TWI288755B - Supported metallocene catalyst for producing syndiotactic styrenic polymer - Google Patents

Abstract

The present invention provides a supported catalyst comprising (A) a polymer, (B) a supporter, (c) a transition metal compound, and optionally (D) (a) a compound which can form an ionic complex by the reaction with the transition metal compound or (b) a specific oxygen-containing compound, and (E) an alkylaluminum compound. The supported catalyst according to present invention, which has a high activity, can be used for preparing a styrenic polymer with a high syndiotacticity. The supported catalyst can be used in combination with a cocatalyst, preferably an alkyl aluminoxane.

Description

1288755 Ref. 90107017 MONTHLY MODIFICATION 5. INSTRUCTION DESCRIPTION OF THE INVENTION (1) Field of the Invention The present invention relates to an auxiliary catalyst for preparing a syndiotactic styrene polymer. More particularly, the present invention relates to a highly active auxiliary catalyst for preparing a syndiotactic styrene polymer having high syndiotacticity and high crystallinity. BACKGROUND OF THE INVENTION Syndiotactic polystyrene was first synthesized in 1986 (I sh ihara et al. at the macromolecule 1 9 8 6, 19, 2 4 6 4) using a titanium-based compound and methyl aluminum oxide (MAO, methylaluminoxane) homogeneous organometallic catalyst system. Syndiotactic polystyrene is a very interesting polymer. This polymer exhibits low specific gravity, low dielectric constant, high modulus of elasticity, and excellent resistance to chemicals. Therefore, syndiotactic polystyrene has become a promising material for many applications in the automotive, electronics and packaging industries. However, the commercialization of syndiotactic polystyrene has some serious problems, namely, severe reactor fouling or agglomeration, and low fluidity of the product powder due to its unsatisfactory morphology. If only a homogeneous catalyst is used, these problems remain unresolved. These problems can be solved by using a catalyst supported to an organic or inorganic carrier instead of a generally homogeneous catalyst for the polymerization. However, the activity of the cocatalyst is generally 10 to 20 times less than the corresponding uniform catalyst activity, and the polymerization activity of the syndiotactic polystyrene is generally much lower than that of the polyene. Therefore, it is very difficult to prepare an auxiliary catalyst for producing a syndiotactic polystyrene having satisfactory activity. To date, four basic methods have been developed to produce polyenes using metal complex catalysts, such as the following:

1288755 —-~ --- Case No. 90107017 Month _g_ Amendment __ V. Description of invention (2) 1 · Direct adsorption of metal complexes onto the surface of the carrier, involving physical adsorption or chemical adsorption of metal complexes (direct Heterogeneity); 2. Start to adsorb MAO, methylaluminoxane into the carrier, and then adsorb the metal complex (freely heterogeneous); 3) by metal complexes by ligand The valence is bonded to the carrier and then activated by MA0; and 4. the organic compound capable of reacting with the hydroxyl group of the inorganic carrier surface such as alumina and forming a complex with the auxiliary metal complex, /, with the following reaction as a The example represents:

Si OH + IKKR — OH—Si—ο~R-0H—Si—R—〇... metal complex wherein R is a hydrocarbon.

) The ruthenium metal complex catalyst is loaded onto the carrier -11 (method 1 is contained in the ami person in J. Polym. Sc; L: Paft 1 9 9 9, 3 7, 2 9 5 9)匕楹仳田·〇lym, Chem·古,土q, no such 仏 仏 is used for the activity of stupid ethylene polymerization. Method 3 is directed to the surface of the carrier with respect to the complex compound. It is difficult to create a metal complex between the carrier and the metal complex.

1288755 ___Case No. 9017017_Yearly revision __ V. Introduction of spacers (3), but reported by Spitz et al. (Macromol. Chem. Phys· 1 9 9 9, 2 0 0, 1 45 3 The results show that there is no increase in the polymerization activity of styrene. Until now, very small amounts have been reported for the use of co-catalysts for the manufacture of syndiotactic & ruthenium polymers. Shi Xitu (K aminsky et al., J. Polym. Sci.: Part A: Polym. Chem. 1999, 372959), Shao Tu (Spitz et al., Macromol·Chem. Phys. 1 9 9 9, 20 0, 1 45 3) and polymers (Yu et al. in J. Polyi Sci. Part A: Polym·Chem. 1996, 34, 2237) have been used as a system.

Preparation of a cocatalyst for the manufacture of a syndiotactic styrene polymer. None, all of these co-catalysts are not suitable for very low activity. It is expected to be used by the South to produce a syndiotactic styrene polymer. Thus, the inventors have developed a highly active auxiliary metal catalyst in combination with a co-catalyst to prepare a polymer having a high syndiotacticity. SUMMARY OF THE INVENTION The present invention provides an auxiliary catalyst comprising (A) a polymer, a carrier, (C) a transition metal compound, and optionally (D) β) to form an ion complex by reaction with a transition metal compound. Compounds a), (b) specific oxygenates, and (E) alkyl aluminum compounds. Do not use a cocatalyst and a cocatalyst, preferably an alkyl aluminoxane, in combination. A feature of the invention will be provided for the preparation of a high-grade ke ~ both this

Page 8 1288755 Case No. 90107817 月 修正 Amendment V. Inventive Note (4) A highly active auxiliary catalyst for olefin polymers. Another feature of the present invention is to provide an auxiliary catalyst for preparing a syndiotactic styrene polymer which can significantly reduce the filth or agglomeration during polymerization and prepare a polymer having good fluidity and high crystallinity. Other features and advantages of the present invention will be apparent from the following disclosure and the appended claims. DETAILED DESCRIPTION OF THE INVENTION Catalyst System The present invention provides an auxiliary catalyst comprising (A) a polymer, (B) a support, (C) a transition metal compound, and optionally (D) (a) formed by reaction with a transition metal compound a compound of an ion complex or (b) a specific oxygenate, and (E) a thiol compound. A detailed description of the components of the catalyst system is as follows. (A) Polymers It is generally believed that the focus of the high activity metal complex assisted catalyst is to isolate the toxic surface of the metal complex catalyst to be supported and the support, most of which is vermiculite without compromising the advantages of the cocatalyst. For example, when a homogeneous catalyst is reacted with an inorganic support, in the case of vermiculite, the catalyst can be adjusted to react with hydroxyl groups or S i -OH groups on the surface of the support. However, this method is not effective because even if the hydroxyl group of the carrier is covered, the surface of the carrier is not a hydroxyl group (in the case of vermiculite,

Page 9 1288755 修正 Amendment — t^9Q107817 Issue 5, invention description ----- ~ S i — 〇 — c * \ poison, still exposed. This exposed acidic surface has been reported to be ineffective for the catalyst. So, this method has been

In view of this idea, the inventors have used a uniform catalyst for the abundance of human A 与 and the toxic + wangwang-S彳-, m double-field, the carrier of the gas early layer. Therefore, the interaction between the present V-carrying agent and the carrier acts as an insulating agent and the carrier of the contact and the Shimi-Ming is not harmful to the performance of the catalyst, 盥 π _ 虹 虹, has a chemical or physical interaction, and is added to the etch. Rhodium catalyzes the insoluble ethylene monomer or polymerization solvent. After the catalyst is 1 s, the above-mentioned polymer is a specific polar group containing a specific polar group Μ + i acting polymer and a surface chemical bite film of the carrier, and the bit 2 〃 1 compound is completely adsorbed. The coating process is formed on the surface of the carrier, and the coating process is carried out. The polar group is formed into a complex catalyst by forming a release and a force. In the case of a catalyst, an insulator is used as a carrier. 代表性 ί A representative polymer for this purpose includes acrylonitrile-containing and copolymerized η copolymers, acrylic acid and propionate vinegar polymerized into a private product, and hydrazine maleic anhydride copolymerization. And maleic anhydride for the extraction of _ . ^ ~ a know about polymers and copolymers, polyethers, polyketones, and _ _ ^ polymers and copolymers. Specific examples of polymers and copolymers are polypropylene, succinyl-benzonitrile, poly(styrene-co-acrylonitrile), r/diene-styrene resin, poly(acrylonitrile-co-) Ding Ershuo), κ acrylonitrile-co-isoprene, etc. Acrylonitrile content in the interpolymer

Page 10 V. INSTRUCTIONS (6) Limitations, but usually approximate. (1). . Λ5%. The poly(styrene-co-acrylonitrile) is preferably from about 2 to 5. The degree of ^) is preferably at least about the amount of the polymer as the insulating layer, and the weight of the tantalum agent is not about 0· _! to 99.999% by weight, but the ratio is preferably better than that of the auxiliary (β) carrier. To prepare both the auxiliary catalyst and the organic vehicle. The carrier of J includes an inorganic carrier. Representative examples of the inorganic carrier include Shixi gel, geishite, mica powder, white clay, sub-existing earth, bismuth oxide, metal carbonate, and metal powder. ::J f: compound, medium, bismuth gel, bismuth oxyaluminate gel and aluminum" machine solid poly(styrene-co-divinylbenzene) beads, and "powder:: solid can be packaged amount of carrier There is no limit, but it is better to stand: π and so on. 0.0 0 0 1 to 99.999% by weight. The weight of the self-catalyst is about (C). The transition metal compound is a transition metal used in the present invention as a homogeneous catalyst. The group IVB metal compound represented by the following formula (I) or (II).

WiW...+c)(1)

MR1dR2eR3cX3-(d+e) (ID wherein Μ is a group of IVB group having 1 to 20 carbon atoms, R1, R2 and R3 are each a hydrogen atom, and 1 to 20 carbon atoms are burned oxygen 1288755 Case No. 90107017 曰 Amendment 5, Invention Description (7) Group, aryl group having 6 to 20 carbon atoms, alkaryl group having 6 to 20 carbon atoms, aryloxy group having 1 to 20 carbon atoms , cyclopentadienyl, substituted cyclopentadienyl or fluorenyl, X is a halogen atom, a, b and c are integers from 0 to 4, and d and e are integers from 0 to 3. Representative examples of R2 or R3 representing an alkyl group having 1 to 20 carbon atoms are methyl, ethyl, propyl, butyl, pentyl, isopentyl, isobutyl, octyl and 2-ethylhexyl Representative examples of alkoxy groups having 1 to 20 carbon atoms are an anthracenyloxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, and a 2-ethylhexyloxy group. Representative examples of aryl, aralkyl or alkaryl groups having 6 to 20 carbon atoms are phenyl, anthracenylphenyl, diphenylphenyl and benzyl. Formulas (I) and (II) Where R1, R2 or R3 may be identical to each other or The transition metal component (C) used in the preparation of the auxiliary catalyst according to the present invention, in addition to the mononuclear catalyst shown in the formula (I) or (II), further includes a dinuclear and multinuclear catalyst. ), ( IV ) or (V ) represents: 1dR2eXV (and e) M1-〇-R4-0-M2R1rfR2exV(d+e) (III) , 0 ——R4—Ο, (IV) (7) Φ R′XW&gt ;2R1fX12_f 〇-R5—Ο Ο——R4—Ο R1M1\·—Ο-R5 Ο-M2R1 Ο-R6——〇

Page 12 I288755 Case No. 90107817 Friends, invention description (8)

And each of them is an atom of the ινβ group in the periodic table; r4, r5 and " are a burnt group having ! to 2 carbon atoms, a aryl group having 6 to 2 carbon charcoal having 6 carbon atoms, having 6 A carbon atom, a pentylene group, a substituted cyclopenta group having an integer of 0 to 2. 〜'2 R5 & R6 represents a representative of an alkyl group having 1 to 20 carbon atoms. Examples: yl, ethyl, propyl, butyl, pentyl, isopentyl, isobutyl and 2-ethylhexyl; representative examples of aryl and aryl: groups having from 6 to 20 are phenyl , tolyl, diphenyl phenyl and ^ ^, R 5 and 1 ^ may be the same or different. In the general formulae (III), and (V), R 4 , R 5 and R 6 may be the same or different from each other. The catalyst is represented by the following formula (VJ): MR1dR2BX1 3-{d+e) (VI) is an alkyl group having 1 to 20 carbon atoms, an alkyl group having 6 to 20 carbon atoms, and having 6 to 20 carbon atoms. Aryl, 6 to 20

Jo'of)., sulfhydryl, and pentylene; the degree of polymerization of the polymer is 5 to 1 UU00, and η is an integer of 0 to 1 Å. The type group Ϊίΐ compound (C) may be used singly or in two or more classes ^ A , . The amount of the transition metal compound (C) is not limited, but is in the range of from about 0.001 to about 30% by weight based on the weight of the earth's and the mother catalyst. Early edition = a mouthpiece which can form an ion complex, or an oxygenate, by reaction with a transition metal compound. For the preparation method of the auxiliary catalyst for the month, it can be used as appropriate

Page 13 1288755 Straight 901f) 7S17 V. Inventive Note (9) (a) A compound, pots can be converted into an ion-compound Λ 2 7 = transition metal compound reaction and form anion and 2) into a Oxygen compound. The above components (4) β (C6H2F3) 4, B (CeH3F): human,): -,,, p(i) 6 that 4) 4 . Specific examples of metal cations include Cp2Fe+, (tBuCp)2Fe+, (Me2Cp)2Fe+, and (Me4C^)2Fe+, (Me5(:P)2Fe+, Ag+, Na+, 1 " other examples including nitrogen Ions such as pyridinium ion, di-nitro-N,N-diethylanilinium ion, diphenylammonium ion, p-american=ammonium, 2,5-dichloroanilinium ion, p-nitro-N, N-dimethyl succinite: porphyrin ion, N,N-dimethylanilinium ion, and N,N-diethylfene, carbene compound such as triphenylcarbene ion, tris(4-甲美^ carbene ion, and: TQ-field and licorice, soil I), ρ-(methylhydrazine basic) carbene ion; burnt-based scaly ions such as CW, c2H5PH3+, C3W, (CH3)2pH2+, Soil & ion JC2H5)2PH2^ (c3h7)2ph2+> (CH3)3ph^ (c2h5) ph+ R( 3H7)3pH+' (CF3)3PH- (CH3)4p+\ cc2h5) pfr; and aryl squamous ions c6H5PH3+, (c6H5)2PH2+, (c 3 pH+ (C6H5)4P+, (C2H5) 2 (C6H5) ph+ ^ (ch3) (CV } PH2 , (CH3 ) 2 (C6H5 ) PH+ and (63⁄4 ) (C2H5 ) 2 ( C6H5) 2PH+. Compound (a) is a borate compound, a straight (C) transition metal The compound reacts to form an ion-disorder and composition. The composition includes B (C6F5)3 (C6HF4)3, B. Boric acid 1288755 MM 90107817 Λ._3 Revision 5, Invention Description (ίο) B ( C6 H3 F2 ) 3 , B_ (. 扎F: P 彡 彡, and AI (C6HF4 y 3 - oxygenate (b) can be represented by the following formula as an alkyl aluminum and a condensed and 雍 # wr μ λ table of fluorenyl aluminum lactide 雒The reaction of the reaction reagent (such as water) β ( C6CF3F4 ) 3, bf3, ρί? 5

(VII)

Wherein R8 is an alkyl group having 1 to 8 carbon atoms and j is 2 to 50

The alkyl chain oxyalkyl chain structure may be a linear or cyclic structure (E) alkyl aluminum compound. In the preparation method of the auxiliary catalyst of the present invention, the hydrazine-based aluminum compound represented by the following formula may be used as appropriate. AIR% (η) ugly is a burnt group having 1 to 8 carbon atoms. I Catalyst: The auxiliary catalyst of the finger ί:I is preferably used in combination with a co-catalyst. To prepare a syndiotactic I compound. Can be knight eight m, a clothing 1 胥 as a common catalyst. () Individually or in combination with ingredient (E) Single electricity: Using the invention quite ^

On page 15 of the preparation of the standard benzene benzene dance poly i: the auxiliary catalyst to polymerize the styrene bake monomer - ° This stupid vinyl dry body represented by the formula (IX): (IX) 1288755 90107811 V, invention description (11 ) CH=CH2

Wherein R1G is selected from a hydrogen atom, a halogen atom, or a substituent containing a carbon atom, an oxygen atom, a nitrogen atom, an & atom, a phosphorus atom or a germanium atom, and k represents an integer of 1 to 3. The styrene monomer may be polymerized or two or more styrene monomers may be copolymerized. The monomer which can be polymerized using the auxiliary catalyst according to the present invention is not limited to the styrene monomer. The olefin monomer represented by the formula r τ main ^ ^ may also be polymerized or copolymerized with other olefin monomers or styrene monomers. ~ CH=ch

R 11 (X) wherein R11 is selected from a hydrogen atom and a right 159^ cyclic alkyl group. And, there are 1 to 2 M solid atoms in a straight chain or in > ((D: auxiliary, a better amount but used to prepare the auxiliary catalysis of the present invention. B), and (6) are basic components And Ge (E) can be combined with ingredients (A), (B), and (c) into a om fine. Finally, the composition (DVVV: system 'two · = --------乜)

Page 16 The amount of ingredients U) and (B) in the cocatalyst is not used. The amount of the component (A) is preferably limited to at least 〇 1% by weight. Preferably at least 70% by weight. The amount of the component (c) is also a knife (B) 1288755 Ά j〇l〇78r^ V. Description of the invention (12) The amount is also not particularly limited. The method for preparing the auxiliary catalyst of the present invention is the following: f: The preparation of the components of the auxiliary catalyst is preferably the procedure and the sequence shown in Fig. 1. The solvent of the group and the tff auxiliary catalyst is not particularly limited, and the G = solvent is the same as #, and the reaction temperature U〇c to i5〇c, preferably 2, of the auxiliary catalyst is generally known to be related to the present invention. 〇 to desire. $ f Μ # &# The following examples will be more fully understood, and it is intended to limit the scope of the invention in any way, and the present invention is limited to the scope of the accompanying patent application. 9 In the following examples, all parts and percentages are in weight units. Year 修正 Corrected ‘Figure. The reverse order is not specifically for fat artisans, usually meant to illustrate the invention of the invention unless otherwise exemplified by a homogeneous catalyst, (CH3) 5CpTi [0C6H4C (CHa) TiCp (CH3) fishing preparation: $! In a dry 25 〇 ml flask with a magnetic stirrer, liters of stupid, 2 · 3 g (1 〇 mmol) of bisphenol a and 5 ml of (3 5 ·) anhydrous triethylamine (Aldrich, purity 99.5) %) in a nitrogen ring ^. The resulting solution was clear and colorless. The solution was taken as acetone-liquid # to -78 °C. In a vigorous scramble, 28 mol of Cp*TiCl® dissolved in 7 ml of toluene was added dropwise. Then the reaction system will be 2c 6h 40 ] and 80 0 9 ohms will be added to the "ice bath cold • 〇 (6. gradually warming up

1288755 -- a case number 90107817 years q - : five, invention description (10) 廿: to the temperature and maintain for about 4 hours. The color of the solution changes from red to y and produces a white precipitate. The precipitate was filtered and the solution was evaporated to dryness. As a result, a quantitative yield such as J 3 · 4 g of a yellow solid. Method 2. In a dry 25 ml flask equipped with a magnetic stirrer, add 80 mils of refined terpene and 2.42 g (10·6 mM) of bisphenol A to the nitrogen ring = f. Then 2.0 g (7.1 2 μl) of Cp*Ti (OCHs) 3 dissolved in 70 ml of toluene was added dropwise with stirring. The reaction system is then maintained at ::: about 4 small b. As a result, a yield of 3.4 g of a yellow solid was obtained. By W NMR and 13C NMR, the following formula (XI) represents the same as HomoCat-1. The product obtained by the above two methods has a structure. Uniform catalyst

(XI)

Example 2 In a bottle equipped with a magnetic stirrer, 9 ς η* 4, (4) dnch, in a 70-generation forged ^2, 5, = bottle, 4 g of Shixi soil stvrene-acrvloni tri 1 0.5 g of benzene B-bonded-acrylonitrile (SAN,

Styren-e aCryl〇nitri·!!^ The nitrile content is 23% by weight, Mw 1288755,----Case No. 9017017_^_月五, invention description (14) ~ _ Fort to ______ 9〇, 00 0) Polymerization The mixture was stirred at room temperature for 2 hours at room temperature until 80 ml of toluene was added to the mixture. After the formation, the toluene is transferred into another container and then fully resolved by the matter element. Thus, the white solid carrier precursor was removed by vacuum drying at 2 millimolar. Because of methylaluminumoxane), it was stirred at 80 °C for 30 minutes, and then added at room temperature. The slurry was then removed by vacuum drying. Stupid use to move into other volume precursors II. Serve to a white solid as a load will be 〇 · 2 millimolar uniform

HomoCat-1' was slurried in 80 ml of toluene using a cannula, and the resulting slurry was maintained at room temperature and stirred into a carrier precursor j j . The body was washed 3 times with 50 ml of hydrazine, and then filtered at a straight rate of 77 minutes. The g and the formed solution of the solution were analyzed by IPC to a degree of about 0 · 0 2 μmol/ml. In 忐3, it can be neglected, and it is used as the final auxiliary catalysis. It is also two: light yellow solid 〇·0433 micromoles/gram. If it is, it can be determined by Jiang. The content of titanium removed by washing is neglected. Therefore, the titanium content in the titanium a granule in which the titanium content of the auxiliary catalyst is directly obtained and the weight of the auxiliary catalyst formed can be calculated as: a pale yellow solid which is formed by using it as a yellow solid. It is determined by IPC to be 0·043 3 micromoles/g: ', chemical agent, 1288755 _ case number 90107017_year and month _ amendment 5. Invention description (15)

Si〇2^ SAN^ MAO^» HomoCat-Ι^ Five 5 quantity^ (g> (free > (亳莫耳) (mole> (micromole/gram) 2.0^ 0.2^ 0.0433^ 2.0 ^ 0·6ρ 0.0433^ 2.0^ 0.8^ 0.0433如2.0^ 0.2^ 0.0433b^ 8.0^ 0.2^ 0.0433b^ 0.2^ 0.2^ 0.0433bV 2 plus 0.2^ 0.04331 2.0^ 0.2^ 0.0433b^ 0^ 0.2^ 0.04331 0 ^ 0.2^ 0.0433b^ ρ C :p*Ti(OCH3) 3* ^ HPΗΡΗΡΗΡΘ ^ ^ ^ ^ ^ 5555555555 ^ Jo οοοοοοο ο Comparison—' 2.0^ 0.2+3 0.0433^^ Example a) Determined by I PC b) The theoretical procedure of Example 3-4 was calculated according to the same procedure as in Example 2 except that the homogeneous catalyst (HomoCat-1) was added as shown in Table 1. Example 5 The same procedure as in Example 2 was followed except that 0.2 g of S was used. The AN polymer was used to prepare the carrier precursor I, and the contents of the components used are shown in Table 1. Examples 6 - 7 The carrier precursor II was prepared in accordance with the same procedure as in Example 2 except that MA0 was added as shown in Table 1.

Page 20 1288755 Case No. 90107017 Revised May 5, Invention Description (16) Example 8 In a dry 250 ml flask equipped with a magnetic stirrer, 4 g of alumina, 2.0 mmol of methyl The aluminoxane was added to 80 ml of toluene under a nitrogen atmosphere. The resulting slurry was stirred at room temperature for 30 minutes, then the toluene was transferred to another vessel and then removed by vacuum drying. Thus, a white powder was obtained. The SAN polymer (same as in Example 2) was injected into the white powder using a cannula in 80 ml of toluene. The resulting slurry was stirred at room temperature for 2 hours and then filtered. The solid was washed 3 times with 50 ml of toluene and then dried in vacuo. As a result, another white powder was obtained. HomoCat-1 prepared in 0.2 mmol of Example 1 was poured into a white powder using a cannula in 80 ml of toluene. The resulting slurry was stirred at room temperature for 30 minutes and then filtered. The filtered solid was washed 3 times with 50 ml of toluene and then dried in vacuo. 0 43 之间摩尔/克。 The resulting pale yellow solid was obtained as a final auxiliary catalyst, the titanium content was determined by IPC to be 0. 0 43 3 micromoles / gram. Example 9 A carrier precursor I was prepared according to the same procedure as in Example 2. HomoCat-1 prepared in 0.2 mol of Example 1 was injected into a can of 80 ml of toluene using a cannula. The resulting slurry was stirred at room temperature for 30 minutes and then filtered. The filtered solid was stirred with 2 mmol of MA0 in 80 mL of toluene at room temperature and then worked for 30 min. The resulting slurry was filtered and then washed 3 times with 50 ml of a solution. After drying in vacuo, a pale yellow solid was obtained which was determined to have a titanium content of 0.

Page 21 1288755 901078Π Case No. 5. Inventive Note (17) 10 The same procedure as in Example 2 was used to prepare the carrier precursor 1. Will enter 。 ·2. The ear was prepared from H〇m〇cat-1 prepared in Example 1 in 80 ml of toluene. The slurry formed of the genus 3 was stirred at room temperature for 30 minutes, and then filtered. The solid after 2 t was washed 3 times with 50 ml of toluene. After vacuum drying, the vapor-colored solid was used as the final co-catalyst, and its titanium was determined by Ipc to be 43 μMole/g. 11 The carrier precursor I丨 was prepared according to the same procedure as in Example 5. 2 于, = uniform catalyst, Cp*Ti (〇CHs) 〆 vapor chemical company) makeup 4 ml of benzene was injected into the carrier precursor 1 1 using a cannula. The formed slurry was stirred at room temperature for 30 minutes and then filtered. The filtered solid was washed 3 times with 5 liters of the house. After vacuum drying, a pale yellow solid was obtained as the final co-catalyst, and its titanium content was determined by IPC to be 〇·〇433 micromoles/gram. 0 Comparative Example 1 The same procedure as in Example 2 was followed except that δΑΝ polymer was not used. The carrier precursor I was prepared, and the contents of the components used are shown in Table 1. Example 1 2 In a dry 1 liter glass reactor equipped with a circulating water jacket for temperature control and a double helix impeller (steel), 200 ml of refined styrene monomer was used.

Page 22 1288755 _ Case No. 9017017~_ Year Month Day Correction _—V. Invention Description (18) and 8 ml 2^1 diisobutyl Ming (8-8, 士!^1〇3131^71&11^11111111) Add in toluene solution. The solution was mixed at 7 Torr and 40 rpm for 1 minute, then 0. 28 ml (〇·8 mmol) 2·8 M methyl aluminoxane and 〇·“g (0·0 0 8 mmol) The auxiliary catalyst prepared in Example 2 (previously floating soybean meal in 3 ml of toluene) was continuously injected until the total amount of 〇·〇4 millimolar auxiliary catalyst and 4 millimolar methylaluminoxane was injected. The total feed time was 4 minutes and the polymerization was spent an additional 80 minutes. The solution was stopped with a large amount of methanol after 2 hours of total polymerization time. The polymer was passed through and dried in i 5 (rc vacuum). , 84. 9g of polymer was obtained. The conversion rate was 46.7 wt%, and the activity was 4 4 · 4 kg / g τ i. The obtained polymer was subjected to NMR and DSC analysis, and the polymers were between heights. Polystyrene, melting point of 7 (TC. The average molecular weight (Mw) of this polymer was determined by GPC to be 54 〇, 4 〇〇, and the molecular weight distribution was 2.22. Example, 13_14 was the same as in Example 12. The procedure was carried out except that the auxiliary catalysts having different contents of titanium were prepared by using Examples 3 and 4, respectively. The data is shown in Table 2. ^ Example 1 5 The same procedure as in Example 12 was used except that the auxiliary catalyst prepared from Example 5 was used. The polymerization reaction data is shown in Table 2. Example 16_11

Page 23 1288755 Case No. 90107017 Revised V. Description of the Invention (19) The same procedure as in Example 12 was followed except that the auxiliary catalysts prepared by Examples 6 and 7 were used, respectively. The polymerization reaction data is shown in Table 2. Example 1 8 - 1 9 The same procedure as in Example 12 was used except that the auxiliary catalysts prepared by Examples 8 and 9 were used, respectively. The polymerization reaction data is shown in Table 2. Example 20 The same procedure as in Example 12 was used except that the auxiliary catalyst prepared from Example 10 was used. The polymerization reaction data is shown in Table 2. Example 2 1 The same procedure as in Example 12 was used except that the auxiliary catalyst prepared from Example 1 1 was used. The polymerization reaction data is shown in Table 2. Table 2

Page 24 1288755 Case No. 90107817 Month 曰

Repair JE V. Invention Description (20) Example θ Auxiliary P conversion rate. Activity w Mw^ mwd7" Catalyst*· (%> (kg/gΉ) (g/mole>group> ^434343^^^ ^οι 2345578911 例例例例例例例例例例例例实实实实实实^ρ^^^^-ρ^ρρ 2345678901 1 1 l· 1 1 1 1 1 2 2 46.7^ 44. Buckle 43.8 ^ 41.6^ 51.3^ 48.8^ 44_0^ 42.5^ 16.0^ 15.2^ 43.0^ 40.1^ 20.4^ 19.4^ 17.5^ 16.6^ 26.4^ 25.5^ 28·如27.4^ 540,400# 2.22^ 524,000^ 2.73^ 560,800^ 4.44^ 559,400^ 2.35^ 695,00CM 2.17^ 684,00(k 1.87^ 557,000^ 2.76^ Compare y Compare w ·々:7 Example 仏Example Polymerization conditions: 200 ml styrene monomer, 〇· 〇4 mmol Catalyst 'Ti 6, triiosbutylaluminum, [TiBA] / [Ti] = 40 0, 4 millimoles total methyl aluminoxane (MA〇, methylaluminumoxane); 70 ° C polymerization temperature · 40 rpm; 2 hours total polymerization time. Comparative Example 2 According to the same procedure as in Example 12, except that the carrier precursor prepared using Comparative Example 1 was prepared without using any SAN polymer. No under polymerization conditions listed in Table 2. The resulting polymer. Example 22 To aid in commercial scale catalytic performance was tested in the examples

Page 25 1288755 Case No. 90107817 V. Invention Description (21) 2 2 is carried out under the scale of magnification. A 1 liter glass pressure cooker reaction tank was used as the auxiliary catalyst polymerization reactor. In a completely dry reactor, 40 g of alumina and 5 g of a benzotriene polymer were added under a nitrogen atmosphere. The reactor was evacuated for 3 Torr. The 30 ml of toluene was transferred to the reactor under nitrogen pressure. The reactor was maintained at 70 ° C and stirred at 40 rpm for 2 hours. After the san polymer was completely dissolved, the toluene was transferred to another vessel and then removed by vacuum drying, and then 2 mmol of the homogeneous catalyst was used, and the "HomoCai:-1" prepared in Example 1 was added in 200 ml of toluene. After stirring at 7 ° C for 3 minutes, the slurry was filtered and the solid was washed 3 times with 100 ml of toluene and then dried in vacuo to give the final product as a pale yellow powder. The titanium content was determined by IPC to be 〇·043 3 mmol/g 0 Example 2 3 The same procedure as in Example 22 was followed except that 2 g of SAN polymer was used instead of 5 g of SAN polymer. Example 2 4 The same as in Example 22 Step, except that the ΜA0 addition step is omitted. In a completely dry reactor, 40 g of alumina and 5 g of styrene-acrylonitrile polymer are added under a nitrogen atmosphere. The reactor is evacuated at 70 ° C for 3 0. In 30 minutes, 30 ml of toluene was transferred to the reactor under nitrogen pressure. The reactor was maintained at 70 ° C and stirred at 40 ° rpm for 2 hours. After the SAN polymer was completely dissolved, the benzene was transferred to other containers. Then by vacuum drying

1288755

_ Case No. 90107817 V. Inventive Note (22) The HomoCat-1 prepared in Example 1 was removed and then 2 millimolar homogeneous catalyst was introduced in 200 ml of hydrazine. After stirring at 70 ° C for 3 minutes, the slurry was filtered and the solid was washed 3 times with 1 〇 ml of toluene and then completely dried in vacuo. As a result, the final product was obtained as a pale yellow powder. ^ The resulting pale yellow solid was determined by I PC using a titanium content of 〇 · 〇 4 3 3 mmol/g. Example 2 5 A 10-liter pressure cooker reactor was blown with nitrogen at 1 °C for 2 hours and then cooled to 70 °C. 200 ml of styrene monomer and 40 ml of TiBA, triiosbutylaluminum were transferred to the reactor under nitrogen pressure. The reactor was maintained at 7 (rc, and was scrambled for 1 〇 min at ^300 rpm in a nitrogen atmosphere. 8 mM methyl aluminoxane (MA〇, methylaluminumoxane) & 〇· 〇 8 mM The ear was prepared by injecting the cocatalyst (in the toluene suspension) of the example & the feeding operation of the hydrazine and the auxiliary catalyst was carried out in the same amount as above. After stirring for 3 minutes at 7 ° C, the utilization of the nail was again transferred to other valleys. The crucible was then removed by vacuum drying, and then 2 mmol = uniform catalyst, H〇m〇Cat-1 prepared in Example 1, added in 2 ml of the mold, and then spoiled at 7 〇C. After a minute, the slurry was washed 3 times with ml of toluene, and then completely dried in vacuo to give the final product as a pale yellow powder. The pale yellow solid formed was determined by IPC to be 〇·〇43 3 mmol. /g.

Page 27 1288755 _ Case No. 90170017_年月日日_^ V. Description of Invention (23) Example Auxiliary ^ Catalyst p (mole/liter_SM> [Ί1ΒΑ]/[Ή] Conversion rate ^ (% by weight) Activity p 25^ Example 22# 0.2^ 100^ 60.9^ 115》 26^ Example 22β 0.1^ 150^ 29.9^ 113.7^ 27^ Example 22# 0.1^ 200^ 28.4^ 108.0^ 28^ Example 23# 0.1^ 200^ 35.6 ^ 135.4^ 29^ Example 2 such as 0.2^ 400^ 30.3^ 57.6^ Polymerization conditions: 200 ml of styrene monomer, "into 0] / [1^] = 100; 70 ° C polymerization temperature; 300 rpm 3 hours total polymerization time. Example 2 6 - 2 7 The same procedure as in Example 2 5 except that the concentration of the catalyst and the ratio of [TiBA] / [Ti ] were different from those of Example 25. The results of the polymerization are shown in the table. Example 2 8 The same procedure as in Example 2 5 was followed except that the carrier precursor of Example 23 was used. The results of the polymerization are shown in Table 3. Example 2 9 · In accordance with the same procedure as in Example 2 5 except The carrier precursor of Example 24 was used. The results of the polymerization are shown in Table 3. Table 4

Page 28 1288755 Case No. 90107017 Lunar New Year Amendment Description (24) Example β Auxiliary ^ [but [ΤίΒΑ] / [Ή] Yield p Active p Catalyst ^ (亳莫耳 / 升-乙貌(kg/mol - Τί - hr) 30^ 2^ 0.2^ 100^ 0 steal 2.2^ Compare ^ Example> 1^ 0.2^ 100^ 2.38^ 58^ Polymerization conditions: 2 Ο 0 ml of hexane, 4 kg / cm ^ 2 ethylene pressure; 70 ° C polymerization temperature; total polymerization reaction time 1 hour. Example 3 0 in a completely dry 1 liter glass pressure cooker, 200 ml of polymerization grade hexane and 2 ml of 2M triisobutyl aluminum toluene solution in 7 After adding 0 ° C in a nitrogen atmosphere, after stirring for 10 minutes at 70 O rpm, the auxiliary catalyst prepared in Example 2 was 0.92 g of a suspension dissolved in 10 ml of toluene, and then ethylene of the polymerization reaction stage was added. The catalyst was maintained at a pressure of 60 psi. The polymerization was terminated with methanol, and the polymer was collected by filtration, and then dried in vacuo. As a result, 2.3 g of a spherical appearance of polyethylene powder was obtained. The activity is 5 8 kg / m ο 1 · T i · hr. Comparative Example 3 According to Example 3 0 The same procedure, except that the drive Example 1 was uniformly before. The polymerization results are shown in Table 4. Table 5

Page 29 1288755 V. Invention Description (25) _ Case No. 90170017 曰 Example # SI [Ή]; « Catalyst ρ (亳莫耳 / Well-SM> (•^ηιοί · ΊΙ» hr) 31# Example 2p 0.1^ 500^ 6.92^ ^ AjCT examples such as ΨΪΗ 0.1^ 500+5 -43 • 346^. ~/丨.W /Γ /T million metric, 70C polymerization temperature; total polymerization time J hours. f Example 31^_^ 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 The methylaluminoxane solution was added in a 7 〇t environment. After mixing for 1 Torr for 7 0, the example auxiliary catalyst 〇·6 6 g (〇·〇 2 mmol) was suspended in 丨. The hydrazine and the float were added, and then the ethylene of the polymerization reaction stage was added. The mixture was cried for 1 hour at a pressure of 60 pSi of ethylene, and the polymerization was terminated with methanol, collected by filtration, and then dried in a vacuum. As a result, & The activity of the catalyst was 346 kg/ffl〇l· Ti· u 2 The conditions and data are shown in Table 5. The winter polymerization was more than the actual Μ 4 The same procedure as in Example 31 was followed. In addition to Example 1 of the precursors. The resulting polymer Shu 3C NMR analysis syndiotactic not found stupid two polyethylene or ethylene-containing copolymers. Ethylene '

</ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; range. Such changes and modifications are intended to be included within the scope of the invention.

Page 31 1288755 Case No. 90107017 Circumstances Correction Brief Description of the Drawings Figure 1 is a schematic diagram of a method for preparing an auxiliary catalyst according to the present invention.

iBiB第32页

Claims (1)

1288755 amendment The auxiliaries of the auxiliary metal complex for the preparation of the syndiotactic styrene polymer are 001 to 99 99% by weight of (A) polymerized to 99.999% by weight of the (B) carrier, And 〇〇 001 to 30 MM aoin7Ri? VI, the scope of application of the patent 丨 7 :: transition metal compounds, the role of the polymer is the insulator of the carrier. The agent for polymerizing a syndiotactic styrene polymer, which further comprises (D) (a) a compound which forms an ion complex with "oxygen: 匕:; b) special It is used to polymerize a syndiotactic styrene polymer, which further comprises (E) an alkylaluminum compound. 3. The auxiliary metal complex catalyst of the second aspect of the patent application. (4): (4) is a complex catalyst, wherein the polymer (A) &amp; catalyst properties, harm, and catalyst are used in the polymerization of the syndiotactic styrene polymer. And the surface of the carrier has a chemical or physical interaction. After being forced into the catalyst, it is insoluble in the styrene monomer or the polymerization solvent. The auxiliary metal complex catalyst of the first aspect of the patent application, the polymer of the group, The polymer (A) is a polar group-containing compound and a copolymer, and a hydroxyl group-containing polymer, which is used for polymerizing a syndiotactic styrene polymer. Page 33 1288755 ____ Case No. 90107017_年月日修修__ VI. Patent application scope and copolymers, acrylic and acrylate polymers and copolymers, maleic anhydride-containing copolymers, acetate-containing polymers It is selected from the group consisting of copolymers, polyethers, polyketones, and polyamine polymers and copolymers. 6. The auxiliary metal complex catalyst for polymerizing a syndiotactic styrene polymer according to claim 5, wherein the polar group-containing polymer is styrene-acrylic-fried (SAN, styrene - Acrylonitrile) polymer. 7. An auxiliary metal complex catalyst for polymerizing a syndiotactic styrene polymer according to claim 6 of the patent application, wherein the styrene-acrylonitrile (SAN, styrene-aCr*yl〇nitriie) polymer has a degree of polymerization At least 5, and containing from 0.1 to 100% by weight of acrylonitrile. 8. The auxiliary metal complex catalyst for polymerizing a syndiotactic styrene polymer according to the scope of the patent application, wherein the polymer (Α) is present in an amount of from 〇·〇〇1 to 99.999% by weight. 9 申申s s patent scope 1 is used to polymerize syndiotactic styrene polymer ό complex catalyst, wherein the carrier is an organic material, from the poly-group to choose a total of t-ethylene stupid beads, starch powder And polyene powder group day 10 · The auxiliary metal complex catalyzed according to the scope of patent application is used to polymerize a syndiotactic styrene polymer agent, wherein the carrier is an inorganic material, by Shi Xi Page 34 1288755 曰 901号90107817 VI. Patent application scope: gel, alumina, yttrium aluminoxy gel, zeolite, mica powder, clay, molecules: "metal compounds, metal-forms, metal carbonates and gold; selected from the group consisting of the last The auxiliary metal complex catalyst for polymerizing a syndiotactic ethylene polymer according to the first aspect of the patent application, wherein the carrier (Β) has a denier 001 to 9 9.99 99% by weight. 12. The auxiliary metal complex catalyst for polymerizing a syndiotactic phenylethyl group polymer according to claim 1, wherein the transition metal compound (&quot;c) is represented by the following formula (A) or (b) Group ivb metal compound · MR1aRW-c) (A) · MR1dR2eR3〇^(d+e) (B) wherein Μ is an atom of group IVB, and R1, R2 &amp; R3 are a hydrogen atom and a carbon atom An aryl group having 20 carbon atoms of a carbon atom, an aralkyl group having 6 to 2 carbon atoms and an aralkyl group having 20 carbon atoms, having a enthalpy to "a carbon atom" ^气某, : pentadienyl, substituted cyclopentadienyl or nodal, 乂 is a dentate worker, a, b and c are integers from 〇 to 4, and d&amp;e is an integer from 〇 to 3. 』 charm tm circumference of the first item used to polymerize syndiotactic styrene polymer ^ auxiliary metal,,,. a catalyst comprising the component (D) which is a compound of the compound (D), wherein the component (1) is an alkyl group. Page 35