Ketone compound modified polybutadiene rubber, preparation method thereof and vulcanized rubber
阅读说明：本技术 一种酮类化合物改性聚丁二烯橡胶及其制备方法和硫化橡胶 (Ketone compound modified polybutadiene rubber, preparation method thereof and vulcanized rubber ) 是由 白晨曦 代全权 祁彦龙 董巍 于 2021-11-11 设计创作，主要内容包括：本发明属于聚合物技术领域,尤其涉及一种酮类化合物改性聚丁二烯橡胶及其制备方法和硫化橡胶。本发明提供的酮类化合物改性聚丁二烯橡胶由丁二烯单体和烷基铝改性酮类化合物在稀土催化剂存在下反应制成；所述烷基铝改性酮类化合物由烷基铝和酮类化合物混合制成；所述烷基铝为三异丁基铝、氢化二异丁基铝、二乙基氢化铝、三辛基铝、三乙基铝、一氯二异丁基铝、一氯二乙基铝和倍半乙基铝中的一种或多种。本发明通过将烷基铝改性酮类化合物原位加到丁二烯聚合反应体系中,使酮类化合物与聚丁二烯以分子形式结合,均匀分散,从而显著提升了聚丁二烯橡胶的力学性能。此外,本发明提供的改性聚丁二烯橡胶的制备过程也较为简单,十分适合大规模生产。(The invention belongs to the technical field of polymers, and particularly relates to ketone compound modified polybutadiene rubber, a preparation method thereof and vulcanized rubber. The ketone compound modified polybutadiene rubber provided by the invention is prepared by reacting a butadiene monomer and an alkyl aluminum modified ketone compound in the presence of a rare earth catalyst; the alkyl aluminum modified ketone compound is prepared by mixing alkyl aluminum and a ketone compound; the alkyl aluminum is one or more of triisobutyl aluminum, diisobutyl aluminum hydride, diethyl aluminum hydride, trioctyl aluminum, triethyl aluminum, diisobutyl aluminum monochloride, diethyl aluminum monochloride and ethyl aluminum sesqui-ethyl. According to the invention, the alkyl aluminum modified ketone compound is added into a butadiene polymerization reaction system in situ, so that the ketone compound and polybutadiene are combined in a molecular form and uniformly dispersed, and the mechanical property of the polybutadiene rubber is obviously improved. In addition, the preparation process of the modified polybutadiene rubber provided by the invention is simple, and the modified polybutadiene rubber is very suitable for large-scale production.)
1. A ketone compound modified polybutadiene rubber is prepared by reacting a butadiene monomer with an alkyl aluminum modified ketone compound in the presence of a rare earth catalyst;
the alkyl aluminum modified ketone compound is prepared by mixing alkyl aluminum and a ketone compound;
the alkyl aluminum is one or more of triisobutyl aluminum, diisobutyl aluminum hydride, diethyl aluminum hydride, trioctyl aluminum, triethyl aluminum, diisobutyl aluminum monochloride, diethyl aluminum monochloride and ethyl aluminum sesqui-ethyl;
the ketone compound is one or more of the following compounds in the general formula: c(n-1)H(2n-3)NO，n≥6；C(n+3)H(2n+2)O，n≥6；CnH2nN2O，n≥5；CnH(2n-1)NO2，n≥5；CnH(2n-8)O2，n≥29。
2. The ketone compound-modified polybutadiene rubber according to claim 1, wherein the ketone compound is one or more of 2-piperidone, isophorone, 4-amino-2-piperidone, 4-hydroxy-2-piperidone and DL- α -tocopherol.
3. The ketone compound-modified polybutadiene rubber according to claim 1, wherein the molar ratio of the alkyl aluminum to the ketone compound is (1-10): 1.
4. the ketone compound-modified polybutadiene rubber according to claim 1, wherein the amount of the alkyl aluminum-modified ketone compound is 0.5 to 3 wt% based on the mass of the butadiene monomer.
5. The ketone compound-modified polybutadiene rubber according to claim 1, wherein the rare earth catalyst is prepared by mixing a rare earth compound, an organoaluminum compound, and a chloride compound in a solvent;
the rare earth compound is one or more of rare earth carboxylate, rare earth acidic phosphonate, alkoxy rare earth, chlorinated rare earth electron donor complex and sulfonic rare earth electron donor complex;
the organic aluminum compound is trialkyl aluminum and/or alkyl aluminum hydride;
the chloride is one or more of diisobutylaluminum chloride, diethylaluminum chloride, ethylaluminum sesqui, tert-butyl chloride, benzyl chloride, allyl chloride, chloromethylsilane and silicon tetrachloride.
6. The ketone compound-modified polybutadiene rubber according to claim 5, wherein the rare earth compound is one or more of neodymium neodecanoate, neodymium isooctanoate, neodymium naphthenate, neodymium (2-ethylhexyl) phosphonate, neodymium mono-2-ethylhexyl (2-ethylhexyl) phosphonate, neodymium ethoxide, neodymium N-propoxide, neodymium isopropoxide, neodymium chloride isopropanol, neodymium chloride tributyl phosphate, neodymium trifluoromethanesulfonate tributyl phosphate, and neodymium benzenesulfonate N, N-dimethylformamide;
the organic aluminum compound is one or more of triisobutylaluminum, diisobutylaluminum hydride, diethylaluminum hydride, trioctylaluminum and triethylaluminum.
7. The ketone compound-modified polybutadiene rubber according to claim 5, wherein the molar ratio of the rare earth atom, the organoaluminum compound and the chloride in the rare earth compound is 1: (10-30): (2-3).
8. The ketone compound-modified polybutadiene rubber according to claim 1, wherein the ratio of the rare earth catalyst to the butadiene monomer in terms of the molar number of rare earth atoms is (2X 10)-6～1×10-5)mol：1g。
9. A method for preparing the ketone compound-modified polybutadiene rubber according to claim 1, comprising the steps of:
in the presence of a rare earth catalyst, a butadiene monomer and an alkyl aluminum modified ketone compound are mixed in an organic solvent for reaction to obtain the ketone compound modified polybutadiene rubber.
10. A vulcanized rubber characterized by comprising the ketone compound-modified polybutadiene rubber according to any one of claims 1 to 8 as a raw material component.
Technical Field
The invention belongs to the technical field of polymers, and particularly relates to ketone compound modified polybutadiene rubber, a preparation method thereof and vulcanized rubber.
Background
Rubber plays an indispensable role as a basic application material in the fields of automobiles, buildings, machinery, electricity and the like, and is an extremely important strategic resource. According to the classification of sources, rubbers can be divided into two categories: one kind is synthetic rubber prepared by using coal, petroleum, natural gas and the like as raw materials and adopting a chemical method; another is natural rubber extracted from rubber-containing plants such as hevea brasiliensis, etc.
The natural rubber has the advantages of large elasticity, high tensile strength, excellent tear resistance and electrical insulation, good wear resistance and drought resistance, good processability and easy adhesion with other materials. Although synthetic rubber has some advantages, such as no geographical limitation, good product consistency, high labor productivity and individual performance superior to natural rubber, etc., such as polybutadiene rubber, the synthetic rubber is the second most common synthetic rubber which is only inferior to styrene butadiene rubber in the world at present, and the advantages of the synthetic rubber include good low temperature resistance, good elasticity, good dynamic performance, etc., and the synthetic rubber is widely applied to the production of rubber products such as tires, adhesive tapes, rubber shoes, etc. However, the comprehensive properties of the polybutadiene rubber cannot catch up with natural rubber so far, and how to further improve the properties of the polybutadiene rubber is a technical problem to be solved urgently by technical personnel in the field.
Disclosure of Invention
In view of the above, the present invention aims to provide a ketone compound modified polybutadiene rubber, a preparation method thereof and a vulcanized rubber, wherein the modified polybutadiene rubber provided by the present invention has high strength and high stress at definite elongation, is simple to prepare, and is produced on a large scale.
The invention provides a ketone compound modified polybutadiene rubber, which is prepared by reacting a butadiene monomer with an alkyl aluminum modified ketone compound in the presence of a rare earth catalyst;
the alkyl aluminum modified ketone compound is prepared by mixing alkyl aluminum and a ketone compound;
the alkyl aluminum is one or more of triisobutyl aluminum, diisobutyl aluminum hydride, diethyl aluminum hydride, trioctyl aluminum, triethyl aluminum, diisobutyl aluminum monochloride, diethyl aluminum monochloride and ethyl aluminum sesqui-ethyl;
the ketone compound is one or more of the following compounds in the general formula: c(n-1)H(2n-3)NO，n≥6；C(n+3)H(2n+2)O，n≥6；CnH2nN2O，n≥5；CnH(2n-1)NO2，n≥5；CnH(2n-8)O2，n≥29。
Preferably, the ketone compound is one or more of 2-piperidone, isophorone, 4-amino-2-piperidone, 4-hydroxy-2-piperidone and DL-alpha-tocopherol.
Preferably, the molar ratio of the alkyl aluminum to the ketone compound is (1-10): 1.
preferably, the amount of the alkyl aluminum modified ketone compound is 0.5-3 wt% of the mass of the butadiene monomer.
Preferably, the rare earth catalyst is prepared by mixing a rare earth compound, an organic aluminum compound and a chloride in a solvent;
the rare earth compound is one or more of rare earth carboxylate, rare earth acidic phosphonate, alkoxy rare earth, chlorinated rare earth electron donor complex and sulfonic rare earth electron donor complex;
the organic aluminum compound is trialkyl aluminum and/or alkyl aluminum hydride;
the chloride is one or more of diisobutylaluminum chloride, diethylaluminum chloride, ethylaluminum sesqui, tert-butyl chloride, benzyl chloride, allyl chloride, chloromethylsilane and silicon tetrachloride.
Preferably, the rare earth compound is one or more of neodymium neodecanoate, neodymium isooctanoate, neodymium naphthenate, neodymium (2-ethylhexyl) phosphonate, neodymium mono-2-ethylhexyl (2-ethylhexyl) phosphonate, neodymium ethoxy, neodymium N-propoxy, neodymium isopropoxy, neodymium chloride isopropanol, neodymium chloride tributyl phosphate, neodymium trifluoromethanesulfonate tributyl phosphate and neodymium benzenesulfonate N, N-dimethylformamide;
the organic aluminum compound is one or more of triisobutylaluminum, diisobutylaluminum hydride, diethylaluminum hydride, trioctylaluminum and triethylaluminum.
Preferably, the molar ratio of the rare earth atoms, the organic aluminum compound and the chloride in the rare earth compound is 1: (10-30): (2-3).
Preferably, the ratio of the rare earth catalyst to the mass of the butadiene monomer in terms of the number of moles of rare earth atoms is (2X 10)-6～1×10-5)mol：1g。
The invention provides a preparation method of ketone compound modified polybutadiene rubber, which comprises the following steps:
in the presence of a rare earth catalyst, a butadiene monomer and an alkyl aluminum modified ketone compound are mixed in an organic solvent for reaction to obtain the ketone compound modified polybutadiene rubber.
The invention provides vulcanized rubber, and the raw material components of the vulcanized rubber comprise the ketone compound modified polybutadiene rubber in the technical scheme.
Compared with the prior art, the invention provides a ketone compound modified polybutadiene rubber, a preparation method thereof and vulcanized rubber. The ketone compound modified polybutadiene rubber provided by the invention is prepared by reacting a butadiene monomer and an alkyl aluminum modified ketone compound in the presence of a rare earth catalyst; the alkyl aluminum modified ketone compound is prepared by mixing alkyl aluminum and a ketone compound; the alkyl aluminum is one or more of triisobutyl aluminum, diisobutyl aluminum hydride, diethyl aluminum hydride, trioctyl aluminum, triethyl aluminum, diisobutyl aluminum monochloride, diethyl aluminum monochloride and ethyl aluminum sesqui-ethyl; the ketone compound is one or more of the following compounds in the general formula: c(n-1)H(2n-3)NO，n≥6；C(n+3)H(2n+2)O，n≥6；CnH2nN2O，n≥5；CnH(2n-1)NO2，n≥5；CnH(2n-8)O2，n≥29. According to the invention, the alkyl aluminum modified ketone compound is added into a butadiene polymerization reaction system in situ, so that the ketone compound and polybutadiene are combined in a molecular form and uniformly dispersed, and thus the mechanical property of the polybutadiene rubber is obviously improved, and the polybutadiene rubber has higher strength and stress at definite elongation. In addition, the preparation process of the modified polybutadiene rubber provided by the invention is simple, is very suitable for large-scale production, and has good market prospect. Experimental results show that the modified polybutadiene rubber provided by the invention has tensile strength of more than 18MPa and 300% stress at definite elongation of more than 11.5MPa after vulcanization.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a ketone compound modified polybutadiene rubber, which is prepared by reacting a butadiene monomer (1, 3-butadiene) with an alkyl aluminum modified ketone compound in the presence of a rare earth catalyst.
In the modified polybutadiene rubber provided by the invention, the alkyl aluminum modified ketone compound is prepared by mixing alkyl aluminum and a ketone compound. Wherein the alkyl aluminum is triisobutyl aluminum Al (i-Bu)3Diisobutylaluminum hydride Al (i-Bu)2H. Diethyl aluminium hydride AlEt2H. Trioctylaluminum (oct)3Triethylaluminum AlEt3Aluminum diisobutylaluminum monochloride Al (i-Bu)2Cl, aluminum diethyl monochloride AlEt2Cl and aluminum sesquiethyl Al2Et3Cl3One or more of; the ketone compound is one or more of the following compounds in the general formula: c(n-1)H(2n-3)NO, n.gtoreq.6, preferably 2-piperidone C5H9NO；C(n+3)H(2n+2)O, n is more than or equal to 6, and is preferably isophorone C9H14O；CnH2nN2O, n is more than or equal to 5, and is preferably 4-amino-2-piperidone C5H10N2O；CnH(2n-1)NO2N.gtoreq.5, preferably 4-hydroxy-2-piperidone C5H9NO2；CnH(2n-8)O2N.gtoreq.29, preferably DL-alpha-tocopherol C29H50O2。
In the modified polybutadiene rubber provided by the invention, the molar ratio of the alkyl aluminum in the alkyl aluminum modified ketone compound to the ketone compound is preferably (1-10): 1, specifically 1:1, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1 or 10: 1.
In the modified polybutadiene rubber provided by the present invention, the amount of the aluminum alkyl modified ketone compound is preferably 0.5 to 3 wt% of the mass of the butadiene monomer, and specifically may be 0.5 wt%, 0.6 wt%, 0.7 wt%, 0.8 wt%, 0.9 wt%, 1 wt%, 1.1 wt%, 1.2 wt%, 1.3 wt%, 1.4 wt%, 1.5 wt%, 1.6 wt%, 1.7 wt%, 1.8 wt%, 1.9 wt%, 2 wt%, 2.1 wt%, 2.2 wt%, 2.3 wt%, 2.4 wt%, 2.5 wt%, 2.6 wt%, 2.7 wt%, 2.8 wt%, 2.9 wt%, or 3 wt%.
In the modified polybutadiene rubber provided by the present invention, the rare earth catalyst is preferably prepared by mixing a rare earth compound, an organoaluminum compound and a chloride in a solvent. The rare earth compound is preferably one or more of rare earth carboxylate, rare earth acidic phosphonate, alkoxy rare earth, chlorinated rare earth electron donor complex and sulfonic rare earth electron donor complex; the rare earth carboxylate is neodymium neodecanoate Nd (vers)3Neodymium isooctanoate Nd (EHA)3And neodymium naphthenate Nd (naph)3One or more of; the rare earth acidic phosphonate is preferably neodymium (2-ethylhexyl) phosphate Nd (P)204)3And/or neodymium (2-ethylhexyl) phosphonate, Nd (P) mono-2-ethylhexyl ester507)3(ii) a The alkoxy rare earth is preferably one or more of neodymium ethoxide, neodymium n-propoxide and neodymium isopropoxide; the preferable rare earth chloride electron donor complex is neodymium chloride isopropanol NdCl3·3PriOH and/or Neodymium chloride tributyl phosphate NdCl3·3TBP; the sulfonic acid rare earth electron donor complex is preferably neodymium trifluoromethanesulfonate tributyl phosphate Nd (CF)3SO3)33TBP and/or Neodymium benzenesulfonate Nd N, N-dimethylformamide (C)18H29SO3)3·3C3H7NO。
In the modified polybutadiene rubber provided by the present invention, the organoaluminum compound in the rare earth catalyst is preferably trialkylaluminum and/or alkylaluminum hydride, more preferably triisobutylaluminum Al (i-Bu)3Diisobutylaluminum hydride Al (i-Bu)2H. Diethyl aluminium hydride AlEt2H. Trioctylaluminum (oct)3And triethylaluminum AlEt3One or more of; the preferred molar ratio of the organic aluminum compound to the rare earth atoms in the rare earth compound is (10-30): 1, specifically 10:1, 11:1, 12:1, 13:1, 14:1, 15:1, 16:1, 17:1, 18:1, 19:1, 20:1, 21:1, 22:1, 23:1, 24:1, 25:1, 26:1, 27:1, 28:1, 29:1 or 30: 1.
In the modified polybutadiene rubber provided by the invention, the chloride in the rare earth catalyst is preferably diisobutylaluminum monochloride Al (i-Bu)2Cl, aluminum diethyl monochloride AlEt2Cl, aluminum sesquiethyl Al2Et3Cl3T-butylchloride t-BuCl, benzyl chloride BzCl, allyl chloride H2C＝CHCH2Cl, chloromethylsilane Me4-nSiCln(n is 1, 2 or 3) and silicon tetrachloride SiCl4One or more of; the preferred molar ratio of the chloride to the rare earth atoms in the rare earth compound is (2-3): 1, specifically 2:1, 2.1:1, 2.2:1, 2.3:1, 2.4:1, 2.5:1, 2.6:1, 2.7:1, 2.8:1, 2.9:1 or 3: 1.
In the modified polybutadiene rubber provided by the invention, the solvent in the rare earth catalyst is preferably one or more of n-hexane, n-pentane, cyclohexane and n-heptane, and more preferably n-hexane; the concentration of the rare earth compound in the solvent is preferably 0.5X 10 in terms of rare earth atom-5～5×10-5mol/mL, specifically 0.5X 10-5mol/mL、1×10-5mol/mL、1.5×10-5mol/mL、2×10-5mol/mL、2.5×10-5mol/mL、3×10-5mol/mL、3.5×10-5mol/mL、4×10-5mol/mL、4.5×10-5mol/mL or 5X 10-5mol/mL。
In the modified polybutadiene rubber provided by the invention, the ratio of the rare earth catalyst to the mass of the butadiene monomer in terms of the mole number of rare earth atoms is preferably (2X 10)-6～1×10-5) mol:1g, specifically 2X 10-6mol:1g、2.5×10- 6mol:1g、3×10-6mol:1g、3.5×10-6mol:1g、4×10-6mol:1g、4.5×10-6mol:1g、5×10-6mol:1g、5.5×10-6mol:1g、6×10-6mol:1g、6.5×10-6mol:1g、7×10-6mol:1g、7.5×10-6mol:1g、8×10-6mol:1g、8.5×10-6mol:1g、9×10-6mol:1g、9.5×10-6mol:1g or 1X 10-6mol:1g。
The invention also provides a preparation method of the ketone compound modified polybutadiene rubber, which comprises the following steps:
in the presence of a rare earth catalyst, a butadiene monomer and an alkyl aluminum modified ketone compound are mixed in an organic solvent for reaction to obtain the ketone compound modified polybutadiene rubber.
In the preparation method provided by the invention, the alkyl aluminum modified ketone compound is prepared by mixing alkyl aluminum and a ketone compound. The specific types and the dosage ratios of the alkyl aluminum and the ketone compounds are introduced in the above description, and are not described again; the specific preparation process of the aluminum alkyl modified ketone compound preferably comprises the following steps: mixing the alkyl aluminum and the ketone compound under the atmosphere of protective gas to obtain an alkyl aluminum modified ketone compound; the protective gas is preferably nitrogen.
In the preparation method provided by the invention, the rare earth catalyst is preferably prepared by mixing a rare earth compound, an organic aluminum compound and a chloride in a solvent. The specific kinds and dosage ratios of the rare earth compound, the organic aluminum compound, the chloride and the solvent of the rare earth catalyst are introduced in the above, and are not described again; the specific preparation process of the rare earth catalyst preferably comprises the following steps: mixing a rare earth compound, an organic aluminum compound, a chloride and a solvent under the atmosphere of protective gas, and aging to obtain a rare earth catalyst; the protective gas is preferably nitrogen; the mixing process is preferably to add the rare earth compound, the organic aluminum compound, the chloride and the solvent into the mixing container in sequence, and more preferably to add the rare earth compound solution, the organic aluminum compound solution, the chloride solution and the solvent into the mixing container in sequence; the temperature of the aging is preferably 0-80 ℃, and specifically can be 0 ℃, 10 ℃, 20 ℃, 30 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃ or 80 ℃; the aging time is preferably 5-60 min, and specifically can be 5min, 10min, 15min, 20min, 24min, 25min, 30min, 35min, 40min, 45min, 50min, 55min or 60 min.
In the preparation method provided by the invention, the organic solvent is preferably one or more of n-hexane, n-pentane, cyclohexane and n-heptane, and more preferably n-hexane.
In the preparation method provided by the invention, the dosage and the ratio of the butadiene monomer, the alkyl aluminum modified ketone compound and the rare earth catalyst are introduced in the above, and are not described again; the amount ratio of the butadiene monomer to the organic solvent is preferably 10g: (50-300) mL, specifically 10g:50mL, 10g:60mL, 10g:70mL, 10g:80mL, 10g:90mL, 10g:100mL, 10g:110mL, 10g:120mL, 10g:130mL, 10g:140mL, 10g:150mL, 10g:170mL, 10g:200mL, 10g:230mL, 10g:250mL, 10g:270mL, or 10g:300 mL.
In the preparation method provided by the present invention, the specific process of mixing the butadiene monomer and the aluminum alkyl modified ketone compound in the presence of the rare earth catalyst in the organic solvent preferably includes: under the protective gas atmosphere, adding a mixture of butadiene monomer and organic solvent into a reactor, then adding an alkyl aluminum modified ketone compound, and finally adding a rare earth catalyst. Wherein the protective gas is preferably nitrogen.
In the preparation method provided by the invention, the reaction temperature is preferably 0-70 ℃, and specifically can be 0 ℃, 5 ℃, 10 ℃, 15 ℃, 20 ℃, 25 ℃, 30 ℃, 35 ℃, 40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃, 65 ℃ or 70 ℃; the reaction time is preferably 1-24 h, and specifically can be 1h, 2h, 4h, 6h, 8h, 10h, 12h, 14h, 16h, 18h, 20h, 22h or 24 h.
In the preparation method provided by the invention, after the reaction is finished, the reaction product is subjected to post-treatment to obtain the ketone compound modified polybutadiene rubber. Wherein, the mode of the post-treatment preferably comprises: and sequentially carrying out alcohol precipitation, alcohol washing and drying.
The invention also provides vulcanized rubber which takes the ketone compound modified polybutadiene rubber in the technical scheme as a main raw material component.
In the vulcanized rubber provided by the invention, raw material components preferably further comprise zinc oxide, stearic acid, an accelerator, sulfur, carbon black and standard oil for rubber test. Wherein the accelerator is preferably an accelerator NS; the carbon black is preferably a universal industrial reference carbon black; the standard oil for rubber test is preferably ASTM103# oil.
In the vulcanized rubber provided by the invention, the content of the zinc oxide in the raw material is preferably 1-5 parts by mass, more preferably 3 parts by mass, based on 100 parts by mass of the ketone compound modified polybutadiene rubber in the raw material; the content of the stearic acid in the raw materials is preferably 1-5 parts by mass, and more preferably 2 parts by mass; the content of the accelerator in the raw materials is preferably 0.5-2 parts by mass, and more preferably 0.9 part by mass; the content of the sulfur in the raw materials is preferably 1-3 parts by mass, and more preferably 1.5 parts by mass; the content of the carbon black in the raw materials is preferably 40-80 parts by mass, and more preferably 60 parts by mass; the content of the standard oil for rubber test in the raw material is preferably 10 to 30 parts by mass, and more preferably 15 parts by mass.
According to the technical scheme, the alkyl aluminum modified ketone compound is added into a butadiene polymerization reaction system in situ, so that the ketone compound and polybutadiene are combined in a molecular form and uniformly dispersed, the mechanical property of the polybutadiene rubber is obviously improved, and the polybutadiene rubber has higher strength and stress at definite elongation. Experimental results show that the modified polybutadiene rubber provided by the invention has tensile strength of more than 18MPa and 300% stress at definite elongation of more than 11.5MPa after vulcanization.
For the sake of clarity, the following examples are given in detail.
Examples 1 to 5
To a dry catalyst reactor, 10mL of 2X 10 in sequence were added under nitrogen blanket-4mol/mL of the hexane solution of the A component (rare earth compound), 30mL of 2X 10-3And (3) a hexane solution of a B component (organic aluminum compound) in mol/mL, wherein the molar ratio of the B component to the rare earth element in the A component is 30:1, 20mL of 2X 10 was added-4And (3) a hexane solution of C component (chloride) in mol/mL, wherein the molar ratio of the C component to the rare earth element in the A component is 2:1, adding hexane solvent to prepare rare earth elements with the concentration of 2 multiplied by 10-5And (3) aging the rare earth catalyst with mol/mL at 80 ℃ for 5 minutes to obtain the rare earth catalyst for preparing polybutadiene rubber.
Under the protection of nitrogen, mixing the alkyl aluminum and the ketone compound according to a molar ratio to obtain an alkyl aluminum modified ketone compound, which is marked as a component D.
Under the protection of nitrogen, 1L of 1, 3-butadiene hexane solution with the monomer concentration of 10g/100mL is added into a polymerization kettle; then adding a component D, wherein the using amount of the component D is 0.5 wt% of the mass of the butadiene monomer; then adding a rare earth catalyst, wherein the mass ratio of the rare earth catalyst to the butadiene monomer is 2 multiplied by 10 according to the molar number of Nd-6mol:1g of a compound; reacting for 24 hours at the temperature of 0 ℃, precipitating the polymer in ethanol, washing and extruding the polymer by the ethanol, and drying the polymer in vacuum to constant weight to obtain the modified polybutadiene rubber.
The modified polybutadiene rubber is used as a main raw material to prepare vulcanized rubber, and the formula of the raw material is as follows: 100.00phr of polybutadiene rubber, 3.00phr of zinc oxide, 2.00phr of stearic acid, 0.90phr of accelerator NS (N-tert-butyl-2-benzothiazole sulfonamide), 1.50phr of sulfur, 60.00phr of general industrial reference carbon black and 15.00phr of ASTM103# oil. The vulcanization process is as follows: setting the temperature of an internal mixer to 50 +/-5 ℃, adding rubber, zinc oxide, stearic acid, carbon black and 103# oil, pressing and mixing for 3 minutes, lifting a top plug, cleaning, mixing for 3 minutes, discharging rubber, discharging sheets of an open mill, and standing for 1-24 hours at room temperature; setting the temperature of an open mill to be 35 ℃, wrapping rubber for 1 minute, adding sulfur and an accelerant, and mixing for 1 minute; the film was left to stand for 2 to 24 hours and was cured using 145 ℃ for 35 min. The resulting vulcanizates were tested for properties and the results are detailed in table 1:
TABLE 1 results of polymer experiments obtained in examples 1 to 5
Examples 6 to 9
To a dry catalyst reactor, 10mL of 2X 10 in sequence were added under nitrogen blanket-4mol/mL of the hexane solution of the A component (rare earth compound), 20mL of 2X 10-3And (3) a hexane solution of a component B (organic aluminum compound) in mol/mL, wherein the molar ratio of the component B to the rare earth elements in the component A is 20:1, 30mL of 2X 10 was added-4And (3) a hexane solution of a C component (chloride) in mol/mL, wherein the molar ratio of the C component to the rare earth element in the A component is 3:1, adding hexane solvent to prepare rare earth elements with the concentration of 2 multiplied by 10-5And (3) aging the rare earth catalyst with mol/mL at 0 ℃ for 24 minutes to obtain the rare earth catalyst for preparing polybutadiene rubber.
Under the protection of nitrogen, mixing the alkyl aluminum and the ketone compound according to a molar ratio to obtain an alkyl aluminum modified ketone compound, which is marked as a component D.
Under the protection of nitrogen, 1L of 1, 3-butadiene hexane solution with the monomer concentration of 10g/100mL is added into a polymerization kettle; then adding a component D, wherein the using amount of the component D is 2.0 wt% of the mass of the butadiene monomer; then adding a rare earth catalyst, wherein the mass ratio of the rare earth catalyst to the butadiene monomer is 7 multiplied by 10 according to the molar number of Nd-6mol:1g of a compound; reacting for 10 hours at 40 ℃, precipitating the polymer in ethanol, washing and extruding by the ethanol, and drying in vacuum to constant weight to obtain the modified polybutadiene rubber.
The modified polybutadiene rubber is used as a main raw material to prepare vulcanized rubber, and the raw material formula and the vulcanization process refer to examples 1-5. The resulting vulcanizates were tested for properties and the results are detailed in table 2:
TABLE 2 results of polymer experiments obtained in examples 6 to 9
Examples 10 to 13
To a dry catalyst reactor, 10mL of 2X 10 in sequence were added under nitrogen blanket-4mol/mL of the hexane solution of the A component (rare earth compound), 10mL of 2X 10-3And (3) a hexane solution of a component B (organic aluminum compound) in mol/mL, wherein the molar ratio of the component B to the rare earth elements in the component A is 10:1, add 25mL of 2X 10-4A mol/mL hexane solution of C component (chloride), wherein the molar ratio of the C component to the rare earth element in the A component is 2.5:1, adding hexane solvent to prepare rare earth elements with the concentration of 2 multiplied by 10-5And (3) aging the rare earth catalyst with mol/mL at 50 ℃ for 60 minutes to obtain the rare earth catalyst for preparing polybutadiene rubber.
Under the protection of nitrogen, mixing the alkyl aluminum and the ketone compound according to a molar ratio to obtain an alkyl aluminum modified ketone compound, which is marked as a component D.
Under the protection of nitrogen, 1L of 1, 3-butadiene hexane solution with the monomer concentration of 10g/100mL is added into a polymerization kettle; then adding a component D, wherein the using amount of the component D is 3.0 wt% of the mass of the butadiene monomer; then adding a rare earth catalyst, wherein the mass ratio of the rare earth catalyst to the butadiene monomer is 1.0 multiplied by 10 according to the molar number of Nd-5mol:1g of a compound; reacting for 1 hour at 70 ℃, precipitating the polymer in ethanol, washing and extruding by the ethanol, and drying in vacuum to constant weight to obtain the modified polybutadiene rubber.
The modified polybutadiene rubber is used as a main raw material to prepare vulcanized rubber, and the raw material formula and the vulcanization process refer to examples 1-5. The resulting vulcanizates were tested for properties and the results are detailed in table 3:
table 3 Experimental results for polymers obtained in examples 10 to 13
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.