CN106832137B - A kind of high-strength composite hydrogel and preparation method thereof - Google Patents
A kind of high-strength composite hydrogel and preparation method thereof Download PDFInfo
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/10—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of amides or imides
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F120/52—Amides or imides
- C08F120/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F120/56—Acrylamide; Methacrylamide
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- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
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- C08J3/075—Macromolecular gels
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- C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
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Abstract
The invention belongs to biomedicine fields, specifically disclose a kind of high-strength composite hydrogel and preparation method thereof.Polyacrylamide is bonded simultaneously inside its surface and duct by the SiO 2 molecular sieve of Nano grade to form.Take the SiO 2 molecular sieve, acrylamide and ammonium persulfate aqueous solution of Nano grade, stirring to dirty solution；It after ultrasonic disperse is uniform, vacuumizes, be centrifuged, take out precipitating, be dried to obtain composite molecular screen；The composite molecular screen prepared is uniformly mixed with acrylamide aqueous solution, is vacuumized, is warming up to 75 ~ 85 DEG C, 30 ~ 40min of isothermal reaction, obtains viscous liquid；It is put into mold, adds N, N- bismethacrylamide aqueous solution, in 50 ~ 60 DEG C of 7 ~ 8h of heating to get composite hydrogel.Gained high-strength composite hydrogel of the invention has good mechanical property, and preparation method is easy to operate.
Description
Technical field
The invention belongs to biomedicine fields, and in particular to a kind of high-strength composite hydrogel and preparation method thereof.
Background technique
In today's society, hydrogel increasingly changes people's lives, it can be used as protection cell or other materials
Medium, and have very high conductibility and biocompatibility.In addition, it can also inject and convenient for being modified, in medical treatment side
Face has very big proper value, is able to solve many social concerns.Specifically there are following several applications, one can be used as biological doctor
With material (pharmaceutical carrier, contact lenses, artificial-muscle)；Second is that in terms of petrochemical industry (oil displacement agent, dehydrating agent)；Third is that in agriculture
In terms of industry (water-retaining agent, moisture condensation preventing agent)；Fourth is that can be used as daily, cosmetics (sanitary napkin, paper diaper, facial mask etc.).Wherein most
Important field is exactly biological medicine engineering.However, greatly limiting it in many fields since hydrogel mechanical strength is lower
Application, such as nondegradable pharmaceutical carrier, tissue engineering bracket, enzyme engineering, cell engineering.It is well known that a large amount of raw
Modulus rank needed for object material is kPa grade, because the modulus of many natural tissues is exactly this rank.Such as the nasal cartilages of people
The articular cartilage (990kPa ± 50kPa) of (234kPa ± 27kPa), ox, thoracic aorta (43.2kPa ± 15kPa) of pig etc..
In tissue engineering bracket field, the mechanical strength of polymer substrate must match with the environment of surrounding tissue.Therefore, hydrogel
Mechanical strength be its one of important performance indexes as bio-medical material.Recent domestic researcher be devoted to as
What improves the mechanical strength of hydrogel.
Summary of the invention
To solve the deficiencies in the prior art, the purpose of the present invention is to provide a kind of preparation sides of high-strength composite hydrogel
Method, gained high-strength composite hydrogel have good mechanical property, and preparation method is easy to operate.
To achieve the above object, the technical solution adopted by the present invention is as follows:
A kind of high-strength composite hydrogel, by the SiO 2 molecular sieve of Nano grade inside its surface and duct simultaneously
Bonding polyacrylamide forms.
Preparation method, comprising the following steps:
S0, acrylamide aqueous solution, ammonium persulfate aqueous solution and N, N- bismethacrylamide water are prepared respectively in advance
Solution: the mass percent concentration of acrylamide aqueous solution is 15 ~ 40%, and the mass percent concentration of ammonium persulfate aqueous solution is
The mass percent concentration of 0.5 ~ 3%, N, N- bismethacrylamide aqueous solution is 0.4 ~ 1%；
The preparation of S1, composite molecular screen:
S1.1, according to mass volume ratio meter, SiO 2 molecular sieve: acrylamide: ammonium persulfate aqueous solution=0.3 ~ 0.7g
: 2 ~ 4g: 20 ~ 30mL takes the SiO 2 molecular sieve, acrylamide and ammonium persulfate aqueous solution of Nano grade, and stirring is to becoming
Uniform dirty solution；
S1.2, by dirty solution ultrasonic disperse it is uniform after, the bubble being evacuated in SiO 2 molecular sieve completely disappears；
S1.3, will vacuumize gained mixed liquor be centrifuged, take out precipitating, be dried to obtain composite molecular screen；
The initiation polymerization of S2, high-strength composite hydrogel:
S2.1, the composite molecular screen for preparing S1 are uniformly mixed with acrylamide aqueous solution, are vacuumized；
S2.2, system obtained by S2.1 is warming up to 75 ~ 85 DEG C, 30 ~ 40min of isothermal reaction, obtains viscous liquid；
S2.3, viscous liquid is put into mold, adds N, N- bismethacrylamide aqueous solution, in 50 ~ 60
DEG C heating 7 ~ 8h to get composite hydrogel；
Wherein, in S2.1 and S2.3, according to mass volume ratio meter, composite molecular screen: acrylamide aqueous solution: N, N- diformazan
Base bisacrylamide aqueous solution=0.5 ~ 2.5g: 45 ~ 55mL: 0.2 ~ 0.4mL.
The SiO 2 molecular sieve addressed in the present invention, macroshape be it is powdered, micro-shape be in elliposoidal, have it is short
And regular duct, be conducive to the activity for making full use of its inner surface；Particle diameter size is about in 10nm-15nm, particle size
It is of substantially equal, it is evenly dispersed, there is more powder structure cells for being exposed to outside.The structure makes one side of SiO 2 molecular sieve powder
Face has biggish specific surface area, and there is short and regular duct to be easy to adhere in surface and duct upper ammonium persulfate etc. and draw
Agent is sent out, preferably initiation acrylamide polymerization；On the other hand there is better adsorption capacity, initiator is in its surface and duct
It can effectively be loaded, so as to grow acrylamide monomer with effectively attachment initiation in duct on the surface thereof.
The present invention causes acrylamide homopolymerization method using nanometer grade silica molecular sieve low pressure and prepares high-intensitive water rubber:
Firstly, dispersing acrylamide monomer and initiator (ammonium persulfate) for the nanometer grade silica molecular sieve with cellular structure
Aqueous solution in, then by well-mixed liquid draw vacuum, so that the bubble in molecular sieve replaces with mixed liquor completely, then be centrifuged
Obtain molecular sieve solid, that is, composite molecular screen；Then, it is added in the aqueous solution of acrylamide using composite molecular screen as initiator
It vacuumizes, low-pressure heating causes acrylamide polymerization, obtains viscous liquid；Finally, crosslinking agent (N, N- bis- is further added
Bisacrylamide) it is allowed to continue to react, hydrogel is made.
The utility model has the advantages that
1, after molecular sieve is by the way that ultrasonic disperse vacuumizes in initiator, contain initiator among microporous molecular sieve,
SiO 2 molecular sieve is both the center for causing acrylamide polymerization, and reinforces the center of polymer strength, and molecular sieve adds
Enter to make acrylamide to carry out network polymerization centered on molecular sieve, the portion's structure for the hydrogel that standardized so that hydrogel by
It is able to be uniformly distributed stress when power, prevents stress concentration from causing the plastic strains such as fracture, and the molecular sieve of Nano grade
Powder can greatly increase surface area, so that the effects of improving the hydrogen bond on surface power, increases intensity, improve mechanical property.
2, nanometer grade silica molecular sieve of the present invention causes acrylamide polymerization under low pressure, eliminates in traditional handicraft
Logical nitrogen link, and reduce heating temperature and heating time, reduce costs.
Detailed description of the invention
Fig. 1 is embodiment 1(A, amplification factor 300) and reference examples 1(B, amplification factor 500) method gained hydrogel
SEM figure.
Fig. 2 compares for the stretching of hydrogel obtained by embodiment 1(A) and reference examples 1 (B) method.
Fig. 3 is the stretching that embodiment 1 and 2 different initiator concentrations and 3 ultraviolet microwave of embodiment cause lower gained hydrogel
Comparison.
Fig. 4 is the stretching comparison of gained hydrogel under embodiment 1 and 4 different acrylamide aqueous solution concentration.
Specific embodiment
Embodiment 1
A kind of high-strength composite hydrogel, by the SiO 2 molecular sieve of Nano grade inside its surface and duct simultaneously
Bonding polyacrylamide forms.
It takes nanometer grade silica molecular sieve low pressure to cause acrylamide homopolymerization method and prepares high-intensitive water rubber, including with
Lower step:
S0, acrylamide aqueous solution, ammonium persulfate aqueous solution and N, N- bismethacrylamide water are prepared respectively in advance
Solution: the mass percent concentration of acrylamide aqueous solution is 30%, and the mass percent concentration of ammonium persulfate aqueous solution is 2%,
The mass percent concentration of N, N- bismethacrylamide aqueous solution is 1%；
The preparation of S1, composite molecular screen:
S1.1, take 0.5g particle diameter distribution in the SiO 2 molecular sieve, 2g acrylamide and 30mL ammonium persulfate of 10-15nm
Aqueous solution is in 250mL beaker, and stirring is to as uniform dirty solution；
S1.2, dirty solution is put into ultrasonic instrument, adjusting frequency is 8000 hertz, and temperature is 45 DEG C, ultrasonic 10min
Afterwards, the bubble being evacuated in SiO 2 molecular sieve completely disappears；
S1.3, will vacuumize gained mixed liquor averagely pour into four centrifuge tubes, put into a centrifuge, turn speed extremely
8000r/min is centrifuged 5min；
Precipitating in S1.4, taking-up centrifuge tube, is dried to obtain composite molecular screen；
The initiation polymerization of S2, high-strength composite hydrogel:
S2.1, the 0.5g S1 composite molecular screen prepared and 50mL acrylamide aqueous solution are mixed into round-bottomed flask,
It vacuumizes；
S2.2, system oil bath obtained by S2.1 is warming up to 80 DEG C, isothermal reaction 35min, obtains viscous liquid；
S2.3, viscous liquid is put into mold, adds 0.2mL N, N- bismethacrylamide aqueous solution, in
55 DEG C of heating 7h are to get composite hydrogel.
Reference examples 1
Cause acrylamide homopolymerization method with the nanometer grade silica molecular sieve low pressure of embodiment 1 and prepares high-intensitive water rubber
(substantive process is: ammonium persulfate first loads over a molecular sieve, causes polymerization again later) is different, and this example is to be directly added into persulfuric acid
Ammonium initiator prepares hydrogel, and steps are as follows:
S0, acrylamide aqueous solution, ammonium persulfate aqueous solution and N, N- bismethacrylamide water are prepared respectively in advance
Solution: the mass percent concentration of acrylamide aqueous solution is 30%, and the mass percent concentration of ammonium persulfate aqueous solution is 2%,
The mass percent concentration of N, N- bismethacrylamide aqueous solution is 1%；
The initiation polymerization of S1, hydrogel:
S1.1,50mL acrylamide aqueous solution is added in round-bottomed flask, 0.2mL ammonium persulfate aqueous solution is added dropwise, taken out
Vacuum；
S1.2, system oil bath obtained by S1.1 is warming up to 80 DEG C, isothermal reaction 35min, obtains viscous liquid；
S1.3, viscous liquid is put into mold, adds 0.2mL N, N- bismethacrylamide aqueous solution, in
55 DEG C of heating 7h are to get hydrogel.
Fig. 1 is embodiment 1(A, amplification factor 300) and reference examples 1(B, amplification factor 500) method gained hydrogel
SEM figure.The hydrogel that two methods obtain all is cellular, but as can be seen from the figure: the honeycomb of A more close and
Tiny, when by stress, stress distribution is more uniform；The honeycomb of B is more loose and irregular, honeycomb distribution dispersion,
Cavity is larger, and consistency is significantly less than the honeycomb of A, is also more easier to be broken in stress raiser when by stress；
Show that the addition of nanometer grade silica molecular sieve improves the inside uniformity coefficient and crosslinked polymer degree of hydrogel, it is regular
The structure of hydrogel, while molecular sieve is that nanoscale contains there are many micropore, increases surface area to increase hydrogen bond number and work
Firmly, to increase the mechanical strength of hydrogel.
Fig. 2 compares for the stretching of hydrogel obtained by embodiment 1(A) and reference examples 1 (B) method.It can be seen that identical answer
Under the conditions of power, the hydrogel that the molecular sieve after load is prepared has more excellent tensile property；Under identical tensile stress, molecular sieve
The hydrogel of initiation has better intensity, should change it is small, deform it is more unobvious, fracture tensile stress also reach
36.5Mpa, and be directly added into initiator ammonium persulfate and then deform under unitstress obvious and just sent out under the stress less than 15MPa
Fracture is given birth to.Illustrate hydrogel tensile strength improvement and molecular sieve use so that acrylamide polymerization it is more regular uniformly,
The increase of polyacrylamide strand crosslink density is related.
Embodiment 2
Difference from example 1 is that: in S0, adjust the mass percent concentration of initiator ammonium persulfate aqueous solution
Respectively 0.5%, 1%, 3%.
Embodiment 3
Difference from example 1 is that S2 takes ultraviolet microwave to cause polymerization, the steps include:
S2.1, the 0.5g S1 composite molecular screen prepared and 50mL acrylamide aqueous solution are placed in pipe, are passed through nitrogen
Sealing orifice after 15min；
S2.2, pipe is placed in microwave ultraviolet ultrasonic wave Trinity synthesis extraction reaction instrument, 80 under ultraviolet microwave
DEG C processing 3h, be made composite hydrogel.
Fig. 3 is the stretching that embodiment 1 and 2 different initiator concentrations and 3 ultraviolet microwave of embodiment cause lower gained hydrogel
Comparison.It can be seen that, with the increase of initiator concentration, just started tensile strength as increase is significant under identical tensile stress, but
Tensile property has micro decline instead after initiator concentration reaches 2 percent, it may be possible to since kinetic chain length is with causing
The half power of agent concentration is inversely proportional { according to v=Kp/2(fKd*Kt) 2* [M]/[I] }, and initiator concentration draws after improving
It is too fast to send out rate, and rate of chain growth increases unhappy, kinetic chain length (i.e. molecular chain length) decline, therefore is in initiator concentration
Tensile strength reaches maximum value when 2%, and mechanical property is the most excellent；And when ultraviolet microwave initiation, microwave can increase molecular sieve table
Face activity, increase energy needed for providing initiation reaction, and since ultraviolet microwave causes, trigger rate is too fast to prepare
Hydrogel intensity is too low, and tensile property is poor.
Embodiment 4
Difference from example 1 is that: in S0, the mass percent concentration for adjusting acrylamide aqueous solution is respectively
15%、20%、25%、35%、40%。
Fig. 4 is the stretching comparison of gained hydrogel under embodiment 1 and 4 different acrylamide aqueous solution concentration.It can be seen that
With the increase of acrylamide aqueous solution concentration, the mechanical property for the hydrogel prepared is gradually more excellent, tensile strength by
Cumulative to add, unit tensile elongation needs bigger drawing force, especially reaches best when acrylamide aqueous solution concentration is 30%,
Then when acrylamide aqueous solution concentration is improved to 35% and 40%, although unit length drawing force increases its breaking strength
Declined, it may be possible to make the hydrogel prepared there are a large amount of monomer remnants since acrylamide aqueous solution concentration is excessive,
So that the mechanical property of hydrogel is declined instead.
Claims (1)
1. a kind of preparation method of high-strength composite hydrogel, which comprises the following steps:
S0, acrylamide aqueous solution, ammonium persulfate aqueous solution and N, N- bismethacrylamide aqueous solution are prepared respectively in advance:
The mass percent concentration of acrylamide aqueous solution is 15 ~ 40%, the mass percent concentration of ammonium persulfate aqueous solution is 0.5 ~
The mass percent concentration of 3%, N, N- bismethacrylamide aqueous solution is 0.4 ~ 1%；
The preparation of S1, composite molecular screen:
S1.1, according to mass volume ratio meter, SiO 2 molecular sieve: acrylamide: ammonium persulfate aqueous solution=0.3 ~ 0.7g: 2 ~
4g: 20 ~ 30mL takes the SiO 2 molecular sieve, acrylamide and ammonium persulfate aqueous solution of Nano grade, and stirring is to as uniform
Dirty solution；
S1.2, by dirty solution ultrasonic disperse it is uniform after, the bubble being evacuated in SiO 2 molecular sieve completely disappears；
S1.3, will vacuumize gained mixed liquor be centrifuged, take out precipitating, be dried to obtain composite molecular screen；
The initiation polymerization of S2, high-strength composite hydrogel:
S2.1, the composite molecular screen for preparing S1 are uniformly mixed with acrylamide aqueous solution, are vacuumized；
S2.2, system obtained by S2.1 is warming up to 75 ~ 85 DEG C, 30 ~ 40min of isothermal reaction, obtains viscous liquid；
S2.3, viscous liquid is put into mold, adds N, N- bismethacrylamide aqueous solution adds in 50 ~ 60 DEG C
7 ~ 8h is to get composite hydrogel for heat；
Wherein, in S2.1 and S2.3, according to mass volume ratio meter, composite molecular screen: acrylamide aqueous solution: N, N- dimethyl are double
Acrylamide aqueous solution=0.5 ~ 2.5g: 45 ~ 55mL: 0.2 ~ 0.4mL.
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| CN101058824A (en) * | 2006-04-21 | 2007-10-24 | 北京化工大学 | Immobilized enzyme biological catalyst, preparation method and application |
| WO2009041870A1 (en) * | 2007-09-27 | 2009-04-02 | Sca Hygiene Products Ab | Claylinked polymer gels |
| CN104667357A (en) * | 2015-02-05 | 2015-06-03 | 中国科学院兰州化学物理研究所 | Structured hydrogel composite lubricating material and preparation method thereof |
| CN105199281A (en) * | 2015-09-09 | 2015-12-30 | 齐鲁工业大学 | Novel hydrogel with ultrahigh mechanical strength and chemical stability |
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| CN104671693B (en) * | 2014-12-24 | 2016-06-29 | 长安大学 | A kind of concrete strengthens conserving material and preparation method thereof in water conservation |
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| CN101058824A (en) * | 2006-04-21 | 2007-10-24 | 北京化工大学 | Immobilized enzyme biological catalyst, preparation method and application |
| WO2009041870A1 (en) * | 2007-09-27 | 2009-04-02 | Sca Hygiene Products Ab | Claylinked polymer gels |
| CN104667357A (en) * | 2015-02-05 | 2015-06-03 | 中国科学院兰州化学物理研究所 | Structured hydrogel composite lubricating material and preparation method thereof |
| CN105199281A (en) * | 2015-09-09 | 2015-12-30 | 齐鲁工业大学 | Novel hydrogel with ultrahigh mechanical strength and chemical stability |
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