TW389772B - A catalyst system to produce highly crystalline polypropylene - Google Patents

Description

Appendix 2: Patent Application No. 85112303 Amendment to the Chinese Manual Revised in March of the Republic of China Fifth, the description of the invention (17) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs

Control TEA1 CMDS Example mmol mmol 1 1 2 2 1 1 3 1 0.5 4 1 0.1 5 1 0.05 6 1 0.033 7 1 0.02 8 1 0.01 g 1 0.002 PIPS 10 1 2 11 1 1 12 1 0.5 13 1 0.1 14 1 0.05 15 1 0.033 ptps 16 1 «0 2 17 1 1 18 1 0. 5 CPDS A1 / Si Table 2 Catalyst m or output β _ 0.5 10 48 1. 0 10 142 2. 0 10 205 10 10 269 20 10 249 30 10 269 50 10 280 100 10 302 500 10 294 0.5 10 163 1.0 10 214 2.0 10 294 10 10 305 20 10 249 30 10 243 0.5 10 274 1.0 10 246 2.0 10 309 B8QS〇msL ·, Λ day — supplemental xylene Isotactic solution.wt%% in m τη m 4.1 0.9 1.5 1.4 95 2.8 7.1 8.7 6.8 93.6 15. 7 91. 6 2.9 92.2 3.1 95 2.9 96 2.4 2.5 2-8 3.9 3.1 96 3.7 (Please read the Please fill in this page again for attention)-^ fv 'Packing -------- Order ----- This paper size is applicable to China National Standard (CNS) A4 (210x297 cm) -20-Central Ministry of Economic Affairs Quasi-office consumer cooperation Du Yin 袈 A7 ___B7_ V. Description of the invention (1) Skills: The present invention provides a catalyst system for supplying propylene polymers to produce A crystalline polypropylene, the system comprising a composition of a conventionally-transformed Giglia-Natta medium and an electron donor compound having the general formula S i R „(OR /), wherein R is selected from the group consisting of an alkyl group, Cycloalkyl, aryl, and vinyl; R — is alkyl: and m is 0 — 3, where R can be the same when R is alkyl; when m is 0, 1 or 2, R / Can be the same or different • 'When m is 1, 2 or 3, the R groups can be the same or different • The electrons have the following formula as 隹: 0¾

Si— R4 〇r3 Wherein 1 is an alkyl or cycloalkyl group, which contains a first-, second- or third-order carbon atom bonded to a silicon atom; R2 & R3 is an alkyl or aryl group, and R4 is an alkyl or ring Alkyl, whose secondary or tertiary carbon atoms are bonded to a silicon atom, RiS r4 may be the same or different * and 112 and 113 may be the same or different. Prior art description: Catalyst systems for the polymerization of hydrocarbons are well known in the art world. These catalysts generally include Giglia-Natta type polymerization catalysts; auxiliary catalysts, usually organoaluminum compounds: and electron donors, usually organic sand compounds. Examples of this catalyst system are shown in USP 4,107, 413; 4, 294, 721: 4, 439, 540; This paper size applies the Chinese National Standard (CNS) A4 format (210 X297 mm) I el. "--_ 1 ^-....... 1 .......- —1— -----, (Please & read the notes on the back and fill in this page again) -4-Central Laboratories of the Ministry of Economy 4. Description of the invention (2) 4,115,319: 4,220,554; 4,460,701; and 4,562,173; the list of these patents is hereby incorporated by reference. These patents are for application only. Some of the facts in the patent are related to catalysts and catalyst systems mainly used to polymerize propylene and ethylene. Conventional monomerized Giglia-Nata polymerization catalysts typically contain A halide, a complex formed with a metal hydride and / or a metal alkyl compound (generally an organoaluminum compound). The catalyst is usually supported on a magnesium compound and Aluminium alkylated titanium halides. External electron donors or selective control agents (SCA) can be added to improve the three-dimensional regularity of the catalyst and produce more crystalline polymers. Development of these polymerization catalysts It has improved catalyst and polymer properties. In addition to the improved catalyst, the improved activation method also increases the efficiency of the catalyst. An improved activation method includes pre-polymerizing the catalyst immediately before introducing the catalyst into the reaction zone. Process * One of this type of pre-polymerization process is shown in USP 4,767,73 5 and its disclosure is here for reference. In addition to the development of new catalysts and novel reaction methods, a kind of Giglia-Nata catalysts work together to form a suitable electron donor for the overall catalyst system, which has a great advantage in the polymerization industry, and greatly improves the properties of catalysts and polymers. In the system, it is believed that the auxiliary catalyst activates the catalyst and initiates the polymer bond. • The auxiliary catalyst that works well with the supported Giglia-Nata catalyst component is an organoaluminum compound, usually Aluminum alkyl Trialkylaluminium is the most typical, such as triethylaluminum (TEAβ) or triisobutylaluminum (TIBAj ^). The Chinese paper standard (CNS) A4 specification (210X297 mm) can be applied to this paper size ---- --- CI— (Please read the note on the back of the page and fill in this page again) Order-5-Printed by Alabaster Consumer Cooperatives, Central Bureau of Standards, Ministry of Economic Affairs, printed A7 B7 V. Description of the invention Other organoaluminum compounds that act as catalysts in Giglia-Nata catalyst components include alkyl aluminum dihalides and dialkyl aluminum halides. Electron donor compounds are used to reduce irregular forms of polymers during polymerization. To control and increase the production of legislative regularity or crystalline polymers. • Although many compounds are well-known electron donors, special catalysts may have specific compounds or groups of compounds that are particularly compatible with them. • High expectations Appropriate types of catalysts can be found, producing good catalyst efficiency, and improving the isotacticity of the desired polymer product and other properties of the product. * An electron is disclosed in USP 4,927,797. * This Invention includes another discovery Silane been found that a particular compound binds to a specific catalyst and an electronic member to the crystallinity of the produced polymer compared to the previously known a substantial increase in crystallinity of the resultant specific catalyst and other catalyst systems. SUMMARY OF THE INVENTION The present invention provides a catalyst system for propylene polymerization, wherein the system includes a combination of a specific catalyst and a specific electron donor compound, which greatly increases the crystallinity of the polymer product. The catalyst contains the conventionally-supported Giglia-Nata catalyst components, organoaluminum auxiliary catalysts, and organosilicon electron donors. The composition produces a catalyst system with a significantly higher crystallinity than (xylene) Less soluble) Polymer product provided by the previous catalyst as explained in the following comparative example • In addition, the catalyst system of the present invention using a specific conventional warp-shaped giglia-nata catalyst component, and Compared with other types of catalyst components, it provides better control of the xylene solubles of the polymer product. The paper size is applicable to the Chinese national standard (CNS > A4 specification (210X297 mm)! ^ — CI — ( (Please read the notes on the back and fill in this page)

, TT 6 Printed by the Shellfish Consumer Cooperative of the Central Bureau of Samples of the Ministry of Economic Affairs A7 ___ B7_ V. Description of Invention (4). In addition, the catalyst system of the present invention using a specific electron donor provides better control of the xylene solubles of the polymer product compared to other types of electron donors. These and other advantages can be further understood from the following detailed description of the invention and the accompanying examples. When the aforementioned catalyst is used in combination with a previously used electron donor, the crystallinity of the polymer product is increased slightly compared with the previously known catalyst, but when it is paired with the electron donor described in the present invention, it is greatly increased. Provides improved operational control for polymer properties such as xylene solubles. The most unexpected result obtained from the catalysts described in USP 4,784,983 and 4,861,847 and the composition of CMDS, DIDS, DTDS, CPDS and CIDS is the polymerization of the catalyst system in the polymerization of propylene. The crystallinity of the material is greatly increased. The catalyst system obviously achieves an efficiency of 30 kg / g-ca t · h at a Si / Ti molar ratio between 4 and 200 yuan. The present invention also provides A method for polymerizing propylene. The method includes: forming a catalyst by contacting a supported Gigliole-Natta catalyst component with an organoaluminum compound, preferably trialkylaluminum; contacting with organoaluminum At the same time or after, the catalyst is brought into contact with an electron donor, which is an organosilicon compound described in the aforementioned general formula, and the catalyst is polymerized in advance by contacting a small amount of monomer with the catalyst as appropriate. The catalyst is introduced into a reaction zone containing monomers under polymerization conditions, and the zone contains additional amounts of organoaluminum compounds and electron donors as appropriate: and this paper size applies Chinese National Standard (CNS) A4 specifications ( 2 丨 OX29? Mm>!, --- S ....... n I ni ^ rcί ^ · ..... I 1 n -I--, 1T (Please read «Read the precautions on the back before filling out this page） Printed by the Shellfish Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs A7 __ ^ _ B7__ 5 5. Description of the invention (5) Take out the polymer product. If the monomer is propylene, the xylene solubles are between 0.6 and 3. OOwt% in Fanyuan, and the Si / Ti ratio in the reaction zone is between 4 and 1. Within the range of 2000. If the electron donor is dicyclopentyldimethoxysilane and the monomer is propylene *, it is defined as the isotacticity of the polymer product (pentavalent of xylene soluble fraction Distribution percentage) has a crystallinity equal to or greater than 98%. DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a composition of a specific compound acting as an electron donor and a specific catalyst for polymerizing propylene. It has been found that the specific electron donor is indeed obvious. To enhance the catalytic properties of conventional Giggle-Natta catalysts • Any conventional Giglie-Natta transition metal compound catalyst component can be used in the present invention. Electron donors are generally based on two methods. Used to form Giglia-Nata catalysts and catalyst systems. • First, when When hydride or metal alkylate is used for reaction, the internal electron donor can be used in the formation reaction of the catalyst. The internal electron donor components suitable for the preparation of Giglia-Nata catalyst components include ethers and ketones. Lactones, electron donor compounds with N, P and / or S atoms and specific esters. Particularly suitable are phthalates, such as diisobutyl phthalate, dioctyl phthalate, diphenyl phthalate And butyl phthalate: malonates such as diisobutyl malonate and diethyl malonate; alkyl pivalate and aryl pivalate: alkyl maleate, maleic acid Naphthenates and aryl maleates: Alkyl carbonates and aryl carbonates, such as diisobutyl carbonate, ethyl carbonate. Paper size is subject to Chinese National Standard (CNS) A4 specifications (21 ×: 297 mm) CI — (Please read the notes on the back before filling this page) Order A7 B7 V. Description of the invention (6) Phenyl ester and diphenyl carbonate; Succinate esters, such as monoethyl succinate and diethyl succinate * Isophthalates are the preferred donors. The second use of electron donors in rhenium systems is as foreign electron donors in polymerization reactions. • modulator and the stereoscopic two cases may be the same compound, but generally different. Generally, the foreign electron donor is an organosilicon compound, such as cyclohexylmethyldimethoxysilane (CMDS). · The descriptions of the two types of gardenia are given by USP4,535 * 068, and the details are shown here for reference. The Gle-Natta hydrazone component includes compounds of the general formula MR, where M is a metal, R is a halide or a hydrocarbyloxy group, and X is a metal valence. M is preferably a transition metal. Groups I VB, VB, or VI B are more 隹, and group I VB is the most 隹, especially titanium. R is preferably gas, bromine, alkoxy, or phenoxy. Chlorine or ethyl gas is better, and gas is the best. Examples of transition metal compound catalyst components are T i C 1 4, T 1 B r 4 * T i (0 C 2H 5) 3c 1, T i (0 c 2 H 5) 3C 1, T i (〇c 3 Η 7) 2 C 1 2 * T i 0 C eH 13) 2 C 1 2 ， T i (0 c 2H s) 2 B Γ 2 and T i (0 c α 2h 2 5) C 1 3 · Available Printed by Shelley Consumer Cooperative, Central Bureau of Standards and Quarantine, Ministry of Mixed Economics of Transition Metal Compounds (please read the precautions on the back before filling this page). As long as there is at least one transition metal compound, the number of transition metal compounds is not limited. The support should be an inert solid, and any one of the components of the conventional Giglia-Nata catalyst is chemically inert. The support is preferably a magnesium compound. Examples of magnesium compounds used to provide a support source for catalyst ingredients are magnesium halides, dialkoxy magnesium, alkoxy magnesium halides, magnesium halides, dialkyl magnesium, oxygen. National Standard (CNS > A4 Specification (210X297mm) Printed by A7 of the Ministry of Economic Affairs, Zhuhai Bureau of Shellfish Consumer Cooperatives __B7_ V. Description of the Invention (7) Magnesium Oxide, Magnesium Hydroxide, and Magnesium Carboxylate · Use The organoaluminum compound as the auxiliary catalyst is preferably an alkyl aluminum of the general formula A 5 R / 3, wherein R ^ is an alkyl or halogen having 1 to 8 nitrogen atoms, and R > same or different, and At least one R-is an alkyl group, and R > same or different. The organoaluminum compound is preferably an alkyl aluminum, an alkyl aluminum dihalide or a dialkyl aluminum halide. The alkyl aluminum is preferably a trialkyl aluminum. , Such as triethylaluminum (TEAJ2) or triisobutylaluminum (ΤΙΒΑί). A specific giglia-nata catalyst component that can be used in the present invention is a commercially available giglia-nata for polymerizing olefins. Catalyst component, including: A catalyst component, consisting essentially of about 1.5-6. 0 wt% titanium, about 10-20% reset About 40-70% by weight are selected from halogen groups including chlorine, bromine and iodine; about 5-2 5% by weight are selected from polycarboxylic acid esters including aliphatic, aromatic and alicyclic polycarboxylic acid esters : And about 0.1-2.5% by weight are selected from organic phosphorus compounds including hydrocarbon esters of phosphoric acid and phosphonic acid, wherein each hydrocarbon group has 1 to 6 carbon atoms, and the catalyst component has the following steps Preparation by kneading method: a) Dissolving a magnesium halide compound in a solvent mixture to form a homogeneous solution, the magnesium halide is selected from the group consisting of a magnesium halide complex of magnesium dentate and water or an alcohol, and a derivative of a magnesium halide * Wherein the halogen atom is replaced by a alkoxy group or a halogenated alkoxy group; the solvent mixture is composed of an organic epoxy compound and an organic phosphorus compound to form a uniform solution, the organic epoxy compound is selected from the group consisting of aliphatic hydrocarbons and Diene oxides, halogenated aliphatic hydrocarbons and dihydrocarbon oxides and glycidyl ethers all have 2 to 8 carbon atoms, and the organic phosphorus compound is selected from the group consisting of alkyl phosphates * aryl phosphates, aryl phosphates Alkyl ester This paper is applicable to Chinese National Standard (CNS) A 4 Specifications (210X297 mm) '-10-CI— (Please read the notes on the back and fill in this page) Order the Ai B7 of the Beijin Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs 5. Description of the invention (8), Phosphorous acid Alkyl esters, aryl phosphites and aralkyl phosphites, in which the alkyl group has 1 to 4 carbon atoms, and the aryl group has 6 to 10 carbon atoms; b) the homogeneous solution has a general formula T i X „(0 R) is a mixture of liquid titanium compounds, where X is halosol, R is the same or different alkyl group, and η is an integer from 0 to 4: c) Add at least one auxiliary precipitant to form a precipitate A compound selected from the group consisting of carboxylic anhydrides, carboxylic acids, ethers and ketones; d) adding a polycarboxylic acid ester when a precipitate appears: e) separating the precipitate from the mixture, using a titanium compound T i X (0 R) 4_ „or a mixture thereof, treating the separated precipitate in an inert diluent, wherein X is halogen, R is a hydrocarbon group and may be the same or different, and π is an integer from 0 to 4; and f) using organic inert dilution Agent to wash the treated precipitate, as disclosed in USP 4,861,847 and 4,874,983, which is disclosed here For reference · The preferred auxiliary precipitation agent for the formation of rhenium is organic carboxylic anhydride, more preferably phthalic anhydride, and the addition is set to 0.03 to 1.0 mole per mole of magnesium halide. The acid ester is selected from the group consisting of aromatic polycarboxylic acid esters, preferably dibutyl phthalate and diisobutyl phthalate. • Better emotional dilution for washing precipitates. 1,2 digasethane. • Suitable titanium tetrahalides are Ti C l4 • TiBr ^^ Ti 14 and TiCl4 is preferred. The present invention is particularly related to a foreign electron donor. The term "a electron donor" used in the present invention means "external donors". Foreign electrons are used as stereoregulators to control the random form of the polymer produced. . Can also increase isotactic paper size Applicable to Chinese National Standards (CNS) A4 specifications (210 mm 297 mm.) '(Please read the notes on the back before filling this page) Order-11-A7 B7 V. Invention Explanation (9) Production of polymers • Organic silicon compounds are known in the art world as electron donors • Examples of electron donors for organic silicon compounds are disclosed in USP 4,218,339; 4,395-360: 4,328 , 122: 4,473,660 and 4,927,797 • As mentioned above, specific catalysts can produce better results when paired with specific electron donors. Examples of such catalysts paired with electron donors are revealed In USP 4,562,173; 4,547,552; and 4,927,797 · The electron donor has the general formula S i Rm (OR /) 4_m, where R is selected from the group consisting of alkyl, cycloalkyl, and aryl And vinyl; R " * is an alkyl group; and m is 0-3, wherein when R is an alkyl group, R may be the same; when m is 0, 1, or 2, the groups may be the same or different; and when When m is 1, 2, or 3, the R groups may be the same or different. * The electrons are preferably selected from organosilicon compounds having the formula: OR, printed by the Shellfish Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs. (Please read the notes on the back before filling out this page) where Rλ is an alkyl or cycloalkyl group, which contains the first, second or third carbon atoms bonded to silicon; R2 and R3 are alkyl or aryl groups: Alkyl or cycloalkyl, having secondary or tertiary carbon atoms bonded to a silicon atom, and R4 and R4 are the same or different, and R2 and R3 are the same or different. In a preferred embodiment, Ri is the second paper with 3 to 5 carbon atoms and mirror symmetry. Applicable to China National Standard (CNS) A4 specification (210 X25 »7 mm). Packing A7 B7 V. Description of the invention (10) k alkyl: R 2 and R 3 are methyl, ethyl, propyl, or butyl, but not necessarily the same: but have a mirror image with 3 to 6 carbon atoms Symmetric secondary alkyl or cycloalkyl. R1々R4 are the same and better, but are cycloalkyl, especially the group with 5 carbon atoms, that is, cyclopentyl. Specific electrons to the hip are cyclohexylmethyldimethoxysilane (CMDS), diisopropyl Dimethoxysilane (D IDS), di-tertiary butyldimethoxysilane (DTDS), dicyclopentyldimethoxysilane (CPD S) and cyclohexyl isopropyldimethoxysilane (CIDS). Cyclopentyldimethoxysilane (CPDS) is the best. The combination of the aforementioned electronic pretreatment and the conventionally-supported Giglia-Nata catalyst produced completely unexpected results that surpass previously known catalyst systems. The electron donor of the present invention may be limited by the stability and ease of operation of the compound, including storage, transportation, and use in a factory. The catalyst system can achieve a high effect at a wide S i / T i ratio (4 to 2 00), and control the formation of random polymers, or control the xylene solubles to a relatively low level. Generates isotacticity. When other catalysts are paired with the aforementioned electron donors, the xylene solubles of the polymer product increase linearly. However, the use of specific supported Giglia-Natta catalyst components with CMDS, DIDS, DTDS, CPDS Or the catalyst system of the present invention of CIDS, when the S i / T i ratio is reduced from 200 to 4 and lower, has a low xylene solubles from about 0.6 to about 3.0%. The catalyst system containing C P D S also provides relatively high crystallinity in the polymer product. The percentage of intermediate pentavalents (mmmm) in the heptane insoluble portion of the polymer product is extremely high, equal to or greater than 9 7%. The present invention also provides a method for polymerizing propylene. The use of the catalyst and the paper size are applicable to China Standard (CNS) A4 specification (210X297 mm) 1 I 11 ί I-—-«-II-—— HI« nm (Please read the notes on the back and fill in this page) -13-A7 B7 V. Description of the invention (11) The electron donor described in the foregoing formula, which includes: a) selecting a conventional single-gilled Giglia-Natta catalyst component; b) bringing the catalyst into contact with an organoaluminum compound; c) bringing the catalyst into contact The medium is in contact with the aforementioned electron donor: d) the catalyst is introduced into the polymerization reaction zone containing the organoaluminum compound, the electron donor and the monomer; and e) the polymer product is taken out of the reactor. Printed by a consumer cooperative (please read the notes on the back before filling out this page) Although the catalyst system can be used in almost any known polymerization method, the preferred method of the present invention involves pre-polymerizing the catalyst, which is based on the catalyst After contacting E-Yu®, The old contact with the catalyst was reached. U S P 4,769,935 and 4,927,797 describe a pre-polymerization method for the previous reference. As described in the disclosure, a hip flow for a catalyst is provided, the catalyst is in contact with an auxiliary catalyst or an organoaluminum compound, the catalyst is in contact with an electron pre-cursor, and the catalyst stream is integrated with a monomer to be polymerized. A relatively small number of contacts are placed, and the catalyst flows through the tubular reactor, and the pre-polymerized catalyst and the catalyst flow are introduced into the polymerization reaction zone. The electron precursor and the auxiliary catalyst are simultaneously contacted with the catalyst. The electron donor can then be removed from the reactor. When using the aforementioned catalyst and the electron donor described in the previous formula, the catalyst can have a S i / T i mole ratio between 1 and 10 van plaques in the reaction * with a higher than 30 kg / g — ca t · 1ι Efficiency * The polymer product can also be characterized by xylene solubles in the range of 2-10 wt%. The following examples and comparative examples will explain the present invention and its various advantages in more detail. • The results are listed in Tables 1 and 2. The catalysts used in the examples are believed to make this paper scale applicable to the Chinese National Standard (CNS) A4 specification ( 210X297 mm) • 14-Printed A7 _B7_ by the Shellfish Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (12)

Prepared using the materials and methods shown in USP4, 861, 847 and 4 * 784, 983. Trademarks sold by Catalyst Resources are | Lynx 1000〃. The catalyst used in the comparative example is believed to be prepared using the materials and methods disclosed in USP 4,927,797; 4,816,433 and 4,839,321. Toho Titanium, Inc. sells the trademarks as Ding 11 (:- 3 2/8, Example 1 Prior to the polymerization, by heating under a fixed exhaust gas of anhydrous nitrogen to a temperature higher than 100 ° C for a minimum of 30 minutes *, any micro-moisture was excluded from the reactor. Air and air • After heating, cool the reactor to room temperature (25 eC) under nitrogen. • Stabilize the reactor at room temperature, then add 32mmoJ? Hydrogen and 1. 45) 2 propylene • reactor at 1 3 00 Stir at pm, and the temperature rises to 70 X. Add 1. Ommoi TEA and 0.1 lmmo and cyclohexylmethyldimethoxysilane (CMDS) to the 40cc tube reactor. Make TE AP and the pre-contact in advance. About 1 minute * Add 10 mg of the catalyst to a suspension of sulphur oil in the 40 cc reaction brief. The catalyst is brought into contact with TEAj? And the precursor mixture for about 2 minutes in advance. The tubular reactor is connected to the inlet of the reactor, filled with liquid propylene at room temperature, and allowed to polymerize for about 5 seconds to perform catalyst pre-treatment. Get together. Pour the contents of the container into a chamber containing 1.45L

Inside the reactor of warm propylene. The total amount of liquid propylene in the reactor was about 2.9L. The polymerization reaction was carried out for 1 hour. At this time, the reaction was terminated by removing the excess propylene and allowing the reactor to cool to room temperature. ) A4 size (210X297 mm) r ------ r pack -11 (Please read the precautions on the back before filling this page) Order -15-A7 B7 V. Description of the invention (l3) Open the reactor to collect Polymer product, dried, weighed and analyzed • Calculate S i / T i molar ratio by dividing the Mohr number of the electron donor used by the Mohr number of the catalyst. • Dissolve the polymer in heat. In toluene, the solution was cooled to 0 ° C to precipitate isotactic form, and the xylene solubles were measured. The xylene solubles are% t% of the polymer soluble in cold xylene. Pentavalent distribution: Dissolve the polymer floc in boiling xylene, and then add the xylene solution dropwise to the formazan with stirring. The polymer precipitates in the intoxicant. Filter out the precipitate. Overnight extraction with boiling heptane • Results are shown in Table 1. Table I-| _ (Please read the notes on the back and fill out this page) Summary of the polymerization conditions printed by the Shell Standard Consumer Cooperative of the Central Bureau of Standards of the Ministry of Catalysts Weight of the catalyst: 10. 0 mg for TEA1 (auxiliary catalyst): 1.0 millimolar for CMDS 1: (electronic to hip): 0.1 millimeter Mohr Al / Ti: 200 Al / Si: 10 Si / Ti: 20 Hydrogen: 240 Δ ps ig Propylene: 2.9L (1500g) Temperature: 70 ° C Time: 1 hour Example 2-9 Repeat the method of Example 1 The general arrangement of CMD S in different places is as shown in Table 1. The paper size of the revised paper is applicable to the Chinese National Standard (CNS) A4 specification (2 丨 0X297 mm) -16-A7 B7 V. The description of the invention (l4) consists of 1 Millimoles became 0.002 millimoles. The results are shown in Table 1. Example 10-15 The method of Example 1 was repeated, except that CMDS was replaced by diisopropyldimethoxysilane (DIDS), and the total amount of DIDS As shown in Table 1, it changed from 2 millimoles to 0.003 millimoles. The results are shown in Table 1. Example 16-18 The method of Example 1 was repeated, except that the second and third butyl dimethyl groups were used. Oxysilane (DTDS) replaced CMDS, and the total set of DTDS was changed from 2 mol to 0.5 mol as shown in Table 1. Results are shown in Table 1. Example 1 9 2 4 Repeat the method of Table 1, except that CMDS is replaced by dicyclopentyldimethoxysilane (CPDS), and the total CPDS is 1: from 2 millimoles to 0.033 millimoles as shown in Table 1. • The results are shown in Table 10. Examples 25-30 The method of Example 1 was repeated, except that cyclohexyl isopropyl dimethoxysilane (CI DS) was used instead of CMDS, and the total amount of CI DS was the same as the standard of this paper. T China National Standards (CNS) 8 4 specifications (2I0X297 mm) 1._. 1 丨 | C clothing—I (please read the precautions on the back before filling out this page). Cooperative printed -17-A7 B7 V. Description of the invention (15) Table 1 changes from 2 奄 moles to 0 as shown in Table 1. 0033 millimolars • Results Comparative Example 1 to 3 0 The method of Example 1 was repeated, except that other commercially available Giglia-Nata catalyst components were used instead of the catalyst components used in Examples 1 to 30. The results are shown in Table 2. · Table 1 Implementation of TEA1 CMDS Catalyst Yield Xylene Isotacticity M_mmol mmol A 1 / Si 〇Lg__S_ Soluble-, "mmm 1 1 2 0.5 1 0 5 1 3. 0 Co-operative print 2 3 4 5 6 7 8 9 10 11 12 13 1 1 1 1 1 1 1 1 0.5. 2.0 0.1 10 0. 05 20 0.033 30 0.02 50 0.01 100 0.002 500 DIPS 2 0.5 1 1.0 0.5 2. 00.1 10 10 10 10 10 10 10 10 10 10 10 10 10 51.4 2.3 102 1.4 195 1.7 216 2.0 172 269 234 124 101 133 204 278 3.2 2.3 5.1 23.70.81.1 1. 2 1.6 --- I -------- ---- Order (please read the precautions on the back before filling this page) 96 This paper size applies to Chinese National Standard (CNS) A4 (210X297 mm) _ 18 _ A7 B7 Shellfish Consumption of Central Standards Bureau, Ministry of Economic Affairs Cooperative printed L, 14 Description of invention 1 (16) 0.05 20 10 223 2.8 15 1 0. 033 30 10 225 2. 1 DTDS 16 1 2 0.5 10 208 1.4 17 1 1 1.0 10 246 1.6 18 1 0.5 2.0 10 195 1.5 CPDS 19 1 2 0.5 10 105 1.1 98. 4 20 1 1 1.0 10 136 1.0 9 8.4 21 1 0.5 2.0 10 210 0. 9 97.9 22 1 0. 1 10 10 260 0. 9 98. 5 23 1 0.05 20 10 315 0. 6 24 1 0.033 30 10 249 0. 6 98.5 CTDS 25 1 2 0.5 10 70 0.9 98. 4 26 1 1 1.0 10 127 0.9 27 1 0. 5 2.0 10 181 0.9 28 1 0.1 10 10 119 1.6 29 1 0.05 20 10 134 2.0 30 1 0.033 30 10 157 2.4

Mu---n ^ i I- 8----I— i ----- I ii · 1- I 1 ·--I---i ml: two | ·-one eJ-(please first Read the note on the back of the page and fill in this page) This paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) -19-Attachment 2: Amendment page of Chinese specification of Patent Application No. 85112303 V. Description of the invention (17) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs

Control TEA1 CMDS Example mmol mmol 1 1 2 2 1 1 3 1 0.5 4 1 0.1 5 1 0.05 6 1 0.033 7 1 0.02 8 1 0.01 g 1 0.002 PIPS 10 1 2 11 1 1 12 1 0.5 13 1 0.1 14 1 0.05 15 1 0.033 ptps 16 1 «0 2 17 1 1 18 1 0. 5 CPDS A1 / Si Table 2 Catalyst m or output β _ 0.5 10 48 1. 0 10 142 2. 0 10 205 10 10 269 20 10 249 30 10 269 50 10 280 100 10 302 500 10 294 0.5 10 163 1.0 10 214 2.0 10 294 10 10 305 20 10 249 30 10 243 0.5 10 274 1.0 10 246 2.0 10 309 B8QS〇msL ·, Λ day — supplemental xylene Isotactic solution.wt%% in m τη m 4.1 0.9 1.5 1.4 95 2.8 7.1 8.7 6.8 93.6 15. 7 91. 6 2.9 92.2 3.1 95 2.9 96 2.4 2.5 2-8 3.9 3.1 96 3.7 (Please read the Please fill in this page for the matters needing attention)-^ fv 'Packing -------- Order ----- This paper size is applicable to China National Standard (CNS) A4 (210x297 cm) -20-V. Description of the invention (18) 19 1 2 0. 5 10 20 1 1 1. 0 10 21 1 0. 5 2.0 10 22 1 0.1 10 10 23 1 0.05 20 10 24 1 0. 033 30 10 CIDS 25 1 2 0. 5 10 26 1 1 1. 0 10 27 1 0.5 2.0 10 28 1 0.1 10 10 29 1 0. 05 20 10 30 1 0.033 30 10 (please read the notes on the back ^ and fill in this note) Order the seal of the Shellfish Consumer Cooperative of the Central Bureau of the Ministry of Economic Affairs The crystallinity of polypropylene is determined by standing hips and random polymers or heptane insolubles. As shown in the dimethyl data, specific electron donors are less ft of xylene solubles. • When PDS is used, this can be enhanced. This phenomenon is as shown in Tables 1 and 2 _ 2 7 and Table 1 and the specific catalyst composition of Table 1 is significantly lower than that of Comparative Examples 1 2 7 and Table 2 * As in Example 16_ A7 B7 140 2, 9 97. 9 209 3. 1 281 2. 9 96. 6 1 294 2. 4 346 2. 5 307 2. 8 97.7 98 2. 4 195 1. 8 237 2. 0 267 2. 3 206 2. 4 224 2. 4 Rules (Isotacticity) (Including control • Through f ~ " Γ | 3 Toluene and / benzene solubles decrease and increase, as before, combined with specific catalyst components to produce compatible specific catalyst components for simultaneous use As shown in C, each electron certificate is compared with the xylene-soluble material of the composition of Example 1 in the same electron donor. Below, usually 2 1 and Tables 1 and 2, as described in the paper size common Chinese National Standard (CNS) A4 specifications (210X297 mm) -21-A7 B7 V. Use the CPDS as described in the description of the invention (19) When used with catalyst components, it produces propylene with the lowest relative xylene solubles and the highest relative crystallinity. The aforesaid composition of CPDS and catalyst component has the activity of other electronic donors and the composition of the catalyst component. "(Please read the precautions on the back before filling this page) The paper size printed by the cooperative is applicable to the Chinese National Standard (CNS) A4 (210 X297 mm) -22-

Claims (1)

Annex 3 (a) Patent Application No. 851 12303 Chinese Comparative Data 6 a L 必 winch 96 εΜ τ19 9Π Τ3MM ^ n ^^^^^ fr 丨. Act as her. Members are requested to indicate whether the original substance will be changed after the amendment-ϋ: 0 'g · 00' Δ · 10 !: CN OJ LO VO σ > σ \ \ D0 > Lrn69 ^ 65Δ6 σ »h in co οϊ n (n oj oa οι σ» h cn m cn c \ ri σ \ in co < N r > (N CM 03 < N OrHOJfO inch in vo r- co rH rH Η «Η, rH« —I «Η« —I «Η 〇 > 〇rH oa m inch * -l 03 CN < N CN CN inch π σ > in ι〇 • · · · · CO 00 卜 00 co CTi Cf > CTt G \ ε Δ · εε 00 c- < Ci Ό 00 H Ο Η «Η Η < N inch VO in r- < 〇〇) σι VD vo rH rH 〇〇〇〇—w WQ§ < 0 CO w QQQ Η H 〇4 QQ a 6 8 Γ inch ε ζ τ OrHOJCO ^ tlO VOf ^ CO C ^ Or-tOJcO ^ «HrHrHHHHrH rHi-ii- ! γΗ〇00〇4 < N < ΝΓΜ Annex 3 (a) Patent Application No. 851 12303 Chinese Comparative Data 6 a L 必 winch 96 εΜ τ19 9Π Τ3MM ^ n ^^^^^ fr 丨. Act as her. Members are requested to indicate whether the original substance will be changed after the amendment-ϋ: 0 'g · 00' Δ · 10 !: CN OJ LO VO σ > σ \ \ D0 > Lrn69 ^ 65Δ6 σ »h in co οϊ n (n oj oa οι σ» h cn m cn c \ ri σ \ in co < N r > (N CM 03 < N OrHOJfO inch in vo r- co rH rH Η «Η, rH« —I «Η« —I «Η 〇 > 〇rH oa m inch * -l 03 CN < N CN CN inch π σ > in ι〇 • · · · · CO 00 卜 00 co CTi Cf > CTt G \ ε Δ · εε 00 c- < Ci Ό 00 H Ο Η «Η Η < N inch VO in r- < 〇〇) σι VD vo rH rH 〇〇〇〇—w WQ§ < 0 CO w QQQ Η H 〇4 QQ a 6 8 Γ inch ε ζ τ OrHOJCO ^ tlO VOf ^ CO C ^ Or-tOJcO ^ «HrHrHHHHrH rHi-ii- ! γΗ〇0〇4 < N < ΝΓΜ in vo r * co σ \ ο (N CN CN CN OJ Π inch · ζ 0 · ζ9 · τ " • ο 6 · 0 々 • 86 6 · 0 in v〇r- co o £ N ON fN (N (N r) common A8B8C8D8 VI. Annex 1 (a) of the scope of patent application:-(锖 Please read the notes on the back before filling this page) No. 85112303 Patent Application Chinese Application for Patent Scope Amendment The Republic of China 89) Month Amendment The catalyst system for polymerizing and copolymerizing propylene contains (a) —a conventional Giglia-Nata catalyst component, which is basically composed of 1.5 to 6.0 weight percent titanium, and 10 to 20% reset magnesium. 40-70% by weight is selected from halogen groups including chlorine, bromine and iodine; 5-25% by weight is selected from polycarboxylic acid esters including aliphatic, aromatic and cycloaliphatic polycarboxylic acids; and 0. 1-2.5% by weight of organic phosphorus compounds selected from the group consisting of hydrocarbon esters of phosphoric acid and phosphonic acid, wherein each hydrocarbon group has 1 to 6 carbon atoms, and the catalyst component is prepared by a method having the following steps: Printed by Shelley Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs a) Dissolving a magnesium halide compound in a solvent mixture to form a homogeneous solution, the magnesium dentate is selected from a magnesium halide complex including magnesium halide and water or alcohol and Derivatives of magnesium halides in which the halogen atom is replaced by an alkoxy or halogenated hydrocarbon The solvent mixture is composed of an organic epoxy compound and an organic phosphorus compound to form a homogeneous solution. The organic epoxy compound is selected from the group consisting of oxides of aliphatic hydrocarbons and diene, halogenated aliphatic hydrocarbons, and dihydrocarbons. The oxides and glycidyl ethers have 2 to 8 carbon atoms, and the organic phosphorus compound is selected from the group consisting of alkyl phosphates, aryl phosphates, aralkyl phosphates, alkyl phosphites, aryl phosphites and Aralkyl phosphite, in which the alkyl group has 1 to 4 carbon atoms and the aryl group has 6 to 10 carbon atoms: b) the homogeneous solution and the general formula TiXn (OR) National Standard (CNS) A4 Specification (210 X 297 mm) 6. Mixing of liquid cyanide compounds applying for profit, where X is halogen, R is the same or different alkyl group, and η is an integer from 0 to 4. ; (Please read the notes on the back before filling this page) c) Add at least one auxiliary precipitant to form a precipitate, which is selected from the group consisting of carboxylic anhydride, carboxylic acid, ether and ketone; Adding polycarboxylic acid esters at the time of the material; e) from the mixture To separate the precipitate, use the titanium compound T i Xn (OR) 4_n or a mixture thereof to treat the separated precipitate in an emotional diluent, where X is a halogen, R is a hydrocarbon group and may be the same or different, and η is given by An integer of 0 to 4; and f) washing the treated precipitate with an organic inert diluent, (b) an organoaluminum compound and (c) a seedling precursor having the formula 0¾ R1—Si—R4 I or3 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, where 111 is an alkyl or cycloalkyl group containing one, two or three carbon atoms bonded to silicon; R2 and R3 are each alkyl or aryl; and 114 is Alkyl or cycloalkyl, having secondary or tertiary carbon atoms bonded to a silicon atom, Chi 1 and R 4 may be the same or different, wherein the Si / Ti molar ratio is 1 to 400. 2. As for the catalyst system of the first item in the scope of patent application, where ruler 1 is a secondary alkyl group with 3 to 5 carbon atoms and mirror symmetry, and this paper size applies the Chinese National Standard (CNS) A4 specification ( 210 X 297 mm) 2 A8B8C8D8 389772 6. The scope of patent application R < t is a secondary alkyl or cycloalkyl group with 3 to 6 carbon atoms and mirror symmetry. 3. If the catalyst system in the scope of patent application No. 2 in which both the ruler and R 4 are both cycloalkyl "4. If the catalyst system in the scope of patent application No. 3 in which R 4 is cyclopentyl base. 5 _ The catalyst system according to item 1 of the scope of patent application, wherein the ruler 2 and is selected from the group consisting of methyl, ethyl, propyl and butyl. 6. For example, the catalyst system of item 5 of the patent scope, in which both the ruler 2 and R 3 are methyl. 7. For example, the catalyst system of the scope of patent application, wherein the electron donor is cyclohexylmethyldimethoxysilane, diisopropyldimethoxysilane, di-tert-butyldimethoxysilane, cyclohexyl iso Propyldimethoxysilane or dicyclopentyldimethoxysilane. 8. If the catalyst system according to item 7 of the patent application scope, wherein the electron donor is dicyclopentyldimethoxysilane. 9. The catalyst system according to item 1 of the scope of patent application, wherein the organoaluminum compound is an alkyl aluminum of the general formula A 1 R, where R > is an alkyl or halogen having 1 to 8 carbon atoms, R / It is the same or different from at least one R1 and is an alkyl group, and R / is the same or different. 10. The catalyst system according to item 9 of the scope of the patent application, wherein the organic aluminum compound is selected from the group consisting of trialkylaluminum, alkylaluminum dihalide, trialkoxyaluminum, and dialkylaluminum halide. . 1 1. If the catalyst system of item 10 in the scope of patent application, the paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) *-Order --------- line !! (Please read the "Notes on the back side before filling out this page"), printed by the Industrial Property Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs * 3-A8B8C8D8 389772, the scope of patent application The organoaluminum compound is trialkylaluminum. 1 2. The catalyst system according to item 11 of the scope of patent application, wherein the organoaluminum compound is triethylaluminum or triisobutyl aluminum. 1 3. The catalyst system according to item 1 of the scope of patent application, where a 1 / Si molar ratio is 0.5 to 500. 14 methods for polymerizing propylene, including: (a) selecting conventional Giglia-Nata catalyst components, consisting essentially of 1.5-6. 0 wt% titanium, 10-20 wt% magnesium, 40- 70% by weight is selected from halogen groups including chlorine, bromine and iodine; 5-2 55% by weight is selected from polycarboxylic acid esters including aliphatic, aromatic and cycloaliphatic polycarboxylic acids; and 0.1 — 2.5% by weight of organic phosphorus compounds selected from the group consisting of hydrocarbon esters of phosphoric acid and phosphonic acid, wherein each hydrocarbon group has 1 to 6 carbon atoms, and the catalyst component is prepared by a method having the following steps: a ) Dissolving a magnesium halide compound in a solvent mixture to form a homogeneous solution, the magnesium dentate is selected from the group consisting of a magnesium halide complex of magnesium halide with water or an alcohol, and a derivative of a magnesium mycide, wherein the halogen atom is replaced by a hydrocarbon Alkoxy or halogenated alkoxy; the solvent mixture is composed of an organic epoxy compound and an organic phosphorus compound to form a homogeneous solution, the organic epoxy compound is selected from oxides including aliphatic hydrocarbons and diene, Oxides and glycidyl ethers of halogenated aliphatic and dihydrocarbons, each with 2 8 carbon atoms, and the organophosphorus compound is selected from the group consisting of alkyl phosphates, aryl phosphates, aralkyl phosphates, alkyl phosphites, aryl phosphites, and aralkyl phosphites, wherein the alkyl group has 1 to 4 carbon atoms, and the aryl group has 6 to 10 carbon atoms; b) the homogeneous solution and the general formula TiXnCOR) ^!-^ This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 Public «) I-order ------ I-- line! · (Please read the precautions on the back before filling this page), 0. Printed by the Shelley Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs-4-A8B8C8D8 38977S VI. Patented liquid titanium compound mixture, where X is tooth element , R is the same or different alkyl group, and η is an integer from 0 to 4; Guess first »Read the notes on the back and then fill out this page) c) Add at least one auxiliary precipitant to form a precipitate. Including carboxylic anhydrides, carboxylic acids, ethers and ketones; d) adding polycarboxylic acid esters when a precipitate appears; e) separating the precipitate from the mixture using a titanium compound T i X n (0 R) 4_n or a mixture thereof, Treating the separated precipitate in an inert diluent, where X is halogen, R is a hydrocarbon group and may be the same or different, and η is an integer from 0 to 4; and f) the treated precipitate is washed with an organic inert diluent (B) contacting the catalyst with an organoaluminum compound; (c) simultaneously or after step (b), contacting the catalyst with an electron donor, the electron donor having the general formula: 0R2 R · ) — Si — R4 I 〇R3 Intellectual Property of the Ministry of Economic Affairs Bureau Consumer Consumption Cooperatives issued R1 is an alkyl or cycloalkyl group containing primary, secondary, or tertiary carbon atoms; R2 and R3 are alkyl or aryl groups; and R4 is an alkyl or cycloalkyl group with a bond The secondary or tertiary carbon rat 'R ^ and R 4 are the same as or different from each other due to the silicon atom »Among them, the Mo / Ti ratio is 1 to 400. The paper size is applicable to China National Standard (CNS) A4 (210 * 297 mm) 5 A8B8C8D8 6. Application for profit-seeking scope (d) The catalyst is introduced into the polymerization reaction zone containing the monomer. < Please read the notes on the back before filling in this page) 1 5 _If the method of patent application No. 14 is used, only 1 is a secondary alkyl group with 3 to 5 carbon atoms and mirror symmetry R 4 is a secondary or cycloalkyl group having 3 to 6 carbon atoms and mirror symmetry. 16. The method according to item 15 of the patent application, wherein both Rl & R 4 are the same as the cycloalkyl group. 1 7 · The method according to item 16 of the patent application, wherein both Rl & R 4 are Is cyclopentyl. .18: The method according to item 17 of the scope of patent application, wherein the electron donor is a cyclohexylmethyldimethoxyacetate compound, a diisopropyldimethoxy compound compound, a second and third butyldimethoxysilane, Cyclohexyl isopropyl dimethoxysilane or dicyclopentyl dimethoxysilane. 19 · The method of claim 18 in the scope of patent application, wherein the electron donor is dicyclopentyldimethoxysilane. _ Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 20. For example, the method of claim 14 in the scope of patent application, wherein the organoaluminum compound is an aluminum alkyl of the general formula A 1R < 3, where R-is 1- A fluorenyl or halide group of 8 carbon atoms, R / is the same or different from at least one R1 and is an alkyl group, and R > is the same or different. 2 1 _ The method of claim 20, wherein the organoaluminum compound is selected from the group consisting of trialkylaluminum, alkylaluminum dihalides, triplex oxyaluminums and dialkylaluminum halides. 2 2. The method according to item 21 of the patent application scope, wherein the organoaluminum compound is a trialkylaluminum. This paper size is applicable to Chinese National Standard (CNS) A4 specifications (210 X 297 Public Love) 389772 A8 B8 C8 D8 VI. Application for patent scope 2. 3. If the method of item 22 of patent scope is applied, where the organoaluminum compound is Triethylaluminum 2 4. The method according to item 14 of the patent application park, wherein the monomer is propylene. 2 5 · The method according to item 14 of the patent application scope, wherein there are other steps after step (c) The steps include: pre-polymerizing the catalyst by contacting a few monomers with the catalyst. 26. The method according to item 14 of the patent application, wherein the reaction zone contains the organic aluminum compound additionally disposed 6-Such as the method of claim 14 of the patent application, wherein the method is characterized by the manufacture of a polymer product, the xylene soluble part of the polymer product is 0.6- 3. Owt% Fan Domestic · 28. If the method of applying for the scope of the patent No. 14 further includes adding a second monomer to form a copolymer · 29. If the method of applying for the scope of the patent No. 14 in which A1 / Si Morse ratio is 0.5 to 500. < Please read the notes on the back first (Fill in this page) d T-Printed by Shelley Consumer Cooperative, Bureau of Intellectual Property, Ministry of Economic Affairs This paper is sized for China National Standard (CNS) A4 (210 X 297 public love)