Summary of the invention
The purpose of this invention is to provide compound colloidal dispersed gel of a kind of organic/inorganic and preparation method thereof, the present invention adopts inorganic crosslinking agent and organic crosslinking agent to carry out composite crosslinking to acrylamide polymer, can in comparatively high temps, larger pH scope and larger salinity scope, the viscosity of acrylamide polymer system can be realized improving, and the control to crosslinking time can be realized.
The compound colloidal dispersed gel of a kind of organic/inorganic provided by the present invention, be comprised of water, acrylamide polymer, inorganic crosslinking agent and organic crosslinking agent;
In described colloidal dispersed gel, the mass body volume concentrations of described acrylamide polymer is 1000mg/L~2000mg/L, the mass body volume concentrations of described inorganic crosslinking agent is 10~130mg/L, and the mass body volume concentrations of described organic crosslinking agent is 50mg/L~1000mg/L;
Described inorganic crosslinking agent is Tiorco 677, and its structural formula is suc as formula shown in I;
Described organic crosslinking agent is tetramethylol glycoluril, and its structural formula is suc as formula shown in II;
The salinity of described water is 2743mg/L~8074mg/L,
In above-mentioned compound colloidal dispersed gel, described acrylamide polymer can be methacrylamide homopolymer and/or acrylamide copolymer.
In above-mentioned compound colloidal dispersed gel, described methacrylamide homopolymer can be partially hydrolyzed polyacrylamide;
The degree of hydrolysis of described partially hydrolyzed polyacrylamide can be 15~30%, and weight-average molecular weight can be 1000~2,000 ten thousand, as degree of hydrolysis be 18%, weight-average molecular weight is about 1,800 ten thousand partially hydrolyzed polyacrylamide.
In above-mentioned compound colloidal dispersed gel, the mass body volume concentrations of described inorganic crosslinking agent can be 110~130mg/L and specifically can be 120mg/L, and/or;
The mass body volume concentrations of described organic crosslinking agent can be 400mg/L~800mg/L, specifically can be 600mg/L.
In above-mentioned compound colloidal dispersed gel, the salinity of described water can be 3500mg/L~7500mg/L.
In above-mentioned compound colloidal dispersed gel, the salinity of described water can be 5000mg/L~7000mg/L, is the water of 6664mg/L if adopted salinity, and it consists of: 6190mg/L NaCl, 81.67mg/L KCl, 263.12mg/LCaCl
2, 151.72mg/L MgCl
2, 9.03mg/L Na
2SO
4, 43.75mg/L NaHCO
3Water with surplus.
Inorganic crosslinking agent and described organic crosslinking agent and acrylamide polymer compound action described in compound colloidal dispersed gel provided by the invention are put forward full-bodied mechanism and be: Tiorco 677 can form crosslinking polymer network with the carboxyl effect of generation after the acrylamide polymer hydrolysis, then thereby the amino in tetramethylol glycoluril and acrylamide polymer forms hydrogen bond and realizes secondary crosslinking, formation is similar to the compound crosslinking system of inierpeneirating network structure, significantly puies forward full-bodied effect thereby reach.
The preparation method of above-mentioned compound colloidal dispersed gel provided by the invention, comprise the steps: to add described acrylamide polymer to obtain polymers soln in described water, and the pH value of the described polymers soln of regulation and control is 6.0~7.5; Then in described polymers soln, add described inorganic crosslinking agent and described organic crosslinking agent, namely obtain described compound colloidal dispersed gel through aging.
In above-mentioned preparation method, described aging temperature can be 35 ℃~85 ℃, and the time can be 2 hours~and 1000 hours.
In above-mentioned preparation method, described aging temperature can be 35 ℃~60 ℃, and the time can be 300 hours~and 500 hours.
Compared with the prior art, its main advantage is in invention:
1, salinity is applied widely.Can in larger salinity scope, significantly improve the viscosity of acrylamide polymer system.
2, the inorganic crosslinking agent sphere of action is wide.Add a small amount of inorganic crosslinking agent can effectively improve the viscosity of acrylamide polymer, all can effectively improve system viscosity in larger inorganic crosslinking agent amount ranges, this is conducive to extensively utilize in industrialized production.
3, gelation time is controlled, can reach by regulating the conditions such as inorganic crosslinking agent concentration, temperature, pH the purpose of regulation and control gelation time
4, the organic crosslinking agent sphere of action is wide.Add a small amount of organic crosslinking agent can effectively improve the viscosity of acrylamide polymer, all can effectively improve system viscosity in larger organic crosslinking agent amount ranges, this is conducive to extensively utilize in industrialized production.
5, temperature applicable range is wide.Can in 35 ℃~85 ℃ scopes, effectively improve the viscosity of acrylamide polymer.
6, cross-linking system is nontoxic, little to environmental influence.
Embodiment
The experimental technique used in following embodiment if no special instructions, is ordinary method.
In following embodiment, material used, reagent etc., if no special instructions, all can obtain from commercial channels.
In the following embodiment of the present invention, sodium hydroxide, hydrochloric acid, sodium-chlor, Repone K, calcium chloride, magnesium chloride, sodium sulfate, sodium carbonate, sodium bicarbonate, all purchased from chemical reagents corporation of traditional Chinese medicines group, are analytical pure; Tiorco 677, purchased from modern technique Industrial Co., Ltd, is chemical pure; Tetramethylol glycoluril, purchased from Beijing lean work company limited that refines, is chemical pure; Partially hydrolyzed polyacrylamide (HPAM, industrial goods, degree of hydrolysis are 18%, weight-average molecular weight is about 1,800 ten thousand), institute's water is water three times.
Comparative Examples 1, preparation CDG-0-600(be adding citric acid aluminium not, adds separately tetramethylol glycoluril)
The configuration salinity is that the mineralized water solution of 6664mg/L (wherein contains 6190mg/L NaCl, 81.67mg/L KCl, 263.12mg/L CaCl
2, 151.72mg/L MgCl
2, 9.03mg/L Na
2SO
4, 43.75mg/L NaHCO
3), add partially hydrolyzed polyacrylamide, stirring and dissolving, being made into concentration is the HPAM solution of 1750mg/L, regulating its pH is 7.0, adds the tetramethylol glycoluril stirring and dissolving to make its content reach 600g/L in solution, obtains 60 ℃ of sample CDG-0-600 constant temperature aging;
With the HPAM that do not add linking agent with as a comparison aging under condition.
Viscosimetric analysis is carried out in sampling when digestion time is 0h, 26h, 47h, 98h, 140h, 240h, 333h, 480h and 866h.
Viscosimetric analysis is carried out under 25.0 ℃, the rotor shearing rate is fixed as 7.26s
-1, various kinds viscosity is listed in table 1.
Under table 160 ℃, the viscosity of aging sample CDG-0-600 and HPAM changes
As can be seen from Table 1, when in HPAM, not adding linking agent or only adding organic linking agent, sample viscosity all is reduction trend.But it is slightly light that the sample that adds tetramethylol glycoluril does not more add linking agent sample viscosity degradation, because can form hydrogen bond between tetramethylol glycoluril and HPAM, thereby viscosity degradation trend is slowed down, but while adding tetramethylol glycoluril separately, hydrogen bond action a little less than, therefore can not change viscosity degradation trend.
Embodiment 1, preparation CDG-25-0 and CDG-25-600
The configuration salinity is that the mineralized water solution of 6664mg/L (wherein contains 6190mg/L NaCl, 81.67mg/L KCl, 263.12mg/L CaCl
2, 151.72mg/L MgCl
2, 9.03mg/L Na
2SO
4, 43.75mg/L NaHCO
3), add partially hydrolyzed polyacrylamide, stirring and dissolving, being made into concentration is the HPAM solution of 1750mg/L, regulating pH is 7.0, gets this sample and is designated as CDG-25-0 to adding in solution the Tiorco 677 stirring and dissolving to make aluminum concentration reach 25mg/L(); Continue to add wherein the tetramethylol glycoluril stirring and dissolving to make its content reach 600g/L, obtain product of the present invention, it is aging that sample number into spectrum is designated as 60 ℃ of degraded sample CDG-25-600 constant temperature.
Viscosimetric analysis is carried out in sampling when digestion time is 0h, 26h, 47h, 98h, 140h, 240h, 333h, 480h and 866h.
Institute get in the middle of sample CDG-25-0 also 60 ℃ aging, when digestion time was 0h, 26h, 47h, 98h, 140h, 240h, 333h, 480h and 866h, viscosimetric analysis was carried out in sampling.
Viscosimetric analysis is carried out under 25.0 ℃, the rotor shearing rate is fixed as 7.26s
-1, each sample viscosity is listed in table 2.
Under table 260 ℃, the viscosity of aging sample CDG-25-0 and CDG-25-600 changes
As can be seen from Table 2, different with sample CDG-0-600 from HPAM, sample CDG-25-0 and CDG-25-600 viscosity all present the trend that first descends and raise afterwards, and final viscosity surpasses initial viscosity, this is because the stretching, extension that has hindered the HPAM molecular chain that adds of Tiorco 677 causes viscosity slightly to descend when initial, then Tiorco 677 carries out the crosslinked viscosity rise that makes to HPAM, because aluminium content is lower, for weak crosslinked, cause the viscosity rise degree little, while on adding the Tiorco 677 basis, continuing to add tetramethylol glycoluril, because can carrying out secondary crosslinking with HPAM, tetramethylol glycoluril can again improve its viscosity, therefore the viscosity of sample CDG-25-600 is all the time higher than CDG-25-0.
Embodiment 3, the preparation CDG-120-0 and CDG-120-600(60 ℃ aging)
The configuration salinity is that the mineralized water solution of 6664mg/L (wherein contains 6190mg/L NaCl, 81.67mg/L KCl, 263.12mg/L CaCl
2, 151.72mg/L MgCl
2, 9.03mg/L Na
2SO
4, 43.75mg/L NaHCO
3), add partially hydrolyzed polyacrylamide, stirring and dissolving, being made into concentration is the HPAM solution of 1750mg/L, regulating pH is 7.0, is designated as CDG-120-0 to adding the Tiorco 677 stirring and dissolving to make aluminum concentration reach this sample of 120mg/L(in solution), in sample CDG-120-0, add the tetramethylol glycoluril stirring and dissolving to make its content reach 600g/L, obtain product of the present invention, it is aging that sample number into spectrum is designated as 60 ℃ of degraded sample CDG-120-600 constant temperature.
Viscosimetric analysis is carried out in sampling when digestion time is 0h, 26h, 47h, 98h, 140h, 240h, 333h, 480h and 866h.
Viscosimetric analysis is carried out under 25 ℃, the rotor shearing rate is fixed as 7.26s
-1, various kinds viscosity is listed in table 3.
Under table 360 ℃, the viscosity of aging sample CDG-120-0 and CDG-120-600 changes
As can be seen from Table 3, only slightly to improve sample viscosity different from sample CDG-25-0 and CDG-25-600, and CDG-120-0 and CDG-120-600 can significantly improve system viscosity.This is that the HPAM molecular chain is crosslinked to be increased owing to making adding in a large number of Tiorco 677, form comparatively firm weak gel structure, and on this comparatively firm weak gel basis, adding of tetramethylol glycoluril makes crosslinked HPAM molecular chain continue to be cross-linked to form the structure of similar interpenetrating(polymer)networks, this makes CDG-120-600 viscosity on the CDG-120-0 basis, again significantly to promote, thereby reaches viscosifying action.
Embodiment 4, preparation CDG-120-1000
Basic identical with the step in embodiment 3, difference is to add tetramethylol glycoluril to make its content reach 1000g/L, obtains product of the present invention, and sample number into spectrum is designated as degraded sample CDG-120-1000, and 60 ℃ of constant temperature are aging.
Viscosimetric analysis is carried out in sampling when digestion time is 0h, 26h, 47h, 98h, 140h, 240h, 333h, 480h and 866h.
Viscosimetric analysis is carried out under 25 ℃, the rotor shearing rate is fixed as 7.26s
-1, various kinds viscosity is listed in table 4.
Under table 460 ℃, aging sample CDG-120-1000 viscosity changes
Digestion time |
Viscosity (mPas) |
0h |
70.13 |
26h |
274.14 |
47h |
535.98 |
98h |
936.19 |
140h |
1379.64 |
240h |
1391.27 |
333h |
1399.40 |
480h |
1412.13 |
866h |
1425.17 |
As can be seen from Table 4, CDG-120-600 compares with sample, while adding the amount of tetramethylol glycoluril to increase to 1000mg/L from 600mg/L, sample CDG-120-1000 viscosity has small size decline on the contrary, this is due to increasing along with the tetramethylol glycoluril amount, cross-linking set in inierpeneirating network structure increases, thus the generation that causes gel to subside, thus cause viscosity slightly to descend than CDG-120-600.
Embodiment 5, the preparation CDG-120-600(35 ℃ aging)
Aluminum concentration 120mg/L, tetramethylol glycoluril content 600g/L, 35 ℃ are aging.
Substantially same with the step of embodiment 3, difference is to say that 35 ℃ of products obtained therefrom degraded sample CDG-120-600 constant temperature are aging.
Viscosimetric analysis is carried out in sampling when digestion time is 0h, 26h, 47h, 98h, 140h, 240h, 333h, 480h and 866h.
Viscosimetric analysis is carried out under 25 ℃, the rotor shearing rate is fixed as 7.26s
-1, various kinds viscosity is listed in table 5.
Under table 535 ℃, aging sample CDG-120-600 viscosity changes
Digestion time |
Viscosity (mPas) |
0h |
70.13 |
26h |
864.17 |
47h |
1413.21 |
98h |
2824.25 |
140h |
3920.83 |
240h |
4032.17 |
333h |
4936.37 |
480h |
5414.74 |
866h |
5926.20 |
As shown in Table 5, sample CDG-120-600 is at 35 ℃ when aging, and when viscosity will be aging higher than 60 ℃, aging temperature reduced, and rate of crosslinking is slack-off, more stable after gel formation, thereby sample viscosity is increased.
Embodiment 6, CDG-120-600(85 ℃ aging)
As described in Example 3, difference is that products obtained therefrom 85 ℃ of the sample CDG-120-600 constant temperature of degrading is aging.
Viscosimetric analysis is carried out in sampling when digestion time is 0h, 26h, 47h, 98h, 140h, 240h, 333h, 480h and 866h.
Viscosimetric analysis is carried out under 25 ℃, the rotor shearing rate is fixed as 7.26s
-1, various kinds viscosity is listed in table 6.
Under table 685 ℃, the viscosity of aging sample CDG-120-600 changes
Digestion time |
Viscosity (mPas) |
0h |
70.13 |
26h |
4179.20 |
47h |
3869.94 |
98h |
3445.86 |
140h |
1869.81 |
240h |
43.78 |
333h |
11.73 |
480h |
6.67 |
866h |
1.57 |
As shown in Table 6, sample CDG-120-600 is at 85 ℃ when aging, along with the viscosity elder generation that increases progressively of time increases rapidly to then reduction rapidly of maximum, illustrate that temperature is higher, thereby the gelation time shortening realizes Quick cross-linking, but under hot conditions, gel stability is not fine, surpasses regular hour viscosity and start to reduce.
Embodiment 7, CDG-120-600-6.0(pH are 6.0)
Basic identical with the step in embodiment 3, difference is to be 6.0 by the HPAM solution of 1750mg/L adjusting pH, adding the Tiorco 677 stirring and dissolving to make aluminum concentration is 120mg/L, continuing to add the tetramethylol glycoluril stirring and dissolving to make tetramethylol glycoluril content is 600g/L, and obtaining product, to be designated as 60 ℃ of degraded sample CDG-120-600-6.0 constant temperature aging.
Viscosimetric analysis is carried out in sampling when digestion time is 0h, 26h, 47h, 98h, 140h, 240h, 333h, 480h and 866h.
Viscosimetric analysis is carried out under 25 ℃, the rotor shearing rate is fixed as 7.26s
-1, various kinds viscosity is listed in table 7.
Under table 760 ℃, the viscosity of aging sample CDG-120-600-6.0 changes
Digestion time |
Viscosity (mPas) |
0h |
70.13 |
26h |
4007.14 |
47h |
4881.17 |
98h |
4453.16 |
140h |
4463.51 |
240h |
3653.22 |
333h |
3335.29 |
480h |
2789.40 |
As shown in Table 7, sample CDG-120-600-6.0 is when aging, viscosity first increases rapidly to then slightly reduction of maximum, this is because under solutions of weak acidity, thereby shortening, gelation time makes crosslinked acceleration, then owing under mild acid conditions, being unfavorable for the stable of weak gel, thereby system viscosity is slightly descended.Though system viscosity has decline, when 866h, its viscosity still surpasses nearly 36 times of initial viscosity, has kept good viscosity characteristics but as can be seen from Table 7.
Embodiment 8, CDG-120-600-7.5(pH are 7.5)
Basic identical with the step in embodiment 3, difference is to be 7.5 by the HPAM solution of 1750mg/L adjusting pH, in solution, add the Tiorco 677 stirring and dissolving to make aluminum concentration reach 120mg/L, continue to add the tetramethylol glycoluril stirring and dissolving to make its content reach 600g/L, obtaining product, to be designated as 60 ℃ of degraded sample CDG-120-600-7.5 constant temperature aging.
Viscosimetric analysis is carried out in sampling when digestion time is 0h, 26h, 47h, 98h, 140h, 240h, 333h, 480h and 866h.
Viscosimetric analysis is carried out under 25 ℃, the rotor shearing rate is fixed as 7.26s
-1, various kinds viscosity is listed in table 8.
Under table 860 ℃, the viscosity of aging sample CDG-120-600-7.5 changes
Digestion time |
Viscosity (mPas) |
0h |
70.13 |
26h |
227.95 |
47h |
269.94 |
98h |
445.86 |
140h |
869.81 |
240h |
1013.78 |
333h |
1231.73 |
480h |
1347.67 |
866h |
1415.57 |
As shown in Table 8, sample CDG-120-600-7.5 is when aging, although viscosity is little than CDG-120-600-6.0, it keeps continuing the trend increased, and its viscosity has stability preferably.
The salinity of embodiment 9, CDG-120-600-2743(water is 2743mg/L)
The configuration salinity is that the mineralized water solution of 2743mg/L (wherein contains 1201.2mg/L NaCl, 3.775mg/LKCl, 130.45mg/L CaCl
2, 24.54mg/L MgCl
2, 137.7mg/LNa
2SO
4, 81.58mg/L Na
2CO
3, 1163.9mg/L NaHCO
3), add acrylamide polymer, stirring and dissolving, being made into concentration is the HPAM solution of 1750mg/L, regulating pH is 7.0, in solution, add the Tiorco 677 stirring and dissolving to make aluminum concentration reach 120mg/L, continue to add the tetramethylol glycoluril stirring and dissolving to make its content reach 600g/L, obtaining product, to be designated as 60 ℃ of degraded sample CDG-120-600-2743 constant temperature aging.
Viscosimetric analysis is carried out in sampling when digestion time is 0h, 26h, 47h, 98h, 140h, 240h, 333h, 480h and 866h.
Viscosimetric analysis is carried out under 25 ℃, the rotor shearing rate is fixed as 7.26s
-1, various kinds viscosity is listed in table 9.
Under table 960 ℃, the viscosity of aging sample CDG-120-600-2743 changes
Digestion time |
Viscosity (mPas) |
0h |
89.37 |
26h |
139.96 |
47h |
145.96 |
98h |
157.97 |
140h |
169.96 |
240h |
171.97 |
333h |
173.12 |
480h |
179.21 |
866h |
180.11 |
As known from Table 9, when sample CDG-120-600-2743 was aging, its viscosity significantly increased, but still good higher than initial value and maintenance, this may be because be unfavorable for the compression of polymer molecular chain electrostatic double layer than low mineralization, thereby while causing cross-linking effect to be 6664mg/L lower than salinity.
The salinity of embodiment 10, CDG-120-600-8074(water is 8074mg/L)
The configuration salinity is that the mineralized water solution of 8074mg/L (wherein contains 6408.4mg/L NaCl, 30.37mg/LKCl, 419mg/L CaCl
2, 324.6mg/L MgCl
2, 36.98mg/L Na
2SO
4, 84.8mg/L Na
2CO
3, 769.8mg/L NaHCO
3) add acrylamide polymer, stirring and dissolving, being made into concentration is the HPAM solution of 1750mg/L, regulating its pH is 7.0, in solution, add the Tiorco 677 stirring and dissolving to make aluminum concentration reach 120mg/L, continue to add the tetramethylol glycoluril stirring and dissolving to make its content reach 600g/L, obtaining product, to be designated as 60 ℃ of degraded sample CDG-120-600-8074 constant temperature aging.
Viscosimetric analysis is carried out in sampling when digestion time is 0h, 26h, 47h, 98h, 140h, 240h, 333h, 480h and 866h.
Viscosimetric analysis is carried out under 25 ℃, the rotor shearing rate is fixed as 7.26s
-1, various kinds viscosity is listed in table 10.
Under table 1060 ℃, the viscosity of aging sample CDG-120-600-8074 changes
Digestion time |
Viscosity (mPas) |
0h |
62.59 |
26h |
257.94 |
47h |
305.93 |
98h |
157.97 |
140h |
803.83 |
240h |
1331.72 |
333h |
1571.6 |
480h |
1531.27 |
866h |
1596.21 |
As shown in Table 10, when CDG-120-600-8074 viscosity will be 2743mg/L higher than salinity, this was because being compressed with of polymer molecular chain electrostatic double layer is beneficial to its cross-linked state of maintenance, thereby keeps higher viscosity level.
By above-described embodiment and Comparative Examples, can be learnt, this organic/inorganic colloidal dispersed gel system can significantly improve the viscosity of acrylamide polymer system in larger salinity and temperature range.And its inorganic crosslinking agent used and organic crosslinking agent sphere of action are wide, without strict its consumption of controlling, can obtain good viscosity characteristics, this is conducive to extensively utilize in industrialized production.