TW387919B - Propylene-ethylene copolymer, preparation thereof and molding thereof - Google Patents

Abstract

This invention provides propylene-ethylene copolymer which gives a molding having an excellent heat resistance and film having both heat sealing in low temperature and rigidity, preparation thereof and molding. A propylene-ethylene copolymer comprising 0.01-15 mol% of ethylene unit, characterized in that in a chain structure in accordance with nuclear magnetic resonance spectrum, triad fraction (PEP), triad fraction (EEE) and <alpha>, <beta>-methylene carbon number fraction (N<alpha><beta>) are in a specific scope; the weight average molecular weight is 50000-1500000, and the distribution of molecular weight is 1.2-3.8. Said copolymer can be prepared by copolymerizing ethylene with propylene in the presence of a catyst comprising a combination of a specific chiral transition metal compound (metallocene) and aluminoxane.

Description

The Central Government Bureau of the Ministry of Economic Affairs, Shellfish Consumption Cooperation, Du Yinhe A7 B7 V. Description of the Invention (1) Inventory 11 (Xie Jie) The invention is based on propylene-ethylene copolymers, especially ethylene unit chains with special characteristics. A propylene-ethylene copolymer having the fewest heterogeneous bonds of a propylene unit and a narrow distribution of molecule 1 and a method for producing the same. The molded article obtained by molding this propylene-ethylene copolymer is also mentioned. Xiyou Zhijie Street knows that propylene-ethylene copolymers have lower crystallinity than straight crystalline polypropylene homopolymers, and have extremely low glass transition temperatures. They are widely used in films and other applications, but in other applications Due to limitations, in order to be used in such applications, various characteristics need to be improved. For example, in the category of the most widely used films, from the viewpoint of energy conservation, low-temperature curing properties are required. Conventionally, a method of reducing the melting point of the copolymer is adopted, and the sacrifice of the films is sacrificed. Therefore, it is necessary to take into account the conflict Brightness and low temperature heat sealability. These conventional propylene-ethylene copolymers are usually made by copolymerizing ethylene and propylene using a titanium catalyst. However, the properties of the propylene-ethylene copolymers obtained by this copolymerization method have been limited. • In recent years, rhenium media have been used.研究 Various methods for preparing olefin (co) polymers by olefin (co) polymerization with different dicomplex metals and aluminoxane glycosides. For example, using a catalyst consisting of a silicon cross leg type dichromium arsine and alumoxane with a specific structure, propylene is polymerized to obtain highly stereoregular polypropylene, with a narrow molecular weight distribution, high melting point, and high rigidity. Kaiping Nos. 3-12406 and 3-1 2407 and &lt; &lt; Chemical Communications &gt; &gt; (pp. 1853-1856, 1989), but there is no technology for revealing propylene-ethylene copolymers. 1 3-(Please read the notes on the back before filling in this page) Binding ·-Ordering This paper size is applicable to China National Standard (CNS) A4 specification (210X297 mm) A7 B7 Printed by the cooperative V. Description of the invention (2) In addition, Tsutsui et al. Observed the use of a catalyst consisting of ethylene bis (1-indenyl) dichloride and methylalumoxane to copolymerize propylene and ethylene. -Ethylene copolymer, the stereoregularity specified by the meso bond unit (BB; divalent radical) of two propylene units of κ, even though it is the same as the copolymer obtained from the conventional titanium-rhenium catalyst component, -The melting point of the propylene-ethylene copolymer obtained from the alumoxane-based catalyst is still lower than that of the copolymer obtained from the titanium-based catalyst component. There are many heterogeneous species of propylene units (Ttsui et al. '&Lt; Polymers &gt;, 30, 1 350 (1 989)). There are many heterogeneous bonds in this propylene unit. The polymerization of propylene using titanium-based rhenium is almost polymerized by 1, 2 insertion reaction. In contrast, the propylene polymerization reaction using these well-known diluent gold sulfonates becomes M — A fixed ratio of 2,1 insertion reaction and 1,3 insertion reaction. Modestness of the box hemp according to the invention According to the conventional technique, when a propylene-ethylene copolymer is used in a molding material such as thin, it is difficult to achieve both good cutting and low-temperature heat-sealability. The object of the present invention is to provide and provide a propylene-ethylene copolymer having good clam properties and low-temperature heat-sealability, a method for producing the same, and a molded product of the copolymer. In order to achieve the above-mentioned objective, the inventors made intensive research results, successfully produced a propylene-ethylene copolymer having ethylene unit specific properties, very few heterogeneous bond amounts of propylene units, and a narrow distribution of molecule 1, and found that it has a specific structure obtained by the production method. Propylene-ethylene copolymer, not only can be made into a film with both good rigidity and low-temperature heat-sealability, or injection with better heat radiation performance. This standard is suitable for Chinese gardeners (CNS &gt; Μ specifications (2 丨 0X297mm) s'. (Please read the precautions on the back before filling this page), tx. Printed by A7 B7, Shellfish Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (5) And the moldability is also good, and the present invention has been completed. The first gist of the present invention is to provide a propylene-ethylene copolymer including ethylene units of 0.01 to 1.5 moles; K and propylene units of 99 9 9 ~ 8 5 Mol! Ϋ, its special 擞 is: (a) The 鐽 structure of the nuclear magnetic resonance spectrum is: (a-1) three monomer bond units (trivalent radicals) in the main 鐽 of the copolymer In the propylene unit-ethylene unit-propylene unit connection (PEP), The relationship between the olefin unit content (C2) and the following formula (I): 0.0070X C2-0. 0020S PEP ^ 0.0070X C2 + 0.0130 (1) and (a-2) three monomers in the main chain of the copolymer In the unit 价 (trivalent base), the ratio of the triplet (EEE) of the ethylene unit and the total ethylene unit content (C2) has the following formula (I): EEE ^ 0.00033X C2 + 0.0010 (I) and, U-3) The ratio of the total α, / 9-methylene carbon number (Ηαcall) to the range of 0 to 1.2 mol with respect to the all propylene unit, (b) the weight average molecular weight (Mw) is 5 0,000 to 1,500,000, Κ And U) The ratio (M &quot; Mη) of the weight average molecular weight (Mw) to the number average molecular weight (Μη) is 1.2 to 3.8. The second gist of the present invention is the method for producing a propylene-ethylene copolymer according to the first gist, which is characterized in that, in the presence of a catalyst composed of an optically active transition metal compound represented by the general formula (1) and an alumoxane, ethylene and Copolymerization of propylene: -5- This paper size applies to China National Standard (CNS) Α4 size (210X297 mm) (Please read the precautions on the back before filling this page)

Printed by the Central Standards Bureau of the Ministry of Economic Affairs and Consumer Cooperatives A7 _ B7 V. Description of Invention (4) / (孓 ιΗ 卜 鼸 只 * ·) \ / X Q Μ (1)

\ (C * Η 4-n R \ Y

In the formula, M is a transition gold atom selected from titanium, Hao, and X, X and Y are the same or different, and are a hydrogen atom, a halogen atom, or a hydrocarbon group, (H 4-m R ^ m) and (C5H "n R2n ) Is a substituted cyclopentadienyl group, wherein R 1 and R 2 are the same or different and are Ci — 20 hydrocarbon groups, which can be combined with two carbon atoms on the ring of cyclopentadiene to form a hydrocarbon ring on K, and It may be substituted by K hydrocarbon group, or a silicon-containing hydrocarbon group, π and n are integers of 1 to 3, Q is selected from hydrocarbon group, unsubstituted silylidene group and hydrocarbon substituted silylidene group, and ((^ N-ιπΙ ^ ιη) and (C5H "nR2n &gt; crosslinked divalent group. In addition, the third aspect of the present invention is characterized in that the propylene-ethylene copolymer of the first aspect is a molding material, and a molded product formed by adding K. Chain "Ming" when the shape of the propylene-ethylene copolymer of the first aspect of the present invention, the copolymer structure, namely the total ethylene unit content (C2), the monomer unit ratio (PEP) and (EEE), K and the total α, /?-Methylene carbon number are a mixed solution of trifluorene / polybrominated benzene = 18/2 at a polymer ratio of 20 and resuspended, using nuclear magnetic resonance at 67.20 MHz, 1 30t: Calculated value of the measurement result. The measurement device may be, for example, a Jeol-GX270 NMR measurement device (manufactured by Bento Electronics Co., Ltd.). The propylene-ethylene copolymer of the first aspect of the present invention contains ethylene units of 0.01 to 15%. Ears 5K, K0.05 to 12 Moore 3! Is preferred, and M 0.05 to 10 Moore χ is particularly preferred. When the content of all ethylene fluorene is below 0.01 Moore κ, a copolymerization of 6- Zhang A degree of this product applies Chinese National Standard (CNS) (210 × 297 mm) C · ^ In- tm ϋ ^ ι HI-»1 ^^^ 1 1¾ In (Please read the precautions on the back before filling this page) Order Printed by the Central Standards Bureau of the Ministry of Economic Affairs, Shellfish Consumer Cooperatives, printed A7 B7 V. Description of the invention (5) When the material exceeds 15 mol Si, the crystallinity of the copolymer will decrease, and the heat resistance will decrease. As used in the description, among the three monomer units (trivalent radicals) in the main unit of the propylene-ethylene copolymer, "propylene unit 4 ethylene unit-propylene unit connection fraction (PEP)" and "ethylene unit triple connection (EEE) j term, which refers to the angle five proposals (&lt; &lt; Giant molecule &gt; &gt;, 1, 5, 1 1 50 (1 982)) using the UC core The propylene and ethylene chains in the trivalent unit of the main bond of the propylene-ethylene copolymer measured by the resonance spectrum are: "propylene unit 々 ethylene unit ~ &gt; fraction when the propylene unit is connected (PEP)", and "ethylene unit- In the first gist of the present invention, the peak of the 13 C nuclear magnetic resonance spectrum is summarized according to the above-mentioned proposal of Cang Wu and so on. «In the propylene-ethylene copolymer of the first aspect of the present invention, the propylene unit 4 ethylene unit 4 propylene unit connected fraction (PEP), the full propylene-ethylene unit in the copolymer main chain, taking into account the triple bond When the unit (trivalent base) is the ratio of the existence of 鼸 single charge to the full trivalent base 鐽 unit in the propylene unit 4 ethylene unit 4 propylene unit, the higher the trivalent base fraction (PEP), the more it is sandwiched between propylene units. The higher the ratio of isolated ethylene units, the higher the randomness. In the propylene-ethylene copolymer of the first aspect of the present invention, the fraction of the propylene unit-ethylene unit-propylene unit phase chain (PEP) and the total ethylene unit content in the copolymer (C2, the unit is SS :) The relationship of the formula (I): 0.0070X C2-0.0020S PEPS 0.0070X C2 +0.0130 (1) It is better to use the aiming system of formula (I '): -7- This paper standard applies to the Chinese National Standard (CNS) A4 size (210X297mm) *. Jrt m · ml m ml ΙΜΊ · ^^^^ 1 · ϋν &gt; Lv / i ^ i ^ — (Please read the precautions on the back before filling this page)

, ^ T Printed by A7 B7, Shellfish Consumer Cooperative of the Central Sample Bureau of the Ministry of Economic Affairs 5. Description of the invention (6) · 0.0070X C2 $ PEPS 0.0070X C2 + 0.0130 (1 '), and the relationship of M formula (I) is the best 0.0070X C2S PEPS 0.0070X C2 + 0.0090 (1 &quot;) Propylene unit-ethylene unit 4 The propylene unit connected fraction (PEP) exceeds the propylene-ethylene copolymer of the formula (I) above, which has not yet been issued within the technical scope of the present invention. On the other hand, when the (PEP) fraction is too small, the low-temperature heat-sealability of the film obtained from the copolymer is deteriorated. On the other hand, the fraction of the ethylene unit triplet (EEE) is all propylene and ethylene units in the main bond of the copolymer. Among them, when taking into account the tritium unit (trivalent radical) of the trivalent monomer, the existence ratio of the trivalent chain unit of the ethylene unit ethylene unit ethylene unit relative to the full trivalent radical unit is the trivalent radical fraction. The higher the (EEE), the higher the block existence ratio of the ethylene unit in the copolymer. In the propylene-ethylene copolymer of the first aspect of the present invention, the ethylene unit-ethylene unit 4 ethylene unit connection fraction (EEE) is copolymerized with Content of all ethylene units ((C2), unit is 萁Between "), the formula (I) is: ΕΕΕ ^ 0.00033 × C2 + 0.0010 (Π) The formula (" *) has a better relationship: 0.00033 × C2-0.0028S EEES 0.00033 × C2 + 0.0005 (H ') and K type U ") Fei series is particularly preferable: 0.00033X 02-0.00022 ^ ΕΕΕ ^ 0.00033 × C2 (I &quot;) Ethylene unit 4 Ethylene unit The ethylene unit is connected to the ethylene unit (EEE), which is larger than the range of the above formula (I) At the time, the low temperature heat sealing of the film obtained from the copolymer-8- (Please read the precautions on the back before filling this page) • -α ·

, tT • HI. (210X297mm) Printed by the Shellfish Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (7) The sex will deteriorate. On the other hand, the (EEE) fraction is too small and has not been found in the technical scope of the present invention. In the present inventors, the ratio of total ex, &gt; 3-methylenesulfonate number to total propylene unit content (C3) (Nα / 8), according to Tsutsui et al. (&Lt; <Polymer >> 30, 1 350 ( 1989)) method, using 13 C nuclear magnetic resonance spectroscopy to measure the ratio of the total α, / 9 -methylene carbon number to the total propylene unit content (C3) in the main propylene-ethylene copolymer (Hct / 3, The unit is 萁 耳 J!), Which is 100 times the value defined in the same reference. This value reflects that the continuous 2,2 insertion reaction of propylene is not based on the α, /?-Methylene carbon spectrum due to the 1, 2- insertion reaction of propylene and the insertion reaction of ethylene. It is due to the copolymer The amount of heterogeneous bonds in the 2,1-insertion reaction of propylene. The ratio of the propylene-ethylene copolymer of the first gist of the present invention to the α, / 3-methylene carbon number (in ears) of the total propylene unit content (C3 in mols) Ua / 3), in the range of 0 to 1.2 Mor 5; M0 to 0.5 Mor 5; preferably, K0 to 0.2 Mor X. When the ratio (Ηαθ) of the methylene carbon number (in moles) to the total propylene unit content (C3 in moles) in the main copolymer of the copolymer is too large, the rigidity and low-temperature heat-sealability of the copolymer molded body Will decrease. »The propylene-ethylene copolymer according to the first aspect of the present invention has a heterocyclic bond of propylene, and has a main structure of a copolymer in which ethylene units are randomly incorporated in the copolymer. The weight-average molecular weight (MW) and number-average molecular weight (Mη) of the propylene-ethylene copolymer of the first gist of the present invention are ortho-dibenzobenzene solutions with an M polymer degree of 0.05 weight X, and are analyzed by gel permeability. (G PC), make the standard of this paper -9- Common Chinese National Standard (CNS) A4 grid (210X297 mm)-&quot; Λ 1. —-H----_ K_ n (Please first listen (Read the notes on the back and fill out this page)

、 1T B7_ V. Description of the invention (β) Mixed polystyrene condensing heating pipe column (for example, PSKgel 6MB 6-HT manufactured by Toray) at 135Oi «Fixed result» The measuring device can be used, for example, GPC-150C ) * The propylene-ethylene copolymer of the first gist of the present invention has a weight average molecular-weight (MW) 5 0,0 〇 | G ~ 1,5 0 0,0 0 0, and 1 0 0,0 0 0 to 1 , 0 0 0, 0 0 0 Fan is better. When the reset average molecular weight (Mw) is large, the melt flowability of the copolymer is reduced, and the moldability is reduced. If it is too small, the strength of the molded product is reduced. The propylene-ethylene copolymer of the first gist of the present invention has a weight average molecular weight (Mw) log average molecular weight (Mη) ratio (Mw / Mn) of 1.2 to 3.8, preferably 1.5 to 3.5. Β This weight average The molecular halo log average molecular weight (Μη) ratio (Η w / Μη) is a measure of the molecular weight distribution. When this ratio (Hw / Mn) is too large, the molecular weight distribution will be too wide. Sealing will deteriorate. On the other hand, (propylene-ethylene copolymers with Mw / MnUb below 1.2 have not yet been published in the technical model letter of the present invention. "Printed by the Central Consumer Bureau of the Ministry of Economic Affairs, the Consumer Cooperatives (Please read the precautions on the back before (Fill in this page) — — .. — — * — i The propylene-ethylene copolymer of the first gist of the present invention is due to its special structure, the melting point of the propylene-ethylene copolymer (Ti) And the total ethylene unit content in the copolymer (C2, the unit is Moore X), the formula (melon, shown as follows: -8.IX C2 + 156.0- &gt; Tb-+-4.4X C2 + 160.0 (ffi ) According to the structural conditions, it has a hurricane of the formula (m Μ: -7. 2 X C2 + 1 56. 0- »Tin-» -4. 9 X C2 + 165.0 (m)鼷 傜 ·· -10- · This book is applicable to the Chinese National Standards (CNS) A4 specifications (210X297 mm) on the Zhang scale. Μ The Central Consumer Standards Bureau of the Ministry of Economic Affairs of the People's Republic of China Consumer Cooperatives A7 B7 5. Invention Description (9) -6 3 X C2 +1 56. 0 彳 Tm · ^ -5.4 X C2 + 165.0 (丨 &quot;) This melting point is a DSC7 differential scanning calorimeter (product of Parkin Mima Co.), which copolymerizes propylene and ethylene. From room temperature Under the temperature rising condition of 30t: / min, and the temperature rising to 230t :, after holding for 10 minutes, the temperature of K-20t: / minute is reduced to -20C, and after holding for 10 minutes, under the temperature rising condition of 20C / minute It shows the value of the peak temperature of the maximum heat absorption during melting. The method for producing a propylene-ethylene copolymer according to the first gist of the present invention is not particularly limited as long as the obtained propylene-ethylene copolymer can meet the foregoing requirements. In the second gist, it is appropriate to use a specific diluoxin catalyst. In the second gist of the present invention, a catalyst combining a combination of optically active gold tincture compound and alumoxane is used as the specific dioxin tincture. It can be used as For the two complexes, there is an optically active transition gold compound represented by the general formula 0): / CsH "Er Q Μ (1)

^ (CH ^ nRV ^^ Y where M is selected from the group consisting of titanium, junction, and given transition metal atoms, χ and γ are the same or different, and are argon, halogen, or hydrocarbyl α5Η4-πιΐΛη) and (C5H4-n θη ) Represents a substituted cyclopentadienyl group, in which R1 and P are the same or different and are Cl-20 hydrocarbon groups, which can be combined with two carbon atoms on the cyclopentadiene ring to form a hydrocarbon ring on 1K. Or silicon-containing hydrocarbon group, m and η are integers of 1 to 3, Q is selected from hydrocarbon group, unsubstituted silylidene group or hydrocarbon-substituted silyl group, and can be used with (C5H4-m) and • -11- This paper size applies Chinese National Standard (CNS) Λ4 specification (21 〇 × 297 mm) h ^ «^^^^ 1 Β4 · -— ϋ eMmmlt a ^ la— (Please read the precautions on the back before filling out this page) -'β.

C A7 B7 V. Description of the invention (10) (C5H "nR2n), the divalent radical to be handed over. The preferred transition metal compound is that in the general formula 0> M is zirconium or a given atom, R1 and R2 are the same or different Is a "-20 alkyl group, X and Y are the same or different, are a halogen atom or a hydrocarbon group, and Q is a dialkylsilylidene group. Specific examples of the optically active transition metal compound represented by the general formula 0) include racemic dimethylsilylidenebis (2-methyl-4,5,6,7-tetrahydroindenyl) dichloride Dimethylmethanesarane bis (2-methyl-4,5,6,7-tetrahydroindenyl) dimethyl step, racemic methylenebis (2-methyl-4,5,6,7 -Tetrahydroindenyl) di-atomization, racemic dimethylsilylidene bis (2-methyl-4-phenylindenyl) di-atomized zirconium, racemic dimethylsilylidene bis (2- Methyl-4-phenylindenyl) dimethylaluminum, racemic dimethylsilylidene bis (2-methyl-4-benzylindenyl), dichloro, mesodimethylsilylidene Bis (2-methyl-4-fluorenylindenyl) zirconium dichloride, racemic dimethylsilylidene bis (2-methyl-4-naphthylindenyl) dimethyl aluminum, racemic dimethyl Methylsilylidenebis (2-methyl-4-naphthylindenyl), dichlorosilylidene, dimethylsilylidene (2,4-dimethylcyclopentadienyl) (3 ', 5 ·- Dimethylcyclopentadienyl) titanium dichloride, dimethylsilylidene (2,4-dimethylcyclopentadienyl) (3,5'-dimethylcyclopentadienyl ) Dichloride, dimethylsilylidene (2, 4-dimethyl Cyclopentadienyl) (3 ', 5' Printed by the Consumer Cooperatives of the Central Bureau of Quasi-Economic Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling out this page)-Dimethylcyclopentadienyl) Dimethyl Zirconium, dimethylsilylidene (2,4-dimethylcyclopentadienyl) (3,5'-dimethylcyclopentadienyl) dichloride, dimethylsilylidene ( 2,4-dimethylcyclopentadienyl) (3,5'-dimethylcyclopentadienyl) dimethyl, dimethylsilylidene (2,3,5-trimethyl Cyclopentadienyl) (2 ', 4', 5'-trimethylcyclopentadienyldi) titanium dichloride, dimethylsilylidene (2,3,5-trimethylcyclopentadiene (Dilute base) (2 · -12- This standard is applicable to the Chinese National Standard (CNS) A4 * y &amp; · (210X297 mm) Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs, printed A7 B7 V. Invention Description (11) , 4 ', 5'-trimethylcyclopentadienyl) di-zirconium zirconium, dimethylsilylidene (2, 3,5-trimethylcyclopentadienyl) (2', 4 ', 5'-trimethylcyclopentadienyl) dimethyl zirconium, dimethylsilylidene (2,3,5-trimethylcyclopentadienyl) (2 ', 4 ', 5 · -trimethylcyclopentadienyl) dichloride, dimethylsilylidene (2,3,5-trimethylcyclopentadienyl) (2', 4 ', 5 * -Trimethylcyclopentadienyl) dimethyl etc. Preferred among these transition gold compounds are: dimethylsilylidene (2,4-dimethylcyclopentadienyl) (3 ', 5'-dimethylcyclopentadienyl) dichloride Zirconium, dimethylsilylidene (2,4-dimethylcyclopentadienyl) (3 ', 5'-dimethylcyclopentadienyl) dimethylzirconium, dimethylsilylidene (2,4-dimethylcyclopentadienyl) (3 ', 5'-dimethylcyclopentadienyl) dichloride, dimethylsilylidene (2,4-dimethylcyclo Pentadienyl &gt; (3 ', 5'-dimethylcyclopentadienyl) dimethyl, dimethylsilylidene (2,3,5-trimethylcyclopentadienyl) ( 2 ', 4', 5'-trimethylcyclopentadienyl) dichloride, dimethylsilylidene (2,3,5-trimethylcyclopentadienyl) (2 ', 4 ', 5'-Trimethylcyclopentadienyl) dimethyl, dimethylsilylidene (2,3,5-trimethylcyclopentadienyl) (2', 4 ', 5' -Trimethylcyclopentadienyl) dichloride, dimethylsilylidene (2,3,5-trimethylcyclopentadienyl) (2 ', 4', 5 · -trimethyl Cyclopentadienyl) dimethyl During synthesis, there is a by-product non-optical structure-13- This paper size is applicable to the Chinese National Standard (CNS) Α4 size (21 〇 × 297 mm), η SI- ma ^ i.— HY ml 1 ^ 1 (please first (Read the notes on the back and fill out this page)

1T 5. Invention description (I2) In the case of the meso-dioxin gold tincture of A7 B7, in practice, it is not necessary that all of the meso-dioxin gold hall is used, even if mixed with the meso-body. However, when using a mixture with a meso, although it depends on the amount of the meso and the propylene-ethylene copolymerization activity, the heteropolymers polymerized from the meso can be extracted by solvent, etc. Removal by known methods, the resulting propylene-ethylene copolymer can meet the requirements of the first gist of the present invention. These optically active di-complexes can be combined with alumoxane as a catalyst, but they can also be carried on a particulate carrier. These particulate carriers are inorganic or organic compounds, and granular or spherical particulate solids with a particle size of 5 to 300 // b, preferably 10 to 200 wm can be used. The inorganic compounds used as the carrier include Si02, Al2O3, MgO, Τ02, ZnO, etc., and mixtures or composite compounds thereof, such as Si02-A1 2 〇3 'SiO 2 -HgO' SiO 2 -TiO 2, SiO 2 -A1 2 0 a -Mg0 and the like. Among them, KSi02 or AI2 03 is preferred. In addition, organic compounds used as the carrier include ethylene, propylene, 1-butene, 4-methyl-pentene, and the like (: 2-12 α-olefin polymer or copolymer, styrene polymer or copolymer. In the propylene-ethylene copolymer manufacturing method of the second gist of the invention, the aluminoxane, which is a combination of a catalyst component and an optically active transition metal compound, has the general formula in.----- n 1- IJ1 In--·· (Please read the precautions on the back before filling out this page), τ Printed by the Staff Consumer Cooperative of the Central Bureau of the Ministry of Economic Affairs

I / IV shows η or

A t s R OA combined f, igA—Ro machine-C has 1

R) ρ H A —ο

• R -14- This standard / paper size applies to Chinese National Standard (CNS) A4 specification (210X297 mm) A7 B7 Printed by the Central Government Bureau of the Ministry of Economic Affairs, Shellfish Consumer Cooperative, V. Invention Description (15) where ^ is ^- 6 hydrocarbyl, KCl-4 is preferred. Specific examples include alkyl such as methyl, ethyl, propyl, butyl, isobutyl, pentyl, hexyl, allyl, 2-methylallyl, and propenyl. , Isopropenyl, 2-methyl-1-propenyl, butenyl and other alkenyl groups, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and other cycloalkyl groups, and aryl groups. Among them, M alkyl group is preferable, and each R 3 may be the same or different. 'P is an integer from 4 to 30, M6 to 30 is preferred, and W8 to 30 is particularly preferred. These alumoxanes are not only one type, but also two types of alkoxides can be used in combination. It is possible to use trimethyl aluminum, triethyl aluminum, triisopropyl aluminum, triisobutyl aluminum, and dimethyl aluminum chloride together. Oxyaluminum compounds. The alumoxane can be prepared under various known conditions. Specific examples include the following methods: (1) a method in which trialkylaluminum is reacted with direct water using an organic solvent such as toluene, diethyl ether, etc .; (2) a trialkylaluminum is reacted with amidines having crystal water, such as copper sulfate Method for reaction of hydrate and aluminum sulfate hydrate; @Method for reaction of trialkylaluminum with impregnated moisture such as silica gel; ⑷Mix trimethylaluminum with triisobutylaluminum and use organic compounds such as toluene and ether Solvent and direct water reaction method: (5) Method of mixing trimethylaluminum with triisobutylaluminum and reacting with salts with crystal water, such as copper sulfate hydrate, aluminum sulfate hydrate; (6) A method in which water is impregnated with silicon gel and the like, reacts with triisobutylaluminum, and then reacts with trimethylaluminum. In the propylene-ethylene copolymer production method of the second gist of the present invention, although -15- (please read the precautions on the back before filling this page)

K equipment

, 1T 4 This paper is applicable to Chinese National Standard (CNS) Α4 standard (210 × 297 mm.). The Ministry of Interest and Economic Development Bureau of the Central Government Procurement Cooperation Du Yin *. A7 B7 V. Inventor Sun and Moon (l4) The catalyst of the above-mentioned combination of dioxofluorene and alumoxane, but the amount of each of the catalyst components is 10-1,000,000, compared with the transition gold atom of the dioxane, and the aluminum atom in the alumoxane is 10 ~ 1,000,000. More preferably, 50 to 50,000 moles are preferred, and 100 to 30,000 moles are particularly preferred. In the second gist of the present invention, in the presence of the catalyst obtained by the combination described above, propylene and ethylene can be copolymerized to prepare the propylene-ethylene copolymer of the first gist of the present invention, but the polymerization method can use a known propylene ( Co-polymerization process, for example, in aliphatic hydrocarbons such as butane, pentane, hexane, heptane, octane, cycloaliphatic hydrocarbons such as cyclopentane, hexane, methylcyclohexane, toluene, xylene, Aromatic hydrocarbons such as ethylbenzyl can be used in inert solvents such as gasoline fractions or gasoline tanks, and the slurry polymerization method of polymerizing propylene and ethylene, and using propylene itself as a solvent, the entire copolymerization with Μ, and Any gas phase copolymerization method in which the copolymerization of propylene and ethylene is performed in the gas phase may be used. In addition, the copolymerization can be carried out in a continuous ore type, a batch type or an f-batch type. In the copolymerization of propylene and ethylene, the above catalysts can be pre-mixed with two components of dioxofluorene and oxaloxane in an inert solvent, and then supplied to the copolymerization reaction. Dioxofluorene and alumoxane can also be separately supplied. To the copolymerization reaction 糸. In addition, before the copolymerization of propylene and ethylene, it is possible to react a small amount of α-olefins in the inert solvent of the catalyst of dioxometallurgy and aluminum oxide, specifically, each mole of dichromium The transition metal is used to make the α-olefin polymerize from about 0.001 to 10 kg. After the catalyst is preactivated, copolymerization of propylene and ethylene is carried out. Finally, good particles of propylene-ethylene copolymer are obtained, which is also effective. -16- This ¥ Zhang scale applies to China's national kneading rate (CNS) Α4 size (210X297 mm) '---- (Please read the note on the back before filling this page) £ Equipment_ Order Zhongji, Central Kneading A7 _ ._B7 ___ printed by the quasi-government industrial-consumer cooperation V. Description of the invention (15) Can be used for pre-activated 0C-olefins, including C2-12 Ot-olefins, specific examples include ethylene, propylene, butene, pentene Ene, hexene, octene, 4-methyl-1-pentene, etc., especially K ethylene, propylene, 4-methyl-1-pentene are preferred. In the second gist of the present invention, if the propylene and ethylene are copolymerized by using the pre-image method in the presence of a pre-activated catalyst, the same polymerization conditions as those commonly known as optically active rhenium catalysts for polymerizing propylene can be used as the copolymerization conditions. . That is, the polymerization degree is from -50 to 150t: JW-10 to 100P is preferred, the polymerization pressure is from atmospheric pressure to 7MPa, and K0.2 to 5MPa is preferred. The propylene and ethylene are supplied into the polymerizer, which is usually carried out for 1 minute to 20 hours. Left and right copolymerization. In addition, during the polymerization, similar to the conventional copolymerization method, an amount of hydrogen can be added to control the molecular weight. After the completion of the copolymerization of propylene and ethylene, if necessary, it may be subjected to post-treatment steps such as a known deactivation treatment step, a residue removal step, and a suspicion step to prepare a soft propylene-ethylene copolymer according to the first step of the present invention. In the method for producing a propylene-ethylene copolymer according to the second gist of the present invention, ethylene and propylene are copolymerized in the presence of a catalyst of a combination of a precursor dichromium metal and an alumoxane. In the insertion reaction, isopyrene hardly occurs. On the other hand, during the ethylene insertion reaction, the ore-sparing insertion reaction of ethylene is suppressed, and the ethylene units are more randomly incorporated in the copolymer. As a result, in the method for preparing a propylene-ethylene copolymer according to the second gist of the present invention, a monomer 鐽 which supports a more random combination of ethylene units, has a small amount of heterogeneous bond of propylene units, and has a narrow molecular weight analysis is the first gist of the present invention. -17- The paper Λ degree applies to the Chinese National Standard (CNS) A4 specification (210X297 cm) (Please read the note on the back before filling out this page) -s ^ _. Printed by the Consumer Cooperatives in the Central Bureau of the Ministry of Economic Affairs A7 _ _B7___ V. Propylene-ethylene copolymer of invention description (16). In the molded article of the third aspect of the present invention, the propylene-ethylene copolymer which is the first aspect of the present invention is optionally blended with an anti-gasification agent, an ultraviolet absorbent, an antistatic tritium, a nucleating agent, a detergent, Various additives such as flame retardants, anti-blocking tinctures, coloring «, filling of inorganic or organic materials, and various synthetic resins, in powder form, or using a melt blender at 190 ~ 35QeC, heating and mixing for 20 seconds to 30 About 0 minutes, and then cut into granules to form a granular state for molding materials. "The molding method can use various known polypropylene molding methods, such as injection molding, extrusion molding, foam molding, hollow molding, etc. Various industrial injection molding components, various containers, non-stretched film, uniaxially stretched film, biaxially stretched film, cast iron, tube, fiber, etc. can be made. Molded products β Sound stealing examples The present invention can be borrowed from examples and comparisons The example further details the β m propion sample-7, sample # & _ &gt; The equipment has a stainless steel mesh polymerizer with inclined blades and a stirrer with a content of 10 OdB3, which is purged with nitrogen. In the aggregator, at 20e C gi degree: n-hexane 50dn 3, methylaluminoxane toluene solution (product of Dongsu Aikesu Company, trade name MMA0, concentration 2id (d · 3), converted to aluminum atom is 2.0 · 〇1, and optical rotation Methylsilylidene (2,3,5-trimethylchenpentadienyl) (2 ·, 4 ·, 5'-trimethylfluorpentadienyl) dicyanide 0.09 mmol and Racemic Dimethyl Silane (2,3,5- -1 8-(Please read the note on the back and write this page first) 〉 A4 specification (210X297 mm) A7 B7 V. Description of the invention (17) Trimethylcyclopentadienyl (2,3,5, -trimethylpyridylcyclopentadienyl) digasified to 0.01 milliliter The mixture of Moore was used as dioxin, together with toluene 0.5 da 3 〇 Then, after the temperature in the polymerizer was raised to 45 υ, the content of propylene was 93.9 mol χ, ethylene 6.0 mol χ and hydrogen oi mol χ. The mixed gas is supplied to the polymerizer at a supply speed of 8dm3 / rain, and the temperature in the polymerizer is maintained at 451C. A part of the mixed gas in the gas phase part of the polymerizer is installed in the polymerizer separately. Phase valve Out of the polymerizer, M kept the pressure at 0.4M Pa, and co-polymerized C and C for 4 hours. Employees' cooperatives of the Central Bureau of Standards, Ministry of Economic Affairs, the consumer co-operatives (please read the precautions on the back before filling out this page) Polymerization After the reaction is completed, unreacted propylene and ethylene are released from the polymerizer, and 2-propanol 3dm 3 is put into the polymerizer, and the catalyst is deactivated at 30t: stirring for 10 minutes. Aeration is added. Aqueous hydrogen solution (concentration: 12ind / dm3 &gt; 0.2dm3 and formazan 8dm3) was treated at 60¾ for 30 minutes. After the treatment is completed, stop stirring, remove the aqueous phase from the bottom of the polymerizer, add the same amount of hydrogen chloride aqueous solution and formazan, and repeat the same operation. Next, add an aqueous solution of sodium hydroxide (concentration: 5.11〇 丨 / € || 113) 0.02 (1113, water 2 &lt; 1 || 13 and methanol 2dm3, and stir for 30 minutes at 30¾. After the treatment, stop the stirring from After removing the water phase part under the polymerizer, add 8dm3 of water again, at 30 t: stirring treatment for 10 minutes, the operation of removing the water phase part is repeated twice, and the polymer slurry is taken out from the polymerizer, dried and dried to obtain A propylene-ethylene copolymer of 2.4 kg was used as the evaluation sample of Example 1. When Pali 2 changed the n-hexane used in Example 1 to toluene 50dm 3 as the polymerization solvent-19. (CNS) A4 specification (210X297 mm) A7 B7 V. Description of the invention (18), the mixed gas component supplied to the polymerizer is propylene 90. 5 mol ", 9.5 mol ethylene, hydrogen / 0, polymerization temperature The temperature is 30C, and the rest is made under the same conditions as in Cell Example 1. A propylene-ethylene copolymer was produced to obtain an evaluation sample of Example 2. —Li Li 3 The composition of the mixed gas supplied to the polymerizer was: propylene 96.8 Moore X, ethylene 3.2 箕 S:, · Hydrogen 0, and polymerization temperature 50 * 0, and the rest were made under the same conditions as in Example 1. A propylene-ethylene copolymer was obtained in Example 3. g 敝 Example 4 The n-hexane used in Example 1 was changed to 50dm3 of toluene as the polymerization solvent, and the composition of the mixed gas supplied to the polymerizer was propylene 84.8. Moore !, ethylene, 15.1 mole V, and hydrogen 0.1 mole. I used the same conditions as in Example 1 to produce a propylene-ethylene copolymer. Example 4 Evaluation Sample 6 was obtained. Printed by Industrial and Commercial Cooperatives (please read the precautions on the back before filling out this page) Use dimethylsilane (2,3,5-trimethylcyclopentadienyl) (2 ', 4!, 5 '-Trimethylcyclopentadienyl) chromium dichloride 0.09 mmol and dimethylsilylidene (2,3,5-trimethylcyclopentadienyl) (2', 3 ', 5 '-Trimethylcyclopentadienyl) dichloride mixture with 0.01 millimolars, as the diluentine, and the mixed gas supplied to the polymerizer becomes propylene 91.1 mol S; ethylene 8.8 Ear S; Hydrogen 0.1 and Ear 3J. After performing propylene-ethylene copolymerization and copolymer purification under the same conditions as in Example 4 of the cell, the solvent portion containing the copolymer was taken out from the polymerizer. • The 珉 standard is applicable to China's National Standards (CNS) M specifications (210X297 cm) /.· V. Description of the invention (19 A7 B7) The copolymer is dissolved in the solvent removed from the printed materials of the Central Government Bureau of the Ministry of Economy All, this solution is put into the solvent depressurization age removal device, and under jg · η;-. '® 701: After distilling off 95¾ methylbenzyl, and cooling to 25¾ .. Put in a manurease to put 3'_ The copolymer was taken out, dried, and dried to produce a propylene-ethylene copolymer. Example 5 Evaluation Sample 0 fch »Li 1 The catalyst used in Example 1 was used as a catalyst (~ chromium metal and methylalumoxane). The chlorinated continuum-bearing type was used instead; the catalyst component of Meijie 1 was converted to Ti with 0.28 millitorr, triethyl sulphate 80 mol, and the diisopropyl dimethoxide of the S component of the catalyst. Before the polymer mixed with silane and 8 moles is supplied to the polymerizer, a mixed gas of propylene and ethylene is supplied to the polymerizer. Fill the polymerizer with gas 〇K j 'hope 5 (&gt; The reaction mixture gas is discharged out of the polymerizer, and M can maintain a supply rate of 0.69 HPa for the polymerization room power, and supply 934 to the polymerizer. Gun alkenyl 6.6 X molar composition of the gas bet engagement and the polymerization temperature was 6〇1〇, than the same process as in Example 1, producing propylene - ethylene copolymer, Comparative Example 1 to obtain evaluation samples. fch age M 2 uses a mixture of racemic ethidium bis (syl) dichloride to give 009 millimoles and meso ethyl bis (syl) dichloride to 0.001 mol, As the same conditions as in Example 1, the propylene-ethylene co-refining step was carried out. The copolymer-containing soluble copolymer was taken out of the polymerizer and dissolved in the solvent. Then, the solvent of Example 5 was added to the formic acid. The copolymer was precipitated and the propylene-ethylene copolymer was obtained to obtain a comparative example 2 evaluation sample. ⑵ and 锸 -7, ene &amp; polymer properties of Shiluo Jinyao, the rest of the polymerization and copolymer agent parts, because the same distillation under reduced pressure and drying, -21- This paper size applies to China National Sample Rate (CNS) Α4 specification (210X297), (please read the precautions on the back before filling out this page) Binding. Order · A7 B7 V. Description of the invention (20) For Examples 1 to 5 and Comparative Example 1 to Each of the obtained evaluation samples was measured for the following physical properties. The evaluation results are shown in Table 1. (a) Total ethylene unit content, measured by ϋ (: nuclear magnetic resonance spectroscopy (unit: χ χ). (b) Trivalent fraction (PEP): three monomer fluorene units (trivalent in the main chain of the copolymer) Base), which is the connection fraction of "propylene unit-ethylene unit / propylene unit", determined by 13 C nuclear magnetic resonance spectroscopy. (C) Trivalent radical fraction (EEE): Three monomer units of the main unit of the copolymer. Trivalent group), which is the connection fraction of "ethylene units, ethylene units, 4 ethylene units," determined by 13 C-NMR spectrum. (D) α, / 3-methylene carbon number relative to the total propylene unit content (C3) Ratio (Nα / 3): GC Nuclear Magnetic Resonance Spectroscopy (Unit: Xerox). (E) Weight average molecular weight (nW): measured by GPC. (F) Number average molecular weight (MrO: measured by GPC. (G) Melting point (Tb): Measured by GPC (unit is 1 ^). --C ^ — (Please read the notes on the back before filling this page) Printed by the Shellfish Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs-22- • Γ ·. This scale is applicable to the Chinese national standard (0 Yang) 8 4 * 1 ^ (210 father 297 mm) A7 B7 V. Description of the invention (21 Table 1 Example Comparative Example No. 3 4 5 1 2 Ethylene content (Molar Si) 3.22 4.41 2.05 7,14 14.3 6.50 4.88 Trivalent base fraction (PEP) (Χίο2) 2.78 3.69 1.66 5.70 10.44 4.60 4.00 Trivalent base fraction (ΕΕΕ) (&gt; (102) 0.00 0.06 0.00 0.12 0.34 0.40 0.06 〇 (, / 3-methylene carbon number ratio 1 &lt; «/ 9 (萁 耳 51!) 0.07 0.07 0.07 0.08 0.20 &lt; 0.01 1.41 weight average molecular weight (Mw) (xl04) 18.9 90.0 18.5 35.3 7.2 19.0 25.8 Mean molecular ratio (Mw / Mn) 2.3 2.8 2.2 1.7 2.2 4.1 2.0 Melting point (Tβ) 〇) 139.7 137.4 150.0 116.1 115.3 139.5 109.5 Γ tj \ r ----I (Please read first Note on the back, please fill in this page again) • Injection molding of IL. @ Propylene-7. 慊 copolymer molded product in 100 parts by weight of the propylene-ethylene copolymer obtained in Example 1, mixed with four [Methylene-3- (3 ', 5'-Di-tert-butyl-4'-hydroxybenzyl) propionate] 0.1 part by weight of methane, and 0.1 part by weight of calcium stearate. This mixture uses a single unit with an extrusion temperature set at 230C and a screw diameter of 40βιβ. Coaxial pellets were pressed out to obtain copolymer pellets. The obtained pellet K injection molding machine was injection molded at a molten resin temperature of 230t :, and a gold contact mold temperature of 50t to prepare a JIS-shaped test sample. hh 齩 利 3 Except using the propylene-ethylene copolymer obtained in Comparative Example 1, the same conditions as in Example 6 were used to prepare a JIS-shaped sample. (4 ·) Estimated maturity resistance of molded products-23- This paper size is applicable to the Chinese garden family (CNS) A4 specification (210X297 mm) _ Order printed by the Central Labor Bureau of the Ministry of Economic Affairs and printed by the Shellfish Consumer Cooperatives A7 B7 V. Description of the invention (22) After the samples prepared in Example 6 and Comparative Example 3 were placed in a room with a relative humidity of 50¾ and a room temperature of 23C for 72 hours, according to JIS K 7207, at a flexural pressure of 45.1 N / cm2 , Measure the twist temperature (HDT) (unit is t :), and evaluate the heat resistance. The distortion temperature (HDT) of the samples of Example 6 and Comparative Example 3 were 1011 and gst, respectively: 〇 The higher the distortion temperature (HDT), the better the surface and the maturity. (5) 丙 锸 -7. Shop common expenses_ 甲 ； 甲 g 呒 莉 7

In 100 parts by weight of the propylene-ethylenic copolymer obtained in Example 1, 0.1 parts by weight of tris (2,4-di-tert-butylphenyl) o-acid was mixed, and tetrakis [methylenefluorene-O ', 5'-di-tert-butyl-4'-hydroxyphenyl) propionate] 0.05 parts by weight of methane, and 0.08 parts by weight of calcium stearate. This mixture was extruded in a single extraction granulator with a set extrusion temperature of 230C and a screw diameter of 40ββ to obtain copolymer pellets. The obtained pellets were melted and extruded at a temperature of 210 P, a cooling roller temperature of 30 t :, and a linear velocity of 20 m / * in, and a T-die method was used to form a film having a thickness of 25 w 1 and a width of 300 μm β. fch Ling LiA Printed by Shellfish Consumer Cooperation Department of the Central Bureau of Standards and Quarantine of the Ministry of Economic Affairs (please read the notes on the back before filling in this purchase) Except using the propylene-ethylene copolymer obtained in Comparative Example 1, use the same conditions as in Example 7 , T-die method was used to make a film with a thickness of 25 wm and a width of 30010 · ^. Existing spicy recipes: The films made in Example 7 and Comparative Example 4 were measured, and the heat-sealing temperature and Young's coefficient were measured by the following methods (direction: MD, transverse direction: TD). &quot; 24- The production scale is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) 'V. Description of the invention (25) Α7 Β7 Printed by the Central Labor Bureau of the Ministry of Economic Affairs, Shellfish Consumer Cooperative (a) Heat seal Temperature: The film was taken out and heat-sealed using a heat-inclined sealing temperature measuring machine (manufactured by Toyo Seiki Co., Ltd.) under the conditions of a sealing pressure of 0.098 MPa and a sealing time of 1 second. Next, the heat-sealed film was cut to a width of 15 mm, with the heat-sealed portion in the center, and subjected to a tensile test at a tensile speed of 300 * m / iiin. The stress at M fracture was the heat-sealing strength of the film, and the heat was measured. The heat seal temperature required when the seal strength reaches 0.0271 ^ 8/15 «11» (the position is ^!). (b) Young's coefficient: The tensile strength of MD (vertical quotient) and TD (horizontal) is measured according to ASTM D 882 (unit is N / bib2). The results of measuring the heat-sealing temperature and Young's coefficient of the films made in Example 7 and Comparative Example 4 are as follows. Table 2 Young's coefficient heat-seal temperature) HD (縦 1¾) TD (transverse) Cell example 7 135 550 Comparative example 4 141 530 The lower heat-seal temperature is advantageous from the viewpoint of energy saving, the higher the Young's coefficient, the better Bigger. As shown in Table 1 of the examples, the propylene-ethylene copolymer of the present invention has almost no propylene insertion, heterogeneous bonds caused by the reaction, ethylene units are more randomly bound, and the molecular distribution is narrow. As a result, the propylene-ethylene copolymer of the present invention is a molded product of a molding material. Compared with a propylene-ethylene copolymer molded product manufactured using a conventional technology and having a melting point similar to that of a conventional technology, the injection molded product has a good performance. Heat resistance, film has good rigidity and excellent low temperature -25- 560 540 For industrial production (please read the note on the back before filling out this page) — * ^ 4 ^ .. The paper size is applicable to the country + country CNS A4 Specification (210X297mm) A7 B7 V. Description of the Invention (24) Heat-sealability can be widely used for the limited use of propylene-ethylene copolymers. Explanation of plaques and simple houses Figure 1 is a 13 C nuclear magnetic resonance spectrum of the propylene-ethylene copolymer of the present invention obtained in Example 1. Figure 2 is a rolling diagram of the propylene-ethylene copolymer manufacturing method of the present invention. &gt; "—J-- · * &quot; ^-(Please read the notes on the back before filling in this page) Ο

C. Printed by Shellfish Consumer Cooperatives, Central Bureau of Standards, Ministry of Economic Affairs -26- This p-scale applies Chinese National Standards (CNS)

Claims (1)

Employees' cooperative of the Central Standards Bureau of the Ministry of Economic Affairs of the People's Republic of China, 7T, applied for patents. Wai 1. A propylene-ethylene copolymer, including 0.01 to 15 Moore X ethylene units and 99.99 to 85 Moore S; acrylic units, which are characterized by: : U) The structure of 鐽 from the nuclear magnetic resonance spectrum is: (a-1) the three pseudo-single bond unit valence groups in the main chain of the copolymer) are owing, and the propylene unit-ethylene unit-propylene unit connection ratio (MP) With the total ethylene unit content (C2), the formula (I) is: (1) 0.0070X C2-0.002 PEP match 0 · 0 07 0 X C.2 + 0. 0 1 3 0 (I) (a-2) in The 3 涸 single-frequency 鐽 -unit (trivalent radical) Φ of the main chain of the copolymer, the total content of 皋 -E (EEE) and S-ene, which are connected to three ethylene units, the total content of r (C2 &gt; m 阚 series: 〇 ^ EEE ^ 0.00 0 3 3 X C2 10 (I) U-3) tfc ratio (, α /?) with respect to the total number of α, / 3-methylene carbons of all propylene units, in 0 ~ 1.2 Molar 3! Range, (b) weight halo · average molecular weight (Mvl is 50,000 ~ 1,500,000, &amp;-(c) weight average molecular weight (My log average molecular weight (Μη) ratio Uw / Hn) is 1.2 to 3.8. 2, such as the first item of the patent application park A propylene-ethylene copolymer in which the melting point (; Tm) of the co-polymer is between Ji and Yuan (C2), and has the formula (I): -8. 1 XG 2 + 1 5 6.0 S T ^ -4.4 x C 2 + 16 5. 0 (The system shown in II I. 3. A method for preparing propylene-ethylene copolymer, the propylene-ethylene copolymer, including 0.01 ~ 15 Moore S: ethylene unit and 9 9.99 ~ 85 Mol J; C'-27- This paper size is in use ® National Standard (CNS &gt; Α4 size (210X297 mm) n II HI V Μ ·-V —l · * n (Please read first (Notes on the back page are to be completed on this page). 1T 'A8 B8 C8 D8 387919 VI. Patent application range paving unit, where: (a) The bond structure of the nuclear magnetic resonance spectrum is: U-1) The three proud singles, in the body chain, the propylene-yuan-yi 1 li i two Li unit unit Li Li put full Biga star_yuan content (C 2), although the formula (I) is 0. 0070 X C2- 0. 0020 ^ PEF ^ 0.0070 x_ U-2) Between the three monomer chains of the main copolymer of the copolymer, the fraction of the ethylene unit ancestors (EEE) of the three units (EEE) and B (C2), the formula (H) 阚Series: 0 S EE ES 0,0003 3 x G2 +0.0410 (a-3) , / 3 -sub-ratio (H e (exhaust), in the range of 0 to 1.2 to 4 -4, (b) the weight average molecular weight (MW) is 50, 0.00 to:-and: (c) heavy average The molecular weight (M * &gt; log-average distraction Mw / Mrt) is 1.2 ~ 3 · δ, which is characterized in that in the presence of JT, which is an optically active transition metal represented by the formula (0), the ethylene and The ratio of propylene trivalent radical (PEP) to ♦ C2 + 0.013HI) yuan (trivalent radical) total olefin unit content of methyl ethyl, total carbon number 1,500,000, the ratio (Mη) of the compound and Shao Yu Co-polymerization: (Please read the note on the back before filling in this page) Printed by the Shellfish Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs II / (C «-aR * β) \ / Q Μ Ns (CH«. nR, n) / XXY (1) In the formula, M is selected from the group consisting of sister, zirconium, and zirconium. The X and Y atoms are different or different, and are hydrogen, halogen, or fluorenyl. (C5 H4, , m Pm) and (c5H4-n R2n &gt; net substituted cyclopentadienyl, in which R 1 and R 2 28 + paper size are used in Chinese national kneading and stringing (CNS &gt; A4 specification (210X297 mm) 3 * 7919 Μ C8 D8 printed by the Shellfish Consumer Cooperative of the Central Bureau of Standards, Ministry of Economic Affairs 6. Patent application park / Same or different, is C 1-20 hydrocarbon group, which can be combined with two carbon atoms on the ring of cyclopentadiene to form a smoke ring on W, which can also be substituted by M hydrocarbon group, or it contains sand. Hydrocarbyl, m and η are integers from 1 to 3, Q is selected from hydrocarbyl, non-methsaldinyl- and dt silylidene, and-(¾ HuR1 #) and C% R2n) can be cross-linked. Bivalent base. 4. If the propylene-ethylene copolymer is manufactured according to item 3 of the scope of application for patents, ~ Xin Qin has searched for 1 Jin Jue custom— 合 is the general formula ⑴ ^, X and Υ are the same or different, are halogen atoms or R1 and R2 are the same or different, and are C 1-.2 alkyl, and Q is dialkylsilylidene. 5. A kind of molding is * its first characteristic is M 逑 propylene-B is a copolymer for the molding material molding, the propylene-fired-acetic copolymer is optional 0.001 ~ I5 mole r ethylene and -9 9 · 9 9 ~ 8 5 Moore X propylene unit • Among them: 丄 U) by -Shu magnetic, the 鐽 structure of its vibration spectrum is: U-1) in the tripyridine unit (trivalent base) of the main bond of the copolymer ... · '. .......--, The fraction (PEP) of the connection of the propylene unit-the B unit-the C unit and the ^ full B JMT element content (&amp; magic, the formula (I ) Actinide: 0. 0 0 70 x02-0.0 020 ^ PEP ^ 0.0070 xC2 + 0.013 0 (I) (a-2) Three ethylene units in the triple-single-single-bond unit (trivalent base) of the primary bond of the copolymer Connected fractions (EEEK and Yihui unit content. (C2, between, formula (I) 81 series: 0 容 ΕΕΕέ 0.00033 X C2 + 0.0010 (1) (a-3) -phase of all acrylic units a,-the ratio of the total carbon number of methylene (N α / 3), in the range of 0 to 1.2 mole X range, -29- this paper size uses two Chinese standards! M CNS &gt; Α4soft pan (210X297 Mm} HI i ^ i ^ — nn —It JMme— n (Please read the note ^^ on the back before filling this page) i11 _Γ A8 D8 VI. Patent application scope (b) Weight average molecular weight (fhf) is 50,000 ~ 1,500,000, r &quot; ^.. And (C) Ratio of weight average molecular weight (Mw) to log average molecular weight (Μη) Uw / Mn j is 1.2 to 3.8. 6. If the molded article in the scope of the patent application is No. 5, the injection molding is made of propylene-ethylene co-enamel. 7. If the molded article in the scope of the patent application is No. 5, Those who are crushed and molded by acrylic-ethylene copolymer. 8C If the molded product of item 5 of the patent application, the molded product is a film. Polymer injection molded. (Please read the note ^^ on the back before filling (This page) Packing. — Order ------ ^ Printed by the Shellfish Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs. -30-Paper paper size is applicable to China National Standard (CNS) A4 (210X297 cm).