CA2050273A1 - Both ends-modified olefin polymers and processes for the production thereof - Google Patents

Abstract

TITLE OF THE INVENTION
Both ends-modlfied olefin polymers and processes for the production thereof ABSTRACT OF THE DISCLOSURE
Polymers of olefins such as ethylene and propylene, having functional groups Introduced into both-the ends thereof, can be provided which are useful as macromonomers for polycondensation. This new polymer comprises a recurring unit represented by the general formula -( - CH,- CHR -) - and having functional groups bonded to both the ends of the polymer and a number average molecular weight of 300 to 500,000, the functional groups being selected from the group consisting of H2C=CH- group and group wherein X is -OH, -OR', a halogen atom or -SO3R2, R1 is a hydrocarbon group of 1 to 5 carbon atoms and R2 is a halogen-substituted or non-substituted hydrocarbon group of 1 to 20 carbon atoms.

TS-718(719)

Description

~ 20~73 B~CKGROUND OF TIIE INVENTION
1. ~leld of the Invention This invention relates to ethylene or propylene polymers each having functional gl'OUpS such as vinyl groups or carbonyl groups at both the ends thereof, and a process for the production of the same.

2. Description of the Prior Art An ethylene polymer having a functional group introduced into one end of the polymer obtained by living anion polymerization of ethylene has been known, but an ethylene polymer having functional groups introduced into both the ends thereof has not been known.
Moreover, a method comprising polymerizing propylene using a polymeriza-tion catalyst consisting of a vanadium chelate compound and a dialkylaluminum halide and modifying the end of the resulting polypropylene with a functional group has been known, but only one end of the polymer can be modified by the prlor art method.
If functional groups can be Introduced into both the ends o~ polymers of oleflns such as ethylene, propylene, etc., broad appllcations thereof can be expected to ~Ises, e.g. macromonmomers of polycondensation.
SUMMARY O~ TIIE INVENTION
It is an object of the present inventlon to provide an ethylene polymer having functional groups introduced into both the ends thereof.
It is another object of the present invention to provide an olefin polymer having vinyl groups introduced at both the ends thereof to be a precursor of the polymer having oxy groups or their derivatives introduced at both the ends thereof.
It is a further object of the present invention to provide a process for the production of an ethylene or propylene polymer into both the ends of which vinyl groups or carbonyl groups are introduced.
These objects can be attained by an olefin polymer comprising a recurring unit represented by the general formula -( - CHz CIIR -) - and having --' 2~273 unctlonal groups bonded to both the ends of the polymer and a number average molecular welght o~ 300 to 500,000, the functional groups being selected from O
the group consisting of ~2C=CH- group and X-C- group wherein X is -OH, -ORl, a halogen atom or -S03Ra, R' is a hydrocarbon group of l to 5 carbon atoms and R2 is a halogen-substituted or non-substituted hydrocarbon group of l to 20 carbon atoms.
DETAILED DESCRIPTION OF THE INVENTION
The inventors have made various efforts to provide an olefin polymer having functional groups bonded to both the ends of the polymer and conse-quently, have found that an ethylene polymer having carbonyl groups intro-duced at both the ends thereof is obtained by polymerizing ethylene using a polymeri~ation initiator consisting of a reaction product of an ~ , ~ '-diolefincompound and an organic lithium compound and a specified amine compound and then reacting with carbon dioxide, and that an olefin polymer having function-al groups bonded to both the ends of the poly~ler can be synthesized by poly-merizing ethylene or propylene in the presence of a reactlon product of a poly-merization catalyst consisting of a vanadium chelate compound and a dialkyl-aluminum halide with an a, ~ -diolefln compound, nnd then reacting the pro-duct with the diolefin compound.
Accordingly, the present invention provides (I) an ethylene polymer com-oprising recurring units of -( - Cl12 CH2 -) - and having X-C- group bonded at both the ends thereof and a number average molecular weight of 300 to 300,000, wherein X represents -OH, -OR', a halogen atom or -SO3R2, R' repre-sents a hydrocarbon group containing 1 to 5 carbon atoms and R2 represents a halogen atom-substituted or non-substitut hydrocarbon group containing 1 to 20 carbon atoms, (2) an olefin polymer comprising recurring units represented by the general formula -~ - CH2 CHR -) - and having H2C=CH- group bonded at both the ends thereof and a number average molecular weight of 300 to 500,000, 2~0273 ~ reirl R is a hydrogen atom or methyl group, (3) a process for the production of the ethylene polymer as described in the above described (1), whicll comprises polymerizing ethylene in the presence of a dilithio compound formed by the reaction of a diolefin compound (I) represented by the general formula }1~ C=CR3 -R~ -CR3 =CI12 wherein R9 represents a hydrocarbon group containing 1 to 10 carbon atoms and R' represents a divalent hydrocarbon group containing 1 to 20 carbon atoms witll (II) an organolithium compound, and (III) a diamine compound represented by the general formula R2aN-R7-NR28 wherein R~ represents a hydrocarbon group containing 1 to 5 carbon atoms and R7 represents a divalent hydrocarbon group containing 1 to 10 carbon atoms, then reacting with carbon dioxide and with a proton donor or sulfonyl halide representecl by the gen-eral formula ZS02R2 wherein Z represents a halogen atom and R2 have the same meaning as described above~ (4) a process for the production of the ethylene polymer as described In the above described (1), which comprises polymerizing ethylene in the presence of a dilithio compound formed by the renction of a diolefin compound (I) represented by the general formula 112C=CR3~R~~CR3=Clla wllereln R3 represents a hy(lrocnrbon group containlng 1 to 10 carbon atoms and R4 represents a dlvalent hytlrocarbon group contalning 1 to 20 carbon atoms with (II) an organollthlllln compound, and (III) a dlnmlne compound rep~esented by the general formula R2N-R7-NR2~ wherein R~ represents a hydrocarbon group containing 1 to 5 carbon atoms and R' represents a divalent hydrocarbon group containing 1 to 10 carbon atoms, then reacting with carbon dio~ide, then with a proton donor and then witll an alcohol represented by the general formula R1011 wherein R' have the same meaning, or a thionyl halide, in particular, X be-ing -ORI or a halogen atom, and (5) a process for the production of an olefin polymer as described in the above described (2), which comprises polymerizing ethylene or propylene in the presence of a reaction product of a polymerization catalyst consisting of a vanadium chelate compound and a dialkylaluminum halide represented by the general formula Rl'2AlX wherein Rl'is an alkyl group contain-ing 1 to 20 carbon atoms and X' is a halogen atom with ana , ~ -diolefin com-2~5~7~
aund represented by the general formula H2C=CH -( - C ~ 112~ -) - CH=CH2 wherein m is l to 15, and then reacting with the diolefin compound and with a proton donor.
The olefin polymer of the present invention, as represented above, in-cludes ethylene polymers when R is hydrogen atom and propylene polymers when R is methyl group, and generally has a number average ~olecualr weight (Mn) 300 to 500,000, preferably 500 to 200,000.
In particular, the ethylene polymer of the present invention can be re-presented above, in which X is -OH, -ORI, a halogen atom or -SO3R2. R' in -OR' is a hydrocarbon group containing l to 5 carbon atoms, preferably an alkyl gr~up, more preferably methyl or ethyl group. The halogen atom includes chlo-rine, bromine, fluorine and iodine. R2 in -SO3R2 is a hydrocarbon atom con-taining l to 20 carbon atoms, specifically an alkyl group, alkenyl group, cyclo-alkyl group, aryl group or aralkyl group each containing l to 20 carbon atoms.
Above all, aryl groups and aralkyl groups are 1prei!erable and R' can be com-bined with an halogen atom such as chlorine, bromine, iodine or fluorine.
Examples of -SO3R are as follows:
~13C
-SO ~ , -SO~- ~ -C113, -S03- ~ -C~

Cl <~
-SO~3 -<~ -Cl, -S03 - ~ , -S03 - ~

X is preferably -OH, -OCH3, -OC2H5, -Cl or -SOa-~, more preferably -OH or -OCH3.
The ethylene polymer of the present invention has a number average mole-cular weight (Mn) of 300 to 300,000, preferably 600 to 150,000.
Preparation of Olefin Polymers 7 ~
(l) Reaction of Polymerization Catalyst with Diolefin Compound ri'he polymerization catnlyst consists of a vanadium chelate compound and a dlalkylaluminum hallde. The vanadlum chelate compound is represented by the following general formula:
... . , . . . , ~ ..

) ~

In this general formula, R2' to R4' represent hydrogen atoms or hydrocarbon groups of l to 8 carbon atoms, but at least one of R2' to R4' must be hydrogen atom and all of R2' to R4' must not be hydrogen atom.

Specific examples of the compound included in the above described general formula will now be illustrated.

Case where R3' is a hydrogen atom and R2' and R4' are hydrocarbon groups:

R2'/R4': Cil3/CH3, CH3/C211~, C2 115 /C2 H5, Cl13~C311s, C2 lls/C811~, C8H~/C811s CH3 /C3H3CH2, C3115CI12/C811sCH2, Ca H!) /C8H5CH2, C8115/CoHsCi12 Case where R3' is a hydrocarbon group and one of R2' and R4' is a hydrogen atom and the other is a hydrocarbon group:

R3' /Ra' or R4':CI13/CI13, Calls/CI13, Cl13 /Ca 115, C2 115 /Calls, C311~/CH3, Cl13/C8H5, C0H5/C2Hs~ C2Hs/C3Hs, C811s/C8Hs, Ca HsCH2/CH3, CH3/C8HsCH2, C9 HsC}12/C8HsCHz, C8}1sCH2/C2Hs C2Hs/C8H5CH2, C~H5CI12/C8Hs. C8115/C8HsCH2 Case where R3' Is a hydrogen atom and one of RZ' and R~' is a hydrogen atom and the other is a hydrocarbon group:

R2' or R4': CH3, C2Hs, C~H5, C~H5CH2 Above all, the following compounds are preferable.

( 119C C~C\ Cil~

.

- ~ .
' ~ ` ~ ''`,"

`' ~ .

V(acetylacetonato) 3 CH~

C/t " ~ ~1 ) V(2-methyl-1,3-butanedionato)9 , .

C ~ C~

V(1,3-butanedlonato)~

Examples of the dlalkylalumlnum hallde represented by the foregoinng ~eneral formula are dlmethylaluminum chloride, ~dlethylaluminum chloride, diethylaluminum bromlde, diethylaluminum iodlde, dlisobutylalumlnum chlorlde nnd the like.
The proportlon of the vanadium chelate compound and dlalkylaluminum halide used is generally 1 to 1,000 moles of the dialkylaluminum hallde per 1 mole of the vanadlum chelate compound.
The a, ~-diolefin compound Is represented by the general formula, H2C=CH - ( ~ C m H2m - ) ~ CH=CH2 where m Is 1 to 15.
Examples of the diolefin compound are 1,4-pentadlene, 1,5-hexadiene, 1,6-heptadiene, 1~7-octadiene~ 1,8-nonadiene, 1,9-decadiene, 1,10-undecadiene, 1,11-dodecadiene, 1,13-tetradecadiene, 1,15-hexadecadiene, 1,17-octadecadiene and the like.
The reaction of the polymeri~atlon catalyst with the diolefin compound 2 ~
i Ireferably carried out in a solvent being inert to the reaction and liquid durlng the reaction, illustrative of which are hydrocarbons such as propane, butane, pentane, hexane, heptane, toluene, etc.
The reaction is carried out at a temperature o~ -50 C or lower~ prefer-ably -65 C or lower for a period of time of 1 minute to 10 hours, preferably 5 minutes to 2 hours. The reaction proprotion of the polymerization catalyst and diolefin compound is controlled in such a manner that the vanadium com-pound in the polymerization catalyst is present in a proportion of 0.1 to 10 moles, preferably 0.5 to 2.0 moles per 1 mole of the diolefin compound.
(2) Polymerization of Olefins The polymerization of oleflns, in particular, ethylene or propylene is carried out in the presence of the reaction product obtained in the aboYe des-cribed (1), preferably by feeding ethylene or propylene to the reaction sys-tem of the above described (1) and effecting the reaction at a temperature range similar to the above described (1) for a longer time than in the case of the above desclrbe(i (1). When the reactlon temperature is ndjusted to -65 C or lower, in partlcular, there can be obtained a polymer having a Mw (weight average molecular weigllt)/Mn (number average molecular Neight) of 1.05 to 1.5, near the monodlsperse system. Furthermore, the yield and mole-cular welght of the polymer cnn be Incrensecl by lengthenlng the polymerization time.

(3) Reaction with Diolefin Compound The reaction of the renction product of the above described (2) with the diolefin compound is preferably carrled out by feeding the diolefin compound to the reaction system of the above described (2) and effecting the reaction under the simialr reaction conditions to those of the above described (1).

(4) Reaction with Proton Donor As the proton donor, there can be used water, alcohols, inorganic acids, etc. The alcohols include methanol, ethanol, propanol and the like and the inorganic acids include hydrochloric acid, nitric acid, sulfuric acid, and the ~\
2~2~
I ~. The use of the proton donor functions to release the polymerization catalyst an~ give proton through action on the ends of the polymer, thereby precipitating the polymer.
The rea~tion with the proton donor is generally carried out at a temper-ature of -100 C to 200 C, preferably 0 to 150 C for 1 minute to 10 hours, preferably 0.1 to 2 hours. The proton donor ia ordinarily used in a largely e,ccessive amount.
Thus, the olefin polymer of the present invention can be produced and it can be assumed that the polymer has the following microstructure containing the skeleton of the diolefin compound and the alkyl group R" of the diallcyl-alumlnum hallde, used in the production, because of adopting the above des-cribed production process.
A -( - CHz CHR - ) n - B
in which A and B are described below and n is an integer corresponding to the number average molecular weight:
A B
(~) H3 C-CH- -Clla -CII-RI ~
Cm ila m Cm lla m llaC =CII Cll=C112 (~) CHa -Clla --CHa -CII-RI ~
Cm H2 m Cm 112 m H2 C =CH Cll=Cllz (~) H3C-Cli- -Cll-CI12-R~
Cm 112 m Cm il2 m Ha C =Cil Cll=CHz CHz -Clla~ -CH2-CH-R"
Cm 1l2 m Cm ~Iz m 2~S~2 J'3 112C -Cll CII=CII, 113C-CII- -CH-(CI12)3-R"
C~ H2~ C~-2H2~-2, H2C =CH CH=CH2 CH2-CH2- - -CH-(CH2)3-RI' :
IC~ H2~ C~-2H~-2, H2C =CH CH=CH2 The olefin polymer of the present invention is then reacted with diborane and then with an alkali metal hydroxide and hydrogen peroxide to obtain a poly-mer hydroxylated at both the ends (-CH2-C1120H).
A polymer having hydroxyl groups introduced at ~ -position of both the ends thereof (-CH-CH3) can be obtained by reacting the olefin polymer of the 0~1 present invention wlth sulfuric acid and water, or by reacting the same with mercuric acetate and water and then with sodlum borohydride (NaBII,).
~ urthermore, the polymer hydroxylated in this way is reacted wlth a silane compound represented by the general formula, R~'3SiY in which R5 is a hydrocarbon group containing 1 to 5 carbon atoms and Y Is a halogen atom, to silyloxylate both the ends thereof [-CH2-Cll~OSiR~'3 or -Cll(O~iR~'3)-CI13], or is rencted wlth 8 carboxyllc acid represented by the general formula, R~'COOH in which R~' is analkyl group containing 1 to 5 carbon atoms, to esterify both the ends thereof [-CH2-CH20-C-R~' or -CH(Q-C-Ri')-CH9].
/~ 11 .
O O
The hydroxylation, silyloxylation and esterification reactions of the polymer of the present inYention wlll now be illustrated:

(5) Reaction wlth diborane The reaction of the olefin polymer of the present invention with diborane is ~rdinarily carried out at 100 to 200 ~c for 1 minute to 10 hours preferably in the presence of a solvent such as ethers. As the ether, there are prefer-~ ~ .

2~0273 D ' llSe(l those having a boiling point of at least tO0 ~C, for exnmple, ali-phatic ethers such as di-n-butyl ether, di-s-butyl ether, di-n-amyl ether, di-i-amyl ether and the like.
The diborane is ordlnarily used in the form of a solution in tetrahydro-furan in a proportion of 0.2 to 100 moles, preferably 0.5 to 20 moles to 1 mole of the whole amount of the diolefin compounds used in the foregoing (1) and (3). (6) Reaction with alkali metal hydroxide and hydrogen peroxide The reaction with an alkali metal hydroxide and hydrogen peroxide is gen-erally carried out at 0 to 100c for 1 hour to 1 week. ~s the alkali metal oxide, there are generally used sodium hydroxide and potassium hydroxide, in general, in the form of aqueous solutions. The hydrogen peroxide is ordinarily used as its aqueous solution.
The alkali metal hydroxide and hydrogen peroxide are ordinarily used in excessive amounts, but It is sufficient to use them respectively in an amount of at !east equimole to the dlborane used in the foregoing (5).
Thus, the olefin polymer of the present invention can be obtained whose both ends are hydroxylated.
(7) Reactioll with sul~ullc acld and water The reactlon of the polymer of the present ,Inventiorl wlth sul~urlc acld and water Is ordinarily carrled out In the presence of water or a mlxture of water and ether at 80 to 150 C for 1 minute to 10 hours.
(8) Reaction with mercuric acetate and water The reaction of the polymer o~ the present invention with mercuric acetate and water is ordinflrily carried out In the presence of a mixture of water and ether at 80 to lS0 C for 1 minute to 10 hours.
(9) Reaction with sodium borohydride The reaction of the product obtained in the ~oregoing (8) with sodium borohydride can be carried out in the similar manner to the reaction method of (8).
(10) Reaction with silane compound and carboxylic acid 3 s~ ~ ~
The silane compound used is represented by the general formula, R53SiY in which R5 ls a hydrocarbon group containing I to 5 carbon atoms, preferably methyl or ethyl group and Y is a halogen atom such as chlorine, bromine, fluo-rine or iodine.
The carboxyllc acid is represented by the general formula, R3COOH in which R is a hydrocarbon group containing l to 5 carbon atoms, preferably methyl or ethyl group.
The reaction of the dihydroxypolyolefin obtained in the foregoing (6), (7) or (9) with a silane compound or carboxylic acid can be carried out by the commonly used method in the case of trialkylsilylating or esterificating an alcohol.
For example. the reaction with the silane compound is ordinarily carried out initially at O to 50 Dc for 1 minute to 5 hours and further at lOO to 150 ~c for l to lO hours, preferably in the presence of a solvent such as amine compounds. As the amine compound, there are most preferably used those havlng a boiling point of at least 100 ~C .
The esterification reaction can be conducted with either a carboxylic acid alone or in comblnation with a small amount of concentrtaed sulfurlc acid or dried hydrogen chlorl(le. Furthermore, a carboxyllc halide can be used instead of the carboxyllc acld.
The amount of the silane compound or carboxylic acld used is preferably at least 2 times by mole as much as the foregoing olefin polymer havin~ hydroxylgroups at both the ends thereof.
Preparation of Ethylene Pol~mers (1) Reaction of Dlolefin Compound (I) with Organolithium Compound The diolefin compound is represented by the general formula, 112C=CR3-R~-CR3=CH2. In this formula, R3 is a hydrocarbon group containing l to lO carbon atoms, illustrative of which are alkyl, cycloalkyl, aryl and aralkyl groups, preferably alkyl and aryl groups. Examples thereof are alkyl groups such as methyl, ethyl, propyl, butyl, hexyl groups, etc. and aryl groups such as 2~2~3 ,t lyl, tolyl, xylyl groups, etc.
R~ is n divalent llydrocarbon group containing 1 to 20 carbon atoms, for example, substituents such as ( - C~12 ~ wherein m = 1 to 12 and - (O > -( - Cil2 - ) ~ - ~> - wherein r = 1 to 6.
Examples of the compound (I) are 2,5-dimethyl-1,5-hexadiene, 2,5-diphenyl-1,5-hexadiene, 2,6-diphenyl-1,6-heptadiene, 2,7-diphenyl-1,7-octadiene, 2,7-dimethyl-1,7-octadiene, 1,2-bis[4-(1-phenylvinyl)phenyl]ethane, 1,4-bis[4 -(1-phenylvinyl)phenyl]butane, 1,2-bis(isopropenyl-4-phenyl)ethane, 1,2-bis(isopropenyl-4-phenyl)butane and the llke.
The organolithium compound (II) is a compound represented by the general formula R5Li, in which R5 is a hydrocarbon group containing 1 to 10 carbon atoms, preferably alkyl groups and aryl groups, more preferably alkyl groups.
As the compound (:[I), for example, there are used methyllithiium, ethyl-lithium, n-propyllithium, l-propylllthium, n-butyllithium, i-butyllithium, s-butyllithi~lm, t-butyllithium, n-pentyllithlum, hexyllithium ancl the lilce.
The reaction o~ the compound (I) and the colnpound (Il) is prererably car-ried out in the presence of an organic solvent. As the organic solvent, there are pre~erably used hydrocarbons, In pnrticular, nliphntic hy(lrocarbons such asheptane, hexane and the lllce and aromatic hytlrocarbons such as benzelle, toluene and the like. Two or more organlc solvents can be used.
The compound (I) and the compound (II) are used in a (II)/(I~ molar ratio of 0.1 to 30, preferably 1 to 5. Both the compounds are reacted at -50 C to +100 C, preferably 0 to 50 C for 1 hour to 1 month, preferably 1 day to 10 days.
(2) Polymerization of Ethylene The polymerization of ethylene is carried out in the presence of a di-lithio compound formed by the reaction of the compounds (I) and (II) as des-cribed in the above described (l) and a diamine compound (III).
The diamine compound (III) is represented by the general formula, 2~5~2~3 ~ ~-R7-NR2~ wherein R~ is a hydrocarbon group of t to 5 carbon atoms, prefer-nbly alkyl group, illustrative of which are methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, n-pentyl and the like, methyl group being particularly preferable, and R7 is a divalent hydrocarbon group of 1 to lO
carbon atoms, preferably a divalent hydrocarbon group represented by the gen-eral formula -C 1 112~ - wherein t = 1 to 10.
Examples of the compound (III) are tetramethylethylenediamine, tetra-methylpropylenediamine, tetramethyldiaminobutane, tetramethyldiaminopentane, tetramethyldiaminohexane, tetraethylenediamine and the like.
The polymerization of ethylene is preferably carried out in the presence Or a solvent such as hydrocarbons, more preferably aromatic hydrocarbons such as benzene, toluene, xylene and the like.
The ratio of the dilithio compound and diamine compound (III) used is 0.1 to 20 moles, preferably 0.5 to 4 moles of the diamine compound (III) to 1 mole o~ the diolefin compound (I).
1`he polymerization of ethylene ls generally carrled out at fl telllperntUre of -100 C to +100 ~C, preferably -30 C to -~30 C for 1 hour to l month, preferably 10 hours to 1 week.
(3) Reaction with carbon dioxide Tlle reactlon Or the ethylene polymer fornle(l In the above descrlbed (2) with carbon dloxlde is generally carried out by feeding carbon dioxide to the reaction system of the above described (2) and bringing into contact with the polymer. The carbon dioxide is present in a proportion of 0.1 to 10,000 moles, preferably 2 to lO0 moles to 1 mole of the diolefin compound (I). The carbon dioxide can be fed in the form of a mixture containing carbon dioxide.
The reaction is generally carried out by feeding carbon dioxide at a re-latively low temperatrue, i.e. -150 C to *50 C, preferably -100 C to 0 C
and then contacting them at a temperature of -50 C to *100 C, preferably 0 to 50 c for 0.1 to 100 hours, preferably 1 to 10 hours, for example, by employing stirring means, etc.

2 7 ~
(~) Reaction wlth proton donor or sulfonyl hallde As the proton donor, there can be used water, alcohols, Inorganic acids, etc. The alcohols include methanol, ethanol, propanol and the like and the inorganic acids include hydrochloric acid, nitric acid, sulfuric acid, and the like.
The sulfonyl halide is represented by the general formula, ZS02R2 in which Z is a halogen atom such as chlorine, bromlne, fluorlne or iodine. R2 in this formula have the same meaning as R2 in a case where the substituent X of the foregoing ethylene polymer is -SO3R2. Therefore, as an example of the sulfonyl halide, there is such a compound that Z, i.e. a halogen atom is bonded to the above described -SOiR2.
The reaction with the proton donor or sulfonyl halide is generally carried out at -100 C to +200 C, preferably O to 150 C for 1 minute to 10 hours, preferably 0.1 to 2 hours. O
The ethylene polymer of the present Invention, in which -C-OH groups are introduced into both the ends thereof, Is obtaine~ by the reaction with the Il proton donor and that havlng -C-SO3R' groups introduced into both the ends thereof is obtalned by the reactlon with the sulfonyl halide.
(5) Reactlon wlth alcohol or thlonyl halide The alcohol to be used is represented by the general formula, R'OH in which R' has the same meaning as described above. Thus, the particularly pre-ferable alcohol is methanol or ethanol. As the thionyl halide, there can be used SOC12, SO2C12, SOBr2, SOI2, SO2Br2, SO2I2 and the like.
The reaction with the alcohol or thionyl halide is generally carried out at -50 C to ~200 C, praferably 50 to 150 C for 1 minute to 1 week, prefer-ably 1 hour to 1 day; The alcohol can either be used individually or in the form of an alcohol complex such as methanol BF, complex.
o The ethylene polymers of the present invention, in which -C-OR' groups 2 ~ 7 3 and C-OX groups (X is a halogen atom) are respectively introduced into both theends thereof, can be produced by reacting the product, obtained by reaction with the proton donor in the above described (4), respectively with the alcohol and with the thionyl halide.
It can be assumed that the polymer of the present invention, obtained in this way, has the following microstructure containing the skeleton of the di-olefin compound and the substituent Rs of the organolithium compound used in the production, because of adopting the above described production process.
XC -( - Cl12- Cll -)~- A -( - C112- C~l -) n~ CX
Il ~
O O
In the above described formula, A is represented as follows, and (m + n) is an integer corresponding to the number average molecular weight:

R3 R9 R3 R3 R3 R~
-C-R4-C- -Cl12-C-R4-C-CI12- or-Cll~-C-R4-C-Cl12 C112 R3 RG R C~12 R~ RD R~

Accordlng to the process of the present inventlon, It ls rendered possi-ble to produce an olefin polymer whose both ends are modifled with vinyl group and rom the polymer of the present invnetion can readlly be produced an olein polymer whose both ends are modlfied with hydroxyl group or its substitued group.
This olefin polymer modified with hydroxyl groups can widely be used as macromonomers for polycondensation~
In addition, according to the process of the present invention, it is rendered possible to produce an ethylene polymer whose both ends are modified with a functional group having at least carbonyl group.

The ethylene polymer of the present invention, having the functional groups at both the ends thereof, can widely be used as macromonomers or poly-condensation.
The following examples are given in order to illustrate the present inven-tion in detail:
Example 1 1000 ml of toluene was charged in a flask of 3000 ml, sufficiently re-placed by nitrogen gas, and then cooled at -65 C, to which 1.2 millimoles of 1,7-octadiene was added at the same temperature. 10 millimoles of Al (C2Hs )2CIand 1 millimole of V(2-methyl-1,3-butanedionato)3 were then added thereto and stirred for 30 minutes. Further, 4.5 g of ethylene was introduced thereinto for 2 hours and 1.2 millimoles of 1,7-octadiene was then added thereto~ ~fter stirring for 10 minutes, the reaction solution was poured in ethanol and fil-tered to obtain a polymer having a number average molecular weight (Mn) of 4.9 x 109 measure(l by the GPC method with a yield of 4.3 g.
Measurement of the proton NMR of the above described polymer told a signal based on the proton of the termlnal double bonds at 5.0 ppm and 5.8 ppm. Tlle assignments thereof are as follows:
(ppm) Assi~nment _ ~ (ppm) l~ssignment 5.0 -Cll- C~l ~ 5.8 -C ll= Cll ~
From the intensity ratlo of this signal and the peak of 1.3 ppm due to the ethylene polymer was obtained Mn of 4.6 x 109 assuming that vinyl groups were present at both the ends thereof. This value was substantially in agree-ment with that obtained by the GPC method. It was concluded therefrom that the thus obtalned polymer was an ethylene polymer having vinyl groups at both ends thereof.
The above described polymer was added to 200 ml of n-butyl ether, to which a solution of diborane in tetrahydrofuran was added at room temperatrue while vigorously stirring and flowlng nitrogen. The amount of the diborane added was 2.5 millimoles. ~fter stirring for 1 hour at the refluxing temperature, 2 ~ 7 3 t tempernture wns lowered and 200 ml of a 3 N aqueous solution of sodium hydroxide and 200 ml of a 30 % aqueous solution of hydrogen peroxide were added thereto, followed by stirring for 1 day. The resulting polymer was ade-quately washed with water, then washed with acetone and dried.
There was found a broad peak at 3300 to 3500 cm~' in the IR (infrared ab-sorption spectrum) chart of the thus formed polymer, from which it was ap-parent that the polymer had hydroxyl group.
The above described ethylene polymer and 10 g of trimethylchlorosilane were added to 200 ml of pyridine, stirred at 25 C for 1 hour and then refluxed for ~ hours. The resulting polymer was washed with methanol and then dried.
Measurement by proton NMR told a slgnal due to the proton of -Si(C~13)9 group at 0.08 ppm. From the intensity ratio of this signal and the peak of 1.3 ppm due to the ethylene polymer was obtained Mn of 5.5 x 109, which was substantially in agreement wlth that obtained from GPC. It was concluded there-frolR that nn ethylne polymer llaving trlmethylsllyloxy groups at both the ends thereof was synthesized from the polymer. As a result of the IR nnnlysis, a peak of 3300 to 3500 cm ~` was not observed In the ethylene polymer hnving trlmetllylsllyloxy groups at both the ends thereof. Thus, it was concluded thatthe polymer before the renctlon wlth trimetllylchlorosllnne wns nn etllylene polymer havlng hydroxyl groups at both the ends thereof.
Example 2 lO00 ml of toluene was charged in a flask of 3000 ml, sufficiently re-placed by nitrogen gas, and then cooled at -78 C, to whlch 0.6 millimole of l,9-decadiene was added at the same temperature. 100 mllllmoles of Al(C2~1s)2CIand 20 millimoles of V(acetylacetonato)9 were then added thereto and stirred for 30 minutes. Further, 1.5 g of ethylene was introduced thereinto for a peri-od of 30 minutes and 0.6 millimoles of l,9-decadiene was then added thereto.
After stirring for 30 minutes, the reaction solution was poured in ethanol and filtered to obtain a polymer with a yield of 1.2 g.
Then, the hydroxylation reaction was carried out in an analogous manner 2 ~
t Jxample 1 except changing the amount of diborane in 1 millimole. I~llen the resulting polymer was subjected to IR analysis, a broad pealc was observed at 3300 to 3500 cm ~'. Measurement of the hydroxylated polymer by GPC told an Mn of 2.6 x 103 .
Example 3 Example 1 was repeated except introducing 1.5 g of ethylene for 30 minutes to synthesize an ethylene polymer of the present invention, having an Mn of 1.5 x 103, measured by proton NMR.
Example 4 1000 ml of toluene was charged in a flask of 3000 ml, sufficiently re-placed by nitrogen gas, and then cooled at -78 C, to which 1.5 millimoles of 1,7-octadiene was added at the same temperature. 100 millimoles of Al(Cz11s)2CIand 20 millimoles of V(acetylacetonato)3 were then added thereto and stirred for 30 minutes. Further, 35 g of propylene was added thereto and polymerized for 1 hollr, to whlch 3.0 millimoles of 1,7-octadiene was then ndded. After stirring for 30 minutes, the reactlon solutlon was pourecl in ethanol an(l fll-tered to obtain a polymer witll a yield of 6.1 g.
Measurement of the proton NMR of the above descllbed polymer told a signal based on the proton of the termlnal double bonds at 5.0 ppm and 5.8 ppm.
From the intenslty ratlo of tllis slgnal and the peak of 0.7-1.7 ppm due to the propylene polymer was obtained Mn of 5.1 x 103 assulning that vlnyl groups were present at both the ends thereof. When this polymer was subjected to GPC
analysis, Mn was 6.0 x 103, from which it was concluded that the thus obtained polymer was a propylene polymer having vinyl groups at both the ends thereof.
The above described polymer was dlssolved in 500 ml of tetrahydrofuran, to which a solution of diborane in TilF was added at room temperatrue while vigo-rously stirring and flowing nitrogen. The amount of the diborane added was 3 millimoles. After stirring for 4 hours at room temperature, a 3 N aqueous solution of sodium hydroxide and 30 % aqueous solution of hydrogen peroxide were added thereto and further stirred for 1 day. The resulting polymer was 2 ~ 7 ~
w ed with water, then washed with acetone and dried.
Wllen the tl~us formed polymer was subjected to IR analysis, a broad peak due to hydroxyl group at 3300 to 3500 cm~' was observed. The number average molecular weight, measured by GPC "~as 4.8 x 103. When the reaction with tri-methylchlorosilane was carried out in the similar manner to Example 1, the proton NMR of the resulting polymer showed a peak due to the hydrogen of the trimethylsilyl group at 0.08 ppm and a peak due to the proton of the propylene polymer at 0.7 to 1.7 ppm. From the intensity ratio of both the peaks was obtained an Mn of 5.6 x iO3 .
Example 5 3 millimoles of 2,7-dl(4-toluyl)-1,7-octadiene was dissolved in 25 ml of a mixed solution of similar volumes of heptane and toluene. This solution was added to 9 millimoles of s-butyllithium and stirrd at room temperature for 5 days. A dilithio compound was precipitated from the reaction solution, fil-tered and washed wlth 25 ml of heptane. 200 ml of dried toluene was added to a reaction vessel of 500 ml, ndequately replaced by nitrogen, to whlch 7 mill~-moles of tetramethylethylenediamine was further added. I~fter cooling to 0 ~C, t~le above descrlbed dllithio compound was added thereto, to whlch ethylene was ndded wlth agltatlon. While supplementlng ethyllene so as to maintain the pres-sure o~ ethylene nt 2 ntm inslde the reactlon system, the Inlxture was stlrred for 2~ hours and an ethylene polymer was synthesized.
After exhausting the ethylene retained in the system, the mixture was cooled to -78 ~ , into which dried carbon dioxide was introduced~ While main-talning the Internal pressure of carbon dioxlde at 2 atm, the temperature was raised to room temperature, followed by stirring for 5 hours.
The product was poured in 10 % HCI and the resulting precipitate was sep-arated by filtration; The precipltate was extracted with hot toluene for 2 days, the toluene was cooled, the resulting product was filtered and dried, thus obtaining a polymer with a yleld of 1.6 g and a number average molecular weight (Mn) of 1.5 x 103, measured by GPC. When this polymer was subjected to I .pectrum nnnlysis, n peak due to carboxylic acid was observed7~
When the polymer was subJected to measurement of the proton NMR, tllere was found a broad peak due to the hydrogen of the carboxylic acid near 11 ppm.
An Mn of 1.7 X 109 was obtained from the intensity ratio of the peak of 1.3 ppm due to the ethylene polymer and the peak of 2.3 ppm due to the hydrogen of the methylene group adjacent to the carboxylic acid. This value was sub-stantially in agreement with that obtained by GPC.
Thus, it was concluded from these results that an ethylene polymer }laving carboxylic groups at both the ends thereof could be synthesized.
Example 6 1.5 g of the ethylene polymer having carboxylic groups at both the ends thereof, obtained in Example 5, was dissolved in 200 ml of xylene at 120 C, to which 8.3 ml of boron trifluoride-methanol complex was added. The result-ing mlxture was reacted by heating with refluxing for 6 hours, flfter which the solvent wns removed under reduced pressure to obtaln n prodllct. ~hen this pro-duct was subjected to measurement of IR spectrum, there were found peaks due to the ester linkage near 1740 cln ~' and 1150 cnl -1, Tllus, It was concluded from these results that the ethylene polymer car-boxylated at both the ends thereof was converted Into an ethylelle polymer methyl-esterified at both the ends thereof.
Example 1 Example 5 was repeated except changing the polymerization tlme of ethylene in 12 hours to synthesize an ethylene polymer of the present invention. When the resulting polymer was subjected to measurement o~ the IR spectrum in an analogous manner to Example 1, there was observed a peak due to the carboxylic acid at 1700 cm ~'. The number average molecular weight, measured from the proton NMR, was 5.1 x 103.

Claims (20)

1. An olefin polymer comprising recurring units represented by the general formula -( - CH2- CHR -) - and having H2C=CH- group bonded at both the ends thereof and 8 number average molecular weight of 300 to 500,000, wherein R is a hydrogen atom or methyl group.

2. The olefin polymer as claimed in Claim 1, wherein the olefin polymer has an Mw/Mn of 1.05 to 1.5.

3. An ethylene polymer comprising recurring units of -( - CH2- CH2 -) -and havinggroup bonded at both the ends thereof and a number average molecular weight of 300 to 300,000, wherein X represents -OH, -OR', a halogen atom or -SO3R2, R' represents a hydrocarbon group containing 1 to 5 carbon atoms and R2 represents a halogen atom-substituted or non-substitut hydrocar-bon group containing I to 20 carbon atoms.

4. A process for the production of an olefin polymer as claimed in Claim 1, which comprises polymerizing ethylene or propylene in the presence of a reactionproduct of a polymerization catalyst consisting of a vanadium chelate compound and a dialkylaluminum halide represented by the general formula Ri, 2AlX' wherein R1' is an alkyl group containing 1 to 20 carbon atoms and X' is a halogen atom with an .alpha. , .omega. -diolefin compound represented by the general formula H2C=CH - ( - C - II2? - ) - CH=CH2 wherein m is 1 to 15, and then reacting with the diolefin compound and with a proton donor.

5. A process for the production of the ethylene polymer as claimed in Claim 3, which comprises polymerizing ethylene in the presence of a dilithio compound formed by the reaction of (I) a diolefin compound represented by the general formula H2C=CR3-R4-CR3=CH2 wherein R3 represents a hydrocarbon group containing 1 to 10 carbon atoms and R1 represents a divalent hydrocarbon group containing 1 to 20 carbon atoms with (II) an organolithium compound, and (III) a diamine compound represented by the general formula R25N-R7-NR26 wherein R6 represents a hydrocarbon group containing I to 5 carbon atoms and R7 repre-s s a divalent hydrocarbon group containing 1 to 10 carbon atoms, then re-acting with carbon dioxide and with a proton donor or sulfonyl halide repre-sented by the general formula ZSO2R2 wherein Z represents a halogen atom and R2 have the same meaning as described above.

6. A process for the production of the ethylene polymer as claimed in Claim 3, which comprises polymerizing ethylene in the presence of a dilithio compound formed by the reaction of (I) a diolefin compound represented by the general formula H2C=CR3-R4-CR3=CH2 wherein R3 represents a hydrocarbon group containing 1 to 10 carbon atoms and R4 represents a divalent hydrocarbon group containing 1 to 20 carbon atoms with (II)an organolithium compound, and (III) a diamine compound represented by the general formula R26N-R7-NR26 wherein R6 represents a hydrocarbon group containing 1 to 5 carbon atoms and R7 represents a divalent hydrocarbon group containing 1 to 10 carbon atoms, then reacting with carbon dioxide, then with a proton donor and then with an alcohol taining 1 to 5 carbon atoms or with a thionyl halide.

7. The process as claimed in Claim 4, wherein the chelate compound is selected from the group consisting of V(acetylacetonato)3, V(2-methyl-1-3-butanedionato)3 and V(1,3-butanedionato)3.

8. The process as claimed in Claim 4, wherein the dialkylaluminum halide is selected from the group consisting of dimethylaluminum chloride, diethyl-aluminum chloride, diethylaluminum bromide, diethylaluminum iodide, dilsobutyl-aluminum chloride and mixtures thereof.

9. The process as claimed in Claim 4, wherein the vanadium chelate com-pound and the dialkylaluminum halide are used in a proportion of 1 to 1,00 moles of dialkylaluminum halide to 1 mole of the vanadium chelate compound.

10. The process as claimed in Claim 4, wherein the diolefin compound is selected from the group consisting of 1,4-pentadiene, 1,5-hexadiene, 1,6-heptadiene, 1,7-octadiene, 1,8-nonadiene, 1,9-decadiene, 1,10-undecadiene, 1,11--dodecadiene, 1,13-tetradecadiene, 1,15-hexadecadiene, 1,17-octadecadiene and ?ures thereof.

11. The process as claimed in Claim 4, wherein the-polymerization catalyst and the diolefin compound are reacted in a proportion of 0.1 to 10 moles of the vanadium compound in the polymerization catalyst to 1 mole of the diolefin compound.

12. The process as claimed in Claim 5 or 6, wherein the diolefin compound (I) is selected from the group consisting of 2,5-dimethyl-1,5-hexadiene, 2,5-diphenyl-1,5-hexadiene, 2,6-diphenyl-1,6-heptadiene, 2,7-diphenyl-1,7-octadiene,2,7-dimethyl-1,7-octadiene, 1,2-bis[4-(1-phenylvinyl)phenyl]ethane, 1,4-bis[4-(1-phenylvinyl)phenyl]butane, 1,2-bis(isopropenyl-4-phenyl)ethane, 1,2-bis-(isopropenyl-4-phenyl)butane and mixtures thereof.

13. The process as claimed in Claim 5 or 6, wherein the organolithium com-pound (II) is selected from the group consisting of methyllithium, ethyllithi-um, n-propyllithium, i-propyllithium, n-butyllithium, i-butyllitllium, s-butyl-lithium, t-butyllithium, n-pentyllithium, hexyllithium and mixtures thereof.

14. The process as claimed in Claim 5 or 6, wherein the diolefin compound (I) and the organolithium compound (II) are used in a proportion of (II)/(I) (molar ratio) of 0.1 to 30.

15. The process as claimed in Claim 5 or 6, wherein the diamine compound (III) is selected from the group consisting of tetramethylethylenediamine, tetramethylpropylenediamine, tetramethyldiaminobutane, tetramethyldiamino-pentane, tetramethyldiaminohexane, tetraethylenediamine and mixtures thereof.

16. The process as claimed in Claim 5 or 6, wherein the dilithio compound and the diamine compound are used to give a proportion of 0.1 to 20 moles of the diamine compound (III) to 1 mole of the diolefin compound (I) used in the production of the dilithio compound.

17. The process as claimed in Claim 5 or 6, wherein the carbon dioxide is used in a proportion of 0.1 to 10,000 moles to 1 mole of the diolefin compound (I).

18. The process as claimed in Claim 5 or 6, wherein the proton donor is ?ected from the group consisting of water, alcohols, inorganic acids and mix-tures thereof.

19. The process as claimed in Claim 6, wherein the alcohol is selected from the group consisting of methanol, ethanol and mixtures thereof.

20. The process as claimed in Claim 6, wherein the thionyl halide is se-lected from the group consisting of SOC12, SO2CI2, SOBr2, SOI2, SO2Br2, SO2I2 and mixtures thereof.