A process for the cyclization polymerization of butadiene, catalysts used and methods of preparation

Abstract

A butadiene cyclization polymerization method is characterized in that the method uses 1,3-butadiene as a raw material, and a cyclization polymerization reaction occurs at 30-90 DEG C in the presence of a heterogeneous catalyst composed of an EMM-23 molecular sieve subjected to silanization treatment and titanium supported thereon, and an alkyl aluminum chloride as a cocatalyst, so that 1,5,9-cyclododecatriene, 1,5-cyclooctadiene and 4-vinyl cyclohexene with high selectivity are obtained.

Description

TECHNICAL FIELD

[0001] The present application relates to a method for cyclization polymerization of butadiene, catalysts used and preparation methods, and further relates to a method for cyclization polymerization of butadiene to produce 1,5,9-cyclododecatriene, 1,5-cyclooctadiene and 4-vinylcyclohexene, catalysts used and preparation methods. BACKGROUND

[0002] Butadiene is one of the three major olefins produced in the petrochemical production process, and is an important organic chemical raw material with a very wide application prospect. It is mainly used in the production of polybutadiene rubber, such as styrene-butadiene rubber, cis-butadiene rubber, nitrile rubber, and chloroprene rubber. With the rapid development of science and technology, the low molecular polymerization technology of olefins, such as dimerization and trimerization, is increasingly valued. Among them, the application prospect is wide and the industrial value is relatively high. It is cyclization trimerization of butadiene to produce 1,5,9-cyclododecatriene (referred to as CDT), cyclization dimerization to produce 1,5-cyclooctadiene (referred to as COD) and 4-vinylcyclohexene (referred to as VCH).

[0003] CDT is a special-purpose, important intermediate of organic chemical and fine chemical industry, which can be used to synthesize saturated or unsaturated diacids and their derivatives, and is also a raw material for polyesters, polyamides, plasticizers, flame retardants, macrocyclic organic compounds and some macrocyclic musk. The product of selective hydrogenation by amine-rhodium catalyst can produce nylon 12, cyclododecanal, n-dodecane, bromododecane, cyclododecane and cyclododecadiene, etc., which has wide industrial application value. Germany and other countries began to use cyclododecatriene as the raw material of nylon 12 dodecanamide in the 1970s.

[0004] COD and VCH also have wide applications. COD and VCH react like typical olefins, such as selective hydrogenation, complete hydrogenation at high temperature and pressure, epoxidation, hydrogenation carboxylation and carbonylation, halogenation, etc. The main use of COD is to produce nylon 8, octanoic acid, octenyl acid, low-temperature-resistant plasticizer, monomer of polyamide fiber, engineering plastic, active diluent of epoxy resin, and third monomer of ethylene-propylene rubber. Halogenated COD and VCH have been used as flame retardants, and VCH is dehydrogenated to produce styrene.

[0005] The existing butadiene cyclization catalysts are mainly homogeneous catalysts, and the cyclotrimersation and cyclodimerization catalysts are different catalysts. The progress of the technology is embodied in improving the conversion rate of butadiene and the selectivity of CDT (or COD) under the homogeneous catalytic system. For example, US008168841 utilizes acetylacetone nickel or titanium halide / ethoxydiethyl aluminum or ethyl aluminum sesquichloride catalyst to prepare 1,5,9-cyclododecatriene from 1,3-butadiene trimerization. CN101070263A adopts titanium tetrachloride / half-ethyl aluminum chloride catalyst, uses trace water, ammonia, amine, phenol or alcohol to adjust butadiene and benzene, and prepares 1,5,9-cyclododecatriene from 1,3-butadiene trimerization. JP2005132770 utilizes I2TiCl2 / AlEt2Cl or BrITiCl2 / AlEt2Cl catalyst, adds trace water, and prepares 1,5,9-cyclododecatriene from butadiene trimerization. CN101970392A provides a method for preparing cyclododecatriene from 1,3-butadiene cyclotrimersation and a method for preparing lauryl lactone. DE1140562 and CN108002970A use Ni-A1-P system as catalyst to prepare COD from 1,3-butadiene cyclodimerization, and the yield can reach 96%. J Am Chem Soc, 1965: 87: 4652 first proposes an iron complex catalytic system to prepare COD from 1,3-butadiene cyclodimerization.

[0006] After the reaction of the homogeneous system is completed, the catalyst needs to be quenched and removed by adding water, alcohol and other polar substances, thereby introducing new impurities and causing problems such as non-recyclable catalyst and solid waste.

[0007] To solve the above problems, a heterogeneous catalyst is a better choice. JP2002060353 discloses a method for preparing butadiene by trimerizing butadiene in the presence of a catalyst containing a titanium compound and an organic aluminum compound, characterized in that 1 to 500 times by weight of a zeolite is added to the reaction system to improve the catalytic activity and the selectivity of cyclododecatriene. The zeolite is added as a third component, which is a solid aluminosilicate containing a Lewis base, and does not form a true heterogeneous catalyst with the active component. "Polymer-supported nickel catalyst for butadiene cyclotrimersation" (Journal of Nanjing College of Chemical Technology, Vol. 15 (1): 41) reports that an organic phosphine ligand is introduced into a polystyrene chain to prepare a zero-valent nickel supported catalyst, which mainly obtains CDT in the butadiene cyclotrimersation reaction.

[0008] EMM-23 molecular sieve is a new type of silicon-aluminum molecular sieve synthesized by ExxonMobil in 2012 for the first time, which has a three-dimensional pore system composed of one-dimensional 21-membered ring pores and two-dimensional 10-membered ring pores, and the topological structure code is EWT. This molecular sieve is the first example of a silicon-aluminum molecular sieve with super-large pores and stable structure in the world. After calcination at 540°C, the molecular sieve still has a very high specific surface area and thermal stability. The super-large pore molecular sieve shows advantages in improving the reactivity of macromolecules, prolonging the service life of molecular sieve and improving the selectivity of products, and is expected to have application prospects in heavy oil processing and organic chemical raw material production, and can be used in catalytic cracking, hydrocracking, disproportionation, alkylation, oligomerization and isomerization reaction processes. SUMMARY

[0009] The inventors found that after modification of EMM-23 super-large pore molecular sieve and then loading titanium compounds to prepare a heterogeneous catalyst, 1,3-butadiene cyclization polymerization can be catalyzed by using the catalyst with half-ethyl aluminum chloride as a cocatalyst to obtain cyclotrimers and cyclodimers with high selectivity of CDT, COD and VCH. Based on this, the present application is formed.

[0010] Therefore, the purpose of the present application is to provide a method for 1,3-butadiene cyclization polymerization to prepare 1,5,9-cyclododecatriene, 1,5-cyclooctadiene and 4-vinylcyclohexene, and to provide a catalyst used in the method and a preparation method thereof.

[0011] In order to achieve the above-mentioned purpose, the first aspect of the present application provides a butadiene cyclization polymerization method, characterized in that the method uses 1,3-butadiene as a raw material, and a cyclization polymerization reaction occurs at 30-90°C in the presence of a heterogeneous catalyst composed of silanized EMM-23 molecular sieve and titanium loaded thereon, and an alkyl aluminum chloride as a cocatalyst to obtain 1,5,9-cyclododecatriene, 1,5-cyclooctadiene and 4-vinylcyclohexene.

[0012] In the cyclization polymerization method, the alkyl aluminum chloride is preferably half-ethyl aluminum chloride and diethyl aluminum chloride. The molar ratio of the cocatalyst to the heterogeneous catalyst is 5-40:1, preferably 10-30:1, and the heterogeneous catalyst is calculated based on titanium.

[0013] In order to achieve the above-mentioned purpose, the second aspect of the present application provides a heterogeneous catalyst, characterized in that it is composed of silanized EMM-23 molecular sieve and titanium loaded thereon, and the titanium content is 1-15% based on the mass of the catalyst. Preferably, the titanium content is 5-12%.

[0014] In order to achieve the above-mentioned purpose, the third aspect of the present application provides a method for preparing a heterogeneous catalyst, characterized in that it comprises the following steps:

[0015] a. ammonium exchange and sodium removal of EMM-23 molecular sieve to obtain a sodium removal EMM-23 molecular sieve with Na2O content of ≤0.5 wt.%;

[0016] b. dealumination treatment of the sodium removal EMM-23 molecular sieve with acid to obtain a dealumination EMM-23 molecular sieve;

[0017] c. mixing the dealumination EMM-23 molecular sieve with a silylating agent and light aromatic hydrocarbon, stirring at 50-90℃ for 5-10h, filtering and drying to obtain a carrier EMM-23 molecular sieve, wherein the silylating agent has a general formula of R"R'N-(CH2)n-Si-A'A" A'" wherein R' and R" are both H or one of R' and R" is H and the other is C1-C4 alkyl, A', A", and A'" are all methoxy or all ethoxy, or when any one of A', A", and A'" is methyl or ethyl, the other two are all methoxy, all ethoxy, or methoxy and ethoxy respectively, and n is 1, 2, 3 or 4, and the weight ratio of the dealumination EMM-23 molecular sieve, the silylating agent and the light aromatic hydrocarbon is 1:0.5-1:2-4;

[0018] d. mixing the carrier EMM-23 molecular sieve, TiCl4 and benzene or toluene under anhydrous and anaerobic reaction conditions and nitrogen protection, stirring at 30-60℃ for 5-30h, separating, washing and drying to obtain a heterogeneous catalyst composed of a silylating treated EMM-23 molecular sieve and titanium loaded thereon, wherein the weight ratio of TiCl4 to the carrier EMM-23 molecular sieve is 0.3-1.2, and the weight ratio of benzene or toluene to the carrier EMM-23 molecular sieve is 5-15.

[0019] In the method for preparing the heterogeneous catalyst provided by the application, the ammonium exchange and sodium removal of step a is the exchange, washing and drying of EMM-23 molecular sieve in an inorganic ammonium salt solution at a reflux temperature, and the weight ratio of the EMM-23 molecular sieve, the inorganic ammonium salt and water is 1:1-10:10-100.

[0020] Preferably, in the dealumination treatment of step b, an acid with a concentration of 4-7 mol / L is used. Preferably, the acid is nitric acid, and the solid-liquid ratio is preferably 1:5-10.

[0021] Preferably, the light aromatic hydrocarbon of step c can be selected from benzene, toluene, ethylbenzene, xylene and the like, and preferably the light aromatic hydrocarbon is toluene.

[0022] Preferably, R' and R" of step c are both H.

[0023] Preferably, the silanization agent in step c is 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldiethoxysilane or N-methyl-3-aminopropyltrimethoxysilane.

[0024] Preferably, the weight ratio of TiCl4 to the support EMM-23 molecular sieve in step d is 0.6-0.9.

[0025] The heterogeneous catalyst provided by the present application is prepared by modifying EMM-23 superlarge-pore molecular sieve and then loading titanium compound, and the catalyst catalyzes 1,3-butadiene cyclization polymerization with half-ethyl aluminum chloride as a cocatalyst, so that the cyclotrimers and cyclodimers with high selectivity of CDT, COD and VCH can be obtained from one catalyst. After the butadiene cyclization polymerization reaction is completed, the catalyst can be reused after filtration or centrifugal separation under anhydrous and anaerobic operation conditions, and the selectivity does not change significantly.

[0026] The present application overcomes the problems in the prior art homogeneous system, such as the need to quench and remove the catalyst by adding polar substances such as water and alcohol after the reaction is completed, thus introducing new impurities, and the catalyst cannot be recycled and solid waste is generated. The heterogeneous solid catalyst can be recycled by simple filtration or centrifugal treatment, and the reaction is recycled, thereby reducing solid waste. DETAILED DESCRIPTION

[0027] The present application is further described below by examples, but the present application is not limited by the examples.

[0028] Examples 1-4 are used to illustrate the heterogeneous catalyst and the preparation method thereof provided by the present application.

[0029] Example 1

[0030] a. Under stirring, 30 g of EMM-23 molecular sieve (produced by Sinopec Jianshang Petrochemical Co., Ltd., SiO2 / Al2O3=95, specific surface area 614 m 2 / g, pore volume 0.332 cm 3 / g), 60 g of NH4Cl and 600 mL of water were mixed, and ion exchange was performed at reflux temperature for 2 h, and then the ion-exchanged EMM-23 molecular sieve was washed with deionized water and dried at 110°C, so that the Na2O content was ≤0.5 wt.%;

[0031] b. 25 g of the ion-exchanged EMM-23 molecular sieve was added into 250 mL of concentrated nitric acid with a concentration of 5 mol / L, and the mixture was treated at reflux temperature for 10 h, then filtered, washed with deionized water and dried at 110°C, so that the dealuminated EMM-23 molecular sieve was obtained;

[0032] c. 22 g of dealuminated EMM-23 molecular sieve, 22 g of 3- aminopropyltriethoxysilane H2N(CH2)3Si(OC2H5)3 (Mw 221.37) and 66 g of toluene were mixed and stirred at 70 °C for 7 h, the solid was filtered and dried at 120 °C to obtain the support EMM-23 molecular sieve.

[0033] d. 30 g of support EMM-23 molecular sieve, 19 g of TiCl4 and 300 g of toluene were mixed under anhydrous and anaerobic conditions under nitrogen protection, stirred at 40 °C for 20 h, filtered, washed with hexane three times and dried to obtain a heterogeneous catalyst, numbered HeC2, with a titanium content of 7.6%.

[0034] Example 2

[0035] a, b, same as example 1.

[0036] c. 22 g of dealuminated EMM-23 molecular sieve, 22 g of 3- aminopropyltriethoxysilane H2N(CH2)3Si(OC2H5)3 (Mw 221.37) and 66 g of toluene were mixed and stirred at 70 °C for 7 h, the solid was filtered and dried at 120 °C to obtain the support EMM-23 molecular sieve.

[0037] d. 30 g of support EMM-23 molecular sieve, 19 g of TiCl4 and 300 g of toluene were mixed under anhydrous and anaerobic conditions under nitrogen protection, stirred at 40 °C for 20 h, filtered, washed with hexane three times and dried to obtain a heterogeneous catalyst, numbered HeC2, with a titanium content of 7.6%.

[0038] Example 3

[0039] a, b, same as example 1.

[0040] c. 22 g of dealuminated EMM-23 molecular sieve, 22 g of 3- aminopropyltriethoxysilane H2N(CH2)3Si(OC2H5)3 (Mw 221.37) and 66 g of toluene were mixed and stirred at 70 °C for 7 h, the solid was filtered and dried at 120 °C to obtain the support EMM-23 molecular sieve.

[0041] d. 30 g of support EMM-23 molecular sieve, 19 g of TiCl4 and 300 g of toluene were mixed under anhydrous and anaerobic conditions under nitrogen protection, stirred at 40 °C for 20 h, filtered, washed with hexane three times and dried to obtain a heterogeneous catalyst, numbered HeC2, with a titanium content of 7.6%.

[0042] Example 4

[0043] a, b, same as example 1.

[0044] c. 19 g of dealuminated EMM-23 molecular sieve, 19 g of N-methyl-3- aminopropyltrimethoxysilane CH3NH(CH2)3Si(OCH3)3 (Mw 193.32) and 57 g of toluene were mixed, stirred at 90 °C for 5 h, and the solid was filtered and dried at 120 °C to obtain the carrier EMM-23 molecular sieve.

[0045] d. 29 g of the carrier EMM-23 molecular sieve, 18 g of TiCl4 and 290 g of toluene were mixed under anhydrous and anaerobic conditions under nitrogen protection, stirred at 60 °C for 5 h, filtered, washed with hexane three times, and dried to obtain a heterogeneous catalyst numbered HeC4, wherein the titanium content was 5.4%.

[0046] Example 5

[0047] This example illustrates the reuse effect of the butadiene cyclization polymerization method and the catalyst provided by the present application.

[0048] 1L Parr reactor was replaced with nitrogen three times, 300 mL of toluene, 14.9 g (60 mmol) of hemiethyl aluminum chloride and 1.9 g (4 mmol of titanium) of the heterogeneous catalyst HeC1 (the molar ratio of the cocatalyst to the heterogeneous catalyst was 15) were added into the reactor under nitrogen protection, stirring was started, 1,3-butadiene was continuously introduced, the temperature was kept at 65 °C, and the pressure was kept at 0.1 MPa, and the reaction was carried out for 3 hours. After the reaction was completed, the solid was filtered under nitrogen protection, and the obtained solid was recorded as Re-HeC1 and stored under nitrogen protection. The obtained liquid was added with methanol to terminate the reaction, and the reaction product was treated by distillation to obtain the fraction composition, the CDT selectivity was 53%, the COD selectivity was 42%, and the VCH selectivity was 4%.

[0049] wherein,

[0050] CDT (1,5,9-cyclododecatriene) selectivity = (the mass of CDT in the product / the total mass of the product) x 100%;

[0051] COD (1,5-cyclooctadiene) selectivity = (the mass of COD in the product / the total mass of the product) x 100%;

[0052] VCH (4-vinylcyclohexene) selectivity = (the mass of VCH in the product / the total mass of the product) x 100%.

[0053] Re-HeC1 was filtered under nitrogen protection, washed with hexane three times, and dried. The 1,3-butadiene cyclization polymerization was carried out again by using Re-HeC1 instead of HeC1 according to the above cyclization polymerization method. The reaction product was treated by distillation to obtain the fraction composition, the CDT selectivity was 51%, the COD selectivity was 43%, and the VCH selectivity was 5%.

[0054] Example 6

[0055] This example illustrates the re-use effect of the butadiene cyclization polymerization method and catalyst provided by the present application.

[0056] The same as Example 5, except that HeC2 is used as the catalyst.

[0057] CDT selectivity 51%, COD selectivity 45%, VCH selectivity 2%

[0058] Re-HeC2 is used instead of HeC2 to perform the 1,3-butadiene cyclization polymerization reaction, CDT selectivity 53%, COD selectivity 42%, VCH selectivity 3%.

[0059] Example 7

[0060] This example illustrates the re-use effect of the butadiene cyclization polymerization method and catalyst provided by the present application.

[0061] The same as Example 5, except that HeC3 is used as the catalyst.

[0062] CDT selectivity 54%, COD selectivity 41%, VCH selectivity 3%

[0063] Re-HeC3 is used instead of HeC3 to perform the 1,3-butadiene cyclization polymerization reaction, CDT selectivity 52%, COD selectivity 42%, VCH selectivity 3%.

[0064] Example 8

[0065] This example illustrates the re-use effect of the butadiene cyclization polymerization method and catalyst provided by the present application.

[0066] The same as Example 5, except that HeC4 is used as the catalyst.

[0067] CDT selectivity 51%, COD selectivity 46%, VCH selectivity 2%

[0068] Re-HeC4 is used instead of HeC4 to perform the 1,3-butadiene cyclization polymerization reaction, CDT selectivity 52%, COD selectivity 45%, VCH selectivity 2%.

[0069] Example 9

[0070] This example illustrates the butadiene cyclization polymerization method provided by the present application.

[0071] The same as Example 5, except that the molar ratio of the co-catalyst and the heterogeneous catalyst is changed to 25:1.

[0072] CDT selectivity 52%, COD selectivity 44%, VCH selectivity 3%.

[0073] Example 10

[0074] This example illustrates the butadiene cyclization polymerization process provided by the present application.

[0075] The same as Example 5 except that the co-catalyst is replaced by diethylaluminum chloride. The CDT selectivity is 52%, the COD selectivity is 43%, and the VCH selectivity is 3%.

[0076] Example 11

[0077] This example illustrates the butadiene cyclization polymerization process provided by the present application.

[0078] The same as Example 5 except that the cyclization polymerization temperature is changed to 80°C.

[0079] The CDT selectivity is 51%, the COD selectivity is 42%, and the VCH selectivity is 3%.

Claims

1. A method for the cyclopolymerization of butadiene, characterized in that The method is to use 1,3-butadiene as raw material, and to carry out ring polymerization at 30-90℃ in the presence of a heterogeneous catalyst composed of silanization-treated EMM-23 molecular sieve and titanium loaded thereon, and an aluminum alkyl chloride as a cocatalyst, to obtain 1,5,9-cyclododecatriene, 1,5-cyclooctadiene and 4-vinylcyclohexene; wherein the heterogeneous catalyst is prepared by a method comprising the following steps: a. ammonium exchange and sodium removal of the EMM-23 molecular sieve to obtain a sodium-removed EMM-23 molecular sieve with a Na2O content of ≤0.5 wt.%; b. dealumination treatment of the sodium-removed EMM-23 molecular sieve with an acid to obtain a dealuminated EMM-23 molecular sieve; c. mixing the dealuminated EMM-23 molecular sieve with a silanization reagent and light aromatic hydrocarbon, stirring and reacting at 50-90°C for 5-10h, filtering and drying to obtain a carrier EMM-23 molecular sieve, wherein the silanization reagent has a general formula of R ″ R ′ N-(CH2)n-Si-A ′ A ″ A ″′ , wherein the R ′ and the R ″ are simultaneously H or one of the R ′ and the R ″ is H and the other is C1-C4 alkyl, the A ′ , A ″ , A ″′ are all methoxy or all ethoxy, or when any one of the A ′ , A ″ , A ″′ is methyl or ethyl, the other two are all methoxy, all ethoxy, or methoxy and ethoxy respectively, and the n is 1, 2, 3 or 4. c. mixing the dealuminated EMM-23 molecular sieve with a silanization reagent and light aromatic hydrocarbon, stirring and reacting at 50-90°C for 5-10h, filtering and drying to obtain a carrier EMM-23 molecular sieve, wherein the silanization reagent has a general formula of R ″ R ′ N-(CH2)n-Si-A ′ A ″ A ″′ , wherein the R ′ and the R ″ are simultaneously H or one of the R ′ and the R ″ is H and the other is C1-C4 alkyl, the A ′ , A ″ , A ″′ are all methoxy or all ethoxy, or when any one of the A ′ , A ″ , A ″′ is methyl or ethyl, the other two are all methoxy, all ethoxy, or methoxy and ethoxy respectively, and the n is 1, 2, 3 or 4. d. mixing the carrier EMM-23 molecular sieve, TiCl4 and benzene or toluene under anhydrous and oxygen-free reaction conditions and nitrogen protection, stirring and reacting at 30-60℃ for 5-30h, and then separating, washing and drying to obtain the heterogeneous catalyst composed of the silanization-treated EMM-23 molecular sieve and titanium loaded thereon.

2. The method according to claim 1, wherein, The aluminum alkyl chloride is hemi-ethyl aluminum chloride or diethyl aluminum chloride.

3. The method according to claim 1, wherein, The molar ratio of the cocatalyst to the heterogeneous catalyst is 5-40:1, and the heterogeneous catalyst is calculated based on the titanium content.

4. The method according to claim 3, wherein, The molar ratio of the cocatalyst to the heterogeneous catalyst is 10-30:

1.

5. The method according to claim 1, wherein, The titanium content in the heterogeneous catalyst composed of the silanization-treated EMM-23 molecular sieve and titanium loaded thereon is 1-15% based on the catalyst mass.

6. The method according to claim 5, wherein, The titanium content is 5-12%.

7. The method according to claim 1, wherein, The ammonium exchange and sodium removal in step a is to exchange, wash and dry the EMM-23 molecular sieve in an inorganic ammonium salt solution at a reflux temperature, and the weight ratio of the EMM-23 molecular sieve, the inorganic ammonium salt and water is 1:1-10:10-100.

8. The method according to claim 1, wherein, In the dealumination treatment in step b, the acid has a concentration of 4-7 mol / L.

9. The method according to claim 1 or 8, wherein, The acid is nitric acid, and the solid-liquid ratio is 1:5-10.

10. The method according to claim 1, wherein, The light aromatic hydrocarbon in step c is toluene.

11. The method according to claim 1, wherein, The weight ratio of the dealuminated EMM-23 molecular sieve, the silanization reagent and the light aromatic hydrocarbon in step c is 1:0.5-1:2-4.

12. The method according to claim 1, wherein, R ′ and R ″ is H.

13. The method according to claim 1, wherein, The silanization reagent in step c is 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldiethoxysilane or N-methyl-3-aminopropyltrimethoxysilane.

14. The method according to claim 1, wherein, The weight ratio of TiCl4 to the carrier EMM-23 molecular sieve in step d is 0.3-1.2, and the weight ratio of benzene or toluene to the carrier EMM-23 molecular sieve is 5-15.

15. The method according to claim 1, wherein, The weight ratio of TiCl4 to the carrier EMM-23 molecular sieve in step d is 0.6-0.9.