ADHESIVE COMPOSITIONS AND METHODS

1 . A polyurethane adhesive composition comprising segments derived from one or more aliphatic polycarbonate polyols having a primary repeating unit with a structure:

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

2 . The polyurethane adhesive composition of claim 1 , wherein the aliphatic polycarbonate polyol is derived from the copolymerization of carbon dioxide and one or more epoxides.

3 . The polyurethane adhesive composition of claim 1 , wherein the aliphatic polycarbonate polyol is characterized in that at least 90% of the end groups are —OH groups.

4 . The polyurethane adhesive composition of claim 1 , wherein the aliphatic polycarbonate polyol is characterized in that at least 95%, at least 96%, at least 97% or at least 98% of the end groups are —OH groups.

5 . The polyurethane adhesive composition of claim 1 , wherein the aliphatic polycarbonate polyol is characterized in that at least 99%, at least 99.5%, at least 99.7%, or at least 99.8% of the end groups are —OH groups.

6 . The polyurethane adhesive composition of claim 1 , wherein the aliphatic polycarbonate polyol is characterized in that at least 99.9% of the end groups are —OH groups.

7 . The polyurethane adhesive composition of claim 1 , wherein the aliphatic polycarbonate polyol comprises a copolymer of carbon dioxide and ethylene oxide.

8 . The polyurethane adhesive composition of claim 1 , wherein the aliphatic polycarbonate polyol comprises a copolymer of carbon dioxide and propylene oxide.

9 . The polyurethane adhesive composition of claim 1 , wherein the aliphatic polycarbonate polyol comprises a terpolymer of carbon dioxide and ethylene oxide along with one or more additional epoxides selected from the group consisting of propylene oxide, 1,2-butene oxide, 2,3-butene oxide, cyclohexene oxide, 3-vinyl cyclohexene oxide, epichlorohydrin, glicydyl esters, glycidyl ethers, styrene oxides, and epoxides of higher alpha olefins.

10 . The polyurethane adhesive composition of claim 9 , wherein the terpolymers contain a majority of repeat units derived from ethylene oxide with lesser amounts of repeat units derived from one or more additional epoxides.

11 . The polyurethane adhesive composition of claim 10 , wherein the terpolymers contain about 50% to about 99.5% ethylene oxide-derived repeat units.

12 . The polyurethane adhesive composition of claim 1 , wherein the aliphatic polycarbonate polyol comprises a terpolymer of carbon dioxide and propylene oxide along with one or more additional epoxides selected from the group consisting of ethylene oxide, 1,2-butene oxide, 2,3-butene oxide, cyclohexene oxide, 3-vinyl cyclohexene oxide, epichlorohydrin, glicydyl esters, glycidyl ethers, styrene oxides, and epoxides of higher alpha olefins.

13 . The polyurethane adhesive composition of claim 12 , wherein the terpolymers contain about 50% to about 99.5% ethylene oxide-derived repeat units.

14 . The polyurethane adhesive composition of claim 1 , wherein the aliphatic polycarbonate polyol has a number average molecular weight (M n ) in the range of about 500 g/mol to about 10,000 g/mol.

15 . The polyurethane adhesive composition of claim 1 , wherein the aliphatic polycarbonate polyol has a number average molecular weight (M n ) between about 500 g/mol and about 5,000 g/mol.

16 . The polyurethane adhesive composition of claim 1 , wherein the aliphatic polycarbonate polyol has a number average molecular weight (M n ) between about 500 g/mol and about 4,000 g/mol.

17 . The polyurethane adhesive composition of claim 1 , wherein the aliphatic polycarbonate polyol has a number average molecular weight (M n ) between about 500 g/mol and about 3,000 g/mol.

18 . The polyurethane adhesive composition of claim 1 , wherein the aliphatic polycarbonate polyol has a number average molecular weight (M n ) between about 500 g/mol and about 2,500 g/mol.

19 . The polyurethane adhesive composition of claim 1 , wherein the aliphatic polycarbonate polyol has a number average molecular weight (M n ) between about 500 g/mol and about 1,500 g/mol.

20 . The polyurethane adhesive composition of claim 1 , wherein the aliphatic polycarbonate polyol is characterized in that it has a PDI less than 2.

21 . The polyurethane adhesive composition of claim 1 , wherein the aliphatic polycarbonate polyol is characterized in that it has a PDI less than about 1.5.

22 . The polyurethane adhesive composition of claim 1 , wherein the aliphatic polycarbonate polyol is characterized in that it has a PDI between about 1.0 and 1.2.

23 . The polyurethane adhesive composition of claim 1 , wherein the aliphatic polycarbonate polyol is characterized in that it has a PDI between about 1.0 and 1.1.

24 . The polyurethane adhesive composition of claim 1 , wherein the aliphatic polycarbonate polyol is characterized in that, on average in the composition, the percentage of carbonate linkages is 85% or greater.

25 . The polyurethane adhesive composition of claim 1 , wherein the aliphatic polycarbonate polyol is characterized in that, on average in the composition, the percentage of carbonate linkages is 90% or greater.

26 . The polyurethane adhesive composition of claim 1 , wherein the aliphatic polycarbonate polyol is characterized in that, on average in the composition, the percentage of carbonate linkages is 95% or greater.

27 . The polyurethane adhesive composition of claim 1 , wherein the aliphatic polycarbonate polyol is characterized in that, on average in the composition, the percentage of carbonate linkages is 98% or greater.

28 . The polyurethane adhesive composition of claim 1 , wherein the aliphatic polycarbonate polyol is characterized in that, on average in the composition, the percentage of carbonate linkages is 99% or greater.

29 . The polyurethane adhesive composition of claim 1 , wherein the aliphatic polycarbonate polyol is derived from one or more mono-substituted epoxides and is characterized in that it is regioregular.

30 . The polyurethane adhesive composition of claim 29 , wherein the aliphatic polycarbonate polyol has a head-to-tail ratio greater than about 80%.

31 . The polyurethane adhesive composition of claim 29 , wherein the aliphatic polycarbonate polyol has a head-to-tail ratio greater than about 85%.

32 . The polyurethane adhesive composition of claim 29 , wherein the aliphatic polycarbonate polyol has a head-to-tail ratio greater than about 90%.

33 . The polyurethane adhesive composition of claim 29 , wherein the aliphatic polycarbonate polyol has a head-to-tail ratio greater than about 95%.

34 . The polyurethane adhesive composition of claim 29 , wherein the aliphatic polycarbonate polyol has a head-to-tail ratio greater than about 97%.

35 . The polyurethane adhesive composition of claim 29 , wherein the aliphatic polycarbonate polyol has a head-to-tail ratio greater than about 99%.

36 . The polyurethane adhesive composition of claim 1 , wherein the aliphatic polycarbonate polyol is characterized in that it has a viscosity less than about 1,000,000 cps at 20° C.

37 . The polyurethane adhesive composition of claim 36 , wherein the aliphatic polycarbonate polyol is characterized in that it has a viscosity less than about 500,000 cps, less than about 150,000 cps, or less than about 50,000 cps at 25° C.

38 . The polyurethane adhesive composition of claim 1 , wherein the aliphatic polycarbonate polyol has a structure P1:

wherein, R 1 , R 2 , R 3 , and R 4 are, at each occurrence in the polymer chain, independently selected from the group consisting of —H, fluorine, an optionally substituted C 1-30 aliphatic group, and an optionally substituted C 1-20 heteroaliphatic group, and an optionally substituted C 6-10 aryl group, where any two or more of R 1 , R 2 , R 3 , and R 4 may optionally be taken together with intervening atoms to form one or more optionally substituted rings optionally containing one or more heteroatoms;

Y is, at each occurrence, independently —H or the site of attachment to any of the chain-extending moieties described in the classes and subclasses herein;

n is at each occurrence, independently an integer from about 3 to about 1,000;

is a multivalent moiety; and

x and y are each independently an integer from 0 to 6, where the sum of x and y is between 2 and 6.

39 . The polyurethane adhesive composition of claim 38 , wherein

is derived from a polyfunctional chain transfer agent having two or more sites from which epoxide/CO 2 copolymerization can occur.

40 . The polyurethane adhesive composition of claim 38 , wherein

is derived from a polyfunctional chain transfer agent having a formula:

41 . The polyurethane adhesive composition of claim 38 , wherein

is derived from a dihydric alcohol.

42 . The polyurethane adhesive composition of claim 41 , wherein the dihydric alcohol comprises a C 2-40 diol.

43 . The polyurethane adhesive composition of claim 41 , wherein the dihydric alcohol is selected from the group consisting of: 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 2,2-dimethylpropane-1,3-diol, 2-butyl-2-ethylpropane-1,3-diol, 2-methyl-2,4-pentane diol, 2-ethyl-1,3-hexane diol, 2-methyl-1,3-propane diol, 1,5-hexanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, 1,12-dodecanediol, 2,2,4,4-tetramethylcyclobutane-1,3-diol, 1,3-cyclopentanediol, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 1,4-cyclohexanediethanol, isosorbide, glycerol monoesters, glycerol monoethers, trimethylolpropane monoesters, trimethylolpropane monoethers, pentaerythritol diesters, pentaerythritol diethers, and alkoxylated derivatives of any of these.

44 . The polyurethane adhesive composition of claim 41 , wherein the dihydric alcohol is selected from the group consisting of: diethylene glycol, triethylene glycol, tetraethylene glycol, higher poly(ethylene glycol), such as those having number average molecular weights of from 220 to about 2000 g/mol, dipropylene glycol, tripropylene glycol, and higher poly(propylene glycols).

45 . The polyurethane adhesive composition of claim 41 , wherein the dihydric alcohol comprises an alkoxylated derivative of a compound selected from the group consisting of: a diacid, a diol, and a hydroxy acid.

46 . The polyurethane adhesive composition of claim 41 , wherein the dihydric alcohol a polymeric diol.

47 . The polyurethane adhesive composition of claim 45 , wherein the polymeric diol is selected from the group consisting of polyethers, polyesters, hydroxy-terminated polyolefins, polyether-copolyesters, polyether polycarbonates, polycarbonate-copolyesters, polyoxymethylene polymers, and alkoxylated analogs of any of these.

48 . The polyurethane adhesive composition of claim 38 , wherein y is 0 and x is greater than 2.

49 . The polyurethane adhesive composition of claim 1 , further comprising one or more additional polyols selected from the group consisting of polyether polyols, polyester polyols, and mixtures of these.

50 . The polyurethane adhesive composition of claim 1 , wherein the aliphatic polycarbonate polyol is selected from the group consisting of:

wherein, t is an integer from 1 to 12 inclusive, and R t is independently at each occurrence —H, or —CH 3 .

51 . The polyurethane adhesive composition of claim 50 , comprising poly(ethylene carbonate) of formula Q1 having an average molecular weight number of between about 500 g/mol and about 3,000 g/mol, a polydispersity index less than about 1.25, at least 85% carbonate linkages, and at least 98% —OH end groups.

52 . The polyurethane adhesive composition of claim 50 , comprising poly(ethylene carbonate) of formula Q1 having an average molecular weight number of about 500 g/mol, a polydispersity index less than about 1.25, at least 85% carbonate linkages, and at least 98% —OH end groups;

53 . The polyurethane adhesive composition of claim 50 , comprising poly(ethylene carbonate) of formula Q1 having an average molecular weight number of about 1,000 g/mol, a polydispersity index less than about 1.25, at least 85% carbonate linkages, and at least 98% —OH end groups;

54 . The polyurethane adhesive composition of claim 50 , comprising poly(ethylene carbonate) of formula Q1 having an average molecular weight number of about 2,000 g/mol, a polydispersity index less than about 1.25, at least 85% carbonate linkages, and at least 98% —OH end groups;

55 . The polyurethane adhesive composition of claim 50 , comprising poly(ethylene carbonate) of formula Q1 having an average molecular weight number of about 3,000 g/mol, a polydispersity index less than about 1.25, at least 85% carbonate linkages, and at least 98% —OH end groups;

56 . The polyurethane adhesive composition of claim 50 , comprising poly(propylene carbonate) of formula Q2 having an average molecular weight number of between about 500 g/mol and about 3,000 g/mol, a polydispersity index less than about 1.25, at least 95% carbonate linkages, and at least 98% —OH end groups;

57 . The polyurethane adhesive composition of claim 50 , comprising poly(propylene carbonate) of formula Q2 having an average molecular weight number of about 500 g/mol, a polydispersity index less than about 1.25, at least 95% carbonate linkages, and at least 98% —OH end groups;

58 . The polyurethane adhesive composition of claim 50 , comprising poly(propylene carbonate) of formula Q2 having an average molecular weight number of about 1,000 g/mol, a polydispersity index less than about 1.25, at least 95% carbonate linkages, and at least 98% —OH end groups;

59 . The polyurethane adhesive composition of claim 50 , comprising poly(propylene carbonate) of formula Q2 having an average molecular weight number of about 2,000 g/mol, a polydispersity index less than about 1.25, at least 95% carbonate linkages, and at least 98% —OH end groups;

60 . The polyurethane adhesive composition of claim 50 , comprising poly(propylene carbonate) of formula Q2 having an average molecular weight number of about 3,000 g/mol, a polydispersity index less than about 1.25, at least 95% carbonate linkages, and at least 98% —OH end groups;

61 . The polyurethane adhesive composition of claim 50 , comprising poly(ethylene-co-propylene carbonate) of formula Q3 having an average molecular weight number of between about 500 g/mol and about 3,000 g/mol, a polydispersity index less than about 1.25, at least 90% carbonate linkages, and at least 98% —OH end groups;

62 . The polyurethane adhesive composition of claim 50 , comprising poly(ethylene-co-propylene carbonate) of formula Q3 having an average molecular weight number of about 500 g/mol, a polydispersity index less than about 1.25, at least 90% carbonate linkages, and at least 98% —OH end groups;

63 . The polyurethane adhesive composition of claim 50 , comprising poly(ethylene-co-propylene carbonate) of formula Q3 having an average molecular weight number of about 1,000 g/mol, a polydispersity index less than about 1.25, at least 90% carbonate linkages, and at least 98% —OH end groups;

64 . The polyurethane adhesive composition of claim 50 , comprising poly(ethylene-co-propylene carbonate) of formula Q3 having an average molecular weight number of about 2,000 g/mol (e.g. n is on average between about 10 and about 11), a polydispersity index less than about 1.25, at least 90% carbonate linkages, and at least 98% —OH end groups;

65 . The polyurethane adhesive composition of claim 50 , comprising poly(ethylene-co-propylene carbonate) of formula Q3 having an average molecular weight number of about 3,000 g/mol, a polydispersity index less than about 1.25, at least 95% carbonate linkages, and at least 98% —OH end groups;

66 . The polyurethane adhesive composition of claim 50 , comprising poly(ethylene carbonate) of formula Q4 having an average molecular weight number of between about 500 g/mol and about 3,000 g/mol (e.g. each n is between about 4 and about 16), a polydispersity index less than about 1.25, at least 95% carbonate linkages, and at least 98% —OH end groups;

67 . The polyurethane adhesive composition of claim 50 , comprising poly(ethylene carbonate) of formula Q4 having an average molecular weight number of about 500 g/mol, a polydispersity index less than about 1.25, at least 85% carbonate linkages, and at least 98% —OH end groups;

68 . The polyurethane adhesive composition of claim 50 , comprising poly(ethylene carbonate) of formula Q4 having an average molecular weight number of about 1,000 g/mol, a polydispersity index less than about 1.25, at least 85% carbonate linkages, and at least 98% —OH end groups;

69 . The polyurethane adhesive composition of claim 50 , comprising poly(ethylene carbonate) of formula Q4 having an average molecular weight number of about 2,000 g/mol, a polydispersity index less than about 1.25, at least 85% carbonate linkages, and at least 98% —OH end groups;

70 . The polyurethane adhesive composition of claim 50 , comprising poly(ethylene carbonate) of formula Q4 having an average molecular weight number of about 3,000 g/mol, a polydispersity index less than about 1.25, at least 85% carbonate linkages, and at least 98% —OH end groups.

71 . The polyurethane adhesive composition of claim 50 , comprising poly(propylene carbonate) of formula Q5 having an average molecular weight number of between about 500 g/mol and about 3,000 g/mol, a polydispersity index less than about 1.25, at least 95% carbonate linkages, and at least 98% —OH end groups;

72 . The polyurethane adhesive composition of claim 50 , comprising poly(propylene carbonate) of formula Q5 having an average molecular weight number of about 500 g/mol, a polydispersity index less than about 1.25, at least 95% carbonate linkages, and at least 98% —OH end groups;

73 . The polyurethane adhesive composition of claim 50 , comprising poly(propylene carbonate) of formula Q5 having an average molecular weight number of about 1,000 g/mol, a polydispersity index less than about 1.25, at least 95% carbonate linkages, and at least 98% —OH end groups;

74 . The polyurethane adhesive composition of claim 50 , comprising poly(propylene carbonate) of formula Q5 having an average molecular weight number of about 2,000 g/mol, a polydispersity index less than about 1.25, at least 95% carbonate linkages, and at least 98% —OH end groups;

75 . The polyurethane adhesive composition of claim 50 , comprising poly(propylene carbonate) of formula Q5 having an average molecular weight number of about 3,000 g/mol, a polydispersity index less than about 1.25, at least 95% carbonate linkages, and at least 98% —OH end groups;

76 . The polyurethane adhesive composition of claim 50 , comprising poly(ethylene-co-propylene carbonate) of formula Q6 having an average molecular weight number of between about 500 g/mol and about 3,000 g/mol, a polydispersity index less than about 1.25, at least 90% carbonate linkages, and at least 98% —OH end groups;

77 . The polyurethane adhesive composition of claim 50 , comprising poly(ethylene-co-propylene carbonate) of formula Q6 having an average molecular weight number of about 500 g/mol, a polydispersity index less than about 1.25, at least 90% carbonate linkages, and at least 98% —OH end groups;

78 . The polyurethane adhesive composition of claim 50 , comprising poly(ethylene-co-propylene carbonate) of formula Q6 having an average molecular weight number of about 1,000 g/mol, a polydispersity index less than about 1.25, at least 90% carbonate linkages, and at least 98% —OH end groups;

79 . The polyurethane adhesive composition of claim 50 , comprising poly(ethylene-co-propylene carbonate) of formula Q6 having an average molecular weight number of about 2,000 g/mol (e.g. n is on average between about 10 and about 11), a polydispersity index less than about 1.25, at least 90% carbonate linkages, and at least 98% —OH end groups; and

80 . The polyurethane adhesive composition of claim 50 , comprising poly(ethylene-co-propylene carbonate) of formula Q6 having an average molecular weight number of about 3,000 g/mol, a polydispersity index less than about 1.25, at least 95% carbonate linkages, and at least 98% —OH end groups.

81 . The polyurethane adhesive composition of claim 1 , comprising 100 parts by weight of a polyol component, wherein the aliphatic polycarbonate polyol comprises from about 5 weight percent to 100 weight percent of the polyol component.

82 . The polyurethane adhesive composition of claim 81 , further comprising 0.01 to 20 parts by weight of one or more chain extender.

83 . The polyurethane adhesive composition of claim 82 , wherein the curative agent comprises water.

84 . The polyurethane adhesive composition of claim 80 , further comprising 0 to 1 parts by weight of one or more catalysts.

85 . The polyurethane adhesive composition of claim 82 , wherein the catalyst comprises tin.

86 . The polyurethane adhesive composition of claim 84 , wherein the catalyst comprises an amine compound.

87 . The polyurethane adhesive composition of claim 81 , further comprising 0 to 20 parts by weight of one or more reactive small molecules, wherein the reactive small molecules comprise one or more functional groups selected from the group consisting of hydroxyls, amines, thiols, and carboxylic acids.

88 . The polyurethane adhesive composition of claim 87 , wherein the reactive small molecule comprises a diol.

89 . The polyurethane adhesive composition of claim 87 , wherein the reactive small molecule comprises a polyol with functionality greater than 2.

90 . The polyurethane adhesive composition of claim 81 , further comprising 0 to 10 parts by weight of one or more additives, wherein the additives are selected from the group consisting of: fillers, clays, blocking agents, stabilizers, thixotropic materials, plasticizers, compatibilizers, colorants, UV stabilizers or flame retardents.

91 . A one-part adhesive composition comprising a polyurethane prepolymer synthesized from the reaction product of polyol in claim 1 and isocyanate combined with an optional catalyst in claim 84 and/or optional additives listed in claim 90 .

92 . A two component polyurethane adhesive composition comprising a first and a second component wherein the first component comprises one or more polyols from claim 1 , one or more catalysts comprising a catalyst and optional additives in claims 84 and 90 , the second component comprising one or more isocyanates.

93 . The adhesive of claim 92 , wherein either component contains a blocking agent used to slow the rate of cure of the polyurethane adhesive.

94 . A moisture-curing polyurethane hot-melt adhesive composition comprising at least one polyurethane prepolymer, said polyurethane prepolymer being the reaction product of reactants comprising: a) at least one aromatic polyisocyanate, b) polyol from claim 1 .

95 . A cured adhesive derived from a composition of any one of claims 1 - 94 wherein a cured bond formed by adhesive retains at least 50% of its room temperature strength when heated to a temperature of at least 50° C.

96 . The cured adhesive of claim 95 , wherein the cured bond formed by adhesive retains at least 50% of its room temperature strength when heated to a temperature of at least 60° C.

97 . The cured adhesive of claim 95 , wherein the cured bond formed by adhesive retains at least 50% of its room temperature strength when heated to a temperature of at least 70° C.