CN104212108A - Preparation method of white carbon black wet-process gross rubber - Google Patents
Preparation method of white carbon black wet-process gross rubber Download PDFInfo
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Abstract
The invention relates to a preparation method of white carbon black wet-process gross rubber. The preparation method comprises the following steps of carrying out chemical and physical treatment on a rubber solution and/or white carbon black dispersion liquid: introducing a hydrophilic group to a rubber molecule main chain so that the rubber molecule main chain has a self-emulsifying function, carrying out surface modification on white carbon black so that the white carbon black has lipophilicity, and preparing and homogenizing rubber and a white carbon black emulsion; removing a solvent and water which are contained in a mixed rubber emulsion to prepare the white carbon black wet-process gross rubber. The method disclosed by the invention is continuous and controllable in process, efficient, energy-saving, less in pollution and uniform and stable in product quality. Compared with the traditional wet-process mixing technology, the method disclosed by the invention has the advantage that the mechanical dispersion method of a mixed emulsion in a rubber solution is more stable and uniform as compared with any filler in the rubber solution because the compatibility between rubber and white carbon black molecules is essentially improved, can especially meet the requirement for retention time essential to the procedures of large-scale production and is suitable for the gross rubber for various rubber products.
Description
Technical field
The present invention relates to synthetic rubber and rubber item field, particularly relate to a kind of preparation method of white carbon black wet method rubber unvulcanizate.
Background technology
Tire and various rubber item mainly adopt dry method mixing technology so far, by solid rubber, filler, softening oil and various auxiliary agent, and the mixing one-tenth master batch of mechanical dry method in Banbury mixer, then carry out machine-shaping, finished product is made in last sulfuration.
The mixing serious power consumption of dry method, contaminate environment and harm workers ' health; Also there is many disadvantages such as the low and batch quality of batch production efficiency is variant.Therefore improve compounding process, be the target that Rubber processing industry is pursued always.
In recent years; environment protection and Sustainable development have become the trend of society; facilitate proposition and the scientific practice of " environment-friendly and green tire " concept, through the effort of nearly 30 years rubber and Tire production industry, " the riding tire of environment-friendly and green " starts by popularization and mass-producing successful Application.Its base mateiral is fixed as novel solution polymerized butadiene styrene rubber and silica system, has walked out traditional emulsion polymerized styrene butadiene rubber and carbon black system.The solution polymerized butadiene styrene rubber of macromole Parameter adjustable and silica bound, have that heat-dissipating is low, low-rolling-resistance, anti-slippery are good, high abrasion resistance and a feature such as dynamic properties is excellent.More outstanding advantage by the requirement of tire different application, can provide all types of special purpose rubber trade mark.The attribute of rubber and application feature are pushed to new development height, created social effect outstanding in environmental protection and energy saving.
Rubber item processing industry, continues to use the mixing method of mechanical dry always and produces rubber/pigmented compound, and after main filler changes white carbon black into, compared with carbon black, the consistency of itself and rubber is poor, and be difficult to be uniformly dispersed, the drawback of mechanical dry mixing method is more outstanding.Domestic in recent years in university, institute and enterprise, carry out the technical research of natural rubber and the co-precipitation of silicon-dioxide wet-mixed, applied for that a collection of patent is as CN102153792A, CN102516418A and CN102775618A etc.
About directly manufacturing the oil-filled casting resin carbonblack master batch of emulsion polymerized styrene butadiene rubber in synthetic rubber manufacturer, the sixties developed countries be developed, the trade mark reach more than 80 plant.Carbon black dispersion adopts two kinds of methods: in water, make carbon black with dispersion agent and stick with paste, then make emulsion with oil with emulsifying agent together with, finally and styrene-butadiene latex to be mixed even feeding autoclave condensed system.Another kind be by carbon black and water after grinding, pass into high pressure spray nozzle high shear mechanical device and form dispersion liquid, then mix with oil and latex, finally send to cohesion.Emulsion styren-butadiene rubber is directly made successful experience and the scientific and technological achievement of gross rubber unvulcanizate by forefathers, and we still can well use for reference today.But there is not yet report so far with solution polymerized butadiene styrene rubber and white carbon black wet method rubber unvulcanizate.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, through development research and the production practice accumulation of contriver's long campaigns China Synthetic Rubber Industry technology, develop filler stable and uniform more in rubber solutions, technique easily controlled continuously, the preparation method of energy-efficient, a kind of white carbon black wet method rubber unvulcanizate of polluting little, quality product stable homogeneous.
The invention provides the preparation method of a kind of white carbon black (with rubber) wet method rubber unvulcanizate, comprise the following steps:
1, the chemical physics process of rubber solutions
In rubber solutions, add polar monomer react with it, rubber backbone introduces polar monomer, make rubber macromolecule have self-emulsifying function; Temperature of reaction is at 70 ~ 120 DEG C, and 5 ~ 60 minutes time, monomer mass mark is 0.5 ~ 5% of rubber quality, is preferably 0.5 ~ 3%, then adds appropriate water, and holding temperature, at 35 ~ 50 DEG C, forms the emulsion of homogeneous stability; Described polar monomer is as benzoyl peroxide, azo compound or organometallics containing the organosilicon compound of the alkene anhydrides of the esters of acrylic acid of ester group, nitrogenous propionyl Ammonia, hydroxyl, silicone-containing base, superoxide; Described rubber solutions is synthetic rubber solution, is preferably the rubber solutions in synthesis step, as utilized the active initiated polymerization of negative ion or end-blocking; Or utilize contained a large amount of unsaturated double-bond on main chain, cause with peroxide radical, carry out graft reaction, process is easily controlled.With the difference of reaction conditions, there is larger difference in the reaction times, autoclave interrupter method, temperature of reaction 70 ~ 90 DEG C, and the reaction times was up to 60 minutes; And continuous screw extrusion reaction method, temperature of reaction 100 ~ 120 DEG C, in 5 ~ 20 minutes reaction times, is more preferably by conjugated diene monomer and aromatic olefin monomers, the homopolymerization of anionic polymerization in varsol, copolymerization homogeneous phase rubber solutions, such as low-cis-polybutadiene, middle and high vinyl polybutadiene, cis-polyisoprene, random styrene-butadiene rubber, block butylbenzene, penta benzene rubber, fourth penta binary or fourth penta benzene ternary rubber etc.Also solid rubber can be dissolved in its good solvent and make rubber solutions, but be difficult to ensure in economy and quality product.
Then carry out physical treatment at above-mentioned treated rubber solutions, under agitation, add terminator and oxidation inhibitor, its viscosity of regulable control is 15000 ~ 50000cp, then adds environmental protection plasticizing oil, under agitation, holding temperature is at 35 ~ 50 DEG C, its polymer concentration of accurate control, becomes equal phase emulsion or solution-stabilized material, and material can stablize storage more than 72 hours.In above-mentioned treated rubber solutions holding temperature at 50 ~ 60 DEG C, accurately control its polymer concentration, become equal phase emulsion or solution-stabilized material, material can stablize storage more than 72 hours.
2, white carbon black surface chemistry and physically modified process.
By micron order, to nano level white carbon black dispersion liquid, (silica aggregate particle is dispersed liquid in water, if commercially available specification is 180 ~ 300 liquid m2/g specific surface areas, solid content is that the commercialization water slurry (white carbon black dispersion liquid) of 30 ~ 50wt% adds in stirring tank, add in above-mentioned white carbon black dispersion liquid again containing sulfenyl, amino, acyl group, glycidyl ether or vinyl etc. (and so on) one or more the mixture (any ratio) of silicoorganic compound, modification is carried out to white carbon black molecular surface, makes it have lipophilicity; Add-on is 1 ~ 5% of white carbon black quality, and temperature, in room temperature ~ 100 DEG C, in 30 ~ 150 minutes reaction times, is preferably 60 ~ 90 minutes.Described silicoorganic compound are two (triethoxysilicane) propyl group tetrasulfide, two (triethoxy is silica-based) propyl group) disulphide, γ-mercaptopropyl trimethoxysilane, γ-aminopropyl triethoxysilane, γ-glycydoxy Trimethoxy silane, γ-methacryloxypropyl trimethoxy silicon temperature in room temperature ~ 100 DEG C, 30 ~ 150 minutes reaction times; Alkane, vinyl three ('beta '-methoxy oxyethyl group) silane or vinyltriacetoxy silane etc.
Physical treatment refer to above-mentioned in the white carbon black dispersion liquid of surface modification treatment mechanical impurity go Xu and large order number Wang Guo Lu in stirring tank, regulating with deionized water afterwards makes solid content be stabilized in 10 ~ 40wt%, be preferably 20 ~ 30wt%, and regulate pH 7 ± 0.5, finally become equal phase emulsion or solution-stabilized material, its storage period is more than 72 hours.
3, the preparation of rubber and white carbon black mixed emulsion and homogenizing
By various required filler and auxiliary agent (additive) by its character, join respectively through above-mentioned steps 1,2, be processed in equal phase emulsion or solution-stabilized material, required filler and auxiliary agent is added and different along with rubber clone is different from the trade mark and rubber item, usual filler and hydrophilic compounds join in the equal phase emulsion of white carbon black, comprise carbon black, talcum powder, calcium carbonate, calcium sulfate, barium sulfate, metal oxide, salt or emulsifying dispersant; Oiliness compound and hydrocarbon compound join in the equal phase emulsion of rubber or solution-stabilized material, comprise (environmental protection) aromatic hydrocarbon oil, naphthenic oil, softening agent, coupling agent, oxidation inhibitor, optothermal stabilizer, fire retardant, dyestuff or fluorescent agent etc., its solid content along with rubber clone different and different from the trade mark and rubber item, general between 5 ~ 50wt%, be preferably 10 ~ 25wt%, obtain rubber latex that two kinds of blending configure or solution and white carbon black emulsion material respectively.
The rubber latex that above-mentioned blending is configured or solution, feeding is made up of in latex homogenization system a speed change stirring tank and speed change emulsion recycle pump carries out homogenizing, under unlatching stirring and pump cycling condition, white carbon black emulsion blending configured with certain flow rate adds in stirring tank first carries out blending, carry out the homogenizing of mixed emulsion material afterwards by different stirring velocitys and pump internal circulating load, its objective is and make two kinds of material Quick uniform mixing and stablize.
In method provided by the invention, do not have the amphiphilic material of additional emulsifying agent class to intercept in mixed emulsion, rubber and white carbon black molecular interface bonding force are improved, and inherently improve the consistency of two class materials.Make to mix difficulty between compatible emulsion or solution significantly to reduce, adopt conventional latex blending means, the mixed emulsion of stable uniform can be obtained.
4, the solvent in mixed emulsion and moisture content is removed
Step 3, the following any one method of obtained mixed emulsion are removed solvent in mixed emulsion and moisture content:
A) mixed emulsion pump is sprayed into rubber condensed system, with water vapor azeotropic desolvation, be that small-particle is scattered in water containing the rubber of white carbon black at mixed emulsion, be separated with water through vibratory screening apparatus, again through extrusion dehydration and expansion drying, obtained water content is down to below 1wt%, and volatile matter is less than the white carbon black wet method rubber unvulcanizate (or claiming white carbon black mixing master batch) of 0.5wt%.This operational path technology maturation is reliable, and the add-on controlling filler in production is crucial.
Or B) adopt a kind of closed two roller pressure refining machines, desolvation and moisture content simultaneously, the obtained mixing rubber master batch of white carbon black wet method.The feature of this flow process is that equipment is easily processed, and filler not easily loses, and particularly also avoid a large amount of water cycle processes, whole energy.
Or C) mixed emulsion good for mixture is sent in twin-screw set under protection of inert gas, desolvation and water simultaneously, then by extrudate compound stalk forming, obtained white carbon black wet method rubber unvulcanizate.Described rare gas element is comprise methane, ethane, propane or butane low-carbon alkanes or their mixture, carbonic acid gas or nitrogen.Mainly determine with the resources supplIes of factory and expense.Carbonic acid gas is the waste gas of petroleum chemical enterprise's discharge, and through reclaiming clean, recycling has double meaning.Described inert gas pressure is 0.3Mpa ~ 3Mpa, is preferably 0.7Mpa ~ 1.5Mpa.Described twin-screw set, its significant parameter is: length is 60 ~ 100, and rotating speed 50 ~ 500rpm is adjustable.The geometrical dimension of screw rod is different and change with output, can directly desolvation and moisture content, and filler does not lose, and does not produce " three wastes ", but equipment is complicated, and one-time investment is larger.The adjustment of the method equipment flexibly, can adapt to the demand that all kinds of rubber masterbatch is produced.
The invention provides the principal feature of the preparation method of a kind of white carbon black (with rubber) wet method rubber unvulcanizate:
1) promote combining closely of synthetic rubber and downstream product processing from the renewal of Technology, be conducive to significantly improving of the overall science and technology of rubber industry and effective levels.
2) to rubber macromolecule and the modification of white carbon black chemical physics, two-way and constitutionally improves the consistency between polarity and non-polar molecule, make two class solution mixture stable uniform, overcome the disadvantage that single high-shear mechanical mix techniques intermediate product is difficult to store, meet the residence time requirement that industrial mass production is necessary to each step sequence, fill up the technology vacancy directly being obtained white carbon black rubber unvulcanizate by synthetic rubber factory intermediates rubber solutions, the demand that all kinds of rubber masterbatch is produced can be adapted to.
3) present method technique easily control continuously, energy-efficient, pollute little, filler stable and uniform more in rubber solutions, quality product stable homogeneous.Compared with existing wet method mixing technology, improve because rubber and the intermolecular consistency of filler obtain essence, mixed emulsion is more more stable and even than the mechanical dispersion process of any filler in rubber solutions, to meet in scale operation the necessary residence time requirement of each step sequence especially, be applicable to the rubber unvulcanizate of various rubber item.
The needs that the rubber masterbatch that the preparation method of a kind of white carbon black provided by the invention (with rubber) wet method rubber unvulcanizate is applicable to various rubber item is produced.
Embodiment
By the following example, the invention will be further described in the present invention, but protection scope of the present invention is not limited to these embodiments following.
Example 1
To in the reactor of drying, add low-cis-polybutadiene and randomly solution polymerized butadiene-styrene rubber with low mixing solutions that 1000g solid content is 10wt%, the mass ratio of two kinds of glue is 10/90.Closed reactor opens stirring, pass into the air in nitrogen replacement still simultaneously, maintain still internal pressure 0.3MPa, open chuck heating, design temperature 90 DEG C, after temperature-stable, add 0.3gBPO and 3g grafted monomer along divinyl acid anhydrides, react after 4 hours at 80 DEG C ~ 90 DEG C, add 0.2g antioxidant 1076 and 0.2g irgasfos 168, be cooled to room temperature and discharge glue, obtain modified rubber solutions.
In above-mentioned modified rubber solutions, add 37.5g environment-friendly aromatic rubber oil, stir 30 minutes, then add 600g deionized water, stirring at normal temperature 30 minutes obtained rubber latexs.
Take the white carbon black dispersion liquid that 300g solid content is 25wt%, progressively join in rubber latex, in mulser, stirring and recycle pump blending form rubber and the white carbon black mixed emulsion of stable uniform after 30 minutes.
By above-mentioned mixed emulsion, spray in condensing field after being pressurized to 0.8MPa with latex pump, pass into steam azeotropic desolvation, then remove moisture content by taper singe screw extrusion dehydration and expansion-exsiccation machine, obtain white carbon black wet method rubber unvulcanizate.
Example 2
To in the reactor of drying, add cis-polyisoprene and randomly solution polymerized butadiene-styrene rubber with low mixing solutions that 1000g solid content is 10wt%, the mass ratio of two kinds of glue is 20/80.Closed reactor opens stirring, pass into the air in nitrogen replacement still simultaneously, maintain still internal pressure 0.3MPa, open heating, design temperature 70 DEG C, after temperature-stable, press-in 2.5g high-purity propylene acid methyl esters, reacts after 6 hours at 70 DEG C, adds 0.2g antioxidant 1076 and 0.2g irgasfos 168, be cooled to room temperature and discharge glue, obtain modified rubber solutions.
In above-mentioned modified rubber solutions, add 37.5g environment-friendly aromatic rubber oil, stir 30 minutes, then add 600g deionized water, stirring at normal temperature 30 minutes obtained rubber latexs.
Take the white carbon black dispersion liquid that 375g solid content is 20%, join in rubber latex, in mulser, stirring and recycle pump blending form rubber and the white carbon black mixed emulsion of stable uniform after 30 minutes.
By above-mentioned mixed emulsion, under the protection of nitrogen, spray in the special twin screw unit rising good temperature in advance, this unit is
incongruous double screw devolatilization machine, has 5 venting ports, and first is normal pressure mouth, and the pressure of all the other venting ports is decremented to 100mm mercury column successively, and desolvation and moisture content, obtain the brown rubber unvulcanizate that product volatile content is less than the color even of 0.5wt% simultaneously.
Example 3
To in the reactor of drying, adding 734g solid content is 15wt% solution polymerized butadiene styrene rubber solution, closed reactor opens stirring, pass into the air in nitrogen replacement still simultaneously, maintain still internal pressure 0.3MPa, unlatching chuck heats, design temperature 80 DEG C, after temperature-stable, add 0.5gBPO and 5g grafted monomer vinyl three ('beta '-methoxy oxyethyl group) silane, react after 5 hours at 80 DEG C, add 0.25g antioxidant 1076 and 0.25g irgasfos 168, be cooled to room temperature and discharge glue, obtain modified rubber solutions.
In above-mentioned modified rubber solutions, add 37.5g environment-friendly aromatic rubber oil, stir 30 minutes, then add 600g deionized water, stirring at normal temperature 30 minutes obtained rubber latexs.
The chemical treatment of white carbon black dispersion liquid
Take the white carbon black dispersion liquid that 300g solid content is 25wt%, add 150g deionized water, add two (triethoxysilicane) propyl group tetrasulfide of 3.75g simultaneously, stir 30 minutes in mulser, obtain modified white carbon black dispersion liquid.
Join in rubber latex by modified white carbon black dispersion liquid, in mulser, stirring and recycle pump blending form rubber and the white carbon black mixed emulsion of stable uniform after 30 minutes.
By above-mentioned mixed emulsion, under the protection of nitrogen, spray in the special twin screw unit rising good temperature in advance, this unit is
incongruous double screw devolatilization machine, has 5 venting ports, and first is normal pressure mouth, and the pressure of all the other venting ports is decremented to 100mm mercury column successively, and desolvation and moisture content, obtain the brown rubber unvulcanizate that product volatile content is less than 0.5% simultaneously.
Take the rubber unvulcanizate that obtains in a certain amount of above-mentioned each embodiment with test performance after the sulfurizing formula sulfuration in table 1.
Table 1 is experiment rubber unvulcanizate sulfurizing formula table respectively
| Component | Comparative example | Example 1 | Example 2 | Example 3 |
| Wet method white carbon black rubber unvulcanizate | 0 | 225.5 | 225 | 227.5 |
| Solution polymerized butylbenzene | 100 | 0 | 0 | 0 |
| Yanshan Mountain BR9000 | 10 | 0 | 0 | 0 |
| Environment-friendly rubber oil | 37.5 | 0 | 0 | 0 |
| Precipitated silica | 75 | 0 | 0 | 0 |
| Carbon black N330 | 10 | 10 | 10 | 10 |
| Zinc oxide | 2.5 | 2.5 | 2.5 | 2.5 |
| Stearic acid | 1.5 | 1.5 | 1.5 | 1.5 |
| Antioxidant 4020 | 2 | 2 | 2 | 2 |
| Accelerator CBS | 1.4 | 1.4 | 1.4 | 1.4 |
| Vulkacit D PG | 1.5 | 1.5 | 1.5 | 1.5 |
| Polymerization sulphur | 1.4 | 1.4 | 1.4 | 1.4 |
| KH-848-4 | 6 | 6 | 6 | 6 |
Cure conditions: 160 DEG C 30 minutes.
The performance test results of the above-mentioned cross-linked rubber of table 2
In test event, press GB/T531.1-2008 test for the 1st.
In test event, press GB/T528-2009 test for 2 ~ 6.
In test event, test with the dark Y3000E compression heat generation trier of Beijing friend for the 7th.
In test event, press GB/T529-2008 test for the 8th.
In test event, test with high ferro GT-7042-REA reisilometer for the 9th.
In test event, test with ALPHA91001SR fillers dispersed instrument for the 10th.
In test event, the 11st presses GB/T1689-1998 test.
In test event, test with GABO company EPLXOR-500N dynamic mechanical analyzer for the 12nd.
Owing to carrying out more distinguishing glue kind with same formula, therefore test result is not best conclusion, but by compare test data, can find out the key distinction of a trend and wet-dry change.
As everyone knows, in hot-fusible pressure-sensitive adhesive formula, add filler, very general in this Application Areas, not only can reduce costs and can shield lights be protected by the object of high smooth finish surface.By wet method, the fillers such as white carbon black and rubber solutions are mixed mutually; the bonding force of hot-fusible pressure-sensitive adhesive macromole and filler molecule can be improved, improve its thermotolerance and electrical insulation capability; especially when being applied to the surface protection of top-grade furniture, automobile and aircraft, the advantage left no trace when there is stripping.
Comparative example 4
Fill a prescription according to the comparative example 4 in table 3, accurately take 25g styrene isoprene styrene block copolymer (SIS), 20g138 resin, 2g C9 resin, 15g C5 resin, 11.5g145 resin, 3g terpine resin T-100,7.5g silicon-dioxide, 20g naphthenic oil KN4010,0.5g antioxidant 1010,0.5g irgasfos 168.
Above-mentioned material is added together the small-sized reactor of a 500ml with adjustable stirring, pass into thermal oil to chuck, temperature of reaction kettle is risen to 165 DEG C, and be incubated more than 30 minutes.Open and stir, pass into nitrogen simultaneously, maintain reacting kettle inner pressure 0.1MPa, react 75 minutes, binder removal is coated with, and carries out bond properties test.
Example 5
The process of styrene isoprene styrene block copolymer (SIS) solution:
To in the reactor of drying, adding 1000g solid content is that 20wt% obtains styrene isoprene styrene block copolymer (SIS) solution from polymerization workshop section, add into 334g hexanaphthene again, closed reactor opens stirring, pass into the air in nitrogen replacement still simultaneously, maintain still internal pressure 0.2MPa, open heating, design temperature 70 DEG C, after temperature-stable, at adding 0.5gBPO and 5g MALEIC ANHYDRIDE 70 DEG C, reaction is after 8 hours, and glue is discharged in cooling, obtains modified styrene isoprene styrene block copolymer (SIS) solution.
In above-mentioned modified styrene isoprene styrene block copolymer (SIS) solution, add 56g naphthenic oil, stir 30 minutes, then add 600g deionized water, stirring at normal temperature 30 minutes obtained rubber latexs.
Take the white carbon black dispersion liquid that 240g solid content is 25%, add 150g deionized water, stir after 30 minutes, join in above-mentioned rubber latex, in mulser, stirring and recycle pump blending form rubber and the white carbon black emulsion of stable uniform after 20 minutes.
By above-mentioned mixed latex, under the protection of nitrogen, spray in the special twin screw unit rising good temperature in advance, desolvation and moisture content, obtain white carbon black and styrene isoprene styrene block copolymer (SIS) wet method rubber unvulcanizate simultaneously.
The preparation of hot-fusible pressure-sensitive adhesive
Fill a prescription according to the example 5 in table 3, accurately take the above-mentioned white carbon black of 40g and styrene isoprene styrene block copolymer (SIS) wet method rubber unvulcanizate, 20g138 resin, 2g C9 resin, 15g C5 resin, 11.5g145 resin, 3g terpine resin T-100,13g naphthenic oil KN4010,0.5g antioxidant 1010,0.5g irgasfos 168.
Above-mentioned material is added together the small-sized reactor of a 500ml with adjustable stirring, pass into thermal oil to chuck, temperature of reaction kettle is risen to 165 DEG C, and be incubated more than 30 minutes.Open and stir, pass into nitrogen simultaneously, maintain reacting kettle inner pressure 0.1MPa, react 75 minutes, binder removal is coated with, and carries out bond properties test.
Example 6
To in the reactor of drying, adding 1000g solid content is that 20wt% obtains styrene isoprene styrene block copolymer (SIS) solution from polymerization workshop section, add into 334g hexanaphthene again, closed reactor opens stirring, pass into the air in nitrogen replacement still simultaneously, maintain still internal pressure 0.2MPa, open heating, design temperature 80 DEG C, after temperature-stable, add 0.6gBPO and 6g vinyl three ('beta '-methoxy oxyethyl group) silane, react at 80 DEG C after 6 hours, be cooled to room temperature and discharge glue, obtain modified styrene isoprene styrene block copolymer (SIS) solution.
In above-mentioned modified styrene isoprene styrene block copolymer (SIS) solution, add 56g naphthenic oil, stir 30 minutes, then add 600g deionized water, stirring at normal temperature 30 minutes obtained rubber latexs.
Take the white carbon black dispersion liquid that 240g solid content is 25wt%, add 150g deionized water, stir after 30 minutes, join in above-mentioned rubber latex, in mulser, stirring and recycle pump blending form rubber and the white carbon black emulsion of stable uniform after 20 minutes.
By above-mentioned mixed latex, under the protection of nitrogen, spray in the special twin screw unit rising good temperature in advance, desolvation and moisture content, obtain white carbon black and styrene isoprene styrene block copolymer (SIS) wet method rubber unvulcanizate simultaneously.
The preparation of hot-fusible pressure-sensitive adhesive:
Fill a prescription according to the example 6 in table 3, accurately take the above-mentioned white carbon black of 40g and styrene isoprene styrene block copolymer (SIS) wet method rubber unvulcanizate, 20g138 resin, 2g C9 resin, 15g C5 resin, 11.5g145 resin, 3g terpine resin T-100,13g naphthenic oil KN4010,0.5g antioxidant 1010,0.5g irgasfos 168.
Above-mentioned material is added together the small-sized reactor of a 500ml with adjustable stirring, pass into thermal oil to chuck, temperature of reaction kettle is risen to 165 DEG C, and be incubated more than 30 minutes.Open and stir, pass into nitrogen simultaneously, maintain reacting kettle inner pressure 0.1MPa, react 75 minutes, binder removal is coated with, and carries out bond properties test.
Table 3 is applied to the formula of environment-friendly type hot melt pressure sensitive adhesive
The above-mentioned hot-fusible pressure-sensitive adhesive performance test of table 4
| Test event | Comparative example 4 | Example 5 | Example 6 |
| Tack | 20# | 18# | 21# |
| Hold viscosity (h) | 120 | 160 | 150 |
| Stripping strength (N/cm) | 45 | 47 | 46 |
| It is residual whether release surface has | Have | Nothing | Nothing |
In test event, tack presses GB4582-84 test
Hold viscosity in test event to test by GB/T4581-1998
In test event, stripping strength presses GB/T2792-1998 test
Example 7
To in the reactor of drying, add the randomly solution polymerized butadiene-styrene rubber with low solution that 1000g solid content is 10wt%, closed reactor opens stirring, pass into the air in nitrogen replacement still simultaneously, maintain still internal pressure 0.3MPa, unlatching chuck heats, design temperature 90 DEG C, after temperature-stable, add 0.3gBPO and 3g grafted monomer along divinyl acid anhydrides, react after 4 hours at 80 DEG C ~ 90 DEG C, add 0.2g antioxidant 1076 and 0.2g irgasfos 168, be cooled to room temperature and discharge glue, obtain modified rubber solutions.
In above-mentioned modified rubber solutions, add 37.5g environment-friendly aromatic rubber oil, stir 30 minutes, then add 600g deionized water, stirring at normal temperature 30 minutes obtained rubber latexs.
Take the white carbon black dispersion liquid that 300g solid content is 25wt%, progressively join in rubber latex, in mulser, stirring and recycle pump blending form rubber and the white carbon black mixed emulsion of stable uniform after 30 minutes.
By above-mentioned mixed emulsion, spray in condensing field after being pressurized to 0.8MPa with latex pump, pass into steam azeotropic desolvation, then remove moisture content by taper singe screw extrusion dehydration and expansion-exsiccation machine, obtain white carbon black wet method rubber unvulcanizate.
Example 8
To in the reactor of drying, adding 1000g solid content is 10wt% randomly solution polymerized butadiene-styrene rubber with low solution, and closed reactor opens stirring, pass into the air in nitrogen replacement still simultaneously, maintain still internal pressure 0.3MPa, open heating, design temperature 70 DEG C, after temperature-stable, press-in 2.5g high-purity propylene acid methyl esters, reacts after 6 hours at 70 DEG C, adds 0.2g antioxidant 1076 and 0.2g irgasfos 168, be cooled to room temperature and discharge glue, obtain modified rubber solutions.
In above-mentioned modified rubber solutions, add 37.5g environment-friendly aromatic rubber oil, stir 30 minutes, then add 600g deionized water, stirring at normal temperature 30 minutes obtained rubber latexs.
Take the white carbon black dispersion liquid that 375g solid content is 20%, join in rubber latex, in mulser, stirring and recycle pump blending form rubber and the white carbon black mixed emulsion of stable uniform after 30 minutes.
By above-mentioned mixed emulsion, under the protection of nitrogen, spray in the special twin screw unit rising good temperature in advance, this unit is
incongruous double screw devolatilization machine, has 5 venting ports, and first is normal pressure mouth, and the pressure of all the other venting ports is decremented to 100mm mercury column successively, and desolvation and moisture content, obtain the brown rubber unvulcanizate that product volatile content is less than the color even of 0.5wt% simultaneously.
Example 9
To in the reactor of drying, adding 1000g solid content is 10wt% randomly solution polymerized butadiene-styrene rubber with low solution, closed reactor opens stirring, pass into the air in nitrogen replacement still simultaneously, maintain still internal pressure 0.3MPa, unlatching chuck heats, design temperature 80 DEG C, after temperature-stable, add 0.5gBPO and 5g grafted monomer vinyl three ('beta '-methoxy oxyethyl group) silane, react after 5 hours at 80 DEG C, add 0.25g antioxidant 1076 and 0.25g irgasfos 168, be cooled to room temperature and discharge glue, obtain modified rubber solutions.
In above-mentioned modified rubber solutions, add 37.5g environment-friendly aromatic rubber oil, stir 30 minutes, then add 600g deionized water, stirring at normal temperature 30 minutes obtained rubber latexs.
The chemical treatment of white carbon black dispersion liquid
Take the white carbon black dispersion liquid that 300g solid content is 25wt%, add 150g deionized water, add two (triethoxysilicane) propyl group tetrasulfide of 3.75g simultaneously, stir 30 minutes in mulser, obtain modified white carbon black dispersion liquid.
Join in rubber latex by modified white carbon black dispersion liquid, in mulser, stirring and recycle pump blending form rubber and the white carbon black mixed emulsion of stable uniform after 30 minutes.
By above-mentioned mixed emulsion, under the protection of nitrogen, spray in the special twin screw unit rising good temperature in advance, this unit is
incongruous double screw devolatilization machine, has 5 venting ports, and first is normal pressure mouth, and the pressure of all the other venting ports is decremented to 100mm mercury column successively, and desolvation and moisture content, obtain the brown rubber unvulcanizate that product volatile content is less than 0.5% simultaneously.
Take the rubber unvulcanizate that obtains in a certain amount of above-mentioned each embodiment with test performance after the sulfurizing formula sulfuration in table 5.
Table 5 is experiment rubber unvulcanizate sulfurizing formula table respectively
| Component | Comparative example | Example 7 | Example 8 | Example 9 |
| Wet method white carbon black rubber unvulcanizate | 0 | 215.5 | 215 | 217.5 |
| Solution polymerized butylbenzene | 100 | 0 | 0 | 0 |
| Environment-friendly rubber oil | 37.5 | 0 | 0 | 0 |
| Precipitated silica | 75 | 0 | 0 | 0 |
| Carbon black N330 | 10 | 10 | 10 | 10 |
| Zinc oxide | 2.5 | 2.5 | 2.5 | 2.5 |
| Stearic acid | 1.5 | 1.5 | 1.5 | 1.5 |
| Antioxidant 4020 | 2 | 2 | 2 | 2 |
| Accelerator CBS | 1.4 | 1.4 | 1.4 | 1.4 |
| Vulkacit D PG | 1.5 | 1.5 | 1.5 | 1.5 |
| Polymerization sulphur | 1.4 | 1.4 | 1.4 | 1.4 |
| KH-848-4 | 6 | 6 | 6 | 6 |
Cure conditions: 160 DEG C 30 minutes.
Table 6 is the performance test of above-mentioned cross-linked rubber
| Sequence number | Test event | Contrast sample | Example 7 | Example 8 | Example 9 |
| 1 | Shore hardness room temperature | 68 | 64 | 65 | 64 |
| 2 | Tensile strength (Mpa) | 17.5 | 18.2 | 18.0 | 18.9 |
| 3 | Elongation rate of tensile failure (%) | 366 | 380 | 375 | 392 |
| 4 | 100% stress at definite elongation (Mpa) | 2.8 | 2.6 | 2.6 | 2.7 |
| 5 | 300% stress at definite elongation (Mpa) | 10.8 | 11.2 | 11 | 12.3 |
| 6 | Tensile set (%) | 18 | 15 | 16 | 14 |
| 7 | Compression set (%) | 3 | 1.6 | 1.7 | 1.5 |
| 8 | Tear strength (N/mm) | 28 | 32 | 30 | 35 |
| 9 | Compression fatigue temperature rise (DEG C) | 27.3 | 23.4 | 24.6 | 20.2 |
| 10 | Resilience (%) | 26 | 32 | 30 | 36 |
[0114]in test event, press GB/T531.1-2008 for the 1st.
In test event, press GB/T528-2009 for 2nd ~ 6.
In test event, press GB/T7759-1996 for the 7th.
In test event, press GB/T529-2008 test for the 8th.
In test event, test with the dark Y3000E compression heat generation trier of Beijing friend for the 9th.
In test event, test with high ferro GT-7042-REA reisilometer for the 10th.
Claims (4)
1. a preparation method for white carbon black wet method rubber unvulcanizate, comprises the following steps:
1), the chemical physics process of rubber solutions
Under agitation, in rubber solutions, add polar monomer react with it, make rubber macromolecule main chain to be introduced polar monomer and there is self-emulsifying function, temperature of reaction is at 70 ~ 120 DEG C, 5 ~ 60 minutes time, polar monomer massfraction is 0.5 ~ 5% of rubber quality, then adds appropriate water, holding temperature, at 35 ~ 50 DEG C, forms the emulsion of homogeneous stability or solution-stabilized material; Described polar monomer is containing the acrylate of ester group, nitrogenous propionyl ammonia, the alkene acid anhydrides of hydroxyl, the organosilicon compound of silicone-containing base or superoxide; Described rubber solutions is synthetic rubber solution; Then carry out physical treatment, under agitation, add terminator and oxidation inhibitor, its viscosity of regulable control is 15000 ~ 50000cp, then adds environmental protection plasticizing oil, accurately controls its polymer concentration, holding temperature, at 50 ~ 60 DEG C, becomes equal phase emulsion or solution-stabilized material;
2), white carbon black surface chemistry and physically modified process
Micron order to nano level white carbon black dispersion liquid is added in stirring tank, then add containing sulfenyl, amino, acyloxy, glycidyl ether or vinyl silicoorganic compound a kind of or with the two or more mixture of any ratio, modified-reaction is carried out to white carbon black molecular surface, make it have lipophilicity, add-on is 1 ~ 5% of white carbon black quality, temperature in room temperature ~ 100 DEG C, 30 ~ 150 minutes reaction times; Physical treatment refers to that mechanical impurity goes Xu and large order number net to cross Lu in stirring tank, and rear deionized water regulates and makes solid content be stabilized in 10 ~ 40wt%, and regulates pH 7 ± 0.5, finally becomes equal phase emulsion;
3), the preparation of mixed emulsion and homogenizing
By various required filler and auxiliary agent, by its character, join respectively through above-mentioned steps 1), 2), equal phase emulsion or solution in, wherein filler and hydrophilic compounds join in the equal phase emulsion of white carbon black; Oiliness compound and hydrocarbon compound join in the equal phase emulsion of rubber or solution-stabilized material, and its solid content is between 5 ~ 50wt%, obtain rubber latex that two kinds of blending configure or solution and the equal phase emulsion of white carbon black respectively;
The rubber latex that above-mentioned blending is configured or solution, feeding is made up of in latex homogenization system a speed change stirring tank and speed change emulsion recycle pump carries out homogenizing, under unlatching stirring and pump cycling condition, white carbon black emulsion blending configured with certain flow rate adds in stirring tank first carries out blending, homogenizing is carried out again, the rubber of obtained stable uniform and white carbon black mixed emulsion with different stirring velocitys and pump internal circulating load;
4) solvent in mixed emulsion and moisture content, is removed
A) by step 3), mixed emulsion pump spray into rubber condensed system, with water vapor azeotropic desolvation, be separated with water by vibratory screening apparatus, then through extrusion dehydration and expansion drying, obtained below water content 1wt%, volatile matter is less than the white carbon black wet method rubber unvulcanizate of 0.5wt%;
Or B) by step 3), a kind of closed two rollers pressure refining machines of mixed emulsion, desolvation and moisture content simultaneously, obtained water content is down to below 1wt%, and volatile matter is less than the white carbon black wet method rubber unvulcanizate of 0.5wt%;
Or C) by step 3), mixed emulsion send in twin-screw set under protection of inert gas, desolvation and water simultaneously, then by extrudate compound stalk forming, obtained white carbon black wet method rubber unvulcanizate, wherein twin-screw set significant parameter is: length is 60100, rotating speed 50 ~ 500rpm; Described inert gas pressure is 0.3Mpa ~ 3Mpa.
2. the preparation method of white carbon black wet method rubber unvulcanizate according to claim 1, it is characterized in that described synthetic rubber solution is low, high-cis polybutadiene, middle and high vinyl polybutadiene, suitable, using trans-polyisoprene, random styrene-butadiene rubber, block butylbenzene, penta benzene rubber, the rubber solutions of fourth penta binary rubber or fourth penta benzene ternary rubber; Described polar monomer massfraction is 0.5 ~ 3% of rubber quality.
3. the preparation method of white carbon black wet method rubber unvulcanizate according to claim 1, is characterized in that the silicoorganic compound of described dialogue carbon blacksurface modification are for two (triethoxysilicane) propyl group tetrasulfide, two (triethoxy is silica-based) propyl group) disulphide, γ-mercaptopropyl trimethoxysilane, γ-aminopropyl triethoxysilane, γ-glycydoxy Trimethoxy silane, γ-methacryloxypropyl trimethoxy silane or vinyl three ('beta '-methoxy oxyethyl group) silane;
Described filler and additive are carbon black, talcum powder, calcium carbonate, calcium sulfate, barium sulfate, metal oxide, salt, emulsifying dispersant, environment-friendly aromatic oil, naphthenic oil, softening agent, coupling agent, oxidation inhibitor, optothermal stabilizer, fire retardant, dyestuff or fluorescent agent.
4. the preparation method of white carbon black wet method rubber unvulcanizate according to claim 1, joins oiliness compound in rubber solutions described in it is characterized in that and hydrocarbon compound is environment-friendly aromatic oil, naphthenic, phenol, amine antioxidants, heat-resisting stabilizing agent or photostabilizer; Joining filler and hydrophilic compounds in white carbon black dispersion liquid is carbon black, calcium carbonate, calcium sulfate, barium sulfate, talcum powder, salt, metal oxide or emulsifying dispersant, and the solid content of dispersion liquid is 30wt% ~ 20wt%.
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| CN105729654A (en) * | 2016-03-17 | 2016-07-06 | 青岛科技大学 | Gas-assisted wet process mixing and preparing device for rubber |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101792546A (en) * | 2009-02-01 | 2010-08-04 | 陈汇宏 | Latex mixing or solution mixing preparation method of rubber powder-rubber compound composition |
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101792546A (en) * | 2009-02-01 | 2010-08-04 | 陈汇宏 | Latex mixing or solution mixing preparation method of rubber powder-rubber compound composition |
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