CN115141313A - Acrylonitrile-styrene-conjugated diene random copolymer rubber and synthetic method and application thereof - Google Patents

Acrylonitrile-styrene-conjugated diene random copolymer rubber and synthetic method and application thereof Download PDF

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CN115141313A
CN115141313A CN202110341456.4A CN202110341456A CN115141313A CN 115141313 A CN115141313 A CN 115141313A CN 202110341456 A CN202110341456 A CN 202110341456A CN 115141313 A CN115141313 A CN 115141313A
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conjugated diene
acrylonitrile
styrene
random copolymer
copolymer rubber
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姚琼
周卫东
黄瑞丽
张建国
蒋文英
朱建军
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Sinopec Baling Petrochemical Co ltd
China Petroleum and Chemical Corp
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Sinopec Baling Petrochemical Co ltd
China Petroleum and Chemical Corp
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
    • C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
    • C08F236/12—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated with nitriles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
    • B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
    • B60C1/0016—Compositions of the tread
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • C08L9/06—Copolymers with styrene
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/80—Technologies aiming to reduce greenhouse gasses emissions common to all road transportation technologies
    • Y02T10/86—Optimisation of rolling resistance, e.g. weight reduction 

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  • Mechanical Engineering (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

The invention discloses an acrylonitrile-styrene-conjugated diene random copolymer rubber and a synthesis method and application thereof. The method comprises the steps of adding an organic phase containing a conjugated diene 1, 2-addition structure regulator, a molecular mass regulator, styrene, acrylonitrile and a conjugated diene into a water phase containing an emulsifier, a dispersant, an electrolyte, a reducing agent, a deoxidizer and an activator, stirring to form a uniform emulsion, adding an initiator to initiate polymerization, terminating the polymerization after the polymerization is finished, and coagulating to obtain the acrylonitrile-styrene-conjugated diene random copolymer rubber which has wide molecular weight distribution, acrylonitrile content of 1-5% and side chain vinyl unit content of about 60%, can be used for tire tread rubber, has the advantages of low heat generation, low rolling resistance, high wet skid resistance and the like, is a good substitute of the existing general SSBR, ESBR and the existing SSBR with low functionalized group mass content, and is an ideal all-steel radial tire tread rubber material.

Description

Acrylonitrile-styrene-conjugated diene random copolymer rubber and synthetic method and application thereof
Technical Field
The invention relates to acrylonitrile-styrene-conjugated diene random copolymer rubber, in particular to acrylonitrile-styrene-conjugated diene random copolymer rubber with wide molecular weight distribution, proper acrylonitrile content and higher content of side-chain vinyl units, a method for synthesizing the acrylonitrile-styrene-conjugated diene random copolymer rubber through low-temperature emulsion polymerization, and application of the acrylonitrile-styrene-conjugated diene random copolymer rubber in tread rubber of a tire, and belongs to the technical field of tire rubber materials.
Background
The conventional lithium-based anionic polymerization is generally performed by copolymerizing styrene and a conjugated diene to form a block or random copolymer, such as commercially available SBS-791, SIS-1209, and solution polymerized styrene-butadiene rubber SSBR 2557S. However, it is impossible to copolymerize acrylonitrile with conjugated dienes or to prepare corresponding copolymers using active lithium, since active lithium is very easily terminated by the strongly polar acrylonitrile monomer. However, the emulsion polymerization can be used to prepare an emulsion styrene-butadiene rubber (such as commercially available ESBR1500, NBR3345C and the like) by copolymerizing styrene or acrylonitrile with butadiene, but the ESBR has low contents of non-polar functional groups and side chain units in its molecule, and thus has the defects of poor wet skid resistance, high dynamic heat generation, large rolling resistance and the like when used as a tread rubber for all-steel radial tires. However, NBR is mainly used as an oil-resistant rubber product because of its high content of acrylonitrile bonded to the molecule, and is not suitable as a tire rubber because of its incompatibility with rubber softening oil, BR, natural Rubber (NR), and the like. For example, chinese patent (CN 201910264584.6) describes SBS modified asphalt and a preparation method thereof, wherein SBS is prepared by styrene and butadiene under the action of an organic lithium initiator. British patent (GB 2029426) and US patent (US 4413089) describe random or block copolymers obtained by the copolymerization of butadiene and isoprene catalysed by barium salt-lithium tributylmagnesium/trialkylaluminium, having a Mooney viscosity of 59, a molecular weight distribution D =1.46, good processability and green tack, and can be used in combination with NR. European patent (EP 0493839B 1) describes a polymer (SSBR) obtained by using butyl lithium (NBL) to initiate the coupling of a styrene-butadiene mixed monomer and tributyltin chloride, and the tan delta (65 ℃) value of the vulcanizate is reduced by 9.46% compared with the NBL-initiated mixed diene monomer, water-terminated polymer (SSBR of the general type); compared with the general SSBR, the polymer which is initiated by diene monomer and terminated by water by tributyl tin lithium has the tan delta (65 ℃) value reduced by 32.9 percent; compared with the general SSBR, the polymer obtained by initiating the coupling of diene monomer and tributyltin chloride by tributyltin lithium has a tan delta (65 ℃) value reduced by 40.1 percent, and the example shows that the active lithium of the polymer before the coupling is less than the active lithium equivalent number during the initiation, the higher the tin blocking rate is, the greater the tan delta (65 ℃) value reduction rate is, and the monomer polymerization in the technology belongs to anionic solution polymerization.
Chinese patent (CN 103665265A) discloses a preparation method of nitrile rubber, and specifically discloses a nitrile rubber prepared by cold batch emulsion polymerization of butadiene and acrylonitrile, which is characterized in that water, an emulsifier, a co-emulsifier, an emulsion stabilizer and part of monomer acrylonitrile in a formula are sequentially added into a polymerization kettle, when the temperature in the polymerization kettle is reduced to 5-10 ℃, an oxidant, a reducing agent, a secondary reducing agent and a chelating agent are sequentially added, the rest acrylonitrile monomers in the formula are supplemented according to the acrylonitrile content requirements of nitrile rubber products with different specifications, the polymerization reaction time is controlled to be 8-12 hours, the monomer conversion rate is controlled to be 65-80%, and a terminator is added to terminate the emulsion polymerization reaction. The nitrile rubber latex is prepared by degassing and coagulating, drying the nitrile rubber product by hot air to obtain a nitrile rubber product; the technical indexes are as follows: 30-95 of Mooney viscosity, 18-46 percent of the total mass of the acrylonitrile content monomer, 20-50 percent of swelling degree and 10-22 MPa of tensile strength. Chinese patent (CN 104628955A) relates to a chemically modified nitrile rubber and its production method, which is prepared from butadiene 64-65 wt%; 20-21 parts of acrylonitrile; butyl acrylate 0.30-0.31; 4.0 to 4.1 portions of sodium oleate; 0.18-0.19 of dodecanethiol and other assistants are copolymerized at 35-45 ℃, the polymerization time is as long as 15-22 hours, the technology does not describe an initiator and an activator, the Mooney viscosity of the synthesized crude rubber is more than 120, and the tensile strength is only 14.5MPa. (nitrile butadiene rubber performance influencing factor research, wangzhong, northwest university, 6 months 2012) introduces that under the condition of adding emulsifiers, activators, EDTA tetrasodium salt, EDTA ferric sodium salt and other assistants into desalted water, the dicumyl peroxide is used for initiating acrylonitrile and butadiene at the temperature of below 8 ℃. As a result, the better monomer conversion rate is not higher than 86%, and the polymerization reaction time is 15-22 h. The above techniques all belong to emulsion polymerization, and the initiators used are all peroxides.
As described above, none of the above techniques relates to a method for producing an acrylonitrile-styrene-conjugated diene copolymer, and the production principles of synthetic rubbers such as NBR, SSBR and ESBR have been described in "C.B. SERGEY LEBEDEV", synthetic rubber, beijing, chemical industry Press, 1982.8.), but styrene-acrylonitrile-conjugated diene terpolymers or multipolymers have not been reported. Further, the use of the acrylonitrile-styrene-conjugated diene random copolymer as a tread rubber for a tire has not been reported in the literature.
Disclosure of Invention
Aiming at the problems that in the prior art, the lithium-based anionic polymerization can not prepare acrylonitrile-styrene-conjugated diene random copolymer, the NBR prepared by the emulsion polymerization method has higher bound acrylonitrile content, so that the NBR can not be compatible with other synthetic rubbers, but the non-functionalized emulsion ESBR has lower content of side chain vinyl units (the content of the vinyl units is not more than 15 percent) in molecules, and when the acrylonitrile-styrene-conjugated diene random copolymer rubber is used as a tread rubber of a radial truck tire, the defects of poor wet skid resistance, high dynamic heat generation, high rolling resistance and the like can occur, the first purpose of the invention is to provide the acrylonitrile-styrene-conjugated diene random copolymer rubber which has wide molecular weight distribution, 1 to 5 percent of acrylonitrile content and about 60 percent of side chain vinyl units, the compatibility with BR or NB can be improved by reducing the content of acrylonitrile units, the side chain branches can be improved to 60 percent, the heat generation vulcanized rubber has good wet skid resistance and low rolling resistance, so that the acrylonitrile-styrene-conjugated diene random copolymer rubber can be used as a tread rubber of a tire, and has the advantages of low rolling resistance, high wet skid resistance and the like.
Another object of the present invention is to provide a method for preparing the acrylonitrile-styrene-conjugated diene random copolymerized polarized rubber (E-NSBR) with simple operation and low cost.
The E-NSBR can be used for manufacturing tread rubber of a radial high-performance semi-steel tire and is also suitable for tread rubber of a radial tire of an all-steel truck, the E-NSBR and other synthetic rubbers have good compatibility and are blended and vulcanized to form a complete compatible whole, and finally the tire has low rolling resistance, high wet-skid resistance, low heat generation and flex fatigue resistance. The existing general solution polymerized styrene-butadiene rubber (SSBR) does not contain functionalized polar groups in molecules, no cheap conjugated diene monomer containing functional groups and capable of initiating chain growth with active lithium is available in the market at present, and the polar compound terminated SSBR developed at present has a terminated blocking rate of not higher than 50 percent and can not reach the B-grade or A-grade standard of European Union tire labeling method for manufacturing tread rubber. The polarized E-NSBR can be applied to preparing tread rubber of all-steel truck radial tires with low heat generation, low rolling resistance and high wet skid resistance, and overcomes the defects of SSBR or ESBR in the existing formula of all-steel truck radial tires.
The invention provides a polarized E-NSBR, wherein E is emulsion polymerization, N is an acrylonitrile unit, S is a styrene unit, B is a double conjugated diene unit, and R is rubber.
In order to achieve the technical purpose, the invention provides a method for synthesizing acrylonitrile-styrene-conjugated diene random copolymer rubber by emulsion polymerization, which comprises the steps of adding an organic phase consisting of a conjugated diene 1, 2-addition structure regulator, a molecular mass regulator, styrene, acrylonitrile and conjugated diene into an aqueous phase comprising an emulsifier, a dispersant, an electrolyte, a reducing agent, a deoxidizer and an activator, stirring to form a uniform emulsion, adding an initiator into the emulsion to initiate polymerization reaction, and after the polymerization reaction is finished, terminating the polymerization reaction and coagulating to obtain the acrylonitrile-styrene-conjugated diene random copolymer rubber.
As a preferred embodiment, the aqueous phase uses deoxygenated water with an oxygen content of <0.05mg/L as solvent. The deoxidized water adopted by the invention is obtained by carrying out membrane deoxidation treatment on deionized water, wherein the oxygen content is less than 0.05mg/L, and the mass ratio of the deoxidized water to total polymerized monomers is 2.0-2.5.
As a preferred embodiment, the activating agent is ferric EDTA sodium salt; the addition amount of the activator relative to the total polymerized monomers is 0.6-0.8 mmol/kg. The total polymerized monomers refer to styrene, acrylonitrile and conjugated diene.
As a preferred embodiment, the emulsifier includes potassium oleate and hydrogenated disproportionated rosin potassium; the addition amount of the emulsifier relative to the total polymerized monomers is 20-30 g/kg. Further preferably, the addition amounts of potassium oleate and hydrogenated disproportionated rosin potassium are 10 to 15g/kg, respectively, relative to the total polymerized monomers.
As a preferred scheme, the dispersing agent is nekal (sodium methylene dinaphthalene sulfonate); the addition amount of the dispersant relative to the total polymerized monomers is 2.0-2.5 g/kg.
As a preferred embodiment, the electrolyte includes at least one of sodium carbonate, potassium phosphate, and potassium chloride; the addition amount of the electrolyte relative to the total polymerization monomers is 5.0-7.0 g/kg.
As a preferred embodiment, the deoxidizer is sodium hydrosulfite; the addition amount of the deoxidizer relative to the total polymerization monomer is 0.10-0.15 g/kg.
As a preferred scheme, the reducing agent is rongalite; the addition amount of the reducing agent relative to the total polymerization monomers is 0.7-1.0 g/kg.
As a preferable embodiment, the conjugated diene 1, 2-addition structure modifier is a lewis base, specifically at least one of tetrahydrofurfuryl alcohol ethyl ether, tetrahydrofurfuryl alcohol n-hexyl ether, and ditetrahydrofurfuryl propane; the addition amount of the conjugated diene 1, 2-addition structure regulator relative to the total polymerized monomers is 0.20-0.30%. The mass fraction of the 1, 2-addition structural unit as the conjugated diene polymerization unit can be controlled to be 58-62% by selecting a proper 1, 2-addition structure regulator of the conjugated diene and the using amount of the regulator.
As a preferred embodiment, the molecular mass regulator is tert-dodecyl mercaptan; the addition amount of the molecular weight relative to the total polymerized monomers is 0.5-0.9%. The Mooney viscosity of the E-NSBR can be controlled to be 45-90 by selecting a proper molecular weight regulator and using amount.
As a preferable scheme, the mass ratio of the styrene, the acrylonitrile and the conjugated diene satisfies: styrene/conjugated diene = (20 to 28)/(80 to 72); acrylonitrile/conjugated diene = (1-5)/(99-95). The styrene, conjugated diene and acrylonitrile monomers adopted by the invention are in polymerization grade, wherein the content of a polymerization inhibitor TBC is less than 5.0mg/kg, the content of oxygen is less than 0.05mg/L, and the total content of calcium, magnesium and iron ions is less than 1.0mg/L. In the emulsion polymerization process, because the monomer can not be completely converted, the preferred styrene/conjugated diene = (20-28)/(80-72) (weight ratio), the preferred acrylonitrile/conjugated diene (weight ratio) = (1-5)/(99-95) can control the combined styrene mass fraction in the polarized E-NSBR molecule to be 20-28%; the mass fraction of the combined acrylonitrile is 1.0-5.0%. If the mass fraction of strongly polar acrylonitrile incorporated in the random copolymer of styrene, conjugated diene and acrylonitrile is too high, the compatibility of the raw rubber with other diene rubbers and mineral rubber oils is reduced, i.e., the content of incorporated acrylonitrile in the copolymer of the present invention is not too high, and the content of incorporated acrylonitrile in the copolymer is not too low, otherwise the rubber does not achieve the purpose of polar functionalization.
As a preferred embodiment, the conjugated diene is butadiene and/or isoprene.
As a preferred embodiment, the polymerization conditions are: the temperature is 5-8 ℃, the time is 4-15 h, and the pressure is 0.2-0.5 MPa.
As a preferable scheme, the initiator used for the polymerization reaction is preferably at least one of p-menthane hydroperoxide PMHP, pinane hydroperoxide PHP and cumene hydroperoxide, and the preferable amount of the initiator is 0.9 to 1.3g/kg of the monomer.
As a preferred embodiment, the polymerization results in a raw gel with a gel content fraction of <0.5%.
In order to achieve the technical purpose, the invention provides an acrylonitrile-styrene-conjugated diene random copolymer rubber obtained by the synthesis method.
Preferably, the molecular mass distribution index is 4.5 to 5.5, the content of the trans 1, 2-addition structural unit in the conjugated diene unit is 58 to 62 percent by mass, the content of the acrylonitrile unit is 1.0 to 5.0 percent by mass, and the acrylonitrile unit is randomly and uniformly distributed in the acrylonitrile-styrene-conjugated diene random copolymer rubber, namely the polarized E-NSBR rubber. Wide molecular weight distribution and good processing performance.
The invention also provides application of the polarized E-NSBR rubber, which is applied to tread rubber of a tire.
The E-NSBR rubber of the invention is further preferably applied to a tread rubber of an all-steel radial tire.
The preferable tread rubber component of the all-steel radial tire comprises 40 to 50 parts of E-NSBR (calibrated as rubber variation); 40-60 parts of Natural Rubber (NR); 50-55 parts of carbon black; 15-20 parts of rubber oil NAP-10; 3 parts of zinc oxide; 1 part of stearic acid; 1.7 parts of sulfur; 1.3 parts of accelerator CZ; and 1.4 parts of an accelerator D.
The preparation method of the tread rubber of the all-steel radial tire comprises the following steps:
firstly, putting the polarized E-NSBR, NR, rubber operating oil, carbon black, stearic acid, zinc oxide, an accelerator and the like into an internal mixer for mixing, and discharging the composite mixed rubber to form master batch after the temperature of the mixed rubber is raised to 130-150 ℃ for mixing for 90 s; then putting the master batch on an open mill at 50-60 ℃, adding sulfur for mixing, cutting 3/4 of the left and right sides of the mill three times respectively with an interval of 15s, adjusting the roll spacing to 0.8mm, alternately passing through each end longitudinally for six times, pressing the rubber material into a rubber compound rubber sheet with the thickness of about 2.2mm, and vulcanizing the rubber sheet of the lower rubber sheet.
The vulcanization of the rubber compound is carried out under the process conditions well known in the industry, and the vulcanization is carried out for 25min at the temperature of 150 ℃.
Compared with the prior art, the technical scheme of the invention has the following beneficial effects:
compared to NBR, the polarized E-NSBR of the present invention is not intended for use as an oil resistant rubber article. Compared with SSBR or ESBR, because a small amount of acrylonitrile is combined in the molecular chain of E-NSBR and is randomly distributed in the terpolymer, the functional cyano-containing polar rubber which is uniformly distributed in the molecular chain does not lose good compatibility with rubber oil; in addition, a higher side branch chain 1, 2-addition structural unit is combined in the E-NSBR molecular chain, and the side branch chain addition unit structure in the existing SSBR or SIBR molecule is reserved.
The E-NSBR of the invention obtains the conversion rate of a polymer monomer by low-temperature emulsion polymerization to be more than 88 percent, the mass fraction of gel in the raw rubber is less than 0.5 percent, the mass fraction of the combined acrylonitrile in the raw rubber can be randomly adjusted between 1.0 to 5.0 percent, the prepared polarized E-NSBR raw rubber has wide molecular mass distribution index and proper Mooney viscosity, is beneficial to the mixing and processing of rubber, can be compatible with NR and diene rubber in any proportion, has no phase separation phenomenon of vulcanized rubber, has only one glass transition temperature, simultaneously shows excellent grip performance and wet skid resistance, is a good substitute of the existing general SSBR, ESBR and the existing SSBR with lower mass content of functional groups, and is an ideal material of tread rubber of all-steel radial tires.
The synthesis method of the polarized E-NSBR provided by the invention is simple to operate, low in cost and beneficial to large-scale production.
Drawings
FIG. 1 shows E-NSBR-like H prepared in example 6 1 -NMR spectrum.
FIG. 2 shows the dynamic visco-elastic spectra of the E-NSBR and SOL-5251H vulcanizates prepared in example 6.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and these ranges or values should be understood to encompass values close to these ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The present invention is illustrated by the following examples, which are not intended to limit the scope or practice of the invention. Microstructure adopts 1 H-NMR measurement; mooney viscosity is measured by a Mooney viscosity analyzer according to GB/T1232-1992 determination of Mooney viscosity of unvulcanized rubber; the tensile stress strain performance of the vulcanized rubber is determined according to the GB/T528-2009 method; mixing and vulcanizing the raw rubber are carried out according to SH/T1611-1995 national standard; the tan delta value at 0 ℃ is measured by a dynamic viscoelastometer to represent the wet skid resistance of vulcanized rubber, the tan delta value at 60 ℃ is used to represent the rolling resistance of the tread rubber of the tire, and the test conditions, the frequency of 5HZ, the heating rate of 3K/min and the temperature of-60-80 ℃ are adopted; the vulcanizate was tested for compression heat generation using a Goodrich compression heat generation tester.
Example 1
1.7 liters of deoxygenated water was charged into a 5 liter polymerization reactor under nitrogen protection, and then 15.0 weight% of potassium oleate 50mL,25 weight% of disproportionated rosin potassium 40mL,0.05mol iron/L aqueous solution of EDTA iron sodium salt 12mL,13.5 weight% aqueous solution of sodium methylenedinaphthalene sulfonate 13mL, aqueous solutions of sodium carbonate, sodium phosphate and potassium chloride each having a mass fraction of 10%, 2.0 weight% aqueous solution of sodium hydrosulfite 5mL,6.0 weight% aqueous solution of sodium formaldehyde sulfoxylate 10mL were added to the polymerization vessel. Then, the auxiliary agent is pressed into a polymerization kettle by nitrogen, stirring is started, circulating cooling water at 5 ℃ is introduced to cool materials in the kettle to below 6 ℃, then 6.5mL of dodecanethiol and 2.3g of tetrahydrofurfuryl alcohol ethyl ether are simultaneously dissolved in a mixed monomer consisting of 200g of styrene, 600g of butadiene and 22g of acrylonitrile, the mixed monomer is pressed into the polymerization kettle by nitrogen at one time, after the materials in the kettle are cooled to 5-6 ℃, 1.10mL of PMHP is added into a polymerization kettle sight glass and pressed into a polymerization system, the polymerization temperature is maintained at 5-7 ℃, after the polymerization temperature is reduced to 5.0 ℃ after reaction for 5 hours, the materials can be discharged, 1.2g of terminator sodium dithiocarbamate and 2.0g of antioxidant are respectively added into emulsion liquid and uniformly mixed, unreacted monomers are removed in vacuum at 85 ℃, then the emulsion is coagulated by sulfuric acid aqueous solution of dinitrile formaldehyde condensation compound with mass fraction of 1.0%, polarity diluted BR is washed by water and dried, thus obtaining 1520-731 g of NSE, and the conversion rate of raw rubber is 89.05-89 g of raw rubber.
The Mooney viscosity of the crude rubber is 55.8 and the molecular mass distribution index of the crude rubber is 4.2 by result sampling; the vinyl unit content was 60.3%, and the bound acrylonitrile amount was 2.56%.
Example 2
The relevant process conditions in example 1 were kept unchanged except that 1.6L of water for polymerization, 6.0mL of dodecanethiol, 2.0g of tetrahydrofurfuryl alcohol n-hexyl ether, 190g of styrene, 20g of acrylonitrile and 1.0mL of PMHPP were added.
As a result: after the polymerization reaction is carried out for 6.5h, 727g of polarized E-NSBR crude rubber is obtained by drying, and the conversion rate of the monomer is 89.75 percent; the Mooney viscosity of the crude rubber is measured to be 61.7, and the molecular mass distribution index of the crude rubber is measured to be 4.8; the vinyl unit content was 60.2%, and the bound acrylonitrile amount was 2.47%.
Example 3
The relevant process conditions in example 1 were kept the same except that 1.9L of water for polymerization, 5.5mL of dodecanethiol, 2.2g of ditetrahydrofurfuryl propane, 175g of styrene, 15g of acrylonitrile, and 1.0mL of PHP were added.
As a result: after the polymerization reaction is carried out for 5.5h, 710g of polarized E-NSBR crude rubber is obtained by drying, and the conversion rate of the monomer is 89.87%; measuring that the Mooney viscosity of the raw rubber is 76.8 and the molecular mass distribution index of the raw rubber is 4.7; the vinyl unit content was 61.6%, and the bound acrylonitrile amount was 1.90%.
Example 4
The relevant process conditions in example 1 were kept unchanged except that 5.0mL of dodecanethiol, 2.0g of ditetrahydrofurfurylpropane, 1.1 mL of PHP, 170g of styrene, 10g of acrylonitrile and 600g of isoprene as butadiene were all added.
As a result: after the polymerization reaction is carried out for 4.5h, 704g of polarized E-NSBR crude rubber is obtained by drying, and the conversion rate of the monomer is 90.25 percent; the Mooney viscosity of the crude rubber is measured to be 92.8, and the molecular mass distribution index of the crude rubber is measured to be 4.8; the isopropenyl unit content was 60.6%, and the bound acrylonitrile amount was 1.28%.
Example 5
The relevant process conditions in example 1 were kept unchanged except that 28g of acrylonitrile, 4.5mL of dodecanethiol and 600g of isoprene as butadiene were all used, and diisopropylbenzene hydroperoxide was used as the initiator.
As a result: after the polymerization reaction is carried out for 14 hours, drying is carried out to obtain 741g of polarized E-NSBR crude rubber, and the conversion rate of the monomer is 89.50 percent.
The Mooney viscosity of the raw rubber is 118, the molecular mass distribution index of the raw rubber is 4.3, the content of isopropenyl units is 58.6 percent, and the content of bound acrylonitrile is 3.38 percent.
Example 6
The relevant process conditions in example 1 were kept constant except that 1.7L of water for polymerization, 6.0mL of dodecanethiol, 2.0g of tetrahydrofurfuryl alcohol n-hexyl ether, 180g of styrene, 40g of acrylonitrile and 1.2mL of PMHPP were added.
As a result: after the polymerization reaction is carried out for 5 hours, 739g of polarized E-NSBR crude rubber is obtained by drying, and the conversion rate of the monomer is 90.12%; measuring that the Mooney viscosity of the raw rubber is 67.4 and the molecular mass distribution index of the raw rubber is 4.3; the vinyl unit content was 59.84%, and the bound acrylonitrile amount was 4.88%.
Polarized E-NSBR-like H prepared in example 6 1 NMR spectrum as shown in FIG. 1: in fig. 1, chemical shifts σ =2.53 represent hydrogen bonded to random acrylonitrile, σ =4.90 to 5.72 represent hydrogen bonded to a butadiene addition unit, σ =7.0 to 7.2 represents hydrogen bonded to random styrene, and σ =6.6 represents hydrogen bonded to no block styrene. The results show that the ternary monomers combined in the prepared polarized E-NSBR molecules are randomly distributed.
Comparative example 1
The relevant process conditions in example 1 were kept unchanged except for 50g of acrylonitrile added.
As a result: obtaining the polarized E-NSBR crude rubber 746g, the conversion rate of the monomer is 90.12 percent; measuring the Mooney viscosity of the raw rubber to be 66.9 and the molecular mass distribution index of the raw rubber to be 4.6; the vinyl unit content was 59.42%, and the bound acrylonitrile amount was 6.02%.
Comparative example 2
The relevant process conditions in example 4 were kept unchanged except that 60g of acrylonitrile was added.
As a result: 742g of polarized E-NSBR crude rubber is obtained, and the conversion rate of the monomer is 89.39%; the Mooney viscosity of the raw rubber is measured to be 97.3, and the molecular mass distribution index of the raw rubber is 4.5; the isopropenyl unit content was 61.13%, and the bound acrylonitrile amount was 7.23%.
Example 7
The polarized E-NSBR prepared in examples 1,2, 3, 4, 5, 6 and comparative examples 1 and 2 and the commercially available functionalized solution-polymerized styrene-butadiene rubber SOL-5251H were prepared and vulcanized according to the formulation of the present invention and the preparation method of the rubber compound, respectively, and the results are shown in Table 1.
TABLE 1 vulcanizate physical Properties
Figure BDA0002999213020000101
Note: the formula (parts by mass) of the all-steel tread rubber vulcanized rubber is as follows: 50 parts of variable sizing; NR,50 parts; carbon black N330, 55 parts; NAP-10, 20 parts; 3 parts of zinc oxide; 1 part of stearic acid; 1.7 parts of sulfur; accelerator CZ1.3 parts; and 1.4 parts of an accelerator D.
As can be seen from Table 1, the physical properties of the vulcanizate are poor due to the higher bound acrylonitrile content in the comparative sample, which is due to the incompatibility of the E-NSBR with the rubber oil; compared with functionalized solution-polymerized styrene-butadiene rubber, the polarized E-NSBR has better physical properties, particularly better dynamic mechanical properties, and shows higher wet skid resistance and lower rolling resistance. The dynamic viscoelastic spectrum of the polarized E-NSBR and SOL-5251H vulcanizate prepared as in example 6 is shown in FIG. 2.

Claims (16)

1. A method for synthesizing acrylonitrile-styrene-conjugated diene random copolymer rubber by emulsion polymerization is characterized in that: adding an organic phase consisting of a conjugated diene 1, 2-addition structure regulator, a molecular mass regulator, styrene, acrylonitrile and a conjugated diene into a water phase containing an emulsifier, a dispersant, an electrolyte, a reducing agent, a deoxidizer and an activator, stirring to form a uniform emulsion, adding an initiator into the emulsion to initiate polymerization, terminating the polymerization after the polymerization is finished, and condensing to obtain the modified styrene/acrylonitrile copolymer emulsion.
2. The method for synthesizing acrylonitrile-styrene-conjugated diene random copolymer rubber by emulsion polymerization according to claim 1, wherein: the water phase adopts deoxidized water with oxygen content less than 0.05mg/L as solvent.
3. The method for synthesizing acrylonitrile-styrene-conjugated diene random copolymer rubber by emulsion polymerization according to claim 1, wherein: the activating agent is EDTA ferric sodium salt; the addition amount of the activator relative to the total polymerized monomers is 0.6-0.8 mmol/kg.
4. The method for synthesizing acrylonitrile-styrene-conjugated diene random copolymer rubber by emulsion polymerization according to claim 1, wherein: the emulsifier comprises potassium oleate and hydrogenated disproportionated rosin potassium; the addition amount of the emulsifier relative to the total polymerized monomers is 20-30 g/kg.
5. The method for synthesizing acrylonitrile-styrene-conjugated diene random copolymer rubber by emulsion polymerization according to claim 1, wherein: the dispersing agent is nekal; the addition amount of the dispersant relative to the total polymerized monomers is 2.0-2.5 g/kg.
6. The method for synthesizing acrylonitrile-styrene-conjugated diene random copolymer rubber by emulsion polymerization according to claim 1, wherein: the electrolyte comprises at least one of sodium carbonate, potassium phosphate and potassium chloride; the addition amount of the electrolyte relative to the total polymerization monomers is 5.0-7.0 g/kg.
7. The method for synthesizing acrylonitrile-styrene-conjugated diene random copolymer rubber by emulsion polymerization according to claim 1, wherein: the deoxidizer is sodium hydrosulfite; the addition amount of the deoxidizer relative to the total polymerization monomers is 0.10-0.15 g/kg.
8. The method for synthesizing acrylonitrile-styrene-conjugated diene random copolymer rubber by emulsion polymerization according to claim 1, wherein: the reducing agent is a rongalite; the addition amount of the reducing agent relative to the total polymerization monomers is 0.7-1.0 g/kg.
9. The method for synthesizing acrylonitrile-styrene-conjugated diene random copolymer rubber by emulsion polymerization according to claim 1, wherein: the conjugated diene 1, 2-addition structure regulator is at least one of tetrahydrofurfuryl alcohol ethyl ether, tetrahydrofurfuryl alcohol n-hexyl ether and ditetrahydrofurfuryl propane; the addition amount of the conjugated diene 1, 2-addition structure regulator relative to the total polymerized monomers is 0.20-0.30%.
10. The method for synthesizing acrylonitrile-styrene-conjugated diene random copolymer rubber by emulsion polymerization according to claim 1, wherein: the molecular mass regulator is tert-dodecyl mercaptan; the addition amount of the molecular weight relative to the total polymerized monomers is 0.5-0.9%.
11. The method for synthesizing acrylonitrile-styrene-conjugated diene random copolymer rubber by emulsion polymerization according to claim 1, wherein: the mass ratio of the styrene to the acrylonitrile to the conjugated diene satisfies the following requirements: styrene/conjugated diene = (20 to 28)/(80 to 72); acrylonitrile/conjugated diene = (1-5)/(99-95).
12. The process for synthesizing an acrylonitrile-styrene-conjugated diene random copolymer rubber by emulsion polymerization according to claim 1 or 11, wherein: the conjugated diene is butadiene and/or isoprene.
13. The method for synthesizing acrylonitrile-styrene-conjugated diene random copolymer rubber by emulsion polymerization according to claim 1, wherein: the conditions of the polymerization reaction are as follows: the temperature is 5-8 ℃, the time is 4-15 h, and the pressure is 0.2-0.5 MPa.
14. An acrylonitrile-styrene-conjugated diene random copolymer rubber, characterized in that: obtained by the synthesis method of any one of claims 1 to 13.
15. The acrylonitrile-styrene-conjugated diene random copolymer rubber according to claim 14, wherein: the molecular mass distribution index is 4.5-5.5, the mass percentage content of trans 1, 2-addition structural unit in the conjugated diene unit is 58-62%, and the mass percentage content of acrylonitrile unit is 1.0-5.0%.
16. The use of an acrylonitrile-styrene-conjugated diene random copolymer rubber according to claim 14 or 15, wherein: the rubber is applied to the tread rubber of the tire.
CN202110341456.4A 2021-03-30 2021-03-30 Acrylonitrile-styrene-conjugated diene random copolymer rubber and synthetic method and application thereof Pending CN115141313A (en)

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