CN117229787B - Holographic polymer dispersed liquid crystal material, volume holographic grating and preparation method thereof - Google Patents
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- 239000000463 material Substances 0.000 title claims abstract description 86
- 239000005276 holographic polymer dispersed liquid crystals (HPDLCs) Substances 0.000 title claims abstract description 83
- 238000002360 preparation method Methods 0.000 title abstract description 6
- 150000001875 compounds Chemical class 0.000 claims abstract description 165
- 239000004973 liquid crystal related substance Substances 0.000 claims abstract description 42
- 239000000178 monomer Substances 0.000 claims abstract description 34
- 230000003287 optical effect Effects 0.000 claims abstract description 14
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 11
- 125000004432 carbon atom Chemical group C* 0.000 claims description 29
- 229910052731 fluorine Inorganic materials 0.000 claims description 23
- 125000001153 fluoro group Chemical group F* 0.000 claims description 20
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 18
- 125000000217 alkyl group Chemical group 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 13
- 125000003545 alkoxy group Chemical group 0.000 claims description 10
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical group C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 claims description 5
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 claims description 4
- 230000001678 irradiating effect Effects 0.000 claims description 2
- -1 acrylic ester Chemical class 0.000 abstract description 4
- 230000000052 comparative effect Effects 0.000 description 14
- 238000006116 polymerization reaction Methods 0.000 description 14
- 229920000642 polymer Polymers 0.000 description 9
- 238000005191 phase separation Methods 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 230000021615 conjugation Effects 0.000 description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 5
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 3
- 125000000876 trifluoromethoxy group Chemical group FC(F)(F)O* 0.000 description 3
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 125000003302 alkenyloxy group Chemical group 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 125000000753 cycloalkyl group Chemical group 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000013307 optical fiber Substances 0.000 description 2
- 230000036632 reaction speed Effects 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- MYWOJODOMFBVCB-UHFFFAOYSA-N 1,2,6-trimethylphenanthrene Chemical compound CC1=CC=C2C3=CC(C)=CC=C3C=CC2=C1C MYWOJODOMFBVCB-UHFFFAOYSA-N 0.000 description 1
- JZEXORLUKMQOFA-UHFFFAOYSA-N 2-(1-ethoxyethyl)-2-(hydroxymethyl)propane-1,3-diol prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.CCOC(C)C(CO)(CO)CO JZEXORLUKMQOFA-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 239000005264 High molar mass liquid crystal Substances 0.000 description 1
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
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Abstract
The invention discloses a holographic polymer dispersed liquid crystal material, a volume holographic grating and a preparation method thereof, wherein the holographic polymer dispersed liquid crystal material comprises a liquid crystal composition, acrylic ester polymerizable monomers and a photoinitiator; the liquid crystal composition comprises compounds shown in the following formulas I-III, and the acrylic polymerizable monomer comprises a trifunctional polymerizable monomer and a compound shown in the following formula IV. According to the holographic polymer dispersed liquid crystal material, the liquid crystal composition with a specific structural formula and the polymerizable monomer are selected, so that the prepared holographic polymer dispersed liquid crystal material has excellent performance, and can be polymerized under the light of a blue light wave band to obtain the volume holographic grating, so that the prepared volume holographic grating has high diffraction efficiency and low haze, can be switched between a holographic state and a transparent state, and can meet the application requirements of the volume holographic optical waveguide.
Description
Technical Field
The invention relates to the technical field of liquid crystal materials, in particular to a holographic polymer dispersed liquid crystal material, a volume holographic grating and a preparation method thereof.
Background
The holographic polymer dispersed liquid crystal (Holographic polymer dispersed liquid crystal, HPDLC) is a novel holographic material and has the outstanding advantages of low cost, simple manufacturing process, high diffraction efficiency, low haze and the like. The holographic polymer dispersed liquid crystal material is subjected to polymerization reaction through exposure to form a volume holographic grating with polymers and liquid crystals arranged periodically, and at present, the green HPDLC material is basically mature, however, as the wavelength of blue light is shorter and the energy is higher than that of green light, the rate of polymerization reaction is difficult to control, and the diffraction efficiency and haze of the volume holographic grating are affected.
Disclosure of Invention
The present invention aims to solve at least one of the technical problems existing in the prior art. Therefore, the invention provides a holographic polymer dispersed liquid crystal material, a volume holographic grating and a preparation method thereof, wherein the holographic polymer dispersed liquid crystal material is designed, and a liquid crystal composition with a specific structural formula and a polymerizable monomer are selected to obtain the holographic polymer dispersed liquid crystal material which has excellent performance, so that the holographic polymer dispersed liquid crystal material can be polymerized under the light of a blue light wave band to obtain the volume holographic grating, and the prepared volume holographic grating has high diffraction efficiency and low haze.
A holographic polymer dispersed liquid crystal material according to the first aspect of the present invention, the holographic polymer dispersed liquid crystal material comprising a liquid crystal composition, an acrylic polymerizable monomer and a photoinitiator;
the liquid crystal composition comprises compounds shown in the following formulas I-III, and the acrylic polymerizable monomer comprises a trifunctional polymerizable monomer and a compound shown in the following formula IV:
a compound of formula i:；
a compound of formula ii:；
a compound of formula iii:；
a compound of formula iv:；
wherein R is 1 、R 2 、R 3 And R is 4 Independent representations、/>、/>、/>An alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, wherein at least one hydrogen atom may be substituted with a fluorine atom;
and->Independent representation->Or->；
X represents F, CF 3 、OCF 3 ；
L 1 ~L 6 Each independently represents a fluorine atom or a hydrogen atom;
m and n each independently represent 0 or 1;
Sp 1 、Sp 2 each independently represents a single bond or a linear alkyl group having 1 to 6 carbon atoms, at least one or more-CH(s) in the linear alkyl group having 1 to 6 carbon atoms 2 -may be substituted by-O-, -COO-, or-c=c-;
Y 1 represents a fluorine atom, a chlorine atom, an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkenyloxy group having 2 to 6 carbon atoms or a cycloalkyl group having 3 to 6 carbon atoms;
p represents 1, 2, 3, 4 or 5; q represents 0, 1, 2, 3 or 4, and when p is 2, 3, 4 or 5, Y 1 And q may be the same or different.
In some embodiments, the compound of formula I comprises at least one of the compounds of formulas I-1 through I-6 as follows:
a compound of formula i-1:；
a compound of formula i-2:；
a compound of formula i-3:；
a compound of formula i-4:；
a compound of formula i-5:；
a compound of formula i-6:。
in some embodiments, the compound of formula II comprises at least one of the compounds of formulas II-1 through II-6:
a compound of formula ii-1:；
a compound of formula ii-2:；
a compound of formula ii-3:；
a compound of formula ii-4:；
of II-5The compounds are shown as follows:；
a compound of formula ii-6:。
in some embodiments, the compound of formula III includes at least one of the compounds of formulas III-1 through III-6 as follows:
a compound of formula iii-1:；
a compound of formula iii-2:；
a compound of formula iii-3:；
a compound of formula iii-4:；
a compound of formula iii-5:；
a compound of formula iii-6:。
in some embodiments, the compound of formula IV comprises at least one of the compounds of formulas IV-1 through IV-4 as follows:
a compound of formula iv-1:；
a compound of formula iv-2:；
a compound of formula iv-3:；
a compound of formula iv-4:。
in some alternative embodiments, the trifunctional polymerizable monomer is trimethylolpropane triacrylate and the photoinitiator is bis 2, 6-difluoro-3-pyrrolophenyltitanocene.
In some alternative embodiments, the method comprises the following steps in percentage by mass:
the compound shown in the formula I is 1% -30%;
the compound shown in the formula II is 5% -40%;
the compound shown in the formula III is 5% -30%;
the compound shown in the formula IV is 40% -70%;
the three-functional group polymerizable monomer is 5% -10%;
the photoinitiator accounts for 0.1% -1%.
In a second aspect, an embodiment of the present invention further provides a method for preparing a volume holographic grating, where the method includes: the holographic polymer dispersed liquid crystal material is irradiated with light in the blue wavelength band to form a volume holographic grating.
In some embodiments, before irradiating the holographic polymer dispersed liquid crystal material with light in the blue wavelength band to form a volume holographic grating, the method further comprises:
according to the formula amount, the liquid crystal composition, the acrylic polymerizable monomer and the photoinitiator are mixed under the light-shielding condition to obtain the holographic polymer dispersed liquid crystal material.
In a third aspect, embodiments of the present invention further provide a volume hologram grating,
the volume holographic grating is prepared by the method.
Compared with the prior art, the invention has the following beneficial effects:
the holographic polymer dispersed liquid crystal material prepared by designing the holographic polymer dispersed liquid crystal material and selecting the liquid crystal composition with a specific structural formula and the polymerizable monomer has excellent performance, can be polymerized under the light of a blue light wave band to obtain the volume holographic grating, has high diffraction efficiency and low haze, can be switched between a holographic state and a transparent state, and can meet the application requirements of the volume holographic optical waveguide.
Additional aspects and advantages of the invention will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention.
Detailed Description
To facilitate understanding of the present invention, examples are set forth below. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
The embodiment of the invention discloses a holographic polymer dispersed liquid crystal material, which comprises a liquid crystal composition, acrylic polymerizable monomers and a photoinitiator; the liquid crystal composition comprises compounds shown in the following formulas I-III, and the acrylic polymerizable monomer comprises a trifunctional polymerizable monomer and a compound shown in the following formula IV.
Specifically, the compounds of formula I are:wherein R is 1 Representation->、/>、/>、/>An alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, wherein at least one hydrogen atom may be substituted with a fluorine atom. It is understood that where at least one hydrogen atom may be replaced by a fluorine atom means、/>、/>、/>An alkyl group having 1 to 7 carbon atoms, wherein in the alkoxy group having 1 to 7 carbon atoms, a hydrogen atom is not substituted with a fluorine atom, or at least one hydrogen atom is substituted with a fluorine atom.
L 1 And L 2 Each independently represents a fluorine atom or a hydrogen atom.
In the embodiment of the invention, the benzene ring and the alkyne bond contained in the compound shown in the formula I have high conjugation, so that the compound shown in the formula I has larger double refractive index, the refractive index modulation degree of the holographic polymer dispersed liquid crystal material can be improved, the diffraction efficiency of the volume holographic grating is improved, and the material intersolubility is improved by trifluoromethoxy, so that the material is not easy to separate out, and the overall performance of the holographic polymer dispersed liquid crystal material is improved.
In embodiments of the present invention, the compound of formula I may be at least one of the following compounds I-1 to I-6:
a compound of formula i-1:；
a compound of formula i-2:；
a compound of formula i-3:；
a compound of formula i-4:；
a compound of formula i-5:；
a compound of formula i-6:。
the above compounds are only examples of some of the compounds represented by the formula i, and should not be construed as limiting the compounds represented by the formula i.
Further, the compound represented by formula II is:wherein R is 2 Representation->、/>、/>、/>An alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, wherein at least one hydrogen atom may be substituted with a fluorine atom. It is understood that wherein at least one hydrogen atom may be substituted by a fluorine atom means +.>、/>、/>、/>An alkyl group having 1 to 7 carbon atoms, wherein in the alkoxy group having 1 to 7 carbon atoms, a hydrogen atom is not substituted with a fluorine atom, or at least one hydrogen atom is substituted with a fluorine atom.
Representation->Or->The method comprises the steps of carrying out a first treatment on the surface of the m represents 0 or 1; l (L) 3 、L 4 、L 5 、L 6 Each independently represents a fluorine atom or a hydrogen atom; x represents F, CF 3 Or OCF (optical clear) 3 。
In the embodiment of the invention, the difluoromethoxy bridge structure in the compound shown in the formula II has excellent intersolubility, so that the intersolubility among various compounds in the holographic polymer dispersed liquid crystal material is improved, the compounds are not easy to separate out, and the overall performance of the holographic polymer dispersed liquid crystal material is improved.
In an embodiment of the present invention, the compound represented by formula II may be at least one of the following compounds II-1 to II-6:
a compound of formula ii-1:；
a compound of formula ii-2:；
a compound of formula ii-3:；
a compound of formula ii-4:；
a compound of formula ii-5:；
a compound of formula ii-6:。
the above compounds are only examples of some of the compounds represented by the formula ii, and should not be construed as limiting the compounds represented by the formula ii.
Further, the compound of formula III is:wherein R is 3 And R is 4 Independent representation->、/>、/>、/>An alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, wherein at least one hydrogen atom may be substituted with a fluorine atom. It is understood that wherein at least one hydrogen atom may be substituted by a fluorine atom means +.>、/>、/>、/>Alkyl groups having 1 to 7 carbon atoms, wherein the hydrogen atoms in the alkoxy groups having 1 to 7 carbon atoms are not replaced by fluorine atomsSubstituted, or at least one hydrogen atom is substituted with a fluorine atom.
Representation->Or->The method comprises the steps of carrying out a first treatment on the surface of the n represents 0 or 1;
in the embodiment of the invention, the terphenyl or the tetrabiphenyl structure in the compound shown in the formula III has extremely high conjugation, so that the compound shown in the formula III has larger double refractive index, the refractive index modulation degree of the holographic polymer dispersed liquid crystal material can be improved, the diffraction efficiency of the volume holographic grating is improved, the compound shown in the formula III has higher clear point, and the temperature application range of the holographic polymer dispersed liquid crystal material can be widened.
In an embodiment of the present invention, the compound represented by formula III may be at least one of the following compounds III-1 to III-6:
a compound of formula iii-1:；
a compound of formula iii-2:；
a compound of formula iii-3:；
a compound of formula iii-4:；
a compound of formula iii-5:；
a compound of formula iii-6:。
the above compounds are only examples of some of the compounds represented by formula iii, and should not be construed as limiting the compounds represented by formula iii.
Further, the compound shown in the formula IV is:wherein Sp is 1 、Sp 2 Each independently represents a single bond or a linear alkyl group having 1 to 6 carbon atoms, at least one or more of which is-CH 2 -may be substituted by-O-, -COO-or-c=c-.
Y 1 Represents a fluorine atom, a chlorine atom, an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkenyloxy group having 2 to 6 carbon atoms or a cycloalkyl group having 3 to 6 carbon atoms.
p represents 1, 2, 3, 4 or 5; q represents 0, 1, 2, 3 or 4. When p represents 2, 3, 4 or 5, Y 1 And q may be the same or different, for example, when p represents 2, two (Y 1 ) q structure, two (Y 1 ) The q structures may be identical, i.e. q are each 0, 1, 2, 3 or 4, and Y 1 The radicals indicated are also identical, e.g. Y 1 All are fluorine atoms and the like; alternatively, two (Y 1 ) The q structure may also be different, wherein two Y's are possible 1 And two different from each other, may be two Y 1 Different or two q different. It will be appreciated that when p represents 3, 4 or 5, Y 1 And q may be the same or different, and are not described in detail herein.
In the embodiment of the invention, the compound shown in the formula IV is a polymerizable monomer containing liquid crystal property, so that the phase state of liquid crystal can be maintained, two acrylic ester reaction sites are arranged in the compound shown in the formula IV, a crosslinked polymer network can be formed, and the central benzene ring structure can promote the intersolubility of the compound shown in the formula IV and the liquid crystal composition and regulate the polymerization reaction rate.
The diffraction efficiency is determined by the refractive index modulation degree of the holographic polymer dispersed liquid crystal, the haze is determined by the size of the formed liquid crystal droplet, the phase separation rate of the liquid crystal composition and the polymerizable monomer during exposure determines the refractive index modulation degree and the liquid crystal droplet size, the polymerization speed is too high, the liquid crystal droplet size is large, the haze is high, the polymerization speed is too slow, the liquid crystal is wrapped by the polymer, the phase separation cannot be completed, and the refractive index modulation degree is low.
In the embodiment of the invention, the holographic polymer dispersed liquid crystal material comprises a compound shown in a formula I, a compound shown in a formula II, a compound shown in a formula III and a compound shown in a formula IV, wherein a benzene ring and an alkyne bond contained in the compound shown in the formula I have high conjugation, and a terphenyl or tetrabiphenyl structure in the compound shown in the formula III has extremely high conjugation, so that the birefringence of a liquid crystal composition can be improved, the refractive index modulation degree of the holographic polymer dispersed liquid crystal material can be improved, the diffraction efficiency of a volume holographic grating can be improved, and the mutual solubility between the liquid crystal composition can be improved by a trifluoromethoxy structure contained in the compound shown in the formula I and a difluoromethoxy bridge structure in the compound shown in the formula II. Therefore, the holographic polymer dispersed liquid crystal material of the embodiment of the invention ensures that the rate of polymerization reaction of the holographic polymer dispersed liquid crystal material under blue light irradiation is moderate through the coordination of various groups in the compound shown in the formula I, the compound shown in the formula II, the compound shown in the formula III and the compound shown in the formula IV, and the holographic polymer dispersed liquid crystal material forms a volume holographic grating with high diffraction efficiency and low haze.
In an embodiment of the present invention, the compound of formula IV may be at least one of the following compounds of formulas IV-1 to IV-6:
a compound of formula iv-1:；
a compound of formula iv-2:；
a compound of formula iv-3:；
a compound of formula iv-4:。
the above compounds are only examples of some of the compounds represented by the formula iv, and should not be construed as limiting the compounds represented by the formula iv.
In practical researches, the inventor finds that when a holographic polymer dispersed liquid crystal material undergoes polymerization reaction, as the polymerization reaction proceeds, liquid crystal and polymer undergo phase separation, the speed of the polymerization reaction is a key factor influencing the phase separation, if the reaction speed is too high, the polymer cannot form a grating structure, if the reaction speed is too low, the liquid crystal can be wrapped by the polymer, the phase separation cannot be completed, the diffraction efficiency is low, the haze is increased, and the wavelength of blue light is shorter, the energy is higher, so that the crosslinking reaction rate of the holographic polymer dispersed liquid crystal material is high during polymerization, the difficulty of controlling the reaction rate is increased, and the phase separation difficulty of the liquid crystal and the polymer is increased.
According to the holographic polymer dispersed liquid crystal material provided by the embodiment of the invention, the holographic polymer dispersed liquid crystal material is designed, and the liquid crystal composition with a specific structural formula and the polymerizable monomer are selected, so that the prepared holographic polymer dispersed liquid crystal material has excellent performance, can be polymerized under the light of a blue light wave band to obtain the volume holographic grating, and the prepared volume holographic grating has high diffraction efficiency and low haze, can be switched between a holographic state and a transparent state, and can meet the application requirements of the volume holographic optical waveguide.
In some embodiments, the trifunctional polymerizable monomer is trimethylolpropane triacrylate (Trimethylolpropane triacrylate, TMPTA) and the photoinitiator is bis 2, 6-difluoro-3-pyrrolophenyltitanocene (784). Of course, the embodiment of the present invention is not limited thereto, and the trifunctional polymerizable monomer may be pentaerythritol triacrylate, pentaerythritol tetraacrylate, pentaerythritol tetra-3-mercapto acrylate, ethoxy trimethylolpropane triacrylate, or the like, and the trifunctional polymerizable monomer may be one, two, or more; the photoinitiator may also be 184, TPO, TPOL, 651, 369, etc.; the photoinitiator may be one kind, two kinds or more.
In some embodiments, the holographic polymer dispersed liquid crystal material provided by the invention has a content of 1% -30% of the compound shown in the formula I, for example, the content of the compound shown in the formula I can be 1%, 5%, 10%, 15%, 20%, 25%, 30% and the like; the content of the compound shown in the formula II is 5% -40%, for example, the content of the compound shown in the formula II can be 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40% and the like; the content of the compound represented by formula III is 5% -30%, for example, the content of the compound represented by formula III may be 5%, 10%, 15%, 20%, 25%, 30%, etc.; the content of the compound shown in the formula IV is 40% -70%, for example, the content of the compound shown in the formula IV can be 40%, 45%, 50%, 55%, 60%, 65%, 70% and the like; the content of the trifunctional polymerizable monomer is 5% -10%, for example, the content of the trifunctional polymerizable monomer may be 5%, 6%, 7%, 8%, 9%, 10%, etc.; the content of the photoinitiator is 0.1% -1%, for example, the content of the photoinitiator may be 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, etc.
The holographic polymer dispersed liquid crystal material provided by the present invention is specifically described below by way of a number of examples.
Example 1
The embodiment provides a holographic polymer dispersed liquid crystal material, which comprises the following components in percentage by weight:
example 2
The embodiment provides a holographic polymer dispersed liquid crystal material, which comprises the following components in percentage by weight:
example 3
The embodiment provides a holographic polymer dispersed liquid crystal material, which comprises the following components in percentage by weight:
example 4
The embodiment provides a holographic polymer dispersed liquid crystal material, which comprises the following components in percentage by weight:
example 5
The embodiment provides a holographic polymer dispersed liquid crystal material, which comprises the following components in percentage by weight:
comparative example 1
The comparative example provides a holographic polymer dispersed liquid crystal material comprising the following components in percentage by weight:
comparative example 2
The comparative example provides a holographic polymer dispersed liquid crystal material comprising the following components in percentage by weight:
comparative example 3
The comparative example provides a holographic polymer dispersed liquid crystal material comprising the following components in percentage by weight:
comparative example 4
The comparative example provides a holographic polymer dispersed liquid crystal material comprising the following components in percentage by weight:
the performance test results of the holographic polymer dispersed liquid crystal materials provided in the above examples and comparative examples are shown in table 1 below:
in comparative example 2, after the phase separation by exposure, liquid crystal particles were precipitated, and it was not possible to test the diffraction efficiency and haze because the liquid crystal could not form a nematic phase at room temperature.
According to the holographic polymer dispersed liquid crystal material provided by the invention, the holographic polymer dispersed liquid crystal material comprises a compound shown in a formula I, a compound shown in a formula II, a compound shown in a formula III and a compound shown in a formula IV, and the benzene ring and alkyne bond contained in the compound shown in the formula I have high conjugation, and the terphenyl or the tetrabiphenyl structure in the compound shown in the formula III has extremely high conjugation, so that the birefringence of a liquid crystal composition can be improved, the refractive index modulation degree of the holographic polymer dispersed liquid crystal material is further improved, the diffraction efficiency of a volume holographic grating is improved, the trifluoro methoxy group contained in the compound shown in the formula I and the difluoro methoxy bridge structure in the compound shown in the formula II can improve the intersolubility between the liquid crystal composition, and meanwhile, the benzene ring structure in the center of the compound shown in the formula IV can improve the intersolubility between the compound shown in the formula IV and the liquid crystal composition, and the polymerization reaction rate is regulated, the rate of the holographic polymer dispersed liquid crystal material is moderate under blue light irradiation, the holographic polymer has the specific structural liquid crystal composition, the holographic diffraction rate can be obtained by selecting the liquid crystal composition, the holographic polymer with the specific structural formula, the holographic polymer dispersed liquid crystal material has the diffraction efficiency, and the holographic diffraction efficiency can be switched between the holographic optical grating and the holographic optical grating with the holographic optical wave band of which can be obtained, and the holographic optical grating has the holographic optical grating with the high diffraction performance of which can be obtained by the holographic optical grating and has the holographic optical grating with the high diffraction state of between the holographic optical fiber 1.77% -1.1.77%, and the holographic optical fiber 1.1.1.
Compared with examples 1-5, if the liquid crystal composition contains only any two of the compounds represented by formula I, formula II or formula III (comparative examples 1-3), the prepared holographic polymer dispersed liquid crystal material has poor properties, and cannot be used for preparing a volume hologram grating (comparative example 2), or the prepared volume hologram grating has low diffraction efficiency (comparative examples 1, 3).
Compared with the embodiment 1-embodiment 5, if the polymerizable monomer with other structural formulas is selected (comparative example 4), the prepared holographic polymer dispersed liquid crystal material has poorer performance, and the prepared volume holographic grating has low diffraction efficiency and higher haze.
In summary, the holographic polymer dispersed liquid crystal material is designed, and the liquid crystal composition with a specific structural formula and the polymerizable monomer are selected, so that the prepared holographic polymer dispersed liquid crystal material has excellent performance, the holographic polymer dispersed liquid crystal material can be polymerized under the light of a blue light wave band to obtain the volume holographic grating, and the prepared volume holographic grating has high diffraction efficiency and low haze, can be switched between a holographic state and a transparent state, and can meet the application requirements of the volume holographic optical waveguide.
In a second aspect, the present invention provides a method for preparing a volume holographic grating, the method comprising the steps of S1: the holographic polymer dispersed liquid crystal material is irradiated with light in the blue wavelength band to form a volume holographic grating.
It is understood that the blue light band refers to light having a wavelength ranging from 400nm to 500nm, and for example, in this embodiment, the holographic polymer dispersed liquid crystal material is irradiated with laser light having a wavelength of 473nm, and the holographic polymer dispersed liquid crystal material is polymerized to form a volume hologram grating.
It can be understood that the shorter wavelength of blue light and higher energy result in fast crosslinking reaction rate of the holographic polymer dispersed liquid crystal material during polymerization, which increases the difficulty of controlling the reaction rate and increases the difficulty of separating liquid crystal from polymer. The holographic polymer dispersed liquid crystal material provided by the embodiment of the invention has excellent performance by selecting the liquid crystal composition with a specific structural formula and the polymerizable monomer, can be polymerized under the light of a blue light wave band to obtain the volume holographic grating, has high diffraction efficiency and low haze, can be switched between a holographic state and a transparent state, and can meet the application requirements of the volume holographic optical waveguide.
In some embodiments, step S1 is preceded by step S0: according to the formula amount, the liquid crystal composition, the acrylic polymerizable monomer and the photoinitiator are mixed under the light-shielding condition to obtain the holographic polymer liquid crystal material.
It should be noted that, since the holographic polymer dispersed liquid crystal material undergoes polymerization reaction after exposure, and the reaction rate is related to the wavelength of light, the liquid crystal composition, the acrylic polymerizable monomer and the photoinitiator are mixed under the condition of light shielding, so that the polymerization reaction rate of the holographic polymer dispersed liquid crystal material can be better controlled, the diffraction efficiency of the volume holographic grating is further improved, and the haze of the volume holographic grating is reduced.
In a third aspect, the present invention provides a volume holographic grating, which is prepared from the holographic polymer dispersed liquid crystal material by the preparation method.
The applicant states that the present invention is illustrated by the above examples as a composition of the holographic polymer dispersed liquid crystal material of the present invention, but the present invention is not limited to the composition of the detailed holographic polymer dispersed liquid crystal material described above, i.e. it does not mean that the present invention must be practiced depending on the composition of the detailed holographic polymer dispersed liquid crystal material described above. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of raw materials for the product of the present invention, addition of auxiliary components, selection of specific modes, etc., falls within the scope of the present invention and the scope of disclosure.
Furthermore, the terms "first," "second," and the like, are used for descriptive purposes only and are not to be construed as indicating or implying a relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include one or more such feature. In the description of the present invention, the meaning of "a plurality" is two or more, unless explicitly defined otherwise.
In the description of the present specification, a description referring to terms "one embodiment," "some embodiments," "examples," "specific examples," or "some examples," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms are not necessarily directed to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, the different embodiments or examples described in this specification and the features of the different embodiments or examples may be combined and combined by those skilled in the art without contradiction.
While embodiments of the present invention have been shown and described, it will be understood by those of ordinary skill in the art that: many changes, modifications, substitutions and variations may be made to the embodiments without departing from the spirit and principles of the invention, the scope of which is defined by the claims and their equivalents.
Claims (8)
1. A holographic polymer dispersed liquid crystal material, characterized in that the holographic polymer dispersed liquid crystal material comprises a liquid crystal composition, an acrylic polymerizable monomer and a photoinitiator;
the liquid crystal composition comprises a compound shown in the following formula I-III, wherein the acrylic polymerizable monomer comprises a trifunctional polymerizable monomer and a compound shown in the following formula IV-1-IV-4, the trifunctional polymerizable monomer is trimethylolpropane triacrylate, and the photoinitiator is bis-2, 6-difluoro-3-pyrrolyl titanocene:
a compound of formula i:；
a compound of formula ii:；
a compound of formula iii:；
a compound of formula iv-1:；
a compound of formula iv-2:；
a compound of formula iv-3:；
a compound of formula iv-4:；
wherein R is 1 、R 2 、R 3 And R is 4 Independent representations、/>、/>、/>An alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, wherein at least one hydrogen atom may be substituted with a fluorine atom;
and->Independent representation->Or->；
X represents F, CF 3 Or OCF (optical clear) 3 ；
L 1 ~L 6 Each independently represents a fluorine atom or a hydrogen atom;
m and n each independently represent 0 or 1.
2. The holographic polymer dispersed liquid crystal material of claim 1, in which the compound of formula i comprises at least one of the compounds of formulae i-1 to i-6:
a compound of formula i-1:；
a compound of formula i-2:；
a compound of formula i-3:；
a compound of formula i-4:；
a compound of formula i-5:；
a compound of formula i-6:。
3. the holographic polymer dispersed liquid crystal material of claim 1, in which the compound of formula ii comprises at least one of the compounds of formulae ii-1 to ii-6:
a compound of formula ii-1:；
a compound of formula ii-2:；
a compound of formula ii-3:；
a compound of formula ii-4:；
a compound of formula ii-5:；
a compound of formula ii-6:。
4. the holographic polymer dispersed liquid crystal material of claim 1, in which the compound of formula iii comprises at least one of the compounds of formulae iii-1 to iii-6:
a compound of formula iii-1:；
a compound of formula iii-2:；
a compound of formula iii-3:；
a compound of formula iii-4:；
a compound of formula iii-5:；
a compound of formula iii-6:。
5. the holographic polymer dispersed liquid crystal material of claim 1, comprising, in mass percent:
the compound shown in the formula I is 1% -30%;
the compound shown in the formula II is 5% -40%;
the compound shown in the formula III is 5% -30%;
the compounds shown in the formulas IV-1 to IV-4 are 40% -70%;
the three-functional group polymerizable monomer is 5% -10%;
the photoinitiator accounts for 0.1% -1%.
6. A method of producing a volume holographic grating, the method comprising: a holographic polymer dispersed liquid crystal material according to any one of claims 1 to 5 irradiated with light in the blue wavelength band to form a volume holographic grating.
7. The method of producing a volume hologram according to claim 6, further comprising, before irradiating the holographic polymer dispersed liquid crystal material according to any one of claims 1 to 5 with light in a blue wavelength band to form a volume hologram, the steps of:
mixing the liquid crystal composition, the acrylic polymerizable monomer and the photoinitiator according to the formula amount under the light-shielding condition to obtain the holographic polymer dispersed liquid crystal material as claimed in any one of claims 1 to 5.
8. A volume holographic grating is characterized in that,
the volume hologram grating is prepared by the method of claim 6 or claim 7.
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