TW419498B - Propylene-based polymer and composition thereof - 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 <13>C 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 (Nf) is 800 or greater accounts for 10 wt% or more of the entirety, and 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

419498 A7 B7 V. Description of the invention (1) The present invention is a propylene-based polymer suitable for automobiles, home appliances, and packaging materials, which are excellent in physical properties, surface hardness, heat resistance, and water vapor barrier properties. Its production method, composition M, polymerization catalyst component and its production method. Propylene-based polymers are generally widely used in industry because they are cheap, and have special properties such as transparency, mechanical strength, heat resistance, surface gloss, chemical resistance, oil resistance, rigidity, and flex fatigue resistance. Materials, food packaging materials, cosmetics packaging materials, pharmaceutical packaging materials, etc. As mentioned above, the propylene-based polymerization system is widely used in various industries such as automobiles, home appliances, and miscellaneous goods, taking advantage of its rigidity and shock resistance. Recently, in order to reduce the weight and price of products, to reduce the thickness of products, or to prevent scratches on the surface of products, research has been conducted to increase the surface hardness. That is, the propylene-based polymer is required to be one having a high rigidity, high surface hardness, and excellent impact resistance. In addition, the requirements for physical properties and processability have gradually increased. In particular, it is strongly desired to improve the retention of rigidity and strength at high temperatures, durability, and moldability of large-scale molded products.

In the past, the Consumers' Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs of the People ’s Republic of China has previously known the methods of high rigidity, transparency improvement, and surface gloss improvement of acrylic polymer polymerization. For example, sodium benzoate), dicarboxylic acid (adipic acid), group III ~ IV metal salts of aliphatic dicarboxylic acids (such as aluminum adipate), dibenzylidene glucosyl derivatives, talc, etc. Methods as shuttle-forming agents (Japanese Patent Publication No. 9-9809, Japanese Patent Publication No. 60-13973, etc.), or methods for expanding the molecular weight distribution of propylene polymers (Japanese Patent Publication No. 56-2) 30 Gazette No. 7, JP 53-Π250 Gazette No. 7, JP 6-2-1 9 500 7 4 (Please read the precautions on the back before filling out this page) The paper size applies to the Chinese National Standard (CMS) A4 Specifications (210X 297 mm) 419498 A7 B7 V. Description of Invention (2), etc.). However, * when using these nucleating agents *, although it has the effect of improving the physical properties mentioned above, it cannot be said that the use is sufficient. Therefore * It is suitable for an acrylic polymer with impact resistance, rigidity, mechanical strength and surface hardness, heat resistance, etc., which is foolish in automobiles, home appliances, and packaging materials. By reducing fillers such as talc, it is expected to reduce product density and Thin the product. Also • Efforts to improve the isotacticity of propylene-based polymers, or broaden the molecular weight distribution, depend on the strength of the high molecular weight distribution, improve durability, and improve moldability such as extrusion molding or hollow molding. . Among them, especially the development of catalysts showing high activity and high stereoregularity has been under full review in recent years. Either way, catalysts made of solid catalyst components containing magnesium, titanium, halogen, and electron-donating compounds as well as organoaluminum and electron-donating compounds are disclosed. For example, JP-A-57- 633 1 0, JP-A 5-8- 3 2604, JP-A 58-83006, JP-A 59, printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling this page) -206408, Hold open Sho 59-219311, JP Sho 60-130607, JP Sho 6 1-20920 7, JP Sho 6 1- 2 1 1 30 9, JP Sho 62-7 2702, JP Sho 62-104811, Tokai Sho 62- 1 1 7 0 5, Tokai Sho 63- 1 9 9703, Tokai Sho 6 3-264603, Tokai Pingbu 126306, Tokai Hei 1-311106, Tokai Hei 3- 62805, Tokai Hei 3- 7071Q, JP 4-10 3 604, JP 4-114DQ9, JP 4-2Q 2505. -Also • The inventors have also recently disclosed in JP 4-4 3407, JP 4-1492 1 7, JP 4-178406, JP 4-180 903, and JP-4 4- This paper standard applies to Chinese national standards (CNS) A4 specifications (2! ΫχΜ7 mm) 419498 A7 B7 V. Description of the invention (3) 18 5 6 1 3. JP-A-Heisei 4-198202, JP-A-Heisei 4- 198204, JP-A-Heisei 5 -9 2 0 9, special Kaiping 5-287019. The xylene of propylene-based polymerization system disclosed in these prior documents extracts less than 99% of insolubles, and the methylation of the polypropylene is determined by shuttle magnetic resonance spectroscopy (M iaC-NMR). The composition ratio (nBBB) is as high as about 93 to 98%. • There are limits on various physical properties such as improving properties and heat retention. The object of the present invention is to provide a propylene-based polymer for automobile, household appliances, and packaging materials that is not detrimental to the original characteristics of propylene-based polymers and is suitable for automobiles, home appliances, and packaging materials with excellent physical properties such as rigidity, surface hardness, heat resistance, and water vapor barrier properties. , Its manufacturing method and composition, and polymerization catalyst component and its manufacturing method. The present inventors reviewed various methods for solving the aforementioned problems. As a result, it was found that a propylene-based polymer can be used. The total fraction of the fractions can be 10% by weight or more, and the fraction is U) 25 * 0. Xylene — extraction of insoluble (XI) above 99.0% by weight; (2) isotactic pentad fraction (IP) measured by nuclear magnetic resonance spectroscopy (IP) Employee Consumer Cooperative, Central Bureau of Standards, Ministry of Economic Affairs Printed (please read the precautions on the back before filling this page) above 98.0%; (3) the average bond length (N) of Shun Cong is 500M; and (4) the xylene insoluble column is measured separately The average length (h) of each partial group obtained is 800 or more * to solve the aforementioned problems and finally complete the present invention. The following describes the characteristics of the propylene-based polymerization of the present invention. (1) Xylene extraction insoluble (XI) is insoluble in 25C xylene. The weight of the polymer is 1%, specifically, once it is temporarily dissolved in 135 = o-xylene, it will precipitate at that time % By weight of polymer. The paper size of this invention is applicable to Chinese National Standards (CNS) A4 (210 × 297), 4 * 9493 A7 B7 printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. XI of the acrylic polymer of the invention description (4) It is preferably 99.0%, preferably 99.5% M or more, more preferably 99.7% M or more. If XI is less than 99.0%, the desired properties, heat resistance, surface hardness, surface gloss, transparency, and water vapor barrier properties are insufficient. (2) Among the polypropylene molecular bonds measured by the so-called nuclear magnetic resonance spectrum, The five-component rate of cis-link (hereinafter • sometimes also referred to as IP) • Measured according to the method of A. Zambelli, Macromolecules, β_, 925 (1 973). That is, the nuclear magnetic resonance spectrum (13 C-NMR) measured using isotopic carbon, the fraction of the same row of five-tuple units in the propylene tritium polymer measured. The IP of the present invention is the measured value of the polypropylene itself obtained by polymerization, and the measured value of the polypropylene after the egg is subjected to the aforementioned xylene extraction, other extraction, and the like. The return of the spectral peak is based on a revised version of the above document described in Macro molecules, 3_, 687 (1975). The intensity fraction of the mas peak in the total absorption spectrum peak of the methyl carbon region of the 13C-NMR spectrum is used. Measure IP. _ The IP in the propylene polymerized fluorene obtained in this way must be 98.0% K * If it is lower than this value, rigidity, heat resistance, surface hardness, surface gloss, transparency, and water vapor barrier properties will be insufficient. It is preferable that the IP in the acrylonitrile aggregate is more than 98.5%. Particularly preferred is a propylene-based polymer having an IP of 99.0% K. (3) The so-called average length (N) of the forward direction is the average length of the coupling of methyl groups in the polypropylene molecule, which can be according to the method reported by J.C. Randall (a Poly Zuer Sequence Distribution, Academic Press, New

York 1 977, chapter)). This paper size applies to Chinese National Standard (CNS) Α4 size (210 X 297 mm) (please read the precautions on the back before filling this page). Λ 419498 A7 _B7__________ 5. Description of the invention (5) Propylene was heated to 130 ¾ and dissolved in a mixed solvent of 1,2,4-trifluorobenzylbenzene and heavy benzene so that the polymer concentration became 10% by weight. This solution was placed in a glass sample tube with an inner diameter of 10 mffl0, and iaC-NMR was measured under the same conditions as the five-component ratio (IP) of the previous coupling. "Shan-Nong ZHU, Xiao-Zhen YANG, Riichiro CHUJO; Polyner Journal, vol.15, No.12, p859-868 (1983) described the two-sided horizontal type definition, that is, assuming that the active point during polymerization has 2 Type. One of them is oligomeric dominant polymerization * and the other is terminal-dominated K polymerization. [The catalyst-dominated polymerization and terminal-dominated polymerization have been described in detail in Junji Furukawa; the essence of polymers and title 2, Γ polymer synthesis ", P73, Chemical Co., Ltd. (1986)]. 2 恻 Horizontal type can be sorted into: a: Probability of the addition of D-body and L-body at the polymerization end of the catalyst-dominated polymerization (enanthiomorphic process). (Bernoulli process) Probability that the meso body added by the ω: the rate on the α side is printed by the Consumers' Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs. The military position is split into 10 spectral peaks. However, in order to make the actual measured value consistent with the calculated intensity (area), κ minimum automultiplication method is used to obtain α, σ, 〇 &gt; Sister's most At ~ Α10. 8 (Please read the notes on the back before filling this page) This paper scale is applicable to the Chinese National Standard (CNS) Α4 ^ grid (2 丨 0X 297 mm) Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs. 4l9498 at B7 V. Description of the invention (6) Intermediate At = nnnmiii = ω (1—5 / 9 + 5/3 a) + (1— ω) σ * Aa — mniiDr = ω (2/3 —6/3 a) + 2 (l-ω) σ3 (1- σ) As = rmmr = ω β a + (1- α &gt;) σ3 (1- σ) β racemic structure A ′ = μγγ = ω (2/3 —6 / 3 2) +2 (1 — ω) σ * (1 — 〇 &quot;) a Αβ = ttiarffl = 2ω β * + 2 (1- ω) σ3 (1- σ) rmiT = 2ct &gt; 0a + 2 (l — ω) σ (1-σ) 3 A? = nnrin = 2ω ^ 33 + 2 (1— ω) σ * (1— σ) 2 Αβ = γγγγ = ω β 3 + 2 (1— α &gt;) (1— σ) * Α9 = ιιΐΓΓΓ = 2ω / 3 * + 2 (1'ω) σ (1-σ) 3 Αι □ = mrrm = ω (β-3 / S s) + (1- ω) σ * (1 ~ σ) * * β = a (1-α) Secondly, the definition of the average length (N) recorded in the aforementioned JC, Ramdall literature S = the number of bonds in the middle pulp / the number of units in the intermediate. The quintuple unit * of Ai-Ar can be obtained by the following formula.

Ai + Aa + Aa + 0.5 (A * + As + As + A7) N =-0.5 (A «+ Ae + Ab + A?) Also, the N value of the present invention is the measured value of the polypropylene obtained by polymerization. * It is not the measured value of polypropylene after the aforementioned xylene extraction, other extractions, etc. The highly stereoregular propylene polymer of the present invention has an N of 500 or more, preferably 700M, and more preferably 800 or more. If N is less than 500, the desired rigidity and heat resistance are insufficient. The size of this paper is applicable to the Chinese National Standard (CM) Λ4 (210: &lt; 297). — — 11 (11 Pack t- ™ t — Order — 〆 (Please read the notes on the back before filling in this Page) Printed by the Central Bureau of Standards of the Ministry of Economic Affairs-Industrial and Consumer Cooperatives 4,9498 at B7 V. Description of the Invention (?)-In general, the 13C-NMR signals of polypropylene are three main groups: methylene, methine, and methyl. Spectral peaks obtained. Among them • If the spectral peak of the methyl region is enlarged, the data as shown in Figure 1 can be obtained...... MBUttimnirriBiiiffliinii... The average length of the same row in the same row can be considered to be the number of incoherent combinations and the inverse relationship. The more the number of incoherent combinations, that is, the more raceways are formed outside the mmmm structure, the average bond length (N) becomes shorter. The calculated average chain length (N) is the sequence length of the crystallizable cis-link structure as described above. Therefore, the longer the length (that is, the less irregular bonding), it is considered to improve the rigidity or heat resistance of the propylene polymer. Physical properties such as water vapor barrier properties, etc. (4) The average 鐽 length of each fraction (D, measured by the column method) was obtained at 1301C. The xylene extracted from (1) was dissolved in para-xylene, and the silicon was added. The temperature of the stone is reduced to 3 flt: at a cooling rate of 10 t: / hour, so that it is put on the silica stone, and this is packed in the column. The temperature is raised from 7QC to 130 every 2.5TC. • The average length (8) of each sub-sister obtained through analysis is obtained by the previous method, and this is used as the average chain length (Nf) of the partial group. In the propylene-based polymer of the present invention, Each fraction obtained by fractionation. The average length of the group (M is 8 GQ or more, the total of the partial group is preferably 10% by weight &gt; the upper one. It is preferably 30% by weight or more, especially From 50 paper waves, the Chinese National Standard (CNS) A4 specification (210X 297 mm) is applied again 10 (Please read the precautions on the back before filling this page)-$ A7 ^ 19498 B7___ V. Description of the invention (8) Weight If the average bond length (Nf) is 800 μM, the total is less than 10% of the child, Properties, surface hardness, heat resistance, and water vapor barrier properties lack improvement effects. Next, the method for producing the propylene-based polymer of the present invention will be described. The propylene fluorene polymer of the present invention can be prepared by using one of (A) The solid catalyst component for polymerization is a K-magnesium compound, a titanium compound, a halogen compound, and the first electron-donating compound are essential components * and the first electron-donating compound supported by the solid catalyst component (D) The ratio of Ding to ear (D / T) to titanium (D / T) is D / T 1; (B) there is an aluminum compound; (C &gt; a polymerization catalyst composed of a second electron donating compound, to It is produced by polymerizing propylene. Here, the magnesium compound may be exemplified by magnesium halides such as magnesium chloride, magnesium bromide, and magnesium iodide; such as dimethoxymagnesium, diethoxymagnesium, dipropoxymagnesium, dibutoxymagnesium, and diphenoxy Magnesium alkoxides such as magnesium laurate, magnesium stearate-and phosphonium phosphonates; such as dimethyl magnesium, diethoxy magnesium, and butyl ethyl magnesium alkyl magnesium. These various magnesium compounds may be used alone or in combination of two or more. It is best to use magnesium halide or magnesium alkoxide. Or, magnesium halide is formed when the catalyst is formed. In particular, the aforementioned halogen is preferred. Titanium compounds can be exemplified: titanium halides such as titanium tetrachloride, titanium trichloride, titanium tetrabromide, and titanium tetraiodide; such as titanium tetramethoxylate and tetraethoxylate. Samarium, tetrapropoxy-titanium, tetrabutoxytitanium, tetraphenoxytitanium alkoxytitanium; oxidized titanium ethoxylate, butoxy titanium chloride, phenoxy titanium chloride, oxidized titanium Titanium butoxide, this paper size applies Chinese National Standard (CNS) grid (21 {rx 297 mm) Binding ^ (Please read the precautions on the back before filling out this page) Printed by the cooperative 11 4,9433 A7 B7 V. Description of the invention (9) Titanium halide alkoxide, etc. These various titanium compounds may be used alone or in combination of two or more kinds. Tetravalent titanium compounds containing vegan are preferred, especially titanium tetravalent titanium. Halogen-containing compounds are halogens such as fluorine, gas, bromine, or iodine, and chlorine is tritium. In fact, the specific compounds exemplified depend on the catalyst composition method, but they can be exemplified by titanium tetrachloride and titanium tetrabromide. Titanium halide, silicon tetrahalide, silicon tetrahalide, silicon halide, phosphorus trichloride, phosphorus pentachloride, etc., but the halogen composition, halogenated hydrocarbons, halogen molecules, Halogenated acid. The first electron-donating compound is generally exemplified by oxygen-containing compounds, nitrogen-containing compounds, phosphorus-containing compounds, and carbon-containing compounds. Examples of the oxygen-containing compound include enzymes, ethers, esters, acid halides, and acid anhydrides. For SS, it can be exemplified: for example, methyl alcohol, ethyl acetate, propionate, butyrate, pentyl alcohol, hexyl alcohol, heptyl alcohol, octyl yeast, nonyl alcohol, decanol, 2-ethyl yeast, oil yeast, benzyl alcohol , Phenylethyl fermentation, phenol, cresol, ethylphenol, naphthalene fermentation;-such as methyl ether, ether, propyl ether, butyl ether, pentyl ether, hexyl ether, tetrahydrofuran, anisole, diphenyl ether Ethers or diethers; printed by the consumer cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs, such as ethyl acetate, ethyl acetate, ethyl propionate, ethyl deer, ethyl acrylate, crotonate, and oleic acid Ethyl ester, Ethyl stearate, Ethyl phenyl acetate, Methyl benzoate, Ethyl benzoate, Propyl benzoate, Butyl benzoate, Butyl phenyl acetate, Methyl ethyl benzoate, Anisic acid Methyl Ester, Ethyl Anisate, Ethoxy Benzoate Methoxylate, Ethoxy Benzoate-Ethyl Acetate, Ethyl Silicate, Dimethyl Peptide, Diethyl Phthalate, Dipropyl Peptide, Phthalate Di-n-butyl acid, diisobutyl peptidate, dihexyl phthalate, peptidic acid 12 ^^ 1 HI n II ^^^ 1 ^^^ 1 ^^^ 1 (Please read the notes on the back before filling (This page) The 伕 standard is applicable to the Chinese National Standard (CNS) A4 specification (210X 297 mm) 4J9498 Α7 Β7 Printed by the Consumers' Cooperative of the China 夬 Standards Bureau of the Ministry of Economic Affairs 5. Description of the Invention (iG) Dioctyl ester, 7-butyrolactone, δ- Esters of valerolactone and ethylene carbonate; such as ethyl sugar, benzoic acid, phenethyl chloride, acid acid, etc .; such as maleic anhydride, phthalic anhydride and so on. These first electron-donating compounds may be used alone * or in combination of two or more kinds. M esters are preferred. M peptide esters are particularly preferred. Of course • Among the four compounds, a magnesium compound, a titanium compound, a halogen compound, and a first electron-donating compound, two or more kinds can be used for one compound. The amount of each of the foregoing components used in the present invention may be any effect as long as the effect can be exhibited. * Generally, however, the following is preferred. The amount of the titanium compound used relative to the amount of the magnesium compound used is such that the ear ratio is in the range of 0.00 1 to 1,000, and the range of K 0.01 to 100 is preferable. Halogen compounds can be used as required. When halogen compounds are used, the amount of titanium compound used does not vary depending on whether the titanium compound or magnesium compound contains no halogen. The amount of molybdenum relative to the magnesium used is Q.Q1. Within the range of ~ 1000, preferably within the range of 0.1 ~ 100. The molar ratio of the first electron-donating compound to the amount of the aforementioned magnesium compound is within a range of 0.001 to 10, and more preferably within a range of 0.01 to 5. The method for preparing the solid catalyst component used in the present invention can be adjusted from a conventionally known solid catalyst component, that is, the magnesium compound, the titanium compound, and the first electron can be temporarily or stepwise The donor is obtained by contacting a chemical compound with a halogen-containing compound and the like. 1.111 n Order 111 — (Please read the notes on the back before filling out this page) This paper size is applicable to China National Standard (CNS) A4 (210X 297 mm). W 349.8 A7 _B7 _ 5. Description of the invention (11) Specific examples of known methods include the following modulation methods. (1) A method of contacting a magnesium halide and a first electron donating compound and a compound as needed. (2) A method of contacting a titanium halide compound and / or a silicon halide compound with a solid component *, and the solid component is obtained by contacting a magnesium halide with a tetraalkoxy titanium and a specific polysilicon compound. (3) A method in which a titanium compound is brought into contact with a solid component, and the solid component is M tetraalkoxy titanium and the first electron-donating compound to dissolve the magnesium compound, and the M halogenating agent or titanium halide compound to precipitate it . (4) A method in which an M phosphorus halide compound treats alumina and magnesium oxide, and contacts the magnesium halide, the first electron donating compound, and the titanium halide compound. (5) A method of contacting a first electron-donating compound with a titanium compound after the Grignard reagent, which is a representative organomagnesium compound, reacts with a suitable agent or a halogenating agent. -(6) A method of contacting a halogenating agent and / or a titanium compound with a magnesium alkoxide compound in the presence or absence of the first electron-donating compound. (7) M tetraalkoxy titanium dissolves magnesium compounds • Polymerization of K silicon compounds after hip treatment • Method of processing M silicon halogen compounds and organometallic compounds 0 (8) M # 1 electron donating compound and titanium halide A method for treating a spherical magnesium compound / fermentation complex, such as a compound. -In order to manufacture the propylene polymer of the present invention, any one of the above-mentioned methods for preparing a solid catalyst component may be used. * At least one must support the standard of the solid paper. Applicable to China National Standard (CNS) Λ4 specification (210X297). PCT) 14 (Please read the notes on the back before filling out this page).

, TT 4 i949g A7 B7 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (12) Molar ratio (D / Τ) of the first electron-donating compound / titanium atomic weight of the catalyst component is D / Τέ 1 Polymerization heating catalyst component. At this time * D / T2 1.5 is better. When D / T &lt; 1, it is difficult to obtain the highly stereoregular propylene polymer of the present invention. Thus, according to the present invention, it is possible to provide a solid catalyst component for ct-olefin polymerization, which is composed of a magnesium compound, a titanium compound, a halogen compound, and a first electron-donating compound. Among the solid catalyst components, The molar ratio (D / T) of the first electron-donating compound (D) and titanium (T) supported is D / T ^ l. This warming catalyst component is used to produce the polypropylene with high stereoregularity. However, it can also be used as a general propylene polymer or a propylene polymer to polymerize α-olefins from outside. Use solid catalyst ingredients. In particular, in order to obtain a propylene-based polymer having high stereoregularity and requiring sugariness and heat resistance, D / T ^ 1.5 is preferred. In the conventional preparation method, even if it is a solid catalyst component that does not satisfy the above conditions (_ D / TS 1), the solid catalyst component that can satisfy the above conditions can be improved by further processing as shown below. And better. At this time, the mole ratio (D / T) of the first tritium donor compound / Ti atom content in the solid catalyst component before the modification, and the first electron donor compound / Ti in the modified catalyst component The atomic content of the ear ratio (1) / T) η · must be at (D / T), &gt; 1 if the system is (D / T) »/ (D / T), a difference of 2 is better. -For example, the solid catalyst components prepared by the various known methods mentioned above include magnesium, titanium, halogen, and the first electron-donating compound as essential components (please read the notes on the back ^ before filling this page) '-° Γ This paper size applies Chinese National Standard (CNS) A4 specification (210X 297 mm) 15 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 4,949β at B7 V. Description of invention (13) • Further to The treatment with the first electron-donating compound and / or the halogen-containing compound can increase the D / T ratio before the treatment and improve the catalyst. There are no restrictions on the order and number of times the first electron-donating compound is used for the temperature and treatment with the dentin compound, but the general treatment method for solid catalyst components is the first electron-donating compound. After supporting, wash and wash with a halogen-containing compound, and then wash with a hydrocarbon. The first electron-donating compound used in the improvement of the catalyst component can be the same or different from the user used in the preparation of the solid catalyst component before the improvement. The first electron-donating compound can be used alone or in combination. More preferred are esters, and more preferred are phthalates. The usage amount of the first electron-donating compound may be in the range of 0.001 to 50,000 mol times with respect to the titanium atom in the solid-state catalyst component. Preferably it is in the range of 0.01 to 50 mol times. It is difficult to obtain the (D / T) m / (D / T), &gt; 1 actinide system when the first electron donor compound is rarely used. Conversely, the first electron donor compound When it is used in an extremely large amount, it is not preferable because the polymerization activity is reduced. The halogen-containing compounds used in catalyst improvement can be the same or different from those used in the preparation of solid catalyst components before modification. Of these, M titanium halide, silicon halide, and halogenated hydrocarbon are preferred. The halogen-containing compounds may be used alone or in combination of two types. The amount of the halogen-containing compound used is in the range of 0.1 to 1Q000 mol ratio relative to the titanium atom in the solid catalyst component, preferably in the range of 1 to 3,000 mol ratio, and more preferably in the range of 5 to 5Q0 mol ratio. Inside. In addition, when the amount of halogen-containing compounds is extremely small, it is difficult to obtain the relationship between (D / T) m / (D / Th &gt; 1) The paper size applies the Chinese National Standard (CNS) A4 specification (210X 297 mm) 16 I Binding I 〆 (Please read the precautions on the reverse side before filling out this page) A7 4t9498 B7 V. Description of the invention (14) • Conversely, when the amount of halogen-containing compounds is extremely high, the polymerization activity will be reduced. • The amount of waste liquid # 变 多 • ture is not good. I--m. 4HI ^^^ 1 ^^^ 1 m 1 ni,-° {Please read the precautions on the back before filling out this page) For improvement • Use the first electronic supply The temperature of the solid catalyst catalyst component treated with the sexual compound is -30 ~ 15ΰΙ, preferably 0 ~ 100 = within the range. Also, the temperature of the solid catalyst catalyst component treated by the halogen-containing compound is Q ~ 20 0¾, preferably in the range of 50 ~ 150 ° C. At these other temperature conditions * Due to the decrease in polymerization activity | It is not good. The improvement treatment with the first electron-donating compound and the halogen-containing compound of the solid SS catalyst component is generally carried out in a hydrocarbon solvent. The hydrocarbons used at this time are preferably: aliphatic carbons such as pentane, hexane, heptane, octane, decane, etc .; aromatic hydrocarbons such as benzene, toluene, xylene, etc. Active hydrocarbons. In addition, these hydrocarbons can be used as a cleaning solvent for the solid catalyst component after being treated with the first electron-donating compound of the solid catalyst component and the halogen-containing compound. The first electron-donating compound of the solid catalyst component before the improvement is processed, and the halogen-containing compound is cleaned. The modified olefin polymerization catalyst is used by the Consumers ’Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs. The temperature at the time of washing is Q ~ Fan, preferably 60 ~ 140Ό. At this time, when the cleaning temperature is extremely low, it is difficult to obtain the relationship of (D / T) m / (D / T), &gt; 1. On the contrary, when the cleaning temperature is extremely high, (D / TU / ( D / Th &gt; 1 actinide, but it is not good because the polymerization activity is reduced. When the solid catalyst component is treated with the first electron-donating compound, if it is not treated with a halogen-containing compound (washing) | Polymerization activity Will be very low, and • The effect of the present invention will not appear. Treatment with halogen-containing compounds 17 This paper size applies Chinese National Standard (CNS) A4 specifications (210X 297 mm) 4 1949s A7 B7 V. Description of the invention (15) The number of times of (washing) is not particularly limited *, but in order to fully show the effect of the present invention * M2 times to 4 times is preferred. When M1 times * the effect of the present invention cannot be fully shown, if the number of times of repetition is too large, the polymerization activity It is unfavorable. Also, in the present invention *, the first electron-donating compound uses the general formula TiXa · Yb (wherein X is a halogen atom of Cl, Br, and Ϊ, and a is 3 or 4 · Y is an electron The titanium compound represented by the donor compound (1),) is treated with the titanium compound, and then washed with a halogen compound and further washed. Μ Hydrocarbon washing • Can be improved to a solid catalyst component with a D / Tgl support. This way | When the solid catalyst component is treated with the first electron-donating compound, generally • The halogen-containing compound of the present invention is used The number of times the compound is processed (washed) must be at least twice as described above. However, when TiXa · Yb is used, the number of times the M halogen-containing compound is processed (washed) is 1 or 2. The effect of the present invention can be sufficient. Appearance. * As described below • The amount of halogen-containing compounds can also be reduced. • The amount of waste liquid discharged when cleaning the solid vehicle components with carbon compounds can also be significantly reduced. — TiXa (in the formula , X is a halogen atom of Cl, Br, I, and a is 3 or 4) · As described in 11.3.?. (] 〇111 ^ 5,?. (]. ¥ &amp; 1163, nine (^ 311 ·

Organometal. Chem., 9_, 135 (1970), 4th edition of New Experimental Chemistry Lecture 17 Inorganic complexes and complexes. Chemical Society of Japan Maruzen (1991) p. 35, HK Kakkoen, J. Pursiainen, TA Pkkanen , M. Ahlgren, B. Iiskola, J. Organomet. Chem .. 453, 17 5 (1S 9 3), etc., the so-called electron-donating compounds are generally known to easily form complexes.

X of TiXa · Yb is a halogen atom of Cl, Br, I, of which KC1 is the paper standard and applies Chinese National Standard (CNS) A4 specification (210X297 mm) ^^ 1 ^^ 1 I--^^ 1 β *! / ^^ 1 ^^^ 1 ^^ 1 mm 1 ^ 1 «3. VT (Please read the notes on the back before filling out this page) Printed by the Staff Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 18 ί9438 Α7 Β7 Central Standards of the Ministry of Economic Affairs Bureau employee consumer cooperative printed i, invention description (16). a is 3 or 4, but 4 is preferred. Y (the first electron-donating compound) can be selected from the aforementioned *. It can also be the same as or different from the one used in the preparation of the solid catalyst component before improvement. When preparing TiXa *, the first electron-donating compound can be used alone or in combination of two or more types. ◦The better Y is the phosphonates. The most preferred is the phosphonates. B of Y is 0 when a is 3; b is 3; a is 4 when a is 4; b helmet 2, the ear ratio of Y relative to TiXa when modulating TiXa · Yt depends on Y The number of electron donors and the atomic value of Ti are determined. The best case is when a is 4 and b is 1. The amount of TiXa · Yb used is relative to the titanium atom in the solid catalyst component before the improvement. It is in the range of 0.0D1 ~ 5Q0, and it is preferably in the range of Q.01 ~ 50, and more preferably It is in the range of 0.1 to 10 mole ratios. In addition, when the amount of TiXa · used is extremely small, it is difficult to obtain the relationship of (D / T) m / (D / T), &gt; 1. Conversely, when the amount of TiXa · Yb2 used is very large, the polymerization activity is reduced * good. -The use of halogen-containing compounds 遒 relative to the grain atoms in solid catalysts is in the range of 0.1 to 10 G0 1, preferably in the range of 1 to 500 mol, especially 5 to 100 mol Inside the fan garden. The selection of the halogen-containing compound may be the same as described above. In addition, the temperature of the MTiXa · Yb-treated solid catalyst component may be the same as that of the first electron-donating compound, and the temperature at which the M-halogen-containing compound cleans the solid catalyst component may be the same as that of the former. -Treatment of TiXa · Yb of Μ solid catalyst components, and cleaning of Μ halogen-containing compounds can be the same as that of the aforementioned first compound donor compound. This paper is based on the general Chinese National Standard (CNS) A4 specification (210X 297). Public Holiday) 19 (Please read the notes on the back of the cabinet before filling out this page) Ding-β 4 t9498 A7 B7 V. Description of the invention (17) Treatment and cleaning with halogen-containing compounds. {Please read the notes on the back before filling this page.) There are no special restrictions on the number of times TiXa · Yb is treated under K, and the number of times of washing with halogen-containing compounds is not limited. However, as mentioned above * If MTiU · Yt is processed, The halogen compound is washed once or even twice, and the effect of the present invention can be sufficiently exhibited. Without washing with a halogen-containing compound, 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 organoaluminum compound and the second electron-donating compound in the post-condensation method, but a small amount can be prepared before polymerization. Of the monomer. In general, the modified solid catalyst component is about O.Olg to about 100Og * per lg. The temperature for preliminary polymerization is arbitrary, but M-30 ~ 80 ° C is preferred. The preliminary polymerization is usually carried out with the coexistence of a hafnium aluminum compound and a second electron-donating compound used in the later-described polymerization.% The preliminary polymerization can generally be carried out in an inactive hydrocarbon solvent *, but it can also be used in In liquid monomer-, gas phase monomer. In addition to propylene, the monomers used in the printing of preliminary polymerization by the Employees' Cooperatives of the China Standards Bureau of the Ministry of Economic Affairs can be used in addition to propylene, such as: ethylene, 1-butene, 3-methyl-butene, 3-methyl-butene Olefins, 4-methyl-pentene, 4,4-dimethyl-pentene, vinylcyclopentane, vinylcyclohexane, etc. £ -olefins, styrene, α-methylbenzene Styrene derivatives such as ethylene, trienes such as butadiene, 1,9-decadiene, and allyltrialkylsilanes. In addition, these military bodies can use not only one type, but also two or more types of pupae-ground or mixed use. It is also possible to use hydrogen as a molecular regulator in the preliminary polymerization. 20 This paper scale is applicable to the Chinese National Standard (CNS) Λ4 is present (210 × 297 mm) Magic 9 &lt; 98 ------ V. Description of the invention (18 Polymerization of printed propylene in the Consumer Cooperatives of the Central Procurement Bureau of the Ministry of Economic Affairs The above-mentioned improved solid catalyst component can polymerize a propylene-based polymer in the presence of a hafnium aluminum compound and a second electron-donating compound. Representative examples of the organoaluminum compounds used in the present invention include: Aluminum, triethylaluminum, tripropylaluminum, tributylaluminum, trihexylaluminum, trialkylaluminum of trioctylaluminum; such as dimethylaluminum hydride, diethylaluminum hydride, dibutyl Alkyl aluminum hydrides of aluminum hydrides; such as dimethyl aluminum chloride, diethyl aluminum chloride, diethyl aluminum chloride, ethyl aluminum half chloride, etc .; such as diethyl Alkyl aluminum alkoxides of aluminum ethoxide, diethylaluminum phenate, etc .; such as methylalumoxane, ethylalumoxane, propylalumoxane, alumoxane. These organoaluminum compounds can be K1 type can be used alone * or 2 or more types can be used together. Preferred is triethylaluminum. Used in the present invention The second electron-donating compound may be the same as or different from the first electron-donating compound. However, representative examples include: aromatic carboxylic acid compounds, having Si-0-C or Si-NC Bonded silicon compounds, acetal compounds, gallium compounds with Ge-0-C bonds, heterocyclic compounds of nitrogen or gas with alkyl substituents. Examples of these compounds can be exemplified as: benzoic acid ethyl S , Aromatic carboxylic acid esters of ethyl p-toluate, ethyl p-anisinate; such as phenyltrimethoxysilane, diphenylmethoxysilane, diphenylmethoxysilane, di-n-propyldimethoxy Silane, diisopropyldimethoxysilane, di-tert-butyldimethoxysilane, dicyclohexyldimethoxysilane, dicyclopentyldimethoxysilane, cyclohexylmethyldimethoxy Silane, tert-butyltrimethoxysalane, cyclohexyltrimethoxysilane, hexyltrimethoxysilane, tetramethoxy This paper is based on the Chinese National Standard (CNS) A4 specification (210: &lt; 297 mm ) 21 --------- ¾Water ------ ίτ ------ ^ (Please read the notes on the back before filling this page) Printed by the Consumer Standards Cooperative of the Ministry of Standards of the People's Republic of China 4 19498 A7 B7 V. Description of the invention (η) Silane compounds of silane and tetraethoxysilane; benzophenone dimethoxy base, dibenzophenone diethoxy Acetal, acetophenadimethoxyacetal, acetophenadioxydiethoxyacetal acetal compounds; such as diphenyldimethoxyoxane, benzyltriethoxyoxane Compounds such as heterocyclic compounds of 2,2,6,6-tetramethylhexahydropyridine. In addition, these electron-donating compounds can be used alone or in combination of two kinds of K. Better It is a silicon compound or a crepe compound, particularly preferably a silicon compound having Si-0-C 鐽. The polymerization method in the manufacturing method of the present invention is not specific, and a known method can be used to remove the slurry polymerization or block polymerization of cypress. In addition to the polymerization method, a gas phase polymerization method may be used. In addition, it is applicable not only to batch polymerization, but also to continuous ore polymerization and back-fraction polymerization. The polymerization solvent used in the slurry polymerization can be used alone or in combination with saturated aliphatic or aromatic argon compounds such as hexane, heptane, cyclohexane, methylbenzyl and the like. In addition, the polymerization method of the manufacturing method of the present invention can also use a multi-stage polymerization of two or more polymerization reactors. — The polymerization temperature is about -50 to 200, preferably K 20 to 150 ¾, and the polymerization pressure is atmospheric 懕 ~ 1 (30 kg / caa G, preferably 3 to 50 kg / ciE 2 G. Also, add appropriate S during polymerization Hydrogen can adjust molecular weight. In addition to the separate polymerization of propylene in the production method of the present invention, it is also possible to make propylene and a hydrocarbon residue of the general formula R-CH = CHa (where R is a hydrogen atom or Ci ~ Cae, (Also branched) can be used for the copolymerization of α-olefins. It can be exemplified by ethylene, butene, 3-methyl-1-butene, and 3-methyl-butene. Ene, 4-methyl-pentene, 4,4-dimethyl-1-pentene, vinylcyclopentane, vinylcyclohexane, etc. In addition, styrene can be exemplified. The paper size applies to Chinese national standards.隼 (CNS) Λ4 specification (210 X 2? 7 mm) 22 I -------- i ------ Order ------ ^ (Please read the notes on the back before filling (This page) ^ i ^ 49g A7 B7 V. Description of the invention (2 (5), ct-methyl-benzyl ethylene and other stilbene derivatives, butadiene, 1,5-hexadiene, 1,7-octadiene Olefins, 1,9-decadiene and other dienes, allyl alkyl silanes. And these monomers can It can also be used as a mixture of two or more types. Also in the propylene-based polymer of the present invention *, a propylene-ethylene block bark copolymer can be produced by multi-stage polymerization of two or more K polymerization reactors * especially in the first stage Polypropylene is preferred. At this time, if the elementary polypropylene taken out after the completion of the first stage polymerization satisfies the constitutional requirements of the present invention, the copolymer finally obtained may also have the physical properties obtained by solving the problems of the present invention. The propylene polymer obtained by the invention can be obtained by adding a known nucleating agent, and M can obtain a resin composition which further improves crystallinity and high-speed moldability. Examples of the nucleating agent include, for example, I of military carboxylic acid, and Ila family of gold tincture (such as sodium benzoate), dicarboxylic acid (adipic acid), aliphatic dicarboxylic acid III-~ IV group of gold tincture salts (such as pt-butyl aluminum benzoate), two Fillers for benzylidene glucosyl derivative, talc, etc. Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling this page). For example: 1,3,2, 4-dibenzylidene grape fermentation 1,3,2,4-bis- (p-methylbenzylidene) glucose, 1,3,2,4-bis- (p-ethylbenzylidene) glucose, 1,3, 2,4-bis- (p-chlorobenzylidene) glucose, 1,3-P-chlorobenzylidene-2,4-p-methylbenzylideneglucose, nano-bis- (4 -t-butylphenyl) phosphate, na-2,2-methylene-bis- (4,4-di-t-butylphenyl-yl) phosphate, na-2-2'-ethylene Inorganic fillers such as bis- (4,6-di-t-butylphenyl) phosphate and talc, calcium carbonate, etc. This paper size applies to China National Standards (CNS) / \ 4 specifications (210 X 297 mm) -2 3-Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs ^ 9q A7 B7 V. Description of the invention (2〇 The amount of the nucleating agent added is at least 0.05 to 15% by weight of the nucleating agent in the propylene-based polymerization bet, and the effect of the present invention is very significant. Although M0.05 to 0.8% by weight is preferred, 0.1 ~ 0.5% by weight is preferred. However, since inorganic compounds such as talc are smaller than the nucleating effect of the nucleating agent exemplified above, 1 to 15% by weight can be added. 2 to 15% by weight is preferred, especially M 5 It is preferably 10% by weight. For the propylene-based polymerized resin or resin product of the present invention, as long as it does not impair the purpose of the present invention, other additives (such as oxidation inhibitors, Weathering stabilizers, charging inhibitors, slip agents, crimp inhibitors, anti-S agents, dyes, oils, rhenium, etc.) For example: Examples of such additives, that is, the oxidation inhibitor is 2,5-di-bubutyl Hydrazone, 2,6-di-bubutyl 1-cresol, 4,4-thio-bis- (64-butylphenol ), 2,2-methylene-bis (4-methyl-6-t-butylphenol), octadecyl-3- (3 ', 5'-di-t-butyl-1'-hydroxyl Benzoyl) propionate, 4,4 · -thio-bis (6-butylphenol), UV absorber is ethyl-2-amino-3,3--dibenzyl acrylate, 2- (2 '-Hydroxy-5-methylbenzyl) phenyl beta nitrogen, 2-hydroxy-4-octyl benzophenone, plasticizers are peptidyl dimethyl cool, diethyl phthalate, amidine, mobile stone , Phosphoric acid, Charge inhibitors are stilbene stearic acid, sorbitan monopalmate acid K, sulfated oleic acid, polycycloethoxylate, carbofluorene, and lubricants are ethylenebisstearylamine, butyl Stearate, etc. * Colorants are carbon black, peptide cyanide, acridine, dihydrofurfural, nitrogen-based pigments, titanium oxide, ferric oxide, etc., and fillers are glass fiber, stone shrink, mica, and silicon. Acid-calcium, aluminum silicate, etc. In addition, many other high molecular compounds can be mixed as long as they do not impair the effect of the present invention. The paper size is in accordance with the Chinese National Standard (CNS) Λ4 specification (2! OX297 mm ) 24 I. III — I III gland (Please read the precautions on the back before filling (Write this page) 4 19498, "94" Central Standard of the Ministry of Economic Affairs, printed by employee consumer cooperatives V. Description of the invention (22) Melt index of the propylene polymer of the present invention (MFR ~ JIS-7210, Table 1 Condition 14) There is no particular limitation. • It can be selected according to the molding method and application. However, the range of K 0.1 to 50 0 g / lG is generally suitable. The propylene polymer of the present invention can be formed by a known melt molding method and press molding. It can be used as injection molding, film, sheet, pipe string, screw, etc., and laminated with carcass and other materials. For example, such a lamination method uses a dry laminating adhesive such as a polyurethane type or a poly grinding type, and accumulates other thermoplastic properties in a single calendar product of the acrylic polymer or resin composition of the present invention. The resin layer * is implemented by the so-called dry accumulation calendar forming method or Sandwitch accumulation calendar method; or * co-extrusion lamination method, co-extrusion (feedbloclt method, fflulti-isanifold method), co-injection molding method, co-extrusion tubular molding method. The multi-layer lamination system obtained in this way uses a vacuum forming machine, an air pressure forming machine, a stretch blow molding machine, and the like, and reheats it, and the method of stretching is added, or a single sleeve or double sleeve stretching is used to laminate this multilayer. Body or Army Zhao-The shaped object is subjected to a heating extension operation. Brief Description of Drawings Fig. 1 is an example of a 13C-NMR spectrum chart of a methyl region of a simple polypropylene. In the following, the present invention will be described in more detail by way of examples. The spring example is also shown in the following. The method and device for measuring various physical properties in the present invention are shown below. (1) Dibenzyl insoluble (XI) 2.5 g of polymer is dissolved in 135¾ of o-xylene (2 50 ml ) -----------* fe, HI n ^^ 1 ^^ 1 ^^ 1 ^^ 1 U3 * ^-5 (Please read the notes on the back before filling this page) Applicable to China National Standard (CNS) Λ4 specification (210X297 mm) 25 A7 4 f9498 B7 5. In the description of the invention (23), the polymer (% by weight) precipitated in 25D is used as the xylene insoluble (XI). (Please read the precautions on the back before filling in this page) (2) The five-point fraction (mmmm) πιηπιπι is the percentage of methyl quintile units in the propylene polymer molecule 鲢. The measurement was performed using JNM-GSX400 (iaC NMR frequency 1QQ MHz) made by Japan Electronics Corporation. The individual signals are attributed to Macronolecules, 13, 267 (198Q) by M A. Zambelli et al. The measurement conditions are shown below. Measurement of chess style U〇de): Protron decoupling method Pulse width: 8.01 &lt; is Pulse round trip time: 3.0 iis Number of horizontal calculations: 20000 times Solvent: 1, 2, 4-trichlorobenzyl / heavy mixed solvent ( 75/25% by volume, Internal standard: Hexamethyldisilazane-Test concentration: 300 * g / 3.0 nl Solvent measurement temperature: 120Ό (3) Average length of Shunlian (N) Staff of Central Bureau of Standards, Ministry of Economic Affairs The average bond length U) printed by the consumer cooperative is calculated according to the method reported by JC Rodall (Polyner Sequence Pistribution Academic Press, New York 1 977, Chapter 2). Specifically, polypropylene is dissolved in a mixed solution of 1,2,4-trifluorobenzene / heavy benzene, and the temperature is increased to 13 ° -υ * K so that the polymer concentration becomes 10% by weight. Put this solution into a glass sample tube with an inner diameter. * Same as 26 paper scales. Applicable to China National Standard (CNS) Λ4 specification (2Ι0 × 297 mm) A7 B7 ^ 19498 5. Description of the invention (24) (Please read the back first Please note this page and fill in this page again) The 13C-NMR was determined by the previous measurement conditions of the pentad fraction (IP). Secondly, as explained earlier, the average bond length (N) is obtained from the number of chains in the intermediate and the number of units in the intermediate as defined below. N = number of intermediates / units of intermediates (4) The column method was used to dissolve xylene non-vortex propylene polymer in p-xylene at 130 ° C. ίου / The cooling rate of time is reduced to 3〇υ, so that it is attached to the silica. Fill this adherent into the column, and raise the temperature from 2. to 130 ¾ each time. • Distill into different parts and group. (5) Injection molding using Toshiba Machine (stock) IS-ΠΟΡΙ (theoretical injection capacity S250 cm3) * At a molding temperature of 220 and a mold cooling temperature of 50¾, Izod impact test pieces, flexural modulus test pieces, and load-flex Temperature test strip, surface gloss test strip (thickness 2 * ×× 15 cnxil cb flat plate). -Secondly, after placing two painting nights in a constant temperature room with a humidity of 50% and a temperature of 23¾, determine these physical properties. (6) Izod® impact strength (with gaps) Printed on the basis of MJIS ΚΠΙ printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs. The device is a ϋ-F impact tester made by Ueshima Manufacturing Co., Ltd. (7) Flexural modulus Pickled in accordance with JIS K72Q3. -(8) Ethylene content is based on 13C-NMR method (Macromolecules, 27 reported by CJ · Carman et al.) This paper size applies to Chinese national standards (CNS M4 specification (210X 29? Mm) Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 419498 A7 B7 V. Description of the invention (25) 10, 537 (1977) Calculated. (9) MFR (Melting Flow Rate) MJIS K7210 Table 1 Condition 14 is based on the implementation of the device using the melting index (10) The load deflection temperature is based on the JIS K7207B method and is implemented using the HDT e VSPT tester manufactured by Toyo Seiki Seisakusho. (11) Extrusion molding machine with Rockwell surface hardness M temperature 23DC The AR-1G Rockwell Hardness Tester manufactured by Toyo Seiki Seisakusho Co., Ltd. was used in accordance with JIS K72Q2. (12) The film was made into a thin film forming machine manufactured by Yoshii Kogyo Co., Ltd. 4Q am 0Τ die. The die temperature is 230C, cooling temperature is 30t :, and the drawing speed is 10 a / min, and a 6Q Jim thick film is made, and the water vapor transmission rate, Haze, and surface-gloss are measured. (13) Haze KJIS K7105 method is based on , Using the sugar test Implemented by Haze meter (HGM-2D) (U4) U4) Surface gloss based on KJIS K7 105 method, implemented by VG-1D gloss meter manufactured by Nippon Denshoku Kogyo Co., Ltd.-(15) Water Vapor transmission through 霣 M ASTM-E96, using Modern Controls Inc. paper size Applicable to China National Standard (CNS) A4 (210X297 mm) 28 t I, 11 11 1 n ^ It Jil ball (Please read first Note on the back, please fill in this page again.) Printed by the Consumers' Cooperative of the Central Procurement Bureau of the Ministry of Economic Affairs 419498_B7_ V. Description of the Invention (26) Permatran W was measured at a temperature of 37.8D and a relative humidity of 90%. (16 ) Catalyst analysis K dilute sulfuric acid decomposes the solid catalyst component before improvement, and solid catalyst component for improved olefin polymerization * K heptane extracts organic matter. Uses atomic absorption AA610S type quantitative water layer made by Shimadzu Corporation .Hitachi Manufacturing Co., Ltd. Gas Chromatography Analysis 2 63-50 Quantitative electron donor compounds in the heptane layer. Example 1 (1) Preparation of solid catalyst components before improvement (conventional usage) Under nitrogen at 1201C in nitrogen Anhydrous magnesium 56.8g (597 · 1) Dissolved in 100 g of anhydrous ethanol (Π4 mmol), vaseline CP15N 5QQ ml made by Idemitsu Kosan Co., Ltd. and silicone oil KF96 50 ml made by Shin-Etsu Silicone Co., Ltd. Use a special TK homomixer made by special chemical industry (stock) to stir this mixture at 120 ¾ M3QQ 0 revolutions per minute for 3 minutes, while _ keeping stirring while transferring to 2 liters of anhydrous heptane. The obtained white solid was thoroughly washed with anhydrous heptane, and dried under vacuum at room temperature. 30 g of the obtained spherical solid of MgCla · 2.5 C, HaOH was suspended in 200 ml of anhydrous heptane. Add 0 50 ml (4 · 5 mol) of tetra-aerated titanium to the bottom of 0¾ while stirring for one hour. Secondly, when the heating started to reach 40¾, diisobutyl titanate 4.96g (17.8 mmol) was added, and the temperature was raised to about 100 ° C in about 1 hour. After 2 hours of reaction, the solid portion was taken off while hot. Then, a suspension of titanium tetra 500 · 1 (4.5 B〇l) was suspended in the ί ^^^^ 1 ^^^^ 1 J-JJ ^^^^ 1 ^^^^ 1 ^^^^ 1 ^ ^^^ 1 (Please read the notes on the back before filling out this page) This paper size is applicable to China National Standard (CNS) A4 (210X29? Mm) 29 Printed by the Bayer Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 419498 A7 B7 V. Description of the invention (27) The reaction product is further reacted at 12Qt for 1 hour. After the reaction was over, the solid portion was taken again while hot, and washed 7 times with 1 liter of hexane in 60 ¾ • Washed 3 times with 1.0 liter of hexane in room temperature. After measuring the titanium content in the obtained solid catalyst component, it was 2.25% by weight. It also contained 7.81% by weight of the electron-donating compound (1). (2) Preparation of improved solid catalyst component 20 g of the solid catalyst component obtained above was suspended in 300 ml of toluene, and reacted with 2.78 g (10 mmol) of diisobutyl titanate at 25¾ for 1 hour. After the reaction was completed, tetratetitanium 100 »1 (900 ml) was added and reacted at 90 t for 1 hour. After the reaction was completed, the solidified portion was taken while being heated. Then, 100 ml (900 nmol) of toluene 300 Bl titanium tetrachloride was suspended in the reaction product, and the reaction was performed at 90 t: 1 hour. After the reaction is over • again • Filtrate the solid part while it is still hot, and wash it 7 times with 90 ml: 500 ml of methylbenzene, and then wash 3 times with 500 ml of hexane at room temperature. The content of titanium in the obtained solid catalyst component was measured and found to be 1.Q1% by weight. In addition, it contains 12.0% by weight of the first electron-donating compound. The analysis results of the catalyst components before and after the comparison are shown in Table 1. (3) Preliminarily polymerize under a nitrogen atmosphere * Put 500 ml of n-heptane, 6.0 g of triethylaluminum (53antol), 0.39 g of dicyclopentyldimethoxysilane into a pressure net with an internal volume of 3 liters ( 17 ubioI) and 10 g of the improved olefin polymerization catalyst component obtained in the above (2). Stir for 5 minutes at a temperature range of 0 to 5C. The second time is to supply propylene in the pressure cooker so that 10 g of propylene can be polymerized per lg of the improved olefin polymerization catalyst component. The polymer is prepared to polymerize for 1 hour in the range of 0 to 5 degrees. : Yang) 6 4 specifications (2 [0 乂;! 97mm) 30 (Please read the precautions on the back before filling out this page) Equipment *,? Τ 4 19498 A7 B7 Printed by the Employees' Cooperatives of the Central Commission of the Ministry of Economic Affairs Preparation 5. Description of the invention (28). The obtained preliminary polymerized solid vehicle component was washed three times with 500 ml of n-heptane and used in the production of the following propylene-based polymer. (4) Under the polymerization nitrogen atmosphere In a 60-liter internal pressure net with a stirrer attached with forceps, put 2.0 g of the preliminary polymerization solid media prepared by the method described above, 1-4 g (100 mmol) of triethylaluminum, and dicyclopentyl di 6.84 g (30 maiol) of methoxysilane, 18 kg of propylene was charged with tritium gas to 13 GD0 »olppm relative to propylene, the temperature was raised to 70¾, and polymerization was performed for 1 hour. After 1 hour, unreacted propylene was removed * The polymerization is finished. Results * 6.56 kg of polypropylene can be obtained, and the polymerization activity is 32.8 kg / g—solid catalyst The MFR of the sub-polymer was 33.0 g / Mθ. 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 the modification was the same as in Example 1. _ (2) TiCMCeH4 (COOlC * H9),] was prepared in a 1.0 liter solution of hexane containing 19 g (100 mmol) of titanium tetrachloride, and while maintaining the same, diisobutyl titanate was dripped over 30 minutes: 27.8% (100 mmol). After the dropping is completed, the temperature is raised to 40 ^ 0, and the reaction is performed for 30 minutes. After the reaction is completed, the solid portion is taken and washed 3 times with 5QG ml of hexane to obtain the target. (3) Improved olefin polymerization catalyst components Modulation. Suspend 2Qg of the solid catalyst component obtained above (in 300 ml, MTiCMCeHWCOOifMhh) at 251, 5, 2g (11 nmol) This paper scale is applicable to China National Standard (CNS) Α4 specification (210X297 mm) 31 -------- • Equipment-- (Please read the precautions on the back before filling in this page)

, 1T 419498 A7 B7 V. Description of the invention (μ)) Treat it for 1 hour to support it. After the end of the support | Take the solid part while it is still hot. Resuspend it in 300 ml of methylbenzyl and IQ ml of tetragas titanium (90 nmol), stir and wash at 90¾ for 1 hour, and filter while hot; take the solid Partially, the reaction was washed 5 times with 500 ml of toluene, and then washed 3 times with 5Q0 ml of hexane at room temperature. When the titanium content in the obtained solid catalyst component was measured *, it was 0.91% by weight. The first electron-donating compound contained 10.6% by weight. The catalyst analysis results before and after the improvement are compared, and are not shown in Table 1. (4) Preliminarily polymerize under a nitrogen atmosphere.Put n-heptane 50 0 nl, 6.0 g (53 mmol) of triethylaluminum, 3.9 g (0.017 mmol) of diphenyldimethoxysilane in a 3 liter pressure cooker. ) And the improved olefin polymerization vehicle component 10 g obtained in (3) of Example 2 above, and stirred at a temperature range of 0 to 5 t: for 5 minutes. Secondly, supply propylene to the pressure cooker so that 1 Dg of propylene can be polymerized per 1 gram of modified olefin polymerization catalyst component. Pre-polymerize at a temperature of Q ~ for 1 hour. The obtained preliminary polymerized solid vehicle component was washed three times with 500 heptane * and used in the production of the following propylene-based polymer. (5) This converged economy is printed by Deng Central Standards Bureau's Consumer Cooperative (please read the precautions on the back before filling this page). In a nitrogen atmosphere, add 60 liters of pressure with stirring force to the above. Preparation of prepared polymeric solid-medullary catalyst component 2.0g, triethylaluminum 11.4g (100 nmol), dicyclopentyldimethoxysilane 6.84g (30 mmol), and 18 kg of propylene were charged The temperature was increased to 130 D mo 1 ppb with respect to propylene − by hydrogen, and the temperature was raised to 701:, and polymerization was performed for 1 hour. After 1 hour, unreacted propylene was removed, and polymerization was polymerized. As a result, it can be obtained that 6.64 paper scales are applicable to the Chinese National Standard (CN'S) A4 specifications (210X297 mm) -32-A7 419498 B7 V. Description of the invention (30) -1-ϊ I-^^ 1 ^^ 1 -Two · — I «^^ 1 ^^ 1 ^^ 1 HH 11 ^^ 1, ν5 (Please read the precautions on the back before filling out this page) kg of polypropylene, polymerization activity is 34kg / g-solid 觭As a vehicle component, the MFR of the polymerized hip was 34.2 g / lQ. The evaluation results of the physical properties of the polymer are shown in Table 2. Comparative Example 1 A 60-liter internal pressure cooker with a blender in a nitrogen atmosphere was charged with a titanium manganese trichloride made of Toyoichi. 23.5 g (195 mmol) of aluminum chloride, followed by charging 18 kg of propylene with hydrogen to 8000 raolppB relative to propylene, heating to 70¾, and polymerizing for 1 hour. After 1 hour, remove unreacted propylene The polymerization was completed. As a result, 6.23 kg of polypropylene was obtained. The MFR of the polymerized hip was 32.2 g / l (3 points. The evaluation results of the physical properties of the polymer are shown in Table 2. Comparative Example 2 Except that it was used in Example 1 (1 ) Modified solid catalyst components before the modification * and * made the hydrogen feed amount 9300 · ο1ρρ · during the polymerization of propylene, and the rest are exactly the same as the method and conditions of Example 2. K was prepolymerized, combined Propylene was polymerized. As a result, 6.88 kg of polypropylene was obtained, and the MFR of the polymer was 33.Qg / 10 minutes. The evaluation results of the physical properties of the polymer are shown in Table 2. Printed by the Consumers ’Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs. Implementation Examples 3 to 5 In addition to adjusting the amount of hydrogen locked in during the production of propylene polymerization, The MFR of polypropylene was 10.5 g / 10 minutes, 2.7 g / 10 minutes, 0.7 g / 10 minutes, and the rest were the same as the method and conditions of Example 2 to produce polypropylene. The obtained polymerization The evaluation results of the physical properties of the polymer are shown in Table 2. Comparative Example 3 33 This paper scale is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm> 419498) V. Description of the invention (31) Except for the adjustment of hydrogen in the production of propylene polymer The feed amount of the polyacrylic polymer produced can be used to produce an MFR of 3.2 g / 10 points or less, and the rest are the same as the method and conditions of Comparative Example 1 to produce a propylene polymer. Evaluation of the physical properties of the obtained polymer The results are shown in Table 2. Actual pickling example 6 (1) Modified solid catalyst components before modification In a nitrogen atmosphere. Anhydrous 47.6 g (500 mmol) of anhydrous magnesium, 250 ml of decane, and 2-ethylhexanoate were made. 234 ml (1.5 · ο1) was heated at 1301 for 2 hours to form a homogeneous solution. Anhydrous phthalic acid ll.lg (75 Biol) was added to the solution, and then stirred at 130C for 1 hour. Anhydrous phthalic acid is dissolved in the homogeneous solution. The resulting homogeneous solution is cooled to room temperature. After warming, drop in 2.0 liters (18 mol) of tetragas hydration maintained at -20C in 1 hour. After the dripping is finished • Increase the temperature of the mixed solution to 110 ¾ in K4 hours. After reaching 110 ¾, add diisobutyl phthalate Cool 26.8 ml (125 βπβοΙ) * Stir at 110 ° C for 2 hours-After the reaction is over, take the solid part while warming up, and then make the titanium of the Central Standards Bureau employee consumer cooperative of the Ministry of Economic Affairs print the titanium. After 2.0 liters (18 aol) was suspended in this reaction, it was reacted at 110¾ for 2 hours. After the reaction, the solid portion was filtered again while hot. • Washed 7 times with 110 t of decane 2.Q liters * and then washed with room temperature hexane 2.0 liters 3 times to obtain a solid catalyst component. The catalyst analysis results are shown in Table 1. (2) TiCMC ^ HWCOO1% !!,))] The preparation is the same as (2) in Example 2-U) Modification of the modified olefin polymerization catalyst component so that 40 g of the solid catalyst component obtained in (1) above Suspended in toluene 600 34 (Please read the precautions on the back before filling out this page) This paper size applies to China National Standard (CNS) A4 specification U10X ;: 97 mm) Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 4t9498 A7 B7 5. Description of the invention In (32) ml, the TiCMLMCOOU ^ h] obtained in (2) above was treated at 90 = 10.3 g (22 mmol) for 1 hour to support it. After the end of holding, take the solid part of the filter while hot filtering * re-suspend 60 0 ml of toluene and 20 ml of titanium tetrachloride (18G mmol), stir and wash at 90¾ for 1 hour | take the solid part while it is hot • Then, the reaction product was washed with 1.Q liters of toluene in M for 5 times, and further washed with 1.Q liters of hexane in room temperature for 3 times to obtain an improved olefin polymerization catalyst component. The catalyst analysis results are shown in Table 1. U) Preliminarily polymerize under a nitrogen atmosphere, put 500 ml of n-heptane, 6.0 g (53 mmol) of triethylaluminum, 4.15 g of diphenyldimethoxysilane (0.017 mmol) ) And the improved olefin polymerization catalyst component 1Dg obtained in (3) of the above-mentioned pickling example 2 and stirred for 5 minutes at a temperature range of 0 to 5C. Next, propylene was supplied to the pressure network so that 10 g of propylene could be polymerized per lg of the improved olefin polymerization catalyst component, and preliminary polymerization was performed at a temperature range of 0 to 5¾ for 1 hour. The obtained preliminary polymerization solid catalyst component was washed 3 times with n-heptane 5Q0 · 1-and used in the production of acrylonitrile polymerized crocodile under M. (5) In a polymerization nitrogen atmosphere of propylene, put into a pressure net with a stirrer with an internal volume of 60 liters * and put in the prepared polymerized solid crocodile catalyst component prepared by the above method 200 lg, triethyl aluminum 11.4 g (100 mmol) 7.32 g (30 mmol) of diphenyldimethoxysilane. Next, a gas was charged into 18 kg of propylene to raise the temperature to 5300 mol ppm relative to propylene, and the temperature was raised to 701 to perform polymerization for 1 hour. After 1 hour, unreacted propylene was removed * to terminate the polymerization. The polymerization activity was 22.0 kg / g ~ solid catalyst component. In addition, the MFR of the obtained polypropylene was 14.5g.-(Please read the precautions on the back before filling in this page)

， 1T This paper size applies to China National Standards (CNs) Α4 specifications (210 × 297 mm) 35

4 19498 A7 B7 5. Description of the invention (33) / 10 points. The evaluation results of the physical properties of the polymer are shown in Table 2. Example 7 Under a nitrogen atmosphere, 50.0 g (440 mmol) of diethoxymagnesium and 15.3 g (55 mmol) of di-n-butyl phthalate were refluxed in 25 G ml of dichloromethane and stirred for 1 hour. The obtained suspension hydraulic pressure was sent to a 2.0-liter (10.0 liter) four-gas hydrazone, and the temperature was raised to no ＊* C · for 2 hours. After the reaction was completed, the precipitated solid solution was reacted with 2.0 liters (18 * 〇1) of titanium tetrachloride at 110 ¾ for 2 hours. After the reaction was completed, wash with 2.Q liters of n-decane three times, and wash with 2.0 liters of M-hexane at room temperature until no chloride ions can be detected. Reduction and drying at 40C, the target solid catalyst component can be obtained. The results of the catalyst analysis are shown in Table 1. (2) Modulation of TiClUCsKCOOiLHOal The same method as in (2) of the second embodiment. (3) Modification of modified olefin polymerization catalyst components: 40g of the solid pulp catalyst component obtained in the above (1) was suspended in 600_ml toluene, and the TiCMLBdCOOUsh obtained in (2) above was treated at 90¾] lfl.3g (22 mmol) for 1 hour to carry it. After the end of the support, take the solid part while it is still hot, and resuspend 600 ml of toluene and 20 ml (180 nmol) of titanium tetrachloride at 90 = 0. Wash and stir for 1 hour, then take the solid part while it is hot. Then * wash the reactant 5 times with 1.0 litres of M9GC, and then wash 3 times with 1.0 litres of hexane at room temperature to obtain improved olefin polymerization. Catalyst components. The results of the catalyst analysis are shown in Table 1.-Both preliminary polymerization and propylene polymerization were performed using the same methods and conditions as in Example 6. Results • Polymerization activity was 21.1 kg / g—solid catalyst component The paper scale is applicable to China National Standard (CNS) A4 (2! 0X 297 mm) --------- n -II--(^^^ 1 I.------.- II (Please read the notes on the back before filling out this page) Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 36 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 4 J949 8 A7 B7 V. Description of the invention (. Moreover, the MFR of the obtained polypropylene is 16.3 g / 1Q. The results of the evaluation of the physical properties of the polymerized polymer are shown in Table 2. Table 1 Catalyst analysis results before the improvement of the solid catalyst Improved composition of olefin polymerization catalyst Di (wt%) T, (Ut96) (D / T), Dm (vt96) Ti (vt96) (D / T) m (D / T) n / (D / T), Example 1 7.81 2.25 0.60 12.0 1.01 2.05 3.42 贲 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 I .------- Ί ------, order ------ ^ (Please read the notes on the back before filling in this page) This paper size is applicable to Chinese national standard (CNS> A4 size (210X M7 mm>) ^ 1949g at B7 V. Description of the invention (35) Comparative Example 3 printed by the Central Standards Bureau of the Ministry of Economic Affairs and Consumer Cooperatives Example 3 Example 7 Example 6 Example 5 Example 4 Example 3 Comparative Example 2 Comparative Example 1 Example 2 Example 1 聃 CD C〇Η- * CO 05 CO CO CO CD Preparation CO CO cn CD to CJ1 ΐΰ 0〇c〇zn 03 05 C £ 3 cn CO CO CJt Xylene extraction insolubles, (heaviest _1 CO σ? CO CO CO CO Ού CT3 ςΰ ① CO Office CO CO CJ1 CO CO CO to ca CO GJl CO iO CJX = Φ Nie s Tree Exhaust% 3 w w ^ 1 W Xueί—1 ο U1 03 —a C3 OS U1 os CO 09 cn h ^ · —3 μ »* · CJl CJ PO 05 CO CO CJ1 00 CO as CXt 1— * · 05 Average chain length of cis-link N 80 05 0〇a &gt; CJI 800 00 N · 虫 骐 垂 _ Sha 3 薛 Xueka 1 _ _ 菡 ^ V f C0 ◦ 〇OJ to — 03 OJ 1— * »£ h. CJ1 o Cv3 -J 1— * C3 CJ1 CO CO o CO ts5 to ω o MFR (g / 10 Points) 泔 2 I 1 ---- nn I-I n I-nin _ _ T m tn I ___ ^, v-port-s (please read the notes on the back first and then fill out this page) The paper music scale is applicable China National Standard (CNS) A4 specification (BOX2? 7mm) 4,9498 at B7 V. Description of invention (36) Comparative Example 3 printed by the Employees' Cooperatives of the Central Bureau of Standards of the Ministry of Economy Example 7 Example 6 Example 5 Example 4 Cell example 3 Comparative example 2 Comparative example 1 Example 2 Example 1 cr St ts5 〇1 DO Ο CO DO CO CO at— * 00 ts5 C3 0—23 23 Izod impact strength (kg · cm / cm) a BB waterlog§n 1 1 1 1 1! 1 ii -20¾ 12300 17500 17300 14200 172 00 17900 16200 14600 18100 17900 ^ suspicion &gt; a 3 Η Γ * Τ -m 1— »Private I— * · cc CP 1— * ro 00 l · —1 — 09 C3 za a H- * to -J h— * 1— * Cji 1— ^ j— * CO ◦ Load Deformation Temperature (¾) CO OS ό t-— ◦ 1— * CO 03 — a CO »—1 o CO — o 1—» CO CO 1— * o Do 1— * o Do Rockwell surface hardness R scale CO 0〇CO 00 CJ \ ro CO CD 00 00 CJT t ** 〇s [N3 00 OJ PO 0〇05 »U 00 &lt; 35 〇 Surface gloss (% ) 1 1 1 μ-t 1-- Od 1— * 1— * 1— * 03 Office CD 1— »to Cs3 to a Surface gloss (%) m Tibet-4 1 I f CJ \ Office cn CJl OT — ca cn Oft tn σΐ 5Γ 关 \ Μ gas m • 妩 g- 遥 3 _ CO Ο CO 1] t OJ to CD OS CO cc CO Ca »Es3 PO Haze (%) 绁 2 I 2 &quot; ----- -^^^ 1 1 ^ 1! J 1 l ^ i— I-^ — ^ 1----1 *-5J.... .. nn 1. (Please read the precautions on the back first (Fill in this page again.) This paper size applies Chinese National Standard (CNS) A4 (210X297 mm). 39 Central Consumers Bureau of the Ministry of Economic Affairs, Consumer Cooperative Cooperative 4 19498 a? B7 Five 'Invention Description (37) Example 8 Same as Implement 2. After mixing the propylene with a stirrer with a mixer of 60 liters in a pressure cooker (step 1), remove the liquid propylene, and then mix the ethylene / propylene = 40/6 0 (mole ratio) gas mixture at 75¾ 2 Νπι3 / Hour, hydrogen supply rate of 20 NL / hour, copolymerization for 40 minutes (stage 2) ° After 40 minutes • Removal of unreacted gas to complete the polymerization. Results * 8.0 kg of a propylene-ethylene-block copolymer was obtained. The ethylene content according to iaC-NMR was 9.7% by weight, and the HFR was 17.8 g / 10 minutes. The results of the physical evaluation of the polymerization are shown in Table 3. In addition, XI, IP, and N in Table 3 refer to the elementary polypropylene taken out after the polymerization in the first stage. Comparative Example 4 Similar to Comparative Example 1, the internal volume of 60 liters was pressured with stirring. After the polymerization of propylene, the liquid propylene was removed. At 65 ° C, a mixture of K ethylene / propylene = 40/60 (its ear ratio) was thought. 2 , 2 Nm3 / hour, hydrogen 20 NL / hour supply rate | Supply for 40 minutes. After 40 minutes, the unreacted gas was removed-* ending the polymerization. As a result, 7.7 kg of a propylene-ethylene-block copolymer was obtained. According to 1 3C-NMR, the ethylene content was 9.6% by weight, and the MFR was 18.3 g / 10 minutes. The evaluation of the physical properties of the polymer is shown in Table 3. XI, IP, and N in Table 3 are military polypropylenes taken out after the polymerization in the first stage. This paper size applies to Chinese National Standards (CNS) Λ4 specifications (210 × 297 mm) 40 I- [H 1 I 丨 ^ 衣 ^ IH Step on (please read the precautions on the back before filling this page) Consumer cooperative print? 9498 A7 B7 V. Description of the invention (38) Comparative Example 4 Example 8 ef nm ^ m m. A zn Cocji CD CO tn Dimethylbenzyl extract insolubles (wt%) CO CO CO CJl = φ Nie s J 3-m 〇〇CQ o The average length of the clink NAN · Stupid fee _ Φ 3 Charm US JsJ pn pm _qing 芷 mmw φ Jia ^ vf 0 = 〇o 1-- 00 CO I- — CO HFR (g / 10 points) (Please read the precautions on the back before filling out this page) This paper size applies the Chinese National Standard (CNS) Λ4 specification (2! 0X297 mm) -41-»^ 9498 V. Description of the Invention (M Α7 Β7 Comparative Example 4 printed by the Employees' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs Example 8 at Public 涔 言 a Slag cn ZJX Office 23 ^ Izod Impact Strength (kg · ciii / cbi) BB Fee Η Ci Ci » CtS OS CO 1 i -20 ^ 1_ 1 12100 14100 Differential elastic modulus (kg / cm8) Η- »»-CO 1— »CO Deformation temperature under private load (V) 00 Ό CO Cs3 Rockwell Surface Hardness R scale 05 CO CO 68 * 1 Surface Gloss (%) i 1 Surface Gloss (96) m Μ 1! 5Γ 兴 \ %% m • m & Fill 3 »1 1 Haze ( 96) Zhejiang 3 丨 2 (Please read the precautions on the back before filling out this page) This paper size is applicable to the Chinese National Standard (CNS) A4 specification (2 丨 〇 × 297 mm) 42 4 ^ 9498 A7 87 _ V. Description of the invention (40) Examples 9, 10 and Comparative Example 5 Examples of propylene-based polymerized hip composition * Di-xylene-p-cresol was added to the propylene-based polymer obtained in the present invention at 0.05% by weight, pentaerythr Tetrabenzyl-tetra [3- (3,5-dibutyl-4-hydroxyphenyl)] propionate 0.10% by weight, calcium carbonate 0.1.10% by weight, 20 liters of ultra-thin produced by Kawata Manufacturing Co., Ltd. Mixing machine (SMV20 type) is used for mixing, and AS30 30iim0 double-sleeve extruder made by Nakatani Machinery Co., Ltd. is used for granulation. * The following is used as a nucleating agent, and the blending should be changed. (Types of nucleating agents) Nucleating agent A: pt-butyl aluminum quaternary acid salt nucleating agent B: 2,2-methylenebis (4,6-di-third-butylphenyl) phosphate sodium A sister compound formed by blending the aforementioned nucleating agent and the like in the polypropylene obtained in Example 2 (Examples 9 and 10) and a composition formed by blending a nucleating agent in the polypropylene obtained in Comparative Example 1 (Comparative example 5)-There is this-Table 4 shows the evaluation results of the physical properties of both. Example 11 and Comparative Example 6 A composition formed by mixing the propylene-ethylene-block copolymer obtained in Example 8 and Example 4 with the nucleating agent and the like of Example 9 was prepared. The physical property evaluation results are as follows: The results are shown in Table 4. This paper size applies to Chinese National Standard (CNS) A4 specification (4ΙΟΧ :: 97 mm) I -------, installed ----- ordered ---- --- (please read the first Note: Please fill in this page again.) Printed by the Central Bureau of Standards of the Ministry of Economic Affairs of the People's Republic of China for Printing 43 4 f9498 a? B7 V. Description of the Invention (41) Printed by the Central Standards Bureau of the Ministry of Economics of the People's Consumer Cooperatives of Printing Comparative Example 6 Example 11 Comparative Example 5 Example 10 Example 9 Kite 98.5 99.5 CO CO CO 99.5 99.5 Xylene extraction insolubles (% by weight) 97.7 99.5 CD 00 CO 99.5 99.5 i_ Cilian's pentad component rate IP mmin ⑼ ϊ ϊ--- ^ 3 〇 &gt; 〇09 DO OS 0〇as 〇〇Ca »a &gt; The average bond length of the cis-link N oo oo &gt;-* CO N- m 骐 费 ^ Φ S IM Jd {ηη η valve Μ 菡 ϊν Η 〇〇ο ο — 00 03 1— ^ 00 cc tSJ 34.2 CO (Si MFR U / 10 points) A 0.2 &gt; 〇D3 ah ^ · t = ao • Ch A 0.2 a weaving spot quenching »Wen Zun Zi Pu N ^ mm Xie Ren I 1

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The paper size of the 1T line paper is in accordance with the Chinese National Standard (CNS) A4 specification (210 × 297 mm) 44 4 Ϊ9498 A7 B7 V. Description of the invention (42) Comparative Example 6 printed by the staff consumer cooperative of the Central Standards Bureau of the Ministry of Economic Affairs Example 11 Comparison Example 5 Example 10 Example 9 菹 oa Csi 1- ^ CO H- »23Ό Izod impact strength (kg · cm / cm) Β Β water an 〇oa OO! -201C 1 1 14600! 1 1! i 16800 '1 1 19200 j 24500 22000 P rm ^ ms ΰϊ 10 ΠΤ H- * CS5 Fenhk Ca? Do μ— CO t— * I- * Private 0〇1— * t— »Load Deformation Temperature (υ) zn CO CO h- * 〇Fs3 1— * o CD — C7I Rockwell surface hardness β scale Oi ΓΟ PO 86.3 CO CO CO surface gloss (96) 1 1 CO C〇CO surface gloss (96) wm 1 1- o Cs? CJl 1— ^ CJ \ CO TO Xing \ m gas m • m »i I CO OO CO 1— * H- * 05 1—» CO tn Haze (96) Zhe A 丨 2 --- n-- --- Shibu --- H---TI n II-I 篆 «1 Fen (Please read the precautions on the back before filling out this page) This paper size applies the Chinese National Standard (CNS) Λ4 specification (2IOX297) (Centimeter) 45 4ί9498 A7 Β7 five Explanation of the invention (43) Comparative Examples 7 to 9 are the same as those of Comparative Example 2 except that the MFR of the resulting polypropylene is adjusted to 11. Og / 10 minutes, 3.0g / 10 minutes, and 0.5g / 1G points, respectively. Methods, conditions, M to produce polypropylene. The physical property evaluation results of the obtained polymer are shown in Table 5. -------- i-- (Please read the notes on the back before filling this page)

1, 1T Printed by the Consumers Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs. The paper size is applicable to China National Standards (CNS) A4 specifications (2 丨 〇χ 2mm) 46 419498 Thai t9498 at B7 V. Description of the invention (44) Ministry of Economic Affairs Printed by the Central Bureau of Standards for Consumer Cooperatives Comparative Example 9 Comparative Example 8 Comparative Example 7 Comparative Example 98.6 CO CO 98.7 Xylene Extraction Insolubles (weight 炻), _1 CD 06 OS CD OS CO CO 00 05 s Xie Feifu 3 Yi Xue 260 290 306 Average bond length of cis-links N 03 η m ^ Φ 3 ρη ρπ 岫 _ 芷 次 Μ 隳 ^ ΦNo ΐν ^ 00 〇◦ C7I CO 〇H- * — MFR (g / ΙΟ points)-binding ^ (Please read the notes on the back before filling out this page) This paper size applies to Chinese National Standard (CNS) Λ4 current (210X297 mm) -47-4 ^ 9498 A7B7 V. Description of invention (45) Central Ministry of Economic Affairs Standard Bureau employee consumer cooperative print 1 Comparative Example 9 Comparative Example 8! Comparative Example 7 cn 03 CO ΓΟ 23¾ Izod Impact Strength (kg · cm / cm) EB gt Waterlog gn 1 1 -20t! Moo 14000 15600 Bendability Rate (fcg / CBla) — Ο ς &gt; — * ts9 W * PC 05 load deformation Temperature Oc) CD IS5 〇〇— o Rockwell surface hardness R scale g cn 09 to 83.1 Surface gloss (96) 1 Ι Ο H-fc to surface gloss (%) mmi 05 H- * 05 ◦ 5Γ 兴 \ m% Wei • m 3 »1 03 〇Haze (96) * Binding (please read the precautions on the back before filling out this page) This paper size is applicable to China National Standard (CNS) A4 (210X297 mm) 48 419498 A7 B7 V. Explanation of the invention (46) By implementing the present invention, because it can produce more excellent rigidity, surface hardness, heat resistance, water vapor resistance and other physical properties than the conventional ones, and it is suitable for automobiles, home appliances, and packaging. The propylene-based polymer and the composition * have sufficient industrial value. --------- ¾ Clothing ------ 1T ------ Μ (Please read the precautions on the back before filling out this page) Printed by the Staff Consumer Cooperative of the Central Bureau of Standards, Ministry of Economic Affairs 49 This paper size applies to the Chinese National Standard (CNS) Λ4 specification (2 [0 × :: 97 mm)

Claims (1)

β 8 9 9 4 4 QV 9 ABCD of the Consumer Cooperatives of the Central Government of the Central Government of the Ministry of Economic Affairs of ABCD ΪRange 1. A kind of polymerization of propylene strips. It contains repeating units of-(CHa-CHCH3)-and is an interpolymer or copolymer or block copolymer. 'The homopolymer is CH3-CH = CH » Homopolymer of propylene * This copolymer is a copolymer of propylene with one or more α-olefins represented by MR_CH = CHa, R represents hydrogen or a hydrocarbon family having 1 to 20 carbon atoms, and the block The copolymer is a block copolymer of propylene and ethylene represented by CHa = CHa; and the propylene-based polymerization system (25T: xylene extracted with insoluble UI) is 99.0% by weight (or) M; ⑵13C nuclear magnetic resonance The isotactic pentad fraction (IP) measured by the spectrum is 38.0% (or M); (3) the average 鐽 length of the cis complex is 500 (or) K; and xylene is The average length (fU) of each fraction (fraction) measured by the insoluble column method is 80 0 (or more), and the total of the fractions is 10% or more of the total. 2. For example, the propylene polymer of the scope of application for patent No.1: Xylene 25¾ xylene extracts the insoluble content (XI) above 99 · 0% by weight; ⑵ 13C-the quintile of NMR measured by NMR spectrum (Isotactic pntad) fraction (IP) is above 98.0%; (3) The average chain length (U) of cis-link is above 500 μM; and the average length of each part of the sister is measured by the column method of xM insoluble xylene. The total of the partial groups whose (N,) is 80 0M is 30% by weight or more of the whole. 3. —A kind of propylene polymer composition, which is at least 0.1 ~ 5 to 15% of the nucleating agent in the propylene fluorene polymer as described in the first patent application scope. This paper size is applicable to China National Standard [CNS] A4 (210X297mm) 50 --------- d ------ ΐτ ------ ^ (Please read the note on the back first (Fill in this page again)