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    公开号:SU784741A3
    申请号:SU762430202
    申请日:1976-12-21
    公开日:1980-11-30
    发明作者:Дж. Арзоуманидис Грегори；Ф. Голд Ричард；Г. Мишель Кристиан
    申请人:Стауффер Кемикалз Компани (Фирма)；
    IPC主号:
    专利说明:

    (54) CATALYTIC COMPOSITION FOR POLYMERIZATION OF α-OLEFINES The invention relates to catalytic compositions for the polymerization of o-olefins. Known catalytic composition for the polymerization of O-olefins on the basis of titanium trichloride, obtained by grinding it together with hydroxide, sulfate, sulfite, phosphate, phosphite, carbonate, cyanide, thiocyanate, nitrate and / or metal nitrate ij The nearest known solution of a similar problem with technical essence and the effect achieved is a catalytic composition for the polymerization of o-α-olefins, containing titanium trichloride and an electron donor compound with a dipole moment of from 0.5 to G, 0 Debu units 2.1. A disadvantage of the known composition is insufficient activity (572 g of polymer / g of catalyst), which is a consequence of the agglomeration that occurs when a known composition is obtained during grinding or grinding in a titanium trichloride ball with an electron-donor compound. To increase the catalytic activity, a composition for the polymerization of o-α-olefins was proposed, containing P-titanium trichlorides, an electron-donating compound, and additionally an agglomeration regulator — a compound selected from the group containing :. a) an ionic compound selected from the group comprising ionic salts of groups IA, 1I A, transition metals, quaternary ammonium salts of the formula RitPX, where R is hydrogen, alkyl C, - C, and X is halogen or sulfate ;; ionic surfactants; finely ground water-soluble ammonium salts of amidopolyphosphonate, obtained from the dry vapor-phase reaction of PjOg and anhydrous ammonia; salts of aliphatic C.-C tribasic acids and their oxyl-displaced derivatives / hydroxyl sulfates Cj, -Cjg of alkali metals; alkaline earth metalplate phosphates, helium-earth metal titanates and non-gas-forming halides, or c) a polarizable compound selected from the group including compounds of the formula ((0) OP (0) A, in which A is selected from the group included from OR, .NRR and OH , where R and R are C - Q alkyls with the proviso that at least one A is either OR or NRR group; trialkyl phosphates of the formula (RO) PO, where R is an alkyl C - C group; selected from the group consisting of amorphous silica and siloxanes; dialkyl phosphoric acid of the formula (RO) -P (0) OH, where R is alkyl Cf group, dialkyl maleates and fumarates, reaction products (C5H5) Q.Si (O and titanate of formula Ti (RO), where R is alkyl C: | - C group; compounds of formula RCONH2, where R is C, is alk and the group and its polymers; solids selected from the group including graphite, carbon, and sulfur starch / alkyl ketones, provided that the total number of carbon atoms in the two alkyl groups is between 20 and 30) epoxides and polymer derivatives C x, j urea and alkyl substituted C - C, m chevins, alkaline salts of dia Intra-acetic acid; water soluble simple cellulose; phthalocyanine dyes; Cj - SL acrylates; Compounds of Formulas RNXji, f where X is chlorine or bromine, and 1 has a value of 2 to 4, compounds of the formula (CgH) ,, Sr, S PS (OH), where R is C - C; -alkyl, and non-gaseous ci-olefins, with the following ratio of components, weight; Electron; donor; compound 2, 15-8.32 Agglomeration regulator 0.009-0.22 titanium trichlorideOther The distinctive features of the new composition are the additional holding of the agglomeration regulator in the catalytic composition selected from ionic or polarized compounds, and the ratio of components. The catalytic composition possesses increased activity as compared to known (1078 g of polymer / g of catalyst}, which is an additional content of the agglomeration rotator, which regulates the aggregative behavior of fine crushed particles resulting from grinding the titanium trichloride catalyst component, and ensures the formation of a powdered product by storing the individual particles in a divided form, generally without agglomeration. TepMiSH agglomeration is defined as the disordered formation of aggregates or clusters of finely divided particles due to grinding of titanium trichloride and electron donor compounds. This undesirable phenomenon, if it exists, usually leads to a decrease in the catalytic activity of the component. Small particles that are polar in nature, such as titanium trichloride, are usually subject to agglomeration during grinding, to the most significant size 1. The tendency to agglomeration is believed to depend on both electrostatic or Coulomb repulsion forces between particles, and van der Waals attraction forces between said particles. Although binding is theory undesirable, observations have shown that for a given distribution of particle size and medium, the degree of agglomeration may depend on the combined potential of joint interactions between, particles and may be no more than the sum (Y) of the electrostatic repulsion potential (Ya ) is the potential of the van der Waals attraction forces (Vqp). For chyutits, spherical in form, mathematical expression Y, J V. Ynp. Since the Enderwalsa gravity forces act on very short distances, these attractive forces typically must prevail over electrostatic repulsive forces when the average particle size in the system decreases. Therefore, fine particles, polar in nature, resulting in intensive and long-lasting grinding, tend to agglomerate more easily, 4-e.i-A relative to -1o large particles. In accordance with the invention, it has been found that the addition of an effective amount of a compound to control agglomeration can regulate agglomeration in a mixture of track and titanium, an electron-donating compound that is milled, can thus maintain the separation of fine particles contained in the mixture. Compounds I and for regulator and agglomeration include the following broad classes of compounds: a) compounds that, upon adsorption on fine particles, can modify the joint forces of interaction and thus are effective in retaining particles. divided state. Examples of this class are ionic compounds. They are supposed to act by increasing the surface potential (Z-potential) of the indicated particles; b) polarizing compounds of sufficient size so that when they are attached to the particles of the catalytic component, they cause steric hindrance for contact, and subsequent agglomeration, of the particles to the analyzer. The compound for agglomeration is a compound that either modifies the joint forces of interaction between the catalyst particles, or creates a steric hindrance or barrier between the parts of Csm, the warning contact and the subsequent agglomeration part, titanium trichloride and electron donor compounds can be used to control the agglomeration, which are milled in the presence of the selected compound to control agglomeration. Titanium trichloride can be produced in a variety of ways, including: a) reduction of titanium tetrachloride with a metal such as aluminum or titanium, with the indicated reduced titanium product being either crushed or unmixed b) reduction of titanium tetrachloride with hydrogen, c) reduction of titanium tetrachloride by a meta-organo compound , such as aluminum alkyl, or d) grinding a mixture of titanium trichloride and a halide metal ill group, such as aluminum halide. Examples of suitable starting products based on titanium trichlorochlorine are well known. The starting material of the ramela is wound together with the electron donor compound and the substance to control the agglomeration to form the corresponding component of the catalyst. The second product in the collocution of our inventive invention is an effective amount of the electron donor Compound to increase the stereospecificity or stereospecificity and activity of the final catalyst. The impurities of suitable electron-donor compounds that can be used in the invention can be selected from the following classes of compounds: organic oxygen-containing compounds, such as aliphatic ethers, aromatic ethers, esters of aliphatic carboxylic acids, cyclic esters of carboxylic acids, esters aromatic carboxylic acids, esters of unsaturated carboxylic acids, aliphatic spins, phenols, aliphatic carboxylic acids: sweats, gsifa acid halides ble of carboxylic acids, lactones, halo idangidridy ,, aromatic carboxylic acids, aliphatic ketones and aromatic ketones} Cpd Neny organic nitrogen such as aliphatic amines, aromatic amines, heterocyclic amine, aliphatic nitriles, aliphatic karbgi Ata, aromatic nitriles, aromatic and aromatic ed 1ianaty azo compounds; mixed oxygen-containing compounds such as aliphatic and aromatic amides and guanidine and its alkyl substituted derivatives; organic phosphorus-containing compounds such as aliphatic phosphines, aromatic phosphines, aliphatic phosphites and aromatic phosphites; mixed phosphorus-containing compounds, such as amides of phosphoric acid; mixed phosphorus-oxygen-containing compounds, such as triphenylphosphine oxide; sulfur-containing compounds, such as carbon disulfide, aliphatic thioesters and aromatic thioesters} organic silicon-containing compounds, including MOriomeric-type compounds, such as tetrahydrocarbolsilanes, organohydridesilanes, organohalidesilanes, organoaminosilanes,. organo-aipoxoxanes, organoaryloxysilanes, organic silicon-containing isocyanates and esters of organosilanol and carboxylic acids} polymeric compounds, such as alkylene polysilanes, orgaiopolysilanes; arananopolysiloxanes; of, W-dihalide organopolysiloxanes, organocyclopoly siloxanes and polysilazanes. The dipole moment of most of the selected electron donor compounds is usually in the general range of about 0.5 to 6.0 Deba units. Examples of some of the most common sites Other compounds that may be used in the practice of the invention are known to those skilled in the art. Other typical examples of individual electron donor compounds can also be found in the well-known solution 2. A third necessary component for the composition of the present invention is a compound for agglomeration control, which prevents titanium trichloride and electron-donating compounds from agglomeration when these components are milled. As briefly described above, in the present invention, two classes of compounds are useful for controlling agglomeration. The first class of compounds includes ionic compounds which, when added to finely ground particles, can make a change in the 2. -potential of the particles and thereby prevent agglomeration.
    The following compounds are typical of such ionic compounds:
    1) Ionic salts of metals of group lA of the periodic table 3. Examples are halide salts such as lithium fluoride, lithium chloride, lithium bromide and lithium iodide, and similar sodium, potassium halide and cesium halide salts. The salts of common metals of other common anions, such as sulfate, nitrate, stearate, borate, silicate, aluminate, citrate and thiosulfate, must also be considered within this class of compounds. Salts of: alkaline metals benolsulfonic acid and C-Cu d-alkylsulfonic acids must also be considered within this class for the invention, one compound of this class of compounds is the benzenesulfonic acid sodium salt
    2) ionic salts of ions of metals of group IlA, which are similar to the salts presented above for subclass 1 /
    3} Ionic salts of transition metals. Especially preferred are stearate salts of copper to zinc.
    4) Quaternary ammonium salts of the general formula RxNX, where R is hydrogen, alkyl, or aryl, and X is halogen or sulfate. Examples of suitable compounds are trialkyl chlorohydrates | brominates and iodohydrates, preferably C-trialkyl compounds of these halohydrates. A characteristic compound is triethylamine hydrochloride,
    5} General class of compounds as ionic supernaturally active substances 4}.
    b) finely divided, water-soluble ammonium salt of amidopolyphosphate, in which essentially all particles have a diameter of less than 5 microns. It is formed by a dry vapor phase reaction with anhydrous ammonia 5j. A typical elemental analysis for such a product is as follows: IaOg 76.1%, M, free 15.4%, NHj, total 22.4%, g1mid nitrogen as NH, 7%; pH (1% solution) 5.6. The corresponding product of this type is available under the name of the special range of chemical department Stauffer Co-Shkl Company from Westport (Connecticut). Although the compound is proposed as a component in a four-component anti-caking and anti-freezing additive for bulk sodium chloride in the form of f6j particles,
    It cannot be assumed that it will effectively act as a compound for controlling agglomeration in creating catalytic KONraoHeHT based on titanium trichloride, as described in this invention. When water-insoluble ammonium polyphosphate is used, then by. an inactive catalytic component is emitted;
    7) aliphatic tribasic salts
    acids, preferably Cj | -anKaH tricarboxylic acids and oxy-substituted derivatives of such acids. One such acid is 2-hydroxy-1,2,3-propanetricarboxylic acid (citric). Alkali salts, alkaline-earth salts and transition metal salts, mixed with one of the anions, are preferred. Two compounds are effective; they are calcium citrate and double salt of ferric citrate 3 and ammonium citrate. The use of salts of dicarboxylic acids, such as tartrates, is inefficient,
     .8) alkali metal alkyl sulfates, preferably Cg-C (g-alkyl substituted compounds. A suitable compound is sodium dodecyl sulfate
    9) alkaline earth metal phosphates. One compound is tribasic calcium phosphate;
    10) alkaline earth metal titanates, including calcium titanate and
    11) non-gaseous halides, such as iodine, which despite the fact that
    5 is covalent in free
    State, reacts with titanium trichloride in Sft-U to create ion sites.
    A second type of compound for controlling agglomeration are polarizing compounds that are adsorbed by the catalyst component particles, creating a steric hindrance and thereby preventing the contact of adjacent catalyst particles based on titanium trichloride. Basically, these substances for controlling agglomeration or for preventing agglomeration of titanium trichloride have a chain length or diameter in a disordered conformation of about 10 to 200 A angstroms.
    Agglomeration usually does not occur.
    if the 2+ K ratio, where 6t, is satisfied, is the barrier distance provided by e1 the first electron donor compound in the system; 4 is the barrier distance provided in the system. a compound for controlling agglomeration; K is a constant, which is learned by reducing a mathematical derivative to a null. expressions for the total system potential. acids and polyacrylamide are characteristic compounds for controlling the agglomeration of this class of compounds; some compounds with a chain length of more than 10, 8} Elementary solid consisting of graphite, amorphous carbon and sulfur. Two preferred substances from this group, including graphite, are one of the crystalline alltropic forms of carbon (the other is diamond) and sulfur. 9) Starch. 10) Alilketones with the proviso that the total number of carbon atoms in the two alkyl groups varies from 20 to 30. Some characteristic ketones are Lauro (which has the formula (and 14-heptacosanone of the formula 4Ci3Hzf} 11)) Epoxides and polymeric derivatives of such compounds, with the exception of monomeric ethylene oxide and propyl oxide. Two compounds from this class include cyclohexenyl tylcyclohexenecarboxylate diepoxide and polyethylene oxide, which is a water-soluble polymer obtained by the polymerization of ethylene oxide, for example by using alkaline catalysts. 12) Trialkylborates5 preferred C-trialkylborates. Some of these compounds have a chain length of less than 10 liters. A characteristic compound of this group is trimethylborate. Boric acid itself does not suppress agglomeration. 13) Urea and alkyl substituted u: urea, preferably C.-Cj-alkyl substituted urea, also include compounds having a chain length of up to 10 L. Two of this class are urea itself and tet. rametilurea. 14) Alkylenediamine tetraacetic (ACIDS, preferably their C-alkylene compounds, especially ethylenediaminetetraacetic acid. Alkali metal salts of such acids are ineffective, 15) Water-soluble cellulose ethers, including methylcellulose and sodium carboxymethyl cellose, 16) Phthalocyanotropic acid, 16-phthalocyanine, 16-phthalocyanine, 16). copper chlorinated phthalocyanine copper sulfated phthalocamine copper. A preferred compound is copper phthalocyanine. 17) C-Acrylates, which thus include compounds with a long chain of less than 10 X. Preferred pent is methyl acrylate. 18) The compound of the formula. where X is chlorine or bromine, au is 2-4, the preferred compound is PN C fj, where n is 3 or 4, 19) Compounds of the formula (C, H,) e S p5 P (PR) (C (j H () a, S p JS, where R is Ci-C-alkyl. Methods for preparing the above compounds are given in Sources 1, v. 20) Non-gaseous o-olefins, such as 1-eicosene. Not all possible polarized compounds will be act as compounds for regulating agglomeration together with a specific electron donor compound. For example, 2-undecanon is not effective at regulating agglomeration and with electron donor and hexamethylphosphoric triamide. The compound efficiency for controlling the reduction of agglomeration is sensitive to the choice of the electron donor compound. To obtain the target component of the catalyst, it is preferred that three components be present in specific amounts. For example, the amount of electron donor compound should vary from 2 to 15 weight% of the product on the basis of trichloride titanium, preferably from 2.5 to 10 wt.%. The amount of electron-donating compound must be in an amount sufficient to form at least a monomolecular layer on titanium trichloride particles. The preferred limit depends on the molecular weight of the electron donor compound and the effective surface area of the product based on titanium trichloride. Using too much of the electron donor compound usually poisons the catalyst component, while using too few does not improve the catalytic properties. For good results you need b wt.% Hexamethylphosphoric triamide (HMPTD). The selected electron-donating compound has the formula L (CHi) o Nj, PO. Molecules that have a smaller cross section during adsorption than HMPTA require a correspondingly larger amount to achieve equivalent efficacy in the formation of a monomolecular layer, then relatively large molecules are used in a smaller amount. Generally effective in preventing agglomeration of an amount of about 0.1-5% B based on the weight of the electron donor compound, preferably 0.6-3.0%. The amount of compound for controlling agglomeration depends on the nature and amount of the electrolyte compound, and on the average particle size of the product based on titanium trichloride, particles that are half-sized when using relatively large particles that are obtained using a slow grinding speed. The grinding rate H, which is determined by Berry 9J, refers to the surface area of the E, the crushed product and the time of grinding by equation .5 / 4.
    Grinding in the invention can be carried out by grinding the two components together with the compounds to control the agglomeration (described above) at ordinary temperatures and times. Grinding can be carried out in a ball mill or in other suitable apparatus without diluents in an inert atmosphere, such as nitrogen or argon, free of oxygen, water and other catalytic deposits, to a pulverized composition, which, after combining with organic organosulfur compounds
    Zugt catalyst having good activity and stereospecificity during polymerization of ot-olefins. Basically, when using a rotating ball mill, grinding takes place in 30-90 hours at 30 -, especially p 50 ° - 60 ° C, for 40 - 80 A suitable apparatus for carrying out such grinding 10 has a fast grinding speed and a grinding time of, for example, 3 to 12 hours. When measuring the temperature, the actual temperature in the inner part of the ball mill is directly measured (should be approximately 70 ° C) catg a schizator and subsequent deactivation of the final catalyst can occur even in the presence of a compound to control the agglomeration of the invention.
    There are many factors encountered in determining the identity and amount of a compound to control agglomeration, which typically operates with an electron donor compound. For example, a polar compound for controlling agglomeration is 1-eicozen and Triton X-100, harmful when milled with dimethylacetamide, while sodium chloride, an ionic compound for regulating agglomeration, provides good results. In addition, excessive amounts of either of the two compounds as electrophoresis may also act to induce or enhance the agglomeration to regulate agglomeration, although a certain amount of electron donor is required in the final polymer to ensure proper properties. As the number of balls in the mill increases, agglomeration is induced when the jjj-butyrolactone is used without a compound to control the agglomeration, while
    The temperature of grinding three times has a similar effect on senzofenon. These data indicate that the compound for controlling agglomeration must be used in commercial development to avoid agglomeration due to unexpected changes in the grinding conditions.
    The product of the invention based on titanium trichloride, an electron donor compound, and a compound for controlling agglomeration can be combined with conventional organo-aluminum compounds for use in the polymerization (X -olphins using standard conditions for this polymerization.
    Suitable alyuminiyorganichvskimi compounds are aluminum alkyls, trymetilalyuminy, triztilalyuminy, tributylaluminum, triisobutylaluminum methylaluminum sesquichloride, etilalyominy sesquichloride, dietilalk shniyhlorid, ethylaluminum chloride, dibutylaluminum chloride, diethylaluminum sesquichloride.
    Ethyl aluminum compounds, such as triethyl aluminum and diethyl aluminum chloride, are preferred as organoaluminum compounds.
    The proposed product can be used to produce o-α-olefin polymers having from 8 children of 8 carbon atoms, including propylene homopolymers, ethylene propylene copolymers, ethylene nomopolymers and butene-1, 3-methylbutene-1 polymers. The polymerization of such monomers is usually carried out at 10-150 ° C at a pressure of from 0.5 to 100 atm.
    Example. A general procedure for the preparation of a catalyst component based on titanium trichloride modified with an electron-donating compound, using compounds for controlling agglomeration to produce finely divided product.
    Pure hexamethylphosphoric triamide (about 3.2 g) is mixed with about 0.032 g of one of the compounds to control agglomeration listed in Table. 1, weighed into a small vial. The mixture is then placed in a stainless steel mill with an inner diameter of 11 cm and a length of 15 cm in a glove box operating under nitrogen in the absence of air and moisture. The mill, which contains 875 g per 1, magnetised stainless steel balls of 1 cm in diameter, is shaken so that a liquid film forms around the balls and on the inner wall of the mill. To this mixture is then added 50 g of titanium trichloride, which is obtained by reduction of titanium tetrachloride with metallic aluminum. It is a co-crystallized product corresponding to the formula 3 TiCtbAtcE, () from Stauffer Chemica Company, Specialty Chemical Division, Westoport, Connecticut. Then the mill is closed for impermeability of air and rotated at a speed of 110 rev / m during those 48 hours at 50 ° C. The temperature is maintained using a system that includes a thermocouple inserted into the oil, gently poured into the inside of the mill, a temperature controller and a register temperature External heating is provided by infrared radiation. By the end of the 48-hour period, The agglomerated, mostly agglomerated and finely divided component of the catalyst is transferred to a can in a dry box (tested for activity and isotacticity index). The agglomeration is observed visually, except for Example 14, where at least 30% of the composition is agglomerated. The catalyst component thus obtained contains 50 g of titanium trichloride, 3.2 g of the electron donor and 0.032 g of the compound of the agglomeration controller, i.e., 93.93%, 6.01% and 0.060%, respectively. EXAMPLE 2: A test procedure for determining the activity and isotactic index of a product formed using catalyst components of the type described in Example 1. In an autoclave with a capacity of 3.85 liters (1 gallon) equipped with a jacket and a stirrer at a speed of 600 rpm load 1 liter of dry heptane. Approximately 0.3 g of the product from Example 1 was suspended in heptane under a nitrogen atmosphere and 8 ml of a 20% solution of diethylaluminium chloride in heptane was added. In the autoclave load another 1 liter of dry heptane, close. The temperature is raised to, gases are released, hydrogen gas of 0.225 kg / cm is charged, and propylene is fed at constant pressure in the reactor at 9.98 kg / cm. Propylene is purified by passing through a column with a copper-based catalytic converter to remove minor amounts of oxygen and through glass sieves (such as Linde 4A) to remove traces of water. The polymerization test is carried out for 4 hours, the catalyst is decomposed by adding a mixture of propanol and water, and the polymer product is filtered off, dried over night and weighed. Approximately 6 g of dry polymer is extracted with heptane for 3 hours in a Soxhlet apparatus. The percentage of the non-extracted portion of the pimer is referred to as C-isotacg. From the aliquot portion of the filtrate, the amount of the polymer to be formed or attacked is divided by evaporation of the solvent. The activity is determined as dry solid polymer in grams per gram of catalyst containing T i C Bi and obtained according to Example 1. The isotactic index (AI) is determined by the formula. C is isotactane solid polymer Total weight of the polymer obtained The total weight of the polymer obtained is insoluble (isotactic) and soluble (atactic) polymer parts. Example 3. Preparation of a catalyst component based on trichloride titanium modified with an electron donor compound in the absence of a compound to control agglomeration. Pure hexamethylphosphoric triamide (approximately 3/2 g) is weighed into a small vial. This compound (hereinafter abbreviated HMFTL) is introduced into a ball mill. Then 50 g of T i C f jA are added to the mill and closed and rotated at a speed of 110 rpm for 48 hours at 50 ° C. By the end of the grinding time, the mill is opened under an inert atmosphere. A mixture of TiCt, H HMPTA is lumpy and tends to adhere to the walls of the mill and to the balls. The product was not satisfactory for the polymerization of propylene. PRI me R 4. Table. Figure 1 represents activity data and isotacticity index for a number of catalyst components, formed as described in Example 1, tested as described in Example 2 and containing one of the compounds for agglomeration control suitable for use in the invention. The catalyst components contain 93.93% titanium trichloride, 6.01% electron pair donor and 0.060% agglomeration regulator. The tendency to agglomerate depends on the particle size oi, which is determined by the various grinding parameters. When grinding is carried out under conditions different from those used in the table. 1, the activity and isotacticity index for the same amount of compound for controlling agglomeration may differ. Example 1). Illustrates increased activity and isotacticity index, which is obtained when grinding the catalyst component in a ball mill is carried out at a prior, respectful temperature limit at 50 ° C compared to grinding at room temperature for both catalyst components containing HMFTD, about 6-8% HYMPT, in the calculation of the id weight of ST and i Ct, &.,. The procedure of Example 1 was used to prepare a component of catalysis, a torus, tested in accordance with the procedure of Example 2 to determine the activity and index of eoacticity. The duration of the grinding time of a component of the catgieat in a ball mill is set at 48 or 72 hours, as shown in Table 2. 2
    Example Prepared and tested according to the general procedures described in examples 1-2, a series of electro, nodone compounds (in Table 3, sokratseino are presented as ED) and addition to regulate agglomeration (PA).
    Example 7: Shows the effect of increasing the amount of the electroiodonon molecule and the amount of the compound to control agglomeration. Larger amounts of the electroiodonon compound usually require the use of higher amounts of the compound to control the agglomeration due to the increased attractive forces between the finely divided particles of trichlorite titanium, which are coated with the donor compound. Hexamethylphosphoric triamide (HMPA) and octamethyl pyrophosphoramide (OMF) are chosen as the preorium compound and the agl microsheracine regulator, respectively. Composition give in table. four.
    The test was carried out in the apparatus described in U.S. Pat. No. 3,688,992, which has a faster grinding speed than the one used in Example 1. The apparatus is loaded with balls with a diameter of 1.27 cm and a weight of 90.72 kg, the grinding is carried out at a speed of 285 rev / min
    Example It illustrates the fact that only minor amounts of an ionic compound to control agglomeration (PA) are required to control the agglomeration of a mixture of titanium trichloride and an electron-donor compound (ED)
    The content of componeitosis and indicators are given in table. five.
    Example 9. Illustrates the fact that relatively small amounts of polarizing compounds regulate agglomeration to regulate agglomeration. The composition and indicators are in the table. b.
    I'll try it on. Illustrates the effect that the defrosting rate has on the degree of agglomeration when the compounds are used to control the agglomeration. The tendency to agglomerate decreases with the use of large quantities of the compound to control the agglomeration and increases with increasing grinding speed. In tab. 7 relatively low activity (experiment 2) shows the onset of agglomeration (experiment 4). .i,
    The grinding rate, R, depends on the surface area of the grinded medium (for example, balls and ball mill) per unit weight of the substance that is ground, as well as on the size of the balls and the diameter of the mill. The characteristics of the grinding rates for various apparatuses are determined empirically. Standard laboratory milling machines, such as those used in Example 1, are classified as mills with a slow grinding speed.
    An example (comparative) presents additional inefficient potential potential agglomeration control compounds that are not listed in Table. 1. The compounds were prepared and tested according to the methods of the examples and 2, the hexamethyl phosphorotriamide was chosen as the electron donor. The results of this table. eight.
    PRI me R 12 (sravd1telny); Shows the individual combinations of the electrolyte compound and the possible compound for controlling agglomeration, which have been tested in the methods of .3 examples, and lead to agglomeration. Non-active combinations occur due to the large excess of the electron-donor compound due to the formation of a more than monomolecular layer. In tab. 9 summarizes the results.
    Example 3 (comparative). Illustrates the results of a series of experiments showing changes in the effects of compounds to control agglomeration on selected electron-donating compounds. Inappropriate combinations are again obtained due to an excess of the electron donor and / or the compound to control the agglomeration. The result is given in table. 0
    Example 14. Demonstrates that a change in the condition: grinding can induce aggls & a radio in the case of a specific electron donor compound. The data also makes it possible to compare a composition based on T i C with a composition based on both an electrone donor compound and a composition based on T1C (electroplating compound h is a compound for controlling agglomeration. In the experiments presented in Table 11, the agglomeration is determined by tracing the crushed kata isator component compositions: an increase in the percentage of particles in the composition, which has an unbounded particle size of less than 75 microns when the compound is used to control agglomeration. and sodium bromide as a compound for controlling agglomeration. The general procedure of Example 1 was used with the exception that 17ijO of balls were taken with a 1 cm diameter
    and the grinding temperature is equal, since Kak determined that benzophenone does not induce agglomeration at the grinding temperature. Polymerization and determination of activity and indos. Isotacticity are carried out as
    described in example 2. Unless otherwise indicated, all data reported for activity and isotacticity index are average values for two polymerization runs. TALES 11 shows the composition and results.
    Table
    Ammonium salt of amidopolyphosphate (water soluble)
    Ammonium salt of amidopolyphosphate (water-insoluble) /
    Amorphous silica
    Hexg1methylsiloxane, Polydime iloxloxane
    Ethyl silicate
    Diy 3 oamylophosphoric acid
    Diethyl maleate
    (C (, H) 3 t (-I i oc Hydrochloride triethyl Propionamide
    Amide stearic acid
    Polyacrylamide
    Graphite
    Sulfur
    Iodine
    Sodium chloride
    Na-salt of benzenesulphonic acid
    Lauron
    Diepoxide cyclohexenylmethyl cyclohex carboxylate
    Polyethylene epoxide borate or chemical trimethylborate
    1357
    94.8

    Note.
    Continued table. one. .
    The compounds do not act as agglomeration control agents and are structurally related to the characteristics immediately preceding them.
    Victa -1cd from the Special Assortment Chemical Department of Staufer Chemical Company, Westport, Connecticut.
    Fochek R-30 from Monsanto Kompany.
    ; Carbosil, grade M-5, from Cabot Corporation.
    It is formed according to the patent SZNA No. 3758535.
    - ERL-4221 from Union Carbide Company.
    It is formed according to the methods of Belgium patents W 783532 and QUA 3264177.
    48
    72
    48 72 P
    Table 2
    86.2
    619
    82.6 88.7 1070 88.2
    93.6
    881
    87.4
    94.0 8Y, 5 1267 en. The actual temperature in the inside of the ball mill is approximately. contains about 0.2% octamethylpyrophosphoramide as a substance for agglomeration control. The catalyst contains 92.1-92.4% titanium trichloropentane, 5.65-7.39%; HMPA and 0.18% agglomeration regulator compound. . Table3
    Continued. 3 n
    Table4 Numbers in parentheses - wt.% Calculated on the total weight of the catalyst component, wt.% Based on the weight of the product based on titanium trichloride. Weight% based on the weight of the electron donor compound. In pac4ejie on the average of two experiments on polymerization. The company Rohm & Haas, is octylphenoxypolyethoxyethanol. Grinding was carried out in a laboratory ball mill containing 875 g of balls with a diameter of 2-1 cm. Grinding was carried out in a laboratory ball mill containing 1750 g of balls with a diameter of 1 cm. P
    Note.
    TaOlitsaB
    The numbers in parentheses are wt% based on the total weight of the catalyst component.
     Based on the amount of products based on titanium trichloride.
     Based on the amount of the electron donor compound.
    Depending on the grinding apparatus, agglomeration usually occurs if the compound is not used to control agglomeration.
    The average of two experiments on polymerization. The numbers in parentheses represent% by weight of the total weight of the catalyst component. Depending on the conditions of performance Based on the amount of products based on titanium trichloride. In terms of the amount of electron-donating compound, grinding apparatus, visible agglomeration occurs when the PA-compound is not used. TABLEB Notes. Sodium trimetaphosphate Toluene Kappa Carrageenan Ammonium dihydrogen phosphate
    Sodium acetate. 12-anisaldehyde
    2-undecanone titanium oxide
    Teflon K-10
    Fluorinated
    polymer
    (ABOUT)
    Dodecyltrimethylammonium diphenyl phosphate
    Methyl amyl ketone (ClHlOib-TiOl
    Prn.mechanie. - these compounds are not tested.
    Table
    Sulfanilamide
    Di-N-propyl disulfide
    Pentaerythritol
    TO
    -Oh
    Phosphorus thioxide
    Ltd
    PKNSNSYALSNATSHR
    -ft
    l -
    Magnesia oxide
    Isoquinoline
     g
    ( R-(),
    Tory oxide
    in polymerization experiments. numbers in parentheses, wt.%, calculated on the total weight of the catalyst component. Ta b faces s
    note

    WE) isotactic index is 91.2.
    T a to l and c-a 9
    The numbers in parentheses are weight% in terms of the total weight of the catalyst x catalyst.
    Based on the weight of the product based on titanium trichloride. Based on the weight of the electron donor compound. Tested in Example 2, the activity levels are 1195 and the activities are 1153 and 1431 and the eotactic indices are 96.0 and 93.8, respectively. The degree of agglomeration is set by visual.
    6.0 (5.66)
    94.29
    Table 10
    0.9 (0.051)
    80
    Note. Notes a.
    Continued table. ten
    The numbers in parentheses are wt% based on the total weight of the catalyst component.
    权利要求:
    Claims (6)
    [1]
    Table 11 The numbers in parentheses are weight% based on the total weight of the catalyst component. Represents the average of three polymerization runs. Formula of the Invention Catalytic composition for G1: olimerization of β-rlephins, containing titanium trichloride and an electron donor compound with a dipole of HHtvi from 0.5 to 6.0 Debun units, with the difference In order to increase the catalytic activity of the composition, it additionally contains an agglomeration regulator — a compound selected from the group containing a) an ionic compound selected from the group comprising ionic salts of groups IA and I1L; transition metals, quaternary ammonium salts of the formula R N X, where R is hydrogen, alkyl. 4 С, X - halogen or sulfate, ionic surface-active agents; finely divided water-soluble and 1-ammonium salts, amidopolyphosphonate, which are hydrolyzed in the dry vapor-phase reaction of anhydrous ammonia, salts of aliphatic C tribasic acids and their oxo-substituted products; alkali metal alkyl sulfates; alkaline earth metal phosphates; titanates are alkaline earth metals: non-gaseous halides, or c) a polarizable compound selected from the group including compounds of formula (A) i7P (0) OP (0) A2, where A is selected from, including OR, NRR and OH, where R and Rc are alkylamine Ci | - € 4, provided that at least one A is either OR or NRR, three form alkyl phosphates. (HU), where R is an alkyl group C.j - Cj, polymeric silicoxy; compounds selected from the group consisting of amorphous two-silicon and siloxanes; dialkylphosphoric acid of the formula (KO) g P (0) OH, where R is alkyla Qj - C i pynna, diethyl maleate, products of the reaction. (C I) (S 1 (OH) 2, Ti (OR) titanate, where R is an alkaline C group; compounds of the formula CSOK, where I is an alkyl group and its polymers; solids selected from the group including graphite, amorphous carbon and uru, starch; alketones, provided that the total number of carbon atoms in two eshkyl groups is in the range from 20 to 30, epoxides and polymeric derivatives of such compounds; trimethylborates 04, urea and alkyl substituted Q - (ureas, alkali salts diaminetetraacetic acid; water soluble ethers phthalocyanine dyes, methyl methacrylate, the compounds are formulated with chlorine or bromine, and h is between 2 and 4J compound form (S hi SP (S) (OR) or (,), Snjj. D® R - Ct-C alkyl, and non-gaseous alpha-olefins in the following ratio of components, wt.%: Electron-donating compound, 15-8,32 Agglomeration regulator 0, 009-0,22% Titanium Trichloride Recycled Sources of information taken into account during the examination 1.Patent Germany No. 2342200, class From 08 F 10/00, published 1974.
    [2]
    2. US patent it 37017G3, cl. 252-429, pub. 1972 (prototype).
    [3]
    3. Handbook of chemistry and physics. 57th edition, CPC, Cleveland, Ohio, p. AT 4.
    [4]
    4. Encyc gopedi surfactants. Ed. J.P. Sisley, New York, vol. 1 and II, 1961, 1964.
    [5]
    5. US patent number 2122122, cl. 210-57, published. 1956
    [6]
    6. US patent number 3428571, cl. 252-383, publ. 1968, 7.niaTBHT Belgium No. 783532, cl. In 01- J, pub. 1973. 8. US patent number 3264177, CL, 424-288, publ. 1966. 9. Works of the International Congress on Surface Activity, London, 1957, p. 156-202. 10. US patent 3,688,992, cl, 241-23, published. 1973.
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    同族专利:
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    US64343875A| true| 1975-12-22|1975-12-22|
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