JPS59105008A - Production of copolymer - Google Patents

Abstract

PURPOSE:To produce a low-density flexible copolymer in good efficiency, by first polymerizing propylene by using a specified Ziegler catalyst, and then copolymerizing ethylene with propylene and/or butene-1 in the absence of any solvent. CONSTITUTION:A flexible copolymer of a density of 0.860-0.910 is produced by using a catalyst comprising (i) a solid catalyst component prepared by reacting, by contact, a Si oxide and/or an Al oxide with a magnesium halide, a compound of formula I (wherein Me is a Group I -VIII element excluding Si, Ti, and V; R is a 1-24C hydrocarbon residue; X is a halogen, z is the valence of Me, and 0<n<=z), a compound of formula II (wherein R<1>, R<2> and R<3> are each a 1- 24C hydrocarbon residue, alkoxy, H or halogen, R<4> is a 1-24C hydrocarbon residue, and 1<=n<=30), a Ti compound and/or a V compound, (ii) a compound of formula II, and (iii) an organometallic compound; first polymerizing propylene and then copolymerizing ethylene with propylene and/or butene-1 in the absence of any solvent.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel method for producing soft olefin copolymers.

More specifically, the present invention uses a highly active Ziegler type catalyst to achieve a density of 0.860 to 0.910 t/cIrL"
A method for producing a novel soft or semi-rigid olefin copolymer in the range of

Conventionally, polyethylene obtained by polymerization using a catalyst consisting of a transition metal compound and an organometallic compound is generally produced by the slurry polymerization method, and its density is low during polymerization, such as precipitation on the inner wall or stirrer inside the reactor, fouling, etc. 0,945, which is said to be the limit without causing
Usually only those with t72s or more are manufactured.

Medium-density or low-density polyethylene with a density of 0.945 t/crrL" or less is usually produced exclusively by the so-called high-pressure method using a radical catalyst, but very recently, a high-temperature solution method using a Ziegler catalyst has been developed. In addition, elastomers have also been produced by copolymerizing ethylene and other α-olefins using vanadium compounds.

However, the polymer synthesized by the above method is either a crystalline resin or a non-quality elastomer, and its characteristics are clear.

Each of these polyolefin-based plastics and nidistomers exhibits excellent performance and is used for a variety of purposes. Therefore, there is a need to improve environmental stress cracking resistance (
・On the contrary, it is a common experience that elastomers are required to have strength based on their crystallinity. However, in many cases, when both components are mixed for such a noticeable difference, the tensile strength -? It is well known that various physical properties such as F6+] properties are reduced.

However, it is possible to synthesize a soft or semi-hard resin that exhibits a high degree of elongation by having an intermediate manufacturing method in which the resin itself is neither a crystalline plastic nor a nydistomer. By mixing it with other plastics, it is possible to impart elastomeric properties and improve the properties of plastics. Soft and semi-hard resin base tips (・are not well known.

Recently, several reports have been made on methods for producing resins exhibiting such intermediate physical properties, but they have various drawbacks and are difficult to implement in industry (there are many problems to be resolved). There is.

For example, Special Publication No. 46-11028 (Koha Ethylene
Although the method for producing an α-olefin conjugate indicates that solution polymerization is carried out using an aromatic hydrocarbon solvent,
This method has disadvantages in that the catalyst efficiency is poor and separation and recovery of the solvent is complicated since it is still a solution polymerization.

In addition, Japanese Patent Publication No. 47-26185 ζ presents a method of copolymerizing ethylene and α-olefin using a halogenated aliphatic hydrocarbon as a solvent. Probably because it acts as a regulator, a large amount of low molecular weight coelectric polymer is produced, which has the disadvantage that the molded product has a sticky surface. In addition, the same patent publication also discloses a method using low-absorbed hydrogen having 3 to 5 carbon atoms as a solvent, but when polymerization is carried out using these solvents, the vapor pressure due to the solvent (thanks to the reaction pressure However, in the solvent recovery process, it is necessary to compress and cool the recovered solvent in order to liquefy it.

Furthermore, (Japanese Patent Application Laid-Open No. 51-41784 ζ discloses a method of slurry copolymerization of ethylene and butene-1) ζ In this case as well, the temperature of the chassis and the composition of the raw materials are specified in detail, and within this range It has been shown that if the temperature is exceeded, the slurry becomes milky or crab-like, making it difficult to operate the reactor and transport the slurry.

First, the present inventors 1l-j: Using a catalyst consisting of a solid mineralized soup containing AfQ, a solid substance containing a titanium compound and/or a vanadium compound, and an organoaluminum compound, ethylene and α-olefin were synthesized. By contacting in the gas phase, the melt index is 0.017Th to 10, and the density is 0.850 to 0.
．． 910? proposed a method for producing soft or semi-rigid ethylene/α-olefin copolymers with
11).

The present invention further improves upon this by using a novel Ziegler catalyst to polymerize propylene in the first stage and then combining ethylene with propylene and/or butene in the substantial absence of this solvent. The present invention relates to a method for efficiently producing a soft copolymer having a density of 0.860 to 0.9102/cm 2 by copolymerizing 1-1. It is particularly desirable to carry out at least one step of the hybridization reaction in the gas phase.The use of O in the process of the present invention makes the resulting polymer even more tacky despite its extremely high activity and ultra-low density. It has a good particle pouring shape and a high bulk density, so even if it is continuously operated for a long period of time, there is very little deposition of polymer particles in the reactor or agglomeration of polymer particles, and the polymerization reaction is extremely stable. It became clear that it could be implemented.

The method of the present invention is therefore not only smoother but also easier to carry out than the prior art methods, and it is a completely unexpected fact that ultra-low density soft copolymers are obtained. I have to say that this is something to be grateful for.

The present invention consists of 0) (1) silicon oxide and/or aluminum oxide, (2) magnesium halide and the general formula Me (011
) nX-z-n (here, Me represents an element from Group I to Group X of the periodic table, excluding Si, Sz, TL and V.

R represents a hydrocarbon residue having 1 to 24 carbon atoms, and X represents a halogen atom. 2 represents the valence of Me, n is a reaction product with a compound represented by 0<nz), 11!1 Hydrocarbon residue having 1 to 24 carbon atoms, alkoxy group, hydrogen or halogen and R4 represents a hydrocarbon residue having 1 to 24 carbon atoms. (n is 1≦n≦30); and (4) a solid catalyst component which is produced by bringing a titanium compound and/or a vanadium compound into contact with each other and reacting with each other.
I R' represents a hydrocarbon residue having 1 to 24 carbon atoms, an alkoxy group, hydrogen or a halogen, and R4 represents a hydrocarbon residue having 01 to .24 carbon atoms. A compound represented by n is 1 (n is 80), and a mark D organometallic compound is used as a catalyst to bind propyle/ in the first step, and then in a substantially solvent-free state. This is a method for producing a soft copolymer having a density of 360 to 0.910 t/CnL" by copolymerizing ethylene and propylene and/or butylene/-1. Although the combined material has extremely low density, it has excellent physical properties that are intermediate between those of elastomers and plastics, with little tackiness, and can be usefully used in a variety of applications.

Furthermore, as mentioned above, the manufacturing process is also superior to the prior art and allows for smoother continuous operation.

The silicon oxide used in the present invention is silica or a double oxide of silicon and at least one other metal from Groups 1 to Vl of the Periodic Table.

The aluminum oxide used in the present invention is a double oxide of alumina and other metals.

Typical double oxides of silicon or aluminum and at least one other metal of Groups I to II of the periodic table include Ah(h"Mclo, A et Qs" C(LO-Alt).
os・S tit , Al2O5・Mg0-Cab
, A12o3・MgO-8ift, AbOs・Cub
.

Ah Os ・F ezos , Ah Os' ・N
Various natural or synthetic complex oxides such as L O, 5if2' A/(70) can be exemplified. Here, the above formula is not a molecular formula, but only affects the composition,
The groove structure and the component ratio of the double oxide used in the present invention are not particularly limited, but it goes without saying that the silicon oxide and/or aluminum oxide used in the present invention adsorbs a small amount of moisture. Even if it contains a small amount of impurities, it can be used without any problem.

The magnesium chloride used in the present invention is substantially anhydrous and includes magnesium heptachloride, magnesium chloride, magnesium bromide, and magnesium iodide, with magnesium chloride being particularly preferred.

Further, in the present invention, these norogenated magnesium may be treated with an electron donor such as alcohol, ester, ketone, carboxylic acid, ether, amine, or phosphine.

General 2 Me (OR>nX, -
n (Here, Me represents an element of Group I to Group II of the periodic table.

However, Si, 71i and V are excluded. R is carbon number 1-
44 hydrocarbon residues, and X represents a halogen atom. Examples of compounds where 2 represents the valence of Me and n is 0 (n≦2) include NaOR, Alg
C0R)2, Kg(OR)X.

Ca(OR)2, ZnC0R)t, Z%(OR) 7%
Cd(OR)t, Al(OR)s, AlC0R)tX,
BCOR)s, BCOR)2X, GaC0R)s, Gg
(OR)4.5nCOR)4, P(OR)s, CrC0
R)x, M7L(0/Tri2, Fe(OR)2, Fe(
Various compounds can be mentioned such as OR)s, co(OR)2, NiC0Rh, and more preferable specific examples include NaOC2B,, Na0CaHo, Ahl
(QCdlo)t, Mg (OC211s)2
,MQCOC,Hfu”h,Ca (0C2H,le,Z
n (0CJs)t, ZnC0C2Ha)C1,A
lC0CR,)s, At(OCJ5)s, A L (0
Ctlis )t G l , Al (QCJi, Paper A
l (QCdlo)11, A l (0C6Hs)
s, BCOC2H5)3, B(OCJs)tcl,
PCOC2Hg)s, P(0Calh)s,
Examples include compounds such as Fe(0Cdlo)s.

In the present invention, in particular, the general formula Mrt(OR), ,X2
-n, At(OR), ILX3-n and BCO
Compounds represented by R)nXs-n are preferred. Also,
As R, an alkyl group having 1 to 4 carbon atoms and a phenyl group are particularly preferable.

Magnesium halide and general formula Me (OR) nX
There is no particular limitation on the method of reaction with the compound represented by
The reaction may be carried out by mixing and heating at a temperature of 0 to 400°C, preferably 50 to 300°C for 5 minutes to 10 hours, or may be carried out by co-pulverization.

In the present invention, a method using co-pulverization is particularly preferred.

There are no particular restrictions on the filtration equipment used for co-grinding, but ball mills, vibration mills, rod mills, T'f @ percussion mills, etc. are usually used, and conditions such as the grinding temperature and grinding time vary depending on the grinding method. This is something that can be easily determined by businesses. Generally, the grinding temperature is 0°C to 200°C, 20°C to 0°C, and the grinding time is 0.5 to 0°C.
50 hours, preferably 1 to 30 hours. Of course, these operations should be carried out under an inert gas atmosphere, and moisture should be avoided as much as possible.

Magnesium halide and general formula Afe (011)n
The reaction rate with the compound represented by Xz n is Mg:
Me (molar ratio) is preferably 1:0.01 to 1.0, preferably 1:0.1 to 5C7).

The general formula used in the present invention is R"+5i-0+nR' (where R', R2, and R3 represent a hydrocarbon group having 1 to 224 carbon atoms, preferably 1 to 18 carbon atoms, an alkoxy group, hydrogen, or a halogen, R4 has 1 to 24 carbon atoms,
Preferably 1 to 18 hydrocarbon residues are shown. n1dl<
Le<80. ), monomethyltrimethoxysilane, monomethyltriethquinsilane, monomethyltri-n-butoxysilane, monomethyltri5ttc-butoxysilane, monomethyltriynepropoxysilane, monomethyltripentoxysilane, monomethyltrioctoxysilane, Monomethyltristearoxysilane, monomethyltriphenoxysilane, dimethyldimethoxysilane, dimethylshedkinsilane, dimethyldiisopropoxysilane/, dimethyldiphenoxysilane, trimethylmonomethoxysilane, trimethylmonoethoxysilane, trimethylmonoinpropoxysilane, trimethylmono Phenoxysilane, monomethyldimethoxymonochlorosilane, monomethyljethoxymonochlorosilane, monomethylmonoethoxydichlorosilane,
Monomethyljethoxymonochlororane, monomethyljethoxymonobromo7rane, monomethyldiphenoxymonochlorosilane, dimethylmonoethoxymonochlorosilane, monoethyltrimethoxysilane, monoethyltriethoxysilane, monoethyltriisopropoquine silane,
Monoethyltriphenoxysilane, diethyldimethoxysilane, diethyljethoxysilane, diethyldiphenoxysilane, triethylmonomethoxysilane, triethylmonoethoxysilane, triethylmonophenoquinesilane, monoethyldimethoxymonochlorosilane, monoethyljethoxymonochlorosilane, Monoethyldiphenoxymonochlorosilane, monoisopropyltrimethoxinelan, monon-butyltrimethoxy7silane, seven-no'I
t-butyltrinidoxinrane, mono5ee-butyltriethoxysilane, monoethyltriethoxycin, diphenyljethoxysilane, diphenylmonoethoxymonochlororane, monomethoxytrichloronerane, monoethoxytrichlororane, monoisopropoxytrichlorosilane, sevenrane η-Butoxytrichlorosilane, monopentoxytrichlorosilane, monooctoxytrichlorosilane, monostearyltrichlorosilane, monophenoxytrichlorosilane, monop-methylphenoxytrichlorosilane, dimethoxydichlorosilane, jetoxydichlorosilane, diynepropoxy Dichlorosilane, mole-butoxydichlorosilane, dioctoxycyclosilane, trimethoxymonochlorosilane, triethoxymonochlorosilane, triisopropoxymonochlorosilane, tri-n-butoxymonochlorosilane, set-
Examples include linear or bicyclic polysiloxanes in which the repeating unit R' obtained by condensing butoxymonochlorosilane, tetraethoxysilane, tetranepropoxysilane and the above compounds is represented by +5i-0+. It can also be used as a mixture of these.

Examples of the titanium compound and/or vanadium compound used in the present invention include titanium and/or vanadium halide compounds, alkali dihalides, alkoxides, and halogenated oxides. Preferred titanium compounds are tetravalent titanium compounds and octavalent titanium compounds, and specific examples of tetravalent titanium compounds include the general formula rz(QR)nX4-n (where R is 1 carbon number).
~20 alkyl, aryl, or aralkyl groups, and X represents ).rogen atom. n is 0≦n≦4) Titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, monomethoxytrichlorotitanium, dimethoxydichlorotitanium, trimethoxymonochlorotitanium, tetramethoxytitanium , monoethoxytrichlorotitanium, jetoxydichlorotitanium, triethoxymonochlorotitanium, tetraethoxytitanium, monoisopropoxytrichlorotitanium, diisopropoxydichlorotitanium, triisopropoxymonochlorotitanium, tetraisopropoxytitanium, monobutoxytrichlorotitanium, dibutoxy Dichlorotitanium, monochlorotitanium, toxoxytrichlorotitanium, monophenoxytrichlorotitanium, diphenoxydichlorotitanium, triphenoxymonochlorotitanium, tetraphenoxytitanium, etc. can be mentioned.

As the octavalent titanium compound, trihalogen obtained by reducing titanium tetrachloride, titanium tetrahalide such as titanium tetrabromide 78 with hydrogen, aluminum, titanium, or an organometallic compound of Group I to ■1 metal of the periodic table. One example is titanium chloride. 1 General formula Tt (C)71)m, ¥'4-rn
(R represents an alkyl group, an aryl group, or an aralkyl group having 1 to 2 carbon atoms, and X represents a halogen atom.

Examples include octavalent titanium compounds obtained by reducing tetravalent halogenated alkoxytitanium represented by mli O<m<4 with an organometallic compound of a metal of Groups I to II of the Periodic Table. Examples of vanadium compounds include tetravalent vanadium compounds such as vanadium tetrachloride, vanadium tetrabromide, vanadium tetraiodide, tetraethoxyvanadium, vanadium oxytrichloride, ethoxydichlorvanadyl, triethoxyvanadyl, and triptoxyvanadyl. Examples include octavalent vanadium compounds such as vanadium compounds, vanadium trichloride, and vanadium triethoxide.

In order to make the present invention even more effective, titanium compounds and vanadium compounds are often used in combination.

At this time, the V/Ti molar ratio is 2/1-(J, [J1/i
A range of is preferred.

As the organometallic compound used in the present invention, organozinc compounds belonging to Groups 1 to III of the periodic table, which are known as components of Ziegler's catalyst, can be used, but 41 aluminum compounds and organozinc compounds are particularly preferred. Specific examples include the general formula R3A1%R2AIX, RAIX2,
R2A1011, RAI(OR)X and RsAIJ (
An organoaluminum compound represented by s (R is an alkyl group or aryl group having 1 to 20 carbon atoms, X is a halogen atom, and R may be the same or different),
Alternatively, there are organic zinc compounds represented by the general formula R2Zn (wherein R is an argyl group having 1 to 20 carbon atoms and may be the same or different), including triethylaluminum, triisopropylaluminium, triisobutylaluminum. , tri5eC-butylaluminum,
tri-tert-butylaluminum, l-lyhexylaluminum, trioctylaluminum, tridecylaluminum, diethylaluminum chloride, diisopropylaluminum chloride, diethylaluminum monoethoxide, ethylaluminum sesquichloride,
Examples include diethylzinc and mixtures thereof.

In the present invention, the amount of the organometallic compound to be used is not particularly limited, but is usually 11 to 1000 relative to the transition metal compound.
Molar times can be used. In addition, together with these organometallic compounds, esters of organic carboxylic acids such as esters, aromatic acid, O- or pt-ruyl, and anise can also be used. In the present invention (1)
silicon oxide and/or aluminum oxide (
Hereinafter, component (abbreviated as IJ-(1)), (2) magnesium halide and general formula A4e (OfυnXz-n
The reaction product with the compound (hereinafter, component [Ll
, -(2) and abbreviated 1 II" product (hereinafter abbreviated as component [1l-(8)) and (4
) a titanium compound and a vanadium compound (hereinafter abbreviated as component CI)-(4)) are brought into contact with each other,
Reaction-4, (4-filtering order and contact method are not particularly limited.

The contact order is component (13-(1) and component (13-(1)).
After contacting (2), component ['D-(8) may be brought into contact with component (ll-(4)), or component (IJ-(1) and component CI]-( After contacting 3), components (1,)-(2) and component [IJ-(4) may be contacted.

There are also no particular restrictions on how you can make contact; people from the public sector and the public sector, as well as Shishi, are welcome to Fukagawa. That is, in the presence or absence of an inert solvent Ic 4 degrees 2O-40 (J-C5 good-'!
L, <LL50~300'C.

Nishinomiya React at a temperature of 5 to 50 hours. Method, co-pulverized skin J
The reaction may be carried out by a method based on 4jK or by an appropriate combination of these methods.

The inert solvent is not particularly limited to 1i1J, and is usually a hydrocarbon compound that does not inactivate the Tidalar type catalyst and /-! Or you could use one of their derivatives. These ingredients (this one-row material contains various aliphatic saturated hydrocarbons, aromatic hydrocarbons, fatty hydrocarbons, Examples include alcohols, ethers, and esters such as ethanol, diethyl ether, tetrahydrofuran, ethyl acetate, and ethyl benzoate.

When the reaction is carried out by co-pulverization, those skilled in the art can easily determine conditions such as the pulverization temperature and time depending on the pulverization method used. Generally, the grinding temperature is 0
~200°C, preferably 9Jθ°C ~ 100°C, and the grinding time is 0.5 to 50 hours, preferably 1 to 80 hours. Of course, these operations should be carried out in an inert gas atmosphere, and moisture should be avoided as much as possible.

The most preferred component in the present invention is [:ll-(1),
(1,)-(2), [item-(8) and [13-(4)
The contact order and contact method are as follows.・That is, the reaction between the magnesium halide of components [1)-(2) and the compound represented by the general formula MeCOR)n - Reaction of (1) and components (1)-(2) from 0 to 8
00°C, preferably 10-200°C, most preferably 2
At 0 to 100°C, 1 minute to 48 hours, preferably 2 minutes to
Perform for 10 hours. As the solvent, alcohol, tetrahydrofuran, ethyl acetate, etc. are preferably used. At this time, the contact ratio between component CD-(1) and component I]-(2) is as follows: component [D-(1)1 P K to component [0-(
2) 0. U l~5? , preferably 0.1 to 21. After the reaction, the solvent was removed and the component (11-(1) and component [
The contact product of D-(2) is obtained.

Next, the compound I
Temperature 20 in the presence of an inert solvent such as benzene, toluene, etc.
It is desirable to conduct the reaction at a temperature of ~400°C, preferably 50~800°C for 5 minutes to 20 hours. Further, there is no problem in simultaneously mixing and reacting magnesium chloride, a compound represented by the general formula MeCoR) nX, -s, and the component (IJ-(3)).

The contact ratio between component CI]-(1) and the contact product of component (1)-(2) and component [1]-(8) is component (1)-(1).
and component [1]-(2) for contact product 11 with component (
13-(8) 0.01~5F, preferably 0.1~
It is 2f.

Next, the contact product of the above component (1)-(1), component [13-(2) and component [,1]-(8) is added to component [l]-
The titanium compound and/or vanadium compound of (4) is added directly or in the presence of an inert solvent such as hexane, heptane, octane, benzene, or toluene at a temperature of 20 to
Heat and mix at 800°C, preferably 5υ to 150°C, for 5 minutes to 10 hours to combine component (1) - (1) and component (1).
- (2) and the component [IJ- Support the titanium compound and/or vanadium compound on the contact product of (8). Preferably component (IJ-(1) and component (IJ-(2)
and component (IJ) to the contact product of components (1)-(8).
- (4) titanium compound and/=i or vanadium compound without solvent at a temperature of 20 to 800 °C, preferably 5
Heat and mix at 0 to 150°C for 5 minutes to 10 hours to prepare components (II-(1), components (1)-(2), and component (1)).
- The titanium compound and/or vanadium compound of component (1)-(4) is supported on the contact product of (3).At this time, the amount of component C1,)-(4) used is determined in the solid component produced. The amount of titanium compound and/or vanadium compound contained in the trap is 05 to 50% by weight, preferably 2<1
It is used so that the amount becomes ~20% by weight. After completion of the reaction, unreacted titanium compounds and/or vanadium compounds are removed by washing the Tidalar catalyst several times with an inert solvent, and then the solvent is evaporated under reduced pressure to obtain a solid powder.

In the present invention, the catalyst component [general formula R3+5 using one trap]
If the amount of the compound represented by i-0±1R' is too large or too small, no effect can be expected. On the other hand, it is within the range of (11 to 10 IJ mol, preferably 0.8 to 20 mol).

A compound represented by 1 nobi 2 may be used by reacting it with the above-mentioned organometallic compound. The reaction rate at this time is the general formula R”
+5i-0+-R': Organometallic compound (molar ratio) is in the range of 1:2 500 to 1:1, more preferably 1:1
It is in the range of 00 to 1:2.

The amount of the product obtained by reacting the general formula R3fSi-0←R4 with an organometallic compound is based on the Si:Ti (molar ratio) relative to the titanium compound in the catalyst component [1,). 0.1
: The range of 1-100:■ is preferable, U, 3: 1
A range of ˜20:1 is more preferred.

In the present invention, propylene is first polymerized.

As the polymerization method at this time, the commonly practiced slurry I
Any of J-polymerization, bulk polymerization, and gas phase polymerization can be used. Of course, at this time, there is no problem even if propylene is copolymerized with a small amount of other 2-olefins such as ethylene and butene-1. As the polymerization conditions, conditions under which propylene is normally polymerized using a Tidalar catalyst can be used, and there are no particular limitations. In this first step, 0, UOt) 1 to 80% by weight, preferably Q, 001 to 70% by weight, more preferably 0.0% by weight of the total amount of polymer produced.
Produce 1-60% by weight polypropylene.

Then, in the second step, ethylene and propylene and/or butene-1 are copolymerized in substantially no solvent. One inch of the mixture may be fed to a second stage, or the combined mixture from the first stage may be flashed to remove volatile fractions such as unreacted monomers and solvents to obtain a solid polymer powder. , and then the second stage reaction may proceed. Particularly in the former case, the volatile fraction can be effectively used to remove the heat of polymerization by evaporating it during the second stage gas phase polymerization reaction. The polymerization reaction temperature is usually 20°C to 110°C, preferably 40°C to 100°C, and the pressure is normal pressure to '70°C.
/cs?・G, preferably 2 to 60 kg/crr?
-G. For the second and subsequent stages, the reaction may be further divided into two or more stages, and the polymerization conditions such as the polymerization temperature, hydrogen concentration, and comonomer concentration in each stage may be changed as appropriate. There is no problem in carrying out the polymerization reaction even if the polymerization reaction is carried out in a gas phase.Preferably, it is particularly desirable to carry out at least one stage of the polymerization reactions from the second stage onwards in a gas phase. In the present invention, butadiene, 1,4-
Various dienes such as hexadiene, 1,5-hexadiene, vinylnorbornene, ethylidenenorbornene and dicyclosuntadiene may be further copolymerized.

Examples are given below, but these are for illustrative purposes to carry out the present invention, and the present invention is not limited thereto.

Example 1 (, z) Method for producing solid catalyst component 8013 (1) In a stainless steel autoclave, 10% of tetrahydrofuran was added. Reaction product 5 obtained by reacting anhydrous magnesium chloride lk, g and aluminum)']-r-t oxide 420s' by pole milling
002 and silica (Fuji Davison + 952) 5 (J tJ ?) calcined at 600°C, reacted at 60°C for 5 hours, and then dried under reduced pressure at 120°C.
Tetrahydrofuran was removed. Next, hexane 5β was added and stirred, and then tetraethoxine was added at 1 fJ.
OmJ was added and the mixture was reacted for 5 hours under refluxing hexane to obtain a solid powder (71).

The solid powder (71) obtained above was placed in titanium tetrachloride 8β, reacted at 120°C for 5 hours, and washed with hexane until titanium tetrachloride was no longer detected in hexane to obtain a solid catalyst component. Ta. Obtained solid catalyst component 1? The titanium content inside was 70In9.

(b) Undercarriage gas phase polymerization device 4 for propylene using gas phase polymerization
A stainless steel mate crepe was used. 60℃
The above solid catalyst component 1002 was placed in an autoclave adjusted to
, triethylaluminum 2.5rrLJ and Hue,
0.25 mo (If:) of dirutriethoxysilane was added, propylene was continuously supplied so that the total pressure was 41 cg/crr?G, and polymerization was carried out for 6 minutes to obtain polypropylene 5 and 9.

(C) Copolymerization of ethylene and propylene by gas phase polymerization A stainless steel autoclave is used as the equipment for gas phase polymerization, and a loop is created with a blower, a flow rate control valve, and a dry Zyclone for separating the produced polymer. Temperature control was performed by running hot water through the jacket.

The polymerization temperature was set at 60°C, the polypropylene prepared in (b) was fed into the autoclave at a rate of 5 f/hr, and the composition (molar ratio) of ethylene, propylene, and hydrogen in the gas fed to the autoclave was determined using a blower. 44% each.

Polymerization was carried out while adjusting the concentrations to be 44% and 12%.

The resulting copolymer is spherical and has a melt index of CMI)
0.82, bulk density 0.40, density 0.883 t/
cm”.

Although the density was extremely low, there was no stickiness and the polymerization activity was extremely high at 114,000 f copolymer/fTi. Moreover, the polypropylene content in this copolymer was 0.62% by weight.

After 200 hours of continuous operation, the polymerization was stopped and the inside of the autoclave was inspected, but no polymer was observed on the inner wall, stirrer, or polymer extraction tube, indicating that long-term continuous operation could be achieved extremely smoothly. I understand.

Comparative Example 1 A catalyst was synthesized in the same manner as in Example 1, except that tetraethoxysilane was not used in the synthesis of the solid catalyst component.

Next, polymerization of propylene and copolymerization of ethylene and propylene were carried out in the same manner as in Example 1, except that the above solid catalyst component was used and 0.5 m0 g of ethyl benzoate was used instead of phenyltriethoxysilane. I did it.

After 80 hours, the polymerization reaction became impossible to stir, and the interior of the autoclave was inspected to find that a large amount of polymer had adhered to the inner walls, stirring blades, shaft, etc. The melt index of the produced copolymer is 0.89, density g O, 88
It was 8f 7cm3.

It is clear that the continuous operability is significantly inferior to Example 1 in which tetraethoxysilane was used as the solid catalyst component and an organoaluminum component and phenyltriethoxysilane were used together.

Example 2 Using the solid catalyst component of Example 1, 0.5 m of phenyltriethoxysilane was used to polymerize propylene.
When propylene was polymerized in the same manner as in Example 1(b) except that oe1M was used and the polymerization time was 1.5 minutes, 1 kg of polypropylene was obtained.

The copolymerization of ethylene and propylene was carried out in the same manner as in Example 1(c), except that the compositions (molar ratios) of ethylene, propylene, and hydrogen were adjusted to 88%, 56%, and 6%, respectively. Polymerization was performed. The resulting copolymer has a spherical shape, MI U, 32, bulk density 0.42,
Density 0.875? It was 7cm3. Although the density is extremely low, there is no stickiness and the polymerization activity is 1ull.
, had very high activity with ULlOf copolymer/S'Ti. The polypropylene content in this copolymer was 0.14 times.

After 200 hours of continuous operation, polymerization was stopped and the inside of the autoclave was inspected, and no polymer was found to be attached to the inner walls, stirring blades, polymer extraction tube, etc.

Example 8 The solid catalyst component of Example 1 was used to polymerize propylene, except that 0.2 ml of tetraethoxysilane was used instead of phenyltriethoxysilane and the polymerization time was 1.6 hours. When propylene was polymerized in the same manner as in Example 1(b), 80 kg of polypropylene was obtained.

Regarding the copolymerization of ethylene and propylene, Example 1 (C
) was done in the same manner.

The resulting copolymer is spherical, has a bulk density of 0.45, and a density of 0.888/side 3, and has no tackiness and a polymerization activity of 1 U even though the density is extremely low.
7. OU U was higher than copolymer/fTi. The polypropylene content in the sweet octopus copolymer was 10.6% by weight.

After 200 hours of continuous operation, polymerization was stopped and the inside of the autoclave was inspected, and no polymer was found to be attached to the inner wall, stirring blade, polymer extraction pipe, etc.

Example 4 Propylene was polymerized in the same manner as in Example]-(b) except that the solid catalyst component of Example 1 was used and the polymerization time was 1.8 hours. Polypropylene was obtained.

Copolymerization of ethylene and propylene was carried out in the same manner as in Example 1 (c) except that no hydrogen was added and the compositions (mole ratio) of ethylene and propylene were changed to 25% and 75%, respectively.

The obtained copolymer was spherical, AflUJ, bulk 78
Degree 0.4z, density Ll, 898? /cm''.Despite the extremely low density, there was no stickiness, and the poly@' activity was as high as 103.fJtJU2 copolymer/?Ti.The polypropylene content in this copolymer was 12. .6% by weight.

After 200 hours of continuous operation, the polymerization was stopped and the inside of the autoclave was inspected, and no polymer was found to be attached to the inner walls, stirring blades, polymer outlet tube, etc.

Example 5 Polymerization of propylene was carried out in the same manner as in Example 1 (1), except that the solid catalyst component of Example 1 was used and the polymerization time was 12 minutes. Polypropylene was obtained.

For copolymerization, butene-1 is used instead of propylene as a comonomer, and the composition (molar ratio) of ethylene, butene-1 and hydrogen in the gas supplied is as follows:
Copolymerization was carried out in the same manner as in Example j+lJ l (c) except that the amounts were adjusted to 4%, 44%, and 12%, respectively.

The obtained copolymer is spherical, M I , +−f),
The bulk density was 0.48, the density tJ, and the 88 U thickness was 7 cm3. Although the density is extremely low, there is no stickiness, and the polymerization activity is 103. IJOUi copolymer/? The polypropylene content in this copolymer was 1.3%.

After 200 hours of continuous operation, the polymerization was stopped and the inside of the autoclave was inspected, and no polymer was found to be attached to the inner walls, stirring blades, polymer outlet tube, etc.

Example 6 (a) Manufacturing method of solid catalyst component In a stainless steel autoclave of 80e, tetrahydrofuran lυp, anhydrous magnesium chloride 7 1 to 9 and aluminum triethoxide 4202 were reacted using a ball mill link to obtain a reaction product 5υoy. and 0 old) ℃
Alumina (Ket jen B) 5 U (
J? After reacting at 60'C for 5 hours,
Drying was performed under reduced pressure at 0°C to remove tetrahydrofuran. Next, after adding Hegizano 5e and stirring, 1 (JUd) of tetranidoxin run was added and reacted for 5 hours under Hegizano reflux to obtain solid powder CB.

The solid powder (B) obtained in step F was placed in titanium tetrachloride 8e, reacted at 12 (J°C) for 5 hours, and washed with hexane until titanium tetrachloride was no longer detected in hexane to dissolve the solid catalyst component. The titanium content in the obtained solid catalyst component 11 was 60 m9.

(b) Polymerization of propylene by gas phase polymerization A stainless steel autoclave was used as a gas phase polymerization apparatus. 60
The above solid Ml component 10 (
1.) Add 2.5 moe of ethylaluminum and 125 moe of phenyltriethoxysilane, continuously supply propylene so that the total pressure becomes 4, 9/crr?-G, polymerize for 2 hours, and make polypropylene. 1100
I got 7G.

(C) Copolymerization of ethylene and propylene by gas phase polymerization A stainless steel autoclave is used as the equipment for gas phase polymerization, and a loop is created with a blower, a flow control valve, and a dry cyclone for separating the produced polymer. Temperature control was performed by running hot water through the jacket.

The polymerization temperature was set at 60°C, the polypropylene prepared in (b) was fed into the autoclave at a rate of 517 hours, and the composition (molar ratio) of ethylene, propylene, and hydrogen in the gas fed to the autoclave was adjusted to 50% each using a blower. , 88%, and 12%.

The resulting copolymer is spherical and has a melt index (MI)
u50, bulk density 0.42, density U, 89 (J f
/cm'.

Although the density is extremely low, there is no stickiness and the polymerization activity is 108. (JOOf copolymer/y7"i was still very active. Also, the polypropylene content in this copolymer was 16.2% by weight.

After 200 hours of continuous operation, the polymerization was stopped and the inside of the autoclave was inspected, but no polymer was observed on the inner wall, stirrer, or polymer extraction tube, indicating that long-term continuous operation could be achieved extremely smoothly. I understand.

Patent applicant: Nippon Oil Co., Ltd.

Claims (1)

[Claims] Propylene is polymerized in the first stage using the following solid catalyst component [I], organosilicon compound and organometallic compound [■] as catalysts, and then substantially the solvent is removed. Copolymerization of ethylene and propylene and/or butene-1 in the absence of 0.860 to 0.910 7c
A method for producing a copolymer, characterized in that it produces a soft copolymer having a density of m''. 2A
(e (OR)nXz-1 (where Me is periodic table I
Indicates the elements of groups ~■. However, Si, Ti and V are excluded. 11 is carbon number 1
˜24 hydrocarbon residues, and X represents a )·rogen atom. 2 represents the valence of Me, n is a reaction product with a compound represented by 0 (n < z), 71 1 is a hydrocarbon residue having 1 to 24 carbon atoms, an alkoxy group, hydrogen or...・R4 represents a hydrocarbon residue having 1 to 24 carbon atoms. A solid catalyst component obtained by contacting and reacting a compound represented by (n is 1tt<30), and (4) a titanium compound and /''If, or a vanadium compound, I R''+Si-〇+nR' (Here, R1, R
2, R3 represents t a hydrocarbon residue having 1 to 24 carbon atoms, an alkoxy group, hydrogen or halogen, and R4 represents a hydrocarbon residue having 1 to 24 carbon atoms. n is 1≦n≦80); and l) organometallic compound.