CN115304698A - Functionalized conjugated diene rubber, composite material and preparation method thereof - Google Patents

Functionalized conjugated diene rubber, composite material and preparation method thereof Download PDF

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CN115304698A
CN115304698A CN202210858757.9A CN202210858757A CN115304698A CN 115304698 A CN115304698 A CN 115304698A CN 202210858757 A CN202210858757 A CN 202210858757A CN 115304698 A CN115304698 A CN 115304698A
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conjugated diene
rubber
diene rubber
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周光远
张松波
胡雁鸣
于琦周
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Dalian Institute of Chemical Physics of CAS
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F136/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F136/02—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
    • C08F136/04—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
    • C08F136/06—Butadiene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
    • B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
    • B60C1/0016—Compositions of the tread
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
    • C08C19/00—Chemical modification of rubber
    • C08C19/20—Incorporating sulfur atoms into the molecule
    • 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
    • C08F136/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F136/02—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
    • C08F136/04—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
    • C08F136/08—Isoprene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
    • C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
    • C08F236/06—Butadiene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
    • C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
    • C08F236/08—Isoprene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L15/00—Compositions of rubber derivatives
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    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/80—Technologies aiming to reduce greenhouse gasses emissions common to all road transportation technologies
    • Y02T10/86—Optimisation of rolling resistance, e.g. weight reduction 

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Abstract

The invention discloses functionalized conjugated diene rubber, a composite material and a preparation method thereof, wherein the conjugated diene rubber is a narrow-distribution functionalized synthetic rubber which is prepared by rare earth catalyst, contains conjugated diene units with cis-form content higher than 96% and is terminated by dithiocarbamate. The introduced dithiocarbamic acid ester group can be activated under the action of hot pressing to promote the crosslinking speed of the crosslinking agent sulfur and the conjugated diene rubber molecular chain, and can interact with various reinforcing fillers used for the tire product, such as carbon black or white carbon black and other nano reinforcing agents, so that the dispersibility of the reinforcing fillers in the diene rubber matrix and the motion capability of the passivated rubber molecular chain end are improved, the frictional heat generation of the conjugated diene rubber molecular chain end is further reduced, and the aims of improving the processing performance of the tire product and reducing the dynamic heat generation are finally fulfilled. The invention has wide application range, low cost, easy industrialization and better economic and social benefits.

Description

Functionalized conjugated diene rubber, composite material and preparation method thereof
Technical Field
The invention belongs to the technical field of functional polymer materials, and particularly relates to functionalized conjugated diene rubber, a composite material and a preparation method thereof.
Background
At present, the synthetic rubber is mainly used for manufacturing tire products, and because the performance of the synthetic rubber base material is poor, the performance of the domestic tire is 2-3 grades worse than that of the foreign tire, the competitiveness is lacked, and the export of the tire in China is greatly limited.
As an important part of the direct contact of the tire with the ground, a tire tread rubber is one of the key components for the preparation of high performance tires. The high cis-stereoregularity endows conjugated diolefins, such as butadiene rubber, with excellent elasticity, wear resistance and flex resistance, making it one of the key rubber types for preparing tire tread rubber. Compared with the active anion polymerization technology, the rare earth coordination polymerization method has the characteristics of high activity and high directionality, and is an ideal choice for synthesizing the conjugated diene rubber with high stereoregularity (the cis content is more than 96%).
The tire material is a multi-component and multi-layer composite material. The key to preparing the green tire with high modulus, low energy consumption and long service life is to promote the interface action between the polar filler and the nonpolar rubber molecular chain and promote the dispersibility of the reinforcing filler in the rubber matrix. The functionalized design is carried out on the conjugated diene rubber, functional groups capable of forming interface action with the reinforcing filler are introduced to the conjugated diene rubber molecular chain, the dispersibility of the reinforcing filler is improved, and the dynamic friction heat generation of the rubber molecular chain is passivated, so that the method is the most effective method for preparing high-end rubber products. Patent CN107466299A discloses a process for the preparation of a silicon-containing functionalized catalyst composition and for the polymerization of conjugated dienes. Patent CN108219067B discloses a functionalized butadiene polymer and a preparation method thereof, using butadiene and silicon-containing polybutadiene as comonomers. Introducing a silicon-containing group to a molecular chain of the butadiene rubber is mainly used for improving the interface action between the butadiene rubber and the white carbon black. However, two or more kinds of reinforcing fillers are often added in a high-performance tire formula, and introduction of a functional group capable of forming an interface action with multiple reinforcing fillers simultaneously into a rubber molecular chain is particularly critical for preparing high-performance conjugated diene rubber. In addition, as a multi-component composite material, the efficient introduction of a functional group which can simultaneously form an interface action with a plurality of reinforcing fillers and has functions of other components (such as an antioxidant, an accelerator and other accessory ingredients) into a rubber molecular chain is another key technical problem for preparing a high-performance rubber material. Therefore, the technical problems to be solved by the application are to develop a functionalized conjugated diene rubber, and introduce a multifunctional group into the chain structure of the functionalized conjugated diene rubber, so that the synthetic rubber matrix can form a strong interface effect with various reinforcing fillers in the processing process, and has the functions similar to the functions of other components in the rubber formula, and the preparation of a high-performance rubber material and the preparation process.
Disclosure of Invention
The invention provides a functionalized conjugated diene rubber, a composite material and a preparation method thereof, wherein a rare earth catalyst is firstly adopted for conjugated diene polymerization, and then a dithiocarbamate-containing functionalized reagent is added in the later period of polymerization to obtain the functionalized butadiene rubber containing dithiocarbamate, wherein the introduced dithiocarbamate group can form strong interaction with various reinforcing fillers and can activate the crosslinking process of rubber products. The technical scheme adopted by the invention is as follows:
the functionalized conjugated diene rubber is a functionalized synthetic rubber, the molecular main chain of which is mainly a conjugated diene cis unit, and the molecular chain end of which contains dithiocarbamate, and comprises the structure shown in the following figure; the cis-structural unit content of conjugated diene in the molecular main chain is higher than 96.0%.
Figure BDA0003755424810000031
Preferably, said functionalized conjugated diene rubber is characterized in that: the conjugated diene includes but is not limited to one, two or more of C4-C6 conjugated dienes (the conjugated diene is preferably selected from butadiene, isoprene or a mixture of the two).
Preferably, said functionalized conjugated diene rubber is characterized in that: the dithiourethane groups have the structure shown below, wherein x = 1-6, R' are each independently selected from alkyl, aryl, cycloalkyl, etc., preferably having a C number not higher than 20.
Figure BDA0003755424810000032
Preferably, said functionalized conjugated diene rubber is characterized in that: the functionalized conjugated diene rubber has a number average molecular weight in the range of 5 x 10 4 —100×10 4 g/mol, molecular weight distribution range of 1.7-2.5, cis content of conjugated diene unit in chain of 90.0-99.9%, content of conjugated diene rubber containing dithio carbamate of 5-100 wt% of whole content of conjugated diene rubber, mooney viscosity (ML 1+4min,100 ℃) of 15-90.
In another aspect, the present invention provides a method for preparing the above functionalized conjugated diene rubber, comprising the steps of:
s1, under the protection of inert gas, preparing a rare earth catalyst, wherein the rare earth catalyst is characterized by comprising a and c in the following components, and one, two or more than one of b and/or d in the following components can be added:
component a, rare earth compounds;
the component b, optional additive or optional additive component, is conjugated diene;
component c, an aluminum compound; to have AlR 3 And/or AlHR 2 One, two or more mixtures of structures wherein R is methyl, ethyl, isobutyl;
the component d is a chlorine-containing compound, and the halogen-containing compound is one, two or more of the following compounds;
has the general formula AlR 2 Alkyl aluminum halide of X, formula Al 2 R 3 X 3 One or more of halogenated hydrocarbons of the general formula RX, wherein R is ethyl, propyl, isopropyl, isobutyl, tert-butyl, etc., and X is bromine or chlorine; also possible are chloromethylsilanes: one, two or more of monochlorotrimethylsilane, dichlorodimethylsilane, trichloromethylsilane or silicon tetrachloride;
s2, adding an organic solvent and a certain mass of conjugated diene into a polymerization reactor, heating and keeping the temperature to be 30-100 ℃;
s3, adding the catalyst prepared in the S1 into a polymerization reactor to initiate a polymerization reaction of conjugated diene for 30min to 6h;
s4, adding a reagent containing dithiocarbamate into the polymerization solution obtained in the step S3, and continuously reacting for 30 min-12 h;
s5, adding a terminator into the polymerization reaction liquid to terminate polymerization, condensing and drying.
Preferably, the rare earth compound in the step S1 is selected from one, two or more of the following compounds:
selected from rare earth carboxylates, is M (RCOO) 3 (ii) a M is one, two or more of the rare earth elements, and RCOO is selected from: one, two or more of naphthenate, decanoate, 2-ethylhexanoate, octanoate or neodecanoate;
one, two or more selected from rare earth phosphate compounds such as neodymium di (2-ethylhexyl) phosphate, neodymium mono 2-ethylhexyl 2-phosphate, or neodymium di (2-ethylhexyl) phosphate;
selected from chlorinated rare earth complexes, MCl 3 nL, n =1-4, M is one, two or more of the above rare earth elements, L is an organic ligand selected from one, two or more of alcohols, ethers or organic phosphates, wherein the alcohol is a C1-C8 alcohol, preferably selected from one, two or more of methanol, ethanol, isopropanol, butanol, pentanol, hexanol, octanol, 2-ethylhexanol; the ether is C1-C8 ether, preferably one, two or more selected from diethyl ether, methyl ethyl ether, butyl ether, tetrahydrofuran and dioxane; the organic phosphate is one or two or more selected from trimethyl phosphate, triethyl phosphate, tripropyl phosphate, tributyl phosphate, triphenyl phosphate, dimethyl phosphate, diethyl phosphate, dipropyl phosphate, dibutyl phosphate and diphenyl phosphate.
Preferably, the aluminium compound in step S1 is of AlR 3 And/or AlHR 2 A mixture of one, two or more of structures, preferably triisobutylaluminum, triethylaluminum, diisobutylaluminum hydride;
preferably, the conjugated diene in the step S1 is preferably butadiene, isoprene, 1, 3-pentadiene;
preferably, the molar ratio of each component of the rare earth catalyst in the step S1 is a: b: c: d =1: (0 to 30): (10-30): (0-5);
preferably, the preparation method of the rare earth catalyst in the step S1 comprises the following steps: in an inert organic solvent, firstly, mixing the component a and the component b for 1-5 min; then adding the component c, and reacting for 10-120 min; finally, adding the component d, and reacting for 30-120 min; the temperature in the preparation process of the catalyst is 20-60 ℃;
or, in an inert organic solvent, firstly reacting the component a with the component c for 10-120 min; finally, adding the component d, and reacting for 20-120 min; the temperature in the preparation process of the catalyst is 20-60 ℃;
or, in an inert organic solvent, firstly mixing the component a and the component b for 1-5 min; then adding the component c, and reacting for 20-120 min; the temperature in the preparation process of the catalyst is 20-60 ℃;
or, in an inert organic solvent, firstly mixing the component a and the component b, and reacting for 20-120 min; the temperature in the preparation process of the catalyst is 20-60 ℃;
preferably, the organic solvent in the step S2 is selected from one or more of non-polar aromatic hydrocarbon and non-polar aliphatic hydrocarbon, and the organic solvent includes but is not limited to pentane, cyclopentane, hexane, cyclohexane, heptane, octane, benzene, toluene;
preferably, the method of preparing the functionalized conjugated diene rubber is characterized in that the dithiocarbamate-containing reagent includes, but is not limited to, tetramethylthiuram monosulfide, tetrabutylthiuram monosulfide, bis (1, 5-pentamethylene) thiuram monosulfide, tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetrabutylthiuram disulfide, bis (1, 5-pentamethylene) thiuram disulfide, dimethyldiphenylthiuram disulfide, diethyldiphenylthiuram disulfide, tetramethylthiuram tetrasulfide, bis (1, 5-pentamethylene) thiuram hexasulfide.
In a third aspect, the invention provides a functionalized conjugated diene rubber composite material, which is characterized by comprising the following raw materials in parts by weight:
x parts of the functionalized conjugated diene rubber;
100-x parts of rubber is used;
2-8 parts of zinc oxide;
0.5-3 parts of stearic acid;
0.5-4 parts of an anti-aging agent;
1-50 parts of a softener;
30-100 parts of reinforcing filler;
0.2-5 parts of an accelerator;
0.5-5 parts of sulfur;
wherein x is 5 to 100;
preferably, the blended rubber is rubber used for tire products, and includes but is not limited to one or more of natural rubber, styrene-butadiene rubber, isoprene rubber and butyl rubber;
preferably, the reinforcing filler is one or more reinforcing fillers including, but not limited to, carbon black, white carbon black, clay, carbon nanotubes, halloysite, and graphene oxide.
In a fourth aspect, the invention also provides a preparation method of the functionalized conjugated diene rubber composite material, which comprises the following steps:
on the basis of the preparation method of the functionalized conjugated diene rubber, the prepared functionalized conjugated diene rubber is used as a rubber matrix and is used together with other rubbers, and the rubber matrix, an anti-aging system, a vulcanization system, a softening system and a reinforcing system with oxygen-containing or nitrogen-containing groups on the surface are mixed and vulcanized to prepare the functionalized conjugated diene rubber composite material containing dithiocarbamate.
High reaction activity exists between the 12 screened out functionalization reagents containing dithiocarbamate groups and a neodymium active center of a catalytic system, and the functionalization conjugated diene rubber terminated with dithiocarbamate groups can be efficiently obtained; the dithiocarbamate group can form strong interaction with various reinforcing fillers with oxygen-containing surfaces, improve the dispersibility of the various reinforcing fillers in a conjugated diene rubber matrix, reduce the dynamic heat generation of rubber molecular chain ends, and activate the formation process of a cross-linked network in the rubber composite material, thereby finally realizing the aim of preparing the green tire tread rubber with high modulus, low energy consumption and long service life.
Drawings
FIG. 1 is an infrared spectrum of the functionalized polybutadiene rubber containing dithiocarbamate prepared in example 2, example 5, example 11 and example 12.
Detailed Description
The following examples are presented as further illustration of the invention and are not intended to limit the scope of the invention as claimed. Analyzing the composition sequence distribution and microstructure of the functionalized conjugated diene rubber by an infrared spectrometer according to GB/T7764-2017 and SH/T1727-2017; analyzing the molecular weight and molecular weight distribution index (ratio of weight average molecular weight to number average molecular weight) of the conjugated diene rubber by gel permeation chromatography; the Mooney viscosity of the functionalized conjugated diene rubber was analyzed with a Mooney viscometer according to GB/T1232-1992.
Example 1
Under the protection of argon, neodymium neodecanoate, butadiene and diethylaluminum hydride are aged for 30min at 10 ℃ according to the molar ratio of 1 to 20, then 1 equivalent of diethylaluminum monochloride of neodymium neodecanoate is added, and the aging is continued for 2h to prepare the catalyst. 50g of butadiene monomer is dissolved in hexane solvent, added into a polymerization reactor, heated to 30 ℃, and the molar ratio of neodymium neodecanoate to butadiene monomer is 5 multiplied by 10 -5 . And adding the aged catalyst into a polymerization reactor, and initiating butadiene polymerization for 6 hours. After dissolving tetramethylthiuram monosulfide in hexane, the solution was added to a polymerization reactor and allowed to react for 12 hours. Finally, adding ethanol to terminate polymerization, condensing and drying. The polymer yield was 93%; the results of the product structure analysis are as follows: the cis content is 96.7%, the number average molecular weight is 150kg/mol, the molecular weight distribution is 1.95, the functionalization blocking efficiency is 89%, and the Mooney viscosity is 45.
Example 2
Under the protection of argon, neodymium neodecanoate, isoprene and diisobutylaluminum hydride are aged at 50 ℃ for 10min according to a molar ratio of 1. 50g of butadiene monomer is dissolved in a hexane solvent, added into a polymerization reactor, heated to a constant temperature of 50 ℃, and the molar ratio of neodymium neodecanoate to butadiene monomer is 5 x 10 -5 . Adding the aged catalyst into a polymerization reactor, and initiating butadiene polymerization for 4h. After the tetrabutylthiuram disulfide was dissolved in hexane, the resulting solution was charged into a polymerization reactor and the reaction was continued for 8 hours. Finally, adding ethanol to terminate polymerization, condensing and drying. The polymer yield was 90%; the results of the product structure analysis are as follows: the cis content is 97.7 percent, the number average molecular weight is 260kg/mol, the molecular weight distribution is 2.05, and the end capping is functionalizedEfficiency 90%, mooney viscosity 55.
Example 3
Under the protection of argon, neodymium isooctanoate and triisobutylaluminum are aged for 5min at 30 ℃ according to the molar ratio of 1. 50g of butadiene monomer is dissolved in toluene solvent, added into a polymerization reactor, heated to 50 ℃, and the molar ratio of neodymium isooctanoate to butadiene monomer is 7 multiplied by 10 -5 . And adding the aged catalyst into a polymerization reactor to initiate butadiene polymerization for 4 hours. Dissolving tetramethylthiuram tetrasulfide in toluene, adding into a polymer reactor, and continuing to react for 30min. Finally adding ethanol to terminate polymerization, condensing and drying. The polymer yield was 96%; the results of the product structure analysis are as follows: the cis content is 98.8%, the number average molecular weight is 1000kg/mol, the molecular weight distribution is 2.5, the functionalization blocking efficiency is 50%, and the Mooney viscosity is 90.
Example 4
Under the protection of argon, the neodymium naphthenate, 1, 3-pentadiene and triethyl aluminum are aged for 15min at 40 ℃ according to a molar ratio of 1. 50g of butadiene monomer is dissolved in hexane and added into a polymerization reactor, and the mixture is heated to a constant temperature of 40 ℃, and the molar ratio of the neodymium naphthenate to the 1.3-pentadiene monomer is 4 multiplied by 10 -3 . And adding the aged catalyst system into a polymerization reactor, and initiating 1, 3-pentadiene to perform polymerization for 2 hours. After dissolving tetrabutylthiuram monosulfide with hexane, the resulting solution was charged into a polymerization reactor and allowed to react for 4 hours. Finally, adding ethanol to terminate polymerization, condensing and drying. The polymer yield was 99%; the results of the product structure analysis are as follows: the cis content is 96.2%, the number average molecular weight is 50kg/mol, the molecular weight distribution is 2.15, the functionalization blocking efficiency is 40%, and the Mooney viscosity is 15.
Example 5
Under the protection of argon, neodymium naphthenate, butadiene and diisobutylaluminum hydride are aged at 60 ℃ for 20min according to a molar ratio of 1. 50g of butadiene monomer was dissolved in n-hexaneAdding the agent into a polymerization reactor, heating and keeping the temperature to 40 ℃, wherein the molar ratio of the neodymium naphthenate to the butadiene monomer is 4 multiplied by 10 -4 . And adding the aged catalyst system into a polymerization reactor to initiate butadiene polymerization for 2 hours. Bis (1, 5-pentylene) thiuram monosulfide was dissolved in toluene and added to the polymerization reactor for polymerization for 6 hours. Finally adding isopropanol to terminate polymerization, condensing and drying. The polymer yield was 98%; the results of the product structure analysis are as follows: the cis content is 96%, the number average molecular weight is 80kg/mol, the molecular weight distribution is 1.95, the functionalized end-capping efficiency is 80%, and the Mooney viscosity is 26.
Example 6
Under the protection of argon, the neodymium bis (2-ethylhexyl) phosphate, butadiene and diethyl aluminum hydride are aged at 40 ℃ for 15min according to a molar ratio of 1. 50g of butadiene monomer is dissolved in pentane solvent and added into a polymerization reactor, the temperature is kept constant at 40 ℃, and the molar ratio of neodymium phosphate to butadiene monomer is 5 multiplied by 10 -5 . And adding the aged catalyst system into a polymerization reactor to initiate butadiene polymerization for 4 hours. The bis (1, 5-pentylidene) thiuram hexasulfide was dissolved in pentane and then introduced into a polymerization reactor for polymerization for 2 hours. Finally adding isopropanol to terminate polymerization, condensing and drying. The polymer yield was 91%; the results of the product structure analysis are as follows: the cis content is 97%, the number average molecular weight is 300kg/mol, the molecular weight distribution is 1.85, the functionalization end-capping efficiency is 96%, and the Mooney viscosity is 65.
Example 7
Under the protection of argon, chlorination rare earth tri-tert-butyl phosphate compound (NdCl) 3· 3 TBP) diisobutylaluminum hydride was aged at 50 ℃ for 1 hour at a molar ratio of 1. 50g of butadiene monomer is dissolved in heptane solvent and added into a polymerization reactor and heated to a constant temperature of 50 ℃, and the molar ratio of neodymium chloride to butadiene monomer is 5 x 10 -5 . And adding the aged catalyst system into a polymerization reactor to initiate butadiene polymerization for 2 hours. Dissolving the bis (1, 5-pentylene) disulfide in toluene, and adding the solution into a polymerization reactor for polymerization for 1 hour. Finally adding isopropanol to terminate the polymerization,condensing and drying. The polymer yield was 92%; the results of the product structure analysis are as follows: the cis content was 96.5%, the number average molecular weight was 500kg/mol, the molecular weight distribution was 1.7, the functionalization capping efficiency was 92%, and the Mooney viscosity was 75.
Example 8
Under the protection of argon, neodymium neodecanoate, isoprene and diisobutylaluminum hydride are aged at 50 ℃ for 15min according to a molar ratio of 1. 50g of isoprene monomer is dissolved in heptane solvent and added into a polymerization reactor, and the temperature is kept constant at 50 ℃ by heating, and the molar ratio of neodymium neodecanoate to isoprene monomer is 5 multiplied by 10 -5 . And adding the aged catalyst system into a polymerization reactor to initiate butadiene polymerization for 2 hours. Dissolving dimethyl diphenyl thiuram disulfide by using toluene, and adding the solution into a polymer reactor for polymerization for 1h. Finally adding isopropanol to terminate polymerization, condensing and drying. The polymer yield was 90%; the results of the product structure analysis are as follows: the cis content is 96.8 percent, the number average molecular weight is 490kg/mol, the molecular weight distribution is 1.89, the functionalization end-capping efficiency is 92 percent, and the Mooney viscosity is 72.
Example 9
Under the protection of argon, neodymium neodecanoate, isoprene, diisobutylaluminum hydride and triethylaluminum are aged at 50 ℃ for 15min according to a molar ratio of 1. 50g of butadiene monomer is dissolved in n-hexane solvent and added into a polymerization reactor, the temperature is kept constant to 50 ℃, and the molar ratio of neodymium neodecanoate to butadiene monomer is 7 multiplied by 10 -5 . And adding the aged catalyst system into a polymerization reactor to initiate butadiene polymerization for 4 hours. Dissolving diethyl diphenyl thiuram disulfide by using toluene, and adding the dissolved diethyl diphenyl thiuram disulfide into a polymerization reactor for polymerization for 1h. Finally adding isopropanol to terminate polymerization, condensing and drying. The polymer yield was 95%; the results of the product structure analysis are as follows: the cis content is 96.8 percent, the number average molecular weight is 200kg/mol, the molecular weight distribution is 2.05, the functionalized end capping efficiency is 98 percent, and the Mooney viscosity is 50.
Example 10
Neodymium neodecanoate, isoprene, diisobutylaluminum hydride, triethylaluminum were aged at 50 ℃ for 15min at a molar ratio of 1. 50g of isoprene monomer is dissolved in n-hexane solvent and added into a polymerization reactor, the temperature is kept constant at 50 ℃, and the molar ratio of neodymium neodecanoate to isoprene monomer is 4 multiplied by 10 -5 . And adding the aged catalyst system into a polymerization reactor to initiate butadiene polymerization for 4 hours. Dissolving diethyl diphenyl thiuram disulfide by using toluene, and adding the solution into a polymerization reactor for polymerization for 1h. Finally adding isopropanol to terminate polymerization, condensing and drying. The polymer yield was 90%; the results of the product structure analysis are as follows: the cis content is 99%, the number average molecular weight is 260kg/mol, the molecular weight distribution is 2.05, the functionalization end-capping efficiency is 98%, and the Mooney viscosity is 69.
Example 11
Under the protection of argon, neodymium neodecanoate, butadiene, diisobutylaluminum hydride and triethylaluminum were aged at 50 ℃ for 15min according to a molar ratio of 1. 50g of butadiene monomer is dissolved in toluene solvent and added into a polymerization reactor, the temperature is kept constant at 50 ℃, and the molar ratio of neodymium neodecanoate to butadiene monomer is 7 multiplied by 10 -5 . And adding the aged catalyst system into a polymerization reactor to initiate butadiene polymerization for 4 hours. Dissolving tetraethyl thiuram disulfide by using toluene, and adding the solution into a polymerization reactor for polymerization for 2 hours. Finally adding isopropanol to terminate polymerization, condensing and drying. The polymer yield was 96%; the results of the product structure analysis are as follows: the cis content is 97.8 percent, the number average molecular weight is 285kg/mol, the molecular weight distribution is 2.04, the functionalized end-capping efficiency is 99 percent, and the Mooney viscosity is 59.
Example 12
Neodymium neodecanoate, butadiene, diisobutylaluminum hydride, triethylaluminum were aged at 50 ℃ for 15min in a molar ratio of 1. 50g of butadiene monomer was dissolved in n-hexane solvent and charged into a polymerization reactorHeating the mixture to 50 ℃, wherein the molar ratio of neodymium neodecanoate to butadiene monomer is 6 multiplied by 10 -5 . And adding the aged catalyst system into a polymerization reactor to initiate butadiene polymerization for 4 hours. Dissolving tetrabutylthiuram disulfide by using n-hexane, and adding the solution into a polymer reactor for polymerization for 2 hours. Finally adding isopropanol to terminate polymerization, condensing and drying. The polymer yield was 92%; the results of the product structure analysis are as follows: the cis content is 97.9%, the number average molecular weight is 295kg/mol, the molecular weight distribution is 2.14, the functionalized end-capping efficiency is 100%, and the Mooney viscosity is 60.
Example 13
Neodymium neodecanoate, butadiene, diisobutylaluminum hydride were aged at 50 ℃ for 15min at a molar ratio of 1. Dissolving 25g of butadiene and 25g of isoprene monomer in a normal hexane solvent, adding the mixture into a polymerization reactor, heating the mixture to a constant temperature of 50 ℃, wherein the molar ratio of neodymium neodecanoate to the monomer is 9 x 10 -5 . And adding the aged catalyst system into a polymerization reactor to initiate polymerization for 4 hours. Dissolving tetrabutylthiuram disulfide by using normal hexane, and adding the solution into a polymer reactor for polymerization reaction for 2 hours. Finally adding isopropanol to terminate polymerization, condensing and drying. The polymer yield was 98%; the results of the product structure analysis are as follows: the cis content of the butadiene structural unit is 98.9 percent, the cis content of the isoprene structural unit is 98.6 percent, the number average molecular weight is 151kg/mol, the molecular weight distribution is 2.35, the functionalization end-capping efficiency is 95 percent, and the Mooney viscosity is 46 percent.
Example 14
Under the protection of argon, neodymium neodecanoate, butadiene and diisobutylaluminum hydride are aged at 50 ℃ for 15min according to a molar ratio of 1. 25g of butadiene and 25g of isoprene monomer are dissolved in n-hexane solvent and added into a polymerization reactor, the temperature is kept constant at 50 ℃, and the molar ratio of neodymium neodecanoate to monomer is 9 multiplied by 10 -5 . And adding the aged catalyst system into a polymerization reactor to initiate polymerization for 4 hours. Dissolving tetrabutylthiuram disulfide with n-hexane, and adding the polymerThe reactor is used for polymerization for 2h. Finally adding isopropanol to terminate polymerization, condensing and drying. The polymer yield was 97%; the results of the product structure analysis are as follows: the cis content of the butadiene structural unit is 99.0 percent, the cis content of the isoprene structural unit is 99.1 percent, the number average molecular weight is 148 kg/mol, the molecular weight distribution is 2.32, the functionalized end-capping efficiency is 95 percent, and the Mooney viscosity is 45 percent.
Comparative example 1
Under the protection of argon, neodymium neodecanoate, butadiene, diisobutylaluminum hydride and triethylaluminum are aged at 50 ℃ for 15min according to a molar ratio of 1. 50g of butadiene monomer is dissolved in n-hexane solvent and added into a polymerization reactor, the temperature is kept to 50 ℃, and the molar ratio of neodymium neodecanoate to butadiene monomer is 8 multiplied by 10 -5 . And adding the aged catalyst system into a polymerization reactor to initiate butadiene polymerization for 4 hours. Finally adding isopropanol to terminate polymerization, condensing and drying. The results of the product structure analysis are as follows: the cis content was 97.9%, the number average molecular weight was 290kg/mol, the molecular weight distribution was 2.14, and the Mooney viscosity was 59.
Comparative example 2
Neodymium chloride, butadiene, diisobutylaluminum hydride, triethylaluminum were aged at 50 ℃ for 1h in a molar ratio of 1. 50g of butadiene monomer is dissolved in n-hexane solvent and added into a polymerization reactor, the temperature is kept constant to 50 ℃, and the molar ratio of neodymium chloride to butadiene monomer is 5.5 multiplied by 10 -5 . And adding the aged catalyst system into a polymerization reactor to initiate butadiene polymerization for 4 hours. Finally adding isopropanol to terminate polymerization, condensing and drying. The results of the product structure analysis are as follows: the cis content was 95.8%, the number average molecular weight was 300kg/mol, the molecular weight distribution was 3.6, and the Mooney viscosity was 59.
Comparative example 3
50g of the cis-butadiene rubber synthesized in comparative example 1 was dissolved in 100ml of hexane, and after complete dissolution, 2-diethylaminoethanethiol (Matrix, 2g, CAS No.: 100-38-9) was added, and stirred at room temperature for 12 hours, and then precipitated and dried to obtain a diethylamino-functionalized cis-butadiene rubber with a functionalization efficiency of 90%.
Application examples 1 to 4
Non-functionalized butadiene rubber is taken as a comparative example 1, butadiene rubber prepared by a neodymium chloride rare earth catalytic system is taken as a comparative example 2, the cis content and the molecular weight of butadiene in the butadiene rubber are controlled to be similar to those of the functionalized butadiene rubber containing dithiocarbamate groups in example 12, and diethylamino functionalized butadiene rubber obtained by utilizing a traditional post-grafting functionalization technology is taken as a comparative example 3. The functionalized butadiene rubber containing dithiocarbamate group synthesized in example 12 and the butadiene rubber synthesized in comparative example 1 and comparative example 2 were plasticated in a thin pass manner for 3 times by using an open mill (Kao Lexan, guangdong) according to the same formulation (see Table 1), and then the butadiene rubber, the styrene-butadiene rubber, zinc oxide, stearic acid, the anti-aging agent 4010NA, paraffin oil, carbon black and white carbon black were sequentially added to disperse the above small materials uniformly in the butadiene rubber and the styrene-butadiene rubber. After the roller is cooled, adding the accelerator CZ and the sulfur in sequence, and mixing uniformly. Finally, the piece is taken out, is parked for 10 hours and is multiplied by 12.5MPa by t at 150 DEG C 90 The sheets were vulcanized out and tested for properties after 16h standing to investigate the effect of the introduction of dithiocarbamate groups on the vulcanization properties, dynamic mechanical properties and static mechanical properties (see table 2).
TABLE 1 Experimental formulation
Figure BDA0003755424810000171
Figure BDA0003755424810000181
TABLE 2 comparison of the Properties of the functionalized butadiene rubbers containing dithiocarbamate groups, prepared separately in application examples 1-4, with unfunctionalized carboxylic acid rare earth butadiene rubbers and chlorinated rare earth butadiene rubbers
Figure BDA0003755424810000182
Figure BDA0003755424810000191
It can be seen that, compared with carboxylic acid rare earth butadiene rubber (application example 2) and chlorinated rare earth butadiene rubber (application example 3), the dithiocarbamate group in the functionalized butadiene rubber (application example 1) prepared by the technical scheme of the invention can form interaction with the groups on the surfaces of carbon black and white carbon black in the mixing process of the rubber material, so that the dispersibility and the interfacial action of the carbon black and the white carbon black in the rubber matrix are improved, the motion capability of the rubber molecular chain is passivated, and the frictional heating of the rubber product is reduced (the loss factor at 60 ℃ is reduced). Meanwhile, compared with the traditional amino functionalized rubber (application example 4), the functionalized butadiene rubber prepared by the technical scheme of the invention has the advantages that under the action of heat in the vulcanization process, the reaction of sulfur and rubber main chain double bonds is promoted by activating the dithiocarbamic acid ester group at the end group of the main chain (the positive vulcanization time t of the process) 90 Shortening), and the crosslinking network strength (crosslinking density is increased) of the rubber product is improved. In conclusion, the dispersibility and interface effect of the carbon black and the white carbon black in the rubber matrix are improved, and the strength of a cross-linked network is enhanced, so that the tensile property (stress at definite elongation and tensile strength) of the rubber composite material prepared from the functionalized rubber synthesized by the method is improved.
The above-mentioned embodiments only express the embodiments of the present invention, but not should be understood as the limitation of the scope of the invention patent, it should be noted that, for those skilled in the art, many variations and modifications can be made without departing from the concept of the present invention, and these all fall into the protection scope of the present invention.

Claims (10)

1. A functionalized conjugated diene rubber is characterized in that: the functionalized conjugated diene rubber is functionalized synthetic rubber with a molecular main chain mainly comprising a conjugated diene cis-structure unit and a molecular chain terminal containing dithiocarbamate;
the content of the conjugated diene cis-structural unit in the molecular main chain is higher than 96.0 percent.
2. The functionalized conjugated diene rubber of claim 1, wherein: the conjugated diene comprises but is not limited to one or more than two of C4-C6 conjugated dienes; the conjugated diene is preferably selected from butadiene, isoprene or a mixture of both.
3. The functionalized conjugated diene rubber of claim 1, wherein: the dithiocarbamate group has the structure shown below, wherein x = 1-6, R and R' are each independently selected from alkyl, aryl, cycloalkyl;
Figure FDA0003755424800000011
4. the functionalized conjugated diene rubber of claim 1, wherein: the functionalized conjugated diene rubber has a number average molecular weight in the range of 5 x 10 4 —100×10 4 g/mol, the molecular weight distribution range is 1.7-2.5, the cis content of the conjugated diene unit in the chain is 96.0% -99.9%, the content of the dithiocarbamate-containing conjugated diene rubber is 5% -100% of the whole mass fraction of the conjugated diene rubber, and the Mooney viscosity (ML 1+4min,100 ℃) is 15-90.
5. A preparation method of functionalized conjugated diene rubber comprises the following steps:
s1, under the protection of inert gas, preparing a rare earth catalyst, wherein the rare earth catalyst is characterized by comprising a and c in the following components, and one or more than two of b and/or d in the following components can be added:
component a, rare earth compound;
the component b, optional additive or optional additive component, is conjugated diene;
component c, an aluminum compound; to have AlR 3 And/or AlHR 2 One kind of structure orTwo or more mixtures, wherein R is methyl, ethyl, isobutyl;
the component d is a halogen-containing compound, and the halogen-containing compound is one, two or more of the following compounds;
has the general formula AlR 2 Alkyl aluminum halide of X, formula Al 2 R 3 X 3 Wherein R is ethyl, propyl, isopropyl, isobutyl, tert-butyl, etc., and X is bromine or chlorine; or chloromethylsilane: one, two or more of chlorotrimethylsilane, dichlorodimethylsilane, trichloromethylsilane or silicon tetrachloride;
s2, adding a nonpolar organic solvent and a certain mass of conjugated diene into a polymerization reactor, and heating to a constant temperature of 30-100 ℃;
s3, adding the catalyst prepared in the S1 into a polymerization reactor to initiate polymerization of conjugated diene for 30min to 6h;
s4, adding a reagent containing dithiocarbamate into the polymerization solution obtained in the step S3, and continuously reacting for 30 min-12 h;
s5, adding a terminator into the polymerization reaction liquid to terminate polymerization, condensing and drying.
6. The process for preparing a functionalized conjugated diene rubber according to claim 5, wherein:
the rare earth compound in the step S1
The rare earth compound is one, two or more of the following compounds:
selected from rare earth carboxylates, is M (RCOO) 3 (ii) a M is one, two or more of the rare earth elements, RCOO is selected from: one, two or more of naphthenate, decanoate, 2-ethylhexanoate, octanoate and neodecanoate;
one, two or more selected from rare earth phosphate compounds such as neodymium di (2-ethylhexyl) phosphate, neodymium mono 2-ethylhexyl 2-phosphate, or neodymium di (2-ethylhexyl) phosphate; selected from chlorinated rare earth complexes, MCl 3 ·nL, n =1-4, M is one, two or more of the rare earth elements, L is an organic ligand selected from one, two or more of alcohols, ethers or organic phosphates, wherein the alcohol is C1-C8 alcohol, preferably selected from one, two or more of methanol, ethanol, isopropanol, butanol, pentanol, hexanol, octanol and 2-ethylhexanol; the ether is C1-C8 ether, preferably one, two or more selected from diethyl ether, methyl ethyl ether, butyl ether, tetrahydrofuran and dioxane; the organic phosphate is one, two or more selected from trimethyl phosphate, triethyl phosphate, tripropyl phosphate, tributyl phosphate, triphenyl phosphate, dimethyl phosphate, diethyl phosphate, dipropyl phosphate, dibutyl phosphate and diphenyl phosphate.
The aluminum compound in the step S1 is provided with AlR 3 And/or AlHR 2 One, two or more mixtures of structures, preferably triisobutylaluminum, triethylaluminum, diisobutylaluminum hydride;
the conjugated diene in the step S1 is preferably butadiene, isoprene, 1, 3-pentadiene;
the mole ratio of each component of the rare earth catalyst in the step S1 is a: b: c: d =1: (0 to 30): (10-30): (0-5);
the preparation method of the rare earth catalyst in the step S1 comprises the following steps: in a non-polar organic solvent, firstly, mixing the component a and the component b for 1-5 min; then adding the component c, and reacting for 10-120 min; finally, adding the component d, and reacting for 30-120 min; the temperature in the preparation process of the catalyst is 20-60 ℃;
or, in an inert organic solvent, firstly, reacting the component a with the component c for 10-120 min; finally, adding the component d, and reacting for 20-120 min; the temperature in the preparation process of the catalyst is 20-60 ℃;
or, in an inert organic solvent, firstly mixing the component a and the component b for 1-5 min; then adding the component c to react for 20-120 min; the temperature in the preparation process of the catalyst is 20-60 ℃;
or, in an inert organic solvent, firstly mixing the component a and the component b, and reacting for 20-120 min; the temperature in the preparation process of the catalyst is 20-60 ℃;
the organic solvent in the step S2 is selected from one or more of non-polar aromatic hydrocarbons and non-polar aliphatic hydrocarbons, and the organic solvent includes, but is not limited to, pentane, cyclopentane, hexane, cyclohexane, heptane, octane, benzene, and toluene.
7. The method for preparing a functionalized conjugated diene rubber according to claim 5, wherein said dithiocarbamate-containing agent includes, but is not limited to, tetramethylthiuram monosulfide, tetrabutylthiuram monosulfide, bis (1, 5-pentylene) thiuram monosulfide, tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetrabutylthiuram disulfide, bis (1, 5-pentylene) thiuram disulfide, dimethyldiphenylthiuram disulfide, diethyldiphenylthiuram disulfide, tetramethylthiuram tetrasulfide, bis (1, 5-pentylene) thiuram hexasulfide.
8. A functionalized conjugated diene rubber composite material is characterized by comprising the following raw materials in parts by weight:
using x parts of the functionalized conjugated diene rubber of any one of claims 1 to 4;
100-x parts of rubber are used;
2-8 parts of zinc oxide;
0.5-3 parts of stearic acid;
0.5-4 parts of an anti-aging agent;
1-50 parts of a softener;
30-100 parts of reinforcing filler;
0.2-5 parts of an accelerator;
0.5-5 parts of sulfur;
wherein x is 5 to 100.
9. The functionalized conjugated diene rubber composite of claim 8, wherein:
the blended rubber is rubber used for tire products, and comprises but is not limited to one or more of natural rubber, styrene-butadiene rubber, isoprene rubber and butyl rubber;
the reinforcing filler is one or more than one of carbon black, white carbon black, clay, carbon nano tubes, halloysite and graphene oxide.
10. A method of preparing a functionalized conjugated diene rubber composite according to claim 8, wherein:
the functionalized conjugated diene rubber composite material containing dithiocarbamate is prepared by using the prepared functionalized conjugated diene rubber as a rubber matrix and other rubbers in combination, and adopting a mixing and vulcanizing process together with an anti-aging system, a vulcanizing system, a softening system and a reinforcing system on the basis of the preparation method of the functionalized conjugated diene rubber as claimed in any one of claims 4 to 6.
CN202210858757.9A 2022-07-20 2022-07-20 Functionalized conjugated diene rubber, composite material and preparation method thereof Pending CN115304698A (en)

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