CN106608946B - For drilling fluid tackifier copolymerization associated matter and preparation method thereof - Google Patents
For drilling fluid tackifier copolymerization associated matter and preparation method thereof Download PDFInfo
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Abstract
The invention discloses one kind for drilling fluid tackifier copolymerization associated matter and preparation method thereof, the copolymerization associated matter contains structural unit A, structural unit B, structural unit C and structural unit D, the structural unit A is N, N- dimethacrylamide, the structural unit B is zwitterionic monomer N- methyl diallyl propane sulfonic acid salt (MAPS), the structural unit C is the ion association body of structural unit B and cationic polyamine, the structural unit D is starch, on the basis of the total amount of the copolymerization associated matter, the N, the content of N- dimethacrylamide is 6-45 weight %, the total content of the zwitterionic monomer N- methyl diallyl propane sulfonic acid salt is 5-35 weight %, the content of the cationic polyamine is 2-30 weight %, the content of the starch is 5-35 weight Measure %.For the tackifier heatproof that preparation method of the present invention obtains up to 180 DEG C, anti-NaCl concentration reaches saturation, anti-CaCl2Concentration also has superior shale inhibition energy and filtrate loss controllability up to 20%.
Description
Technical field
The present invention relates to polymer for drilling fluid in Process of Oil Well Drilling and preparation method thereof, more particularly to a kind of drilling well
Liquid high temperature resistant anticalcium graft starch tackifier and preparation method thereof.
Background technique
In drilling process, in order to guarantee drilling fluid viscosity with higher and good rheological characteristic under low solid phase, usually
Need to add tackifier to improve the viscosity of drilling fluid.Drilling fluid tackifier is the very long water soluble polymer polymerization of strand
Object, tackifier also tend to also serve as shale control agent (coating agent), fluid loss additive and flow pattern modifier in addition to that can play tackifying effect
Deng.Therefore, the rheological characteristic for being often conducive to improve drilling fluid using tackifier, is also beneficial to wellbore stability.
Drilling fluid tackifier is one kind mostly important in drilling well auxiliary agent, is broadly divided into natural plant and synthesis macromolecule
Two major classes play a significant role in terms of guaranteeing drilling fluid safe construction, taking abrasive band.However existing drilling fluid tackifier
Such as xanthan gum, 80A51 are not well positioned to meet construction at high temperature needs, and most of tackifier are under the conditions of being higher than 150 DEG C
Efficient Adhesive Promotion declines rapidly, even disappears completely.In terms of salt resistance, also drilling fluid field is urgently for anti-high calcium chloride concentration
It solves the problems, such as, is more than 15% polymer almost without anti-calcium chloride concentration in currently used tackifier, thus often at present
Tackifier for drilling fluid heat resistance and anti-calcium and anti-salt performance tend not to take into account.
Anticalcium polymeric viscosifiers disclosed in CN102372818A and CN102464761A, mainly by acryloyl
Sulfonation group or hydrophobic grouping are introduced in amine polymer and is obtained, and only can satisfy calcium ion concentration not higher than 2000mg/L's
(less than 100 DEG C) use demand under cryogenic conditions.Disclosed in CN101955564A, CN103113518A and CN102127401A
The high temperature resistance of high temperature resistant tackifier, tackifier is obviously improved, and heatproof reaches 200 DEG C or more；Anti-calcium and anti-salt performance is not
It refers to, but speculates from monomer used and preparation method, anti-calcium and anti-salt performance is not improved.
Summary of the invention
In view of the deficiencies of the prior art, the present invention provides a kind of for drilling fluid tackifier copolymerization associated matter and its preparation side
Method.For the tackifier heatproof that the method for the present invention obtains up to 200 DEG C, anti-NaCl concentration reaches saturation, anti-CaCl2Concentration is up to 20%.In height
Higher apparent viscosity is maintained after warm aging, while also there is preferable yield value.
The present invention provides one kind to be copolymerized associated matter for drilling fluid tackifier, and the copolymerization associated matter contains structural unit
A, structural unit B, structural unit C and structural units D, the structural unit A are N,N-DMAA, the structure list
First B be zwitterionic monomer N- methyl diallyl propane sulfonic acid salt (MAPS), the structural unit C be structural unit B and sun from
The ion association body of sub- polyamine, the structural unit D are starch, on the basis of the total amount of the copolymerization associated matter, the N, N-
The content of dimethacrylamide is 6-45 weight %, preferably 10-40 weight %；Two allyl of zwitterionic monomer N- methyl
The total content of base propane sulfonic acid salt is 5-35 weight %, preferably 10-32 weight %；The content of the cationic polyamine is 2-30 weight
Measure %, preferably 5-28 weight %；The content of the starch is 5-35 weight %, preferably 10-32 weight %；The copolymerization associated matter
It is 40-70mPas in 180 DEG C of apparent viscosities after aging 16 hours.
The tackifier copolymerization associated matter provided according to the present invention, the knot of the structural unit A N,N-DMAA
Structure formula are as follows:Formula (I), the structural unit B zwitterionic monomer N- methyl diallyl
The structural formula of propane sulfonic acid salt (MAPS) are as follows:Formula (II), the structural unit C have
Structure shown in following formula:
Formula (III)
Wherein, dotted line ... indicates ion association, X-For inorganic anion；R,R9、R9’、R10、R10' respectively following
Structure shown in formula (IV):Formula (IV), wherein R11For H, replace
Or unsubstituted C1-C5 alkyl, t are the integer of 1-5, z is the integer of 0-5；
N, p is respectively the integer of 1-5；X is the integer of 0-10, and y is the integer of 1-10；L, the value of l ' and l " makes described
The kinematic viscosity of cationic polyamine is 100-500mm2/ s, cationic degree 0.5-2mmol/g.The further preferred cation
The kinematic viscosity of polyamine is 150-450mm2/ s, cationic degree 0.5-1.5mmol/g.
The structural formula of the structural unit D starch are as follows:, specific described
Starch can for green starch, tapioca, sweet potato starch, starch from sweet potato, potato starch, wheat starch, water caltrop starch,
One or more of Rhizoma Nelumbinis starch, cornstarch, preferably cornstarch or potato starch.
Above-mentioned cationic polyamine can have multiple nitrogen cations and corresponding balance anion, preferable case to be various
Under, the cationic polyamine holds haloalkylene oxide shown in cyclic ethers shown in amine and formula (VI) and formula (VII) as shown in formula (V)
It is obtained by condensation reaction
T, n, p are respectively the integer of 1-5；X is the integer of 0-10, and y is the integer of 1-10.When x is 0, formula (V) indicates end
Diamines, y are preferably the integer of 1-7；When x is not equal to 0, and when y=2, formula (V) indicates that polyethylene polyamine, x are the integer of 1-10.
Wherein the definition of substituent group and subscript with it is identical above.
Specifically, the cationic polyamine can be made by following methods: to end at stirring condition and 50-120 DEG C
Cyclic ethers is added dropwise in amine, cyclic ethers and the molar ratio for holding amine are 2-4:1, react 1-4 hours after completion of dropwise addition, then heat to 80-150
DEG C, haloalkylene oxide is added dropwise under stirring condition, haloalkylene oxide and the molar ratio for holding amine are 0.2-0.7:1, anti-after completion of dropwise addition
It answers 1-4 hours, then terminates reaction.
It should be noted that although 50-120 DEG C of temperature range before heating has with 80-150 DEG C of temperature range after heating
It partly overlaps, but the temperature of the latter must be higher than the former temperature.
Reaction can be terminated by the way that hydrochloric acid is added.The additional amount of hydrochloric acid is preferably hydrochloric acid: end amine=1-3:1(molar ratio).
Under preferable case, the end amine is ethylenediamine, propane diamine, butanediamine, hexamethylene diamine, diethylenetriamine, triethylene four
One of amine, tetraethylenepentamine are a variety of.
Under preferable case, the cyclic ethers is one of ethylene oxide, propylene oxide, tetrahydrofuran or a variety of.
Under preferable case, the haloalkylene oxide be one of epoxychloropropane, epoxy bromopropane, epoxy chlorobutane or
It is a variety of.
The copolymerization associated matter provided according to the present invention, under preferable case, the weight average molecular weight of the copolymerization associated matter is 50
Ten thousand-500 ten thousand, further preferably 1,000,000-300 ten thousand.
In the present invention, copolymerization associated matter refer to both included in polymer by copolymerization formed structure, also include by from
The structure that sub- association is formed, wherein structural unit A, structural unit B and structural unit D are formed by copolymerization, structural unit B
It is combined together with cationic polyamine by ion association, forms structural unit C.Dotted line ... in each structural formula indicate from
Sub- association.
In the present invention, the content for being copolymerized cationic polyamine in associated matter, which refers to, to be provided in copolymerization associated matter by cationic polyamine
Various structure types total content, including formed copolymerization associated matter cationic polyamine amount, also include it is not formed copolymerization form
Close the amount of the cationic polyamine of object.
The means of testing grasped due to inventor is limited and/or limitation based on existing means of testing, copolymerization of the invention
The content of each structural unit of associated matter is only capable of test and is the content of structural unit corresponding with monomer, and cannot measure structural unit
The content of C can not measure the amount for participating in the zwitterionic structural elements for associating and having neither part nor lot in association, i.e., above-mentioned amphoteric ion knot
The content of structure unit includes the zwitterionic structural elements i.e. structural unit B for associating with cationic polyamine and forming structural unit C
Content also includes not forming the content of the zwitterionic structural elements of structural unit C with associating with cationic polyamine.
In the present invention, the content of each structural unit can be calculated by reaction front and back content of monomer or nuclear magnetic resonance combines
The mode of infrared spectrum analysis determines.
In the present invention, the alkyl of the C1-C5 can be methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group,
One of tert-butyl, n-pentyl, isopentyl, tertiary pentyl, neopentyl are a variety of.The substituent group of the alkyl of the C1-C5 is for example
It can be halogen or hydroxyl.
The copolymerization associated matter provided according to the present invention is wherein normal between structural unit A, structural unit B and structural unit D
The covalent polymerization methods of rule, i.e., between by Covalent bonding together, and structural unit C then pass through its anion and it is cationic respectively with
Cation and anion on structural unit B become the structural unit of copolymerization associated matter with ion association, thus by it
Network structure is introduced into copolymerization associated matter, so that copolymerization associated matter shear force with higher and heat-resistant salt-resistant.Above-mentioned ion is formed
Cooperation with can by by its with by by between structural unit A, structural unit B, structural unit D copolymerization associated matter and sun from
The mixture that sub- polyamine is simply mixed measures the greatest differences of its shear force and heat-resistant salt-resistant simultaneously under the same conditions
Speculate to obtain in conjunction with the principles of chemistry.
In the present invention, the content of each structural unit can be calculated by reaction front and back content of monomer or nuclear magnetic resonance combines
The mode of infrared spectrum analysis determines.
The present invention also provides a kind of preparation method of above-mentioned tackifier for drilling fluid copolymerization associated matter, the method includes with
Lower step:
(1) inorganic salts are mixed with water, prepares the inorganic salt solution of 2wt%~30wt%；
(2) cationic polyamine and water are hybridly prepared into cationic polyamine aqueous solution, the cationic polyamine aqueous solution
Mass concentration is 0.5%~3%；
(3) weigh starch and mixed with the inorganic salt solution that part steps (1) are prepared, at 60~80 DEG C stir 20~
50min obtains gelatinized starch after processing；
(4) N is passed through in the gelatinized starch obtained to step (3)2, initiator is added after reacting 15~60min；
(5) remainder in N- methyl diallyl propane sulfonic acid salt and N, N- dimethacrylamide and step (1) is weighed
The inorganic salt solution mixing that (1) is prepared step by step, is added in the gelatinized starch that step (4) obtains, until completely dissolved 50
1~2h is reacted at~70 DEG C.Wherein, N- methyl diallyl propane sulfonic acid salt, N,N-DMAA and starch monomer are total
Mass concentration is 5%~20%, and according to N,N-DMAA, N- methyl diallyl propane sulfonic acid salt, starch and sun
On the basis of the total amount of polyamine, the dosage of N,N-DMAA is 6-45 weight %, preferably 10-40 weight %；N-
The dosage of methyl diallyl propane sulfonic acid salt is 5-35 weight %, preferably 10-32 weight %；Starch dosage is 5-35 weight %, excellent
It is selected as 10-32 weight %；
(6) the cationic polyamine aqueous solution that step (2) are prepared is added in the reaction product that step (5) obtains, is mixed
60~80 DEG C uniformly are warming up to simultaneously, the reaction was continued 3~5h；Wherein, according to N,N-DMAA, two allyl of N- methyl
On the basis of the total amount of base propane sulfonic acid salt, starch and cationic polyamine, cationic polyamine dosage is 2-30 weight %, preferably 5-28
Weight %.
(7) reaction product that step (6) obtains is washed with acetone soln, the solid sediment obtained after washing is through overdrying
Purpose product is obtained after dry and crushing.
The preparation method of the copolymerization associated matter provided according to the present invention, a main function of the inorganic salts are to provide two
Property ionic structure unit on anion and cation exchange with the cationic and anion on cationic polyamine/association
Environment, as long as therefore being capable of providing the inorganic salts of above-mentioned environment and may be used as inorganic salts of the invention.Under preferable case, institute
Stating inorganic salts is one of ammonium salt, calcium salt, magnesium salts, mantoquita, zinc salt, aluminium salt, zirconates or a variety of.The inorganic salts are preferably with molten
Liquid form uses.
The present inventor is by research it has furthermore been found that different types of inorganic salts, reach the solution of optimum efficiency
Concentration is different, for example, the inorganic salt solution concentration is preferably 10wt%~30wt% when the inorganic salts are ammonium salt；The nothing
When machine salt is calcium salt, magnesium salts, mantoquita, zinc salt, the inorganic salt solution concentration is preferably 5%~15%, and more preferably 10%~15%；
When the inorganic salts are aluminium salt, the inorganic salt solution concentration is preferably 2wt%~10wt%；When the inorganic salts are zirconates, institute
The inorganic salt solution concentration stated is preferably 2wt%~5wt%.The concentration of above-mentioned inorganic salt solution only considers inorganic salts and its solvent
Amount, does not consider the amount of other substances such as monomer.
When the inorganic salts be ammonium salt when, be specifically as follows ammonium chloride, ammonium bromide, ammonium nitrate it is one or more；Work as institute
State inorganic salts be calcium salt when, be specifically as follows calcium chloride, calcium bromide；When the inorganic salts are magnesium salts, it is specifically as follows chlorination
Magnesium, magnesium bromide, magnesium sulfate, magnesium nitrate it is one or more；When the inorganic salts are aluminium salt, it is specifically as follows aluminium chloride, bromine
Change aluminium, aluminum sulfate, aluminum nitrate it is one or more；When the inorganic salts be mantoquita when, be specifically as follows copper chloride, copper bromide,
Copper sulphate, copper nitrate it is one or more；When the inorganic salts are zinc salt, it is specifically as follows zinc chloride, zinc bromide, zinc nitrate
It is one or more；When the inorganic salts be zirconates when, be specifically as follows zirconium chloride, zirconium bromide, zirconium oxychloride, zirconium nitrate one
Kind is a variety of.
The preparation method of the copolymerization associated matter provided according to the present invention, the type and dosage of the initiator are referred to existing
There is technology progress.Under preferable case, the initiator can be one of sodium peroxydisulfate, potassium peroxydisulfate, ammonium persulfate or more
Kind.The dosage of the initiator is preferably the 0.3-0.7wt% of monomer total amount.
The preparation method of copolymerization associated matter provided by the invention, the starch can be green starch, tapioca, sweet
One or more of sweet potato starch, starch from sweet potato, potato starch, wheat starch, water caltrop starch, Rhizoma Nelumbinis starch, cornstarch, it is excellent
Select cornstarch or potato starch.
What is provided according to the present invention is copolymerized the preparation method of associated matter, and inorganic salt solution used in the step (5) is
The 1/2~3/5 of inorganic salt solution total amount in step (3).
In the method for the present invention, the monomer gross mass concentration is the ratio of monomer mass and water gross mass.
The preparation method of the copolymerization associated matter provided according to the present invention, the cationic polyamine have shown in following formula (i)
Structure:
Formula (i)
Wherein, X-For inorganic anion；R,R9、R9’、R10、R10' it is respectively structure shown in following formula (IV)s
Formula (IV), wherein R11For H, substituted or unsubstituted
C1-C5 alkyl, t be 1-5 integer, z be 0-5 integer；N, p is respectively the integer of 1-5, and x is the integer of 0-10, y 1-
10 integer；L, the value of l ' and l ' ' makes the kinematic viscosity of the cationic polyamine be 100-500mm2/ s, cationic degree are
0.5-2mmol/g。
Above-mentioned cationic polyamine be referred to the preparation method of cationic polyamine polymer disclosed in CN103773332A into
Row preparation: it is obtained by the way that amine, cyclic ethers and epoxy alkyl halide will be held to carry out polymerization reaction.The end amine can be alkyl diamine such as carbon
Atomicity is the alkyl diamine of 1-6, specific such as ethylenediamine, propane diamine, butanediamine, pentanediamine or hexamethylene diamine；It may be polyenoid
Polyamines such as NH2-(CH2-CH2-NH)nThe H integer that wherein n is 1-5, such as diethylenetriamine, triethylene tetramine or tetraethylenepentamine.
The cyclic ethers can be cyclic ethers such as ethylene oxide, propylene oxide, the epoxy butane that carbon atom number is 2-6.The epoxy alkyl halide
It such as can be epoxychloropropane, epoxy bromopropane or epoxy chlorobutane.But in order to ensure association and obtain preferably brill
The kinematic viscosity of well liquid performance, the cationic polyamine should control as 100-500mm2/ s, cationic degree, which should control, is
0.5-2mmol/g.Kinematic viscosity and cationic degree can be controlled upper by the additional amount of control cyclic ethers and epoxy alkyl halide
It states in range.Generally the molar ratio of control terminal amine and cyclic ethers is 1:(2-4).Holding the molar ratio of amine and epoxy alkyl halide is 1:
(0.2-0.7).Other reaction conditions and operation are referred to the above-mentioned prior art and carry out.
The cationic polyamine preferably uses as an aqueous solution, and the concentration of cationic polyamine aqueous solution is preferably 0.5-
3wt%, wherein the amount of water is the total Water in reaction system.
The method provided according to the present invention, the purpose of step (6) products therefrom acetone washing are to remove unreacted
Component, dry temperature can be 100-120 DEG C, and the dry time can be 16-24 hours.
In the method for the present invention, MAPS used can be synthesized by step as described below: weighing molar ratio respectively is 2:1~9:1, excellent
It is selected as the N- amide and 1,3-propane sultone of 2.5:1~8:1, and is added 1 into N- amide,
3-N-morpholinopropanesulfonic acid lactone；Then 20 DEG C~90 DEG C at a temperature of react 0.5-4h, preferably 60~80 DEG C at a temperature of react 1-
3h, finally through filtering, extracting, dry obtained N- methyl diallyl propane sulfonic acid salt.The 1,3- propane sultone can be added dropwise
Into N- amide, can also directly be added at one time in N- amide, it is preferably directly disposable
Adding manner.When using directly mode is added at one time, N- amide and 1,3-propane sultone molar ratio are excellent
It is selected as 5.2:1~7.8:1；When using dropwise addition mode, N- amide and 1,3-propane sultone molar ratio are preferred
For 2.5:1~5:1,1,3-propane sultone can be heated and be melted before dropwise addition.The extraction solvent selects methanol or ethyl alcohol, excellent
Ethyl alcohol is selected, extraction times are 1~3h, and drying temperature is 30~50 DEG C, and drying time is 10~20h.
Compared with prior art, tackifier copolymerization associated matter provided by the invention and preparation method thereof advantage is as follows:
(1) copolymerization associated matter provided by the invention, by containing N,N-DMAA knot simultaneously with certain proportion
Structure unit, zwitterionic structural elements, starch unit and cationic polyamine structural unit, and cationic polyamine structural unit has
Specific kinematic viscosity and cationic degree, when so that the copolymerization associated matter being used as drilling fluid tackifier, gained drilling fluid not only exists
There is good apparent viscosity after high temperature ageing, but also there is preferable shear force, and heatproof resists at least up to 180 DEG C or more
NaCl concentration reaches saturation, anti-CaCl2Concentration is up to 20%.
(2) in the preparation method of tackifier copolymerization associated matter of the present invention, the phase is by using high concentration inorganic salts before the reaction
Solution can make sulfonic group zwitterionic monomer form special construction in conjunction with inorganic salts, due to metal ion in inorganic salts
In the presence of so that the structure of sulfonic group zwitterionic monomer more stretches, when polymerization, is substantially reduced intermolecular steric hindrance, makes list
Body molecules align is even closer, considerably increases the molecular weight of polymer.The phase is by being added low molecular weight cationic after the reaction
Polyamine is further sent out with the sulfonic group in zwitterionic monomer by the ammonium cation on low molecular weight cationic polyamine structure
Raw effect, forms more stable network structure, strengthens the structural viscosity of polymer, is guaranteeing tackifier with good table
While seeing viscosity, and it is provided with preferable shear force.
(3) the tackifier copolymerization associated matter of the method for the present invention preparation has long-chain branch and rigid annular group.In aqueous solution
In due to long-chain branch and rigid annular group presence, increase the steric hindrance of polymer, increase the fluid force of polymer
Volume is learned, the trend for causing polymer to be affected by temperature fracture hydrolysis is reduced, to improve the performance of its heatproof, heatproof is at least
Up to 180 DEG C, some has reached 200 DEG C.
Detailed description of the invention
Fig. 1 and Fig. 2 is respectively MAPS's1HNMR and13CNMR spectrogram.
Specific embodiment
The effect and effect of the method for the present invention are illustrated below with reference to embodiment, but following embodiment is not constituted to this
The limitation of scheme of the invention.The present invention is described further for the following examples.In following embodiment, kinematic viscosity is used
265 oil product kinematic viscosity measuring method of national standard GB/T and dynamic viscosity calculating method measure；Cationic degree uses colloidal titration side
Method measures；Apparent viscosity and yield value are measured by six fast rotational viscometer methods.Wherein, shear force indicates that the structure that system has is viscous
Degree, shear force is bigger, illustrates that the performance of the suspension landwaste of drilling fluid is better.
Starch used in the embodiment of the present invention and comparative example is the wide cornstarch of middle sugared family, potato starch used
For.
MAPS monomer used in the embodiment of the present invention and comparative example can be prepared as follows: weigh 650g N-
Amide pours into reactor, is then placed in thermostat water bath, heats and starts to stir.122g 1 is weighed again,
3-N-morpholinopropanesulfonic acid lactone is added directly into N- amide, and reaction temperature is 80 DEG C, is obtained after being stirred to react 3h
The crude product of MAPS.MAPS crude product is transferred in large stretch of filter paper and is wrapped, is placed in Soxhlet extraction device, is using ethyl alcohol
Filter paper packet is placed in drying box by solvent extraction 3h after extracting, dry at 50 DEG C, and it is mono- to finally obtain pure MAPS
Body.
Cationic polyamine used is prepared as follows in the embodiment of the present invention and comparative example:
In 1000mL four round flask, 60g ethylenediamine is added, is warming up to 70 DEG C under agitation, then gradually
116g propylene oxide is added dropwise, controls 60-100 DEG C of reaction temperature, is warming up to 95 DEG C after reacting 1h, 185g epoxy chloropropionate is gradually added dropwise
Alkane, control reaction temperature is 90-150 DEG C, and when thickening behavior occurs in reaction system, hydrochloric acid at least is added after maintenance half an hour,
The molar ratio of hydrochloric acid and ethylenediamine is 2:1, and reaction 4h obtains cationic polyamine 1.The kinematic viscosity of cationic polyamine 1 is
330mm2/ s, cationic degree 1.8mmol/g.
Wherein, R9、R9’、R10、R10' it is respectively structure shown in following formula (IV-1)
Formula (IV-1)
In 1000mL four round flask, 60g hexamethylene diamine is added, is warming up to 70 DEG C under agitation, then gradually
116g ethylene oxide is added dropwise, controls 60-100 DEG C of reaction temperature, is warming up to 95 DEG C after reacting 1h, 185g epoxy bromine third is gradually added dropwise
Alkane, control reaction temperature is 90-150 DEG C, and when thickening behavior occurs in reaction system, hydrochloric acid at least is added after maintenance half an hour,
The molar ratio of hydrochloric acid and hexamethylene diamine is 2:1, and reaction 4h obtains cationic polyamine 2.The kinematic viscosity of cationic polyamine 2 is
460mm2/ s, cationic degree are 1.9 mmol/g.
In 1000mL four round flask, be added 60g triolefin tetramine, be warming up to 70 DEG C under agitation, then by
116g epoxy butane is gradually added dropwise, controls 60-100 DEG C of reaction temperature, is warming up to 95 DEG C after reacting 1h, 185g epoxy chlorine is gradually added dropwise
Butane, control reaction temperature is 90-150, and when thickening behavior occurs in reaction system, hydrochloric acid at least is added after maintenance half an hour,
The molar ratio of hydrochloric acid and triolefin tetramine is 2:1, and reaction 4h obtains cationic polyamine 3.The kinematic viscosity of cationic polyamine 3 is 410
mm2/ s, cationic degree are 1.5 mmol/g.
Embodiment 1
170g MAPS is weighed respectively, and 140g DMAM and 100g cornstarch is spare, then weighs 6730g deionization respectively
Water and 1758gNaCl are configured to NaCl solution, and solution is divided into two parts.By cornstarch be added a part of NaCl solution in
80 DEG C of gelatinization 30min, are passed through N2 3.7g potassium peroxydisulfate is added after 30min, then DMAM and MAPS are added to remainder NaCl
It in solution, is transferred in gelatinized starch after dissolution, obtains intermediate product after reacting 2h at 65 DEG C.Again by 140g cationic polyamine
1 is dissolved in 300g deionized water and is configured to cationic polyamine solution, and then cationic polyamine solution is added to intermediate product
In, it is uniformly mixed, while being warming up to 75 DEG C, the reaction was continued 4 hours.It is cleaned to obtain sediment with acetone, the sediment is existed
Graft starch tackifier are crushed to obtain after dry 12h at 70 DEG C.
Embodiment 2
150g MAPS is weighed respectively, and 112g DMAM and 100g potato starch is spare.Weigh respectively again 2870g go from
Sub- water and 330g CaCl2It is configured to CaCl2Solution is divided into two parts of volume ratio 6:4 by solution.It is added in potato starch
In more a part of CaCl2Solution is passed through N in 70 DEG C of gelatinization 30min2 1.7g sodium peroxydisulfate is added after 30min, then by DMAM and
Remaining few CaCl is added in MAPS2It is transferred in gelatinized starch reactor after solution dissolution, is obtained after reacting 1.5h at 70 DEG C
Intermediate product.30g cationic polyamine 2 is dissolved in 100g deionized water again and is configured to cationic polyamine solution, it then will be positive
Polyamine solution is added into intermediate product, is uniformly mixed, while being warming up to 80 DEG C, the reaction was continued 3 hours.It is cleaned with acetone
Obtain sediment.Sediment crushes to obtain graft starch tackifier after dry 12h at 80 DEG C.
Embodiment 3
130g MAPS is weighed respectively, and 168g DMAM and 100g potato starch is spare.Weigh respectively again 1785g go from
Sub- water and 105g AlCl3It is configured to AlCl3Solution is divided into two parts by solution.A part of AlCl is added in potato starch3
Solution is passed through N in 60 DEG C of gelatinization 30min2 5.3g ammonium persulfate is added after 30min, then remainder is added in DMAM and MAPS
AlCl3It is transferred in gelatinized starch reactor after solution dissolution, obtains intermediate product after reacting 2h at 60 DEG C.Again by 60g sun
Polyamine 3, which is dissolved in 200g deionized water, is configured to cationic polyamine solution, then by cationic polyamine solution be added to
In intermediate product, it is uniformly mixed, while being warming up to 70 DEG C, the reaction was continued 4 hours.It is cleaned to obtain sediment with acetone.Sediment
Graft starch tackifier are crushed to obtain after dry 12h at 80 DEG C.
Embodiment 4
100g MAPS is weighed respectively, and 140g DMAM and 100g cornstarch is spare.Weigh 1100g deionized water respectively again
With 63g ZrCl4It is configured to ZrCl4Solution is divided into two parts of volume ratio 6:4 by solution.Cornstarch is added thereto more
A part of ZrCl4Solution is passed through N in 75 DEG C of gelatinization 30min2 3g potassium peroxydisulfate is added after 30min, then DMAM and MAPS are added
Enter remaining few ZrCl4It is transferred in gelatinized starch reactor after solution dissolution, obtains intermediate production after reacting 1.5h at 65 DEG C
Object.30g cationic polyamine 2 is dissolved in 100g deionized water again and is configured to cationic polyamine solution, it is then that cation is poly-
Amine aqueous solution is added into intermediate product, is uniformly mixed, while being warming up to 77 DEG C, the reaction was continued 4.5 hours.It cleans to obtain with acetone
Sediment.Sediment crushes to obtain graft starch tackifier after dry 12h at 75 DEG C.
Inorganic salts are not added in comparative example 1()
150g MAPS is weighed respectively, and 112g DMAM and 100g potato starch is spare.Weigh respectively again 2870g go from
Deionized water is divided into two parts by sub- water.A part of deionized water is added in 70 DEG C of gelatinization 30min in potato starch, is led to
Enter N2 1.7g sodium peroxydisulfate is added after 30min, then DMAM and MAPS are added after another part deionized water dissolving and are transferred to paste
Change in starch reaction device, obtains intermediate product after reacting 1.5h at 70 DEG C.30g cationic polyamine 2 is dissolved in 100g again
It is configured to cationic polyamine solution in ionized water, then cationic polyamine solution is added into intermediate product, is uniformly mixed, together
When be warming up to 80 DEG C, the reaction was continued 3 hours.It is cleaned to obtain sediment with acetone.Sediment crushes after dry 12h at 80 DEG C
Graft starch tackifier.
Cationic polyamine is not added in comparative example 2()
150g MAPS is weighed respectively, and 112g DMAM and 100g potato starch is spare.Weigh respectively again 2970g go from
Sub- water and 330g CaCl2It is configured to CaCl2Solution is divided into two parts of volume ratio 6:4 by solution.It is added in potato starch
In more a part of CaCl2Solution is passed through N in 70 DEG C of gelatinization 30min2 1.7g sodium peroxydisulfate is added after 30min, then by DMAM and
Remaining few CaCl is added in MAPS2It is transferred in gelatinized starch reactor after solution dissolution, obtains glue after reacting 5h at 80 DEG C
Shape solid is cleaned to obtain sediment with acetone.Sediment crushes to obtain graft starch tackifier after dry 12h at 80 DEG C.
Comparative example 3
Pass through commercially available purchase tackifier 80A51.
Comparative example 4
Pass through commercially available purchase tackifier xanthan gum.
Above-described embodiment and comparative example using saliferous calcic base slurry evaluation thickening property, it is specific evaluation method is as follows:
Base slurry is prepared: 40g calcium bentonite and 5g sodium carbonate, high-speed stirred 20min, room temperature decentralization being added in 1000mL water
It sets maintenance for 24 hours, obtains fresh water-based slurry；Continuously add 200g CaCl2, high-speed stirred 20min, placement maintenance for 24 hours, obtains at room temperature
To evaluation with containing 20% CaCl2Base slurry.
Evaluation method: measuring the base slurry of 350mL, and 2% tackifier, high-speed stirred 20min are added, and room temperature maintenance is surveyed afterwards for 24 hours
Its apparent viscosity.Apparent viscosity is measured again after aging 16h at 180 DEG C again, calculates apparent viscosity retention.
The different tackifier temperature-resistant anti-salt anticalcium performance comparison tables of table 1
| Apparent viscosity (after high temperature ageing)/mPa s | Apparent viscosity conservation rate/% | Yield value (after high temperature ageing)/mPa s | |
| Embodiment 1 | 53 | 88.2 | 21 |
| Embodiment 2 | 65 | 92.1 | 26 |
| Embodiment 3 | 60 | 90.2 | 25 |
| Embodiment 4 | 65 | 92.8 | 24 |
| Comparative example 1 | 18 | 51.3 | 2 |
| Comparative example 2 | 43 | 74.5 | 8 |
| Comparative example 3 | 4 | 12.5 | 0 |
| Comparative example 4 | 6 | 8.33 | 0 |
Note: the dosage of 4 xanthan gum of comparative example is 0.5%.
It is higher to can be seen that the tackifier of the invention apparent viscosity conservation rate after high temperature ageing from the result of table 1, says
Preferable heatproof and salt resistant character is illustrated；And yield value ensure that wellbore fluid also in preferable level after high temperature ageing
The rock of taking of system under the high temperature conditions mentions grittiness energy.
Claims (28)
1. one kind is copolymerized associated matter for drilling fluid tackifier, the copolymerization associated matter contains structural unit A, structural unit B, knot
Structure unit C and structural units D, the structural unit A are N,N-DMAA, and the structural unit B is amphoteric ion
Monomer N- methyl diallyl propane sulfonic acid salt (MAPS), the structural unit C is structural unit B and the ion of cationic polyamine is formed
Zoarium, the structural unit D are starch, on the basis of the total amount of the copolymerization associated matter, the N,N-DMAA
Content be 6-45 weight %, the total content of the zwitterionic monomer N- methyl diallyl propane sulfonic acid salt is 5-35 weight %,
The content of the cationic polyamine is 2-30 weight %, and the content of the starch is 5-35 weight %, and the copolymerization associated matter is 180
Apparent viscosity DEG C after aging 16 hours is 40-70mPas；
Wherein, the cationic polyamine held as shown in formula (V) amine with it is halogenated shown in cyclic ethers shown in formula (VI) and formula (VII)
Alkylene oxide is obtained by condensation reaction
T, n, p are respectively the integer of 1-5；X is the integer of 0-10, and y is the integer of 1-10, R11For H, substituted or unsubstituted C1-
C5 alkyl.
2. copolymerization associated matter described in accordance with the claim 1, it is characterised in that: on the basis of the total amount of the copolymerization associated matter,
The content of the N,N-DMAA is 10-40 weight %, the zwitterionic monomer N- methyl diallyl propane sulfonic acid
The total content of salt is 10-32 weight %, and the content of the cationic polyamine is 5-28 weight %, and the content of the starch is 10-32
Weight %.
3. copolymerization associated matter described in accordance with the claim 1, it is characterised in that: when x is 0, formula (V) indicates end diamines, y 1-
7 integer.
4. copolymerization associated matter described in accordance with the claim 1, it is characterised in that: when x is not equal to 0, and when y=2, formula (V) indicates more
Ethylene polyamine, x are the integer of 1-10.
5. copolymerization associated matter described in accordance with the claim 1, it is characterised in that: the structural unit C has knot shown in following formula
Structure:
Formula (III)
Wherein, dotted line ... indicates ion association, X-For inorganic anion；R,R9、R9’、R10、R10' it is respectively following formula (IV)s
Shown in structure:Formula (IV), wherein R11For H, replaces or do not take
The C1-C5 alkyl in generation, t are the integer of 1-5, and z is the integer of 0-5；N, p is respectively the integer of 1-5；X is the integer of 0-10, and y is
The integer of 1-10；L, the value of l ' and l " makes the kinematic viscosity of the cationic polyamine be 100-500mm2/ s, cationic degree
For 0.5-2mmol/g.
6. being copolymerized associated matter according to claim 5, it is characterised in that: the kinematic viscosity of the cationic polyamine is 150-
450mm2/ s, cationic degree 0.5-1.5mmol/g.
7. copolymerization associated matter described in accordance with the claim 1, it is characterised in that: the cationic polyamine passes through following methods system
: cyclic ethers is added dropwise into end amine at stirring condition and 50-120 DEG C, cyclic ethers and the molar ratio for holding amine are 2-4:1, completion of dropwise addition
It reacts 1-4 hours afterwards, then heats to 80-150 DEG C, haloalkylene oxide, haloalkylene oxide and end amine are added dropwise under stirring condition
Molar ratio is 0.2-0.7:1, reacts 1-4 hours after completion of dropwise addition, then terminates reaction.
8. being copolymerized associated matter according to claim 7, it is characterised in that: the end amine is ethylenediamine, propane diamine, fourth two
One of amine, hexamethylene diamine, diethylenetriamine, triethylene tetramine, tetraethylenepentamine are a variety of.
9. being copolymerized associated matter according to claim 7, it is characterised in that: the cyclic ethers is ethylene oxide, propylene oxide, four
One of hydrogen furans is a variety of.
10. being copolymerized associated matter according to claim 7, it is characterised in that: the haloalkylene oxide is epoxychloropropane, ring
One of oxygen N-Propyl Bromide, epoxy chlorobutane are a variety of.
11. copolymerization associated matter described in accordance with the claim 1, it is characterised in that: the starch be green starch, tapioca,
One or more of starch from sweet potato, potato starch, wheat starch, water caltrop starch, Rhizoma Nelumbinis starch, cornstarch.
12. being copolymerized associated matter according to claim 11, it is characterised in that: the starch is that cornstarch or potato are formed sediment
Powder.
13. the preparation method as described in any claim in claim 1-12 for drilling fluid tackifier copolymerization associated matter,
The preparation method comprises the following steps:
(1) inorganic salts are mixed with water, prepares the inorganic salt solution of 2wt%~30wt%；
(2) cationic polyamine and water are hybridly prepared into cationic polyamine aqueous solution, the quality of the cationic polyamine aqueous solution
Concentration is 0.5%~3%；
(3) it weighs starch and is mixed with the inorganic salt solution that part steps (1) are prepared, 20~50min is stirred at 60~80 DEG C,
Gelatinized starch is obtained after processing；
(4) N is passed through in the gelatinized starch obtained to step (3)2, initiator is added after reacting 15~60min；
(5) the remainder substep in N- methyl diallyl propane sulfonic acid salt and N, N- dimethacrylamide and step (1) is weighed
Suddenly the inorganic salt solution mixing that (1) is prepared, is added in the gelatinized starch that step (4) obtains, until completely dissolved 50~70
1~2h is reacted at DEG C；Wherein, N- methyl diallyl propane sulfonic acid salt, N,N-DMAA and starch monomer gross mass
Concentration is 5%~20%, and according to N,N-DMAA, N- methyl diallyl propane sulfonic acid salt, starch and cation
On the basis of the total amount of polyamine, the dosage of N,N-DMAA is 6-45 weight %, N- methyl diallyl propane sulfonic acid salt
Dosage is 5-35 weight %, and starch dosage is 5-35 weight %；
(6) the cationic polyamine aqueous solution that step (2) are prepared is added in the reaction product that step (5) obtains, is uniformly mixed
60~80 DEG C are warming up to simultaneously, the reaction was continued 3~5h；Wherein, according to N,N-DMAA, N- methyl diallyl third
On the basis of the total amount of sulfonate, starch and cationic polyamine, cationic polyamine dosage is 2-30 weight %；
(7) reaction product that step (6) obtains is washed with acetone soln, the solid sediment obtained after washing passes through drying simultaneously
Purpose product is obtained after crushing.
14. according to the method for claim 13, it is characterised in that: according to N,N-DMAA, N- methyl diene
On the basis of the total amount of propyl propane sulfonic acid salt, starch and cationic polyamine, the dosage of N,N-DMAA is 10-40 weight
Measure %；The dosage of N- methyl diallyl propane sulfonic acid salt is 10-32 weight %；Starch dosage is 10-32 weight %.
15. according to the method for claim 13, it is characterised in that: according to N,N-DMAA, N- methyl diene
On the basis of the total amount of propyl propane sulfonic acid salt, starch and cationic polyamine, cationic polyamine dosage is 5-28 weight %.
16. according to the method for claim 13, it is characterised in that: the inorganic salts are ammonium salt, calcium salt, magnesium salts, mantoquita, zinc
One of salt, aluminium salt, zirconates are a variety of.
17. according to method described in claim 13 or 16, it is characterised in that: the inorganic salts use in the form of a solution, and institute
State inorganic salts be ammonium salt when, the inorganic salt solution concentration be 10wt%~30wt%；The inorganic salts be calcium salt, magnesium salts, mantoquita,
When zinc salt, the inorganic salt solution concentration is 5wt%~15wt%, when the inorganic salts are aluminium salt, the inorganic salt solution concentration
For 2wt%~10wt%；When the inorganic salts are zirconates, the inorganic salt solution concentration is 2wt%~5wt%.
18. according to the method for claim 17, it is characterised in that: when the inorganic salts are calcium salt, magnesium salts, mantoquita, zinc salt,
The inorganic salt solution concentration is 10%~15%.
19. according to the method for claim 13, it is characterised in that: the initiator is sodium peroxydisulfate, potassium peroxydisulfate, over cure
One of sour ammonium is a variety of, and the dosage of the initiator is the 0.3-0.7wt% of monomer total amount.
20. according to the method for claim 13, it is characterised in that: the cationic polyamine has to be tied shown in following formula (i)
Structure:
Formula (i)
Wherein, X-For inorganic anion；R,R9、R9`、R10、R10` is respectively structure shown in following formula (IV)sFormula (IV), wherein R11For H, substituted or unsubstituted C1-C5 alkane
Base, t are the integer of 1-5, and z is the integer of 0-5；
N, p is the integer of 1-5；X is the integer of 0-10, and y is the integer of 1-10；L, the value of l` and l`` makes the cation
The kinematic viscosity of polyamine is 100-500mm2/ s, cationic degree 0.5-2mmol/g.
21. according to the method for claim 20, it is characterised in that: the cationic polyamine held as shown in formula (V) amine with
Haloalkylene oxide shown in cyclic ethers and formula (VII) shown in formula (VI) is obtained by condensation reaction
。
22. according to the method for claim 21, it is characterised in that: the cationic polyamine is made by following methods:
It is added dropwise cyclic ethers at stirring condition and 50-120 DEG C into end amine, the molar ratio of cyclic ethers and end amine is 2-4:1, is reacted after completion of dropwise addition
1-4 hours, 80-150 DEG C is then heated to, haloalkylene oxide, the molar ratio of haloalkylene oxide and end amine are added dropwise under stirring condition
For 0.2-0.7:1, is reacted after completion of dropwise addition 1-4 hours, then terminate reaction.
23. according to the method for claim 22, it is characterised in that: the end amine be ethylenediamine, propane diamine, butanediamine, oneself
One of diamines, diethylenetriamine, triethylene tetramine, tetraethylenepentamine are a variety of.
24. according to the method for claim 22, it is characterised in that: the cyclic ethers is ethylene oxide, propylene oxide, tetrahydro furan
It one of mutters or a variety of.
25. according to the method for claim 22, it is characterised in that: the haloalkylene oxide is epoxychloropropane, epoxy bromine
One of propane, epoxy chlorobutane are a variety of.
26. according to the method for claim 13, it is characterised in that: the starch is green starch, tapioca, sweet potato
One or more of starch, potato starch, wheat starch, water caltrop starch, Rhizoma Nelumbinis starch, cornstarch.
27. according to the method for claim 26, it is characterised in that: the starch is cornstarch or potato starch.
28. according to the method for claim 13, it is characterised in that: inorganic salt solution used in step (5) is step (3)
The 1/2~3/5 of middle inorganic salt solution total amount.
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