CN111848499B - Compound light stabilizer, and preparation method and application thereof - Google Patents
Compound light stabilizer, and preparation method and application thereof Download PDFInfo
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- CN111848499B CN111848499B CN201910350437.0A CN201910350437A CN111848499B CN 111848499 B CN111848499 B CN 111848499B CN 201910350437 A CN201910350437 A CN 201910350437A CN 111848499 B CN111848499 B CN 111848499B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
- C07D211/92—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with a hetero atom directly attached to the ring nitrogen atom
- C07D211/94—Oxygen atom, e.g. piperidine N-oxide
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
- C09K19/54—Additives having no specific mesophase characterised by their chemical composition
Abstract
The invention belongs to the field of light stabilizers, and particularly relates to a compound light stabilizer, wherein the structural formula of the compound is shown as the general formula (I)
Description
Technical Field
The present invention is in the field of light stabilizers. In particular to a compound light stabilizer, a preparation method and application thereof.
Background
The stabilizer is an additive of a high molecular product, can shield or absorb the energy of ultraviolet rays, quenches singlet oxygen groups, decomposes peroxide into inactive substances and the like, and is capable of eliminating or slowing down the possibility of photochemical reaction and preventing or delaying the process of photoaging under the radiation of light, thereby achieving the purpose of prolonging the service life of the high molecular product.
In recent years there have been successive reports of photoinitiators for liquid-crystalline media, however, for many practical applications of liquid-crystalline displays, the known liquid-crystalline media are not sufficiently stable, in particular their stability to UV and even to conventional backlight radiation leads to impairment in particular of the electrical properties, for example, a significant increase in the electrical conductivity, etc. According to the disclosure therein, liquid crystal mixtures using these types of stabilizers have their voltage holding ratio reduced after exposure to light, and moreover color yellowing and the like often occur.
The prior art liquid-crystalline media with correspondingly low addressing voltages have relatively low resistance values or low VHR and often lead to undesirable flicker and inadequate transmission in the display, and furthermore they are not sufficiently stable to thermal and UV exposure. On the other hand, the addressing voltages of prior art displays with high VHR are generally high, in particular for displays which are not directly or discontinuously connected to the supply network, so that the response time of the liquid-crystalline medium in the display has to be improved, i.e. has to be reduced, which is particularly important for displays for television or multimedia applications, for which there has been repeated mention in the past of optimizing the rotational viscosity of the liquid-crystalline medium, achieving the lowest possible rotational viscosity, however, the results achieved are not sufficient for many applications, and further optimization methods have therefore to be sought.
Sufficient stabilization of the media with respect to extreme loads, in particular with respect to UV exposure and heating, is of utmost importance, in particular in the case of display applications for mobile devices, the MLC displays disclosed to date having disadvantages due to their relatively low contrast, relatively high viewing angle dependence and the difficulty of producing gray levels in these displays, as well as their inadequate VHR and their inadequate service life.
There is thus still a great need for a device having a very high specific resistance while having a large operating temperature range, a short response time and a low threshold voltage, by means of which various gray levels can be produced and which has a good and stable VHR.
Disclosure of Invention
The first object of the present invention is to provide a novel light stabilizer compound having good heat resistance, mutual solubility, stability and low rotational viscosity, and a liquid crystal composition containing the light stabilizer compound has a high specific resistance value, a low threshold voltage, good stability especially against degradation by heat and UV exposure and a stable high VHR, and has important application values.
The compound provided by the invention has the following structure (shown in a general formula I):
the R is2Denotes H, F, alkyl or alkoxy of 1 to 12 carbon atoms or alkanyl or alkoxyalkenyl having 2 to 12 carbon atoms in which H may be substituted by F, one or more non-adjacent-CH2-may each independently be substituted by-O-, but with the proviso that the O atoms are not directly attached to each other;
z is1、Z2、Z3Independently of one another- (CH)2) One of- (O-), - (C ═ O) -, or- (C ═ C) -, but does not simultaneously represent-O-;
m and n are the same or different, and m + n is more than or equal to 0 and less than or equal to 12;
0≤K≤12。
preferably, said R is2Denotes H, F, alkyl or alkoxy of 1 to 6 carbon atoms or alkanyl or alkoxyalkenyl having 2 to 6 carbon atoms in which H may be substituted by F, one or more non-adjacent-CH2-may each independently be substituted by-O-, but with the proviso that the O atoms are not directly attached to each other;
z is1、Z2Independently of one another- (CH)2)-；
Z is3Is represented by- (CH)2) -, -O-or- (C ═ C) -, the O atoms not being directly linked to each other;
m and n are the same or different, and m + n is more than or equal to 0 and less than or equal to 12;
0≤K≤6。
preferably, K ═ 0, the compound has the formula (II)
Preferably, the structure is selected from one or more of the following structures:
further preferably, the structural formula is:
the invention also provides a preparation method of the compound light stabilizer, which comprises the following steps:
to be provided with
As raw materials, the raw materials are subjected to esterification reaction to obtain
Wherein R in the compound involved in each step2、m、n、k、Z1、Z2、Z3With R in the resulting compound product2、m、n、k、Z1、Z2、Z3The radicals represented correspond.
Preferably, the
The feeding molar ratio of (2.0-4.0): 1;
further preferably, the molar ratio is (2.0 to 3.0): 1.
Preferably, the temperature of the esterification reaction is between-30 ℃ and 50 ℃.
Further preferably, the reaction temperature is-10 ℃ to 30 ℃;
preferably, the esterification reaction time is 4-12 h;
further preferably, the reaction time is 6-10 h;
preferably, the catalyst used in the reaction process is one or more of dicyclohexylcarbodiimide, concentrated sulfuric acid, p-toluenesulfonic acid and the like;
more preferably dicyclohexylcarbodiimide.
As described above
Can be synthesized by publicly available commercial methods or by methods known per se in the literature.
The method of the invention, if necessary, involves conventional post-treatment, such as: extracting with dichloromethane, ethyl acetate or toluene, separating, washing with water, drying, evaporating with vacuum rotary evaporator, and purifying the obtained product by reduced pressure distillation or recrystallization and/or chromatographic separation, without any special limitation.
The compound of the invention can be stably and efficiently obtained by the preparation method.
A third object of the invention is to protect compositions containing stabilizers for said compounds.
The amount of the compound stabilizer added is preferably 1ppm to 1000ppm, more preferably 1ppm to 800ppm, and still more preferably 1ppm to 500 ppm.
The fourth object of the present invention is to protect the use of said compounds and compositions containing said compounds in the field of liquid crystal displays, preferably in liquid crystal display devices. The liquid crystal display device includes, but is not limited to, TN, ADS, VA, PSVA, FFS or IPS liquid crystal display.
The compound stabilizer has good rotational viscosity and liquid crystal intersolubility, excellent low-temperature working effect performance, excellent thermal stability, chemical stability, optical stability, mechanics and other performances, and a liquid crystal composition containing the compound has high specific resistance, low threshold voltage and high response speed, particularly has good stability and stable high VHR for thermal and UV exposed degradation, and has important application value.
Detailed Description
The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
The starting materials are commercially available from the open literature unless otherwise specified.
According to the conventional detection method in the field, various performance parameters of the compound are obtained through linear fitting, wherein the specific meanings of the performance parameters are as follows:
Δ n represents optical anisotropy (25 ℃); Δ ε represents the dielectric anisotropy (25 ℃, 1000 Hz); ε | represents the dielectric constant (25 ℃, 1000Hz) in the direction parallel to the molecular axis; cp represents a clearing point; k represents the elastic constant (25 ℃); VHR represents a voltage holding ratio; v0 threshold voltage, capacitive, 20 ℃ (V); γ 1 represents the rotational viscosity (mPa.s, 25 ℃).
Example 1
This example provides a compound having the formula:
this example also provides the synthetic route for the preparation of compound BYLC-01 as follows:
the method comprises the following specific steps:
under the protection of nitrogen, 43.2g of 2,2,6, 6-tetramethylpiperidine-1, 4-diol, 23.2g of 2-cyclohexylmalonic acid, 3.1g of 4-dimethylaminopyridine and 400ml of dichloromethane are added into a reaction bottle, stirred for 0.5 hour, the temperature is controlled to be-10-5 ℃, a solution consisting of 52.5g of dicyclohexylcarbodiimide and 100ml of dichloromethane is added dropwise, and the reaction is carried out for 6 hours at room temperature. Conventional work-up, chromatographic purification and elution with n-hexane gave 51.8g of a light pink solid (compound BYLC-01), LC: 99.8%, yield: 83.6 percent.
The resulting BYLC-01 was analyzed by LC-MS and the M/z of the product was 496.1(M +).
Elemental analysis: c: 65.28, H: 9.73, N: 5.64, O: 19.32.
example 2
This example provides a compound having the formula:
this example also provides the synthetic route for the preparation of compound BYLC-02 as follows:
the method comprises the following specific steps:
under the protection of nitrogen, 38.0g of 2,2,6, 6-tetramethylpiperidine-1, 4-diol, 23.5g of 3-cyclohexylglutaric acid, 2.8g of 4-dimethylaminopyridine and 500ml of dichloromethane are added into a reaction bottle, stirred for 0.5 hour, the temperature is controlled to be-5 ℃, a solution consisting of 47.4g of dicyclohexylcarbodiimide and 100ml of dichloromethane is added dropwise, and the reaction is carried out for 8 hours at room temperature. Conventional work-up was carried out, purified by chromatography and eluted with n-hexane to give 45.3g of a light pink solid (compound BYLC-02), LC: 99.7%, yield: 78.6 percent.
The BYLC-02 obtained was analyzed by LC-MS and the M/z of the product was 524.1(M +).
Elemental analysis: c: 66.38, H: 9.98, N: 5.34, O: 18.28.
example 3
This example provides a compound having the formula:
the present example also provides a preparation method: 55.4g (compound BYLC-03) was synthesized in the same manner as in example 1 and example 2, using 2,2,6, 6-tetramethylpiperidine-1, 4-diol and 4-cyclohexylpimelic acid as starting materials (LC: 99.6%, yield: 82.5 percent.
The resulting BYLC-03 was analyzed by LC-MS and the M/z of the product was 552.1(M +).
Elemental analysis: c: 67.35, H: 10.21, N: 5.07, O: 17.37.
example 4
This example provides a compound having the formula:
the present example also provides a preparation method: using 2,2,6, 6-tetramethylpiperidine-1, 4-diol and 2-cyclohexylsuccinic acid as raw materials, 43.8g (compound BYLC-04) was synthesized in the same manner as in example 1, LC: 99.8%, yield: 86.2 percent.
The BYLC-04 analysis by LC-MS gave a product with M/z of 510.1(M +).
Elemental analysis: c: 65.85, H: 9.87, N: 5.46, O: 18.80.
example 5
This example provides a compound having the formula:
this example was prepared in the same manner as in example 1 except that 52.6g (compound BYLC-05) was synthesized, LC: 99.8%, yield: 81.7 percent.
The BYLC-05 obtained was analyzed by LC-MS and the M/z of the product was 514.1(M +).
Elemental analysis: c: 63.02, H: 9.21, F: 3.68, N: 5.44, O: 18.66.
example 6
This example provides a compound having the formula:
this example was prepared in the same manner as in example 1 except that 22.8g (compound BYLC-06), LC: 99.7%, yield: 75.9 percent.
The BYLC-06 product was analyzed by LC-MS and had M/z of 566.1(M +).
Elemental analysis: c: 67.80, H: 10.31, N: 4.94, O: 11.94.
example 7
This example provides a compound having the formula:
this example was prepared in the same manner as in examples 1 and 2, and 28.6g (compound BYLC-07) was synthesized, LC: 99.8%, yield: 88.2 percent.
The BYLC-07 obtained was analyzed by LC-MS and the M/z of the product was 522.1(M +).
Elemental analysis: c: 66.63, H: 9.64, N: 5.36, O: 18.36.
according to the technical schemes of the embodiment 1 and the embodiment 2, other compounds provided by the patent can be obtained only by simply replacing corresponding raw materials and not changing any substantial operation.
Comparative example
Photostability test
Selecting a liquid crystal mixture, wherein the liquid crystal type is as follows: BYLC-HJ-1100, (manufactured by billions of space-time liquid crystal technologies ltd.) first, the stability of the voltage holding ratio of the liquid crystal mixture (BYLC-HJ-1100) itself was determined, and the stability of the liquid crystal mixture (BYLC-HJ-1100) itself to light was investigated by means of cold cathode ((CCFL) -LCD backlight) illumination in a test cell with electrodes for homeotropic alignment material and planar ITO. In a specific operation, the corresponding test cell is exposed to light for 1000 hours and then the voltage holding ratio is determined in each case after 5 minutes at a temperature of 100 ℃. Setting six parallel experiments in the testing process, wherein the shown values are the average value of six single values and the standard deviation of the six single values, including the condition that the standard deviation is smaller than the precision of the measured value;
thermal stability test
The test cell obtained above was stored in a sealed manner in a conventional laboratory heating cabinet at 100 ℃ for 120 hours, and the voltage holding ratio thereof was measured after 5 minutes at 100 ℃, 1V and 60Hz (VHR, heat, 120 hours).
Experimental example 1
250ppm of the compound of example 1 (i.e.BYLC-01) were added to the liquid crystal mixture BYLC-HJ-1100 of comparative example 1 (manufactured by Byobo space-time liquid Crystal technology Co., Ltd.) to give a mixture M-1, 250ppm of example 2(BYLC-02) were added to the liquid crystal mixture BYLC-HJ-1100 (manufactured by Byobo space-time liquid Crystal technology Co., Ltd.) to give a mixture M-2, and the stability was investigated in accordance with the method described above, with the results shown in the following table:
photostability test Table 1
Thermal stability test Table 2
As can be seen from the above mixture experimental examples, the starting mixture without using a stabilizer shows considerable reduction in VHR after backlight exposure, whereas the mixture using the compound provided by the present invention has a VHR before exposure superior to that of the mixture of comparative example, and the VHR does not change much after exposure, shows excellent thermal stability, chemical stability, optical stability, etc., has good stability against degradation by thermal and UV exposure and a stable high VHR, effectively reduces the occurrence probability of image delay, maintains a low threshold voltage, improves response time, and prolongs service life.
Experimental example 2
200ppm of the compound of example 3 (i.e., BYLC-03) were added to a liquid crystal mixture BYLC-HJ-1100 (manufactured by billions of space-time liquid Crystal technology Co., Ltd.) to give a mixture M-3, 200ppm of example 4(BYLC-04) were added to a liquid crystal mixture BYLC-HJ-1100 (manufactured by billions of space-time liquid Crystal technology Co., Ltd.) to give a mixture M-4, and the stability was investigated in accordance with the above-mentioned method, and the results are shown in the following table.
Photostability test Table 3
Thermal stability test Table 4
As can be seen from the above mixture experimental examples, the starting mixture without using a stabilizer shows considerable reduction in VHR after backlight exposure, whereas the mixture using the compound provided by the present invention has a VHR before exposure superior to that of the mixture of comparative example, and the VHR does not change much after exposure, shows excellent thermal stability, chemical stability, optical stability, etc., has good stability against degradation by thermal and UV exposure and a stable high VHR, effectively reduces the occurrence probability of image delay, maintains a low threshold voltage, improves response time, and prolongs service life.
Although the invention has been described in detail hereinabove by way of general description, specific embodiments and experiments, it will be apparent to those skilled in the art that many modifications and improvements can be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.
Claims (15)
1. A compound light stabilizer, which is characterized in that the structural formula of the compound is shown as the general formula (II)
R2Represents H;
Z1、Z2independently of one another- (CH)2)-；
m and n are the same or different, and m + n is more than or equal to 0 and less than or equal to 12.
2. The compound light stabilizer of claim 1, selected from one of the following structures:
3. a compound light stabilizer according to claim 1 or 2, characterized in that it has the formula:
4. a process for producing the compound as claimed in claim 1,
to be provided with
As raw materials, the raw materials are subjected to esterification reaction to obtain
Wherein R in the compound involved in each step2、m、n、Z1、Z2With R in the resulting compound product2、m、n、Z1、Z2The radicals represented correspond.
5. The method of claim 4, wherein the step of preparing the composition is carried out in the presence of a catalyst
The feeding molar ratio of (2.0-4.0): 1.
6. the method of claim 5, wherein the step of preparing the composition is carried out in a batch process
The feeding molar ratio of (2.0-3.0): 1.
7. The process according to claim 4 or 5, wherein the esterification reaction is carried out at a temperature of between-30 ℃ and 50 ℃;
and/or the esterification reaction time is 4-12 h;
and/or the catalyst used in the reaction process is one or more of dicyclohexylcarbodiimide, concentrated sulfuric acid and p-toluenesulfonic acid.
8. The method according to claim 7, wherein the esterification reaction is carried out at a reaction temperature of-10 ℃ to 30 ℃.
9. The preparation method according to claim 7, wherein the reaction time of the esterification reaction is 6-10 h.
10. A composition comprising the compound light stabilizer according to any one of claims 1 to 3, wherein the compound light stabilizer is added in an amount of 1ppm to 1000 ppm.
11. The composition of claim 10, wherein the compound light stabilizer is added in an amount of 1ppm to 800 ppm.
12. The composition of claim 11, wherein the compound light stabilizer is added in an amount of 1ppm to 500 ppm.
13. Use of the composition according to any one of claims 10 to 12 in the field of liquid crystal displays.
14. Use of the composition of any one of claims 10 to 12 in a liquid crystal display device.
15. The use according to claim 14, wherein the liquid crystal display device is a TN, ADS, VA, PSVA, FFS or IPS liquid crystal display.
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| CN102746218A (en) * | 2011-04-21 | 2012-10-24 | 默克专利股份有限公司 | Compounds and liquid crystalline medium |
| WO2013022607A1 (en) * | 2011-08-08 | 2013-02-14 | Transitions Optical, Inc. | Mesogenic stabilizers |
| CN103773388A (en) * | 2012-10-18 | 2014-05-07 | 默克专利股份有限公司 | Liquid crystal medium, method for the stabilisation thereof and liquid crystal display |
| CN103834414A (en) * | 2012-10-18 | 2014-06-04 | 默克专利股份有限公司 | Liquid-crystalline medium, method for the stabilization thereof, and liquid-crystal display |
| CN105384681A (en) * | 2014-09-02 | 2016-03-09 | 默克专利股份有限公司 | Compounds and liquid-crystalline medium |
| CN108373441A (en) * | 2017-01-30 | 2018-08-07 | 默克专利股份有限公司 | Compound and liquid crystal media |
| CN108373924A (en) * | 2017-01-30 | 2018-08-07 | 默克专利股份有限公司 | Compound and liquid crystal media |
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2019
- 2019-04-28 CN CN201910350437.0A patent/CN111848499B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102746218A (en) * | 2011-04-21 | 2012-10-24 | 默克专利股份有限公司 | Compounds and liquid crystalline medium |
| WO2013022607A1 (en) * | 2011-08-08 | 2013-02-14 | Transitions Optical, Inc. | Mesogenic stabilizers |
| CN103773388A (en) * | 2012-10-18 | 2014-05-07 | 默克专利股份有限公司 | Liquid crystal medium, method for the stabilisation thereof and liquid crystal display |
| CN103834414A (en) * | 2012-10-18 | 2014-06-04 | 默克专利股份有限公司 | Liquid-crystalline medium, method for the stabilization thereof, and liquid-crystal display |
| CN105384681A (en) * | 2014-09-02 | 2016-03-09 | 默克专利股份有限公司 | Compounds and liquid-crystalline medium |
| CN108373441A (en) * | 2017-01-30 | 2018-08-07 | 默克专利股份有限公司 | Compound and liquid crystal media |
| CN108373924A (en) * | 2017-01-30 | 2018-08-07 | 默克专利股份有限公司 | Compound and liquid crystal media |
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