阅读说明：本技术 一种氢化双组分聚苯乙烯-b-共轭二烯共聚物及其制备方法和应用 (Hydrogenated bi-component polystyrene-b-conjugated diene copolymer and preparation method and application thereof ) 是由 张建国 邢立江 蒋文英 姚琼 文新荷 朱建军 于 2020-04-29 设计创作，主要内容包括：本发明公开了一种氢化双组分聚苯乙烯-b-共轭二烯共聚物及其制备方法和应用,该氢化双组分聚苯乙烯-b-共轭二烯共聚物由双组分聚苯乙烯-b-共轭二烯共聚物氢化得到；所述双组分聚苯乙烯-b-共轭二烯共聚物包含数均分子量分别为不低于60000和不高于17000的两种聚苯乙烯-b-共轭二烯无规共聚物,这种氢化双组分聚苯乙烯-b-共轭二烯共聚物体现出热塑性行为,具有在室温下挺性高、冷流低、静态稳定性好、低温内聚力低、易剥离,并在150℃以下体现出熔点低、熔体流动性好、操作弹性大、不交联的特点,特别适合用于金属器具或配合组合件切削加工保护填充定位用材料。(The invention discloses a hydrogenated bi-component polystyrene-b-conjugated diene copolymer, a preparation method and application thereof, wherein the hydrogenated bi-component polystyrene-b-conjugated diene copolymer is obtained by hydrogenating a bi-component polystyrene-b-conjugated diene copolymer; the bi-component polystyrene-b-conjugated diene copolymer comprises two polystyrene-b-conjugated diene random copolymers with the number average molecular weights of not less than 60000 and not more than 17000 respectively, the hydrogenated bi-component polystyrene-b-conjugated diene copolymer shows thermoplastic behavior, has the characteristics of high stiffness, low cold flow, good static stability, low-temperature cohesion, easy peeling at room temperature, low melting point below 150 ℃, good melt flowability, high operating elasticity and no crosslinking, and is particularly suitable for being used as a material for protecting, filling and positioning metal appliances or matched assemblies in cutting processing.)

1. A hydrogenated bicomponent polystyrene-b-conjugated diene copolymer characterized by: obtained by hydrogenation of bi-component polystyrene-b-conjugated diene copolymer;

the bi-component polystyrene-b-conjugated diene copolymer comprises two polystyrene-b-conjugated diene random copolymers with number average molecular weights of not less than 60000 and not more than 17000;

the two polystyrene-b-conjugated diene copolymers each have the following expression: S-B-B/D;

wherein the content of the first and second substances,

s is a polystyrene block;

b is a poly-conjugated diene block;

d is the divinylbenzene branching nodes randomly distributed in the B block.

2. A hydrogenated bicomponent polystyrene-b-conjugated diene copolymer according to claim 1, wherein: the mass ratio of the polystyrene-b-conjugated diene random copolymer with the number average molecular weight not less than 60000 to the two polystyrene-b-conjugated diene random copolymers with the number average molecular weight not more than 17000 is (20-25)/(80-75).

3. A hydrogenated bicomponent polystyrene-b-conjugated diene copolymer according to claim 1, wherein: the degree of hydrogenation of the conjugated diene unit in both of the polystyrene-b-conjugated diene copolymers is greater than 95%.

4. A hydrogenated bicomponent polystyrene-b-conjugated diene copolymer according to claim 1, wherein: the conjugated diene in the poly-conjugated diene block comprises at least one of butadiene, isoprene and piperylene.

5. A hydrogenated bicomponent polystyrene-b-conjugated diene copolymer according to claim 1, wherein: the mass ratio of the blocks of the two polystyrene-B-conjugated diene copolymers is S/B ═ 20-30)/(80-70).

6. A hydrogenated bicomponent polystyrene-b-conjugated diene copolymer according to claim 1, wherein: the number average molecular weights of the two polystyrene-b-conjugated diene copolymers are 60000-65000 and 12000-17000 respectively.

7. A hydrogenated bicomponent polystyrene-b-conjugated diene copolymer according to claim 1, wherein: the mass distribution index of the two polystyrene-b-conjugated diene copolymers is less than 1.05.

8. A hydrogenated bicomponent polystyrene-b-conjugated diene copolymer according to claim 1, wherein: the content of 3, 4-addition units in the conjugated diene units of the two polystyrene-b-conjugated diene copolymers is 10-60 percent.

9. A hydrogenated bicomponent polystyrene-b-conjugated diene copolymer according to claim 1, wherein: the mass of the divinylbenzene units in the two polystyrene-conjugated diene random copolymers accounts for 0.08-0.16% of the mass of the conjugated diene, and the branching degree of the divinylbenzene units is 3-6.

10. The process for producing a hydrogenated two-component polystyrene-b-conjugated diene copolymer according to any one of claims 1 to 9, wherein: the method comprises the following steps:

1) adding a solvent and an activating agent into a polymerization reaction kettle, heating to the initial polymerization temperature, adding an initiator and styrene into the polymerization reaction kettle for first-stage polymerization, adding a mixed monomer of divinylbenzene and conjugated diene after the first-stage polymerization is finished, and performing second-stage polymerization to obtain a polystyrene-b-conjugated diene copolymer glue solution; wherein, in the first-stage polymerization process, two polystyrene-b-conjugated diene random copolymer glue solutions with the number average molecular weights of not less than 60000 and not more than 17000 are obtained by controlling the dosage of the initiator;

2) uniformly mixing the two polystyrene-conjugated diene copolymer glue solutions, transferring the mixed glue solutions into a hydrogenation reaction kettle, carrying out hydrogenation reaction, condensing water vapor after the hydrogenation reaction is finished, and drying to obtain the polystyrene-conjugated diene copolymer glue solution; or transferring the two polystyrene-conjugated diene copolymer glue solutions into a hydrogenation reaction kettle respectively, carrying out hydrogenation reaction, after the hydrogenation reaction is finished, uniformly mixing the two hydrogenated polystyrene-conjugated diene copolymer glue solutions, condensing with water vapor, and drying to obtain the polystyrene-conjugated diene copolymer glue solution.

11. The method of claim 10, wherein the hydrogenated bicomponent polystyrene-b-conjugated diene copolymer comprises: the initial polymerization temperature is 50-60 ℃.

12. The method of claim 10, wherein the hydrogenated bicomponent polystyrene-b-conjugated diene copolymer comprises: the first-stage polymerization reaction time is 20-25 min, the temperature in the second-stage polymerization reaction process is controlled to be not more than 95 ℃, and the polymerization reaction time is 20-25 min.

13. The method of claim 10, wherein the hydrogenated bicomponent polystyrene-b-conjugated diene copolymer comprises: the hydrogenation reaction adopts a titanium system or nickel system catalytic system to carry out selective catalytic hydrogenation.

14. The method of claim 10, wherein the hydrogenated bicomponent polystyrene-b-conjugated diene copolymer comprises: in the hydrogenation reaction process, the temperature is controlled to be 65-85 ℃, the time is 2.5-3.0 h, and the hydrogen pressure is 1.2-1.6 MPa.

15. Use of a hydrogenated bicomponent polystyrene-b-conjugated diene copolymer according to any one of claims 1 to 9, wherein: the material is used as a filling positioning protection material in the cutting processing of metal tools or matching assemblies.

Technical Field

The invention relates to a hydrogenated bi-component polystyrene-conjugated diene random copolymer, a preparation method and application thereof, in particular to a hydrogenated bi-component polystyrene-conjugated diene random copolymer with thermoplastic behavior, a method for preparing the hydrogenated bi-component polystyrene-conjugated diene random copolymer by anionic polymerization and application of the hydrogenated bi-component polystyrene-conjugated diene random copolymer as a filling positioning protection material in cutting processing of metal appliances or matching assemblies, and belongs to the technical field of special high-molecular materials for filling protection.

Background

The metal, especially titanium alloy, of high-end precision apparatus or mating parts needs to be fixed during the machining, cutting and forming process of machine tool, otherwise the rotating parts are easy to deform during cutting and forming, which results in the precision reduction of the apparatus mating parts, excessive error or poor effect during use, such as the manufacture of the air exhaust parts for stabilizing the aircraft.

The filler used in the manufacture of the appliance or the fitting piece has the characteristics of low modulus, easy cutting, low melting point, high stiffness, no cold flow, low high-temperature sagging flow, no crosslinking at the melting temperature, good thermal stability, easy stripping and removal (like the stripping of a balsam peel) after the product is formed and the like. The existing polymers such as styrene butadiene rubber for shoe materials and tires, SBS, SEBS, SEPS or polyolefin and the like do not have the characteristics. The original appliance or the filler of the matching part is mainly solid paraffin, namely the paraffin is melted and then poured into the combination part, and the combination part is cut after cooling and solidification. The melting point of the paraffin is not higher than 80 ℃, and the paraffin removed in the processing or cleaning of the assembly belongs to Newtonian fluid and is easy to flow vertically to other parts to influence other links or processing procedures, so the method is not adopted at present.

The existing filler is polystyrene thermoplastic polymer, such as K25S, the melting point of which is not higher than 150 ℃, the polymer is formed by mixing two polymers, and the polymer moleculesContaining a small amount of butadiene 1, 2-addition units and polystyrene block units, but no literature is available describing the preparation process and the behavior of the polymer. However, chinese patent (CN107793542A) describes a method for synthesizing a hydrogenated styrene/isoprene block copolymer, which comprises synthesizing a diblock copolymer or a multiblock copolymer comprising a styrene block and an isoprene block in an anionic polymerization system using nonpolar alkane and toluene as polymerization solvents, and then hydrogenating the copolymer to obtain a hydrogenated styrene/isoprene block copolymer, wherein the diblock or multiblock hydrogenated styrene/isoprene block copolymer is used for optical fibers and optical cable filling ointments. In Chinese patent (CN102731739A), a star polymer used as a viscosity index improver of lubricating oil and a preparation method and application thereof are disclosed, and particularly, the star polymer is provided with asymmetric arms and consists of two different types of polymer arms, wherein the first type of arm is hydrogenated polyisoprene homopolymer, the second type of arm is a copolymer with a hydrogenated polyisoprene-hydrogenated polybutadiene-polystyrene block structure, a polystyrene block is close to the core of the star polymer in the copolymer arm, a hydrogenated polybutadiene block is in the middle of the arm, and a hydrogenated isoprene block is outside the arm, the polymer shows excellent tackifying effect and shear stability of oil products, and has lower pumping viscosity and low-temperature start viscosity in formulated engine oil. The star polymer has too high molecular weight and low melt index, and is not suitable for being used as a material for filling and protecting metal appliances or fittings. In addition, Chinese patent (CN104945559A) describes a hydrogenated polystyrene-b-styrene/butadiene/isoprene random copolymer and a preparation method and application thereof. The hydrogenated polystyrene-b-styrene/butadiene/isoprene random copolymer consists of S_n-b-BS_mIR、(S_n-b-BS_mI)₂Si(CH₃)₂、(S_n-b-BS_mI)₃SiCH₃And (S)_n-b-BS_mI)₄The mixed polymer of Si composition is obtained by hydrogenation. The obtained hydrogenated polystyrene-b-styrene/butadiene/isoprene random copolymerization has comprehensive mechanical properties and aging resistanceGood and has double bonds available for vulcanization; the polymer is suitable for outdoor sealing materials, but is not suitable for filling and protecting metal appliances or fittings. In the chemical industry and engineering, preparation and characterization of star-shaped hydrogenated random copolymer HSSIBR in 2012, star-shaped styrene-isoprene-butadiene ternary random copolymer (SSIBR) is prepared by anionic polymerization with Divinylbenzene (DVB) as coupling agent and cyclohexane as solvent; nickel naphthenate and triisobutyl aluminum are used as catalysts to react for 4 hours at 60 ℃ and 4.0MPa hydrogen pressure, and hydrogenated star-shaped styrene-isoprene-butadiene ternary random copolymer (HSSIBR) with the hydrogenation degree of 100% is prepared. The additive is used as a viscosity index improver of lubricating oil, the shear stability of the additive is improved, and the low-temperature performance of the additive is obviously improved. Similarly, in the text (science and engineering of polymer materials, molecular structure of viscosity index improver HSD at stage 11 of 2012), a hydrogenated styrene/conjugated diene (butadiene, isoprene) copolymer (HSD) is introduced as a viscosity index improver, where HSD is a highly hydrogenated styrene-butadiene block copolymer with high butadiene content, styrene has a mass fraction of 18.5%, butadiene has a mass fraction of 81.5%, butadiene has a degree of hydrogenation of 98.0%, the number-average molecular weight of one arm is 6.47 × 104g/mol, the number of coupling arms is 7.10, and the coupling efficiency is 86.44%. The polymer is also used as a thickener for lubricating oil, but the polymer has the defects of large molecular weight, high modulus, high strength, high melting point and the like, so that the polymer is not suitable for being used as a filling protective material for metal appliances or processing matching parts. However, hydrogenated polymers such as SEPS-4010, SEPS-4030 and SEBS-501 available on the market have too high molecular weight, a melting point of 200 ℃ or higher, poor melt fluidity and low handling elasticity, and are not suitable for filling and protecting materials in metal appliances or processing matching parts.

In view of the above, the conventional literature and commercially available polymers such as styrene-conjugated dienes, hydrides and polyolefins mainly exhibit the defects of high strength, high viscosity, difficult peeling, high melting point, difficult flowing, poor thermal stability, easy crosslinking, and loss of fluidity, and thus cannot satisfy the filling protection of the processing and molding of metal appliances or mating members.

Disclosure of Invention

Aiming at the defects that the polymer in the prior art has low stiffness, large cold flow property, poor static stability, high melting point, poor melt fluidity, low operation elasticity and easy crosslinking at high temperature, or the polymer has the behaviors of large cohesion, high modulus and difficult stripping and is not suitable for being used as a metal appliance or a material for filling and protecting a mating member. The first object of the present invention is to provide a hydrogenated bicomponent polystyrene-b-conjugated diene copolymer which exhibits thermoplastic behavior, has high stiffness at room temperature, low cold flow, good static stability, low cohesion at low temperature, is easily peelable, and exhibits characteristics of being easily meltable at 150 ℃ or lower, good melt fluidity, large operational elasticity, and being non-crosslinked, and which is mainly used as a material for protecting, filling and positioning in cutting processing of metal appliances or mating assemblies, such as filling for cutting protection in processing of aircraft engines, missile empennage exhaust assemblies, etc., and the hydrogenated thermoplastic polymer filled in cutting processing of metal appliances or mating assemblies is cut along with cutting of the metal or alloy assemblies, and after the assembly is molded, the filled thermoplastic polymer is easily peeled off like a balsa leather, easy to clear; in addition, the filled thermoplastic polymer also has the characteristics of easy melting and convenient casting and forming.

Another object of the present invention is to provide a process for producing a hydrogenated bicomponent polystyrene-b-conjugated diene random copolymer with a simple operation at a low cost.

The third purpose of the invention is to provide the application of hydrogenated bi-component polystyrene-b-conjugated diene copolymer as a filling, positioning and protecting material in the cutting processing of metal appliances or matching assemblies, the copolymer is used for filling in the cutting protection in the processing process of aircraft engines, missile empennage exhaust assemblies and the like, is easy to strip out and remove, and has the characteristics of convenient melting and casting molding.

In order to achieve the above technical objects, the present invention provides a hydrogenated two-component polystyrene-b-conjugated diene copolymer, which is obtained by hydrogenating a two-component polystyrene-b-conjugated diene copolymer;

the bi-component polystyrene-b-conjugated diene copolymer comprises two polystyrene-b-conjugated diene random copolymers with number average molecular weights of not less than 60000 and not more than 17000;

the two polystyrene-b-conjugated diene copolymers each have the following expression: S-B-B/D;

wherein the content of the first and second substances,

s is a styrene block;

b is a conjugated diene block;

d is the divinylbenzene branching nodes randomly distributed in the B block.

The hydrogenated bicomponent polystyrene-b-conjugated diene copolymers provided by the present invention may also be referred to as filled thermoplastic polymers. The hydrogenated bi-component polystyrene-b-conjugated diene copolymer is obtained by combining two polystyrene-b-conjugated diene copolymers with different molecular weights, and hydrogenating double bonds in a poly-conjugated diene segment except a benzene ring in a molecule into' -carbon-bonds. The two copolymers of the hydrogenated two-component polystyrene-b-conjugated diene copolymer have the same molecular formula and can be simply expressed by, for example: the 3 expressions of S-b-EB/D or S-b-EP/D or S-b-EBP/D are mainly due to the fact that the polystyrene-b-conjugated diene copolymer generated by adopting different conjugated dienes has certain difference in structure, and different structural units are formed after hydrogenation. Wherein S is a styrene unit; e is an ethylene unit; b is an isobutyl unit; p is an isopropyl unit; d is a divinylbenzene branching node.

The molecular chain of the hydrogenated bi-component polystyrene-b-conjugated diene copolymer provided by the invention can be straight-chain molecules or long-chain branched molecules, the preferred hydrogenated bi-component polystyrene-b-conjugated diene copolymer has a long-chain branched molecular structure, and the long-chain branched polymer has the characteristics of high entanglement degree between molecular chains and cold flow resistance.

As a preferable mode, the mass ratio of the polystyrene-b-conjugated diene random copolymer having a number average molecular weight of not less than 60000 to the two polystyrene-b-conjugated diene random copolymers having a data molecular weight of not more than 17000 is (20 to 25)/(80 to 75). The hydrogenated bi-component polystyrene-b-conjugated diene copolymer contains a small amount of hydrogenated polystyrene-b-conjugated diene copolymer with high molecular weight, so that the stiffness of the compound adhesive is favorably improved, the compound adhesive does not flow vertically at normal temperature, and the hydrogenated polystyrene-b-conjugated diene copolymer with more component proportion and lower molecular weight is favorable for the compound mixture to have lower melting temperature and lower casting viscosity, namely favorable for molding. Therefore, the hydrogenated bi-component polystyrene-b-conjugated diene copolymer and the modified polystyrene-b-conjugated diene copolymer are matched and used according to a proper proportion, so that better comprehensive performance is obtained, the hydrogenated bi-component polystyrene-b-conjugated diene copolymer can be ensured to have lower melting temperature and higher melt flowability, and meanwhile, the hydrogenated bi-component polystyrene-b-conjugated diene copolymer has higher stiffness and stability at room temperature, namely, the polymer after casting does not flow cold.

In a preferred embodiment, the hydrogenation degree of the conjugated diene unit in each of the two polystyrene-b-conjugated diene copolymers is greater than 95%, more preferably greater than 98%. If the degree of hydrogenation is low, the iodine value is too high, which results in that the hydrogenated polystyrene-conjugated diene random copolymer gels when melted by heating due to crosslinking of the double bonds, thereby losing fluidity and being unfavorable for the cast molding of the assembly.

As a preferred embodiment, the conjugated diene in the conjugated diene block includes at least one of butadiene, isoprene, and piperylene.

In a preferred embodiment, the block mass ratio of the two polystyrene-B-conjugated diene copolymers is S/B ═ 20 to 30)/(80 to 70). An appropriate amount of styrene is important for maintaining high stiffness and stability of the hydrogenated polystyrene-conjugated diene random copolymer at room temperature.

In a preferred embodiment, the number average molecular weights of the two polystyrene-b-conjugated diene copolymers are 60000-65000 and 12000-17000 respectively.

As a preferred embodiment, the molecular mass distribution index of each of the two polystyrene-b-conjugated diene copolymers is less than 1.05.

In a preferred embodiment, the content of the 3, 4-addition unit in the conjugated diene of each of the two polystyrene-b-conjugated diene copolymers is 10% to 60%.

In a preferred embodiment, the two polystyrene-conjugated diene random copolymers each have a divinylbenzene unit content of 0.08 to 0.16% by mass based on the mass of the conjugated diene, and the divinylbenzene unit has a branching degree of 3 to 6. A proper amount of divinylbenzene is introduced to generate a long-chain branched molecular structure, and the long-chain branched polymer has the characteristics of high entanglement degree between molecular chains and cold flow resistance.

The hydrogenated bicomponent polystyrene-b-conjugated diene copolymer (thermoplastic polymer for filling) of the present invention preferably has a melting temperature of not higher than 150 ℃; the melt index is 1500-1800 g/10 min; the melt casting glue does not sag and is easy to strip at room temperature.

The invention also provides a preparation method of the hydrogenated bi-component polystyrene-b-conjugated diene copolymer, which comprises the following steps:

1) adding a solvent and an activating agent into a polymerization reaction kettle, heating to the initial polymerization temperature, adding an initiator and styrene into the polymerization reaction kettle for first-stage polymerization, adding a mixed monomer of divinylbenzene and conjugated diene after the first-stage polymerization is finished, and performing second-stage polymerization to obtain a polystyrene-b-conjugated diene copolymer glue solution; wherein, in the first-stage polymerization process, two polystyrene-b-conjugated diene random copolymer glue solutions with the number average molecular weights of not less than 60000 and not more than 17000 are obtained by controlling the dosage of the initiator;

2) uniformly mixing the two polystyrene-conjugated diene copolymer glue solutions, transferring the mixed glue solutions into a hydrogenation reaction kettle, carrying out hydrogenation reaction, condensing water vapor after the hydrogenation reaction is finished, and drying to obtain the polystyrene-conjugated diene copolymer glue solution; or transferring the two polystyrene-conjugated diene copolymer glue solutions into a hydrogenation reaction kettle respectively, carrying out hydrogenation reaction, after the hydrogenation reaction is finished, uniformly mixing the two hydrogenated polystyrene-conjugated diene copolymer glue solutions, condensing with water vapor, and drying to obtain the polystyrene-conjugated diene copolymer glue solution.

In a preferred embodiment, the initial polymerization temperature is 50 to 60 ℃.

As a preferable scheme, the first-stage polymerization reaction time is 20-25 min, the temperature in the second-stage polymerization reaction process is controlled not to exceed 95 ℃, and the polymerization reaction time is 20-25 min.

As a preferable scheme, the hydrogenation reaction adopts a titanium-based or nickel-based catalytic system to carry out selective catalytic hydrogenation. For example, the specific catalytic system can be selected from dicyclopentadiene titanium dichloride (titanium system) or a coordination complex (nickel system) formed by mixing triisobutylaluminum and nickel naphthenate. Generally speaking, the amount of dicyclopentadiene titanium dichloride used for titanium hydrogenation is 0.025-0.035 g/100g polymer; the amount of the nickel-aluminum complex used for hydrogenation of nickel is 0.4 to 0.6m.mol/100g polymer in terms of Ni.

As a preferable scheme, in the hydrogenation reaction process, the temperature is controlled to be 65-85 ℃, the time is 2.5-3.0 h, and the hydrogen pressure is 1.2-1.6 MPa. Can ensure that the hydrogenation degree of the conjugated diene unit of the polystyrene-b-conjugated diene copolymer is not less than 98 percent.

The two polystyrene-b-conjugated diene copolymer crude rubbers of the technical scheme of the invention can be prepared by adopting the traditional lithium polymerization process.

The treatment method of the hydrogenated bi-component polystyrene-b-conjugated diene copolymer glue solution in the technical scheme of the invention can be carried out by adopting the traditional treatment method of lithium polymers such as SEBS and the like, namely, the mixed glue solution is subjected to water vapor condensation, baking dehydration and briquetting.

The preparation of the hydrogenated bi-component polystyrene-b-conjugated diene copolymer provided by the invention can be completed by the following three-step method:

the first step is as follows: preparation of polystyrene-b-conjugated diene random copolymer: the preparation or polymerization method is a method known in the industry technology, cyclohexane is used as a polymerization solvent, n-butyl lithium is used as an initiator, and tetrahydrofuran is used as an activator. The specific operation method comprises the following steps:

adding quantitative cyclohexane, an activator THF (tetrahydrofuran) and quantitative styrene into a steel container with a stirring seal, heating a polymerization solution to 50-60 ℃ by using a hot water bath, adding a set amount of n-butyllithium to initiate polymerization for 20-25 min, adding a conjugated diene monomer containing 0.05-0.10% of divinylbenzene by mass at one time, and polymerizing for 25min at a polymerization temperature of not higher than 95 ℃ to obtain a polystyrene-b-conjugated diene copolymerized glue solution (note: according to different addition amounts of monomers and butyl lithium, two types of polystyrene-b-conjugated diene random copolymers with different molecular weights can be respectively prepared.

The second step is that: hydrogenation of polystyrene-b-conjugated diene random copolymer:

and respectively adding the prepared polystyrene-b-conjugated diene copolymer glue solutions with different molecular weights into a hydrogenation kettle, adding a catalyst for hydrogenation, introducing hydrogen, stopping hydrogenation when the hydrogenation degree of the polymer is higher than 98%, and adding an antioxidant 1076 with the weight part of 0.3-0.4% of the total dry glue into the glue solution.

The third step: mixing, homogenizing and drying the hydrogenated glue solution.

And (3) mixing the A and B polymerized-hydrogenated glue solutions prepared in the two-step method respectively according to the ratio of A/B (dry polymer) to (80-75)/(20-25), uniformly stirring, and then condensing, drying and briquetting the mixed glue solution by using water vapor to obtain the thermoplastic polymer for filling.

The invention also provides an application of the hydrogenated bi-component polystyrene-b-conjugated diene copolymer as a filling positioning protection material in the cutting processing of metal appliances or matching assemblies.

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

compared with the existing SEPS, SEBS, polyolefin and other polymers, the high-molecular-weight high-melting-point high-melt-flowability high-molecular-weight high-melt-flowability high-melt-modulus material cannot meet the requirements of metal appliances or matching parts for processing, molding, filling and protecting. The hydrogenated bi-component polystyrene-b-conjugated diene copolymer prepared by the invention has proper molecular mass and wider molecular mass distribution index, and is beneficial to the lower melting temperature of the polymer when being heated; the branched chain links contained in the polymer endow the polymer with higher entanglement or high entanglement among molecular chains, and the polymer (or melt) has difficult relative movement among molecules under the dragging of the branched chains of long-chain molecules, does not flow cold at room temperature and keeps higher stiffness. On the other hand, the polymer with high entanglement degree can be oriented and unwound among molecules under the actions of melting, stirring and shearing, good thixotropy is reflected, the melt viscosity becomes thin, the melt fluidity is good, and the casting is easy; the adoption of a homogeneous catalytic hydrogenation method gives a polymer with a lower iodine value, which is beneficial to the fact that the polymer is not decomposed or crosslinked at a high melting temperature; the cast polymer has the characteristics of low modulus, easy stripping and cleaning and the like. Namely, the hydrogenated bicomponent polystyrene-b-conjugated diene copolymer prepared by the present invention is very suitable for being used as a material for processing, molding, filling and protecting metal appliances or fittings.

The hydrogenated bi-component polystyrene-b-conjugated diene copolymer can be prepared by using traditional equipment and processes, has simple preparation method and low cost, and can be used as a technical index and characteristic behavior of a thermoplastic filling polymer which are comparable with those of the prior commercially available K25S polymer.

Drawings

FIG. 1 is a HNR diagram of a hydrogenated bi-component polystyrene-b-conjugated diene copolymer prepared according to the present invention;

FIG. 2 is a GPC chart of a hydrogenated bicomponent polystyrene-b-conjugated diene copolymer prepared according to the present invention.

Detailed Description

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

The number average molecular weight and molecular weight distribution index of the polymer were measured by Gel Permeation Chromatography (GPC) in the following examples; determining the microstructure content of the polymer by H-NMR spectroscopy by using Aacend (TM) 400; the melt index of the finished green polymer was determined using a Zwick Roell Mflow tester at 150 ℃.

Example 1

Preparation of polymerization liquid a 1:

adding 3500mL of cyclohexane solution of 10 mass percent n-hexane into a 5-liter polymerization kettle under the protection of nitrogen, then adding 0.35mL of tetrahydrofuran into the polymerization kettle, then heating the materials to 55-60 ℃ by using steam, adding 100g of styrene, immediately adding 8.5mL of 1.02mol/L n-butyllithium solution into the polymerization kettle, starting the polymerization reaction, after reacting for 20min, adding a mixed monomer mixed with 390g of butadiene and 0.45mL of divinylbenzene into a monomer metering tank into the polymerization kettle at one time, controlling the polymerization temperature to be not higher than 95 ℃ and the polymerization time to be not less than 25 min.

As a result, it was found that the polymer crude rubber had Mn of 61200 for the number average molecular weight, a molecular mass distribution index of 1.03 and a vinyl unit content of 12.9%. The obtained polymerization copolymerization glue solution is marked as polymerization A1 glue solution.

Example 2

Preparation of polymerization liquid a 2:

the relevant process conditions in preparation example 1 were unchanged except that 7mL of butyllithium, 350g of butadiene and 0.25mL of divinylbenzene were added.

As a result, it was found that the polymer crude rubber had a number average molecular weight of Mn-64300, a molecular mass distribution index of 1.04 and a vinyl unit content of 12.7%. The obtained polymerization copolymerization glue solution is marked as polymerization A2 glue solution.

Example 3

Preparation of polymerization liquid a 3:

the relevant process conditions in preparation example 1 were unchanged except that 8mL of butyllithium, 200g of butadiene, 170g of isoprene and 0.30mL of divinylbenzene were added.

As a result, it was found that the polymer crude rubber had Mn of 61400 for the number average molecular weight, a molecular mass distribution index of 1.04, a vinyl unit content of 11.9% and a3, 4-adduct content of 14.8%. The obtained polymerization copolymerization glue solution is marked as polymerization A3 glue solution.

Example 4

Preparation of polymerization liquid a 4:

the relevant process conditions in preparation example 1 were unchanged except that 6.5mL of butyllithium, 50g of butadiene, 300g of isoprene and 0.35mL of divinylbenzene were added.

As a result, it was found that the polymer crude rubber had Mn of 64500 for the number average molecular weight, a molecular mass distribution index of 1.03, a vinyl unit content of 13.8% and a3, 4-adduct content of 14.2%. The obtained polymerization copolymerization glue solution is marked as polymerization A4 glue solution.

Example 5

Preparation of polymerization liquid B1:

adding 3500mL of cyclohexane solution of 10% by mass of n-hexane into a 5L polymerization kettle under the protection of nitrogen, then adding 0.30mL of tetrahydrofuran into the polymerization kettle, then heating the materials to 55-60 ℃ by using steam, adding 100g of styrene, immediately adding 35mL of 1.02mol/L n-butyllithium solution into the polymerization kettle, starting the polymerization reaction, after reacting for 20min, adding a mixed monomer mixed with 400g of butadiene and 0.35mL of divinylbenzene into a monomer metering tank into the polymerization kettle at one time, controlling the polymerization temperature to be not higher than 95 ℃ and the polymerization time to be not less than 25 min.

As a result, it was found that the polymer crude rubber had a number average molecular weight of Mn 15400, a molecular mass distribution index of 1.03 and a vinyl unit content of 12.7%. The obtained polymerization copolymerization glue solution is marked as polymerization B1 glue solution.

Example 6

Preparation of polymerization liquid B2:

the relevant process conditions in preparation B1 were unchanged except that 33mL of butyllithium, 300g of butadiene and 0.30mL of divinylbenzene were added.

As a result, it was found that the polymer crude rubber had a number average molecular weight of Mn 12800, a molecular mass distribution index of 1.04 and a vinyl unit content of 12.6%. The obtained polymerization copolymerization glue solution is marked as polymerization B2 glue solution.

Example 7

Preparation of polymerization liquid B3:

the relevant process conditions in preparation B1 were unchanged except that 36mL of butyllithium, 100g of butadiene and 350g of isoprene were added.

As a result, it was found that the polymer crude rubber had a number average molecular weight of Mn 16100, a molecular mass distribution index of 1.05, a vinyl unit content of 12.2% and a3, 4-addition unit content of 15.9%. The obtained polymerization copolymerization glue solution is marked as polymerization B3 glue solution.

Example 8

Preparation of polymerization liquid B4:

the relevant process conditions in preparation B1 were unchanged except that 35mL of butyllithium and 430g of isoprene were added.

As a result, it was found that the polymer crude rubber had Mn of 15200 for the number average molecular weight, a molecular mass distribution index of 1.06 and a content of 3, 4-addition units of 17.2%. The obtained polymerization copolymerization glue solution is marked as polymerization B4 glue solution.

Example 9

Taking 300g of A1 polymerized glue solution and 1200g of B1 polymerized glue solution, simultaneously adding the A1 polymerized glue solution and the B1 polymerized glue solution into a hydrogenation kettle, then adding a titanium catalyst, controlling the hydrogen pressure to be 1.3-1.5 MPa, after hydrogenation is carried out for 150min at the temperature of 70-80 ℃, measuring the iodine value of a polymer to be 2.5g/100g of a polymer, stopping the hydrogenation reaction at the moment, adding 1.2g of 1076 antioxidant into the glue solution, uniformly mixing, condensing by water vapor, and drying to obtain the crude rubber.

Measuring the melt index of the hydride to be 1744g/10 min; after the briquetting glue is kept still for 24 hours at 65 ℃, no phenomena of vertical flow and cold flow of the glue blocks are seen; the complete melting temperature of the raw rubber is 143-147 ℃, and the melt is easy to flow.

Example 10

350g of A1 polymerized glue solution and 1200g of B3 polymerized glue solution are taken and added into a hydrogenation kettle at the same time, then a nickel catalyst is added, the hydrogen pressure is controlled to be 1.3-1.5 MPa, after hydrogenation is carried out for 130min, the iodine value of the polymer is measured to be 4.3g/100g of the polymer, the hydrogenation degree is 95.8%, at the moment, the hydrogenation reaction is stopped, and the glue solution is coagulated by water vapor and dried to obtain the crude rubber.

Measuring the melt index of the hydride 1565g/10 min; after the briquetting rubber is kept static at 65 ℃ for 24 hours, no phenomena of vertical flow and cold flow of rubber blocks are seen, the complete melting temperature of raw rubber is 141-144 ℃, and the melt is easy to flow.

Example 11

Respectively mixing A2 with glue solutions in B3 and B4 (the mixed glue numbers are respectively A2-B3 and A2-B4); and the glue solutions of A3 and B1 and B4 respectively (the mixed glue numbers are A3-B1 and A3-B4 respectively); the A4 and the glue solutions in B1 and B2 (the mixed glue numbers are A4-B1 and A4-B2 respectively) are mixed according to the proportion in the example 9, and hydrogenation is carried out according to the conditions of the hydrogenation example 1. The resulting hydrogenated green rubber properties are shown in Table 1:

TABLE 1

Example 12

Respectively preparing polymerization glue solutions according to the same process method of the preparation example A2 of the polymerization solution A and the preparation example B4 of the polymerization solution B, respectively hydrogenating the two prepared glue solutions according to the hydrogenation method in the embodiment 10, respectively marking the obtained hydrogenated glue solutions as A 'and B', uniformly mixing 750g of the glue solution A ', 2500g of the hydrogenated glue solution B' and 2.5g of the antioxidant 1076, and condensing and drying the mixed glue solution by using steam to obtain the raw glue. The melt index of the raw rubber is 1571g/10min, the raw rubber is completely melted at 143-147 ℃, the melt fluidity is good, and the cast rubber of the melt has high stiffness and does not flow at room temperature.