CN105860588B - A kind of preparation method of modified white carbon black - Google Patents
A kind of preparation method of modified white carbon black Download PDFInfo
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- CN105860588B CN105860588B CN201510030454.8A CN201510030454A CN105860588B CN 105860588 B CN105860588 B CN 105860588B CN 201510030454 A CN201510030454 A CN 201510030454A CN 105860588 B CN105860588 B CN 105860588B
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- white carbon
- carbon black
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Abstract
The present invention provides a kind of preparation methods of primary structure graft modification white carbon, under high temperature, high pressure, shear conditions, white carbon aggregation is set to dissociate, form primary structure, pass through the graft reaction of primary structure white carbon and modifying agent, primary structure white carbon modifying agent graft is ultimately formed, solves the problems, such as that white carbon from reuniting, is realized and is uniformly modified to white carbon.
Description
Technical field
The present invention relates to field of inorganic nonmetallic material, and in particular to a kind of preparation method of modified white carbon black.
Background technology
The features such as white carbon is also known as silica, has more structures, and large specific surface area, chemical stability is good, high temperature resistant,
Rubber reinforcing filler is had been widely used for, as a kind of excellent active reinforcing agent, the tear resistance of sizing material can be significantly improved,
Through being the second largest reinforcing agent for being only second to carbon black.But since there are a large amount of Sol-Gel groups and hydroxyl on its surface so that
It is with stronger hydrophily and autohemagglutination, therefore its application performance is a greater impact.
In recent years, people have done many researchs on white carbon modification technology, and CN200910050337.2 refers to one kind
The method of reinforcing performance of tread rubber of lorry tyre by resin acceptor modified white carbon black dilutes coupling agent using ethyl alcohol, sprays in white carbon
On powder, then modification is stirred in low speed kneader.This method still falls within simple dry blending and is modified, white carbon and
Mostly between coupling agent is limited with the lower hydrogen bond of bond energy and Van der Waals force combination rather than chemical bonds, modified effect.
CN200910142771.3 refers to a kind of preparation method of modified white carbon black, using activation white carbon under the action of ethyl alcohol with
Silane coupling agent mixes, and is once modified, then mixed with toluene diisocyanate, and progress is twice-modified, this is owned by France in wet
Method is modified, and is still to be combined with the lower hydrogen bond of bond energy and Van der Waals force between coupling agent and white carbon, and its process operability
It is complicated.CN201010504667.7 mentions a kind of method of modifying of the Nano carbon white of the rubber chemicals of high dispersive, uses
Nano carbon white is scattered in deionized water, then the method for silane coupling agent ethanol solution, this method are added dropwise into mixed liquor
Belong to wet-process modified, does not also solve the low problem of bond energy between white carbon and coupling agent.201110356195.X referring to a kind of gas
Pre-activate white carbon is added and is modified by the subacidity liquid phase that water, ethyl alcohol, silane coupling agent form by phase method white carbon method of modifying
System is modified, and deviating from low molecule using 150 DEG C of vacuum obtains modified product, this is owned by France in wet-process modified, vacuum work
The purpose of skill is dry, devolatilization, and facilitation is had no to Silanization reaction.
White carbon is typically to exist in the form of aggregation, in above-mentioned white carbon modified technique either it is wet-process modified still
Dry blending is modified, and is the modification of dialogue carbon black aggregate, the i.e. partial modification on dialogue carbon black aggregate surface, and white carbon
Mostly between modifying agent be with the lower hydrogen bond of bond energy and Van der Waals force is combined rather than chemical bonds.Therefore, existing modification
The technical barrier that technology cannot effectively solve the dispersion of white carbon difficulty, easily reunite, modified effect are limited.
Invention content
To solve the above-mentioned problems, the present invention provides a kind of preparation method of primary structure graft modification white carbon,
Under high temperature, high pressure, shear conditions, white carbon aggregation is made to dissociate, form primary structure, by primary structure white carbon and changed
Property agent graft reaction, ultimately form primary structure white carbon modifying agent graft, efficiently solve white carbon from reunite asking
Topic, realizes and is uniformly modified to white carbon.
Primary structure of the present invention refers to white carbon primary partical either by the molecular size of a small amount of bioblast
The basic component units of roughly the same branch and branch-like primary particle and white carbon aggregation with primary partical.
To achieve the above object, solution of the invention is as follows：
(1) white carbon constitutive activation：Reaction kettle is added in white carbon, is vacuumized, is heated to 130~150 DEG C, stirring 2~3
Hour；
(2) white carbon aggregate structure dissociates：4~6MPa is boosted to using inert gas, it is small to shear 1~1.5 for constant temperature
When；
(3) graft reaction：Modifying agent is sprayed into, 150~165 DEG C is warming up to, vacuumizes simultaneously, is stirred, is reacted 1~2 hour,
Dry, discharging.
The present invention also provides a kind of preparation methods of optimization, are described below：
(1) reaction kettle is added in white carbon, vacuumized, stirred (30~80r/min of rate), be heated to 130~150 DEG C,
Carry out white carbon constitutive activation 2~3 hours.
(2) white carbon after constitutive activation boosts to 4~6MPa, 135~145 DEG C of constant temperature using inert gas, and shearing (is cut
900~1200r/min of cutting speed rate), structure dissociates 1~1.5 hour.
(3) modifying agent is at the uniform velocity sprayed into the form of spraying, and is stirred (90~150r/min of rate), is warming up to 150~165
DEG C, it vacuumizes simultaneously, carries out coupling condensation graft reaction 1~2 hour.The mass ratio of modifying agent and white carbon be 0.06~
0.18：1, preferably 0.08~0.16:1；
(4) dry, discharging：(30~80r/min of rate), drying are stirred, temperature of reaction kettle is down to room temperature, it is cooling, it takes
Go out.
Method of modifying of the present invention it is characterized in that：
1, under the high temperature, condition of high voltage of inert gas shielding, strong shear makes white carbon aggregation realize structure dissociation, shape
At white carbon primary structure, the misty modifying agent at the uniform velocity sprayed into is enable to adsorb and be evenly distributed on primary structure white carbon surface
On.
2, the temperature of graft reaction be 150~165 DEG C, preferably 155 DEG C~160 DEG C, this be the present invention must satisfy want
It asks.Coupling condensation reaction cannot carry out when temperature is less than 150 DEG C, and temperature is excessively high, modifying agent can be caused to decompose.
3, graft reaction carries out under vacuum, this is the requirement that the present invention must satisfy.Graft reaction is substantially exactly
Modifying agent is chemically reacted with white carbon surface group, is formed chemical bond, is generated the process of small-molecule substance.Reaction environment
The factors such as temperature, concentration, pressure have a direct impact the movement of chemical reaction equilibrium, process of grafting according to the present invention
Will generate small-molecule substance (H2O, C2H50H etc.), with reaction carry out, constant temperature, constant volume reaction kettle small molecular substance it is dense
Degree and pressure are continuously increased, and the positive mobile trend of chemical reaction equilibrium will be suppressed, and graft reaction, which weakens, even to be stopped.This
The invention vacuum technology, will be such that reaction kettle small molecular substance is constantly removed, effectively reduce reaction kettle pressure and
Product concentration forces chemical reaction equilibrium to be moved to positive reaction direction, and graft reaction carries out more abundant, and grafting rate is substantially
It improves.
4, the mass ratio of modifying agent and white carbon is 0.06~0.18：1, preferably 0.08~0.16:1；Wherein modifying agent packet
It includes：Silane coupling agent, titante coupling agent, polyalcohols coupling agent, such as：γ-(methacryloxy) propyl front three
Oxysilane (KH570), γ-(2,3- the third oxygen of epoxy) propyl trimethoxy silicane (KH560), bis- (triethoxysilylpropyls) four
It is sulfide (Si69), hard containing difunctional (carboxyl and double build) polymer-type coupling agent (C800), pentaerythrite, pentaerythrite
One kind in resin acid ester, pentaerythritol triacrylate.
Compared with prior art the invention has the advantages that：
1, the present invention is that the part of surface graft modification rather than white carbon aggregation based on primary structure white carbon changes
Property, graft is evenly distributed on white carbon surface, and grafting rate is high, and the autohemagglutination degree of modified white carbon black is low, good dispersion.
2, the modifying agent that the present invention uses is common coupling agent, cheap.
3, the present invention uses dry method modification, and the processes such as activation, structure dissociation, grafting, the drying of white carbon are in grafting kettle
It completes, belongs to one-pass molding, it is simple for process, it can be with large-scale production.
Specific implementation mode
In order to facilitate the present invention is understood, by embodiment, the present invention is further described, but protection scope of the present invention is not
It is limited to embodiment.
A kind of preparation method of modified white carbon black, includes the following steps：
Step 1：Reaction kettle is added in white carbon, is vacuumized, is heated to 130~150 DEG C, is stirred 2~3 hours；
Step 2：4~6MPa is boosted to using inert gas, constant temperature is sheared 1~1.5 hour；And
Step 3：Modifying agent is sprayed into, 150~165 DEG C is warming up to, vacuumizes simultaneously, is stirred, is reacted 1~2 hour, dry,
Discharging.
(1) material source
White carbon Rhodia
Bis- (triethoxysilylpropyl) the tetrasulfide Degussas of modifying agent
Propyl trimethoxy silicane Shanghai is quiet melts the limited public affairs of biotechnology by modifying agent γ-(2,3- the third oxygen of epoxy)
Modifying agent pentaerythrite Jinan century sensible Chemical Co., Ltd.
The Dushanzi rubber solution polymerized butadiene styrene rubber SSBR2557S petrochemical industry branch company
Other auxiliary agents are rubber industry usual auxiliaries.
(2) analysis method
White carbon structural characterization：Using DBP absorption values.I.e. under prescribed test conditions, 100g white carbons absorb DBP
Volume (cm3) number of (dibutyl phthalate) is white carbon aggregation and degree of agglomeration for characterizing the aggregation extent of carbon black
Measurement.
Graft modification efficiency characterizes：Using German NETZSCH companies synchronous solving (TG, DSC etc.), after acquisition drying
20~600 DEG C of graft modification white carbon within the scope of Weight loss data.
White carbon modified effect characterizes：It is mixed using the SSBR2557S of carbon black dispersion Instrumental Analysis reinforcement containing modified white carbon black
The carbon black dispersion percentage of refining glue.
(3) embodiment
Embodiment 1
(1) graft reaction kettle is added in 1000 grams of white carbons, vacuumized, stirred (rate 50r/min), be heated to 135 DEG C,
Carry out white carbon constitutive activation 2 hours.
(2) 4MPa, 140 DEG C of constant temperature, strong shear (shear rate 950r/min), structure solution are boosted to using inert gas
From 1 hour.
(3) 80 grams of bis- (triethoxysilylpropyl) tetrasulfides are slowly at the uniform velocity sprayed into the form of spraying, and stir (rate
90r/min), 155 DEG C are warming up to, is vacuumized simultaneously, carries out graft reaction 1.5 hours.
(4) it is cooled down through dry, obtains graft modification white carbon.
Comparative example 1-1
It is only completed the product (activation white carbon) of 1 (1) step of embodiment.
Comparative example 1-2
It is only completed the product (primary structure white carbon) of embodiment 1 (1), (2) step.
Comparative example 1-3
In (3) of embodiment 1, vacuum technology cancel, it is other in the same manner as in Example 1.
Comparative example 1-4
(2) of embodiment 1 cancel, i.e., are dissociated without structure, it is other in the same manner as in Example 1.
It is analyzed and characterized result such as table 1：
1 embodiment 1 of table and its comparative example analysis result
Embodiment 2
(1) graft reaction kettle is added in 1000 grams of white carbons, vacuumized, stirred (rate 60r/min), be heated to 135 DEG C,
Carry out white carbon constitutive activation 2 hours.
(2) 4MPa, 140 DEG C of constant temperature, strong shear (shear rate 1100r/min), structure are boosted to using inert gas
Dissociation 1.5 hours.
(3) 120 grams of γ-(2,3- the third oxygen of epoxy) propyl trimethoxy silicanes, are slowly at the uniform velocity sprayed into the form of spraying, are stirred
(rate 90r/min) is mixed, 155 DEG C is warming up to, vacuumizes simultaneously, carries out graft reaction 1.5 hours.
(4) diameter drying cooling, obtains graft modification white carbon.
Comparative example 2-1
It is only completed the product (activation white carbon) of 1 (1) step of embodiment.
Comparative example 2-2
It is only completed the product (primary structure white carbon) of embodiment 1 (1), (2) step.
Comparative example 2-3
In (3) of embodiment 2, vacuum technology cancel, it is other in the same manner as in Example 2.
Comparative example 2-4
(2) of embodiment 2 cancel, i.e., are dissociated without structure, it is other in the same manner as in Example 1.
It is analyzed and characterized result such as the following table 2：
2 embodiment 2 of table and its comparative example analysis result
Embodiment 3
(1) graft reaction kettle is added in 1000 grams of white carbons, vacuumized, stirred (rate 70r/min), be heated to 135 DEG C,
Carry out white carbon constitutive activation 2 hours.
(2) 4MPa, 140 DEG C of constant temperature, strong shear (shear rate 1000r/min), structure are boosted to using inert gas
Dissociation 1 hour.
(3) 100 grams of dipentaerythritol stearates, are slowly at the uniform velocity sprayed into the form of spraying, stir (rate 90r/
Min), 160 DEG C are warming up to, is vacuumized simultaneously, carries out graft reaction 1.5 hours.
(4) diameter drying cooling, obtains graft modification white carbon.
Comparative example 3-1
It is only completed the product (activation white carbon) of 1 (1) step of embodiment.
Comparative example 3-2
It is only completed the product (primary structure white carbon) of embodiment 1 (1), (2) step.
Comparative example 3-3
In (3) of embodiment 3, vacuum technology cancel, it is other in the same manner as in Example 1.
Comparative example 3-4
(2) of embodiment 3 cancel, i.e., are dissociated without structure, it is other in the same manner as in Example 1.
It is analyzed and characterized result such as the following table 3：
3 embodiment 3 of table and its comparative example analysis result
It is learnt from above-described embodiment and comparative example analysis result, modified white carbon black prepared by method using the present invention connects
Branch rate is higher, being uniformly dispersed in rubber matrix, and white carbon is effectively controlled from reuniting.
Solution polymerized butadiene styrene rubber reinforcement experiment is carried out using above-mentioned modified white carbon black, reinforcing effect is as indicated at 4：
Reinforcing effect of 4 modified white carbon black of table to SSBR2557S
From table 4, it can be seen that above-mentioned modified white carbon black reinforcement SSBR2557S, wherein embodiment 1,2,3 sample stretches by force
Degree is high, and 0 DEG C of fissipation factor height, 60 DEG C of fissipation factors are low, show its physical mechanical property, wet-sliding resistant performance, rolling resistance compared with
Comparative example increases substantially, the good combination property of sizing material.Therefore, the improvement of the carbon black modified technology of dialogue of the present invention is highly significant
's.
Certainly, the present invention can also have other various embodiments, without deviating from the spirit and substance of the present invention, ripe
Various corresponding change and deformations, but these corresponding change and deformations can be made according to the present invention by knowing those skilled in the art
The protection domain of the claims in the present invention should all be belonged to.
Claims (10)
1. a kind of preparation method of modified white carbon black, which is characterized in that include the following steps：
Step 1：Reaction kettle is added in white carbon, is vacuumized, is heated to 130~150 DEG C, is stirred 2~3 hours；
Step 2：4~6MPa is boosted to using inert gas, constant temperature is sheared 1~1.5 hour, and shear rate is 900~
1200r/min；And
Step 3：Modifying agent is sprayed into, 150~165 DEG C is warming up to, vacuumizes simultaneously, is stirred, is reacted 1~2 hour, drying goes out
Material；
The modifying agent is silane coupling agent, titante coupling agent or polyalcohols coupling agent.
2. the preparation method of modified white carbon black according to claim 1, which is characterized in that the stirring speed in the step 1
Rate is 30~80r/min.
3. the preparation method of modified white carbon black according to claim 1, which is characterized in that the constant temperature in the step 2 is
135~145 DEG C.
4. the preparation method of modified white carbon black according to claim 1, which is characterized in that the stirring speed in the step 3
Rate is 90~150r/min.
5. the preparation method of modified white carbon black according to claim 1, which is characterized in that reaction temperature in the step 3
It is 155~160 DEG C.
6. the preparation method of modified white carbon black according to claim 1, which is characterized in that modifying agent in the step 3
Feed postition is at the uniform velocity sprayed into the form of spraying.
7. the preparation method of modified white carbon black according to claim 1, which is characterized in that the modifying agent is γ-(methyl
Acryloxy) propyl trimethoxy silicane, γ-(2,3- the third oxygen of epoxy) propyl trimethoxy silicane, bis- (triethoxysilicanes third
Base) tetrasulfide, contain bifunctional polymer's type coupling agent, pentaerythrite, pentaerythritol stearate or pentaerythrite three
One kind in acrylate.
8. the preparation method of modified white carbon black according to claim 7, which is characterized in that described to polymerize containing difunctional
Functional group in object type coupling agent is carboxyl and double bond.
9. the preparation method of modified white carbon black according to claim 1, which is characterized in that the modifying agent and white carbon
Mass ratio is 0.06~0.18：1.
10. the preparation method of modified white carbon black according to claim 1, which is characterized in that the modifying agent and white carbon
Mass ratio be 0.08~0.16:1.
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| CN106315599B (en) * | 2016-08-27 | 2018-08-28 | 安徽龙泉硅材料有限公司 | A kind of preparation method of rubber roller for industry precipitated silica used for rubber reinforcement |
| CN106241822B (en) * | 2016-08-27 | 2018-08-28 | 安徽龙泉硅材料有限公司 | A kind of preparation method of dry powder farm chemical carrier precipitated silica |
| CN106833027A (en) * | 2017-01-12 | 2017-06-13 | 温州市炬邦新材料有限公司 | A kind of improved silica production technology |
| CN107082913B (en) * | 2017-05-26 | 2019-06-14 | 成都微熵科技有限公司 | A kind of hydrophobic titanium dioxide silicon modified rubber and preparation method |
| CN107603280A (en) * | 2017-08-07 | 2018-01-19 | 湖州同泰新材料有限公司 | A kind of preparation method of white carbon |
| CN109942003B (en) * | 2019-04-17 | 2020-09-18 | 华东理工大学 | Method for dry grinding modified precipitated white carbon black |
| CN112375253A (en) * | 2020-10-26 | 2021-02-19 | 贵州大学 | Preparation method of modified sulfur and white carbon black blend for rubber |
| CN115594978B (en) * | 2022-10-29 | 2024-03-05 | 江苏加富新材料科技有限公司 | High-voltage-resistant insulating rubber plate and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997040095A2 (en) * | 1996-08-26 | 1997-10-30 | Bridgestone Corporation | Rubber composition and pneumatic tire made by using the same |
| CN101061188A (en) * | 2004-11-18 | 2007-10-24 | 德古萨有限责任公司 | Hydrophobic silicon dioxide and its application in silicon rubber |
| CN101108730A (en) * | 2006-07-18 | 2008-01-23 | 德古萨股份公司 | Surface modified silicon dioxide |
| CN103059572A (en) * | 2013-01-31 | 2013-04-24 | 沈阳化工股份有限公司 | Surface modification gas-phase silicon dioxide capable of enhancing high temperature resistant property of silicon rubber and production method thereof |
-
2015
- 2015-01-21 CN CN201510030454.8A patent/CN105860588B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997040095A2 (en) * | 1996-08-26 | 1997-10-30 | Bridgestone Corporation | Rubber composition and pneumatic tire made by using the same |
| CN101061188A (en) * | 2004-11-18 | 2007-10-24 | 德古萨有限责任公司 | Hydrophobic silicon dioxide and its application in silicon rubber |
| CN101108730A (en) * | 2006-07-18 | 2008-01-23 | 德古萨股份公司 | Surface modified silicon dioxide |
| CN103059572A (en) * | 2013-01-31 | 2013-04-24 | 沈阳化工股份有限公司 | Surface modification gas-phase silicon dioxide capable of enhancing high temperature resistant property of silicon rubber and production method thereof |
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