CN107045022A - The detection method of four kinds of UV stable agent contents in the products such as plastics, rubber - Google Patents

The detection method of four kinds of UV stable agent contents in the products such as plastics, rubber Download PDF

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CN107045022A
CN107045022A CN201710073188.6A CN201710073188A CN107045022A CN 107045022 A CN107045022 A CN 107045022A CN 201710073188 A CN201710073188 A CN 201710073188A CN 107045022 A CN107045022 A CN 107045022A
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sample
detection method
extract
mixed mark
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CN107045022B (en
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袁奇
杜适
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Suzhou Letter Measurement Standard Technology Service Co Ltd
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Suzhou Letter Measurement Standard Technology Service Co Ltd
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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/04—Preparation or injection of sample to be analysed
    • G01N30/06—Preparation
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/04—Preparation or injection of sample to be analysed
    • G01N30/06—Preparation
    • G01N2030/062—Preparation extracting sample from raw material

Abstract

The invention discloses the detection method of four kinds of UV stable agent contents in the products such as a kind of plastics, rubber, including taking appropriate amount of sample after organic solvent ultrasonic extraction, purified, concentration, filtering, enter GC MS test analysis, the detection method separating degree of the present invention, linear coefficient and have good stability, quantitative accurate, the rate of recovery is high, and simple, convenient.

Description

The detection method of four kinds of UV stable agent contents in the products such as plastics, rubber
Technical field
The present invention relates to four kinds of ultra-violet stabilizer (UV320/UV327/UV328/ in the products such as a kind of plastics, rubber UV350) the detection method of content, belongs to chemical analysis detection field.
Background technology
Ultra-violet stabilizer UV 320, Chinese is also known as 2- (2'- hydroxyls -3', 5'- di-tert-butyl-phenyl)-BTA, Outward appearance is white powder or buff powder, No. CAS：3846-71-7, molecular formula is C20H25N3O, molecular weight is 325.5, fusing point For 152 DEG C~154 DEG C, flash-point is 215 DEG C, and density is 1.1g/cm3, boiling point is that 444 DEG C of at 760mmHg, UV 320 are efficient Light stabilizer, is widely used in plastics and other organic matters, is particularly suitable for use in unsaturated polyester, PVC, PVC plasticising glue etc.；
Ultra-violet stabilizer UV 327, Chinese is also known as 2- (2 ˊ-hydroxyl -3 ˊ, 5 ˊ-di-tert-butyl-phenyl) -5- chlorobenzenes And triazole, outward appearance is faint yellow or white powder, No. CAS：3864-99-1, molecular formula is C20H24ClN3O, and molecular weight is 357.9, fusing point is 150 DEG C -158 DEG C, and flash-point is 237.6 DEG C, and density is 1.18g/cm3, and boiling point is 469.2 DEG C of at 760mmHg, UV 327 has larger solubility in benzene, toluene, styrene, hexamethylene equal solvent, is slightly soluble in alcohol, ketone, insoluble Yu Shui, is excellent light stabilizer, with other antioxidant and with there is good synergy, it is adaptable to polypropylene, polyethylene, poly- Formaldehyde, ABS resin, polymethyl methacrylate, polyurethane and multiple coating；
Ultra-violet stabilizer UV 328, Chinese also known as 2- [2- hydroxyls -3,5- bis- (1,1- dimethyl propyl phenyl)] - 2H- BTAs, outward appearance is buff powder, No. CAS：25973-55-1, molecular formula is C22H29N3O, and molecular weight is 351.5, fusing point is 80 DEG C -83 DEG C, and density is 1.08g/cm3, and boiling point is that 469.1 DEG C of at 760mmHg, UV 328 are dissolved in benzene, first Benzene, ethyl acetate and petroleum ether, are slightly soluble in ethanol and methanol, be mainly used in polyethylene, polypropylene, polystyrene, polyvinyl chloride, Polyester, epoxy resin, ABS resin and celluosic resin etc., also have excellent light stablizing effect in various coating；
Ultra-violet stabilizer UV 350, Chinese is also known as 2- (2'- hydroxyl -3'- isobutyl group -5'- tert-butyl-phenyls) benzo Triazole, outward appearance is buff powder, No. CAS：36437-37-3, molecular formula is C20H25N3O, and molecular weight is 323.4, and fusing point is 81 DEG C~84 DEG C, density is 1.12g/cm3, and boiling point is 458 DEG C of at 760mmHg, is mainly used in makrolon, polyester, polyamides Amine, arene copolymer, hot shortness's polyurethane and polyurethane, the list of styrene gather and copolymer；
UV 320, UV 328 and UV 327, UV 350 are European chemical balance motion office (ECHA) respectively in December, 2014 The highest attention material (SVHC) that 17 days and on December 17th, 2015 announce, according to REACH regulations (EC) No.1907/2006 and The classification of dangerous substance, packaging, sign instruction (67/548/EEC) UV 327, UV 350, UV 320, UV 328 is regarded as height Persistently, high bioaccumulation material (vPvB), UV 320, UV 328 is also regarded as persistence, bioaccumulation and toxicant (PBT)；Meanwhile, these four ultra-violet stabilizers, the OEKO-TEX also newly revised by International Environmental Protection weaving association (OEKO-TEX) Standard 100:Included in 2016 editions in the IVth class product (family's exterior material), the IVth class product (family's exterior material) four kinds it is ultraviolet The limit value of line stabilization agent is 0.1%；However, in REACH regulations (EC) No.1907/2006 and OEKO-TEX Standard 100:Do not have specific detection method in 2016, the present invention is four kinds of UV stable agent contents in the products such as plastics, rubber Measure provide clear and definite detection method.
The content of the invention
The technical problems to be solved by the invention are to overcome the shortcoming of prior art there is provided the products such as a kind of plastics, rubber In four kinds of UV stable agent contents detection method, the detection method separating degree, linear coefficient and have good stability, quantitative standard Really, the rate of recovery is high, and simple, convenient.
In order to solve the above technical problems, the present invention provides four kinds of ultra-violet stabilizers in the products such as a kind of plastics, rubber The detection method of content, the detection method specifically includes following steps：
(1) preparation of the mixed mark working solution of sample
Four kinds of ultra-violet stabilizer UV320, UV327, UV328 and UV350 standard items are weighed respectively in 50mL volumetric flasks, Then with toluene constant volume and shake up, obtain the mixed mark stock solution of one-level of four kinds of ultra-violet stabilizers, then will remaining pure standby liquid Stored in 40mL brown bottles at 0-5 DEG C, pipette the mixed mark stock solution of the one-level prepared in 20mL volumetric flasks, use toluene Constant volume is simultaneously shaken up, and obtains two grades of mixed mark stock solutions, and remaining pure standby liquid is stored in 8mL brown bottles at 0-5 DEG C, and thus two The mixed mark stock solution of level is further prepared into mixed mark working solution, by the mixed mark working solution of preparation in 8mL brown sample injection bottles Stored at 0-5 DEG C, take the mixed mark working solution of preparation to be tested in sample introduction bottle with GC-MC respectively, obtain respective chromatogram Figure, collects the peak area and appearance time on respective chromatogram and makes standard curve for point；
(2) pre-treatment of testing sample
Testing sample is chosen, it is broken into the particle that particle diameter is 2mm-3mm with scissors or pulverizer, is well mixed, weighs The testing sample handled well adds organic solvent in sample bottle, closed, after testing sample is sufficiently humidified so as to, is put into ultrasonic wave In water-bath, instrument is extracted by ultrasonic wave and obtains extract, the power of ultrasonic wave is 1600w, and shelves are adjusted to 100%；
(3) when the extract that ultrasonic extraction is obtained in step (2) matrix effect occurs or be substantially muddy, first carry out net Change operation, purification run is specially：
Tripoli solid-phase extraction column in fluorine sieve is placed on solid-phase extraction device, activated with 6mL dichloromethane, then use 6mL N-hexane infiltrates, and keeps 1mm liquid levels to wait loading, and the extract loading that step (2) ultrasonic extraction is obtained simultaneously uses dichloromethane Alkane elute, control during elution extract flow velocity be 1.5mL/min, collect eluent and merged after post liquid use purity >= 99.999% nitrogen blows and constant volume, or collects eluent and merged after post liquid and concentrated with vacuum rotary evaporator at 40 DEG C Concentrate is obtained to closely dry, transfer concentrate and leacheate carry out nitrogen into nitrogen drying instrument and blown, and step (4) is then carried out again Operation；
Directly carried out when matrix effect or substantially muddiness does not occur in the extract that ultrasonic extraction is obtained in step (2) The operation of step (4)；
(4) analyze
Liquid to be extracted is cooled to after room temperature, through 0.22 μm of pin type PTFE filter membrane into sample injection bottle, then carries out GC-MC surveys Examination, the standard curve then made using in step (1) is the content that testing sample middle-ultraviolet lamp stabilizer is obtained with reference to analysis.
The technical scheme that further limits of the present invention is：
Further, in the product such as foregoing plastics, rubber in the detection method of four kinds of UV stable agent contents, step (1) the linear coefficient R of standard curve is more than or equal to 0.995.
In the products such as foregoing plastics, rubber in the detection method of four kinds of UV stable agent contents, ultrasonic wave in step (2) Temperature is room temperature during extraction, and ultrasonic time is 60min.
In the products such as foregoing plastics, rubber in the detection method of four kinds of UV stable agent contents, described in step (2) Organic solvent is toluene.
The beneficial effects of the invention are as follows：
The detection method of four kinds of UV stable agent contents, separating degree (UV 328 and UV 327 in the PE materials of the present invention Quota ion, qualitative ion it is different, mutually noiseless, for details, see the appendix A, Appendix B, appendix C, Appendix D), linear relationship And have good stability, it is quantitative accurate, the rate of recovery more than 80%, also with it is simple, convenient the characteristics of.
Brief description of the drawings
Fig. 1 is the chromatogram of four kinds of stabilizers UV320, UV327, UV328, UV350 of the present invention mixed mark working solution；
Fig. 2 is the chromatogram of UV327, UV328 in testing sample；
Fig. 3 a are standard items UV320 mass spectrogram；
Fig. 3 b are standard items UV350 mass spectrogram；
Fig. 3 c are standard items UV328 mass spectrogram；
Fig. 3 d are standard items UV327 mass spectrogram.
Embodiment
INSTRUMENT MODEL used is as follows in the present embodiment：
Gas chromatograph-mass spectrometer (GC-MS) (GC-MS)：SHIMADZU QP2010Ultra, ultrasonic extraction instrument：Kunshan Shu Mei KQ-A2000KDE (power adjustable), electronic balance：METTLER TOLEDO XS204B, solid-phase extraction device：Tripoli in fluorine sieve Solid-phase extraction column is 2g/10mL, or quite, bottleneck knockout：25mL, BRAND, volumetric flask：B grades of 10mL, 20mL, 50mL More than, micropipette pin：10 μ L, 50 μ L, 100 μ L, liquid-transfering gun：20 μ L, 200 μ L, 1mL, 5mL, brown sample bottle：40mL、 8mL, is accurate to 0.1mg, vacuum rotary evaporator：Tokyo physics and chemistry N-1100V-WD, full-automatic nitrogen dries up instrument：Newly open up in Shanghai XT-NS1；
In the present embodiment analysis reagent used be gas-chromatography it is pure/the residual level of agriculture or liquid chromatogram it is pure.
Some preferred embodiments of the present invention are exemplified below, to help further understanding the present invention, protection scope of the present invention It is not limited to these preferred embodiments.
Embodiment 1
The detection method of four kinds of UV stable agent contents in the products such as a kind of plastics, the rubber that the present embodiment is provided, Experiment is first carried out before detection optimal processing parameter is tested out using unitary variant method, wherein, constant constant factor：Testing sample, Sampling amount (0.2g ± 0.005g), extraction mode (ultrasonic extraction), extractant volume (25mL), Variable Factors：Extractant, Extraction temperature, extraction time；
The selection of extractant：
Weigh 0.2g ± 0.005g and handle testing sample well in sample bottle, add 25mL organic solvent toluenes or tetrahydrochysene furan Mutter or acetone or dichloromethane or ethyl acetate, it is closed, after testing sample is sufficiently humidified so as to, it is put into ultrasound bath, in room Ultrasound 40min under conditions of temperature, extracts instrument by ultrasonic wave and obtains extract, the power of ultrasonic wave is 1600w, and shelves are adjusted to 100%；
When the extract that ultrasonic extraction is obtained matrix effect occurs or be substantially muddy, purification run is first carried out, is purified Operation is specially：
Tripoli solid-phase extraction column in fluorine sieve is placed on solid-phase extraction device, activated with 6mL dichloromethane, then use 6mL N-hexane infiltrates, and keeps 1mm liquid levels to wait loading, and the extract loading that ultrasonic extraction is obtained simultaneously uses dichloromethane eluent, The flow velocity that extract is controlled during elution is 1.5mL/min, collects eluent and merged after post liquid with purity >=99.999% Nitrogen is blown and constant volume arrives 1.0mL, or collection eluent and merged after post liquid is concentrated into vacuum rotary evaporator at 40 DEG C Closely dry to obtain concentrate, transfer concentrate and leacheate carry out nitrogen into nitrogen drying instrument and are blown to 1.0mL, and GC- is then carried out again MC test analysis；
When the extract that ultrasonic extraction is obtained matrix effect does not occur or be substantially muddy, liquid to be extracted is cooled to room Wen Hou, through 0.22 μm of pin type PTFE filter membrane into sample injection bottle, then carries out GC-MC test analysis, analysis result is as shown in table 2：
Table 2 containing UV 328 for 1150mg/kg PE materials testing sample different extractant when test data
The selection of extraction temperature：
Weigh 0.2g ± 0.005g and handle testing sample (being accurate to 0.1mg) well in sample bottle, add 25mL organic molten Agent toluene or tetrahydrofuran or acetone (preferably toluene), it is closed, after testing sample is sufficiently humidified so as to, it is put into ultrasound bath, The ultrasound 40min under conditions of room temperature, 40 DEG C, 60 DEG C, extracts instrument by ultrasonic wave and obtains extract, the power of ultrasonic wave is 1600w, shelves are adjusted to 100%；
When the extract that central ultrasonic extraction is obtained matrix effect occurs or be substantially muddy, purification run is first carried out, only Changing operation is specially：
Tripoli solid-phase extraction column in fluorine sieve is placed on solid-phase extraction device, activated with 6mL dichloromethane, then use 6mL N-hexane infiltrates, and keeps 1mm liquid levels to wait loading, and the extract loading that ultrasonic extraction is obtained simultaneously uses dichloromethane eluent, The flow velocity that extract is controlled during elution is 1.5mL/min, collects eluent and merged after post liquid with purity >=99.999% Nitrogen is blown and constant volume arrives 1.0mL, or collection eluent and merged after post liquid is concentrated into vacuum rotary evaporator at 40 DEG C Closely dry to obtain concentrate, transfer concentrate and leacheate carry out nitrogen into nitrogen drying instrument and are blown to 1.0mL, and GC- is then carried out again MC test analysis；
When the extract that ultrasonic extraction is obtained matrix effect does not occur or be substantially muddy, liquid to be extracted is cooled to room Wen Hou, through 0.22 μm of pin type PTFE filter membrane into sample injection bottle, then carries out GC-MC test analysis, analysis result is as shown in table 3：
Table 3 is the test data under the different extraction temperatures of testing sample of 1150mg/kg PE materials containing UV 328
The selection of extraction time：
Weigh 0.2g ± 0.005g and handle testing sample (being accurate to 0.1mg) well in sample bottle, add 25mL organic molten Agent toluene or tetrahydrofuran or acetone (preferably toluene), it is closed, after testing sample is sufficiently humidified so as to, it is put into ultrasound bath, Under conditions of room temperature, 40 DEG C ultrasound 20min, 40min, 50min, 60min, 80min, 100min, 120min, 140min, 160min, 180min, extract instrument by ultrasonic wave and obtain extract, the power of ultrasonic wave is 1600w, and shelves are adjusted to 100%；
When the extract that central ultrasonic extraction is obtained matrix effect occurs or be substantially muddy, purification run is first carried out, only Changing operation is specially：
Tripoli solid-phase extraction column in fluorine sieve is placed on solid-phase extraction device, activated with 6mL dichloromethane, then use 6mL N-hexane infiltrates, and keeps 1mm liquid levels to wait loading, and the extract loading that ultrasonic extraction is obtained simultaneously uses dichloromethane eluent, The flow velocity that extract is controlled during elution is 1.5mL/min, collects eluent and merged after post liquid with purity >=99.999% Nitrogen is blown and constant volume arrives 1.0mL, or collection eluent and merged after post liquid is concentrated into vacuum rotary evaporator at 40 DEG C Closely dry to obtain concentrate, transfer concentrate and leacheate carry out nitrogen into nitrogen drying instrument and are blown to 1.0mL, and GC- is then carried out again MC test analysis；
When the extract that ultrasonic extraction is obtained matrix effect does not occur or be substantially muddy, liquid to be extracted is cooled to room Wen Hou, through 0.22 μm of pin type PTFE filter membrane into sample injection bottle, then carries out GC-MC test analysis, analysis result is as shown in table 4：
Table 4 is the test data under the different extraction times of testing sample of 1150mg/kg PE materials containing UV 328
Embodiment 2
In advance lower selection suitable reagent and parameter of the present embodiment after the experiment of above-described embodiment 1 are carried out, the present embodiment The detection method of four kinds of UV stable agent contents in the products such as a kind of plastics, rubber is provided, the detection method specifically include with Lower step：
(1) preparation of the mixed mark working solution of sample
0.05 ± 0.005g four kinds of ultra-violet stabilizer UV320, UV327, UV328 and UV350 standard items are weighed respectively In 50mL volumetric flasks, then with toluene constant volume and shake up, obtain the mixed mark stock solution of one-level of four kinds of ultra-violet stabilizers 1000 μ g/mL, then by the storage at 0-5 DEG C in 40mL brown bottles of the pure standby liquid of residue, accurately pipette 1.0mL is prepared one The mixed mark stock solution of level with toluene constant volume and shakes up in 20mL volumetric flasks, obtains two grades of mixed mark μ g/mL of stock solution 50, remains Remaining pure standby liquid is stored in 8mL brown bottles at 0-5 DEG C, and thus two grades of mixed mark stock solutions are further prepared into mixed mark work Solution is as shown in table 1；
The mixed mark working solution of 1 four kinds of ultra-violet stabilizers of table
Constant volume, the mixed mark working solution of the four kinds of ultra-violet stabilizers shaken up are stored up in 8mL brown sample injection bottles at 0-5 DEG C Deposit, the mixed mark working solution of each graticule takes 0.5mL to prepare respectively four kinds of ultra-violet stabilizers when making is used in sample introduction bottle GC-MC is tested, and obtains respective chromatogram, collects the peak area and appearance time on respective chromatogram bent for point making standard Line, show that standard curve y=kx+b, as graticule, specific k and b is obtained according to point；
(2) pre-treatment of testing sample
Testing sample is chosen, it is broken into the particle that particle diameter is 2mm-3mm with scissors or pulverizer, is well mixed, weighs The testing sample 0.2g handled well in sample bottle, add 25mL organic solvent toluenes (analyzed from the table 2 in embodiment 1, with reference to The rate of recovery uses toluene), it is closed, after testing sample is sufficiently humidified so as to, it is put into ultrasound bath, extracting instrument by ultrasonic wave obtains Extract, the power of ultrasonic wave is 1600w, and shelves are adjusted to 100%, at room temperature under conditions of ultrasound 60min (from embodiment 1 Table three and table four analyze, with reference to cost factor, take that extraction temperature is room temperature and extraction time is 60min),
(3) when the extract that ultrasonic extraction is obtained in step (2) matrix effect occurs or be substantially muddy, first carry out net Change operation, described purification run is specially：
Tripoli solid-phase extraction column in fluorine sieve is placed on solid-phase extraction device, activated with 6mL dichloromethane, then use 6mL N-hexane infiltrates, and keeps 1mm liquid levels to wait loading, and the extract loading that step (2) ultrasonic extraction is obtained simultaneously uses dichloromethane Alkane elute, control during elution extract flow velocity be 1.5mL/min, collect eluent and merged after post liquid use purity >= 99.999% nitrogen blows and constant volume, or collects eluent and merged after post liquid and concentrated with vacuum rotary evaporator at 40 DEG C Concentrate is obtained to closely dry, transfer concentrate and leacheate carry out nitrogen into nitrogen drying instrument and blown, and step (4) is then carried out again Operation；
Directly carried out when matrix effect or substantially muddiness does not occur in the extract that ultrasonic extraction is obtained in step (2) The operation of step (4)；
(4) analyze
Liquid to be extracted is cooled to after room temperature, through 0.22 μm of pin type PTFE filter membrane into sample injection bottle, then carries out GC-MC surveys Examination, draws chromatogram, and the standard curve made according to the chromatographic peak area of each testing sample and then using in step (1) is reference point Analysis obtains the content of testing sample middle-ultraviolet lamp stabilizer.
The instrument parameter of gas chromatograph-mass spectrometer (GC-MS) (GC-MS) is shown in Table 5 in the embodiment of the present invention：
The parameter of the gas chromatograph-mass spectrometer (GC-MS) of table 5 (GC-MS)
Positive findings judges
In the total ion chromatogram of testing sample solution and the mixed mark working solution of four kinds of ultra-violet stabilizers, sample and each The retention time of the corresponding chromatographic peak of standard substance is consistent, total ion of the mixed mark working solution of such as tetra- kinds of ultra-violet stabilizers of Fig. 1 Flow chromatography figure, such as Fig. 2 take the PE materials containing UV 328 and UV 327 to be the chromatogram that testing sample is tested out, and chromatographic peak retains Time consistency；
Characteristic ion abundance ratio at testing sample chromatographic peak corresponding with each standard substance should be consistent, each standard substance Mass spectrogram as Fig. 3 a-3d shown in, the characteristic ion and its abundance ratio of each standard substance are shown in Table 6；
The characteristic ion and its abundance ratio data of each standard substance of table 6
Material title CAS.NO. Quota ion Qualitative ion Abundance ratio
UV 320 3846-71-7 308 308 323 309 100:28:23
UV 350 36437-37-3 308 308 294 323 100:49:37
UV 328 25973-55-1 322 322 323 351 100:23:14
UV 327 3864-99-1 342 342 344 357 100:36:25
During relative abundance ＞ 50%, it is allowed to have ± 10% deviation；20% ＜ relative abundance≤50%, it is allowed to have 15% Deviation；10% ＜ relative abundance≤20%, it is allowed to have 20% deviation；Relative abundance≤10%, it is allowed to have 50% deviation.
At the trial, linear coefficient R >=0.995 of standard curve；Each batch of sample or 20 samples should do a method Blank；Each batch of sample or 20 samples should at least do a Duplicate Samples, and Duplicate Samples deviation should be less than 20%；Each batch of sample or 20 samples should at least make a mark-on reclaims sample, and the rate of recovery should be greater than 80%；Each batch of sample or 20 samples should be subject to Persistently correction validation criteria product (CCV) are corrected, and CCV retakings of a year or grade rate should be located between the 85%~115% of theoretical value.
Detection method separating degree, linear coefficient in the present invention and have good stability, quantitative accurate, the rate of recovery is high, and behaviour Make simply, conveniently.
In addition to the implementation, the present invention can also have other embodiment.All use equivalent substitution or equivalent transformation shape Into technical scheme, all fall within the protection domain of application claims.

Claims (4)

1. the detection method of four kinds of UV stable agent contents in the products such as a kind of plastics, rubber, it is characterised in that the detection side Method specifically includes following steps：
（1）The preparation of the mixed mark working solution of sample
Four kinds of ultra-violet stabilizer UV320, UV327, UV328 and UV350 standard items are weighed respectively in 50mL volumetric flasks, then With toluene constant volume and shake up, obtain the mixed mark stock solution of one-level of four kinds of ultra-violet stabilizers, then by the pure standby liquid of residue in Stored in 40mL brown bottles at 0-5 DEG C, pipette the mixed mark stock solution of the one-level prepared in 20mL volumetric flasks, it is fixed with toluene Hold and shake up, obtain two grades of mixed mark stock solutions, remaining pure standby liquid is stored in 8mL brown bottles at 0-5 DEG C, thus two grades Mixed mark stock solution is further prepared into mixed mark working solution, by the mixed mark working solution of preparation in 8mL brown sample injection bottles Stored at 0-5 DEG C, take the mixed mark working solution of preparation to be tested in sample introduction bottle with GC-MC respectively, obtain respective chromatogram, Collect the peak area and appearance time on respective chromatogram and make standard curve for point；
（2）The pre-treatment of testing sample
Testing sample is chosen, it is broken into the particle that particle diameter is 2mm-3mm with scissors or pulverizer, is well mixed, weighs processing Good testing sample adds organic solvent in sample bottle, closed, after testing sample is sufficiently humidified so as to, is put into ultrasound bath In, instrument is extracted by ultrasonic wave and obtains extract, the power of ultrasonic wave is 1600w, and shelves are adjusted to 100%；
（3）Work as step（2）When the extract that middle ultrasonic extraction is obtained matrix effect occurs or be substantially muddy, purification behaviour is first carried out Make, described purification run is specially：
Tripoli solid-phase extraction column in fluorine sieve is placed on solid-phase extraction device, with 6mL dichloromethane activate, then with 6mL just oneself Alkane infiltrates, and keeps 1mm liquid levels to wait loading, by step（2）Extract loading that ultrasonic extraction is obtained simultaneously is washed with dichloromethane De-, the flow velocity that extract is controlled during elution is 1.5mL/min, collects eluent and merged and purity >=99.999% is used after post liquid Nitrogen blow and constant volume, or collect eluent and merged after post liquid be concentrated into vacuum rotary evaporator at 40 DEG C it is near dry To concentrate, transfer concentrate and leacheate carry out nitrogen into nitrogen drying instrument and blown, and step is then carried out again（4）Operation；
Work as step（2）There is not matrix effect or directly carries out step when substantially muddy in the extract that middle ultrasonic extraction is obtained （4）Operation；
（4）Analysis
Liquid to be extracted is cooled to after room temperature, through 0.22 μm of pin type PTFE filter membrane into sample injection bottle, then carries out GC-MC tests, so Afterwards with step（1）The standard curve of middle making is the content that testing sample middle-ultraviolet lamp stabilizer is obtained with reference to analysis.
2. the detection method of four kinds of UV stable agent contents in the products such as plastics according to claim 1, rubber, it is special Levy and be：Step（1）The linear coefficient R of standard curve is more than or equal to 0.995.
3. the detection method of four kinds of UV stable agent contents in the products such as plastics according to claim 1, rubber, it is special Levy and be：The step（2）Temperature is room temperature during middle ultrasonic extraction, and ultrasonic time is 60min.
4. the detection method of four kinds of UV stable agent contents in the products such as plastics according to claim 1, rubber, it is special Levy and be：Step（2）Described in organic solvent be toluene.
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CN107782824A (en) * 2017-10-25 2018-03-09 广东产品质量监督检验研究院 The quick determination method of a variety of UV stabilizers in a kind of PET bottle
CN111579670A (en) * 2020-05-26 2020-08-25 亿科检测认证有限公司 Method for detecting bisphenol F in food contact plastic product
CN114088680A (en) * 2021-10-14 2022-02-25 安徽中科赛飞尔科技有限公司 Rapid detection method for trace amount of drugs in hair dyeing sample

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001220486A (en) * 2000-02-09 2001-08-14 Techno Polymer Co Ltd Thermoplastic resin composition having excellent recyclability and regenerated molding material
CN103063763A (en) * 2012-12-21 2013-04-24 林维宣 High performance liquid chromatography detection method for residual quantity of multiple ultraviolet absorbents in cosmetics
CN105021753A (en) * 2015-07-03 2015-11-04 中华人民共和国台州出入境检验检疫局 Liquid chromatography UV method for detection of specific migration of 9 specific UV absorbers
CN105606727A (en) * 2015-12-25 2016-05-25 广州广电计量检测股份有限公司 Method for detecting benzotriazole ultraviolet absorbent in plastic product
CN106033082A (en) * 2015-03-12 2016-10-19 谱尼测试集团上海有限公司 Detection method for four benzotriazole ultraviolet absorbers in plastics and related products

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001220486A (en) * 2000-02-09 2001-08-14 Techno Polymer Co Ltd Thermoplastic resin composition having excellent recyclability and regenerated molding material
CN103063763A (en) * 2012-12-21 2013-04-24 林维宣 High performance liquid chromatography detection method for residual quantity of multiple ultraviolet absorbents in cosmetics
CN106033082A (en) * 2015-03-12 2016-10-19 谱尼测试集团上海有限公司 Detection method for four benzotriazole ultraviolet absorbers in plastics and related products
CN105021753A (en) * 2015-07-03 2015-11-04 中华人民共和国台州出入境检验检疫局 Liquid chromatography UV method for detection of specific migration of 9 specific UV absorbers
CN105606727A (en) * 2015-12-25 2016-05-25 广州广电计量检测股份有限公司 Method for detecting benzotriazole ultraviolet absorbent in plastic product

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
勾新磊等: "固相萃取－超高效液相色谱－串联质谱法同时测定食品接触塑料制品中 10 种苯并三唑类紫外吸收剂", 《色谱》 *
王成云等: "气相色谱／串联质谱法同时测定电子电气产品塑料部件中6种苯并三唑类紫外线吸收剂", 《塑料助剂》 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107782824A (en) * 2017-10-25 2018-03-09 广东产品质量监督检验研究院 The quick determination method of a variety of UV stabilizers in a kind of PET bottle
CN107782824B (en) * 2017-10-25 2020-06-30 广东产品质量监督检验研究院 Method for rapidly detecting multiple ultraviolet stabilizers in PET plastic bottle
CN111579670A (en) * 2020-05-26 2020-08-25 亿科检测认证有限公司 Method for detecting bisphenol F in food contact plastic product
CN114088680A (en) * 2021-10-14 2022-02-25 安徽中科赛飞尔科技有限公司 Rapid detection method for trace amount of drugs in hair dyeing sample
CN114088680B (en) * 2021-10-14 2023-06-27 安徽中科赛飞尔科技有限公司 Rapid detection method for trace drugs in hair dyeing sample

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