CN114835659A - 一种酸敏性环氧单体及其合成方法和应用 - Google Patents
一种酸敏性环氧单体及其合成方法和应用 Download PDFInfo
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- CN114835659A CN114835659A CN202210173522.6A CN202210173522A CN114835659A CN 114835659 A CN114835659 A CN 114835659A CN 202210173522 A CN202210173522 A CN 202210173522A CN 114835659 A CN114835659 A CN 114835659A
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- alkyl
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- epoxy monomer
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- 238000001308 synthesis method Methods 0.000 title abstract description 8
- 229920000642 polymer Polymers 0.000 claims abstract description 33
- 229920002120 photoresistant polymer Polymers 0.000 claims abstract description 18
- 125000000217 alkyl group Chemical group 0.000 claims description 43
- 125000002947 alkylene group Chemical group 0.000 claims description 27
- 125000001424 substituent group Chemical group 0.000 claims description 27
- 229910052760 oxygen Inorganic materials 0.000 claims description 25
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical group O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 24
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 23
- -1 Alkyl radical Chemical class 0.000 claims description 18
- 229910052757 nitrogen Inorganic materials 0.000 claims description 18
- 229910052717 sulfur Inorganic materials 0.000 claims description 16
- 229910052739 hydrogen Inorganic materials 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 14
- 229910052799 carbon Inorganic materials 0.000 claims description 13
- 125000005843 halogen group Chemical group 0.000 claims description 13
- 238000006116 polymerization reaction Methods 0.000 claims description 13
- 229910052710 silicon Inorganic materials 0.000 claims description 13
- 125000003545 alkoxy group Chemical group 0.000 claims description 12
- 239000001569 carbon dioxide Substances 0.000 claims description 12
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 12
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- 125000004437 phosphorous atom Chemical group 0.000 claims description 10
- 239000002994 raw material Substances 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 8
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- 125000000027 (C1-C10) alkoxy group Chemical group 0.000 claims description 4
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims description 4
- NHQDETIJWKXCTC-UHFFFAOYSA-N 3-chloroperbenzoic acid Chemical group OOC(=O)C1=CC=CC(Cl)=C1 NHQDETIJWKXCTC-UHFFFAOYSA-N 0.000 claims description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 4
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- DXHPZXWIPWDXHJ-UHFFFAOYSA-N carbon monosulfide Chemical compound [S+]#[C-] DXHPZXWIPWDXHJ-UHFFFAOYSA-N 0.000 claims description 4
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 4
- 239000003999 initiator Substances 0.000 claims description 4
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- 125000001118 alkylidene group Chemical group 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
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- OLRJXMHANKMLTD-UHFFFAOYSA-N silyl Chemical compound [SiH3] OLRJXMHANKMLTD-UHFFFAOYSA-N 0.000 claims description 3
- 125000006832 (C1-C10) alkylene group Chemical group 0.000 claims description 2
- 239000000011 acetone peroxide Substances 0.000 claims description 2
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- 125000000304 alkynyl group Chemical group 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 150000005840 aryl radicals Chemical class 0.000 claims description 2
- 125000004429 atom Chemical group 0.000 claims description 2
- 125000004122 cyclic group Chemical group 0.000 claims description 2
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- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical compound OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 125000004185 ester group Chemical group 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 238000002390 rotary evaporation Methods 0.000 description 3
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- 238000010189 synthetic method Methods 0.000 description 3
- 238000005292 vacuum distillation Methods 0.000 description 3
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- 101150116295 CAT2 gene Proteins 0.000 description 2
- 101100326920 Caenorhabditis elegans ctl-1 gene Proteins 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 241001274216 Naso Species 0.000 description 2
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- 229920002472 Starch Polymers 0.000 description 2
- 150000001263 acyl chlorides Chemical class 0.000 description 2
- 125000005073 adamantyl group Chemical group C12(CC3CC(CC(C1)C3)C2)* 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
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- 125000003518 norbornenyl group Chemical group C12(C=CC(CC1)C2)* 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
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- JSSXHAMIXJGYCS-UHFFFAOYSA-N piperazin-4-ium-2-carboxylate Chemical compound OC(=O)C1CNCCN1 JSSXHAMIXJGYCS-UHFFFAOYSA-N 0.000 description 2
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- JKOZWMQUOWYZAB-UHFFFAOYSA-N 2-methyladamantan-2-ol Chemical compound C1C(C2)CC3CC1C(C)(O)C2C3 JKOZWMQUOWYZAB-UHFFFAOYSA-N 0.000 description 1
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- SBQIJPBUMNWUKN-UHFFFAOYSA-M diphenyliodanium;trifluoromethanesulfonate Chemical compound [O-]S(=O)(=O)C(F)(F)F.C=1C=CC=CC=1[I+]C1=CC=CC=C1 SBQIJPBUMNWUKN-UHFFFAOYSA-M 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/48—Compounds containing oxirane rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms, e.g. ester or nitrile radicals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/14—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with organic peracids, or salts, anhydrides or esters thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/12—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms
- C07D303/16—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms by esterified hydroxyl radicals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/38—Compounds containing oxirane rings with hydrocarbon radicals, substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D303/40—Compounds containing oxirane rings with hydrocarbon radicals, substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals by ester radicals
- C07D303/42—Acyclic compounds having a chain of seven or more carbon atoms, e.g. epoxidised fats
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D407/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00
- C07D407/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00 containing two hetero rings
- C07D407/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00 containing two hetero rings linked by a chain containing hetero atoms as chain links
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
- C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
- C07D493/04—Ortho-condensed systems
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
- C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
- C07D493/08—Bridged systems
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0803—Compounds with Si-C or Si-Si linkages
- C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
- C07F7/0812—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/40—Polyesters derived from ester-forming derivatives of polycarboxylic acids or of polyhydroxy compounds, other than from esters thereof
- C08G63/42—Cyclic ethers; Cyclic carbonates; Cyclic sulfites; Cyclic orthoesters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/20—General preparatory processes
- C08G64/32—General preparatory processes using carbon dioxide
- C08G64/34—General preparatory processes using carbon dioxide and cyclic ethers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/04—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers only
- C08G65/22—Cyclic ethers having at least one atom other than carbon and hydrogen outside the ring
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Abstract
本发明公开了一种酸敏性环氧单体,化学式如式(1)~式(3)之一所示,R3为式A~式C之一,并公开了其合成方法,以及制备酸敏性聚合物的应用。本发明提供的具有酸敏性的环氧单体可以对pH值,尤其是酸性环境进行响应,使其得到的聚合物材料具有刺激响应性。因此酸敏性聚合物可以用于化学放大光刻胶领域,从而赋予其更多的功能性和更高的附加值。
Description
技术领域
本发明涉及有机化合物领域,具体涉及一种酸敏性环氧单体及其合成方法和应用。
背景技术
环氧化合物是一类高反应活性的聚合单体,可以在金属或无金属催化剂的催化下进行均聚得到聚醚,也可以与一氧化碳、二氧化碳等小分子共聚得到更为刚性的聚酯和聚碳酸酯(J.Am.Chem.Soc.2020,142,12245;Angew.Chem.Int.Ed.2020,59,2;Macromolecules 2021,54,9427;CN201710046977.0;CN200610154860.6)。环氧基聚合物由于主链具有易于断裂的化学键和基团,是一类典型的可降解聚合物。然而,常见的环氧单体缺少富有反应性的功能基团,这使得环氧基的聚合物只能作为通用材料使用,而缺乏功能性,并且与传统的聚烯烃材料相比,环氧基的聚合物在成本与力学性能上并不占据优势。因此,开发具有功能性的环氧单体以制备高附加值的环氧基聚合物材料十分重要。
发明内容
本发明的目的在于针对现有技术的不足,提供一种酸敏性环氧单体,并提供其合成方法。
本发明的另一目的在于提供该酸敏性环氧单体的应用。
本发明提供的技术方案为:
一种酸敏性环氧单体,所述的酸敏性环氧单体的化学式如式(1)~式(3)之一所示:
所述式(1)~式(3)中,R1、R2各自独立为H、未取代的或具有取代基的C1-C20烷基,所述烷基的碳链内含有或不含有O、S、N、Si、P原子中的一种或多种;所述烷基上的取代基选自卤素原子、C1-C20的支链或直链的烷基、C1-C20的支链或直链的烷氧基中的一种或多种;
优选R1为H或C1-C10的烷基;优选R2为H或C1-C10的烷基;
所述式(1)或式(2)中,R3为下列基团式A~式C之一:
式A中,K1为0、C1-C20亚烷基、苯基、或碳链中含有氧或硫原子的C1-C20亚烷基,所述亚烷基、苯基上的H不被取代或被C1-C10的烷基或C1-C10的烷氧基取代;优选为0、C1-C10亚烷基或苯基;K1为0即代表酯基连接环氧环;
式B中,K2为0、C1-C20亚烷基、苯基、或碳链中含有氧或硫原子的C1-C20亚烷基,所述亚烷基、苯基上的H不被取代或被C1-C10的烷基或C1-C10的烷氧基取代;优选K2为0或C1-C10亚烷基;进一步,式(1)中的K2不可为0,优选C1-C10亚烷基;式(2)中的K2可以为0,优选为0或C1-C10亚烷基;
式C中,K3为C1-C20次烷基,优选为C1-C6次烷基;
式A~式C中,R6、R7、R8、R9各自独立选自包含或不包含取代基的以下基团:C1-C30烷基、C3-C30环烷基、C3-C30炔基、C4-C30硅烷基、C6-C30芳香基、C3-C30杂环基或C5-C30杂芳香基,或者为碳链中含有O、S、N、Si、P原子中的一种或多种的所述基团;其中所述取代基选自卤素原子、羟基、三氟甲基、六氟异丙基、C1-C20的支链或直链的烷基、C1-C20的支链或直链的烷氧基、C3-C20的支链或直链的环烷基、C6-C30的芳香基、C5-C30的杂芳香基中的一种或多种;
优选R6、R7、R8、R9各自独立选自包含或不包含取代基的以下基团:C1-C10烷基,C3-C15环烷基、C4-C10硅烷基、C6-C15芳香基、C3-C15杂环基或C5-C15杂芳香基,所述取代基选自卤素原子、羟基、三氟甲基、六氟异丙基、C1-C10的支链或直链的烷基、C1-C10的支链或直链的烷氧基中的一种或多种;所述的环烷基优选为降冰片烯基及其衍生基团、金刚烷基及其衍生基团;
更优选R6、R7、R8、R9各自独立为包含或不包含取代基的以下基团:C1~C5的烷基、C3-C7的环烷基、C3~C7的杂环基、三氟甲基、六氟异丙基、降冰片烯基及其衍生基团、金刚烷基及其衍生基团,或者为碳链中含有O、S、Si原子中的一种或多种的所述基团;所述取代基选自卤素原子、羟基、三氟甲基、C1-C5的烷基、C1-C10的烷氧基中的一种或多种。
所述式(1)中,R4为H、未取代的或具有取代基的C1-C20烷基,或者为式A~式C之一;所述烷基的碳链内含有或不含有O、S、N、Si、P原子中的一种或多种;所述烷基上的取代基选自卤素原子、C1-C10的支链或直链的烷基、C1-C10的支链或直链的烷氧基中的一种或多种;式A~式C中K1、K2、K3、R6、R7、R8、R9的定义如前所述;
优选R4为H、C1-C10烷基,或者为式A~式C之一;更优选R4为H、C1-C10烷基,或者和R3相同;
式(2)中,i代表Q环上R3的个数,i=1或2,i=2时,代表Q环上有2个R3,两个R3可以相同或也可以不同;
当i=2时,式(2)也可以用下式表达:
其中的R3’的定义同R3,在同一化学式中有两个R3取代基时,用R3和R3’进行区分,R3和R3’可以相同也可以不同;
所述式(2)中,Q环代表环氧基团上的两个碳原子和碳链连接成环的环状基团,所述Q环为下列之一:
其中Z表示O、N、S、C1-C20亚烷基或碳链中含有氧、氮或硫原子中的一种或多种的C1-C20亚烷基;Z优选为O、N、S、C1-C5亚烷基或碳链中含有氧、氮或硫原子中的一种或多种的C1-C5亚烷基;
所述式(2)中,Rq代表Q环上除R3以外的取代基,Rq为未取代的或具有取代基的C1-C20烷基,所述烷基的碳链内含有或不含有O、S、N、Si、P原子中的一种或多种;所述烷基上的取代基选自卤素原子、C1-C10的支链或直链的烷氧基中的一种或多种;
j代表Q环上Rq的个数,j为0~3的整数,j=0时代表Q环上只有R3取代基,没有其他的取代基,j为2以上的整数时,各个Rq相同或不同;优选j=0或1;
优选Rq为C1-C10烷基;
所述式(3)中,m1、m2各自独立的取自0-20之间的整数,但不可同时取0;优选m2为0~5的整数,m1为1~5的整数。
所述式(3)中,环氧基团上的两个碳原子和酯基成环得到内酯,R5为内酯环中碳链上的取代基,R5为未取代的或具有取代基的C1-C20烷基,所述烷基的碳链内含有或不含有O、S、N、Si、P原子中的一种或多种;所述烷基上的取代基选自卤素原子、C1-C10的支链或直链的烷氧基中的一种或多种;k代表内酯环上R5的个数,k为0~3的整数,k=0时代表内酯环上没有取代基,k为2以上的整数时,各个R5相同或不同;优选k为0~2的整数;
优选R5为C1-C10烷基。
进一步,优选所述的酸敏性环氧单体的化学式如下列通式之一所示:
式(1-1)、(1-2)、(1-3)中,R4为H或C1-C10烷基;
式(2-1)、(2-2)中,Z为O或C1-C4亚烷基;
式(3)中,m2=0或1,m1=1或2;
式(1-4),(2-2)中,K1’的定义同K1,在同一化学式中有两个R3取代基时,用K1’和K1进行区分,K1’和K1可以相同也可以不同;R6’的定义同R6,在同一化学式中有两个R6取代基时,用R6’和R6进行区分,R6’和R6可以相同也可以不同;
上述通式中,R1、R2、K1、K2、K3、R5~R9、Rq、j、k的定义如前所述。
更进一步,所述的酸敏性环氧单体的化学结构优选为以下结构之一:
本发明还提供所述酸敏性环氧单体的合成方法,所述方法为,将式(4)~式(6)所示的烯烃类原料在过氧化物的作用下,进行氧化反应,分别相应制得所述式(1)~式(3)所示的酸敏性环氧单体;
作为优选,所述的过氧化物为间氯过氧苯甲酸、过氧乙酸、过氧化氢或过氧丙酮。
所述过氧化物和式(4)~式(6)所示的烯烃类原料的物质的量之比为1.1~1.5:1。
所述氧化反应的温度为室温,反应时间为1~20h。
氧化反应一般在有机溶剂中进行,所述有机溶剂通常为四氢呋喃、苯、甲苯、氯仿、己烷、乙醚、二氯甲烷、乙酸乙酯、二甲基亚砜、四氯化碳、1,4-二氧六环、吡啶中的一种或多种;优选为二氯甲烷。
有机溶剂的体积用量通常以式(4)~式(6)所示的烯烃类原料的物质的量计为1~10mL/mmol。
氧化反应后将反应液后处理制得所述式(1)~式(3)所示的酸敏性环氧单体,反应液后处理方法通常为,加入饱和NaSO3溶液至淀粉碘化钾试纸不变蓝,依次用饱和NaHCO3溶液、饱和NaCl溶液洗涤,干燥后蒸除溶剂后减压蒸馏,制得所述式(1)~式(3)所示的酸敏性环氧单体。
所述方法中,所述的式(4)或式(5)所示的烯烃类原料中含有酯基,可以通过相应的含有双键的羧酸类化合物和醇类化合物进行酯化反应得到,或者也可以通过相应的含有双键的羧酸类化合物和氯化亚砜反应得到酰氯化合物,再和醇类化合物经过酯化反应得到。这是本领域技术人员公知的制备酯基化合物的方法。
进一步,所述式(1)中,当R1、R2、R4为H,R3为式B所示的基团、其中的K2为亚甲基时,也可以由缩水甘油和环氧羧酸进行酯化反应得到。
本发明还提供了所述酸敏性环氧单体在制备酸敏性聚合物中的应用,具体的,本发明提供的酸敏性环氧单体可以在催化剂或引发剂的作用下,通过环氧开环的方式进行聚合反应制备得到酸敏性聚合物。其中,所述的环氧开环的方式包括阳离子聚合、阴离子聚合或配位聚合等方法。
所述的酸敏性环氧单体在进行聚合反应时,所述聚合反应可以是一种酸敏性环氧单体进行自聚合反应或多个酸敏性环氧单体进行共聚合反应得到聚醚,也可以是一种或多种酸敏性环氧单体与反应性单体进行共聚合反应得到聚碳酸酯、聚酯、硫代聚碳酸酯或硫代聚酯等;所述的反应性单体包括二氧化碳、一氧化碳、氧硫化碳或一硫化碳。
聚合反应一般在惰性溶剂,如氯仿、二氯甲烷、甲苯、四氢呋喃或酸敏性环氧单体本体中进行,优选以甲苯或酸敏性环氧单体本体作为溶剂,
所述聚合反应可采用文献(DOI:10.1021/jacs.0c03651、10.1002/anie.202002815、10.1021/acs.macromol.1c00250)公开的具有亲电亲核双功能的有机无金属催化剂作为聚合反应的催化剂。
本发明还提供酸敏性环氧单体通过环氧开环的方式进行聚合反应制备得到的酸敏性聚合物。所述的酸敏性聚合物是在催化剂或引发剂的作用下,一种酸敏性环氧单体进行自聚合反应或多个酸敏性环氧单体进行共聚合反应得到的聚醚,或者是一种或多种酸敏性环氧单体与反应性单体进行共聚合反应得到的聚碳酸酯、聚酯、硫代聚碳酸酯或硫代聚酯等;所述的反应性单体包括二氧化碳、一氧化碳、氧硫化碳或一硫化碳。
酸敏性环氧单体制得的酸敏性聚合物可以应用于化学放大光刻胶领域。
同现有技术相比,本发明的有益效果在于:本发明提供的具有酸敏性的环氧单体可以对pH值,尤其是酸性环境进行响应,使其得到的聚合物材料具有刺激响应性。用于化学放大光刻胶领域时,由于曝光时光敏剂产酸,本申请的酸敏性聚合物对酸产生响应发生脱保护,从而显影刻蚀。因此酸敏性聚合物可以用于化学放大光刻胶领域,从而赋予其更多的功能性和更高的附加值。
通过本发明提供的酸敏性环氧单体得到的化学放大光刻胶具有酸敏感的聚合物主链及侧链,在光刻过程中可以同时发生主链与侧链结构的断裂,并产生羟基、羧基等强极性基团,提高了与非曝光区域的溶解度差异,从而可以得到更高的灵敏度、对比度、分辨率以及更低的线边缘粗糙度。
附图说明
图1为实施例1中酸敏性环氧单体A的核磁共振氢谱图。
图2为实施例2中酸敏性环氧单体B的核磁共振氢谱图。
图3为实施例3中酸敏性环氧单体C的核磁共振氢谱图。
图4为实施例4中酸敏性环氧单体D的核磁共振氢谱图。
图5为实施例5中酸敏性环氧单体E的核磁共振氢谱图。
图6为实施例6中酸敏性环氧单体F的核磁共振氢谱图。
图7为应用例1中酸敏性聚合物P-A的凝胶渗透色谱图。
图8为应用例2中酸敏性聚合物P-B的凝胶渗透色谱图。
图9为应用例3中酸敏性聚合物P-C的凝胶渗透色谱图。
图10为应用例4中酸敏性聚合物P-D的凝胶渗透色谱图。
图11为应用例5中酸敏性聚合物P-E的凝胶渗透色谱图。
图12为应用例6中酸敏性聚合物P-F的凝胶渗透色谱图。
图13为应用例7中光刻胶P-A的分辨率表征结果。
具体实施方式
为使本发明的目的、技术方案及优点更加清楚明白,以下结合附图及实施例对本发明进行进一步的详细说明。应当理解,此处所描述的具体实施方式仅仅用以解释本发明,并不限定本发明的保护范围。
实施例1
环氧单体A的结构及合成路线如下:
向63g 3-环己烯-1-甲酸中滴加72g(1.2摩尔当量)的氯化亚砜,室温反应2h后,减压蒸馏得到3-环己烯-1-甲酰氯。向44g(1.2摩尔当量)叔丁醇中加入200mL二氯甲烷和60g三乙胺,冷却至0℃后,滴加3-环己烯-1-甲酰氯,室温反应1h后,过滤,饱和NaHCO3溶液洗涤3遍,饱和NaCl溶液洗涤1遍,无水Na2SO4干燥,旋蒸除去二氯甲烷后减压蒸馏,得66g原料a。
将原料a溶解于1L二氯甲烷,加入87g(纯度为85wt%,1.2摩尔当量)间氯过氧苯甲酸(m-CPBA),室温反应12h后,加入饱和NaSO3溶液至淀粉碘化钾试纸不变蓝,饱和NaHCO3溶液洗涤3遍,饱和NaCl溶液洗涤1遍,无水Na2SO4干燥,旋蒸除去二氯甲烷后减压蒸馏,得56g环氧单体A。核磁共振氢谱如图1所示。
实施例2
环氧单体B的结构及合成路线如下:
通过与实施例1相同的合成方法可以得到环氧单体B,只是将酯化反应中的叔丁醇改为2-甲基-2-金刚烷醇。由如图2所示的核磁共振氢谱图可知,得到了环氧单体B。
实施例3
环氧单体C的结构及合成路线如下:
通过与实施例1相同的合成方法可以得到环氧单体C,只是将酯化反应中的3-环己烯-1-甲酸改为4-环己烯-1,2-二甲酸。由如图3所示的核磁共振氢谱图可知,得到了环氧单体C。
实施例4
环氧单体D的结构及合成路线如下:
通过与实施例1相同的合成方法可以得到环氧单体D,只是将酯化反应中的3-环己烯-1-甲酸改为丙烯酸。由如图4所示的核磁共振氢谱图可知,得到了环氧单体D。
实施例5
环氧单体E的结构及合成路线如下:
由于缩水甘油是一种常见的有机化合物,因此此类环氧单体可以直接从缩水甘油酯化得到。
向61g苯甲酸中滴加72g(1.2摩尔当量)的氯化亚砜,室温反应2h后,减压蒸馏得到苯甲酰氯。向44g(1.2摩尔当量)叔丁醇中加入200mL二氯甲烷和60g三乙胺,冷却至0℃后,滴加苯甲酰氯,室温反应1h后,过滤,饱和NaHCO3溶液洗涤3遍,饱和NaCl溶液洗涤1遍,无水Na2SO4干燥,旋蒸除去二氯甲烷后减压蒸馏,得59g环氧单体E,核磁共振氢谱如图5所示。
实施例6
环氧单体F的结构及合成路线如下:
α-当归内酯是一种植物提取物,环氧单体F可由α-当归内酯通过与实施例1相同的氧化方法直接环氧化得到,由如图6所示的核磁共振氢谱图可知,得到了环氧单体F。
将环氧单体A-F均聚或与一氧化碳、二氧化碳共聚制备酸敏性聚合物,下列应用例中,催化剂cat1和cat2公开于文献中,可按照文献(DOI:10.1021/jacs.0c03651、10.1002/anie.202002815、10.1021/acs.macromol.1c00250)公开的方法制备得到。
应用例1
环氧单体A与二氧化碳共聚得到聚碳酸酯P-A的合成路线如下:
在高压反应釜中称取33mg双功能有机硼催化剂cat1,加入19.8g环氧单体A,向反应釜中充入3MPa二氧化碳,80℃下反应2h。将产物溶解于二氯甲烷,在乙醇中沉析得到白色聚合物P-A。P-A的数均分子量43kDa,分子量分布1.13,凝胶渗透色谱如图7所示。
应用例2
环氧单体A和环氧单体B与二氧化碳共聚得到聚碳酸酯P-B的合成路线如下:
在高压反应釜中称取33mg双功能有机硼催化剂cat1,加入9.9g环氧单体A和14.5g环氧单体B,向反应釜中充入3MPa二氧化碳,80℃下反应2h。将产物溶解于二氯甲烷,在乙醇中沉析得到白色聚合物P-B。P-B的数均分子量35kDa,分子量分布1.11,凝胶渗透色谱如图8所示。
应用例3
环氧单体C与二氧化碳共聚得到聚碳酸酯P-C的合成路线如下:
通过与应用例1相同的合成方法可以得到聚碳酸酯P-C,只是将反应原料由环氧单体A改为环氧单体C。P-C的数均分子量41kDa,分子量分布1.10,凝胶渗透色谱如图9所示。
应用例4
环氧单体D自聚合反应得到聚醚P-D的合成路线如下:
在高压反应釜中称取49mg双功能有机硼催化剂cat2,加入14.4g环氧单体D,25℃下反应1h。将产物溶解于二氯甲烷,在乙醇中沉析得到白色聚合物P-D。P-D的数均分子量48kDa,分子量分布1.25,凝胶渗透色谱如图10所示。
应用例5
环氧单体E与一氧化碳共聚得到聚酯P-E的合成路线如下:
在高压反应釜中称取33mg双功能有机硼催化剂cat1,加入17.8g环氧单体E,向反应釜中充入3MPa一氧化碳,80℃下反应12h。将产物溶解于二氯甲烷,在乙醇中沉析得到白色聚合物P-E。P-E的数均分子量33kDa,分子量分布1.22,凝胶渗透色谱如图11所示。
应用例6
环氧单体F与二氧化碳共聚得到聚碳酸酯P-F的合成路线如下:
通过与应用例1相同的合成方法可以得到聚碳酸酯P-F,只是将反应原料由环氧单体A改为环氧单体F。P-F的数均分子量27kDa,分子量分布1.10,凝胶渗透色谱如图12所示。
应用例7
将应用例1~6中合成的酸敏性聚合物P-A~P-F作为化学放大光刻胶的应用方法如下:
将1g聚合物树脂,50mg二苯基碘鎓三氟甲磺酸盐,5mg三辛胺溶解于20g丙二醇单甲醚乙酸酯中,用0.22μm过滤器过滤后得到光刻胶溶液。以4000转每分钟的转速将光刻胶溶液旋涂到硅片上,120℃避光前烘5min除去溶剂,得到光刻胶薄膜。
利用Raith Elphy Quantum电子束光刻系统对光刻胶薄膜进行曝光,电压20kV,束流40pA。曝光后,120℃后烘5min,冷却至室温后,在2.38wt%的四甲基氢氧化铵(TMAH)水溶液中显影1min,在水中定影1min,即可得到光刻图案。根据NRT分析法(Normalizedremaining thickness)测得灵敏度和对比度数据,分辨率(临界尺寸)通过曝光光栅结构得到。由酸敏性环氧单体得到的化学放大光刻胶的光刻性能参数如表1所示,光刻胶P-A的分辨率表征结果如图13所示。图13为光栅结构的SEM照片。
表1基于酸敏性环氧单体的化学放大光刻胶的光刻性能参数
与现有技术相比,通过本发明提供的酸敏性环氧单体得到的化学放大光刻胶具有酸敏感的聚合物主链及侧链,在光刻过程中可以同时发生主链与侧链结构的断裂,并产生羟基、羧基等强极性基团,提高了与非曝光区域的溶解度差异,从而可以得到更高的灵敏度、对比度、分辨率以及更低的线边缘粗糙度。
以上所述的具体实施方式对本发明的技术方案和有益效果进行了详细说明,应理解的是以上所述仅为本发明的最优选实施例,并不用于限制本发明,凡在本发明的原则范围内所做的任何修改、补充和等同替换等,均应包含在本发明的保护范围之内。
Claims (10)
1.一种酸敏性环氧单体,其特征在于所述的酸敏性环氧单体的化学式如式(1)~式(3)之一所示:
所述式(1)~式(3)中,R1、R2各自独立为H、未取代的或具有取代基的C1-C20烷基,所述烷基的碳链内含有或不含有O、S、N、Si、P原子中的一种或多种;所述烷基上的取代基选自卤素原子、C1-C20的支链或直链的烷基、C1-C20的支链或直链的烷氧基中的一种或多种;
所述式(1)或式(2)中,R3为下列基团式A~式C之一:
式A中,K1为0、C1-C20亚烷基、苯基、或碳链中含有氧或硫原子的C1-C20亚烷基,所述亚烷基上的H不被取代或被C1-C10的烷基或C1-C10的烷氧基取代;
式B中,K2为0、C1-C20亚烷基、苯基、或碳链中含有氧或硫原子的C1-C20亚烷基,所述亚烷基上的H不被取代或被C1-C10的烷基或C1-C10的烷氧基取代;
式C中,K3为C1-C20次烷基;
式A~式C中,R6、R7、R8、R9各自独立选自包含或不包含取代基的以下基团:C1-C30烷基、C3-C30环烷基、C3-C30炔基、C4-C30硅烷基、C6-C30芳香基、C3-C30杂环基或C5-C30杂芳香基,或者为碳链中含有O、S、N、Si、P原子中的一种或多种的所述基团;其中所述取代基选自卤素原子、羟基、三氟甲基、六氟异丙基、C1-C20的支链或直链的烷基、C1-C20的支链或直链的烷氧基、C3-C20的支链或直链的环烷基、C6-C30的芳香基、C5-C30的杂芳香基中的一种或多种;
所述式(1)中,R4为H、未取代的或具有取代基的C1-C20烷基,或者为式A~式C之一;式A~式C中K1、K2、K3、R6、R7、R8、R9的定义如前所述;所述烷基的碳链内含有或不含有O、S、N、Si、P原子中的一种或多种;所述烷基上的取代基选自卤素原子、C1-C10的支链或直链的烷基、C1-C10的支链或直链的烷氧基中的一种或多种;
所述式(2)中,i代表Q环上R3的个数,i=1或2;
所述式(2)中,Q环代表环氧基团上的两个碳原子和碳链连接成环的环状基团,所述Q环为下列之一:
其中Z表示O、N、S、C1-C20亚烷基或碳链中含有氧、氮或硫原子中的一种或多种的C1-C20亚烷基;
所述式(2)中,Rq代表Q环上除R3以外的取代基,Rq为未取代的或具有取代基的C1-C20烷基,所述烷基的碳链内含有或不含有O、S、N、Si、P原子中的一种或多种;所述烷基上的取代基选自卤素原子、C1-C10的支链或直链的烷氧基中的一种或多种;
j代表Q环上Rq的个数,j为0~3的整数;
所述式(3)中,R5为未取代的或具有取代基的C1-C20烷基,所述烷基的碳链内含有或不含有O、S、N、Si、P原子中的一种或多种;所述烷基上的取代基选自卤素原子、C1-C10的支链或直链的烷氧基中的一种或多种;k代表内酯环上R5的个数,k为0~3的整数;
所述式(3)中,m1、m2各自独立的取自0-20之间的整数,但不可同时取0。
2.如权利要求1所述的酸敏性环氧单体,其特征在于所述R1为H或C1-C10的烷基;R2为H或C1-C10的烷基;
K1为0、C1-C10亚烷基或苯基;K2为0或C1-C10亚烷基;K3为C1-C6次烷基;
R6、R7、R8、R9各自独立选自包含或不包含取代基的以下基团:C1-C10烷基,C3-C15环烷基、C4-C10硅烷基、C6-C15芳香基、C3-C15杂环基或C5-C15杂芳香基,或者为碳链中含有O、S、Si原子中的一种或多种的所述基团;所述取代基选自卤素原子、羟基、三氟甲基、六氟异丙基、C1-C10的支链或直链的烷基、C1-C10的支链或直链的烷氧基中的一种或多种;
R4为H、C1-C10烷基,或者为式A~式C之一;
Z为O、N、S、C1-C5亚烷基或碳链中含有氧、氮或硫原子中的一种或多种的C1-C5亚烷基;
Rq为C1-C10烷基;j=0或1;
R5为C1-C10烷基;k为0~2的整数;
m2为0~5的整数,m1为1~5的整数。
6.如权利要求5所述的方法,其特征在于所述的过氧化物为间氯过氧苯甲酸、过氧乙酸、过氧化氢或过氧丙酮。
7.如权利要求1~4之一所述的酸敏性环氧单体在制备酸敏性聚合物中的应用,所述应用的方法为,酸敏性环氧单体在催化剂或引发剂的作用下,通过环氧开环的方式进行聚合反应制备得到酸敏性聚合物。
8.如权利要求7所述的应用,其特征在于所述的酸敏性环氧单体在进行聚合反应制备酸敏性聚合物时,所述聚合反应为一种酸敏性环氧单体进行自聚合反应或多个酸敏性环氧单体进行共聚合反应得到聚醚,或者是一种或多种酸敏性环氧单体与反应性单体进行共聚合反应得到聚碳酸酯、聚酯、硫代聚碳酸酯或硫代聚酯;所述的反应性单体为二氧化碳、一氧化碳、氧硫化碳或一硫化碳。
9.如权利要求1~4之一所述的酸敏性环氧单体通过环氧开环的方式进行聚合反应制备得到的酸敏性聚合物;所述的酸敏性聚合物是在催化剂或引发剂的作用下,一种酸敏性环氧单体进行自聚合反应或多个酸敏性环氧单体进行共聚合反应得到的聚醚,或者是一种或多种酸敏性环氧单体与反应性单体进行共聚合反应得到的聚碳酸酯、聚酯、硫代聚碳酸酯或硫代聚酯;所述的反应性单体为二氧化碳、一氧化碳、氧硫化碳或一硫化碳。
10.如权利要求9所述的酸敏性聚合物在化学放大光刻胶中的应用。
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