CN110845650B - Slurry polymerization method for preparing bimodal distribution star-shaped branched butyl rubber by using terminal imino functionalized macromolecular branching agent - Google Patents
Slurry polymerization method for preparing bimodal distribution star-shaped branched butyl rubber by using terminal imino functionalized macromolecular branching agent Download PDFInfo
- Publication number
- CN110845650B CN110845650B CN201911155805.2A CN201911155805A CN110845650B CN 110845650 B CN110845650 B CN 110845650B CN 201911155805 A CN201911155805 A CN 201911155805A CN 110845650 B CN110845650 B CN 110845650B
- Authority
- CN
- China
- Prior art keywords
- butyl rubber
- branching agent
- star
- imino
- branched butyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- 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
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/08—Styrene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
- C08F8/32—Introducing nitrogen atoms or nitrogen-containing groups by reaction with amines
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention belongs to the technical field of butyl rubber preparation, and relates to a slurry polymerization method for preparing bimodal distribution star-shaped branched butyl rubber by using an imino-functionalized macromolecular branching agent. The slurry polymerization method comprises two steps of synthesizing an imino-functionalized macromolecular branching agent and synthesizing star-branched butyl rubber with amino, a copolymer of styrene and derivatives thereof and isoprene is prepared by adopting a living anion polymerization technology, and the imino-containing branching agent macromolecules are obtained by using Schiff bases for end capping. Dissolving a branching agent in methyl chloride, adding the solution into a butyl rubber slurry polymerization kettle, and preparing star-shaped branched butyl rubber with bimodal distribution as a grafting agent and a slurry stabilizer for cationic polymerization; the Mooney stress relaxation and the intrinsic viscosity are lower, and the processability is better; the imino group introduced during the end sealing can increase the polarity of the branching agent, is beneficial to the dispersion of carbon black in a butyl rubber matrix, improves the compatibility of the butyl rubber and the carbon black and reduces the system energy.
Description
Technical Field
The invention belongs to the technical field of butyl rubber preparation, and particularly relates to a slurry polymerization method for preparing bimodal distribution star-shaped branched butyl rubber by using an imino-functionalized macromolecular branching agent; in particular to a method for preparing bimodal distribution star-shaped branched butyl rubber by a slurry polymerization method by taking imino functionalized macromolecules as branching agents; namely a preparation method for synthesizing star-shaped branched butyl rubber by using diblock terminal imino copolymer of styrene and derivatives thereof and isoprene as a branching agent and a slurry stabilizer.
Background
Butyl rubber is polymerized from isobutene and a small amount of isoprene, and is the only industrial product of the existing cationic polymerization. The molecular chain unsaturation degree of the butyl rubber is extremely low, about 0.5 to 3.3 percent (mol), which is far lower than that of the natural rubber, but the molecular chain unsaturation degree is enough to form a cross-linked network structure, and because of the high saturation structure, the butyl rubber has excellent aging resistance, low air permeability and air tightness which is 20 times that of the natural rubber; excellent shock-absorbing performance, good weather resistance and ozone resistance, thus being widely used for manufacturing medical bottle stoppers, rubber gloves and high-quality radial tires. The butyl rubber and the ethylene propylene diene monomer rubber have better heat resistance when being blended, and the durability and the storage life are better than those of a natural rubber inner tube.
Although butyl rubber has many advantages, the molecular structure is arranged closely, and has huge methyl group, which causes the stress relaxation to be slow in processing, the energy consumption is high, the processing performance is poor, in order to solve the problem, star-shaped branched butyl rubber is researched, and the star-shaped branched butyl rubber is a bimodal polymer which is composed of a graft structure with high molecular mass and a linear component with low molecular mass, has excellent viscoelasticity, has faster stress relaxation compared with the linear butyl rubber, and has lower energy consumption in processing.
In the process of preparing the star-branched butyl rubber, the key to the successful preparation of the star-branched butyl rubber is the synthesis of an effective branching agent. Researchers have conducted many studies on star-type branching systems using divinylbenzene as a branching agent. 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. A large number of double bonds exist in an isoprene segment in poly (styrene-isoprene), and a polyisobutylene chain segment is formed in the polymerization process of butyl rubber to attack the double bonds in the polyisoprene segment to form a high-branching structure. The isoprene connecting segment formed by anionic polymerization has two microstructures of a 1, 4 structure and a 3,4 structure, the isoprene of the 3,4 structure is polymerized into a 1, 1-substituted vinyl polymer, the steric hindrance of a substituent group is small, the polarization degree is increased, and the double bond on the main chain of the 3, 4-structured polyisoprene is easily attacked by the polyisobutyl chain segment. Therefore, the polarity regulator such as amine or tetrahydrofuran is used for regulating the microstructure of polyisoprene to be mainly 3,4 structure, so that the grafting efficiency of the branching agent can be improved, and the average arm number and the macromolecular content of branched macromolecules can be increased.
The slurry polymerization is adopted in the industrial production of butyl rubber in China, the slurry polymerization has high conversion rate and is more economical compared with solution polymerization slurry polymerization, but in the slurry polymerization process, products are easy to agglomerate and block polymerization equipment, and a slurry stabilizer is added into a polymerization system to prevent agglomeration, prolong continuous polymerization time and improve energy efficiency.
Carbon black is the most widely applied reinforcing filler in rubber, butyl rubber has high molecular chain saturation degree, no polar group, poor compatibility with carbon black during processing, obvious payne effect, obviously reduced mechanical property and high processing energy consumption, and imino is introduced into a branching agent to enhance the molecular chain polarity of the butyl rubber, improve the compatibility of the butyl rubber and the reinforcing filler and also reduce the processing energy consumption.
Up to now, no report has been published on the synthesis of star-branched butyl rubber by using imino-terminated styrene and its derivatives and 3,4 structure-based isoprene diblock copolymer as branching agent and slurry stabilizer, which can improve the processability of butyl rubber, prolong the polymerization period and improve the compatibility of butyl rubber and carbon black. The synthesized star-shaped branched butyl rubber with double peak distribution is suitable for being used as the components of tire inner liners, inner tubes and sealing elements.
Disclosure of Invention
The invention aims to provide a slurry polymerization method for preparing bimodal distribution star-branched butyl rubber by using an imino-terminated functionalized macromolecular branching agent, which is characterized by comprising the following specific experimental steps:
step 1, synthesis of a terminal imino-functionalized macromolecular branching agent:
step 2, synthesizing star-shaped branched butyl rubber with amino groups:
wherein X is H, CH 3 、C(CH 3 ) 3 Or Cl; the solvent selected in the synthesis process is a nonpolar solvent, and mainly comprises one or more of n-hexane, cyclohexane, pentane, cyclopentane, isopentane, n-heptane, octane and isooctane; the initiator is an alkyl monolithium compound RLi, wherein R is a linear or branched chain alkyl, cycloalkyl or aryl containing 1-12 carbon atoms, and n-butyllithium and tert-butyllithium are specifically selected; the end capping agent is Schiff base (Schiff base) with a structural formula of R 1 R 2 C＝NR 3 Wherein R is 1 、R 2 、R 3 Is alkyl, aryl or alkoxy; or selecting one of benzaldehyde condensed aniline, benzaldehyde condensed p-methylaniline and p-N, N-dimethylaminobenzoic acid condensed aniline;
the specific experiment of the step 1 comprises the following steps:
(1) adding a solvent, styrene and derivatives thereof, Tetramethylethylenediamine (TMEDA) and an initiator into a polymerization bottle under anhydrous and anaerobic conditions, shaking up and sealing, reacting at 20-50 ℃ for 3-5 hours, adding isoprene, reacting at 20-50 ℃ for 3-6 hours, adding Schiff base with the same amount as the initiator, reacting at 50-60 ℃ for 30min, adding a polymerization solvent and a terminator methanol after the reaction is finished, repeatedly dissolving and flocculating, washing off unreacted end-capping reagent, and drying in a vacuum drying oven at 30 ℃ for later use;
(2) dissolving a prepared branching agent sample, adding the sample, isobutene and isoprene into a polymerization kettle, reducing the temperature to below-85 ℃, adding a prepared initiator, adding methanol within 1min after the reaction starts, stopping, and carrying out vacuum drying on the sample to obtain the star-shaped branched butyl rubber with bimodal distribution; the synthesized star-branched butyl rubber has a number average molecular weight of 1.17 × 10 5 ～33.1×10 5 Weight average molecular weight of 3.26X 10 5 ～1.56×10 6 The molecular weight distribution is 1.8-3.4. The content of the synthesized star-shaped branched butyl rubber polymer region is 3-15%, and the molecular weight of the polymer region is 5.91 multiplied by 10 5 ～8.82×10 6 And the average arm number is 4-12.
Preparing the initiator: adding a certain amount of saturated dichloromethane solution of water into aluminium trichlorotriethylcomplex, and adding 10-50 mL of water for removing waterMethylene dichlorideDiluting and aging at room temperature for 10-30 min.
In the process of synthesizing the terminal imino functionalized macromolecular branching agent, the content of the polystyrene and the derivatives thereof accounts for 40-80wt% of the copolymer, the content of the 3,4 structures in the polyisoprene accounts for 10-80%, the end-capping efficiency of the end-capping agent is 70%, and the molecular weight of the branching agent is 5 multiplied by 10 3 ～9.2×10 4 。
In the process of synthesizing the terminal imino group functionalized macromolecular branching agent, the polymerization time of styrene and derivatives thereof is 1-4 h, the polymerization time of isoprene is 2-6 h, and the end capping agent is added for reaction for 20-60 min. The reaction temperature of the polystyrene and the derivatives thereof and the polyisoprene is 20-50 ℃, the reaction rate can be increased by raising the temperature, and the reaction temperature is 50-60 ℃ when the Schiff base is used for end sealing.
The amount of the branching agent used in the synthesis of the star-branched butyl rubber is 0.2 to 3 percent, and the branching agent can also play a role of a slurry stabilizer, and the slurry stability is better when the proportion of the polystyrene and the derivative thereof is higher. After the slurry stabilizer is added, the continuous polymerization time is prolonged from 30-40 hours to 40-80 hours.
The diluent is chloromethane; the polymerization solvent for dissolving the branching agent during polymerization is chloromethane, dichloromethane, trichloromethane, carbon tetrachloride, 1, 2-dichloroethane, chlorobutane, chloropentane, 2-chloropropane, chlorocyclopentane, chlorocyclohexane, toluene and homologs thereof, all of which are polar solvents. The main initiator can be water, 2-chloro-2, 4, 4-trimethylpentane, HCl, BrH, HF, HClO 4 、HClSO 3 、H 2 SO 4 、H 3 PO 4 One of (1); the coinitiator may be BeCl 2 、ZnCl 2 、CdCl 2 、HgCl 2 、BF 3 、BCl 3 、AlCl 3 、Al 2 Et 3 Cl 3 、AlEt 2 Cl、AlBr 3 、RAl 3 、R n AlX n-3 、SnCl 4 、TiCl 4 、TiBr 4 、ZrCl 4 、VCl 4 、WCl 5 、FeCl 3 Wherein R represents C1-C8 alkane, X represents halogen atom, and n represents an integer of 0-3.
During the synthesis of star-branched butyl rubber, the total concentration of the monomers isobutene and isoprene is 10-30 wt%, preferably 30% of the reaction system. The monomer isoprene accounts for 2-6 wt% of the total monomer.
The reaction temperature for synthesizing the star-shaped branched butyl rubber is between 60 ℃ below zero and 100 ℃ below zero, and the molecular weight can be improved by reducing the reaction temperature.
The method has the beneficial effects that the imino group is introduced at the tail end of the branching agent, the molecular chain polarity of the butyl rubber is enhanced, the compatibility of the butyl rubber and the reinforcing filler is improved, and the compatibility of the butyl rubber and the carbon black is improved. The synthesized star-shaped branched butyl rubber has lower solution viscosity, higher molecular weight, better carbon black compatibility, faster stress relaxation and far lower processing energy consumption than linear butyl rubber. The N in the terminal imino group can increase the electron cloud density on the double bond of the isobutene and the isoprene, is beneficial to the attack of cation active species and the existence of electron-pushing groups, improves the condition of rare electron cloud on carbon, reduces the system energy and increases the stability of cation polymerization.
Detailed Description
The invention provides a slurry polymerization method for preparing bimodal distribution star-shaped branched butyl rubber by using a terminal imino functionalized macromolecular branching agent, wherein the grafting efficiency of the branching agent is related to the microstructure of polyisoprene, and the polyisoprene with a 3,4 structure as a main structure has better grafting effect compared with the polyisoprene with a 1,2 structure as a main structure; styrene and its derivatives in the diblock copolymer of styrene and its derivatives with isoprene act to increase the solubility of the branching agent and the slurry stabilizer; the terminal imino groups of the branching agent increase the molecular polarity and improve the compatibility of the butyl rubber with carbon black. The synthesized star-shaped branched butyl rubber has lower solution viscosity, higher molecular weight, better carbon black compatibility, faster stress relaxation and far lower processing energy consumption than linear butyl rubber.
The invention is further illustrated by the examples in order to provide a better understanding of the invention.
(1) The raw material sources are as follows:
styrene, petroleum Yanshan petrochemical company, China;
isobutylene, petroleum Yanshan petrochemical, China;
monochloromethane, China Petroleum Yanshan petrochemical Co
Isoprene, petroleum Yanshan petrochemical company, China;
cyclohexane, petroleum Yanshan petrochemical, China;
n-butyllithium, lark technologies ltd;
trichlorotriethylaluminum, largeway technologies ltd;
n, N, N ', N' -tetramethylethylenediamine, Prodwellin technologies, Inc.;
p-N, N-dimethylaminobenzoic acid anilide, Bailingwei science and technology Co., Ltd;
dichloromethane, beijing chemical plant;
anhydrous methanol, beijing chemical plant.
(2) The analysis method comprises the following steps:
the molecular weight and molecular weight distribution of the polymer, and the data of the content of the high molecular region were measured by using a combined equipment (SEC) of differential Refractive Index (RI)/multi-angle laser Light Scattering (LS) of Wyatt. The mobile phase was THF, flow rate was 1.0mL/min, and the test temperature was 35 ℃. A chromatographic column: 500-, 103-, 104-105-, the data processing software is Wyatt ASTRA.
Microstructure of polymer by hydrogen nuclear magnetic resonance spectroscopy 1 H-NMR measurement. With CDCl 3 (DMSO) as solvent, TMS as internal standard, at room temperature using a Bruker Vance 400MHZ nuclear magnetic resonance apparatus 1 H-NMR measurement.
The average arm number f is the molecular weight (Mw) passing through the polymer domain 1 (branched)) and molecular weight (Mw) of the low molecular region 0 (linear)) the average number of arms of the branched butyl rubber was calculated, i.e., f ═ Mw 1 /Mw 0
Example 1
(1) Under anhydrous and anaerobic conditions, 250mL of cyclohexane, 16mL of styrene and 1mL of Tetramethylethylenediamine (TMEDA) are added into a polymerization flask, 0.7mL of N-butyllithium (0.9M hexane solution) is added, the mixture is shaken and sealed, the mixture is reacted at 50 ℃ for 5 hours, then 12mL of isoprene is added, the mixture is reacted at 50 ℃ for 6 hours, 2mL of p-N, N-dimethylaminobenzoic acid anilide (0.1M cyclohexane solution) is added, the reaction is carried out at 60 ℃ for 30 minutes, cyclohexane and methanol are added to repeatedly flocculate and dissolve the product, unreacted p-N, N-dimethylaminobenzoic acid anilide is washed off, and the product is dried in a vacuum drying oven at 30 ℃ for standby and is numbered SI-1.
(2) Dissolving a branching agent sample accounting for 0.2% of the total monomer weight in 40mL of dichloromethane, adding to a 4L polymerization kettle in total volume, adding 1296mL of methyl chloride, 536mL of isobutylene, 29mL of isoprene, 190r/min of rotation speed of a stirring paddle, reducing the temperature to below-85 ℃, adding 2.65mL of water in saturated dichloromethane solution to 10mL of tri-chloroethyl aluminum (0.4M in hexane), and adding 40mL of water-removed CH 2 Cl 2 And aging for 20min, adding the system, adding methanol when the temperature rises to-40 ℃ after the reaction starts, stopping adding the methanol, and drying the sample in vacuum to obtain a bimodal distribution star branched butyl rubber sample with the number of 1.
Comparative example 1
1296mL of methyl chloride, 536mL of isobutene and 29mL of isoprene are added into a 4L polymerization kettle, the rotation speed of a stirring paddle is 190r/min, the temperature is reduced to be below-85 ℃, 2.65mL of water-dichloromethane saturated solution is added into 10mL of trichlorotriethylaluminum (0.4M hexane solution), and 40mL of dehydrated CH is added 2 Cl 2 Aging for 20min, adding the system, adding methanol when the temperature rises to-40 ℃ after the reaction starts, stopping, and carrying out vacuum drying on the sample to obtain a bimodal distribution star-shaped branched butyl rubber sample, wherein the number is 2.
Example 2
(1) Under anhydrous and anaerobic conditions, adding 250mL of cyclohexane, 16mL of styrene and 1mL of Tetramethylethylenediamine (TMEDA) into a polymerization bottle, adding 0.7mL of N-butyllithium (0.9M hexane solution), shaking up and sealing, reacting at 50 ℃ for 5 hours, then adding 12mL of isoprene, reacting at 50 ℃ for 6 hours, adding 2mL of p-N, N-dimethylaminobenzoic acid anilide (0.1M cyclohexane solution), reacting at 60 ℃ for 30 minutes, adding cyclohexane and methanol to repeatedly flocculate and dissolve the product, washing off unreacted p-N, N-dimethylaminobenzoic acid anilide, and drying in a vacuum drying oven at 30 ℃ for later use, wherein the number is SI-1.
(2) Dissolving a branching agent sample accounting for 0.5 percent of the total weight of monomers in 40mL of dichloromethane, adding the solution into a 4L polymerization kettle with the total volume, adding 1296mL of methyl chloride, 536mL of isobutene and 29mL of isoprene, rotating a stirring paddle at the speed of 190r/min, reducing the temperature to be below-85 ℃, adding 2.65mL of water in saturated dichloromethane solution into 10mL of trichlorotriethylaluminum (0.4M hexane solution), and adding 40mL of dehydrated CH 2 Cl 2 Aging for 20min, adding the system, adding methanol when the temperature rises to-40 ℃ after the reaction starts, stopping, and carrying out vacuum drying on the sample to obtain a bimodal distribution star-shaped branched butyl rubber sample, wherein the number is 3.
Example 3
(1) Under anhydrous and anaerobic conditions, adding 250mL of cyclohexane, 16mL of styrene and 1mL of Tetramethylethylenediamine (TMEDA) into a polymerization bottle, adding 0.7mL of N-butyllithium (0.9M hexane solution), shaking up and sealing, reacting at 50 ℃ for 5 hours, then adding 12mL of isoprene, reacting at 50 ℃ for 6 hours, adding 2mL of p-N, N-dimethylaminobenzoic acid anilide (0.1M cyclohexane solution), reacting at 60 ℃ for 30 minutes, adding cyclohexane and methanol to repeatedly flocculate and dissolve the product, washing off unreacted p-N, N-dimethylaminobenzoic acid anilide, and drying in a vacuum drying oven at 30 ℃ for later use, wherein the number is SI-1.
(2) Dissolving a branching agent sample accounting for 1.0 percent of the total weight of monomers in 40mL of dichloromethane, adding the solution into a 4L polymerization kettle with the total volume, adding 1296mL of methyl chloride, 536mL of isobutene and 29mL of isoprene, rotating a stirring paddle at the speed of 190r/min, reducing the temperature to below-85 ℃, adding 2.65mL of water in saturated dichloromethane solution into 10mL of trichlorotriethylaluminum (0.4M hexane solution), and adding 40mL of dehydrated CH 2 Cl 2 And aging for 20min, adding the system, adding methanol when the temperature rises to-40 ℃ after the reaction starts, stopping, and carrying out vacuum drying on the sample to obtain a bimodal distribution star-shaped branched butyl rubber sample, wherein the number is 4.
Example 4
(1) Under anhydrous and anaerobic conditions, 250mL of cyclohexane, 16mL of styrene and 1mL of Tetramethylethylenediamine (TMEDA) are added into a polymerization flask, 0.7mL of N-butyllithium (0.9M hexane solution) is added, the mixture is shaken and sealed, the mixture is reacted at 50 ℃ for 5 hours, then 12mL of isoprene is added, the mixture is reacted at 50 ℃ for 6 hours, 2mL of p-N, N-dimethylaminobenzoic acid anilide (0.1M cyclohexane solution) is added, the reaction is carried out at 60 ℃ for 30 minutes, cyclohexane and methanol are added to repeatedly flocculate and dissolve the product, unreacted p-N, N-dimethylaminobenzoic acid anilide is washed off, and the product is dried in a vacuum drying oven at 30 ℃ for standby and is numbered SI-1.
(2) Dissolving a branching agent sample accounting for 3.0 percent of the total weight of monomers in 40mL of dichloromethane, adding the solution into a 4L polymerization kettle with the total volume, adding 1296mL of methyl chloride, 536mL of isobutene and 29mL of isoprene, rotating a stirring paddle at the speed of 190r/min, reducing the temperature to be below-85 ℃, adding 2.65mL of water in saturated dichloromethane solution into 10mL of trichlorotriethylaluminum (0.4M hexane solution), and adding 40mL of dehydrated CH 2 Cl 2 And aging for 20min, adding the system, adding methanol when the temperature rises to-40 ℃ after the reaction starts, stopping adding the methanol, and drying the sample in vacuum to obtain a bimodal distribution star branched butyl rubber sample with the number of 5.
Example 5
(1) Under anhydrous and anaerobic conditions, adding 250mL of cyclohexane and 16mL of styrene into a polymerization bottle, adding 0.7mL of N-butyllithium (0.9M hexane solution), shaking up and sealing, reacting at 50 ℃ for 5 hours, then adding 12mL of isoprene, reacting at 50 ℃ for 6 hours, adding 2mL of p-N, N-dimethylaminobenzoic acid anilide (0.1M cyclohexane solution), reacting at 60 ℃ for 30 minutes, adding cyclohexane and methanol to repeatedly flocculate and dissolve the product, washing off unreacted p-N, N-dimethylaminobenzoic acid anilide, and drying in a vacuum drying oven at 30 ℃ for later use, wherein the number is SI-2.
(2) Dissolving a branching agent sample accounting for 1.0% of the total weight of monomers in 40mL of dichloromethane, adding the solution into a 4L polymerization kettle with the total volume, adding 1296mL of methyl chloride, 536mL of isobutene and 29mL of isoprene, rotating a stirring paddle at the speed of 190r/min, reducing the temperature to below-85 ℃, adding 2.65mL of water in saturated dichloromethane solution into 10mL of trichlorotriethylaluminum (0.4M in hexane), and adding 40mL of dehydrated CH 2 Cl 2 Aging for 20min, adding into the system,and (3) adding methanol to stop when the temperature rises to-40 ℃ after the reaction starts, and carrying out vacuum drying on the sample to obtain a bimodal distribution star-shaped branched butyl rubber sample, wherein the number is 6.
Example 6
(1) Under anhydrous and anaerobic conditions, adding 250mL of cyclohexane, 16mL of styrene and 0.4mL of Tetramethylethylenediamine (TMEDA) into a polymerization bottle, adding 0.7mL of N-butyllithium (0.9M hexane solution), shaking uniformly, sealing, reacting at 50 ℃ for 5 hours, then adding 12mL of isoprene, reacting at 50 ℃ for 6 hours, adding 2mL of p-N, N-dimethylaminobenzoic acid anilide (0.1M cyclohexane solution), reacting at 60 ℃ for 30 minutes, adding cyclohexane and methanol to repeatedly flocculate and dissolve the product, washing off unreacted p-N, N-dimethylaminobenzoic acid anilide, and drying in a vacuum drying oven at 30 ℃ for standby, wherein the number is SI-3.
(2) Dissolving a branching agent sample accounting for 1.0 percent of the total weight of monomers in 40mL of dichloromethane, adding the solution into a 4L polymerization kettle with the total volume, adding 1296mL of methyl chloride, 536mL of isobutene and 29mL of isoprene, rotating a stirring paddle at the speed of 190r/min, reducing the temperature to below-85 ℃, adding 2.65mL of water in saturated dichloromethane solution into 10mL of trichlorotriethylaluminum (0.4M hexane solution), and adding 40mL of dehydrated CH 2 Cl 2 Aging for 20min, adding the system, adding methanol when the temperature rises to-40 ℃ after the reaction starts, stopping, and carrying out vacuum drying on the sample to obtain a bimodal distribution star-shaped branched butyl rubber sample, wherein the number is 7.
Example 7
(1) Under anhydrous and anaerobic conditions, adding 250mL of cyclohexane, 16mL of styrene and 0.7mL of Tetramethylethylenediamine (TMEDA) into a polymerization bottle, adding 0.7mL of N-butyllithium (0.9M hexane solution), shaking uniformly, sealing, reacting at 50 ℃ for 5 hours, then adding 12mL of isoprene, reacting at 50 ℃ for 6 hours, adding 2mL of p-N, N-dimethylaminobenzoic acid anilide (0.1M cyclohexane solution), reacting at 60 ℃ for 30 minutes, adding cyclohexane and methanol to repeatedly flocculate and dissolve the product, washing off unreacted p-N, N-dimethylaminobenzoic acid anilide, and drying in a vacuum drying oven at 30 ℃ for standby, wherein the number is SI-4.
(2) A 1.0% sample of branching agent by total weight of monomers was dissolved in 40mL of methylene chloride,adding into a 4L polymerization kettle, adding 1296mL of chloromethane, 536mL of isobutene and 29mL of isoprene, rotating the stirring paddle at 190r/min, reducing the temperature to below-85 deg.C, adding 2.65mL of water in saturated dichloromethane solution into 10mL of aluminium trichlorotriethylate (0.4M hexane solution), adding 40mL of dehydrated CH 2 Cl 2 Aging for 20min, adding the system, adding methanol when the temperature rises to-40 ℃ after the reaction starts, stopping, and carrying out vacuum drying on the sample to obtain a bimodal distribution star-shaped branched butyl rubber sample, wherein the number is 8.
Example 8
(1) Under anhydrous and anaerobic conditions, adding 250mL of cyclohexane, 14mL of styrene and 1mL of Tetramethylethylenediamine (TMEDA) into a polymerization bottle, adding 0.7mL of N-butyllithium (0.9M hexane solution), shaking up and sealing, reacting at 50 ℃ for 5 hours, then adding 14mL of isoprene, reacting at 50 ℃ for 6 hours, adding 2mL of p-N, N-dimethylaminobenzoic acid anilide (0.1M cyclohexane solution), reacting at 60 ℃ for 30 minutes, adding cyclohexane and methanol to repeatedly flocculate and dissolve the product, washing off unreacted p-N, N-dimethylaminobenzoic acid anilide, and drying in a vacuum drying oven at 30 ℃ for later use, wherein the number is SI-5.
(2) Dissolving a branching agent sample accounting for 1.0 percent of the total weight of monomers in 40mL of dichloromethane, adding the solution into a 4L polymerization kettle with the total volume, adding 1296mL of methyl chloride, 536mL of isobutene and 29mL of isoprene, rotating a stirring paddle at the speed of 190r/min, reducing the temperature to below-85 ℃, adding 2.65mL of water in saturated dichloromethane solution into 10mL of trichlorotriethylaluminum (0.4M hexane solution), and adding 40mL of dehydrated CH 2 Cl 2 Aging for 20min, adding the system, adding methanol when the temperature rises to-40 ℃ after the reaction starts, stopping, and carrying out vacuum drying on the sample to obtain a bimodal distribution star-shaped branched butyl rubber sample, wherein the number is 9.
Example 9
(1) Under anhydrous and anaerobic conditions, adding 250mL of cyclohexane, 17mL of styrene and 1mL of Tetramethylethylenediamine (TMEDA) into a polymerization bottle, adding 0.7mL of N-butyllithium (0.9M hexane solution), shaking up and sealing, reacting at 50 ℃ for 5 hours, then adding 11.5mL of isoprene, reacting at 50 ℃ for 6 hours, adding 2mL of p-N, N-dimethylaminobenzoic acid anilide (0.1M cyclohexane solution), reacting at 60 ℃ for 30 minutes, adding cyclohexane and methanol to repeatedly flocculate and dissolve the product, washing off unreacted p-N, N-dimethylaminobenzoic acid anilide, and drying in a vacuum drying oven at 30 ℃ for standby, wherein the number is SI-6.
(2) Dissolving a branching agent sample accounting for 1.0 percent of the total weight of monomers in 40mL of dichloromethane, adding the solution into a 4L polymerization kettle with the total volume, adding 1296mL of methyl chloride, 536mL of isobutene and 29mL of isoprene, rotating a stirring paddle at the speed of 190r/min, reducing the temperature to below-85 ℃, adding 2.65mL of water in saturated dichloromethane solution into 10mL of trichlorotriethylaluminum (0.4M hexane solution), and adding 40mL of dehydrated CH 2 Cl 2 Aging for 20min, adding the system, adding methanol when the temperature rises to-40 ℃ after the reaction starts, stopping, and carrying out vacuum drying on the sample to obtain a bimodal distribution star-shaped branched butyl rubber sample with the number of 10.
Example 10
(1) Under anhydrous and anaerobic conditions, adding 250mL of cyclohexane, 20mL of styrene and 1mL of Tetramethylethylenediamine (TMEDA) into a polymerization bottle, adding 0.7mL of N-butyllithium (0.9M hexane solution), shaking up and sealing, reacting at 50 ℃ for 5 hours, then adding 10mL of isoprene, reacting at 50 ℃ for 6 hours, adding 2mL of p-N, N-dimethylaminobenzoic acid anilide (0.1M cyclohexane solution), reacting at 60 ℃ for 30 minutes, adding cyclohexane and methanol to repeatedly flocculate and dissolve the product, washing off unreacted p-N, N-dimethylaminobenzoic acid anilide, and drying in a vacuum drying oven at 30 ℃ for later use, wherein the number is SI-7.
(2) Dissolving a branching agent sample accounting for 1.0 percent of the total weight of monomers in 40mL of dichloromethane, adding the solution into a 4L polymerization kettle with the total volume, adding 1296mL of methyl chloride, 536mL of isobutene and 29mL of isoprene, rotating a stirring paddle at the speed of 190r/min, reducing the temperature to below-85 ℃, adding 2.65mL of water in saturated dichloromethane solution into 10mL of trichlorotriethylaluminum (0.4M hexane solution), and adding 40mL of dehydrated CH 2 Cl 2 Aging for 20min, adding the system, adding methanol when the temperature rises to-40 ℃ after the reaction starts, stopping, and carrying out vacuum drying on the sample to obtain a bimodal distribution star-shaped branched butyl rubber sample, wherein the number is 11.
Example 11
(1) Under anhydrous and anaerobic conditions, 250mL of cyclohexane, 16mL of styrene and 1mL of Tetramethylethylenediamine (TMEDA) are added into a polymerization flask, 0.6mL of N-butyllithium (0.9M hexane solution) is added, the mixture is shaken and sealed, the mixture is reacted at 50 ℃ for 5 hours, then 12mL of isoprene is added, the mixture is reacted at 50 ℃ for 6 hours, 2mL of p-N, N-dimethylaminobenzoic acid anilide (0.1M cyclohexane solution) is added, the reaction is carried out at 60 ℃ for 30 minutes, cyclohexane and methanol are added to repeatedly flocculate and dissolve the product, unreacted p-N, N-dimethylaminobenzoic acid anilide is washed off, and the product is dried in a vacuum drying oven at 30 ℃ for standby and is numbered SI-8.
(2) Dissolving a branching agent sample accounting for 1.0% of the total weight of monomers in 40mL of dichloromethane, adding the solution into a 4L polymerization kettle with the total volume, adding 1296mL of methyl chloride, 536mL of isobutene and 29mL of isoprene, rotating a stirring paddle at the speed of 190r/min, reducing the temperature to below-85 ℃, adding 2.65mL of water in saturated dichloromethane solution into 10mL of trichlorotriethylaluminum (0.4M in hexane), and adding 40mL of dehydrated CH 2 Cl 2 Aging for 20min, adding the system, adding methanol when the temperature rises to-40 ℃ after the reaction starts, stopping, and carrying out vacuum drying on the sample to obtain a bimodal distribution star-shaped branched butyl rubber sample with the number of 12.
Example 12
(1) Under anhydrous and anaerobic conditions, adding 250mL of cyclohexane, 16mL of styrene and 1mL of Tetramethylethylenediamine (TMEDA) into a polymerization bottle, adding 0.5mL of N-butyllithium (0.9M hexane solution), shaking up and sealing, reacting at 50 ℃ for 5 hours, then adding 12mL of isoprene, reacting at 50 ℃ for 6 hours, adding 2mL of p-N, N-dimethylaminobenzoic acid anilide (0.1M cyclohexane solution), reacting at 60 ℃ for 30 minutes, adding cyclohexane and methanol to repeatedly flocculate and dissolve the product, washing off unreacted p-N, N-dimethylaminobenzoic acid anilide, and drying in a vacuum drying oven at 30 ℃ for later use, wherein the number is SI-9.
(2) Dissolving a branching agent sample accounting for 1.0 percent of the total weight of monomers in 40mL of dichloromethane, adding the solution into a polymerization kettle with the total volume of 4L, adding 1296mL of methyl chloride, 536mL of isobutene and 29mL of isoprene, reducing the rotation speed of a stirring paddle to 190r/min, reducing the temperature to below-85 ℃, and adding 2.65mL of water in a dichloromethane saturated solution to 10mL of trichlorotriethylTo the complex aluminum (0.4M in hexane) was added 40mL of CH removed 2 Cl 2 Aging for 20min, adding the system, adding methanol when the temperature rises to-40 ℃ after the reaction starts, stopping, and carrying out vacuum drying on the sample to obtain a bimodal distribution star-shaped branched butyl rubber sample, wherein the number is 13.
Example 13
(1) Under anhydrous and anaerobic conditions, 250mL of cyclohexane, 16mL of styrene and 1mL of Tetramethylethylenediamine (TMEDA) are added into a polymerization flask, 0.45mL of N-butyllithium (0.9M hexane solution) is added, the mixture is shaken and sealed, the mixture is reacted at 50 ℃ for 5 hours, then 12mL of isoprene is added, the mixture is reacted at 50 ℃ for 6 hours, 2mL of p-N, N-dimethylaminobenzoic acid anilide (0.1M cyclohexane solution) is added, the reaction is carried out at 60 ℃ for 30 minutes, cyclohexane and methanol are added to repeatedly flocculate and dissolve the product, unreacted p-N, N-dimethylaminobenzoic acid anilide is washed off, and the product is dried in a vacuum drying oven at 30 ℃ for standby and is numbered SI-10.
(2) Dissolving a branching agent sample accounting for 1.0% of the total weight of monomers in 40mL of dichloromethane, adding the solution into a 4L polymerization kettle with the total volume, adding 1296mL of methyl chloride, 536mL of isobutene and 29mL of isoprene, rotating a stirring paddle at the speed of 190r/min, reducing the temperature to below-85 ℃, adding 2.65mL of water in saturated dichloromethane solution into 10mL of trichlorotriethylaluminum (0.4M in hexane), and adding 40mL of dehydrated CH 2 Cl 2 Aging for 20min, adding the system, adding methanol when the temperature rises to-40 ℃ after the reaction starts, stopping, and carrying out vacuum drying on the sample to obtain a bimodal distribution star-shaped branched butyl rubber sample, wherein the number is 14.
Example 14
(1) Under anhydrous and anaerobic conditions, adding 250mL of cyclohexane, 16mL of styrene and 1mL of Tetramethylethylenediamine (TMEDA) into a polymerization bottle, adding 0.7mL of N-butyllithium (0.9M hexane solution), shaking up and sealing, reacting at 50 ℃ for 5 hours, then adding 12mL of isoprene, reacting at 50 ℃ for 6 hours, adding 2mL of p-N, N-dimethylaminobenzoic acid anilide (0.1M cyclohexane solution), reacting at 60 ℃ for 30 minutes, adding cyclohexane and methanol to repeatedly flocculate and dissolve the product, washing off unreacted p-N, N-dimethylaminobenzoic acid anilide, and drying in a vacuum drying oven at 30 ℃ for later use, wherein the number is SI-1.
(2) Dissolving a branching agent sample with 1.0% of the total weight of monomers in 40mL of dichloromethane, adding the solution into a 4L polymerization kettle with the total volume, adding 1296mL of methyl chloride, 536mL of isobutene and 29mL of isoprene, rotating a stirring paddle at 190r/min, reducing the temperature to below-85 ℃, adding 0.02mL of 2-chloro-2, 4, 4-trimethylpentane (TMPCL, 0.01M hexane solution) into 10mL of trichlorotriethylaluminum (0.4M hexane solution), and adding 40mL of CH (CH) for removing water 2 Cl 2 Aging for 20min, adding the system, adding methanol when the temperature rises to-40 ℃ after the reaction starts, stopping, and carrying out vacuum drying on the sample to obtain a bimodal distribution star-shaped branched butyl rubber sample, wherein the number is 15.
Test results
Table 1 branching agent test data
TABLE 2 Star-branched butyl rubber test data
Claims (2)
1. A slurry polymerization method for preparing bimodal distribution star-shaped branched butyl rubber by using an imino-functionalized macromolecular branching agent is characterized by comprising the following specific experimental steps of:
step 1: synthesis of terminal imino-functionalized macromolecular branching agent:
wherein X is H, CH 3 、C(CH 3 ) 3 Or Cl; the solvent selected in the synthesis process is selected from nMore than one of hexane, cyclohexane, pentane, cyclopentane, isopentane, n-heptane, octane and isooctane; the initiator is selected from n-butyl lithium and tert-butyl lithium; the end capping agent is Schiff base selected from p-N, N-dimethylaminobenzoic acid aniline;
adding the solvent, styrene and X is CH into a polymerization bottle under the anhydrous and oxygen-free conditions 3 、C(CH 3 ) 3 Or a styrene derivative of Cl, tetramethylethylenediamine and the initiator are shaken up and sealed, reacted for 3-5 hours at 20-50 ℃, added with isoprene, reacted for 3-6 hours at 20-50 ℃, added with Schiff base with the same amount as the initiator, reacted for 30 minutes at 50-60 ℃, added with a polymerization solvent and a terminator methanol for repeated dissolution and flocculation after the reaction is finished, washed off the unreacted end-capping reagent, and dried in a vacuum drying oven at 30 ℃ for later use;
in the imino-functionalized macromolecular branching agent, polystyrene and X are CH 3 、C(CH 3 ) 3 Or Cl styrene derivative 40-80wt%, polyisoprene 3,4 structure 10-80 wt%, and branching agent molecular weight 5X 10 3 ~9.2×10 4 ；
Step 2: synthesis of star-branched butyl rubber with amino groups:
dissolving the terminal imino functionalized macromolecular branching agent prepared in the step 1, adding the dissolved terminal imino functionalized macromolecular branching agent, isobutene and isoprene into a polymerization kettle, reducing the temperature to be below-85 ℃, adding a prepared initiator, adding methanol within 1min after the reaction starts, stopping the reaction, and carrying out vacuum drying on a sample to obtain the bimodal distribution star-shaped branched butyl rubber;
the solvents in which the imino-functional macromolecular branching agent is dissolved are methyl chloride and methylene chloride;
the reaction temperature for synthesizing the star-shaped branched butyl rubber is-60 ℃ to-100 ℃;
the dosage of the branching agent is 0.2-3% when synthesizing the star-shaped branched butyl rubber, the branching agent can also play the role of a slurry stabilizer, and the slurry stability is better when the proportion of the polystyrene and the derivative thereof is higher; after adding the slurry stabilizer, the continuous polymerization time is prolonged from 30-40 h to 40-80 h;
the synthesized star-branched butyl rubber has a number average molecular weight of 1.17 × 10 5 ～33.1×10 5 Weight average molecular weight of 3.26X 10 5 ～1.56×10 6 The molecular weight distribution is 1.8-3.4; the content of the synthesized star-shaped branched butyl rubber polymer area is 3-15 percent, and the number average molecular weight of the polymer area is 5.91 multiplied by 10 5 ～8.82×10 6 And the average arm number is 4-12.
2. A slurry polymerization process as claimed in claim 1, wherein:
the imino-terminated functionalized macromolecular branching agent is a copolymer of styrene and isoprene of which the end-capping agent is p-N, N-dimethylaminobenzoic acid aniline;
in the imino-terminated functionalized macromolecular branching agent, the content of styrene, the content of isoprene with a 3,4 structure and the molecular weight are selected from one of the following SI-1 to SI-8:
。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911155805.2A CN110845650B (en) | 2019-11-22 | 2019-11-22 | Slurry polymerization method for preparing bimodal distribution star-shaped branched butyl rubber by using terminal imino functionalized macromolecular branching agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911155805.2A CN110845650B (en) | 2019-11-22 | 2019-11-22 | Slurry polymerization method for preparing bimodal distribution star-shaped branched butyl rubber by using terminal imino functionalized macromolecular branching agent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110845650A CN110845650A (en) | 2020-02-28 |
| CN110845650B true CN110845650B (en) | 2022-09-16 |
Family
ID=69603741
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911155805.2A Active CN110845650B (en) | 2019-11-22 | 2019-11-22 | Slurry polymerization method for preparing bimodal distribution star-shaped branched butyl rubber by using terminal imino functionalized macromolecular branching agent |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110845650B (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113493556B (en) * | 2020-04-08 | 2023-09-26 | 中国石油天然气股份有限公司 | Preparation method of hyperbranched butyl rubber |
| CN113493550B (en) * | 2020-04-08 | 2023-10-31 | 中国石油天然气股份有限公司 | Preparation method of high-width distribution high-branching butyl rubber |
| CN113493548B (en) * | 2020-04-08 | 2023-09-26 | 中国石油天然气股份有限公司 | Preparation method of branched butyl rubber |
| CN113493546B (en) * | 2020-04-08 | 2023-11-28 | 中国石油天然气股份有限公司 | Preparation method of butyl rubber with wide molecular weight distribution |
| CN113493547B (en) * | 2020-04-08 | 2023-11-28 | 中国石油天然气股份有限公司 | Preparation method of hyperbranched butyl rubber |
| CN113493549B (en) * | 2020-04-08 | 2023-10-31 | 中国石油天然气股份有限公司 | Preparation method of high-width distribution and high-branching butyl rubber |
| CN112315074B (en) * | 2020-09-28 | 2024-01-23 | 中国辐射防护研究院 | Multi-layer tritium-proof glove and manufacturing method thereof |
| CN112409522B (en) * | 2020-11-16 | 2022-11-15 | 山东京博中聚新材料有限公司 | Preparation method of butyl rubber |
| CN112375180B (en) * | 2020-11-16 | 2022-05-31 | 山东京博中聚新材料有限公司 | Branching agent for synthesizing star-shaped branched butyl rubber and preparation method thereof, and star-shaped branched butyl rubber and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1982342A (en) * | 2005-10-04 | 2007-06-20 | 株式会社普利司通 | Amine functionalized polymer |
| CN101041708A (en) * | 2007-04-25 | 2007-09-26 | 大连海事大学 | Method for synthesizing terminal amido SBS and application in modified pitch |
| CN105209268A (en) * | 2013-03-15 | 2015-12-30 | 株式会社普利司通 | Polymers functionalized with heterocyclic imines |
| CN105985487A (en) * | 2015-01-29 | 2016-10-05 | 中国石油天然气股份有限公司 | Double-end functionalized butadiene-isoprene copolymer rubber and preparation method thereof |
| CN108368204A (en) * | 2015-08-17 | 2018-08-03 | 巴黎市工业物理化学学校 | Including composition, preparation method and purposes containing the crosslinking polymer network for connecting and being crosslinked connection by aldehyde-imines and/or the tradable pendant of imines-imines exchange reaction |
-
2019
- 2019-11-22 CN CN201911155805.2A patent/CN110845650B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1982342A (en) * | 2005-10-04 | 2007-06-20 | 株式会社普利司通 | Amine functionalized polymer |
| CN101041708A (en) * | 2007-04-25 | 2007-09-26 | 大连海事大学 | Method for synthesizing terminal amido SBS and application in modified pitch |
| CN105209268A (en) * | 2013-03-15 | 2015-12-30 | 株式会社普利司通 | Polymers functionalized with heterocyclic imines |
| CN105985487A (en) * | 2015-01-29 | 2016-10-05 | 中国石油天然气股份有限公司 | Double-end functionalized butadiene-isoprene copolymer rubber and preparation method thereof |
| CN108368204A (en) * | 2015-08-17 | 2018-08-03 | 巴黎市工业物理化学学校 | Including composition, preparation method and purposes containing the crosslinking polymer network for connecting and being crosslinked connection by aldehyde-imines and/or the tradable pendant of imines-imines exchange reaction |
Non-Patent Citations (1)
| Title |
|---|
| 正离子聚合制备具有双峰分布丁基橡胶及其结构性能研究;张兰等;《高分子学报》;20150930(第9期);第1028-1035页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110845650A (en) | 2020-02-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110845650B (en) | Slurry polymerization method for preparing bimodal distribution star-shaped branched butyl rubber by using terminal imino functionalized macromolecular branching agent | |
| US9834619B2 (en) | Modified conjugated diene-based polymer, modified rubber composition containing same, and method for preparing modified conjugated diene-based polymer | |
| JP2007524722A (en) | End-capped polymer chains and their products | |
| US7056985B2 (en) | End-capped polymer chains and products thereof | |
| CN112250783B (en) | Copolymer of alpha-olefin and 2, 3-dimethyl-1, 3-butadiene, preparation method thereof and rare earth metal complex | |
| CN113307912A (en) | Silica functionalized SIBR (silicon-oxygen-functionalized-polymer-based elastomer) integrated rubber with star-shaped coupling structure and preparation method thereof | |
| CN112011018B (en) | Method for preparing bimodal distribution star-shaped branched butyl rubber by slurry method | |
| CN107652381B (en) | Preparation method of high cis-diene polymer | |
| CN112011019B (en) | Preparation method of halogenated bimodal distribution star-shaped branched butyl rubber | |
| US9725526B2 (en) | Modified conjugated diene polymer, modified rubber composition comprising same, and method for producing modified conjugated diene polymer | |
| CN113087829B (en) | End group functionalized synthetic rubber and preparation method and application thereof | |
| CN113307913A (en) | Nitrogen/silicon-oxygen-containing functionalized SIBR (silicon-rubber-based elastomer) integrated rubber with star-shaped coupling structure and preparation method thereof | |
| CN112011017B (en) | Method for preparing bimodal distribution star-shaped branched butyl rubber by solution method | |
| CN106046227B (en) | A method of adjusting low cis polyisoprene rubber molecular weight distribution | |
| CN108219067B (en) | Functionalized butadiene polymer and preparation method thereof | |
| CA2594650A1 (en) | End-capped polymer chains and products thereof | |
| CN112011003B (en) | Preparation method of functionalized four-arm star-shaped branching agent for branching butyl rubber | |
| CN114478953B (en) | Preparation method of three-arm comb-shaped star-branched butyl rubber | |
| CN114478950B (en) | Three-arm comb-shaped star-shaped branched butyl rubber and preparation method thereof, and preparation method of three-arm star-shaped nucleating agent | |
| CN112375180B (en) | Branching agent for synthesizing star-shaped branched butyl rubber and preparation method thereof, and star-shaped branched butyl rubber and preparation method thereof | |
| CN107522816B (en) | Method for synthesizing high cis-diene polymer | |
| CN107602747B (en) | Synthesis method of high cis-polydiene | |
| CN113912798B (en) | Star block copolymer based on DPE derivatives, butadiene, isoprene and styrene monomers and preparation method thereof | |
| KR100780478B1 (en) | Copolymerization of SBR and High cis Polybutadiene, and its Preparation | |
| CN107459596B (en) | Method for synthesizing high cis-polydiene |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |