CN102675562A - Polyethylene glycol macromonomer cross-linked high-strength hydrogel and photo-initiation radical polymerization process thereof - Google Patents
Polyethylene glycol macromonomer cross-linked high-strength hydrogel and photo-initiation radical polymerization process thereof Download PDFInfo
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Abstract
The invention discloses a polyethylene glycol macromonomer cross-linked high-strength hydrogel and a photo-initiation radical polymerization process thereof; the hydrogel is prepared by copolymerizing 2-vinyl-4, 6-diamido-1, 3, 5-triazine and polyethylene glycol diacrylate by free radical polymerization, dissolving the 2-vinyl-4, 6-diamido-1, 3, 5-triazine, the polyethylene glycol diacrylate and initiator into solvent, initiating unsaturated bonds of the molecules of the 2-vinyl-4, 6-diamido-1, 3, 5-triazine and the polyethylene glycol diacrylate by the initiator, and carrying out a free radical polymerization reaction. The hydrogel has high stretch resistance and compression resistance, and is good in biocompatibility and optical property.
Description
Technical field
The present invention relates to crosslinked high intensity hydrogel of a kind of polyoxyethylene glycol macromonomer and preparation method thereof; More particularly, relate to polyethyleneglycol diacrylate-copolymerization-2-vinyl-4, the 6-diaminostilbene; 3,5-triazine (PEGDA-co-PVDT) hydrogel and preparation method thereof.
Background technology
Hydrogel is to have hydrophilic radical, can be expanded but water-fast three-dimensional cross-linked network structure polymer by water-soluble.Has higher water-intake rate (water cut is greater than 50% of total mass usually).Because effects such as physical entanglement of polymkeric substance interchain and chemically crosslinked and can not being dissolved in the water can only be swelling to certain shape.Simultaneously, hydrogel has good water permeate, biocompatibility, and stimulating responsive, and cytotoxicity is low, can reduce untoward reaction as body implant.Therefore hydrogel has obtained widespread use in cosmetics of everyday use, environmental engineering (drought-resistant water-preserving), biomedical engineering (wound dressing, drug release carrier, contact lens) and organizational project fields such as (tissue filling material, joint cartilage, supports).
The hydrogel of ordinary construction often when water cut is low, has certain mechanical property; But when higher moisture (as＞90%), physical strength significantly descends, even just chipping under extremely low external force effect, has therefore limited it as the biomaterial especially application of mechanics device.The energy-to-break of bibliographical information typical hydrogels is at 10-1-100J/m2.Some soft tissues in the human body (like flesh leg, ligament, meniscal cartilage etc.) also are made up of gelatinous mass, and this type of tissue has good characteristics such as softness, tough and tensile, shock resistance.If can prepare with the human body soft tissue mechanical property near and have the soft tissue analogue of good biocompatibility, will be a kind of favorable tissue engineering materials.
Why cracked when high-moisture they are, mainly is the heterogeneity because of the hydrogel microtexture, i.e. cross-linking set distribution is unordered, and each chain link is different in size, and the stress that makes every chain can bear is different.Hydrogel begins fracture from the most weak segment, finally causes breaking of whole aquogel system, so the hydrogel overall mechanical properties is very poor.In order to solve this problem of the relatively poor mechanical property of hydrogel; Several kinds of high intensity hydrogels below scientists has been developed in the recent period: dual network (DN) hydrogel; Inorganic nano combined hydrogel of intercalation (NC) and polymer microsphere composite aquogel (MMC), slip ring hydrogel (TP) or the like.But except double-network hydrogel; Other high intensity hydrogel does not have high stretch-proof and incompressible function (Yoshimi Tanaka concurrently; JianPing Gong, Yoshihito Osada.Novel hydrogels with excellent mechanical Performance.Prog.Polym.Sci.2005; 30:1-9.).Simultaneously, these high intensity hydrogels lack good fatigue performance.
Polyoxyethylene glycol (PEG) is as a kind of water-soluble polymer, and its hydrogel cytotoxicity is low, and good biocompatibility is widely used in biomedicine and pharmaceutical material.In addition, the end group of PEG molecular chain is functional group a---hydroxyl, is easy to take place chemical reaction and obtains the polyoxyethylene glycol function monomer; PEG is easy to crystallization in addition, and the range of application of its molecular weight very wide (from hundreds of to several ten thousand), is the polymeric biomaterial through the nondegradation of U.S. FDA approval.South China Science & Engineering University's hair sword has prepared polyethyleneglycol diacrylate cross-linked hydrogel support (patent CN 1010846026A), and this support contains living fat mescenchymal stem cell, finally can form the soft tissue of predetermined shape and size.This shows, utilize PEG to have a good application prospect for matrix prepares hydrogel.
Gather 2-vinyl-4,6-diaminostilbene, 3; 5-triazine (PVDT) can effectively be discerned nucleic acid base and verivate thereof in water: the VDT monomer can form three hydrogen bond actions with uridylic and thymus pyrimidine; Form two hydrogen bonds with VITAMIN B4, form single hydrogen bond action (Hiroyuki Asanuma, Takeshi Ban with guanine; Sumie Gotoh; Takayuki Hishiya, Makoto Komiyama.Hydrogen bonding in water by poly (vinyldiaminotriazine) for the molecular recognition of nucleic acid bases and their derivatives.Macromolecules, 1998; 31:371-377.).Polymkeric substance with the VDT preparation can increase the nonpolar microenvironment in the water, helps the formation of hydrogen bond.Be rich in hydrogen bond donor and acceptor in the DNA base, can effectively discern and act on target molecule through hydrogen bond action.Existing bibliographical information PVDT can form the effective transfectional cell of mixture (Zhiqiang Cao with DNA; Wenguang Liu; Dongehun Liang; Gang Guo, Jingyu Zhang.Design of poly (vinyl diamino triazine)-based nonviral veetors via specific hydrogen bonding with nueleic acid base pairs.Adv.Funct.Mater.2007; 17:246-252.) be different from traditional transfection method (DNA is compressed into and joins behind the nanoparticle in the training base and cells contacting); Anti-phase transfection (reverse transfaction) method can fixed dna in the top layer of solid material; To increase the chance that cell contacts with DNA like this, improve transfection efficiency.And do not rely on transfection reagent, can reduce the toxicity that transfection reagent brings.Hydrogel behind the PVDT light initiation polymerization, surperficial hydrogen bond action is adsorption of DNA effectively.In addition, the strong hydrogen bonding effect of body makes the stretching of hydrogel and compression performance significantly improve.
It is method commonly used that radical polymerization prepares the PEG hydrogel, and radical transmits generation chain polymerization through unsaturated ethylene group on the PEG macromonomer, thereby obtains crosslinking structure.Radical polymerization can be selected different initiating methods, mainly contains initiator initiation and UV-light and causes.Visible light or UV-light can produce radical with the light trigger effect, thereby initiated polymerization obtains cross-linked hydrogel.Photopolymerization reaction has been compared following advantage with traditional polymerization technique: can under room temperature or physiological condition, carry out; Laser curing velocity fast (from several seconds to several minutes); The reaction liberated heat is few; Reaction conditions is gentle, can pair cell and tissue cause damage.
Summary of the invention
Based on above technical background, the invention provides crosslinked high intensity hydrogel of a kind of polyoxyethylene glycol macromonomer and preparation method thereof.Mainly be to cause copolymerization by initiator, obtain all good high intensity hydrogel of tensile property and compression performance through PEGDA macromonomer and VDT.
The object of the present invention is to provide a kind of HS polyethyleneglycol diacrylate-copolymerization-2-vinyl-4; The 6-diaminostilbene; 3; 5-triazine (PEGDA-co-PVDT) hydrogel and preparation method thereof, this hydrogel has very strong stretch-proof and resistance to compression, and has excellent biological compatibility and optical property.
The object of the invention is achieved through following technical proposals:
The crosslinked high intensity hydrogel of a kind of polyoxyethylene glycol macromonomer, by 2-vinyl-4, the 6-diaminostilbene; 3,5-triazine and polyethyleneglycol diacrylate form through the radical polymerization copolymerization, with 2-vinyl-4; 6-diamino-1,3,5-triazines, polyethyleneglycol diacrylate and initiator are dissolved in the solvent; Cause 2-vinyl-4,6-diaminostilbene, 3 through initiator; Unsaturated link(age) on 5-triazine, the polyethyleneglycol diacrylate molecule is prepared hydrogel through Raolical polymerizable.
In technical scheme of the present invention; With polyethyleneglycol diacrylate and 2-vinyl-4; The 6-diaminostilbene; 3, the 5-triazine is as comonomer, and it (is the backbone structure of peg molecule---(CH that the molecular chain two ends of polyethyleneglycol diacrylate molecule have the skeleton structure that links to each other for " oxygen-carbon-to-carbon-oxygen " singly-bound in the middle of two keys, the molecular chain
2CH
2O)
n), adopt thermal source or light source to make initiator that radical is provided, cause polyethyleneglycol diacrylate and 2-vinyl-4 by radical again, copolyreaction takes place in the two keys in 6-diamino--triazine.In the hydrogel material of final preparation, have polyethyleneglycol diacrylate and gather 2-vinyl-4, the segment of two kinds of materials of 6-diamino-1,3,5-triazines.Wherein, 2-vinyl-4,6-diaminostilbene; 3, form a large amount of hydrogen bonds between a large amount of amino on the 5-triazine molecule, greatly improved the toughness and the intensity of hydrogel; The polyethyleneglycol diacrylate structure provides flexible hydrophilic segment, and above-mentioned two portions synergy makes whole hydrogel material embody high-hydroscopicity; HS and bigger elongation at break, and excellent biological compatibility.
The radical that utilizes initiator to provide causes polyethyleneglycol diacrylate and 2-vinyl-4, and the 6-diamino-1,3,5-triazines reacts.Wherein initiator can be selected thermal initiator commonly used in the high molecular polymerization field; Like Diisopropyl azodicarboxylate (ABIN), Lucidol (BPO); Perhaps light trigger; As 1-[4-(2-hydroxy ethoxy)-phenylene]-2-hydroxyl-2 ', 2 '-dimethyl-ethyl ketone (Irgacure 2959), methyl vinyl ketone, st-yrax.If selection thermal initiator; Then need at first utilize rare gas element (like nitrogen, argon gas or helium) to get rid of the oxygen in the reaction system; To avoid its inhibition,, reaction system is heated on the kick off temperature of used initiator and keeps considerable time then according to the activity and the consumption of initiator; As more than the 1h or longer (1-5h); To impel initiator can produce abundant radical for a long time, the initiation reaction system continues Raolical polymerizable takes place, and finally prepares hydrogel of the present invention.If selective light initiator; Then can select transparent airtight reaction vessel for use; Under the condition of UV-irradiation, cause radical polymerization, because light-initiated efficient is higher than thermal initiation, when adjusting irradiation time with consumption according to the activity of selected initiator; Irradiation time can be shorter than the heat-up time of thermal initiation, like 20 minutes or longer (30min-1h).
In technical scheme of the present invention; Should be according to the solvability of comonomer, the initiator that select to use; The solvent that selection can be dissolved above-mentioned substance fully or can be dissolved each other fully with above-mentioned substance; To mix reaction system, for example N, N,N-DIMETHYLACETAMIDE, THF, DMSO 99.8MIN..
In the preparation scheme, monomer polyethyleneglycol diacrylate (number-average molecular weight is 2000-4000) and 2-vinyl-4, the mass ratio of 6-diamino-1,3,5-triazines is (0.5～5): 1, the quality of initiator is 2%～3% of a monomer total mass.After the reaction end, from reaction vessel, take out multipolymer, after removal is participated in monomer, initiator and the solvent of reaction, be immersed in the water until reaching swelling equilibrium (as soaking 7 days, every separated 12h replacing primary water reaches swelling equilibrium).As shown in Figure 1, along with the rising of PEGDA and VDT mass ratio (P/V), hydrogel progressively shows as transparence, and the balance water regain also rises gradually.
A kind of HS PEGDA-co-PVDT hydrogel provided by the invention is with polyethyleneglycol diacrylate and 2-vinyl-4, and the 6-diamino-1,3,5-triazines is a raw material, and copolymerization is processed under the initiator existence causes.Make hydrogel combine polyethyleneglycol diacrylate and 2-vinyl-4 simultaneously, the character of 6-diamino-1,3,5-triazines has very high water-intake rate, and very strong stretch-proof and resistance to compression have excellent biological compatibility and optical property.This hydrogel at room temperature prepares, and the preparation method is simple, and it is low to consume energy, and product is easy to prolonged preservation and long-distance transport.
Description of drawings:
Fig. 1 is PEGDA-co-PVDT hydrogel (used PEG molecular weight is 2000) the swelling equilibrium photo of different PEGDA and VDT mass ratio (P/V), P/V:a among the figure: 0.5, b: 1, c: 2, d: 3, e: 5.
Embodiment
Further specify technical scheme of the present invention below in conjunction with specific embodiment.
Wherein polyoxyethylene glycol double methacrylate (PEGDA) can directly be bought the Sigma company from the U.S., and selects corresponding molecular weight; Perhaps select corresponding molecular weight polyethylene glycol to synthesize: under the cooling and stirring effect, the PEG (Mn=2000-4000) of 10g vacuum-drying to be dissolved in the 50ml methylene dichloride according to following step; After the dissolving evenly, dropwise add triethylamine, and then dropwise add acrylate chloride; Guarantee that triethylamine and acrylate chloride are excessive with respect to PEG; Its mol ratio can be selected n (triethylamine): n (acrylate chloride): n (PEG)=(4-6): (4-6): 1, and under the nitrogen protection, room temperature 20-25 ℃ of reaction 24h.Leave standstill, decompress filter removes the deposition that dereaction generates then, separates out the product in the solution with cold diethyl ether then, places vacuum drying oven dry two days, promptly obtains polyethyleneglycol derivative---PEGDA.
Embodiment 1:
1) polyoxyethylene glycol (Mn=2000) diacrylate is synthetic: under the cooling and stirring effect, the PEG (Mn=2000) of 10g vacuum-drying is dissolved in the 60ml methylene dichloride; After the dissolving evenly, dropwise add 2.790ml (0.02mol) triethylamine, and then dropwise add 1.625ml (0.02mol) acrylate chloride (its mol ratio: n (triethylamine): n (acrylate chloride): n (PEG)=4: 4: 1); Under the nitrogen protection, room temperature reaction 24h.Leave standstill, decompress filter removes the deposition that dereaction generates then, in filtrating, adds the 300ml cold diethyl ether then, separates out the product in the solution, places vacuum drying oven dry two days, and products therefrom is polyethyleneglycol diacrylate (PEGDA);
2) preparation of macromole polyoxyethylene glycol hydrogel: with PEGDA (13.3mg), the 2-vinyl-4 of above method preparation; 6-diamino--triazine (26.7mg); With light trigger 2-hydroxyl-4-(2-hydroxy ethoxy)-2-methyl phenyl ketone (Igracure2959; 0.8mg), be dissolved in 204 μ l DMSO 99.8MIN. (DMSO) solvents, be mixed with homogeneous solution.Gained solution is injected the printing opacity closed mold, and mould shines 30min under the 360nm UV-light, forms gel network to cause radical polymerization.Open mould subsequently and take out gel, then the gained gel is immersed in the deionized water, changed primary water in per 12 hours, the medium DMSO in the former gelling system is replaced into water, promptly obtain hydrogel through the double diffusion effect.
Embodiment 2:
1) synthesis step of polyoxyethylene glycol (Mn=2000) diacrylate is the same;
2) preparation of macromole polyoxyethylene glycol hydrogel: with above-mentioned PEGDA (20mg), 2-vinyl-4; 6-diamino--triazine (20mg); With light trigger Igracure 2959 (0.8mg), be dissolved in 204 μ l DMSO 99.8MIN. (DMSO) solvents, be mixed with homogeneous solution.Gained solution is injected the printing opacity closed mold, and mould shines 30min under the 360nm UV-light, forms gel network to cause radical polymerization.Open mould subsequently and take out gel, then the gained gel is immersed in the deionized water, changed primary water in per 12 hours, the medium DMSO in the former gelling system is replaced into water, promptly obtain hydrogel through the double diffusion effect.This gel equilibrium water absorption is greater than 95%, and light transmission is good, but intensity is relatively low.
Embodiment 3:
1) polyethyleneglycol diacrylate (Mn ≈ 4000) is synthetic: under the cooling and stirring effect, the PEG (Mn 4000) of 10g (2.5mmol) vacuum-drying is dissolved in the 60ml methylene dichloride; After the dissolving evenly, dropwise add 1.674ml triethylamine (15mmol), and then dropwise add 0.975ml acrylate chloride (15mmol); Under the nitrogen protection, room temperature reaction 24h.Leave standstill, decompress filter removes the deposition that dereaction generates then, in filtrating, adds the 300ml cold diethyl ether then, separates out the product in the solution, places vacuum drying oven dry two days, promptly obtains polyethyleneglycol diacrylate (PEGDA).
2) preparation of macromole polyoxyethylene glycol hydrogel: with PEGDA (26.7mg), the 2-vinyl-4 of above-mentioned prepared in reaction; 6-diamino--triazine (13.3mg); With light trigger Igracure 2959 (0.8mg), be dissolved in 204 μ l DMSO 99.8MIN. (DMSO) solvents, be mixed with homogeneous solution.Gained solution is injected the printing opacity closed mold, and mould shines 30min under the 360nm UV-light, forms gel network to cause radical polymerization.Open mould subsequently and take out gel, then the gained gel is immersed in the deionized water, changed primary water in per 12 hours, the medium DMSO in the former gelling system is replaced into water, promptly obtain hydrogel through the double diffusion effect.
Embodiment 4:
1) synthesis step of polyethyleneglycol diacrylate (Mn ≈ 4000) is with embodiment three steps;
2) preparation of macromole polyoxyethylene glycol hydrogel: with PEGDA (30mg), the 2-vinyl-4 of above-mentioned prepared in reaction; 6-diamino--triazine (10mg); With light trigger Igracure 2959 (0.8mg), be dissolved in 204 μ l DMSO 99.8MIN. (DMSO) solvents, be mixed with homogeneous solution.Gained solution is injected the printing opacity closed mold, and mould shines 30min under the 360nm UV-light, forms gel network to cause radical polymerization.Open mould subsequently and take out gel, then the gained gel is immersed in the deionized water, changed primary water in per 12 hours, the medium DMSO in the former gelling system is replaced into water, promptly obtain hydrogel through the double diffusion effect.This gel equilibrium water absorption is greater than 90%, and light transmission is good, but intensity is relatively low.
Embodiment 5:
1) synthesis step of polyethyleneglycol diacrylate (Mn ≈ 4000) is with embodiment three steps;
2) preparation of macromole polyoxyethylene glycol hydrogel: with PEGDA (50mg), the 2-vinyl-4 of above-mentioned prepared in reaction; 6-diamino--triazine (10mg); With light trigger Igracure 2959 (1.2mg), be dissolved in 306 μ l DMSO 99.8MIN. (DMSO) solvents, be mixed with homogeneous solution.Gained solution is injected the printing opacity closed mold, and mould shines 30min under the 360nm UV-light, forms gel network to cause radical polymerization.Open mould subsequently and take out gel, then the gained gel is immersed in the deionized water, changed primary water in per 12 hours, the medium DMSO in the former gelling system is replaced into water, promptly obtain hydrogel through the double diffusion effect.This gel equilibrium water absorption is up to 90%, and light transmission is good, but intensity is relatively low.
Embodiment 6:
1) preparation of polyethyleneglycol diacrylate is referring to above-mentioned steps.
2) preparation of polyethyleneglycol diacrylate hydrogel: with the PEGDA (40mg) and the light trigger Igracure 2959 (0.8mg) of above-mentioned prepared in reaction, be dissolved in 204 μ l DMSO 99.8MIN. (DMSO) solvents, be mixed with homogeneous solution.Gained solution is injected the printing opacity closed mold, and mould shines 30min under the 360nm UV-light, forms gel network to cause radical polymerization.Open mould subsequently and take out gel, then the gained gel is immersed in the deionized water, changed primary water in per 12 hours, the medium DMSO in the former gelling system is replaced into water, promptly obtain hydrogel through the double diffusion effect.This gel equilibrium water absorption is greater than 90%, and light transmission is good, but intensity is relatively low, and toughness is relatively poor.
For the above hydrogel of respectively organizing, prepare sheet or column sample by same steps as, use WGW microcomputer control electronics universal testing machine (Jinan Instr Ltd. in epoch in epoch) to carry out Mechanics Performance Testing.The sample that wherein carries out the tensile property test is of a size of 30mm * 4mm, and thick is the sheet gel of 500 μ m.The sample size of carrying out the compression performance test is diameter 8mm, the cylinder of high 10mm.Elongation test speed is 50mm/min, and compression speed is 10mm/min.The various performance parameters of the hydrogel sample that table 1 obtains for the foregoing description (the PEG molecular weight is 4000).It is thus clear that it has higher equilibrium water absorption, and good mechanical property.
Table 1.PEGDA-co-PVDT hydrogel performance perameter table
"-" refers to that this gel is depressed into ultimate strain and does not rupture
More than the present invention has been done exemplary description; Should be noted that; Under the situation that does not break away from core of the present invention, the replacement that is equal to that any simple distortion, modification or other those skilled in the art can not spend creative work all falls into protection scope of the present invention.
Claims (7)
1. the high intensity hydrogel that the polyoxyethylene glycol macromonomer is crosslinked is characterized in that, by 2-vinyl-4; 6-diamino-1,3,5-triazines and polyethyleneglycol diacrylate form through the radical polymerization copolymerization; With 2-vinyl-4,6-diaminostilbene, 3; 5-triazine, polyethyleneglycol diacrylate and initiator are dissolved in the solvent, cause 2-vinyl-4,6-diaminostilbene through initiator; 3, the unsaturated link(age) on 5-triazine, the polyethyleneglycol diacrylate molecule is prepared hydrogel through Raolical polymerizable.
2. the crosslinked high intensity hydrogel of a kind of polyoxyethylene glycol macromonomer according to claim 1 is characterized in that the number-average molecular weight of polyethyleneglycol diacrylate is 2000-4000.
3. the crosslinked high intensity hydrogel of a kind of polyoxyethylene glycol macromonomer according to claim 1 is characterized in that monomer polyethyleneglycol diacrylate and 2-vinyl-4, the mass ratio of 6-diamino-1,3,5-triazines are (0.5～5): 1.
4. one kind prepares the crosslinked high intensity hydrogel method of polyoxyethylene glycol macromonomer, it is characterized in that, carries out according to following step: with 2-vinyl-4; 6-diamino-1,3,5-triazines, polyethyleneglycol diacrylate and initiator are dissolved in the solvent; Cause 2-vinyl-4,6-diaminostilbene, 3 through initiator; Unsaturated link(age) on 5-triazine, the polyethyleneglycol diacrylate molecule is prepared hydrogel through Raolical polymerizable.
5. a kind of crosslinked high intensity hydrogel method of polyoxyethylene glycol macromonomer for preparing according to claim 4 is characterized in that monomer polyethyleneglycol diacrylate and 2-vinyl-4, the mass ratio of 6-diamino-1,3,5-triazines are (0.5～5): 1; The quality of initiator is 2%～3% of a monomer total mass.
6. a kind of crosslinked high intensity hydrogel method of polyoxyethylene glycol macromonomer for preparing according to claim 4 is characterized in that the number-average molecular weight of polyethyleneglycol diacrylate is 2000-4000.
7. a kind of crosslinked high intensity hydrogel method of polyoxyethylene glycol macromonomer for preparing according to claim 4 is characterized in that said solvent is N, N,N-DIMETHYLACETAMIDE, THF or DMSO 99.8MIN.; Said initiator is azo Diisopropyl azodicarboxylate, Lucidol, 1-[4-(2-hydroxy ethoxy)-phenylene]-2-hydroxyl-2 ', 2 '-dimethyl-ethyl ketone, methyl vinyl ketone or st-yrax.
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Application publication date: 20120919 |