US2014135455A1PendingUtilityA1
Transketalized compositions, synthesis, and applications
Est. expiryApr 16, 2028(~1.8 yrs left)· nominal 20-yr term from priority
C07D 407/12C07D 493/04C07D 407/14C07D 493/22C07D 317/22C07D 317/12C07D 407/04C08G 63/668C07D 493/16C08L 77/06C08G 69/48C08G 69/28C07D 493/18C07D 493/10C08L 77/12C07D 493/14C07D 317/30C08G 69/26C08G 69/44
63
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Claims
Abstract
The present disclosure relates to the preparation of ketal compounds from polyols and oxocarboxylates, and uses thereof.
Claims
exact text as granted — not AI-modified1 - 62 . (canceled)
63 . A compound comprising structure II
wherein
R 1 is hydrogen, a metal cation, an organic cation, a linear, branched, or cyclic alkyl, a linear, branched, or cyclic alkenyl, alkynyl, aryl, alkaryl, or an oligomeric or polymeric moiety;
R 2 is a covalent bond or a linear or branched alkyl group;
R 3 is hydrogen, a linear, branched, or cyclic alkyl group;
R 4 and R 5 are independently linear, branched, or cyclic alkyl groups; and
Z is O or NR, wherein R is hydrogen or a linear or branched alkyl group having between 1 and 6 carbon atoms.
64 . The compound of claim 63 wherein R 2 is —CH 2 CH 2 —, R 3 is CH 3 —, Z is O, and R 1 is a cation or a linear or branched alkyl group having between 1 and 8 carbon atoms.
65 . A compound comprising structure IIIa or IIIb
wherein
R 3 and R 5 are independently isobutyl or
wherein
R 1 is hydrogen, a metal cation, an organic cation, a linear, branched, or cyclic alkyl, a linear, branched, or cyclic alkenyl, alkynyl, aryl, alkaryl, or an oligomeric or polymeric moiety;
R 2 is a covalent bond or a linear or branched alkyl group; and
Z is O or NR where R is hydrogen or a linear or branched alkyl group having between 1 and 6 carbon atoms; and
R 4 and R 6 are independently hydrogen or linear, branched, or cyclic alkyl groups.
66 . The compound of claim 65 wherein both R 3 and R 5 are
R 2 is —CH 2 —CH 2 —, and R 4 and R 6 are methyl.
67 . A compound comprising structure Ic
R 1 is a divalent linear, branched, or cyclic alkyl, a linear, branched, or cyclic alkenyl, alkynyl, aryl, or alkaryl moiety;
R 2 is a covalent bond, a linear, branched, or cyclic alkyl group, or a linear, cyclic, or branched alkenyl group;
R 3 , R 5 and R 6 are independently hydrogen or linear, branched, or cyclic alkyl groups, or linear, cyclic, or branched alkenyl groups; and
R 4 is a covalent bond or a linear, branched, or cyclic alkyl group, or linear, cyclic, or branched alkenyl group, or a linear or branched alkynyl, aryl, aralkyl, or aralkenyl group; and
Z and Z′ are independently O or NR, wherein R is hydrogen or an alkyl group having between 1 and 6 carbon atoms.
68 . The compound of claim 67 wherein
R′ is selected from —(CH 2 ) 2 —, —(CH 2 ) 3 —, —(CH 2 ) 4 —, —(CH 2 ) 5 —, —(CH 2 ) 6 —, —(CH 2 ) 2 —O—(CH 2 ) 2 —, or
R 4 is selected from a covalent bond or
wherein R 7 and R 8 are independently linear alkyl groups, branched alkyl groups, cyclic alkyl groups, linear alkenyl groups, branched alkenyl groups, cyclic alkenyl groups, alkynyl groups, aryl groups, aralkyl groups, or aralkenyl groups; or R 7 and R 8 are connected to each other as part of an alkyl or alkenyl ring having 5 to 12 members,
one of R 5 or R 6 is
wherein R 7 and R 8 are independently linear alkyl groups, branched alkyl groups, cyclic alkyl groups, linear alkenyl groups, branched alkenyl groups, or cyclic alkenyl groups, alkynyl groups, aryl groups, aralkyl groups, or aralkenyl groups; or R 7 and R 8 are connected to each other as part of an alkyl or alkenyl ring having 5 to 12 members, and
R 2 is —CH 2 CH 2 — and R 3 is —CH 3 .
69 . A compound comprising at least one repeat unit corresponding to structure IV:
wherein
R 1 is a divalent linear, branched, or cyclic alkyl, a linear, branched, or cyclic alkenyl, alkynyl, aryl, or alkaryl moiety, wherein R 1 is the same or different for each occurrence;
R 2 is a covalent bond or a linear or branched alkyl group wherein R 2 is the same or different for each occurrence;
R 3 is hydrogen, a linear, branched, or cyclic alkyl wherein R 3 is the same or different for each occurrence;
R 4 is a covalent bond, methylene, or alkylmethylene, wherein a covalent bond indicates a 5-membered ring and a methylene or alkylmethylene indicates a 6-membered ring, wherein R 4 is the same or different for each occurrence;
R 5 is a covalent bond, methylene, ethylene, hydroxymethylene, —CH 2 —O—CH 2 —, or a polymeric moiety wherein R 5 is the same or different for each occurrence;
R 6 and R 7 are independently linear, branched, or cyclic alkyl groups;
R 8 and R 9 are independently hydrogen, a linear, branched, or cyclic alkyl, a linear, branched, or cyclic alkenyl, alkynyl, aryl, alkaryl, or a polymeric moiety;
Z and Z′ are independently O or NR where R is hydrogen or an alkyl group having between 1 and 6 carbon atoms;
α is an integer of at least 1 and defines a ketal unit, wherein a ketal units are disposed contiguously to R 5 , R 8 , R 9 , or a combination thereof; and
δ is an integer of at least 1.
70 . The compound of claim 69 wherein α is 1, all R 2 are —CH 2 CH 2 —, all R 3 are CH 3 —, R 8 and R 9 are hydrogen, and all R 4 and R 5 are covalent bonds.
71 . The compound of claim 69 wherein one or more Z or Z′ are NH and the compound is a polyamide, a copolyamide, or a poly(ester amide).
72 . The compound of claim 69 wherein all Z and Z′ are O and the compound further comprises ester, isocyanate, urethane, carbonate, polymerized allyl, polymerized epoxy, polymerized acrylate, or polymerized methacrylate groups or a combination of one or more thereof.
73 . The compound of claim 69 wherein R 6 and R 7 are chosen from the group consisting of methyl, ethyl, and isobutyl.
74 . A compound comprising at least one repeat unit corresponding to structure Va, Vb, or a combination thereof
wherein
R 1 is a divalent linear, branched, or cyclic alkyl, a linear, branched, or cyclic alkenyl, alkynyl, aryl, or alkaryl moiety, wherein R 1 is the same or different for each occurrence;
R 2 is a covalent bond or a linear or branched alkyl group wherein R 2 is the same or different for each occurrence;
R 3 is hydrogen, a linear, branched, or cyclic alkyl wherein R 3 is the same or different for each occurrence;
Z and Z′ are independently O or NR where R is hydrogen or an alkyl group having between 1 and 6 carbon atoms; and
δ is between about 1 and 500.
75 . The compound of claim 74 wherein one or more Z or Z′ are NH and the compound is a polyamide, a copolyamide, or a poly(ester amide).
76 . The compound of claim 74 wherein all Z and Z′ are O and the compound further comprises ester, isocyanate, urethane, carbonate, allylic, epoxy, acrylate, or methacrylate groups or a combination of one or more thereof.
77 . A method of making a compound having structure I, comprising
a. contacting a compound comprising structure VI
wherein
R 4 is a covalent bond, methylene, or alkylmethylene, wherein a covalent bond indicates a 5-membered ring and a methylene or alkylmethylene indicates a 6-membered ring, wherein R 4 is the same or different for each occurrence;
R 5 is a covalent bond, methylene, ethylene, hydroxymethylene, —CH 2 —O—CH 2 —, or a polymeric moiety, and R 5 is the same or different for each occurrence;
R 8 and R 9 are independently hydrogen, a linear, branched, or cyclic alkyl, a linear, branched, or cyclic alkenyl, alkynyl, aryl, alkaryl, or a polymeric moiety; and α and β are integers of at least 1 such that the sum α+β is at least 2,
with at least (α+β) moles of one or more compounds comprising structure VII
wherein
R 1 is hydrogen, a metal cation, an organic cation, a linear, branched, or cyclic alkyl, a linear, branched, or cyclic alkenyl, alkynyl, aryl, alkaryl, or an oligomeric or polymeric moiety;
R 2 is a covalent bond or a linear or branched alkyl group;
R 3 is a linear, branched, or cyclic alkyl group;
Z is O or NR, wherein R is hydrogen or a linear or branched alkyl group having between 1 and 6 carbon atoms;
b. reacting the compound VI and the compound VII to form a first ketal in the presence of a catalyst;
c. contacting the first ketal with at least a equivalents of a dialkyl ketone of the formula O═CR 6 R 7 wherein R 6 and R 7 are independently linear, branched, or cyclic alkyl groups; and
d. reacting the first ketal with the dialkyl ketone to form a second ketal having structure I
wherein
Z, R, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , and R 9 are as defined in structures VI and VII;
γ is an integer of at least 1; and
α and β are independently 0 or 1 for each γ such that at least one α is 1 and at least one β is 1, and α and β are the same or different for each γ.
78 . The method of claim 77 wherein the catalyst is a strong protic acid catalyst and further comprising neutralizing the catalyst after affecting the first reaction, the second reaction, or both.
79 . The method of claim 77 further comprising removing the compound of structure VII during or after forming the second ketal.
80 . A method of making a compound having structure I wherein R 8 and R 9 are hydrogen, all Z are O, and all R 4 and R 5 are covalent bonds, the method comprising
a. reacting sorbitol or mannitol with at least 3 molar equivalents of a dialkyl ketone of the formula O═CR 6 R 7 wherein R 6 and R 7 are independently linear, branched, or cyclic alkyl groups having between 3 and 6 carbon atoms to form a first ketal in the presence of a catalyst; and b. reacting the first ketal with at least one molar equivalent of one or more compounds comprising structure VII
wherein
R 1 is hydrogen, a metal cation, an organic cation, a linear, branched, or cyclic alkyl, a linear, branched, or cyclic alkenyl, alkynyl, aryl, alkaryl, or an oligomeric or polymeric moiety;
R 2 is a covalent bond or a linear or branched alkyl group;
R 3 is a linear, branched, or cyclic alkyl group; and
Z is O
to form a second ketal having a structure comprising compound I
wherein
R, R 1 , R 2 , R 3 , R 6 , and R 7 are as defined in structure VII;
R 8 and R 9 are hydrogen,
all Z are O,
all R 4 and R 5 are covalent bonds,
γ is an integer of at least 1, and
α and β are independently 0 or 1 for each γ such that at least one α is 1 and at least one β is 1, and α and β are the same or different for each γ.
81 . The method of claim 80 wherein the catalyst is a strong protic acid catalyst and further comprising neutralizing the catalyst.
82 . The method of claim 80 further comprising removing dialkyl ketone after forming the second ketal.
83 . The method of claim 80 wherein greater than about 80 mole percent of compound I comprises
84 . A method of making a compound comprising at least one repeat unit of structure (IV) wherein Z and Z′ are NR where R is hydrogen or an alkyl group having between 1 and 6 carbon atoms, the method comprising:
a) contacting a bisketal carboxylate of formula (I)
wherein
R 1 is R 1 is hydrogen, a linear, branched, or cyclic alkyl, a linear, branched, or cyclic alkenyl, alkynyl, aryl, alkaryl, or an oligomeric or polymeric moiety, wherein R 1 is the same or different for each occurrence;
R 2 is a covalent bond or a linear or branched alkyl group wherein R 2 is the same or different for each occurrence;
R 3 is the same or different for each occurrence and is a linear, branched, or cyclic alkyl group, or at least one R 3 is
wherein
n is 0, 1, or 2,
R′ is a linear or branched alkyl having between 1 and 6 carbon atoms, and
X is O or NR, wherein R is hydrogen or a linear or branched alkyl group having six or less carbon atoms;
R 4 is a covalent bond, methylene, or alkylmethylene, wherein a covalent bond indicates a 5-membered ring and a methylene or alkylmethylene indicates a 6-membered ring, wherein R 4 is the same or different for each occurrence;
R 5 is a covalent bond, methylene, ethylene, hydroxymethylene, —CH 2 —O—CH 2 —, or a polymeric moiety, wherein R 5 is the same or different for each occurrence;
R 6 and R 7 are independently linear, branched, or cyclic alkyl groups;
R 8 and R 9 are independently hydrogen, a linear, branched, or cyclic alkyl, a linear, branched, or cyclic alkenyl, alkynyl, aryl, alkaryl, or a polymeric moiety;
Z is O;
γ is an integer of at least 1; and
α is 0 or 1 and β is at least two for each γ, and α and β are the same or different for each γ
and a diamine of formula RHN—R 1 —NRH
wherein
R is hydrogen or an alkyl group having between 1 and 6 carbon atoms and
R 1 is a divalent linear, branched, or cyclic alkyl, a linear, branched, or cyclic alkenyl, alkynyl, aryl, or alkaryl moiety; and
b. heating the contacted bisketal carboxylate of formula (I) and the diamine at a pressure and for a time effective to form the polymer of formula IV:
wherein
R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , Z, Z′, and α are as defined above; and δ is an integer of at least 1.Cited by (0)
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