CN112011003B - Preparation method of functionalized four-arm star-shaped branching agent for branching butyl rubber - Google Patents
Preparation method of functionalized four-arm star-shaped branching agent for branching butyl rubber Download PDFInfo
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
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- C08F210/04—Monomers containing three or four carbon atoms
- C08F210/08—Butenes
- C08F210/10—Isobutene
- C08F210/12—Isobutene with conjugated diolefins, e.g. butyl rubber
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Abstract
The invention provides a preparation method of a functionalized four-arm star-shaped branching agent for branching butyl rubber, which comprises the following specific steps: (1) Adding a solvent, styrene and an initiator into a closed polymerization reactor for removing water and oxygen, reacting for 1-4 hours at the reaction temperature of 20-65 ℃ under stirring, then adding a second monomer at the reaction temperature of 20-65 ℃, reacting 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) After dissolving a silicon-containing branching agent sample, continuously introducing HCl gas at-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. Compared with the prior art, the synthesized silicon-and-chlorine-containing four-arm star-shaped branching agent has lower Mooney stress relaxation and intrinsic viscosity, and can be used as the branching agent for preparing star-shaped branched butyl rubber.
Description
Technical Field
The invention relates to a preparation method of a functionalized four-arm star-shaped branching agent for branching butyl rubber, in particular to a preparation method of a functionalized star-shaped styrene and conjugated diene copolymer.
Background
With the rapid development of the synthetic rubber product industry and the continuous and deep research on the correlation between the rubber structure and the performance, the synthesis of synthetic rubber products with specific structures and better comprehensive performance becomes the development trend in the future. With the continuous deepening of the research on the polymerization theory and the continuous improvement of the polymerization technology, researchers can control and adjust the structure, the composition, the relative molecular mass, the distribution and the like of a target polymer from the relationship between the structure and the performance. The star-branched structure endows the synthetic rubber with a unique three-dimensional shape and a highly branched structure. Compared with synthetic rubber with a linear structure, the star-branched synthetic rubber has the characteristics of lower solution viscosity and bulk viscosity, faster stress relaxation, insensitivity to shearing and the like. Therefore, the research on the star-branched synthetic rubber technology, products and processing application performance becomes one of the hot spots of polymer research.
The advantages of star-branched polymers are mainly their rheological, processing and mechanical properties. The butyl rubber has a regular special molecular chain molecular structure, and the star-shaped branched structure contributes most to the processing performance of the butyl rubber.
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 production process of butyl rubber is mainly divided into a slurry method and a solution method. The slurry method for preparing the butyl rubber takes chloromethane as a diluent and H 2 0、AlC1 3 The synthesis method is characterized in that the synthesis method adopts ethyl sesquialuminum chloride and the like as an initiating system, and isobutene and a small amount of isoprene are synthesized through cationic copolymerization at a low temperature (about-100 ℃). The technical development research of the solution method for manufacturing the butyl rubber has long history, but only the Russian Togliatti industrial device realizes the solution method butyl rubber production in the world. The production process of the device takes water and alkyl aluminum chloride as an initiator system, uses isopentane and chloroethane as solvents, and carries out the copolymerization of isobutene and isoprene at the temperature of-70 ℃ to-80 ℃. The technical differences between the solution process and the slurry process for producing butyl rubber are as follows. Firstly, the solution method can reduce energy consumption by the polymerization reaction under the condition of higher temperature; secondly, the toxicity of the mixed solvent of isopentane and chloroethane is lower than that of chloromethane, so that the pollution to the environment is light. The solvent has small corrosivity, and the investment of related equipment can be reduced; thirdly, the viscosity of the solution polymerization glue solution is obviously increased along with the increase of the conversion rate, and in order to ensure the timely conduction of reaction heat, the conversion rate of the monomer isobutene is only 20-30%. The content of the polymer in the glue solution is generally about 10 percent; fourth, the molecular weight distribution of solution butyl rubber is greatly affected by the solvent. The technical economy of the slurry method is better than that of the solution method as a whole, and the processing technological performance of the slurry method product is better than that of the solution method product. But the solution method still has many advantages, the reaction temperature is relatively high, and the energy consumption of the device is reduced; the use of a chloromethane yard is reduced, andthe environmental pollution is relatively small; the polymerization reaction rate is slow, and the reaction is easier to control; the glue hanging phenomenon is reduced in the production, and the continuous production period of the device is prolonged; the produced butyl rubber solution can be directly brominated, so that the steps of coagulation, drying and redissolution are omitted, and the method is very convenient.
The unsaturation degree of the butyl rubber is only 0.5 to 3.3 percent (mol) and is about 1/50 of that of natural rubber, so that the structure has very low functionality, 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. And the molecules are closely arranged, so that the damping performance is good, the stress relaxation is slow, and the processing performance is poor. 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 processing 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 green strength and stress relaxation rate.
Researches on the star-branched butyl rubber compound rubber and a vulcanization system find that the star-branched butyl rubber not only has obvious advantages in the aspects of unvulcanized rubber strength, stress relaxation, extrusion property and the like, but also has obvious advantages in wide range of 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.
At present, the star-branched rubber is mainly prepared by a first-arm-then-core method, a first-core-then-arm method and a core-arm simultaneous method, and different methods have own characteristics and have great differences in product performance.
The arm-first and core-second method generally comprises the steps of synthesizing an active polyisobutylene chain by using a monofunctional initiator, and adding a bifunctional or polyfunctional vinyl compound to react to form a coupled core. Shell company initiates isobutene polymerization to generate active polymer, and then diisopropenyl benzene is used for coupling the active polymer to obtain star polymer with poly diisopropenyl benzene as core and isobutene polymer as arm (Macromolecules, 1988,21 (7): 2175-2183). By adopting the coupling technology, although the star-shaped polymer is easy to synthesize, the number of arms is not easy to be accurately controlled, gel is easy to form, and the product performance is unstable.
The core-arm-first method, i.e., the polyfunctional initiator method, uses a polyfunctional initiator as a core and a newly produced polymer as an arm in polymerization. The technology has obvious advantages in controlling the number of arms, the arm length and the sequence structure of the star polymer. Zhang Xingying et al synthesized polyfunctional organolithium initiator, and synthesized star-shaped medium vinyl polybutadiene rubber (CN 1148053) in one-step method in raffinate oil. Puskas et al prepared multi-arm star polymers by living cationic polymerization using a free radical copolymer of 4- (2-hydroxy-methylethyl) styrene and styrene as an initiator (Journal of Polymer Science Part A Polymer Chemistry,2002,40 (21): 3725-3733). Zhang Taoyi et al synthesized random star-type integral rubbers using polyfunctional organolithium initiators (synthetic rubber industry, 2001,24 (6): 373). The polar regulator has obvious influence on the microstructure in the synthesis process, the content of the 1,2 structure of butadiene and the 3,4 structure of isoprene in the integrated rubber is increased when the using amount is increased, and the composition of the integrated rubber is closer to the monomer proportion. The improvement of functionality during polymerization has no significant effect on microstructure content.
Gong Huiqin and the like adopt an active positive ion polymerization method, 2-chloro-2,4,4-trimethylpentane/titanium tetrachloride is taken as an initiator, monochloromethane/cyclohexane is taken as a solvent, and star-shaped branched polymers taking divinylbenzene as a core and polyisobutylene as an arm are synthesized at the temperature of minus 80 ℃. 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 devices 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), 362-365).
Wang Xiaodong star-branched polyisobutylene and star-branched butyl rubber with low gel content were prepared by typical cationic polymerization using divinylbenzene as the branching agent, and the effect of different addition sequences of the branching agent on the star-branched polymerization product was examined. The effect of the branching agent concentration on star-branched polymer products was examined. By controlling the concentration of branching agentThe self-made macromolecule initiator styrene-vinylidene chloride with proper amount is added to prepare the product with the number-average relative molecular mass of 1.21 multiplied by 10 5 Star-branched butyl rubber with low gel content having a bimodal molecular weight distribution with a molecular weight distribution of 6.10, a number of branching points of 29 and a gel content of 0.2% (master's academic paper of Beijing university of chemical industry, 2006).
A system using divinylbenzene as a branching agent is easy to synthesize the star-branched-structure 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.
The simultaneous core-arm method, which polymerizes monomers in the presence of bifunctional or polyfunctional monomers or polymers, is an effective means for preparing a polymer having a bimodal distribution. The company Exxon has invented a technique for preparing star-branched bimodal butyl rubbers using a hydrochlorinated polystyrene-isoprene copolymer as initiator (U.S. Pat. No. 5,5071913,5182333,EP 0678529 (A2), CN 88108392.5). 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 Li Shuxin 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 silicon and chlorine groups at the tail end as an initiating grafting agent for positive ion polymerization, and directly participate in the positive ion polymerization; the star-branched polyisobutylene and butyl rubber products (CN 200710129810.7 and CN 200710129812.6) are prepared by initiating cationic polymerization through a silicon-chlorine group and participating in a grafting reaction through an unsaturated bond. Song Gaiyun and the like synthesize star-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 in a bimodal distribution is produced (Polymer science and engineering, 2005, 21 (2), 135-138). The nuclear-arm simultaneous method is the most advanced and reasonable technical route for preparing the star-shaped branched polymer.
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, the stress relaxation is related to the molecular weight, and the stress relaxation corresponding to the reduced molecular weight contributes to the stress relaxation of the whole butyl rubber. Silicon atoms are introduced into the molecular chain of the branching agent, so that the branching agent can be better combined with filler white carbon black in the later processing and application process.
The living anion polymerization has unique advantages in the aspects of molecular chain structure design and molecular weight control. Compared with the traditional free radical polymerization, the mechanism characteristics of the anionic polymerization can be summarized as fast initiation, slow growth, no termination and no transfer, and the mechanism characteristics are based on the no termination. In industrial applications, polystyrene and styrene/diolefin block copolymers of ultra-high molecular weight can be obtained by anionic polymerization, for example: SBS thermoplastic elastomer, solution styrene butadiene rubber, and the like.
Up to now, there has been no disclosure of the synthesis of silicon-and chlorine-containing four-arm star-branched agents for use in the synthesis of star-branched butyl rubber. The invention aims to provide a preparation method of chlorine-silicon-containing four-arm star poly (styrene-conjugated diene) suitable for serving as a butyl rubber branching agent by utilizing an anion polymerization technology. After synthesizing poly (styrene-conjugated diene) by adopting an anion polymerization technology, introducing silicon tetrachloride for coupling to prepare star-shaped poly (styrene-conjugated diene) with silicon as a core and four branched chains, and then adding the star-shaped poly (styrene-conjugated diene) with silicon and silicon into hydrogen chloride to synthesize the chlorine and silicon-containing four-arm star-shaped poly (styrene-conjugated diene) branching agent. The synthesized four-arm star poly (styrene-conjugated diene) is an effective branching agent for synthesizing star-branched butyl rubber.
Disclosure of Invention
The invention aims to provide a preparation method of silicon and chlorine-containing four-arm star poly (styrene-conjugated diene) for butyl rubber branching, wherein the star structure can reduce the stress relaxation of poly (styrene-conjugated diene) macromolecules, silicon can improve the later-stage technical performance, and chlorine is used as an active group in the process of synthesizing butyl rubber and participates in polymerization.
The invention discloses a preparation method of a functionalized four-arm star-shaped branching agent for branching butyl rubber, which comprises the following specific steps:
(1) In a closed water-removing and oxygen-removing polymerization reactor, firstly adding a solvent, then adding styrene and an initiator, keeping the system at the water-free and oxygen-free state to start polymerization reaction 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, adding a terminator after the reaction is finished, discharging, washing and drying to obtain a silicon-containing 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, distilling under reduced pressure, and drying the sample in vacuum to obtain the silicon-and-chlorine-containing functionalized four-arm star-shaped branching agent.
The invention discloses a preparation method of a functionalized four-arm star-shaped branching agent for branching butyl rubber.
Silicon-and chlorine-containing functionalized quadriarmed star branching agents
(R 1 -R 6 Is H, C 1 -C 6 Hydrocarbyl, chlorinated C 1 -C 6 Alkyl radical)
The invention discloses a preparation method of a functionalized four-arm star-shaped branching agent for branching butyl rubber, which is characterized in that the mass ratio of styrene to conjugated diene is controlled within the range of 80-20, preferably 70-40.
The invention discloses a preparation method of a functionalized four-arm star-shaped branching agent for branching butyl rubber, which is characterized in that conjugated dienes copolymerized with styrene are butadiene, isoprene, 1,3-pentadiene, 2,4-dimethylbutadiene, piperylene, 3-methyl-1,3 pentadiene, 2,4-hexadiene, 2,4-hexadiene, 2-neopentyl butadiene, 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 and isoprene.
The invention discloses a preparation method of a functionalized four-arm star-shaped branching agent for butyl rubber branching, which is characterized in that all selected solvents are nonpolar solvents, mainly comprise pentane, cyclopentane, isopentane, n-hexane, cyclohexane, n-heptane, octane, isooctane and methylcyclohexane, and cyclopentane and cyclohexane are preferably selected.
The invention discloses a preparation method of a functionalized four-arm star-shaped branching agent for branching butyl rubber, which is characterized in that an initiator for initiating reaction is a hydrocarbon-based monolithium compound, namely RLi, wherein R is a saturated aliphatic hydrocarbon group, a cycloaliphatic hydrocarbon group, an aromatic hydrocarbon group or a compound group of the saturated aliphatic hydrocarbon group, the cycloaliphatic hydrocarbon group and the aromatic hydrocarbon group containing 1-20 carbon atoms, and n-butyl lithium and t-butyl lithium are preferred.
The invention discloses a preparation method of a functionalized four-arm star-shaped branching agent for branching butyl rubber, which is characterized in that the stirring speed of polymerization reaction is controlled at 50-300 r/min.
The invention discloses a preparation method of a functionalized four-arm star-shaped branching agent for branching butyl rubber, which is characterized in that the reaction temperature is 20-65 ℃, and the reaction rate can be accelerated by increasing the reaction temperature.
The invention discloses a preparation method of a functionalized four-arm star-shaped branching agent for branching butyl rubber, which is characterized in that the reaction time of a polystyrene section and a poly-conjugated diene section is 1-4 hours.
The invention discloses a preparation method of a functionalized four-arm star-shaped branching agent for branching butyl rubber, which is characterized in that a silicon-containing reagent for coupling poly (styrene-conjugated diene) is silicon tetrachloride, and the using amount of the silicon tetrachloride is 1/4 of that of an effective initiator, namely a hydrocarbon-based monolithium compound.
The invention discloses a preparation method of a functionalized four-arm star-shaped branching agent for branching butyl rubber, which is characterized in that chloralkane containing a silicon branching agent is dissolved, wherein the chloralkane mainly comprises methyl chloride, methylene chloride, trichloromethane, carbon tetrachloride, 1,2-dichloroethane, chlorobutane, chloropentane, 2-chloropropane, chlorocyclopentane, chlorocyclohexane and the like, and the methyl chloride, the methylene chloride and the trichloromethane are preferably selected.
The invention discloses a preparation method of a functionalized four-arm star-shaped branching agent for branching butyl rubber, which is characterized in that a terminating agent is a polar substance containing-OH.
The invention discloses a preparation method of a functionalized four-arm star-shaped branching agent for branching butyl rubber, which is characterized in that a terminating agent is a polar substance containing-OH, and the polar substance comprises water, alcohols, organic acids and phenols, preferably methanol and ethanol.
The invention discloses a preparation method of a functionalized four-arm star-shaped branching agent for branching butyl rubber, which is characterized in that silicon-containing poly (styrene-conjugated diene) contains about 0.1 to 2.0 weight percent of chlorine after hydrohalogenation reaction.
The invention discloses a preparation method of a functionalized four-arm star-shaped branching agent for branching butyl rubber, wherein the operation process is well known to those skilled in the art.
Drawings
FIG. 1 is a multiangular laser light scattering pattern of a silicon-and chlorine-containing functionalized four-armed star-shaped branching agent, the weight average molecular weight of which was calculated by integration to be 3.67 ten thousand and the molecular weight distribution 1.17.
Detailed Description
In order to better understand the present invention, the present invention is further illustrated by examples, but the scope of the present invention is not limited to the examples.
(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;
anhydrous methanol, beijing chemical plant;
absolute ethanol, beijing chemical plant.
(2) The analysis method comprises the following steps:
the molecular weight, molecular weight distribution and intrinsic viscosity data of the polymer were measured by three pieces of equipment (SEC) of Wyatt Corp differential Refractive Index (RI)/polygonal laser Light Scattering (LS)/on-line viscosity detector (Vis). The mobile phase was tetrahydrofuran, the flow rate was 1.0mL/min, and the test temperature was 30 ℃. A chromatographic column: 500-103-104-105, ASTRA, wyatt corporation, is data processing software.
The determination of the stress relaxation adopts Mooney stress relaxation, adopts a high-speed rail GT-7080S2 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 used 80 Time taken for the torque to decay 80% (remaining 20%) []And X30 (percentage of remaining torque after the rotor stops rotating for 30 s) expresses the stress relaxation behavior of the rubber.
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-butyl lithium initiator, keeping the system at 35 ℃ in water and oxygen insulation to start polymerization reaction, controlling the stirring speed at 100r/min, reacting for 3 hours, then adding 13mL of isoprene, reacting at 35 ℃ for 4 hours, adding 0.2mL of silicon tetrachloride, adding 50mL of methanol after the reaction is finished, discharging, washing and drying to obtain a silicon-containing branching agent sample.
(2) And (2) dissolving the silicon-containing branching agent sample obtained in the step (1) 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 the silicon-and-chlorine-containing functionalized four-arm star-shaped branching agent, wherein the sample is named as A-1.
Comparative example 1
(1) In a closed water-removing and oxygen-removing polymerization reactor, firstly adding 250mL of cyclohexane, then adding 15mL of styrene, adding 1.2mL of n-butyl lithium initiator, keeping the system at 35 ℃ in water and oxygen insulation to start polymerization reaction, controlling the stirring speed at 100r/min, reacting for 3 hours, then adding 13mL of isoprene, reacting at 35 ℃ for 4 hours, adding 10mL of methanol after the reaction is finished, discharging, washing and drying to obtain a branching agent sample.
(2) And (2) dissolving the branching agent sample in the step (1) in 200mL of dichloromethane, continuously introducing HCl gas at 0 ℃ for 5 hours, washing the product to be neutral, adding 10mL 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 star-shaped branching agent, wherein the sample is named as B-1.
TABLE 1 test results
Example 2
(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 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 at 60 ℃, reacting for 2 hours, adding 0.2mL of silicon tetrachloride, adding 50mL of methanol after the reaction is finished, discharging, washing and drying to obtain a silicon-containing branching agent sample.
(2) And (2) dissolving the silicon-containing branching agent sample obtained in the step (1) 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 the silicon-and-chlorine-containing functionalized four-arm star-shaped branching agent, wherein the sample is named as A-2.
Comparative example 2
(1) In a closed water-removing and oxygen-removing polymerization reactor, firstly adding 250mL of cyclohexane, then adding 15mL of styrene, adding 1.2mL of n-butyllithium initiator, keeping the system at 60 ℃ in water and oxygen insulation to start polymerization reaction, controlling the stirring speed at 100r/min, reacting for 2 hours, then adding 7g of butadiene, reacting at 60 ℃ for 2 hours, adding 50mL of methanol after the reaction is finished, discharging, washing and drying to obtain a silicon-containing branching agent sample.
(2) And (2) dissolving the branching agent sample obtained in the step (1) in 200mL of dichloromethane, continuously introducing HCl gas at 0 ℃ for 5 hours, washing the product to be neutral, adding 10mL of methanol to separate out the product, carrying out reduced pressure distillation, and carrying out vacuum drying on the sample to obtain the branching agent, wherein the sample is named as B-2.
TABLE 2 test results
Example 3
(1) In a closed water-removing and oxygen-removing polymerization reactor, 250mL of cyclopentane is added, 15mL of styrene is added, 2mL of tert-butyl lithium initiator is added, the system is kept in water-free and oxygen-free state to start polymerization reaction, the reaction temperature is 35 ℃, the stirring speed is controlled at 150r/min, the reaction time is 3 hours, 4mL of isoprene is added, the reaction temperature is 35 ℃, the reaction time is 4 hours, 0.1mL of silicon tetrachloride is added, 50mL of methanol is added after the reaction is finished, and a silicon-containing branching agent sample is obtained by discharging, washing and drying.
(2) And (2) dissolving the silicon-containing branching agent sample obtained in the step (1) 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 the silicon-and-chlorine-containing functionalized four-arm star-shaped branching agent, wherein the sample is named as A-3.
Comparative example 3
(1) In a closed water-removing and oxygen-removing polymerization reactor, 250mL of cyclopentane is added, 15mL of styrene is added, 2mL of tert-butyl lithium initiator is added, the system is kept in water-free and oxygen-free state to start polymerization reaction, the reaction temperature is 35 ℃, the stirring speed is controlled at 150r/min, the reaction time is 3 hours, 4mL of isoprene is added, the reaction temperature is 35 ℃, the reaction time is 4 hours, 50mL of methanol is added after the reaction is finished, and the silicon-containing branching agent sample is obtained by discharging, washing and drying.
(2) And (2) dissolving the branching agent sample obtained in the step (1) 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 the branching agent, wherein the sample is named as B-3.
TABLE 3 test results
Example 4
(1) In a closed water-removing and oxygen-removing polymerization reactor, 250mL of cyclopentane is added, 15mL of styrene is added, 3mL of tert-butyl lithium initiator is added, the system is kept in water-free and oxygen-free state to start polymerization reaction, the reaction temperature is 45 ℃, the stirring speed is controlled at 150r/min, the reaction time is 3 hours, 5g of butadiene is added, the reaction temperature is 45 ℃, the reaction time is 3 hours, 0.15mL of silicon tetrachloride is added, 50mL of methanol is added after the reaction is finished, and a silicon-containing branching agent sample is obtained by discharging, washing and drying.
(2) And (2) dissolving the sample of the silicon-containing branching agent (1) in 200mL of carbon tetrachloride, continuously introducing HCl gas at 0 ℃ for 6 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 star-shaped branching agent, wherein the sample is named as A-4.
Comparative example 4
(1) In a closed water-removing and oxygen-removing polymerization reactor, 250mL of cyclopentane is added firstly, 15mL of styrene is added, 3mL of tert-butyl lithium initiator is added, the system is kept in water-free and oxygen-free state to start polymerization reaction, the reaction temperature is 45 ℃, the stirring speed is controlled at 150r/min, the reaction time is 3 hours, 5g of butadiene is added, the reaction temperature is 45 ℃, the reaction time is 3 hours, 50mL of methanol is added after the reaction is finished, and a silicon-containing branching agent sample is obtained after discharging, washing and drying.
(2) And (2) dissolving the branching agent sample in the step (1) in 200mL of carbon tetrachloride, continuously introducing HCl gas at 0 ℃ for 6 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 branching agent, wherein the sample is named as B-4.
TABLE 4 test results
Example 5
(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 at 55 ℃ and at 100r/min for polymerization reaction, adding 10mL of piperylene, reacting at 55 ℃ for 4 hours, adding 0.2mL of silicon tetrachloride, adding 50mL of methanol after the reaction is finished, discharging, washing and drying to obtain a silicon-containing branching agent sample.
(2) And (2) dissolving the sample of the silicon-containing branching agent (1) in 200mL of dichloromethane, continuously introducing HCl gas at 0 ℃ for 10 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 star-shaped branching agent, wherein the sample is named as A-5.
Comparative example 5
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 at 55 ℃ and at 100r/min for polymerization reaction, adding 10mL of piperylene, reacting at 55 ℃ for 4 hours, adding 0.2mL of silicon tetrachloride, adding 50mL of methanol after the reaction is finished, discharging, washing and drying to obtain a silicon-containing branching agent sample named as B-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 at the absolute water and the absolute oxygen to start polymerization reaction, controlling the reaction temperature at 45 ℃, the stirring speed at 80r/min, reacting for 2 hours, then adding 10mL of piperylene, reacting at 45 ℃, reacting for 2 hours, adding 0.2mL of silicon tetrachloride, adding 50mL of methanol after the reaction is finished, discharging, washing and drying to obtain a silicon-containing branching agent sample.
(2) And (2) dissolving the silicon-containing branching agent sample obtained in the step (1) in 200mL of dichloromethane, continuously introducing HCl gas at-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 star-shaped branching agent, wherein the sample is named as A-6.
Comparative 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 at the absolute water and the absolute oxygen to start polymerization reaction, controlling the reaction temperature at 45 ℃, the stirring speed at 80r/min, reacting for 2 hours, then adding 10mL of piperylene, reacting at 45 ℃, reacting for 2 hours, adding 0.2mL of silicon tetrachloride, adding 50mL of methanol after the reaction is finished, discharging, washing and drying to obtain a silicon-containing branching agent sample.
(2) And (2) dissolving the silicon-containing branching agent sample obtained in the step (1) in 200mL of dichloromethane, continuously introducing HCl gas at-5 ℃ for 4 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 star-shaped branching agent, wherein the sample is named as B-6.
TABLE 6 test results
Example 7
(1) In a closed water-removing and oxygen-removing polymerization reactor, 250mL of cyclopentane is added, 15mL of styrene is added, 3mL of tert-butyl lithium initiator is added, the system is kept in water-free and oxygen-free state to start polymerization reaction, the reaction temperature is 35 ℃, the stirring speed is controlled at 120r/min, the reaction time is 3 hours, 5g of butadiene is added, the reaction temperature is 35 ℃, the reaction time is 3 hours, 0.15mL of silicon tetrachloride is added, 50mL of methanol is added after the reaction is finished, and a silicon-containing branching agent sample is obtained by discharging, washing and drying.
(2) And (2) dissolving the sample of the silicon-containing branching agent (1) in 200mL of carbon tetrachloride, continuously introducing HCl gas at 0 ℃ for 10 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 star-shaped branching agent, wherein the sample is named as A-7.
Comparative example 7
(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 35 ℃, controlling the stirring speed at 120r/min, reacting for 3 hours, then adding 5g of butadiene, reacting at 35 ℃, reacting for 3 hours, adding 0.15mL of silicon tetrachloride, adding 50mL of methanol after the reaction is finished, discharging, washing and drying to obtain a silicon-containing branching agent sample.
(2) And (2) dissolving the silicon-containing branching agent sample obtained in the step (1) in 200mL of carbon tetrachloride, continuously introducing HCl gas at-10 ℃ 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 the silicon-and-chlorine-containing functionalized star-shaped branching agent, wherein the sample is named as B-7.
TABLE 7 test results
In conclusion, by adopting the anionic polymerization technology, the synthesized series of silicon-and-chlorine-containing four-arm star-shaped branching agents have lower Mooney stress relaxation and intrinsic viscosity, and can be used as branching agents for preparing star-shaped branched butyl rubber.
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 a functionalized four-arm star-shaped branching agent for branching 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 a reaction temperature of 20-65 ℃ under stirring, then adding a second monomer at a 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, continuously introducing HCl gas at the temperature of-20 to 0 ℃ for 3 to 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; the second monomer is a conjugated diene.
2. The method for preparing the functionalized four-armed star-shaped branching agent for branching butyl rubber according to claim 1, wherein the mass ratio of styrene to conjugated diene is controlled within the range of 80 to 20.
3. The method of claim 1, wherein the conjugated diene is butadiene, isoprene, 1,3-pentadiene, 2,4-dimethylbutadiene, 3-methyl-1,3 pentadiene, 2,4-hexadiene, 2-neopentylbutadiene, 2,5-dimethyl-2,4-hexadiene, cyclopentadiene, methylcyclopentadiene.
4. The method of claim 1, wherein the solvent is a non-polar solvent.
5. The process according to claim 1, wherein the initiator of the initiation reaction is a hydrocarbon-based monolithium compound (RLi), where R is a saturated aliphatic hydrocarbon group, alicyclic hydrocarbon group, or aromatic hydrocarbon group containing 1 to 20 carbon atoms.
6. The method for preparing the functionalized four-armed star-shaped branching agent for branching butyl rubber as claimed in claim 1, wherein the stirring speed of the polymerization reaction is controlled within 50 to 300r/min.
7. The process for preparing functionalized four-armed star-shaped branching agents for branching of butyl rubber as claimed in claim 5, characterized in that the amount of silicon tetrachloride used is 1/4 of the amount of the effective initiator, hydrocarbyl monolithium compound.
8. The method of claim 1, wherein the silicon-containing branching agent is dissolved in chlorinated alkane.
9. The process according to claim 1, wherein the terminating agent is a polar OH-containing substance.
10. The method of claim 1, wherein the terminating agent is water, alcohols, phenols.
11. The method of claim 1, wherein the silicon-containing four-arm star-shaped branching agent contains 0.1 to 2.0 weight percent of chlorine after hydrohalogenation.
12. The method for preparing the functionalized four-arm star-shaped branching agent for butyl rubber branching according to claim 2, wherein the mass ratio of styrene to conjugated diene is controlled within a range of 70 to 40.
13. The method of claim 3, wherein the conjugated diene is butadiene or isoprene.
14. The method of claim 4, wherein the solvent is pentane, cyclopentane, n-hexane, cyclohexane, n-heptane, octane, methylcyclohexane.
15. The method of claim 14, wherein the solvent is cyclopentane, cyclohexane.
16. The method of claim 5, wherein the initiator is n-butyl lithium or t-butyl lithium.
17. The process of claim 8, wherein the chlorinated alkane is methyl chloride, methylene chloride, chloroform, carbon tetrachloride, 1,2-dichloroethane, chlorobutane, chloropentane, 2-chloropropane, chlorocyclopentane, chlorocyclohexane.
18. The method of claim 17, wherein the chlorinated alkane is methyl chloride, methylene chloride, or chloroform.
19. The method of claim 10, wherein the terminating agent is methanol or ethanol.
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| CN1036022A (en) * | 1987-12-11 | 1989-10-04 | 埃克森化学专利公司 | Improved the isoolefin polymer of processing characteristics |
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| CN101353386A (en) * | 2007-07-27 | 2009-01-28 | 北京石油化工学院 | Initiation system for polymerization of star-branched polyisobutene or isobutene-diene rubber positive ion |
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