Acid-sensitive epoxy monomers protected by acetal / ketal and methods of synthesis and use thereof

Abstract

The application discloses an acetal / ketal-protected acid-sensitive epoxy monomer, chemical formula as shown in one of formula (1) to formula (3), R3 is one of formula A to formula C, and discloses a synthesis method and application of the acetal / ketal-protected acid-sensitive polymer. The acetal / ketal-protected acid-sensitive epoxy monomer can respond to pH value, especially an acid environment, so that the obtained polymer material has a stimulus response. Therefore, the acetal / ketal-protected acid-sensitive polymer can be used in the field of chemical amplification photoresist, so as to give more functionality and higher added value.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of organic compounds, in particular to an acetal / ketal-protected acid-sensitive epoxy monomer, a synthesis method and application thereof. BACKGROUND

[0002] Epoxy compounds are a class of highly reactive polymerization monomers, which can be homopolymerized under the catalysis of metal or non-metal catalyst to obtain polyether, and can be copolymerized with small molecules such as carbon monoxide and carbon dioxide to obtain more rigid polyester and polycarbonate (J. Am. Chem. Soc. 2020, 142, 12245; Angew. Chem. Int. Ed. 2020, 59, 2; Macromolecules 2021, 54, 9427; CN201710046977.0; CN200610154860.6). Epoxy-based polymers are a typical class of degradable polymers due to the presence of chemical bonds and groups in the main chain that are prone to breakage. However, common epoxy monomers lack reactive functional groups, which makes epoxy-based polymers only be used as general-purpose materials, and lack of functionality, and compared with traditional polyolefin materials, epoxy-based polymers do not have advantages in cost and mechanical properties. Therefore, it is very important to develop functional epoxy monomers to prepare high-value-added epoxy-based polymer materials. SUMMARY

[0003] The present application aims at the deficiencies of the prior art, and provides an acetal / ketal-protected acid-sensitive epoxy monomer, and a synthesis method thereof.

[0004] Another object of the present application is to provide the application of the acid-sensitive epoxy monomer.

[0005] The technical scheme provided by the present application is as follows:

[0006] An acetal / ketal-protected acid-sensitive epoxy monomer, the chemical formula of the acetal / ketal-protected acid-sensitive epoxy monomer is shown in one of formula (1) to formula (3):

[0007]

[0008] In formula (1) to formula (3), R1, R2 are each independently H, unsubstituted or substituted C1-C 20 alkyl, which may or may not contain one or more of O, S, N, Si, P atoms in the carbon chain; the substituents on the alkyl group are selected from one or more of halogen atoms, C1-C 20 branched or straight chain alkyl, C1-C 20 branched or straight chain alkoxy;

[0009] R1 is preferably H or Cl-C 10 Alkyl group; preferably R2 is H or C1-C 10 Alkyl groups;

[0010] In formula (1) or formula (2), R3 is one of the following group formulas A to C:

[0011]

[0012] Indicates a connection key;

[0013] In formula A, K1 is 0, C1-C 20 Alkylene, phenyl, or C1-C carbon chains containing oxygen or sulfur atoms 20 Alkylene, wherein the H on the alkylene or phenyl group is not substituted or is C1-C2. 10 Alkyl or C1-C 10 Alkyl substitution; preferably 0 or C1-C 10 Alkylene; furthermore, K1 in formula (1) cannot be 0, preferably C1-C 10 Alkylene; K1 in formula (2) can be 0, preferably 0 or C1-C 10 Alkylene;

[0014] In equation B, K2 is 0, C1-C 20 Alkylene, phenyl, or C1-C carbon chains containing oxygen or sulfur atoms 20 Alkylene, wherein the H on the alkylene or phenyl group is not substituted or is C1-C2. 10 Alkyl or C1-C 10 Alkyl substitution; preferably 0 or C1-C 10 Alkylene; furthermore, K2 in formula (1) cannot be 0, preferably C1-C 10 Alkylene; K2 in formula (2) can be 0, preferably 0 or C1-C 10 Alkylene;

[0015] In formula B, K3 represents C1 to C2. 20 Alkylene, or C1-C carbon chains containing oxygen or sulfur atoms. 20 Alkylene; preferably C1-C 10 Alkylene, more preferably C1 to C5 alkylene;

[0016] In formula C, K4 represents C1 to C2. 20 Pyrenesic, preferably C1-C6 pyrenesic;

[0017] In formula A, R8 and R9 are each independently H or selected from the following groups, with or without substituents: C1 to C9. 30 Alkyl or C6-C 30an aromatic group, or one or more of said groups containing one or more of the elements O, S, N, Si, P in the carbon chain; wherein said substituents are selected from the group consisting of halogen atoms, hydroxyl groups, C1-C 20 branched or linear alkyl groups, C1-C 20 branched or linear alkoxy groups, C3-C 20 branched or linear cycloalkyl groups, C6-C 30 aromatic groups, C5-C 30 heteroaromatic groups;

[0018] Preferably, R8, R9are each independently H or selected from the group consisting of C1-C 10 alkyl groups or C6-C 10 aromatic groups, said substituents being selected from the group consisting of halogen atoms, hydroxyl groups, C1-C 10 branched or linear alkyl groups, C1-C 10 branched or linear alkoxy groups;

[0019] Further, in said formula A, preferably R8is H or C1-C 10 alkyl groups, R9is C1-C 10 alkyl groups or C6-C 10 aromatic groups;

[0020] In said formula B, R 11 is H or C1-C 30 alkyl groups, preferably H or C1-C 10 alkyl groups, more preferably H;

[0021] In formula C, R 13 , R 14 are each independently H or selected from the group consisting of C1-C 30 alkyl groups or C6-C 30 aromatic groups, or one or more of said groups containing one or more of the elements O, S, N, Si, P in the carbon chain; wherein said substituents are selected from the group consisting of halogen atoms, hydroxyl groups, C1-C 20 branched or linear alkyl groups, C1-C 20 branched or linear alkoxy groups, C3-C 20 branched or linear cycloalkyl groups, C6-C 30 aromatic groups, C5-C 30 heteroaromatic groups;

[0022] Preferably, R 13 , R 14 are each independently H or C1-C 10 alkyl groups;

[0023] In said formula A, R10 The following groups, with or without substituents: C1-C 30 Alkyl, C3-C 30 cycloalkyl, C3-C 30 alkynyl group, C4-C 30 Silyl, C6-C 30 Aromatic group, C3-C 30 Heterocyclic groups or C5-C 30 The substituent is a heteroaryl group, or a group containing one or more of the following atoms in the carbon chain: O, S, N, Si, and P; wherein the substituent is selected from halogen atoms, hydroxyl groups, C1-C6 atoms, or C2-C4 atoms. 20 Branched or straight-chain alkyl groups, C1-C 20 Branched or straight-chain alkoxy groups, C3-C 20 Branched or straight-chain cycloalkyl groups, C1-C 20 Branched or straight-chain silanes, C6-C 30 Aromatic group, C5-C 30 One or more of the heteroaryl groups;

[0024] Preferred R 10 The following groups, with or without substituents: C1-C 10 Alkyl, C3-C 15 cycloalkyl, C4-C 10 Silyl, C6-C 15 Aromatic group, C3-C 15 Heterocyclic groups or C5-C 15 The substituent is a heteroaryl group, or a group containing one or more of the following atoms: O, S, N, Si, and P in the carbon chain; the substituent is selected from halogen atoms, hydroxyl groups, C1-C... 10 Branched or straight-chain alkyl groups, C1-C 10 One or more of branched or straight-chain alkoxy groups and phenyl groups; the cycloalkyl group is preferably norbornene group and its derivatives, adamantyl group and its derivatives;

[0025] More preferably R 10 For C1~C 10 Alkyl groups, C3-C7 heterocyclic groups, trifluoromethyl, hexafluoroisopropyl, pyrrolidone, butyrolactone, phenyl, benzyl, norbornene and their derivatives, adamantyl and their derivatives.

[0026] In equation B, R 12 R is a substituent on an oxygen heterocycle. 12 C1-C, whether unsubstituted or substituent 20 Alkyl group, wherein the carbon chain of the alkyl group contains or does not contain one or more of O, S, N, Si, and P atoms; the substituents on the alkyl group are selected from halogen atoms, C1-C6 atoms, and C2-C4 atoms.10 Branched or straight-chain alkyl groups, C1-C 10 One or more of the branched or straight-chain alkoxy groups; t represents R on the oxygen heterocycle. 12 The number of Rs, where t is an integer from 0 to 3, where t = 0 indicates that there are no substituents on the oxygen heterocycle, and when t is an integer greater than 2, each R 12 Same or different; preferably t is an integer from 0 to 2;

[0027] Preferred R 12 For C1-C 10 alkyl.

[0028] In the formula C, n1 and n2 are each independently taken from integers between 1 and 20; preferably, n1 and n2 are each independently taken from integers between 1 and 5.

[0029] In the formula C, R 15 R is a substituent on an oxygen heterocycle. 15 C1-C, whether unsubstituted or substituent 20 Alkyl group, wherein the carbon chain of the alkyl group contains or does not contain one or more of O, S, N, Si, and P atoms; the substituents on the alkyl group are selected from halogen atoms, C1-C6 atoms, and C2-C4 atoms. 10 Branched or straight-chain alkyl groups, C1-C 10 One or more of the branched or straight-chain alkoxy groups; s represents R on the oxygen heterocycle. 15 The number of R, where s is an integer from 0 to 3, where s = 0 indicates that there are no substituents on the oxygen heterocycle, and when s is an integer greater than 2, each R 15 Same or different; preferably s is an integer from 0 to 2; preferably R 15 For C1-C 10 alkyl.

[0030] In formula (1), R4 is H, unsubstituted or substituent C1-C 20 Alkyl group, or one of formulas A to C; the carbon chain of the alkyl group may or may not contain one or more of O, S, N, Si, and P atoms; the substituents on the alkyl group are selected from halogen atoms, C1-C1 atoms, and C2-C3 atoms. 10 Branched or straight-chain alkyl groups, C1-C 10 One or more of branched or straight-chain alkoxy groups; K1 to K4, R8 to R in formulas A to C. 15 The definitions of n1, n2, t, and s are as described above;

[0031] R4 is preferably H, Cl-C 10 Alkyl group, or one of formulas A to C; more preferably, R4 is H, C1-C. 10 Alkyl group, or the same as R3;

[0032] In formula (2), i represents the number of R3on the Q ring, i = 1 or 2, and when i = 2, it represents that there are two R3on the Q ring, which can be the same or different;

[0033] When i = 2, formula (2) can also be expressed as:

[0034]

[0035] wherein R3' is defined the same as R3, and when there are two R3substituents in the same chemical formula, R3and R3' are used to distinguish them, which can be the same or different;

[0036] In formula (2), the Q ring represents a cyclic group in which two carbon atoms of an epoxy group and a carbon chain are connected to form a ring, and the Q ring is one of the following:

[0037]

[0038] represents a bond;

[0039] wherein Z represents O, N, S, C1-C5alkylene or C1-C5alkylene containing one or more of O, N or S atoms in the carbon chain; 20 alkylene; Z is preferably O, N, S, C1-C5alkylene or C1-C5alkylene containing one or more of O, N or S atoms in the carbon chain; 20 alkylene; Z is preferably O, N, S, C1-C5alkylene or C1-C5alkylene containing one or more of O, N or S atoms in the carbon chain;

[0040] In formula (2), R q represents a substituent on the Q ring other than R3, R q is a C1-C 20 alkyl group which can be unsubstituted or substituted, and which can contain or not contain one or more of O, S, N, Si, P atoms in the carbon chain; the substituents on the alkyl group are selected from one or more of halogen atoms, C1-C 10 branched or straight chain alkoxy groups;

[0041] j represents the number of R q on the Q ring, j is an integer from 0 to 3, and when j = 0, it represents that there is only R3substituent on the Q ring, and no other substituents, and when j is an integer of 2 or more, each R q is the same or different; preferably j = 0 or 1;

[0042] Preferably R q is a C1-C 10 alkyl group;

[0043] In formula (3), m1 and m2 are each independently an integer from 1 to 20; preferably m1 and m2 are each independently an integer from 1 to 5.

[0044] R5, R6in the formula (3) are each independently H, unsubstituted or substituted C1-C 30 alkyl, or unsubstituted or substituted C6-C 30 aryl, or the group containing one or more of O, S, N, Si, P atoms in the carbon chain; wherein the substituent is selected from the group consisting of halogen atom, hydroxyl group, C1-C 20 branched or straight chain alkyl, C1-C 20 branched or straight chain alkoxy, C3-C 20 branched or straight chain cycloalkyl, C6-C 30 aryl, C5-C 30 heteroaryl;

[0045] R5, R6are each independently H, C1-C 10 alkyl or phenyl; more preferably, R5is H or C1-C 10 alkyl, R6is C1-C 10 alkyl or phenyl;

[0046] R7in the formula (3) is a substituent on the oxygen ring, R7is unsubstituted or substituted C1-C 20 alkyl, which can or can not contain one or more of O, S, N, Si, P atoms in the carbon chain; the substituent on the alkyl group is selected from the group consisting of halogen atom, C1-C 10 branched or straight chain alkoxy; k represents the number of R7on the oxygen ring, k is an integer of 0 to 3, k = 0 means no substituent on the oxygen ring, when k is an integer of 2 or more, each R7is the same or different; preferably k is an integer of 0 to 2;

[0047] R7is preferably C1-C 10 alkyl.

[0048] Further, the acid-sensitive epoxy monomer protected by acetal / ketal is preferably represented by one of the following general formulae:

[0049]

[0050]

[0051] R4in the formulae (1-1), (1-2), (1-3) is H or C1-C 10 alkyl;

[0052] Z in the formulae (2-1), (2-2) is an oxygen atom or C1-C4alkylene;

[0053] m2 = 1 or 2, m1 = 1 or 2 in the formula (3).

[0054] In formula (1-4), (2-2), K1' is defined as K1, and when there are two R3 substituents in the same chemical formula, K1' and K1 are distinguished, and K1' and K1 can be the same or different; R8', R9', and R 10 are defined as R8, R9, and R 10 , respectively. 10 When there are two R8, R9, and R 10 substituents in the same chemical formula, R8', R9', and R 10 are distinguished from R8, R9, and R 10 , respectively. 10 R8', R9', and R 11 can be the same or different.

[0055] In the above general formula, R1, R2, K1-K4, R5, R6, R8, R9, R 13 , R 14 , R q , j, m1, m2, n1, and n2 are defined as described above.

[0056] Further, the chemical formula of the acetal / ketal-protected acid-sensitive epoxy monomer is preferably one of the following structures:

[0057]

[0058]

[0059] The present application also provides a synthesis method of the acetal / ketal-protected acid-sensitive epoxy monomer, which comprises: subjecting an olefin raw material represented by formula (4)-(6) to an oxidation reaction under the action of a peroxide, to obtain the acetal / ketal-protected acid-sensitive epoxy monomer represented by formula (1)-(3), respectively.

[0060]

[0061] In formula (4)-(6), R1-R7, Q ring, R q , i, j, k, m1, and m2 are defined as described above.

[0062] As a preferred embodiment, the peroxide is meta-chloroperoxybenzoic acid, peroxyacetic acid, hydrogen peroxide, or peroxyacetone.

[0063] The molar ratio of the peroxide to the olefin raw material represented by formula (4)-(6) is 1.1-1.5:1.

[0064] The temperature of the oxidation reaction is room temperature, and the reaction time is 1-20 hours.

[0065] The oxidation reaction is generally carried out in an organic solvent, which is usually one or more of tetrahydrofuran, benzene, toluene, chloroform, hexane, diethyl ether, dichloromethane, ethyl acetate, dimethyl sulfoxide, carbon tetrachloride, 1,4-dioxane, pyridine; preferably dichloromethane.

[0066] The volume of the organic solvent is usually 1-10 mL / mmol based on the amount of substance of the olefin raw material shown in formula (4)-(6).

[0067] After the oxidation reaction, the reaction solution is post-treated to obtain the acetal / ketal-protected acid-sensitive epoxy monomer shown in formula (1)-(3). The post-treatment method of the reaction solution is usually as follows: saturated NaSO3 solution is added until the starch iodide paper does not turn blue, then saturated NaHCO3 solution and saturated NaCl solution are sequentially washed, dried, and then the solvent is removed by rotary evaporation and distilled under reduced pressure to obtain the acetal / ketal-protected acid-sensitive epoxy monomer shown in formula (1)-(3).

[0068] In the method, the olefin raw material contains an acetal / ketal group, and the olefin raw materials of formula (4) and formula (5) can be obtained by addition of a corresponding monohydroxy olefin and a linear or cyclic alkenyl ether when R3 is formula A and formula B; can be obtained by condensation of a corresponding dihydroxy olefin and an aldehyde (ketone) when R3 is formula C; and the raw material of formula (3) can be obtained by condensation of a corresponding dihydroxy olefin and an aldehyde (ketone). This is a method for preparing acetal / ketal compounds known to those skilled in the art.

[0069] Further, in formula (1), when R1, R2, R4 are H, and R3 is a group represented by formula A or formula B, wherein K1, K2 are methylene, it can also be obtained by addition of glycidol and a linear or cyclic alkenyl ether.

[0070] The application also provides the use of the acetal / ketal-protected acid-sensitive epoxy monomer in the preparation of an acetal / ketal-protected acid-sensitive polymer. Specifically, the acetal / ketal-protected acid-sensitive epoxy monomer provided by the application can be polymerized by ring-opening of the epoxy group under the action of a catalyst or an initiator to obtain an acetal / ketal-protected acid-sensitive polymer. The ring-opening of the epoxy group includes cationic polymerization, anionic polymerization, or coordination polymerization, etc.

[0071] The acetal / ketal-protected acid-labile epoxy monomer can be used for polymerization reaction, which can be self-polymerization of one acetal / ketal-protected acid-labile epoxy monomer or copolymerization of multiple acetal / ketal-protected acid-labile epoxy monomers to obtain polyether, or copolymerization of one or more acetal / ketal-protected acid-labile epoxy monomers and reactive monomers to obtain polycarbonate, polyester, thio-polycarbonate or thio-polyester, etc.

[0072] The polymerization reaction is generally carried out in an inert solvent, such as chloroform, dichloromethane, toluene, tetrahydrofuran or the body of the acid-labile epoxy monomer, preferably toluene or the body of the acid-labile epoxy monomer as the solvent,

[0073] The polymerization reaction can use the organic metal-free catalyst with electrophilic nucleophilic bifunction disclosed in the literature (DOI: 10.1021 / jacs.0c03651, 10.1002 / anie.202002815, 10.1021 / acs.macromol.1c00250) as the catalyst for polymerization reaction.

[0074] The application also provides an acetal / ketal-protected acid-labile polymer prepared by polymerization of the acetal / ketal-protected acid-labile epoxy monomer through ring opening of the epoxy group. The acetal / ketal-protected acid-labile polymer is obtained by self-polymerization of one acetal / ketal-protected acid-labile epoxy monomer or copolymerization of multiple acetal / ketal-protected acid-labile epoxy monomers under the action of a catalyst or an initiator to obtain polyether, or copolymerization of one or more acetal / ketal-protected acid-labile epoxy monomers and reactive monomers to obtain polycarbonate, polyester, thio-polycarbonate or thio-polyester, etc.; the reactive monomers include carbon dioxide, carbon monoxide, carbon oxysulfide or carbon monosulfide.

[0075] The acetal / ketal-protected acid-labile polymer prepared from the acetal / ketal-protected acid-labile epoxy monomer can be applied in the field of chemical amplification photoresist.

[0076] Compared with the prior art, the acetal / ketal-protected acid-labile epoxy monomer provided by the application can respond to pH value, especially acidic environment, so that the polymer material obtained thereby has stimulus responsiveness. When used in the field of chemical amplification photoresist, the acid-sensitive polymer of the application responds to acid and is deprotected due to the generation of acid by the photosensitizer during exposure, thereby developing and etching. Therefore, the acetal / ketal-protected acid-labile polymer can be used in the field of chemical amplification photoresist, thereby endowing it with more functionality and higher added value.

[0077] The chemically amplified photoresist obtained by the acid-sensitive epoxy monomer protected by acetal / ketal provided by the present application has an acid-sensitive polymer main chain and side chain, and the main chain and side chain structure can be broken at the same time in the photoetching process, and strong polar groups such as hydroxyl and carboxyl are generated, which improves the solubility difference with the non-exposed area, so that higher sensitivity, contrast, resolution and lower line edge roughness can be obtained. BRIEF DESCRIPTION OF DRAWINGS

[0078] Figure 1 The nuclear magnetic resonance hydrogen spectrum of the acid-sensitive epoxy monomer A in Example 1.

[0079] Figure 2 The nuclear magnetic resonance hydrogen spectrum of the acid-sensitive epoxy monomer B in Example 2.

[0080] Figure 3 The nuclear magnetic resonance hydrogen spectrum of the acid-sensitive epoxy monomer C in Example 3.

[0081] Figure 4 The nuclear magnetic resonance hydrogen spectrum of the acid-sensitive epoxy monomer D in Example 4.

[0082] Figure 5 The nuclear magnetic resonance hydrogen spectrum of the acid-sensitive epoxy monomer E in Example 5.

[0083] Figure 6 The nuclear magnetic resonance hydrogen spectrum of the acid-sensitive epoxy monomer F in Example 6.

[0084] Figure 7 The gel permeation chromatogram of the acid-sensitive polymer P-A in Application Example 1.

[0085] Figure 8 The gel permeation chromatogram of the acid-sensitive polymer P-B in Application Example 2.

[0086] Figure 9 The gel permeation chromatogram of the acid-sensitive polymer P-C in Application Example 3.

[0087] Figure 10 The gel permeation chromatogram of the acid-sensitive polymer P-D in Application Example 4.

[0088] Figure 11 The gel permeation chromatogram of the acid-sensitive polymer P-E in Application Example 5.

[0089] Figure 12 The gel permeation chromatogram of the acid-sensitive polymer P-F in Application Example 6.

[0090] Figure 13 The resolution characterization result of the photoresist P-A in Application Example 7. DETAILED DESCRIPTION

[0091] In order to make the objectives, technical solutions and advantages of the present application clearer, the present application will be further described in detail below with reference to the accompanying drawings and examples. It should be understood that the specific embodiments described herein are merely intended to explain the present application and do not limit the protection scope of the present application.

[0092] Example 1

[0093] The structure and synthesis route of the epoxy monomer A are as follows:

[0094]

[0095] To 56 g of 3-cyclohexen-1-methanol, 0.5 g of p-toluenesulfonic acid (TsOH) was added, and 60 g (1.2 molar equivalents) of t-butyl vinyl ether was slowly added dropwise. After reaction at 60°C for 2 h, it was cooled to room temperature, 1 g of NaHCO3 and 2 g of anhydrous Na2SO4 solid were added and stirred for 1 h. After removing the solid by filtration, the raw material a was obtained by distillation under reduced pressure.

[0096] The raw material a was dissolved in 1 L of dichloromethane, and 87 g (85 wt% purity, 1.2 molar equivalents) of m-chloroperbenzoic acid (m-CPBA) was added. After reaction at room temperature for 12 h, saturated NaSO3 solution was added until the starch iodide paper did not turn blue. It was washed with saturated NaHCO3 solution for 3 times, washed with saturated NaCl solution for 1 time, dried with anhydrous Na2SO4, and distilled under reduced pressure after removing dichloromethane by rotary evaporation. 86 g of epoxy monomer A was obtained. The nuclear magnetic resonance hydrogen spectrum is shown as follows: Figure 1

[0097] Example 2

[0098] The structure and synthesis route of the epoxy monomer B are as follows:

[0099]

[0100] The epoxy monomer B can be obtained by the same synthesis method as in Example 1, except that t-butyl vinyl ether in the addition reaction is replaced by 2-methyl-2-adamantyl vinyl ether. It can be known from the nuclear magnetic resonance hydrogen spectrum shown as follows that the epoxy monomer B is obtained. Figure 2

[0101] Example 3

[0102] The structure and synthesis route of the epoxy monomer C are as follows:

[0103]

[0104] ​​Epoxy monomer C can be obtained by the same synthetic method as Example 1, except that 3-cyclohexene-l-methanol in the addition reaction is replaced by 1,2- cyclohexandien-4-ol and the amount of t-butyl vinyl ether is increased to 2.2 equivalents. Epoxy monomer C is obtained as shown by the nuclear magnetic resonance hydrogen spectrum shown in Figure 1. Figure 3 Epoxy monomer C is obtained as shown by the nuclear magnetic resonance hydrogen spectrum shown in Figure 1.

[0105] Example 4

[0106] The structure and synthetic route of epoxy monomer D are as follows:

[0107]

[0108] Since glycidol is a common organic compound, such epoxy monomers can be obtained directly from glycidol.

[0109] To 37 g of glycidol, 0.5 g of p-toluenesulfonic acid (TsOH) is added, and 60 g (1.2 mole equivalents) of t-butyl vinyl ether is slowly added dropwise. After 2 h of reaction at 60 °C, the mixture is cooled to room temperature, and 1 g of NaHCO3 and 2 g of anhydrous Na2SO4 solid are added and stirred for 1 h. The solid is removed by filtration, and 59 g of epoxy monomer D is obtained after distillation under reduced pressure. The nuclear magnetic resonance hydrogen spectrum is shown in Figure 2. Figure 4

[0110] Example 5

[0111] The structure and synthetic route of epoxy monomer E are as follows:

[0112]

[0113] Epoxy monomer E can be obtained by the same synthetic method as Example 4, except that t-butyl vinyl ether in the addition reaction is replaced by t-butyl phenyl styryl ether. Epoxy monomer E is obtained as shown by the nuclear magnetic resonance hydrogen spectrum shown in Figure 3. Figure 5

[0114] Example 6

[0115] The structure and synthetic route of epoxy monomer F are as follows:

[0116]

[0117] To 44 g of 1,2-dihydroxymethyl ethylene and 53 g of benzaldehyde, 40 g of toluene (TOL) is added, and the mixture is heated to reflux and water is removed. After 2 h, the mixture is cooled to room temperature, washed with saturated NaHCO3 and saturated NaCl solutions, respectively, and dried with anhydrous Na2SO4. The solid is removed by filtration, and the toluene is removed by rotary evaporation. Epoxy monomer F is obtained after distillation under reduced pressure.

[0118] ​​The raw material f was dissolved in 1 L of dichloromethane, 87 g (85 wt% purity, 1.2 mole equivalents) of m-chloroperbenzoic acid (m-CPBA) was added, and after reaction at room temperature for 12 h, saturated NaSO3 solution was added until the starch iodide paper did not turn blue, saturated NaHCO3 solution was washed 3 times, saturated NaCl solution was washed 1 time, anhydrous Na2SO4 was dried, and after removing dichloromethane by rotary evaporation, it was distilled under reduced pressure to obtain 61 g of epoxy monomer F. The nuclear magnetic resonance hydrogen spectrum is shown in Figure 6 .

[0119] The epoxy monomers A-F were homopolymerized or copolymerized with carbon monoxide, carbon dioxide to prepare acid-sensitive polymers. In the following application examples, the catalysts cat1 and cat2 are disclosed in the literature, which can be prepared according to the method disclosed in the literature (DOI: 10.1021 / jacs.0c03651, 10.1002 / anie.202002815, 10.1021 / acs.macromol.1c00250).

[0120]

[0121] Application Example 1

[0122] The synthesis route of the copolymerization of epoxy monomer A with carbon dioxide to obtain polycarbonate P-A is as follows:

[0123]

[0124] In a high-pressure reaction kettle, 33 mg of bifunctional organic boron catalyst cat1 was weighed, 22.8 g of epoxy monomer A was added, 3 MPa of carbon dioxide was filled into the reaction kettle, and the reaction was carried out at 80°C for 2 h. The product was dissolved in dichloromethane, and white powder polymer P-A was obtained by precipitation in ethanol. The number average molecular weight of P-A was 48 kDa, and the molecular weight distribution was 1.13. The gel permeation chromatogram is shown in Figure 7 .

[0125] Application Example 2

[0126] The synthesis route of the copolymerization of epoxy monomer A and epoxy monomer B with carbon dioxide to obtain polycarbonate P-B is as follows:

[0127]

[0128] In a high-pressure reaction kettle, 33 mg of bifunctional organic boron catalyst cat1 was weighed, 11.4 g of epoxy monomer A and 16.0 g of epoxy monomer B were added, 3 MPa of carbon dioxide was filled into the reaction kettle, and the reaction was carried out at 80°C for 2 h. The product was dissolved in dichloromethane, and white polymer P-B was obtained by precipitation in ethanol. The number average molecular weight of P-B was 57 kDa, and the molecular weight distribution was 1.14. The gel permeation chromatogram is shown in Figure 8 .

[0129] Application Example 3

[0130] The synthetic route of the copolymerization of the epoxy monomer C with carbon dioxide to obtain polycarbonate P-C is as follows:

[0131]

[0132] The polycarbonate P-C can be obtained by the same synthetic method as in Application Example 1, except that the reaction raw material is changed from the epoxy monomer A to the epoxy monomer C. The number average molecular weight of P-C is 38 kDa, and the molecular weight distribution is 1.17. The gel permeation chromatogram is shown in Figure 9 .

[0133] Application Example 4

[0134] The synthetic route of the copolymerization of the epoxy monomer D with carbon monoxide to obtain polyester P-D is as follows:

[0135]

[0136] In a high-pressure reaction kettle, 33 mg of the bifunctional organoboron catalyst cat1 was weighed, 17.4 g of the epoxy monomer D was added, 4 MPa of carbon monoxide was filled into the reaction kettle, and the reaction was carried out at 80°C for 12 h. The product was dissolved in dichloromethane, and a white polymer P-D was obtained by precipitation in ethanol. The number average molecular weight of P-D is 18 kDa, and the molecular weight distribution is 1.23. The gel permeation chromatogram is shown in Figure 10 .

[0137] Application Example 5

[0138] The synthetic route of the copolymerization of the epoxy monomer E with carbon monoxide to obtain polyester P-E is as follows:

[0139]

[0140] In a high-pressure reaction kettle, 33 mg of the bifunctional organoboron catalyst cat1 was weighed, 25.0 g of the epoxy monomer E was added, 3 MPa of carbon monoxide was filled into the reaction kettle, and the reaction was carried out at 80°C for 12 h. The product was dissolved in dichloromethane, and a white polymer P-E was obtained by precipitation in ethanol. The number average molecular weight of P-E is 23 kDa, and the molecular weight distribution is 1.25. The gel permeation chromatogram is shown in Figure 11 .

[0141] Application Example 6

[0142] The synthetic route of the self-polymerization of the epoxy monomer F to obtain polyether P-F is as follows:

[0143]

[0144] In a high-pressure reactor, 49 mg of bifunctional organoboron catalyst cat2 was weighed, and 19.2 g of epoxy monomer F was added. The reaction was carried out at 25°C for 2 h. The product was dissolved in dichloromethane, and a white polymer P-F was obtained by precipitation in ethanol. The number average molecular weight of P-F was 66 kDa, and the molecular weight distribution was 1.11. The gel permeation chromatogram is shown in Figure 12 .

[0145] Application Example 7

[0146] The application methods of the acetal / ketal-protected acid-sensitive polymers P-A to P-F synthesized in Application Examples 1 to 6 as chemically amplified photoresists are as follows:

[0147] 1 g of polymer resin, 50 mg of diphenyl iodonium triflate, and 5 mg of trioctylamine were dissolved in 20 g of propylene glycol monomethyl ether acetate, and a photoresist solution was obtained by filtration with a 0.22 μm filter. The photoresist solution was spin-coated on a silicon wafer at a rotation speed of 4000 rpm, and a photoresist film was obtained by removing the solvent at 120°C in the dark for 5 min.

[0148] The photoresist film was exposed by using a Raith Elphy Quantum electron beam lithography system at a voltage of 20 kV and a beam current of 40 pA. After exposure, the photoresist film was baked at 120°C for 5 min, and then developed in isopropyl alcohol for 1 min and fixed in water for 1 min to obtain a photoresist pattern. The sensitivity and contrast data were measured by the NRT analysis method (Normalized remaining thickness), and the resolution (critical dimension) was obtained by exposing a grating structure. The photoresist performance parameters of the chemically amplified photoresist obtained from the acid-sensitive epoxy monomer are shown in Table 1, and the resolution characterization results of the photoresist P-A are shown in Figure 13 . Figure 13 SEM photos of grating structures.

[0149] Table 1 Photoresist performance parameters of chemically amplified photoresists based on acid-sensitive epoxy monomers

[0150]

[0151] Compared with the prior art, the chemically amplified photoresist obtained from the acetal / ketal-protected acid-sensitive epoxy monomer provided by the present application has an acid-sensitive polymer main chain and side chain, and the main chain and side chain structure can be broken at the same time during the photoresist process, and hydrophilic hydroxyl groups are generated, which improves the solubility difference with the non-exposed area, so that higher sensitivity, contrast, resolution, and lower line edge roughness can be obtained.

[0152] The above detailed description of the specific embodiments of the present application has described the technical solutions and beneficial effects of the present application, and it should be understood that the above description is only the most preferred embodiment of the present application and is not intended to limit the present application. Any modifications, supplements and equivalent replacements made within the principle range of the present application shall be included in the protection range of the present application.

Claims

1. Use of an acetal / ketal-protected acid-sensitive epoxy monomer in the preparation of an acetal / ketal-protected acid-sensitive polymer, wherein the acetal / ketal-protected acid-sensitive epoxy monomer is polymerized by ring-opening polymerization of the epoxy group in the presence of a catalyst or an initiator to obtain the acetal / ketal-protected acid-sensitive polymer, and wherein the polymerization is a self-polymerization of the acetal / ketal-protected acid-sensitive epoxy monomer or a copolymerization of a plurality of acetal / ketal-protected acid-sensitive epoxy monomers to obtain a polyether, or a copolymerization of one or more acetal / ketal-protected acid-sensitive epoxy monomers with a reactive monomer to obtain a polycarbonate or a polyester, and wherein the reactive monomer is carbon dioxide or carbon monoxide, and wherein the acetal / ketal-protected acid-sensitive epoxy monomer has a chemical formula represented by Formula (1) to Formula (3): ###0001### ###0002### ###0003### wherein R3 in Formula (1) or Formula (2) is a group represented by Formula A: ###0004### wherein i in Formula (2) represents the number of R3 groups on the Q ring, and i = 1 or 2, wherein the Q ring in Formula (2) represents a cyclic group in which two carbon atoms of an epoxy group and a carbon chain are connected to form a ring, and the Q ring is one of the following: ###0005### wherein Z represents a C1-C5 alkylene group, and wherein m1 and m2 are each independently an integer from 1 to 5. In equations (1) to (3), R1 is H or C1-C. 10 Alkyl group; R2 is H or C1-C 10 Alkyl groups; 2. The acetal / ketal-protected acid-sensitive polymer obtained by ring-opening polymerization of the acetal / ketal-protected acid-sensitive epoxy monomer, wherein the polymer is obtained by a self-polymerization of the acetal / ketal-protected acid-sensitive epoxy monomer or a copolymerization of a plurality of acetal / ketal-protected acid-sensitive epoxy monomers to obtain a polyether, or a copolymerization of one or more acetal / ketal-protected acid-sensitive epoxy monomers with a reactive monomer to obtain a polycarbonate or a polyester, and wherein the reactive monomer is carbon dioxide or carbon monoxide, and wherein the acetal / ketal-protected acid-sensitive epoxy monomer has a chemical formula represented by Formula (1) to Formula (3): ###0006### ###0007### ###0008### wherein R3 in Formula (1) or Formula (2) is a group represented by Formula A: ###0009### wherein i in Formula (2) represents the number of R3 groups on the Q ring, and i = 1 or 2, wherein the Q ring in Formula (2) represents a cyclic group in which two carbon atoms of an epoxy group and a carbon chain are connected to form a ring, and the Q ring is one of the following: ###0010### wherein Z represents a C1-C5 alkylene group, and wherein m1 and m2 are each independently an integer from 1 to 5. represents a bond; In formula A, K1is absent or C1-C 10 alkylene; In formula A, R8is H or C1-C 10 alkyl, R9is C1-C 10 alkyl or C6-C 10 aromatic; In the formula A, R 10 is a C1-C 10 alkyl group, a C3-C7 heterocyclic group, a pyrrolidone, a butyrolactone group, a phenyl group, a benzyl group, a norbornene group, an adamantyl group; In the formula (1), R4is H, C1-C 10 alkyl, or is of the formula A; 3. The acetal / ketal-protected acid-sensitive polymer obtained by ring-opening polymerization of the acetal / ketal-protected acid-sensitive epoxy monomer, wherein the polymer is obtained by a self-polymerization of the acetal / ketal-protected acid-sensitive epoxy monomer or a copolymerization of a plurality of acetal / ketal-protected acid-sensitive epoxy monomers to obtain a polyether, or a copolymerization of one or more acetal / ketal-protected acid-sensitive epoxy monomers with a reactive monomer to obtain a polycarbonate or a polyester, and wherein the reactive monomer is carbon dioxide or carbon monoxide, and wherein the acetal / ketal-protected acid-sensitive epoxy monomer has a chemical formula represented by Formula (1-1) to Formula (3): ###0011### ###0012### ###0013### wherein R3 in Formula (1-1) or Formula (2-1) is a group represented by Formula A: ###0014### wherein i in Formula (2-1) represents the number of R3 groups on the Q ring, and i = 1 or 2, wherein the Q ring in Formula (2-1) represents a cyclic group in which two carbon atoms of an epoxy group and a carbon chain are connected to form a ring, and the Q ring is one of the following: ###0015### wherein Z represents a C1-C4 alkylene group, and wherein m1 and m2 are each independently an integer from 1 to 5.

4. The acetal / ketal-protected acid-sensitive polymer obtained by ring-opening polymerization of the acetal / ketal-protected acid-sensitive epoxy monomer, wherein the polymer is obtained by a self-polymerization of the acetal / ketal-protected acid-sensitive epoxy monomer or a copolymerization of a plurality of acetal / ketal-protected acid-sensitive epoxy monomers to obtain a polyether, or a copolymerization of one or more acetal / ketal-protected acid-sensitive epoxy monomers with a reactive monomer to obtain a polycarbonate or a polyester, and wherein the reactive monomer is carbon dioxide or carbon monoxide, and wherein the acetal / ketal-protected acid-sensitive epoxy monomer has a chemical formula represented by Formula (1) to Formula (3): ###0016### ###0017### ###0018### wherein R3 in Formula (1) or Formula (2) is a group represented by Formula A: ###0019### wherein i in Formula (2) represents the number of R3 groups on the Q ring, and i = 1 or 2, wherein the Q ring in Formula (2) represents a cyclic group in which two carbon atoms of an epoxy group and a carbon chain are connected to form a ring, and the Q ring is one of the following: ###0020### wherein Z represents a C1-C5 alkylene group, and wherein m1 and m2 are each independently an integer from 1 to 5. represents a bond; 5. Use of the acetal / ketal-protected acid-sensitive polymer of claim 4 in a chemically amplified photoresist. In the formula (3), R5is H or C1-C4alkyl, R6is C1-C4alkyl or phenyl; and R7is H or C1-C4alkyl. 10 In the formula (3), R5is H or C1-C4alkyl, R6is C1-C4alkyl or phenyl; and R7is H or C1-C4alkyl. 10 ​ ​ 2. Use according to claim 1, wherein ​ In formulae (1-1), (1-2), (1-3), R4is H or C1-C 10 alkyl; ​ ​ in the formulae (1-4), (2-2), K1' is the same as K1; R8', R9', R 10 ' are the same as R8, R9, R 10 , respectively; In the above general formula, R1, R2, K1, R5, R6, R8, R 10 , m1, m2 are defined as in claim 1.

3. The use according to claim 1, wherein ​ ​ ​ In equations (1) to (3), R1 is H or C1-C. 10 Alkyl group; R2 is H or C1-C 10 Alkyl groups; ​ represents a bond; In formula A, K1is absent or C1-C 10 alkylene; In formula A, R8is H or C1-C 10 alkyl, R9is C1-C 10 alkyl or C6-C 10 aromatic; In the formula A, R 10 is a C1-C 10 alkyl group, a C3-C7 heterocyclic group, a pyrrolidone, a butyrolactone group, a phenyl group, a benzyl group, a norbornene group, an adamantyl group; In the formula (1), R4is H, C1-C 10 alkyl, or is of the formula A; ​ ​ represents a bond; ​ In the formula (3), R5is H or C1-C4alkyl, R6is C1-C4alkyl or phenyl; and R7is H or C1-C4alkyl. 10 In the formula (3), R5is H or C1-C4alkyl, R6is C1-C4alkyl or phenyl; and R7is H or C1-C4alkyl. 10 ​ ​ ​ 6. A method of synthesizing an acetal / ketal-protected acid-sensitive epoxy monomer, characterized by The method is to oxidize the olefin raw material shown in formula (4) to (6) under the action of peroxide to obtain the acetal / ketal protected acid-sensitive epoxy monomer shown in formula (1) to (3) respectively. In formula (4) to (6), R1 to R6, Q ring, i, m1, and m2 are defined in claim 1.

7. The method of claim 6, wherein The peroxide is meta-chloroperoxybenzoic acid, peroxyacetic acid, hydrogen peroxide, or peroxyacetone.

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