Oligomers with multiple chemically functional end caps
AssigneeThe Boeing Company
InventorsHyman R. Lubowitz, Clyde H. Sheppard
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Abstract
Thermomechanical and thermo-oxidative stabilities in resin composites across the range of aerospace "engineering thermoplastic" resins are improved by forming four crosslinks at each addition polymerization site in the backbone of the resin using crosslinking functionalities of the general formula: ##STR1## wherein Z= ##STR2## .beta.=the residue an organic radical selected from the group consisting of: ##STR3## R.sub.R =a divalent organic radical; X=halogen; Me=methyl T=allyl or methallyl. G=--CH.sub.2 --,--S--, --CO--, --SO--, --O--, --CHR.sub.3 --, or --C(R.sub.3).sub.2 --; i=1 or 2; R.sub.3 =hydrogen, lower alkyl, lower alkoxy, aryl, or aryloxy; and .theta.=--C.tbd.N, --O--C.tbd.N, --S--C.tbd.N, or --CR.sub.3 .dbd.C(R.sub.3).sub.2 --
Claims32
A linear or multidimensional oligomer having two or four crosslinking sites at each end of its backbone, comprising:
- ##STR115## wherein Z is ##STR116## i is 1 or2 .O slashed. is phenylene;
- E is ##STR117## .O slashed. is --C.tbd.N, --O--C.tbd.N, --S--C.tbd.N, or --CR.sub.3 =C(R.sub.3).sub.2 ;
- .differential. is an organic hub;
- w is 3 or4
- Me is methyl;
- G is --CH.sub.2 --, --C(HR.sub.3)--, --C(R.sub.3).sub.2 --, --S--, --SO.sub.2 --, --O--, or --CO--;
- R.sub.3 is lower alkyl, lower alkoxy, aryl, aryloxy or hydrogen;
- T is allyl or methallyl;
- and
- R.sub.4 is a divalent organic radical.
A multiple chemically functional ester oligomer of the formula:
- ##STR118## wherein P.sub.# is ##STR119## .delta. is phenylene or pyrimidinylene;
- i is 1 or2;
- Z is ##STR120## .O slashed. is phenylene;
- ##STR121## .O slashed. is --C.tbd.N, --O--C.tbd.N, --S--C.tbd.N, or --CR.sub.3 .dbd.C(R.sub.3).sub.2 ;
- j is 0, 1, or 2;
- G is --CH.sub.2 --, --C(HR.sub.3)--, --C(R.sub.3).sub.2 --, --S--, --SO.sub.2 --, --O--, or --CO--;
- R.sub.3 is hydrogen, lower alkyl, lower alkoxy, aryl, or aryloxy;
- Me is methyl;
- and
- T is methallyl or allyl.
- R.sub.@ is a divalent ester hydrocarbon radical formed by the condensation of a diol with a diacid halide, wherein at least one of the diol or diacid halide has a repeating unit of the formula:
- --.O slashed.--L--.O slashed.--
- or
- --.O slashed.--O--.O slashed.--L--.O slashed.--O--.O slashed.--
- wherein L is --SO.sub.2 --, --S--, --CO--, --(CF.sub.3).sub.2 C--, or --(CH.sub.3).sub.2 C--.
A crosslinkable polyimide oligomer having the general formula:
- ##STR122## wherein .xi. is the residue of an extended amine end cap monomer of the formula:
- ##STR123## wherein .xi. is ##STR124## i is 1 or 2;
- .O slashed. is phenylene;
- ##STR125## Me is methyl;
- G is --CH.sub.2 --, --SO.sub.2 --, --CO--, --S--, --O--, --C(HR.sub.3)--, or C(R.sub.3).sub.2 --;
- .beta. is --O--.O slashed.--NH.sub.2 ;
- R.sub.3 is independently any of hydrogen, lower alkyl, lower alkoxy, aryl, or aryloxy;
- .O slashed. is --C.tbd.N, --O--C.tbd.N, --S--C--.tbd.N, or --CR.sub.3 .dbd.C(R.sub.3).sub.2 ;
- X is halogen;
- T is allyl or methallyl;
- R.sub.8 &R*.sub.8 is a divalent organic aromatic radical,
- provided that .O slashed. is not --C.tbd.N, --OCN, or --SCN, when .beta. is --O--R*.sub.8 --OCN;
- A is the residue of a dianhydride;
- B is the residue of a diamine;
- and
- m is a small integer, generally less than 20.
A coreactive oligomer blend comprising a mixture of a first oligomer of the general formula:
- .xi.--A--.xi.
- wherein A is a hydrocarbon backbone;
- and
- .xi. is an unsaturated hydrocarbon residue of an end cap monomer of the formula:
- ##STR126## and a second oligomer of the general formula:
- Z*.sub.k --B--Z*.sub.k
- wherein k is 1, 2, or 4;
- B is a hydrocarbon backbone;
- Z* is a hydrocarbon residue terminating in any of:
- ##STR127## Y is ##STR128## i is 1 or 2;
- E is an unsaturated organic radical being any of:
- ##STR129## R.sub.1 is lower alkyl, lower alkoxy, aryl, or aryloxy;
- R.sub.3 is lower alkyl, lower alkoxy, aryl, aryloxy or hydrogen;
- j is 0, 1 or 2;
- G is --CH.sub.2 --, --S--, --O--, --(Me)CH--, or --(Me).sub.2 C--;
- Me is methyl;
- T is methallyl or allyl;
- .O slashed. is --C.tbd.N, --O--C.tbd.N, --S--C.tbd.N, or --CR.sub.3 .dbd.C(R.sub.3).sub.2 ;
- Z is ##STR130## .O slashed. is phenylene;
- .beta. is an organic radical being any of:
- ##STR131## R.sub.8 and R*.sub.8 is a divalent organic aromatic radial, provided that .O slashed. is not --C.tbd.N, --OCN, or --SCN, when .beta. is --O--R*.sub.8 --OCN.
A linear polyamideimide oligomer, comprising a compound of the general formula:
- .xi.--A--.xi.
- wherein A is a divalent radical including at least one segment selected from the group consisting of:
- ##STR132## .xi. is a residue of an extended amine end cap monomer of the formula:
- ##STR133## Z is ##STR134## i is 1 or 2;
- .O slashed. is phenylene;
- ##STR135## Me is methyl;
- G is --CH.sub.2 --, --SO.sub.2 --, --CO--, --S--, --O--, --C(HR.sub.3)--, or --C(R.sub.3).sub.2 --;
- .beta. is --O--.O slashed.--NH.sub.2 or --O--.O slashed.--COX;
- R.sub.3 is independently any of hydrogen, lower alkyl, lower alkoxy, aryl, or aryloxy;
- .O slashed. is --C.tbd.N, --O--C.tbd.N, --S--C.tbd.N, or --CR.sub.3 .dbd.C(R.sub.3).sub.2 ;
- X is halogen;
- T is allyl or methallyl;
- R*.sub.8 are a divalent organic aromatic radical;
- R.sub.2 is phenylene;
- and
- R.sub.8 is the residue of a diamine.
An advanced composite blend comprising a mixture of at least one oligomer of the general formula:
- .mu.--a--.xi.
- wherein t is an unsaturated hydrocarbon residue of an end cap monomer of the formula:
- ##STR136## .O slashed. is phenylene;
- .beta. is an organic radical being any of:
- ##STR137## and R.sub.8 and R*.sub.8 is a divalent organic aromatic radial, provided that .O slashed. is not --C.tbd.N, --OCN, or --SCN, when .beta. is --O--R*.sub.8 --OCN.
- i is 1 or 2;
- E is an unsaturated organic radical being any of:
- ##STR138## R.sub.1 is lower alkyl, lower alkoxy, aryl, or aryloxy;
- R.sub.3 is lower alkyl, lower alkoxy, aryl, aryloxy or hydrogen,
- j is 0, 1or2;
- G is --CH.sub.2 --, --S--, --O--, --(Me)CH--, or --(Me).sub.2 C--;
- Me is methyl;
- T is methallyl or allyl;
- .O slashed. is --C.tbd.N, --O--C.dbd.N, --S--C.tbd.N, or --CR.sub.3 .dbd.C(R.sub.3).sub.2 ;
- and
- A is a hydrocarbon residue including an aromatic, aliphatic, or mixed aromatic and aliphatic backbone, and at least one compatible polymer from a different chemical family than the oligomer.
An advanced composite blend comprising a mixture of at least one linear or multidimensional crosslinkable oligomer having at least four unsaturated hydrocarbon functionalities at each end of a linear backbone or of a multidimensional arm and at least one noncrosslinking polymer, wherein, prior to curing, the oligomer has an average formula weight less than that of the polymer.
A crosslinkable oligomer having the general formula:
- ##STR139## wherein .xi. is a residue of an extended amine end cap of the formula:
- Z--.delta.--.O slashed.--NH.sub.2 ;
- .delta. is phenylene or pyrimidinylene;
- i is 1 or2;
- Z is ##STR140## E is ##STR141## .O slashed. is --C.tbd.N, --O--C.tbd.N, --S--C.tbd.N, or --CR.sub.3 .dbd.C(R.sub.3).sub.2 ;
- j is 0, 1, or 2;
- G is --CH.sub.2 --, --SO.sub.2 --, --CO--, --S--, --O--, --C(HR.sub.3)--, or --C(R.sub.3).sub.2 --;
- R.sub.3 is hydrogen, lower alkyl, lower alkoxy, aryl, or aryloxy
- Me is methyl;
- T is methallyl or allyl;
- w is 3 or4
- .differential. is an organic hub of valency "w";
- A is the residue of a dianhydride;
- and
- B is the residue of a diamine.
A multiple chemically functional ether oligomer of the formula:
- ##STR142## wherein .delta. is phenylene or pyrimidinylene;
- i is 1 or 2;
- Z is ##STR143## .O slashed. is phenylene;
- ##STR144## .O slashed. is --C.tbd.N, --O--C.tbd.N, --S--C.tbd.N, or --CR.sub.3 .dbd.C(R.sub.3).sub.2 ;
- j is 0, 1,or2;
- G is --CH.sub.2 --, --C(HR.sub.3)--, --C(R.sub.3).sub.2 --, --S--, --SO.sub.2 --, --O--, or --CO--;
- R.sub.3 is hydrogen, lower alkyl, lower alkoxy, aryl, or aryloxy;
- Me is methyl;
- and
- T is methallyl or allyl.
- R.sub.e is a divalent ester hydrocarbon radical formed by the condensation of a diol with a dihalogen or dinitro, wherein at least one of the diol or the dihalogen/dinitro has a repeating unit of the formula:
- --.O slashed.--L--.O slashed.--
- or
- --.O slashed.--O--.O slashed.--L--.O slashed.--O--.O slashed.--
- wherein L is --SO.sub.2 --, --S--, --CO--, --(CF.sub.3).sub.2 C--, or --(CH.sub.3).sub.2 C--.
An ether or ester oligomer useful in forming advanced composites that have thermal stability and high glass transition temperatures, comprising a multidimensional compound of the general formula:
- Ar--(--P--(R--T--).sub.n --.xi.)hd 3
- wherein P is ##STR145## T is ##STR146## n is an integer such that the molecular weight of the repeating --R--T segment is between about 0-3000;
- R is phenyl, biphenyl, naphthyl, or a hydrocarbon chain having linked aromatic radicals connected with at least one electronegative linkage selected form the group consisting of --SO.sub.2 --, --CO--, --S--, and --(CF.sub.3).sub.2 C--,
- Ar is a trivalent aromatic radical;
- .xi. is phenylene or pyrimidinylene;
- i is 1 or2;
- Z is ##STR147## .O slashed. is --C.tbd.N, --O--C.tbd.N, --S--C.tbd.N, or --CR.sub.3 =C(R.sub.3).sub.2 ;
- j is O,1,or2;
- G is --CH.sub.2 --, --C(HR.sub.3)--, --C(R.sub.3).sub.2 --, --S--, --SO.sub.2 --, --O--, or --CO--;
- R.sub.3 is hydrogen, lower alkyl, lower alkoxy, aryl, or aryloxy;
- Me is methyl;
- and
- T is methallyl or allyl.
A carbonate oligomer of the formula:
- ##STR148## wherein R.sub.c is a divalent organic carbonate radical or a carbonate linkage;
- i is 1 or 2;
- w is 3 or 4;
- .delta. is phenylene or pyrimidinylene;
- .differential. is a "w" valent organic radical;
- w is 3 or 4 ##STR149## G is --CH.sub.2 --, --SO.sub.2 --, --CO--, --S--, --O--, --C(HR.sub.3)--, or --C(R).sub.3 --;
- T is allyl or methallyl;
- Me is methyl;
- R.sub.3 is lower alkyl, lower alkoxy, aryl, aryloxy, or hydrogen;
- and
- .O slashed. is --C.tbd.N, --O--C.tbd.N, --S--C.tbd.N, or --CR.sub.3 .dbd.C(R.sub.3).sub.2.
Dependencies are inferred from the claim text.