JPS598705A - Polymerization of ethylene - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

Detailed Description of the Invention [1'3 Background of the Invention The present invention relates to a method for producing a polymer of ethylene.
Ru.

More specifically, the present invention relates to a process for the high temperature, high pressure polymerization of ethylene in which the ``f'' filter catalyst used has a characteristic metal.

There are two methods for polymerizing ethylene that are used industrially on a large scale:

The first method involves applying ethylene at high temperatures and pressures, such as above 125°C and above 500kg/LIn2, typically between 14tl and 300°C and between 1000 and 3000°C.
Polymerization is carried out under conditions of 1 hour, h or more. The chassis is
Free radicals? The polymerization is carried out in the presence of a polymerization initiator consisting of a compound formed, typically a peroxide or an acid complex, or a combination thereof.

The second method is to use ethylene at relatively low temperatures and low pressures, such as below 250°C and 200 hours A, below Tn2,
Normally 50~・)0℃ and) below group 1/cin2,
This is a method of polymerizing under the following conditions. A typical catalyst used in this method is an organometallic complex compound also called a Ziegler type catalyst.

In recent years, a third method has been proposed, for example, in the UK % Eave 828, No. 828 #In, olefin, ethylene, and a total amount of (at a temperature of 175°C, at least 4)
Ziegler H at a pressure of 5011 kg/rM2 (+ψ (i.e. organometallic compounds and Na,
Va.

Alternatively, a method has been proposed in which 25 to 500 ppm by weight of gold of Group Va (v) complex compound catalyst with a compound other than an oxide is added to the total olefin for polymerization.

Recently, a method for producing linear low density polyethylene (r, r, pp) (i'') by copolymerizing ethylene with α-olefin has also recently been proposed.

However, due to the convenient use of Ziegler type catalysts under this wide range of conditions and high pressure, ethylene production is possible! Regarding the 11 method, the catalyst may be severely deactivated due to the rt% range and use under high pressure.
In addition, since the residence time is generally short, the catalytic activity is not within the optical range. If the catalyst activity is low, catalyst decomposition and purification steps are necessary due to the large amount of catalyst residue in the produced olefin polymer. In addition, the ion market method under high temperature and high pressure is time-consuming since it is possible to use a polyethylene manufacturing equipment with a car chassis on the first floor of the high school. A large-scale equipment remodeling will be carried out, and the 41-unit manufacturing cost associated with this first one will be drastically reduced.

- In the polymerization of force ゛, stripe width, and circulation pressure ①, if the catalyst is deactivated due to thermal decomposition etc. and the catalytic activity cannot be fully exerted, it will have a negative effect on the quality of the produced polymer. It can also cause the formation of gehuishuai.

The development of a catalyst with sufficiently high catalytic activity in the Φ reaction under high crystal and tensile pressures is a key point in commercializing this technology.

[Explanation] The purpose of the present invention is to solve the above-mentioned problems, and it is an attempt to achieve this purpose by using a filter for all transfer metal catalysts made in the manner of Samurai W. It's something you do.

Therefore, the method for polymerizing ethylene according to the present invention has a low (
Both 2 (pressure of 10 kg/lv2 and at least 12
At a temperature of 5 DEG C., a combination of component A and component B described below is applied to a catalyst having a gold group 4i with ethylene or ethylene and at least -411! What about Ll-olefins and ``bugs''? k) It is expressed as a percentage.

Component (A) A contact product of the following component (A1) and component (A2) Component (A1) A contact product of a polymeric silicon compound having a structure represented by magnesium nohalide, titanium tetraal 1 1 group) ri minute (A2) At least one of the following components (a) to (c) faJ
Liquid titanium compound (however, when used in combination with the total percentage sword and component (c), this titanium compound must be a halogen-functionalized one) fb) Silicon θ) Halogen compound 2 (c) Si -0-(R2t3, R'to1i
A polymeric silicon compound component having a structure represented by the general formula R: (-m''XTn (where R3 has 1 to 1 carbon atoms)
0 hydrocarbon residue, t is halogen, m is O< m ri2
According to the present invention, the monomerization of ethylene and the oxidation of ethylene and a (Tomo-san's other method) When co-association with I-olefin is carried out, both the acid produced per transition metal and the polymer produced per solid catalyst are good, and even without decatalyzing the catalyst in the polymer There is very little residue.Also, there are almost no polymer fish eyes, so it is suitable as a film resin.

The method of the present invention is particularly suitable for the production of copolymers of ethylene and α-olefins, and can be used to obtain ethylene copolymers of medium to other markets in high yields.

These copolymers have characteristics such as not having a long lead content and having a narrow molecular weight distribution (Q value) of 3 to 5, and have high mechanical strength, especially tensile strength. Signed for strength.

The reason why the catalyst of the present invention has high activity in sieves and polymerization under low pressure is not necessarily clear, but it is explained by the chemical interaction of the components used in the present invention and the usable solid component (A
) and the special physical properties of the resulting catalyst components.

Solid catalyst component A) is a contact product of component (A1) and component (A2).

1) E1! (A1) Component (A1) is a magnesium halide, a titanium tetraalkoxide, and bV during contact of a polymeric silicon compound having a structure represented by 18t-0- (R' is a hydrocarbon residue). It is a thing.

(1)) There are magnesium halides such as φ, MgF2, MgC+2, MgBr2, etc.

These may be used in combination.

(2) A titanium tetraalkoxide alkyl group having 1 to 2 carbon atoms (about m-1 can generally be used).

One example of a suitable titanium tetraalkoxide is Hf
, T + (nC2T(5)4, TI (0-1C3H
7) 4, TI (0-nC4Hg) 4, Ti (0-n
C3H7')4, TI (0-IC4H9)4.

TI (0-CH2CH(CH3)2) 4, TI(
OC(CH3)5)4, TI (o-nc5uB)4,
TI (0-nC6H,3)4, Ti (0-nc71
j5)4, Ti(:0CH(C3H7)214,'l
'i I': (ICH(CH3)C, iHg14, Ti
(1')C8H17)4, TI(()CHIH21
)4, Ti rOcf(2CH(C2H5)C4H
q 14 and A9. These may be used in combination. % is preferable for T + (OC2H
D ) 4, T + (0-nC4Hg) 4, T t (
(1-nc, 6H) '3) 4.

(3) Polymer silicon compound This compound is represented by the formula -8+-o-. Here ■ ( R1, is about 1 to 1 carbon number (), (p!j is 1 to 6
It is a hydrocarbon residue of culm.

Specific examples of such polymeric silicon compounds having structural units include methylhydropolysiloxane, ethylhydropolysiloxane, phenylhydropolysiloxane,
Cyclohexylhydropolysiloxane temple is not mentioned.

The degree of polymerization is not particularly limited, but it is preferable that the dry I# is about 10 centistokes to 100 centistokes when handled completely. Furthermore, although the terminal structure of the hydropolysiloxane does not have a large influence, it is preferable that if it is an inert group, the terminal structure is blocked by a trialkylsilyl group.

(4) Contact of each component (component ratio) The use of the components (A,) may be arbitrary as long as the use of the components of the present invention is carried out, but in general, the following Preferably within this range.

The amount of titanium tetraalkoxide to be used may be within a molar ratio of 0.1 to 1 (Q), preferably within a range of 1.8 to 4, relative to magnesium dihalide. .

,i? The molar ratio of the remer silicon compound to the magnesium dihalide ranges from 1X10 to 100 (preferably from 0.1 to 10).

(Contact method) fj'1 min (A1) is obtained by contacting all of the above three components. Contacting the three components can be carried out by any generally known method. Generally, -1OO″
(Pv to 20 (+ "C1, preferably 0 to 100 degrees Celsius). The contact time is usually about 0 minutes to 7 hours, preferably about 1 hour to 5 hours Pv,
It is.

It is preferable to mix the three components while stirring, and also to avoid mixing the three components. -Contact can also be achieved by mechanical crushing using a lumi mill, a photo mill, etc. The order of contacting F and by may be arbitrary as long as the effectiveness of the present invention is not recognized. Compound'? +8 touch θ) is common. In this case, due to the +arIl't+ of magnesium nohalide and titanium tetraalcoquine 1, magnesium halogenide becomes a state that is commonly understood in terms of real N. Then, contact of the polymer silicon compound's proboscis produces H-shaped solid particles.

The three-component cloud, catalyst, in the presence of #1 medium or dispersion medium,
You can also do it. Examples of dispersion media in this case include hydrocarbons, halogenated hydrocarbons, and noalkylpolysiloxanes. Examples of hydrocarbons include hexa/, heptane, toluene, and cyclohexane, and specific examples of halogenated hydrocarbons include n-butyl chloride,
, 2-dichloroethylene, carbon tetrachloride, and chlorobenzene, and specific examples of dialkylborisiloxane include nomethylborisiloxane, methyl-phenyllisiloxane, and the like.

Termination of contact, that is, completion of component (A1) is 1. J between dino-magnesium rogenide and titanium tetraalcogide
e It can be determined by the formation of solid particles σ) that are precipitated by contacting the catalytic product with a polymeric silicon compound. In addition, the component (A,) is washed with an organic solvent for at least one of its raw components, particularly the polymer silicon compound,
It is preferable to remove all free raw material components. Examples of organic solvents in this case include hydrocarbons, chlorogenated hydrocarbons, and the like. Specific examples of carbon/hydrogen include hexane,
Heptane, toluene, cyclohexane, etc. (A'), specific examples of norogenated hydrocarbons include n-butyl chloride, chlorobenzene, etc.

2) Component (A2) Component (A2) is at least one of the following components (a) to (C), namely (a), (b), (a) + (b)
, (a) + (C), (h) + (c) dimension or la) +
(b) + fc).

Fa) Liquid 4 major titanium compounds 4 Of course, ``Ida-like 1'' means not only those that are liquid themselves (including those that are complexed and become liquid), but also those that are liquid as a solution. Includes all liquids.

Typical compounds include general formula T1(OR3)4-n
X2n (where R3 is a hydrocarbon residue, preferably having about 1 to 10 carbon atoms, and X represents) rogene,
Indicates a number of n x O x 4, preferably 1 < n x 4.
Name the compound represented by.

As a specific example of this compound, T ]C] 4, Tl
Br4, Ti (OC2H5) C13, TI (OC2
H5)2C12, T1(OC2)(5)3CI.

'I''+ (0-1c3H7)C10, Tl (0-n
c4H9)C13, Ti(0-nC4Hg)2c12.
TI(OC2H5)Br3, Tj(OC2145)(
OC4T(g)2C1, Ti(0-nC4Hg)3CI
, T + (o-c6H5)c l 3, TI(0-I
C,sHg)2cI2,TI (OC5H11)C13
,TI (OC6Ht3)C13,Ti (OC2H5
)4, TI (o-nc3H7)4, TI(0-iC
3H7)4, Ti(, O-no-nC4H, etc.).

r Moreover, this liquid titanium compound may be a molecular compound in which TlX4 (herein, X3 represents all rogens) is fully reacted with an electron donor.

Specific examples of this compound include Tt(14・CH3COC2H5, TIC+ 4・CH
3CO2C2H5, T i Cl 4・C6115NO
2, T I CI4・Cll3COC11TICI4・
C6H5COCl, T i C] 4・C6H5CO2
C2H5, TlC14・ClCO2C2[I5, TlC
14・C41 (40 etc. cannot be given.

Component (A2) must be fully halogen-containing. Similarly, when component (A2) consists only of components (, ) or when it consists of components (a) and (c), component (a) must contain all halogens.

fb) Silicon halogen compound A compound represented by the general formula R44-n S lX4n can be used (where R is hydrogen or a hydrocarbon residue (about 1 to 6 carbon atoms), and X4 is... rogene, n is a number with 1 <, n < 4).

Specific examples of this compound include 5iCI H81CI
3.4% CH35IC13, S+Br4, (C2H5)2SIC
12, (CH3)3SiCI, etc.

(c) Polymeric silicon compound The emplacement of this polymeric silicon compound is the same as that to be used when producing the entire component (A1). Component (c) may be the same as or different from the compound used for producing component (A1).

3) Contact between component (A,) and component (A2) (1) −
: Ratio The use of each component ψ is arbitrary as long as the effect of the present invention is not recognized; however, it is generally preferred to be within the following range.

The amount of liquid titanium compound (,) used is component (A1)k
? M may be in a molar ratio of 1X10 to 100, preferably 0
．． Within the range of 1 to 1 (l).

The amount of silicon halogen compound (b) used is based on the component (Al
)'z The molar ratio of IXI to the constituent magnesium halide is within the range of 1 to 100 (preferably within the range of 0.1 to 10).

The fecal dose of polymeric silicon compound (c) is as follows: component (A1)
The molar ratio is within the range of 1 x 10 to 100) (preferably
It is within the range of 0605 to 5.0.

(2) Contact method The homogeneous catalyst component of the present invention (Al is the above-mentioned solid component (A1
) and component (A2) Dingnawachi (, ), (b), (a) +
(b), (a) + (c), (11+ + (cl), or (al + (b) + (c)).

In general, the insects may be contacted at a temperature range of -](Ml'C to 200'C1, preferably 0°C to 100°C.

The contact time is usually about 1 minute to 9 hours, preferably 1 hour.
About 5 hours.

It is preferable to bring the solid component (A1) into contact with the components (a) to (c) under stirring, and sufficient contact can also be achieved by mechanical grinding using a ball mill, camera mill, etc. . The order of contact may be arbitrary as long as the effect of the present invention is reduced. Solid component (A1
) for components (a), (b) or (and) (C
) may be brought into contact with total light. Further, the contact in the present invention can also be carried out in the presence of a dispersion medium or an intoxicant. At that time, the solid component (
For manufacturing A1), the same one used for 1φ can be used.

2. Component (B) General formula R33-mAIX1m (where It' is 1 carbon number
〜River hydrocarbon residue, Xl halogen, m is Okm 2
It is an organoaluminum compound represented by h, which is the number of h.

Specific examples include (a) dialkyl aluminum halide, inverted diethylaluminum chloride, diimbutyl aluminum chloride 1, etc.; (b) alkylaluminum sesquihalide, inverted ethenium dihalide, such as ethyl aluminum, -) chloride; , n-
butylaluminum dichloride etc.

Furthermore, it is also possible to use trialkylaluminum and alkyl aluminum alkoxide in combination by substituting the above alkyl aluminum halide. In this case, the molar ratio of the alkyl aluminum halide to the alkyl aluminum halide is in the range of 0.01 to 0.4.

3. Offshore production of ethylene 1) Polymerization (a) Can the polymerization method of the present invention be implemented as a batch operation?
It is common to do this in a continuous manner.

The chassis device can be of the type generally used in high-pressure radical polymerization of ethylene.

Specifically, there is a continuous stirring type continuous stirring type reactor or a continuous type pre-type reactor.

The chassis can be used as a single-zone process using a single reactor, or multiple reactors can be used in series, possibly with a full cooler, or a multi-zone process can be used. It is also possible to use a single reactor, the interior of which is effectively divided into several zones.

Is this a polymer produced in one or more reactors? It can be separated from unreacted monomers and treated as in conventional high pressure processes without removing all catalyst residues.

The catalyst is, for example, kneaded as a uniform dispersion in a suitable inert body and injected directly into the reactor using a high-pressure pump. Suitable inert liquids include, for example, pentane,
Examples include hexane, cyclohexane, heptane, and toluene.

2) Monomer The polymerization carried out using the catalyst thread of the present invention is homopolymerization of ethylene, or ethylene and --- General formula R-CH=CH
2 with at least one other α-olefin. In the case of homopolymerization of ethylene, the resulting polymer is usually high-density polyethylene with a specific gravity in the range of 0.95 to 0.97.

General formula R5CH=CH2 (so R5 has 1 to 1 carbon atoms
2 hydrocarbon residues. ) Specific examples of comonomers represented by: propylene, butene-1, pentene-1
, hexene-1,4-methylpentene-1, etc. These α-olefins may be copolymerized in the resulting copolymer up to a weight of 1 to 15 mm, preferably from 1 to 15 mm.

:c) Coordination conditions (1) Polymerization pressure The polymerization pressure employed in the present invention is at least 20
The pressure is 0 to 9/17n, preferably 3oo~
3.000 kg/*v, more preferably 500+
The pressure is in the range of ~2,000 Eastm.

(2) Polymerization temperature offshore temperature is at least 125°C, but preferably 1
φ) Concave circle of 50 to 350°C, more preferably C, within the range of 180 to 280°C.

Although it is not essential, under the combined conditions of polymerization pressure and chassis temperature employed, the polymerization reaction mixture:
A single fluid phase may be formed or two phases may be separated.

(3) Reactor supply gas composition The reactor supply gas composition employed in the present invention is based on ethylene weight - 100 weight ratio, at least one (χ-olefinic comonomer 0 to () 5 t%, and the molecular weight of hydrogen as regulator is usually within the range of 0 to 20 molar proportions.

(4) Residence Time The average residence time in the reactor is related to the duration of activity of the catalyst under the reaction conditions employed. In the catalyst of the present invention, the E-level retention time is within the range of 2 to 600 seconds, preferably 10 seconds to 150 seconds, and more preferably 10 seconds to 150 seconds.
8 (2013).

4) Usage ratio of component A and component B The usage ratio of component A and component B is not particularly limited, and is preferably in the range of 1 to 100 in AI/T1 atomic ratio, more preferably 1 to 30. is within the range of

Examples Example 1) Synthesis of solid component (A1) Dehydrated and deoxygenated n
- 50 ml of hebutane is introduced, then MgC12
kO, 1 mol and TI(0-nBu)4kO
, 2 moles were introduced, and the reaction was carried out at 90°C for 2 hours. After the reaction was completed, the temperature was lowered to 40°C, and then methylhydrothene polysiloxane (20 centistoke) i1
2 ml of the solution was introduced and the reaction was allowed to proceed for 2 hours.

Raw 1j'2 L solid ingredients (washed with 5n-hbutane,
Part of it? When I took it out and analyzed its composition, I found that Ti
= 14.3 weight + JA-cent, CI = 11.7 weight, l
t, 6-cent, 碌-5,3 weight percent, St
"" 1.5 heavy cavalry) ξ - cent. Also, BET
When the specific surface area was measured using the 6111 method, the specific surface area was too small to be determined, but it is estimated to be about 1 m2/g.

2) Production of solid catalyst component (A) Dehydrated and deoxygenated N
-50ml of 1\zotan was introduced, the isotropic component (A+) synthesized above was introduced, and then TiCl4 (
Component (a)) (1.1 mol and milliliter of n-hebutane) were completely introduced and reacted at 50°C for 2 hours.

After the reaction is finished, the solid catalyst component (
A). When a part of it was taken out and analyzed for composition, it was found that Ti = 10.7'dj%.

3) Preparation of catalyst dispersion Add 1 ml of thoroughly degassed and purified n-hexene (Z 30) to a 1 liter flask containing 4 barrels, then add the above [^11 Component (A)' to 5+; Furthermore, diethylaluminum chloride (A in atomic ratio)
10.8 g of 1-hexene (At/Ti = 8), 10 ml of 1-hexene (atomic ratio: At/Ti = 8) was heated to FIl'C and pressed for 00 minutes.

This catalyst suspension was placed in a catalyst preparation tank with a stirrer purged with completely dry nitrogen, and then thoroughly degassed and purified n-hexane was added to
Add until it becomes a little, and adjust the linearity of the solid component to 0.2 g.
/ liter. This was designated as catalyst (a)-1.

4) Contents of high-pressure polymerization of ethylene Ethylene and propylene were copolymerized in a 1.5 liter stirring autoclave continuous reactor under the reaction conditions shown in Table 1. The catalyst is the above-mentioned (a)-1'f
-Used. The polymerization results are shown in Table-1.

Examples 2 to 4 Same as Example-1 except that the organoaluminum compound used in preparing the catalyst dispersion of Example-1 was changed as shown below.
Catalyst dispersion (a) = 2 to (a)-4 in exactly the same manner as in 1.
'! I prepared it and completed the entire chassis. The results are shown in Table-1.

Example-5 1) Production of solid catalyst component (A) Dehydrated and deoxygenated n
- ml of heptane was introduced, solid component (A) synthesized in the same manner as in Example-1 was introduced, and then 'ric
14 (component (a)) 0.075 mol, 5ICI4 (
Component (b)) 0.025 mol and n-hebutane 5
QmiIJ Little was introduced and reacted at 50°C for 2 hours.

After the reaction is completed, the catalyst component (A) is washed with n-hebutane.
And so. It was 11.4% by weight in T.

2) Preparation of catalyst dispersion and high-pressure polymerization of ethylene Preparation of catalyst dispersion and high-pressure polymerization of ethylene were carried out in exactly the same manner as in Example-1. The results obtained are shown in Table-1.

Example-6 1) Production of solid catalyst component (A) Dehydrated and deoxygenated n
-Solid component (A) synthesized in the same manner as in Example-1 by introducing 50 ml of hebutane'? 4 people, then TlC
04 mol of n-heptane (component (a)) and 1 ml of n-heptane were added, and 1 ml of methylhylene and 12 ml of noene polysiloxane (component (c)) were introduced, and the mixture was heated at 70°C for 2 hours. Made it react.

After the reaction is finished, the solid catalyst component (
A). Ti was 14.9%.

2) Preparation of catalyst dispersion liquid and high-pressure polymerization of ethylene The catalyst dispersion liquid manufactured by Furukawa and high-pressure polymerization of ethylene were prepared in Example-1.
The same procedure was carried out.The first results obtained are shown in Table 1.

The same apparatus and catalyst dispersion as in Example-1 ((a)-1
) was used to carry out copolymerization of ethylene and other α-olefins. The types of I-olefins employed and the polymerization results are shown in Table 1.

Claims (1)

Claims: A combination of components A and B at a pressure of at least 200 kp/c+n2 and a temperature of at least 125° CO)? Polymerization of ethylene, which is characterized by contacting the basic catalyst with ethylene or ethylene and a small amount (both with one type of α-olefin).Contact with component (A1) and component (A2) Product component (A1) Contact product component (A2) of a polymeric silicon compound having a structure of magnesium nohalide, titanium tetraalkoxide and -81-0- (R1 is a hydrocarbon residue) The components (,) ~ fc) are small (tomo - glaze (,)
Liquid titanium compound (however, when used in combination with konezen-single use and ingredient c), this titanium compound must be a halogen-containing substance) (b) Silicon halogen compound 2 (c) A polymer silicon compound having a structure represented by -s+ -o- (R2 is a hydrocarbon residue that is the same as or different from R1). Component (Bl General formula R33-mAIXm (where R3 has 1 to 1 carbon atoms)
0 hydrocarbon residue, X is halogen, m is O < m < 2
is the number of ).