Process for the preparation of a high isotactic polybutene-1

Abstract

The application belongs to the technical field of polymer preparation, and discloses a preparation method of high isotactic polybutene-1. 10 The application discloses a preparation method of high isotactic polybutene-1, which comprises the following steps: carrying out a polymerization reaction on butene-1 and optional C2-C 10 α-olefin monomers under the action of a Ziegler-Natta catalyst system; the Ziegeller-Natta catalyst system contains a solid catalyst component, an organic aluminum compound and an external electron donor; the solid catalyst component contains a catalyst carrier, an internal electron donor and a reaction product of a halide containing titanium, and the internal electron donor contains a carboxylic acid ester compound and a polyhydric alcohol ester compound; the polymerization reaction conditions include that the polymerization temperature is 0-150 DEG C, and the polymerization pressure is higher than the saturated steam pressure of butene-1 at the corresponding polymerization temperature. The preparation method has high polymerization activity, and the obtained polymer has high isotacticity.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of polymer preparation, and particularly relates to a preparation method of high isotactic polybutene-1. BACKGROUND

[0002] Polybutene-1 is a polymorphic polymer, and the polymer of high isotactic I type crystal form has good physical comprehensive performance, excellent anti-creep performance and other advantages, and is more applied in the fields of easy-opening film, hot melt adhesive, plastic modification, high-grade pressure-resistant pipe and electromechanical fittings, and particularly occupies a high-end position in the field of pipe material. However, due to the complex production process and difficult product structure control, the market share is limited, and the industrial scale is small.

[0003] At present, there are three kinds of preparation methods of polybutene-1: gas phase method, slurry method and bulk method. The gas phase polymerization activity is too low. The patent document 99800235.6 of Montell Technology Limited uses Z-N catalytic system for gas phase polymerization, and the polymerization is carried out at 60℃ in the first gas phase kettle for 11 hours, and the yield is 1.4 kgPB / g catalyst, and then the polymerization is carried out at 70℃ in the second gas phase kettle for 9 hours, and the yield is 5 kgPB / g catalyst. Such low polymerization activity leads to high ash content in the product, and low industrial value.

[0004] The slurry polymerization process using inert solvent is widely used in the polyolefin industry. This process can dissolve the sticky soluble substances in the polymer into the solvent, further separate and remove them, and obtain high-quality polymer products, and also can reduce the risk of polymer adhesion. However, the solubility of polybutene-1 in the inert solvent used in the conventional slurry reaction is relatively high, and when the reaction temperature is relatively high, a homogeneous solution system is formed. The patent document US5237013 of Japan Idemitsu Corporation uses n-hexane as a solvent to realize the solution polymerization of butene-1. The disadvantage of this method is also obvious, and a large amount of solvent needs to be recovered, and the process is complex, low in efficiency and high in cost.

[0005] Bulk polymerization is the most important polymerization method for producing polybutene-1 at present. Qingdao University of Science and Technology has done a lot of work in the synthesis of polybutene-1. The patent document 200710013587.X provides a bulk precipitation synthesis method of high isotactic polybutene-1, which uses Z-N catalytic system to carry out bulk polymerization at 50℃, and the isotacticity of the polymer is greater than 98%, and the powder-like polybutene-1 can be directly obtained. However, the polymerization activity is relatively low due to the control of the reaction temperature. The patent document 03800736.3 of Basell Company uses Z-N catalytic system to carry out bulk polymerization at 70-75℃, and the polymerization activity is 50 kgPB / g cat.·2h, and the isotacticity of the polymer can reach 99%.

[0006] Patent document 201210422461.9 of Beijing Chemical Research Institute adopts high-temperature bulk solution method for butene-1 polymerization, the difference is that Z-N catalyst containing diol ester is used as main catalyst, after being pretreated with alkyl aluminum and external electron donor, butene-1 polymerization is carried out, and high-activity, high-stereoregularity polybutene-1 product can be obtained. The polymerization activity can reach 30 kgPB / gcat·h, and the stereoregularity of the polymer is above 98%. SUMMARY

[0007] The inventors of the present application have found that, when butene-1 polymerization is carried out under high-temperature bulk conditions by using titanium ester compound and polysiloxane substance protected and treated alkoxymagnesium particles as carrier, solid catalyst component prepared by using carboxylic acid ester compound and polyhydric alcohol ester compound as internal electron donor, and catalyst system combined with organic aluminum compound and external electron donor, the polymerization has the characteristics of high polymerization activity and high stereoregularity, and based on this, the purpose of the present application is to provide a high-stereoregularity polybutene-1 preparation method.

[0008] The present application provides a high-stereoregularity polybutene-1 preparation method, which comprises: butene-1 and optional C2-C 10 α-olefin monomers are subjected to polymerization reaction under the action of Ziegler-Natta type catalyst system;

[0009] The Ziegler-Natta type catalyst system contains solid catalyst component, organic aluminum compound and external electron donor; the solid catalyst component contains catalyst carrier, internal electron donor and reaction product of halide containing titanium, and the internal electron donor contains carboxylic acid ester compound and polyhydric alcohol ester compound;

[0010] The conditions of the polymerization reaction include: the polymerization temperature is 0-150℃, preferably 40-100℃; and the polymerization pressure is higher than the saturated vapor pressure of butene-1 at the corresponding polymerization temperature.

[0011] Compared with the prior art, the present application has the following beneficial effects:

[0012] The preparation method of the present application has high polymerization activity, and the highest activity can reach 50 kgPB / gcat·h, and the stereoregularity of the obtained polybutene-1 is high, and the highest can reach 99.3wt%.

[0013] Other features and advantages of the present application will be described in detail in the following specific embodiments. DETAILED DESCRIPTION

[0014] The specific embodiments of the present application are described in detail below. It should be understood that the specific embodiments described herein are only used to illustrate and explain the present application, and are not used to limit the present application.

[0015] According to the present application, there is provided a process for preparing a high isotactic polybutene-1, the process comprising: polymerizing butene-1 and optionally C2-C 10 α-olefin monomers in the presence of a Ziegler-Natta type catalyst system;

[0016] The Ziegler-Natta type catalyst system contains a solid catalyst component, an organic aluminum compound and an external electron donor; the solid catalyst component contains a catalyst support, an internal electron donor and a reaction product of a halide containing titanium, the internal electron donor contains a carboxylic acid ester compound and a polyhydric alcohol ester compound;

[0017] The conditions of the polymerization reaction include: a polymerization temperature of 0-150°C, preferably 40-100°C; a polymerization pressure higher than the saturated vapor pressure of butene-1 at the corresponding polymerization temperature.

[0018] In the present application, the catalyst support contains a reaction product of alkoxy magnesium particles and a particle protective agent, the particle protective agent being a titanate compound and a polysiloxane substance.

[0019] The structure of the alkoxy magnesium particles is shown in Formula I:

[0020] Mg(OR9) 2-p (OR 10 ) p Formula I

[0021] In Formula I, R9 and R 10 are the same or different, each being selected from C1-C8 linear alkyl, C3-C8 branched alkyl, 0≤p≤2.

[0022] Preferably, R9 and R 10 are each selected from methyl, ethyl, propyl, isopropyl, butyl, isobutyl, n-hexyl, (2-ethyl)hexyl; more preferably, R9 and R 10 are the same, the alkoxy magnesium particles being selected from at least one of dimethoxy magnesium, diethoxy magnesium, dipropoxy magnesium, diisopropoxy magnesium, dibutoxy magnesium, diisobutoxy magnesium, dipentoxy magnesium, dihexyloxy magnesium and di(2-ethyl)hexyloxy magnesium; particularly preferably, the alkoxy magnesium particles are diethoxy magnesium or a mixture of diethoxy magnesium and other alkoxy magnesium.

[0023] It should be further noted that formula I only represents the composition of each alkoxy group in the alkoxy magnesium particles, and does not represent the specific structure of the alkoxy magnesium particles. Specifically, Mg(OEt)(OiPr) only represents that the molar ratio of ethoxy group to isopropoxy group in the alkoxy magnesium particles is 1, which can be a mixture of diethoxy magnesium and diisopropoxy magnesium with a molar ratio of 1, can be an ethoxy isopropoxy magnesium compound, or can be a mixture of the three; it can also be a mixture of a plurality of structures of alkoxy magnesium compounds with a total molar ratio of ethoxy group to isopropoxy group of 1. Wherein Et represents ethyl, and iPr represents isopropyl.

[0024] In the present application, the structure of the titanate compound is shown in formula II:

[0025] (R1’O) a Ti(OR2’) b (OR3’) c X d Formula II

[0026] In formula II, R1’, R2’ and R3’ are the same or different, and each is selected from H or an alkyl group, preferably a C1-C 10 alkyl group, X is selected from an alkoxy group, a carboxyl group, chlorine, a sulfonic acid group, a phosphoric acid group or a sulfuric acid group, a, b, c and d are independently integers from 0 to 4, and a+b+c+d=4.

[0027] The titanate compound can be selected from at least one of tetramethyl titanate, tetraethyl titanate, tetrapropyl titanate, tetrabutyl titanate, tetrapentyl titanate, tetrahexyl titanate, tetraheptyl titanate, tetraisooctyl titanate, tetralauryl titanate, tetradecyl titanate and isomers thereof; preferably at least one of tetraethyl titanate, tetraisopropyl titanate and tetrabutyl titanate.

[0028] The molar ratio of the titanate compound to magnesium in the alkoxy magnesium particles can be (0.01-5):1, preferably (0.02-2):1.

[0029] According to the present application, the structure of the polysiloxane substance is shown in formula III:

[0030] (R 1 R 2 R 3 )SiO[(R 7 R 8 )SiO] n …[(R y R z )SiO] m Si(R 4 R 5 R 6 ) Formula III

[0031] in formula III, R 1 -R z identical or different, are each selected from the group consisting of linear, branched or cyclic alkyl groups having from 1 to 20 carbon atoms, linear, branched or cyclic aralkyl groups having from 7 to 20 carbon atoms, linear, branched or cyclic aralkenyl groups having from 8 to 20 carbon atoms, substituted or unsubstituted aromatic hydrocarbon groups having from 6 to 20 carbon atoms, linear, branched or cyclic alkenyl groups having from 2 to 20 carbon atoms, hydrogen, hydroxyl, alkoxy, acetoxy, chlorine, cyano, amino, carboxyl, mercapto, carbon functional groups, polyether chains; the sum of the polymerization degrees n+m is an integer from 2 to 100; it is to be noted that R 12 12 10 20 20 12 y , R z are groups arranged in the order following R 8 , and R z is arranged following R y , as R y may be R 11 , R z may be R 12 , R 1 -R z refers to all groups in formula III.

[0032] The polysiloxane substance is preferably at least one of a polymethylsiloxane, a polyethylsiloxane, a polyphenylsiloxane, a polymethylhydrogenosiloxane, a polymethylphenylsiloxane, a polymethylchlorophenylsiloxane, a polymethylethoxysiloxane, a polymethyltrifluoropropylsiloxane, a polymethylvinylsiloxane, a polymethylhydroxysiloxane, a polyethylhydrogenosiloxane, a polyhydroxylhydrogenosiloxane, a polycyanosiloxane, a polyaminosiloxane, a polyepoxysiloxane, a polyethersiloxane, a polycarboxysiloxane, a polyalcoholhydroxysiloxane, a polyphenolhydroxysiloxane, a polymercaptosiloxane and a modified body thereof, more preferably at least one of a polymethylsiloxane, a polyethylsiloxane, a polymethylphenylsiloxane, a polyethersiloxane, a polycyanosiloxane and a modified body thereof. The modified body can be a conventional modified body of each polysiloxane, such as an epoxy-modified polymethylsiloxane, a polyether-modified polysiloxane, an epoxy-modified polysiloxane, a fluoroalkyl-modified polysiloxane.

[0033] The molar ratio of the polysiloxane substance to magnesium in the magnesium alkoxide particles can be (0.01-5) : 1, preferably (0.02-2) : 1.

[0034] In the present application, the carboxylic acid ester compound can be selected from a benzoic acid monoester compound or a phthalic acid ester compound having a structure as shown in formula IV,

[0035] ​​​​​​

[0036] In Formula IV, R1 and R2 are independently selected from substituted or unsubstituted C1-C8 alkyl groups, C3-C6 alkyl groups, and C4-C6 alkyl groups. 10 cycloalkyl or C6-C 20 The aromatic group; R3-R6 are independently selected from hydrogen, halogen, C1-C4 alkyl or C1-C4 alkoxy, preferably, at least three of R3-R6 are hydrogen.

[0037] Specifically, the carboxylic acid ester compound may be selected from ethyl benzoate, propyl benzoate, butyl benzoate, amyl benzoate, hexyl benzoate, heptyl benzoate, octyl benzoate, nonyl benzoate, decyl benzoate, dimethyl phthalate, diethyl phthalate, dipropyl phthalate, di-n-butyl phthalate, diisobutyl phthalate, dipentyl phthalate, dihexyl phthalate, diheptyl phthalate, dioctyl phthalate, and other carboxylic acid esters. Dinonyl phthalate, didecyl phthalate, methyl ethyl phthalate, methyl propyl phthalate, methyl butyl phthalate, methyl pentyl phthalate, ethyl propyl phthalate, ethyl butyl phthalate, ethyl pentyl phthalate, ethyl hexyl phthalate, propyl butyl phthalate, propyl pentyl phthalate, propyl hexyl phthalate, butyl pentyl phthalate, butyl hexyl phthalate, pentyl hexyl phthalate, and at least one of their isomers.

[0038] The molar ratio of the carboxylic acid ester compound to magnesium in the alkoxy magnesium particles is (0.01-5):1, preferably (0.02-2):1.

[0039] According to the present invention, the polyol ester compound is selected from diol ester compounds with structures as shown in Formula V.

[0040]

[0041] In formula V, R 1’ and R 2’ Whether the C1-Cs are the same or different, they are each selected from substituted or unsubstituted C1-Cs. 20 Straight-chain alkyl, C3-C 20 Branched alkyl groups, C3-C 20 cycloalkyl, C6-C 20 aryl, C7-C 20 alkylaryl, C7-C 20 Aryl groups, C2-C 10 olefin group, C 10 -C 20 Fused ring aryl group; R 3’ -R 8’ They may be the same or different, each selected from hydrogen, halogen, substituted or unsubstituted C1-C. 20 Straight-chain alkyl, C3-C 20branched alkyl, C3-C 20 cycloalkyl, C6-C 20 aryl, C7-C 20 alkylaryl, C7-C 20 aralkyl, C7-C 10 alkenyl, C 10 -C 20 fused ring aryl; or R 3’ -R 6’ at least one of R 7’ -R 8’ forms a ring with at least one of R

[0042] The dihydric alcohol ester compound specifically includes, but is not limited to, 2-ethyl-1,3-propanediol dibenzoate, 2-propyl-1,3-propanediol dibenzoate, 2-isopropyl-2-isopentyl-1,3-propanediol dibenzoate, 1,3-butanediol dimethylbenzoate, 2-methyl-1,3-butanediol di-m-chlorobenzoate, 2,3-dimethyl-1,3-butanediol dibenzoate, 1,3-pentanediol di-neopentanoate, 2,4-pentanediol dibenzoate, 2-methyl-1,3-pentanediol benzoate cinnamate, 2,2-dimethyl-1,3-pentanediol dibenzoate, 2,4-heptanediol dibenzoate, 3,5-heptanediol dibenzoate, 4-ethyl-3,5-heptanediol dibenzoate, 2-methyl-3,5-heptanediol dibenzoate, and the like. The dihydric alcohol ester compound is preferably at least one of 3,5-heptanediol dibenzoate, 4-ethyl-3,5-heptanediol dibenzoate, and 2,4-pentanediol dibenzoate.

[0043] The molar ratio of the polyhydric alcohol ester compound to magnesium in the magnesium alkoxide particles is (0.01-5) : 1, and preferably (0.02-2) : 1.

[0044] According to the present application, the titanium-containing halide has a structure represented by Formula VI,

[0045] TiX 1 e (OR7) 4-e Formula VI

[0046] In Formula VI, X 1 is halogen, preferably chlorine, R7 is a hydrocarbon group, preferably C1-C5 alkyl, and e is an integer of 0-4. 20

[0047] The amount of the titanium-containing halide can be determined with reference to the prior art and as needed.

[0048] ​In the present application, the preparation of the solid catalyst component can be carried out using the conventional methods in the prior art, and specifically can use the following method: first, the alkoxymagnesium particles are dispersed to form a suspension with an inert diluent, a particle protective agent is added for treatment, and a catalyst mother liquor is obtained by contacting with a titanium-containing halide and an internal electron donor. The solid material in the mother liquor is treated by filtration, titanium treatment, filtration again, washing, drying and other treatments to obtain the solid catalyst component. Among them, the inert diluent can use at least one of n-hexane, n-heptane, n-octane, n-decane, benzene, toluene and xylene, and the amount of the inert diluent is 0.5-100 mol, preferably 1-50 mol. The contact temperature of each component is usually -40°C to 200°C, preferably -20°C to 150°C, and the contact time is 1 min-20 h, preferably 5 min-8 h. The number of titanium treatments is 0-10 times, preferably 1-5 times.

[0049] According to the present application, the organoaluminum compound can be selected from an alkylaluminum compound, preferably from a trialkylaluminum, and in particular can be selected from trimethylaluminum, triethylaluminum, triisobutylaluminum, trihexylaluminum, tri-n-butylaluminum, tri(2-methyl-3-phenyl-butyl)aluminum, tri(2-phenyl-butyl)aluminum and the like.

[0050] The molar ratio of aluminum in the organoaluminum compound to titanium in the solid catalyst component can be (10-500) : 1, preferably (25-100) : 1.

[0051] In the present application, the external electron donor can be selected from ethers, esters and silane compounds, and preferably selected from silane compounds.

[0052] The silane compound can be specifically selected from at least one of tetramethoxysilane, tetraethoxysilane, trimethylmethoxysilane, trimethylethoxysilane, trimethylphenoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, methyl tert-butyl dimethoxysilane, methyl isopropyl dimethoxysilane, diphenyloxydimethoxysilane, diphenyldiethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, vinyltrimethoxysilane, cyclohexylmethyldimethoxysilane, dicyclopentyldimethoxysilane, diisopropyl dimethoxysilane, diisobutyl dimethoxysilane, 2-ethylpiperidinyl-2-tert-butyl dimethoxysilane, (1,1,1-trifluoro-2-propyl)-2-ethylpiperidinyl dimethoxysilane and (1,1,1-trifluoro-2-propyl)-methyl dimethoxysilane.

[0053] The molar ratio of silicon in the silane compound to aluminum in the organoaluminum compound is 1: (1-100), preferably 1: (10-60).

[0054] According to the present application, the components of the Ziegler-Natta catalyst system are optionally pre-complexed before entering the polymerization reactor. The solid catalyst component, the organoaluminum compound and the external electron donor are pre-complexed before being fed into the polymerization reactor. The pre-complexing treatment can improve the polymerization activity and stereoregulation ability of the catalyst system. Preferably, the Ziegler-Natta catalyst system is pre-complexed before being used in the polymerization reaction. The pre-complexing treatment is carried out at a temperature of -10°C to 60°C, preferably 0-30°C, for a time period of 0.1-180 min, preferably 5-30 min. The pre-complexing treatment can be carried out in a continuous stirred tank reactor or in other vessels that can provide sufficient mixing, such as a loop reactor, a pipe with static mixer or even a pipe in which the material is in turbulent flow.

[0055] In the present application, the polymerization reaction can be carried out in an inert organic solvent or in liquid butene-1. Preferably, the polymerization reaction is carried out in liquid butene-1. The inert organic solvent can be a conventional inert organic solvent in the art, and can be n-hexane, isobutane, n-pentane, propane and isopentane, etc.

[0056] The polymerization monomer can be butene-1 and optionally C2-C 10 α-olefin monomer, i.e. the polymerization reaction is homopolymerization of butene-1 or random copolymerization of butene-1 with other C2-C 10 d olefins such as ethylene and propylene.

[0057] In addition, hydrogen can be introduced during the polymerization reaction. Hydrogen acts as a molecular weight regulator, and the hydrogen partial pressure is in the range of 0-2 MPa. With the increase of hydrogen partial pressure, the intrinsic viscosity of the polymer gradually decreases, and the molecular weight of the polymer also gradually decreases. In addition to regulating the molecular weight of the polymer, appropriate amount of hydrogen can also improve the polymerization activity and the stereoregulation ability of the active center, so that the isotacticity of the polymer is improved. However, when the amount of hydrogen is excessive, the activity and isotacticity will decrease.

[0058] In the present application, the polymerization reaction can be carried out continuously or intermittently. The continuous polymerization can be carried out in two or more liquid phase reactors connected in series, and the liquid phase reactor can be a loop reactor or a stirred tank reactor.

[0059] According to the present application, the preparation method comprises: discharging the product of the polymerization reaction into hot water, introducing steam to remove unreacted monomers, and then filtering to obtain a solid, which is dried to obtain polybutene-1. The removed unreacted monomers are rectified and recycled. The dried polymer can be extruded and granulated, and additives commonly used in the technical field, such as antioxidants, light stabilizers, heat stabilizers, colorants and fillers, etc. can be added during the granulation.

[0060] In the present application, the "highly regulated" refers to the isotacticity of 95wt% or more, especially 97wt% or more.

[0061] The substances, devices and process parameters not defined in the present application can be selected according to the prior art, which are conventional technical means in the art.

[0062] The present application will be further described below in conjunction with examples. However, it is not limited by these examples.

[0063] In the following examples and comparative examples, the relevant data are obtained according to the following test methods:

[0064] 1. Determination of isotacticity: A certain amount of sample was placed in a 70℃ vacuum oven for vacuum drying to extract the residual monomer and moisture in the sample. Vacuum drying was performed until the constant weight was reached. 1-2g of sample was accurately weighed in a filter paper cylinder, which was sealed with a paper clip, and placed in an extractor for extraction with boiling ether for 24h. After being taken out, it was dried to constant weight in a vacuum oven. The content of the unextractable material was used as the isotacticity of polybutene-1.

[0065] 2. Determination of melt flow rate (MFR): GB / T 3682.1-2018, using CEAST 7026 type melt index instrument, under the conditions of 2.16kg load and 190℃.

[0066] Preparation Example 1

[0067] The method of preparing alkoxy magnesium particles in reference patent document CN102453150B was used: After the 16L pressure-resistant reactor with a stirrer was sufficiently replaced with nitrogen, ethanol 10200mL and 2-ethylhexanol 300mL were added to the reactor, and iodine 6g and magnesium chloride 4g were added to dissolve them. After stirring, the temperature was raised until the reflux temperature of the reaction system was reached. Then magnesium powder 640g was added gradually. The reaction was carried out until it was completed, i.e. no hydrogen gas was discharged. Then washing, separation and drying were carried out. The obtained dialkoxy magnesium carrier had an average particle size (D50) of 47.0μm and a particle size distribution index of 0.82, and the content of isooctyloxy magnesium was 1.7wt%.

[0068] Preparation of the solid catalyst component: in a 100 mL reactor purged with high purity nitrogen, 10 g of the above magnesium alkoxide particles, 50 mL of toluene, 3.0 mL of poly- methylsiloxane having a kinematic viscosity of 100 cSt, and 2.0 mL of tetraethyl titanate were introduced, and the temperature was raised to 60°C and maintained for 8 hours to obtain a suspension X1. Meanwhile, in a 300 mL reactor purged with high purity nitrogen, 10 mL of toluene and 90 mL of titanium tetrachloride were introduced, and the temperature was raised to 80°C, then the suspension X1 was added, and the temperature was slowly raised to 115°C, and 3.0 mL of di-n-butyl phthalate, 1.0 mL of diethyl phthalate, and 1.0 mL of 3,5-heptanediol dibenzoate were added during the temperature raising process, and the temperature was maintained for 2 hours, then the liquid was filtered off. Then, 30 mL of titanium tetrachloride and 120 mL of toluene were added, the temperature was raised to 110°C, and the temperature was maintained for 1 hour, then the liquid was filtered off. Then, 120 mL of titanium tetrachloride and 30 mL of toluene were added, the temperature was raised to 110°C, and the mixture was stirred for 1 hour, and this process was repeated twice, then the liquid was filtered off, the obtained solid was washed with 150 mL of hexane at 60°C for 4 times, the liquid was filtered off and dried, and a solid powder was obtained, which was the solid catalyst component 1.

[0069] Preparation Example 2

[0070] The difference from Preparation Example 1 is that 1.0 mL of 2,4-pentanediol dibenzoate was used instead of 1.0 mL of 3,5-heptanediol dibenzoate, and the rest was the same, and the solid catalyst component 2 was obtained.

[0071] Preparation Example 3

[0072] The difference from Preparation Example 1 is that 3.0 mL of diisobutyl phthalate was used instead of 3.0 mL of di-n-butyl phthalate, and the rest was the same, and the solid catalyst component 3 was obtained.

[0073] Preparation Example 4

[0074] The difference from Preparation Example 1 is that 3.0 mL of 100 cSt epoxy-modified poly- methylsiloxane and 2.0 mL of tetraisopropyl titanate were used instead of 3.0 mL of poly- methylsiloxane and 2.0 mL of tetraethyl titanate, and the rest was the same, and the solid catalyst component 4 was obtained.

[0075] Example 1

[0076] Into a 5L high-pressure reactor, solid catalyst component 1, triisobutylaluminum, dicyclopentyl dimethoxysilane pre-complexed at room temperature for 2 minutes, and hydrogen were added, followed by the addition of 2.3L of butene, and then the temperature was raised to start polymerization. The polymerization was carried out at 70°C for 1 hour. After the reaction, the polymer was discharged into a discharge container containing hot water, and steam was introduced to remove unreacted monomers. Then, the solid was filtered and dried to obtain the polymer. The specific process conditions and polymerization results are shown in Table 1.

[0077] Example 2

[0078] The difference from Example 1 is that the amount of hydrogen added is different, and the rest is the same. The specific process conditions and polymerization results are shown in Table 1.

[0079] Example 3

[0080] The difference from Example 1 is that the amount of hydrogen added is different, and the rest is the same. The specific process conditions and polymerization results are shown in Table 1.

[0081] Example 4

[0082] The difference from Example 1 is that the amount of hydrogen added is different, and the rest is the same. The specific process conditions and polymerization results are shown in Table 1.

[0083] Example 5

[0084] The difference from Example 1 is that the amount of hydrogen added is different, and the rest is the same. The specific process conditions and polymerization results are shown in Table 1.

[0085] Example 6

[0086] The difference from Example 1 is that the temperature of the polymerization reaction is different, and the rest is the same. The specific process conditions and polymerization results are shown in Table 1.

[0087] Example 7

[0088] The difference from Example 1 is that the temperature of the polymerization reaction is different, and the rest is the same. The specific process conditions and polymerization results are shown in Table 1.

[0089] Example 8

[0090] The difference from Example 1 is that the temperature of the polymerization reaction is different, and the rest is the same. The specific process conditions and polymerization results are shown in Table 1.

[0091] Example 9

[0092] The difference from Example 1 is that solid catalyst component 2 is used instead of solid catalyst component 1 in the catalyst system, and the rest is the same.

[0093] Example 10

[0094] The difference between Example 1 and Example 2 is that in the catalyst system, solid catalyst component 3 is used instead of solid catalyst component 1, and the rest is the same.

[0095] Example 11

[0096] The difference between Example 1 and Example 2 is that in the catalyst system, solid catalyst component 4 is used instead of solid catalyst component 1, and the rest is the same.

[0097] Comparative Example 1

[0098] The difference between Example 2 and Comparative Example 1 is that the solid catalyst component used is a catalyst prepared by the method described in Example 1 of patent document CN93102795, and the Ti content is 2.2wt%. The specific process conditions and polymerization results are shown in Table 1.

[0099] Table 1

[0100]

[0101] As can be seen from Table 1, the catalyst system of the present application is used for butene-1 bulk polymerization, and the polymerization activity is higher than that of the conventional Z-N catalyst, and the highest activity can reach 50kgPB / gcat·h, and the isotacticity of polybutene-1 is also greatly improved, and the highest can reach 99.3wt%. Examples 1-5 carried out polymerization reaction with different hydrogen addition amounts, and appropriate hydrogen can not only act as a molecular weight regulator, but also can improve the polymerization activity and the isotacticity of the polymer. Examples 6-8 carried out polymerization reaction at different temperatures, and under different temperatures, the catalyst activity and hydrogen regulation performance are different.

[0102] The above has described various embodiments of the present application, and the above description is exemplary, not exhaustive, and is not limited to the disclosed embodiments. Many modifications and changes are obvious to those skilled in the art without departing from the scope and spirit of the described embodiments.

Claims

1. A process for the preparation of a high isotactic polybutene-1, characterized in that, The preparation method comprises: polymerizing butene-1 and optional C2-C 10 α-olefin monomers in the presence of a Ziegler-Natta type catalyst system; The Ziegler-Natta catalyst system contains a solid catalyst component, an organic aluminum compound, and an external electron donor; the solid catalyst component contains a reaction product of a catalyst carrier, an internal electron donor, and a titanium-containing halide, the internal electron donor contains a carboxylic acid ester compound and a polyhydric alcohol ester compound; the catalyst carrier contains a reaction product of alkoxy magnesium particles and a particle protective agent, the particle protective agent is a titanate compound and a polysiloxane substance; The conditions of the polymerization reaction include: the polymerization temperature is 0-150℃; the polymerization pressure is higher than the saturated vapor pressure of butene-1 at the corresponding polymerization temperature.

2. The process for the preparation of the high isotactic polybutene-1 according to claim 1, wherein, The polymerization temperature is 40-100℃.

3. The method for preparing high isotactic polybutene-1 according to claim 1, wherein, The structure of the alkoxy magnesium particles is shown in formula I: Mg(OR9) 2-p (OR 10 ) p Formula I In formula I, R9and R 10 each independently selected from the group consisting of C1-C8 linear alkyl, C3-C8 branched alkyl, 0 < p < 2.

4. The process for the preparation of the high isotactic polybutene-1 according to claim 3, wherein, R9and R 10 In another embodiment, the alkyl magnesium particles are selected from at least one of diethyl magnesium, di-n-propyl magnesium, diisopropyl magnesium, di-n-butyl magnesium, diisobutyl magnesium, di-n-amyl magnesium, diisopentyl magnesium, di-n-hexyl magnesium, di(2-ethyl)hexyl magnesium, di-n-octyl magnesium, di(2-ethyl)hexyl magnesium, di-n-decyl magnesium, di(2-ethyl)hexyl magnesium, di-n-dodecyl magnesium, di(2-ethyl)hexyl magnesium, di-n-tetradecyl magnesium, di(2-ethyl)hexyl magnesium, di-n-hexadecyl magnesium, di(2-ethyl)hexyl magnesium, di-n-octadecyl magnesium, di(2-ethyl)hex 5. The method of preparing high isotactic polybutene-1 according to claim 1, wherein, The structure of the titanate compound is shown in formula II: (R1’O) a Ti(OR2’) b (OR3’) c X d Formula II In formula II, R1', R2' and R3' are the same or different, each is selected from H or alkyl, X is selected from alkoxy, carboxyl, chlorine, sulfonic acid group, phosphoric acid group or sulfuric acid group, a, b, c and d are independently integers of 0-4, and a+b+c+d=4; The structure of the polysiloxane substance is shown in formula III: (R 1 R 2 R 3 )SiO[(R 7 R 8 )SiO] n··· [(R y R z )SiO] m Si(R 4 R 5 R 6 ) Formula III In Equation III, R 1 -R z Whether the C1-Cs are the same or different, they are each selected from substituted or unsubstituted C1-Cs. 12 Straight-chain alkyl, C3-C 12 Branched alkyl groups, C3-C 10 cycloalkyl, C7-C 20 alkylaryl, substituted or unsubstituted C6-C 20 Aromatic groups, C2-C 12 The chain consists of alkenyl, hydrogen, hydroxyl, alkoxy, acetoxy, chlorine, amino, carboxyl, mercapto, carbon functional groups, and polyether chains; the degree of polymerization n+m is an integer from 2 to 100.

6. The method of preparing high isotactic polybutene-1 according to claim 5, wherein, R 1 -R z selected from cyano.

7. The method of preparing high isotactic polybutene-1 according to claim 5, wherein, R1', R2' and R3' are each selected from the group consisting of C1-C 10 alkyl.

8. The method of preparing high isotactic polybutene-1 according to claim 7, wherein, The titanate compound is selected from at least one of tetramethyl titanate, tetraethyl titanate, tetrapropyl titanate, tetrabutyl titanate, tetrapentyl titanate, tetrahexyl titanate, tetraheptyl titanate, tetraisooctyl titanate, tetrapelargonyl titanate, tetradecyl titanate and isomers thereof.

9. The method of preparing high isotactic polybutene-1 according to claim 8, wherein, The titanate compound is at least one of tetraethyl titanate, tetraisopropyl titanate and tetrabutyl titanate.

10. The method of preparing high isotactic polybutene-1 according to claim 5, wherein, The polysiloxane substance is selected from at least one of polymethylsiloxane, polyethylsiloxane, polyphenylsiloxane, polymethylhydrosiloxane, polymethylphenylsiloxane, polymethylchlorophenylsiloxane, polymethylethoxysiloxane, polymethyltrifluoropropylsiloxane, polymethylvinylsiloxane, polymethylhydroxysiloxane, polyethylhydrosiloxane, polyhydroxylhydrosiloxane, polycyanosiloxane, polyaminosiloxane, polyepoxysiloxane, polyethersiloxane, polycarboxysiloxane, polyalcoholhydroxysiloxane, polyphenolhydroxysiloxane, polysulfhydrylsiloxane and modified bodies thereof.

11. The method of preparing high isotactic polybutene-1 according to claim 10, wherein, The polysiloxane substance is at least one of polymethylsiloxane, polyethylsiloxane, polymethylphenylsiloxane, polyethersiloxane, polycyanosiloxane and modified bodies thereof.

12. The method of preparing high isotactic polybutene-1 according to claim 5, wherein, The molar ratio of the titanate compound to magnesium in the alkoxy magnesium particles is (0.01-5):1; the molar ratio of the polysiloxane substance to magnesium in the alkoxy magnesium particles is (0.01-5):

1.

13. The method of preparing high isotactic polybutene-1 according to claim 12, wherein, The molar ratio of the titanate compound to magnesium in the alkoxy magnesium particles is (0.02-2):1; the molar ratio of the polysiloxane substance to magnesium in the alkoxy magnesium particles is (0.02-2):

1.

14. The method of preparing high isotactic polybutene-1 according to claim 1, wherein, The carboxylic acid ester compound is selected from benzoic acid monoester compounds or phthalate compounds with the structure shown in formula IV, Formula IV In formula IV, R1and R2are independently selected from substituted or unsubstituted C1-C8alkyl, C3-C10cycloalkyl, or C6-C10aromatic group; R3-R6are independently selected from hydrogen, halogen, C1-C4alkyl, or C1-C4alkoxy; and n is an integer from 0 to 4. 10 In formula IV, R1and R2are independently selected from substituted or unsubstituted C1-C8alkyl, C3-C10cycloalkyl, or C6-C10aromatic group; R3-R6are independently selected from hydrogen, halogen, C1-C4alkyl, or C1-C4alkoxy; and n is an integer from 0 to 4. 20 In formula IV, The polyhydric alcohol ester compound is selected from dihydric alcohol ester compounds with the structure shown in formula V, The polyhydric alcohol ester compound is selected from dihydric alcohol ester compounds with the structure shown in formula V, Formula V In formula V, R 1’ and R 2’ Whether the C1-Cs are the same or different, they are each selected from substituted or unsubstituted C1-Cs. 20 Straight-chain alkyl, C3-C 20 Branched alkyl groups, C3-C 20 cycloalkyl, C6-C 20 aryl, C7-C 20 alkylaryl, C7-C 20 Aryl groups, C2-C 10 olefin group, C 10 -C 20 Fused ring aryl group; R 3’ -R 8’ They may be the same or different, each selected from hydrogen, halogen, substituted or unsubstituted C1-C. 20 Straight-chain alkyl, C3-C 20 Branched alkyl groups, C3-C 20 cycloalkyl, C6-C 20 aryl, C7-C 20 alkylaryl, C7-C 20 Aryl groups, C2-C 10 olefin group, C 10 -C 20 Fused ring aryl; or R 3’ -R 6’ At least one of them is related to R 7’ -R 8’ At least one of them forms a ring; The molar ratio of the carboxylic acid ester compound to magnesium in the alkoxymagnesium particles is (0.01-5):1; the molar ratio of the polyhydric alcohol ester compound to magnesium in the alkoxymagnesium particles is (0.01-5):

1.

15. The method of preparing a high isotactic polybutene-1 according to claim 14, wherein, At least three of R3-R6 are hydrogen.

16. The method of preparing a high isotactic polybutene-1 according to claim 15, wherein, The carboxylic acid ester compound is at least one of ethyl benzoate, propyl benzoate, butyl benzoate, pentyl benzoate, hexyl benzoate, heptyl benzoate, octyl benzoate, nonyl benzoate, decyl benzoate, dimethyl phthalate, diethyl phthalate, dipropyl phthalate, di-n-butyl phthalate, diisobutyl phthalate, dipentyl phthalate, dihexyl phthalate, diheptyl phthalate, dioctyl phthalate, dinonyl phthalate, didecyl phthalate, methyl ethyl phthalate, methyl propyl phthalate, methyl butyl phthalate, methyl pentyl phthalate, ethyl propyl phthalate, ethyl butyl phthalate, ethyl pentyl phthalate, ethyl hexyl phthalate, propyl butyl phthalate, propyl pentyl phthalate, propyl hexyl phthalate, butyl pentyl phthalate, butyl hexyl phthalate, pentyl hexyl phthalate, and isomers thereof.

17. The method of preparing a high isotactic polybutene-1 according to claim 14, wherein, The dihydric alcohol ester compound is at least one of 2-ethyl-1,3-propanediol dibenzoate, 2-propyl-1,3-propanediol dibenzoate, 2-isopropyl-2-isopentyl-1,3-propanediol dibenzoate, 1,3-butanediol dimethyl benzoate, 2-methyl-1,3-butanediol di-m-chlorobenzoate, 2,3-dimethyl-1,3-butanediol dibenzoate, 1,3-pentanediol dineopentanoate, 2,4-pentanediol dibenzoate, 2-methyl-1,3-pentanediol benzoate cinnamate, 2,2-dimethyl-1,3-pentanediol dibenzoate, 2,4-heptanediol dibenzoate, 3,5-heptanediol dibenzoate, 4-ethyl-3,5-heptanediol dibenzoate, and 2-methyl-3,5-heptanediol dibenzoate.

18. The method of preparing a high isotactic polybutene-1 according to claim 17, wherein, The dihydric alcohol ester compound is at least one of 3,5-heptanediol dibenzoate, 4-ethyl-3,5-heptanediol dibenzoate, and 2,4-pentanediol dibenzoate.

19. The method of preparing high isotactic polybutene-1 according to claim 14, wherein, The molar ratio of the carboxylic acid ester compound to magnesium in the alkoxymagnesium particles is (0.02-2):1; the molar ratio of the polyhydric alcohol ester compound to magnesium in the alkoxymagnesium particles is (0.02-2):

1.

20. The method of preparing high isotactic polybutene-1 according to claim 1, wherein, The structure of the titanium-containing halide is shown in Formula VI, TiX 1 e (OR7) 4-e Formula VI In formula VI, X is halogen, R7is a C1-C4hydrocarbon group, and e is an integer from 0 to 4. 1 20 In formula VI, X is halogen, R7is a C1-C4hydrocarbon group, and e is an integer from 0 to 4.​ 21. The method of preparing a high isotactic polybutene-1 according to claim 20, wherein, X 1 R7 is C1-C5 alkyl, and R8 is hydrogen or C1-C5 alkyl.

22. The method of preparing a high isotactic polybutene-1 according to claim 1, wherein, The organoaluminum compound is selected from an alkylaluminum compound; The molar ratio of aluminum in the organoaluminum compound to titanium in the solid catalyst component is (10-500):

1.

23. The method of preparing a high isotactic polybutene-1 according to claim 22, wherein, The organoaluminum compound is a trialkylaluminum.

24. The method of preparing a high isotactic polybutene-1 according to claim 23, wherein, The organoaluminum compound is at least one of trimethylaluminum, triethylaluminum, triisobutylaluminum, trihexylaluminum, tri-n-butylaluminum, tris(2-methyl-3-phenyl-butyl)aluminum, and tris(2-phenyl-butyl)aluminum.

25. The method of preparing a high isotactic polybutene-1 according to claim 22, wherein, The molar ratio of aluminum in the organoaluminum compound to titanium in the solid catalyst component is (25-100):

1.

26. The method of preparing a high isotactic polybutene-1 according to claim 1, wherein, The external electron donor is selected from ethers, esters, and silane compounds; The molar ratio of silicon in the silane compound to aluminum in the organoaluminum compound is 1:(1-100).

27. The method of preparing a high isotactic polybutene-1 according to claim 26, wherein, The external electron donor is selected from silane compounds.

28. The method of preparing a high isotactic polybutene-1 according to claim 27, wherein, The silane compound is selected from at least one of tetramethoxysilane, tetraethoxysilane, trimethylmethoxysilane, trimethylethoxysilane, trimethylphenoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, methyl-tert-butyldimethoxysilane, methylisopropyldimethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, vinyltrimethoxysilane, cyclohexylmethyldimethoxysilane, dicyclopentyldimethoxysilane, diisopropyldimethoxysilane, diisobutyldimethoxysilane, 2-ethylpiperidinyl-2-tert-butyldimethoxysilane, (1,1,1-trifluoro-2-propyl)-2-ethylpiperidinyl dimethoxysilane, and (1,1,1-trifluoro-2-propyl)-methyldimethoxysilane.

29. The method of preparing a high isotactic polybutene-1 according to claim 26, wherein, The molar ratio of silicon in the silane compound to aluminum in the organoaluminum compound is 1:(10-60).

30. The method of preparing a high isotactic polybutene-1 according to claim 1, wherein, The Ziegler-Natta catalyst system is pre-complexed before being used in the polymerization reaction, the pre-complexing temperature is -10-60°C, and the pre-complexing time is 0.1-180 min.

31. The method of preparing a high isotactic polybutene-1 according to claim 30, wherein, The pre-complexing temperature is 0-30°C, and the pre-complexing time is 5-30 min.

32. The method of preparing a high isotactic polybutene-1 according to claim 1, wherein, The polymerization reaction is carried out in liquid butene-1, and hydrogen is introduced during the polymerization.

33. The method of preparing a high isotactic polybutene-1 according to claim 1, wherein, The preparation method comprises discharging the product of the polymerization reaction into hot water, introducing steam to remove unreacted monomers, and then filtering to obtain a solid, which is dried to obtain polybutene-1. The preparation method comprises discharging the product of the polymerization reaction into hot water, introducing steam to remove unreacted monomers, and then filtering to obtain a solid, which is dried to obtain polybutene-1.

Images