CN114478808A - Cellulose acetate containing benzene ring substituent, preparation method and application thereof - Google Patents
Cellulose acetate containing benzene ring substituent, preparation method and application thereof Download PDFInfo
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- 229920002301 cellulose acetate Polymers 0.000 title claims abstract description 133
- 238000002360 preparation method Methods 0.000 title description 10
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 50
- 238000006243 chemical reaction Methods 0.000 claims abstract description 39
- 238000000034 method Methods 0.000 claims abstract description 39
- 239000000178 monomer Substances 0.000 claims abstract description 37
- 239000007788 liquid Substances 0.000 claims abstract description 32
- 150000001266 acyl halides Chemical class 0.000 claims abstract description 27
- 239000012970 tertiary amine catalyst Substances 0.000 claims abstract description 18
- 239000003495 polar organic solvent Substances 0.000 claims abstract description 17
- 238000005886 esterification reaction Methods 0.000 claims abstract description 14
- 239000012295 chemical reaction liquid Substances 0.000 claims abstract description 11
- 239000008367 deionised water Substances 0.000 claims abstract description 11
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000000926 separation method Methods 0.000 claims abstract description 10
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 5
- 229920000875 Dissolving pulp Polymers 0.000 claims abstract description 3
- 239000010408 film Substances 0.000 claims description 61
- 239000012788 optical film Substances 0.000 claims description 46
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 21
- 230000003287 optical effect Effects 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 15
- 239000002253 acid Substances 0.000 claims description 11
- 239000007787 solid Substances 0.000 claims description 11
- 230000035484 reaction time Effects 0.000 claims description 10
- 150000004820 halides Chemical class 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
- 150000002148 esters Chemical class 0.000 claims description 7
- 125000001424 substituent group Chemical group 0.000 claims description 6
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- 125000002252 acyl group Chemical group 0.000 claims description 3
- 230000000052 comparative effect Effects 0.000 description 22
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 20
- 238000012360 testing method Methods 0.000 description 19
- 230000009477 glass transition Effects 0.000 description 15
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 description 12
- 230000033228 biological regulation Effects 0.000 description 12
- 230000008569 process Effects 0.000 description 11
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 10
- 239000004973 liquid crystal related substance Substances 0.000 description 9
- 238000002834 transmittance Methods 0.000 description 8
- 239000000654 additive Substances 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 7
- 238000006555 catalytic reaction Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 238000002464 physical blending Methods 0.000 description 6
- 150000001242 acetic acid derivatives Chemical class 0.000 description 5
- 230000001105 regulatory effect Effects 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- -1 tertiary amine compound Chemical class 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229920002284 Cellulose triacetate Polymers 0.000 description 2
- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- MDKAAWDKKBFSTK-UHFFFAOYSA-N 2-ethoxybenzoyl chloride Chemical compound CCOC1=CC=CC=C1C(Cl)=O MDKAAWDKKBFSTK-UHFFFAOYSA-N 0.000 description 1
- NQUVCRCCRXRJCK-UHFFFAOYSA-N 4-methylbenzoyl chloride Chemical compound CC1=CC=C(C(Cl)=O)C=C1 NQUVCRCCRXRJCK-UHFFFAOYSA-N 0.000 description 1
- FBBRKYLXMNQFQU-UHFFFAOYSA-N 4-pentylbenzoyl chloride Chemical compound CCCCCC1=CC=C(C(Cl)=O)C=C1 FBBRKYLXMNQFQU-UHFFFAOYSA-N 0.000 description 1
- 235000010724 Wisteria floribunda Nutrition 0.000 description 1
- 230000021736 acetylation Effects 0.000 description 1
- 238000006640 acetylation reaction Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000009529 body temperature measurement Methods 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- QKIUAMUSENSFQQ-UHFFFAOYSA-N dimethylazanide Chemical compound C[N-]C QKIUAMUSENSFQQ-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
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- 239000012265 solid product Substances 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B3/00—Preparation of cellulose esters of organic acids
- C08B3/22—Post-esterification treatments, including purification
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
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- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Biochemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Optics & Photonics (AREA)
- Engineering & Computer Science (AREA)
- General Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Polarising Elements (AREA)
Abstract
The invention discloses a cellulose acetate containing benzene ring substituent, preparing method and application, which comprises the following steps: dissolving cellulose acetate in a polar organic solvent; adding a tertiary amine catalyst and an acyl halide monomer containing a benzene ring into the obtained solution in sequence, and reacting the acyl halide monomer containing the benzene ring with cellulose acetate to obtain a reaction solution containing an esterification reaction product; pouring the reaction liquid into deionized water to obtain heterogeneous liquid; and carrying out solid-liquid separation on the heterogeneous liquid to obtain the cellulose acetate containing the benzene ring substituent.
Description
Technical Field
The disclosure belongs to the technical field of functional optical film preparation, and particularly relates to cellulose acetate containing benzene ring substituent, and a preparation method and application thereof.
Background
Liquid Crystal Displays (LCDs) have been widely used in various display fields such as color liquid crystal televisions, tablet computers, smart phones, etc. because of their light weight, thinness, portability, and low power consumption, and have been the leading position in the display industry. Polarizers are the most central technical components of LCDs. The triacetyl cellulose film (TAC) is used as a protective film of a polarizer as an important component of an optical film device due to excellent characteristics of transparency, heat resistance, proper moisture permeability and the like, a compensation film prepared from the TAC is an indispensable material for improving color shift and visual angle of a liquid crystal display, and the adjustment and control of in-plane and out-of-plane birefringence of the compensation film are very important for improving the imaging quality of a liquid crystal screen.
At present, the production and processing techniques of TAC compensation films are mainly mastered by fuji and konica, japan. The in-plane and out-of-plane birefringence of the TAC compensation film are mainly realized by formula regulation and control and physical blending process regulation and control, the formula regulation and control are mainly realized by additives such as retardation reinforcing agents, retardation inhibitors and the like, and the process regulation and control are mainly realized by regulating a stretching mode, a stretching ratio and the like. However, the additive added by formula regulation is easy to cause the problems of uneven distribution, migration and precipitation in the production process and the like, thereby influencing the uniformity and consistency of the optical performance of the TAC compensation film. In addition, the industrialized physical blending process can only obtain the single regulation and control effect and rule of a certain specific additive, and the precise control and quantitative regulation of the compensation performance cannot be realized. Thus, there is still a need for a process that provides a cellulose film that provides accurate control and quantitative adjustment of compensation properties, and avoids the need for an industrial physical blending process.
Disclosure of Invention
In view of the above technical problems, the present disclosure provides a cellulose acetate containing benzene ring substituent, and a preparation method and applications thereof, so as to at least partially solve the above technical problems.
In order to solve the above technical problem, one technical solution of the present disclosure is as follows:
a method for preparing cellulose acetate containing benzene ring substituent comprises the following steps:
dissolving cellulose acetate in a polar organic solvent;
adding a tertiary amine catalyst and an acyl halide monomer containing a benzene ring into the obtained solution in sequence, and reacting the acyl halide monomer containing the benzene ring with cellulose acetate to obtain a reaction solution containing an esterification reaction product;
pouring the reaction liquid into deionized water to obtain heterogeneous liquid;
and carrying out solid-liquid separation on the heterogeneous liquid to obtain the cellulose acetate containing the benzene ring substituent.
In one embodiment, the above cellulose acetate ester containing a phenyl ring substituent has the following structural formula:
In one embodiment, the polar organic solvent includes any one of: dimethylformamide, dimethylacetamide, dimethyl sulfoxide, acetone;
the structural formula of the acyl halide monomer containing the benzene ring is as follows:
The tertiary amine catalyst includes any one of:
In one embodiment, the mass ratio of the cellulose acetate to the polar organic solvent is in the range including: 1: 10 to 15.
In one embodiment, the range of the molar ratio of the tertiary amine catalyst to the benzene ring-containing acid halide monomer includes: 1: 1-3: 1;
the mole ratio of the benzene ring-containing acyl halide monomer to the cellulose acetate is in the range of 1.2-10: 1;
the reaction temperature range for obtaining the reaction solution includes: 20-100 ℃;
the reaction time range for obtaining the reaction solution includes: 2-24 h.
In one embodiment, the mass ratio of the reaction solution to the deionized water ranges from: 1: 50-200.
In one embodiment, the method further comprises the following steps: after the heterogeneous liquid is subjected to solid-liquid separation, purifying and drying the obtained solid;
the drying method comprises the following steps: vacuum drying;
the temperature range of the drying comprises: 80-120 ℃;
the time ranges of the drying include: 2-48 h.
Another technical solution of the present disclosure includes: the cellulose acetate containing benzene ring substituent prepared by the method.
Still another technical solution of the present disclosure includes: the cellulose acetate containing benzene ring substituent is applied to optical films.
In another embodiment, the optical film includes an optical compensation film.
The cellulose acetate containing benzene ring substituent group, the preparation method and the application thereof provided by the disclosure have at least one of the following beneficial effects:
(1) in the embodiment of the disclosure, a tertiary amine catalyst and an acyl halide monomer containing a benzene ring substituent are sequentially added into a polar organic solvent containing cellulose acetate, on one hand, the acyl halide monomer containing a benzene ring can fully react with the cellulose acetate due to the existence of the catalyst; on the other hand, the acyl halide monomer containing the benzene ring substituent and cellulose acetate are subjected to esterification reaction to generate cellulose acetate reaction liquid containing the benzene ring substituent. And pouring the obtained cellulose acetate reaction liquid containing the benzene ring substituent into deionized water, and cleaning redundant catalyst or acyl halide monomer containing the benzene ring to obtain heterogeneous liquid containing white solid, wherein the heterogeneous liquid contains the cellulose acetate containing the benzene ring substituent. And then, carrying out solid-liquid separation on the heterogeneous liquid, and purifying and drying to obtain the cellulose acetate containing the benzene ring substituent. The structure of the obtained cellulose acetate containing benzene ring substituent can be controlled by adjusting the parameters such as the proportion of reaction substrates, the reaction time, the reaction temperature and the like in the esterification reaction of the cellulose acetate and the acyl halide monomer containing benzene ring under the catalysis of the tertiary amine catalyst, and further the basic parameters and the optical performance of the optical film prepared from the cellulose acetate containing benzene ring substituent can be regulated and controlled.
(2) In the embodiment of the disclosure, the cellulose acetate containing a benzene ring substituent is applied to the optical film, and the aromatic substituent containing a benzene ring with a specific structure is introduced into the cellulose acetate optical film, so that the polarizability and the refractive index of the material can be effectively improved, and the modified cellulose acetate has good optical transmittance and birefringence on the premise of keeping the original heat resistance and mechanical properties of the cellulose acetate. Compared with the traditional physical blending process and formula regulation mode, the double refraction performance can be regulated without adding additives, and the phenomena of uneven distribution and migration precipitation of the additives caused by physical blending are effectively avoided.
(3) In the embodiment of the disclosure, the preparation method of the cellulose acetate containing the benzene ring is simple, has low technical requirements and wide raw material sources, has high popularization and application values and wide development prospects, and is beneficial to application in display equipment such as liquid crystal display devices and flexible display devices.
Drawings
Fig. 1 is a principal component diagram of a conventional liquid crystal display device;
FIG. 2 is a flow chart of a process for preparing cellulose acetate esters containing a benzene ring substituent according to an embodiment of the present disclosure.
Detailed Description
In order to make the objects, technical solutions and advantages of the present disclosure more apparent, the present disclosure is further described in detail below with reference to the accompanying drawings in combination with the embodiments.
Aiming at the problems of uneven additive distribution, easy precipitation in the production process, incapability of carrying out precise control and quantitative regulation and the like existing in the preparation of a cellulose triacetate optical compensation film by using a formula regulation technology and a physical blending process and considering different requirements of different display device applications on the retardation value of the optical compensation film, the disclosure provides a cellulose acetate containing a benzene ring substituent, a preparation method and an application thereof The method has the advantages of low technical requirement, wide source, higher popularization and application value and wider development prospect, and is favorable for application in display equipment such as liquid crystal display devices, flexible display devices and the like.
Fig. 1 is a main composition diagram of a conventional liquid crystal display device.
As can be seen from fig. 1, in the liquid crystal display device, an optical thin film (e.g., a compensation film) is an important component.
FIG. 2 is a flow chart of a process for preparing cellulose acetate esters containing a benzene ring substituent according to an embodiment of the present disclosure.
As shown in FIG. 2, the method for preparing cellulose acetate containing a benzene ring substituent comprises: steps S201 to S204.
In step S201, cellulose acetate is dissolved in a polar organic solvent.
In step S202, a tertiary amine catalyst and an acid halide monomer containing a benzene ring are sequentially added to the obtained solution, and the acid halide monomer containing a benzene ring is reacted with cellulose acetate to obtain a reaction solution containing an esterification reaction product.
In step S203, the reaction solution is poured into deionized water to obtain a heterogeneous liquid.
In step S204, the heterogeneous liquid is subjected to solid-liquid separation to obtain cellulose acetate containing a benzene ring substituent.
According to an embodiment of the present disclosure, the above steps S201 to S204 may be performed in sequence. In the embodiment of the disclosure, a tertiary amine catalyst and an acyl halide monomer containing a benzene ring substituent are sequentially added into a polar organic solvent containing cellulose acetate, and the acyl halide monomer containing a benzene ring can fully react with the cellulose acetate due to the existence of the catalyst; meanwhile, the acyl halide monomer containing the benzene ring substituent and cellulose acetate are subjected to esterification reaction to generate cellulose acetate reaction liquid containing the benzene ring substituent. And pouring the obtained cellulose acetate reaction liquid containing the benzene ring substituent into deionized water, and cleaning redundant catalyst or acyl halide monomer containing the benzene ring to obtain heterogeneous liquid containing white solid, wherein the heterogeneous liquid contains the cellulose acetate containing the benzene ring substituent. And then, carrying out solid-liquid separation on the heterogeneous liquid, and purifying and drying to obtain the cellulose acetate containing the benzene ring substituent. The structure of the cellulose acetate containing the benzene ring substituent can be controlled by adjusting the parameters such as the proportion of reaction substrates (cellulose acetate, tertiary amine catalyst and polar organic solvent), the reaction time, the reaction temperature and the like in the esterification reaction of the cellulose acetate and acyl halide monomer containing the benzene ring under the catalysis of the tertiary amine catalyst, so that the basic parameters and the optical performance of the optical film prepared from the cellulose acetate containing the benzene ring substituent are regulated and controlled.
According to an embodiment of the present disclosure, in step S201, the polar organic solvent includes any one of: dimethylformamide, dimethylacetamide, dimethyl sulfoxide, acetone.
According to embodiments of the present disclosure, the cellulose acetate includes cellulose acetate of different acetylation degree, which can be distinguished by hydroxyl content, and in embodiments of the present disclosure, the hydroxyl content of the cellulose acetate ranges from 10% to 90%, optionally 10%, 20%, 40%, 60%, 80%, 90%, and the like, wherein 60% is preferred.
By the embodiment of the disclosure, cellulose acetate with higher hydroxyl content can be connected with more benzene ring structures, so that the performance of the prepared cellulose acetate optical film containing benzene ring substituent is further improved.
According to an embodiment of the present disclosure, the mass ratio range of the cellulose acetate to the polar organic solvent includes: 1: 10-15, wherein the mass ratio can be selected from 1: 10. 1: 11. 1: 12. 1: 13. 1: 14. 1: 15, etc., the mass ratio of the cellulose acetate to the polar organic solvent is preferably 1: 12 to 15.
By the embodiments of the present disclosure, the mass ratio of cellulose acetate to polar organic solvent is in the range of 1: within 10-15, the cellulose acetate can be sufficiently dissolved.
According to an embodiment of the present disclosure, in step S202, the structure of the benzene ring-containing acyl halide monomer is as follows:
According to embodiments of the present disclosure, the tertiary amine catalyst includes any one of:
According to an embodiment of the present disclosure, the range of the molar ratio of the tertiary amine catalyst to the benzene ring-containing acid halide monomer includes: 1: 1-3: 1, wherein, optionally 1: 1. 2: 1. 3: 1, etc.
According to the embodiment of the disclosure, the mole ratio range of the acyl halide monomer containing the benzene ring to the cellulose acetate comprises 1.2-10: 1, wherein, optionally 1.2: 1. 1.5: 1. 2: 1. 2.5: 1. 3: 1. 4: 1. 5: 1. 6: 1. 7: 1. 8: 1. 9: 1. 10: 1, etc.
According to an embodiment of the present disclosure, the temperature range of the reaction to obtain the reaction liquid includes: 20-100 ℃, wherein the temperature can be 20, 30, 40, 50, 60, 70, 80, 90, 100 ℃ and the like.
According to an embodiment of the present disclosure, the reaction time range for obtaining the reaction solution includes: 2-24 h, wherein the time can be selected from 2, 4, 6, 8, 10, 12, 14, 16, 18, 20, 22, 24h and the like.
According to the embodiment of the disclosure, preferably, under an inert gas (such as argon or nitrogen), a tertiary amine compound is used as a catalyst, and after the acyl halide monomer containing the benzene ring and the cellulose acetate are stirred and reacted at 20-100 ℃ for 2-24 hours, a reaction solution containing an esterification reaction is obtained, and with the increase of temperature and the extension of reaction time, the acyl halide monomer containing the benzene ring and the cellulose acetate are favorably subjected to a sufficient reaction under the catalysis of the tertiary amine compound, so that the reaction efficiency is improved.
According to the embodiment of the present disclosure, in step S203, the range of the mass ratio of the reaction liquid to the deionized water includes: 1: 50-200, wherein the ratio of 1: 50. 1: 100. 1: 150. 1: 200, etc.
Through the embodiment of the disclosure, deionized water with a certain proportion is added into the reaction solution, the mixture is vigorously stirred, the pH value is adjusted to be about 7, and after repeated cleaning, residual tertiary amine catalyst or acyl halide monomer containing benzene ring in the reaction solution can be cleaned, so as to obtain heterogeneous liquid containing white solid.
According to the embodiment of the present disclosure, in step S204, the heterogeneous liquid is subjected to solid-liquid separation and purification, and the obtained white solid is dried, so that cellulose acetate containing a phenyl ring substituent can be obtained.
According to embodiments of the present disclosure, cellulose acetate esters containing a benzene ring substituent have the following structural formula:
According to an embodiment of the present disclosure, a method of drying the resulting white solid includes: vacuum drying; the temperature range for drying includes: 80-120 ℃, wherein the temperature can be selected from 80, 90, 100, 110, 120 ℃ and the like; the time ranges for drying include: 2-48 h, wherein the time can be 2, 8, 14, 20, 26, 32, 38, 44, 48h and the like.
According to the embodiment of the disclosure, the obtained white solid is dried at 80-120 ℃ for 2-48 h, so that the moisture in the white solid can be effectively removed, and the cellulose acetate solid containing the benzene ring substituent can be obtained.
The disclosure also provides a cellulose acetate containing benzene rings, which can be applied to optical films.
According to the embodiment of the disclosure, the preparation method of the cellulose acetate optical film containing the benzene ring substituent comprises the following steps: adding the cellulose acetate containing the benzene ring substituent into a polar organic solvent, fully stirring until the cellulose acetate is completely dissolved, standing and defoaming, uniformly casting on a flat glass plate, and drying in vacuum to obtain the cellulose acetate optical film containing the benzene ring substituent.
According to an embodiment of the present disclosure, the organic solvent includes: dimethylformamide, dimethylacetamide, dimethylsulfoxide, acetone, and the like.
According to the embodiments of the present disclosure, the mass ratio range of the cellulose acetate containing benzene ring substituent to the organic solvent includes: 1: 15-20, wherein the ratio of 1: 15. 1: 16. 1: 17. 1: 18. 1: 19. 1: 20, etc.
According to the embodiment of the disclosure, the time for static defoaming comprises: 0.5-2 h and the pressure is about-0.1 MPa.
Through the embodiment of the disclosure, bubbles in the solvent can be effectively discharged after static defoaming for 0.5-2 h under about-0.1 MPa.
According to the embodiment of the disclosure, a glass plate of cast cellulose acetate containing benzene ring substituent is placed in a vacuum drying oven, and is firstly kept at 45-60 ℃ for 30-60 min, so that the solvent in the optical film is slowly evaporated, and cracking caused by bubbles generated on the surface of the film is prevented; and then, keeping the temperature at 90 ℃ for 2-24 h, so that the polar organic solvent remained in the optical film can be fully volatilized, and the cellulose acetate film containing the benzene ring substituent can be obtained.
According to the embodiment of the disclosure, the average thickness of the cellulose acetate film containing the benzene ring substituent comprises 10-200 μm, the light transmittance is above 88%, and the haze is below 3%.
According to the embodiment of the disclosure, the preferable range of the average thickness of the cellulose acetate film containing the benzene ring substituent group is 20-180 μm, the light transmittance is more than 90%, and the haze is less than 2%; furthermore, the preferable range of the average thickness of the cellulose acetate containing the benzene ring substituent is 40-150 μm, the light transmittance is more than 92%, and the haze is less than 1.5%.
According to embodiments of the present disclosure, there is provided the use of cellulose acetate esters containing a benzene ring substituent to prepare optical compensation films in display devices.
Through the embodiment of the disclosure, the cellulose acetate optical film containing the benzene ring substituent provided by the disclosure can meet the use requirements of different display devices on the compensation film by adjusting the proportion among the catalyst, the acyl halide monomer containing the benzene ring and the cellulose acetate according to the retardation value requirements of different display devices.
In order to make the objects, technical solutions and advantages of the present disclosure more clear and definite, the present disclosure will be further described in detail and accurately with reference to specific embodiments. It is to be understood that the specific embodiments described herein are merely illustrative of some, but not all, of the present disclosure, and that the following examples are intended to illustrate and not limit the present disclosure.
The instruments or reagents used in the present disclosure are not indicated by manufacturers, and are all conventional products on the market.
To further understand the present disclosure, the performance of cellulose acetate esters containing a phenyl ring substituent is examined in the following manner, using examples and comparative examples to more particularly illustrate the present disclosure.
Thickness measurement of thin films
The thickness of the cellulose acetate film containing the benzene ring substituent was measured using a micrometer screw.
Average refractive index measurement
The refractive index of the cellulose acetate film containing a benzene ring substituent was measured using an Abbe refractometer (model: ATAGO NAR-1T).
Measurement of light transmittance and haze
The light transmittance and haze of the cellulose acetate film containing a benzene ring substituent were measured using a light transmittance/haze meter (model: SGW-820, manufacturer: electro-optical).
Measurement of delay value
The in-plane retardation value and the out-of-plane retardation value of the cellulose acetate film containing a benzene ring substituent were measured using a phase difference meter (model: RETS-100L, manufactured by Otsuka Japan).
Glass transition temperature measurement
The glass transition temperature of cellulose acetate containing a benzene ring substituent was measured using a dynamic mechanical analysis tester (model: DMA2980, manufacturer: TA, USA).
In the embodiments of the present disclosure, the specific types of the tertiary amine catalyst and the acyl halide monomer containing a benzene ring are not limited, and based on the considerations of catalytic efficiency, acid-binding effect, solubility, safety, and the ease of purification of the cellulose acetate ester product containing a benzene ring substituent, the performance of the product, etc., in the embodiments of the present disclosure, pyridine is selected as the tertiary amine catalyst.
Example 1
According to the mass ratio of cellulose acetate to dimethyl amide of 1: 15, cellulose acetate (hydroxyl group content: 60%) was dissolved in dimethylformamide with stirring.
Then, pyridine and benzoyl chloride are sequentially slowly and dropwise added into a dimethylformamide solvent containing cellulose acetate, an esterification reaction is carried out under the protection of nitrogen atmosphere, and after the reaction is carried out for 2 hours at the reaction temperature of 20 ℃, a reaction solution containing an esterification reaction product can be obtained, wherein the pyridine is used as a catalyst and an acid-binding agent, the benzoyl chloride is used as an aromatic acyl halide monomer providing a benzene ring substituent, and the molar ratio of the pyridine to the benzoyl chloride to the cellulose acetate is 1.5: 1.5: 1.
then, a large amount of deionized water is slowly poured into the obtained reaction liquid and stirred vigorously to obtain heterogeneous liquid containing white solids, and the obtained heterogeneous liquid is repeatedly cleaned until the pH value is adjusted to about 7, so that the system is neutral.
And finally, carrying out solid-liquid separation on the washed heterogeneous liquid, and washing, purifying and drying the obtained white solid product to obtain the cellulose acetate containing the benzene ring substituent. The obtained cellulose acetate containing the benzene ring substituent is prepared into an optical film, basic performance parameters of the film, such as the thickness and the glass transition temperature of the film, are tested, and the specific test results are shown in table 1.
Example 2
The process of example 2 is the same as example 1, except that the molar ratio of pyridine and benzoyl chloride to cellulose acetate is 3: 3: 1. the obtained cellulose acetate containing the benzene ring substituent is prepared into an optical film, basic performance parameters of the film, such as the thickness and the glass transition temperature of the film, are tested, and the specific test results are shown in table 1.
Example 3
The process of example 3 is the same as example 1, except that the molar ratio of pyridine and benzoyl chloride to cellulose acetate is 4.5: 4.5: 1. the obtained cellulose acetate containing the benzene ring substituent is prepared into an optical film, basic performance parameters of the film, such as the thickness and the glass transition temperature of the film, are tested, and the specific test results are shown in table 1.
Example 4
The process of example 4 is the same as example 1, except that the molar ratio of pyridine and benzoyl chloride to cellulose acetate is 6: 6: 1. the obtained cellulose acetate containing benzene ring substituent is prepared into an optical film, basic performance parameters of the film such as film thickness and glass transition temperature are tested, and specific test results are shown in table 1.
Example 5
The procedure of example 5 is the same as in example 1, except that the esterification reaction of cellulose acetate and benzoyl chloride (benzene ring-containing acid halide monomer) is carried out under pyridine catalysis at a temperature of 60 ℃. The obtained cellulose acetate containing the benzene ring substituent is prepared into an optical film, basic performance parameters of the film, such as the thickness and the glass transition temperature of the film, are tested, and the specific test result is shown in table 1.
Example 6
The procedure of example 6 was the same as in example 1, except that the esterification reaction of cellulose acetate and benzoyl chloride (benzene ring-containing acid halide monomer) was carried out under pyridine catalysis for 18 hours. The obtained cellulose acetate containing the benzene ring substituent is prepared into an optical film, basic performance parameters of the film, such as the thickness and the glass transition temperature of the film, are tested, and the specific test result is shown in table 1.
Example 7
The procedure in example 7 is the same as in example 1, except that benzoyl chloride (benzene ring-containing acid halide monomer) is changed to 4-n-pentylbenzoyl chloride. The obtained cellulose acetate containing the benzene ring substituent is prepared into an optical film, basic performance parameters of the film, such as the thickness and the glass transition temperature of the film, are tested, and the specific test results are shown in table 1.
Example 8
The procedure in example 8 is the same as in example 1, except that benzoyl chloride is changed to 2-ethoxybenzoyl chloride. The obtained cellulose acetate containing the benzene ring substituent is prepared into an optical film, basic performance parameters of the film, such as the thickness and the glass transition temperature of the film, are tested, and the specific test result is shown in table 1.
Example 9
The procedure in example 9 was the same as in example 1, except that benzoyl chloride was changed to p-methylbenzoyl chloride. The obtained cellulose acetate containing the benzene ring substituent is prepared into an optical film, basic performance parameters of the film, such as the thickness and the glass transition temperature of the film, are tested, and the specific test result is shown in table 1.
Example 10
The procedure of example 10 is the same as in example 9, except that the esterification reaction of cellulose acetate and benzoyl chloride (benzene ring-containing acid halide monomer) is carried out under pyridine catalysis for 4 hours. The obtained cellulose acetate containing the benzene ring substituent is prepared into an optical film, basic performance parameters of the film, such as the thickness and the glass transition temperature of the film, are tested, and the specific test result is shown in table 1.
Comparative example 1
Cellulose acetate ester containing no benzene ring substituent was prepared in the same manner as in example 1, using the same cellulose acetate as in example 1, which was completely dissolved in dimethylformamide. The obtained cellulose acetate containing no benzene ring substituent is prepared into an optical film, basic performance parameters of the film, such as film thickness and glass transition temperature, are tested, and specific test results are shown in table 1.
It should be noted that, in order to better understand the application of the present disclosure to the optical film, the performance of the optical film is compared, and all of the above-mentioned examples and comparative examples are the performance tests after being prepared into the film.
The experimental conditions of all the above examples and comparative examples and the basic performance parameters of the optical films prepared are shown in table 1 below.
TABLE 1 reaction conditions and basic Performance parameters
Comparing the test results of all examples and comparative examples, it is apparent from table 1 that the following regularity can be obtained:
as can be seen by comparing all the examples and comparative examples, the glass transition temperature of the cellulose acetate film containing benzene ring substituent prepared by the method is not greatly reduced, and is still in a more desirable state compared with the comparative example.
The retardation value of the optical film is mainly classified into in-plane retardation (R)e) And out-of-plane retardation value (R)th) Two items. Because the thicknesses of the prepared cellulose acetate optical films are different, for convenience of comparison, the retardation values of the obtained optical films are converted into in-plane and out-of-plane refractive indexes for comparison, and the meanings of the formula and related parameters used in specific calculation are as follows:
Re＝Δne×d (1)
Rth＝Δnth×d (2)
wherein R iseIs an in-plane retardation value, RthIs the out-of-plane retardation value, Δ neIs an in-plane birefringence value, Δ nthThe out-of-plane birefringence value, d, is the thickness of the film.
The specific results of the optical property test of the optical films prepared in all the above examples and comparative examples are shown in table 2 below.
TABLE 2 optical Property test results
Comparing the test results of all examples with the comparative examples, the following regularity can be obtained from table 2:
(1) the refractive index of the cellulose acetate optical film containing the benzene ring substituent is obviously increased compared with that of the cellulose acetate optical film containing no benzene ring substituent, and the refractive index is related to reaction conditions. As the charge ratio is increased, the reaction temperature is increased, the reaction time is prolonged, the reaction degree is improved, and the increase of the refractive index is also facilitated. Therefore, the optical thin film material with larger refractive index can be obtained by adjusting the reaction conditions, such as the charge ratio, the reaction temperature, the reaction time and the like, so as to meet the required optical compensation film.
(2) As can be seen by comparing all the examples and comparative examples, the light transmittance and haze of the cellulose acetate optical film introduced with the aromatic group containing a benzene ring structure still meet the basic requirements of the optical film (the transparency is more than 90%, and the haze is less than 3%), and the optical film can be applied to a display device as the optical film.
(3) In-plane retardation value (R)e) The in-plane retardation value of the unstretched optical film is small and is basically 0nm by regulating and controlling through stretching; out-of-plane retardation value (R)th) Mainly depends on external additives for regulation and control. In the disclosed embodiments, the cellulose acetate ester containing a benzene ring substituent essentially chemically bonds the benzene ring containing molecular structure to the cellulose acetate, and the embodiments of the disclosure are prior to un-stretching, so the in-plane retardation values (R) of the embodiments of the disclosure and the comparative examples aree) Are all small, substantially all 0nm, i.e. the in-plane birefringence value (Δ n)e) Smaller, substantially 0. Accordingly, the disclosure is primarily discussed herein with respect to out-of-plane retardation values (R)th) The control effect of, i.e. the out-of-plane birefringence value (. DELTA.n)th) The regulation and control function of (1). As can be seen by comparing all of the above examples with the comparative examples, the out-of-plane retardation value (R) of the cellulose acetate having a benzene ring substituentth) Compared with a cellulose acetate optical film without benzene rings, the method has the advantages of obvious reduction and certain correlation with reaction conditions. As the feeding ratio is increased, the reaction temperature is increased, the reaction time is prolonged, and the out-of-plane birefringence value can be reduced to different degrees.
(4) The use requirement of IPS (in-plane switching) screen in the market is Rth<15-30 nm, and the preferred thickness range is 20-60 μm. As can be seen by comparing all of the above examples with the comparative examples, all of the examples provided by the present disclosure satisfy the requirements for IPS use at a film thickness of 50 μm, where R is preferredth<10 to 15 nm. The above examples 3, 5 and 10 were satisfactory when the film thickness was 50 μm. According to different use requirements, the optical compensation film with different retardation values can be customized by adjusting the reaction conditions.
For further understanding of the disclosure, all of the above examples and comparative examples were subjected to a stretching process similar to the industrial process flow, and the specific stretching parameters and procedures were as follows:
all the examples and comparative examples described above were subjected to a stretching treatment using a homemade uniaxial film stretching apparatus (refer to patents CN103063689A, CN 203275319U). Wherein the stretching temperature is 10 +/-0.5 ℃ above the glass transition temperature of the examples and the comparative examples, the stretching rate is 0.5mm/s, the preheating time of the sample strips before stretching is 15min, and 3 stretching ratios are set for each sample of the examples and are respectively 1.0, 1.2 and 1.5.
The Draw Ratio (DR) is defined as follows:
DR＝Lafter stretching/LBefore stretchingAnd L is the length of the tensile spline.
In an embodiment of the present disclosure, the method specifically includes the following stretching steps:
the method comprises the following steps: all the films of the above examples and comparative examples were previously baked and cut into standard tensile specimens.
Step two: fixing the sample strip by a clamp, and then placing the sample strip at a corresponding stretching temperature for heat preservation treatment for 15 min.
Step three: each example was subjected to stretching 1.0, 1.2 and 1.5 times at a stretching rate of 0.5mm/s, respectively, and when the stretching was carried out to the corresponding stretching ratio, the stretching was stopped and quenched with liquid nitrogen to reduce the shrinkage after stretching and the relaxation behavior of the internal orientation.
The tensile test results for all examples and comparative examples were counted and compared as shown in table 3 and table 3 below.
TABLE 3 tensile conditions and optical Property test results
TABLE 3 tensile conditions and optical Property test results
From table 3 and table 3 the following rules can be derived:
(1) when all the above examples are compared with comparative example 1, it can be seen that the retardation value of the cellulose acetate optical film containing no benzene ring varies greatly as the draw ratio increases; and the retardation value of the cellulose acetate film containing the benzene ring substituent is less changed along with the increase of the stretching ratio.
In comparison of example 1 with comparative example 1, when DR is 1.2, R of the cellulose acetate optical film containing no benzene ring is representede＝60.55nm，Rth34.25 nm; r of cellulose acetate containing benzene ring substituente＝33.9nm，Rth7.5nm, the latter being clearly smaller than the former.
(2) It can be seen from examples 1, 2 and 3 that the reaction conditions are different, and that the R of the cellulose acetate containing a benzene ring substituent increases with increasing charge ratio at the same draw ratioeR decreases with increasing feed ratiothRegulation from positive to negative values can be achieved.
(3) As can be seen from the test results of comparative example 1 and example 4, the optical film of example 4 has no matter R at a stretch ratio of 1.2eOr RthAre greatly reduced compared with comparative example 1, Re＝2.9nm，Rth0.5nm, at a film thickness of 50 μm, has reached the optimum use requirement (R) for IPS in the marketth<3 nm). If a smaller retardation value is required, the film can be made thinner as desired, or the stretch ratio can be adjusted appropriately.
(4) By comparing examples 1, 2, 5 and 6, it can be understood that the retardation value can be controlled by changing the reaction conditions at the same draw ratio under the same draw conditions and at the same draw ratio, with the increase of the charge ratio, the increase of the reaction temperature and the extension of the reaction time.
(5) According to the test results of the above embodiments, the retardation value of the cellulose acetate optical compensation film containing a benzene ring substituent provided by the present disclosure is significantly reduced compared with a cellulose acetate optical compensation film containing no benzene ring, the retardation value can be adjusted and controlled by changing reaction conditions and stretching parameters, a double-zero film meeting IPS use requirements can be prepared, and a new concept and method are provided for customizing optical compensation films with different requirements.
The above-mentioned embodiments are intended to illustrate the objects, aspects and advantages of the present disclosure in further detail, and it should be understood that the above-mentioned embodiments are only illustrative of the present disclosure and are not intended to limit the present disclosure, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present disclosure should be included in the scope of the present disclosure.
Claims (10)
1. A method for preparing cellulose acetate containing benzene ring substituent comprises the following steps:
dissolving cellulose acetate in a polar organic solvent;
sequentially adding a tertiary amine catalyst and an acyl halide monomer containing a benzene ring into the obtained solution, and reacting the acyl halide monomer containing the benzene ring with cellulose acetate to obtain a reaction solution containing an esterification reaction product;
pouring the reaction liquid into deionized water to obtain heterogeneous liquid;
and carrying out solid-liquid separation on the heterogeneous liquid to obtain the cellulose acetate containing the benzene ring substituent.
2. The method of claim 1, wherein the cellulose acetate ester containing a benzene ring substituent has the following structural formula:
3. The method of claim 1, wherein the polar organic solvent comprises any one of: dimethylformamide, dimethylacetamide, dimethyl sulfoxide, acetone;
the structural formula of the acyl halide monomer containing the benzene ring is as follows:
The tertiary amine catalyst comprises any one of the following components:
4. The method of claim 1, wherein the mass ratio of the cellulose acetate to the polar organic solvent ranges from: 1: 10 to 15.
5. The method according to claim 1, wherein the range of the molar ratio of the tertiary amine catalyst to the benzene ring-containing acid halide monomer comprises: 1: 1-3: 1;
the mole ratio range of the acyl halide monomer containing the benzene ring to the cellulose acetate is 1.2-10: 1;
the temperature range of the reaction for obtaining the reaction solution includes: 20-100 ℃;
the reaction time range for obtaining the reaction solution includes: 2-24 h.
6. The method of claim 1, wherein the mass ratio of the reaction liquid to the deionized water ranges from: 1: 50 to 200.
7. The method of claim 1, further comprising: after the heterogeneous liquid is subjected to solid-liquid separation, purifying and drying the obtained solid;
the drying method comprises the following steps: vacuum drying;
the temperature range of the drying includes: 80-120 ℃;
the time ranges for drying include: 2-48 h.
8. A cellulose acetate ester containing a benzene ring substituent prepared by the method of any one of claims 1 to 7.
9. The use of the cellulose acetate ester containing a phenyl ring substituent of claim 8 in optical films.
10. The use of claim 9, the optical film comprising an optical compensation film.
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| CN101392071A (en) * | 2007-09-21 | 2009-03-25 | 富士胶片株式会社 | Cellulose acylate film, phase difference film, optical compensation film, polaroid and image display device |
| CN103534274A (en) * | 2011-04-13 | 2014-01-22 | 伊士曼化工公司 | Cellulose ester optical films |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101392071A (en) * | 2007-09-21 | 2009-03-25 | 富士胶片株式会社 | Cellulose acylate film, phase difference film, optical compensation film, polaroid and image display device |
| CN103534274A (en) * | 2011-04-13 | 2014-01-22 | 伊士曼化工公司 | Cellulose ester optical films |
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| CN115386113A (en) * | 2022-08-16 | 2022-11-25 | 中国科学技术大学 | Optical film based on modified cellulose acetate and preparation method and application thereof |
| CN115386113B (en) * | 2022-08-16 | 2024-01-05 | 中国科学技术大学 | Optical film based on modified cellulose acetate, preparation method and application thereof |
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