CA2121051A1 - Oxidation inhibited arylcyclobutene polymers - Google Patents
Oxidation inhibited arylcyclobutene polymersInfo
- Publication number
- CA2121051A1 CA2121051A1 CA002121051A CA2121051A CA2121051A1 CA 2121051 A1 CA2121051 A1 CA 2121051A1 CA 002121051 A CA002121051 A CA 002121051A CA 2121051 A CA2121051 A CA 2121051A CA 2121051 A1 CA2121051 A1 CA 2121051A1
- Authority
- CA
- Canada
- Prior art keywords
- antioxidant
- compound
- hydrogen
- group
- arylcyclobutene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
- C08K5/3432—Six-membered rings
- C08K5/3435—Piperidines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
- C08K5/134—Phenols containing ester groups
- C08K5/1345—Carboxylic esters of phenolcarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/17—Amines; Quaternary ammonium compounds
- C08K5/18—Amines; Quaternary ammonium compounds with aromatically bound amino groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
- C08K5/3432—Six-membered rings
- C08K5/3437—Six-membered rings condensed with carbocyclic rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/37—Thiols
- C08K5/375—Thiols containing six-membered aromatic rings
Abstract
The invention is a composition containing a polymer formed by side ring opening of an arylcyclobutene compound and an antioxidant compound of formulae (1), (2), (3), (4), wherein R is hydrogen, an electron withdrawing or electron donating group; and oligomers thereof; hindered amines of formula (5), wherein R is hydrogen, an electron withdrawing group or an electron donating group; each R1 is independently hydrogen, an electron withdrawing group or an electron donating group, with the proviso that two R1 attached to the same carbon may represent a single moiety joined to said carbon by a double bond; each R2 is independently methyl, ethyl, n-propyl or isopropyl; said antioxidant being effective to inhibit oxidation.
Description
W093/11189 2 i2105~ PCI/US~2/10173 OXIDATION INHIBITEDARYLCYCLOBUTENE POLYMERS
This invention relates to polymeric compositions made from arylcyclobutene containing monomers and methods for preventing autoxidation of said polymers.
Arylcyclobutene monomeric compositions are useful in preparing thermoset and thermoplastic polymeric compositions. Such polymeric compositions are highly desirable because they exhibit hydrophobicity, excellent thermal stability, chemital resistance and electrical insulative properties. Such polymeric compositions typical Iy can exhibit thermal degradation temperatures above 300C, are insoluble in many organic solvents and in water 10 and have dielectric constants of less than 3.0 at 1 MHz. Therefore, they find uses as films, coatings, adhesives and as interlayer dielectrics in multichip modules and other multilayer electronic circuits.
Johnson et al. disclose in IEEE Transactions On Components, Hybrids, and Manufacturing Technology, Vol. 13, No. 2, June, 1990, that a polymer of C~ ~Si -o-si~
CH=CH ~ ' CH=CH
~H3 CH3 1,3-bis(2-bicyclo~4.2.0]octa-1,3,5-trien-3-ylethenyl)-1,1,3,3-tetramethyldisiloxane ~hereinafter DVS), available as a partially polymerized solution in mesitylene from The Dow Chemical Company as Cyclotene 3022~ ~hereinafter partially thermal Iy polymeri~ed DVS or DVS
prepolymer) may be used as an interlayer dielectric to construct thin film multichip modules.
25 The partially thermally polymerized DVS may be appl ied by spin coating a solution of a prepolymer onto a substratel evaporating the solvent and then polymerizing by heating to 250C for one hour in nitrogen. Catalysts and/or initiators are not required for the polymerization.
W093/ 8 ~121t)5 ~
I I I 9 PCI'/US92/10173 ,~
When exposed to air arylcyclobutene polymers undergo oxidation. At elevated temperatures the oxidation is accelerated . When the polymer oxidizes, its electrical insulating properties are degraded. Oxidation may lead to a yellow discoloration of the polymer, and in severe cases to an amber color even in thin films.
One may encapsulate the arylcyclobutene polymer by forming an oxygen barrier around it. However, this adds costly steps to a fabrication process. Barrier coatings are also :
subject to breakage and/or cracking, particularly under thermal cycling, which leads to loss of `
the barrier protection. .
To preserve optical clarity and important electrical properties such as low `
10 dielectric constant and low water uptake without the use of hermetic packaging or barrier coatings, it would be advantageous to have an arylcyclobutene polymer composition that is less susceptible to oxidation when exposed to air. .:
The invention is a composition containing a compound containing an ~:
arylcyclobutene moiety and antioxidant compounds of the formulae: .
1) (~--CH--~--N--~--C3--2) E~ c~2CHtc~c~ c :~
This invention relates to polymeric compositions made from arylcyclobutene containing monomers and methods for preventing autoxidation of said polymers.
Arylcyclobutene monomeric compositions are useful in preparing thermoset and thermoplastic polymeric compositions. Such polymeric compositions are highly desirable because they exhibit hydrophobicity, excellent thermal stability, chemital resistance and electrical insulative properties. Such polymeric compositions typical Iy can exhibit thermal degradation temperatures above 300C, are insoluble in many organic solvents and in water 10 and have dielectric constants of less than 3.0 at 1 MHz. Therefore, they find uses as films, coatings, adhesives and as interlayer dielectrics in multichip modules and other multilayer electronic circuits.
Johnson et al. disclose in IEEE Transactions On Components, Hybrids, and Manufacturing Technology, Vol. 13, No. 2, June, 1990, that a polymer of C~ ~Si -o-si~
CH=CH ~ ' CH=CH
~H3 CH3 1,3-bis(2-bicyclo~4.2.0]octa-1,3,5-trien-3-ylethenyl)-1,1,3,3-tetramethyldisiloxane ~hereinafter DVS), available as a partially polymerized solution in mesitylene from The Dow Chemical Company as Cyclotene 3022~ ~hereinafter partially thermal Iy polymeri~ed DVS or DVS
prepolymer) may be used as an interlayer dielectric to construct thin film multichip modules.
25 The partially thermally polymerized DVS may be appl ied by spin coating a solution of a prepolymer onto a substratel evaporating the solvent and then polymerizing by heating to 250C for one hour in nitrogen. Catalysts and/or initiators are not required for the polymerization.
W093/ 8 ~121t)5 ~
I I I 9 PCI'/US92/10173 ,~
When exposed to air arylcyclobutene polymers undergo oxidation. At elevated temperatures the oxidation is accelerated . When the polymer oxidizes, its electrical insulating properties are degraded. Oxidation may lead to a yellow discoloration of the polymer, and in severe cases to an amber color even in thin films.
One may encapsulate the arylcyclobutene polymer by forming an oxygen barrier around it. However, this adds costly steps to a fabrication process. Barrier coatings are also :
subject to breakage and/or cracking, particularly under thermal cycling, which leads to loss of `
the barrier protection. .
To preserve optical clarity and important electrical properties such as low `
10 dielectric constant and low water uptake without the use of hermetic packaging or barrier coatings, it would be advantageous to have an arylcyclobutene polymer composition that is less susceptible to oxidation when exposed to air. .:
The invention is a composition containing a compound containing an ~:
arylcyclobutene moiety and antioxidant compounds of the formulae: .
1) (~--CH--~--N--~--C3--2) E~ c~2CHtc~c~ c :~
3) OH
tCH3)3C~/C(CH3)3 OCH2cH2 --S
W0 93/1 1 189 ~ 5 1 PCl'/US92/10173 4) R~;<CE13 N CH3 : ~.
H ~:
wherein R is hydrogen, an electron withdrawing or electron donating group; and - -oligomers thereof;
tCH3)3C~/C(CH3)3 OCH2cH2 --S
W0 93/1 1 189 ~ 5 1 PCl'/US92/10173 4) R~;<CE13 N CH3 : ~.
H ~:
wherein R is hydrogen, an electron withdrawing or electron donating group; and - -oligomers thereof;
5) hindered aminesof the formula~
; ,.
(R1 )2 ( R l ) 2 ~p~ t ) 2 ( R~ R2 ) 2 R
wherein R is hydrogen, an electron withdrawing group or an electron donating group; :
each R' is independently, hydrogen, an electron withdrawing group or an -:
electron donating group, with the proviso that two Rl attached to the same carbon may represent a single moiety joined to said carbon by a double bond;
each R2 is independently, methyl, ethyl, n-propyl or isopropyl;
said antioxidant being effective to inhibit oxidation of polymer formed by side ring opening of 30 the arylcyclobutene.
In another aspect, the invention is a composition containing a polymer formed bythe side ring opening of an arylcyclobutene moiety and an amount of said antioxidant sufficient to inhibit oxidation of the polymer.
In another aspect, the invention is a method for inhibiting oxidation c f a polymer 35 formed by the side ring opening of compounds containing one or more arylcyclobutene W093/lll8g 2l2ln5l PCI/USg2/1~173 moieties by adding to the monomer compound, the prepolymer or polymer of the compound, an amount of said antioxidant sufficient to inhibit oxidation of the polymer.
In another aspect, the invention is an article containing a component which is apolymer formed by the side ring opening of an arylcyclobutene moiety and an amount of said 5 antioxidant sufficient to inhibit oxidation of the polymer.
A feature of the invention is that the polymer formed by the side ring opening of :
an arylcyclobutene moiety contains said oxidation inhibitor in an amount effective to prevent oxidation of said polymer. :~
An advantage of the invention is that said oxidation inhibitors inhibit oxidation 10 of the polymer formed by the side ring opening of an arylcyclobutene moiety. Inhibition of oxidation delays an increase in the dielectric constant and the formation or darkening of color in the polymer. An additional advantage is that said oxidation inhibitars are compatible with the compositions in that they do not precipitate or separate from the composition and thus ~ecome ineffec~ive. An additional advantage is that cured films may have substantially the ~ -15 same dielectric constant as the uninhibited cured films. An additional advantage is that cured films may have the same hydrophobicity as the uninhibited cured films.
In one aspect, the compositions of this invention contain compounds having an arylcyclobutene moiety. Compounds having one arylcyclobutene moiety are referred to hereinafter as mono-arylcyclobutene compounds. Compounds containing two or more 20 arylcyclobutene moieties are hereinafter referred to as poly-arylcyclobutene compounds.
Compounds containing arylcyclobutene moieties are described in U. S. Patents 4,724,260;
4,783,514; 4,826,997; 4,965,329; 4,661,193; 4,642,329; 4,~99,449; 4,540,763; 4,812,588.
Preferred mono-arylcyclobutene compounds contain a 1,2 diaromatic substituted ethylenically unsaturated moiety such asthose described in U. S. Patent 4,783,514, a maleimide moiety such as those described in U . S. Patent 4,826,997; or another moiety which is reactive with an arylcyclobutene moiety. Exemplary poly-arylcyclobutenes are those formed by the partial polymerization of mono-arylcyclobutenes, those disclosed in U. S. Patent 4,999,449, the DVS
monomer described hereinbefore and partially thermally polymerized compositions of said monomer.
The inventive composition can contain other materials which do not interfere with the usefulness of the composition such as, for example, monomers copolymerizable with the arylcyclobutene compounds such as other monomers containing arylcyclobutene moieties, ethylenically unsaturated moieties, acetylenic moieties, and other compositions which can undergo addition polymerization reactions; miscible compositions, such as blowing agents and 35 fire-retarding agents; reinforcing fillers such as glass or carbon fibers, or organic fibers such as aramid fibers; fillerssuch as quartz glass and powdered silica; metal and ceramic powders for electrical conductive and insulative properties.
W0~3/1118~ 2~ 2 ~ PCI/US42/10173 The inventive composition may also be partially polymeri~ed. To be partially polymerized, at least some of the side rings of the arylcyclobutene compounds are opened and reacted to create dimers, trimers and higher oligomers and polymers. However, some of the side rings of the arylcyclobutene compounds remain unreacted in the partially polymerized 5 composition. The mixture comprising the partially polymerized form may contain unreacted monomer, oligomers, polymers in a variety of branching configurations and gelled polymer as well as materials described hereinbefore as optional components of the inventive composition. :~
Preferably, the partially polymerized composition is not polymerized to its gel point. For DVS, one may use FT-IR to measure the appearance of the tetralin structure at 1500 cm ', the 10 disappearance of the side rings at 1472 cm ' or the vinyl groups at 985 cm 1. One may el iminate concentration and path length differences between tests by measuring the ratio of these peaks to the peak at 1254 cm-1 for Si-methyl rocking mode which remains constant through the polymerization and curing process. Using a given polymerization method, one may determine the degree of polymerization that gives undesirable gels empirically and then use that number 15 to monitor subsequent polymerizations. Typically, for DVS, 35 to 40 percent polymerization is preferred.
Aryl moieties are those referred to as aromatic compounds which contain (4n~2)nelectronsasdescribedinMorrisonandBoyd, OrganicChemistry, 3rded.,1973.
Examples of suitable aryl moieties include benzene, naphthalene, phenanthrene, anthracene, 20 pyridine, a biaryl moiety, or 2 or more aromatic moieties bridged by alkylene or cycloalkylene moieties. Preferred aryl moieties are benzene, naphthalene, biphenyl or pyridine moieties.
The most preferred aryl moiety is a benzene moiety.
An arylcyclobutene moiety is an aryl moiety to which one or more cyclobutene rings are fused such that the tWO carbons of the cyclobutene rings, not part of the benzene 25 ring, are bonded directly to two adjacent carbons on the same aryl ring. Exemplary structures include:
'3~ ~1 ' ~ ' ~or ~) W0~3/lll~ 21210.~1 Pcr/usg2/lol73 The 'side ring' of an arylcyclobutene contains two carbon atoms not in the h aromatic ring that are connected to adjacent carbon atoms on the same aryl ring, the bond betvveen said carbon atoms and the two bonds between the carbon atoms and the aryl ring. , Arylcyclobutenes are ~hought to react by the opening of this ring between the two carbon atoms which can produce an orthoxylylene moiety as a reactive intermediate. The orthoxylylene moiety is a diene which may react with dienophiles and with other orthoxylylene moieties. The orthoxylylene moiety may also participate in free radical reactions. A feature of the side ring opening reaction is the breaking of the bond between the two side ring carbons and their bonding to other atoms.
The side ring of the arylcyclobutene can be opened by subjecting it to sufficient heat. Typicaliy, temperatures frorn 1 50C to 300C are sufficient to open the ring.
Polymerization solvents, catalysts or initiators are unnecessary. Preferably, the side ring opening is conducted in an inert atmosphere such as nitrogen containing less than 100 ppm oxygen.
One may also cure a thi n film of an arylcyclobutene by passing it through an i infrared furnace with an inert atmosphere such as nitrogen. This will permit cures to 92 percent conversion at 300C in 20 seconds with a total thermal cycle time of three minutes ''r~
above room temperature.
Electron-donating moieties are molecular or nuclear groups which donate 20 electrons more than a hydrogen atom would if accompanying the same site.
Electron-withdrawing moieties are groups which more readily withdraw an electron relative to a hydrogen atom.
Examples of suitable electron-withdrawing moieties include -N02, -CN, Br, I, Cl, F, -C02H, -C02R, .. .. .. .- ..
-C-R, -C-Aryl , -S-R , -S-Aryl , -S-R, O
and aryl.
Examples of suitable electron-donating moieties include alkyl, aryl, alkoxy, aryloxy, hydrocarbyl, hydrocarbyloxy, hydrocarbylthio,-OH,-OR, -NH2,-NHR, -NR2.
Hydrocarbyl refers to any organic moiety containing only carbon and hydrogen atoms; hydrocarbyloxy refers to such organic moieties which further contain a hydroxyl-moiety; and hydrocarbylthio refers to organic moieties which further contain a thiol moiety.
In a second aspect of this invention, a polymer is formed by the side ring opening :
of an arylcyclobutene compound. This polymer contains structures which are susceptible to autoxidation. Exemplarystructurescontainbenzylichydrogens.
; ,.
(R1 )2 ( R l ) 2 ~p~ t ) 2 ( R~ R2 ) 2 R
wherein R is hydrogen, an electron withdrawing group or an electron donating group; :
each R' is independently, hydrogen, an electron withdrawing group or an -:
electron donating group, with the proviso that two Rl attached to the same carbon may represent a single moiety joined to said carbon by a double bond;
each R2 is independently, methyl, ethyl, n-propyl or isopropyl;
said antioxidant being effective to inhibit oxidation of polymer formed by side ring opening of 30 the arylcyclobutene.
In another aspect, the invention is a composition containing a polymer formed bythe side ring opening of an arylcyclobutene moiety and an amount of said antioxidant sufficient to inhibit oxidation of the polymer.
In another aspect, the invention is a method for inhibiting oxidation c f a polymer 35 formed by the side ring opening of compounds containing one or more arylcyclobutene W093/lll8g 2l2ln5l PCI/USg2/1~173 moieties by adding to the monomer compound, the prepolymer or polymer of the compound, an amount of said antioxidant sufficient to inhibit oxidation of the polymer.
In another aspect, the invention is an article containing a component which is apolymer formed by the side ring opening of an arylcyclobutene moiety and an amount of said 5 antioxidant sufficient to inhibit oxidation of the polymer.
A feature of the invention is that the polymer formed by the side ring opening of :
an arylcyclobutene moiety contains said oxidation inhibitor in an amount effective to prevent oxidation of said polymer. :~
An advantage of the invention is that said oxidation inhibitors inhibit oxidation 10 of the polymer formed by the side ring opening of an arylcyclobutene moiety. Inhibition of oxidation delays an increase in the dielectric constant and the formation or darkening of color in the polymer. An additional advantage is that said oxidation inhibitars are compatible with the compositions in that they do not precipitate or separate from the composition and thus ~ecome ineffec~ive. An additional advantage is that cured films may have substantially the ~ -15 same dielectric constant as the uninhibited cured films. An additional advantage is that cured films may have the same hydrophobicity as the uninhibited cured films.
In one aspect, the compositions of this invention contain compounds having an arylcyclobutene moiety. Compounds having one arylcyclobutene moiety are referred to hereinafter as mono-arylcyclobutene compounds. Compounds containing two or more 20 arylcyclobutene moieties are hereinafter referred to as poly-arylcyclobutene compounds.
Compounds containing arylcyclobutene moieties are described in U. S. Patents 4,724,260;
4,783,514; 4,826,997; 4,965,329; 4,661,193; 4,642,329; 4,~99,449; 4,540,763; 4,812,588.
Preferred mono-arylcyclobutene compounds contain a 1,2 diaromatic substituted ethylenically unsaturated moiety such asthose described in U. S. Patent 4,783,514, a maleimide moiety such as those described in U . S. Patent 4,826,997; or another moiety which is reactive with an arylcyclobutene moiety. Exemplary poly-arylcyclobutenes are those formed by the partial polymerization of mono-arylcyclobutenes, those disclosed in U. S. Patent 4,999,449, the DVS
monomer described hereinbefore and partially thermally polymerized compositions of said monomer.
The inventive composition can contain other materials which do not interfere with the usefulness of the composition such as, for example, monomers copolymerizable with the arylcyclobutene compounds such as other monomers containing arylcyclobutene moieties, ethylenically unsaturated moieties, acetylenic moieties, and other compositions which can undergo addition polymerization reactions; miscible compositions, such as blowing agents and 35 fire-retarding agents; reinforcing fillers such as glass or carbon fibers, or organic fibers such as aramid fibers; fillerssuch as quartz glass and powdered silica; metal and ceramic powders for electrical conductive and insulative properties.
W0~3/1118~ 2~ 2 ~ PCI/US42/10173 The inventive composition may also be partially polymeri~ed. To be partially polymerized, at least some of the side rings of the arylcyclobutene compounds are opened and reacted to create dimers, trimers and higher oligomers and polymers. However, some of the side rings of the arylcyclobutene compounds remain unreacted in the partially polymerized 5 composition. The mixture comprising the partially polymerized form may contain unreacted monomer, oligomers, polymers in a variety of branching configurations and gelled polymer as well as materials described hereinbefore as optional components of the inventive composition. :~
Preferably, the partially polymerized composition is not polymerized to its gel point. For DVS, one may use FT-IR to measure the appearance of the tetralin structure at 1500 cm ', the 10 disappearance of the side rings at 1472 cm ' or the vinyl groups at 985 cm 1. One may el iminate concentration and path length differences between tests by measuring the ratio of these peaks to the peak at 1254 cm-1 for Si-methyl rocking mode which remains constant through the polymerization and curing process. Using a given polymerization method, one may determine the degree of polymerization that gives undesirable gels empirically and then use that number 15 to monitor subsequent polymerizations. Typically, for DVS, 35 to 40 percent polymerization is preferred.
Aryl moieties are those referred to as aromatic compounds which contain (4n~2)nelectronsasdescribedinMorrisonandBoyd, OrganicChemistry, 3rded.,1973.
Examples of suitable aryl moieties include benzene, naphthalene, phenanthrene, anthracene, 20 pyridine, a biaryl moiety, or 2 or more aromatic moieties bridged by alkylene or cycloalkylene moieties. Preferred aryl moieties are benzene, naphthalene, biphenyl or pyridine moieties.
The most preferred aryl moiety is a benzene moiety.
An arylcyclobutene moiety is an aryl moiety to which one or more cyclobutene rings are fused such that the tWO carbons of the cyclobutene rings, not part of the benzene 25 ring, are bonded directly to two adjacent carbons on the same aryl ring. Exemplary structures include:
'3~ ~1 ' ~ ' ~or ~) W0~3/lll~ 21210.~1 Pcr/usg2/lol73 The 'side ring' of an arylcyclobutene contains two carbon atoms not in the h aromatic ring that are connected to adjacent carbon atoms on the same aryl ring, the bond betvveen said carbon atoms and the two bonds between the carbon atoms and the aryl ring. , Arylcyclobutenes are ~hought to react by the opening of this ring between the two carbon atoms which can produce an orthoxylylene moiety as a reactive intermediate. The orthoxylylene moiety is a diene which may react with dienophiles and with other orthoxylylene moieties. The orthoxylylene moiety may also participate in free radical reactions. A feature of the side ring opening reaction is the breaking of the bond between the two side ring carbons and their bonding to other atoms.
The side ring of the arylcyclobutene can be opened by subjecting it to sufficient heat. Typicaliy, temperatures frorn 1 50C to 300C are sufficient to open the ring.
Polymerization solvents, catalysts or initiators are unnecessary. Preferably, the side ring opening is conducted in an inert atmosphere such as nitrogen containing less than 100 ppm oxygen.
One may also cure a thi n film of an arylcyclobutene by passing it through an i infrared furnace with an inert atmosphere such as nitrogen. This will permit cures to 92 percent conversion at 300C in 20 seconds with a total thermal cycle time of three minutes ''r~
above room temperature.
Electron-donating moieties are molecular or nuclear groups which donate 20 electrons more than a hydrogen atom would if accompanying the same site.
Electron-withdrawing moieties are groups which more readily withdraw an electron relative to a hydrogen atom.
Examples of suitable electron-withdrawing moieties include -N02, -CN, Br, I, Cl, F, -C02H, -C02R, .. .. .. .- ..
-C-R, -C-Aryl , -S-R , -S-Aryl , -S-R, O
and aryl.
Examples of suitable electron-donating moieties include alkyl, aryl, alkoxy, aryloxy, hydrocarbyl, hydrocarbyloxy, hydrocarbylthio,-OH,-OR, -NH2,-NHR, -NR2.
Hydrocarbyl refers to any organic moiety containing only carbon and hydrogen atoms; hydrocarbyloxy refers to such organic moieties which further contain a hydroxyl-moiety; and hydrocarbylthio refers to organic moieties which further contain a thiol moiety.
In a second aspect of this invention, a polymer is formed by the side ring opening :
of an arylcyclobutene compound. This polymer contains structures which are susceptible to autoxidation. Exemplarystructurescontainbenzylichydrogens.
~2~S ~1 WO 93/11189 PCr/US92/10173 Exemp!ary structures include:
H H
or H H H H
15 -~
which are two of the possible structures formed when two side rings open and react with each other; and ~ or --N~
wherein one side ring opens forming the orthoxylylene which reacts with a dienophiie, the first 30 instance being an example c f the product formed by the reaction of the orthoxylylene and a vinyl group and the second bei ng an example of the product formed by the reaction of the orthoxylylene and a maleimide.
Some of the benzylic hydrogens in these structures are depicted for the purpose 35 of illustration When thin films of the arylcyclobutene polymers depicted are exposed to elevated temperatures such as 1 00C or 200C for extended periods of time, such as 200 hours, in an inert atmosphere, such as nitrogen, there may be no changes i n the dielectric constant or WO 93/11 IX9 2 ~ 2 .L 0 S 1 PCr/US92/10173 - ~
the FT-IR spectrum. When thin films of the arylcyclobutene polymers depicted are exposed to oxygen-containing atmospheres such as air, they form a yellow color, the dielectric constant increases and the FT-IR spectrum changes. The oxidized arylcyclobutene polymer absorbs water more readily than unoxidized arylcyclobutene polymer. Any increase in water content leads to 5 a further increase in the dielectric constant. The changes in the dielectric constant and those in the FT-IR spectrum directly correlate, so that one may monitor changes in the dielectric constant by measuring changes in the FT-IR spectrum.
FT-IR studies show that sites with benzylic hydrogens are generally more susceptible to oxidation than other sites in the polymer or prepolymer. For such studies, thin films of the arylcyclobutene polymer are placed on bare silicon substrates having no silicon oxide coating so that the strong absorbance of silicon oxide does not mask the FT-IR spectrum in the area of interest. One may monitor the FT-IR bands at 2952, 1700, 1500, 1254 or 1050 cm-t.
The band at 1500 cm ' is particularly useful as it indicates a ring bending mode for the polymer's tetrahydronaphthalene structure. The spectral absorbance of this band decreases with the 5 decrease in concentration of the tetrahydronaphthalene structure as oxidation occurs. The broad band between 1800 to 1600 cm ', particularly at 1700 cm-1 is an absorption band for aryl carbonyl moieties. The absorbance of this band increases with the concentration of benzylic carbonyls. During polymer thin film oxidation, there is a strong correlation between the reduction in the absorbance at 1 500cm 1 and the increase in absorbance at 1700 cm-'.
The 'dielectric' lifetime or as hereinafter nominated, the 'lifetime' of a thin film polymer coating made from a compound containing an arylcyclobutene n oiety is nominally defined as the time it takes at a given temperature in air for the dielectric constant of the polymer to increase by ten percent. This approximately correlates with the time it takes for the 25 FT-IR absorbance band at 1500 cm 1 to decrease to 80 percent of its initial value. It also correlates well with the ti me it takes for the absorbance at 1700 cm ', divided by the film thickness, to reach 0.02 llm l . Si nce changes in the FT-IR spectrum are easier to measure than changes in the dielectric constant, the changes in the FT-IR may be used to measure lifetimes.
The preferred arylcyclobutene compounds of this invention include compounds 30 of the structure WO 93/1 1 189 2 ~ ~ ~ Q ~ ~ PCr/US92/10173 ( R6 ) r ~ R, 3 --R, 3 - 5 )~R4----Si-0----Si-R4~
(R6)r ~/ R3 R3 ~\(R6)r (R5)q -- -- (R5)q n 1u wherein each R3 is independently C, 6 alkyl, cycloalkyl, aralkyl, or phenyl;
each R4 is independently ethenyl, propenyl or 2-methyl propenyl;
each Rs is independently Cl 6 alkyl, methoxy, or chloro;
each R6 is independently Cl 6 alkyl, chloro, or cyano;
n is an integer of 1 or more; and :
each q and r is independently an integer of zero or l . -The most preferred compound (DVS) is represented by the formula:
[~ Si O S
CH=CH~ ~ I ~ CH=CH
The depictions of this compound herein should not be construed to define any particulargeometric isomer or spatial orientation about the ethenylene double bonds.
Compounds made by the processes disclosed herein contain positional isomers about these double bonds.
These organopolysiloxane bridged bisbenzocyclobutene monomers can be 30 prepared by methodsdisclosed in U.S. Patent 4,812,588 and EP published application 0506314.
These organopolysiloxane bridged bisbenzocyclobutene monomers can be prepared by reacting an excess of a 3- or 4-halo benzocyclobutene, preferably 4-bromobenzocyclobutene, with the desired diterminal vinyl, allyl or methal!yl organo- ;
polysiloxane compound. Typically, a molar ratio of the bromobenzocyclobutene to the - 35 organopolysiloxane bridgi ng group of at least 1.5:1 is desired, preferably at least 2: t .
Preferably, the bromobenzocyclobutene is a 4-bromobenzocyclobutene represented by the formula:
WO 93/11189 21 ~ 1 0 S 1 PCI~/US92JIOt73 s (R6)r ~\13r (R5)q wherein Rs iS Cl 6 alkyl, methoxy, or chloro;
R6 iS Cl 6 alkyl, chloro, or cyano; and each q and r is independently an integer of zero or 1.
A preferred organopolysiloxane compound is represented by the formula:
r R3 ¦ R~
R4 --Si-O-- Si-R4 _ _ n 20 wherein each R3 is independently C1 6 alkyl, cycloalkyl, aralkyl, or phenyl; i-each R4 is independently vinyl (-CH = CH,), allyl (-CH,-CH = CH2), or methallyl ~-CH2-C=C~ .
~ ' ~ ; and :
n is an integer of 1 or more. ~ - -For R3, the preferred cycloalkyl is cyclohexyi and the preferred aralkyl is benzyl.
30 Most preferably, R3 is methyl, R4 is vinyl and q and r are 0.
The coupling reaction of the organopolysiloxane compound with the halobenzocyclobutene is possible because the organopolysiloxane compound is a bisvinyl or bisallyl bridging group. The substitution reaction of an olefinic compound possessing at least one hydrogen on a vinylic position with an organic halide is known and disclosed in U.S.
35 Patent 3,922,299 (Heck) Heck discloses the substitution reaction of aryl halides with olefinic compounds in the presence of a Group Vlll metal, a trivalent arsenic or phosphorous compound, and a soluble WO 93/1 1 189 2 1 ~ ~ ~J ~ ~ PCr/US92/10173 trialkylamine. The reaction displaces a hydrogen on a vinylic or allylic position with the organic compound. For example, the most preferred bisbenzocyclobutene monomer can be prepared by reacting about 2 moles of bromobenzocyclobutene with about one mole of 1,3-divinyl-1,1,3,3-tetramethyl-disiloxane in the presence of a catalytic amount of palladium 5 acetate and tri(orth~tolyl)phosphi ne, in addition to triethylamine, which acts as an acid scavenger.
Organopolysiloxanes and processes for preparing them are known and disclosed in U.S. Patents 3,584,027; 3,701,195; 3,770,768; and 3,803,196. Processes for preparing bromobenzocyclobutene are disclosed in U.S. Patents 4,822,930 and 4,891,455 and by 10 Lloyd et al., Tetrahedron, Vol.21, pp. 245-254 (1965) at page 253.
Following one of the procedures for making the preferred monomer, one will obtain a mixture containing as a major component divinyltetramethyldisiloxane-bis-benzocyclobutene monomer. This monomer mixture has a low viscosity.
Partial thermal polymerization of the arylcyclobutene compound forms a 15 prepolymer which may have more desirable properties in use, such as a wider temperature range between the melting point and the cure temperature and a more desirable viscosity. The prepolymer retains its solubility in organic solvents because it is not polymerized to the gel point. The prepolymer may retain its density and shrinks less than the monomer upon curing. ~ .
The prepolymer can be employed to prepare cured polymeric compositions.
If the arylcyclobutene compound is not already a liquid, it will often melt to aliquid upon heating before it polymerizes. The melted arylcyclobutene compound, typically, has a low viscosity. As polymerization proceeds, the arylcyclobutene compound reaction mixture becomes more viscous.
The prepolymer contains both reacted and unreacted polymerization sites. It may 25 contain completely unreacted arylcyclobutene compound, oligomers and cured polymer as well as other unreacted materials included in the arylcyclobutene compound.
In one method of forming the prepolymer by partial thermal polymerization, an amount of the arylcyclobutene compound is heated to a temperature sufficient to initiate and sustain polymerization. Arylcyclobutene compounds may also be partially polymerized with 30 any type of radiation such as X-ray or E-beam or i n any way that will lead to polymerization.
Polymerization with E-beam or X-ray is not recommended for compositions already containing the antioxidants represented in group 4) such as AgeRite~ MA.
Partial thermal polymerization may be effected over a wide range of temperatures. The lower the temperature the longer the process will take. Partial thermal - 35 polymerization takes place at a temperature effective to polymerize the arylcyclobutene compound. Such a temperature is preferably above 150C and below 220C. The reaction mixture is removed from the heat after it attains an appropriate viscosity which is greater than WO 93/1 1 189 2 ~ PCl/US92/10173 the initial viscosity of the melted arylcyclobutene compound and which enables more effective use of the partially polymerized composition.
The viscous, partially thermally polymerized composition can be employed as a film wherein an effective amount of the neat partially polymerized composition is applied to a S surface, and subsequently further polymerized. Or, the partially polymerized composition can be mixed with a suitable solvent. The solution can then be applied to a surface, the solvent evaporated, and the partially polymerized composition further polymerized to provide a polymer film.
The partial thermal polymerization of DVS to form partially thermally 10 polymerized DVS may be performed by heating the DVS at 1 95C for two hours under nitrogen or alternatively, by heating the DVS at t 70C for 22 hoùrs under nitrogen. Most preferably, the DVS is heated and stirred at 160 to 180C for a period of time of 20 to 24 hours, to reach a weight averaged molecular weight of 30 to 35,000 as measured by gel permeation chromatography against a polystyrene standard.
The partially thermally polymerized DVS and fully cured DVS may contain units oftheformula ''- =`''-' `~
~Si ~CH3 : .
CH3 O ~Si CH3 .:
25 wherein the tetralin structure is formed by the Diels-Alder reaction of one of the vinyl groups and the side ring openi ng of one of the benzocyclobutene moieties.
When coati ng a substrate with a benzocyclobutene, it may be desirable to use anadhesion promoter. Suitable adhesion promoters include triethoxyvinylsilane ~CAS# 78-08-û) andotherorganosilaneadhesionpromotersastaughtforexampleinU.S.patent4,831,172.
The adhesion promoter is most advantageously used when bonding the polymer to an inorganic surface. The adhesion promoter may be coated onto the surface prior to application of the compound containing an arylcyclobutene functionality or it may be mixed in and applied with the compound containing an arylcyclobutene functionality. Preferably the triethoxyvinylsilane adhesion promoter is applied as a thin coating to the surface and a 35 partially thermally polymerized DVS in solution is coated over it. Then, after removal of the solvent, the adhesion promoter and partially thermally polymerized DVS are subjected to conditions sufficient to polymerize the DVS at least beyond its gel point.
WO 93/1 1 189 2 1 2 i ~3 t j ~ PCI /US92/10173 The gel point is described in the Concise Encvclo,~edia Of Polvmer Science And Enaineerinq; Wiley Interscience, 1990, pp. 430-2. The gel point describes a critical point in the polymerization from a monomer to a fully cured polymer. Before the gel point, the polymer is soluble in good solvents. It is called a sol and is a liquid even if highly viscous. Beyond the gel 5 point the polymer is not completely soluble, even in a good solvent. However low molecular weiyhtfractions(sol fraction) maystill beextractable.
Preferably, the gel point can be defined as that point wherein one part of polymerwill notcompletelydissolvein 100partsofagoodsolventatitsboilingpoint. Good solvents include aromatic hydrocarbons such as toluene, xylene, mesitylene; aliphatic 10 hydrocarbons such as pentane, hexane; hetero atom containing hydrocarbons such as N-methyl pyrrolidone and methyl ethyl ketone. More preferably the gel point can be defined as that point wherein one part of polymer will not completely dissolve in ten parts of xylene at its boiling point.
Antioxidants and stabilizers may be chosen frorn broad classes of known materials 15 such as those disclosed in: Oxidation Inhibition In Oraanic Materials, Ed~ Pospisil and Klemchuk, CRC Press, Inc., Boca Raton, Florida, 1990, which is incorporated herein by reference.
Antioxidants useful in this invention are those effective to prevent autoxidation of a polymer made by the side ring opening of an arylcyclobutene.
Exemplary antioxidants include:
1) a compound of the formula:
H3 ~ CH3 25 which is nominally called 4,4'-bis(~l-methylbenzyl)diphenylamine and is commereially available from Goodyear as Wingstay~ 29.
2) a compound of the formula;
~~ C~12C~COOCi~ C
which is nominally cailed tetrakis [methylene (3,5-di-tert-butyl-4-hydroxyhydrocinnamate) methane (CA5 No. 6683-19-6) and is commercially available from ~iba-Geigy as Irganox~ 1010.
WO g3/l 1 189 2 ~ 2 ~ 0 5 1 PCl/US92/10173 3) a compound of the formula:
OH --5(C~3)3C~/C(CE~3)3 OcH2cH 2 S
10 which is nominally called thiodiethylene bis-(3,5-di-tert-butyl-4-hydroxy)hydrocinnamate (CAS No. 41484-35-9) and is commer~ially available from Ciba-Geigy as Irganox~ 1035. ~ -4) compounds of the formula:
CH3 ~:
R~q/~C}i3 H :
20 wherein R is hydrogen, an electron withdrawing or electron donating yroup; and - :oligomers thereof. Preferably R is hydrogen, but it also can be any substituent that does not interfere with the antioxidant activity of the compound. Preferred R substituents are phenyl, ~:
Cl 20 alkyl and alkoxy.
This group also contains the oligomer of the formula <C~3 H \ H / n wherein R is as hereinbefore defined and n is 0-6.
2,2,4-trimethyl-1,2-dihydroquinoline, wherein R is hydrogen, is available as AgeRite~ MA from R. T. Vanderbilt as an oligomer with a degree of polymerization of about 3 or 4 (n is about 1 or 2). :
6-ethoxy-2,2,~trimethyl-1 ,2-dihydroquinoline of the formula WO g3/1 1 189 ~ 1 2 1 ~ PCT/US92/10173 E~sC20~<
N
H
wherein R is ethoxy, is available as Permanax~ ETMQ from Vulnax.
~dodecyl-2,2,4-trimethyl-1 ,2-dihydroquinoline of the formula C12~2~
N
H
wherein R is dodecyl, is available as Santoflex~ DD from Monsanto.
The hereinbefore recited oligomer is available as 600drite 3140 or AgeRite MA X9 Type from B F. Goodrich wherein the manufacturer is said to remove the terminai vinyl group and n is 0 to 5) hindered amines of the formula:
l)2 ( R~) 2 ~R 1 ) 2 ~
( R~\N / ( R2 ) 2 wherein R is hydrogen, an electron withdrawing group or an electron donating group;
each R' is independently, hydrogen, an electron withdrawing group or an . - 15-WO 93/1 1 189 2 1 2 1 0 ~i ~ PCI'/US92/10173 electron donating group, with the proviso that two R1 attached to the same carbon may represent a single moiely joined to said carbon by a double bond; and each R2 is independently, methyl, ethyl, n-propyl or isopropyl.
These compounds belong to a known class called hindered amine light stabilizers as described in Oxidation Inhibition In Oraanic Materials, Ed. Pospisil, J. and Klemchuk, P. P., CRC Publishing, Boca Raton, Florida, 1990, Vol. Il, pp. 1-28, which is hereby incorporated by reference. The structure includes a six-membered ring with one or two nitrogen atoms and four or five carbon atoms and no hydrogens on the carbon atoms adjacent to the hindered nitrogen atoms.
In order to prepare these compounds one may react acetone or another appropriate ketone with ammonia under known conditions to form triacetoneamine or a derivative thereof. This is then reduced to make the alcohol of the formula:
OH
tR1)2 ~R1)2 (R~ I (R2)2 R' and R2 are selected based on the ketone used in the synthesis. The hydroxy function may be converted to an ester function by treatment with the appropriate acid and 25 removal of by-product water using conventional techniques. The ketone function may be converted to an amine function by treatment with the appropriate amine with catalyst and hydrogen using conventional techniques.
WO 93/1 1 189 .~ 1 2 1 ~ Pcr~usg2/1ol73 Exemplary structures include:
C4Hg ~0~ CH2--C-C-~N-Cl13 Cl=O
tO >~
N ;~
which is available as Tinuvin~ 144 from Ciba-Geigy;
1l 1 ,, O-C-~CH2)8--C-O
: ,, ,, .
N N
~: CH3 CH3 25 which is available as Ti nuvin~ 292 or Ti nuvi n~ 765 from Ciba-Geigy or as Sanol~ LS-292 from Sankyo Co. Ltd.;
HN~ O-C- ( CH2 ) 8 -17-~7<~H
whichisavailableasTinuvin~770fromCiba-GeigyorasSanol~LS-770fromSankyoCo~Ltd~;
r~ 1 o 1 ~ n WO 93/1 1 189 2 ~ 2 1 0 ~i ~ PCr/USg2/10173 which is available as Tinuvin~ 622 from Ciba-Geigy;
t'$~ (CH2 6~
O H H n which is available as Cyasorb~ UV-3346 from American Cyanamid Co.;
_--N--(CH2)6--N-(cH2)2--_ ~5 ~
H H n which is available as Spinuvex'9 A-36 from Montefluos, (Borg-Warner for U.S. and Canada);
"~ >~P ~
: HN N-CH2-CH2-N NH
which is available as Goodrite~ 3034 from B. F~ Goodrich;
.' ~ ' W093/11189 ~ PCT/US92/10173 H H
N
rO~N--(CH )6--N~
: fH3 CH3 CH3 CH3 . - n whichis available as Chimassorb~ 944 from Ciba-Geigy;
r ~ 1 r " B
lH-0- ~ N-(CH2)20~ ~ H30-C-(CH2)2 C OC
whichis available as Tinuvin~ 622 as a polymer from Ciba-Geigy;
., ~
' :~
WO 93/1 1 189 2 1 2 1 0 5 ~ PCI`/US92/10173 R R
R-NH(CH2)3N(CH2)2 N(CH2)3 NH R
C4~9 .
wherein R = ~/~ N~N--CH3 ~N
I ~ `~
C4Hg--N ~<N--CH3 which is available as Chimassorb~ 119 FL from Ciba-Geigy.
The antioxidant is added to a compound containing an arylcyclobutene moiety in a manner in which is effective to inhibit oxidation of polymer formed by side ring opening of the arylcyclobutene. The antioxidant may be combined with an arylcyclobutene monomer in liquid or solid form. The arylcyclobutene monomer and antioxidant may both be dissolved in a mutual solvent. The antioxidant may be dissolved in a liquid arylcyclobutene monomer. As the arylcyclobutene monomer is heated to polymerize it, the antioxidant may mix uniformly with it and maintain intimate contact with the polymer.
The antioxidant may be added to a partially polymerized compound containing an arylcyclobutene moiety. The arylcyclobutene prepolymer and antioxidant may both be dissolved in a mutual solvent. The antioxidant may be dissolved in a iiquid partially polymerized arylcyclobutene monomer. As the partially polymerized arylcyclobutene monomer is heated to polymerize it, the antioxidant rnay mix uniformly with it and maintain inti mate contact with the polymer.
Preferablyr effective antioxidants for polymers formed by side ring opening of an arylcyclobutene moiety, will survive the polymer cure without decomposing, blooming, evaporating or reacting disadvantageously with the monomer containing an arylcyclobutene moiety. AgeRite~ MA may deteriorate in effect if the monomer or prepolymer composition containing it is polymerized using electron bean (E-beam) radiation.
The antioxidant is added to a compound containing an arylcyclobutene moiety in an amount which is effective to inhibit oxidation of polymer formed by side ring opening of the arylcyclobutene. The lower limit is defined by the amount necessary to obtain measurable extension of the oxidation lifetime. The upper limit is defined by the amount of antioxidant which degrades polymer properties to an unacceptable level or beyond which additional WO 93/1 1 189 ~ ~ 2 ~ ~ ~ !~ PCI`/US92/ 10173 antioxidant does not extend the useful lifeti me. A preferred amount ranges from 0.1 to l O
weight percent of the antioxidant based on the compound containing an arylcyclobutene moiety. A more preferred amount ranges from 0.5 to 6 weight percent of the antioxidant based on the compound containing an arylcyclobutene moiety. A most preferred amount for S the DVS ranges from 1 to 4 weight percent of the Agerite~ MA antioxidant based on the DVS.
Since the DVS polymer finds a major use as a thin film dielectric, ionic contamination is preferably avoided. Agerite~ MA antioxidant contains sodium chloride and it is recommended that this be removed prior to addition to the compound containing an arylcyclobutene moiety. It can be removed by contacting the antioxidant with water to extract 10 the sodium chloride. Preferably it is dissolved in an organic solvent such as mesitylene to enhance the extraction. The antioxidant may then be isolated from the solvent and water by decantation, vacuum distillation and/or freeze drying.
The following examples are given to illustrate the invention and should not be interpreted as limiting it in any way. Unless stated otherwise, all parts and percentages are 15 given by weight.
Procedure A: Preparation of a Bisbenzocyclobutene Monomer Represented by the Formula:
2~ C~CN CH~S1 0 S1~ )~ (VI) A solution of 3.0 grams (g) ~1 .64x 1 0-2m) 4-bromobenzocyclobutene, 1.52 g 25 (8.2x103m) 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, 1.66g(1.64xl02m)triethylamine,0.152g (5.0x104m) tri-o-tolylphosphine, 72 milligrams (mg) (3.21xlO~m) palladium (il) acetate, and l O cm3 acetonitrile in a 50 cm3 2-neck round bottom flask equipped with a reflux condenser and magnetic stirring bar is heated to reflux for 24 hours. After 24 hours, the reaction mixture is cooled to room temperature and then poured i nto 60 cm3 of l O percent aqueous hydrochloric 30 acid. The resulting mixture is extracted with two 50 cm3 portions of methylene chloride and the combined methylene chloride solutions were washed with three l OO cm3 portions of water.
The organic phase is dried over anhydrous magnesium sulfate, filtered, and evaporated in vacuo to yield a yellow oil. The oil is chromatographed on silica gel eluting with 20 percent toluene in heptane. The product was removed ~rom the column and the solvent removed to 35 yield a colorless oil. Reverse phase high per~ormance liquid chromatography showed a mixture withonemajorcomponent. 'H-NMR(CDCI3)7.3-6.1 (m, 10H),3.2(s,8H),0.2(s, 12H)ppm.
.~
WO93/11189 2l~l.n5l PCI/US92J10173 Procedure B: Preparation of Bisbenzocyclobutene Monomer Derived From an Olefinic Aromatic Compound And Corresponding to the Formula ~ ~ C=CEI ~CII=CH ~ ~ U
(a) q = 3 A 25-cm3 flask equipped with a reflux condenser, nitrogen inlet, and magnetic stirring bar is charged with m-dibromobenzene (1.0 9, 4.2 x 10'3 m), m-divinylbenzene (2.75 g, 15 2.1x102m),tri-n-butylamine(8.4x103m),tri-o-tolylphosphine(64mg,2.1x104m),palladium (Il) acetate (20 mg, 8.4 x 10 5 m), and acetonitrile (10 cm3). The mixture is stirred under nitrogen and heated to reflux for 2 hours. The grey siurry is cooled to room temperature and stirred into 60 cm3 of 10 percent aqueous hydrogen chloride. The resulting precipitate is collected by filtration, washed with water, and air dried. This product is dissolved in ethylacetate, filtere~, 20 and the solvent evaporated to yield a yellow residue.
Recrystallization of the residue from heptane gives 0.60 g (42 percent yield) of a compound of the formula 25 cll2-C~ ~ Cll=C~ ~CII=CII ~ CY=CU2 hereinafter referred to as diterminal olefin, with a melting point of 105C.
A 25-cm3 flask e~uipped with a reflux condenser, nitrogen inlet and magnetic 30 stirring bar is charged with 4-bromobenzocyclobutene ( 1.5 9, 8 x 10-3 moles), the diterminal olefin from part A ( 1.34 9, 4 x 10 3 moles), tri-n-butylamine ( 1.8 g, 9.7 x 10-3 moles), tri-o-tolylphosphine (62 mg, 4.0 x 104 moles), palladium 11 acetate (18 mg, 8.0 x 10 5 moles) and acetonitrile (5 cm3). The reaction rnixture is heated to reflux under nitrogen for 4 hours. The mixture is cooled to room temperature and stirred into 60 cm3 of 10 percent hydrochloric acid.
35 The precipitate is collected by filtration, washed with water and air dried. The dried precipitate is then dissolved in 150 crn3 of boiling toluene, filtered hot and cooled tO yield 310 mg of the productq = 3. Themonomerhasameltingpointof180Cto215C.
WO 93/1 1 189 ~ O cJ ~ PCI`/US92/10173 (b) q = t A 25-cm3 flask equipped with a reflux condenser, nitrogen inlet, and magnetic stirri ng bar is charged with 4-bromobenzocyclobutene ( 1. 50 g, 8.0 x 10 3 m), m-di vinyl benzene (4.0 x 10'3 m), tri-n-butylamine ( 1.8 9, 9.7 x 10 3 m), tri-o-tolylphosphine (62 mg, 4.0 x 10 4 m), palladium(Il)acetate(18mg,8.0x10;m),andacetonitrile(5 cm3). Thereactionmixtureisheated to reflux under nitrogen with stirring for 4 hours. The solidified mixture is cooled to room temperature and stirred into 60 cm3 of 10 percent aqueous hydrogen chloride. The resulting precipitate is collected by filtration, washed with water, and air dried.
The precipitate is dissolved in 75 cm3 of boiling ethylacetate, filtered hot, and cooled to yield 800 mg (60 percent) of the desi red monomer with a melting point of 1 50C to Procedure C:
A Partially Polymerized Composition From The Compound Of The BisbenzocyclobuteneDerived From Meta-Divinyl Benzene Of Procedure B (b) H H H H H H H
H j~ l = l~ l = !~
A 1 g samp!e of the monomer of Procedure B (b) is heated from 189 to 222C at 25 the rate of 1C per minute. The partially polymerized composition has a viscosity of 249 poise at 220C, the partially polymerized composition is solid at room temperature and becomes gel-li ke at 180 to 1 90C. The partially polymerized composition contains 51 percent unreacted polymerizable functionality as determined by differential scanning calorimetry.
Exam~!es The noted antioxidant is dissolved in a partially thermally polymerized 1 ,3-bis(2 -bicyclo~4.2.0jocta- 1 ,3,5-trien-3-ylethenyl)- 1,1,3,3--tetramethyldisiloxane, available as a solution in mesitylene from The Dow Chemical Company as Cyclotene 3022~ at one weight percent based on the weight of the prepolymer A control, containing no antioxidant, is run for comparison purposes. The solutions are spin coated onto 35 oxide free silicon wafers at thicknesses resulting in polymer coatings of about ten microns~
The coating thickness can be controlled by selecting the viscosity of the solution, the spin speed and the spin time. Viscosity may be controlled by adjusting the concentration of WO g3/1 1 IX9 PCI/US92/10173 ~
:2121~Sl prepolymer in the solution. Preferably, a solution containing 55 per~ent DVS prepolymer in mesitylene and 1 percent antioxidant based on the weight of the prepolymer is puddled onto a silicon wafer. The wafer is then spun for about 3 seconds at 500 rpm and then spun for about 30 seconds at 5000 rpm tO spread the prepolymer evenly.
After spin coating a film, the solvent is evaporated and the film is thermally cured at 250C for one hour under a nitrogen atmosphere, preferably containing less than 100 ppm oxygen. The cured-polymer coated wafers are then placed in air purged ovens at the temperatures noted and are withdrawn periodically to obtain FT-IR spectral absorbance measurements.
Lifetimes of the films are based on the time it takes the absorbance at 1500 cm ' to reach 80 percent of its initial value. This band indicates the presence of tetralin which contains the benzylic hydrogens. Comparisons have shown that this corresponds to about a 10 percent increase in the dielectric constant which is the real indicator of i nterest in thin film dielectrics.
The use of silicon wafers permits the taking of the absorbance spectral 15 measurements through the transparent wafer and polymer film without degrading the film.
Absorbance measurements in this context refer to the definition given by:
A = -logT
wherein T is the transmittance and A is the absorbance. Transmittance is defined as:
T Is/lb 20 wherein Is is the intensity of light transmitted by the cured-polymer coated silicon wafer and Ib istheintensityoflighttransmitted bythesiliconwaferalone.
The absorbance band at 1500 cm ' typically does not have a local baseline at zero absorbance. Therefore, the absorbance at 1500 cm ' is measured relative to a line connecting two points taken as the lo.cal spectral baseline. 1520 cm ' and 1470 cm may advantageously be usedtodefinethelocal baseline.
The lifetime of the control at 100C is greaterthan 3500 hrs. Lifetimes of curedDVS with 1 percent by weight of the noted antioxidants, at oven temperatures of 1 25C and 1 50C are shown in the TABLE 1.
093/11189 ~ ~ ~ PCT/US92/10173 TABLE I
Polymer/Antioxidant Lifetimes Lifetime (Hrs) - SamPle at 150C at 125C
1*Control 97 450 2*AgeRite 94 447 Stalite~
(Vanderbilt) 3~bis(diphenyl 95 440 phosphino) methane 4*Irganox0 1076 95 456 (CIBA-GEIGY) 5 *A~eRite~ DPPD lO0 . 482 (Vanderbilt) 6*Irganox~ B215 108 528 (CIBA-GEIGY) 7Wingstay~ 29 121 669 :~ (Goodyear) 8Irganox~ 1035 127 631 (Ciba-Geigy) .
9Irganox~ lOlO 131 678 (Ciba-Geigy) :
10AgeRite~ MA 431 2790 ``
: (Vanderbilt) * not an example of the invention Similarly, various other antioxidants are screened. The exposure to air is conducted in an oven at 1 70C and accordingly the times are shorter than in TABLE 1. Each antioxidant is added to a sol ution of DVS prepolymer at one weight percent based on the weight of the prepolymer. Four controls, containing no antioxidant, are run for comparison purposes. The solutions are spin coated onto oxide free silicon wafers at thicknesses resulting in polymer coatings of about ten microns.
After spin coating a film, the solvent is evaporated and the film is thermally cured at 250C for one hour under a nitrogen atmosphere, preferably containing less than 100 ppm oxygen. The cured-polymer coated wafers are then placed in air purged ovens at 1 70~C and are withdrawn periodically to obtain FT-IR spectral absorbance measurements.
.~ ~
~ -25-2 1 2 1 0 5 1 PCr/USg2/lOt73 Lifetimes of the films are based on the time it takes the absorbance at 1700 cm ', expressed as a ratio relative to the film thickness reaches 0.02 microns l This ratio has been shown to correlate with a ten percent increase in the dielectric constant. Lifetimes are less than those indicated in Table I because the test temperature is higher. Results are reported in -5 TABLE ll TABLE II
Polymer/Antioxidant Lifetimes Lifetime Sample At 170C
(Hrs) 1la*Control 30 1lb*Control 28 11c*Control 28 1ld*Control 31 12AgeRite~ MA 136 -: 13Chimassorb~ 944 102 14Cyasorb~ W-3346 95 15Tinuvin~ 144 66 16Tinuvin~ 292 47 17*6-dodecyl-1,2-dihydro- 35 2,2,4-trimethyl quinoline 18*Tinuvin~ 770 32 19*Tinuvin~ 622 29 20*6-ethoxy-1,2-dihydro- 28 2,2,4-trimethyl quinoline * not an example of the invention 2 :3 2 3[ ~ 5 ~
It is expected that the reason for failure of some of these antioxidants to function as such in this system is that the antioxidant is not soluble in the prepolymer solution or the antioxidant volatilizes or decomposes under the elevated temperatures of the cure process.
Antioxidants within the scope of the invention must be tested for function in this use because 5 of thffe properties which are unassociated with thei r ability to prevent oxidation in similar systems to those tested .
Similarly, Agerite~ MA is tested as an antioxidant for the prepolymer made in Procedure C. The exposure to air is conducted in an oven at 1 70~C. The antioxidant is added to a solution of the prepolymer at one weight percent based on the weight of the prepolymer.
10 The solutions are spin coated onto oxide free silicon wafers at thicknesses resulting in polymer coatings of about ten microns.
After spin coating a film, the solvent is evaporated and the film is thermally cured at250Cforonehourunderanitrogenatmosphere,preferablycontaininglessthan 100ppm oxygen. The cured-polymer coated wafers are then placed in air purged ovens at 1 70C and are 15 withdrawn periodically to obtain FT-IR spectral absorbance measurements.
Lifetimes of the films are based on the time it takesthe absorbance at 1 7ûO cm-1, expressed as a ratio relative to the film thickness reaches 0.02 microns-l Results are reported in TABLE lll TABLE III
Polymer/Antioxidant Lifetimes Lifetime Sample At 170C
(Hrs) 21 *Control 6 22 AgeRite MA~ 15 *not an example of the invention 30 The polymer stabilized i n this test differs from the polymer tested in the other tests in that the vinyl groups are not fully reacted. Accordingly, since these vinyl groups are susceptible to oxidation, the times given are much shorter than for the other polymer.
Similarly, Agerite~ MA is tested as an antioxidant for the Cyclotene 3022 prepolymer at the weight percents indicated i n TABLE IV based on the weight of the 35 prepolymer.
WO93/11189 ,~ 0S / PCI/US92/10!73 ..
The solutions are spin coated onto oxide free silicon wafers at thicknesses resuiting in polymer coatings of about ten microns. After spin coating a film, the solvent is evaporated and the film is partially cured using E-beam at the doses stated in the TABLE IV.
After the stated E-beam dose is administered the film is cured at 250C for one 5 hour under a nitrogen atmosphere, preferably containing less than 100 ppm oxygen. The cured-polymer coated wafers are then placed in air purged ovens at 1 50C and are withdrawn periodically to obtain FT-IR spectral absorbance measurements.
Lifetimes of the films are based on the time it takes the absorbance at 1700 cm ', expressed as a ratio relative to the film thickness reaches 0.02 microns ' Results are reported in TABLE III
Polymer/Antioxidant Lifetimes Antioxidant E-Beam Dose Lifetime Concentration~microcoulombs) 23 ~0 0 102 26 ~0 200 96 28 2 20~ 640 29 *0 1200 96 * not an example of the invention 30 These results indicate that E-beam curing may have a negative impact on the antioxidant effect of AgeRite~ MA. But in all cases the polymer containing AgeRite~ MA is thermooxidatively more stable than the polymer without it.
Testing with fully hydrogenated DVS polymers and other fully saturated bisbenzocyclobutene polymers indicates that similar extensions of polymer lifetimes may be 35 obtainecd
H H
or H H H H
15 -~
which are two of the possible structures formed when two side rings open and react with each other; and ~ or --N~
wherein one side ring opens forming the orthoxylylene which reacts with a dienophiie, the first 30 instance being an example c f the product formed by the reaction of the orthoxylylene and a vinyl group and the second bei ng an example of the product formed by the reaction of the orthoxylylene and a maleimide.
Some of the benzylic hydrogens in these structures are depicted for the purpose 35 of illustration When thin films of the arylcyclobutene polymers depicted are exposed to elevated temperatures such as 1 00C or 200C for extended periods of time, such as 200 hours, in an inert atmosphere, such as nitrogen, there may be no changes i n the dielectric constant or WO 93/11 IX9 2 ~ 2 .L 0 S 1 PCr/US92/10173 - ~
the FT-IR spectrum. When thin films of the arylcyclobutene polymers depicted are exposed to oxygen-containing atmospheres such as air, they form a yellow color, the dielectric constant increases and the FT-IR spectrum changes. The oxidized arylcyclobutene polymer absorbs water more readily than unoxidized arylcyclobutene polymer. Any increase in water content leads to 5 a further increase in the dielectric constant. The changes in the dielectric constant and those in the FT-IR spectrum directly correlate, so that one may monitor changes in the dielectric constant by measuring changes in the FT-IR spectrum.
FT-IR studies show that sites with benzylic hydrogens are generally more susceptible to oxidation than other sites in the polymer or prepolymer. For such studies, thin films of the arylcyclobutene polymer are placed on bare silicon substrates having no silicon oxide coating so that the strong absorbance of silicon oxide does not mask the FT-IR spectrum in the area of interest. One may monitor the FT-IR bands at 2952, 1700, 1500, 1254 or 1050 cm-t.
The band at 1500 cm ' is particularly useful as it indicates a ring bending mode for the polymer's tetrahydronaphthalene structure. The spectral absorbance of this band decreases with the 5 decrease in concentration of the tetrahydronaphthalene structure as oxidation occurs. The broad band between 1800 to 1600 cm ', particularly at 1700 cm-1 is an absorption band for aryl carbonyl moieties. The absorbance of this band increases with the concentration of benzylic carbonyls. During polymer thin film oxidation, there is a strong correlation between the reduction in the absorbance at 1 500cm 1 and the increase in absorbance at 1700 cm-'.
The 'dielectric' lifetime or as hereinafter nominated, the 'lifetime' of a thin film polymer coating made from a compound containing an arylcyclobutene n oiety is nominally defined as the time it takes at a given temperature in air for the dielectric constant of the polymer to increase by ten percent. This approximately correlates with the time it takes for the 25 FT-IR absorbance band at 1500 cm 1 to decrease to 80 percent of its initial value. It also correlates well with the ti me it takes for the absorbance at 1700 cm ', divided by the film thickness, to reach 0.02 llm l . Si nce changes in the FT-IR spectrum are easier to measure than changes in the dielectric constant, the changes in the FT-IR may be used to measure lifetimes.
The preferred arylcyclobutene compounds of this invention include compounds 30 of the structure WO 93/1 1 189 2 ~ ~ ~ Q ~ ~ PCr/US92/10173 ( R6 ) r ~ R, 3 --R, 3 - 5 )~R4----Si-0----Si-R4~
(R6)r ~/ R3 R3 ~\(R6)r (R5)q -- -- (R5)q n 1u wherein each R3 is independently C, 6 alkyl, cycloalkyl, aralkyl, or phenyl;
each R4 is independently ethenyl, propenyl or 2-methyl propenyl;
each Rs is independently Cl 6 alkyl, methoxy, or chloro;
each R6 is independently Cl 6 alkyl, chloro, or cyano;
n is an integer of 1 or more; and :
each q and r is independently an integer of zero or l . -The most preferred compound (DVS) is represented by the formula:
[~ Si O S
CH=CH~ ~ I ~ CH=CH
The depictions of this compound herein should not be construed to define any particulargeometric isomer or spatial orientation about the ethenylene double bonds.
Compounds made by the processes disclosed herein contain positional isomers about these double bonds.
These organopolysiloxane bridged bisbenzocyclobutene monomers can be 30 prepared by methodsdisclosed in U.S. Patent 4,812,588 and EP published application 0506314.
These organopolysiloxane bridged bisbenzocyclobutene monomers can be prepared by reacting an excess of a 3- or 4-halo benzocyclobutene, preferably 4-bromobenzocyclobutene, with the desired diterminal vinyl, allyl or methal!yl organo- ;
polysiloxane compound. Typically, a molar ratio of the bromobenzocyclobutene to the - 35 organopolysiloxane bridgi ng group of at least 1.5:1 is desired, preferably at least 2: t .
Preferably, the bromobenzocyclobutene is a 4-bromobenzocyclobutene represented by the formula:
WO 93/11189 21 ~ 1 0 S 1 PCI~/US92JIOt73 s (R6)r ~\13r (R5)q wherein Rs iS Cl 6 alkyl, methoxy, or chloro;
R6 iS Cl 6 alkyl, chloro, or cyano; and each q and r is independently an integer of zero or 1.
A preferred organopolysiloxane compound is represented by the formula:
r R3 ¦ R~
R4 --Si-O-- Si-R4 _ _ n 20 wherein each R3 is independently C1 6 alkyl, cycloalkyl, aralkyl, or phenyl; i-each R4 is independently vinyl (-CH = CH,), allyl (-CH,-CH = CH2), or methallyl ~-CH2-C=C~ .
~ ' ~ ; and :
n is an integer of 1 or more. ~ - -For R3, the preferred cycloalkyl is cyclohexyi and the preferred aralkyl is benzyl.
30 Most preferably, R3 is methyl, R4 is vinyl and q and r are 0.
The coupling reaction of the organopolysiloxane compound with the halobenzocyclobutene is possible because the organopolysiloxane compound is a bisvinyl or bisallyl bridging group. The substitution reaction of an olefinic compound possessing at least one hydrogen on a vinylic position with an organic halide is known and disclosed in U.S.
35 Patent 3,922,299 (Heck) Heck discloses the substitution reaction of aryl halides with olefinic compounds in the presence of a Group Vlll metal, a trivalent arsenic or phosphorous compound, and a soluble WO 93/1 1 189 2 1 ~ ~ ~J ~ ~ PCr/US92/10173 trialkylamine. The reaction displaces a hydrogen on a vinylic or allylic position with the organic compound. For example, the most preferred bisbenzocyclobutene monomer can be prepared by reacting about 2 moles of bromobenzocyclobutene with about one mole of 1,3-divinyl-1,1,3,3-tetramethyl-disiloxane in the presence of a catalytic amount of palladium 5 acetate and tri(orth~tolyl)phosphi ne, in addition to triethylamine, which acts as an acid scavenger.
Organopolysiloxanes and processes for preparing them are known and disclosed in U.S. Patents 3,584,027; 3,701,195; 3,770,768; and 3,803,196. Processes for preparing bromobenzocyclobutene are disclosed in U.S. Patents 4,822,930 and 4,891,455 and by 10 Lloyd et al., Tetrahedron, Vol.21, pp. 245-254 (1965) at page 253.
Following one of the procedures for making the preferred monomer, one will obtain a mixture containing as a major component divinyltetramethyldisiloxane-bis-benzocyclobutene monomer. This monomer mixture has a low viscosity.
Partial thermal polymerization of the arylcyclobutene compound forms a 15 prepolymer which may have more desirable properties in use, such as a wider temperature range between the melting point and the cure temperature and a more desirable viscosity. The prepolymer retains its solubility in organic solvents because it is not polymerized to the gel point. The prepolymer may retain its density and shrinks less than the monomer upon curing. ~ .
The prepolymer can be employed to prepare cured polymeric compositions.
If the arylcyclobutene compound is not already a liquid, it will often melt to aliquid upon heating before it polymerizes. The melted arylcyclobutene compound, typically, has a low viscosity. As polymerization proceeds, the arylcyclobutene compound reaction mixture becomes more viscous.
The prepolymer contains both reacted and unreacted polymerization sites. It may 25 contain completely unreacted arylcyclobutene compound, oligomers and cured polymer as well as other unreacted materials included in the arylcyclobutene compound.
In one method of forming the prepolymer by partial thermal polymerization, an amount of the arylcyclobutene compound is heated to a temperature sufficient to initiate and sustain polymerization. Arylcyclobutene compounds may also be partially polymerized with 30 any type of radiation such as X-ray or E-beam or i n any way that will lead to polymerization.
Polymerization with E-beam or X-ray is not recommended for compositions already containing the antioxidants represented in group 4) such as AgeRite~ MA.
Partial thermal polymerization may be effected over a wide range of temperatures. The lower the temperature the longer the process will take. Partial thermal - 35 polymerization takes place at a temperature effective to polymerize the arylcyclobutene compound. Such a temperature is preferably above 150C and below 220C. The reaction mixture is removed from the heat after it attains an appropriate viscosity which is greater than WO 93/1 1 189 2 ~ PCl/US92/10173 the initial viscosity of the melted arylcyclobutene compound and which enables more effective use of the partially polymerized composition.
The viscous, partially thermally polymerized composition can be employed as a film wherein an effective amount of the neat partially polymerized composition is applied to a S surface, and subsequently further polymerized. Or, the partially polymerized composition can be mixed with a suitable solvent. The solution can then be applied to a surface, the solvent evaporated, and the partially polymerized composition further polymerized to provide a polymer film.
The partial thermal polymerization of DVS to form partially thermally 10 polymerized DVS may be performed by heating the DVS at 1 95C for two hours under nitrogen or alternatively, by heating the DVS at t 70C for 22 hoùrs under nitrogen. Most preferably, the DVS is heated and stirred at 160 to 180C for a period of time of 20 to 24 hours, to reach a weight averaged molecular weight of 30 to 35,000 as measured by gel permeation chromatography against a polystyrene standard.
The partially thermally polymerized DVS and fully cured DVS may contain units oftheformula ''- =`''-' `~
~Si ~CH3 : .
CH3 O ~Si CH3 .:
25 wherein the tetralin structure is formed by the Diels-Alder reaction of one of the vinyl groups and the side ring openi ng of one of the benzocyclobutene moieties.
When coati ng a substrate with a benzocyclobutene, it may be desirable to use anadhesion promoter. Suitable adhesion promoters include triethoxyvinylsilane ~CAS# 78-08-û) andotherorganosilaneadhesionpromotersastaughtforexampleinU.S.patent4,831,172.
The adhesion promoter is most advantageously used when bonding the polymer to an inorganic surface. The adhesion promoter may be coated onto the surface prior to application of the compound containing an arylcyclobutene functionality or it may be mixed in and applied with the compound containing an arylcyclobutene functionality. Preferably the triethoxyvinylsilane adhesion promoter is applied as a thin coating to the surface and a 35 partially thermally polymerized DVS in solution is coated over it. Then, after removal of the solvent, the adhesion promoter and partially thermally polymerized DVS are subjected to conditions sufficient to polymerize the DVS at least beyond its gel point.
WO 93/1 1 189 2 1 2 i ~3 t j ~ PCI /US92/10173 The gel point is described in the Concise Encvclo,~edia Of Polvmer Science And Enaineerinq; Wiley Interscience, 1990, pp. 430-2. The gel point describes a critical point in the polymerization from a monomer to a fully cured polymer. Before the gel point, the polymer is soluble in good solvents. It is called a sol and is a liquid even if highly viscous. Beyond the gel 5 point the polymer is not completely soluble, even in a good solvent. However low molecular weiyhtfractions(sol fraction) maystill beextractable.
Preferably, the gel point can be defined as that point wherein one part of polymerwill notcompletelydissolvein 100partsofagoodsolventatitsboilingpoint. Good solvents include aromatic hydrocarbons such as toluene, xylene, mesitylene; aliphatic 10 hydrocarbons such as pentane, hexane; hetero atom containing hydrocarbons such as N-methyl pyrrolidone and methyl ethyl ketone. More preferably the gel point can be defined as that point wherein one part of polymer will not completely dissolve in ten parts of xylene at its boiling point.
Antioxidants and stabilizers may be chosen frorn broad classes of known materials 15 such as those disclosed in: Oxidation Inhibition In Oraanic Materials, Ed~ Pospisil and Klemchuk, CRC Press, Inc., Boca Raton, Florida, 1990, which is incorporated herein by reference.
Antioxidants useful in this invention are those effective to prevent autoxidation of a polymer made by the side ring opening of an arylcyclobutene.
Exemplary antioxidants include:
1) a compound of the formula:
H3 ~ CH3 25 which is nominally called 4,4'-bis(~l-methylbenzyl)diphenylamine and is commereially available from Goodyear as Wingstay~ 29.
2) a compound of the formula;
~~ C~12C~COOCi~ C
which is nominally cailed tetrakis [methylene (3,5-di-tert-butyl-4-hydroxyhydrocinnamate) methane (CA5 No. 6683-19-6) and is commercially available from ~iba-Geigy as Irganox~ 1010.
WO g3/l 1 189 2 ~ 2 ~ 0 5 1 PCl/US92/10173 3) a compound of the formula:
OH --5(C~3)3C~/C(CE~3)3 OcH2cH 2 S
10 which is nominally called thiodiethylene bis-(3,5-di-tert-butyl-4-hydroxy)hydrocinnamate (CAS No. 41484-35-9) and is commer~ially available from Ciba-Geigy as Irganox~ 1035. ~ -4) compounds of the formula:
CH3 ~:
R~q/~C}i3 H :
20 wherein R is hydrogen, an electron withdrawing or electron donating yroup; and - :oligomers thereof. Preferably R is hydrogen, but it also can be any substituent that does not interfere with the antioxidant activity of the compound. Preferred R substituents are phenyl, ~:
Cl 20 alkyl and alkoxy.
This group also contains the oligomer of the formula <C~3 H \ H / n wherein R is as hereinbefore defined and n is 0-6.
2,2,4-trimethyl-1,2-dihydroquinoline, wherein R is hydrogen, is available as AgeRite~ MA from R. T. Vanderbilt as an oligomer with a degree of polymerization of about 3 or 4 (n is about 1 or 2). :
6-ethoxy-2,2,~trimethyl-1 ,2-dihydroquinoline of the formula WO g3/1 1 189 ~ 1 2 1 ~ PCT/US92/10173 E~sC20~<
N
H
wherein R is ethoxy, is available as Permanax~ ETMQ from Vulnax.
~dodecyl-2,2,4-trimethyl-1 ,2-dihydroquinoline of the formula C12~2~
N
H
wherein R is dodecyl, is available as Santoflex~ DD from Monsanto.
The hereinbefore recited oligomer is available as 600drite 3140 or AgeRite MA X9 Type from B F. Goodrich wherein the manufacturer is said to remove the terminai vinyl group and n is 0 to 5) hindered amines of the formula:
l)2 ( R~) 2 ~R 1 ) 2 ~
( R~\N / ( R2 ) 2 wherein R is hydrogen, an electron withdrawing group or an electron donating group;
each R' is independently, hydrogen, an electron withdrawing group or an . - 15-WO 93/1 1 189 2 1 2 1 0 ~i ~ PCI'/US92/10173 electron donating group, with the proviso that two R1 attached to the same carbon may represent a single moiely joined to said carbon by a double bond; and each R2 is independently, methyl, ethyl, n-propyl or isopropyl.
These compounds belong to a known class called hindered amine light stabilizers as described in Oxidation Inhibition In Oraanic Materials, Ed. Pospisil, J. and Klemchuk, P. P., CRC Publishing, Boca Raton, Florida, 1990, Vol. Il, pp. 1-28, which is hereby incorporated by reference. The structure includes a six-membered ring with one or two nitrogen atoms and four or five carbon atoms and no hydrogens on the carbon atoms adjacent to the hindered nitrogen atoms.
In order to prepare these compounds one may react acetone or another appropriate ketone with ammonia under known conditions to form triacetoneamine or a derivative thereof. This is then reduced to make the alcohol of the formula:
OH
tR1)2 ~R1)2 (R~ I (R2)2 R' and R2 are selected based on the ketone used in the synthesis. The hydroxy function may be converted to an ester function by treatment with the appropriate acid and 25 removal of by-product water using conventional techniques. The ketone function may be converted to an amine function by treatment with the appropriate amine with catalyst and hydrogen using conventional techniques.
WO 93/1 1 189 .~ 1 2 1 ~ Pcr~usg2/1ol73 Exemplary structures include:
C4Hg ~0~ CH2--C-C-~N-Cl13 Cl=O
tO >~
N ;~
which is available as Tinuvin~ 144 from Ciba-Geigy;
1l 1 ,, O-C-~CH2)8--C-O
: ,, ,, .
N N
~: CH3 CH3 25 which is available as Ti nuvin~ 292 or Ti nuvi n~ 765 from Ciba-Geigy or as Sanol~ LS-292 from Sankyo Co. Ltd.;
HN~ O-C- ( CH2 ) 8 -17-~7<~H
whichisavailableasTinuvin~770fromCiba-GeigyorasSanol~LS-770fromSankyoCo~Ltd~;
r~ 1 o 1 ~ n WO 93/1 1 189 2 ~ 2 1 0 ~i ~ PCr/USg2/10173 which is available as Tinuvin~ 622 from Ciba-Geigy;
t'$~ (CH2 6~
O H H n which is available as Cyasorb~ UV-3346 from American Cyanamid Co.;
_--N--(CH2)6--N-(cH2)2--_ ~5 ~
H H n which is available as Spinuvex'9 A-36 from Montefluos, (Borg-Warner for U.S. and Canada);
"~ >~P ~
: HN N-CH2-CH2-N NH
which is available as Goodrite~ 3034 from B. F~ Goodrich;
.' ~ ' W093/11189 ~ PCT/US92/10173 H H
N
rO~N--(CH )6--N~
: fH3 CH3 CH3 CH3 . - n whichis available as Chimassorb~ 944 from Ciba-Geigy;
r ~ 1 r " B
lH-0- ~ N-(CH2)20~ ~ H30-C-(CH2)2 C OC
whichis available as Tinuvin~ 622 as a polymer from Ciba-Geigy;
., ~
' :~
WO 93/1 1 189 2 1 2 1 0 5 ~ PCI`/US92/10173 R R
R-NH(CH2)3N(CH2)2 N(CH2)3 NH R
C4~9 .
wherein R = ~/~ N~N--CH3 ~N
I ~ `~
C4Hg--N ~<N--CH3 which is available as Chimassorb~ 119 FL from Ciba-Geigy.
The antioxidant is added to a compound containing an arylcyclobutene moiety in a manner in which is effective to inhibit oxidation of polymer formed by side ring opening of the arylcyclobutene. The antioxidant may be combined with an arylcyclobutene monomer in liquid or solid form. The arylcyclobutene monomer and antioxidant may both be dissolved in a mutual solvent. The antioxidant may be dissolved in a liquid arylcyclobutene monomer. As the arylcyclobutene monomer is heated to polymerize it, the antioxidant may mix uniformly with it and maintain intimate contact with the polymer.
The antioxidant may be added to a partially polymerized compound containing an arylcyclobutene moiety. The arylcyclobutene prepolymer and antioxidant may both be dissolved in a mutual solvent. The antioxidant may be dissolved in a iiquid partially polymerized arylcyclobutene monomer. As the partially polymerized arylcyclobutene monomer is heated to polymerize it, the antioxidant rnay mix uniformly with it and maintain inti mate contact with the polymer.
Preferablyr effective antioxidants for polymers formed by side ring opening of an arylcyclobutene moiety, will survive the polymer cure without decomposing, blooming, evaporating or reacting disadvantageously with the monomer containing an arylcyclobutene moiety. AgeRite~ MA may deteriorate in effect if the monomer or prepolymer composition containing it is polymerized using electron bean (E-beam) radiation.
The antioxidant is added to a compound containing an arylcyclobutene moiety in an amount which is effective to inhibit oxidation of polymer formed by side ring opening of the arylcyclobutene. The lower limit is defined by the amount necessary to obtain measurable extension of the oxidation lifetime. The upper limit is defined by the amount of antioxidant which degrades polymer properties to an unacceptable level or beyond which additional WO 93/1 1 189 ~ ~ 2 ~ ~ ~ !~ PCI`/US92/ 10173 antioxidant does not extend the useful lifeti me. A preferred amount ranges from 0.1 to l O
weight percent of the antioxidant based on the compound containing an arylcyclobutene moiety. A more preferred amount ranges from 0.5 to 6 weight percent of the antioxidant based on the compound containing an arylcyclobutene moiety. A most preferred amount for S the DVS ranges from 1 to 4 weight percent of the Agerite~ MA antioxidant based on the DVS.
Since the DVS polymer finds a major use as a thin film dielectric, ionic contamination is preferably avoided. Agerite~ MA antioxidant contains sodium chloride and it is recommended that this be removed prior to addition to the compound containing an arylcyclobutene moiety. It can be removed by contacting the antioxidant with water to extract 10 the sodium chloride. Preferably it is dissolved in an organic solvent such as mesitylene to enhance the extraction. The antioxidant may then be isolated from the solvent and water by decantation, vacuum distillation and/or freeze drying.
The following examples are given to illustrate the invention and should not be interpreted as limiting it in any way. Unless stated otherwise, all parts and percentages are 15 given by weight.
Procedure A: Preparation of a Bisbenzocyclobutene Monomer Represented by the Formula:
2~ C~CN CH~S1 0 S1~ )~ (VI) A solution of 3.0 grams (g) ~1 .64x 1 0-2m) 4-bromobenzocyclobutene, 1.52 g 25 (8.2x103m) 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, 1.66g(1.64xl02m)triethylamine,0.152g (5.0x104m) tri-o-tolylphosphine, 72 milligrams (mg) (3.21xlO~m) palladium (il) acetate, and l O cm3 acetonitrile in a 50 cm3 2-neck round bottom flask equipped with a reflux condenser and magnetic stirring bar is heated to reflux for 24 hours. After 24 hours, the reaction mixture is cooled to room temperature and then poured i nto 60 cm3 of l O percent aqueous hydrochloric 30 acid. The resulting mixture is extracted with two 50 cm3 portions of methylene chloride and the combined methylene chloride solutions were washed with three l OO cm3 portions of water.
The organic phase is dried over anhydrous magnesium sulfate, filtered, and evaporated in vacuo to yield a yellow oil. The oil is chromatographed on silica gel eluting with 20 percent toluene in heptane. The product was removed ~rom the column and the solvent removed to 35 yield a colorless oil. Reverse phase high per~ormance liquid chromatography showed a mixture withonemajorcomponent. 'H-NMR(CDCI3)7.3-6.1 (m, 10H),3.2(s,8H),0.2(s, 12H)ppm.
.~
WO93/11189 2l~l.n5l PCI/US92J10173 Procedure B: Preparation of Bisbenzocyclobutene Monomer Derived From an Olefinic Aromatic Compound And Corresponding to the Formula ~ ~ C=CEI ~CII=CH ~ ~ U
(a) q = 3 A 25-cm3 flask equipped with a reflux condenser, nitrogen inlet, and magnetic stirring bar is charged with m-dibromobenzene (1.0 9, 4.2 x 10'3 m), m-divinylbenzene (2.75 g, 15 2.1x102m),tri-n-butylamine(8.4x103m),tri-o-tolylphosphine(64mg,2.1x104m),palladium (Il) acetate (20 mg, 8.4 x 10 5 m), and acetonitrile (10 cm3). The mixture is stirred under nitrogen and heated to reflux for 2 hours. The grey siurry is cooled to room temperature and stirred into 60 cm3 of 10 percent aqueous hydrogen chloride. The resulting precipitate is collected by filtration, washed with water, and air dried. This product is dissolved in ethylacetate, filtere~, 20 and the solvent evaporated to yield a yellow residue.
Recrystallization of the residue from heptane gives 0.60 g (42 percent yield) of a compound of the formula 25 cll2-C~ ~ Cll=C~ ~CII=CII ~ CY=CU2 hereinafter referred to as diterminal olefin, with a melting point of 105C.
A 25-cm3 flask e~uipped with a reflux condenser, nitrogen inlet and magnetic 30 stirring bar is charged with 4-bromobenzocyclobutene ( 1.5 9, 8 x 10-3 moles), the diterminal olefin from part A ( 1.34 9, 4 x 10 3 moles), tri-n-butylamine ( 1.8 g, 9.7 x 10-3 moles), tri-o-tolylphosphine (62 mg, 4.0 x 104 moles), palladium 11 acetate (18 mg, 8.0 x 10 5 moles) and acetonitrile (5 cm3). The reaction rnixture is heated to reflux under nitrogen for 4 hours. The mixture is cooled to room temperature and stirred into 60 cm3 of 10 percent hydrochloric acid.
35 The precipitate is collected by filtration, washed with water and air dried. The dried precipitate is then dissolved in 150 crn3 of boiling toluene, filtered hot and cooled tO yield 310 mg of the productq = 3. Themonomerhasameltingpointof180Cto215C.
WO 93/1 1 189 ~ O cJ ~ PCI`/US92/10173 (b) q = t A 25-cm3 flask equipped with a reflux condenser, nitrogen inlet, and magnetic stirri ng bar is charged with 4-bromobenzocyclobutene ( 1. 50 g, 8.0 x 10 3 m), m-di vinyl benzene (4.0 x 10'3 m), tri-n-butylamine ( 1.8 9, 9.7 x 10 3 m), tri-o-tolylphosphine (62 mg, 4.0 x 10 4 m), palladium(Il)acetate(18mg,8.0x10;m),andacetonitrile(5 cm3). Thereactionmixtureisheated to reflux under nitrogen with stirring for 4 hours. The solidified mixture is cooled to room temperature and stirred into 60 cm3 of 10 percent aqueous hydrogen chloride. The resulting precipitate is collected by filtration, washed with water, and air dried.
The precipitate is dissolved in 75 cm3 of boiling ethylacetate, filtered hot, and cooled to yield 800 mg (60 percent) of the desi red monomer with a melting point of 1 50C to Procedure C:
A Partially Polymerized Composition From The Compound Of The BisbenzocyclobuteneDerived From Meta-Divinyl Benzene Of Procedure B (b) H H H H H H H
H j~ l = l~ l = !~
A 1 g samp!e of the monomer of Procedure B (b) is heated from 189 to 222C at 25 the rate of 1C per minute. The partially polymerized composition has a viscosity of 249 poise at 220C, the partially polymerized composition is solid at room temperature and becomes gel-li ke at 180 to 1 90C. The partially polymerized composition contains 51 percent unreacted polymerizable functionality as determined by differential scanning calorimetry.
Exam~!es The noted antioxidant is dissolved in a partially thermally polymerized 1 ,3-bis(2 -bicyclo~4.2.0jocta- 1 ,3,5-trien-3-ylethenyl)- 1,1,3,3--tetramethyldisiloxane, available as a solution in mesitylene from The Dow Chemical Company as Cyclotene 3022~ at one weight percent based on the weight of the prepolymer A control, containing no antioxidant, is run for comparison purposes. The solutions are spin coated onto 35 oxide free silicon wafers at thicknesses resulting in polymer coatings of about ten microns~
The coating thickness can be controlled by selecting the viscosity of the solution, the spin speed and the spin time. Viscosity may be controlled by adjusting the concentration of WO g3/1 1 IX9 PCI/US92/10173 ~
:2121~Sl prepolymer in the solution. Preferably, a solution containing 55 per~ent DVS prepolymer in mesitylene and 1 percent antioxidant based on the weight of the prepolymer is puddled onto a silicon wafer. The wafer is then spun for about 3 seconds at 500 rpm and then spun for about 30 seconds at 5000 rpm tO spread the prepolymer evenly.
After spin coating a film, the solvent is evaporated and the film is thermally cured at 250C for one hour under a nitrogen atmosphere, preferably containing less than 100 ppm oxygen. The cured-polymer coated wafers are then placed in air purged ovens at the temperatures noted and are withdrawn periodically to obtain FT-IR spectral absorbance measurements.
Lifetimes of the films are based on the time it takes the absorbance at 1500 cm ' to reach 80 percent of its initial value. This band indicates the presence of tetralin which contains the benzylic hydrogens. Comparisons have shown that this corresponds to about a 10 percent increase in the dielectric constant which is the real indicator of i nterest in thin film dielectrics.
The use of silicon wafers permits the taking of the absorbance spectral 15 measurements through the transparent wafer and polymer film without degrading the film.
Absorbance measurements in this context refer to the definition given by:
A = -logT
wherein T is the transmittance and A is the absorbance. Transmittance is defined as:
T Is/lb 20 wherein Is is the intensity of light transmitted by the cured-polymer coated silicon wafer and Ib istheintensityoflighttransmitted bythesiliconwaferalone.
The absorbance band at 1500 cm ' typically does not have a local baseline at zero absorbance. Therefore, the absorbance at 1500 cm ' is measured relative to a line connecting two points taken as the lo.cal spectral baseline. 1520 cm ' and 1470 cm may advantageously be usedtodefinethelocal baseline.
The lifetime of the control at 100C is greaterthan 3500 hrs. Lifetimes of curedDVS with 1 percent by weight of the noted antioxidants, at oven temperatures of 1 25C and 1 50C are shown in the TABLE 1.
093/11189 ~ ~ ~ PCT/US92/10173 TABLE I
Polymer/Antioxidant Lifetimes Lifetime (Hrs) - SamPle at 150C at 125C
1*Control 97 450 2*AgeRite 94 447 Stalite~
(Vanderbilt) 3~bis(diphenyl 95 440 phosphino) methane 4*Irganox0 1076 95 456 (CIBA-GEIGY) 5 *A~eRite~ DPPD lO0 . 482 (Vanderbilt) 6*Irganox~ B215 108 528 (CIBA-GEIGY) 7Wingstay~ 29 121 669 :~ (Goodyear) 8Irganox~ 1035 127 631 (Ciba-Geigy) .
9Irganox~ lOlO 131 678 (Ciba-Geigy) :
10AgeRite~ MA 431 2790 ``
: (Vanderbilt) * not an example of the invention Similarly, various other antioxidants are screened. The exposure to air is conducted in an oven at 1 70C and accordingly the times are shorter than in TABLE 1. Each antioxidant is added to a sol ution of DVS prepolymer at one weight percent based on the weight of the prepolymer. Four controls, containing no antioxidant, are run for comparison purposes. The solutions are spin coated onto oxide free silicon wafers at thicknesses resulting in polymer coatings of about ten microns.
After spin coating a film, the solvent is evaporated and the film is thermally cured at 250C for one hour under a nitrogen atmosphere, preferably containing less than 100 ppm oxygen. The cured-polymer coated wafers are then placed in air purged ovens at 1 70~C and are withdrawn periodically to obtain FT-IR spectral absorbance measurements.
.~ ~
~ -25-2 1 2 1 0 5 1 PCr/USg2/lOt73 Lifetimes of the films are based on the time it takes the absorbance at 1700 cm ', expressed as a ratio relative to the film thickness reaches 0.02 microns l This ratio has been shown to correlate with a ten percent increase in the dielectric constant. Lifetimes are less than those indicated in Table I because the test temperature is higher. Results are reported in -5 TABLE ll TABLE II
Polymer/Antioxidant Lifetimes Lifetime Sample At 170C
(Hrs) 1la*Control 30 1lb*Control 28 11c*Control 28 1ld*Control 31 12AgeRite~ MA 136 -: 13Chimassorb~ 944 102 14Cyasorb~ W-3346 95 15Tinuvin~ 144 66 16Tinuvin~ 292 47 17*6-dodecyl-1,2-dihydro- 35 2,2,4-trimethyl quinoline 18*Tinuvin~ 770 32 19*Tinuvin~ 622 29 20*6-ethoxy-1,2-dihydro- 28 2,2,4-trimethyl quinoline * not an example of the invention 2 :3 2 3[ ~ 5 ~
It is expected that the reason for failure of some of these antioxidants to function as such in this system is that the antioxidant is not soluble in the prepolymer solution or the antioxidant volatilizes or decomposes under the elevated temperatures of the cure process.
Antioxidants within the scope of the invention must be tested for function in this use because 5 of thffe properties which are unassociated with thei r ability to prevent oxidation in similar systems to those tested .
Similarly, Agerite~ MA is tested as an antioxidant for the prepolymer made in Procedure C. The exposure to air is conducted in an oven at 1 70~C. The antioxidant is added to a solution of the prepolymer at one weight percent based on the weight of the prepolymer.
10 The solutions are spin coated onto oxide free silicon wafers at thicknesses resulting in polymer coatings of about ten microns.
After spin coating a film, the solvent is evaporated and the film is thermally cured at250Cforonehourunderanitrogenatmosphere,preferablycontaininglessthan 100ppm oxygen. The cured-polymer coated wafers are then placed in air purged ovens at 1 70C and are 15 withdrawn periodically to obtain FT-IR spectral absorbance measurements.
Lifetimes of the films are based on the time it takesthe absorbance at 1 7ûO cm-1, expressed as a ratio relative to the film thickness reaches 0.02 microns-l Results are reported in TABLE lll TABLE III
Polymer/Antioxidant Lifetimes Lifetime Sample At 170C
(Hrs) 21 *Control 6 22 AgeRite MA~ 15 *not an example of the invention 30 The polymer stabilized i n this test differs from the polymer tested in the other tests in that the vinyl groups are not fully reacted. Accordingly, since these vinyl groups are susceptible to oxidation, the times given are much shorter than for the other polymer.
Similarly, Agerite~ MA is tested as an antioxidant for the Cyclotene 3022 prepolymer at the weight percents indicated i n TABLE IV based on the weight of the 35 prepolymer.
WO93/11189 ,~ 0S / PCI/US92/10!73 ..
The solutions are spin coated onto oxide free silicon wafers at thicknesses resuiting in polymer coatings of about ten microns. After spin coating a film, the solvent is evaporated and the film is partially cured using E-beam at the doses stated in the TABLE IV.
After the stated E-beam dose is administered the film is cured at 250C for one 5 hour under a nitrogen atmosphere, preferably containing less than 100 ppm oxygen. The cured-polymer coated wafers are then placed in air purged ovens at 1 50C and are withdrawn periodically to obtain FT-IR spectral absorbance measurements.
Lifetimes of the films are based on the time it takes the absorbance at 1700 cm ', expressed as a ratio relative to the film thickness reaches 0.02 microns ' Results are reported in TABLE III
Polymer/Antioxidant Lifetimes Antioxidant E-Beam Dose Lifetime Concentration~microcoulombs) 23 ~0 0 102 26 ~0 200 96 28 2 20~ 640 29 *0 1200 96 * not an example of the invention 30 These results indicate that E-beam curing may have a negative impact on the antioxidant effect of AgeRite~ MA. But in all cases the polymer containing AgeRite~ MA is thermooxidatively more stable than the polymer without it.
Testing with fully hydrogenated DVS polymers and other fully saturated bisbenzocyclobutene polymers indicates that similar extensions of polymer lifetimes may be 35 obtainecd
Claims (9)
1. A composition containing a compound containing an arylcyclobutene moiety and an antioxidant compound of the formula:
1) 2) 3) 4) wherein R is hydrogen, an electron withdrawing or electron donating group; and oligomers thereof;
5) hindered amines of the formula:
wherein R is hydrogen, an electron withdrawing group or an electron donating group;
each R1 is independently, hydrogen, an electron withdrawing group or an electron donating group, with the proviso that two R1 attached to the same carbon may represent a single moiety joined to said carbon by a double bond;
each R2 is independently, methyl, ethyl, n-propyl or isopropyl;
said antioxidant being effective to inhibit oxidation of polymer formed by side ring opening of the arylcyclobutene.
1) 2) 3) 4) wherein R is hydrogen, an electron withdrawing or electron donating group; and oligomers thereof;
5) hindered amines of the formula:
wherein R is hydrogen, an electron withdrawing group or an electron donating group;
each R1 is independently, hydrogen, an electron withdrawing group or an electron donating group, with the proviso that two R1 attached to the same carbon may represent a single moiety joined to said carbon by a double bond;
each R2 is independently, methyl, ethyl, n-propyl or isopropyl;
said antioxidant being effective to inhibit oxidation of polymer formed by side ring opening of the arylcyclobutene.
2. The composition of Claim 1 wherein the antioxidant is a compound of the formula:
wherein R is hydrogen, an electron withdrawing or electron donating group; or an oligomer thereof.
wherein R is hydrogen, an electron withdrawing or electron donating group; or an oligomer thereof.
3. The composition of Claim 2 wherein the antioxidant is a compound selected from the group consisting of 2,2,4-trimethyl-1,2-dihydroquinoline, oligomers thereof, or oligomers thereof with the terminal vinyl group removed.
4. The composition of Claim 3 wherein the antioxidant is an oligomer of 2,2,4-trimethyl-1,2-dihydroquinoline with a degree of polymerization of about 3 or 4.
5. The composition of Claim 4 wherein the compound with an arylcyclobutene moiety is DVS, a compound of the formula:
or a prepolymer or polymer thereof.
or a prepolymer or polymer thereof.
6. The composition of Claim 5 wherein the compound with an arylcyclobutene moiety is a partially thermally polymerized DVS
prepolymer.
prepolymer.
7. A composition containing a polymer formed by the side ring opening of an arylcyclobutene compound and an antioxidant compound of the formula:
1) 2) 3) 4) wherein R is hydrogen, an electron withdrawing or electron donating group; and oligomers thereof;
5) hindered amines of the formula:
wherein R is hydrogen, an electron withdrawing group or an electron donating group;
each R1 is independently, hydrogen, an electron withdrawing group or an electron donating group, with the proviso that two R1 attached to the same carbon may represent a single moiety joined to said carbon by a double bond;
each R2 is independently, methyl, ethyl, n-propyl or isopropyl;
said antioxidant being effective to inhibit oxidation.
1) 2) 3) 4) wherein R is hydrogen, an electron withdrawing or electron donating group; and oligomers thereof;
5) hindered amines of the formula:
wherein R is hydrogen, an electron withdrawing group or an electron donating group;
each R1 is independently, hydrogen, an electron withdrawing group or an electron donating group, with the proviso that two R1 attached to the same carbon may represent a single moiety joined to said carbon by a double bond;
each R2 is independently, methyl, ethyl, n-propyl or isopropyl;
said antioxidant being effective to inhibit oxidation.
8. A method for inhibiting oxidation of a polymer formed by the side ring opening of compounds containing one or more arylcyclobutene moieties by adding to the compound, a partially polymerized prepolymer of said compound or a polymer of the compound, an amount of an antioxidant sufficient to inhibit oxidation of said said polymer, said antioxidant being selected from the group consisting of:
1) 2) 3) 4) wherein R is hydrogen, an electron withdrawing or electron donating group; and oligomers thereof;
5) hindered amines of the formula:
wherein R is hydrogen, an electron withdrawing group or an electron donating group;
each R1 is independently, hydrogen, an electron withdrawing group or an electron donating group, with the proviso that two R1 attached to the same carbon may represent a single moiety joined to said carbon by a double bond;
each R2 is independently, methyl, ethyl, n-propyl or isopropyl.
1) 2) 3) 4) wherein R is hydrogen, an electron withdrawing or electron donating group; and oligomers thereof;
5) hindered amines of the formula:
wherein R is hydrogen, an electron withdrawing group or an electron donating group;
each R1 is independently, hydrogen, an electron withdrawing group or an electron donating group, with the proviso that two R1 attached to the same carbon may represent a single moiety joined to said carbon by a double bond;
each R2 is independently, methyl, ethyl, n-propyl or isopropyl.
9. An article containing a component which is a polymer formed by side ring opening of an arylcyclobutene moiety and an antioxidant in an amount sufficient to inhibit oxidation of the polymer, said antioxidant being selected from the group consisting of:
1) 2) 3) 4) wherein R is hydrogen, an electron withdrawing or electron donating group; and oligomers thereof;
5) hindered amines of the formula:
wherein R is hydrogen, an electron withdrawing group or an electron donating group;
each R1 is independently, hydrogen, an electron withdrawing group or an electron donating group, with the proviso that two R1 attached to the same carbon may represent a single moiety joined to said carbon by a double bond;
each R2 is independently, methyl, ethyl, n-propyl or isopropyl.
1) 2) 3) 4) wherein R is hydrogen, an electron withdrawing or electron donating group; and oligomers thereof;
5) hindered amines of the formula:
wherein R is hydrogen, an electron withdrawing group or an electron donating group;
each R1 is independently, hydrogen, an electron withdrawing group or an electron donating group, with the proviso that two R1 attached to the same carbon may represent a single moiety joined to said carbon by a double bond;
each R2 is independently, methyl, ethyl, n-propyl or isopropyl.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US07/800,787 US5185391A (en) | 1991-11-27 | 1991-11-27 | Oxidation inhibited arylcyclobutene polymers |
| US07/800,787 | 1991-11-27 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2121051A1 true CA2121051A1 (en) | 1993-06-10 |
Family
ID=25179359
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002121051A Abandoned CA2121051A1 (en) | 1991-11-27 | 1992-11-23 | Oxidation inhibited arylcyclobutene polymers |
Country Status (10)
| Country | Link |
|---|---|
| US (1) | US5185391A (en) |
| EP (1) | EP0614474B1 (en) |
| JP (1) | JP3213000B2 (en) |
| KR (1) | KR100249583B1 (en) |
| CA (1) | CA2121051A1 (en) |
| DE (1) | DE69229558T2 (en) |
| MY (1) | MY110821A (en) |
| SG (1) | SG44646A1 (en) |
| TW (1) | TW221702B (en) |
| WO (1) | WO1993011189A1 (en) |
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| US5411969A (en) * | 1993-04-16 | 1995-05-02 | Bristol-Myers Squibb Company | Antihyperlipidemic/antioxidant dihydroquinolines |
| US5532817A (en) * | 1994-10-03 | 1996-07-02 | The Dow Chemical Company | Method of optical inspection |
| US5994489A (en) * | 1994-10-24 | 1999-11-30 | The Dow Chemical Company | Adhesion promoter and self-priming arylcyclobutene resin compositions |
| US5668210A (en) * | 1994-10-24 | 1997-09-16 | The Dow Chemical Company | Adhesion promoter and self-priming arylcyclobutene resin compositions |
| US6184284B1 (en) | 1998-08-24 | 2001-02-06 | The Dow Chemical Company | Adhesion promoter and self-priming resin compositions and articles made therefrom |
| US6361926B1 (en) * | 1998-10-23 | 2002-03-26 | The Dow Chemical Company | Acid functional polymers based on benzocyclobutene |
| US6420093B1 (en) | 2000-02-02 | 2002-07-16 | The Dow Chemical Company | Toughened benzocyclobutene based polymers and their use in building-up printed wiring boards |
| US6903505B2 (en) | 2001-12-17 | 2005-06-07 | General Electric Company | Light-emitting device with organic electroluminescent material and photoluminescent materials |
| US6891330B2 (en) * | 2002-03-29 | 2005-05-10 | General Electric Company | Mechanically flexible organic electroluminescent device with directional light emission |
| US7449246B2 (en) * | 2004-06-30 | 2008-11-11 | General Electric Company | Barrier coatings |
| US20050181212A1 (en) * | 2004-02-17 | 2005-08-18 | General Electric Company | Composite articles having diffusion barriers and devices incorporating the same |
| US20060208634A1 (en) * | 2002-09-11 | 2006-09-21 | General Electric Company | Diffusion barrier coatings having graded compositions and devices incorporating the same |
| US7015640B2 (en) | 2002-09-11 | 2006-03-21 | General Electric Company | Diffusion barrier coatings having graded compositions and devices incorporating the same |
| US6809781B2 (en) * | 2002-09-24 | 2004-10-26 | General Electric Company | Phosphor blends and backlight sources for liquid crystal displays |
| US7019093B2 (en) | 2002-10-18 | 2006-03-28 | Dow Global Technologies Inc. | Aqueous developable, photosensitive benzocyclobutene-based oligomers and polymers with high moisture resistance |
| US7585785B2 (en) * | 2003-02-05 | 2009-09-08 | Dow Global Technologies | Sacrificial benzocyclobutene copolymers for making air gap semiconductor devices |
| US20090110892A1 (en) * | 2004-06-30 | 2009-04-30 | General Electric Company | System and method for making a graded barrier coating |
| US8034419B2 (en) * | 2004-06-30 | 2011-10-11 | General Electric Company | Method for making a graded barrier coating |
| CA2574581A1 (en) * | 2004-07-23 | 2006-02-09 | Polnox Corporation | Anti-oxidant macromonomers and polymers and methods of making and using the same |
| DE602005022743D1 (en) * | 2004-10-13 | 2010-09-16 | Dow Global Technologies Inc | Polymer formulations based on benzocyclobutene base and method for processing such formulations in oxidative environments |
| US8143360B2 (en) * | 2004-10-13 | 2012-03-27 | Dow Global Technologies Llc | Aqueous developable benzocyclobutene-based polymer composition and method of use of such compositions |
| EP1828104A1 (en) | 2004-12-03 | 2007-09-05 | Polnox Corporation | Synthesis of aniline and phenol-based antioxidant macromonomers and corresponding polymers |
| WO2006091705A2 (en) | 2005-02-22 | 2006-08-31 | Polnox Corporation | Nitrogen and hindered phenol containing dual functional macromolecular antioxidants: synthesis , performances and applications |
| EP1866279A2 (en) * | 2005-03-25 | 2007-12-19 | Polnox Corporation | Alkylated and polymeric macromolecular antioxidants and methods of making and using the same |
| TWI391436B (en) * | 2005-10-13 | 2013-04-01 | Dow Global Technologies Llc | Benzocyclobutene based polymer formulations and methods for processing such formulations in oxidative environments |
| US7705176B2 (en) * | 2005-10-27 | 2010-04-27 | Polnox Corporation | Macromolecular antioxidants based on sterically hindered phenols and phosphites |
| US20070149660A1 (en) * | 2005-10-27 | 2007-06-28 | Vijayendra Kumar | Stabilized polyolefin compositions |
| US20070106059A1 (en) * | 2005-10-27 | 2007-05-10 | Cholli Ashok L | Macromolecular antioxidants and polymeric macromolecular antioxidants |
| WO2007064843A1 (en) | 2005-12-02 | 2007-06-07 | Polnox Corporation | Lubricant oil compositions |
| CN100374448C (en) * | 2005-12-30 | 2008-03-12 | 四川大学 | Diene silicoxyane linking disbenzocyclobutylene monomer and process for preparing prepolymer |
| WO2008005358A2 (en) | 2006-07-06 | 2008-01-10 | Polnox Corporation | Novel macromolecular antioxidants comprising differing antioxidant moieties: structures, methods of making and using the same |
| US7767853B2 (en) | 2006-10-20 | 2010-08-03 | Polnox Corporation | Antioxidants and methods of making and using the same |
| US20080138624A1 (en) * | 2006-12-06 | 2008-06-12 | General Electric Company | Barrier layer, composite article comprising the same, electroactive device, and method |
| US20080138538A1 (en) * | 2006-12-06 | 2008-06-12 | General Electric Company | Barrier layer, composite article comprising the same, electroactive device, and method |
| US7781031B2 (en) | 2006-12-06 | 2010-08-24 | General Electric Company | Barrier layer, composite article comprising the same, electroactive device, and method |
| JP5628474B2 (en) | 2008-03-31 | 2014-11-19 | 東レ・ダウコーニング株式会社 | Organopolysiloxane, method for producing the same, curable silicone composition, and cured product thereof |
| US20100080929A1 (en) * | 2008-09-30 | 2010-04-01 | General Electric Company | System and method for applying a conformal barrier coating |
| US8033885B2 (en) * | 2008-09-30 | 2011-10-11 | General Electric Company | System and method for applying a conformal barrier coating with pretreating |
| US9472783B2 (en) * | 2009-10-12 | 2016-10-18 | General Electric Company | Barrier coating with reduced process time |
| US9209067B2 (en) * | 2013-11-14 | 2015-12-08 | Rohm And Haas Electronic Materials Llc | Gap-fill methods |
| US10294423B2 (en) | 2013-11-22 | 2019-05-21 | Polnox Corporation | Macromolecular antioxidants based on dual type moiety per molecule: structures, methods of making and using the same |
| US9752051B2 (en) | 2015-04-06 | 2017-09-05 | Rohm And Haas Electronic Materials Llc | Polyarylene polymers |
| US10113024B2 (en) * | 2015-12-21 | 2018-10-30 | Dow Global Technologies Llc | Arylcyclobutenes |
| US20180251695A1 (en) | 2017-03-01 | 2018-09-06 | Polnox Corporation | Macromolecular Corrosion (McIn) Inhibitors: Structures, Methods Of Making And Using The Same |
| US20220002474A1 (en) | 2020-07-02 | 2022-01-06 | Rohm And Haas Electronic Materials Llc | Bisbenzocyclobutene formulations |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS50138050A (en) * | 1974-04-23 | 1975-11-04 | ||
| US4642329A (en) * | 1984-08-27 | 1987-02-10 | The Dow Chemical Company | Prepolymer processing of arylcyclobutene monomeric compositions |
| US4540763A (en) * | 1984-09-14 | 1985-09-10 | The Dow Chemical Company | Polymers derived from poly(arylcyclobutenes) |
| US4960593A (en) * | 1985-01-30 | 1990-10-02 | Hilmont Incorporated | Process for preparing thermally stable olefinic polymers |
| US4622375A (en) * | 1986-03-28 | 1986-11-11 | Shell Oil Company | Amorphous ethylene/propylene polymers |
| US4783514A (en) * | 1986-02-28 | 1988-11-08 | The Dow Chemical Company | Polymeric monoarylcyclobutane compositions |
| JP2579937B2 (en) * | 1987-04-15 | 1997-02-12 | 株式会社東芝 | Electronic circuit device and method of manufacturing the same |
| US4822839A (en) * | 1987-11-25 | 1989-04-18 | Hercules Incorporated | Polyunsaturated hydrocarbon polymer-compatible antioxidant compositions |
| US4812588A (en) * | 1987-12-14 | 1989-03-14 | The Dow Chemical Company | Polyorganosiloxane-bridged bisbenzocyclobutene monomers |
| JPH02165662A (en) * | 1988-12-20 | 1990-06-26 | Dainippon Printing Co Ltd | Mounting method for semiconductor integrated circuit |
-
1991
- 1991-11-27 US US07/800,787 patent/US5185391A/en not_active Expired - Lifetime
-
1992
- 1992-11-23 KR KR1019940701768A patent/KR100249583B1/en not_active IP Right Cessation
- 1992-11-23 SG SG1996004922A patent/SG44646A1/en unknown
- 1992-11-23 JP JP51023493A patent/JP3213000B2/en not_active Expired - Lifetime
- 1992-11-23 EP EP93900651A patent/EP0614474B1/en not_active Expired - Lifetime
- 1992-11-23 DE DE69229558T patent/DE69229558T2/en not_active Expired - Lifetime
- 1992-11-23 WO PCT/US1992/010173 patent/WO1993011189A1/en active IP Right Grant
- 1992-11-23 CA CA002121051A patent/CA2121051A1/en not_active Abandoned
- 1992-11-27 MY MYPI92002181A patent/MY110821A/en unknown
- 1992-12-02 TW TW081109651A patent/TW221702B/zh not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| WO1993011189A1 (en) | 1993-06-10 |
| EP0614474A1 (en) | 1994-09-14 |
| EP0614474A4 (en) | 1995-06-28 |
| DE69229558D1 (en) | 1999-08-12 |
| JPH07501572A (en) | 1995-02-16 |
| KR100249583B1 (en) | 2000-03-15 |
| EP0614474B1 (en) | 1999-07-07 |
| DE69229558T2 (en) | 2000-03-30 |
| US5185391A (en) | 1993-02-09 |
| SG44646A1 (en) | 1997-12-19 |
| TW221702B (en) | 1994-03-11 |
| MY110821A (en) | 1999-05-31 |
| JP3213000B2 (en) | 2001-09-25 |
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| FZDE | Discontinued |