CN117092057A - Method for testing MQ ratio in MQ silicon resin - Google Patents
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- 238000000034 method Methods 0.000 title claims abstract description 33
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 29
- 239000010703 silicon Substances 0.000 title claims abstract description 28
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 229920005989 resin Polymers 0.000 title claims abstract description 25
- 239000011347 resin Substances 0.000 title claims abstract description 25
- 238000012360 testing method Methods 0.000 title claims abstract description 9
- 238000010521 absorption reaction Methods 0.000 claims abstract description 52
- 238000002329 infrared spectrum Methods 0.000 claims abstract description 38
- 229910002808 Si–O–Si Inorganic materials 0.000 claims abstract description 26
- 238000011088 calibration curve Methods 0.000 claims abstract description 19
- 229920002050 silicone resin Polymers 0.000 claims description 34
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 14
- 229920001296 polysiloxane Polymers 0.000 claims description 10
- 229910004283 SiO 4 Inorganic materials 0.000 claims description 4
- 238000010586 diagram Methods 0.000 claims description 4
- 229910003849 O-Si Inorganic materials 0.000 claims description 3
- 229910003872 O—Si Inorganic materials 0.000 claims description 3
- 238000005452 bending Methods 0.000 claims description 3
- 238000001514 detection method Methods 0.000 claims description 3
- 229920000734 polysilsesquioxane polymer Polymers 0.000 claims description 3
- VNRWTCZXQWOWIG-UHFFFAOYSA-N tetrakis(trimethylsilyl) silicate Chemical compound C[Si](C)(C)O[Si](O[Si](C)(C)C)(O[Si](C)(C)C)O[Si](C)(C)C VNRWTCZXQWOWIG-UHFFFAOYSA-N 0.000 claims description 3
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 3
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 abstract 1
- 235000019353 potassium silicate Nutrition 0.000 description 8
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 8
- 238000004566 IR spectroscopy Methods 0.000 description 7
- 238000005481 NMR spectroscopy Methods 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 6
- 229920002554 vinyl polymer Polymers 0.000 description 6
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000012512 characterization method Methods 0.000 description 5
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-M acrylate group Chemical group C(C=C)(=O)[O-] NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 229910008051 Si-OH Inorganic materials 0.000 description 3
- 229910006358 Si—OH Inorganic materials 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000010813 internal standard method Methods 0.000 description 3
- 125000000962 organic group Chemical group 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- 229910018557 Si O Inorganic materials 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 238000004611 spectroscopical analysis Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- 239000004944 Liquid Silicone Rubber Substances 0.000 description 1
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- -1 chloropropyl Chemical group 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical compound [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000012844 infrared spectroscopy analysis Methods 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 150000001367 organochlorosilanes Chemical class 0.000 description 1
- 150000003961 organosilicon compounds Chemical class 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000004451 qualitative analysis Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000002076 thermal analysis method Methods 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/35—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light
- G01N21/3563—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light for analysing solids; Preparation of samples therefor
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- Biochemistry (AREA)
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Abstract
The invention discloses a method for testing the ratio of MQ in MQ silicon resin, which adopts infrared spectrum to specific groups (1080 cm) ‑1 Si-O-Si and 1250cm ‑1 Si-CH at 3 ) And (3) integrating the absorption peaks, establishing a quantitative relation between the peak area ratio and the MQ ratio, and fitting to obtain a corresponding calibration curve. According to the calibration curve, the MQ ratio of the MQ silicon resin can be accurately calculated by combining the infrared spectrum of the MQ silicon resin, and the result obtained by the method has better comparability with the nuclear magnetic resonance spectrum and has the advantages of simplicity and strong operability.
Description
Technical Field
The invention relates to a method for testing the MQ ratio in MQ silicon resin, in particular to a method for testing the MQ ratio in MQ silicon resin by using FTIR, which belongs to the technical field of high polymer material detection.
Background
MQ silicones are a class of silicone resins composed of monofunctional M-mer (R 3 SiO 1/2 ) And tetrafunctional Q-mer (SiO 4/2 ) The typical (planar) chemical structure of the constructed silicone resin with a three-dimensional sphere-like shape is shown in fig. 1. Compared with organic high molecular compounds, the MQ silicone resin has better high and low temperature resistance, hydrophobicity, chemical resistance, electrical insulation, weather resistance, flexibility, film forming property, adhesion and excellent mechanical properties, and is widely applied to the fields of pressure sensitive adhesives, liquid silicone rubber reinforcement, cosmetics, high temperature resistant coatings, release agents, defoamers, organic silicone leather and the like. Currently, there are two main methods for synthesizing MQ silicone resins, namely, a water glass method and a silicate method. Specifically, the former is formed by hydrolysis condensation reaction by taking organochlorosilane or various disiloxane as an M chain unit monomer and water glass as a Q chain unit monomer; the latter is formed by using ethyl orthosilicate (methyl) as a precursor of the Q chain unit, and carrying out a hydrolysis condensation reaction and then (partial) end capping by an M chain unit monomer. The physical and chemical properties of MQ silicon resin synthesized by a water glass method or a silicate method are greatly dependent on the chemical composition and structure of the resin, such as the type of R group, the size of MQ ratio, the size and distribution of molecular weight, the three-dimensional topological structure, the content of silicon hydroxyl and the like. Wherein, the MQ ratio (the ratio of the mole number of M to the mole number of Q chain links) is taken as the most important structural parameter of the MQ silicone resin, the physical and chemical properties of the MQ silicone resin are deeply influenced, and the difference of topological structures can be brought, for example, the MQ ratio can determine the density, the transparency, the viscosity, the softening point, the thermal stability, the reactivity, the film forming property and the like of the MQ silicone resin, while the smaller the MQ ratio is, the more the four-functionality Q chain links are, the more compact the MQ network is, and the structure tends to be like sphere; the greater the MQ ratio, the more M mer of monofunctional, and the more the structure tends to be hyperbranched, therefore, accurate measurement of the MQ ratio of MQ silicone is critical to understanding the structure and performance relationship and application of MQ silicone.
The current test method for the MQ ratio comprises the following steps: based on initial feed ratio, thermogravimetric analysis (organosilicon material, 2007, 120 (02): 76-80+115), solid state nuclear magnetic resonance silicon spectroscopy (Applied Magnetic Resonance, 2013, 44:1015-1025), nuclear magnetic resonance hydrogen spectroscopy internal standard method (Journal ofapplied polymer science, 2013, 128 (6): 4189-4200.), and the like. Wherein, the initial charge ratio based method deviates seriously from the actual MQ ratio because of the presence of a certain amount of unreacted monomer in the system, resulting in a significant error; thermogravimetric analysis is based on the fact that the M-mer in MQ silicone is first cracked and weightless at high temperature, while the Si-O-Si network (i.e. Q-mer) remains, so that the MQ ratio can be calculated by the mass residual rate on the thermogravimetric loss curve, but the method is also extremely error, because the Si-O-Si bond may be broken/rearranged or other mechanisms (such as pyrolysis and cyclization) to produce organosilicon compounds with various molecular weights, which sublimate at higher temperature, resulting in reduced mass residual rate of Si and O and extremely large deviation of the results; while nuclear magnetic resonance spectroscopy is the most commonly used characterization method of the MQ ratio at present, the nuclear magnetic resonance spectrometer is expensive and is difficult to be applied to actual production. There is therefore a need to develop a simple, effective and accurate method of characterizing the MQ ratio of MQ silicone.
Infrared spectroscopy has been widely used for qualitative and quantitative analysis of various organic and inorganic components and structures, and when organic molecules are irradiated with infrared light, vibration absorption can occur in chemical bonds or functional groups in the molecules, and absorption frequencies of different chemical bonds or functional groups are different. For example Peng Di, when the MQ silicone resin is subjected to infrared spectroscopic analysis in "preparation of MQ silicone resin by water trapping" ("organosilicon Material"; 2009,33 (3): 171-175), the synthesized compounds are each 2960cm in their FTIR patterns -1 、1250cm -1 、845cm -1 、754cm -1 In the order of 1080cm -1 The nearby stretching vibration peak shows that it has methyl, si-CH 3 And Si-O-Si-groups, which are methyl MQ silicone resins; further, based on the a, b, and c curves in the FTIR chart, the intensity of the Si-OH absorption peak and 2960cm were found -1 The variation in intensity of the C-H absorption peak is related to the ratio of the M chain segment to the Q chain segment in the compound, and thus can be based on the intensity of the Si-OH absorption peak and 2960cm -1 The intensity change of the C-H absorption peak is used for judging the magnitude of the MQ ratio in the MQ silicon resin, but most of the MQ ratio has low hydroxyl content<1%) of the MQ ratio to hydroxyl content of the MQ silicone resin was notThe method can only qualitatively judge the relative magnitude of the M/Q value on the premise of known feed ratio, and based on the relative magnitude, when the MQ ratio of the MQ silicon resin is required to be measured, the intensity of Si-OH and C-H absorption peaks can be obtained even by adopting infrared spectrum, but the MQ ratio in the MQ silicon resin cannot be quantitatively represented.
Disclosure of Invention
The invention aims to provide a method for testing the MQ ratio in MQ silicon resin, which integrates the absorption peak of a specific group on an infrared spectrum through a series of standard samples with known MQ ratio, establishes a quantitative relation between the peak area ratio and the MQ ratio, fits to obtain a corresponding calibration curve, and combines the infrared spectrum of the MQ silicon resin according to the extrapolated part of the calibration curve to reversely calibrate the MQ ratio.
The invention is realized by the following technical scheme: a method of testing MQ ratios in MQ silicone resins, comprising the steps of:
s1, preparing a standard sample with a known MQ ratio;
s2, carrying out infrared spectrum detection by adopting a standard sample, and selecting Si-O-Si groups and Si-CH in the standard sample 3 Integrating the absorption peaks of the groups to obtain Si-O-Si groups and Si-CH 3 The quantitative relation between the area ratio of the group absorption peak and the MQ ratio is reconstructed to obtain a calibration curve;
s3, detecting the MQ silicon resin sample to be detected by adopting infrared spectrum to obtain Si-O-Si groups and Si-CH in the MQ silicon resin sample 3 And (3) the area ratio of the group absorption peak is obtained according to the standard curve.
In the S1, the MQ ratio of the standard sample is arranged in an equal gradient manner and comprises trimethylsilyl cage-shaped polysilsesquioxane (M 8 Q 8 ) Tetra (trimethylsiloxy) silane (M) 4 Q) and its complex.
In S2, 1080cm of the standard sample is selected -1 Si-O-Si symmetrical telescopic vibration absorption peak and 1250cm -1 Si-CH at 3 The bending vibration absorption peak is integrated.
In the S2, the molecular formula is [ (CH) 3 ) 3 SiO 1/2 ] m [SiO 4/2 ] q The integral area formula of the Si-O-Si group absorption peak calculated by the methyl MQ silicone resin is shown in the following formula (1):
（1）
in the formula (1), A 1 An integrated area of an absorption peak for Si-O-Si groups;
Si-CH 3 the integral area formula of the absorption peak of the group is shown in the following formula (2):
（2）
in the formula (2), A 2 Is Si-CH 3 The integrated area of the radical absorption peak.
Further, si-O-Si groups and Si-CH 3 The quantitative relationship between the area ratio of the group absorption peak and the ratio of MQ is shown in the following formula (3):
（3）
based on the above formula (3), si-O-Si groups and Si-CH 3 The area ratio of the radical absorption peaks is taken as the ordinate, (M/Q)/[ M/Q+4 ]]And drawing a scatter diagram of 7 standard samples as an abscissa, and linearly fitting to obtain a standard curve. According to the calibration curve, the MQ ratio can be accurately calculated by combining the infrared spectrum of the MQ silicon resin.
Compared with the prior art, the invention has the following advantages:
(1) The method is characterized based on infrared spectrum, is convenient and quick, does not need pretreatment, and is suitable for MQ silicon resins with different molecular weights, synthesis methods and organic groups.
(2) Compared with the existing MQ ratio characterization method of MQ silicon resin, the method is not influenced by acid-base residues and other impurities in the sample, and the characterization result has good comparability with a nuclear magnetic resonance hydrogen spectrum internal standard method.
Drawings
FIG. 1 is a block diagram of an MQ silicone resin (R, R ', R "are organic groups including hydrogen, methyl, vinyl, phenyl, chloropropyl, (meth) acrylate groups, and the like, wherein R, R', R" may be the same or different).
FIG. 2 is a trimethylsilyl cage polysilsesquioxane (M 8 Q 8 ) And tetrakis (trimethylsiloxy) silane (M) 4 Structure of Q).
FIG. 3 is M 8 Q 8 Is a fitting curve.
FIG. 4 is an infrared spectrum calibration curve obtained for a standard sample based on a known MQ ratio.
FIG. 5 is an infrared spectrum of methyl MQ silicone resin in example 1.
FIG. 6 is an infrared spectrum of methyl MQ silicone resin in example 2.
FIG. 7 is an infrared spectrum of methyl MQ silicone (i.e., wake 803) in example 3.
FIG. 8 is an infrared spectrum of the vinyl MQ silicone resin in example 4.
FIG. 9 is an infrared spectrum of phenyl MQ silicone of example 5.
FIG. 10 is an infrared spectrum of the (meth) acrylate-based MQ silicone resin in example 6.
Detailed Description
The objects, technical solutions and advantageous effects of the present invention will be described in further detail below.
It is noted that the following detailed description is exemplary and is intended to provide further explanation of the invention as claimed, and unless otherwise indicated, 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.
The invention can realize the determination of the MQ ratio of MQ silicon resin with different molecular weights, synthesis methods and organic groups, can complete the calibration of the MQ ratio of commercial MQ silicon resin by means of infrared spectrum, and has the advantages of convenience, rapidness and higher accuracy.
The specific test mode can be summarized as follows:
and selecting a series of MQ standard samples with known MQ ratio, integrating the absorption peaks of the specific groups by adopting infrared spectrum, establishing a quantitative relation between the peak area ratio and the MQ ratio, fitting to obtain a corresponding calibration curve, and calculating the MQ ratio by combining the infrared spectrum of the MQ silicon resin according to the calibration curve. The method comprises the following specific steps:
step one, configuration of MQ standard samples and infrared spectrum test
Experimental samples: m is M 8 Q 8 And M 4 Q (see fig. 2) and a series of MQ standard samples (see table below) of the MQ ratio of the isocratic formulated;
experimental instrument: an infrared spectrometer;
experimental parameters: spectral range 4000-400 cm -1 Spectral resolution 4 cm -1 And a transmission mode.
Step two, analysis of infrared spectrum
Firstly, the absorption peak of an infrared spectrogram is attributed to Si-CH 3 The bending vibration absorption peak of (2) is generally 1250cm -1 About, the Si-O-Si symmetrical telescopic vibration absorption peak is generally 1080cm -1 About, the two absorption peaks can be fitted separately, taking M8Q8 as an example, see fig. 3, whose fitted curve equation is y=0.28143x+0.07475, where y=a (si—ch 3 )/A(Si-O-Si)，x=(M/Q)/[M/Q+4]。
Step three, establishment of quantitative relation
Taking the product of the intensity of the absorption peak (I) and the full width at half maximum (FWHM) as a quantitative basis (see table below), the integrated area (a=i×fwhm) is proportional to the chain link content (see 3 formulas below)
Methyl MQ silicone resin has a molecular formula of [ (CH) 3 ) 3 SiO 1/2 ] m [SiO 4/2 ] q
The quantitative relationship of peak area ratio to MQ ratio is as follows:
（1）
（2）
（3）
in the formula (1), A 1 1080cm of -1 Fitting peak area of Si-O-Si bond at A 2 1250cm -1 Si-CH at 3 The fitted peak area of bonds, where M mer contains 1 part Si-O bond and 3 parts Si-CH 3 A key; the Q chain segment contains 4 parts of Si-O bonds,
formulas (1) and (2) are proportional relations between integral areas and chain link compositions
Equation (3) is obtained by dividing equation (1) and equation (2), and thus a quantitative relationship between the peak area ratio and the MQ ratio is established.
Step four, establishing a calibration curve
The infrared spectrum is used for characterizing a series of MQ standard samples with known MQ ratio in S1, the infrared spectrum is analyzed by a method in S2, and the peak area ratio (A 2 /A 1 ) The ordinate is the (M/Q)/[ M/Q+4)]And (5) drawing a scatter diagram of 7 standard samples, and linearly fitting to obtain a calibration curve (see figure 4).
Characterization of MQ ratio of commercial MQ Silicone
Characterization of commercial MQ silicone resin using infrared spectra, analysis of the infrared spectra using the method in S2, fitting to obtain the peak area ratio of the two absorption peaks (a 2 /A 1 ) And referring to the calibration curve, the MQ ratio can be converted.
The "MQ ratio" according to the present invention may be also referred to as "M/Q value", and "M" according to the present invention is the same as "M" and "Q" is the same as "Q".
The following exemplary embodiments of the present invention will be described by way of illustration, but the scope of the present invention is not limited to the following exemplary embodiments, and the detailed procedures and parameters are referred to the above test methods of the present invention.
Example 1:
this example uses infrared spectroscopy to characterize a higher molecular weight methyl MQ silicone resin (water glass synthesis) to give an infrared spectrum, see fig. 5.
The two characteristic absorption peaks on the infrared spectrum are first assigned, wherein 1250cm -1 About is Si-CH 3 Is 1080cm -1 The left and right Si-O-Si symmetrical telescopic vibration absorption peaks are respectively fitted to obtain peak area ratio, then MQ ratio is converted according to calibration curve equation,
this gives the high molecular weight methyl MQ silicone resin in this example an MQ ratio of 0.57.
Example 2:
this example uses infrared spectroscopy to characterize a lower molecular weight methyl MQ silicone resin (water glass synthesis) to give an infrared spectrum, see fig. 6.
The two characteristic absorption peaks on the infrared spectrum are first assigned, wherein 1250cm -1 About is Si-CH 3 Is 1080cm -1 The left and right Si-O-Si symmetrical telescopic vibration absorption peaks are respectively fitted to obtain peak area ratio, then MQ ratio is converted according to calibration curve equation,
from this calculation, the MQ ratio of the low molecular weight methyl MQ silicone resin in this example was 0.90.
Example 3:
this example uses infrared spectroscopy to characterize an MQ silicone resin synthesized by the tetraethyl orthosilicate method (TEOS method), resulting in an infrared spectrum, see fig. 7.
The two characteristic absorption peaks on the infrared spectrum are first assigned, wherein 1250cm -1 About is Si-CH 3 Is 1080cm -1 The left and right Si-O-Si symmetrical telescopic vibration absorption peaks are respectively fitted to obtain peak area ratio, then MQ ratio is converted according to calibration curve equation,
from this, the MQ ratio of the MQ silicone resin synthesized by the tetraethyl orthosilicate method (TEOS method) in this example was calculated to be 0.58.
Example 4:
this example uses infrared spectroscopy to characterize a vinyl MQ silicone resin (water glass synthesis) to give an infrared spectrum, see fig. 8.
The three characteristic absorption peaks on the infrared spectrogram are firstly attributed, wherein 1640 and 1640 cm -1 Left and right are Si-ch=ch 2 (c=c) the telescopic vibration absorption peak, 1250cm -1 About is Si-CH 3 Is 1080cm -1 The symmetrical stretching vibration absorption peak of Si-O-Si is left and right, because the vinyl mole fraction of the MQ silicon resin is only 3.54%, the vinyl peak is very weak, can be ignored first, and still is used for Si-CH first 3 Fitting with two absorption peaks of Si-O-Si to obtain peak area ratio, converting the MQ ratio according to the calibration curve equation,
from this, the MQ ratio of the vinyl MQ silicone resin in this example was calculated to be 0.86.
Example 5:
this example uses infrared spectroscopy to characterize a phenylmq silicone resin (water glass synthesis) to give an infrared spectrum, see fig. 9.
The two characteristic absorption peaks on the infrared spectrum are first assigned, wherein 1250cm -1 About is Si-CH 3 Is 1080cm -1 The left and right Si-O-Si symmetrical telescopic vibration absorption peaks are respectively fitted to obtain peak area ratio, then MQ ratio is converted according to calibration curve equation,
from this calculation, the MQ ratio of the phenylmq silicone resin in this example was 0.55.
Example 6:
this example uses infrared spectroscopy to characterize a (meth) acrylate based MQ silicone resin (water glass synthesis) to give an infrared spectrum, see fig. 10.
The two characteristic absorption peaks on the infrared spectrum are first assigned, wherein 1250cm -1 About is Si-CH 3 Is 1080cm -1 The left and right Si-O-Si symmetrical telescopic vibration absorption peaks are respectively fitted to obtain peak area ratio, then MQ ratio is converted according to calibration curve equation,
from this, the MQ ratio of the (meth) acrylate-based MQ silicone resin in this example was calculated to be 0.54.
MQ silicone resins of examples 1 to 6 were subjected to the nuclear magnetic resonance hydrogen spectrum internal standard method 1 H NMR) and thermal analysis (TGA) to calibrate the MQ ratio thereof, and the silicon hydroxyl group contents of the above examples 1 to 6 and the silicon hydroxyl group contents after titration are summarized as shown in the following table.
The foregoing description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way, and any simple modification, equivalent variation, etc. of the above embodiment according to the technical matter of the present invention fall within the scope of the present invention.
Claims (6)
1. A method for testing MQ ratio in MQ silicone resin, characterized by: the method comprises the following steps:
s1, preparing a standard sample with a known MQ ratio;
s2, carrying out infrared spectrum detection by adopting a standard sample, and selecting Si-O-Si groups and Si-CH in the standard sample 3 Integrating the absorption peaks of the groups to obtain Si-O-Si groups and Si-CH 3 The quantitative relation between the area ratio of the group absorption peak and the MQ ratio is reconstructed to obtain a calibration curve;
s3, detecting the MQ silicon resin sample to be detected by adopting infrared spectrum to obtain Si-O-Si groups and Si-CH in the MQ silicon resin sample 3 And (3) the area ratio of the group absorption peak is obtained according to the standard curve.
2. The method according to claim 1, characterized in that: in the S1, the MQ ratio of the standard sample is arranged in an equal gradient manner and comprises trimethylsilyl cage-shaped polysilsesquioxane (M 8 Q 8 ) Tetra (trimethylsiloxy) silane (M) 4 Q) and its complex.
3. The method according to claim 1, characterized in that: in S2, 1080cm of the standard sample is selected -1 Si-O-Si symmetrical telescopic vibration absorption peak and 1250cm -1 Si-CH at 3 The bending vibration absorption peak is integrated.
4. The method according to claim 1, characterized in that: in the S2, the molecular formula is [ (CH) 3 ) 3 SiO 1/2 ] m [SiO 4/2 ] q The integral surface of the Si-O-Si group absorption peak calculated for the methyl MQ silicone resinThe product formula is shown in the following formula (1):
（1）
in the formula (1), A 1 An integrated area of an absorption peak for Si-O-Si groups;
Si-CH 3 the integral area formula of the absorption peak of the group is shown in the following formula (2):
（2）
in the formula (2), A 2 Is Si-CH 3 The integrated area of the radical absorption peak.
5. The method according to claim 4, wherein: in the S2, si-O-Si group and Si-CH 3 The quantitative relationship between the area ratio of the group absorption peak and the ratio of MQ is shown in the following formula (3):
（3）
6. the method according to claim 5, wherein: combining Si-O-Si groups with Si-CH 3 The area ratio of the radical absorption peaks is taken as the ordinate, (M/Q)/[ M/Q+4 ]]And drawing a scatter diagram of 7 standard samples as an abscissa, and linearly fitting to obtain a standard curve.
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