US4987200A — Preparation of polymer incorporating masked funct…

Claim 1

Independent Claim 155 words

A method for forming a masked functionalized polymer of polymer chain monomers, said monomers selected from the group consisting of ethylene, alpha-olefins, and non-conjugated dienes, and functional group-containing monomers comprising: (a) reacting at a temperature of less than 60° C. (i) functional group-containing monomers having a general formula of: R.sup.1 --(X).sub.n wherein R 1 comprises an ethylenically unsaturated hydrocarbyl radical, n is an integer of at least 1, and X is selected from the group consisting of carboxyl, hydroxyl, cyano, thio, amino, carbonyl and imino groups, with (ii) a masking agent comprising at least one non-halogenated metallic compound to form the corresponding masked functional group-containing monomers; (b) reacting said masked functional group-containing monomers with a C 2 -C 5 alcohol; and (c) polymerizing in the presence of a Ziegler polymerization catalyst said polymer chain monomers with said masked functional group-containing monomers to produce a polymerization product comprising a polymer chain including masked functional group-containing monomers.

Claim 2

Independent Claim 155 words

A method for forming a masked functionalized polymer of polymer chain monomers, said monomers selected from the group consisting of ethylene, alpha-olefins, and non-conjugated dienes, and functional group-containing monomers comprising: (a) reacting at a temperature of less than 60° C. (i) functional group-containing monomers having a general formula of: R.sup.1 --(X).sub.n wherein R 1 comprises an ethylenically unsaturated hydrocarbyl radical, n is an integer of at least 1, and X is selected from the group consisting of carboxyl, hydroxyl, cyano, thio, amino, carbonyl and imino groups, with (ii) a masking agent comprising at least one non-halogenated metallic compound to form the corresponding masked functional group-containing monomers; (b) reacting said masked functional group-containing monomers with a C 2 -C 5 alcohol; and (c) polymerizing in the presence of a Ziegler polymerization catalyst said polymer chain monomers with said masked functional group-containing monomers to produce a polymerization product comprising a polymer chain including masked functional group-containing monomers.

Claim 3

Dependent Claim 24 words

The method for forming a masked functionalized polymer in accordance with claim 1, wherein said functionalized polymer comprises less than 0.10% by weight halogens.

Claim 4

Dependent Claim 24 words

The method for forming a masked functionalized polymer in accordance with claim 2, wherein said functionalized polymer comprises less than 0.03% by weight halogens.

Claim 5

Dependent Claim 22 words

The method for forming a masked functionalized polymer in accordance with claim 1, wherein R 1 contains less than 25 carbon atoms.

Claim 6

Dependent Claim 23 words

The method for forming a masked functionalized polymer in accordance with claim 4, wherein R 1 contains not greater than 16 carbon atoms.

Claim 7

Dependent Claim 30 words

The method for forming a masked functionalized polymer in accordance with claim 4, wherein R 1 is selected from the group consisting of radicals from alpha-olefins, norbornene and aklkyl-substituted norbornenes.

Claim 8

Dependent Claim 28 words

The method for forming a masked functionalized polymer in accordance with claim 4, wherein said R 1 is selected from the group consisting of vinyl and allyl radicals.

Claim 9

Dependent Claim 38 words

The method for forming a masked functionalized polymer in accordance with claim 5, wherein R 1 is derived from alpha-olefins having the general formula of: H.sub.2 C═CH(C.sub.m H.sub.2m)-- wherein m is an integer of from 1 to 30.

Claim 10

Dependent Claim 46 words

The method for forming a masked functionalized polymer in accordance with claim 1, wherein R 1 is selected from the group consisting of radicals from norbornene and homologues of norbornene having the general formula of: ##STR41## wherein p is an integer of from 1 to 30.

Claim 11

Dependent Claim 41 words

The method for forming a masked functionalized polymer in accordance with claim 9, wherein said functional group-containing monomer is selected from the group consisting of norbornene carboxylic acids, norbornene dicarboxylic acids, norbornene methanols, norbornene carboxaldehydes, norbornene methyl amines, and norbornene carboximines.

Claim 12

Dependent Claim 22 words

The method for forming a masked functionalized polymer in accordance with claim 10, wherein said functional group-containing monomer is norbornene carboxylic acid.

Claim 13

Dependent Claim 21 words

The method for forming a masked functionalized polymer in accordance with claim 11, wherein said norbornene carboxylic acid is 5-norbornene-2-carboxylic acid.

Claim 14

Dependent Claim 22 words

The method for forming a masked functionalized polymer in accordance with claim 10, wherein said functional group-containing monomer is norbornene dicarboxylic acid.

Claim 15

Dependent Claim 21 words

The method for forming a masked functionalized polymer in accordance with claim 13, wherein said norbornene dicarboxylic acid is 5-norbornene-2,3-dicarboxylic acid.

Claim 16

Dependent Claim 19 words

The method for forming a masked functionalized polymer in accordance with claim 10, wherein said norbornene methanol is 5-norbornene-2-methanol.

Claim 17

Dependent Claim 19 words

The method for forming a masked functionalized polymer in accordance with claim 10, wherein said norbornene methylamine is 5-norbornene-2-methylamine.

Claim 18

Dependent Claim 22 words

The method for forming a masked functionalized polymer in accordance with claim 4, wherein said functional group-containing monomer is vinyl acetic acid.

Claim 19

Dependent Claim 21 words

The method for forming a masked functionalized polymer in accordance with claim 4, wherein said functional group-containing monomer is allyl alcohol.

Claim 20

Dependent Claim 102 words

The method for forming a masked functionalized polymer in accordance with claim 1, wherein said non-halogenated metallic compound is an organometallic compound of the formula: M--(Y).sub.r wherein M is a member selected from Group IB, IIA, IIB, IIIA, IVA, and the transition metals elements, Y is at least one of R 2 , R 3 , R 4 and R 5 , wherein R 2 -R 5 are independently selected from the group consisting of hydrogen, and non-halogenated C 1 -C 16 hydrocarbyl radicals, and non-halogenated C 1 -C 16 hydrocarbyloxy radicals and r is an integer of from 1 to 4.

Claim 21

Dependent Claim 44 words

The method for forming a masked functionalized polymer in accordance with claim 19, wherein said non-halogenated C 1 -C 16 radicals are selected from the group consisting of C 1 -C 16 alkyl, C 1 -C 16 aryl, and C 1 -C 16 alkoxy.

Claim 22

Dependent Claim 54 words

The method for forming a masked functionalized polymer in accordance with claim 20, wherein R 2 -R 5 are non-halogenated members independently selected from the group consisting of hydrogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tertiary butyl, pentyl, hexyl, phenyl, tolyl, ethylphenyl, naphthyl, methoxy, ethoxy, propoxy, hexoxy, pentoxy, phenoxy, methylphenoxy, iso-butoxy and tertiary butoxy.

Claim 23

Dependent Claim 28 words

The method for forming a masked functionalized polymer in accordance with claim 19, wherein M is an element selected from the group consisting of aluminum, magnesium, and zinc.

Claim 24

Dependent Claim 32 words

The method for forming a masked functionalized polymer in accordance with claim 22, wherein said organometallic compound is selected from the group consisting of triisobutylaluminum, triethylaluminum, diisobutyl aluminum hydride, diethylzinc, and di-n-hexylmagnesium.

Claim 25

Dependent Claim 30 words

The method for forming a masked functionalized polymer in accordance with claim 23, wherein said organometallic compound is selected from the group consisting of triisobutylaluminum, triethylaluminum, and diisobutyl aluminum hydride.

Claim 26

Dependent Claim 35 words

The method for forming a masked functionalized polymer in accordance with claim 1, wherein said polymerization catalyst comprises at least one member selected from the group consisting of vanadium compounds, titanium compounds and zirconium compounds.

Claim 27

Dependent Claim 35 words

The method for forming a masked functionalized polymer in accordance with claim 25, wherein said vanadium compounds include a member selected from the group consisting of vanadium halides, vanadium oxyhalide and vanadium salts of beta-diketonates.

Claim 28

Dependent Claim 20 words

The method for forming a masked functionalized polymer in accordance with claim 26, wherein said vanadium halide is vanadium tetrachloride.

Claim 29

Dependent Claim 36 words

The method for forming a masked functionalized polymer in accordance with claim 25, wherein said titanium compounds are selected from the group consisting of TiCl 3 , TiCl 4 , and TiCl 3 .1/3AlCl 3 .

Claim 30

Dependent Claim 34 words

The method for forming a masked functionalized polymer i accordance with claim 28, wherein said titanium compounds are electron donor modified versions of TiCl 4 , TiCl 3 and TiCl 3 .1/3AlCl 3 .

Claim 31

Dependent Claim 55 words

The method for forming a masked functionalized polymer in accordance with claim 25, wherein said polymerization catalyst further comprises an organoaluminum co-catalyst having the formula R x AlX.sub.(3-x) wherein X is a halogen, R is a member selected from the group consisting of alkyl and aryl, and x is greater than 0 up to 3.

Claim 32

Dependent Claim 35 words

The method for forming a masked functionalized polymer in accordance with claim 30, wherein R of said organoaluminum co-catalyst is a member selected from the group consisting of C 1 -C 16 alkyl and phenyl.

Claim 33

Dependent Claim 36 words

The method for forming a masked functionalized polymer in accordance with claim 31, wherein said organoaluminum co-catalyst is a member selected from the group consisting of ethyl aluminum dichloride, diethyl aluminum chloride, and ethyl aluminum sesquichloride.

Claim 34

Dependent Claim 26 words

The method for forming a masked functionalized polymer in accordance with claim 31, wherein x of said organoaluminum co-catalyst is greater than 0 up to 2.

Claim 35

Dependent Claim 42 words

The method for forming a masked functionalized polymer in accordance with claim 31, wherein said at least one vanadium compound and said organoaluminum co-catalyst are present in said catalyst in a molar ratio of vanadium to aluminum of about 1:2 to 1:30.

Claim 36

Dependent Claim 36 words

The method for forming a masked functionalized polymer in accordance with claim 1, wherein said alcohol is a C 3 -C 4 alkanol selected from the group consisting of isopropyl alcohol, isobutyl alcohol, and t-butyl alcohol.

Claim 37

Dependent Claim 36 words

The method for forming a masked functionalized polymer in accordance with claim 1, wherein said polymer chain monomers are members selected from the group consisting of ethylene, C 3 -C 25 alpha olefins and non-conjugated dienes.

Claim 38

Dependent Claim 30 words

The method for forming a masked functionalized polymer in accordance with claim 36, wherein said alpha-olefins are selected from the group consisting of propylene, 1-butene, 1-pentene, 1-hexene, 1-octene and 1-dodecene.

Claim 39

Dependent Claim 36 words

The method for forming a masked functionalized polymer in accordance with claim 36, wherein said non-conjugated diene is selected from the group of straight chain, branched chain and cyclic hydrocarbon diolefins having 6 to 15 carbons.

Claim 40

Dependent Claim 29 words

The method for forming a masked functionalized polymer in accordance with claim 36, wherein said non-conjugated dienes are selected from the group consisting of dicyclopentadiene, 1,4-hexadiene, 5-methyl-2-norbornene and 5-ethylidene-2-norbornene.

Claim 41

Dependent Claim 27 words

The method for forming a masked functionalized polymer in accordance with claim 39, wherein said non-conjugated dienes are selected from the group consisting of 5-ethylidene-2-norbornene, and 1,4-hexadiene.

Claim 42

Dependent Claim 27 words

The method for forming a masked functionalized polymer in accordance with claim 36, wherein said polymer chain monomers are a mixture consisting essentially of ethylene and propylene.

Claim 43

Dependent Claim 40 words

The method for forming a masked functionalized polymer in accordance with claim 41, wherein said polymer chain comprises about 20 wt %-90 wt % ethylene and about 10 wt %-80 wt % propylene by total weight of said functionalized polymer.

Claim 44

Dependent Claim 40 words

The method for forming a masked functionalized polymer in accordance with claim 1, wherein said masked, functional group-containing monomers are present in a range of about 0.1 wt % to 40 wt % by total weight of said polymerization product.

Claim 45

Dependent Claim 20 words

The method in accordance with claim 1, wherein said reacting is performed at a temperature of less than +30° C.

Claim 46

Dependent Claim 27 words

The method in accordance with claim 44, further comprising maintaining said masked, functional group-containing monomers at a temperature of less than +30° C. prior to said polymerizing.

Claim 47

Dependent Claim 16 words

The method in accordance with claim 45, wherein said reacting is performed in an inert atmosphere.

Claim 48

Dependent Claim 44 words

The method in accordance with claim 46, wherein said functional group-containing monomers include at least two different functional group-containing monomers wherein X of each different functional group-containing monomers is independently selected from said group consisting of carboxyl, hydroxyl, cyano, amino, carbonyl and imino groups.

Claim 49

Dependent Claim 36 words

The method according to claim 47 wherein said masked functionalized polymer chain contains functional group-containing monomers, said functional groups being at least two of the group consisting of carboxyl, hydroxyl, cyano, amino, carbonyl and imino groups.

Claim 50

Dependent Claim 57 words

The method in accordance with claim 48, wherein said at least two different functional group-containing monomers include functional group-containing monomers wherein X is independently selected from the group consisting of carboxyl groups and hydroxyl groups, and wherein said masked functionalized polymer chain contains multiple functionality provided by carboxylic acid residues and alcohol residues on said polymer chain.

Claim 51

Independent Claim 164 words

A method for forming a masked functionalized polymer of polymer chain monomers, said monomers selected from the group consisting of ethylene, alpha-olefin, and non-conjugated dienes, and functional group-containing monomers comprising: (a) reacting at a temperature of less than 60° C. (i) functional group-containing-monomers having the general formula of R.sup.1 --(X).sub.n wherein R 1 is selected from the group consisting of radicals from norbornene and homologues of norbornene having the general formula of: ##STR42## wherein p is an integer from 1 to 30, n is an integer of at least 1, and X is selected from the group consisting of carboxyl, hydroxyl, cyano, thio, amino, carbonyl and imino groups, with (ii) a masking agent comprising at least one non-halogenated metallic compound to form the corresponding masked functional group-containing monomers; and (b) polymerizing in the presence of a Ziegler polymerization catalyst said polymer chain monomers with said masked, functional group containing monomers to produce a polymerization product comprising a polymer chain including masked functional group-containing monomers.

Claim 52

Independent Claim 164 words

A method for forming a masked functionalized polymer of polymer chain monomers, said monomers selected from the group consisting of ethylene, alpha-olefin, and non-conjugated dienes, and functional group-containing monomers comprising: (a) reacting at a temperature of less than 60° C. (i) functional group-containing-monomers having the general formula of R.sup.1 --(X).sub.n wherein R 1 is selected from the group consisting of radicals from norbornene and homologues of norbornene having the general formula of: ##STR42## wherein p is an integer from 1 to 30, n is an integer of at least 1, and X is selected from the group consisting of carboxyl, hydroxyl, cyano, thio, amino, carbonyl and imino groups, with (ii) a masking agent comprising at least one non-halogenated metallic compound to form the corresponding masked functional group-containing monomers; and (b) polymerizing in the presence of a Ziegler polymerization catalyst said polymer chain monomers with said masked, functional group containing monomers to produce a polymerization product comprising a polymer chain including masked functional group-containing monomers.

Claim 53

Dependent Claim 41 words

The method for forming a masked functionalized polymer in accordance with claim 50, wherein said functional group-containing monomer is selected from the group consisting of norbornene carboxylic acids, norbornene dicarboxylic acids, norbornene methanols, norbornene carboxaldehydes, norbornene methyl amines, and norbornene carboximines.

Claim 54

Dependent Claim 22 words

The method for forming a masked functionalized polymer in accordance with claim 51 wherein said functional group-containing monomer is norbornene carboxylic acid.

Claim 55

Dependent Claim 21 words

The method for forming a masked functionalized polymer in accordance with claim 52 wherein said norbornene carboxylic acid is 5-norbornene-2-carboxylic acid.

Claim 56

Dependent Claim 22 words

The method for forming a masked functionalized polymer in accordance with claim 51 wherein said functional group-containing monomer is norbornene dicarboxylic acid.

Claim 57

Dependent Claim 21 words

The method for forming a masked functionalized polymer in accordance with claim 54 wherein said norbornene dicarboxylic acid is 5-norbornene-2,3-dicarboxylic acid.

Claim 58

Dependent Claim 19 words

The method for forming a masked functionalized polymer in accordance with claim 51 wherein said norbornene methanol is 5-norbornene-2-methanol.

Claim 59

Dependent Claim 19 words

The method for forming a masked functionalized polymer in accordance with claim 51 wherein said norbornene methylamine is 5-norbornene-2-methylamine.

Claim 60

Independent Claim 113 words

A method for forming a masked functionalized polymer of polymer chain monomers, said monomers selected from the group consisting of ethylene, alpha-olefin, and non-conjugated dienes, and functional group-containing monomers comprising: (a) reacting at a temperature of less than 60° C. (i) a functional group-containing monomer selected from the group consisting of vinyl acetic acid and allyl alcohol with (ii) a masking agent comprising at least one non-halogenated metallic compound to form the corresponding masked functional group-containing monomers; and (b) polymerizing in the presence of a Ziegler polymerization catalyst said polymer chain monomers with said masked, functional group containing monomers to produce a polymerization product comprising a polymer chain including masked, functional group-containing monomers.

Claim 61

Independent Claim 113 words

A method for forming a masked functionalized polymer of polymer chain monomers, said monomers selected from the group consisting of ethylene, alpha-olefin, and non-conjugated dienes, and functional group-containing monomers comprising: (a) reacting at a temperature of less than 60° C. (i) a functional group-containing monomer selected from the group consisting of vinyl acetic acid and allyl alcohol with (ii) a masking agent comprising at least one non-halogenated metallic compound to form the corresponding masked functional group-containing monomers; and (b) polymerizing in the presence of a Ziegler polymerization catalyst said polymer chain monomers with said masked, functional group containing monomers to produce a polymerization product comprising a polymer chain including masked, functional group-containing monomers.

Claim 62

Dependent Claim 16 words

The method in accordance with claim 58 wherein said functional group-containing monomer is vinyl acetic acid.

Claim 63

Dependent Claim 15 words

The method in accordance with claim 59 wherein said functional group-containing monomer is allyl alcohol.

Annuity Stage	Window Opens	Payment Deadline	Surcharge Period Until	Estimated Fee	Status
3.5 Years (Year 4)	1994-01-21	1994-07-23	1995-01-22	$2000.00	Window Closed / Lapsed
7.5 Years (Year 8)	1998-01-21	1998-07-23	1999-01-22	$3760.00	Window Closed / Lapsed
11.5 Years (Year 12)	2002-01-21	2002-07-23	2003-01-22	$7700.00	Window Closed / Lapsed

Preparation of polymer incorporating masked functional group-containing monomers

Abstract

Inventors

Bibliographic Details

Claims Analysis

References Cited (Backward Citations)

USPTO Annuity & Maintenance Windows

Assigned Categories & Tags

Assign Category Tag