Polymers and uses thereof
11708446 · 2023-07-25
Assignee
Inventors
Cpc classification
C08F120/14
CHEMISTRY; METALLURGY
C08F212/12
CHEMISTRY; METALLURGY
C08F293/005
CHEMISTRY; METALLURGY
C08F4/06
CHEMISTRY; METALLURGY
C08F2/38
CHEMISTRY; METALLURGY
C08F120/14
CHEMISTRY; METALLURGY
C08F2438/01
CHEMISTRY; METALLURGY
C08F293/005
CHEMISTRY; METALLURGY
C08F2438/03
CHEMISTRY; METALLURGY
International classification
C08F293/00
CHEMISTRY; METALLURGY
C08F4/06
CHEMISTRY; METALLURGY
C08F212/12
CHEMISTRY; METALLURGY
Abstract
The present invention provides polymers and methods of preparing the same. In certain embodiments, the polymers comprise acrylate repeating units that have been derivatized (e.g., reduced and/or substituted) to form new polymeric structures. In certain embodiments, the polymers described herein self-assemble to form well-defined nanostructures. In some instances, the nanostructures exhibit relatively small d-spacing (e.g., a d-spacing value of 10 nm or less). Due to their properties, the polymers described herein are useful in a variety of applications including functional materials and biomedical applications.
Claims
1. A method of preparing a block copolymer of the formula: ##STR00053## the method comprising reducing an original block copolymer of the formula: ##STR00054## wherein: R.sup.4 is hydrogen or C.sub.1-6 alkyl; R.sup.1, R.sup.2, and R.sup.3 are each independently hydrogen or C.sub.1-6 alkyl; T.sup.1 and T.sup.2 are each independently a terminal group selected from hydrogen, halogen, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted heteroalkyl, optionally substituted carbocyclyl, optionally substituted heterocyclyl, optionally substituted aryl, optionally substituted heteroaryl, and optionally substituted acyl; R.sup.5, R.sup.6, and R.sup.7 are each independently hydrogen or C.sub.1-6 alkyl; R.sup.8 is optionally substituted alkyl, optionally substituted carbocyclyl, optionally substituted heterocyclyl, optionally substituted aryl, optionally substituted heteroaryl, or optionally substituted acyl; or R.sup.8 is a polymer; and n and m are each independently an integer from 1 to 2000, inclusive.
2. The method of claim 1, wherein the original block copolymer is of the formula: ##STR00055##
3. The method of claim 2, wherein the original block copolymer is of the formula: ##STR00056## wherein: each instance of R.sup.8a is independently halogen, —CN, —NO.sub.2, —N.sub.3, optionally substituted alkyl, optionally substituted carbocyclyl, optionally substituted heterocyclyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted acyl, —OR.sup.O, —SR.sup.S, or —N(R.sup.N).sub.2; each instance of R.sup.O is independently hydrogen, optionally substituted alkyl, optionally substituted carbocyclyl, optionally substituted heterocyclyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted acyl, or an oxygen protecting group; each instance of R.sup.N is independently hydrogen, optionally substituted alkyl, optionally substituted carbocyclyl, optionally substituted heterocyclyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted acyl, or a nitrogen protecting group; optionally wherein two R.sup.N attached to the same nitrogen atom are joined together with the intervening atoms to form optionally substituted heterocyclyl or optionally substituted heteroaryl; each instance of R.sup.S is independently hydrogen, optionally substituted alkyl, optionally substituted carbocyclyl, optionally substituted heterocyclyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted acyl, or a sulfur protecting group; and p is 0, 1, 2, 5, 4, or 5.
4. The method of claim 1, wherein the step of reducing is carried out in the presence of a hydride donor.
5. The method of claim 1, wherein the step of reducing is carried out in the presence of a reducing reagent selected from the group consisting of lithium aluminum hydride (LiAlH.sub.4), hydrogen gas, sodium amalgam, sodium-lead alloy, diborane, sodium borohydride, dithionates, thiosulfates, hydrazine, diisobutylaluminium hydride (DIBAL), oxalic acid, formic acid, ascorbic acid, lithium triethylborohydride, diborane, borane-tetrahydrofuran, borane-dimethyl sulfide, samarium, sodium bis(2-methoxyethoxy)aluminium hydride, sodium triacetoxyborohydride, and zinc.
6. The method of claim 4, wherein the hydride donor is lithium aluminum hydride (LiAlH.sub.4).
7. The method of claim 1 further comprising polymerizing two or more monomers to produce the original block copolymer, wherein at least one monomer is an acrylate of the formula: ##STR00057##
8. The method of claim 7, wherein the polymerization step is a polymerization selected from the group consisting of living radical polymerization, reversible-deactivation radical polymerization, atom transfer radical polymerization (ATRP), nitroxide mediated radical polymerization (NMP), and reversible addition-fragmentation chain transfer (RAFT) polymerization.
9. The method of claim 7, wherein the polymerization uses an iniferter, initiator, or chain transfer agent.
10. The method of claim 9, wherein the iniferter, initiator, or chain transfer agent is selected from the group consisting of dithiobenzoates, trithiocarbonates, dithiocarbamates, xanthates, and alkyl halides.
11. The method of claim 10, wherein the dithiobenzoate is selected from the group consisting of benzyl benzodithioate, cyanomethyl benzodithioate, 4-cyano (phenylcarbonothioylthio)pentanoic acid, 4-cyano-4-(phenylcarbonothioylthio)pentanoic acid N-succinimidyl ester, 2-cyano-2-propyl benzodithioate, 2-cyano-2-propyl 4-cyanobenzodithioate, ethyl 2-(4-methoxyphenylcarbonothioylthio)acetate, ethyl 2-methyl-2-(phenylthiocarbonylthio)propionate, ethyl 2-(phenylcarbonothioylthio)-2-phenylacetate, ethyl 2-(phenylcarbonothioylthio)propionate, 1-(methoxycarbonyl)ethyl benzodithioate, 2-(4-methoxyphenylcarbonothioylthio)ethanoic acid, 2-nitro-5-(2-propynyloxy)benzyl 4-cyano-4-(phenylcarbonothioylthio)pentanoate, 2-(phenylcarbonothioylthio)propanoic acid, and 2-phenyl-2-propyl benzodithioate.
12. The method of claim 10, wherein the trithiocarbonate is selected from the group consisting of 3,5-bis(2-dodecylthiocarbonothioylthio-1-oxopropoxy)benzoic acid, 2-cyanobutan-2-yl 4-chloro-3,5-dimethyl-1H-pyrazole-1-carbodithioate, 2-cyanobutanyl-2-yl 3,5-dimethyl-1H-pyrazole-1-carbodithioate, 4-cyano-4-[(dodecylsulfanylthiocarbonyl)sulfanyl]pentanoic acid, 4-cyano-4-[(dodecylsulfanylthiocarbonyl)sulfanyl]pentanol, cyanomethyl (3,5-dimethyl-1H-pyrazole)-carbodithioate, cyanomethyl dodecyl trithiocarbonate, cyanomethyl [3-(trimethoxysilyl)propyl] trithiocarbonate, 2-cyano-2-propyl dodecyl trithiocarbonate, S,S-dibenzyl trithiocarbonate, 2-(dodecylthiocarbonothioylthio)propionic acid, 2-(dodecylthiocarbonothioylthio)-2-methylpropionic acid 3-azido-1-propanol ester, 2-(dodecylthiocarbonothioylthio)-2-methylpropionic acid N-hydroxysuccinimide ester, 2-(dodecylthiocarbonothioylthio)-2-methylpropionic acid pentafluorophenyl ester, phthalimidomethyl butyl trithiocarbonate, methyl 2-(dodecylthiocarbonothioylthio)-2-methylpropionate, 2,2′-(thiocarbonylbis(sulfanediyl))bis(2-methylpropanoic acid), dibenzyl 2,2′-(thiocarbonylbis(sulfanediyl))bis(2-methylpropanoate), dibenzyl 2,2′-(thiocarbonylbis(sulfanediyl))dipropionate, and 2-(((dodecylthio)carbonothioyl)thio)propanoic acid.
13. The method of claim 10, wherein the dithiocarbamate is selected from the group consisting of benzyl 1H-pyrrole-1-carbodithioate, cyanomethyl diphenylcarbamodithioate, cyanomethyl methyl(phenyl)carbamodithioate, cyanomethyl methyl(4-pyridyl)carbamodithioate, 2-cyanopropan-2-yl N-methyl-N-(pyridin-4-yl)carbamodithioate, methyl 2-[methyl(4-pyridinyl)carbamothioylthio]propionate, and 1-succinimidyl-4-cyano-4-[N-methyl-N-(4-pyridyl)carbamothioylthio]pentanoate.
14. The method of claim 10, wherein the xanthate is selected from the group consisting of ethyl 2-(((ethylthio)carbonothioyl)thio)propanoate, methyl (4-methoxyphenoxy)carbonothioylsulfanyl acetate, methyl (methoxycarbonothioyl)sulfanyl acetate, methyl (ethoxycarbonothioyl)sulfanyl acetate, and methyl (isopropoxycarbonothioyl)sulfanyl acetate.
15. The method of claim 10, wherein the alkyl halide is selected from the group consisting of ethyl 2-bromo-2-phenylacetate, dodecyl 2-bromoisobutyrate, ethyl 2-bromoisobutyrate, ethyl 2-bromopropionate, 2-hydroxyethyl 2-bromoisobutyrate, octadecyl 2-bromoisobutyrate, 2-(2-bromoisobutyryloxy)ethyl methacrylate, 1-bromoethylbenzene, 2-bromoisobutanoic acid N-hydroxysuccinimide ester, 2-bromoisobutyric anhydride, 2-azidoethyl 2-bromoisobutyrate, bis[2-(2′-bromoisobutyryloxy)ethyl]disulfide, and bis[2-(2-bromoisobutyryloxy)undecyl] disulfide.
16. The method of claim 7, wherein one or more other monomers are selected from the group consisting of styrenes, acrylamides, vinyl halides, vinyl alcohols, vinyl esters, and vinyl amides.
17. The method of claim 7, wherein the polymerization involves transfer radical polymerization (ATRP).
18. The method of claim 1, wherein the original block copolymer is poly(methyl methacrylate)-b-polystyrene (PMMA-b-PS), and the block copolymer is poly(hydroxyisobutylene)-b-polystyrene (PiBOH-b-PS).
19. The method of claim 1, wherein the original block copolymer is poly(methyl acrylate)-b-polystyrene (PMA-b-PS), and the block copolymer is poly(hydroxypropylene)-b-polystyrene (PPOH-b-PS).
20. The method of claim 1, wherein the original block copolymer is poly(methyl acrylate)-b-poly(tert-butylstyrene) (PMA-b-PtBS), and the block copolymer is poly(hydroxypropylene)-b-poly(tert-butylstyrene) (PPOH-b-PtBS).
21. A method of using a block copolymer prepared by the method of claim 1, the method comprising substituting the —OH groups of the block copolymer to form a block copolymer of the formula: ##STR00058## wherein: R.sup.A is —OR.sup.O, —SR.sup.S, —N(R.sup.N).sub.2, or substituted phosphorous; R.sup.O is optionally substituted alkyl, optionally substituted carbocyclyl, optionally substituted heterocyclyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted acyl, or an oxygen protecting group; each instance of R.sup.N is independently hydrogen, optionally substituted alkyl, optionally substituted carbocyclyl, optionally substituted heterocyclyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted acyl, or a nitrogen protecting group; optionally wherein two R.sup.N attached to the same nitrogen atom are joined together with the intervening atoms to form optionally substituted heterocyclyl or optionally substituted heteroaryl; and R.sup.S is hydrogen, optionally substituted alkyl, optionally substituted carbocyclyl, optionally substituted heterocyclyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted acyl, or a sulfur protecting group.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
(1) The accompanying drawings, which constitute a part of this specification, illustrate several embodiments of the invention and together with the description, serve to explain the principles of the invention.
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DETAILED DESCRIPTION OF CERTAIN EMBODIMENTS
(17) Provided herein are polymers that, in certain embodiments, self-assemble to form well-defined nanostructures. In some instances, the nanostructures exhibit relatively small d-spacing (e.g., a d-spacing value of 10 nm or less), which can lead to more well-defined nanostructures. Due to their properties, the polymers described herein are useful in a variety of applications including functional materials and biomedical applications (e.g., drug delivery systems, nanowires, bit-patterned storage media, filtration membranes, and more). Also provided herein are compositions and materials comprising the polymers, and uses of the polymers.
(18) In certain embodiments, the polymers are prepared from derivatization (e.g., reduction) of polymers (e.g., homopolymers, copolymers, block copolymers) comprising acrylate repeating units. Another aspect of the present invention provides methods for preparing the polymers provided herein. These methods may involve assembling a homopolymer or copolymer, followed by derivatization (e.g., reduction, substitution, etc.) of the acrylate portions of the polymer.
(19) Polymers
(20) In one aspect, the present invention provides polymers (e.g., homopolymers, copolymers, block copolymers). In certain embodiments, the polymers comprise polyacrylate repeating units that have been derivatized (e.g., reduced, and optionally further derivatized). For example, in certain embodiments, the present invention provides homopolymers or copolymers comprising acrylate repeating units, wherein the acrylate repeating units have been reduced. In certain embodiments, the acrylate repeating units are not poly(methyl methacrylate) (PMMA) repeating units. The present invention also provides block copolymers (e.g., diblock, triblock, tetrablock copolymers) wherein at least one block comprises acrylate repeating units, wherein the acrylate repeating units have been reduced. In certain embodiments, the polymers have useful properties, such as defined structures after self-assembly. In certain embodiments, the polymers self-assemble to form specific morphologies (e.g., lamellar, hexagonal cylinder, body centered cubic morphology) with certain d-spacing values (e.g., less than 10 nm). The well-defined morphologies and relatively small d-spacing values of polymers described herein can confer advantageous properties, and thus the polymers are useful in, e.g., functional materials and biomedical applications (e.g., drug delivery systems, nanowires, bit-patterned storage media, filtration membranes, and more).
(21) Provided herein are polymers comprising repeating units of the following formula:
(22) ##STR00009##
wherein:
(23) R.sup.1, R.sup.2, and R.sup.3 are independently hydrogen, halogen, optionally substituted alkyl, optionally substituted carbocyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl;
(24) R.sup.A is halogen, —OR.sup.O, —SR.sup.S, —N(R.sup.N).sub.2, or substituted phosphorous;
(25) each instance of R.sup.O is independently hydrogen, optionally substituted alkyl, optionally substituted carbocyclyl, optionally substituted heterocyclyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted acyl, or an oxygen protecting group;
(26) each instance of R.sup.N is independently hydrogen, optionally substituted alkyl, optionally substituted carbocyclyl, optionally substituted heterocyclyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted acyl, or a nitrogen protecting group; optionally wherein two R.sup.N attached to the same nitrogen atom are joined together with the intervening atoms to form optionally substituted heterocyclyl or optionally substituted heteroaryl;
(27) each instance of R.sup.O is independently hydrogen, optionally substituted alkyl, optionally substituted carbocyclyl, optionally substituted heterocyclyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted acyl, or an oxygen protecting group; and
(28) each instance of R.sup.S is independently hydrogen, optionally substituted alkyl, optionally substituted carbocyclyl, optionally substituted heterocyclyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted acyl, or a sulfur protecting group;
(29) provided that the repeating unit is not of the formula:
(30) ##STR00010##
(31) In certain embodiments, the polymer comprises repeating units of one of the following formulae:
(32) ##STR00011##
(33) In certain embodiments, the polymer comprises repeating units of the following formula:
(34) ##STR00012##
(35) In certain embodiments, the polymer comprises repeating units of the following formula:
(36) ##STR00013##
(37) In certain embodiments, the polymer is a reduced form of poly(methyl acrylate), comprising repeating units of the following formula:
(38) ##STR00014##
(39) In certain embodiments, the polymer is a block copolymer. Provided herein are block copolymers, wherein at least one of the polymer blocks comprises repeating units of the following formula:
(40) ##STR00015##
wherein:
(41) R.sup.1, R.sup.2, and R.sup.3 are independently hydrogen, halogen, optionally substituted alkyl, optionally substituted carbocyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl;
(42) R.sup.A is halogen, —OR.sup.O, —SR.sup.S, —N(R.sup.N).sub.2, or substituted phosphorous;
(43) each instance of R.sup.O is independently hydrogen, optionally substituted alkyl, optionally substituted carbocyclyl, optionally substituted heterocyclyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted acyl, or an oxygen protecting group;
(44) each instance of R.sup.N is independently hydrogen, optionally substituted alkyl, optionally substituted carbocyclyl, optionally substituted heterocyclyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted acyl, or a nitrogen protecting group; optionally wherein two R.sup.N attached to the same nitrogen atom are joined together with the intervening atoms to form optionally substituted heterocyclyl or optionally substituted heteroaryl;
(45) each instance of R.sup.O is independently hydrogen, optionally substituted alkyl, optionally substituted carbocyclyl, optionally substituted heterocyclyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted acyl, or an oxygen protecting group; and
(46) each instance of R.sup.S is independently hydrogen, optionally substituted alkyl, optionally substituted carbocyclyl, optionally substituted heterocyclyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted acyl, or a sulfur protecting group.
(47) In certain embodiments, at least one of the polymer blocks of the block copolymer comprises repeating units of one of the following formulae:
(48) ##STR00016##
(49) In certain embodiments, at least one of the polymer blocks of the block copolymer comprises repeating units of the following formula:
(50) ##STR00017##
(51) In certain embodiments, at least one of the polymer blocks of the block copolymer comprises repeating units of the following formula:
(52) ##STR00018##
(53) In certain embodiments, at least one of the polymer blocks of the block copolymer comprises repeating units of the following formula:
(54) ##STR00019##
(55) In certain embodiments, at least one of the polymer blocks of the block copolymer comprises repeating units of the following formula:
(56) ##STR00020##
(57) In certain embodiments, the block copolymer is a diblock copolymer. In certain embodiments, the block copolymer is a triblock or tetrablock copolymer. In certain embodiments, the block copolymer comprises five or more polymer blocks.
(58) The additional polymer blocks of the block copolymer described herein can be composed of any polymeric material (e.g., any monomers). Examples of polymers include, but are not limited to, polyvinyl polymers (e.g., polyvinyl chloride), polyethylenes (e.g., polyethylene, polytetrafluoroethylene), polypropylenes, polyacetylenes, polyethers (e.g., polyethylene glycol, polyoxymethylene, polypropylene glycol, polytetramethylene glycol, poly(ethyl ethylene) phosphate, poly(oxazoline)), polyamines, polyesters (e.g., polyglycolic acid, polylactic acid, poly(lactic-co-glycolic acid), polycaprolactone, polyhydroxyalkanoate, polyhydroxybutryate, polyethylene adipate, polybutylene succinate, poly(3-hydroxybutyrate-co-3-hydroxyvalerate), polysilanes, polysiloxanes (e.g., polydimethylsiloxane), polyacrylates (e.g., polymethacrylate, poly(n-butyl acrylate), poly(tert-butyl acrylate)), polystyrenes, polylactides (e.g., polylactic acid), polyamino acids, polypeptides, polyamides, polyacrylamides (e.g., polymethylacrylamide), and polysaccharides.
(59) For example, in certain embodiments, the block copolymer comprises a second polymer block, wherein the second polymer block comprises repeating units of the formula:
(60) ##STR00021##
wherein:
(61) R.sup.5, R.sup.6, and R.sup.7 are independently hydrogen, halogen, optionally substituted alkyl, optionally substituted carbocyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl;
(62) each instance of R.sup.8a is independently hydrogen, halogen, —CN, —NO.sub.2, —N.sub.3, optionally substituted alkyl, optionally substituted carbocyclyl, optionally substituted heterocyclyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted acyl, —OR.sup.O, —SR.sup.S, or —N(R.sup.N).sub.2;
(63) each instance of R.sup.O is independently hydrogen, optionally substituted alkyl, optionally substituted carbocyclyl, optionally substituted heterocyclyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted acyl, or an oxygen protecting group;
(64) each instance of R.sup.N is independently hydrogen, optionally substituted alkyl, optionally substituted carbocyclyl, optionally substituted heterocyclyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted acyl, or a nitrogen protecting group; optionally wherein two R.sup.N attached to the same nitrogen atom are joined together with the intervening atoms to form optionally substituted heterocyclyl or optionally substituted heteroaryl;
(65) each instance of R.sup.S is independently hydrogen, optionally substituted alkyl, optionally substituted carbocyclyl, optionally substituted heterocyclyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted acyl, or a sulfur protecting group; and
(66) p is 0, 1, 2, 5, 4, or 5.
(67) In certain embodiments, the second polymer block is a polymer composed of optionally substituted styrene monomers. In certain embodiments, the second polymer block is polystyrene (PS), poly(4-vinylanisole), poly(4-acetoxystyrene), poly(4-tert-butoxystyrene), poly(4-fluorostyrene), poly(3-nitrostyrene), poly(α-methylstyrene), poly(methylstyrene), or poly(4-tert-butylstyrene).
(68) In certain embodiments, the block copolymer comprises a polystyrene (PS) block, wherein the repeating units of the second polymer block are of the formula:
(69) ##STR00022##
In certain embodiments, the block copolymer comprises a poly(4-tert-butylstyrene) (PtBS) block wherein the repeating units of the second polymer block are of the formula:
(70) ##STR00023##
(71) In certain embodiments, the block copolymers provided herein are of Formula (I):
(72) ##STR00024##
wherein:
(73) T.sup.1 and T.sup.2 are independently terminal groups selected from the group consisting of hydrogen, halogen, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted heteroalkyl, optionally substituted carbocyclyl, optionally substituted heterocyclyl, optionally substituted aryl, optionally substituted heteroaryl, and optionally substituted acyl, and polymers;
(74) R.sup.A is halogen, —OR.sup.O, —SR.sup.S, —N(R.sup.N).sub.2, or substituted phosphorous;
(75) each instance of R.sup.O is independently hydrogen, optionally substituted alkyl, optionally substituted carbocyclyl, optionally substituted heterocyclyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted acyl, or an oxygen protecting group;
(76) each instance of R.sup.N is independently hydrogen, optionally substituted alkyl, optionally substituted carbocyclyl, optionally substituted heterocyclyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted acyl, or a nitrogen protecting group; optionally wherein two R.sup.N attached to the same nitrogen atom are joined together with the intervening atoms to form optionally substituted heterocyclyl or optionally substituted heteroaryl;
(77) each instance of R.sup.O is independently hydrogen, optionally substituted alkyl, optionally substituted carbocyclyl, optionally substituted heterocyclyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted acyl, or a sulfur protecting group; and
(78) each instance of R.sup.S is independently hydrogen, optionally substituted alkyl, optionally substituted carbocyclyl, optionally substituted heterocyclyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted acyl, or a sulfur protecting group
(79) R.sup.1, R.sup.2, and R.sup.3 are independently hydrogen, halogen, optionally substituted alkyl, optionally substituted carbocyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl;
(80) R.sup.5, R.sup.6, and R.sup.7 are independently hydrogen, halogen, optionally substituted alkyl, optionally substituted carbocyclyl, optionally substituted heterocyclyl, optionally substituted aryl, or optionally substituted heteroaryl;
(81) R.sup.8 is optionally substituted alkyl, optionally substituted carbocyclyl, optionally substituted heterocyclyl, optionally substituted aryl, optionally substituted heteroaryl, or optionally substituted acyl; or R.sup.8 is a polymer; and
(82) n and m are independently integers from 1 to 2000, inclusive.
(83) In certain embodiments, the block copolymer is of one of the following formulae:
(84) ##STR00025##
(85) In certain embodiments, the block copolymer is of Formula (II):
(86) ##STR00026##
(87) In certain embodiments, the block copolymer is of Formula (III):
(88) ##STR00027##
(89) In certain embodiments, the block copolymer is of the formula:
(90) ##STR00028##
(91) In certain embodiments, the block copolymer is of the formula:
(92) ##STR00029##
wherein:
(93) each instance of R.sup.8a is independently hydrogen, halogen, —CN, —NO.sub.2, —N.sub.3, optionally substituted alkyl, optionally substituted carbocyclyl, optionally substituted heterocyclyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted acyl, —OR.sup.O, —SR.sup.S, or —N(R.sup.N).sub.2; and
(94) p is 0, 1, 2, 5, 4, or 5.
(95) In certain embodiments, the block copolymer is of the formula:
(96) ##STR00030##
(97) In certain embodiments, the block copolymer is of the formula:
(98) ##STR00031##
(99) In certain embodiments, the block copolymer is of the formula:
(100) ##STR00032##
(101) In certain embodiments, the block copolymer is of the formula:
(102) ##STR00033##
(103) In certain embodiments, the block copolymer is of the formula:
(104) ##STR00034##
(105) As generally defined herein, n is an integer from 1-2000, inclusive. In certain embodiments, n is from 2-1000, inclusive. In certain embodiments, n is from 2-200, inclusive. In certain embodiments, n is from 2-100, inclusive. In certain embodiments, n is from 2-50, inclusive. In certain embodiments, n is from 2-40, inclusive. In certain embodiments, n is from 2-30, inclusive. In certain embodiments, n is from 2-20, inclusive. In certain embodiments, n is from 2-10, inclusive. In certain embodiments, n is from 5-20, inclusive.
(106) As generally defined herein, m is an integer from 1-2000, inclusive. In certain embodiments, m is from 2-1000, inclusive. In certain embodiments, m is from 2-200, inclusive. In certain embodiments, m is from 2-100, inclusive. In certain embodiments, m is from 2-50, inclusive. In certain embodiments, m is from 2-40, inclusive. In certain embodiments, m is from 2-30, inclusive. In certain embodiments, m is from 2-20, inclusive. In certain embodiments, m is from 2-10, inclusive. In certain embodiments, m is from 5-20, inclusive.
(107) The ratio of n to m can be any ratio. In certain embodiments, the ratio of n to m is approximately 1:1. In certain embodiments, the ratio of n to m is approximately from 1:1 to 1:2. In certain embodiments, the ratio of n to m is approximately 1:1.1. In certain embodiments, the ratio of n to m is approximately 1:1.2. In certain embodiments, the ratio of n to m is approximately 1:1.3. In certain embodiments, the ratio of n to m is approximately 1:1.4. In certain embodiments, the ratio of n to m is approximately 1:1.5. In certain embodiments, the ratio of n to m is approximately 1:1.6. In certain embodiments, the ratio of n to m is approximately 1:1.7. In certain embodiments, the ratio of n to m is approximately 1:1.8. In certain embodiments, the ratio of n to m is approximately 1:1.9. In certain embodiments, the ratio of n to m is approximately 1:2.0.
(108) In certain embodiments, the ratio of m to n is approximately from 1:1 to 1:2. In certain embodiments, the ratio of m to n is approximately 1:1.1. In certain embodiments, the ratio of m to n is approximately 1:1.2. In certain embodiments, the ratio of m to n is approximately 1:1.3. In certain embodiments, the ratio of m to n is approximately 1:1.4. In certain embodiments, the ratio of m to n is approximately 1:1.5. In certain embodiments, the ratio of m to n is approximately 1:1.6. In certain embodiments, the ratio of m to n is approximately 1:1.7. In certain embodiments, the ratio of m to n is approximately 1:1.8. In certain embodiments, the ratio of m to n is approximately 1:1.9. In certain embodiments, the ratio of m to n is approximately 1:2.0.
(109) The polymers described herein may self-assemble into form structures with any morphology. In certain embodiments, the polymers self-assemble into structures with hexagonal cylindrical, gyroid, spherical, lamellar, ellipsoidal, polyhedral, or cubic morphologies. In certain embodiments, the polymer has a lamellae, hexagonal cylinder, or body-centered cubic morphology.
(110) Self-assembled polymers described herein have d-spacing values which can be measured. “d-spacing,” as used herein, refers to the spacing or distance between successive planes of atoms in an ordered nanostructure. In certain embodiments, the d-spacing value is from 1-50 nm. In certain embodiments, the d-spacing value is from 1-40 nm. In certain embodiments, the d-spacing value is from 1-30 nm. In certain embodiments, the d-spacing value is from 1-20 nm. In certain embodiments, the d-spacing value is less than 20 nm. In certain embodiments, the d-spacing value is less than 25 nm. In certain embodiments, the d-spacing value is less than 24 nm. In certain embodiments, the d-spacing value is less than 23 nm. In certain embodiments, the d-spacing value is less than 22 nm. In certain embodiments, the d-spacing value is less than 21 nm. In certain embodiments, the d-spacing value is less than 20 nm. In certain embodiments, the d-spacing value is less than 19 nm. In certain embodiments, the d-spacing value is less than 18 nm. In certain embodiments, the d-spacing value is less than 17 nm. In certain embodiments, the d-spacing value is less than 16 nm. In certain embodiments, the d-spacing value is less than 15 nm. In certain embodiments, the d-spacing value is less than 14 nm. In certain embodiments, the d-spacing value is less than 13 nm. In certain embodiments, the d-spacing value is less than 12 nm. In certain embodiments, the d-spacing value is less than 11 nm. In certain embodiments, the d-spacing value is less than 10 nm. In certain embodiments, the d-spacing value from 1-10 nm. In certain embodiments, the d-spacing value from 5-10 nm. In certain embodiments, the d-spacing value is less than 9 nm. In certain embodiments, the d-spacing value is less than 8 nm. In certain embodiments, the d-spacing value is less than 7 nm. In certain embodiments, the d-spacing value is less than 6 nm. In certain embodiments, the d-spacing value is less than 5 nm. In a preferred embodiment, the d-spacing value is less than 10 nm.
(111) Polymers described herein may be of any molecular weight. A polymer may have an overall molecular weight of approximately 10 Da or greater, approximately 20 Da or greater, approximately 30 Da or greater, approximately 50 Da or greater, approximately 100 Da or greater, approximately 500 Da or greater, approximately 1000 Da or greater, approximately 2000 Da or greater, approximately 5000 Da or greater, approximately 10000 Da or greater, approximately 20000 Da or greater, or approximately 50000 Da or greater.
(112) The following R group definitions apply to all polymers, compounds, and methods described herein.
(113) As generally defined herein, R.sup.A is halogen, —OR.sup.O, —SR.sup.S, —N(R.sup.N).sub.2, or substituted phosphorous. In certain embodiments, R.sup.A is halogen (e.g., —Cl, —F, —Br, —I). In certain embodiments, R.sup.A is —OR.sup.O. In certain embodiments, R.sup.A is —SR.sup.S. In certain embodiments, R.sup.A is —N(R.sup.N).sub.2. In certain embodiments, R.sup.A is substituted phosphorous (e.g., —P(R.sub.cc).sub.2, —P(OR.sub.cc).sub.2, —P(R.sub.cc).sub.3.sup.+X.sup.−, —P(OR.sub.cc).sub.3.sup.+X.sup.−, —P(R.sub.cc).sub.4, —P(OR.sub.cc).sub.4, —P(═O)(N(R.sub.bb).sub.2).sub.2, —P(═O)(R.sub.aa).sub.2, or —P(═O)(OR.sub.cc).sub.2).
(114) As generally defined herein, R.sup.1 is hydrogen, halogen, optionally substituted alkyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted carbocyclyl, or optionally substituted heterocyclyl. In certain embodiments, R.sup.1 is hydrogen. In certain embodiments, R.sup.1 is halogen (e.g., —Cl, —F, —Br, —I). In certain embodiments, R.sup.1 is optionally substituted alkyl. In certain embodiments, R.sup.1 is optionally substituted aryl. In certain embodiments, R.sup.1 is optionally substituted heteroaryl. In certain embodiments, R.sup.1 is optionally substituted carbocyclyl. In certain embodiments, R.sup.1 is optionally substituted heterocyclyl. In certain embodiments, R.sup.1 is optionally substituted C.sub.1-6 alkyl. In certain embodiments, R.sup.1 is unsubstituted C.sub.1-6 alkyl. In certain embodiments, R.sup.1 is optionally substituted C.sub.1-3 alkyl. In certain embodiments, R.sup.1 is unsubstituted C.sub.1-3 alkyl. In certain embodiments, R.sup.1 is selected from the group consisting of methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, iso-butyl, and tert-butyl. In certain embodiments, R.sup.1 is methyl.
(115) As generally defined herein, R.sup.2 is hydrogen, halogen, optionally substituted alkyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted carbocyclyl, or optionally substituted heterocyclyl. In certain embodiments, R.sup.2 is hydrogen. In certain embodiments, R.sup.2 is halogen (e.g., —Cl, —F, —Br, —I). In certain embodiments, R.sup.2 is optionally substituted alkyl. In certain embodiments, R.sup.2 is optionally substituted aryl. In certain embodiments, R.sup.2 is optionally substituted heteroaryl. In certain embodiments, R.sup.2 is optionally substituted carbocyclyl. In certain embodiments, R.sup.2 is optionally substituted heterocyclyl. In certain embodiments, R.sup.2 is optionally substituted C.sub.1-6 alkyl. In certain embodiments, R.sup.2 is unsubstituted C.sub.1-6 alkyl. In certain embodiments, R.sup.2 is optionally substituted C.sub.1-3 alkyl. In certain embodiments, R.sup.2 is unsubstituted C.sub.1-3 alkyl. In certain embodiments, R.sup.2 is selected from the group consisting of methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, iso-butyl, and tert-butyl. In certain embodiments, R.sup.2 is methyl.
(116) As generally defined herein, R.sup.3 is hydrogen, halogen, optionally substituted alkyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted carbocyclyl, or optionally substituted heterocyclyl. In certain embodiments, R.sup.3 is hydrogen. In certain embodiments, R.sup.3 is halogen (e.g., —Cl, —F, —Br, —I). In certain embodiments, R.sup.3 is optionally substituted alkyl. In certain embodiments, R.sup.3 is optionally substituted aryl. In certain embodiments, R.sup.3 is optionally substituted heteroaryl. In certain embodiments, R.sup.3 is optionally substituted carbocyclyl. In certain embodiments, R.sup.3 is optionally substituted heterocyclyl. In certain embodiments, R.sup.3 is optionally substituted C.sub.1-6 alkyl. In certain embodiments, R.sup.3 is unsubstituted C.sub.1-6 alkyl. In certain embodiments, R.sup.3 is optionally substituted C.sub.1-3 alkyl. In certain embodiments, R.sup.3 is unsubstituted C.sub.1-3 alkyl. In certain embodiments, R.sup.3 is selected from the group consisting of methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, iso-butyl, and tert-butyl. In certain embodiments, R.sup.3 is methyl.
(117) In certain embodiments, R.sup.1, R.sup.2, and R.sup.3 are each hydrogen. In certain embodiments, R and R.sup.2 are hydrogen; and R.sup.3 is methyl. In certain embodiments, R.sup.3 is not methyl.
(118) As generally defined herein, R.sup.5 is hydrogen, halogen, optionally substituted alkyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted carbocyclyl, or optionally substituted heterocyclyl. In certain embodiments, R.sup.5 is hydrogen. In certain embodiments, R.sup.5 is halogen (e.g., —Cl, —F, —Br, —I). In certain embodiments, R.sup.5 is optionally substituted alkyl. In certain embodiments, R.sup.5 is optionally substituted aryl. In certain embodiments, R.sup.5 is optionally substituted heteroaryl. In certain embodiments, R.sup.5 is optionally substituted carbocyclyl. In certain embodiments, R.sup.5 is optionally substituted heterocyclyl. In certain embodiments, R.sup.5 is optionally substituted C.sub.1-6 alkyl. In certain embodiments, R.sup.5 is unsubstituted C.sub.1-6 alkyl. In certain embodiments, R.sup.5 is optionally substituted C.sub.1-3 alkyl. In certain embodiments, R.sup.5 is unsubstituted C.sub.1-3 alkyl. In certain embodiments, R.sup.5 is selected from the group consisting of methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, iso-butyl, and tert-butyl. In certain embodiments, R.sup.5 is methyl.
(119) As generally defined herein, R.sup.6 is hydrogen, halogen, optionally substituted alkyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted carbocyclyl, or optionally substituted heterocyclyl. In certain embodiments, R.sup.6 is hydrogen. In certain embodiments, R.sup.6 is halogen (e.g., —Cl, —F, —Br, —I). In certain embodiments, R.sup.6 is optionally substituted alkyl. In certain embodiments, R.sup.6 is optionally substituted aryl. In certain embodiments, R.sup.6 is optionally substituted heteroaryl. In certain embodiments, R.sup.6 is optionally substituted carbocyclyl. In certain embodiments, R.sup.6 is optionally substituted heterocyclyl. In certain embodiments, R.sup.6 is optionally substituted C.sub.1-6 alkyl. In certain embodiments, R.sup.6 is unsubstituted C.sub.1-6 alkyl. In certain embodiments, R.sup.6 is optionally substituted C.sub.1-3 alkyl. In certain embodiments, R.sup.6 is unsubstituted C.sub.1-3 alkyl. In certain embodiments, R.sup.6 is selected from the group consisting of methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, iso-butyl, and tert-butyl. In certain embodiments, R.sup.6 is methyl.
(120) As generally defined herein, R.sup.7 is hydrogen, halogen, optionally substituted alkyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted carbocyclyl, or optionally substituted heterocyclyl. In certain embodiments, R.sup.7 is hydrogen. In certain embodiments, R.sup.7 is halogen (e.g., —Cl, —F, —Br, —I). In certain embodiments, R.sup.7 is optionally substituted alkyl. In certain embodiments, R.sup.7 is optionally substituted aryl. In certain embodiments, R.sup.7 is optionally substituted heteroaryl. In certain embodiments, R.sup.7 is optionally substituted carbocyclyl. In certain embodiments, R.sup.7 is optionally substituted heterocyclyl. In certain embodiments, R.sup.7 is optionally substituted C.sub.1-6 alkyl. In certain embodiments, R.sup.7 is unsubstituted C.sub.1-6 alkyl. In certain embodiments, R.sup.7 is optionally substituted C.sub.1-3 alkyl. In certain embodiments, R.sup.7 is unsubstituted C.sub.1-3 alkyl. In certain embodiments, R.sup.7 is selected from the group consisting of methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, iso-butyl, and tert-butyl. In certain embodiments, R.sup.7 is methyl.
(121) In certain embodiments, R.sup.5, R.sup.6, and R.sup.7 are each hydrogen.
(122) As generally defined herein, R.sup.8 is optionally substituted alkyl, optionally substituted carbocyclyl, optionally substituted heterocyclyl, optionally substituted aryl, optionally substituted heteroaryl, or optionally substituted acyl; or R.sup.8 is a polymer. In certain embodiments, R.sup.8 is optionally substituted alkyl. In certain embodiments, R.sup.8 is optionally substituted carbocyclyl. In certain embodiments, R.sup.8 is optionally substituted heterocyclyl. In certain embodiments, R.sup.8 is optionally substituted aryl. In certain embodiments, R.sup.8 is optionally substituted heteroaryl. In certain embodiments, R.sup.8 is optionally substituted acyl. In certain embodiments, R.sup.8 is a polymer sidechain. In certain embodiments, R.sup.8 is optionally substituted phenyl. In certain embodiments, R.sup.8 is of the formula:
(123) ##STR00035##
(124) In certain embodiments, R.sup.8 is of one of the following formulae:
(125) ##STR00036##
(126) In certain embodiments, R.sup.8 is of the formula:
(127) ##STR00037##
In certain embodiments, R.sup.8 is of the formula:
(128) ##STR00038##
In certain embodiments, R.sup.8 is of the formula:
(129) ##STR00039##
(130) As defined herein, each instance of R.sup.8a is independently hydrogen, halogen, —CN, —NO.sub.2, —N.sub.3, optionally substituted alkyl, optionally substituted carbocyclyl, optionally substituted heterocyclyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted acyl, —OR.sup.O, —SR.sup.S, or —N(R.sup.N).sub.2. In certain embodiments, at least one instance of R.sup.8a is hydrogen. In certain embodiments, at least one instance of R.sup.8a is halogen. In certain embodiments, at least one instance of R.sup.8a is —CN. In certain embodiments, at least one instance of R.sup.8a is —NO.sub.2. In certain embodiments, at least one instance of R.sup.8a is —N.sub.3. In certain embodiments, at least one instance of R.sup.8a is optionally substituted alkyl. In certain embodiments, at least one instance of R.sup.8a is optionally substituted carbocyclyl. In certain embodiments, at least one instance of R.sup.8a is optionally substituted heterocyclyl. In certain embodiments, at least one instance of R.sup.8a is optionally substituted aryl. In certain embodiments, at least one instance of R.sup.8a is optionally substituted heteroaryl. In certain embodiments, at least one instance of R.sup.8a is optionally substituted acyl. In certain embodiments, at least one instance of R.sup.8a is —OR.sup.O. In certain embodiments, at least one instance of R.sup.8a is —SR.sup.S. In certain embodiments, at least one instance of R.sup.8a is —N(R.sup.N).sub.2. In certain embodiments, at least one instance of R.sup.8a is unsubstituted C.sub.1-6 alkyl. In certain embodiments, at least one instance of R.sup.8a is optionally substituted C.sub.1-3 alkyl. In certain embodiments, at least one instance of R.sup.8a is unsubstituted C.sub.1-3 alkyl. In certain embodiments, at least one instance of R.sup.8a is selected from the group consisting of methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, iso-butyl, and tert-butyl. In certain embodiments, at least one instance of R.sup.8a is tert-butyl.
(131) As generally defined herein, p is 0, 1, 2, 3, 4, or 5. In certain embodiments, p is 0. In certain embodiments, p is 1. In certain embodiments, p is 2. In certain embodiments, p is 3. In certain embodiments, p is 4. In certain embodiments, p is 5.
(132) As generally defined herein, T.sup.1 is a terminal group selected from the group consisting of hydrogen, halogen, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted heteroalkyl, optionally substituted carbocyclyl, optionally substituted heterocyclyl, optionally substituted aryl, optionally substituted heteroaryl, and optionally substituted acyl, and polymers. In certain embodiments, T.sup.1 is hydrogen. In certain embodiments, T.sup.1 is halogen. In certain embodiments, T.sup.1 is optionally substituted alkyl. In certain embodiments, T.sup.1 is optionally substituted alkenyl. In certain embodiments, T.sup.1 is optionally substituted alkynyl. In certain embodiments, T.sup.1 is optionally substituted heteroalkyl. In certain embodiments, T.sup.1 is optionally substituted carbocyclyl. In certain embodiments, T.sup.1 is optionally substituted heterocyclyl. In certain embodiments, T.sup.1 is optionally substituted aryl. In certain embodiments, T.sup.1 is optionally substituted heteroaryl. In certain embodiments, T.sup.1 is and optionally substituted acyl. In certain embodiments, T.sup.1 is optionally substituted C.sub.1-6 alkyl. In certain embodiments, T.sup.1 is of one of the following formulae:
(133) ##STR00040##
(134) As generally defined herein, T.sup.2 is a terminal group selected from the group consisting of hydrogen, halogen, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted heteroalkyl, optionally substituted carbocyclyl, optionally substituted heterocyclyl, optionally substituted aryl, optionally substituted heteroaryl, and optionally substituted acyl, and polymers. In certain embodiments, T.sup.2 is hydrogen. In certain embodiments, T.sup.2 is halogen. In certain embodiments, T.sup.2 is optionally substituted alkyl. In certain embodiments, T.sup.2 is optionally substituted alkenyl. In certain embodiments, T.sup.2 is optionally substituted alkynyl. In certain embodiments, T.sup.2 is optionally substituted heteroalkyl. In certain embodiments, T.sup.2 is optionally substituted carbocyclyl. In certain embodiments, T.sup.2 is optionally substituted heterocyclyl. In certain embodiments, T.sup.2 is optionally substituted aryl. In certain embodiments, T.sup.2 is optionally substituted heteroaryl. In certain embodiments, T.sup.2 is and optionally substituted acyl. In certain embodiments, T.sup.2 is optionally substituted C.sub.1-6 alkyl. In certain embodiments, T.sup.2 is of one of the following formulae:
(135) ##STR00041##
(136) As generally defined herein, R.sup.O hydrogen, optionally substituted alkyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted carbocyclyl, optionally substituted heterocyclyl, optionally substituted acyl, or an oxygen protecting group. In certain embodiments, R.sup.O is hydrogen. In certain embodiments, R.sup.O is optionally substituted alkyl. In certain embodiments, R.sup.O is optionally substituted C.sub.1-6 alkyl. In certain embodiments, R.sup.O is unsubstituted C.sub.1-6 alkyl. In certain embodiments, R.sup.O is selected from the group consisting of methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, iso-butyl, and tert-butyl. In certain embodiments, R.sup.O is methyl. In certain embodiments, R.sup.O is optionally substituted aryl. In certain embodiments, R.sup.O is optionally substituted heteroaryl. In certain embodiments, R.sup.O is optionally substituted carbocyclyl. In certain embodiments, R.sup.O is optionally substituted heterocyclyl. In certain embodiments, R.sup.O is optionally substituted acyl. In certain embodiments, R.sup.O is an oxygen protecting group.
(137) As generally defined herein, each instance of R.sup.N is independently hydrogen, optionally substituted alkyl, optionally substituted carbocyclyl, optionally substituted heterocyclyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted acyl, or a nitrogen protecting group; or optionally two R.sup.N on the same nitrogen atom are taken together with the intervening atoms to form optionally substituted heterocyclyl or optionally substituted heteroaryl. In certain embodiments, R.sup.N is hydrogen. In certain embodiments, R.sup.N is optionally substituted alkyl. In certain embodiments, R.sup.N is optionally substituted C.sub.1-6 alkyl. In certain embodiments, R.sup.N is unsubstituted C.sub.1-6 alkyl. In certain embodiments, R.sup.N is optionally substituted C.sub.1-3 alkyl. In certain embodiments, R.sup.N is unsubstituted C.sub.1-3 alkyl. In certain embodiments, R.sup.N is selected from the group consisting of methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, iso-butyl, and tert-butyl. In certain embodiments, R.sup.N is optionally substituted carbocyclyl. In certain embodiments, R.sup.N is optionally substituted heterocyclyl. In certain embodiments, R.sup.N is optionally substituted aryl. In certain embodiments, R.sup.N is optionally substituted heteroaryl. In certain embodiments, R.sup.N is or a nitrogen protecting group. In certain embodiments, R.sup.N on the same nitrogen atom are taken together with the intervening atoms to form optionally substituted heterocyclyl or optionally substituted heteroaryl.
(138) As generally defined herein, R.sup.S hydrogen, optionally substituted alkyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted carbocyclyl, optionally substituted heterocyclyl, optionally substituted acyl, or a sulfur protecting group. In certain embodiments, R.sup.S is hydrogen. In certain embodiments, R.sup.S is optionally substituted alkyl. In certain embodiments, R.sup.S is optionally substituted C.sub.1-6 alkyl. In certain embodiments, R.sup.S is unsubstituted C.sub.1-6 alkyl. In certain embodiments, R.sup.S is selected from the group consisting of methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, iso-butyl, and tert-butyl. In certain embodiments, R.sup.S is methyl. In certain embodiments, R.sup.S is optionally substituted aryl. In certain embodiments, R.sup.S is optionally substituted heteroaryl. In certain embodiments, R.sup.S is optionally substituted carbocyclyl. In certain embodiments, R.sup.S is optionally substituted heterocyclyl. In certain embodiments, R.sup.S is optionally substituted acyl. In certain embodiments, R.sup.S is a sulfur protecting group.
(139) Uses and Compositions
(140) Polymers described herein can be used in material and biomedical applications. For example, polymers described herein can be used in functional materials such as photonics (e.g., photonic crystals), chromatography media (e.g., filtration membranes), stimuli-responsive materials, lubricants, coatings, nanowires, nanolithography, storage media, films, and batteries (e.g., lithium-air batteries). Polymers described herein are also useful in biomedical applications such as drug delivery, materials (e.g., an injectable implant) for tissue or cartilage repair, cosmetic implantation, and lubrication of tissues or biological membranes.
(141) Also provided herein are compositions comprising a polymer described herein and one or more carriers. The carrier may be a pharmaceutically acceptable carrier or another chemical medium (e.g., a solvent or other medium). In certain embodiments, the composition is a pharmaceutical compostion optionally comprising one or more additional agents (e.g., therapeutic agents)
(142) Also provided herein are particles (e.g., nanoparticles, microparticles) comprising a polymer described herein. In another aspect, the present invention provides gels (e.g., hydrogels) comprising polymers described herein.
(143) Also provided herein are kits comprising one or more polymers described herein, or a composition or material thereof. The kit may further comprise instructions for use of the polymer, composition, or material.
(144) Methods for Preparing Polymers
(145) Provided herein are methods for preparing the polymers described herein. In general, the methods comprise polymerizing one or more monomers to form a homopolymer or copolymer, wherein at least one of the monomers is an acrylate. The polyacrylate portions of the homopolymer or copolymer can then be reduced to form polymeric segments with hydroxyl sidechains. The hydroxyl groups of the resulting polymer can then be reacted (e.g., substituted or protected) to form a derivatized polymer. This process is outlined in Scheme A.
(146) ##STR00042##
(147) Provided herein is a method for preparing a polymer, the method comprising reducing an original polymer; wherein the original polymer comprises polyacrylate repeating units. In certain embodiments, the polyacrylate repeating units are not poly(methyl methacrylate) repeating units. The acrylate repeating units of the original polymer may be fully or partially reduced. In certain embodiments, the acrylate repeating units are approximately 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, or 99% reduced.
(148) In certain embodiments, the polyacrylate repeating units of the original polymer are of the formula:
(149) ##STR00043##
and the polyacrylate repeating units of the original polymer are reduced to form a polymer with repeating units of the formula:
(150) ##STR00044##
wherein:
(151) R.sup.4 is hydrogen, optionally substituted alkyl, optionally substituted carbocyclyl, optionally substituted heterocyclyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted acyl, or an oxygen protecting group.
(152) As generally defined herein, R.sup.4 is hydrogen, optionally substituted alkyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted carbocyclyl, optionally substituted heterocyclyl, optionally substituted acyl, or an oxygen protecting group. In certain embodiments, R.sup.4 is hydrogen. In certain embodiments, R.sup.4 is optionally substituted alkyl. In certain embodiments, R.sup.4 is optionally substituted aryl. In certain embodiments, R.sup.4 is optionally substituted heteroaryl. In certain embodiments, R.sup.4 is optionally substituted carbocyclyl. In certain embodiments, R.sup.4 is optionally substituted heterocyclyl. In certain embodiments, R.sup.4 is optionally substituted acyl. In certain embodiments, R.sup.4 is an oxygen protecting group. In certain embodiments, R.sup.4 is optionally substituted C.sub.1-6 alkyl. In certain embodiments, R.sup.4 is unsubstituted C.sub.1-6 alkyl. In certain embodiments, R.sup.4 is optionally substituted C.sub.1-3 alkyl. In certain embodiments, R.sup.4 is unsubstituted C.sub.1-3 alkyl. In certain embodiments, R.sup.4 is selected from the group consisting of methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, iso-butyl, and tert-butyl. In certain embodiments, R.sup.4 is methyl.
(153) In certain embodiments, the method further comprises a step of reacting the —OH groups of the repeating units to form repeating units of the formula:
(154) ##STR00045##
In certain embodiments, the —OH groups are protected (e.g., alkylated, arylated, heteroarylated) to transform the —OH groups to groups of the formula —OR.sup.O. In certain embodiments, the —OH groups are substituted (e.g., transformed into a leaving group and then treated with a nucleophile) to transform the —OH groups to groups of the formula —R.sup.A. Non-limiting examples of protection and substitution reactions of this kind are outlined in the Figures.
(155) As described above, in certain embodiments, a polymer provided herein is a block copolymer. Therefore, provided herein is a method of preparing a block copolymer, the method comprising reducing an original block copolymer, wherein the original block copolymer is of the formula:
(156) ##STR00046##
to yield a block copolymer of the formula:
(157) ##STR00047##
(158) The acrylate repeating units of the original block copolymer may be fully or partially reduced. In certain embodiments, the acrylate repeating units are approximately 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, or 99% reduced.
(159) In certain embodiments, the original block copolymer is of the formula:
(160) ##STR00048##
(161) In certain embodiments, the original block copolymer is of the formula:
(162) ##STR00049##
(163) In certain embodiments, the method further comprises a step of reacting the —OH groups of the block copolymer to form a block copolymer of the formula:
(164) ##STR00050##
(165) As described above, in certain embodiments, the —OH groups are protected (e.g., alkylated, arylated, heteroarylated) to transform the —OH groups to groups of the formula —OR.sup.O. In certain embodiments, the —OH groups are substituted (e.g., transformed into a leaving group and then treated with a nucleophile) to transform the —OH groups to groups of the formula —R.sup.A. Non-limiting examples of protection and substitution reactions of this kind are outlined in the Figures.
(166) In certain embodiments, the step of reducing (i.e., the step of reducing a group of the formula —CO.sub.2R.sup.4 to a group of the formula —CH.sub.2OH) is carried out in the presence of a reducing agent. In certain embodiments, the reduction is carried out in the presence of one or more of lithium aluminum hydride, hydrogen gas, sodium amalgam, sodium-lead alloy, diborane, sodium borohydride, dithionates, thiosulfates, hydrazine, diisobutylaluminium hydride (DIBAL), oxalic acid, formic acid, ascorbic acid, lithium triethylborohydride, diborane, borane-tetrahydrofuran, borane-dimethyl sulfide, samarium, sodium bis(2-methoxyethoxy)aluminium hydride, sodium triacetoxyborohydride, or zinc.
(167) In certain embodiments, the reduction is carried out in the presence of a hydride donor. In certain embodiments, the hydride donor is diisobutylaluminium hydride (DIBAL) or lithium aluminum hydride (LAH). In certain embodiments, the hydride donor is LAH.
(168) The methods described herein may further comprise one or more polymerization steps in order to prepare an original homopolymer or copolymer. For instance, in certain embodiments, the methods may further comprise steps of polymerizing two or more monomers to produce the original polymer or block copolymer, wherein at least one monomer is an acrylate of the formula:
(169) ##STR00051##
(170) In certain embodiments, the monomer is not poly(methyl methacrylate) (PMMA).
(171) In certain embodiments, the polymerization step is a polymerization selected from the group consisting of living radical polymerization, reversible-deactivation radical polymerization, atom transfer radical polymerization (ATRP), nitroxide mediated radical polymerization (NMP), and reversible addition-fragmentation chain transfer (RAFT) polymerization.
(172) In certain embodiments, the polymerization uses an iniferter, initiator, or chain transfer agent. The term“iniferter” refers to a chemical compound that simultaneously acts as a initiator, transfer agent, and terminator. The term “initiator” refers to a chemical compound that can produce radical species and/or promote radical reactions. The term “chain transfer agent” refers to a a chemical compound that is able to react with a chain carrier by a reaction in which the original chain carrier is deactivated and a new chain carrier is generated. In certain embodiments, the iniferter, initiator, or chain transfer agent is selected from the group consisting of dithiobenzoates, trithiocarbonates, dithiocarbamates, xanthates, and alkyl halides.
(173) Examples of dithiobenzoate include, but are not limited to, benzyl benzodithioate, cyanomethyl benzodithioate, 4-cyano-4-(phenylcarbonothioylthio)pentanoic acid, 4-cyano-4-(phenylcarbonothioylthio)pentanoic acid N-succinimidyl ester, 2-cyano-2-propyl benzodithioate, 2-cyano-2-propyl 4-cyanobenzodithioate, ethyl 2-(4-methoxyphenylcarbonothioylthio)acetate, ethyl 2-methyl-2-(phenylthiocarbonylthio)propionate, ethyl 2-(phenylcarbonothioylthio)-2-phenylacetate, ethyl 2-(phenylcarbonothioylthio)propionate, 1-(methoxycarbonyl)ethyl benzodithioate, 2-(4-methoxyphenylcarbonothioylthio)ethanoic acid, 2-nitro-5-(2-propynyloxy)benzyl 4-cyano-4-(phenylcarbonothioylthio)pentanoate, 2-(phenylcarbonothioylthio)propanoic acid, and 2-phenyl-2-propyl benzodithioate.
(174) Examples of trithiocarbonates include, but are not limited to,3,5-bis(2-dodecylthiocarbonothioylthio-1-oxopropoxy)benzoic acid, 2-cyanobutan-2-yl 4-chloro-3,5-dimethyl-1H-pyrazole-1-carbodithioate, 2-cyanobutanyl-2-yl 3,5-dimethyl-1H-pyrazole-1-carbodithioate, 4-cyano-4-[(dodecylsulfanylthiocarbonyl)sulfanyl]pentanoic acid, 4-cyano-4-[(dodecylsulfanylthiocarbonyl)sulfanyl]pentanol, cyanomethyl (3,5-dimethyl-1H-pyrazole)-carbodithioate, cyanomethyl dodecyl trithiocarbonate, cyanomethyl [3-(trimethoxysilyl)propyl]trithiocarbonate, 2-cyano-2-propyl dodecyl trithiocarbonate, S,S-dibenzyl trithiocarbonate, 2-(dodecylthiocarbonothioylthio)propionic acid, 2-(dodecylthiocarbonothioylthio)-2-methylpropionic acid 3-azido-1-propanol ester, 2-(dodecylthiocarbonothioylthio)-2-methylpropionic acid N-hydroxysuccinimide ester, 2-(dodecylthiocarbonothioylthio)-2-methylpropionic acid pentafluorophenyl ester, phthalimidomethyl butyl trithiocarbonate, methyl 2-(dodecylthiocarbonothioylthio)-2-methylpropionate, 2,2′-(thiocarbonylbis(sulfanediyl))bis(2-methylpropanoic acid), dibenzyl 2,2′-(thiocarbonylbis(sulfanediyl))bis(2-methylpropanoate), dibenzyl 2,2′-(thiocarbonylbis(sulfanediyl))dipropionate, and 2-(((dodecylthio)carbonothioyl)thio)propanoic acid.
(175) Examples of dithiocarbamates include, but are not limited to, benzyl 1H-pyrrole-1-carbodithioate, cyanomethyl diphenylcarbamodithioate, cyanomethyl methyl(phenyl)carbamodithioate, cyanomethyl methyl(4-pyridyl)carbamodithioate, 2-cyanopropan-2-yl N-methyl-N-(pyridin-4-yl)carbamodithioate, methyl 2-[methyl(4-pyridinyl)carbamothioylthio]propionate, and 1-succinimidyl-4-cyano-4-[N-methyl-N-(4-pyridyl)carbamothioylthio]pentanoate. Examples of xanthates include, but are not limited to, ethyl 2-(((ethylthio)carbonothioyl)thio)propanoate, methyl (4-methoxyphenoxy)carbonothioylsulfanyl acetate, methyl (methoxycarbonothioyl)sulfanyl acetate, methyl (ethoxycarbonothioyl)sulfanyl acetate, and methyl (isopropoxycarbonothioyl)sulfanyl acetate.
(176) Examples of alkyl halides include, but are not limited to, ethyl 2-bromo-2-phenylacetate, dodecyl 2-bromoisobutyrate, ethyl 2-bromoisobutyrate, ethyl 2-bromopropionate, 2-hydroxyethyl 2-bromoisobutyrate, octadecyl 2-bromoisobutyrate, 2-(2-bromoisobutyryloxy)ethyl methacrylate, 1-bromoethylbenzene, 2-bromoisobutanoic acid N-hydroxysuccinimide ester, 2-bromoisobutyric anhydride, 2-azidoethyl 2-bromoisobutyrate, bis[2-(2′-bromoisobutyryloxy)ethyl]disulfide, and bis[2-(2-bromoisobutyryloxy)undecyl] disulfide.
(177) In certain embodiments, the polymerization involves transfer radical polymerization (ATRP). In certain embodiments, the ATRP uses a catalyst. In certain embodiments, the catalyst is a metal catalyst. In certain embodiments, the polymerization involves addition-fragmentation chain transfer (RAFT) polymerization.
(178) In addition to the acrylate monomers incorporated into the polymers described herein, one or more other monomers may be incorporated via polymerization to form a copolymer (e.g., a block copolymer described herein). In certain embodiments, one or more other monomers are selected from the group consisting of styrenes, methacrylates, acrylates, acrylamides, vinyl halides, vinyl alcohols, vinyl esters, and vinyl amides. Further examples of polymers that may be incorporated include, but are not limited to, polyvinyl polymers (e.g., polyvinyl chloride), polyethylenes (e.g., polyethylene, polytetrafluoroethylene), polypropylenes, polyacetylenes, polyethers (e.g., polyethylene glycol, polyoxymethylene, polypropylene glycol, polytetramethylene glycol, poly(ethyl ethylene) phosphate, poly(oxazoline)), polyamines, polyesters (e.g., polyglycolic acid, polylactic acid, poly(lactic-co-glycolic acid), polycaprolactone, polyhydroxyalkanoate, polyhydroxybutryate, polyethylene adipate, polybutylene succinate, poly(3-hydroxybutyrate-co-3-hydroxyvalerate), polysilanes, polysiloxanes (e.g., polydimethylsiloxane), polyacrylates (e.g., polymethacrylate, poly(n-butyl acrylate), poly(tert-butyl acrylate)), polystyrenes, polylactides (e.g., polylactic acid), polyamino acids, polypeptides, polyamides, polyacrylamides (e.g., polymethylacrylamide), and polysaccharides.
EXAMPLES
(179) Poly(meth)acrylate BCPs can be derivatized to achieve higher χ parameters. Herein, it is presented in the first place that using LiAH.sub.4, the block copolymers of poly(methyl methyacrylate) (PMMA) or poly(methyl acrylate) (PMA) can be reduced in a controlled manner. The microphase separation between pristine BCP samples and the reduction products is compared to demonstrate the massive increase in χ values. Small d-spacing was achieved. It is envisioned that this work will demonstrate an important strategy for the convenient synthesis of high χ BCPs to approach the downscaling limit. A generic representation of the synthesis of PiBOH and PPOH polymers is shown in Scheme 1.
(180) ##STR00052##
(181) The work started with reducing the BCPs of methyl methacrylate or methyl acrylate in a controlled manner (Scheme 1). The pristine poly(methyl methacrylate)-b-polystyrene (PMMA-b-PS), poly(methyl acrylate)-b-polystyrene (PMA-b-PS), and poly(methyl acrylate)-b-poly(tert-butylstyrene) (PMA-b-PtBS) were synthesized with narrow molecular weight (MW) distribution, with either atom transfer radical polymerization (ATRP) or reversible addition-fragmentation chain transfer radical polymerization (RAFT) technique. It is noted here that, for RAFT synthesized BCPs, the trithiocarbonate end groups were removed before LiAH.sub.4 reduction, using the method reported by: Rizzardo et al. “Thiocarbonylthio End Group Removal from RAFT-Synthesized Polymers by a Radical-Induced Process”, J. Polym. Sci. PartA Polym. Chem. 2009, 47 (23), 6704-6714. This was based on the consideration that the trithiocarbonate end-groups would be reduced into thiol, which could lead to end-linking reactions. Then the BCPs were dissolved in THF and degassed by sparging with N.sub.2, followed by dropwise addition onto LiAlH.sub.4. Upon refluxing overnight, the reaction was quenched via adding excess water. To remove the inorganic side products, the resultant precipitate was boiled at 100° C. with first HCl solution (3˜5 M, 2*30 mL per gram of polymer) and then DI-water (5*30 mL per gram of polymer). After drying, it was found that in the Fourier transformed-infrared spectra (Supporting Information), the peak corresponding to the carbonyl stretching, originally at 1727 cm.sup.−1, disappeared, which confirmed the elimination of ester groups. At the same time, the absence of signals at δ>160 ppm in .sup.13C NMR proved that aldehyde, acid, or amide, were not generated in this reaction. The MW distributions were measured using gel permeation chromatography (GPC) with 0.025M LiBr in DMF as the eluent. The low D values were retained, proving the suppression of backbone degradation. In the GPC traces (
(182) TABLE-US-00001 TABLE 1 Summary of Block Copolymers Investigated. BCP Method.sup.a DP.sub.OH.sup.b DP.sub.S.sup.b Ð.sup.c N.sup.d f.sub.OH.sup.e (%) Phase.sup.f d.sup.g (nm) PiBOH.sub.185-b-PS.sub.168 ATRP 185 168 1.16 (1.29) 401.9 40.7 LAM 41.89 PiBOH.sub.185-b-PS.sub.145 ATRP 185 145 1.35 (1.37) 369.5 44.3 LAM 46.20 PiBOH.sub.185-b-PS.sub.100 ATRP 185 100 1.31 (1.33) 306.0 53.5 LAM 35.70 PiBOH.sub.120-b-PS.sub.122 ATRP 120 122 1.28 (1.24) 279.7 38.0 LAM 42.74 PiBOH.sub.185-b-PS.sub.51 ATRP 185 51 1.31 (1.35) 237.0 71.7 HEX 26.10 PiBOH.sub.84-b-PS.sub.51 ATRP 84 51 1.24 (1.11) 147.9 50.5 LAM 22.52 PiBOH.sub.65-b-PS.sub.49 RAFT-ER 65 49 1.28 (1.29) 128.3 45.0 LAM 21.08 PiBOH.sub.65-b-PS.sub.43 RAFT-ER 65 43 1.22 (1.30) 119.8 48.2 LAM 19.27 PiBOH.sub.65-b-PS.sub.36.5 RAFT-ER 65 36.5 1.24 (1.22) 110.7 52.3 LAM 18.37 PiBOH.sub.65-b-PS.sub.27.5 RAFT-ER 65 27.5 1.22 (1.22) 98.0 59.1 LAM 17.75 PiBOH.sub.30-b-PS.sub.43 RAFT-ER 30 43 1.19 (1.10) 88.9 30.1 HEX 12.57 PiBOH.sub.30-b-PS.sub.28.5 RAFT-ER 30 28.5 1.25 (1.26) 68.5 39.2 LAM 12.32 PiBOH.sub.21-b-PS.sub.23.4 RAFT-ER 21 23.4 1.16 (1.24) 53.4 35.4 HEX 9.24 PiBOH.sub.21-b-PS.sub.14 RAFT-ER 21 14 1.18 (1.15) 40.1 47.3 LAM 7.66 PiBOH.sub.16-b-PS.sub.14 RAFT-ER 16 14 1.31 (1.20) 35.7 40.6 LAM 7.18 PiBOH.sub.16-b-PS.sub.13 RAFT-ER 16 13 1.25 (1.15) 34.3 46.2 DIS N.A. PiBOH.sub.10.8-b-PS.sub.12.6 RAFT-ER 10.8 12.6 1.21 (1.15) 29.1 37.5 DIS N.A. PPOH.sub.11.7-b-PS.sub.21 ATRP 11.7 21 1.08 (1.05) 38.1 22.3 HEX 7.27 (7.29) PPOH.sub.11.7-b-PS.sub.18.4 ATRP 11.7 18.4 1.06 (1.04) 34.4 24.7 HEX 7.51 (7.52) PPOH.sub.11.7-b-PS.sub.14.5 ATRP 11.7 14.5 1.08 (1.06) 28.9 29.4 HEX 7.27 (7.29) PPOH.sub.11.7-b-PtBS.sub.15.2 ATRP 11.7 15.2 1.06 (1.02) 44.6 19.1 BCC (7.11) PPOH.sub.8.6-/b-PtBS.sub.13.8 ATRP 8.6 13.8 1.06 (1.03) 39.2 16.4 ODT (6.68) PPOH.sub.11.7-b-PtBS.sub.11.3 ATRP 11.7 11.3 1.06 (1.02) 35.3 24.1 HEX (6.53) PPOH.sub.9.1-b-PtBS.sub.8 ATRP 9.1 8 1.12 (1.01) 25.8 26.3 DIS N.A. For Table 1 .sup.aThe technique utilized in pre-polymer synthesis before LiAlH.sub.4 reduction, either ATRP or RAFT-ER (RAFT with the end-group removal process). .sup.bDP.sub.OH and DP.sub.S are degrees of polymerization for the polyhydroxy and polystyrenic blocks, respectively, which are calculated by end-group analysis using .sup.1H NMR spectra. .sup.cMeasured by GPC. The values in the parentheses are on the pre-polymer before LiAlH.sub.4 reduction (for RAFT-ER synthesized BCPs, the values were obtained after the removal of trithiocarbonate groups). .sup.dCalculated using a reference volume of 118 Å.sup.3, based on the density of PiBOH, PS, and PtBS being 1.15, 1.04, and 0.95 g/cm.sup.3, respectively, while the density of PPOH being estimated to be 1.22 g/cm.sup.3. .sup.eVolume fraction of polyhydroxy block domains. .sup.fMorphologies observed upon thermal annealing. HEX denotes hexagonally packed cylinders, LAM denotes lamellae, BCC is for spheres with body centered cubic packing, DIS stands for disordered phase, while ODT means the sample was in order-disorder transition state. .sup.gThe d-spacing achieved by thermal annealing at 134 ± 1° C., and the values in the parentheses are at 179 ± 1° C..
(183) For Table 1: .sup.aThe technique utilized in pre-polymer synthesis before LiAlH.sub.4 reduction, either ATRP or RAFT-ER (RAFT with the end-group removal process). .sup.bDP.sub.OH and DP.sub.s are degrees of polymerization for the polyhydroxy and polystyrenic blocks, respectively, which are calculated by end-group analysis using .sup.1H NMR spectra. .sup.cMeasured by GPC. The values in the parentheses are on the pre-polymer before LiAlH.sub.4 reduction (for RAFT-ER synthesized BCPs, the values were obtained after the removal of trithiocarbonate groups). .sup.dCalculated using a reference volume of 118 Å.sup.3, based on the density of PiBOH, PS, and PtBS being 1.15, 1.04, and 0.95 g/cm.sup.3, respectively, while the density of PPOH being estimated to be 1.22 g/cm.sup.3. .sup.eVolume fraction of polyhydroxy block domains. .sup.fMorphologies observed upon thermal annealing. HEX denotes hexagonally packed cylinders, LAM denotes lamellae, BCC is for spheres with body centered cubic packing, DIS stands for disordered phase, while ODT means the sample was in order-disorder transition state. .sup.gThe d-spacing achieved by thermal annealing at 134±1° C., and the values in the parentheses are at 179±1° C.
(184) To investigate the bulk morphologies, the BCPs were applied to thermal annealing at designated temperatures for at least 12 hours and then quenched to room temperature to achieve equilibrated morphologies. By investigating the small angle X-ray scattering (SAXS) pattern achieved using synchrotron beam, the morphologies of the BCPs before and after reduction were compared. In
(185) A series of PiBOH-b-PS samples were investigated on their morphologies. Most of these BCPs, as shown in Table 1, have volume fractions close to 50%, and they displayed lamellar morphologies as confirmed by SAXS. For example, PiBOH.sub.84-b-PS.sub.51 is shown in
(186) Then, the morphologies of BCPs with various N values were investigated. The shortest PiBOH-b-PS sample that showed a sharp peak (
(187) In contrast, the polymer with N=34.3 (PiBOH.sub.16-b-PS.sub.13) showed only a broad peak in the SAXS pattern. This suggests that the χ.sub.effN value crossed the critical point of being 10.5, when N changes from 35.7 to 34.3. So, one can estimate the effective χ parameter (χ.sub.eff) to be 0.3 at 134° C. This gives PiBOH.sub.16-b-PS.sub.14 a χ.sub.effN value of 10.7, which is in good consistency with the previously observed order-disorder transition (ODT). Comparing with PMMA-b-PS at similar conditions (χ.sub.eff=0.03, with a reference volume of 118 Å.sup.3 at 150° C.), it is demonstrated here that the χ.sub.eff value can be increased by one order of magnitude using a basic organic reaction that is approachable in any chemistry labs. See, e.g., Koo et al. “Directed Self-Assembly of Block Copolymers in the Extreme: Guiding Microdomains from the Small to the Large”, Soft Matter 2013, 9 (38), 9059; Russell et al. “Temperature Dependence of the Interaction Parameter of Polystyrene and Poly (Methyl Methacrylate)”, Macromolecules 1990, 23, 890-893. To further elucidate the significance, here compare with the high χ.sub.eff values reported in literature that were determined using ODT. For example, poly(cyclohexylethylene)-b-poly(ethylene oxide) possesses a χ.sub.eff being 0.22 at 150° C. and a reference volume of 118 Å.sup.3, while under similar conditions, polystyrene-b-polydimethylsiloxane, poly(cyclohexylethylene)-b-poly(methyl methacrylate), poly(tert-butyl styrene)-b-poly(2-vinylpyridine), and poly(methyl methacrylate)-b-polydimethylsiloxane were found to have χ.sub.eff values being 0.11, 0.053, 0.11, and 0.24, respectively. See, e.g., Kennemur et al. “Sub-5 Nm Domains in Ordered Poly(cyclohexylethylene)-Block-Poly(methyl Methacrylate) Block Polymers for Lithography,” Macromolecules 2014, 47 (4), 1411-1418; Andersen et al. “Surface Morphology of PS-PDMS Diblock Copolymer Films”, J. Electron Spectros. Relat. Phenomena 2001, 121 (1-3), 93-110. Various χ values were reported on poly(4-vinylpyridine)/polystyrene pair depending on the testing methodology, while ODT has not been used. However, from the work by Chang Dae Han et al., it is estimated that the χ.sub.eff (ODT) value should be lower than 0.34, when the temperature and reference volume being 160° C. and 118 Å.sup.3. See, e.g., Zha et al. “Origin of the Difference in Order-Disorder Transition Temperature between Polystyrene-Block-poly(2-Vinylpyridine) and Polystyrene-Block-poly(4-Vinylpyridine) Copolymers”, Macromolecules 2007, 40 (6), 2109-2119. On poly(3,4-dihydroxystyrene)-b-polystyrene, the χ value was computed to be ˜0.7 by fitting the SAXS profiles with Leibler theory, while the χ.sub.eff value is reduced to be between 0.37 and 0.50 when merely using the molecular weights below and above ODT (the temperature and reference volume being 170° C. and 118 Å.sup.3, respectively). Similarly, poly(trimethylsilylstyrene)-b-poly(D,L-lactide) was investigated to reveal its χ.sub.eff value being 0.42 at 140° C. using the absolute scattering intensity. See, e.g., Cushen et al. “Thin Film Self-Assembly of Poly(trimethylsilylstyrene-B-D,L-Lactide) with Sub-10 Nm Domains”, Macromolecules 2012, 45 (21), 8722-8728. However, it was re-estimated the χ.sub.eff (ODT) to be no larger than 0.35. So far, it has been demonstrated that the χ.sub.eff value obtained on PiBOH-b-PS is amongst the highest.
(188) To better understand how d is affected by N, the d values of lamellar samples are plotted against N in
(189) To access even smaller spacing values, the PPOH-b-PS samples were examined. Annealed at 134° C., PPOH.sub.11.7-b-PS.sub.21 and PPOH.sub.11.7-b-PS.sub.18.4 exhibited peaks at position ratios of 1:√3: √5 indicating hexagonal morphologies, and d-spacing values being 7.51 and 7.38 nm, respectively. With an N value of 28.9, PPOH.sub.11.7-b-PS.sub.14.5 also had a hexagonal morphology (d=7.27 nm), since a set of sharp peaks with a position ratio of 1:√3:√4:√5 were observed in the SAXS pattern (
(190) Similarly, the PPOH-b-PtBS samples were thermally annealed at 179° C. (due to the Tg of PtBS). Interestingly, PPOH.sub.11.7-b-PtBS.sub.15.2, having N=44.6 and f.sub.OH=19.1%, displayed a set of peaks with a position ratio of 1:√2:√3:√4:√5 (
(191) In conclusion, this work demonstrated that LiAlH.sub.4 can be used to reduce block copolymer of PMMA or PMA in a controlled manner. The change in chemical structure endows the new BCPs much enhanced χ.sub.eff interaction parameters, which allows them to form well-ordered morphologies with a very short chain length, i.e. N=28.5 in this work. The smallest spacing achieved in this work is 7.18 nm for lamellae, 6.53 nm for hexagonally packed cylinders, and 7.11 nm for body centered cubic morphologies.
EQUIVALENTS AND SCOPE
(192) In the claims articles such as “a,” “an,” and “the” may mean one or more than one unless indicated to the contrary or otherwise evident from the context. Claims or descriptions that include “or” between one or more members of a group are considered satisfied if one, more than one, or all of the group members are present in, employed in, or otherwise relevant to a given product or process unless indicated to the contrary or otherwise evident from the context. The invention includes embodiments in which exactly one member of the group is present in, employed in, or otherwise relevant to a given product or process. The invention includes embodiments in which more than one, or all of the group members are present in, employed in, or otherwise relevant to a given product or process.
(193) Furthermore, the invention encompasses all variations, combinations, and permutations in which one or more limitations, elements, clauses, and descriptive terms from one or more of the listed claims is introduced into another claim. For example, any claim that is dependent on another claim can be modified to include one or more limitations found in any other claim that is dependent on the same base claim. Where elements are presented as lists, e.g., in Markush group format, each subgroup of the elements is also disclosed, and any element(s) can be removed from the group. It should it be understood that, in general, where the invention, or aspects of the invention, is/are referred to as comprising particular elements and/or features, certain embodiments of the invention or aspects of the invention consist, or consist essentially of, such elements and/or features. For purposes of simplicity, those embodiments have not been specifically set forth in haec verba herein.
(194) It is also noted that the terms “comprising” and “containing” are intended to be open and permits the inclusion of additional elements or steps. Where ranges are given, endpoints are included. Furthermore, unless otherwise indicated or otherwise evident from the context and understanding of one of ordinary skill in the art, values that are expressed as ranges can assume any specific value or sub-range within the stated ranges in different embodiments of the invention, to the tenth of the unit of the lower limit of the range, unless the context clearly dictates otherwise.
(195) This application refers to various issued patents, published patent applications, journal articles, and other publications, all of which are incorporated herein by reference. If there is a conflict between any of the incorporated references and the instant specification, the specification shall control. In addition, any particular embodiment of the present invention that falls within the prior art may be explicitly excluded from any one or more of the claims. Because such embodiments are deemed to be known to one of ordinary skill in the art, they may be excluded even if the exclusion is not set forth explicitly herein. Any particular embodiment of the invention can be excluded from any claim, for any reason, whether or not related to the existence of prior art.
(196) Those skilled in the art will recognize or be able to ascertain using no more than routine experimentation many equivalents to the specific embodiments described herein. The scope of the present embodiments described herein is not intended to be limited to the above Description, but rather is as set forth in the appended claims. Those of ordinary skill in the art will appreciate that various changes and modifications to this description may be made without departing from the spirit or scope of the present invention, as defined in the following claims.