CN1910433A - Impermeability tests of closed systems with the aid of fluorescent dyes - Google Patents

Impermeability tests of closed systems with the aid of fluorescent dyes Download PDF

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Publication number
CN1910433A
CN1910433A CNA200580002680XA CN200580002680A CN1910433A CN 1910433 A CN1910433 A CN 1910433A CN A200580002680X A CNA200580002680X A CN A200580002680XA CN 200580002680 A CN200580002680 A CN 200580002680A CN 1910433 A CN1910433 A CN 1910433A
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leakproofness
check
radicals
fluorescent dye
replaced
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H·朗哈尔斯
K－H·布林克曼
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Theodor Heimeier Metallwerk GmbH
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Theodor Heimeier Metallwerk GmbH
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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01M—TESTING STATIC OR DYNAMIC BALANCE OF MACHINES OR STRUCTURES; TESTING OF STRUCTURES OR APPARATUS, NOT OTHERWISE PROVIDED FOR
    • G01M3/00—Investigating fluid-tightness of structures
    • G01M3/02—Investigating fluid-tightness of structures by using fluid or vacuum
    • G01M3/04—Investigating fluid-tightness of structures by using fluid or vacuum by detecting the presence of fluid at the leakage point
    • G01M3/20—Investigating fluid-tightness of structures by using fluid or vacuum by detecting the presence of fluid at the leakage point using special tracer materials, e.g. dye, fluorescent material, radioactive material
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B5/00—Dyes with an anthracene nucleus condensed with one or more heterocyclic rings with or without carbocyclic rings
    • C09B5/62—Cyclic imides or amidines of peri-dicarboxylic acids of the anthracene, benzanthrene, or perylene series
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01M—TESTING STATIC OR DYNAMIC BALANCE OF MACHINES OR STRUCTURES; TESTING OF STRUCTURES OR APPARATUS, NOT OTHERWISE PROVIDED FOR
    • G01M3/00—Investigating fluid-tightness of structures
    • G01M3/02—Investigating fluid-tightness of structures by using fluid or vacuum
    • G01M3/04—Investigating fluid-tightness of structures by using fluid or vacuum by detecting the presence of fluid at the leakage point
    • G01M3/20—Investigating fluid-tightness of structures by using fluid or vacuum by detecting the presence of fluid at the leakage point using special tracer materials, e.g. dye, fluorescent material, radioactive material
    • G01M3/22—Investigating fluid-tightness of structures by using fluid or vacuum by detecting the presence of fluid at the leakage point using special tracer materials, e.g. dye, fluorescent material, radioactive material for pipes, cables or tubes; for pipe joints or seals; for valves; for welds; for containers, e.g. radiators
    • G01M3/226—Investigating fluid-tightness of structures by using fluid or vacuum by detecting the presence of fluid at the leakage point using special tracer materials, e.g. dye, fluorescent material, radioactive material for pipes, cables or tubes; for pipe joints or seals; for valves; for welds; for containers, e.g. radiators for containers, e.g. radiators
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01M—TESTING STATIC OR DYNAMIC BALANCE OF MACHINES OR STRUCTURES; TESTING OF STRUCTURES OR APPARATUS, NOT OTHERWISE PROVIDED FOR
    • G01M3/00—Investigating fluid-tightness of structures
    • G01M3/02—Investigating fluid-tightness of structures by using fluid or vacuum
    • G01M3/04—Investigating fluid-tightness of structures by using fluid or vacuum by detecting the presence of fluid at the leakage point
    • G01M3/20—Investigating fluid-tightness of structures by using fluid or vacuum by detecting the presence of fluid at the leakage point using special tracer materials, e.g. dye, fluorescent material, radioactive material
    • G01M3/22—Investigating fluid-tightness of structures by using fluid or vacuum by detecting the presence of fluid at the leakage point using special tracer materials, e.g. dye, fluorescent material, radioactive material for pipes, cables or tubes; for pipe joints or seals; for valves; for welds; for containers, e.g. radiators
    • G01M3/226—Investigating fluid-tightness of structures by using fluid or vacuum by detecting the presence of fluid at the leakage point using special tracer materials, e.g. dye, fluorescent material, radioactive material for pipes, cables or tubes; for pipe joints or seals; for valves; for welds; for containers, e.g. radiators for containers, e.g. radiators
    • G01M3/228—Investigating fluid-tightness of structures by using fluid or vacuum by detecting the presence of fluid at the leakage point using special tracer materials, e.g. dye, fluorescent material, radioactive material for pipes, cables or tubes; for pipe joints or seals; for valves; for welds; for containers, e.g. radiators for containers, e.g. radiators for radiators

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
  • Examining Or Testing Airtightness (AREA)
  • Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)

Abstract

The invention relates to a method wherein the impermeability of closed systems can be tested with the aid of fluorescent dyes. As a result, preferably powerful fluorescent perylene dyes are used.

Description

Closed system is by the leakproofness check of fluorescent dye
Foreword
The leakproofness of closed system is checked particular importance technically.Although parts are usually made institute's decision by it but closely knit very reliably such as managing, yet every kind of connection such as weld seam or fine weld seam, bolt connection or flange connection are weak link basically, and its inspection needs SC.In most cases leak and can tolerate, in needing all systems of constant volume, the leakproofness check is a special problem.A kind of such example is liquid-temperature movement sensor, at first loses the adjusting accuracy owing to the loss of its content liquid, loses its function then.Effective and inspection reliably is indispensable for such system.
Can confirm minimum leak very delicately by helium.The shortcoming of this method is, is not to test with final unit of filling, but must fills afterwards, thereby can not aware the non-leakproofness that produces by subsequent process.Another shortcoming that need mention is that this method has too high sensitivity, because this method can be found the most tiny leak, and this leak is inappreciable for the operation of most equipment fully.What need mention at last is the technology cost of these leak testing instruments.
But, at present, it is not too suitable at first obviously and easily to check that the system of filling is still by accurate weighing, only be that very little weight changes because must determine a large amount of materials, so this measurement is highly susceptible to losing efficacy.Here, inappreciable surface oxidation process and corrosion for normal running have the very influence of obstruction property to the weight constant.In addition, still have the small amount of matter can be from surface evaporation, it be absorbed or partly overflows from the lacquer shape.Even this be inappreciable amount fully for system operation, for the weight constant of check thing adverse influence is arranged also.
If use in order to fill closed system to be easy to evaporated liquid, then can check the steam of ambient gas liquid that the space is filled with of the check thing of final filling.Can imagine that this point can be measured effective organic vapor with it with for example being undertaken by the known flame ionization detecting device (FID) of gas chromatography.Owing to usually also have other materials to evaporate, so this method is insecure from the surface that technology makes.In order fundamentally to improve the reliability of method, need to carry out the check of molecule specificity here, for example mass spectrum for example uses quadrupole mass spectroscope, can realize this point.Such equipment also need be mentioned the interference source that this method of inspection is important except high technical costs: the liquid of being filled begins and can partly adsorb from the teeth outwards from filling process, slowly discharges then.Thereby have the assay of error.This can compensate more or less the check threshold value that raises arbitrarily, but on the other hand from and the method that makes be insecure.
A kind of in order to confirm that easy, the reliable and low cost method of leak is brought obvious progress in the final check thing of filling.If assay can visually check, then meet hope especially especially, like this, when automatic gauging, can spot-check sample and come the compliance test result.
Describe
The fluorescence of suitable dyestuff is to introduce very much attention, can be confirmed that therefore, fluorescence is suitable for surveying leak in principle than high sensitivity ground.But, a lot of fluorescent dye light stability are very poor, and for example fluorescein perhaps usually is medium chemical stability.
Here ， perylene-3,4:9,10-tetracarboxylic acid diimide 1 shows its excellent especially performance, for example extra high photochemistry and chemical stability, fluorescence quantum yield is about 100%, and shows high molar absorption coefficient ([ε] is about 85000 to 95000).Perylene diimides is indissoluble normally, so it can not be with the fluorescent dye that acts on homogeneous solution.This problem can be solved as 1-hexyl heptyl by adding the secondary alkyl of the deliquescent group of raising such as the tert-butyl group or long-chain (" dovetail group ").Dyestuff 1a according to this concept development is soluble in organic solvent commonly used such as chloroform or the ethyl acetate, and can be used as fluorescent dye and be used for uniform solution.Because high molar absorption coefficient, therefore naked eyes identify 10 without a doubt -6To 10 -7The solution of volumetric molar concentration.When machinery is checked, can also fundamentally improve sensitivity.
Figure A20058000268000082
Study the leakproofness that this fluorescent dye is used to check closed system.As an example, select liquid-temperature movement sensor here, wherein, carry out temperature statistics by the expansion of the liquid capacity in the locking device.Select ethyl acetate as liquid, owing to multiple reason, it is particularly suitable for this device, especially must worry anything but on the toxicity study.In this liquid-temperature movement sensor, be similar in the thermometer like that, because the mechanism of liquid thermal expansion, a bearing pin is moved; The mobile of this bearing pin is that adjustment process is necessary.The liquid capacity of sealing is placed in the housing of encapsulation, and this housing is owing to making former thereby containing fine weld seam or weld seam and sealer.Obviously, the leakproofness of this device is vital for its function, even because the loss of very little liquid also can exert an influence to regulating accuracy immediately, be insupportable therefore.More liquid loss can cause defective regulator.When with 13g ethyl acetate typically during the filling temp displacement transducer, calculate in 8 years maximum endurable loss be 45mg, this means microgram every days 15.In order clearly to get rid of so little leakage, need very sensitive test.
Making concentration with dyestuff 1a is the ethyl acetate dyeing of 40mg/L, thereby obtains sending out the solution of hyperfluorescence; The low content of dye solution (owing to the high absorption coefficient of 1a becomes possibility) is important, thus the viscosity of the solvent that can obviously not raise.Like this, this temperature movement sensor obtains filling, wash with this solvent then, and the result, this surface of the work does not have fluorescigenic impurity; When flowing out, used solvent do not have every kind of fluorescence this point as can be seen from washing.Because the metal surface of this dyestuff raw material commonly used relatively is complete inertia, so, on the one hand, this dyestuff is not a problem for the metal part of temperature movement sensor, on the other hand, this dyestuff can be by latter's attack yet, thereby has guaranteed the long-life of filling material color.Thereby can check leakproofness for a long time.
The temperature movement sensor of filling with ethyl acetate and dyestuff 1a produces surprising quick, easy and sensitive check to very little leak, referring to Fig. 1.Even such leak can not be found through the time near 100 days with weighing method, because the fluctuation of the weight of so industrial workpiece is under conventional environmental baseline, if fill, obviously surpass above-mentioned value of standing (three times and more times) owing to various process without solvent.In Fig. 1 left side as seen, in the left side of sealed spheroid, the solvent that contains fluorescent dye 1a flows out.Can see clearly that in the enlarged drawing of right side fluorescigenic ethyl acetate flows out from this spheroid left side.The dyestuff that flows out can be used solvent, as ethyl acetate, washes off from workpiece.Thereby can also be by adsorbing or finding quantitatively to leak by fluorescence intensity more delicately.But, under most technology relevant situation, be enough to the confirmation that reaches easy, quantitative, visual according to Fig. 1.
By can also be on the principle of verification of fluorescence, thereby can realize effectively inspection by robotization.Optical excitation can be carried out with polychromatic light (for example white light), perhaps can also carry out with monochromatic light; A kind of the exciting under the situation in back can make scattered light fade out effectively.Can use blue streak for example at the UV of 365nm light with for example mercury vapor lamp for this reason, for example use indium mercury vapo(u)r lamp (451nm), with thallium mercury vapo(u)r lamp (535nm), perhaps argon gas-the ion laser with 488nm excites.Under latter's wavelength situation, the mole adsorption coefficient even be 52400 of dyestuff.
Figure A20058000268000101
Can confirm to leak with soluble, a hyperfluorescence De perylene dyestuff in principle.1b is a kind of suitable dyestuff equally, wherein, by the tert-butyl group dissolubility is raise.Another example is and the dyestuff of 1a homology that wherein, the positive alkyl of side chain can be lengthened out or shorten.Shorten side chain and cause dissolubility to reduce, so check is debatable under the short chain situation.Add long-chain and cause dissolubility to raise, 19 carbon atoms can reach its maximal value altogether in whole side chain, but descend again afterwards.Dyestuff 1a has good compromise property between dissolubility and good synthetic realizability, because for the dyestuff that has than long alkyl chain, purification ratio 1a obviously more expends.Test is significant especially to dyestuff with 1-butyl amyl group side chain for leak, because it shows outstanding solid fluorescence, this is particularly advantageous for visual leak test.
In principle, the leak check also can be carried out with Qi Ta perylene derivant.Here, Te other Shi perylene dianhydride carboxylic acid acid imide is as 2 He perylene tetracarboxylic acid Zhi such as perylene tetracarboxylic acid tetramethyl ester 3 or the methyl ester that can be replaced by long alkyl chain wherein, and they also can have branching.
Figure A20058000268000111
Qi Ta perylene derivant that is used for the leakproofness check is 3-Yi Xian Ji perylene and wherein methyl and the more homolog of long alkyl chain exchange, and also can have branching.Can mention that equally dicarboxylic ester 4 is as the dyestuff that is used for the leakproofness check.In the case, methyl can exchange with the alkyl of long-chain more equally.
Described leakproofness check can be used for multiple closed system.An example at this is the temperature movement sensor.Other examples are system such as cooling device or the air-conditioning equipments with closed circulation.
The mark inventory
Fig. 1. contain the temperature movement sensor of fluorescent dye-solvent-filling material.The non-leakproofness in sealed spheroid left side.A left side: above the following sensor with sealed spheroid.Right: the spheroid of amplification, left side have solvent-dyestuff-outlet (light areas at spheroid edge).
Fig. 2. formula 1.
Fig. 3. formula 1a.
Fig. 4. formula 1b.
Fig. 5. formula 2 and 3.
Fig. 6. formula 4.
Claims
(according to the modification of the 19th of treaty)
1. be filled with the method for leakproofness check of the closed system of liquid, wherein, same fluorescent dye is dissolved in the liquid and is used for the leakproofness check, wherein system's polychromatic light of being used in the long wavelength absorption region of dyestuff excites and directly detects the leak point that may exist, it is characterized in that system is a kind of temperature movement sensor, to its sealer and/or solder joint and/or weld seam detection leakproofness, dyestuff has solid fluorescence and temperature movement sensor solvent processing, makes the dyestuff that flows out at leak point place produce fluorescence solution.
2. the method for checking according to the leakproofness of claim 1 is characterized in that, uses low viscous solvent, particularly ethyl acetate.
3. the method for checking according to the leakproofness of claim 1 is characterized in that, direct vision detects the non-leakproofness of leak point.
4. the method for checking according to the leakproofness of claim 1 is characterized in that solvent is an ethyl acetate.
5. the method for checking according to the leakproofness of claim 1 is characterized in that, detects the leak point automatically with formation method.
6. the method for leakproofness check wherein, in the method according to claim 1, is used general formula I De perylene-fluorescent dye
Figure A20058000268000181
Wherein, radicals R 1To R 2Each other can be identical or different, and expression contains at least one and the straight chained alkyl of 37 carbon atoms at the most independently of one another, wherein, 1 to 10 CH 2-unit can be replaced by following group respectively independently of one another: carbonyl, oxygen atom, sulphur atom, selenium atom, tellurium atom, suitable-or anti--CH=CH-group, one of them CH-unit also can be replaced by nitrogen-atoms, acetylene series C ≡ C-group, 1,2-, 1,3-or 1, the phenyl that 4-replaces, 2,3-, 2,4-, 2,5-, 2,6-, 3,4-or 3,5-Disubstituted pyridine base, 2,3-, 2,4-, 2,5-or 3, the dibasic thienyl of 4-, 1,2-, 1,3-, 1,4-, 1,5-, 1,6-, 1,7-, 1,8-, 2,3-, 2,6-or 2, the dibasic naphthyl of 7-, one of them or two CH-groups can be replaced by nitrogen-atoms, and 1,2-, 1,3-, 1,4-, 1,5-, 1,6-, 1,7-, 1,8-, 1,9-, 1,10-, 2,3-, 2,6-, 2,7-, 2,9-, 2,10-or 9, the dibasic anthryl of 10-, wherein-individual or two CH-groups can replace by nitrogen-atoms; CH 2Even also can distinguishing independently of one another on identical C-atom, 12 single hydrogen atoms at the most of-group replaced: halogens fluorine, chlorine, bromine or iodine or cyano group or contain the linear alkyl chain of 18 carbon atoms at the most, wherein 1 to 6 CH by following 2-unit can be replaced by following group independently of one another: carbonyl, oxygen atom, sulphur atom, selenium atom, tellurium atom, suitable-or anti--CH=CH-group, one of them CH-unit also can be replaced by nitrogen-atoms, acetylene series C ≡ C-group, 1,2-, 1,3-or 1, the phenyl that 4-replaces, 2,3-, 2,4-, 2,5-, 2,6-, 3,4-or 3,5-Disubstituted pyridine base, 2,3-, 2,4-, 2,5-or 3, the dibasic thienyl of 4-, 1,2-, 1,3-, 1,4-, 1,5-, 1,6-, 1,7-, 1,8-, 2,3-, 2,6-or 2, the dibasic naphthyl of 7-, one of them or two carbon atoms can be replaced by nitrogen-atoms, and 1,2-, 1,3-, 1,4-, 1,5-, 1,6-, 1,7-, 1,8-, 1,9-, 1,10-, 2,3-, 2,6-, 2,7-, 2,9-, 2,10-or 9, the dibasic anthryl of 10-, one of them or two carbon atoms can be replaced by nitrogen-atoms.The CH of alkyl 2Even also can distinguishing independently of one another on identical C-atom, 12 single hydrogen atoms at the most of-group replaced: halogens fluorine, chlorine, bromine or iodine or cyano group or contain the linear alkyl chain of 18 carbon atoms at the most, wherein 1 to 6 CH by following 2-unit can be independently of one another by carbonyl, oxygen atom, sulphur atom, selenium atom, tellurium atom, suitable-or anti--CH=CH-group, one of them CH-unit also can be replaced by nitrogen-atoms, acetylene series C ≡ C-group, 1,2-, 1,3-or 1, the phenyl that 4-replaces, 2,3-, 2,4-, 2,5-, 2,6-, 3,4-or 3,5-Disubstituted pyridine base, 2,3-, 2,4-, 2,5-or 3, the dibasic thienyl of 4-, 1,2-, 1,3-, 1,4-, 1,5-, 1,6-, 1,7-, 1,8-, 2,3-, 2,6-or 2, the dibasic naphthyl of 7-, one of them or two carbon atoms can be replaced by nitrogen-atoms, and 1,2-, 1,3-, 1,4-, 1,5-, 1,6-, 1,7-, 1,8-, 1,9-, 1,10-, 2,3-, 2,6-, 2,7-, 2,9-, 2,10-or 9, the dibasic anthryl of 10-, one of them or two carbon atoms can be replaced by nitrogen-atoms; Replace having substituting group, the free valence of methine or quaternary carbon atom can connect in couples, thereby forms ring, for example cyclohexane ring; Radicals R 3To R 6Can be hydrogen or be independently of one another one to four for R 1To R 2Described group.
7. according to the method for the leakproofness of claim 1 check, it is characterized in that this fluorescent dye is combined in the polymkeric substance, described polymkeric substance dissolves in the liquid in the system that is filled with liquid.
8. the method for checking according to the leakproofness of claim 7 is characterized in that this polymkeric substance is polymethylmethacrylate (PMMA).
9. the method for leakproofness check according to Claim 8 is characterized in that, polymethylmethacrylate by monomer whose be present in free radical polymerization in the oil phase be deposited in fluorescent dye at the interface.
10. the method for checking according to the leakproofness of claim 7 is characterized in that this fluorescent dye is scattered in the water before polymerization.
11. the method for the check of leakproofness according to Claim 8 is characterized in that, is sealed by little in conjunction with the fluorescent dye of acrylate.
12. the method according to the leakproofness of claim 11 is checked is characterized in that described sealing by home position polymerization reaction realized.
13. method according to the check of the leakproofness of claim 11, it is characterized in that, little fluorescent dye of sealing in conjunction with acrylate adds in the ducted body of temperature movement sensor with particle form, with this ducted body of liquid filling, seal this ducted body, with this ducted body annealing, the system that calibration provides like this, the method for carrying out the leakproofness check then.

Claims (22)

1. the method for leakproofness check, wherein, use fluorescent dye to be used for the leakproofness check, be preferred for the leakproofness check of closed system, more preferably be filled with the closed system of liquid such as the leakproofness check of cooling device or temperature movement sensor, the most preferably leakproofness of temperature movement sensor check.
2. the method for leakproofness check wherein, adds fluorescent dye to the closed system according to 1, preferred same fluorescent dye, thus preferably make this fluorescent dye in being filled with the system of liquid, be dissolved in this liquid.
3. the method for leakproofness check wherein, is used low viscous solvent in according to 1 and 2 leakproofness check.Ethyl acetate, butyl acetate, chloroform, normal heptane, n-pentane, tetramethylsilane, HMDO, chloroform, methylene chloride and toluene.Ethyl acetate most preferably.
4. the method for leakproofness check wherein, is preferably studied sealer, fine weld seam and weld seam.
5. the method for leakproofness check, wherein, in according to 1 to 4 method, the direct non-leakproofness of visualize leak point.At this moment, preferably contain the fluorescent dye of solid fluorescence thing, for example 1a.
6. the method for leakproofness check wherein, in according to 1 to 4 method, by using solvent, is preferably handled workpiece and is carried out non-leakproofness with ethyl acetate, makes the dyestuff that flows out produce fluorescigenic solution.
7. the method for leakproofness check wherein, in according to 1 to 4 method, detects the leak point automatically, for example with the exploring laser light bundle or use various formation method.
8. the method for leakproofness check wherein, in according to 1 to 7 method, excites with polychromatic light, preferably is used in the light of the long wave binding domain of dyestuff.
9. the method for leakproofness check wherein, in according to 1 to 7 method, uses monochromatic light to carry out fluorescence excitation, and preferred mercury vapor lamp is at the light of 365nm, and the indium mercury vapo(u)r lamp is at light or the laser of 451nm, and the preferred argon gas-ion laser of the latter is at the laser of 488nm.The preferred exciting light that filters is preferably used interference filter in these methods.
10. the method for leakproofness check wherein, in according to 1 to 9 method, is used general formula I De perylene-fluorescent dye
Figure A2005800026800003C1
Wherein, radicals R 1To R 2Each other can be identical or different, and expression contains at least one and the straight chained alkyl of 37 carbon atoms at the most independently of one another, wherein, 1 to 10 CH 2-unit can be replaced by following group respectively independently of one another: carbonyl, oxygen atom, sulphur atom, selenium atom, tellurium atom, suitable-or anti--CH=CH-group, one of them CH-unit also can be replaced by nitrogen-atoms, acetylene series C ≡ C-group, 1,2-, 1,3-or 1, the phenyl that 4-replaces, 2,3-, 2,4-, 2,5-, 2,6-, 3,4-or 3,5-Disubstituted pyridine base, 2,3-, 2,4-, 2,5-or 3, the dibasic thienyl of 4-, 1,2-, 1,3-, 1,4-, 1,5-, 1,6-, 1,7-, 1,8-, 2,3-, 2,6-or 2, the dibasic naphthyl of 7-, one of them or two CH-groups can be replaced by nitrogen-atoms, and 1,2-, 1,3-, 1,4-, 1,5-, 1,6-, 1,7-, 1,8-, 1,9-, 1,10-, 2,3-, 2,6-, 2,7-, 2,9-, 2,10-or 9, the dibasic anthryl of 10-, one of them or two CH-groups can be replaced by nitrogen-atoms; CH 2Even also can distinguishing independently of one another on identical C-atom, 12 single hydrogen atoms at the most of-group replaced: halogens fluorine, chlorine, bromine or iodine or cyano group or contain the linear alkyl chain of 18 carbon atoms at the most, wherein 1 to 6 CH by following 2-unit can be replaced by following group independently of one another: carbonyl, oxygen atom, sulphur atom, selenium atom, tellurium atom, suitable-or anti--CH=CH-group, one of them CH-unit also can be replaced by nitrogen-atoms, acetylene series C ≡ C-group, 1,2-, 1,3-or 1, the phenyl that 4-replaces, 2,3-, 2,4-, 2,5-, 2,6-, 3,4-or 3,5-Disubstituted pyridine base, 2,3-, 2,4-, 2,5-or 3, the dibasic thienyl of 4-, 1,2-, 1,3-, 1,4-, 1,5-, 1,6-, 1,7-, 1,8-, 2,3-, 2,6-or 2, the dibasic naphthyl of 7-, one of them or two carbon atoms can be replaced by nitrogen-atoms, and 1,2-, 1,3-, 1,4-, 1,5-, 1,6-, 1,7-, 1,8-, 1,9-, 1,10-, 2,3-, 2,6-, 2,7-, 2,9-, 2,10-or 9, the dibasic anthryl of 10-, one of them or two carbon atoms can be replaced by nitrogen-atoms.The CH of alkyl 2Even also can distinguishing independently of one another on identical C-atom, 12 single hydrogen atoms at the most of-group replaced: halogens fluorine, chlorine, bromine or iodine or cyano group or contain the linear alkyl chain of 18 carbon atoms at the most, wherein 1 to 6 CH by following 2-unit can be independently of one another by carbonyl, oxygen atom, sulphur atom, selenium atom, tellurium atom, suitable-or anti--CH=CH-group, one of them CH-unit also can be replaced by nitrogen-atoms, acetylene series C ≡ C-group, 1,2-, 1,3-or 1, the phenyl that 4-replaces, 2,3-, 2,4-, 2,5-, 2,6-, 3,4-or 3,5-Disubstituted pyridine base, 2,3-, 2,4-, 2,5-or 3, the dibasic thienyl of 4-, 1,2-, 1,3-, 1,4-, 1,5-, 1,6-, 1,7-, 1,8-, 2,3-, 2,6-or 2, the dibasic naphthyl of 7-, one of them or two carbon atoms can be replaced by nitrogen-atoms, and 1,2-, 1,3-, 1,4-, 1,5-, 1,6-, 1,7-, 1,8-, 1,9-, 1,10-, 2,3-, 2,6-, 2,7-, 2,9-, 2,10-or 9, the dibasic anthryl of 10-, one of them or two carbon atoms can be replaced by nitrogen-atoms; Replace having substituting group, the free valence of methine or quaternary carbon atom can connect in couples, thereby forms ring, for example cyclohexane ring; Radicals R 3To R 6Can be hydrogen or be independently of one another one to four for R 1To R 2Described group.
11. the method for leakproofness check wherein, in according to 1 to 9 method, is used general formula I I De perylene-fluorescent dye,
Figure A2005800026800004C1
Wherein, radicals R 1Has radicals R in 10 1Or R 2Definition, and radicals R 2To R 7Each other can be identical or different, and have radicals R in 10 independently of one another 3To R 6Definition.
12. the method for leakproofness check wherein, in according to 1 to 9 method, is used general formula III De perylene-fluorescent dye,
Figure A2005800026800004C2
Wherein, radicals R 1Has radicals R in 10 1Or R 2Definition, and radicals R 2To R 5Each other can be identical or different, and have radicals R in 10 independently of one another 3To R 6Definition.
13. the method for leakproofness check wherein, in according to 1 to 9 method, is used general formula III De perylene-fluorescent dye,
Wherein, radicals R 1Has radicals R in 10 1Or R 2Definition, and radicals R 2To R 5Each other can be identical or different, and have radicals R in 10 independently of one another 3To R 6Definition.
14. the method for leakproofness check wherein, in according to 1 to 9 method, is used general formula I V De perylene-fluorescent dye,
Figure A2005800026800005C2
Wherein, radicals R 1Has radicals R in 10 1Or R 2Definition, and radicals R 2To R 7Each other can be identical or different, and have radicals R in 10 independently of one another 3To R 6Definition.
15. the method according to the check of the leakproofness of claim 1 is characterized in that this fluorescent dye is combined in the polymkeric substance, described polymkeric substance dissolves in the liquid in the system that is filled with liquid.
16. the method according to the leakproofness of claim 15 is checked is characterized in that this polymkeric substance is polymethylmethacrylate (PMMA).
17. the method according to the check of the leakproofness of claim 15 is characterized in that, polymethylmethacrylate by monomer whose be present in free radical polymerization in the oil phase be deposited in fluorescent dye at the interface.
18. the method according to the leakproofness of claim 15 is checked is characterized in that this fluorescent dye is scattered in the water before polymerization.
19. the method according to the leakproofness of claim 15 is checked is characterized in that, uses the radical initiator of ammonium peroxydisulfate (APS) as free radical polymerization.
20. the method according to the leakproofness of claim 15 is checked is characterized in that, is encapsulated in the layer that is formed by butanediol diacrylate (BDDA) in conjunction with the fluorescent dye of acrylate is little.
21. the method according to the leakproofness of claim 20 is checked is characterized in that described sealing by home position polymerization reaction realized.
22. method according to the check of the leakproofness of claim 15, it is characterized in that, little fluorescent dye of sealing in conjunction with acrylate adds in the ducted body with particle form, with this ducted body of liquid filling, seal this ducted body, with this ducted body annealing, the system that calibration provides like this, the method for carrying out the leakproofness check then.
CNA200580002680XA 2004-02-20 2005-02-18 Impermeability tests of closed systems with the aid of fluorescent dyes Pending CN1910433A (en)

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