CN106084292B - A kind of method of coating modification sulphur - Google Patents
A kind of method of coating modification sulphur Download PDFInfo
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- CN106084292B CN106084292B CN201610410842.3A CN201610410842A CN106084292B CN 106084292 B CN106084292 B CN 106084292B CN 201610410842 A CN201610410842 A CN 201610410842A CN 106084292 B CN106084292 B CN 106084292B
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- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/06—Sulfur
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- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
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- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
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- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
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- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- C08K2003/222—Magnesia, i.e. magnesium oxide
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- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
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- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
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- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
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- C08K2003/265—Calcium, strontium or barium carbonate
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- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
- C08K2003/3045—Sulfates
Abstract
The present invention relates to a kind of methods of coating modification sulphur.The following steps are included: inorganic particle is mixed with water, prepare inorganic particle suspension, modifying agent is added, it is ground after processing, sulphur will be stirring evenly and then adding into the cladding agent emulsion inorganic particle suspension that is added to that treated, obtain inorganic filler/cladding agent emulsion/sulphur mixture, drying crushes, and sieving obtains coating modification sulphur.Method equipment requirement according to the present invention is simple, and preparation process is rapidly and efficiently, environmental-friendly pollution-free, and product sulphur is high in sulfurating stage release rate, and no blooming may be used as vulcanizer, has preferable economic benefit.
Description
Technical field
The present invention relates to a kind of methods of coating modification sulphur, belong to chemical products field, are mainly used in rubber product
In such as tire industry.
Background technique
With the rapid development of China's automobile industry, the annual output of tire also increases year by year, and sulphur is as the main of rubber
Vulcanizing agent, demand also rise year by year.But common solubility of the sulphur in rubber is limited, molten in rubber mixing process
Xie Du can increase as the temperature rises, and temperature can be precipitated in the form of crystallizing when reducing on rubber compound surface, move to glue
The surface of material forms so-called " bloom " phenomenon in tire and rubber product production, has seriously affected the appearance and drop of product
The low adhesiveness of product.
The problems such as in order to solve common sulphur bloom, insoluble sulfur (IS) product come into being, insoluble sulfur (IS),
It is a kind of high molecular polymer of line style long-chain of sulphur (S) deep processing, the number of sulfur atoms on strand is up to 108 or more；No
It is dissolved in carbon disulfide, therefore claims insoluble sulfur.IS is that generally acknowledged have the characteristics that the best vulcanizer of no blooming, tool at present
1. having the advantage that makes sizing material have good tack.The adhesive strength that each interlayer of multilayer rubber product can be improved, especially may be used
The bond properties of steel wire and rubber when improving manufacture tire.2. insoluble sulfur is uniformly distributed in sizing material, effectively reduce
When sizing material is stored the phenomenon that incipient scorch, sizing material storage period is extended, ensure that vulcanization uniformly, improves rubber product quality.3. by
Rubber is not dissolved in it, bloom is generated due to without moving to sizing material surface, ensure that the presentation quality of light color article.In vapour
In the production of vehicle full steel wire radial tyre, insoluble sulfur is optimal vulcanizer and promotor, and substitution there is no to produce at present
Product.
Due to technical, that there are purity is relatively low, ash content is high, heat-resisting for the insoluble sulfur product of domestic enterprise's production
The problems such as property is poor, gap is still larger compared with the product of the companies such as external Flexsys.
Although insoluble sulfur performance is prominent, generally there is also productions for the technology of production insoluble sulfur both at home and abroad
Cost is big, energy consumption is high, equipment seriously corroded, and high pressure is easy to produce accident, while insoluble sulfur exists not during storage
Stability is easy the problems such as being converted to common sulphur.Thus, the country is while developing insoluble sulfur technology, in recent years
In the cladding sulfur cream new process for seeking exploitation Environmental Safety, but at present, these new process majorities are still in laboratory stage,
Not yet realize industrialization.
Patent ZL 200910180589.7 discloses a kind of raw material for producing and can be used as the sulfur microcapsule of vulcanizer
Formula, it is made of sublimed sulfur, urea, 37% formalin, gelatin or polyvinyl alcohol, formic acid, triethanolamine, water, through original position
Polymerization prepares sulfur microcapsule product, coats shell fusing at a certain temperature and releases sulphur, can play vulcanization rubber
The effect of glue.
Patent ZL 200910009077.4 discloses a kind of composition of raw materials for producing single-shell sulfur microcapsule, it is by rising
Magnificent sulphur, toluene di-isocyanate(TDI), water, ethylenediamine, diethylenetriamine composition.The micro- glue of single shell sulfur is prepared through interfacial polymerization
Capsule, fusing releases sulphur at a certain temperature, can play the role of vulcanization.It can be prepared by the proportion of feed change
Single-shell sulfur microcapsule of the mass fraction of sulphur in 5-53% range out.
Patent ZL201310715696.1 discloses a kind of preparation method of high-temperature stable steamed stuffed bun sulphur, the high-temperature stable packet
Sub- sulphur is the high-temperature stability sulphur coated using composite polymer material as membrane material.By HBA-400, butadiene-vinylpyridine copylymer latex, silicic acid
The ratio investment mixer of aluminium, silica and water 4-6:4-6:4:4:500 by weight stir evenly；Then under stirring
50 parts of common sulphur powder is dispersedly added, after stirring 1 hour, filtering, then at constant dry dehydration to moisture < 0.3%, through powder
Broken, sieving secures satisfactory grades sub- compound cutan cladding sulphur.
Patent ZL 200910005110.6 discloses a kind of composition of raw materials for producing bilaminar membrane sulfur microcapsule, it is by rising
Magnificent sulphur, toluene di-isocyanate(TDI), water, ethylenediamine, diethylenetriamine, urea and formaldehyde composition, are prepared double through interfacial polymerization
Tunic sulfur microcapsule, core material are sublimed sulfurs, and first layer shell material is ethylenediamine, diethylenetriamine and toluene di-isocyanate(TDI)
The poly- arteries and veins of interfacial polymerization product；Second layer shell material is Lauxite.The sulfur microcapsule environmental pollution prepared is relatively small, and
It is simple process, safe operation, low in cost, it may be used as vulcanizer.
Patent ZL201510289745.9 discloses a kind of preparation method of coated with silica sulfur microcapsule, is related to one
The preparation method of the new inorganic membrane material cladding sulphur of kind, coats upper layer of silicon dioxide shell material in the sulphur microparticle surfaces of synthesis,
Inorganic membrane material is realized to effective cladding of sulphur.
Patent ZL200910180590.X discloses a kind of composition of raw materials for producing sulfur microcapsules using melamine resins, it is by rising
Magnificent sulphur, melamine, 37% formalin, formic acid, gelatin or polyvinyl alcohol, dodecyl sodium sulfate or OP-10 surface-active
Agent, 10% sodium carbonate liquor composition, prepare single-shell sulfur microcapsule through situ aggregation method, coat shell at a certain temperature
Fusing releases sulphur, can play the role of vulcanized rubber.
Patent ZL201510292383.9 discloses a kind of technique for producing polymer overmold sulphur and formula, polymerize owner
It to be made of polymethyl methacrylate.The present invention prepares the microcapsules of polymer overmold sulphur through in-situ grafting polymerization method,
Its core material is the sulphur simple substance generated in the presence of protecting colloid polyvinyl alcohol, forms work on surface after sulphur is surface modified
Property site, polymethyl methacrylate in the presence of initiator Adsorption point carry out in-situ grafting polymerization, generate poly- first
Base methyl acrylate covering material.Safety and environmental protection during the cladding sulfur cream that the present invention prepares, release rate is high, and sulphur contains
Amount is high, low in cost, may be used as vulcanizer.
Patent ZL200910009078.9 discloses a kind of preparation method of single-shell sulfur microcapsule.Using interfacial polymerization
Method prepares single-shell sulfur microcapsule, simple process, efficient, low in cost.The sulfur microcapsule that the present invention prepares, one
Determine fusing at temperature and release sulphur, may be used as vulcanizer.Pass through the proportion of feed change, thus it is possible to vary in microcapsules
The clad ratio of sulphur.Further, since sulfur microcapsule shell wall is high molecular material, therefore has good compatibility with rubber,
And the property such as ageing-resistant and anti-incipient scorch taken into account the thermal stability and chemical stability of sulphur, and rubber product can also be improved
Energy.
Summary of the invention
The present invention relates to a kind of methods of coating modification sulphur, and inorganic particle is mixed with water, prepare inorganic particle and suspend
Liquid is added modifying agent, grinds after processing, will stir evenly in the cladding agent emulsion inorganic particle suspension that is added to that treated
After sulphur is added, obtain inorganic filler/cladding agent emulsion/sulphur mixture, dry, crush, sieving obtain coating modification sulphur
Sulphur.It is characterized by: inorganic particle is mixed with water, prepares the inorganic particle that mass percent concentration is 10%~50% and suspend
Liquid, it is 1~100 μm of finely dispersed inorganic powder that 0.1~5% modifier treatment of inorganic particle dry weight, which is added, and is ground to partial size
Liquid suspension will stir 5~120min in the cladding agent emulsion suspension that is added to that treated, add sulphur, and stirring 5~
Inorganic particle/covering/sulphur mixture is obtained after 120min, wherein inorganic particle quality is the 1~40% of sulphur quality,
Covering quality is the 1~20% of sulphur quality, and drying and dewatering crushes, sieving obtains coating modification sulphur.
The inorganic particle be preferably zinc oxide, silica, talcum powder, Cab-O-sil, clay, aluminium oxide, barium sulfate,
Magnesia, calcium carbonate, alumina silicate, zinc silicate or the above two above powder mixture.
The modifying agent is preferably polyethylene glycol, polyvinyl alcohol, polyalcohol, fatty alcohol polyoxyethylene ether, the coupling of silicon oxygen
Agent or two or more mixtures, dosage are the 0.1%~5% of inorganic particle quality.
The covering is aqueous polyurethane emulsion, water-based acrylic resin lotion, vinylite, neoprene cream
Liquid, butadiene-styrene-vinyl pyridine rubber lotion, butadiene-vinylpyridine rubber lotion, nature rubber latex, butyl rubber lotion, acrylonitrile-butadiene rubber latex, Huo Zheshang
State the mixture of two or more lotions.
The drying and dewatering temperature is preferably 50~150 DEG C.
The smashed coating modification drusen object diameter is 20~400 μm.
The coating modification sulphur that the application is previously mentioned, is a kind of core-shell structure product, shell select covering be organic film and
Inorganic particle is inoranic membrane, and sulphur is core, forms core-shell structure.Inorganic particle is inoranic membrane, and dominant mechanism is by inorganic
The suction-operated of powder and fine particle size and organic film form comparatively dense film, while inorganic particle rises in whole system
To the effect of interleaving agent, coating modification sulphur may make to form powder granule after the drying, avoids assembling to form block because of covering
Shape or sheet products.But inorganic particle is configured to suspension in Jia Shui and is easy to happen sedimentation agglomeration, needs to be added
Emulsifier, the anti-modifying agent such as heavy agent, dispersing agent that drop are handled, and are then added in milling apparatus and are ground, are divided to be formed
It dissipates well, suspension of the particle diameter distribution at 1~100 μm, such suspension can be mixed preferably with covering, be formed containing packet
It covers the clad of agent and inorganic particle and plays the effect of isolation.Covering selection have good extensibility, adhesive force and
The material of closed performance.Coating mechanics are that emulsion particle and inorganic particulate are adsorbed by polarity or adhesive force is in sulphur surface shape
At one layer of fine and close film, relatively stable core-shell structure is formed, this layer of dense film can be in higher temperature (such as 120 DEG C or so) condition
Lower holding intensity and be unlikely to dissolve or become fluid, so as to effectively trap heat, do not release sulphur.It adds
The buffer action of inorganic particle also can help to the fusing point and thermal stability that improve coating modification sulphur to a certain extent.
In general, the bloom phenomenon of common sulphur, is because sizing material temperature tends to reach in sizing material internal mixing pass
115 DEG C or so, solubility is higher at high temperature for sulphur, and after sizing material cools down, sulphur can move to sizing material surface and generate
Bloom.
Coating modification sulfur product, clad is notheated decomposition or fusing to release during rubber compounding
Sulphur efficiently avoids sulphur and leads to the problem of bloom due to temperature change solubility also changes therewith.Coating modification sulphur
Mainly work in sulfidation, when temperature continues to heat, clad can be thermally decomposed or be fused into rheological body, or
So that melting sulphur is released sulphur by the porous structure of shell material, achievees the purpose that rubber product vulcanizes.
The coating modification sulphur of the application proposed, difficult point are the selection of covering and the control of covered effect,
And the dispersion of inorganic filler.The film coated cannot be too thick, can not be too thin.Clad is too thick, is easy to appear high temperature
Clad is non-fusible in sulfidation, decomposes, and causes to coat the problem of sulphur can not discharge sulphur, can not be vulcanized.If
Clad is too thin, is unable to reach the purpose of the fusing point and thermal stability that improve coating modification sulphur, also just loses coating modification
Meaning.In process of production, the selection of the selection and inorganic particle of coating thickness and covering as adsorbent is controlled
It is all the core process of the application.And the application propose technique have the following the utility model has the advantages that
Beneficial effect
A kind of method of coating modification sulphur according to the present invention, the advantage is that:
(1) equipment requirement is simple, and process characteristic is suitble to heavy industrialization, consecutive production.
(2) raw material needed for is simple and easy to get, and simple process is easy to operate, and modification is low in cost, and coating modification is high-efficient.
(3) coating modification sulfur cream process safety involved in is high, environmental-friendly, three-waste free discharge.
(4) coating product rate is high, can effectively improve thermal stability height, does not occur bloom phenomenon in rubber mixed.
(5) this product can be uniformly distributed in sizing material, and incipient scorch when effectively reducing sizing material storage extends sizing material storage period,
Improve rubber product quality.
(6) product comprehensive performance is prominent, improves the tack of sizing material, the adhesiveness of steel wire and rubber when improving manufacture tire
Can, assign the good comprehensive performance of rubber product.
(7) the application technique avoids insoluble sulfur in production in the high request of equipment and subsequent processes
Existing high risk.
(8) this product modification is at low cost, and stable product quality is high, and the market competitiveness is strong, with good economic efficiency.
Detailed description of the invention
Fig. 1 is one of the clad structure for coating sulfur product and showing under scanning electron microscope.
Fig. 2 is coat the clad structure that sulfur product is shown under scanning electron microscope two.
Fig. 3 is coat the clad structure that sulfur product is shown under scanning electron microscope three.
Fig. 4 is coat the clad structure that sulfur product is shown under scanning electron microscope four.
Specific embodiment
Inorganic particle used, cladding agent emulsion are commercial product, and covering emulsion solid content is about 40-60%.
Embodiment 1
Weigh 20g silica, 20g talcum powder is mixed with 360g water, the suspension that preparation mass percent concentration is 10%
Liquid, it is 100 μm or less finely dispersed suspension that 0.04g silicon oxygen coupling agent KH550, which is added, and handles and is ground to partial size, by 20g
5min is stirred in aqueous polyurethane A539 is added to that treated suspension, 100g sulphur is added, is wrapped after stirring 5min
The mixture for covering modified sulfur, the drying and dewatering in 80 DEG C of baking ovens crushes, sieving obtains 400 μm of coating modification sulphur below.
7.5g cladding sulphur is taken to be tested, 120 DEG C of mixer mixings, 1502 butadiene-styrene rubbers 100 of formula, zinc oxide 5, accelerant CZ 0.6,
N234 carbon black 30 carries out the physical property detection of rubber according to national standards.
Embodiment 2
Weighing 10g aluminium oxide, 10g clay are mixed with 20g water, are prepared the suspension that mass percent concentration is 50%, are added
Entering 0.2g polyvinyl alcohol to handle and be ground to partial size is 10 μm or less finely dispersed suspension, and 1g methyl acrylate is added to
120min is stirred in treated suspension, adds 100g sulphur, obtains the mixing of coating modification sulphur after stirring 120min
Object, the drying and dewatering in 88 DEG C of baking ovens crushes, sieving obtains 200 μm of coating modification sulphur below.Take 7.5g coat sulphur into
Row experiment, 120 DEG C of mixer mixings, 1502 butadiene-styrene rubbers 100 of formula, zinc oxide 5, accelerant CZ 0.6, N234 carbon black 30, according to
National standard carries out the physical property detection of rubber.
Embodiment 3
It weighs 1g alumina silicate to mix with 9g water, prepares the suspension that mass percent concentration is 10%, the poly- second of 0.05g is added
It is 1 μm or less finely dispersed suspension that glycol, which handles and is ground to partial size, by 15g acrylic resin anionic emulsion 3M-68
60min is stirred in the suspension that is added to that treated, 100g sulphur is added, obtains coating modification sulphur after stirring 30min
Mixture, the drying and dewatering in 100 DEG C of baking ovens crushes, sieving obtains 100 μm of coating modification sulphur below.7.5g is taken to coat
Sulphur is tested, 120 DEG C of mixer mixings, is formulated 1502 butadiene-styrene rubbers 100, zinc oxide 5, accelerant CZ 0.6, N234 carbon black
30, the physical property detection of rubber is carried out according to national standards.
Embodiment 4
10g silica and 10g barium sulfate, 10g zinc oxide are weighed, is mixed with 70g water, preparing mass percent concentration is
30% suspension, it is 20 μm or less finely dispersed suspensions that 0.6g silicon oxygen coupling agent KH590, which is added, and handles and is ground to partial size
Liquid will stir 100min in the 7g butadiene-vinylpyridine rubber lotion suspension that is added to that treated, add 100g sulphur, stir 10min
The mixture for obtaining coating modification sulphur afterwards, the drying and dewatering in 80 DEG C of baking ovens crushes, sieving obtains 20 μm of claddings below and changes
Property sulphur.7.5g cladding sulphur is taken to be tested, 120 DEG C of mixer mixings are formulated 1502 butadiene-styrene rubbers 100, and zinc oxide 5 promotes
Agent CZ0.6, N234 carbon black 30 carries out the physical property detection of rubber according to national standards.
Embodiment 5
It weighs 5g magnesia to mix with 5g calcium carbonate, 10g Cab-O-sil with 80g water, preparing mass percent concentration is 20%
Suspension, 0.4g glycerol is added and handle and is ground to partial size for 50 μm or less finely dispersed suspension, by 6g butylbenzene pyrrole rubber
30min is stirred in latex solution is added to that treated suspension, 100g sulphur is added, obtains coating modification after stirring 60min
The mixture of sulphur, 150 DEG C of expansion drying dehydrations crush, sieving obtains 400 μm of coating modification sulphur below.Take 7.5g packet
It covers sulphur to be tested, 120 DEG C of mixer mixings, is formulated 1502 butadiene-styrene rubbers 100, zinc oxide 5, accelerant CZ 0.6, N234 carbon black
30, the physical property detection of rubber is carried out according to national standards.
Embodiment 6
5g zinc oxide and 5g aluminium oxide are weighed, 2g silica is mixed with 12g water, and preparing mass percent concentration is 50%
Suspension, 0.6g polyvinyl alcohol is added and handle and is ground to partial size for 80 μm or less finely dispersed suspension, by 5g butyl
40min is stirred in rubber latex and 5g acrylic resin HBA-400A are added to that treated suspension, adds 100g sulphur,
Obtain the mixture of coating modification sulphur after stirring 22min, drying and dewatering in 120 DEG C of baking ovens, crush, sieving obtain 250 μm with
Under coating modification sulphur.7.5g cladding sulphur is taken to be tested, 120 DEG C of mixer mixings are formulated 1502 butadiene-styrene rubbers 100, oxygen
Change zinc 5, accelerant CZ 0.6, N234 carbon black 30 carries out the physical property detection of rubber according to national standards.
Embodiment 7
3g silica and 7g aluminium oxide are weighed, is mixed with 15g water, the suspension that mass percent concentration is 40% is prepared
Liquid, it is 5 μm or less finely dispersed suspension that 0.2g silicon oxygen coupling agent KH550, which is added, and handles and is ground to partial size, by 10g fourth pyrrole
30min is stirred in rubber latex and 10g aqueous polyurethane emulsion S339A are added to that treated suspension, adds 100g sulphur
Sulphur obtains the mixture of coating modification sulphur after stirring 90min, and 90 DEG C of expansion drying dehydrations crush, sieving obtains 80 μm or less
Coating modification sulphur.7.5g cladding sulphur is taken to be tested, 120 DEG C of mixer mixings are formulated 1502 butadiene-styrene rubbers 100, oxidation
Zinc 5, accelerant CZ 0.6, N234 carbon black 30 carry out the physical property detection of rubber according to national standards.
Embodiment 8
4g zinc oxide and 4g barium sulfate are weighed, 2g alumina silicate is mixed with 40g water, and preparing mass percent concentration is 20%
Suspension, it is 25 μm or less finely dispersed suspension that 0.4g polyethylene glycol, which is added, and handles and is ground to partial size, and 6g is aqueous poly-
120min is stirred in urethane and 2g vinylite are added to that treated suspension, 100g sulphur is added, after stirring 6min
The mixture of coating modification sulphur is obtained, drying and dewatering in 88 DEG C of baking ovens crushes, sieving obtains 100 μm of coating modifications below
Sulphur.7.5g cladding sulphur is taken to be tested, 120 DEG C of mixer mixings are formulated 1502 butadiene-styrene rubbers 100, zinc oxide 5, promotor
CZ0.6, N234 carbon black 30 carries out the physical property detection of rubber according to national standards.
Embodiment 9
4g silica and 2g alumina silicate, 2g magnesia are weighed, 2g barium sulfate is mixed with 10g water, prepares mass percent
The suspension that concentration is 10%, it is 100 μm that 0.2g fatty alcohol polyoxyethylene ether, which is added, and handles with 0.3gKH550 and is ground to partial size
Finely dispersed suspension below will stir in 1g nature rubber latex and 5g the ethyl acrylate suspension that is added to that treated
36min, adds 100g sulphur, stirs and obtains the mixture of coating modification sulphur after 60min, drying and dewatering in 80 DEG C of baking ovens,
It crushes, sieving obtains 50 μm of coating modification sulphur below.7.5g cladding sulphur is taken to be tested, 120 DEG C of mixer mixings are matched
1502 butadiene-styrene rubbers 100 of side, zinc oxide 5, accelerant CZ 0.6, N234 carbon black 30 carry out the physical property inspection of rubber according to national standards
It surveys.
Embodiment 10
10g silica and 15g zinc silicate are weighed, 5g barium sulfate is mixed with 70g water, is prepared mass percent concentration and is
50% suspension, it is 40 μm or less finely dispersed suspensions that 0.3g silicon oxygen coupling agent KH590, which is added, and handles and is ground to partial size
Liquid will stir 12min in 10g aqueous polyurethane XH960 and 5g the neoprene latex suspension that is added to that treated, add
100g sulphur obtains the mixture of coating modification sulphur after stirring 70min, and drying and dewatering in 130 DEG C of baking ovens crushes, is sieved
To 20 μm of coating modification sulphur below.7.5g cladding sulphur is taken to be tested, 120 DEG C of mixer mixings are formulated 1502 butylbenzene
Glue 100, zinc oxide 5, accelerant CZ 0.6, N234 carbon black 30 carry out the physical property detection of rubber according to national standards.
Embodiment 11
1g magnesia and 1g zinc oxide are weighed, is mixed with 1g alumina silicate with 13g water, preparing mass percent concentration is 20%
Suspension, be added 0.15g ethylene glycol handle and be ground to partial size be 15 μm or less finely dispersed suspension, by 1g it is aqueous gather
30min is stirred in urethane A539 and 1g acrylonitrile-butadiene rubber latex are added to that treated suspension, 100g sulphur is added, stirs
The mixture of coating modification sulphur is obtained after 48min, drying and dewatering in 65 DEG C of baking ovens crushes, sieving obtains 30 μm of packets below
Cover modified sulfur.7.5g cladding sulphur is taken to be tested, 120 DEG C of mixer mixings, 1502 butadiene-styrene rubbers 100 of formula, zinc oxide 5,
Accelerant CZ 0.6, N234 carbon black 30 carry out the physical property detection of rubber according to national standards.
Embodiment 12
15g silica and 5g zinc oxide and 5g alumina silicate are weighed, 5g barium sulfate is mixed with 70g water, prepares quality percentage
The suspension that specific concentration is 30%, addition 0.3g silicon oxygen coupling agent KH550 and 0.6g polyvinyl alcohol, which handles and is ground to partial size, is
4g methyl methacrylate and 6g butadiene-vinylpyridine rubber lotion, are added to that treated suspends by 22 μm or less finely dispersed suspension
60min is stirred in liquid, adds 100g sulphur, stirs and obtains the mixture of coating modification sulphur after 20min, in 120 DEG C of baking ovens
Drying and dewatering crushes, sieving obtains 50 μm of coating modification sulphur below.7.5g cladding sulphur is taken to be tested, 120 DEG C of mixings
Machine is kneaded, 1502 butadiene-styrene rubbers 100 of formula, zinc oxide 5, accelerant CZ 0.6, and N234 carbon black 30 carries out rubber according to national standards
Physical property detection.
Comparative example 1:
The common sulphur of 7.5g is taken to be tested, 120 DEG C of mixer mixings are formulated 1502 butadiene-styrene rubbers 100, and zinc oxide 5 promotes
Agent CZ0.6, N234 carbon black 30 carries out the physical property detection of rubber according to national standards.
Comparative example 2:
7.5g insoluble sulfur (OT20) is taken to be tested, 120 DEG C of mixer mixings are formulated 1502 butadiene-styrene rubbers 100, oxidation
Zinc 5, accelerant CZ 0.6, N234 carbon black 30 carry out the physical property detection of rubber according to national standards.
White carbon black performance test results in table 1, embodiment
Claims (3)
1. a kind of method of coating modification sulphur, it is characterised in that: mix inorganic particle with water, prepare mass percent concentration
For 10%~50% inorganic particle suspension, 0.1~5% modifier treatment of inorganic particle dry weight is added and is ground to partial size
For 1~100 μm of finely dispersed inorganic particle suspension, by stirring 5 in the covering suspension that is added to that treated~
120min adds sulphur, obtains inorganic particle/covering/sulphur mixture after stirring 5~120min, wherein inorganic powder
Weight is the 1~40% of sulphur quality, and covering quality is the 1~20% of sulphur quality, and drying and dewatering crushes, is sieved
To coating modification sulphur；
Inorganic particle be zinc oxide, silica, talcum powder, Cab-O-sil, clay, aluminium oxide, barium sulfate, magnesia, calcium carbonate,
The mixture of alumina silicate, zinc silicate or the above two above powder；
Modifying agent selects polyalcohol, fatty alcohol polyoxyethylene ether, silicon oxygen coupling agent or two or more mixtures, and dosage is inorganic powder
The 0.1%~5% of weight；
Covering is aqueous polyurethane emulsion, water-based acrylic resin lotion, vinylite, neoprene latex, butylbenzene pyrrole
Rubber latex, butadiene-vinylpyridine rubber lotion, nature rubber latex, butyl rubber lotion, acrylonitrile-butadiene rubber latex or two or more lotions
Mixture.
2. preparation method according to claim 1, it is characterised in that: drying and dewatering temperature is 50~150 DEG C.
3. preparation method according to claim 1, it is characterised in that: smashed coating modification drusen object diameter is
20~400 μm.
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| CN109485917A (en) * | 2016-12-08 | 2019-03-19 | 北京橡胶工业研究设计院有限公司 | A kind of preparation method for the cladding sulfur vulcanizing agent can be used as rubber production |
| CN107189104B (en) * | 2017-05-12 | 2019-05-17 | 北京化工大学 | A kind of preparation method being sustained sulphur |
| CN108912420B (en) * | 2018-08-14 | 2021-05-14 | 兰溪市华橡工贸有限公司 | Preparation method of high-wear-resistance rubber material for tires |
| CN109306075B (en) * | 2018-09-30 | 2020-12-15 | 嘉兴华维新能源有限公司 | Preparation method of rubber auxiliary agent-calcium carbonate coated vulcanizing agent VA-7 microspheres |
| CN115678129A (en) * | 2022-09-02 | 2023-02-03 | 河南汇龙液压科技股份有限公司 | High-stiffness rubber material and production process thereof |
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| CN103788414A (en) * | 2013-12-23 | 2014-05-14 | 山东沾化奥仕化学有限公司 | Preparation method of high-temperature stable coated sulfur |
| CN104724681A (en) * | 2015-03-18 | 2015-06-24 | 无锡华盛橡胶新材料科技股份有限公司 | Highly dispersed high-stability insoluble sulfur and preparation method thereof |
| CN105037803A (en) * | 2015-06-06 | 2015-11-11 | 青岛科技大学 | Preparation method of composite double-layer-film coated sulfur microcapsule |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103788414A (en) * | 2013-12-23 | 2014-05-14 | 山东沾化奥仕化学有限公司 | Preparation method of high-temperature stable coated sulfur |
| CN104724681A (en) * | 2015-03-18 | 2015-06-24 | 无锡华盛橡胶新材料科技股份有限公司 | Highly dispersed high-stability insoluble sulfur and preparation method thereof |
| CN105037803A (en) * | 2015-06-06 | 2015-11-11 | 青岛科技大学 | Preparation method of composite double-layer-film coated sulfur microcapsule |
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