CN105694160A - Method for preparing neoprene positive samples with ethylene thiourea - Google Patents
Method for preparing neoprene positive samples with ethylene thiourea Download PDFInfo
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- CN105694160A CN105694160A CN201610238742.7A CN201610238742A CN105694160A CN 105694160 A CN105694160 A CN 105694160A CN 201610238742 A CN201610238742 A CN 201610238742A CN 105694160 A CN105694160 A CN 105694160A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/39—Thiocarbamic acids; Derivatives thereof, e.g. dithiocarbamates
- C08K5/405—Thioureas; Derivatives thereof
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Abstract
The invention belongs to the field of preparation of neoprene positive samples, and particularly relates to a method for preparing neoprene positive samples with ethylene thiourea. The method includes main steps of 1), adding solution of ethylene thiourea solid standard substances into liquid neoprene adhesive to obtain liquid positive samples; 2), drying moisture and organic solvents in the liquid positive samples to obtain initial solid positive samples; 3), treating the initial solid positive samples according to processes specified by national standard GB/T17783-1999 Preparation of Vulcanized Rubber Samples And Test Specimens-Chemical Tests to obtain the neoprene positive samples with the ethylene thiourea. The method has the advantages that the method is scientific and reasonable and is high in operability, the neoprene positive samples prepared by the aid of the method are good in uniformity, high in stability and easy to store and can be used for verifying standard methods and controlling the quality of routine detection, and the like.
Description
Technical field
The invention belongs to the preparation field of neoprene positive, the preparation method being specifically related to a kind of neoprene positive containing ethylene thiourea。
Background technology
Ethylene thiourea (2-Imidazolidinethione), another name ethylene thiourea (ETU), fusing point 196-200 DEG C, boiling point 347.2 DEG C, is a kind of white needles or granular crystal powder, CAS:96-45-7, and molecular weight is: 102.1581。In the production process of neoprene and goods thereof, ethylene thiourea is commonly used for vulcanization accelerator。Add the ethylene thiourea with reference to consumption is 0.25 ~ 1.5 part when the vulcanization of rubber and can accelerate curingprocess rate, shorten cure time, reduce curing temperature, reduce the application of vulcanizing agent, the physical and mechanical properties of vulcanite can be improved simultaneously, make goods have the advantages that tensile strength height, permanent compression set are little。
Research shows that this material has carcinogenic and teratogenesis, can cause solid edema, thyromegaly, and other diseases reduced with thyromegaly hormone。For this, on June 1st, 2007 is played enforcement " registration of chemicals, assessment, mandate and restriction " regulation (being called for short REACH regulation) in by European Union, ethylene thiourea is classified as the tenth batch and shows great attention to material, and it is made strict demand in test specification of content, limitation parameter, test complexity etc. in rubber and goods thereof。The technology barriers come to China's rubber and product row industrial belt thereof to tackle this regulation to be likely to, the plan target about " rubber and the detection method of ethylene thiourea in goods thereof " standard formulation has been assigned by China national certification and accreditation Watch-dog committee in 2015, and sets detection and be limited to 10mg/kg。
According to the regulation of China's standard formulation, the standard detecting method of formulation needs associated mechanisms that it is verified, and just can get the Green Light enforcement after being verified。And positive must be used just effectively to verify the standard formulated；Additionally, in daily sample analysis detection process, it is known that the positive of concentration is also commonly used for detection quality control。Visible, positive is all most important to the reliability of validation criteria method and the stability of guarantee routine testing quality。
Currently, market there is no the positive neoprene production marketing containing ethylene thiourea。This brings great difficulty to the relevant checking of formulation standard and the control of routine testing quality。In order to change this present situation, the present invention proposes a kind of formulation neoprene positive preparation method containing ethylene thiourea。Positive prepared by application this method has uniform, stable and is prone to the plurality of advantages such as preservation。
Summary of the invention
Present invention aim at for the deficiencies in the prior art, it is provided that the preparation method of a kind of neoprene positive containing ethylene thiourea。The method has the features such as scientific and reasonable, workable, and preparation-obtained positive has that uniformity is good, stability is high, the advantage of easy preservation, can be used for the quality control of the checking of standard method and routine testing。
The preparation method of a kind of neoprene positive containing ethylene thiourea, comprises the following steps:
1) preparation of liquid positive: precise definite value have certificate ethylene thiourea solid-state standard substance, obtain homogeneous liquid ethylene thiourea solution with organic solvent dissolution；This solution is added in the chloroprene rubber adhesive of liquid, stirring and evenly mixing, obtain homogeneous liquid containing ethylene thiourea chloroprene rubber adhesive positive；
2) liquid positive is dry: the liquid positive of mix homogeneously be poured in flat bottom glass vessel, and is placed in fume hood by glass drying oven the system of drying in the air, and volatilize most organic solvent；After the system of drying in the air, glass drying oven is put into vacuum drying oven, at a set temperature evacuation, and keep certain time with most of organic solvent and the moisture of volatilizing, obtain preliminary solid-state positive；
3) prepared by the sample of solid-state positive: according to the method for national standard " GB/T17783-1999 cured rubber samples and sample prepare chemical test " defined, solid sample tentatively shreds processed, after processing in freezing mode, viscous the sticking of dispersion tentatively shreds sample, and then shred into the granule that granularity is less, after freezing mode processes, glutinous granule is glued in dispersion, prepare after crossing testing sieve and can be used for chemico-analytic solid-state positive sample, be placed in the exsiccator equipped with variable color silica gel and adopt sealing bag to carry out subpackage。
More specifically, the preparation method of a kind of neoprene positive containing ethylene thiourea, particularly as follows:
Step 1) concretely comprises the following steps:
A. the definite value weighing 0.1000g in the glass of 200mL is 98.5% ethylene thiourea standard substance, adds the methanol of 10mL, after ultrasonic dissolution, adds the toluene solvant of 100mL, is uniformly mixed, obtains ethylene thiourea solution；
B. take 2000mL glass beaker and be placed on agitator, it is added to the commercially available chloroprene rubber adhesive of 1600mL, and the ethylene thiourea solution prepared is joined in beaker, 3 ~ 4h is stirred with the speed of 1000 ~ 1500r/min, and in the process of stirring mixing, constantly add toluene solvant 500mL, xylene solvent 100mL, with the volatilization of supplementary organic solvent；Namely uniform liquid positive is obtained after liquid sample is sufficiently agitated；
Step 2) particularly as follows:
Uniform liquid positive is poured onto in flat glass culture dish one by one；Will be equipped with the glass culture dish of liquid positive and put into the system 5 ~ 10 days of drying in the air under room temperature in fume hood so that most of organic solvents volatilization in liquid sample, obtain the solid sample of surface cure；Will be equipped with the glass culture dish of sample and put into vacuum drying oven, temperature is arranged on 20 ~ 30 DEG C, and vacuum drying 12 ~ 24h, pressure remains 1000Pa；
Step 3) particularly as follows:
By step 2) the preliminary solid-state positive that obtains takes out in glass culture dish, shred into the granule that granularity is 3mm × 3mm granularity, put into-18 DEG C of refrigerator freezing 3 ~ 6h, viscous will stick Granular composite, and use shears to be shredded into fine particle, put into-18 DEG C of refrigerator freezing 3 ~ 6h, will viscous glutinous Granular composite mistake 10 mesh sieves, obtained sample splitting to aluminium foil bag, every bag of about 15g, seal, be placed in the exsiccator equipped with variable color silica gel room temperature and preserve。
The uniformity testing of obtained solid-state positive: detecting according to ethylene thiourea in solid positive to preparation of the method for testing of chemical industry standard " HG/T2343-2012 vulcanization accelerator ETU " defined, completing the uniformity testing of positive by result being calculated statistic F。
It is an advantage of the current invention that:
1) present invention is with commercially available chloroprene rubber adhesive commodity for preparing the neoprene positive substrate containing ethylene thiourea, and raw material sources are extensive, cheap；
2) present invention adopts organic solvent diluting to prepare positive in conjunction with the mode of stirring and evenly mixing, product uniformity is good, stability is high, be prone to the features such as preservation, fill up the blank that there is no the positive neoprene sample containing ethylene thiourea on market, there is good market application foreground。
Accompanying drawing explanation
Fig. 1 ethylene thiourea (ETU) contrast color spectrogram；Water water, standardsolution standard solution,
Blanksample blank sample, spikedsample mark-on sample。
Detailed description of the invention
For the open further rather than restriction present invention, below in conjunction with example, the present invention is described in further detail。
Embodiment 1
One, the preparation of liquid positive
1, the preparation of ethylene thiourea solution:
In the glass of 200mL, weigh the ethylene thiourea standard substance (having certificate, definite value is 98.5%) of 0.1000g, add the methanol of 10mL, after ultrasonic dissolution, add the toluene solvant of 100mL, be uniformly mixed, obtain uniform ethylene thiourea solution；
2, the preparation of liquid positive:
Universal mixer is placed in fume hood, take 2000mL glass beaker and be placed on agitator, it is added to the commercially available chloroprene rubber adhesive of 1600mL, and the ethylene thiourea solution prepared is joined in beaker, stir 3h with the speed of 1500r/min, and in the process of stirring mixing, constantly add toluene solvant 500mL, xylene solvent 100mL, with the volatilization of supplementary organic solvent, liquid is kept to have good mobility；Namely uniform liquid positive is obtained after liquid sample is sufficiently agitated；
Two, liquid positive is dry
The liquid positive of above-mentioned mixing is poured onto in flat glass culture dish one by one；Will be equipped with the glass culture dish of liquid positive and put into the system of drying in the air under room temperature in fume hood 8 days so that most of organic solvents volatilization in liquid sample, obtain the solid sample of surface cure；Will be equipped with the glass culture dish of sample and put into vacuum drying oven, temperature is arranged on 25 DEG C, and vacuum drying 18h (keeps 1000Pa)；
Three, prepared by the sample of solid-state positive
Above-mentioned sample is taken out in glass culture dish, the granule that granularity is 3mm × 3mm granularity is shredded into according to national standard " GB/T17783-1999 cured rubber samples prepares chemical test with sample " regulation, put into-18 DEG C of refrigerator freezing 5h, viscous will stick Granular composite, shears is used to be shredded into fine particle, put into-18 DEG C of refrigerator freezing 5h, viscous will stick Granular composite and cross 10 mesh sieves (aperture 1.7mm), obtained sample splitting is to aluminium foil bag, every bag of about 15g, seal, be placed in the exsiccator equipped with variable color silica gel room temperature and preserve。
Four, the uniformity testing of solid-state positive
The following is the method for testing according to chemical industry standard " HG/T2343-2012 vulcanization accelerator ETU " defined ethylene thiourea in the solid positive sample of preparation is detected, the extracting method of positive carries out with reference to inspection and quarantining for import/export industry standard " in SN/T0190-2012 export Fruit and vegetable ethylene thiourea determination of residual amount method GC-MS "；Specific embodiment of the invention experiment and effect data are only and absolutely prove the present invention further, but the invention is not restricted to this。
1, the mensuration of ethylene thiourea in solid-state positive
1.1 instruments and reagent
Agilent1200 chromatograph of liquid, Agilent company of the U.S.；Agitator, WIGGENS company of Germany；RV10 Rotary Evaporators, IKA company of Germany；3K-15 refrigerated centrifuger, Sigma company of Germany；SartoriusBS1100S type analysis balance (100,000/, Germany)。
Ethylene thiourea standard substance (purity 98.5.0%), Dr.Ehrenstorfer company of Germany。
1.2 extract and constant volume
In the centrifuge tube of 50mL, weigh sample 0.500g(be accurate to 0.001g), add 30mL methanol, ultrasonic 60min at 40 DEG C, with the centrifugal 5min of 3000r/min, take whole extracting solution；Bring up again once, united extraction liquid。By extracting solution rotary evaporated to dryness at 40 DEG C, add the mobile phase constant volume of 2.00mL, cross 0.22 μm of filter membrane, to be analyzed。
1.3 liquid phase chromatogram conditions
Liquid phase chromatogram condition chromatographic column: C18 (4.6mm × 250mm, 5 μm)；Mobile phase: methanol: water=1.5:98.5, flow velocity: 2.0mL/min；Sample size: 10.0 μ L；Wavelength: 220nm；Quantitative approach: area normalization method。
2, uniformity testing
The present invention adopts one factor analysis of variance to carry out uniformity test。According to total sample unit number 2 × N1/3Randomly drawing 12 samples, each sample parallel measures 3 times, carries out single factor analysis。Calculating the mean square deviation in every group and the mean square deviation between group, respective degree of freedom, significance level, the method given according to variance test is calculated statistic F。Look into F-distribution table, find F marginal value, compare with calculated F value, it is determined whether uniformly。Wherein each testing result all represents with chromatographic work station Software Integration peak area。
The uniformity testing result of the table 1 neoprene positive containing ethylene thiourea
The uniformity testing variance analysis of the table 2 neoprene positive containing ethylene thiourea
Uniformity testing conclusion:
Analyze it is shown that F value=2.049 < F0.05(11,24)=2.216 marginal values, it was shown that the uniformity of sample is good。
The foregoing is only presently preferred embodiments of the present invention, all equalizations done according to the present patent application the scope of the claims change and modify, and all should belong to the covering scope of the present invention。
Claims (5)
1. the preparation method of the neoprene positive containing ethylene thiourea, it is characterised in that: comprise the following steps:
1) preparation of liquid positive: the ethylene thiourea solid-state standard substance of precise definite value, obtains homogeneous liquid ethylene thiourea solution with organic solvent dissolution；This solution is added in the chloroprene rubber adhesive of liquid, stirring and evenly mixing, obtain uniform liquid positive；
2) liquid positive is dry: the liquid positive of step 1) mix homogeneously be poured in flat bottom glass vessel, and is placed in fume hood by glass drying oven the system of drying in the air, and volatilize most organic solvent；After the system of drying in the air, glass drying oven is put into vacuum drying oven, at a set temperature evacuation, and keep certain time, obtain preliminary solid-state positive；
3) prepared by the sample of solid-state positive: by step 2) the preliminary solid-state positive that obtains processes according to the method for national standard " GB/T17783-1999 cured rubber samples and sample prepare chemical test " defined, prepares the neoprene positive containing ethylene thiourea。
2. the preparation method of the neoprene positive containing ethylene thiourea according to claim 1, it is characterised in that: step 1) concretely comprises the following steps:
A. the definite value weighing 0.1000g in the glass of 200mL is 98.5% ethylene thiourea standard substance, adds the methanol of 10mL, after ultrasonic dissolution, adds the toluene solvant of 100mL, is uniformly mixed, obtains ethylene thiourea solution；
B. take 2000mL glass beaker and be placed on agitator, it is added to the commercially available chloroprene rubber adhesive of 1600mL, and the ethylene thiourea solution prepared is joined in beaker, 3 ~ 4h is stirred with the speed of 1000 ~ 1500r/min, and in the process of stirring mixing, constantly add toluene solvant 500mL, xylene solvent 100mL, with the volatilization of supplementary organic solvent；Namely uniform liquid positive is obtained after liquid sample is sufficiently agitated。
3. the preparation method of the neoprene positive containing ethylene thiourea according to claim 1, it is characterised in that: step 2) particularly as follows:
Uniform liquid positive is poured onto in flat glass culture dish one by one；Will be equipped with the glass culture dish of liquid positive and put into the system 5 ~ 10 days of drying in the air under room temperature in fume hood so that most of organic solvents volatilization in liquid sample, obtain the solid sample of surface cure；Will be equipped with the glass culture dish of sample and put into vacuum drying oven, temperature is arranged on 20 ~ 30 DEG C, and vacuum drying 12 ~ 24h, pressure remains 1000Pa。
4. the preparation method of the neoprene positive containing ethylene thiourea according to claim 1, it is characterized in that: step 3) is particularly as follows: by step 2) the preliminary solid-state positive that obtains takes out in glass culture dish, shred into the granule that granularity is 3mm × 3mm granularity, put into-18 DEG C of refrigerator freezing 3 ~ 6h, viscous will stick Granular composite, shears is used to be shredded into fine particle, put into-18 DEG C of refrigerator freezing 3 ~ 6h, viscous will stick Granular composite and cross 10 mesh sieves, obtained sample splitting is to aluminium foil bag, every bag of about 15g, seal, it is placed in the exsiccator equipped with variable color silica gel room temperature and preserves。
5. the neoprene positive containing ethylene thiourea that the preparation method as described in any one of claim 1-4 prepares。
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112557564A (en) * | 2020-12-09 | 2021-03-26 | 苏州博莱特新材料有限公司 | Method for determining content of benzene solvent in solvent type acrylate adhesive |
| CN114778262A (en) * | 2022-03-04 | 2022-07-22 | 福州海关技术中心 | Preparation method and application of edible oil matrix cannabinoid standard sample |
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| CN104764835A (en) * | 2015-04-28 | 2015-07-08 | 中华人民共和国福清出入境检验检疫局 | Potato powder matrix standard sample containing flumorph residue and preparation method thereof |
| CN105353066A (en) * | 2015-07-29 | 2016-02-24 | 广东风华高新科技股份有限公司 | Determination method of ethylene thiourea content in plastic product |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104502468A (en) * | 2014-11-26 | 2015-04-08 | 广州广电计量检测股份有限公司 | Detection method for ethlenethiourea in plastic products |
| CN104764835A (en) * | 2015-04-28 | 2015-07-08 | 中华人民共和国福清出入境检验检疫局 | Potato powder matrix standard sample containing flumorph residue and preparation method thereof |
| CN105353066A (en) * | 2015-07-29 | 2016-02-24 | 广东风华高新科技股份有限公司 | Determination method of ethylene thiourea content in plastic product |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112557564A (en) * | 2020-12-09 | 2021-03-26 | 苏州博莱特新材料有限公司 | Method for determining content of benzene solvent in solvent type acrylate adhesive |
| CN112557564B (en) * | 2020-12-09 | 2021-10-22 | 苏州博莱特新材料有限公司 | Method for determining content of benzene solvent in solvent type acrylate adhesive |
| CN114778262A (en) * | 2022-03-04 | 2022-07-22 | 福州海关技术中心 | Preparation method and application of edible oil matrix cannabinoid standard sample |
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