US 6,645,743 B1Granted

Polyhydroxyalkanoate copolymer containing in molecule unit with vinylphenyl structure in its side chain and method of manufacturing the same

AssigneeCanon Kabushiki Kaisha

InventorsTsutomu Honma, Etsuko Sugawa, Tetsuya Yano, Takeshi Imamura, Takashi Kenmoku, Tatsuki Fukui

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Abstract

A polyhydroxyalkanoate (PHA) having a desired configuration is produced using a raw material containing ω-(4-vinylphenyl)-alkanoic acid and (ω-substituted alkanoic acid in which a group having a ring structure selected from phenyl, thienyl, and cyclohexyl structures substitutes therefor on the end thereof by producing a PHA copolymer containing the corresponding 3-hydroxy-ω-(4-vinylphenyl)-alkanoate unit and the corresponding 3-hydroxy-ω-substituted alkanoate unit by making use of a microorganism capable of producing the PHA or by oxidizing a predetermined portion of the corresponding PHA.

Claims16

Dependent claims

A polyhydroxyalkanoate copolymer comprising in the same molecule:

a 3-hydroxy-ω-(4-vinylphenyl)-alkanoate unit represented by the general formula (1):
where n represents an integer of 0 to 7, and n independently represents the integer for each unit when the plural units are present;
and
at least one unit selected from the group consisting of:
a 3-hydroxy-ω-substituted alkanoate unit represented by the general formula (2):
where m represents an integer of 1 to 8, and R1 represents a group having a residue with a ring structure selected from a phenyl structure and a thienyl structure;
and
a 3-hydroxy-ω-cyclohexyl-alkanoate unit represented by the general formula (3):
where R2 represents a substituent for a cyclohexyl group and R2 represents a hydrogen atom, a CN group, an NO2 group, a halogen atom, a CH3 group, a C2H5 group, a C3H7 group, a CF3 group, a C2F5 group, or a C3F7 group, and k represents an integer of 0 to 8, in which m and R1 independently represent the integer and the group, respectively, for each unit when the plural units represented by the general formula (2) are present, and k and R2 independently represent the integer and the substituent, respectively, for each unit when the plural units represented by the general formula (3) are present.

6 more elements

A method of manufacturing a polyhydroxyalkanoate copolymer that contains in the same molecule:

a 3-hydroxy-ω-(4-vinylphenyl)-alkanoate unit represented by the general formula (1):
where n represents an integer of 0 to 7, and n independently represents the integer for each unit when the plural units are present;
and
at least one unit selected from the group consisting of:
a 3-hydroxy-ω-substituted alkanoate unit represented by the general formula (19):
where s represents an integer of 1 to 8, and R19 represents a group having a residue with a ring structure selected from a phenyl structure and a thienyl structure;
and
a 3-hydroxy-ω-cyclohexyl-alkanoate unit represented by the general formula (3):
where R2 represents a substituent for a cyclohexyl group and R2 represents a hydrogen atom, a CN group, an NO2 group, a halogen atom, a CH3 group, a C2H5 group, a C3H7 group, a CF3 group, a C2F5 group, or a C3F7 group, and k represents an integer of 0 to 8, in which s and R19 independently represent the integer and the group, respectively, for each unit when the plural units represented by the general formula (19) are used, and k and R2 independently represent the integer and the substituent, respectively, for each unit when the plural units represented by the general formula (3) are present,
the method comprising:
allowing a microorganism capable of synthesizing the polyhydroxyalkanoate copolymer from a raw material to synthesize the polyhydroxyalkanoate by making the microorganism act on the raw material including:
(A) at least one ω-(4-vinylphenyl)-alkanoic acid represented by the following general formula (16):
where p represents an integer of 0 to 7;
and
(B) at least one component selected from the group consisting of ω-substituted alkanoic acid represented by the general formula (17):
where q represents an integer of 1 to 8, and R17 represents a group containing a residue with a ring structure selected from a phenyl structure and a thienyl structure, and
ω-cyclohexyl-alkanoic acid represented by the general formula (18):
where R18 represents a hydrogen atom, a CN group, an NO2 group, a halogen atom, a CH3 group, a C2H5 group, a C3H7 group, a CF3 group, a C2F5 group, or a C3F7 group, and r represents an integer of 0 to 8.

15 more elements

A method of manufacturing a polyhydroxyalkanoate that contains in the same molecule:

at least a 3-hydroxy-ω-(4-vinylphenyl)-alkanoate unit represented by the general formula (1):
where n represents an integer of 0 to 7, and n independently represents the integer for each unit when the plural units represented by the general formula (1) are present;
and
at least one unit selected from the group consisting of a 3-hydroxy-ω-substituted alkanoate unit represented by the general formula (2):
where m represents an integer of 1 to 8, and R1 represents a group containing a residue with a ring structure selected from a phenyl structure and a thienyl structure, and a 3-hydroxy-ω-cyclohexyl-alkanoate acid unit represented by the general formula (3):
where R2 represents a substituent for a cyclohexyl group and R2 represents a hydrogen atom, a CN group, an NO2 group, a halogen atom, a CH3 group, a C2H5 group, a C3H7 group, a CF3 group, a C2F5 group, or a C3F7 group, and k represents an integer of 0 to 8, in which m and R1 independently represent the integer and the group, respectively, for each unit when the plural units represented by the general formula (2) are present, and k and R2 independently represent the integer and the substituent, respectively, for each unit when the plural units represented by the general formula (3) are present,
the R1 containing at least a group selected from the group consisting of a substituted phenyl group represented by the following general formula (4′), an unsubstituted or substituted phenylsulfinyl group represented by the general formula (12), and an unsubstituted or substituted phenylsulfonyl group represented by the general formula (13):
where R3′ represents COOR4 (R4 represents a hydrogen atom, a sodium atom, or a potassium atom);
where R13 represents a hydrogen atom, a halogen atom, a CN group, an NO2 group, COOR14, SO2R15 (R14 represents H, Na, K, CH3, or C2H5, and R15 represents OH, ONa, OK, a halogen atom, OCH3, or OC2H5), a CH3 group, a C2H5 group, a C3H7 group, a (CH3)2—CH group, or a (CH3)3—C group;
and
where R16 represents a hydrogen atom, a halogen atom, a CN group, an NO2 group, COOR17, SO2R18 (R17 represents H, Na, K, CH3, or C2H5, and R18 represents OH, ONa, OK, a halogen atom, OCH3, or OC2H5), a CH3 group, a C2H5 group, a C3H7 group, a (CH3)2—CH group, or a (CH3)3—C group,
the method comprising one of the steps of:
(a) oxidizing a part of a vinyl group contained in a phenyl group of a group represented by the general formula (1) of a raw material to form the group represented by the general formula (4′) as the R1, with the raw material including a polyhydroxyalkanoate copolymer containing in the same molecule:
two or more 3-hydroxy-ω-(4-vinylphenyl)-alkanoate units represented by the general formula (1):
where n represents an integer of 0 to 7, and n independently represents the integer for each unit;
and at least one unit selected from the group consisting of a 3-hydroxy-ω-substituted alkanoate unit represented by the general formula (19):
where s represents an integer of 1 to 8 and R19 represents a group having a residue with a ring structure selected from a phenyl structure and a thienyl structure, and a 3-hydroxy-ω-cyclohexyl-alkanoate unit represented by the general formula (3):
where R2 represents a substituent for a cyclohexyl group and R2 represents a hydrogen atom, a CN group, an NO2 group, a halogen atom, a CH3 group, a C2H5 group, a C3H7 group, a CF3 group, a C2F5 group, or a C3F7 group, and k represents an integer of 0 to 8, in which s and R19 independently represent the integer and the group, respectively, for each unit when the plural units represented by the general formula (19) are present, and k and R2 independently represent the integer and the substituent, respectively, for each unit when the plural units represented by the general formula (3) are present;
and
(b) selectively oxidizing —S— of the substituent represented by the general formula (7) in a polyhydroxyalkanoate copolymer provided as a raw material to be converted to a group represented by the general formula (12) or a group represented by the general formula (13), with the polyhydroxyalkanoate copolymer containing in the same molecule:
a 3-hydroxy-ω-(4-vinylphenyl)-alkanoate unit represented by the general formula (1):
where n represents an integer of 0 to 7, and n independently represents the integer for each unit when the plural units represented by the general formula (1) are present;
and at least one unit selected from the group consisting of a 3-hydroxy-ω-substituted alkanoate unit represented by the general formula (2):
where m represents an integer of 1 to 8, and R1 represents an unsubstituted or substituted phenylsulfanyl group represented by the general formula (7):
where R7 represents a hydrogen atom, a halogen atom, a CN group, an NO2 group, COOR8, SO2R9 (R8 represents H, Na, K, CH3, or C2H5, and R9 represents OH, ONa, OK, a halogen atom, OCH3, or OC2H5), a CH3 group, a C2H5 group, a C3H7 group, a (CH3)2—CH group, or a (CH3)3—C group, and a 3-hydroxy-ω-cyclohexyl-alkanoate unit represented by the general formula (3):
where R2 represents a substituent for a cyclohexyl group and R2 represents a hydrogen atom, a CN group, an NO2 group, a halogen atom, a CH3 group, a C2H5 group, a C3H7 group, a CF3 group, a C2F5 group, or a C3F7 group, and k represents an integer of 0 to 8, in which m and R1 independently represent the integer and the group, respectively, for each unit when the plural units represented by the general formula (2) are present, and k and R2 independently represent the integer and the substituent, respectively, for each unit when the plural units represented by the general formula (3) are present.

23 more elements

Dependencies are inferred from the claim text.

Facts

Application: 10/372,285Filed 25 Feb 2003
Priority: JP 2002-05489728 Feb 2002
Published: US 2003/0204044 A130 Oct 2003
Granted: 11 Nov 2003
Term ends: Not estimatedThe source records don’t support an estimate.

Classification9 codes

C08G 63/06
Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds: derived from hydroxycarboxylic acids
C08G 63/6882
Containing sulfur: derived from hydroxy carboxylic acids
C12P 7/625
Carboxylic acid esters: polyesters of hydroxy carboxylic acids
C12P 11/00
Preparation of sulfur-containing organic compounds