JPS6025042B2 - Production method of olefin polymerization catalyst - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for producing a catalyst composition for polymerizing 1-olefins. Molded objects, particularly blow molded structures such as bottles, are generally formed by the polymerization of 1-olefins such as polyethylene. It is important to the commercial use of a given polymer system that the converted product, such as a bottle, exhibits an optimal balance of properties, such as acceptable pressure cracking resistance and flexibility hardness. In order to enhance their utilization, it is also necessary that the polymers exhibit suitable processability, ie, satisfactory rheological properties under flow and deformation during the process. The viscoelastic properties of polymer melts have been the subject of considerable research;
The possibility of transferring in-process performance to the end-use article in such a way as to selectively determine polymerization and especially catalyst requirements has not been demonstrated. Moreover, in any case catalyst performance must be evaluated in terms of efficiency or productivity and stability over a sensitive lifetime. In the following, a supported catalyst system for the production of polymers has been identified which is well suited for the processing of superior blow molded objects. According to the invention, the reaction product of chromium trioxide with organophosphorus compounds such as phosphates and organophosphites, the organic portion of which is a hydrocarbon group, such as alkyl, aralkyl, aryl, Supported catalyst compositions with preformed materials such as dichloroalkyls or combinations thereof have been disclosed. Typical supports are inorganic materials with large area, especially large pore volume (>1.96 cc')
Composed of silica xerogel. Catalytically promoted polymerization of 1-olefins effectively results in products with applications particularly amenable to molding, particularly the production of blow molded articles. The polymerization activity of the catalyst composition is promoted by heating in a dry, oxygen-containing atmosphere. Furthermore, the above catalysts are used in conjunction with other catalyst components such as organometallic and/or organononmetallic reducing agents. Louise J. Rekers (Lovis)
J. National Distillers and Chemical Corporation (NationalDis
tille and Chemical Corporation
U.S. Pat. . Further research has shown that such compounds are useful in the preparation of supported catalyst systems useful for the polymerization of 4-olefins, and that the polymerization activity is significantly enhanced by heating the catalyst in a dry oxygen-containing atmosphere. It is. It has further been discovered from this work that the resulting catalysts produce polymers of 1-olefins or copolymers or interpolymers thereof with a very good combination of properties when used with certain reducing agents. The use of organometallic and/or organononmetallic reducing agents with air/thermal treatment catalysts not only enhances catalytic activity but also provides more diversity in the balance of polymer properties. U.S. Patent No. 5, issued February 3, 1970, filed by National Distillers and Chemical Company in the name of Louise J. announced the polymerization of 1-olefins in the presence of olefins. Other researchers also have other questions about the gutter. researches silica and phosphorus compounds and their use in olefin polymerization. For example, Hogan
US Patent No. 2 published on March 26, 195 by Gan) et al.
Chromium oxide and silica as a catalyst in No. 825721,
A process for the polymerization of olefins is provided using at least one material selected from the group consisting of alumina, zirconia and thoria, and in which at least a portion of the chromium is in the hexavalent state during the initial contact of the catalyst and the hydrocarbon. Are listed. Hogan et al., U.S. Pat. A method for preparing the catalyst is described. Clyde. Viii. U.S. Patent No. 29450 issued on July 12, 1960 under the name CIyde Vr.
No. 15 describes a process for the polymerization of 1-olefins using a supported catalyst of chromium oxide and phosphorus oxide and in which at least some of the chromium is in the hexavalent state in the catalyst. Supported chromium catalyst with limited productivity is covered by U.S. Pat.
No. 349,067, it is described as an ester of chromyl chloride and, for example, tricresyl orthophosphate. of
reported the use of various silyl chromates and polycyclic chromic acid esters as catalysts for olefin polymerization. In particular, Union Carbide
U.S. Patent Nos. 3,324,095 and 332,410, filed June 6, 1967, filed by
No. 1: No. 3,642,749 published on February 15, 1972; please refer to No. 3,704,287, published on November 28, 1972. The last of this group is U.S. Patent No. 347
No. 408 phosphochromate ester is applied to a support and the catalyst is aluminum, prior to contacting with the olefin.
It has been announced that agnesium or gallium is reduced by heating to high temperature in the presence of an organometallic compound. Processes for the preparation and use of improved large pore volume silica xerogel materials suitable as catalyst supports are provided by National Petrochemicals.
Belgian Patent No. 74143 filed by Companylm
No. 7 and U.S. Pat. Nos. 3,652,214, 36,522
No. 15 and No. 3,652,216. Although such chrome media, support materials, and combination systems have been utilized for applications in the art, and may be used selectively in the production of polymers that can be converted into molded articles such as pins, they have not yet been disclosed in the present invention. No operational system has been provided that provides the desired characteristics of The present invention relates to the polymerization of 1-olefins, particularly ethylene, to form either polyethylene or ethylene interpolymers and other 1-olefins particularly suitable for molding operations. The present invention involves reacting chromium trioxide with a phosphorous compound and depositing the resulting organic phosphorylchromium reaction product from an organic solvent onto a solid inorganic support, and then
Heat treating the support and the organic phosphorylchromium reaction product in a dry oxygen-containing atmosphere at a temperature above F (about 205q0) and below a temperature at which the structure of the support is damaged, and further adding an organic reducing agent. The present invention provides a method for producing an olefin polymerization catalyst composition characterized by: Particularly convenient catalyst compositions are obtained when silica xerogels with large pore volumes, such as >1.96 cc/day, are used as supports. The catalyst compositions of the present invention, when combined with known polymerization methods such as suspension, solution, vapor phase, etc., can produce polymers with a variety of molecular weights and molecular weight distributions, which are typical of high and medium density polyethylene. applications, especially extrusion applications,
For example, it enables a wide range of processes such as blow molding, sheet and film production, etc. According to an exemplary embodiment of the invention, the organophosphorus compound and chromium trioxide are mixed together in a suitable inert solvent such as cyclohexane, n-hexane, methylene chloride, carbon tetrachloride, and the like. At this stage of the production of the catalyst system, solid Cr0
3 is slurried in a solvent and an organic phosphorus compound is added. The reaction between the compounds continues for a suitable period of time, for example about 1 hour, and the chromium trioxide disappears. During this time the solution turns reddish-brown. Normally, simply pass the sample to confirm that there is no unreacted C-3. This solution can be applied to a support such as silica using a suitable wet coating method.
The catalyst solution is applied to the support in such a way that the catalyst solution can be precipitated onto the support, such as by spraying onto aluminum or the like. Typically, the solution is added to a dispersion of a good silica gel support. A good support is silica xerogel with large pore volume (>1.96 cc/night). The solvent is removed from the substrate by drying, for example using heat, inert gas stripping or vacuum alone or a combination thereof. In this way the reaction product is deposited on the support. An organic phosphoryl chromium reaction product is preformed. Thus, it would be advantageous to bind the reactive entities before applying them to the support. The active catalyst is therefore believed not to originate from chromium trioxide, but rather from the organic phosphorylchromium reaction product as described. The supported catalyst is heated in a dry oxygen-containing atmosphere, such as dry air, resulting in a significant increase in polymerization activity. Heating is approximately 400T (approximately 205oo) to 20,000F (
It is carried out at a temperature in the range of about 109 degrees C), but about 10,000F.
(approximately 53 is C) to 19,700F (approximately 147,500) is preferred. The heating time varies depending on the temperature, but is usually 2 to 1 hour, preferably about 6 to 1 hour. The reaction products supported by heat treatment are organometallic and/or organo-nonmetallic reducing agents for the polymerization of 1-olefins such as trialkylaluminum, dialkylzinc, dialkylmagnesium, dialkylaluminum chloride, dialkylaluminium alkoxide compounds, triethyl Used with organoaluminum compounds such as boron, organozinc compounds, organomagnesium compounds, and organoboron compounds. When such a reducing agent is used, it is possible to ensure the properties of the polymer, particularly the preferred range of molecular weight distribution, as well as excellent catalyst productivity. In the following, measurements of the shear elasticity of polymer melts are made using melt index values (MI tested at loads 2k9 and 19000 by ASTM-D-12 spots).
Shear sensitivity (response of melt viscosity to differential shear rate) is reflected in the HLMI/MI ratio. Generally, the broader the molecular weight distribution, the more sensitive the viscosity is to shear rate, ie, the higher the HLMI/MI ratio. The lowest value of the melting index measured with reasonable precision is about 0.1, but qualitative observations of meaningfully low ratios are often "low".
, which represents an actual value of 0.09 degrees lower or lower. Performance tests show HLMI/MI ratios that are consistent with other quantitative results. The organophosphorus compound used in the catalyst composition of the present invention is a compound of the formula or (where R is alkyl, aralkyl, aryl, cycloalkyl, or hydrogen, but at least one R is other than hydrogen) There are triorganophosphates and diorganophosphates, including compounds such as triphenyl phosphate, tributyl phosphate, triethyl phosphate trioctylate, trityl phosphate, and the like. Mono(dihydrogen) phosphate or phosphite and di(hydrogen)
Phosphate derivatives (including, illustratively, monobutyl phosphate, dibutyl phosphate and monoethyl phosphite) are also suitable, as are mixtures of these substances. Organic phosphorus chromium reaction products, which are reaction products of these organic phosphorus compounds and chromium trioxide, have the following formula: (
However, in the above formula, X is P-(OR)3 or PH(OR
)2, in which R is alkyl, aralkyl, aryl, cycloalkyl, or hydrogen, but at least one R is other than hydrogen. ) is believed to be expressed as Preference is given to alkyl derivatives, especially trialkyl phosphates. A representative manufacturing example of the catalyst system is as follows. Catalyst production #1 a Nitrogen inlet for charging, gas outlet, electromagnetic mesh accompaniment and 100

[Put 125' of dichloromethane into a three-necked 500 flask with an injection filter attached. A flask containing dichloromethane solvent was filled with nitrogen, and 39.70 m (0.097 mol) of C was added thereto while the flask was filled with nitrogen. Inject 17.5 mol (0.097 mol) of triethyl phosphate dissolved in 75 ml of dichloromethane from one filter to the other.
Added over 0 minutes. Within 5 minutes of starting the addition of triethyl phosphate, the solution in the flask turned reddish brown.
After 1 hour, C3 was completely dissolved and the solution turned reddish brown. The weight of the solution was 217.6 mm. To deposit the compound onto the support, a rotating microspheroidal silica gel (Davison MS952) was placed in a 2000 round bottom flask equipped with a dropper and a nitrogen plunket.
I put in 210 evenings. Next, add 800M dichloromethane to the flask containing the gel.
I added some water to the gel to evenly moisten it. Then, 90 g of the dark brown filtrate was added to the flask containing the gel and dichloromethane solvent. After the rope group was closed for about 15 minutes, the rope adjuster was stopped to allow the gel to settle. At this point, the gel turned brown, indicating that the dichloromethane solvent was almost colorless. This indicated that the catalyst compound was adsorbed on the gel very strongly and selectively. The surface liquid was filtered off and the gel was dried in a rotary evaporator under vacuum at 55 mils and 29 inches of mercury. The dried catalyst-coated gel containing 0.9 weight percent chromium and 0.60 weight percent phosphorous was then treated at high temperature, i.e., 11100 F., for 6 hours while simultaneously passing dry air through the catalyst. b It was found that chromium dioxide does not react with tributyl phosphate under the same conditions that chromium trioxide reacts. Catalyst Preparation #2 250M dichloromethane was placed in a 3500' flask equipped with a plank nitrogen inlet, gas outlet tube, electromagnetic strainer, and 100' injection funnel. After covering with nitrogen, 2.9 mol (0.029 mol) of Cr was added to the flask containing the dichloromethane solvent. From the injection funnel, 5.6 g (0.029 mol) of dipyl phosphite dissolved in 25 g of dichloromethane was added.
Added over 0 minutes. Within 5 minutes of beginning the addition of dibutyl phosphite, the solution in the flask turned reddish-brown in color. The rope was continued for 2 hours, and C3 disappeared and the solution became clear reddish brown. When I weighed out the solution, it was still warm by $3. To attach the compound to the support, a 2000 round bottom flask with a rope strainer and a nitrogen plunket was equipped with a Polypor.
) Silica gel (pongee hole volume 2.5 cc/unit) 42 units was added. 100 g of the reddish brown liquid solution (the solution was filtered to ensure that there was no unreacted Cr03) was added to the flask containing the polypore silica gel. After 12 minutes, the gel turned brown and the dichloromethane solvent became almost colorless. This indicated that the catalyst compound was adsorbed on the gel very strongly and selectively. Separate the top liquid and put it in a rotary evaporator.
The gel was dried in a 29 inch mercury vacuum at YO. chrome 1
．． The dried catalyst-coated gel containing 0.2% by weight of phosphorus and 0.6% by weight of phosphorus was then treated at an elevated temperature of 16500F for 6 hours while simultaneously passing dry air over the catalyst. Catalyst manufacturing #
3 Same as Example #2 except that 3.66 moles (0.0366 mol) of CrQ and 7.23 moles (0.0373 mol) of dibutyl phosphite were used in 373 moles of total dichloromethane as the reaction soot and solvent. A solution of dibutyl head phosphate chromium trioxide compound was prepared using the method described in the following. This solution was used to coat Polypore Silica Gel 195 with 0.97% chromium and 0.9% phosphorus by weight. It was expressed as turtle weight %.
After removing the dichloromethane, the coated polypore silica gel was treated at 16500F for 6 hours with air passing through the sample. The catalysts of the above examples were utilized in the polymerization examples below for the polymerization of ethylene with various reducing agents such as triisobutylaluminum and triethylboron. The amount of organic phosphoryl chromium compound deposited on the support may vary widely depending on the nature of the compound and the desired amount of phosphorus. The amount of reducing agent used with the organic phosphosphoryl catalyst may vary as well. It has been found that the most effective catalyst is when the content of the organic phosphoryl chromium compound is about 0.25 to 2.5% by weight of Cr on the support, but about 0.5 to 1.25% by weight of Cr. Weight percent is preferred. Note that usable catalysts can be obtained even outside the above range. Usually the catalysts are prepared in equimolar ratios, although an excess of the organophosphorus compound can be used. Calculation based on elemental weight in supported catalyst Cr/
The P ratio is 1:0.6 as standard. Although the ratio of the amount of reducing agent to the amount of organic phosphoryl chromium compound can be used within a very wide range, certain criteria have been established consistent with good yield, favorable polymer properties, and economical use of raw materials. For example, the parameters shown below are typical in the use of organometallic and organononmetallic reducing agents with sufficient bases of organophosphoryl chromium compounds such that the Cr is about 1% by weight of the support. The atomic ratio is based on the calculation of the amount of chromium in the metal in the organometallic reducing agent and the nonmetal in the organo-nonmetallic ring-forming agent to the organic phospheryl chromium compound. Preferred types of organometallic reducing agents to be used therewith are based on the amount of organophosphorus chromium compound containing, for example, about 1% by weight of Cr based on the weight of the support, such as triisobutylaluminum (formerly AL). At about 11.4% by weight, the AI/Cr atomic ratio is about 3/1. A good range for the atomic ratio of N to Cr is about 1/1 to 5/1 or TIBAL
, about 3.8 to about 19% by weight. The total usable limit of T-light AL is approximately 0.1/1 to 20/1 in terms of AI/Cr atomic ratio, and approximately 0.1 to 20/1 in terms of weight. Yuno approximately 75% by weight
It is. Another example of an organometallic reducing agent for use with organic phosphorylchromium compounds is triethylaluminum. A good amount of triethylaluminum (TEA), again based on the amount of organic phosphoryl chromium compound containing about 1% Cr by weight based on the weight of the support, is about 6.6% by weight, giving an N/Cr atomic ratio of about 3/1. . A preferred range for the atomic ratio of AI to Cr is from about 1/1 to about 5/1, or from about 2.2 to about 11% by weight TEA. The general usable limit of TEA is Mt/C
In terms of r ratio, it is about 0.1/1 to 20/1, and in terms of weight, it is about 0. Pine is approximately 44% by weight. Triethyl boron (TEB) is a good example of the proportion of a non-metallic reducing agent used with an organic phosphoryl chromium compound. The preferred amount of TEB, again based on the amount of organic phosphoryl chromium compound containing about 1% by weight Cr, is about 5% by weight, resulting in a B/C atomic ratio of about 2.7/1.
The preferred range of the atomic ratio of B to Cr is about 0.1/1 to 1.
0/1, and the TEB is about 0.19 to about 19%.
The overall usable limit is approximately 0.01/ in terms of B/Cr ratio.
1 to about 20/1, and in terms of weight, it is about 0.02 to about *% by weight. For supported catalysts in which the organic phosphoryl chromium compound is sub-deposited on the support, the processing conditions at high temperatures can be changed. Generally, the catalyst is dried in dry air or dry oxygen-containing gas for about 400 min.
It is heated at temperatures above 00F, preferably above about 6500F, for about 2 hours or more. Using the large pore, small volume silica gel support described above, it is desirable to heat to a range of about 14,500 F to about 16,500 F for up to about 6 hours. For other supports, heat curing for about 6 hours at about 4,000 F or higher, preferably 10,000 F or higher is effective.
Dry air or other oxygen-containing gases must be dehumidified to the extent possible to obtain maximum productivity from the catalyst. Characteristically, the air used in the method described in this example is dry to less than about 2 to 3 feet of moisture. As noted above, the catalyst compositions of the present invention are conveniently used in conventional polymerization processes under temperature and pressure conditions commonly used in the art, such as from about 1000F to about 4000F, such as those used in slurry polymerization.
F (about 205 qo), preferably about 1600 F (about 890
0) to about 2300F (about 110C) and 20
0 to 100 cape sig, preferably 300 to 80 snake sj
It is suitable for polymerization carried out at a pressure of 1.5 g. The "organophosphorylchromium" reaction products underlying the novel supported catalyst compositions of the present invention are inert, as can be demonstrated by the dissolution of the distinctive chromium trioxide as seen in the examples above. It can be formed empirically from organophosphorus compounds in reaction with chromium trioxide in a solvent. Appropriate organophosphorus compounds can be easily selected for their efficacy with reference to this test. The following example illustrates the use of the catalyst system of the present invention in a process for polymerizing alpha olefins such as ethylene. Polymerization Example 1 Isobutane 0.9k9 while passing through an autoclave,
Ethylene at 13 sig pressure to give 10 mol % in liquid phase, 0.33 mol per solvent k9, supported catalyst 0.82
0.99% by weight of chromium and 0.99% by weight of chromium. Add the triethylphosphorylchromium compound adhered to the Davison Ms 952 gel to give 6% by weight at 11100F.
time air/heat treatment and aluminum to chromium atomic ratio 1. Enough triisobutylaluminum was added to cover 1:1. The autoclave containing the above contents was heated to 2000F with stirring. The total pressure was 435 psig. Polymerization began almost immediately as observed with ethylene filling the reactor from the required ethylene feed system. After 1 hour of polymerization, the reactor contents were passed through a pressure reduction system to terminate the reaction. Before homogenizing, melt index (MI) 0.21 and high load melt index (HLMI) 16 (ASTMD-12 paper) (H
319 pieces of polyethylene with LMI/MI=76) were recovered. The yield, based on a catalyst charge of 0.82 hours, was 390 hours, polyethylene/hour, catalyst/hour. Polymerization examples
2 Isobutane 0.9k9 while fixing the autoclave
, ethylene at a pressure of 13 sig to give a concentration of 10 mol % in the liquid phase, and 0.0 mol of hydrogen per solvent k9. Supported catalyst 1 of Example 1
．． Sufficient triethyl boron was added to give a boron to chromium atomic ratio of 3.8 to 1. 200 while admiring the autoclave with the contents inside.
It was heated to F. At this time the total pressure was 435 psig.
Polymerization began to be observed almost immediately with ethylene entering the reactor from the required ethylene feed system. After 1 hour of polymerization, the reactor solution was placed in a pressure reduction system to terminate the reaction. As a result, the melting index (MI) before homogenization was 0.036 and the high load melting index (HLMI) was 10 (LMI = 278).
Polyethylene 439 having the following properties was recovered. The yield, based on a catalyst bag loading of 1.59 kg, was 275 tapoethylene/h, catalyst/h. Polymerization Example 3 While cleaning the autoclave, add isobutane 0.9k9 and 1 in the liquid phase.
Ethylene, 1.0 mol hydrogen per k9 solvent, supported catalyst as described in Catalyst Preparation #2, i.e. 1.02 wt% chromium and 0.0 mol % chromium and 0.0 mole % chromium and 0.0 mole % hydrogen per 9 mol % ethylene. 0.46% of the isobutylphosphorylchromium compound adhered to the polypore silica gel was added to give 1650% by weight of bamboo.
Heated at T for 6 hours until the atomic ratio of aluminum to chromium was 1. Enough tri-isobutyl aluminum was added to give a ratio of 1 to 1. 20 minutes while eating an autoclave with the above contents
It was heated to 00F. The total pressure at this time was 415 psig. Polymerization began almost immediately as observed with ethylene entering the reactor from the required ethylene supply system. 1
After an hour of polymerization, the reactor contents were placed in a pressure drop system to terminate the reaction. In the end, 298 pieces of polyethylene with a melting index (texture) of 1.45 and a high load melting index (HLMI) of 75 (HLMI/MI=52) before homogenization was recovered. The yield based on a catalyst charge of 0.46 was 650 hours, polyethylene/hour, catalyst/hour. Polymerization Example 4 Using an autoclave, add 0.9 k9 of isobutane, ethylene at a pressure of 13 kig to give a concentration of 10 mol % in the liquid phase, 0.57 kg of supported catalyst from Catalyst Production #3, and boron to chromium. Atomic ratio 2. Enough triethyl boron was added to give a ratio of 1:10,000. 20 minutes while holding the autoclave containing the above contents.
It was heated to 00F. The total pressure at this time was 435 psig. Polymerization began almost immediately as evidenced by the ethylene entering the reactor from the required ethylene feed system. 1
After an hour of polymerization, the reaction was terminated by placing the reactor contents in a pressure drop system. In the end, a polyethylene material having a melting index (MI) of less than 0.1 and a high load melting index (HLMI) of 16.7 (ASTMD=12 paper) before homogenization was recovered. Catalyst charging 0.57
The yield based on sawing was 1137 hours, polyethylene/hour, catalyst/hour. Polymerization Example 5 Isobutane 0.9k9,
Ethylene, catalyst preparation #3 supported catalyst 0.0.0. Sufficient tri-isobutyl aluminum was added to give a solid base and an N/Cr ratio of 1.5. 20 minutes while worshiping the autoclave with the above contents
It was heated to 00F. The total pressure at this time was 39 sig. After an induction period of approximately 3 minutes, the polymerization reaction began as observed by the required ethylene feed into the reactor from the ethylene feed system. After 1 hour of polymerization, the reactor contents were passed through a pressure drop system to terminate the reaction. In the end, 652 pieces of polyethylene having a melting index (MI) of 0.07 and a high load melting index of 10.5 (ASTMD-12 total) before homogenization was recovered. The yield based on a catalyst charge of 0.53 was 1230 hours, polyethylene/hour, catalyst/hour. The use of various organophosphorylchromium compounds in combination with an organometallic reducing agent (triisoptylaluminium) in supported heat-treated catalyst systems for the polymerization of 1-olefins is further described in Table 1. Illustrated with data. Table I (1) 1 mole of this compound and 1 mole of this compound were reacted to form the desired reaction product. The substrate Si02 is Davison MS952. The substrate was pretreated with an organic phosphoryl chromium compound. (3) The base material is Volibon Rica gel with a pore volume of about 2.5 ratio/layer and a surface area of about 350 ratio/layer. (4) For A, triisobutylaluminum was added as a reducing agent. (5) Polymerization temperature 200F. Hydrogen concentration is 0.
The solvent was changed from 33 to 1.0 m/K. (6) The catalyst consists of organic phosphorylchromium deposited on a support. From the above data, various organic phosphorus/phosphorus trioxides, including the products of the reaction of phosphorus compounds with alkyl to aryl substitution with CrOG. It will be readily appreciated that the reaction products are suitable for use in this invention. Further, the use of this new catalyst will be illustrated when polymerization is carried out using trisoptylaluminium as a reducing agent and varying the AI/Cr ratio. The data in Table D also showed that intermediate concentrations of triisobutylaluminum showed better catalyst productivity. Furthermore, as shown by H peak 11, the polymer fluidity increases with increasing N/Cr atomic ratio. Table 11 [1} Catalyst heat treated in air at 11100F/6 hours on polypore silica gel (pore volume 2.3cc/night). The catalyst contains approximately 1% chromium and 0.6% phosphorus. ■ Polypore silica gel (pore volume 2.5cc/night) top 16500F
/Catalyst subjected to air heat treatment for 6 hours. The catalyst contains approximately 1% chromium and 0.6% phosphorus. Polymerization conditions temperature 2000F solvent
isobutane ethylene
10 mol% pressure (total) 42
sig specific concentration of 0. Madarayu/k9 Solvent Further illustrating the variability of the present catalyst composition, Table m shows the effect of increasing polymerization temperature on the MI of polymers made using the new catalyst. It is also important to note that when triethylphosphorylchromium compounds are prepared using excess phosphate compounds, such as a 2/1 molar ratio of phosphate to C3, there are no harmful effects. be. Table 1.11 [1] 1% chromium and 1.2 on Davison MS952
Triethylphosphorylchromium catalyst containing % phosphorus and heat treated at 11100F/6 hours air/heat treated. [21 Aluminum as triisoptylaluminium. Polymerization conditions Solvent Isobutane ethylene 10 mol% Pressure (total) Shimisaki sig specific concentration
0.33 m/k9, solvent A further extension of the present catalyst composition is the type of substrate that can be used as a support for the catalyst. It can be easily seen in Table W that either MgC03 or AI203 and Si02 are suitable supports for the catalyst. After the triethylphosphorylchromium compound was deposited on the designated support, heat treatment was carried out in air. Preferred substrate materials generally have a surface area of 1,000 to 1,000 mm/ta or more. table
IV (1) A O as triisobutyl aluminum (2)
Polymerization conditions: Solvent: Isobutane Day 2 Pressure: 10-5
0 pslg polymerization temperature: 190-200F Zenshoto: 3
70-435 pslg Ethylene: 10 moles* (3) Hydromacnesite from Ncwall's Ltd. (U.K.) Extensive test results are presented using various reducing agents with air/heat-treated supported catalysts. Shown in V. These reducing agents can be mixed with the air/heat treated catalyst in various ways, such as by placing the triethyl boron agent in a solvent stream in the reactor or by pre-contacting the reducing agent with the catalyst before entering the reactor or with the solvent stream. Regardless, the above-mentioned reducing agent can be brought into contact with a diluent directly into the reactor. In addition, when dibutylmagnesium was used alone without being used in combination with triethylaluminum, almost the same results as when using triethylaluminum alone were obtained. Table V '1} Triethylphosphorylchromiwam (1% Cr) attached to MS952 Air/Heat treatment 11100F/
6 hours. [21 K/Cr [3'B/Cr ■Drop; Mata'ma AI+Mg Cr ■Zn/Cr '6' Large pore volume (2.5cc/night) Catalyst on silica gel. Air/heat treatment 16500F/6 hours. [7-X/Cr
is the atomic ratio of metal or nonmetal to Cr. Polymerization conditions Solvent Isobutane ethylene 10 mol% hydrogen
1.65 m/kg solvent total pressure
435 psig polymerization temperature
2000F In the best embodiment of the present invention, the organic phosphoryl chromium compound is subsequently deposited onto a silica gel support material, particularly silica gel with large pore volume (>0.96 cc/night), and then exposed to a dry oxygen-containing gas, e.g., air. It has been found that particularly good results can be obtained when the catalyst is heated for a suitable time to increase productivity of the catalyst, with a temperature of about 4,000F and a boiling temperature of 6,500F or more. In particular, when used together with triethyl boron (TEB), favorable properties can be obtained in the polymer. The effect of TEB on silica gel supported organophosphorylchromium catalysts is shown in the table below. Table {1} MS9
Catalyst on 52 gel (1wt% Cr+0.wt%P) air/heat treatment 4700F/6 hours. Polymerization conditions A. ■ B/Cr atomic ratio. Boron as triethyl boron {3} Catalyst on polypore silica gel, air/heat treated at 16500F/6 hours. Polymerization condition B. The effectiveness of using large pore volume silica xerogels as support materials is illustrated on the epidermis. Silica xerogels with a pore volume of 1.96 cc/unit are often commercially available under the trade name Polypore. As mentioned above, the method for producing such silica gels is described in U.S. Patent No. 36.
No. 52214, No. 3652215 and No. 36522
It is described in No. 16. The polypore support material is approximately 1.9
In addition to having a pore volume greater than 6 cc/unit, the majority of said pore volume has a pore diameter in the range of about 300 to 600 Δ and a surface area in the range of about 200 to 500 cc/unit. is a feature. The pore volume is, for example, p. H. Written by Emme
tt. P. H), New York, New York, Reinhold Publishing Co., Ltd.
Corp. ) Published by Catal Oreis, Volume 0, 1
It is determined by the well-known nitrogen adsorption-desorption method described on pages 11-116. (Run against P/Po is 0.9
In the case of 67, it corresponds to 600A of Tsumugiko object quality. ) When using a polypore supported catalyst, heat treatment in dry air to promote polymerization activity is minimal at about 10,000F to about 20,000F.
Although it can be carried out for about 2 hours, it is preferably carried out for about 6 to 1 hour at a temperature range of about 15,000F to about 16,500F. The heat treatment temperature may generally be varied up to the maximum temperature capable of promoting polymerization activity without damaging the structure of the support. -t:～】・Hitsujinhi (1) The catalyst on the gel is 1son○r and 0.6%P. MS95
2 Air/Heat Treatment 1470. F No.6 hour polybore silica gel air/heat treatment 1650
0F/6 hours■ B/or atomic ratio. Boron as triethyl boron. Polymerization conditions reaction temperature
2100F specific pressure 1
Misaki sig total pressure 435ps
ig solvent isobutane ethylene
The effectiveness of TEB as a reducing agent is also observed on the skin when using large pore volume silica gel as the 145 psig catalyst support. TEB as a reducing agent with only a slight change in the MI of the polymer
The density of the polymer changes considerably when using Thus, the use of TEB as a reducing agent allows for the adjustment of the density of the catalyzed polymer on a larger pore volume silica gel. Furthermore, the influence of the use of triethyl boron on the molecular weight distribution of the resulting polymer can be seen from the skin table. The molecular weight distribution (evaluated by HLMI/MI ratio) is 9 when using triethylphosphorylchromium catalyst on polypores.
1 to 151 when triethyl boron is included at a B/Cr ratio of 5.4/1. This broadening of the molecular weight distribution makes a significant contribution to improving the shear response of the polymer. Further illustrating the versatility of the catalyst deposited on barley area silica gel (Polypore) of the present invention is its response to hydrogen, in which the M of the resulting polymer increases with increasing hydrogen pressure during polymerization. This is exemplified by a wheat field. Table Dish {1) Catalyst on polybore silica gel. 1% Cr and 0.6% P. Air/heat treatment 1650 or/6 hours. Poor polymerization conditions. ■ B
/Cr atomic ratio. Boron as triethyl boron. Compared to polymers made using conventional catalyst systems, polymers made using the catalysts of the present invention exhibit better end-use properties such as hardness, stress cracking resistance, and processability necessary for blow molding resins. It shows balance. For example, the following table shows a comparison of the properties of three resins produced under optimal industrial reactor conditions. Specifically, Resin A, that is, a resin produced using the catalyst composition of the present invention in which triethyl boron is added as a reducing agent to the catalyst, was compared with a polyethylene resin produced using ordinary C-3 on a Si02 catalyst. There is. Table IX [1] Shear rate Poise x 1 at 100 steps-1
0-3 [2' Time until 50% destruction. ASTM D-169 condition B (corrected) Resin A was made by attaching a triethylphosphoryl chromium compound to polypore silica gel and treated in dry air at 16500F for 6 hours to obtain a B/Cr atomic ratio of 2.4/1. was prepared in a continuous slurry reaction system using a catalyst composition with triethyl boron. Resin B was produced in a continuous slurry reaction system using a conventional C3 catalyst on Si02 made at optimal conditions. The density of the resin is determined by adding ethylene and hexene for copolymerization to the reactor.
1 was added separately. Resin C is a molten mixture of both resins made in a continuous slurry reaction system. For both component resins, a conventional Cr03 type catalyst on SiQ was used under conditions to achieve optimal mixing properties. In other words, resin C is a mixture of two different molecular weight resins and has a wider M than resin B.
Gives WD product. The density of the product was adjusted by separately adding putene-1 for copolymerization of putene-1 in the high molecular weight component. Table K clearly shows that Resin A has a better balance of properties than Resin B, which is a simple reactor product, and than Resin C, which is an expensive and difficult product. That is, resins of the present invention with at least the same processability (as seen in viscosity) have superior hardness and stress cracking resistance. Therefore, unique and valuable blow molded products can be effectively produced through the use of polymers made according to the instructions herein. Although one does not wish to rely on any proposed mechanism, the desirable properties of these structures are due, at least in part, to the polymers produced by this invention under flow and deformation during processing of the final product. It is believed that the contribution of molecular weight balance to creating rheological behavior and properties can be attributed. The properties of the polymer can be adjusted in the present invention by selectively using the catalyst composition as described above. H.L.M.I.
Polymers with excellent shear sensitivities, expressed by /MI ratios of 40 or 50 or higher, are optimally produced at melting indexes ranging from below measurable molecular weights to about 1 or 2. Preferably, the HLMI value ranges from about 5 to about 75. Embodiments of the invention are as follows. (1) The manufacturing method according to claim 1. (21 '1) above, organic phosphorylchromium has the formula: (However, X in the above formula is P(OR)3 or PH(O
R)2 in which R is alkyl, aralkyl, aryl, cycloalkyl or hydrogen, and at least one R is other than hydrogen. ) is the manufacturing method. '3} The manufacturing method in Appearance 1}, wherein the supporting material is silica gel. {4' In the above {1' or (2), a manufacturing method in which chromium trioxide is reacted with an organic phosphorus compound in a molar ratio of at least 1:1. '5} The method according to any one of '1' to '4' above, wherein the organic phosphorus compound is an organic phosphate or an organic phosphate. Shelf The manufacturing method in [5} above, wherein the organic phosphate compound is an alkyl phosphate. {7} When applied to the skin, the alkyl phosphate is
The manufacturing method that is ethyl phosphate. Shelf In any of items m to [7] above, the organic phosphorylchromium product is precipitated as a solution in an inert solvent and the deposit is C based on the weight of the support material.
A manufacturing method in which the ratio is such that r is about 0.25 to about 2.5% by weight. [9} In any of m to {7) above, chromium trioxide is reacted with an organophosphorus compound in an inert solvent medium to form a solution of the melted organic phosphoryl chromium reaction product, The solution is contacted with a solid inorganic support material having a barley area and the solvent is removed such that the organic phosphoryl chromium reaction product is in a proportion from about 0.25 to about 25% by weight Cr based on the weight of the support material. A certain manufacturing method. OQ In any of the above tl' to {9}, the supporting material is a silica xerogel having a surface area in the range of 200 to 500 cc/cm and a pore volume as large as 1.96 cc/cm, and the pore volume is A method in which the majority of holes are made of vertical holes with diameters in the range of about 300 to about 600 amps. (11) In the above 00, the temperature of about 2 to 12
A process comprising the step of heat treating the composition for a period of time. (12) In any of the above '1} to (11),
A manufacturing method in which the organic reducing agent comprises an organometallic compound. (13) The method according to (12) above, wherein the organometallic compound is a compound selected from the group consisting of alkylaluminum, alkylaluminum halides, and alkylaluminium alkoxide compounds. (10) In (13) above, the reducing agent is triethylaluminum. (15) In (13) above, the reducing agent is triisobutylaluminum. (16) (13) to (15) above. in which the compound has an aluminum to chromium atomic ratio of about 1:1.
to about 5:1. (17) In any of the above '1} to (11),
A manufacturing method in which the reducing agent is triethyl boron. (18) The method according to (17) above, wherein the triethyl boron is present in an amount sufficient to have a boron to chromium atomic ratio in the range of about 0.1: to about 20:1. (19) 1-Olefins are contacted with a catalyst composition that deposits an organic phosphorylchromium product on a solid inorganic support material under polymerization conditions of temperature and pressure, and further deposits an organic reducing agent. In the method for polymerizing 1-olefins, the method for producing polymers, copolymers and interpolymers of 1-olefins by
The catalyst composition in a dry oxygen-containing atmosphere at a temperature above about 4000F and below the temperature at which the structure of the support is damaged for a period of time sufficient to enhance the polymerization activity of the catalyst composition for the polymerization of 1-olefins. 1. A method for polymerizing 1-olefins, which comprises heat-treating and further depositing an organic reducing agent. (20) In the above (19), organic phosphorylchromium has the formula (however, X in the above formula is P(OR)3 or PH(
OR) 2 and R is alkyl, aralkyl, aryl, cycloalkyl or hydrogen, and at least one R is other than hydrogen. ). (21) The method according to (19) or (20) above, in which the supporting material is made of silica gel. (22) In the above (21), the supporting material is about 1.
A silica xerogel with a pore volume larger than 96 cc/m and the majority of its pore volume is about 300 to about 600 A
A method consisting of pores with a pore diameter within the range of . (23) The method according to any one of (19) to (22) above, in which the organic reducing agent comprises an organometallic compound. (2) In the above (23), the organometallic compound is a compound selected from the group consisting of alkyl aluminum, an alkyl aluminum halide, and an alkyl aluminum alkoxide compound. (25) In the above (24), A method in which the reducing agent is triethylaluminum. (26) A method in the above (24), wherein the reducing agent is triisobutylaluminum. (27) A method in which the above compound is Aluminum to chromium atomic ratio is approximately 1:1
5:1 to about 5:1. (28) The method according to any one of (19) to (22) above, wherein the organic reducing agent is triethyl boron. (2
9) The method of (28) above, wherein the triethyl boron is present in an amount sufficient to provide a boron to chromium atomic ratio in the range of about 0.1:1 to about 20:1. (30) A method according to any of (19) to (29) above, wherein the polymerization is carried out in the presence of hydrogen. (31) The method according to (30) above, wherein the hydrogen pressure is in the range of about 10 to about 75 psig. (32) In any of (19) through (31) above, further having a melting index (MI) of less than about 2, a high load melting index (HLMI) of at least 25, and an HLM of at least 40.
A method comprising the step of recovering a polyolefin characterized by an I/MI ratio. ($) A polyolefin for blow molding, comprising the product of any of the methods (19) to (32) above. (34) A structure blow-molded from the polymer according to any one of (19) to (32) above. (35) A bottle blow-molded from the polymer of (32) above. (Phrase 3. An improved method for producing blow-molded articles from polyolefins, comprising blow-molding such articles from the polymer of (33) above.

Claims (1)

[Claims] 1. Chromium trioxide is expressed by the formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (Here, R is alkyl, aralkyl, aryl, cycloalkyl, or hydrogen. at least one R is other than hydrogen), the resulting organic phosphoryl chromium reaction product is deposited from an organic solvent onto a solid inorganic support, and then 4
Heat treating the support and the organic phosphoryl chromium reaction product in a dry oxygen-containing atmosphere at a temperature above 00°F (about 205°C) and below a temperature at which the structure of the support is damaged; aluminum compounds,
A method for producing an olefin polymerization catalyst, which comprises adding at least one organic reducing agent selected from the group consisting of an organozinc compound, an organomagnesium compound, and an organoboron compound. 2 The ratio of the metal component of the reducing agent to the chromium of the organic phosphoryl chromium reaction product is 0.1/1 to 20
The method according to claim 1, wherein: /1.