CN110092946A - Non-migrating type anti-aging agent and its preparation method and application - Google Patents
Non-migrating type anti-aging agent and its preparation method and application Download PDFInfo
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- CN110092946A CN110092946A CN201910428581.1A CN201910428581A CN110092946A CN 110092946 A CN110092946 A CN 110092946A CN 201910428581 A CN201910428581 A CN 201910428581A CN 110092946 A CN110092946 A CN 110092946A
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- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
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- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
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- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
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- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
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- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
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Abstract
Non-migrating type anti-aging agent and its preparation method and application, it is related to high-performance rubber product technical field, the preparation method of the non-migrating type anti-aging agent is the following steps are included: step 1: white carbon black and anti-aging agent being added in solvent, form uniform dispersion liquid after ultrasonic disperse；Step 2: the dispersion liquid of step 1 is added to atomizer, atomizer temperature is room temperature, and atmosphere is air or inert gas；Step 3: dispersion liquid is atomized by the atomizer in step 2 and is sprayed, the product collected after spray drying is the non-migratory anti-aging agent.The primary partical scale effect of white carbon black had not only been maintained by non-migrating type anti-aging agent prepared by the above method, but also has realized function enhancing, has had both anti ageing property and reinforcing property.
Description
Technical field
The invention belongs to high-performance rubber product technical fields, and in particular to one kind is provided simultaneously with anti-aging function and reinforcement
Non-migrating type anti-aging agent of function and its preparation method and application.
Background technique
It is well known that having polydiene material (such as natural rubber, the styrene fourth of a large amount of unsaturated carbon-to-carbon double bonds
Diene rubber and butadiene rubber etc.) there is outstanding high resiliency, all there is irreplaceability in many industrial circles.But
Carbon-to-carbon double bond and methyl in rubber molecular chain be easy to cause degradation aging under heat and the collective effect of oxygen, make rubber product mistake
Early failure, leads to a large amount of wastes of annual rubber sources, or even threaten the safety of the mankind.Therefore, by postponing its thermal oxide
Ageing process is very important to extend the service life of rubber product.
In order to improve the heat oxygen aging resistance ability of rubber product, aromatic amine or phenol derivatives etc. are added in rubber mass
Chemical antiaging agent is most one of the short-cut method for preventing rubber material from thermo-oxidative ageing occurs.But due to these antioxidant compounds
Molecular weight is low, is easy to migrate from rubber mass, reduces the protection effect of anti-aging agent, and in addition the antioxidant of these migrations is to ring
What border also will cause cannot be neglected pollution.Currently, researcher proposes the preparation method of many non-migrating type anti-aging agents,
The relative molecular weight for such as increasing antioxidant arrives polymer chain for anti-oxidant grafted, makes antioxidant from capsule or hollow material
The methods of sustained release in material (such as galapectite, carbon nanotube), but universal low efficiency, hardly result in large-scale application.
White carbon black is commonly used for rubber-reinforcing filler, and white carbon black reinforced rubber product has the advantage of at least three aspects: epipodium
The problem of guarantor property, very good solution " black pollution "；Energy saving, low-rolling-resistance 22%~35% are every to reduce by 6% rolling resistance
Power can reduce by 1% or so fuel consumption；Traffic safety and riding comfort, green tire have excellent wet-sliding resistant performance and road holding.But
Being white carbon black as reinforcing agent, there are still some defects: 1) white carbon black surface is weakly acidic, and hydrophily is stronger, easily adsorbs in rubber
Compounding agent etc., will lead to vulcanization delay and the problems such as crosslink density reduces, seriously affected reinforcing property；2) white carbon black itself
It is easy to reunite, is difficult to be dispersed in rubber matrix.
Summary of the invention
An object of the present invention is to provide a kind of method of anti-aging agent for preparing non-migrating type, is prepared by this method
Non-migrating type anti-aging agent has both anti-aging and reinforcing property.
To achieve the goals above, the present invention adopts the following technical scheme: a kind of preparation method of non-migrating type anti-aging agent,
Characterized by comprising the following steps:
Step 1: white carbon black and anti-aging agent are added in solvent, form uniform dispersion liquid after ultrasonic disperse；
Step 2: the dispersion liquid of step 1 is added to atomizer, atomizer temperature is room temperature, and atmosphere is air or inertia
Gas；
Dispersion liquid: being atomized by the atomizer in step 2 and sprayed by step 3, the product collected after spray drying
The as described non-migratory anti-aging agent.
Wherein, the mass ratio of the white carbon black and anti-aging agent is (0.05~0.5): 1.
Preferably, the mass ratio of the white carbon black and anti-aging agent is (0.09~0.3): 1.
Wherein, the white carbon black is precipitated silica, fumed silica, superfine silicon dioxide gel, coupling agent change
Property one or more of white carbon black or other surfaces modified white carbon black.
Wherein, the anti-aging agent is one or more of amine, phenol antiager.
Preferably, the anti-aging agent is ketoamine, N- phenyl-α-aniline, N- phenyl-β-naphthylamine, N- phenyl-N'- isopropyl-
One or more of p-phenylenediamine, p-phenylenediamine, N-N'- diphenyl-p-phenylenediamine.
Wherein, the time of ultrasonic disperse is 0.1~3 hour in the step 1, and ultrasonic power is 50~800 watts；It is described
Spray drying temperature is 110~250 DEG C in step 3.
Wherein, in the step 1, the mass ratio of white carbon black and solvent is (0.001~0.2): 1.
On the other hand, the present invention also provides a kind of non-migrating type anti-aging agents being prepared using above-mentioned preparation method, should
Non-migrating type anti-aging agent can be used in rubber product.
Compared with prior art, the present invention at least has following advantages: 1, the non-migrating type that the present invention is prepared is anti-old
What agent was included is rubber product usual component, does not introduce other compounding agents other than rubber product Recipe, will not generate
Generating uncontrollable performance to product influences.2, the present invention is the Surface grafting reaction based on white carbon black primary structure, anti-aging agent
White carbon black primary structure surface can be uniformly coated and be grafted on, grafting rate is high, rather than the part grafting of white carbon black aggregation changes
Property, the non-migratory anti-aging agent surface being prepared can be smaller, easily disperses, does not reunite.3, the present invention uses spray drying process, prevents
The processes such as old agent and the activation of white carbon black, twice dispersing, grafting, drying are completed in spray-drying process, and one kettle way is belonged to
Single step reaction, simple process are suitble to modelling production.
Detailed description of the invention
Fig. 1 is the stereoscan photograph of non-migrating type anti-aging agent prepared by the embodiment of the present invention 1.
Fig. 2 is the infared spectrum of non-migrating type anti-aging agent prepared by the embodiment of the present invention 1.
Fig. 3 is burn-in test sample digital photograph figure prepared by the embodiment of the present invention 2.
Fig. 4 is burn-in test sample digital photograph figure prepared by the embodiment of the present invention 3.
Specific embodiment
To more fully understand difference with the prior art of the present invention convenient for those skilled in the art, below with reference to specific implementation
Example is next, and the present invention will be further explained.
Following embodiment is generally based on following thinking: under atomizer effect, dissociating white carbon black aggregation, is formed
Primary structure forms the graft with good ability of resisting to migration by the graft reaction of primary structure and anti-aging agent molecule, by
This non-migrating type anti-aging agent easily dispersed.The non-migrating type anti-aging agent had both maintained the primary partical scale effect of white carbon black
It answers, and realizes function enhancing, have both anti ageing property and reinforcing property.
Specific implementation step includes: the pre-dispersed of (1), anti-aging agent and white carbon black: antioxidant compound and white carbon black is former
Material is scattered in solvent, ultrasonic disperse 0.1~3 hour, forms uniform dispersion；(2) anti-aging agent and white carbon black graft reaction: will
The dispersion liquid of anti-aging agent and white carbon black carries out atomisation in air or inert gas, spray drying temperature control 110~
250 DEG C, the Spray dried products of collection are non-migrating type anti-aging agent.In above process, can be made by ultrasonic wave effect white
Carbon black aggregate realizes primary structure dispersion, then so that anti-aging agent is adsorbed under atomizer effect again and is evenly coated at primary
The white carbon black surface of structure forms misty anti-aging agent and coats white carbon black drop.Temperature (the i.e. aforementioned spray drying temperature of graft reaction
Degree) it can be determined according to the type and reaction temperature of anti-aging agent and white carbon black in industrialized production, it should be noted that
The too low solvent of temperature cannot volatilize very well, grafting rate is low, the excessively high decomposition that will lead to anti-aging agent of temperature.Spray drying in air or
Atmosphere of inert gases carries out, and on the one hand product can be made preferably to disperse and dry by gas flowing, on the other hand can adjusted
Whole atmosphere adapts to different anti-aging agent reaction conditions.In addition, the mass ratio of white carbon black and solvent be preferably controlled in (0.001~
0.2): 1, the mass ratio control of anti-aging agent and white carbon black is in (0.05~0.5): 1, preferably (0.09~0.3): 1；Anti-aging agent is
By functional form classification can choose thermo oxidative aging anti-aging agent, ozone-resistant aging anti-aging agent, harmful metal ion function inhibitor,
The one or more of antifatigue anti-aging agent, ultra-violet radiation resisting anti-aging agent；It can choose amine, ketoamine, N- according to chemical component
Phenyl-α-aniline, N- phenyl-β-naphthylamine, N- phenyl-N'- isopropyl-p-phenylenediamine, p-phenylenediamine, N-N'- diphenyl-are to benzene
The one or more of the anti-aging agents such as diamines, phenols agent；White carbon black can select in conventional white carbon black and modified white carbon black and group
Close, such as can choose precipitated silica, fumed silica and superfine silicon dioxide gel etc., it also can choose coupling agent
Modified white carbon black or other surfaces modified white carbon black.
Embodiment 1:
In the present embodiment non-migrating type anti-aging agent preparation method the following steps are included:
(1) white carbon black aggregation and p-phenylenediamine, deionized water are configured to a certain concentration according to the mass ratio of 1 ︰, 2 ︰ 100
Suspension, ultrasonic disperse 5 minutes, obtain uniform dispersion liquid；
(2) non-migrating type anti-aging agent is prepared using spray dryer: the dispersion liquid of (1) step is added in spray bottle,
It is spraying using vaporizer, it is passed through argon gas and sprays into atomized drop in the quartz ampoule for being warming up to 150 DEG C in advance.
(3) the non-migrating type anti-aging agent of spray-dried preparation is collected.
Product characterization: the pattern of surface sweeping Electronic Speculum such as attached drawing 1, aggregation has been dispersed, and presents the one of white carbon black
The loose shape of secondary structure degree of dissociation；Infrared spectrum characterization such as attached drawing 2, the white carbon black (SiO after graft modification2) occur in infrared figure
- NH absorption peak (1650cm from p-phenylenediamine-1), and correspond to the absorption peak of-CN of p-phenylenediamine open loop grafting
(2260cm-1).The non-migrating type anti-aging agent for proving that p-phenylenediamine is grafted with white carbon black is successfully prepared.
Performance test: non-migratory anti-aging agent obtained is applied in rubber product, anti-old to compare the non-migratory
The performance difference of agent and existing anti-aging agent, the sample that performance test is used include three groups, the basic recipe (quality point of three groups of samples
Number) it is natural rubber 100, zinc oxide 5, accelerant CZ 1, sulphur 2, stearic acid 2, white carbon black 40 prevents old in three groups of samples
The dosage of agent is varied, wherein plus in the sample sets of anti-aging agent anti-aging agent content is not 0, antioxidant 4010 and Jia Ben is added to implement
Anti-aging agent content is 2 in the involved sample sets for adding non-migrating type anti-aging agent of example.By the formula with conventional side on double rod open mills
Method is kneaded, and is parked 1 day, 150 DEG C of vulcanizations on vulcanizing press.To not plus anti-aging agent plus antioxidant 4010NA, plus non-migratory
Anti-aging agent and three groups of samples without aging carry out Mechanics Performance Testing, and result be the test result of addition non-migratory anti-aging agent
Be substantially better than plus antioxidant 4010NA and not plus anti-aging agent sample, illustrate non-migrating type anti-aging agent involved by this example can to
To preferable reinforcing effect.Since it the present invention relates to anti-aging agent, should be paid close attention in the test knot after thermo-oxidative ageing
Fruit.The thermo-oxidative ageing of 48h is carried out under the conditions of 100 DEG C, the mechanical property of three groups of samples is as shown in table 1.
Mechanical property after 1 three groups of sample aging 48h of table.
As can be seen from the above table, after aging, the film performance for adding non-migratory anti-aging agent is better than not adding anti-aging agent
With the film of common 4010NA anti-aging agent, illustrates non-migrating type anti-aging agent involved by this example while there is preferable anti-aging
Energy.
Embodiment 2:
In the present embodiment non-migrating type anti-aging agent preparation method the following steps are included:
(1) in mass ratio it is the ratio of 100:20 by the white carbon black of vapor phase method and silane coupling agent Si69, stirs at 145 DEG C
30 minutes.Acceptor modified white carbon black is dried to obtain through extracting.
(2) modified white carbon black and mutual-amido two polyaniline, deionized water will be configured to centainly according to the mass ratio of 1 ︰, 2 ︰ 100
The suspension of concentration ultrasonic disperse 5 minutes, obtains uniform dispersion liquid；
(3) dispersion liquid of (1) step is added in spray bottle, spraying using vaporizer, being passed through argon gas will be atomized
Drop penetrating is warming up in 150 DEG C of quartz ampoule in advance.
Performance test: non-migratory anti-aging agent obtained is applied in rubber product, anti-old to compare the non-migratory
The performance difference of agent and existing anti-aging agent, the sample that performance test is used include three groups, the basic recipe (quality point of three groups of samples
Number) it is natural rubber 100, zinc oxide 5, accelerant CZ 1, sulphur 2, stearic acid 2, white carbon black 40, the addition manner ginseng of anti-aging agent
Examine embodiment 1.It is kneaded, parks 1 day, 145 DEG C of sulphur on vulcanizing press in conventional manner on double rod open mills by the formula
Change.
To anti-aging agent plus antioxidant 4010NA plus non-migratory anti-aging agent is not added and three groups of samples without aging carry out
Mechanics Performance Testing, test result and embodiment 1 are consistent.In addition, to adding antioxidant 4010NA and adding this example non-migrating
2 groups of samples of property anti-aging agent have carried out the thermo-oxidative ageing of 48h under the conditions of 100 DEG C, are stretched on universal tensile testing machine
Product number photo such as attached drawing 3 after strength test.After the thermo-oxidative ageing by 48 hours, the glue of conventional anti-aging agent is added
For piece under tensile stress effect, many anti-aging agents, tensile strength 13.4MPa has been precipitated in surface.The glue of non-migratory anti-aging agent
Piece does not occur transport phenomena (such as attached drawing 3, the table of anti-aging agent after aging 48 hours under tensile stress effect yet
Face is still very smooth), tensile strength is still up to 22.6MPa, it was demonstrated that non-migrating type anti-aging agent performance is anti-better than small molecule old
Agent 4010NA.
Embodiment 3:
In the present embodiment non-migrating type anti-aging agent preparation method the following steps are included:
(1) white carbon black of vapor phase method and coupling agent KH560 are pre-processed in toluene solvant, by the matter of white carbon black and Si69
Amount compares the ratio for 100:40, is stirred at reflux 5 hours at 90 DEG C.Acceptor modified white carbon black is dried to obtain through extracting.
(2) modified white carbon black is configured to mutual-amido two polyaniline, deionized water according to the mass ratio of 1 ︰, 2 ︰ 100 certain dense
The suspension of degree ultrasonic disperse 5 minutes, obtains uniform dispersion liquid；
(3) dispersion liquid of (1) step is added in spray bottle, spraying using vaporizer, being passed through argon gas will be atomized
Drop sprays into is warming up to drying in 150 DEG C of quartz ampoule in advance.
Performance test: non-migratory anti-aging agent obtained is applied in rubber product, anti-old to compare the non-migratory
The performance difference of agent and existing anti-aging agent, the sample that performance test is used include three groups, the basic recipe (quality point of three groups of samples
Number) it is natural rubber 100, zinc oxide 5, accelerant CZ 1, sulphur 2, stearic acid 2, white carbon black 40, the addition manner ginseng of anti-aging agent
Examine embodiment 1.It is kneaded, parks 1 day, 150 DEG C of sulphur on vulcanizing press in conventional manner on double rod open mills by the formula
Change.
In the same manner as in Example 2, to not plus anti-aging agent plus antioxidant 4010NA plus non-migratory anti-aging agent and without aging
Three groups of samples carry out Mechanics Performance Testing, test result is equally consistent with embodiment 1.Antioxidant 4010NA, addition will be added originally
2 groups of samples of example non-migratory anti-aging agent have carried out the thermo-oxidative ageing of 48h under the conditions of 100 DEG C, in universal tensile testing machine
Product photo figure such as attached drawing 4 after upper carry out tensile strength test.After the thermo-oxidative ageing by 48 hours, conventional anti-aging agent
Film under tensile stress effect, the visible one layer of white small-molecule substance in surface, it was demonstrated that anti-aging agent migration, volatilization are very bright
It is aobvious, tensile strength 13.8MPa.The film of non-migratory anti-aging agent is after aging 48 hours, even if under tensile stress effect
The transport phenomena (such as attached drawing 4, surface are still very smooth) of anti-aging agent is not occurred yet, tensile strength is still up to 25.5MPa,
Non-migrating type anti-aging agent performance is demonstrated better than small molecule antioxidant 4010NA.
Embodiment 4:
In the present embodiment non-migrating type anti-aging agent preparation method the following steps are included:
(1) white carbon black of vapor phase method and polymer substance are carried out surface to be modified, by white carbon black and epoxy natural rubber ENR
In mass ratio it is the ratio of 100:120, is kneaded 5 hours in 160 DEG C of torque rheometers.It is white that ENR modification is dried to obtain through extracting
Carbon black.
(2) modified white carbon black and mutual-amido two polyaniline, deionized water will be configured to centainly according to the mass ratio of 1 ︰, 2 ︰ 100
The suspension of concentration ultrasonic disperse 5 minutes, obtains uniform dispersion liquid；
(3) dispersion liquid of (1) step is added in spray bottle, spraying using vaporizer, being passed through argon gas will be atomized
Drop sprays into is warming up to drying in 150 DEG C of quartz ampoule in advance.
Performance test: non-migratory anti-aging agent obtained is applied in rubber product, anti-old to compare the non-migratory
The performance difference of agent and existing anti-aging agent, the sample that performance test is used include three groups, the basic recipe (quality point of three groups of samples
Number) it is natural rubber 100, zinc oxide 5, accelerant CZ 1, sulphur 2, stearic acid 2, white carbon black 40, the addition manner ginseng of anti-aging agent
Examine embodiment 1.It is kneaded, parks 1 day, 150 DEG C of sulphur on vulcanizing press in conventional manner on double rod open mills by the formula
Change.
To anti-aging agent plus antioxidant 4010NA plus non-migratory anti-aging agent is not added and three groups of samples without aging carry out
Mechanics Performance Testing, test result are equally consistent with embodiment 1.Anti-aging agent plus antioxidant 4010NA will not added, add this example
It is as shown in table 2 that three groups of samples of non-migratory anti-aging agent have carried out the thermo-oxidative ageing of 48h, mechanical property under the conditions of 100 DEG C.
After aging, using ENR it is modified grafting mutual-amido two polyaniline non-migratory anti-aging agent film performance better than other two
The film of group, it was demonstrated that advantage of the non-migrating type anti-aging agent in rubber product involved by the present embodiment.
Mechanical property after 2 three groups of sample aging 48h of table
Above-described embodiment is the preferable implementation of the present invention, and in addition to this, the present invention can be realized with other way,
Do not depart from the technical program design under the premise of it is any obviously replace it is within the scope of the present invention.
In order to allow those of ordinary skill in the art more easily to understand the improvements of the present invention compared with the existing technology, this
Some attached drawings of invention and description have been simplified, and for the sake of clarity, present specification is omitted some other members
Element, the element that those of ordinary skill in the art should be aware that these are omitted also may make up the contents of the present invention.
Claims (10)
1. a kind of preparation method of non-migrating type anti-aging agent, which comprises the following steps:
Step 1: white carbon black and anti-aging agent are added in solvent, form uniform dispersion liquid after ultrasonic disperse；
Step 2: the dispersion liquid of step 1 is added to atomizer, atomizer temperature is room temperature, and atmosphere is air or indifferent gas
Body；
Dispersion liquid: being atomized by the atomizer in step 2 and sprayed by step 3, and the product collected after spray drying is
The non-migratory anti-aging agent.
2. the preparation method of non-migrating type anti-aging agent as described in claim 1, it is characterised in that: the white carbon black and anti-aging agent
Mass ratio be (0.05~0.5): 1.
3. the preparation method of non-migrating type anti-aging agent as claimed in claim 2, it is characterised in that: the white carbon black and anti-aging agent
Mass ratio be (0.09~0.3): 1.
4. the preparation method of non-migrating type anti-aging agent as described in claim 1, it is characterised in that: the white carbon black is precipitating two
In silica, fumed silica, superfine silicon dioxide gel, acceptor modified white carbon black or other surfaces modified white carbon black
It is one or more of.
5. the preparation method of non-migrating type anti-aging agent as described in claim 1, it is characterised in that: the anti-aging agent be amine,
One or more of phenol antiager.
6. the preparation method of non-migrating type anti-aging agent as described in claim 1, it is characterised in that: the anti-aging agent be ketoamine,
N- phenyl-α-aniline, N- phenyl-β-naphthylamine, N- phenyl-N'- isopropyl-p-phenylenediamine, p-phenylenediamine, N-N'- diphenyl-right
One or more of phenylenediamine.
7. the preparation method of non-migrating type anti-aging agent as claimed in claim 3, it is characterised in that: in the step 1, hard charcoal
The black mass ratio with solvent is (0.001~0.2): 1.
8. the preparation method of non-migrating type anti-aging agent as claimed in claim 7, it is characterised in that: ultrasound point in the step 1
The scattered time is 0.1~3 hour, and ultrasonic power is 50~800 watts；Spray drying temperature is 110~250 in the step 3
℃。
9. non-migrating type anti-aging agent, it is characterised in that: be prepared into using preparation method described in any one of claim 1-8
It arrives.
10. application of the non-migrating type anti-aging agent as claimed in claim 9 in rubber product.
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| CN110092946B (en) | 2022-02-08 |
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