经由芳酰环系衍生的多官能团或聚合型酰基膦氧化合物 Aroyl ring system is derived via a multi-functional group or polymeric acylphosphine oxide compound

【技术领域】 TECHNICAL FIELD

[0001] 本发明涉及辐射聚合固化新材料技术领域，特别涉及一类结构通式(1-1II)所示的新颖芳酰环系衍生的多官能团或聚合型酰基膦氧化合物，其化学制备方法，其作为含烯不饱和化合物体系进行辐射聚合固化的光引发剂的用途，以及含有该类化合物的辐射聚合固化复合材料体系。 [0001] The present invention relates to the field of radiation polymerization curing technology and new materials, and in particular (1-1II) illustrated novel aroyl ring system derived from polyfunctional or polymeric acylphosphine oxide compounds, a class of chemical structural formula preparation , as ethylenically unsaturated compound photoinitiator system for use in radiation polymerization curing agent, and radiation polymerizable compound containing such cured composite material system.

【背景技术】 BACKGROUND OF THE INVENTION

[0002] 在辐射(紫外光或可见光或电子束或X-射线)固化领域，光引发剂是关键的复合组分之一，关于光引发剂结构与制造工艺的研究文献已经有相当丰富的披露，具有特别重要工业应用价值的例如下图所示的羟基酮型光引发剂1173和酰基膦氧型光引发剂ΤΡ0, TP0-L，和ΒΑΡ0。 [0002] In the radiation (ultraviolet or visible light or electron beams or X- rays) curing in the field, a photoinitiator is one of the key components of the complex, the research literature on photo-initiator and manufacturing process of structural change has been quite extensive disclosure of particular importance in industrial applications such as the value shown below hydroxyketone photoinitiator 1173 and acyl phosphine oxide type photoinitiator ΤΡ0, TP0-L, and ΒΑΡ0. 近年来，随着辐射固化技术进步和工业应用标准的不断提升，在对传统光引发剂的引发活性基本要求之外，更加关注其环保和健康友好性，突出表现在发展高效率新一代光引发剂产品的同时，强调其低挥发性有害有机化合物(Volatile OrganicCompounds,简称V0C)的释放,低残余不良气味，以及低迁移性等。 In recent years, with the radiation curing technology advances and industry application standards rising, the traditional photo-initiator initiating activity beyond the basic requirements of agents, pay more attention to their environmental and health friendliness, outstanding performance in the development of a new generation of high efficiency photoinitiator At the same time agents of products, emphasizing its low volatility, harmful organic compounds (Volatile OrganicCompounds, referred V0C) release, low residual bad odor and low migration and so on. 在此领域典范性的例子是原Ciba公司开发的Irgacure 127以及Lamberti公司开发的150双官能团轻基酮光引发剂，与单官能团型光引发剂1173相比，在增加官能度和分子量后，127和150化合物展现了更高的光聚合引发效率，更低的VOC释放量，以及更低的迁移倾向等优良性能，正得到日 Examples in this area a model of the former Ciba developed Irgacure 127 and Lamberti has developed 150 bifunctional light ketone photoinitiator, and monofunctional photoinitiators 1173 compared to after increasing the functionality and molecular weight, 127 and 150 compounds demonstrated higher light polymerization initiator efficiency, lower VOC emission, as well as a lower tendency to migrate, excellent performance, being the date

益广泛的市场应用。 Benefit a wide range of market applications.

[0003] [0003]

[0004] 与多官能团羟基酮型光引发剂的活跃研发与成功产业化形成鲜明对比的是，文献鲜有对酰基膦氧型光引发剂多官能团化的披露，已知的极为有限的例子例如W02011/003772A1，W02003104245A1，和W02006/056541A1。 [0004] and multifunctional hydroxy ketone photoinitiator active research and development and successful industrialization in stark contrast to the literature few of acyl phosphine oxide type agent polyfunctional disclosure photoinitiator known very limited examples such as W02011 / 003772A1, W02003104245A1, and W02006 / 056541A1. 值得特别强调的是，文献披露结果分为两类，即或者是通过改变磷原子取代基制备酰基膦氧型化合物，或者是使用已经含有某种所需芳环取代基的芳酰基前体和适当含磷前体偶联进行酰基膦氧型化合物的制备；而尚未有任何在酰基膦氧C(O)-P(O)核心光活性官能团存在下直接对其芳酰环系进行结构改造的报道(即直接利用TPO或BAPO型结构为起始原料)，这样的技术一旦突破其优势是明显的，因为可以更加快速而高效地实现多种酰基膦氧型光引发剂的“砌块式”组装制备。 Of particular emphasis is literature disclose the results fall into two categories, i.e., either substituted acyl phosphine oxide type compound prepared by changing the phosphorus atom, or a certain desired to use already containing an aromatic ring substituted aroyl group precursor and appropriate Preparation of an acyl phosphine oxide type compounds containing phosphorus precursor coupled conduct; and yet there is no report in the acyl phosphine oxide C (O) -P (O) core photoactive functional group directly tie their aroyl ring in the presence of structural transformation (ie, the direct use of TPO or BAPO structure as a starting material), this technology breakthrough once its advantages are obvious, because they can more quickly and efficiently achieve a variety of acyl phosphine oxide type photoinitiator "block type" assembly Preparation. [0005] 综上所述，由于对单官能团酰基膦氧化合物结构改造的技术困难性以及高昂的成本，迄今为止尚未有任何关于多官能团酰基膦氧型光引发剂成功产业化的报道。 [0005] In summary, because of the monofunctional acyl phosphine oxide compound of the structural transformation of the technical difficulties and high costs, have so far not had any reports of polyfunctional acyl phosphine oxide type photoinitiator successful industrialization.

【发明内容】 SUMMARY OF THE INVENTION

[0006] 本项申请现已意外地发现，从简单的文献已知的单或双官能团型酰基膦氧型光弓I发剂(例如TP0，TP0_L，BAP0)出发，通过一类酸促进的卤烷基化技术，可以简洁而快速地制备一系列新型结构的多官能团或聚合型型酰基膦氧型光引发剂。 [0006] The term application has now surprisingly been found that known from the literature from simple mono or bifunctional type acyl phosphine oxide type light bow I initiators (such as TP0, TP0_L, BAP0) departure, promoted by a class of acid halide alkylation technology, simple and quick to prepare a series of new structures or polymeric polyfunctional acyl phosphine oxide type photoinitiator. 这是一个具有里程碑意义的重大反应技术突破，因为它首次实现了在酰基膦氧C(O)-P(O)光活性官能团原位存在下对其芳酰环系的直接结构改造，首次鉴定发现了一系列分子砌块(Building-Block)式酰基膦氧化合物结构，且首次使得经济而高效地获得多官能团或聚合型酰基膦氧型光引发剂从化学合成反应方法学上成为可能！ This is a major technological breakthrough in the reaction of a landmark, since it was first achieved in the acyl phosphine oxide C (O) -P (O) photoactive functional group in situ under the direct presence of structural transformation of their aroyl ring system, first identified We discovered a series of molecular block (Building-Block) acylphosphine oxide compound of the formula, and the first economical and efficient way to obtain such a polyfunctional polymer or an acyl phosphine oxide type photoinitiator possible reaction from the chemical synthesis methodology!

[0007] 本项申请披露下述通式(1-1II)所示的多官能团或聚合型酰基膦氧化合物结构: [0007] The present application discloses the following general formula item (1-1II) polyfunctional shown or polymeric acylphosphine oxide compound structure:

[0008] [0008]

[0009] 在通式(1-1II)中，n取值I或2或3，优选的，n取值为I或2 ;m取值O或I ;X是氧或硫。 [0009] In the general formula (1-1II), n is 2 or 3 the values ​​I or, preferably, n is a value of I or 2; m value of O or I; X is oxygen or sulfur. p，r，和s是描述官能度的整数，其中P取值大于或等于I的整数，r和s取值大于或等于2的整数。 p, r, and s are integers described functionality, wherein the value of P is greater than or equal to the integer I, r and s values ​​of integer greater than or equal to 2.

[0010] R1, R2,和R3分别独立地是氢，卤素,碳原子数为1-24(标记为C1-C24,下同)的含有一或多个取代基的支链或直链，含有或不含有C3-C12环系结构的烷基，或是一个C2-C24的含有一或多个取代基的支链或直链，含有或不含有C3-C12环系结构的烯基，或是一个碳原子数为C6-C24的未取代或被取代1-4次的芳基(苯基，萘基，蒽基，或联苯基)或杂芳基。 [0010] R1, R2, and R3 are each independently hydrogen, halo, 1-24 carbon atoms (labeled C1-C24, the same below) a branched or straight chain comprising one or more substituents, comprising or not containing C3-C12 alkyl ring system structure, or contain one or more substituents of a straight chain or branched chain C2-C24 containing or not containing C3-C12 alkenyl ring architecture, or carbon atoms an unsubstituted or substituted C6-C24 aryl group 1-4 times (phenyl, naphthyl, anthryl or biphenyl) or heteroaryl. R1, R2,和R3的链段彼此独立地可以被1-6个非连续的氧原子，氮原子，硅原子，或硫原子间断。 Segment R1, R2, and R3 independently of each other may be interrupted 1-6 non-consecutive oxygen atom, a nitrogen atom, a silicon atom, or a sulfur atom. R1,R2，和R3任意二者之间也可以形成一个环结构。 R1, can also form a ring structure among R2, R3 and optionally both. R1, R2，和R3的链段与其联结的苯环之间彼此独立地也可以被一个氧，硫，或一个含有C1-C4烷基或烷氧取代基的氮，硅，或磷插入。 R1, R2, R3 and between its coupling segments independently of each other a benzene ring may be substituted with one oxygen, sulfur, or C1-C4 alkyl group containing an alkoxy substituent or nitrogen, silicon, phosphorus, or insertion.

[0011] 当η取值为2或3时，即存在多个R1, R2，和R3取代芳环时，其多个芳环的满足上述定义的R1, R2，和R3取代基彼此独立地可以相同或不同；当η取值为2或3时，即存在多个R1, R2，和R3取代芳环时，优选的，在通式(I)中，Q和其中一个芳环键联；在(III)中，R12和其中一个芳环键联。 [0011] When η a value of 2 or 3, that is, multiple R1, R2, and R3 when substituted aromatic ring, R1 more aromatic rings which meet the above definition, R2, and R3 each independently substituted may be based the same or different; when η a value of 2 or 3, that is, multiple R1, R2, and R3-substituted aryl ring, preferably, in the general formula (I), Q is and one of the aromatic ring bonded; in (III) in, R12 and one of the aromatic ring linkages.

[0012] R4是碳原子数为C1-C24的含有一或多个取代基的支链或直链，含有或不含有C3-C12环系结构的烷基或烷氧基，或是一个C2-C24的含有一或多个取代基的支链或直链，含有或不含有C3-C12环系结构的烯基。 [0012] R4 carbon atoms containing one or more substituents of branched or straight chain C1-C24 containing or not containing alkyl or alkoxy C3-C12 ring system structure, or a C2- contain one or more substituents C24 branched or straight chain, and with or without a C3-C12 alkenyl ring system structure. R4的链段可以被1-6个非连续的氧原子，氮原子，硅原子，或硫原子间断。 R4 segments may be interrupted 1-6 non-consecutive oxygen atom, a nitrogen atom, a silicon atom, or a sulfur atom.

[0013] R5是氢，0H，碳原子数为C1-C24的含有一或多个取代基的支链或直链，含有或不含有C3-C12环系结构的烧基或满足这样条件的烧氧基或烧疏基或娃烧基,碳原子数为C6-C24的未取代或被取代1-4次的芳基(苯基，萘基，蒽基，或联苯基)或杂芳基或满足这样条件的酚氧基或硫酚基。 [0013] R5 is hydrogen, 0H, carbon atoms containing one or more substituents of branched or straight chain C1-C24, and burning with or without a C3-C12 ring system burning structure or satisfying this condition group or a mercapto group or a burn baby burn group, carbon atoms, an unsubstituted or substituted C6-C24 aryl group 1-4 times (phenyl, naphthyl, anthryl, or biphenyl) or heteroaryl satisfying such condition or phenol group or a thiophenol group. R5的链段可以被1-6个非连续的氧原子，卤素原子，氮原子，硅原子，硫原子，双键，或三键间断。 R5 segments may be non-contiguous 1-6 oxygen atoms, a halogen atom, a nitrogen atom, a silicon atom, a sulfur atom, a double bond or triple bond intermittent.

[0014] R6是氢,碳原子数为C1-C24的含有一或多个取代基的支链或直链,含有或不含有C3-C12环系结构的烧基或满足这样条件的烧氧基或烧疏基或娃烧基,碳原子数为C6-C24的未取代或被取代1-4次的芳基(苯基，萘基，蒽基，或联苯基)或杂芳基或满足这样条件的酚氧基或硫酚基的链段可以被1-6个非连续的氧原子，卤素原子，氮原子，硅原子，硫原子，双键，或三键间断。 [0014] R6 is hydrogen, carbon atoms containing one or more substituents of branched or straight chain C1-C24, the firing group having or not having C3-C12 burn-yl ring system or structure satisfying such conditions burning or mercapto group or a baby burning carbon atoms an unsubstituted or substituted C6-C24 aryl group 1-4 times (phenyl, naphthyl, anthryl, or biphenyl) or heteroaryl or meet phenoxy or thiophenol group segments such conditions can be 1-6 non-consecutive oxygen atoms, a halogen atom, a nitrogen atom, a silicon atom, a sulfur atom, a double bond or triple bond intermittent.

[0015] R8, R9，和R10的定义与R1, R2，和R3相同。 [0015] R8, R9, and R10 are as defined R1, R2, and R3 are the same.

[0016] R11的定义与R6相同。 [0016] R11 and R6 are the same definition.

[0017] Q是一个P价基团。 [0017] Q is a monovalent group P. 当P取值为I时，Q是形式为CR13R14(R15)的一价取代基，其中R13和R14分别独立地是氢或C1-C6的烷基，优选的，Q是CH2 (R15)；当P取值为2时，Q是C =0，或Q是形式为CR13R14 的二价联结基团，优选的，Q是CH2，或Q是一个二价的满足R15条件的联结基团。 When the value of I when P, Q is the form CR13R14 (R15) is a monovalent substituent, wherein R13 and R14 are each independently hydrogen or C1-C6 alkyl group, preferably, Q is CH2 (R15); when when the value P 2, Q is C = 0, or Q is CR13R14 form a divalent linking group, preferably, Q is CH2, or Q is a divalent linking group satisfies condition R15 groups. 当P取值为大于或等于3的整数时，Q是一个P价的满足R15条件的联结基团。 When the P value is an integer greater than or equal to 3, when, Q is a P-value of R15 to meet the conditions of the coupling group.

[0018] R15是未取代的直链或支链的含有1-24个碳原子的烷基或含有2-24个碳原子的烯基；或是含有一或多个取代基的直链或支链的含有1-24个碳原子的烷基或含有2-24个碳原子的烯基，这些一或多个取代基可以是卤素原子，-NCO基，-CN基，环氧乙烷基，N-烷基(C1-C8 烷基)取代的酰亚胺基，-OR16 基，-CO-R16 基，-CONR16R17 基，-NR16R17 基，-SiR16R17R18基，-OSiR16R17R18 基，-NR-CO-R16 基，-NR-CO-OR16 基，-NR-COR16R17 基，-SR16 基，-SO2R16基，-SO2-OR16 基，-SO2-NR16R17 基，-PO-OR16-OR17 基，-PO- (OR16) (OM1)基，-PO- (OM1) (OM2)基，-PO-R16R17 基，-COOR16 基，-OC (O) R16 基，-CH = CH-CO-OR16 基，或-C (C1-C4 烷基)=C (C1-C4烧基)-CO-OR16 ； [0018] R15 is unsubstituted straight-chain or branched alkyl having 1 to 24 carbon atoms or an alkenyl group having 2 to 24 carbon atoms; or one or more substituents containing a linear or branched containing 1 to 24 carbon atoms containing 2 to 24 carbon atoms or alkenyl chains, these one or more substituents may be a halogen atom, -NCO group, -CN group, oxirane group, N- alkyl (C1-C8 alkyl) substituted imide group, -OR16 group, -CO-R16 group, -CONR16R17 group, -NR16R17 group, -SiR16R17R18 group, -OSiR16R17R18 group, -NR-CO-R16 group, -NR-CO-OR16 groups, -NR-COR16R17 group, -SR16 group, -SO2R16 group, -SO2-OR16 group, -SO2-NR16R17 group, -PO-OR16-OR17 group, -PO- (OR16) (OM1) group, -PO- (OM1) (OM2) group, -PO-R16R17 group, -COOR16 group, -OC (O) R16 group, -CH = CH-CO-OR16 groups, or -C (C1- C4 alkyl) = C (C1-C4 burn-yl) -CO-OR16;

[0019] 这里R16, R17, R18彼此独立地是氢，C1-C24烷基，为一或多个非连续性氧或硫或氮原子所间断的C2-C24基，含一或多个乙烯醇单元的取代基,C3-C24环状烷基，2-呋喃基，四氢呋喃基，苯基-C1-C4-亚烧基,苯基-C1-C4-烯基，含有齒素或环己基或环戍基或四氢呋喃基或呋喃基的C1-C6烷基，C2-C18烯基，苯基，未取代的萘基或联苯基，含有一至五个C1-C8烷基或C1-C8烷氧基或C1-C8烷硫基或卤素取代基的苯基或萘基或联苯基；R16，R17,或R18的一个或多个氢原子还可以被氟原子取代； [0019] where R16, R17, R18 independently of one another are hydrogen, C1-C24 alkyl group, or a plurality of discontinuous oxygen or nitrogen atom or a sulfur interrupted C2-C24 group containing one or more vinyl alcohol substituted unit group, C3-C24 cyclic alkyl, 2-furyl, tetrahydrofuranyl, phenyl -C1-C4- alkylene burning, phenyl -C1-C4- alkenyl group containing biotin or teeth or cyclohexyl ring pentyl or tetrahydrofuranyl group or a furyl C1-C6 alkyl, C2-C18 alkenyl, phenyl, unsubstituted naphthyl or biphenyl, containing one to five C1-C8 alkyl or C1-C8 alkoxy or C1-C8 alkylthio or halo-substituted phenyl or naphthyl group or biphenyl; R16, R17, or R18 one or more hydrogen atoms may also be substituted by fluorine atoms;

[0020] M1和M2彼此独立地是一个金属阳离子或铵盐阳离子； [0020] M1 and M2 are each independently a metal cation or ammonium cation;

[0021 ]或R15 是被-CO-，-COO-, -0C0-, -0C00-, -CO-NR16-, -NR16-CO-, -NR16-CO-NR16-, -NR16-COO-, -COO-C1-C18-亚烧基，-COS-C1-C18-亚烧基，-SO2-, -SO2-Q-, -SO2-NR16-, -SiR16R17-, -SiOR16R17-, -SiOR16OR17-, -PO-OR16-, -PO- (OM1) -，-PO- (OM1) (OM2)，-PO-R16-,-苯基-C1-C4-亚烷基_，-C6H4-,萘环，联苯环，C5-C12环，或含氧或硫或氮原子的五或六元杂环间断的C1-C24烷基或C2-C24稀基； [0021] or R15 is -CO -, - COO-, -0C0-, -0C00-, -CO-NR16-, -NR16-CO-, -NR16-CO-NR16-, -NR16-COO-, - COO-C1-C18- alkylene group burned, -COS-C1-C18- alkylene group burned, -SO2-, -SO2-Q-, -SO2-NR16-, -SiR16R17-, -SiOR16R17-, -SiOR16OR17-, - PO-OR16-, -PO- (OM1) -, - PO- (OM1) (OM2), - PO-R16 -, - phenyl -C1-C4- alkylene _, - C6H4-, naphthalene ring, biphenyl benzene, C5-C12 cycloalkyl, or an oxygen-containing or sulfur or nitrogen atom a five or six-membered heterocyclic ring interrupted C1-C24 alkyl or C2-C24 dilute base;

[0022] 或R15是苯基-C1-C4-烧基，苯基，萘基，联苯基，C5-C12环烧基，或含氧或硫或氮原子的五或六元杂环；这里这些取代基均可以含有一或多个C1-C8烷基或C1-C8烷氧基或C1-C8烷硫基或氯原子或-NR16R17取代基； [0022] R15 is phenyl or -C1-C4- burning, phenyl, naphthyl, biphenyl, C5-C12 cycloalkyl group burn, or five or six membered heterocyclic ring containing oxygen or sulfur or nitrogen atom; here These substituents each may contain one or more of C1-C8 alkyl or C1-C8-alkoxy or C1-C8 alkylthio group -NR16R17 or chlorine atom or a substituent;

[0023] R7是形式为CR13R14的二价联结基团，优选的，R7是CH2。 [0023] R7 is CR13R14 form a divalent linking group, preferably, R7 is CH2.

[0024] R12是一个二价的满足R15条件的联结基团。 [0024] R12 is a divalent linking meet the conditions R15 groups.

[0025] 通式⑴化合物包括但不局限于下述示例性结构: [0025] Formula ⑴ compounds include, but are not limited to the following exemplary structures:

[0026] [0026]

.[0029] 通式(II)化合物包括但不局限于下述示例性结构: . [0029] Formula (II) compounds include, but are not limited to the following exemplary structures:

[0030] [0030]

[0031] 通式(III)化合物包括但不局限于下述示例性结构: [0031] Formula (III) compounds include, but are not limited to the following exemplary structures:

[0032] [0032]

[0033] 令人意外地，在一些已知单体酰基膦氧化合物中，即便强吸电子的酰基膦氧-C(O)-P(O)-官能团显著钝化了其含有的芳酰环系，本项申请现已发现依然可以在合适条件下实现对其芳酰环系的直接卤烷基化反应，进而实现系列通式(1-1II)化合物的快速而经济实用地制备。 [0033] Surprisingly, in some known monomeric acyl phosphine oxide compounds, even a strong electron-withdrawing acyl phosphine oxide -C (O) -P (O) - functional group significantly passivation aroyl ring which contains system, this item has been found that the application can still achieve its immediate halogen aroyl ring system alkylation reaction under suitable conditions, so as to realize rapid and cost-effective series prepared formula (1-1II) compounds.

[0034] 通式⑴化合物的制备反应通式如下:从文献已知的单体酰基膦氧化合物A出发，在酸和甲醛作用下发生Friedel-Crafts烷基化反应得到氯甲基化中间体B，这里的酸可以是路易斯酸如三氯化铝，二氯化锌，二氯化镁，三氯化铁，三氯化铟，稀土金属的形式为LaHal3(La代表一个稀土兀素,Hal代表一个齒素原子)的齒化物或形式为La(OTf)3的磺酸盐等，或是无机或有机的质子酸例如盐酸，硫酸，磷酸，甲酸，乙酸，磺酸。 [0034] The general reaction scheme for preparing compounds of formula ⑴ follows: monomer known from the literature acyl phosphine oxide compound A departure occurred Friedel-Crafts alkylation reaction chloromethylated intermediate B in the role of acid and formaldehyde , where the acid may be a Lewis acid such as aluminum chloride, zinc chloride, magnesium chloride, ferric chloride, indium trichloride, a rare form of LaHal3 (La represents a rare Wu Su, Hal represents a tooth Su atom) of the teeth or in the form of La (OTf) 3, etc. sulfonate, or an inorganic or organic protonic acid such as hydrochloric acid, sulfuric acid, phosphoric acid, formic acid, acetic acid, sulfonic acid.

[0035] B和形式为YH的阴离子(Y = O, S)或其等价物发生取代反应生成化合物C。 [0035] B and anionic form YH (Y = O, S) or an equivalent thereof substitution reaction to form compound C. 由此得到的结构B和C代表了两个关键的酰基膦氧化合物分子砌块。 The thus obtained structure B and C represent two key blocks acylphosphine oxide compound molecules. B的氯苄官能团和C的苄醇官能团与一系列多元(硫)醇E1，多元羧酸E2，多元酰氯E3，多元异氰酸酯E4，多元不饱和羰基化合物E5，或多元环氧化物E6反应即可制备一些通式(I)化合物。 Chlorobenzyl B functional groups and C of benzyl alcohol functional group with a range of poly (sulfur) alcohol E1, polycarboxylic acids E2, pluralistic chloride E3, polyisocyanate E4, polyunsaturated carbonyl compound E5, or poly epoxides E6 reaction to preparation of some of the general formula (I) compound. 具体而言，对本领域从业专业技术人员所熟知的化学官能团转化反应是，B可以和El或E2发生取代反应；而C可以和E2和E3发生酯化反应，和E4和E5发生加成反应，和E6发生环氧开环反应。 Specifically, practitioners in the art of professional skill in the art chemical functional group transformation reactions, B substitution reactions can occur and El or E2; and C E2 and E3 can be esterified, and E4 and E5 addition reaction, and E6 epoxy ring-opening reaction occurs. C同时可衍生为合适的含有酰基膦氧结构的可聚合的不饱和酯或不饱和烯烃或氯硅烷单元，进而经由自由基或水解聚合反应制备高分子型(I)结构。 C while derivatized to suitable unsaturated ester containing an acyl phosphine oxide structure or an unsaturated polymerizable olefin or chlorosilane unit, and then the polymerization reaction of polymer (I), or a radical structure via hydrolysis. 例如，C和不饱和酰氯或不饱和羧酸酯化得到结构D，D即可在自由基引发剂存在下聚合得到高分子型(I)目标分子。 For example, C and the unsaturated carboxylic acid ester or unsaturated acid chloride of structure D, D can be in the presence of a radical polymerization initiator to give a polymer electrolyte (I) target molecule.

[0036] [0036]

[0037] 通式(II)化合物的制备反应通式如下:从文献已知的双酰基膦氧单体化合物F出发，在酸和甲醛作用下在两个芳环上依次发生Friedel-Crafts烷基化反应得到亚甲基联结的聚合型结构(II)，这里的酸可以是路易斯酸如三氯化铝，二氯化锌，二氯化镁，三氯化铁，三氯化铟，稀土金属的形式为LaHal3(La代表一个稀土兀素,Hal代表一个齒素原子)的卤化物或形式为La(OTf)3的磺酸盐等，或是无机或有机的质子酸例如盐酸，硫酸，磷酸，甲酸，乙酸，磺酸。 Preparation of the reaction of the general formula [0037] Formula (II) compound as follows: from the literature known bisacylphosphine oxide compound F monomeric starting acid and formaldehyde in effect Friedel-Crafts-alkyl occurs sequentially in two aromatic rings coupling reaction to obtain a methylene polymeric structure (II), where the acid may be a Lewis acid such as aluminum trichloride, zinc dichloride, magnesium dichloride, iron trichloride, indium trichloride, in the form of rare earth metal is LaHal3 (La represents a rare earth elements Wu, Hal represents a tooth prime atom) or a halide form La (OTf) 3, etc. sulfonate, or an inorganic or organic protonic acid such as hydrochloric acid, sulfuric acid, phosphoric acid, formic acid , acetic acid, sulfonic acid. 或者，自F经由Friedel-Crafts卤烷基化制备得到关键分子砌块型中间体G(其中Z是Cl，OH, SH, NH2等)，G和Ε1-Ε6聚合反应得到结构(II)。 Alternatively, since the block type F key molecule to give intermediate G via Friedel-Crafts alkylation of Preparation halide (wherein Z is Cl, OH, SH, NH2, etc.), G, and Ε1-Ε6 polymerization of structure (II).

[0038] [0038]

[0039] 通式(III)化合物的制备反应通式如下:从文献已知的酰基膦氧单体化合物H出发，在酸和甲醛作用下在同一芳环上依次发生两次Friedel-Crafts烷基化反应得到关键分子砌块型中间体I(其中Z是C1，0H，SH，NH2等)，I和E1-E6聚合反应得到结构(II)。 Preparation of the reaction of the general formula [0039] Formula (III) compounds are as follows: known from the literature acyl phosphine oxide monomer compound H starting role in acid and formaldehyde Friedel-Crafts alkyl occur twice successively on the same aromatic ring reaction to give the key intermediate molecular block type I (where Z is C1,0H, SH, NH2, etc.), I and E1-E6 polymerization of structure (II). 这里的酸可以是路易斯酸如三氯化铝，二氯化锌，二氯化镁，三氯化铁，三氯化铟，稀土金属的形式为LaHal3(La代表一个稀土兀素,Hal代表一个齒素原子)的齒化物或形式为La(OTf)3 Here's the acid may be a Lewis acid such as aluminum chloride, zinc chloride, magnesium chloride, ferric chloride, indium trichloride, a rare form of LaHal3 (La represents a rare Wu Su, Hal represents a tooth vegetarian atoms), or in the form of the teeth of the La (OTf) 3

的磺酸盐等，或是无机或有机的质子酸例如盐酸，硫酸，磷酸，甲酸，乙酸，磺酸。 Sulfonates, etc., or an inorganic or organic protonic acid such as hydrochloric acid, sulfuric acid, phosphoric acid, formic acid, acetic acid, sulfonic acid.

[0040] [0040]

[0041] 本项申请同时披露一类合适的辐射(紫外光或可见光或电子束或X-射线或等价光源)固化体系。 [0041] The term application also disclosed a class of suitable radiation (UV or visible light or electron beam sources or X- rays or equivalent) cure system. 这样的体系包含至少一种可聚合的含烯键不饱和组分，且包含至少一种通式(1-1II)化合物为光引发剂或光引发剂组分之一。 Such a system comprises at least one polymerizable ethylenically unsaturated component, and comprising at least one formula (1-1II) compound as photoinitiator or photoinitiator one agent component. 以体系中含烯键不饱和组分总量每100份重量计算，含有的通式(1-1II)化合物的合适的量是0.01-25重量份，优选0.1_10重量份。 In systems containing ethylenically unsaturated component of the total weight per 100 parts, containing the appropriate amount of formula (1-1II) compound is 0.01 to 25 parts by weight, preferably 0.1_10 parts by weight. 本项申请披露的合适辐射固化体系包含的可聚合的含烯键不饱和组分是可以通过该双键的自由基聚合反应被交联的化合物或混合物，这种含烯键不饱和组分可以是单体，低聚物或预聚物，或是它们的混合物或共聚物。 Ethylenically polymerizable suitable radiation curing system of the present item disclosed herein contain unsaturated components polymerization can be crosslinked by free radical compounds or mixtures of the double bond, the ethylenically unsaturated component can They are monomers, oligomers or prepolymers, or mixtures or copolymers thereof.

[0042] 这样的合适辐射固化体系还可以含有根据实际需要所添加的无机或有机填充剂和/或着色剂(例如颜料或染料等)，以及其它添加剂(例如紫外线吸收剂，光稳定剂，阻燃齐U，流平剂，或消泡剂等)和溶剂等任意成分。 [0042] Suitable radiation curable systems such may also contain added as required, inorganic or organic fillers and / or colorants (e.g., pigments or dyes, etc.), as well as other additives (e.g. ultraviolet absorber, light stabilizer, hindered Qi burning optional components U, leveling agents or defoamers, etc.) and solvents.

[0043] 合适的自由基聚合的单体是例如含烯键可聚合单体，包括但不限于(甲基)丙烯酸酯，丙烯醒，烯烃，共轭双烯烃，苯乙烯，马来酸酐，富马酸酐，乙酸乙烯酯，乙烯基吡咯烷酮，乙烯基咪唑，(甲基)丙烯酸，(甲基)丙烯酸衍生物例如(甲基)丙烯酰胺，乙烯基卤化物，亚乙烯基卤化物等。 [0043] Suitable free-radical polymerizable monomers, for example ethylenically polymerizable monomers, including but not limited to (meth) acrylate, propylene wake, an olefin, a conjugated diene, styrene, maleic anhydride, Fu Horse anhydride, vinyl acetate, vinylpyrrolidone, vinylimidazole, (meth) acrylic acid, (meth) acrylic acid derivatives such as (meth) acrylamides, vinyl halides, vinylidene halides. 合适的预聚物和低聚物包括但不限于(甲基)丙烯酰官能基的(甲基)丙烯酸共聚物，聚氨酯甲酸酯(甲基)丙烯酸酯，聚酯(甲基)丙烯酸酯，不饱和聚酯，聚醚(甲基)丙烯酸酯，硅氧烷(甲基)丙烯酸酯，环氧树脂(甲基)丙烯酸酯等。 Suitable prepolymers and oligomers include, but are not limited to (meth) acryloyl-functional (meth) acrylic acid copolymer, polyurethane-carboxylate (meth) acrylates, polyester (meth) acrylate, unsaturated polyesters, polyether (meth) acrylates, silicone (meth) acrylate, epoxy (meth) acrylate. 其合适的数均分子量可在例如500至10000间变动，优选500-5000取值范围。 Its suitable number average molecular weight from 500 to 10,000, for example, variation, preferably in the range 500-5000.

[0044] 与已知文献方法相比，本发明披露的化合物具有突出的结构新颖性，制备方法简捷高效性，反应条件温和性，以及光引发活性的高效性和环境友好性。 [0044] Compared with known literature methods, the compounds disclosed in the present invention has outstanding structural novelty, simple and efficient method for the preparation of the mild reaction conditions, as well as photo-initiator activity efficiency and environmental friendliness.

【具体实施方式】 [DETAILED DESCRIPTION]

[0045] 下面结合具体实施例进一步说明本发明要点。 [0045] The following examples further illustrate with reference to specific elements of the present invention. [0046] 实施例一: [0046] Example One:

[0047] [0047]

[0048] 将350毫克TPO溶解于2毫升氯仿中，依次加入100毫克多聚甲醛和200毫克无水三氯化铝，体系升温至60摄氏度回流反应17小时，加入5毫升水淬灭反应，分离有机相，水相用5毫升氯仿萃取三次，合并有机相，无水Na2SO4干燥，脱除溶剂后残余物在硅胶柱色谱上以乙酸乙酯/正己烷(I: 4至3: I)为洗脱液梯度淋洗，得到181毫克目标产物。 [0048] 350 mg of TPO was dissolved in 2 ml of chloroform, were added 100 mg of paraformaldehyde and 200 mg of anhydrous aluminum chloride, the system was heated to 60 ° C the reaction was refluxed for 17 hours, 5 ml of water was added to quench the reaction, separation The organic phase, the aqueous phase was extracted three times with 5 ml of chloroform, and the combined organic phase was dried over anhydrous Na2SO4, the solvent was removed and the residue was purified on silica gel column chromatography using ethyl acetate / n-hexane (I: 4 至 3: I) to wash deliquored gradient elution to give 181 mg of the desired product.

[0049]核磁共振数据=1H-Nmr(Cdci3JOOmHz):8.01-7.95 (m, 8H), 7.54-7.44 (m, 12H)，6.77(s，2H)，3.92(s，2H)，2.04(s，6H)，1.89(s，6H)，1.80ppm(s，6H)； [0049] NMR data = 1H-Nmr (Cdci3JOOmHz): 8.01-7.95 (m, 8H), 7.54-7.44 (m, 12H), 6.77 (s, 2H), 3.92 (s, 2H), 2.04 (s, 6H), 1.89 (s, 6H), 1.80ppm (s, 6H);

[0050] 13C-NMR(CDCl3, 75MHz):220.3(d, J = 287Hz)，139.3，137.6，137.1，135.4，133.3，132.3，131.8，131.7，131.6，131.0，130.1，128.9，128.7，128.5,76.6,21.1，19.1，18.2ppm。 [0050] 13C-NMR (CDCl3, 75MHz): 220.3 (d, J = 287Hz), 139.3,137.6,137.1,135.4,133.3,132.3,131.8,131.7,131.6,131.0,130.1,128.9,128.7,128.5,76.6 , 21.1,19.1,18.2ppm.

[0051] 实施例二: [0051] Example Two:

[0052] [0052]

[0053]自实施例一实验同时分离得到108毫克该目标产物。 [0053] The embodiment of a self-test while isolated 108 mg of the target product.

[0054]核磁共振数据,H-NMR(O)Cl3, 300MHz):8.06-7.99 (m, 4H)，7.62-7.27 (m, 6H)， [0054] NMR data, H-NMR (O) Cl3, 300MHz): 8.06-7.99 (m, 4H), 7.62-7.27 (m, 6H),

6.89 (s, 1H) ,4.59(s,2H)，2.39(s,3H)，2.13(s,3H)，1.97ppm(s,3H)； 6.89 (s, 1H), 4.59 (s, 2H), 2.39 (s, 3H), 2.13 (s, 3H), 1.97ppm (s, 3H);

[0055] 13C-匪R (CDCl3, 75MHz):290 (d, J = 290Hz)，140.0，137.7，137.2，134.9，134.4，132.5，132.4，132.2，131.8，131.7，130.7，130.3，129.8，129.4，128.8，128.6，126.2,76.6，40.2，19.4，16.6ppm.[0056] 实施例三: [0055] 13C- bandit R (CDCl3, 75MHz): 290 (d, J = 290Hz), 140.0,137.7,137.2,134.9,134.4,132.5,132.4,132.2,131.8,131.7,130.7,130.3,129.8,129.4, . 128.8,128.6,126.2,76.6,40.2,19.4,16.6ppm [0056] Example Three:

[0057] [0057]

[0058] 将214毫克实施例一化合物和120毫克碳酸钾置于5毫升1/1体积比的四氢呋喃/水溶剂中，在室温下搅拌反应，用TLC跟踪监测至原料消失(约2小时)。 [0058] 214 mg of the compound of Example A and 120 mg of potassium carbonate into THF / water solvent ratio of 1/1 volume of 5 ml, and the reaction was stirred at room temperature, followed by TLC to monitor the disappearance of starting material (about 2 hours). 脱除溶剂，残余物和1/1体积比的二氯甲烷/水混合振摇，分离有机相，水相用二氯甲烷萃取2次，合并有机相，硫酸镁干燥，过滤，脱除溶剂后残余物在硅胶柱色谱上以乙酸乙酯/正己烷(I: 2至3: 1)为洗脱液梯度淋洗，得到137毫克淡黄色油状目标产物。 After the solvent was removed, and the residue was 1/1 volume of methylene chloride / water mixture was shaken, the organic phase was separated, the aqueous phase was extracted twice with dichloromethane, organic phases were combined, dried over magnesium sulfate, filtered, and the solvent removed The residue was purified on silica gel column chromatography using ethyl acetate / n-hexane (I: 2 至 3: 1) as eluent gradient elution, to give 137 mg of the desired product as a pale yellow oil. HRMS高分辩质谱:理论值C23H24O3P(M+H):379.1463 ;实测值:379.1471。 HRMS high resolution mass spectrometry: Theory C23H24O3P (M + H): 379.1463; Found: 379.1471.

[0059] 实施例四: [0059] Example Four:

[0060] [0060]

[0061] 在氮气保护下，将350毫克实施例三化合物置于20毫升CH2Cl2中，冷却到零度，缓缓向其加入含有90毫克新鲜蒸馏的丙烯酰氯的2毫升CH2Cl2溶液，加入175微升Et3N和2毫克DMAP后反应液搅拌2小时。 [0061] Under nitrogen, 350 mg of the compound of Example III is placed in 20 ml CH2Cl2, cooled to zero degrees, to which was added slowly 2 ml CH2Cl2 solution containing 90 mg of freshly distilled acryloyl chloride, Et3N was added 175 microliters After 2 mg of DMAP and the reaction was stirred for 2 hours. 混合液回至室温继续反应I小时后倒入50毫升水中，分离有机相，用20毫升CH2Cl2萃取水相2次，合并有机相后用饱和食盐水洗涤并在Na2SO4上干燥，过滤浓缩得到的粗产物以乙酸乙酯和正己烷为洗脱液在硅胶柱色谱上分离得到淡黄色油状产物，产率83%。 The reaction mixture was returned to room temperature continued I hour and poured into 50 ml of water, the organic phase was separated, extracted with 20 ml CH2Cl2 aqueous phase twice, combined organic phases were washed with saturated brine and dried over Na2SO4, filtered and concentrated to give crude The product with ethyl acetate and n-hexane as eluent on a silica gel column chromatography to give a pale yellow oily product, yield 83%. HRMS高分辩质谱:理论值C26H26O4P(M+H):433.1569 ;实测值:433.1574。 HRMS high resolution mass spectrometry: Theory C26H26O4P (M + H): 433.1569; Found: 433.1574.

[0062] 实施例五: [0062] Example five:

[0063] [0063]

[0064] 在氮气保护下，将76毫克实施例四化合物置于4毫升甲苯中，加入7毫克AIBN后混合液在60摄氏度搅拌反应2小时。 [0064] Under nitrogen, 76 mg of the compound of Example IV in 4 ml of toluene, 7 mg of AIBN was added after the mixture was stirred at 60 ° C for 2 hours. 减压脱除溶剂后即定量地得到淡黄色粉末目标聚合产物。 The solvent was removed under reduced pressure to give a pale yellow powder after the quantitative polymerization product of the target.

[0065] 实施例六: [0065] Example VI:

[0066] [0066]

[0067] 在氮气保护下将378毫克实施例三化合物和15毫克的双丁基锡双月桂酯混合于2毫升二氧六环溶剂中，向其滴加84毫克1，6_己二异氰酸酯在I毫升二氧六环中的溶液。 [0067] Under nitrogen 378 mg of the compound of Example III and 15 mg of dibutyl tin bis lauryl sulfate mixed in 2 ml of dioxane solvent solution of 84 mg 1,6_ its hexamethylene diisocyanate in I ml The dioxane. 滴毕缓缓升温至70摄氏度反应2小时。 Bi dropwise slowly warmed to 70 ° C for 2 hours. 减压脱除溶剂后残余物直接在硅胶柱色谱上以乙酸乙酯和己烷(3/1)为洗脱液分离得到210毫克淡黄色腊状目标产物。 After the solvent was removed under reduced pressure and the residue was chromatographed on a silica gel column with ethyl acetate and hexane (3/1) to give 210 mg of the desired product as a pale yellow waxy isolated directly as eluant. HRMS高分辩质谱:理论值C54H59O8P2N2 (M+H):925.3747 ;实测值:925.3754。 HRMS high resolution mass spectrometry: Theory C54H59O8P2N2 (M + H): 925.3747; Found: 925.3754.

[0068] 实施例七: [0068] Example VII:

[0069] [0069]

[0070] 参照实施例一的反应条件，自420毫克BAPO在5毫升氯仿中和150毫克多聚甲醛及280毫克无水三氯化铝反应制备避光下硅胶柱色谱分离得到了137毫克黄色固体产物。 [0070] The reaction conditions of Example with reference to one embodiment, from 420 mg BAPO in 5 ml of chloroform and 150 mg of paraformaldehyde and 280 mg of dark prepared under anhydrous silica gel column chromatography to give the aluminum trichloride reaction 137 mg of a yellow solid product. HRMS 高分辩质谱:理论值C53H55O6P2 (M+H):849.3474 ;实测值:849.3479。 HRMS high resolution mass spectrometry: Theory C53H55O6P2 (M + H): 849.3474; Found: 849.3479.

[0071] 实施例八: [0071] Example Eight:

[0072] [0072]

[0073] 在实施例七的反应中同时分离得到了164毫克该目标产物，黄色油状液体。 [0073] In the seventh embodiment of the reaction while isolated 164 mg of the desired product as a yellow oily liquid. HRMS高分辩质谱:理论值C27H29ClO3P (M+H):467.1543 ;实测值:467.1552。 HRMS high resolution mass spectrometry: Theory C27H29ClO3P (M + H): 467.1543; Found: 467.1552.

[0074] 实施例九: [0074] Example IX:

[0075] [0075]

[0076] 在实施例七的反应中同时分离得到了74毫克黄色无定型粉末状该聚合物。 [0076] In the seventh embodiment of the reaction while isolated 74 mg of a yellow amorphous powder form of the polymer.

[0077] 实施例十: [0077] Example Ten:

[0078] 依照下述的重量百分比配制光辐射固化测试样品:28份:环氧丙烯酸酯；35份:聚酯丙烯酸酯；5份:已二醇二丙烯酸酯；5份:季戊四醇三丙烯酸酯；23份:二氧化钛颜料；4份:选取的实施例酰基膦氧光引发剂化合物。 [0078] In accordance with the following formulation in weight percent radiation curable optical test sample: 28 parts: epoxy acrylate; 35 parts: polyester acrylates; 5 parts: hexanediol diacrylate; 5 parts: pentaerythritol triacrylate; 4 parts; titanium dioxide pigment:: Select embodiment acyl phosphine oxide photoinitiator compound 23 parts.

[0079] 取部分上述混合物充分研磨均匀后喷涂在白色基板上，在空气下形成约20微米的涂层。 [0079] A portion of the above mixture is thoroughly ground uniformly sprayed on a white board, a coating of about 20 microns is formed in air. 以250W高压汞灯为光源于距离样品12厘米处辐照。 With 250W high-pressure mercury lamp as a light source at 12 cm from the sample is irradiated at. 指压刮擦法判定涂层完全固化情况。 Acupressure scratch coating method determines the situation is completely cured. 上述实施例化合物一，三，四，五，六，七和九均引发膜层固化完全，显示了良好的光敏引发性能。 A compound of the above embodiments, three, four, five, six, seven, and nine were caused by the film is completely cured, exhibited good performance photoinitiator.