阅读说明：本技术 一种含氮多官能化液体橡胶聚合物及其制备和应用 (Nitrogen-containing multifunctional liquid rubber polymer and preparation and application thereof ) 是由 徐国梁 王优 夏斌 王小荣 范汝良 谢治国 刘军 董栋 张宁 于 2020-07-20 设计创作，主要内容包括：本发明涉及一种含氮多官能化液体橡胶聚合物及其制备和应用,其由二烯烃单体与含氮单体反应聚合生成共聚物后,再接入含氮官能团终止剂终止聚合反应得到,其中,所述的二烯烃单体选自1,3-丁二烯或异戊二烯的一种或多种。与现有技术相比,本发明聚合物具有较多官能度的特点,以及分子量可控及可以合成多官能化液体橡胶,因此可用在在橡胶轮胎领域内如橡胶偶联剂以及加工用作基体胶料制备高性能橡胶,对合成的新型含氮官能化聚合物用作炭黑键合剂进行NR/炭黑体系混胶,并对胶料进行相应的测试,测试结果表明样品具有良好的拉伸性能以及抗湿滑性能。(The invention relates to a nitrogenous polyfunctional liquid rubber polymer, and preparation and application thereof, wherein a diene monomer and a nitrogenous monomer react to polymerize to generate a copolymer, and then a nitrogenous functional group terminator is connected to terminate the polymerization reaction to obtain the nitrogenous polyfunctional liquid rubber polymer, wherein the diene monomer is selected from one or more of 1, 3-butadiene or isoprene. Compared with the prior art, the polymer has the characteristic of higher polyfunctionality, has controllable molecular weight and can synthesize polyfunctional liquid rubber, so that the polymer can be used in the field of rubber tires, such as rubber coupling agents and matrix rubber materials for preparing high-performance rubber, the synthesized novel nitrogen-containing functionalized polymer is used as a carbon black bonding agent for NR/carbon black system rubber mixing, and the rubber materials are correspondingly tested, and the test result shows that the sample has good tensile property and wet skid resistance.)

1. The nitrogen-containing multifunctional liquid rubber polymer is characterized by being prepared by polymerizing a diene monomer and a nitrogen-containing monomer to generate a copolymer, and then connecting a nitrogen-containing functional group terminator to terminate the polymerization reaction, wherein the diene monomer is selected from one or more of 1, 3-butadiene and isoprene, and the chemical structural formula of the nitrogen-containing monomer is respectively shown as the following formula (II):

wherein m is an integer of 1 to 4, and Z is a nitrogen-containing functional group.

2. The nitrogen-containing polyfunctional liquid rubber polymer according to claim 1, wherein Z is any one or a combination of groups having the following chemical structural formula:

wherein the content of the first and second substances,

R₂、R₅each independently is a straight or branched chain alkyl, aryl or allyl group of 1 to 10 carbon atoms;

R₃、R₄each independently is a hydrogen atom, or a linear or branched alkyl or aryl group containing 1 to 4 carbon atoms;

R₆the group is hydrogen atom, or one of linear or branched alkyl, aryl, allyl or alkoxy containing 1 to 10 carbon atoms;

y is one of nitrogen, oxygen, sulfur or silicon;

a. b and n are integers of 2-10.

3. The nitrogen-containing polyfunctional liquid rubber polymer according to claim 1, wherein the nitrogen-containing monomer is prepared by the following method:

(1) placing a secondary amine compound in a reagent bottle, and pretreating by adopting calcium oxide and oxygen removal to obtain a reagent A;

(2) placing a styrene derivative containing chloroalkyl in a nonpolar solvent, and carrying out pretreatment of removing oxygen, impurities and polymerization inhibitor to obtain a reagent B;

(3) adding the reagent A into the reagent B in an ice-water bath environment, then stirring and reacting at room temperature, standing and layering to obtain supernatant, and removing a non-polar solvent to obtain a target product;

wherein, the secondary amine compound is selected from one or a mixture of compounds in the following chemical structural formula:

the chemical structural formula of the styrene derivative containing the chloroalkyl is as follows:

4. the process for producing a nitrogen-containing polyfunctional liquid rubber polymer according to any one of claims 1 to 3, comprising the steps of:

placing an organic solvent in a reaction bottle under the protection of anhydrous and oxygen-free inert gas, sequentially adding a nitrogen-containing monomer and a diene monomer, simultaneously adding a structure regulator, and then adding an initiator to perform anionic polymerization reaction to obtain a polymer molecular chain with an active center;

and (II) after the polymerization reaction is finished, taking out the reaction bottle, cooling to room temperature, adding a nitrogen-containing functional group terminator for termination reaction, and removing volatile matters from the obtained reaction product under negative pressure to obtain the target product.

5. The method according to claim 4, wherein in the step (one), the inert gas is nitrogen or argon; the organic solvent is one or a combination of several of n-hexane, pentane, cyclopentane, cyclohexane, toluene or tetrahydrofuran.

6. The method according to claim 4, wherein in step (one), the structure modifier is anisole, tetrahydrofuran, a nitrogen-containing structure modifier or an oligomeric oxolanyl alkane, wherein the nitrogen-containing structure modifier is one or a mixture of tetramethylethylenediamine, N-dimethyltetrahydrofurfuryl amine or furylpropane, and the oligomeric oxolanyl alkane has the following structural formula:

the polymerization degree of the oligomeric oxolanyl alkane is 1-5.

7. The method according to claim 4, wherein in step (one), the initiator is one of alkyl lithium, alkali metal amide or sodium naphthalene, wherein the alkyl lithium is one or more of n-butyl lithium, sec-butyl lithium, tert-butyl lithium or iso-butyl lithium, and the alkali metal amide is sodium amide or lithium amide.

8. The process according to claim 4, wherein in step (ii), an antioxidant is further added to the reaction product in an amount of 0.5 to 5% by mass based on the mass of the monomer to be polymerized, and the antioxidant is one or more selected from the group consisting of 2, 6-di-tert-butyl-4-methylphenol, 2, 6-di-tert-butylphenol, 2-methylenebis (4-methyl-6-tert-butylphenol), 4, 6-bis (octylthiomethyl) o-cresol and tris (2, 4-di-tert-butyl) phenyl phosphite.

9. The method according to claim 4, wherein in the step (one), the ratio of the amount of the nitrogen-containing monomer to the amount of the diene monomer added is 0.5 to 30: 100, respectively; the ratio of the addition amount of the structure regulator to the addition amount of the initiator is 0.1-0.5: 1;

the temperature of the polymerization reaction is 20-90 ℃, and the polymerization reaction time is 30-300 min.

10. Use of a nitrogen-containing polyfunctional liquid rubber polymer according to any one of claims 1 to 3 for the production of rubber.

Technical Field

The invention belongs to the technical field of high-performance synthetic rubber, and relates to a nitrogenous polyfunctional liquid rubber polymer, and preparation and application thereof.

Background

The main components of the rubber material are high elastic rubber polymer and reinforcing filler, wherein the filler is not uniformly dispersed in the rubber, and the poorly dispersed particles further adversely affect the rubber, such as the rolling resistance and wet skid performance of the tire material are reduced. The dispersibility of the filler is mainly related to the interaction between the fillers and the interaction between the filler and the polymer, and thus the dispersibility of the filler can be improved by improving these interactions. The method for improving the interaction between the filler and the matrix polymer is characterized in that the high-performance rubber is prepared by synthesizing the functionalized rubber polymer, the rubber polymer elastomer with the functional group is mixed with the used filler, or the rubber polymer elastomer is added into a rubber mixing formula as a low-molecular-weight liquid rubber coupling agent, so that the interaction between the filler particles and the rubber is enhanced, the compatibility of the filler particles in a rubber matrix is increased, the delay of the rubber composition can be reduced, the rubber product has less heat generation and the performance of improving the rolling resistance, and the wet-skid resistance of the tire product is improved to a certain extent due to the addition of the functional group.

US6670471 discloses a process for the synthesis of a rubbery polymer consisting of a functionalized styrene monomer and another conjugated diene, the functionalized styrene having the following structural formula:

wherein R represents an alkyl group having 1 to 10 carbon atoms or a hydrogen atom, and wherein R¹And R²May be the same or different and represents a hydrogen atom or a group selected from:

wherein R is³The groups may be the same or different and represent alkyl groups having from 1 to about 10 carbon atoms, aryl groups, allyl groups and the formula- (CH-) - (CH)₂)_y—O—(CH₂)_z—CH₃Wherein Z represents a nitrogen-containing heterocyclic compound, wherein R⁴Representative is selected from 1 to about 10Members of alkyl, aryl and allyl radicals of carbon atoms, in which n, X, y and Z represent integers from 1 to 10, R¹And R²Cannot be simultaneously hydrogen atoms. The functionalized monomers of the invention increase the compatibility of the rubber with filler types commonly used in rubber compounds such as carbon black and silica, thereby achieving improved polymer properties.

Chinese patent application CN108017757B discloses a method for synthesizing functionalized solution-polymerized styrene-butadiene rubber in a silane coupling agent modified chain, which comprises the following steps of (1) adding butadiene and styrene into a hydrocarbon solvent under the protection of argon, wherein the mass ratio of the butadiene to the styrene is 1: 9-5: 5, adding organolithium to kill impurities and using the organolithium as an initiator, and adding the organolithium to the solvent to obtain the modified styrene-butadiene rubber with the mass fraction of 60-40 × 10^-6The structure regulator of (1), the random copolymerization of butadiene and styrene is carried out at 40-80 ℃; (2) when the conversion rate of the copolymerization reaction is close to 100 percent, adding organic lithium into the hydrocarbon solution of the non-terminated activated solution polymerized styrene-butadiene rubber, and reacting for 5-30 minutes at 40-80 ℃ to obtain a glue solution; (3) adding a silane coupling agent into the glue solution, keeping the temperature of 40-80 ℃ for reaction for 30-120 minutes, stopping adding an antioxidant after the reaction is finished by water, discharging, and performing wet condensation and drying on the glue solution to obtain branched in-chain functionalized solution polymerized styrene-butadiene rubber; the amount of the substance of the silane coupling agent is 80-200% of the amount of the organic lithium substance; the amount of antioxidant is 0.5-5% of the total w.t.% of the monomers.

Although the functionalized rubber polymer with remarkable effect can be obtained in the above patent, some defects still exist, such as no preparation strategy for preparing liquid rubber with excellent processability is available, and secondly, the most common silica functional group in the functional groups of the functionalized liquid polymer can effectively improve the dispersibility of silica in a rubber matrix, and has very important influence on the performance of the functional rubber, but the silica group has remarkable coupling side reaction in the active anion polymerization process, and has certain defects. Meanwhile, most of functionalized rubber polymers existing in the market are monofunctional or bifunctional rubber polymers, so that a novel nitrogen-containing multifunctional liquid rubber polymer is developed, the molecular weight of the novel nitrogen-containing multifunctional liquid rubber polymer is controllable, and the prepared low-weight functionalized liquid rubber polymer is used as a coupling agent or a bonding agent of a rubber material or used as a multifunctional liquid rubber with excellent processing performance to be applied to a rubber material, so that the important significance is realized in preparing high-performance rubber and improving the performance of tires in the rubber tire industry.

Disclosure of Invention

The invention aims to provide a nitrogenous polyfunctional liquid rubber polymer, and preparation and application thereof, so as to improve the rolling resistance, tensile property and/or wet skid resistance and other properties of rubber products.

The purpose of the invention can be realized by the following technical scheme:

one of the technical schemes of the invention provides a nitrogenous polyfunctional liquid rubber polymer, which is obtained by reacting and polymerizing a diene monomer and a nitrogenous monomer to generate a copolymer and then connecting a nitrogenous functional group terminator to terminate the polymerization reaction, wherein the diene monomer is selected from one or more of 1, 3-butadiene or isoprene, and the chemical structural formulas of the nitrogenous monomers are respectively shown in the following formula (II):

wherein m is an integer of 1 to 4, and Z is a nitrogen-containing functional group.

Further, the structural schematic diagram of the nitrogen-containing polyfunctional liquid rubber polymer is shown as the following formula (I):

wherein, the black solid line represents the polymer chain segment composed of the diene monomer, and the round dots represent the polymer chain segment composed of the nitrogen-containing monomer, that is, the wavy line represents the resulting random polymer chain composed of the diene and the nitrogen-containing monomer. X is derived from a nitrogen-containing functional group terminator attached to the polymer chain at the end of the anionic polymerization reaction, wherein the nitrogen-containing functional group terminator has the chemical formula shown in formula (III) below:

in the formula, R₁Is a hydrogen atom, or a linear or branched alkyl or aryl group containing 1 to 4 carbon atoms.

Further, Z is any one or combination of several of the groups in the following chemical structural formula:

wherein the content of the first and second substances,

R₂、R₅each independently is a straight or branched chain alkyl, aryl or allyl group of 1 to 10 carbon atoms;

R₃、R₄each independently is a hydrogen atom, or a linear or branched alkyl or aryl group containing 1 to 4 carbon atoms;

R₆the group is hydrogen atom, or one of linear or branched alkyl, aryl, allyl or alkoxy containing 1 to 10 carbon atoms;

y is one of nitrogen, oxygen, sulfur or silicon;

a. b and n are integers of 2-10. Further, R₅Preferably methyl or ethyl; r₂、R₃、R₄、R₆It may preferably be a methyl group or a hydrogen atom; in addition, the aryl group is preferably a phenyl group. Further, n is preferably 4, 5 or 6; a. b is preferably 2 or 3 independently of each other. R₂、R₃、R₄A group is a group linked to a ring.

Further, the nitrogen-containing monomer is prepared by the following method:

(1) placing a secondary amine compound in a reagent bottle, and pretreating by adopting calcium oxide and oxygen removal to obtain a reagent A;

(2) placing a styrene derivative containing chloroalkyl in a nonpolar solvent, and carrying out pretreatment of removing oxygen, impurities and polymerization inhibitor to obtain a reagent B;

(3) adding the reagent A into the reagent B in an ice-water bath environment, then stirring at room temperature for reaction, standing for layering to obtain supernatant, and storing (at the moment, a mixture containing a nonpolar solvent) to obtain a target product nitrogen-containing monomer dissolved in the nonpolar solvent;

wherein, the secondary amine compound is selected from one or a mixture of several compounds in the following chemical structural formula:

the chemical structural formula of the styrene derivative containing the chloroalkyl is as follows:

specifically, the preparation method of the nitrogen-containing monomer can refer to the following chemical reaction formula:

further, the molar ratio of the reagent A to the reagent B is 2:1, and the feeding process is as slow as possible. The reaction time with stirring at room temperature is 12 to 48 hours, preferably 12 to 24 hours.

The second technical scheme of the invention provides a preparation method of a nitrogenous polyfunctional liquid rubber polymer, which comprises the following steps:

placing an organic solvent in a reaction bottle under the protection of anhydrous and oxygen-free inert gas, sequentially adding a nitrogen-containing monomer and a diene monomer, simultaneously adding a structure regulator, and then adding an initiator to perform anionic polymerization reaction to obtain a polymer molecular chain with an active center;

and (II) after the polymerization reaction is finished, taking out the reaction bottle, cooling to room temperature, adding a nitrogen-containing functional group terminator for termination reaction, and removing volatile matters from the obtained reaction product under negative pressure to obtain the target product.

Further, in the step (one), the inert gas is nitrogen or argon; the organic solvent is one or a combination of several of n-hexane, pentane, cyclopentane, cyclohexane, toluene or tetrahydrofuran.

Further, in the step (one), the structure regulator is anisole, tetrahydrofuran, a nitrogen-containing structure regulator or an oligomeric oxolanyl alkane. Furthermore, the nitrogen-containing structure regulator is one or a mixture of more of tetramethylethylenediamine, N-dimethyltetrahydrofurfuryl amine or furyl propane. Further, the oligomeric oxolanyl alkane is of the formula:

y represents a positive integer, and the degree of polymerization of the oligomeric oxolanyl alkane is 1 to 5.

Further, in the step (one), the initiator is one of alkyl lithium, alkali metal amide or sodium naphthalene, wherein the alkyl lithium is one or more of n-butyl lithium, sec-butyl lithium, tert-butyl lithium or isobutyl lithium, and the alkali metal amide is sodium amide or lithium amide.

Further, in the step (two), the anti-aging agent is selected from one or more of 2, 6-di-tert-butyl-4-methylphenol, 2, 6-di-tert-butylphenol, 2-methylenebis (4-methyl-6-tert-butylphenol), 4, 6-bis (octylthiomethyl) o-cresol or tris (2, 4-di-tert-butyl) phenyl phosphite.

Further, in the step (one), the ratio of the addition amount of the nitrogen-containing monomer to the diene monomer is 0.5 to 30: 100, respectively; the ratio of the addition amount of the structure regulator to the addition amount of the initiator is 0.1-0.5: 1.

further, the temperature of the polymerization reaction is 20-90 ℃, and the polymerization reaction time is 30-300 min;

in the step (II), an anti-aging agent can be added into the reaction product, and the dosage of the anti-aging agent is 0.5-5% of the mass dosage of the polymerization monomer (namely the mass sum of the diene monomer and the nitrogen-containing monomer).

The third technical scheme of the invention provides an application of a nitrogenous polyfunctional liquid rubber polymer in rubber preparation.

Further, the nitrogenous polyfunctional liquid rubber polymer can be used as a matrix polymer and used for preparing rubber materials, and at the moment, the correspondingly applicable filler is carbon black or white carbon black;

meanwhile, the nitrogenous polyfunctional liquid rubber polymer can also be used as a bonding agent and used for preparing rubber materials, and at the moment, correspondingly applicable material systems are a natural rubber/carbon black system (or white carbon black), a styrene butadiene rubber/carbon black system (or white carbon black), a butadiene rubber/carbon black system (or white carbon black), an isoprene rubber/carbon black system (or white carbon black), a chloroprene rubber/carbon black system (or white carbon black), a butyl rubber/carbon black system (or white carbon black) and an ethylene propylene rubber/carbon black system (or white carbon black).

Without being bound by any theory, the following reasoning is that the rubber polymer elastomer with functional groups is mixed with the used filler, or is added into a rubber mixing formula as a low molecular weight liquid rubber coupling agent, so that the interaction between the filler particles and the colloid can be strengthened, the compatibility of the filler particles in a rubber matrix can be increased, and the hysteresis of the rubber composition can be reduced, so that the rubber product has the performances of less heat generation and improvement of rolling resistance, and the wet skid resistance of the tire product can be improved to a certain extent due to the addition of the functional groups.

Compared with the prior art, the novel nitrogen-containing multifunctional liquid rubber polymer has simple preparation process and controllable molecular weight, and is very suitable for industrial production. The high molecular weight polymer product can be used as a matrix polymer in a rubber material, and simultaneously, a low-weight functionalized liquid rubber polymer can be prepared to be used as a coupling agent or a bonding agent in the rubber material, so that the rolling resistance, the tensile property and/or the wet skid resistance and the like of the rubber product can be improved. The preparation of high-performance rubber and the improvement of the performance of tires in the rubber tire industry are of great significance.

Drawings

FIG. 1 shows the final product obtained in example 1¹H NMR spectrum, using deuterochloroform (containing 1.0% TMS) as solvent.

Detailed Description

The present invention will be described in detail with reference to specific examples. The present embodiment is implemented on the premise of the technical solution of the present invention, and a detailed implementation manner and a specific operation process are given, but the scope of the present invention is not limited to the following embodiments.

In each of the following examples, the treatment of monomers with solvents: the pretreatment of the monomer and the solvent uses a molecular sieve and alumina to remove impurities, uses calcium hydride to remove water, and uses nitrogen bubbling to remove oxygen. The required molecular sieve and calcium oxide are put into a wide-mouth bottle and then put into a vacuum oven for drying. Taking out, under nitrogen protection, immediately sealing, and sealing with waterproof adhesive tape. After a positive pressure bottle (generally a big bottle) is opened, a molecular sieve, alumina (both of which are treated) and calcium hydride are sequentially put into the positive pressure bottle, a reagent (monomer or solvent) is added into the positive pressure bottle by a funnel, a rubber pad and a metal cover are used for sealing the bottle opening, and nitrogen is bubbled for 10-12 hours. After pretreatment, the solvent is placed at room temperature, and the monomer needs to be stored in a freezing way.

Methyl pyrrolidone solution terminator: the methyl pyrrolidone reagent was added to the toluene reagent to prepare a 1mol/L solution, and then the oxygen removal operation of nitrogen bubbling was performed.

Isopropanol terminating agent: preparing a certain amount of antioxidant 2, 6-di-tert-butyl-4-methylphenol (BHT) into isopropanol solution containing 3% BHT, and carrying out nitrogen bubbling deoxygenation operation.

Furyl propane structure modifier: dissolving a certain amount of furyl propane in the n-hexane solution after removing water and oxygen to prepare 1.76mol/L

0.60mol/L of n-butyllithium: a commercially available n-butyllithium reagent (1.6 mol/L) dissolved in n-hexane was diluted to a concentration of 0.60mol/L with n-hexane after removing water and oxygen.

The remainder, unless otherwise indicated, are all conventional commercial starting materials or conventional processing reagents in the art.