Butadiene polymerization catalyst system, method of making and butadiene polymerization method
By replacing nickel naphthenate catalysts with organophosphates and cyclic alkylates, the problems of unstable catalyst quality and resource scarcity were solved, achieving stable and efficient polymerization in cis-butadiene rubber production, reducing costs and improving the physical and mechanical properties of the product.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- PETROCHINA CO LTD
- Filing Date
- 2024-12-28
- Publication Date
- 2026-06-30
AI Technical Summary
The existing nickel naphthenate catalyst is of unstable quality, which leads to unstable quality of butadiene rubber production. In addition, resources are scarce, increasing production costs. Furthermore, the high gel content of the polymerization product can easily cause pipeline blockage.
By using organophosphate nickel and cyclic alkyl nickel oxide instead of naphthenate nickel as catalysts, and through mixing of specific ratios and components, a simple and high-purity catalytic system is prepared, reducing the influence of impurities and improving polymerization conversion and physical and mechanical properties.
This simplifies the catalyst preparation process and stabilizes product quality, reduces production costs, decreases gel content, and ensures long-term operation and environmental friendliness of the equipment.
Abstract
Description
Technical fields:
[0001] This invention relates to the field of butadiene polymerization technology, and particularly to a butadiene polymerization catalytic system, preparation method, and butadiene polymerization method. Background technology:
[0002] Butadiene rubber (CBR) is a synthetic rubber technology independently developed in my country, and it has always adopted a nickel naphthenate-triisobutylaluminum-boron trifluoride diethyl ether complex system. Nickel naphthenate, a green, transparent, viscous liquid, is the main catalyst in CBR production. Its preparation process mainly consists of three steps: saponification reaction, where naphthenic acid is saponified with sodium hydroxide to form sodium naphthenate; the addition of nickel chloride to undergo a metathesis reaction to generate nickel naphthenate; and then the removal of inorganic salts such as sodium chloride through washing, dehydration, and desolventizing. In the catalytic system, the main catalyst, nickel naphthenate, has naphthenic acid as its ligand. Naphthenic acid is a general term for organic acids in crude oil and is a viscous liquid mixture. Due to limitations in production processes and crude oil sources, the quality of naphthenic acid is unstable, which leads to unstable product quality of nickel naphthenate, the main catalyst for CBR, thus adversely affecting the stability of product quality and process conditions for CBR manufacturers. At the same time, naphthenic acid resources are becoming increasingly scarce, leading to higher costs and making the production of nickel-based CBR dependent on the supply of naphthenic acid. Furthermore, when naphthenic acid is used as a ligand for the nickel catalyst, the gel content of the polymerization product is typically high during the production process. Excessive gel content can lead to glue buildup in the system, causing pipeline blockage and affecting the long-term operation of the equipment. Summary of the Invention:
[0003] The technical problem to be solved by this invention is to provide a butadiene polymerization catalytic system, preparation method, and butadiene polymerization method. The preparation process of the catalyst of this invention is simpler, the product has higher purity, a defined composition, and the raw materials are widely available and in sufficient supply, thereby achieving the goals of reducing costs, stabilizing the production process and product quality; reducing impurities in naphthenic acid, reducing the impact of the catalyst on the production process and the quality of the polymerized product, and improving the environmental friendliness of production; using the technical solution provided by this invention to produce nickel-based cis-butadiene rubber results in a high polymerization conversion rate of butadiene monomer, good physical and mechanical properties of the product, and low gel content.
[0004] The technical solution adopted in this invention is: a butadiene polymerization catalytic system, comprising component A, component B, component C and component D, wherein component B is an alkyl aluminum compound, component C is a boron trifluoride complex, and component D is a homogenizing agent; component A is composed of two parts, component A1 and component A2, wherein component A1 is nickel organophosphate and component A2 is alkyl nickel acid with a cyclic structure.
[0005] Further, the ligand of component A1 is selected from one or more of (2-ethylhexyl) phosphate and 2-ethylhexylphosphonic acid mono-2-ethylhexyl ester, and component A2 is selected from C6 to C6. 20 One or more of alkyl nickel oxides having a cyclic structure, wherein the cyclic structure is one or more of a four-membered ring, a five-membered ring, a six-membered ring, or a benzene ring.
[0006] Furthermore, component B is selected from one or more of triethylaluminum, tripropylaluminum, triisobutylaluminum, trihexylaluminum, and diisobutylaluminum hydride.
[0007] Further, the complex of component C is selected from one or more of alcohol R1(OH), ether R2(O)R3, and ketone R4(CO)R5, wherein R1, R2, R3, R4, and R5 are each independently selected from C1 to C5. 20 Alkyl or substituted alkyl, C3-C 20 cycloalkyl, C3-C 20 alkenyl, C6-C 20 aryl, C7~C 20 alkylaryl or C7~C 20 One or more of the aryl groups.
[0008] Furthermore, component D is selected from one or more of butadiene, isoprene, and isoprene.
[0009] Further, the molar ratio of nickel in component A1 and component A2 is 1:0.05 to 20, the molar ratio of nickel in component A to aluminum in component B is 1:0.1 to 5, the molar ratio of nickel in component A to boron in component C is 1:0.1 to 10, and the molar ratio of nickel in component A to component D is 1:0.001 to 200.
[0010] A method for preparing component A in a butadiene polymerization catalytic system, the method comprising the following steps:
[0011] S701, acidic phosphate ester and alkyl acid with cyclic structure are mixed in an organic solvent and heated;
[0012] S702, a saponification reaction is carried out by adding sodium hydroxide solution to a mixed solvent of acidic phosphate ester, alkyl acid with cyclic structure and organic solvent;
[0013] S703, after the saponification reaction is completed, nickel chloride solution is added to the reaction solution to carry out the metathesis reaction;
[0014] S704, after the metathesis reaction is completed, the reaction products are allowed to stand and separate into layers.
[0015] S705, after standing and stratification, the lower aqueous phase is separated and removed to obtain the upper oil phase product;
[0016] S706, the obtained upper oil phase product is refluxed using an organic solvent to remove the water and acid, and the resulting product is component A.
[0017] Further, in S701, the heating temperature is 20℃~60℃ and the heating time is 0.1h~4h; in S702, the saponification reaction temperature is 30℃~70℃ and the reaction time is 0.5h~10h; in S703, the metathesis reaction temperature is 30℃~70℃ and the reaction time is 0.5h~10h; in S704, the settling and stratification time is 4h~48h; and in S706, the reflux time is 0.5h~4h.
[0018] A method for preparing component A in a butadiene polymerization catalytic system, the method comprising the following steps:
[0019] S901, acidic phosphate esters are mixed in an organic solvent and heated;
[0020] S902, a saponification reaction is carried out by adding sodium hydroxide solution to a mixed solvent of acidic phosphate ester and organic solvent;
[0021] S903, after the saponification reaction is completed, nickel chloride solution is added to the reaction solution to carry out the metathesis reaction;
[0022] S904, After the metathesis reaction is completed, the reaction products are allowed to stand and separate into layers.
[0023] S905, after the sedimentation is completed, the lower aqueous phase is separated and removed to obtain the upper oil phase product, which is component A1.
[0024] S906, alkyl acids with cyclic structures are mixed in an organic solvent and heated;
[0025] S907, a saponification reaction is carried out by adding sodium hydroxide solution to a mixed solvent of alkyl acid with cyclic structure and organic solvent;
[0026] S908, after the saponification reaction is completed, nickel chloride solution is added to the reaction solution to carry out the metathesis reaction;
[0027] S909, After the metathesis reaction is completed, the reaction products are allowed to stand and separate into layers.
[0028] S910, after the sedimentation is completed, the lower aqueous phase is separated and removed to obtain the upper oil phase product, which is component A2.
[0029] S911, the prepared components A1 and A2 are mixed, and the mixture of components A1 and A2 is refluxed using an organic solvent to remove the water and acid. The resulting product is component A.
[0030] Further, in S901 and S906, the heating temperature is 20℃~60℃ and the heating time is 0.1h~4h; in S902 and S907, the saponification reaction temperature is 30℃~70℃ and the reaction time is 0.5h~10h; in S903 and S908, the metathesis reaction temperature is 30℃~70℃ and the reaction time is 0.5h~10h; in S904 and S909, the settling and stratification time is 1h~48h; and in S911, the reflux time is 0.5h~4h.
[0031] Furthermore, the organic solvent is selected from one or more of hexane, cyclohexane, heptane, hydrogenated gasoline, chlorobenzene, toluene, and xylene.
[0032] A method for butadiene polymerization using a butadiene polymerization catalytic system, the method comprising the following steps:
[0033] S1201, Component A is mixed with an organic solvent, component D is added to the mixed solvent, and after mixing evenly, component B is added and mixed evenly to obtain the first catalytic component;
[0034] S1202, add perhydrated butadiene to an organic solvent, mix well, and then add component C to obtain the second catalytic component;
[0035] S1203, add organic solvent and butadiene monomer to the polymerization reactor, mix evenly and then preheat;
[0036] After S1204, organic solvent and butadiene monomer are preheated, the first catalytic component and the second catalytic component are added in sequence to start the polymerization reaction;
[0037] After the polymerization reaction of S1205 is completed, the released liquid is treated with solvent removal to obtain butadiene polymer product.
[0038] Furthermore, the organic solvent is selected from one or more of hexane, cyclohexane, heptane, hydrogenated gasoline, chlorobenzene, toluene, and xylene.
[0039] Furthermore, the preheating temperature of S1203 is 20℃~60℃, the polymerization reaction temperature of S1204 is 30℃~120℃, and the polymerization reaction pressure is 0.35MPa~0.7MPa.
[0040] Furthermore, the obtained butadiene polymerization product has a butadiene conversion rate >85%.
[0041] Furthermore, the gel content of the butadiene polymer product is ≤0.3%.
[0042] Furthermore, the butadiene polymer product has a cis content ≥96% and a molecular weight distribution ≤2.5.
[0043] Furthermore, the butadiene polymer product vulcanizate has a 300% elongation ≥11.4 MPa, a tensile strength ≥17.6 MPa, and an elongation ≥480%.
[0044] The beneficial effects of this invention are:
[0045] 1. A mixture of organophosphate nickel and cyclic alkyl nickel oxide is used to replace nickel naphthenate as the nickel catalyst in the production of cis-butadiene rubber. Since the ligands of both organophosphate nickel and cyclic alkyl nickel oxide are organic compounds with defined compositions that can be synthesized, their preparation process is simpler than that of naphthenic acids. Furthermore, the product has higher purity, a defined composition, and a wide and sufficient supply of raw materials, thereby achieving the goals of reducing costs and stabilizing the production process and product quality.
[0046] 2. A mixture of organophosphate nickel and cyclic alkylate nickel is used to replace nickel naphthenate as the nickel catalyst in the production of cis-butadiene rubber. This technical solution can reduce impurities such as light oils, butter, paraffin wax, and asphalt in naphthenic acids, reduce the impact of the catalyst on the production process and the quality of the polymerized product, and improve the environmental friendliness of the production process.
[0047] 3. The production of nickel-based cis-butadiene rubber using the technical solution provided by this invention results in a high polymerization conversion rate of butadiene monomer and good physical and mechanical properties of the product. Simultaneously, the product has a low gel content, minimizing the problems of pipe adhesion and blockage caused by high gel content, thus ensuring long-term stable operation of the equipment. Detailed implementation method:
[0048] Example 1
[0049] The butadiene polymerization catalytic system used in this embodiment includes component A, component B, component C and component D. Component B is an alkyl aluminum compound, component C is a boron trifluoride complex, and component D is a homogenizing agent. Component A is composed of two parts, component A1 and component A2, wherein component A1 is nickel organophosphate and component A2 is alkyl nickel acid with a cyclic structure.
[0050] The ligand of component A1 is (2-ethylhexyl) phosphate, and component A2 is nickel cyclopentaacetate.
[0051] Component B is triisobutylaluminum.
[0052] The complex of component C is diethyl ether.
[0053] Component D is butadiene.
[0054] The molar ratio of nickel in component A1 and component A2 is 1:1, the molar ratio of nickel in component A to aluminum in component B is 1:0.2, the molar ratio of nickel in component A to boron in component C is 1:0.1, and the molar ratio of nickel in component A to component D is 1:0.01.
[0055] The preparation method of component A in the butadiene polymerization catalytic system includes the following steps:
[0056] S701, acidic phosphate ester and alkyl acid with cyclic structure are mixed in an organic solvent and heated;
[0057] S702, a saponification reaction is carried out by adding sodium hydroxide solution to a mixed solvent of acidic phosphate ester, alkyl acid with cyclic structure and organic solvent;
[0058] S703, after the saponification reaction is completed, nickel chloride solution is added to the reaction solution to carry out the metathesis reaction;
[0059] S704, after the metathesis reaction is completed, the reaction products are allowed to stand and separate into layers.
[0060] S705, after standing and stratification, the lower aqueous phase is separated and removed to obtain the upper oil phase product;
[0061] S706, the obtained upper oil phase product is refluxed using an organic solvent to remove the water and acid, and the resulting product is component A.
[0062] In S701, the heating temperature is 40℃ and the heating time is 0.5h; in S702, the saponification reaction temperature is 40℃ and the reaction time is 1h; in S703, the metathesis reaction temperature is 60℃ and the reaction time is 1.5h; in S704, the standing and stratification time is 4h; and in S706, the reflux time is 1h.
[0063] The organic solvent is hexane.
[0064] A method for butadiene polymerization using a butadiene polymerization catalytic system includes the following steps:
[0065] S1201, Component A is mixed with an organic solvent, component D is added to the mixed solvent, and after mixing evenly, component B is added and mixed evenly to obtain the first catalytic component;
[0066] S1202, add perhydrated butadiene to an organic solvent, mix well, and then add component C to obtain the second catalytic component;
[0067] S1203, add organic solvent and butadiene monomer to the polymerization reactor, mix evenly and then preheat;
[0068] After S1204, organic solvent and butadiene monomer are preheated, the first catalytic component and the second catalytic component are added in sequence to start the polymerization reaction;
[0069] S1205, after the polymerization reaction is completed, the released liquid is treated by solvent removal and other processes to obtain the polymerized product.
[0070] The organic solvent is hexane.
[0071] The preheating temperature of S1203 is 40℃. The polymerization reaction temperature of S1204 is 70℃, and the polymerization reaction pressure is 0.4MPa.
[0072] The conversion rate of butadiene was 85.61%.
[0073] The butadiene polymer obtained by the polymerization method in this embodiment has a gel content of 0.25%, a cis content of 96.41%, and a molecular weight distribution of 2.43.
[0074] The butadiene polymer vulcanizate has a 300% elongation of 11.48 MPa, a tensile strength of 17.63 MPa, and an elongation of 486%.
[0075] Example 2
[0076] The butadiene polymerization catalytic system used in this embodiment includes component A, component B, component C and component D. Component B is an alkyl aluminum compound, component C is a boron trifluoride complex, and component D is a homogenizing agent. Component A is composed of two parts, component A1 and component A2, wherein component A1 is nickel organophosphate and component A2 is alkyl nickel acid with a cyclic structure.
[0077] The ligand of component A1 is ethylhexylphosphonic acid mono-2-ethylhexyl ester, and component A2 is nickel cyclopentanoate.
[0078] Component B is diisobutylaluminum hydrogenation.
[0079] The complex of component C is diethyl ether.
[0080] Component D is butadiene.
[0081] The molar ratio of nickel in component A1 and component A2 is 1:0.05, the molar ratio of nickel in component A to aluminum in component B is 1:0.1, the molar ratio of nickel in component A to boron in component C is 1:0.1, and the molar ratio of nickel in component A to component D is 1:0.001.
[0082] The method for preparing component A in the butadiene polymerization catalytic system includes the following steps:
[0083] S901, acidic phosphate esters are mixed in an organic solvent and heated;
[0084] S902, a saponification reaction is carried out by adding sodium hydroxide solution to a mixed solvent of acidic phosphate ester and organic solvent;
[0085] S903, after the saponification reaction is completed, nickel chloride solution is added to the reaction solution to carry out the metathesis reaction;
[0086] S904, After the metathesis reaction is completed, the reaction products are allowed to stand and separate into layers.
[0087] S905, after the sedimentation is completed, the lower aqueous phase is separated and removed to obtain the upper oil phase product, which is component A1.
[0088] S906, alkyl acids with cyclic structures are mixed in an organic solvent and heated;
[0089] S907, a saponification reaction is carried out by adding sodium hydroxide solution to a mixed solvent of alkyl acid with cyclic structure and organic solvent;
[0090] S908, after the saponification reaction is completed, nickel chloride solution is added to the reaction solution to carry out the metathesis reaction;
[0091] S909, After the metathesis reaction is completed, the reaction products are allowed to stand and separate into layers.
[0092] S910, after the sedimentation is completed, the lower aqueous phase is separated and removed to obtain the upper oil phase product, which is component A2.
[0093] S911, the prepared components A1 and A2 are mixed, and the mixture of components A1 and A2 is refluxed using an organic solvent to remove the water and acid. The resulting product is component A.
[0094] The heating temperature in S901 and S906 is 30℃ and the heating time is 1h; the saponification reaction temperature in S902 and S907 is 30℃ and the reaction time is 0.5h; the metathesis reaction temperature in S903 and S908 is 30℃ and the reaction time is 0.5h; the settling and stratification time in S904 and S909 is 8h; and the reflux time in S911 is 1h.
[0095] The organic solvent is cyclohexane.
[0096] A method for butadiene polymerization using a butadiene polymerization catalytic system includes the following steps:
[0097] S1201, Component A is mixed with an organic solvent, component D is added to the mixed solvent, and after mixing evenly, component B is added and mixed evenly to obtain the first catalytic component;
[0098] S1202, add perhydrated butadiene to an organic solvent, mix well, and then add component C to obtain the second catalytic component;
[0099] S1203, add organic solvent and butadiene monomer to the polymerization reactor, mix evenly and then preheat;
[0100] After S1204, organic solvent and butadiene monomer are preheated, the first catalytic component and the second catalytic component are added in sequence to start the polymerization reaction;
[0101] S1205, after the polymerization reaction is completed, the released liquid is treated by solvent removal and other processes to obtain the polymerized product.
[0102] The organic solvent is cyclohexane.
[0103] The preheating temperature of S1203 is 20°C. The polymerization reaction temperature of S1204 is 30°C, and the polymerization reaction pressure is 0.35 MPa.
[0104] The conversion rate of butadiene was 85.76%.
[0105] The butadiene polymer obtained by the polymerization method in this embodiment has a gel content of 0.27%, a cis content of 96.39%, and a molecular weight distribution of 2.49.
[0106] The butadiene polymer vulcanizate has a 300% elongation of 11.43 MPa, a tensile strength of 17.89 MPa, and an elongation of 490%.
[0107] Example 3
[0108] The butadiene polymerization catalytic system used in this embodiment includes component A, component B, component C and component D. Component B is an alkyl aluminum compound, component C is a boron trifluoride complex, and component D is a homogenizing agent. Component A is composed of two parts, component A1 and component A2, wherein component A1 is nickel organophosphate and component A2 is alkyl nickel acid with a cyclic structure.
[0109] The ligand of component A1 is ethylhexylphosphonic acid mono-2-ethylhexyl ester, and component A2 is nickel cyclopentaacetate.
[0110] Component B is triisobutylaluminum.
[0111] The complex of component C is diethyl ether.
[0112] Component D is butadiene.
[0113] The molar ratio of nickel in component A1 and component A2 is 1:0.1, the molar ratio of nickel in component A to aluminum in component B is 1:0.2, the molar ratio of nickel in component A to boron in component C is 1:0.2, and the molar ratio of nickel in component A to component D is 1:0.002.
[0114] The method for preparing component A in the butadiene polymerization catalytic system includes the following steps:
[0115] S701, acidic phosphate ester and alkyl acid with cyclic structure are mixed in an organic solvent and heated;
[0116] S702, a saponification reaction is carried out by adding sodium hydroxide solution to a mixed solvent of acidic phosphate ester, alkyl acid with cyclic structure and organic solvent;
[0117] S703, after the saponification reaction is completed, nickel chloride solution is added to the reaction solution to carry out the metathesis reaction;
[0118] S704, after the metathesis reaction is completed, the reaction products are allowed to stand and separate into layers.
[0119] S705, after standing and stratification, the lower aqueous phase is separated and removed to obtain the upper oil phase product;
[0120] S706, the obtained upper oil phase product is refluxed using an organic solvent to remove the water and acid, and the resulting product is component A.
[0121] The heating temperature in S701 is 40℃ and the heating time is 2h; the saponification reaction temperature in S702 is 40℃ and the reaction time is 4h; the metathesis reaction temperature in S703 is 40℃ and the reaction time is 4h; the settling and stratification time in S704 is 8h; and the reflux time in S706 is 2h.
[0122] The organic solvent is cyclohexane.
[0123] A method for butadiene polymerization using a butadiene polymerization catalytic system includes the following steps:
[0124] S1201, Component A is mixed with an organic solvent, component D is added to the mixed solvent, and after mixing evenly, component B is added and mixed evenly to obtain the first catalytic component;
[0125] S1202, add perhydrated butadiene to an organic solvent, mix well, and then add component C to obtain the second catalytic component;
[0126] S1203, add organic solvent and butadiene monomer to the polymerization reactor, mix evenly and then preheat;
[0127] After S1204, organic solvent and butadiene monomer are preheated, the first catalytic component and the second catalytic component are added in sequence to start the polymerization reaction;
[0128] S1205, after the polymerization reaction is completed, the released liquid is treated by solvent removal and other processes to obtain the polymerized product.
[0129] The organic solvent is cyclohexane.
[0130] The preheating temperature of S1203 is 20°C. The polymerization reaction temperature of S1204 is 30°C, and the polymerization reaction pressure is 0.4 MPa.
[0131] The butadiene conversion rate was 86.25%.
[0132] The butadiene polymer obtained by the polymerization method in this embodiment has a gel content of 0.27%, a cis content of 96.33%, and a molecular weight distribution of 2.44.
[0133] The butadiene polymer vulcanizate has a 300% elongation of 11.50 MPa, a tensile strength of 17.88 MPa, and an elongation of 482%.
[0134] Example 4
[0135] The butadiene polymerization catalytic system used in this embodiment includes component A, component B, component C and component D. Component B is an alkyl aluminum compound, component C is a boron trifluoride complex, and component D is a homogenizing agent. Component A is composed of two parts, component A1 and component A2, wherein component A1 is nickel organophosphate and component A2 is alkyl nickel acid with a cyclic structure.
[0136] The ligand of component A1 is (2-ethylhexyl) phosphate, and component A2 is nickel cyclopentanoate.
[0137] Component B is diisobutylaluminum hydrogenation.
[0138] The complex of component C is diethyl ether.
[0139] Component D is butadiene.
[0140] The molar ratio of nickel in component A1 and component A2 is 1:0.2, the molar ratio of nickel in component A to aluminum in component B is 1:1, the molar ratio of nickel in component A to boron in component C is 1:1, and the molar ratio of nickel in component A to component D is 1:0.01.
[0141] The method for preparing component A in the butadiene polymerization catalytic system includes the following steps:
[0142] S901, acidic phosphate esters are mixed in an organic solvent and heated;
[0143] S902, a saponification reaction is carried out by adding sodium hydroxide solution to a mixed solvent of acidic phosphate ester and organic solvent;
[0144] S903, after the saponification reaction is completed, nickel chloride solution is added to the reaction solution to carry out the metathesis reaction;
[0145] S904, After the metathesis reaction is completed, the reaction products are allowed to stand and separate into layers.
[0146] S905, after the sedimentation is completed, the lower aqueous phase is separated and removed to obtain the upper oil phase product, which is component A1.
[0147] S906, alkyl acids with cyclic structures are mixed in an organic solvent and heated;
[0148] S907, a saponification reaction is carried out by adding sodium hydroxide solution to a mixed solvent of alkyl acid with cyclic structure and organic solvent;
[0149] S908, after the saponification reaction is completed, nickel chloride solution is added to the reaction solution to carry out the metathesis reaction;
[0150] S909, After the metathesis reaction is completed, the reaction products are allowed to stand and separate into layers.
[0151] S910, after the sedimentation is completed, the lower aqueous phase is separated and removed to obtain the upper oil phase product, which is component A2.
[0152] S911, the prepared components A1 and A2 are mixed, and the mixture of components A1 and A2 is refluxed using an organic solvent to remove the water and acid. The resulting product is component A.
[0153] The heating temperature in S901 and S906 is 60℃ and the heating time is 3h; the saponification reaction temperature in S902 and S907 is 50℃ and the reaction time is 6h; the metathesis reaction temperature in S903 and S908 is 50℃ and the reaction time is 6h; the settling and stratification time in S904 and S909 is 16h; and the reflux time in S911 is 3h.
[0154] The organic solvent is hexane.
[0155] A method for butadiene polymerization using a butadiene polymerization catalytic system includes the following steps:
[0156] S1201, Component A is mixed with an organic solvent, component D is added to the mixed solvent, and after mixing evenly, component B is added and mixed evenly to obtain the first catalytic component;
[0157] S1202, add perhydrated butadiene to an organic solvent, mix well, and then add component C to obtain the second catalytic component;
[0158] S1203, add organic solvent and butadiene monomer to the polymerization reactor, mix evenly and then preheat;
[0159] After S1204, organic solvent and butadiene monomer are preheated, the first catalytic component and the second catalytic component are added in sequence to start the polymerization reaction;
[0160] S1205, after the polymerization reaction is completed, the released liquid is treated by solvent removal and other processes to obtain the polymerized product.
[0161] The organic solvent is hexane.
[0162] The preheating temperature of S1203 is 30°C. The polymerization reaction temperature of S1204 is 60°C, and the polymerization reaction pressure is 0.5 MPa.
[0163] The conversion rate of butadiene was 85.09%.
[0164] The butadiene polymer obtained by the polymerization method in this embodiment has a gel content of 0.29%, a cis content of 96.44%, and a molecular weight distribution of 2.45.
[0165] The butadiene polymer vulcanizate has a 300% elongation of 11.46 MPa, a tensile strength of 17.88 MPa, and an elongation of 487%.
[0166] Example 5
[0167] The butadiene polymerization catalytic system used in this embodiment includes component A, component B, component C and component D. Component B is an alkyl aluminum compound, component C is a boron trifluoride complex, and component D is a homogenizing agent. Component A is composed of two parts, component A1 and component A2, wherein component A1 is nickel organophosphate and component A2 is alkyl nickel acid with a cyclic structure.
[0168] The ligand of component A1 is (2-ethylhexyl) phosphate, and component A2 is nickel cyclopentaacetate.
[0169] Component B is triisobutylaluminum.
[0170] The complex of component C is diethyl ether.
[0171] Component D is butadiene.
[0172] The molar ratio of nickel in component A1 and component A2 is 1:1, the molar ratio of nickel in component A to aluminum in component B is 1:5, the molar ratio of nickel in component A to boron in component C is 1:5, and the molar ratio of nickel in component A to component D is 1:0.02.
[0173] The method for preparing component A in the butadiene polymerization catalytic system includes the following steps:
[0174] S701, acidic phosphate ester and alkyl acid with cyclic structure are mixed in an organic solvent and heated;
[0175] S702, a saponification reaction is carried out by adding sodium hydroxide solution to a mixed solvent of acidic phosphate ester, alkyl acid with cyclic structure and organic solvent;
[0176] S703, after the saponification reaction is completed, nickel chloride solution is added to the reaction solution to carry out the metathesis reaction;
[0177] S704, after the metathesis reaction is completed, the reaction products are allowed to stand and separate into layers.
[0178] S705, after standing and stratification, the lower aqueous phase is separated and removed to obtain the upper oil phase product;
[0179] S706, the obtained upper oil phase product is refluxed using an organic solvent to remove the water and acid, and the resulting product is component A.
[0180] In S701, the heating temperature is 20℃ and the heating time is 4h; in S702, the saponification reaction temperature is 60℃ and the reaction time is 8h; in S703, the metathesis reaction temperature is 60℃ and the reaction time is 8h; in S704, the standing and stratification time is 24h; and in S706, the reflux time is 4h.
[0181] The organic solvent is cyclohexane.
[0182] A method for butadiene polymerization using a butadiene polymerization catalytic system includes the following steps:
[0183] S1201, Component A is mixed with an organic solvent, component D is added to the mixed solvent, and after mixing evenly, component B is added and mixed evenly to obtain the first catalytic component;
[0184] S1202, add perhydrated butadiene to an organic solvent, mix well, and then add component C to obtain the second catalytic component;
[0185] S1203, add organic solvent and butadiene monomer to the polymerization reactor, mix evenly and then preheat;
[0186] After S1204, organic solvent and butadiene monomer are preheated, the first catalytic component and the second catalytic component are added in sequence to start the polymerization reaction;
[0187] S1205, after the polymerization reaction is completed, the released liquid is treated by solvent removal and other processes to obtain the polymerized product.
[0188] The organic solvent is cyclohexane.
[0189] The preheating temperature of S1203 is 40℃. The polymerization reaction temperature of S1204 is 90℃, and the polymerization reaction pressure is 0.6MPa.
[0190] The conversion rate of butadiene was 85.93%.
[0191] The butadiene polymer obtained by the polymerization method in this embodiment has a gel content of 0.25%, a cis content of 96.69%, and a molecular weight distribution of 2.40.
[0192] The butadiene polymer vulcanizate has a 300% elongation of 11.43 MPa, a tensile strength of 17.85 MPa, and an elongation of 481%.
[0193] Example 6
[0194] The butadiene polymerization catalytic system used in this embodiment includes component A, component B, component C and component D. Component B is an alkyl aluminum compound, component C is a boron trifluoride complex, and component D is a homogenizing agent. Component A is composed of two parts, component A1 and component A2, wherein component A1 is nickel organophosphate and component A2 is alkyl nickel acid with a cyclic structure.
[0195] The ligand of component A1 is 2-ethylhexylphosphonic acid mono-2-ethylhexyl ester, and component A2 is nickel cyclopentaacetate.
[0196] Component B is diisobutylaluminum hydrogenation.
[0197] The complex of component C is diethyl ether.
[0198] Component D is butadiene.
[0199] The molar ratio of nickel in component A1 and component A2 is 1:5, the molar ratio of nickel in component A to aluminum in component B is 1:0.1, the molar ratio of nickel in component A to boron in component C is 1:10, and the molar ratio of nickel in component A to component D is 1:0.1.
[0200] The method for preparing component A in the butadiene polymerization catalytic system includes the following steps:
[0201] S901, acidic phosphate esters are mixed in an organic solvent and heated;
[0202] S902, a saponification reaction is carried out by adding sodium hydroxide solution to a mixed solvent of acidic phosphate ester and organic solvent;
[0203] S903, after the saponification reaction is completed, nickel chloride solution is added to the reaction solution to carry out the metathesis reaction;
[0204] S904, After the metathesis reaction is completed, the reaction products are allowed to stand and separate into layers.
[0205] S905, after the sedimentation is completed, the lower aqueous phase is separated and removed to obtain the upper oil phase product, which is component A1.
[0206] S906, alkyl acids with cyclic structures are mixed in an organic solvent and heated;
[0207] S907, a saponification reaction is carried out by adding sodium hydroxide solution to a mixed solvent of alkyl acid with cyclic structure and organic solvent;
[0208] S908, after the saponification reaction is completed, nickel chloride solution is added to the reaction solution to carry out the metathesis reaction;
[0209] S909, After the metathesis reaction is completed, the reaction products are allowed to stand and separate into layers.
[0210] S910, after the sedimentation is completed, the lower aqueous phase is separated and removed to obtain the upper oil phase product, which is component A2.
[0211] S911, the prepared components A1 and A2 are mixed, and the mixture of components A1 and A2 is refluxed using an organic solvent to remove the water and acid. The resulting product is component A.
[0212] The heating temperature in S901 and S906 is 40℃ and the heating time is 1h; the saponification reaction temperature in S902 and S907 is 70℃ and the reaction time is 10h; the metathesis reaction temperature in S903 and S908 is 70℃ and the reaction time is 10h; the settling and stratification time in S904 and S909 is 36h; and the reflux time in S911 is 1h.
[0213] The organic solvent is hydrogenated gasoline.
[0214] A method for butadiene polymerization using a butadiene polymerization catalytic system includes the following steps:
[0215] S1201, Component A is mixed with an organic solvent, component D is added to the mixed solvent, and after mixing evenly, component B is added and mixed evenly to obtain the first catalytic component;
[0216] S1202, add perhydrated butadiene to an organic solvent, mix well, and then add component C to obtain the second catalytic component;
[0217] S1203, add organic solvent and butadiene monomer to the polymerization reactor, mix evenly and then preheat;
[0218] After S1204, organic solvent and butadiene monomer are preheated, the first catalytic component and the second catalytic component are added in sequence to start the polymerization reaction;
[0219] S1205, after the polymerization reaction is completed, the released liquid is treated by solvent removal and other processes to obtain the polymerized product.
[0220] The organic solvent is hydrogenated gasoline.
[0221] The preheating temperature of S1203 is 50°C. The polymerization reaction temperature of S1204 is 120°C, and the polymerization reaction pressure is 0.7 MPa.
[0222] The conversion rate of butadiene was 86.12%.
[0223] The butadiene polymer obtained by the polymerization method in this embodiment has a gel content of 0.25%, a cis content of 96.77%, and a molecular weight distribution of 2.46.
[0224] The butadiene polymer vulcanizate has a 300% elongation of 11.49 MPa, a tensile strength of 17.75 MPa, and an elongation of 486%.
[0225] Example 7
[0226] The butadiene polymerization catalytic system used in this embodiment includes component A, component B, component C and component D. Component B is an alkyl aluminum compound, component C is a boron trifluoride complex, and component D is a homogenizing agent. Component A is composed of two parts, component A1 and component A2, wherein component A1 is nickel organophosphate and component A2 is alkyl nickel acid with a cyclic structure.
[0227] The ligand of component A1 is (2-ethylhexyl) phosphate, and component A2 is nickel cyclopentaacetate.
[0228] Component B is triisobutylaluminum.
[0229] The complex of component C is diethyl ether.
[0230] Component D is butadiene.
[0231] The molar ratio of nickel in component A1 and component A2 is 1:10, the molar ratio of nickel in component A to aluminum in component B is 1:0.2, the molar ratio of nickel in component A to boron in component C is 1:0.1, and the molar ratio of nickel in component A to component D is 1:0.001.
[0232] The method for preparing component A in the butadiene polymerization catalytic system includes the following steps:
[0233] S701, acidic phosphate ester and alkyl acid with cyclic structure are mixed in an organic solvent and heated;
[0234] S702, a saponification reaction is carried out by adding sodium hydroxide solution to a mixed solvent of acidic phosphate ester, alkyl acid with cyclic structure and organic solvent;
[0235] S703, after the saponification reaction is completed, nickel chloride solution is added to the reaction solution to carry out the metathesis reaction;
[0236] S704, after the metathesis reaction is completed, the reaction products are allowed to stand and separate into layers.
[0237] S705, after standing and stratification, the lower aqueous phase is separated and removed to obtain the upper oil phase product;
[0238] S706, the obtained upper oil phase product is refluxed using an organic solvent to remove the water and acid, and the resulting product is component A.
[0239] In S701, the heating temperature is 60℃ and the heating time is 2h; in S702, the saponification reaction temperature is 30℃ and the reaction time is 1h; in S703, the metathesis reaction temperature is 30℃ and the reaction time is 10h; in S704, the standing and stratification time is 48h; and in S706, the reflux time is 2h.
[0240] The organic solvent is hexane.
[0241] A method for butadiene polymerization using a butadiene polymerization catalytic system includes the following steps:
[0242] S1201, Component A is mixed with an organic solvent, component D is added to the mixed solvent, and after mixing evenly, component B is added and mixed evenly to obtain the first catalytic component;
[0243] S1202, add perhydrated butadiene to an organic solvent, mix well, and then add component C to obtain the second catalytic component;
[0244] S1203, add organic solvent and butadiene monomer to the polymerization reactor, mix evenly and then preheat;
[0245] After S1204, organic solvent and butadiene monomer are preheated, the first catalytic component and the second catalytic component are added in sequence to start the polymerization reaction;
[0246] S1205, after the polymerization reaction is completed, the released liquid is treated by solvent removal and other processes to obtain the polymerized product.
[0247] The organic solvent is hexane.
[0248] The preheating temperature of S1203 is 60°C. The polymerization reaction temperature of S1204 is 60°C, and the polymerization reaction pressure is 0.4 MPa.
[0249] The conversion rate of butadiene was 87.39%.
[0250] The butadiene polymer obtained by the polymerization method in this embodiment has a gel content of 0.28%, a cis content of 96.33%, and a molecular weight distribution of 2.48.
[0251] The butadiene polymer vulcanizate has a 300% elongation of 11.48 MPa, a tensile strength of 17.64 MPa, and an elongation of 489%.
[0252] As shown in Examples 1-7, the production of nickel-based cis-butadiene rubber using the technical solutions provided by this invention results in a high polymerization conversion rate of butadiene monomer and good physical and mechanical properties of the product. Simultaneously, the product has a low gel content, minimizing the problems of pipe adhesion and blockage caused by high gel content, thus ensuring long-term stable operation of the equipment.
[0253] It is understood that the above specific description of the present invention is only for illustrating the present invention and is not limited to the technical solutions described in the embodiments of the present invention. Those skilled in the art should understand that modifications or equivalent substitutions can still be made to the present invention to achieve the same technical effect; as long as the use needs are met, they are all within the protection scope of the present invention.
Claims
1. A butadiene polymerization catalytic system, comprising component A, component B, component C, and component D, wherein component B is an alkylaluminum compound, component C is a boron trifluoride complex, and component D is a homogenizing agent; characterized in that: Component A consists of two parts: component A1 and component A2, wherein component A1 is nickel organophosphate and component A2 is nickel alkyl acid with a cyclic structure.
2. The butadiene polymerization catalytic system according to claim 1, characterized in that: The ligand of component A1 is selected from one or more of (2-ethylhexyl) phosphate and 2-ethylhexylphosphonic acid mono-2-ethylhexyl ester, and component A2 is selected from C6 to C6. 20 One or more of alkyl nickel oxides having a cyclic structure, wherein the cyclic structure is one or more of a four-membered ring, a five-membered ring, a six-membered ring, or a benzene ring.
3. The butadiene polymerization catalytic system according to claim 1, characterized in that: Component B is selected from one or more of triethylaluminum, tripropylaluminum, triisobutylaluminum, trihexylaluminum, and diisobutylaluminum hydride.
4. The butadiene polymerization catalytic system according to claim 1, characterized in that: The complex of component C is selected from one or more of alcohols R1(OH), ethers R2(O)R3, and ketones R4(CO)R5, wherein R1, R2, R3, R4, and R5 are each independently selected from C1 to C5. 20 Alkyl or substituted alkyl, C3-C 20 cycloalkyl, C3-C 20 alkenyl, C6-C 20 aryl, C7~C 20 alkylaryl or C7~C 20 One or more of the aryl groups.
5. The butadiene polymerization catalytic system according to claim 1, characterized in that: The component D is selected from one or more of butadiene, isoprene and isoprene.
6. The butadiene polymerization catalytic system according to claim 1, characterized in that: The molar ratio of nickel in component A1 and component A2 is 1:0.05 to 20, the molar ratio of nickel in component A to aluminum in component B is 1:0.1 to 5, the molar ratio of nickel in component A to boron in component C is 1:0.1 to 10, and the molar ratio of nickel in component A to component D is 1:0.001 to 200.
7. A method for preparing component A in the butadiene polymerization catalytic system according to claim 1, characterized in that: The method includes the following steps: S701, acidic phosphate ester and alkyl acid with cyclic structure are mixed in an organic solvent and heated; S702, a saponification reaction is carried out by adding sodium hydroxide solution to a mixed solvent of acidic phosphate ester, alkyl acid with cyclic structure and organic solvent; S703, after the saponification reaction is completed, nickel chloride solution is added to the reaction solution to carry out a metathesis reaction; S704, After the metathesis reaction is completed, the reaction products are allowed to stand and separate into layers. S705, after standing and stratification, the lower aqueous phase is separated and removed to obtain the upper oil phase product; S706, the obtained upper oil phase product is refluxed using an organic solvent to remove the water and acid, and the resulting product is component A.
8. The method for preparing component A in the butadiene polymerization catalytic system according to claim 7, characterized in that: In S701, the heating temperature is 20℃~60℃ and the heating time is 0.1h~4h; in S702, the saponification reaction temperature is 30℃~70℃ and the reaction time is 0.5h~10h; in S703, the metathesis reaction temperature is 30℃~70℃ and the reaction time is 0.5h~10h; in S704, the standing and stratification time is 4h~48h; and in S706, the reflux time is 0.5h~4h.
9. A method for preparing component A in the butadiene polymerization catalytic system according to claim 1, characterized in that: The method includes the following steps: S901, acidic phosphate esters are mixed in an organic solvent and heated; S902, a saponification reaction is carried out by adding sodium hydroxide solution to a mixed solvent of acidic phosphate ester and organic solvent; S903, after the saponification reaction is completed, nickel chloride solution is added to the reaction solution to carry out the metathesis reaction; S904, After the metathesis reaction is completed, the reaction products are allowed to stand and separate into layers. S905, after the sedimentation is completed, the lower aqueous phase is separated and removed to obtain the upper oil phase product, which is component A1. S906, alkyl acids with cyclic structures are mixed in an organic solvent and heated; S907, a saponification reaction is carried out by adding sodium hydroxide solution to a mixed solvent of alkyl acid with cyclic structure and organic solvent; S908, after the saponification reaction is completed, nickel chloride solution is added to the reaction solution to carry out a metathesis reaction; S909, After the metathesis reaction is completed, the reaction products are allowed to stand and separate into layers. S910, after the sedimentation is completed, the lower aqueous phase is separated and removed to obtain the upper oil phase product, which is component A2. S911, the prepared components A1 and A2 are mixed, and the mixture of components A1 and A2 is refluxed using an organic solvent to remove the water and acid. The resulting product is component A.
10. The method for preparing component A in the butadiene polymerization catalytic system according to claim 9, characterized in that: The heating temperature in S901 and S906 is 20℃~60℃, and the heating time is 0.1h~4h; the saponification reaction temperature in S902 and S907 is 30℃~70℃, and the reaction time is 0.5h~10h; the metathesis reaction temperature in S903 and S908 is 30℃~70℃, and the reaction time is 0.5h~10h; the settling and stratification time in S904 and S909 is 1h~48h, and the reflux time in S911 is 0.5h~4h.
11. The method for preparing component A in the butadiene polymerization catalytic system according to claims 7 and 9, characterized in that: The organic solvent is selected from one or more of hexane, cyclohexane, heptane, hydrogenated gasoline, chlorobenzene, toluene, and xylene.
12. A method for butadiene polymerization using the butadiene polymerization catalytic system according to claim 1, characterized in that: The method includes the following steps: S1201, Component A is mixed with an organic solvent, component D is added to the mixed solvent, and after mixing evenly, component B is added and mixed evenly to obtain the first catalytic component; S1202, add perhydrated butadiene to an organic solvent, mix well, and then add component C to obtain the second catalytic component; S1203, add organic solvent and butadiene monomer to the polymerization reactor, mix evenly and then preheat; After S1204, organic solvent and butadiene monomer are preheated, the first catalytic component and the second catalytic component are added in sequence to start the polymerization reaction; After the polymerization reaction of S1205 is completed, the released liquid is treated with solvent removal to obtain butadiene polymer product.
13. The method for butadiene polymerization using a butadiene polymerization catalytic system according to claim 12, characterized in that: The organic solvent is selected from one or more of hexane, cyclohexane, heptane, hydrogenated gasoline, chlorobenzene, toluene, and xylene.
14. The method for butadiene polymerization using a butadiene polymerization catalytic system according to claim 12, characterized in that: The preheating temperature of S1203 is 20℃~60℃, the polymerization reaction temperature of S1204 is 30℃~120℃, and the polymerization reaction pressure is 0.35MPa~0.7MPa.
15. The method for butadiene polymerization using a butadiene polymerization catalytic system according to claim 12, characterized in that: The obtained butadiene polymerization product has a butadiene conversion rate >85%.
16. The method for butadiene polymerization using a butadiene polymerization catalytic system according to claim 12, characterized in that: The gel content of the butadiene polymer product is ≤0.3%.
17. The method for butadiene polymerization using a butadiene polymerization catalytic system according to claim 16, characterized in that: The butadiene polymer product has a cis content ≥96% and a molecular weight distribution ≤2.
5.
18. The method for butadiene polymerization using a butadiene polymerization catalytic system according to claim 16, characterized in that: The butadiene polymer vulcanizate has a 300% elongation ≥11.4 MPa, a tensile strength ≥17.6 MPa, and an elongation ≥480%.