CN107266692A - nanometer composite hydrogel material and preparation method - Google Patents
nanometer composite hydrogel material and preparation method Download PDFInfo
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Abstract
The invention provides a kind of Nanometer composite hydrogel material and preparation method, by calcium hydroxide nanometer spherocrystal (CNS) RPP acid amides, Nanometer composite hydrogel material is prepared.Hydrogel is by by tricalcium silicate, dicalcium silicate, Portland cement or the calcium ion of other binder materials containing Calcium compounds are crystallized under the conditions of 0 DEG C forms CNS, and is uniformly diffused into acrylamide polymer matrix, is prepared from by acrylamide polymer in-situ polymerization with CNS crosslinkings.Dispersed CNS is 0 degree of hydrated product of the binder materials containing Calcium compounds, and crosslinking agent is played a part of in polyacrylamide polymers network.Compared to traditional macromolecule hydrogel that property is crisp and recovery is poor, Nanometer composite hydrogel of the invention has superpower mechanical strength, elasticity, superelevation limiting strain, toughness and restorability.The transparent and low cost of traditional PAM hydrogels has been remained in that by the Nanometer composite hydrogel for the CNS formation for adding low content.
Description
Technical field
The present invention relates to technical field of hydrogel, more particularly to Nanometer composite hydrogel material and preparation method
Background technology
The fatal defects of conventional polymer hydrogel are low intensities, and fragility is high, and transparency is low or deformability is poor.These are not
Evitable problem seriously limits its industry and biomedical applications.Although having been proven that the inorganic nano of several types
Grain, such as clay and graphene oxide (GO) can form the polymer nanocomposite with the mechanical performance significantly increased and be combined
(NC) hydrogel, but the complicated processing of clay and the black color of polymer/GO hydrogels seriously limit their application.
Common inorganic nano-particle, includes the silica and titanium dioxide of nano-scale, it is impossible to form polymer NC hydrogels.Cause
This, the formation and exploitation of high-performance novel polymer NC hydrogels turn into a significant challenge.
Such as Chinese patent CN105419190A discloses a kind of method for preparing medical PVA hydrogel, its feature
It is, comprises the following steps：1) raw material is weighed by following parts by weight：Polyvinyl alcohol 5~20；NMF 8~12；Water or 1% second
Acid 68~87；Preservative 0.1-1；The NMF includes one kind in glycerine, propane diols, sorbierite or polyethylene glycol；It is described
Preservative includes：One kind in sodium benzoate, sorbic acid or parabens；The alcoholysis degree of the polyvinyl alcohol is no less than 88%；
2) polyvinyl alcohol is added to the water, after 50 DEG C~70 DEG C are soaked 10~90 minutes, adds NMF, preservative, continue to heat
It is dissolved to 85 DEG C~100 DEG C, solution A is obtained；By solution A using ultrasonic method or the separation of decompression method and discharge foam；Except de-soak
Solution after foam is poured into mould, be placed at -10 DEG C~-20 DEG C place 10~48 hours, take out, normal temperature decentralization set to 0 .5~
10 hours, hydrogel is packed, irradiated using cobalt -60, irradiation dose 50KGy~150KGy is produced.The water-setting of the preparation
Enter in glue and translucency accordingly studied, however need to take into full account the intensity of rate hydrogel in actual use, it is crisp
The integration capabilities such as property, transparency and deformability.
And for example Chinese patent CN104114591A disclose it is a kind of prepare the method for water-absorbing polymeric particles, including make to contain
Have the aqueous monomers solution or suspension polymerization of following material to obtain waterborne polymeric gel, a) it is at least one with carboxyl and
The ethylenically unsaturated monomers that can be at least partially neutralized, b) at least one crosslinking agent, c) at least one initiator, d) optionally
Ground one or more can with a) in the ethylenically unsaturated monomers of monomer copolymerizable that refer to, it is and e) optionally one or more
Water-soluble polymer, polymer gel described in heated drying is crushed through dry polymer gel to obtain polymer beads, and
Polymer beads obtained by classification, methods described includes the heat foamable agent for being substantially free of inorganic anion being mixed into polymerizable aqueous
In thing gel.Swelling ratio and permeability in the gelatin polymer in preparation process only to gel, do not consider solidifying
The integration capabilities such as glue intensity, deformability, fragility, therefore, its hydrogel have significant limitations in use.
The content of the invention
The problem of to overcome elastic low and poor recovery present in prior art, the invention provides one kind is nano combined
Hydrogel material and preparation method.
The present invention discloses a kind of Nanometer composite hydrogel material, its innovative point is：The composite aquogel is by polymerizeing
Thing constitutes for matrix material, and the nanometer spherocrystal that addition size is less than 10nm is used as crosslinking agent；The polymeric matrix is with propylene
Acid amides AM is monomer, and ammonium persulfate APS is initiator, prepares polyacrylamide PAM；Wherein add N, N, N ', N '-tetramethyl
Base-ethylenediamine is used as catalyst.
Further, the nanometer spherocrystal is calcium hydroxide nanometer spherocrystal；The calcium hydroxide nanometer spherocrystal diameter is less than
10nm。
Further, the composite aquogel contains the nanometer spherocrystal of the content counted using hydrogel weight as 1-500ppm.
Further, the content of the polymer is the 10wt% to 50wt% of hydrogel weight total amount.
Invention further discloses a kind of method for preparing Nanometer composite hydrogel, its innovative point is：Specific steps
It is as follows：
S1, at 0 DEG C in ice bath, by tricalcium silicate/dicalcium silicate/Portland cement/white cement or its compound particles
Grain mixing is hydrated to form calcium hydroxide nanometer spherocrystal, and its calcium hydroxide nanometer spherocrystal is scattered in deionized water translucent to obtain
Water-borne dispersions, obtain homogeneous dispersion after being stirred 10 minutes under ultrasonication, homogeneous dispersion is outstanding for calcium hydroxide
Supernatant liquid；
S2, mixture is made in addition polymer, initiator and catalyst in calcium hydroxide suspension；
S3, mixture is kept for 72 hours in 0 DEG C of ice bath, so that the abundant aquation of tricalcium silicate；
S4, passes through polymerization formation Nanometer composite hydrogel material under 0.01atm；
Wherein, mixing speed is 10rpm to 1000rpm.
Further, the polymer is water-soluble polymer, and water-soluble polymer is selected from polyacrylamide, N- isopropyls
Acrylamide, polyvinyl alcohol or its mixture；The initiator is water-soluble polymer, and the water-soluble polymer is persulfuric acid
Ammonium, potassium peroxydisulfate, sodium peroxydisulfate or 2,2 '-azo diisobutyl amidine dihydrochloride；By dispersant be added in S2 mixture with
Improve the dispersiveness of calcium hydroxide nanometer spherocrystal；The dispersant is anion surfactant, the anion surface active
Agent is polycarboxylate ether, lauryl sodium sulfate, neopelex, PAMA or isethionic acid
Sodium.
Further, the hydration temperature scope of the calcium hydroxide nanometer spherocrystal is -10 DEG C to 40 DEG C.
Further, the polymerization is radical polymerization in situ.
Further, nano particle is added in the mixture in S2 further to improve the mechanicalness of composite aquogel
Energy.
Further, the nano particle is selected from hectorite, montmorillonite, graphene oxide, layered double-hydroxide, titanium
Silicate nanometer piece, controllable active nano gel or its mixture.
Compared with prior art, the beneficial effects of the invention are as follows：
(1) PAM/CNS hydrogel characters are adjusted by CNS concentration, can obtain high-expansion, extension property, rupture stress
And restorability.It can be obtained in unpolymerized CNS by portland cement suspension instead of tricalcium silicate, and another
A kind of macromolecule hydrogel can further obtain performance enhancement by in-situ polymerization.As a result show, the individually scattered ball less than 5nm
Crystalline substance can be obtained by tricalcium silicate in low temperature hydration reaction, and this nanometer of spherocrystal helps hydrogel enhancing cross-linked network and characteristic.
(2) stress when being ruptured by the composite aquogel that 40ppmCNS is modified is 430KPa, and draw ratio is 121,200ppm
CNS composite aquogel has 630KPa stress when draw ratio is 65, and under 100MPa stress, returns to original
The 90% of size.Under same polymer content, the transparency of composite aquogel is identical with original polyacrylamide.
(3) due to oligomerization, small size and dispersed CNS, C200 transparency and initial PAM hydrogels are almost
Equally, the connection between PAM functional groups and CNS is set up by the acid-base reaction of initiator ammonium peroxydisulfate and calcium hydroxide
's.
(4) in 20-80nm xerogel there is a large amount of parallel and crosslinking filament, these structures in the size of loose structure
Size is regularly distributed in hole between 50nm-2um.It is crosslinked between silk and hole inside and there is obvious projection in tie point,
Show possess strong ties power, the attachment force plays an important role in the expansion characteristics and mechanical performance of hydrogel.
(5) polymer molecule in hydrogel cross-linked network is free, high resiliency, mobility, is between CNS
Existing random conformation.
Brief description of the drawings
Fig. 1 is tricalcium silicate particle release CNS TEM figures；
Fig. 2 is the CNS discharged from tricalcium silicate hydration reaction electron diffraction pattern；
Fig. 3 is CNS (the CNS concentration for having 200ppm in PAM/CNS) TEM figures disperseed in C200；
Fig. 4 is the optical photograph of cylindrical C200 samples；
Fig. 5 is the gelatine figure of the PAM/CNS hydrogels under 0.01atm after being placed 10 days under the conditions of 0 DEG C and 1atm；
Fig. 6 is the gelatine for the PAM/CNS hydrogels for placing 3h after being placed 1 day under 0 DEG C and 1atm under 0.01atm
Figure；
Fig. 7 is the gelatine for the PAM/CNS hydrogels for placing 3h after being placed 3 days under 0 DEG C and 1atm under 0.01atm
Figure；
Fig. 8 is the gelatine figure for placing 3hPAM/CNS hydrogels after being placed 5 days under 0 DEG C and 1atm under 0.01atm；
Fig. 9 is the schematic diagram of CNS in PAM crosslinking tricalcium silicates；
Figure 10 is (SO in PAM and C2004CH-And SO4CH2 -) last group and (CN-And CNO-) anion is relative in pendant groups
Peak strength block diagram；
Figure 11 is relative peak intensities curve map in C200；
Figure 12 is the SEM figures of C40 xerogel；
Figure 13 is the SEM scaling figures of boxed area in Figure 12；
Figure 14 is boxed area SEM scaling figures in Figure 13；
Figure 15 is the SEM figures of C200 xerogel；
Figure 16 is boxed area SEM scaling figures in Figure 15；
Figure 17 is boxed area SEM scaling figures in Figure 16；
Figure 18 is that C40, C100 and C200 are soaked in deionized water the expandable hydrogel optical picture after 3 weeks；
Figure 19 is C40, C200 and CA DSC curve；
Figure 20 be CNS concentration be 0,40 and 200ppm under PAM hydrogels tensile stress-strain curve figure；
Figure 21 is the PAM hydrogel compressive stress strain curve figures under C40 and C200；
Figure 22 is that C200 extends 5 times of figures in four cyclic tension load-deformation curves；
Figure 23 is the cyclic stress-strain curve figure of 5 times of amplification during C200 is circulated at four；
Figure 24 is that C200 extends 10 times of figures in four cyclic tension load-deformation curves；
Figure 25 is the cyclic stress-strain curve figure of 10 times of amplification during C200 is circulated at four；
Figure 26 is gelling reaction figure when PAM is mixed respectively with tricalcium silicate and sodium hydroxide at normal temperatures；
Figure 27 is the TEM figures of calcium hydroxide micro-crystal；
Figure 28 is that TEM picture of the concentration of 3 days for the CNS in 500ppm Portland cement suspension is placed in 0 DEG C；
Figure 29 is the SEM pictures that tricalcium silicate disperses in concentration is 500ppm ethanol.
Embodiment
Below in conjunction with drawings and examples, the present invention will be described in further detail.It should be appreciated that described herein
Specific embodiment only to explain the present invention, is not intended to limit the present invention.
Common inorganic nanoparticles, include the silica and titanium dioxide of nanoscale, it is impossible to form polymer nano
Rice composite aquogel.Therefore, the formation of high-performance novel Nanometer composite hydrogel polymer and develop and turn into one and great choose
War.To solve the above problems, calcium hydroxide nanometer spherocrystal is combined with polyacrylamide matrix, the calcium hydroxide with small size is received
Rice spherocrystal plays a part of crosslinking agent.This polyacrylamide base calcium hydroxide nanometer spherocrystal hydrogel (PAM/CNS hydrogels)
The draftability and and uncommon multilayer point pore structure of superelevation are shown under low inorganic content.
To make explanation briefly, in the remainder of present embodiment, calcium hydroxide nanometer spherocrystal (CNS) is only used only in we
To replace C3S、C2S, Portland cement and white cement statement.
Embodiment 1
The present invention discloses the method that one kind prepares Nanometer composite hydrogel (PAM/CNS), preparation process is followed successively by silicic acid
Prepared by the synthesis of DFP, calcium hydroxide CNS suspension, prepared by PAM/CNS Nanometer composite hydrogels material.
The synthesis of tricalcium silicate：Calcium carbonate and silicon silica are mixed with mol ratio 3: 1, are screened by 63um sieve,
Then 1-2h is mixed.The fine powder of acquisition is compressed into thin slice, is placed in crucible and calcines 5h, and temperature is 1500 DEG C, and
Normal temperature is rapidly cooled in 10min.The product of acquisition wears into subdivision, another second compression and calcining.It is last after being repeated 4 times
Tricalcium silicate size is less than 500nm.
It is prepared by calcium hydroxide CNS suspension：
Tricalcium silicate/dicalcium silicate/Portland cement/white cement or its compound particles are mixed and are hydrated to form hydrogen-oxygen
Change calcium nanometer spherocrystal, work as C3S、C2When S, Portland cement or white cement particle are dispersed in water, Ca2+From C3S (or C2S, baud
Blue cement, white cement) in discharge, in aqueous formed calcium hydroxide spherocrystal.Hydration temperature is in whole preparation process
It is vital, hydration temperature is controlled between -10-40 DEG C, preferably hydration temperature is 0 DEG C, mainly due in this temperature
Under, from C3The Ca of S releases2+Rate of release be just enough to form calcium hydroxide spherocrystal, simultaneously as crystallization temperature is low, right hydrogen
Calcium oxide nanometer spherocrystal diameter is less than 10nm, and preferably diameter is less than 5nm, in theory, the small hydrogen-oxygen of good dispersion, size
The performance of novel nano compound water congealing xanthan polymer can be improved by changing calcium nanometer spherocrystal.Calcium hydroxide nanometer spherocrystal is scattered in deionization
To obtain translucent water-borne dispersions in water, homogeneous dispersion is obtained after being stirred 10 minutes under ultrasonication, uniform point
Granular media is calcium hydroxide suspension；The mixing speed is 10rpm to 1000rpm, and preferably mixing speed is 500rpm.Further
, dispersant can be added in mixture to improve the dispersiveness of calcium hydroxide nanometer spherocrystal.The dispersant is anion
Surfactant, selected from polycarboxylate ether, lauryl sodium sulfate, neopelex, PAMA or
It is prepared by sodium isethionate.
It is prepared by PAM/CNS Nanometer composite hydrogels material：
PAM/CNS hydrogels are prepared by radical polymerization in situ；Polymer, initiator and catalyst addition CNS are hanged
In supernatant liquid, wherein polymer is adopted as water-soluble polymer, and water-soluble polymer is selected from polyacrylamide, N- isopropyl acrylamides
Polyacrylamide is used in amine, polyvinyl alcohol or its mixture, present embodiment；Initiator be selected from ammonium persulfate, potassium peroxydisulfate,
Ammonium persulfate APS is used in sodium peroxydisulfate or 2,2 '-azo diisobutyl amidine dihydrochloride, present embodiment；Catalyst is N,
N, N ', N '-tetramethylethylenediamine TEMED.Nano particle is added in mixture further to improve the machine of composite aquogel
Tool performance；Each component ratio is CNS suspension/AM/APS/TEMED=60g/15g/0.03g/48 μ L, wherein CNS in suspension
CNS concentration is 40ppm in suspension.For CNS and APS complete reaction, mixture is maintained to 0 DEG C at least 72 in ice bath
Hour.Polymerization process is carried out 6 hours in 0 DEG C of vacuum environment (0.01atm).
Embodiment 2
It is prepared by PAM/CNS Nanometer composite hydrogels material：
PAM/CNS hydrogels are prepared by radical polymerization in situ；Polymer, initiator and catalyst addition CNS are hanged
In supernatant liquid, wherein polymer is adopted as water-soluble polymer, and water-soluble polymer is selected from polyacrylamide, poly-N-isopropyl propylene
Monomeric acrylamide AM is used in acid amides, polyvinyl alcohol or its mixture, present embodiment；Initiator is selected from ammonium persulfate, mistake
Ammonium persulfate APS is used in potassium sulfate, sodium peroxydisulfate or 2,2 '-azo diisobutyl amidine dihydrochloride, present embodiment；Catalysis
Agent is N, N, N ', N '-tetramethylethylenediamine TEMED；Each component ratio is CNS suspension/AM/APS/TEMED=in suspension
CNS concentration is 200ppm in 60g/15g/0.03g/48 μ L, wherein CNS suspension., will be mixed for CNS and APS complete reaction
Compound is maintained at 0 DEG C at least 72 hours in ice bath.Polymerization process is carried out 6 hours in 0 DEG C of vacuum environment (0.01atm).
It is that CNS is discharged in tricalcium silicate particle to obtain Fig. 1-4, Fig. 1 by hydrogel in comparative example 1 and embodiment 2
In TEM figure, whole figure base chi be 100nm, illustration base chi be 5nm.The CNS that Fig. 2 discharges from tricalcium silicate in hydration reaction
Electron diffraction pattern, the base chi be 51/nm.Fig. 3 TEM are that the CNS disperseed in C200 (has 200ppm CNS dense in PAM/CNS
Degree), base chi is 30nm.The optical photograph of Fig. 4 cylinder C200 samples, relative to background picture, its sample is diameter 2.7cm, thick
1.2cm, base chi is 1cm.It can be seen from figure 1 that C200 transparency is almost identical with initial PAM hydrogels.
Embodiment 3
It is different for embodiment 1, calcium hydroxide nanometer in PAM/CNS hydrogels in the present embodiment
Spherocrystal replaces with calcium hydroxide micron spherocrystal.
Embodiment 4
Different for embodiment 1, in the present embodiment, polymer is in PAM/CNS hydrogels
20wt% and 500ppm tricalcium silicates.Placed 10 days under 0 DEG C and 1atm, be gelatine, such as Fig. 5 occur under 1atm.
Embodiment 5
Different for embodiment 4, hydrogel is placed 1 day under 0 DEG C and 1atm in the present embodiment,
There is gelatine, such as Fig. 6 after placing 3h under 0.01atm.
Embodiment 6
Different for embodiment 4, the present embodiment hydrogel is placed 3 days under 0 DEG C and 1atm,
There is gelatine, such as Fig. 7 after placing 3h under 0.01atm.
Embodiment 7
Different for embodiment 4, hydrogel is placed 5 days under 0 DEG C and 1atm in the present embodiment,
There is gelatine, such as Fig. 8 after placing 3h under 0.01atm.
Embodiment 8
Different for embodiment 4, polymer concentration is in the present embodiment PAM/CNS hydrogels
20wt%, without tricalcium silicate, PAN gelling reactions add tricalcium silicate and sodium hydroxide at normal temperatures, and gelling time is
20min, at room temperature, 0H cause the S in initiator2O8 2-Reduce, therefore be difficult to polymerize.
Embodiment 9
It is different for embodiment 8, after the present embodiment addition 500ppm tricalcium silicates, gelling time
300min is extended to from 20min.Do not occur gelling reaction in time after addition 500ppm sodium hydroxide, this shows in polymerization
By OH when initial-Suppress, such as Fig. 9.
Embodiment 10
, should by the CNS of PAM/CNS hydrogels form in embodiment 1-2 and distribution by tem study
Microscope is provided with energy-dispersive spectroscopy system.The structure of gel is scanned by high resolution scanning electron microscope.Hydrogel
Glass transition temperature measured by differential scanning calorimetry.The last groups of SIMS detection PAM and pendant groups and CNS.
PAM and hydrogel C200 static SIMS is obtained by SIMS Pyatyi spectroscope.It is a large amount of in sample
Add Bi3+Ion, by 0.3pa, 25kv average pulse electric current accelerates supply.Grating region is 200um × 200 μm, each light
The spectrum collection time is 40s, equivalent to ＜ 4x1011ion.cm-2Ion dose.Three of each sample are recorded at diverse location
Positive and negative spectrum, obtains Figure 10-11.
Embodiment 11
It is different for embodiment 1, polymeric matrix is used in the present embodiment for N- isopropyl propylene
Acid amides, nano particle selection hectorite, hectorite 30000ppm prepares hydrogel, it is stretched and examination is compressed
Test, mechanical test is to be carried out using MTS testing machines in 25 DEG C.It is to use 30mm length in tension test, 3.2mm makees for diameter
For sample.It for C40 length is that 2.0mm, C200 length are 1.8mm that the extension of sample, which is, and sample tensile loads rate is
50mmmin-1.In compression test before use preparation hydrogel cylindrical sample, C40 sample sizes be 11.8mm diameters,
6.1mm is high, and C200 sample sizes are that diameter 10.3mm, 5.7mm are high, carry out cross in multiple dimension circulating compression test, compression test
Head speed is 1mmmin-1, it is loaded onto 8400N and reaches maximum load power, then stops loading.
Embodiment 12
It is different for embodiment 11, use polymer different for N- in the present embodiment in the present embodiment
Propylacrylamide, nano particle selection hectorite, hectorite 125000ppm.
Embodiment 13
It is different for embodiment 11, polymer is used for poly- third in the present embodiment in the present embodiment
Acrylamide (PAM), nano particle selection montmorillonite (MMT), montmorillonite (MMT) is 8700ppm.
Embodiment 14
It is different for embodiment 13, polymer is used in the present embodiment for polyacrylamide
(PAM), nano particle selection montmorillonite (MMT), montmorillonite (MMT) is 80800ppm.
Embodiment 15
It is different for embodiment 12, polymer is used in the present embodiment for polyacrylamide
(PAM), nano particle selective oxidation graphene (GO), graphene oxide (GO) is 80ppm.
Embodiment 16
It is different for embodiment 15, polymer is used in the present embodiment for polyacrylamide
(PAM), nano particle selective oxidation graphene (GO), graphene oxide (GO) is 480ppm.
Embodiment 17
It is different for embodiment 13, polymer is used in the present embodiment for polyacrylamide
(PAM), nano particle selection layered double-hydroxide (LDH), layered double-hydroxide (LDH) is 8000ppm.
Embodiment 18
It is different for embodiment 13, polymer is used in the present embodiment for polyacrylamide
(PAM), additive selection alginates, alginates are 110000ppm.
Embodiment 19
It is different for embodiment 17, polymer is used in the present embodiment for polyacrylamide
(PAM), additive selection alginates, alginates are 330000ppm.
Embodiment 20
The hydrogel prepared in embodiment 1 is subjected to expansion test, expansion test is by the way that hydrogel is immersed in into 25 DEG C
In 3 week in deionized water, deionized water is highly higher than hydrogel height, in order to reach swelling equilibrium.In the process, go from
Sub- water is periodically replaced.Sample expanded is then frozen drying.Expansion ratio Q is calculated by using Q=Ws/Wd, and wherein Ws is
Sample expanded weight, Wd be dry after example weight, wherein in PAM/CNS hydrogels CNS concentration be adopted as successively 40ppm,
100ppm and 200ppm.
Embodiment 21
The invention provides a kind of Nanometer composite hydrogel material, composite aquogel is made up of polymer for matrix material,
Addition nanometer spherocrystal is used as crosslinking agent；The polymeric matrix is that, using acrylamide as monomer, the ammonium sulfate of peroxidating two is initiation
Agent, prepares polyacrylamide PAM；Wherein add N, N, N ', N '-tetramethyl-ethylenediamine is used as catalyst.The nanometer spherocrystal
It is calcium hydroxide nanometer spherocrystal；Calcium hydroxide nanometer spherocrystal diameter is less than 10nm, and preferably diameter is less than 5nm；Composite aquogel contains
There is the nanometer spherocrystal of the content counted using hydrogel weight as 1-500ppm；Preferably it is 40-200ppm nanometer spherocrystal, polymer
Content be hydrogel weight total amount 10wt% to 50wt%, preferably 20wt%.
In Nanometer composite hydrogel material is prepared, using main component tricalcium silicate (Ca3SiO5) Portland cement
Hydration reaction prepares calcium hydroxide nanometer spherocrystal CNS.When the particulate of tricalcium silicate is dispersed in water, divalent calcium ions (Ca2 +) separated from tricalcium silicate and constitute calcium hydroxide in the solution.0 DEG C is optimum temperature, because at this temperature, calcium
Ion is just enough to generate calcium hydroxide crystals from the rate of release in tricalcium silicate, likewise, due to relatively low crystallization temperature
The size of crystal also is suppressed.
Clearly seen from Fig. 1, a circumgranular electron microscopic of the tricalcium silicate being hydrated is shown in figure
The photo of mirror.Fig. 1 a bulk of tricalcium silicate of left side correspondence, is highly 500 nanometers, and Fig. 1 the right and the picture of insertion are shown
Fine particle of the diameter below 5 nanometers.Energy spectrum analysis confirms these fine particles containing only calcium constituent and oxygen element, Fig. 8
Electron diffraction diagram and Fig. 1 in illustration in observe crystal structure show that those are exactly CNS crystal.It is 200ppm in concentration
The aqueous solution in, the potential that the electric double layer that CNS surfaces are produced by ion balance has -10mV (tests true by dynamic light scattering
It is fixed)；These ion balances ensure that CNS can effectively spread 40 into 200ppm concentration and reunited without any.It is dense comprising nppm
CNS (being named as Cn as specimen discerning) Nanometer composite hydrogel material is spent by CNS suspension, with acrylamide
Radical polymerization in situ is made.As shown in figure 5, for C200 (the CNS samples of 200ppm concentration), diameter is less than 5 nanometers
Particle in PAM matrix disperse it is really highly uniform.Due to soilless sticking, small size and dispersed CNS, C200's is saturating
Lightness and initial PAM hydrogels (Fig. 4) are about the same.Connection between PAM segments functional group and CNS is by initiator mistake
What the acid-base reaction of two ammonium sulfate and calcium hydroxide was set up.
At room temperature, OH-So that the S in initiator2O8 2-Reduce, therefore be difficult to occur polymerization (Figure 26).But at 0 DEG C
When, S2O8 2-And OH-Between redox reaction be suppressed；Excessive OH-Energy and NH4+Reaction generation NH3, NH3Can be by vacuum
Pump is got rid of.Moreover, oxygen is removed in aspiration procedure.Therefore, (0.01atm) (figure occurs under vacuum conditions for polymerization
5-8).Embodied entirely preparing CNS- preparations PAM/CNS hydrogels process all in schematic diagram, such as Fig. 9, CNS and PAM terminal groups
By Ca2+And S2O8 2-Between ionic bond set up connection.To prove this principle, initial PAM is obtained using SIMS
With C200 characteristic ion peak.With the CH in PAM-For reference, work as CN-And CNO-For pendant groups, anion SO4CH-And SO4CH2-
Relative peak region be selected to represent the terminal groups of PAM chains.With initial PAM, SO4CH-And SO4CH2-Relative peak intensities subtract
Curve a in the reduction of the last groups of C200, such as Figure 10-11, Figure 11 is indicated less and represents C200, and curve b represents PAM.Similarly, exist
It can be produced by-CONH in vacuum2Pendant groups energy and OH-Reaction forms NH3Ammonia, and Ca can be connected on CNS surfaces2+Be hydrolyzed into-
COO-, such response path is by CN-And CNO-Relative peak intensities reduce confirmed.The CaSO in C200 samples4CH-With
CaSO4CH2-The appearance of peak value effectively indicates chemical bond (Figure 11) between CNS and PAM terminal groups.Moreover, theirs is relative
Intensity does not change in the tension test of front and rear 60 times, it is meant that CNS and PAM terminal groups have strong connection.
In expansion test, xerogel of the C40 (CNS40ppm concentration samples) by freeze-drying, front and rear in deionization
In water expand 3 week, only lose less than 0.1wt% weight fraction, indicate 40ppm concentration hydrogels form one it is complete
Whole cross-linked network.In same volume content, CNS particles are because less than 5nm, its number density size is respectively higher than lithium and covers de-
Stone, GO, LDH and TiNS about 1000,2000,200 and 5.0 × 105Times.CNS is scattered more uniform as crosslinking points, relative to
More than 2800nm2Function surface nanometer sheet, its CNS surface area be less than 78.5nm2.The distribution of crosslinking points and density are being built
Played a key effect in vertical cross-linked network.For example, calcium hydroxide micro particles are from room temperature to be cooled to 0 by calcium hydroxide suspension
℃.CA200 (sample contains the PAM hydrogels of 200ppm calcium hydroxide micro particles), using with PAM/CNS hydrogel phase Tongfangs
Method is prepared from.In identical calcium hydroxide weight, the number density of crosslinking points is only 1/ relative to hydrogel in CA200
3.8×106.So low crosslink density prepares poor network structure, and mechanical performance enhancing is limited, will not continue to expansion anti-
And can be completely dissolved in water.Due to the high quantity density of CNS particles and uniformly dispersed, cross-linked network in hydrogel can be by
CNS density Effective Regulations.Concentration is by disperseing 100ppm tricalcium silicates in 0 DEG C of water, when disperseing for 40ppm CNS suspension
Between to produce within 3 days.CNS Cmaxs are 200ppm, are by the acquisition in scattered 3 days of 500ppm tricalcium silicates in 0 DEG C of water.This is dense
Degree can't with tricalcium silicate increase or hydration time it is higher and increase, be due to the calcium ion concentration in tricalcium silicate suspension
There is the upper limit.Figure 12 presents typical SEM pictures, indicates C40 dry sample and the crystal morphology of C200 xerogel.Area
Not in NC hydrogel nano flakes, such as PAM/LDH hydrogels possess classifying porous form, and micron and Nano grade particle are deposited
It is being randomly distributed, C40 xerogel illustrates that there is a kind of 200-400 microns loose structure is uniformly distributed.Interconnected
Nanochannel is found (Figure 13) in the inwall of loose structure.Moreover, Figure 14 further demonstrates that most of nanochannels are respectively less than
300nm, it means that crosslinking points are dispersed with Nano grade.With the increase of cross-linker density, the size of loose structure
It is similar with C40 in C200 xerogel, about in 20-80nm, there is a large amount of parallel and crosslinking filament, these physical dimensions
Between 50nm-2um, regularly it is distributed in hole (Figure 13).It is crosslinked between silk and hole inside in tie point in the presence of substantially convex
Rise, show possess strong ties power, the attachment force plays an important role in the expansion characteristics and mechanical performance of hydrogel.
Relative to C200, C40 cross-linked network has larger expansion characteristics, possesses bigger duct mainly due to it
Size and the thread connection of less crosslinking.When C40 maintains original dimension, its expansion rate Q values are 253.4, are about higher by C100
With C200 2.6 and 5.7 times (CNS100ppm concentration stands 3 days by 0 DEG C of 250ppm tricalcium silicates suspension and is made).Institute
So that Q values scope can be controlled from concentration of the simple adjustment CNS in hydrogel from 44.8-253.4.Serial type bulge-structure can be micro-
(Figure 17 and Figure 16) is found in the C200 xerogel duct of meter ruler cun.It is considered that a diameter of 100-500 nanometers projection be by
The CNS of PAM chains cladding.The distance (700nm-3 μm) of the thickness (100-500nm) of cladding and projection show CNS introducing for
The mobility of polymer molecule and elasticity have few effect of restraint in the NC gels of the present invention.Another evidence is shown to be by glass
Glass transition temperature Tg causes, and (Figure 19) is detected by differential scanning calorimetry DSC.Tg (the C40 of hydrogel：182.6 DEG C and
C200：183.2 DEG C) it is slightly above the linear Tg of PAM (182.3 DEG C), the value and with relying on CNS concentration.On the contrary, CA200 Tg has
Substantially increase, Tg is 196.7 DEG C, and this shows there is strong restraint force between the particle of large-size.Therefore, it is crosslinked in hydrogel
Polymer molecule in network is free, high resiliency, mobility, and random conformation is presented between CNS.
The mechanical performance of hydrogel is influenceed strongly by CNS concentration, controls its polymer network structure (as shown in Figure 1),
To set up contact between network structure and mechanical performance, at ambient temperature, stretching examination is done to the hydrogel under different CNS concentration
Test, representational stress-extension curve is indicated to be increased by the maximum stress of the hydrogel of matrix of polyacrylamide from 20KPa
Greatly to 430KPa, while fracture elongation increases to 121 from 10, as shown in Figure 20 and Figure 26, curve III represents CNS in Figure 20
Concentration is stress-extension curve under 0ppm, r=920%, and curve II is represented under CNS concentration is 40ppm, r=905%
Stress-extension curve, it is stress-extension curve under 200ppm, r=290% that curve I, which represents CNS concentration,.
R is residual deformation ratio, and it is defined as after loading force is released, script sample-size edge loading force direction
Length change ratio, residual deformation ratio is taken as modified index.After 121 tension tests, C40 samples recover to full size
90.5%, it is meant that it has excellent restorability.
It is compressed and tension test by 11 to 19 pairs of hydrogels of embodiment, obtains table 1, table 2 and Figure 21-25, Figure 21
Middle curve i represents compression-strain curve under CNS40ppm, r=51.5%, and curve ii represents CNS200ppm, r=9.6%
Under compression-strain curve；Curve A represents the fracture cyclic tension stress curve of the 5th cycle period, square frame area in Figure 22
It is to expand the 1st to 4 cyclic tension stress curve after 5 times in domain；It is to be followed for the 1st to 4 time in boxed area in Figure 22 in Figure 23
Curve map after 5 times of ring tensile stress curve magnification, curve A represents the fracture cyclic tension stress curve of the 5th cycle period,
Curve B represents the fracture cyclic tension stress curve in first circulation cycle, and the fracture cyclic tension in curve C second circulation cycles should
Force curve, the fracture cyclic tension stress curve of the cycle periods of curve D the 3rd, the fracture circulation of the cycle periods of curve E the 4th is drawn
Stretch stress curve；Figure 24 is that C200 expands ten times greater cyclic tension load-deformation curve and the 5th time in the 4th cycle period
The fracture strength curve of cycle period, wherein curve A represent the fracture cyclic tension stress curve of the 5th cycle period, square frame area
It is to expand the 1st to 4 cyclic tension stress curve after 10 times in domain；Figure 25 is to expand ten times greater in Figure 24 boxed areas
1 to 4 cyclic tension stress curve, curve A represents the fracture cyclic tension stress curve of the 5th cycle period, and curve B is represented
The fracture cyclic tension stress curve in first circulation cycle, the fracture cyclic tension stress curve in curve C second circulation cycles is bent
The fracture cyclic tension stress curve of the cycle periods of line D the 3rd, the fracture cyclic tension stress of the cycle periods of curve E the 4th is bent
Line.
In same volume content and allocability, the population density less than 5nm CNS is respectively higher than hectorite, oxygen
Graphite alkene, layered double-hydroxide, titanate thin slice and calcium hydroxide spherocrystal 1000,2000,200,5.0 × 105With 3.8 ×
106Times.
Table 1 is to add the composite elastic hydrogel extension at break stress and draw ratio prepared after different crosslinking agents
The cross-linking nanoparticles size comparison of table 2.
The fracture elongation of C40 fracture elongation hydrogel that all reported literatures are crossed higher than before, and identical
Exceed 4 times (such as tables 1) of the maximum stress of report under stage.C40 fracture toughness reaches 33.9MJm-3It is due to that it can be in phase
With acquisition high stress and deep drawing quality energy in the time.This tensile properties of C40 can be by following explanation：Unpolymerized CNS
Size is less than 5nm, uniform micropore can be provided in polymer network, CNS concentration is lower to cause connection fiber fewer, hole
Size is bigger, more contributes to deformation.C200 stress is issued to 630KPa in 65 fracture elongation, and residual deformation ratio reaches
290% (Figure 20 and Figure 27), equivalent to 2.7 times that mix alginate transparent polypropylene acid amides hydrogel reported (simultaneously
Stretchable multiple is higher by 16 times, referring to table 1).C200 fracture toughness is 26.2MJm-3, less than C40, mainly due to polymer
The decline of network deformability.However, for C200, fibre structure between smaller pore-size and connecting hole inwall
Foundation can provide a high mechanical properties and restoring force.In compression test, it is bearing 100MPa compression stress, strain
After 95%, C200 almost recovers to original size, and residual deformation is than r=9.6%, conversely, although C40 can bear 78MPa,
Strain the compressive stress for 99% and do not have fracture, but be only capable of recovering (there are r=51.5% remnants to the half of original size
Deformation ratio).
C200 excellent restorability further can embody (Fig. 8) by cyclic tension experiment.Loaded when from first time
To the 5th loading, its C200 is extended 5 times, and its cyclic tension load-deformation curve is each almost close overlapping, and this shows sample
By small after reaction in product.Residual deformation is 22.3%, four cyclic tensions after than r in being circulated in first time
1.1% is increased in experiment, such as Figure 22-25.Its extensibility is all by recovering length computation in circulating each time for sample, most
There is slight non-reversible deformation in a drawing process afterwards.Therefore, because the non-reversible deformation in elongation occurs before,
The fracture elongation of C200 samples is about 40% in being circulated at the 5th time, has residual deformation to compare 205%.The stretching of increase should
The stretch modulus that force-strain curve indicates circulation for the first time in fig 23 is slightly above remaining circulation, and now stretching is less than four times,
And reduced in further stretching.This shows in the drawing process of beginning, exist in cross-linked network it is slight can not
Inverse deformation.Then, the restorability of hydrogel is embodied after the deformation adjustment of initial cross-linked network.Restorability also may be used
Embodied (Figure 24 and 25) in stretching C200 hydrogels.Hydrogel is primarily due to obtain into the 4th circulation in first time
To high extensibility, residual deformation is than all higher than the residual deformation ratio in five times of cyclic tests in each circulation.However, with
More fully conformation is adjusted, and is followed residual deformation at the 5th time and is reduced than r to 196%.This shows there is excellent along stretching force direction
Different is restorative, and by being found in initial slight irreversible transformation.
In summary, PAM/CNS hydrogels are adjusted by CNS concentration, can obtain high-expansion, extension property, rupture stress
And restorability.CNS can more be obtained by portland cement suspension instead of tricalcium silicate, and greatly reduction prepares cost.
As a result show, CNS nanometers of spherocrystal finely dispersed less than 5nm can be obtained by tricalcium silicate in low temperature hydration reaction, and this is received
Rice spherocrystal helps hydrogel enhancing cross-linked network and each side characteristic.
The preferred embodiments of the present invention have shown and described in described above, as previously described, it should be understood that not office of the invention
Be limited to form disclosed herein, be not to be taken as the exclusion to other embodiment, and available for various other combinations, modification and
Environment, and can be changed in invention contemplated scope described herein by the technology or knowledge of above-mentioned teaching or association area
It is dynamic., then all should be appended by the present invention and the change and change that those skilled in the art are carried out do not depart from the spirit and scope of the present invention
In scope of the claims.
Claims (10)
1. a kind of Nanometer composite hydrogel material, it is characterised in that：The composite aquogel is made up of polymer for matrix material,
Addition nanometer spherocrystal is used as crosslinking agent；The polymeric matrix is that, using acrylamide AM as monomer, ammonium persulfate APS is initiation
Agent, prepares polyacrylamide PAM；Wherein add N, N, N ', N '-tetramethyl-ethylenediamine is used as catalyst.
2. Nanometer composite hydrogel material according to claim 1, it is characterised in that：The nanometer spherocrystal is calcium hydroxide
Nanometer spherocrystal；The calcium hydroxide nanometer spherocrystal diameter is less than 10nm.
3. Nanometer composite hydrogel material according to claim 1, it is characterised in that：The composite aquogel contains with water
The content of gel weight meter is 1-500ppm nanometer spherocrystal.
4. Nanometer composite hydrogel material according to claim 1, it is characterised in that：The content of the polymer is water-setting
The 10wt% to 50wt% of glue weight total amount.
5. a kind of method for preparing Nanometer composite hydrogel in claim 1, it is characterised in that：Comprise the following steps that：
S1, at 0 DEG C in ice bath, tricalcium silicate/dicalcium silicate/Portland cement/white cement or its compound particles are mixed
Calcium hydroxide nanometer spherocrystal is hydrated to form, its calcium hydroxide nanometer spherocrystal is scattered in deionized water translucent aqueous to obtain
Dispersion, obtains homogeneous dispersion, homogeneous dispersion is calcium hydroxide suspension after being stirred 10 minutes under ultrasonication；
S2, mixture is made in addition polymer, initiator and catalyst in calcium hydroxide suspension；
S3, mixture is kept for 72 hours in 0 DEG C of ice bath, so that the abundant aquation of tricalcium silicate；
S4, passes through polymerization formation Nanometer composite hydrogel material under 0.01atm；
Wherein, the mixing speed is 10rpm to 1000rpm.
6. the preparation method of Nanometer composite hydrogel according to claim 5, it is characterised in that：The polymer is water-soluble
Property polymer, water-soluble polymer be selected from polyacrylamide, NIPA, polyvinyl alcohol, polyacrylate or its
Mixture；The initiator is water-soluble polymer, and the water-soluble polymer is ammonium persulfate, potassium peroxydisulfate, sodium peroxydisulfate
Or 2,2 '-azo diisobutyl amidine dihydrochloride；Dispersant is added in S2 into mixture to improve calcium hydroxide nanometer spherocrystal
Dispersiveness；The dispersant is anion surfactant, and the anion surfactant is polycarboxylate ether, dodecane
Base sodium sulphate, neopelex, PAMA or sodium isethionate.
7. the preparation method of Nanometer composite hydrogel according to claim 5, it is characterised in that：The calcium hydroxide nanometer
The hydration temperature scope of spherocrystal is -10 DEG C to 40 DEG C.
8. the preparation method of Nanometer composite hydrogel according to claim 5, it is characterised in that：The polymerization is former
Position radical polymerization.
9. the preparation method of Nanometer composite hydrogel according to claim 5, it is characterised in that：Nano particle is added to
Further to improve the mechanical performance of composite aquogel in mixture in S2.
10. the preparation method of Nanometer composite hydrogel according to claim 9, it is characterised in that：The nano particle choosing
From hectorite, montmorillonite, graphene oxide, layered double-hydroxide, titanate nanometer sheet, controllable active nano gel or its
Mixture.
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| CN108043047A (en) * | 2017-11-17 | 2018-05-18 | 河北金丰新材料科技有限公司 | Water for bathing colored suspended gel and preparation method thereof |
| CN110003374A (en) * | 2019-04-04 | 2019-07-12 | 澳门大学 | A kind of superabsorbent water hydrogel material and its preparation method and application |
| CN110016148A (en) * | 2019-03-27 | 2019-07-16 | 澳门大学 | Conductive polymer hydrogel material and preparation method thereof |
| CN110028276A (en) * | 2019-04-23 | 2019-07-19 | 佛山市世为创意家具有限公司 | A kind of high-effective water-proof dustproof fiber cement plate |
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| US6846881B2 (en) * | 2002-02-27 | 2005-01-25 | Bio-Rad Laboratories, Inc. | Preparation of defect-free polyacrylamide electrophoresis gels in plastic cassettes |
| KR20050013217A (en) * | 2002-06-19 | 2005-02-03 | 쇼와 덴코 가부시키가이샤 | Hydrous gel and production process and use of the hydrous gel |
| CN100406499C (en) * | 2006-08-07 | 2008-07-30 | 东华大学 | Nanometer composite hydrogel and preparation method thereof |
| CN101658485B (en) * | 2009-09-10 | 2011-11-09 | 东华大学 | Nanometer hybridized hydrogel with durable broad spectrum antibacterial performance and preparation method thereof |
| CN102675658A (en) * | 2011-03-07 | 2012-09-19 | 远东新世纪股份有限公司 | Method for preparing polysiloxane hydrogel with high moisture content |
| CN102964528B (en) * | 2012-11-09 | 2014-09-24 | 海安常大技术转移中心有限公司 | Novel high-strength microgel composite hydrogel |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108043047A (en) * | 2017-11-17 | 2018-05-18 | 河北金丰新材料科技有限公司 | Water for bathing colored suspended gel and preparation method thereof |
| CN110016148A (en) * | 2019-03-27 | 2019-07-16 | 澳门大学 | Conductive polymer hydrogel material and preparation method thereof |
| CN110016148B (en) * | 2019-03-27 | 2022-05-17 | 澳门大学 | High-molecular conductive hydrogel material and preparation method thereof |
| CN110003374A (en) * | 2019-04-04 | 2019-07-12 | 澳门大学 | A kind of superabsorbent water hydrogel material and its preparation method and application |
| CN110003374B (en) * | 2019-04-04 | 2021-08-27 | 澳门大学 | Super water-absorbing hydrogel material and preparation method and application thereof |
| CN110028276A (en) * | 2019-04-23 | 2019-07-19 | 佛山市世为创意家具有限公司 | A kind of high-effective water-proof dustproof fiber cement plate |
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