CN108469501A - The method for quickly measuring red phosphorus stability - Google Patents
The method for quickly measuring red phosphorus stability Download PDFInfo
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- CN108469501A CN108469501A CN201810613397.XA CN201810613397A CN108469501A CN 108469501 A CN108469501 A CN 108469501A CN 201810613397 A CN201810613397 A CN 201810613397A CN 108469501 A CN108469501 A CN 108469501A
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Abstract
The invention discloses a kind of methods of quick measurement red phosphorus stability, the defects of time-consuming existing for traditional red phosphorus 4stability determination, analytic process is complicated, required pharmacy variety is more, the present invention is that red phosphorus is oxidized to phosphoric acid in the red phosphorus water phase there are oxidant, it measures before suspension constant temperature and the pH value of different constant temperature time, red phosphorus oxidation stability is judged according to the size of pH value variable quantity.This method has the characteristics that easy to operate, quick, the intermediate control especially suitable for the production of microencapsulation red phosphorus.
Description
Technical field
The invention belongs to chemical technology fields, are related to a kind of assay method of red phosphorus stability.
Background technology
Red phosphorus be in fire retardant uniquely can direct applied fire-retardant simple substance since it contains only ignition-proof element be existing add
Add that reach identical flame retardant effect additive amount in type fire retardant minimum.Red phosphorus ensures with extremely low additive amount by flame-retardant polymer
It keeps also having the advantages that press down cigarette, low toxicity while good mechanical mechanics property and electric property.However, red phosphorus can slowly with
Oxygen and moisture in air react generate phosphoric acid, the oxyacid of different valence states such as phosphorous acid and release it is inflammable and explosive,
There is the phosphine gas of severe toxicity, thus directly do fire retardant using red phosphorus, is greatly limited.In consideration of it, red phosphorus is micro-
Encapsulation techniques come into being, by red phosphorus Surface Creation clad, reduce red phosphorus in air moisture and oxygen contact
Probability improves the stability of microencapsulation red phosphorus to reduce oxidation reaction of red phosphorus during manufacture, transport, use.For
The clad of the excellent flame retardant characteristic for keeping red phosphorus itself to have, microencapsulation red phosphorus is unsuitable blocked up, therefore, in its manufacturing process
It is middle necessarily have a small amount of red phosphorus surface be not formed effect cladding so that microencapsulation red phosphorus in air moisture and oxygen contact
Oxidation reaction occurs.Stability is a good and bad important indicator of microencapsulation red phosphorus cladding, and the yield of hydrogen phosphide and phosphorus
Oxyacid yield be again microencapsulation red phosphorus determination of stability important indicator.
Many documents use characterization parameter of one index of hydrogen phosphide occurrence quantity as red phosphorus stability, specific by measuring
The external environment and number of the yield of hydrogen phosphide judges red phosphorus stability under the conditions of the time.Japan Patent
Quantitative red phosphorus sample is placed in full of the closed of nitrogen in JP2001089113A, JP2001323267A, JP2013023660A
In container, after being kept for 1-3 hours at 250 DEG C, testing tube of hydrogen phosphide gas is used（0 15ppm of detectable concentration, the industry of north pool
Co. Ltd. system）Hydrogen phosphide in detection container in gas phase（PH3）After concentration, determine that every gram of red phosphorus generates the amount of hydrogen phosphide.
In above-mentioned patent, under the detection temperature condition, red phosphorus has the risk of burning, explosion so that equipment related with detection process,
The security risk of personnel increased dramatically.Chinese patent CN201410298045.1, CN201410798274.X,
20 grams of samples and 40 grams of water are configured to suspension in 500 milliliters of conical flasks in CN200810120570.9,40 after sealing
It is placed 24 hours at a temperature of DEG C, hydrogen phosphide is oxidized to after oxyacid by gas extraction with oxidant and is contained surely with Mu indigo plant Bi Se Fa Measuring
The content of oxygen acid, so that it is determined that every gram of sample hydrogen phosphide yield hourly.Such method is longer due to taking, as micro- glue
The control of the production process of encapsulated red phosphorus has hysteresis quality；Such method analyte detection process is more, complicated for operation simultaneously, is easy to draw
Enter human error, to influence final result.
Also document characterizes the stability of red phosphorus with the oxidizing acid yield of phosphine gas and phosphorus simultaneously.It is Chinese special
Sharp CN201010550396.9, United States Patent (USP) US4113841A, US4136154A are described with thermometer, reflux condensation mode
Pipe, gas-guide tube, electromagnetic agitation there-necked flask in 1 gram of sample and 450 milliliters of distilled water are added, be warming up to 80 DEG C, stirring, with 10
Liter/min rate be passed through oxygen, by hydrogen phosphide and oxygen import together two continuously be equipped with 100 milliliter of 5% concentration（Weight
Amount）The drexel bottle of mercuric chloride solution, by drop reaction generate hydrochloric acid content so that it is determined that hydrogen phosphide content.It is present in round bottom
Oxyacid amount in flask is determined also by titration.Due to being taken out of hydrogen phosphide as carrier gas using oxygen in such method,
A small amount of oxygen reacts with hydrogen phosphide and generates phosphorous oxides during this, causes the fearless loss of hydrogen phosphide so that most
Whole Phosphine content is relatively low；The analytic process is complicated simultaneously, more using varieties of reagent, increases analysis testing cost.
The surface plate that 5.0 grams of red phosphorus are placed in 50 millimeters is described in US4853288A, US5093199A, US4698215A
In, and it is put into 50 DEG C -80 DEG C of constant temperature, the closed glass container of 100% relative atmospheric humidity condition is kept for 168 hours.It is formed by
Hydrogen phosphide is taken out of with 10 ls/h of air stream from glass container, and 2.5% concentration is used in combination（Weight）Mercuric chloride solution carry out
Absorb, by titrate generate hydrochloric acid content so that it is determined that hydrogen phosphide yield.Sample in above-mentioned surface plate is put into 250 millis
It rises in beaker, the hydrochloric acid of 200 milliliter of 1% concentration is added, be uniformly mixed, heating is boiled 10 minutes and filtered, and molybdenum blue colorimetric method is used
Determine the amount of oxyacid.Time-consuming for such method, has serious hysteresis quality, is related to that varieties of reagent is more, analytic process is complicated, appearance
It is easily introduced human error；The oxygen when being drawn hydrogen phosphide using air in air can be reacted with hydrogen phosphide simultaneously, from
And reduce final result.
United States Patent (USP) US4210630A describes 25.0 grams of red phosphorus and is placed in crystallising dish, and is put into 50 DEG C of constant temperature, and 72% is opposite
The closed glass container of atmospheric humidity condition is kept for 28 days.Hydrogen phosphide is formed by take out of from glass container by nitrogen stream,
5% concentration is used in combination（Weight）Mercuric chloride solution is absorbed, the P of formation（HgCl）3It is aoxidized with excessive iodine, excessive iodine
It is titrated by sodium thiosulfate standard liquid, so that it is determined that the phosphatization hydrogen amount that every gram of red phosphorus generates per hour.Take 5 grams of above-mentioned red phosphorus
It is suspended in 100 milliliters of distilled water, and the suspension is heated to boiling.It filters and is washed for several times with hot water.By filtrate and 15
Gram NaCl is mixed and 0.1N sodium hydroxide solutions is used to titrate, so that it is determined that the amount of oxidizing acid.Although this method avoids phosphatization
The defect that hydrogen is aoxidized when drawing, but it is not improved yet the defects of time-consuming, flow is complicated.
Invention content
To solve existing for traditional red phosphorus 4stability determination, time-consuming, analytic process is complicated, required pharmacy variety is more
The defects of, for needing judge in time product quality in the production of microencapsulation red phosphorus, there are great hysteresis qualitys, to produce control
Bring great inconvenience.The present invention proposes a kind of method of judgement red phosphorus stability easy to operate, quick, and this method is especially suitable
Close the middle control analysis of microencapsulation red phosphorus production process.
In order to achieve the above objectives, the present invention uses following technological means：It is in oxygen quickly to measure the method for red phosphorus stability
In red phosphorus water phase existing for agent, red phosphorus is oxidized to phosphoric acid by oxidant, by before suspension constant temperature and under different constant temperature times
The size of the pH value variable quantity of suspension, to judge the stability of red phosphorus.Concrete scheme is：Weigh quantitative red phosphorus sample with
Distilled water is configured to suspension, and quantitative oxidant is added and is uniformly mixed, is counted with PH and measures its pH value.Above-mentioned solution is placed in water
Constant temperature in bath, and the pH value of different constant temperature time suspension is measured respectively, it can determine that according to pH value variable quantity size tested
The stability of red phosphorus sample.
In the present invention, oxidant select nitrate, hydrogen peroxide, chlorate, hypochlorite, one kind in permanganate or
It is several.Oxidant selection aqueous solution is in the best of alkalescence or neutrality in the present invention, and aqueous solution is in acid or strong basicity oxidation
Agent is since the pH value variable quantity in initial reaction stage suspension is smaller, unfavorable realization quickly detection.
In the present invention, thermostat temperature is 60-90 DEG C, most preferably 80-90 DEG C.Thermostat temperature is low, and oxidizing reaction rate is slow,
PH value changes unobvious, and then affects measurement result.
In the present invention, constant temperature time is 30-90 minutes, most preferably 30-60 minutes.Constant temperature time is too short, oxidation reaction
Not exclusively, pH value changes unobvious；Constant temperature time grows the timeliness for reducing analytic process.
Specific implementation mode
The protection content of the present invention, is described in detail, by specific embodiment for what is be specifically discussed in detail
Embodiment only belongs to an example in range as defined in the claims, is only used for specific example, not representation
Sharp claim full scope claimed.In all embodiments and comparative example, unless otherwise mentioned, all ratios are all
Weight ratio.
The following raw material is used in all examples：
1# samples, microencapsulation red phosphorus, Yunnan Jianglin Group Co., Ltd., red phosphorus content 85%, 7 microns of average particle size；
2# samples, microencapsulation red phosphorus, Yunnan Jianglin Group Co., Ltd., red phosphorus content 75%, 7 microns of average particle size；
3# samples, industrial red phosphorus, Yunnan Jianglin Group Co., Ltd., 150 mesh of granularity（~100 microns）.
Embodiment 1-18
It weighs the sample and 95 milliliters of distilled water determined in 5 grams of tables 1 and is configured to suspension in 250 milliliters of beakers, be added by table 1
Quantitative oxidant is uniformly mixed, using the laboratory PH meter cooperations of Shanghai INESA Scientific Instrument Co., Ltd.'s PHSJ-4A types
E-201-C-9 type combination electrodes measure pH value, are listed in Table 1 below.Above-mentioned suspension is subjected to constant temperature by the temperature in table 1.Respectively
The pH value that mixed solution when measuring constant temperature 30 minutes, 60 minutes is counted with above-mentioned PH, is listed in Table 1 below.
Comparative example 1-3
Weigh the sample determined in 5 grams of tables 2 be placed in gas-guide tube, reflux condensing tube, electromagnetic agitation there-necked flask in, and be added
180 ml deionized waters, 80 DEG C of constant temperature in water-bath start stirring, and nitrogen is passed through with 10 liters/min of rate in gas-guide tube,
The mixed gas of hydrogen phosphide and nitrogen enters two by reflux condensing tube and concatenated 100 milliliter of 5% mercuric chloride solution is housed
Drexel bottle, the P of formation（HgCl）3It being aoxidized with excessive iodine, excessive iodine is titrated by sodium thiosulfate standard liquid, from
And determine the phosphatization hydrogen amount that every gram of sample generates per hour.The suspension in above-mentioned there-necked flask is filtered, is dripped with sodium hydroxide solution
Determine filtrate, the oxidizing acid yield of phosphorus is indicated with the milligram number of every gram of sample consumption sodium hydroxide.Acquired results are listed in table 2
In.
1 embodiment measurement result of table
2 comparative example testing result of table
To obtained by the determination method of the present invention it can be seen from same sample results contrast and traditional determination method in table 1,2
Result it is with uniformity, moreover, whole measurement process take it is few.From the point of view of detection process, operating process of the present invention is easy,
Reagent used, instrument are few.Therefore the present invention has good grasp using the stability of pH value variable quantity directly perceived characterization red phosphorus
The property made.
Claims (4)
1. the method for quickly measuring red phosphorus stability, it is characterised in that：It is added in the suspension that red phosphorus sample is prepared with distilled water
Quantitative oxidant, under the conditions of constant temperature and certain time, red phosphorus is oxidized to phosphoric acid by oxidant, measure before suspension constant temperature and
The pH value of different constant temperature times judges the stability of red phosphorus according to the size of pH value variable quantity.
2. the method for quick measurement red phosphorus stability according to claim 1, it is characterised in that：Red phosphorus suspension constant temperature temperature
Degree is 60-90 DEG C, and constant temperature time is 30-90 minutes.
3. the method for quick measurement red phosphorus stability according to claim 2, it is characterised in that：Red phosphorus suspension constant temperature temperature
Degree is 80-90 DEG C, and constant temperature time is 30-60 minutes.
4. the method for quick measurement red phosphorus stability according to claim 1 or 2, it is characterised in that：Oxidant selects nitre
One or more of hydrochlorate, hydrogen peroxide, chlorate, hypochlorite, permanganate.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1429251A (en) * | 2000-05-25 | 2003-07-09 | 日本化学工业株式会社 | Red phosphorus fire retardant for epoxy, red phosphorus fire retardant composition for epoxy, their mfg. method, epoxy composition for semiconductor sealing materials |
| CN104059388A (en) * | 2014-06-27 | 2014-09-24 | 南京化工职业技术学院 | Double-coated microencapsulated red phosphorus and preparation method thereof |
| CN203858177U (en) * | 2014-05-28 | 2014-10-01 | 天津大学 | Device for testing amount of hydrogen phosphide released from flame-retardant red phosphorus polymer material |
| CN105403657A (en) * | 2014-05-28 | 2016-03-16 | 天津大学 | Method for testing release amount of hydrogen phosphide in red phosphorus inflaming retarding polymer material |
| CN107722356A (en) * | 2017-10-19 | 2018-02-23 | 云南江磷集团股份有限公司 | Melamine cyanurate microencapsulation Red Phosphorus Flame Retardant product and preparation method thereof |
-
2018
- 2018-06-14 CN CN201810613397.XA patent/CN108469501A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1429251A (en) * | 2000-05-25 | 2003-07-09 | 日本化学工业株式会社 | Red phosphorus fire retardant for epoxy, red phosphorus fire retardant composition for epoxy, their mfg. method, epoxy composition for semiconductor sealing materials |
| CN203858177U (en) * | 2014-05-28 | 2014-10-01 | 天津大学 | Device for testing amount of hydrogen phosphide released from flame-retardant red phosphorus polymer material |
| CN105403657A (en) * | 2014-05-28 | 2016-03-16 | 天津大学 | Method for testing release amount of hydrogen phosphide in red phosphorus inflaming retarding polymer material |
| CN104059388A (en) * | 2014-06-27 | 2014-09-24 | 南京化工职业技术学院 | Double-coated microencapsulated red phosphorus and preparation method thereof |
| CN107722356A (en) * | 2017-10-19 | 2018-02-23 | 云南江磷集团股份有限公司 | Melamine cyanurate microencapsulation Red Phosphorus Flame Retardant product and preparation method thereof |
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