-silica hydridization blends that third walks on purl machine, curing temperature 140 DEG C, time 60min, the ENR-35/pre-silica hybrid materials vulcanized.ENR-35/pre-silica hybrid materials Physical mechanical property is as shown in table 2.
Table 2
As shown in Table 2, in ENR/pre-silica constant 1:In the case of 1 proportioning, the hydridization that is equally matched in contrast table 1 Material, after epoxide number improves, the mechanical performance index of hybrid material is obviously improved.This illustrates the increasing of epoxy group content More, white carbon rises with the probability that epoxy glue chemically reacts, and improves the overall mechanical properties of hybrid material.
Embodiment 3
The first step is by 30g galapectites（HNTs, particle diameter 50nm）It is added in tap water and is configured to mass concentration and is 17.5% suspension, stirring；
The methylene sodium diisopropylnaphthalene sulfonate of 7.75 wt% of HNTs dosages is added drop-wise to suspension obtained by the first step by second step In, stir 15h 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 to constant weight；
Third step is by the HNTs that second step is modified and solid ENR-50 according to different proportionings on 100 DEG C of open mill Blending, while the boron trifluoride of 2 wt% of HNTs dosages is added dropwise, mill 17.5min obtains ENR/HNTs hydridization blends；
4th step vulcanizes the ENR/HNTs hydridization blends that third walks on purl machine, 160 DEG C of curing temperature, the time 37.5min, the ENR-50/HNTs hybrid materials vulcanized.The mechanical property of ENR-50/HNTs is as shown in table 3.
Table 3
As shown in Table 3, in hybrid material galapectite content increase, the stress at definite elongation of material, tensile strength, fracture The mechanical performance indexs parameter such as elongation, tearing strength, hardness number increases.Since the activity group content on galapectite surface is low In white carbon, therefore, in the crosslinking degree of the system or the severity of reaction not as good as white carbon system, low mechanics is shown Performance parameter.Simultaneously as the nano tubular structure that galapectite is special, in ENR hybridisation process, with filler orientation Phenomenon, as shown in Figure 2 and Figure 3.Galapectite is orientated significantly in rubber material drawing process, and hybrid material mechanical property is carried It rises to have and definitely act on.In addition, Fig. 4, Fig. 5 compared galapectite and the nanotube transmission electron microscope photo before and after ENR blending hydridization. It can be seen from the figure that being handled by hydridization, the outer diameter of part galapectite pipe significantly increases, edge blurry.This explanation, ENR has been grafted to galapectite surface, and the similar crosslinking and reinforcement that galapectite is played the role of have been confirmed in side.
Embodiment 4
The first step is by 30g aerosils（F-silica, particle diameter 10um）It is added in tap water and is configured to matter A concentration of 15% suspension is measured, is stirred；
Second step drips double-[γ-(triethoxysilicane) propyl] tetrasulfide of 10 wt% of aerosil dosage It is added in suspension obtained by the first step, 8h is stirred under the conditions of 70 DEG C；Take out modified silica slurry, rinsing, centrifugation 3 times Afterwards, 30 DEG C of freeze-day with constant temperature are to constant weight；
The third step silica for being modified second step and the epoxidized natural latex for containing 10 wt% admittedly matched in right amount （Epoxy content 40%）0.5h, 80 DEG C of temperature are stirred in mixing；
4th step uses the CaCl of mass concentration 15%2Spray solution is carried out in mixed liquor obtained by third step at solidification Reason, and be dehydrated, crush, obtaining the coprecipitated glue of ENR/F-silica after 110 DEG C of dryings；
The coprecipitated glue of ENR/F-silica of 4th step is blended 5th step on a mill, 80 DEG C, time 15min of temperature, Obtain blend.
6th step vulcanizes the blend of the 5th step on purl machine, and 160 DEG C of curing temperature, time 30min obtains sulphur The ENR-40/F-silica hybrid materials of change.The physical mechanical property of ENR-40/F-silica is as shown in table 4.
Table 4
As shown in Table 4, in hybrid material aerosil content be continuously increased, the stress at definite elongation of material is drawn It stretches the mechanical property parameters such as intensity, tearing strength, hardness constantly to increase, shows that the interface of epoxy glue and aerosil is made Enhanced with the increase of filling mixture ratio in system, silicon dioxide granule is crosslinked rubber phase and the effect of reinforcement is brighter It is aobvious.
Embodiment 5
The first step is by 30g aerosils（F-silica, particle diameter 8nm）It is added in tap water and is configured to matter A concentration of 17% suspension is measured, is stirred；
Second step drips double-[γ-(triethoxysilicane) propyl] tetrasulfide of 10 wt% of aerosil dosage It is added in suspension obtained by the first step, 8h is stirred under the conditions of 70 DEG C；Take out modified silica slurry, rinsing, centrifugation 3 times Afterwards, 80 DEG C of freeze-day with constant temperature are to constant weight；
The third step silica for being modified second step and the epoxidized natural latex for containing 40 wt% admittedly matched in right amount （Epoxy content 40%）Mixing is stirred for 24 hours, 30 DEG C of temperature；
4th step is sprayed in third step gained mixed liquor using the formic acid solution of mass concentration 10% and carries out solidification processing, And it is dehydrated, crushes, obtaining the coprecipitated glue of ENR/F-silica after 50 DEG C of dryings；
The coprecipitated glue of ENR/F-silica of 4th step is blended 5th step on a mill, and adds in 1 wt% of ENR dosages M-xylene diamine, temperature 60 C, time 15min obtains blend.
6th step vulcanizes the blend of the 5th step on purl machine, and 160 DEG C of curing temperature, time 30min obtains sulphur The ENR-40/F-silica hybrid materials of change.The mechanical property of ENR-40/F-silica hybrid materials is as shown in table 5.
Table 5
As shown in Table 5, in hybrid material aerosil content be continuously increased, the stress at definite elongation of material is drawn The mechanical property parameters such as intensity, tearing strength, hardness are stretched constantly to increase, show the interface interaction of epoxy glue and silica with It the increase of filling mixture ratio in system and enhances, silicon dioxide granule is crosslinked rubber phase and the effect of reinforcement is more obvious.It is right Than data in table 4, it can be seen that the selection of the solidification mode and modifying agent of coprecipitated glue influences very the performance of final hybrid material Significantly.
Embodiment 6
The first step is by 30g aerosils（F-silica, particle diameter 15nm）It is added in tap water and is configured to matter A concentration of 17% suspension is measured, is stirred；
Second step drips the γ of 10 wt% of aerosil dosage-methacryloxypropyl trimethoxy silane It is added in suspension obtained by the first step, 8h is stirred under the conditions of 70 DEG C；Take out modified silica slurry, rinsing, centrifugation 3 times Afterwards, 80 DEG C of freeze-day with constant temperature are to constant weight；
The third step silica for being modified second step and the epoxidized natural latex for containing 25 wt% admittedly matched in right amount （Epoxy content 50%）12.5h, 55 DEG C of temperature are stirred in mixing；
4th step uses the acetum and 8% CaCl of mass concentration 1%2Spray solution is in mixed liquor obtained by third step In carry out solidification processing, and be dehydrated, crush, obtaining the coprecipitated glue of ENR/F-silica after 80 DEG C of dryings；
The coprecipitated glue of ENR/F-silica of 4th step is blended 5th step on a mill, and adds in 2 wt% of ENR dosages Diethylaminopropylamine, 80 DEG C of temperature, time 20min obtains blend.
6th step vulcanizes the blend of the 5th step on purl machine, and 170 DEG C of curing temperature, time 30min obtains sulphur The ENR-50/F-silica hybrid materials of change.The mechanical property of ENR-50/F-silica hybrid materials is as shown in table 6.
Table 6
As shown in Table 6, in hybrid material aerosil content be continuously increased, the stress at definite elongation of material is drawn The mechanical property parameters such as intensity, tearing strength, hardness are stretched constantly to increase, show the interface interaction of epoxy glue and silica with It the increase of filling mixture ratio in system and enhances, silicon dioxide granule is crosslinked rubber phase and the effect of reinforcement is more obvious.It should Under system, 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, which is characterized in that include the following steps：
（1）Inorganic filler is added to the suspension for being made into that mass concentration is 10 ~ 25% in solvent；
（2）Modifying agent is added in suspension, it is stirred to react 6 at 40 ~ 100 DEG C ~ for 24 hours, and filtering, rinsing, centrifugation, 30 ~ 80 It is DEG C dry to constant weight, obtain modified inorganic filler；
（3）Modified inorganic filler is mixed with epoxy natural rubber, on the basis of other vulcanization aids are not added directly Epoxy natural rubber organic/inorganic hybridization material is obtained after hot-forming；
The addition of the 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 in.
2. a kind of preparation method of epoxy natural rubber organic/inorganic hybridization material, which is characterized in that include the following steps：
（1）Inorganic filler is added to the suspension for being made into that mass concentration is 10 ~ 25% in solvent；
（2）Modifying agent is added in suspension, it is stirred to react 6 at 40 ~ 100 DEG C ~ for 24 hours, and filtering, rinsing, centrifugation, 30 ~ 80 It is DEG C dry to constant weight, obtain modified inorganic filler；
（3）Modified inorganic filler and epoxy natural rubber latex are stirred 0.5 at 30 ~ 80 DEG C ~ for 24 hours；
（4）By step（3）Gained mixed emulsion is in acid or CaCl2It is solidified in the case of spray solution, and is dehydrated, crushes, It is dried in 50 ~ 110 DEG C of convection oven to constant weight, obtains the coprecipitated glue of epoxy natural rubber of Inorganic Fillers Filled；
（5）By step（4）The obtained coprecipitated glue mixing of epoxy natural rubber, it is straight on the basis of other vulcanization aids are not added Connect it is hot-forming after obtain epoxy natural rubber organic/inorganic hybridization material.
3. according to claim 1,2 any one of them preparation methods, which is characterized in that step（1）The inorganic filler is heavy One or more of shallow lake method silica, aerosil, galapectite, carbon black, carbon nanotube and montmorillonite, it is described inorganic to fill out The particle diameter of material is 5nm ~ 20um；The solvent is ethyl alcohol, acetone, pure water or tap water.
4. according to claim 1,2 any one of them preparation methods, which is characterized in that step（2）The modifying agent is silane One or more of class coupling agent, epoxy hardener or catalyst, surfactant.
5. preparation method according to claim 4, which is characterized in that the silane coupling agent is three second of γ-aminopropyl Oxysilane, γ-glycidoxypropyltrime,hoxysilane, γ-methacryloxypropyl trimethoxy silane, γ- Mercaptopropyi trimethoxy silane, γ-mercapto propyldimethoxy-silane, vinyltriethoxysilane and tetra-sulfurized pair（Three second Oxygroup propyl）One or more of silane；The epoxy hardener or catalyst are triethanolamine, ethylenediamine, hexamethylene diamine, three second Alkene tetramine, diethylaminopropylamine, m-phenylene diamine (MPD), 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；Alkyl phenol, methylene sodium dinaphthalenesulfonate, two fourths of the surfactant for ethoxylation Base sodium naphthalene sulfonate, methylene sodium diisopropylnaphthalene sulfonate, methylene potassium diisopropyl naphthalene sulfonate, sodium pyrophosphate, cetyl trimethyl It is one or more mixed in ammonium bromide, hexadecyltrimethylammonium chloride, neopelex and dodecyl sodium sulfate It closes.
6. preparation method according to claim 1, which is characterized in that step（3）The epoxy natural rubber is solid Epoxy natural rubber；The epoxy content of the epoxy natural rubber is 20 ~ 50%.
7. according to claim 1,2 any one of them preparation methods, which is characterized in that the amount of modifier is inorganic filler The 0.5%~15% of quality；The inorganic filler dosage is the 10~100% of epoxy natural rubber quality.
8. according to claim 1,2 any one of them preparation methods, which is characterized in that the mixing is using mixing, mill One or two, mechanical blending temperature are 30 ~ 100 DEG C, and the time is 5 ~ 30min；The hot-forming temperature is 140 ~ 180 DEG C, the time is 15 ~ 60min.
9. preparation method according to claim 2, which is characterized in that step（3）The epoxy natural rubber latex Epoxy content is 20 ~ 50%, and mass concentration is 10 ~ 40%；Step（4）The mass concentration of the acid is 1 ~ 10%；CaCl2The matter of solution Measure a concentration of 1 ~ 15%.
10. preparation method according to claim 2, which is characterized in that step（4）The acid is in organic acid and inorganic acid More than one；The organic acid is formic acid, acetic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, leukotrienes, benzene sulfonic acid, amino One or more of acid, malic acid, ethanedioic acid；The inorganic acid is hydrochloric acid, sulfuric 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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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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