Method of preparing modified polysiloxane containing polymers

Claim 3

The method according to claim 1 in which said siloxane-containing polyimide or poly(amide-imide) is a thermoplastic and/or soluble polyimide or poly(amide-imide).

Claim 4

The method according to claim 1 in which said polyimide of poly(amide-imide) is heated to a temperature of at least about 150° C.

Claim 5

The method according to claim 1 in which said siloxane-containing polyimide or poly(amide-imide) contains a siloxane unit of formula ##STR24## where Q is a substituted or unsubstituted aromatic group Z is ##STR25## D is unsubstituted or substituted hydrocarbylene; R 1 , R 2 , R 3 , R 4 , R 5 and R 6 each independently is unsubstituted or substituted hydrocarbyl; x, y and z each independently has a value from 0 to 100.

Claim 6

The method according to claim 4 in which Q is substituted or unsubstituted carbocyclic aromatic of 6 to 18 ring carbon atoms or substituted or unsubstituted heterocyclic aromatic of 5 to 18 ring atoms where the hetero atoms are selected from N, O and S, and where the substituents are alkyl of 1 to 12 carbon atoms, alkenyl of 2 to 12 carbon atoms, alkynyl of 2 to 12 carbon atoms, cycloalkyl of 4 to 8 carbon atoms, alkoxy of 1 to 12 carbon atoms, alkylthio of 1 to 12 carbon atoms, phenyl, alkylphenylene having 1 to 12 carbon atoms in the alkyl group, phenoxy, phenylthio, alkylcarbonyloxy of 2 to 12 carbon atoms, phenylalkylene of 1 to 12 carbon atoms in the alkylene group, alkylcarbonyl of 2 to 12 carbon atoms, alkoxycarbonyl of 2 to 12 carbon atoms, bromo, chloro, fluoro, iodo, nitro, cyano, cyanothio, carboxy, carbonyl, hydroxy, mercapto, formyl, thioformyl or mercaptocarbonyl; D is substituted or unsubstituted hydrocarbylene of 1 or 3 to 18 carbon atoms; R 1 , R 2 , R 3 , R 4 , R 5 and R 6 each independently, is an unsubstituted or substituted alkyl of 1 to 12 carbon atoms, alkenyl of 2 to 12 carbon atoms, alkynyl of 2 to 12 carbon atoms, cycloalkyl of 4 to 8 carbon atoms, phenyl, alkylphenylene where the alkyl group contains 1 to 12 carbon atoms, phenylalkylene where the alkylene group contains 1 to 12 carbon atoms, or alkenylphenylene with 2 to 12 carbon atoms in the alkenyl group and when substituted, these hydrocarbyl groups are substituted by Br, Cl, I, F, --NC, --NO 2 , --OCN, alkoxy of 1 to 8 carbon atoms, --S--(C 1 -C 8 )alkyl, ##STR26## --S--S--(C 1 -C 8 )alkyl, --COOH, --COSH, --CSOH, --CONH 2 , --CN, --CHO, --CHS, --OH, --SH, --NCO or --NR 7 R 8 where R 7 and R 8 independently are hydrogen or lower alkyl.

Claim 7

The method according to claim 5 in which Q is unsubstituted or substituted carbocyclic aromatic of 6 to 18 ring carbon atoms; D is branched or linear alkylene of 1 or 3 to 12 carbon atoms; and x, y and z is each 0.

Claim 8

The method according to claim 6 which the siloxane unit has the formula ##STR27## where v is 0 to 4 R 9 is each independently lower alkyl, lower alkenyl, lower alkynyl, cycloalkyl of 4 to 8 carbon atoms, lower alkoxy, lower alkylthio, phenyl, loweralkylphenylene, phenyl loweralkylene, loweralkenylphenylene, phenoxy, phenylthio, loweralkylcarbonyl, loweralkylcarbonyloxy, loweralkoxycarbonyl, bromo, chloro, fluoro, iodo, nitro, cyano, cyanothio, carboxyl, carbonyl, hydroxyl, mercapto or mercaptocarbonyl; Z is ##STR28## D 1 is methylene or alkylene of 3 to 8 carbon atoms; R 1 is lower alkyl, lower alkenyl, lower alkynyl, phenyl, loweralkylphenylene, phenylloweralkylene, or loweralkenylphenylene.

Claim 9

The method according to claim 7 in which v is 0 or 1 and R 1 is lower alkyl.

Claim 10

The method according to claim 7 in which v is 0 or 1; Z is --O--; R 1 is lower alkyl.

Claim 11

The method according to claim 7 in which v is 0 or 1; Z is --O--; D 1 is methylene, propylene or butylene; R 1 is alkyl of 1 to 3 carbon atoms.

Claim 12

The method according to claim 7 in which v is 0; Z is --O--; D 1 is methylene or butylene; and R 1 is methyl.

Claim 13

The method according to claim 5 in which Q is unsubstituted or substituted carbocyclic aromatic of 6 to 18 ring carbon atoms; D is branched or linear alkylene of 1 or 3 to 12 carbon atoms; x has a value from 0 to 100; y has a value from 0 to 20; z has a value from 0 to 20.

Claim 14

The method according to claim 4 in which R 1 is unsubstituted hydrocarbyl of 1 to 18 carbon atoms; R 2 is alkyl of 1 to 12 carbon atoms; R 3 is phenyl, alkylphenylene of 7 to 18 carbon atoms, or alkyl of 1 to 12 carbon atoms; R 4 is alkyl of 1 to 12 carbon atoms, phenyl, alkylphenylene of 7 to 18 carbon atoms, or alkenyl of 2 to 12 carbon atoms; R 5 is alkenyl of 2 to 12 carbon atoms, or substituted alkyl of 1 to 12 carbon atoms; R 6 is alkyl of 1 to 12 carbon atoms, phenyl, alkylphenylene of 7 to 18 carbon atoms, or alkenyl of 2 to 12 carbon atoms.

Claim 15

The method according to claim 13 in which the siloxane unit has the formula ##STR29## where v is 0 or 4; R 9 is each independently lower alkyl, lower alkenyl, lower alkynyl, cycloalkyl of 4 to 8 carbon atoms, lower alkoxy, lower alkylthio, phenyl, loweralkylphenylene, phenylloweralkylene, loweralkenylphenylene, phenoxy, phenylthio, loweralkylcarbonyl, loweralkylcarbonyloxy, loweralkoxycarbonyl, bromo, chloro, fluoro, iodo, nitro, cyano, cyanothio, carboxyl, carbonyl, hydroxyl, mercapto or mercaptocarbonyl; Z is ##STR30## D 1 is methylene or alkylene of 3 to 8 carbon atoms.

Claim 16

The method according to claim 14 in which R 1 is lower alkyl, lower alkenyl, lower alkynyl, phenyl, lower alkylphenylene, phenyl lower alkylene, or lower alkenylphenylene; R 2 is alkyl of 1 to 12 carbon atoms; R 3 is phenyl, alkyl phenylene of 7 to 18 carbon atoms or alkyl of 1 to 12 carbon atoms; R 4 is alkyl of 1 to 12 carbon atoms, phenyl, alkylphenylene of 7 to 18 carbon atoms, or alkenyl of 2 to 12 carbon atoms; R 5 is alkynyl of 2 to 12 carbon atoms or substituted alkyl of 1 to 12 carbon atoms; R 6 is alkyl of 1 to 12 carbon atoms, phenyl, alkylphenylene of 7 to 18 carbon atoms, or alkenyl of 2 to 12 carbon atoms.

Claim 17

The method according to claim 15 in which v is 0 or 1; D 1 is methylene or alkylene of 3 to 8 carbon atoms; R 1 is lower alkyl; R 2 is lower alkyl; R 3 is lower alkyl or phenyl; R 4 is lower alkyl, phenyl, or lower alkenyl; R 5 is lower alkenyl or substituted lower alkyl; R 6 is lower alkyl or lower alkenyl; the substituents on R 4 , R 5 and R 6 lower alkyls being independently selected from halogen, amino, cyano, --CONH 2 , hydroxyl and mercapto; x has a value from 0 to 100; y has a value from 0 to 20; and z has a value from 0 to 20.

Claim 18

The method according to claim 16 in which v is 0 or 1; Z is --O-- or --S--; D 1 is methylene, propylene or butylene; R 1 is alkyl of 1 to 3 carbon atoms; R 2 is alkyl of 1 to 3 carbon atoms; R 3 is alkyl of 1 to 3 carbon atoms or phenyl; R 4 is alkyl of 1 to 3 carbon atoms, alkenyl of 2 to 4 carbon atoms, phenyl or said alkyl substituted by amino, cyano, hydroxyl or --CONH 2 ; R 5 is alkenyl of 2 to 4 carbon atoms or alkyl of 1 to 3 carbon atoms substituted by amino, cyano, hydroxyl or --CONH 2 ; R 6 is alkyl of 1 to 3 carbon atoms, alkenyl of 2 to 4 carbon atoms or alkyl of 1 to 3 carbon atoms substituted by amino, cyano, hydroxyl or --CONH 2 ; x has a value from 0 to 100; y has a value from 0 to 20; and z has a value from 0 to 20.

Claim 19

The method according to claim 13 in which v is 0; Z is --O--; D 1 is methylene or butylene; R 1 is methyl; R 2 is methyl; R 3 is methyl or phenyl; R 4 is methyl, vinyl or phenyl; R 5 is vinyl or methyl, ethyl or propyl substituted by amine, cyano, hydroxyl or --CONH 2 ; R 6 is methyl, vinyl or methyl, ethyl or propyl substituted by amino, cyano, hydrogen or --CONH 2 ; x has a value from 0 to 100; y has a value from 0 to 20; and z has a value from 0 to 10.

Claim 20

The method according to claim 5 in which Q is substituted or unsubstituted heterocyclic aromatic of 5 to 18 ring atoms, where the hetero atoms are selected from N, O and S; D is branched or linear alkylene of 1 or 3 to 12 carbon atoms; and x, y and z, each, independently, has a value from 0 to 100.

Claim 21

The method according to claim 19 in which the heterocyclic nucleus is pyridinyl, pyridazinyl, pyrimidinyl, pyrazinyl, furanyl, thiofuranyl, pyrrollinyl, indenyl, benzofuranyl, benzothiofuranyl, indolinyl, quinolinyl or isoquinolinyl.

Claim 22

The method according to claim 1 in which said polyimide or poly(amide-imide) comprises the reaction product of an organic acid, anhydride or acid-anhydride with a bis(amino)polysiloxane of formula ##STR31## where Q is a substituted or unsubstituted aromatic group; Z is ##STR32## D is unsubstituted or substituted hydrocarbylene; R 1 , R 2 , R 3 , R 4 , and R 5 and R 6 each independently is unsubstituted or substituted hydrocarbyl; x, y and z each independently has a value from 0 to 100.

Claim 23

The method according to claim 1 in which said polyimide comprises the reaction product of a dianhydride component with an amine component, the dianhydride component comprising a dianhydride of formula ##STR33## where A is a tetravalent benzene or naphthalene nucleus or a tetravalent group of formula ##STR34## wherein G is phenylene or a group of formula ##STR35## and where m and m 1 is each 0 or 1 and E and E 1 is each ##STR36## where y is an integer from 1 to 8; the amine component comprising a bis(amino)polysiloxane having the formula ##STR37## where Q is a substituted or unsubstituted aromatic group; Z is ##STR38## D is substituted or unsubstituted hydrocarbylene of 1 or 3 to 18 carbon atoms; R 1 , R 2 , R 3 , R 4 , R 5 and R 6 each independently is unsubstituted or substituted hydrocarbyl; and x, y and z, each independently, has a value from 0 to 100.

Claim 24

The method according to claim 1 in which said polyimide or poly(amide-imide) contains a siloxane unit which is a C.sub.(3-8) alkylene terminated polydiorganosiloxane.

Claim 25

The method according to claim 23 in which said siloxane unit is of the formula ##STR39## wherein R 1 is a monovalent hydrocarbon radical; R 2 is a divalent hydrocarbon radical; and s is zero or a whole number of at least 1.

Claim 26

The method according to claim 1 in which said reactive hydrogen containing compounds is an organic alcohol or a thiol.

Claim 27

The method according to claim 25 in which said reactive hydrogen containing compound contains at least three reactive hydrogen containing groups.

Claim 28

A polyimide or poly(amide-imide) which is prepared by the method of claim 1.

Claim 29

A polyimide or poly(amide-imide) which is prepared by the method of claim 25.

Claim 30

A polyimide or poly(amide-imide) which is prepared by the method of claim 26.

Claim 33

The method according to claim 30 in which said siloxane-containing polyimide or poly(amide-imide) contains said alcohol, phenol or thiol incorporated therein.

Claim 34

The method according to claim 30 in which said polyimide or poly(amide-imide) contains a siloxane unit of formula ##STR40## where Q is a substituted or unsubstituted aromatic group Z is ##STR41## D is unsubstituted or substituted hydrocarbylene; R 1 , R 2 , R 3 , R 4 , R 5 and R 6 each independently is unsubstituted or substituted hydrocarbyl; x, y and z each independently has a value from 0 to 100.

Claim 35

The method according to claim 30 in which said polyimide or poly(amide-imide) contains a siloxane unit which is a C.sub.(3-8) alkylene terminated polydiorganosiloxane.

Claim 36

The method according to claim 30 in which said polyimide or poly(amide-imide) is dissolved in a solvent.

Claim 37

The method according to claim 33 in which said substrate comprises a semiconductor device.

Claim 38

The method according to claim 33 in which said substrate comprises conductive wire, or fibers or filaments of carbon, glass, metal, ceramic, polyimide or fabrics woven therefrom.

Claim 39

The method according to claim 3 in which said polyimide or poly(amide-imide) is heated for at least about 30 minutes.

Claim 40

The method according to claim 30 in which said substrate is heated for at least about 30 minutes.

Claim 41

A siloxane containing polyimide or poly(amide-imide) composition containing an organic alcohol, a phenol or a thiol.

Claim 42

A siloxane containing polyimide or poly(amide-imide) composition containing an organic alcohol, a phenol or a thiol.

Claim 43

The composition according to claim 39 in which said alcohol, phenol or thiol is present in an amount of at least 0.5 mole percent based on the weight of said composition.

Claim 44

The method according to claim 22 wherein the amine component includes an organic diamine having the formula H.sub.2 N--Y--NH.sub.2 where Y is phenylene, diphenylene, naphthylene or a group of formula ##STR42## where R 7 is branched or linear alkylene of 1 to 20 carbon atoms, ##STR43## or --O--, or R 7 is --O--G'--O--, where G' is phenylene or group of formula ##STR44## where m 3 is 0 or 1 and E 3 is ##STR45## or linear or branched alkylene of 1 to 8 carbon atoms.