JPS5850243B2 - Olefin Oyobi Diolefin Noji Yugokiyouji Yugo Oyobio Oligomer Kahou - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to catalytic polymerization processes, and more particularly to olefin and diolefin polymerization, copolymerization and oligomerization processes.

The process of the invention is suitable for the production of polyethylene, polypropylene, copolymers of ethylene and propylene or butene, or for the production of ethylene-propylene-diolefin rubbers and oligomeric olefin products using the so-called low-pressure process (Ziegle).
It is widely used because it is manufactured by the r method).

Formula; MXn (wherein M represents a metal or metal oxide of groups IVA to VIA and group II of the periodic table, and X represents a halogen, hydrogen, alkoxy group, aryloxy group, amide group or cyclopentadienyl group) and n represents an integer representing the valence of the metal M];
General formula; M'RpZk.

(In the formula, M1 represents a metal from Groups ■ to ■ of the periodic table, R represents a hydrocarbon residue, or represents a halogen, hydrogen, alkoxy group, or amide group, and k represents the valence of M'(7). Processes for the polymerization, copolymerization and oligomerization of olefins over two-component catalyst systems consisting of organometallic compound components having an integer of G., Gaylord.
Herman F., Mark, co-author, Linear
and 5tereorecular additi-
on polymers: polymerization
with controlled propagati
on, 1959, Interscience Pu.
Blishers, Inc., New York).

In order to increase the activity of the complex catalysts for the polymerization and copolymerization of olefins and to adjust the kinetic parameters of the catalyst-induced polymerization process and the properties of the polymers formed, the components of the catalyst or their The reaction product is fixed onto an inorganic support, ie, an oxide, hydroxide or oxyhalide of a certain metal.

In fact, although the activity of this type of catalyst increases, the inorganic support remains in the resulting polymer and increases its ash content.

In recent years, attempts have been made to eliminate this drawback.

For this purpose, catalysts have been proposed for the polymerization and copolymerization of olefins and diolefins on carbon- and hetero-chain polymers containing fragments capable of fixing polymeric carriers, namely the compounds MXn or M'R,Zk-. It was done.

For example, catalysts such as the reaction products of T iCl , activated with diethyl-aluminum chloride, and the hydroxyl groups of banknote cellulose, polyhydric alcohols, polyglycols are known (UK Patent No. 834,217, CI (1) )
BOIj, May 4, 1960).

Also, avoid reaction products of TiCl4 with hydrolyzed copolymers of ethylene and vinyl acetate or vinyl chloride containing 1 to 20% hydroxyl groups, which are activated with organoaluminum compounds. , olefin polymerization and copolymerization catalysts are also known.

When the respective component solutions are mixed together, TiCl4 is immobilized by their hydroxyl groups on the polymer as described above (French Patent Nos. 1,405,371 and 1,588,369); Nitrogen-containing polymers containing functional amino groups, imino groups, imido groups, urethane groups, nitrile groups or tritro groups (Belky Patent No. 706659, C08fs,
May 17, 1968) and sulfur-containing polymers such as polysulfone (Belky Patent No. 690008, C08f
Catalysts for the polymerization and copolymerization of olefins are also known, including reaction products of MXn and MXn activated with organoaluminum compounds.

Furthermore, this type of catalyst is activated with an organoaluminium compound and is composed of an element having unshared electrons with MXn (>N −
, -0-, -8- or >P-) (USSR Inventor's Certificate No. 420330, BOIj, 11/84, 197
4 years).

Also known as polymerization and copolymerization compound catalysts are mixtures of MXn and organoaluminum compounds fixed on polymeric carriers containing >C=0 groups, >C≦N-groups, or -C≦N groups. (Belky Patent No. 716375, C08
Class f, December 11, 1968).

However, the aforementioned polymerization and copolymerization catalysts do not meet the requirements of modern industry for producing polyolefins, since they have a number of drawbacks that limit their usability and in some cases render them unusable.

The most important drawbacks inherent in known catalysts for the polymerization and copolymerization of olefins are listed below.

1. The activity in polymerization and copolymerization reactions of olefins and diolefins is relatively low (for example, the yield of polyethylene does not exceed 1-2ky/9M).

This is because most of the components (MXn or M'R, Zk-) that are fixed to the polymer carrier are drawn into the polymer carrier and do not participate in the generation of active centers of polymerization.

The utilization of the components used is less than 2-3%.

2. Complicated operations are required to wash away catalyst residues (after use in the polymerization process) that reduce the stability of the resulting product.

3. If MXn is fixed to a polymer carrier, the consumption coefficient for the second component of the catalyst (M'R, Zk,) is high.

This is due to the emptiness (v) that always exists in this type of polymer carrier.
acant) fragments.

4. The polymeric carrier of the catalyst is not necessarily fully compatible with the resulting product due to its different properties.
This has an undesirable effect on the properties of the resulting polyolefins or copolymers thereof.

5. Said polymer carrier obtained by polymerization or copolymerization with expensive monomers is not easily accessible.

6. The properties (molecular weight, bulk weight and composition) of the resulting polymerization product are difficult to control.

The object of the present invention is to polymerize olefins and diolefins over catalysts which produce polymers in high yields, whose bulk weight and molecular weight can be easily controlled, and which can be easily washed out from the resulting polymers. , and a method for copolymerizing the same.

This objective is accomplished by providing olefin and diolefin polymerization and copolymerization catalysts as described below.

That is, the catalyst according to the present invention comprises component A, component B and component C.
Component A is one of the following, and the component A has the general formula;
represents hydrogen, a cyclopentadienyl group, an alkoxyl group, an aryloxyl group, or an amide group, and n represents an integer representing the valence of the metal M), and the component B has the general formula; % formula % [ In the formula, M' represents a metal of groups 1 to 2 of the periodic table, R represents a hydrocarbon residue, Z represents a halogen, hydrogen, an alkoxy group, an aryloxy group, or an amide group, and k represents M
represents an integer indicating the valence of ', and p <k], and the component C is a reaction product of the Mxn and M'R, Zk, that is, the general formula; % formula % [In the formula, M' represents a metal of groups I to II of the periodic table, R represents a hydrocarbon residue, Z represents a halogen, hydrogen, alkoxy group, aryloxy group, or amide group, k is M
' represents an integer indicating the valence of
and M′R9Zk-p, i.e., a compound having the general formula;
Each of these components has the general formula;
3, C2H5, CH2-CH or C6H5, W
represents H or CH3, R''' represents H or CH3, and Y represents OH, NHR', SR.

C0CHCHOH, CHNHR', C0OH, OCOC
H3゜3 tsu 22 COOCH3, C3N, N(Fj')2. -8, 80
□“.

5000], component A is activated with the compound M'RZk- and component B is activated with the compound MXn. It is characterized by being

Reactions of carbon chain polymers containing the above-mentioned fragments on their surfaces with compounds MXn, M'RpZ k-, and MRmXn-m have not been previously known.

The catalyst according to the invention has the following general formula: (where M represents a transition metal or an oxide of a metal belonging to groups IVA to VIA or group II of the periodic table, and X represents a halogen, hydrogen,
a cyclopentadienyl group, an alkoxyl group, an aryloxyl group, or an amide group, n is an integer representing the valence of the metal M), and the catalyst compound has the following general formula: R' represents H2CH3, C2H5, CH2-CH or C6H5, R'' represents H or CH3, R''
' represents H or CH3, Y is OH, NHR'SR,
COCH3, CH20H, CH2NHR'.

C0OH,0COCHC00CH8,C3N,N(R'
)2゜3 ft represents an average degree of polymerization of 4 to 5000], and is chemically bonded solely to the surface of the carbon chain polymer carrier, and the compound M'R
In the ZC formula, V represents a metal from group 1) k-p 1 to ■ of the periodic table, R represents a hydrocarbon residue,
Z represents a halogen, hydrogen, an alkoxy group, an aryloxy group, or an amide group, and k represents an integer representing the valence of M', which is 1 to 1. .

According to the invention, the olefin and diolefin polymerization and copolymerization catalysts may be in the following embodiments.

(2) Component A is a compound of the formula: MXn, which binds to the surface of the polymer carrier activated with one of the organometallic compounds having the formula; represents a number from 50 to 1500).

The catalyst of this embodiment can be represented as follows: Component A where -X-X-X- represents the surface of the carbon chain polymer.

Typical catalysts of this type are listed below: 1. TiCl4 is combined with the surface of hydrolyzed polyethylene-gr,-polyvinyl acetate activated with A1(C2H5>3C1) catalyst.

In this specification, 11 gr and 11 represent "crafted".

2. Catalyst in which TiCl4 is combined with the surface of hydrolyzed polyethylene-gr,-polyvinyl acetate activated with AI(C2H5)s.

3. A catalyst in which VCI is combined with the surface of hydrolyzed polypropylene-gr,-polyvinyl acetate activated with AI(C2H5)2C1.

4. Hydrolyzed polystyrene-gr in which VCl4 was activated with AI<iso-C,H,)2H.

-Catalyst combined with the surface of polyvinyl acetate.

5. Catalyst in which VCl4 is combined with the surface of hydrolyzed poly(ethylene-copropylene)-gr,-polyvinyl acetate activated with AI(C2H5)2CI.

6. Catalyst in which MoCl5 is combined with the surface of hydrolyzed polyethylene-gr,-polyvinyl acetate activated with AI(C2H5)2C1.

7, Ti(OC4Ho) 4 is AI(C2H5)2
Hydrolyzed polyethylene-g activated with C1
r, - a catalyst combined with the surface of polyvinyl acetate.

8, (C5)(5)2TIC12 is Al(C2H5
) 2C1-activated catalyst combined with the surface of hydrolyzed polyethylene-gr,-polyvinyl acetate.

9, (C5H5)2TIC12 is At(isoC4
H9) 2C1-activated catalyst combined with the surface of hydrolyzed polyethylene-gr6-polyvinyl acetate.

(2) Component A is a compound of the formula: MXn and has the above formula: M'R, Zk-, on the surface of a polymer carrier activated with an organometallic compound 4, and a fragment (where t is (representing a number from 100 to 2000).

This type of catalyst can be shown as follows: Component A Representatives of this catalyst are listed below: 1. TiC
Catalyst in which l4 is combined with the surface of reduced polyethylene-gr,-polymethyl vinyl ketone activated with AI(C2H3)2C1.

2. Catalyst in which VCI is combined with the surface of reduced polyethylene-gr,-polymethyl vinyl ketone activated with Al(C2H6)2Cl.

3. T i (0-C2H5)2 is AI(C2H
5) Reduced polyethylene activated with 2C1-
gr, - a catalyst combined with the surface of polymethyl vinyl ketone.

4 (C5H5)2TIC12 is AI (C2H5
) 2C1 activated reduced polyethylene gr
, - a catalyst combined with the surface of polymethylvinyl ketone.

5. Catalyst in which MoC1, is combined with the surface of reduced polyethylene-gr,-polymethyl vinyl ketone activated with AI(C2H6)2C1.

6. TlC14 was activated with Al(C2H5)2C1, reduced poly(ethylene-copropylene)-
gr, - a catalyst combined with the surface of polymethyl vinyl ketone.

7. Catalyst in which VOCl3 is combined with the surface of reduced polystyrene-gr,-polymethyl vinyl ketone activated with Al(iso-C4H9)2C1.

(2) the surface of a polymeric carrier whose predominant component is one of the compounds of the formula MXn, which is activated with one of the organometallic compounds having the formula M'RZk-; 300).

This type of catalyst can be represented as follows: Component A Typical of this type of catalyst are: 1. TiCl4 is reduced, activated with AI(C2H5)2C1. A catalyst that is combined with the surface of polyethylene-gr,-polyisopropylidene acetone.

2. VCI, but AI (iso-C,H0)2(,
Reduced polyethylene activated with t-gr,-
Catalyst combined with the surface of polyisopropylidene acetone.

3. Catalyst in which VOCl3 is combined with the surface of reduced polystyrene-gr,-polyisopropylideneacetone activated with A1(C2H6)2C1.

V, component A is one of the compounds having the formula M (representing the number 9).

This type of catalyst can be represented as follows: Component A Typical of this type of catalyst are: 1. TiC1+ is activated with AI(C2H6)2C1 polyethylene-gr , - a catalyst combined with the surface of polyallyl alcohol.

2. A catalyst in which TlC14 is combined with the surface of AI (iso-C,H9) di-activated polypropylene-gr,-polyallyl alcohol.

3. VCI, but AI (iso-C4H0)2C1
catalyst combined with the surface of activated poly(ethylene-copropylene).

4. A catalyst in which VOCl3 is combined with the surface of polystyrene-gr,-polyallyl alcohol activated with Al(C2H5)3.

5. A catalyst in which VCI is combined with the surface of polyethylene-gr,-polyallyl alcohol activated with AI(C2H5)2C1.

6. Catalyst in which MoCl5 is combined with the surface of polyethylene-gr,-polyallyl alcohol activated with AI(C2H5)2C1.

7. A catalyst in which WCI is activated with AI(C2H5)2C1 and combined with the surface of tafolyethylene-gr,-polyallyl alcohol.

8. Ti(QC4H9)+ is AI(C2H5)2
Catalyst combined with the surface of C1-activated polyethylene-gr,-polyallyl alcohol.

9, TI (OC4H9)4 is AI□(C2H5
) A catalyst combined with the surface of polyethylene-gr,-polyallyl alcohol activated with 3C13.

10, (C6H5)2TiC12 is AI(C2H5)
Catalyst combined with the surface of polyethylene-gr,-polyallyl alcohol activated with 2C1.

11. A catalyst in which VCI is combined with a polyethylene-gr,-polyallyl alcohol surface activated with Zn(CHs)s.

12. A catalyst in which VCI is combined with the surface of polyethylene-gr,-polyallyl alcohol activated with L I C4Ho.

13. Tl (OC4H9)4 is AlC2H5CI
Catalyst combined with the surface of polyethylene-gr,-polyallyl alcohol activated with 2.

■, the surface of a polymer carrier in which the precipitate component is one of the compounds having the formula MXn, which is activated with one of the organometallic compounds of the formula M'RZk-, and the fragment: (where t is 4 to (representing the number 9).

This type of catalyst can be illustrated as follows: Component A Typical catalysts of this type are as follows.

1. A catalyst in which TlC14 is combined with the surface of polyethylene-gr,-polycrotyl alcohol activated with AI (C2H5)2Cl.

2, VCI, but AI (iso-”4H9)2C1
catalyst combined with the surface of polystyrene-gr,-polycrotyl alcohol activated with.

3. A catalyst in which VCl4 is combined with the surface of polyethylene-g,r-polycrotyl alcohol activated with At(iso-C4H0)2H.

(2) Component A is one of the compounds of the formula MXn, which forms the surface of a polymer carrier activated with an organometallic compound of the formula M'RZk-, and the fragment: (where t is a number from 4 to 9). a catalyst that is combined via

This type of catalyst can be represented as follows: Component A Representative of this type of catalyst is as follows: 1. TiCl4 is activated with AI(C2H5)2CI polyethylene- gr, - a catalyst combined with the surface of the polycin alcohol.

2. Catalyst in which VCl4 is activated with AI(C2H5)2C1 and combined with the surface of tahouriethylene-gr,-polycin alcohol.

■, Component A is a compound of formula MXn, which is a compound of formula M'R
The surface of a polymeric carrier activated with an organometallic compound of 2Zk-p and the fragment: (where t is 500-20
(representing the number 00).

This type of catalyst can be represented as follows: Component A Representative of this type of catalyst are: 1. TiCl4 activated with A1(C2H5)2C1; Catalyst combined with the surface of reduced polyethylene-gr,-polyacrylonitrile.

2. Catalyst in which VCI is combined with the surface of reduced polyethylene-gr,-polyacrylonitrile activated with A1(C2H5)2C1.

3. Catalyst in which VOCl3 is combined with the surface of reduced polyethylene-gr,-polyacrylonitrile activated with AI(C2H5)2C1.

■, Component A is a compound of formula Mxn, which is a compound of formula M'R
.

This type of catalyst can be represented as follows: Component A Representative catalysts of this type are listed below; , - a catalyst combined with the surface of polydiallylamine.

2. Catalyst in which VCl4 is combined with the surface of polyethylene-gr,-polydiallylamine activated with AI(C2H6)2Cl.

3. A catalyst in which VOCl3 is combined with and warps the surface of polypropylene-gr,-polydiallylamine activated with AI(C2H5)2C1.

4. Catalyst in which MoCl5 is combined with the surface of poly(ethylene-copropylene)-gr--polydiallylamine activated with AI(C2H6)2C1.

5. Ti(OC+)(o)4 is A1ζC2H3)
Catalyst combined with the surface of polyethylene-gr,-polydiallylamine activated with 2C1.

6, (C5H5)2T s C12 is (C2H5)2
Catalyst combined with the surface of polyethylene-gr,-polydiallylamine activated with AIC1.

7. Catalyst in which VCl4 is combined with the surface of polyethylene-gr,-polydiallylamine activated with AI(iso-C4H9)2H.

8, ■0(OC2H5)3 is AI (C2H6)2C
Catalyst combined with the surface of polyethylene-gr,-polydiallylamine activated with l.

9. Catalyst in which VCI is combined with the surface of polystyrene-gr,-polydiallylamine activated with AI(C2H5)2C1.

(2) Component A is a compound of the general formula MXn, which is a fragment of the formula M'R,
A catalyst combined with the surface of a polymeric carrier activated with an organometallic compound of Zk.

This catalyst can be shown as below; Component A. Typical of this type of catalyst are as follows: 1. Polyethylene-gr in which TlC14 is activated with AI(C2H6)2C1; -Catalyst combined with the surface of polyallylamine.

2. A catalyst in which VCI is combined with the surface of polyethylene-gr,-polyallylamine activated with A1(C2H6)2C1.

3. Catalyst in which VOCl3 is combined with the surface of polystyrene-gr,-polyallylamine activated with AI (iso-C,H0)2C1.

X, component A is a compound of the general formula Mxn, which is a fragment:
A catalyst combined with the surface of a polymeric carrier activated with an organometallic compound of Zk.

This type of catalyst can be represented as follows; Component A Representative of this catalyst is as follows: 1. TiC1, polyethylene-gr activated with AI(C2H5)2C1; -Catalyst combined with the surface of polyallyl mercaptan.

2. A catalyst in which VCI is combined with the surface of polyethylene-gr,-polyallyl mercaptan activated with AI(C2H5)2C1.

3. A catalyst in which VCI is combined with the surface of polyethylene-gr,-polyallyl mercaptan activated with AI (iso-C,H,)2'H.

4. VCl4 was activated with AI (iso-C,H,)2H poly(ethylene-copropylene)-gr
, - a catalyst combined with the surface of polyallyl mercaptan.

(2) A catalyst in which component A is a compound of the formula MX, which is combined via the fragment: with the surface of a polymeric carrier activated with one of the organometallic compounds of the formula M'R2Zk-p.

This type of catalyst can be illustrated as follows.

Component A Representative examples of this catalyst are as follows: 1. A catalyst in which TiCl4 is combined with the surface of polyethylene-gr,-polymethacrylic acid activated with Al(C2H5)2C1.

2. Catalyst in which VCl4 is combined with the surface of polypropylene-gr,-polymethacrylic acid activated with A1(C2H5)2C1.

3, Ti(QC4H9)-≦, Al(C2H5)2C
A catalyst combined with the surface of polyethylene-gr,-polymethacrylic acid activated in 1.

4. Catalyst in which VCl4 is combined with the surface of polystyrene-gr,-polymethacrylic acid activated with AI(C2H,)2C1.

Component A is a compound of formula MXn, which is a compound of formula M
'RZk--catalyst combined with the surface of a polymeric carrier activated with an organometallic compound.

This type of catalyst can be represented as:

Component A Representative catalysts are listed below: 1. TiC
Catalyst in which l4 is combined with the surface of polyethylene-gr,-polyacrylonitrile activated with AI(C2H5)2C1.

2. A catalyst in which VCI is combined with the surface of polyethylene-gr,-polyacrylonitrile activated with Al(C2H5)3.

3. VCI is activated with AI(C2H5)2C1 and becomes 7': HoIJ(ethylene-copropylene)-g
r, -Catalyst combined with the surface of polyacrylonitrile.

4. Catalyst in which VCl4 is combined with the surface of polypropylene-gr,-polyacrylonitrile activated with AI(C2H5)2CI.

5. Catalyst in which MoCl5 is combined with the surface of polyethylene-gr,-polyacrylonitrile activated with Al(C2H5)2C1.

6, VCl4 is A1. Catalyst combined with the surface of polypropylene-gr,-polyacrylonitrile activated with (iso-C4H,)2H.

Xl, component A is a compound of the general formula □ odor, which is a fragment: (wherein t represents a number from 500 to 5000),
A catalyst combined with the surface of a polymeric carrier activated with an organometallic compound of the formula M'R, Zk.

This type of catalyst can be represented as follows: Component A Representative of this type of catalyst are: 1. Polyethylene-activated with TiC14JJi, AI(C2H5)2C1 gr, - a catalyst combined with the surface of poly(2-vinylpyridine).

2.VCI is polyethylene-gr,-poly(2-vinylpyridine) activated with Al(C2H5)2C1
catalyst combined with the surface of.

3. A catalyst in which VCl4 is combined with the surface of polypropylene-gr,-poly(2-vinylpyridine) activated with Al(C2H5)3.

4. A catalyst in which VOCl3 is combined with the surface of polystyrene-gr,-poly(2-vinylpyridine) activated with AI(iso-C,H0)2H.

XIV, component A is a fragment: (wherein t represents a number from 500 to 5000),
A catalyst combined with the surface of a polymeric carrier activated with an organometallic compound of the formula M'RZk-.

This type of catalyst can be represented as:

Component A Representative catalysts of this type are listed below: 1. TiCl4 is combined with the surface of polyethylene-gr,-poly(4-vinylpyridine) activated with AI(C2H5)2C1. A catalyst.

2, VCI, polyethylene-gr,-poly(4-vinylpyridine) activated with AI(C2H5)2C1
catalyst combined with the surface of.

3. A catalyst in which VCI is combined with the surface of poly(pyrene-gr,-poly(4-vinylpyridine)) activated with Al(C2H6)2C1.

4. A catalyst in which VOCI is combined with the surface of polystyrene-gr,-poly(4-vinylpyridine) activated with AI(iso-C4H9)2H.

5. Catalyst in which CoCl2 is combined with the surface of polyethylene-gr,-poly(4-vinylpyridine) activated with AI(C2H5)2C1.

xv precept component is a compound of formula MXn, fragment
~--- (in the formula, t represents a number from 400 to 4000),
A catalyst combined with the surface of a polymeric carrier activated with an organometallic compound of the formula M'R, Z k□p.

This type of catalyst can be represented as follows: Component A Typical of this type of catalyst are: 1. Polyethylene in which TiC1+ is activated with AI(C2H5)2C1 -gr, -Catalyst combined with the surface of polymethyl methacrylate.

2. Catalyst in which VOCl3 is combined with the surface of polystyrene-gr,-polymethyl methacrylate activated with AI(C2H5)2C1.

XVl, a polymer in which component A is a compound of formula MXn, which is activated with an organometallic compound of formula M'R, Zk, via fragmentation f13 (wherein t represents a number from 50 to 1500); Catalyst combined with the surface of the carrier.

This type of catalyst can be shown as follows: Typical catalysts of this type are listed below: 1. TiC
A catalyst in which 1+ is combined with the surface of polyethylene-gr,-polyvinyl acetate activated with AI(C2H5)2C1.

2. A catalyst in which TiCl4 is combined with the surface of polystyrene-gr,-polyvinyl acetate activated with Al(iso-〇4H0)CI.

(2) Component A is a compound of the formula MXn, which is capable of forming a compound via a fragment (in the formula, t represents a number from ioo to 2000),
A catalyst combined with the surface of a polymeric carrier activated with an organometallic compound of the formula M'R, Zk.

This type of catalyst is designated as: 1, TiC1
, on the surface of polyethylene-gr,-polymethyl vinyl ketone activated with AI(C2H5)2C1.

2. Catalyst in which VCl4 is applied on the surface of polystyrene-gr,-polymethyl vinyl ketone activated with AI(C2H5)2C1.

3. Catalyst in which VCl4 is applied on the surface of polyethylene-gr,-polymethyl vinyl ketone activated with AI(iso-C4H0)2H.

■ Component A is a compound of the formula MXn, which is a fragment of the formula M'RZk via a fragment: (wherein t is a number from 4 to 9)
- a catalyst in combination with the surface of a polymeric carrier activated with an organometallic compound.

This catalyst can be represented as follows: Component A Typical catalysts of this type are listed below: 1. Ti
A catalyst in which C1, is combined with the surface of polyethylene-gr,-polydiallyl sulfide activated with Al(C2H6)2C1.

2. Catalyst in which VCl4 is combined with the surface of polyethylene-gr,-polydiallyl sulfide activated with AI(C2H5)2C1.

3. A catalyst in which VCI is combined with the surface of polypropylene-gr,-polydiallyl sulfide activated with AI(C2H5)2C1.

(2) is a compound of the formula MXn for the component, and this is a compound of the formula M'R,
A catalyst combined with the surface of a polymeric carrier activated with an organometallic compound of Zk.

This type of catalyst can be represented as follows: Component A Typical of this type of catalyst are the following compounds: 1. TiCl4 activated with Al(C2H6)2C1 A catalyst combined with the surface of polyethylene-gr,-polydiallylsulfone.

2. Catalyst in which TiCl4 is combined with the surface of polystyrene-gr,-polydiallylsulone activated with AI(C2H6)2C1.

(2) Component B is an organometallic compound of the formula M'R9Zk-p, which is bonded to the compound of the formula Mxn on the surface of the carrier, and the fragment (in the formula, "represents R or H") Component B of this type Representative catalysts are as follows: 1. A catalyst in which Al(C2H5)3 is combined with the surface of polyethylene-gr,-polyacrylonitrile combined with VCl4.

2. A catalyst in which AI(iso-C4H0)2H is combined with the surface of polypropylene-gr,-polyacrylonitrile bound to VCI4.

When component B is a compound of the formula M'R, Zk, it is combined with the surface of the polymer carrier bonded with a compound of the formula MXn via a fragment (where t represents a number from 100 to 200). catalyst.

This type of catalyst can be represented as follows: Component B Typical catalysts of this type are as follows: 1. Polyethylene- gr, - a catalyst combined with the surface of polymethylvinylkene.

2. A catalyst in which AI (iso-C4H0)3 is combined with the surface of polystyrene-gr,-polymethyl vinyl ketone bonded to (1)0CI3.

XXl1. It is a reaction product of MXn and M'RpZk-, and has the general formula MRmXn-m (wherein M , X ,
n, M', m.

R2Z, p and k are as defined above), and the component C is combined with the surface of the polymer carrier via fragments, in which t represents a number from 4 to 9.

This type of catalyst can be represented as: Representative catalysts of this type are as follows.

1. A catalyst in which T 1 (CH2C6H5)4 is combined with the surface of polyethylene-gr,-polyallyl alcohol.

2. 'V(CH2C6H5)4 is polyethylene-
gr.

-Catalyst combined with the surface of polyallyl alcohol.

Yano, the reaction product of said MXn and M'R, Zk, which has the formula MRmXm-n, and which is a reaction product of the aforementioned MXn and M'R, Zk, which has the formula MRm A catalyst containing component C combined with.

The catalyst can be represented as follows: The olefin and diolefin polymerization, copolymerization and oligomerization catalyst according to the invention comprises a suspension of a polymer carrier in a hydrocarbon or halogenated hydrocarbon solvent. MXn5M'R9
Zk-p or MRmXn-m compound (or solution thereof)
and the free product is isolated by chemical methods,
A compound of the formula M'R, Zk can be prepared by activating the obtained component A with the obtained composition of component B and MXn.

To apply MXn to the surface of a polymeric carrier (to produce component A of the catalyst), for example VCI and Ti (OC4H
9) Reacting 4 with polyethylene-gr,-polyallyl alcohol This shows a reaction route for producing component A, where MXn is reacted with a polymeric carrier via a fragment containing one of the groups Y below. NiOH, -NH2, which is combined with the surface of
>NH, -COOH, R'NH, RouOH, or -CH2
SH (C5H5)2TiC12, Ti(OC4H9)4
or ■ Contrary to the typical homogeneous catalyst, which uses 0(OC2H5)3 as a substrate and is activated with M'RZk-, two transition metal compounds (component A) are used as substrates and is activated with M'R9Zk-p. It can be seen that one catalyst according to the present invention was an average-catalyst component A $ medium.

Fragment has functional group Y; SR', COCH3, CH2
5R', OCOCH3, Co0cH3° Produced by receptor mechanism (generation of complex compound).

The following formula shows the case where Y represents -C3N. Component B of the polymerization and copolymerization catalyst for niolefins and diolefins is a polymer carrier and a suspension of the fragments M'R, Zk-, , (or a solution thereof in a hydrocarbon solvent), for example by reacting with component C: For example, the carrier for the polymerization and copolymerization catalyst for niolefins and diolefins obtained by the reaction described below is produced as follows.

Carbon chain chains can be conjugated mechanochemically, by radiation or by chemical action in the presence of a compound of the formula: [wherein R', R'', R'' and Y are as defined above], in other words: Carbon-carbon double bond on one side and MXn, M'R, Zk, or MR on the other side
Due to the presence of a compound containing a functional group that can fix mXn-□,
Process.

Carbon-carbon double bonds are important for graft polymerization of compounds having the formula to form said fragments, and the polymerization initiation method is only at the surface of the carrier carbon-carbon polymer as shown below. The grafting/polymerization of a compound having: selected to be grafted onto the surface of a carbon chain polymer using ionizing radiation (C
It is most effective to start with the gamma line of the o60 isotope, accelerated electrons, radio frequency discharge).

This method uses any carbon chain polymer (with the same properties as synthetic polymers or (including similar ones).

Moreover, grafting onto the macromolecules of the surface layer does not result in any change in the substance of the carbon chain polymer, so that the grafted fragments are only present on the surface of the carrier.

The thus produced fragment-grafted Saleta carbon chain polymers are MXn, M'l'(pZk-, or MR
mXn-□ can be used on top of it, and the grafted fragment can be used to produce functional groups with different properties (e.g., hydrolysis of acetate groups to hydroxyl groups, reduction of ketone groups to hydroxyl groups, reduction of the di-IJ group to an amino group), polymer-like transformations (Polymer
-analogous tra-nsformatio
n) may occur.

Polymer-like transformations of grafted fragments at the surface of carbon chain polymers occur in quantitative yields, without side reactions in suspension, and under relatively mild conditions, e.g. Allyl-type compounds containing OH, 2N)l, -NH2 (allyl alcohol, allylamine, diallylamine,
Allyl mercaptan).

These are due to high degenerative chain transfer on the 7mer,
It is said that it is difficult to polymerize compounds.

As a result, there is no homopolymer of the allylic compound to be grafted, and only short (t-4 to 9) polymer fragments are produced.

This latter fact is extremely important.

This is because this fact allows sufficient steric accessibility for the chemical bond between the functional group of the Y fragment and MXn, M'R, Zk-p or MRmXn-m.

The olefin and diolefin polymerization and copolymerization catalysts according to the invention have component A of the formula M'R,Zk-.

(according to reaction formula I-)IX).

M'R,Zk-'' relative to M in component A. The molar ratio of M' therein is from 5 to 500, in particular from 10 to 100.

The first step of interconversion in the MX M'RZk- system is the formation of the active polymeric bond M-R.

As component A reacts with M'R, Zk, the active center of polymerization also comes to include the metal-carbon bond M-R.

Yes ■. and depending on the nature of the fragment, this active bond can be present on the surface of the polymer, for example, as follows: Alternatively, component A reacts with M'R, Zk, and transfers from the surface of the carrier. The metal is completely or partially eliminated to form active centers outside the polymer carrier: (the arrows in the above formula indicate the points at which the polymerizable monomers are most likely to be bound).

Component A is T i (OC4H9) 4 on the carrier
Or VO(QC2H5)3 catalysts for polymerization, copolymerization and oligomerization of olefins and diolefins induce polymerization according to reaction formula XXXI, and when other transition metals are used, polymerization is of the active center type (XXXI). and Abyss)
It happens.

Active centers likewise occur in catalysts containing component B present in composition with chemical MXn.

In this case, M' in component B,,! =MX, the molar ratio of M in it is 20 to 200. In particular, it is between 50 and 100.

In the catalyst containing component C, the active bond MR is MRmXn
−□Already present when combining with the surface of Charya.

The olefin and diolefin polymerization, copolymerization and oligozeta-ization catalysts according to the invention have the following advantages over known catalysts used for the same purpose.

1. The catalyst according to the invention is 5 to 100 times more active (in terms of final product yield) than the known catalyst.

The yield of polyethylene with the catalyst according to the invention is 1000 kg per gram of total transition set.

2. The high activity of the catalyst facilitates the otherwise complicated operation of removing catalyst residues from the resulting polymer, and in some cases this operation is completely unnecessary, making it possible to eliminate catalyst residues from the polymerization process. Make flowsheets extremely simple.

3. The catalyst according to the invention is easy to use, since the polymers obtained are already effective in the polymerization stage.

They have high fluidity in the melt, high bulk weight and good physico-mechanical properties.

Furthermore, when T i (QC4H9) 4 is used for the production of component A, the melt index of the molten polyethylene obtained at a pressure of 10 atm is 0.1-3.0 g710 min (with hydrogen as a molecular weight regulator). Without using).

Component A is a vanadium compound (VCl2.VO(QC2H
5)3. When using catalysts containing VOCl2), it is sufficient to contain 10 to 15 volumes of hydrogen in the gaseous state to obtain polyethylene with a melt index of 10 to 12 g/l 0 min.

The bulk weight of the polyethylene powder obtained with the catalyst according to the invention is 530 g/l.

4. The catalyst according to the present invention can be used to produce low-molecular olefin oligomers with a degree of polymerization of 10 to 20 depending on the combination of components and reaction conditions, and can be used independently.

The yield of liquid reaction product is 500 k/g of transition metal
It is g.

5. The catalyst according to the invention is suitable for use in olefin copolymers, especially copolymers of olefins and dienes containing an almost unlimited amount of starting monomers, and polyolefin rubbers, such as ethylene and propylene and ethylene-ethylidene norbornene. It can be used advantageously to produce copolymers, and these copolymers can be further transformed.

The fact that the catalysts of the invention are also used in oligomerization processes further widens their field of application.

The catalyst according to the invention is considered versatile from the point of view of the range of applications of the products produced.

6. Known catalysts using vanadium compounds as substrates are unstable at polymerization temperatures, i.e., 20-40°C (the speed of the polymerization process reaches its maximum immediately after mixing the catalyst components and rapidly decreases). In contrast, the catalyst according to the invention, in which component A contains one of the compounds VCl4゜■0C13,■0(OC2H5)3, combined with the surface and activated with M'R, Zk, , even at high temperatures (80-90°C) for long periods of time (
It exerts a stable effect over several hours).

This greatly simplifies the equipment used in the polymerization process.

No crystallization or fibrillation occurs during the polymerization process.

7. The catalyst according to the invention comprises as a carrier a polymer which is the same or similar (with respect to its properties) to the product obtained.

Therefore, the polymeric carrier does not have to be removed from the final product without impairing the properties of the final product.

8. The method for producing the catalyst according to the present invention is relatively simple.

Polymers of any nature can be used to produce the catalysts according to the invention.

This may be a polyolefin, a copolymer of olefins, a polydiene, a polystyrene.

MXn. The fragment interposed between the chemical bond between M'R, Zk, or MRmXn-□ and the surface of the carbon chain polymer is a readily available substance.

The method for crafting this onto the surface of a carbon chain polymer is simple and can be carried out by any known graft polymerization method.

The advantages listed above are not remotely matched by the known catalysts used in the polymerization and copolymerization of olefins and diolefins.

The catalysts for the polymerization, copolymerization and oligomerization of olefins and diolefins according to the invention can be produced in both batch and continuous processes and can be used in existing and newly installed plants for producing polyolefins and copolymers thereof in low-pressure processes. Can be used in certain conditions.

Next, the present invention will be explained in detail based on Examples, but the present invention is not limited thereto.

Example 1 Two-chamber glass ampoule with independent thermostat (
4.1 g of low-pressure polyethylene (molecular weight 923,000, ash content 0.06) is charged into the upper part of the supply chamber and reaction chamber.

In the supply chamber, CuCl20.05. ? (to prevent vinyl acetate from homopolymerizing in the supply chamber).

The entire ampoule is evacuated to 1 x 10-3 Hg.

Next, freshly distilled, pure vinyl acetate 0.9221
．． ! 7 and seal the ampoule.

A gamma ray source, the radioactive isotope Co60, is used to initiate the radio-vapor phase grafting of vinyl acetate onto polyethylene.

The dose rate of 0.8 mrad/hour is kept constant throughout the entire experiment.

The absorbed dose is 6.0 mrad.

The supply room shall be protected from irradiation.

After grafting, the resulting product, i.e. polyethylene-g, was washed with monopolyvinyl acetate (4.9 g) with hot benzene;
Dry in a vacuum dryer until a certain amount is reached.

The degree of grafting (% by weight of grafted vinyl acetate relative to the weight of starting polyethylene) is 12.5%.

The radiation-chemical yield determined by the following formula is 3 x 102 mol/100 eV; where N represents Avogadro's number, Po represents the weight of the grafted monomer, and AP represents the initial polymer weight. represents the weight of 1, D represents the absorbed dose (rad, ), and M
represents the molecular weight of the monomer and ρ represents the density of the polymer.

Hydrolysis of the grafted fragment of vinyl acetate is carried out as follows.

Methyl alcohol (heating a suspension of 2.5 g of the obtained polyethylene-gr,-polyvinyl acetate in 100 rIIO and sodium methyl alcohol in 20 ml of methyl alcohol) 0.3. ! i' is added gradually (over 2 hours) with vigorous stirring.

The hydrolyzed copolymer is washed with methyl alcohol, then several times with distilled water, and dried to a constant volume.

The yield is 4.3% (measured by the Verley method) of hydroxyl groups simply present on the surface of polyethylene, a carrier for catalysts for polymerization and copolymerization of olefins, -polyethylene-g
In a two-headed flask equipped with a reflux condenser and a separating funnel, 2.2 g of r,-polyvinyl alcohol was obtained.
Hydrolyzed polyethylene gr, -polyvinyl acetate 1
．． 5g and 70ml of freshly distilled pure carbon tetrachloride!
Charge the suspension from the container.

At a temperature of 70°C, the flask is charged with an excess of TiCl4 (0.5.9 in CC1420TLl).

The reaction is complete in 3 hours (tested with gaseous HC7).

The reaction product was transferred under an inert atmosphere into a vacuum filter and filtered with H
Washed three times with CA25-3077il and dried to a certain amount, pale yellow powder containing Ti64/72j7 per gram of product, i.e. component A1 of catalyst for polymerization, copolymerization and oligomerization of olefins and diolefins. Obtain .3g.

The olefin and diolefin polymerization, copolymerization and oligomerization steps are carried out in a stainless steel thermally controlled reactor with vigorous stirring of the reaction mixture using a shielded motor and a paddle type stirrer (approximately 150 Or, p, m, )
implement.

The reactor is dried in vacuo at a temperature of 60° C. and blown with ethylene.

The reactor is charged as follows.

First, the obtained product 0.05. ? The capacity is 1. Charge the O1 reactor in an inert atmosphere.

The reactor is then evacuated to I.times.10@-2 mrnHg and charged with 200 ml of freshly distilled pure n-heptane.

The temperature in the reactor is maintained at 70°C using a thermostat.

desired pressure (10 atm) into the reactor from a special metering cylinder
Add ethylene in the amount necessary to ensure
) g is introduced from a syringe (batcher).

The polymerization process is continued for 3 hours at constant pressure, which is achieved by continuously feeding ethylene into the reactor as it is consumed in the polymerization process.

After the pressure inside the reactor drops to 1 atm, the reaction is stopped by adding 20rrLl of ethyl alcohol, the reaction product is taken out, the solvent is removed from it, the product is dried to a certain amount, and weighed. do.

The yield of polymeric crystalline polyethylene was 39g (12Kp/
EI Ti).

Example 2 Under conditions similar to those described in Example 1, T i CA 40-06 &amp;
Charge 30.64 y of i (C2H3).

Polymerization was continued for 4 hours to form polymeric crystalline polyethylene 15.
5,! i' (4Kp/g Ti) is obtained.

Example 3 Under conditions similar to those described in Example 1, vinyl acetate (0,
4,9) is grafted onto polypropylene powder (4,2,!il).

The yield is 4.5 g of polymer carrier for polymerization catalyst.

This is hydrolyzed under the same conditions as described in Example 1, but
Using 0-xylene as a solvent, the temperature is 85~90''
Keep it at C.

The obtained hydrolyzed polypropylene-gr.

- 1.4 g of polyvinyl acetate in a solution of carbon tetrachloride Example 1
Same as VCA40.6. ! React with 7.

There are 1.3 g of a light brown product (component A) containing 2.15% vanadium.

Under the conditions of Example 1, the product obtained in the reactor was 0.14. !
il and (C2H5)2AlclO,64! Charge j.

The polymerization process continues for 3 hours. The yield of polyethylene is 31.
5 g, which corresponds to a yield of 10.5 Kp/gV.

Polymer 18 is characterized by containing 0.19 double bonds per 1000 carbon atoms, having 60% vinyl carbon atoms and a vinyl (absent trans-vinyritine) saturation of 40.

Yield point 245 Kg/cyn' by physical-mechanical test
, a neck length of 1.3, a tensile strength of 350 Kp/cm'', and an elongation at break of 200% or more.

Example 4 Under the conditions of Example 1, 17.4 g of polyethylene powder [[1.1 g of vinyl acetate was grafted and 5.9 g of the product was hydrolyzed as in Example 1, resulting in hydrolyzed polyethylene-g
5.1 g of r--polyvinyl acetate is produced.

Under the conditions of Example 1, 2.4 g of the carrier obtained were reacted in a suspension of 200 ml of toluene and 20.1 g of (C3H5)2TicA to produce the product, component A1 of the polymerization catalyst.
．． Pale pink powder containing 0.51729 Ti per g 2
．． Produce 3g.

Polymerization is continued in benzene under conditions as given in Example 1.

(C3H5)2T chemically bonded to the surface of hydrolyzed polyethylene-gr,-polyvinyl acetate in the reactor
iCA20.4Fl and (iso-C4Ho)2Al
C10,28,! Enter i'.

Polymerization was carried out for 4 hours and polymerized polyethylene (30Kp
/gTi) to produce 7.5 g.

Example 5 Hydrolyzed polyethylene-gr obtained in Example 4.

-2.4 g of polyvinyl acetate and T i (OC4H9)
4 is reacted in benzene under the conditions of Example 1 to produce a powder of the same color as the starting polymer.

This powder contains 74/72@ TiO per gram of product.

The polymerization is carried out analogously to Example 1 in benzene.

0.49 g of the product obtained and Al(C2H5)2C#
0.3.9 into the reactor.

Polymerization was continued for 4 hours and polyethylene 16.9 (44K
P/,! 7Ti) is obtained.

Melt index is 0.3412.9/10 minutes.

Example 6 Vinyl acetate (0,34F) was prepared with a molecular weight of 350 in the same manner as in Example 1.
00 polystyrene (1,7,F), the irradiation intensity is 1.0 mrad per hour, and the absorption line of gamma rays is 4.5 mrad.

The yield is 1.9 g and the degree of grafting is 20fo.

Hydrolysis was carried out analogously to Example 1 to obtain polymeric carrier 1.
Obtain 6g.

The carrier is then reacted with excess TiCl4 to produce component A1.45' of the catalyst for the polymerization, copolymerization and oligomerization of olefins and diolefins, containing 68r119 Ti/g of product.

0.0428. of this product to the reactor. ! li! and (C2
H5) Add 96g of 2AlClO, and add polyethylene (
10KP/, 9Ti)29. ! 7 is manufactured.

Example 7 Vinyl acetate (1,:l) is grafted onto a copolymer of ethylene and propylene (7,8,!ii') containing 1.4 molar bonds of propylene as described in Example 1.

The obtained poly(ethylene-copropylene)-gr.

- 3.4 g of polyvinyl acetate were hydrolyzed to obtain 3.1 g of hydrolyzed copolymer, which was reacted with VO (J'30.94,@) as described in Example 1 to give 54.9 g of polyvinyl acetate. 11
1Q V/,? brown powder containing 3.0. ! Manufacture i'.

This product 0.0711 and (C2H5)2AlC10
, 950g to form polyethylene 43',! ii
' (14Ky/jj V).

Example 8 Hydrolyzed poly(ethylene-copropylene)-gr--polyvinyl acetate obtained in Example 7 containing 54.1/729 and (C2H5)2AIC 70,66,9 per gram was added to the reactor. Charge 30.6 g of combined VOCl.

The composition of the gas mixture fed to the polymerization is as follows: 65.4 parts by volume ethylene, 34.6 parts by volume propylene, the total pressure in the reactor is 5.0 atmospheres.

Copolymerization is continued for 1 hour. The yield of an elastic rubbery copolymer containing 45 moles of propylene and 55 moles of ethylene is 24
It is g.

Its total unsaturation is 1.0 double bonds per 1000 carbon atoms.
(vinylidene 50%, trans-vinylene 30%
, and 20% vinyl bonds).

According to physical-mechanical tests, the polymer can be said to belong to the class of rubbery ethylene-propylene polymers (S-shaped elongation curve): the tensile strength is 120 Kp/cm";
The growth rate is 330 or higher.

Example 9 Methyl vinyl ketone (3.0 g) was subjected to the conditions as described in Example 1 at 1.6 m2/,! It is grafted onto a polyethylene powder (70,!i+) having a specific surface area of i'.

The irradiation intensity is 0.15 Mrad/n (42 Roentgen/sec) and is kept constant for 10 hours.

The absorbed dose of gamma rays is 1.5 Mrad.

After grafting, the product was kept in benzene for 27 hours to remove the homopolymer of polymethyl vinyl ketone remaining in the product, passed through a filter, and dried in a vacuum dryer for 80 hours.
Dry at ℃ until a certain amount is reached.

The degree of grafting is 4.2φ.

The radiochemical yield is 4 × 10 molecules/100 eV.

In addition to the main absorption band of polyethylene, the infrared spectrum of polyethylene-gr,-polyethyl vinyl ketone also includes a strong absorption band at 1728cIrL-1 due to the valence vibration of the carbonyl group of the grafted fragment.

The carbonyl group is reduced to a hydroxyl group as described below.

A suspension consisting of freshly distilled pure cyclohexane 1507711 and 30 g of polyethylene grafted with polymethyl vinyl ketone is placed under an argon atmosphere into a two-headed flask equipped with a reflux condenser and a separating funnel.

At a temperature of 60°C, with vigorous stirring, L I AI
Ether suspension of H4 50TrLl (L r AlH4
12 g) are added dropwise from a separatory funnel over the course of 1 hour.

The reaction mixture was kept at this temperature with stirring for a further 60 min, then excess LiAl)I4 was removed and 10% HCl
Add 50mA.

The polymer is washed sequentially with water, alcohol and petroleum ether for 14 hours at 80°C and lmmHg.

Infrared spectral analysis of the obtained polymer shows that the reduction of carbonyl groups is almost complete.

1725c1rL-1 has an extremely weak absorption band, and 3
A broad and strong absorption band with a maximum at 445Cr/L-' is observed, which is due to the valence vibration of the hydroxyl group.

The polymer has the following structure; OH group content (measured by Verley method) is 1.47
%.

Hydroxyl groups are present only on the surface of polyethylene.

The transition metal compound is chemically fixed to the surface of such a polymeric carrier (forming component A) by the procedure described in Example 1.

CCA! A suspension containing 4.1 g of reduced polyethylene-gr,-polymethyl vinyl ketone in 4100 TILl is reacted with 9 g of vcz,o, in CCA'430ml for 3 hours at a temperature of 70<0>C.

The product is filtered under an inert atmosphere, washed to remove free components and dried on a vacuum oven to give a light brown powder containing 17.5 ml of V per component Aig of catalyst. ? get.

Into the reactor of the polymerization plant, under the conditions of Example 1, the product obtained was 0.1192. ! i', benzene 1507 as solvent
711 and AA! (C2H5)2CA O, 5288g
Charge.

Polymerization is continued for 3 hours.

The yield of high-molecular crystalline polyethylene is 36. F (18K
P/,! i'V).

Example 10 In a reactor with a capacity of 0.57, H-
Heptane 15077211 Product obtained in Example 9 0.062
g and A7 (C2H3)2Cd O, 3966,! i
' is inserted.

Polymerization is continued for 5 hours.

The yield of linear polyethylene (molecular weight 2,880,000) is 1
5 g (17.2 Ki, !7 V).

Example 11 0.05 of the product obtained in Example 9 was added to the reactor under the conditions of Example 10.
0. ! 7 and Al (C2H3)2ClO, 3966&
Charge.

To control the molecular weight of the polyethylene produced, 10 volumes of hydrogen are introduced into the reactor.

The yield of polyethylene was 13.0. ! 1il (15KF!
/, 9V).

The molecular weight is 474,000. Example 12 Under the conditions of Example 10, to adjust the molecular weight of the polymer, 3
Zero volumes of hydrogen are introduced into the reactor.

The product obtained in Example 9 0.0663.9 and A7 (C2H5)2ClO,4,! i' to react with polyethylene 11.5 i (10Kp/,!i'V
) was obtained.

The molecular weight is 186,000.

Example 13 0.0635 of the product prepared in Example 9 under the conditions of Example 10
, 9 and A11(C2H5)2clO, 4g are reacted.

The composition of the gaseous mixture is 40 parts by volume hydrogen and 60 parts by volume ethylene.

The yield of polyethylene was 12.7 g (11, OKp/
&V).

The molecular weight is 88,800.

Example 14 Under the conditions of Example 10, 0.0669 g of the product obtained in Example 9 and 10.4 g of Al(C2H5)2C are reacted.

The composition of the gaseous mixture is hydrogen 50% by volume and C2H450
I am in charge of capacity.

The yield of polyethylene is 5.5 g (4.6 g/gV”)
It is.

The molecular weight is 59,600.

Example 15 Under the conditions of Example 10, 0.1034 g of the product obtained in Example 9,
/<7in150m1 and Al(C2H5)2C10,
1 to react with 25g of high molecular weight polyethylene (14Kp
/, 9V) is obtained.

Example 16 Reduced polyethylene-gr,-polymethyl vinyl ketone obtained in Example 9 4.03. ! VC in i' and CCl4
15 TILl of a 10.47% solution of 14 is reacted to produce a brown-yellow powder 4, Og containing V12.8/729 per g of component A of the polymerization catalyst.

0.1372 g of the product obtained and (iso-C4Hg
)2 kilclO,4fj is reacted under the conditions of Example 10 to obtain 16 g (2/g/g in 10) of linear polyethylene.

Example 17 Mesityl oxide (4-
(Methyl-3-penten-2-one) rough raft.

2.5 g of mesityl oxide is grafted onto 30.0 g of polyethylene (irradiation intensity is 1.0 m rad/R
, the absorbed dose is 60 mrad).

After grafting, the product was placed in benzene, kept for 24 hours, filtered and dried to constant volume, polyethylene-gr,-poly(4-methyl-3-penten-2-one) 30.5 ．． ! get i/.

The degree of grafting is 16% and the radiochemical yield is 3 mol/
It is 100eV.

The carbonyl groups in 3.3 g of the obtained polymer are reduced in the same manner as in Example 9.

3.2 g of reduced polyethylene-gr,-methyl-3-penten-2-one) was added to TiC140,
When treated with 4 g, a pale brown product 3.2S containing 2.11119 T i /g is obtained.

The product obtained was 0.4. ! 7 and AA (C2H5)2
ClO,19 was reacted under the conditions of Example 10 to obtain 8.5 g of polymeric linear crystalline polyethylene (10,IKV'
,! i' Ti ).

Example 18 75 g of reduced polyethylene-gr,-polyvinylketo obtained in Example 9 and 40 m of freshly distilled pure benzene
1 in an inert atmosphere to a suspension consisting of benzene 13
Add 3 g of (C5H5)2T's c12o dissolved in 0TrLl.

The reaction mixture is then heated to 60-70°C and the reaction is continued for 2 hours with vigorous stirring.

After draining and washing three times with benzene (50 Tll),
TiO, 46rI per 11 product (component A of polymerization catalyst)
4.9 g of a pale yellow powder containing 100 g of chloride is obtained.

0.416:l of the product obtained, 150 ml of toluene and 4 g of Al(C2H3)2Cl are reacted under the conditions of Example 10.

Polymerization was continued for 3 hours, and 3.5 g (1
8Kg) 7'g Ti) is obtained.

Example 19 Methyl vinyl ketone (0,5,9) is grafted onto polystyrene (7,19) under the conditions of Example 1 (irradiation intensity is 0).
．． 6 mrad/hour, the absorbed dose is 4.2 mrad)
.

3.2 g of the obtained polystyrene-gr,-polymethyl vinyl ketone is reduced with K L s A13 H4 in the same manner as in Example 9 to obtain 2.9 g of reduced polystyrene-gr,-polymethyl vinyl ketone.

This is reacted with 42.04 g of TI(OC4H9) in benzene.

The product obtained is a powder (3,0,?) whose color does not differ from that of the starting polymer.

This contains 1.1 ■Ti/g of product.

The obtained product 0.65765' and Al(C2I(5)2clO, 52889) were placed in a reactor.

The reaction was carried out under the conditions of Example 9 and polyethylene 14.8
El (21KF?/, 9Ti) is obtained.

Example 20 Reaction product of reduced polystyrene-gr,-polymethyl vinyl ketone with Tt(OC4H9)40
．． 49! ! and Al(iso-C4H0)2ClO,3,
9 is placed in the reactor as in Example 19.

The yield is high molecular crystalline polyethylene (28Kp, !9Ti
) 14 g.

Example 21 Under the conditions of Example 1, allyl alcohol (1,106 g) is grafted onto dense polyethylene powder (9,2 g).

The irradiation intensity is 1.2 mrad and is kept constant for 20 hours (the absorbed dose of Gatsuma rays is 24 mrad).

Wash the product with benzene. Yield: polyethylene-g
", -1.4 g of polyallyl alcohol.

In addition to the characteristic absorption band of polyethylene, the infrared spectrum of the product also has a broad, moderately intense absorption band with a maximum at 3480 crIL-1, which is due to the valence vibrations of the hydroxyl groups.

■The hydroxyl group content measured by the Erley method is 0.86%.

The reaction of T iCIJ 4 with the obtained polymer was carried out as described in Example 1, and 4 g of polyethylene-gr,-polyallyl alcohol in C(J!4100 rnl) was reacted with T1
Ti3 per gram of product by reacting with Cl, 0.5.9
3.9 g of a light brown powder containing U9 is obtained.

Polymerization is carried out as described in Example 1.

The resulting product 2.0.9 and klJ (C2H5)
2 cll, 06 g are placed in the reactor.

The yield is linear polymeric crystalline polyethylene with a total unsaturation degree (number of double bonds per 1000 carbon atoms) of 0.20.
0 g (12KV, ?Ti).

Yield point is 260 Kg/cx2, tensile strength is 330 to 7
cyn2, elongation at break is 36%.

Example 22 Under the conditions of Example 1, 1.1 g of allyl alcohol was grafted onto 7.1 g of polystyrene (irradiation intensity: 1.0 mrad).
/hour, absorbed dose 10 Mrad), OHHO218%
Polystyrene-gr,-polyallyl alcohol containing 7
．． Obtain 0g.

This was treated with ■0C13 in the same manner as in Example 1 to obtain 6.8 g of a brown powder containing 3.5 ■■ per gram of product.

Ethylene is polymerized with this product as described in Example 1.

The product obtained in the reactor is 0.2'8. ? and Al(C2
H5) 0.8 g of 2Cl is added to obtain polyethylene 25 i (2sKp, yV) with the following properties: total unsaturation 0.20, yield point 200 Kpm", tensile strength 270 Ky7'cm' at break. Elongation of 30fO0 Example 23 The product 0.7.!9 obtained in Example 21 and A7(iso-C4H9)2ClO,4,!i' were reacted under the conditions of Example 1, and the following physico-mechanical properties were obtained. Polyethylene 34,!i' (17KV, 9Ti) is obtained with a total unsaturation degree of 0.30 and a yield point of 180 Ky/cr.
n", tensile strength 250Kg/cm", elongation at break 44
0 person in charge.

Example 24 Specific surface area 1.6 for ampoule for gas phase/radiation graft polymerization
m2/,! Charge 70.9 g of polyethylene powder i' and 5 ml of allyl alcohol.

The irradiation intensity was 1.25 mrad/hour and the exposure time was 48 hours.

The procedure is the same as described in Example 21.

The yield is polyethylene-gr,- containing 271% OHHO.
Polyallyl alcohol69. :l.

To a suspension containing 7 g of the polymer obtained in 4150 ml of CCV are added 15 ml of a 10% solution of TiC14 in CCl4 in an inert atmosphere.

The reaction is continued for 3 hours at 65-70°C. After treating the product as in Example 1, 6.8 g of a light brown product containing 1.5/72@ of Ti per g are obtained.

0.1527 g of the product obtained and Al(C2)-I5
) 14 g of 2ClO are placed in the reactor.

Yield: 9.6 fl of polyethylene (42.5 KpgT
i).

Example 25 The product obtained in Example 24 0.2243.9 and Al(C2H
5) A gas mixture consisting of 60 parts by volume of ethylene and 40 parts by volume of propylene is fed into a polymerization reactor containing a catalyst consisting of 10.4 g of 2C.

Continue the reaction for 4 hours.

Yield: 8 g of elastic copolymer of ethylene and propylene
(24KV″gTi).

Example 26 Polyethylene-gr obtained in Example 24 in CC14 medium,
- 6 g of polyallyl alcohol and 6% V in 'CCl4
15 TLl of Cl4 solution is allowed to react.

The product is processed as in Example 1 to obtain 5.7 g of a dark brown product containing 8772 FV/.9.

Obtained product 0.25] 1, n-heptane 150 ml
, ethylene (10 atm) and Al(C2H5)2CI
Charge 0.3 g to the reactor.

Polymerization was continued for 2 hours to obtain polymer crystalline polyethylene 108
,! F (55Kp/, !7V) is obtained.

Example 27 0.1773 g of the product obtained in Example 26 as catalyst and n-
0.3 g Al(C2H5)2Cl in 5 ml hebutane
Gas phase polymerization of ethylene is carried out using

Polymerization was continued for 1 hour, and 38 g (14
Kip/, 9V) is obtained.

Example 28 In an autoclave with a content of 1.51 and equipped with a paddle stirrer, 0.51 of hexane as solvent, 0.227.9 of the product obtained in Example 26 and Al(iso-C4H9)2HO15
Charge g.

Polymerization is carried out at a temperature of 70-75°C.

The composition of the gas mixture is 70 parts by volume ethylene and 30 parts by volume hydrogen.

Continue the reaction for 2 hours. Yield: 80 g of polyethylene (4
3.5 Kp/gV).

Example 29 Under the conditions of Example 28, 0.15 g of the product obtained in Example 26 and 14 g of Al(iso-C4H9)2HO are placed in an autoclave.

The composition of the gas mixture is 90 parts by volume ethylene and 10 parts by volume hydrogen, and the total pressure in the reactor is 15.5 atmospheres.

Polymerization was continued for 2 hours, and 72 g of polyethylene (60 g/g/
gV): melt index is 2.18 g/
It's 10 minutes.

Example 30 0.1 g of the product obtained in Example 26, 150 ml of benzene recovered after polymerization and 15 g of Al(C2H5)2Cl2O are placed in an autoclave.

Polymerization is continued at a temperature of 80° C. and an ethylene pressure of 4 atmospheres.

The yield of polyethylene was 15.7 g (19.6 Kp/
gV).

Example 31 Reactor with a capacity of 0.81 cm, benzene recovered after polymerization (boiling point 68 °C) 0.1, product obtained in Example 26 0.302
1 g and Al(C2H5) 2 clo, s g.

Polymerization is continued for 1 hour at 4 atmospheres of ethylene pressure.

The yield of high molecular weight (molecular weight 1,648,000) polyethylene (bulk weight 531 g/l, ash content 0.03%) is 86.9
It is.

Example 32 Polyethylene-gr,-polyallyl alcohol obtained by grafting 3 ml of allyl alcohol onto 14 g of polyethylene and containing 256% OHHO was prepared in the same manner as in Example 22.
(OC2H5)3 and V2 per gram of product.
．． 13.79 of a pale yellow powder containing 8m, g is produced.

In a reactor with a capacity of 1.31, the obtained product 0.6358
250 mA of n-heptane and ethylene (total pressure of 12.5 atm) were added, and polymerization was continued for 1 hour at a temperature of 90°C to produce 48 g of polyethylene (30 KP/gV).
Manufacture.

Example 33 The product obtained in Example 32 (0,527,9) and Al(C2
H5) Polymerization is carried out using 2 cl (0,4 & ) at a temperature of 70° C. for 1 hour at an ethylene pressure of 10 atm, using 150 ml of benzene as solvent.

The yield is 86.9.9 (64 Kp/gV) of polyethylene with a bulk weight of 311 g/l and an ash content of 0.02%. ! i', Al(C2H
5) Put 126 g of 2ClO and 100 ml of benzine into an autoclave.

The pressure of ethylene was 3 atm, the polymerization temperature was 70°C,
The duration of the process is 1 hour.

Yield: 8.1g of polyethylene (20.7Kp/, ?V)
It is.

Example 35 0.155 g of the product obtained in Example 32 and 10.1 g of Al(C2H5)2C were heated at a temperature of 80° C.
Charge the autoclave under the conditions of Example 34 at an ethylene pressure of atm.

Polymerization was continued for 1 hour and 13 g of polyethylene (28,6
Kp/gV) is obtained.

Example 36 A reactor with a capacity of 0.51 was charged with 0.0 ml of the product prepared in Example 32.
2814g, benzine 250ml and AA! (C2H
5) Charge 2 ci o, s g.

A gas mixture consisting of 7 parts by volume of propylene and 93 parts by volume of ethylene is copolymerized at a total pressure of 4 atmospheres.

During the course of this step, equal amounts of pure ethylidenenorbornene (3 rnl in 10 ml of benzene!) are introduced into the reactor.

Continue this process for 90 minutes. The yield of terpolymer-ethylene-propylene-ethylidene norbornene is 14i (
17Kp/, 9V).

The product (powder) has significant unsaturated bonds (in the infrared spectrum there is a strong absorption band at 1640 cm-' and weak absorption bands at 880 and 910 CrrL-'.

Example 37 Under the conditions of Example 36, ethylene is copolymerized with propylene and ethylidene norbornene in the presence of 3 ml of ethylidene norbornene in an ethylene:propylene ratio of 50:60.

The catalyst was the product 0.34.9 obtained in Example 32 and A12 (
C2H5)3c130.4 g.

The resulting polymeric rubbery terpolymer has a high degree of unsaturation.

Example 38 Allyl alcohol (0.9 g) is grafted onto polyethylene (8.3 g) after treatment with radio-frequency discharge.

The resulting product is polyethylene-gr,-polyallyl alcohol containing 272% OHHO.

3.4 g of this product was mixed under the conditions of Example 1 with MoC1) 50.
8g of pale yellow powder 3 containing Mo7923η
．． Obtain 3g.

The polymerization is carried out analogously to Example 1; the reaction catalyst is 0.4076 g of the product obtained and Al(C2I-(5)2ClO,
It is 25.9.

The yield of high molecular weight polyethylene is 14.5g (1.5KW/
fl Mo).

Example 39 4.9 g of polyethylene-gr,-polyallyl alcohol obtained in Example 38 and 1.1 g of WC761 are reacted.

The resulting product is 42.1 m? /W/,! It is a brown powder containing 9.

The yield is 5. (N9. Ethylene as described in Example 1, the resulting product 0.05.? and Al(iso-C
4H9) 2CI 0.6! polymerize with j.

The yield of polyethylene is 3.4.9 (1.7 KP/, 9
W).

Example 40 Ethylene is polymerized as in Example 1, but using benzene as solvent.

The catalyst used in the reaction was 0.2% of the product obtained in Example 26.
5.9 and Z n (CHa) 20.95. ! It is i'.

The yield of polyethylene was 8.5g (4,2Ky/'9V
).

Example 41 Ethylene and α-butene are polymerized under the conditions of Example 1.

The copolymerization is carried out by feeding into the reactor a gas mixture containing 97 parts by volume of ethylene and 3 parts by volume of alpha-butene.

The catalyst used in the reaction was the product obtained in Example 26, 0.2.9
and Al(C2H5)2ClO,64,9.

The yield of copolymer of ethylene and butene is 3351 (20
KP/, 9V): the product contains 1.7 CH3 groups per 1000 carbon atoms.

Example 42 The polymerization of ethylene is carried out analogously to Example 40.

The catalyst in this case was the product made in Example 26, 0.335'
and LiC4Hol, 9 g.

The yield of polyethylene obtained as a result of polymerization is 5.3
fl (2,I Ky7KpV).

Example 43 8.9 g of polyethylene-gr,-polyallyl alcohol obtained in Example 24 and 20.2 g of (C5Hs)2Ticz are reacted under the conditions of Example 1 in toluene.

The product has Ti 0.5j'2 per 1g? 88 g of a yellowish substance containing

The resulting product 0.4.9 and AJI! was added to the reactor. (C
2H3) Charge 64 g of 2ClO.

The polymerization is carried out under the conditions of Example 1, but using 200 ml of benzene as solvent.

The yield of polyethylene is 6 g (30Kp/,!i'T
i).

Example 44 9 g of polyethylene-gr,-polyallyl alcohol obtained in Example 24 and 1 OT of Ti(OC4H9)4 (benzene)
Component A of the polymerization catalyst is prepared by reacting 27711) in benzene.

The reaction is carried out analogously to 9111, but using 200 ml of benzene as solvent.

The catalyst used in the reaction produced a product of 0.985. i
7 and Al(C2H5)2C104g.

Polymerization was continued for 3 hours and polyethylene 50.5. ! 7 (8
4KP/,! ? 50.5 g of Ti) is produced.

The molecular weight of the product is 668,000.

Example 45 The operating conditions are the same, except that the polymerization is carried out using 0.4 g of the product obtained in Example 44 as catalyst and the polymerization is continued for 4 hours.

The yield of polyethylene is 30.2! i' (112Kg
f/, 9Ti).

Melt index is 0.487,? It is 710 minutes.

The weight is 240.9/A.

Example 46 0, 2368 & Al obtained in Example 44 (C21-TI
, IC70,4,! if is reacted under the conditions of Example 44.

The yield of polyethylene is 20.0.9 (125 Ky/, 9
Ti).

Example 47 Under the conditions of Example 24, allyl alcohol 0. 'l is polyethylene 18. (Graft to l.

The obtained product was prepared in Example 44 under the specified conditions by Ti(OC4H
g) React with 41.5 vertical.

The resulting product is a white powder (17,8,!il) containing 25j729 TiO/g.

Polymerizations using this product were carried out under the conditions described in Example 44.
Implement time.

The obtained product 0.62P and Al(C2H
5) 2C10,4! Enter j.

The yield of polyethylene is 37. ? (250Kp/, 9Ti
).

Melt index is 0.338.9/10 minutes.

Example 48 Under the conditions of Example 47, 0.712.9 of the product obtained in Example 47 and A12(C2H5)3CA? Charge 30.4697 g.

The yield of low molecular polyethylene is 27.7fl (160K
p/f! Ti).

The fluidity of the melt is extremely high (no load).

Example 49 Under the conditions of Example 47 (but at a temperature of 90'C), a reactor was charged with 0.65.9% of the product obtained in Example 47 and Al(C2
H3)2C1O,4,? Charge.

The yield of polyethylene was 46.0! i' (290 to 2/,!?Ti).

The bulk weight of the product is 18551/l, the intrinsic viscosity in Tetrawan at 135° C. is 0.35 and the tart index is 3.0.9710 min.

Example 50 Under the conditions of Example 47, 0 of the product obtained in Example 47 was added to the polymerization reactor.
．． Charge 2'# and Al(C2H5)2clO, 2g.

Polymerization is carried out at 30 atmospheres of ethylene pressure for 7 hours.

The yield of polyethylene is 68. ? (1015Kp/, 9T
i).

Melt index is 0.116.

Example 51 Under the conditions of Example 47, 0.542 g of the product obtained in Example 47 and AlC2H5Cl2O,4,! Charge i' into the polymerization reactor.

The reaction product is a liquid oligomer. This product is KO
Wash with a 10% solution of H and then with water and separate on a separating funnel.

Vacuum distill the solvent. Oligomers (linear olefins, waxes and alkylation products of benzene with olefins)
The yield was 24 g (177 g/g Ti).

Example 52 Under the conditions of Example 51 (ethylene pressure 30 atm), 0.7185 g of the product obtained in Example 47 and AlC2H5Cl
Charge 2O,5,9 to the reactor.

The yield of oligomer, ie a product similar to that obtained in Example 51, is 81.85' (432 Kp/, 9Ti).

Example 53 Under the conditions of Example 52, 1.1 g of the product obtained in Example 47 and Al
Charge 8 g of C2H5Cl2O to the reactor.

The yield of oligomer with the same structure as Example 51 is 138 g.
(5051Q;=/EI T i).

Example 54 Polypropylene powder (6,3,9) is grafted with crotyl alcohol (γ-methylallyl alcohol).

The irradiation intensity is 1. Omrad/hour and exposure is 48 hours.

The resulting polypropylene gr,-polycrotyl alcohol was treated with TiCl under the conditions of Example 1 to obtain TiCl per gram.
6.0 g of light brown powder containing O,4 is obtained.

The polymerization using the product (0,5,9) activated with 14 g of Al(C2H6)2ClO is carried out under the conditions of Example 47.

The yield of high molecular weight polyethylene is 6.0 & (30Kp/
fi Ti).

Example 55 Polyethylene powder (4, 7, 9) and cinnamic alcohol (
0,351) and the resulting product was grafted in Example 1
Treated with TIC140.8g under the conditions of
4.5 g of a light brown powder containing i0.38.9 are obtained.

The products obtained o, s, y and Al(C2H5)2Cl
O,96,! Polymerization of ethylene was carried out using i' as a catalyst under the conditions of Example 47 to yield 4.2 g (1
4Kyl 9 Ti).

Example 56 Diallylamine (di-2-
1.7 g of propenylamine) are grafted.

The irradiation intensity was 1.0 Mrad/hour, and the absorbed dose was 60
This is Mrad.

The polyethylene-gr,-polydiallylamine is treated with dry benzene and dried to constant weight in a vacuum dryer.

The yield of pale yellow powder containing 0.35% nitrogen is 4.0! ! It is.

Infrared spectral analysis of a compression molded film made from this material revealed that in addition to the characteristic absorption band of polymeric crystalline unbranched polyethylene, there is also an absorption band at 3380 cm-' (due to the valence vibrations of the associated N-H bonds). ) and the absorption bands of 1612 and 1640 鑞-1 (bending vibration of the N--H bond and the terminal vinyl group; along with a moderately strong absorption band at 914crrL-1) are also found.

All this proves the structure of the polymer polyethylene-g'-polydiallylamine.

2.3 g of the obtained product and T 1C14o, 6 jj
The reaction with is carried out under the conditions of Example 1.

The yield of pale yellow and light brown powder containing 12.1/729 Ti per gram was 2.2 g.

Except for increasing the ethylene pressure to 6 atmospheres,
The test was carried out under the conditions of Example 1.

The product obtained is 0.0688. ! i', hexane 150
ml and 10,44 g of Al(C2H5)2C are placed in the reactor.

The yield of high molecular crystalline polymer is 8.2,! i' (10
Ky/,? Ti).

The molecular weight is 685,000. Example 57 Under the conditions of Example 1, 71.0 g of polyethylene is grafted with diallylamine 3.97'H1.

Irradiation intensity is 0.8 mrad at 7 o'clock, absorbed dose is 40m
It is rad.

The yield of pale yellow powder containing 0.45% nitrogen is 70.5.9
It is.

The obtained polyethylene-gr. polydiallylamine 10
．． ! As in Example 1, change i+ to ■C1C14 (15') 6.
9. A brown powder containing Vl, 92% was obtained by treatment with a solution of 9.
Obtain 9g.

Ethylene is polymerized as in Example 1, but the ethylene pressure is 6 atm, and 1 liter of freshly distilled pure cyclohexane is added.
50 ml are used as solvent.

0.1585 g of the product obtained in the reactor and Al(C2
H5) Charge 0,6795 g of 2CI.

The yield of crystalline polyethylene is 44,! i' (13,4
Ky/fiV) There is.

The molecular weight is 3.886,000.

Example 58 Gas phase polymerization of ethylene is carried out in the absence of solvent.

0.094 L9 of the product prepared in Example 57 and A
Charge 0.68 F of 1(C2H5)2Cl (solution in 5 ml of cyclohexane).

The reaction was continued for 3 hours and polyethylene 14.5 & (8
To? /i V ) is obtained.

The molecular weight is 1,621,000.

Example 59 9 g of polyethylene-gr--polydiallylamine obtained in Example 57 and T I (OC4HQ) 4 1.95
By reacting with g-, Ti O per 1 g, 7/11?
8.5 g of white powder containing:

The catalyst used in the polymerization process is such that the resulting product is 0.24
F and (iso-C4I-(9)2AlClO,64,?
It is.

Benzene is used as a solvent.

The yield of polyethylene is 11 ji (70 to 7.9 Ti
).

The molecular weight is 59,500. Example 60 On an electron accelerator with an energy of 5 mev, polyethylene (4
0.5 g).

The total absorbed dose is 40 mrad.

The product is kept in benzene for 3 days and dried to constant weight.

Yield of yellowish product containing 1.47% nitrogen is 40.0
& is.

The infrared spectrum of the obtained product shows additional absorption bands as a broad absorption band with absorption maxima at 3380 crrL-1 (NH2 group valence vibration) and 1070 cIrL-1 (NH2 bending vibration). be.

This means that the structure of the obtained product is polyethylene-gr,
Prove that it is polyallylamine.

By reacting 5 g of this polymer with 41.2 g of VCl,
Vl2.2/7T? This yields 4.9 g of a dark brown powder containing /g.

In a reactor with a capacity of 1.31, 250 ml of heptane, 0.15 g of the product obtained and Al(iso-C4H0)2HO
Charge 14 g.

The polymerization is carried out at a temperature of 70° C. and a pressure of 10 atmospheres.

The yield of polyethylene was 154.5g (81.5Kp/,
! 7V).

The intrinsic viscosity is 13.3 (in tetralin at 135°C).

Ash content is 0.02%.

Example 61 Polyethylene-gr,-polyallylamine (5,(1) obtained in Example 60 and T I (oc4H9)4 1.9
5g under the conditions of Example 1, Ti 0.3"
White powder containing 'if/g 48. ? occurs.

Example 6 except that 200 ml of benzene is used as solvent
Polymerization using the powder is carried out in the same manner as in Example 0.

The product obtained was 0.21 and kl(C2H5)2 cl
Charge O,4El to the reactor.

The yield of polyethylene was 20.2 g (84Kp/gT
i).

Example 62 4.9 g of polyethylene-gr,-polyallylamine and (
C5H5)2 T 1cJl! 20.1 React with El to produce a pale yellow powder containing 4 µ/g of TiO3.
Obtain 7g.

The resulting product 0.5N and Al(iso-"4H9)2CIo, 45j! were added to the reactor.
and carry out the polymerization under the conditions described in Example 61.

The yield of polyethylene is 10. ! 7 (50Kp/gTi
).

Example 63 51.3 g of MoCA was added to polyethylene-gr under the conditions of Example 1.
--Polyallylamine5. By reacting with Og, Mo 1
4.7 g of a brown product containing 101119/El are obtained.

The polymerization of ethylene is carried out under the conditions described in Example 61.

The products obtained in the reactor are 0.17El and A7(C2H
5) Charge 2C1O,74,9.

The yield of polyethylene was 3.7 g (2Kp/9Mo)
It is.

Example 64 A glass ampoule with a chamber for the polymer carrier and a chamber for the monomer to be grafted is filled with low-pressure polyethylene (molecular weight 928,000) and freshly distilled acrylonitrile (CuCl20.05.! to prevent homopolymerization). i
' stabilized) 3. 'Charge #.

The irradiation intensity is 1.1 Mrad/hr and the absorbed dose is 5.5 Mrad.

The nitrile fragment of polyethylene-gr,-polyacrylonitrile is reduced analogously to Example 9 with LiAlH4.

The thus obtained reduced polyethylene-gr,-polyacrylonitrile 5.4! ! T + C under the conditions of Example 1
141.1 g.

The yield of brown-yellow powder containing 7.01119/g of Ti is 5.
．． It is 2g.

Polymerization using this product is carried out in benzene as described in Example 1.

0.144% of the product obtained was added to the reactor. ? and Al(C
2H5) Charge 0.8 g of 2CI.

The yield of polyethylene is 20.5.9 (20.5Kp/,
9Ti).

Example 65 3.1 g of allyl mercaptan are grafted as in Example 1 onto 50.0 g of polyethylene powder.

Irradiation intensity was 0.3 mrad at 7 o'clock, absorbed dose was 2.4
This is Mrad.

Yield of pale yellow product containing 0.16% sulfur, i.e. polyethylene-gr,-polyallyl mercaptan, is 50.2 g.
It is.

The obtained polymers s, og and Tic142.0,! i
' was reacted under the conditions of Example 1, TiO,7rll'i/
7.8 g of yellow powder are obtained containing g.

The product obtained in the polymerization reactor was 0.3126. ! 7 and A
4 g of z(C2H5)2ClO are charged and the polymerization is carried out as in Example 1.

The yield of polyethylene is 4.5g (20-5Ky/9
Ti).

Example 66 6.0 g of polyethylene-gr,-allyl mercaptan were treated with 1.5.9 g of VCl4 (solution in CC14) and
5.9 g of a gray powder containing V2.21119/g are produced.

The polymerization is carried out analogously to Example 1.

0.411? of the produced product is added to the reactor. and Al(C2
H5) Charge 4 g of 2 clo.

The polymerization is carried out analogously to Example 1. The reactor is charged with 0.414 g of the product obtained and 0.4 g of Al(C2H5)2CI.

Polymerization was carried out for 3 hours to obtain polyethylene 28.9 (31
Kp/, yv) is obtained.

The molecular weight is 2,085,000. Example 67 1.0 g of allylmerkabutane was mixed into a copolymer of ethylene and propylene (the methylene group content was 0.37 per 1000 carbon atoms, the intrinsic viscosity in tetralin at 135°C was 2.03, and the tart The index is O, El/1
0 minutes and the ash content is 0.018)4.3. ! 7
graft to.

The ionizing radiation is 0.5 mrad/hour and the absorbed dose is 7
．． It is 0mrad.

The resulting poly(ethylene-copropylene) -gr,
- 4.4 g of polyallyl mercaptan with 0.5 g of VCl
Processed with Vl, 5m? Dark brown powder containing /g 4.2
get g.

The reactor was charged with 0.3112 g of the obtained product and Al(iso-C4H9)2HO,6,! i+ (solvent-benzene 0.21) and polymerization was continued for 5 hours under the conditions of Example 1 to produce high molecular weight polyethylene 29.9 (62 KP/,! i'V
).

Example 68 Grafting 0.4 g of methyl mercaptan onto 2.7 g of polystyrene under the conditions of Example 1 (absorbed dose of gamma rays is 1
．． 4 Mrad).

2.9 g of the obtained polystyrene-gr,-polymethyl methacrylate was reacted with VCl4 to form a brown powder, i.e., a complex compound of VCl4 and polystyrene-gr,-polymethacrylate, i.e., a polymerization catalyst containing 9 g/g. Component A
, 2. : Get 1.

In the reactor under the conditions of Example 1, the product obtained was 0.1248.
9 and 10,48 g of Al(C2H5)2C are charged.

The yield of high-molecular crystalline polyethylene is 46F (41KP/
! ! V).

Example 69 3.7 g of polyethylene-gr,-polymethyl vinyl ketone obtained in Example 9 and 40.7 g of VCl, ? was reacted in CCV 4 medium to produce VCl containing V7.21119/j9.
3.6 g of a complex compound of No. 4 and polyethylene-gr,-polymethylvinyl ketone were prepared.

The products obtained in the reactor were 0.1523.9 and A7 (
Charge C2H3)2C1O,4,9.

Polymerization is continued for 2 hours under the conditions of Example 1 to obtain 57.5 g (57.5 Kp/, 9V) of high molecular weight crystalline polyethylene.

The intrinsic viscosity in tetralin is 16.0 (at 135°C).

Example 70 The product obtained in Example 69 0.1428.9 and Al(iso-
C4H0)2C70,7,9 is charged into the reactor.

The gas mixture fed into the reactor for copolymerization contains 58.6 volumes of ethylene and 41.4 volumes of propylene, with a total monomer pressure of 6.66 atm, and 200 ml of n-hebutane as a solvent. Use as.

Copolymerization is continued for 4 hours to obtain 26 g of a highly elastic copolymer of ethylene and propylene.

This material is completely soluble in n-hebutane at the polymerization temperature (70°C).

Example 71 Polyethylene-gr obtained from Example 64 with TiC74.

React with polyacrylonitrile under the conditions of Example 1.

Polyethylene-gr,-polyacrylonitrile 1.4g
and TiCA40.5g to form Ti18rng
1.6 g of a pale yellow product containing /i is obtained.

The polymerization is carried out analogously to Example 1.

0.2015 g of the product obtained and AA (C2H3)
8 g of 2C1O is placed in the reactor.

The yield of polymeric crystalline polyethylene is 45,9' (12,
5Kp/g Ti).

Example 72 7.8 g of acrylonitrile was added to 180 g of polypropylene powder.
! graft to j.

The ionizing radiation is 40 rad/second (0,144 mrad/hour).

The absorbed dose is 0.86 Mrad.

VCl4 (0,5,?) is reacted with polypropylene-gr,-polyacrylonitrile (7,(1)) analogously to Example 1.

Yield is V O,9/fi? Light brown powder 6 containing / , 9
．． It is 8g.

The polymerization of propylene is carried out analogously to Example 1. The pressure is 5.
It is 0 atmospheres.

0.5 g of the product obtained and Al(C2H5)2CA'
Charge 0.96 g.

The yield is polypropylene 3.7.9 (8KP/, ?V
).

Example 73 Analogously to Example 1, 0.9 g of freshly distilled pure 2-vinylpyridine are grafted onto 7.4 g of polyethylene powder.

The product was treated with VCl 41.3 & to give a light brown powder containing 4.3 ay (C14 combined with polyethylene-gr, poly(2-vinylpyridine)) per gram of product.
．． (Produce L9.

Product obtained in the reactor 0.2. ? and Al(C2H5
)2C4O,61? Put in.

The yield of polyethylene is 8.71 (IOKP/,!ii'
V).

Example 74 12 g of polypropylene in ampoule for radiochemical grafting
to which 1.1 g of 4-vinyl-pyridine is grafted (irradiation intensity 0.5 Mrad 7 o'clock, absorbed dose 4.7 Mrad).

The obtained product was kept in boiling benzene for 10 hours and after drying to a certain amount, polypropylene-gr,-
The yield of poly(4 vinylpyridine) is 12.7 El.

3.4 g of the obtained polymer and 20.711 CoCl are reacted in the same manner as in Example 1 to obtain 3.5 g of a gray powder containing 12 /g of Co.

The product obtained was 0.25.9 and Al(iso-C4H0
)2CI 0.64 F is charged to the reactor under the conditions of Example 1.

The yield of polyethylene was 7.5g (2,5Ky/9C
o).

Example 75 Polypropylene-gr,-poly(4-vinylpyridine)
4. :l is reacted with vc14o, s, and y under the conditions of Example 1 to form V14/'Z? 4.5 g of a brown powder containing /, 9 result.

The resulting product 0.2F and Al(C2H5) 2C
Charge 014 g of IJ to the reactor.

Ethylene was polymerized in the same manner as in Example 1 to obtain polyethylene 6.9
g (24Ky/gV).

Example 76 Diaryl sulfide (0,6P) was added to polyethylene (4,
2,9) and the obtained polyethylene-g
, -polydiallyl sulfide as described in Example 1.
Processed with CI4, V 1.2 /72@/,? A light brown product containing4. Obtain Og.

0.4274.9 of the complex compound obtained is charged to the reactor as in Example 1.

Add Al(C2H5)2C1O,4,9.

The yield of high molecular weight polyethylene is 14.5Kp (28Kp/
,! 7V).

Example 77 Under the conditions of Example 1 (however, the ionizing radiation intensity was set to 0.75 Mra)
d/hr and the total absorbed dose is 15 mrad), diallylsulfone 0.6.9 is grafted onto polyethylene 7,0.9.

The obtained polyethylene-gr,-polydiallylsulfone was treated with VCI, (0,6,9) to give V3.1/7
6.9 g of light brown product containing 2 g/g are obtained.

The polymerization is carried out analogously to Example 1. The product obtained was 0.5.
9 and 10.4 g of Al(C2H5)2C are charged.

Polyethylene yield is 17 fl (11Ki, 9V)
It is.

Example 78 In a two-headed flask (evacuated and flushed with alcone), 15. (l and freshly distilled n-hebutane 1
Charge 00ml.

Stir the ingredients vigorously and heat the reaction mixture to 60°C.

32.4 g of Al(C2H6) (solution in 50 TL of n-hebutane) are added slowly from a separating funnel.

The reaction is carried out for 3 hours at the same temperature.

The suspension is transferred to a strainer under an inert atmosphere, washed four times with n-hebutane and dried in vacuo.

Yield: 16.0% bright yellow powder containing 0.01997% aluminum. ! ii'.

The powder is component A of the olefin polymerization catalyst.

In the IR spectrum of the obtained product, there is no absorption band of 2240CrIL-'', which is characteristic of the valence vibration of -C=N, but there is a new absorption band with an absorption maximum at 1630cTrL', which is - This is a characteristic of valence vibration of C=N-.

The structure of the product obtained can be summarized as follows.

This, along with chemical analysis data, Prove 100% change.

Nitrile groups are Example 79 Polyethylene powder (low pressure) 10.2. ! i' in a glass ampoule and irradiated with high frequency discharge for 30 minutes, after which the polyethylene thus obtained was treated with gaseous acrylonitrile 2.
Add 1g.

After grafting, the product is washed with benzene and dried to constant weight in a vacuum dryer.

Yield: 0.13E of polyacrylonitrile per gram of product
M-containing polyethylene-gr,-polyacrylonitrile 11.1.

Under the conditions of Example 1, 5.4 g of polyethylene-gr,-polyacrylonitrile and Al(iso-C4H9)2H1,3
5 g are reacted to obtain 64 g of a bright yellow powder containing 10.0374 gl of A1.

The product obtained is component B of the olefin polymerization catalyst.

Example 80 Glass ampoule for radiation polymerization was made of low pressure polyethylene (specific surface area 1.6 m2/g) 70,! i' and CuCl
20.1. ! Freshly distilled methyl vinyl ketone stabilized with i'3. Charge Og.

Grafting is carried out using ionizing radiation of 0.15 mrad/hour with an exposure of 10 hours and an absorbed dose of 1.5 mrad.

After washing the obtained product and drying it to a certain amount, 0.034 i of polymethyl vinyl ketone was added to 1 g of the product.
- The yield of polyethylene-gr and polymethyl vinyl ketone is 72ji.

AA (C2H5) 3 is reacted with polyethylene-gr,-polymethyl vinyl ketone under the conditions of Example 1.

Take the reactants in the following amounts: 6.8 g of polyethylene-gr,-polymethyl vinyl ketone and Al(C2H3)30
．． 4,? .

0.055. ? The yield of white powder containing /g is 7.
It is 1g.

This is component B of the olefin polymerization melt.

In the IR spectrum of the obtained compound, there is no characteristic absorption band (1728 crrL-1) of the valence vibration of the carbonyl group.

The product has the following structure. Example 81 The reactor was evacuated and ethylene was introduced, resulting in Example 78,
Polypropylene-gr,-polyacrylonitrile and Al(C2H5)3 containing AAo, 01'l per gram of product
Reaction product with 1.330. ! 7 and freshly distilled pure n-hebutane 2007721.

The capacity of the reactor is 1.31. The temperature of the reactor is 70℃,
Fresh ethylene is supplied at a pressure of 10.0 atm.

VCl2 (freshly prepared solution in n-heptane) 1
．． After adding 57729, polymerization begins.

Polymerization is continued for 2 hours (polymerization temperature and ethylene pressure are kept constant throughout the entire polymerization process).

The polymer is washed with ethyl alcohol and water and dried in a vacuum oven.

The yield of polymeric crystalline polyethylene is 12.5.9 (8.3 Kplg VCII4, or 31.0 Kp
/gV and 0.55 Kplg Al).

Example 82 Polyethylene-containing AlO,0374ji/9 prepared in Example 72 under the conditions of Example 81, except that 250 rILl of freshly distilled pure benzene was used as solvent.
gr, -polyacrylonitrile and Al (iso-C4H9
) 0.4084 g of reaction product with 2H and TiC742
, 5 g (in n-heptane) are polymerized for 3 hours.

The obtained polymer was treated in the same manner as in Example 81, and the yield of high molecular weight crystalline polyethylene was 11,0 jj (4,4K?/
gTt c14, or 18Kp/gTi and 0.73
Kp/gA,z).

Example 83 Reaction product of polyethylene-gr,-polymethyl vinyl ketone obtained in Example 80 and A'[C2H3)3 0.485
g and VOCls 1.2 1 (solution in n-hebutane) are charged to the reactor under the conditions of Example 82.

Polymerization was continued for 2 hours to form polymeric crystalline polyethylene 17.
3 g (VOC1314,5 g/g, or 50 K9
/, yv and 0.64 Ky/g Al).

Example 84 In a two-headed flask equipped with a stirrer, reflux condenser and separating funnel, polyethylene-gr obtained in Example 24 was added.

Polyallyl alcohol 12.0. ! i' and 707 rLl of freshly distilled pure n-hebutane.

Tetrabenzyl-titanium Ti (CH2C6H5)
A toluene solution of 4 (containing 0.1 mol in 1) 1.1.
! i' is added dropwise from a separating funnel over a period of 2 hours at a temperature of 60°C.

The reaction is continued for an additional 2 hours at the same temperature. The product is separated on a filter, washed with n-hebutane (3x50 TILl) in an inert atmosphere and dried under vacuum to constant volume.

The yield of yellowish powder containing TiO,357729/,9 was 11.8. ? It is.

Under the conditions of Example 1, but using benzene as the solvent, the product obtained in the reactor was 0.9237. ! Charge i'.

The yield of high-molecular crystalline polyethylene is 6.9,! i'
(17 Ky/EI Ti ).

The ash content is 0.01.

Example 85 Under the conditions of Example 84, 0 of the product obtained in Example 84 was added to the reactor.
．． 623. ? Charge.

The yield of high molecular weight polyethylene is 5.1, Si' (20
Ky7.9Ti).

Example 86 Under the conditions of Example 83 (however, toluene is used as a solvent and the reaction temperature is 30°C), polyethylene
Allyl alcohol 4.0.9 to tetrabenzyruhanadium v (CH2C6H5) 40.45! 3.8 g of a light brown powder containing 42 g/i of V 2 O are obtained.

In the reactor under the conditions of Example 84, the product obtained was 0.834
4g of polymer crystalline polyethylene 14.0
g (38Kp/, 9V).

Ash content is 0, o1%. Example 87 8.6 g of polyethylene-gr,-polydiallylamine obtained in Example 57 and 0.89 g of tetrabenzyl-titanium.
9 is reacted under the conditions of Example 84.

The yield of pale yellow powder is 8.4 g.

The Ti content is 0.28772 per gram of product? It is.

0.4412.9 of the product obtained is charged to the reactor and the polymerization is carried out as in Example 84, but the length of the polymerization process is 6 hours.

The yield of polyethylene was 5.3 g (40Ki, 9Ti
).

Claims (1)

[Scope of Claims] 1. A method for polymerizing, copolymerizing, or oligomerizing olefins and diolefins in the presence of a catalyst, the catalyst having the following general formula: (wherein M is a transition metal or a metal of the periodic table) represents an oxide of a metal belonging to groups IVA to VIA or group II, where X is a halogen,
hydrogen, a cyclopencdienyl group, an alkoxyl group, an aryloxyl group, or an amine group, and n represents an integer representing the valence of the metal M), and the catalyst compound has the following general formula: [ In the formula, “is H2CH3, C2H
6, CH2-CH or C6H6, R" represents H or CH3, R" represents H or CH3, Y represents O
H, NHR', SR. COCH3, CH20H, CH2NHα, C0OH,0
COCH8°COOCH3, CAN, N(R')2. −
8.802R'. 5000], and the compound M'R1Zk-
p [In the formula, M' represents a metal from Groups ■ to ■ of the periodic table, R represents a hydrocarbon residue, Z represents a halogen, hydrogen, an alkoxy group, an aryloxy group, or an amide group, and k represents M
' represents an integer indicating the valence of 1ζp<k].