CN106674593A - Silane coupling agent containing vinyl ether chain segment, and preparation method and application thereof - Google Patents
Silane coupling agent containing vinyl ether chain segment, and preparation method and application thereof Download PDFInfo
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- CN106674593A CN106674593A CN201611098399.7A CN201611098399A CN106674593A CN 106674593 A CN106674593 A CN 106674593A CN 201611098399 A CN201611098399 A CN 201611098399A CN 106674593 A CN106674593 A CN 106674593A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/548—Silicon-containing compounds containing sulfur
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/28—Compounds of silicon
- C09C1/30—Silicic acid
- C09C1/3081—Treatment with organo-silicon compounds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/12—Treatment with organosilicon compounds
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Abstract
The invention discloses a silane coupling agent containing a vinyl ether chain segment, and a preparation method and an application thereof. The silane coupling agent is a novel silane coupling agent. The silane coupling agent is acquired through the catalytic reaction of the traditional coupling agent with a formula (IV) structure and fatty alcohol-polyoxyethylene ether or alicyclic alcohol polyoxyethylene ether. The application of the silane coupling agent disclosed by the invention in preparing a high-performance tread rubber by in situ modifying white carbon black can effectively reduce the VOC discharge in the size mixing process and in the use process of rubber products. The silane coupling agent disclosed by the invention also can be used for modifying the liquid phase of the white carbon black; the wet-process mixing can be realized; the problems of single method for modifying the white carbon black with the traditional silane coupling agent, large energy consumption in the processing process and serious pollution can be effectively solved; and the traditional coupling agent with the formula (IV) structure and the fatty alcohol-polyoxyethylene ether in low cost are taken as the synthesis raw materials, so that the use cost of the coupling agent is lowered.
Description
Technical field
The present invention relates to organic chemistry filed, more particularly, to a kind of silane coupler and its preparation method and application.
Background technology
Tread rubber is prepared using white carbon black modified by silane coupling agent can improve dispersion of the white carbon in rubber matrix,
Obtained sizing material has the clear superiorities such as low rolling resistance, high wet-sliding resistant.Common rubber silane coupler has sulfydryl one type of silane
With polysulfide one type of silane.The silane coupler crosslinking rate of sulfydryl class is fast, easy with rubber mixing process that incipient scorch occurs.Especially
It is that incipient scorch, scaling-off phenomenon are particularly evident when having the compounding rubber of double bond structure with side chain, this is also limited to a certain extent
Its application is made.Comparatively, silane coupler crosslinking rate containing polysulfide is moderate, can be mixed at higher temperatures
Refining.Separately studies have found that, two ends are respectively provided with the coupling agent of silica group, by taking Si69 as an example, its two ends can respectively be connected on white carbon
Surface forms network-like white carbon.The coupling agent connected between white carbon, preferably prevents contacting with each other for Linesless charcoal night,
Ensure that the good dispersion in rubber matrix of white carbon.
Although larger improvement is served to the performance of rubber currently with conventional silanes coupling agent, due to traditional silicon
Alkane coupling agent contains multiple methoxies, ethoxy group, the meeting during modified filler, compounding rubber and final tire product use
The lower boiling VOC such as methanol, ethanol is discharged, lower alcohol is discharged in air, photochemical reaction can be carried out and broken
Bad atmosphere, therefore be also difficult to meet the requirement of green tire coupling agent；At the same time, behaviour is also resulted in the industrial production
Make workman and produce the symptoms such as headache, dim eyesight.
Meanwhile, liquid phase modified white carbon black, wet method calendering process compares dry method mixing process course of processing simplicity, can overcome dry
Method mixed refining process energy consumption is big, the problems such as course of processing pollution is big, has a clear superiority.But most conventional silanes coupling agents are not due to
Water is dissolved in, wet-process modified white carbon is not suitable for, processing conditionss are limited, and coupling agent superperformance is also constrained to a great extent
Performance.
To sum up, invention one kind can reduce VOC emission, and wet method calendering process is can be suitably used for again, and have good to white carbon
Development of the environmental protection, High Efficient Bonding Agents of good modified effect to rubber industry has great importance.
The content of the invention
Analyze in view of more than, it is an object of the invention to provide one kind can be used for dry process modified white carbon black, subtract
VOC emission during few mixing process and rubber use, can be used for the novel coupling agent and its system of wet-process modified white carbon again
Standby and application, while requiring that the coupling agent modified white carbons of Jing are well dispersed in rubber matrix, obtained sizing material possesses low rolling
Resistance, the advantage of high wet-sliding resistant.
For achieving the above object, the technical scheme is that：Silane coupler containing vinyl ethers segment and its
Prepare and apply.The present invention is achieved through the following technical solutions：
The coupling agent has the silane coupler of formula I (II) (III) architectural feature：
Wherein
1)R1For methyl or ethyl；
2)R2It is with hydrophilic fatty alcohol-polyoxyethylene ether group or alicyclic ring polyoxyethylenated alcohol group, it is preferred that R2
HaveStructure, k=3-20, preferably 7,8,9), R4Architectural feature be it is identical or different,
With straight or branched or ring-type, saturation or undersaturated alkyl or alkylene, R4Institute's carbon atom quantity at least 12, preferably
Have 12,13,14,15,16,18.
3)R3Be C2-C20 straight or brancheds or ring-type also or alkyl or alkylene with phenyl ring；
4)-SmRepresent polysulfide bond, m=1-6；
In being implemented within example, the silane coupler is selected from：
Can be seen that from the structural formula of above-mentioned coupling agent：Compared to conventional silanes coupling agent and filler white carbon hydroxyl reaction
Oxyalkylene segment mostly be methoxy or ethoxy group, coupling agent of the present invention with the fatty alcohol-polyoxyethylene ether group of long-chain or
Alicyclic ring polyoxyethylenated alcohol group replaces part methoxy or ethoxy group, can effectively reduce silane coupler with filler, sizing material
Methanol during mixing process and final products use, the volatilization of second alcohols material；Coupling agent of the present invention is containing hydrophilicVinyl Ether segment, it is hydrophilic to adjust coupling agent by the recurring units number k for adjusting vinyl ethers segment
Property, k=3-20 can realize application of the silane coupler in wet-process modified white carbon.
Coupling agent two ends of the present invention are respectively provided with silica group, and its two ends can respectively be connected on white carbon surface and form network
The white carbon of shape, it is ensured that the good dispersion in rubber matrix of white carbon.Coupling agent of the present invention belongs to multiple sulfides idol
Connection agent, compared with sulfydryl class coupling agent for, be less susceptible to incipient scorch in mixing process.
Present invention also offers the preparation method of silane coupler, is included in traditional coupling agent and R of formula IV structure2-
Catalyst is added or be added without in the mixture of OH, is mixed and is produced the step of inventing the silane coupler.
It is to improve reaction rate in above-mentioned preparation method, catalyst, the catalyst can be added to urge for acidity in system
Agent sulphuric acid, p-methyl benzenesulfonic acid or metallic catalyst butyl titanate, at least one or generic catalyst in stannous chloride
It is used in mixed way, the consumption of preferred catalyst is the 0.1%-3% of reacting material mixture weight.
In above-mentioned preparation method, traditional coupling agent of formula IV structure and R2The mol ratio that-OH feeds intake is 1:1-6, can lead to
Overregulate the coupling agent that raw material rate of charge obtains (I) (II) and (III) different structure.
In above-mentioned preparation method, after reaction raw materials mixing, kept for preferred 80 DEG C -200 DEG C of reaction temperature, response time
0.5-4h。
In above-mentioned preparation method, reaction system will ensure dried over anhydrous, be to reduce reactant from polycondensation and other side reactions,
Reaction is carried out under conditions of nitrogen protection.
In above-mentioned preparation method, the R produced in course of reaction2- OH will in time steam reaction system, after the completion of reaction, Jing
Vacuum distillation removes by-product, obtains described coupling agent.The R that course of reaction is produced2- OH can be used or straight as industrial products
Pin is sold.
Present invention also offers the silane coupler is made in the in-situ modified white carbon of dry method and wet-process modified white carbon
Application in standby high-performance rubber.
In above-mentioned application process, in the original location dry method modification white carbon prepares application in high-performance rubber to silane coupler.
Its key step includes：
1) by rubber, white carbon black filler, other rubber chemicals outside vulcanisation auxiliary agent, silane coupler sequentially adds mill
Mixing is carried out in machine or banbury and obtains elastomeric compound；
2) above-mentioned elastomeric compound carries out at 100-150 DEG C high temperature is counter to be refined；
3) elastomeric compound after anti-refining adds vulcanization aid in mill or banbury；
4) elastomeric compound is vulcanized, and obtains vulcanite.
In above-mentioned preparation method, the addition of filler is elastomeric compound gross mass 20%wt-50%wt, the silane coupler
Addition for packing quality 4%wt-20%wt.
The wet-process modified white carbon of the coupling agent that also provides of the present invention to prepare high-performance rubber in applying step bag
Include：
1) by white carbon water slurry, silane coupler is stirred under the conditions of 25-60 DEG C and obtains modified white carbon black water slurry；
2) add latex in above-mentioned modified white carbon black water slurry, agitated, flocculation, washing, be dried after obtain filled with white
The rubber master batch of white carbon black；
3) rubber master batch filled with white carbon, other rubber chemicals outside vulcanisation auxiliary agent, sequentially adds mill or banburying
Mixing is carried out in machine and obtains elastomeric compound；
4) above-mentioned elastomeric compound carries out at 100-150 DEG C high temperature is counter to be refined；
5) elastomeric compound after anti-refining adds vulcanization aid in mill or banbury；
6) elastomeric compound is vulcanized, and obtains vulcanite.
In above-mentioned preparation method, filler and coupling agent addition are in-situ modified with dry method consistent.The addition of filler is
Elastomeric compound gross mass 20%wt-50%wt, the addition of the silane coupler is the 4%wt-20%wt of packing quality.
Compared with prior art, the present invention has following effect：
Coupling agent of the present invention is a kind of new silane coupler, can be carried with the hydroxyl reaction on white carbon surface
The dispersibility of high white carbon and the combination property of rubber.Meanwhile, cheap silane monomer is adopted for raw material preparation, drop
The low use cost of silane coupler, has a good application prospect.
Coupling agent of the present invention is applied to into the in-situ modified white carbon of dry method, it is same in the combination property for improving rubber
When, rubber compounding process and the VOC emission during final products use can be reduced.Meet the requirement of green tire.
Coupling agent of the present invention can also be successfully applied to wet-process modified white carbon, modified technique more simply, be easy to
Commercial Application, overcomes the problems such as dry method mixed refining process energy consumption is big, and course of processing environmental pollution is big.
Specific embodiment
For a further understanding of the present invention, with reference to embodiment to silane coupler of the present invention and preparation method thereof
Be described using preferred embodiment, but it is to be understood that these descriptions are intended merely to be described in more detail the spy of the present invention
Seek peace advantage, but the claims in the present invention are limited never in any form.
Embodiment 1
By 26.95g pair-(γ-triethoxy silicon substrate propyl group) tetrasulfide, i.e. Si69 and 49.5g aliphatic alcohol polyethenoxies
Ether primary alconol AEO-7, structural formula isThe commercially produced product of BASF AG's production.Wherein, R4
For the fat hydrocarbon chain of straight chain, C=12-16, EO number k=7, the tri- mouthfuls of burnings of 200ml equipped with agitating device and distilling apparatus are put into
In bottle, molar ratio 1:2, add 0.230g tetrabutyl titanate catalysts, stirring reaction 3h under the conditions of 100 DEG C of temperature, instead
Should carry out under nitrogen protection, the ethanol produced in course of reaction constantly distills out system.80 DEG C of mixture postmenstruation, 50mpa
Under the conditions of revolving be met the yellow liquid of formula I, wherein R1For ethyl, R2ForR3
For-CH2CH2CH2-。
Embodiment 2
By 26.95g pair-(γ-triethoxy silicon substrate propyl group) tetrasulfide, i.e. Si69 and 49.5g aliphatic alcohol polyethenoxies
Ether primary alconol AEO-7, structural formula isWherein, R4For the fat hydrocarbon chain of straight chain, C=12-16,
EO number k=7, in putting into the 200ml there-necked flasks equipped with agitating device and distilling apparatus, molar ratio 1:2, addition
To benzene methanesulfonic acid catalyst, stirring reaction 2.5h under the conditions of 120 DEG C of temperature, reaction is carried out under nitrogen protection 0.230g, instead
The ethanol produced during answering constantly distills out system.80 DEG C of mixture postmenstruation, revolving is met formula under the conditions of 50mpa
(I) yellow liquid, wherein R1For ethyl, R2ForR3For-CH2CH2CH2-。
Embodiment 3
By 40.43g pair-(γ-triethoxy silicon substrate propyl group) tetrasulfide, i.e. Si69 and 148.5g aliphatic alcohol polyethenoxies
Ether primary alconol AEO-7, structural formula isWherein, R4For the fat hydrocarbon chain of straight chain, C=12-16,
EO number k=7, in putting into the 500ml there-necked flasks equipped with agitating device and distilling apparatus, molar ratio 1:4, addition
To benzene methanesulfonic acid catalyst, stirring reaction 3h under the conditions of 120 DEG C of temperature, reaction is carried out under nitrogen protection, reacted 0.510g
During produce ethanol constantly distill out system.80 DEG C of mixture postmenstruation, revolving is met formula II under the conditions of 50mpa
Yellow liquid, wherein R1For ethyl, R2ForR3For-CH2CH2CH2-。
Embodiment 4
161.7g couple-(γ-triethoxy silicon substrate propyl group) tetrasulfide, i.e. Si69 and 699.4g is fatty
Polyoxyethylenated alcohol primary alconol AEO-9, BASF AG's production, structural formula, its
In, R4For the fat hydrocarbon chain of straight chain, C=12-18, EO number k=9, the 2L tri- equipped with agitating device and distilling apparatus is put into
In mouth flask, molar ratio 1:4, add 0.861g tetrabutyl titanate catalysts, the stirring reaction under the conditions of 120 DEG C of temperature
4h, reaction is carried out under nitrogen protection, and the ethanol produced in course of reaction constantly distills out system.80 DEG C of mixture postmenstruation,
Revolving is met the yellow liquid of formula II under the conditions of 50mpa, and wherein R1 is ethyl, R2ForR3For-CH2CH2CH2-。
Embodiment 5
By 53.9g it is double-(γ-triethoxy silicon substrate propyl group) tetrasulfide, i.e. the alcohol Polyethylene oxide of Si69 and 240g isomeries 13
Ether, structural formula isTrade mark TO-81308, BASF AG's production, wherein R4It is containing 13 carbon
Isomerization hydrocarbon chain, EO number k=8 put into during tri- mouthfuls of the 500ml equipped with agitating device and distilling apparatus burns, feed intake and rub
You compare 1:4, add 0.881g butyl titanate catalytic reactions, stirring reaction 6h under the conditions of 80 DEG C of temperature is reacted in nitrogen bottle gas
Carry out under protection, the ethanol produced in course of reaction constantly distills out system.80 DEG C of mixture postmenstruation, 50mpa condition backspins
Steaming is met the yellow liquid of formula II, wherein R1For ethyl, R2ForR3For-
CH2CH2CH2-。
Embodiment 6
By 53.9g it is double-(γ-triethoxy silicon substrate propyl group) tetrasulfide, i.e. the alcohol Polyethylene oxide of Si69 and 240g isomeries 13
Ether, structural formula isTrade mark TO-81308, BASF AG's production, wherein R4It is containing 13 carbon
Isomerization hydrocarbon chain, EO number k=8 put into during tri- mouthfuls of the 500ml equipped with agitating device and distilling apparatus burns, feed intake and rub
You compare 1:4, add 0.881g concentrated sulfuric acid catalysts, stirring reaction 6h under the conditions of 100 DEG C of temperature is reacted under nitrogen bottle gas shielded
Carry out, the ethanol produced in course of reaction constantly distills out system.80 DEG C of mixture postmenstruation, revolving is obtained under the conditions of 50mpa
Meet the yellow liquid of formula II, wherein R1For ethyl, R2ForR3For-CH2CH2CH2-。
Embodiment 7
By 16.17g it is double-(γ-triethoxy silicon substrate propyl group) tetrasulfide, i.e. the alcohol Polyethylene oxide of Si69 and 30g isomeries 13
Ether, structural formula isTrade mark TO-71307, BASF AG's production, wherein R4It is containing 13 carbon
Isomerization hydrocarbon chain, EO number k=7 put into during tri- mouthfuls of the 100ml equipped with agitating device and distilling apparatus burns, feed intake and rub
You compare 1:2, add 0.062g butyl titanate catalytic reactions, stirring reaction 2h under the conditions of 130 DEG C of temperature is reacted in nitrogen bottle gas
Carry out under protection, the ethanol produced in course of reaction constantly distills out system.80 DEG C of mixture postmenstruation, 50mpa condition backspins
Steaming is met the yellow liquid of formula I, wherein R1For ethyl, R2ForR3For-
CH2CH2CH2-。
Embodiment 8
By 53.9g it is double-(γ-triethoxy silicon substrate propyl group) tetrasulfide, i.e. the alcohol Polyethylene oxide of Si69 and 252g isomeries 13
Ether, structural formula isTrade mark TO-91300, BASF AG's production, wherein R4It is containing 13 carbon
Isomerization hydrocarbon chain, EO number k=9 put into during tri- mouthfuls of the 500ml equipped with agitating device and distilling apparatus burns, feed intake and rub
You compare 1:4, add 0.061g butyl titanate catalytic reactions, stirring reaction 3h under the conditions of 110 DEG C of temperature is reacted in nitrogen bottle gas
Carry out under protection, the ethanol produced in course of reaction constantly distills out system.80 DEG C of mixture postmenstruation, 50mpa condition backspins
Steaming is met the yellow liquid of formula II, wherein R1For ethyl, R2ForR3For-
CH2CH2CH2-。
Embodiment 9
Below by taking product obtained in embodiment 1 as an example, using dry method modification white carbon in situ and implement dry method rubber respectively
Mixing, while with the group without coupling agent and addition Si69 coupling agents as matched group, testing the application performance of its rubber.Prepare
The basic recipe of rubber/white carbon see the table below 1, and refining glue step is as follows：
1) NR, white carbon, coupling agent, ZnO, SA, 50 DEG C of mixings, 3 minutes back glues are added in banbury；
2) 140 DEG C of addition sizing materials carry out heat treatment 5min back glues in banbury；
3) treat that sizing material cools down room temperature, add in mill and promote CZ and S-80, slice after mixing is uniform.
Table 1
Made by the respective performances of corresponding vulcanizate see the table below 2.
Table 2
| Performance indications | 1 | 2 | 3 |
| MH | 31.2 | 37.39 | 33.40 |
| ML | 6.12 | 7.98 | 7.59 |
| MH-ML | 25.07 | 29.41 | 25.80 |
| T10 | 6.5 | 8.8 | 7.5 |
| T90 | 18.8 | 14.3 | 12.5 |
| Tensile strength Mpa | 21.6 | 25.5 | 27.6 |
| Tearing strength Mpa | 77.7 | 105.5 | 107.5 |
| Elongation at break % | 539 | 523 | 560 |
| 100% stress at definite elongation Mpa | 2.0 | 2.4 | 2.1 |
| 300% stress at definite elongation | 6.5 | 10.4 | 9.4 |
| 0 DEG C of tan δ-value | 0.101 | 0.120 | 0.118 |
| 60 DEG C of tan δ-value | 0.041 | 0.060 | 0.043 |
| Akron abrasion loss | 0.366 | 0.259 | 0.268 |
| Dynamic temperature rise | 10.4 | 15.4 | 14.6 |
In the case of coupling agent, white carbon compounded rubber is difficult, there is more white carbon loss.By table 2
Data can be seen that this product compares S69 can reduce tan δ-value and dynamic temperature rise of the final sizing material at 60 DEG C, final sizing material it is stagnant
After lose low, energy consumption can be reduced.The comprehensive mechanical property of sizing material is preferable, by contrasting three kinds of sizing material VOC in mixing process
Burst size：The not silane-containing of sizing material 1 is contrasted, sizing material 2 contains 5 parts of silicon Si69, and sizing material 3 contains 5 parts of coupling agents.The coupling agent contains two
Individual ethyoxyl and 4 polymerizable substituents, the latter is non-volatile, and the Si69 for adding same quality is compared with the coupling agent, the idol
Connection agent mole is few, and for Si69, VOC can about reduce 94%.
The coupling agent can be realized to the effective control of VOC emission amount in mixing process, while discharging in rubber
The reduction of thing is also beneficial to realize the requirement of environmental protection.
Embodiment 10
Below by taking product obtained in embodiment 4 as an example, using liquid phase modified white carbon black, the product wet method mixing system is illustrated
The feasibility of standby rubber master batch.Formula is similar to No. 3 samples in table 1, and NR is changed to NR latex, and white carbon is changed to white carbon water slurry, addition
Number is constant.Preparation process is as follows：
1) by white carbon water slurry, silane coupler is stirred under the conditions of 40 DEG C and obtains modified white carbon black water slurry；
2) NR latex is added in above-mentioned modified white carbon black water slurry, is filled with after agitated, flocculation, washing, drying
The rubber master batch of white carbon；
3) rubber master batch filled with white carbon, ZnO, SA, 50 DEG C of mixings, 3 minutes back glues are added in banbury；
4) 120 DEG C of addition sizing materials carry out heat treatment 5min back glues in banbury；
5) treat that sizing material cools down room temperature, add in mill and promote CZ and S-80, slice after mixing is uniform.
Coupling agent Si69 is water insoluble, it is impossible to realize wet-process modified, and coupling agent Si69 is placed in water, and Si69 can float on table
Face, white carbon water slurry can be remained in flocculation liquid, the white muddy state of flocculation liquid.Preparing the rubber master batch process filled with white carbon
In, using coupling agent liquid phase modified white carbon black described in this patent, wet method prepares rubber master batch process, and flocculation liquid color is clear, and flocculate liquid
Middle to remain without white carbon, it is feasible that wet method prepares rubber master batch.The property of final sizing material is as shown in table 3 in embodiment 10.
Table 3
Claims (10)
1. there is the silane coupler of formula I (II) or (III) architectural feature：
1)R1For methyl or ethyl；
2)R2For fatty alcohol-polyoxyethylene ether group or alicyclic ring polyoxyethylenated alcohol group；
3)R3Be C2-C20 straight or brancheds or ring-type also or alkyl or alkylene with phenyl ring；
4)-SmRepresent polysulfide bond, m=1-6.
2. silane coupler according to claim 1, it is characterised in that R2Be withStructure
Long carbon chain fatty alcohol-polyoxyethylene ether or alicyclic ring polyoxyethylenated alcohol group, wherein k=3-20, R4Architectural feature for identical or
It is different, with straight or branched or ring-type, saturation or undersaturated, the alkyl containing heterogeneous structure or without heterogeneous structure
Or alkylene, R4Institute's carbon atom quantity at least 12.
3. silane coupler according to claim 2, it is characterised in that the silane coupler structure optionally from：
4. the method for preparing the silane coupler as described in claim 1-3 any one, it is characterised in that using with formula IV
Traditional coupling agent of structure and R2- OH is stirred at 80 DEG C -200 DEG C and protected in nitrogen under conditions of adding or being added without catalyst
0.5-4 hours are reacted under the conditions of shield, Jing is distilled off the by-product R in system1- OH, obtains final product the coupling agent；Wherein R1, R2,
R3Represented implication is with above-mentioned consistent.
5. the preparation method of silane coupler according to claim 4, it is characterised in that the catalyst is acidic catalyst
Sulphuric acid, p-methyl benzenesulfonic acid or metallic catalyst butyl titanate, stannous chloride, catalyst is one or more of above-mentioned catalyst
Catalyst is used in mixed way, and addition is the 0.1%-3% of raw material addition.
6. the preparation method of silane coupler according to claim 4, it is characterised in that reaction unit will ensure drying.
7. in the original location dry method modification white carbon prepares high-performance rubber to the silane coupler as described in claim 1-3 any one
In application, it is characterised in that comprise the following steps：
1) by rubber, white carbon black filler, other rubber chemicals outside vulcanisation auxiliary agent, silane coupler sequentially add mill or
Mixing is carried out in banbury and obtains elastomeric compound；
2) above-mentioned elastomeric compound carries out at 100-150 DEG C high temperature is counter to be refined；
3) elastomeric compound after anti-refining adds vulcanization aid in mill or banbury；
4) elastomeric compound is vulcanized, and obtains vulcanite.
8. silane coupler application according to claim 7, it is characterised in that step 1) in, the addition of white carbon black filler
For elastomeric compound gross mass 20%wt-50%wt, the addition of the silane coupler is the 4%wt- of white carbon black filler quality
20%wt.
9., in liquid phase modified white carbon black as described in claim 1-3 any one, wet method mixing prepares answering in high-performance rubber
With, it is characterised in that comprise the following steps：
1) by white carbon water slurry, silane coupler is stirred under the conditions of 25-60 DEG C and obtains modified white carbon black water slurry；
2) latex is added in above-mentioned modified white carbon black water slurry, is obtained filled with white carbon after agitated, flocculation, washing, drying
Rubber master batch；
3) rubber master batch filled with white carbon, other rubber chemicals outside vulcanisation auxiliary agent, in sequentially adding mill or banbury
Carry out mixing and obtain elastomeric compound；
4) above-mentioned elastomeric compound carries out at 100-150 DEG C high temperature is counter to be refined；
5) elastomeric compound after anti-refining adds vulcanization aid in mill or banbury；
6) elastomeric compound is vulcanized, and obtains vulcanite.
10. silane coupler application according to claim 9, it is characterised in that step 1) in, filler addition is elastomeric compound
Gross mass 20%wt-50%wt, the addition of the silane coupler is the 4%wt-20%wt of packing quality.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611098399.7A CN106674593A (en) | 2016-12-03 | 2016-12-03 | Silane coupling agent containing vinyl ether chain segment, and preparation method and application thereof |
Applications Claiming Priority (1)
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| CN109709276A (en) * | 2019-01-04 | 2019-05-03 | 中策橡胶集团有限公司 | The detection method of white carbon black and silane coupling agent Silanization reaction degree in a kind of silica compound |
| CN111019198A (en) * | 2019-12-26 | 2020-04-17 | 河南大学 | Natural rubber/nano silicon dioxide composite material and preparation method thereof |
| CN111073079A (en) * | 2018-10-18 | 2020-04-28 | 中国石油天然气股份有限公司 | Rubber composition for anti-slippery tire and preparation method thereof |
| CN111635428A (en) * | 2020-07-28 | 2020-09-08 | 荆州市江汉精细化工有限公司 | Preparation method of sulfur-containing silane coupling agent containing long-chain alkoxy |
| CN112175418A (en) * | 2019-07-05 | 2021-01-05 | 北京化工大学 | Modified white carbon black, preparation method thereof and masterbatch |
| CN113444285A (en) * | 2021-05-06 | 2021-09-28 | 北京化工大学 | Coupling agent without VOC (volatile organic compound) emission as well as preparation method and application thereof |
| CN113861533A (en) * | 2021-09-29 | 2021-12-31 | 中策橡胶集团有限公司 | White carbon black filled tire tread rubber composition, mixing method and tire |
| CN113980366A (en) * | 2021-11-02 | 2022-01-28 | 华南理工大学 | Preparation method of sulfur-containing silane copolymer modified white carbon black-rubber composite material |
| CN114605464A (en) * | 2022-03-22 | 2022-06-10 | 山东阳谷华泰化工股份有限公司 | Silane coupling agent containing alkoxy chain segment, and preparation method and application thereof |
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| CN109709276A (en) * | 2019-01-04 | 2019-05-03 | 中策橡胶集团有限公司 | The detection method of white carbon black and silane coupling agent Silanization reaction degree in a kind of silica compound |
| CN112175418B (en) * | 2019-07-05 | 2022-05-17 | 北京化工大学 | Modified white carbon black, preparation method thereof and masterbatch |
| CN112175418A (en) * | 2019-07-05 | 2021-01-05 | 北京化工大学 | Modified white carbon black, preparation method thereof and masterbatch |
| CN111019198A (en) * | 2019-12-26 | 2020-04-17 | 河南大学 | Natural rubber/nano silicon dioxide composite material and preparation method thereof |
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| CN113861533A (en) * | 2021-09-29 | 2021-12-31 | 中策橡胶集团有限公司 | White carbon black filled tire tread rubber composition, mixing method and tire |
| CN113980366A (en) * | 2021-11-02 | 2022-01-28 | 华南理工大学 | Preparation method of sulfur-containing silane copolymer modified white carbon black-rubber composite material |
| CN113980366B (en) * | 2021-11-02 | 2022-11-29 | 华南理工大学 | Preparation method of sulfur-containing silane copolymer modified white carbon black-rubber composite material |
| CN114605464A (en) * | 2022-03-22 | 2022-06-10 | 山东阳谷华泰化工股份有限公司 | Silane coupling agent containing alkoxy chain segment, and preparation method and application thereof |
| CN114605464B (en) * | 2022-03-22 | 2023-08-18 | 山东阳谷华泰化工股份有限公司 | Silane coupling agent containing alkoxy chain segment, and preparation method and application thereof |
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