PHENOL-BASED HOT MELT ADHESIVES FOR REWORK, REPAIR AND RECYCLE

Abstract

The present disclosure provides polymers prepared by a method comprising reacting a polymerization mixture comprising one or more types of diols, one or more types of polyols, and one or more types of isocyanates, wherein at least one type of the diols and/or at least one type of the polyols are phenols, wherein each of the phenols is independently a diol or polyol, wherein one or more instances of OH, NH.sub.2, and/or NH are aryl-bound. At least one instance of COH of at least one instance of the diols or polyols may react with NCO of the isocyanates to form COC(O)NH bonds. The polymers may be a thermoset under ambient conditions. At elevated temperatures, the polymers may undergo a transition from a cross-linked state to a lightly cross-linked or un-crosslinked state (e.g., at least in part because at least one instance of the COC(O)NH bonds may be cleaved (e.g., to form COH and NCO)). The transition may be reversable (e.g., by changing the temperature). The polymers of the present disclosure may be useful as hot melt adhesives. The present disclosure also provides compositions, kits, methods of preparation, methods of bonding, and methods of de-bonding.

Claims

1. A polymer prepared by a method comprising reacting a polymerization mixture comprising one or more types of diols, one or more types of polyols, and one or more types of isocyanates at a first temperature for a first time duration sufficient to forming the polymer, wherein: each type of the diols is independently a compound comprising zero or more instances of COH, zero or more instances of NH.sub.2, zero or more instances of NH, and zero instances of each of NOH and NCO, wherein the combined number of COH, NH.sub.2, and NH of each of the diols is two; each type of the polyols is independently a compound comprising zero or more instances of COH, zero or more instances of NH.sub.2, zero or more instances of NH, and zero instances of each of NOH and NCO, wherein the combined number of COH, NH.sub.2, and NH of each of the polyols is at least three; at least one type of the diols and/or at least one type of the polyols are phenols, wherein each of the phenols is independently a diol or polyol, wherein one or more instances of OH, NH.sub.2, and/or NH are aryl-bound; and each type of the isocyanates is independently a compound comprising two or more instances of NCO and zero instances of each of OH, NH.sub.2, and NH.

2. A method of preparing a polymer comprising reacting a polymerization mixture comprising one or more types of diols, one or more types of polyols, and one or more types of isocyanates at a first temperature for a first time duration sufficient to forming the polymer, wherein: each type of the diols is independently a compound comprising zero or more instances of COH, zero or more instances of NH.sub.2, zero or more instances of NH, and zero instances of each of NOH and NCO, wherein the combined number of COH, NH.sub.2, and NH of each of the diols is two; each type of the polyols is independently a compound comprising zero or more instances of COH, zero or more instances of NH.sub.2, zero or more instances of NH, and zero instances of each of NOH and NCO, wherein the combined number of COH, NH.sub.2, and NH of each of the polyols is at least three; at least one type of the diols and/or at least one type of the polyols are phenols, wherein each of the phenols is independently a diol or polyol, wherein one or more instances of OH, NH.sub.2, and/or NH are aryl-bound; and each type of the isocyanates is independently a compound comprising two or more instances of NCO and zero instances of each of OH, NH.sub.2, and NH.

3-4. (canceled)

5. The polymer of claim 1, wherein at least one type of the phenols is of the formula: ##STR00033## or a tautomer, isotopically labeled compound, salt, solvate, polymorph, or co-crystal thereof, wherein: each instance of G.sup.2 is independently OH, NH.sub.2, or NHR.sup.3; each instance of R.sup.3 is independently substituted or unsubstituted alkyl, substituted or unsubstituted aryl, or a nitrogen protecting group; each instance of Ring A is aryl; each instance of R.sup.5 is independently halogen, substituted or unsubstituted alkyl, O-(substituted or unsubstituted alkyl), O-(substituted or unsubstituted aryl), or O-(oxygen protecting group); each instance of k is independently 0, 1, 2, 3, or 4, as valency permits; each instance of L.sup.1 is independently a single bond, substituted or unsubstituted alkylene, substituted or unsubstituted alkenylene, substituted or unsubstituted alkynylene, substituted or unsubstituted heteroalkylene, substituted or unsubstituted heteroalkenylene, or substituted or unsubstituted heteroalkynylene; each instance of Ring D is independently aryl, heteroaryl, carbocyclyl, or heterocyclyl; each instance of R.sup.9 is independently halogen, substituted or unsubstituted alkyl, O-(substituted or unsubstituted alkyl), O-(substituted or unsubstituted aryl), or O-(oxygen protecting group); each instance of v is independently 0, 1, 2, 3, or 4, as valency permits; each instance of x is independently 0 or 1; each instance of G.sup.4 is independently OH, NH.sub.2, or NHR.sup.4; each instance of R.sup.4 is independently substituted or unsubstituted alkyl, substituted or unsubstituted aryl, or a nitrogen protecting group; and each instance of m is independently 1, 2, 3, 4, or 5, as valency permits.

6-26. (canceled)

27. The polymer of claim 1, wherein at least one type of the phenols is of the formula: ##STR00034## ##STR00035## or a tautomer, isotopically labeled compound, salt, solvate, polymorph, or co-crystal thereof.

28-32. (canceled)

33. The polymer of claim 1, wherein at least one type of the diols is of the formula: ##STR00036## or an isotopically labeled compound thereof, wherein p is an integer between 10 and 30.

34-39. (canceled)

40. The polymer of claim 1, wherein at least one type of the polyols is of the formula: ##STR00037## or a tautomer, isotopically labeled compound, salt, solvate, polymorph, or co-crystal thereof.

41-43. (canceled)

44. The polymer of claim 1, wherein at least one type of the isocyanates is of the formula: ##STR00038## or a tautomer, isotopically labeled compound, salt, solvate, polymorph, or co-crystal thereof, wherein: each instance of u is independently 0 or 1; each instance of Ring B is independently aryl, heteroaryl, carbocyclyl, or heterocyclyl; each instance of R.sup.6 is independently halogen, substituted or unsubstituted alkyl, O-(substituted or unsubstituted alkyl), O-(substituted or unsubstituted aryl), or O-(oxygen protecting group); each instance of q is independently 0, 1, 2, 3, or 4, as valency permits; each instance of L.sup.3 is independently a single bond, substituted or unsubstituted alkylene, substituted or unsubstituted alkenylene, substituted or unsubstituted alkynylene, substituted or unsubstituted heteroalkylene, substituted or unsubstituted heteroalkenylene, or substituted or unsubstituted heteroalkynylene, wherein zero or more backbone carbon atoms of the alkylene, alkenylene, alkynylene, heteroalkylene, heteroalkenylene, or heteroalkynylene are independently replaced with substituted or unsubstituted arylene, substituted or unsubstituted heteroarylene, substituted or unsubstituted carbocyclylene, or substituted or unsubstituted heterocyclylene, or a combination thereof, as valency permits; or a single bond when at least one of u and t is 1; each instance of t is independently 0 or 1; each instance of Ring C is independently aryl, heteroaryl, carbocyclyl, or heterocyclyl; each instance of R.sup.7 is independently halogen, substituted or unsubstituted alkyl, O-(substituted or unsubstituted alkyl), O-(substituted or unsubstituted aryl), or O-(oxygen protecting group); and each instance of r is independently 0, 1, 2, 3, or 4, as valency permits.

45-52. (canceled)

53. The polymer of claim 1, wherein at least one type of the isocyanates is of the formula: ##STR00039## or a tautomer, isotopically labeled compound, solvate, polymorph, or co-crystal thereof.

54. The polymer of claim 1, wherein at least one type of the isocyanates is of the formula: ##STR00040## or a tautomer, isotopically labeled compound, solvate, polymorph, or co-crystal thereof.

55. The polymer of claim 1, wherein at least one type of the isocyanates is of the formula: ##STR00041## or a tautomer, isotopically labeled compound, salt, solvate, polymorph, or co-crystal thereof, wherein: each instance of L.sup.4 is independently substituted or unsubstituted alkylene, substituted or unsubstituted alkenylene, substituted or unsubstituted alkynylene, substituted or unsubstituted heteroalkylene, substituted or unsubstituted heteroalkenylene, or substituted or unsubstituted heteroalkynylene, wherein zero or more backbone carbon atoms of the alkylene, alkenylene, alkynylene, heteroalkylene, heteroalkenylene, or heteroalkynylene are independently replaced with substituted or unsubstituted arylene, substituted or unsubstituted heteroarylene, substituted or unsubstituted carbocyclylene, or substituted or unsubstituted heterocyclylene, or a combination thereof, as valency permits; and each instance of R.sup.8 is independently hydrogen or NCO.

56-57. (canceled)

58. The polymer of claim 1, wherein at least one type of the isocyanates is of the formula: ##STR00042## or a tautomer, isotopically labeled compound, solvate, polymorph, or co-crystal thereof.

59. The polymer of claim 1, wherein at least one type of the isocyanates is of the formula: ##STR00043## or a tautomer, isotopically labeled compound, solvate, polymorph, or co-crystal thereof.

60-92. (canceled)

93. The polymer of claim 1, wherein the diols, polyols, and isocyanates are: TABLE-US-00003 Polymer number Diol Polyol Isocyanate 1-5 (11) (101) 1-11 (11) and Glycerol (100), (201) or a tautomer, isotopically labeled compound, salt, solvate, polymorph, or co-crystal thereof.

94-97. (canceled)

98. A composition comprising the polymer of claim 1.

99. (canceled)

100. A kit comprising: the polymer of claim 1; and instructions for using the polymer or composition.

101-106. (canceled)

107. A method of bonding comprising: applying the polymer of any one of claim 1 to a surface of a first solid substrate; contacting the polymer or composition on the surface of the first solid substrate with a surface of a second solid substrate; and curing the polymer or composition on the surface of the first solid substrate to form bonded first and second substrates; or applying the polymer or composition to a surface of a first solid substrate and a surface of a second solid substrate; contacting the polymer or composition on the surface of the first solid substrate with the polymer or composition on the surface of the second solid substrate; and curing the polymer or composition on the surface of the first solid substrate and the polymer or composition on the surface of the second solid substrate to form bonded first and second substrates; wherein the first solid substrate is the same or different from the second solid substrate.

108-114. (canceled)

115. A method of debonding comprising maintaining the bonded first and second substrates recited in claim 107 at a fifth temperature for a fifth time duration sufficient to form debonded first and solid substrates, wherein: the fifth temperature is between 40 and 60, between 60 and 80, between 80 and 100, between 100 and 120, between 120 and 140, between 140 and 160, between 160 and 180, or between 180 and 200 C., e.g., between 50 and 150 C.; and the fifth time duration is between 10 and 60 seconds, between 1 and 10 minutes, between 10 and 60 minutes, between 1 and 8 hours, or between 8 and 24 hours, e.g., between 10 seconds and 2 minutes.

116-119. (canceled)

Description

DETAILED DESCRIPTION OF CERTAIN EMBODIMENTS OF THE DISCLOSURE

[0121] In one aspect, the present disclosure provides a polymer prepared by a method comprising reacting a polymerization mixture comprising one or more types of diols, one or more types of polyols, and one or more types of isocyanates at a first temperature for a first time duration sufficient to forming the polymer, wherein: [0122] each type of the diols is independently a compound comprising zero or more instances of COH, zero or more instances of NH.sub.2, zero or more instances of NH, and zero instances of each of NOH and NCO, wherein the combined number of COH, NH.sub.2, and NH of each of the diols is two; [0123] each type of the polyols is independently a compound comprising zero or more instances of COH, zero or more instances of NH.sub.2, zero or more instances of NH, and zero instances of each of NOH and NCO, wherein the combined number of COH, NH.sub.2, and NH of each of the polyols is at least three; [0124] at least one type of the diols and/or at least one type of the polyols are phenols, wherein each of the phenols is independently a diol or polyol, wherein one or more instances of OH, NH.sub.2, and/or NH are aryl-bound; and [0125] each type of the isocyanates is independently a compound comprising two or more instances of NCO and zero instances of each of OH, NH.sub.2, and NH.

[0126] In another aspect, the present disclosure provides a method of preparing a polymer comprising reacting a polymerization mixture comprising one or more types of diols, one or more types of polyols, and one or more types of isocyanates at a first temperature for a first time duration sufficient to forming the polymer, wherein: [0127] each type of the diols is independently a compound comprising zero or more instances of COH, zero or more instances of NH.sub.2, zero or more instances of NH, and zero instances of each of NOH and NCO, wherein the combined number of COH, NH.sub.2, and NH of each of the diols is two; [0128] each type of the polyols is independently a compound comprising zero or more instances of COH, zero or more instances of NH.sub.2, zero or more instances of NH, and zero instances of each of NOH and NCO, wherein the combined number of COH, NH.sub.2, and NH of each of the polyols is at least three; [0129] at least one type of the diols and/or at least one type of the polyols are phenols, wherein each of the phenols is independently a diol or polyol, wherein one or more instances of OH, NH.sub.2, and/or NH are aryl-bound; and [0130] each type of the isocyanates is independently a compound comprising two or more instances of NCO and zero instances of each of OH, NH.sub.2, and NH.

[0131] In certain embodiments, the first temperature is between 20 and 40, between 40 and 60, between 60 and 80, between 80 and 100, or between 10 and 120 C., e.g., between 4 and 60 C. In certain embodiments, the first temperature is substantially constant over the first time duration. In certain embodiments, the first temperature is a variable temperature (e.g., 5, 10, 15, or 20 C.) over the first time duration.

[0132] In certain embodiments, the first time duration is between 1 minute and 1 hour, between 1 and 8 hours, between 8 and 24 hours, between 1 and 3 days, or between 3 and 7 days, e.g. between 8 and 24 hours. In certain embodiments, the first time duration is between 8 hours and 3 days.

[0133] In certain embodiments, at least one (e.g., each) type of the diols is independently a compound comprising two instances of COH and zero instances of each of NH.sub.2, NH, NOH, and NCO. In certain embodiments, at least one (e.g., each) type of the diols is independently a compound comprising one instance of COH, one instance of NH.sub.2 or NH, and zero instances of each of NOH and NCO. In certain embodiments, at least one (e.g. each) type of the diols is independently a compound comprising zero instances of COH, zero or more instances of NH.sub.2, zero or more instances of NH, and zero instances of each of NOH and NCO, wherein the combined number of NH.sub.2 and NH of the at least one (e.g., each) type of the diols is two. In certain embodiments, at least one (e.g., each) type of the diols is alkane or polyethylene (e.g., polyethylene having a number average molecular weight of between 300 and 3,000 g/mol), each of which is substituted with two instances of OH and optionally one or more substituents independently selected from the group consisting of halogen, unsubstituted alkyl, and O-(unsubstituted alkyl), as valency permits. In certain embodiments, at least one (e.g. each) type of the diols is alkane substituted with two instances of OH and optionally one or more substituents that do not comprise OH. In certain embodiments, at least one (e.g., each) type of the diols is polyethylene substituted with two instances of OH and optionally one or more substituents that do not comprise OH. In certain embodiments, at least one (e.g., each) type of the diols does not comprise two or more instances of OH attached to the same atom (e.g., carbon atom). In certain embodiments, at least one (e.g., each) type of the diols is alkane substituted with one instance of OH, one instance of NH.sub.2 or NH, and optionally one or more substituents that do not comprise OH, NH.sub.2, and/or NH. In certain embodiments, at least one (e.g., each) type of the diols is polyethylene substituted with one instance of OH, one instance of NH.sub.2 or NH, and optionally one or more substituents that do not comprise OH, NH.sub.2, and/or NH.

[0134] In certain embodiments, at least one (e.g., each) instance of NH.sub.2 is part of CNH.sub.2. In certain embodiments, at least one (e.g., each) instance of NH is part of CNHC. In certain embodiments, at least one (e.g., each) instance of NH is non-aromatic NH. In certain embodiments, at least one (e.g., each) instance of NH is aromatic NH.

[0135] In certain embodiments, the polyethylene has a number average molecular weight of between 300 and 600, between 600 and 1,000, between 1,000 and 2,000, or between 2,000 and 3,000, g/mol.

[0136] In certain embodiments, the number average molecular weight is as determined by gel permeation chromatography.

[0137] In certain embodiments, at least one (e.g., each) type of the diols is heteroalkane or polyether (e.g., polyether having a number average molecular weight of between 300 and 3,000 g/mol), each of which is substituted with two instances of OH and optionally one or more substituents independently selected from the group consisting of halogen, unsubstituted alkyl, and O-(unsubstituted alkyl), as valency permits. In certain embodiments, at least one (e.g. each) type of the diols is heteroalkane substituted with two instances of OH and optionally one or more substituents that do not comprise OH. In certain embodiments, each heteroatom of at least one (e.g., each) instance of the heteroalkene is O. In certain embodiments, at least one (e.g., each) type of the diols is polyether substituted with two instances of OH and optionally one or more substituents that do not comprise OH. In certain embodiments, at least one (e.g., each) type of the diols is heteroalkane substituted with one instance of OH, one instance of NH.sub.2 or NH, and optionally one or more substituents that do not comprise OH, NH.sub.2, and/or NH. In certain embodiments, at least one (e.g., each) type of the diols is polyether substituted with one instance of OH, one instance of NH.sub.2 or NH, and optionally one or more substituents that do not comprise OH, NH.sub.2, and/or NH. In certain embodiments, the polyether has a number average molecular weight of between 300 and 600, between 600 and 1,000, between 1,000 and 2,000, or between 2,000 and 3,000, g/mol.

[0138] In certain embodiments, at least one (e.g., each) type of the diols is of the formula:

##STR00008##

or an isotopically labeled compound thereof, wherein each instance of p1 is independently 1, 2, 3, 4, or 5; and each instance of p is independently an integer between 3 and 300. In certain embodiments, at least one (e.g., each) instance of p1 is 1. In certain embodiments, at least one (e.g., each) instance of p1 is 3. In certain embodiments, at least one (e.g., each) instance of p is independently an integer between 3 and 10, between 10 and 30, between 30 and 100, or between 100 and 300. In certain embodiments, at least one (e.g., each) instance of p is independently an integer between 10 and 20. In certain embodiments, at least one (e.g., each) type of the diols is of the formula:

##STR00009##

or an isotopically labeled compound thereof, wherein each instance of p is independently an integer between 10 and 30.

[0139] In certain embodiments, at least one (e.g., each) type of the diols comprises one or two instances of CNHC. In certain embodiments, at least one (e.g., each) type of the diols comprises one instance of COH and one instance of CNHC.

[0140] In certain embodiments, the number of types of the diols that are not the phenols is zero. In certain embodiments, the number of types of the diols that are not the phenols is one. In certain embodiments, the number of types of the diols that are not the phenols is two.

[0141] In certain embodiments, the molecular weight of at least one (e.g., each) type of the diols is between 30 and 100, between 100 and 300, between 300 and 1,000, or between 1,000 and 3,000, g/mol.

[0142] In certain embodiments, the number of types of the diols is one. In certain embodiments, the number of types of the diols is two.

[0143] In certain embodiments, each type of the diols is substantially free of water.

[0144] In certain embodiments, each substantially free of water is independently between 90% and 95%, between 95% and 97%, between 97% and 99%, between 99% and 99.5%, or between 99.5% and 99.9%, free of water.

[0145] In certain embodiments, at least one (e.g., each) type of the polyols is a triol, wherein each of the triols is independently a compound comprising zero or more instances of COH, zero or more instances of NH.sub.2, zero or more instances of NH, and zero instances of each of NOH and NCO, wherein the combined number of COH, NH.sub.2, and NH of each of the triols is three.

[0146] In certain embodiments, at least one (e.g., each) type of triols is independently a compound comprising three instances of COH and zero instances of each of NH.sub.2, NH, NOH, and NCO. In certain embodiments, at least one (e.g., each) type of the triols is independently a compound comprising two instances of COH, one instance of NH.sub.2 or NH, and zero instances of each of NOH and NCO. In certain embodiments, at least one (e.g., each) type of the triols is independently a compound comprising one instance of COH, zero or more instances of NH.sub.2, zero or more instances of NH, and zero instances of each of NOH and NCO, wherein the combined number of NH.sub.2 and NH of the at least one (e.g., each) type of the triols is two. In certain embodiments, at least one (e.g., each) type of the triols is independently a compound comprising zero instances of COH, zero or more instances of NH.sub.2, zero or more instances of NH, and zero instances of each of NOH and NCO, wherein the combined number of NH.sub.2 and NH of the at least one (e.g., each) type of the triols is three. In certain embodiments, at least one (e.g., each) type of the triols is alkane substituted with three instances of OH and optionally one or more substituents independently selected from the group consisting of halogen, unsubstituted alkyl, and O-(unsubstituted alkyl), as valency permits. In certain embodiments, at least one (e.g., each) type of the triols is alkane substituted with three instances of OH.

[0147] In certain embodiments, at least one (e.g., each) type of the polyols is glycerol, or an isotopically labeled compound thereof.

[0148] In certain embodiments, at least one (e.g., each) type of the polyols is a tetraol, wherein each of the tetraols is independently a compound comprising zero or more instances of COH, zero or more instances of NH.sub.2, zero or more instances of NH, and zero instances of each of NOH and NCO, wherein the combined number of COH, NH.sub.2, and NH of each of the tetraols is four. In certain embodiments, at least one (e.g., each) type of the tetraols is independently a compound comprising four instances of COH and zero instances of each of NH.sub.2, NH, NOH, and NCO.

[0149] In certain embodiments, the molecular weight of at least one (e.g., each) type of the polyols is between 60 and 100, between 100 and 200, between 200 and 300, between 300 and 400, or between 400 and 600, g/mol.

[0150] In certain embodiments, the number of types of the polyols is one. In certain embodiments, the number of types of the polyols is two.

[0151] In certain embodiments, the number of types of the triols is one. In certain embodiments, the number of types of the triols is two.

[0152] In certain embodiments, the equivalent ratio of the combination of all types of the diols to the combination of all types of polyols is between 1:0.01 and 1:0.7, e.g., between 1:0.1 and 1:0.5.

[0153] In certain embodiments, the equivalent ratio of the combination of all types of the diols to the combination of all types of polyols is between 1:0.01 and 1:0.03, between 1:0.03 and 1:0.1, between 1:0.1 and 1:0.3, between 1:0.3 and 1:0.5, between 1:0.5 and 1:0.6, or between 1:0.6 and 1:0.7.

[0154] In certain embodiments, each type of the polyols is substantially free of water.

[0155] In certain embodiments, at least one (e.g., each) type of the diols and/or at least one (e.g., each) type of the polyols is a phenol, wherein each of the phenols is independently a diol or polyol, wherein one or more instances of OH, NH.sub.2, and/or NH are aryl-bound. In certain embodiments, at least one (e.g., each) type of the phenols is a diol, wherein two instances of OH are aryl-bound. In certain embodiments, at least one (e.g., each) type of the phenols is a diol, wherein one instance of OH is aryl-bound. In certain embodiments, at least one (e.g., each) type of the phenols is a diol, wherein zero or more instances of NH.sub.2 are aryl-bound, and zero or more instances of NH are aryl-bound, wherein the combined number of aryl-bound NH.sub.2 and aryl-bound NH is one. In certain embodiments, at least one (e.g., each) type of the phenols is a diol, wherein zero or more instances of NH.sub.2 are aryl-bound, and zero or more instances of NH are aryl-bound, wherein the combined number of aryl-bound NH.sub.2 and aryl-bound NH is two. In certain embodiments, at least one (e.g., each) type of the phenols is a triol, wherein each of the triols is independently a compound comprising zero or more instances of COH, zero or more instances of NH.sub.2, zero or more instances of NH, and zero instances of each of NOH and NCO, wherein the combined number of COH, NH.sub.2, and NH of each of the triols is three. In certain embodiments, at least one (e.g., each) type of the phenols is a triol, wherein three instances of OH are aryl-bound. In certain embodiments, at least one (e.g., each) type of the phenols is a triol, wherein two instances of OH are aryl-bound. In certain embodiments, at least one (e.g., each) type of the phenols is a triol, wherein one instance of OH is aryl-bound. In certain embodiments, at least one (e.g., each) type of the phenols is a triol, wherein zero or more instances of NH.sub.2 are aryl-bound, and zero or more instances of NH are aryl-bound, wherein the combined number of aryl-bound NH.sub.2 and aryl-bound NH is one. In certain embodiments, at least one (e.g., each) type of the phenols is a triol, wherein zero or more instances of NH.sub.2 are aryl-bound, and zero or more instances of NH are aryl-bound, wherein the combined number of aryl-bound NH.sub.2 and aryl-bound NH is two. In certain embodiments, at least one (e.g. each) type of the phenols is a triol, wherein zero or more instances of NH.sub.2 are aryl-bound, and zero or more instances of NH are aryl-bound, wherein the combined number of aryl-bound NH.sub.2 and aryl-bound NH is three.

[0156] In certain embodiments, the aryl of at least one (e.g., each) type of the phenols is phenyl optionally substituted with one or more substituents that do not comprise OH, NH.sub.2, and/or NH.

[0157] In certain embodiments, at least one (e.g., each) type of the phenols is of the formula:

##STR00010##

or a tautomer, isotopically labeled compound, salt, solvate, polymorph, or co-crystal thereof, wherein: [0158] each instance of G.sup.2 is independently OH, NH.sub.2, or NHR.sup.3; [0159] each instance of R.sup.3 is independently substituted or unsubstituted alkyl, substituted or unsubstituted aryl, or a nitrogen protecting group; [0160] each instance of Ring A is aryl; [0161] each instance of R.sup.5 is independently halogen, substituted or unsubstituted alkyl, O-(substituted or unsubstituted alkyl), O-(substituted or unsubstituted aryl), or O-(oxygen protecting group); [0162] each instance of k is independently 0, 1, 2, 3, or 4, as valency permits; [0163] each instance of L.sup.1 is independently a single bond, substituted or unsubstituted alkylene, substituted or unsubstituted alkenylene, substituted or unsubstituted alkynylene, substituted or unsubstituted heteroalkylene, substituted or unsubstituted heteroalkenylene, or substituted or unsubstituted heteroalkynylene; [0164] each instance of Ring D is independently aryl, heteroaryl, carbocyclyl, or heterocyclyl; [0165] each instance of R.sup.9 is independently halogen, substituted or unsubstituted alkyl, O-(substituted or unsubstituted alkyl), O-(substituted or unsubstituted aryl), or O-(oxygen protecting group); [0166] each instance of v is independently 0, 1, 2, 3, or 4, as valency permits; [0167] each instance of x is independently 0 or 1; [0168] each instance of G.sup.4 is independently OH, NH.sub.2, or NHR.sup.4; [0169] each instance of R.sup.4 is independently substituted or unsubstituted alkyl, substituted or unsubstituted aryl, or a nitrogen protecting group; and [0170] each instance of m is independently 1, 2, 3, 4, or 5, as valency permits.

[0171] In certain embodiments, at least one (e.g., each) type of the phenols is of the formula:

##STR00011##

or a tautomer, isotopically labeled compound, salt, solvate, polymorph, or co-crystal thereof.

[0172] In certain embodiments, at least one (e.g. each) type of the phenols is of the formula:

##STR00012##

or a tautomer, isotopically labeled compound, salt, solvate, polymorph, or co-crystal thereof.

[0173] In certain embodiments, at least one (e.g., each) type of the phenols is of the formula:

##STR00013##

or a tautomer, isotopically labeled compound, salt, solvate, polymorph, or co-crystal thereof.

[0174] In certain embodiments, at least one (e.g., each) type of the phenols is of the formula:

##STR00014##

or a tautomer, isotopically labeled compound, salt, solvate, polymorph, or co-crystal thereof.

[0175] In certain embodiments, at least one (e.g., each) type of the phenols is of the formula:

##STR00015##

or a tautomer, isotopically labeled compound, salt, solvate, polymorph, or co-crystal thereof.

[0176] In certain embodiments, at least one (e.g., each) type of the phenols is of the formula:

##STR00016##

or a tautomer, isotopically labeled compound, salt, solvate, polymorph, or co-crystal thereof.

[0177] In certain embodiments, at least one (e.g., each) instance of R.sup.3 is independently substituted or unsubstituted alkyl. In certain embodiments, at least one (e.g., each) instance of R.sup.3 is independently unsubstituted C.sub.1-3 alkyl. In certain embodiments, at least one (e.g., each) instance of R.sup.3 is CH.sub.3.

[0178] In certain embodiments, at least one (e.g., each) instance of R.sup.4 is independently substituted or unsubstituted alkyl. In certain embodiments, at least one (e.g., each) instance of R.sup.4 is independently unsubstituted C.sub.1-3 alkyl. In certain embodiments, at least one (e.g., each) instance of R.sup.4 is CH.sub.3.

[0179] In certain embodiments, at least one (e.g., each) instance of G.sup.2 is OH.

[0180] In certain embodiments, at least one (e.g., each) instance of Ring A is phenyl.

[0181] In certain embodiments, at least one (e.g., each) instance of R.sup.5 is independently halogen, unsubstituted alkyl, or O-(unsubstituted alkyl). In certain embodiments, at least one (e.g., each) instance of R.sup.5 is independently halogen, unsubstituted C.sub.1-3 alkyl, or O-(unsubstituted C.sub.1-3 alkyl) (e.g., OCH.sub.3).

[0182] In certain embodiments, at least one (e.g., each) instance of k is independently 0 or 1.

[0183] In certain embodiments, at least one (e.g., each) instance of L.sup.1 is a single bond. In certain embodiments, at least one (e.g., each) instance of L.sup.1 is substituted or unsubstituted alkylene or substituted or unsubstituted alkenylene. In certain embodiments, at least one (e.g., each) instance of L.sup.1 is unsubstituted alkylene or unsubstituted alkenylene. In certain embodiments, at least one (e.g., each) instance of L.sup.1 is alkylene or alkenylene, each of which is independently substituted with one or more halogen, unsubstituted alkyl, and/or O-(unsubstituted alkyl), as valency permits. In certain embodiments, at least one (e.g., each) instance of L.sup.1 is CH.sub.2, (CH.sub.2).sub.2, (CH.sub.2).sub.3, (CH.sub.2).sub.4, (CH.sub.2).sub.5, (CH.sub.2).sub.6, (E)-CHCH, or (Z)CHCH. In certain embodiments, at least one instance of L.sup.1 is (unsubstituted C.sub.1-6 alkylene or unsubstituted C.sub.1-6 alkenylene).sub.0-1-C(O)NH-(unsubstituted C.sub.1-6 alkylene or unsubstituted C.sub.1-6 alkenylene).sub.0-1-, -(unsubstituted C.sub.1-6 alkylene or unsubstituted C.sub.1-6 alkenylene).sub.0-1-NHC(O)-(unsubstituted C.sub.1-6 alkylene or unsubstituted C.sub.1-6 alkenylene).sub.0-1-, -(unsubstituted C.sub.1-6 alkylene or unsubstituted C.sub.1-6 alkenylene).sub.0-1-OC(O)NH-(unsubstituted C.sub.1-6 alkylene or unsubstituted C.sub.1-6 alkenylene).sub.0-1-, -(unsubstituted C.sub.1-6 alkylene or unsubstituted C.sub.1-6 alkenylene).sub.0-1-NHC(O)O-(unsubstituted C.sub.1-6 alkylene or unsubstituted C.sub.1-6 alkenylene).sub.0-1-, or -(unsubstituted C.sub.1-6 alkylene or unsubstituted C.sub.1-6 alkenylene).sub.0-1-NHC(O)NH-(unsubstituted C.sub.1-6 alkylene or unsubstituted C.sub.1-6 alkenylene).sub.0-1-.

[0184] In certain embodiments, at least one (e.g., each) instance of x is 0. In certain embodiments, at least one (e.g., each) instance of x is 1.

[0185] In certain embodiments, at least one (e.g., each) instance of Ring D is phenyl.

[0186] In certain embodiments, at least one (e.g., each) instance of m is 1.

[0187] In certain embodiments, at least one (e.g., each) instance of G.sup.4 is OH. In certain embodiments, at least one (e.g., each) instance of G.sup.4 is independently NH.sub.2 or NH-(unsubstituted alkyl). In certain embodiments, at least one (e.g., each) instance of G.sup.4 is independently NH.sub.2 or NH-(unsubstituted C.sub.1-3 alkyl) (e.g., NHCH.sub.3).

[0188] In certain embodiments, at least one (e.g., each) type of the diols (which are phenols) is of the formula:

##STR00017## ##STR00018##

or a tautomer, isotopically labeled compound, salt, solvate, polymorph, or co-crystal thereof.

[0189] In certain embodiments, least one (e.g., each) type of the polyols (which is a triol and a phenol) is of the formula:

##STR00019##

or a tautomer, isotopically labeled compound, salt, solvate, polymorph, or co-crystal thereof.

[0190] In certain embodiments, the molecular weight of at least one (e.g., each) type of the phenols is between 110 and 200, between 200 and 300, between 300 and 400, or between 400 and 600, g/mol.

[0191] In certain embodiments, the number of types of the phenols is one. In certain embodiments, the number of types of the phenols is two.

[0192] In certain embodiments, each type of the phenols is substantially free of water.

[0193] In certain embodiments, at least one (e.g., each) type of the isocyanates is a diisocyanate, wherein each of the diisocyanates is independently a compound comprising two instances of NCO and zero instances of each of OH, NH.sub.2, and NH.

[0194] In certain embodiments, at least one (e.g., each) type of the isocyanates is of the formula:

##STR00020##

or a tautomer, isotopically labeled compound, salt, solvate, polymorph, or co-crystal thereof, wherein: [0195] each instance of u is independently 0 or 1; [0196] each instance of Ring B is independently aryl, heteroaryl, carbocyclyl, or heterocyclyl; [0197] each instance of R.sup.6 is independently halogen, substituted or unsubstituted alkyl, O-(substituted or unsubstituted alkyl), O-(substituted or unsubstituted aryl), or O-(oxygen protecting group); [0198] each instance of q is independently 0, 1, 2, 3, or 4, as valency permits; [0199] each instance of L.sup.3 is independently substituted or unsubstituted alkylene, substituted or unsubstituted alkenylene, substituted or unsubstituted alkynylene, substituted or unsubstituted heteroalkylene, substituted or unsubstituted heteroalkenylene, or substituted or unsubstituted heteroalkynylene, wherein zero or more (e.g., one or two) backbone carbon atoms of the alkylene, alkenylene, alkynylene, heteroalkylene, heteroalkenylene, or heteroalkynylene are independently replaced with substituted or unsubstituted arylene, substituted or unsubstituted heteroarylene, substituted or unsubstituted carbocyclylene, or substituted or unsubstituted heterocyclylene, or a combination thereof, as valency permits; or a single bond when at least one (e.g., each) of u and t is 1; [0200] each instance of t is independently 0 or 1; [0201] each instance of Ring C is independently aryl, heteroaryl, carbocyclyl, or heterocyclyl; [0202] each instance of R.sup.7 is independently halogen, substituted or unsubstituted alkyl, O-(substituted or unsubstituted alkyl), O-(substituted or unsubstituted aryl), or O-(oxygen protecting group); and [0203] each instance of r is independently 0, 1, 2, 3, or 4, as valency permits.

[0204] In certain embodiments, at least one (e.g., each) instance of u is 0. In certain embodiments, at least one (e.g., each) instance of u is 1.

[0205] In certain embodiments, at least one (e.g., each) instance of Ring B is independently phenyl or cyclohexyl. In certain embodiments, at least one (e.g., each) instance of Ring B is independently monocyclic, 4- to 8-membered carbocyclyl.

[0206] In certain embodiments, at least one (e.g., each) instance of R.sup.6 is independently halogen, unsubstituted alkyl, or O-(unsubstituted alkyl).

[0207] In certain embodiments, at least one (e.g., each) instance of q is 0. In certain embodiments, at least one (e.g., each) instance of q is 1.

[0208] In certain embodiments, at least one (e.g., each) instance of t is 0. In certain embodiments, at least one (e.g., each) instance of t is 1.

[0209] In certain embodiments, at least one (e.g., each) instance of Ring C is independently phenyl or cyclohexyl. In certain embodiments, at least one (e.g., each) instance of Ring C is independently monocyclic, 4- to 8-membered carbocyclyl.

[0210] In certain embodiments, at least one (e.g., each) instance of R.sup.7 is independently halogen, unsubstituted alkyl, or O-(unsubstituted alkyl).

[0211] In certain embodiments, at least one (e.g., each) instance of r is 0. In certain embodiments, at least one (e.g., each) instance of r is 1.

[0212] In certain embodiments, at least one (e.g., each) type of the isocyanates is of the formula:

##STR00021##

or a tautomer, isotopically labeled compound, salt, solvate, polymorph, or co-crystal thereof.

[0213] In certain embodiments, at least one (e.g., each) instance of L.sup.3 is a single bond. In certain embodiments, at least one (e.g., each) instance of L.sup.3 is substituted or unsubstituted alkylene or substituted or unsubstituted heteroalkylene, wherein zero or more (e.g., one or two) backbone carbon atoms of the alkylene or heteroalkylene are replaced with substituted or unsubstituted heterocyclylene, as valency permits. In certain embodiments, at least one (e.g., each) instance of L.sup.3 is substituted or unsubstituted alkylene. In certain embodiments, at least one (e.g., each) instance of L.sup.3 is CH.sub.2, (CH.sub.2).sub.2, (CH.sub.2).sub.3, (CH.sub.2).sub.4, (CH.sub.2).sub.5, or (CH.sub.2).sub.6.

[0214] In certain embodiments, at least one (e.g., each) type of the isocyanates is of the formula:

##STR00022##

or a tautomer, isotopically labeled compound, solvate, polymorph, or co-crystal thereof.

[0215] In certain embodiments, at least one (e.g. each) type of the isocyanates is of the formula:

##STR00023##

or a tautomer, isotopically labeled compound, solvate, polymorph, or co-crystal thereof, wherein each instance of R.sup.14 is H, substituted or unsubstituted alkyl, substituted or unsubstituted aryl, or an oxygen protecting group. In certain embodiments, at least one (e.g., each) instance of R.sup.14 is unsubstituted alkyl (e.g., unsubstituted C.sub.1-3 alkyl).

[0216] In certain embodiments, at least one (e.g., each) type of the isocyanates is of the formula:

##STR00024##

or a tautomer, isotopically labeled compound, solvate, polymorph, or co-crystal thereof.

[0217] In certain embodiments, at least one (e.g., each) type of the isocyanates is a polyisocyanate. In certain embodiments, a polyisocyanate is a compound comprising three or more (e.g., four) instances of NCO and zero instances of each of OH, NH.sub.2, and NH. In certain embodiments, at least one (e.g., each) type of the isocyanates is a Desmodur polyisocyanate (e.g., a Desmodur aliphatic polyisocyanate, e.g., Desmodur N 3200, Desmodur N 3300, Desmodur N 3400, Desmodur N 3500, Desmodur N 3600, Desmodur N 3700, Desmodur N 3800, Desmodur N 3900, Desmodur N 31000, or DesmodurR N 31100, or a mixture thereof).

[0218] In certain embodiments, at least one (e.g., each) type of the isocyanates is of the formula:

##STR00025##

or a tautomer, isotopically labeled compound, salt, solvate, polymorph, or co-crystal thereof, wherein: [0219] each instance of L.sup.4 is independently substituted or unsubstituted alkylene, substituted or unsubstituted alkenylene, substituted or unsubstituted alkynylene, substituted or unsubstituted heteroalkylene, substituted or unsubstituted heteroalkenylene, or substituted or unsubstituted heteroalkynylene, wherein zero or more (e.g., one or two) backbone carbon atoms of the alkylene, alkenylene, alkynylene, heteroalkylene, heteroalkenylene, or heteroalkynylene are independently replaced with substituted or unsubstituted arylene, substituted or unsubstituted heteroarylene, substituted or unsubstituted carbocyclylene, or substituted or unsubstituted heterocyclylene, or a combination thereof, as valency permits; and [0220] each instance of R.sup.8 is independently hydrogen or NCO.

[0221] In certain embodiments, at least one (e.g., each) type of the isocyanates is a triisocyanate, wherein each of the triisocyanates is independently a compound comprising three instances of NCO and zero instances of each of OH, NH.sub.2, and NH.

[0222] In certain embodiments, at least one (e.g., each) instance of R.sup.8 is NCO.

[0223] In certain embodiments, at least one (e.g., each) instance of L.sup.4 is substituted or unsubstituted alkylene or substituted or unsubstituted heteroalkylene, wherein zero or more (e.g., one or two) backbone carbon atoms of the alkylene or heteroalkylene are replaced with substituted or unsubstituted heterocyclylene, as valency permits. In certain embodiments, at least one (e.g., each) instance of L.sup.4 is substituted or unsubstituted alkylene (e.g., unsubstituted unbranched C.sub.2-12 alkylene). In certain embodiments, at least one (e.g., each) instance of L.sup.4 is CH.sub.2, (CH.sub.2).sub.2, (CH.sub.2).sub.3, (CH.sub.2).sub.4, (CH.sub.2).sub.5, (CH.sub.2).sub.6, (CH.sub.2).sub.7, or (CH.sub.2).sub.8.

[0224] In certain embodiments, at least one (e.g., each) type of the isocyanates is of the formula:

##STR00026##

or a tautomer, isotopically labeled compound, solvate, polymorph, or co-crystal thereof.

[0225] In certain embodiments, at least one (e.g., each) type of the isocyanates is of the formula:

##STR00027##

or a tautomer, isotopically labeled compound, solvate, polymorph, or co-crystal thereof.

[0226] In certain embodiments, the molecular weight of at least one (e.g., each) type of the isocyanates is between 100 and 200, between 200 and 300, between 300 and 400, or between 400 and 600, g/mol.

[0227] In certain embodiments, the number of types of the isocyanates is one. In certain embodiments, the number of types of the isocyanates is two.

[0228] In certain embodiments, each type of the isocyanates is substantially free of water. In certain embodiments, each type of the isocyanates is independently between 90% and 95%, between 95% and 97%, between 97% and 99%, between 99% and 99.5%, or between 99.5% and 99.9%, free of water.

[0229] In certain embodiments, the equivalent ratio of all types of the polyols to all types of the isocyanates is between 0.037:1 and 0.33:1, e.g., between 0.074:1 and 0.17:1. In certain embodiments, the equivalent ratio of all types of the polyols to all types of the isocyanates is between 0.037:1 and 0.074:1 or between 0.17:1 and 0.33:1. In certain embodiments, the equivalent ratio of all types of the polyols to all types of the isocyanates is between 0.15:1 and 0.8:1, e.g., between 0.15:1 and 0.3:1. In certain embodiments, the equivalent ratio of all types of the polyols to all types of the isocyanates is between 0.3:1 and 0.5:1 or between 0.5:1 and 0.8:1.

[0230] A polymer with excess amount of all types of isocyanates may show increased strength while still maintaining the debonding characteristics. In certain embodiments, the equivalent ratio of the combination of all types of the diols and all types of the polyols to all types of the isocyanates is between 0.3:1 and 0.8:1, e.g., between 0.6:1 and 0.7:1. In certain embodiments, the equivalent ratio of the combination of all types of the diols and all types of the polyols to all types of the isocyanates is between 0.3:1 and 0.4:1, between 0.4:1 and 0.5:1, between 0.5:1 and 0.6:1, or between 0.7:1 and 0.8:1. In certain embodiments, the equivalent ratio of the combination of all types of the diols and all types of the polyols to all types of the isocyanates is between 0.8:1 and 1.1:1, e.g., between 0.9:1 and 1:1. In certain embodiments, the equivalent ratio of the combination of all types of the diols and all types of the polyols to all types of the isocyanates is between 0.8:1 and 0.85:1, between 0.85:1 and 0.9:1, between 0.9:1 and 0.95:1, or between 0.95:1 and 1:1. In certain embodiments, the equivalent ratio of the combination of all types of the diols and all types of the polyols to all types of the isocyanates is between 1:1 and 1.1:1.

[0231] In certain embodiments, the equivalent ratio of all types of the diols to all types of the polyols to all types of the isocyanates is about 3:1.5:4.75-5. In certain embodiments, the equivalent ratio of all types of the diols to all types of the polyols to all types of the isocyanates is about 3:1.5:4.75. In certain embodiments, the equivalent ratio of all types of the diols to all types of the polyols to all types of the isocyanates is about 3:1.5:5.

[0232] In certain embodiments, the polymerization mixture further comprises a polymerization catalyst (e.g., catalyst for preparing polymers). In certain embodiments, the polymerization mixture of the one-step method further comprises a polymerization catalyst. In certain embodiments, the polymerization mixture of the two-step method is substantially free (e.g., between 90% and 95%, between 95% and 97%, between 97% and 99%, between 99% and 99.5%, or between 99.5% and 99.9%, free) of a polymerization catalyst. In certain embodiments, the polymerization catalyst is an organometallic catalyst for preparing polymers. In certain embodiments, the polymerization catalyst is an organometallic catalyst comprising Sn(II), Sn(IV), Na(I), K(I), Ca(II), or Fe(III). In certain embodiments, the polymerization catalyst is dibutyltin dilaurate, dibutyltin mercaptide, dibutyltin thiocarboxylate, tin(II) 2-ethylhexanoate, sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, calcium carbonate, calcium bicarbonate, tris(acetylacetonato)iron(III), triethylenediamine, 1,4-diazabicyclo[2.2.2]octane, dimethylcyclohexylamine, dimethylethanolamine, or bis-(2-dimethylaminoethyl)ether, or a salt, solvate, polymorph, or co-crystal thereof, or a mixture thereof.

[0233] In certain embodiments, the weight ratio of the polymerization catalyst to the combination of: all types of the diols, all types of the polyols, and all types of the isocyanates is between 0.003:1 and 0.03:1, e.g., between 0.005:1 and 0.02:1. In certain embodiments, the weight ratio of the polymerization catalyst to the combination of: all types of the diols, all types of the polyols, and all types of the isocyanates is between 0.001:1 and 0.003:1, between 0.003:1 and 0.01:1, between 0.01:1 and 0.03:1, or between 0.03:1 and 0.1:1.

[0234] In certain embodiments, the polymerization mixture further comprises a solvent. In certain embodiments, the solvent is substantially one single solvent. In certain embodiments, the solvent is a mixture of two or more (e.g., three) solvents (e.g., solvents described in this paragraph). In certain embodiments, the solvent is an organic solvent. In certain embodiments, the solvent is a non-aromatic organic solvent. In certain embodiments, the solvent is acetone. In certain embodiments, the solvent is methyl ethyl ketone. In certain embodiments, the solvent is a mixture of acetone and methyl ethyl ketone. In certain embodiments, the solvent is a mixture of acetone and methyl ethyl ketone, wherein the volume ratio of acetone to methyl ethyl ketone is between 1:9 and 9:1, e.g., between 1:2 and 2:1. In certain embodiments, the solvent is a mixture of acetone and methyl ethyl ketone, wherein the volume ratio of acetone to methyl ethyl ketone is between 1:1.5 and 1.5:1, between 1:3 and 3:1, or between 1:5 and 5:1. In certain embodiments, the solvent is a mixture of acetone and methyl isopropyl ketone. In certain embodiments, the solvent is a mixture of acetone and 2-pentanone. In certain embodiments, the solvent is a mixture of acetone and 3-pentanone. In certain embodiments, the solvent is acetonitrile, dioxane, tetrahydrofuran, methyl tert-butyl ether, or 2-methyltetrahydrofuran, or a mixture thereof. In certain embodiments, the solvent is N,N-dimethylacetamide. In certain embodiments, the solvent is substantially free (e.g., between 90% and 95%, between 95% and 97%, between 97% and 99%, between 99% and 99.5%, or between 99.5% and 99.9%, free) of N,N-dimethylacetamide. In certain embodiments, the boiling point of the solvent at 1 atm is between 50 and 60, between 60 and 70, between 70 and 80, between 80 and 90, between 90 and 100, or between 100 and 120 C. (e.g., between 5 and 90 C.). The solvent may be adjusted to improve film quality and prevent bubbles during solvent flash at elevated temperature during drying.

[0235] In certain embodiments, the solvent is substantially free of water. In certain embodiments, the polymerization mixture is substantially free of water. In certain embodiments, the solvent is substantially free of dioxygen. In certain embodiments, the polymerization mixture is substantially free of dioxygen. In certain embodiments, the solvent is substantially free of water and dioxygen. In certain embodiments, the polymerization mixture is substantially free of water and dioxygen. In certain embodiments, each substantially free of dioxygen is independently between 90% and 95%, between 95% and 97%, between 97% and 99%, between 99% and 99.5%, or between 99.5% and 99.9%, free of dioxygen. In certain embodiments, the polymerization mixture is under an inert atmosphere.

[0236] In certain embodiments, the ratio of the combined weight of all types of diols, all types of polyols, and all types of isocyanates to the volume of the solvent is about 1:0.7 g/ml. In certain embodiments, the ratio of the combined weight of all types of diols, all types of polyols, and all types of isocyanates to the volume of the solvent is between 1:0.3 and 1:10 g/ml. In certain embodiments, the ratio of the combined weight of all types of diols, all types of polyols, and all types of isocyanates to the volume of the solvent is between 1:0.1 and 1:0.3, between 1:0.3 and 1:0.7, between 1:0.7 and 1:1, between 1:1 and 1:2, between 1:2 and 1:3, between 1:3 and 1:5, between 1:5 and 1:10, between 1:10 and 1:20, or between 1:20 and 1:40, g/ml.

[0237] Unless otherwise provided, any of the mixtures and steps is under a pressure between 0.5 and 1.1 atm (e.g., between 0.8 and 1.1 atm).

[0238] In certain embodiments, the polymerization mixture is prepared by a method (one-step method) comprising reacting a first mixture comprising one or more types of diols, one or more types of isocyanates, and one or more types of polyols at a sixth temperature for a sixth time duration.

[0239] In certain embodiments, the polymerization mixture is prepared by a method (two-step method) comprising: [0240] reacting a first mixture comprising one or more types of diols and one or more types of isocyanates at a sixth temperature for a sixth time duration; and [0241] mixing the first mixture, one or more types of diols, and one or more types of polyols.

[0242] The two-step method may be advantageous over the one-step method at least because the polymers prepared by the former may show higher strength than the polymers prepared by the latter.

[0243] In certain embodiments, at least one type of the diols of the first mixture is the same as at least one type of the diols of the step of mixing. In certain embodiments, at least one type of the diols of the first mixture is different from at least one type of the diols of the step of mixing.

[0244] In certain embodiments, the first mixture is substantially free (e.g., between 90% and 95%, between 95% and 97%, between 97% and 99%, between 99% and 99.5%, or between 99.5% and 99.9%, free) of a solvent. In certain embodiments, the first mixture further comprises a solvent.

[0245] In certain embodiments, the first mixture is substantially free of water and dioxygen. In certain embodiments, the first mixture is substantially free of water. In certain embodiments, the first mixture is substantially free of dioxygen. In certain embodiments, the first mixture is under an inert atmosphere.

[0246] In certain embodiments, the sixth temperature is between 40 and 60, between 60 and 80, between 80 and 100, between 100 and 120, or between 12 and 140 C., e.g., between 9 and 110 C.

[0247] In certain embodiments, the sixth time duration is between 10 minutes and 1 hour, between 1 and 3 hours, between 3 and 8 hours, between 8 and 24 hours, or between 1 and 3 days, e.g., between 0.5 and 4 hours.

[0248] In certain embodiments, the method further comprises cooling the first mixture to between 2 and 30 C., wherein the step of cooling is subsequent to the step of reacting and prior to the step of mixing.

[0249] In certain embodiments, the method further comprises curing the polymerization mixture at a seventh temperature for a seventh time duration.

[0250] In certain embodiments, the seventh temperature is between 30 and 40, between 40 and 50, between 50 and 60, between 60 and 70, or between 7 and 80 C., e.g., between 4 and 60 C.

[0251] In certain embodiments, the seventh time duration is between 1 and 3 hours, between 3 and 8 hours, between 8 and 24 hours, or between 1 and 3 days, e.g., between 6 and 24 hours.

[0252] In certain embodiments, the step of removing comprises an eighth temperature, an eighth pressure, and an eighth time duration.

[0253] In certain embodiments, the eighth temperature is between 30 and 40, between 40 and 50, between 50 and 60, between 60 and 80, or between 8 and 100 C., e.g., between 5 and 80 C.

[0254] In certain embodiments, the eighth pressure is between 10.sup.7 and 10.sup.6, between 10.sup.6 and 10.sup.5, between 10.sup.5 and 10.sup.4, between 10.sup.4 and 10.sup.3, or between 10.sup.3 and 10.sup.2 atm, e.g., between 10.sup.6 and 10.sup.4 atm.

[0255] In certain embodiments, the eighth time duration is between 1 and 3 hours, between 3 and 8 hours, between 8 and 24 hours, between 1 and 3 days, or between 3 and 7 days, e.g., between 12 and 48 hours.

[0256] In certain embodiments, the method comprising reacting the polymerization mixture and the method of preparing a polymer further comprise removing substantially all the solvent. In certain embodiments, the step of removing substantially all the solvent comprises evaporating substantially all the solvent under reduced pressure at a temperature of between 50 and 60, between 60 and 70, between 70 and 80, or between 8 and 90 C., for a time duration of between 1 and 8 hours, between 8 and 24 hours, between 1 and 3 days, between 3 and 7 days, or between 7 and 14 days. In certain embodiments, the reduced pressure is between 0.001 and 0.01, between 0.01 and 0.1, or between 0.1 and 1 atm. In certain embodiments, substantially all the solvent is between 90% and 95%, between 95% and 97%, between 97% and 99%, between 99% and 99.5%, or between 99.5% and 99.9% of the solvent.

[0257] In certain embodiments, the diols, polyols, and isocyanates are:

TABLE-US-00001 Polymer number Diol Polyol Isocyanate 1-5 [00028] [00029] [00030] 1-11 [00031] Glycerol [00032]
or a tautomer, isotopically labeled compound, salt, solvate, polymorph, or co-crystal thereof.

[0258] In certain embodiments, the diols, polyols, and isocyanates, and the equivalents thereof, are:

TABLE-US-00002 Molar ratio of combined equivalents of diol and Polymer Isocyanate/ polyol to equivalent of number Diol/Equivalent Polyol/Equivalent Equivalent isocyanate 1-5A (11)/0.84 10% (10)/0.11 10% (101)/1 49 2%:51 2% 1-11A (11)/0.42 10% Glycerol/0.11 10% (100)/1 49 2%:51 2% and (201)/0.42 10%
or a tautomer, isotopically labeled compound, salt, solvate, polymorph, or co-crystal thereof.

[0259] In certain embodiments, the polymer is a polyurethane, polyurea, polyurethaneurea, or a combination (e.g., blend) thereof. In certain embodiments, the polymer is a polyurethane. In certain embodiments, the polymer is a polyurea. In certain embodiments, the polymer is a polyurethaneurea. In certain embodiments, the polymer is a combination of a polyurethane and a polyurea. In certain embodiments, the polymer is a combination of a polyurethane and a polyurethaneurea. In certain embodiments, the polymer is a combination of a polyurea and a polyurethaneurea. In certain embodiments, the polymer is a combination of a polyurethane, a polyurea, a polyurethaneurea.

[0260] In certain embodiments, the number average molecular weight of the polymer is between 5,000 and 10,000, between 10,000 and 30,000, between 30,000 and 100,000, between 100,000 and 300,000, or between 300,000 and 1,000,000, g/mol.

[0261] In certain embodiments, the dispersity of the polymer is between 1.0 and 1.5, between 1.5 and 2.0, between 2.0 and 2.5, or between 2.5 and 3.0.

[0262] In certain embodiments, the average crosslinking degree of the polymer is between 10% and 20%, between 20% and 30%, between 30% and 40%, between 40% and 50%, or between 50% and 60%, mole:mole. In certain embodiments, the average crosslinking degree is determined by swelling measurements.

[0263] In certain embodiments, the polymer is crosslinked. In certain embodiments, the polymer is a thermoset. In certain embodiments, the polymer is capable of undergoing a reversable transition from a cross-linked state to a lightly cross-linked or un-crosslinked state. In certain embodiments, the polymer is capable of undergoing a reversable transition from a thermoset state to a thermoplastic state.

[0264] In certain embodiments, the polymer is with a transition temperature between 50 and 170 C., e.g., between 6 and 160 C., e.g., between 7 and 150 C. In certain embodiments, the polymer is with a transition temperature between 50 and 60, between 60 and 70, between 70 and 80, between 80 and 100, between 100 and 120, between 120 and 140, or between 14 and 160 C.

[0265] In certain embodiments, the viscosity of the polymer at 10 C. above the transition temperature is between 1 cP and 250,000 cP, between 100 cP and 75,000 cP, or between 1000 cP and 20,000 cP. In certain embodiments, the viscosity of the polymer at 10 C. above the transition temperature is between 1 and 10, between 10 and 100, between 100 and 1,000, between 1,000 and 10,000, or between 10,000 and 100,000 cP.

[0266] In certain embodiments, the polymer is transparent (e.g., having a total transmittance of between 80% and 85%, between 85% and 90%, between 90% and 95%, between 95% and 99%, or between 99% and 99.9%.) under American Society for Testing and Materials (ASTM) Standard D 1746.

[0267] In another aspect, the present disclosure provides compositions comprising the polymer. In certain embodiments, the composition further comprises one or more excipients. In certain embodiments, the composition further comprises one or more adhesion promoters, one or more fillers, and/or one or more rheology modifiers.

[0268] Adhesion promoters may facilitate bonding among the components of the composition and/or between the composition and a surface of a solid substrate. In certain embodiments, the adhesion promoter is a silane compound (e.g., N-ethylaminoisobutyl trimethoxysilane, tris(3-(trimethoxysilyl)propyl)-isocyanurate, 3-aminopropyltriethoxysilane, 3-isocyanatopropyl trimethoxysilane, 3-isocyanatopropyl triethoxysilane, or 3-glycidoxypropylmethyldiethoxysilanem, or a mixture thereof).

[0269] Fillers may be used to adjust the density and/or viscosity of the composition. In certain embodiments, the filler is a fine particle filler (e.g., a clay, polysilica, highly dispersed, pyrogenic, hydrophilic silica, montmorillonite, kaolinite, halloysite, aluminum hydroxide, aluminum oxide hydrate, aluminum silicate, talc, quartz mineral, chalk, magnesium hydroxide, molecular sieves, mica, calcium carbonate, kaolin, titanium oxide, diatomaceous earth, urea-based resin, styrene beads, calcined clay, or starch, or a mixture thereof).

[0270] In certain embodiments, the rheology modifier is a clay, gum, cellulosic, hydrophobically modified ethoxylated urethane, surfactant gel, polyester, or polysaccharide (e.g., chitin), or a mixture thereof.

[0271] In another aspect, the present disclosure provides kit comprising the polymer or the composition; and instructions for using the polymer or composition. In certain embodiments, the kit comprises a first container, wherein the first container comprises the polymer or the composition. In some embodiments, the kit further comprises a second container. In certain embodiments, the second container comprises the one or more excipients, one or more adhesion promoters, one or more fillers, and/or one or more rheology modifiers. In certain embodiments, the second container comprises the instructions. In certain embodiments, each of the first and second containers is independently a vial, ampule, bottle, syringe, dispenser package, tube, or box.

[0272] In certain embodiments, the polymer or composition is in the form of a film (e.g., die cut film), powder, pellet, solid, rod, cylinder, or tube (e.g., die cut tube). In certain embodiments, the polymer or composition is in the form of a film, wherein the average thickness of the film is between 0.001 and 1 mm, e.g., between 0.15 and 0.5 mm. In certain embodiments, the polymer or composition is in the form of a film, wherein the average thickness of the film is between 0.001 and 0.01 mm, between 0.01 and 0.05 mm, between 0.05 and 0.1, between 0.1 and 0.2, between 0.2 and 0.4, between 0.4 and 0.7, or between 0.7 and 1 mm.

[0273] In certain embodiments, the polymer or composition is capable of bonding to a solid substrate below the transition temperature of the polymer.

[0274] In certain embodiments, the polymer or composition is capable of, after bonding to the solid substrate, reversable de-bonding from the solid substrate at or above the transition temperature of the polymer.

[0275] In certain embodiments, the polymer or composition is suitable for use as a hot melt adhesive.

[0276] In another aspect, the present disclosure provides methods of bonding comprising: [0277] applying the polymer or composition to a surface of a first solid substrate; contacting the polymer or composition on the surface of the first solid substrate with a surface of a second solid substrate; and curing the polymer or composition on the surface of the first solid substrate to form bonded first and second substrates; or [0278] applying the polymer or composition to a surface of a first solid substrate and a surface of a second solid substrate; contacting the polymer or composition on the surface of the first solid substrate with the polymer or composition on the surface of the second solid substrate; and curing the polymer or composition on the surface of the first solid substrate and the polymer or composition on the surface of the second solid substrate to form bonded first and second substrates; [0279] wherein the first solid substrate is the same or different from the second solid substrate.

[0280] In certain embodiments, at least one (e.g., each) surface is an outer surface. In certain embodiments, at least one (e.g., each) surface is an inner surface.

[0281] In certain embodiments, the methods further comprise heating the polymer or composition to a second temperature, wherein: the polymer or composition are flowable at the second temperature, and the step of heating the polymer or composition to a second temperature occurs: [0282] prior to the step of applying the polymer or composition; [0283] subsequent to the step of applying the polymer or composition and prior to the step of contacting the polymer or composition; or [0284] subsequent to the step of contacting the polymer or composition and prior to the step of curing the polymer or composition.

[0285] In certain embodiments, the second temperature is between 5 and 170 C., e.g., between 6 and 160 C., e.g., between 7 and 150 C. In certain embodiments, the second temperature is between 50 and 60, between 60 and 70, between 70 and 80, between 80 and 100, between 100 and 120, between 120 and 140, or between 14 and 160 C. In certain embodiments, the second temperature is between 100% and 110%, between 110% and 120%, between 120% and 130%, between 130% and 150%, between 150% and 170%, or between 170% and 200% of the transition temperature.

[0286] In certain embodiments, the step of applying the polymer or composition is substantially free of water. In certain embodiments, the step of contacting the polymer or composition is substantially free of water. In certain embodiments, the step of curing the polymer or composition is substantially free of water.

[0287] In certain embodiments, the step of curing the polymer or composition comprises: [0288] maintaining the polymer or composition at a third temperature for a third time duration, wherein the third temperature is between 5 and 220 C.; and [0289] maintaining the polymer or composition at a fourth temperature for a fourth time duration, wherein the fourth temperature is between 2 and 30 C.

[0290] In certain embodiments, the third temperature is between 5 and 170 C., e.g., between 6 and 160 C., e.g., between 7 and 150 C. In certain embodiments, the third temperature is between 50 and 60, between 60 and 70, between 70 and 80, between 80 and 100, between 100 and 120, between 120 and 140, or between 14 and 160 C. In certain embodiments, the third temperature is between 100 and 120, between 120 and 140, between 140 and 160, between 160 and 180, between 180 and 200, or between 20 and 220 C., e.g., between 13 and 200 C. In certain embodiments, the third temperature is between 100% and 110%, between 110% and 120%, between 120% and 130%, between 130% and 150%, between 150% and 170%, or between 170% and 200% of the transition temperature.

[0291] In certain embodiments, the third time duration is between 5 and 20 minutes, between 20 minutes and 1 hour, between 1 and 3 hours, between 3 and 8 hours, or between 8 and 24 hours, e.g., between 10 minutes and 8 hours.

[0292] In certain embodiments, the third temperature is between 13 and 150 C., and the third time duration is between 2 and 8 hours. In certain embodiments, the third temperature is between 15 and 200 C., and the third time duration is between 10 minutes and 3 hours.

[0293] In certain embodiments, the fourth temperature is between 2 and 24 C.

[0294] In certain embodiments, the fourth time duration is between 10 minute and 1 hour, between 1 and 8 hours, between 8 and 24 hours, between 1 and 3 days, between 3 and 7 days, between 7 and 14 days, or between 14 to 30 days, e.g., between 3 and 14 days, e.g., between 30 minutes and 4 days. In certain embodiments, the fourth time duration is between 30 minute and 2 hours.

[0295] In another aspect, the present disclosure provides methods of de-bonding comprising maintaining the bonded first and second substrates at a fifth temperature for a fifth time duration sufficient to form de-bonded first and solid substrates, wherein: [0296] the fifth temperature is between 40 and 60, between 60 and 80, between 80 and 100, between 100 and 120, between 120 and 140, between 140 and 160, between 160 and 180, or between 18 and 200 C., e.g., between 5 and 150 C.; and [0297] the fifth time duration is between 10 and 60 seconds, between 1 and 10 minutes, between 10 and 60 minutes, between 1 and 8 hours, or between 8 and 24 hours, e.g., between 10 seconds and 2 minutes.

[0298] In certain embodiments, the solid substrate is a metal (e.g., metal alloy, anodized metal, or metal oxide), glass, ceramic, composite, plastic (e.g., filled plastic or blend of plastic), or wood. In certain embodiments, the solid substrate is stainless steel, aluminum, anodized aluminum, aluminum alloy, or anodized aluminum alloy. In certain embodiments, the solid substrate is acrylonitrile butadiene styrene, polycarbonate, polycarbonate siloxane copolymer, polyamide, or polybutylene terephthalate. In certain embodiments, the solid substrate is polyamide 66, polyamide 6, polyamide 510, or polyamide 1,6. In certain embodiments, the solid substrate is a glass fiber filled polymer, e.g., glass fiber filled polyamide or glass fiber filled polybutylene terephthalate. In certain embodiments, the solid substrate is polymer blend, e.g., polycarbonate-polybutylene terephthalate blend. In certain embodiments, the solid substrate is a textile (e.g., textile bonded to plastic), leather, paper, or cardboard.

[0299] In certain embodiments, the solid substrate is part of: an electronic device, soft goods, aircraft, vehicle, civil engineering structure, or building. In certain embodiments, the electronic device is a phone (e.g., mobile phone), computer (e.g., laptop computer or tablet computer), watch, keyboard, or display, or a component thereof (e.g., phone cover or watch strap).

EQUIVALENTS AND SCOPE

[0300] 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.

[0301] 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. It is also noted that the terms comprising, including, and containing, and all other tenses thereof, are intended to be open and permits the inclusion of additional possibilities (e.g., 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.

[0302] 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.

[0303] 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.