CN106188675A - Anti-old white carbon and preparation method thereof and the application in natural rubber - Google Patents
Anti-old white carbon and preparation method thereof and the application in natural rubber Download PDFInfo
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- CN106188675A CN106188675A CN201610638055.4A CN201610638055A CN106188675A CN 106188675 A CN106188675 A CN 106188675A CN 201610638055 A CN201610638055 A CN 201610638055A CN 106188675 A CN106188675 A CN 106188675A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L7/00—Compositions of natural rubber
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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
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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
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
Abstract
The invention discloses a kind of anti-old white carbon and preparation method thereof and the application in natural rubber.The present invention uses the synthetic route of two-step method, by γ-aminopropyl triethoxysilane and 3,5 di-t-butyl 4 hydroxyl phenylacetic acids are grafted to white carbon surface, make white carbon official energy dough, so not only improve white carbon surface characteristic, make it have preferable dispersibility, make it have certain anti-old function simultaneously, moreover it is possible to suppress age resistor volatilization in rubber and migration.And, environment will not be impacted by such mode, also avirulence, safe and reliable.The present invention is simple, with low cost, and using effect is good.
Description
Technical field
The invention belongs to materials science field, especially one prevents old white carbon and preparation method thereof and natural rubber
Application in glue.
Background technology
White carbon black and white carbon are the reinforcing agents that the application of current rubber industry field is most.Along with oil, natural gas etc. can not
Regenerated resources the most in short supply, and white carbon black is in use to factors such as the harm that environment and health cause, limits
The application of white carbon black.White carbon alternative carbon black completely is used to become the focus of current rubber materials research.White carbon is a kind of
The dendritic aggregation of chain, chemical composition is mainly amorphous silica.A large amount of silicone hydroxyl is contained on its surface, in hydrophilic, easily rolls into a ball
Poly-, cause the poor compatibility of itself and rubber matrix, the dispersibility in rubber is deteriorated therewith.Additionally, in Vulcanization Process of Rubber,
Surface is the compounding ingredient that weakly acidic white carbon easily adsorbs in rubber, postpones sulfuration and causes the problems such as crosslink density reduction, sternly
Heavily have impact on its reinforcing property.In order to solve this problem, need it is modified before using white carbon.Currently used most
It is silane coupler Si69, by sulfide linkage, white carbon is keyed on rubber molecular chain.
In addition to the reinforcing property of rubber, thermal-oxidative aging property is also the important symbol weighing rubber quality.Hot oxygen
Aging belong to radical chain self-catalyzed oxidating reaction, be a kind of irreversible reaction, eventually result in rubber internal structure and destroy,
Lose its use value.Therefore generally require when preparing rubber and add appropriate age resistor, to extend the use of rubber
Life-span.The age resistor used in current rubber broadly falls into greatly diphenylamine, and this kind of age resistor has hypotoxicity.This outer rubber makes
Note also during with that age resistor can volatilize from rubber, migrate, reduce its protection effect.
Phenol age resistor is that a class is nontoxic and have preferable thermal oxidative aging and the feature of environmental protection.By phenol age resistor
It is grafted to white carbon surface be still rarely reported.And about the heat of phenol age resistor grafting white carbon/native rubber composite material
Oxygen aging performance study not yet system is carried out.
Summary of the invention
It is an object of the invention to: provide a kind of anti-old white carbon and preparation method thereof and the application in natural rubber,
It has preferable dispersibility, and also has anti-old function, also inhibits age resistor volatilization in rubber and migration simultaneously,
To overcome prior art not enough.
The present invention is achieved in that anti-old white carbon, calculates by weight, including with 20～30 parts of white carbons, 2～
3 parts of Silane coupling agent KH550s, 1～1.5 part of N, N'-dicyclohexylcarbodiimide and 1.5～2 part 3,5-di-t-butyl-4-hydroxyl
Phenylacetic acid is for preparing raw material.
The preparation method of anti-old white carbon, by above-mentioned mass fraction, is the ethanol of 90% by white carbon and mass percent
Solution mixes, and after sonic oscillation 45min, mixed solution is heated to 55-65 DEG C, and regulates pH value to 6～7, drips water in advance
The Silane coupling agent KH550 solved, under agitation reflux condensation mode 3～5h；Afterwards temperature is increased to 95～100 DEG C, treats
Add N, N'-dicyclohexylcarbodiimide and 3,5-di-t-butyl-4-hydroxyl phenylacetic acid after temperature stabilization, react 2-4h；Finally
Carry out sucking filtration after fully washing with dehydrated alcohol, filtrate is dried in the vacuum drying oven of 85-95 DEG C 10-15h, obtain anti-old
White carbon.
Use glacial acetic acid regulation pH value.
White carbon is 25:200 with the solid-liquid ratio of ethanol solution, and unit is g/mL.
Silane coupling agent KH550 specifically, is added to the water and carries out by the described Silane coupling agent KH550 hydrolyzed in advance
Ultrasonic hydrolysis；The solid-liquid ratio of hydrolysis is 2.5:10～15, and unit is g/mL.
The application in natural rubber is processed of the anti-old white carbon, by anti-old white carbon as reinforcing filler and age resistor,
Anti-old white carbon is 1:2 with the mass ratio of natural rubber.
The reaction principle of the present invention is as follows:
Owing to have employed technique scheme, compared with prior art, the present invention uses the synthetic route of two-step method, will
γ-aminopropyl triethoxysilane and 3,5-di-t-butyl-4-hydroxyl phenylacetic acid is grafted to white carbon surface, makes white carbon official
Energy dough, so not only improves white carbon surface characteristic so that it is have preferable dispersibility, makes it have certain preventing simultaneously
Old function, moreover it is possible to suppress age resistor volatilization in rubber and migration.And, environment will not be impacted by such mode,
Also avirulence, safe and reliable.The present invention is simple, with low cost, and using effect is good.
Accompanying drawing explanation
Accompanying drawing 1 is the infrared spectrogram of rear white carbon before modified；
Accompanying drawing 2 is the TGA collection of illustrative plates of rear white carbon before modified；
Accompanying drawing 3 is storage modulus G of white carbon/native rubber composite material at 60 DEG C ' and the graph of relation of strain
Accompanying drawing 4 is the elongation at break rate of change relation after white carbon/native rubber composite material thermo-oxidative ageing；
Accompanying drawing 5 is the hot strength rate of change relation after white carbon/native rubber composite material thermo-oxidative ageing；
Accompanying drawing 6 is the hardness conservation rate relation after white carbon/native rubber composite material thermo-oxidative ageing；
Accompanying drawing 7 is the thermo-oxidative stability of white carbon/natural rubber vulcanized rubber under air atmosphere；
Accompanying drawing 8 is the thermal cracking of white carbon/natural rubber vulcanized rubber under nitrogen atmosphere；
Accompanying drawing 9 is the TG-DSC figure of comparative example 1 white carbon/natural rubber vulcanized rubber；
Accompanying drawing 10 is the TG-DSC figure of comparative example 2 white carbons/natural rubber vulcanized rubber；
Accompanying drawing 11 is the TG-DSC figure of embodiment 2 white carbons/natural rubber vulcanized rubber；
Accompanying drawing 12 different formulations white carbon/natural rubber apparent activation energy and the relation curve of thermal weight loss rate.
Detailed description of the invention
In below implementing, white carbon selects precipitated silica, model TS-180, Changzhou Le Huan Chemical Co., Ltd.；Rubber
Glue oil, model KN4010, Guangzhou Pei Rui Chemical Co., Ltd.；Natural rubber (NR), zinc oxide, stearic acid, sulfur, diphenylguanidine,
Captax, altax, accelerator TDTM, antioxidant 4020 are provided by Guizhou tire plant；Silane coupler Si69, Dongguan City
Chang Pingyu letter plastifies business department；Silane coupling agent KH550, Dongguan City Chang Pingyu letter plastifies business department；Dehydrated alcohol, analytical pure,
Chongqing Chuan Dong Chemical Co., Ltd.；Glacial acetic acid, analytical pure, Tianjin richness space fine Chinese workers company limited；N, N'-dicyclohexyl carbon
Diimine, analytical pure, Aladdin reagent (Shanghai) Co., Ltd.；3,5-di-t-butyl-4-hydroxyl phenylacetic acids, analytical pure, I
Fourth reagent (Shanghai) Co., Ltd..
Embodiments of the invention 1: the preparation of anti-old white carbon, is 90% by 25g white carbon and 200ml mass percent
Alcohol-water solution is blended in the there-necked flask of 500ml, abundant sonic oscillation 45min, and the frequency of ultrasonic instrument is 40KHZ, power
For 200W；In being moved into oil bath pan, when temperature reaches 60 DEG C, with glacial acetic acid regulation pH value to 6～7, the water in advance of dropping
The 2.5g Silane coupling agent KH550 solved；Whole course of reaction carries out 4h, afterwards by temperature under reflux condensing tube with mechanical agitation
Degree is increased to 97 DEG C, adds the N of 1.5g, N'-dicyclohexylcarbodiimide (DCC), rub by reacting with KH550 after temperature stabilization
You add 3,5-di-t-butyl-4-hydroxyl phenylacetic acid (about 2.96g) than for 1:1, react 3h；Repeatedly with dehydrated alcohol finally
Washing, sucking filtration, white carbon black powder is put into 90 DEG C of vacuum drying ovens and dries 12h, obtain the white carbon black powder with anti-old function.
Embodiments of the invention 2: anti-old white carbon application in natural rubber is processed,
Adding natural rubber in banbury, banbury initial temperature is set to 90 DEG C, and rotor speed is 80r/min, plasticates
After 1min, successively add white carbon and rubber oil, banburying 5min, prepare masterbatch, the masterbatch that banburying is good is put into out
Begin to pratise on refining machine, after masterbatch bag roller, add zinc oxide, stearic acid, diphenylguanidine, M, DM, TDTM, antioxidant 4020 successively
And sulfur.After mix homogeneously, respectively pack three times in left and right, and at thin logical five times, roll spacing modulation 2mm goes out roller and prepares elastomeric compound.By mixing
24h placed at normal temperatures by glue, after using vulcameter to test its sulfurizing time, vulcanizes on vulcanizing press, sulfuration temperature
Degree is 145 DEG C, and in the present embodiment, natural rubber is 2:1 with the mass ratio of white carbon.
In order to verify the technique effect of the present invention, applicant has also carried out contrast test, and the formula employed in experiment is such as
Shown in table 1.
Table 1 (unit: mass parts)
1. Materials testing and characterization
1.1 structural characterizations preventing old type white carbon
Nicolet 6700 Fourier infrared spectrograph using U.S. Sai Mofei company characterize white carbon before modified after
Infrared structure, measures scope 4000～400cm-1；NETZSCH209 type thermal analyzer (Nai Chi company of Germany) is used to characterize Linesless charcoal
Black before modified after heat stability, temperature elevating range 70-700,20 DEG C/min of heating rate.
1.2 vulcanization characteristics tests
Use the vulcanization characteristics of the MD-3000A rheometer test elastomeric compound of Taiwan high ferro Science and Technology Co., Ltd., test
Temperature 145 DEG C, testing time 15min；
1.3RPA test
The rubber machining analyzer RPA2000 using U.S. Alpha Co., Ltd carries out strain sweep to elastomeric compound: temperature 60
DEG C, frequency 1Hz, strain amplitude 0.7～400%；
The test of 1.4 mechanical properties
Use the Insekt10 universal testing machine of Hui Bo testing of materials company of Germany according to GB/T528-1998 test sulfuration
The hot strength of batten, elongation at break and stretching strength, test speed is 500mm min-1；According to GB/T529-1999
The tearing strength of test bars；Shore A type hardness tester according to GB/T531-1999 test bars；
1.5 thermal-oxidative aging property tests
Use the JZ401A type ageing oven of Yangzhou Jing Zhuo test machines factory, measure sulfur according to GB/T3512-2001
Changing glue heatproof air aging performance, aging temperature is 100 DEG C, and ageing time is respectively 1,2,3,4 days, after aging end, by sample
Its correlated performance is measured after placing 10h；
1.6 hot oxygen decomposition kinetics tests
NETZSCH209 type thermal analyzer (Nai Chi company of Germany) is used composite vulcanizate to be tested, intensification model
Enclosing for room temperature～700 DEG C, heating rate is respectively 5,10,20,30 DEG C/min, and atmosphere is nitrogen or air.
2. result and discussion
2.1 infrared spectrograms preventing old white carbon
Fig. 1 is the infrared spectrogram of rear white carbon before modified.In figure, 1104cm-1 is Si O Si antisymmetric stretching vibration
Peak, 958cm-1 is the stretching vibration peak of white carbon surface Si OH, 801cm-1 with 475cm-1 is respectively the right of Si O Si
Claiming stretching vibration peak and bending vibration peak, the absworption peak of 3404cm-1 is by caused by white carbon surface adsorption water.Relative to not
The infrared spectrum of modified white carbon black, modified anti-old type white carbon occurs in that CH at 2932cm-12Stretching vibration peak,
CO stretching vibration absworption peak and the bending vibration absworption peak of NH of amide groups (CONH) is occurred in that at 1629cm-1 and 1516cm-1,
Make carbon black modified success clear.
2.2 heat stability preventing old white carbon
Fig. 2 is the TGA collection of illustrative plates of rear white carbon before modified.Before thermogravimetric test, sample is put into 1h in the baking oven of 70 DEG C, to go
Except white carbon surface adsorption water.It is seen that before 150 DEG C, the weight-loss ratio of unmodified white carbon is more than modified Linesless charcoal
Black, this part weightlessness is to be caused by the absorption water of white carbon remained on surface；After 150 DEG C, unmodified white carbon weight-loss ratio
Decline is to cause due to its surface Si-OH condensation dehydration.Two kinds of modified white carbon hydrophilic weaken, before 150 DEG C,
Weight-loss ratio is less than unmodified white carbon.For the white carbon that age resistor is modified, in the range of 150 DEG C～230 DEG C, under thermal weight loss
Fall is caused by the coupling agent low molecular weight volatile under residual in experimentation；After 230 DEG C, the weightlessness of modified white carbon black
Rate declines further, and declines by a big margin, and this is partially due to caused by the grafting and coating age resistor on white carbon surface.From
Figure understands, unmodified white carbon, and white carbon and the white carbon weight-loss ratio of age resistor modification that KH550 is modified are respectively
The grafting amount of 5.70%, 7.11%, 9.74%, i.e. KH550 is about 1.41%, and the grafting amount of age resistor is about 2.63%.
The vulcanization characteristics of 2.3 white carbons/native rubber composite material
Table 2
Table 2 is the vulcanization characteristics of white carbon/native rubber composite material.Can be seen that the time of scorch change of four kinds of samples
Not quite, and the differing greatly of sulfurizing time.Owing to antioxidant 4020 contains some amine groups, it is possible to promote sulfuration, therefore
The sulfurizing time that with the addition of 4020 age resistor formula b reduces 12.1% than comparative example 1；The sulfurizing time comparison of formula c
Ratio 1 reduces 51.1%, and this is except the effect of amine groups on antioxidant 4020, and topmost reason is that the addition of Si69 makes
White carbon surface polarity is greatly improved, and reduces the white carbon absorption to accelerator, thus sulfurizing time significantly shortens；
The sulfurizing time of formula d reduces 35.4%.From comparative example 2,3, white carbon, can be significantly after silane coupler processes
Shorten sulfurizing time, reduce production cost.MLIt is the minimum torque of sulfuration, phase interaction between its big I indirect reaction filler
With.MLThe least, illustrate that the interaction between filler and filler is the most weak.From comparative example 1,2 sample, adding of antioxidant 4020
Enter MLChange little.The sample of embodiments of the invention 2 reduces compared to the minimum torque of comparative example 2 sample
15.05%, and add the formula c of Si69, minimum torque MLReduce 45.77%, illustrate that white carbon modified for Si69 is natural
Dispersion effect in rubber is optimal.
The mechanical property of 2.4 white carbons/native rubber composite material
Table 3
Shore a hardness is relevant with the crosslinking degree of composite.For comparative example 1,2, owing to accelerator is had by white carbon
Absorption adsorption, promotes sulfuration not exclusively, and natural rubber crosslinking degree is relatively low, causes hardness minimum.And formula comparative example 3 and
Embodiment 2, white carbon is after coupling agent modified, and crosslinking degree all increases, and wherein the hardness of comparative example 3 is up to because in Si69
-S4-take part in sulfuration, crosslinking degree is maximum.
300% stress at definite elongation is often as the foundation judging rubber and filler interaction size.Knowable to from upper table, right
Ratio 3 and embodiment 2 are due to the reunion degree reduction of modified white carbon black, and dispersibility improves, and 300% stretches surely more than unmodified
SiO2The comparative example 1,2 of/NR.And the 300% of comparative example 3 stretches more than embodiment 2 surely, reason is that white carbon modified for Si69 is at sulfur
During change, white carbon can be keyed on rubber macromolecule chain.
Hot strength and tearing strength are to pass judgment on the important indicator of rubber composite mechanical property.As can be seen from the table,
Grafting age resistor is to the formula d on white carbon surface relative to formula b, and hot strength improves 15.44%, and tearing strength improves
11.2%, but the amplification of below formula c.Understand antioxidant 4020 from formula a, b the fracture of native rubber composite material is stretched
Long rate has no significant effect.The SiO that Si69 is modified2/ NR has the elongation at break of minimum, the SiO of grafting age resistor2/ NR's is disconnected
Split percentage elongation also to decline to a great extent, reach 789%.This demonstrate Si69 and can improve vulcanizate with the use preventing old coupling agent
Performance.
The dynamic viscoelastic analysis of 2.5 white carbons/native rubber composite material
Generally, the phenomenon that storage modulus drastically declines along with the increase of strain is referred to as Payne effect.Payne effect can
Reflection filler dispersibility in rubber, Payne effect is the most obvious, illustrates that filler interphase interaction is strong, and dispersibility is the poorest.Fig. 3
It is storage modulus G of white carbon/native rubber composite material at 60 DEG C ' and the graph of relation of strain.As can be known from Fig. 3,
When strain reaches 400%, storage modulus G of all curves ' substantially reach unanimity.Unmodified white carbon be not added with 4020 right
The Payne effect change of the sample that the sample of ratio 1 adds the comparative example 2 of 4020 with unmodified white carbon is little, illustrates anti-old
Agent 4020 is little on white carbon dispersibility impact in natural rubber, and the sample of the unmodified white carbon of both little should
Storage modulus G under Bianing ' higher than other samples, this is because the interaction between unmodified white carbon particle is relatively big, group
The reason that poly-degree is the most serious.From figure it is also seen that the sample of embodiment 2 due to white carbon after modified, the organic one-tenth in surface
Point increasing, surface polarity weakens, and the agglomeration between filler such as weakens at the reason, under small strain, and storage modulus G ' less than not
The sample of the comparative example 1,2 of modified white carbon black.But the sample of the comparative example 3 more than Si69 modified white carbon black, illustrates surface grafting
The white carbon of age resistor dispersibility in natural rubber is improved, but the white carbon that its effect is modified less than Si69.This with
M in vulcanization characteristicsLAnalysis result match.
The thermal-oxidative aging property of 2.6 white carbons/native rubber composite material
Fig. 4 is the elongation at break rate of change relation after white carbon/native rubber composite material thermo-oxidative ageing.From Fig. 4
Understand, unmodified be not added with 4020 SiO2The elongation at break rate of change fall of/NR is maximum, and this is due to thermo-oxidative ageing
During, rubber molecular chain thermal degradation and cause；Si69 modification SiO2/ NR is after being aged for one day, and extension at break subtracts after taking the lead in increasing,
It is likely due to Si69 and there is anti-return originality, it is possible to play the reason of preferable equilibrium cure effect；Surface grafting age resistor
SiO2/ NR, after aging 2 days, its elongation at break rate of change is basically unchanged, and shows to synthesize and is grafted to the anti-of white carbon surface
Old agent has preferably heatproof air aging performance.
Fig. 5 is the hot strength rate of change relation after white carbon/native rubber composite material thermo-oxidative ageing.Unmodified do not add
Add the SiO of 4020 age resistor2/ NR is after aging 1 day, and hot strength rate of change declines to a great extent, and fall slows down afterwards, four kinds
In formula, it is maximum that it declines degree.The comparative example 3 of Si69 modified white carbon black, after aging 2 days, hot strength change takes the lead in increasing
After subtract, ageing resistace is best.And with the addition of the comparative example 2 of 4020 after aging 2 days, its hot strength rate of change is less than grafting
The embodiment 2 of age resistor, illustrates after aging 2 days, antioxidant 4020 compared to synthesis anti-old white carbon to SiO2/ NR draws
Stretch strength retention preferable.
Fig. 6 is the hardness conservation rate relation after white carbon/native rubber composite material thermo-oxidative ageing.As can be known from Fig. 6, exist
Before aging 2 days, the hardness of all formula all increased, and this is due to during thermo-oxidative ageing, the vulcanizate of each formula
There is follow-up sulfuration in sample interior, state of cure (vulcanization) improves, and causes the hardness of vulcanizate to increase.After aging 2 days, due to for a long time
Aging, rubber generation thermal degradation, molecular chain rupture, crosslink density reduce, cause the sample of unmodified white carbon comparative example 1,2
Hardness declines.On the contrary, comparative example 3 is due to the equilibrium cure effect of Si69, and hardness then continues to increase；The hardness of embodiment 2 continues
Keep constant after increase, it may be possible to because the age resistor being grafted to white carbon surface is the most volatile, it is possible to effectively hinder natural rubber
The thermal degradation of glue, shows that the phenol age resistor being grafted to white carbon surface has the most anti-old effect.
The thermo-oxidative stability of 2.7 white carbons/native rubber composite material and thermal cracking stability
As can be seen from Figure 7, during thermo-oxidative ageing, the thermogravimetric curve of white carbon/natural rubber vulcanized rubber is divided into
In two stages, first stage is 200～420 DEG C, and second stage is 420～520 DEG C.After adding age resistor, white carbon/
The thermal weight loss temperature of natural rubber vulcanized rubber increases.Wherein it is grafted to the thermal weight loss temperature of the embodiment 2 on white carbon surface
Relative to not adding the comparative example 1 of any age resistor, thermal weight loss temperature improves 13.4 DEG C, but less than adding the right of antioxidant 4020
Ratio 2,3.The thermo-oxidative ageing process of natural rubber is autocatalysis oxidizing process, belongs to free chain reaction, generates a large amount of
Oxygen radical.For embodiment 2, first these oxygen radicals are captured the hydrogen atom on age resistor phenolic hydroxyl group and are terminated, and lose
Go reactivity, and formed new Phenoxy radical and terminate with other free radical couplings again, finally inhibit white carbon/natural
The carrying out of the thermo-oxidative ageing process of vulcanization of rubber glue.
Under nitrogen atmosphere, as shown in Figure 8, the thermogravimetric curve repeatability of white carbon/natural rubber vulcanized rubber is higher, anti-
The addition of old agent does not produce how many change to thermogravimetric curve.Relative to the heat mistake under air atmosphere, in thermal cracking processes
Weight curve only one of which step.The heat scission reaction of natural rubber vulcanized rubber is carried out with free radical mechanism, mainly happens is that nothing
Rule chain-breaking reaction, by Fig. 7, can be seen that antioxidant 4020 and is grafted to the phenol antiager on white carbon surface to thermo-oxidative ageing in 8
Process just has certain effect that slows down, and the reaction on the random scission of natural rubber vulcanized rubber thermal cracking does not affect.
The thermal oxide activation energy of 2.8 white carbons/native rubber composite material
2.8.1Kissinger method (differentiation)
Kissinger method is a kind of under same sweep speed, the data on a thermal analysis curve record reaction
The method clicking on action mechanical analysis.Kissinger equation is expressed as follows:
In formula: β is heating rate；TpFor the temperature value that thermal analysis curve spectral peak is corresponding；A is pre-exponential factor；R is thermodynamics
Constant；E is thermal oxide activation energy.By ln (β/Tp 2)～1/TpMake graph of a relation, straight slope can try to achieve E, can ask from intercept
Obtain A.Result of calculation is as shown in table 1.
Table 4
The size of activation energy indicates the complexity of sample thermal degradation, and activation energy is the biggest, then needed for there is degradation reaction
The energy wanted is relatively big, i.e. this sample is more difficult to thermal degradation.Table 4 is the thermal oxide activation energy of each formula vulcanizate different phase.From
Understanding in table, with the addition of the vulcanizate of age resistor, the thermal oxide activation energy in its two stages of thermal weight loss is anti-old compared to being not added with
The vulcanizate of agent significantly improves.The thermal oxide activation energy first stage being wherein grafted phenol age resistor improves 10.41kJ/
Mol, second stage improves 14.29kJ/mol, but two stages are below the thermal oxide activation energy of 4020, illustrates to be grafted to white
The anti-aging effect of the phenol age resistor of carbon blacksurface is less than antioxidant 4020.
2.8.1Flynn-Wall-Ozawa method (integration method)
Flynn-Wall-Ozawa method is a kind of method of multiple scaaning speed, i.e. to measured under different heating rates
A plurality of thermal analysis curve is analyzed, thus obtains the kinetic parameter being correlated with.This method can be avoided because of the vacation of reaction mechanism function
If error that is different and that may bring, it is possible to directly obtain activation energy.Can calculate white by Flynn-Wall-Ozawa method
The thermal oxide activation energy of white carbon black/native rubber composite material vulcanizate.Computing formula is:
In formula: β is heating rate；R is thermodynamic equilibrium constant；A is thermal oxidative reaction conversion ratio；E is thermal oxide activation energy；α
For thermal weight loss rate.
Under same reaction depth α (now G (α) is a steady state value), there is phase therewith for different heating rate β i
Corresponding temperature Ti, will often organize data (βi, Ti) bring in (2) formula, available one group of linear equation.This linear equation finally may be used
Matching obtains lg βiThe straight line relevant to 1/Ti, can be obtained activation energy by its slope, and also available activation energy with
The variation relation of reaction depth α.In Practical Calculation, α value is 0.15,0.175,0.2,0.225,0.25,0.275,0.3,
0.325、0.35.Result of calculation such as table 5.
Table 5
By table 5 with Figure 12 it can be seen that along with the increase of thermal weight loss rate, the thermal oxide of white carbon/natural rubber vulcanized rubber
Activation energy is divided into two stages: the first stage, in this stage, the weight-loss ratio with 0.2 was boundary from initiateing weight-loss ratio 0.3,
Before 0.2, thermal oxide activation energy amplitude of variation is little, and after 0.2, thermal oxide activation energy amplitude of variation drastically declines, and this can
Can correspond to thermal oxide automatically speeds up process；Second stage is weight-loss ratio 0.3～0.35, and thermal oxide activation energy is gradually increased,
Decomposition and the aggravation of thermal oxidation process corresponding to oxidation products.It is seen that anti-old white carbon vulcanizate is in difference
Thermal oxide activation energy under thermal weight loss is all higher than the vulcanizate being not added with any age resistor, but less than adding antioxidant 4020 sulfuration
The thermal oxide activation energy of glue.Visible, the novel age resistor being grafted to white carbon surface has certain subtracting to thermo-oxidative ageing process
Slow effect, but effect is weaker than antioxidant 4020, and this is consistent with Kissinger method result.
3. conclusion
The present invention is with silane KH550 as bridge, by amino with carboxyl reaction by 3, and 5-di-t-butyl-4-hydroxyl phenylacetic acid
It is grafted to white carbon surface, makes white carbon have double effects, i.e. improve the dispersibility of white carbon and give its certain preventing always
Function.This anti-old white carbon is applied in natural rubber, when finding the incipient scorch of anti-old white carbon/native rubber composite material
Between change little, sulfurizing time shortens, and minimum torque reduces；Hot strength and tearing strength are not added with 4020 than unmodified
White carbon/natural rubber has been respectively increased 15.0% and 16.4%, but amplification is less than drawing of Si69 modified white carbon black/natural rubber
Stretch intensity and tearing strength；After thermo-oxidative ageing, the performance of various composites is the most on a declining curve, the most unmodified not
White carbon/natural rubber the downward trend of interpolation 4020 is the most obvious, and anti-old white carbon/natural rubber and Si69 modification Linesless charcoal
Black/natural rubber can keep preferable performance.
Claims (6)
1. an anti-old white carbon, it is characterised in that: calculate by weight, including with 20～30 parts of white carbons, 2～3 parts of silicon
Alkane coupling agent KH550,1～1.5 part of N, N'-dicyclohexylcarbodiimide and 2.5～3 part 3,5-di-t-butyl-4-hydroxy benzenes second
Acid is for preparing raw material.
2. the preparation method of the most anti-old white carbon, it is characterised in that: by above-mentioned mass fraction, will
White carbon mixes with the ethanol solution that mass percent is 90%, after sonic oscillation 45min, mixed solution is heated to 55-65
DEG C, and regulate pH value to 6～7, the Silane coupling agent KH550 that dropping hydrolyzes in advance, under agitation reflux condensation mode 3～
5h；Afterwards temperature is increased to 95～100 DEG C, after temperature stabilization, adds N, N'-dicyclohexylcarbodiimide and 3,5-bis-uncle
Butyl-4-hydroxyl phenylacetic acid, reacts 2-4h；Sucking filtration is carried out with dehydrated alcohol, by filtrate at 85-95 DEG C after finally fully washing
Vacuum drying oven is dried 10-15h, obtains anti-old white carbon.
Preparation method the most according to claim 2, it is characterised in that: use glacial acetic acid regulation pH value.
Preparation method the most according to claim 2, it is characterised in that: white carbon is 25 with the solid-liquid ratio of ethanol solution:
200, unit is g/mL.
Preparation method the most according to claim 2, it is characterised in that: the described silane coupler hydrolyzed in advance
Silane coupling agent KH550 specifically, is added to the water and carries out ultrasonic hydrolysis by KH550；The solid-liquid ratio of hydrolysis is 2.5:10～15, single
Position is g/mL.
6. prevent the application in natural rubber is processed of the old white carbon as claimed in claim 1 for one kind, it is characterised in that: will be anti-old
White carbon is 1:2 as reinforcing filler and age resistor, anti-old white carbon with the mass ratio of natural rubber.
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| CN109400987A (en) * | 2018-10-31 | 2019-03-01 | 漯河市邦威橡胶有限公司 | A kind of ageing-resistant high-pressure hose internal layer rubber |
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| CN113817241A (en) * | 2021-10-25 | 2021-12-21 | 徐州工业职业技术学院 | Anti-aging rubber material and preparation method thereof |
| CN114959994A (en) * | 2022-06-01 | 2022-08-30 | 江苏东图纺织有限公司 | Preparation process of wool-polyester pearl fiber shirt fabric |
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| CN109054462A (en) * | 2018-06-22 | 2018-12-21 | 确成硅化学股份有限公司 | A method of it improving white carbon black and prevents old performance |
| CN109054462B (en) * | 2018-06-22 | 2021-02-12 | 确成硅化学股份有限公司 | Method for improving aging resistance of white carbon black |
| CN109400987A (en) * | 2018-10-31 | 2019-03-01 | 漯河市邦威橡胶有限公司 | A kind of ageing-resistant high-pressure hose internal layer rubber |
| CN110562992A (en) * | 2019-10-16 | 2019-12-13 | 广西马中粮油有限公司 | Method for producing rubber reinforcing agent by using rice husk as raw material |
| CN110562992B (en) * | 2019-10-16 | 2022-12-06 | 广西马中粮油有限公司 | Method for producing rubber reinforcing agent by using rice husk as raw material |
| CN113444289A (en) * | 2021-06-15 | 2021-09-28 | 徐业成 | Novel preparation method of antioxidant functionalized white carbon black filler |
| CN113789069A (en) * | 2021-08-18 | 2021-12-14 | 浦林成山（青岛）工业研究设计有限公司 | White carbon black dispersing auxiliary agent and preparation method and application thereof |
| CN113817241A (en) * | 2021-10-25 | 2021-12-21 | 徐州工业职业技术学院 | Anti-aging rubber material and preparation method thereof |
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Application publication date: 20161207 |