CN112011019A - Preparation method of halogenated bimodal distribution star-shaped branched butyl rubber - Google Patents
Preparation method of halogenated bimodal distribution star-shaped branched butyl rubber Download PDFInfo
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Abstract
The invention provides a method for preparing bimodal distribution star-shaped branched butyl rubber by a slurry method, and belongs to the field of chemical technology application. Synthesizing a poly (styrene-conjugated diene) block polymer by adopting an anion polymerization technology, and coupling by using silicon tetrachloride to obtain a four-arm star-shaped block polymer; dissolving the copolymer, and continuously introducing HCl gas at the temperature of-20-0 ℃ for 3-12 hours to obtain a functionalized quadri-arm star-shaped branching agent containing silicon and chlorine; dissolving a silicon-and-chlorine-containing functionalized four-arm star-shaped branching agent in a solvent, adding isobutene and isoprene, reducing the temperature to below-60 ℃, mixing and aging a main initiator and a coinitiator, adding the mixture into a system, polymerizing for 3-30min under stirring, adding a terminator to terminate the reaction, distilling under reduced pressure, and drying a sample in vacuum; and halogenating the mixture to obtain halogenated bimodal distribution star-shaped branched butyl rubber. Compared with the prior art, the bimodal distribution star-branched butyl rubber provided by the invention has the advantages of relaxed Mooney stress, lower intrinsic viscosity and better processability.
Description
Technical Field
The invention relates to a preparation method of halogenated butyl rubber, in particular to a preparation method of halogenated bimodal distribution star-shaped branched butyl rubber.
Background
Butyl rubber is the only commercial product produced by the cationic polymerization process and is a copolymer of isobutylene with a small amount of isoprene. The butyl rubber has good chemical stability and thermal stability, and excellent air tightness and water tightness.
The unsaturation degree of the butyl rubber is only 0.5 to 3.3 percent (mol), which is about 1/50 of natural rubber, so that the functionality degree of the structure is very low, the low-functionality elastomer has extremely low chemical unsaturation degree, but is enough to form a cross-linked network structure with low modulus, and most of saturated structures in a molecular chain are inert chain segments which do not play a chemical role, so that the elastomer has a series of excellent characteristics: the air permeability is low, and the air tightness is 20 times of that of natural rubber; the thermal stability is good; the ozone resistance and the weather aging resistance are good; the shock absorption performance is good; good chemical corrosion resistance and water gas erosion resistance, and the like, is the best rubber for manufacturing tire inner tubes, and is also an essential raw material of high-quality radial tires. The butyl rubber has excellent heat resistance and tear resistance, and the butyl rubber inner tube can still maintain good tensile strength and tear strength after being exposed to a hot environment for a long time. The butyl rubber and ethylene propylene diene monomer combined inner tube has more excellent heat resistance, and is particularly suitable for high-temperature areas and heavy-duty diagonal tires. The butyl rubber inner tube has excellent weather resistance and ozone aging resistance, so that the butyl rubber inner tube has excellent degradation resistance, and the durability and the storage life are superior to those of a natural rubber inner tube.
Although butyl rubber has many advantages, its processability is poor, and in order to overcome these disadvantages, research and development of star-branched butyl rubber have been conducted. The star-branched butyl rubber has unique processing characteristics. The butyl rubber has a molecular structure with a large methyl group and is closely arranged among molecules, so that the butyl rubber has excellent air tightness and has irreplaceable advantages in application to tires and sealing materials. The tight molecular arrangement results in good damping, slow stress relaxation and poor processability. The star-branched butyl rubber has a unique three-dimensional shape and a high-branching structure, and shows excellent viscoelastic property, so that the processing property of the butyl rubber can be greatly improved. The branched butyl rubber polymer exhibits different processability from the original linear butyl rubber molecule in terms of the balance of crumb strength and stress relaxation.
The energy consumption for processing star-branched polymers is much lower than that for linear polymers. The star-branched butyl rubber is a bimodal polymer consisting of a graft structure with high molecular mass and a linear component with low molecular mass. The star-branched butyl rubber has a polymer with a unique three-dimensional shape and a highly-branched structure, so that the star-branched butyl rubber has the characteristics of lower solution viscosity and bulk viscosity, faster stress relaxation, insensitivity to shearing and the like, particularly shows different processing performances from the original linear butyl rubber molecule in the aspect of the balance of colloidal particle strength and stress relaxation, and the processing energy consumption of the star-branched polymer is far lower than that of the linear polymer. For this reason, star-branched butyl rubbers have been developed in recent years to improve their processability, thereby achieving a balance between the green strength and the stress relaxation rate.
Researches on star-branched butyl rubber compound rubber and a vulcanization system show that the star-branched butyl rubber has obvious advantages in the aspects of unvulcanized rubber strength, stress relaxation, extrusion property and the like, and in wide-range carbon black and oil consumption. This difference compared to conventional linear butyl rubber is attributed to the presence of a bimodal distribution in the molecular composition of the star-branched butyl rubber. Star-branched butyl rubber also has a higher cure modulus than linear butyl rubber.
In the process of preparing the star-branched butyl rubber, the synthesis of an effective branching agent is the key to successfully prepare the star-branched butyl rubber. Researchers have conducted many studies on star-type branching systems using divinylbenzene as a branching agent.
Gong Hui Qin, etc. adopts active positive ion polymerization process, uses 2-chloro-2, 4, 4-trimethyl pentane/titanium tetrachloride as initiator and monochloromethane/cyclohexane as solvent to synthesize star-shaped branched polymer with divinylbenzene as core and polyisobutylene as arm at-80 deg.C. The influence of the arm length and the core size of the polymer on star-branched polyisobutene was investigated. The results show that the enlargement of the core and the extension of the polymerization time are beneficial to the proceeding of the graft polymerization reaction and the formation of the star-shaped branched polymer; the star-branched structure is indeed generated in the system as determined by three combined equipment of a differential refractive index meter (RI)/a multi-angle laser light scattering meter (LS)/an online viscosity detector (Vis) (synthetic rubber industry, 2008, 31(5), 362-.
Star-branched polyisobutenes and star-branched butyl rubbers having a low gel content were prepared by classical cationic polymerization using divinylbenzene as branching agent in the Wang-Dong, and the influence of different feed sequences of the branching agent on the star-branched polymerization product was examined. The effect of the branching agent concentration on the star-branched polymer product was examined. By controlling the concentration of the branching agent and adding a proper amount of self-made macroinitiator styrene-vinylidene chloride, star-shaped branched butyl rubber with low gel content and bimodal molecular weight distribution, with the number average relative molecular mass of 1.21X 105, the molecular mass distribution of 6.10, the number of branching points of 29 and the gel content of 0.2%, was prepared (Beijing university of chemical industry, Master's academic thesis, 2006).
The system using divinylbenzene as a branching agent is easy to synthesize star-branched butyl rubber, can be used for researching the synthesis rule research and the structure characterization method research of the star-branched structure, but is not suitable for industrial application according to the current research result because the gel content is very high along with the increase of the molecular weight of the polymer.
Chlorohydrogenated random triblock poly (styrene-isoprene-styrene) from Exxon Mobil, USA, was used as a branching agent to produce star-branched butyl rubber (US 5071913, US 5182333, EP 0678529(A2), CN 88108392.5), and at the same time, star-branched butyl rubber was synthesized using unsaturated double bond-containing polymers such as low molecular weight polybutadiene as a branching agent. The technical raw materials are easy to obtain and have certain economical efficiency, but no report is published on the aspects of structural design and functional group introduction of the subsequent branching agent. The Beijing petrochemical industry institute Lishuxin and the like adopt a polystyrene/isoprene block copolymer with a silicon-chlorine group at the tail end or a polystyrene/butadiene block copolymer with a silicon-chlorine group at the tail end as an initiating grafting agent for cationic polymerization to directly participate in the cationic polymerization; star-branched polyisobutylene and butyl rubber products (CN200710129810.7, CN200710129812.6) are prepared by initiating cationic polymerization through silicon chloride groups and participating in grafting reaction through unsaturated bonds.
Song Dyme and the like synthesize star-shaped branched butyl rubber by using low-molecular-weight polybutadiene as a branching agent, and discuss the mechanism and the synthesis rule thereof. The low molecular weight polybutadiene is added into the monomer solution before initiating the reaction, so that the molecular weight of the product is not obviously increased, the molecular weight is reduced, and the molecular weight distribution is not greatly increased; when added to the reaction system after initiation of the propagation reaction, the molecular weight of the product is significantly increased and the distribution is broadened. When added in appropriate amounts, the desired star-branched butyl rubber with a bimodal distribution is formed (science and engineering of high molecular weight materials, 2005, 21(2), 135-138).
There are three main methods for synthesizing star-branched butyl rubber. First, the core-arm-first method, i.e., the polyfunctional initiator method, is affected by steric hindrance, initiation efficiency, chemical structure, etc., and the number of initiator functional groups is often limited, so that the number of arms of the star-branched butyl rubber synthesized by the polyfunctional initiator method is small. The initiator of polyfunctional group cyclic hydrocarbon and calixarene derivatives has complex preparation and high price, and is not beneficial to industrialization. Secondly, in the arm-first and core-second method, which is called a continuous copolymerization/coupling method of adding bifunctional or polyfunctional vinyl compounds, in the coupling prepolymer chain reaction process, the steric hindrance around the cross-linking point is large, the coupling reaction is slow, and the reaction between the macromolecular chain and the coupling agent is difficult to be carried out quantitatively, so that it is difficult to accurately control the formed core structure, the number of designed arms, and the distribution thereof by using the method. Thirdly, the core-arm simultaneous method, namely the multifunctional coupling agent connection method, is adopted for the production of commercial star-branched butyl rubber, and the research related to the preparation of star-branched butyl rubber by the core-arm simultaneous method is mainly concentrated in the companies of Exxon Mobil, Langshen and the like.
Halogenated butyl rubbers include chlorinated butyl rubbers and brominated butyl rubbers. After the butyl rubber is halogenated, the original excellent performance of the butyl rubber can be maintained, the vulcanization speed can be increased, the miscibility and the vulcanization performance of the butyl rubber with other rubbers are improved, and the caking property is also obviously improved. The halogenated butyl rubber has the application of common butyl rubber, and is particularly suitable for manufacturing inner sealing layers of tubeless tires, sidewalls of radial tires, adhesives and the like.
Polysar-301 produced by Polysar of Canada, Uibo et al, was dissolved and brominated to prepare brominated butyl rubber, and the influence of residence time and reaction temperature on Mooney viscosity, unsaturation, bromine content and microstructure of the product was examined. The result shows that the Mooney viscosity and the unsaturation degree of the product are reduced rapidly when the retention time is within 2min, and the change is not large after the retention time exceeds 2 min; increasing the reaction temperature decreases the Mooney viscosity with less effect on unsaturation. The increase of the reaction temperature and the prolongation of the residence time are not only beneficial to the increase of the bromine content in the product, but also beneficial to the rearrangement of the molecular structure, namely the phenomenon that the brominated secondary allyl configuration is transferred to the more stable brominated primary allyl configuration. (synthetic rubber industry, 2006, 29(4): 267-270).
Xunchoude et al can effectively inhibit the isomerization of secondary structure to primary structure in halogenated butyl rubber and slow down the deterioration rate of halogenated butyl rubber by adding one or more of small amount of alkali metal carbonate or bicarbonate and alkaline earth metal carbonate or bicarbonate into the product under the condition of reducing the dosage of traditional stabilizer. Meanwhile, the content of the epoxidized soybean oil of the small molecular organic matter is reduced, so that the product is purer (CN 201711443449.5).
On the basis of the existing research, the three-dimensional structure control and the introduction of other functional groups of the butyl rubber branching agent become the research trend. The polymeric branching agents currently reported for the synthesis of star-branched butyl rubber are all linear in structure. After the branching agent of the butyl rubber is designed into a star-shaped structure, the molecular weight of the branching agent is reduced, and the stress relaxation is related to the size of the molecular weight, and the stress relaxation corresponding to the reduction of the molecular weight contributes to the stress relaxation of the whole butyl rubber. Silicon atoms are introduced into the molecular chain of the branching agent, and the branching agent can be better combined with the filler white carbon black in the later processing and application process. After the star-branched butyl rubber is synthesized by using the star-branched branching agent, if the star-branched butyl rubber is halogenated, the performance is further improved, and the application range is further widened.
Up to now, there has been no report on the preparation of halogenated star butyl rubber by synthesizing star-branched butyl rubber using a star-branching agent containing silicon and chlorine and then reacting the star-branched butyl rubber with halogen. The invention aims to provide a method for preparing halogenated star-branched butyl by using star-shaped poly (styrene-conjugated diene) containing chlorine and silicon as a branching agent, adopting a slurry or solution polymerization process to prepare star-branched butyl rubber and then reacting the star-branched butyl rubber with halogen. After synthesizing poly (styrene-conjugated diene) by adopting an anion polymerization technology, introducing silicon tetrachloride for coupling to prepare star poly (styrene-conjugated diene) which takes silicon as a core and has four branched chains, and then adding the star poly (styrene-conjugated diene) with silicon and chlorine into hydrogen chloride to synthesize the star poly (styrene-conjugated diene) branching agent containing the silicon and the chlorine. The polystyrene segment as a lyophilic component can be dissolved in methyl chloride, and the chlorine of the poly-conjugated diene segment generates a polymer after initiating polymerization reaction and the polymer as a lyophobic component is not dissolved in the methyl chloride, so that a layer of soluble polymer layer is formed around the precipitated polymer, and the stability of the slurry is kept. The macromolecular zone butyl rubber obtained by polymerization on a silicon and chlorine four-arm star-shaped poly (styrene-conjugated diene) branching agent forms star-shaped macromolecules which take silicon as a core, poly (styrene-conjugated diene) as an inner layer and a butyl rubber molecular chain as an outer layer. Meanwhile, isobutylene and isoprene in the reaction system are copolymerized to generate the low molecular region linear butyl rubber. Bimodal distribution star-branched butyl rubber was synthesized. Reacting the bimodal distribution star-branched butyl rubber with halogen to prepare halogenated bimodal distribution star-branched butyl rubber. The halogenated bimodal distribution star-shaped branched butyl rubber is easy to process and vulcanize, and can be widely applied to components of tire inner liners, inner tubes and sealing elements.
Disclosure of Invention
The invention aims to provide a method for preparing halogenated bimodal distribution star-shaped branched butyl rubber by using silicon-chlorine-containing four-arm star-shaped poly (styrene-conjugated diene) as a branching agent to synthesize bimodal distribution star-shaped branched butyl rubber and reacting the bimodal distribution star-shaped branched butyl rubber with halogen. The star-shaped structure enables the butyl rubber to have lower solution viscosity and faster stress relaxation, the processing energy consumption is far lower than that of linear butyl, the vulcanization speed is increased after halogenation, the miscibility and the vulcanization performance with other rubbers are improved, and the caking property is also obviously improved.
The invention discloses a preparation method of halogenated bimodal distribution star-shaped branched butyl rubber, which comprises the following specific steps:
(1) adding a solvent into a closed dehydration and deoxidization polymerization reactor, adding styrene and an initiator, starting polymerization reaction under stirring at the reaction temperature of 20-65 ℃ for 1-4 hours, then adding a second monomer at the reaction temperature of 20-65 ℃ for 1-4 hours, adding silicon tetrachloride for coupling to obtain a four-arm star polymer, adding a terminator after the reaction is finished, discharging, washing and drying to obtain a silicon-containing four-arm star branching agent sample.
(2) Dissolving a silicon-containing branching agent sample in chloralkane, continuously introducing HCl gas at the temperature of-20-0 ℃ for 3-12 hours, washing the product to be neutral, adding a terminating agent to separate out the product, carrying out reduced pressure distillation, and carrying out vacuum drying on the sample to obtain the silicon-and-chlorine-containing functionalized four-arm star-shaped branching agent.
(3) Dissolving a silicon-and-chlorine-containing functionalized four-arm star-shaped branching agent in a solvent, adding isobutene and isoprene, reducing the temperature to below-60 ℃, mixing a main initiator and a co-initiator, diluting, aging, adding into the system, polymerizing for 3-30min under stirring, adding a terminator to terminate the reaction, distilling under reduced pressure, and drying the sample in vacuum to obtain the bimodal-distribution star-shaped branched butyl rubber sample.
(4) Fully dissolving the synthesized bimodal distribution star-shaped branched butyl rubber in a solvent, adding halogen into a reaction system, violently stirring, adding alkali liquor for neutralization, adding an auxiliary agent, removing the solvent, and drying to obtain the halogenated bimodal distribution star-shaped branched butyl rubber, wherein the reaction residence time is 3-30 min.
The invention discloses a preparation method of halogenated bimodal distribution star-shaped branched butyl rubber, which is characterized in that a synthesized silicon-chlorine-containing four-arm star-shaped poly (styrene-conjugated diene) branching agent has the following structure.
Silicon-chlorine-containing functionalized four-armed star-shaped branching agent
(R1-R6Is H, C1-C6Hydrocarbyl, chlorinated C1-C6Alkyl radical)
The invention discloses a preparation method of halogenated bimodal distribution star-shaped branched butyl rubber, which is characterized in that the mass ratio of styrene to conjugated diene in the process of synthesizing silicon-chlorine-containing four-arm star-shaped poly (styrene-conjugated diene) is controlled within the range of 80: 20-20: 80, and preferably 70: 30-40: 60.
The invention discloses a preparation method of halogenated bimodal distribution star-shaped branched butyl rubber, which is characterized in that conjugated diene copolymerized with styrene in the process of synthesizing silicon-chlorine-containing four-arm star-shaped poly (styrene-conjugated diene) is butadiene, isoprene, 1, 3-pentadiene, 2, 4-dimethylbutadiene, piperylene, 3-methyl-1, 3-pentadiene, 2, 4-hexadiene, 2-neopentylbutadiene, 2-methyl-1, 5-hexadiene, 2, 5-dimethyl-2, 4-hexadiene, 2-methyl-1, 4-pentadiene, 2-methyl-1, 6-heptadiene, cyclopentadiene, methylcyclopentadiene and cyclohexadiene, preferably butadiene, isoprene, butadiene, isoprene, butadiene, isoprene, Isoprene.
The invention discloses a preparation method of halogenated bimodal distribution star-shaped branched butyl rubber, which is characterized in that all solvents selected in the process of synthesizing silicon-and-chlorine-containing four-arm star-shaped poly (styrene-conjugated diene) are nonpolar solvents, mainly comprise pentane, cyclopentane, isopentane, n-hexane, cyclohexane, n-heptane, octane, isooctane and methylcyclohexane, and preferably cyclopentane and cyclohexane.
The invention discloses a preparation method of halogenated bimodal distribution star-shaped branched butyl rubber, which is characterized in that an initiator for initiating reaction in the process of synthesizing silicon-and-chlorine-containing four-arm star-shaped poly (styrene-conjugated diene) is a hydrocarbyl monolithium compound, namely RLi, wherein R is saturated aliphatic hydrocarbyl, alicyclic hydrocarbyl, aromatic hydrocarbyl containing 1-20 carbon atoms or a composite group of the above radicals, and n-butyllithium and tert-butyllithium are preferred.
The invention discloses a preparation method of halogenated bimodal distribution star-shaped branched butyl rubber, which is characterized in that a silicon-containing reagent for coupling poly (styrene-conjugated diene) in the process of synthesizing silicon-and-chlorine-containing four-arm star-shaped poly (styrene-conjugated diene) is silicon tetrachloride, and the amount of the silicon tetrachloride is 1/4 of an effective initiator, namely an alkyl monolithium compound.
The invention discloses a preparation method of halogenated bimodal distribution star-shaped branched butyl rubber, which is characterized in that a diluent selected in the polymerization process of preparing the star-shaped branched butyl rubber by adopting a slurry polymerization process is one or a mixture of more of dichloromethane, chloromethane, chloroethylene, chlorohexane and the like, and preferably chloromethane.
The invention discloses a preparation method of halogenated bimodal distribution star-shaped branched butyl rubber, which is characterized in that a solvent selected in the polymerization process of preparing the star-shaped branched butyl rubber by adopting a solution polymerization process is one or a mixture of more of methyl chloride and ethyl chloride and one or more of pentane, isopentane, n-hexane, cyclohexane, n-heptane, octane, isooctane, methylcyclohexane and isopentane.
The invention discloses a preparation method of halogenated bimodal distribution star-shaped branched butyl rubber, which is characterized in that a main initiator can be water, 2-chloro-2, 4, 4-trimethylpentane, HCl, BrH, HF and HClO4、HClSO3、H2SO4、H3PO4One of them, preferably water, 2-chloro-2, 4, 4-trimethylpentane, HCl.
The invention discloses a preparation method of halogenated bimodal distribution star-shaped branched butyl rubber, which is characterized in that a coinitiator can be BeCl2、ZnCl2、CdCl2、HgCl2、BF3、BCl3、AlCl3、AlBr3、RAl3、RnAlXn-3、SnCl4、TiCl4、TiBr4、ZrCl4、VCl4、WCl5、FeCl3Etc., preferably AlCl3、C6H15Al2Cl3、C2H5AlCl2Wherein R represents C1-C8 alkane, and n represents an integer of 0-3.
The invention discloses a preparation method of halogenated bimodal distribution star-branched butyl rubber, which is characterized in that in a test for synthesizing the star-branched butyl rubber, the total concentration of monomer isobutene and isoprene is 10-40%.
The invention discloses a preparation method of halogenated bimodal distribution star-branched butyl rubber, which is characterized in that in a test for synthesizing the star-branched butyl rubber, monomer isoprene accounts for 2-6 wt% of the total amount of monomers.
The invention discloses a preparation method of halogenated bimodal distribution star-shaped branched butyl rubber, which is characterized in that a solvent for dissolving bimodal distribution star-shaped branched butyl rubber is one or a mixture of pentane, hexane and heptane, or a solvent formed by mixing one or a mixture of isopentane, cyclopentane, cyclohexane, n-hexane, heptane and the like with monochloromethane and dichloromethane.
The invention discloses a preparation method of halogenated bimodal distribution star-shaped branched butyl rubber, which is characterized in that after the bimodal distribution star-shaped branched butyl rubber is dissolved, the concentration of the bimodal distribution star-shaped branched butyl rubber is 5-25 wt%.
The invention discloses a preparation method of halogenated bimodal distribution star-shaped branched butyl rubber, which is characterized in that halogenating agents of the halogenated bimodal distribution star-shaped branched butyl rubber are chlorine and bromine.
The invention discloses a preparation method of halogenated bimodal distribution star-shaped branched butyl rubber, which is characterized in that the temperature of the butyl rubber in the halogenation process is controlled at 20-65 ℃, preferably 45-60 ℃.
The invention discloses a preparation method of halogenated bimodal distribution star-shaped branched butyl rubber, which is characterized in that HCl and HBr generated by neutralization reaction are neutralized by diluted water-soluble alkali, and mainly comprise sodium hydroxide, potassium hydroxide, barium hydroxide, strontium hydroxide, rubidium hydroxide, cesium hydroxide, thallium hydroxide, lithium hydroxide, radium hydroxide and the like.
The invention discloses a preparation method of halogenated bimodal distribution star-branched butyl rubber, which is characterized in that the content of halogen in the halogenated bimodal distribution star-branched butyl rubber is 0.5-3 wt%.
The invention discloses a preparation method of halogenated bimodal distribution star-branched butyl rubber, wherein the operation process is well known to those skilled in the art.
Detailed Description
The following examples illustrate the invention in detail: the present example is carried out on the premise of the technical scheme of the present invention, and detailed embodiments and processes are given, but the scope of the present invention is not limited to the following examples, and the experimental methods without specific conditions noted in the following examples are generally performed according to conventional conditions.
(1) The raw material sources are as follows:
butadiene, petroleum, Lanzhou petrochemical, China;
styrene, petroleum, Lanzhou petrochemical, China;
isoprene, petroleum landification, china;
cyclohexane, central chemical research in petroleum lanzhou, china;
cyclopentane, central chemical research in petroleum lanzhou, china;
n-butyllithium, shanghai meirui chemical technology ltd;
tert-butyl lithium, shanghai meirui chemical technology ltd;
silicon tetrachloride, shanghai maireil chemical technology limited;
liquid bromine, beijing chemical plant;
anhydrous methanol, beijing chemical plant;
absolute ethanol, beijing chemical plant.
(2) The analysis method comprises the following steps:
the molecular weight, molecular weight distribution, intrinsic viscosity and high molecular zone content of the polymer are measured by three combined devices (SEC) of Wyatt corporation refractive index indicator (RI)/multi-angle laser light scattering instrument (LS)/online viscosity detector (Vis). The mobile phase was THF, flow rate was 1.0mL/min, and the test temperature was 30 ℃. A chromatographic column: 500-, 103-, 104-105, and ASTRA of Wyatt corporation is data processing software.
The average number of arms is calculated by comparing the molecular weight in the high molecular weight region (mw) (branched) with the molecular weight in the low molecular weight region (mw (linear)).
The determination of the stress relaxation adopts Mooney stress relaxation, adopts a high-speed rail GT-7080S2 model Mooney viscometer, stops the rotor from rotating quickly (within 0.1S) after the Mooney viscosity test is finished, and records the attenuation of the Mooney viscosity value along with the time extension. The torque after the rotor was stopped (within 0.1 s) was set as 100%, and t was used80Time taken for the torque to decay 80% (remaining 20%) []And X30(percentage of torque remaining after the rotor stopped rotating for 30 s) the stress relaxation behavior of the rubber is expressed.
The chlorine content and the bromine content are detected by a nuclear magnetic resonance method, bromine atoms in different chemical environments have absorption peaks at different positions of a spectrogram, the absorption peak area is in direct proportion to the structure content, and qualitative and quantitative analysis can be carried out through spectrogram analysis.
Example 1
(1) In a closed water-removing and oxygen-removing polymerization reactor, firstly adding 250mL of cyclohexane, then adding 15mL of styrene, adding 4mL of n-butyllithium initiator, keeping the system water-free and oxygen-free to start polymerization reaction, controlling the reaction temperature at 35 ℃, the stirring speed at 100r/min, reacting for 3 hours, then adding 13mL of isoprene, reacting for 4 hours at 35 ℃, adding 0.2mL of silicon tetrachloride to couple to obtain a four-arm star polymer, adding 50mL of methanol after the reaction is finished, discharging, washing and drying to obtain a silicon-containing four-arm star branching agent sample, and marking as ZHJ-1.
(2) Dissolving a silicon-containing four-arm star-shaped branching agent ZHJ-1 sample in 200mL of dichloromethane, continuously introducing HCl gas at 0 ℃ for 5 hours, washing the product to be neutral, adding 50mL of methanol to separate out the product, carrying out reduced pressure distillation, and carrying out vacuum drying on the sample to obtain a silicon-and-chlorine-containing functionalized four-arm star-shaped branching agent ZHJ-1-1.
(3) Dissolving a silicon-and-chlorine-containing functionalized four-arm star-shaped branching agent ZHJ-1-1 accounting for 3 wt% of the total weight of monomers in methyl chloride, adding the mixture into a reactor, wherein the total amount of the methyl chloride is 400mL, adding 230mL of isobutene and 8mL of isoprene, reducing the temperature to-80 ℃, and adding 1.5mL of dichloromethane saturated aqueous solution and 10mL of C6H15Al2Cl3Mixing, diluting, aging for 10min, addingIn the system, polymerization is carried out for 10min under stirring, 20mL of methanol is added to stop the reaction, reduced pressure distillation is carried out, and a sample is dried in vacuum to obtain a bimodal distribution star-shaped branched butyl rubber sample, which is marked as A-1.
(4) Dissolving 20g of a synthesized bimodal distribution star-shaped branched butyl rubber A-1 sample in a cyclohexane solvent, wherein the concentration is 8 wt%, adding 0.7g of bromine into a reaction system, violently stirring, keeping the temperature at 45 ℃, keeping the reaction time for 5min, adding 30% of sodium hydroxide alkali liquor for neutralization, adding 0.4g of calcium stearate and 0.25g of epoxy soybean oil, removing the solvent, and drying to obtain brominated bimodal distribution star-shaped branched butyl rubber, which is marked as A-1-1.
Comparative example 1
(1) Measuring 400mL of chloromethane, adding into a reactor, adding 230mL of isobutene and 8mL of isoprene, reducing the temperature to be below-80 ℃, and adding 1.5mL of dichloromethane saturated aqueous solution and 10mL of C6H15Al2Cl3Mixing, diluting and aging for 10min, adding the mixture into the system, polymerizing for 10min under stirring, adding 20mL of methanol to terminate the reaction, distilling under reduced pressure, and drying the sample in vacuum to obtain a butyl rubber sample, which is recorded as B-1.
(2) Dissolving 20g of a synthesized butyl rubber B-1 sample in a cyclohexane solvent, wherein the concentration is 8 wt%, adding 0.7g of bromine into a reaction system, violently stirring, keeping the temperature at 45 ℃, keeping the reaction time for 5min, adding 30% sodium hydroxide alkali liquor for neutralization, adding 0.4g of calcium stearate and 0.25g of epoxidized soybean oil, removing the solvent, and drying to obtain brominated butyl rubber, which is marked as B-1-1.
TABLE 1 test results
Example 2
(1) In a closed water and oxygen removal polymerization reactor, firstly adding 250mL of cyclohexane, then adding 15mL of styrene, adding 4mL of n-butyllithium initiator, keeping the system absolute water and absolute oxygen to start polymerization reaction, controlling the reaction temperature at 60 ℃, the stirring speed at 100r/min, reacting for 2 hours, then adding 7g of butadiene, reacting for 2 hours at 35 ℃, adding 0.2mL of silicon tetrachloride to couple to obtain a four-arm star polymer, adding 50mL of absolute ethanol after the reaction is finished, discharging, washing and drying to obtain a silicon-containing four-arm star branching agent sample, and marking as ZHJ-2.
(2) Dissolving a silicon-containing four-arm star-shaped branching agent ZHJ-2 sample in 200mL of dichloromethane, continuously introducing HCl gas at 0 ℃ for 5 hours, washing the product to be neutral, adding 50mL of absolute ethanol to separate out the product, distilling under reduced pressure, and drying the sample in vacuum to obtain a silicon-and-chlorine-containing functionalized four-arm star-shaped branching agent, which is recorded as ZHJ-2-2.
(3) Dissolving a silicon-and-chlorine-containing functionalized four-arm star-shaped branching agent ZHJ-2-2 accounting for 2 wt% of the total weight of monomers in methyl chloride, adding the mixture into a reactor, wherein the total amount of the methyl chloride is 400mL, adding 230mL of isobutene and 10mL of isoprene, reducing the temperature to-75 ℃, and adding 2mL of dichloromethane saturated aqueous solution and 8mL of C6H15Al2Cl3Mixing, diluting and aging for 10min, adding the mixture into the system, polymerizing for 10min under stirring, adding 20mL of absolute ethyl alcohol to terminate the reaction, distilling under reduced pressure, and drying the sample in vacuum to obtain a bimodal distribution star-shaped branched butyl rubber sample, which is marked as A-2.
(4) Dissolving 20g of a synthesized bimodal distribution star-shaped branched butyl rubber A-2 sample in a mixed solvent of cyclohexane and methane chloride, wherein the concentration is 10 wt%, adding 0.6g of bromine into a reaction system, violently stirring, keeping the temperature at 55 ℃, keeping the reaction time for 8min, adding 50% sodium hydroxide alkali liquor for neutralization, adding 0.4g of calcium stearate and 0.25g of epoxy soybean oil, removing the solvent, and drying to obtain the brominated bimodal distribution star-shaped branched butyl rubber, which is marked as A-2-2.
Comparative example 2
(1) 400mL of methyl chloride was measured and added to the reactor, 230mL of isobutylene and 10mL of isoprene were added, the temperature was lowered to-75 ℃ and 2mL of a saturated aqueous solution of methylene chloride and 8mL of C6H15Al2Cl3Mixing, diluting and aging for 10min, adding the mixture into the system, polymerizing for 10min under stirring, adding 20mL of absolute ethyl alcohol to terminate the reaction, distilling under reduced pressure, and drying the sample in vacuum to obtain a butyl rubber sample, which is recorded as B-2.
(2) Dissolving 20g of a synthesized butyl rubber B-2 sample in a mixed solvent of cyclohexane and methane chloride, wherein the concentration is 10 wt%, adding 0.6g of bromine into a reaction system, violently stirring at 55 ℃, keeping the reaction time for 8min, adding 50% of sodium hydroxide alkali liquor for neutralization, adding 0.4g of calcium stearate and 0.25g of epoxy soybean oil, removing the solvent, and drying to obtain the brominated butyl rubber, wherein the mark is B-2-2.
TABLE 2 test results
Example 3
(1) In a closed water-removing and oxygen-removing polymerization reactor, firstly adding 250mL of cyclopentane, then adding 15mL of styrene, adding 2mL of tert-butyl lithium initiator, keeping the system absolute water and absolute oxygen to start polymerization reaction, controlling the reaction temperature at 35 ℃, the stirring speed at 150r/min, reacting for 3 hours, then adding 4mL of isoprene, reacting for 4 hours at 35 ℃, adding 0.1mL of silicon tetrachloride to couple to obtain a four-arm star polymer, adding 50mL of methanol after the reaction is finished, discharging, washing and drying to obtain a silicon-containing four-arm star branching agent sample, and marking as ZHJ-3.
(2) Dissolving a silicon-containing four-arm star-shaped branching agent ZHJ-3 sample in 200mL of dichloromethane, continuously introducing HCl gas at-10 ℃ for 8 hours, washing the product to be neutral, adding 50mL of methanol to separate out the product, carrying out reduced pressure distillation, and carrying out vacuum drying on the sample to obtain a silicon-and-chlorine-containing functionalized four-arm star-shaped branching agent, which is recorded as ZHJ-3-3.
(3) Dissolving a silicon-and-chlorine-containing functionalized four-arm star-shaped branching agent ZHJ-3-3 accounting for 3.5 wt% of the total weight of monomers in methyl chloride, adding the methyl chloride into a reactor, wherein the total amount of the methyl chloride is 400mL, adding 220mL of isobutene and 10mL of isoprene, reducing the temperature to-85 ℃, and adding 1.6mL of dichloromethane saturated aqueous solution and 4mL of C2H5AlCl2Mixing, diluting, aging for 10min, adding into the system, polymerizing for 10min under stirring, adding 20mL methanol to terminate the reaction, distilling under reduced pressure, and vacuum drying the sample to obtain the star-branched butyl rubber with bimodal distributionSample, noted A-3.
(4) Dissolving 20g of a synthesized bimodal distribution star-shaped branched butyl rubber A-3 sample in a mixed solvent of cyclopentane and monochloromethane, wherein the concentration is 10 wt%, introducing 0.4g of chlorine gas into a reaction system, violently stirring, keeping the temperature at 45 ℃, keeping the reaction time for 20min, adding 10% sodium hydroxide alkali liquor for neutralization, adding 0.4g of calcium stearate and 0.25g of epoxy soybean oil, removing the solvent, and drying to obtain brominated bimodal distribution star-shaped branched butyl rubber, which is marked as A-3-3.
Comparative example 3
(1) A silicon-containing four-armed star-shaped branching agent sample ZHJ-3 was synthesized according to example 3, step (1).
(2) Dissolving silicon-containing four-arm star-shaped branching agent ZHJ-3 accounting for 3.5 wt% of the total weight of monomers in methyl chloride, adding the mixture into a reactor, wherein the total amount of the methyl chloride is 400mL, adding 220mL of isobutene and 10mL of isoprene, reducing the temperature to-85 ℃, and adding 1.mL of dichloromethane saturated aqueous solution and 4mL of C2H5AlCl2And mixing, diluting and aging for 10min, adding the mixture into the system, polymerizing for 10min under stirring, adding 50mL of methanol to terminate the reaction, distilling under reduced pressure, and drying the sample in vacuum to obtain a star-branched butyl rubber sample, which is recorded as B-3.
(3) Dissolving 20g of a synthesized star-shaped branched butyl rubber B-3 sample in a mixed solvent of cyclopentane and monochloromethane, wherein the concentration is 10 wt%, introducing 0.4g of chlorine gas into a reaction system, violently stirring, keeping the temperature at 45 ℃, keeping the reaction time for 20min, adding 10% sodium hydroxide alkali liquor for neutralization, adding 0.4g of calcium stearate and 0.25g of epoxy soybean oil, removing the solvent, and drying to obtain brominated bimodal distribution star-shaped branched butyl rubber, which is marked as B-3-3.
TABLE 3 test results
Example 4
(1) In a closed water-removing and oxygen-removing polymerization reactor, firstly adding 250mL of cyclopentane, then adding 15mL of styrene, adding 3mL of tert-butyl lithium initiator, keeping the system water-free and oxygen-free to start polymerization reaction, keeping the reaction temperature at 45 ℃, controlling the stirring speed at 150r/min, reacting for 3 hours, then adding 5g of butadiene, reacting at 45 ℃, reacting for 3 hours, adding 0.15mL of silicon tetrachloride to couple to obtain a four-arm star polymer, adding 50mL of methanol after the reaction is finished, discharging, washing and drying to obtain a silicon-containing four-arm star branching agent sample, which is recorded as ZHJ-4.
(2) Dissolving a silicon-containing four-arm star-shaped branching agent ZHJ-4 sample in 200mL of carbon tetrachloride, continuously introducing HCl gas at 0 ℃ for 6 hours, washing the product with water to be neutral, adding 50mL of methanol to separate out the product, carrying out reduced pressure distillation, and carrying out vacuum drying on the sample to obtain a silicon-and-chlorine-containing functionalized four-arm star-shaped branching agent, which is recorded as ZHJ-4-4.
(3) Dissolving a silicon-and-chlorine-containing functionalized four-arm star-shaped branching agent ZHJ-4-4 accounting for 3.5 wt% of the total weight of monomers in methyl chloride, adding the methyl chloride into a reactor, wherein the total amount of the methyl chloride is 400mL, adding 220mL of isobutene and 10mL of isoprene, reducing the temperature to-85 ℃, and adding 1.6mL of dichloromethane saturated aqueous solution and 4mL of C2H5AlCl2Mixing, diluting and aging for 10min, adding the mixture into the system, polymerizing for 10min under stirring, adding 20mL of methanol to terminate the reaction, distilling under reduced pressure, and drying the sample in vacuum to obtain a bimodal distribution star-branched butyl rubber sample, which is marked as A-4.
(4) Dissolving 20g of a synthesized bimodal distribution star-shaped branched butyl rubber A-4 sample in a mixed solvent of isopentane and dichloromethane, wherein the concentration is 12 wt%, adding 0.75g of bromine into a reaction system, stirring vigorously at the temperature of 50 ℃, keeping the reaction time for 5min, adding 20% of sodium hydroxide alkali liquor for neutralization, adding 0.4g of calcium stearate and 0.25g of epoxy soybean oil, removing the solvent, and drying to obtain the brominated bimodal distribution star-shaped branched butyl rubber, which is marked as A-4-4.
Comparative example 4
(1) A silicon-containing four-armed star-shaped branching agent sample ZHJ-4 was synthesized according to example 4, step (1).
(2) Dissolving 3.5 wt% of silicon-containing branching agent ZHJ-4 in the total weight of monomers in methyl chloride (400 mL), adding 220mL of isobutylene and 10mL of isoprene, cooling to-85 deg.C, and adding 1.6mL of twoSaturated aqueous solution of methyl chloride and 4mL of C2H5AlCl2And mixing, diluting and aging for 10min, adding the mixture into the system, polymerizing for 10min under stirring, adding 50mL of methanol to terminate the reaction, distilling under reduced pressure, and drying the sample in vacuum to obtain a star-branched butyl rubber sample, which is recorded as B-4.
(3) Dissolving 20g of a synthesized star-branched butyl rubber B-4 sample in a mixed solvent of isopentane and dichloromethane, wherein the concentration is 12 wt%, adding 0.75g of bromine into a reaction system, violently stirring at 50 ℃, keeping the reaction time for 5min, adding 20% of sodium hydroxide alkali liquor for neutralization, adding 0.4g of calcium stearate and 0.25g of epoxy soybean oil, removing the solvent, and drying to obtain brominated bimodal-distribution star-branched butyl rubber, wherein the mark is B-4-4.
TABLE 4 test results
Example 5
(1) In a closed dehydration and deoxidization polymerization reactor, firstly adding 250mL of cyclohexane, then adding 15mL of styrene, adding 4mL of n-butyllithium initiator, keeping the system absolute water and absolute oxygen to start polymerization reaction, controlling the reaction temperature at 55 ℃, the stirring speed at 100r/min, reacting for 3 hours, then adding 10mL of piperylene, reacting for 4 hours at 55 ℃, adding 0.2mL of silicon tetrachloride to couple to obtain a four-arm star polymer, adding 50mL of absolute ethanol after the reaction is finished, discharging, washing and drying to obtain a silicon-containing four-arm star branching agent sample, and marking as ZHJ-5.
(2) Dissolving a silicon-containing four-arm star-shaped branching agent ZHJ-5 sample in 200mL of dichloromethane, continuously introducing HCl gas at 0 ℃ for 10 hours, washing the product to be neutral, adding 50mL of absolute ethanol to separate out the product, distilling under reduced pressure, and drying the sample in vacuum to obtain a silicon-and-chlorine-containing functionalized four-arm star-shaped branching agent, which is recorded as ZHJ-5-5.
(3) Dissolving a silicon-and-chlorine-containing functionalized four-arm star-shaped branching agent ZHJ-5-5 accounting for 5 wt% of the total weight of the monomers in methyl chloride, adding the mixture into a reactor, wherein the total amount of the methyl chloride is 400mL,220mL of isobutylene, 12mL of isoprene were added, the temperature was lowered to-80 ℃ and 3mL of HCl-dissolved methyl chloride and 8mL of C were added6H15Al2Cl3Mixing, diluting and aging for 10min, adding the mixture into the system, polymerizing for 20min under stirring, adding 20mL of absolute ethyl alcohol to terminate the reaction, distilling under reduced pressure, and drying the sample in vacuum to obtain a bimodal distribution star-shaped branched butyl rubber sample, which is marked as A-5.
(4) Dissolving 20g of a synthesized bimodal distribution star-shaped branched butyl rubber A-5 sample in a mixed solvent of isopentane and dichloromethane, wherein the concentration is 15 wt%, adding 0.65g of bromine into a reaction system, violently stirring, keeping the temperature at 60 ℃, keeping the reaction time for 8min, adding 20% sodium hydroxide alkali liquor for neutralization, adding 0.4g of calcium stearate and 0.25g of epoxy soybean oil, removing the solvent, and drying to obtain the brominated bimodal distribution star-shaped branched butyl rubber, which is marked as A-5-5.
Comparative example 5
(1) Adding 250mL of cyclohexane, 15mL of styrene and 4mL of n-butyllithium initiator into a closed water-removing and oxygen-removing polymerization reactor, keeping the system at 55 ℃ and the anaerobic condition to start polymerization reaction, controlling the stirring speed at 100r/min, reacting for 3 hours, adding 10mL of piperylene, reacting at 55 ℃ and 4 hours, adding 50mL of absolute ethanol after the reaction is finished, discharging, washing and drying to obtain a linear poly (styrene-isoprene) branching agent sample.
(2) Dissolving a linear poly (styrene-isoprene) branching agent in an amount of 5 wt% based on the total weight of the monomers in methyl chloride (400 mL total), adding 220mL of isobutylene and 12mL of isoprene, cooling to-80 deg.C, and adding 3mL and 8mL of HCl-dissolved methyl chloride C6H15Al2Cl3Mixing, diluting and aging for 10min, adding the mixture into the system, polymerizing for 20min under stirring, adding 50mL of absolute ethyl alcohol to terminate the reaction, distilling under reduced pressure, and drying the sample in vacuum to obtain a star-branched butyl rubber sample, which is recorded as B-5.
(3) Dissolving 20g of a synthesized star-shaped branched butyl rubber B-5 sample in a mixed solvent of isopentane and dichloromethane, wherein the concentration is 15 wt%, adding 0.65g of bromine into a reaction system, violently stirring at the temperature of 60 ℃, keeping the reaction time for 8min, adding 20% of sodium hydroxide alkali liquor for neutralization, adding 0.4g of calcium stearate and 0.25g of epoxy soybean oil, removing the solvent, and drying to obtain the brominated star-shaped branched butyl rubber, wherein the mark is B-5-5.
TABLE 5 test results
Example 6
(1) In a closed water-removing and oxygen-removing polymerization reactor, firstly adding 250mL of cyclopentane, then adding 15mL of styrene, adding 4mL of tert-butyl lithium initiator, keeping the system water-free and oxygen-free to start polymerization reaction, keeping the reaction temperature at 45 ℃, controlling the stirring speed at 100r/min, reacting for 2 hours, then adding 10mL of piperylene, reacting at 45 ℃, reacting for 2 hours, adding 0.2mL of silicon tetrachloride to couple to obtain a four-arm star polymer, adding 50mL of methanol after the reaction is finished, discharging, washing and drying to obtain a silicon-containing four-arm star branching agent sample, and marking as ZHJ-6.
(2) Dissolving a silicon-containing four-arm star-shaped branching agent ZHJ-6 sample in 200mL of dichloromethane, continuously introducing HCl gas at the temperature of-5 ℃ for 8 hours, washing the product to be neutral, adding 50mL of methanol to separate out the product, carrying out reduced pressure distillation, and carrying out vacuum drying on the sample to obtain the silicon-and-chlorine-containing functionalized four-arm star-shaped branching agent, wherein the sample is named as ZHJ-6-6.
(3) 4 wt% of silicon-and chlorine-containing functionalized four-arm star-shaped branching agent ZHJ-6-6 based on the total weight of monomers is dissolved in methyl chloride, the mixture is added into a reactor, the total amount of the methyl chloride is 400mL, 230mL of isobutene and 8mL of isoprene are added, the temperature is reduced to-95 ℃, 1.8mL of dichloromethane saturated aqueous solution and 10mL of C6H15Al2Cl3Mixing, diluting and aging for 10min, adding the mixture into the system, polymerizing for 20min under stirring, adding 20mL of methanol to terminate the reaction, distilling under reduced pressure, and drying the sample in vacuum to obtain a bimodal distribution star-branched butyl rubber sample, which is marked as A-6.
(4) Dissolving 20g of a synthesized bimodal distribution star-shaped branched butyl rubber A-6 sample in a mixed solvent of cyclopentane and monochloromethane, wherein the concentration is 10 wt%, introducing 0.6g of chlorine gas into a reaction system, violently stirring, keeping the temperature at 45 ℃, keeping the reaction time for 20min, adding 10% sodium hydroxide alkali liquor for neutralization, adding 0.4g of calcium stearate and 0.25g of epoxy soybean oil, removing the solvent, and drying to obtain brominated bimodal distribution star-shaped branched butyl rubber, which is marked as A-6-6.
Comparative example 6
(1) Dissolving a silicon-and-chlorine-containing functionalized star-shaped branching agent ZHJ-1-1 accounting for 4 wt% of the total weight of monomers in methyl chloride, adding the mixture into a reactor, wherein the total amount of the methyl chloride is 400mL, adding 230mL of isobutene and 8mL of isoprene, reducing the temperature to-95 ℃, and adding 1.8mL of dichloromethane saturated aqueous solution and 10mL of C6H15Al2Cl3And mixing, diluting and aging for 10min, adding the mixture into the system, polymerizing for 20min under stirring, adding 20mL of methanol to terminate the reaction, distilling under reduced pressure, and drying the sample in vacuum to obtain a star-branched butyl rubber sample, which is recorded as B-6.
(2) Dissolving 20g of a synthesized star-shaped branched butyl rubber B-6 sample in a mixed solvent of cyclopentane and monochloromethane, wherein the concentration is 10 wt%, introducing 0.6g of chlorine gas into a reaction system, violently stirring, keeping the temperature at 45 ℃, keeping the reaction time for 20min, adding 10% sodium hydroxide alkali liquor for neutralization, adding 0.4g of calcium stearate and 0.25g of epoxy soybean oil, removing the solvent, and drying to obtain brominated bimodal distribution star-shaped branched butyl rubber, which is marked as B-6-6.
TABLE 6 test results
In conclusion, the synthesized series of silicon-chlorine-containing star-shaped branching agents are adopted, the bimodal distribution star-shaped branched butyl rubber is successfully synthesized by adopting a slurry process, and the bimodal distribution star-shaped branched butyl rubber is reacted with halogen to finally prepare the halogenated bimodal distribution star-shaped branched butyl rubber. Compared with linear butyl rubber, the halogenated bimodal distribution star-branched butyl rubber has lower Mooney stress relaxation, intrinsic viscosity and quick vulcanization characteristic, and the lower Mooney stress relaxation and quick vulcanization characteristic endows the butyl rubber with better processing performance.
The present invention is capable of other embodiments, and various changes and modifications may be made by one skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (19)
1. A preparation method of halogenated bimodal distribution star-shaped branched butyl rubber is characterized by comprising the following specific steps: (1) adding a solvent, styrene and an initiator into a closed water-removing and oxygen-removing polymerization reactor, reacting for 1-4 hours at 20-65 ℃ under stirring, then adding a second monomer, reacting for 1-4 hours at 20-65 ℃, adding silicon tetrachloride for coupling to obtain a four-arm star polymer, adding a terminator after the reaction is finished, discharging, washing and drying to obtain a silicon-containing four-arm star branching agent sample; (2) dissolving a silicon-containing branching agent sample, continuously introducing HCl gas at the temperature of-20-0 ℃ for 3-12 hours, washing the product to be neutral, adding a terminator to separate out the product, carrying out reduced pressure distillation, and carrying out vacuum drying on the sample to obtain a silicon-and-chlorine-containing functionalized four-arm star-shaped branching agent; (3) dissolving a silicon-and-chlorine-containing functionalized four-arm star-shaped branching agent, adding isobutene and isoprene, reducing the temperature to below-60 ℃, mixing and aging a main initiator and a co-initiator, adding the mixture into a system, polymerizing for 3-30min under stirring, adding a terminator, distilling under reduced pressure, and drying a sample in vacuum to obtain a bimodal distribution star-shaped branched butyl rubber sample; (4) fully dissolving the synthesized bimodal distribution star-shaped branched butyl rubber in a solvent, adding halogen into a reaction system, violently stirring, adding alkali liquor for neutralization, adding an auxiliary agent, removing the solvent, and drying to obtain the halogenated bimodal distribution star-shaped branched butyl rubber, wherein the reaction residence time is 3-30 min.
2. The method for preparing halogenated bimodal distribution star-branched butyl rubber according to claim 1, wherein the synthesized silicon-chlorine-containing four-arm star-shaped poly (styrene-conjugated diene) branching agent has the following structure,
wherein R is1-R6Is H, C1-C6Hydrocarbyl, chlorinated C1-C6A hydrocarbyl group.
3. The preparation method of the halogenated bimodal distribution star-shaped branched butyl rubber according to claim 1, is characterized in that the mass ratio of styrene to conjugated diene in the process of synthesizing the silicon-and-chlorine-containing four-arm star-shaped poly (styrene-conjugated diene) is controlled within the range of 80: 20-20: 80, and preferably 70: 30-40: 60.
4. The method for preparing halogenated bimodal distribution star-branched butyl rubber according to claim 1, wherein the conjugated diene copolymerized with styrene in the synthesis of silicon-chlorine-containing four-arm star poly (styrene-conjugated diene) is butadiene, isoprene, 1, 3-pentadiene, 2, 4-dimethylbutadiene, piperylene, 3-methyl-1, 3-pentadiene, 2, 4-hexadiene, 2-neopentylbutadiene, 2-methyl-1, 5-hexadiene, 2, 5-dimethyl-2, 4-hexadiene, 2-methyl-1, 4-pentadiene, 2-methyl-1, 6-heptadiene, cyclopentadiene, methylcyclopentadiene, cyclohexadiene, preferably butadiene, Isoprene.
5. The method for preparing halogenated bimodal distribution star-shaped branched butyl rubber according to claim 1, wherein the solvents selected in the process of synthesizing the silicon-and-chlorine-containing four-arm star-shaped poly (styrene-conjugated diene) are nonpolar solvents, mainly comprising pentane, cyclopentane, isopentane, n-hexane, cyclohexane, n-heptane, octane, isooctane and methylcyclohexane, and preferably cyclopentane and cyclohexane.
6. The preparation method of the halogenated bimodal distribution star-shaped branched butyl rubber according to claim 1, characterized in that an initiator for initiating a reaction in the process of synthesizing the silicon and chlorine-containing four-arm star-shaped poly (styrene-conjugated diene) is a hydrocarbyl monolithium compound, namely RLi, wherein R is a saturated aliphatic hydrocarbyl group, an alicyclic hydrocarbyl group, an aromatic hydrocarbyl group or a complex group of the above groups, containing 1-20 carbon atoms, and preferably n-butyl lithium and t-butyl lithium.
7. The preparation method of the halogenated bimodal distribution star-branched butyl rubber according to claim 1, characterized in that a silicon-containing reagent for coupling the poly (styrene-conjugated diene) in the synthesis of the silicon-and chlorine-containing four-arm star-shaped poly (styrene-conjugated diene) is silicon tetrachloride, and the amount of the silicon tetrachloride is 1/4 of an effective initiator, namely the hydrocarbyl monolithium compound.
8. The preparation method of halogenated bimodal distribution star-branched butyl rubber according to claim 1, characterized in that the diluent selected in the polymerization process for preparing star-branched butyl rubber by adopting a slurry polymerization process is one or a mixture of dichloromethane, methyl chloride, vinyl chloride, chlorohexane and the like, preferably methyl chloride.
9. The preparation method of the halogenated bimodal distribution star-shaped branched butyl rubber according to claim 1, characterized in that a solvent selected in a polymerization process of preparing the star-shaped branched butyl rubber by adopting a solution polymerization process is one or a mixture of more of methyl chloride and ethyl chloride and one or more of pentane, isopentane, n-hexane, cyclohexane, n-heptane, octane, isooctane, methylcyclohexane and isopentane.
10. The method for preparing halogenated bimodal distribution star-branched butyl rubber according to claim 1, wherein the main initiator is selected from the group consisting of water, 2-chloro-2, 4, 4-trimethylpentane, HCl, BrH, HF, HClO4、HClSO3、H2SO4、H3PO4One of them, preferably water, 2-chloro-2, 4, 4-trimethylpentane, HCl.
11. According to the rightThe preparation method of halogenated bimodal distribution star-branched butyl rubber according to claim 1, characterized in that the coinitiator can be BeCl2、ZnCl2、CdCl2、HgCl2、BF3、BCl3、AlCl3、AlBr3、RAl3、RnAlXn-3、SnCl4、TiCl4、TiBr4、ZrCl4、VCl4、WCl5、FeCl3Preferably AlCl3、C6H15Al2Cl3、C2H5AlCl2Wherein R represents C1-C8 alkane, and n represents an integer of 0-3.
12. The method for preparing halogenated bimodal distribution star-branched butyl rubber according to claim 1, wherein in a test for synthesizing the star-branched butyl rubber, the total concentration of monomer isobutene and isoprene is 10% -40%.
13. The preparation method of the halogenated bimodal distribution star-branched butyl rubber according to claim 1, wherein in a test for synthesizing the star-branched butyl rubber, the monomer isoprene accounts for 2-6 wt% of the total monomer amount.
14. The preparation method of halogenated bimodal distribution star-branched butyl rubber according to claim 1, wherein the solvent for dissolving bimodal distribution star-branched butyl rubber is one or a mixture of pentane, hexane and heptane, or a mixture of one or more of isopentane, cyclopentane, cyclohexane, n-hexane and heptane, and the solvent is obtained by mixing the mixture with monochloromethane and dichloromethane.
15. The method of claim 1, wherein the bimodal distribution star-branched butyl rubber is dissolved at a concentration of 5-25 wt%.
16. The method for preparing halogenated bimodal distribution star-branched butyl rubber according to claim 1, wherein the halogenating agent for halogenated bimodal distribution star-branched butyl rubber is chlorine or bromine.
17. The method for preparing halogenated bimodal distribution star-branched butyl rubber according to claim 1, characterized in that the temperature of the butyl rubber halogenation process is controlled between 20 ℃ and 65 ℃, preferably between 45 ℃ and 60 ℃.
18. The method for preparing halogenated bimodal distribution star-branched butyl rubber according to claim 1, wherein HCl and HBr generated by the neutralization reaction are neutralized by diluted water-soluble alkali, mainly sodium hydroxide, potassium hydroxide, barium hydroxide, strontium hydroxide, rubidium hydroxide, cesium hydroxide, thallium hydroxide, lithium hydroxide and radium hydroxide.
19. The method of claim 1, wherein the halogenated bimodal star-branched butyl rubber has a halogen content of 0.5 to 3 wt%.
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| CN113583286A (en) * | 2021-09-07 | 2021-11-02 | 温州宏武鞋材有限公司 | PU (polyurethane) material sole for women's shoes and preparation method thereof |
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| CN113583286A (en) * | 2021-09-07 | 2021-11-02 | 温州宏武鞋材有限公司 | PU (polyurethane) material sole for women's shoes and preparation method thereof |
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