CN105419009A - Method for preparing high-filling composite masterbatch through semi-open type superheated steam spray-drying method - Google Patents
Method for preparing high-filling composite masterbatch through semi-open type superheated steam spray-drying method Download PDFInfo
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Abstract
The invention provides a method for preparing high-filling composite masterbatch through a semi-open type superheated steam spray-drying method, and relates to the field of preparation of high-filling composite rubber masterbatch. Modification treatment is conducted on inorganic filler through a modifying agent, the modified inorganic filler is ground and uniformly dispersed into a rubber emulsion, and then the technology of using a spray-drying technology to prepare the high-filling composite masterbatch is adopted. The technology comprises the steps that inorganic suspension liquid is prepared by adding water, the modifying agent is added for treatment, the fully-ground inorganic suspension liquid is added to the rubber emulsion and stirred to be uniform, spray drying is conducted under the condition without demulsification, and a powder or microbead-shaped composite masterbatch product is obtained. According to the method for preparing the high-filling composite masterbatch through the semi-open type superheated steam spray-drying method, the technology is simple, the rubber component is completely reserved, the problem of high-filling masterbatch is solved, no flocculant is added, pollution does not exist, the drying time is short, human factors are few, continuous production can be achieved, the product quality is stable, and industrialization is easy. By means of the nano composite masterbatch, the inorganic filler can be uniformly dispersed in a rubber matrix in a nano-scaled mode, and the nano composite masterbatch can be applied to the fields such as saloon car tires and engineering tread rubber.
Description
Technical field
The present invention relates to a kind of method that semi-open type superheated vapour spray-drying process prepares high filled composite rubber master batch.The method gained rubber height is filled nano combined rubber master batch and is mainly used in car tread rubber, the fields such as engineering tread rubber.
Background technology
The method that tradition prepares rubber is raw material with rubber latex, through acid coagulation, then through compressing tablet or granulation, drying and dehydrating and the rubber made.Traditional technology not only the preparation time cycle long, and substantially for manual operation, there is comparatively big error.Need a large amount of acid to be siccative in production process, the waste water produced in treating processes cannot process, contaminate environment.Meanwhile, tradition preparation rubber process quality is wayward, result in homogeneity of product poor.
In rubber industry field, drying process with atomizing has a small amount of application.But rubber latex is comparatively large due to its viscosity, make easily to glue wall in spray-drying process, blocking feed-pipe, even blocks the problems such as spraying gun, constrains the application of spraying dry in rubber dryness field.
In order to solve the problem, nanometer composite technology is incorporated into spray drying art by people.In traditional technology, the addition manner of mineral filler in rubber matrix is often that dry method is mixing.No matter be that mill is added, or add in Banbury mixer, all there is highly energy-consuming, not easily realize the effect of nano-scale dispersion, this is also the gordian technique that acquisition composite material combination property significantly promotes.
Instantly, rubber master batch technology becomes the focus of rubber materials research, and the nano-scale dispersion of mineral filler in rubber latex such as carbon black, white carbon black, clay become the emphasis studied in rubber master batch technology.
Mineral filler after treatment agent process, with the mixing process of rubber latex in mutually intert after buffer action and define the structure of disperseing good mineral filler and rubber grain compound.And also because mineral filler exists between latex particle and latex particle, forming a kind of mutually isolated effect makes adhesion between latex particle become block to block feed-pipe, thus solve the difficult point that drying process with atomizing prepares plugging in rubber process.
The human hairs such as the Qiao Jin fine strain of millet professor of Beijing Chemical Institute of China Petrochemical Corporation understand a kind of preparation method's (patent No.: 00816450.9) of fully vulcanized powder rubber.They are that to utilize irradiation to realize the emulsion particle of rubber latex cross-linking vulcanized, after carry out the powdered rubber that spraying dry obtains full sulfuration.It is very easily dispersed in plastic substrate, can be used for preparing various toughened plastics and thermoplastic elastomer.The human hairs such as professor Zhu Yuefeng of Tsing-Hua University understand a kind of powder natural rubber (patent No.: 200510058999.6) of carbon nano-tube modification; They disperse after carbon nano tube surface process in water, mix with natural rubber latex, then adopt the powder natural rubber of spray-drying process preparation containing carbon nano-tube modification.
But spraying dry is applied and be there is many problems in rubber materials, thus limit the development of spraying dry in rubber dryness field.Mainly be limited in drying process, because the too high meeting of local temperature causes rubber thermo-oxidative ageing comparatively serious, even the phenomenons such as burning can occur.The most important thing is rubber dryness, because rubber viscous, can make latex blocking pipe, the phenomenons such as wall built-up occur.
Current superheated vapour belongs to advanced technologies at spray drying technology in dry field, its drying mechanism be by the liquid starting material such as suspension, solution under the effect of high speed centrifugation or high pressure, form fine atomized droplets, considerably increase the be heated specific surface area of liquid starting material in drying medium, shorten rate of drying dramatically, simultaneously, superheated vapour spray drying device due to its drying medium be steam, thus ensure that material can not produce localized hyperthermia in drying process, decrease thermooxidizing and the degree of aging of material.
Adopt semi-open type Vapojet dryer, this is because water vapour is in drying process, constantly increase, if closed superheated vapour, spray tower internal pressure can extend along with the reaction times and increase.When pressure reaches 1.5MPa, pressure valve can be opened automatically, is discharged in tower by unnecessary water vapour, thus realizes tower internal pressure balance.
By to mineral filler modification, mixed grinding adopts spraying dry to prepare the nano combined rubber master batch of high filling after forming mixed solution, the process employs a step drying mode of comparatively simple and fast, decrease in traditional technology and flocculate, the processes such as washing, shorten the process time and have saved cost simultaneously.And the water of condensation produced in process of production, ethanol etc. also will use as recovery.Respond the policy of national environmental protection just, decrease waste and the environmental pollution of water resources,
Summary of the invention
The object of the invention is to propose a kind of simple to operate, cost is low, be easy to industrialized novel height fills nano combined rubber master batch production technology, provides a kind of method that semi-open type superheated vapour spray-drying process prepare the nano combined rubber master batch of high filling.Processing step is mainly and mineral filler is mixed with suspension slurry, carries out clearly blended after modification grinding with glue, stirs and ensures that mixed solution is without under the condition of breakdown of emulsion, carries out superheated vapour spraying dry and obtains the nano combined rubber master batch of high filling.
In this technique, mineral filler number is 25 ~ 120 parts, in general dry method is mixing, still belongs to high number fill process.Through the mineral filler of modifier treatment, in milled processed process, particle surface structure there occurs change, with rubber latex effect, form the mixed emulsion of not breakdown of emulsion, the fine drop of 30 ~ 100 μm is formed after the spraying gun high speed centrifugation effect of spray drying device, larger specific surface area quick dewatering drying in the steam medium of 100 ~ 350 DEG C, because exist containing a large amount of fillers, define good sealing coat, make to form Powdered or particulate state sizing material to stick together because of viscosity own, the phenomenons such as wall built-up.Finally bring delivery area into through air inducing effect again, obtain powder height and fill nano combined rubber master batch.Such rubber master batch preparation technology, solve in traditional technology add acid treatment, flocculation wastewater treatment not easily, the problem such as flocculation blob of viscose not easily cleans, drying room time of drying is long.In addition, because mineral filler is after modification, the mineral fillers such as white carbon black, carbon black, clay can be better compatible with sizing material, also solves the problems such as the mixing middle mineral filler of conventional dry not easily disperses in rubber matrix, energy consumption is large, dust is large.Superheated vapour drying process with atomizing exists because of superheated vapour, be different from warm air directly and the contact of sizing material, make sizing material drying efficiency fast, avoid the features such as time of drying in conventional drying processes is long, sizing material is oxidizable, aging, the nano combined rubber master batch thermal history obtained is low, deterioration by oxidation is few, low power consumption and other advantages.
Solve technique of the present invention and adopt following steps:
1. a semi-open type superheated vapour spray-drying process prepares the method for high filled composite rubber master batch, it is characterized by: the formulation content that adds water is the mineral filler suspension of 2% ~ 30%, 15min is ground after adding modifier treatment, mineral filler suspension after process is added rubber latex, mineral filler quality is 25 ~ 120% of rubber latex dry glue quality, the mixing suspension of mineral filler/rubber latex is obtained after stirring, in mixing suspension, particulate matter diameter is 5 ~ 20 μm, spray drying treatment, atomization droplets diameter is 30 ~ 100 μm, spray drying device inlet temperature 150 ~ 350 DEG C, temperature out 100 ~ 120 DEG C, obtain Powdered rubber combined rubber master batch.
Further, mineral filler is carbon black, white carbon black or clay.
When mineral filler is carbon black powder, suspension concentration is 3 ~ 30%, and carbon black loading is 30 ~ 60% of rubber latex dry glue quality.Properties-correcting agent selects ethanol as treating compound, and ethanol consumption is 50 ~ 100% of carbon black mass.
When mineral filler is white carbon black powder, suspension concentration is 10 ~ 30%, and white carbon black consumption is 30 ~ 120% of rubber latex dry glue quality.Properties-correcting agent selects polyoxyethylene glycol, silica coupling agent, polyvalent alcohol, and consumption is 1% ~ 5% of white carbon black quality, and white carbon black suspension, before mixing with latex, need process 1 ~ 3h under 70 ~ 90 DEG C of heating conditions.
When mineral filler is clay, suspension concentration is 2 ~ 20%, and clay consumption is 25 ~ 120% of rubber latex dry glue quality.Properties-correcting agent is quaternary ammonium salt, and the preferred main chain of the quaternary ammonium salt used is the quaternary ammonium salt of 12 to 18 containing carbon number, and the mass ratio of itself and clay is 0.1% ~ 5%.
Further, rubber latex is the clear emulsion of glue, nature rubber latex, SBR emulsion, neoprene latex, acrylonitrile-butadiene rubber latex, vinylpyridiene-styrene-butadiene rubber emulsion, vinylpyridine-butadiene rubber emulsion, and the mixing of above-mentioned rubber latex.
Mineral filler is selected pressed powder to add water and is mixed with suspension, treated dose of process obtains homogeneous suspension, the more difficult infiltration of such as carbon black and water forms comparatively homogeneous suspension, therefore needs to add treating compound process, adds shredder and repeatedly grinds down and can be prepared into homogeneous aqueous solution.And white carbon black adds water to be mixed with after suspension sedimentation agglomeration easily occurs, need to add that some organic modifiers are anti-to fall heavy thus form the uniform aqueous solution.Inorganic clay is after quaternary ammonium salt-modified organising, and its laminated structure changes, and sheet interlayer spacing increases, and make when with micelle effect, effect is more well good.
After uniform carbon black, white carbon black suspension add and stirs in rubber latex, because of the effect of properties-correcting agent, can make together with a large amount of inorganic particulates acts on rubber particles, can obtain disperseing good rubber master batch product after rapid drying.
And clay is added to the water hydration formation clay liquid, add suitable properties-correcting agent, the sheet interlayer spacing of clay can be increased, thus make the latex particle in rubber latex better enter the sheet interlayer of clay alteration clay, in spraying dry wink-dry technique, the structure that latex particle embeds clay layer is able to intact reservation, the good clay filled rubber product of forming property.
Beneficial effect of the present invention
A kind of semi-open type superheated vapour spray-drying process prepares the method for high filled composite rubber master batch, processing step is mainly and mineral filler is mixed with finely disseminated suspension slurry, modification is ground afterwards and rubber latex is carried out blended, stir and ensure without under the condition of breakdown of emulsion, carry out spraying dry and obtain nano combined rubber master batch, the advantage of this method is:
1. avoid using strong acid as peptizer, without sewage disposal, environmental friendliness.
2. reduce production cost, reduce the waste of water resources.
3. the present invention adopts properties-correcting agent to carry out modification to mineral filler, improves mineral filler dispersiveness in rubber matrix.
4. non-glue composition retains complete, promotes the quality of rubber.
5. technique is simple, and equipment requirements is low, and production efficiency is high.
6. superheat steam drying, product thermal history is low, deterioration by oxidation is few.
7. the nano combined rubber master batch prepared of the inventive method, solve the dust from flying caused in dry method mixing process, the problem of contaminate environment, decreases environmental pollution, provides cost savings.
8. preparation technology of the present invention, saves flocculation time, shortens life cycle of the product, and save manpower and energy consumption, technique artifical influence factor is little, is easy to obtain stay-in-grade product, is applicable to successional suitability for industrialized production.
Facilities and equipments of the present invention are conventional equipment, and all properties testing standard is all carried out according to corresponding national standard.
Embodiment
Embodiment 1
Commercially available carbon black N234 powder 30g is added in 970g water, after stirring, adds 15g ethanol, after stirring, grind 15min, obtain carbon black suspension.Under agitation, be mixed into the natural emulsion that 333.3g solid content is 30%, obtain the mixed solution that particle diameter is 5 μm of micelles, the mixed solution stirred is carried out semi-open type superheated vapour spray drying treatment, atomizing droplet controls at 30 μm, and spraying dry inlet temperature is 150 DEG C, and temperature out is 80 DEG C, obtain Powdered nano combined rubber master batch, in drying process, ethanol is reclaimed in condensation.Get above-mentioned rubber master batch 130phr, ZnO5phr, stearic acid 2phr, anti-aging agent 1010NA1phr, accelerant CZ 1.2phr, sulphur 2phr, refining glue, surveys vulcanization curve and Rubber processing performance, sulfuration at 143 DEG C after parking 8h, survey mechanical property.
Embodiment 2
Commercially available carbon black N330 powder 60g is added in 140g water, after stirring, adds 60g ethanol, after stirring, grind 15min, obtain carbon black suspension.Under agitation, be mixed into the natural rubber latex that 333.3g solid content is 30%, obtain the mixed solution that particle diameter is 20 μm of micelles, the mixed solution stirred is carried out semi-open type superheated vapour spray drying treatment, atomizing droplet controls at 100 μm, and spraying dry inlet temperature is 350 DEG C, and temperature out is 120 DEG C, obtain Powdered nano combined rubber master batch, in drying process, ethanol is reclaimed in condensation.Get above-mentioned rubber master batch 160phr, all the other steps are with embodiment 1.
Embodiment 3
Commercially available carbon black N110 powder 50g is added in 450g water, after stirring, adds 30g ethanol, after stirring, grind 15min, obtain carbon black suspension.Under agitation, be mixed into the styrene-butadiene latex that 250g solid content is 40%, obtain the mixed solution that particle diameter is 10 μm of micelles, the mixed solution stirred is carried out semi-open type superheated vapour spray drying treatment, atomizing droplet controls at 50 μm, and spraying dry inlet temperature is 250 DEG C, and temperature out is 100 DEG C, obtain Powdered nano combined rubber master batch, in drying process, ethanol is reclaimed in condensation.Get above-mentioned rubber master batch 150phr, all the other steps are with embodiment 1.
Embodiment 4
Commercially available carbon black N234 powder 50g is added in 450g water, after stirring, adds 30g ethanol, after stirring, grind 15min, obtain carbon black suspension.Under agitation, be mixed into 200g solid content be 25% field natural rubber latex and 125g solid content be the SBR emulsion of 40%, obtain the mixed solution that particle diameter is 5 μm of micelles, the mixed solution stirred is carried out semi-open type superheated vapour spray drying treatment, atomizing droplet controls at 70 μm, and spraying dry inlet temperature is 300 DEG C, and temperature out is 120 DEG C, obtain Powdered nano combined rubber master batch, in drying process, ethanol is reclaimed in condensation.Get above-mentioned rubber master batch 150phr, all the other steps are with embodiment 1.
Embodiment 5
Commercially available white carbon black powder 30g is added in 270g water, after stirring, adds 0.3g PEG 8000, under 70 DEG C of heating, process 3h, grind 15min after process, obtain white carbon black suspension.Under agitation, be mixed into the styrene-butadiene emulsion that 200g solid content is 40%, obtaining is the mixed solution of 1 μm of micelle containing particle diameter, the mixed solution stirred is carried out semi-open type superheated vapour spray drying treatment, atomizing droplet controls at 30 μm, spraying dry inlet temperature is 350 DEG C, and temperature out is 120 DEG C, obtains Powdered nano combined rubber master batch.Get above-mentioned rubber master batch 130phr, all the other steps are with embodiment 1.
Embodiment 6
Commercially available white carbon black powder 120g is added in 280g water, after stirring, adds 4g isobutyl triethoxy silane, under 90 DEG C of heating, process 1h, grind 15min after process, obtain white carbon black suspension.Under agitation, be mixed into the concentrated natural latex that 166.7g solid content is 60%, obtain the mixed solution that particle diameter is 6 μm of micelles, the mixed solution stirred is carried out semi-open type superheated vapour spray drying treatment, atomizing droplet controls at 60 μm, spraying dry inlet temperature is 220 DEG C, and temperature out is 110 DEG C, obtains Powdered nano combined rubber master batch.Get above-mentioned rubber master batch 180phr, all the other steps are with embodiment 1.
Embodiment 7
Commercially available white carbon black powder 60g is added in 140g water, after stirring, adds 2.4g propyl carbinol, under 90 DEG C of heating, process 2h, pour in colloidal mill after process and grind 15min, obtain white carbon black suspension.Under agitation, be mixed into the neoprene latex that 250g solid content is 40%, obtain the mixed solution that particle diameter is 8 μm of micelles, the mixed solution stirred is carried out semi-open type superheated vapour spray drying treatment, atomizing droplet controls at 80 μm, spraying dry inlet temperature is 180 DEG C, and temperature out is 100 DEG C, obtains the nano combined rubber master batch of particulate state.Get above-mentioned rubber master batch 160phr, all the other steps are with embodiment 1.
Embodiment 8
Commercially available white carbon black powder 60g is added in 140g water, after stirring, adds 2.4g silica coupling agent KH590, under 90 DEG C of heating, process 2h, pour in colloidal mill after process and grind 15min, obtain white carbon black suspension.Under agitation, be mixed into 125g solid content be 40% SBR emulsion and 125g solid content be 40% vinylpyridine-butadiene rubber emulsion, obtain the mixed solution that particle diameter is 10 μm of micelles, the mixed solution stirred is carried out semi-open type superheated vapour spray drying treatment, atomizing droplet controls at 70 μm, spraying dry inlet temperature is 280 DEG C, and temperature out is 110 DEG C, obtains the nano combined rubber master batch of particulate state.Above-mentioned rubber master batch 160phr, all the other steps are with embodiment 1.
Embodiment 9
Commercially available natural sodium bentonite 500g is added in 10L deionized water, stirs 5 hours under the rotating speed of 800r/min, leave standstill after 24 hours, obtain clay/aqeous suspension that solid content is 2.0%; Get 1250g clay/aqeous suspension, add 1g hexadecyl brometo de amonio, pour in colloidal mill after process and grind 15min, obtain white carbon black suspension.Under agitation, be mixed into the clear emulsion of glue that 1250g solid content is 8%, obtain the mixed solution that particle diameter is 13 μm of micelles, the mixed solution stirred is carried out semi-open type superheated vapour spray drying treatment, atomizing droplet controls at 70 μm, spraying dry inlet temperature is 280 DEG C, and temperature out is 90 DEG C, obtains Powdered nano combined rubber master batch.Above-mentioned rubber master batch 125phr, all the other steps are with embodiment 1.
Embodiment 10
Commercially available natural sodium bentonite 100g is added in 400g deionized water, obtains clay/aqeous suspension that solid content is 20%, add 1g octadecyl bromination ammonium, pour in colloidal mill after process and grind 15min, obtain uniform slurry.Under agitation, be mixed into the natural emulsion that 333.3g solid content is 30%, obtain the mixed solution that particle diameter is 15 μm of micelles, the mixed solution stirred is carried out semi-open type superheated vapour spray drying treatment, atomizing droplet controls at 90 μm, spraying dry inlet temperature is 260 DEG C, and temperature out is 110 DEG C, obtains Powdered nano combined rubber master batch.Get above-mentioned rubber master batch 200phr, all the other steps are with embodiment 1.
Embodiment 11
Commercially available natural sodium bentonite 50g is added in 450g deionized water, obtains clay/aqeous suspension that solid content is 10%, add 1g tetradecyl ammonium chloride, pour in colloidal mill after process and grind 15min, obtain uniform slurry.Under agitation, be mixed into the vinylpyridiene-styrene-butadiene rubber emulsion that 250g solid content is 40%, obtain the mixed solution that particle diameter is 10 μm of micelles, the mixed solution stirred is carried out semi-open type superheated vapour spray drying treatment, atomizing droplet controls at 30 μm, spraying dry inlet temperature is 350 DEG C, and temperature out is 110 DEG C, obtains Powdered nano combined rubber master batch.Get above-mentioned rubber master batch 150phr, all the other steps are with embodiment 1.
Embodiment 12
Commercially available natural sodium bentonite 60g is added in 340g deionized water, obtains clay/aqeous suspension that solid content is 15%, add 1.2g lauryl ammonium chloride, pour in colloidal mill after process and grind 15min, obtain uniform slurry.Under agitation, be mixed into 125g solid content be 40% vinylpyridiene-styrene-butadiene rubber emulsion and 125g solid content be the acrylonitrile-butadiene rubber latex of 40%, obtain the mixed solution that particle diameter is 20 μm of micelles, the mixed solution stirred is carried out semi-open type superheated vapour spray drying treatment, atomizing droplet controls at 40 μm, spraying dry inlet temperature is 350 DEG C, and temperature out is 110 DEG C, obtains Powdered nano combined rubber master batch.Get above-mentioned rubber master batch 150phr, all the other steps are with embodiment 1.
Comparative example 1
By formula on two roller begins to pratise machine: natural gum (No. 1, cloud mark) 100phr, carbon black 30phr, all the other Synergist S-421 95s are as embodiment 1, and all the other steps are as embodiment 1.
Comparative example 2
By formula on two roller begins to pratise machine: natural gum (No. 1, cloud mark) 100phr, white carbon black 30phr, all the other Synergist S-421 95s are as embodiment 1, and all the other steps are as embodiment 1.
Comparative example 3
By formula on two roller begins to pratise machine: natural gum (No. 1, cloud mark) 100phr, clay 20phr, all the other Synergist S-421 95s are as embodiment 1, and all the other steps are as embodiment 1.
Comparative example 4
By formula on two roller begins to pratise machine: butadiene-acrylonitrile rubber 100phr, carbon black (N330) 50phr, all the other Synergist S-421 95s are as embodiment 1, and all the other steps are as embodiment 1
Comparative example 5
By formula on two roller begins to pratise machine: neoprene latex 100phr, white carbon black 60phr, all the other Synergist S-421 95s are as embodiment 1, and all the other steps are as embodiment 1
Comparative example 6
By formula on two roller begins to pratise machine: natural gum and butadiene-styrene rubber epoxy glue 100phr, carbon black 50phr, all the other Synergist S-421 95s are as embodiment 1, and all the other steps are as embodiment 1.
Comparative example 7
Commercially available carbon black N234 powder 30g is added in 970g water, after stirring, adds 15g ethanol, pour in colloidal mill after stirring and grind 15min, obtain carbon black suspension.The field natural emulsion being 25% with 400g mass percent is uniformly mixed, add sulphuric acid soln to flocculate, cleaning is to neutral, dry the nano composite material obtaining 30g carbon black/100g natural rubber, by formula on two roller begins to pratise machine: get above-mentioned materials 130phr, all the other Synergist S-421 95s are as embodiment 1, and all the other steps are as embodiment 1.
Comparative example 8
Commercially available white carbon black powder 30g is added in 970g water, after stirring, adds 0.3g PEG 8000, under 90 DEG C of heating, process 2h, pour in colloidal mill after process and grind 15min, obtain white carbon black suspension.The field natural emulsion being 25% with 400g mass percent is uniformly mixed, add sulphuric acid soln to flocculate, cleaning is to neutral, dry the nano composite material obtaining 30g white carbon black/100g natural rubber, by formula on two roller begins to pratise machine: get above-mentioned materials 130phr, all the other Synergist S-421 95s are as embodiment 1, and all the other steps are as embodiment 1.
Comparative example 9
Commercially available natural sodium bentonite 500g is added in 10L deionized water, stirs 5 hours under the rotating speed of 800r/min, leave standstill after 24 hours, obtain clay/aqeous suspension that solid content is 2.0%; Get 1000g clay/aqeous suspension, the field natural emulsion being 25% with 400g mass percent is uniformly mixed, add sulphuric acid soln to flocculate, cleaning is to neutral, dry the nano composite material obtaining 20g clay/100g natural rubber, by formula on two roller begins to pratise machine: get above-mentioned materials 120phr, all the other Synergist S-421 95s are as embodiment 1, and all the other steps are as embodiment 1.
Table one embodiment and the contrast of comparative example mechanical property
Claims (7)
1. a semi-open type superheated vapour spray-drying process prepares the method for high filled composite rubber master batch, it is characterized in that: the preparation mass percent concentration that adds water is the mineral filler suspension of 2% ~ 30%, 15min is ground after adding modifier treatment, mineral filler suspension after process is added rubber latex, mineral filler quality is 25 ~ 120% of rubber latex dry glue quality, the mixing suspension of mineral filler/rubber latex is obtained after stirring, in mixing suspension, particulate matter diameter is 5 ~ 20 μm, semi-open type superheated vapour spray drying treatment, atomization droplets diameter is 30 ~ 100 μm, spray drying device inlet temperature 150 ~ 350 DEG C, temperature out 100 ~ 120 DEG C, obtain the Powdered or rubber combined rubber master batch of microballon shape.
2. preparation method according to claim 1, is characterized in that: mineral filler is carbon black, white carbon black or clay.
3. preparation method according to claim 1, is characterized in that: mineral filler is carbon black powder, and suspension quality percentage concentration is 3 ~ 30%, and carbon black loading is 30 ~ 60% of rubber latex dry glue quality; Properties-correcting agent selects ethanol as treating compound, and ethanol consumption is 50 ~ 100% of carbon black mass.
4. preparation method according to claim 1, is characterized in that: mineral filler is white carbon black powder, and suspension concentration is 10 ~ 30%, and white carbon black consumption is 30 ~ 120% of rubber latex dry glue quality; Properties-correcting agent selects polyoxyethylene glycol, silica coupling agent, polyvalent alcohol, and consumption is 1% ~ 5% of white carbon black quality, and white carbon black suspension, before mixing with latex, need process 1 ~ 3h under 70 ~ 90 DEG C of heating conditions.
5. preparation method according to claim 1, is characterized in that: mineral filler is clay, and suspension concentration is 2 ~ 20%, and clay consumption is 25 ~ 100% of rubber latex dry glue quality; Properties-correcting agent is quaternary ammonium salt, and the mass ratio of itself and clay is 0.1% ~ 5%.
6. preparation method according to claim 1, is characterized in that: the quaternary ammonium salt used is the quaternary ammonium salt of 12 to 18 for main chain contains carbon number.
7. preparation method according to claim 1, it is characterized in that: rubber latex is the clear emulsion of glue, nature rubber latex, SBR emulsion, neoprene latex, acrylonitrile-butadiene rubber latex, vinylpyridiene-styrene-butadiene rubber emulsion, vinylpyridine-butadiene rubber emulsion, or the mixing of above-mentioned rubber latex.
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| WO2017088503A1 (en) * | 2015-11-29 | 2017-06-01 | 北京化工大学 | Method for preparing high-filling composite masterbatch by means of semi-open type superheated steam spray drying method |
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| WO2017088503A1 (en) | 2017-06-01 |
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