前苏联专利SU1025322A3 Catalyst for homopolymerization of ethylene and method of producing the same

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专利摘要:
A catalyst for the preparation of ethylene polymers having higher melt indexes comprises a silyl chromate deposited on a silica support containing both aluminum and titanium.
公开号:SU1025322A3
申请号:SU782568008
申请日:1978-01-20
公开日:1983-06-23
发明作者:Джекоб Ливайн Исаак；Джон Кэрол Фредерик
申请人:Юнион Карбид Корпорейшн (Фирма)；
IPC主号:

专利说明:

10 The invention relates to catalysts for goiopolymer eats | and ethylene and its copolymerization with 6-C-C olefins and methods for their preparation. Known catalyst for olefin polymerization, including 2t3% chromium oxide on an aluminosilicate carrier, with a holder of 90 AED of silicon dioxide and 10 weight K of alumina t and a method for its addition by treating {(luminescent silica carrier with 4); impregnation with chromic anhydride and acidification in air at 500 ° C ij. However, this catalyst is sensitive to the action of moisture, so it should not be in contact with the atmosphere, the dew point of which exceeds em. Polymerized ethylene and, the solvent should not contain Ojj, “210 or COj. The closest to the invention in its technical essence and the effect achieved is a catalyst for the homo polymerization of ethylene and its copolymerization. with eft-olefins, contents of triphenylsilyl chromate, alumina on a silica carrier with the following content of components, wt.%: triphenylsil chromate 3.0-3.1 oxide oxide 0,, 9; the carrier is the rest, and the method of its emission by heat treatment of silica carriers, containing alumina, at 750-820 ° C, followed by cooling and applying triphenylsilyl chromate 2 on it. However, the catalyst obtained in a known manner has insufficient activity. the "" and "th in the presence of a catalyst prepared according to a known method is 0.28, the yield strength is 11.7. The aim of the invention is to increase the activity of the catalyst. The proposed objective is achieved by the fact that the catalyst for homopolymerization of ethylene and copolymerization of it with β6 Ci-Clefines containing triphenylsilylchromate, aluminum oxide on a silica carrier, additionally contains titanium dioxide, with the following t6 reduction of components, by weight. 22-11.7 Aluminum oxide 2 Titanium dioxide. 7, A-8.7 Carrier Else Moreover, the catalyst additionally contains 0.53 weight D of fluorine. According to the method for preparing a catalytic agent for homopolymerization of ethylene and its copolymerization with Cj-Cj α-olefins by heat treatment of silica carrier containing alumina, at 750-820 ° C, followed by cooling and applying triphenylsilylchromate on it, in addition to heat treatment, tetropropoxide or tetraisopropoxide oxide . Moreover, at the stage of heat treatment, ammonium hexafluorosilicate is additionally introduced. The proposed catalyst in comparison with the known has a high activity. For example, the melt index of polyhexene obtained in the presence of a catalyst prepared by the inventive method is 2.81, the flow index, 1. The catalysts are prepared by thermally treating a silica carrier containing aluminum and titanium, followed by the application of silyl chromate. After applying the silyl chromate to the silica substrate, no heat treatment of the catalyst is carried out. The operation of applying the silyl chromate to the silica substrate is carried out from its solution in an organic solvent. A class of examples of silica carriers with a large surface area includes a microspherical, intermediate density silica carrier (NSPP) with a specific surface area of 300 Mvr, a pore diameter of about 200 A, and an average particle size of about 70 microns, which is approximately equal to 0,0028 inches, (varieties U. R. Grace C-952); intermediate density silica (PP), whose specific surface area is approximately 300 pore diameter is about 1 bO A, and the average particle size is about 103 MKj which is approximately 0 inches (grade P.R. Grace C-56) and silica Varieties Devidson 9b7 ,. whose specific surface area is a specific pore volume of about 0.90 cm / g. Silica or silica of the variety Davidson 9b7 contains about 13 wt.% Alumina.
Aluminum can be introduced into the proposed catalyst either by selecting silica with chemically bound alumina already present in it, for example, Devidson9b7 | or by treating the cracksmith with a solution of an aluminum compound, in particular aluminum nitrate.
Titanium compounds, which are used in the preparation of the catalyst, include tetrapropoxide or titanium tetraisopropoxide.
Aluminum is introduced into silica but-. a sieve by treating said silica carrier with a solution of an aluminum compound HIM, but aluminum may already be present in the cream of an unearthly precursor material in the form of alumina. In the case of using such catalysts, when changes in molecular weight distribution and changes in the rate of copolymerization of ethylene with a comonomer are desired, a fluorination agent, such as ammonium hexafluorosilicate, can be used. In the case of the use of a fluorination agent, it is combined with a silica carrier before the application of silichromate. Fluorine compounds deposit a silica substrate from aqueous solutions of these compounds or by dry displacement of solid fluorine compounds with other components of the catalyst during its preparation. Reference Example 1. A silica support is obtained. In a solution of 1.5 g of nocanhydrate tetra ta aluminum in 150 ml of water, 20 g of Polypor grade silica are added. The pore size of this silica is 250-270 A, and its specific surface area is ZUO-OO. This mixture is filtered and 7k ml of filtrate is isolated. Then the silica residue is dried. A portion of the dry residue is subjected to aging at 820 ° for 16. h in a stream of nitrogen, followed by cooling. The aluminum content in the final silica nsuyuite- 50
le in terms of aluminum oxide is 0.5 wt.
Triggers get a polymerization catalyst by mixing 0.98 g of silica carrier with 50 ml of n-hexane and 0.030 g of bis-triphenylsilyl chromate. This mixture is stirred in a stream of nitrogen at room temperature for 1 h.
The final slurry is used as a polymerization catalyst.
Evaluate the properties of a polymerization catalyst;) as follows.
The slurry is loaded into a stirred high pressure reaction vessel with a capacity of 1000 ml together with 500 ml of n-hexane and ml of 1-hexane. Then this vessel is tightly closed and ethylene is supplied. An increased pressure is created in it, which reaches 200 PS / IPT, kg / m). The polymerization is carried out for a period of
equal to 1.0 dg / min.
Example 1. For a silica carrier, a solution of 1.50 g of aluminum nitrate nonahydrite in 150 ml of water is added with 20 g of Polypora grade silica described in reference example 1. This mixture is filtered to give 7 ml of filtrate. Balance su75 min. The yield is 185 g of ethylene copolymer, the melt index of which is 0.28 dg / min, the flow index is 11.7 dg / min, and the density is 939 g / cm. The control example is p. 2. The experiment of control example 1 is repeated completely, using the fact that 0.93 g of silica carrier is used in conjunction with 0.030 g of bis-triphenylsilyl chromate during the preparation of the catalyst. Instead of 1 hexene, a pressure of 20 pounds / inch (1 kg / cm) is created by means of propylene. To evaluate the properties of the resulting polymerization catalyst, after 110 minutes, 31 g of ethylene copolymer is obtained, the melt index of which is 2.69 dg / min, the flow index is 243 g / min, and the density is 0, 90 g / cmE. The control example 3. The procedure of control example 1 is repeated completely, but in this case, 0.98 g of silica carrier is used in conjunction with 0.030 g of bis-triphenylsilium chromate in the preparation of the catalyst, and no co-monomer is used together with ethylene. To evaluate the properties of the catalyst obtained, after 105 minutes of polymerization, 159 g of ethylene homopolymer is obtained. The resulting homopolymer does not have any melt index, and its flow index is shat. With the use of a sample of this residue, which is pre-dried, a suspension of 100 MP of pentene is prepared, with its combination with 2.8 g of titanium tetrathioopropoxide. The solvent is evaporated and the residue is stirred in an oxygen atmosphere at 9 tO C for 17 liters to obtain a carrier. The content of aluminum in the support in terms of alumina is 0.5%, and the content of titanium in terms of titanium dioxide is 7.5%. A polycurization catalyst is obtained by mixing 1.0 g of the obtained silica carrier, with 50 ml of n-hexane and 0.030 g of bis-triphenylsilyl chromate. This mixture was stirred in a stream of nitrogen at room temperature for 1 hour. The final suspension was used as a LLMeration catalyst. To evaluate the properties of the polymerization catalyst, the catalytic suspension is loaded into a reaction vessel used under high pressure, together with 500 ml of hexane and kG ml of 1-hexene. This vessel is then sealed and pressurized ethylene is increased to 200 pounds / inch (k,} kg / cm). Then at | The polymerization reaction is carried out for 40 minutes. Thus, 136 g of a copolymer of ethylene with 1-hexene is obtained, the melt index of which is 2.81 dg / min, the flow index is 92.1 dg / min, and the density is 0.932 g / cm. Example 6 p 2. The experiment of Example 1 is repeated using the same catalytic suspension, but instead of 1-hexene, propylene is used, by means of which an increased pressure of 20 pounds / inch (1 .tl kg / cm) is created in the polymerization reactor. The polymerization process is carried out for 90 minutes at 86 ° C. As a result, 93 g of ethylene-propylene polymer is obtained, whose paplav index is 27.5 dg / min and its density is 0.895 g / cm. Froze In order to obtain a silica carrier, a sample of a diamond of Polypor variety is dried at and then a suspension is prepared in 100 ml of pentane using 10.1 g of this silica. 0.115 g of triisopropoxide in a toluene solution and then 3.0 are added to the suspension. g titanetrapropoksid. This solvent is removed by evaporation and the residue is aged for 16 hours under an oxygen atmosphere. The aluminum content in terms of alumina is 0.3 wt.%, And the content of titanium in terms of titanium dioxide is 7.6 wt.%. A Polymerizable catalyst is obtained by mixing 1.0 g of the resulting silica carrier with 0, g of bistriphenylsilyl chromate and 50 ml hexaIa. This mixture is stirred in a stream of nitrogen at room temperature for 1 hour. The suspension thus prepared is used as a polymerization catalyst. To evaluate the properties of the polymerization catalyst, a suspension is loaded into the reaction vessel together with 500 ml of n-hexane. This vessel is tightly closed and, by the introduction of compressed ethylene, the pressure in it is increased to 200 pounds / inch (kg / cm). After 50 minutes of polymerization at 8 bps, 108 g of ethylene homopolymer are obtained, whose flow index is 4.0 dg / min. During the standard tests to determine the melt index, no expiration was detected. The properties of catalysts containing and not containing titanium are presented in Table 1. .. T a b l i c a 1
Continued table. one
None None
Check 3
"There is Missing,. EXAMPLE The experiment described in Example 3 was repeated completely, but the catalytic suspension was prepared using 0.96 g cream of an unearthly carrier, together with 10 g of bis-trifenylsilyl chromate and introduced into the reaction vessel. hydrogen up to. pressure of 30 pounds / inch (2.11 kg / cm) after which ethylene is injected, pressure is increased to 200 pounds / inch (I, 1 kg / / cm). During the course of the reaction at a reaction temperature of 8bC for L5 min, 17 g of ethyl 4-homopolymer are obtained, whose melting index is 0.19 dg / min, and the flow index is 3bg dg / min. The presence of hydrogen increases the melt index of the resulting ethylene homopimer. EXAMPLE 5 In order to obtain a silica carrier, the experiment of Example 3 was repeated except for the changes, which in this case use 9.0 g of Neepam cream of Polypor variety, 0.110 g of aluminum t of riisopropoxide, 2.7 g titanetra-ihropropoxide and an additional 0.09 g of ammonium hexafluorosilicate. This mixture is subjected to "incubation in nitrogen atmosphere in the dark of 17 m, followed by cooling. The aluminum content of the thus obtained silica carrier in terms of alumina is 0.3 wt.%, And the content of tetanum in it in terms of titanium dioxide is 7.8 wt.%, The catalytic suspension is prepared in accordance with example 1 with using 0.93 g of silica carrier 50 MP n-hexane and 0.0 g of bis-triphenylsilyl chromate. To evaluate the properties of the polymerization catalyst, the catalytic suspension in the reaction vessel together with 500 ml of n-hexane. This vessel (InoTHO is closed and injected; compressed ethylene is pressurized to 200 psi / inch (Itfl. Kg / cm
Without flow, 1.0 Without flow ti, 0 After going through the reaction for 30 NIN at a polymerization temperature of 86 ° C, 55 g of ethylene is obtained. homopolymer, which in the course of- Neither tests with a definite melt index show any leakage, while its turnover rate is 9f5 dg / min. EXAMPLE 6 To obtain an intermediate carrier medium, 12.8 g of silica and alumina of variety 9b7 are dried at 200 ° C, after which a suspension of 100 MP of pentane is prepared using this product. Then this suspension is combined with 3 grams of titanium tetraisopropoxide. The solvent is removed and the residue is maintained under an oxygen atmosphere for 17 hours, followed by cooling. The aluminum content in the silica carrier in terms of alumina is 13 wt.%, And the content of titanium) in terms of titanium dioxide is 7.5 wt.%. The catalytic suspension was prepared using 1.0 f of silica carrier, 50 ml of n-hexane and 0.03 g & 1C - tripheny / y, and liromat a. To evaluate the properties of the polymerization catalyst, catalytic sus-. Pencil 3arpymai6f in the reaction vessel together with 500 ml of n-hexane and ifO.Mn 1-hexane. Then this vessel is tightly closed and its pressure is increased by introducing compressed e-bee to 200 pounds / per inch (1, 1 kg / cn). The rear limbs are held for 90 min. 80 g of ethylene copolymer are obtained, the melt index of which is 3, dg / min, and the density is 0.933 g / cm 3. Not looking at the fact that the flow rate of this copolymer varies with the flow rate of the polymers of the previous and control examples, it should be borne in mind that this flow rate largely depends on the physical structure of the silica carrier. Thus, the flow index varies with the particular silica support that is used to prepare the catalyst for the polymerization of ethylene. However, titanium-modified silyl chromate catalysts with any ice cream of unearthly carrier make it possible to obtain ethylene polymers, whose flow index exceeds that of polymers obtained using catalysts, are obtained without titanium treatment. EXAMPLE repeated in full flow, however, instead of kQ ml of 1-hexane, propylene is used as ethylene comonomer, with a pressure of 20 psi (1, kg / s) created, the reaction is carried out for 9 0 min, resulting in a yield of 85 g of ethylene-propylene copolymer, the melt index of which. is 2.88 dg / min, the density indicator is 137 dg / min, and the density is 0, 905 g / cm. PRI me R 8, The process of polymerization of ethylene in a fluidized bed. During the process, ethylene polymers with a reduced flow index are obtained in a pseudo-batch cement layer compared to those with a hydrogen / ethylene ratio. Comonomer Properties of poly2 obtained, 21 measures Flow index Melt Index The ratio between melt index and melt index, 0.959 Density, G / C1 The content of products extracted by cycloM3 hexane is obtained using a catalyst in the form of a suspension. To obtain catalysts that are used in such experiments, 500 g of Lolipor grade silica is mixed with a solution of 18.7 g of aluminum nitrate nonahydrate in 3 liters of water. This mixture is filtered to provide 1, 5 L of filtrate. The residue is dried at, and then used as a catalytic carrier. The dried carrier is suspended in isopentane and 35 g of tetraisopropoxide is added per 100 g of carrier. The solvent is then evaporated, the residue is subjected to heat treatment first at 150 ° C in a stream of nitrogen for 2 hours, then in air for 2 hours and finally in a stream of air for 8 hours. After cooling, the heat-treated carrier is suspended in isopentane and 18 g of bis-triphenylsilyl chromate are added to the suspension. After stirring for 1 h, the plant is mixed. the evaporator is evaporated. The results of using titanium-modified silyl chromate catalysts in the process of ethylene polymerization in a fluidized bed are given in Table 2, Tabl 2 0.05 | (0.0802 Butene 3.07 0.132, 0.73 108.0 - 119 , 0 77.2 0, 0.956 0,. 0.953. The melt index is determined according to the ASTM standard D-1238 PRE, and it is expressed in kilogram in millimuths. The yield index is determined in accordance with the standard ASTH D-1238 using quantities that 10 times the weight of the material used in the tests to determine the index The ratio between the melt index and the flow index is calculated by dividing each other (respectively). The content of products extracted by cyclohexane is determined by measuring the percentage of the ethylene sample in the sample which are extracted by cyclohexane after refluxing in for 18 hours. Numerical values of the components extracted by cyclohexane. water content of low molecular weight p. polymers that have been formed using: a particular catalyst. Example 9. To prepare a carrier, porous silicon dioxide with a decay of 2Cg is suspended with a solution of 1.8 g A1 (NOpj 9H2 in 180 ml of ode. The mixture is filtered and 9% of the filtrate is removed. The residue is dried at 3.1 g Too ml of pentane is mixed with 10.3 g of the indicated carrier. The solvent is evaporated; i the residue is mixed with 0.103 (NH) SIF. The mixture is heated at 0 "for 17 hours. The composition is 0, wt.% wt. TY and. ,, .., ,, .0, 55 wt. F, and the rest is silicon dioxide. To prepare the catalyst, g of the support is suspended in. Hexane and add. O-.OI g of bis-trivinylsilyl {} omate. Silyl chromate 10 212 precipitate for 1 hour. Composition of the catalyst, wt.%: o, TlOj, 7.53; F 0.53 and silyl chromate 3 Cr 0.2o, the rest is silicon dioxide. The copolymerization is carried out with the indicated: catalyst for 35 minutes, using 40 ml of 1-hexane 4 and ethylene at a total pressure of 200 psig / inch M13 (b092 atm). Output 78 g of Copolymer. The melt index, flow index and polymer density are O, O I, 7 and 0, respectively. :,. l - - EXAMPLE 10. To obtain a carrier, 20 g of porous silicon oxide are suspended with a solution of 0.75 g of AINO) 9HjiO in 150 ml of water. The mixture is filtered and separated with Jk ml of water. The residue is dried at. g vysu | Supported media with a solution of 2.7 g of tetraisopropyl titanium in 100 ml of pentane. Peitan is evaporated and the residue is heated to 0 for 1 The material contains 0.24% by weight of AliO and 7.8% by weight of Tio-g, the rest is Creme dioxide. To obtain a catalyst, to a suspension in hexane of 1.90 g of this carrier, 0.080 g of bis-triphenyl silyl chromate is added. Silyl chromate is left to be precipitated for 1 hour. The catalyst contains 0.23% by weight 7.5% by weight of TU and 1 | , 0 wt.% Silyl chromate, ... (0.33 wt.% Cr), the rest is silica dioxide. The copolymerization is carried out at 80 ° C with indicated / catalytic acid (using 60 "P 1-hexane at a total pressure of 200 pounds / inch (13.6092 atm). Output89 g. The melt index, the flow index and the polymer nitoTHocT are 3.09, 87.3 and 0, respectively. In the given composition of catalysts .. T a b l and C a 3
O.iS
7,6
2.9 0.5
7.6 2.9
7. 3.8 0.25, 0
7.1 0.25.
7. 0.27 11.7 2.9
7.5
7.5 11.7 2.9
8, 3.8 0.22
ABOUT.
7.53
", 0 0.23
7.5
Equivalent to 0.91 on a 1 | separator before heat treatment (the compound decomposes during heating).
Continued tab. 3
89.05
ABOUT
oh oh oh
ABOUT
89.05
8iB.55
ABOUT
ABOUT
88.35

87.70
53
ABOUT
ABOUT
ABOUT
oh oh
77.90
ABOUT
87., 28

88.11
0.53
about
88.27 O

权利要求:
Claims (4)
[1]
I · A catalyst for homopolymerization of ethylene and its copolymerization with C ^ -C ^ α-olefins containing triphenylsilylchromat, alumina on a silica support, characterized in that, in order to increase the activity of the catalyst, it additionally contains titanium dioxide at the following content components, weight,%:
Triphenylsilyl Chromate 2.9-4.1
Alumina 0.22-11.7
Titanium dioxide 7.4-8.7
Media ’Else
[2]
2. The catalyst according to claim 1, about t l and the fact that it additionally contains 0.53 wt.% Fluorine.
[3]
3. A method of producing a catalyst for * homopolymerization of ethylene and copolymerization of it with C ^ -C ^ o-olefins by heat treatment of a silica support containing alumina, § at 750-820 ° С followed by cooling and deposition of triphenylsilyl chromate on it, characterized in that , in order to obtain a catalyst with increased activity, titanium tetrapropoxide or titanium tetraisopropoxide is additionally introduced at the heat treatment stage.
[4]
4. The method according to claim 1, which consists in the fact that at the heat treatment stage, ammonium hexafluorosilicate is additionally introduced.

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法律状态:

优先权:

申请号 | 申请日 | 专利标题

US05/761,213|US4100105A|1977-01-21|1977-01-21|Titanium-modified silyl chromate catalysts for ethylene polymerization|

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