CN110016151A - A kind of modified butadiene rubber and its preparation method and application - Google Patents
A kind of modified butadiene rubber and its preparation method and application Download PDFInfo
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- CN110016151A CN110016151A CN201810014254.7A CN201810014254A CN110016151A CN 110016151 A CN110016151 A CN 110016151A CN 201810014254 A CN201810014254 A CN 201810014254A CN 110016151 A CN110016151 A CN 110016151A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
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- B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
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- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/205—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase
- C08J3/21—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase the polymer being premixed with a liquid phase
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- C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
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- C08J2457/02—Copolymers of mineral oil hydrocarbons
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- C08J2461/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
- C08J2461/04—Condensation polymers of aldehydes or ketones with phenols only
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- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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Abstract
The present invention provides a kind of modified butadiene rubber and its preparation method and application.Wherein, the preparation method of the modification butadiene rubber includes: that butadiene rubber is dissolved in organic solvent, obtains rubber solutions；The agent of rubber tear-proof, rubber stiffener and above-mentioned rubber solutions are uniformly mixed, mixture is obtained；The organic solvent in said mixture is removed, modified butadiene rubber is obtained.The preparation method of modified butadiene rubber provided by the invention can significantly improve the tearing toughness of vulcanized rubber and rubber product, resistance to puncture ability and resistance to collapse use up block ability after over cure such as processes at the processing.
Description
Technical field
The invention belongs to technique for modifying rubbers fields, and in particular to a kind of modified butadiene rubber and preparation method thereof and answer
With more particularly to a kind of high tear performance modification butadiene rubber and its modified technique and the modification butadiene rubber in vapour
Application in the rubber products such as wheel tire.
Background technique
Butadiene rubber (BR) is cis--Isosorbide-5-Nitrae-polybutadiene rubber abbreviation, is the knot as made of butadiene monomers
The regular synthetic rubber of structure, cis-structure content is 95% or more.Since the molecular structure of butadiene rubber is more regular, molecule
Chain is very submissive, and therefore, compared with the synthetic rubber such as natural rubber or butadiene-styrene rubber, butadiene rubber usually has more outstanding
Flexibility, elasticity, wearability, flexible resistance, resistance to low temperature etc., therefore in automobile tire, shoemaking and building field etc., all
It has a very wide range of applications.Especially, use butadiene rubber for raw material, the automobile tire obtained after the processing such as vulcanizing treatment
Have the characteristics that high wet-sliding resistant and low-rolling-resistance；Simultaneously as the preparation process of butadiene rubber developed it is more mature,
Cost of material and processing cost are all lower, and therefore, butadiene rubber is the preferred material of always automobile tire rubber.
But due to the limitation of butadiene rubber own molecular structure, the vulcanized rubber and vapour that cause its following process to obtain
The tearing strength of the rubber products such as wheel tire is lower, resistance to puncture ability and resistance to collapses that use up block ability also all undesirable.Therefore, with
When preparing the rubber products such as automobile tire, butadiene rubber has to be used in combination with other glue kinds such as butadiene-styrene rubber, while along fourth rubber
The dosage of glue should be usually more than 30%, to guarantee automobile tire while maintaining high wet-sliding resistant and low-rolling-resistance
Tearing strength, resistance to puncture ability and resistance to collapse use up block ability and meet related request.
Therefore, how butadiene rubber is modified, the modification butadiene rubber made for vulcanized rubber or into
When one step is for rubber products such as automobile tires, can have good tearing strength, resistance to puncture ability and resistance to collapse to use up block energy
Power is that have technical problem to be solved at present.
Summary of the invention
For the above-mentioned problems in the prior art, the present invention provides a kind of modified butadiene rubber and preparation method thereof,
Block energy is used up for improving tearing strength, resistance to puncture ability and resistance to collapse of the butadiene rubber when for vulcanized rubber and rubber product
Power；The present invention also provides application of the above-mentioned modified butadiene rubber in rubber product, and use above-mentioned modified butadiene rubber institute
Process obtained vulcanized rubber.
For the tearing strength for improving butadiene rubber, present invention firstly provides a kind of preparation method of modified butadiene rubber, packets
It includes:
Butadiene rubber is dissolved in organic solvent, rubber solutions are obtained；
The agent of rubber tear-proof, rubber stiffener and above-mentioned rubber solutions are uniformly mixed, mixture is obtained；
The organic solvent in said mixture is removed, modified butadiene rubber is obtained.
Above-mentioned preparation method is actually modified butadiene rubber using the agent of rubber tear-proof and rubber stiffener
Process.In this modifying process, realize that being sufficiently mixed between the agent of rubber tear-proof, rubber stiffener and butadiene rubber is to close
Key.
Butadiene rubber is dissolved in organic solvent by the present invention first, so that butadiene rubber is used as " solute ", is uniformly dispersed
In organic solvent this " solvent ", more uniform rubber solutions have been obtained；Then by rubber solutions and the agent of rubber tear-proof,
Rubber stiffener mixing, enables the agent of rubber tear-proof and rubber stiffener to be scattered in the molecular structure of butadiene rubber.It compares
The direct physical mixed in solid form in conventional method, or stirred by heating melting and realize mixing, it is provided by the present invention
Mixed method, be easier to realize the agent of rubber tear-proof and rubber stiffener it is evenly dispersed in butadiene rubber.
Also, the study found that compared with using vulcanized rubber made from unmodified butadiene rubber, using above-mentioned hybrid mode
Obtained modification butadiene rubber, then the vulcanized rubber obtained through vulcanizing treatment, tearing strength, resistance to puncture ability and resistance to collapse flower
Chip off-falling ability, which has, to be obviously improved.Inventor's analysis, it may be possible to due to the addition of the agent of rubber tear-proof and rubber stiffener, change
The molecular chain structure of butadiene rubber script is become.So subsequent carrying out the processing such as vulcanizing modified butadiene rubber to prepare vulcanization
During rubber and rubber product, the molecular network structure of butadiene rubber also changes, and is conducive to improve modified along fourth
Interaction force between rubber and filler, and then the tearing that can be improved the rubber products such as vulcanized rubber even automobile tire is strong
Degree, resistance to puncture ability and resistance to collapse use up block ability.
Above-mentioned mixed process can be and the agent of rubber tear-proof and rubber stiffener are added in butadiene rubber solvent, so
Implement adequately stirring afterwards, the agent of rubber tear-proof and rubber stiffener can be homogeneously dispersed in butadiene rubber.Then, i.e.,
It can remove the organic solvent in said mixture.
The progress of this field conventional technology can be used in the process for removing organic solvent in mixture.As the present invention
One of preferred embodiment, can use terminator, remove mixture in organic solvent.Specifically, being to mixture
Middle addition terminator is precipitated the agent of rubber tear-proof, rubber stiffener and butadiene rubber in mixture from organic solvent, so
By separation of solid and liquid, obtained block-like elastic solid (Hookean body) is modified butadiene rubber.
It is appreciated that above-mentioned terminator used, can make butadiene rubber, the agent of rubber tear-proof and the rubber in mixture
Reinforcing agent is precipitated from organic solvent, and in the process, does not influence butadiene rubber, the agent of rubber tear-proof and rubber reinforcement also
Uniform mixing between agent.
Specifically, above-mentioned terminator can be according to organic solvent and the physicochemical property of the agent of rubber tear-proof, rubber stiffener
Etc. factors reasonably select, such as can be at least one of containing methanol, ethyl alcohol, ethylene glycol and glycerine in the terminator.?
In specific implementation process of the present invention, commonly used terminator is methanol, ethyl alcohol, ethylene glycol or glycerine, will be organic molten
Agent is sufficiently separated with butadiene rubber, the agent of rubber tear-proof and rubber stiffener.
In specific implementation process of the present invention, above-mentioned terminator is added in mixture, then contains butadiene rubber, rubber
The solid mixture of tear-proof agent and rubber stiffener is layered with the liquid mixture containing organic solvent and terminator, so
By separation of solid and liquid, modified butadiene rubber is finally obtained, specially block-like elastic solid (Hookean body).
It is appreciated that may also remain a small amount of organic solvent in above-mentioned block-like elastic solid (Hookean body), therefore can also be to it
Further implement to be dried, to completely remove organic solvent therein.
It is appreciated that during above-mentioned modified to butadiene rubber, rationally control butadiene rubber, the agent of rubber tear-proof and
Ratio between reinforcing agent can make finally obtained vulcanized rubber and rubber product be able to maintain butadiene rubber itself original
Performance advantage, and improve tearing strength, resistance to puncture ability and resistance to collapse simultaneously and use up block ability.
In specific implementation process of the present invention, butadiene rubber: rubber tear-proof agent: the weight ratio of rubber stiffener is 100:
(1~50): (1~10).That is, being in terms of 100 parts by the weight of butadiene rubber, the weight of rubber tear-proof agent is 1~50 part, rubber
The dosage of glue reinforcing agent is 1~10 part.
Modified butadiene rubber, can be butadiene rubber commonly used in the art, for example prepare vapour at present used in the present invention
Butadiene rubber raw material commonly used by wheel tire.It is appreciated that the molecular weight and molecular weight distribution of butadiene rubber are rationally controlled, for
Make modified rubber that the advantages such as the original low-rolling-resistance of butadiene rubber and high wet-sliding resistant performance be kept to be advantageous, it is usually controllable
The number-average molecular weight of butadiene rubber is 80,000~120,000, and molecular weight distributing index be (weight average molecular weight and number-average molecular weight
Ratio) it is 1.5~5.0.
Correspondingly, above-mentioned for dissolving the organic solvent of butadiene rubber, can be this field is commonly used by prepare glue
One of organic solvent, including but not limited to hexane, hexamethylene, toluene and tetrahydrofuran are a variety of.
Rubber tear-proof agent used in the present invention, also referred to as tear-proof modifying agent.The study found that if rubber tear-proof agent
Molecular structure in contain double bond functional group and/or amino group, for improving butadiene rubber tearing strength after curing, resistance to
Puncture ability and resistance to collapse that use up block ability be very favorable.In specific implementation process of the present invention, rubber tear-proof used
Agent is selected from phenolic resin, terpene resin, C 5 petroleum resin (5 resin of carbon), C 9 petroleum resin (9 resin of carbon), acrylamide
At least one of with polyacrylamide.
Further, the mass ratio between above-mentioned tear-proof modifying agent and butadiene rubber can be (20~50): 100, lead to
Often it is (20~30): 100.
Rubber stiffener used in the present invention can be common reinforcing agent during current rubber processing.In this hair
In bright specific implementation process, rubber stiffener used can be at least one in carbon black, white carbon black, calcium carbonate and magnesia
Kind, it is also possible to other reinforcing agents.
Specifically, the mass ratio between above-mentioned rubber stiffener and butadiene rubber can be (1~8): 100, usually control
Mass ratio between rubber stiffener and butadiene rubber is (5~8): 100.
The present invention also provides a kind of using modified butadiene rubber made from above-mentioned preparation method.
It is appreciated that the modification butadiene rubber enabled to is being used to prepare vulcanized rubber due to above-mentioned preparation method
And when rubber product, the tearing strength, resistance to puncture ability and resistance to collapse that can significantly improve vulcanized rubber and rubber product use up block
Ability.
Secondly the present invention provides a kind of vulcanized rubber, be to be obtained using above-mentioned modified butadiene rubber through vulcanization processing.
Specifically, carrying out the technique of vulcanization processing to butadiene rubber at present, provided by the present invention change may be applicable to
Property butadiene rubber, such as can be according to recording in " GB/T 8660-2008 polymerisation in solution type butadiene rubber (BR) evaluation method "
Code test formula (table 1, non-oil-filled glue) and method C2 carry out mixing vulcanization.Specific mixing formula are as follows: 100 parts by weight it is upper
State modified butadiene rubber, the stearic acid of 2 parts by weight, the zinc oxide of 3 parts by weight, the accelerator TBBS of 0.9 parts by weight, 60 parts by weight
Universal industrial reference black, 15 parts by weight ASTM103# operation oil and 1.5 parts by weight sulphur.After tested, compared to not
The vulcanized rubber that modified butadiene rubber is prepared, vulcanized rubber provided by the present invention, in tearing strength, resistance to puncture ability
With it is resistance to collapse use up block ability in terms of be obviously improved.
The present invention finally provides application of the above-mentioned modified butadiene rubber in rubber product.
Above-mentioned rubber product, for example can be automobile tire, rubber overshoes etc..As described above, modification provided by the present invention is suitable
Buna can assign the rubber product tearing strength more outstanding when for rubber products such as automobile tires.
For manufacturing automobile tire, using modified butadiene rubber provided by the present invention as raw material, replace original suitable
Buna, can improve the tearing strength of automobile tire, and be still able to keep performance advantage brought by butadiene rubber.
Moreover, increasing usage amount of the butadiene rubber in automobile tire, the tearing strength of automobile tire can not only be improved,
And the other performances such as high wet-sliding resistant and low-rolling-resistance also still can be good at keeping, to significantly reduce automotive wheels
The cost of material of tire.
The present invention provides a kind of modified butadiene rubber, for the modification butadiene rubber when being used for vulcanized rubber, tearing is strong
Degree, resistance to puncture ability and resistance to collapse use up block ability and all have clear improvement, and wherein the tearing strength of vulcanized rubber improves more before modified
30%~60%, resistance to puncture ability improves 45%~65%, and resistance to collapse is used up block ability and be also obviously improved.
The present invention provides the preparation method of above-mentioned modified butadiene rubber, the preparation method step simple possibles, convenient for big
The promotion and application of scale.
It the present invention also provides a kind of vulcanized rubber, is obtained by above-mentioned modified butadiene rubber vulcanization processing.Institute of the present invention
The vulcanized rubber of offer, the more unmodified obtained vulcanized rubber of butadiene rubber in tearing strength, resistance to puncture ability and resistance to collapse
It all has clear improvement in terms of using up block ability.
The present invention also provides application of the above-mentioned modified butadiene rubber in the rubber products such as automobile tire.Using the present invention
Modification butadiene rubber when being that raw material manufactures the rubber products such as automobile tire, under conditions of butadiene rubber high usage amount, not only
Rubber product tear resistance can be improved, and the performance advantages such as its original wet-sliding resistant performance and low-rolling-resistance still obtain
Good holding is arrived, it is thus possible to significantly reduce the cost of material of rubber product；And under the premise of identical usage amount, it can
Improve the tearing strength of rubber product, resistance to puncture ability and it is resistance to collapse block ability of using up, and the assigned rubber product of butadiene rubber
Excellent performance also still can be good at keeping.
Detailed description of the invention
The drawings herein are incorporated into the specification and forms part of this specification, and shows the implementation for meeting the disclosure
Example, and together with specification for explaining the principles of this disclosure.
Fig. 1 is the flow chart of modified butadiene rubber preparation method provided by the embodiment of the present invention.
Through the above attached drawings, it has been shown that the specific embodiment of the disclosure will be hereinafter described in more detail.These attached drawings
It is not intended to limit the scope of this disclosure concept by any means with verbal description, but is by referring to specific embodiments
Those skilled in the art illustrate the concept of the disclosure.
Specific embodiment
In order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below in conjunction with the embodiment of the present invention
In attached drawing, technical scheme in the embodiment of the invention is clearly and completely described, it is clear that described embodiment is
A part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, those of ordinary skill in the art
Every other embodiment obtained without making creative work, shall fall within the protection scope of the present invention.
In the present invention, the test of tearing strength is in accordance with national standard " GB/T 529-2008 vulcanized rubber or thermoplastic elastomer
The measurement of tearing strength ".
Thorn resistance can be measured using rubber dynamic cutting test machine, and puncture frequency is 100 beats/min, be claimed before and after puncture
Quality is measured, thorn resistance energy is evaluated by vulcanized rubber mass decrement.
Resistance to collapse uses up block ability by the appearance measurement of the sample after observation rubber dynamic cutting test machine experiment, no
Be more than the blob of viscose of 0.5cm it is excellent, it is poor more than the blob of viscose of 1.0cm that the blob of viscose of 0.5cm~1.0cm, which is good,.
Butadiene rubber used in following embodiment and comparative example is purchased from middle petroleum Dushanzi petro-chemical corporation.
Embodiment 1
The present embodiment provides a kind of preparation method of modified butadiene rubber, concrete technology flow process is walked referring to table 1, including as follows
It is rapid:
In hexane by the butadiene rubber dissolution of 100 parts by weight, rubber solutions are obtained, wherein the equal molecule of the number of butadiene rubber
Amount about 8.2 ten thousand, molecular weight distributing index 1.8；
The carbon black of phenolic resin and 5 parts by weight that 20 parts by weight are added into above-mentioned rubber solutions obtains after mixing evenly
Mixture；
Ethyl alcohol is added into said mixture, analyses the solid mixture being made of butadiene rubber, phenolic resin and carbon black
It is layered out, is thermally dried through being separated by solid-liquid separation, and to obtained solid mixture, further removes organic solvent therein,
Obtain modified butadiene rubber.
The standard examination recorded according to table 1 in " GB/T 8660-2008 polymerisation in solution type butadiene rubber (BR) evaluation method "
The method C2 for testing formula (non-oil-filled glue) and recording, by the modification butadiene rubber of 100 parts by weight, the stearic acid of 2 parts by weight, 3
The zinc oxide of parts by weight, the accelerator TBBS of 0.9 parts by weight, the universal industrial reference blacks of 60 parts by weight, 15 parts by weight
The sulphur of ASTM103# operation oil and 1.5 parts by weight, vulcanizes in mixing and is kneaded, vulcanizes in opening rubber mixing machine, vulcanized
Rubber.
It tests the tear resistance of vulcanized rubber, thorn resistance energy and resistance to collapses block ability of using up, specific test result such as table 1
It is shown.
Comparative example 1
Using the butadiene rubber in embodiment 1 before modified as raw rubber, according in embodiment 1 formula and method preparation vulcanization
Rubber.
That is, by the butadiene rubber of 100 parts by weight, the stearic acid of 2 parts by weight, the zinc oxide of 3 parts by weight, 0.9 parts by weight
Accelerator TBBS, the universal industrial reference black of 60 parts by weight, 15 parts by weight ASTM103# operation oil and 1.5 parts by weight sulphur
Sulphur is kneaded in opening rubber mixing machine, vulcanizes, obtains vulcanized rubber.
It tests the tear resistance of vulcanized rubber, thorn resistance energy and resistance to collapses block ability of using up, specific test result such as table 1
It is shown.
The test result of comparative example 1 and comparative example 1 is it is found that using the modification butadiene rubber in embodiment 1 as former
Expect vulcanized rubber obtained, tear resistance, which improves 38.2%, thorn resistance, can improve 63.5%, and resistance to collapse uses up block energy
There has also been be obviously improved for power.
Embodiment 2
The present embodiment provides a kind of preparation method of modified butadiene rubber, concrete technology flow process is walked referring to table 1, including as follows
It is rapid:
The butadiene rubber of 100 parts by weight is dissolved in toluene, rubber solutions are obtained, wherein the equal molecule of the number of butadiene rubber
Amount about 10.5 ten thousand, molecular weight distributing index 2.0.
The terpene resin of 25 parts by weight and the white carbon black of 6 parts by weight are added into above-mentioned rubber solutions, stirs evenly, obtains
Mixture；
Methanol is added into said mixture, makes the solid mixture being made of butadiene rubber, terpene resin and white carbon black
Layering is precipitated, is thermally dried, further removes therein organic molten through being separated by solid-liquid separation, and to obtained solid mixture
Agent obtains modified butadiene rubber.
According to the formula and method in embodiment 1, by this implement in modification butadiene rubber mixed in opening rubber mixing machine
Refining, vulcanization, obtain vulcanized rubber.
It tests the tear resistance of vulcanized rubber, thorn resistance energy and resistance to collapses block ability of using up, specific test result such as table 1
It is shown.
Comparative example 2
Using the butadiene rubber in embodiment 2 before modified as raw rubber, according in embodiment 1 formula and method preparation vulcanization
Rubber.
That is, by the butadiene rubber of 100 parts by weight, the stearic acid of 2 parts by weight, the zinc oxide of 3 parts by weight, 0.9 parts by weight
Accelerator TBBS, the universal industrial reference black of 60 parts by weight, 15 parts by weight ASTM103# operation oil and 1.5 parts by weight sulphur
Sulphur is kneaded in opening rubber mixing machine, vulcanizes, obtains vulcanized rubber.
It tests the tear resistance of vulcanized rubber, thorn resistance energy and resistance to collapses block ability of using up, specific test result such as table 1
It is shown.
The test result of comparative example 2 and comparative example 2 is it is found that using the modification butadiene rubber in embodiment 2 as former
Expect vulcanized rubber obtained, tear resistance, which improves 56.5%, thorn resistance, can improve 56.0%, and resistance to collapse uses up block energy
There has also been be obviously improved for power.
Embodiment 3
The present embodiment provides a kind of preparation method of modified butadiene rubber, concrete technology flow process is walked referring to table 1, including as follows
It is rapid:
The butadiene rubber of 100 parts by weight is dissolved in tetrahydrofuran, rubber solutions are obtained, wherein the number of butadiene rubber is equal
Molecular weight is about 11.2 ten thousand, molecular weight distributing index 3.5.
The C 5 petroleum resin of 30 parts by weight and the calcium carbonate of 8 parts by weight are added into above-mentioned rubber solutions, stirs evenly
Afterwards, mixture is obtained；
Ethylene glycol is added into said mixture, makes the solid being made of butadiene rubber, C 5 petroleum resin and calcium carbonate
Layering is precipitated in mixture, is thermally dried through being separated by solid-liquid separation, and to obtained solid mixture, and further removing therein has
Solvent obtains modified butadiene rubber.
According to the formula and method in embodiment 1, by this implement in modification butadiene rubber mixed in opening rubber mixing machine
Refining, vulcanization, obtain vulcanized rubber.
It tests the tear resistance of vulcanized rubber, thorn resistance energy and resistance to collapses block ability of using up, specific test result such as table 1
It is shown.
Comparative example 3
Using the butadiene rubber in embodiment 3 before modified as raw rubber, according in embodiment 1 formula and method preparation vulcanization
Rubber.
That is, by the butadiene rubber of 100 parts by weight, the stearic acid of 2 parts by weight, the zinc oxide of 3 parts by weight, 0.9 parts by weight
Accelerator TBBS, the universal industrial reference black of 60 parts by weight, 15 parts by weight ASTM103# operation oil and 1.5 parts by weight sulphur
Sulphur is kneaded in opening rubber mixing machine, vulcanizes, obtains vulcanized rubber.
It tests the tear resistance of vulcanized rubber, thorn resistance energy and resistance to collapses block ability of using up, specific test result such as table 1
It is shown.
The test result of comparative example 3 and comparative example 3 is it is found that using the modification butadiene rubber in embodiment 3 as former
Expect vulcanized rubber obtained, tear resistance, which improves 44.4%, thorn resistance, can improve 52.1%, and resistance to collapse uses up block energy
There has also been certain improvement for power.
Embodiment 4
The present embodiment provides a kind of preparation method of modified butadiene rubber, concrete technology flow process is walked referring to table 1, including as follows
It is rapid:
The butadiene rubber of 100 parts by weight is dissolved in hexamethylene, rubber solutions are obtained, wherein the number of butadiene rubber is divided equally
Son amount about 12.3 ten thousand, molecular weight distributing index 4.6.
The magnesia of acrylamide and 7 parts by weight that 25 parts by weight are added into above-mentioned rubber solutions obtains after mixing evenly
To mixture；
Glycerine is added into said mixture, mixes the solid being made of butadiene rubber, acrylamide and magnesia
Layering is precipitated in object, is thermally dried, further removes therein organic molten through being separated by solid-liquid separation, and to obtained solid mixture
Agent obtains modified butadiene rubber.
According to the formula and method in embodiment 1, by this implement in modification butadiene rubber mixed in opening rubber mixing machine
Refining, vulcanization, obtain vulcanized rubber.
It tests the tear resistance of vulcanized rubber, thorn resistance energy and resistance to collapses block ability of using up, specific test result such as table 1
It is shown.
Comparative example 4
Using the butadiene rubber in embodiment 4 before modified as raw rubber, according in embodiment 1 formula and method preparation vulcanization
Rubber.
That is, by the butadiene rubber of 100 parts by weight, the stearic acid of 2 parts by weight, the zinc oxide of 3 parts by weight, 0.9 parts by weight
Accelerator TBBS, the universal industrial reference black of 60 parts by weight, 15 parts by weight ASTM103# operation oil and 1.5 parts by weight sulphur
Sulphur is kneaded in opening rubber mixing machine, vulcanizes, obtains vulcanized rubber.
It tests the tear resistance of vulcanized rubber, thorn resistance energy and resistance to collapses block ability of using up, specific test result such as table 1
It is shown.
The test result of comparative example 4 and comparative example 4 is it is found that using the modification butadiene rubber in embodiment 4 as former
Expect vulcanized rubber obtained, tear resistance, which improves 48.6%, thorn resistance, can improve 46.9%, and resistance to collapse uses up block energy
There has also been be obviously improved for power.
Embodiment 5
The present embodiment provides a kind of preparation method of modified butadiene rubber, concrete technology flow process is walked referring to table 1, including as follows
It is rapid:
The butadiene rubber of 100 parts by weight is dissolved in tetrahydrofuran, wherein the number-average molecular weight of butadiene rubber is about
10.5 ten thousand, molecular weight distributing index 2.0.
The carbon black of polyacrylamide and 5 parts by weight that 30 parts by weight are added into above-mentioned rubber solutions obtains after mixing evenly
To mixture；
Ethylene glycol is added into said mixture, mixes the solid being made of butadiene rubber, polyacrylamide and carbon black
Layering is precipitated in object, is thermally dried, further removes therein organic molten through being separated by solid-liquid separation, and to obtained solid mixture
Agent obtains modified butadiene rubber.
According to the formula and method in embodiment 1, by this implement in modification butadiene rubber mixed in opening rubber mixing machine
Refining, vulcanization, obtain vulcanized rubber.
It tests the tear resistance of vulcanized rubber, thorn resistance energy and resistance to collapses block ability of using up, specific test result such as table 1
It is shown.
Embodiment 6
The present embodiment provides a kind of preparation method of modified butadiene rubber, concrete technology flow process is walked referring to table 1, including as follows
It is rapid:
The butadiene rubber of 100 parts by weight is dissolved in tetrahydrofuran, rubber solutions are obtained, wherein the number of butadiene rubber is equal
Molecular weight is about 11.2 ten thousand, molecular weight distributing index 3.5.
The C 9 petroleum resin of 20 parts by weight and the white carbon black of 8 parts by weight are added into above-mentioned rubber solutions, stirs evenly
Afterwards, mixture is obtained；
Ethylene glycol is added into said mixture, makes the solid being made of butadiene rubber, C 9 petroleum resin and white carbon black
Layering is precipitated in mixture, is thermally dried through being separated by solid-liquid separation, and to obtained solid mixture, and further removing therein has
Solvent obtains modified butadiene rubber.
According to the formula and method in embodiment 1, by this implement in modification butadiene rubber mixed in opening rubber mixing machine
Refining, vulcanization, obtain vulcanized rubber.
It tests the tear resistance of vulcanized rubber, thorn resistance energy and resistance to collapses block ability of using up, specific test result such as table 1
It is shown.
The performance data table of vulcanized rubber in 1 embodiment of table and comparative example
| Performance | Tearing strength/KNm-1 | Thorn resistance energy/g | Resistance to collapse uses up block ability |
| Embodiment 1 | 52.8 | 0.19 | It is excellent |
| Comparative example 1 | 38.2 | 0.52 | Difference |
| Embodiment 2 | 61.2 | 0.22 | It is excellent |
| Comparative example 2 | 39.1 | 0.50 | Difference |
| Embodiment 3 | 55.6 | 0.23 | It is good |
| Comparative example 3 | 38.5 | 0.48 | Difference |
| Embodiment 4 | 58.1 | 0.26 | It is excellent |
| Comparative example 4 | 39.1 | 0.49 | Difference |
| Embodiment 5 | 53.1 | 0.21 | It is excellent |
| Embodiment 6 | 54.2 | 0.25 | It is excellent |
Embodiment 7
Using the modification butadiene rubber in embodiment 1 as raw material, automobile tire is prepared, raw materials used and its quality is as follows:
The modification butadiene rubbers of 20 parts by weight, the oil-extended styrene buadiene rubber (Qilu Petrochemical, the trade mark 1712) of 82.5 parts by weight, 20
Commercially available industrial SMR20 natural rubber, the carbon black N234 of 62.5 parts by weight, the white carbon black of 15 parts by weight, 4 parts by weight of parts by weight
Coupling agent, 3.5 parts by weight aromatic naphtha, preventing aging system (antioxidant 4020 of 1 parts by weight, the anti-aging agent RD of 2 parts by weight, 2 weights
Measure the protection wax of part), the stearic acid of 2 parts by weight, the zinc oxide of 3 parts by weight, the accelerator TBBS of 1.2 parts by weight, 2 parts by weight
Sulphur.
Mixer (capacity 1L) is tested using rubber and plastic, mixer initial temperature is 80 ± 5 DEG C, and rotor speed is 70 revs/min；
Thin logical and back mixing heats opening rubber mixing machine with 8 inches of steam of XK-200 type, preceding roll temperature: 50 ± 5 DEG C, rear roll temperature: 50 ± 5
DEG C, specific calendering process is referring to table 2.
The calendering process of 2 automobile tire of table
It parks 12 hours or more and is vulcanized after bottom sheet, vulcanization uses the vulcanizing press of XLB-400 × 40, conditions of vulcanization
For 150 DEG C × 30min.
The tearing and mechanical property of tire tread glue are tested, concrete outcome is referring to table 3.
Comparative example 5
Modification butadiene rubber in embodiment 7 is replaced with butadiene rubber, and (number-average molecular weight is about 8.2 ten thousand, molecular weight point
1.8) cloth index is that other raw materials and consumptions remain unchanged；And according to process provided in embodiment 7, it is kneaded
And vulcanization, obtain tread rubber of automobile tires.The tear resistance and mechanical property of obtained tread rubber of automobile tires are tested,
Specific test result is referring to table 3.
Comparative example 7 with the result of comparative example 5 it is found that under conditions of identical additional amount, using modified butadiene rubber
Replace common butadiene rubber, the tearing strength of obtained automobile tire increases, and wet and slippery coefficient of friction, rebound value,
The performance parameters such as hardness, tensile strength, compression fatigue temperature rise then maintain substantially, illustrate modified along fourth rubber provided by embodiment 7
Glue can improve the tear resistance of automobile tire, and the performance advantages such as high wet-sliding resistant and low-rolling-resistance have still obtained very well
Holding.
Embodiment 8
Using the modification butadiene rubber in embodiment 1 as raw material, automobile tire is prepared, in which: raw materials used and its quality is such as
Under:
The modification butadiene rubbers of 82.5 parts by weight, the oil-extended styrene buadiene rubber (Qilu Petrochemical, the trade mark 1712) of 20 parts by weight, 20
The commercially available industrial SMR20 natural rubber of parts by weight, other raw materials used and formula are same as Example 7.
Using the process conditions completely the same with embodiment 7, automobile tire is obtained, tearing and mechanics to tire tread glue
Performance is tested, and specific test result is referring to table 3.
According to table 3, with the increase of modified butadiene rubber dosage, the tearing strength and elongation at break of automobile tire
It is consequently increased, meanwhile, the parameters such as hardness, compression fatigue temperature rise, wet and slippery coefficient of friction, rebound value of automobile tire are kept substantially
It is constant, illustrate that obtained automobile tire maintains advantage brought by original butadiene rubber.
The performance test results of automobile tire in 3 embodiment of table and comparative example
| Embodiment 7 | Comparative example 5 | Embodiment 8 | |
| Shao's A hardness, degree | 65 | 66 | 65 |
| Tensile strength, MPa | 22.71 | 21.65 | 23.15 |
| Elongation at break, % | 467 | 459 | 489 |
| Tensile set, % | 12 | 13 | 11 |
| Tearing strength, kN/m | 72 | 65 | 81 |
| Compression fatigue temperature rise, DEG C | 24.1 | 28.2 | 23.0 |
| Power consumption, J/r | 2.05 | 1.99 | 1.98 |
| Wet and slippery coefficient of friction | 38 | 37 | 37 |
| Rebound value, % | 35 | 33 | 34 |
Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention., rather than its limitations；To the greatest extent
Pipe present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that: its according to
So be possible to modify the technical solutions described in the foregoing embodiments, or to some or all of the technical features into
Row equivalent replacement；And these are modified or replaceed, various embodiments of the present invention technology that it does not separate the essence of the corresponding technical solution
The range of scheme.
Claims (10)
1. a kind of preparation method of modified butadiene rubber characterized by comprising
Butadiene rubber is dissolved in organic solvent, rubber solutions are obtained；
The agent of rubber tear-proof, rubber stiffener and above-mentioned rubber solutions are uniformly mixed, mixture is obtained；
The organic solvent in mixture is removed, the modified butadiene rubber is obtained.
2. preparation method according to claim 1, which is characterized in that by weight, butadiene rubber: rubber tear-proof agent:
Reinforcing agent is 100:(1~50): (1~10).
3. preparation method according to claim 1 or 2, which is characterized in that the number-average molecular weight of the butadiene rubber is 80,
000~120,000, molecular weight distribution is 1.5~5.0.
4. preparation method according to claim 3, which is characterized in that the organic solvent includes hexane, toluene, hexamethylene
At least one of with tetrahydrofuran.
5. preparation method according to claim 1 or 2, which is characterized in that the rubber tear-proof agent be selected from phenolic resin,
At least one of terpene resin, C 5 petroleum resin, C 9 petroleum resin, acrylamide and polyacrylamide.
6. preparation method according to claim 1 or 2, which is characterized in that the rubber stiffener is selected from carbon black, hard charcoal
At least one of black, calcium carbonate and magnesia.
7. preparation method according to claim 1, which is characterized in that the organic solvent in the removal mixture, specifically
Include:
Terminator is added into the mixture, make the agent of rubber tear-proof, rubber stiffener and butadiene rubber in mixture from
It is precipitated in the organic solvent, is then separated by solid-liquid separation, obtain the modified butadiene rubber,
Wherein, at least one of methanol, ethyl alcohol, ethylene glycol and glycerine are included at least in the terminator.
8. modified butadiene rubber made from any one of the claim 1-7 preparation method.
9. a kind of vulcanized rubber, which is characterized in that be to be processed using modified butadiene rubber according to any one of claims 8 through vulcanization
It arrives.
10. application of the modified butadiene rubber according to any one of claims 8 in rubber product.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114805641A (en) * | 2021-01-21 | 2022-07-29 | 中国科学院大连化学物理研究所 | Polybutadiene low-temperature-resistant rubber base rubber and preparation method thereof |
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|---|---|---|---|---|
| CN102120835A (en) * | 2010-12-24 | 2011-07-13 | 中国科学院长春应用化学研究所 | Method for processing high-molecular-weight rare earth butadiene rubber |
| CN104387599A (en) * | 2014-11-03 | 2015-03-04 | 怡维怡橡胶研究院有限公司 | Application of continuously prepared rubber masterbatch to sidewall rubber of car tire |
| CN105330906A (en) * | 2015-11-17 | 2016-02-17 | 山东祥通橡塑集团有限公司 | Cover rubber for impact and tear resisting steel cord conveyor belt and preparing method thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102120835A (en) * | 2010-12-24 | 2011-07-13 | 中国科学院长春应用化学研究所 | Method for processing high-molecular-weight rare earth butadiene rubber |
| CN104387599A (en) * | 2014-11-03 | 2015-03-04 | 怡维怡橡胶研究院有限公司 | Application of continuously prepared rubber masterbatch to sidewall rubber of car tire |
| CN105330906A (en) * | 2015-11-17 | 2016-02-17 | 山东祥通橡塑集团有限公司 | Cover rubber for impact and tear resisting steel cord conveyor belt and preparing method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114805641A (en) * | 2021-01-21 | 2022-07-29 | 中国科学院大连化学物理研究所 | Polybutadiene low-temperature-resistant rubber base rubber and preparation method thereof |
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