JPH05306312A - Process for producing graft-modified polyolefin - Google Patents

Abstract

(57) [Summary] (Modified) [Structure] Unsaturated copolymer having a carbon-carbon double bond formed by copolymerizing ethylene or α-olefin with a diene compound represented by the formula (I) or (II). 100 parts by weight of a polymer (however, the unit concentration based on the diene compound in the copolymer is 0.05 to 50 mol%) and 0.05 to 300 parts by weight of a radical-polymerizable monomer. ,
Graft-modified polyolefin obtained by polymerizing the monomer in the absence of a solvent or in the presence of a solvent of 30 parts by weight or less and subjecting the monomer to polymerization initiation conditions generated by 0.001 to 10 parts by weight of a radical initiator. Manufacturing method. (M is an integer of 1 to 10, R ¹ , R ² and R ³ each represent hydrogen or a hydrocarbon group having up to 8 carbon atoms.) (R ⁴ represents a hydrocarbon group having 1 to 6 carbon atoms, R ⁵ represents hydrogen or a hydrocarbon group having 1 to 8 carbon atoms, and n represents an integer of 0 or 1.) Effect The graft-modified polyolefin is Since it can be obtained with a sufficiently high grafting rate or grafting efficiency, the modification effect by introducing the radically polymerizable monomer is highly obtained.

Description

Detailed Description of the Invention

BACKGROUND OF THE INVENTION

BACKGROUND OF THE INVENTION The present invention relates to an unsaturated copolymer consisting of an α-olefin and a specific diene compound and a radically polymerizable monomer in the radical of the latter in the presence of substantially no solvent. By subjecting it to polymerization conditions, adhesiveness,
The present invention relates to a method for producing a graft-modified copolymer having excellent printability, paintability, hydrophilicity, and compatibility with polymer blends.

[0002]

2. Description of the Related Art Homopolymers of α-olefins (including ethylene in the present invention) and copolymers thereof are inexpensive and have excellent mechanical strength, gloss and transparency. Since it has moldability, moisture resistance, chemical resistance, etc., it is widely used alone or as a component of a polymer blend. However, since the α-olefin polymer has a non-polar molecular structure, it has a poor affinity with other substances, and is extremely inferior in adhesiveness, printability, and compatibility with polymer blends.

In order to improve this property, many methods have long been attempted for producing a modified polymer by graft-polymerizing a radical-polymerizable monomer onto an α-olefin polymer.

However, in general, the radical grafting method does not have a sufficiently high grafting ratio or grafting efficiency, and in many cases, a radical polymerization initiator such as an organic or inorganic peroxide is used. Many problems remain, such as the tendency of polymer molecular cleavage and crosslinking reaction to occur.

Various inventions have been proposed for the purpose of solving these problems. Among them, the one which is considered to be particularly closely related to the present invention is Japanese Patent Application Laid-Open No. Hei 2
There is a publication of -140201. This invention is to react a radically polymerizable monomer having an epoxy group to the particles of polyolefin, but since polyolefin particles not containing an unsaturated bond are used, both have a low graft modification rate, and The recovery of the solvent is required in order to use it in a considerable amount, which is not a practical technique.

[0006]

Although the above-mentioned conventional techniques are useful as such, it was difficult to say that they are sufficiently satisfactory in terms of grafting efficiency.

[0007]

[Means for Solving the Problems]

[Summary of the Invention] <Gist> The present invention is intended to solve these problems.

That is, the method for producing a graft-modified polyolefin according to the present invention is a carbon-carbon double bond obtained by copolymerizing ethylene or α-olefin with a diene compound represented by the following general formula (I) or (II). 100 parts by weight of an unsaturated copolymer having a unit concentration of 0.05 to 50 mol% based on the diene compound in the copolymer, and a radical-polymerizable monomer of 0.0
5 to 300 parts by weight of the monomer is subjected to a polymerization initiation condition in which 0.001 to 10 parts by weight of a radical initiator is generated in the absence of a solvent or in the presence of a solvent of 30 parts by weight or less. Is polymerized.

[0009]

[Chemical 3] (Where m is an integer from ^{1 to} 10, R ¹ , R ² and R ³
Each represents hydrogen or a hydrocarbon group having up to 8 carbon atoms. )

[0010]

[Chemical 4] (Here, R ⁴ represents a hydrocarbon group having 1 to 6 carbon atoms, R ⁵ represents hydrogen or a hydrocarbon group having 1 to 8 carbon atoms, and n represents an integer of 0 or 1.) <Effect> Book The graft-modified polyolefin according to the present invention is a radical-polymerizable polyolefin introduced as a graft chain without impairing the properties inherently possessed by an α-olefin polymer, such as excellent mechanical strength, transparency, moldability and chemical resistance. It is provided with characteristics based on a monomer, such as adhesiveness or dyeability of various inks and paints. Since such a graft-modified polyolefin according to the present invention can be obtained with a sufficiently high graft ratio or graft efficiency, the modification effect by introducing a radical-polymerizable monomer is highly obtained. Further, the graft-modified polyolefin according to the present invention has a high affinity with other resins,
Exhibits excellent compatibility effects in polymer blends. Further, since the amount of the solvent used in the polymerization is small (in the present invention, the polymerization can be carried out without using the solvent), it is efficient and economical. [Detailed Description of the Invention] << Unsaturated Copolymer to be Modified >><GeneralDescription> The unsaturated copolymer used in the present invention is ethylene or α-olefin, preferably ethylene or C 3 -C 3 A copolymer of 12 α-olefins, more preferably ethylene or α-olefins having 3 to 8 carbon atoms, and a specific diene compound represented by the above formula (I) or (II). The unit concentration on the basis is 0.05 to 50 mol%, preferably 0.1 to 30 mol%, more preferably 0.1 to 20 mol%, and particularly preferably 0.1 to 10 mol%.

Ethylene, α-olefins and formula (I)
Alternatively, the diene compounds of (II) may be used alone or in combination of two or more. The diene compound of formula (I) or (II) may be distributed randomly in the unsaturated copolymer, or may be distributed in blocks. <Ethylene or α-olefin> One component of the unsaturated copolymer is ethylene or α-olefin.

Examples of the above α-olefins are α-olefins having 3 to 12 carbon atoms, preferably 3 to 8 carbon atoms, specifically propylene, 1-butene, 1-hexene, 3- Methyl-1-butene, 3-methyl-1-pentene, 4-methyl-1-pentene, 3,3-dimethyl-
1-butene, 4,4-dimethyl-1-pentene, 3-methyl-1-hexene, 4-methyl-1-hexene, 4,
4-dimethyl-1-hexene, 5-methyl-1-hexene, etc. may be mentioned. These ethylene or α-olefins may be used alone or in combination of two or more. Among these, preferred examples are ethylene, propylene, 1-butene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 4-methyl-1-pentene, 3-methyl-1- Hexene and the like can be mentioned, in particular, propylene alone or propylene and 3-methyl-1-butene and 1 or 4-
The mixed use of methyl-1-pentene is preferred. <Diene Compound of Formula (I)>

[0013]

[Chemical 5] (Where m is an integer of 1 to 10 and R ¹ , R ² and R ³ are each hydrogen or a hydrocarbon group having up to 8 carbon atoms) Of the diene compounds represented by the formula (I), preferred Wherein R ¹ , R ² and R ³ are each a hydrogen atom or an alkyl group having 1 to 4 carbon atoms,
More preferably, m is 1 to 3 and R ¹ has ¹ carbon atom.
~ 3 alkyl group, R ² and R ³ are hydrogen atoms or alkyl groups having 1 to 3 carbon atoms, R ² and R ³ are not hydrogen atoms at the same time, and m is 5 to 10, R ¹
And R ² are both hydrogen atoms.

Specific examples of such a diene compound include the following. (A) 2-methyl-1,4-pentadiene, 4-methylidene-1-hexene, 1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 1,4 -Heptadiene, 4-ethyl-1,
4-hexadiene, 4,5-dimethyl-1,4-hexadiene, 4-methyl-1,4-heptadiene, 4-ethyl-1,4-heptadiene, 5-methyl-1,4-heptadiene, 5-methyl- Chain-like 1,4-dienes such as 1,4-octadiene, (b) 1,5-heptadiene,
Chain 1,5-dienes such as 1,5-octadiene, 5-methyl-1,5-heptadiene, 6-methyl-1,5-heptadiene, 2-methyl-1,5-hexadiene,
(C) 1,6-octadiene, 6-methyl-1,6-
Octadiene, 7-methyl-1,6-octadiene, 2
-Methyl-1,6-heptadiene, 6-methylidene-1
-Octene, 6-ethyl-1,6-octadiene, 6,
7-dimethyl-1,6-octadiene, 1,6-nonadiene, 6-ethyl-1,6-nonadiene, 7-methyl-
Chain-like 1,6-dienes such as 1,6-nonadiene and 7-methyl-1,6-decadiene, (d) 1,7-nonadiene, 7-methyl-1,7-nonadiene, 8-methyl-
Chain-like 1,7-dienes such as 1,7-nonadiene, 2-methyl-1,7-octadiene, (e) 8-methyl-
Chain-like 1,8-dienes such as 1,8-decadiene and 9-methyl-1,8-decadiene. (F) α, ω-dienes such as 1,8-nonadiene, 1,10-decadiene and 1,12-tridecadiene.

Among these examples, a particularly preferable example is 4
-Methyl-1,4-hexadiene, 5-methyl-1,4
-Hexadiene, 7-methyl-1,6-octadiene,
1,8-nonadiene, 1,10-decadiene and 1,
It is 12-tridecadiene.

These diene compounds may be used alone or in combination of two or more, and the preferable example of the latter is a combination of 4-methyl-1,4-hexadiene and 5-methyl-1,4-hexadiene (weight: Ratios of 95: 5 to 5:95). <Diene compound of formula (II)>

[0017]

[Chemical 6] (Here, R ⁴ represents a hydrocarbon group having 1 to 6 carbon atoms, R ⁵ represents hydrogen or a hydrocarbon group having 1 to 8 carbon atoms, and n represents an integer of 0 or 1.) Formula (II) The diene compound shown is a compound in which two alkenyl groups are bonded to one benzene ring, as is apparent from the above formula, that is, dialkenylbenzene. The bonding positions of the two alkenyl groups are arbitrary, and thus the dialkenylbenzene is in the o-form,
It may be any of isomers such as m-form and p-form, and may be a mixture of these isomers. Furthermore, each derivative in which the benzene ring is substituted with a hydrocarbon group other than R ⁴ may be used.

Specifically, divinylbenzene, isopropenylstyrene, divinyltoluene, divinylnaphthalene, 1-phenyl-1- (4-vinylphenyl) ethylene, 1- (4-methylphenyl) -1- (4-vinyl Phenyl) ethylene and 1- (4-propenylphenyl) -1- (4-vinylphenyl) ethylene.

Particularly preferred among these examples are divinylbenzene, isopropenylstyrene and 1-phenyl-1- (4-vinylphenyl) ethylene. <Unsaturated Copolymer Production Catalyst> The unsaturated copolymer used in the present invention can be produced using a known Ziegler-Natta type catalyst.

Typical examples of the Ziegler-Natta type catalyst that can be used in the present invention include the following two catalysts. <Catalyst (No. 1)> Examples of Ziegler-Natta type catalysts used in the production of unsaturated copolymers are shown in Periodic Tables IV to VI.
It is composed of a combination of a transition metal compound of Group I (halide, alkoxide, acetylacetonate, etc.) and an organometallic compound of Group I to III of the periodic table. here,
The term "combined" means not only a combination product of the above-mentioned two kinds of compounds, but also a combination product with other components which improve the combination effect of these compounds or do not substantially impair the effect. To do.

A typical transition metal compound is titanium,
It is a compound of vanadium and zirconium. Explaining in more detail using titanium as an example, the titanium compound is
TiCl ₄ , TiCl _p (OR ⁶ ) _4-p (wherein R ⁶
Is a hydrocarbon residue, p = 0-4), TiCl ₃ · qAlC
_{l 3 (q = 0~1 / 3} ) and the so-called supported titanium compound these compounds supported on a magnesium chloride and the like. Further, these transition metal compounds may be modified with known electron donating compounds (esters, ethers, amines, etc.).

Organometallic compounds of Groups I to III of the Periodic Table include organometallic compounds having at least one carbon-metal bond, such as lithium, sodium, magnesium and aluminum, which have the general formula R ⁷ Li, R ⁷ _r Me
X ¹ _2-r or AlR ⁷ _s X ¹ _3-s (R ⁷ is an aliphatic, alicyclic or aromatic hydrocarbon residue having up to 20 carbon atoms, X
¹ is a halogen, r is 1 or 2, and s is a number of 1 to 3).

Specifically, ethyl lithium, n-propyl lithium, isopropyl lithium, n-butyl lithium, sec-butyl lithium, tert-butyl lithium, n
-Decyl lithium, phenyl lithium, benzyl lithium, 1-naphthyl lithium, p-tolyl lithium, cyclohexyl lithium, α-methylstyryl lithium, sodium naphthalene, ethyl magnesium chloride,
Butyl magnesium chloride, dibutyl magnesium, triethyl aluminum, triisobutyl aluminum, trihexyl aluminum, diethyl aluminum chloride, diisobutyl aluminum chloride,
Examples thereof include diisobutylaluminum hydride.

These organometallic compounds may be used in combination with a known electron donating compound in combination with a transition metal compound to form a Ziegler-Natta type catalyst.

The amount ratio of the above-mentioned organometallic compound and transition metal compound used is not particularly limited, but is 0.5 to 500 (molar ratio).
It is generally used in the range of. <Ziegler-Natta type catalyst (2)> A second example of the Ziegler-Natta type catalyst used for the production of the unsaturated copolymer is, for example, the following component (A) and component (B). is there. Here, "consisting of" means
It does not mean that the ingredients are only those listed (ie, (A) and (B)), but does not exclude the coexistence of purposefully other ingredients. <Component (A)> Component (A) is a general formula _{Q a (C 5 H 5-} ab R 8 b) (C 5 H 5-ac R 9 c) a transition metal compound represented by Mexy.

Here, Q is a bonding group that bridges two conjugated five-membered ring ligands. Specifically, (i) an alkylene group having 1 to 3 carbon atoms such as a methylene group, an ethylene group, an isopropylene group, a phenylmethylmethylene group, a diphenylmethylene group, a cyclohexylene group or a carbon-substituted product thereof having a total carbon number of 1 ~ 20 divalent hydrocarbon residues,
(B) silylene group, dimethylsilylene group, phenylmethylsilylene group, diphenylsilylene group, disilylene group,
A mono- or oligo-silylene group which may have a hydrocarbon residue having a carbon number of about 1 to 20 such as a tetramethyldisililen group as a substituent, (C) germanium, phosphorus, nitrogen, boron or aluminum containing 1 carbon atoms To about 20 hydrocarbon groups (specifically, (CH ₃ ) ₂ Ge groups, (C
₆ H ₅ ) ₂ Ge group, (CH ₃ ) P group, (C ₆ H ₅ ) P group
_Group, (C _{4 H} 9) N _group, (C _{6 H} 5) N group, _(CH 3)
B group, (C ₄ H ₉ ) B group, (C ₆ H ₅ ) B group, (C ₆ H
₅ ) Al group, (CH ₃ O) Al group, etc.) and the like. Preferred are alkylene groups and silylene groups. a is 0 or 1.

(C ₅ H _5-ab R ⁸ _b ) and (C ₅ H
_The conjugated five-membered ring ligand represented by _5-ac R ⁹ _c ) is defined separately, but b and c and R ⁸ and R ⁹ are the same in definition (details below). It goes without saying that the two conjugated five-membered ring groups may be the same or different. One specific example of this conjugated 5-membered ring group is a cyclopentadienyl group of b = 0 (or c = 0) (without a substituent other than the bridging group Q). When this conjugated five-membered ring group is b ≠ 0 (or c ≠ 0) and has a substituent, one specific example of R ⁸ (or R ⁹ ) is a hydrocarbon group (C _1- ). C _20, preferably C ₁ -C ₁₂₎ a but, the hydrocarbon group that two other respectively when it also be bonded to a cyclopentadienyl group is present a plurality as monovalent group They may be bonded at the ends to form a ring together with a part of the cyclopentadienyl group. A typical example of the latter is that in which R ⁸ (or R ⁹ ) shares a double bond of the cyclopentadienyl group to form a condensed 6-membered ring, that is, the conjugated 5-membered ring group is an indenyl group or A fluorenyl group. That is, typical examples of the conjugated 5-membered ring group are a substituted or unsubstituted cyclopentadienyl group, an indenyl group and a fluorenyl group.

R ⁸ and R ⁹ are each the above C ₁
To C ₂₀ , preferably C _{1 to} C ₁₂ hydrocarbon groups,
Halogen group (eg, fluorine, chlorine, bromine), alkoxy group (eg, C _{1 to} C ₁₂ ), silicon-containing hydrocarbon group (eg, silicon atom to —Si— (R ¹⁰ )).
(R ¹¹ ) (R ¹² ) group containing about 1 to 24 carbon atoms, phosphorus-containing hydrocarbon group (for example, phosphorus atom is -P.
- (R ¹³⁾ group of about 1 to 18 carbon atoms, including in the form of (R ^13)), nitrogen-containing hydrocarbon group (e.g., nitrogen atom and -N
(A group containing about 1 to 18 carbon atoms in the form of (R ¹⁴ ) (R ¹⁵ ))
Alternatively, it is a boron-containing hydrocarbon group (for example, a group having a carbon atom in the form of —B— (R ¹⁶ ) (R ¹⁷ ) and having about 1 to 18 carbon atoms). b (or c) is 2 or more and R
When a plurality of ⁸ (or R ⁹ ) are present, they may be the same or different.

B and c are 0≤b≤ when a is 0.
5, 0 ≦ c ≦ 5, when a = 1, 0 ≦ b ≦ 4, 0 ≦ c ≦
4 is an integer that satisfies the requirement.

Me is a group IVB transition metal of the periodic table selected from titanium, zirconium and hafnium, preferably titanium and zirconium, particularly preferably zirconium.

X and Y are each hydrogen, a halogen group, a hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms,
An amino group, a phosphorus-containing hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms (specifically, for example, diphenylphosphine group), or 1 to 20 carbon atoms, preferably 1 carbon atom
.About.12, a silicon-containing hydrocarbon group (specifically, for example, a trimethylsilyl group). X and Y may be the same or different. Of these, a halogen group and a hydrocarbon group are preferable. Particularly, those in which X and Y are halogen are preferable.

Specifically, (1) bis (cyclopentadienyl) dimethylzirconium, (2) bis (cyclopentadienyl) diethylzirconium, (3) bis (cyclopentadienyl) methylzirconium monochloride, ( 4) bis (cyclopentadienyl) ethylzirconium monochloride, (5) bis (cyclopentadienyl) methylzirconium monobromide, (6) bis (cyclopentadienyl) methylzirconium monoiodide, (7) bis ( Cyclopentadienyl) zirconium dichloride, (8) bis (cyclopentadienyl) zirconium dibromide, (9) ethylenebis (cyclopentadienyl) zirconium dichloride, (10) ethylenebis (cyclopentadienyl) methylzirconium mono Chloride, (11) Ethi Renbis (cyclopentadienyl) dimethylzirconium, (12) methylenebis (cyclopentadienyl) zirconium dichloride, (13) propylenebis (cyclopentadienyl) zirconium dichloride (14) ethylenebis (indenyl) zirconium dichloride, (15) Ethylenebis (indenyl) zirconium monochloride monohydride, (16) ethylenebis (indenyl) dimethylzirconium, (17) ethylenebis (indenyl) diphenylzirconium, (18) ethylenebis (indenyl) zirconium dibromide,
(19) Ethylenebis (4,5,6,7-tetrahydro-
1-indenyl) dimethyl zirconium, (20) ethylenebis (4,5,6,7-tetrahydro-1-indenyl) zirconium dichloride, (21) ethylenebis (4
-Methyl-1-indenyl) zirconium dichloride,
(22) ethylenebis (2,3-dimethyl-1-indenyl) zirconium dichloride, (23) dimethylsilylbis (cyclopentadienyl) dimethylzirconium,
(24) Dimethylsilylbis (cyclopentadienyl) zirconium dichloride, (25) Dimethylsilylbis (methylcyclopentadienyl) zirconium dichloride,
(26) dimethylsilylbis (dimethylcyclopentadienyl) zirconium dichloride, (27) bis (cyclopentadienyl) dimethyltitanium, (28) bis (cyclopentadienyl) methyltitanium monochloride,
(29) bis (cyclopentadienyl) titanium dichloride, (30) ethylenebis (indenyl) titanium dichloride, (31) ethylenebis (4,5,6,7-tetrahydro-1-indenyl) titanium dichloride,
(32) Methylenebis (cyclopentadienyl) titanium dichloride, (33) Methylene (cyclopentadienyl) (3,4-dimethylcyclopentadienyl) zirconium dichloride, (34) Methylene (cyclopentadienyl) (3 4-dimethylcyclopentadienyl) zirconium chloride hydride, (35) methylene (cyclopentadienyl) (3,4-dimethylcyclopentadienyl) zirconium dimethyl, (36) methylene (cyclopentadienyl) (3,4 -Dimethylcyclopentadienyl) zirconium diphenyl, (37) methylene (cyclopentadienyl) (trimethylcyclopentadienyl)
Zirconium dichloride, (38) methylene (cyclopentadienyl) (tetramethylcyclopentadienyl) zirconium dichloride, (39) isopropylidene (cyclopentadienyl) (3,4-dimethylcyclopentadienyl) zirconium dichloride, ( 40) isopropylidene (cyclopentadienyl) (3-methylindenyl) zirconium dichloride, (41) isopropylidene (2-methylcyclopentadienyl) (fluorenyl)
Zirconium dichloride, (42) isopropylidene (cyclopentadienyl) (fluorenyl) zirconium dichloride, (43) isopropylidene (2,5-dimethylcyclopentadienyl) (3 ', 4'-dimethylcyclopentadienyl) zirconium Dichloride, (44) Isopropylidene (2,5-dimethylcyclopentadienyl) (fluorenyl) zirconium dichloride, (45)
Ethylene (cyclopentadienyl) (3,5-dimethylcyclopentadienyl) zirconium dichloride, (4
6) ethylene (cyclopentadienyl) (fluorenyl) zirconium dichloride, (47) ethylene (2,5
-Dimethylcyclopentadienyl) (fluorenyl) zirconium dichloride, (48) ethylene (2,5-diethylcyclopentadienyl) (fluorenyl) zirconium dichloride, (49) diphenylmethylene (cyclopentadienyl) (3,4- Dimethylcyclopentadienyl) zirconium dichloride, (50) diphenylmethylene (cyclopentadienyl) (3,4-diethylcyclopentadienyl) zirconium dichloride, (51) cyclohexylidene (cyclopentadienyl) (fluorenyl) zirconium Dichloride, (52) cyclohexylidene (2,5-dimethylcyclopentadienyl) (3 ',
4'-Dimethylcyclopentadienyl) zirconium dichloride, (53) dimethylsilylene (cyclopentadienyl) (3,4-dimethylcyclopentadienyl) zirconium dichloride, (54) dimethylsilylene (cyclopentadienyl) (trimethyl Cyclopentadienyl)
Zirconium dichloride, (55) dimethylsilylene (cyclopentadienyl) (tetramethylcyclopentadienyl) zirconium dichloride, (56) dimethylsilylene (cyclopentadienyl) (3,4-diethylcyclopentadienyl) zirconium dichloride, (57) Dimethylsilylene (cyclopentadienyl) (triethylcyclopentadienyl) zirconium dichloride, (58)
Dimethylsilylene (cyclopentadienyl) (tetraethylcyclopentadienyl) zirconium dichloride,
(59) Dimethylsilylene (cyclopentadienyl) (fluorenyl) zirconium dichloride, (60) Dimethylsilylene (cyclopentadienyl) (2,7-di-t-
Butylfluorenyl) zirconium dichloride, (61)
Dimethylsilylene (cyclopentadienyl) (octahydrofluorenyl) zirconium dichloride, (62) dimethylsilylene (2-methylcyclopentadienyl)
(Fluorenyl) zirconium dichloride, (63) dimethylsilylene (2,5-dimethylcyclopentadienyl) (fluorenyl) zirconium dichloride, (64)
Dimethylsilylene (2-ethylcyclopentadienyl)
(Fluorenyl) zirconium dichloride, (65) dimethylsilylene (2,5-diethylcyclopentadienyl) (fluorenyl) zirconium dichloride, (66)
Dimethylsilylene (2-methylcyclopentadienyl)
(2,7-di-t-butylfluorenyl) zirconium dichloride, (67) dimethylsilylene (2,5-dimethylcyclopentadienyl) (2,7-di-t-butylfluorenyl) zirconium dichloride, (68) Dimethylsilylene (2-ethylcyclopentadienyl) (2,7
-Di-t-butylfluorenyl) zirconium dichloride, (69) dimethylsilylene (diethylcyclopentadienyl) (2,7-di-t-butylfluorenyl) zirconium dichloride, (70) dimethylsilylene (methylcyclo Pentadienyl) (octahydrofluorenyl)
Zirconium dichloride, (71) Dimethylsilylene (dimethylcyclopentadienyl) (octahydrofluorenyl) zirconium dichloride, (72) Dimethylsilylene (ethylcyclopentadienyl) (octahydrofluorenyl) zirconium dichloride, (73) Dimethylsilylene (diethylcyclopentadienyl) (octahydrofluorenyl) zirconium dichloride, (74) dimethylgermane (cyclopentadienyl) (fluorenyl) zirconium dichloride, (75) phenylalumino (cyclopentadienyl) (fluorenyl) Zirconium dichloride, (76) Phenylalumino (cyclopentadienyl) (fluorenyl) zirconium dichloride,
And so on. <Component (B)> The component (B) is alumoxane. What is preferably used in the present invention is the following general (III)
Alternatively, it is an organoaluminum compound represented by (IV).

[0033]

[Chemical 7] In this general formula, each R ¹⁸ independently has 1 carbon atom.
To 5 alkyl groups, for example, methyl group, ethyl group, propyl group, butyl group and the like, particularly preferably methyl group, and t is an integer of 2 or more, preferably 4 or more and 100 or less.

This component (B) is a product obtained by reacting one kind of trialkylaluminum or two or more kinds of trialkylaluminum with water. Specifically, (a) methyl alumoxane, ethyl alumoxane, propyl alumoxane, butyl alumoxane, isobutyl alumoxane obtained from one type of trialkylaluminum, and (b) two types of trialkylaluminum obtained from water. Examples thereof include methyl ethyl alumoxane, methyl butyl alumoxane and methyl isobutyl alumoxane. Of these, methylalumoxane is particularly preferable.

A plurality of these alumoxanes can be used in combination in each group and between each group, and they can be used in combination with other alkylaluminum compounds such as trimethylaluminum, triethylaluminum, triisobutylaluminum and dimethylaluminum chloride. It is also possible to do so.

These alumoxanes can be prepared under various known conditions. Specifically, the following methods can be exemplified. (A) a method in which a trialkylaluminum is directly reacted with water using a suitable organic solvent such as toluene, benzene or ether; and (b) a salt hydrate containing trialkylaluminum and water of crystallization, such as copper sulfate or aluminum sulfate. A method of reacting with a hydrate, (c) a method of reacting trialkylaluminum with water impregnated in silica gel, etc., (d) a mixture of trimethylaluminum and triisobutylaluminum, and mixing with toluene, benzene, ether or the like. A method of directly reacting with water using an organic solvent,
(E) A method in which trimethylaluminum and triisobutylaluminum are mixed and reacted by heating with a salt hydrate having water of crystallization, for example, copper sulfate or aluminum sulfate hydrate, (f) Silica gel is impregnated with water, and After treatment with isobutylaluminum, a method of additional treatment with trimethylaluminum, (to) methylalumoxane and isobutylalumoxane are synthesized by a known method, a predetermined amount of these two components is mixed, and a method of heating reaction, preferably, Method (a) is used. <Production of Unsaturated Copolymer> The copolymerization of α-olefin and diene compound is usually carried out in a hydrocarbon solvent.
Specific examples of the hydrocarbon solvent include aliphatic hydrocarbons such as hexane, heptane, octane, decane, cyclohexane and kerosene, and aromatic hydrocarbons such as benzene, toluene and xylene. These can be used alone or as a mixture.

As the polymerization method, a liquid phase polymerization method such as a suspension polymerization method or a solution polymerization method can be used. The polymerization temperature is -78 to 150 ° C, preferably -60 to 90 ° C.
The polymerization pressure is generally 0 to 50 kg / cm ² , preferably 0 to 30 kg / cm ² . In the present invention, hydrogen can be used for controlling the molecular weight of the copolymer.

After the completion of the polymerization reaction, the unsaturated olefin copolymer is obtained by treating the polymerization reaction solution by a conventional method. << Modification of Unsaturated Copolymer >> The monomer to be graft-polymerized is a compound which can be homopolymerized or copolymerized by a radical polymerization mechanism.

In the present invention, the unsaturated graft copolymer and the radical-polymerizable monomer obtained as described above are subjected to polymerization initiation conditions to produce a radical-initiator to obtain the desired graft-modified polyolefin. To manufacture. From this, it is understood that a graft-modified polyolefin having a structure in which a polymer chain derived from a radical-polymerizable monomer is added as a branch polymer is produced.

Examples of such monomers include vinyl monomers, vinylidene monomers, α, β-unsaturated carboxylic acids and their derivatives.

Specifically, for example, (a) styrene-based monomer, for example, unsubstituted or core- and / or side-chain-substituted styrene (substituent is halogen, lower alkyl group, halo lower alkyl group, etc.) , Especially styrene, nuclear-substituted styrenes such as methylstyrene, dimethylstyrene,
Ethylstyrene, isopropylstyrene, chlorostyrene, chloromethylstyrene, α-substituted styrenes such as α-methylstyrene, α-ethylstyrene, (b) vinyl halides or vinylidene halides such as vinyl chloride, vinyl bromide, vinylidene chloride. , Vinylidene bromide, (c) unsaturated nitriles such as acrylonitrile, methacrylonitrile, (di) vinyl esters such as vinyl acetate, (e) basic or nitrogen-containing monomers such as vinylcarbazole, vinylpyridine, vinylpyrrolidone. , (F) unsaturated ketones such as methyl vinyl ketone, aromatic monomers other than (to) styrene such as vinylnaphthalene, allylbenzene, (thi) conjugated dienes such as butadiene, isoprene, chloroprene, (ri) unsaturated Saturated carbo Acids and derivatives thereof, such as acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, hymic acid, crotonic acid, 1 the carbon number of these esters (alcohol component
About 10. Glycidyl alcohol, including halohydrins and ether alcohols), anhydrides, metal salts, amides, imides.

Among these, styrene, α-methylstyrene, vinyl chloride, acrylonitrile, vinyl acetate, acrylic acid, methacrylic acid, maleic acid or fumaric acid ester, and glycidyl acrylate whose alcohol component is an alkyl group having 1 to 8 carbon atoms. , Glycidyl methacrylate, alkyl (having 1 to 8 carbon atoms) glycidyl maleate, alkyl (having 1 to 8 carbon atoms) glycidyl fumarate, and maleic anhydride are preferably used. in particular,
Those belonging to the unsaturated carboxylic acid and its derivative of (i) are preferably used.

These monomers may be used alone or in combination of two or more within a group or between groups. The unsaturated carboxylic acid or its derivative is often used in combination with another monomer.

The amount of the monomer used is 100% of the unsaturated copolymer.
0.05 to 300 with respect to parts (parts by weight; the same applies hereinafter)
Parts, preferably 0.1 to 200 parts, particularly preferably 0.
5 to 50 parts. If the amount of the monomer is less than 0.05 part, the improving effect according to the present invention is scarce, and if it exceeds 300 part, the mechanical properties of the unsaturated copolymer are difficult to be exhibited.

This reaction is carried out using a radical initiator.

As the radical initiator, organic peroxides, azo compounds and the like are usually used. Specific examples of the organic peroxide initiator include dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-bis (tert-butylperoxy) hexane and 2,5-dimethyl-2. 5-bis (tert-butylperoxy) hexyne-3,1,3-bis (tert-butylperoxyisopropyl) benzene, 1,1-bis (te
rt-Butylperoxy) -3,3,5-trimethylcyclohexane, n-butyl-4,4-bis (tert-butylperoxy) valerate, dibenzoyl peroxide,
tert-butylperoxybenzoate, acetyl peroxide, isobutyryl peroxide, octanoyl peroxide, decanoyl peroxide, lauroyl peroxide, 3,3,5-trimethylhexanoyl peroxide, 2,4-dichlorobenzoyl peroxide, m-
Examples thereof include toluoyl peroxide. Moreover, azobisisobutyronitrile etc. are mentioned as an azo compound. Such radical initiators can be used alone or in combination. Among such radical initiators, dibenzoyl peroxide is particularly preferable.

The amount of the radical initiator used is 0.001 to 10 parts by weight, preferably 0.005 to 8 parts by weight, and more preferably 0.0 to 10 parts by weight based on 100 parts by weight of the unsaturated copolymer.
It is 1 to 6 parts by weight.

The contact of the unsaturated copolymer, the radical-polymerizable monomer and the radical initiator can be carried out in the presence or absence of a small amount of solvent.

When the solvent is present, the solvent is
(A) Benzene, toluene, xylene and other aromatic hydrocarbon solvents, (b) pentane, hexane, heptane, octane, nonane, decane and other aliphatic hydrocarbon solvents,
(C) alicyclic hydrocarbon solvents such as cyclohexane, methylcyclohexane, decahydronaphthalene, (di) chlorobenzene, dichlorobenzene, trichlorobenzene,
Examples thereof include chlorinated hydrocarbon solvents such as methylene chloride, chloroform, carbon tetrachloride and tetrachloroethylene.

It is also possible to use a poor solvent mixed with the above-mentioned solvent in an appropriate amount. Examples of the poor solvent include alcohol solvents such as methanol, ethanol, n-propanol, iso-propanol, n-butanol, sec-butanol and tert-butanol, ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone, ethyl acetate, Examples thereof include ester solvents such as dimethyl phthalate, and ether solvents such as dimethyl ether, diethyl ether, di-n-amyl ether, tetrahydrofuran and dioxyanisole.

When a solvent is used, the amount of the solvent used is 30 parts by weight or less, preferably 20 parts by weight or less, more preferably 10 parts by weight or less based on 100 parts by weight of the unsaturated copolymer.

There is no particular limitation on the contact method and order of the unsaturated copolymer, the radically polymerizable monomer and the radical initiator.

The contact of the above three components is usually carried out at a temperature at which the shape of the unsaturated copolymer powder is substantially maintained, that is, at a temperature at which the copolymer powder is melted and the powder particles are not fused to each other. Is. This temperature depends on the type of unsaturated copolymer used, but should be a temperature at which sufficient decomposition of the radical initiator occurs.

The reaction time can be set arbitrarily in consideration of the reaction temperature and other conditions.

The reactor is not particularly limited as long as the above components can be mixed and heated. << Graft-Modified Polyolefin >> The thus-obtained graft-modified polyolefin according to the present invention is an unsaturated copolymer obtained by copolymerizing ethylene or α-olefin with a specific diene compound, and has the formula (I) When the diene compound of

[0056]

[Chemical 8] When the diene of formula (II) is used,

[0057]

[Chemical 9] In the form of a structure in which a polymer chain produced from a radically polymerizable monomer is added as a "branch" polymer to each carbon-carbon double bond based on the diene compound of the copolymer. It is believed to be a graft copolymer.

Such a graft-modified polyolefin according to the present invention can be used not only as a molding material itself, but also as a compatibilizing agent for a mixture of polyolefin and various resins or as an adhesive between polyolefin and various resins. Further, it can be widely used as an olefin copolymer having improved adhesiveness, dyeability, printability, miscibility with other polar resins, and the like.

The graft copolymerization in the present invention is
In the presence of a "stem" polymer, equivalent to polymerizing a monomer to give a "branch" polymer, it does not "branch" beyond the ideal backbone-branched copolymer It is often observed that a polymer of this monomer itself is a by-product. Therefore,
Also in the present invention, the “graft-modified copolymer” includes a mixture containing such a by-product.

[0060]

【Example】

[Unsaturated Copolymer Production Example-1] Internal volume 5 equipped with a stirring blade
In a liter stainless steel autoclave, 1.-methyl-1,6-octadiene was added to 1.
After charging 5 liters, 3.0 g of triethylaluminum and 1.0 g of a solid titanium catalyst containing magnesium were added. After adding 0.05Nl of hydrogen, the total pressure is 1.0kg / cm
While pressurizing with propylene to ² (gauge pressure), 7
Copolymerization was carried out at 0 ° C. for 5 hours. The copolymer slurry that had been detouched was steam stripped and then dried under reduced pressure to obtain 540 g of a copolymer.

The melt index (23
(0 ° C.) was 2.5 g / 10 minutes, and the 7-methyl-1.6-octadiene content was 3.3 mol%. This copolymer is referred to as resin A. [Unsaturated Copolymer Production Example-2] 1-phenyl-1- (4
-Vinylphenyl) ethylene 25g instead of divinylbenzene (Tokyo Kasei Co., m- and p-mixture)
A copolymerization operation was carried out in exactly the same manner as in the unsaturated copolymer production example-1 except that 8 ml was used and 280 ml of hydrogen was used instead of 480 ml of hydrogen. As a result, 50.2 g of a copolymer powder polymer was obtained (catalytic activity 500 g copolymer / g
TiCl ₃ , MFR = 2.23 g / 10 min). The content of copolymerized divinylbenzene in this copolymer was measured by an ultraviolet spectrum method and found to be 0.16 mol%. This is referred to as resin B. [Unsaturated Copolymer Production Example-3] First, 1-phenyl-1
-(4-Vinylphenyl) ethylene is disclosed in JP-A-63-13.
It was synthesized according to the synthesis example of 9905.

Internal volume 1 with stirring and temperature control
After repeating vacuum propylene displacement several times in a liter stainless steel autoclave, 500 ml of sufficiently dehydrated and deoxygenated n-heptane was added to the 1-phenyl-1- (4-vinylphenyl) ethylene synthesized above. Two
5 g, diethylaluminum chloride 0.92 g and Marubeni Solvay's titanium trichloride 0.1 g were added in this order, and further 480 ml of hydrogen was added to the mixture of propylene and 1-phenyl-1- (4-vinylphenyl) ethylene. Polymerization was initiated. Copolymerization conditions are propylene pressure 7 kg / cm ²
G / 65 ° C./2 hours.

After completion of the copolymerization, the residual monomer was purged,
The polymer slurry is filtered to obtain a copolymer powder polymer 19
0.7 g was obtained (catalytic activity 1907 g copolymer / g T
iCl _3, MFR = 1.82g / 10 minutes). The content of copolymerized 1-phenyl-1- (4-vinylphenyl) ethylene in this copolymer was analyzed by NMR method,
It was 2.05 mol%. This is designated as resin C. [Example-1] In a 300 ml flask that had been sufficiently replaced with nitrogen, 20 g of Resin A, 1 ml of toluene, and 4 maleic anhydride were used.
g, and dibenzoyl peroxide 200 mg,
These were stirred under nitrogen at room temperature for 1 hour at 100 revolutions / minute, then heated to 100 ° C., and further stirred for 4 hours to cause reaction. After the reaction, the reaction product was dissolved in xylene, precipitated in acetone, and filtered and dried.

The maleic anhydride content in the dried polymer was measured by IR spectroscopy, and it was found that 5.6 wt% of maleic anhydride was grafted. [Example-2] Example-except that toluene was not added
A polymer was produced by the same method as in Example 1, and the amount of maleic anhydride grafted was measured in the same manner. as a result,
It was found that 4.63 wt% maleic anhydride was grafted into the polymer. [Example-3] 1 ml of toluene was replaced with 1 ml of n-heptane, and 4 g of maleic anhydride was replaced with 4 g of glycidyl methacrylate.
A polymer was produced in the same manner as in Example 1 except that acetone was changed to methanol instead of g, and the graft amount was measured by the same method. as a result,
It was found that 4.89 wt% of glycidyl methacrylate was grafted. [Example-4] A 1-liter autoclave having squid-type blades was sufficiently replaced with nitrogen, and 100 g of Resin B was added to the autoclave.
3 ml of xylene and 500 of azobisisobutyronitrile
mg and 10 g of 2-hydroxyethyl methacrylate
Then, after stirring at room temperature for 1 hour at 50 rpm, 10
These were reacted by stirring at 0 ° C. for 2 hours at 100 rpm. The obtained polymer was dissolved in xylene, precipitated in methanol, filtered and dried.

The content of 2-hydroxyethyl methacrylate in the polymer obtained by drying was analyzed by IR spectroscopy, and it was found that 1.60 wt% of 2-hydroxyethyl methacrylate was grafted. [Example-5] The polymer was produced by the same method as in Example-1, except that the resin A was changed to the resin C and the maleic anhydride was changed to methyl methacrylate, and the graft amount was measured by the same method. did. As a result, 3.50 wt%
It was found that the methyl methacrylate of 1. was grafted. [Comparative Example-1] A polymer was produced in the same manner as in Example-1, except that the resin A was changed to TA8 (polypropylene powder MFR = 0.95 g / 10 minutes manufactured by Mitsubishi Petrochemical Co., Ltd.). The graft amount was measured by the same method. As a result, it was found that 0.15 wt% of maleic anhydride was grafted. [Comparative Example-2] Example-except that the resin A was changed to TA8.
The polymer was produced by the same method as in 2, and the graft amount was measured by the same method. As a result, it was found that maleic anhydride was not grafted. [Application Example-1] The modified polyolefin and the resin A obtained in Example 1 and the polyamide (nylon 6 manufactured by BASF, trade name Ultramid KR4411) were respectively used in a hydraulic press molding machine manufactured by Toyo Seiki Seisakusho 280
C., 240.degree. C., pressure molding is performed to form a sheet having a thickness of 2 mm, and then the sheet of the resin of Example-1 and the sheet of polyamide and the sheet of resin A and the polyamide of Example-1 are superposed so as to be bonded to each other with a width of 3 mm. , 50 kg / cm ² for 10 minutes to prepare a composite sheet. Using this as a test piece having a width of 1.5 cm and a length of 7 cm, a shear tensile test was conducted.

The shear tensile test was carried out by using Autograph AG1000A (trade name) manufactured by Shimadzu Corporation at a tensile speed of 3 mm / min. The results are shown in Table 1.

Table 1 Exam number (1) (2) Sample Combination Resin / Polyamide of Example-1 Resin A / Polyamide Shear tensile strength _{1.4 0.1} (kg / mm ² )

[0068]

Since the modified polyolefin according to the present invention can be obtained with a sufficiently high graft ratio or graft efficiency, it is highly possible to obtain a high modification effect by the introduction of a radical-polymerizable monomer. It has been described above in the "Summary of Invention" section.

Claims (1)

[Claims] 1. An unsaturated copolymer having a carbon-carbon double bond obtained by copolymerizing ethylene or α-olefin and a diene compound represented by the following general formula (I) or (II) The unit concentration based on the diene compound in the copolymer is 0.05 to 50 mol%) and 100 parts by weight of the radically polymerizable monomer in the absence of a solvent. Alternatively, in the presence of 30 parts by weight or less of a solvent, the monomer is polymerized by subjecting the monomer to a polymerization initiation condition generated by 0.001 to 10 parts by weight of a radical initiator. Manufacturing method. [Chemical 1] (Where m is an integer from ^{1 to} 10, R ¹ , R ² and R ³
Each represents hydrogen or a hydrocarbon group having up to 8 carbon atoms. ) [Chemical 2] (Here, R ⁴ represents a hydrocarbon group having 1 to 6 carbon atoms, R ⁵ represents hydrogen or a hydrocarbon group having 1 to 8 carbon atoms, and n represents an integer of 0 or 1.)