CN109777379A - A kind of low-molecular weight polymer shale control agent and preparation method thereof - Google Patents
A kind of low-molecular weight polymer shale control agent and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a kind of low-molecular weight polymer shale control agents and preparation method thereof.The described method includes: accurately controlling total monomer, a certain amount of Sodium Allyl Sulfonate for being dissolved in deionized water is weighed, trihydroxyethyl allylic bromination ammonium is sequentially added, methyl methacrylate and chain-transferring agent is added dropwise；It is sprinkled into etc. the K of quality rapidly2S2O8And NaHSO3And seal, polymerization reaction, washing, shear granulation and product obtained by drying occur for mixed solution.The product thermal stability is strong, small to drilling fluid system rheology impact, and it is cheap and easily-available to prepare raw material, can be directly used for industrialized production and situ of drilling well application.
Description
Technical field
The present invention relates to a kind of low-molecular weight polymer shale control agent AS/THAAB/MMA and preparation method thereof, specifically
Say the low-molecular weight polymer shale control agent AS/THAAB/MMA for being related to a kind of high temperature and pressure high-density water-based drilling fluid and
Preparation method.
Background technique
During oil gas drilling, when boring chance mud shale stratum, the hydration swelling of mud shale, dispersion will lead to borehole wall mistake
Surely, bit balling and a series of problems, such as difficult hole cleaning.Wellbore Stability is frequently encountered in oil/gas drilling engineering
Sufficiently complex global problem.According to statistics.The funds that World Oil Industry is used to handle every year wellbore stability accident are beautiful up to 700,000,000
The height of member.To solve these problems, oil field scientific research personnel has developed oil base and water base drilling fluid system in recent years, but oil base bores
Well liquid somewhat expensive and to environment nocuousness, therefore water-base drilling fluid has more researching value.
Shale control agent can be added in water-base drilling fluid in brittle property shale formation to prevent borehole wall aquation from dispersing and collapsing
Fold block etc., and with a large amount of exploitations of caving ground, the new and effective research and development that can inhibit shale hydration inhibition agent are compeled
In the eyebrows and eyelashes.The polymer of high molecular weight can be coated in clay surface, inhibit Shale Hydration dispersion, but excessively high molecular weight is to drilling well
Liquid system rheological characteristic has certain influence and should not use in high-temperature high-density.Therefore, in large arch dam water-base drilling fluid
The research and development of applicable low molecular weight shale control agent have certain practical significance.Low-molecular weight polymer is applied in drilling fluid
Seldom, the research work of this patent low-molecular weight polymer shale control agent can provide one for the design and synthesis of oil field chemical
Fixed reference.
Summary of the invention
The present invention provide a kind of low-molecular weight polymer shale control agent AS/THAAB/MMA and
Preparation method, low molecular weight part can enter between shale clay mineral crystal layer, and high molecular weight moieties can wrap up
In shale outer surface, by absorption and coated synergistic effect, achievees the purpose that while Shale Hydration being inhibited to expand and disperse, and
Play good shale inhibitory effect.
In order to achieve the above objectives, the invention adopts the following technical scheme: a kind of low-molecular weight polymer shale control agent AS/
THAAB/MMA, it is characterised in that: accurately control total monomer, weigh a certain amount of allyl sulphonic acid for being dissolved in deionized water
Sodium (AS) is placed in three-necked flask, leads to nitrogen deoxygenation 10min；Sequentially add a certain amount of novel cation monomer trihydroxyethyl allyl
Base ammonium bromide (THAAB) is added dropwise a certain amount of methyl methacrylate (MMA) and chain-transferring agent and seals at once, is sprinkled into rapidly
The K of quality2S2O8And NaHSO3And it seals.Polymerization reaction after a certain period of time, obtains under different shape mixed solution at a certain temperature
Product.Product is sufficiently washed through dehydrated alcohol, is toppled over, filters or is evaporated ethyl alcohol and be placed on certain time in vacuum drying oven
A kind of low-molecular weight polymer shale control agent AS/THAAB/MMA of product is obtained afterwards.AS/THAAB/MMA reaction equation is as follows:
X=1~5, y=2~5, z=2~4
A kind of low-molecular weight polymer shale control agent AS/THAAB/MMA, synthesis step is: it is total to accurately control monomer
Concentration 30wt%~70wt%, weighs 0.2~0.4g and is dissolved in the Sodium Allyl Sulfonate (AS) of deionized water and be placed in three mouthfuls of burnings
In bottle, lead to nitrogen deoxygenation 10min；Sequentially add 0.4~0.5g trihydroxyethyl allylic bromination ammonium (THAAB), 0.2~0.3g methyl
Methyl acrylate (MMA) and chain-transferring agent isopropanol simultaneously seal at once, and the chain-transferring agent isopropanol dosage accounts for AS, THAAB
Total mass ratio with MMA is 1.0wt%~6wt%,；It is sprinkled into etc. the K of 1.0wt%~4.5wt% of quality rapidly2S2O8With
NaHSO3And it seals.Mixed solution after polymerization reaction 3~8 hours, obtains the product under different shape at a temperature of 40~90 DEG C.It produces
Object is sufficiently washed through dehydrated alcohol, topple over, filter or evaporate ethyl alcohol be placed in vacuum drying oven after a certain period of time product
A kind of low-molecular weight polymer shale control agent AS/THAAB/MMA.
Preferred 70 DEG C of reaction temperature；Reaction time 6h；Total monomer 50wt%；g(AS):g(THAAB):g(MMA)
=40: 40: 20；Chain-transferring agent isopropanol dosage is 5.0wt%, initiator amount 2.0wt%.
Above-mentioned synthetic method is by choosing different reaction temperatures, reaction time, total monomer, monomer molar
Factor than, the influences synthesis such as chain-transferring agent isopropanol, initiator is tested, and is rolled back with linear expansion inhibiting rate and shale
Yield is overall target, is obtained after groping by test of many times, and this method can be low point of acquisition function admirable of high conversion
Sub- weight polymers shale control agent AS/THAAB/MMA.
Compared with prior art, the invention has the following beneficial effects: (1) this inhibitor has developed a kind of new polymerized monomer
THAAB, temporarily without document report in the research and development of inhibitor；(2) this inhibitor preparation method yield is high, and raw material is cheaply easy
, reaction condition is mild, and it is easily controllable, it can be used for industrial production；(3) this inhibitor salt ion containing quaternary ammonium and great amount of hydroxy group,
With adsorbing clays particle, the function of effectivelying prevent Shale Hydration to disperse；(4) this method preparation product thermal stability compared with
Good, molecular weight is lower, on the rheological property of drilling fluid almost without influence；(5) product is soluble easily in water, can be directly used for high temperature height
It presses in high-density water-based drilling fluid.
Detailed description of the invention
Fig. 1 is the infrared spectrum of AS/THAAB/MMA；
Fig. 2 is the molecular weight determination of AS/THAAB/MMA, wherein (1) is the 1st measurement result, (2) are the 2nd survey
Determine as a result, (3) are the 3rd measurement result；
Fig. 3 is the hot weight-differential heat curve graph of AS/THAAB/MMA；
Fig. 4 is the flocculating experiment figure that AS/THAAB/MMA starches base；
The near-infrared sedimentation stability that Fig. 5 is AS/THAAB/MMA is analyzed；
Fig. 6 is influence of the AS/THAAB/MMA to dry state clay crystal layer spacing, wherein (a) pure Na-MMT；(b)AS/
THAAB/MMA dosage 1.0wt%；(c) AS/THAAB/MMA dosage 1.5wt%；(d) AS/THAAB/MMA dosage 2wt%；
Fig. 7 is the scanning electron microscope (SEM) photograph that AS/THAAB/MMA influences scanning electron microscope fresh water-based slurry surface topography, and wherein a- is put
It is 150 times big；B- amplifies 500 times；C- amplifies 1000 times；D- amplifies 5000 times.
Embodiment
Below by embodiment, the invention will be further described.It should be understood that the method for the embodiment of the present invention
It is only used for illustrating the present invention, rather than limiting the invention, to preparation side of the invention under concept thereof of the invention
The simple modifications of method belong to the scope of protection of present invention.
Embodiment 1:
Total monomer 30wt% is accurately controlled, Sodium Allyl Sulfonate (AS) juxtaposition that 0.4g is dissolved in deionized water is weighed
In three-necked flask, lead to nitrogen deoxygenation 10min；It sequentially adds 0.4g trihydroxyethyl allylic bromination ammonium (THAAB), 0.2g first is added dropwise
Base methyl acrylate (MMA) and 0.05g chain-transferring agent simultaneously seal at once；It is sprinkled into the K of 0.01g rapidly2S2O8And NaHSO3And it is close
Envelope.Mixed solution after 4 hours of polymerization reaction, obtains thick product at a temperature of 40 DEG C.Product is sufficiently washed through dehydrated alcohol
Wash, topple over, filter or evaporate ethyl alcohol be placed in vacuum drying oven after a certain period of time 0.94g low-molecular weight polymer shale
Inhibitor AS/THAAB/MMA.Number-average molecular weight Mn is 18932, and weight average molecular weight Mw is 21369.
Embodiment 2:
Total monomer 40wt% is accurately controlled, 0.30g is weighed and is dissolved in the Sodium Allyl Sulfonate (AS) of deionized water simultaneously
It is placed in three-necked flask, leads to nitrogen deoxygenation 10min；It sequentially adds 0.45g trihydroxyethyl allylic bromination ammonium (THAAB), be added dropwise
0.25g methyl methacrylate (MMA) and 0.05g chain-transferring agent simultaneously seal at once；It is sprinkled into the K of 0.01g rapidly2S2O8With
NaHSO3And it seals.Mixed solution after 5 hours of polymerization reaction, obtains thick product at 50 °C.Product is through anhydrous
Ethyl alcohol sufficiently washs, topple over, filter or evaporate ethyl alcohol be placed in vacuum drying oven after a certain period of time 0.91g low molecular weight
Polymer shale control agent AS/THAAB/MMA.Number-average molecular weight Mn is 18736, and weight average molecular weight Mw is 21126.
Embodiment 3:
Total monomer 50wt% is accurately controlled, 0.20g is weighed and is dissolved in the Sodium Allyl Sulfonate (AS) of deionized water simultaneously
It is placed in three-necked flask, leads to nitrogen deoxygenation 10min；It sequentially adds 0.50g trihydroxyethyl allylic bromination ammonium (THAAB), be added dropwise
0.30g methyl methacrylate (MMA) and 0.04g chain-transferring agent simultaneously seal at once；It is sprinkled into the K of 0.01g rapidly2S2O8With
NaHSO3And it seals.Mixed solution after 5 hours of polymerization reaction, obtains thick product at a temperature of 70 DEG C.Product is through anhydrous
Ethyl alcohol sufficiently washs, topple over, filter or evaporate ethyl alcohol be placed in vacuum drying oven after a certain period of time 0.89g low molecular weight
Polymer shale control agent AS/THAAB/MMA.Number-average molecular weight Mn is 19561, and weight average molecular weight Mw is 12963.
Embodiment 4:
Total monomer 60wt% is accurately controlled, 0.30g is weighed and is dissolved in the Sodium Allyl Sulfonate (AS) of deionized water simultaneously
It is placed in three-necked flask, leads to nitrogen deoxygenation 10min；It sequentially adds 0.40g trihydroxyethyl allylic bromination ammonium (THAAB), be added dropwise
0.30g methyl methacrylate (MMA) and 0.10g chain-transferring agent simultaneously seal at once；It is sprinkled into the K of 0.03g rapidly2S2O8With
NaHSO3And it seals.Mixed solution after 6 hours of polymerization reaction, obtains thick product at a temperature of 70 DEG C.Product is through anhydrous
Ethyl alcohol sufficiently washs, topple over, filter or evaporate ethyl alcohol be placed in vacuum drying oven after a certain period of time 0.86g low molecular weight
Polymer shale control agent AS/THAAB/MMA.Number-average molecular weight Mn is 19686, and weight average molecular weight Mw is 23695.
Embodiment 5:
Total monomer 70wt% is accurately controlled, 0.40g is weighed and is dissolved in the Sodium Allyl Sulfonate (AS) of deionized water simultaneously
It is placed in three-necked flask, leads to nitrogen deoxygenation 10min；It sequentially adds 0.40g trihydroxyethyl allylic bromination ammonium (THAAB), be added dropwise
0.20g methyl methacrylate (MMA) and 0.10g chain-transferring agent simultaneously seal at once；It is sprinkled into the K of 0.05g rapidly2S2O8With
NaHSO3And it seals.Mixed solution after 6 hours of polymerization reaction, obtains thick product at a temperature of 70 DEG C.Product is through anhydrous
Ethyl alcohol sufficiently washs, topple over, filter or evaporate ethyl alcohol be placed in vacuum drying oven after a certain period of time 0.92g low molecular weight
Polymer shale control agent AS/THAAB/MMA.Number-average molecular weight Mn is 19471, and weight average molecular weight Mw is 21540.
Performance test:
For the inhibitory effect for evaluating this shale control agent, synthetic method resulting product in embodiment 5 is carried out following point
Analysis:
1. infrared analysis
The sample dried under the conditions of vacuum drying is taken, using KBr tabletting sample preparation, with Prestige-21 type infrared spectrometer
Infrared spectrum analysis is done, sees Fig. 1.
Infrared spectrum phenetic analysis is carried out to AS/THAAB/MMA and each comonomer, data are as follows: 3360cm-1Neighbouring
The stretching vibration absworption peak that strong absorption peak is-OH in THAAB；1750cm-1It is nearby C=O base stretching vibration absworption peak,
1040cm-1And 1070cm-1Neighbouring absorption peak is attributed to-SO respectively3Stretching vibration absworption peak, show Sodium Allyl Sulfonate join
With copolymerization；1400cm-1And 960cm-1It is attributed to the feature stretching vibration absworption peak of quaternary ammonium root in THAAB；1160cm-1With with
1066cm-1It is the bending vibration absorption peak of carbonyl C-O-C, it is meant that the presence of ester group in polymer；Contain in AS/THAAB/MMA
There is characteristic group's absorption peak of each monomer, shows that AS, THAAB and MMA successfully have occurred copolyreaction and generate target
Product AS/THAAB/MMA.
2. polymer molecular weight measures
Three groups of parallel experimental samples are done by synthetic method resulting product in embodiment 5, it is solidifying using Alliance e2695
Glue chromatograph (Waters, the U.S.) detects the weight average molecular weight and number-average molecular weight of polymer.Determination condition are as follows: with three
Chlorobenzene is mobile phase, and flow 1mL/min, chromatogram column temperature is 150 DEG C, and test result is as shown in Figure 2 and Table 1.
The molecular weight distribution data of 1 AS/THAAB/MMA of table
It may be seen that AS/THAAB/MMA has certain molecular weight distribution, but molecule from Fig. 2 and table 12
Measure narrow distribution.A certain amount of molecular weight distribution can guarantee that AS/THAAB/MMA not only can be with intercalation between clay crystal layer, but also can
It is coated in clay surface, inhibits clay hydration swelling and dispersion effect to reach.By what is surveyed under the conditions of parallel laboratory test three times
Data are it is found that similar morphology is presented in molecular weight distribution, and surveyed molecular weight difference is little three times.Survey three times average Mn be 19471,
Average Mw is 21540, average MP is 21822.Since AS/THAAB/MMA has relatively small molecular weight, drilling well is made an addition to
When in liquid system, the influence generated to the rheological characteristic of system will not be very big.All properties are tested using first time product as sample
Product.
The hot weight-differential heat figure of 3.AS/THAAB/MMA
TG-DSC analysis has been carried out to the AS/THAAB/MMA for purifying and drying, has been carried out by the temperature resistance ability to itself
Testing research has done preparatory investigation for it under the application environment of specific drilling fluid, has as a result seen Fig. 3.
It can be seen that the weight-loss curve of AS/THAAB/MMA can substantially be divided into four heats from TG-DSC analysis chart
Lose step: first stage is the weightlessness of 40~246 DEG C of 10.55wt%, and the weightlessness in this stage is primarily due to AS/
The evaporation of water is adsorbed in THAAB/MMA in aquation group；The weightlessness of 25.95wt% is main in 246~352 DEG C of sections in second stage
It is attributed to the decomposition of quaternary ammonium salt group；The weightlessness of (352~446 DEG C) 48.99wt% is mainly due to AS/ in three phases
The decomposition of-C-C- chain in THAAB/MMA.The last stage (446~600 DEG C), 30% or so.In addition, in DSC curve
In, 288 DEG C nearby it is observed that the appearance of a strong trough, i.e. polymer starts the stage acutely decomposed for this.TGA-
The synchronous differential thermal analysis of DSC demonstrates AS/THAAB/MMA with preferable temperature resistance effect.
4. normal temperature and pressure linear expansion and rolling recovery experiment
Inhibitor dosage is bigger, the inhibition of aqueous solution should be stronger, desk research AS/THAAB/MMA dosage pair
The influence of polymer rejection has substantially grasped its Shale Hydration and has inhibited rule, as shown in table 2:
The research of 2 AS/THAAB/MMA aqueous solution rejection of table
Note: hot 100 DEG C × 16h of rolling condition
As can be seen from Table 2, with the increase of AS/THAAB/MMA amount, while enhancing along with inhibitory effect, aqueous solution
Viscosity can be also gradually increasing.When dosage is 2.0wt%, normal temperature and pressure linear expansion height and shale rolling rate of recovery are respectively
6.7mm and 91.6%.When AS/THAAB/MMA dosage continues to increase, the raising of aqueous solution rejection is not it is obvious that at this time
The viscosity of solution is also promoted, and the very forbidden word of drilling fluid additive one is exactly to generate to drilling fluid system rheological characteristic
It influences.Therefore, the dosage of AS/THAAB/MMA in aqueous solution is that 2.0wt% is more appropriate.
The rejection of different polymer-type shale control agents has been investigated, as shown in table 3:
Table 3 polymerize the comparison of species inhibitor rejection
Note: hot 100 DEG C × 16h of rolling condition
As can be known from Table 3, the rolling recycling and linear expansion of 2wt%AS/THAAB/MMA is respectively 91.6% and 6.7mm；
Amphoteric ion inhibitor of the XY-27 as small molecule, rejection ability is limited, and rolling rate of recovery is only 56.8%；Coating agent
FA-367 possesses good Shale Hydration dispersion and hydration swelling rejection ability；Containing a large amount of on poly- dimethylamine-epoxychloropropane
Adsorptivity group hydroxy, have good clay aquation rejection；PF-CMJ can be firmly adsorbed in glutinous as film forming agent
Native surface, to play coating shale effect.Several polymeric inhibitors evaluated all have higher Shale Hydration dispersion
Rejection.
The flocculating experiment that 5.AS/THAAB/MMA starches base
As amphoteric ion polymer, with clay surface Electrostatic Absorption can occur for AS/THAAB/MMA, should have certain
Compress diffusion electric double layer ability.Therefore, from theoretical and empirical analysis, AS/THAAB/MMA should have certain wadding to drilling well base slurry
Solidifying ability.4g Na-MMT is added in 100mL 2.0wt%AS/THAAB/MMA solution, stirs evenly and is placed in colorimetric cylinder,
Sedimentation stability of the Na-MMT in its solution is tested, as a result sees Fig. 4.
Influence of the clay hydrate inhibiter of different dosage AS/THAAB/MMA to base slurry sedimentation stability is investigated, from a left side
It is followed successively by right AS/THAAB/MMA dosage as 1.0wt%, 1.5wt% and 2.0wt% and fresh water-based slurry.It can from Fig. 4
There is certain flocculation to fresh water-based slurry to AS/THAAB/MMA, but effect is not fairly obvious.AS/THAAB/MMA tool
There are adsorptivity group hydroxy and quaternary ammonium foundation group, can firmly be adsorbed in clay surface.Itself molecular weight is low, on the one hand can lack
Permitted to enter and compress diffusion electric double layer between the crystal layer of clay, so that clay aggregation is agglomerating, is sunk under gravity；Another party
Face can trap the clay particle in fresh water-based slurry, and the quality on strand aggravates, to cause the hair of fresh water-based slurry flocculation phenomenon
It is raw
The near-infrared sedimentation stability of 6.AS/THAAB/MMA is analyzed
1g Na-MMT is added in the 2.0%AS/THAAB/MMA solution of 100mL, is placed in instrument after mixing evenly,
Real-time monitoring has been carried out to the experiment of its sedimentation stability using infrared diaphanoscopy analyzer, has as a result seen Fig. 5.
When AS/THAAB/MMA dosage is 2.0wt%, the settling height of base slurry is 31mm, and the time increases and decreases to the left side 3h
It is right, it is known that clay can settle in AS/THAAB/MMA solution, but decrease speed is slow.It is attached on clay particle at this time
Suspending power, the common power of pulling force is mutually pulled between gravity and clay and clay, be unfavorable for the decline of product in a short time.But
It is that the final settlement height of base slurry but can decrease, and AS/THAAB/MMA expands between showing certain compression clay crystal layer
Dissipate the ability of electric double layer.
Influence of the 7.AS/THAAB/MMA to dry state clay crystal layer spacing；
It is well known that clay crystal layer spacing, especially d001Other factors between by clay crystal layer, such as hydrone, cationization
Close the influence of object, adsorbent, intercalator etc..Therefore by the variation of clay crystal layer spacing, can quantitatively find out between clay crystal layer
Whether have the replacement of other materials, replace etc..AS/THAAB/MMA overall molecule amount is although small, but relative to typical glutinous
Native intercalator, molecular weight are again much larger.Influence of the AS/THAAB/MMA to clay crystal layer spacing is had studied using XRD, is as a result seen
Fig. 6.
As shown in Figure 6: the bentonitic crystal layer spacing of dry state is 1.28nm, uses 1.0wt%, 1.5wt% and 2.0wt% respectively
The crystal layer spacing of the Na-MMT of processing is 1.29nm, 1.29nm and 1.29nm.By data it is found that AS/THAAB/MMA is processed
The crystal layer spacing variation of dry state soil only has slight variations, and the amount for illustrating that AS/THAAB/MMA can be entered inside crystal layer is seldom.
The scanning electron microscope image that 8.AS/THAAB/MMA influences scanning electron microscope fresh water-based slurry surface topography
In order to investigate the specific mode of action of AS/THAAB/MMA and clay, to the fresh water-based slurry of AS/THAAB/MMA processing
Processing mode it is as follows: the AS/THAAB/MMA solution of configuration 100mL 2.0wt% is added 4g into solution and has dried
Na-MMT；After stirring 2h, gained AS/THAAB/MMA base slurry solution is placed in the drilling fluid cup of normal temperature and pressure drop dehydration device,
Free settling dehydration is done, the filter cake on filter paper is taken after 12 hours, drying under natural conditions does electron-microscope scanning analysis to filter cake.This
The purpose that sample is done is to try to exclude the influence of external force, the function and effect of simple investigation polymer and Na-MMT.
It will be seen that one layer of accordion object of clay adsorption is attached to clay appearance from scanning electron microscope Fig. 7
Face, this is the composite products after clay inhibitor and soil interaction, this scanning result is glutinous with intercalation reported in the literature
The exterior appearance of soil coincide.Continue to amplify, it can be seen that there is accordion chain object under the conditions of × 500, it may be possible to macromolecule it
Between mutually wind the macromolecular chain being formed by." the strand rope " that AS/THAAB/MMA can use oneself bundlees clay
Get up, to play coating effect.It is coated with two ways, the first is " binding type ", and second is " film forming cover type ".From
This map analysis observation, the coated form of AS/THAAB/MMA is the first.Image is after amplifying, high molecular " rope " view
Feel that effect is more obvious (7c).
Claims (9)
1. a kind of low-molecular weight polymer shale control agent, it is characterised in that as shown in following Formulas I:
Wherein, R1ForR2ForR3ForX=1~5, y=2~5, z=2~4；Preferably, x
=4, y=4, z=2；Or x=3, y=4.5, z=2.5；Or x=2, y=5, z=3；Or x=3, y=4, z=3；Or x=4, y
=4, z=2.
2. low-molecular weight polymer shale control agent according to claim 1, it is characterised in that: number-average molecular weight Mn is
18000~20000, weight average molecular weight Mw are 20000~25000；Preferably, number-average molecular weight Mn is 18932, weight average molecular weight
Mw is 21369；Or number-average molecular weight Mn is 18736, weight average molecular weight Mw is 21126；Or number-average molecular weight Mn is 19561, weight
Average molecular weight Mw is 12963；Or number-average molecular weight Mn is 19686, weight average molecular weight Mw is 23695；Or number-average molecular weight Mn is
19471, weight average molecular weight Mw are 21540.
3. the preparation method of the low-molecular weight polymer shale control agent of claims 1 or 2, it is characterised in that: by allyl sulphur
Sour sodium (AS), reacts with trihydroxyethyl allylic bromination ammonium (THAAB) and methyl methacrylate (MMA).
4. preparation method according to claim 3, it is characterised in that include the following steps: the allyl that will be dissolved in deionized water
Sodium sulfonate (AS) is placed in three-necked flask, leads to nitrogen deoxygenation 10min；Sequentially add trihydroxyethyl allylic bromination ammonium (THAAB), drop
Methylate methyl acrylate (MMA) and chain-transferring agent simultaneously seal at once, the K of quality such as are sprinkled into rapidly2S2O8And NaHSO3And it is close
Envelope；Polymerization reaction, washing, filtering or evaporation, vacuum drying occur for mixed solution.
5. preparation method according to claim 3, it is characterised in that include the following steps:
X=1~5, y=2~5, z=2~4.
6. preparation method according to claim 3, it is characterised in that:
Preferably, AS, THAAB and MMA total monomer are 30wt%~70wt%；
Preferably, the polymeric reaction temperature is 40~90 DEG C；
Preferably, the polymerization reaction time is 3~8 hours；
Preferably, g (AS): g (THAAB): g (MMA)=40~20: 40~50: 20~30；
Preferably, chain-transferring agent be isopropanol and dosage to account for the total mass ratio of AS, THAAB and MMA be 1.0wt%~6wt%；
Preferably, the initiator K2S2O8And NaHSO3Dosage is the 1.0wt%~4.5wt% for accounting for monomer gross mass.
7. preparation method according to claim 3, it is characterised in that: 70 DEG C of polymeric reaction temperature；Polymerization reaction time 6h；Monomer
Total concentration 50wt%；G (AS): g (THAAB): g (MMA)=40: 40: 20；Chain-transferring agent isopropanol dosage is 5.0wt%, is caused
Agent dosage is 2.0wt%.
8. application of the low-molecular weight polymer shale control agent of any of claims 1 or 2 in terms of petrochemical industry.
9. the application method of low-molecular weight polymer shale control agent of any of claims 1 or 2, it is characterised in that: with configuration
In drilling fluid system on the basis of the quality of water, the dosage of inhibitor is 0.5wt%~3.0wt%.
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| CN112919882A (en) * | 2021-03-30 | 2021-06-08 | 江西省萍乡市华东出口电瓷有限公司 | High-strength high-hardness weather-resistant porcelain insulator and preparation method thereof |
| CN114231261A (en) * | 2021-12-31 | 2022-03-25 | 西安石油大学 | Organosilicate polymer inhibitor for well drilling and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104151491A (en) * | 2014-07-15 | 2014-11-19 | 中国石油集团长城钻探工程有限公司钻井液公司 | Enveloping inhibitor for drilling fluid and preparation method of enveloping inhibitor |
| CN106279522A (en) * | 2015-06-08 | 2017-01-04 | 中国石油化工股份有限公司 | A kind of Instant PAMC class coating agent and preparation method thereof |
| CN108587582A (en) * | 2018-06-07 | 2018-09-28 | 西安石油大学 | A kind of microemulsion shale control agent and preparation method thereof |
-
2019
- 2019-03-21 CN CN201910219867.9A patent/CN109777379B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104151491A (en) * | 2014-07-15 | 2014-11-19 | 中国石油集团长城钻探工程有限公司钻井液公司 | Enveloping inhibitor for drilling fluid and preparation method of enveloping inhibitor |
| CN106279522A (en) * | 2015-06-08 | 2017-01-04 | 中国石油化工股份有限公司 | A kind of Instant PAMC class coating agent and preparation method thereof |
| CN108587582A (en) * | 2018-06-07 | 2018-09-28 | 西安石油大学 | A kind of microemulsion shale control agent and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 刘磊: ""低分子量聚羧酸盐粘土抑制剂的合成及性能研究"", 《中国优秀硕士学位论文全文数据库 工程科技Ⅱ辑》 * |
| 蒲晓林: "多羟基有机铵黏土防膨剂的合成及应用", 《石油化工》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112919882A (en) * | 2021-03-30 | 2021-06-08 | 江西省萍乡市华东出口电瓷有限公司 | High-strength high-hardness weather-resistant porcelain insulator and preparation method thereof |
| CN112919882B (en) * | 2021-03-30 | 2022-09-16 | 江西省萍乡市华东出口电瓷有限公司 | High-strength high-hardness weather-resistant porcelain insulator and preparation method thereof |
| CN114231261A (en) * | 2021-12-31 | 2022-03-25 | 西安石油大学 | Organosilicate polymer inhibitor for well drilling and preparation method thereof |
| CN114231261B (en) * | 2021-12-31 | 2023-10-17 | 西安石油大学 | Organic silicate polymer inhibitor for drilling and preparation method thereof |
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| Publication number | Publication date |
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| CN109777379B (en) | 2021-02-09 |
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