TW316909B - Method for producing propylene-based polymer, catalyst component for propylene polymerization and method for producing the catalyst component - Google Patents

Abstract

There are provided a propylene-based polymer characterized in that (1) the xylene-extraction insoluble portion (XI) is 99.0 wt% or greater, (2) the isotactic pentad ratio (IP) is 98.0% or greater as measured by 13C nuclear magnetic resonance spectroscopy, (3) the isotactic average chain length (N) is 500 or greater, and (4) the total amount of each of the fractions obtained by column separation of the xylene insolubles whose average chain length (N1) is 800 or greater accounts for 10 wt% or more of the entirety, and a method for its production, as well as a propylene-based polymer composition prepared by combining with this propylene-based polymer at least a nucleating agent in the range of 0.05-15 wt%. In addition, there are provided a polymerization catalyst component allowing the production of such a propylene-based polymer, and a method for its production.

Description

3 ^ 69〇9 The Ministry of Economic Affairs, Central Standard Falcon Bureau, Negative Work Consumer Cooperation Du Printed A7 B7 V. Description of the invention (1) The present invention relates to a physical property suitable for rigidity, surface hardness, heat resistance, steam vapour shielding, etc. The manufacturing method and composition of excellent propylene strip polymerization hips for autos, home appliances, and packaging materials, as well as the catalyst components for polymerization and their preparation methods. Propylene-based polymers generally make use of their cheap, ultra-fine properties such as transparency, mechanical strength, heat resistance, surface gloss, chemical resistance, oil resistance, bin resistance, and buckling fatigue resistance, and are widely used in Industrial materials / food packaging materials department, cosmetic packaging materials, first-class packaging materials, etc. As mentioned above, the propylene polymer SS is based on its rigidity, impact resistance, etc., and is widely used in various industries such as automatic vehicles, household appliances, and grocery. Recently, in order to reduce the weight or price of products, to reduce the thickness of products or to prevent scratches on the surface of products, studies have been conducted to improve the surface hardness of products. That is, the propylene-based polymer rancidity is required to have high rigidity, high surface hardness, and excellent impact resistance. In addition, the requirements for physical properties and workability are gradually being improved. In particular, there is a strong desire to improve the retention of rigidity and strength at high temperatures,-durability, and moldability of large molded products. In the past, the well-known methods of high rigidity or transparency improvement and surface gloss improvement of propylene-based polymers include: la and Ila group metal salts of monocarboxylic acids (such as sodium benzoate) and dicarboxylic acids ( Adipic acid), Group III ~ IV metal salts of aliphatic dicarboxylic acids (such as aluminum adipic acid), dibenzylidene glucose fermentation derivatives, talc and other fillers as a nucleating agent method (special public Zhao 39 -1809, JP-A 60-139731, etc.),-or, a method of increasing the molecular weight distribution of propylene-based polymerization® (JP-A 56-2307, JP-A 59-1 7 2507 , Special Open 62- 1 95007 The standard of this paper is the general Chinese National Standard (CNS) Λ4 present format (210X 297mm) (please read the precautions on the back before filling in this page)

.tT 3169Q9 A7 _____B7_ V. Description of the Invention (Gazette No. 2), etc.). However, when these nucleating agents are used *, although they have the effect of improving the aforementioned physical properties, * the use cannot be said to be sufficiently sufficient. Therefore, it is used in a propylene-based polymer with excellent mechanical strength, surface hardness, and heat radiance, such as blasting impact resistance, rigidity, etc., propylene polymer for packaging materials, packaging materials, and the like. Product density and thin the product. In addition, efforts to improve the stereotacticity of propylene-based polymers * or, to broaden the molecular weight distribution, depend on the strength of the high molecular weight distribution, improve durability, and improve the moldability of extrusion molding or hollow molding are also supported. With. Among them, in particular, the development of catalysts with high activity and high stereoregularity are also under review in recent years. Either way, it reveals a solid 18 catalyst component containing magnesium, titanium, halogen, and electron-donating compounds as essential components, and a catalyst system composed of aluminum, electron-donating compounds, for example: Tekai Sho ' 57-63310, Special Open 58-32604, Special Open 58-83006, Special Open 59-206408, Special Open 59-21931 1, Special Open 60-130607, Special Open 6b 209207, Special Open 6 Bu 2 1 1309, JP-A 62-72702, JP-A Zhao Ministry of Economic Affairs, Central Bureau of Economic Development, Male Workers' Consumer Cooperative Printed (Please read the precautions on the back before filling this page) 62-104811, JP-62 1 1705, Tekai Sho 63-199703, Tekai Sho 63-264609, Tekai Hei 1-126306, Tekai Hei 1-311106, Tekai Hei 3-62805, Tekai Hei 3-707 10, Tekai Hei 4-103604, Tekai Hei 4-114009, Japanese Unexamined Patent Publication No. 4-2025Q5. -In addition, the inventors have also recently disclosed in JP 4-434Q7, JP 4-1-1492 17, JP 4-178 406, JP 4-180 903, JP 4-Heihe Country for Taizhi Ruchi. Kneading m (CNS) A4 specification (210X 297 bomb) 3ί6 & 〇9 Ministry of Economic Affairs Central Falcon Bureau employee consumer cooperative printed Α7 Β7 5. Invention description (3) 185613, Tekai 4-198202, Telu 4- 198204, JP-A 5-9209, JP-A 5-287019, etc. The propylene-based polymerized xylenes disclosed in these prior documents extracted less than 99% of the insoluble content, and the methyl cis quintuple of polypropylene determined by nuclear magnetic resonance spectroscopy (hereinafter referred to as -NMR) The fraction is as high as 93 ~ 98%. • It has limits on improving physical properties such as rigidity and heat resistance. An object of the present invention is to provide a propylene strip for an automobile, household goods, and packaging materials that is excellent in physical properties such as rigidity, surface hardness, heat resistance, and water vapor barrier properties without compromising the original properties of a propylene-based polymer. Polymeric hip, its manufacturing method and composition Μ, polymerization agent components and its preparation method. After reviewing various methods for solving the aforementioned problems, the present inventors found that it is possible to bury it with a propylene-based polymer, and the total of its fractions is more than 10% by weight of the whole * and this partial composition (1) 25¾ 之 二甲 笨-The insoluble fraction (XI) is extracted above 99.0% by weight; (2) The isotactic pent ad fraction (IP) measured by nuclear magnetic resonance spectroscopy is 98.98; ( 3) The average length of Shunlian (N) is more than 500; and (4) The average chain length of each part of the xylene-insoluble fraction measured by the column method is 800 or more to solve the aforementioned problems To complete the present invention. The specific description of the propylene polymer of the present invention will be described below. (1) Xylene extraction insoluble fraction (XI) is the weight% of the polymer insoluble in 25t of xylene-specifically, it is the polymerization that precipitates at 25Ό once it is temporarily dissolved in o-xylene at 135Ό Zhao's weight%. The present invention (please read the precautions on the back before filling in this page). The water-based paper size is applicable to the Chinese National Standard (CNS) Λ4 specification (210X297 mm) 316 ^ 09 Ministry of Economic Affairs Chongyang Standard Falcon Bureau Consumption A7 B7 printed by the cooperative. V. Description of the invention (4) The XI of the propylene polymer is 99.0%, preferably 99.5% M, more preferably 99.7% M. If XI is less than 39.0%, the desired rigidity, heat resistance, surface hardness, surface gloss, transparency, water vapor barrier properties, etc. are insufficient. (2) Of the polypropylene molecules measured by the so-called K13C nuclear magnetic resonance spectroscopy The rate of quintuple component (hereinafter, sometimes referred to as IP) is determined by the method of A. Zambelli, Macromolecules, 925 (1 973). That is, the nuclear magnetic resonance spectrum (13 C-NMR) measured by isotope carbon is used to determine the fraction of the same row of quintet units in the propylene silicate polymer. In addition, the IP of the present invention is based on the measured value of polypropylene itself obtained by polymerization, not the measured value of polypropylene after the aforementioned xylene extraction, other extraction, and separation. Spectral peaks are based on the modified version of the aforementioned document described in Macronocules, & 687 (1975). The M-quot; C-NMR spectrum has an intensity score of ββββ in the -full absorption peak of the methyl carbon region Rate to determine IP. -The IP of the propylene-based polymer buried in this way must be 98.0% or more. If it is lower than this value, the rigidity, heat resistance, surface hardness, surface gloss, transparency, water vapor barrier properties, etc. will be insufficient. Preferably, the IP in the propylene polymer is 98.5% or more. In particular, the propylene shit polymer with an IP of 99. Q% K is even better. (3) The so-called average ray length (10 is the average chain length of Shuncong of the methyl group in the polypropylene molecule, according to the method reported by J.C. Randall (~ Polymer Sequence Distribution, Academic Press, New

York 1 977, chapter2) calculated. The size of this paper adopts the Chinese National Standard (CNS) A4 format (210X297mm) (Please read the precautions on the back before filling this page)

、 -IT 316909 A7 B7 V. Description of the invention (5), specifically, the polypropylene is heated to 130Ό and dissolved in the mixed solvent of 1,2,4-trichlorobenzene / heavy benzene K to make the polymer dehydrated 10% by weight. This solution was put into a glass sample tube with an inner diameter of 1OBB0, and M was measured by the same C-NMR as the measurement conditions of the quintuple component ratio (IP) previously followed. "Shan-Nong ZHU, Xiao-Zhen YANG, Riichiro CHUJO; Polymer Journal, vol.15, No.12, P859-868 (1983), the 2-side horizontal definition, that is, assuming that the active point during polymerization is 2 Kind. One of them is catalyst-controlled polymerization and the other is terminal-controlled polymerization. [The catalyst-controlled polymerization and terminal-controlled polymerization have been described in detail in Junji Furukawa; Essence of Polymer and Title 2, "Polymer Synthesis" , P73, Chemical Co., Ltd. (1986)]. The two-sided model can be organized as follows: ot: D-body and L-body are added to the end of the polymerization end of the catalyst-dominated polymerization (enanthiomorphic process), that is, the degree of chaos in the aiming component-refers to-σ: same as The end dominates the middle of the bonus

Ueso) The rate of achievement ω: the probability of the ct side. The Ministry of Economic Affairs Central Bureau of Accreditation and Employee's Consumer Cooperative Printed 51 (please read the precautions on the back before filling in this page). The three-dimensional regularity of the polypropylene is K The group unit is split into 10 spectral peaks. However, in order to make the actual measured value coincide with the calculated intensity (face millet), the minimum self-multiplication of M finds α, σ * ω, and each quintet unit is obtained according to the following formula The amount A »~) U. . This paper uses the Chinese National Standard (CNS) A4 specifications (2 丨 0 X 297 mm) Α7 Β7 5. Description of the invention (6) Intermediate hip At = HBim = ω (1-5 ^ + 5/9 *) + ^-ω ^ σ Aa = π pass βγ = ω (2/3 — 6/9 a) + 2 (1-ω) σ (I-σ) A3 = rmnr = ω; 9 * + (1-ω) σ * (1-0 ^ racemic structure A4 = Bnrr = ω (2y8-6; S a) + 2U- ω) σ ^ (1-σ) a Αβ = amri = ζω β Λ + 1 {\-ω ) 〇3 σ ^ Α6 = rinrr = 2ω / 3 * + 2 (1—ω) σ (1—σ) 3 Α? = Rmrffl = 2ω / 38 + 2 (1 — < y) cra (l_ < 7) * Αβ = γγγγ = ω β Β + 2 (1— ω) (1 " σ Α3 = βιγγγ = 2ω / 93 + 2 (1- ω) σ (I- J) 3 At〇 = mmn = ω (β-3 / 3a) + (l- < y) aa (l- σ) 8 * β = a (1- α) (please read the precautions on the back before filling in this page) Install • 1Τ Ministry of Economics Central Falcon Bureau Printed by the Industrial and Consumer Cooperatives, followed by the definition of the average bond length (N) described in the aforementioned JC Randall document Ν = the number of intermediates / the number of units of the intermediate marrow apply the quintuple of Ai ~ Ar obtained above The military position can be obtained according to the following formula.

Ai + Aa + A3 + 0.5 (Α4 + Αβ + Αβ + A?) Ν =-0.5 (Α '+ Αβ + Αβ + Ατ) In addition, the N value of the present invention is the measured value of the polypropylene itself obtained by polymerization, It is not the measured value of polypropylene after applying the aforementioned xylene extraction, other extraction, separation, etc. In the highly stereoregular propylene polymer of the present invention, N is 5QQ or more, preferably 7Q0 or more, especially K80QM. If H is less than 500, the desired clarity and heat resistance are insufficient. This paper scale is applicable to the Chinese National Standard (CNS) Λ4 specification (2 丨 0X297mm) A7 B7____ printed by the Employee Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs V. Invention description (7) Generally, the l3C-NMR signal of polypropylene is sub-Asian Obtained three main peaks such as methyl, methine, and methyl. Among them, if the spectrum peak of the methyl region is enlarged, the integrated form such as the number of the first country > rT... Nmmnirininina...> NmiiDiniiiinrriiDinfliin .. can be obtained. The average row length of the same row that can be crystallized can be considered to be the number of incomplete bonds and the reciprocal knot system. The greater the number of irregular bonds, that is, the more racemic structures cut off the MB1B structure, the shorter the average bond length (N). The average bond length (U) obtained in this way indicates the sequence length of the crystallizable tandem structure as described above, so the longer the length (ie, the less the irregular bonding), the higher the rigidity of the propylene polymer or Physical properties such as heat resistance and water vapor barrier properties. (4) The average length of each fraction (M, measured by the so-called column separation method of xylene insoluble fraction) (M, which is obtained by (1) at the death of 130-the xylene extracts the insoluble fraction of poly Propylene is dissolved in p-xylene, plutonium silica is added, and the temperature is reduced to 3010 at a cooling rate of 10〇 / hour, so that it is deposited on the plutonium silica, and this is filled in the column. The temperature is raised to 1301C, and partial groups are obtained by fractional distillation. The average length (N) of each partial group obtained by subdivision is obtained by the previous method, and this is taken as the average length (Nf) of the partial sisters. In the propylene-based polymer of the invention, the total chain length (I) of each fraction-group obtained by fractionation is 8Q0 or more, and the total is preferably 10% by weight or more, preferably 30%. More than 50% by weight, especially 50 sheets of paper. The Chinese National Standard (CNS) Λ4 specification (210X297mm) is applicable. 10 (Please read the precautions on the back before filling this page)

* 1T ui6S〇9 A7 _B7____ 5. Description of the invention (8) It is better that the weight is higher than Μ. If the average bond length (Nf) is 800 Μ or more, if the total weight is less than 10% by weight, the rigidity, surface hardness, thermal conductivity, and water vapor barrier properties are insufficient and the effect is not good. Next, the method for producing the propylene polymer of the present invention will be explained. The propylene-based polymer of the present invention can be obtained by using a solid catalyst component for (Α) polymerization, which is an M magnesium compound, a titanium compound, a halogen compound, and the first electron-donating compound as essential components, and The mole ratio (D / T) of the first donation compound (D) and titanium (Τ) held in the catalyst component is D / T21; (B) Aluminium compound; (C) The polymerization catalyst composed of the second electron-donating compound, K, is produced by polymerizing propylene. Here, the magnesium compound may be exemplified by magnesium halides such as magnesium oxychloride, magnesium bromide, magnesium sulfide; such as dimethoxymagnesium, diethoxymagnesium, dipropoxymagnesium, dibutoxymagnesium, Magnesium alkoxides of phenoxymagnesium; such as magnesium laurate, magnesium stearate, and magnesium carboxylate; such as dimethylmagnesium, diethoxymagnesium, and butylethyl, Ministry of Economic Affairs Magnesium alkyl magnesium is printed by consumer cooperatives. In addition, these various magnesium compounds may be used alone or in combination. It is preferable to use magnesium halide, magnesium alkoxide, or those that form magnesium halide when the catalyst is formed. In particular, the aforementioned halogen is preferably an atmosphere. Titanium compounds can be exemplified by titanium halides such as titanium tetrachloride, titanium trichloride, titanium tetrahydride, and titanium iodide; such as titanium tetramethoxy, tetraethoxy Titanium, tetrapropyl-oxytitanium, tetrabutoxytitanium, tetraphenoxytitanium alkoxide; ethoxylated titanium chloride, titanium butoxylate, titanium phenoxylate, titanium dioxide Titanium butoxide, 11 (please read "Notes on the back before filling in this page"). The paper size is applicable to the Chinese National Standard (CNS) Λ4 present grid (210X 297mm) Printed by the Employee Consumer Cooperative of the Central Bureau of Economics, Ministry of Economic Affairs A7 B7 V. Description of the invention (9) Gasified tributoxy titanium halogenated titanium alkoxide, etc. In addition, these various titanium compounds can be used in one kind of military martial arts, and can also be used in combination on 2 ° K. The most preferred are tetravalent titanium compounds containing halogens, especially K-aerosol. The halogen-containing compound is halogen, which is fluorine, atmosphere, desert, or iodine, preferably gas. In fact, the compounds with hips exemplified are dependent on the catalyst composition modulation method, but can be exemplified by titanium tetrachloride, tetrabromide Titanium halides, silicon tetrachloride, silicon tetrabromide and other silicon halides, phosphorus trichloride, phosphorus pentachloride, phosphorus halides', but the catalyst composition modulation method can also use halogenated hydrocarbons, halogen molecules , Halogenated hydrogen acid. The first No.1 donation compound can generally be exemplified by oxygen-containing compounds, nitrogen-containing compounds, phosphorus-containing compounds, carbon-containing compounds, etc. Examples of oxygen-containing compounds include enzymes, ethers, esters, acid halides, and acid anhydrides. More specific examples can be given: such as formazan, ethylenzyme, propanol, butanol, pentanoenzyme, hexacycline, heptanozyme, caprylic enzyme, nonanol, decanolytic enzyme, 2-ethylenzyme, oleaginous enzyme, benzylase Phenylethyl yeast, phenol, cresol, ethyl phenol, naphthalene yeast; such as methyl ether, ethyl chain, propyl ether, butyl ether, pentyl ether, hexyl ether, tetrahydrofuran, anisole, diphenyl ether Ethers or diethers; such as ethyl acetate, ethyl acetate, ethyl propionate, ethyl ester, ethyl acrylate, ethyl crotonate, ethyl oleate, ethyl stearate, phenyl Ethyl acetate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, butyl phenylacetate, methyl ethyl benzoate, methyl anisate, ethyl anise, ethoxy Benzoic acid methyl alcohol, ethoxybenzoic acid ethyl ester, ethyl silicic acid ethyl ester, dimethyl peptidoate, diethyl phthalate, dipropyl phthalate, di-n-butyl phthalate, diisobutyl peptidate Ester, peptide acid dihexanone, peptide acid paper paper scales are applicable to China National Standard (C: NS) Λ4 specifications (210X297mm) -12 _ (please read the precautions on the back before filling in Page) Binding. Order 316 & 09 A7 B7_ V. Description of the invention (1Q) Dioctyl ester, butyrolactone, δ-valerolactone, ethylene carbonate esters; such as acetic acid atmosphere, benzoic acid atmosphere, benzene Acid atmospheres of ethyl atmosphere and phthalic acid chloride; such as maleic anhydride and anhydride of phthalic anhydride. In addition, these first electron-donating compounds may be used alone or in combination of two or more. M esters are preferred, especially phthalate esters. Of course, among the four compounds of magnesium compound, titanium compound, halogen compound, and the first electron-donating compound, * 1 compound can be used for 2 kinds of M. The use of the aforementioned components may be any as long as the effect can be exhibited in the present invention, but the following ranges are generally preferred. The use amount of the titanium compound is in the range of 0.0001 to 1000, and preferably in the range of K0.01 to 100, with respect to the use of the magnesium compound for the use of the ear-energy ratio. Halogen compounds can be used as needed. When using halogen compounds, the amount of titanium compound used does not change depending on whether the titanium compound or magnesium compound contains no halogen. The amount of titanium compound used relative to the amount of magnesium used is Within 0.01 ~ 1000 of the Ministry of Economics Central Bureau of Standards and Staff Employee Cooperative Printed in the Fan Garden, M 0.1 ~ 10 0 is better. The use of the No. 1 難 子 donor compound is higher in the range of Q.001 to 10, and more preferably in the range of 0.01 to 5, relative to the use of the magnesium compound. The method for preparing the solid catalyst component used in the present invention is a method for adjusting the known solid catalyst component using K. That is, the magnesium compound, the compound, and the first electron are supplied at once or in stages. It is obtained by contacting with sexual compounds-and then auxiliaries such as halogen-containing compounds as needed. 13 (Please read the precautions on the back before filling in this page) This paper scale is applicable to the Chinese National Standard (CNS) Α4 specification (210Χ 297 mm) A7 B7_ printed by the Consumer Cooperative of the Central Falcon Bureau of the Ministry of Economic Affairs 11) Specific examples of known methods include the following modulation methods. (1) A method of contacting magnesium halide and the first electron-donating compound and titanium compound as required. (2) A method of bringing a titanium halide compound and / or a silicon halogen compound into contact with a solid component obtained by contacting a magnesium halide with titanium tetraalkoxy and a specific polysilicon compound. (3) A method of contacting a titanium compound with a solid component which is dissolved by a tetraalkoxy titanium and a first electron-donating compound to dissolve the magnesium compound and is precipitated by a halogenating agent or a titanium halide compound . (4) A method of treating aluminum oxide and magnesium oxide with a phosphorus halide compound, and contacting the magnesium halide, the first electron-donating compound, and the halide compound. _ (5) A method of contacting the first electron-donating compound with a titanium compound after allowing a representative Grignard reagent of an organomagnesium compound to react with a Siam reagent or a halogenating agent. -(6) A method of contacting the halogenating agent and / or the titanium compound with the magnesium alkoxide compound in the presence or absence of the first electron-donating compound. (7) Dissolve the magnesium compound with titanium tetraalkoxy titanium, and then polymerize the silicon compound with the silicon compound. Method of treatment with silicon halide compound and aurant compound 0 (8) The first electron donor compound and the first A method for treating spherical magnesium compounds / fermented complexes such as titanium halide compounds. -In order to produce the propylene polymer of the present invention, any one of the above solid catalyst component preparation methods can also be used. * At least one must be supported on the size of the solid paper. The Chinese National Standard (CNS) A4 specification (210X 297 Mm) 14 -------------- IT ------ ^ Feng (please read the precautions on the back before filling in this I) 3i6S〇9 A7 B7 5. Description of the invention ( 12) The first molar donor compound / titanium atom-containing molar ratio (D / T) of the first catalyst component of the catalyst component is the polymerization catalyst component of D / T containing 1. In this case, D / T3 1.5 is even better. When D / T < 1, it is difficult to obtain the highly regular regular propylene polymerization of the present invention ». In this way, according to the present invention, a solid catalyst component for α-olefin polymerization can be provided. It contains magnesium compound, titanium compound, halogen compound and the first electron-donating compound as essential components, and a solid SS catalyst The mole ratio (D / T) of the first electron-donating compound (D) and titanium (Τ) held in the composition is D / T21. In addition, this solid catalyst component is used to develop high stereoregular high polypropylene manufacturing users. However, it can also be used as a general propylene polymer or a propylene polymer other than α-olefin general polymerization solid Catalyst ingredients. In particular, KD / T2 1.5 is preferable in order to obtain a propylene-based polymer with high three-dimensional regularity, high heat resistance, and heat resistance. In addition, in the conventional modulation method, even if it is a solid Zhao catalyst component that does not satisfy the above condition (-D / T2 1), further processing as shown below can improve the solid catalyst component that satisfies the above condition • Better. Printed by the Employee Consumer Cooperative of the Central Standard Falcon Bureau of the Ministry of Economic Affairs. At this time, the first ratio of the donor compound / Ti atomic content (Ti / T) of the solid catalyst component before the improvement and the improved catalyst component The first electron donating compound / Ti atom content in the ear ratio (D / T) »· must be in the (D / T) n / (D / T),> 1 Kan system, if it is (D / T) ) · »/ (D / Th έ 2 is better.-For example, the composition of Gu Zhao catalyst prepared by the above-mentioned various well-known methods is magnesium, 竑, halogen and the first electron donating compound as essential components 15 (Please read the precautions on the back before filling in this page) This paper is generally compliant with the Chinese National Standard Falcon (CNS) Λ4 specification (210X297mm) Printed by the Ministry of Economic Affairs, Central Bureau of Standardization, Beigong Consumer Cooperative A7 _B7_ V. Description of invention ( 13) Furthermore, further treatment with the first electron-donating compound and / or dentin-containing compound can increase the D / T than before the treatment and improve the catalyst. K The first electron-donating compound is subjected to temperature And there is no limit to the order and frequency of treatment with halogen compounds. However, the general treatment method for solid catalyst components is After the treatment with the donor compound, the K contains halogen compound treatment, and then the K hydrocarbon is washed. The first electron donor compound used in the catalyst composition improvement may be the same or different Used in the preparation of solid catalyst components before improvement. The first electron-donating compound can be used alone, or it can be used together with 2 types of M. The preferred ones are esters * the most preferred ones are peptides. Acid esters. The use of the first electron-donating compound can be in the range of 0.001 to 500 times the ear of the titanium atom in the solid medium component, preferably in the range of 0.01 to 50 moles. When the amount of the first donor compound is extremely small, it is difficult to obtain and obtain the (D / T) »/ (D / Th> 1) Kang system, on the contrary, the first electron donor-and-sex compound When the amount of use is extremely large | Because the polymerization activity is reduced, it is not good. The halogen-containing compound used for catalyst improvement can be the same or different from the user when the solid catalyst component before modification is prepared. Among them, titanium halide, Halogenated silicon and halogenated hydrocarbons are preferred. Halogen-containing compounds can be used alone It can be used in combination of two or more types. The amount of halogen-containing compound used is in the range of 0.1 to 10,000 molar ratio relative to the titanium atom in the solid catalyst component, preferably 1 to 3000 molar ratio-range , It is better to be in the range of 5 to 500 Gum ratio. In addition, when the amount of halogen-containing compounds used is very small * It is difficult to obtain (D / T) »/ (D / Th> 1) This paper scale is applicable to Chinese national standards (CNS) A4 specification (210 X 297 mm) -16- -------- ^ ^ ------ 1T ------ ^ ^ * (Please read the notes on the back first (Fill in this page) A7 B7_ V. Description of the invention (14) Conversely, when the amount of halogen-containing compounds used is extremely large, the polymerization activity will decrease and the amount of waste liquid will increase, which is not good. For improvement, the temperature of the solid catalyst component treated with the No. 1 Xiaozi donor compound is -3 0 ~ 150X3, preferably 0 ~ 100¾. In addition, the temperature of the solid catalyst component treated with a halogen-containing compound is 0 to 200 ° • preferably 50 to 150 scoops. At other temperature conditions, the polymerization activity is lowered, which is not good. The first electron-donating compound and halogen-containing compound of the K solid catalyst component can be generally modified in a hydrocarbon solvent. The hydrocarbons used at this time are preferably aliphatic hydrocarbons such as pentane, hexane, heptane, octane, and decane; aromatic hydrocarbons such as benzene, toluene, and xylene are not Activated hydrocarbons. In addition, these hydrocarbons can be used as a cleaning solvent for the solid catalyst component treated with the first electron-donating compound and halogen-containing compound of the solid catalyst component. Improving olefin polymerization compound No. 1¾ of the solid catalyst component before the improvement-treatment, cleaning with halogen-containing compounds Improving olefin polymerization Catalyst printed by the Ministry of Economic Affairs Central Standards Bureau Employee's Consumer Cooperatives after the above hydrocarbon cleaning The temperature at the time is in the range of 0 ~, preferably 60 ~ 140¾. At this time, when the cleaning temperature is extremely low, it is difficult to obtain (D / T) ... / (D / ThSl's reed system, on the contrary, when the cleaning temperature is extremely high, although (D / T) »/ (D / T), > 1 of the Kan system, but the polymerization activity is lowered, so it is not good. If the solid catalyst component is treated with the first Xiaozi donor compound, if it is not-treated with a halogen-containing compound (washed) * polymerization The living room is very low *, and does not show the effect of the present invention. W halogenated compounds for processing 17 (please read the precautions on the back before filling in this page) The paper scale is applicable to China National Standard (CNS) A4 specifications ( 210X297mm) The A7 B7 printed by the Negative Consumers Cooperative of the Central Bureau of Economic Affairs of the Ministry of Economic Affairs 5. The number of invention descriptions (15) (washing) is not particularly limited. 4 times is better. When Ml times, the effect of the present invention cannot be fully exhibited * If the number of repetitions is too large, the polymerization activity is lowered and not good. Also • In the present invention • The first electron-donating compound uses the general formula TiXa k (where · Χ is a halogen atom of Cl, Br, I, a is 3 or 4, Y is a donating compound (1) QSb3) The titanium compound represented by 3), after being supported by this treatment, M halogen compounds are washed and then M hydrocarbons are washed, which can be improved to support a solid content of D / T containing 1 In this way, when treating the solid and strong catalyst component with the first electron-donating compound, in general, the number of treatments (washing) with the halogen-containing compound of the present invention must be at least 2 as described above, but use In the case of TiXa · Yb, the number of treatments (washing) of M halogen-containing compounds is 1 or 2, and the effect of the present invention can be fully exhibited. In addition, as described later, the amount of halogen-containing compounds used can also be reduced The amount of waste liquid discharged when the hydrogen compound is washed with an improved solid catalyst component can also be greatly reduced. — TiXa (where X is a halogen atom of Cl, Br, I, and a is 3 or 4) Recorded in RSP Coutts, PC Wailes, Advan. Organometal. Chem ·, 9_, 135 (1 970), 4th edition of New Experimental Chemistry Lecture 17 No complex complexes · Hetero complex complex hips Japan Chemical Shewan Maru (1991) p. 35, HK Kakkoen, J. Pursiainen, TA Pkkanen, M. Ahlgren, B. Iiskola, J. Organomet. 1 7 5 (1 99 3), etc., commonly known as Dianzi donor compounds-known to easily form complexes.

TiU_ Yv ^ X is a halogen atom of Cl, Br «, I, of which KC1 is the paper standard applicable to the Chinese National Standard (CNS) Λ4 present grid (210X297mm) (please read the precautions on the back before filling this page) 袈·

.1T 18 Printed by the Employees ’Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs A7 B7 V. Invention Instructions (16) Good. a is 3 or 4, but K4 is better. Y (the first electron-donating compound) can be selected from the aforementioned ones. It may also be the same or different from that used when the catalyst composition of the pre-improving solid medullary is modulated. In the preparation of TiXa · ¥ ^, the first 難 子 donor compound can be used alone, or it can be used together with 2 types of M. The preferred ones are organic acid esters, and the most preferred are peptide acid esters. Υ's b is when the aforementioned a is 3, it is 0 < b ≦ 3, when a is 4, it is 0 < b each 2, the Y when the TiXa · Yb is modulated relative to the feeding ratio of TiXa is based on Y The number of electron donor bases and the atomic valence of Ti depend. The best situation is when b is 1 when a is 4.

The amount of TiXa · 7 > »is in the range of 0.0Q1 ~ 500 to the ratio of titanium atoms in the solid catalyst component before the improvement, preferably in the range of 0.01 to 50 molar ratio, especially preferred Fan Gunet is 0.1 ~ 10 mole. In addition, when the amount of TiXa · is very small, it is difficult to obtain the relationship of (D / T) »/ (D / T),> 1. Conversely, when the amount of TiXa · Yb2 is extremely large, the polymerization activity is reduced, which is not good . -The amount of halogen-containing compounds used is within the range of 0.1 ~ 1QQQ molar ratio relative to the titanium atom in the solid catalyst, preferably within the range of 1 ~ 500 molar ratio, especially 5 ~ 10 0Qi Compared to the Fanpu. Also, the selection of the halogen-containing compound may be the same as described above. In addition, the temperature of the solid catalyst component treated with TiXa · Yb may be the same as the treatment temperature of the aforementioned first electron-donating compound. * The temperature of the MH halogen-containing compound cleaning solid catalyst component may also be the same as described above . -Treatment with TiXa · Yb of solid pollinating media components · Washing of halogen-containing compounds can also be carried out in the same way as the above-mentioned electronic donating compounds for the first paper is applicable to the Chinese national standard (CNS) Λ4 specifications (210Χ 297 mm) 19 (Please read the precautions on the back before filling out this page) _ _, 1Τ 316909 Α7 Β7 Employee Consumer Cooperation of the Central Bureau of Standards of the Ministry of Economic Affairs • Printed by the company V. Description of invention (17) Treatment and M halogenated compounds Wash it. The following TiXa · Υ-the number of treatments and the number of times of washing with halogen-containing compounds are not particularly limited, but, as mentioned above * If MTiXa · Yb treatment, the M halogen-containing compound is washed once or even twice * The effect can be fully demonstrated. When the M-containing halogen compound is not washed, the high performance obtained in the present invention cannot be obtained. The improved solid catalyst component prepared by the above method can be used in the polymerization of propylene by combining the later-mentioned aluminum compound and the second Xiaozi donor compound, but it can be prepared before polymerization A small amount of single hip. In general, the modified solid catalyst component prepared is about 0.01 g to about 1000 g per lg, and the temperature for preliminary polymerization is arbitrary, but K-30 ~ is preferable. The preliminary polymerization is usually carried out in the coexistence of the organoaluminum compound used in the polymerization described later and the second electron-donating compound. Preparative polymerization is generally marinated in inactive hydrocarbon solvents, but can also be carried out in liquid military bodies-and gas-phase single hips. In addition to propylene, monomers used in preliminary polymerization can also be used: ethylene, 1-butene, 3-methyl-1-butene, 3-methyl-1-pentene, 4-methyl-1- Ot-olefins such as pentene, 4,4-dimethyl-1-pentene, vinylcyclopentane, vinylcyclohexane, styrene derivatives such as styrene, α-methylstyrene, Trienes such as butadiene and 1,9-decadiene, and allyl trialkyl silanes. Moreover, not only one type of these monomers, but also two or more types may be used or mixed. In addition, hydrogen may be used as a molecular weight regulator during preliminary polymerization. (Please read the precautions on the back before filling out this page) Bound paper paper standard Universal Chinese National Standard (CNS) Μ specification (2l0x 297 gala) 20 V. Description of invention (18) A7 B7 Male worker, Central Bureau of Standards, Ministry of Economic Affairs The consumer cooperative printed the propylene polymerization. The above-mentioned improved solid catalyst component can polymerize the propylene polymer under the coexistence of the aluminum compound and the second electron-donating compound. Representative examples of organoaluminum compounds used in the present invention can be exemplified by: trimethylaluminum, triethylaluminum, tripropylaluminum, tributylaluminum, trihexylaluminum, trioctylaluminum, and trialkylaluminum; Such as dimethyl aluminum hydride, diethyl aluminum hydride, alkyl aluminum hydride of dibutyl aluminum hydride; such as dimethyl aluminum hydride, diethyl aluminum hydride, diethyl aluminum bromide, Alkyl aluminum halides such as ethyl aluminum semi-halogenated compounds; such as alkyl aluminum alkoxides such as diethyl aluminum ethyl acetate M, diethyl aluminum aluminum phenol lithium, etc .; such as methyl aluminoxane, ethyl aluminoxane, Propyl aluminoxane, aluminoxane. In addition, these aluminum compounds can be used alone or in combination of two or more. It is preferably triethylaluminum. The second electron-donating compound used in the present invention may be the same as or different from the first electron-donating compound. However, typical examples include aromatic carboxylate compounds and Si-0. -C or Si-NC silicon compounds, acetal compounds, gallium compounds with Ge-QC bonds, heterocyclic compounds of nitrogen or oxygen with alkyl substituents. Specific examples of these compounds can be exemplified by aromatic carboxylic acids such as ethyl benzoate, ethyl p-toluate, and ethyl p-anisate; such as phenyltrimethoxysilane and diphenylmethoxysilane , Dibenzylmethanyl silane, di-n-propyl dimethoxy silane, diisopropyl dimethoxy silane, di third butyl dimethoxy silane, dicyclohexyl dimethoxy silane, di Cyclopentyldimethoxysilane, cyclohexylmethyldimethoxysilane, tert-butyltrimethoxysilane, cyclohexyltrimethoxysilane, hexyltrimethoxysilane, tetramethoxy (please read the back first (Notes to fill out this page)

, 1T i This paper scale is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm). 21 Printed 3l6y〇g A7 _B7_ by the Central Standard Falcon Bureau Employee Consumer Cooperative of the Ministry of Economic Affairs. 5. Description of the invention (19) Silane, tetraethoxy Silicon compound of silane; benzophenone dimethyl gas base Xue Xue, benzophenone diethoxy acetal, acetophenone dimethoxy acetal, acetophenone diethoxy diethoxy acetal Acetal compounds; such as diphenyldimethoxyxane, phenyltriethoxygermane compounds; such as 2,2,6,6-tetramethylhexahydropyridine heterocyclic compounds. In addition, these electron-donating compounds may be used in one kind of army, or may be used together in two or more kinds. It is preferably a silicon compound or an acetal compound, and particularly preferably a silicon compound having a Si-0-C bond. The polymerization method in the production method of the present invention is not particularly limited, and a well-known method can be used. In addition to the liquid phase polymerization method of slurry polymerization or bulk polymerization, the gas phase polymerization method can also be used. In addition, not only batch polymerization, but also the method of link polymerization and split polymerization. The polymerization solvent at the time of slurry polymerization can be used alone or mixed with saturated aliphatic or aromatic hydrocarbons such as hexane, heptane, cyclohexane, toluene and the like. In addition, the polymerization method of the production method of the present invention can also use multi-stage polymerization of two or more polymerization reactors. -The polymerization temperature is about -50 ~ 2Q0, M 20 ~ 150t! Is better, the polymerization pressure is atmospheric pressure ~ 100 kg / cna G, preferably 3 ~ 50 kg / cn * G. In addition, the addition of hydrogen equivalent during polymerization can determine the molecular weight. Also in the production method of the present invention, in addition to the separate polymerization of propylene, propylene and hydrocarbon residues of the general formula R-CH = CHa (R is a hydrogen atom or ~ %%) can also be used as a branch The α-olefin represented by the group) is copolymerized together. Specific examples include ethylene, butene, 3-methyl-1-butene, 3-methyl-1-pentene, 4-methyl-1-pentene, and 4,4-dimethylene. S-1-pentene, vinyl cyclopentane, vinyl sulfonate, etc. In addition, it can be exemplified that the paper standard of styrene paper is applicable to the Chinese National Standard (CNS) Λ4 specification (2 丨 0X 297mm) 22 (please read the precautions on the back before filling in this page). 316909 A7 B7__ 5. Invention Description (20), styrene derivatives such as ct-methylstyrene, butadiene, 1,5-hexadiene, 1,7-octadiene, 1,9-decadiene and other dienes , Allyl alkyl silanes. In addition, these types of single Zhao can be used alone or in combination of two or more. Also, in the propylene polymer of the present invention, the propylene-ethylene block copolymer can be produced by multi-stage polymerization of two or more M-polymerized reactors. In particular, the production of military polypropylene in the first stage is preferred. At this time, if the military polypropylene taken out after the polymerization of the first stage is completed satisfies the constitutional requirements of the present invention, the copolymer obtained finally may also have the physical properties obtained by solving Class S of the present invention. Furthermore, the propylene-based polymer hip obtained in the present invention can be thinned by adding a well-known nucleating agent, K, to obtain a resin composition that further improves crystallinity and high-speed moldability. Examples of the nucleating agent include: I of monocarboxylic acid, and M of Ila group Jinji (such as sodium benzoate), dicarboxylic acid (adipic acid), and III-~ IV group of aliphatic dicarboxylic acid Jin Yizhi »(such as pt-butyl benzoic acid absolute M), dibenzylidene glucose fermentation derivatives, talc and other fillers. For example: 1,3,2,4-dibenzylidene glucosylase, 1,3,2, printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling this page) 4-di- (ρ-methylbenzylidene) glucose fermentation, 1,3,2,4-di- (ρ-ethylbenzylidene) glucose fermentation, 1,3, 2,4-di- (Ρ -Chlorobenzylidene) glucose fermentation, 1,3-P-chlorobenzylidene-2,4-ρ-methylbenzylidene glucose fermentation, nabutylphenyl) phosphate, sodium-2,2-methylene Methyl-bis- (4,4-di-t-butylphenyl-yl) phosphate_, sodium-2-2'-ethylene-bis (4,6-di-t-butylphenyl) phosphate Cool and other, and talc, calcium carbonate and other non-smooth fillers. This paper scale is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) -2 3-Printed by the National Standards Bureau of the Ministry of Economy, A7 B7 V. The invention description (21) The addition of these nucleating agents The amount is in the range of at least 0.05 to 15% by weight of the S nucleating agent in the propylene polymer. The effect of the present invention is very significant. M0.0 5 ~ 0.8 is better, especially adding 0.1 ~ 0.5 weight 1%. However, since the inorganic compound such as talc is smaller than the nucleating agent exemplified above, it can be added in an amount of 1 to 15% by weight. It is preferably 2 to 15% by weight, especially 5 to 10% by weight. As long as the propylene resin polymer or resin composition of the present invention is suitable for blending other additives used in thermoplastic resins within the scope not detrimental to the purpose of the present invention (for example, oxidation inhibitors, weather stabilizers, and inhibitors) , Slip agent, crimp inhibitor, anti-S agent, dye, oil, wax, etc.). For example: an example of such an additive, that is, the oxidation inhibitor is 2,5-di-t-butyloxin, 2,6-di-t-butyl-p-methyl cool, 4,4-sulfur-bis_ (6-t-butylphenol), 2,2-methylene-bis (4-methyl-6-t-butylphenol), octadecyl-3- (3 ', 5'-di-t -Butyl-1'-hydroxybenzyl) propionate, 4,4'-sulfur-bis (6-butylphenol), the ultraviolet absorbing agent is ethyl-2-cyano-3,3-one-two Phenyl acrylic acid_, 2- (2'-hydroxy-5-methylphenyl) phenyl azide, 2-hydroxy-4-octyl benzophenone, plasticizer is dimethyl peptidate, phthalic acid Diethyl ester, pantone, flowing stone relay, phosphate ester, charged inhibitor is monostearic acid, sorbitan monopalmitic acid, sulfated oleic acid, polyethoxylane, carbohydride, slip agent is ethylene Bistearic amine, butyl stearate, etc. • Colorants are carbon black, phthalocyanine, quinolidine, dihydrovaleroline, nitrogen-based pigments, oxidized iron, ferric oxide, etc., fillers For glass fiber, asbestos, mildew, silicate-calcium, aluminum silicate, etc. In addition, many other high molecular compounds can be mixed as long as the effects of the present invention are not impaired. The size of clothing paper is applicable to China National Standard Rate (CNS) Α4 specification (210X297mm) 24 (Please read the precautions on the back and then fill out this page) 装-* 1Τ 3! 69〇9 A7 B7 Fifth, invention description (22) (Please read the precautions on the back before filling in this page) The melt index of the propylene-based polymerization of the present invention (MFR ~ JIS-7210, Condition 14 in Table 1) is not particularly limited • It can be determined according to the molding method and use, However, a fan garden of 0.1 to 500 g / 10 points is usually appropriate. The propylene-based polymer of the present invention can be formed into injection-molded mantles, films, sheets, pipes, screws, etc. by the well-known melt-molding method and compression molding method, and can also be used as a military body and other materials. For example, such accumulation method uses dry accumulation adhesives such as polyurethane, polyester, etc., while laminating other heat in the single layer product of the propylene polymer or resin composition of the present invention The plastic resin layer, that is, K is called dry lamination forming method or Sandwitch lamination method, or co-extrusion lamination method, co-extrusion (feedblock method, multi-manifold ^ S), co-injection molding method, co-extrusion tube molding method. The multi-layer laminate II thus obtained is a method of reheating using a vacuum forming roll, a pressure forming roll, a stretch blow molding machine, etc., followed by a stretching operation, or | using a single-sleeve or double-sleeve stretcher for this multilayer laminate Or Juntong-the molding is heated and stretched. Brief description of the drawing Printed by the Employee Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economy Figure 1 is an example of the C-NMR spectrum of the methyl region of elemental polypropylene. Hereinafter, the present invention will be described in more detail with examples. Examples and the method and apparatus for measuring the physical property values in the present invention are shown below 0-(1) Dimethylbenzidine insoluble fraction (XI) 2.5 g of polymer is dissolved in 135C o-xylene (2 5 0 ml ) 25 This paper scale applies the Chinese National Standard (CNS> Λ4 specification (210X 297 mm) A7 B7 printed by the Employee Consumer Cooperative of the Central Bureau of Economics of the Ministry of Economic Affairs _ 5. In the description of invention (23), the aggregation precipitated at 25υ η (% by weight) as the insoluble part of dimethyl dibenzyl (XI). (2) The cis-component ratio (nmmin) of MDffl is the cis-position of the methyl quintet in the propylene-based polymer Zhao molecule. The joint fraction. The measurement is carried out using JNM-GSX400 (l3C NMR frequency 100 MHz) manufactured by JEOL Co., Ltd. The individual signals are attributed to A. Zaiabelli et al. Macromolecules, 13, 267 (1980) The measurement selection is shown below. Measurement mode (node): protron decoupling pulse width: 8.01ms pulse round-trip time: 3.0 tts Total times: 2QQG0 times solvent: 1,2,4-trichlorobenzene / heavy benzene Mixed solvent (7 5/25% by volume) Internal standard: Hexamethyldisilazane-Sample irrigation degree: 30 0 Measurement temperature of mg / 3.0 ml solvent: 120 (3) The average length of Shunlian (N) The average length of Shunlian (N) is based on the method reported by JC Rodall (Polymer Sequence Pistribution Academic Press, New York 1 977, Chapter 2) Calculated. Specifically, dissolve polypropylene in a mixture of 1,2,4-trichlorobenzene / heavy benzene, and heat to 130-π · to make the polymer concentration be 10% by weight Fill this solution into a test tube made of glass with an inner diameter of 10 mm 0, and apply the Chinese National Standard (CNS) Λ4 format (210X297mm) at the same size as this paper. 26 (Please read the precautions on the back first (Fill in this page) Pack. * 11 A7 B7 V. Description of the invention (24) The previous determination of the condition (IP) of the Shunlian Wuyuanjie fraction (IP) " C-NMR. Secondly, as previously explained, from the intermediate The number of bonds and the number of units of the intermediate are calculated according to the following definition to obtain the average chain length (N). N = the number of bonds of the intermediate / the number of units of the intermediate (4) The column method separates the xylene at a temperature of 13QO The propylene-based polymer of the vortex is dissolved in p-xylene, plutonium silica is placed, and the temperature is reduced to a cooling rate of 10 t: / time to 301, attach it to cerium silica. Fill this attachment in the column, and increase the temperature from 70¾ to 2.5¾ each time to 130¾, distill it into different parts and group. (5) For injection molding, use Toshiba Toki (unit) equipment IS-170FI (theoretical injection volume 250 cm3), at the molding temperature of 220 and the cooling temperature of the chess set 50 ¾, to prepare Izod impact test piece, bending elastic modulus test piece, Load flexible temperature test piece, surface gloss test piece (thickness 2 111 father 15 (: 111 father 11〇11 flat plate). Second-after the second painting night in a constant temperature room with a humidity of 50% and a temperature of 23t: Measure these physical properties. (6) Izod impact strength (notched) Printed by the Beigong Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling in this page). Implemented based on JIS K711Q. Device It uses the UF impact tester manufactured by Ueshima Manufacturing Co., Ltd. (7) Flexural modulus M JIS K7 2 0 3 is based on curing.-(8) Ethylene content is based on the l3C-HMR method reported by C, J. Carman et al. (Macromolecules, this paper scale is applicable to the Chinese National Standard (CNS) Λ4 specification (21 OX 297 mm) -27-A7 _B7_ V. Description of the invention (25) 10,537 (1977) Calculated. (9) MFR (melt Flow rate) MJIS K721D Table 1 Condition 14 is based on the implementation It is based on the melt index made by Bao (Share) Co., Ltd. (10) The load deflection temperature is based on the JIS K7 2Q7B method and is implemented using the HDT ε VSPT tester manufactured by Toyo Seiyu. (11) Rockwell surface hardness ΜTemperature 230t: Extrusion molding, to prepare a sample for measurement, using AR-10 Rockwell hardness tester made by Toyo Socks Co., Ltd. · MJIS K72Q2. (12) Yoshii Cut-off (Strand) 40 mm ΦΤ die film forming process, chessboard temperature 23QC, cooling temperature 30¾, drawing speed 10 π / min, made a 60-thick film, measuring water vapor transmission, Haze, surface-gloss (13) Haze, which is based on the MJIS K71Q5 method of the Employee Consumer Cooperative of the Central Prototype Bureau of the Ministry of Economic Affairs, is implemented using the Haze meter of the HGM-2D model manufactured by the Sigang Testing Machine (Co). (14) Surface gloss MJIS K7105 method Based on this, it was implemented using the gloss meter VG-1D manufactured by Nippon Denshoku Industries Co., Ltd.-(15) Based on the water vapor transmission rate MASTM-E96, using 28 manufactured by Modern Controls Inc. (please read the back Matters needing attention before filling this page) This paper The Zhang scale applies to the Chinese National Standard (CNS) Λ4 specification (210X 297mm) Printed by the Central Bureau of Economic Affairs of the Ministry of Economic Affairs Consumer Cooperative 316909 A7 B7 V. Description of invention (26)

Pernatran W was measured at a temperature of 37.8C and a relative humidity of 90%. (16) Catalyst analysis M dilute sulfuric acid decomposes the solid catalyst component before modification and the solid catalyst component for improved olefin polymerization, and extracts the debris with heptane. Use the atomic absorption AA610S type quantitative water layer Ti produced by Shimadzu Corporation. ^ Hitachi Manufacturing Co., Ltd. Gas Chromatography 263-50 quantifies the electron donor compounds in the heptane layer. Example 1 (1) Preparation of catalyst composition before modification (conventional method) Dissolve 56.8 g (597 mmol) of anhydrous magnesium chloride in 100 g (174 mmol) of anhydrous ethylenzyme under nitrogen at 120 ° C Vaseline CP15N 500 ml (share) system and Shin-Etsu Silicone (share) silicone oil 096 500 ml. Using a special TK honoBixer made by the chemical industry Co., Ltd., the mixture was stirred at 3000 t / min for 3 minutes at 120 t !, while transferring the mixture to 2 liters of anhydrous heptane while keeping the stirring at no more than 0. The resulting white solid M anhydrous heptane was thoroughly washed and dried under vacuum at room temperature. 30g of the obtained spherical solid MgCla2.5CaHe0H was suspended in anhydrous heptane 200B1. On the next side, 500 ml (4.5 mol) of titanium tetrachloride was added dropwise for one hour on the next side. Secondly, when the heating starts to reach 4010, diisobutyl titanate 4.96g (17 · 8 nmol) is added and the temperature is raised to loot: about 1 hour. After reacting for 2 hours in loot, the solid part was taken while meeting the filter while it was hot. Then * make the titanium tetrachloride 500 Bl (4.5 B〇1) suspended on the paper scale applicable to the Chinese National Standard (CNS) Λ4 specifications (2 丨 〇 < 297mm) 29 (please read the back (Notes to fill out this page), install ·, 11 A7 B7 Fifth, the description of the invention (27) reactants • M 120Ό reaction for 1 hour. After the reaction was completed, the solid part was taken again while hot, and M 60 was washed 7 times with 1 liter of hexane * KK room temperature was washed with 1.0 liter of 3 times. After measuring the content rate of the solid catalyst component obtained, it was 2.2 5 wt%. In addition, it contains 7.81% by weight of the electron-donating compound (1). (2) Preparation of improved solid marrow catalyst component 20g of the solid catalyst component obtained above was suspended in 300 ml of toluene, and reacted with 2.78g (10 Biuol) of diisobutyl titanate at 25¾ for 1 hour. After the reaction was completed, titanium tetrachloride 100 ml (90 ml) was added and reacted at 90 ° C for 1 hour. After the anti-condensation is over | Take the solid part while it is hot. Then, suspend 100 mL (900 nmol) of titanium tetrachloride 100 ml (900 nmol) in toluene and react for 1 hour at 9Q1C. After the reaction is over, take the hip fixation part again while the heat is over, wash it 7 times with 90D nail stupid 500 ml, then wash it 3 times with room temperature hexane 5QQ ml. The content of titanium in the obtained solid catalyst component was 1.Q1% by weight. In addition, it contains the first electron-donor-donating compound 12. Q% by weight. The analysis results of the catalyst components before and after the improvement are shown in Table 1. (3) Prepared by the Ministry of Economic Affairs, Central Central Bureau of Industry and Commerce Employee Consumer Cooperative (Please read the precautions on the back before filling out this page) Under a nitrogen atmosphere, < put n-heptane 50 into a pressure cooker with an internal volume of 3 liter 1111, triethylaluminum 6.01 (53 111 〇1), dicyclopentyldimethoxysilane 0.39g (17 mmol), and, the improved olefin polymerization vehicle component obtained in (2) above l 〇g * Stir for 5 minutes in the temperature range of 0 ~. The second time * Propylene is supplied to the pressure cooker so that each lg of modified olefin polymerization catalyst component can polymerize log propylene, and the polymerization is prepared for 1 hour in the temperature range of 0 ~ 5Ό. 210X297 mm) -30-A7 ___B7 ___ printed by the Employee Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs V. Description of the invention (28). The obtained preliminary polymerization solid catalyst component M n-heptane 500 Bl was washed three times and used in the following propylene-based polymerization Zhao Zhi. (4) In this polymerized nitrogen atmosphere, in a pressure net with an internal volume of 60 liters and carrying a mixing bowl, put 2.0 g of pre-polymerized solid catalyst component prepared by the above method and 11.4 g of triethyl aluminum (100 mmol) ), Dicyclopentyldimethoxysilane 6.84g (30 inniol), 18 kg of propylene, hydrogen gas was charged to make it 130 (30 molppm relative to propylene), and the temperature was raised to 7QTC. 1 hour for polymerization. 1 After hours, the unreacted propylene was removed to complete the polymerization. As a result, 6.56 kg of polypropylene could be obtained with a polymerization activity of 32.8 kg / g-the solid catalyst component * the MFR of the polymer was 33.Q g / 10 minutes. The evaluation results of the physical properties of the polymer are shown in Table 2. Example 2 (1) The preparation of the solid catalyst component before improvement is the same as Example 1. One (2) The preparation of TiCU [CsIh (COOiCMh) contains titanium tetrachloride 19g (100 ππηοΐ) of hexane 1.0 liter solution, while maintaining at 0¾-surface was added dropwise in 30 minutes diisobutyl titanate: CbHJCOO1.! ^), 27.8% (100 mmol). After the end of the drop, the temperature was raised To 4Qt :, the reaction is 3Q minutes. After the reaction is completed, the solid part is taken and washed 3 times with hexane 50 ml to obtain the target substance (3) Modification of catalyst component for olefin polymerization-20g of solid catalyst component obtained in (1) above was suspended in 300 · 1, under 25¾ with TiClUCefMCOITiMMa] 5.2g (11 mmol This paper size is applicable to China National Sample Standard (CNS) A4 Specification (210X297mm) -31- (Please read the precautions on the back before filling in this I) Pack ·, ιτ A7 B7_ printed by Beigong Consumer Cooperative, Central Bureau of Economic Development, Ministry of Economic Affairs Instructions (29)) Treat it for 1 hour to support it. After the captivity is over, take the hot part and take the solid part. Resuspend in 300 ml of toluene and 10 ml (90 nmol) of titanium tetrachloride. Stir and wash at 90 ° for 1 hour, filter while hot; take the solid part, then, wash the reaction 5 times with M9Qt: 500 ml of toluene, and then wash 3 times with room temperature hexane 500 Bl. The titanium content in the solid catalyst component obtained was 0.91% by weight. It also contained 10.6% weight of the first electron-donating compound. The results of catalyst analysis before and after the improvement were compared and shown in Table 1. (4) Preparing for polymerization under a nitrogen atmosphere, put n-heptane 500 in a pressure cooker with an internal volume of 3 liters ml, 6.0g (53 mmol) of triethylaluminum, 3.9g (0.017 mmol) of diphenyldimethoxysilane and 10g of the modified olefin polymerization catalyst component obtained in (3) of the above S Example 2, Stir for 5 minutes at a temperature range from 0 to 5¾. Secondly: Propylene M is supplied to the pressure net so that 10g of propylene can be polymerized per 1g of modified olefin polymerization catalyst component, and preliminary polymerization is carried out at a temperature ranging from 0 to 5¾-1 hour. The obtained pre-polymerized solid catalyst component was washed three times with 500 ml of n-heptane, and used in the production of the following propylene-based polymer. (5) In this polymerization nitrogen atmosphere, put into a pressure net with a 60-liter internal volume equipped with a stirrer, put 2.0 g of preliminary polymerization solid catalyst component prepared by the above method, 11.4 g (100 mmol) of triethylaluminum, and 2 6.84 g (30 nmol) of cyclopentyldimethoxysilane, 18 kg of propylene, hydrogen gas was charged to make it 130 0 mo 1 ppm relative to propylene, the temperature was raised to 70 C, and polymerization was carried out for 1 hour. After 1 hour • Remove unreacted propylene to polymerize. Results | Available 6.64 The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297mm) 32 (Please read the precautions on the back before filling this page)

、 TT Ministry of Economic Affairs Central Standards Bureau Beigong Consumer Cooperative Printed A7 Β7 V. Description of invention (3〇) kg of polypropylene, polymerization activity is 34kg / g-solid catalyst component • polymer MFR is 34.2 g / lQ points . Table 2 shows the evaluation results of the physical properties of the polymer. Comparative Example 1 The content under a nitrogen atmosphere was 6Q liter with a stirring pressure wa, to which A-type titanium trichloride 6.0g and diethyl acetyl aluminum chloride 23.5g (195) nmol), followed by charging 18 kg of propylene with hydrogen to 80 (30 molppm relative to propylene), and raising the temperature to 70 t: for 1 hour. After 1 hour, the unreacted propylene was removed to complete the polymerization. It can obtain 6.23 kg of polypropylene, and the MFR of the polymer is 32.2 g / lQ. The evaluation results of the physical properties of the polymer are shown in Table 2. Comparative Example 2 Except for the one prepared in (1) of Example 1 The catalyst composition of the solid stern before the improvement and the amount of hydrogen snapper during the polymerization of propylene were 9300 Bolppn * The rest are completely the same as the method and conditions of Example 2 to prepare for polymerization and propylene polymerization. Polypropylene 6.88 kg can be obtained, and the MFR of the polymer is 3 3.0 g / 10 min. The evaluation results of the physical properties of the polymer are shown in Table 2. Examples 3 to 5 except for adjusting the hydrogen feed during the production of the propylene polymer The amount can make the MFR of the produced polypropylene to be 0.5 g / l0 min, 2.7 g / 10 min, 〇. Except 7g / 10min, the rest are the same as the method and conditions of Example 2 of S to produce-polypropylene. The results of physical properties evaluation of the obtained polymer are shown in Table 2. Comparative Example 3 This paper music standard is applicable to China Standard (CNS) Α4 specification (210X 297mm) 33 (Please read the precautions on the back before filling in this page) Packed. Ordered by the Central Bureau of Standards, Ministry of Economic Affairs, Negative Consumer Cooperatives, Indochina A7 ______ B7 V. Description of Invention (31) Except for adjusting the hydrogen feed amount during the production of the propylene polymer, the MFR of the produced polypropylene polymer was 3.2 g / 10 min K, and the rest were the same as the method and conditions of Comparative Example 1. Manufacture of propylene strips Polymer. The results of evaluation of the physical properties of the obtained polymer are shown in Table 2. Example 6 (1) Preparation of the solid catalyst component before modification In anhydrous nitrogen atmosphere, 47.6 g (500 mmol) of anhydrous magnesium chloride and decane 2 were used. 50 ml and 234 ml (1.5 mol) of 2-ethylhexylase were heated at 130C for 2 hours to form a uniform solution. To this solution was added anhydrous phthalic acid ll.lg (75 mmol), which was then carried out at 13QTC Mix by mixing for 1 hour to dissolve the anhydrous peptide acid in In a homogeneous solution. After cooling the resulting homogeneous solution to room temperature, the whole amount was dripped in 2.0 liters (18 mol) of titanium tetrachloride kept at -20t: 1 hour. After the dripping was completed, the temperature of the mixed solution was K4 Heat up to llQt: in hour, reach UQt: After adding 26.8 ml (125 mmol) of diisobutyl phthalate, let it stir at 110 ° C for 2 hours. After the reaction was over, the solid part was taken while it was hot, and then 2.0 liters (18 mol) of titanium tetrachloride was allowed to become turbid after this reaction material • at 110 °; the reaction was carried out for 2 hours. After the reaction was completed, the solid part was taken again while hot, and washed 7 times with 2.0 liters of decane 110 t, and 3 times with 2.Q liter of hexane at room temperature to obtain a solid catalyst component. The catalyst analysis results are shown in Table 1. (2) The preparation of TiCl ^ CeKCOOiiM),] is the same as (2) of Example 2-(3) Modification of the modified olefin polymerization catalyst component makes the solid catalyst component obtained in (1) above suspended at 4〇g For Toluene 600, the paper size is in accordance with Chinese National Standard (CNS) A4 specification (210X 297mm) 34 -------- Gas loop-• «(Please read the precautions on the back before filling this page) 3 ^ 69〇9 Printed A7 B7 by the Consumer Labor Cooperative of the Central Prototype Bureau of the Ministry of Economic Affairs. V. Description of invention (32) In ml, process the TiCl * [CsMCOOlC4Hs) al 10.3g (22 bboI) 1 hour to support it. After the support is over, take the solid part while the heat is over. * Toluene 600 pass 1 and four gasification 20 Bl (180 mmol) are resuspended, stirred and washed at 90 ° for 1 hour, and take the hip part while hot. Then, the reactant was washed 5 times with 1.Q liter of toluene at 90% * and then washed 3 times with 1.0 liter of hexane at room temperature to obtain an improved olefin polymerization catalyst component. The catalyst analysis results are shown in Table 1. (4) To prepare for polymerization under a nitrogen atmosphere, put n-heptane 5000 ml, triethylaluminum 6.0g (53 mmol), diphenyldimethoxysilane 4.15g (0.017 mmol) and the modified olefin polymerization catalyst component 1Qg * obtained in (3) of the above Example 2 were stirred for 5 minutes at a temperature ranging from 0 to 5¾. Next, propylene M was supplied to the pressure net so that 10 g of propylene could be polymerized per 1 g of the modified olefin polymerization medium component. The polymerization was prepared for 1 hour at a temperature range of 0 to 5¾. The obtained pre-polymerized solid catalyst component Μ-n-heptane 500 ml-washed 3 times * and used in the production of propylene-based polymerization under Μ. (5) Under the atmosphere of polymerized nitrogen in propylene, in a pressure stage with an internal volume of 60 liters equipped with a stirrer, put in the pre-polymerized solid catalyst component 200 ng prepared by the method above and 11.4 g of triethylaluminum (100 bboI) 3. 7.32g (30 mmol) of diphenyldimethoxysilane, followed by adding hydrogen to propylene 18 fcg to 5300 molppm relative to propylene, and raising the temperature to 70t :, conducting polymerization for 1 hour. 1 hour-after time * remove the unreverse propylene to complete the polymerization. Polymerization activity is 22.0 kg / g-solid catalyst component. In addition, the MFR of the obtained polypropylene is 14.5g. The paper size is in accordance with Chinese National Standard (CNS) A4 (210X29 * 7mm) 35

Ir ^, 袈-(please read the precautions on the back before filling in this page) Order A7 __B7 Printed by the Employee Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (33) / 10 points. Table 2 shows the evaluation results of the physical properties of the polymerized stern. Example 7 Under a gas atmosphere, 50.0 g (440 mnol) of diethoxymagnesium and 15.3 g (55 anol) of di-n-butyl diorate were stirred in 250 ml of dichloromethane under reflux for 1 hour. The resulting suspended hydraulic pressure was sent to titanium tetrachloride 2.D liter (18 mol), the temperature was raised to ΙΙΟΌ, and the reaction was carried out for 2 hours. After the reaction was over, the precipitated solid was reacted with 2.0 liters (18 mol) of titanium tetrachloride at 110 TC for 2 hours. After the reaction was completed, MllOt was washed three times with 2.0 liters of n-decane, and at room temperature, 2.0 liters of K-n-hexane was washed until no gaseous male was detected. Drying under reduced pressure at 40¾ • The desired solid catalyst component can be obtained. The catalyst analysis results are shown in Table 1. (2) The modulation of TiClUCsfUiCOiTiMU) *] is the same as (2) of Example 2. (3) Modified preparation of olefin polymerization catalyst components. Suspend 40g of the solid catalyst component obtained in (1) above in 600-ml of toluene. • At 90t: TiCl4 [C6MCO (TC * H3) a] 10.3g (22 mmol) for 1 hour to support it. After the support is over, take the solid part while it is hot. Make toluene 60 0 ml and titanium tetrachloride 20 b1 (180 n.mol) resuspend, and wash with stirring at 90¾ for 1 hour. Take the solid part while hot Then, wash the antifouling 5 times with 1.0 litre of 90¾ of toluene | then wash 3 times with 1.0 litre of hexane at room temperature to obtain an improved olefin polymerization catalyst component. The catalyst analysis results are shown in Table 1. -Both the preliminary polymerization and the propylene polymerization were carried out in the same manner and in the same conditions as in Example 6. As a result, the polymerization activity is 21.1 kg / g—solid catalyst component. The paper size is in accordance with the Chinese National Standard (CNS) A4 specification (2 丨 0X297 issued) 36 (please read the precautions on the back before filling this page) Binding 316 * 909 A7 B7 printed by the Employee Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs V. Description of Invention (34). Also, the MFR of the obtained polypropylene was 16 · 3g / 1Qmin. The evaluation results of the physical properties of the polymer are shown in Table 2. Table 1. Results of catalyst analysis before solidification. Catalyst composition Modified olefin polymerization catalyst composition Di (vt%) Τι (vt96) (D / T), Dm (vt96) Ti (vt96) (D / TU (D / T) „/ (D / T). Example 1 7.81 2.25 0.60 12.0 1.01 2.05 3.42 Example 2 7.81 2.25 0.60 10.6 0.91 2.01 3.35 Example 6 10.1, 2.57 0.75 15.6 1.01 1.98 2.64 Example 7 9.80 2.31 0.73 13.3 1.22 1.53 2.10 (Please read the precautions on the back before filling in this page) Binding. Book 37 This paper size is applicable to the Chinese National Standard (CNS) A4 specifications (210 X 297 mm) A7 B7 5. Invention description (35) Ministry of Economic Affairs Comparative Example 3 printed by the Central Standards Bureau Employee Consumer Cooperative 3 Example 7 Example 6 Example 5 Example 4 Example 3 Comparative Example 2 Comparative Example 1 Example 2 Example 1 Slag m C £ 00 ί— * CO CO CD CO C〇CO CO CO CO CJT CD CO CXI CO 00 00 CO 00 03 CO CO CJ1 C2 CO CJT Dimethylbenzyl extract insoluble fraction (%) _1 CO Ο CO CO CO CO CO c * a CO CO CO CO CO CO CO CJ1 CO 00 CO CO —3 —J CO CO CJT CO CO cn S Duan 3 Xie Fan S 3 a W A Xue Η- * ο CJ1 03 Ol o CO CJl c〇00 0 3 CJ1 h-► — CJ1 CO CS9 03 CO tsD cn 00 with 03 00 as the average key length of the sequential connection N / \ < 35 00 03 CJ1 o 八 〇〇co N " S 番 番 _ Φ S 薛 薛 书 mm ^ 次 _ 骘 w φ 揶 Grid, f «〇〇CO CO — 05 H * cn o -J CS9 o cn CO 09 o 03 to CS3 CO Ps5 ω CO o MFR (g / 10 points) (please read the back Please pay attention to this page and then fill out this page) This paper scale is applicable to the Chinese National Standard (CNS) Λ4 specification (210X 297mm) W6S09 A7 B7 V. Description of invention (36) Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs rr n M Μ n EF rr cr n 飈 e? M S mmmmmmm shading mm mm slag C0 people 1 σι CO DO — DO t—k PO to Cs9 DO DO H-fc CO > — * — DO cn o 〇00 〇〇 〇o 00 d Izod impact strength kg · cm / c 1 | | 1 III 1 II 1 DO 〇d B? «Η— CO H- * I- * Office Η- * 1—fc-* 3 09 I— * Office h-fc 09 H- * $ e CO ο Cl o CO o CS9 Ο DO Ο CO o CO o 03 o — c CD 〇r 、、 通 B ο oo Ο ◦ ao ◦ oog L 漭t it I— * ο h- ts3 h- * DO Η · * μ- * — CO (—k CO H * Cs3 h- t—k) — »h- * giaW Office 00 00 α ο o CO 1—» 〇S »)« Waterlogging ϋ r 5 Hong Kong Tea an CO CO I- * ό H- * ot— »CD 09 h— Ο DC H- * 〇09 1—fc o 1—fc CO CO hk a Office o Office a 0〇h- »00 cn 0〇CJX C〇 & j 00 private C〇CJX 03 prepared 0〇OS 00 CD CO 〇d CO CsD CO CO — Cs3 CO o H-fc I— * I— * H- H -* 1 1 1 1— * OJ H- * — 〇d 〇i ts3 DO DO 〇 " Business to Γ close \ m | CJ \ cn 03 CJ1 CJt sim Private CJX H «* CO 09 03 g · 遥« 4 , Lt * pine DO o CO 1 1 C * 9 o ro CO OJ PO DO CO CO CO C ^ 9 Haze (96) shower 2 丨 2 (please read the precautions on the back before filling this page) This paper size is applicable to China National Standard (CNS) Λ4 specification (210X297 mm) 39 A7 B7_ printed by the Employee Consumer Cooperative of the Central Bureau of Economic Affairs of the Ministry of Economic Affairs 5. Description of the invention (37) Example 8 Same as Example 2 After the polymerization of propylene in a pressure cooker with stirring capacity of 6 liters (M 1), the liquid propylene is removed, and at 751, the mixture gas of ethylene / propylene = 40/60 (Dur ratio) is 2.2 Nm3 / hour, hydrogen 20 NL / hour supply rate, copolymerization for 40 minutes (Section 2). After 40 minutes, the unreacted gas noodles were removed to complete the polymerization. As a result, 8.0 kg of propylene-ethylene-bulk copolymer can be obtained. The ethylene content according to 13 C-NMR was 9.7% by weight, and the MFR was 17.8 g / 10 minutes. The physical evaluation results of the polymer are shown in Table 3. In addition, XI, IP, and N in Table 3 are military polypropylenes taken out after the end of the first polymerization. Comparative Example 4 Same as Comparative Example 1, after propylene was polymerized in a 60-liter Lipot with a stirrer, the liquid propylene was removed, and at 65t: a mixed gas of ethylene / propylene = 40/60 (mole ratio) 2.2 Nm3 / hour, 20 NL / hour supply rate of hydrogen for 40 minutes. After 40 minutes, remove the unreacted gas — to end the polymerization. As a result, 7.7 kg of propylene-ethylene-bulk copolymer can be obtained. According to 13〇- ^ 1? Ethylene content is 9.6% by weight, to discuss? 11 is 18.3 per / 10 points. The physical property evaluation of polymerization «is shown in Table 3. In addition, XI, IP and H in Table 3 are elemental polypropylenes taken out after the polymerization in the first stage. The standard of this paper is applicable to China National Standard (CNS) Λ4 specification (210X297mm) 40 (please read the precautions on the back before filling in this page)-binding 16909 A7 B7 5. Description of invention (38) Employees of Central Bureau of Standards, Ministry of Economic Affairs Comparative Example 4 Printed by Consumer Cooperatives Example 8? W m m CO 00 CJ1 CO CD cn xylene extraction insoluble fraction (% by weight) CO CO CO CJl = Φ 丽 3 揋 番 5 3 Yi Xue ΓΟ Η * -α 00 CO o The average chain length of cis-linkage N octalithium _ Φ § ΠΠΠΗ »Jil μΟ (ΐ μ33 > 1 _ _ 次 次 M 露 一 Φ 揶 树 V AZ Ν» 〇〇Ο 〇I— »〇〇Ca3 — CO MFR (g / 10 points) --I ----- ^ -installed --- I--order ------- C Bing- y, (please read the precautions on the back before filling this page) This paper wave scale is applicable to the Chinese National Standard (CNS) Λ4 specification (210X 297 mm) 41 V. Description of invention (39 A7 B7 Printed Comparative Example 4 of the Employee Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 4 Example 8 CJ1 cn 03 23V Aizod Impact strength (kg · cm / cm) B 3π CJ CO -20V 12100 14100 ^ H ^ s > a 3 lS »ΓΤΓ Yixie Η-k Η-» PS3 1-► CO load change Forming temperature (V) S CD CS5 Rockwell surface hardness R scale 62.3 68.1 Surface gloss (96) 1 1 Surface gloss (%) it hidden 1 1 \ m% m • mg · Is 3 m I Haze (96) » 3 — 2 I --.----- Γ. 装 ------ 定 ----- ^ (Please read the precautions on the back before filling out this page) This paper size is applicable to the Chinese National Standard (CNS ) Λ4 specifications (210X 297 mm) -42-A7 B7 printed by the Employee Consumer Cooperative of the Ministry of Economic Affairs, A5, B5. Description of invention (40) Examples 9, 10 and Comparative Example 5 Examples of propylene-based polymer compositions In the propylene polymer obtained in the present invention, di-tert-butyl-p-cresol 0.05% by weight, pentaerythritol-tetrakis [3- (3,5-dibutyl- 4-hydroxyphenyl)] Propionate 0.10% by weight 1%, calcium carbonate 0.1% by weight, using a 20-liter supermixer (SMV20 type) manufactured by Kawada Manufacturing Co., Ltd. * Use AS30 manufactured by Nakatani Toki Machinery Co., Ltd. Type 30 ΙΠΒ10 double-sleeved extruder for granulation. In addition, using the lower Μ as the nucleating agent, the amount of formulation is appropriately changed. (Types of nucleating agents) Nucleating agent A: pt-butyl benzoic acid aluminum salt nucleating agent B: phosphoric acid 2, bmethylene bis (4,6-di-third butylphenyl) is contained in the examples 2 The composition obtained by blending the above-mentioned nucleating agent etc. in the obtained polypropylene (Examples 9 and 10) and the composition formed by blending the nucleating agent in the polypropylene obtained in Comparative Example 1 (Comparative Example 5) ), The physical property evaluation results of the two are shown in Table 4. Example 11 and Comparative Example 6 The propylene-ethylene-bulk copolymer obtained in Example 8 and Comparative Example 4 was blended with the same nucleating agent as in Example 9 to form a composition. It is shown in Table 4. (Please read the precautions on the back before filling out this page) Binding _ Order ---- This paper size is applicable to China National Standard (CNS) A4 specification (2IOX297mm) 43 &26; δ〇9 V. Description of invention (41) A7 B7 Printed Comparative Example 6 Example 11 Comparative Example 5 Example 10 Example 9 FM 98.5 CD CO CJl CO CO 00 99.5 99.5 Dimethyl stupid extracted insolubles (% by weight) CO CO CO cn CO CO ca CO CO CJX iD ca CJl g Φ 蠹 a 湶 | 3 Yi Xue DC Η- * —3 CO CO o Ού CS3 03 CO CO 05 c〇CO Cd Shunlian average average length N eight CO 00 N1聂 氆 番 luati 2 £ Jd PSI pES _ Jin Ji _ Ba Yi Φ ϊν μ »〇9 Ο Ο 1—» 00 03 CO CO CO ts5 34.2 CO CS3 MFR (g / l〇 points) _i A 0.2 A 0.2 03 〇03 〇 > 〇PO _ 蕺 踵 -mm »4: 丨 1 (please read the precautions on the back before filling in this page) The size of the bound paper is applicable to China National Standard Falcon (CNS) Λ4 specifications (210X 297 %) 44 A7 B7 V. Description of invention (42) Comparative example 6 printed by the Employee Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs Example 6 Example 11 Comparative example 5 Example 10 Example 9 cn CO as PO H- * -a > — * CO — 23t: Izod impact strength (kg · cm / cm) a BB m ΗΠ CO ο CO 00 1 1! -20Ό 14600 16800 19200 24500 22000 P rt rt 2 3 u £ β ΓΗ · 一 树 Η— Office CO Hk Cd I— * Office 00 — Load deformation temperature (V) CO CO CO — o CO > — * o CD 〇cn Rockwell surface hardness R scale Oi —3 ΓΟ PO CO 86.3 93.8 Ci3 H- * Surface gloss (96) 1 1 Ca9 to CO 00 Surface gloss (96) Wet 1 1 PC CJ1 1— * ot OS Water vapor transmission rate (g / m * · Day) 1 1 CO 05 CO — 03 t— CJl Haze (%) Zheren 丨 2 (Please read the precautions on the back before filling this page)

、 1T The size of this paper is applicable to 31 national standards (CNS) Α4 specifications (210 X 297 mm) 45 A7 B7 5. Description of invention (43) Comparative examples 7 ~ 9 Except for adjustment, the MFR of the produced polypropylene is 11.0g / lQ points, 3. Og / 10 points, 0.5g / 10 points, the rest are the same as the method and conditions of Comparative Example 2 to produce polypropylene. Table 5 shows the evaluation results of the physical properties of the obtained polymer. -J ----- ^ f 袈-(Please read the notes on the back before filling this page)

* tT The paper standard printed by the Employee Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs applies the Chinese National Standard (CNS) Λ4 specification (210X2 ^ 7mm) 46 Printed by the Employee Consumer Cooperative of the Central Bureau of Samples of the Ministry of Economy ° 169〇g Description of the invention (4〇'Comparative Example 9 Comparative Example 8 Comparative Example 7 1 Comparative Example CO 00 • 05 98.7 98.7 Xylene extraction insolubles (% by weight) 03 C3 CO 00 00 CO 03 C0 3 Broadcast Gong SS 囲 260 290 306 Shunlian's average chain length Ν 03 Ν 虫 鹹 intercepted secluded book_ _ 进 w 冰 ίίπ ϊν Η »OS ο ο 〇CJ1 CO 〇μ— Η— ◦ MFR (g / l〇 points) (please read the back first (Notes to fill out this page) 袈

、 1T The size of this paper is in accordance with the Chinese National Standard (CNS) Λ4 specification (210Χ 297mm) 47 A7 B7 V. Description of invention (45) Printed and printed comparative example of the employee consumer cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs 9 Comparative example 8 Comparative example 7 Shen Resignation mm CO • c * a «〇CO CS3 23V Izod impact strength (kg · cm / cm) B m flood π 1 1 1 -20t: 12800 14000 15600 Flexural modulus (kg / cm®) 〇CJI Η— CsD Ο) Load deformation temperature CC) CO DO — 〇◦ h- Ο PO Rockwell surface hardness R scale 80.5 82.4 83.1 Surface gloss (96) 1 Ο -J — — Surface gloss (%) m Μ 1 03 a > o 5Γ 兴 \ m 气 i • 氰 氐 m 3 _ 1 Oi Office o Haze (96) 浙 5 I 2 (Please read the precautions on the back before filling this page)

、 TT This paper scale is applicable to the Chinese National Standard (CNS) Λ4 specification (210X297mm) 48 316909 A7 B7 5. Description of the invention (46) The box is implemented by the present invention. Because it can be manufactured, it is more excellent than traditional knowledge, surface The properties such as hardness, heat resistance, water vapor barrier, etc. are suitable for use in automobiles, household appliances, and packaged propylene-based polymers and finished products, and have sufficient industrial value. . '"· (Please read the precautions on the back before filling out this page) Binding. Order Printed by Employee Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs This paper standard is applicable to China National Standard (CNS) A4 (210X297mm) 49

Claims (1)

Magic 69〇, Bulletin A8 B8 C8 D8 A, Patent Application Scope Printed by the Central Liangzhun Bureau of the Ministry of Economic Affairs, Beigong Consumer Cooperatives *. No. 83104361, Application for Patent Scope Amendment Date: July 86, 1. A propylene The manufacturing method of solid «medium component for polymerization includes the following step K: (1) forming a solid« «medium component for polymerization; it is a magnesium compound of MS self-dentifying magnesium and magnesium alkoxide, selected from titanium halide The titanium compound of titanium alkoxide, the halogen compound selected from titanium halide and silicon halide, and the first sub-donor compound selected from yeast, ether, ester, acid halide, acid liver are essential components, and solid contact The first electron-donating compound (D) and titanium (T) held in the media component has an ear ratio of (D / Th; and, (2) Treating the aforementioned polymerization solids "« Media component, which is Μ The first electron-donating compound is treated and supported, and then treated with a halogen compound to clean it, and further, it is washed with a hydrogen compound; the composition of the solid medium for polymerization described above is modified to be supported The first ear of the donor compound (D) and titanium (Τ) It is (D / TU's solid catalyst component for polymerization, here (D / T> m / (D / T) ·> 1. 2. If you apply for the method of item 1 of the Lifan Garden, its (D / T ) «/ (D / Th έ 2 〇3. For example, the method of applying for patent fan garden item 1 or 2, in which the step fee for processing the aforementioned susceptible media components ⑵ includes the following steps: With the general formula Ti) UYb (where X represents a halogen atom of Cl, Br and / or I, a is 3 or 4, Y represents the first donor compound, 0 < b each 3) before the treatment of the halogen-containing titanium compound This paper uses the Chinese National Standard (CNS) A4 specification (210X297mm) (The first item on the back of Mtt must be filled out with the $ item, then fill in this K) 50 3ί63〇9 Α8 Β8 C8 D8 apply for a patent Fan Yuan Yu Ji Ministry Central # Rate Bureau Bei X consumer cooperative printing and printing "catalyst component" to support it; then, M halogenated compound washes the aforementioned solid catalyst component ; Further, the nitrate compound was used to wash the solid hydration medium components. . A method of manufacturing a propylene strip polymerization compound, which includes a step of polymerizing propylene using a polymerization medium. The polymerization catalyst contains: (i > solid catalyst component for polymerization, which is a patent application of M The method produced by any one of items 1 to 3; (u> an organoaluminum compound escaped from trialkyl aluminum, alkyl aluminum alkoxide, aluminoxane; and < itt) selected from yeast and ether , 醮, acid liver, silicon compounds with Si-0-C or Si-NC bond, rabbits with alkyl substituents or oxygen heterocyclic compounds of the second-best donor compounds. Item 4. The manufacturing method of item 4, wherein the prepared propylene stripe polymer contains a repeating unit of-(CH2-CHCH3>-) and is a homopolymer or copolymer or block copolymer * The homopolymer is CH3- CH = CH * is a homopolymer of propylene, which is a copolymer of propylene and α-olefin represented by MR-CH = CH2, R represents hydrogen or has 1-20 sulfur atoms In the genus of the family, the block copolymer is a block copolymer of propylene and ethylene shown in CH2 = CH *; in addition, the polymerization of propylene strips is ⑴ 25t bis Toluene extracts the insoluble fraction (XΠ is above 99.0% by weight; ⑵ the isotactic pentad fraction measured by 13C nuclear magnetic resonance spectroscopy (IP> is above 98.096M; (3) the average bond of cislink The length (N) is more than 500; and (4) The average chain length of each component group (Nd is 800M) measured by the column method of (4) M xylene insolubles separately (please first «read the note on the back side $« and fill in this Page) -si installed · Alt • i private paper standard is in use • 鬭 家 样 准 (CNS) Λ4 specifications (210X297mm) 51 3i69〇9 ~ ——__, part of the patent application range A8 B8 C8 D8 The total of the groups is 10% or more. 6. The manufacturing method as described in item 5 of the patent application, wherein the step of polymerizing propylene using the polymerization * medium M includes step (1) preliminary polymerization M and steps (2) Proprietary polymerization of propylene. 7. For example, the method of applying patent patent item 6 *, in which propylene strip polymerization is ⑴ 25t: Xylene extracts insoluble fraction (XI> on 99.0 heavy Dong; M13C nuclear magnetic resonance The isotacticpntad score (IP) measured by the spectrum is above 98_5%; (¾ the waist The average spread length (N) is 500M; and (4) The average bond length (N,) of each partial group measured by the column method of (M) xylene insolubles separately is 30 weights. It should be more than 8%. 8. For example, the method of application of item 5 of the Lifan Garden, in which the insoluble fraction 0 (1) extracted from the propylene-based polymer polymerization system (O 25T in xylene) is at 99.0% by weight; ⑵ with 13C nuclear magnetic resonance The quintuple (18〇13 «: 14? 1 ^ 3 (1) fraction (1?) Measured by the spectrum is above 98.5%; (3) The average chain length (N) of the tandem is above 500 ; And (4) The total chain length (N,) of each partial group measured by the column method of xylene-insoluble fractions is 800 or more, the total of the partial groups is more than 30 weights. (Please read "Notes on the back of the $ item and then 4 copies to buy > T outfit .. • Order the Ministry of Economic Affairs Central Bureau of Rates Staff Consumer Cooperative, 2- *.? -F Standard (CNS) A4 specification (210X297mm) -52-