GB2243365A - Carboxy iodonium bisulfate salts - Google Patents
Carboxy iodonium bisulfate salts Download PDFInfo
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- GB2243365A GB2243365A GB9108436A GB9108436A GB2243365A GB 2243365 A GB2243365 A GB 2243365A GB 9108436 A GB9108436 A GB 9108436A GB 9108436 A GB9108436 A GB 9108436A GB 2243365 A GB2243365 A GB 2243365A
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C63/00—Compounds having carboxyl groups bound to a carbon atoms of six-membered aromatic rings
- C07C63/04—Monocyclic monocarboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/682—Polyesters containing atoms other than carbon, hydrogen and oxygen containing halogens
- C08G63/6824—Polyesters containing atoms other than carbon, hydrogen and oxygen containing halogens derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/6826—Dicarboxylic acids and dihydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/04—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers only
- C08G65/06—Cyclic ethers having no atoms other than carbon and hydrogen outside the ring
- C08G65/08—Saturated oxiranes
- C08G65/10—Saturated oxiranes characterised by the catalysts used
- C08G65/105—Onium compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
- C08G69/28—Preparatory processes
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- Materials For Photolithography (AREA)
Abstract
Carboxy iodonium bisulfate salts of the formula, <IMAGE> where R is a C(1-8)alkyl radical and a is equal to 0 to 3.
Description
CARBOXY IODONIUM BISULFATE SALTS
BACKGROUND OF THE INVENTION
The present invention is divided from
GB 2210379, Application No. 8822036.3. The present
invention relates to carboxy iodonium bisulfate salts.
Prior to the present invention, Y. Yamada and M.
Okawara reported the synthesis of phenyl polystyryliodonium salts having the iodonium structure as a pendant group on the main chain, Macromol. Chem. 152, 153, 163 (1972). H.K.
Livingston and J.W. Sullivan, J. Polym. Sci. C., 195 (1968) synthesized polymeric iodonium materials by various procedures including the condensation of a dicarboxylic acid and an organoiodosodiacetate. Additional investigations by
Y. Yamada, K. Kashima, and M. -Okawara IJ. Polym. Sci.,
Polym. Let. Ed. 14, 65 (197) ] reported the reaction of 4,4'-methylene bis(phenyliodoso diacetate) with diphenylmethane resulting in the production of an oligomeric iodonium salt.
According to the present invention there are provided
Carboxy iodonium bisulfate salts of the formula,
where R is a C (1-8) alkyl radical and a is ecual to O to 2.
GB 2210379A is based on the discovery that high molecular weight resins containing iodonium salt components in the main chain can be made by initially effecting the interfacial polymerization of the diacidhalide of dicarboxydialkyldiphenyliodonium bisulfate of the formula,
with diamines, difunctional alcohols, or phenols to produce the corresponding iodonium containing polyamides and polyesters, where R is a C 8) alkyl radical, X is a halogen radical, and a is a whole number equal to O to 3 inclusive.Polymeric photosensitive iodonium salts are provided comprising chemically combined units of the formula,
which can be metathesized with an alkali metal or alkaline earth metal hexafluoro compounds of the formula Fn ' (3) to produce the corresponding polymeric polyfluoro metalloid iodonium salts, where R1 and R2 are selected from C(6 14) divalent aryl radicals and C(6-14) divalent aryl radicals substituted with 1-4 monovalent radicals inert during interfacial polymerization, Q is a member selected from
R4 and R5 are the same or different monovalent radicals selected from hydrogen or C(l4) radicals, R3 is a divalent C (1-14) hydrocarbon radical or divalent C(1 14) hydrocarbon radical substituted with monovalent radicals inert during interfacial polymerization, 6 is a divalent C divalent organo radical, M is an element selected from hydrogen, sodium, potassium or magnesium, Y is selected from
B, P, As and Sb, and n is an integer having a value of 4-6.
There is provided by GB 2210379A polymeric iodonium salts comprising chemically combined units of the formula,
where R1, R2, Q, Y, and n are as previously defined.
There are included by R, R4, and R5 radicals of formulas (1) and (2), C(1 8) alkyl radicals such as methyl, ethyl, propyl, butyl, pentyl, hexyl, etc. Radicals included within R3 are, for example, divalent alkylene radicals such as methylene, dimethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene; arylene radicals such as phenylene, xylylene, tolylene, naphthylene, anthrylene. R1 and and R2 are, for example, arylene radicals included within R3 and such divalent aryl radicals substituted with C(1 4) alkyl, halogen such as chloro, nitro, alkoxy.Radicals included within R6 are, for example, # (1-8) alkylene radicals and C arylene radicals, such as phenylene radicals, xylylene, toluene, and divalent radicals of the formula,
where Z is a divalent radical selected from
x is an integer equal to 1 to 5, and b is equal to O or 1.
In the practice of the invention, the dicarboxydiaryl iodonium bisulfate salts such as shown by formula (1) are initially made by effecting reaction between an alkyl substituted arylcarboxylic acid, such as o-toluic acid and an alkali metal iodate, such as potassium iodate, in the presence of acetic anhydride, sulfuric acid and an inert organic solvent. Typical inert organic solvents are, for example, methylene chloride, chloroform, nitromethane, nitroethane, nitropropane, carbon tetrachloride, and o-dichlorobenzene. The formation of the iodonium bisulfate salt can be effected by maintaining the reaction mixture at a temperature from about -30 to 300C. during the sulfuric acid addition. After the addition, the mixture can be stirred under ambient temperatures for several days.
Recovery of the iodonium bisulfate salt can be achieved by addition of water to the reaction mixture followed by filtration in accordance with the standard procedures.
Conversion of the dicarboxydiaryliodonium bisulfate salt to the corresponding acid halide can be achieved by use of a halogenating agent, such as thionylchloride in accordance with standard techniques. For example, a mixture of the diaryl iodonium dicarboxylic acid and thionyl chloride can be heated to reflux and hydrogen chloride can be separated.
Intercondensation of the diaryliodonium dicarboxylic halide salt of formula (1) with organic diamine can be achieved in the absence of light and in the presence of an organic solvent and base, while the temperature is maintained at about 00C to 600C. with agitation.
Substantially equal molar amounts of the diamine and diaryliodonium dicarboxylic halide can be used. Suitable organic diamines which can be employed in the practice ofthe present invention to make the iodonium polyamides are compounds included within the formula,
where R4, R3, and R5 are as previously defined. Some of the organic diamines which can be used are, for example, ethylenediamine, 1,6-hexamethylenediamine, 1,3-propanediamine, 1,4-butanediamine, 1,4-cyclohexanediamine, 1, 4-phenylenediamine, ) 3#phenylenediamine, toluene-2,4-diamine, 1,4-napthalenediamine, 4,4'-methylenedianiline, 4,4'-oxydianiline, 2,5-dimethylpiperazine, piperazine, and 4,4'-sulfonyldianiline.
In instances where a polyester copolymer is desired, suitable organic dihydroxy compounds can be used, such as HO-R6 -OH, where R6 is as previously defined.
Some of the organic dihydroxy compounds are, for example, ethyleneglycol, 1,4-butanediol, 1,3-propanediol, 1,4-cyclohexanediol, 1,6-hexanediol, diethyleneglycol, triethyleneglycol, bisphenol-A, hydroquinone, resorcinol, catechol, 4,4'-oxydiphenol, 4,4'-biphenol, 4,4'-thiobiphenol, 1,4-cyclohexanedimethanol, and neopentylglycol.
It has also been found that in particular instances it can be advantageous to employ aromatic dicarboxylic acid halides, such as phthaloyl chloride, isophthaloylchloride and terephthaloylchloride as comonomers to improve the solubility of the resulting iodonium salt containing photopolymers in common organic solvents. A proportion of up to 50 mole % of aromatic dicarboxylic acid halide can be used based on total moles of diaryliodonium dicarboxylic halide bisulfate and aromatic dicarboxylic halide to avoid adversely affecting the photo-sensitivity of the resulting copolymer.
The photosensitive iodonium polymer comprising chemically combined units of formula (2) can be metathesized with an alkali metal or alkaline earth metal hexafluoro compound of formula (3).
Reference is made to the method shown by Crivello,
U.S. Patent 3,981,897, assigned to the same assignee as the present invention and incorporated herein by reference. The preferred photosensitive iodonium polymers have 0.1 to 10% by weight of antimony based on the weight of photosensitive iodonium polymer.
It has been found that heat curable compositions can be obtained by using the photosensitive iodonium polymer having chemically combined YFn groups with an effective amount of a copper compound as a cocatalyst to provide heat curable compositions as defined hereinafter. Suitable copper compounds are, for example, copper salts, such as cupric chloride, cuprous sulfate, cupric stearate; copper chelates such as copper acetylacetonate.
The heat curable compositions of the present invention can be made by using an effective amount of cocatalyst with cationically polymerizable organic material.
Suitable cationically polymerizable organic materials are, for example, epoxy resins, thermosetting organic condensation resins, vinyl organic prepolymers, cyclic ethers, cyclic amines, lactones, etc.
An effective amount of photosensitive iodonium polymer in the heat curable compositions is an amount sufficient to provide at least 1% by weight of iodine based on the weight of heat curable composition and preferably 1% to 10% by weight of iodine based on the weight of heat curable composition. The copper compound can be used in amounts by weight sufficient to provide 10% to 70 by weight copper, based on the weight of photosensitive iodonium polymer.
The heat curable compositions can be combined with inactive ingredients such as silica, clays, talc, glass fibers, extenders, hydrated alumina, carbon fibers, process aids in amounts of up to 500 parts of filler, per 100 parts of cationically polymerizable organic material.
In order that those skilled in the art will be better able to practice the present invention, the following example is given by way of illustration and not by way of limitation. All parts are by weight.
EXAMPLE 1
There was added 25 ml of concentrated sulfuric acid drop-wise to a cooled mixture at 0-50C of 40.85 grams (0.3 mole) of o-toluic acid, 25.0 grams (0.116 mole) of potassium iodate, 120 ml of methylene chloride, and 50 ml of acetic anhydride. After the addition of the sulfuric acid was completed, the reaction mixture was allowed to stir at room temperature for several days. Then 50 ml of water was added to dissolve the potassium bisulfate formed during the reaction. The resulting methylene chloride layer was separated, and an off-white product was collected by filtration. There was obtained a 19.1 grams of product which, based on method of preparation, was 4,4'-dimethyl-3,3'-dicarboxydiphenyliodonium bisulfate.
Examination of the proton NMR spectrum confirmed the identity of the product.
Claims (6)
1. Carboxy iodonium bisulfate salts of the formula,
where R is a C(l8) alkyl radical and a is equal to O to 3.
2. A process for producing a carboxy iodonium salt as claimed in claim 1 which comprises reacting an alkyl substituted arylcarboxylic acid and an alkali metal iodate in the presence of acetic anhydride, sulfuric acid and an inert solvent.
3. A process as claimed in claim 2 wherein the reaction is maintained at a temperature from about -30 to 300C during the addition of sulfuric acid.
4. An iodonium salt as claimed in claim 1 substantially as hereinbefore described in the example.
5. A process of making an iodonium salt as claimed in claim 2 or claim 3 substantially as hereinbefore described in the example.
6. An iodonium salt when produced by a method as claimed in claim 2 or claim 3.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US07/103,156 US4840977A (en) | 1987-10-01 | 1987-10-01 | Polymeric iodonium salts, method for making, and heat curable compositions |
| GB8822036A GB2210379B (en) | 1987-10-01 | 1988-10-27 | Polymeric iodonium salts, method for making, and heat curable compositions |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| GB9108436D0 GB9108436D0 (en) | 1991-06-05 |
| GB2243365A true GB2243365A (en) | 1991-10-30 |
| GB2243365B GB2243365B (en) | 1992-04-29 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB9108436A Expired - Fee Related GB2243365B (en) | 1987-10-01 | 1991-04-18 | Carboxy iodonium bisulfate salts |
Country Status (1)
| Country | Link |
|---|---|
| GB (1) | GB2243365B (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1491540A (en) * | 1974-05-08 | 1977-11-09 | Minnesota Mining & Mfg | Aromatic iodonium complex salts |
-
1991
- 1991-04-18 GB GB9108436A patent/GB2243365B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1491540A (en) * | 1974-05-08 | 1977-11-09 | Minnesota Mining & Mfg | Aromatic iodonium complex salts |
Also Published As
| Publication number | Publication date |
|---|---|
| GB2243365B (en) | 1992-04-29 |
| GB9108436D0 (en) | 1991-06-05 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PCNP | Patent ceased through non-payment of renewal fee |
Effective date: 19940920 |