CN115406984A - Method suitable for simultaneously analyzing various bisphenol compounds in building materials - Google Patents
Method suitable for simultaneously analyzing various bisphenol compounds in building materials Download PDFInfo
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- CN115406984A CN115406984A CN202210987588.9A CN202210987588A CN115406984A CN 115406984 A CN115406984 A CN 115406984A CN 202210987588 A CN202210987588 A CN 202210987588A CN 115406984 A CN115406984 A CN 115406984A
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- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 title claims abstract description 91
- 238000000034 method Methods 0.000 title claims abstract description 52
- 239000004566 building material Substances 0.000 title claims abstract description 42
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 75
- 238000004128 high performance liquid chromatography Methods 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000004458 analytical method Methods 0.000 claims abstract description 12
- 238000000227 grinding Methods 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 229930185605 Bisphenol Natural products 0.000 claims description 52
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 claims description 28
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 claims description 26
- PVFQHGDIOXNKIC-UHFFFAOYSA-N 4-[2-[3-[2-(4-hydroxyphenyl)propan-2-yl]phenyl]propan-2-yl]phenol Chemical compound C=1C=CC(C(C)(C)C=2C=CC(O)=CC=2)=CC=1C(C)(C)C1=CC=C(O)C=C1 PVFQHGDIOXNKIC-UHFFFAOYSA-N 0.000 claims description 25
- 238000010828 elution Methods 0.000 claims description 23
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 claims description 22
- BATCUENAARTUKW-UHFFFAOYSA-N 4-[(4-hydroxyphenyl)-diphenylmethyl]phenol Chemical compound C1=CC(O)=CC=C1C(C=1C=CC(O)=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 BATCUENAARTUKW-UHFFFAOYSA-N 0.000 claims description 22
- VKOUCJUTMGHNOR-UHFFFAOYSA-N Diphenolic acid Chemical compound C=1C=C(O)C=CC=1C(CCC(O)=O)(C)C1=CC=C(O)C=C1 VKOUCJUTMGHNOR-UHFFFAOYSA-N 0.000 claims description 22
- GIXXQTYGFOHYPT-UHFFFAOYSA-N Bisphenol P Chemical compound C=1C=C(C(C)(C)C=2C=CC(O)=CC=2)C=CC=1C(C)(C)C1=CC=C(O)C=C1 GIXXQTYGFOHYPT-UHFFFAOYSA-N 0.000 claims description 16
- ZFVMWEVVKGLCIJ-UHFFFAOYSA-N bisphenol AF Chemical compound C1=CC(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C=C1 ZFVMWEVVKGLCIJ-UHFFFAOYSA-N 0.000 claims description 15
- 238000000926 separation method Methods 0.000 claims description 15
- VOWWYDCFAISREI-UHFFFAOYSA-N Bisphenol AP Chemical compound C=1C=C(O)C=CC=1C(C=1C=CC(O)=CC=1)(C)C1=CC=CC=C1 VOWWYDCFAISREI-UHFFFAOYSA-N 0.000 claims description 14
- HCNHNBLSNVSJTJ-UHFFFAOYSA-N 1,1-Bis(4-hydroxyphenyl)ethane Chemical compound C=1C=C(O)C=CC=1C(C)C1=CC=C(O)C=C1 HCNHNBLSNVSJTJ-UHFFFAOYSA-N 0.000 claims description 13
- OWEYKIWAZBBXJK-UHFFFAOYSA-N 1,1-Dichloro-2,2-bis(4-hydroxyphenyl)ethylene Chemical compound C1=CC(O)=CC=C1C(=C(Cl)Cl)C1=CC=C(O)C=C1 OWEYKIWAZBBXJK-UHFFFAOYSA-N 0.000 claims description 13
- HTVITOHKHWFJKO-UHFFFAOYSA-N Bisphenol B Chemical compound C=1C=C(O)C=CC=1C(C)(CC)C1=CC=C(O)C=C1 HTVITOHKHWFJKO-UHFFFAOYSA-N 0.000 claims description 13
- SDDLEVPIDBLVHC-UHFFFAOYSA-N Bisphenol Z Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)CCCCC1 SDDLEVPIDBLVHC-UHFFFAOYSA-N 0.000 claims description 12
- 229920005989 resin Polymers 0.000 claims description 11
- 239000011347 resin Substances 0.000 claims description 11
- 239000003822 epoxy resin Substances 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 10
- 229920000647 polyepoxide Polymers 0.000 claims description 10
- 239000012086 standard solution Substances 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- -1 bisphenol compound Chemical class 0.000 claims description 8
- 229920001568 phenolic resin Polymers 0.000 claims description 8
- 229920002492 poly(sulfone) Polymers 0.000 claims description 8
- 229920005668 polycarbonate resin Polymers 0.000 claims description 8
- 239000004431 polycarbonate resin Substances 0.000 claims description 8
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 7
- 238000001514 detection method Methods 0.000 claims description 7
- 239000005011 phenolic resin Substances 0.000 claims description 7
- 238000013375 chromatographic separation Methods 0.000 claims description 6
- 230000003247 decreasing effect Effects 0.000 claims description 5
- 238000002137 ultrasound extraction Methods 0.000 claims description 5
- 238000010521 absorption reaction Methods 0.000 claims description 4
- 239000000945 filler Substances 0.000 claims description 4
- 238000002347 injection Methods 0.000 claims description 4
- 239000007924 injection Substances 0.000 claims description 4
- YTJSFYQNRXLOIC-UHFFFAOYSA-N octadecylsilane Chemical compound CCCCCCCCCCCCCCCCCC[SiH3] YTJSFYQNRXLOIC-UHFFFAOYSA-N 0.000 claims description 4
- 238000004445 quantitative analysis Methods 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 230000014759 maintenance of location Effects 0.000 claims description 3
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 2
- 229920000570 polyether Polymers 0.000 claims description 2
- 238000004451 qualitative analysis Methods 0.000 claims description 2
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 15
- 239000007788 liquid Substances 0.000 description 14
- 230000000694 effects Effects 0.000 description 6
- 229920001225 polyester resin Polymers 0.000 description 6
- 239000004645 polyester resin Substances 0.000 description 6
- 239000011159 matrix material Substances 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 238000011084 recovery Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 229920000515 polycarbonate Polymers 0.000 description 4
- 239000004417 polycarbonate Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000007865 diluting Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 description 1
- JOOXCMJARBKPKM-UHFFFAOYSA-N 4-oxopentanoic acid Chemical class CC(=O)CCC(O)=O JOOXCMJARBKPKM-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 239000000556 agonist Substances 0.000 description 1
- 230000001833 anti-estrogenic effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000005548 dental material Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229940011871 estrogen Drugs 0.000 description 1
- 239000000262 estrogen Substances 0.000 description 1
- 230000001076 estrogenic effect Effects 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- YLQWCDOCJODRMT-UHFFFAOYSA-N fluoren-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3C2=C1 YLQWCDOCJODRMT-UHFFFAOYSA-N 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 125000004464 hydroxyphenyl group Chemical group 0.000 description 1
- 229920006150 hyperbranched polyester Polymers 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000013332 literature search Methods 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
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- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 210000001685 thyroid gland Anatomy 0.000 description 1
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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
- G01N30/26—Conditioning of the fluid carrier; Flow patterns
- G01N30/28—Control of physical parameters of the fluid carrier
- G01N30/34—Control of physical parameters of the fluid carrier of fluid composition, e.g. gradient
-
- 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
- G01N30/62—Detectors specially adapted therefor
- G01N30/74—Optical detectors
-
- 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
- G01N30/86—Signal analysis
- G01N30/8624—Detection of slopes or peaks; baseline correction
- G01N30/8631—Peaks
- G01N30/8634—Peak quality criteria
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- Physics & Mathematics (AREA)
- Biochemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Engineering & Computer Science (AREA)
- Quality & Reliability (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for simultaneously analyzing a plurality of bisphenol compounds in building materials, which can simultaneously separate and analyze fourteen bisphenol compounds in 40min through single operation, and the specific scheme is as follows: the bisphenol compounds in the building material to be detected are extracted by grinding and ultrasonic wave assistance, and are analyzed by adopting a high performance liquid chromatography, and when the high performance liquid chromatography is adopted for analysis, a mobile phase is generated by mixing a mobile phase A and a mobile phase B on line through a gradient elution program, wherein the mobile phase A is methanol, and the mobile phase B is water.
Description
Technical Field
The invention relates to the technical field of environmental analytical chemistry, in particular to a method suitable for simultaneously analyzing various bisphenol compounds in building materials.
Background
The statements in this section merely provide background information related to the present disclosure and may not necessarily constitute prior art.
Bisphenols (BPs) are a class of compounds formed by connecting two hydroxyphenyl functional groups through a bridging carbon or other chemical structure, and include twenty kinds of analogs, such as bisphenol a (BPA), bisphenol S (BPs), bisphenol F (BPF), bisphenol AF (BPAF), diphenolic acid (DPA), bisphenol E (BPE), bisphenol B (BPB), bisphenol AP (BPAP), bisphenol C (BPC), bisphenol fluorene (BPFL, DHPF), bisphenol Z (BPZ), bisphenol BP (BPBP), bisphenol M (BPM), and bisphenol P (BPP). Among them, the toxicity, the standard of use restriction and the analytical method of bisphenol A, bisphenol S, bisphenol F, bisphenol AF and the like are known, and the research thereof has been made or has been paid attention to by researchers. Therefore, in order to avoid the production of such chemicals, other bisphenol components having similar structures (e.g., bisphenol acids, bisphenol fluorenes, bisphenol BP, bisphenol M, etc.) are increasingly used as substitutes. However, the analytical methods, toxicity and biological and environmental impact of these alternatives have not been clarified. Therefore, the development of analysis methods for components such as diphenolic acid, bisphenol fluorene, bisphenol BP and bisphenol M becomes a precondition for the intensive research on human health and potential environmental pollution.
It is reported that diphenolic acid is an important derivative of levulinic acid, and the diphenolic acid serving as an organic synthesis intermediate and a monomer of a high polymer is mainly applied to preparation of high polymer materials such as epoxy resin, polycarbonate, water-soluble resin, hyperbranched polyester and the like. Bisphenol fluorene is a bisphenol compound with Cardo skeleton structure prepared by condensation reaction of 9-fluorenone and phenol as raw materials in the presence of an acid catalyst. The structure of the polymer is unique, so that the heat resistance of the polymer can be improved, and the polymer has good chemical properties and formability, and also has the characteristics of excellent transparency, high refractive index, easy dissolution and the like, so that the polymer becomes a raw material or an improver for synthesizing novel heat-resistant polycarbonate, epoxy resin and polyester. However, bisphenol fluorene has been found to have a strong antiestrogenic effect. Bisphenol BP is used in the production of flame retardants, polycarbonate plastic articles and furniture. However, studies have shown that bisphenol BP is an estrogen agonist with even greater estrogenic potency than bisphenol a. Bisphenol M is useful in the production of thermoplastics, polycarbonate plastic articles and dental materials. Bisphenol M also has strong thyroid interference effect. At present, the high performance liquid chromatography analysis method for simultaneously analyzing fourteen bisphenol compounds including diphenolic acid, bisphenol fluorene, bisphenol BP and bisphenol M has not been reported yet. As a result of literature search, although nine types of bisphenol compounds such as bisphenol a, bisphenol F, bisphenol B, bisphenol E, bisphenol AF, bisphenol S, bisphenol AP, bisphenol Z, and bisphenol C can be analyzed by High Performance Liquid Chromatography (HPLC), no methods for analyzing bisphenol components including bisphenol acid, bisphenol fluorene, bisphenol BP, and bisphenol M, which are monomers of bisphenol components that can be eluted from building materials, have been reported.
Further, chinese patent No. CN111198242a discloses a method for measuring bisphenol compounds in food simulants, and specifically discloses detection of bisphenol compounds BPA, BPF, BPB, BPC, BPS, TBBPA, BPAF, BPE, BPG, DMBPA, BPOPPA, BPAP, BPBP, BPP, but the above-mentioned schemes cannot detect bisphenol S (BPS), diphenolic acid (DPA), bisphenol F (BPF), bisphenol E (BPE), bisphenol a (BPA), bisphenol B (BPB), bisphenol AF (BPAF), bisphenol AP (BPAP), bisphenol C (BPC), bisphenol fluorene (BPFL), bisphenol Z (BPZ), bisphenol BP (BPBP), bisphenol M (BPM), and bisphenol P (BPP) at the same time. However, the inventor finds that: due to the different types of bisphenol compounds, the method is not suitable for simultaneously analyzing a plurality of bisphenol compounds in the building materials.
Disclosure of Invention
In view of the defects of the prior art, the present invention provides a method for simultaneously analyzing a plurality of bisphenol compounds in building materials, which is capable of simultaneously separating and analyzing fourteen bisphenol compounds including bisphenol S (BPS), diphenolic acid (DPA), bisphenol F (BPF), bisphenol E (BPE), bisphenol a (BPA), bisphenol B (BPB), bisphenol AF (BPAF), bisphenol AP (BPAP), bisphenol C (BPC), bisphenol fluorene (BPFL), bisphenol Z (BPZ), bisphenol BP (BPBP), bisphenol M (BPM) and bisphenol P (BPP) in a single run within 40min.
In order to achieve the purpose, the invention is realized by the following technical scheme:
a method suitable for simultaneously analyzing various bisphenol compounds in building materials is characterized in that bisphenol compounds in building materials to be detected are extracted by grinding and ultrasonic wave assistance, and are analyzed by a high performance liquid chromatography;
the building material comprises phenolic resin, epoxy resin, polycarbonate resin, polysulfone resin and polyether resin;
the bisphenol compounds include bisphenol S (BPS), diphenolic acid (DPA), bisphenol F (BPF), bisphenol E (BPE), bisphenol a (BPA), bisphenol B (BPB), bisphenol AF (BPAF), bisphenol AP (BPAP), bisphenol C (BPC), bisphenol fluorene (BPFL), bisphenol Z (BPZ), bisphenol BP (BPBP), bisphenol M (BPM), and bisphenol P (BPP);
when the high performance liquid chromatography is adopted for analysis, the mobile phase is generated by mixing a mobile phase A and a mobile phase B on line through a gradient elution program, wherein the mobile phase A is methanol, and the mobile phase B is water;
the procedure of gradient elution is 0-3min, and the mobile phase A is kept at 45%;3-18min, increasing the mobile phase A from 45% to 80%; keeping the mobile phase A for 80% for 18-25 min; the mobile phase A is decreased from 80% to 45% in 25-33 min; 33-40min, mobile phase a remains 45%, and mobile phase a + mobile phase B =100% in the procedure of gradient elution.
The mobile phase is generated by mixing methanol and water on line. The experimental results show that compared with acetonitrile/water, the separation effect of methanol/water is better: when acetonitrile/water is the mobile phase, the components cannot be separated efficiently, although the elution time of the bisphenols is relatively advanced. When 70% acetonitrile/30% water is used as a mobile phase, the bisphenol compounds cannot be completely separated; when 60% acetonitrile/40% water is used as a mobile phase, BPAF and BPAP, and BPP and BPM cannot be separated; when 50% acetonitrile/50% water was used as the mobile phase, the separation was still impossible and the elution time exceeded 40min.
The gradient elution procedure when methanol and water are mobile phase is as described above. The experimental results show that: when 70% methanol/30% water is used as a mobile phase, the separation effect is best, but the BPS and the DPA cannot be separated, the elution time of the BPM and the BPP exceeds 35min, but the BPS and the DPA can be separated by 45% methanol/55% water, and the elution time of the BPM and the BPP is within 12min when 80% methanol/20% water is used as the mobile phase; further gradient elution procedures (methanol ratios from 40%, 45%, 50% to 75%, 80%, 85%) showed that the best gradient elution procedure was from 45% to 80% methanol and other gradient elution procedures had unstable baseline or less than 1.5 degrees of separation of BPS and DPA, BPM and BPP.
Further, the chromatographic column used in the high performance liquid chromatography is a reverse phase chromatographic column; the detector is an ultraviolet visible absorption detector.
Further, the reverse phase chromatographic column is an octadecylsilane chemically bonded silica chromatographic column, the specification of the chromatographic column is 250mm multiplied by 4.6mm, and the particle size of the filler is 5 μm.
Further, it is characterized in that the detection wavelength of the detector is 218-238nm, preferably 228nm.
Further, grinding the building material to be detected to the particle size of 200-300 meshes, wherein the solvent used for ultrasonic-assisted extraction is methanol, and the mass volume ratio of the sample solvent is 0.1g:1mL, 30min time, 25 ℃.
Further, the high performance liquid chromatography comprises: and (3) preparing a standard solution from a standard substance of the target component for chromatographic separation, wherein the retention time of a chromatographic peak of the obtained standard solution is the basis for qualitative analysis of the component in the building material sample to be detected, the peak area of the chromatographic peak of the obtained standard solution is the basis for quantitative analysis of the component in the building material sample to be detected, and the standard curve method is adopted for quantitative analysis.
Further, when a standard solution is prepared by using a standard substance of a target component for chromatographic separation, the separation degree of any two components obtained by chromatographic separation of fourteen standard substance standard solutions is more than 1.5, and baseline separation is realized.
Further, it is characterized in that the flow rate of the gradient elution procedure is 0.5-1.5mLmin -1 Preferably 1mLmin -1 。
Further characterized in that the column temperature of the gradient elution procedure is 25-35 ℃, preferably 30 ℃.
Further, it is characterized in that the injection volume of the gradient elution procedure is 5-10 μ L, preferably 10 μ L.
The beneficial effects of the invention are as follows:
1) The invention provides a high performance liquid chromatography analysis method suitable for simultaneously analyzing fourteen bisphenol compounds such as free DPA, BPFL, BPBP and BPM in building materials, which realizes simultaneous detection of the fourteen bisphenol compounds through a specific elution program, has good separation effect, can simultaneously separate and analyze fourteen bisphenol compounds (the separation degree is more than 1.5) within 40min through single operation, and has strong reproducibility and simple operation.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate exemplary embodiments of the invention and together with the description serve to explain the invention and not to limit the invention.
Fig. 1 is a schematic chemical structure diagram of fourteen bisphenol compounds in one embodiment of the present invention.
FIG. 2 shows 1mg L of the first embodiment of the present invention -1 High performance liquid chromatogram of fourteen bisphenol compounds.
FIG. 3 shows 1mg L of the second embodiment of the present invention -1 High performance liquid chromatograms of fourteen bisphenols in different matrices (3 a: matrix is water, 3b: matrix is methanol).
FIG. 4 is a high performance liquid chromatogram of bisphenol components in phenolic resin in example III of the present invention.
FIG. 5 is a high performance liquid chromatogram of bisphenol component in epoxy resin in example four of the present invention.
FIG. 6 is a high performance liquid chromatogram of bisphenol component in polycarbonate resin in example V of the present invention.
FIG. 7 is a high performance liquid chromatogram of bisphenol component in polyester resin according to example six of the present invention.
FIG. 8 is a high performance liquid chromatogram of bisphenol components in polysulfone resin in example seven of the present invention.
Detailed Description
It is to be understood that the following detailed description is exemplary and is intended to provide further explanation of the invention as claimed. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the invention. As used herein, the singular forms "a", "an", and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof;
for convenience of description, the words "up", "down", "left" and "right" in the present invention, if any, merely indicate correspondence with the directions of up, down, left and right of the drawings themselves, and do not limit the structure, but merely facilitate the description of the invention and simplify the description, rather than indicate or imply that the device or element referred to must have a particular orientation, be constructed and operated in a particular orientation, and therefore should not be construed as limiting the invention.
The term interpretation section: the terms "mounted," "connected," "fixed," and the like in the present invention are to be understood in a broad sense, and for example, the terms "mounted," "connected," and "fixed" may be fixed, detachable, or integrated; the two components can be connected mechanically or electrically, directly or indirectly through an intermediate medium, or connected internally or in an interaction relationship, and the terms used in the present invention should be understood as having specific meanings to those skilled in the art.
The invention aims to provide a high performance liquid chromatography analysis method suitable for simultaneously analyzing fourteen bisphenol compounds such as free diphenolic acid, bisphenol fluorene, bisphenol BP, bisphenol M and the like in building materials, which can simultaneously separate and analyze the fourteen bisphenol compounds by single operation within 40min. The bisphenol compounds include bisphenol S (BPS), diphenolic acid (DPA), bisphenol F (BPF), bisphenol E (BPE), bisphenol a (BPA), bisphenol B (BPB), bisphenol AF (BPAF), bisphenol AP (BPAP), bisphenol C (BPC), bisphenol fluorene (BPFL), bisphenol Z (BPZ), bisphenol BP (BPBP), bisphenol M (BPM), and bisphenol P (BPP).
In order to achieve the above object, the present invention provides the following technical solutions:
(1) Grinding the building material to be detected into particles;
(2) And (2) placing the granular building material to be detected obtained in the step (1) into a brown glass bottle, adding methanol, and extracting the bisphenol components in the granular building material by an ultrasonic-assisted extraction method.
(3) And (3) performing centrifugal separation on the extracting solution obtained in the step (2).
(4) Filtering the supernatant obtained in the step (3) by using a needle filter, and diluting the filtrate by using methanol.
(5) And (4) injecting the solution to be detected obtained in the step (4) into a high performance liquid chromatography, and determining the content of the bisphenol component in the building material to be detected by adopting a gradient elution program.
In the step (1), the building material to be tested comprises phenolic resin, epoxy resin, polycarbonate resin, polyester resin and polysulfone resin.
In the step (2), the particle size of the granular building material to be detected is 200-300 meshes, and the mass is 0.1g; the volume of the methanol is 1mL; the ultrasonic-assisted extraction method has ultrasonic time of 30min and temperature of 25 deg.C.
In the step (3), the rotation speed of the centrifugation is 4000rpm, and the time is 3min.
In the step (4), the needle type filter is a 0.22 mu m polytetrafluoroethylene needle type filter; diluted 10 (or 50) fold with methanol.
In the step (5), the chromatographic column of the high performance liquid chromatography is an octadecylsilane chemically bonded silica chromatographic column, the specification is 250mm multiplied by 4.6mm, and the particle size of the filler is 5 mu m;
the detector is an ultraviolet visible absorption detector, and the detection wavelength is 218-238nm, preferably 228nm;
gradient elution procedure is 0-3min, mobile phase A is kept 45%;3-18min, increasing the mobile phase A from 45% to 80%; keeping the mobile phase A for 80% for 18-25 min; the mobile phase A is decreased from 80% to 45% in 25-33 min; 33-40min, mobile phase a remains 45% (mobile phase a is methanol, mobile phase B is water, mobile phase a + mobile phase B = 100%);
furthermore, the column temperature of the gradient elution procedure is 25-35 ℃, preferably 30 ℃;
the flow rate of the gradient elution procedure is 0.5-1.5mL min -1 Preferably, it is 1mL min -1 ；
The injection volume for the gradient elution procedure is 5-10. Mu.L, preferably 10. Mu.L.
Example one
A high performance liquid chromatography analysis method suitable for simultaneously analyzing fourteen bisphenol compounds such as free diphenolic acid, bisphenol fluorene, bisphenol BP, bisphenol M and the like in building materials adopts the following high performance liquid chromatography conditions: the chromatographic column adopts an octadecylsilane chemically bonded silica reverse chromatographic column, the specification is 250mm multiplied by 4.6mm, and the particle size of the filler is 5 mu m; the detector adopts an ultraviolet visible absorption detector, and the detection wavelength is 228nm; the mobile phase adopts a mobile phase A and a mobile phase B, wherein the mobile phase A is methanol, and the mobile phase B is water; a gradient elution procedure was used: keeping the mobile phase A for 45% in 0-3 min; 3-18min, increasing the mobile phase A from 45% to 80%; keeping the mobile phase A for 80% for 18-25 min; the mobile phase A is decreased from 80% to 45% in 25-33 min; 33-40min, mobile phase a remains 45% (mobile phase a + mobile phase B = 100%); the column temperature is 30 ℃; flow rate 1mL min -1 (ii) a The injection volume was 10. Mu.L.
The method for measuring the content of the bisphenol component in the building material to be measured comprises the following steps:
(1) Grinding the building material to be detected to particles with the particle size of 200-300 meshes;
(2) And (2) placing 0.1g of the granular building material to be detected obtained in the step (1) into a brown glass bottle, adding 1mL of methanol, and extracting the bisphenol component in the granular building material by ultrasonic for 30min (at the temperature of 25 ℃) by adopting an ultrasonic-assisted extraction method.
(3) And (3) carrying out centrifugal separation on the extracting solution obtained in the step (2) at the rotating speed of 4000rpm for 3min.
(4) Filtering the supernatant obtained in the step (3) by using a 0.22 mu m polytetrafluoroethylene needle filter, and diluting the filtrate by 10 times by using methanol.
(5) And (4) injecting the solution to be tested obtained in the step (4) into a high performance liquid chromatography to determine the content of the bisphenol component in the building material to be tested.
As shown in figure 2, the separation degree of the invention is more than 1.5, the separation effect is good, and the fourteen bisphenol compounds can be simultaneously separated and analyzed by single operation within 40min.
The method has the following analysis performance:
TABLE 1 Retention time, degree of separation and tailing factor
TABLE 2 Linear Range, regression equation, regression coefficients, detection limits, quantitation limits, and relative Standard deviations
a C BPs ＝0.05mg L -1 ,n＝7.
Example two
The difference between this embodiment and the first embodiment is: the matrix is different
Following the procedures and conditions described in example one, the matrix of the sample was replaced with water, resulting in a high performance liquid chromatogram as shown in FIG. 3 a.
EXAMPLE III
Following the procedure and conditions described in example one, the matrix of the sample was replaced with methanol, resulting in a high performance liquid chromatogram as shown in FIG. 3 b.
As can be seen from the comparison of FIGS. 2, 3a and 3b, when the sample is based on methanol/water (45%: 55%), the separation effect is the best and the peak pattern is better; as can be seen from FIG. 3a, the peak intensity is lower when the sample is based on water; as can be seen from FIG. 3b, the peak intensity was slightly decreased when the sample was methanol-based.
Example four
Determining bisphenol components in the phenolic resin:
the measurements were performed according to the procedure and conditions described in example one and the phenol formaldehyde resins were subjected to a standard recovery test, the results of which are shown in table 3.
TABLE 3 determination of bisphenol component in phenolic resin
a n.d.: not detected.
The high performance liquid chromatogram of the bisphenol component in the phenolic resin shown in FIG. 4 was obtained.
EXAMPLE five
Determination of bisphenol components in epoxy resins:
the measurements were carried out according to the procedure and conditions described in example one and the epoxy resins were subjected to a standard recovery test, the results of which are shown in Table 4.
TABLE 4 determination of bisphenol component in epoxy resin
a n.d.: not detected.
The high performance liquid chromatogram of the bisphenol component in the epoxy resin shown in FIG. 5 was obtained.
EXAMPLE six
Determination of bisphenol component in polycarbonate resin:
the chromatographic conditions and procedures described in example one were followed and the polycarbonate resin was subjected to a standard recovery test with the results shown in Table 5.
TABLE 5 determination of bisphenol component in polycarbonate resin
a n.d.: not detected.
A high performance liquid chromatogram of the bisphenol component in the medium polycarbonate resin was obtained as shown in FIG. 6.
EXAMPLE seven
Determination of bisphenol component in polyester resin:
the chromatographic conditions and procedures described in example one were followed and the polyester resin was subjected to a standard recovery test with the results shown in Table 6.
TABLE 6 determination of bisphenol component in polyester resin
a n.d.: not detected.
The high performance liquid chromatogram of the bisphenol component in the medium polyester resin shown in FIG. 7 was obtained.
Example eight
Determining bisphenol components in the polysulfone resin:
the chromatographic conditions and procedures described in example one were followed and the polysulfone resin was subjected to a standard recovery test with the results shown in Table 7.
TABLE 7 determination of bisphenol component in polysulfone resin
a n.d.: not detected.
The high performance liquid chromatogram of the bisphenol component in the polysulfone resin shown in FIG. 8 was obtained.
Therefore, the invention provides a high performance liquid chromatography analysis method suitable for simultaneously analyzing fourteen bisphenol compounds such as free DPA, BPFL, BPBP and BPM in the building materials, and is applied to separating and analyzing the content of bisphenol components in the building materials to be detected.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A method suitable for simultaneously analyzing a plurality of bisphenol compounds in building materials is characterized in that the bisphenol compounds in the building materials to be detected are extracted by grinding and ultrasonic wave assistance, and are analyzed by a high performance liquid chromatography;
the building material comprises phenolic resin, epoxy resin, polycarbonate resin, polysulfone resin and polyether resin;
the bisphenol compound comprises bisphenol S, diphenolic acid, bisphenol F, bisphenol E, bisphenol A, bisphenol B, bisphenol AF, bisphenol AP, bisphenol C, bisphenol fluorene, bisphenol Z, bisphenol BP, bisphenol M and bisphenol P;
when the high performance liquid chromatography is adopted for analysis, the mobile phase is generated by mixing a mobile phase A and a mobile phase B on line through a gradient elution program, wherein the mobile phase A is methanol, and the mobile phase B is water;
the gradient elution procedure is 0-3min, and the mobile phase A is kept at 45%;3-18min, increasing the mobile phase A from 45% to 80%; keeping the mobile phase A at 80% for 18-25 min; the mobile phase A is decreased from 80% to 45% in 25-33 min; 33-40min, mobile phase a remains 45%, and mobile phase a + mobile phase B =100% in the procedure of gradient elution.
2. The method for simultaneously analyzing a plurality of bisphenol compounds in building materials according to claim 1, wherein the chromatographic column used in the high performance liquid chromatography is a reverse phase chromatographic column; the detector is an ultraviolet visible absorption detector.
3. The method as claimed in claim 2, wherein the reverse phase chromatographic column is an octadecylsilane chemically bonded silica chromatographic column, the specification of the chromatographic column is 250mm x 4.6mm, and the particle size of the filler is 5 μm.
4. The method for simultaneously analyzing a plurality of bisphenol compounds in building materials according to claim 2, wherein the detection wavelength of the detector is 218-238nm, preferably 228nm.
5. The method for simultaneously analyzing a plurality of bisphenol compounds in building materials according to claim 1, wherein the building material to be tested is ground to have a particle size of 200-300 meshes, the solvent used in the ultrasonic-assisted extraction is methanol, and the mass volume ratio of the sample solvent is 0.1g:1mL, 30min time, 25 ℃.
6. The method for simultaneously analyzing a plurality of bisphenol compounds in building materials according to claim 1, wherein the high performance liquid chromatography comprises: and (3) preparing a standard solution from a standard substance of the target component for chromatographic separation, wherein the retention time of a chromatographic peak of the obtained standard solution is the basis for qualitative analysis of the component in the building material sample to be detected, the peak area of the chromatographic peak of the obtained standard solution is the basis for quantitative analysis of the component in the building material sample to be detected, and the standard curve method is adopted for quantitative analysis.
7. The method as claimed in claim 6, wherein when the standard solution is prepared from the standard substance of the target component for chromatographic separation, the resolution of any two components obtained by chromatographic separation of the fourteen standard solutions is greater than 1.5, and baseline separation is achieved.
8. The method as claimed in claim 1, wherein the flow rate of the gradient elution procedure is 0.5-1.5mLmin -1 Preferably 1mLmin -1 。
9. The method for simultaneously analyzing a plurality of bisphenol compounds in building materials according to claim 1, wherein the column temperature of the gradient elution procedure is 25-35 ℃, preferably 30 ℃.
10. The method for simultaneously analyzing a plurality of bisphenol compounds in building materials according to claim 1, wherein the sample injection volume of the gradient elution procedure is 5-10 μ L, preferably 10 μ L.
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