CN110845713B - Main chain type biodegradable liquid crystal polymer and preparation method thereof - Google Patents

Main chain type biodegradable liquid crystal polymer and preparation method thereof Download PDF

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CN110845713B
CN110845713B CN201911145242.9A CN201911145242A CN110845713B CN 110845713 B CN110845713 B CN 110845713B CN 201911145242 A CN201911145242 A CN 201911145242A CN 110845713 B CN110845713 B CN 110845713B
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杨立群
胡建设
陈超先
陈思文
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Abstract

The invention belongs to the technical field of biodegradable medical high polymer materials, and particularly relates to a main chain type biodegradable liquid crystal polymer and a preparation method thereof. The liquid crystal intermediate is prepared by taking natural products such as cholesterol, diosgenin, menthol, isosorbide and the like as liquid crystal cores and hydroxyl-terminated alkanoic acid or amino acid as flexible spacers, and is used as an initiator to initiate ring-opening polymerization reaction of one or a mixture of two or more of monomers such as trimethylene carbonate, caprolactone, lactide, glycolide, p-dioxanone, propiolactone, butyrolactone, octalactone, caprolactam, morpholine-2, 5-dione, dianhydride and the like and derivatives thereof, so as to obtain the main chain type biodegradable liquid crystal polymer. The main chain type biodegradable liquid crystal polymer has good liquid crystal performance, is easy to orient to form an ordered structure, not only responds to the outside such as temperature, pH, stress, an electric field, a magnetic field and the like, but also has good biocompatibility and degradation performance.

Description

Main chain type biodegradable liquid crystal polymer and preparation method thereof
Technical Field
The invention belongs to the technical field of biodegradable medical high polymer materials, and particularly relates to a main chain type biodegradable liquid crystal polymer and a preparation method thereof.
Background
Biodegradable high molecular materials have wide application value in the biomedical fields of drug carriers, tissue engineering, surgical medicine and the like, the research on the biodegradable high molecular materials is more and more concerned by people, and the degradation performance, biocompatibility, surface performance and the like of the polymers can be further improved by carrying out structural modification on the biodegradable high molecular materials, such as introduction of functional groups and the like, so that the biodegradable high molecular materials are better suitable for adhesion, growth and the like of cells or tissues and organs, and the polymers have controllable molecular structures, mechanical properties and degradation performance.
The liquid crystal material can be self-assembled to obtain various ordered structures, and can respond to changes of external conditions such as temperature, pH, stress, electric field, magnetic field and the like; research shows that most of basic substances such as DNA, phospholipid and the like which form the living body are biological liquid crystals, and the substances and information of the living body are transmitted by the liquid crystals. The liquid crystal state is the existing state of a living body, and substances such as proteins, phospholipids and the like on the cell membrane of the living body are in the liquid crystal state, so that the cell membrane of living cells of the living body is in the liquid crystal state, and various sensitive sensory mechanisms of the living body are related to liquid crystal in the living body. Therefore, the research on biodegradable liquid crystal polymers is undoubtedly of great academic and potential application value. The components with liquid crystal property and bioactivity are introduced into the chain structure of the biodegradable high polymer, so that the material has double excellent properties of the biodegradable polymer and the liquid crystal compound, the biocompatibility of the material can be improved, the response capability of the material to the outside can be improved, and the degradation property and the mechanical property of the material can be further improved; at present, few research reports about biodegradable liquid crystal at home and abroad are available.
Disclosure of Invention
Aiming at the defects that the existing biodegradable medical high polymer material lacks environmental responsiveness and the like, the invention provides a main chain type biodegradable liquid crystal polymer and a preparation method thereof, which introduces components with liquid crystal performance and bioactivity into the chain structure of the biodegradable high polymer, so that the material has double excellent performances of the biodegradable polymer and the liquid crystal compound, thereby not only improving the biocompatibility, but also improving the response capability of the material to the outside, and further improving the degradation performance and the mechanical property of the material.
The technical scheme of the invention is as follows:
a main chain type biodegradable liquid crystal polymer, the structural formula of the main chain type biodegradable liquid crystal polymer is as follows:
Figure BDA0002281975290000021
wherein n is 2-12, 15-17
Or
Figure BDA0002281975290000022
Wherein n is 2-12, 15
M1, M2, M3: one or two or more of trimethylene carbonate, caprolactone, lactide, glycolide, p-dioxane ketone, lactide, butyrolactone, octalactone, caprolactam, morpholine-2, 5-dione and dianhydride;
x、y、z：0～1000
Figure BDA0002281975290000023
the main chain type biodegradable liquid crystal polymer has a molecular structure comprising a liquid crystal core, a flexible spacer and a degradable chain segment; the liquid crystal nucleus is natural products of cholesterol, diosgenin, menthol or isosorbide; the degradation chain segment is one of homopolymer of trimethylene carbonate, caprolactone, lactide, glycolide, p-dioxane ketone, lactide, butyrolactone, octalactone, caprolactam, morpholine-2, 5-diketone and dianhydride or copolymer of any two or more monomers; the flexible spacer is terminal hydroxyl alkanoic acid or terminal amino acid, the terminal hydroxyl alkanoic acid is glycolic acid, 3-hydroxypropionic acid, 4-hydroxybutyric acid, 5-hydroxypentanoic acid, 6-hydroxyhexanoic acid, 7-hydroxyheptanoic acid, 8-hydroxyoctanoic acid, 9-hydroxynonanoic acid, 10-hydroxydecanoic acid, 11-hydroxyundecanoic acid, 12-hydroxydodecanoic acid, 15-hydroxypentadecanoic acid, 16-hydroxyhexadecanoic acid or 17-hydroxyheptadecanoic acid; the terminal amino acid is 2-aminoacetic acid, 3-aminopropionic acid, 4-aminobutyric acid, 5-aminopentanoic acid, 6-aminocaproic acid, 7-aminoheptanoic acid, 8-aminocaprylic acid, 9-aminononanoic acid, 10-aminodecanoic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid or 15-aminopentadecanoic acid.
The preparation method of the main chain type biodegradable liquid crystal polymer comprises the following steps:
(1) preparation of end-group protected alkanoic acids
(1.1) dissolving a hydroxy-terminated alkanoic acid or amino-terminated acid in a reactor containing a solution of dichloromethane and triethylamine, wherein: the molar ratio of the hydroxyl-terminated alkanoic acid or the terminal amino acid to the triethylamine is 1: 1-10;
(1.2) under the ice-water bath cooling condition, dropwise adding a dichloromethane solution of triphenylchloromethane under stirring, wherein the molar weight ratio of the dropwise adding amount of the triphenylchloromethane to the molar weight ratio of the terminal hydroxy alkanoic acid or the terminal amino acid is 1: 1-10;
(1.3) reacting at room temperature for 6-12 h after dripping;
(1.4) use in sequenceWater, 1 mol. L-1Washing with hydrochloric acid, saturated sodium bicarbonate solution and saturated salt solution, drying with anhydrous sodium sulfate, concentrating to dryness, and recrystallizing with petroleum ether to obtain terminal group protected alkanoic acid;
(2) preparation of end group protection alkanoic acid liquid crystal nucleus ester
(2.1) adding a methylene chloride solution of end-group protected alkanoic acid into a reactor, adding dimethylformamide according to needs, and then dropwise adding a methylene chloride solution of oxalyl chloride into the reactor under an ice bath condition, wherein the molar ratio of the oxalyl chloride to the end-group protected alkanoic acid is (1-5): 1;
(2.2) reacting at room temperature for 1-6 h, and then performing rotary evaporation to obtain end group protection alkanoyl chloride;
(2.3) adding cholesterol, diosgenin, menthol or isosorbide liquid crystal nucleus into a reactor, dissolving chloroform, dropwise adding pyridine according to needs, and then continuously dropwise adding the chloroform solution of the end-group protection alkanoyl chloride prepared in the step (2.2), wherein the molar ratio of the end-group protection alkanoyl chloride to the liquid crystal nucleus is 1: (1-8);
(2.4) carrying out reflux reaction for 2-36 h; cooling, performing rotary evaporation, precipitating with methanol, and filtering to obtain a crude product;
(2.5) recrystallizing the crude product by using a mixed solution of chloroform and methanol, filtering and drying to obtain end group protection alkanoic acid liquid crystal nucleus ester;
(3) preparation of liquid crystal initiator
(3.1) adding a dichloromethane solution of the end-group-protected alkanoic acid liquid crystal nucleus ester and triethylsilane into a reactor, wherein the molar ratio of the end-group-protected alkanoic acid liquid crystal nucleus ester to the triethylsilane is 1: (1-6);
(3.2) adding a dichloromethane solution of trifluoroacetic acid into the reactor under stirring, wherein the molar ratio of the end-group-protected alkanoic acid liquid crystal nucleus ester to the trifluoroacetic acid is 1: (1-6);
(3.3) reacting at room temperature for 0.5-6 h; after rotary evaporation, dissolving in ethyl acetate, washing with water and saturated saline solution in sequence, standing for crystallization, filtering, concentrating the filtrate, and performing column chromatography to obtain a liquid crystal initiator;
(4) preparation of main chain type biodegradable liquid crystal polymer
(4.1) adding a liquid crystal initiator and one or two or more than two degradation chain segment monomers of trimethylene carbonate, caprolactone, lactide, glycolide, p-dioxane ketone, lactide, butyrolactone, octalactone, caprolactam, morpholine-2, 5-diketone and dianhydride into a reactor, wherein the molar ratio of the liquid crystal initiator to the degradation chain segment monomers is 1: (50 to 20000);
(4.2) carrying out vacuum pumping for 2-4 times under reduced pressure, and adding an anhydrous toluene solution of stannous octoate according to needs, wherein the mole number of the stannous octoate is 0-2% of that of the degradation chain segment monomer;
(4.3) carrying out vacuum pumping for 2-4 times again under reduced pressure, sealing the reactor, and then heating to 80-160 ℃ for reaction for 8-72 h;
(4.4) use of CHCl for the product3Dissolving, precipitating in methanol, cleaning, and drying to constant weight to obtain main chain type biodegradable liquid crystal polymer.
The main chain type biodegradable liquid crystal polymer is prepared by the method, wherein the structural formula of the end group protection alkanoic acid is as follows:
Figure BDA0002281975290000041
wherein n is 2-12, 15-17
Or
Figure BDA0002281975290000042
Wherein n is 2-12, 15.
The structural formula of the end group protection alkane acid liquid crystal nucleus ester is as follows:
Figure BDA0002281975290000043
wherein n is 2-12, 15-17
Or
Figure BDA0002281975290000044
Wherein n is 2-12, 15
Figure BDA0002281975290000045
The preparation method of the main chain type biodegradable liquid crystal polymer comprises the following steps:
Figure BDA0002281975290000051
wherein n is 2-12, 15-17
Or
Figure BDA0002281975290000052
Wherein n is 2-12, 15
Figure BDA0002281975290000053
The preparation method of the main chain type biodegradable liquid crystal polymer comprises the steps that (1.1) the concentration of a solution for dissolving the terminal hydroxy alkanoic acid or the terminal amino acid is an unsaturated solution or a saturated solution; the dichloromethane solution of triphenylchloromethane in the step (1.2) has the concentration of unsaturated solution or saturated solution.
In the preparation method of the main chain type biodegradable liquid crystal polymer, in the step (2.1), the concentration of a dichloromethane solution of the terminal group protected alkanoic acid is an unsaturated solution or a saturated solution, the concentration of a dichloromethane solution of oxalyl chloride is an unsaturated solution or a saturated solution, and the addition amount of dimethylformamide is 0-80% of the volume of the dichloromethane solution; in the step (2.3), the concentration of the chloroform solution of the liquid crystal nucleus is an unsaturated solution or a saturated solution, and the addition amount of pyridine is 0-80% of the volume of the dichloromethane solution; the concentration of the chloroform solution of the end group protection alkanoyl chloride is unsaturated solution or saturated solution; and (2.5) in the mixed solution of chloroform and methanol, the volume ratio of chloroform to methanol is 1: 1-1: 20.
In the preparation method of the main chain type biodegradable liquid crystal polymer, in the step (3.1), the concentration of a dichloromethane solution of the terminal group protected alkanoic acid liquid crystal nucleus ester is an unsaturated solution or a saturated solution; in the step (3.2), the concentration of the dichloromethane solution of trifluoroacetic acid is unsaturated solution or saturated solution.
In the preparation method of the main chain type biodegradable liquid crystal polymer, in the step (4.2), the concentration of the anhydrous toluene solution of stannous octoate is 0-2 mol/L.
The design idea of the invention is as follows:
the invention takes natural products such as cholesterol, diosgenin, menthol, isosorbide and the like as liquid crystal nuclei, introduces hydroxyl-terminated alkanoic acid or amino acid into the structure of the liquid crystal nuclei through chain extension reaction such as esterification and the like to obtain a liquid crystal intermediate with primary hydroxyl/amino to improve the reaction activity of the liquid crystal nuclear hydroxyl, and further takes the liquid crystal intermediate as an initiator to initiate ring-opening polymerization reaction of one or a mixture of two or more than two of monomers such as trimethylene carbonate, caprolactone, lactide, glycolide, p-dioxanone, propiolactone, butyrolactone, octalactone, caprolactam, morpholine-2, 5-dione, dianhydride and the like and derivatives thereof, thereby obtaining the main chain type biodegradable liquid crystal polymer.
The invention has the advantages and beneficial effects that:
1. the structure of the main chain type biodegradable liquid crystal polymer prepared by the invention contains cholesterol or diosgenin or menthol or isosorbide and other bioactive elements, so that the biocompatibility and the affinity of the material can be greatly improved;
2. the main chain type biodegradable liquid crystal polymer prepared by the invention has good liquid crystal performance, liquid crystal elements are easy to orient to form an ordered structure, and the application range of the liquid crystal polymer can be widened by the response of the liquid crystal polymer to the outside such as temperature, pH, stress, electric field, magnetic field and the like;
3. the main chain type biodegradable liquid crystal polymer prepared by the invention has controllable degradation rate and physical properties, can be accurately regulated and controlled through the molecular weight, copolymerization types and copolymerization proportion, and can meet different clinical application requirements.
4. The preparation raw materials (liquid crystal nucleus, flexible spacer, melting reduction section and the like) required by the main-chain biodegradable liquid crystal polymer prepared by the invention have wide sources and low price, are suitable for large-scale preparation and production, and are beneficial to reducing the production cost.
Drawings
FIG. 1 is a drawing showing a main chain type biodegradable liquid crystal polymer prepared in example 1 of the present invention1H-NMR spectrum.
FIG. 2 is a schematic view (200X) of the main chain type biodegradable liquid crystal polymer prepared in example 1 of the present invention.
FIG. 3 is an XRD spectrum of a main chain type biodegradable liquid crystal polymer prepared in example 1 of the present invention; in the figure, the abscissa 2 θ represents the diffraction angle (°), and the ordinate Relative Intensity represents the Relative Intensity.
FIG. 4 is a DSC spectrum of main chain type biodegradable liquid crystal polymer prepared in example 1 of the present invention; in the figure, Temperature on the abscissa represents Temperature (. degree. C.), and Heat Flow on the ordinate represents Heat Flow (mW/mg).
FIG. 5 is a scanning electron microscope picture of the main chain type biodegradable liquid crystal polymer prepared in example 1 of the present invention after degradation under rat skin.
FIG. 6 is a graph showing the relationship between the weight loss rate and the degradation time of the main-chain type biodegradable liquid crystal polymer prepared in example 1 of the present invention implanted subcutaneously in rats. In the figure, the abscissa Time represents the degradation Time (d), and the ordinate Mass Loss represents the weight Loss ratio (%).
FIG. 7 is a HE section in which a main chain type biodegradable liquid crystal polymer prepared in example 1 of the present invention was implanted in a subcutaneous post-implantation site of a rat.
Detailed Description
In the specific implementation process, the molecular structure of the main chain type biodegradable liquid crystal polymer comprises a liquid crystal core, a flexible spacer and a degradable chain segment; the liquid crystal nucleus is natural products such as cholesterol, diosgenin, menthol, isosorbide and the like; the degradation chain segment is homopolymer of trimethylene carbonate, caprolactone, lactide, glycolide, p-dioxane ketone, lactide, butyrolactone, octalactone, caprolactam, morpholine-2, 5-diketone and dianhydride or copolymer of any two or more monomers. The flexible spacer is glycolic acid, 3-hydroxypropionic acid, 4-hydroxybutyric acid, 5-hydroxypentanoic acid, 6-hydroxyhexanoic acid, 7-hydroxyheptanoic acid, 8-hydroxyoctanoic acid, 9-hydroxynonanoic acid, 10-hydroxydecanoic acid, 11-hydroxyundecanoic acid, 12-hydroxydodecanoic acid, 15-hydroxypentadecanoic acid, 16-hydroxyhexadecanoic acid, 17-hydroxyheptadecanoic acid, etc., as well as 2-aminoacetic acid, 3-aminopropionic acid, 4-aminobutyric acid, 5-aminopentanoic acid, 6-aminocaproic acid, 7-aminoheptanoic acid, 8-aminocaprylic acid, 9-aminononanoic acid, 10-aminodecanoic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, 15-aminopentadecanoic acid, etc.
The preparation method of the main chain type biodegradable liquid crystal polymer is carried out according to the following steps:
1. preparation of end-group protected alkanoic acids
1.1, dissolving a hydroxy-terminated alkanoic acid or a hydroxy-terminated amino acid in a reactor filled with dichloromethane and triethylamine solution, wherein the molar ratio of the hydroxy-terminated alkanoic acid or the hydroxy-terminated amino acid to the triethylamine is 1: (1-10);
1.2, slowly dripping dichloromethane solution of triphenylchloromethane under stirring under the cooling condition of ice-water bath, wherein the dripping amount of the triphenylchloromethane is that the molar weight ratio of terminal hydroxyl alkanoic acid or terminal amino acid is 1: (1-10) times;
1.3, reacting at room temperature for 6-12 h after dripping;
1.4, sequentially using water and 1 mol. L-1Washing with hydrochloric acid, saturated sodium bicarbonate solution and saturated salt solution, drying with anhydrous sodium sulfate, concentrating to dryness, and recrystallizing with petroleum ether to obtain the terminal group-protected alkanoic acid.
2. Preparation of end group protection alkanoic acid liquid crystal nucleus ester
2.1, adding a methylene chloride solution of the end-group protected alkanoic acid into a reactor, adding a small amount of Dimethylformamide (DMF), and then dropwise adding a methylene chloride solution of oxalyl chloride into the reactor under an ice bath condition, wherein the molar ratio of the oxalyl chloride to the end-group protected alkanoic acid is (1-5): 1;
2.2, reacting at room temperature for 1-6 h, and then performing rotary evaporation to obtain end group protection alkanoyl chloride;
2.3, adding liquid crystal nuclei such as cholesterol, diosgenin, menthol, isosorbide and the like into the reactor, dissolving chloroform, dropwise adding a small amount of pyridine, and then continuously dropwise adding (2.2) the prepared chloroform solution of the end group protection alkanoyl chloride, wherein the molar ratio of the end group protection alkanoyl chloride to the liquid crystal nuclei is 1: (1-8);
and 2.4, carrying out reflux reaction for 2-36 h. Cooling, rotary evaporating, precipitating with methanol, and filtering to obtain crude product.
And 2.5, recrystallizing the crude product by using a mixed solution of chloroform and methanol, filtering and drying to obtain the end group protection alkanoic acid liquid crystal nucleus ester.
3. Preparation of liquid crystal initiator
3.1 addition of a solution of the terminal-protected alkanoic acid in nuclear ester in dichloromethane and triethylsilane (Et)3SiH), terminal group protected alkanoic acid liquid crystal nucleus ester and Et3The molar ratio of SiH is 1: (1-6);
3.2, slowly adding a dichloromethane solution of trifluoroacetic acid into the reactor under stirring, wherein the molar ratio of the end group protected alkanoic acid liquid crystal nucleus ester to the trifluoroacetic acid is 1: (1-6);
3.3, reacting at room temperature for 0.5-6 h. After rotary evaporation, ethyl acetate is dissolved, the mixture is washed by water and saturated saline solution in sequence, an organic phase is dried by anhydrous magnesium sulfate, the filtration is carried out, a filtrate is concentrated, and a liquid crystal initiator is obtained through column chromatography.
4. Preparation of main chain type biodegradable liquid crystal polymer
4.1, adding a liquid crystal initiator and one or two or more than two degradation chain segment monomers of trimethylene carbonate, caprolactone, lactide, glycolide, p-dioxane ketone, propiolactone, butyrolactone, octalactone, caprolactam, morpholine-2, 5-diketone and dianhydride into a reactor, wherein the molar ratio of the liquid crystal initiator to the degradation chain segment monomers is 1: 50-20000;
4.2, decompressing and vacuumizing for 2-4 times, and adding an anhydrous toluene solution of stannous octoate, wherein the mole number of the stannous octoate is 0-2% (preferably 0.1-1.5%) of the mole number of the degradation chain segment monomer;
4.3, carrying out vacuum pumping for 2-4 times again under reduced pressure, sealing the reactor, and then heating to 80-160 ℃ for reaction for 8-72 hours;
4.4 CHCl was used for the product3Dissolving, precipitating in methanol, cleaning, and drying to constant weight to obtain main chain type biodegradable liquid crystal polymer.
The structural formula of the terminal group protection alkanoic acid is as follows:
Figure BDA0002281975290000081
wherein n is 2-12, 15-17
Or
Figure BDA0002281975290000082
Wherein n is 2-12, 15
The structural formula of the terminal group protection alkanoic acid liquid crystal nucleus ester is as follows:
Figure BDA0002281975290000091
wherein n is 2-12, 15-17
Or
Figure BDA0002281975290000092
Wherein n is 2-12, 15
Figure BDA0002281975290000093
The structural formula of the liquid crystal initiator is as follows:
Figure BDA0002281975290000094
wherein n is 2-12, 15-17
Or
Figure BDA0002281975290000095
Wherein n is 2-12, 15
Figure BDA0002281975290000096
The structural formula of the main chain type biodegradable liquid crystal polymer is as follows:
Figure BDA0002281975290000101
wherein n is 2-12, 15-17
Or
Figure BDA0002281975290000102
Wherein n is 2-12, 15
M1, M2, M3: one or two or more of trimethylene carbonate, caprolactone, lactide, glycolide, p-dioxane ketone, lactide, butyrolactone, octalactone, caprolactam, morpholine-2, 5-dione and dianhydride;
x、y、z：0～1000
Figure BDA0002281975290000103
the following examples are presented to enable those skilled in the art to more readily understand and practice the present invention, but they are not to be considered as limiting the scope of the invention, but merely as exemplifications and representations thereof. The present invention is further modified and adapted by the skilled person in view of the above disclosure, and shall not be limited thereto.
Example 1
In this example, the main chain type biodegradable liquid crystal polymer and the preparation method thereof were as follows:
(1) a solution of 18g (200mmol) of 3-hydroxypropionic acid in dichloromethane (300mL) and 83mL (600mmol) of triethylamine were added to the reaction flask, the mixture was cooled in an ice-water bath, and a solution of 55.8g (200mmol) of triphenylchloromethane in dichloromethane (200mL) was slowly added dropwise with stirring. After dropping, the reaction was carried out at room temperature for 8 hours. Sequentially using water and 1mol L-1Washing with hydrochloric acid, saturated sodium bicarbonate solution and saturated sodium chloride solution, drying with anhydrous sodium sulfate, concentrating to dryness, and recrystallizing with petroleum ether to obtain white end group protected propionic acid. Yield: 73%, melting point: 163 to 165 ℃.
(2) A solution of 16.6g (50mmol) of end-capped propionic acid in dichloromethane (300mL) and 80mL of Dimethylformamide (DMF) were added to the reaction flask, cooled in an ice-water bath, and a solution of 16.9mL (200mmol) of oxalyl chloride in dichloromethane (200mL) was slowly added dropwise with stirring. After dropping, reacting at room temperature for 2h, and performing rotary evaporation to obtain the end group protection propionyl chloride.
(3) 19.33g (50mmol) of cholesterol was charged into a reaction flask, 100mL of chloroform and 20mL of pyridine were added thereto and dissolved, 10.5g (30mmol) of the end-group-protected propionyl chloride was added dropwise, and the reaction was refluxed for 36 hours. Cooling, evaporating 90% chloroform solution, precipitating with methanol, filtering, recrystallizing with chloroform-methanol mixed solution (the volume ratio of chloroform to methanol is 1: 2), filtering, and oven drying to obtain white end group-protected propionic acid crystal nucleus ester solid. Yield: 42%, melting point: 206 to 208 ℃.
(4) 35.05g (50mmol) of a solution of the crystal nucleus ester of the terminal-protected propionic acid solution in dichloromethane (400mL) and triethylsilane (Et)3SiH)25mL (150mmol), and trifluoroacetic acid 10.7mL (150mmol) was added slowly with stirring and reacted at room temperature for 1 h. The solvent was spin-dried under reduced pressure, the residue was dissolved in ethyl acetate, washed with water and saturated brine in that order, the organic phase was dried over anhydrous magnesium sulfate, filtered, the filtrate was concentrated, and white liquid crystal initiator crystals were obtained by column chromatography separation. Yield 87%, melting point: 140 to 143 ℃.
(5) 0.092g (0.2mmol) of liquid crystal initiator crystals and 10.2g (0.1mol) of trimethylene carbonate were charged in a reactor, followed by 0.02mmol of a stannous octoate solution in anhydrous toluene (concentration 0.25 mol/L). And (4) filling nitrogen, vacuumizing for 3-5 times by using an oil pump, and then sealing the pipe. The sealed polymerization tube was placed in an oil bath at a temperature of 140 ℃ and reacted for 12 hours under these conditions. After the reaction, the polymerization tube was crushed, the obtained product was dissolved in chloroform, the crushed glass pieces were removed by filtration, and then ethanol was slowly added to the chloroform solution in which the polymer was dissolved to precipitate the polymer. Putting the obtained product in a vacuum drying oven overnight to obtain the main chain type biodegradable liquid crystal polymer with the yield of 90 percent.
(6) The prepared backbone-type biodegradable liquid crystal polymer was molded into a sheet. Soaking in detergent powder water, washing for 1 hr, rinsing with tap water and distilled water repeatedly for several times, and soaking in 75% alcohol for 3 hr for disinfection. Rinsing with sterile normal saline for three times, and drying under sterile conditions. The sterilized main chain type biodegradable liquid crystal polymer film is embedded in the back of a rat under the aseptic operation. After surgery gentamicin was given by weight to diminish inflammation. The implant materials were taken out at the designated time points, washed with distilled water, vacuum-dried to constant weight, and the weight loss rate of the sample was calculated according to the following formula.
Figure BDA0002281975290000111
In the formula, Mass loss is a sample weight loss ratio (%), Wi and Wd are an initial Mass and a dried Mass of the sample, respectively.
The invention takes out animal tissues and carries out relevant treatment to carry out HE staining observation so as to evaluate the biocompatibility of the main chain type biodegradable liquid crystal polymer.
As shown in FIG. 1, from the main chain type biodegradable liquid crystalline polymer prepared in example 1 of the present invention1It can be seen from the H-NMR spectrum that the position of delta-5.27 ppm corresponds to the double bond methine (-CH-C) in the cholesteric group<) A signal; delta-4.60 ppm corresponds to the last methyl group of the cholesteryl group adjacent to the oxygen atom of the ester bond (ii) ((iii))>CH-O-CH2CH2) A signal; δ 4.21ppm and 1.88ppm correspond to-OCH in TMC repeat units, respectively2-CH2-CH2and-OCH2-CH2-CH2A signal. Delta-4.55 ppm corresponds to-CH between the cholesteric liquid crystal nuclei and the TMC repeat units2The OCO signal.1Analysis of the H-NMR spectrum showed that the hydroxyl group of the liquid crystal initiator prepared in example 1 successfully initiated the polymerization reaction of TMC.
As shown in fig. 2, from the optical texture pattern (200 ×) of the main chain type biodegradable liquid crystal polymer prepared in example 1 of the present invention, it can be seen that the main chain type biodegradable liquid crystal polymer gradually appears small fan-shaped texture in the slow temperature decreasing process, and as the temperature decreases, the texture grows up, and when the temperature decreases to 96 ℃, clear fan-shaped texture can be seen, which indicates that the main chain type biodegradable liquid crystal polymer is smectic phase texture.
As shown in fig. 3, from the XRD spectrum of the main chain type biodegradable liquid crystal polymer prepared in example 1 of the present invention, it can be seen that a strong and sharp peak appears at a small angle 2 θ of 1.8 °, indicating that the molecule has long-range interlayer order, and a weak dispersion peak appears at a wide angle 2 θ of 15.7 °, indicating that the molecules have short-size order of lateral mutual stacking, and the polymer is smectic a phase in combination with polarization observation.
As shown in fig. 4, a DSC spectrogram of the main chain type biodegradable liquid crystal polymer prepared in example 1 of the present invention shows that the glass transition temperature of the main chain type biodegradable liquid crystal polymer is-25 ℃, and that a clearing point appears at 98.3 ℃, which indicates that the obtained main chain type biodegradable liquid crystal polymer is in a liquid crystal state at-25 to 98.3 ℃, and can respond to external stress, electric field, magnetic field, and other stimuli at a physiological temperature of a human body (37 ℃).
As shown in FIG. 5, after the main chain type biodegradable liquid crystal polymer prepared in example 1 of the present invention was implanted in the back of rats, the surface thereof was gradually roughened and severely corroded as observed by a scanning electron microscope, indicating that the polymer was degraded in the rat.
As shown in fig. 6, the weight loss rate of the main-chain biodegradable liquid crystal polymer prepared in example 1 of the present invention on the back of rats gradually increased with time, indicating that the main-chain biodegradable liquid crystal polymer has good degradation performance.
As shown in FIG. 7, after the main chain type biodegradable liquid crystal polymer prepared in example 1 of the present invention was implanted in the back of rats, no inflammatory reaction was observed in the tissues of the implanted sites, indicating that the main chain type biodegradable liquid crystal polymer has good biocompatibility.
Example 2
In this example, the main chain type biodegradable liquid crystal polymer and the preparation method thereof were as follows:
(1) a reaction flask was charged with 13.2g (100mmol) of 6-hydroxycaproic acid in dichloromethane (300mL) and 55mL triethylamine (400mmol), ice waterThe bath was cooled and a solution of triphenylchloromethane (55.8 g (200mmol) in dichloromethane (200mL) was slowly added dropwise with stirring. After dropping, the reaction was carried out at room temperature for 8 hours. Sequentially using water and 1mol L-1Washing with hydrochloric acid, saturated sodium bicarbonate solution and saturated sodium chloride solution, drying with anhydrous sodium sulfate, concentrating to dryness, and recrystallizing with petroleum ether to obtain white end group protected caproic acid. Yield: 62%, melting point: 117-119 ℃.
(2) A solution of end-protected hexanoic acid 18.7g (50mmol) in dichloromethane (300mL) and methylformamide (DMF)80mL were added to the reaction flask, cooled in an ice-water bath, and oxalyl chloride 16.9mL (200mmol) in dichloromethane (200mL) was slowly added dropwise with stirring. After dropping, reacting at room temperature for 2h, and performing rotary evaporation to obtain the end group-protected caproyl chloride.
(3) 20.7g (50mmol) of diosgenin is added into a reaction bottle, 100mL of chloroform and 20mL of pyridine are added for dissolution, 7.84g (20mmol) of end group protected caproyl chloride is added dropwise, and the reflux reaction is carried out for 24 hours. After cooling, a chloroform solution with the volume percentage of 90 percent in the solution is distilled out, the concentrated solution is precipitated by a large amount of methanol, filtered, recrystallized by a mixed solution of chloroform and methanol (the volume ratio of the chloroform to the methanol is 1: 1.5), filtered and dried to obtain a white end group protected caproic acid liquid crystal nucleus ester solid. Yield: 53%, melting point: 194-196 ℃.
(4) 7.7g (10mmol) of a solution of the core ester of the end-protected adipic acid solution in dichloromethane (200mL) and triethylsilane (Et)3SiH)7mL (42mmol), and trifluoroacetic acid 4mL (56mmol) was added slowly with stirring and reacted at room temperature for 2 h. The solvent was spin-dried under reduced pressure, the residue was dissolved in ethyl acetate, washed with water and saturated brine in that order, the organic phase was dried over anhydrous magnesium sulfate, filtered, the filtrate was concentrated, and white liquid crystal initiator crystals were obtained by column chromatography separation. Yield 76%, melting point: 172-175 ℃.
(5) Into the reactor were charged 0.11g (0.2mmol) of liquid crystal initiator crystals, 10.2g (0.1mol) of trimethylene carbonate and 11.4g (0.1mol) of caprolactone. And (4) filling nitrogen, vacuumizing for 3-5 times by using an oil pump, and then sealing the pipe. The sealed polymerization tube was placed in an oil bath at a temperature of 130 ℃ and reacted under these conditions for 24 hours. After the reaction, the polymerization tube was crushed, the obtained product was dissolved in chloroform, the crushed glass pieces were removed by filtration, and then ethanol was slowly added to the chloroform solution in which the polymer was dissolved to precipitate the polymer. The obtained product is placed in a vacuum drying oven overnight to obtain the main chain type biodegradable liquid crystal polymer, and the yield is 87%.
Example 3
In this example, the main chain type biodegradable liquid crystal polymer and the preparation method thereof were as follows:
(1) a reaction flask was charged with 10.3g (100mmol) of 4-aminobutyric acid in DMSO (300mL) and 55mL (400mmol) of triethylamine, cooled in an ice-water bath, and slowly added dropwise with stirring with 55.8g (200mmol) of triphenylchloromethane in dichloromethane (200 mL). After dropping, the reaction was carried out at room temperature for 12 hours. Sequentially using water and 1mol L-1Washing with hydrochloric acid, saturated sodium bicarbonate solution and saturated sodium chloride solution, drying with anhydrous sodium sulfate, concentrating to dryness, and recrystallizing with petroleum ether to obtain the end group protected aminobutyric acid. Yield: 68%, melting point: 138-140 ℃.
(2) A solution of the end-capped aminobutyric acid (17.26 g, 50mmol) in dichloromethane (300mL) and methylformamide (DMF) (80 mL) were added to the reaction flask, cooled in an ice-water bath, and a solution of oxalyl chloride (20.3 mL, 240mmol) in dichloromethane (200mL) was slowly added dropwise with stirring. After dropping, reacting at room temperature for 4h, and performing rotary evaporation to obtain the end group-protected aminobutyryl chloride.
(3) 12.5g (80mmol) of menthol was charged into a reaction flask, 100mL of chloroform and 20mL of pyridine were added and dissolved, 7.60g (20mmol) of the end-group-protected aminobutyrylchloride was added dropwise and the reaction was refluxed for 18 hours. After cooling, a chloroform solution with the volume percentage of 91 percent in the solution is distilled out, the concentrated solution is precipitated by a large amount of methanol, filtered, recrystallized by a chloroform-methanol mixed solution (the volume ratio of the chloroform to the methanol is 1: 1), filtered and dried to obtain the solid of the terminal group-protected aminobutyrate crystal nucletide. Yield: 70%, melting point: 142-144 ℃.
(4) A reactor was charged with a solution of 4.8g (10mmol) of the crystalline nuclear ester of aminobutyrate with end group protection in dichloromethane (200mL) and triethylsilane (Et)3SiH)10mL (60mmol), and trifluoroacetic acid 4mL (56mmol) was added slowly with stirring and reacted at room temperature for 4 h. The solvent was spin-dried under reduced pressure, the residue was dissolved in ethyl acetate, washed successively with water and saturated brine, andthe organic phase is dried by anhydrous magnesium sulfate, filtered, concentrated, and separated by column chromatography to obtain white liquid crystal initiator crystal. Yield 66%, melting point: 37-39 ℃.
(5) 0.148g (0.6mmol) of liquid crystal initiator crystals, 10.2g (0.1mol) of trimethylene carbonate, 14.4g (0.1mol) of lactide, and 11.6g (0.1mol) of glycolide were charged in a reactor. And (4) filling nitrogen, vacuumizing for 3-5 times by using an oil pump, and then sealing the pipe. The sealed polymerization tube was placed in an oil bath at a temperature of 130 ℃ and reacted under these conditions for 48 hours. After the reaction, the polymerization tube was crushed, the obtained product was dissolved in chloroform, the crushed glass pieces were removed by filtration, and then ethanol was slowly added to the chloroform solution in which the polymer was dissolved to precipitate the polymer. The obtained product is placed in a vacuum drying oven overnight to obtain the main chain type biodegradable liquid crystal polymer with the yield of 78 percent.
The results of the examples show that the invention uses natural products such as cholesterol, diosgenin, menthol, isosorbide and the like as liquid crystal cores, uses terminal hydroxy alkanoic acid or terminal amino acid as flexible spacers to prepare liquid crystal intermediates, and uses the liquid crystal intermediates as initiators to initiate ring-opening polymerization reaction of one or a mixture of two or more of monomers such as trimethylene carbonate, caprolactone, lactide, glycolide, p-dioxanone, propiolactone, butyrolactone, octalactone, caprolactam, morpholine-2, 5-dione, dianhydride and derivatives thereof, so as to obtain the main chain type biodegradable liquid crystal polymer. The main chain type biodegradable liquid crystal polymer has good liquid crystal performance, is easy to orient to form an ordered structure, not only responds to the outside such as temperature, pH, stress, an electric field, a magnetic field and the like, but also has good biocompatibility and controllable degradation performance, and has huge application prospect in the field of biomedicine.

Claims (9)

1. A main chain type biodegradable liquid crystal polymer, wherein the structural formula of the main chain type biodegradable liquid crystal polymer is as follows:
Figure FDA0003096243120000011
wherein n is＝2～12，15～17
Or
Figure FDA0003096243120000012
Wherein n is 2-12, 15
M1, M2, M3: one or two or more of trimethylene carbonate, caprolactone, lactide, glycolide, p-dioxane ketone, lactide, butyrolactone, octalactone, caprolactam, morpholine-2, 5-dione and dianhydride; x, y, z: 0 to 1000
Figure FDA0003096243120000013
The preparation method of the main chain type biodegradable liquid crystal polymer comprises the following steps:
(1) preparation of end-group protected alkanoic acids
(1.1) dissolving a hydroxy-terminated alkanoic acid or amino-terminated acid in a reactor containing a solution of dichloromethane and triethylamine, wherein: the molar ratio of the hydroxyl-terminated alkanoic acid or the terminal amino acid to the triethylamine is 1: 1-10;
(1.2) under the ice-water bath cooling condition, dropwise adding a dichloromethane solution of triphenylchloromethane under stirring, wherein the molar weight ratio of the dropwise adding amount of the triphenylchloromethane to the molar weight ratio of the terminal hydroxy alkanoic acid or the terminal amino acid is 1: 1-10;
(1.3) reacting at room temperature for 6-12 h after dripping;
(1.4) Water, 1 mol. L in sequence-1Washing with hydrochloric acid, saturated sodium bicarbonate solution and saturated salt solution, drying with anhydrous sodium sulfate, concentrating to dryness, and recrystallizing with petroleum ether to obtain terminal group protected alkanoic acid;
(2) preparation of end group protection alkanoic acid liquid crystal nucleus ester
(2.1) adding a methylene dichloride solution of end-group protected alkanoic acid into a reactor, adding dimethylformamide according to needs, and then dropwise adding a methylene dichloride solution of oxalyl chloride into the reactor under an ice bath condition, wherein the molar ratio of the oxalyl chloride to the end-group protected alkanoic acid is (1-5) to 1;
(2.2) reacting at room temperature for 1-6 h, and then performing rotary evaporation to obtain end group protection alkanoyl chloride;
(2.3) adding cholesterol, diosgenin, menthol or isosorbide liquid crystal nucleus into a reactor, dissolving chloroform, dropwise adding pyridine according to needs, and then continuously dropwise adding the chloroform solution of the end group protection alkanoyl chloride prepared in the step (2.2), wherein the molar ratio of the end group protection alkanoyl chloride to the liquid crystal nucleus is 1: 1-8;
(2.4) carrying out reflux reaction for 2-36 h; cooling, performing rotary evaporation, precipitating with methanol, and filtering to obtain a crude product;
(2.5) recrystallizing the crude product by using a mixed solution of chloroform and methanol, filtering and drying to obtain end group protection alkanoic acid liquid crystal nucleus ester;
(3) preparation of liquid crystal initiator
(3.1) adding a dichloromethane solution of end group protection alkanoic acid liquid crystal nucleus ester and triethylsilane into a reactor, wherein the molar ratio of the end group protection alkanoic acid liquid crystal nucleus ester to the triethylsilane is 1: 1-6;
(3.2) adding a dichloromethane solution of trifluoroacetic acid into the reactor under stirring, wherein the molar ratio of the terminal group protected alkanoic acid liquid crystal nucleus ester to the trifluoroacetic acid is 1: 1-6;
(3.3) reacting at room temperature for 0.5-6 h; after rotary evaporation, dissolving in ethyl acetate, washing with water and saturated saline solution in sequence, standing for crystallization, filtering, concentrating the filtrate, and performing column chromatography to obtain a liquid crystal initiator;
(4) preparation of main chain type biodegradable liquid crystal polymer
(4.1) adding a liquid crystal initiator and one or two or more than two degradation chain segment monomers of trimethylene carbonate, caprolactone, lactide, glycolide, p-dioxane ketone, lactide, butyrolactone, octalactone, caprolactam, morpholine-2, 5-diketone and dianhydride into a reactor, wherein the molar ratio of the liquid crystal initiator to the degradation chain segment monomers is 1: 50-20000;
(4.2) carrying out vacuum pumping for 2-4 times under reduced pressure, and adding an anhydrous toluene solution of stannous octoate according to needs, wherein the mole number of the stannous octoate is 0-2% of that of the degradation chain segment monomer;
(4.3) carrying out vacuum pumping for 2-4 times again under reduced pressure, sealing the reactor, and then heating to 80-160 ℃ for reaction for 8-72 h;
(4.4) use of CHCl for the product3Dissolving, precipitating in methanol, cleaning, and drying to constant weight to obtain main chain type biodegradable liquid crystal polymer.
2. The main chain type biodegradable liquid crystal polymer according to claim 1, wherein the molecular structure of the main chain type biodegradable liquid crystal polymer comprises a liquid crystal nucleus, a flexible spacer and a degradation segment; the liquid crystal nucleus is natural products of cholesterol, diosgenin, menthol or isosorbide; the degradation chain segment is one of homopolymer of trimethylene carbonate, caprolactone, lactide, glycolide, p-dioxane ketone, lactide, butyrolactone, octalactone, caprolactam, morpholine-2, 5-diketone and dianhydride or copolymer of any two or more monomers; the flexible spacer is terminal hydroxyl alkanoic acid or terminal amino acid, the terminal hydroxyl alkanoic acid is glycolic acid, 3-hydroxypropionic acid, 4-hydroxybutyric acid, 5-hydroxypentanoic acid, 6-hydroxyhexanoic acid, 7-hydroxyheptanoic acid, 8-hydroxyoctanoic acid, 9-hydroxynonanoic acid, 10-hydroxydecanoic acid, 11-hydroxyundecanoic acid, 12-hydroxydodecanoic acid, 15-hydroxypentadecanoic acid, 16-hydroxyhexadecanoic acid or 17-hydroxyheptadecanoic acid; the terminal amino acid is 2-aminoacetic acid, 3-aminopropionic acid, 4-aminobutyric acid, 5-aminopentanoic acid, 6-aminocaproic acid, 7-aminoheptanoic acid, 8-aminocaprylic acid, 9-aminononanoic acid, 10-aminodecanoic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid or 15-aminopentadecanoic acid.
3. The main chain type biodegradable liquid crystal polymer according to claim 1, wherein the terminal-protected alkanoic acid has the formula:
Figure FDA0003096243120000031
wherein n is 2-12, 15-17
Or
Figure FDA0003096243120000032
Wherein n is 2-12, 15.
4. The main chain type biodegradable liquid crystal polymer according to claim 1, wherein the end-protected alkanoic acid liquid crystal nucleus ester has the formula:
Figure FDA0003096243120000033
wherein n is 2-12, 15-17
Or
Figure FDA0003096243120000034
Wherein n is 2-12, 15
Figure FDA0003096243120000035
5. The main chain type biodegradable liquid crystal polymer according to claim 1, wherein the liquid crystal initiator has a structural formula of:
Figure FDA0003096243120000041
wherein n is 2-12, 15-17
Or
Figure FDA0003096243120000042
Wherein n is 2-12, 15
Figure FDA0003096243120000043
6. Main chain type biodegradable liquid crystal polymer according to claim 1,
the concentration of the solution for dissolving the hydroxyl-terminated alkanoic acid or the amino acid in the step (1.1) is an unsaturated solution or a saturated solution;
the dichloromethane solution of triphenylchloromethane in the step (1.2) has the concentration of unsaturated solution or saturated solution.
7. Main chain type biodegradable liquid crystal polymer according to claim 1,
in the step (2.1), the concentration of the dichloromethane solution of the terminal group protected alkanoic acid is an unsaturated solution or a saturated solution, the concentration of the dichloromethane solution of oxalyl chloride is an unsaturated solution or a saturated solution, and the addition amount of dimethylformamide is 0-80% of the volume of the dichloromethane solution;
in the step (2.3), the concentration of the chloroform solution of the liquid crystal nucleus is an unsaturated solution or a saturated solution, and the addition amount of pyridine is 0-80% of the volume of the dichloromethane solution; the concentration of the chloroform solution of the end group protection alkanoyl chloride is unsaturated solution or saturated solution;
and (2.5) in the mixed solution of chloroform and methanol, the volume ratio of chloroform to methanol is 1: 1-1: 20.
8. Main chain type biodegradable liquid crystal polymer according to claim 1,
in the step (3.1), the concentration of the dichloromethane solution of the terminal group protected alkanoic acid liquid crystal nucleus ester is an unsaturated solution or a saturated solution;
in the step (3.2), the concentration of the dichloromethane solution of trifluoroacetic acid is unsaturated solution or saturated solution.
9. The main-chain biodegradable liquid crystal polymer according to claim 1, wherein in the step (4.2), the concentration of the anhydrous toluene solution of stannous octoate is 0 to 2 mol/L.
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US6017984A (en) * 1996-10-21 2000-01-25 Clariant Gmbh Colored cholesteric liquid-crystal polymers having optically variable properties
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* Cited by examiner, † Cited by third party
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US6017984A (en) * 1996-10-21 2000-01-25 Clariant Gmbh Colored cholesteric liquid-crystal polymers having optically variable properties
CN103409144A (en) * 2013-08-16 2013-11-27 东北大学 Steroid-element-containing cyclic carbonate active liquid crystal monomer and preparation method thereof
CN104356375A (en) * 2014-10-09 2015-02-18 东北大学 Biodegradable liquid crystal copolymer for side chain sterides comprising primitive and preparation method for copolymer

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