TWI791994B - Polymerizable compound, liquid crystal composition, liquid crystal display element and liquid crystal display - Google Patents

Abstract

本發明涉及可聚合化合物、液晶組合物、液晶顯示元件及液晶顯示器。本發明的可聚合化合物結構如下式I所示，包含該可聚合化合物的液晶組合物具有高的電壓保持率及較高的RM轉化率，應用於PS-(聚合物穩定)或PSA-(聚合物穩定配向)型液晶顯示元件中時，能夠降低殘像，藉以提高產品品質。 The present invention relates to a polymerizable compound, a liquid crystal composition, a liquid crystal display element and a liquid crystal display. The structure of the polymerizable compound of the present invention is shown in the following formula I. The liquid crystal composition comprising the polymerizable compound has a high voltage retention rate and a higher RM conversion rate, and is applied to PS- (polymer stabilization) or PSA- (polymerization When used in material-stable alignment) type liquid crystal display elements, image retention can be reduced, thereby improving product quality.

Description

可聚合化合物、液晶組合物、液晶顯示元件及液晶顯示器 Polymerizable compound, liquid crystal composition, liquid crystal display element and liquid crystal display

本發明屬於液晶顯示技術領域，具體涉及一種可聚合化合物、包含該可聚合化合物的液晶組合物，以及包含有該可聚合化合物或液晶組合物的液晶顯示元件或液晶顯示器。 The invention belongs to the field of liquid crystal display technology, and in particular relates to a polymerizable compound, a liquid crystal composition containing the polymerizable compound, and a liquid crystal display element or a liquid crystal display containing the polymerizable compound or the liquid crystal composition.

隨著顯示技術的發展，液晶顯示元件(Liquid Crystal Display，LCD)等平面顯示裝置因具有高畫質、省電、機身薄及應用範圍廣等優點，而被廣泛的應用於手機、電視、個人數位助理、數位相機、筆記型電腦、台式電腦等各種消費性電子產品，成為顯示裝置中的主流。 With the development of display technology, liquid crystal display (Liquid Crystal Display, LCD) and other flat display devices are widely used in mobile phones, TVs, Various consumer electronic products such as personal digital assistants, digital cameras, notebook computers, and desktop computers have become the mainstream of display devices.

反應性液晶(Reactive Mesogen,RM)目前是液晶顯示行業非常熱門且重要的研究方向，其可能應用的領域包括聚合物穩定配向(PSA)液晶顯示，聚合物穩定藍相(PS-BP)液晶顯示以及圖形化位元相差膜(Pattern Retarder Film)等。 Reactive liquid crystal (Reactive Mesogen, RM) is currently a very popular and important research direction in the liquid crystal display industry. Its possible application fields include polymer stabilized alignment (PSA) liquid crystal display, polymer stabilized blue phase (PS-BP) liquid crystal display And patterned bit phase difference film (Pattern Retarder Film) and so on.

但是，液晶化合物與RM混合後在PSA模式顯示器中的應用方面仍具有一些缺點。首先，到目前為止並不是所有RM都適合用於PSA顯示器；同時，如果採用紫外光(Ultraviolet light)而不添加光引發劑使RM進行聚合，則能夠選擇RM種類變得更少；另外，要求液晶化合物與所選擇的RM組合形成的液晶組合物具有較高的轉化率和較低的殘留量，以及高的電壓保持率(VHR) 以達到預期顯示效果。PSA-VA顯示模式，採用紫外光輻照後的液晶組合物仍然具有高的VHR是非常重要的，否則會導致顯示器出現殘像等問題。通常液晶化合物與RM組成的液晶組合物在液晶顯示元件或液晶顯示器製備過程需要經過兩個階段的紫外光照射製程，使RM聚合，並在RM聚合後儘量少的殘留在液晶組合物中。 However, the application of liquid crystal compounds mixed with RMs in PSA mode displays still has some disadvantages. First of all, not all RMs are suitable for PSA displays so far; at the same time, if the RMs are polymerized using Ultraviolet light without adding a photoinitiator, fewer RM types can be selected; in addition, the requirements Liquid crystal compounds combined with selected RMs form liquid crystal compositions with high conversion and low residuals, as well as high voltage holding ratio (VHR) to achieve the desired display effect. In the PSA-VA display mode, it is very important that the liquid crystal composition still has a high VHR after being irradiated with ultraviolet light, otherwise it will cause problems such as afterimages on the display. Usually, the liquid crystal composition composed of liquid crystal compound and RM needs to go through two stages of ultraviolet light irradiation process in the preparation process of liquid crystal display element or liquid crystal display, so that RM is polymerized, and after RM is polymerized, as little as possible remains in the liquid crystal composition.

為了克服反應性液晶(RM)聚合轉化率低、殘留量大和VHR低的問題，獲得具有RM轉化效率高、殘留量少、VHR高的液晶組合物，本發明人等進行了深入研究，發現通過在液晶組合物中含有本發明的化合物能夠解決該問題，藉以完成了本發明。 In order to overcome the problems of low polymerization conversion rate, large residual amount and low VHR of reactive liquid crystal (RM), and obtain a liquid crystal composition with high RM conversion efficiency, low residual amount and high VHR, the inventors have conducted in-depth research and found that by Containing the compound of the present invention in a liquid crystal composition can solve this problem, thereby completing the present invention.

具體地，本發明包含以下內容：本發明的第一方面，提供一種化合物，該化合物為式I所示的化合物，

Specifically, the present invention includes the following content: the first aspect of the present invention provides a compound, which is a compound represented by formula I,

其中，L₁、L₂、L₃、L₄各自獨立地表示F原子、Cl原子、-CN、具有1至25個C原子的直鏈烷基、具有3至25個C原子的支鏈烷基、具有3至25個C原子的環狀烷基、具有2至25個C原子的烯基或具有2至25個C原子的炔基，其中 一個或多個不相鄰的-CH₂-基團任選地被-O-、-S-、-NH-、-CO-、-CO-O-、-O-CO-、-O-CO-O-，以使得-O-和/或-S-和/或-NH-彼此不直接相連的方式取代，和其中一個或多個H原子任選地被鹵素原子取代；r₁、r₃各自獨立地表示0、1、2、3或4；r₂、r₄各自獨立地表示0、1、2或3；x₁、x₂、x₃、x₄各自獨立地表示0、1或2，且x₁+x₂+x₃+x₄

3；Sp₁、Sp₂、Sp₃、Sp₄、Sp₅、Z₁、Z₂各自獨立地表示單鍵、具有1至25個C原子的直鏈烷基、具有3至25個C原子的支鏈烷基、具有3至25個C原子的環狀烷基、具有2至25個C原子的烯基或具有2至25個C原子的炔基，且其中一個或多個不相鄰的-CH₂-基團任選地被-O-、-S-、-CO-、-CO-O-、-O-CO-、-O-CO-O-以使得-O-和/或-S-彼此不直接相連的方式取代，其中一個或多個H原子任選被F原子或Cl原子取代；P₁、P₂、P₃、P₄各自獨立地表示可聚合基團。 Wherein, L ₁ , L ₂ , L ₃ , and L ₄ each independently represent an F atom, a Cl atom, -CN, a straight chain alkyl group having 1 to 25 C atoms, a branched chain alkyl group having 3 to 25 C atoms A group, a cyclic alkyl group having 3 to 25 C atoms, an alkenyl group having 2 to 25 C atoms or an alkynyl group having 2 to 25 C atoms, wherein one or more non-adjacent -CH ₂ - The group is optionally replaced by -O-, -S-, -NH-, -CO-, -CO-O-, -O-CO-, -O-CO-O-, such that -O- and/or -S- and/or -NH- are substituted in such a way that they are not directly connected to each other, and wherein one or more H atoms are optionally substituted by halogen atoms; r ₁ and r ₃ each independently represent 0, 1, 2, 3 or 4; r ₂ , r ₄ each independently represent 0, 1, 2 or 3; x ₁ , x ₂ , x ₃ , x ₄ each independently represent 0, 1 or 2, and x ₁ +x ₂ +x ₃ + _x4

3; Sp ₁ , Sp ₂ , Sp ₃ , Sp ₄ , Sp ₅ , Z ₁ , and Z ₂ each independently represent a single bond, a straight-chain alkyl group having 1 to 25 C atoms, an alkyl group having 3 to 25 C atoms Branched chain alkyl, cyclic alkyl having 3 to 25 C atoms, alkenyl having 2 to 25 C atoms or alkynyl having 2 to 25 C atoms, and one or more of the non-adjacent The -CH ₂ - group is optionally replaced by -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O- such that -O- and/or - S-substituted in a way that is not directly connected to each other, wherein one or more H atoms are optionally substituted by F atoms or Cl atoms; P ₁ , P ₂ , P ₃ , and P ₄ each independently represent a polymerizable group.

本發明的第二方面，提供一種液晶組合物，所述液晶組合物包含一種或多種式I所示的可聚合化合物。 The second aspect of the present invention provides a liquid crystal composition, which contains one or more polymerizable compounds represented by formula I.

本發明的第三方面，提供一種液晶顯示元件或液晶顯示器，所述液晶顯示元件或液晶顯示器包含一種或多種式I所示的可聚合化合物或包含一種或多種式I所示的可聚合化合物的液晶組合物。 A third aspect of the present invention provides a liquid crystal display element or a liquid crystal display, the liquid crystal display element or liquid crystal display comprising one or more polymerizable compounds represented by formula I or comprising one or more polymerizable compounds represented by formula I liquid crystal composition.

本發明提供了一種新型的可聚合化合物，與習知技術相比，含本發明的可聚合化合物的液晶組合物具有高的電壓保持率(VHR)及包含本發明 的可聚合化合物或包含本發明的可聚合化合物的液晶組合物在製成顯示元件時，轉化率高、RM殘留量低，應用於PS-(聚合物穩定)或PSA-(聚合物穩定配向)型液晶顯示元件中時，能夠降低殘像、縮短聚合操作時間，有利於提升產品品質和降低操作成本。 The invention provides a novel polymerizable compound, compared with the prior art, the liquid crystal composition containing the polymerizable compound of the present invention has high voltage retention (VHR) and comprises the present invention When the polymerizable compound or the liquid crystal composition comprising the polymerizable compound of the present invention is made into a display element, the conversion rate is high and the residual amount of RM is low, and it is applied to PS- (polymer stabilized) or PSA- (polymer stabilized alignment) When used in a type liquid crystal display element, it can reduce afterimages, shorten the polymerization operation time, and help improve product quality and reduce operating costs.

圖1示出式I-2-1所示可聚合化合物的¹H-NMR譜圖； Fig. 1 shows the ¹ H-NMR spectrogram of the polymerizable compound shown in formula I-2-1;

本發明公開了一種上述式I所示的可聚合化合物。 The present invention discloses a polymerizable compound represented by the above formula I.

本發明公開的可聚合化合物，較佳地，在式I所示的化合物中：L₁、L₂、L₃、L₄各自獨立地表示碳原子數為1-5的烷基、氟取代的碳原子數為1-5的烷基、碳原子數為2-5的烯基、碳原子數為1-5的烷氧基、氟取代的碳原子數為1-5的烷氧基、F原子或Cl原子；r₁、r₃各自獨立地表示0、1或2；r₂、r₄各自獨立地表示0或1；x₁、x₂、x₃、x₄各自獨立地表示0或1，且x₁+x₂+x₃+x₄

3；Sp₁、Sp₂、Sp₃、Sp₄、Sp₅、Z₁、Z₂各自獨立地表示單鍵、碳原子數為1-10的烷基、碳原子數為2-10的烯基或碳原子數為2-10的炔基，其中一個或多個不相鄰的-CH₂-基團任選地被-O-、-CO-、-CO-O-、-O-CO-取代，一個或多個H原子任選被F原子取代； P₁、P₂、P₃、P₄各自獨立地表示

、

、

、

、

、

In the polymerizable compound disclosed in the present invention, preferably, in the compound represented by formula I: L ₁ , L ₂ , L ₃ , and L ₄ each independently represent an alkyl group with 1-5 carbon atoms, fluorine-substituted Alkyl group with 1-5 carbon atoms, alkenyl group with 2-5 carbon atoms, alkoxy group with 1-5 carbon atoms, alkoxy group with 1-5 carbon atoms substituted by fluorine, F atom or Cl atom; r ₁ , r ₃ each independently represent 0, 1 or 2; r ₂ , r ₄ each independently represent 0 or 1; x ₁ , x ₂ , x ₃ , x ₄ each independently represent 0 or 1, and x ₁ +x ₂ +x ₃ +x ₄

3; Sp ₁ , Sp ₂ , Sp ₃ , Sp ₄ , Sp ₅ , Z ₁ , and Z ₂ each independently represent a single bond, an alkyl group with 1-10 carbon atoms, and an alkenyl group with 2-10 carbon atoms Or an alkynyl group with 2-10 carbon atoms, wherein one or more non-adjacent -CH ₂ - groups are optionally replaced by -O-, -CO-, -CO-O-, -O-CO- Substitution, one or more H atoms are optionally substituted by F atoms; P ₁ , P ₂ , P ₃ , P ₄ each independently represent

,

,

,

,

,

本發明公開的可聚合化合物，更佳地，其選自下述的式I-1-1至式I-17-2所示化合物所組成的群組，

The polymerizable compound disclosed in the present invention, more preferably, is selected from the group consisting of compounds represented by the following formula I-1-1 to formula I-17-2,

本發明還提供一種液晶組合物，該液晶組合物包含一種或多種前述的本發明的可聚合化合物。 The present invention also provides a liquid crystal composition comprising one or more of the aforementioned polymerizable compounds of the present invention.

做為本發明的一個方案的液晶組合物，含有前述的式I所示的化合物。液晶組合物中，除了式I所示的化合物之外，還可以含有式I所示的化合物之外的液晶化合物以及其他添加材料。 The liquid crystal composition as one aspect of the present invention contains the compound represented by the aforementioned formula I. In addition to the compound represented by the formula I, the liquid crystal composition may contain liquid crystal compounds other than the compound represented by the formula I and other additive materials.

較佳地，本發明的液晶組合物還包含一種或多種下述的式II所示化合物以及一種或多種下述的式III所示化合物，

Preferably, the liquid crystal composition of the present invention further comprises one or more compounds represented by the following formula II and one or more compounds represented by the following formula III,

式II中，R₁、R₂各自獨立地表示碳原子數為1-10的烷基、氟取代的碳原子數為1-10的烷基、碳原子數為1-10的烷氧基、氟取代的碳原子數為1-10的烷氧基、碳原子數為2-10的鏈烯基、氟取代的碳原子數為2-10的鏈烯基、碳原子數為3-8的鏈烯氧基或氟取代的碳原子數為3-8的鏈烯氧基；

、

各自獨立地表示

或

； 式III中，R₃、R₄各自獨立地表示碳原子數為1-10的烷基、氟取代的碳原子數為1-10的烷基、碳原子數為1-10的烷氧基、氟取代的碳原子數為1-10的烷氧基、碳原子數為2-10的鏈烯基、氟取代的碳原子數為2-10的鏈烯基、碳原子數為3-8的鏈烯氧基或氟取代的碳原子數為3-8的鏈烯氧基，且R₃、R₄中任意一個或多個不相鄰的-CH₂-任選被亞環戊基、亞環丁基或亞環丙基取代；Z₁、Z₂各自獨立地表示單鍵、-CH₂CH₂-、-CH₂O-或-OCH₂-；

、

各自獨立地表示

、

、

、

、

m₁表示1或2，當m₁表示2時，

相同或不同； n₁表示0、1或2，當n₁表示2時，

相同或不同。 In formula II, R ₁ and R ₂ each independently represent an alkyl group with 1-10 carbon atoms, an alkyl group with 1-10 carbon atoms substituted by fluorine, an alkoxy group with 1-10 carbon atoms, Alkoxy group with 1-10 carbon atoms substituted by fluorine, alkenyl group with 2-10 carbon atoms, alkenyl group with 2-10 carbon atoms substituted by fluorine, and alkenyl group with 3-8 carbon atoms Alkenyloxy or fluorine-substituted alkenyloxy with 3-8 carbon atoms;

,

express independently

or

In formula III, R ₃ and R ₄ independently represent an alkyl group with 1-10 carbon atoms, an alkyl group with 1-10 carbon atoms substituted by fluorine, and an alkoxy group with 1-10 carbon atoms , alkoxy group with 1-10 carbon atoms substituted by fluorine, alkenyl group with 2-10 carbon atoms, alkenyl group with 2-10 carbon atoms substituted with fluorine, 3-8 carbon atoms Alkenyloxy or alkenyloxy with 3-8 carbon atoms substituted by fluorine, and any one or more non-adjacent -CH ₂ - in R ₃ and R ₄ is optionally replaced by cyclopentylene, Substituted by cyclobutylene or cyclopropylene; Z ₁ and Z ₂ each independently represent a single bond, -CH ₂ CH ₂ -, -CH ₂ O- or -OCH ₂ -;

,

express independently

,

,

,

,

m ₁ means 1 or 2, when m ₁ means 2,

same or different; n ₁ means 0, 1 or 2, when n ₁ means 2,

same or different.

通過在本發明的液晶組合物中含有式II所示化合物、式III所示化合物的組合，獲得的液晶組合物具有低的旋轉黏度低藉以有利於提高液晶組合物的反應速度，且具有負介電各項異性，能夠調節組合物的驅動電壓。 By containing the compound shown in the formula II and the combination of the compound shown in the formula III in the liquid crystal composition of the present invention, the obtained liquid crystal composition has a low rotational viscosity, which is beneficial to improve the reaction speed of the liquid crystal composition, and has a negative medium Electrical anisotropy, capable of adjusting the driving voltage of the composition.

本發明中，將除式I所示化合物之外的其他化合物的總質量記為100%，式I所示化合物的質量與其他化合物的總質量之間比值的百分數，記為液晶組合物中式I所示化合物的質量分數。例如，在液晶組合物中只包含有式I、式II及式III所示化合物的情況下，則式II和式III所示化合物的總含量記為100%，式I所示化合物的加入量與式II和式III所示化合物的總質量之間比值的百分數，記為式I所示化合物的質量分數。 In the present invention, the total mass of other compounds other than the compound shown in formula I is recorded as 100%, and the percentage of the ratio between the mass of the compound shown in formula I and the total mass of other compounds is recorded as formula I in the liquid crystal composition Mass fractions of indicated compounds. For example, when the liquid crystal composition only contains compounds shown in formula I, formula II and formula III, the total content of compounds shown in formula II and formula III is recorded as 100%, and the amount of compound shown in formula I The percentage of the ratio to the total mass of the compounds represented by formula II and formula III is recorded as the mass fraction of the compound represented by formula I.

本發明的液晶組合物中，較佳地，前述式II所示化合物選自式II-1至式II-17所示化合物所組成的群組，

In the liquid crystal composition of the present invention, preferably, the compound represented by the aforementioned formula II is selected from the group consisting of compounds represented by formula II-1 to formula II-17,

較佳地，前述式III所示化合物選自式III-1至式III-15所示化合物所組成的群組，

Preferably, the compound represented by the aforementioned formula III is selected from the group consisting of compounds represented by formula III-1 to formula III-15,

其中，R₃₁、R₄₁各自獨立地表示碳原子數為1-10的烷基、氟取代的碳原子數為1-10的烷基、碳原子數為1-10的烷氧基、氟取代的碳原子數為1-10的烷氧基、碳原子數為2-10的鏈烯基、氟取代的碳原子數為2-10的鏈烯基、碳原子數為3-8的鏈烯氧基或氟取代的碳原子數為3-8的鏈烯氧基，並且R₃、R₄所示基團中任意一個或多個不相鄰的-CH₂-任選被亞環戊基、亞環丁基或亞環丙基取代。 Wherein, R ₃₁ and R ₄₁ each independently represent an alkyl group with 1-10 carbon atoms, an alkyl group with 1-10 carbon atoms substituted by fluorine, an alkoxy group with 1-10 carbon atoms, a fluorine-substituted Alkoxy groups with 1-10 carbon atoms, alkenyl groups with 2-10 carbon atoms, alkenyl groups with 2-10 carbon atoms substituted by fluorine, alkenyl groups with 3-8 carbon atoms An alkenyloxy group with 3-8 carbon atoms substituted by oxo or fluorine, and any one or more non-adjacent -CH ₂ - in the groups represented by R ₃ and R ₄ is optionally replaced by a cyclopentylene group , cyclobutylene or cyclopropylene.

本發明公開的液晶組合物中，較佳地，還包含一種或多種式IV所示的化合物，

In the liquid crystal composition disclosed in the present invention, preferably, it also contains one or more compounds represented by formula IV,

其中，R₅、R₆各自獨立地表示碳原子數為1-10的烷基、氟取代的碳原子數為1-10的烷基、碳原子數為1-10的烷氧基、氟取代的碳原子數為1-10的烷氧基、碳原子數為2-10的鏈烯基、氟取代的碳原子數為2-10的鏈烯基、碳原子 數為3-8的鏈烯氧基或氟取代的碳原子數為3-8的鏈烯氧基，並且R₅、R₆中任意一個或多個不相鄰的-CH₂-任選被亞環戊基、亞環丁基或亞環丙基替代；W表示-O-、-S-或-CH₂O-。 Wherein, R ₅ and R ₆ each independently represent an alkyl group with 1-10 carbon atoms, an alkyl group with 1-10 carbon atoms substituted by fluorine, an alkoxy group with 1-10 carbon atoms, a fluorine-substituted Alkoxy groups with 1-10 carbon atoms, alkenyl groups with 2-10 carbon atoms, alkenyl groups with 2-10 carbon atoms substituted by fluorine, alkenyl groups with 3-8 carbon atoms Alkenyloxy group with 3-8 carbon atoms substituted by oxo or fluorine, and any one or more non-adjacent -CH ₂ - in R ₅ and R ₆ is optionally replaced by cyclopentylene, cyclobutylene group or cyclopropylene; W represents -O-, -S- or -CH ₂ O-.

通過在本申請的液晶組合物中含有前述的式IV所示的化合物，藉以能夠使得液晶組合物具有較大的負的介電各向異性，有利於降低元件的驅動電壓。 By including the compound represented by the aforementioned formula IV in the liquid crystal composition of the present application, the liquid crystal composition can have relatively large negative dielectric anisotropy, which is beneficial to reduce the driving voltage of the device.

進一步地，前述式IV所示的化合物選自式IV-1至式IV-10所示化合物，

其中，R₅₁、R₆₁表示碳原子數為1-6的烷基；本發明公開的液晶組合物中，較佳地，還包含一種或多種式V所示的化合物，

Further, the compound shown in the aforementioned formula IV is selected from the compounds shown in formula IV-1 to formula IV-10,

Among them, R ₅₁ and R ₆₁ represent an alkyl group with 1-6 carbon atoms; the liquid crystal composition disclosed in the present invention preferably further contains one or more compounds represented by formula V,

其中，R₇、R₈各自獨立地表示碳原子數為1-10的烷基、氟取代的碳原子數為1-10的烷基、碳原子數為1-10的烷氧基、氟取代的碳原子數為1-10的烷氧基、碳原子數為2-10的鏈烯基、氟取代的碳原子數為2-10的鏈烯基、碳原子數為3-8的鏈烯氧基或氟取代的碳原子數為3-8的鏈烯氧基；

、

各自獨立地表示

、

或

。 Wherein, R ₇ and R ₈ each independently represent an alkyl group with 1-10 carbon atoms, an alkyl group with 1-10 carbon atoms substituted by fluorine, an alkoxy group with 1-10 carbon atoms, or an alkyl group with 1-10 carbon atoms substituted by fluorine. Alkoxy groups with 1-10 carbon atoms, alkenyl groups with 2-10 carbon atoms, alkenyl groups with 2-10 carbon atoms substituted by fluorine, alkenyl groups with 3-8 carbon atoms Alkenyloxy group with 3-8 carbon atoms substituted by oxy group or fluorine;

,

express independently

,

or

.

進一步地，上述式V所示的化合物較佳選自式V-1至式V-4所示化合物所組成的群組，

其中，R₇₁、R₈₁各自獨立的表示碳原子數為2-6的烷基或碳原子數為2-6的烯基；其中，做為碳原子數為2-6的烯基可以列舉出例如乙烯基、2-丙烯基或者3-戊烯基；R₈₂表示碳原子數為1-5的烷氧基；通過在本發明的液晶組合物中含有式V所示的化合物，能夠獲得高的清晰點、高的彈性常數，尤其是展曲彈性常數K₃₃，有利於提升液晶組合物的參數性能。 Further, the compound represented by the above formula V is preferably selected from the group consisting of compounds represented by formula V-1 to formula V-4,

Among them, R ₇₁ and R ₈₁ each independently represent an alkyl group with 2-6 carbon atoms or an alkenyl group with 2-6 carbon atoms; among them, the alkenyl group with 2-6 carbon atoms can be listed For example vinyl, 2-propenyl or 3-pentenyl; R ₈₂ represents the alkoxyl group that carbon number is 1-5; By containing the compound shown in formula V in the liquid crystal composition of the present invention, can obtain high The clear point and high elastic constant, especially the splay elastic constant K ₃₃ , are beneficial to improve the parameter performance of the liquid crystal composition.

本發明公開的液晶組合物中，較佳地，還包含一種或多種式VI所示化合物，

其中，R₉、R₁₀各自獨立地表示碳原子數為1-10的烷基、氟取代的碳原子數為1-10的烷基、碳原子數為1-10的烷氧基、氟取代的碳原子數為1-10的烷氧基、 碳原子數為2-10的鏈烯基、氟取代的碳原子數為2-10的鏈烯基、碳原子數為3-8的鏈烯氧基或氟取代的碳原子數為3-8的鏈烯氧基；

表示

、

或

。 In the liquid crystal composition disclosed in the present invention, preferably, it also contains one or more compounds represented by formula VI,

Wherein, R ₉ and R ₁₀ each independently represent an alkyl group with 1-10 carbon atoms, an alkyl group with 1-10 carbon atoms substituted by fluorine, an alkoxy group with 1-10 carbon atoms, or an alkyl group with 1-10 carbon atoms substituted by fluorine. Alkoxy groups with 1-10 carbon atoms, alkenyl groups with 2-10 carbon atoms, alkenyl groups with 2-10 carbon atoms substituted by fluorine, alkenyl groups with 3-8 carbon atoms Alkenyloxy group with 3-8 carbon atoms substituted by oxy group or fluorine;

express

,

or

.

進一步地，前述式VI所示的化合物較佳選自式VI-1至VI-3所示化合物所組成的群組，

其中，R₉₁、R₁₀₁各自獨立地較佳表示碳原子數為2-6的烷基或原子數為2-6的烯基。 Further, the compound represented by the aforementioned formula VI is preferably selected from the group consisting of compounds represented by the formulas VI-1 to VI-3,

Among them, R ₉₁ and R ₁₀₁ each independently preferably represent an alkyl group with 2-6 carbon atoms or an alkenyl group with 2-6 atoms.

通過在液晶組合物中含有選自式VI-1至VI-3所示的化合物，能夠提高液晶組合物的清晰點。 The clear point of the liquid crystal composition can be improved by including the compound selected from the group consisting of formulas VI-1 to VI-3 in the liquid crystal composition.

較佳地，本發明的液晶組合物按照質量百分數包含：0.01-1%的式I所示化合物，30-60%的式II所示化合物，30-60%的式III所示化合物，1-10%的式VI所示化合物；較佳地，本發明的液晶組合物按照質量百分數包含：0.01-1%的式I所示化合物，15-60%的式II所示化合物，20-60%的式III所示化合物，1-15%的式IV所示化合物，1-10%的式VI所示化合物；較佳地，本發明的液晶組合物按照質量百分數包含：0.03-0.2%的式I所示化 合物，35-45%的式II所示化合物，45-50%的式III所示化合物，2-10%的式IV所示化合物，2-5%的式VI所示化合物。 Preferably, the liquid crystal composition of the present invention comprises: 0.01-1% of the compound shown in formula I, 30-60% of the compound shown in formula II, 30-60% of the compound shown in formula III, 1- 10% of the compound shown in formula VI; preferably, the liquid crystal composition of the present invention comprises: 0.01-1% of the compound shown in formula I, 15-60% of the compound shown in formula II, 20-60% The compound shown in the formula III, 1-15% of the compound shown in the formula IV, 1-10% of the compound shown in the formula VI; preferably, the liquid crystal composition of the present invention comprises: 0.03-0.2% of the formula I show compound, the compound shown in the formula II of 35-45%, the compound shown in the formula III of 45-50%, the compound shown in the formula IV of 2-10%, the compound shown in the formula VI of 2-5%.

較佳地，本發明的液晶組合物按照質量百分數包含：0.01-1%的式I所示化合物，15-60%的式II所示化合物，20-60%的式III所示化合物，1-30%的式V所示化合物，1-10%的式VI所示化合物；較佳地，本發明的液晶組合物按照質量百分數包含：0.03-0.2%的式I所示化合物，25-40%的式II所示化合物，35-50%的式III所示化合物，5-20%的式V所示化合物，2-5%的式VI所示化合物。 Preferably, the liquid crystal composition of the present invention comprises according to mass percentage: 0.01-1% of the compound shown in formula I, 15-60% of the compound shown in formula II, 20-60% of the compound shown in formula III, 1- 30% of the compound shown in formula V, 1-10% of the compound shown in formula VI; preferably, the liquid crystal composition of the present invention comprises: 0.03-0.2% of the compound shown in formula I, 25-40% Compound shown in formula II, 35-50% compound shown in formula III, 5-20% compound shown in formula V, 2-5% compound shown in formula VI.

較佳地，本發明的液晶組合物按照質量百分數包含：0.01-1%的式I所示化合物，15-60%的式II所示化合物，20-60%的式III所示化合物，1-15%的式IV所示化合物，1-30%的式V所示化合物，1-10%的式VI所示化合物；較佳地，本發明的液晶組合物按照質量百分數包含：0.03-0.2%的式I所示化合物，20-40%的式II所示化合物，30-50%的式III所示化合物，2-10%的式IV所示化合物，5-20%的式V所示化合物，2-5%的式VI所示化合物。 Preferably, the liquid crystal composition of the present invention comprises according to mass percentage: 0.01-1% of the compound shown in formula I, 15-60% of the compound shown in formula II, 20-60% of the compound shown in formula III, 1- 15% of the compound shown in formula IV, 1-30% of the compound shown in formula V, 1-10% of the compound shown in formula VI; preferably, the liquid crystal composition of the present invention comprises: 0.03-0.2% by mass percentage The compound shown in formula I, 20-40% of the compound shown in formula II, 30-50% of the compound shown in formula III, 2-10% of the compound shown in formula IV, 5-20% of the compound shown in formula V , 2-5% of the compound shown in the formula VI.

本發明公開的液晶組合物中，還可以加入各種功能的摻雜劑，在含有摻雜劑的情況下，摻雜劑的含量較佳在液晶組合物中所占的質量百分比為0.01-1%，這些摻雜劑可以列舉出例如抗氧化劑、紫外線吸收劑、手性劑。 In the liquid crystal composition disclosed in the present invention, dopants with various functions can also be added. In the case of containing dopants, the content of the dopant is preferably 0.01-1% by mass in the liquid crystal composition. , These dopants include, for example, antioxidants, ultraviolet absorbers, and chiral agents.

抗氧化劑、紫外線吸收劑可以列舉出，

t表示1-10的整數。 Examples of antioxidants and ultraviolet absorbers include,

t represents an integer of 1-10.

本發明的液晶顯示元元件包含前述的本發明的可聚合化合物或者包含前述的本發明的液晶組合物，該顯示元元件為主動矩陣顯示元元件或被動矩陣顯示元元件。 The liquid crystal display element of the present invention comprises the aforementioned polymerizable compound of the present invention or the aforementioned liquid crystal composition of the present invention, and the display element is an active matrix display element or a passive matrix display element.

較佳地，本發明的液晶顯示元元件較佳主動矩陣液晶顯示元元件。 Preferably, the liquid crystal display element of the present invention is preferably an active matrix liquid crystal display element.

較佳地，本發明的主動矩陣顯示元元件為PSVA-TFT或IPS-TFT液晶顯示元元件。 Preferably, the active matrix display element of the present invention is a PSVA-TFT or IPS-TFT liquid crystal display element.

對於前述的本發明的液晶顯示元元件，只要在其使用的液晶組合物中含有本發明的式I所示化合物，則對其結構沒有任何限定，本領域具有通常知識者能夠根據所需的性能選擇合適的液晶顯示元元件的結構。 For the aforesaid liquid crystal display element of the present invention, as long as the compound shown in the formula I of the present invention is contained in the liquid crystal composition used in it, then its structure is not limited, and those skilled in the art can determine the desired performance Select the appropriate structure of the liquid crystal display element.

做為本發明的液晶顯示器的一個實施方式，可以列舉，例如下述的結構：包括第一基板、第二基板，以及設置在第一基板和第二基板之間的液晶組合物，第一基板與第二基板平行相對設置，第一基板和第二基板的靠近液晶組合物一側設有配向層，第一基板設有公共電極、第二基板設有畫素電極， 第一基板與第二基板之間散佈有間隔物。 As an embodiment of the liquid crystal display of the present invention, can enumerate, for example following structure: comprise the first substrate, the second substrate, and the liquid crystal composition that is arranged between the first substrate and the second substrate, the first substrate It is arranged parallel to the second substrate, an alignment layer is provided on the side of the first substrate and the second substrate close to the liquid crystal composition, the first substrate is provided with a common electrode, and the second substrate is provided with a pixel electrode, Spacers are scattered between the first substrate and the second substrate.

做為本發明的液晶顯示器的製備方法，本領域具有通常知識者能夠根據本領域的常識選擇合適的方法進行製備。做為本發明的液晶顯示器的製備方法的一個例子，例如，包括下述步驟的製備方法：在第一基板和第二基板的表面均勻塗布配向材料，配向材料可以選用聚醯亞胺，對均勻塗布的配向材料進行加熱固化，加熱溫度為210-250℃，形成配向層；在第二基板表面散佈間隔物，並沿第一基板的邊緣塗布邊框膠，並在100℃-150℃下進行固化；將第一基板和第二基板相對設置，貼合形成具有夾層空間的結構；將液晶組合物注入第一基板和第二基板之間的夾層空間，密封固化，藉以將液晶組合物密封在第一基板和第二基板之間，並同時進行加電、紫外光照射。紫外光照射分為第一階段紫外光照射(UV1)、第二階段紫外光照射(UV2)的兩個階段。在UV1階段，紫外光波長為360nm-370nm，紫外光輻照度為60-72mw/cm²。做為紫外光照射的時間，可以為例如50-65s，較佳為50-60s。 As the preparation method of the liquid crystal display of the present invention, those skilled in the art can select an appropriate method for preparation according to common knowledge in the field. As an example of the preparation method of the liquid crystal display of the present invention, for example, the preparation method comprising the following steps: uniformly coating the alignment material on the surface of the first substrate and the second substrate, the alignment material can be selected from polyimide, for uniform The coated alignment material is heated and cured at 210-250°C to form an alignment layer; spacers are spread on the surface of the second substrate, and frame glue is coated along the edge of the first substrate, and cured at 100°C-150°C ; The first substrate and the second substrate are arranged oppositely, and bonded to form a structure with an interlayer space; the liquid crystal composition is injected into the interlayer space between the first substrate and the second substrate, sealed and solidified, so as to seal the liquid crystal composition in the second substrate between the first substrate and the second substrate, and carry out power supply and ultraviolet light irradiation at the same time. The ultraviolet light irradiation is divided into two stages of the first stage ultraviolet light irradiation (UV1) and the second stage ultraviolet light irradiation (UV2). In the UV1 stage, the wavelength of ultraviolet light is 360nm-370nm, and the irradiance of ultraviolet light is 60-72mw/cm ² . The time for ultraviolet light irradiation may be, for example, 50-65s, preferably 50-60s.

在第一階段的光照射結束後進行第二階段光照射(UV2)，UV2中所使用的光可以列舉出例如紫外光。第二階段紫外光照射(UV2)紫外光波長例如為360nm-370nm，在UV2階段使用紫外光輻照度為例如3-8mw/cm²。通過採用這樣的輻照度，能夠使得未發生聚合的式I所示化合物緩慢的完全聚合，提高可聚合化合物的轉化率，藉以使得液晶組合物中不存在可聚合化合物的殘留。並且由於聚合緩慢，該過程不會對已經形成的預傾角產生影響。UV2階段的紫外光照射時間可以為例如100-150min。 The second-stage light irradiation (UV2) is performed after the first-stage light irradiation is completed, and the light used in UV2 includes, for example, ultraviolet light. In the second stage of ultraviolet irradiation (UV2), the wavelength of ultraviolet light is, for example, 360nm-370nm, and the irradiance of ultraviolet light used in the UV2 stage is, for example, 3-8mw/cm ² . By adopting such irradiance, the unpolymerized compound represented by formula I can be slowly and completely polymerized, and the conversion rate of the polymerizable compound can be improved, so that there is no residue of the polymerizable compound in the liquid crystal composition. And because the polymerization is slow, the process has no effect on the pretilt angle already formed. The ultraviolet light irradiation time in the UV2 stage can be, for example, 100-150 min.

實施例 Example

為了更清楚地說明本發明，下面結合較佳實施例和附圖對本發明做進一步的說明。附圖中相似的部件以相同的附圖標記進行表示。本領域具有通常知識者應當理解，下面所具體描述的內容是說明性的而非限制性的，不應以此限制本發明的保護範圍。 In order to illustrate the present invention more clearly, the present invention will be further described below in conjunction with preferred embodiments and accompanying drawings. Similar parts in the figures are denoted by the same reference numerals. Those skilled in the art should understand that the content specifically described below is illustrative rather than restrictive, and should not limit the protection scope of the present invention.

本發明中，製備方法如無特殊說明則均為常規方法，所用的原料如無特別說明均可從公開的商業途徑獲得，百分比均是指質量百分比，溫度為攝氏度(℃)，液晶化合物也成為液晶單體，其他符號的具體意義及測試條件如下：Cp表示液晶清晰點(℃)，DSC定量法測試；△n表示光學各向異性，△n=n_e-n_o，其中，n_o為尋常光的折射率，n_e為非尋常光的折射率，測試條件為25±2℃，589nm，阿貝折射儀測試；△ε表示介電各向異性，△ε=ε∥-ε⊥，其中，ε∥為平行於分子軸的介電常數，ε⊥為垂直於分子軸的介電常數，測試條件為25±0.5℃，20微米垂直盒，INSTEC：ALCT-IR1測試；VHR表示電壓保持率(%)，測試條件為20±2℃、電壓為±5V、脈衝寬度為10ms、電壓保持時間16.7ms。測試設備為TOYO Model6254液晶性能綜合測試儀；γ₁表示旋轉黏度(mPa．s)，測試條件為25±0.5℃，20微米垂直盒，INSTEC：ALCT-IR1測試。 In the present invention, the preparation method is a conventional method unless otherwise specified, and the raw materials used can be obtained from open commercial channels if not otherwise specified, and the percentages all refer to mass percentages, and the temperature is degrees Celsius (° C.), and the liquid crystal compound also becomes Liquid crystal monomer, the specific meanings and test conditions of other symbols are as follows: Cp means liquid crystal clear point (°C), tested by DSC quantitative method; △n means optical anisotropy, △n=n _e -n _o , where n _o is The refractive index of ordinary light, ne _is the refractive index of extraordinary light, the test condition is 25±2°C, 589nm, Abbe refractometer test; △ε means dielectric anisotropy, △ε=ε∥-ε⊥, Among them, ε∥ is the dielectric constant parallel to the molecular axis, ε⊥ is the dielectric constant perpendicular to the molecular axis, the test condition is 25±0.5°C, 20 micron vertical cell, INSTEC: ALCT-IR1 test; VHR means voltage hold Rate (%), the test condition is 20±2℃, the voltage is ±5V, the pulse width is 10ms, and the voltage hold time is 16.7ms. The test equipment is TOYO Model6254 liquid crystal performance comprehensive tester; _γ1 means rotational viscosity (mPa.s), the test condition is 25±0.5°C, 20 micron vertical cell, INSTEC: ALCT-IR1 test.

本發明實施例中，液晶組合物的製備所用的設備和儀器為：液晶組合物的製備方法如下：將各可聚合化合物按照一定配比稱量後放入不鏽鋼燒杯中，將裝有各可聚合化合物的不鏽鋼燒杯置於磁力攪拌儀器上加熱融化，待不鏽鋼燒杯中的可聚合化合物融化後，往不鏽鋼燒杯中加入磁力轉子，將混合物攪拌均勻，冷卻到室溫後即得液晶組合物。 In the embodiment of the present invention, the equipment and instruments used for the preparation of the liquid crystal composition are as follows: the preparation method of the liquid crystal composition is as follows: put each polymerizable compound into a stainless steel beaker after weighing according to a certain proportion, and put each polymerizable compound into a stainless steel beaker. The stainless steel beaker of the compound is heated and melted on a magnetic stirring apparatus, and after the polymerizable compound in the stainless steel beaker is melted, a magnetic rotor is added to the stainless steel beaker, the mixture is stirred evenly, and the liquid crystal composition is obtained after cooling to room temperature.

本發明的實施例中的液晶顯示元件的製備方法如下：首先，在第一基板和第二基板的表面均勻塗布配向材料，配向材料可以選用聚醯亞胺，對均勻塗布的配向材料進行加熱固化，加熱溫度為230℃，形成配向層；其次，在第二基板表面散佈間隔物，並沿第一基板的邊緣塗布邊框膠，並在120℃下進行固化；然後，將第一基板和第二基板相對設置，貼合形成具有夾層空間的結構；最後，將液晶組合物注入第一基板和第二基板之間的夾層空間，密封固化，藉以將液晶組合物密封在第一基板和第二基板之間，並同時進行加電、紫外光照射。紫外光照射分為兩個階段，包括第一階段紫外光照射(UV1)、第二階段紫外光照射(UV2)。在UV1階段，以紫外光波長為365nm，輻照度為64mw/cm²進行光照射，在第一階段的光照射結束後進行第二階段光照射(UV2)，UV2中使用波長365nm的紫外光，輻照度為5mw/cm²，光照射時間為100-150min。 The preparation method of the liquid crystal display element in the embodiment of the present invention is as follows: First, uniformly coat the alignment material on the surface of the first substrate and the second substrate, the alignment material can be polyimide, and heat and cure the evenly coated alignment material , the heating temperature is 230°C to form an alignment layer; secondly, spacers are spread on the surface of the second substrate, and frame glue is coated along the edge of the first substrate, and cured at 120°C; then, the first substrate and the second The substrates are arranged oppositely and bonded to form a structure with interlayer space; finally, the liquid crystal composition is injected into the interlayer space between the first substrate and the second substrate, sealed and cured, so that the liquid crystal composition is sealed on the first substrate and the second substrate Between, and at the same time, power-on, ultraviolet light irradiation. The ultraviolet light irradiation is divided into two stages, including the first stage ultraviolet light irradiation (UV1) and the second stage ultraviolet light irradiation (UV2). In the UV1 stage, the ultraviolet light is irradiated with a wavelength of 365nm and an irradiance of 64mw/ ^cm2 . After the first stage of light irradiation is completed, the second stage of light irradiation (UV2) is carried out. In UV2, ultraviolet light with a wavelength of 365nm is used. The irradiance is 5mw/cm ² , and the light irradiation time is 100-150min.

RM的轉化率的計算公式為：

。 The formula for calculating the conversion rate of RM is:

.

本發明實施例中使用的液晶單體結構用代碼表示，液晶環結構、端基、連接基團的代碼表示方法見下表1、表2。 The structures of the liquid crystal monomers used in the embodiments of the present invention are represented by codes, and the code representation methods of liquid crystal ring structures, terminal groups, and linking groups are shown in Table 1 and Table 2 below.

舉例：

，其代碼為CC-Cp-V1；

，其代碼為PGP-Cpr1-2；

，其代碼為CPY-2-O2；

，其代碼為CCY-3-O2；

，其代碼為COY-3-O2；

，其代碼為CCOY-3-O2；

，其代碼為Sb-CpO-O4；

，其代碼為Sc-CpO-O4；

，其代碼為COYL-Cprl-O2；

，其代碼為COYL-1-OV1。 Example:

, whose code is CC-Cp-V1;

, whose code is PGP-Cpr1-2;

, whose code is CPY-2-O2;

, whose code is CCY-3-O2;

, whose code is COY-3-O2;

, whose code is CCOY-3-O2;

, whose code is Sb-CpO-O4;

, whose code is Sc-CpO-O4;

, whose code is COYL-Cprl-O2;

, whose code is COYL-1-OV1.

以下採用以下具體實施例來對本發明進行說明： Below adopt following specific embodiment to illustrate the present invention:

[液晶化合物] [Liquid crystal compound]

本發明的式I所示化合物可根據下述方案進行合成：

Compound shown in formula I of the present invention can be synthesized according to following scheme:

其中，L₁、L₂、L₃、L₄、r₁、r₃、r₂、r₄、x₁、x₂、x₃、x₄、Sp₁、Sp₂、Sp₃、Sp₄、Sp₅、Z₁、Z₂、P₁、P₂、P₃、P₄各自獨立地和上述式I所示化合物中的定義相同。 Among them, L ₁ , L ₂ , L ₃ , L ₄ , r ₁ , r ₃ , r ₂ , r ₄ , x ₁ , x ₂ , x ₃ , x ₄ , Sp 1 , Sp ₂ , Sp ₃ , _{Sp 4 ,} Sp ₅ , Z ₁ , Z ₂ , P ₁ , P ₂ , P ₃ , and P ₄ are each independently as defined in the compound represented by formula I above.

S₁、S₂各自獨立地表示醛基、羥基、羧基。 S ₁ and S ₂ each independently represent an aldehyde group, a hydroxyl group, or a carboxyl group.

B₁、B₂、B₃、B₄各自獨立地表示羥基的保護基。 B ₁ , B ₂ , B ₃ , and B ₄ each independently represent a protecting group for a hydroxyl group.

合成通式中原材料及試劑均可通過常規合成或商業途徑購買而得，此類方法原理、操作過程、常規後處理、過矽膠柱、重結晶提純等手段是本領域合成人員所熟知的，完全可以實現合成過程，得到目標產物。 The raw materials and reagents in the general synthesis formula can be purchased through conventional synthesis or commercial channels. Means such as such method principle, operation process, conventional post-treatment, silica gel column, recrystallization and purification are well known to those skilled in the art. The synthesis process can be realized to obtain the target product.

上述所有方法的所有步驟的反應均在溶劑中進行；所述溶劑均選自四氫呋喃、N,N-二甲基甲醯胺、乙醇、甲醇、二氯甲烷、丙酮、甲苯和去離子水中的至少一種。 The reactions of all the steps of the above-mentioned methods are carried out in a solvent; the solvent is selected from tetrahydrofuran, N,N-dimethylformamide, ethanol, methanol, methylene chloride, acetone, toluene and deionized water at least A sort of.

合成通式中原材料及試劑均可通過常規合成或商業途徑購買而得，此類方法原理、操作過程、常規後處理、過矽膠柱、重結晶提純等手段是本領域合成人員所熟知的，完全可以實現合成過程，得到目標產物。 The raw materials and reagents in the general synthesis formula can be purchased through conventional synthesis or commercial channels. Means such as such method principle, operation process, conventional post-treatment, silica gel column, recrystallization and purification are well known to those skilled in the art. The synthesis process can be realized to obtain the target product.

上述所有方法的所有步驟的反應均在溶劑中進行；所述溶劑均選 自四氫呋喃、N,N-二甲基甲醯胺、乙醇、甲醇、二氯甲烷、丙酮、甲苯和去離子水中的至少一種。 The reaction of all steps of above-mentioned all methods is all carried out in solvent; Described solvent is all selected At least one selected from tetrahydrofuran, N,N-dimethylformamide, ethanol, methanol, methylene chloride, acetone, toluene and deionized water.

實施例1 Example 1

化合物結構式如下式I-1-1所示：

The compound structural formula is shown in the following formula I-1-1:

其製備路線如下：

Its preparation route is as follows:

製備的具體操作流程： The specific operation process of preparation:

在5L三口瓶中投入0.3mol的對苄氧基苯硼酸、0.3mol的2-苄氧基-5-溴-3-氟苯酚，2.0L甲苯，0.7L水，0.36mol碳酸鉀，催化劑0.3g，加熱回流反應3小 時。靜置分液，柱層析分離，甲苯/乙醇重結晶，得到化合物1-1黃色固體。HPLC：93%，收率Y=76%。 Put 0.3mol of p-benzyloxyphenylboronic acid, 0.3mol of 2-benzyloxy-5-bromo-3-fluorophenol, 2.0L of toluene, 0.7L of water, 0.36mol of potassium carbonate, and 0.3g of catalyst in a 5L three-necked flask , heated to reflux for 3 hours hour. The liquid was separated by standing, separated by column chromatography, and recrystallized from toluene/ethanol to obtain compound 1-1 as a yellow solid. HPLC: 93%, yield Y=76%.

用2-溴-5-苄氧基苯酚替代2-苄氧基-5-溴-3-氟苯酚，按照化合物1-1的合成步驟合成化合物A。 Using 2-bromo-5-benzyloxyphenol instead of 2-benzyloxy-5-bromo-3-fluorophenol, compound A was synthesized according to the synthetic steps of compound 1-1.

在2L三口瓶中投0.22mol的化合物1-1、0.22mol的溴丙醇、0.25mol的無水碳酸鉀，1.2L DMF，N₂保護下控溫120℃反應4小時。反應完畢，降溫，邊攪拌邊倒入冰水中，攪拌30min，過濾，0.5L石油醚打漿，可得到化合物1-2，HPLC：95%，收率Y=74%。 Into a 2L three-neck flask, 0.22mol of compound 1-1, 0.22mol of bromopropanol, 0.25mol of anhydrous potassium carbonate, 1.2L of DMF, and reacted at 120°C for 4 hours under the protection of _N2 . After the reaction is completed, cool down, pour into ice water while stirring, stir for 30 minutes, filter, and beat with 0.5L petroleum ether to obtain compound 1-2, HPLC: 95%, yield Y=74%.

在2L三口瓶中投0.1mol的化合物1-2、0.1mol的化合物A、0.15mol的三苯基膦，1.0L THF，N₂保護下控溫0℃，滴加0.15mol的DEAD，滴加完畢室溫反應4小時。反應完畢，邊攪拌邊倒入冰水中，攪拌30min，過濾，0.5L石油醚打漿，可得到化合物1-3，HPLC：97%，收率Y=70%。 Put 0.1mol of compound 1-2, 0.1mol of compound A, 0.15mol of triphenylphosphine, 1.0L of THF in a 2L three-necked flask, and control the temperature at 0°C under the protection of _N2 , drop 0.15mol of DEAD, dropwise Complete the reaction at room temperature for 4 hours. After the reaction is completed, pour into ice water while stirring, stir for 30 minutes, filter, and beat with 0.5L petroleum ether to obtain compound 1-3, HPLC: 97%, yield Y=70%.

將0.08mol化合物1-3、6.6g的Pd/C、0.5L的THF和0.5L的EtOH加入1L三口瓶中，N₂置換三次，H2置換三次，40℃加氫脫苄，反應6小時。反應完畢，矽藻土過濾，濾液濃縮，PE：EA=10：1打漿，攪拌10min，得到化合物1-4，HPLC：97%，收率Y=72%。 Add 0.08 mol of compound 1-3, 6.6 g of Pd/C, 0.5 L of THF and 0.5 L of EtOH into a 1 L three-neck flask, replace with N ₂ three times, H 2 three times, hydrogenate debenzylation at 40°C, and react for 6 hours. After the reaction was completed, filter with diatomaceous earth, concentrate the filtrate, beat PE:EA=10:1, and stir for 10 minutes to obtain compound 1-4, HPLC: 97%, yield Y=72%.

在1L三口瓶中投0.02mol的化合物1-4、0.1mol的三乙胺、0.5L的DCM，N₂保護下控溫0℃滴加0.1mol甲基丙烯醯氯。滴畢，室溫反應3小時。反應完畢，加水分液，水相用DCM萃取，合併有機相，飽和食鹽水洗一次，無水硫酸鈉乾燥，過濾，濾液濃縮，5倍甲苯45℃溶解，過50g矽膠柱，3倍甲苯沖柱，濃縮，3倍甲苯3倍乙醇加熱溶解，-20℃冰箱冷凍4h，吸慮，按照相同的方法再重結晶三次，晾乾，得白色固體化合物I-1-1，HPLC：99.5%，收率Y=40%。 Put 0.02mol of compound 1-4, 0.1mol of triethylamine, and 0.5L of DCM into a 1L three-neck flask, and add 0.1mol of methacryloyl chloride dropwise at 0°C under the protection of _N2 . After dropping, react at room temperature for 3 hours. After the reaction is complete, add water, extract the aqueous phase with DCM, combine the organic phases, wash once with saturated brine, dry over anhydrous sodium sulfate, filter, concentrate the filtrate, dissolve 5 times of toluene at 45°C, pass through a 50 g silica gel column, and wash the column with 3 times of toluene. Concentrate, heat to dissolve with 3 times of toluene and 3 times of ethanol, freeze at -20°C for 4 hours, inhale, recrystallize three times according to the same method, and dry to obtain white solid compound I-1-1, HPLC: 99.5%, yield Y=40%.

實施例2 Example 2

化合物結構式如下式I-2-1所示：

The compound structural formula is shown in the following formula I-2-1:

其製備路線如下：

Its preparation route is as follows:

製備的具體操作流程： The specific operation process of preparation:

用2-氟-4-苄氧基苯硼酸代替對苄氧基苯硼酸，2苄氧基-5-溴苯酚代替2-苄氧基-5-溴-3-氟苯酚，按照實施例1合成化合物1-1的步驟合成化合物2-1. Use 2-fluoro-4-benzyloxyphenylboronic acid instead of p-benzyloxyphenylboronic acid, 2-benzyloxy-5-bromophenol instead of 2-benzyloxy-5-bromo-3-fluorophenol, and synthesize according to Example 1 The steps of compound 1-1 synthesize compound 2-1.

再用2-氟-4-苄氧基苯硼酸代替對苄氧基苯硼酸，2-溴-5-苄氧基苯酚替代2苄氧基-5-溴苯酚，按照實施例1合成化合物1-1的步驟合成化合物B。 Then use 2-fluoro-4-benzyloxyphenylboronic acid to replace p-benzyloxyphenylboronic acid, 2-bromo-5-benzyloxyphenol to replace 2-benzyloxy-5-bromophenol, and synthesize compound 1- 1 to synthesize compound B.

在2L三口瓶中投0.25mol的化合物2-1、0.25mol的溴己醇、0.30mol的無水碳酸鉀，1.2L DMF，N₂保護下控溫120℃反應4小時。反應完畢，降溫，邊攪拌邊倒入冰水中，攪拌30min，過濾，0.5L石油醚打漿，可得到化合物2-2，HPLC：95%，收率Y=74%。 In a 2L three-neck flask, 0.25mol of compound 2-1, 0.25mol of bromohexanol, 0.30mol of anhydrous potassium carbonate, 1.2L of DMF, and reacted at 120°C for 4 hours under the protection of _N2 . After the reaction is completed, cool down, pour into ice water while stirring, stir for 30 minutes, filter, and beat with 0.5L petroleum ether to obtain compound 2-2, HPLC: 95%, yield Y=74%.

在2L三口瓶中投0.1mol的化合物2-2、0.1mol的化合物B、0.15mol的三苯基膦，1.0L THF，N₂保護下控溫0℃，滴加0.15mol的DEAD，滴加完畢室溫反應4小時。反應完畢，邊攪拌邊倒入冰水中，攪拌30min，過濾，0.5L石油醚打漿，可得到化合物2-3，HPLC：97%，收率Y=70%。 Put 0.1mol of compound 2-2, 0.1mol of compound B, 0.15mol of triphenylphosphine in a 2L three-necked flask, 1.0L of THF, and control the temperature at 0°C under the protection of _N2 , dropwise add 0.15mol of DEAD, dropwise Complete the reaction at room temperature for 4 hours. After the reaction is completed, pour into ice water while stirring, stir for 30 minutes, filter, and beat with 0.5L petroleum ether to obtain compound 2-3, HPLC: 97%, yield Y=70%.

將0.08mol化合物2-3、6.6g的Pd/C、0.5L的THF和0.5L的EtOH加入1L三口瓶中，N₂置換三次，H₂置換三次，40℃加氫脫苄，反應6小時。反應完畢，矽藻土過濾，濾液濃縮，PE：EA=10：1打漿，攪拌10min，得到化合物2-4，HPLC：97%，收率Y=75%。 Add 0.08mol of compound 2-3, 6.6g of Pd/C, 0.5L of THF and 0.5L of EtOH into a 1L three-neck flask, replace with N ₂ three times, H ₂ three times, hydrodebenzylation at 40°C, and react for 6 hours . After the reaction was completed, filter with diatomaceous earth, concentrate the filtrate, beat PE:EA=10:1, and stir for 10 minutes to obtain compound 2-4, HPLC: 97%, yield Y=75%.

在1L三口瓶中投0.02mol的化合物2-4、0.1mol的三乙胺、0.5L的DCM，N₂保護下控溫0℃滴加0.1mol甲基丙烯醯氯。滴畢，室溫反應3小時。反應完畢，加水分液，水相用DCM萃取，合併有機相，飽和食鹽水洗一次，無水硫酸鈉乾燥，過濾，濾液濃縮，5倍甲苯45℃溶解，過50g矽膠柱，3倍甲苯沖柱，濃縮，3倍甲苯3倍乙醇加熱溶解，-20℃冰箱冷凍4h，吸慮，按照相同的方法再重結晶三次，晾乾，得白色固體化合物I-2-1，HPLC：99.0%，收率Y=42%。化合物I-2-1的¹H-NMR譜圖如圖1所示。 Put 0.02mol of compound 2-4, 0.1mol of triethylamine, and 0.5L of DCM into a 1L three-neck flask, and add 0.1mol of methacryloyl chloride dropwise at 0°C under the protection of _N2 . After dropping, react at room temperature for 3 hours. After the reaction is complete, add water, extract the aqueous phase with DCM, combine the organic phases, wash once with saturated brine, dry over anhydrous sodium sulfate, filter, concentrate the filtrate, dissolve 5 times of toluene at 45°C, pass through a 50 g silica gel column, and wash the column with 3 times of toluene. Concentrate, heat to dissolve with 3 times of toluene and 3 times of ethanol, refrigerate at -20°C for 4 hours, inhale, recrystallize three times according to the same method, and dry to obtain white solid compound I-2-1, HPLC: 99.0%, yield Y=42%. The ¹ H-NMR spectrum of compound I-2-1 is shown in Fig. 1 .

實施例3 Example 3

化合物結構式如下式I-6-2所示：

The compound structural formula is shown in the following formula I-6-2:

其製備路線如下：

Its preparation route is as follows:

製備的具體操作流程： The specific operation process of preparation:

在2L三口瓶中投入0.5mol的4-苄氧基苯硼酸、0.5mol的5-苄氧基-2-溴苯甲醛，2.0L甲苯，0.7L水，0.36mol碳酸鉀，催化劑0.3g，加熱回流反應3小時。靜置分液，柱層析分離，甲苯/乙醇重結晶，得到化合物3-1黃色固體。HPLC：97%，收率Y=73%。 Put 0.5mol of 4-benzyloxyphenylboronic acid, 0.5mol of 5-benzyloxy-2-bromobenzaldehyde, 2.0L of toluene, 0.7L of water, 0.36mol of potassium carbonate, 0.3g of catalyst in a 2L three-necked flask, and heat The reaction was refluxed for 3 hours. After static separation, separation by column chromatography, and recrystallization from toluene/ethanol, compound 3-1 was obtained as a yellow solid. HPLC: 97%, yield Y=73%.

用2-苄氧基-5-溴苯酚替代5-苄氧基-2-溴苯甲醛，按照合成化合物 3-1的步驟與4-苄氧基苯硼酸反應，合成化合物C。 Substituting 2-benzyloxy-5-bromophenol for 5-benzyloxy-2-bromobenzaldehyde, the compound was synthesized according to Step 3-1 reacts with 4-benzyloxyphenylboronic acid to synthesize compound C.

在2L三口瓶中投0.1mol的5-溴戊醇三苯基膦鹽，加降溫至0到-10℃之間，分批緩慢加入0.2mol的叔丁醇鉀，控溫0到-10℃之間反應1h，將0.1mol的化合物3-1溶於THF滴加到上述體系，N₂保護下控溫-10℃反應2小時。反應完畢，降溫，邊攪拌邊倒入冰水中，攪拌30min，過濾0.5L石油醚打漿，可得到化合物3-2，LC：94%，收率Y=84%。 Put 0.1mol of 5-bromopentyl triphenylphosphine salt into a 2L three-necked flask, add and cool down to between 0 and -10°C, slowly add 0.2mol of potassium tert-butoxide in batches, and control the temperature from 0 to -10°C After reacting for 1 h, 0.1 mol of compound 3-1 dissolved in THF was added dropwise to the above system, and reacted at -10°C for 2 hours under the protection of N ₂ . After the reaction is completed, cool down, pour into ice water while stirring, stir for 30 minutes, filter 0.5L of petroleum ether and beat to obtain compound 3-2, LC: 94%, yield Y=84%.

在2L三口瓶中加入0.1mol的化合物3-2再加入0.1mol化合物C，氮氣保護，降溫至0℃，再加入0.15mol三苯基膦和0.15mol的DEAD，加料完畢室溫反應4小時，反應完畢，降溫，邊攪拌邊倒入冰水中，攪拌30min，乙酸乙酯萃取，旋幹，2倍乙醇和1倍石油醚重結晶，可得到化合物3-3，LC：94%，收率Y=70%。 Add 0.1 mol of compound 3-2 and then 0.1 mol of compound C into a 2L three-necked flask, protect with nitrogen, cool down to 0°C, then add 0.15 mol of triphenylphosphine and 0.15 mol of DEAD, and react at room temperature for 4 hours after the addition. After the reaction is completed, cool down, pour into ice water while stirring, stir for 30 minutes, extract with ethyl acetate, spin dry, recrystallize with 2 times ethanol and 1 times petroleum ether, and obtain compound 3-3, LC: 94%, yield Y =70%.

將0.05mol化合物3-3、3g的Pd/C、0.5L的THF和0.5L的EtOH加入1L三口瓶中，N₂置換三次，H₂置換三次，40℃加氫脫苄，反應6小時。反應完畢，矽藻土過濾，濾液濃縮，PE：EA=10：1打漿，攪拌10min，得到化合物3-4，LC：95%，收率Y=73%。 Add 0.05 mol of compound 3-3, 3 g of Pd/C, 0.5 L of THF and 0.5 L of EtOH into a 1 L three-neck flask, replace with N ₂ three times, H ₂ three times, hydrodebenzyle at 40°C, and react for 6 hours. After the reaction was completed, filter with diatomaceous earth, concentrate the filtrate, beat PE:EA=10:1, and stir for 10 minutes to obtain compound 3-4, LC: 95%, yield Y=73%.

在1L三口瓶中投0.02mol的3-4、0.1mol的三乙胺、0.5L的DCM，N₂保護下控溫0℃滴加0.1mol甲基丙烯醯氯。滴畢，室溫反應3小時。反應完畢，加水分液，水相用DCM萃取，合併有機相，飽和食鹽水洗一次，無水硫酸鈉乾燥，過濾，濾液濃縮，5倍甲苯45℃溶解，過50g矽膠柱，3倍甲苯沖柱，濃縮，3倍甲苯3倍醇加熱溶解，-20℃冰箱冷凍4h，吸慮，按照相同的方法再重結晶三次次，晾乾，得白色固體化合物I-6-2，HPLC：99.8%，收率Y=40%。 Put 0.02mol of 3-4, 0.1mol of triethylamine, and 0.5L of DCM into a 1L three-neck flask, and add 0.1mol of methacryloyl chloride dropwise at 0°C under the protection of _N2 . After dropping, react at room temperature for 3 hours. After the reaction is complete, add water, extract the aqueous phase with DCM, combine the organic phases, wash once with saturated brine, dry over anhydrous sodium sulfate, filter, concentrate the filtrate, dissolve 5 times of toluene at 45°C, pass through a 50 g silica gel column, and wash the column with 3 times of toluene. Concentrate, heat to dissolve 3 times toluene and 3 times alcohol, freeze at -20°C for 4 hours, inhale, recrystallize three times according to the same method, and dry to obtain white solid compound I-6-2, HPLC: 99.8%, yield Rate Y=40%.

實施例4 Example 4

化合物結構式如下式I-7-1所示：

The compound structural formula is shown in the following formula I-7-1:

其製備路線如下：

Its preparation route is as follows:

製備的具體操作流程： The specific operation process of preparation:

在2L三口瓶中投入0.3mol的3-氟-4-苄氧基苯硼酸、0.3mol的2-苄氧基-5-溴-2-苯甲酸，2.0L甲苯，0.7L水，0.6mol碳酸鉀，催化劑0.3g，加熱回流反應3 小時。靜置分液，柱層析分離，甲苯/乙醇重結晶，得到化合物4-1黃色固體。HPLC：97%，收率Y=80%。 Put 0.3mol of 3-fluoro-4-benzyloxyphenylboronic acid, 0.3mol of 2-benzyloxy-5-bromo-2-benzoic acid, 2.0L of toluene, 0.7L of water, and 0.6mol of carbonic acid into a 2L three-necked flask Potassium, catalyst 0.3g, heated to reflux reaction 3 Hour. The liquid was separated by standing, separated by column chromatography, and recrystallized from toluene/ethanol to obtain compound 4-1 as a yellow solid. HPLC: 97%, yield Y=80%.

用2-溴-5-苄氧基苯甲酸替代2-苄氧基-5-溴苯甲酸，按照合成化合物4-1的步驟與3-氟-4-苄氧基苯硼酸反應，合成化合物D。 Replace 2-benzyloxy-5-bromobenzoic acid with 2-bromo-5-benzyloxybenzoic acid, and react with 3-fluoro-4-benzyloxyphenylboronic acid according to the steps of compound 4-1 to synthesize compound D .

在2L三口瓶中投0.20mol的化合物4-1、0.20mol的溴丙醇、0.30mol的無水碳酸鉀，1.2L DMF，N₂保護下控溫120℃反應4小時。反應完畢，降溫，邊攪拌邊倒入冰水中，攪拌30min，過濾，0.5L石油醚打漿，可得到化合物4-2，HPLC：94%，收率Y=75%。 In a 2L three-neck flask, 0.20mol of compound 4-1, 0.20mol of bromopropanol, 0.30mol of anhydrous potassium carbonate, 1.2L of DMF, and reacted at 120°C for 4 hours under the protection of _N2 . After the reaction is completed, cool down, pour into ice water while stirring, stir for 30 minutes, filter, and beat with 0.5L petroleum ether to obtain compound 4-2, HPLC: 94%, yield Y=75%.

在3L三口瓶中投0.2mol的化合物4-2、0.2mol的化合物D、0.05mol的DMAP，1.0L THF，N₂保護下控溫0℃滴加0.3molDCC的THF溶液。滴畢，室溫反應6小時。反應完畢，過濾，濾液濃縮，3倍乙醇重結晶，得到化合物4-3，GC：93%，收率Y=75%。 In a 3L three-necked flask, 0.2mol of compound 4-2, 0.2mol of compound D, 0.05mol of DMAP, 1.0L of THF, and 0.3mol of THF solution of DCC were added dropwise at 0°C under the protection of _N2 . After dropping, react at room temperature for 6 hours. After completion of the reaction, filter, concentrate the filtrate, and recrystallize from 3 times ethanol to obtain compound 4-3, GC: 93%, yield Y=75%.

將0.06mol化合物5-3、5.2g的Pd/C、0.3L的THF和0.2L的EtOH加入1L三口瓶中，N₂置換三次，H2置換三次，40℃加氫脫苄，反應6小時。反應完畢，矽藻土過濾，濾液濃縮，PE：EA=10：1打漿，攪拌10min，得到化合物4-4，HPLC：95%，收率Y=81%。 Add 0.06 mol of compound 5-3, 5.2 g of Pd/C, 0.3 L of THF and 0.2 L of EtOH into a 1 L three-neck flask, replace with N ₂ three times, H 2 three times, hydrodebenzyle at 40°C, and react for 6 hours. After the reaction was completed, filter with diatomaceous earth, concentrate the filtrate, beat PE:EA=10:1, and stir for 10 minutes to obtain compound 4-4, HPLC: 95%, yield Y=81%.

在500ml三口瓶中投0.02mol的化合物4-4、0.1mol的三乙胺、0.2L的DCM，N₂保護下控溫0℃滴加0.1mol甲基丙烯醯氯。滴畢，室溫反應3小時。反應完畢，加水分液，水相用DCM萃取，合併有機相，飽和食鹽水洗一次，無水硫酸鈉乾燥，過濾，濾液濃縮，5倍甲苯45℃溶解，過50g矽膠柱，3倍甲苯沖柱，濃縮，3倍甲苯3倍醇加熱溶解，-20℃冰箱冷凍4h，吸慮，按照相同的方法再重結晶四次，晾乾，得白色固體化合物I-7-1，HPLC：99%，收率Y=35%。 Put 0.02mol of compound 4-4, 0.1mol of triethylamine, and 0.2L of DCM into a 500ml three-necked flask, and add 0.1mol of methacryloyl chloride dropwise at 0°C under the protection of _N2 . After dropping, react at room temperature for 3 hours. After the reaction is complete, add water, extract the aqueous phase with DCM, combine the organic phases, wash once with saturated brine, dry over anhydrous sodium sulfate, filter, concentrate the filtrate, dissolve 5 times of toluene at 45°C, pass through a 50 g silica gel column, and wash the column with 3 times of toluene. Concentrate, heat to dissolve 3 times toluene and 3 times alcohol, freeze at -20°C for 4 hours, inhale, recrystallize four times according to the same method, and dry to obtain white solid compound I-7-1, HPLC: 99%, yield Rate Y=35%.

實施例5 Example 5

化合物結構式如下式I-8-3所示：

The compound structural formula is shown in the following formula I-8-3:

其製備路線如下：

Its preparation route is as follows:

製備的具體操作流程： The specific operation process of preparation:

用3-甲氧基-4-苄氧基苯硼酸替代3-氟-4-苄氧基苯硼酸，參考合成實施例5中化合物5-1的步驟與2-苄氧基-5-溴-2-苯甲酸反應，合成化合物5-1。 Replace 3-fluoro-4-benzyloxyphenylboronic acid with 3-methoxy-4-benzyloxyphenylboronic acid, refer to the steps of compound 5-1 in Synthesis Example 5 and 2-benzyloxy-5-bromo- 2-Benzoic acid reaction to synthesize compound 5-1.

用6-溴己醇替代3-溴丙醇，參考實施例5中合成4-2的步驟與化合物5-1反應合成5-2。 6-bromohexanol was used instead of 3-bromopropanol, and the step of synthesizing 4-2 in Example 5 was reacted with compound 5-1 to synthesize 5-2.

用2-溴-5-苄氧基苯甲酸替代2-苄氧基-5-溴苯甲酸，按照合成化合物5-1的步驟與3-甲氧基-4-苄氧基苯硼酸反應，合成化合物E。 Replace 2-benzyloxy-5-bromobenzoic acid with 2-bromo-5-benzyloxybenzoic acid, react with 3-methoxy-4-benzyloxyphenylboronic acid according to the steps of synthetic compound 5-1, and synthesize Compound E.

在3L三口瓶中投0.2mol的化合物5-2、0.2mol的化合物E、0.05mol的DMAP，1.0L THF，N₂保護下控溫0℃滴加0.3molDCC的THF溶液。滴畢，室溫反應6小時。反應完畢，過濾，濾液濃縮，3倍乙醇重結晶，得到化合物5-3，GC：93%，收率Y=75%。 In a 3L three-necked flask, 0.2mol of compound 5-2, 0.2mol of compound E, 0.05mol of DMAP, 1.0L of THF, and 0.3mol of DCC in THF were added dropwise at 0°C under the protection of _N2 . After dropping, react at room temperature for 6 hours. After completion of the reaction, filter, concentrate the filtrate, and recrystallize from 3 times ethanol to obtain compound 5-3, GC: 93%, yield Y=75%.

將0.06mol化合物5-3、5.2g的Pd/C、0.3L的THF和0.2L的EtOH加入1L三口瓶中，N₂置換三次，H₂置換三次，40℃加氫脫苄，反應6小時。反應完畢，矽藻土過濾，濾液濃縮，PE：EA=10：1打漿，攪拌10min，得到化合物5-4，HPLC：95%，收率Y=81%。 Add 0.06mol of compound 5-3, 5.2g of Pd/C, 0.3L of THF and 0.2L of EtOH into a 1L three-necked flask, replace with N ₂ three times, H ₂ three times, hydrogenate debenzylation at 40°C, and react for 6 hours . After the reaction was completed, filter with diatomaceous earth, concentrate the filtrate, beat PE:EA=10:1, and stir for 10 minutes to obtain compound 5-4, HPLC: 95%, yield Y=81%.

在500ml三口瓶中投0.02mol的化合物5-4、0.1mol的三乙胺、0.2L的DCM，N₂保護下控溫0℃滴加0.1mol甲基丙烯醯氯。滴畢，室溫反應3小時。反應完畢，加水分液，水相用DCM萃取，合併有機相，飽和食鹽水洗一次，無水硫酸鈉乾燥，過濾，濾液濃縮，5倍甲苯45℃溶解，過50g矽膠柱，3倍甲苯沖柱，濃縮，3倍甲苯3倍醇加熱溶解，-20℃冰箱冷凍4h，吸慮，按照相同的方法再重結晶四次，晾乾，得白色固體化合物I-8-1，HPLC：99.8%，收率Y=43%。 Put 0.02mol of compound 5-4, 0.1mol of triethylamine, and 0.2L of DCM into a 500ml three-neck flask, and add 0.1mol of methacryloyl chloride dropwise at 0°C under the protection of _N2 . After dropping, react at room temperature for 3 hours. After the reaction is complete, add water, extract the aqueous phase with DCM, combine the organic phases, wash once with saturated brine, dry over anhydrous sodium sulfate, filter, concentrate the filtrate, dissolve 5 times of toluene at 45°C, pass through a 50 g silica gel column, and wash the column with 3 times of toluene. Concentrate, heat to dissolve with 3 times of toluene and 3 times of alcohol, freeze at -20°C for 4 hours, inhale, recrystallize four times according to the same method, and dry to obtain white solid compound I-8-1, HPLC: 99.8%, yield Rate Y=43%.

製備液晶組合物： Preparation of liquid crystal composition:

母體液晶組合物1 Matrix liquid crystal composition 1

母體液晶組合物1的配方及相應的性能如下表3所示。 The formulation and corresponding properties of the matrix liquid crystal composition 1 are shown in Table 3 below.

表3：母體液晶組合物1的配方及相應的性能

Table 3: Formula and corresponding properties of matrix liquid crystal composition 1

母體液晶組合物2 Matrix liquid crystal composition 2

母體液晶組合物2的配方及相應的性能如下表4所示。 The formulation and corresponding properties of the matrix liquid crystal composition 2 are shown in Table 4 below.

母體液晶組合物3 Matrix liquid crystal composition 3

液晶組合物的配方及相應的性能如下表5所示。 The formula and corresponding properties of the liquid crystal composition are shown in Table 5 below.

母體液晶組合物4 Matrix liquid crystal composition 4

液晶組合物的配方及相應的性能如下表6所示。 The formula and corresponding properties of the liquid crystal composition are shown in Table 6 below.

對比化合物：

Comparative compound:

向測試母體液晶組合物中分別添加一定量的式I所示可聚合化合物；做為對比，分別向測試母體1添加一定量的RM-1、RM-2、RM-3做為對比例1、對比例2、對比例3，以上述提到的液晶組合物製備方法製備成液晶組合物。 Add a certain amount of polymerizable compounds shown in formula I respectively to the test matrix liquid crystal composition; as a comparison, add a certain amount of RM-1, RM-2, RM-3 to the test matrix 1 respectively as comparative examples 1, In Comparative Example 2 and Comparative Example 3, liquid crystal compositions were prepared by the above-mentioned method for preparing liquid crystal compositions.

液晶組合物的信賴性通過紫外、高溫老化試驗並進行VHR測試來進行，液晶面板紫外、高溫試驗前後的VHR資料變化越小，抗紫外、抗高溫能力越強。因此，通過比較各個實施例、對比例在試驗前後的VHR資料的差來 判斷抗紫外、抗高溫能力。 The reliability of the liquid crystal composition is carried out through ultraviolet and high temperature aging tests and VHR tests. The smaller the VHR data changes before and after the ultraviolet and high temperature tests of the liquid crystal panel, the stronger the anti-ultraviolet and high-temperature resistance. Therefore, by comparing each embodiment, the difference of the VHR data of comparative example before and after test Judging the ability of anti-ultraviolet and high temperature resistance.

紫外老化試驗：將液晶組合物放置在波長為365nm的紫外燈下照射5000mJ能量。 Ultraviolet aging test: the liquid crystal composition is placed under an ultraviolet lamp with a wavelength of 365nm and irradiated with 5000mJ energy.

高溫老化試驗：將液晶組合物放置在100℃烘箱內一小時。 High temperature aging test: the liquid crystal composition is placed in an oven at 100° C. for one hour.

在老化試驗後VHR資料相對於初始VHR資料變化越小，說明該液晶組合物抗紫外、抗高溫的能力越強，藉以可以判斷該液晶組合物在工作過程中抵抗外界環境破壞的能力越強，因此，該液晶組合物的信賴性就越高。液晶組合物實施例與對比例的VHR資料見表7。 The smaller the change of the VHR data after the aging test relative to the initial VHR data, the stronger the anti-ultraviolet and high-temperature resistance of the liquid crystal composition, so that it can be judged that the stronger the ability of the liquid crystal composition to resist external environmental damage during the working process, Therefore, the reliability of the liquid crystal composition becomes higher. See Table 7 for the VHR data of the liquid crystal composition examples and comparative examples.

將聚合性化合物添加於組合物中，所述聚合性化合物因聚合而被消耗來形成聚合物(UV1階段)。這一反應的轉化率較佳為大轉化率。這是因為：就圖像的殘像觀點而言，聚合物化合物的殘量(未反應的聚合性化合物的量)較佳為少(UV2階段)。從表8可以看出，相對於對比例1-3，本發明的聚合性化合物能夠提供較高轉化率和較低的殘留量。 A polymerizable compound is added to the composition, which is consumed by polymerization to form a polymer (UV1 stage). The conversion of this reaction is preferably a large conversion. This is because the remaining amount of the polymer compound (the amount of the unreacted polymerizable compound) is preferably small (UV2 stage) from the viewpoint of afterimage of the image. It can be seen from Table 8 that, compared with Comparative Examples 1-3, the polymerizable compound of the present invention can provide higher conversion rate and lower residual amount.

顯然，本專利公開的上述實施例僅僅是為清楚地說明本專利所作的舉例，而並非是對本專利的實施方式的限定，對於所屬領域的普通具有通常知識者來說，在上述說明的基礎上還可以做出其它不同形式的變化或變動，這裡無法對所有的實施方式予以窮舉，凡是屬於本公開的技術方案所引伸出的顯而易見的變化或變動仍處於本專利的保護範圍之列。 Obviously, the above-mentioned embodiments disclosed in this patent are only examples for clearly illustrating this patent, rather than limiting the implementation of this patent. Other changes or changes in different forms can also be made, and all implementation modes cannot be exhausted here, and all obvious changes or changes derived from the technical solutions of the present disclosure are still within the scope of protection of this patent.

Claims (6)

一種液晶組合物，包含一種或多種式I-1-1、I-2-1及式I-6-2所示可聚合化合物所組成的群組，

A liquid crystal composition, comprising a group consisting of one or more polymerizable compounds represented by formula I-1-1, I-2-1 and formula I-6-2,

根據請求項1所述之液晶組合物，其中，所述式II所示化合物選自式II-1至式II-17所示化合物之一或由之所組成的群組，

所述式III所示化合物選自式III-1至式III-15所示化合物之一或由之所組成的群組，

其中，R₃₁表示

，R₄₁表示碳原子數為2的烷基。 The liquid crystal composition according to claim 1, wherein the compound shown in formula II is selected from one of the compounds shown in formula II-1 to formula II-17 or a group consisting of them,

The compound shown in the formula III is selected from one of the compounds shown in the formula III-1 to the formula III-15 or a group consisting of it,

Among them, R ₃₁ means

, R ₄₁ represents an alkyl group having 2 carbon atoms. 根據請求項1所述之液晶組合物，其中，所述液晶組合物還包含一種或複數種式IV所示的化合物，

其中，R₅、R₆各自獨立地表示碳原子數為1-10的烷基、氟取代的碳原子數為1-10的烷基、碳原子數為1-10的烷氧基、氟取代的碳原子數為1-10的烷氧基、碳原子數為2-10的鏈烯基、氟取代的碳原子數為2-10的鏈烯基、碳原子數為3-8的鏈烯氧基或氟取代的碳原子數為3-8的鏈烯氧基，並且其中任意一個或複數個不相鄰的-CH₂-任選被亞環戊基、亞環丁基或亞環丙基替代；W表示-O-、-S-或-CH₂O-。 The liquid crystal composition according to claim 1, wherein the liquid crystal composition further comprises one or more compounds represented by formula IV,

Wherein, R ₅ and R ₆ each independently represent an alkyl group with 1-10 carbon atoms, an alkyl group with 1-10 carbon atoms substituted by fluorine, an alkoxy group with 1-10 carbon atoms, a fluorine-substituted Alkoxy groups with 1-10 carbon atoms, alkenyl groups with 2-10 carbon atoms, alkenyl groups with 2-10 carbon atoms substituted by fluorine, alkenyl groups with 3-8 carbon atoms An alkenyloxy group with 3-8 carbon atoms substituted by oxo or fluorine, and any one or a plurality of non-adjacent -CH ₂ -s are optionally replaced by cyclopentylene, cyclobutylene or cyclopropylene Substitution; W represents -O-, -S- or -CH ₂ O-. 根據請求項3所述之液晶組合物，其中，所述液晶組合物還包含一種或複數種式V所示的化合物，

其中，R₇、R₈各自獨立地表示碳原子數為1-10的烷基、氟取代的碳原子數為1-10的烷基、碳原子數為1-10的烷氧基、氟取代的碳原子數為1-10的烷氧基、碳原子數為2-10的鏈烯基、氟取代的碳原子數為2-10的鏈烯基、碳原子數為3-8的鏈烯氧基或氟取代的碳原子數為3-8的鏈烯氧基；

、

各自獨立地表示

、

或

。 The liquid crystal composition according to claim 3, wherein the liquid crystal composition further comprises one or more compounds represented by formula V,

Wherein, R ₇ and R ₈ each independently represent an alkyl group with 1-10 carbon atoms, an alkyl group with 1-10 carbon atoms substituted by fluorine, an alkoxy group with 1-10 carbon atoms, or an alkyl group with 1-10 carbon atoms substituted by fluorine. Alkoxy groups with 1-10 carbon atoms, alkenyl groups with 2-10 carbon atoms, alkenyl groups with 2-10 carbon atoms substituted by fluorine, alkenyl groups with 3-8 carbon atoms Alkenyloxy group with 3-8 carbon atoms substituted by oxy group or fluorine;

,

express independently

,

or

. 根據請求項4所述之液晶組合物，其中，所述液晶組合物還包含一種或複數種式VI所示化合物，

其中，R₉、R₁₀各自獨立地表示碳原子數為1-10的烷基、氟取代的碳原子數為1-10的烷基、碳原子數為1-10的烷氧基、氟取代的碳原子數為1-10的烷氧基、碳原子數為2-10的鏈烯基、氟取代的碳原子數為2-10的鏈烯基、碳原子數為3-8的鏈烯氧基或氟取代的碳原子數為3-8的鏈烯氧基；

表示

、

或

； F₁、F₂、F₃各自獨立地表示H原子或F原子，且F₂、F₃不同時為F原子。 The liquid crystal composition according to claim 4, wherein the liquid crystal composition further comprises one or more compounds represented by formula VI,

Wherein, R ₉ and R ₁₀ each independently represent an alkyl group with 1-10 carbon atoms, an alkyl group with 1-10 carbon atoms substituted by fluorine, an alkoxy group with 1-10 carbon atoms, or an alkyl group with 1-10 carbon atoms substituted by fluorine. Alkoxy groups with 1-10 carbon atoms, alkenyl groups with 2-10 carbon atoms, alkenyl groups with 2-10 carbon atoms substituted by fluorine, alkenyl groups with 3-8 carbon atoms Alkenyloxy group with 3-8 carbon atoms substituted by oxy group or fluorine;

express

,

or

; F ₁ , F ₂ , and F ₃ each independently represent an H atom or an F atom, and F ₂ and F ₃ are not F atoms at the same time. 一種液晶顯示元件，其包含請求項1-5中任一項所述之液晶組合物，所述顯示元件為主動矩陣顯示元件或被動矩陣顯示元件。 A liquid crystal display element, which comprises the liquid crystal composition described in any one of Claims 1-5, and the display element is an active matrix display element or a passive matrix display element.

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