CN112229892B - Phenolic resin composition testing and quantitative analysis method and application - Google Patents
Phenolic resin composition testing and quantitative analysis method and application Download PDFInfo
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- 239000005011 phenolic resin Substances 0.000 title claims abstract description 105
- 229920001568 phenolic resin Polymers 0.000 title claims abstract description 104
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 title claims abstract description 89
- 238000012360 testing method Methods 0.000 title claims abstract description 56
- 239000000203 mixture Substances 0.000 title abstract description 50
- 238000000034 method Methods 0.000 title abstract description 19
- 238000004445 quantitative analysis Methods 0.000 title abstract description 10
- 238000010438 heat treatment Methods 0.000 claims abstract description 20
- 238000004458 analytical method Methods 0.000 claims abstract description 14
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 69
- 238000000434 field desorption mass spectrometry Methods 0.000 claims description 67
- 229920005989 resin Polymers 0.000 claims description 48
- 239000011347 resin Substances 0.000 claims description 48
- 229920001187 thermosetting polymer Polymers 0.000 claims description 36
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 26
- -1 methylol groups Chemical group 0.000 claims description 20
- 238000001228 spectrum Methods 0.000 claims description 17
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 16
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 16
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 16
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 15
- 150000002500 ions Chemical class 0.000 claims description 10
- 230000001133 acceleration Effects 0.000 claims description 9
- 229920001169 thermoplastic Polymers 0.000 claims description 9
- 239000004416 thermosoftening plastic Substances 0.000 claims description 9
- XKZQKPRCPNGNFR-UHFFFAOYSA-N 2-(3-hydroxyphenyl)phenol Chemical group OC1=CC=CC(C=2C(=CC=CC=2)O)=C1 XKZQKPRCPNGNFR-UHFFFAOYSA-N 0.000 claims description 8
- 150000001793 charged compounds Chemical class 0.000 claims description 8
- 229910052788 barium Inorganic materials 0.000 claims description 7
- 239000003153 chemical reaction reagent Substances 0.000 claims description 6
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 5
- CQOZJDNCADWEKH-UHFFFAOYSA-N 2-[3,3-bis(2-hydroxyphenyl)propyl]phenol Chemical group OC1=CC=CC=C1CCC(C=1C(=CC=CC=1)O)C1=CC=CC=C1O CQOZJDNCADWEKH-UHFFFAOYSA-N 0.000 claims description 4
- 239000002798 polar solvent Substances 0.000 claims description 4
- OOBDZXQTZWOBBQ-UHFFFAOYSA-N hexaphenol Chemical group C1C2=CC(O)=C(O)C=C2CC2=CC(O)=C(O)C=C2CC2=C1C=C(O)C(O)=C2 OOBDZXQTZWOBBQ-UHFFFAOYSA-N 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- XQPRBTXUXXVTKB-UHFFFAOYSA-M caesium iodide Chemical compound [I-].[Cs+] XQPRBTXUXXVTKB-UHFFFAOYSA-M 0.000 claims description 2
- UVNKQUXHHOZJLS-UHFFFAOYSA-N 2-undecylphenol Chemical group CCCCCCCCCCCC1=CC=CC=C1O UVNKQUXHHOZJLS-UHFFFAOYSA-N 0.000 claims 4
- 238000004364 calculation method Methods 0.000 abstract description 6
- 230000003595 spectral effect Effects 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 16
- 239000000463 material Substances 0.000 description 12
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 9
- 238000005227 gel permeation chromatography Methods 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 238000004321 preservation Methods 0.000 description 6
- 238000005259 measurement Methods 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 238000009210 therapy by ultrasound Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 229920003986 novolac Polymers 0.000 description 4
- 229920005992 thermoplastic resin Polymers 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000000539 dimer Substances 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- SLGWESQGEUXWJQ-UHFFFAOYSA-N formaldehyde;phenol Chemical compound O=C.OC1=CC=CC=C1 SLGWESQGEUXWJQ-UHFFFAOYSA-N 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 238000010907 mechanical stirring Methods 0.000 description 3
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 239000011342 resin composition Substances 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 238000002679 ablation Methods 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 2
- 229910001863 barium hydroxide Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000011033 desalting Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000013638 trimer Substances 0.000 description 2
- 230000000007 visual effect Effects 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- DPTHFGSQSGEHEW-UHFFFAOYSA-N C=O.C1(=CC=CC=C1)O.[Ba] Chemical compound C=O.C1(=CC=CC=C1)O.[Ba] DPTHFGSQSGEHEW-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000019771 cognition Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
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- 238000010276 construction Methods 0.000 description 1
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- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 238000002270 exclusion chromatography Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
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- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000003880 polar aprotic solvent Substances 0.000 description 1
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- 230000008569 process Effects 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- CQRYARSYNCAZFO-UHFFFAOYSA-N salicyl alcohol Chemical compound OCC1=CC=CC=C1O CQRYARSYNCAZFO-UHFFFAOYSA-N 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 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
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/62—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating the ionisation of gases, e.g. aerosols; by investigating electric discharges, e.g. emission of cathode
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Phenolic Resins Or Amino Resins (AREA)
Abstract
本发明提供了一种酚醛树脂组成测试和定量分析方法，采用软电离的特征离子源、合适的扫描速率、扫描间隔、灯丝加热速率、离子化电压等测试参数，确保了测试得到的谱图信噪比高、稳定性好；本发明提出的数据计算方法具有数据准确、算法简单、重现性好、稳定可靠的特点，适合用作酚醛树脂的组成和分子量特征分析的定量分析。
The invention provides a method for testing and quantitative analysis of the composition of phenolic resin, which adopts the characteristic ion source of soft ionization, suitable scanning rate, scanning interval, heating rate of filament, ionization voltage and other test parameters, so as to ensure the spectral information obtained by the test. High noise ratio and good stability; the data calculation method proposed by the invention has the characteristics of accurate data, simple algorithm, good reproducibility, stability and reliability, and is suitable for quantitative analysis of composition and molecular weight characteristic analysis of phenolic resin.
Description
Technical Field
The invention relates to a phenolic resin composition testing and quantitative analysis method and application, which can be used for determining phenolic resin composition characteristics and molecular weight and belongs to the field of quantitative measurement.
Background
Phenolic resin is a kind of high molecular materials prepared by the addition condensation reaction between phenols and aldehydes, has developed nearly 150 years since the first synthesis of the resin in the laboratory by Bayer, German scientist in 1872, and belongs to one of the most widely synthesized high molecular materials with the earliest human knowledge. The phenolic resin has a series of excellent properties, such as high temperature resistance, high carbon residue, excellent dimensional stability, flame retardant property, low smoke toxicity and the like. Therefore, phenolic resin is widely used in the fields of construction (such as thermal insulation materials), transportation (such as aircrafts and vehicle interior parts), metallurgy (such as refractory materials) and the like, and is also the matrix resin of the most common ablation heat-proof composite material in national defense and aerospace industries.
By changing the reaction conditions such as the molar ratio of the phenolic compound and the aldehyde compound as raw materials, and the type of the catalyst (acid or base), a thermoplastic phenol resin and a thermosetting phenol resin can be prepared, respectively, and the synthetic route and the molecular structural characteristics of the resins are illustrated in fig. 1. As can be seen from fig. 1, the degree of polymerization (n) and the number of methylol groups (m, k, h), etc. of the phenolic resin are variable, and the methylene group between the phenol rings may be in the para-or ortho-position to the phenolic hydroxyl group. Therefore, the thermoplastic phenolic resin and the thermosetting phenolic resin are all mixtures composed of different polymerization degrees and different isomer components. Their composition is very complex, especially in the case of thermosetting phenol resins, the number of methylol groups on the capped phenol ring may be 1 or 2, and may also contain a small number of ether bond structures, thereby resulting in a more complex resin composition and structure, so that the determination of the composition and definite structure of the phenol resin has hitherto been a recognized technical problem.
The molecular structure of phenolic resins is often characterized qualitatively based on their structural and compositional complexity, for example, infrared spectroscopy (FT-IR) is commonly used to identify the phenolic hydroxyl, methylene, and methylol functional groups in the resin, but it is difficult to quantify these groups. The average molecular weight of the phenolic resin and the content of hydroxymethyl and methylene can be tested by using nuclear magnetic resonance spectroscopy (NMR); however, the obtained characteristics are overall characteristics based on the average composition of the resin, and more definite composition characteristics such as relative contents of trimers, tetramers and the like in the phenolic novolak resin cannot be obtained.
Gel Permeation Chromatography (GPC) is a commonly used technique for characterizing polymer composition, molecular weight, and molecular weight distribution. The technical means is volume exclusion chromatography, the molecular weight and the distribution of a sample are mainly distinguished through the size of molecular volume, different components are distinguished through the leaching time, and the method is a very effective technical means. For GPC for measuring molecular weight of phenolic resin, polystyrene is generally used as a standard, the molecular weight obtained by the measurement is relative molecular weight to the standard, not absolute molecular weight of a sample, and the difference in polarity between the phenolic resin and the polystyrene results in a large difference in molecular weight of the resin obtained by GPC measurement from its true molecular weight due to the large polarity of the molecule and the non-polarity of the polystyrene. In addition, although GPC can distinguish between free phenol, monohydroxymethylphenol, and dimers in the resin, as the degree of polymerization of the components increases, the difference in molecular volume is not large, the elution times between the components overlap, and it is difficult to distinguish between them with the separation efficiency of the column, and components such as trimers, tetramers, and pentamers in the phenol-formaldehyde-thermoplastic resin are broad peaks in the GPC curve and cannot be distinguished, and it is more difficult to quantify the relative contents of components having different degrees of polymerization. In addition, in order to ensure the separation efficiency, the GPC test time is generally about 40 minutes, and the test efficiency is also to be improved.
In summary, the current technical means for testing the composition of phenolic resins, especially GPC, has significant disadvantages. How to rapidly and efficiently measure the relative content of components with different polymerization degrees in the phenolic resin and to determine the composition characteristics of the resin still is a technical problem to be solved urgently.
Disclosure of Invention
The invention aims to overcome the defects in the prior art, and provides a phenolic resin composition testing and quantitative analysis method, which is used for obtaining visual spectrograms of components with different polymerization degrees and different substitution degrees of phenolic resin, calculating the relative content of the components in the phenolic resin and realizing the rapid and efficient determination of the composition characteristics of the thermoplastic phenolic resin.
The above object of the present invention is achieved by the following technical solutions:
according to one embodiment of the present invention, there is provided a method of testing the composition of a phenolic resin, comprising the steps of:
the ion source temperature is room temperature, the scanning mass range is 80-1200 u, the scanning speed is 1-5s/d, the scanning interval is 0.2-0.6s, the heating speed of the emission wire is 9-10mA/min, preferably 9.5mA/min, the ionization voltage is 4.5-5.0kV, preferably 4.8kV, and the acceleration voltage is 4.5-5.0kV, preferably 4.8 kV.
According to one embodiment of the invention, the mass spectrometer is a German Thermo Fisher DFS high resolution dual focus magnetic mass spectrometer.
According to an embodiment of the present invention, the aprotic polar solvent in step 1 is one of acetone, Tetrahydrofuran (THF), N-Dimethylformamide (DMF), or Dimethylsulfoxide (DMSO), preferably THF or DMF; wherein the preferred solvent is chromatographically pure, guaranteed reagent or standard reagent.
According to one embodiment of the invention, the mass spectrometer is mass calibrated with one of PFK (perfluorokerosene), cesium iodide or UltraMark.
According to one embodiment of the invention, the peak at m/z 58 of acetone is tuned to the strongest at the TUNE window.
According to an embodiment of the present invention, the present invention provides a method for quantitatively analyzing a composition of a phenolic resin, including the following steps:
the ion source temperature is room temperature, the scanning mass range is 80-1200 u, the scanning speed is 1-5s/d, the scanning interval is 0.2-0.6s, the heating speed of the emission wire is 9-10mA/min, preferably 9.5mA/min, the ionization voltage is 4.5-5.0kV, preferably 4.8kV, and the acceleration voltage is 4.5-5.0kV, preferably 4.8 kV;
and 3, obtaining source data of an FD-MS spectrogram according to the test conditions, determining the relative abundance of molecular ion peaks of each phenol ring component in the phenolic resin, calculating the relative content of the phenol ring component according to the proportion of the relative abundance of the molecular ion peaks of each phenol ring component in the relative abundance of the total component, and further calculating the average molecular weight of the resin.
According to an embodiment of the present invention, each of the phenol ring components of step 3 includes a monophenol ring component, a diphenol ring component, a trishenol ring component, a tetraphenol ring component, a pentaphenol ring component, a hexaphenol ring component, a heptaphenol ring component, an octaphenol ring component, a nonaphenol ring component, a decaphenol ring component, up to an undecaphenol ring component;
the monophenol ring component is defined as Am 1With a relative abundance of RAm 1The diphenol ring component is defined as Am 2With a relative abundance of RAm 2The triphenol ring component is defined as Am 3With a relative abundance of RAm 3And so on until the undecaphenol ring component is defined as Am 11With a relative abundance of RAm 11；Am 1The relative content of the components is defined as Cm 1，Am 2The relative content of the components is defined as Cm 2，Am 3The relative content of the components is defined as Cm 3And so on until the undecaphenol ring group Am 11Relative content of Cm 11；Am 1The molecular weight of the component Mm 1，Am 2The molecular weight of the component Mm 2，Am 3Molecules of ComponentsAmount is Mm 3And so on until the undecaphenol ring group Am 11Has a molecular weight of Mm 11。
According to an embodiment of the present invention, the relative amounts of the phenolic ring components of the phenolic resin are determined according to equation (1):
Cm n＝RAm n/(RAm 1+RAm 2+……+RAm 11) (1)
n in formula (1) is 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, which represents the number of phenolic rings in components containing different numbers of phenolic rings in the phenolic resin; m is 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12; m represents the number of methylol groups attached to components containing different numbers of phenolic rings, wherein the phenolic resin does not contain methylol groups (m ═ 0), and the thermosetting phenolic resin has m ≧ 1.
According to an embodiment of the present invention, the average Molecular Weight (MW) of the phenolic resin is determined according to formula (2):
MW＝Mm 1×Cm 1+Mm 2×Cm 2+……+Mm 10×Cm 11 (2)。
the invention has the beneficial effects that:
(1) the method for testing and analyzing by using the field desorption mass spectrometry (FD-MS) can definitely give the molecular ion peaks of each component in the phenolic resin, and the spectrogram is visual, simple and clear and is easier to analyze. Compared with the traditional mass spectrum, the energy required for analyzing the composition molecules of the sample adsorbed on the filament in the FD-MS is far lower than the gasification energy of the sample, the C-C bond of the molecule cannot be broken, so that a fragment peak is not generated, the molecular ion peak of the composition molecules of the sample is intuitively provided by a spectrogram, and the molecular weight of the molecules can be directly read.
(2) The FD-MS testing and analyzing method provided by the invention defines typical parameters of a testing instrument, including scanning rate, scanning interval, heating rate of the emitting wire and the like, can ensure that a spectrogram with high signal-to-noise ratio and high quality is obtained, and can ensure the accuracy and stability of a quantitative calculation result.
(3) The FD-MS testing and analyzing method provided by the invention has the advantages of simple sample preparation, convenient operation, high detection speed and high efficiency, and has obvious advantages in determining the composition characteristics (including the relative content of each phenol ring component and the average molecular weight of the phenolic resin) of the phenolic resin.
Drawings
FIG. 1 is a schematic diagram of a phenolic resin synthesis route and a molecular structure;
FIG. 2 is a field desorption mass spectrometry (FD-MS) spectrum of a typical phenol-formaldehyde thermoplastic resin (PF-8020) in example 1;
FIG. 3 is a field desorption mass spectrometry (FD-MS) spectrum of a typical phenol novolac resin (PF-8013) in example 2;
FIG. 4 is a field desorption mass spectrometry (FD-MS) spectrum of the high purity phenolic resin of example 3;
FIG. 5 is a field desorption mass spectrometry (FD-MS) spectrum of the thermosetting barium-phenolic resin of example 4;
FIG. 6 is a field desorption mass spectrometry (FD-MS) spectrum of a typical thermosetting phenol resin (BaPF) in example 5.
Detailed Description
The method and application of the present invention will be described in further detail with reference to specific examples. It is to be understood that the following examples are only illustrative and explanatory of the present invention and should not be construed as limiting the scope of the present invention. All the technologies realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.
Unless otherwise indicated, the raw materials and reagents used in the following examples are all commercially available products or can be prepared by known methods.
The invention relates to a method for testing and quantitatively analyzing the composition characteristics, the relative content and the average molecular weight of components of phenolic resin, which comprises the following steps:
Preferably, in one embodiment of the present invention, the organic solvent used is one of acetone, Tetrahydrofuran (THF), N-Dimethylformamide (DMF), dimethyl sulfoxide (DMSO), preferably THF, DMF; wherein the preferred solvent is chromatographically pure, guaranteed reagent or standard reagent.
Preferably, in one embodiment of the present invention, the concentration of the formulated phenolic resin test sample is preferably 16-35mg/mL, and specifically may be 16mg/mL, 20mg/mL, 22mg/mL, 25mg/mL, 30mg/mL or 35 mg/mL.
According to the method for testing the composition, the relative content and the molecular weight of the phenolic resin, provided by the invention, by adopting the characteristic ion source of soft ionization, proper scanning rate, scanning interval, filament heating rate, ionization voltage and other testing parameters during FD-MS testing, the high signal-to-noise ratio and the good stability of a spectrogram obtained by testing are ensured; the data calculation method provided by the invention has the characteristics of accurate data, simple algorithm, good reproducibility, stability and reliability, and is suitable for quantitative analysis of the composition and molecular weight characteristic analysis of the phenolic resin.
The invention also provides a quantitative analysis method for the composition of the phenolic resin, which comprises the following steps:
and 3, obtaining an FD-MS spectrogram by the testing method, and determining the component characteristics, the component content and the average molecular weight of the phenolic resin according to the FD-MS spectrogram.
Specifically, according to the determined molecular ion peaks of the components of the phenolic resin, the relative content of the components is calculated by combining the FD-MS spectrogram relative abundance of the molecular ion peaks, and the molecular weight of the resin is further calculated.
In one embodiment, the relative amounts of each component described in step 3 comprise:
determining the relative contents of the components of the phenolic resin according to the formula (1):
Cm n＝RAm n/(RAm 1+RAm 2+……+RAm 11) (1)
in one embodiment, determining the average Molecular Weight (MW) of the phenolic resin from the FD-MS spectrum of step 3 comprises:
the average Molecular Weight (MW) of the phenolic novolac resin is determined according to formula (2):
MW＝Mm 1×Cm 1+Mm 1×Cm 1+……+Mm 10×Cm 11 (2)
in the formula:
the monophenol ring component is defined as Am 1And its relative abundance is defined as RAm 1The diphenol ring component is defined as Am 2With a relative abundance of RAm 2The triphenol ring component is defined as Am 3With a relative abundance of RAm 3And so on until the undecaphenol ring component is defined as Am 11With a relative abundance of RAm 11；
Am 1The relative content of the components is defined as Cm 1，Am 2The relative content of the components is defined as Cm 2，Am 3The relative content of the components is defined as Cm 3And so on until the undecaphenol ring group Am 11Relative content of Cm 11；Am 1The molecular weight of the component Mm 1，Am 2The molecular weight of the component Mm 2，Am 3The molecular weight of the component Mm 3And so on until the undecaphenol ring group Am 11Has a molecular weight of Mm 11。
n-1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, which represent components of different numbers of phenolic rings in the phenolic resin; m is 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, representing the number of methylol groups attached to the components of varying number of phenolic rings, wherein the phenolic thermoplastic resin does not contain methylol groups and thus m is 0, and the phenolic thermosetting resin is 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12.
The method can simply, quickly and comprehensively determine the composition, the relative content of each component and the average molecular weight characteristics of the phenolic resin. The following are several specific embodiments of the invention:
example 1
The measurement of FD-MS spectrogram of a sample of a thermoplastic phenolic resin (available from the Fukeda corporation, Inc., having a softening point of 105-.
(1) Preparation of test samples
Placing a PF-8020 resin sample in a sample bottle, drying in an oven at 105 ℃ for 30 minutes to remove water absorbed in the sample bottle, cooling the sample bottle by a dryer, and grinding the dried sample bottle into fine powder. Taking chromatographic pure Tetrahydrofuran (THF), measuring 10mL, and adding into a sample dissolving bottle; weighing 200mg of PF-8020 powder sample, dissolving in 10mL of THF, performing ultrasonic treatment to completely dissolve the sample, and preparing into a solution with a concentration of 20mg/mL for later use.
(2) FD-MS spectrogram test
The FD-MS spectrogram of PF-8020 resin is tested by adopting a German Thermo Fisher DFS high-resolution double-focusing magnetic mass spectrometer, and the test parameters are as follows:
the ion source temperature is room temperature, the scanning mass range is 80-1200 u, the scanning speed is 1s/d, the scanning interval is 0.6s, the heating speed of the emission wire is 9.5mA/min, the ionization voltage is 4.8kV, and the acceleration voltage is 4.8 kV.
The above test was completed to obtain an FD-MS spectrum of the PF-8020 sample.
(3) Spectrogram analysis and data processing
And (3) carrying out quantitative analysis on the FD-MS spectrogram to determine the composition characteristics of the PF-8020 resin, the relative content of the components containing different numbers of phenol rings and the average molecular weight of the resin.
PF-8020 is a phenol-formaldehyde thermoplastic resin which is composed of components having different numbers of phenolic rings and does not contain a methylol group in its molecular structure, i.e., m is 0, and its FD-MS spectrum is shown in FIG. 2 and its composition characteristics are shown in Table 1.
TABLE 1 PF-8020 resin of example 1 having different amounts of phenolic ring-containing components and molecular weights
As described above, the relative percentages of components containing different amounts of phenolic rings in the PF-8020 resin can be determined from Table 1 and the results show that the resin is characterized by the composition: the resin is basically free of free phenol (monophenol ring component), the content of diphenol ring components with low molecular weight is only 7.63%, three, four, five and hexaphenol ring components account for the main part, and meanwhile, the resin contains more heptaphenol ring components and octaphenol ring components with high molecular weight, and the calculated average molecular weight of the resin is 577.30.
Example 2
The measurement of FD-MS spectrogram of a sample of thermoplastic phenolic resin (available from the Furan corporation of the Shengquan group of Jinan, No. PF-8013, softening point 89-94 ℃) and the calculation of the component characteristics, the relative contents of the components and the average molecular weight thereof.
(1) Preparation of test samples
Placing a PF-8013 resin sample in a sample bottle, drying in an oven at 105 ℃ for 30 minutes to remove water absorbed in the sample bottle, cooling the sample bottle by a dryer, and grinding into fine powder. Taking chromatographic pure N, N-Dimethylformamide (DMF), measuring 10mL, and adding into a sample dissolving bottle; weighing 250mg of PF-8013 powder sample, dissolving in 10mL of THF, and performing ultrasonic treatment to completely dissolve the sample to prepare a solution with a concentration of 25mg/mL for later use.
(2) FD-MS spectrogram test
The FD-MS spectrogram of PF-8013 resin is tested by adopting a German Thermo Fisher DFS high-resolution double-focusing magnetic mass spectrometer, and the test parameters are as follows:
the ion source temperature is room temperature, the scanning mass range is 80-1200 u, the scanning speed is 5s/d, the scanning interval is 0.2s, the heating speed of the emission wire is 9.5mA/min, the ionization voltage is 4.8kV, and the acceleration voltage is 4.8 kV.
The above test was completed to obtain an FD-MS spectrum of the PF-8013 sample.
(3) Spectrogram analysis and data processing
And quantitatively analyzing the FD-MS spectrogram to determine the composition characteristics of the PF-8013 resin, the relative contents of the components containing different numbers of phenol rings and the average molecular weight of the resin.
PF-8013 is a phenol novolac resin, which is composed of components with different phenolic ring contents, and has no methylol group in the molecular structure, i.e., m ═ 0, and its FD-MS spectrum is shown in fig. 3, and its composition characteristics are shown in table 2.
TABLE 2 PF-8013 resin of example 2 contains different amounts of phenolic rings and has different molecular weights
As described above, the relative percentages of components having different numbers of phenolic rings in PF-8013 resin can be determined from Table 2, and the results show that the resin is characterized by the following composition: the resin contains a small amount of free phenol (monophenol ring component), the highest content of diphenol ring components with low molecular weight reaches 23.50%, the secondary, tertiary, quaternary and pentaphenol ring components account for the main part, and the low content of hepta-, octa-and nonaphenol ring components with high molecular weight, and the average molecular weight of the resin is calculated to be low and is 439.27.
Example 3
The FD-MS spectrogram of a high-purity phenolic resin sample (with the softening point of 80-85 ℃) self-made by the chemical research institute of Chinese academy of sciences is measured, and the component characteristics, the relative content of each component and the average molecular weight are calculated.
(1) Preparation of thermoplastic high-purity phenolic resin prepared by chemical industry
Adding 94.11 g of phenol, 64.04 g of formaldehyde and 1.58 g of oxalic acid into a 250mL three-neck flask equipped with a mechanical stirring device, a thermometer and a condenser tube, and stirring for 10 minutes to uniformly mix the materials; and heating the reaction materials by adopting an oil bath, raising the temperature to 70 ℃ after 30 minutes, carrying out heat preservation reaction for 1.5 hours, further raising the temperature to 85 ℃, and continuing the heat preservation reaction for 2 hours. After the reaction, deionized water was added, the mixture was washed with water to neutrality, and the aqueous layer was aspirated. Heating the materials to 60 ℃, starting to dewater under reduced pressure for 3 hours, heating the materials to 83 ℃, and finishing the reaction to obtain 103.4 g of white solid blocky high-purity phenolic resin.
(2) Preparation of test samples
Placing a high-purity phenolic resin sample in a sample bottle, drying in an oven at 105 ℃ for 30 minutes, removing water absorbed in the sample bottle, cooling in a dryer, and grinding into fine powder. Taking chromatographic pure acetone, measuring 10mL, and adding into a sample dissolving bottle; 160mg of a high-purity phenolic resin powder sample is weighed and dissolved in 10mL of THF, the sample is completely dissolved through ultrasonic treatment, and a solution with the concentration of 16mg/mL is prepared for later use.
(3) FD-MS spectrogram test
The FD-MS spectrogram of PF-8013 resin is tested by adopting a German Thermo Fisher DFS high-resolution double-focusing magnetic mass spectrometer, and the test parameters are as follows:
the ion source temperature is room temperature, the scanning mass range is 80-1200 u, the scanning speed is 3s/d, the scanning interval is 0.4s, the heating speed of the emission wire is 9.5mA/min, the ionization voltage is 4.8kV, and the acceleration voltage is 4.8 kV.
The test is completed, and an FD-MS spectrogram of a high-purity phenolic resin sample prepared by the institute of chemistry of Chinese academy of sciences is obtained.
(4) Spectrogram analysis and data processing
And (3) carrying out quantitative analysis on the FD-MS spectrogram to determine the composition characteristics of the high-purity phenolic resin, the relative content of the components containing different numbers of phenolic rings and the average molecular weight of the resin.
The high-purity phenolic resin is thermoplastic phenolic resin which is composed of components with different phenolic ring contents, does not contain hydroxymethyl in a molecular structure, namely m is 0, and has an FD-MS spectrum shown in figure 4 and composition characteristics shown in Table 3.
Table 3 example 3 the high purity phenolic resin in example 3 contains components with different amounts of phenolic rings and molecular weights
As noted above, the relative percentages of the components containing different numbers of phenolic rings in the high purity phenolic resin can be determined from Table 3 and the results show that the resin is characterized by the composition: the high-purity phenolic resin contains a small amount of low-molecular free phenol (monophenol ring component) and a diphenol ring component (15.05%), wherein medium-molecular-weight tri-, tetra-and penta-phenol ring components account for the main part, the total content of the components is highest and reaches 65.69% cumulatively, meanwhile, the high-molecular-weight 6-11 phenol ring component is less and has a total content of 18.83%, the distribution characteristics of the components lay a foundation for excellent technological performance and ablation performance of the high-purity phenolic resin, and the average molecular weight of the high-purity phenolic resin is 429.75 through further calculation.
Example 4
The FD-MS spectrogram of a thermosetting barium-phenolic resin sample prepared by the institute of chemistry of the Chinese academy of sciences is measured, and the component characteristics, the relative content of each component and the average molecular weight of each component are calculated.
(1) And (3) preparing thermosetting phenolic resin.
188.22 g of phenol, 256.25 g of formaldehyde and 4.7 g of barium hydroxide are taken and added into a 1000mL three-neck flask with a mechanical stirring device, a thermometer and a condenser pipe, and the mixture is stirred for 20 minutes to uniformly mix the materials; and heating the reaction materials by adopting an oil bath, raising the temperature to 55 ℃ after 30 minutes, carrying out heat preservation reaction for 1.0 hour, further raising the temperature to 80 ℃, and continuing the heat preservation reaction for 2 hours. After the reaction is finished, adding phosphoric acid for neutralization, neutralizing, filtering and desalting. Heating the mixture to raise the temperature of the material to 60 ℃, starting to dehydrate under reduced pressure for 2 hours, raising the temperature of the material to 75 ℃, continuing to dehydrate for 40 minutes, and ending the reaction to obtain 225.6 grams of thermosetting barium-phenolic resin.
(2) Preparation of test samples
Taking chromatographic pure acetone, measuring 10mL, and adding into a sample dissolving bottle; 350mg of thermosetting phenolic resin powder sample is weighed and dissolved in the 10mL of dimethyl sulfoxide (DMSO), the sample is completely dissolved through ultrasonic treatment, and a solution with the concentration of 35mg/mL is prepared for standby.
(3) FD-MS spectrogram test
The FD-MS spectrogram of the thermosetting phenolic resin is tested by adopting a German Thermo Fisher DFS high-resolution double-focusing magnetic mass spectrometer, and the test parameters are as follows:
the ion source temperature is room temperature, the scanning mass range is 80-1200 u, the scanning speed is 4s/d, the scanning interval is 0.3s, the heating speed of the emission wire is 9.5mA/min, the ionization voltage is 4.8kV, and the acceleration voltage is 4.8 kV.
The above test was completed to obtain an FD-MS spectrum of the thermosetting barium phenolic resin.
(4) Spectrogram analysis and data processing
And quantitatively analyzing the FD-MS spectrogram to determine the composition characteristics of the thermosetting barium-phenolic resin, the relative content of the components containing different numbers of phenolic rings and the average molecular weight of the resin.
The thermosetting barium phenolic resin is a thermosetting phenolic resin and consists of components with different phenolic ring numbers and different hydroxymethyl substitution numbers, an FD-MS spectrogram of the thermosetting barium phenolic resin is shown in figure 5, and the composition characteristics are shown in table 4.
TABLE 4 example 4 thermosetting barium phenol-formaldehyde resin having different content of components having different phenolic rings and different number of methylol groups and molecular weight
The component in Table 4 in which m is 0 means the unreacted free phenol in the system.
As described above, the relative percentages of the components containing different amounts of phenolic rings and substituted by different amounts of methylol groups in the thermosetting barium phenolic resin can be determined from Table 4 and the results show that the resin has a compositional profile of: the polymerization degree of the thermosetting phenolic resin is relatively small, and the thermosetting phenolic resin only contains four phenolic rings at most and has little content; the highest content of diphenol ring components not containing hydroxymethyl functional groups is 33.47%; the hydroxymethyl-substituted monophenol ring-containing component accounts for the main part of the resin composition, and the cumulative content thereof is 48.65%; the higher molecular weight hydroxymethyl-substituted tri-and tetraphenol ring components are present in a small amount, amounting to only 2.85%, resulting in a low average molecular weight of only 192.75 for the thermosetting phenolic resin.
Example 5
The method comprises the steps of measuring an FD-MS spectrogram of a thermosetting barium-phenolic resin (BaPF) sample, and calculating the component characteristics, the relative content of each component and the average molecular weight of the sample, wherein the FD-MS spectrogram is manufactured by the institute of chemistry of Chinese academy of sciences.
(1) Preparation of thermosetting phenol formaldehyde resin (BaPF).
Adding 94.11 g of phenol, 128 g of formaldehyde and 2.35 g of barium hydroxide into a 500mL three-neck flask equipped with a mechanical stirring device, a thermometer and a condenser tube, and stirring for 20 minutes to uniformly mix the materials; and heating the reaction materials by adopting an oil bath, raising the temperature to 55 ℃ after 30 minutes, carrying out heat preservation reaction for 1.0 hour, further raising the temperature to 80 ℃, and continuing the heat preservation reaction for 2 hours. After the reaction is finished, adding phosphoric acid for neutralization, neutralizing, filtering and desalting. Heating the mixture to 60 ℃, starting to dehydrate the mixture under reduced pressure for 2.0 hours, heating the mixture to 80 ℃, continuing to dehydrate the mixture for 60 minutes, and finishing the reaction to obtain 110 g of thermosetting barium-phenolic resin (BaPF).
(2) Preparation of test samples
Taking chromatographic pure acetone, measuring 10mL, and adding into a sample dissolving bottle; 220mg of BaPF resin sample is weighed and dissolved in 10mL of N, N-dimethyl Diamide (DMF), and the sample is completely dissolved by ultrasonic treatment to prepare a solution with the concentration of 22mg/mL for later use.
(3) FD-MS spectrogram test
The FD-MS spectrogram of the thermosetting phenolic resin is tested by adopting a German Thermo Fisher DFS high-resolution double-focusing magnetic mass spectrometer, and the test parameters are as follows:
the ion source temperature is room temperature, the scanning mass range is 80-1200 u, the scanning speed is 3s/d, the scanning interval is 0.5s, the heating speed of the emission wire is 9.5mA/min, the ionization voltage is 4.8kV, and the acceleration voltage is 4.8 kV.
The above test was completed to obtain an FD-MS spectrum of a thermosetting phenol resin (BaPF).
(4) Spectrogram analysis and data processing
The FD-MS spectra were quantitatively analyzed to determine the compositional characteristics of the thermosetting phenol-formaldehyde resin (BaPF), the relative amounts of the components containing different numbers of phenolic rings, and the average molecular weight of the resin.
The thermosetting phenol resin (BaPF) is composed of components having different numbers of phenol rings, and has a molecular structure containing a large number of thermally crosslinkable methylol functional groups, and its FD-MS spectrum is shown in fig. 6, and its composition characteristics are shown in table 5.
TABLE 5 relative amounts of components containing different phenolic rings and substituted with different numbers of methylol groups and their average molecular weights in thermosetting phenol-formaldehyde (BaPF) resins of example 5
The component in Table 5 in which m is 0 means the unreacted free phenol in the system.
As described above, the relative percentages of the different amounts of phenolic rings substituted by different amounts of methylol groups in the chemically prepared thermosetting phenolic resins can be determined from Table 5, and the results show that the resins are characterized by the following composition:
the resin is mainly composed of hydroxymethyl-containing oligomer, wherein hydroxymethyl-substituted dimer is the main part of the resin, and the content of the hydroxymethyl-substituted dimer reaches 58.36%; the second highest content is hydroxymethyl substituted monophenol ring component, and the content of the hydroxymethyl substituted monophenol ring component is 30.02 percent; the highest molecular weight component was the hydroxymethyl-substituted triphenol ring component, but the content was low, only 8.22%. Overall, BaPF phenolic resin consists of low phenolic ring number oligomers with a low molecular weight, calculated as the relative amounts of the components, of 248.4.
Compared with the thermosetting barium phenolic aldehyde in the embodiment 4, the thermosetting barium phenolic aldehyde (BaPF) resin prepared in the embodiment has the same feeding ratio, but the dehydration condition is strengthened, so that the content of the high-molecular component in the prepared BaPF resin is improved, the average molecular weight of the resin is increased, the conventional cognition is met, the influence of the process parameters on the resin composition characteristics is reflected, and the effectiveness of the test method provided by the invention is verified.
From the test and calculation results of the above examples, it can be seen that the field desorption mass spectrometry (FD-MS) test and analysis method provided by the present invention is applicable to both thermoplastic phenolic resins and thermosetting phenolic resins, and can clearly and efficiently determine the phenolic resin composition, the relative content of each component, and the average molecular weight information.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. 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.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1212021A (en) * | 1996-01-23 | 1999-03-24 | 拉普吉恩公司 | Method and compositions for determining sequence of nucleic acid molecules |
| CN108918572A (en) * | 2018-06-22 | 2018-11-30 | 航天材料及工艺研究所 | A kind of phenolic resin dactylotype test method and quantitative analysis method |
-
2020
- 2020-10-22 CN CN202011142466.7A patent/CN112229892B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1212021A (en) * | 1996-01-23 | 1999-03-24 | 拉普吉恩公司 | Method and compositions for determining sequence of nucleic acid molecules |
| CN108918572A (en) * | 2018-06-22 | 2018-11-30 | 航天材料及工艺研究所 | A kind of phenolic resin dactylotype test method and quantitative analysis method |
Non-Patent Citations (9)
| Title |
|---|
| Direct Mass Spectrometric Analysis of Phenol-Formaldehyde Oligocondensates: A Comparative Desorption Ionization Study;Laszlo Prokai等;《Macromolecules》;19921231;全文 * |
| Investigation of Phenol-Formaldehyde Condensates by Field Desorption Mass Spectrometry;LASZLO PRdKAI等;《Journal of Polymer Science: Part C: Polymer Letters》;19861231;全文 * |
| Liquid injection field desorption/ionization of reactive transition metal complexes;Jürgen H. Gross等;《Anal Bioanal Chem》;20060614;全文 * |
| Preparation and characterization of a self‐catalyzed fluorinated novolac‐phthalonitrile resin;Zheng Li等;《Polym Adv Technol》;20180211;全文 * |
| 场解吸离子源在质谱中的应用;辽宁省理化测试中心质谱组;《分析测试通报》;19830331;全文 * |
| 王娟等.酚醛树脂分子量及分布场解吸质谱表征方法研究.《高分子学报》.2012,(第2期),第103-110页. * |
| 聚硅氧烷的合成与分析研究;王彦琳;《中国优秀硕士学位论文全文数据库 工程科技I辑》;20181115(第11期);正文第46、55页 * |
| 苯酚-多聚甲醛热固性酚醛树脂合成反应过程研究;王娟等;《高分子学报》;20131031(第10期);全文 * |
| 酚醛树脂分子量及分布场解吸质谱表征方法研究;王娟等;《高分子学报》;20121231(第2期);第103-110页 * |
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