TW202130792A - Polymerizable compound and application thereof - Google Patents

Polymerizable compound and application thereof Download PDF

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TW202130792A
TW202130792A TW109117710A TW109117710A TW202130792A TW 202130792 A TW202130792 A TW 202130792A TW 109117710 A TW109117710 A TW 109117710A TW 109117710 A TW109117710 A TW 109117710A TW 202130792 A TW202130792 A TW 202130792A
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carbon atoms
iii
liquid crystal
fluorine
formula
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TWI809275B (en
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姜軍
李明
王一平
鮑永鋒
孫新戰
王東梅
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大陸商石家莊誠志永華顯示材料有限公司
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Abstract

The 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 is represented by formula I shown in the description, the liquid crystal composition containing the polymerizable compound has a high voltage retention rate and a stable pre-tilt angle, and when the polymerizable compound is applied to the PS (polymer stabilization) or PSA (polymer stabilization alignment) type liquid crystal display device, residual images can be reduced, the contrast ratio can be increased, and therefore the product quality can be improved.

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 present invention belongs to the technical field of liquid crystal display, and specifically 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, flat-panel display devices such as liquid crystal display (Liquid Crystal Display, LCD) have been widely used in mobile phones, TVs, etc. due to their advantages of high image quality, power saving, thin body and wide application range. 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 Mesogen (RM) is currently a very popular and important research direction in the liquid crystal display industry. Its possible applications include polymer stable alignment (PSA) liquid crystal displays, polymer stable blue phase (PS-BP) liquid crystal displays And graphical 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優良的擴散性。在液晶化合物與RM混合後，需要進行10天左右的低溫測試，因此需要RM 有很好的低溫溶解性。However, there are still some shortcomings in the application of the liquid crystal compound and the RM in the PSA mode display. First of all, not all RMs are suitable for use in PSA displays so far; at the same time, if UV light (Ultraviolet light) is used without adding a photoinitiator to polymerize RM, fewer types of RM can be selected; in addition, it is required The liquid crystal composition formed by the combination of the liquid crystal compound and the selected RM has excellent diffusibility. After the liquid crystal compound is mixed with the RM, a low-temperature test of about 10 days is required, so RM is required to have good low-temperature solubility.

為了克服反應性液晶（RM）低溫溶解度差和擴散性差的問題，獲得具有低溫溶解性好和擴散性均勻的液晶組合物，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 poor low-temperature solubility and poor diffusibility of reactive liquid crystals (RM) and obtain a liquid crystal composition with good low-temperature solubility and uniform diffusibility, the inventors conducted intensive studies and found that the liquid crystal composition contains The compound of the invention can solve this problem, thereby completing the present invention.

本發明還提供含有本發明的化合物的液晶組合物，及包含該液晶組合物的液晶顯示元件或液晶顯示器。The present invention also provides a liquid crystal composition containing the compound of the present invention, and a liquid crystal display element or liquid crystal display containing the liquid crystal composition.

本發明提供的式Ⅰ所示化合物做為反應性液晶(RM)在液晶組合物中使用，具有較好的低溫互溶性。另外，本發明的式Ⅰ所示化合物在混晶中良好的擴散性，藉以能夠在液晶中均勻聚合。The compound represented by formula I provided by the present invention is used as a reactive liquid crystal (RM) in a liquid crystal composition, and has good low-temperature miscibility. In addition, the compound represented by formula I of the present invention has good diffusibility in mixed crystals, so that it can be uniformly polymerized in liquid crystals.

具體地，本發明包含以下內容： 本發明的第一方面，提供一種式Ⅰ所示的可聚合化合物

Figure 02_image003
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。Specifically, the present invention includes the following content: The first aspect of the present invention provides a polymerizable compound represented by formula I
Figure 02_image003
Ⅰ Wherein, L 1 , L 2 , L 3 , and L 4 each independently represent F atom, Cl atom, -CN, linear alkyl group having 1 to 25 C atoms, branched chain having 3 to 25 C atoms Alkyl, cyclic alkyl having 3 to 25 C atoms, alkenyl having 2 to 25 C atoms, or alkynyl having 2 to 25 C atoms, of which one or more non-adjacent -CH 2 -Groups are optionally -O-, -S-, -NH-, -CO-, -CO-O-, -O-CO-, -O-CO-O-, so that -O- and/ Or -S- and/or -NH- are not directly connected to each other, and 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 +x 4 ≥3; Sp 1 , Sp 2 , Sp 3 , Sp 4 , Sp 5 , Z 1 , and Z 2 each independently represent a single bond, a linear alkyl group having 1 to 25 C atoms, having 3 to 25 A branched alkyl group having three C atoms, 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, and one or more of them Non-adjacent -CH 2 -groups are optionally -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O- such that -O- And/or -S- are not directly connected to each other in a way that 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。In a second aspect of the present invention, there is provided a liquid crystal composition, the liquid crystal composition comprising 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。 發明效果In a third aspect of the present invention, there is provided a liquid crystal display element or liquid crystal display, the liquid crystal display element or liquid crystal display comprising one or more polymerizable compounds represented by formula I or containing one or more polymerizable compounds represented by formula I Liquid crystal composition. Invention effect

本發明提供了一種新型可聚合化合物（RM），其在液晶組合物中具有較高的低溫溶解性和良好的擴散性，能夠降低低溫存儲過程中的析出風險和提高應用時的良品率、顯示品質，以達到節約成本的目的。The present invention provides a new type of polymerizable compound (RM), which has higher low-temperature solubility and good diffusibility in liquid crystal compositions, can reduce the risk of precipitation during low-temperature storage and improve the yield and display Quality in order to achieve the purpose of saving costs.

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

Figure 02_image004
、
Figure 02_image006
、
Figure 02_image008
、
Figure 02_image010
、
Figure 02_image012
、
Figure 02_image014
、
Figure 02_image016
、
Figure 02_image018
、
Figure 02_image020
、
Figure 02_image022
、
Figure 02_image024
、
Figure 02_image026
或
Figure 02_image028
。 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，
Figure 02_image030
I-1-1
Figure 02_image032
I-1-2
Figure 02_image034
I-1-3
Figure 02_image036
     I-2-1
Figure 02_image038
      I-2-2
Figure 02_image040
 I-2-3
Figure 02_image042
I-2-4
Figure 02_image044
I-2-5
Figure 02_image046
I-2-6
Figure 02_image048
   I-2-7
Figure 02_image050
I-2-8
Figure 02_image052
 I-2-9
Figure 02_image054
  I-2-10
Figure 02_image056
   I-2-11
Figure 02_image058
  I-2-12
Figure 02_image060
I-3-1
Figure 02_image062
I-3-2
Figure 02_image064
  I-3-3
Figure 02_image066
  I-4-1  
Figure 02_image068
  I-4-2
Figure 02_image070
  I-4-3
Figure 02_image072
  I-4-4
Figure 02_image074
I-4-5
Figure 02_image076
 I-4-6
Figure 02_image078
  I-4-7
Figure 02_image080
I-4-8
Figure 02_image082
  I-4-9
Figure 02_image084
I-4-10
Figure 02_image086
 I-4-11
Figure 02_image088
 I-4-12
Figure 02_image090
I-5-1
Figure 02_image092
  I-5-2
Figure 02_image094
I-6-1
Figure 02_image096
  I-6-2
Figure 02_image098
I-6-3
Figure 02_image100
  I-6-4
Figure 02_image102
I-6-5
Figure 02_image104
I-6-6
Figure 02_image106
I-6-7
Figure 02_image108
  I-6-8
Figure 02_image110
I-6-9
Figure 02_image112
  I-7-1
Figure 02_image114
I-8-1
Figure 02_image116
 I-8-2
Figure 02_image118
I-8-3  
Figure 02_image120
 I-8-4
Figure 02_image122
I-8-5
Figure 02_image124
 I-8-6
Figure 02_image126
I-8-7
Figure 02_image128
I-8-8
Figure 02_image130
 I-8-9
Figure 02_image132
I-10-1
Figure 02_image134
 I-10-2
Figure 02_image136
 I-10-3
Figure 02_image138
 I-10-4
Figure 02_image140
  I-10-5
Figure 02_image142
 I-10-6
Figure 02_image144
  I-10-7
Figure 02_image146
 I-10-8
Figure 02_image148
 I-10-9
Figure 02_image150
  I-12-1
Figure 02_image152
 I-12-2
Figure 02_image154
  I-12-3  
Figure 02_image156
I-12-4
Figure 02_image158
  I-12-5
Figure 02_image160
 I-12-6
Figure 02_image162
 I-12-7
Figure 02_image164
    I-12-8
Figure 02_image166
  I-12-9
Figure 02_image168
 I-14-1
Figure 02_image170
 I-14-2
Figure 02_image172
  I-14-3
Figure 02_image174
 I-14-4
Figure 02_image176
  I-14-5
Figure 02_image178
I-14-6
Figure 02_image180
I-14-7
Figure 02_image182
 I-14-8
Figure 02_image184
I-14-9
Figure 02_image186
I-15-1
Figure 02_image188
  I-15-2
Figure 02_image190
I-15-3
Figure 02_image192
 I-16-1
Figure 02_image194
 I-16-2
Figure 02_image196
 I-16-3
Figure 02_image198
  I-17-1
Figure 02_image200
 I-17-2。 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 having 1 to 5 carbon atoms, a fluorine-substituted Alkyl groups with 1-5 carbon atoms, alkenyl groups with 2-5 carbon atoms, alkoxy groups with 1-5 carbon atoms, fluoro-substituted alkoxy groups with 1-5 carbon atoms, 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 , Z 2 each independently represent a single bond, and the number of carbon atoms is 1- 10 alkyl, 2-10 alkenyl or 2-10 alkynyl, 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 , and P 4 each independently represents
Figure 02_image004
,
Figure 02_image006
,
Figure 02_image008
,
Figure 02_image010
,
Figure 02_image012
,
Figure 02_image014
,
Figure 02_image016
,
Figure 02_image018
,
Figure 02_image020
,
Figure 02_image022
,
Figure 02_image024
,
Figure 02_image026
or
Figure 02_image028
. The polymerizable compound disclosed in the present invention is more preferably selected from the group consisting of the following compounds represented by formula I-1-1 to formula I-17-2,
Figure 02_image030
I-1-1
Figure 02_image032
I-1-2
Figure 02_image034
I-1-3
Figure 02_image036
I-2-1
Figure 02_image038
I-2-2
Figure 02_image040
I-2-3
Figure 02_image042
I-2-4
Figure 02_image044
I-2-5
Figure 02_image046
I-2-6
Figure 02_image048
I-2-7
Figure 02_image050
I-2-8
Figure 02_image052
I-2-9
Figure 02_image054
I-2-10
Figure 02_image056
I-2-11
Figure 02_image058
I-2-12
Figure 02_image060
I-3-1
Figure 02_image062
I-3-2
Figure 02_image064
I-3-3
Figure 02_image066
I-4-1
Figure 02_image068
I-4-2
Figure 02_image070
I-4-3
Figure 02_image072
I-4-4
Figure 02_image074
I-4-5
Figure 02_image076
I-4-6
Figure 02_image078
I-4-7
Figure 02_image080
I-4-8
Figure 02_image082
I-4-9
Figure 02_image084
I-4-10
Figure 02_image086
I-4-11
Figure 02_image088
I-4-12
Figure 02_image090
I-5-1
Figure 02_image092
I-5-2
Figure 02_image094
I-6-1
Figure 02_image096
I-6-2
Figure 02_image098
I-6-3
Figure 02_image100
I-6-4
Figure 02_image102
I-6-5
Figure 02_image104
I-6-6
Figure 02_image106
I-6-7
Figure 02_image108
I-6-8
Figure 02_image110
I-6-9
Figure 02_image112
I-7-1
Figure 02_image114
I-8-1
Figure 02_image116
I-8-2
Figure 02_image118
I-8-3
Figure 02_image120
I-8-4
Figure 02_image122
I-8-5
Figure 02_image124
I-8-6
Figure 02_image126
I-8-7
Figure 02_image128
I-8-8
Figure 02_image130
I-8-9
Figure 02_image132
I-10-1
Figure 02_image134
I-10-2
Figure 02_image136
I-10-3
Figure 02_image138
I-10-4
Figure 02_image140
I-10-5
Figure 02_image142
I-10-6
Figure 02_image144
I-10-7
Figure 02_image146
I-10-8
Figure 02_image148
I-10-9
Figure 02_image150
I-12-1
Figure 02_image152
I-12-2
Figure 02_image154
I-12-3
Figure 02_image156
I-12-4
Figure 02_image158
I-12-5
Figure 02_image160
I-12-6
Figure 02_image162
I-12-7
Figure 02_image164
I-12-8
Figure 02_image166
I-12-9
Figure 02_image168
I-14-1
Figure 02_image170
I-14-2
Figure 02_image172
I-14-3
Figure 02_image174
I-14-4
Figure 02_image176
I-14-5
Figure 02_image178
I-14-6
Figure 02_image180
I-14-7
Figure 02_image182
I-14-8
Figure 02_image184
I-14-9
Figure 02_image186
I-15-1
Figure 02_image188
I-15-2
Figure 02_image190
I-15-3
Figure 02_image192
I-16-1
Figure 02_image194
I-16-2
Figure 02_image196
I-16-3
Figure 02_image198
I-17-1
Figure 02_image200
I-17-2.

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 invention also provides a liquid crystal composition comprising one or more of the aforementioned polymerizable compounds of the 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, which is an aspect of the present invention, contains the compound represented by the aforementioned formula I. In addition to the compound represented by formula I, the liquid crystal composition may also contain liquid crystal compounds other than the compound represented by formula I and other additives.

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，

Figure 02_image202
Ⅱ
Figure 02_image204
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；
Figure 02_image206
、
Figure 02_image208
各自獨立地表示
Figure 02_image210
或
Figure 02_image212
； 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、-CH2 CH2 -、-CH2 O-或-OCH2 -；
Figure 02_image214
、
Figure 02_image216
各自獨立地表示
Figure 02_image210
、
Figure 02_image212
、
Figure 02_image218
、
Figure 02_image220
、
Figure 02_image222
、
Figure 02_image224
、
Figure 02_image226
或
Figure 02_image228
； m1 表示1或2，當m1 表示2時，
Figure 02_image216
相同或不同； n1 表示0、1或2，當n1 表示2時，
Figure 02_image216
相同或不同。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,
Figure 02_image202
Ⅱ
Figure 02_image204
Ⅲ In formula II, R 1 and R 2 each independently represent an alkyl group with 1-10 carbon atoms, a fluorine-substituted alkyl group with 1-10 carbon atoms, and an alkoxy group with 1-10 carbon atoms. , Fluorine-substituted alkoxy with 1-10 carbon atoms, alkenyl with 2-10 carbon atoms, fluorine-substituted alkenyl with 2-10 carbon atoms, 3-8 carbon atoms Alkenyloxy or fluorine-substituted alkenyloxy with 3-8 carbon atoms;
Figure 02_image206
,
Figure 02_image208
Expressed independently of each other
Figure 02_image210
or
Figure 02_image212
; In formula III, R 3 and R 4 each independently represent an alkyl group having 1-10 carbon atoms, a fluorine-substituted alkyl group having 1-10 carbon atoms, and an alkoxy group having 1-10 carbon atoms. , Fluorine-substituted alkoxy with 1-10 carbon atoms, alkenyl with 2-10 carbon atoms, fluorine-substituted alkenyl with 2-10 carbon atoms, 3-8 carbon atoms Alkenyloxy group or fluorine-substituted alkenyloxy group having 3-8 carbon atoms, and any one or more of R 3 and R 4 that are not adjacent -CH 2 -are optionally cyclopentylene, Cyclobutylene or cyclopropylene substitution; Z 1 and Z 2 each independently represent a single bond, -CH 2 CH 2 -, -CH 2 O- or -OCH 2 -;
Figure 02_image214
,
Figure 02_image216
Expressed independently of each other
Figure 02_image210
,
Figure 02_image212
,
Figure 02_image218
,
Figure 02_image220
,
Figure 02_image222
,
Figure 02_image224
,
Figure 02_image226
or
Figure 02_image228
; M 1 means 1 or 2, when m 1 means 2,
Figure 02_image216
Same or different; n 1 represents 0, 1 or 2, when n 1 represents 2,
Figure 02_image216
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 combination of the compound represented by formula II and the compound represented by 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 increase the reaction speed of the liquid crystal composition, and has a negative medium. The electrical anisotropy can adjust 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 except the compound represented by formula I is recorded as 100%, and the percentage of the ratio between the mass of the compound represented by formula I and the total mass of other compounds is recorded as the formula I in the liquid crystal composition The mass fraction of the compound shown. For example, when the liquid crystal composition contains only the compounds represented by formula I, formula II and formula III, the total content of the compounds represented by formula II and formula III is recorded as 100%, and the added amount of the compound represented by formula I The percentage of the ratio to the total mass of the compound 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，

Figure 02_image230
Ⅱ-1
Figure 02_image232
 Ⅱ-2
Figure 02_image234
 Ⅱ-3
Figure 02_image236
 Ⅱ-4
Figure 02_image238
 Ⅱ-5
Figure 02_image240
 Ⅱ-6
Figure 02_image242
 Ⅱ-7
Figure 02_image244
 Ⅱ-8
Figure 02_image246
 Ⅱ-9
Figure 02_image248
 Ⅱ-10
Figure 02_image250
 Ⅱ-11
Figure 02_image252
 Ⅱ-12
Figure 02_image254
 Ⅱ-13
Figure 02_image256
 Ⅱ-14
Figure 02_image258
 Ⅱ-15
Figure 02_image260
 Ⅱ-16
Figure 02_image262
 Ⅱ-17。 In the liquid crystal composition of the present invention, preferably, the compound represented by formula II is selected from the group consisting of compounds represented by formula II-1 to formula II-17,
Figure 02_image230
 Ⅱ-1
Figure 02_image232
 Ⅱ-2
Figure 02_image234
 Ⅱ-3
Figure 02_image236
 Ⅱ-4
Figure 02_image238
 Ⅱ-5
Figure 02_image240
 Ⅱ-6
Figure 02_image242
 Ⅱ-7
Figure 02_image244
 Ⅱ-8
Figure 02_image246
 Ⅱ-9
Figure 02_image248
 Ⅱ-10
Figure 02_image250
 Ⅱ-11
Figure 02_image252
 Ⅱ-12
Figure 02_image254
 Ⅱ-13
Figure 02_image256
 Ⅱ-14
Figure 02_image258
 Ⅱ-15
Figure 02_image260
 Ⅱ-16
Figure 02_image262
 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，

Figure 02_image264
Ⅲ-1
Figure 02_image266
 Ⅲ-2
Figure 02_image268
 Ⅲ-3
Figure 02_image270
 Ⅲ-4
Figure 02_image272
 Ⅲ-5
Figure 02_image274
 Ⅲ-6
Figure 02_image276
 Ⅲ-7
Figure 02_image278
 Ⅲ-8
Figure 02_image280
 Ⅲ-9
Figure 02_image282
 Ⅲ-10
Figure 02_image284
 Ⅲ-11
Figure 02_image286
 Ⅲ-12
Figure 02_image288
 Ⅲ-13
Figure 02_image290
 Ⅲ-14
Figure 02_image292
 Ⅲ-15 Preferably, the compound represented by formula III is selected from the group consisting of compounds represented by formula III-1 to formula III-15,
Figure 02_image264
 Ⅲ-1
Figure 02_image266
 Ⅲ-2
Figure 02_image268
 Ⅲ-3
Figure 02_image270
 Ⅲ-4
Figure 02_image272
 Ⅲ-5
Figure 02_image274
 Ⅲ-6
Figure 02_image276
 Ⅲ-7
Figure 02_image278
 Ⅲ-8
Figure 02_image280
 Ⅲ-9
Figure 02_image282
 Ⅲ-10
Figure 02_image284
 Ⅲ-11
Figure 02_image286
 Ⅲ-12
Figure 02_image288
 Ⅲ-13
Figure 02_image290
 Ⅲ-14
Figure 02_image292
 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, a fluorine-substituted alkyl group with 1-10 carbon atoms, an alkoxy group with 1-10 carbon atoms, and a fluorine-substituted Alkyloxy with 1-10 carbon atoms, alkenyl with 2-10 carbon atoms, fluorine-substituted alkenyl with 2-10 carbon atoms, and alkenyl with 3-8 carbon atoms Oxy or fluorine-substituted alkenyloxy with 3-8 carbon atoms, and any one or more non-adjacent groups represented by R 3 and R 4 -CH 2 -are optionally cyclopentylene , Cyclobutylene or cyclopropylidene substitution.

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，

Figure 02_image294
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-CH2 O-。The liquid crystal composition disclosed in the present invention preferably further contains one or more compounds represented by formula IV,
Figure 02_image294
Ⅳ Wherein, R 5 and R 6 each independently represent an alkyl group with 1-10 carbon atoms, a fluorine-substituted alkyl group with 1-10 carbon atoms, an alkoxy group with 1-10 carbon atoms, fluorine Substituted alkoxy groups with 1-10 carbon atoms, alkenyl groups with 2-10 carbon atoms, fluorine-substituted alkenyl groups with 2-10 carbon atoms, chains with 3-8 carbon atoms Alkenyloxy or fluorine-substituted alkenyloxy having 3-8 carbon atoms, and any one or more of R 5 and R 6 that are not adjacent to -CH 2 -are optionally substituted by cyclopentylene or ring Butyl or cyclopropylene substitution; 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 aforementioned compound represented by Formula IV in the liquid crystal composition of the present application, the liquid crystal composition can be made to have a 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，

Figure 02_image296
Ⅳ-1
Figure 02_image298
Ⅳ-2；
Figure 02_image300
Ⅳ-3
Figure 02_image302
Ⅳ-4；
Figure 02_image304
Ⅳ-5
Figure 02_image306
Ⅳ-6；
Figure 02_image308
Ⅳ-7
Figure 02_image310
Ⅳ-8；
Figure 02_image312
Ⅳ-9；
Figure 02_image314
Ⅳ-10； 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，
Figure 02_image316
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；
Figure 02_image318
、
Figure 02_image320
各自獨立地表示
Figure 02_image210
、
Figure 02_image212
或
Figure 02_image226
。Further, the aforementioned compound represented by formula IV is selected from the group consisting of compounds represented by formula IV-1 to formula IV-10,
Figure 02_image296
Ⅳ-1
Figure 02_image298
Ⅳ-2;
Figure 02_image300
Ⅳ-3
Figure 02_image302
Ⅳ-4;
Figure 02_image304
Ⅳ-5
Figure 02_image306
Ⅳ-6;
Figure 02_image308
Ⅳ-7
Figure 02_image310
Ⅳ-8;
Figure 02_image312
Ⅳ-9;
Figure 02_image314
IV-10; wherein R 51 and R 61 represent an alkyl group with a carbon number of 1-6; the liquid crystal composition disclosed in the present invention preferably further contains one or more compounds represented by formula V,
Figure 02_image316
Ⅴ where R 7 and R 8 each independently represent an alkyl group with 1-10 carbon atoms, a fluorine-substituted alkyl group with 1-10 carbon atoms, an alkoxy group with 1-10 carbon atoms, fluorine Substituted alkoxy groups with 1-10 carbon atoms, alkenyl groups with 2-10 carbon atoms, fluorine-substituted alkenyl groups with 2-10 carbon atoms, chains with 3-8 carbon atoms Alkenyloxy or fluorine-substituted alkenyloxy with 3-8 carbon atoms;
Figure 02_image318
,
Figure 02_image320
Expressed independently of each other
Figure 02_image210
,
Figure 02_image212
or
Figure 02_image226
.

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，

Figure 02_image322
Ⅴ-1；
Figure 02_image324
Ⅴ-2；
Figure 02_image326
Ⅴ-3；
Figure 02_image328
Ⅴ-4； 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 formula V is preferably selected from the group consisting of compounds represented by formula V-1 to formula V-4,
Figure 02_image322
Ⅴ-1;
Figure 02_image324
Ⅴ-2;
Figure 02_image326
Ⅴ-3;
Figure 02_image328
Ⅴ-4; wherein 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, as an alkene with 2-6 carbon atoms Examples of the group include vinyl, 2-propenyl or 3-pentenyl; R 82 represents an alkoxy group having 1 to 5 carbon atoms; by including the compound represented by formula V in the liquid crystal composition of the present invention , It is possible to obtain high sharpness points and high elastic constants, especially the splay elastic constant K 33 , which is 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，

Figure 02_image330
Ⅵ； 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；
Figure 02_image332
表示
Figure 02_image210
、
Figure 02_image212
或
Figure 02_image226
。The liquid crystal composition disclosed in the present invention preferably further contains one or more compounds represented by formula VI,
Figure 02_image330
Ⅵ; wherein R 9 and R 10 each independently represent an alkyl group having 1-10 carbon atoms, a fluorine-substituted alkyl group having 1-10 carbon atoms, an alkoxy group having 1-10 carbon atoms, Fluorine-substituted alkoxy groups with 1-10 carbon atoms, alkenyl groups with 2-10 carbon atoms, fluorine-substituted alkenyl groups with 2-10 carbon atoms, and 3-8 carbon atoms Alkenyloxy or fluorine-substituted alkenyloxy with 3-8 carbon atoms;
Figure 02_image332
Express
Figure 02_image210
,
Figure 02_image212
or
Figure 02_image226
.

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，

Figure 02_image334
Ⅵ-1；
Figure 02_image336
Ⅵ-2；
Figure 02_image338
Ⅵ-3； 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 formula VI is preferably selected from the group consisting of compounds represented by formula VI-1 to VI-3,
Figure 02_image334
Ⅵ-1;
Figure 02_image336
Ⅵ-2;
Figure 02_image338
VI-3: Among them, R 91 and R 101 each independently preferably represent an alkyl group having 2-6 carbon atoms or an alkenyl group having 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。By containing the compound selected from formula VI-1 to VI-3 in the liquid crystal composition, the clear point of the liquid crystal composition can be improved.

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 contains 0.01-1% of the compound represented by formula I, 30-60% of the compound represented by formula II, 30-60% of the compound represented by formula III, and 1- 10% of the compound represented by formula VI; Preferably, the liquid crystal composition of the present invention contains 0.01-1% of the compound represented by formula I, 15-60% of the compound represented by formula II, 20-60% of the compound represented by formula III, and 1- 15% of the compound represented by formula IV, 1-10% of the compound represented by formula VI; Preferably, the liquid crystal composition of the present invention contains in mass percentage: 0.03-0.2% of the compound represented by formula I, 35-45% of the compound represented by formula II, 45-50% of the compound represented by formula III, 2- 10% of the compound represented by formula IV, 2-5% of the compound represented by 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，1-30 %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 contains 0.01-1% of the compound represented by formula I, 15-60% of the compound represented by formula II, 20-60% of the compound represented by formula III, and 1- 30% of the compound represented by formula V, 1-10% of the compound represented by formula VI; Preferably, the liquid crystal composition of the present invention contains 0.03-0.2% of the compound represented by formula I, 25-40% of the compound represented by formula II, 35-50% of the compound represented by formula III, and 5- 20% of the compound represented by formula V, 2-5% of the compound represented by 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 contains 0.01-1% of the compound represented by formula I, 15-60% of the compound represented by formula II, 20-60% of the compound represented by formula III, and 1- 15% of the compound represented by formula IV, 1-30% of the compound represented by formula V, and 1-10% of the compound represented by formula VI; Preferably, the liquid crystal composition of the present invention contains in mass percentage: 0.03-0.2% of the compound represented by formula I, 20-40% of the compound represented by formula II, 30-50% of the compound represented by formula III, 2- 10% of the compound represented by formula IV, 5-20% of the compound represented by formula V, and 2-5% of the compound represented by 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, various functional dopants can also be added. In the case of containing dopants, the content of the dopants is preferably 0.01-1% by mass in the liquid crystal composition. Examples of these dopants include antioxidants, ultraviolet absorbers, and chiral agents.

抗氧化劑、紫外線吸收劑可以列舉出，

Figure 02_image340
；
Figure 02_image342
；
Figure 02_image344
；
Figure 02_image346
；
Figure 02_image348
；
Figure 02_image350
； t表示1-10的整數。Antioxidants and UV absorbers can be listed,
Figure 02_image340
；
Figure 02_image342
；
Figure 02_image344
；
Figure 02_image346
；
Figure 02_image348
；
Figure 02_image350
; 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 includes 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 aforementioned liquid crystal display element of the present invention, as long as the compound represented by formula I of the present invention is contained in the liquid crystal composition used, its structure is not limited in any way. Those with ordinary knowledge in the art can determine the required performance Choose 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, for example, the following structure: including a first substrate, a second substrate, and a liquid crystal composition disposed between the first substrate and the second substrate, the first substrate It is arranged in parallel with the second substrate. The first substrate and the second substrate are provided with an alignment layer on the side close to the liquid crystal composition, the first substrate is provided with a common electrode, the second substrate is provided with a pixel electrode, the first substrate and the second substrate Spacers are scattered between the substrates.

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：As the method for preparing the liquid crystal display of the present invention, a person with ordinary knowledge in the field can select a suitable method for preparation according to the common knowledge in the field. As an example of the manufacturing method of the liquid crystal display of the present invention, for example, a manufacturing method including the following steps:

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360 nm-370 nm，紫外光輻照度為60-72 mw/cm2 。做為紫外光照射的時間，可以為例如50-65s，較佳為50-60s。Coat the alignment material uniformly on the surface of the first substrate and the second substrate. Polyimide can be selected as the alignment material. The uniformly coated alignment material is heated and cured at a heating temperature of 210-250 ℃ to form an alignment layer; on the second substrate Spread spacers on the surface, and apply frame glue along the edge of the first substrate, and cure it at 100 ℃-150 ℃; Place the first substrate and the second substrate oppositely and bond them to form a structure with interlayer space; Combine liquid crystals The substance is injected into the interlayer space between the first substrate and the second substrate, and is sealed and cured, so that the liquid crystal composition is sealed between the first substrate and the second substrate, and the power is applied and the ultraviolet light is irradiated at the same time. Ultraviolet light irradiation is divided into two stages: 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 360 nm-370 nm, and the irradiance of ultraviolet light is 60-72 mw/cm 2 . As the time of ultraviolet light irradiation, it can 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360 nm-370 nm，在UV2階段使用紫外光輻照度為例如3-8 mw/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100-150 min。 實施例After the first stage of light irradiation is completed, the second stage of light irradiation (UV2) is performed. The light used in UV2 can be, for example, ultraviolet light. In the second stage ultraviolet light irradiation (UV2), the ultraviolet light wavelength is, for example, 360 nm-370 nm, and the ultraviolet light irradiance used in the UV2 stage is, for example, 3-8 mw/cm 2 . By adopting such irradiance, the compound represented by formula I that has not undergone polymerization can be slowly and completely polymerized, and the conversion rate of the polymerizable compound can be increased, so that there is no residue of the polymerizable compound in the liquid crystal composition. And because the polymerization is slow, the process will not affect the pretilt angle that has been formed. The ultraviolet light irradiation time in the UV2 stage can be, for example, 100-150 min. 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 explain the present invention more clearly, the present invention will be further described below in conjunction with preferred embodiments and drawings. Similar components in the drawings are denoted by the same reference numerals. Those with ordinary knowledge in the art should understand that the content described below is illustrative rather than restrictive, and should not be used to limit the scope of protection 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； Δn表示光學各向異性，Δn=ne -no ，其中，no 為尋常光的折射率，ne 為非尋常光的折射率，測試條件為25±2 ℃，589 nm，阿貝折射儀測試； Δε表示介電各向異性，Δε=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10 ms、電壓保持時間16.7 ms。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 methods are conventional methods unless otherwise specified. The raw materials used can be obtained from publicly disclosed commercial channels unless otherwise specified. The specific meanings and test conditions of liquid crystal monomers and other symbols are as follows: Cp represents the clear point of liquid crystal (℃), measured by DSC quantitative method; Δn represents optical anisotropy, Δn=n e -n o , where n o is ordinary light The refractive index of n e is the refractive index of extraordinary light, and the test conditions are 25±2 ℃, 589 nm, tested by Abbe refractometer; Δε represents dielectric anisotropy, Δε=ε∥-ε⊥, where 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 ℃, 20 micron vertical box, INSTEC: ALCT-IR1 test; VHR represents the voltage retention rate (% ), the test conditions are 20±2 ℃, voltage is ±5V, pulse width is 10 ms, and voltage holding time is 16.7 ms. The test equipment is TOYO Model 6254 liquid crystal performance comprehensive tester; γ 1 represents rotational viscosity (mPa·s), the test condition is 25±0.5 ℃, 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 in the preparation of the liquid crystal composition are: The preparation method of the liquid crystal composition is as follows: each polymerizable compound is weighed according to a certain ratio and then put into a stainless steel beaker, the stainless steel beaker containing each polymerizable compound is placed on a magnetic stirring instrument and heated and melted. After the polymerizable compound is melted, a magnetic rotor is added to the stainless steel beaker, the mixture is stirred uniformly, 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365 nm，輻照度為64 mw/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365 nm的紫外光，輻照度為5 mw/cm2 ，光照射時間為100-150 min。The preparation method of the liquid crystal display element in the embodiment of the present invention is as follows: firstly, the alignment material is uniformly coated on the surfaces of the first substrate and the second substrate, and the alignment material can be polyimide, and the uniformly coated alignment material is heated and cured , The heating temperature is 230 ℃ to form an alignment layer; secondly, spacers are spread on the surface of the second substrate, and frame glue is applied along the edge of the first substrate and cured at 120 ℃; then, the first substrate and the second substrate 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, and sealed and cured, thereby sealing the liquid crystal composition on the first substrate and the second substrate In between, and at the same time power up, ultraviolet light irradiation. 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, light irradiation is performed with an ultraviolet wavelength of 365 nm and an irradiance of 64 mw/cm 2. After the first stage of light irradiation is completed, the second stage of light irradiation (UV2) is performed. In UV2, a wavelength of 365 nm is used. Ultraviolet light, the irradiance is 5 mw/cm 2 , and the light irradiation time is 100-150 min.

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。 表1 環結構的對應代碼 環結構 對應代碼

Figure 02_image352
C
Figure 02_image354
 P
Figure 02_image356
 L
Figure 02_image358
 G
Figure 02_image360
 Gi
Figure 02_image362
 Y
Figure 02_image364
 Sb
Figure 02_image366
 Sc 表2 端基與鏈接基團的對應代碼 端基與連結基團 對應代碼 Cn H2n+1 - n- Cn H2n+1 O- nO- -CF3 -T -OCF3 -OT -CH2 O- -O- -F -F -CH2 CH2 - -E- -CH=CH- -V- -CH=CH-Cn H2n+1 Vn-
Figure 02_image368
 Cp-
Figure 02_image370
Figure 02_image372
 Cpr-
Figure 02_image374
 Cpr1-
Figure 02_image376
 CpO
Figure 02_image378
 CprO 舉例：
Figure 02_image380
，其代碼為CC-Cp-V1；
Figure 02_image382
，其代碼為PGP- Cpr1-2；
Figure 02_image384
，其代碼為CPY-2-O2；
Figure 02_image386
，其代碼為CCY-3-O2；
Figure 02_image388
，其代碼為COY-3-O2；
Figure 02_image390
，其代碼為CCOY-3-O2；
Figure 02_image392
，其代碼為Sb-CpO-O4；
Figure 02_image394
，其代碼為Sc-CpO-O4；
Figure 02_image396
，其代碼為COYL-Cprl-O2；
Figure 02_image398
，其代碼為COYL-1-OV1。The structure of the liquid crystal monomer used in the embodiment of the present invention is represented by a code, and the code representation method of the liquid crystal ring structure, terminal group, and connecting group is shown in Table 1 and Table 2 below. Table 1 Corresponding codes of ring structure Ring structure Corresponding code
Figure 02_image352
 C
Figure 02_image354
 P
Figure 02_image356
 L
Figure 02_image358
 G
Figure 02_image360
 Gi
Figure 02_image362
 Y
Figure 02_image364
 Sb
Figure 02_image366
 Sc Table 2 Corresponding codes of end groups and linking groups End group and linking group Corresponding code C n H 2n+1- n- C n H 2n+1 O- nO- -CF 3 -T -OCF 3 -OT -CH 2 O- -O- -F -F -CH 2 CH 2- -E- -CH=CH- -V- -CH=CH-C n H 2n+1 Vn-
Figure 02_image368
 Cp-
Figure 02_image370
Figure 02_image372
 Cpr-
Figure 02_image374
 Cpr1-
Figure 02_image376
 CpO
Figure 02_image378
 CprO For example:
Figure 02_image380
, Its code is CC-Cp-V1;
Figure 02_image382
, Its code is PGP- Cpr1-2;
Figure 02_image384
, Its code is CPY-2-O2;
Figure 02_image386
, Its code is CCY-3-O2;
Figure 02_image388
, Its code is COY-3-O2;
Figure 02_image390
, Its code is CCOY-3-O2;
Figure 02_image392
, Its code is Sb-CpO-O4;
Figure 02_image394
, Its code is Sc-CpO-O4;
Figure 02_image396
, Its code is COYL-Cprl-O2;
Figure 02_image398
, And its 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： [液晶化合物] 本發明的式I所示化合物可根據下述方案進行合成：

Figure 02_image400
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 各自獨立地表示與上述式Ⅰ所示的可聚合化合物中的定義相同； S1 、S2 各自獨立地表示醛基、羥基、羧基； B1 、B2 、B3 、B4 各自獨立地表示羥基的保護基。The following specific examples are used to illustrate the present invention: [Liquid Crystal Compound] The compound represented by formula I of the present invention can be synthesized according to the following scheme:
Figure 02_image400
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 each independently represent the same definition as in the polymerizable compound shown in the above formula I; S 1 , S 2 each independently represent an aldehyde group , Hydroxyl group, carboxyl group; B 1 , B 2 , B 3 , and B 4 each independently represent a protective 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具有通常知識者所熟知的，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. The principle, operation process, conventional post-treatment, silica gel column, recrystallization purification and other methods of such methods are well known to those with ordinary knowledge in the field. , The synthesis process can be fully realized and the target product can be obtained.

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 in all steps of all the above methods are carried out in a solvent; the solvents are selected from at least tetrahydrofuran, N,N-dimethylformamide, ethanol, methanol, dichloromethane, acetone, toluene and deionized water A sort of.

實施例1 化合物結構式如下式I-1-1所示：

Figure 02_image030
I-1-1 其製備路線如下：
Figure 02_image402
製備的具體操作流程： 在5 L三口瓶中投入0.3 mol的對苄氧基苯硼酸、0.3 mol的2-苄氧基-5-溴-3-氟苯酚，2.0 L甲苯，0.7 L水，0.36 mol碳酸鉀，催化劑0.3 g，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:92 %，收率Y=77 %。Example 1 The structural formula of the compound is shown in the following formula I-1-1:
Figure 02_image030
The preparation route of I-1-1 is as follows:
Figure 02_image402
The specific operation process of the preparation: Put 0.3 mol of p-benzyloxyphenylboronic acid, 0.3 mol of 2-benzyloxy-5-bromo-3-fluorophenol, 2.0 L of toluene, 0.7 L of water, and 0.36 into a 5 L three-necked flask. mol potassium carbonate, 0.3 g of catalyst, heated to reflux for 3 hours. Standing for liquid separation, column chromatography separation, and toluene/ethanol recrystallization to obtain compound 1-1 as a yellow solid. HPLC: 92%, yield Y=77%.

在2 L三口瓶中投0.22 mol的化合物1-1、0.1 mol的1,3-二溴丙烷、0.22 mol的無水碳酸鉀，1.2 L 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30 min，過濾，0.5 L石油醚打漿，可得到化合物1-2，HPLC:90 %，收率Y=75 %。In a 2 L three-necked flask, 0.22 mol of compound 1-1, 0.1 mol of 1,3-dibromopropane, 0.22 mol of anhydrous potassium carbonate, 1.2 L of DMF, and N 2 protection were put into the reaction at 120 ℃ for 4 hours. After the reaction is completed, the temperature is lowered, and the mixture is poured into ice water while stirring, stirred for 30 min, filtered, and beaten with 0.5 L of petroleum ether to obtain compound 1-2, HPLC: 90%, yield Y=75%.

將0.08 mol化合物1-2、6.6g的Pd/C、0.5 L的THF和0.5 L的EtOH加入1 L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10 min，得到化合物1-3，HPLC:98 %，收率Y=70 %。Add 0.08 mol of compound 1-2, 6.6 g of Pd/C, 0.5 L of THF and 0.5 L of EtOH into a 1 L three-necked flask, replace with N 2 three times, and replace with H 2 three times. Hydrodebenzylation at 40°C, react for 6 hours . After the reaction is complete, the celite is filtered, the filtrate is concentrated, PE:EA=10:1, and the mixture is stirred for 10 min to obtain compound 1-3, HPLC: 98%, yield Y=70%.

在1 L三口瓶中投0.02 mol的化合物1-3、0.1 mol的三乙胺、0.5 L 的DCM，N2 保護下控溫0 ℃滴加0.1 mol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50 g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4 h，吸濾，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:99.1 %，收率Y=42 %。化合物I-1-1的1 H- NMR譜圖如圖1所示。Put 0.02 mol of compound 1-3, 0.1 mol of triethylamine, 0.5 L of DCM into a 1 L three-necked flask, and add 0.1 mol of methacrylic acid chloride dropwise under the protection of N 2 and the temperature is controlled at 0 ℃. After dripping, react at room temperature for 3 hours. After the reaction is complete, add water solution, extract the aqueous phase with DCM, combine the organic phases, wash with saturated brine, dry with anhydrous sodium sulfate, filter, concentrate the filtrate, dissolve 5 times toluene at 45 ℃, pass through a 50 g silica gel column, and wash with 3 times toluene. , Concentrated, 3 times of toluene and 3 times of ethanol heated to dissolve, frozen at -20 ℃ for 4 h, suction filtered, recrystallized three times according to the same method, and dried to obtain a white solid compound I-1-1, HPLC: 99.1%, Yield Y=42%. The 1 H-NMR spectrum of compound I-1-1 is shown in FIG. 1.

實施例2 化合物結構式如下式I-2-1所示：

Figure 02_image036
I-2-1 其製備路線如下：
Figure 02_image404
用3-氟-4-苄氧基苯硼酸代替苄氧基苯硼酸，2苄氧基-3-溴苯酚代替2-苄氧基-5-溴-3-氟苯酚，合成化合物2-1. 製備的具體操作流程：同上(I-1-1操作)。Example 2 The structural formula of the compound is shown in the following formula I-2-1:
Figure 02_image036
I-2-1 The preparation route is as follows:
Figure 02_image404
Using 3-fluoro-4-benzyloxyphenylboronic acid instead of benzyloxyphenylboronic acid and 2benzyloxy-3-bromophenol instead of 2-benzyloxy-5-bromo-3-fluorophenol, compound 2-1 was synthesized. The specific operation process of the preparation: Same as above (I-1-1 operation).

實施例3 化合物結構式如下式I-4-1所示：

Figure 02_image066
I-4-1 其製備路線如下：
Figure 02_image406
製備的具體操作流程： 在2 L三口瓶中投入0.3 mol的3-氟-4-苄氧基苯硼酸、0.3 mol的2-苄氧基-5-溴-2-苯甲醛，2.0 L甲苯，0.7 L水，0.36 mol碳酸鉀，催化劑0.3 g，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:95 %，收率Y=75 %。Example 3 The structural formula of the compound is shown in the following formula I-4-1:
Figure 02_image066
I-4-1 The preparation route is as follows:
Figure 02_image406
The specific operation process of the preparation: Put 0.3 mol of 3-fluoro-4-benzyloxyphenylboronic acid, 0.3 mol of 2-benzyloxy-5-bromo-2-benzaldehyde, 2.0 L of toluene into a 2 L three-necked flask, 0.7 L water, 0.36 mol potassium carbonate, 0.3 g catalyst, heated and refluxed for 3 hours. Standing for liquid separation, column chromatography separation, and toluene/ethanol recrystallization to obtain compound 3-1 as a yellow solid. HPLC: 95%, yield Y=75%.

在2 L三口瓶中投0.1 mol的膦鹽，加降溫至0到-10 ℃之間，分批緩慢加入0.2 mol的叔丁醇鉀，控溫0到-10 ℃之間反應1h、，將0.05 mol的化合物3-1溶於THF滴加到上述反應液，N2 保護下控溫0 ℃反應4小時。反應完畢，降溫，邊攪拌邊倒入冰水中，攪拌30 min，過濾0.5 L石油醚打漿，可得到化合物3-2，LC:90 %，收率Y=80 %。Put 0.1 mol of phosphine salt into a 2 L three-necked flask, add the temperature to 0 to -10 ℃, slowly add 0.2 mol of potassium tert-butoxide in batches, control the temperature between 0 to -10 ℃, and react for 1 hour. 0.05 mol of compound 3-1 was dissolved in THF and added dropwise to the above reaction solution, and reacted for 4 hours under the protection of N 2 at 0°C. After the reaction is completed, the temperature is lowered, and the mixture is poured into ice water while stirring, stirred for 30 min, filtered 0.5 L of petroleum ether to make a slurry, and compound 3-2 can be obtained, LC: 90%, yield Y=80%.

將0.08 mol化合物3-2、6.6 g的Pd/C、0.5 L的THF和0.5 L的EtOH加入1 L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10 min，得到化合物3-3，LC:92 %，收率Y=83 %。Add 0.08 mol of compound 3-2, 6.6 g of Pd/C, 0.5 L of THF and 0.5 L of EtOH into a 1 L three-necked flask, replace with N 2 three times, and replace with H 2 three times. Hydrodebenzylation at 40 ℃, reaction 6 Hour. After the reaction was completed, the celite was filtered, the filtrate was concentrated, PE:EA=10:1, and stirred for 10 min to obtain compound 3-3, LC: 92%, yield Y=83%.

在1 L三口瓶中投0.02 mol的1、0.1 mol的三乙胺、0.5 L 的DCM，N2 保護下控溫0 ℃滴加0.1 mol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50 g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4 h，吸濾，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-4-1， HPLC:99.5 %，收率Y=47 %。Put 0.02 mol of 1, 0.1 mol of triethylamine, 0.5 L of DCM in a 1 L three-necked flask, and add 0.1 mol of methacrylic acid chloride under the protection of N 2 and the temperature is controlled at 0 ℃. After dripping, react at room temperature for 3 hours. After the reaction is complete, add water solution, extract the aqueous phase with DCM, combine the organic phases, wash with saturated brine, dry with anhydrous sodium sulfate, filter, concentrate the filtrate, dissolve 5 times toluene at 45 ℃, pass through a 50 g silica gel column, and wash with 3 times toluene. , Concentrated, 3 times toluene and 3 times alcohol heated to dissolve, frozen at -20 ℃ for 4 h, suction filtered, recrystallized three times according to the same method, and dried to obtain white solid compound I-4-1, HPLC: 99.5% , The yield Y=47%.

實施例4 化合物結構式如下式I-6-2所示：

Figure 02_image096
Ⅰ-6-2 其製備路線如下：
Figure 02_image408
製備的具體操作流程： 在2 L三口瓶中投入0.5 mol的4-苄氧基苯硼酸、0.5 mol的2-苄氧基-5-溴-2-苯甲醛，2.0 L甲苯，0.7 L水，0.36 mol碳酸鉀，催化劑0.3 g，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:95 %，收率Y=75 %。Example 4 The structural formula of the compound is shown in the following formula I-6-2:
Figure 02_image096
Ⅰ-6-2 The preparation route is as follows:
Figure 02_image408
The specific operation process of the preparation: Put 0.5 mol of 4-benzyloxyphenylboronic acid, 0.5 mol of 2-benzyloxy-5-bromo-2-benzaldehyde, 2.0 L of toluene, 0.7 L of water into a 2 L three-necked flask, 0.36 mol potassium carbonate, 0.3 g catalyst, heating and refluxing for 3 hours. Standing for liquid separation, column chromatography separation, and toluene/ethanol recrystallization to obtain compound 4-1 as a yellow solid. HPLC: 95%, yield Y=75%.

用2-苄氧基-5-溴-2-苯酚替代2-苄氧基-5-溴-2-苯甲醛，按照合成化合物4-1的步驟合成化合物A。Using 2-benzyloxy-5-bromo-2-phenol instead of 2-benzyloxy-5-bromo-2-benzaldehyde, compound A was synthesized according to the procedure of compound 4-1.

在2 L三口瓶中投0.1 mol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0.2 mol的叔丁醇鉀，控溫0到-10 ℃之間反應1h、，將0.1 mol的化合物4-1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30 min，過濾0.5 L石油醚打漿，可得到化合物4-2，LC:94 %，收率Y=85 %。Put 0.1 mol of 5-bromopentanol triphenylphosphine salt into a 2 L three-necked flask, add the temperature to 0 to -10 ℃, slowly add 0.2 mol of potassium tert-butoxide in batches, and control the temperature from 0 to -10 After reacting at ℃ for 1 hour, 0.1 mol of compound 4-1 was dissolved in THF and added dropwise to the above system, and reacted at -10 ℃ under the protection of N 2 for 2 hours. After the reaction is completed, the temperature is lowered, and the mixture is poured into ice water while stirring, stirred for 30 min, filtered 0.5 L of petroleum ether to make a slurry, and compound 4-2 can be obtained, LC: 94%, yield Y=85%.

在2 L三口瓶中加入0.1 mol的化合物4 -2再加入0.1 mol化合物A，氮氣保護，降溫至0 ℃，再加入0.15 mol三苯基膦和0.15 mol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30 min，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4-3，LC:94 %，收率Y=70 %。Add 0.1 mol of compound 4-2 to a 2 L three-necked flask, then add 0.1 mol of compound A, protect with nitrogen, and cool to 0 ℃, then add 0.15 mol of triphenylphosphine and 0.15 mol of DEAD, and react at room temperature for 4 hours after the addition is complete After the reaction is complete, cool down, pour into ice water while stirring, stir for 30 min, extract with ethyl acetate, spin dry, recrystallize with 2 times ethanol and 1 times petroleum ether to obtain compound 4-3, LC: 94%, yield Rate Y=70%.

將0.05 mol化合物4-3、3 g的Pd/C、0.5 L的THF和0.5 L的EtOH加入1 L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10 min，得到化合物4-4，LC:95 %，收率Y=73 %。Add 0.05 mol of compound 4-3, 3 g of Pd/C, 0.5 L of THF, and 0.5 L of EtOH into a 1 L three-necked flask, replace with N 2 three times, and replace with H 2 three times. Hydrodebenzylation at 40 ℃, reaction 6 Hour. After the reaction was completed, the celite was filtered, the filtrate was concentrated, PE:EA=10:1, and stirred for 10 min to obtain compound 4-4, LC: 95%, yield Y=73%.

在1 L三口瓶中投0.02 mol的1、0.1 mol的三乙胺、0.5 L 的DCM，N2 保護下控溫0 ℃滴加0.1 mol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50 g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4 h，吸濾，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 0.02 mol of 1, 0.1 mol of triethylamine, 0.5 L of DCM in a 1 L three-necked flask, and add 0.1 mol of methacrylic acid chloride under the protection of N 2 and the temperature is controlled at 0 ℃. After dripping, react at room temperature for 3 hours. After the reaction is complete, add water liquid, extract the aqueous phase with DCM, combine the organic phases, wash with saturated brine, dry with anhydrous sodium sulfate, filter, concentrate the filtrate, dissolve 5 times toluene at 45 ℃, pass through a 50 g silica gel column, and rinse with 3 times toluene. , Concentrated, 3 times toluene and 3 times alcohol heated to dissolve, frozen at -20 ℃ for 4 h, suction filtered, recrystallized three times according to the same method, and dried to obtain white solid compound I-6-2, HPLC: 99.8% , Yield Y=40%.

實施例5 化合物結構式如下式I-7-1所示：

Figure 02_image112
Ⅰ-7-1 其製備路線如下：
Figure 02_image410
製備的具體操作流程： 在2 L三口瓶中投入0.3 mol的3-氟-4-苄氧基苯硼酸、0.3 mol的2-苄氧基-5-溴-2-苯甲酸，2.0 L甲苯，0.7 L水，0.6 mol碳酸鉀，催化劑0.3 g，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5-1黃色固體。HPLC:97 %，收率Y=80 %。Example 5 The structural formula of the compound is shown in the following formula I-7-1:
Figure 02_image112
Ⅰ-7-1 The preparation route is as follows:
Figure 02_image410
The specific operation process of the preparation: Put 0.3 mol of 3-fluoro-4-benzyloxyphenylboronic acid, 0.3 mol of 2-benzyloxy-5-bromo-2-benzoic acid, and 2.0 L of toluene into a 2 L three-necked flask. 0.7 L water, 0.6 mol potassium carbonate, 0.3 g catalyst, heated and refluxed for 3 hours. Standing for liquid separation, column chromatography separation, and toluene/ethanol recrystallization to obtain compound 5-1 as a yellow solid. HPLC: 97%, yield Y=80%.

在3 L三口瓶中投0.2 mol的化合物5-1、0.1 mol的丙二醇、0.05 mol的DMAP，1.0L THF，N2 保護下控溫0 ℃滴加0.3 molDCC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5-2，GC:93 %，收率Y=75 %。In a 3 L three-necked flask, 0.2 mol of compound 5-1, 0.1 mol of propylene glycol, 0.05 mol of DMAP, 1.0L of THF, and N 2 protection were added dropwise with 0.3 mol of DCC in THF at 0°C. After dripping, react at room temperature for 6 hours. After the reaction is complete, filter, concentrate the filtrate, and recrystallize with 3 times ethanol to obtain compound 5-2, GC: 93%, yield Y=75%.

將0.06 mol化合物5-2、5.2g的Pd/C、0.3 L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10 min，得到化合物5-3，HPLC:95 %，收率Y=81 %。Add 0.06 mol of compound 5-2, 5.2g of Pd/C, 0.3 L of THF and 0.2L of EtOH into a 1L three-necked flask, replace with N 2 three times, and replace with H 2 three times. Hydrodebenzylation at 40°C, react for 6 hours . After the reaction was completed, the celite was filtered, the filtrate was concentrated, PE:EA=10:1, and stirred for 10 min to obtain compound 5-3, HPLC: 95%, yield Y=81%.

在500 ml三口瓶中投0.02 mol的5-3、0.1 mol的三乙胺、0.2L 的DCM，N2 保護下控溫0 ℃滴加0.1 mol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4 h，吸濾，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 0.02 mol of 5-3, 0.1 mol of triethylamine, 0.2L of DCM into a 500 ml three-necked flask, and add 0.1 mol of methacrylic acid chloride dropwise under the protection of N 2 and the temperature is controlled at 0 ℃. After dripping, react at room temperature for 3 hours. After the reaction is complete, add water liquid, extract the aqueous phase with DCM, combine the organic phases, wash with saturated brine, dry with anhydrous sodium sulfate, filter, concentrate the filtrate, dissolve 5 times toluene at 45 ℃, pass through a 50g silica gel column, and wash with 3 times toluene. Concentrate, 3 times toluene and 3 times alcohol to dissolve by heating, freezing in a refrigerator at -20 ℃ for 4 h, suction filtering, recrystallizing four times according to the same method, and drying to obtain a white solid compound I-7-1, HPLC: 99%, Yield Y=35%.

實施例6 化合物結構式如下式I-8-3所示：

Figure 02_image412
Ⅰ-8-3 其製備路線如下：
Figure 02_image414
用3-甲氧基-4-苄氧基苯硼酸替代3-氟-4-苄氧基苯硼酸，合成化合物6-2，具體操作過程參考實施例5。Example 6 The structural formula of the compound is shown in the following formula I-8-3:
Figure 02_image412
Ⅰ-8-3 The preparation route is as follows:
Figure 02_image414
Using 3-methoxy-4-benzyloxyphenylboronic acid instead of 3-fluoro-4-benzyloxyphenylboronic acid, compound 6-2 was synthesized. Refer to Example 5 for the specific operation process.

實施例7 化合物結構式如下式I-10-2所示：

Figure 02_image134
Ⅰ-10-2 其製備路線如下：
Figure 02_image416
製備的具體操作流程： 在5 L三口瓶中投入0.3 mol的對苄氧基苯硼酸、0.3 mol的2-苄氧基-5-溴苯酚，2.0 L甲苯，0.7 L水，0.36 mol碳酸鉀，催化劑0.3 g，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7-1黃色固體。HPLC:98 %，收率Y=75 %。Example 7 The structural formula of the compound is shown in the following formula I-10-2:
Figure 02_image134
Ⅰ-10-2 The preparation route is as follows:
Figure 02_image416
The specific operation process of the preparation: Put 0.3 mol of p-benzyloxyphenylboronic acid, 0.3 mol of 2-benzyloxy-5-bromophenol, 2.0 L of toluene, 0.7 L of water, and 0.36 mol of potassium carbonate into a 5 L three-necked flask. The catalyst was 0.3 g, heated and refluxed to react for 3 hours. Standing for liquid separation, column chromatography separation, and toluene/ethanol recrystallization to obtain compound 7-1 as a yellow solid. HPLC: 98%, yield Y=75%.

在3 L三口瓶中投0.2 mol的7-1、0.1 mol的己二酸、0.05 mol的DMAP，1.0L THF，N2 保護下控溫0 ℃滴加0.3 molDCC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7-2，GC:94 %，收率Y=82 %。In a 3 L three-necked flask, 0.2 mol of 7-1, 0.1 mol of adipic acid, 0.05 mol of DMAP, 1.0L of THF, and N 2 protection were added dropwise to 0.3 mol of DCC in THF solution at 0°C. After dripping, react at room temperature for 6 hours. After the reaction is complete, filter, concentrate the filtrate, and recrystallize with 3 times ethanol to obtain compound 7-2, GC: 94%, yield Y=82%.

將0.06 mol化合物7-2、6.0g的Pd/C、0.3 L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10 min，得到化合物7-3，HPLC:95 %，收率Y=75 %。Add 0.06 mol of compound 7-2, 6.0 g of Pd/C, 0.3 L of THF and 0.2 L of EtOH into a 1L three-necked flask, replace with N 2 three times, and replace with H 2 three times. Hydrodebenzylation at 40°C, react for 6 hours . After the reaction was completed, the celite was filtered, the filtrate was concentrated, PE:EA=10:1, and the mixture was stirred for 10 min to obtain compound 7-3. HPLC: 95%, yield Y=75%.

在500 ml三口瓶中投0.02 mol的7-3、0.1 mol的三乙胺、0.2L 的DCM，N2 保護下控溫0 ℃滴加0.1 mol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4 h，吸濾，按照相同的方法再重結晶四次，晾乾，得白色固體化合物I-10-2， HPLC:99.4 %，收率Y=30 %。 [液晶組合物]Put 0.02 mol of 7-3, 0.1 mol of triethylamine, 0.2L of DCM into a 500 ml three-necked flask, and add 0.1 mol of methacrylic acid dropwise under the protection of N 2 and the temperature is controlled at 0 ℃. After dripping, react at room temperature for 3 hours. After the reaction is complete, add water liquid, extract the aqueous phase with DCM, combine the organic phases, wash with saturated brine, dry with anhydrous sodium sulfate, filter, concentrate the filtrate, dissolve 5 times toluene at 45 ℃, pass through a 50g silica gel column, and wash with 3 times toluene. Concentrate, 3 times toluene and 3 times alcohol to dissolve by heating, freeze in a refrigerator at -20 ℃ for 4 h, suction filter, recrystallize four times according to the same method, and air dry to obtain white solid compound I-10-2, HPLC: 99.4%, Yield Y=30%. [Liquid crystal composition]

實施例8 液晶組合物的配方及相應的性能如下表3所示。 表3：液晶組合物的配方及相應的性能 類別 液晶單體代碼 含量（ %） 液晶組合物性能 Ⅲ CCY-3-O2 11 Δε[1KHz, 25 ℃]：-4.7 Δn[589 nm, 25 ℃]：0.099 Cp：81 ℃ γ1 ： 95 mPa.s 該液晶介質在-20 ℃放置240h後未析晶 Ⅲ CPY-3-O2 9 Ⅲ PYP-3-O2 12 Ⅲ COY-5-O2 10 Ⅳ Sb-CpO-O4 8 Ⅱ PP-5-1 10 Ⅱ CC-3-V 25 Ⅱ CC-3-2 5 Ⅴ CCP-3-1 5 Ⅵ CPPC-5-3 5 Ⅰ Ⅰ-1-1 0.15 Example 8 The formula and corresponding properties of the liquid crystal composition are shown in Table 3 below. Table 3: The formula and corresponding properties of the liquid crystal composition category LCD monomer code Content (%) Liquid crystal composition performance Ⅲ CCY-3-O2 11 Δε[1KHz, 25 ℃]: -4.7 Δn[589 nm, 25 ℃]: 0.099 Cp: 81 ℃ γ 1 : 95 mPa.s The liquid crystal medium did not crystallize after being placed at -20 ℃ for 240h Ⅲ CPY-3-O2 9 Ⅲ PYP-3-O2 12 Ⅲ COY-5-O2 10 Ⅳ Sb-CpO-O4 8 Ⅱ PP-5-1 10 Ⅱ CC-3-V 25 Ⅱ CC-3-2 5 Ⅴ CCP-3-1 5 Ⅵ CPPC-5-3 5 Ⅰ Ⅰ-1-1 0.15

實施例9 液晶組合物的配方及相應的性能如下表4所示。 表4：液晶組合物的配方及相應的性能 類別 液晶單體代碼 含量（ %） 液晶組合物性能 Ⅲ CCY-3-O2 11 Δε[1KHz, 25 ℃]：-3.4 Δn[589 nm, 25 ℃]：0.099 Cp：88 ℃ γ1 ： 95mPa.s 該液晶介質在-20 ℃放置240h後未析晶 Ⅲ CPY-3-O2 10 Ⅲ PYP-3-O2 7 Ⅲ CCOY-5-O2 10 Ⅲ COY-3-O2 10 Ⅲ CY-3-O2 5 Ⅲ LY-Cp-O2 5 Ⅲ CLY-3-OCPr 3 Ⅱ CC-3-V 20 Ⅴ CCP-V-1 4 Ⅴ CPP-3-2V1 5 Ⅴ CPP-1V-2 5 Ⅵ CGPC-3-3 5 Ⅰ Ⅰ-2-1 0.1 Example 9 The formula and corresponding properties of the liquid crystal composition are shown in Table 4 below. Table 4: The formula and corresponding properties of the liquid crystal composition category LCD monomer code Content (%) Liquid crystal composition performance Ⅲ CCY-3-O2 11 Δε[1KHz, 25 ℃]: -3.4 Δn[589 nm, 25 ℃]: 0.099 Cp: 88 ℃ γ 1 : 95mPa.s The liquid crystal medium did not crystallize after being placed at -20 ℃ for 240h Ⅲ CPY-3-O2 10 Ⅲ PYP-3-O2 7 Ⅲ CCOY-5-O2 10 Ⅲ COY-3-O2 10 Ⅲ CY-3-O2 5 Ⅲ LY-Cp-O2 5 Ⅲ CLY-3-OCPr 3 Ⅱ CC-3-V 20 Ⅴ CCP-V-1 4 Ⅴ CPP-3-2V1 5 Ⅴ CPP-1V-2 5 Ⅵ CGPC-3-3 5 Ⅰ Ⅰ-2-1 0.1

實施例10 液晶組合物的配方及相應的性能如下表5所示。 表5：液晶組合物的配方及相應的性能 類別 液晶單體代碼 含量（ %） 液晶組合物性能 Ⅲ CCY-3-O2 11 Δε[1KHz, 25 ℃]：-4.9 Δn[589 nm, 25 ℃]：0.101 Cp：83 ℃ γ1 ： 106 mPa.s 該液晶介質在-20 ℃放置240h後未析晶 Ⅲ CPY-3-O2 9 Ⅲ PYP-3-O2 12 Ⅲ CLY-5-O2 10 Ⅳ Sb-CpO-O4 4 Ⅳ Sb-4O-O4 4 Ⅱ PP-5-1 10 Ⅱ CC-3-V 25 Ⅱ CC-3-2 10 Ⅵ CPGiP-5-2 5 Ⅰ Ⅰ-4-1 0.3 Example 10 The formula and corresponding properties of the liquid crystal composition are shown in Table 5 below. Table 5: The formula and corresponding properties of the liquid crystal composition category LCD monomer code Content (%) Liquid crystal composition performance Ⅲ CCY-3-O2 11 Δε[1KHz, 25 ℃]: -4.9 Δn[589 nm, 25 ℃]: 0.101 Cp: 83 ℃ γ 1 : 106 mPa.s The liquid crystal medium did not crystallize after being placed at -20 ℃ for 240h Ⅲ CPY-3-O2 9 Ⅲ PYP-3-O2 12 Ⅲ CLY-5-O2 10 Ⅳ Sb-CpO-O4 4 Ⅳ Sb-4O-O4 4 Ⅱ PP-5-1 10 Ⅱ CC-3-V 25 Ⅱ CC-3-2 10 Ⅵ CPGiP-5-2 5 Ⅰ Ⅰ-4-1 0.3

實施例11 液晶組合物的配方及相應的性能如下表6所示。 表6：液晶組合物的配方及相應的性能 類別 液晶單體代碼 含量（ %） 液晶組合物性能 Ⅲ CY-3-O2 9 Δε[1KHz, 25 ℃]：-4.4 Δn[589 nm, 25 ℃]：0.101 Cp：70 ℃ γ1 ：91 mPa.s 該液晶介質在-20 ℃放置240h後未析晶 Ⅲ CY-5-O2 7 Ⅲ CCY-3-O2 7 Ⅲ CPY-3-O2 10 Ⅲ COY-3-O2 9 Ⅲ CCOY-3-O2 9 Ⅲ PY-3-O2 2 Ⅱ CC-3-V 15 Ⅱ CC-2-3 7 Ⅱ CP-3-O2 4 Ⅱ CP-5-O2 3 Ⅱ CP-3-O1 1 Ⅱ PP-5-1 3 Ⅴ CPP-3-2 3 Ⅴ CPP-1V-2 2 Ⅴ CPP-3-2V1 5 Ⅳ Sc-Cp1O-O4 2 Ⅳ Sb-Cp1O-O4 2 Ⅰ Ⅰ-6-2 0.25 Example 11 The formula and corresponding properties of the liquid crystal composition are shown in Table 6 below. Table 6: The formula and corresponding properties of the liquid crystal composition category LCD monomer code Content (%) Liquid crystal composition performance Ⅲ CY-3-O2 9 Δε[1KHz, 25 ℃]: -4.4 Δn[589 nm, 25 ℃]: 0.101 Cp: 70 ℃ γ 1 : 91 mPa.s The liquid crystal medium did not crystallize after being placed at -20 ℃ for 240h Ⅲ CY-5-O2 7 Ⅲ CCY-3-O2 7 Ⅲ CPY-3-O2 10 Ⅲ COY-3-O2 9 Ⅲ CCOY-3-O2 9 Ⅲ PY-3-O2 2 Ⅱ CC-3-V 15 Ⅱ CC-2-3 7 Ⅱ CP-3-O2 4 Ⅱ CP-5-O2 3 Ⅱ CP-3-O1 1 Ⅱ PP-5-1 3 Ⅴ CPP-3-2 3 Ⅴ CPP-1V-2 2 Ⅴ CPP-3-2V1 5 Ⅳ Sc-Cp1O-O4 2 Ⅳ Sb-Cp1O-O4 2 Ⅰ Ⅰ-6-2 0.25

實施例12 液晶組合物的配方及相應的性能如下表7所示。 表7：液晶組合物的配方及相應的性能 類別 液晶單體代碼 含量（ %） 液晶組合物性能 Ⅲ CY-5-O2 11 Δε[1KHz, 25 ℃]：-3.0 Δn[589 nm, 25 ℃]：0.097 Cp：70 ℃ γ1 ：76 mPa.s 該液晶介質在-20 ℃放置240h後未析晶 Ⅲ PY-3-O2 9 Ⅲ COY-3-O2 16 Ⅳ Sc-CpO-O4 4 Ⅱ PP-5-1 10 Ⅱ CC-3-V1 25 Ⅱ CC-3-2 7 Ⅴ CCP-3-1 12 Ⅴ CPP-3-2 6 Ⅰ Ⅰ-7-1 0.4 Example 12 The formula and corresponding properties of the liquid crystal composition are shown in Table 7 below. Table 7: The formula and corresponding properties of the liquid crystal composition category LCD monomer code Content (%) Liquid crystal composition performance Ⅲ CY-5-O2 11 Δε[1KHz, 25 ℃]: -3.0 Δn[589 nm, 25 ℃]: 0.097 Cp: 70 ℃ γ 1 ：76 mPa.s The liquid crystal medium did not crystallize after being placed at -20 ℃ for 240h Ⅲ PY-3-O2 9 Ⅲ COY-3-O2 16 Ⅳ Sc-CpO-O4 4 Ⅱ PP-5-1 10 Ⅱ CC-3-V1 25 Ⅱ CC-3-2 7 Ⅴ CCP-3-1 12 Ⅴ CPP-3-2 6 Ⅰ Ⅰ-7-1 0.4

實施例13 液晶組合物的配方及相應的性能如下表8所示。 表8：液晶組合物的配方及相應的性能 類別 液晶單體代碼 含量（ %） 液晶組合物性能 Ⅲ CY-3-O2 7 Δε[1KHz, 25 ℃]：-3.5 Δn[589 nm, 25 ℃]：0.120 Cp：83 ℃ γ1 ：95 mPa.s 該液晶介質在-20 ℃放置240h後未析晶 Ⅲ CLY-3-O2 5 Ⅲ CLY-4-O2 2 Ⅲ PY-2O-O2 3 Ⅲ PY-2O-O4 5 Ⅲ PYP-2-3 5 Ⅲ PYP-Cpr1-2 3 Ⅲ CPY-3-O2 7 Ⅲ CCY-3-O2 3 Ⅲ CCOY-3-O2 2 Ⅲ CCOY-4-O2 3 Ⅱ CC-2-3 15 Ⅱ CC-3-V1 3 Ⅱ CC-1-3 2 Ⅱ CC-3-V 7 Ⅱ PP-5-O2 5 Ⅱ PP-1-2V 3 Ⅴ CCP-V-1 3 Ⅴ CPP-3-2 5 Ⅴ CCP-3-1 2 Ⅴ CCP-3-O1 1 Ⅴ CPP-3-2V1 2 Ⅳ Sc-2O-O4 4 Ⅳ Sb-4O-O4 3 Ⅰ Ⅰ-8-3 0.2 Example 13 The formula and corresponding properties of the liquid crystal composition are shown in Table 8 below. Table 8: The formula and corresponding properties of the liquid crystal composition category LCD monomer code Content (%) Liquid crystal composition performance Ⅲ CY-3-O2 7 Δε[1KHz, 25 ℃]: -3.5 Δn[589 nm, 25 ℃]: 0.120 Cp: 83 ℃ γ 1 : 95 mPa.s The liquid crystal medium did not crystallize after being placed at -20 ℃ for 240h Ⅲ CLY-3-O2 5 Ⅲ CLY-4-O2 2 Ⅲ PY-2O-O2 3 Ⅲ PY-2O-O4 5 Ⅲ PYP-2-3 5 Ⅲ PYP-Cpr1-2 3 Ⅲ CPY-3-O2 7 Ⅲ CCY-3-O2 3 Ⅲ CCOY-3-O2 2 Ⅲ CCOY-4-O2 3 Ⅱ CC-2-3 15 Ⅱ CC-3-V1 3 Ⅱ CC-1-3 2 Ⅱ CC-3-V 7 Ⅱ PP-5-O2 5 Ⅱ PP-1-2V 3 Ⅴ CCP-V-1 3 Ⅴ CPP-3-2 5 Ⅴ CCP-3-1 2 Ⅴ CCP-3-O1 1 Ⅴ CPP-3-2V1 2 Ⅳ Sc-2O-O4 4 Ⅳ Sb-4O-O4 3 Ⅰ Ⅰ-8-3 0.2

對比例1 將實施例8中的式Ⅰ所示化合物替換為RM-1，得到對比例1。

Figure 02_image418
RM-1 表9：液晶組合物的配方及相應的性能 類別 液晶單體代碼 含量（ %） 液晶組合物性能 Ⅲ CCY-3-O2 11 Δε[1KHz, 25 ℃]：-4.7 Δn[589 nm, 25 ℃]：0.099 Cp：81 ℃ γ1 ： 95 mPa.s 該液晶介質在-10 ℃放置120h後析晶 Ⅲ CPY-3-O2 9 Ⅲ PYP-3-O2 12 Ⅲ COY-5-O2 10 Ⅳ Sb-CpO-O4 8 Ⅱ PP-5-1 10 Ⅱ CC-3-V 25 Ⅱ CC-3-2 5 Ⅴ CCP-3-1 5 Ⅵ CPPC-5-3 5   RM-1 0.15 Comparative Example 1 The compound represented by Formula I in Example 8 was replaced with RM-1 to obtain Comparative Example 1.
Figure 02_image418
RM-1 Table 9: Liquid crystal composition formula and corresponding properties category LCD monomer code Content (%) Liquid crystal composition performance Ⅲ CCY-3-O2 11 Δε[1KHz, 25 ℃]: -4.7 Δn[589 nm, 25 ℃]: 0.099 Cp: 81 ℃ γ 1 ： 95 mPa.s The liquid crystal medium will crystallize after being placed at -10 ℃ for 120h Ⅲ CPY-3-O2 9 Ⅲ PYP-3-O2 12 Ⅲ COY-5-O2 10 Ⅳ Sb-CpO-O4 8 Ⅱ PP-5-1 10 Ⅱ CC-3-V 25 Ⅱ CC-3-2 5 Ⅴ CCP-3-1 5 Ⅵ CPPC-5-3 5 RM-1 0.15

對比例2 將實施例9中的式Ⅰ所示化合物替換為RM-2，得到對比例2。

Figure 02_image420
RM-2 表10：液晶組合物的配方及相應的性能 類別 液晶單體代碼 含量（ %） 液晶組合物性能 Ⅲ CCY-3-O2 11 Δε[1KHz, 25 ℃]：-3.4 Δn[589 nm, 25 ℃]：0.099 Cp：88 ℃ γ1 ： 95mPa.s 該液晶介質在-10 ℃放置120h後析晶 Ⅲ CPY-3-O2 10 Ⅲ PYP-3-O2 7 Ⅲ CCOY-5-O2 10 Ⅲ COY-3-O2 10 Ⅲ CY-3-O2 5 Ⅲ LY-Cp-O2 5 Ⅲ CLY-3-OCPr 3 Ⅱ CC-3-V 20 Ⅴ CCP-V-1 4 Ⅴ CPP-3-2V1 5 Ⅴ CPP-1V-2 5 Ⅵ CGPC-3-3 5   RM-2 0.1 Comparative Example 2 The compound represented by Formula I in Example 9 was replaced with RM-2, and Comparative Example 2 was obtained.
Figure 02_image420
RM-2 Table 10: Liquid crystal composition formula and corresponding properties category LCD monomer code Content (%) Liquid crystal composition performance Ⅲ CCY-3-O2 11 Δε[1KHz, 25 ℃]: -3.4 Δn[589 nm, 25 ℃]: 0.099 Cp: 88 ℃ γ 1 : 95mPa.s The liquid crystal medium will crystallize after being placed at -10 ℃ for 120h Ⅲ CPY-3-O2 10 Ⅲ PYP-3-O2 7 Ⅲ CCOY-5-O2 10 Ⅲ COY-3-O2 10 Ⅲ CY-3-O2 5 Ⅲ LY-Cp-O2 5 Ⅲ CLY-3-OCPr 3 Ⅱ CC-3-V 20 Ⅴ CCP-V-1 4 Ⅴ CPP-3-2V1 5 Ⅴ CPP-1V-2 5 Ⅵ CGPC-3-3 5 RM-2 0.1

對比例3 將實施例10中的式Ⅰ所示化合物替換為RM-3，得到對比例3。

Figure 02_image422
RM-3 表11：液晶組合物的配方及相應的性能 類別 液晶單體代碼 含量（ %） 液晶組合物性能 Ⅲ CCY-3-O2 11 Δε[1KHz, 25 ℃]：-4.9 Δn[589 nm, 25 ℃]：0.101 Cp：83 ℃ γ1 ： 106 mPa.s 該液晶介質在-10 ℃放置120h後析晶 Ⅲ CPY-3-O2 9 Ⅲ PYP-3-O2 12 Ⅲ CLY-5-O2 10 Ⅳ Sb-CpO-O4 4 Ⅳ Sb-4O-O4 4 Ⅱ PP-5-1 10 Ⅱ CC-3-V 25 Ⅱ CC-3-2 10 Ⅵ CPGiP-5-2 5   RM-3 0.3 由實施例8-13與對比例1-3可以看出，含有本發明可聚合化合物的液晶組合物，在-20 ℃的溫度下，10d未析出，顯示出較好的低溫穩定性。Comparative Example 3 The compound represented by formula I in Example 10 was replaced with RM-3, and Comparative Example 3 was obtained.
Figure 02_image422
RM-3 Table 11: Liquid crystal composition formula and corresponding properties category LCD monomer code Content (%) Liquid crystal composition performance Ⅲ CCY-3-O2 11 Δε[1KHz, 25 ℃]: -4.9 Δn[589 nm, 25 ℃]: 0.101 Cp: 83 ℃ γ 1 : 106 mPa.s The liquid crystal medium will crystallize after being placed at -10 ℃ for 120h Ⅲ CPY-3-O2 9 Ⅲ PYP-3-O2 12 Ⅲ CLY-5-O2 10 Ⅳ Sb-CpO-O4 4 Ⅳ Sb-4O-O4 4 Ⅱ PP-5-1 10 Ⅱ CC-3-V 25 Ⅱ CC-3-2 10 Ⅵ CPGiP-5-2 5 RM-3 0.3 From Examples 8-13 and Comparative Examples 1-3, it can be seen that the liquid crystal composition containing the polymerizable compound of the present invention does not precipitate for 10 days at a temperature of -20°C, showing good low-temperature stability.

擴散性實驗 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，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，最後將一定量含RM的液晶組合物滴入第一基板和第二基板之間的夾層空間的一端的注入口。靜置7h，將夾層結構平均切割，分為兩片：A片和B片，HPLC分別檢測每片的RM含量。其實施例8-13和對比例1-3的測試資料如表12所示。 表12：RM擴散性實驗資料 實驗編號 A片RM含量（ppm） B片RM含量（ppm） AB片含量偏差 實施例8 1521 1556 35 實施例9 1032 1009 23 實施例10 3045 3078 33 實施例11 2511 2551 40 實施例12 4044 4008 34 實施例13 2095 2058 37 對比例1 1512 1619 107 對比例2 986 1099 113 對比例3 3135 3022 113 In the diffusivity experiment, the alignment material was uniformly coated on the surfaces of the first and second substrates. The alignment material can be polyimide. The uniformly coated alignment material is heated and cured at a heating temperature of 230 ℃ to form an alignment layer. Spread spacers on the surface of the substrate, and apply frame glue along the edge of the first substrate, and cure it at 120°C. Then, the first substrate and the second substrate are placed opposite to each other to form a structure with interlayer space. Finally, a certain amount of The RM-containing liquid crystal composition was dropped into the injection port at one end of the interlayer space between the first substrate and the second substrate. After standing for 7 hours, the sandwich structure was evenly cut into two pieces: piece A and piece B, and the RM content of each piece was detected by HPLC. The test data of Examples 8-13 and Comparative Examples 1-3 are shown in Table 12. Table 12: RM diffusion test data Experiment number A piece of RM content (ppm) B slice RM content (ppm) AB tablets content deviation Example 8 1521 1556 35 Example 9 1032 1009 twenty three Example 10 3045 3078 33 Example 11 2511 2551 40 Example 12 4044 4008 34 Example 13 2095 2058 37 Comparative example 1 1512 1619 107 Comparative example 2 986 1099 113 Comparative example 3 3135 3022 113

通過實施例8-13和對比例1-3的擴散性實驗資料可以看出，相比於習知技術，含有本發明可聚合化合物的液晶組合物在A、B兩片中的RM含量偏差較小，顯示出較高的擴散性。It can be seen from the diffusivity experimental data of Examples 8-13 and Comparative Examples 1-3 that, compared with the prior art, the liquid crystal composition containing the polymerizable compound of the present invention has a relatively large deviation in the RM content of the two sheets A and B. Small, showing high diffusivity.

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本領域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，凡是屬於本專利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 merely examples to clearly illustrate this patent, and are not meant to limit the implementation of this patent. For those of ordinary knowledge in the field, the above description Other different forms of changes or changes can be made on this basis. It is not possible to list all the implementation methods here. Any obvious changes or changes derived from the technical solutions of this patent are still within the scope of protection of this patent. .

無without

圖1示出式I-1-1所示可聚合化合物的1 H- NMR譜圖； Figure 1 shows the 1 H-NMR spectrum of the polymerizable compound represented by formula I-1-1;

Claims (10)

一種式Ⅰ所示的可聚合化合物，
Figure 03_image003
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，其中一個或複數個不相鄰的-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，和其中一個或複數個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，且其中一個或複數個不相鄰的-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，其中一個或複數個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。A polymerizable compound represented by formula I,
Figure 03_image003
Ⅰ Wherein, L 1 , L 2 , L 3 , and L 4 each independently represent F atom, Cl atom, -CN, linear alkyl group having 1 to 25 C atoms, branched chain having 3 to 25 C atoms Alkyl group, cyclic alkyl group having 3 to 25 C atoms, alkenyl group having 2 to 25 C atoms, or alkynyl group having 2 to 25 C atoms, of which one or more non-adjacent -CH 2 -Groups are optionally -O-, -S-, -NH-, -CO-, -CO-O-, -O-CO-, -O-CO-O-, so that -O- and/ Or -S- and/or -NH- are not directly connected to each other, and one or more of the 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 +x 4 ≥3; Sp 1 , Sp 2 , Sp 3 , Sp 4 , Sp 5 , Z 1 , and Z 2 each independently represent a single bond, a linear alkyl group having 1 to 25 C atoms, having 3 to 25 A branched alkyl group with three C atoms, a cyclic alkyl group with 3 to 25 C atoms, an alkenyl group with 2 to 25 C atoms, or an alkynyl group with 2 to 25 C atoms, and one or more of them Non-adjacent -CH 2 -groups are optionally -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O- such that -O- And/or -S- are not directly connected to each other in a way that 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 . 根據請求項1所述的可聚合化合物，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，其中一個或複數個不相鄰的-CH2 -基團任選地被-O-、-CO-、-CO-O-、-O-CO-取代，一個或複數個H原子任選被F原子取代； P1 、P2 、P3 、P4 各自獨立地表示
Figure 03_image004
、
Figure 03_image006
、
Figure 03_image008
、
Figure 03_image010
、
Figure 03_image012
、
Figure 03_image014
、
Figure 03_image016
、
Figure 03_image018
、
Figure 03_image020
、
Figure 03_image022
、
Figure 03_image024
、
Figure 03_image026
或
Figure 03_image028
。The polymerizable compound according to claim 1, in the compound represented by formula I: L 1 , L 2 , L 3 , and L 4 each independently represent an alkyl group having 1 to 5 carbon atoms, a fluorine-substituted carbon Alkyl groups with 1 to 5 atoms, alkenyl groups with 2 to 5 carbon atoms, alkoxy groups with 1 to 5 carbon atoms, fluorine-substituted alkoxy groups with 1 to 5 carbon atoms, 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 , and 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 , Z 2 each independently represent a single bond, and the number of carbon atoms is 1-10 The alkyl group, the alkenyl group with 2-10 carbon atoms, or the alkynyl group with 2-10 carbon atoms, 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 , and P 4 each independently represent
Figure 03_image004
,
Figure 03_image006
,
Figure 03_image008
,
Figure 03_image010
,
Figure 03_image012
,
Figure 03_image014
,
Figure 03_image016
,
Figure 03_image018
,
Figure 03_image020
,
Figure 03_image022
,
Figure 03_image024
,
Figure 03_image026
or
Figure 03_image028
. 根據請求項2所述的可聚合化合物，其特徵在於，其選自下述的式Ⅰ-1-1至式Ⅰ-17-2所示化合物之一或由之所組成的群組，
Figure 03_image030
I-1-1
Figure 03_image032
I-1-2
Figure 03_image034
I-1-3
Figure 03_image036
      I-2-1
Figure 03_image038
      I-2-2
Figure 03_image040
 I-2-3
Figure 03_image042
I-2-4
Figure 03_image044
I-2-5
Figure 03_image046
I-2-6
Figure 03_image048
   I-2-7
Figure 03_image050
  I-2-8
Figure 03_image052
 I-2-9
Figure 03_image054
  I-2-10
Figure 03_image056
   I-2-11
Figure 03_image058
  I-2-12
Figure 03_image060
I-3-1
Figure 03_image062
I-3-2
Figure 03_image064
  I-3-3
Figure 03_image066
  I-4-1  
Figure 03_image068
  I-4-2
Figure 03_image070
  I-4-3
Figure 03_image072
  I-4-4
Figure 03_image074
I-4-5
Figure 03_image076
 I-4-6
Figure 03_image078
  I-4-7
Figure 03_image080
  I-4-8
Figure 03_image082
  I-4-9
Figure 03_image084
  I-4-10
Figure 03_image086
 I-4-11
Figure 03_image088
 I-4-12
Figure 03_image090
I-5-1
Figure 03_image092
  I-5-2
Figure 03_image094
I-6-1
Figure 03_image096
  I-6-2
Figure 03_image098
I-6-3
Figure 03_image100
  I-6-4
Figure 03_image102
I-6-5
Figure 03_image104
I-6-6
Figure 03_image106
I-6-7
Figure 03_image108
  I-6-8
Figure 03_image110
    I-6-9
Figure 03_image112
  I-7-1
Figure 03_image114
I-8-1
Figure 03_image116
 I-8-2
Figure 03_image118
I-8-3
Figure 03_image120
 I-8-4
Figure 03_image122
I-8-5
Figure 03_image124
 I-8-6
Figure 03_image126
I-8-7
Figure 03_image128
I-8-8
Figure 03_image130
 I-8-9
Figure 03_image132
I-10-1
Figure 03_image134
 I-10-2
Figure 03_image136
 I-10-3
Figure 03_image138
 I-10-4
Figure 03_image140
    I-10-5
Figure 03_image142
 I-10-6
Figure 03_image144
  I-10-7
Figure 03_image146
 I-10-8  
Figure 03_image148
 I-10-9
Figure 03_image150
  I-12-1
Figure 03_image152
 I-12-2
Figure 03_image154
  I-12-3  
Figure 03_image156
I-12-4
Figure 03_image158
  I-12-5
Figure 03_image160
 I-12-6
Figure 03_image162
 I-12-7
Figure 03_image164
    I-12-8
Figure 03_image166
  I-12-9
Figure 03_image168
 I-14-1
Figure 03_image170
 I-14-2
Figure 03_image172
  I-14-3
Figure 03_image174
 I-14-4
Figure 03_image176
  I-14-5
Figure 03_image178
I-14-6
Figure 03_image180
I-14-7
Figure 03_image182
 I-14-8
Figure 03_image184
I-14-9
Figure 03_image186
I-15-1
Figure 03_image188
  I-15-2
Figure 03_image190
I-15-3
Figure 03_image192
 I-16-1
Figure 03_image194
 I-16-2
Figure 03_image196
 I-16-3
Figure 03_image198
  I-17-1
Figure 03_image200
 I-17-2。
The polymerizable compound according to claim 2, characterized in that it is selected from the group consisting of one of the following compounds represented by formula I-1-1 to formula I-17-2,
Figure 03_image030
I-1-1
Figure 03_image032
I-1-2
Figure 03_image034
I-1-3
Figure 03_image036
I-2-1
Figure 03_image038
I-2-2
Figure 03_image040
I-2-3
Figure 03_image042
I-2-4
Figure 03_image044
I-2-5
Figure 03_image046
I-2-6
Figure 03_image048
I-2-7
Figure 03_image050
I-2-8
Figure 03_image052
I-2-9
Figure 03_image054
I-2-10
Figure 03_image056
I-2-11
Figure 03_image058
I-2-12
Figure 03_image060
I-3-1
Figure 03_image062
I-3-2
Figure 03_image064
I-3-3
Figure 03_image066
I-4-1
Figure 03_image068
I-4-2
Figure 03_image070
I-4-3
Figure 03_image072
I-4-4
Figure 03_image074
I-4-5
Figure 03_image076
I-4-6
Figure 03_image078
I-4-7
Figure 03_image080
I-4-8
Figure 03_image082
I-4-9
Figure 03_image084
I-4-10
Figure 03_image086
I-4-11
Figure 03_image088
I-4-12
Figure 03_image090
I-5-1
Figure 03_image092
I-5-2
Figure 03_image094
I-6-1
Figure 03_image096
I-6-2
Figure 03_image098
I-6-3
Figure 03_image100
I-6-4
Figure 03_image102
I-6-5
Figure 03_image104
I-6-6
Figure 03_image106
I-6-7
Figure 03_image108
I-6-8
Figure 03_image110
I-6-9
Figure 03_image112
I-7-1
Figure 03_image114
I-8-1
Figure 03_image116
I-8-2
Figure 03_image118
I-8-3
Figure 03_image120
I-8-4
Figure 03_image122
I-8-5
Figure 03_image124
I-8-6
Figure 03_image126
I-8-7
Figure 03_image128
I-8-8
Figure 03_image130
I-8-9
Figure 03_image132
I-10-1
Figure 03_image134
I-10-2
Figure 03_image136
I-10-3
Figure 03_image138
I-10-4
Figure 03_image140
I-10-5
Figure 03_image142
I-10-6
Figure 03_image144
I-10-7
Figure 03_image146
I-10-8
Figure 03_image148
I-10-9
Figure 03_image150
I-12-1
Figure 03_image152
I-12-2
Figure 03_image154
I-12-3
Figure 03_image156
I-12-4
Figure 03_image158
I-12-5
Figure 03_image160
I-12-6
Figure 03_image162
I-12-7
Figure 03_image164
I-12-8
Figure 03_image166
I-12-9
Figure 03_image168
I-14-1
Figure 03_image170
I-14-2
Figure 03_image172
I-14-3
Figure 03_image174
I-14-4
Figure 03_image176
I-14-5
Figure 03_image178
I-14-6
Figure 03_image180
I-14-7
Figure 03_image182
I-14-8
Figure 03_image184
I-14-9
Figure 03_image186
I-15-1
Figure 03_image188
I-15-2
Figure 03_image190
I-15-3
Figure 03_image192
I-16-1
Figure 03_image194
I-16-2
Figure 03_image196
I-16-3
Figure 03_image198
I-17-1
Figure 03_image200
I-17-2.
一種液晶組合物，其特徵在於，其包含一種或複數種請求項1-3任一項所述的可聚合化合物。A liquid crystal composition, characterized in that it contains one or more of the polymerizable compounds described in any one of claims 1-3. 根據請求項4所述的液晶組合物，其特徵在於，其還包含一種或複數種下述的式Ⅱ所示化合物以及一種或複數種下述的式Ⅲ所示化合物，
Figure 03_image202
Ⅱ
Figure 03_image204
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；
Figure 03_image206
、
Figure 03_image208
各自獨立地表示
Figure 03_image210
或
Figure 03_image212
； 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 中任意一個或複數個不相鄰的-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、-CH2 CH2 -、-CH2 O-或-OCH2 -；
Figure 03_image214
、
Figure 03_image216
各自獨立地表示
Figure 03_image210
、
Figure 03_image212
、
Figure 03_image218
、
Figure 03_image220
、
Figure 03_image222
、
Figure 03_image224
、
Figure 03_image226
或
Figure 03_image228
m1 表示1或2，當m1 表示2時，
Figure 03_image216
相同或不同； n1 表示0、1或2，當n1 表示2時，
Figure 03_image214
相同或不同。The liquid crystal composition according to claim 4, characterized in that it further comprises one or more compounds represented by the following formula II and one or more compounds represented by the following formula III,
Figure 03_image202
Ⅱ
Figure 03_image204
Ⅲ In formula II, R 1 and R 2 each independently represent an alkyl group with 1-10 carbon atoms, a fluorine-substituted alkyl group with 1-10 carbon atoms, and an alkoxy group with 1-10 carbon atoms. , Fluorine-substituted alkoxy with 1-10 carbon atoms, alkenyl with 2-10 carbon atoms, fluorine-substituted alkenyl with 2-10 carbon atoms, 3-8 carbon atoms Alkenyloxy or fluorine-substituted alkenyloxy with 3-8 carbon atoms;
Figure 03_image206
,
Figure 03_image208
Expressed independently of each other
Figure 03_image210
or
Figure 03_image212
; In formula III, R 3 and R 4 each independently represent an alkyl group having 1-10 carbon atoms, a fluorine-substituted alkyl group having 1-10 carbon atoms, and an alkoxy group having 1-10 carbon atoms. , Fluorine-substituted alkoxy with 1-10 carbon atoms, alkenyl with 2-10 carbon atoms, fluorine-substituted alkenyl with 2-10 carbon atoms, 3-8 carbon atoms Alkenyloxy or fluorine-substituted alkenyloxy with 3-8 carbon atoms, and any one of R 3 and R 4 or multiple non-adjacent -CH 2 -are optionally cyclopentylene, Cyclobutylene or cyclopropylene substitution; Z 1 and Z 2 each independently represent a single bond, -CH 2 CH 2 -, -CH 2 O- or -OCH 2 -;
Figure 03_image214
,
Figure 03_image216
Expressed independently of each other
Figure 03_image210
,
Figure 03_image212
,
Figure 03_image218
,
Figure 03_image220
,
Figure 03_image222
,
Figure 03_image224
,
Figure 03_image226
or
Figure 03_image228
m 1 means 1 or 2, when m 1 means 2,
Figure 03_image216
Same or different; n 1 represents 0, 1 or 2, when n 1 represents 2,
Figure 03_image214
Same or different. 根據請求項5所述的液晶組合物，其特徵在於，所述式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，
Figure 03_image230
 Ⅱ-1
Figure 03_image232
 Ⅱ-2
Figure 03_image234
 Ⅱ-3
Figure 03_image236
 Ⅱ-4
Figure 03_image238
 Ⅱ-5
Figure 03_image240
 Ⅱ-6
Figure 03_image242
 Ⅱ-7
Figure 03_image244
 Ⅱ-8
Figure 03_image246
 Ⅱ-9
Figure 03_image248
 Ⅱ-10
Figure 03_image250
 Ⅱ-11
Figure 03_image252
 Ⅱ-12
Figure 03_image254
 Ⅱ-13
Figure 03_image256
 Ⅱ-14
Figure 03_image258
 Ⅱ-15
Figure 03_image260
 Ⅱ-16
Figure 03_image262
 Ⅱ-17
所述式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，
Figure 03_image264
 Ⅲ-1
Figure 03_image266
 Ⅲ-2
Figure 03_image268
 Ⅲ-3
Figure 03_image270
 Ⅲ-4
Figure 03_image272
 Ⅲ-5
Figure 03_image274
 Ⅲ-6
Figure 03_image276
 Ⅲ-7
Figure 03_image278
 Ⅲ-8
Figure 03_image280
 Ⅲ-9
Figure 03_image282
 Ⅲ-10
Figure 03_image284
 Ⅲ-11
Figure 03_image286
 Ⅲ-12
Figure 03_image288
 Ⅲ-13
Figure 03_image290
 Ⅲ-14
Figure 03_image292
 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取代。The liquid crystal composition according to claim 5, wherein the compound represented by formula II is selected from the group consisting of compounds represented by formula II-1 to formula II-17,
Figure 03_image230
 Ⅱ-1
Figure 03_image232
 Ⅱ-2
Figure 03_image234
 Ⅱ-3
Figure 03_image236
 Ⅱ-4
Figure 03_image238
 Ⅱ-5
Figure 03_image240
 Ⅱ-6
Figure 03_image242
 Ⅱ-7
Figure 03_image244
 Ⅱ-8
Figure 03_image246
 Ⅱ-9
Figure 03_image248
 Ⅱ-10
Figure 03_image250
 Ⅱ-11
Figure 03_image252
 Ⅱ-12
Figure 03_image254
 Ⅱ-13
Figure 03_image256
 Ⅱ-14
Figure 03_image258
 Ⅱ-15
Figure 03_image260
 Ⅱ-16
Figure 03_image262
 Ⅱ-17
The compound represented by formula III is selected from the group consisting of compounds represented by formula III-1 to formula III-15,
Figure 03_image264
 Ⅲ-1
Figure 03_image266
 Ⅲ-2
Figure 03_image268
 Ⅲ-3
Figure 03_image270
 Ⅲ-4
Figure 03_image272
 Ⅲ-5
Figure 03_image274
 Ⅲ-6
Figure 03_image276
 Ⅲ-7
Figure 03_image278
 Ⅲ-8
Figure 03_image280
 Ⅲ-9
Figure 03_image282
 Ⅲ-10
Figure 03_image284
 Ⅲ-11
Figure 03_image286
 Ⅲ-12
Figure 03_image288
 Ⅲ-13
Figure 03_image290
 Ⅲ-14
Figure 03_image292
 Ⅲ-15
Wherein, R 31 and R 41 each independently represent an alkyl group with 1-10 carbon atoms, a fluorine-substituted alkyl group with 1-10 carbon atoms, an alkoxy group with 1-10 carbon atoms, and a fluorine-substituted Alkyloxy with 1-10 carbon atoms, alkenyl with 2-10 carbon atoms, fluorine-substituted alkenyl with 2-10 carbon atoms, and alkenyl with 3-8 carbon atoms Oxy or fluorine-substituted alkenyloxy with 3-8 carbon atoms, and any one or more of non-adjacent -CH 2 -is optionally substituted by cyclopentylene, cyclobutylene or cyclopropylene Substitution. 根據請求項4-6任一項所述的液晶組合物，其特徵在於，所述液晶組合物還包含一種或複數種式Ⅳ所示的化合物，
Figure 03_image294
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-CH2 O-。The liquid crystal composition according to any one of claims 4-6, wherein the liquid crystal composition further comprises one or more compounds represented by formula IV,
Figure 03_image294
Ⅳ Wherein, R 5 and R 6 each independently represent an alkyl group with 1-10 carbon atoms, a fluorine-substituted alkyl group with 1-10 carbon atoms, an alkoxy group with 1-10 carbon atoms, fluorine Substituted alkoxy groups with 1-10 carbon atoms, alkenyl groups with 2-10 carbon atoms, fluorine-substituted alkenyl groups with 2-10 carbon atoms, chains with 3-8 carbon atoms Alkenyloxy or fluorine-substituted alkenyloxy with 3-8 carbon atoms, and any one or more of the non-adjacent -CH 2 -is optionally substituted by cyclopentylene, cyclobutylene or cyclylene Propyl substitution; W represents -O-, -S- or -CH 2 O-. 根據請求項7所述的液晶組合物，其特徵在於，所述液晶組合物還包含一種或複數種式Ⅴ所示的化合物，
Figure 03_image316
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；
Figure 03_image318
、
Figure 03_image320
各自独立地表示
Figure 03_image210
、
Figure 03_image212
或
Figure 03_image226
。The liquid crystal composition according to claim 7, wherein the liquid crystal composition further comprises one or more compounds represented by formula V,
Figure 03_image316
Ⅴ where R 7 and R 8 each independently represent an alkyl group with 1-10 carbon atoms, a fluorine-substituted alkyl group with 1-10 carbon atoms, an alkoxy group with 1-10 carbon atoms, fluorine Substituted alkoxy groups with 1-10 carbon atoms, alkenyl groups with 2-10 carbon atoms, fluorine-substituted alkenyl groups with 2-10 carbon atoms, chains with 3-8 carbon atoms Alkenyloxy or fluorine-substituted alkenyloxy with 3-8 carbon atoms;
Figure 03_image318
,
Figure 03_image320
Expressed independently of each other
Figure 03_image210
,
Figure 03_image212
or
Figure 03_image226
. 根據請求項8所述的液晶組合物，其特徵在於，所述液晶組合物還包含一種或複數種式Ⅵ所示化合物，
Figure 03_image330
Ⅵ； 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；
Figure 03_image332
表示
Figure 03_image210
、
Figure 03_image212
或
Figure 03_image226
； 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 8, wherein the liquid crystal composition further comprises one or more compounds represented by formula VI,
Figure 03_image330
Ⅵ; wherein R 9 and R 10 each independently represent an alkyl group having 1-10 carbon atoms, a fluorine-substituted alkyl group having 1-10 carbon atoms, an alkoxy group having 1-10 carbon atoms, Fluorine-substituted alkoxy groups with 1-10 carbon atoms, alkenyl groups with 2-10 carbon atoms, fluorine-substituted alkenyl groups with 2-10 carbon atoms, and 3-8 carbon atoms Alkenyloxy or fluorine-substituted alkenyloxy with 3-8 carbon atoms;
Figure 03_image332
Express
Figure 03_image210
,
Figure 03_image212
or
Figure 03_image226
; 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. 一種液晶顯示元件或液晶顯示器，其包含請求項1-3任一項所述之化合物，或者請求項4-9中任一項所述之液晶組合物，所述顯示元件或顯示器為主動矩陣顯示元件或顯示器或被動矩陣顯示元件或顯示器。A liquid crystal display element or liquid crystal display comprising the compound according to any one of claims 1-3, or the liquid crystal composition according to any one of claims 4-9, the display element or display being an active matrix display Element or display or passive matrix display element or display.
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