阅读说明：本技术 一种端环氧基聚硫橡胶改性ssbr及其制备方法和在半钢子午线轮胎胎面胶中的应用 (End-epoxy-terminated polysulfide rubber modified SSBR, preparation method thereof and application thereof in tread rubber of semi-steel radial tire ) 是由 邢立江 张建国 刘篪 姚琼 蒋文英 于 2018-06-07 设计创作，主要内容包括：本发明公开了一种端环氧基聚硫橡胶改性SSBR及其制备方法和在半钢子午线轮胎胎面胶中的应用。改性SSBR的制备过程：以苯乙烯和丁二烯为聚合单体,通过有机锂引发聚合到含活性端基锂的丁苯无规共聚物溶胶,丁苯无规共聚物溶胶采用端环氧基聚硫橡胶偶合,即得端环氧基聚硫橡胶改性丁苯无规共聚物；该聚合物保留丁苯无规聚合物原有的力学性能,且赋予了聚硫橡胶的低温柔顺性、耐溶剂性、耐候和耐老化性,与现有的市售的通用SSBR相比,通过中端聚硫橡胶改性SSBR所制备的半钢子午线轮胎滚动阻力改善率达至25～30％。(The invention discloses an end-epoxy-terminated polysulfide rubber modified SSBR, a preparation method thereof and application thereof in tread rubber of a semi-steel radial tire. The preparation process of the modified SSBR comprises the following steps: styrene and butadiene are used as polymerization monomers, organic lithium is used for initiating polymerization to styrene-butadiene random copolymer sol containing active end group lithium, and the styrene-butadiene random copolymer sol is coupled by epoxy-terminated polysulfide rubber to obtain the epoxy-terminated polysulfide rubber modified styrene-butadiene random copolymer; the polymer retains the original mechanical properties of the styrene-butadiene random polymer, and endows the polysulfide rubber with low-temperature flexibility, solvent resistance, weather resistance and aging resistance, and compared with the existing commercial general SSBR, the improvement rate of the rolling resistance of the semi-steel radial tire prepared by the middle-end polysulfide rubber modified SSBR reaches 25-30%.)

1. An end-epoxy-terminated polysulfide rubber modified SSBR, which is characterized in that: has the structure of formula 1:

Wherein the content of the first and second substances,

a is 3-28;

b is 1-4;

R is a terminator residue;

R₁Is a random copolymerization chain segment of butadiene and styrene;

R₂Is C₁～C₁₀An alkyl chain or an alkoxy ether chain.

2. The SSBR according to claim 1, wherein said SSBR comprises: r₁has a number average molecular weight of 2X 10⁴～6×10⁴。

3. The SSBR according to claim 2, wherein said SSBR comprises: r₁The block ratio of butadiene to styrene is (20-40)/(80-60).

4. The SSBR according to claim 3, wherein said SSBR comprises: the polymerization ratio of 1, 2-in the butadiene block is 40-65%.

5. the SSBR according to claim 1, wherein said SSBR comprises: r is hydrogen or alkyl.

6. The SSBR according to claim 1, wherein said SSBR comprises: the number average molecular weight of the end epoxy group polysulfide rubber modified SSBR is 8 x 10⁴～9×10⁴The Mooney viscosity is 55-80.

7. The method for preparing an end-epoxy-terminated polysulfide rubber modified SSBR of any of claims 1 to 3, wherein the method comprises the following steps: styrene and butadiene are used as polymerization monomers, organic lithium is used for initiating polymerization to styrene-butadiene random copolymer sol containing active end group lithium, and the styrene-butadiene random copolymer sol is obtained by coupling epoxy-terminated polysulfide rubber.

8. The method for preparing an end-epoxy-terminated polysulfide rubber modified SSBR of claim 7, wherein: the end epoxy group polysulfide rubber has a structure of formula 2:

Wherein the content of the first and second substances,

a is 3-28;

b is 1-4;

R₂Is C₁～C₁₀An alkyl chain or an alkoxy ether chain.

9. the method for preparing an end-epoxy-terminated polysulfide rubber modified SSBR of claim 7, wherein: the molar ratio of active lithium to the epoxy group of the epoxy-terminated polysulfide rubber in the styrene-butadiene random copolymer sol is 1: 1-2.

10. The method for preparing an end-epoxy-terminated polysulfide rubber modified SSBR according to any of claims 7 to 9, wherein: in the coupling process, the reaction temperature is 50-70 ℃ and the time is 30-35 min.

11. Use of the end-epoxy-terminated polysulfide rubber modified SSBR of any of claims 1 to 6, characterized in that: the rubber is applied as a raw material of a tread rubber formula of a semi-steel radial tire.

12. the use of an end-epoxy-terminated polysulfide rubber modified SSBR as claimed in claim 11, wherein: the formula of the tread rubber of the semi-steel radial tire comprises the following components in percentage by mass: 125 parts of end-epoxy-group polysulfide rubber modified SSBR, 30-40 parts of high cis-BR, 90-110 parts of white carbon black 175GR, 6-10 parts of carbon black N3306, 10 parts of Si-696, 2-4 parts of stearic acid, 4-5 parts of zinc oxide, 02-5 parts of anti-aging agent 40202, 2-5 parts of promoter CZ, 2-4 parts of promoter D, 50-70 parts of TDAE oil and 2-5 parts of sulfur.

Technical Field

The invention relates to a modified styrene-butadiene rubber material, in particular to a method for preparing an epoxy-terminated polysulfide rubber modified styrene-butadiene random copolymer by using an epoxy-terminated polysulfide rubber as a coupling agent of an anionic polymer SSBR (styrene-butadiene rubber), and also relates to the use of the epoxy-terminated polysulfide rubber modified styrene-butadiene random copolymer as a raw material of a tread rubber formula of a semi-steel radial tire, belonging to the technical field of modified styrene-butadiene rubber.

background

As a coupling agent for solution-polymerized styrene-butadiene rubber (SSBR), tin tetrachloride, low molecular weight organosiloxane, epoxy compound and the like are generally used. Such as epoxidized soybean oil, 3-N, N-bis (trimethylsilyl) aminopropyl (methyl) diethoxysilane, and N-benzylidene-3-triethoxysilyl-1-propylamine. In the text "20 th century SSBR Synthesis technology progress", "synthetic rubber industry", 1999-09-15 "second generation solution polymerized styrene-butadiene rubber (SSBR) is introduced, which combines low rolling resistance and high wet skid resistance of rubber by chain end modification inside coupling and reasonable adjustment of styrene and vinyl chain link content and sequence distribution thereof, thereby more fully adapting to energy saving and safety requirements of tires. Representative examples thereof include Cariflex S-1215 (U.S. Shell), SL series tin-coupled SSBR (JSR, Japan), NS series SSBR (Zeon, Japan), and the like. The technique of the Shell company patent is characterized by a steep styrene chain distribution at the end of the macromolecular chain, it being possible to use diethyl adipate as coupling agent. The JSR products are characterized by tin coupling reactions in the presence of lithium butadienyl at the living chain end. Zeon modifies the end of the living polymer with benzophenone compounds containing amino groups, so that the resilience of the vulcanized rubber is obviously improved, and the wet skid resistance of the rubber is not damaged. However, the SSBR synthesized by the technology belongs to the second generation solution polymerized styrene-butadiene rubber, and can not meet the development requirement of the current ultrahigh-performance tire. For example, in Japanese patent (JP2009287020A), SSBR obtained by polymerizing butadiene and styrene in cyclohexane and end-capping coupling with 3-N, N-bis (trimethylsilyl) aminopropyl (methyl) diethoxysilane is coupled, and this method is of the coupled type, in which the polar nitrogen atom is in the middle stage of the polymer, which is end-functionalized in the molecular chain. In the US patent (US5616704A) SSBR is described which is synthesized by reacting secondary amines with butyl lithium to form secondary aminolithium as initiator for the polymerization of styrene and butadiene and finally terminating the polymerization with trialkyltin chloride or 4,4 "-bis (methylene) benzophenone or other N, N" -dialkyl-amino-alkyl ketones or aldehydes or N, N "-dialkyl-amino-alkyl alkenes. However, the secondary amino lithium is affected by temperature and equilibrium reaction in the preparation process, and a small amount of secondary amine always exists in the secondary amino lithium solution, which seriously affects the polymerization reaction kinetics, causes incomplete polymerization reaction, does not remove the molecular weight of the polymer, and the like. European patent (EP0493839B1) discloses "Tin associating elastomer and products having reduced polymerization properties", wherein tributyl Tin lithium is used to initiate polymerization, and finally tributyl Tin chloride is used to end-cap polymer, wherein the tributyl Tin lithium has fast decomposition rate during storage, large amount of initiator is used, the molecular weight of polymer is unstable, and organotin remains in the polymer, which is harmful to the health of operators. Lihantang (modified synthetic rubber for white carbon black and carbon black filled tread rubber [ J ]. modern rubber technology, 2012,38(5):12-17.) A reference is made to the modification of styrene-butadiene copolymers with 2% by weight of a main chain modifier such as C16-C18 fatty chain terminal sulfur-containing species, a comparative polymer being prepared according to the same formulation except that no modifier is added. As a result, the tensile strength and 300% stress at definite elongation of the vulcanizate of the main chain modified polymer are both improved, the rolling resistance performance (60 ℃ tan S) of the vulcanizate of the main chain modified polymer is improved by l 9-32%, and the wet grip performance (0 ℃ tan S) is slightly reduced by 3-15%. That is, the rolling resistance measured for the backbone modified polymer is greatly improved as compared to the unmodified comparative polymer, while the heat generation of the vulcanizate is reduced. The hysteresis properties of the chain end modified polymers can be further improved by employing backbone modification techniques. However, the mechanism of modifying the C16-C18 fatty chain sulfur-containing end groups with the styrene-butadiene copolymer backbone is not further described in the art.

At present, various tire companies in the world produce semi-steel radial tires by SSBR, the rolling resistance and the wet skid resistance can generally reach B/C grade standards, higher-grade double A or double B or A/B grade standards are difficult to reach, and functionalization is the most effective method for realizing high performance of the SSBR. The significance of high performance is that the rolling resistance and the wet skid resistance are comprehensively balanced, so that a safe, comfortable and energy-saving green tire is manufactured. It is therefore desirable to select a highly polar, higher molecular weight oligomer for use in the intermediate-end modification of SSBR and for the preparation of ultra-high performance tires having low rolling resistance.

The traditional polysulfide rubber with mercaptan at the molecular chain end is rubber, has the advantages of low-temperature flexibility, solvent resistance, stress relaxation, weather resistance, good aging resistance and the like after being vulcanized, and is mainly used for manufacturing oil delivery rubber pipes, automobile oil tanks, sealing gaskets, deformation shrinkage joints of airport runways and buildings, printing rubber rollers, sealing rings, sealing adhesives and the like. Is a synthetic rubber obtained by polycondensation of a dihaloalkane and a polysulfide of an alkali metal or an alkaline earth metal. The liquid polysulfide rubber is cured and molded by condensation of thiol at the molecular chain terminal with metal oxide or ring-opening crosslinking with oligomer of epoxy group, but the liquid polysulfide rubber cannot be used as a coupling agent of anion polymerization active lithium.

Disclosure of Invention

Aiming at the defects of the existing low molecular compound used for modifying the SSBR polymer, the invention provides an epoxy-terminated polysulfide rubber modified styrene-butadiene random copolymer, which retains the original elasticity of the styrene-butadiene random copolymer and endows the polysulfide rubber with low-temperature flexibility, solvent resistance, weather resistance and aging resistance, and compared with the existing commercial general SSBR, the rolling resistance improvement rate of the semi-steel radial tire prepared by the middle-end polysulfide rubber modified SSBR reaches 25-30%.

The second purpose of the invention is to provide a method for preparing the epoxy-terminated polysulfide rubber modified styrene-butadiene random copolymer with simple steps and low cost.

The third purpose of the invention is to provide an application of the modified styrene-butadiene random copolymer with the epoxy-terminated polysulfide rubber as the tread rubber of the semi-steel radial tire, wherein the modified styrene-butadiene random copolymer introduces low-temperature flexibility, solvent resistance, weather resistance and aging resistance through the polysulfide rubber, and simultaneously retains the original elasticity of the styrene-butadiene random copolymer, so that the rolling resistance of the semi-steel radial tire can be obviously improved.

In order to achieve the above technical object, the present invention provides an end-epoxy-group polysulfide rubber modified SSBR having the structure of formula 1:

Wherein the content of the first and second substances,

a is 3-28;

b is 1-4;

R is a terminator residue;

R₁Is a random copolymerization chain segment of butadiene and styrene;

R₂is C₁～C₁₀an alkyl chain or an alkoxy ether chain.

preferred embodiment, R₁Has a number average molecular weight of 2X 10⁴～6×10⁴. More preferably 3X 10⁴～5×10⁴。

Preferred embodiment, R₁the block ratio (mass ratio) of the butadiene to the styrene is (20-40)/(80-60). More preferably (22-38)/(78-62).

In a preferred embodiment, the 1, 2-polymerization ratio in the butadiene block is 40 to 65%.

In a preferred embodiment, R is hydrogen or alkyl (alkyl is lower alkyl, generally lower than C)₅)。

Preferably, the number average molecular weight of the end-epoxy-group polysulfide rubber modified SSBR is 8X 10⁴～9×10⁴The Mooney viscosity is 55-80. Molecular weight distribution index M_Wand/Mn is 1.5-1.8. Weight average molecular weight M_W＝12×10⁴～16×10⁴。

The invention also provides a preparation method of the end-epoxy-group-terminated polysulfide rubber modified SSBR, which takes styrene and butadiene as polymerization monomers, and the styrene-butadiene random copolymer sol containing active end-group lithium is initiated and polymerized by organic lithium, and the styrene-butadiene random copolymer sol is obtained by coupling the end-epoxy-group-terminated polysulfide rubber.

Preferably, the end-epoxy-group polysulfide rubber has a structure of formula 2:

Wherein the content of the first and second substances,

a is 3-28;

b is 1-4;

R₂Is C₁～C₁₀An alkyl chain or an alkoxy ether chain.

Preferably, the molar ratio of active lithium to the epoxy group of the epoxy-terminated polysulfide rubber in the styrene-butadiene random copolymer sol is 1: 1-2.

In the preferable scheme, in the coupling process, the reaction temperature is 50-70 ℃ and the time is 30-35 min.

In the preparation process of the end epoxy group polysulfide rubber modified SSBR, water or alcohols are adopted to terminate the reaction after the coupling reaction is finished.

The invention also provides application of the end-epoxy-group polysulfide rubber modified SSBR, which is applied as a raw material of a tread rubber formula of a semi-steel radial tire.

according to the preferable scheme, the formula of the tread rubber of the semi-steel radial tire comprises the following components in percentage by mass: 125 parts of end-epoxy-group polysulfide rubber modified SSBR, 30-40 parts of high cis-BR, 90-110 parts of white carbon black 175GR, 6-10 parts of carbon black N3306, 10 parts of Si-696, 2-4 parts of stearic acid, 4-5 parts of zinc oxide, 02-5 parts of anti-aging agent 40202, 2-5 parts of promoter CZ, 2-4 parts of promoter D, 50-70 parts of TDAE oil and 2-5 parts of sulfur.

the preparation method of the end-epoxy-group polysulfide rubber modified SSBR of the invention synthesizes the SSBR by the conventional method. The preparation method comprises the steps of preparing a random styrene-butadiene random copolymer with active lithium at the tail end by using a mixed monomer of styrene and butadiene monomers and initiating anionic polymerization by using butyl lithium, and finally carrying out coupling reaction on the active polymer by using liquid polysulfide rubber with an end epoxy group to obtain the modified styrene-butadiene random copolymer. During the polymerization process, a regulator for regulating the vinyl unit structure, such as at least one of tetrahydrofurfuryl alcohol ethyl ether, ditetrahydrofurfuryl propane, tetrahydrofurfuryl alcohol hexyl ether and the like, can be adopted, wherein the concentration of the regulator in the polymerization solvent cyclohexane is 170-400 mg/kg. The polymerization initiator is n-butyl lithium or sec-butyl lithium; the polymerization temperature is 45-70 ℃; the polymerization time is 25-60 min.

The preparation method of the end epoxy group-terminated polysulfide rubber comprises the steps of reacting the polysulfide rubber with an alkyl lithium reagent in advance, and converting thiol groups in the polysulfide rubber into sulfur-lithium bonds to obtain a sulfur-lithium polymer; and then carrying out end-capping reaction on the lithium sulfide polymer and a halogenated epoxy organic raw material to obtain the lithium sulfide/epoxy resin composite material.

The polysulfide rubber of the invention has a structure of formula 3:

Wherein a is an integer of 3 to 28, and b is an integer of 1 to 4.

the preferable number average molecular weight of the polysulfide rubber is 1000 to 5000. A functionality of 2.1 to 2.7. The mass content of HS-group (mercapto) is 1.2-7.7%, and the viscosity is 7.5-200 pas.

The polysulfide rubber of the invention can be selected from series products such as LP or JLY type products and the like which are sold in the market.

The halogenated epoxy organic raw material has a structure shown in a formula 4:

Wherein R is₂Is C₁～C₁₀An alkyl chain of, or C₁～C₁₀An alkoxy ether chain, and X is halogen.

The preparation method of the epoxy-terminated liquid polysulfide rubber comprises two steps, wherein the first step is to mix the liquid polysulfide rubber (formula 3) with a solvent, and to add quantitative lithium alkyl (R) under the technological conditions of no oxygen, no water vapor and the like while stirring₃Li，R₃Alkyl), the thiol group (-SH) in the polysulfide rubber molecule is converted into a sulfur lithium bond (-SLi), and a sulfur lithium polymer (formula A) is obtained; and in the second step (also called end-capping reaction), adding a certain amount of epoxy organic chlorine raw material (formula 4) into the reaction solution to condense with the lithium sulfur group of formula A, and introducing epoxy groups into the ends of the polysulfide rubber molecules to obtain the end-epoxy-terminated polysulfide rubber (formula B). The reaction circuit is as follows:

The process conditions of the first step reaction are as follows: the reaction environment is preferably anhydrous and anaerobic and is carried out under the protection of nitrogen or argon, and the reaction solvent is aromatic solvent; preferably at least one of benzene, toluene and xylene. The mass content of the polysulfide rubber in the solvent is selected to be 20-50%. The lithium alkyl has the formula R₃Li, preferably n-butyllithium and/or sec-butyllithium; most preferably, the concentration of the alkyllithium in the solvent is 0.5 to 1.0 mol/L. The dosage of the alkyl lithium is 1.05-1.1 times of the theoretical molar weight of the complete reaction of the mercaptan in the polysulfide rubber. The reaction temperature is 10-80 ℃. The reaction time is 20-40 min. And after the alkyl lithium reacts with the polysulfide rubber, adding a terminator for terminating the excessive alkyl lithium into the reaction system, and then adding the epoxy organic chlorine raw material to carry out end-capping reaction. The terminating agent is alcohol or ketone, so that the excessive butyl lithium is terminated, and the next step of ring-opening reaction between the excessive butyl lithium and the epichlorohydrin is avoided. The using amount of the terminating agent is the total mass of the butyl lithium5-10% of the total weight of the composition. The reaction is stopped at 10-80 ℃ for 20 min.

The conditions of the second step reaction: the dosage of the halogenated epoxy organic raw material is 1.05 to 1.1 times of the theoretical dosage of completely blocking the polysulfide rubber. The temperature of the end-capping reaction is 50-80 ℃. The end capping reaction time is 60-120 min. And after the end-capping reaction is finished, adding water into the reaction system, separating out a water phase, and removing the solvent from the residual material to obtain the epoxy-terminated polysulfide rubber.

The invention discloses an end epoxy group polysulfide rubber, which has a structure shown in formula 2:

Wherein the content of the first and second substances,

a is 3-28;

b is 1-4;

R₂is C₁～C₁₀An alkyl chain or an alkoxy ether chain (e.g., an oligoethylene glycol such as an oligoethylene glycol having an oxygen atom number of 2,3 or 4).

The molecular structure of the epoxy terminated polysulfide rubber only contains ethylene ether, so that the rubber has better flexibility and elasticity, and overlong linear alkyl group shows plasticity and the rebound resilience is reduced. The number average molecular weight of the end epoxy group polysulfide rubber is 1000-5000; the viscosity is 7.5 to 200 pas, the epoxy value is 0.034 to 0.189mol/100g, and the mercapto group mass content is 1.2 to 7.7%.

The epoxy terminated polysulfide rubber is used as a coupling agent of anion polymerized styrene-butadiene random copolymer terminal active lithium (S-B-Li), and the coupled polysulfide rubber modified styrene-butadiene random polymer (also called middle-end coupling SSBR for short) is mainly used as high-performance tread rubber.

The epoxy-terminated polysulfide rubber is prepared into a solution with the mass percent concentration of 20-70% by an organic solvent for use. The preferable mass percentage is 40-60%; the solvent used is preferably at least one of benzene, toluene, xylene or THF, with toluene being preferred.

The molecular chain of the epoxy-terminated polysulfide rubber modified styrene-butadiene random copolymer (middle-end coupled SSBR) of the invention keeps the ethylene ether and sulfur-thioether bond of the original polysulfide rubber, and can still embody the flexibility and elasticity of the original polysulfide rubber. The polymer chain containing long-chain polar groups forms a new main chain modification technology, so that the hysteresis loss of vulcanized rubber can be further reduced, and the rolling heat generation of tires can be reduced; in addition, in the 'silicon formula' of the tire tread rubber, the middle-end coupling SSBR can have excellent powder-eating-compatibility with white carbon black, the processing performance of the composite mixture and the dispersibility of the carbon black in mixing and vulcanized rubber are improved, and the Payne effect is reduced. Namely, compared with the existing commercial general SSBR, the middle-end coupling SSBR has the advantages that the rolling resistance improvement rate of the prepared semi-steel radial tire reaches 25-30%, and the fuel consumption of an automobile is reduced.

the preferred silicon formula for the middle-end coupling SSBR of the invention used as the tread rubber of the semi-steel radial tire is as follows:

125 parts of middle-end coupling SSBR, 35 parts of high cis-BR, 175GR 100 parts of white carbon black, N3308 parts of carbon black, Si-698, 3 parts of stearic acid, 4.5 parts of zinc oxide, 40202.5 parts of an anti-aging agent, 2.7 parts of a promoter CZ, 2.3 parts of a promoter D, 60 parts of TDAE oil and 2.3 parts of sulfur.

The mixing and vulcanizing process of the tread rubber of the semi-steel radial tire is carried out according to the silicon formula manufacturing process well known in the industry.

compared with the prior art, the technical scheme of the invention has the following beneficial effects:

1. the epoxy-terminated polysulfide rubber modified styrene-butadiene random copolymer provided by the invention introduces a strong-polarity polysulfide rubber molecule long chain into the middle section of a polymer molecule with high styrene content or high vinyl content, and endows the polysulfide rubber with low-temperature flexibility, solvent resistance, weather resistance, aging resistance and the like on the premise of ensuring that the original mechanical properties of the styrene-butadiene rubber are not influenced.

the epoxy-terminated polysulfide rubber modified butadiene styrene random copolymer is used as a tread material of a semi-steel radial high-performance tire, and a strong polar molecular chain has good compatibility with white carbon black, so that the white carbon black is easy to uniformly disperse in SSBR, the Payne effect of vulcanized tread rubber of a composite material can be reduced, and heat generation and hysteresis loss in periodic deformation can be reduced, and compared with the traditional general SSBR, the rolling resistance improvement rate reaches 30%. Meanwhile, the low-temperature resistance and the ground gripping performance of the vulcanized rubber compound are also slightly improved.

The polysulfide rubber modified solution polymerized butadiene styrene random rubber has simple polymerization and coupling processes, can be synthesized by utilizing the existing mature process, and has easy control of reaction and easy industrialization.

Detailed Description

The present invention is illustrated by the following examples, which are not intended to limit the scope or practice of the invention.

and (3) measuring the physical properties of the vulcanized rubber by adopting an INSTRON tensile machine.

The epoxy value of epoxy group in the epoxy-terminated polysulfide rubber is determined by direct titration of brominated quaternary ammonium salt.

the molecular mass and molecular weight distribution index of the polymer were determined by gel permeation chromatography GPC.

The dynamic mechanical property of the vulcanized rubber is determined by adopting a dynamic viscoelastic spectrum, the gripping performance is represented by a value of 0 ℃/tan delta, and the rolling resistance performance is represented by a value of 60 ℃/tan delta.

The dynamic heat generation of the vulcanizate was measured using a DUNLOP power loss meter.

The end epoxy group-terminated polysulfide rubber is prepared by the following method:

Preparation of end epoxy group-terminated polysulfide rubber (1)

The first step is that 100g of JLY-121 type polysulfide rubber (average molecular weight 1000, viscosity 8 Pa.s, mercapto mass content 6.50%) and 400g of toluene are respectively put into a 1L clean three-neck flask, saturated water in materials is removed by an azeotropic dehydration method, then the temperature is reduced to below 80 ℃, under the protection of nitrogen and stirring, under the temperature of 10-80 ℃ of reaction liquid, 206mL of 1.0mol/L n-butyl lithium is continuously dropped into the reaction liquid in the flask within 20min, then the reaction is carried out for 40min, and 0.6mL of ethanol is sucked by an injector and injected into the reaction flask for terminating the reaction for 20 min.

And the second step is to add 18.5g of epichlorohydrin into the reaction liquid in the first step, stir the mixture for reaction for 60min at 50-80 ℃, add 20mL of deionized water into the reaction liquid, stir the mixture for 15min, stand the mixture to remove a water phase, and finally remove the solvent and other low-boiling organic impurities by a reduced pressure distillation method under the conditions of temperature of 100 ℃ plus one year and pressure of-0.05 MPa to obtain the amber viscous liquid. The viscosity of the end-ring oxidized polysulfide rubber was found by analysis to be 8.2 pas and the epoxy value was found to be 0.189mol/100 g.

Preparation of end epoxy group-terminated polysulfide rubber (2)

The relevant process conditions in preparation example (1) were unchanged.

Only in the first step, 100g of JLY-1225 type (average molecular weight 2500, viscosity 17 pas, mercapto group mass content 2.62%) and 100g of toluene were selected as polysulfide rubber, 87mL of n-butyllithium was used, the reaction time was 30min, and 0.5mL of ethanol was added as a terminator.

And 8.08g of epoxy chloropropane is added in the second step of reaction, the reaction time is 120min, 30mL of deionized water is used for stirring for 15min after the reaction is finished, the mixture is statically separated to remove a water phase, and the solvent and other organic impurities with low boiling point are removed by reduced pressure distillation. The viscosity of the amber viscous liquid was found by analysis to be 18.5 pas and the epoxy value to be 0.076mol/100 g.

Preparation of end epoxy group-terminated polysulfide rubber (3)

The relevant process conditions in preparation example (1) were unchanged.

Only in the first step, 100g of JLY-124 type (average molecular weight 4000, viscosity 70 pas, mercapto mass content 1.64%) and 300g of toluene were selected as polysulfide rubber, 54mL of n-butyllithium was used, the reaction time was 25min, and 0.4mL of ethanol was added as a terminator.

4.8g of epichlorohydrin is added in the second step of reaction, the reaction time is 80min, 40mL of deionized water is used for stirring for 15min after the reaction is finished, the mixture is statically separated to remove a water phase, and a reduced pressure distillation method is used for removing a solvent and other organic impurities with low boiling point. The viscosity of the amber viscous liquid was determined by analysis to be 72.1 pas and the epoxy value to be 0.048mol/100 g.

Preparation of end epoxy group-terminated polysulfide rubber (4)

The relevant process conditions in preparation example (1) were unchanged.

Only in the first step, 100g of JLY-155 type (average molecular weight 5000, viscosity 96 Pa.s, mercapto mass content 1.24%) and 400g of toluene were selected as polysulfide rubber, 79mL of 0.5mol/L n-butyllithium was used, the reaction time was 20min, and 0.3mL of ethanol was added as a terminator.

And 3.8g of epoxy chloropropane is added in the second step of reaction, the reaction time is 60min, 40mL of deionized water is used for stirring for 15min after the reaction is finished, the mixture is statically separated to remove a water phase, and a reduced pressure distillation method is used for removing a solvent and other organic impurities with low boiling point. The viscosity of the amber viscous liquid determined by analysis was 98.6 pas and the epoxy value was 0.036mol/100 g.