An elastomeric material and its preparation and crosslinked polymer

Abstract

The present invention provides a preparation technology for an elastomer material with high mechanical properties, resistance to high and low temperatures, and ablation resistance. The elastomer material of the present invention has the structure shown in Formula I, and the local structure at the crosslinking position of the crosslinked elastomer material has the structure shown in Formula IV. The elastomer material provided by the present invention is a copolymer obtained by catalytic polymerization of two monomers, monomer A and monomer B. Since monomer B destroys the chain regularity of the original homopolymer of monomer A, the low-temperature crystallinity of the copolymer is reduced, greatly improving the low-temperature elasticity of the material. On the other hand, due to the presence of the side group R2 in monomer B, the presence of the R2 group reduces the degree of aging degradation of the material under high-temperature conditions, improves the high-temperature resistance of the material, and endows it with the ability to resist ablation. The elastomer material provided by the present invention has high mechanical strength, resistance to high and low temperatures, and ablation resistance after crosslinking. Experimental results show that the tensile strength of the crosslinked elastomer material prepared by the present invention can reach 18.9 MPa, the service temperature range is -60°C - 150°C, and the oxyacetylene ablation rate ≤ 0.20 mm / s.

Description

Technical Field

[0001] The present invention belongs to the technical field of the preparation of polymer elastomer materials, and particularly relates to a preparation method of an elastomer with high mechanical properties, high and low temperature resistance, and ablation resistance. Background Art

[0002] Elastomer materials are a very important type of materials in the polymer field. They are between plastics and rubbers, and can be used as a single material for polymer processing or as the main matrix of composite materials for cross-linking molding. In recent years, the research and patents on polymer functional monomers and their polymers have increased significantly, but the research on the copolymerization of functional monomers and traditional monomers to prepare elastomer copolymers and their subsequent application properties is very scarce. Based on the traditional Ziegler-Natta coordination catalyst, the present invention copolymerizes the existing commonly used monomer A(II) and the functional monomer B(III) to obtain an elastomer copolymer with very excellent high and low temperature resistance. At the same time, by changing the R2 group on the side chain of the copolymer, the material is given the property of ablation resistance, and the excellent mechanical properties of the homopolymer of monomer A(II) are maintained. On the other hand, the present invention mixes the elastomer copolymer with stearic acid, zinc oxide, vulcanization aids, anti-aging agents, reinforcing agents, plasticizers, flame retardants, etc., and obtains a cross-linked elastomer material with high mechanical strength, wide temperature range, and ablation resistance through hot pressing cross-linking. The tensile strength of this material can reach 18.9 MPa, the high temperature resistance can reach 150 °C, the low temperature resistance can reach -60 °C, and the oxyacetylene ablation rate is ≤ 0.20 mm / s.

[0003] In the prior art, there is only a preparation technology for polymerizing the common monomer A(II) with the traditional Ziegler-Natta coordination catalyst. Among them, the coordination catalyst can only prepare monomers with similar reactivity ratios, and the homopolymer or copolymer has poor high temperature resistance, a narrow use temperature range, and is flammable.

[0004] In view of this, the present invention provides a preparation method of a raw rubber and cross-linked material of an elastomer with high mechanical properties, high and low temperature resistance, and ablation resistance. The material prepared by the present invention has stronger high and low temperature resistance (-60 °C - 150 °C) compared with the copolymer of the traditional coordination polymerized monomer A(II) (-25 °C - 80 °C), excellent ablation resistance, and higher mechanical properties than the polymer of the traditional coordination polymerized monomer A(II). The polymerization method and the material cross-linking preparation method of the present invention have not been reported in the literature and patents. Summary of the Invention

[0005] 1. An elastomer material with high mechanical properties, high and low temperature resistance, and ablation resistance, having the structure shown in Formula I:

[0006]

[0007] The elastomer material with high mechanical properties, high and low temperature resistance, and ablation resistance is obtained by copolymerizing monomer A and monomer B with a catalyst.

[0008] Monomer A has the structure shown in Formula II:

[0009]

[0010] The said R1 has any one of the structures shown in Formula II-1 to Formula II-2:

[0011] -H -CH3

[0012] Formula II-1 Formula II-2

[0013] Monomer B has the structure shown in Formula III:

[0014]

[0015] The said R2 has any one of the structures shown in Formula III-1 to Formula III-3:

[0016]

[0017] 2. After the elastomer material is mixed with additives and filler materials and under the action of hot pressing, a cross-linked polymer is formed, and the local structure at the cross-linking position has the structure shown in Formula IV:

[0018]

[0019] In Formula IV, M is selected from one or more of the structures shown in Formula IV-1 to Formula IV-4:

[0020]

[0021] In Formula IV-3, X is 3 to 8 after sulfur.

[0022] 3. A preparation method of an elastomer with high mechanical properties, resistance to high and low temperatures and ablation resistance, comprising the following steps:

[0023] (1) Under anhydrous and anaerobic conditions, the main catalyst, aluminum agent, chlorine source, isoprene monomer and solvent are put into the reaction kettle according to a molar ratio of 1.0∶20.0 - 50.0∶2.0∶1.0 - 5.0∶5.0 - 20.0 to mix and prepare a highly efficient heterogeneous catalyst. The mixing temperature is 25°C - 50°C, the mixing time is 10 - 20 minutes, and the aging time after the heterogeneous catalyst is mixed is 1 - 12 hours for standby;

[0024] The said catalyst includes the main catalyst, aluminum agent and chlorine source, and can be a three-component catalyst polymerization or a binary-component polymerization of the catalyst and aluminum agent. The specific ratio therein is not limited as long as polymerization can be carried out;

[0025] The main catalyst described above includes one or more of neodymium octoate, neodymium naphthenate, neodymium isopropoxide, nickel naphthenate, and butyl lithium;

[0026] The aluminum agent described above includes one or more of trimethyl aluminum, triisobutyl aluminum, octyl aluminum, and triethyl aluminum;

[0027] The chlorine source described above includes one or more of diethyl aluminum monochloride, dibutyl aluminum monochloride, ethyl aluminum dichloride, butyl aluminum dichloride, and chloroform;

[0028] The isoprene monomer is a polymerization-grade compound, and it is sufficient if it has the same quality as monomer A;

[0029] The solvent described above is hexane, with a water content of 10 ppm (10 -6 ) or less. As long as it can polymerize, the quality is not restricted;

[0030] The high-efficiency heterogeneous catalyst is composed of a main catalyst, an aluminum agent, a chlorine source, an isoprene monomer, and a solvent. Preferably, the molar ratio is 1.0∶20.0 - 50.0∶2.0∶1.0 - 5.0∶5.0 - 20.0.

[0031] The high-efficiency heterogeneous catalyst needs to be mixed for a certain time at a specific temperature. Preferably, the mixing temperature is 25°C - 50°C, and the mixing time is 10 - 20 minutes.

[0032] After the catalyst is prepared, it needs to be aged, and the aging time is 1 - 12 hours.

[0033] (2) Under anhydrous and anaerobic conditions, monomer A with the structure shown in Formula II, monomer B with the structure shown in Formula III, the high-efficiency heterogeneous catalyst, and the solvent are put into the reaction kettle. Among them, the molar ratio of the main catalyst, monomer A with the structure shown in II, monomer B with the structure shown in Formula III, and the solvent is 1.0 - 10.0:0.75×10 5 ~0.95×10 5 :0.05×10 5 ~0.25×10 5 :5 - 10×10 5 , the reaction temperature is 30°C - 80°C, and the reaction time is 5 - 10 minutes.

[0034] Preferably, the reaction kettle is a 20 - 50 liter reaction kettle, the temperature adjustment range of the reaction kettle is 25°C - 100°C, and the pressure adjustment range is 0.1 - 1.0 MP;

[0035] The solvent described above is hexane, with a water content of 10 ppm (10 -6 ) or less. As long as it can polymerize, the quality is not restricted;

[0036] Preferably, the molar ratio of the main catalyst, monomer A with the structure shown in II, monomer B with the structure shown in formula III, and the solvent is 1.0 to 10.0∶0.75×10 5 ~0.95×10 5 ∶0.05×10 5 ~0.25×10 5 ∶5~10×10 5 ;

[0037] The polymerization reaction needs to be carried out at a specific temperature. Preferably, the reaction temperature is 30°C to 80°C;

[0038] The polymerization reaction needs to be carried out for a specific time. Preferably, the reaction time is 5 to 10 minutes;

[0039] (3) A chain transfer agent is used to achieve the chain growth of the copolymer of monomer A with the structure shown in II and monomer B with the structure shown in formula III. After the reaction temperature is 30°C to 80°C and the reaction time is 10 to 30 minutes, the chain transfer agent is added to the reaction kettle. The molar ratio of the chain transfer agent to the main catalyst is 1.0 to 10.0∶5.0 to 20.0.

[0040] The chain transfer agent includes one or more of diisobutylaluminum hydride, triethylaluminum, and diethylmagnesium;

[0041] Preferably, the molar ratio of the chain transfer agent to the main catalyst is 1.0 to 10.0∶5.0 to 20.0;

[0042] The polymerization reaction needs to be mixed at a specific temperature for a certain time. Preferably, the reaction temperature is 30°C to 80°C and the reaction time is 10 to 30 minutes.

[0043] (4) After each component reacts in the reaction kettle for 2 to 8 hours, the number-average molecular weight of the polymer increases by 80,000 to 150,000. The polymerization reaction is terminated with a chain terminator. The molar ratio of the chain terminator to the main catalyst is 100.0 to 200.0∶1.0 to 10.0, and the reaction temperature is 30°C to 80°C. After coagulation and drying, an elastomer raw rubber is obtained;

[0044] The chain terminator includes one or more of 2,2'-methylenebis-(4-methyl-6-tert-butylphenol), 2,6-di-tert-butyl-p-cresol, n-octadecyl 3,5-di-tert-butyl-4-hydroxyphenylpropionate, 2,4-bis(n-octylthiomethylene)-6-methylphenol, and ethanol;

[0045] The number-average molecular weight of the copolymer increases by 80,000 to 150,000;

[0046] The polymerization reaction needs to be mixed at a specific temperature for a certain time. Preferably, the reaction temperature is 30°C to 80°C and the reaction time is 2 to 8 hours.

[0047] (5) Mix the raw rubber of the elastomer material with stearic acid, zinc oxide, vulcanization accelerator, vulcanizing agent, antioxidant, reinforcing agent, plasticizer and flame retardant in a mixing device according to the mass ratio of 100∶2∶4∶0.5 - 1.0∶0.5 - 2.0∶1∶30 - 50∶5 - 10∶10 - 20. After mixing for 10 - 20 minutes, take out the sheet with an open mill, and carry out vulcanization molding at 150 °C and 10 MPa pressure in an oil hydraulic molding machine for more than 20 minutes to obtain a cross-linked elastomer test piece. Test the mechanical properties, high and low temperature resistance properties and ablation properties of the cross-linked elastomer test piece.

[0048] The mixing device mentioned above is an open mill, a closed mill or other equipment that can mix elastomers. The mixing temperature and rotation speed of the equipment are conventional parameters. The equipment type is not limited as long as it can mix evenly.

[0049] The stearic acid and zinc oxide mentioned above are common additives for rubber materials. The quality is not limited as long as it can cross-link.

[0050] The vulcanization accelerators include one or more of aldehyde amines (hexamethylenetetramine / accelerator H), guanidines (diphenylguanidine / accelerator D), thiurams (tetramethylthiuram disulfide / accelerator TMTD), thiazoles (2-mercaptobenzothiazole / accelerator M), dithiocarbamates (zinc dimethyldithiocarbamate / accelerator ZDMC), xanthates (zinc butylxanthate / accelerator ZBX), thioureas (ethylenethiourea / accelerator NA-22), sulfenamides (N-cyclohexyl-2-benzothiazolesulfenamide / accelerator CZ) and / or peroxide accelerators: triallyl isocyanurate (accelerator TAIC), N,N'-m-phenylene bismaleimide (HVA2), trimethylolpropane trimethacrylate (TMPTMA), etc.

[0051] The vulcanizing agents include one or more of sulfur, dicumyl peroxide (DCP), benzoyl peroxide (BPO), 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane (bis-2,5) and di-tert-butyl peroxide (DTBP), etc.

[0052] The antioxidants include one or more of N-phenyl-β-naphthylamine (antioxidant D), 2,2,4-trimethyl-1,2-dihydroquinoline polymer (antioxidant RD), 2-mercaptobenzimidazole (antioxidant MB), nickel dibutyldithiocarbamate (antioxidant NBC) and N-isopropyl-N`-phenyl-p-phenylenediamine (antioxidant 4010NA), etc.

[0053] The reinforcing agent described above includes one or more of carbon black, silica, calcium carbonate, calcium oxide, titanium dioxide, etc., preferably carbon black and silica;

[0054] The plasticizer described above includes one or more of naphthenic oil, aromatic oil, paraffin oil, etc.;

[0055] The flame retardant includes: one or more of tributyl phosphate, tris(2-ethylhexyl) phosphate, tris(2-chloroethyl) phosphate, triphenyl phosphate, (2-ethylhexyl) diphenyl phosphate, chlorendic anhydride, pentabromoethylbenzene, tetrabromobisphenol A, tris(dibromopropyl) phosphate, halogenated cyclohexane, magnesium hydroxide, aluminum hydroxide, borate, etc.

[0056] Preferably, the mixing ratio of the raw rubber of the elastomer, stearic acid, zinc oxide, vulcanization accelerator, vulcanizing agent, antioxidant, reinforcing agent, plasticizer and flame retardant is 100∶2∶4∶0.5 - 1.0∶0.5 - 2.0∶1∶30 - 50∶5 - 10∶10 - 20;

[0057] Preferably, after the raw rubber of the elastomer and other additives are mixed for 10 - 20 minutes, the sheet is taken out by an open mill.

[0058] Compared with the prior art, the beneficial effects of the present invention are:

[0059] The present invention provides a high mechanical property, high and low temperature resistant and ablation resistant elastomer and its preparation method. The elastomer material described has the structure shown in Formula I. The elastomer material provided by the present invention contains a side group R2. The presence of the R2 group makes the elastomer material have high mechanical properties, excellent high and low temperature resistance and ablation resistance. The tensile strength of the cross-linked elastomer material prepared by the present invention can reach 18.5 MPa, the use temperature range is -50°C - 150°C, and the oxyacetylene ablation rate ≤ 0.20 mm / s. Specific Embodiments

[0060] In order to further illustrate the present invention, the following describes in detail the preparation method of a high mechanical property, high and low temperature resistant and ablation resistant elastomer provided by the present invention in combination with embodiments, but they cannot be understood as limiting the protection scope of the present invention.

[0061] Example 1

[0062] (1) Under anhydrous and anaerobic conditions, neodymium octanoate, triisobutylaluminum, diethylaluminum chloride, isoprene monomer, and hexane were added to a 5-L reaction kettle in a molar ratio of 1.0∶25.0∶2.0∶2.0∶10.0 (each catalyst component was a 1 mol / L ethane solution purchased from InnoChem Co., Ltd., and the solvent for preparation was hexane. A total of 4000 mL was added to the 5-L reaction kettle according to 100 mL∶2500.0 mL∶200.0 mL∶200.0 mL∶1000.0 mL, corresponding to 0.025 mol / mL of the main catalyst neodymium octanoate) to mix and prepare a highly efficient heterogeneous catalyst. The mixing temperature was 25 °C, the mixing time was 10 minutes, and the aging time of the heterogeneous catalyst after mixing was 1 hour for standby;

[0063] (2) Polymerization of two monomers was carried out using the heterogeneous catalyst. Under anhydrous and anaerobic conditions, monomer A with the structure shown in Formula II (R1 is II-1), monomer B with the structure shown in Formula III (R2 is III-3), 37.5 mL (15×10 -5 mol) of the highly efficient heterogeneous catalyst, and the solvent hexane were added to a 20-L reaction kettle. The temperature in the kettle was controlled at 30 °C, and the pressure in the kettle was controlled at 0.5 MPa. The molar ratio of the main catalyst (neodymium octanoate), monomer A with the structure shown in Formula II, monomer B with the structure shown in Formula III, and hexane was 1.0∶0.75×10 5 ∶0.05×10 5 ∶5×10 5 . The reaction temperature was 30 °C, and the reaction time was 5 minutes.

[0064] (3) Chain transfer agent triethylaluminum was used to achieve chain growth of the copolymer of monomer A with the structure shown in Formula II (R1 is II-1) and monomer B with the structure shown in Formula III (R2 is III-3). Triethylaluminum was added to the reaction kettle in the above step (2). The molar ratio of triethylaluminum to the main catalyst was 8.0∶10.0. The reaction temperature was 30 °C, and the reaction time was 10 minutes;

[0065] (4) After the components reacted in the reaction kettle for 2 hours, the number-average molecular weight of the polymer increased by 146,000. The polymerization reaction was terminated with the chain terminator 2,2'-methylenebis(4-methyl-6-tert-butylphenol). The molar ratio of the chain terminator to the main catalyst was 100.0∶1.0. The reaction temperature was 30 °C. After coagulation and drying, an elastomer raw rubber was obtained;

[0066] (5)Mix the raw elastomer rubber with stearic acid, zinc oxide, accelerator TMTD, sulfur, antioxidant RD, reinforcing agent carbon black N330, naphthenic oil, and tributyl phosphate in a mixing device according to a mass ratio of 100∶2∶4∶0.7∶1.0∶1∶40∶6∶10. After mixing for 20 minutes, take out the sheet with an open mill, and cure and mold it at 150 °C and a pressure of 10 MPa for 20 minutes in an oil hydraulic molding machine to obtain a cross-linked elastomer specimen. Test the mechanical properties, high and low temperature resistance properties, and ablation properties of the cross-linked elastomer specimen, and the test results are shown in Table 2.

[0067] Example 2

[0068] (1) Under anhydrous and anaerobic conditions, put neodymium naphthenate, triisobutylaluminum, diethylaluminum monochloride, isoprene monomer, and hexane into a 2-liter reaction kettle according to a molar ratio of 1.0∶35∶2.0∶3.0∶12.0 (each catalyst preparation component is a 1 mol / L solution purchased from InnoChem Co., Ltd., and the preparation solvent is hexane. A total of 1060 ml is put into the 2-liter reaction kettle according to 20 ml∶700.0 ml∶40.0 ml∶60.0 ml∶240.0 ml, and the main catalyst is 0.019 mol / ml), mix and configure a highly efficient multiphase catalyst, with a mixing temperature of 35 °C and a mixing time of 15 minutes. After mixing the multiphase catalyst, let it age for 8 hours for standby;

[0069] (2) Under anhydrous and anaerobic conditions, put monomer A with the structure shown in Formula II (R1 is II-2), monomer B with the structure shown in Formula III (R2 is III-3), 190.0 ml (20×5×10 -5 mol) of the highly efficient multiphase catalyst, and the solvent hexane into a 28-liter reaction kettle, control the temperature in the kettle at 50 °C, and control the pressure in the kettle at 0.5 MPa. The molar ratio of the main catalyst, monomer A with the structure shown in Formula II, monomer B with the structure shown in Formula III, and the solvent is 5.0∶0.80×10 5 ∶0.10×10 5 ∶5×10 5 , the reaction temperature is 50 °C, and the reaction time is 8 minutes.

[0070] (3) Use the multiphase catalyst for the polymerization of the two monomers, and adopt the chain transfer agent diisobutylaluminum hydride to achieve the chain growth of the copolymer of monomer A with the structure shown in Formula II (R1 is II-2) and monomer B with the structure shown in Formula III (R2 is III-3). Add diisobutylaluminum hydride to the reaction kettle in the above step (2), and the molar ratio of diisobutylaluminum hydride to the main catalyst is 10.0:15.0, the reaction temperature is 50 °C, and the reaction time is 20 minutes.

[0071] (4) After the components react in the reactor for 4 hours, the number-average molecular weight of the polymer increases by 108,000, and the polymerization reaction is terminated with 2,4-bis(n-octylthiomethylene)-6-methylphenol. The molar ratio of the chain terminator to the main catalyst is 150:5.0, the reaction temperature is 50 °C, and after coagulation and drying, the raw rubber of the elastomer is obtained;

[0072] (5) The raw rubber of the elastomer, stearic acid, zinc oxide, vulcanization accelerator CZ, sulfur, antioxidant RD, reinforcing agent carbon black N660, plasticizer naphthenic oil and pentabromoethylbenzene are mixed in a mixing device according to the mass mixing ratio of 100:2:4:0.7:1.0:1:45:6:15. After mixing is completed, the mixture is sheeted out with an open mill and vulcanized and molded at 150 °C and a pressure of 10 MPa for 20 minutes in an oil hydraulic molding machine to obtain a crosslinked elastomer test piece. The crosslinked elastomer test piece is tested for mechanical properties, ablation properties and service temperature range, and the test results are shown in Table 2.

[0073] Example 3

[0074] (1) Under anhydrous and anaerobic conditions, neodymium naphthenate, triisobutylaluminum, diethylaluminum chloride, isoprene monomer and hexane are put into a 2-liter reactor according to a molar ratio of 1.0:50:2.0:5.0:20.0 (each catalyst preparation component is a 1 mol / L solution purchased from Aladdin Reagent Co., Ltd., and the preparation solvent is hexane. A total of 780 ml is put into a 1-liter reactor according to 10 ml:500.0 ml:20.0 ml:50.0 ml:200.0 ml, and the main catalyst is 0.013 mol / ml) to mix and prepare a highly efficient multiphase catalyst. The mixing temperature is 50 °C, the mixing time is 20 minutes, and the aging time of the multiphase catalyst after mixing is 12 hours for standby;

[0075] (2) Under anhydrous and anaerobic conditions, monomer A of the structure shown in Formula II (R1 is II-1) and monomer B of the structure shown in Formula III (R2 is III-2), 260.0 ml (20×10×10 -5 mol) of the highly efficient multiphase catalyst and the solvent hexane are put into a 50-liter reactor, the temperature in the reactor is controlled at 80 °C, and the pressure in the reactor is controlled at 0.5 MPa. The molar ratio of the main catalyst, monomer A of the structure shown in Formula II, monomer B of the structure shown in Formula III and the solvent is 10.0:0.95×10 5 :0.25×10 5 :10×10 5 , the reaction temperature is 80 °C, and the reaction time is 10 minutes.

[0076] (3) The polymerization of two monomers is carried out using a heterogeneous catalyst, and chain growth of the copolymer of monomer A with the structure shown in II (R1 is II-1) and monomer B with the structure shown in formula III (R2 is III-2) is achieved by using the chain transfer agent diethylmagnesium. Diethylmagnesium is added to the reaction kettle in the above step (2). The molar ratio of diethylmagnesium to the main catalyst is 10.0:20.0. The reaction temperature is 80 °C and the reaction time is 30 minutes.

[0077] (4) After the components react in the reaction kettle for 8 hours, the number-average molecular weight of the polymer increases by 108,000. The polymerization reaction is terminated with 2,6-di-tert-butyl-p-cresol. The molar ratio of the chain terminator to the main catalyst is 200:10.0. The reaction temperature is 80 °C. After coagulation and drying, the raw rubber of the elastomer is obtained;

[0078] (5) The raw rubber of the elastomer, stearic acid, zinc oxide, the vulcanization accelerator TAIC, the vulcanizing agent DCP, the antioxidant 4010NA, the reinforcing agent carbon black N660, the plasticizer naphthenic oil, and aluminum hydroxide are mixed in a mixing device according to the mixing ratio of 100:2:4:1.0:0.8:1:50:10:20. After mixing, the mixture is sheeted out with an open mill and vulcanization-molded at 150 °C and a pressure of 10 MPa for 20 minutes in an oil hydraulic molding machine to obtain a crosslinked elastomer test piece. The crosslinked elastomer test piece is tested for mechanical properties, ablation properties, and service temperature range. The test results are shown in Table 2.

[0079] Comparative Example 1

[0080] Steps (1), (3), (4), and (5) are the same as those in Example 2, where the number-average molecular weight in step (4) increases to 103,000; in step (2), under anhydrous and anaerobic conditions, 972.0 g (20 mol × 0.90) of monomer A with the structure shown in formula II (R1 is II-1), 190.0 mL (20 × 5 × 10 -5 mol) of the highly efficient heterogeneous catalyst, and the solvent hexane are put into a 28 L reaction kettle. The temperature inside the kettle is controlled at 50 °C and the pressure inside the kettle is controlled at 0.5 MPa. The molar ratio of the main catalyst, monomer A with the structure shown in II, and the solvent is 5.0:0.9 × 10 5 : 5 × 10 5 , the reaction temperature is 50 °C, and the others are the same as those in Example 2. The test results are shown in Table 2.

[0081] Comparative Example 2

[0082] Steps (1), (3), (4), and (5) are the same as those in Example 2, where the number-average molecular weight in step (4) increases to 99,000; in step (2), under anhydrous and anaerobic conditions, 1224.0 g (20 mol × 0.90) of monomer A with the structure shown in formula II (R1 is II-2), 190.0 mL (20 × 5 × 10 -5mol) and solvent hexane were put into a 28-liter reactor, the temperature in the reactor was controlled at 50°C, and the pressure in the reactor was controlled at 0.5 MPa. The molar ratio of the main catalyst, the monomer A of the structure shown in Ⅱ, and the solvent was 5.0:0.9×10 5 : 5×10 5 , reaction temperature 50°C, and other parameters were consistent with those in Example 2. The test results are shown in Table 2.

[0083] Comparative Example 3

[0084] Steps (1)(3)(4)(5) are consistent with Example 2, wherein in step (4), the number average molecular weight increases to 107,000; in step (2), under anhydrous and oxygen-free conditions, 4536.0 g (20 mol×0.90) of monomer B (R2 is III-3) of the structure shown in formula III, 190.0 ml (20×5×10 -5 mol) and solvent hexane were put into a 50-liter reactor, the temperature in the reactor was controlled at 50°C, and the pressure in the reactor was controlled at 0.5 MPa. The molar ratio of the main catalyst, the monomer A of the structure shown in Ⅱ, and the solvent was 5.0:0.9×10 5 : 5×10 5 , reaction temperature 50°C, and other parameters were consistent with those in Example 2. The test results are shown in Table 2.

[0085] Table 1 Parameters of copolymers of the present invention and comparative examples

[0086]

[0087]

[0088] Table 2 Performance test results of the embodiments of the present invention and the comparative examples

[0089] Performance *Tensile strength, MPa *Ablation resistance rate, mm *Service temperature range, °C Example 1 18.2 0.21 -60～+150 Example 2 18.9 0.20 -60～+150 Example 3 18.0 0.37 -60～+100 Comparative Example 1 14.3 0.62 -30～+80 Comparative Example 2 18.7 0.43 -25～+80 Comparative Example 3 16.8 0.34 -25～+90

[0090] "Tensile strength" test method: characterized in accordance with the national standard "GB / T 528-2009 Determination of tensile stress-strain properties of vulcanized rubber or thermoplastic rubber";

[0091] "Ablation resistance" test method: According to the national military standard "GJB 490-1988 Flexible ablation resistant materials"

[0092] Appendix C Method Determination;

[0093] "Use temperature range" test method: Maximum use temperature: GB / T 20028-2005 uses the Arrhenius diagram to calculate the storage life and maximum use temperature of polymer materials; Minimum use temperature: According to "HG / T3866-2006 Determination of compression cold resistance coefficient of vulcanized rubber", the compression cold resistance coefficient is higher than 0.5, which is determined as the minimum use temperature.

[0094] As can be seen from the above embodiments, the present invention provides a preparation method of an elastomer with high mechanical strength, wide temperature range and ablation resistance, having the structure shown in Formula I. The material provided by the present invention contains two monomers. The introduction of monomer B hinders the low-temperature crystallization process of monomer A, making the material have good elasticity at low temperatures. On the other hand, the material provided by the present invention contains a side group R2. The presence of the R2 group improves the high-temperature resistance of the material, broadens the temperature range of the material's use, and also has a certain degree of ablation resistance. The polymerized material of the present invention has high mechanical properties, good high and low temperature resistance and excellent ablation resistance after vulcanization. The experimental results show that the tensile strength of the elastomer material prepared by the present invention after crosslinking can reach 18.9 MPa, the use temperature range is -60°C - 150°C, and the oxyacetylene ablation rate ≤ 0.20 mm / s.

[0095] The above are only the preferred embodiments of the present invention. It should be noted that for those of ordinary skill in the art, without departing from the principle of the present invention, several improvements and refinements can be made, and these improvements and refinements should also be regarded as the present invention.

Claims

1. A method for preparing an elastomeric material, characterized in that, The elastomeric material described is obtained by copolymerizing monomer A and monomer B with a catalyst; Monomer A has the structure shown in Formula II: ； The R1 has any one of the structures shown in Formula II-1 to Formula II-2: ； Monomer B has the structure shown in Formula III: ； The R2 has the structure shown in III-3: ； The elastomeric material described has the structure shown in Formula I below: ； n is the degree of polymerization: the average number of polymer repeating units.

2. The preparation method according to claim 1, characterized in that, Preparation of the catalyst: Under anhydrous and anaerobic conditions, the main catalyst, aluminum agent, chlorine source, isoprene monomer and solvent are put into a reaction kettle and mixed according to a molar ratio of 1.0: 20.0 to 50.0: 0 to 2.0: 1.0 to 5.0: 5.0 to 20.

0. The mixing temperature is 25 °C to 50 °C, the mixing time is 10 to 20 minutes, and after mixing, it is aged for 1 to 12 hours for later use; The main catalyst described includes one or more of neodymium octanoate, neodymium naphthenate, neodymium isopropoxide, nickel naphthenate, butyllithium; The aluminum agent described includes one or more of trimethylaluminum, triisobutylaluminum, octylaluminum, triethylaluminum; The chlorine source described includes one or more of diethylaluminum chloride, dibutylaluminum chloride, dichloroethylaluminum, dichlorobutylaluminum, chloroform.

3. The preparation method according to claim 2, characterized in that, The reaction kettle for preparing the catalyst is a 1-liter to 5-liter reaction polymerization kettle with a stirrer paddle and capable of heating; the temperature adjustment range of the reaction kettle is 25 °C to 50 °C; the pressure adjustment range is 0.1 to 0.5 MPa; The isoprene monomer described is a polymer with a purity exceeding 99.99% and free of impurities that react with the catalyst; The solvent described is hexane with a water content of 10 ppm (10 -6 ) or less.

4. The preparation method according to claim 2 or 3, characterized in that, It includes the following steps: (1) Polymerization of two monomers: Under anhydrous and anaerobic conditions, monomer A, monomer B, a catalyst, and a solvent are added to a reaction kettle. The molar ratio of the main catalyst, monomer A, monomer B, and the solvent is 1.0~10.0: 0.75×10 5 ~0.95×10 5 : 0.05×10 5 ~0.25×10 5 : 5×10 5 ~10×10 5 , the reaction temperature is 30°C~80°C, and the reaction time is 5~10 minutes; (2) Achieving chain growth of the copolymer of monomer A and monomer B by using a chain transfer agent: adding a chain transfer agent to the reaction kettle, and the molar ratio of the chain transfer agent to the main catalyst is 1.0 to 10.0: 5.0 to 20.0; the reaction temperature is 30 °C to 80 °C, and the reaction time is 10 to 30 minutes; (3) After the components react in the reaction kettle for 2 to 8 hours, the number-average molecular weight of the polymer increases by 80,000 to 150,000. The polymerization reaction is terminated with a chain terminator, and the molar ratio of the chain terminator to the main catalyst is 100.0 to 200.0: 1.0 to 10.

0. The reaction temperature is 30 °C to 80 °C. After coagulation and drying, the raw rubber of the elastomeric material is obtained.

5. The preparation method according to claim 4, characterized in that, In step (1), the reaction kettle described is a 10-liter to 80-liter reaction polymerization kettle with a stirrer paddle and capable of heating; the temperature adjustment range of the reaction kettle is 25 °C to 200 °C; the pressure adjustment range is 0.1 to 1.0 MPa; The solvent described is hexane with a water content of 10 ppm (10 -6 ) or less.

6. The preparation method according to claim 5, characterized in that, In step (1), the reaction kettle described is a 20- to 50-liter reaction polymerization kettle with a stirrer paddle and capable of heating; the temperature adjustment range of the reaction kettle is 25 °C to 100 °C.

7. The preparation method according to claim 4, characterized in that, In step (2), the chain transfer agent described includes one or several of diisobutylaluminum hydride, triethylaluminum, diethylmagnesium; In step (3), the chain terminator described includes one or more of 2,2'-methylenebis-(4-methyl-6-tert-butylphenol), 2,6-di-tert-butyl-p-cresol, n-octadecyl 3,5-di-tert-butyl-4-hydroxyphenylpropionate, 2,4-bis(n-octylthiomethylene)-6-methylphenol and ethanol.

8. An elastomeric material cross-linked polymer, characterized in that, The partial structure schematic diagram of the cross-linking position has the structure shown in Formula IV: ； In Formula IV, M is selected from one or more of the structures shown in Formula IV-1 to Formula IV-3: ； In Formula IV-3, after vulcanization, X is the number of polysulfide bonds, which is 3 to 8.

9. The crosslinked polymer according to claim 8, wherein, The crosslinking polymerization process of the elastomeric crosslinked polymer includes: mixing the raw rubber of the elastomeric material with stearic acid, zinc oxide, vulcanization accelerator, vulcanizing agent, antioxidant, reinforcing agent, plasticizer and flame retardant in a mass ratio of 100:2:4:0.5 - 1.0:0.5 - 2.0:1:30 - 50:5 - 10:10 - 20 in a mixing device. After mixing for 10 - 20 minutes, the mixture is sheeted out with an open mill and vulcanized and molded at 150 °C and a pressure of 10 MPa for more than 20 minutes in an oil hydraulic molding machine to obtain a crosslinked elastomeric specimen.

10. The crosslinked polymer according to claim 9, wherein, The vulcanization accelerator is: hexamethylenetetramine (accelerator H), diphenylguanidine (accelerator D), tetramethylthiuram disulfide (accelerator TMTD), 2-mercaptobenzothiazole (accelerator M), zinc dimethyldithiocarbamate (accelerator ZDMC), zinc butylxanthate (accelerator ZBX), ethylenethiourea (accelerator NA-22), N-cyclohexyl-2-benzothiazolesulfenamide (accelerator CZ), triallyl isocyanurate (accelerator TAIC), N,N'-m-phenylene bismaleimide (HVA2), trimethylolpropane trimethacrylate (TMPTMA), or one or more of them; The vulcanizing agent includes: sulfur, dicumyl peroxide (DCP), benzoyl peroxide (BPO), 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane (bis-2,5), di-tert-butyl peroxide (DTBP), or one or more of them; The antioxidant includes: N-phenyl-β-naphthylamine (antioxidant D), 2,2,4-trimethyl-1,2-dihydroquinoline polymer (antioxidant RD), 2-mercaptobenzimidazole (antioxidant MB), nickel di-n-butyldithiocarbamate (antioxidant NBC), N-isopropyl-N'-phenyl-p-phenylenediamine (antioxidant 4010NA), or one or more of them; The reinforcing agent includes: carbon black, white carbon black, calcium carbonate, calcium oxide, titanium dioxide, or one or more of them; The plasticizer includes: naphthenic oil, aromatic oil, paraffin oil, or one or more of them; The flame retardant includes: tributyl phosphate, tris(2-ethylhexyl) phosphate, tris(2-chloroethyl) phosphate, triphenyl phosphate, (2-ethylhexyl)diphenyl phosphate, chlorendic anhydride, pentabromoethylbenzene, tetrabromobisphenol A, tris(dibromopropyl) phosphate, halogenated cyclohexane, magnesium hydroxide, aluminum hydroxide, borate, or one or more of them.

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