TW206242B - - Google Patents

Description

No. 81107904 Amendment Page of Chinese Specification for Patent Application Case

April 82, 1992 I. Description of the invention (1) The present invention relates to a method and catalyst for the preparation of ethylene polymers, especially ethylene homopolymers and copolymers of ethylene and high α-olefins. In particular, the present invention relates to a solution polymerization method for such polymers, in which the procedure is operated at a temperature of at least 180 °, and the catalyst is activated with an aluminum alkoxyalkyl compound. Ethylene polymers, for example, ethylene homopolymers and copolymers of ethylene and high alpha-olefins, have a variety of uses, for example, films, fibers, molded or thermoformed products, tube coatings, and the like. There are two methods for making polyethylene, including polymerizing monomers in the presence of a coordinating catalyst in an inert liquid medium, ie, the operator below the melting or dissolution temperature of the polymer and above the melting or dissolution temperature of the polymer operator. The latter is called the 'solution' method, and its example is described in the Canadian patents 6 6 0, 8 6 9 of A.W. Anderson, E.L. Fallw-el 1 and J.M. Bruce, which was filed on April 9, 1963. In the solution method, the procedure is operated when both the monomer and the polymer are dissolved in the reaction medium. The precise control of the degree of polymerization and the molecular weight of the resulting polymer can be achieved by the control of the reaction temperature. In the solution polymerization method, it is preferably at an extremely high temperature, for example, > 2 5 0 t :, the operating procedure and the heat of polymerization are used to distill off the solvent from the resulting polymer solution. Although the step of removing the catalyst from the polymer can be taken after the procedural polymerization step, the solution polymerization method is preferably operated without a catalyst removal step. Therefore, the catalyst remains in the polymer, and this catalyst, which can be called '" catalyst residue, ", can make the resulting polymer appear colored and break the polymer during or after polymer processing. The amount of catalyst residues, at least in part, is related to the total activity of the catalyst used in the procedure polymerization step, because the higher the total activity of the catalyst, the less the catalyst, usually, that is, what is needed to carry out the polymerization at an acceptable rate . Thus has a high total

E (Please read the precautions on the back before filling in this page) i Pack ·-Order-Printed by the Beigong Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs. The paper size is compliant with China National Standard (CNS) Grade 4 (210 X 297 mm) ) One 3-206242 I supplement no A6 B6, 2 V. Description of the invention (active catalyst is beneficial to the solution polymerization method. (Please read the precautions before filling in this page> Two important factors to determine the total activity of the catalyst The factor is under the operating conditions, especially the instantaneous activity of the catalyst and the stability of the catalyst at the operating temperature. Many catalysts that are extremely active in the low temperature polymerization method also have high instantaneous activity at the high temperature used in the solution method, but in the solution method It is easy to decompose in a very short period of time, and the total activity is quite low. This catalyst has no industrial value in the solution method. Other catalysts may have an acceptable total activity at the high temperature of the solution method, but it is easy to produce a molecular weight distribution that is too broad or The molecular weight is too low to be used as a polymer in the production of a variety of useful finished products. Therefore, the requirements and performance of the solution polymerization method catalyst are quite different from those used in the low temperature polymerization method, as is familiar with this Known by the artist. The preparation of ethylene polymer in the solution polymerization method is described in PCT Patent Application W〇91 published on January 14, 1991 by MC Hughson and VG Zboril. / 17193, and the attached patent application. The catalyst activated with siloxane can polymerize ethylene at very high temperature. However, the residue of siloxane from this catalyst is easy to be attached to the solvent in the polymerization process The recovery and recycling part has a significant adverse effect on the performance of the adsorbent used to purify the solvent. The Central Technology Bureau of the Ministry of Economic Affairs printed the previous technology. At 90 ° C) Warm ethylene and its adjuvants for the polymerization of alpha-olefins to increase the activity and / or stereospecificity of catalysts have been studied in detail. Aromatic acids such as toluene or benzoic acid, ether and alcohol esters are often used here However, most of the electron donors that can be used at low temperatures break the catalyst activity with the increase of the polymerization temperature. For example of using electron donors, Greeenners et al. Mentioned USP on June 27, 1978. This paper standard is universal China. National Standard Standard (CNS) «P 4 specification (210 X 2 mm) 1-4 A6 B6 206242 V. Description of the invention (3) 4 0 9 7 659 shows a low-temperature polymerization method at a temperature of 20-1 001C in an inert solvent Operate within the scope, in which detailed examples of activators include dimethyl monobutyl aluminum chloride, monodecyl aluminum propoxy aluminum chloride, and monobutyl aluminum monobutyl aluminum oxide. As described below, even part of the trialkyl aluminum . SP 4 097 659 used aluminum alkoxy alkyl substitution, even if the temperature is only 13010, which is the lowest operating temperature of the solution polymerization method, the activity of the media is still substantially reduced. Surprisingly, it was found that at high temperatures, the tendency of this catalyst activity to decrease is reversed and the catalyst activated by alkylaluminum alkylaluminum has superior activity at temperatures above about 18 ΟΌ. Therefore, the present invention proposes a solution preparation method of α-olefin high molecular weight polymer, the polymer is selected from the group consisting of ethylene homopolymers and copolymers of ethylene and C3-Cu high α-olefins, and its pseudo is in the catalytic amount Polymerization of ethylene and / or a mixture of ethylene and C3 — (:; 2 high olefins) in the presence of a titanium-containing coordination catalyst in an inert solvent and at a temperature exceeding 105 ° C. Its improved characteristics are: (a) catalyst Activated by a solution of alkane alkyl aluminum in an inert solvent; and (b) This procedure is operated at least in part at a temperature of at least 180 ° C. The present invention also proposes a solution preparation method of high molecular weight polymer of α-olefin The olefin is selected from the group consisting of ethylene homopolymers and copolymers of ethylene and C. A Cu high alpha-olefin copolymer, this method includes the selection of a group containing ethylene and ethylene and at least one-(:, 2 high "-olefin For the monomers of the mixture, the size of the clothes and paper is in accordance with the Chinese Standard (CNS) A 4 specifications (210 X 297 male yak) _ 5 „Please read the back first. Please pay attention to the matters before filling in this booklet-Ministry of Economics Printed by the Central Bureau of Standards, 3 Industrial and Consumer Cooperatives 81 .9.25,000 A6 B6 is formed by polymerizing the monomer and recovering the temperature component from 0 to 3201C. The first group of bases and the aluminum alkyl and alkane A 1 R, Ο R 〃… and each is selected from 20 is 1 to 3 and m is ◦ 1. Please read the notes and matters on the back side first, then fill in this Ss with 206242. 5. Description of the invention (4) The coordination catalyst and inert hydrocarbon solvent are fed into the reactor. The pending symbol is that the monomer is polymerized at 18 and the coordination agent is composed of a first component and a second titanium-containing component and the second component is selected from the group consisting of a mixture of aluminum aluminum alkoxides. The general formula is, in the formula, R, and R 〃 are the same or different alkyl atoms or aryl groups, X is halogen, η 2 〇-8 sulfonic atom alkyl group and 3, and R 〃 are each with 2- 8 carbon atom alkyl group and m = 2 In the preferred embodiment of the invention method, R is 2 η-In the example of the invention method, the second component is in the form of a mixture of trialkyl aluminum and alcohol, in which the amount of alcohol is less than The stoichiometric amount of dialkylalkane aluminum, especially trialkylaluminum is A 1 RS, where R3 is an alkyl group with 〃〃nitrate and the general formula is R40H, where R4 is a sulfonogen with 1-20 Alkyl or aryl groups, especially those with 1 to 16 atoms. In another example of the method, the first component is formed from the following: Printed by the Central Bureau of Standards of the Ministry of Economic Affairs wk industrial and consumer cooperatives (i) MgRS and A1 A mixture of R%, wherein R / and R2 are the same or different and are each selected from alkyl groups with 1 to 1 ◦ large atoms; (ii) reactive chlorine component; and (m) titanium tetrachloride. Or The first component can be blended with a titanium tetrachloride solution at a temperature of less than 30 ° C, which optionally contains vanadium trihalide and organic aluminum compounds, such as trialkyl aluminum or dialkyl aluminum halides, And heat the resulting admixture to 150 81.9.25.000 [Paper Scale General Chinese General Standard (CXS) A 4 specifications (210 X 297 male yak) _ 6 A6 B6 206242 V. Description of the invention (5) — 3 0 0t: 5 seconds to 60 minutes to form quickly. In another example, the formation and blending of the first and second components are performed at a temperature connection of less than 3 Ot :. The present invention is directed to a method for preparing a polymer of α-olefin polymer, which is intended to be used to make finished products by extrusion molding, injection molding, thermoforming, rotary molding, and the like. In particular, the α-olefin polymers are ethylene homopolymers and ethylene and high α-olefins, that is, α-olefins of ethylene, especially high α-olefins with 3 to 12 atoms, ie C 3-C / 2 α -Olefins, such as copolymers of 1-butene, 1-hexene and 1-octene. In addition, the cyclic bridged methylenediene can be fed into the program with ethylene or a mixture of ethylene and mono-olefin. Such polymers are known. In the method of the invention, the monomer, coordination catalyst, inert hydrocarbon solvent, and optionally hydrogen are fed into the reactor. The monomer may be ethylene or a mixture of ethylene and at least one C3-C 〃high alpha-olefin, preferably ethylene or ethylene and at least one C4-C /. A mixture of high alpha-olefins; alpha-olefins are known to be hydrocarbons. The coordination catalyst is formed by two components, namely the first component and the second component. The first component contains titanium or its blend with other transition metals below the maximum valence, and is an organometallic component commonly used in solution polymerization. The first component may be in solid form. Examples of the first component are shown above. The second component is a solution of alkylaluminum alkyl or alkylaluminum and alkylaluminum alkyl in an inert solvent; the ratio of aluminum alkyl to aluminum alkoxide in the mixture can be used to control the process. Aluminium alkyl formula A 1 and alkoxy aluminum alkyl formula

Ai? R / m〇R, where R, and R 〃 are alkyl or aryl I (please read the precautions on the back before filling in this! /, _Install_ order. Printed by Beigong Consumer Cooperatives, Central Standards Bureau, Ministry of Economic Affairs This paper is again suitable for the Chinese National Standard (CXS) A4 (210 X 297 male wear) -7-81.9.25,000 A6 B6 2,00242 V. Description of the invention (6) (Please read the notes on the back first Fill in this first one again, it has 1-20 carbon atoms, X is halogen, especially gas, atmosphere or bromine, η is 1-3 and m is 2. The preferred halogen is chlorine. Alkyl alkane can be blended by The corresponding aluminum alkyl and the corresponding alcohol are prepared to form alkane aluminum alkyl. Preferably, the aluminum alkyl is the same as the aluminum alkyl in the second component. In fact, the preferred method for forming the second component is to The amount of alcohol added to the aluminum alkyl is less than the stoichiometric amount required to convert all the aluminum alkyls to alkane aluminum alkyls. The mixing can be carried out simply at a temperature of less than 301 to make the reaction proceed for the shortest time. The time depends on the type and reactivity of the components used to prepare the specific catalyst. As shown below, the alcohol is fed directly to the polymerization Harmful. The ratio of alcohol to aluminum alkyl used to control the polymerization process is 0.1-1 (alcohol: aluminum). The concentration of the components of the solution used in the preparation of the catalyst is not standard, but the practicality is generally considered. The availability is low Concentrations up to 25 ppm are based on weight, but higher concentrations, such as 100ρργπ and above, are preferred. As described below, the sequence of steps for preparing the catalyst is extremely important for obtaining highly active catalyst. Central Bureau of Standards, Ministry of Economic Affairs 8 Industrial and Consumer Cooperatives Co., Ltd.? The coordination catalyst described in this article is used in the inventive process without separating any components of the catalyst. In particular, the liquid or solid parts are not separated by the catalyst before being fed into the reactor. In addition, the catalyst Its components are not slurried. All components are easy to handle and store stable liquids. The solvents used in the preparation of coordination catalysts are inert hydrocarbons, especially hydrocarbons inert to coordination catalysts. It is known and includes, for example, hexane, hexane, octane, cyclohexane, methylcyclohexane, and gasified naphtha. The paper size of the catalyst preparation is applicable to China National Standards (CNS) A4 specifications (210 X 297 male yak) -8 81.9.25,000 2062 42 A6 B6 Printed by the Central Standards Bureau of the Ministry of Economic Affairs, Industry and Consumer Cooperatives 5. The description of invention (7) The solvent used is preferably the same as that sent to the reactor for the polymerization process. The first component of the catalyst described in this article can be, According to the method of the present invention, it is used at a wide range of temperatures used in the α-olefin polymerization method operating under solution conditions. For example, the polymerization temperature can be 105-320 ° C, especially 105-3 1 ◦ t: However, as follows As mentioned above, the activator is particularly effective at a temperature of 180 ° C. Therefore, the inventive method, at least in part, operates at this high temperature. The pressure used in the inventive method is known to the solution polymerization method, for example, about 4-2. MPa pressure. In the method of the present invention, α-olefin monomer is polymerized in the presence of a catalyst in the reactor. The pressure and temperature are controlled to keep the formed polymer in the solution. Less hydrogen is placed, for example, 1_100 parts per 1 million weight, based on the total solution sent to the reactor, it can be added to the feed to improve the melt index and / Or the control of molecular weight distribution and thus is conducive to the production of more uniform products, as shown in Canadian patents 703, 704. The solution passing through the polymerization reactor is generally treated to deactivate any catalyst remaining in the solution. A variety of catalyst energy dissipating agents are known, examples of which include fatty acids, alkaline earth metal salts of aliphatic carboxylic acids, alcohols and trialkanolamines, examples of which are triisopropanolamine. The hydrocarbon solvent used for energy dissipation is preferably the same as that used in the polymerization procedure. If different solvents are used, they must be compatible with the solvents used in the polymerization mixture and have no adverse effect on the solvent recovery system accompanying the polymerization process. After the catalyst is deactivated, the polymer-containing solution is passed through a bed of activated alumina or bauxite, which removes some or all of the deactivated catalyst residue and / or (please read the precautions on the back before slamming) Write a copy! — Loading · .-ΤΓ.. Thread. Applicable to China National Standard (CXS) A 4 specifications (210 X 297 male yak) -9-81.9.25,000 ^ 〇6242 A6 B6 Central Standards Bureau of the Ministry of Hydrocarbon Economy® : Printed by the Industry and Consumer Cooperatives 5. Description of the invention (8) Impure substances. However, it is better to operate without removing the residue of the catalyst after the extinguishment. Then the solvent is flashed from the polymer, which is then squeezed into water and cut into pieces Pellets or other suitable finely divided shapes. The recovered polymer can be treated with saturated steam at atmospheric pressure to, for example, reduce the amount of volatiles and improve the color of the polymer. This treatment is carried out for about 1 to 16 hours, after which the polymer is dried and Cool with airflow for 1 to 4 hours. Pigments, anti-gas agents, UV shielding agents, hindered amine light stabilizers and other additives can be added to the polymer before or after the polymer is initially formed into pellets or other finely divided shapes. Polymerization from the method of the invention The antioxidant may be, for example, a single antioxidant, such as a hindered phenol antioxidant, or a mixture of antioxidants, such as a combination of a hindered phenol antioxidant and a secondary antioxidant, such as phosphite. Anti-gas agents are known in the art. For example, the ratio of phenolic anti-chlorine agent to secondary antioxidant can be 0.1: 1 to 5: 1, and the total amount of antioxidant is 200 to 300 ppm. The inventive method can be used to crack ethylene homopolymers and copolymers of ethylene and high α-olefins, the density of which is, for example, about ◦0.90〇.97〇g / cm3, especially 〇.915-0. 965 g X cm 3; high-density polymer, such as about 0.96 ◦ and above, is a homopolymer. This polymer has a melt index, measured by the method of ASTM D-1 2 3 8 and condition E, about 〇. 1-2 Especially about 0.1-12〇dg / min. It can produce polymers with narrow or wide molecular weight distribution. For example, the polymer can have a stress index, a measurement of molecular weight distribution, about 1.1- 2. 5, especially about 1. 3-2. 〇. Stress index using AS TM melt index test method in two stress (clothing paper scale is applicable to China National Standard (CNS) A 4 Grid (210X297 male yak) _ 1〇_ 81.9.25,000 (please read the precautions on the back and face before filling in this book. Packing. Ordering 206242 A6 B6 V. Description of the invention (9) 2160g and 6480g load) The body index flux depends on the following formula: (wt. Stress index saved by 6480g wt.> Ε 0.477 (wt. Extruded at 2160g wt.) (Please read the precautions on the back first and then focus on this one {Printed by W Industrial and Consumer Cooperative, Central Bureau of Standards, Ministry of Economic Affairs

Stress index values less than about 1.40 show a narrow molecular weight distribution, while values above about 1.70 show a narrow molecular weight distribution. The polymer produced by the method of the present invention can be made into a variety of products, known as ethylene homopolymer and copolymer of ethylene and c (one olefin. Unless otherwise stated, the following examples use the following method: The reactor is equipped 8 1 m free volume (regular inner type, about 15 X 90 mm) pressurized container with 6 fixed baffles at regular intervals. The container is equipped with a paddle turbine propeller, heating sleeve, pressure and temperature control Device, three feed tubes and a single outlet. The feed tube is located at the top of the container, the distance from the shaft is 40mm each, and the outlet tube is axial with the agitating drive shaft. The catalyst precursor and other reagents are in the hexane The solution was prepared by using nitrogen vapor in advance to pass through the bed of activated alumina, molecular sieve and silica gel. Ethylene was introduced into the reactor with a cyclohexane solution prepared by dissolving pure gas ethylene in a pure solvent. The feed rate of the components is adjusted to produce the desired reactor condition. The residence time in the catalyst tube is achieved by adjusting the tube length of the component. The residence time in the reactor is adjusted by adjusting the flow of solvent to the reactor so that the total The flow remains fixed and remains fixed. The pressure of the reactor should be maintained at 7. 5M nails.. Line. L paper scale is applicable to China National Standard (CNS) A 4 specifications (210 X 297 mm) -H-81.9.25,000 206242 A6 B6 Employee Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs Printed 5

5. Description of the invention (10) Pa and the temperature and flow are kept constant in each experiment. % The initial (unconverted) monomer concentration in the reactor is 3-4 wt.%. The energy killer is triisopropanolamine or triacid, and the solution in toluene or cyclohexane is injected into the reactor effluent at the reactor outlet. · The logistics pressure drops to about llOKPa (Abs.) And unreacted monomers are detected by gas phase analysis. The catalyst activity is defined as Kp-(QW1-Q)) (1 / HUT) (1 / catalyst concentration) where Q is the portion of the ethylene (monomer) converted into polymer, and HUT is the reactor retention expressed in minutes The time and the catalyst concentration are expressed in mm. The concentration in the reaction vessel is also corrected for impurities. The catalyst concentration is based on the sum of transition metals. Calculate the polymerization activity (K p). The invention is illustrated by the following examples. Unless otherwise stated, the solvent used in each case was cyclohexane, the monomer was ethylene and the reactor residence time was fixed at 3.0 m i η. Fenshi Example I The catalyst was mixed with a solution of dibutylmagnesium, triethylaluminum, t-butyl chloride and tetra-vaporized titanium in cyclohexane at room temperature (approximately 30 ° C). It is prepared by adding a solution of triethylaluminum in hexane. The concentration and flow rate of each substance are adjusted to obtain the following molar ratio: Nitrogen (from tert-butyl gas) m Please read the intention first. Please fill out the matter before this. Μ The paper size of the binding book is applicable to the Chinese National Standard (CNS) A 4 Specifications (210 X 297 public) -γχ ~ 81.9.25,000 2,06242 A6 B6 V. Description of the invention (11) Magnesium / Titanium = 5.0; Aluminum (first triethylaluminum) / Titanium aluminum (second third Ethyl aluminum) / titanium 0 3 9; 〇〇 reactor polymerization at a temperature of 2 3 Ot :, measured in the reactor, operation. The solution passing through the reactor is deactivated and the polymer is recovered, as described above. The catalyst activity (Kp) was calculated and the results obtained are shown in Table 1. The recorded C5 // Mg ratio is the optimal ratio required to obtain maximum catalyst activity at the indicated Mg / Ti and / Mg ratios. In the second and third pass, the catalyst was prepared as above, except that 1 molar equivalent of T-butanol (per mole of Al 2) was added to the second triethylaluminum (thus forming an alkoxide). Please read the note on the back first-the matter will be written in the field. • Threads are printed by the Industrial and Consumer Cooperative of the Central Standards Bureau of the Ministry of Economics and Economy. 81.9.25,000 A6 B6 V. Description of the invention (12) Table I Process ratio Cl / Mg Mg / T i A 17 / Mg A 12 / Mg Alcohol temperature Kp 1 2.4 5.0 0.9 3.0 No 230 13.9 2 2.2 5.0 0.9 6.0 t- Butanol 230 31.7 3 2.4 5.0 0 9 3.0 t_butanol 230 4.8 4 2.3 5.0 0.9 3.0 Phenol 230 30.4 5 2.2 5.0 0.9 3.0 Ethanol 230 24.9 6 2.3 5.0 0.9 4.5 η-decanol 230 24.1 7 2.2 5.0 0.9 3.0 New Pentyl 230 29.3 Alcohol 8 2.3 5.0 0-9 6.0 t_ Butanol 230 2.7 Note: 1 The ratio of triethylaluminum to titanium when first added 0 2 Triethylaluminum or alkyldiethylaluminum when first added For Titanium-< (Please read the precautions on the back first and then fill in your own.-Installed. Nail · Thread. Printed proportion of 8 industrial and consumer cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs.

The polymer rate constant calculated by Kp, m i η 〇 3 is added to the reactor instead of t-butanol of the catalyst. The first, second and third stages show that the proportion of the catalyst component used in the alkane gas strip has a significant effect on the increase in activity, which changes as expected with the type and composition of other catalyst groups and the type of operation of the program However, it is stated that the size of the coat paper can be applied to the Chinese National Standard (CNS) A 4 specifications (210 X 297 male yak) 81.9.25,000 14-A6 B6 V. Description of the invention (13) The catalytic activity of one of the two factors Increase. The comparison between the third pass and the second pass shows that the catalyst activity is sensitive to the component ratio, and it can be used to control the program. Uses of alcohols other than 4, 5, 6 and 7 Chengfumin butanol. Stage 8 illustrates the adverse effects of adding alcohol directly to the reactor rather than the second triethylaluminum stream. This proves that it is necessary to form the aluminum alkyl chloride first. Comparing Example I with other known activators used in the high-temperature polymerization method, the activator and reaction temperature shown by the user ϋ repeat the method of Example I. The results are as follows. (Please read the notes on < 6 'first, and then write 1 < Public)) _ 15 _ 81.9.25,000% 0624¾ __--- * A6 B6 Five 'Invention Description (14)

Table] I scale ratio C1 / Mg Mg / T i A1 VMg A1 2 / Mg Activator temperature Kp 9 2.3 5 • 0 0.9 6.0 BUODEAL 200 93.7 10 2.2 5 .0 0.9 6.0 BUODEAL 230 31.7 11 2.3 5 .0 0- 9 6.0 BUODEAL 260 7.4 12 2.3 5 .0 0 · 9 3.0 DESI 200 155.7 13 2.3 5 .0 0.9 3.0 DESI 230 35.4 14 2.4 5 .0 0.9 3.0 DESI 260 9.1 15 2.2 5 .0 0.9 1.5 DIBALO 200 58.0 16 2.3 5 .0 0.9 1.5 DIBALO 230 16.2 17 2.2 5 .0 0.9 1.5 DIBALO 260 2.8 18 2.2 5 .0 0.9 1. 5 TEAL 230 13.9

Please read the precautions on the back before filling in this A BUODEAL t-Butyl Diethyl Aluminum DESI Diethyl Aluminum Ethylene Dimethicone DIBALO Diisobutyl Aluminoxane TEAL Triethyl Aluminum 1 Mole Ratio of Triethyl Aluminum to Titanium 2 Activator vs. titanium mole bb Kp 1 / mm 〇1 / min in 0 Printed by DK Industrial and Consumer Cooperatives, Central Bureau of Standards, Ministry of Economic Affairs * 1 Clothing This example shows that t-butane diethylaluminum is compared with other activators. This paper scale is applicable to China National Standards (CNS) A 4 specifications (21〇X 297 public) -16 " 81.9.25,000 Α6 Β6 V. Description of the invention (15) The temperature catalyst activity has been considerably improved. Cao Shi Example M The catalyst consists of a solution of titanium tetrachloride, three atmospheres of vanadium and triethylaluminum in cyclohexane. The blending solution is heat-treated for 1 1 ◦1 1 2 0 seconds by blending with the hot cyclohexane solvent at 205-2 1 ου. Then add activator to activate the catalyst. The polymerization reactor was conducted at the temperature shown in Table 3. The solution obtained from the reactor was deactivated and the polymer was recovered as above. Calculate catalyst activity. The results obtained are as follows; in each pass, (a certain Ti) / (mol ν) = 1. * (Please read the precautions on the back before filling in this one {丨 installation. Order-• Line · Printed by the Staff Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 81.9.25,000 This paper standard is applicable to China National Standard (CNS) A4 specifications (210 X 297 father's foot) -17- Printed by the Central Standards Bureau of the Ministry of Economic Affairs, Labor and Consumer Cooperatives l ------ A6 _'_ ~ B6 Fifth, the description of the invention (Table III program. Proportion number A 1 V (Ti + V) Al2 / (Ti + V) activator temperature Kp 19 1. 0 4.0 TEAL 200 72.8 20 1.1 2.0 TEAL 230 20.0 21 1.1 2.0 TEAL 260 5. 3 22 1.1 2.7 DES I 230 33. 1 23 1.0 2.7 DES I 260 11.5 24 1.0 1.3 DIBALO 200 71.7 25 1.0 1.3 DIBALO 230 21.7 26 1.0 1.3 DIBALO 260 6.4 27 1.0 2.0 DEODEAL 200 123.5 28 1.0 2. 0 DEODEAL 230 37.9 29 1.1 2. 0 DEODEAL 260 11.7 DEODEAL decyloxy diethyl Aluminum DES I Diethylaluminum ethylenedimethicone DIBALO Diisobutylaluminoxane TEAL Triethylaluminum 1 Diethylaluminum chloride molar ratio of titanium and vanadium 2 Activator molar ratio of titanium and vanadium Compare (please read the notes on the back before writing this page) This paper Of the applicable Chinese National Standard (CNS) A 4 Specifications (210 X 2 Ding mm) 18 -. 82.3 40,000

Use 1 to make it clear that it is possible to change this to Wuliang, which can be converted into aluminum-based ethylenedioxide IV.

3 rH Use 9 Use. The following agents are like fruit, and the result is the same. The method is compared with the square aluminum m-based alkyl-clad double-oxygen, and the alkylene temperature comparator should be anti-OC.

Table IV Proportional number AlV (Ti + V) A 1 2 / (T i + V) Activator temperature Kp 30 1.0 2.0 TEAL 130 231 31 1.2 2 _ 7 DES 1 130 89 32 1.1 2. 0 DIBALO 130 292 33 1.0 3. 5 DEODEAL 130 75 (Please read the notes on the back before writing this page) Binding DEMODEAL decyl diethyl aluminum DES I diethyl aluminum ethylene dimethysiloxane DI BALO Diisobutylaluminoxane TEAL Triethylaluminum 1 Molar ratio of the sum of titanium and vanadium by diethylaluminum chloride 2 Molar ratio of the sum of titanium and vanadium by the activator The standard of this paper is the Chinese National Standard (CNS) A 4 specifications (210 X 297 mm> 19-82.3. 40,000 A6 B6 V. Description of the invention (18) This example illustrates the low temperature activity of the catalyst when using dialkyl aluminum alkane as the activator, so it is unexpectedly good The high temperature activity. Please read the notes on the back side first and then fill in this booklet-booked by the Central Standards Bureau of the Ministry of Economic Affairs, printed by the 8th Industrial Cooperative Cooperative L. The paper size is applicable to the Chinese National Standard (CMS) A 4 specifications (210 X 297 public ) -20 81.9.25,000 Annex III A: Chinese Supplement for Patent Application No. 81107904 The data of the test data in the Republic of China in April, 1982, the Central Committee of the People's Republic of China} Guju 7, > |: Greek; > The number of melt index stress index JVI η M w 1 43.8 1.51 11712 46666 4 24.8 1.29 15851 56409 e 9.1 1.34 16495 69440 11 79.3 — 11303 43069 12 8.9 1.36 17926 69619 16 48.9 1.41 11409 49298 18 43.8 1.51 11712 46666 20 7.9 1.47 15506 75543 21 26.7 1.41 11376 52644 22 6.8 1.36 17549 77629 Ά 1.7 1.40 20063 115519 25 8.9 1.39 12110 72177 2G 40.6 1.50 11277 48872 28 7,6 1.36 16983 75016 29 32.7 1.31 13886 52110

Claims (1)

206242 1 repair it to fill Wutai Α7 Β7 C7 D7 Ministry of Economic Affairs Central Standard Ju Beigong Consumer Cooperative Printed $ 六 、 Applying Patent Exemplary Group Annex A A: Patent Application No. 81107904 Amendment of Chinese Application Patent Scope Amendment April 2000 1. A solution preparation method of α-olefin high molecular weight polymer, the polymer is selected from the group consisting of ethylene homopolymer and copolymers of ethylene and (: 3-Cu high ct-olefin, and its content in catalytic amount Polymerization of ethylene and / or a mixture of ethylene and C 3-C 〃 high olefins in the presence of a titanium coordination catalyst in an inert solvent and at a temperature of 105-320Ϊ: The modified special emblem is: (a) Alkane alkyl aluminum solution is activated in an inert solvent. The general formula of aluminum alkyl is Ai ^ R ^ OR ", where R / and R " · are the same or different and are selected from the group consisting of 1 to 12 atoms Alkyl or OR " is phenoxy, X is dentin, η is 1 to 3 and m is 0 to 2; and (b) this procedure is at least partially operated at a temperature of 180-32〇υ2. 2.—α —Solvent preparation method of olefin high molecular weight polymer, the olefin is selected from the group consisting of ethylene homopolymer and ethylene with C3 — Ci2 high α -Groups of olefin copolymers, this method involves feeding monomers selected from the group consisting of ethylene and a mixture of ethylene and at least one C 3 -C 2 2 high α-olefin, a coordination catalyst and an inert hydrocarbon solvent into the reaction The polymer is used to polymerize the monomer and recover the resulting polymer, which is characterized in that the monomer polymerizes at a temperature of 180 °-320 ° C and the coordination catalyst is formed by the first component and the second component , The first component contains titanium and the second component is selected from the group consisting of alkyl alkoxy aluminum and a mixture of aluminum alkyl and aluminum alkoxy alkyl, the general formula of aluminum alkyl is A 1 R / m〇R , In the formula (please read the precautions on the back before writing this page) .— install _ l · order · The paper size is applicable to China National Standard (CNS) A 4 specifications (210 X 297 mm)-= 1-11 A7 B7 C7 D7 VI. Scope of patent application (please read the precautions on the back before writing this page) R, R- and R 〃 are the same or different and are each selected from a hospital or OR "; Is a phenoxy group, X is a halogen, η is 1 to 3 and m is 0-2 〇3. Such as the method of claim 1 or 2, wherein r is a 2-8 atoms Base and n = 3, and R- and R 〃 are each alkyl groups with 2 to 8 atoms and m = 2. 4. As in the method of claim 3, where the first component is less than 3 The titanium tetrachloride solution is blended at a temperature of 0 ° C, which optionally contains vanadium trihalide, and organic aluminum, and is prepared at a temperature of 150-300. (The temperature of 0 is heated to form the admixture for 5 seconds to 60 minutes. . 5 ♦ The method as claimed in item 3 of the patent application, wherein the second component is in the form of a mixture of trialkyl aluminum and alcohol, wherein the amount of alcohol is less than the stoichiometric amount required to form the dialkyl aluminum alkoxide. 6 ♦ The method as claimed in item 5 of the patent application, wherein the trialkyl aluminum is A5R3, wherein R3 is an alkyl group with 1 to 1 ◦ atoms and the general formula of alcohol is R4〇H, where R4 is alkyl or aromatic The base, which has 1 2 ◦ Shuo atoms. 7. As for the method of applying for the third item of patent scope, the first component is formed from the following: The Ministry of Economic Affairs Central Standards Bureau employee consumer cooperative printed (i) a mixture of MgRS and A1 R23, where R; and R 2 are the same Different and each is selected from alkyl groups with 1 to 10 atoms; (ϋ) reactive chlorine component; and (m) titanium tetrachloride 0 8. The method as claimed in item 4 of the patent application, in which organic The size of the aluminum compound paper is in accordance with the Chinese National Standard (CNS) A4 specifications (210 X 297 mm) ~ 2 ~ A7 recognition 6 said C7 _ D7 Sixth, the patent application model is trialkyl aluminum or dialkyl. halide. 9. The method as described in item 7 of the patent application park, in which the halide is a vapor. 1 0 · As in the method of claim 3, where the formation of the first and second catalyst components and their blending are performed at a temperature of less than 30 ° C. 1 1 For example, the method of applying for items 1, 2, 4, 5, 6, 7, 8, 9 or 10 in the patent garden, where the coordination catalyst is used without separating any of its components. 1 2. The method as claimed in item 3 of the patent application, in which the coordination catalyst is used without separating any of its components. (Please read the precautions on the back first and then write this page) 丨 Packed. The paper printed by the Central Stack Prospective Staff Consumer Cooperative of the Ministry of Economic Affairs is printed in accordance with the Chinese National Standard (CNS) Grade 4 (210 X 297 mm). ,