CA2226849A1 - Stable polynitrile oxides and their use as curing agent especially for latex - Google Patents
Stable polynitrile oxides and their use as curing agent especially for latex Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D261/00—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings
- C07D261/02—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings
- C07D261/04—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C291/00—Compounds containing carbon and nitrogen and having functional groups not covered by groups C07C201/00 - C07C281/00
- C07C291/02—Compounds containing carbon and nitrogen and having functional groups not covered by groups C07C201/00 - C07C281/00 containing nitrogen-oxide bonds
- C07C291/06—Nitrile oxides
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C317/00—Sulfones; Sulfoxides
- C07C317/44—Sulfones; Sulfoxides having sulfone or sulfoxide groups and carboxyl groups bound to the same carbon skeleton
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2603/00—Systems containing at least three condensed rings
- C07C2603/02—Ortho- or ortho- and peri-condensed systems
- C07C2603/04—Ortho- or ortho- and peri-condensed systems containing three rings
- C07C2603/22—Ortho- or ortho- and peri-condensed systems containing three rings containing only six-membered rings
- C07C2603/24—Anthracenes; Hydrogenated anthracenes
Abstract
The present invention is an aqueous dispersion of a stable polynitrile oxide represented by the structure: R-(CN-O-)x, whre x is an integer greater than 1, R is an aromatic, aliphatic, or cycloaliphatic group having at least one substituent adjacent to each nitrile oxide group, the substituent characterized by inhibiting dimerization of nitrile oxide, and being non-interfering with a reaction between nitrile oxide groups and unsaturated groups. The present invention is also a method of curing a latex having a polyunsaturated disperse phase, comprising the steps of: a) mixing the latex with a stable polynitrile oxide; and b) removing water form the mixture. The present invention provides a simple means of preparing one-part coating systems that can be cured at room temperature without the release of by-products.
Description
42,452A-F 1 , , 7 ~ ,,, "" ,,~,.. , ~''' ' 7 ' 7' ~ , POLYNITRILE OXIDES
The present invention relates to stable polynitrile oxides.
Nitrile oxides react with unsaturated compounds to form cyclic compounds. For 5 example, nitrile oxides reactwith a) olefins and alkynes to form isoxazolines and isoxazoles, respectively; b) aldehydes and ketones to form 1,3,4-dioxazoles; c) thiocarbonyls to form thiooxazoles; d) imino compounds to form 1,2,4-oxadiazolines; e) isocyanates to form 1,2,4-oxadiazolinones; and fl carboxyls to form hydroximic acids. (See Grundmann and Grunanger, Nitrile Oxides, Springer, NewYork, pp. 85-139, 1971.) Nitrile oxides can be prepared by a number of methods, most notably from the dehydrohalogenation of the corresponding hydroximic acid halide, which can be prepared by the halogenation of the corresponding aldoxime. The aldoxime, in turn, can be prepared by reacting the corresponding aldehyde with a hydroxyl amine. General methods that teach the preparation of nitrile oxides are described in Nitrile Oxides, supra, pp.31-61.
Because nitrile oxides tend to dimerize in the absence of stabilizing groups, it is desirable to either prepare the nitrile oxides in situ, or to prepare stabilized nitrile oxides.
Nitrile oxides can be stabilized by the presence of substituents, such as ethyl, methyl, methoxy, or methylsulfide groups adjacentto the nitrile oxide group (see Nitrile Oxides, supra, p.14).
Examples of stable nitrile oxides, including stable bis-nitrile oxides are disclosed in Nitrile 20 Oxides, supra, pp.16-21; Izv. Akad. Nauk SSSR, Ser. Khim., No. 5, pp.1201-1203 (1991); and izv.Akad.NaukSSSR,Ser.Khim.,No.7,pp.1609-1615(1991). Onesuchstablebis-nitrileoxide, 2,4,6-triethylbenzene-1,3-bis(nitrile oxide), has been shown to be useful for the vulcanization of natural rubber.
None of the above-cited art suggests the use of stable polynitrile oxides as 25 curatives for latexes. It would be an advance in the artto cure latexes using a one-part, room-temperature curative.
The present invention is a water-insoluble aqueous dispersion comprising a stable polynitrile oxide represented by the structure:
G-(C g N +-O~)~
30 where x is an integer greater than 1, G is an aromatic, aliphatic, or cycloaliphatic group having at least one substituent adjacent to each nitrile oxide group, the substituent characterized by inhibiting dimerization of nitrile oxide, and being non-interfering with a reaction between nitrile oxide groups and unsaturated groups.
In a second aspect, the present invention is a method of curing a latex having a35 polyunsaturated disperse phase, comprising the steps of:
a) mixing with the latex a water-insoluble, stable polynitrile oxide represented by the structure:
G-(C = N +-~~)x ~MEI~E~ S~IE~T
where x i5 an integer greater than 1, preferably an integer from 2 to 6, G is anaromatic, aliphatic, or cycloaliphatic group having at least one substituent adjacent to each nitrile oxide group, the substituent characterized by inhibiting dimerization of nitrile oxide, and being non-interfering with a reaction betweennitrile oxide groups and unsaturated groups; and b) removing water from the mixture, preferably by evaporation.
In a further aspect, the present invention is a compound having the structure:
Ç5N+-O-~
(R~) ~ X' Y' n~
15 wherein each R' is independently C1-C12-alkyl, F, Cl, Br, I, O-C1-C12-alkyl, or S-C1-C12-alkyl; each R~ is a substituent that does not spontaneously react with the nitrile oxide group; each n' is independently 0, 1, or 2; n " is an integer greater than 1; each X' is independently a bond or a connecting group; and Y' is a polyvalent radical containing an ether, ester, amide, amine, carbonate, ketone, urethane, arylene, or thioether moiety; or each X' and Y' together are a 20 bond connecting the benzene rings.
The present invention provides a simple means of preparing one-part coating systems that can be cured at room temperature without the release of by-products.
The polynitrile oxides suitable for the practice of the present invention are hindered polynitrile oxides. The term "polynitrile oxide" is used herein to referto two or more 25 aromatic nitrile oxide groups per molecule. It is to be understood that the term "aromatic"
includes heteroaromatic moieties such as pyridines, furans and thiophenes. The term "unsaturated" is used herein to denote a site of the type A=A', or A=A', where A is a carbon atom, and A' is a carbon, oxygen, nitrogen, sulfur, or phosphorus atom. For the purposes of this invention, a nitrile oxide group is not an unsaturated group. The term " polyunsaturated "
30 is used herein to denote more than one unsaturated group. The preferred unsaturated groups include olefins and alkynes.
Each nitrile oxide is adjacent to at least one substituent that is 1 ) unreactive with nitrile oxide and 2) non-interfering with the reaction between the nitrile oxide groups and unsaturated groups, preferably olefinically or acetylenically unsaturated groups.
Traditionally, nitrile oxides are prepared in situ in the presence of an unsaturated r substrate with which the nitrile oxides are intended to react. However, the stable polynitrile oxide used as a curing agent in the present invention can be prepared separately and is sufficiently stable in the absence of the reactive substrate to be effective as a curing agent.
W O 97/03034 PCT~US96/11499 Preferably, the stable polynitrile oxide forms less than 10 percent, more preferably less than 5 percent, and most preferably less than 1 percent dimers in 30 days at room temperature.
Examples of hindered aromatic polynitrile oxides include:
(~C----N+--O ) i C----N+-O-R~,R2 R~R7 R3 C----N+ - O -( -O -N+--C ) ~ ( C--N+ - O~ ) n R~ ( C----N+ - O - ) n (-O-N+--C) where Rl, R2, and R3, and R4 are each independently H, R, halo, SH, SR, SOR, SO2R, hydroxy, or OR, with the proviso that at least one of Rl, R2, R3, and R4 that is adjacent to a nitrile oxide group is not H; R5, R6, R7, and R8 are each independently H, R, halo, S-H, SR, SOR, 502R, hydroxy, or OR, wherein R is a C1-C12 linear, branched, or cyclic alkyl group, preferably a Cl-C4 25 linear or branched alkyl group, more preferably ethyl or methyl; or R5 and R6, or R7 and R8~
together with the carbon atoms to which they are attached, form a benzene ring, wherein at least one of R5 or R7 is not H, and at least one of R6 or R8 is not H;iis 2 or 3; m and n are each 0, 1, or 2, and n + m 2 2, preferably 2 or 3.
Other examples of hindered aromatic polynitrile oxides include compounds 30 represented by the following structures:
( -O-N+----C~ C--N+-O- ) u where R9, Rl~, R11, and Rl2are each independently H, R, halo, SH, SR, SOR, 5O2R, hydroxy, or OR
with the proviso that at least one of R9 and Rllis not H when a nitrile oxide group is adjacent to (-O-N+-- C)p (C a N+-O )r R9 Rl~ (C a N+-O )r (-O-N+ - C)~ 12 , and ~ ~ C -- Nt-O-)r (-O-N+ a C) ~ R12 both R9 and R11, and at least one of R10 and R12 is not H when a nitrile oxide group is adjacent to both R10 and R12; m, p, and r are each 0, 1, or 2, and p + r 2 2; X is CHz, C(R)2, carbonyl, O, S, 20 SO, SO2, NH, SO2NH, SO2NR, or NR; t and u are each 0, 1, 2, or 3; and t + u 2 2; Y is a bond, CH2, C(R)2, carbonyl, O, S, SO, 5~2, NH, NR, 9,9'-fluoreno, or phenylene.
Examples of specific hindered aromatic polynitrile oxides that are suitable for the practice of the present invention include the following compounds:
C, - N+-O-2 ~
C - N+-O-3 O-N+ - C C, - N+-O-~ ' ~
~o2cH3 _-O-N+ a C ~ C -- N+-O
~ ' W097/03034 PCT~US96/11499 ~ ~~
O-N+-c C-N+-O--O-N+-C ~ C -- N+-O
~ , and -O-N+ - C~ = N+-O
W~ .
Stable aliphatic or cycloaliphatic polynitrile oxides can be prepared from a suitably functionalized aliphatic or cycloaliphatic polyaldehyde. The polyaldehyde can then be reacted with hydroxylamine to form the polyaldoxime, which can then be treated with bleach and caustic treatment to form the desired aliphatic polynitrile oxide.
A suitably functionalized aromatic mononitrile oxide or monoaldehyde can be used to prepare a polynitrile oxide represented by the following formula:
~ - N+-O-(R~)n~ X~ Y
n~
wherein each R' is independently Cl-C12-alkyl, F, Cl, Br, 1, O-C1-C12-alkyl, or S-C1-C12-alkyl; more preferably ethyl, methyl, n-propyl, isopropyl, n-butyl, isobutyl, methoxy, ethoxy; most preferably ethyl, methyl, or methoxy; each R~ is a substituent that does not spontaneously react with the nitrile oxide group, preferably ethyl, methyl, n-propyl, isopropyl, n-butyl, isobutyl, 30 methoxy, ethoxy, F, Cl, Br, or l; each n' is independently 0, 1, or 2; n' is an integer greater than 1, preferably 2,3, or 4, more preferably 2 or 3, and most preferably 2; each X' is independently a bond or a connecting group such as an alkylene, cycloalkylene, or arylene group, more preferably a bond, a methylene group, or a phenylene group; and Y' is a polyvalent radical, preferably a divalent radical, containing an ether, ester, amide, carbonate, ketone, urethane, 35 arylene, or thioether group; or each X' and Y' together are a bond connecting the benzene rings.
CA 02226849 1998-01-13 ~-W O 97/03034 PCT~US96/11499 Suitablyfunctionalized hindered aromatic mononitrile oxides or monoaldehydes preferably include 2,6-disubstituted benzonitrile oxides or benzaldehydes having an ester, acetate, hydroxy, epoxy, fluorine, chlorine, bromine, or iodine group connected directly to the benzene ring or indirectly through a connecting group. Preferably, the suitably functionalized 5 2,6-disubstituted benzonitrile oxide or benzaldehydes is represented by the following structure:
Q
R
( R~ ) X ' - Z ' where R', R~, X', and n' are previously defined; Q is -C--N+O- or -CHO; and Z' is an ester, acetate, amine, hydroxy, epoxy, amide, keto, aldehyde, fluorine, chlorine, bromine, or iodine 1 5 group.
For example, 3-hydroxymethyl-2,4,6-trimethylbenzonitrile oxide or its corresponding benzaldehyde precursor can be: (a) transesterified with a diester or condensed with a diacid chloride to form a dinitrile oxide diester; (b) reacted with phosgene to form a dinitrile oxide containing a carbonate group; (c) reacted with a diisocyanate to form a dinitrile 20 oxide containing urethane groups; (d) reacted with a dibenzyl chloride to form a dinitrile oxide containing two ether groups; (e) reacted with a diglycidyl ether to form a dinitrile oxide containing ether groups and hydroxy groups reacted with an acid to form a dinitrile oxido dibenzyl ether.
Similarly, the suitably functionalized hindered aromatic nitrile oxide can be 25 reacted with a second suitably functionalized hindered aromatic nitrile oxide to form a dinitrile oxide. For example, 3-hydroxymethyl-2,4,6-trimethylbenzonitrile oxide can be reacted with 3-chloromethyl-2,6-dimethylbenzene nitrile oxide to form a bis(nitrile oxide) dimethyl ether.
Polynitrile oxides having a functionality of greater than 2 ffor example, a trinitrile oxide) can readily be prepared by reacting a dinitrile oxide with a compound having more than 30 2 unsaturated sites. For example, 2,4,6-triethylbenzene-1,3-dinitrile oxide can be reacted with trimethylol propane triacrylate to form the following trinitrile oxide:
c33c z-o-c~\c~2c~3 W O 97/03034 PCTrUS96111499 An aqueous dispersion of the stable polynitrile oxide is prepared, then advantageously combined with an aqueous dispersion of a polyunsaturated monomer or polymer or a combination thereof, to make a stable multicomponent dispersion. The term ~ "stable multicomponent dispersion" is used herein to mean that microscopic mixing (and 5 therefore, the reaction rate) of the polynitrile oxide and the polyunsaturated monomer and/or . polymer is slower than it would be in the absence of the aqueous medium. Preferably, the extent of the reaction between the polynitrile oxide and polyunsaturated monomer and/or polymer dispersions is less than 10 percent in 8 hours, more preferably less than 10 percent in 30 days, and most preferably less than 10 percent in 1 year.
The aqueous dispersion of the polynitrile oxide can be prepared by emulsifying an emulsifiable concentrate of the polynitrile oxide. This concentrate can be prepared, for example, by mixing a solution of the polynitrile oxide with a surfactant.
The polynitrile oxide may itself be prepared as a surfactant, for example, by reacting an excess of a dinitrile oxide with a polyunsaturated surfactant:
Ar-(C-N+-O )2 + = = ~ X"
(excess) I
~ ~ Ar-C-N+-O- ~ ~ Ar-C--N+-O-\ \ X"
or, for example, by reacting a trinitrile oxide with a monounsaturated surfactant:
Ar-(C-N+-O )3 + = X"
C-N+-O
-O-N+-C-Ar ~
X "
where X" is a hydrophilic group, such as a poly(oxyethylene), a carboxylate, or a sulfate.
Other methods of forming a polynitrile oxide surfactant include reacting the polynitrile oxide with a polymeric surfactant having polyunsaturation:
W O 97/03034 PCT~US96/11499 I COOH
Ç=~ b o + R(C -- N+-O-)2 0cH2c9(oH)cH2oc-cH=cH2 COOH
1 ~ ~ RC - N+-O-f=~_ b R ~, 'y OCH2CH(OH)CH2OC ~C CH2 H
where b i5 an integer greater than 1.
Aqueous dispersions of polyunsaturated polymers are disperse polymers having a plurality of untaturated sites, which dispersions can be prepared by emulsion polymerization of suitable monomers or by emulsification of previously prepared polymers (artificial latexes).
Suitable emulsion polymers can be prepared from the emulsion polymerization of a-olefinically unsaturated aromatic monomers and dienes, preferably conjugated dienes, such as styrene-butadiene latex, ~-methylstyrene-butadiene latex, styrene-isoprene latex, and a-methylstyrene-isoprene latex.
However, the unsaturated latexes need not be prepared from conjugated diene monomers, but may be prepared by polymerizing or copolymerizing unsaturated monomers containing unsaturated groups having different reactivity. For example, the emulsion copolymerization of a monofunctional alkyl acrylate or methacrylate, such as methyl or butyl acrylate or methacrylate, with a difunctional acrylate or methacrylate having a vinyl group and a less reactive double bond, such as crotyl acrylate or methacrylate, can produce a latex having a plurality of pendant olefin groups.
A suitably functionalized latex, which need not be unsaturated, may be post-reacted with compounds that impart unsaturated sites to the latex, for example, by reacting a latex containing carboxyl functionality, such as a poly(methylmethacrylate/butylmethacrylate/methacrylic acid) latex, with glycidylmethacrylate. Similarly, a latex containing pendant benzyl chloride groups can be reacted with a vinyl monomer containing a tertiary amine group to form the polyunsaturated latex.
Artificial latexes, particularly polyunsaturated triblock copolymers of unsaturated aromatic monomers and conjugated dienes, such as ~-methylstyrene-butadiene-~-methylstyrene, ~-methylstyrene-isoprene-~-methylstyrene, styrene-isoprene-styrene, and styrene-butadiene-styrene are also suitable.
Other suitable aqueous dispersions include those of polyester resins, such as ~ maleate- and fumarate-containing polyesters and vinylically and allylically unsaturated acrylate 5 copolyesters; butadiene-acrylonitrile copolymers; ethylene-propylene-dicyclopentadiene ~ terpolymers; polyisoprene; polybutadiene, including 1,2-polybutadiene; unsaturated polyurethanes; and polyether copolymers and terpolymers containing at least two unsaturated epoxide constituents, such as propylene oxide-allyl glycidyl ether copolymers and ethylene oxide-epichlorohydrin-allyl glycidyl etherterpolymers.
Aqueous dispersions of polyunsaturated monomers include dispersions of conjugated or non-conjugated monomers, particularly monomers having a boiling point greaterthan 100~C.
The polynitrile oxide is used at an effective amount to cure the polyunsaturatedlatex. Preferably, the concentration of polynitrile oxide is in the range of about 0.01 to about 1.10 nitrile oxide groups per unsaturated group.
The following examples are for illustrative purposes only and are not intended to limitthe scope of the invention.
Example 1 - Curing an S/B Latex with an Emulsifiable Concentrate of 2,4,6-Triethylbenzene-1,3-Dinitrile Oxide 20 A. Preparation of a Polymeric Surfactant and an Emulsifiable Concentrate of 2,4,6-Triethylbenzene-1,3-Dinitrile Oxide A polymeric surfactant suitable for forming an emulsifiable concentrate of the dinitrile oxide was prepared in two stages as follows:
Stage 1 - Hydrophobic Monomer Polymerization A mixture of 793.8 parts TERGITOL'~ NP-7 surfactant (a trademark of Union Carbide) and 18.4 parts t-butyl peroctoate were heated to 90~C in a stirred glass reactor and blanketed with an inert atmosphere of nitrogen. A mixture of 433.1 parts styrene, 144.4 parts 2-ethylhexyl acrylate, 35.0 parts glycidyl methacrylate and a separate feed of 18.4 parts t-butyl peroctoate were added continuously and proportionately to the reactor over 1.5 hours. During 30 this addition period, the reaction temperature reached a maximum temperature of 99~C.
Stage 2 - Hydrophilic Monomer Polymerization The following feed solutions were added continuously and proportionately to the reactor over 1.5 hours with the reaction temperature decreasing from 99~C to 92~C: 1 ) 87.5 parts 2-acrylamido-2-methylpropane sulfonic acid (AMPS) admixed with 87.5 parts deionized 35 (Dl) water, and 41.0 parts dibutyl amine; 2) 1176.7 parts TERGlTOL'" NP-7; and 3) 0.7 parts 2-mercaptoethanol admixed with 15.8 parts Dl water. The reactor contents were maintained at 90~C for an additional 2 hours. The polymer/non-ionic/water reaction mixture (PC-3) was transferred to a steam still and the residual monomers were removed with the aid of a vacuum.
g W O 97/03034 PCT~US96/11499 A solution containing 1.9 9 of 2,4,6-triethylbenzene-1,3-dinitrile oxide (TON-2)and 5.8 9 butyl benzyl phthalate was prepared and mixed with 1.1 9 of PC-3 along with 2.9 9 of TERGlTOL'~ NP-7 to form the emulsifiable concentrate.
B. The Curing Step The emulsifiable concentrate from Part A was diluted with 11.7 9 of distilled water and shaken to form an aqueous dispersion. This aqueous dispersion was then added to 76.6 9 of a polyunsaturated styrene/butadiene/acrylic acid latex (54.7 percent styrene, 43.3 percent butadiene,2 percent acrylic acid) having a pH of 3.5 and containing 38.7 9 solids and 37.9 9 water. This material was cast into 10-mil (0.25 mm) films on a glass substrate and cured 10 upon evaporation of water, at room temperature for 24 hours. When a portion of the resultant film (0.42 9) was mixed with 8.5 9 of toluene, the film swelled, but ddid not dissolve.
In contrast, a comparable film that was prepared in the same manner, but did not contain the dinitrile oxide, was found to dissolve partially in toluene. Thus, the dinitrile oxide-treated film was found to be more highly crosslinked than the control that does not contain the dinitrile oxide curative.
Exam~ie 2 - Crosslinking of Crotyl Methacrylate-Containing Latex with TON-2 Phase (A): Synthesis of a Latex A 5-L, five-necked round-bottomed flask equipped with a nitrogen inlet, a refluxcondenser connected to an oil bubbler with a nitrogen outlet, a mechanical stirrer, and five 20 feed streams was immersed into a water bath and purged with nitrogen a suspension of latex seed (prepared from styrene/acrylic acid 96/4; median particle size 240 A; 40 weight percent;
22.28 9) and VERSENOLrU 120 chelating agent (a trademark of The Dow Chemical Company, 8.32 9 of 1 percent solution) in water (642.8 9) were placed into the flask and heated at 60~C.
Butyl acrylate (399.36 9), methyl methacrylate (357.6 9), and methacrylic acid (16.64 9) were 25 pre-mixed to give a basic monomer mixture (773.6 9). Using five syringes and syringe pumps, the following components were added to the flask while constantly maintaining the nitrogen atmosphere and the temperature of 60~C:
(a) crotyl methacrylate (43.2 9) and a portion of the basic monomer mixture (40 9);
(b) the remaining basic monomer mixture (733.6 9);
(c) t-dodecyl mercaptan (16.649);
(d) the solution of t-butyl hydroperoxide (4.64 9 of 70 percent active; 3.25 percent active) and DOWFAX'U (a trademark of The Dow Chemical Company) 2EP
surfactant (17.76 9) in water (83.2 9); and (e) the solution of sodium formaldehyde sulfoxylate (SFS, 2.52 9 in 28 9 of water). Y
Component (b) was added over the first five hours, followed by the addition of component (a) over an additional hour. Components (c), (d), and (e) were added over six hours.
After the addition of all components, stirring at 60~C was continued for an additional hour.
CA 02226849 1998-01-13 ..
W O 97/03034 PCT~US96/11499 The resuiting latex was then filtered through a 200-mesh screen and cooled to ambient temperature. The conversion was 99.4 percent, and the recovery 97.8 percent. This latex had 50.4 percent solids, and particles with a mean and median size of 1442 A and 1341 A, ~ respectively.
5 Phase (B): Crosslinking of a Coating An emulsion of TON-2 (12.5 weight percent in ethyl benzoate/water) was prepared by a slow addition of the solution of TON-2 (3.125 9) in ethyl benzoate (9.375 9) to a solution of RHODAPEX'~ C0-436 surfactant (a trademark of Rhane Poulenc,0.215 9 of 58 percent aqueous solution) in water (12.285 9) with high shear. A portion (8.01 9) of this 10 emulsion was added to the crotyl methacrylate-containing latex (42.00 9) described in Phase (A) of this example. The resulting latex/TON-2 mixture was cast and dried, and aged at 22~C
and 50 percent relative humidityfor 18 hours. A piece of the resulting film (about 1 9) was isolated and weighed, then placed in a vial with toluene (35 mL). The mixture was shaken at high speed for 1 hour, and the soluble phase was removed. The mass of the residual gel-state polymer in a wet state was recorded and the wet gel was then dried in vacuo at 65~C. The mass of the resulting dry gel was recorded, and the swell index (that is, the difference in weights of wet gel and dry gel divided by the weight of a dry gel) and percent gel (that is, the ratio of weights of dry gel and the initial sample multiplied by 100) measured. In this example, the film prepared from the latex/TON-2 mixture hadsa swell index of 4.2 and 86.8 percent gel, 20 indicating a high degree of crosslinking. A reference coating prepared from the same latex, but without TON-2 added dissolved completely, confirming the absence of crosslinking in latex alone.
Example 3 - Crosslinking of Glycidyl Methacrylate- Containing Latex with TON-2 Phase (A): Synthesis of a Latex To a 1-gallon reactor equipped with a reflux condenser, a mechanical stirrer, and nitrogen inlet and outlet was placed a suspension of latex seed (prepared from styrene/acrylic acid96/4;medianparticlesize270A;40weightpercent; 19.34g)andVERSENOL'4 120(15.299of 1 percent solution) in water (1255.32 9). The flask was maintained at a temperature of 90~C
under a nitrogen purge. The following components were simultaneously added to the flask 30 over 230 minutes:
(a) butyl acrylate (779.60 9) and methacrylic acid (91.72 9);
(b) methyl methacrylate (657.31 9) and t-dodecylmercaptan (15.29 9); and (c) the solution of ammonium persulfate (7.64 9) and DOWFAX~" 2EP surfactant (33.97 9) in water (152.86 9).
After all the components were added, stirring at 90~C was continued for 30 minutes. The resulting latex was then filtered through a 200-mesh screen and cooled to ambienttemperature. This latex had 51.9 percentsolids, particleswith a median size of 1380A, andapHof2.2.
CA 02226849 l998-0l-l3 W 097/03034 PCT~US96/11499 The latex (250 9) was adjusted to a pH of 7.8, whereupon water (Z0 9) and 4-methoxyphenol (0.20 9) were added. This solution was placed into the 500-mL,3-necked round-bottomed flask equipped with an air inlet, a reflux condenser with an air outlet, and a mechanical stirrer. The flask was immersed into a water bath, heated to 90~C, and the air-flow was established. Glycidyl methacryiate (5.2 9) was added over 3 hours, and the resulting latex was cooled to ambient temperature. A milky suspension with no coagulates was obtained, having 46.3 percent solids.
Phase (B): Crosslinking of a Coating An emulsion of TON-Z as prepared in Example 2 (12.5 weight percent in ethyl benzoate/water; 8.01 9) was added to the glycidyl methacrylate-containing latex (65.34 9) described in Phase (A) of this example. The resulting latex/TON-2 mixture was cast to give a coating with 61.3 percent gel.
Exam,ole 4 - Crosslinking of S/B Latex with TON-2 The S/B latex used in this example was prepared using styrene (57.5 percent), butadiene (38 percent with a 1,2: 1,4 ratio of 15/85), and acrylic acid (4.5 percent). An emulsion of TON-2 (12.5 percent in toluene/water) was prepared by a slow addition of the solution of TON-2 (3.125 9) in toluene (9 375 g) to a solution of RHODAPEX'~ C0-436 surfactant (0.215 g of 58 percent aqueous solution) in water (12.285 9) with high shear. A portion of this emulsion (6.40 9) was added to the S/B latex (100.0 9), and toluene was evaporated off. The resulting latex/TON-2 mixture gave a coating which had 90.9 percent gel, a swell index of 4.9, and a tensile strength of 1032.2 psi.
Exam,~le 5 - Preparation Of Di(3-Fulmido-2,4,6-trimethyl)-benzyl Ether Di(3-fulmido-2,4,6-trimethyl)-benzyl ether was prepared in two steps from 3-hydroxymethyl-2,4,6-trimethylbenzaldehyde, which was prepared according to A. P.
Yakubov et al. in Izv. Akd. Nauk SSR, Ser. Khim., No.7, pp.1609-1615.
To a flask fitted by a 10-cm Vigeux column to which was attached a Barret trap and reflux condenser was added a mixture of 3-hydroxymethyl-2,4,6-trimethylbenzaldehyde (23 9, 0.129 mole) and sulfuric acid (0.2 9,96 percent in 130 mL of benzene). The mixture was refluxed vigorously for 60 minutes. Benzene was removed in vacuo and the crude product was dissolved in chloroform (about 60 mL), whereupon isopropanol (about 200 mL) was added at 60~C. The mixture was cooled to 5~C, and a crystalline precipate was filtered and determined to be di(3-formyl-2,4,6-trimethyl)benzyl ether (18.7 g,85 percent yield), m.p.158~C to 161~C.
To a flask containing di(3-formyl-2,4-6-trimethyl)benzyl ether (9.8 9, 0.029 mole) and ethanol (110 mL) was added in one portion a solution of NaOH (4.64 9,0.116 mole) and hydroxylamine hydrochloride (8.06 9,0.116 mole) in water (20 mL). The mixture was heated for ~f 2.5 hours with vigorous stirring, then cooled to 5~C, whereupon a crystalline precipitate was filtered and washed with ethanol (30 mL) and water. The precipitate was predetermined to be W O 97/03034 PCTrUS96/11499 di(3-hydroximinomethyl-2,4,6-trimethyl)benzyl ether (8.9 9, 83 percent yield), m.p. 210~C to 213~C.
To a flask maintained at 5~C and containing a vigorousiy stirred suspension of di(3-hydroximinomethyl-2,4,6-trimethyl)benzyl ether (7.9 9 0.0215 mole) in methylene chloride (100 mL) was added (NaOCI (53 mL of a 15 percent solution). The reaction mixture was stirred for 2 hours at 5~C to 10~C, whereupon the organic layer was separated, and the aqueous phase was extracted with methylene chloride (50 mL). The organic phases were combined, then washed with water (3 x 200 mL). The solvent was then removed in vacuo, and the resultant mixture was cooled to 20~C. A crystalline precipitate was filtered and determined to be di(3-fulmido-2,4,6-trimethyl)benzyl ether (7.5 9, 96 percent yield), m.p.156~C to 158~C.
Infrared spectroscopy showed a strong narrow band at 2300 cm~l corresponding to nitrile oxide.
The present invention relates to stable polynitrile oxides.
Nitrile oxides react with unsaturated compounds to form cyclic compounds. For 5 example, nitrile oxides reactwith a) olefins and alkynes to form isoxazolines and isoxazoles, respectively; b) aldehydes and ketones to form 1,3,4-dioxazoles; c) thiocarbonyls to form thiooxazoles; d) imino compounds to form 1,2,4-oxadiazolines; e) isocyanates to form 1,2,4-oxadiazolinones; and fl carboxyls to form hydroximic acids. (See Grundmann and Grunanger, Nitrile Oxides, Springer, NewYork, pp. 85-139, 1971.) Nitrile oxides can be prepared by a number of methods, most notably from the dehydrohalogenation of the corresponding hydroximic acid halide, which can be prepared by the halogenation of the corresponding aldoxime. The aldoxime, in turn, can be prepared by reacting the corresponding aldehyde with a hydroxyl amine. General methods that teach the preparation of nitrile oxides are described in Nitrile Oxides, supra, pp.31-61.
Because nitrile oxides tend to dimerize in the absence of stabilizing groups, it is desirable to either prepare the nitrile oxides in situ, or to prepare stabilized nitrile oxides.
Nitrile oxides can be stabilized by the presence of substituents, such as ethyl, methyl, methoxy, or methylsulfide groups adjacentto the nitrile oxide group (see Nitrile Oxides, supra, p.14).
Examples of stable nitrile oxides, including stable bis-nitrile oxides are disclosed in Nitrile 20 Oxides, supra, pp.16-21; Izv. Akad. Nauk SSSR, Ser. Khim., No. 5, pp.1201-1203 (1991); and izv.Akad.NaukSSSR,Ser.Khim.,No.7,pp.1609-1615(1991). Onesuchstablebis-nitrileoxide, 2,4,6-triethylbenzene-1,3-bis(nitrile oxide), has been shown to be useful for the vulcanization of natural rubber.
None of the above-cited art suggests the use of stable polynitrile oxides as 25 curatives for latexes. It would be an advance in the artto cure latexes using a one-part, room-temperature curative.
The present invention is a water-insoluble aqueous dispersion comprising a stable polynitrile oxide represented by the structure:
G-(C g N +-O~)~
30 where x is an integer greater than 1, G is an aromatic, aliphatic, or cycloaliphatic group having at least one substituent adjacent to each nitrile oxide group, the substituent characterized by inhibiting dimerization of nitrile oxide, and being non-interfering with a reaction between nitrile oxide groups and unsaturated groups.
In a second aspect, the present invention is a method of curing a latex having a35 polyunsaturated disperse phase, comprising the steps of:
a) mixing with the latex a water-insoluble, stable polynitrile oxide represented by the structure:
G-(C = N +-~~)x ~MEI~E~ S~IE~T
where x i5 an integer greater than 1, preferably an integer from 2 to 6, G is anaromatic, aliphatic, or cycloaliphatic group having at least one substituent adjacent to each nitrile oxide group, the substituent characterized by inhibiting dimerization of nitrile oxide, and being non-interfering with a reaction betweennitrile oxide groups and unsaturated groups; and b) removing water from the mixture, preferably by evaporation.
In a further aspect, the present invention is a compound having the structure:
Ç5N+-O-~
(R~) ~ X' Y' n~
15 wherein each R' is independently C1-C12-alkyl, F, Cl, Br, I, O-C1-C12-alkyl, or S-C1-C12-alkyl; each R~ is a substituent that does not spontaneously react with the nitrile oxide group; each n' is independently 0, 1, or 2; n " is an integer greater than 1; each X' is independently a bond or a connecting group; and Y' is a polyvalent radical containing an ether, ester, amide, amine, carbonate, ketone, urethane, arylene, or thioether moiety; or each X' and Y' together are a 20 bond connecting the benzene rings.
The present invention provides a simple means of preparing one-part coating systems that can be cured at room temperature without the release of by-products.
The polynitrile oxides suitable for the practice of the present invention are hindered polynitrile oxides. The term "polynitrile oxide" is used herein to referto two or more 25 aromatic nitrile oxide groups per molecule. It is to be understood that the term "aromatic"
includes heteroaromatic moieties such as pyridines, furans and thiophenes. The term "unsaturated" is used herein to denote a site of the type A=A', or A=A', where A is a carbon atom, and A' is a carbon, oxygen, nitrogen, sulfur, or phosphorus atom. For the purposes of this invention, a nitrile oxide group is not an unsaturated group. The term " polyunsaturated "
30 is used herein to denote more than one unsaturated group. The preferred unsaturated groups include olefins and alkynes.
Each nitrile oxide is adjacent to at least one substituent that is 1 ) unreactive with nitrile oxide and 2) non-interfering with the reaction between the nitrile oxide groups and unsaturated groups, preferably olefinically or acetylenically unsaturated groups.
Traditionally, nitrile oxides are prepared in situ in the presence of an unsaturated r substrate with which the nitrile oxides are intended to react. However, the stable polynitrile oxide used as a curing agent in the present invention can be prepared separately and is sufficiently stable in the absence of the reactive substrate to be effective as a curing agent.
W O 97/03034 PCT~US96/11499 Preferably, the stable polynitrile oxide forms less than 10 percent, more preferably less than 5 percent, and most preferably less than 1 percent dimers in 30 days at room temperature.
Examples of hindered aromatic polynitrile oxides include:
(~C----N+--O ) i C----N+-O-R~,R2 R~R7 R3 C----N+ - O -( -O -N+--C ) ~ ( C--N+ - O~ ) n R~ ( C----N+ - O - ) n (-O-N+--C) where Rl, R2, and R3, and R4 are each independently H, R, halo, SH, SR, SOR, SO2R, hydroxy, or OR, with the proviso that at least one of Rl, R2, R3, and R4 that is adjacent to a nitrile oxide group is not H; R5, R6, R7, and R8 are each independently H, R, halo, S-H, SR, SOR, 502R, hydroxy, or OR, wherein R is a C1-C12 linear, branched, or cyclic alkyl group, preferably a Cl-C4 25 linear or branched alkyl group, more preferably ethyl or methyl; or R5 and R6, or R7 and R8~
together with the carbon atoms to which they are attached, form a benzene ring, wherein at least one of R5 or R7 is not H, and at least one of R6 or R8 is not H;iis 2 or 3; m and n are each 0, 1, or 2, and n + m 2 2, preferably 2 or 3.
Other examples of hindered aromatic polynitrile oxides include compounds 30 represented by the following structures:
( -O-N+----C~ C--N+-O- ) u where R9, Rl~, R11, and Rl2are each independently H, R, halo, SH, SR, SOR, 5O2R, hydroxy, or OR
with the proviso that at least one of R9 and Rllis not H when a nitrile oxide group is adjacent to (-O-N+-- C)p (C a N+-O )r R9 Rl~ (C a N+-O )r (-O-N+ - C)~ 12 , and ~ ~ C -- Nt-O-)r (-O-N+ a C) ~ R12 both R9 and R11, and at least one of R10 and R12 is not H when a nitrile oxide group is adjacent to both R10 and R12; m, p, and r are each 0, 1, or 2, and p + r 2 2; X is CHz, C(R)2, carbonyl, O, S, 20 SO, SO2, NH, SO2NH, SO2NR, or NR; t and u are each 0, 1, 2, or 3; and t + u 2 2; Y is a bond, CH2, C(R)2, carbonyl, O, S, SO, 5~2, NH, NR, 9,9'-fluoreno, or phenylene.
Examples of specific hindered aromatic polynitrile oxides that are suitable for the practice of the present invention include the following compounds:
C, - N+-O-2 ~
C - N+-O-3 O-N+ - C C, - N+-O-~ ' ~
~o2cH3 _-O-N+ a C ~ C -- N+-O
~ ' W097/03034 PCT~US96/11499 ~ ~~
O-N+-c C-N+-O--O-N+-C ~ C -- N+-O
~ , and -O-N+ - C~ = N+-O
W~ .
Stable aliphatic or cycloaliphatic polynitrile oxides can be prepared from a suitably functionalized aliphatic or cycloaliphatic polyaldehyde. The polyaldehyde can then be reacted with hydroxylamine to form the polyaldoxime, which can then be treated with bleach and caustic treatment to form the desired aliphatic polynitrile oxide.
A suitably functionalized aromatic mononitrile oxide or monoaldehyde can be used to prepare a polynitrile oxide represented by the following formula:
~ - N+-O-(R~)n~ X~ Y
n~
wherein each R' is independently Cl-C12-alkyl, F, Cl, Br, 1, O-C1-C12-alkyl, or S-C1-C12-alkyl; more preferably ethyl, methyl, n-propyl, isopropyl, n-butyl, isobutyl, methoxy, ethoxy; most preferably ethyl, methyl, or methoxy; each R~ is a substituent that does not spontaneously react with the nitrile oxide group, preferably ethyl, methyl, n-propyl, isopropyl, n-butyl, isobutyl, 30 methoxy, ethoxy, F, Cl, Br, or l; each n' is independently 0, 1, or 2; n' is an integer greater than 1, preferably 2,3, or 4, more preferably 2 or 3, and most preferably 2; each X' is independently a bond or a connecting group such as an alkylene, cycloalkylene, or arylene group, more preferably a bond, a methylene group, or a phenylene group; and Y' is a polyvalent radical, preferably a divalent radical, containing an ether, ester, amide, carbonate, ketone, urethane, 35 arylene, or thioether group; or each X' and Y' together are a bond connecting the benzene rings.
CA 02226849 1998-01-13 ~-W O 97/03034 PCT~US96/11499 Suitablyfunctionalized hindered aromatic mononitrile oxides or monoaldehydes preferably include 2,6-disubstituted benzonitrile oxides or benzaldehydes having an ester, acetate, hydroxy, epoxy, fluorine, chlorine, bromine, or iodine group connected directly to the benzene ring or indirectly through a connecting group. Preferably, the suitably functionalized 5 2,6-disubstituted benzonitrile oxide or benzaldehydes is represented by the following structure:
Q
R
( R~ ) X ' - Z ' where R', R~, X', and n' are previously defined; Q is -C--N+O- or -CHO; and Z' is an ester, acetate, amine, hydroxy, epoxy, amide, keto, aldehyde, fluorine, chlorine, bromine, or iodine 1 5 group.
For example, 3-hydroxymethyl-2,4,6-trimethylbenzonitrile oxide or its corresponding benzaldehyde precursor can be: (a) transesterified with a diester or condensed with a diacid chloride to form a dinitrile oxide diester; (b) reacted with phosgene to form a dinitrile oxide containing a carbonate group; (c) reacted with a diisocyanate to form a dinitrile 20 oxide containing urethane groups; (d) reacted with a dibenzyl chloride to form a dinitrile oxide containing two ether groups; (e) reacted with a diglycidyl ether to form a dinitrile oxide containing ether groups and hydroxy groups reacted with an acid to form a dinitrile oxido dibenzyl ether.
Similarly, the suitably functionalized hindered aromatic nitrile oxide can be 25 reacted with a second suitably functionalized hindered aromatic nitrile oxide to form a dinitrile oxide. For example, 3-hydroxymethyl-2,4,6-trimethylbenzonitrile oxide can be reacted with 3-chloromethyl-2,6-dimethylbenzene nitrile oxide to form a bis(nitrile oxide) dimethyl ether.
Polynitrile oxides having a functionality of greater than 2 ffor example, a trinitrile oxide) can readily be prepared by reacting a dinitrile oxide with a compound having more than 30 2 unsaturated sites. For example, 2,4,6-triethylbenzene-1,3-dinitrile oxide can be reacted with trimethylol propane triacrylate to form the following trinitrile oxide:
c33c z-o-c~\c~2c~3 W O 97/03034 PCTrUS96111499 An aqueous dispersion of the stable polynitrile oxide is prepared, then advantageously combined with an aqueous dispersion of a polyunsaturated monomer or polymer or a combination thereof, to make a stable multicomponent dispersion. The term ~ "stable multicomponent dispersion" is used herein to mean that microscopic mixing (and 5 therefore, the reaction rate) of the polynitrile oxide and the polyunsaturated monomer and/or . polymer is slower than it would be in the absence of the aqueous medium. Preferably, the extent of the reaction between the polynitrile oxide and polyunsaturated monomer and/or polymer dispersions is less than 10 percent in 8 hours, more preferably less than 10 percent in 30 days, and most preferably less than 10 percent in 1 year.
The aqueous dispersion of the polynitrile oxide can be prepared by emulsifying an emulsifiable concentrate of the polynitrile oxide. This concentrate can be prepared, for example, by mixing a solution of the polynitrile oxide with a surfactant.
The polynitrile oxide may itself be prepared as a surfactant, for example, by reacting an excess of a dinitrile oxide with a polyunsaturated surfactant:
Ar-(C-N+-O )2 + = = ~ X"
(excess) I
~ ~ Ar-C-N+-O- ~ ~ Ar-C--N+-O-\ \ X"
or, for example, by reacting a trinitrile oxide with a monounsaturated surfactant:
Ar-(C-N+-O )3 + = X"
C-N+-O
-O-N+-C-Ar ~
X "
where X" is a hydrophilic group, such as a poly(oxyethylene), a carboxylate, or a sulfate.
Other methods of forming a polynitrile oxide surfactant include reacting the polynitrile oxide with a polymeric surfactant having polyunsaturation:
W O 97/03034 PCT~US96/11499 I COOH
Ç=~ b o + R(C -- N+-O-)2 0cH2c9(oH)cH2oc-cH=cH2 COOH
1 ~ ~ RC - N+-O-f=~_ b R ~, 'y OCH2CH(OH)CH2OC ~C CH2 H
where b i5 an integer greater than 1.
Aqueous dispersions of polyunsaturated polymers are disperse polymers having a plurality of untaturated sites, which dispersions can be prepared by emulsion polymerization of suitable monomers or by emulsification of previously prepared polymers (artificial latexes).
Suitable emulsion polymers can be prepared from the emulsion polymerization of a-olefinically unsaturated aromatic monomers and dienes, preferably conjugated dienes, such as styrene-butadiene latex, ~-methylstyrene-butadiene latex, styrene-isoprene latex, and a-methylstyrene-isoprene latex.
However, the unsaturated latexes need not be prepared from conjugated diene monomers, but may be prepared by polymerizing or copolymerizing unsaturated monomers containing unsaturated groups having different reactivity. For example, the emulsion copolymerization of a monofunctional alkyl acrylate or methacrylate, such as methyl or butyl acrylate or methacrylate, with a difunctional acrylate or methacrylate having a vinyl group and a less reactive double bond, such as crotyl acrylate or methacrylate, can produce a latex having a plurality of pendant olefin groups.
A suitably functionalized latex, which need not be unsaturated, may be post-reacted with compounds that impart unsaturated sites to the latex, for example, by reacting a latex containing carboxyl functionality, such as a poly(methylmethacrylate/butylmethacrylate/methacrylic acid) latex, with glycidylmethacrylate. Similarly, a latex containing pendant benzyl chloride groups can be reacted with a vinyl monomer containing a tertiary amine group to form the polyunsaturated latex.
Artificial latexes, particularly polyunsaturated triblock copolymers of unsaturated aromatic monomers and conjugated dienes, such as ~-methylstyrene-butadiene-~-methylstyrene, ~-methylstyrene-isoprene-~-methylstyrene, styrene-isoprene-styrene, and styrene-butadiene-styrene are also suitable.
Other suitable aqueous dispersions include those of polyester resins, such as ~ maleate- and fumarate-containing polyesters and vinylically and allylically unsaturated acrylate 5 copolyesters; butadiene-acrylonitrile copolymers; ethylene-propylene-dicyclopentadiene ~ terpolymers; polyisoprene; polybutadiene, including 1,2-polybutadiene; unsaturated polyurethanes; and polyether copolymers and terpolymers containing at least two unsaturated epoxide constituents, such as propylene oxide-allyl glycidyl ether copolymers and ethylene oxide-epichlorohydrin-allyl glycidyl etherterpolymers.
Aqueous dispersions of polyunsaturated monomers include dispersions of conjugated or non-conjugated monomers, particularly monomers having a boiling point greaterthan 100~C.
The polynitrile oxide is used at an effective amount to cure the polyunsaturatedlatex. Preferably, the concentration of polynitrile oxide is in the range of about 0.01 to about 1.10 nitrile oxide groups per unsaturated group.
The following examples are for illustrative purposes only and are not intended to limitthe scope of the invention.
Example 1 - Curing an S/B Latex with an Emulsifiable Concentrate of 2,4,6-Triethylbenzene-1,3-Dinitrile Oxide 20 A. Preparation of a Polymeric Surfactant and an Emulsifiable Concentrate of 2,4,6-Triethylbenzene-1,3-Dinitrile Oxide A polymeric surfactant suitable for forming an emulsifiable concentrate of the dinitrile oxide was prepared in two stages as follows:
Stage 1 - Hydrophobic Monomer Polymerization A mixture of 793.8 parts TERGITOL'~ NP-7 surfactant (a trademark of Union Carbide) and 18.4 parts t-butyl peroctoate were heated to 90~C in a stirred glass reactor and blanketed with an inert atmosphere of nitrogen. A mixture of 433.1 parts styrene, 144.4 parts 2-ethylhexyl acrylate, 35.0 parts glycidyl methacrylate and a separate feed of 18.4 parts t-butyl peroctoate were added continuously and proportionately to the reactor over 1.5 hours. During 30 this addition period, the reaction temperature reached a maximum temperature of 99~C.
Stage 2 - Hydrophilic Monomer Polymerization The following feed solutions were added continuously and proportionately to the reactor over 1.5 hours with the reaction temperature decreasing from 99~C to 92~C: 1 ) 87.5 parts 2-acrylamido-2-methylpropane sulfonic acid (AMPS) admixed with 87.5 parts deionized 35 (Dl) water, and 41.0 parts dibutyl amine; 2) 1176.7 parts TERGlTOL'" NP-7; and 3) 0.7 parts 2-mercaptoethanol admixed with 15.8 parts Dl water. The reactor contents were maintained at 90~C for an additional 2 hours. The polymer/non-ionic/water reaction mixture (PC-3) was transferred to a steam still and the residual monomers were removed with the aid of a vacuum.
g W O 97/03034 PCT~US96/11499 A solution containing 1.9 9 of 2,4,6-triethylbenzene-1,3-dinitrile oxide (TON-2)and 5.8 9 butyl benzyl phthalate was prepared and mixed with 1.1 9 of PC-3 along with 2.9 9 of TERGlTOL'~ NP-7 to form the emulsifiable concentrate.
B. The Curing Step The emulsifiable concentrate from Part A was diluted with 11.7 9 of distilled water and shaken to form an aqueous dispersion. This aqueous dispersion was then added to 76.6 9 of a polyunsaturated styrene/butadiene/acrylic acid latex (54.7 percent styrene, 43.3 percent butadiene,2 percent acrylic acid) having a pH of 3.5 and containing 38.7 9 solids and 37.9 9 water. This material was cast into 10-mil (0.25 mm) films on a glass substrate and cured 10 upon evaporation of water, at room temperature for 24 hours. When a portion of the resultant film (0.42 9) was mixed with 8.5 9 of toluene, the film swelled, but ddid not dissolve.
In contrast, a comparable film that was prepared in the same manner, but did not contain the dinitrile oxide, was found to dissolve partially in toluene. Thus, the dinitrile oxide-treated film was found to be more highly crosslinked than the control that does not contain the dinitrile oxide curative.
Exam~ie 2 - Crosslinking of Crotyl Methacrylate-Containing Latex with TON-2 Phase (A): Synthesis of a Latex A 5-L, five-necked round-bottomed flask equipped with a nitrogen inlet, a refluxcondenser connected to an oil bubbler with a nitrogen outlet, a mechanical stirrer, and five 20 feed streams was immersed into a water bath and purged with nitrogen a suspension of latex seed (prepared from styrene/acrylic acid 96/4; median particle size 240 A; 40 weight percent;
22.28 9) and VERSENOLrU 120 chelating agent (a trademark of The Dow Chemical Company, 8.32 9 of 1 percent solution) in water (642.8 9) were placed into the flask and heated at 60~C.
Butyl acrylate (399.36 9), methyl methacrylate (357.6 9), and methacrylic acid (16.64 9) were 25 pre-mixed to give a basic monomer mixture (773.6 9). Using five syringes and syringe pumps, the following components were added to the flask while constantly maintaining the nitrogen atmosphere and the temperature of 60~C:
(a) crotyl methacrylate (43.2 9) and a portion of the basic monomer mixture (40 9);
(b) the remaining basic monomer mixture (733.6 9);
(c) t-dodecyl mercaptan (16.649);
(d) the solution of t-butyl hydroperoxide (4.64 9 of 70 percent active; 3.25 percent active) and DOWFAX'U (a trademark of The Dow Chemical Company) 2EP
surfactant (17.76 9) in water (83.2 9); and (e) the solution of sodium formaldehyde sulfoxylate (SFS, 2.52 9 in 28 9 of water). Y
Component (b) was added over the first five hours, followed by the addition of component (a) over an additional hour. Components (c), (d), and (e) were added over six hours.
After the addition of all components, stirring at 60~C was continued for an additional hour.
CA 02226849 1998-01-13 ..
W O 97/03034 PCT~US96/11499 The resuiting latex was then filtered through a 200-mesh screen and cooled to ambient temperature. The conversion was 99.4 percent, and the recovery 97.8 percent. This latex had 50.4 percent solids, and particles with a mean and median size of 1442 A and 1341 A, ~ respectively.
5 Phase (B): Crosslinking of a Coating An emulsion of TON-2 (12.5 weight percent in ethyl benzoate/water) was prepared by a slow addition of the solution of TON-2 (3.125 9) in ethyl benzoate (9.375 9) to a solution of RHODAPEX'~ C0-436 surfactant (a trademark of Rhane Poulenc,0.215 9 of 58 percent aqueous solution) in water (12.285 9) with high shear. A portion (8.01 9) of this 10 emulsion was added to the crotyl methacrylate-containing latex (42.00 9) described in Phase (A) of this example. The resulting latex/TON-2 mixture was cast and dried, and aged at 22~C
and 50 percent relative humidityfor 18 hours. A piece of the resulting film (about 1 9) was isolated and weighed, then placed in a vial with toluene (35 mL). The mixture was shaken at high speed for 1 hour, and the soluble phase was removed. The mass of the residual gel-state polymer in a wet state was recorded and the wet gel was then dried in vacuo at 65~C. The mass of the resulting dry gel was recorded, and the swell index (that is, the difference in weights of wet gel and dry gel divided by the weight of a dry gel) and percent gel (that is, the ratio of weights of dry gel and the initial sample multiplied by 100) measured. In this example, the film prepared from the latex/TON-2 mixture hadsa swell index of 4.2 and 86.8 percent gel, 20 indicating a high degree of crosslinking. A reference coating prepared from the same latex, but without TON-2 added dissolved completely, confirming the absence of crosslinking in latex alone.
Example 3 - Crosslinking of Glycidyl Methacrylate- Containing Latex with TON-2 Phase (A): Synthesis of a Latex To a 1-gallon reactor equipped with a reflux condenser, a mechanical stirrer, and nitrogen inlet and outlet was placed a suspension of latex seed (prepared from styrene/acrylic acid96/4;medianparticlesize270A;40weightpercent; 19.34g)andVERSENOL'4 120(15.299of 1 percent solution) in water (1255.32 9). The flask was maintained at a temperature of 90~C
under a nitrogen purge. The following components were simultaneously added to the flask 30 over 230 minutes:
(a) butyl acrylate (779.60 9) and methacrylic acid (91.72 9);
(b) methyl methacrylate (657.31 9) and t-dodecylmercaptan (15.29 9); and (c) the solution of ammonium persulfate (7.64 9) and DOWFAX~" 2EP surfactant (33.97 9) in water (152.86 9).
After all the components were added, stirring at 90~C was continued for 30 minutes. The resulting latex was then filtered through a 200-mesh screen and cooled to ambienttemperature. This latex had 51.9 percentsolids, particleswith a median size of 1380A, andapHof2.2.
CA 02226849 l998-0l-l3 W 097/03034 PCT~US96/11499 The latex (250 9) was adjusted to a pH of 7.8, whereupon water (Z0 9) and 4-methoxyphenol (0.20 9) were added. This solution was placed into the 500-mL,3-necked round-bottomed flask equipped with an air inlet, a reflux condenser with an air outlet, and a mechanical stirrer. The flask was immersed into a water bath, heated to 90~C, and the air-flow was established. Glycidyl methacryiate (5.2 9) was added over 3 hours, and the resulting latex was cooled to ambient temperature. A milky suspension with no coagulates was obtained, having 46.3 percent solids.
Phase (B): Crosslinking of a Coating An emulsion of TON-Z as prepared in Example 2 (12.5 weight percent in ethyl benzoate/water; 8.01 9) was added to the glycidyl methacrylate-containing latex (65.34 9) described in Phase (A) of this example. The resulting latex/TON-2 mixture was cast to give a coating with 61.3 percent gel.
Exam,ole 4 - Crosslinking of S/B Latex with TON-2 The S/B latex used in this example was prepared using styrene (57.5 percent), butadiene (38 percent with a 1,2: 1,4 ratio of 15/85), and acrylic acid (4.5 percent). An emulsion of TON-2 (12.5 percent in toluene/water) was prepared by a slow addition of the solution of TON-2 (3.125 9) in toluene (9 375 g) to a solution of RHODAPEX'~ C0-436 surfactant (0.215 g of 58 percent aqueous solution) in water (12.285 9) with high shear. A portion of this emulsion (6.40 9) was added to the S/B latex (100.0 9), and toluene was evaporated off. The resulting latex/TON-2 mixture gave a coating which had 90.9 percent gel, a swell index of 4.9, and a tensile strength of 1032.2 psi.
Exam,~le 5 - Preparation Of Di(3-Fulmido-2,4,6-trimethyl)-benzyl Ether Di(3-fulmido-2,4,6-trimethyl)-benzyl ether was prepared in two steps from 3-hydroxymethyl-2,4,6-trimethylbenzaldehyde, which was prepared according to A. P.
Yakubov et al. in Izv. Akd. Nauk SSR, Ser. Khim., No.7, pp.1609-1615.
To a flask fitted by a 10-cm Vigeux column to which was attached a Barret trap and reflux condenser was added a mixture of 3-hydroxymethyl-2,4,6-trimethylbenzaldehyde (23 9, 0.129 mole) and sulfuric acid (0.2 9,96 percent in 130 mL of benzene). The mixture was refluxed vigorously for 60 minutes. Benzene was removed in vacuo and the crude product was dissolved in chloroform (about 60 mL), whereupon isopropanol (about 200 mL) was added at 60~C. The mixture was cooled to 5~C, and a crystalline precipate was filtered and determined to be di(3-formyl-2,4,6-trimethyl)benzyl ether (18.7 g,85 percent yield), m.p.158~C to 161~C.
To a flask containing di(3-formyl-2,4-6-trimethyl)benzyl ether (9.8 9, 0.029 mole) and ethanol (110 mL) was added in one portion a solution of NaOH (4.64 9,0.116 mole) and hydroxylamine hydrochloride (8.06 9,0.116 mole) in water (20 mL). The mixture was heated for ~f 2.5 hours with vigorous stirring, then cooled to 5~C, whereupon a crystalline precipitate was filtered and washed with ethanol (30 mL) and water. The precipitate was predetermined to be W O 97/03034 PCTrUS96/11499 di(3-hydroximinomethyl-2,4,6-trimethyl)benzyl ether (8.9 9, 83 percent yield), m.p. 210~C to 213~C.
To a flask maintained at 5~C and containing a vigorousiy stirred suspension of di(3-hydroximinomethyl-2,4,6-trimethyl)benzyl ether (7.9 9 0.0215 mole) in methylene chloride (100 mL) was added (NaOCI (53 mL of a 15 percent solution). The reaction mixture was stirred for 2 hours at 5~C to 10~C, whereupon the organic layer was separated, and the aqueous phase was extracted with methylene chloride (50 mL). The organic phases were combined, then washed with water (3 x 200 mL). The solvent was then removed in vacuo, and the resultant mixture was cooled to 20~C. A crystalline precipitate was filtered and determined to be di(3-fulmido-2,4,6-trimethyl)benzyl ether (7.5 9, 96 percent yield), m.p.156~C to 158~C.
Infrared spectroscopy showed a strong narrow band at 2300 cm~l corresponding to nitrile oxide.
Claims (18)
1. A composition comprising an aqueous dispersion of a stable polynitrile oxide represented by the structure:
G-(C~N+-O-)x where x is an integer greater than 1, G is an aromatic, aliphatic, or cycloaliphatic group having at least one substituent adjacent to each nitrile oxide group, the substituent characterized by being non-interfering with a reaction between nitrile oxide groups and unsaturated groups, and by being R, halo, SH, SR, SOR, SO2R, hydroxy, or OR, where R is a C1-12 linear, branched, or cyclic alkyl group.
G-(C~N+-O-)x where x is an integer greater than 1, G is an aromatic, aliphatic, or cycloaliphatic group having at least one substituent adjacent to each nitrile oxide group, the substituent characterized by being non-interfering with a reaction between nitrile oxide groups and unsaturated groups, and by being R, halo, SH, SR, SOR, SO2R, hydroxy, or OR, where R is a C1-12 linear, branched, or cyclic alkyl group.
2. The composition of Claim 1 which further comprises an aqueous dispersion of a polyunsaturated monomer or polymer.
3. The composition according to either Claim 1 or 2 wherein the stable polynitrile oxide is represented by the structure:
, or where R1, R2, R3, and R4 are each independently H, R, halo, SH, SR, SOR, SO2R, hydroxy, or OR, with the proviso that at least one of R1, R2, R3, and R4 that is adjacent to a nitrile oxide group is not H; where R5, R6, R7, and R8 are each independently H, R, halo, SH, SR, SOR, SO2R, hydroxy, or OR; or R5 and R6, or R7 and R8, together with the carbon atoms to which they are attached, form a benzene ring, wherein at least one of R5 or R7 is not H, and at least one of R6 or R8 is not H; R is a C1-C12 linear, branched, or cyclic alkyl group; i is 2 or 3; m and n are each 0, 1, or 2, and n + m~2.
, or where R1, R2, R3, and R4 are each independently H, R, halo, SH, SR, SOR, SO2R, hydroxy, or OR, with the proviso that at least one of R1, R2, R3, and R4 that is adjacent to a nitrile oxide group is not H; where R5, R6, R7, and R8 are each independently H, R, halo, SH, SR, SOR, SO2R, hydroxy, or OR; or R5 and R6, or R7 and R8, together with the carbon atoms to which they are attached, form a benzene ring, wherein at least one of R5 or R7 is not H, and at least one of R6 or R8 is not H; R is a C1-C12 linear, branched, or cyclic alkyl group; i is 2 or 3; m and n are each 0, 1, or 2, and n + m~2.
4. The composition according to either Claim 1 or 2 wherein the stable polynitrile oxide is represented by the structure:
,or where R9, R10, R11, and R12 are each independently H, R, halo, SH, SR, SOR, SO2R, hydroxy, or OR, with the proviso that at least one of R9 and R11 is not H when a nitrile oxide group is adjacent to both R9 and R11, and at least one of R10 and R12 is not H when a nitrile oxide group is adjacent to both R10 and R12; R1, R2, and R3, are each independently H, alkyl, halo, SH, SR, SOR, SO2R, hydroxy, or OR, with the proviso that at least one of R1, R2, and R3 that is adjacent to a nitrile oxide group is not H; p and r are each 0, 1, or 2, and p + r~2; X is CH2, C(R)2, carbonyl, O,S,SO,SO2,NH,SO2NH, or NR; t and u are each 0,1,2, or 3; and t + u ~ 2; Y is a bond, CH2, C(R)2, carbonyl, O,S,SO2,NH,NR, 9,9'-fluoreno, or phenylene; and R is a C1-C12 linear, branched, or cyclic alkyl group.
,or where R9, R10, R11, and R12 are each independently H, R, halo, SH, SR, SOR, SO2R, hydroxy, or OR, with the proviso that at least one of R9 and R11 is not H when a nitrile oxide group is adjacent to both R9 and R11, and at least one of R10 and R12 is not H when a nitrile oxide group is adjacent to both R10 and R12; R1, R2, and R3, are each independently H, alkyl, halo, SH, SR, SOR, SO2R, hydroxy, or OR, with the proviso that at least one of R1, R2, and R3 that is adjacent to a nitrile oxide group is not H; p and r are each 0, 1, or 2, and p + r~2; X is CH2, C(R)2, carbonyl, O,S,SO,SO2,NH,SO2NH, or NR; t and u are each 0,1,2, or 3; and t + u ~ 2; Y is a bond, CH2, C(R)2, carbonyl, O,S,SO2,NH,NR, 9,9'-fluoreno, or phenylene; and R is a C1-C12 linear, branched, or cyclic alkyl group.
5. The composition according to either Claim 1 or 2 wherein the stable polynitrile oxide is represented by the structure:
,or
,or
6. The composition of any of Claims 1, 2, or 5 wherein the stable polynitrile oxide is represented by the structure:
7. The composition of Claim 2 wherein the aqueous dispersion of the polyunsaturated polymer is an emulsion polymer of an .alpha.-olefinically unsaturated aromatic monomer and a conjugated diene.
8. The composition of Claim 7 wherein the emulsion polymer is a styrene-butadiene latex, an .alpha.-methylstyrene-butadiene latex, a styrene-isoprene latex or an .alpha.-methylstyrene-isoprene latex.
9. The composition of Claim 2 wherein the aqueous dispersion of the polyunsaturated polymer is an emulsion polymer of .alpha.-methylstyrene-butadiene-.alpha.-methylstyrene, .alpha.-methylstyrene-isoprene-.alpha.-methylstyrene, styrene-isoprene-styrene, or styrene-butadiene-styrene.
10. The composition of Claim 2 wherein the aqueous dispersion of the polyunsaturated polymer is a maleate- or fumarate-containing polyester; a vinylically or allylically unsaturated acrylate copolyester; a butadiene-acrylonitrile copolymer; an ethylene-propylene-dicyclopentadiene terpolymer; a polyisoprene; a polybutadiene; an unsaturated polyurethane; or a polyether copolymer or terpolymer containing at least two unsaturated epoxide constituents.
11. The composition of Claim 2 wherein the aqueous dispersion of the polyunsaturated polymer is an emulsion polymer of a monofunctional alkyl acrylate or methacrylate and crotyl acrylate or methacrylate.
12. The composition of Claim 2 wherein the aqueous dispersion of the polyunsaturated polymer is formed by the reaction of glycidyl methacrylate and an aqueous dispersion containing carboxyl functionality.
13. The composition of Claim 12 wherein the aqueous dispersion containing carboxyl functionality is an aqueous dispersion of poly(methylmethacrylate/butylmeth-acrylate/methacrylic acid).
14. The composition of Claim 2 wherein the aqueous dispersion of the polyunsaturated polymer is formed by the reaction of a latex containing pendant benzyl chloride groups and a vinyl monomer containing a tertiary amine group.
15. A method of curing a latex having a polyunsaturated disperse phase, comprising the steps of:
a) mixing with the latex a water-insoluble, stable polynitrile oxide represented by the structure:
G-(C~N+-O~)x where x is an integer greater than 1, G is an aromatic, aliphatic, or cycloaliphatic group having at least one substituent adjacent to each nitrile oxide group, the substituent characterized by inhibiting dimerization of nitrile oxide, and beingnon-interfering with a reaction between nitrile oxide groups and unsaturated groups; and b) removing water from the mixture.
a) mixing with the latex a water-insoluble, stable polynitrile oxide represented by the structure:
G-(C~N+-O~)x where x is an integer greater than 1, G is an aromatic, aliphatic, or cycloaliphatic group having at least one substituent adjacent to each nitrile oxide group, the substituent characterized by inhibiting dimerization of nitrile oxide, and beingnon-interfering with a reaction between nitrile oxide groups and unsaturated groups; and b) removing water from the mixture.
16. A compound having the structure:
wherein each R' is independently C1-C12-alkyl, F, Cl, Br, l, O-C1-C12-alkyl, or S-C1-C12-alkyl; each R° is a substituent that does not spontaneously react with the nitrile oxide group; each n' is independently 0, 1, or 2; n" is an integer greater than 1; each X' is independently a bond or a connecting group; and Y' is a polyvalent radical that comprises an ether, ester, amide, amine, carbonate, ketone, urethane, or arylene.
wherein each R' is independently C1-C12-alkyl, F, Cl, Br, l, O-C1-C12-alkyl, or S-C1-C12-alkyl; each R° is a substituent that does not spontaneously react with the nitrile oxide group; each n' is independently 0, 1, or 2; n" is an integer greater than 1; each X' is independently a bond or a connecting group; and Y' is a polyvalent radical that comprises an ether, ester, amide, amine, carbonate, ketone, urethane, or arylene.
17. The compound of Claim 16 wherein each R' is independently methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, methoxy, or ethoxy; R° is ethyl, methyl, n-propyl, isopropyl, n-butyl, isobutyl, methoxy, ethoxy, F, Cl, Br, or l; n' is 0 or 1; n" is 2 or 3; and each X' is a bond, an alkylene group, a cycloalkylene group, or arylene group.
18. The compound of Claim 17 wherein each R° and each R' are independently methyl, ethyl, or methoxy; each X' is a bond, a methylene group, or a phenylene group; n" is 2;
and Y' is a divalent radical that comprises an ether or ester moiety.
and Y' is a divalent radical that comprises an ether or ester moiety.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US101895P | 1995-07-10 | 1995-07-10 | |
| US60/001,018 | 1995-07-10 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2226849A1 true CA2226849A1 (en) | 1997-01-30 |
Family
ID=21693987
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002226849A Abandoned CA2226849A1 (en) | 1995-07-10 | 1996-07-10 | Stable polynitrile oxides and their use as curing agent especially for latex |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP0842147A2 (en) |
| AU (1) | AU709961B2 (en) |
| BR (1) | BR9609523A (en) |
| CA (1) | CA2226849A1 (en) |
| WO (1) | WO1997003034A2 (en) |
Families Citing this family (27)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2245780A1 (en) * | 1997-09-17 | 1999-03-17 | Dane Kenton Parker | Synthesis of stable nitrile oxide compounds |
| US6355838B1 (en) | 1999-02-02 | 2002-03-12 | National Starch And Chemical Investment Holding Corporation | Reagents for heat activated polymer crosslinking |
| US6252009B1 (en) * | 1999-02-24 | 2001-06-26 | The Goodyear Tire & Rubber Company | Process for curing acrylic polymers |
| WO2002006391A1 (en) * | 2000-07-14 | 2002-01-24 | National Starch And Chemical Investment Holding Corporation | Reagents for heat activated polymer crosslinking |
| PE20020506A1 (en) | 2000-08-22 | 2002-07-09 | Glaxo Group Ltd | PIRAZOLE DERIVATIVES FUSED AS PROTEIN KINASE INHIBITORS |
| BR0114504A (en) | 2000-09-28 | 2003-10-21 | Dow Global Technologies Inc | Latex cross-linking with blocked nitrile oxides or epoxy silanes and process for using the obtained product |
| GB0124941D0 (en) | 2001-10-17 | 2001-12-05 | Glaxo Group Ltd | Chemical compounds |
| GB0124936D0 (en) | 2001-10-17 | 2001-12-05 | Glaxo Group Ltd | Chemical compounds |
| GB0124934D0 (en) | 2001-10-17 | 2001-12-05 | Glaxo Group Ltd | Chemical compounds |
| GB0124931D0 (en) | 2001-10-17 | 2001-12-05 | Glaxo Group Ltd | Chemical compounds |
| GB0124939D0 (en) | 2001-10-17 | 2001-12-05 | Glaxo Group Ltd | Chemical compounds |
| GB0124933D0 (en) | 2001-10-17 | 2001-12-05 | Glaxo Group Ltd | Chemical compounds |
| GB0124938D0 (en) | 2001-10-17 | 2001-12-05 | Glaxo Group Ltd | Chemical compounds |
| DE60334651D1 (en) | 2002-02-12 | 2010-12-02 | Glaxosmithkline Llc | Nicotinamide and its use as P38 inhibitors |
| GB0308186D0 (en) | 2003-04-09 | 2003-05-14 | Smithkline Beecham Corp | Novel compounds |
| GB0308185D0 (en) | 2003-04-09 | 2003-05-14 | Smithkline Beecham Corp | Novel compounds |
| GB0308201D0 (en) | 2003-04-09 | 2003-05-14 | Smithkline Beecham Corp | Novel compounds |
| GB0318814D0 (en) | 2003-08-11 | 2003-09-10 | Smithkline Beecham Corp | Novel compounds |
| US7294678B2 (en) | 2005-01-28 | 2007-11-13 | Regent Medical Limited | Thin walled polynitrile oxide crosslinked rubber film products and methods of manufacture thereof |
| JP2010037288A (en) * | 2008-08-06 | 2010-02-18 | Air Water Inc | Trifunctional nitrile oxide and method for producing the same |
| US11247424B1 (en) | 2016-12-13 | 2022-02-15 | Bridgestone Americas Tire Operations, Llc | Methods for retreading tires |
| EP4328046A1 (en) * | 2021-05-17 | 2024-02-28 | Sumitomo Rubber Industries, Ltd. | Nitrile oxide compound and ionic-functional-group-containing polymer |
| CN115819288A (en) * | 2022-11-18 | 2023-03-21 | 西安近代化学研究所 | Nitrile oxide, bifunctional nitrile oxide and preparation method thereof |
| CN115784941B (en) * | 2022-12-19 | 2024-03-22 | 西安近代化学研究所 | Trifunctional nitrile oxide, preparation method and application thereof |
| CN116003299A (en) * | 2022-12-19 | 2023-04-25 | 西安近代化学研究所 | Difunctional nitrile oxide, preparation method and application thereof |
| CN116332803A (en) * | 2023-03-20 | 2023-06-27 | 西安近代化学研究所 | Trifunctional aromatic nitrile oxide compound and synthesis method thereof |
| CN116462612A (en) * | 2023-03-20 | 2023-07-21 | 西安近代化学研究所 | Tetrafunctional aromatic nitrile oxide compound and synthesis method thereof |
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| US3670023A (en) * | 1966-10-04 | 1972-06-13 | Hercules Inc | Polyfunctional carbonyl nitride oxides |
-
1996
- 1996-07-10 AU AU64876/96A patent/AU709961B2/en not_active Ceased
- 1996-07-10 BR BR9609523-7A patent/BR9609523A/en unknown
- 1996-07-10 CA CA002226849A patent/CA2226849A1/en not_active Abandoned
- 1996-07-10 EP EP96924413A patent/EP0842147A2/en not_active Withdrawn
- 1996-07-10 WO PCT/US1996/011499 patent/WO1997003034A2/en active Application Filing
Also Published As
| Publication number | Publication date |
|---|---|
| EP0842147A2 (en) | 1998-05-20 |
| AU6487696A (en) | 1997-02-10 |
| WO1997003034A2 (en) | 1997-01-30 |
| BR9609523A (en) | 2001-11-13 |
| AU709961B2 (en) | 1999-09-09 |
| WO1997003034A3 (en) | 1997-03-13 |
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