CN114136909A - Method for testing hydroxyl protection rate of poly (4-hydroxystyrene-co-tert-butoxyacyloxystyrene) - Google Patents
Method for testing hydroxyl protection rate of poly (4-hydroxystyrene-co-tert-butoxyacyloxystyrene) Download PDFInfo
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 title claims abstract description 69
- 238000000034 method Methods 0.000 title claims abstract description 43
- 238000012360 testing method Methods 0.000 title claims abstract description 23
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims abstract description 55
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 45
- 238000001514 detection method Methods 0.000 claims abstract description 17
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 claims description 27
- 238000002329 infrared spectrum Methods 0.000 claims description 24
- 239000002904 solvent Substances 0.000 claims description 19
- 238000004528 spin coating Methods 0.000 claims description 15
- 238000000576 coating method Methods 0.000 claims description 14
- 230000003595 spectral effect Effects 0.000 claims description 9
- 238000004566 IR spectroscopy Methods 0.000 claims description 8
- 238000001228 spectrum Methods 0.000 claims description 8
- 230000001681 protective effect Effects 0.000 claims description 3
- 229920002120 photoresistant polymer Polymers 0.000 abstract description 7
- 239000011347 resin Substances 0.000 abstract description 7
- 229920005989 resin Polymers 0.000 abstract description 7
- 238000004458 analytical method Methods 0.000 abstract description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 24
- FUGYGGDSWSUORM-UHFFFAOYSA-N 4-hydroxystyrene Chemical compound OC1=CC=C(C=C)C=C1 FUGYGGDSWSUORM-UHFFFAOYSA-N 0.000 description 7
- -1 carbonyl Chemical group 0.000 description 7
- 238000004377 microelectronic Methods 0.000 description 7
- 125000006239 protecting group Chemical group 0.000 description 7
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 4
- 238000002835 absorbance Methods 0.000 description 4
- 239000002313 adhesive film Substances 0.000 description 4
- 238000010606 normalization Methods 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 3
- 238000004364 calculation method Methods 0.000 description 3
- 238000012937 correction Methods 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 2
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 231100000086 high toxicity Toxicity 0.000 description 2
- 238000012417 linear regression Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 125000004213 tert-butoxy group Chemical group [H]C([H])([H])C(O*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- AAHNIBROSVVFRO-RMKNXTFCSA-N (e)-3-(4-butoxyphenyl)prop-2-enoic acid Chemical compound CCCCOC1=CC=C(\C=C\C(O)=O)C=C1 AAHNIBROSVVFRO-RMKNXTFCSA-N 0.000 description 1
- 241001391944 Commicarpus scandens Species 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001343 alkyl silanes Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229940116333 ethyl lactate Drugs 0.000 description 1
- 238000009499 grossing Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 231100000171 higher toxicity Toxicity 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 238000012690 ionic polymerization Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 238000000206 photolithography Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical group COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- 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
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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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Abstract
The application relates to the technical field of photoresist resin, and provides a method for testing the hydroxyl protection rate of poly (4-hydroxystyrene-co-tert-butoxystyrene), wherein a regression equation for obtaining a standard curve is established by obtaining the ratio of the total area of two characteristic peaks of carbonyl in a poly (4-hydroxystyrene-co-tert-butoxystyrene) sample with known hydroxyl protection rate to the area of the characteristic peak of a para-substituent of a benzene ring; substituting the ratio of the total area of two characteristic peaks of carbonyl in a poly (4-hydroxystyrene-co-tert-butoxyacyloxystyrene) sample to be detected to the characteristic peak area of a benzene ring para-substituent into the regression equation, and calculating to obtain the hydroxyl protection rate of the sample to be detected; the method can accurately obtain the hydroxyl protection rate of the poly (4-hydroxystyrene-co-tert-butoxyacyloxystyrene) sample to be detected, and has the advantages of simplicity, convenience, high analysis speed, high accuracy, small error, low detection cost and the like.
Description
Technical Field
The application relates to the technical field of photoresist resin, in particular to a method for testing the hydroxyl protection rate of poly (4-hydroxystyrene-co-tert-butoxyacyloxystyrene).
Background
Photoresist is a critical material for the photolithography process in microelectronics manufacturing, and photoresist resin is a main component of photoresist. In a 248nm photoresist system, the film-forming resin is poly-p-hydroxystyrene and derivatives thereof. Poly (4-hydroxystyrene-co-t-butoxyacyloxystyrene) is one of them.
The poly (4-hydroxystyrene-co-tert-butoxystyrene) (tBOC-PHS) prepared by taking tert-butoxyacyloxy as a protecting group has a structural formula shown in a formula (I):
when the hydroxyl is partially protected by the tert-butoxy group, the poly-p-hydroxystyrene is insoluble in alkaline water, and the conditions that the adhesive film is brittle and easy to crack, poor in adhesion and excessively shrunk can be avoided, so that the poly-p-hydroxystyrene partially protected by the tert-butoxy group becomes a main film-forming resin. However, the accuracy of the existing testing method for the hydroxyl protection rate of poly (4-hydroxystyrene-co-tert-butoxyacyloxystyrene) is not high, and the method is complex and still needs to be improved.
Disclosure of Invention
The application aims to provide a method for testing the hydroxyl protection rate of poly (4-hydroxystyrene-co-tert-butoxystyrene) so as to accurately obtain the hydroxyl protection rate of poly (4-hydroxystyrene-co-tert-butoxystyrene), and the testing method is simple and convenient.
The application provides a method for testing the hydroxyl protection rate of poly (4-hydroxystyrene-co-tert-butoxyacyloxystyrene), which comprises the following steps:
s1, taking 5-10 poly (4-hydroxystyrene-co-tert-butoxyacyloxystyrene) samples with different known hydroxyl protection rates, carrying out infrared spectrum detection under the same spectrum condition, respectively obtaining infrared spectrogram of each sample, and obtaining the ratio of the total area of two characteristic peaks of carbonyl groups in each sample to the area of the characteristic peak of a para-substituent of a benzene ring;
wherein the structural formula of the poly (4-hydroxystyrene-co-tert-butoxyacyloxystyrene) is shown as the formula (I):
m and n are the number of two kinds of repeating units in poly (4-hydroxystyrene-co-tert-butoxyacyloxystyrene); protective ratio of hydroxyl group
S2, establishing a standard curve by taking the ratio of the total area of the two characteristic peaks of the carbonyl group to the area of the characteristic peak of the para-substituent of the benzene ring as an abscissa and the hydroxyl protection rate as an ordinate, and obtaining a regression equation Y of the standard curve as aX + b;
wherein X is the ratio of the total area of two characteristic peaks of carbonyl to the area of the characteristic peak of a para-substituent of a benzene ring, Y is the hydroxyl protection rate, and a and b are constants;
s3, taking a poly (4-hydroxystyrene-co-tert-butoxyacyloxystyrene) sample to be detected, carrying out infrared spectrum detection under the same spectrum condition as that in the step S1 to obtain an infrared spectrogram of the sample to be detected, and obtaining the ratio of the total area of two characteristic peaks of a carbonyl group in the sample to be detected to the area of a characteristic peak of a para-substituent of a benzene ring;
and S4, calculating the hydroxyl protection rate of the sample to be detected according to the regression equation of the standard curve and the ratio of the total area of the two characteristic peaks of the carbonyl group in the sample to be detected to the area of the characteristic peak of the para-substituent of the benzene ring.
In some embodiments, the spectral conditions comprise: the spectral scanning range is 400-4000cm-1The scanning times are 16-64 times, and the resolution is 4cm-1Or 8cm-1。
In some embodiments, the wavenumbers of the two characteristic peaks of the carbonyl group are 1756 ± 5cm, respectively-1And 1732. + -. 5cm-1The wave number of the characteristic peak of the para-substituent of the benzene ring is 830 +/-5 cm-1。
In some embodiments, the regression equation for the standard curve is Y ═ 0.1824X-0.1788.
In some embodiments, the poly (4-hydroxystyrene-co-t-butoxyacyloxystyrene) sample with known hydroxyl protection is prepared by a coating method or a potassium bromide tabletting method; wherein the coating method comprises: poly (4-hydroxystyrene-co-tert-butoxyacyloxystyrene) with known hydroxyl protection rate is spin-coated on a potassium bromide salt sheet and baked until the solvent is completely removed.
In some embodiments, the poly (4-hydroxystyrene-co-t-butoxyacyloxystyrene) sample to be tested is prepared by a coating method or a potassium bromide tabletting method; wherein the coating method comprises: the poly (4-hydroxystyrene-co-tert-butoxyacyloxystyrene) solution is spin-coated on a potassium bromide salt sheet and baked until the solvent is completely removed.
In some embodiments, the spin coating method is performed at a spin speed of 1000-.
In some embodiments, the baking temperature is 110-130 ℃ and the baking time is 90-180s in the coating method.
In some embodiments, the infrared spectroscopy is detection using a fourier infrared spectrometer.
According to the method for testing the hydroxyl protection rate of poly (4-hydroxystyrene-co-tert-butoxyacyloxystyrene), a regression equation for obtaining a standard curve is established by obtaining the ratio of the total area of two characteristic peaks of carbonyl in a poly (4-hydroxystyrene-co-tert-butoxyacyloxystyrene) sample with known hydroxyl protection rate to the area of the characteristic peak of a para-substituent of a benzene ring; substituting the ratio of the total area of two characteristic peaks of carbonyl in a poly (4-hydroxystyrene-co-tert-butoxyacyloxystyrene) sample to be detected to the characteristic peak area of a benzene ring para-substituent into the regression equation, and calculating to obtain the hydroxyl protection rate of the sample to be detected; the method can accurately obtain the hydroxyl protection rate of the poly (4-hydroxystyrene-co-tert-butoxyacyloxystyrene) sample to be detected, and has the advantages of simplicity, convenience, high analysis speed, high accuracy, small error, low detection cost and the like.
Of course, not all advantages described above need to be achieved at the same time in the practice of any one product or method of the present application.
Drawings
In order to more clearly illustrate the technical solutions in the present application or the prior art, the drawings needed for describing the embodiments or the prior art are briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present application, and other embodiments can be obtained by those skilled in the art according to the drawings.
FIG. 1 is a graph of the infrared spectrum of a poly (4-hydroxystyrene-co-t-butoxystyrene) standard sample of example 1 after ordinate normalization;
FIG. 2 is a standard graph established in example 1;
FIG. 3 is an infrared spectrum of a poly (4-hydroxystyrene-co-t-butoxystyrene) sample to be tested in example 2-6 after ordinate normalization.
Detailed Description
The technical solutions in the present application will be described clearly and completely with reference to the accompanying drawings in the present application, and it is obvious that the described embodiments are only a part of the embodiments of the present application, and not all of the embodiments. All other embodiments that can be derived by one of ordinary skill in the art from the description herein are intended to be within the scope of the present disclosure.
The inventor of the present invention has found that, in a p-hydroxystyrene monomer, a hydroxyl group capable of forming a hydrogen bond is contained, and if the phenolic hydroxyl group is not protected by a protecting group, spontaneous polymerization is easy, and the phenolic hydroxyl group is easy to be oxidized and difficult to stably exist for a long time, and a large amount of benzene rings and hydroxyl groups exist in a generated polymer, so that a certain polymerization inhibition effect is generated. Therefore, in the preparation of poly-p-hydroxystyrene, a direct polymerization method of p-hydroxystyrene monomers is not generally adopted, but a derivative monomer with protected phenolic hydroxyl groups is synthesized, then a high polymer is formed by adopting a free radical polymerization, an ionic polymerization and the like, and finally a protecting group is removed. Examples of the protective group for protecting the phenolic hydroxyl group include acetyl group, benzoyl group, and alkylsilane.
Pure Polyhydroxystyrene (PHS) is optically clear at 248 nm. Poly (4-hydroxystyrene-CO-tert-butoxystyrene) (hereinafter referred to as tBOC-PHS) prepared by taking tert-butoxyacyloxy (hereinafter referred to as tBOC) as a protective group is more transparent at 248nm, is insoluble in an alkali solution, is easy to remove the protective group under the heating or acidic condition, and generates CO2And isobutene gas and discharging.
However, when the protection ratio of tBOC is 100%, a large amount of energy is consumed for removing the protecting group, and a large amount of energy is released during baking after exposureAmount of CO2And isobutene gas, which causes excessive shrinkage of the adhesive film in the exposure area and pollutes the environment; the adhesive film is easily broken during development and has poor adhesion to the substrate. When the tBOC part is used for protection, the adhesive film can be prevented from being fragile, easy to break, poor in adhesion, excessively contracted and the like. Therefore, p-hydroxystyrene protected by the tBOC part becomes the main film-forming resin of the 248nm photoresist, and the accurate acquisition of the tBOC-PHS hydroxyl protection rate is particularly important.
The application provides a method for testing tBOC-PHS hydroxyl protection rate, which comprises the following steps:
s1, taking 5-10 tBOC-PHS samples with different known hydroxyl protection rates, carrying out infrared spectrum detection under the same spectrum condition, respectively obtaining an infrared spectrogram of each sample, and obtaining the ratio of the total area of two characteristic peaks of carbonyl groups in each sample to the area of a characteristic peak of a para-substituent of a benzene ring;
wherein the structural formula of tBOC-PHS is shown as the formula (I):
m and n are the number of two kinds of repeating units in tBOC-PHS; protective ratio of hydroxyl group
S2, establishing a standard curve by taking the ratio of the total area of two characteristic peaks of carbonyl to the area of the characteristic peak of a para-substituent of a benzene ring as an abscissa and the hydroxyl protection rate as an ordinate, and obtaining a regression equation Y of the standard curve which is aX + b;
wherein X is the ratio of the total area of two characteristic peaks of carbonyl to the area of the characteristic peak of a para-substituent of a benzene ring, Y is the hydroxyl protection rate, and a and b are constants;
s3, taking a tBOC-PHS sample to be detected, and carrying out infrared spectrum detection under the same spectrum condition as the step S1 to obtain an infrared spectrogram of the sample to be detected, and obtaining the ratio of the total area of two characteristic peaks of carbonyl in the sample to be detected to the area of a characteristic peak of a para-substituent of a benzene ring;
and S4, calculating the hydroxyl protection rate of the sample to be detected according to the regression equation of the standard curve and the ratio of the total area of the two characteristic peaks of the carbonyl group in the sample to be detected to the area of the characteristic peak of the para-substituent of the benzene ring.
tBOC-PHS shown in formula (I) of the application has a molecular formula: (C)8H8O)m(C13H16O3)n1mol of tBOC-PHS contains n mol of carbonyl
And (n + m) mol of para-substituents of benzene ring
The molar ratio of the carbonyl group to the para-substituent of the benzene ring is
Due to hydroxyl protection rate of tBOC-PHS
Therefore, the molar ratio of carbonyl to para-substituent of the benzene ring can be used to characterize the hydroxyl protection ratio of tBOC-PHS.
According to the lambert-beer law, the intensity of the absorbance of a group at a characteristic wavelength is proportional to its molarity within a certain range. In the application, the peak area in an infrared spectrogram is used for expressing the intensity of an absorption peak, the peak area of a characteristic peak of a carbonyl group is in direct proportion to the molar concentration of the carbonyl group, and the peak area of the characteristic peak of a para-substituent of a benzene ring is in direct proportion to the molar concentration of the para-substituent of the benzene ring; thus, the molar concentration ratio of carbonyl groups to para-substituents of the benzene ring
And the peak area ratio of the characteristic peak of carbonyl group to the characteristic peak of para-substituent of benzene ring
Is in direct proportion.
In the same solution, the solution is mixed,molar concentration ratio of carbonyl group to para-substituent of benzene ring
And the molar ratio of carbonyl groups to para-substituents of the benzene ring
Are equal. Thus, the molar ratio of carbonyl groups to para-substituents of the benzene ring
And the peak area ratio of the characteristic peak of carbonyl group to the characteristic peak of para-substituent of benzene ring
Proportional ratio, i.e. hydroxyl protection ratio
And the peak area ratio of the characteristic peak of carbonyl group to the characteristic peak of para-substituent of benzene ring
In direct proportion.
According to the method, through establishing a linear regression equation Y of a standard curve as aX + b, for a tBOC-PHS sample to be detected, the ratio of the characteristic peak area of a carbonyl group in the sample to be detected to the characteristic peak area of a benzene ring para-substituent is obtained only through an infrared spectrum, the ratio is substituted into the regression equation Y as aX + b, the ratio is converted into percentage, and the hydroxyl protection rate of the sample to be detected can be obtained through calculation.
In step S1 of the present application, a carbonate ester
Is connected with a benzene ring structure on one side, and is connected with a tert-butyl group on the other side. In the infrared spectroscopy, the characteristic carbonyl peak of the carbonate is split into two partially overlapping carbonyl peaks due to the influence of intramolecular structural factors, and therefore, the characteristic peak area of the carbonyl group in the present application refers to the total area of the two characteristic peaks of the partially overlapping carbonyl group.
In the step S1, when tBOC-PHS samples with different known hydroxyl protection rates are selected, a plurality of samples with certain gradient distribution of the hydroxyl protection rates can be selected, which is favorable for improving the accuracy of the regression equation of the obtained standard curve; the number of samples is not particularly limited, and the regression equation is more accurate when the number of samples is large, for example, 5 to 10 samples are selected in the present application.
In step S1, infrared spectrum detection is performed on all samples under the same spectral condition, so that the influence of different spectral conditions on the result during the test can be removed, and the accuracy of the regression equation for establishing the obtained standard curve can be improved.
In step S1, the specific method for obtaining the ratio of the total area of the two characteristic peaks of the carbonyl group in the sample to the characteristic peak area of the para-substituent of the benzene ring according to the infrared spectrogram is not limited as long as the purpose of the present application can be achieved, for example, converting the collected infrared spectrogram into an infrared spectrogram with absorbance as ordinate and wave number as abscissa, and then performing ordinate normalization; and measuring the total peak area of the two characteristic peaks of the carbonyl group after baseline correction, and measuring the peak area of the characteristic peak of the benzene ring para-substituent after baseline correction, so as to obtain the ratio of the total area of the two characteristic peaks of the carbonyl group in the sample to the characteristic peak area of the benzene ring para-substituent.
In step S2, since the ratio of the total area of the two characteristic peaks of the carbonyl group in each sample to the characteristic peak area of the para-substituent of the benzene ring is determined, and the hydroxyl group protection rate of each sample is a known value, a and b are both constants determined by numerical values in the regression equation Y ═ aX + b of the established standard curve.
In step S3, the infrared spectrum detection is performed on the sample to be tested under the same spectrum condition as in step S1, so that the influence of different spectrum conditions on the result during the test can be eliminated, and the accuracy of the hydroxyl protection rate obtained by the test can be improved.
The method provided by the application can accurately obtain the hydroxyl protecting rate of the tBOC-PHS sample, has the advantages of simplicity, high analysis speed, high accuracy, small error, low detection cost and the like, does not need to additionally introduce an internal standard to eliminate the influence of the film thickness, does not need to adopt complex calculation modes such as a convolution smoothing method and a second derivative, and does not need to carry out complex molecular weight calculation. The regression equation can be used all the time once established, repeated establishment is not needed, and economy and high efficiency are achieved. Furthermore, tBOC-PHS is usually stored in a solvent, and a nuclear magnetic analysis method needs to remove the solvent for storing the tBOC-PHS and then dissolve the solvent in a good solvent for testing, and some good solvents have higher toxicity; the method provided by the application does not need to use a good solvent with high toxicity to dissolve the tBOC-PHS sample, is simple and convenient to operate, and is safe and environment-friendly.
In some embodiments of the present application, the spectral scan range is 400-4000cm-1The scanning times are 16-64 times, and the resolution is 4cm-1Or 8cm-1. By adopting the spectral conditions, the total area of two characteristic peaks of carbonyl and the characteristic peak area of a benzene ring para-substituent can be accurately obtained, and the accuracy of the hydroxyl protection rate of final determination can be improved.
In some embodiments of the present application, the wavenumbers of the two characteristic peaks of the carbonyl group are 1756 ± 5cm, respectively-1And 1732. + -. 5cm-1The wave number of the characteristic peak of the para-substituent of the benzene ring is 830 +/-5 cm-1. In infrared spectrum, due to the influence of intramolecular structural factors, the characteristic peak of carbonyl in carbonate can be split into two peaks respectively positioned at 1756 +/-5 cm-1And 1732. + -. 5cm-1And the two carbonyl peaks partially overlap; the characteristic peak of the para-substituent of the benzene ring is positioned at 830 +/-5 cm-1。
In some embodiments of the present application, the regression equation for the standard curve is Y ═ 0.1824X-0.1788. The regression equation established by the method can be used all the time without repeated establishment, and is economical and efficient.
In some embodiments of the present application, tBOC-PHS samples of known hydroxyl protection were prepared using a coating process or a potassium bromide tableting process; wherein, the coating method includes: and spin-coating a tBOC-PHS solution with known hydroxyl protection rate on a potassium bromide salt plate, and baking until the solvent is completely removed.
The tBOC-PHS solution described herein is a solution obtained by dissolving tBOC-PHS in a solvent, and the kind of the solvent is not limited in the present application as long as the object of the present application can be achieved, and for example, the solvent is propylene glycol methyl ether acetate, ethyl lactate, or the like.
The spin coating apparatus used in the coating method is not limited as long as the purpose of the present application can be achieved, and for example, spin coating is performed using a spin coater for spin coating.
The concrete steps of the potassium bromide tabletting method are not limited in the application, as long as the purpose of the potassium bromide tabletting method can be achieved, for example, a tBOC-PHS solid sample with known hydroxyl protection rate and diluent potassium bromide powder are put in an agate mortar together, and are added into a tabletting mold after being uniformly ground; vacuumizing and pressurizing by adopting a tablet press to prepare a tablet; and then infrared spectrum detection is carried out.
In some embodiments of the present application, the tBOC-PHS sample to be tested is prepared by a coating method or a potassium bromide tabletting method; wherein, the coating method includes: and spin-coating the tBOC-PHS solution on a potassium bromide salt sheet, and baking until the solvent is completely removed.
The contents of a spin coating device, a potassium bromide tabletting method and the like adopted by the tBOC-PHS sample to be detected are the same as the corresponding contents, and the description is not repeated here.
In some embodiments of the present application, the spin coating speed is 1000-. The spin-coating rotating speed within the range is favorable for forming a thin layer on a potassium bromide salt sheet by more uniformly spin-coating the tBOC-PHS solution.
In some embodiments of the present application, the baking temperature is 110-. The application adopts the baking temperature and time within the range, which is beneficial to more thoroughly removing the solvent and avoiding the residual solvent from interfering the infrared spectrum detection result.
In some embodiments of the present application, the infrared spectroscopy is performed by fourier infrared spectroscopy (hereinafter referred to as FTIR). The FTIR scanning speed that this application adopted is fast, resolution ratio is high, wave number precision is high, is favorable to improving the degree of accuracy that infrared spectroscopy detected.
The experimental materials and methods used in the following examples are, unless otherwise specified, conventional materials and methods.
The instrument comprises the following steps: FTIR: PerkinElmer, FT-IR; spin coating instrument for spin coating: laurell, WS-400 BZ.
Example 1
Materials: 7 tBOC-PHS resin solutions with known hydroxyl protection rate (all from Kowa microelectronic materials Co., Ltd.) have a structural formula shown in formula (I):
merchant-provided 7 product information: protection rate of poly (4-hydroxystyrene-co-tert-butoxyacyloxystyrene) hydroxyl
Respectively 20.0% (corresponding to standard sample 1), 27.0% (corresponding to standard sample 2), 28.0% (corresponding to standard sample 3), 29.0% (corresponding to standard sample 4), 33.0% (corresponding to standard sample 5), 34.0% (corresponding to standard sample 6), 41.0% (corresponding to standard sample 7).
S1, respectively taking 1.0mL of the tBOC-PHS solution, and spin-coating by adopting a spin coater with the rotating speed of 1500 rpm; baking the sample on an electric hot plate at 115 ℃ for 120s to remove the solvent, and cooling the sample to room temperature to obtain 7 tBOC-PHS standard samples;
adopting FTIR to carry out infrared spectrum detection at 400-4000cm-1Scanning 64 times in range with 4cm resolution-1(ii) a Firstly, collecting a background, and then respectively collecting the infrared spectrograms of the 7 tBOC-PHS standard samples;
respectively converting the 7 collected infrared spectrograms into infrared spectrograms with absorbance as a vertical coordinate and wave number as a horizontal coordinate, and carrying out normalization processing on the vertical coordinate to obtain the infrared spectrograms shown in the figure 1; in fig. 1, a corresponds to the infrared spectrum of the standard sample 1, B corresponds to the infrared spectrum of the standard sample 2, C corresponds to the infrared spectrum of the standard sample 3, D corresponds to the infrared spectrum of the standard sample 4, E corresponds to the infrared spectrum of the standard sample 5, F corresponds to the infrared spectrum of the standard sample 6, and G corresponds to the infrared spectrum of the standard sample 7.
Two characteristic peaks (1756 +/-5 cm) of carbonyl groups corresponding to different samples in the graph 1 are respectively measured-1And 1732. + -. 5cm-1Point) is corrected by base line, and then characteristic peaks (830 +/-5 cm) of para-substituent of benzene ring are respectively measured-1And) the peak area after baseline correction, the ratio of the total area of two characteristic peaks of carbonyl groups in 7 samples to the characteristic peak area of the para-substituent of the benzene ring can be obtained, and the specific results are shown in table 1.
Table 1 example 1 standard sample information and test results
S2, taking the ratio of the total area of the two characteristic peaks of the carbonyl group in the 7 samples to the characteristic peak area of the para-substituent of the benzene ring as an abscissa and the hydroxyl protection rate as an ordinate, and performing linear regression analysis to obtain a standard curve as shown in figure 2, wherein the corresponding regression equation is that Y is 0.1824X-0.1788, and the correlation coefficient R is20.9972; wherein X is the ratio of the total area of two characteristic peaks of carbonyl to the area of the characteristic peak of a para-substituent of a benzene ring, and Y is the hydroxyl protection rate.
And S3, substituting the ratio of the total area of two characteristic peaks of carbonyl groups in the 7 samples obtained in the step S1 to the area of the characteristic peak of a para-substituent of a benzene ring as an X value into Y of 0.1824X-0.1788, converting the X value into a percentage, and calculating the test values of the hydroxyl protection rate Y of the 7 samples respectively, wherein the specific results are shown in Table 2.
Table 2 test results of hydroxyl group protecting rate of the standard sample of example 1
As can be seen from the results in Table 2, the infrared spectroscopy provided by the present application can accurately obtain the hydroxyl protecting rate of the tBOC-PHS sample, the absolute error value is 0.7% at most, and the absolute error value is not higher than 0.7%.
Example 2
Materials: the tBOC-PHS solution to be tested (from Kehua microelectronic materials Co., Ltd.) has a structural formula shown in formula (I):
product information provided by the merchant: protection rate of poly (4-hydroxystyrene-co-tert-butoxyacyloxystyrene) hydroxyl
It was 28.0%.
S1, taking 1.0mL of the tBOC-PHS solution to be detected, and spin-coating by adopting a spin coater with the rotating speed of 1500 rpm; baking the sample on an electric hot plate at 115 ℃ for 120s to remove the solvent, and cooling the sample to room temperature to obtain a tBOC-PHS sample to be detected;
adopting FTIR to carry out infrared spectrum detection at 400-4000cm-1Scanning 64 times in range with 4cm resolution-1(ii) a Firstly, collecting a background, and then collecting an infrared spectrogram of a tBOC-PHS sample to be detected;
converting the collected infrared spectrogram into an infrared spectrogram with absorbance as a vertical coordinate and wave number as a horizontal coordinate, and normalizing the vertical coordinate to obtain a spectral line A' of the infrared spectrogram shown in figure 3;
two characteristic peaks (1756 +/-5 cm) of carbonyl corresponding to the infrared spectrum line A' in the graph 3 are measured-1And 1732. + -. 5cm-1Point) was corrected for baseline to a total peak area of 23.840, and the characteristic peak (830. + -.5 cm) of the para-substituent of the benzene ring was measured-1Treatment) via baseline correctionThe peak area is 9.554, and the ratio of the total area of two characteristic peaks of carbonyl in the sample to be detected to the characteristic peak area of the benzene ring para-substituent is 2.50.
S2, substituting the ratio of the total area of the two characteristic peaks of the carbonyl group obtained in step S1 to the area of the characteristic peak of the para-substituent of the benzene ring as the X value into Y ═ 0.1824X-0.1788, that is, Y ═ 0.1824 × 2.50-0.1788 ≈ 0.277, and converting the ratio into percentage, the hydroxyl protection ratio Y is calculated to be 27.7%.
Example 3
Except that the tBOC-PHS solution to be tested comes from a laboratory of Kowa microelectronic materials Co., Ltd., product information provided by a merchant: protection rate of poly (4-hydroxystyrene-co-tert-butoxyacyloxystyrene) hydroxyl
The rest is the same as in example 2. See table 3 for details.
Example 4
Except that the tBOC-PHS solution to be tested comes from a laboratory of Kowa microelectronic materials Co., Ltd., product information provided by a merchant: protection rate of poly (4-hydroxystyrene-co-tert-butoxyacyloxystyrene) hydroxyl
The rest is the same as in example 2. See table 3 for details.
Example 5
Except that the tBOC-PHS solution to be tested comes from a laboratory of Kowa microelectronic materials Co., Ltd., product information provided by a merchant: protection rate of poly (4-hydroxystyrene-co-tert-butoxyacyloxystyrene) hydroxyl
The rest is the same as in example 2. See table 3 for details.
Example 6
Except that the tBOC-PHS solution to be tested comes from a laboratory of Kowa microelectronic materials Co., Ltd., product information provided by a merchant: protection rate of poly (4-hydroxystyrene-co-tert-butoxyacyloxystyrene) hydroxyl
The rest is the same as in example 2. See table 3 for details.
The test results are shown in tables 3 and 4.
TABLE 3 information on test samples and test results of examples 2-6
TABLE 4 comparison of hydroxyl radical protection rates of test samples of examples 2-6
As can be seen from the results in Table 4, the infrared spectroscopy provided by the application can accurately obtain the hydroxyl protection rate of the tBOC-PHS sample to be tested, the absolute error value is 0.6% at most, and the absolute error value is not higher than 0.7%.
In conclusion, according to the method for testing the tBOC-PHS hydroxyl protection rate, a regression equation for obtaining a standard curve is established by obtaining the ratio of the total area of two characteristic peaks of carbonyl in a tBOC-PHS sample with known hydroxyl protection rate to the characteristic peak area of a para-substituent of a benzene ring; substituting the ratio of the total area of two characteristic peaks of carbonyl in a tBOC-PHS sample to be detected to the characteristic peak area of a benzene ring para-substituent into the regression equation, and calculating to obtain the hydroxyl protection rate of the sample to be detected; the method can accurately obtain the hydroxyl protection rate of the tBOC-PHS sample, does not need to use a good solvent with high toxicity to dissolve the sample, and has the advantages of simplicity, convenience, high analysis speed, high accuracy, small error, low detection cost, safety, environmental protection and the like.
All the embodiments in the present specification are described in a related manner, and the same and similar parts among the embodiments may be referred to each other, and each embodiment focuses on the differences from the other embodiments.
The above description is only for the preferred embodiment of the present application and is not intended to limit the scope of the present application. Any modification, equivalent replacement, improvement and the like made within the spirit and principle of the present application are included in the protection scope of the present application.
Claims (9)
1. A method for testing the hydroxyl protection rate of poly (4-hydroxystyrene-co-tert-butoxyacyloxystyrene) is characterized by comprising the following steps:
s1, taking 5-10 poly (4-hydroxystyrene-co-tert-butoxyacyloxystyrene) samples with different known hydroxyl protection rates, carrying out infrared spectrum detection under the same spectrum condition, respectively obtaining infrared spectrogram of each sample, and obtaining the ratio of the total area of two characteristic peaks of carbonyl groups in each sample to the area of the characteristic peak of a para-substituent of a benzene ring;
wherein the structural formula of the poly (4-hydroxystyrene-co-tert-butoxyacyloxystyrene) is shown as the formula (I):
m and n are the number of two kinds of repeating units in poly (4-hydroxystyrene-co-tert-butoxyacyloxystyrene); protective ratio of hydroxyl group
S2, establishing a standard curve by taking the ratio of the total area of the two characteristic peaks of the carbonyl group to the area of the characteristic peak of the para-substituent of the benzene ring as an abscissa and the hydroxyl protection rate as an ordinate, and obtaining a regression equation Y of the standard curve as aX + b;
wherein X is the ratio of the total area of two characteristic peaks of carbonyl to the area of the characteristic peak of a para-substituent of a benzene ring, Y is the hydroxyl protection rate, and a and b are constants;
s3, taking a poly (4-hydroxystyrene-co-tert-butoxyacyloxystyrene) sample to be detected, carrying out infrared spectrum detection under the same spectrum condition as that in the step S1 to obtain an infrared spectrogram of the sample to be detected, and obtaining the ratio of the total area of two characteristic peaks of a carbonyl group in the sample to be detected to the area of a characteristic peak of a para-substituent of a benzene ring;
and S4, calculating the hydroxyl protection rate of the sample to be detected according to the regression equation of the standard curve and the ratio of the total area of the two characteristic peaks of the carbonyl group in the sample to be detected to the area of the characteristic peak of the para-substituent of the benzene ring.
2. The method of claim 1, wherein the spectral conditions comprise: the spectral scanning range is 400-4000cm-1The scanning times are 16-64 times, and the resolution is 4cm-1Or 8cm-1。
3. The method according to claim 1, wherein the wave numbers of the two characteristic peaks of the carbonyl group are 1756 ± 5cm respectively-1And 1732. + -. 5cm-1The wave number of the characteristic peak of the para-substituent of the benzene ring is 830 +/-5 cm-1。
4. The method of claim 1, wherein the regression equation for the standard curve is Y-0.1824X-0.1788.
5. The method of claim 1, wherein the poly (4-hydroxystyrene-co-t-butoxystyrene) sample with known hydroxyl protection is prepared by a coating method or a potassium bromide tabletting method; wherein the coating method comprises: poly (4-hydroxystyrene-co-tert-butoxyacyloxystyrene) with known hydroxyl protection rate is spin-coated on a potassium bromide salt sheet and baked until the solvent is completely removed.
6. The method as claimed in claim 1, wherein the poly (4-hydroxystyrene-co-t-butoxyacyloxystyrene) sample to be tested is prepared by a coating method or a potassium bromide tabletting method; wherein the coating method comprises: the poly (4-hydroxystyrene-co-tert-butoxyacyloxystyrene) solution is spin-coated on a potassium bromide salt sheet and baked until the solvent is completely removed.
7. The method as claimed in claim 5 or 6, wherein the spin coating speed is 1000-2000 rpm.
8. The method as claimed in claim 5 or 6, wherein the baking temperature is 110 ℃ and 130 ℃, and the baking time is 90-180 s.
9. The method of claim 1, wherein the infrared spectroscopy is performed using a fourier infrared spectrometer.
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| KR20020015948A (en) * | 2000-08-23 | 2002-03-02 | 고오사이 아끼오 | Method of quantifying protection ratio of hydroxyl group of polymer compound |
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| KR20020015948A (en) * | 2000-08-23 | 2002-03-02 | 고오사이 아끼오 | Method of quantifying protection ratio of hydroxyl group of polymer compound |
| CN103245631A (en) * | 2013-05-13 | 2013-08-14 | 长安大学 | Method of detecting styrene-butadiene-styrene segmented copolymer content in modified asphalt through dissolution method |
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