JPH03292304A - Production of terminal-modified olefin polymer - Google Patents

Abstract

PURPOSE:To obtain a terminal-modified olefin polymer desirable as a resin additive or a material for functional resins by polymerizing an olefin monomer in the presence of a transition metal compound catalyst, adding a specified compound to the polymerization system, and reacting it. CONSTITUTION:A monomer selected from among ethylene, a 3-20C alpha-olefin (e.g. propylene) and a nonconjugated linear or cyclic diene or polyene monomer (e.g. 1,4-hexadiene) is polymerized in the presence of a transition metal compound catalyst (e.g. TiCl4). A compound selected from among a compound having a group of formula I (e.g. ethylene oxide), a compound having a group of formula II (e.g. maleic anhydride) and a compound having a group of formula III (e.g. caprolactone) is added to the polymerization system and reacted to produce a terminal-modified olefin polymer. In the formulas, X<1>, X<2>, X<3>, X<4> and X<5> are each O, S or NR; X<6> is C=O, C=S, C=NR or CH2; R is hydrocarbyl; and n is 1-4.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing a terminal-modified olefin-based polymer and a terminal-modified olefin-based polymer.

More specifically, the present invention relates to a method for producing a terminal-modified olefin polymer that can be used as a resin additive, a functional resin raw material, etc., and a terminal-modified olefin polymer.

[Prior Art] Conventionally, methods for modifying olefin polymers include a method of oxidizing the olefin polymer, a method of grafting a vinyl compound onto the olefin polymer, and the like.

[Problems to be Solved by the Invention] However, in the prior art, no method of modifying only the terminals was known, and it was extremely difficult to synthesize, for example, a graft copolymer having a polyolefin in its side chain.

[Means for Solving the Problems] In order to solve the above problems, the present inventors conducted intensive studies on terminal-modified polyolefins, and as a result, they arrived at the present invention.

That is, the present invention involves polymerizing a monomer selected from the group consisting of ethylene, an α-olefin having 3 to 20 carbon atoms, and a linear or cyclic diene or polyene monomer having a nonconjugated double bond in the presence of a transition metal compound catalyst. After that, the general formula (wherein X1 is 0, S or NRI, and R1 is a hydrocarbon group) is added to the reaction system.
A compound having a group represented by the general formula C, X2, X3
, X4 is a group represented by 0, S or NR2, R2 is a hydrocarbon group), a compound having the general formula % (wherein n is 1 to 4, XI is O, S or NR", X6
is C=O1C=S, C=NR" or CH2, R3 is a hydrocarbon group). A method for producing a polymer, and a terminal-modified olefin polymer.

Specific examples of α-olefins having 3 to 20 carbon atoms include propylene, 1-butene, 1-pentene, 4-methyl-1
-pentene, 1-octene, 1-dodecene, 1-octadecene, 1-eicosene and the like. Specific examples of linear or cyclic diene or polyene monomers having non-conjugated double bonds include 1,4-hexadiene, 8
-Methyl-1,5-hebutadiene, cyclohebutane-1,4, dicyclopentadiene, 5-ethylidene-
Examples include 2-norbornene and methyltetrahydroindene.

The type of transition metal compound catalyst used in the present invention is not particularly limited, and any known catalyst system can be used.

Examples of transition metal compounds include vanadium compounds (vanadium tetrachloride, vanadium oxytrichloride, reaction products of these with alcohols (methanol, isopropyl alcohol, etc.), vanadium trisacetylacetonate, etc.);
Titanium compounds (titanium trichloride, titanium tetrachloride, reaction products of these with alcohol, etc.) and nickel compounds,
cobalt compounds, chromium compounds, zirconium compounds,
Examples include zinc compounds, E1)ium compounds, hafnium compounds, europium compounds, samarium compounds, and mixtures thereof.

Organoaluminum compounds are used as co-catalysts if necessary, and include diethylaluminum chloride, diisobutylaluminum bromide, ethylaluminum sesquichloride, ethylaluminum dichloride, and mixtures thereof. Further, a reaction product of an aluminum compound and alcohol or water can also be used. As catalyst activators, halogenated alkyl esters such as methyl trichloroacetate, aromatic esters such as methyl benzoate, and derivatives thereof can also be used.

Moreover, those catalyst systems treated with or supported by magnesium chloride compounds (magnesium chloride, magnesium hydroxychloride, etc.), silica, aluminas, and mixtures thereof can also be used. Among these, preferred combinations are vanadium compounds and organic aluminum compounds, or titanium compounds and aluminum compounds, specifically vanadium oxytrichloride and ethylaluminum sesquichloride, or titanium tetrachloride and triethylaluminum chloride. It is a magnesium carrier.

A hydrocarbon polymerization medium is usually used in the production of olefin polymers. The polymerization medium used is not particularly limited and can be varied depending on the monomer and catalyst, but commonly used hydrocarbons (hexane, heptane, kerosene, refined mineral oil, cyclohexane,
toluene, etc.) or halogenated hydrocarbons (chloroform, trichloroethylene, tetrachloroethane, 1.
2-dichloroethane, etc.). Moreover, it can also be carried out using a raw material monomer as a medium. Preferred among these polymerization media are heptane and toluene.

The amount of the catalyst used varies depending on the composition and molecular weight of the target terminal-modified olefin polymer, but the amount of the transition metal compound used per medium IL is usually 0. OO1=
100 m-ol, preferably 0゜1~lQ+s
It is mol. The amount of the organoaluminum compound used is usually 0 to 100 times, preferably 1 to 30 times, per mole of the transition metal compound.

The polymerization temperature can be varied within a wide range, but is usually -70°C.
℃~200℃, especially preferably in the range of -30℃~80℃.

Polymerization is carried out at atmospheric pressure or under increased pressure, with 1 to 10
It is preferable to carry out at 0 kg/am”, especially 1 to 3
Preferably it is between 0 kg and 0 kg.

The molecular weight of the obtained olefin polymer is not particularly limited, and usually has a number average molecular weight of several hundred to several million, depending on its use.

In general formulas (1), (2), (3), R1, R
Examples of the hydrocarbon group represented by 2 and R3 include alkyl groups having 1 to 4 carbon atoms (methyl, ethyl, isopropyl, butyl groups, etc.) and substituted hydrocarbon groups (halogen-substituted hydrocarbon groups, etc.).

Examples of compounds that grow groups represented by general formula (1) include alkylene oxides (ethylene oxide, propylene oxide, phenylene oxide, octene oxide).
1, etc.), epichlorohydrin, glycidyl compounds and their derivatives (glycidyl (meth)acrylate, polyalkylene glycol diglycidyl ethers, polyesters, polyamides, etc.), glycidyl (meth)acrylate and vinyl monomers (methyl methacrylate, alkyl methacrylate, styrene, (meth)acrylonitrile, acrylamide, butadiene, etc.), ethylene sulfide and its derivatives, N-substituted ethyleneimine (N-methylethyleneimine, N-(N', Nゝ-dimethylamino), ethylethyleneimine, etc.) and derivatives thereof.

Examples of compounds having a group represented by general formula (2) include maleic anhydride and its derivatives, dithiomaleic anhydride and its derivatives, N-substituted maleic acid imide and its derivatives, and the like.

Examples of compounds that support the group represented by general formula (3) include tetrahydrofuran, caprolactone and its derivatives, N-substituted caprolactam and its derivatives, N-substituted -
Examples include 2-pyrrolidone.

The amount of compound added after polymerization of the monomers is determined by the general formula (
Although it can be varied depending on the content of the groups represented by 1) to (3) or the structure of the desired end-modified polymer, the amount of general formula (1) per mol of the transition metal compound used in the polymerization is The amount of groups represented by ~(3) is usually 0.
001 to 10oooo times the mole, preferably 0. 1~
The amount is 1000 times the molar amount.

The terminal-modified olefin polymer can be obtained by adding a compound to a monomer polymerization reaction system and reacting it, and the reaction temperature and pressure may be the same as or different from the monomer polymerization conditions. The reaction time varies depending on the viscosity of the system, but is usually 1 minute to 50 hours, preferably 0.5 hours. 5
~2 hours.

The compound can be added to the polymerization reaction system after being diluted with a solvent or without being diluted, and examples of the solvent include the above-mentioned polymerization medium. In particular, it is preferable to dilute it with the same solvent as the polymerization medium used in the polymerization, or add it without diluting it.

The terminal-modified olefin polymer in the present invention is terminal-modified polyethylene when ethylene is selected as the monomer. When propylene is selected as the monomer, it is a terminally modified polypropylene, and when another α-olefin is selected, it is a terminally modified polyα-olefin. In addition, when ethylene and propylene are selected as the seven polymers, it is terminally modified EPM, and when linear or cyclic diene or polyene monomers with non-conjugated double bonds are added, terminally modified EPDM It is.

[Example] Hereinafter, the present invention will be further explained with reference to Examples, but the present invention is not limited thereto.

Example 1 A 2L separable flask was equipped with a stirrer, a thermometer, a dropping funnel, and a reflux condenser, and the flask was dried under reduced pressure and heated, and then replaced with nitrogen. Pour purified and dried normal hexane IL into this flask, keep it at a constant temperature of 30°C, and add 10 L of a mixed gas of 40 mol% ethylene and 60 mol% propylene to this flask.
It was saturated by flowing at a rate of 30 minutes. Then, 0.0% vanadium oxytrichloride was added. 8 mmol and 3.2-ol of ethylaluminum sesquichloride were added into the flask to initiate ethylene/propylene copolymerization.

Further, a mixed gas of ethylene and propylene was flowed for 10 minutes while stirring to perform polymerization. Stop the mixed gas supply,
After cooling to 0° C., 5 g of styrene oxide was added from the dropping funnel and stirred for 30 minutes.

Next, after adding 30 g of methanol, the reaction mixture was poured into a large amount of methanol to precipitate a copolymer. The precipitate was purified by rubber membrane dialysis with petroleum ether to obtain a terminal-modified polyolefin polymer as a white amorphous solid. The intrinsic viscosity of this polymer is 0. 94dl/w
in (30° C., toluene solution), the molar ratio of ethylene/propylene was 60/40, and the presence of a benzene ring derived from styrene was confirmed by IRl NMR.

Example 2 Toluene was used instead of normal hexane, and 50w of glycidyl methacrylate-methyl methacrylate copolymer (glycidyl methacrylate content 10 wt%, weight average molecular weight 10000) was used instead of styrene oxide.
The same procedure as in Example 1 was carried out except that 20 g of t% toluene solution was added.

The intrinsic viscosity of the obtained white solid was 1. 2 dl/i+I
n (30° C., toluene solution), ethylene/propylene molar ratio: 80/40, and the presence of a glycidyl methacrylate-methyl methacrylate copolymer segment was confirmed by IRl NMR.

Example 3 After saturated by flowing a mixed gas of 40 mol% ethylene and 60 mol% propylene at a rate of 10 L/min for 30 minutes, 5 g of ethylidene norbornene was added, and 50 w of glycidyl methacrylate-methyl methacrylate copolymer was added.
50w of maleic anhydride instead of t% toluene solution
The same procedure as in Example 2 was carried out except that 2 g of t% toluene solution was added.

The intrinsic viscosity of the obtained white amorphous solid is 0.90 dl/m
ln (30°C, toluene solution), ethylene/propylene/ethylidene norbornene molar ratio: 58/38/4
The presence of COCH=CH-COOH derived from maleic anhydride was confirmed by IR and NMR.

Example 4 The same procedure as Example 3 was carried out except that N-methylcaprolactam was used instead of maleic anhydride.

The intrinsic viscosity of the obtained white amorphous solid is 0.98 dl/w
(30° C., toluene solution), the molar ratio of ethylene/propylene was E34/44, and the presence of -COCH2CH2CH2N HCH3 derived from N-methylcaprolactam was confirmed by IRlNMR.

Example 5 1. After drying the SL autoclave and purging with nitrogen, 0.
5 L of purified and dried normal hexane was added, and a catalyst prepared from separately prepared titanium tetrachloride and magnesium hydroxychloride (containing 13 mg of Ti per Ig)74
1 mg of triethylaluminum and 67 mg of triethylaluminum in hexane suspension (20 ml of hexane). Here, 25
After adding 0 g of ethylene, the mixture was reacted at 50° C. for 5 hours. Next, 100 g of polyethylene glycol diglycidyl ether (number average molecular weight 2000) was press-fitted and stirred for 1 hour. After purging unreacted ethylene, the reaction suspension was poured into a large amount of methanol, washed with stirring, and then the polymer was separated. The precipitate was purified by extraction with isopropyl alfur to obtain a white solid. The intrinsic viscosity of this polymer at 140°C is 0.3 L/g,
IR.

The presence of polyethylene glycol segments was confirmed by NMR.

[Effects of the Invention] By the production method of the present invention, terminal-modified olefin polymers having various properties can be synthesized. The terminal-modified olefin polymer of the present invention is not conventional and is effective as a synthetic raw material for new resins and graft copolymers having polyolefins in their side chains.

Claims (1)

[Scope of Claims] 1. In the presence of a transition metal compound catalyst, ethylene with 3 to 3 carbon atoms
There are polymerized monomers selected from the group consisting of 20 α-olefins and linear or cyclic diene or polyene monomers having non-conjugated double bonds, and general formulas ▲ mathematical formulas, chemical formulas, tables, etc. ▼ (1 ) (In the formula, X^1 is O, S or NR^1, R^1 is a hydrocarbon group) Compounds having a group represented by the general formula ▲ Numerical formula, chemical formula, table, etc. Medium X^2, X^3, X^4 are O, S or NR^
2, R^2 is a hydrocarbon group), and general formulas ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (3) (In the formula, n is 1 to 4, X^5 is O , S or NR^3,
X^6 is C=O, C=S, C=NR^3 or CH_2
, R^3 is a hydrocarbon group),
A method for producing a terminal-modified olefin polymer, the method comprising reacting a compound selected from the group consisting of: 2. In the presence of a transition metal compound catalyst, ethylene, carbon number 3-
After polymerizing one or more monomers selected from the group consisting of 20 α-olefins and linear or cyclic diene or polyene monomers having non-conjugated double bonds, the reaction system is added with the general formula ▲mathematical formula, chemical formula, There are tables, etc. ▼ (1) Compounds having a group represented by (in the formula, X^1 is O, S or NR^1, R^1 is a hydrocarbon group), general formula ▲ Numerical formula, chemical formula, table, etc. Yes▼(2) (In the formula, X^2, X^3, and X^4 are O, S, or NR^
2, R^2 is a hydrocarbon group), and general formulas ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (3) (In the formula, n is 1 to 4, X^5 is O , S or NR^3, X^6 is C=O, C=S, C=NR^3, or CH_2, R^3 is a hydrocarbon group). A method for producing a terminal-modified olefin polymer, which comprises adding and reacting a compound selected from among the above. 3. The manufacturing method according to claim 1 or 2, wherein the transition metal compound catalyst is a combination of a vanadium compound and an organoaluminium compound. 4. The terminal end of the polymer of a monomer selected from the group consisting of ethylene, an α-olefin having 3 to 20 carbon atoms, and a linear or cyclic diene or polyene monomer having a non-conjugated double bond has the general formula ▲ mathematical formula, chemical formula , tables, etc. ▼(1) Compounds having a group represented by (in the formula, X^1 is O, S or NR^1, R^1 is a hydrocarbon group), and general formulas ▲ Numerical formula, chemical formula, There are tables, etc.▼(2) (In the formula, X^2, X^3, and X^4 are O, S, or NR^
2, R^2 is a hydrocarbon group), and general formulas ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (3) (In the formula, n is 1 to 4, X^5 is O , S or NR^3,
X^8 is C=O, C=S, C=NR^3 or CH_2
, R^3 is a hydrocarbon group).