CN109485837A - A kind of backbone chain type liquid crystal elastomer of side group cross-linking monomer containing cinnamyl and preparation method thereof - Google Patents
A kind of backbone chain type liquid crystal elastomer of side group cross-linking monomer containing cinnamyl and preparation method thereof Download PDFInfo
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Abstract
The invention discloses backbone chain type liquid crystal elastomers of a kind of side group cross-linking monomer containing cinnamyl and preparation method thereof.This kind of liquid crystal elastic body is that liquid crystal copolyester is prepared in the method that liquid crystal unit, photo-crosslinking monomer and linking group this three are first passed through high-temperature fusion polycondensation, then film in homogeneous thickness is obtained by hot pressing, it is carried out under liquid crystal state stretching orientation (single domain alignment state), it recycles the photochemical reaction of cortex cinnamomi group in molecule side group that the single domain alignment state crosslinking of liquid crystal is fixed up, multi-functional single domain liquid crystal elastic body intellectual material is prepared.This preparation method does not need solvent, expensive catalyst, and no small molecule monomer residual can be realized cleanly production, and in combination with various macromolecular orientation technique such as spinning, film stretching etc. can realize industrialized production.The single domain liquid crystal elastomer has very quick responsive actuation to heat, can be realized a variety of response modes and respondent behavior after special surface treatment.
Description
Technical field
The present invention relates to a kind of single domain liquid crystal elastomer field of Thermoreversibly deformation, in particular to a kind of side group contains cortex cinnamomi
Backbone chain type liquid crystal elastomer of base cross-linking monomer and preparation method thereof.
Background technique
Orientation of the liquid crystal elastic body of single domain in combination with caoutchouc elasticity (entropic elasticity) and liquid crystal state of polymer network
Order can equally generate very big shape to a series of extraneous stimulations (such as heat, light, electric field, magnetic field or pH) and change.
Artificial-muscle can imitate human muscle, may be implemented under the action of outside stimulus reversible flexible, and bending is tightened or expanded
Function is all the hot spot studied both at home and abroad all the time.The French physician P.G.de Gennes famous early in 1975 is just
The good selection of artificial thews material can be become by predicting liquid crystal elastic body, can satisfy the index of its properties.Only
The liquid crystal elastic body of single domain orientation just has generates spontaneous reversible shrink/expanded behavior between isotropic phase-liquid crystalline phase,
In heating, material is macroscopically showing as shrinking；When cooling, material is stretched or is expanded macroscopically showing as again.By institute
The miniature deformation for having the liquid crystal unit orientation in farmland to be consistent, therefore generate in this reversible process could be whole in macroscopic view
It shows as significantly shrinking and stretching on body, this characteristic is the devices such as various actuators, artificial-muscle and microrobot
Exploitation with application provide the foundation.
Realize this above-mentioned function, most important is exactly the liquid crystal elastic body for preparing single domain orientation.It is closed according to chemistry
At classification, there are mainly two types of the traditional preparation methods of single domain liquid crystal elastomer, is two step cross-linking methods and one-step synthesis respectively
Method.The two respectively has its advantage and unique distinction, but there is also some limitations.The former is before first preparing liquid crystal polymer
Then body uses cross-linking agents again, be made generally by hydrosilylation reactions, tail can be prepared by MOLECULE DESIGN
Direct type, waist direct type liquid crystal elastic body, and the azo single domain liquid crystal elastomer with light sensitivity.But its maximum deficiency is
Polymerization reaction cannot be carried out thoroughly, lead to still have a small amount of monomer residue in the liquid crystal elastic body being prepared, these small molecules
Monomer may occur to migrate and mutually separate over time, this will affect the service performance of its final product and service life；One
Step synthetic method is directly formed cross-linked network structure, and polymerization reaction directly occurs for liquid crystal polymer and crosslinking agent, compared to big point
Son, small molecule liquid crystal are easier to be orientated and can be used for a variety of preparation methods.But difficult point is to meet polymerization technique, assign
Give that small molecule liquid crystal monomer is multiple functionalized, the structure of liquid crystal monomer is relative complex, needs multistep organic synthesis just and can obtain and is corresponding
Monomer.In addition, limitation existing for the above method limits the large area preparation and industrialized production of single domain liquid crystal elastomer,
Therefore it needs to inquire into out simpler easy preparation method.Comparison based on above method advantage and disadvantage is ground to before related
Study carefully, we are inspired in many Review literatures: smectic type liquid crystal polymer being first subjected to orientation stretching in liquid crystal state, then
Its orientation texture is crosslinked with covalent bond again and is fixed, single domain liquid crystal elastomer can equally be prepared.
Summary of the invention
The technical problem to be solved in the present invention are as follows: a kind of backbone chain type liquid crystal elasticity of side group cross-linking monomer containing cinnamyl is provided
Body (also referred to as single domain liquid crystal elastomer) and preparation method thereof, in two kinds of traditional preparation methods in order to solve single domain liquid crystal elastomer
Existing limitation and deficiency.Wherein the polymerization reaction of two step cross-linking methods is not thorough, and has monomer residual in the liquid crystal elastic body of preparation
It stays；The difficult point of one-step synthesis is that synthesis step is complex cumbersome.These shortcoming and defect limit single domain liquid crystal elasticity
The large area of body prepares and industrialized production.Applicant of the present invention's research and probe go out a kind of simple and easy novel preparation method with
And the preparation process cleaned, novel single domain liquid crystal elastomer intelligent material is designed and successfully prepares, i.e. side group contains cinnamyl
The backbone chain type liquid crystal elastomer of cross-linking monomer.
The technical scheme adopted by the invention is as follows: a kind of backbone chain type liquid crystal elastomer of side group cross-linking monomer containing cinnamyl,
The backbone chain type liquid crystal elastomer is that present invention applicant accumulates the physical crosslinking to be formed work in research before using phenyl ring
With a kind of, thermoplasticity main chain smectic crystal elastomer (PBDPS) of synthesis, draw in the flexible molecule chain of this liquid crystal elastic body
Asymmetric phenyl ring side group is entered, strand is arranged in a manner of folded chain, and side group phenyl ring passes through the parallel accumulation of dislocation and formed strongly
The function of physical crosslinking point is played in π-π interaction.The photo-crosslinking monomer of the group containing cortex cinnamomi is introduced by MOLECULE DESIGN
In the strand side group of PBDPS, it is orientated in liquid crystal state, then utilizes the photochemical reaction of cinnamyl by liquid crystal single domain
Alignment state crosslinking is fixed up, so that it may the multi-functional single domain liquid crystal with quick thermal actuation and multiple response behavior be prepared
Elastomer intelligent material.
Specific technical solution is as follows:
A kind of backbone chain type liquid crystal copolyesters of side group cross-linking monomer containing cinnamyl, concrete structure formula are as follows:
A kind of backbone chain type liquid crystal elastomer of side group cross-linking monomer containing cinnamyl is passed through by the above-mentioned liquid crystal copolyester of liquid crystal state
Orientation, then the crosslinking of liquid crystal single domain alignment state is fixed up through photochemical reaction and is made.
Further, the liquid crystal copolyester is handed over by following structural unit [I] liquid crystal unit biphenyl dioxy hexanol, [II] light
Receipts or other documents in duplicate body 2,2'- (cinnamoyl azane diyl) diethyl diethyl phthalate and [III] linking group phenylsuccinic acid randomly form:
Wherein, the molfraction of [I] accounts for the 50% of all structural units, and the molfraction of [II] accounts for all structural units
10~50%, remaining is [III].
The method for preparing backbone chain type liquid crystal elastomer of above-mentioned side group cross-linking monomer containing cinnamyl, specifically includes following step
It is rapid:
(1) by liquid crystal unit biphenyl dioxy hexanol (BHHBP), photo-crosslinking monomer 2,2'- (cinnamoyl azane diyl) two
Diethyl acetate (DCA) and linking group phenylsuccinic acid (PSA) are under the effect of catalyst and the protection of nitrogen, and 170~220
DEG C heating stirring reacts 2~4h；Then the reaction was continued under vacuum conditions for the system after reacting, and cools down, obtains after reaction
Liquid crystal copolyester.The catalyst can be zinc acetate, antimony oxide, stannous octoate, dialkyltin or ethylene glycol
Any one in antimony.
(2) the obtained liquid crystal copolyester of step (1) is subjected to hot pressing and cut, regular required faciola shape is made on demand
Film batten, and stretching orientation is carried out to batten in certain temperature, then ultraviolet lighting is crosslinked, and is obtained side group and is crosslinked containing cinnamyl
The backbone chain type liquid crystal elastomer of monomer.
The thermal station temperature of ultraviolet light cross-linking is 25~55 DEG C, and the wavelength of ultraviolet light is 280~365nm, film batten two sides
The homogeneous cross-link time be 1~3h.
Wherein, the uniform film thickness being pressed into can be 0.2mm, and the width of batten can be 4mm after cutting, and water-bath is drawn
The temperature stretched can be 30~60 DEG C, and stretching ratio can be 200%~500%.
In conjunction with above-mentioned preparation method, the concrete mode control of 2~4h will be reacted in step (1) in 170~220 DEG C of heating stirrings
Be made as: in 170-200 DEG C of reaction 1h, then half an hour is warming up to 190-220 DEG C of reaction 1-3h；What the reaction was continued under vacuum condition
Mode controls are as follows: control vacuum degree is less than 30Pa, and the reaction temperature of heating stirring is 190-220 DEG C, and the reaction time is 1~4h.
In this way it is possible to prevente effectively from monomer, which decomposes, occurs side reaction, and effectively avoid remaining small molecule in liquid crystal copolyester.
Beneficial technical effect obtained by the present invention is as follows:
1) present invention solves deficiency and limitation existing for single domain liquid crystal elastomer traditional preparation methods, has explored one kind
Simple and easy novel preparation method and the preparation process cleaned design and successfully prepare the single domain of novel quickly thermotropic response
Liquid crystal elastic body intellectual material.
2) the present invention provides backbone chain type liquid crystal elastomers of a kind of side group cross-linking monomer containing cinnamyl and preparation method thereof.
Compared with existing thermotropic response single domain liquid crystal elastomer and its technology of preparing and technique, the invention has the following advantages that of the invention
A kind of method for preparing backbone chain type liquid crystal elastomer of the side group cross-linking monomer containing cinnamyl provided, overcomes traditional preparation methods
Existing polymerization reaction is not thorough the disadvantages of complicated cumbersome with synthesis step and limitation, while not needing solvent and expensive and urging
Agent will not remain small molecule monomer in polymer, and preparation method is simple, can be real in conjunction with various Process Technology of Polymer techniques
Existing industrialized production.
3) asymmetric phenyl ring side group is introduced in the flexible molecule chain of this liquid crystal elastic body, strand is in a manner of folded chain
Arrangement, side group phenyl ring are formed strong π-π interaction by the parallel accumulation of dislocation, play the function of physical crosslinking point.It is this
Special structure imparts its good physical mechanical property, film forming, spinnability and excellent shape memory function.Separately
Outside, [2+2] cycloaddition reaction occurs under the ultraviolet light of certain wavelength for the cortex cinnamomi group DCA introduced on strand, poly-
It closes in object and forms a large amount of covalent cross-linking network, the orientation cross-linked structure of single domain liquid crystal elastomer can be fixed up, thus
It realizes and the multiple circulating and reversible of temperature is responded.
Detailed description of the invention
Fig. 1 is the nuclear magnetic spectrogram of the liquid crystal copolyester of embodiment 6.
Specific embodiment
In order to determine the content of photo-crosslinking monomer DCA to the backbone chain type liquid crystal elastomer of side group cross-linking monomer containing cinnamyl
The influence of stimuli responsive degree and crosslink density, we are reflected by reversible actuating degree and gel content respectively.Orientation
The backbone chain type liquid crystal elastomer thin film of side group cross-linking monomer containing cinnamyl of crosslinking, during being heated to the phase of isotropism state
It can slowly shrink, can constantly be stretched during being cooled to LC phase, the actuating amplitude during which generated is defined as reversible actuating
It spends (RAD).After liquid crystal elastic body batten after crosslinking is sufficiently impregnated in a solvent, the mass fraction of undissolved part is defined
For gel content (GF).
In order to preferably illustrate the purpose of the present invention, technical problem, technical scheme and beneficial effects, below by specific
Embodiment carries out more detailed description and explanation to above-mentioned several parts of the invention.
Embodiment 1
(1) by biphenyl dioxy hexanol 3.8652g (1 × 10-2) and 2,2'- (cinnamoyl azane diyl) oxalic acid two mol
Ethyl ester 3.19g (1 × 10-2Mol it) is added in three neck reaction flasks, catalyst acetic acid zinc 0.0353g is additionally incorporated, in nitrogen atmosphere
Lower 170 DEG C of protection be stirred to react 1h, after be warming up to 190 DEG C the reaction was continued 1h.
(2) high vacuum condition and continuation introduced within 30Pa into the system after step (1) reaction heats at 190 DEG C
It is stirred to react 4h, is cooled down after reaction, obtained liquid crystal copolyester number-average molecular weight is 50000.
(3) step (2) obtained liquid crystal copolyester is hot pressed into the uniform film of 0.2mm thickness at 110 DEG C, is cut
It is 20mm at length, width is the standard batten of 4mm, and stretch to batten along its length in 60 DEG C of water-bath and take
To stretching ratio 500%.
(4) the film batten after step (3) to be stretched to orientation carries out at 55 DEG C and under the ultraviolet light of 280nm wavelength
Double-faced uniform ultraviolet lighting is crosslinked total 3h, obtains the backbone chain type liquid crystal elastomer of side group cross-linking monomer containing cinnamyl.
By the backbone chain type liquid crystal elastomer thin film batten of the preparation-obtained side group cross-linking monomer containing cinnamyl of the present embodiment
Its reversible actuating degree (RAD) is first surveyed between 20 DEG C (liquid crystal states) and 80 DEG C (isotropism state)；It places it in chloroform and is swollen
Reach for 24 hours, its gel content (GF) was surveyed in vacuum drying later for 24 hours.As shown in table 1.
Embodiment 2
(1) by biphenyl dioxy hexanol 3.8652g (1 × 10-2Mol), 2,2'- (cinnamoyl azane diyl) oxalic acid diethyl
Ester 2.871g (9.0 × 10-3) and phenylsuccinic acid 0.1942g (1.0 × 10 mol-3Mol it) is added in three neck reaction flasks, in addition
Be added the catalytic antimony trioxide 0.0347g, be stirred to react 1h for 170 DEG C under the protection of nitrogen atmosphere, after be warming up to 190 DEG C after
Continuous reaction 1.5h.
(2) it introduces at 190 DEG C of the high vacuum condition within 30Pa and continuation to heat into the system after step (1) reaction and stir
Reaction 3.5h is mixed, is cooled down after reaction, the number-average molecular weight for obtaining liquid crystal copolyester is 46500.
(3) step (2) obtained liquid crystal copolyester is prepared into standard batten by embodiment 1, and in 55 DEG C of water-bath
Stretching orientation, stretching ratio 500% are carried out to batten.
(4) the film batten after step (3) to be stretched to orientation carries out at 50 DEG C and under the ultraviolet light of 313nm wavelength
Double-faced uniform is crosslinked total 3h, obtains the backbone chain type liquid crystal elastomer of side group cross-linking monomer containing cinnamyl.
Backbone chain type of the related operating method of reference embodiment 1 to side group cross-linking monomer containing cinnamyl manufactured in the present embodiment
Liquid crystal elastic body carries out the dependence test of reversible actuating degree (RAD) and gel content (GF), as shown in table 1.
Embodiment 3
(1) by biphenyl dioxy hexanol 3.8652g (1 × 10-2Mol), 2,2'- (cinnamoyl azane diyl) oxalic acid diethyl
Ester 2.7115g (8.5 × 10-3) and phenylsuccinic acid 0.2913g (1.5 × 10 mol-3Mol it) is added in three neck reaction flasks, separately
Outer addition octoate catalyst stannous 0.0343g, is stirred to react 1h for 180 DEG C under the protection of nitrogen atmosphere, after be warming up to 190 DEG C after
Continuous reaction 1.5h.
(2) it introduces at 190 DEG C of the high vacuum condition within 30Pa and continuation to heat into the system after step (1) reaction and stir
Reaction 3.5h is mixed, is cooled down after reaction, the number-average molecular weight for obtaining liquid crystal copolyester is 43600.
(3) step (2) obtained liquid crystal copolyester is prepared into standard batten by embodiment 1, and in 55 DEG C of water-bath
Stretching orientation, stretching ratio 450% are carried out along its length to batten.
(4) the film batten after step (3) to be stretched to orientation carries out at 50 DEG C and under the ultraviolet light of 365nm wavelength
Double-faced uniform ultraviolet lighting is crosslinked total 2.5h, obtains the backbone chain type liquid crystal elastomer of side group cross-linking monomer containing cinnamyl.
Backbone chain type of the related operating method of reference embodiment 1 to side group cross-linking monomer containing cinnamyl manufactured in the present embodiment
Liquid crystal elastic body carries out the dependence test of reversible actuating degree (RAD) and gel content (GF), as shown in table 1.
Embodiment 4
(1) by biphenyl dioxy hexanol 3.8652g (1 × 10-2Mol), 2,2'- (cinnamoyl azane diyl) oxalic acid diethyl
Ester 2.3925g (7.5 × 10-3) and phenylsuccinic acid 0.4855g (2.5 × 10 mol-3Mol it) is added in three neck reaction flasks, separately
Outer addition the catalytic antimony trioxide 0.0337g, is stirred to react 1h for 180 DEG C under the protection of nitrogen atmosphere, after be warming up to 200 DEG C
The reaction was continued 2h.
(2) it introduces at 200 DEG C of the high vacuum condition within 30Pa and continuation to heat into the system after step (1) reaction and stir
Reaction 3h is mixed, is cooled down after reaction, the number-average molecular weight for obtaining liquid crystal copolyester is 39000.
(3) step (2) obtained liquid crystal copolyester is prepared into standard batten by embodiment 1, and in 50 DEG C of water-bath
Stretching orientation, stretching ratio 450% are carried out along its length to batten.
(4) the film batten after step (3) to be stretched to orientation carries out at 45 DEG C and under the ultraviolet light of 313nm wavelength
Double-faced uniform ultraviolet lighting is crosslinked total 2.5h, obtains the backbone chain type liquid crystal elastomer of side group cross-linking monomer containing cinnamyl.
Backbone chain type of the related operating method of reference embodiment 1 to side group cross-linking monomer containing cinnamyl manufactured in the present embodiment
Liquid crystal elastic body carries out the dependence test of reversible actuating degree (RAD) and gel content (GF), as shown in table 1.
Embodiment 5
(1) by biphenyl dioxy hexanol 3.8652g (1 × 10-2Mol), 2,2'- (cinnamoyl azane diyl) oxalic acid diethyl
Ester 1.914g (6.0 × 10-3) and phenylsuccinic acid 0.7767g (4.0 × 10 mol-3Mol it) is added in three neck reaction flasks, in addition
Be added octoate catalyst stannous 0.0328g, be stirred to react 1h for 190 DEG C under the protection of nitrogen atmosphere, after be warming up to 200 DEG C of continuation
React 2h.
(2) it introduces at 200 DEG C of the high vacuum condition within 30Pa and continuation to heat into the system after step (1) reaction and stir
Reaction 3h is mixed, is cooled down after reaction, the number-average molecular weight for obtaining liquid crystal copolyester is 34300.
(3) step (2) obtained liquid crystal copolyester is prepared into standard batten by embodiment 1, and in 45 DEG C of water-bath
Stretching orientation, stretching ratio 400% are carried out along its length to batten.
(4) the film batten after step (3) to be stretched to orientation carries out at 40 DEG C and under the ultraviolet light of 365nm wavelength
Double-faced uniform ultraviolet lighting is crosslinked total 2h, obtains the backbone chain type liquid crystal elastomer of side group cross-linking monomer containing cinnamyl.
Backbone chain type of the related operating method of reference embodiment 1 to side group cross-linking monomer containing cinnamyl manufactured in the present embodiment
Liquid crystal elastic body carries out the dependence test of reversible actuating degree (RAD) and gel content (GF), as shown in table 1.
Embodiment 6
(1) by biphenyl dioxy hexanol 3.8652g (1 × 10-2Mol), 2,2'- (cinnamoyl azane diyl) oxalic acid diethyl
Ester 1.595g (5.0 × 10-3) and phenylsuccinic acid 0.9709g (5.0 × 10 mol-3Mol it) is added in three neck reaction flasks, in addition
Be added catalyst dialkyltin 0.0322g, be stirred to react 1h for 190 DEG C under the protection of nitrogen atmosphere, after be warming up to 200 DEG C
The reaction was continued 2.5h.
(2) it introduces at 200 DEG C of the high vacuum condition within 30Pa and continuation to heat into the system after step (1) reaction and stir
Reaction 2.5h is mixed, is cooled down after reaction, the number-average molecular weight for obtaining liquid crystal copolyester is 28500.
(3) step (2) obtained liquid crystal copolyester is prepared into standard batten by embodiment 1, and in 45 DEG C of water-bath
Stretching orientation, stretching ratio 350% are carried out along its length to batten.
(4) the film batten after step (3) to be stretched to orientation carries out at 40 DEG C and under the ultraviolet light of 313nm wavelength
Double-faced uniform ultraviolet lighting is crosslinked total 2h, obtains the backbone chain type liquid crystal elastomer of side group cross-linking monomer containing cinnamyl.
Backbone chain type of the related operating method of reference embodiment 1 to side group cross-linking monomer containing cinnamyl manufactured in the present embodiment
Liquid crystal elastic body carries out the dependence test of reversible actuating degree (RAD) and gel content (GF), as shown in table 1.
Embodiment 7
(1) by biphenyl dioxy hexanol 3.8652g (1 × 10-2Mol), 2,2'- (cinnamoyl azane diyl) oxalic acid diethyl
Ester 1.276g (4.0 × 10-3) and phenylsuccinic acid 1.1651g (6.0 × 10 mol-3Mol it) is added in three neck reaction flasks, in addition
Catalyst acetic acid zinc 0.0315g is added, is stirred to react 1h for 190 DEG C under the protection of nitrogen atmosphere, after be warming up to 210 DEG C continue it is anti-
Answer 2.5h.
(2) it introduces at 210 DEG C of the high vacuum condition within 30Pa and continuation to heat into the system after step (1) reaction and stir
Reaction 2.5h is mixed, is cooled down after reaction, the number-average molecular weight for obtaining liquid crystal copolyester is 22300.
(3) step (2) obtained liquid crystal copolyester is prepared into standard batten by embodiment 1, and in 40 DEG C of water-bath
Stretching orientation, stretching ratio 300% are carried out along its length to batten.
(4) the film batten after step (3) to be stretched to orientation carries out at 35 DEG C and under the ultraviolet light of 313nm wavelength
Double-faced uniform is crosslinked total 1.5h, obtains the backbone chain type liquid crystal elastomer of side group cross-linking monomer containing cinnamyl.
Backbone chain type of the related operating method of reference embodiment 1 to side group cross-linking monomer containing cinnamyl manufactured in the present embodiment
Liquid crystal elastic body carries out the dependence test of reversible actuating degree (RAD) and gel content (GF), as shown in table 1.
Embodiment 8
(1) by biphenyl dioxy hexanol 3.8652g (1 × 10-2Mol), 2,2'- (cinnamoyl azane diyl) oxalic acid diethyl
Ester 1.1165g (3.5 × 10-3) and phenylsuccinic acid 1.2622g (6.5 × 10 mol-3Mol it) is added in three neck reaction flasks, separately
Outer addition the catalytic antimony trioxide 0.0312g, is stirred to react 1h for 190 DEG C under the protection of nitrogen atmosphere, after be warming up to 210 DEG C
The reaction was continued 3h.
(2) it introduces at 210 DEG C of the high vacuum condition within 30Pa and continuation to heat into the system after step (1) reaction and stir
Reaction 2h is mixed, is cooled down after reaction, the number-average molecular weight for obtaining liquid crystal copolyester is 15700.
(3) step (2) obtained liquid crystal copolyester is prepared into standard batten by embodiment 1, and in 40 DEG C of water-bath
Stretching orientation, stretching ratio 250% are carried out along its length to batten.
(4) the film batten after step (3) to be stretched to orientation carries out at 35 DEG C and under the ultraviolet light of 280nm wavelength
Double-faced uniform is crosslinked total 1.5h, obtains the backbone chain type liquid crystal elastomer of side group cross-linking monomer containing cinnamyl.
Backbone chain type of the related operating method of reference embodiment 1 to side group cross-linking monomer containing cinnamyl manufactured in the present embodiment
Liquid crystal elastic body carries out the dependence test of reversible actuating degree (RAD) and gel content (GF), as shown in table 1.
Embodiment 9
(1) by biphenyl dioxy hexanol 3.8652g (1 × 10-2Mol), 2,2'- (cinnamoyl azane diyl) oxalic acid diethyl
Ester 0.7975g (2.5 × 10-3) and phenylsuccinic acid 1.4564g (7.5 × 10 mol-3Mol it) is added in three neck reaction flasks, separately
Outer addition catalyst dialkyltin 0.0306g, is stirred to react 1h for 200 DEG C under the protection of nitrogen atmosphere, after be warming up to 220
DEG C the reaction was continued 3h.
(2) it introduces at 220 DEG C of the high vacuum condition within 30Pa and continuation to heat into the system after step (1) reaction and stir
Reaction 1.5h is mixed, is cooled down after reaction, the number-average molecular weight for obtaining liquid crystal copolyester is 9900.
(3) step (2) obtained liquid crystal copolyester is prepared into standard batten by embodiment 1, and in 35 DEG C of water-bath
Stretching orientation, stretching ratio 250% are carried out along its length to batten.
(4) the film batten after step (3) to be stretched to orientation carries out at 30 DEG C and under the ultraviolet light of 313nm wavelength
Double-faced uniform is crosslinked total 1h, obtains the backbone chain type liquid crystal elastomer of side group cross-linking monomer containing cinnamyl.
Backbone chain type of the related operating method of reference embodiment 1 to side group cross-linking monomer containing cinnamyl manufactured in the present embodiment
Liquid crystal elastic body carries out the dependence test of reversible actuating degree (RAD) and gel content (GF), as shown in table 1.
Embodiment 10
(1) by biphenyl dioxy hexanol 3.8652g (1 × 10-2Mol), 2,2'- (cinnamoyl azane diyl) oxalic acid diethyl
Ester 0.638g (2.0 × 10-3) and phenylsuccinic acid 1.5534g (8.0 × 10 mol-3Mol it) is added in three neck reaction flasks, in addition
Be added catalyst glycol antimony 0.0303g, be stirred to react 1h for 200 DEG C under the protection of nitrogen atmosphere, after be warming up to 220 DEG C of continuation
3h is reacted,
(2) it introduces at 220 DEG C of the high vacuum condition within 30Pa and continuation to heat into the system after step (1) reaction and stir
Reaction 1h is mixed, is cooled down after reaction, the number-average molecular weight for obtaining liquid crystal copolyester is 5000.
(3) step (2) obtained liquid crystal copolyester is prepared into standard batten by embodiment 1, and in 30 DEG C of water-bath
Stretching orientation, stretching ratio 200% are carried out along its length to batten.
(4) the film batten after step (3) to be stretched to orientation carries out at 25 DEG C and under the ultraviolet light of 313nm wavelength
Double-faced uniform is crosslinked total 1h, obtains the backbone chain type liquid crystal elastomer of side group cross-linking monomer containing cinnamyl.
Backbone chain type of the related operating method of reference embodiment 1 to side group cross-linking monomer containing cinnamyl manufactured in the present embodiment
Liquid crystal elastic body carries out the dependence test of reversible actuating degree (RAD) and gel content (GF), as shown in table 1.
The reversible actuating degree and gel content measured from table 1, comparative analysis it can be found that photo-crosslinking monomer DCA content
It has a significant effect to the reversible deformation of liquid crystal elastic body and crosslinking degree.The reversible actuating degree RAD of liquid crystal elastic body contains with DCA
The increase of amount and slowly decline, drop to 25% from 54%；Crosslink density is continuously increased, and gel content GF is gradually increasing from 42%
To 91%.
The reversible deformation and friendship of the backbone chain type liquid crystal elastomer of side group cross-linking monomer containing cinnamyl of 1 difference DCA content of table
Connection degree
In upper table, reversible actuating degree (RAD) is calculate by the following formula:
RAD=(LLC-Liso)/Liso× 100%,
Wherein, LisoThe length of liquid crystal elastic body batten when for high temperature (80 DEG C),
LLCThe length of liquid crystal elastic body batten when for low temperature (20 DEG C).
Gel content (GF) is calculated by formula below:
GF=m1/m0× 100%,
Wherein, m0For the initial mass of liquid crystal elastic body batten,
m1The quality in chloroform for 24 hours and under 45 DEG C of vacuum conditions after drying for 24 hours is placed in for liquid crystal elastic body batten.
Claims (6)
1. a kind of backbone chain type liquid crystal copolyesters of side group cross-linking monomer containing cinnamyl, it is characterised in that: the liquid crystal copolyester
Concrete structure formula is as follows:
2. a kind of backbone chain type liquid crystal elastomer of side group cross-linking monomer containing cinnamyl, it is characterised in that: the backbone chain type liquid crystal bullet
Property body is orientated by the liquid crystal copolyester as described in claim 1 under liquid crystal state, then through photochemical reaction by liquid crystal single domain
Alignment state crosslinking is fixed up and is made.
3. the backbone chain type liquid crystal elastomer of side group cross-linking monomer containing cinnamyl as claimed in claim 2, it is characterised in that: described
It include liquid crystal unit biphenyl dioxy hexanol shown in structural unit [I], the friendship of light shown in structural unit [II] in liquid crystal copolyester
Linking group phenyl fourth two shown in receipts or other documents in duplicate body 2,2'- (cinnamoyl azane diyl) diethyl diethyl phthalate and structural unit [III]
Acid；Wherein the molfraction of liquid crystal unit biphenyl dioxy hexanol accounts for the 50% of all structural units, photo-crosslinking monomer 2,2'- (meat
Osmanthus acyl group azane diyl) molfraction of diethyl diethyl phthalate accounts for the 10~50% of all structural units, and remaining is linking group
Phenylsuccinic acid；
4. the system of the backbone chain type liquid crystal elastomer of side group cross-linking monomer containing cinnamyl as described in any one of Claims 2 or 3
Preparation Method, it is characterised in that: the preparation method of the liquid crystal elastic body comprises the steps of:
(1) by liquid crystal unit biphenyl dioxy hexanol, photo-crosslinking monomer 2,2'- (cinnamoyl azane diyl) diethyl diethyl phthalate and
For linking group phenylsuccinic acid under the effect of catalyst and the protection of nitrogen, 170~220 DEG C of heating stirrings react 2~4h；So
The reaction was continued under vacuum conditions for system after reacting afterwards, cools down after reaction, obtains liquid crystal copolyester；
(2) the obtained liquid crystal copolyester of step (1) is subjected to hot pressing and cut, regular thin band-like film sample is made on demand
Item, and stretching orientation is carried out to batten in certain temperature, it is then crosslinked at 25-55 DEG C through ultraviolet lighting, the wavelength of ultraviolet light
Crosslinking time for 280~365nm, film batten two sides is 1~3h, obtains the backbone chain type liquid of side group cross-linking monomer containing cinnamyl
Brilliant elastomer.
5. the method for preparing backbone chain type liquid crystal elastomer of side group cross-linking monomer containing cinnamyl as claimed in claim 4, special
Sign is: reacting the concrete mode of 2~4h in step (1) in 170~220 DEG C of heating stirrings are as follows: in 170-200 DEG C of reaction 1h,
Then half an hour is warming up to 190-220 DEG C of reaction 1-3h；The mode that the reaction was continued under vacuum condition are as follows: control vacuum degree is less than
30Pa, the reaction temperature of heating stirring are 190-220 DEG C, and the reaction time is 1~4h.
6. the method for preparing backbone chain type liquid crystal elastomer of side group cross-linking monomer containing cinnamyl as claimed in claim 4, special
Sign is: catalyst described in step (1) is zinc acetate, antimony oxide, stannous octoate, dialkyltin or ethylene glycol
Any one in antimony.
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