CN113185673A - Carbon-based catalyst, preparation method thereof and catalyst system for dicyclopentadiene polymerization - Google Patents
Carbon-based catalyst, preparation method thereof and catalyst system for dicyclopentadiene polymerization Download PDFInfo
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- C08G61/06—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms prepared by ring-opening of carbocyclic compounds
- C08G61/08—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms prepared by ring-opening of carbocyclic compounds of carbocyclic compounds containing one or more carbon-to-carbon double bonds in the ring
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Abstract
The invention relates to the technical field of dicyclopentadiene polymerization catalysts, and provides a carbon-based catalyst, a preparation method thereof and a catalyst system for dicyclopentadiene polymerization. The invention adopts acid to carry out activation pretreatment on the carbon carrier, so that a large amount of phenolic hydroxyl groups are formed on the surface of the carbon carrier, and then the active component is loaded on the carbon carrier through chelation of transition metal ions and the phenolic hydroxyl groups, thereby improving the activity and stability of the catalyst. The carbon-based catalyst provided by the invention has higher activity and stability and is stable to air, and the mechanical property of a product can be improved by taking the carbon-based catalyst as a main catalyst for dicyclopentadiene polymerization, so that the polymerization reaction has a proper operation window, and the industrial production is facilitated.
Description
Technical Field
The invention relates to the technical field of dicyclopentadiene polymerization catalysts, in particular to a carbon-based catalyst, a preparation method thereof and a catalyst system for dicyclopentadiene polymerization.
Background
The dicyclopentadiene is a byproduct of ethylene preparation by petroleum cracking and coal coking, has a structure shown in formula I, contains two unsaturated double bonds, can generate ring-opening metathesis polymerization reaction on two rings containing the unsaturated double bonds, and can easily generate self-polymerization reaction on a dicyclopentadiene monomer. The dicyclopentadiene has wide application prospect in the fields of fine chemical engineering and high-molecular chemistry, has great scientific research value and economic benefit, and the polymer thereof is widely applied to the industries such as agriculture, automobiles, chemical engineering and the like by excellent performance.
The dicyclopentadiene reaction injection molding process was a technology developed by Hercules and Goodrich in the United states in the 80 th century and allows the rapid preparation of complex shaped articles from low viscosity monomers. At present, the technology is widely applied to the preparation of automobile covering parts, and the technology must replace glass fiber reinforced plastic products to become a main body of light weight materials of vehicles.
The ring-opening metathesis polymerization is the key for preparing polydicyclopentadiene and is also the key link of the dicyclopentadiene reaction injection molding process. The catalyst is the core of ring-opening metathesis polymerization, and the structure and performance of the product can be influenced by the factors such as activity, stability and the like of the catalyst, and the industrial application value of the catalyst is also determined. At present, dicyclopentadiene ring-opening metathesis polymerization catalysts are mainly classified into two types, two-component catalysts and single-component catalysts. The single-component catalyst is metal carbene and metal alkyl alkene, and the catalyst has high activity and good environmental stability, but has high price and poor manufacturability, and is not widely applied in industry.
The bi-component catalyst consists of a main catalyst and an auxiliary catalyst, wherein the main catalyst is a complex of transition metals such as tungsten, molybdenum, ruthenium and the like, and the auxiliary catalyst is a metal organic matter such as aluminum, magnesium, tin, zinc and the like. The main catalyst plays a determining role in the formation of the metal carbene, and the auxiliary catalyst can promote the formation of the metal carbene and improve the catalytic activity. WCl6And MoCl5The complex with the substituted hindered phenol is a main catalyst applied in the industry at present, and the benzene oxide or the phenol salt of tungsten can well catalyze the ring opening metathesis polymerization of dicyclopentadiene under the action of a metal organic cocatalyst. The electronic effect and steric hindrance of the substituted sterically hindered phenolic ligands are determinative of the catalyst activity and stabilityKey factors of sex. WCl6And MoCl5The stability of the catalyst can be improved after the catalyst is coordinated with substituted sterically hindered phenol, the electron donating performance of the phenol ligand increases the electron cloud density of metal ions, and the stability of the metal carbene complex is improved, so that the catalytic efficiency of the catalyst is improved.
The steric hindrance effect of the ligand also has great influence on the activity of the catalyst, and researches show that the larger the steric hindrance around the metal central ion, the higher the catalytic activity is. Loading the transition metal central ion on the solid surface will undoubtedly increase the steric hindrance around the metal ion. Currently, researchers have catalyzed dicyclopentadiene polymerization with polystyrene and molecular sieve supported tungsten catalysts. Researches show that the activity of the polystyrene supported catalyst is higher than that of the unsupported catalyst, the stability is better, and the catalyst supported by the molecular sieve also shows higher activity. However, the polystyrene supported tungsten catalyst belongs to physical embedding, the specific surface area is small, the utilization rate of the catalyst is low, the molecular sieve has large specific surface area, but the coordination group on the surface of the molecular sieve is not as good as the phenoxy group in the aspect of power supply, and the dispersion of the molecular sieve in dicyclopentadiene has some problems, which can affect the properties of polydicyclopentadiene.
Disclosure of Invention
In view of the above, the present invention is directed to a carbon-based catalyst, a method for preparing the same, and a catalyst system for dicyclopentadiene polymerization. The carbon-based catalyst is used as a main catalyst for catalyzing the polymerization of dicyclopentadiene, and the obtained catalyst system has high activity, good stability, high utilization rate of the catalyst and good dispersibility in dicyclopentadiene.
In order to achieve the above object, the present invention provides the following technical solutions:
a preparation method of a carbon-based catalyst comprises the following steps:
(1) activating and pretreating the carbon carrier by using acid to obtain an activated carbon carrier;
(2) mixing the activated carbon carrier and the active component mixed solution for impregnation to obtain a carbon-based catalyst; the active component in the active component mixed solution comprises a transition metal oxychloride complex.
Preferably, the preparation method of the active component mixed solution comprises the following steps:
mixing a first ligand, a transition metal chloride and a solvent for reaction to obtain a reaction solution;
sequentially adding a second ligand and a third ligand into the reaction solution to obtain an active component mixed solution;
the transition metal chloride comprises WCl6、MoCl5And RuCl4One or more of the above; the first ligand comprises tert-butyl alcohol and/or di-tert-butyl-p-cresol; the second ligand comprises one or more of nonyl phenol, 4-dimethyl-6-tert-butyl phenol, 2, 6-diamyl hydroquinone, 2, 6-diamyl tert-butyl phenol, 4' -ethylidene bis (6-tert-butyl-o-cresol), polyhydric phenol ligand, bisphenol ligand, tert-butyl catechol, hydrogen phenol, resorcinol and 1,2, 3-benzenetriol; the third ligand comprises one or more of 2, 4-pentanedione and acetylacetone ester ligands;
the molar ratio of the first ligand to the transition metal chloride is 0.1-1: 1; the molar ratio of the second ligand to the transition metal chloride is 1-5: 1; the molar ratio of the third ligand to the transition metal chloride is 1-5: 1.
Preferably, in the reaction solution, the molar ratio of the transition metal chloride to the transition metal oxychloride is 0.5-5: 1.
Preferably, after adding the second ligand, the method comprises the step of adding the obtained feed liquid N2Bubbling for 1-2 h; after the third ligand is added, the method also comprises the step of adding the obtained feed liquid N2Bubbling for 1-2 h.
Preferably, the acid comprises one or more of nitric acid, acetic acid, hydrochloric acid and sulfuric acid; the weight ratio of the carbon carrier to the acid is 1: 2-3, the temperature of the activation pretreatment is 30-80 ℃, and the treatment time is 3-8 hours.
Preferably, the dosage ratio of the activated carbon carrier to the active component mixed solution is 1g: 20-200 mL, and the impregnation time is 20-30 h.
The invention also provides a carbon-based catalyst prepared by the preparation method in the scheme, which comprises an activated carbon carrier and an active component loaded on the activated carbon carrier, wherein the active component comprises a transition metal oxychlorid complex.
The invention also provides a catalyst system for dicyclopentadiene polymerization, which comprises a main catalyst and a cocatalyst which are independently and separately packaged, wherein the main catalyst is the carbon-based catalyst in the claim 7, and the cocatalyst is an organic aluminum compound.
The invention also provides a method for preparing dicyclopentadiene polymeric material by using the catalyst system in the scheme, which comprises the following steps:
(1) respectively dispersing a main catalyst and a cocatalyst in materials to be polymerized with the same volume under a protective atmosphere to obtain a component A and a component B;
the material to be polymerized is a dicyclopentadiene monomer, or the material to be polymerized comprises a cyclopentadiene monomer and a composite component;
(2) and mixing the component A and the component B under a protective atmosphere, and carrying out heat treatment to obtain the dicyclopentadiene polymeric material.
Preferably, the molar ratio of the total molar quantity of the dicyclopentadiene in the component A and the component B to the main catalyst and the cocatalyst is (1200-1500): 1 (10-30); the molar weight of the main catalyst is calculated by the molar weight of a transition metal element, and the molar weight of the auxiliary catalyst is calculated by the mass of an Al element.
The invention provides a preparation method of a carbon-based catalyst, which comprises the steps of carrying out activation pretreatment on a carbon carrier by using acid, mixing the obtained activated carrier and an active component mixed solution, and impregnating to obtain the carbon-based catalyst; the active component in the active component mixed solution comprises a transition metal oxychloride complex. According to the invention, the carbon carrier is subjected to activation pretreatment by using acid, so that a large amount of phenolic hydroxyl groups are formed on the surface of the carbon carrier, and the phenolic hydroxyl groups can be chelated and coordinated with transition metal ions to form a stable complex, thereby being beneficial to improving the stability and catalytic activity of the catalyst; in addition, carbonyl and pyrone groups on the surface of the carbon carrier can play a role of Lewis base and control the electron cloud density around the active center of the transition metal, so that the activity of the catalyst is regulated, a polymerization reaction has a proper operation window, and the industrial production is facilitated.
Compared with a polystyrene supported tungsten catalyst, the transition metal ions in the carbon-based catalyst provided by the invention form coordination bonds with phenolic hydroxyl groups on the surface of a carbon carrier, the obtained complex has a stable structure, the polystyrene supported tungsten catalyst is only physically embedded and does not have a chemical bond effect, and the structure of the catalyst is unstable; furthermore, the carbon carrier adopted by the invention has higher specific surface area, can load more active components, and has high utilization rate of the catalyst, smaller specific surface area of polystyrene and lower utilization rate of the catalyst.
Compared with a molecular sieve supported catalyst, although the molecular sieve has a larger specific surface area, coordination groups on the surface of the molecular sieve have poor electricity supply performance and poor regulation and control effect on the electron density of transition metal ions, and the activated carbon carrier can play a role in regulating and controlling the electron cloud density and increase an operation window; furthermore, only mesopores are arranged in the molecular sieve without pores with other pore diameters, which can influence the transmission of cocatalyst and monomer to central ions and reduce the utilization rate of the central ions, and the carbon carrier adopted by the invention has larger pore diameter distribution (0.8-1.1 cm)3/g) and has some through holes to facilitate the transport of cocatalyst and monomer; in addition, the dispersibility of the carbon carrier in the dicyclopentadiene monomer is much better than that of the inorganic molecular sieve, and the property of the polydicyclopentadiene product cannot be influenced.
The invention also provides a catalyst system for dicyclopentadiene polymerization, which comprises a main catalyst and a cocatalyst which are independently and separately packaged, wherein the main catalyst is the carbon-based catalyst in the scheme. The carbon-based catalyst provided by the invention has higher activity and stability and is stable to air, and the carbon-based catalyst is used as a main catalyst for polymerization of dicyclopentadiene, so that the polymerization reaction has a proper operation window, the production operation is convenient, and the industrial production is convenient.
The invention also provides a method for preparing the dicyclopentadiene polymeric material, which comprises the steps of respectively dispersing the main catalyst and the cocatalyst into a material to be polymerized containing dicyclopentadiene monomers with the same volume to obtain a component A and a component B, and then mixing the component A and the component B for polymerization reaction. The method provided by the invention is convenient to operate, and the obtained product has high mechanical property.
Detailed Description
The invention provides a preparation method of a carbon-based catalyst, which comprises the following steps:
(1) activating and pretreating the carbon carrier by using acid to obtain an activated carbon carrier;
(2) mixing the activated carbon carrier and the active component mixed solution for impregnation to obtain a carbon-based catalyst; the active component in the active component mixed solution comprises a transition metal oxychloride complex.
The invention uses acid to carry out activation pretreatment on the carbon carrier to obtain the activated carbon carrier. The invention uses acid to carry out activation pretreatment on the carbon carrier to obtain the activated carbon carrier. In the invention, the carbon carrier is preferably one or more of activated carbon, carbon black and mesoporous carbon; the specific surface area of the carbon carrier is preferably 500-3000 m2A concentration of 1500 to 2000m2The particle size is preferably 1 to 20 μm, more preferably 1 to 5 μm.
In the invention, the acid preferably comprises one or more of nitric acid, acetic acid, hydrochloric acid and sulfuric acid; the concentration of the nitric acid is preferably 0.5-7 mol/L, more preferably 1-6 mol/L, the concentration of the acetic acid is preferably 0.1-5 mol/L, more preferably 1-4 mol/L, the concentration of the hydrochloric acid is preferably 0.1-5 mol/L, more preferably 1-4 mol/L, and the concentration of the sulfuric acid is preferably 0.1-3 mol/L, more preferably 1-2 mol/L; the weight ratio of the carbon carrier to the acid is preferably 1: 2-3, more preferably 1:2.5, the temperature of the activation pretreatment is preferably 30-80 ℃, more preferably 40-70 ℃, and the treatment time of the activation pretreatment is preferably 3-8 hours, more preferably 4-7 hours. In the invention, the activation pretreatment is to soak the carbon carrier in acid, take out the carbon carrier after soaking, wash the carbon carrier with distilled water for 3 times, and dry the carbon carrier at 120 ℃ to constant weight. The carbon carrier has high specific surface area and proper pore diameter, a large number of phenolic hydroxyl groups are formed on the surface after activation pretreatment, the phenolic hydroxyl groups can be chelated and coordinated with transition metal ions to form stable complexes, and the formed complexes are stable and have higher steric hindrance than micromolecular phenolic ligands.
After the activated carbon carrier is obtained, the activated carbon carrier and the active component mixed solution are mixed and impregnated to obtain the carbon-based catalyst. In the present invention, the active component in the active component mixture solution includes a transition metal oxychloride complex.
In the present invention, the preparation method of the active ingredient mixed solution preferably includes the steps of:
mixing a first ligand, a transition metal chloride and a solvent for reaction to obtain a reaction solution;
and sequentially adding a second ligand and a third ligand into the reaction solution to obtain an active component mixed solution.
According to the invention, a first ligand, a transition metal chloride and a solvent are mixed for reaction to obtain a reaction solution. In the present invention, the transition metal chloride preferably comprises WCl6、MoCl5And RuCl4One or more of the above; the first ligand comprises tert-butyl alcohol and/or di-tert-butyl-p-cresol; the molar ratio of the first ligand to the transition metal chloride is 0.1-1: 1, and more preferably 0.25: 1; the solvent is preferably toluene and/or xylene; the toluene and xylene are preferably used after drying; the amount ratio of the transition metal chloride to the solvent is preferably 2 g: 7 mL. In the present invention, the reaction is preferably carried out in a protective atmosphere, preferably N2(ii) a The reaction time is preferably 5-25 h, and the reaction temperature is preferably room temperature; taking tungsten chloride and tert-butyl alcohol as an example, the reaction process is as follows:
WCl6+ROH→ROWCl5→WOCl4+RCl
in the present invention, the molar ratio of the transition metal chloride to the transition metal oxychloride in the reaction solution is preferably 0.5 to 5:1, and more preferably 3: 1.
After the reaction solution is obtained, the second ligand and the third ligand are sequentially added into the reaction solution to obtain the active component mixed solution. In the present invention, the second ligand preferably includes one or more of nonylphenol, 4-dimethyl-6-tert-butylphenol, 2, 6-dipentylhydroquinone, 2, 6-di-tert-butylphenol, 4' -monoethylene bis (6-tert-butyl-o-cresol), polyhydric phenol ligands, bisphenol ligands, tert-butylcatechol, hydroquinone, resorcinol and 1,2, 3-benzenetrisol; the molar ratio of the second ligand to the transition metal chloride is preferably 1-5: 1, and more preferably 2-3: 1; in the invention, a second ligand is preferably dissolved in a solvent to obtain a second ligand solution, and then the second ligand solution is added into the reaction solution, wherein the solvent is consistent with the solvent used in the scheme in kind, and is not described herein again; the concentration of the second ligand solution is preferably 0.3-0.4 g/mL; according to the invention, it is preferred that a solution of the second ligand is added to the reaction solution, and then N2Bubbling for 1-2 h to remove HCl generated in the coordination process. In the present invention, the nonylphenol as a ligand can coordinate with a transition metal chloride and a transition metal oxychloride in the reaction solution, and further, the nonylphenol can play a role in oxidation resistance and catalyst deactivation prevention.
In the invention, the third ligand preferably comprises one or more of 2, 4-pentanedione and acetylacetone ester ligands, and the molar ratio of the third ligand to the transition metal chloride is preferably 1-5: 1, and more preferably 2-3: 1. The invention preferably uses a syringe to add 2, 4-pentanedione into the feed liquid; after the addition of the 2, 4-pentanedione is complete, N is again preferred in the present invention2Bubbling for 1-2 h to remove HCl generated in the coordination process. In the present invention, the 2, 4-pentanedione can coordinate with the transition metal chloride and the transition metal oxychloride in the reaction liquid and at the same time, functions to stabilize the complex.
In the present invention, the components of the active component mixed solution finally obtained by the above method are transition metal oxychloride with different coordination numbers. The ligand is adopted for coordination, so that the activity of the transition metal chloride can be reduced, the main catalyst is prevented from directly initiating monomer polymerization in the application process, and the stability of the catalyst is improved.
After the active component mixed solution is obtained, the activated carbon carrier and the active component mixed solution are mixed and impregnated. In the invention, the dosage ratio of the activated carbon carrier to the active component mixed solution is preferably 1g: 20-200 mL, and more preferably 1g: 50-150 mL; the soaking time is preferably 20-30 h, and more preferably 24 h; the impregnation is preferably carried out with stirring and under nitrogen protection. In the dipping process, the transition metal ions and the phenolic hydroxyl on the carbon carrier are chelated and coordinated, so that the carbon-based catalyst with high activity and high stability is obtained.
In the invention, the feed liquid obtained after impregnation is the suspension of the carbon-based catalyst, and the suspension is directly used as the catalyst without any treatment.
The invention provides a carbon-based catalyst prepared by the preparation method in the scheme, which comprises an activated carbon carrier and an active component loaded on the activated carbon carrier, wherein the active component comprises a transition metal oxychlorid complex; the ligands in the transition metal oxychloride complex preferably include the first ligand, the second ligand and the third ligand described in the above scheme, and the metal central ion in the active component and the phenolic hydroxyl group on the surface of the activated carbon support form a stable chelate. In the invention, the loading amount of the transition metal element in the carbon-based catalyst is preferably 5-50 wt%, and more preferably 10-40 wt%.
The invention also provides a catalyst system for dicyclopentadiene polymerization, which comprises a main catalyst and a cocatalyst which are independently and separately packaged, wherein the main catalyst is the carbon-based catalyst in the scheme, and the cocatalyst is an organic aluminum compound; the organic aluminum compound is preferably diethyl aluminum chloride, triethyl aluminum or ethyl aluminum dichloride.
The invention also provides a method for preparing dicyclopentadiene polymeric material by using the catalyst system in the scheme, which comprises the following steps:
(1) respectively dispersing a main catalyst and a cocatalyst in materials to be polymerized with the same volume under a protective atmosphere to obtain a component A and a component B;
(2) and mixing the component A and the component B under a protective atmosphere, and carrying out heat treatment to obtain the dicyclopentadiene polymeric material.
In the invention, under the protective atmosphere, a main catalyst and a cocatalyst are respectively dispersed in a material to be polymerized with the same volume to obtain a component A and a component B. In the present invention, the protective atmosphere is preferably an inert gas or nitrogen; the material to be polymerized is dicyclopentadiene monomer, or the material to be polymerized comprises cyclopentadiene monomer and a composite component, wherein the composite component preferably comprises one or more of vinyl norbornene monomer, methacryloyl norbornene monomer and butadiene-styrene block copolymer.
In the invention, when the material to be polymerized is dicyclopentadiene monomer, the final product is polydicyclopentadiene; when the material to be polymerized is a mixture of cyclopentadiene monomers and vinyl norbornene monomers, the mass fraction of the vinyl norbornene monomers in the mixture is preferably 5%, and the final product is a copolymer of dicyclopentadiene and vinyl norbornene; when the material to be polymerized is a mixture of cyclopentadiene monomers and methacryloyl norbornene monomers, the mass fraction of the methacryloyl norbornene monomers in the mixture is preferably 5%, and the final product is a copolymer of dicyclopentadiene and methacryloyl norbornene; when the material to be polymerized is a mixture of cyclopentadiene monomers and butadiene-styrene block copolymers, the mass fraction of the butadiene-styrene block copolymers in the mixture is preferably 6%, and the final product is a composite material of dicyclopentadiene and butadiene-styrene block copolymers; when the material to be polymerized is a mixture of cyclopentadiene monomer, vinyl norbornene monomer and butadiene-styrene block copolymer, the mass fraction of vinyl norbornene monomer in the mixture is preferably 5%, the mass fraction of butadiene-styrene block copolymer is preferably 6%, and the final product is a composite material of dicyclopentadiene-methacryloyl norbornene copolymer and butadiene-styrene block copolymer. In the present invention, the butadiene-styrene block copolymer functions as a reinforcing material.
In the invention, when the material to be polymerized is dicyclopentadiene, a main catalyst and a cocatalyst are directly and respectively added into the dicyclopentadiene with the same volume for mixing; when the material to be polymerized comprises cyclopentadiene monomers and a composite component, the cyclopentadiene monomers and the composite component are preferably mixed and then divided into two parts with equal volumes, then a main catalyst and a cocatalyst are respectively added, and particularly, when the composite component comprises a butadiene-styrene block copolymer, the dicyclopentadiene and the butadiene-styrene block copolymer are preferably mixed and then stirred for 30-60 min at 60 ℃ to obtain a uniform and transparent solution, then the solution is divided into two parts with equal volumes, and then the subsequent steps are carried out.
In the present invention, the main catalyst is preferably directly added in the form of the carbon-supported catalyst suspension obtained in the above scheme, and the cocatalyst is preferably dissolved in toluene and then added in the form of a diethylaluminum chloride solution.
In the invention, the molar ratio of the total molar amount of dicyclopentadiene in the component A and the component B to the main catalyst and the cocatalyst is preferably (1200-1500): 1 (10-30), more preferably (1300-1400): 1 (15-25); the molar weight of the main catalyst is calculated by the molar weight of a transition metal element, and the molar weight of the auxiliary catalyst is calculated by the mass of an Al element.
After the component A and the component B are obtained, the component A and the component B are mixed and subjected to heat treatment under a protective atmosphere to obtain the dicyclopentadiene polymeric material. In the present invention, the temperature of the heat treatment is preferably 70 ℃; the component A and the component B are preferably quickly mixed together, the viscosity of the mixture is increased within 10-30 s, the mixture is transferred into a preheated mold, and the mixture is quickly cured within 60-200 s to form a crosslinked solid, so that the dicyclopentadiene polymeric material is obtained.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention.
In the following examples, activated carbon is used as a carrier, and the specific surface area of the activated carbon is 500 to 2000m2(iii) a particle size of 0.02 to 20 μm/g.
Example 1: preparation of carbon-supported tungsten catalyst
(1) Under the protection of nitrogen, tert-butyl alcohol and WCl are added6Mixing with dry toluene, and stirring for 10 hr, wherein WCl6In an amount of 20g, toluene in a volume of 70mL, tert-butanol and WC16The molar ratio was 0.25 to obtain a reaction solution in which WC1 was present6And WOC14Has a total concentration of 0.73mol/L, WC16With WOCl4Is 3: 1.
(2) Adding 11.1g of nonylphenol to 30 ml of toluene to obtain a nonylphenol solution, adding the nonylphenol solution to the reaction solution of step (1), and then adding N2The HCl was removed by bubbling for 1 hour, after which 10.1g of 2, 4-pentanedione were added by syringe and the mixture was again purged with N2Bubbling for 1h to remove HCl and obtain a mixed active ingredient solution.
(3) The activated carbon is subjected to activation pretreatment by using 1mol/L nitric acid, the weight ratio of the carbon carrier to the nitric acid is 1:3, the treatment temperature is 30 ℃, the treatment time is 3 hours, the treated carbon carrier is washed three times by using distilled water, and the carbon carrier is dried to constant weight at the temperature of 120 ℃ to obtain the activated carbon carrier.
(4) And (3) adding 5g of the activated carbon carrier prepared in the step (3) into the mixed active component solution in the step (2), and stirring for 24 hours under the protection of nitrogen to form uniform and stable black suspension, namely the carbon-supported tungsten catalyst.
Example 2: preparation of carbon-supported molybdenum catalyst
(1) Under the protection of nitrogen, adding di-tert-butyl-p-cresol and MoCl5Mixing with dry toluene, stirring for 10h, wherein MoCl5The amount of the compound (B) is 10g, the volume of the methylbenzene is 50mL, and the di-tert-butyl-p-cresol and MoCl are5The molar ratio was 0.25 to obtain a reaction solution in which MoC1 was present5And MoOC13Has a total concentration of 0.73mol/L and MoC15With MoOCl4Is about 3: 1.
(2) Will be provided with11.1g of nonylphenol was added to 30 ml of toluene to obtain a nonylphenol solution, and the nonylphenol solution was added to the reaction solution of step (1), followed by adding N2The HCl was removed by bubbling for 1 hour, after which 10.1g of 2, 4-pentanedione were added by syringe and the mixture was again purged with N2Bubbling for 1h to remove HCl and obtain a mixed active ingredient solution.
(3) Activating and pretreating activated carbon by using 1mol/L acetic acid, wherein the weight ratio of a carbon carrier to nitric acid is 1:3, the treatment temperature is 30 ℃, the treatment time is 3 hours, the treated carbon carrier is washed by using distilled water for three times, and the carbon carrier is dried to constant weight at the temperature of 120 ℃. Obtaining the activated carbon carrier.
(4) And (3) adding 5g of the activated carbon carrier prepared in the step (3) into the mixed active component solution in the step (2), and stirring for 24 hours under the protection of nitrogen to form uniform and stable black suspension, namely the carbon-supported molybdenum catalyst.
Example 3: preparation of carbon-supported ruthenium catalyst:
(1) under the protection of nitrogen, di-tert-butyl-p-cresol and RuCl are added4Mixing with dry toluene and stirring for 10h, wherein RuCl6The amount of the compound (B) is 10g, the volume of the toluene is 70mL, and the di-tert-butyl-p-cresol and MoCl are adopted6The molar ratio was 0.25, and a reaction solution was obtained.
(2) Adding 11.1g of nonylphenol to 30 ml of toluene to obtain a nonylphenol solution, adding the nonylphenol solution to the reaction solution obtained in the step (1), and then adding N2The HCl was removed by bubbling for 1 hour, after which 10.1g of 2, 4-pentanedione were added by syringe and the mixture was again purged with N2Bubbling for 1h to remove HCl and obtain a mixed active ingredient solution.
(3) Activating and pretreating activated carbon by using 1mol/L hydrochloric acid, wherein the weight ratio of a carbon carrier to nitric acid is 1:3, the treatment temperature is 30 ℃, the treatment time is 3 hours, the treated carbon carrier is washed three times by using distilled water, and the carbon carrier is dried to constant weight at the temperature of 120 ℃. Obtaining the activated carbon carrier.
(4) And (3) adding 5g of the activated carbon carrier prepared in the step (3) into the mixed active component solution in the step (2), and stirring for 24 hours under the protection of nitrogen to form a uniform and stable black suspension, namely the carbon-supported ruthenium catalyst.
Example 4: preparation of polydicyclopentadiene
Experiment one: the catalyst suspension solution of carbon-supported tungsten prepared in example 1 was diluted with dicyclopentadiene liquid to a tungsten concentration of 0.1mol/L to obtain a catalyst diluent of carbon-supported tungsten, and 5g of dicyclopentadiene liquid was added to a glass test tube, and 0.19mL (tungsten content: 0.019mmol) of the catalyst diluent of carbon-supported tungsten was added to obtain a component a. In another tube, 5g of dicyclopentadiene liquid was added, and 0.72mL of a diethylaluminum monochloride solution (1.0mol/L in toluene) was added to obtain a B component. Based on the total amount of the component A and the component B, the concentration of the active aluminum is 0.07mol/L, and the concentration of the tungsten is 0.0019 mol/L.
The component A and the component B are rapidly mixed together, the viscosity of the mixture becomes large in a short time, and the mixture is transferred to a mold preheated to 70 ℃ and rapidly cured to form a crosslinked solid, so that the polydicyclopentadiene is obtained.
Experiment two: the catalyst suspension solution of carbon-supported molybdenum prepared in example 2 was diluted with dicyclopentadiene liquid to a molybdenum concentration of 0.1mol/L to obtain a catalyst dilution of carbon-supported molybdenum, and 5g of dicyclopentadiene liquid was added to a glass test tube, and 0.15mL (molybdenum content: 0.015mmol) of the catalyst dilution of carbon-supported molybdenum was added to obtain component a. In another tube, 5g of dicyclopentadiene liquid was added, and 0.72mL of a diethylaluminum monochloride solution (1.0mol/L in toluene) was added to obtain a B component. Based on the total amount of the component A and the component B, the total molar concentration of the active aluminum is 0.07mol/L, and the concentration of the molybdenum is 0.0015 mol/L.
The component A and the component B are rapidly mixed together, the viscosity of the mixture becomes large in a short time, and the mixture is transferred to a mold preheated to 70 ℃ and rapidly cured to form a crosslinked solid, so that the polydicyclopentadiene is obtained.
Experiment three: the catalyst suspension solution of ruthenium on carbon prepared in example 3 was diluted with dicyclopentadiene liquid to a ruthenium concentration of 0.1mol/L to obtain a catalyst dilution of ruthenium on carbon, and 5g of dicyclopentadiene liquid was added to a glass test tube, and 0.10mL (ruthenium content: 0.010mmol) of the catalyst dilution of ruthenium on carbon was added to obtain a component a. In another tube, 5g of dicyclopentadiene liquid was added, and 0.72mL of a diethylaluminum monochloride solution (1.0mol/L in toluene) was added to obtain a B component. The total molar concentration of the active aluminum is 0.07mol/L and the concentration of the ruthenium is 0.0010mol/L based on the total amount of the component A and the component B.
And (3) rapidly mixing the component A and the component B together, transferring the mixture into a preheated 70 ℃ mold with the viscosity increased within 10-30 s, and forming a crosslinked solid within 60-200 s to obtain the polydicyclopentadiene.
The physical properties of the polydicyclopentadiene obtained and the swelling properties in toluene are shown in Table 1.
TABLE 1 Performance test results for polydicyclopentadiene
| Kind of main catalyst | Gel/% | Swelling/% | Tg/℃ | Tensile strength/MPa |
| Tungsten | 96 | 67 | 116 | 37 |
| Molybdenum (Mo) | 95 | 77 | 114 | 43 |
| Ruthenium (II) | 97 | 64 | 109 | 41 |
In table 1: the gel% represents the crosslinking degree of the cured resin and is tested by a dynamic mechanical tester; swelling represents the swelling property of polydicyclopentadiene in toluene, and the test method is as follows: soaking the obtained polydicyclopentadiene in toluene for 10-24 h until swelling is stable, and calculating the volume change rate before and after swelling; tg denotes the glass transition temperature.
Example 5: preparation of polydicyclopentadiene
Other conditions were the same as in the experiment of example 4, except that the amount of the catalyst diluent of tungsten supported on carbon was changed to 0.098mL and 0.38mL, respectively.
The physical properties of the polydicyclopentadiene obtained and the swelling properties in toluene are shown in Table 2.
TABLE 2 Performance test results for polydicyclopentadiene
| Amount of main catalyst | Gel/% | Swelling/% | Tg/℃ | Tensile strength/MPa |
| 0.098mL | 95 | 50 | 105 | 29 |
| 0.19mL | 96 | 67 | 116 | 37 |
| 0.38mL | 97 | 92 | 119 | 45 |
The test methods for% gel and swelling properties in table 2 are consistent with those in table 1.
As can be seen from Table 2, polydicyclopentadiene prepared by using the catalyst system of the present invention has excellent physical properties and high strength.
Example 6: preparation of copolymer of dicyclopentadiene and vinyl norbornene
Experiment one: the catalyst suspension solution of tungsten supported on carbon prepared in example 1 was diluted with dicyclopentadiene liquid to a tungsten concentration of 0.1mol/L to obtain a catalyst dilution solution of tungsten supported on carbon, and 5g of a mixture of dicyclopentadiene liquid and a vinyl norbornene monomer, the mass fraction of which was 5%, was added to a glass test tube. Adding 0.19mL of catalyst diluent (the tungsten content is 0.019mmol) loaded with tungsten to prepare a component A. In another test tube, 5g of a mixture of dicyclopentadiene liquid and a vinyl norbornene monomer, the mass fraction of which was 5%, was added, and 0.72mL of a diethylaluminum monochloride solution (1.0mol/L in toluene) was added to obtain a B component. The total molar concentration of the active aluminum is 0.07mol/L and the concentration of the tungsten is 0.0019mol/L based on the total amount of the component A and the component B.
And (3) rapidly mixing the component A and the component B together, transferring the mixture into a preheated 70 ℃ mold within 10-30 s when the viscosity of the mixture is increased, and curing the mixture within 60-200 s to form a crosslinked solid, thus obtaining the dicyclopentadiene and vinyl norbornene copolymer.
Experiment two: other conditions and experiment one were the same, and the amount of catalyst diluent loaded with tungsten alone was changed to 0.098 mL.
Experiment three: other conditions and experiment one were the same, except that the amount of the catalyst diluent supporting tungsten was changed to 0.38 mL.
The physical properties of the resulting copolymer of dicyclopentadiene and vinyl norbornene and the swelling properties in toluene are shown in Table 3.
TABLE 3 Performance test results for copolymers of Dicyclopentadiene and vinyl norbornene
| Amount of main catalyst | Gel% | Swelling of the composition | Tg | Tensile strength/MPa | Flexural Strength/MPa | Impact Strength/KJ/m2 |
| 0.098mL | 97 | 55 | 110 | 39 | 49 | 81 |
| 0.19mL | 98 | 77 | 121 | 41 | 52 | 77 |
| 0.38mL | 99 | 93 | 125 | 45 | 50 | 76 |
The test methods for% gel and swelling properties in table 3 are consistent with those in table 1.
As can be seen from Table 3, the copolymer of dicyclopentadiene and vinyl norbornene prepared using the catalyst system of the present invention has excellent physical properties and high strength.
Example 7: preparation of dicyclopentadiene and methacryloyl norbornene copolymer composition
Experiment one: the catalyst suspension solution of tungsten supported on carbon prepared in example 1 was diluted with dicyclopentadiene liquid to a tungsten concentration of 0.1mol/L to obtain a catalyst dilution solution of tungsten supported on carbon, and 5g of a mixture of dicyclopentadiene liquid and a methacryloyl norbornene monomer, in which the mass fraction of the vinyl norbornene monomer was 5%, was added to a glass test tube. 0.19mL (tungsten content: 0.019mmol) of the tungsten-supporting catalyst suspension solution prepared in example 1 was added to obtain component A. In another test tube, 5g of a mixture of dicyclopentadiene liquid and a vinyl norbornene monomer, wherein the mass fraction of the methacryloyl norbornene monomer was 5%, was added. 0.72mL of a diethylaluminum monochloride solution (1.0mol/L in toluene) was added to obtain a B component. The total molar concentration of the active aluminum is 0.07mol/L and the concentration of the tungsten is 0.0019mol/L based on the total amount of the component A and the component B.
And (3) rapidly mixing the dicyclopentadiene and the methacryloyl norbornene together, transferring the mixture into a mold preheated to 70 ℃ within 10-30 s when the viscosity of the mixture is increased, and curing the mixture within 60-200 s to form a crosslinked solid, namely the dicyclopentadiene and methacryloyl norbornene copolymer.
Experiment two: other conditions and experiment one were the same, and the amount of catalyst diluent loaded with tungsten alone was changed to 0.098 mL.
Experiment three: other conditions and experiment one were the same, except that the amount of the catalyst diluent supporting tungsten was changed to 0.38 mL.
The physical properties of the resulting copolymer of dicyclopentadiene and methacryloyl norbornene and the swelling properties in toluene are shown in Table 4.
TABLE 4 Performance test results for copolymers of Dicyclopentadiene and methacryloyl norbornene
| Amount of main catalyst | Gel% | Swelling of the composition | Tg | Tensile strength/MPa | Flexural Strength/MPa | Impact Strength/KJ/m2 |
| 0.098mL | 99 | 45 | 116 | 41 | 61 | 40 |
| 0.19mL | 99 | 66 | 124 | 44 | 63 | 37 |
| 0.38mL | 98 | 73 | 131 | 47 | 70 | 39 |
The test methods for% gel and swelling properties in table 4 are consistent with those in table 1.
As can be seen from Table 4, the copolymer of dicyclopentadiene and methacryloyl norbornene prepared by using the catalyst system of the present invention has excellent physical properties and high strength.
Example 8: preparation of dicyclopentadiene and butadiene-styrene block copolymer (SBS) composite material
Experiment one: diluting the catalyst suspension solution of the carbon-supported molybdenum prepared in the example 2 with dicyclopentadiene liquid until the concentration of molybdenum is 0.1mol/L to obtain a catalyst diluent of the carbon-supported molybdenum; a glass test tube was charged with 10g of a mixture of dicyclopentadiene liquid and SBS, a butadiene-styrene block copolymer, wherein the SBS block polymer was present in a mass fraction of 6%. Stirring at 60 deg.C for 30min to obtain a uniform transparent solution, and uniformly dividing into two parts. 0.19mL of catalyst diluent of carbon-supported molybdenum (the molybdenum content is 0.019mmol) is added into one part of the mixture to obtain a component A. In another tube, 0.72mL of a diethylaluminum monochloride solution (1.0mol/L in toluene) was added to obtain a B component. Based on the total amount of the component A and the component B, the total molar concentration of the active aluminum is 0.07mol/L, and the concentration of the molybdenum is 0.0019 mol/L.
Rapidly mixing the component A and the component B together, increasing the viscosity of the mixture within 10-30 s, transferring the mixture into a mold preheated to 70 ℃, and curing within 60-200 s to form a crosslinked solid.
Experiment two: other conditions were the same as in the first experiment, except that the amount of the molybdenum-supported catalyst diluent was changed to 0.098 mL.
Experiment three: other conditions were the same as in the first experiment, except that the amount of the molybdenum-supported catalyst diluent was changed to 0.38 mL.
The physical properties of the resulting composite as well as the swelling properties in toluene are shown in table 5.
TABLE 5 Performance test results for Dicyclopentadiene and butadiene-styrene Block copolymer composites
The test methods for% gel and swelling properties in table 5 are consistent with those in table 1.
As can be seen from Table 5, the dicyclopentadiene and butadiene-styrene block copolymer composites prepared by using the catalyst system of the present invention have excellent physical properties and high strength.
Example 9: preparation of dicyclopentadiene-vinylnorbornene-butadiene-styrene block copolymer (SBS) composite material
Experiment one: diluting the catalyst suspension solution of the carbon-supported molybdenum prepared in the example 2 with dicyclopentadiene liquid until the concentration of molybdenum is 0.1mol/L to obtain a catalyst diluent of the carbon-supported molybdenum; a glass test tube was charged with 10g of a mixture of dicyclopentadiene liquid, a vinyl norbornene monomer and a butadiene-styrene block copolymer, wherein the mass fraction of the vinyl norbornene monomer was 5% and the mass fraction of the SBS block copolymer was 6%. Stirring at 60 deg.C for 30min to form a uniform transparent solution. The mixture was uniformly divided into two portions, and 0.15mL (molybdenum content: 0.015mmol) of the molybdenum-supported catalyst diluent prepared in example 2 was added to one portion to obtain component A. In another tube, 0.72mL of a diethylaluminum monochloride solution (1.0mol/L in toluene) was added to obtain a component B. Based on the total amount of the component A and the component B, the total molar concentration of the active aluminum is 0.07mol/L, and the concentration of the molybdenum is 0.0015 mol/L.
The two are quickly mixed together, the viscosity of the mixture is increased within 10-30 s, the mixture is transferred to a mold preheated to 70 ℃, and the mixture is cured within 60-200 ℃ to form a cross-linked solid.
Experiment two: other conditions were the same as in the first experiment, except that the amount of the molybdenum-supported catalyst diluent was changed to 0.098 mL.
Experiment three: other conditions were the same as in the first experiment, except that the amount of the molybdenum-supported catalyst diluent was changed to 0.38 mL.
The physical properties of the resulting composite as well as the swelling properties in toluene are shown in Table 6.
TABLE 6 dicyclopentadiene-vinylnorbornene-SBS composite Performance test results
The test method for% gel in table 6 is consistent with that in table 1.
As can be seen from Table 6, the dicyclopentadiene-vinylnorbornene-SBS composite prepared by using the catalyst system of the present invention has excellent physical properties and high strength.
Example 10: preparation of dicyclopentadiene-vinylnorbornene-butadiene-styrene block copolymer (SBS) composite material
Experiment one: diluting the catalyst suspension solution of carbon-supported ruthenium prepared in example 3 with dicyclopentadiene liquid to a ruthenium concentration of 0.1mol/L to obtain a catalyst diluent of carbon-supported molybdenum; a glass test tube was charged with 10g of a mixture of dicyclopentadiene liquid, vinyl norbornene monomer and SBS, a butadiene-styrene block copolymer, wherein the mass fraction of the vinyl norbornene monomer was 5% and the mass fraction of the SBS block polymer was 6%. Stirring was carried out at 60 ℃ for 30min to form a uniform and transparent solution, which was divided into two portions, and 0.10mL (ruthenium content: 0.010mmol) of the ruthenium-supported catalyst suspension prepared in example 3 was added to one portion to obtain component A. In another tube, 0.72mL of a diethylaluminum monochloride solution (1.0mol/L in toluene) was added to obtain a component B. The total molar concentration of the active aluminum is 0.07mol/L and the concentration of the ruthenium is 0.0010mol/L based on the total amount of the component A and the component B.
The two are rapidly mixed together, the viscosity of the mixture is increased within 10-30 s, the mixture is transferred to a mold preheated to 70 ℃, and the mixture is cured within 60-200 s to form a crosslinked solid.
Experiment two: other conditions were the same as in the first experiment, except that the amount of the diluted ruthenium-supported catalyst solution was changed to 0.05 mL.
Experiment three: other conditions were the same as in the first experiment, except that the amount of the diluted ruthenium-supported catalyst solution was changed to 0.20 mL.
The physical properties of the resulting composite as well as the swelling properties in toluene are shown in Table 7.
TABLE 7 Performance test results of dicyclopentadiene-vinylnorbornene-SBS composite
The test method for% gel in table 7 is consistent with that in table 1.
As can be seen from Table 7, the dicyclopentadiene-vinylnorbornene-SBS composite prepared by using the catalyst system of the present invention has excellent physical properties and high strength.
In addition, as can be seen from the data in tables 1 to 7, the gel% of the material is higher when the catalyst system of the present invention is used for preparing dicyclopentadiene polymeric materials, which indicates that the catalyst system of the present invention can improve the monomer conversion rate.
And (3) testing the stability of the catalyst:
the catalyst suspension solutions prepared in examples 1 to 3 were exposed to air for 24 hours, then dicyclopentadiene was prepared using 3 catalyst suspensions according to the method of example 4, the reaction gel condition was observed, and finally the gelation time was recorded, and the results showed that the gelation time was substantially unchanged from that of example 4 after exposure to air for 24 hours, indicating that it had excellent stability.
The embodiments show that the carbon-based catalyst provided by the invention has high activity and stability, and can be used as a main catalyst for initiating the ring-opening metathesis polymerization of dicyclopentadiene, so that the monomer conversion rate and the product performance can be improved, and the process performance of a polymerization system can be improved; in addition, the carbon-based catalyst provided by the invention has the advantages of simple preparation method, low production cost, mass production and good application prospect.
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.
Claims (10)
1. A preparation method of a carbon-based catalyst is characterized by comprising the following steps:
(1) activating and pretreating the carbon carrier by using acid to obtain an activated carbon carrier;
(2) mixing the activated carbon carrier and the active component mixed solution for impregnation to obtain a carbon-based catalyst; the active component in the active component mixed solution comprises a transition metal oxychloride complex.
2. The method according to claim 1, wherein the method for preparing the active ingredient mixed solution comprises the steps of:
mixing a first ligand, a transition metal chloride and a solvent for reaction to obtain a reaction solution;
sequentially adding a second ligand and a third ligand into the reaction solution to obtain an active component mixed solution;
the transition metal chloride comprises WCl6、MoCl5And RuCl4One or more of the above; the first ligand comprises tert-butyl alcohol and/or di-tert-butyl-p-cresol; the second ligand comprises one or more of nonyl phenol, 4-dimethyl-6-tert-butyl phenol, 2, 6-diamyl hydroquinone, 2, 6-diamyl tert-butyl phenol, 4' -ethylidene bis (6-tert-butyl-o-cresol), polyhydric phenol ligand, bisphenol ligand, tert-butyl catechol, hydrogen phenol, resorcinol and 1,2, 3-benzenetriol; the third ligand comprises one or more of 2, 4-pentanedione and acetylacetone ester ligands;
the molar ratio of the first ligand to the transition metal chloride is 0.1-1: 1; the molar ratio of the second ligand to the transition metal chloride is 1-5: 1; the molar ratio of the third ligand to the transition metal chloride is 1-5: 1.
3. The method according to claim 2, wherein the molar ratio of the transition metal chloride to the transition metal oxychloride in the reaction solution is 0.5 to 5: 1.
4. The method according to claim 2, wherein the adding of the second ligand comprises adding N to the resulting feed solution2Bubbling for 1-2 h; after the third ligand is added, the method also comprises the step of adding the obtained feed liquid N2Bubbling for 1-2 h.
5. The preparation method according to claim 1, wherein the acid comprises one or more of nitric acid, acetic acid, hydrochloric acid and sulfuric acid; the weight ratio of the carbon carrier to the acid is 1: 2-3, the temperature of the activation pretreatment is 30-80 ℃, and the treatment time is 3-8 hours.
6. The preparation method according to claim 1, wherein the amount of the activated carbon carrier and the active component mixed solution is 1 g/20-200 mL, and the immersion time is 20-30 h.
7. The carbon-based catalyst prepared by the preparation method of any one of claims 1 to 6, comprising an activated carbon support and an active component supported on the activated carbon support, wherein the active component comprises a transition metal oxychloride complex.
8. A catalyst system for dicyclopentadiene polymerization, which comprises a main catalyst and a cocatalyst, wherein the main catalyst and the cocatalyst are independently packaged, the main catalyst is the carbon-based catalyst of claim 7, and the cocatalyst is an organic aluminum compound.
9. A method of making a dicyclopentadiene polymeric material using the catalyst system of claim 8, comprising the steps of:
(1) respectively dispersing a main catalyst and a cocatalyst in materials to be polymerized with the same volume under a protective atmosphere to obtain a component A and a component B;
the material to be polymerized is a dicyclopentadiene monomer, or the material to be polymerized comprises a cyclopentadiene monomer and a composite component;
(2) and mixing the component A and the component B under a protective atmosphere, and carrying out heat treatment to obtain the dicyclopentadiene polymeric material.
10. The preparation method of claim 9, wherein the molar ratio of the total molar amount of dicyclopentadiene in the A and B components to the primary catalyst and the co-catalyst is (1200-1500): 1 (10-30); the molar weight of the main catalyst is calculated by the molar weight of a transition metal element, and the molar weight of the auxiliary catalyst is calculated by the mass of an Al element.
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| CN116970148A (en) * | 2023-06-15 | 2023-10-31 | 天津大学 | Cycloolefin copolymer with high performance and wide processing window and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114835905A (en) * | 2022-06-01 | 2022-08-02 | 常州巨德新材料有限公司 | Polyphosphazene amide metal complex catalyst for catalytic polymerization and preparation method thereof |
| CN116970148A (en) * | 2023-06-15 | 2023-10-31 | 天津大学 | Cycloolefin copolymer with high performance and wide processing window and preparation method thereof |
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