CN102775984A - Pasty chemiluminescent composition with low oxidizability and high stability - Google Patents
Pasty chemiluminescent composition with low oxidizability and high stability Download PDFInfo
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- CN102775984A CN102775984A CN2011101233217A CN201110123321A CN102775984A CN 102775984 A CN102775984 A CN 102775984A CN 2011101233217 A CN2011101233217 A CN 2011101233217A CN 201110123321 A CN201110123321 A CN 201110123321A CN 102775984 A CN102775984 A CN 102775984A
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Abstract
The invention relates to a pasty chemiluminescent composition with low oxidizability and high stability. The composition comprises: (1) an oxalate-containing ''oxalate component'', with the oxalate accounting for 1%-30% of chemiluminescent composition; and (2) an ''activator component'' containing an oxidizing agent. The ''oxalate component'' and the ''activator component'' are in a weight ratio of 1:50-3:1. The ''oxalate component'' and/or the ''activator component'' contain/contains a fluorescent agent, a catalyst, a chelating agent, a solvent and a thickener. The composition is characterized in that the oxidizing agent in the ''activator component'' accounts for 0.7%-2% of the chemiluminescent composition. The invention has the advantages that: the use of a low-concentration oxidizing agent reduces the oxidizability of the chemiluminescent composition, decreases the damage to organisms. Meanwhile, the storage stability of the chemiluminescent composition is greatly improved, and an excellent chemiluminescent property is maintained.
Description
(1) technical field:
The present invention relates to the chemical luminous composite field, particularly a kind of pasty chemical luminous composite of low oxidative high stability.
(2) background technology:
The compsn of barkite-oxygenant-dyestuff chemistry luminescence system is known by people and is utilized, for example the oxidation chemistry light emitting composition described in USP 3816326,4313843 and 5122306.Traditional oxidation chemistry light emitting composition is the LV liquid state, and this has just determined it under certain container containing restriction, to use, and has so just limited its range of application.
One Chinese patent application 200610129552.8 has been described a kind of full-bodied relatively pasty chemical luminous composite with 7674406 of USPs; Be used for coating use under open environment; They all utilize water-soluble polymer to make water be thickened to required viscosity, thereby reach predetermined application target.But when this based composition is used for the coating of human hair or skin, its oxidant concentration more the hyperoxia voltinism then pungency is strong more more by force, can make organism receive corresponding infringement.Simultaneously since its oxygenant with water-soluble polymer in same component, cause that water-soluble polymer is made viscosity degradation by the oxygenant oxidation of high density in the storage process, until becoming liquid state fully, can't satisfy predetermined application target.Therefore, when making pasty chemical luminous composite, choosing of oxygenate content will produce great effect to this making.
(3) summary of the invention
The object of the present invention is to provide a kind of pasty chemical luminous composite with low oxidative high stability; It is based on the barkite is " the barkite component " of activeconstituents and is " activator component " of activeconstituents with the oxygenant; And the chemical luminous composite that is contained in one or more fluorescent agents, catalyzer, sequestrant, solvent and thickening material in said " barkite component " and/or " activator component "; Viscosity is greater than 1000mPas, and particularly the content of oxygenant in chemical luminous composite in " activator component " is 0.7% to 2%.
Technical scheme of the present invention: a kind of pasty chemical luminous composite with low oxidative high stability, it comprises:
(1) a kind of " barkite component " that contains barkite, the content of barkite in chemical luminous composite is 1%-30%;
(2) a kind of " activator component " that contains oxygenant;
The weight ratio of " barkite component " and " activator component " is in 1: 50 to 3: 1 scope; Contain fluorescent agent, catalyzer, sequestrant, solvent and thickening material in " barkite component " and/or " activator component ",
It is characterized in that the content of oxygenant in chemical luminous composite in " activator component " is 0.7% to 2%.
Above-mentioned said barkite component can be solid-state, liquid state and paste; The barkite component can be single barkite, can be barkite and fluorescent agent and/or mixture of catalysts, also can be barkite or barkite and fluorescent agent and/or the catalyzer mixture with non-aqueous solvent.
Above-mentioned said activator component is solution, suspension-s, colloid or the emulsion of viscosity greater than 1000mPas, comprises oxygenant, one or more solvents and/or fluorescent agent, catalyzer, sequestrant; Contain thickening material in the activator component simultaneously, so that activator component reaches the viscosity that needs.
Barkite in the above-mentioned said barkite component is two (2,4,5-three chloro-6-carbonyls penta oxygen phenyl) barkites, two (2,4; The 5-trichlorophenyl) barkite, two (2,4, the own oxygen phenyl of 5-three bromo-6-carbonyls) barkite, two (2;-nitrophenyl) barkite, two (2, the 4-dinitrophenyl) barkite, two (2,6-two chloro-4-nitrophenyls) barkite, two (2; 4,6-trichlorophenyl) barkite, two (3-trifluoromethyl-4-nitrophenyl) barkite, two (1,2-dimethyl--4; The 6-dinitrophenyl) barkite, two (2,4 dichloro benzene base) barkite, two (2, the 4-dinitrophenyl) barkite, two (2; The 5-dinitrophenyl) barkite, two (2-formyl-4-nitrophenyl) barkite, two (five chlorophenyl) barkite, two (1,2-dihydro-2-oxo--1-pyridyl) oxalic dialdehyde, two (2,4-dinitrobenzene-6-aminomethyl phenyl) barkite; Said barkite preferably comprises two (2,4,5-three chloro-6-carbonyls penta oxygen phenyl) barkite (being called " CPPO ") or two (2,4, the 5-trichlorophenyl) barkites (being called " TCPO ").
Oxygenant in the above-mentioned said activator component is hydrogen peroxide, sodiumperoxide, peroxo-trisodium phosphate, urea peroxide, sodium perborate, peroxo-Histidine, tertbutyl peroxide and peroxo-phenylformic acid; Preferred oxide compound is a urea peroxide.
The fluorescent agent that contains in above-mentioned said " barkite component " and/or " activator component " has the spectral emissions of 330nm-1000nm scope, and it is present in barkite component, activator component or the two kinds of components; Said fluorescent agent is a USP 3729426,3948797, the fluorescent agent described in 4017415 and 5122306, and such as 9,10-diphenylanthrancene, 9; 10-tolane base anthracene, 1,8-two chloro-9,10-tolane base anthracene, 2-ethyl-9,10-tolane base anthracene, 1; 6,7,12-four phenoxys-N, N '-two (2; 5 diisopropyl phenyls)-3,4,9,10-perylene dicarboximide etc.; Preferred fluorescent agent is 9,10-tolane base anthracene and 1,8-two chloro-9,10-tolane base anthracene; The content of said fluorescent agent in chemical luminous composite is 0.01%-1%.
The catalyzer that contains in above-mentioned said " barkite component " and/or " activator component " is SS, potassium salicylate, lithium salicylate, 5-chloro-salicylic acid sodium, 5-chloro-salicylic acid lithium, sodium trifluoroacetate, Woodtreat A potassium, Whitfield's ointment TBuA, phenylformic acid TBuA, TBAP, benzyltriethylammoinium chloride, Tetrabutyl amonium bromide, cetyl trimethylammonium bromide, X 2073, Sodium palmityl sulfate, trolamine, water glass; Preferred catalyzer is SS, trolamine and benzyltriethylammoinium chloride; The content of said catalyzer in chemical luminous composite is 0.01%-5%.
The sequestrant that contains in above-mentioned said " barkite component " and/or " activator component " is YD 30 and one of which sodium, disodium, trisodium, tetra-na salt; Preferred sequestrant is an EDTA Disodium; The content of said sequestrant in chemical luminous composite is 0.02%-2%.
The solvent that contains in above-mentioned said " barkite component " and/or " activator component " is ETHYLE ACETATE, dimethyl phthalate, butyl benzoate, ethyl benzoate, wintergreen oil, salicylic ether, glycerine, the trimethyl carbinol and water; Preferred solvent is dimethyl phthalate, butyl benzoate and water; The content of said solvent in chemical luminous composite is 40%-95%.
The thickening material that contains in above-mentioned said " barkite component " and/or " activator component " is a water-soluble polymer, and it and water are formed the matrix of activator component jointly; Said thickening material is W-Gum, Viscogum BE, guar gum, XG 550, gelatin, CMC 99.5, TKK 021, Natvosol, ROHM, polyacrylic acid derivative, polyoxyethylene glycol and Vinylpyrrolidone polymer; Preferred thickening is XG 550, Natvosol and polyacrylic acid derivative, like CBP; The content of said thickening material in chemical luminous composite is 0.07%-35%.
Meliority of the present invention is: owing to used the oxygenant of lower concentration, the oxidisability of this chemical luminous composite is reduced, reduced the infringement to organism; Its stability in storage is improved greatly, and kept the excellent in chemical luminescent properties.
Chemical analysis of the present invention: contain oxygenant in this chemical luminous composite, so the concentration of oxygenant directly influences the oxidisability of compsn.Among the present invention oxidant concentration is reduced significantly, reduced by 1 one magnitude than the concentration of oxygenant in the previous related invention, the also corresponding reduction of its oxidisability has reduced the infringement to organism.Have a small amount of evidence to prove that (data source is in Chinese oral cleaning nursing article TIA website) concentration of urea peroxide in dental bleaching gel is higher than and has had bleaching toxicity at 10% o'clock, it is comparatively safe that concentration is lower than 10%.The oxidant concentration upper limit of the present invention has only 2%, and this provides more assurance for security.
(4) embodiment:
Embodiment 1
The tabulation of table 1 embodiment 1 composition
| Composition | Content | |
| The barkite component | ||
| Polyoxyethylene glycol-400 | 8.7％ | |
| Polyoxyethylene glycol-4000 | 18.987％ | |
| CPPO | 21.7％ | |
| 9,10-tolane base anthracene | 0.7％ | |
| Dimethyl phthalate | 3.5％ | |
| Activator component | ||
| Water | 43.3％ | |
| Urea peroxide | 1.8％ | |
| Trolamine | 0.004％ | |
| SS | 0.009％ | |
| XG 550 | 1.3％ | |
| Amount to | 100％ |
Be listed in by table 1 and add polyoxyethylene glycol-4000, CPPO, 9 in the polyoxyethylene glycol-400,10-tolane base anthracene and dimethyl phthalate, stirring is the barkite component.
In water, add urea peroxide, trolamine, SS and XG 550, stirring is activator component.Wherein, the content of oxygenant urea peroxide is 1.8%, greatly is lower than prior art.
Above-mentioned barkite component is mixed with activator component, produce green chemoluminescence.The weight ratio of barkite component and activator component is 1.15: 1.
Viscosity is greater than 1000mPas.
Embodiment 2
The tabulation of table 2 embodiment 2 compositions
| Composition | Content | |
| The barkite component | ||
| CPPO | 9.3％ |
| Activator component | ||
| Water | 81.2％ | |
| Urea peroxide | 1.3％ | |
| Trolamine | 0.93％ | |
| Benzyltriethylammoinium chloride | 0.28％ | |
| CBP | 0.93％ | |
| 9,10-tolane base anthracene | 0.46％ | |
| Dimethyl phthalate | 5.6％ | |
| Amount to | 100％ |
Listed CPPO is the barkite component by table 2.
In water, add urea peroxide, trolamine, benzyltriethylammoinium chloride, CBP, 9,10-tolane base anthracene and dimethyl phthalate, stirring is activator component.Wherein, the content of oxygenant urea peroxide is 1.3%, greatly is lower than prior art.
Above-mentioned barkite component is mixed with activator component, produce green chemoluminescence.The weight ratio of barkite component and activator component is 9.7: 1.
Embodiment 3
The tabulation of table 3 embodiment 3 compositions
| Composition | Content | |
| The barkite component | ||
| CPPO | 3.75％ | |
| Activator component | ||
| Water | 87.5％ | |
| Urea peroxide | 0.875％ | |
| Trolamine | 1.25％ | |
| Benzyltriethylammoinium chloride | 0.125％ | |
| EDTA Disodium | 0.875％ | |
| CBP | 0.875％ | |
| Natvosol | 0.875％ | |
| 1,8-two chloro-9,10-tolane base anthracene | 0.125％ |
| Dimethyl phthalate | 3.75％ | |
| Amount to | 100％ |
Listed CPPO is the barkite component by table 3.
In water, add urea peroxide, trolamine, benzyltriethylammoinium chloride, EDTA Disodium, CBP, Natvosol, 1,8-two chloro-9,10-tolane base anthracene and dimethyl phthalate, stirring is activator component.Wherein, the content of oxygenant urea peroxide is 0.875%, greatly is lower than prior art.
Above-mentioned barkite component is mixed with activator component, produce the xanchromatic chemoluminescence.The weight ratio of barkite component and activator component is 25.7: 1.
The related oxygenant of present technique scheme choose thing hydrogen peroxide, sodiumperoxide, peroxo-trisodium phosphate, urea peroxide, sodium perborate, peroxo-Histidine, tertbutyl peroxide and peroxo-phenylformic acid etc.; They have the known oxide compound performance that is equal to; The foregoing description preferred oxides urea peroxide; Do not hinder among above-mentioned each embodiment, guaranteeing to replace urea peroxide by other oxygenants under the prerequisite of former ratio, this is that the applicant has obtained the fact that proves in a large amount of tests; Omit the embodiment that replaces urea peroxide by other oxygenants here.The embodiment 1,2,3 that this case provides has enumerated higher value, smaller value and the intermediate value of oxide compound urea peroxide content, and with the feasibility and the meliority of explanation oxide compound value in pasty chemical luminous composite, this meaning is equally applicable to above-mentioned other oxygenant.
Comparative example
1#, 2# data are data shown in the present, and the 3# data are the prior art data, and for technique effect of the present invention is described, the spy compares with 3# data and 1#, 2# data.
Under whipped state, in 35g water, add 0.1g EDTA Disodium, 0.1g benzyltriethylammoinium chloride, 0.3g trolamine, 0.4g CBP and 0.2g Natvosol; Back adding 0.2g9 stirs; 10-tolane base anthracene and 1.5g dimethyl phthalate, continuing to be stirred to viscosity no longer increases, and adds the 0.3g urea peroxide at last; Be stirred to dissolving, be activator component 1
#
Operation more than repeating only changes the quantity that adds the oxygenant urea peroxide, and being respectively adding 0.75g urea peroxide is activator component 2#; Adding the 5.0g urea peroxide is activator component 3#.Corresponding urea peroxide concentration is respectively 1 in three kinds of activator component
#0.79%, 2
#1.95%, 3
#11.7%.
Three kinds of activator component are sealed respectively put into 60 ℃ of baking ovens, it becomes the liquid time of water sample by paste and sees table 4.Can find out that from the simultaneous test data stability of the present composition is superior to prior art combinations.
The test of table 4 activator component baking oven
| Activator component | 1 # | 2 # | 3 # |
| Become the liquid time of water sample | ＞30 days | 8 days | 3 days |
In activator component 2# and 3#, add 3gCPPO respectively, mixing both, all to produce Green Chemistry luminous, detects two samples with luxmeter and begin the different luminous intensities constantly in luminous back, and detected value is seen table 5.The field of the present invention design is a chemical luminous composite, no matter therefore other performance how, luminescent properties is the most basic performance, can find out from the simultaneous test data, and the luminescent properties of the present composition is suitable with prior art compositions.
Table 5 pasty chemical luminous composite sample luminous intensity values (unit: LUX)
| 15min | 60min | 120min | 180min | |
| 2# | 36.4 | 30.7 | 22.7 | 15.8 |
| 3# | 34.4 | 32.5 | 18.5 | 7.8 |
Claims (10)
1. pasty chemical luminous composite with low oxidative high stability, it comprises:
(1) a kind of " barkite component " that contains barkite, the content of barkite in chemical luminous composite is 1%-30%;
(2) a kind of " activator component " that contains oxygenant;
The weight ratio of " barkite component " and " activator component " is in 1: 50 to 3: 1 scope; Contain fluorescent agent, catalyzer, sequestrant, solvent and thickening material in " barkite component " and/or " activator component ",
It is characterized in that the content of oxygenant in chemical luminous composite in " activator component " is 0.7% to 2%.
2. according to the said a kind of pasty chemical luminous composite of claim 1, it is characterized in that said barkite component can be solid-state, liquid state and paste with low oxidative high stability; The barkite component can be single barkite, can be barkite and fluorescent agent and/or mixture of catalysts, also can be barkite or barkite and fluorescent agent and/or the catalyzer mixture with non-aqueous solvent.
3. according to the said a kind of pasty chemical luminous composite of claim 1 with low oxidative high stability; It is characterized in that said activator component is solution, suspension-s, colloid or the emulsion of viscosity greater than 1000mPas, comprises oxygenant, one or more solvents and/or fluorescent agent, catalyzer, sequestrant; Contain thickening material in the activator component simultaneously, so that activator component reaches the viscosity that needs.
4. according to the said a kind of pasty chemical luminous composite of claim 1, it is characterized in that the barkite in the said barkite component is two (2,4 with low oxidative high stability; 5-three chloro-6-carbonyls penta oxygen phenyl) barkite, two (2,4, the 5-trichlorophenyl) barkite, two (2; 4, the own oxygen phenyl of 5-three bromo-6-carbonyls) barkite, two (2 ,-nitrophenyl) barkite, two (2; The 4-dinitrophenyl) barkite, two (2,6-two chloro-4-nitrophenyls) barkite, two (2,4; The 6-trichlorophenyl) barkite, two (3-trifluoromethyl-4-nitrophenyl) barkite, two (1,2-dimethyl--4,6-dinitrophenyl) barkite, two (2; The 4-dichlorophenyl) barkite, two (2, the 4-dinitrophenyl) barkite, two (2, the 5-dinitrophenyl) barkite, two (2-formyl-4-nitrophenyl) barkite, two (five chlorophenyl) barkite, two (1; 2-dihydro-2-oxo--1-pyridyl) oxalic dialdehyde, two (2,4-dinitrobenzene-6-aminomethyl phenyl) barkite; Said barkite preferably comprises two (2,4,5-three chloro-6-carbonyls penta oxygen phenyl) barkite (being called " CPPO ") or two (2,4, the 5-trichlorophenyl) barkites (being called " TCPO ").
5. according to the said a kind of pasty chemical luminous composite of claim 1, it is characterized in that the oxygenant in the said activator component is hydrogen peroxide, sodiumperoxide, peroxo-trisodium phosphate, urea peroxide, sodium perborate, peroxo-Histidine, tertbutyl peroxide and peroxo-phenylformic acid with low oxidative high stability; Preferred oxide compound is a urea peroxide.
6. according to the said a kind of pasty chemical luminous composite of claim 1 with low oxidative high stability; It is characterized in that the fluorescent agent that contains in said " barkite component " and/or " activator component " has the spectral emissions of 330nm-1000nm scope, it is present in barkite component, activator component or the two kinds of components; Said fluorescent agent is a USP 3729426,3948797, the fluorescent agent described in 4017415 and 5122306, and such as 9,10-diphenylanthrancene, 9; 10-tolane base anthracene, 1,8-two chloro-9,10-tolane base anthracene, 2-ethyl-9,10-tolane base anthracene, 1; 6,7,12-four phenoxys-N, N '-two (2; 5 diisopropyl phenyls)-3,4,9,10-perylene dicarboximide etc.; Preferred fluorescent agent is 9,10-tolane base anthracene and 1,8-two chloro-9,10-tolane base anthracene; The content of said fluorescent agent in chemical luminous composite is 0.01%-1%.
7. according to the said a kind of pasty chemical luminous composite of claim 1, it is characterized in that the catalyzer that contains in said " barkite component " and/or " activator component " is SS, potassium salicylate, lithium salicylate, 5-chloro-salicylic acid sodium, 5-chloro-salicylic acid lithium, sodium trifluoroacetate, Woodtreat A potassium, Whitfield's ointment TBuA, phenylformic acid TBuA, TBAP, benzyltriethylammoinium chloride, Tetrabutyl amonium bromide, cetyl trimethylammonium bromide, X 2073, Sodium palmityl sulfate, trolamine, water glass with low oxidative high stability; Preferred catalyzer is SS, trolamine and benzyltriethylammoinium chloride; The content of said catalyzer in chemical luminous composite is 0.01%-5%.
8. according to the said a kind of pasty chemical luminous composite of claim 1, it is characterized in that the sequestrant that contains in said " barkite component " and/or " activator component " is YD 30 and one of which sodium, disodium, trisodium, tetra-na salt with low oxidative high stability; Preferred sequestrant is an EDTA Disodium; The content of said sequestrant in chemical luminous composite is 0.02%-2%.
9. according to the said a kind of pasty chemical luminous composite of claim 1, it is characterized in that the solvent that contains in said " barkite component " and/or " activator component " is ETHYLE ACETATE, dimethyl phthalate, butyl benzoate, ethyl benzoate, wintergreen oil, salicylic ether, glycerine, the trimethyl carbinol and water with low oxidative high stability; Preferred solvent is dimethyl phthalate, butyl benzoate and water; The content of said solvent in chemical luminous composite is 40%-95%.
10. according to the said a kind of pasty chemical luminous composite of claim 1 with low oxidative high stability; It is characterized in that the thickening material that contains in said " barkite component " and/or " activator component " is a water-soluble polymer, it and water are formed the matrix of activator component jointly; Said thickening material is W-Gum, Viscogum BE, guar gum, XG 550, gelatin, CMC 99.5, TKK 021, Natvosol, ROHM, polyacrylic acid derivative, polyoxyethylene glycol and Vinylpyrrolidone polymer; Preferred thickening is XG 550, Natvosol and polyacrylic acid derivative, like CBP; The content of said thickening material in chemical luminous composite is 0.07%-35%.
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| CN111635389A (en) * | 2020-05-07 | 2020-09-08 | 中国人民解放军陆军军医大学 | Hydrogen peroxide responsive compound for imaging and therapy and synthesis method thereof |
| CN112625424A (en) * | 2020-12-18 | 2021-04-09 | 郑州大学 | Chemiluminescence gel based on fluorescent carbon dots and preparation method and application thereof |
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| CN112625424A (en) * | 2020-12-18 | 2021-04-09 | 郑州大学 | Chemiluminescence gel based on fluorescent carbon dots and preparation method and application thereof |
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