CN109061026A - The method that the PEEK sample of a kind of pair of synthesis carries out analysis detection - Google Patents
The method that the PEEK sample of a kind of pair of synthesis carries out analysis detection Download PDFInfo
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Abstract
The present invention relates to a kind of methods that the PEEK sample to synthesis carries out analysis detection, comprising steps of S11: preparing the high performance liquid chromatograph for being furnished with UV detector and chromatographic column, it is acetonitrile/pure water=65/35 isocratic elution that mobile phase parameter, which is arranged, 30 DEG C of column temperature, UV detector wavelength 235nm；S12: acetonitrile 65/35 is mixed into obtain mobile phase by volume with pure water；S13: taking hydroquinone, diphenyl sulphone (DPS), 4 respectively, and the standard items of 4 '-difluoro benzophenones are configured to the standard items sample of various concentration with mobile phase；S14: the determinand of known quality is taken to be diluted to solution example to be measured with mobile phase；S15: sample introduction is analyzed after instrument stabilizer, and appearance order is hydroquinone, diphenyl sulphone (DPS) and 4, and 4- difluoro benzophenone records each absorption peak；S16: fitting absorbs concentration-absorbance standard curve of peak area and standard solution, calculates contained hydroquinone, diphenyl sulphone (DPS), 4 in the determinand, the content of 4 '-three kinds of substances of difluoro benzophenone using peak area and extension rate.This method is quick, reproducible.
Description
Technical field
The present invention relates to a kind of chemical analysis method, especially a kind of PEEK sample to synthesis carries out the side of analysis detection
Method.
Background technique
Polyether-ether-ketone (Polyether Ether Ketone, abbreviation PEEK resin), i.e. PEEK is contained in backbone structure
The high polymer for having the repetitive unit of a ketonic bond and two ehter bonds to be constituted belongs to special polymer material.With high temperature resistant, resistance toization
The physical and chemical performances such as drug corrosion are learned, are a kind of crystalline polymers materials, 334 DEG C of fusing point, 168 DEG C of softening point, tensile strength
132~148MPa can be used as high temperature structural materials and electrically insulating material, can enhance with the compound preparation of glass fibre or carbon fiber
Material.Since polyether-ether-ketone PEEK has excellent comprehensive performance, the tradition such as metal, ceramics can be substituted in many special dimensions
Material.The high temperature resistants of the plastics, self-lubricating, wear-resistant and antifatigue etc. characteristics, make current most popular high-performance work
One of engineering plastics, it is mainly used in the fields such as aerospace, auto industry, electric and medical instrument.
PEEK is that '-difluoro benzophenone and hydroquinone are made molten in the presence of alkali carbonate with diphenyl sulphone (DPS) by 4,4
Agent carries out condensation reaction and is made.Simple PEEK synthesis is as follows:
After the reaction process for synthesizing PEEK in industrial production or laboratory, the reaction to synthesis PEEK is generally required
Component in system carries out quantitative detecting analysis, calculates the yield of reaction, and measure the molecular size range of polymer P EEK, is used for
Control and research to the reaction process.
But rarely have at present document report with a kind of method can detect simultaneously hydroquinone in the reaction system of synthesis PEEK,
The content of diphenyl sulphone (DPS), 4,4 '-three kinds of substances of difluoro benzophenone.Gold and jade is purple along using in " synthesis and purification of polyether-ether-ketone "
External spectrum technology measures diphenyl sulphone (DPS)；Wang Yong narration in " progress of catechol and hydroquinone detection method in water body "
The detection method of hydroquinone has chromatography, spectrophotometer and electrochemical method, and wherein chromatography accuracy is high, sensitivity
It is good；Liang Cheng describes the content that 4,4 '-difluoro benzophenones are detected with vapor phase method.It can be seen that rarely having a kind of test side at present
Method can detect the content of hydroquinone, diphenyl sulphone (DPS) and 4,4 '-difluoro benzophenones in the reaction system of synthesis PEEK simultaneously.
In addition, synthesis PEEK is after reaction, the also more difficult measurement of the molecular weight of product PEEK.PEEK material has excellent
Chemical resistance, do not influenced, be only soluble in strong or anhydrous oxidant by many organic and inorganic chemicals.J.Devaux,
The test method that D.Delimoy is used to analyze PEEK molecular weight needs to run on the mixed of trichloro-benzenes and phenol under 115 DEG C of high temperature
It closes in object, Analysis of Polymers by GPC/SEC energy&ChemiCAl APPliCAtions then records one kind
The molecular weight of PEEK is tested using the mixed solvent of dichloroacetic acid and chloroform.In two kinds of test methods, the former is to instrument
Requirement is rather harsh and mobile phase not environmentally (trichloro-benzenes can be absorbed and be more toxic through skin, and phenol is that WHO is included in the cause of 3 classes
Cancer object), requirement of the latter to temperature be unknown and chloroform not environmentally, meet illumination can be acted on the oxygen in air decompose generate it is acute
The phosgene (phosgene) and hydrogen chloride of poison.
Summary of the invention
(1) goal of the invention
In order to solve the above problem of the prior art, it is an object of the invention to provide a kind of PEEK samples to synthesis to divide
The method for analysing detection, this method can be simultaneously to hydroquinone, the diphenyl sulphone (DPS), 4 in PEEK, 4 '-three kinds of difluoro benzophenone objects
Matter carries out assay, and method detection of the invention is quick, easy to operate, reproducible, stability is high, and solvent is more environmentally friendly,
Operation temperature is thus low to instrument requirements close to room temperature.
Further, the method still further comprises the measurement to the PEEK molecular weight of synthesis, for understanding synthesis
The molecular size range and the degree of polymerization of PEEK.
(2) technical solution
In order to achieve the above object, the main technical schemes that the present invention uses include:
The method that the PEEK sample of a kind of pair of synthesis carries out analysis detection comprising, to hydroquinone, two in reaction system
Benzene sulfone and 4, the detection method of 4- difluoro benzophenone content, the operating procedure of the detection method are as follows:
S11: preparing the high performance liquid chromatograph for being furnished with UV detector and chromatographic column, and adjusting sample volume is 5 μ L, if
Set mobile phase parameter be acetonitrile/pure water=65/35 isocratic elution, be arranged flow velocity 1.0mL/min, 30 DEG C of column temperature, ultraviolet detection
Device wavelength 235nm；
S12: by acetonitrile and pure water 65/35 mixed preparing mobile phase by volume；
S13: taking appropriate hydroquinone, diphenyl sulphone (DPS), 4 respectively, and the standard items of 4 '-difluoro benzophenones are prepared with mobile phase
It is stand-by at the standard solution sample of various concentration, to obtain concentration-absorbance standard curve；
S14: taking the determinand of known quality, is diluted to solution to be measured according to certain extension rate with prepared mobile phase
Sample, it is stand-by after filtering；
S15: setting sequential parameter, sample introduction is analyzed after high performance liquid chromatograph is stablized, the appearance time of solution example to be measured
Sequence is followed successively by hydroquinone, diphenyl sulphone (DPS) and 4, and 4- difluoro benzophenone records each absorption peak by UV detector；
S16: fitting absorbs concentration-absorbance standard curve of peak area and standard solution sample, using peak area and
Extension rate calculates separately out contained hydroquinone in the determinand, diphenyl sulphone (DPS), 4,4 '-difluoro benzophenone three kinds of substances and contains
Amount.
Preferably, the chromatographic column is C18 reversed-phase column.
Preferably, in step S13, the standard solution sample concentration include 5mg/L, 50mg/L, 100mg/L,
250mg/L and 500mg/L.
Preferably, in step S14, the determinand of 4g ± 0.2g is taken, in the volumetric flask with mobile phase constant volume to 100mL, system
At solution example to be measured, organic membrane filtration is stand-by.
It according to the method for the present invention, further include detection method to the PEEK molecular weight synthesized in reaction system, the inspection
The operating procedure of survey method are as follows:
S21: preparing the gel permeation chromatograph for being furnished with Composition distribution and gel chromatographic columns, and quantitative loop is 25 μ L,
Setting sample volume is 20~40 μ L, and mobile phase parameter is dichloroacetic acid/methylene chloride=7/3~9/1 isocratic elution, setting stream
0.7~1.0mL/min of speed, analysis time: is not less than 30min by 30 DEG C of column temperature；
S22: by dichloroacetic acid and methylene chloride according to 7/3~9/1 mixed preparing mobile phase by volume；
S23: it takes the high molecular polymer standard items of three kinds of different weight average molecular weight Mw to be dissolved in mobile phase respectively, is configured to
10mg/mL standard solution sample is stand-by, to obtain equation of linear regression；
S24: taking the product PEEK of known quality to be dissolved in mobile phase, and the solution example to be measured that mass fraction is 2 ‰ is made,
It is stand-by after filtering；
S25: after gel permeation chromatograph is stablized, the analysis of standard solution sample feeding, record shows dyeing spectrogram, by GPC
Special-purpose software draws standard curve, equation of linear regression logMw=a+bRT；
Wherein, Mw is the known weight average molecular weight of standard solution sample, and RT is the retention time of standard solution sample；
S26: and then sample introduction is analyzed by solution example to be measured, record shows dyeing spectrogram, in conjunction with equation of linear regression, molecular weight
It calculates as follows:
Weight average molecular weight Mw=Σ (RIi*Mi)/Σ RIi；
Number-average molecular weight Mn=Σ RIi/ Σ (RIi/Mi)；
Coefficient of dispersion D=Mw/Mn；
Wherein, RIi is the peak height for showing dyeing spectrogram of solution example to be measured, and Mi shows dyeing spectrogram for solution example to be measured
I time point substitutes into the molecular weight of standard curve acquisition.
It preferably, is using M in step S23WThe polystyrene standards of=193000Da, 42600Da, 16200Da.
Preferably, in step S21, the types of the gel chromatographic columns is Agilent MIXED-B, 300mm × 7.5mm,
10 μm, usage quantity is 2.
Preferably, in step S24, sample is first dissolved as to 1% solution with dichloroacetic acid under the conditions of 150 DEG C, then
It is 2 ‰ sample solutions with methylene chloride dilute sample, organic membrane filtration is spare.
Preferably, step S25~S26 is executed by operation dedicated program software.
It should be noted that detection method of the invention, wherein to the detection method of PEEK molecular weight independent of to anti-
Answer contained hydroquinone, diphenyl sulphone (DPS) and 4 in system, the detection method of the content of 4- difluoro benzophenone, in other words, the two
Detection method can both use in a set of detection scheme, can also separate and individually use.
(3) beneficial effect
The beneficial effects of the present invention are:
The method of the present invention, can rapidly detect simultaneously three kinds of raw materials in the reaction system of synthesis PEEK (hydroquinone,
4,4 "-difluoro benzophenones, diphenyl sulphone (DPS)) respective content, and it is easy to operate, reproducible, relative deviation is small, stability is high；
Chromatogram column temperature is 30 DEG C in the detection process, thus lower to instrument requirements.
The method of the present invention can quickly detect weight average molecular weight, the number-average molecular weight of PEEK material, easy to operate fast
Prompt, stability height, and solvent for use (mobile phase) is more environmentally-friendly, for operation temperature close to room temperature, the requirement to instrument is lower.
Detailed description of the invention
Fig. 1 be using equipped with UV detector high performance liquid chromatograph to PEEK sample detection, successively come out to benzene
Diphenol, 4,4 '-difluoro benzophenones, the liquid chromatogram of diphenyl sulphone (DPS).
Specific embodiment
In order to preferably explain the present invention, in order to understand, with reference to the accompanying drawing, by specific embodiment, to this hair
It is bright to be described in detail.
Following example 1~4 are remaining reaction raw materials hydroquinone in PEEK, 4,4 '-difluoro benzophenones, diphenyl sulphone (DPS)
The specific embodiment of the detection method of three kinds of content of material.
Embodiment 1
(1) prepare the high performance liquid chromatograph for being furnished with UV detector, chromatographic column AQ-C18.
(2) experiment condition is arranged: sample volume is 5 μ L；Mobile phase: isocratic elution, A/B=65/35, wherein A phase is acetonitrile,
B phase is water, detector wavelength: 235nm；Flow velocity: 1.0mL/min；Column temperature: 30 DEG C；Analysis time: 18min.
(3) mobile phase A/B=65/35 is prepared, wherein A phase is acetonitrile, and B phase is water.
(4) standard items for taking appropriate hydroquinone, with mobile phase be configured to 5mg/L, 50mg/L, 100mg/L, 250mg/L,
The standard solution sample of 500mg/L.
(5) it takes the PEEK sample mobile phase constant volume of 4.0197g into the volumetric flask of 100mL, it is molten to be configured to sample to be tested
Liquid, organic membrane filtration are spare.
(6) sequential parameter is set, starts sample introduction after instrument stabilizer.It is 2.91min that hydroquinone, which goes out peak position, and standard is bent
Line is y=3.782x+16.638, R2=0.9994.Establishing criteria curve calculates the content 47.24mg/ of hydroquinone in sample
g。
Embodiment 2
(1) prepare the high performance liquid chromatograph for being furnished with UV detector, chromatographic column AQ-C18.
(2) experiment condition is arranged: sample volume is 5 μ L；Mobile phase: isocratic elution, A/B=65/35, wherein A phase is acetonitrile,
B phase is water, detector wavelength: 235nm；Flow velocity: 1.0mL/min；Column temperature: 30 DEG C；Analysis time: 18min.
(3) mobile phase A/B=65/35 is prepared, wherein A phase is acetonitrile, and B phase is water.
(4) standard items for taking appropriate diphenyl sulphone (DPS), with mobile phase be configured to 5mg/L, 50mg/L, 100mg/L, 250mg/L,
The standard solution sample of 500mg/L.
(5) it takes the PEEK sample mobile phase constant volume of 4.0197g into the volumetric flask of 100mL, it is molten to be configured to sample to be tested
Liquid, organic membrane filtration are spare.
(6) sequential parameter is set, starts sample introduction after instrument stabilizer.It is 5.76min, standard curve that diphenyl sulphone (DPS), which goes out peak position,
For y=19.578x+23.921, R2=1.Establishing criteria curve calculates the content 328.35mg/g of diphenyl sulphone (DPS) in sample.
Embodiment 3
(1) prepare the high performance liquid chromatograph for being furnished with UV detector, chromatographic column AQ-C18.
(2) experiment condition is arranged: sample volume is 5 μ L；Mobile phase: isocratic elution, A/B=65/35, wherein A phase is acetonitrile,
B phase is water, detector wavelength: 235nm；Flow velocity: 1.0mL/min；Column temperature: 30 DEG C；Analysis time: 18min.
(3) mobile phase A/B=65/35 is prepared, wherein A phase is acetonitrile, and B phase is water.
(4) appropriate 4 are taken, the standard items of 4 '-difluoro benzophenones are configured to 5mg/L, 50mg/L, 100mg/ with mobile phase
L, the standard solution sample of 250mg/L, 500mg/L.
(5) it takes the PEEK sample mobile phase constant volume of 4.0197g into the volumetric flask of 100mL, it is molten to be configured to sample to be tested
Liquid, organic membrane filtration are spare.
(6) sequential parameter is set, starts sample introduction after instrument stabilizer.The appearance time of 4,4 '-difluoro benzophenones is
8.9min, standard curve y=7.9916x+7.5675, R2=1.Establishing criteria curve calculates 4,4 '-difluorodiphenyls in sample
The content 672.61mg/g of ketone.
Embodiment 4
(1) prepare the high performance liquid chromatograph for being furnished with UV detector, chromatographic column AQ-C18.
(2) experiment condition is arranged: sample volume is 5 μ L；Mobile phase: isocratic elution, A/B=65/35, wherein A phase is acetonitrile,
B phase is water, detector wavelength: 235nm；Flow velocity: 1.0mL/min；Column temperature: 30 DEG C；Analysis time: 18min.
(3) mobile phase A/B=65/35 is prepared, wherein A phase is acetonitrile, and B phase is water.
(4) suitable hydroquinone standard items, 4,4 '-difluoro benzophenone standard items, diphenyl sulphone (DPS) standard items are taken respectively, and
The standard solution sample of 5mg/L, 50mg/L, 100mg/L, 250mg/L, 500mg/L are diluted to mobile phase.
(5) it takes the PEEK sample mobile phase constant volume of 4.0200g into the volumetric flask of 100mL, it is molten to be configured to sample to be tested
Liquid, organic membrane filtration are spare.
(6) sequential parameter is set, sample feeding 6 times, starts sample introduction after instrument stabilizer.Wherein, testing sample solution
Peak sequence is successively: hydroquinone, diphenyl sulphone (DPS) and 4,4- difluoro benzophenone, as shown in Figure 1.Hydroquinone, 4,4 '-difluoros
Benzophenone, diphenyl sulphone (DPS) appearance time be followed successively by 2.91min, 8.9min, 5.76min.The peak face of 2mg/L standard solution sample
Product is obviously different from the peak area variation tendency of other concentration.It therefore, is 5mg/L, 50mg/L, 100mg/ to standard solution sample
L, 250mg/L, 500mg/L do respective standard curve, and hydroquinone concentration versus absorbance writes music line as y=3.782x+16.638, R2
=0.9994；Diphenyl sulphone (DPS) concentration versus absorbance is write music line are as follows: y=19.578x+23.921, R2=1；4,4 '-difluoro benzophenones are dense
Degree-trap curve is y=7.9916x+7.5675, R2=1.
(7) establishing criteria curve calculates hydroquinone in sample, 4,4 '-difluoro benzophenones, the content difference of diphenyl sulphone (DPS)
For 47.05mg/g, 328.10mg/g, 672.48mg/g.RSD% is followed successively by 0.3%, 0.08%, 0.08%, and detection limit reaches
5mg/L.Specific data see the table below 1.
The repeated experiment data of 1 PEEK sample 20180323 of table
Following example 5~9 are the specific embodiment to the detection method of PEEK molecular weight in PEEK sample.
Embodiment 5
(1) prepare one be furnished with Composition distribution gel permeation chrommatograph, chromatographic column be Agilent MIXED-B, 2.
(2) experiment condition is arranged: sample volume is 20 μ L；Mobile phase: isocratic elution, A/B=7:3, wherein A phase is two chloroethenes
Acid, B phase are methylene chloride, flow velocity: 1mL/min；Column temperature: 30 DEG C；Analysis time: 30min.
(3) mobile phase A/B volume ratio=7:3 is prepared, wherein A phase is dichloroacetic acid, and B phase is methylene chloride.
(4) with flowing phase dilution weight average molecular weight MW=193000Da, 42600Da, 16200Da polystyrene, are made
10mg/L standard solution sample.
(5) sample is first dissolved as under the conditions of 150 DEG C with dichloroacetic acid 1% solution, it is then dilute with methylene chloride again
Sample is released, the testing sample solution of mass fraction 2 ‰ is made, organic membrane filtration is spare.
(6) after gel permeation chrommatograph is stablized, start hand sampling.
Record standard sample solution shows dyeing spectrogram, draws standard curve by GPC special-purpose software, equation of linear regression is
Log molecular weight=9.1845-0.3042v.
(7) by solution example to be measured, sample introduction is analyzed, and record testing sample solution shows dyeing spectrogram, in conjunction with linear regression side
Journey log molecular weight=9.1845-0.3042v, calculates the weight average molecular weight M of sampleW, number-average molecular weight Mn and coefficient of dispersion D points
It Wei not 81677Da, 38617g/mol, 2118190.
Embodiment 6
(1) prepare one be furnished with Composition distribution gel permeation chrommatograph, chromatographic column be Agilent MIXED-B, 2.
(2) experiment condition is arranged: sample volume is 40 μ L；Mobile phase: isocratic elution, A/B=9:1, wherein A phase is two chloroethenes
Acid, B phase are methylene chloride, flow velocity: 1mL/min；Column temperature: 30 DEG C；Analysis time: 30min.
(3) mobile phase A/B volume ratio=9:1 is prepared, wherein A phase is dichloroacetic acid, and B phase is methylene chloride.
(4) with flowing phase dilution weight average molecular weight MW=193000Da, 42600Da, 16200Da polystyrene, are made
10mg/L standard solution sample.
(5) sample is first dissolved as under the conditions of 150 DEG C with dichloroacetic acid 1% solution, it is then dilute with methylene chloride again
Sample is released, the testing sample solution of mass fraction 2 ‰ is made, organic membrane filtration is spare.
(6) start hand sampling after instrument stabilizer.Record standard sample solution shows dyeing spectrogram, dedicated soft by GPC
Part draws standard curve, and equation of linear regression is log molecular weight=9.3458-0.313v.
(7) by solution example to be measured, sample introduction is analyzed, and record testing sample solution shows dyeing spectrogram, in conjunction with linear regression side
Journey log molecular weight=9.3458-0.313v, calculates the weight average molecular weight M of sampleW, number-average molecular weight Mn and the coefficient of dispersion difference
For 81600Da, 38601g/mol, 2118123.
Embodiment 7
(1) prepare one be furnished with Composition distribution gel permeation chrommatograph, chromatographic column be Agilent MIXED-B, 2.
(2) experiment condition is arranged: sample volume is 40 μ L；Mobile phase: isocratic elution, A/B=8:2, wherein A phase is two chloroethenes
Acid, B phase are methylene chloride, flow velocity: 1mL/min；Column temperature: 30 DEG C；Analysis time: 30min.
(3) mobile phase A/B volume ratio=8:2 is prepared, wherein A phase is dichloroacetic acid, and B phase is methylene chloride.
(4) with flowing phase dilution weight average molecular weight MW=193000Da, 42600Da, 16200Da polystyrene, are made
10mg/L standard solution sample.
(5) sample is first dissolved as under the conditions of 150 DEG C with dichloroacetic acid 1% solution, it is then dilute with methylene chloride again
Sample is released, the testing sample solution of mass fraction 2 ‰ is made, organic membrane filtration is spare.
(6) after gel permeation chrommatograph is stablized, start hand sampling.
Record standard sample solution shows dyeing spectrogram, draws standard curve by GPC special-purpose software, equation of linear regression is
Log molecular weight=9.2756-0.3086v.
(7) by solution example to be measured, sample introduction is analyzed, and record testing sample solution shows dyeing spectrogram, in conjunction with linear regression side
Journey calculates the weight average molecular weight M of sampleW, number-average molecular weight Mn and the coefficient of dispersion be respectively 81494Da, 38475g/mol,
2118096。
Embodiment 8
(1) prepare one be furnished with Composition distribution gel permeation chrommatograph, chromatographic column be Agilent MIXED-B, 2.
(2) experiment condition is arranged: sample volume is 40 μ L；Mobile phase: isocratic elution, A/B=8:2, wherein A phase is two chloroethenes
Acid, B phase are methylene chloride, flow velocity: 0.7mL/min；Column temperature: 30 DEG C；Analysis time: 30min.
(3) prepare mobile phase A/B volume ratio=8:2, wherein A phase is dichloroacetic acid, and B phase is methylene chloride.
(4) with flowing phase dilution weight average molecular weight MW=193000Da, 42600Da, 16200Da polystyrene, are made
10mg/L standard solution sample.
(5) sample is first dissolved as under the conditions of 150 DEG C with dichloroacetic acid 1% solution, is then diluted with methylene chloride
Sample is the testing sample solution of mass fraction 2 ‰, and organic membrane filtration is spare.
(6) after gel permeation chrommatograph is stablized, start hand sampling.Record standard sample solution shows dyeing spectrogram.By GPC
Special-purpose software draws standard curve, and equation of linear regression is log molecular weight=10.434-0.3408v.
(7) by solution example to be measured, sample introduction is analyzed, and record testing sample solution shows dyeing spectrogram, in conjunction with linear regression side
Journey calculates the weight average molecular weight M of sampleW, number-average molecular weight Mn and the coefficient of dispersion be respectively 81500Da, 38499g/mol,
2118111。
Table 2 is the different eluent of embodiment 5~8 to molecular weight=193000Da, 42600Da, 16200Da polyphenyl second
The separating degree of alkene standard items.
| Eluant component and ratio | Eluent flow rate | Column temperature | Separating degree |
| Methylene chloride: dichloroacetic acid 3:7 | 1ml/min | 30℃ | 1.5 |
| Methylene chloride: dichloroacetic acid 1:9 | 1ml/min | 30℃ | 1.2 |
| Methylene chloride: dichloroacetic acid 2:8 | 1ml/min | 30℃ | 1.8 |
| Methylene chloride: dichloroacetic acid 2:8 | 0.7ml/min | 30℃ | 2.0 |
It as a result is when eluent is that dichloroacetic acid/methylene chloride is mixed according to 7/3~9/1 volume ratio, to molecular weight
Polystyrene separation degree for 193000Da, 42600Da, 16200Da is preferable, and the peak of polystyrene can be completely separable, it is ensured that
The sensitivity and stability of detection.
Claims (8)
1. a kind of method that the PEEK sample to synthesis carries out analysis detection, including to hydroquinone, hexichol in reaction system
Sulfone and 4, the detection method of 4- difluoro benzophenone content, which is characterized in that the operating procedure of the detection method are as follows:
S11: preparing the high performance liquid chromatograph for being furnished with UV detector and chromatographic column, and adjusting sample volume is 5 μ L, setting stream
Dynamic phase parameter is acetonitrile/pure water=65/35 isocratic elution, is arranged flow velocity 1.0mL/min, 30 DEG C of column temperature, UV detector wavelength
235nm；
S12: by acetonitrile and pure water 65/35 mixed preparing mobile phase by volume；
S13: taking appropriate hydroquinone, diphenyl sulphone (DPS), 4 respectively, and the standard items of 4 '-difluoro benzophenones are configured to not with mobile phase
Standard solution sample with concentration is stand-by, to obtain concentration-absorbance standard curve；
S14: taking the determinand of known quality, solution example to be measured is diluted to according to certain extension rate with mobile phase, after filtering
For use；
S15: setting sequential parameter, sample introduction is analyzed after high performance liquid chromatograph is stablized, the appearance order of solution example to be measured according to
Secondary is hydroquinone, diphenyl sulphone (DPS) and 4, and 4- difluoro benzophenone, UV detector records each absorption peak；
S16: being fitted concentration-absorbance standard curve that solution example to be measured absorbs peak area and standard solution sample, utilizes
Peak area and extension rate calculate separately out contained hydroquinone in the determinand, diphenyl sulphone (DPS), three kinds of 4,4 '-difluoro benzophenone
The content of substance.
2. the method according to claim 1, wherein the chromatographic column is C18 reversed-phase column.
3. the method according to claim 1, wherein in step S13, the standard solution sample concentration packet
Include 5 mg/L, 50 mg/L, 100 mg/L, 250 mg/L and 500mg/L.
4. the method according to claim 1, wherein the determinand of 4g ± 0.2g is taken in step S14, with flowing
Solution example to be measured is made into the volumetric flask of 100mL in phase constant volume, and organic membrane filtration is stand-by.
5. the method according to claim 1, wherein further including to the PEEK molecular weight synthesized in reaction system
Detection method, the operating procedure of the detection method are as follows:
S21: preparing the gel permeation chromatograph for being furnished with Composition distribution and gel chromatographic columns, and quantitative loop is 25 μ L, setting
Sample volume be 20 ~ 40 μ L, mobile phase parameter be dichloroacetic acid/methylene chloride=7/3 ~ 9/1 isocratic elution, setting flow velocity 0.7~
1.0mL/min, analysis time: is not less than 30min by 30 DEG C of column temperature；
S22: by dichloroacetic acid and methylene chloride according to 7/3 ~ 9/1 mixed preparing mobile phase by volume；
S23: it takes the high molecular polymer standard items of three kinds of different weight average molecular weight Mw to be dissolved in mobile phase respectively, is configured to
10mg/mL standard solution sample is stand-by, to obtain equation of linear regression；
S24: taking the product PEEK of known quality to be dissolved in mobile phase, and the solution example to be measured that mass fraction is 2 ‰ is made, filtering
It is stand-by afterwards；
S25: after gel permeation chromatograph is stablized, the analysis of standard solution sample feeding, record shows dyeing spectrogram, special by GPC
With Software on Drawing standard curve, equation of linear regression logMw=a+bRT；
Wherein, Mw is the known weight average molecular weight of standard solution sample, and RT is the retention time of standard solution sample；
S26: and then sample introduction is analyzed by solution example to be measured, record shows dyeing spectrogram, and in conjunction with equation of linear regression, molecular weight is calculated
It is as follows:
Weight average molecular weight Mw=Σ (RIi*Mi)/Σ RIi；Number-average molecular weight Mn=Σ RIi/ Σ (RIi/Mi);
Coefficient of dispersion D=Mw/Mn;
Wherein, RIi is the peak height for showing dyeing spectrogram of solution example to be measured, and Mi shows i on dyeing spectrogram for solution example to be measured
Time point substitutes into the molecular weight that standard curve obtains.
6. according to the method described in claim 5, it is characterized in that, being using M in step S23W=193000Da、42600Da、
The polystyrene standards of 16200Da.
7. according to the method described in claim 5, it is characterized in that, in step S21, the type of the gel chromatographic columns is
Agilent MIXED-B, 300mm × 7.5mm, 10 μm, usage quantity are 2.
8. according to the method described in claim 5, it is characterized in that, first using dichloroacetic acid under the conditions of 150 DEG C in step S24
Sample is dissolved as to 1% solution, is then 2 ‰ sample solutions with methylene chloride dilute sample, organic membrane filtration is spare.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114062560A (en) * | 2021-11-29 | 2022-02-18 | 中钢集团鞍山热能研究院有限公司 | High performance liquid chromatography analysis method for distribution of components with different polymerization degrees of phthalonitrile resin |
| CN114755339A (en) * | 2022-04-21 | 2022-07-15 | 湖北中烟工业有限责任公司 | Method for detecting 4, 4' -difluorobenzophenone in plastic product |
| CN114778732A (en) * | 2022-04-21 | 2022-07-22 | 湖北中烟工业有限责任公司 | Method for detecting hydroquinone in plastic product |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103808832A (en) * | 2014-03-16 | 2014-05-21 | 国家烟草质量监督检验中心 | Method for measuring main phenolic compounds in electronic cigarette liquid |
| CN105705553A (en) * | 2013-11-08 | 2016-06-22 | 阿科玛股份有限公司 | Modification of polyamides |
| CN106167545A (en) * | 2008-10-24 | 2016-11-30 | 索维高级聚合物股份有限公司 | High-purity diphenyl sulphone (DPS), its preparation and be used for preparing the purposes of poly-(aryl ether ketones) |
| CN109843974A (en) * | 2016-09-26 | 2019-06-04 | 威格斯制造有限公司 | Polymer and its manufacturing method |
-
2018
- 2018-09-05 CN CN201811031138.2A patent/CN109061026B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106167545A (en) * | 2008-10-24 | 2016-11-30 | 索维高级聚合物股份有限公司 | High-purity diphenyl sulphone (DPS), its preparation and be used for preparing the purposes of poly-(aryl ether ketones) |
| CN105705553A (en) * | 2013-11-08 | 2016-06-22 | 阿科玛股份有限公司 | Modification of polyamides |
| CN103808832A (en) * | 2014-03-16 | 2014-05-21 | 国家烟草质量监督检验中心 | Method for measuring main phenolic compounds in electronic cigarette liquid |
| CN109843974A (en) * | 2016-09-26 | 2019-06-04 | 威格斯制造有限公司 | Polymer and its manufacturing method |
Non-Patent Citations (3)
| Title |
|---|
| T.H.MOUREY 等: "Size-exclusion chromatography of nylons in methylene chloride-dichloroacetic acid", 《JOURNAL OF CHROMATOGRAPHY A》 * |
| 徐利敏 等: "聚醚醚酮的合成与表征", 《化工新型材料》 * |
| 罗忻 等: "加速溶剂萃取 － 高效液相色谱法测定高分子食品接触材料中二苯砜和 4，4’-二氯二苯砜", 《分析试验室》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114062560A (en) * | 2021-11-29 | 2022-02-18 | 中钢集团鞍山热能研究院有限公司 | High performance liquid chromatography analysis method for distribution of components with different polymerization degrees of phthalonitrile resin |
| CN114755339A (en) * | 2022-04-21 | 2022-07-15 | 湖北中烟工业有限责任公司 | Method for detecting 4, 4' -difluorobenzophenone in plastic product |
| CN114778732A (en) * | 2022-04-21 | 2022-07-22 | 湖北中烟工业有限责任公司 | Method for detecting hydroquinone in plastic product |
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