Aliphatic polycarbonate compositions and methods

Abstract

In one aspect, the present invention pertains to novel block materials comprising an aliphatic polycarbonate (APC) chain bound to a hydrocarbon. The invention also provides methods of making the block materials and using them as compatibilizers for polymer blends. In another aspect, the present invention encompasses methods of making blends of APCs with polyolefins. In certain embodiments, the methods comprise the step of blending one or more APCs with one or more polyolefins in the presence of a compatibilizer as described herein. In another aspect, the present invention encompasses novel blends of APCs with polyolefins. In certain embodiments, the blends comprise one or more APCs; at least one polyolefin and a compatibilizer as described herein.

Claims

1. A method of compatibilizing a blend of two or more polymers comprising the step of admixing with the polymers an effective amount of the block copolymer comprising the formula: ##STR00372## where the moiety ##STR00373## comprises an alternating copolymer of CO.sub.2 and one or more epoxides; and the moiety ##STR00374##  consisting of a saturated or unsaturated hydrocarbon.

2. The method of claim 1, wherein the blend of two or more polymers comprises at least one polyolefin and at least one aliphatic polycarbonate.

3. The method of claim 2, wherein a polyolefin is selected from polyethylene and polypropylene.

4. The method of claim 2, wherein the aliphatic polycarbonate is selected from poly(propylene carbonate); poly(ethylene carbonate); poly(cyclohexene carbonate); and blends or copolymers of two or more of the aliphatic polycarbonate.

Description

DETAILED DESCRIPTION OF CERTAIN EMBODIMENTS

(1) I. Novel Block Copolymer Compositions

(2) The present invention provides, among other things, novel block polymers. In certain embodiments, such block polymers have utility as compatibilizers for polymer blends. In certain embodiments, the novel block polymers comprise linear diblock materials where a first block comprises an alternating copolymer of CO.sub.2 and one or more epoxides and a second block comprises a hydrocarbon.

(3) In certain embodiments, the novel block copolymers have a formula I:

(4) ##STR00006## where the moiety

(5) ##STR00007##  comprises an alternating copolymer of one or more epoxides and CO.sub.2; and the moiety

(6) ##STR00008##  comprises a saturated or unsaturated hydrocarbon.
a. Detailed Description of the APC Segment

(7) In certain embodiments, the moiety

(8) ##STR00009##
comprises repeating units having a structure:

(9) ##STR00010## where R.sup.1, R.sup.2, R.sup.3, and R.sup.4 are, at each occurrence in the polymer chain, independently selected from the group consisting of —H, fluorine, an optionally substituted C.sub.1-40 aliphatic group, an optionally substituted C.sub.1-20 heteroaliphatic group, and an optionally substituted aryl group, where any two or more of R.sup.1, R.sup.2, R.sup.3, and R.sup.4 may optionally be taken together with intervening atoms to form one or more optionally substituted rings optionally containing one or more heteroatoms.

(10) In certain embodiments, the moiety

(11) ##STR00011##
is derived from copolymerization of carbon dioxide with ethylene oxide, propylene oxide, 1,2 butene oxide, 1,2 hexene oxide, oxides of higher alpha olefins (e.g. C.sub.6-40 alpha olefins), butadiene monoepoxide, epichlorohydrin, ethers or esters of glycidol, cyclopentene oxide, cyclohexene oxide, 3 vinyl cyclohexene oxide, 3-ethyl cyclohexene oxide, or combinations of any two or more of these.

(12) In certain embodiments, the moiety

(13) ##STR00012##
is derived from propylene oxide. In certain embodiments, the moiety

(14) ##STR00013##
is derived from propylene oxide and one or more additional epoxides. In certain embodiments, the moiety

(15) ##STR00014##
is derived from ethylene oxide. In certain embodiments, the moiety

(16) ##STR00015##
is derived from ethylene oxide and one or more additional epoxides.

(17) In certain embodiments, in copolymers of formula 1, the copolymer has a formula P1:

(18) ##STR00016## where each of R.sup.1, R.sup.2, R.sup.3, R.sup.4, n, and

(19) ##STR00017##  are as defined above and in the classes and subclasses herein, and n is an integer from about 4 to about 5,000.

(20) In certain embodiments, the copolymer has a formula P1a:

(21) ##STR00018## where each of n and

(22) ##STR00019##  are as defined above and in the classes and subclasses herein; and R.sup.1a is, independently at each occurrence in the polymer chain, selected from the group consisting of —H, —CH.sub.3, —CH.sub.2CH.sub.3, —CH.sub.2Cl, —CH.sub.2OR.sup.x, —CH.sub.2OC(O)R.sup.x, and —(CH.sub.2).sub.qCH.sub.3, where each R.sup.x is independently an optionally substituted moiety selected from the group consisting of C.sub.1-20 aliphatic, C.sub.1-20 heteroaliphatic, 3- to 14-membered carbocyclic, 6- to 10-membered aryl, 5- to 10-membered heteroaryl, and 3- to 12-membered heterocyclic, and q is an integer from 2 to 40.

(23) In certain embodiments, where copolymers of the present invention have a formula P1a, R.sup.1a is —H. In certain embodiments, R.sup.1a is —CH.sub.3. In certain embodiments, R.sup.1a is —CH.sub.2CH.sub.3. In certain embodiments, R.sup.1a is a mixture of —H and —CH.sub.3. In certain embodiments, R.sup.1a is a mixture of H and —CH.sub.2CH.sub.3. In certain embodiments, R.sup.1a is a mixture of H and —CH.sub.2Cl. In certain embodiments, R.sup.1a is a mixture of —CH.sub.3 and —CH.sub.2CH.sub.3. In certain embodiments, R.sup.1a is a mixture of —CH.sub.3 and —CH.sub.2Cl. It will be appreciated that such “mixtures” of R.sup.1a or other substituents refers to cases where for multiple occurrences of the substituent across the polymer, each individual occurrence is selected from one of the specified groups, e.g., hydrogen or —CH.sub.3.

(24) In certain embodiments for compositions of formulae P1 or P1a, n is an integer from 4 to about 4,000. Compositions of the present invention can be regarded as belonging to several distinct categories based on the size of the APC (“aliphatic polycarbonate”) segment. In certain embodiments, the APC segment has a relatively low number of repeat units (e.g. the APC chains have an average of about 4 to about 50 repeat units) hereinafter denoted Category 1. A second category of compositions contain high molecular weight APC segments (e.g. those having more than about 400 repeat units) denoted hereinafter as Category 2. A third category encompasses the intermediate materials where the APC segment has between about 50 and about 400 repeat units, and hereinafter referred to as Category 3. For example, for poly(propylene carbonate)-based compositions, materials of Category 1 having a value of n between about 4 and 50 have APC segments with molecular weights ranging from about 400 to about 5,000 g/mol since the PPC repeat unit has a molecular weight of 102 g/mol. Similar materials belonging to Category 2 contain PPC chains with molecular weights above about 40,000 g/mol, and those in Category 3 contain PPC chains with molecular weights between about 5,000 and about 40,000 g/mol. As discussed in more detail below, each category of materials has advantages for particular applications.

(25) In certain embodiments, compositions of formulae P1, or P1a are further characterized by how highly alternating the APC chains are. During copolymerization of epoxides with CO.sub.2 certain catalysts and conditions lead to the sequential incorporation of two or more epoxides without an interceding carbon dioxide molecule. This produces ether linkages in the polymer chain. There exists a continuum from pure polycarbonates with perfectly alternating structures through polyether-polycarbonates containing proportions of ether and carbonate linkages to pure polyethers where no CO.sub.2 is incorporated.

(26) In certain embodiments, compositions of the present invention contain highly alternating APC segments. In certain embodiments, such compositions comprise APC chains containing greater than 90% carbonate linkages and less than 10% ether linkages. In certain embodiments, such compositions comprise APC chains containing greater than 92%, greater than 93%, greater than 94%, greater than 95%, greater than 96%, greater than 97%, greater than 98%, greater than 99%, or greater than 99.5% carbonate linkages. In certain embodiments, the compositions comprise APC chains with no detectable ether linkages (e.g. as determined by .sup.1H or .sup.13C NMR spectroscopy).

(27) In certain embodiments, compositions of the present invention contain APC segments containing ether linkages. In certain embodiments, such compositions comprise APC chains containing between about 40% and about 90% carbonate linkages with the balance comprising ether linkages. In certain embodiments, such compositions comprise APC chains containing between about 50% and about 90% carbonate linkages, between about 50% and about 80% carbonate linkages carbonate linkages, between about 60% and about 80% carbonate linkages, between about 40% and about 60% carbonate linkages, or between about 80% and about 90% carbonate linkages.

(28) In certain embodiments, compositions of formulae I, P1, and P1a, are further characterized by the distribution of APC chain lengths in the composition. This distribution of chain lengths (and therefore molecular weight) can be assessed by measurement of the polydispersity index (PDI) of the composition. In certain embodiments, compositions of the present invention contain APC segments with a narrow molecular weight distribution. In certain embodiments, the PDI of the composition is less than about 2. In certain embodiments, the PDI is less than about 1.6, less than about 1.4, less than about 1.3, less than about 1.2, or less than about 1.1.

(29) In certain instances, it may be desirable to have a relatively broad PDI. This can be controlled using known methods including those described in co-owned U.S. Pat. No. 7,858,729. Therefore, in certain embodiments, compositions of the present invention contain APC segments with a relatively broad molecular weight distribution. In certain embodiments, the PDI is between about 2 and about 8. In certain embodiments, the PDI is between about 2 and about 5, between about 2 and about 4, between about 2 and about 3, or between about 3 and about 5.

(30) b. Detailed Description of the Hydrocarbon Segment

(31) In its broadest embodiment, the moiety

(32) ##STR00020##
comprises a saturated or unsaturated hydrocarbon. Compositions of the present invention contain hydrocarbon segments

(33) ##STR00021##
that can be regarded as falling into two categories: a first category (hereinafter Category A) comprises polymeric materials such as polyolefins which have a relatively large size (for example those containing more than about 80 and up to many thousands of carbon atoms); a second category (hereinafter Category B) contains smaller hydrocarbon moieties spanning the range from about 4 carbon atoms up to the lower range of category A. In certain embodiments, for materials either category A or B, the moiety

(34) ##STR00022##
is saturated, while in other embodiments, the moiety

(35) ##STR00023##
is partially unsaturated. In certain embodiments, for materials either category, the moiety

(36) ##STR00024##
further comprises one or more aromatic groups.

(37) Turning first to Category A where the moiety

(38) ##STR00025##
comprises a polymeric material, certain embodiments of the present invention encompass materials having a polyefin segment linked to an APC moiety. Suitable polyolefins include polyethylene (PE), polypropylene (PP), polyisobutylene (PIB), polymethylpentene (PMP), polybutene-1 (PB-1), as well as copolymers of any of these with each other or with other olefins such as butadiene, higher alpha olefins, styrene, and the like.

(39) In certain embodiments, for materials of formulae I and P1, and P1a, the moiety

(40) ##STR00026##
comprises polyethylene. In certain embodiments, the moiety

(41) ##STR00027##
comprises a polyethylene moiety having between about 80 and about 500 carbon atoms. In certain embodiments, the moiety

(42) ##STR00028##
comprises a polyethylene moiety having between about 500 and about 2,500 carbon atoms. In certain embodiments, the moiety

(43) ##STR00029##
comprises a polyethylene moiety having between about 2,500 and about 10,000 carbon atoms. In certain embodiments, the moiety

(44) ##STR00030##
comprises a polyethylene moiety having between about 10,000 and about 50,000 carbon atoms. In certain embodiments, the moiety

(45) ##STR00031##
comprises a polyethylene moiety having between about 50,000 and about 100,000 carbon atoms. In certain embodiments, such polyethylene moieties are linear. In certain embodiments, such polyethylene moieties contain long chain branching. In certain embodiments, such polyethylene moieties contain branches introduced by copolymerization of ethylene with alpha olefins.

(46) In certain embodiments, for materials of formulae I, P1, and P1a, the moiety

(47) ##STR00032##
comprises polypropylene. In certain embodiments, the moiety

(48) ##STR00033##
comprises a polypropylene moiety having between about 80 and about 500 carbon atoms. In certain embodiments, the moiety

(49) ##STR00034##
comprises a polypropylene moiety having between about 500 and about 2,500 carbon atoms. In certain embodiments, the moiety

(50) ##STR00035##
comprises a polypropylene moiety having between about 2,500 and about 10,000 carbon atoms. In certain embodiments, the moiety

(51) ##STR00036##
comprises a polypropylene moiety having between about 10,000 and about 50,000 carbon atoms. In certain embodiments, the moiety

(52) ##STR00037##
comprises a polypropylene moiety having between about 50,000 and about 100,000 carbon atoms. In certain embodiments, such polypropylene moieties are linear. In certain embodiments, such polypropylene moieties contain long chain branching. In certain embodiments, such polypropylene moieties contain branches introduced by copolymerization of propylene with higher alpha olefins. In certain embodiments, such polypropylene moieties are isotactic. In certain embodiments, such polypropylene moieties are syndiotactic. In other embodiments, such polypropylene moieties are atactic.

(53) In certain embodiments, for materials of formulae I and P1, and P1a, the moiety

(54) ##STR00038##
comprises polypropylene. In certain embodiments, the moiety

(55) ##STR00039##
comprises a polyisobutylene moiety having between about 80 and about 500 carbon atoms. In certain embodiments, the moiety

(56) ##STR00040##
comprises a polyisobutylene moiety having between about 500 and about 2,500 carbon atoms. In certain embodiments, the moiety

(57) ##STR00041##
comprises a polyisobutylene moiety having between about 2,500 and about 10,000 carbon atoms. In certain embodiments, the moiety

(58) ##STR00042##
comprises a polyisobutylene moiety having between about 10,000 and about 50,000 carbon atoms.

(59) Of particular utility are

(60) ##STR00043##
derived from polyolefins containing a substituent such as a hydroxyl or carboxyl group since these provide a means of attaching the APC moiety to the polyolefin (i.e. using methods described more fully below). Suitable methods are known in the art for the manufacture of polyethylene and other polyolefins with a hydroxyl or carboxyl group at one chain terminus. For example, manufacture of hydroxyl-terminated polyethylene is described in Macromolecules 2002, 35, 8923-8925 which is incorporated herein by reference.

(61) As noted above, a second category of materials encompassed by the present invention comprise compositions having an APC moiety bound to a hydrocarbon having between about 4 and about 80 carbon atoms (Category B). In certain embodiments, for materials of formulae I, P1, and P1a, the moiety

(62) ##STR00044##
comprises a C.sub.4 to C.sub.80 aliphatic group. In certain embodiments, for materials of formulae I, P1, and P1a, the moiety

(63) ##STR00045##
comprises a saturated C.sub.4 to C.sub.80 aliphatic group. In certain embodiments, for materials of formulae I, P1, and P1a, the moiety

(64) ##STR00046##
comprises an unsaturated saturated C.sub.4 to C.sub.80 aliphatic group. In certain embodiments, for materials of formulae I, P1, and P1a, the moiety

(65) ##STR00047##
comprises a straight-chain C.sub.4 to C.sub.80 aliphatic group. In certain embodiments, for materials of formulae I, P1, and P1a, the moiety

(66) ##STR00048##
comprises a branched-chain C.sub.4 to C.sub.80 aliphatic group.

(67) In embodiments, for compounds of formulae I, P1, and P1a,

(68) ##STR00049##
comprises a straight-chain aliphatic group. In certain embodiments, such aliphatic groups comprise 6 to 80 carbon atoms. In certain embodiments,

(69) ##STR00050##
comprises a C.sub.7-12 straight-chain aliphatic group. In certain embodiments,

(70) ##STR00051##
comprises a C.sub.12-16 straight-chain aliphatic group. In certain embodiments,

(71) ##STR00052##
comprises a C.sub.16-20 straight-chain aliphatic group. In certain embodiments,

(72) ##STR00053##
comprises a C.sub.20-24 straight-chain aliphatic group, a C.sub.24-28 straight-chain aliphatic group, a C.sub.28-36 straight-chain aliphatic group, or a C.sub.36-40 straight-chain aliphatic group. In certain embodiments,

(73) ##STR00054##
comprises a C.sub.40-60 straight-chain aliphatic group or a C.sub.60-80 straight-chain aliphatic group. In certain embodiments, such straight-chain aliphatic groups are saturated, while in other embodiments, they contain one or more sites of unsaturation. In certain embodiments, such groups comprise or are derived from the chain of a naturally-occurring material such as a long-chain fatty acid.

(74) In embodiments where

(75) ##STR00055##
comprises a saturated straight aliphatic chain, suitable chains include, but are not limited to those corresponding to common fatty acids. In certain embodiments suitable chains for compounds conforming to formula P1 include, but are not limited to those shown in Table 1:

(76) TABLE-US-00001 TABLE 1 Examples of Saturated Fatty Acids Common name of fatty acid Aliphatic group Caprylic acid CH.sub.3(CH.sub.2).sub.6— Capric acid CH.sub.3(CH.sub.2).sub.8— Laurie acid CH.sub.3(CH.sub.2).sub.10— Myristic acid CH.sub.3(CH.sub.2).sub.12— Palmitic acid CH.sub.3(CH.sub.2).sub.14— Stearic acid CH.sub.3(CH.sub.2).sub.16— Rachidic acid CH.sub.3(CH.sub.2).sub.18— Behenic acid CH.sub.3(CH.sub.2).sub.20— Lignoceric acid CH.sub.3(CH.sub.2).sub.22— Cerotic acid CH.sub.3(CH.sub.2).sub.24—

(77) In embodiments where

(78) ##STR00056##
comprises an unsaturated straight aliphatic chain, suitable chains include, but are not limited to those corresponding to unsaturated fatty acids. In certain embodiments suitable chains include, but are not limited to those shown in Table 2:

(79) TABLE-US-00002 TABLE 2 Examples of Unsaturated Fatty Acids Common name of fatty acid Corresponding Aliphatic Group Δ.sup.x Myristoleic CH.sub.3(CH.sub.2).sub.3CH═CH(CH.sub.2).sub.7— cis-Δ.sup.9 acid Palmitoleic CH.sub.3(CH.sub.2).sub.5CH═CH(CH.sub.2).sub.7— cis-Δ.sup.9 acid Sapienic CH.sub.3(CH.sub.2).sub.8CH═CH(CH.sub.2).sub.4— cis-Δ.sup.6 acid Oleic acid CH.sub.3(CH.sub.2).sub.7CH═CH(CH.sub.2).sub.7— cis-Δ.sup.9 Elaidic acid CH.sub.3(CH.sub.2).sub.7CH═CH(CH.sub.2).sub.7— trans-Δ.sup.9 Vaccenic CH.sub.3(CH.sub.2).sub.5CH═CH(CH.sub.2).sub.9— trans-Δ.sup.11 acid Linoleic CH.sub.3(CH.sub.2).sub.4CH═CHCH.sub.2CH═CH(CH.sub.2).sub.7— cis,cis- acid Δ.sup.9,Δ.sup.12 Linoelaidic CH.sub.3(CH.sub.2).sub.4CH═CHCH.sub.2CH═CH(CH.sub.2).sub.7— trans, trans- acid Δ.sup.9,Δ.sup.12 α-Linolenic CH.sub.3CH.sub.2CH═CHCH.sub.2CH═CHCH.sub.2CH═CH(CH.sub.2).sub.7— cis, cis, cis- acid Δ.sup.9,Δ.sup.12,Δ.sup.15 Arachidonic CH.sub.3(CH.sub.2).sub.4CH═CHCH.sub.2CH═CHCH.sub.2CH═CHCH.sub.2CH═CH(CH.sub.2).sub.3— cis,cis,cis, acid cis-Δ.sup.5,Δ.sup.8, Δ.sup.11,Δ.sup.14 Eicosapent- CH.sub.3CH.sub.2CH═CHCH.sub.2CH═CHCH.sub.2CH═CHCH.sub.2CH═CHCH.sub.2CH═CH(CH.sub.2).sub.3— cis, cis, cis, aenoic acid cis, cis-Δ.sup.5, Δ.sup.8, Δ.sup.11,Δ.sup.14,Δ.sup.17 Erucic acid CH.sub.3(CH.sub.2).sub.7CH═CH(CH.sub.2).sub.11— cis-Δ.sup.13 Docosahex- CH.sub.3CH.sub.2CH═CHCH.sub.2CH═CHCH.sub.2CH═CHCH.sub.2CH═CHCH.sub.2CH═CHCH.sub.2CH═CH(CH.sub.2).sub.2— cis,cis,cis, aenoic acid cis,cis,cis- Δ.sup.4,Δ.sup.7,Δ.sup.10, Δ.sup.13,Δ.sup.16,Δ.sup.19

(80) In certain embodiments,

(81) ##STR00057##
comprises a semisynthetic derivative of a fatty acid. Numerous processes are known in the art for the chemical modification of fatty acid feedstocks, such processes include, but are not limited to: complete or partial hydrogentation, olefin isomerization, olefin metathesis, hydride reduction and the like. Such semisynthetic materials and processes will be readily apprehended by the skilled artisan and can be utilized to make inventive compounds of formulae I, P1, and P1a.

(82) In embodiments, for compounds of formulae I, P1, and P1a,

(83) ##STR00058##
comprises a branched aliphatic group. In certain embodiments, such aliphatic groups comprise from 4 to about 80 carbon atoms. In certain embodiments,

(84) ##STR00059##
comprises a C.sub.4-6 branched-chain aliphatic group. In certain embodiments,

(85) ##STR00060##
comprises a C.sub.7-12 branched-chain aliphatic group. In certain embodiments,

(86) ##STR00061##
comprises a C.sub.12-16 branched-chain aliphatic group. In certain embodiments,

(87) ##STR00062##
comprises a C.sub.16-20 branched-chain aliphatic group. In certain embodiments,

(88) ##STR00063##
comprises a C.sub.20-24 branched-chain aliphatic group, a C.sub.24-28 branched-chain aliphatic group, a C.sub.28-36 branched-chain aliphatic group, or a C.sub.36-40 branched-chain aliphatic group. In certain embodiments,

(89) ##STR00064##
comprises a C.sub.40-60 branched-chain aliphatic group or a C.sub.60-80 branched-chain aliphatic group. In certain embodiments, such branched-chain aliphatic groups are saturated, while in other embodiments, they contain one or more sites of unsaturation.

(90) In certain embodiments,

(91) ##STR00065##
comprises a saturated aliphatic group with a branch present at the site of attachment of the

(92) ##STR00066##
moiety to the aliphatic polycarbonate moiety. In certain other embodiments, the point of attachment of the

(93) ##STR00067##
moiety to the aliphatic polycarbonate moiety is not a point of branching.

(94) In certain embodiments where

(95) ##STR00068##
comprises a saturated aliphatic group with a branch resent at a site other than the site of attachment to the polycarbonate moiety, the

(96) ##STR00069##
moiety comprises a C.sub.3-40 straight carbon chain with one or more alkyl substituents. In certain embodiments, the

(97) ##STR00070##
moiety comprises a C.sub.4-40 straight carbon chain with 1-12 alkyl substituents. In certain embodiments, the

(98) ##STR00071##
moiety comprises a C.sub.4-40 straight carbon chain with 1-12 alkyl substituents, where each alkyl substituent is independently a C.sub.1-12 straight or branched alkyl. In certain embodiments, the

(99) ##STR00072##
moiety comprises a C.sub.4-20 straight carbon chain with 1-6 alkyl substituents, where each alkyl substituent is independently a C.sub.1-6 straight or branched alkyl. In certain embodiments, the

(100) ##STR00073##
moiety comprises a C.sub.6-12 straight carbon chain with 1-4 alkyl substituents, where each alkyl substituent is independently a C.sub.1-4 straight or branched alkyl. In certain embodiments, the

(101) ##STR00074##
moiety comprises a C.sub.4-20 straight carbon chain with 1-6 alkyl substituents, where each alkyl substituent is independently a methyl or ethyl group.

(102) In certain embodiments where

(103) ##STR00075##
comprises a saturated aliphatic group with a branch present at a site other than the site of attachment to the polycarbonate moiety, the

(104) ##STR00076##
moiety comprises a moiety selected from the group consisting of: sec-butyl, 2-methylbutane, 3-methylbutane, 2-methylpentane, 3-methylpentane, 4-methylpentane, 2-methylhexane, 3-methylhexane, 4-methylhexane, 5-methylhexane, 2-methylheptane, 3-methylheptane, 4-methylheptane, 5-methylheptane, 6-methylheptane, 2-methyloctane, 3-methyloctane, 4-methyloctane, 5-methyloctane, 6-methyloctane, 7-methyloctane, 2-methylnonane, 3-methylnonane, 4-methylnonane, 5-methylnonane, 6-methylnonane, 7-methylnonane, 8-methylnonane, 2-methyldecane, 3-methyldecane, 4-methyldecane, 5-methyldecane, 6-methyldecane, 7-methyldecane, 8-methyldecane, 9-methyldecane, 2-methylundecane, 3-methylundecane, 4-methylundecane, 5-methylundecane, 6-methylundecane, 7-methylundecane, 8-methylundecane, 9-methylundecane, 10-methylundecane, 2-methyldodecane, 3-methyldodecane, 4-methyldodecane, 5-methyldodecane, 6-methyldodecane, 7-methyldodecane, 8-methyldodecane, 9-methyldodecane, 10-methyldodecane, 11-methyldodecane, 2-ethylbutane, 2-ethylpentane, 3-ethylpentane, 2-ethylhexane, 3-ethylhexane, 4-ethylhexane, 2-ethylheptane, 3-ethylheptane, 4-ethylheptane, 5-ethylheptane, 2-ethyloctane, 3-ethyloctane, 4-ethyloctane, 5-ethyloctane, 6-ethyloctane, 2-ethylnonane, 3-ethylnonane, 4-ethylnonane, 5-ethylnonane, 6-ethylnonane, 7-ethylnonane, 2-ethyldecane, 3-ethyldecane, 4-ethyldecane, 5-ethyldecane, 6-ethyldecane, 7-ethyldecane, 8-ethyldecane, 2-ethylundecane, 3-ethylundecane, 4-ethylundecane, 5-ethylundecane, 6-ethylundecane, 7-ethylundecane, 8-ethylundecane, 9-ethylundecane, 2-ethyldodecane, 3-ethyldodecane, 4-ethyldodecane, 5-ethyldodecane, 6-ethyldodecane, 7-ethyldodecane, 8-ethyldodecane, 9-ethyldodecane, 10-ethyldodecane, and combinations of any two or more of these.

(105) For avoidance of doubt with respect to interpretation of chemical structures, where a

(106) ##STR00077##
moiety is selected from the group above, the point of connection to the APC moiety is to be interpreted as C-1. Therefore, if

(107) ##STR00078##
in a compound of formula P1 were chosen from the group above to be 5-methylheptane, then the compound would have a structure:

(108) ##STR00079##

(109) In certain embodiments where

(110) ##STR00080##
comprises a saturated aliphatic group with a branch present at a site other than the site of attachment to the polycarbonate moiety,

(111) ##STR00081##
comprises a moiety selected from the group consisting of: a C.sub.5 straight chain alkyl having two substituents independently selected from C.sub.1-4 straight or branched alkyl; a C.sub.6 straight chain alkyl having 2-3 substituents independently selected from C.sub.1-4 straight or branched alkyl; a C.sub.7 straight chain alkyl having 2-3 substituents independently selected from C.sub.1-4 straight or branched alkyl; a C.sub.8 straight chain alkyl having 2-4 substituents independently selected from C.sub.1-4 straight or branched alkyl; a C.sub.6 straight chain alkyl having 2-4 substituents independently selected from C.sub.1-4 straight or branched alkyl; a C.sub.10 straight chain alkyl having 2-4 substituents independently selected from C.sub.1-4 straight or branched alkyl; a C.sub.111-12 straight chain alkyl having 2-4 substituents independently selected from C.sub.1-4 straight or branched alkyl; a C.sub.12-16 straight chain alkyl having 2-5 substituents independently selected from C.sub.1-4 straight or branched alkyl; a C.sub.16-20 straight chain alkyl having 2-6 substituents independently selected from C.sub.1-4 straight or branched alkyl; and a C.sub.20-40 straight chain alkyl having 2-12 substituents independently selected from C.sub.1-4 straight or branched alkyl.

(112) In certain embodiments, a

(113) ##STR00082##
moiety comprises

(114) ##STR00083##
where * represents the site of attachment of the

(115) ##STR00084##
moiety to the polycarbonate moiety, and f is an integer from 1 to 12.

(116) In certain embodiments, a

(117) ##STR00085##
moiety is selected from the group consisting of:

(118) ##STR00086##
where k is an integer from 0 to 10.

(119) In embodiments, where a branch occurs at the site of attachment of the

(120) ##STR00087##
moiety to the aliphatic polycarbonate moiety, such a compound can conform to formula P3a:

(121) ##STR00088## where each of R.sup.1, R.sup.2, R.sup.3, R.sup.4, and n is as defined above and in the classes and subclasses herein, and R.sup.a1 and R.sup.a2 are each independently a C.sub.1-40 aliphatic group.

(122) In certain embodiments for compounds conforming to formula P3a, each of R.sup.a1 and R.sup.a2 comprises a straight chain aliphatic group. In certain embodiments, each of R.sup.a1 and R.sup.a2 is independently selected from the group consisting of C.sub.1-40 aliphatic groups, wherein R.sup.a1 and R.sup.a2 taken together with the carbon atom to which they are attached contain more than 4 carbon atoms. In certain embodiments, R.sup.a1 and R.sup.a2 together with the carbon atom to which they are attached contain between 4 and 80 carbon atoms. In certain embodiments, R.sup.a1 and R.sup.a2 and the carbon atom to which they are attached comprise at least 6, at least 8, at least 10, at least 12, at least 16, at least 20, at least 24, at least 30, at least 34, or at least 38 carbon atoms.

(123) In certain embodiments,

(124) ##STR00089##
is selected from the group consisting of: 2-butane, 2-pentane, 3-pentane, 2-hexane, 3-hexane, 2-heptane, 3-heptane, 4-heptane, 2-octane, 3-octane, 4-octane, 2-nonane, 3-nonane, 4-nonane, 5-nonane, 2-decane, 3-decane, 4-decane, 5-decane, 2-undecane, 3-undecane, 4-undecane, 5-undecane, 6-undecane, 2-dodecane, 3-dodecane, 4-dodecane, 5-dodecane, 6-dodecane, and combinations of any two or more of these.

(125) For avoidance of doubt with respect to interpretation of chemical structures, if

(126) ##STR00090##
in a compound of formula P3a were chosen from the group above to be 4-heptane, then the compound would have a structure:

(127) ##STR00091##

(128) In certain embodiments for compounds conforming to formula P3a, at least one of R.sup.a1 and R.sup.a2 comprises one or more branch points. As used herein, the term “branch point” refers to an atom which is attached to three or more non-hydrogen atoms. In some embodiments, a branch point is a carbon atom attached to three or more carbon atoms.

(129) In certain embodiments, one or more of R.sup.a1 and R.sup.a2 comprises methyl or ethyl substituents. In certain embodiments, R.sup.a1 and R.sup.a2 are independently selected from the group consisting of: methyl, ethyl, propyl, butyl, n-pentane, n-hexane, n-heptane, n-octane, any C.sub.9-40 n-alkyl, isopropyl, isobutyl, sec-butyl, 2-methylbutane, 3-methylbutane, 2-methylpentane, 3-methylpentane, 4-methylpentane, 2-methylhexane, 3-methylhexane, 4-methylhexane, 5-methylhexane, 2-methylheptane, 3-methylheptane, 4-methylheptane, 5-methylheptane, 6-methylheptane, 2-methyloctane, 3-methyloctane, 4-methyloctane, 5-methyloctane, 6-methyloctane, 7-methyloctane, 2-methylnonane, 3-methylnonane, 4-methylnonane, 5-methylnonane, 6-methylnonane, 7-methylnonane, 8-methylnonane, 2-methyldecane, 3-methyldecane, 4-methyldecane, 5-methyldecane, 6-methyldecane, 7-methyldecane, 8-methyldecane, 9-methyldecane, 2-methylundecane, 3-methylundecane, 4-methylundecane, 5-methylundecane, 6-methylundecane, 7-methylundecane, 8-methylundecane, 9-methylundecane, 10-methylundecane, 2-methyldodecane, 3-methyldodecane, 4-methyldodecane, 5-methyldodecane, 6-methyldodecane, 7-methyldodecane, 8-methyldodecane, 9-methyldodecane, 10-methyldodecane, 11-methyldodecane, 2-ethylbutane, 2-ethylpentane, 3-ethylpentane, 2-ethylhexane, 3-ethylhexane, 4-ethylhexane, 2-ethylheptane, 3-ethylheptane, 4-ethylheptane, 5-ethylheptane, 2-ethyloctane, 3-ethyloctane, 4-ethyloctane, 5-ethyloctane, 6-ethyloctane, 2-ethylnonane, 3-ethylnonane, 4-ethylnonane, 5-ethylnonane, 6-ethylnonane, 7-ethylnonane, 2-ethyldecane, 3-ethyldecane, 4-ethyldecane, 5-ethyldecane, 6-ethyldecane, 7-ethyldecane, 8-ethyldecane, 2-ethylundecane, 3-ethylundecane, 4-ethylundecane, 5-ethylundecane, 6-ethylundecane, 7-ethylundecane, 8-ethylundecane, 9-ethylundecane, 2-ethyldodecane, 3-ethyldodecane, 4-ethyldodecane, 5-ethyldodecane, 6-ethyldodecane, 7-ethyldodecane, 8-ethyldodecane, 9-ethyldodecane, 10-ethyldodecane, and combinations of any two or more of these; wherein R.sup.a1 and R.sup.a2 together with the carbon atom to which they are attached comprise at least 4 carbon atoms. In certain embodiments, R.sup.a1 and R.sup.a2 together with the carbon atom to which they are at attached comprise at least 6, at least 8, at least 10, at least 12, at least 16, at least 20, at least 24, at least 30, at least 34 or at least 38 carbon atoms.

(130) For avoidance of doubt with respect to interpretation of chemical structures, in a compound of formula P1 where the

(131) ##STR00092##
comprises

(132) ##STR00093##
and R.sup.a1 and R.sup.a2 are selected from the group above such that R.sup.a1 is n-butyl and R.sup.a2 is 3-methylhexane, then the compound would have a structure:

(133) ##STR00094##

(134) In certain embodiments for compounds conforming to formula P3a, at least one of R.sup.a1 and R.sup.a2 is selected from the group consisting of: a C.sub.5 straight chain alkyl having 1-2 substituents independently selected from C.sub.1-4 straight or branched alkyl; a C.sub.6 straight chain alkyl having 1-3 substituents independently selected from C.sub.1-4 straight or branched alkyl; a C.sub.7 straight chain alkyl having 1-3 substituents independently selected from C.sub.1-4 straight or branched alkyl; a C.sub.8 straight chain alkyl having 1-4 substituents independently selected from C.sub.1-4 straight or branched alkyl; a C.sub.6 straight chain alkyl having 1-4 substituents independently selected from C.sub.1-4 straight or branched alkyl; a C.sub.10 straight chain alkyl having 1-4 substituents independently selected from C.sub.1-4 straight or branched alkyl; a C.sub.11-12 straight chain alkyl having 1-4 substituents independently selected from C.sub.1-4 straight or branched alkyl; a C.sub.12-16 straight chain alkyl having 1-5 substituents independently selected from C.sub.1-4 straight or branched alkyl; a C.sub.16-20 straight chain alkyl having 1-6 substituents independently selected from C.sub.1-4 straight or branched alkyl; and a a C.sub.20-40 straight chain alkyl having 1-12 substituents independently selected from C.sub.1-4 straight or branched alkyl.

(135) In certain embodiments, at least one of R.sup.a1 and R.sup.a2 comprises

(136) ##STR00095##
where * represents the site of attachment of the

(137) ##STR00096##
moiety to the polycarbonate moiety, and f is an integer from 1 to 12.

(138) In certain embodiments, at least one of R.sup.a1 and R.sup.a2 comprises is selected from the group consisting of:

(139) ##STR00097##
where k is an integer from 0 to 10.
c. Detailed Description of the Block Copolymers

(140) Having described in some detail the structures and characteristics of each of the two components which make up the block copolymer materials of the present invention, we now turn to the combinations of those components. The present invention encompasses materials of formula P1 comprising any of the APC segments described above in combination with any of the hydrocarbon segments described above. In certain embodiments, the invention encompasses compositions comprising mixtures of any two or more such materials.

(141) The present invention can be regarded as encompassing a family of related materials that can be divided into genera based on two primary characteristics: i) the size of the hydrocarbon moiety

(142) ##STR00098##  which can be in Category A (polymers with more than about 80 carbon atoms) or Category B (aliphatic groups with between about 4 and 80 carbon atoms); and ii) the molecular weight range of the APC unit, which can be in any of three ranges described above as Category 1 (400 to 5,000 g/mol), Category 2 (40,000+ g/mol), and Category 3 (5,000 to 40,000 g/mol).

(143) For convenience, compositions of the present invention are described below based on their association within these three categories. For example, a compound referred to as type P1-B-2 will conform to formula P1, and in certain embodiments will contain a

(144) ##STR00099##
moiety with fewer than 80 carbon atoms and will have an APC moiety having more than about 40 repeat units in the chain. Materials in each of the resulting 6 families (P1-A-1; P1-A-2; P1-A-3; P1-B-1; P1-B-2; and P1-B-3) have unique features and can be profitably employed for specific applications. For example, materials belonging to category P1-A-1 have a high hydrocarbon-to-APC ratio and are therefore more hydrophobic than materials in other categories. Conversely, materials belonging to category P1-B-2 have low hydrocarbon-to-APC ratios. Materials in any of category P1A-1 through P1-A-3 and P1-B-2 have relatively high molecular weights and are mostly solids, glasses, or waxes. Materials in categories B-1 and B-3 have relatively lower molecular weights and include materials that are liquids. The choice of whether to apply a composition from one genus or another will depend upon the intended application as further described below.

(145) In certain embodiments, the present invention provides compositions denoted P1-A-1. These materials are generally solids or waxes and are relatively hydrophobic.

(146) Such materials conform to formula P1:

(147) ##STR00100## where each of R.sup.1, R.sup.2, R.sup.3, and R.sup.4 are as defined above and in the classes and subclasses herein; n is an integer from 4 to about 50; and the moiety

(148) ##STR00101##  comprises a hydrocarbon having more than about 80 carbon atoms.

(149) In certain embodiments, compositions of the present invention comprise materials of category P1-A-1 wherein each of the variables R.sup.1, R.sup.2, R.sup.3, and R.sup.4 is at each occurrence —H (e.g. the APC portion of the molecule comprises a poly(ethylene carbonate) chain. In certain embodiments, compositions of the present invention comprise materials of category P1-A-1 wherein three of the variables R.sup.1, R.sup.2, R.sup.3, and R.sup.4 are at each occurrence —H and the remaining variable is —CH.sub.3 (e.g. the APC portion of the molecule comprises a poly(propylene carbonate) chain.

(150) In certain embodiments, compositions of the present invention comprise materials of category P1-A-1 wherein n is, on average in the composition, between about 4 and about 8. In certain embodiments, compositions of the present invention comprise materials of category P1-A-1 wherein n is, on average in the composition, between about 6 and about 10. In certain embodiments, compositions of the present invention comprise materials of category P1-A-1 wherein n is, on average in the composition, between about 8 and about 12. In certain embodiments, compositions of the present invention comprise materials of category P1-A-1 wherein n is, on average in the composition, between about 12 and about 16. In certain embodiments, compositions of the present invention comprise materials of category P1-A-1 wherein n is, on average in the composition, between about 16 and about 20. In certain embodiments, compositions of the present invention comprise materials of category P1-A-1 wherein n is, on average in the composition, between about 20 and about 40. In certain embodiments, compositions of the present invention comprise materials of category P1-A-1 wherein n is, on average in the composition, between about 30 and about 50.

(151) In certain embodiments, compositions of the present invention comprise materials of category P1-A-1 wherein the moiety

(152) ##STR00102##
comprises a polyethylene chain. In certain embodiments, compositions of the present invention comprise materials of category P1-A-1 wherein the moiety

(153) ##STR00103##
comprises polyethylene with an Mn of between about 1,000 and about 5,000 g/mol. In certain embodiments, the moiety

(154) ##STR00104##
in materials of category P1-A-1 comprises polyethylene with an Mn of between about 3,500 and about 10,000 g/mol. In certain embodiments, the moiety

(155) ##STR00105##
in materials of category P1-A-1 comprises polyethylene with an Mn of between about 3,500 and about 10,000 g/mol. In certain embodiments, the moiety

(156) ##STR00106##
in materials of category P1-A-1 comprises polyethylene with an Mn of between about 10,000 and about 100,000 g/mol.

(157) In certain embodiments, compositions of the present invention comprise materials of category P1-A-1 wherein the moiety

(158) ##STR00107##
comprises a polypropylene chain. In certain embodiments, compositions of the present invention comprise materials of category P1-A-1 wherein the moiety

(159) ##STR00108##
comprises polypropylene with an Mn of between about 1,000 and about 5,000 g/mol. In certain embodiments, the moiety

(160) ##STR00109##
in materials of category P1-A-1 comprises polypropylene with an Mn of between about 3,500 and about 10,000 g/mol. In certain embodiments, the moiety

(161) ##STR00110##
in materials of category P1-A-1 comprises polypropylene with an Mn of between about 3,500 and about 10,000 g/mol. In certain embodiments, the moiety

(162) ##STR00111##
in materials of category P1-A-1 comprises polypropylene with an Mn of between about 10,000 and about 100,000 g/mol.

(163) In certain embodiments, the present invention comprises materials of category P1-A-1 selected from Table 3.

(164) TABLE-US-00003 TABLE 3 CxHy Desig- iden- CxHy nation APC identity n tity (g/mol) P1-A- 1a 4 PE 1,000 P1-A- 1b 4 PE 1,000 P1-A- 1c 6 PE 1,000 P1-A- 1d 6 PE 1,000 P1-A- 1e 8 PE 1,000 P1-A- 1f 8 PE 1,000 P1-A- 1g 12 PE 1,000 P1-A- 1h 12 PE 1,000 P1-A- 1i 0 4 PP 1,000 P1-A- 1j 4 PP 1,000 P1-A- 1k 6 PP 1,000 P1-A- 1l 6 PP 1,000 P1-A- 1m 8 PP 1,000 P1-A- 1n 8 PP 1,000 P1-A- 1o 12 PP 1,000 P1-A- 1p 12 PP 1,000 P1-A- 1q 4 PE 2,000 P1-A- 1r 4 PE 2,000 P1-A- 1s 0 6 PE 2,000 P1-A- 1t 6 PE 2,000 P1-A- 1u 8 PE 2,000 P1-A- 1v 8 PE 2,000 P1-A- 1w 12 PE 2,000 P1-A- 1x 12 PE 2,000 P1-A- 1y 4 PP 2,000 P1-A- 1z 4 PP 2,000 P1-A- 1aa 6 PP 2,000 P1-A- 1ab 6 PP 2,000 P1-A- 1ac 0 8 PP 2,000 P1-A- 1ad 8 PP 2,000 P1-A- 1ae 12 PP 2,000 P1-A- 1af 12 PP 2,000 P1-A- 1a 4 PE 3,000 P1-A- 1b 4 PE 3,000 P1-A- 1c 6 PE 3,000 P1-A- 1d 6 PE 3,000 P1-A- 1e 8 PE 3,000 P1-A- 1f 8 PE 3,000 P1-A- 1g 0 12 PE 3,000 P1-A- 1h 12 PE 3,000 P1-A- 1i 4 PP 3,000 P1-A- 1j 4 PP 3,000 P1-A- 1k 6 PP 3,000 P1-A- 1l 6 PP 3,000 P1-A- 1m 8 PP 3,000 P1-A- 1n 8 PP 3,000 P1-A- 1o 12 PP 3,000 P1-A- 1p 12 PP 3,000 P1-A- 1q 0 4 PE 10,000 P1-A- 1r 4 PE 10,000 P1-A- 1s 6 PE 10,000 P1-A- 1t 6 PE 10,000 P1-A- 1u 8 PE 10,000 P1-A- 1v 8 PE 10,000 P1-A- 1w 12 PE 10,000 P1-A- 1x 12 PE 10,000 P1-A- 1y 4 PE 20,000 P1-A- 1z 4 PE 20,000 P1-A- 1aa 0 6 PE 20,000 P1-A- 1ab 6 PE 20,000 P1-A- 1ac 8 PE 20,000 P1-A- 1ad 8 PE 20,000 P1-A- 1ae 12 PE 20,000 P1-A- 1af 12 PE 20,000

(165) In certain embodiments, the present invention provides compositions denoted P1-A-2. Such materials have a formula P1:

(166) ##STR00176## where each of R.sup.1, R.sup.2, R.sup.3, and R.sup.4 are as defined above and in the classes and subclasses herein; n is an integer from 400 to about 5,000; and the moiety

(167) ##STR00177##  comprises a hydrocarbon having more than about 80 carbon atoms.

(168) In certain embodiments, compositions of the present invention comprise materials of category P1-A-2 wherein each of the variables R.sup.1, R.sup.2, R.sup.3, and R.sup.4 is at each occurrence —H (e.g. the APC portion of the molecule comprises a poly(ethylene carbonate) chain. In certain embodiments, compositions of the present invention comprise materials of category P1-A-2 wherein three of the variables R.sup.1, R.sup.2, R.sup.3, and R.sup.4 are at each occurrence —H and the remaining variable is —CH.sub.3 (e.g. the APC portion of the molecule comprises a poly(propylene carbonate) chain.

(169) In certain embodiments, compositions of the present invention comprise materials of category P1-A-2 wherein n is, on average in the composition, between about 400 and about 600. In certain embodiments, compositions of the present invention comprise materials of category P1-A-2 wherein n is, on average in the composition, between about 500 and about 1,500. In certain embodiments, compositions of the present invention comprise materials of category P1-A-2 wherein n is, on average in the composition, between about 1,500 and about 3,000. In certain embodiments, compositions of the present invention comprise materials of category P1-A-2 wherein n is, on average in the composition, between about 3,000 and about 5,000.

(170) In certain embodiments, compositions of the present invention comprise materials of category P1-A-2 wherein the moiety

(171) ##STR00178##
comprises a polyethylene chain. In certain embodiments, compositions of the present invention comprise materials of category P1-A-2 wherein the moiety

(172) ##STR00179##
comprises polyethylene with an Mn of between about 1,000 and about 5,000 g/mol. In certain embodiments, the moiety

(173) ##STR00180##
in materials of category P1-A-2 comprises polyethylene with an Mn of between about 3,500 and about 10,000 g/mol. In certain embodiments, the moiety

(174) ##STR00181##
in materials of category P1-A-2 comprises polyethylene with an Mn of between about 3,500 and about 10,000 g/mol. In certain embodiments, the moiety

(175) ##STR00182##
in materials of category P1-A-2 comprises polyethylene with an Mn of between about 10,000 and about 100,000 g/mol. In certain embodiments, the moiety

(176) ##STR00183##
in materials of category P1-A-2 comprises polyethylene with an Mn above about 100,000 g/mol.

(177) In certain embodiments, compositions of the present invention comprise materials of category P1-A-2 wherein the moiety

(178) ##STR00184##
comprises a polypropylene chain. In certain embodiments, compositions of the present invention comprise materials of category P1-A-2 wherein the moiety

(179) ##STR00185##
comprises polypropylene with an Mn of between about 1,000 and about 5,000 g/mol. In certain embodiments, the moiety

(180) ##STR00186##
in materials of category P1-A-2 comprises polypropylene with an Mn of between about 3,500 and about 10,000 g/mol. In certain embodiments, the moiety

(181) ##STR00187##
in materials of category P1-A-2 comprises polypropylene with an Mn of between about 3,500 and about 10,000 g/mol. In certain embodiments, the moiety

(182) ##STR00188##
in materials of category P1-A-2 comprises polypropylene with an Mn of between about 10,000 and about 100,000 g/mol. In certain embodiments, the moiety

(183) ##STR00189##
in materials of category P1-A-2 comprises polypropylene with an Mn above about 100,000 g/mol.

(184) In certain embodiments, the present invention comprises materials of category P1-A-2 selected from Table 4.

(185) TABLE-US-00004 TABLE 4 CxHy CxHy Desig- iden- (g/ nation APC identity n tity mol) P1-A- 1a 0 400 PE 1,000 P1-A- 1b 400 PE 1,000 P1-A- 1c 750 PE 1,000 P1-A- 1d 750 PE 1,000 P1-A- 1e 1000 PE 1,000 P1-A- 1f 1000 PE 1,000 P1-A- 1g 2000 PE 1,000 P1-A- 1h 2000 PE 1,000 P1-A- 1i 400 PP 1,000 P1-A- 1j 400 PP 1,000 P1-A- 1k 00 750 PP 1,000 P1-A- 1l 01 750 PP 1,000 P1-A- 1m 02 1000 PP 1,000 P1-A- 1n 03 1000 PP 1,000 P1-A- 1o 04 2000 PP 1,000 P1-A- 1p 05 2000 PP 1,000 P1-A- 1q 06 400 PE 2,000 P1-A- 1r 07 400 PE 2,000 P1-A- 1s 08 750 PE 2,000 P1-A- 1t 09 750 PE 2,000 P1-A- 1u 0 1000 PE 2,000 P1-A- 1v 1000 PE 2,000 P1-A- 1w 2000 PE 2,000 P1-A- 1x 2000 PE 2,000 P1-A- 1y 400 PP 2,000 P1-A- 1z 400 PP 2,000 P1-A- 1aa 750 PP 2,000 P1-A- 1ab 750 PP 2,000 P1-A- 1ac 1000 PP 2,000 P1-A- 1ad 1000 PP 2,000 P1-A- 1ae 0 2000 PP 2,000 P1-A- 1af 2000 PP 2,000 P1-A- 1a 400 PE 10,000 P1-A- 1b 400 PE 10,000 P1-A- 1c 750 PE 10,000 P1-A- 1d 750 PE 10,000 P1-A- 1e 1000 PE 10,000 P1-A- 1f 1000 PE 10,000 P1-A- 1g 2000 PE 10,000 P1-A- 1h 2000 PE 10,000 P1-A- 1i 0 400 PP 20,000 P1-A- 1j 400 PP 20,000 P1-A- 1k 750 PP 20,000 P1-A- 1l 750 PP 20,000 P1-A- 1m 1000 PP 20,000 P1-A- 1n 1000 PP 20,000 P1-A- 1o 2000 PP 20,000 P1-A- 1p 2000 PP 20,000 P1-A- 1q 400 PE 100,000 P1-A- 1r 400 PE 100,000 P1-A- 1s 0 750 PE 100,000 P1-A- 1t 750 PE 100,000 P1-A- 1u 1000 PE 100,000 P1-A- 1v 1000 PE 100,000 P1-A- 1w 2000 PE 100,000 P1-A- 1x 2000 PE 100,000 P1-A- 1y 400 PE 200,000 P1-A- 1z 400 PE 200,000 P1-A- 1aa 750 PE 200,000 P1-A- 1ab 750 PE 200,000 P1-A- 1ac 0 1000 PE 200,000 P1-A- 1ad 1000 PE 200,000 P1-A- 1ae 2000 PE 200,000 P1-A- 1af 2000 PE 200,000

(186) In certain embodiments, the present invention provides compositions denoted P1-B-2. These materials are generally solids or waxes and are relatively hydrophobic.

(187) Such materials conform to formula P1:

(188) ##STR00254## where each of R.sup.1, R.sup.2, R.sup.3, and R.sup.4 are as defined above and in the classes and subclasses herein; n is an integer from 4 to about 50; and the moiety

(189) ##STR00255##  comprises a hydrocarbon having between about 4 and about 80 carbon atoms.

(190) In certain embodiments, compositions of the present invention comprise materials of category P1-B-2 wherein each of the variables R.sup.1, R.sup.2, R.sup.3, and R.sup.4 is at each occurrence —H (e.g. the APC portion of the molecule comprises a poly(ethylene carbonate) chain. In certain embodiments, compositions of the present invention comprise materials of category P1-B-2 wherein three of the variables R.sup.1, R.sup.2, R.sup.3, and R.sup.4 are at each occurrence —H and the remaining variable is —CH.sub.3 (e.g. the APC portion of the molecule comprises a poly(propylene carbonate) chain.

(191) In certain embodiments, compositions of the present invention comprise materials of category P1-B-2 wherein n is, on average in the composition, between about 4 and about 8. In certain embodiments, compositions of the present invention comprise materials of category P1-B-2 wherein n is, on average in the composition, between about 6 and about 10. In certain embodiments, compositions of the present invention comprise materials of category P1-B-2 wherein n is, on average in the composition, between about 8 and about 12. In certain embodiments, compositions of the present invention comprise materials of category P1-B-2 wherein n is, on average in the composition, between about 12 and about 16. In certain embodiments, compositions of the present invention comprise materials of category P1-B-2 wherein n is, on average in the composition, between about 16 and about 20. In certain embodiments, compositions of the present invention comprise materials of category P1-B-2 wherein n is, on average in the composition, between about 20 and about 40. In certain embodiments, compositions of the present invention comprise materials of category P1-B-2 wherein n is, on average in the composition, between about 30 and about 50.

(192) In certain embodiments, compositions of the present invention comprise materials of category P1-B-2 wherein

(193) ##STR00256##
comprises a straight-chain aliphatic group. In certain embodiments, compositions of the present invention comprise materials of category P1-B-2 wherein

(194) ##STR00257##
comprises a straight chain aliphatic group containing 6 to 80 carbon atoms.

(195) In certain embodiments, compositions of the present invention comprise materials of category P1-B-2 wherein

(196) ##STR00258##
is selected from the group consisting of: a C.sub.7-12 straight-chain aliphatic group; a C.sub.12-16 straight-chain aliphatic group; a C.sub.16-20 straight-chain aliphatic group; a C.sub.24-28 straight-chain aliphatic group; a C.sub.36-40 straight-chain aliphatic group; a C.sub.40-60 straight-chain aliphatic group; and a C.sub.60-80 straight-chain aliphatic group.
In certain embodiments, such straight-chain aliphatic groups are saturated, while in other embodiments, they contain one or more sites of unsaturation. In certain embodiments, such groups comprise or are derived from the chain of a naturally occurring material such as a long-chain fatty acid.

(197) In certain embodiments, compositions of the present invention comprise materials of category P1-B-2 wherein the hydrocarbon moiety comprises the aliphatic chain of a fatty acid. In certain embodiments, compositions of the present invention comprise materials of category P1-B-2 wherein

(198) ##STR00259##
is selected from the group consisting of the compounds shown in Table 1. In certain embodiments, compositions of the present invention comprise materials of category P1-B-2 wherein

(199) ##STR00260##
is selected from the group consisting of the compounds shown in Table 2.

(200) Representative compositions of the present invention comprising materials of category P1-B-2 with straight chain aliphatic groups are shown in Table 5.

(201) TABLE-US-00005 TABLE 5 Designation APC identity n identity P1-B-2a 4 P1-B-2b 4 P1-B-2c 4 P1-B-2d 4 P1-B-2e 0 4 P1-B-2f 4 P1-B-2g 4 P1-B-2h 6 P1-B-2i 8 P1-B-2j 0 12 P1-B-2k 4 P1-B-2l 4 P1-B-2m 4 P1-B-2n 4 P1-B-2o 0 8 P1-B-2p 20 P1-B-2q 6

(202) In certain embodiments, compositions of the present invention comprise materials of category P1-B-2 wherein

(203) ##STR00296##
comprises a branched C.sub.4-80 aliphatic group. In certain embodiments for compositions of type P1-B-2,

(204) ##STR00297##
comprises a C.sub.4-6 branched-chain aliphatic group. In certain embodiments for compositions of type P1-B-2,

(205) ##STR00298##
comprises a C.sub.7-12 branched-chain aliphatic group; a C.sub.12-16 branched-chain aliphatic group; a C.sub.16-20 branched-chain aliphatic group; a C.sub.20-24 branched-chain aliphatic group; a C.sub.24-28 branched-chain aliphatic group; a C.sub.28-36 branched-chain aliphatic group; or a C.sub.36-40 branched-chain aliphatic group. In certain embodiments for compositions of type P1-B-2,

(206) ##STR00299##
comprises a C.sub.40-60 branched-chain aliphatic group or a C.sub.60-80 branched-chain aliphatic group. In certain embodiments for compositions of type P1-B-2, branched-chain aliphatic groups are saturated, while in other embodiments, they contain one or more sites of unsaturation.

(207) In certain embodiments, for compositions of type P1-B-2,

(208) ##STR00300##
comprises a saturated aliphatic group with a branch present at the site of attachment of the

(209) ##STR00301##
moiety to the aliphatic polycarbonate moiety. In certain other embodiments for compositions of type P1-B-2, the point of attachment of the

(210) ##STR00302##
moiety to the aliphatic polycarbonate moiety is not a point of branching.

(211) In certain embodiments, for compositions of type P1-B-2, the

(212) ##STR00303##
moiety is selected from the group consisting of: a C.sub.3-40 straight carbon chain with one or more alkyl substituents; a C.sub.4-40 straight carbon chain with 1-12 alkyl substituents; a C.sub.4-40 straight carbon chain with 1-12 alkyl substituents where each alkyl substituent is independently a C.sub.1-12 straight or branched alkyl; a C.sub.4-20 straight carbon chain with 1-6 alkyl substituents, where each alkyl substituent is independently a C.sub.1-6 straight or branched alkyl; a C.sub.6-12 straight carbon chain with 1-4 alkyl substituents, where each alkyl substituent is independently a C.sub.1-4 straight or branched alkyl; and a C.sub.4-20 straight carbon chain with 1-6 alkyl substituents, where each alkyl substituent is independently a methyl or ethyl group.

(213) In certain embodiments, for compositions of type P1-B-2, the

(214) ##STR00304##
moiety is selected from the group consisting of: sec-butyl, 2-methylbutane, 3-methylbutane, 2-methylpentane, 3-methylpentane, 4-methylpentane, 2-methylhexane, 3-methylhexane, 4-methylhexane, 5-methylhexane, 2-methylheptane, 3-methylheptane, 4-methylheptane, 5-methylheptane, 6-methylheptane, 2-methyloctane, 3-methyloctane, 4-methyloctane, 5-methyloctane, 6-methyloctane, 7-methyloctane, 2-methylnonane, 3-methylnonane, 4-methylnonane, 5-methylnonane, 6-methylnonane, 7-methylnonane, 8-methylnonane, 2-methyldecane, 3-methyldecane, 4-methyldecane, 5-methyldecane, 6-methyldecane, 7-methyldecane, 8-methyldecane, 9-methyldecane, 2-methylundecane, 3-methylundecane, 4-methylundecane, 5-methylundecane, 6-methylundecane, 7-methylundecane, 8-methylundecane, 9-methylundecane, 10-methylundecane, 2-methyldodecane, 3-methyldodecane, 4-methyldodecane, 5-methyldodecane, 6-methyldodecane, 7-methyldodecane, 8-methyldodecane, 9-methyldodecane, 10-methyldodecane, 11-methyldodecane, 2-ethylbutane, 2-ethylpentane, 3-ethylpentane, 2-ethylhexane, 3-ethylhexane, 4-ethylhexane, 2-ethylheptane, 3-ethylheptane, 4-ethylheptane, 5-ethylheptane, 2-ethyloctane, 3-ethyloctane, 4-ethyloctane, 5-ethyloctane, 6-ethyloctane, 2-ethylnonane, 3-ethylnonane, 4-ethylnonane, 5-ethylnonane, 6-ethylnonane, 7-ethylnonane, 2-ethyldecane, 3-ethyldecane, 4-ethyldecane, 5-ethyldecane, 6-ethyldecane, 7-ethyldecane, 8-ethyldecane, 2-ethylundecane, 3-ethylundecane, 4-ethylundecane, 5-ethylundecane, 6-ethylundecane, 7-ethylundecane, 8-ethylundecane, 9-ethylundecane, 2-ethyldodecane, 3-ethyldodecane, 4-ethyldodecane, 5-ethyldodecane, 6-ethyldodecane, 7-ethyldodecane, 8-ethyldodecane, 9-ethyldodecane, 10-ethyldodecane, and combinations of any two or more of these.

(215) In certain embodiments, compositions of type P1-B-2 comprise a

(216) ##STR00305##
moiety selected from the group consisting of: a C.sub.5 straight chain alkyl having two substituents independently selected from C.sub.1-4 straight or branched alkyl; a C.sub.6 straight chain alkyl having 2-3 substituents independently selected from C.sub.1-4 straight or branched alkyl; a C.sub.7 straight chain alkyl having 2-3 substituents independently selected from C.sub.1-4 straight or branched alkyl; a C.sub.8 straight chain alkyl having 2-4 substituents independently selected from C.sub.1-4 straight or branched alkyl; a C.sub.6 straight chain alkyl having 2-4 substituents independently selected from C.sub.1-4 straight or branched alkyl; a C.sub.10 straight chain alkyl having 2-4 substituents independently selected from C.sub.1-4 straight or branched alkyl; a C.sub.11-12 straight chain alkyl having 2-4 substituents independently selected from C.sub.1-4 straight or branched alkyl; a C.sub.12-16 straight chain alkyl having 2-5 substituents independently selected from C.sub.1-4 straight or branched alkyl; a C.sub.16-20 straight chain alkyl having 2-6 substituents independently selected from C.sub.1-4 straight or branched alkyl; and a C.sub.20-40 straight chain alkyl having 2-12 substituents independently selected from C.sub.1-4 straight or branched alkyl.

(217) In certain embodiments, for compositions of type P1-B-2, the

(218) ##STR00306##
moiety comprises

(219) ##STR00307##
where * represents the site of attachment of the

(220) ##STR00308##
moiety to the polycarbonate moiety, and f is an integer from 1 to 12.

(221) In certain embodiments, for compositions of type P1-B-2, a

(222) ##STR00309##
moiety is selected from the group consisting of:

(223) ##STR00310##
where k is an integer from 0 to 10.

(224) In certain embodiments, for compositions of type P1-B-2, where

(225) ##STR00311##
comprises an aliphatic group with a branch point at the site of attachment of the

(226) ##STR00312##
moiety to the aliphatic polycarbonate moiety, the

(227) ##STR00313##
has a formula:

(228) ##STR00314## where R.sup.a1 and R.sup.a2 are each an aliphatic group.

(229) In certain embodiments, for compositions of type P1-B-2, where

(230) ##STR00315##
comprises

(231) ##STR00316##
each of R.sup.a1 and R.sup.a2 comprises a straight chain aliphatic group. In certain embodiments each of R.sup.a1 and R.sup.a2 is independently selected from the group consisting of C.sub.1-78 aliphatic groups where R.sup.a1 and R.sup.a2 together with the carbon atom to which they are attached contain at least 4 but less than 80 carbon atoms. In certain embodiments, R.sup.a1 and R.sup.a2 and the carbon atom to which they are attached comprise at least 6, at least 8, at least 10, at least 12, at least 16, at least 20, at least 24, at least 30, at least 34 or at least 38 carbon atoms. In certain embodiments, R.sup.a1 and R.sup.a2 and the carbon atom to which they are attached comprise between 6 and 10, between 8 and 12, between 12 and 16, between 16 and 20, between 20 and 24, between 24 and 30, between 30 and 40, between 40 and 60, or between 60 and 80 carbon atoms.

(232) In certain embodiments,

(233) ##STR00317##
is selected from the group consisting of: 2-butane, 2-pentane, 3-pentane, 2-hexane, 3-hexane, 2-heptane, 3-heptane, 4-heptane, 2-octane, 3-octane, 4-octane, 2-nonane, 3-nonane, 4-nonane, 5-nonane, 2-decane, 3-decane, 4-decane, 5-decane, 2-undecane, 3-undecane, 4-undecane, 5-undecane, 6-undecane, 2-dodecane, 3-dodecane, 4-dodecane, 5-dodecane, 6-dodecane, and combinations of any two or more of these.

(234) In certain embodiments, for compositions of type P1-B-2, where

(235) ##STR00318##
comprises

(236) ##STR00319##
at least one of R.sup.a1 and R.sup.a2 comprises one or more branch points. In certain embodiments, one or more of R.sup.a1 and R.sup.a2 comprises an alkyl group bearing methyl or ethyl substituents. In certain embodiments, R.sup.a1 and R.sup.a2 are independently selected from the group consisting of: methyl, ethyl, propyl, butyl, n-pentane, n-hexane, n-heptane, n-octane, any C.sub.9-40 n-alkyl, isopropyl, isobutyl, sec-butyl, 2-methylbutane, 3-methylbutane, 2-methylpentane, 3-methylpentane, 4-methylpentane, 2-methylhexane, 3-methylhexane, 4-methylhexane, 5-methylhexane, 2-methylheptane, 3-methylheptane, 4-methylheptane, 5-methylheptane, 6-methylheptane, 2-methyloctane, 3-methyloctane, 4-methyloctane, 5-methyloctane, 6-methyloctane, 7-methyloctane, 2-methylnonane, 3-methylnonane, 4-methylnonane, 5-methylnonane, 6-methylnonane, 7-methylnonane, 8-methylnonane, 2-methyldecane, 3-methyldecane, 4-methyldecane, 5-methyldecane, 6-methyldecane, 7-methyldecane, 8-methyldecane, 9-methyldecane, 2-methylundecane, 3-methylundecane, 4-methylundecane, 5-methylundecane, 6-methylundecane, 7-methylundecane, 8-methylundecane, 9-methylundecane, 10-methylundecane, 2-methyldodecane, 3-methyldodecane, 4-methyldodecane, 5-methyldodecane, 6-methyldodecane, 7-methyldodecane, 8-methyldodecane, 9-methyldodecane, 10-methyldodecane, 11-methyldodecane, 2-ethylbutane, 2-ethylpentane, 3-ethylpentane, 2-ethylhexane, 3-ethylhexane, 4-ethylhexane, 2-ethylheptane, 3-ethylheptane, 4-ethylheptane, 5-ethylheptane, 2-ethyloctane, 3-ethyloctane, 4-ethyloctane, 5-ethyloctane, 6-ethyloctane, 2-ethylnonane, 3-ethylnonane, 4-ethylnonane, 5-ethylnonane, 6-ethylnonane, 7-ethylnonane, 2-ethyldecane, 3-ethyldecane, 4-ethyldecane, 5-ethyldecane, 6-ethyldecane, 7-ethyldecane, 8-ethyldecane, 2-ethylundecane, 3-ethylundecane, 4-ethylundecane, 5-ethylundecane, 6-ethylundecane, 7-ethylundecane, 8-ethylundecane, 9-ethylundecane, 2-ethyldodecane, 3-ethyldodecane, 4-ethyldodecane, 5-ethyldodecane, 6-ethyldodecane, 7-ethyldodecane, 8-ethyldodecane, 9-ethyldodecane, 10-ethyldodecane, and combinations of any two or more of these.

(237) In certain embodiments, for compositions of type P1-B-2, where

(238) ##STR00320##
comprises

(239) ##STR00321##
at least one of R.sup.a1 and R.sup.a2 is selected from the group consisting of: a C.sub.5 straight chain alkyl having 1-2 substituents independently selected from C.sub.1-4 straight or branched alkyl; a C.sub.6 straight chain alkyl having 1-3 substituents independently selected from C.sub.1-4 straight or branched alkyl; a C.sub.7 straight chain alkyl having 1-3 substituents independently selected from C.sub.1-4 straight or branched alkyl; a C.sub.8 straight chain alkyl having 1-4 substituents independently selected from C.sub.1-4 straight or branched alkyl; a C.sub.6 straight chain alkyl having 1-4 substituents independently selected from C.sub.1-4 straight or branched alkyl; a C.sub.10 straight chain alkyl having 1-4 substituents independently selected from C.sub.1-4 straight or branched alkyl; a C.sub.11-12 straight chain alkyl having 1-4 substituents independently selected from C.sub.1-4 straight or branched alkyl; a C.sub.12-16 straight chain alkyl having 1-5 substituents independently selected from C.sub.1-4 straight or branched alkyl; a C.sub.16-20 straight chain alkyl having 1-6 substituents independently selected from C.sub.1-4 straight or branched alkyl; and a C.sub.20-40 straight chain alkyl having 1-12 substituents independently selected from C.sub.1-4 straight or branched alkyl.

(240) In certain embodiments, for compositions of type P1-B-2, where

(241) ##STR00322##
comprises

(242) ##STR00323##
at least one of R.sup.a1 and R.sup.a2 comprises

(243) ##STR00324##
where * represents the site of attachment of the

(244) ##STR00325##
moiety to the polycarbonate moiety, and f is an integer from 1 to 12. In certain embodiments, at least one of R.sup.a1 and R.sup.a2 comprises is selected from the group consisting of:

(245) ##STR00326##
where k is an integer from 0 to 10.

(246) Representative compositions of the present invention comprising materials of category P1-B-2 with straight chain aliphatic groups are shown in Table 6.

(247) TABLE-US-00006 TABLE 6 Designation APC identity n identity P1-B-2r 4 P1-B-2s 0 4 P1-B-2t 4 P1-B-2u 4 P1-B-2v 4 P1-B-2w 4 P1-B-2x 0 4 P1-B-2y 8 P1-B-2z 12 P1-B-2aa 4 P1-B-2ab 4 P1-B-2ac 0 4 P1-B-2ad 4 P1-B-2ae 4 P1-B-2af 4 P1-B-2ag 4 P1-B-2ah 0 4
II. Methods of Making

(248) In another aspect, the present invention encompasses methods of making the compositions described above.

(249) One method for making compounds of the present invention involves copolymerizing one or more epoxides with CO.sub.2 in the presence of a chain transfer agent, where the chain transfer agent is a hydrocarbon moiety having one functional group capable of acting as a polymerization initiator for epoxide CO.sub.2 copolerization. In certain embodiments, such functional groups include an alcohol or carboxylic acid group (or a salt thereof). Suitable reaction conditions and catalysts for such reactions are disclosed in U.S. Pat. No. 8,247,520 the entirety of which is incorporated herein by reference.

(250) One method for making compounds of the present invention involves copolymerizing one or more epoxides with CO.sub.2 in the presence of a chain transfer agent, where the chain transfer agent is a hydrocarbon moiety having one functional group capable of acting as a polymerization initiator for epoxide CO.sub.2 copolerization. In certain embodiments, such functional groups include an alcohol or carboxylic acid group (or a salt thereof).

(251) In certain embodiments, methods of the present invention include the step of contacting a monofunctional alcohol or carboxylic acid of formula Z1

(252) ##STR00362##

(253) with one or more epoxides and carbon dioxide in the presence of a catalyst that promotes the copolymerization of epoxides and carbon dioxide to provide a product of formula I

(254) ##STR00363## wherein, Q comprises a functional group selected from —OH and —CO.sub.2H; z is 0 or 1; and each of

(255) ##STR00364##  is as defined above and in the classes and subclasses herein.
Using Carboxylic Acid Starting Materials

(256) In certain embodiments, methods of the present invention include the step of contacting a monofunctional carboxylic acid of formula Z1b

(257) ##STR00365##

(258) with one or more epoxides and carbon dioxide in the presence of a catalyst that promotes the copolymerization of epoxides and carbon dioxide to provide a product of formula P1

(259) ##STR00366## where each of R.sup.1, R.sup.2, R.sup.3, R.sup.4,

(260) ##STR00367##  and n is as defined above and in the classes and subclasses herein.

(261) In certain embodiments, the alcohol Z1b comprises a carboxylic acid-functionalized polyolefin or a salt thereof. In certain embodiments, Z1a comprises a carboxylic acid-functionalized polyethylene. In certain embodiments, Z1a comprises a carboxylic acid-functionalized polypropylene.

(262) In certain embodiments, for the method above, Z1b comprises a C.sub.4-80 aliphatic carboxylic acid (or a salt thereof).

(263) In certain embodiments, the alcohol Z1b comprises a straight-chain carboxylic acid. In certain embodiments, such carboxylic acids comprise 6 to 80 carbon atoms. In certain embodiments, Z1b comprises a C.sub.7-12 straight-chain carboxylic acid. In certain embodiments, Z1b comprises a C.sub.12-16 straight-chain carboxylic acid. In certain embodiments, Z1b comprises a C.sub.16-20 straight-chain carboxylic acid. In certain embodiments, Z1b comprises a C.sub.20-24 straight-chain carboxylic acid, a C.sub.24-28 straight-chain carboxylic acid, a C.sub.28-36 straight-chain carboxylic acid, or a C.sub.36-40 straight-chain carboxylic acid. In certain embodiments, Z1b comprises a C.sub.40-60 straight-chain carboxylic acid or a C.sub.60-80 straight-chain carboxylic acid. In certain embodiments, such straight-chain carboxylic acid are saturated, while in other embodiments, they contain one or more sites of unsaturation. In certain embodiments, Z1b comprises or is derived from a naturally occurring material such as a long-chain fatty acid.

(264) In embodiments where Z1b comprises a saturated straight aliphatic carboxylic acid, suitable chains include, but are not limited to those derived from common fatty acids. In certain embodiments Z1b is selected from Table 7:

(265) TABLE-US-00007 TABLE 7 Examples of Saturated Fatty acids Common name of fatty acid Structure Caprylic acid CH.sub.3(CH.sub.2).sub.6—CO.sub.2H Capric acid CH.sub.3(CH.sub.2).sub.8—CO.sub.2H Lauric acid CH.sub.3(CH.sub.2).sub.10—CO.sub.2H Myristic acid CH.sub.3(CH.sub.2).sub.12—CO.sub.2H Palmitic acid CH.sub.3(CH.sub.2).sub.14—CO.sub.2H Stearic acid CH.sub.3(CH.sub.2).sub.16—CO.sub.2H Rachidic acid CH.sub.3(CH.sub.2).sub.18—CO.sub.2H Behenic acid CH.sub.3(CH.sub.2).sub.20—CO.sub.2H Lignoceric acid CH.sub.3(CH.sub.2).sub.22—CO.sub.2H Cerotic acid CH.sub.3(CH.sub.2).sub.24—CO.sub.2H

(266) In embodiments where Z1b comprises an unsaturated straight aliphatic carboxylic acid, suitable carboxylic acids include, but are not limited to common naturally-occurring unsaturated fatty acids. In certain embodiments, suitable carboxylic acids include, but are not limited to those shown in Table 8:

(267) TABLE-US-00008 TABLE 8 Examples of Unsaturated Fatty Acids Common name of Corresponding Aliphatic fatty acid Carboxylic acid Δ.sup.x Myristoleic CH.sub.3(CH.sub.2).sub.3CH═CH(CH.sub.2).sub.7—CO.sub.2H cis-Δ.sup.9 Palmitoleic CH.sub.3(CH.sub.2).sub.5CH═CH(CH.sub.2).sub.7—CO.sub.2H cis-Δ.sup.9 Sapienic CH.sub.3(CH.sub.2).sub.8CH═CH(CH.sub.2).sub.4—CO.sub.2H cis-Δ.sup.6 Oleic CH3(CH.sub.2).sub.7CH═CH(CH.sub.2).sub.7—CO.sub.2H cis-Δ.sup.9 Elaidic CH.sub.3(CH.sub.2).sub.7CH═CH(CH.sub.2).sub.7—CO.sub.2H trans-Δ.sup.9 Vaccenic CH.sub.3(CH.sub.2).sub.5CH═CH(CH.sub.2).sub.9—CO.sub.2H trans-Δ.sup.11 Linoleic CH.sub.3(CH.sub.2).sub.4CH═CHCH.sub.2CH═CH(CH.sub.2—)CO.sub.2H cis,cis- Δ.sup.9,Δ.sup.12 Linoelaidic CH.sub.3(CH.sub.2).sub.4CH═CHCH.sub.2CH═CH(CH.sub.2).sub.7—CO.sub.2H trans, trans- Δ.sup.9,Δ.sup.12 α-Linolenic CH.sub.3CH.sub.2CH═CHCH.sub.2CH═CHCH.sub.2CH═CH(CH.sub.2).sub.7—CO.sub.2H cis,cis,cis- Δ.sup.9,Δ.sup.12,Δ.sup.15 Arachidonic CH.sub.3(CH.sub.2).sub.4CH═CHCH.sub.2CH═CHCH.sub.2CH═CHCH.sub.2CH═CH(CH.sub.2).sub.3—CO.sub.2H cis,cis, cis,cis- Δ.sup.5,Δ.sup.8, Δ.sup.11,Δ.sup.14 Eicosa- CH.sub.3CH.sub.2CH═CHCH.sub.2CH═CHCH.sub.2CH═CHCH.sub.2CH═CHCH.sub.2CH═CH(CH.sub.2).sub.3—CO.sub.2H cis,cis, pentaenoic cis,cis,cis- Δ.sup.5,Δ.sup.8,Δ.sup.11, Δ.sup.14,Δ.sup.17 Erucic CH.sub.3(CH.sub.2).sub.7CH═CH(CH.sub.2).sub.11—CO.sub.2H cis-Δ.sup.13 Docosahex- CH.sub.3CH.sub.2CH═CHCH.sub.2CH═CHCH.sub.2CH═CHCH.sub.2CH═CHCH.sub.2CH═CHCH.sub.2CH═CH(CH.sub.2).sub.2—CO.sub.2H cis,cis,cis, aenoic cis,cis,cis- Δ.sup.4,Δ.sup.7,Δ.sup.10, Δ.sup.13,Δ.sup.17, Δ.sup.16,Δ.sup.19

(268) In certain embodiments, Z1b comprises a branched aliphatic carboxylic acid. In certain embodiments, such carboxylic acids comprise from 4 to about 80 carbon atoms. In certain embodiments, Z1b comprises a C.sub.4-6 branched-chain carboxylic acid. In certain embodiments, Z1b comprises a C.sub.7-12 branched-chain carboxylic acid. In certain embodiments, Z1b comprises a C.sub.12-16 branched-chain carboxylic acid. In certain embodiments, Z1b comprises a C.sub.16-20 branched-chain carboxylic acid. In certain embodiments, Z1b comprises a C.sub.20-24 branched-chain carboxylic acid, a C.sub.24-28 branched-chain carboxylic acid, a C.sub.28-36 branched-chain carboxylic acid, or a C.sub.36-40 branched-chain carboxylic acid. In certain embodiments, Z1b comprises a C.sub.40-60 branched-chain carboxylic acid or a C.sub.60-80 branched-chain carboxylic acid. In certain embodiments, such branched-chain carboxylic acids are saturated, while in other embodiments, they contain one or more sites of unsaturation.

(269) In certain embodiments, Z1b comprises a carboxylic acid having a C.sub.3-40 straight carbon chain. In certain embodiments, the carbon chain of the carboxylic acid Z1b also contains one or more alkyl substituents. In certain embodiments, Z1b comprises a C.sub.4-40 straight carbon chain with 1-12 alkyl substituents. In certain embodiments, Z1b comprises a C.sub.4-40 straight carbon chain with 1-12 alkyl substituents, where each alkyl substituent is independently a C.sub.1-12 straight or branched alkyl. In certain embodiments, Z1b comprises a C.sub.4-20 straight carbon chain with 1-6 alkyl substituents, where each alkyl substituent is independently a C.sub.1-6 straight or branched alkyl. In certain embodiments, Z1b comprises a C.sub.6-12 straight carbon chain with 1-4 alkyl substituents, where each alkyl substituent is independently a C.sub.1-4 straight or branched alkyl. In certain embodiments, Z1b comprises a C.sub.4-20 straight carbon chain with 1-6 alkyl substituents, where each alkyl substituent is independently a methyl or ethyl group.

(270) In certain embodiments, Z1b comprises a carboxylic acid selected from the group consisting of: sec-butanoic, 2-methylbutanoic acid, 3-methylbutanoic acid, 2-methylpentanoic acid, 3-methylpentanoic acid, 4-methylpentanoic acid, 2-methylhexanoic acid, 3-methylhexanoic acid, 4-methylhexanoic acid, 5-methylhexanoic acid, 2-methylheptanoic acid, 3-methylheptanoic acid, 4-methylheptanoic acid, 5-methylheptanoic acid, 6-methylheptanoic acid, 2-methyloctanoic acid, 3-methyloctanoic acid, 4-methyloctanoic acid, 5-methyloctanoic acid, 6-methyloctanoic acid, 7-methyloctanoic acid, 2-methylnonanoic acid, 3-methylnonanoic acid, 4-methylnonanoic acid, 5-methylnonanoic acid, 6-methylnonanoic acid, 7-methylnonanoic acid, 8-methylnonanoic acid, 2-methyldecanoic acid, 3-methyldecanoic acid, 4-methyldecanoic acid, 5-methyldecanoic acid, 6-methyldecanoic acid, 7-methyldecanoic acid, 8-methyldecanoic acid, 9-methyldecanoic acid, 2-methylundecanoic acid, 3-methylundecanoic acid, 4-methylundecanoic acid, 5-methylundecanoic acid, 6-methylundecanoic acid, 7-methylundecanoic acid, 8-methylundecanoic acid, 9-methylundecanoic acid, 10-methylundecanoic acid, 2-methyldodecanoic acid, 3-methyldodecanoic acid, 4-methyldodecanoic acid, 5-methyldodecanoic acid, 6-methyldodecanoic acid, 7-methyldodecanoic acid, 8-methyldodecanoic acid, 9-methyldodecanoic acid, 10-methyldodecanoic acid, 11-methyldodecanoic acid, 2-ethylbutanoic acid, 2-ethylpentanoic acid, 3-ethylpentanoic acid, 2-ethylhexanoic acid, 3-ethylhexanoic acid, 4-ethylhexanoic acid, 2-ethylheptanoic acid, 3-ethylheptanoic acid, 4-ethylheptanoic acid, 5-ethylheptanoic acid, 2-ethyloctanoic acid, 3-ethyloctanoic acid, 4-ethyloctanoic acid, 5-ethyloctanoic acid, 6-ethyloctanoic acid, 2-ethylnonanoic acid, 3-ethylnonanoic acid, 4-ethylnonanoic acid, 5-ethylnonanoic acid, 6-ethylnonanoic acid, 7-ethylnonanoic acid, 2-ethyldecanoic acid, 3-ethyldecanoic acid, 4-ethyldecanoic acid, 5-ethyldecanoic acid, 6-ethyldecanoic acid, 7-ethyldecanoic acid, 8-ethyldecanoic acid, 2-ethylundecanoic acid, 3-ethylundecanoic acid, 4-ethylundecanoic acid, 5-ethylundecanoic acid, 6-ethylundecanoic acid, 7-ethylundecanoic acid, 8-ethylundecanoic acid, 9-ethylundecanoic acid, 2-ethyldodecanoic acid, 3-ethyldodecanoic acid, 4-ethyldodecanoic acid, 5-ethyldodecanoic acid, 6-ethyldodecanoic acid, 7-ethyldodecanoic acid, 8-ethyldodecanoic acid, 9-ethyldodecanoic acid, 10-ethyldodecanoic acid, and combinations of any two or more of these.

(271) For avoidance of doubt with respect to interpretation of these methods, where Z1b is chosen from the group above to be 5-methylheptanoic acid, the compound of formula P1 thereby produced will have a structure:

(272) ##STR00368##

(273) In certain embodiments, Z1b comprises a saturated carboxylic acid with multiple branches. In certain embodiments, Z1b comprises a carboxylic acid selected from the group consisting of: a C.sub.5 straight chain alkanoic acid having two substituents independently selected from C.sub.1-4 straight or branched alkyl; a C.sub.6 straight chain alkanoic acid having 2-3 substituents independently selected from C.sub.1-4 straight or branched alkyl; a C.sub.7 straight chain alkanoic acid having 2-3 substituents independently selected from C.sub.1-4 straight or branched alkyl; a C.sub.8 straight chain alkanoic acid having 2-4 substituents independently selected from C.sub.1-4 straight or branched alkyl; a C.sub.6 straight chain alkanoic acid having 2-4 substituents independently selected from C.sub.1-4 straight or branched alkyl; a C.sub.10 straight chain alkanoic acid having 2-4 substituents independently selected from C.sub.1-4 straight or branched alkyl; a C.sub.11-12 straight chain alkanoic acid having 2-4 substituents independently selected from C.sub.1-4 straight or branched alkyl; a C.sub.12-16 straight chain alkanoic acid having 2-5 substituents independently selected from C.sub.1-4 straight or branched alkyl; a C.sub.16-20 straight chain alkanoic acid having 2-6 substituents independently selected from C.sub.1-4 straight or branched alkyl; and a C.sub.20-40 straight chain alkanoic acid having 2-12 substituents independently selected from C.sub.1-4 straight or branched alkyl.

(274) In certain embodiments, Z1b comprises

(275) ##STR00369##
where f is an integer from 1 to 12.

(276) In certain embodiments, Z1b comprises a branched fatty acid. In certain embodiments, such branched fatty acids include naturally occurring materials such as methyl branched fatty acids, iso-methyl branched fatty acids (which have the branch point on the penultimate carbon), anteiso-methyl-branched fatty acids (which have the branch point on the ante-penultimate carbon atom (two from the end), isoprenoid fatty acids, and other similar materials.

(277) In certain embodiments, Z1b comprises an isoprenoid fatty acid. In certain embodiments, Z1b is selected from the group consisting of:

(278) ##STR00370##
where k is an integer from 0 to 10.

(279) In certain embodiments, for any of the methods above, the epoxide has a formula:

(280) ##STR00371##
where each of R.sup.1, R.sup.2, R.sup.3, and R.sup.4, is as defined above and in the classes and subclasses herein.

(281) In certain embodiments, for any of the methods above, the epoxide is selected from the group consisting of: ethylene oxide, propylene oxide, 1,2 butene oxide, 1,2 hexene oxide, oxides of higher alpha olefins (e.g. C.sub.6-40 alpha olefins), butadiene monoepoxide, epichlorohydrin, ethers or esters of glycidol, cyclopentene oxide, cyclohexene oxide, 3 vinyl cyclohexene oxide, and 3-ethyl cyclohexene oxide, or with combinations of any two or more of these.

(282) In certain embodiments, for any of the methods above, the epoxide comprises ethylene oxide. In certain embodiments, for any of the methods above, the epoxide comprises propylene oxide. In certain embodiments, for any of the methods above, the epoxide comprises cyclohexene oxide.

(283) In certain embodiments, the methods above include the step of allowing the copolymerization to proceed until a desired chain length of epoxide-CO.sub.2 copolymer has been formed. In certain embodiments, the method includes a further step of terminating the polymerization reaction and isolating the product.

(284) III. Applications

(285) In another aspect, the present invention includes methods of using the block copolymeric materials described above. The inventive materials are suitable for a range of applications. As noted above, one application is as effective compatibilizers for polymer blends. However, the new block materials are contemplated to have numerous other applications. Many of the inventive materials provided are amphiphilic and therefore suggest themselves for applications where there is a desire to compatibilize or solubilize dissimilar materials. In addition to compatibilizing polymer blends the materials may have applications as emulsifiers for liquids or gels, as detergents or surfactants, viscosity or lubricity modifiers, plasticizers, fuel additives, in tie-layer and adhesive applications and in a host of related uses which will be apparent to the skilled artisan.

(286) In certain embodiments, the present invention provides materials useful for forming blends of a polyolefin with a relatively polar polymer such as a polycarbonate, a polyester, or a polyether. In particular, the inventive materials described above have application for making thermoplastic blends comprising a polyolefin (such as polyethylene or polyprpopylene) and an aliphatic polycarbonate (such as poly(propylene carbonate), poly(ethylene carbonate), and poly(cyclohexene carbonate).

Other Embodiments

(287) The foregoing has been a description of certain non-limiting embodiments of the invention. Accordingly, it is to be understood that the embodiments of the invention herein described are merely illustrative of the application of the principles of the invention. Reference herein to details of the illustrated embodiments is not intended to limit the scope of the claims, which themselves recite those features regarded as essential to the invention.