CN104292129B - A kind of dendroid monomer, using inorganic agent of the monomer and preparation method thereof - Google Patents

A kind of dendroid monomer, using inorganic agent of the monomer and preparation method thereof Download PDF

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CN104292129B
CN104292129B CN201410268089.XA CN201410268089A CN104292129B CN 104292129 B CN104292129 B CN 104292129B CN 201410268089 A CN201410268089 A CN 201410268089A CN 104292129 B CN104292129 B CN 104292129B
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monomer
dendroid
formula
preparation
drilling fluid
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CN104292129A (en
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王中华
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China Petrochemical Corp
Drilling Engineering Technology Research Institute of Sinopec Zhongyuan Petroleum Engineering Co Ltd
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China Petrochemical Corp
Drilling Engineering Technology Research Institute of Sinopec Zhongyuan Petroleum Engineering Co Ltd
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Abstract

The present invention relates to a kind of dendroid monomer, using inorganic agent of the monomer and preparation method thereof, belong to the synthetically prepared technical field of water-soluble high-molecular material.For the present invention by dendroid monomer, sulfonic acid monomer, amide monomer, the amount ratio according to material is (0.05~0.25)：(0.10~0.35)：The ratio of (0.35~0.75), under conditions of pH value is 6.0~9.0, under water-soluble azo initiator or/and addition redox initiation system effect, obtained by aqueous solution polymerization, drying.The present invention both has stronger heat and salinity tolerance ability, the polymer drop inorganic agent in calcium chloride drilling liquor is can act as again, product good water solubility, there is preferably thickening and filtrate reducing characteristic more than 180 DEG C, under the conditions of saturated brine and high calcium, high-temperature stability is good, has good Efficient Adhesive Promotion in calcium chloride solution.

Description

A kind of dendroid monomer, using inorganic agent of the monomer and preparation method thereof
Technical field
The present invention relates to a kind of dendroid monomer, using inorganic agent of the monomer and preparation method thereof, belong to water-soluble high The synthetically prepared technical field of molecular material, more precisely, being a kind of high temperature resistance anticalcium polymer drilling well containing dendritic branch Liquid inorganic agent and preparation method thereof.
Background technology
Develop for oil-gas exploration and development to deep, drilling strata becomes increasingly complex, and it is more next to be drilled the difficulty that well is faced Bigger practical problem, domestic and foreign scholars surround the needs of superhigh temperature water base drilling fluid, carry out in terms of the inorganic agent of oil field A series of activities.The modification of acrylamido copolymer is focused on, new monomer is introduced and is copolymerized with acrylamide, prepared various Fluid loss additive.But because synthesis monomer and method do not change, inorganic agent performance has no obvious progress, at present with or research The inorganic agent of exploitation is still straight chain linear polymer, due to the limitation of molecule heat endurance and shear stability, inorganic agent temperature resistance What property of drilling fluid was safeguarded under limited ability, with ultra-high temperature condition needs gap also be present.Want to improve deep-well, ultra-deep well drilling It the heat and salinity tolerance performance of liquid, must just increase its dosage, but as dosage improves and adds the viscosity of drilling fluid, particularly exist In the case of content of calcium and magnesium height, mud property control is more difficult, and existing additive for drilling fluid can not fully meet brill The needs of well.And the polymer of the structure containing dendritic branch is compared with traditional flexible-chain polymer, because the steric hindrance of side chain is imitated Should and side chain on group influence each other, the heat endurance of macromolecular structure can significantly improve, the group enriched on molecule side chain It ensure that inorganic agent has good absorption and hydrating capacity, so as to improve the temperature resistance of inorganic agent and anti-shear ability,《Middle external enwergy Source》2013,18(1):Disclosed in 36-46《High performance drilling inorganic agent mentality of designing》It is following high performance drilling inorganic agent Developing direction.Therefore, dendroid monomer and acrylamide, 2- acrylamido -2- methyl-prop sulphur of the present invention using synthesis The monomers such as acid are raw material, prepare the copolymer containing dendritic branch, the copolymer as high temperature resistant drilling fluids inorganic agent, have compared with Strong filtrate reducing effect and preferable heat and salinity tolerance ability.
The content of the invention
It is an object of the invention to overcome existing water-base drilling fluid inorganic agent due to molecule heat endurance and shear stability Limitation, cause water-base drilling fluid inorganic agent heat and salinity tolerance limited ability and a kind of dendroid monomer and a kind of drilling fluid be provided and used Polymer treatment agent and the preparation method of the two containing dendritic branch, it can meet that shaft bottom high temperature and/or high salt (sodium chloride) are high The needs of safety drilling construction under calcium environment, can control rheological characteristic under water-base drilling fluid high-temperature and high-pressure conditions, suspending stabilized Property and filter loss.
A kind of dendroid monomer, it is characterised in that：Shown in its general structure such as formula (I)：
In formula, R1Expression carbon number is H, and methyl, q is 2~8 integer, and p is 4~8 integer.
A kind of polymer drilling fluid finishing agent of drilling fluid containing dendritic branch, its general structure such as formula (II)：
In formula, R1Expression carbon number is H, methyl, R2-R5It is identical or different, it is each independently H, carbon number 1- 4 alkyl or phenyl, the integer that X is NH or O, q are 2~8, p are 4~8 integer, and n is 1~4 integer；M is K or Na；a： b：C=(0.5~2.5)：(1~3.5)：(3.5~7.5).
The drilling fluid of the present invention preparation method of the polymer treatment agent containing dendritic branch, comprises the following steps:
(1) water, sodium hydroxide or potassium hydroxide are added into reactor, after its dissolving, adds dendroid monomer (I), sulphur Acid monomers (III), after stirring, with the sodium hydroxide of mass fraction 10%~20% or potassium hydroxide solution by the pH of system Then value regulation adds amide monomer (IV), stirring makes its dissolving, wherein dendroid monomer (I), sulfonic acid or carboxylic to 6.0~9.0 Acid monomers (III) and amide monomer (IV) anabolic reaction monomer mixture A, the matter of control reaction monomers mixture A in aqueous Fraction is measured 20%~50%, wherein, dendroid monomer (I)：Sulfonic acid or carboxylic acid monomer (III)：The material of amide monomer (IV) Measure ratio=(0.05~0.25)：(0.10~0.35)：(0.35~0.75).
(2) add water-soluble azo initiator to the aqueous solution obtained by step (1) under agitation or/and add redox Initiation system, wherein, water-soluble azo initiator accounts for the 0.05%~0.5% of reaction monomers mixture A gross masses；Redox Oxidant, the reducing agent of initiation system respectively account for the 0.10%~0.75% of reaction monomers mixture A gross masses；
(3) initial temperature of the polymerisation of the aqueous solution obtained by regulating step (2) is 30~60 DEG C, maintains polymerisation 15~60 minutes, obtain sticky or gum-like product；
(4) the sticky or gum-like product for obtaining step (3) at 140~160 DEG C drying, amidatioon, crush and produce brill Polymer treatment agent of the well liquid containing dendritic branch.
Described dendroid monomer (I)：Sulfonic acid or carboxylic acid monomer (III)：Amide monomer (IV), structural formula difference are as follows：
In formula (I)~(IV), R1Expression carbon number is H, methyl, R2-R5It is identical or different, it is each independently H, carbon Atomicity is 1-4 alkyl or phenyl, and the integer that X is NH or O, q are 2~8, p is 4~8 integer, and n is 1~4 integer.
X is NH, R in described formula (III)1And R2For CH3, n 1；Or X NH, R2And R3For H, n 1；Or X is O, R2And R3For CH3, n 1；Or X O, R2And R3For H, n 3.
In described formula (IV), R4And R5For H；Or R4And R5For CH3；Or R4And R5For CH2CH3；Or R4For H, R5For CH (CH3)CH3, or, R4For H, R5For C (CH3)2CH3。
In preparation method of the drilling fluid of the present invention with the polymer treatment agent containing dendritic branch, step (1) water is used Measure as water：Monomer gross mass=(8~5)：(2~5) (mass ratio), that is, control monomer mass fraction 20%~50%.
In preparation method of the drilling fluid of the present invention with the polymer treatment agent containing dendritic branch, step (1) described hydrogen-oxygen It is (3 × dendroid monomer molar number+sulfonic acid monomer molal quantity) to change sodium (or potassium hydroxide) dosage.
Described sulfonic acid monomer is 2- acrylamide-2-methylpro panesulfonic acids, 2- acrylamidos ethyl sulfonic acid or 2- propylene Amide oxygen -2- methyl propane sulfonic acids.
Described amide monomer is acrylamide, N,N-DMAA, N, N- acrylamides, isopropyl Acrylamide or isobutyl group acrylamide monomer.
Described initiator is the isobutyl imidazoline hydrochloride of azo two, azo diisobutyl amidine hydrochloride, azo dicyano Valeric acid or azo dicyclohexyl formonitrile HCN, water-soluble azo initiator are the 0.05%~0.5% of monomer gross mass,；Oxidation-also The oxidant of former initiation system is potassium peroxydisulfate or ammonium persulfate, and reducing agent is sodium hydrogensulfite, sodium pyrosulfite, sodium sulfite Or one kind in sodium thiosulfate, oxidant are respectively to account for the 0.10%~0.75% of monomer gross mass with reducing agent.
The dendroid monomer of described formula (I), reacted by the intermediate and acryloyl chloride of formula (V) structure polyamide：
Wherein, in formula (V), q is 2~8 integer, and p is 4~8 integer.
The formula is the dendroid monomer of formula (I), is prepared using process for acylating, its process is as follows：
The intermediate of formula (V) structure polyamide, organic solvent and the agent of beam acid are added into the reaction bulb equipped with cooling device In, 5 DEG C are cooled to, is then slowly added into acryloyl chloride, wherein, the intermediate of formula (V) structure polyamide：Organic solvent：Beam acid Agent：The mol ratio of acryloyl chloride is 6：18~22：1.0~1.1：1.0~1.05.Temperature is no more than 15 DEG C, third in adition process After alkene acyl chlorides adds, 1~7h is reacted at 10 DEG C.Reactant is stood, separates organic phase, with saturated salt sodium bicarbonate solution With wash for several times, with anhydrous sodium sulfate drying, steam organic solvent and produce crude product, crude product is further purified, produce polymerization The dendroid monomer (I) of level.
Described organic solvent is dimethyl acetamide, dichloromethane, chloroform or dichloroethanes.
Described beam acid agent is triethylamine, three n-propyl amine or tri-n-butyl amine.
The intermediate of formula (V) the structure polyamide directly uses commodity, can also use reaction well known in the art, By methyl acrylate, the Michael addition reaction product of monoethanolamine and ethylenediamine, methyl acrylate by Michael's addition, acylation Reaction is obtained, and it is concretely comprised the following steps：
(1) methyl acrylate, monoethanolamine and methanol are added in a kettle, first in 10~25 DEG C and logical protective gas situation 30~40 DEG C of 3~7h of holding are warming up to after 10~60min of lower stirring, is then evaporated under reduced pressure to remove methanol, obtains such as formula (V a) The product of shown structure.
(2) product of structure shown in formula (V a) and methanol are added in reactor, under 10~40 DEG C of stirring conditions, drop Add ethylenediamine, then react 20~35h at this temperature, be then evaporated under reduced pressure to remove methanol, that is, obtain formula (V b) structure institute The intermediate product shown.
(3) intermediate product of structure shown in formula (V b) and methanol are added in reactor, under 10~40 DEG C of stirring conditions, Methyl acrylate is added dropwise, reacts 20~35h, is evaporated under reduced pressure and removes methanol, obtains the intermediate product of the structure as shown in formula (V c).
(4) intermediate product of modus ponens (V c) structure and methanol are added in reactor, under 10~40 DEG C of stirring conditions, are added dropwise Diamine, 20~35h is reacted, is evaporated under reduced pressure the intermediate product to remove methanol, obtained as shown in formula (V d) structure.
(5) intermediate product of modus ponens (V d) structure is 1 according to mol ratio with binary acid：1~1.05 ratio, 110~ 2~6h is reacted at 160 DEG C, is obtained such as the dendroid intermediate of formula (V) structure.
The beneficial effects of the invention are as follows：It is copolymerized, is obtained using the monomer and sulfonic acid monomer, amide monomer of dendritic structure Polymer treatment agent containing dendritic branch, because the monomer of dendritic structure has the bases such as abundant imido grpup, carbonyl, carboxyl Group, and molecule chain rigidity is strong, both has stronger heat and salinity tolerance ability, can act as the polymer drop in calcium chloride drilling liquor again Fluid loss agents, product good water solubility, prepared using aqueous solution rapid polymerization method, course of reaction is easily controlled, is simple to operate, product Steady quality, production and drying course power consumption are low, environmentally safe, in high temperature (more than 180 DEG C) high salt (saturated brine) and There is preferably thickening, suppression and filtrate reducing characteristic, high-temperature stability is good, has in calcium chloride solution good under the conditions of high calcium Efficient Adhesive Promotion.
Embodiment
The present invention and its effect are described further with reference to specific embodiment.
Embodiment 1
The preparation example 1 of dendroid monomer：
(1) methyl acrylate, monoethanolamine and methanol are added in a kettle, first in 25 DEG C and logical N2In the case of stir 40 DEG C of holding 3h are warming up to after 10min, are then evaporated under reduced pressure the product for remove methanol, obtaining the structure as shown in formula (V a).
(2) product of structure shown in formula (V a) and methanol are added in reactor, under 10 DEG C of stirring conditions, second is added dropwise Diamines, then reacts 35h at this temperature, is then evaporated under reduced pressure the centre to remove methanol, that is, obtained shown in formula (V b) structure Product.
(3) intermediate product of structure shown in formula (V b) and methanol are added in reactor, under 40 DEG C of stirring conditions, are added dropwise Methyl acrylate, 35h is reacted, be evaporated under reduced pressure and remove methanol, obtain the intermediate product of the structure as shown in formula (V c).
(4) intermediate product of modus ponens (V c) structure and methanol are added in reactor, and under 40 DEG C of stirring conditions, fourth two is added dropwise Amine, 20h is reacted, is evaporated under reduced pressure the intermediate product to remove methanol, obtained as shown in formula (V d) structure.
(5) intermediate product of modus ponens (V d) structure is 1 according to mol ratio with adipic acid：1.05 ratio, at 160 DEG C 2h is reacted, is obtained such as the branch intermediate of formula (V) structure.
(6) dendroid intermediate：Dimethyl acetamide：Triethylamine：Acryloyl chloride is 6：18：1.0：1.0 (mol ratios), will Formula (V) structure dendroid intermediate, dimethyl acetamide and triethylamine are added in the reaction bulb equipped with cooling device, are cooled to 5 DEG C, acryloyl chloride is then slowly added into, temperature is no more than 15 DEG C in adition process, after acryloyl chloride adds, is reacted at 10 DEG C 1h.Reactant is stood, separates organic phase, is neutralized and is washed for several times with saturated salt sodium bicarbonate solution, with anhydrous sodium sulfate drying, steamed Go out dimethyl acetamide and produce crude product, crude product is further purified, produce the dendroid monomer of polymer grade.
Water (its dosage is so that monomer mass fraction is counted 20%), 0.55 mole of sodium hydroxide are added into reactor, treated After it dissolves, 0.05 mole of preparation example 1 is obtained into monomer containing dendritic branch and 0.35 mole of 2- acrylamido -2- methyl-prop Sulfonic acid adds reactor, after stirring, with the potassium hydroxide solution of mass fraction 20% by the pH value regulation of system to 9.0, Then add and 0.35 mole percent acrylamide, stirring make its dissolving obtain reaction mixture.Add under agitation and account for total weight of monomer The ammonium persulfate of amount 0.15%, the sodium hydrogensulfite of total monomer weight 0.15% is accounted for, the initial temperature of polymerisation is 60 DEG C, is maintained Polymerization reaction time is 120 minutes, finally obtains gum-like product.Obtained gum-like product is dried at 140 DEG C, crushes and produces Polymer treatment agent of the drilling fluid containing dendritic branch.
Embodiment 2
Dendroid monomer preparation example 2：
(1) methyl acrylate, monoethanolamine and methanol are added in a kettle, first in 25 DEG C and logical N2In the case of stir 30 DEG C of holding 7h are warming up to after 60min, are then evaporated under reduced pressure the product for remove methanol, obtaining the structure as shown in formula (V a).
(2) product of structure shown in formula (V a) and methanol are added in reactor, under 10 DEG C of stirring conditions, second is added dropwise Diamines, then reacts 20h at this temperature, is then evaporated under reduced pressure the centre to remove methanol, that is, obtained shown in formula (V b) structure Product.
(3) intermediate product of structure shown in formula (V b) and methanol are added in reactor, under 10 DEG C of stirring conditions, are added dropwise Methyl acrylate, 20h is reacted, be evaporated under reduced pressure and remove methanol, obtain the intermediate product of the structure as shown in formula (V c).
(4) intermediate product of modus ponens (V c) structure and methanol are added in reactor, and under 10 DEG C of stirring conditions, second two is added dropwise Amine, 20h is reacted, is evaporated under reduced pressure the intermediate product to remove methanol, obtained as shown in formula (V d) structure.
(5) intermediate product of modus ponens (V d) structure is 1 according to mol ratio with suberic acid：1 ratio, reacted at 110 DEG C 6h, obtain such as the branch intermediate of formula (V) structure.
(6) dendroid intermediate：Dichloromethane：Triethylamine：Acryloyl chloride is 6：22：1.1：1.05 (mol ratios), by formula (V) structure dendroid intermediate, dichloromethane and triethylamine are added in the reaction bulb equipped with cooling device, are cooled to 5 DEG C, so After be slowly added into acryloyl chloride, temperature is no more than 10 DEG C in adition process, after acryloyl chloride adds, reacts 7h at 10 DEG C.Will Reactant is stood, and separates organic phase, is neutralized and is washed for several times with saturated salt sodium bicarbonate solution, with anhydrous sodium sulfate drying, steams two Chloromethanes produces crude product, and crude product is further purified, and produces the dendroid monomer of polymer grade.
Water (its dosage is so that monomer mass fraction is counted 50%), 1.1 moles of sodium hydroxide are added into reactor, treat it After dissolving, 0.25 mole of preparation example 2 is obtained into monomer containing dendritic branch and 0.10 mole of 2- acrylamido -2- methyl-prop sulphur Acid adds reactor, after stirring, with the sodium hydroxide solution of mass fraction 15% by the pH value regulation of system to 7.0, so Add afterwards and 0.75 mole percent acrylamide, stirring make its dissolving obtain reaction mixture.Add under agitation and account for total monomer weight 1.0% ammonium persulfate, the sodium hydrogensulfite of total monomer weight 1.0% is accounted for, the initial temperature of polymerisation is 30 DEG C, maintains polymerization Reaction time is 45 minutes, finally obtains viscous product.Obtained viscous product is dried at 160 DEG C, crushes and produces drilling well Polymer treatment agent of the liquid containing dendritic branch.
Embodiment 3
Dendroid monomer preparation example 3：
(1) methyl acrylate, monoethanolamine and methanol are added in a kettle, first in 20 DEG C and logical N2In the case of stir 35 DEG C of holding 5h are warming up to after 50min, are then evaporated under reduced pressure the product for remove methanol, obtaining the structure as shown in formula (V a).
(2) product of structure shown in formula (V a) and methanol are added in reactor, under 25 DEG C of stirring conditions, second is added dropwise Diamines, then reacts 30h at this temperature, is then evaporated under reduced pressure the centre to remove methanol, that is, obtained shown in formula (V b) structure Product.
(3) intermediate product of structure shown in formula (V b) and methanol are added in reactor, under 35 DEG C of stirring conditions, are added dropwise Methyl acrylate, 30h is reacted, be evaporated under reduced pressure and remove methanol, obtain the intermediate product of the structure as shown in formula (V c).
(4) intermediate product of modus ponens (V c) structure and methanol are added in reactor, under 35 DEG C of stirring conditions, are added dropwise pungent two Amine, 30h is reacted, is evaporated under reduced pressure the intermediate product to remove methanol, obtained as shown in formula (V d) structure.
(5) intermediate product of modus ponens (V d) structure is 1 according to mol ratio with succinic acid：1.02 ratio, at 140 DEG C 4h is reacted, is obtained such as the dendroid intermediate of formula (V) structure.
(6) dendroid intermediate：Chloroform：Tri-n-butyl amine：Acryloyl chloride is 6：20：1.05：1.0~1.025 (rub That ratio), formula (V) structure dendroid intermediate, chloroform and tri-n-butyl amine are added into the reaction bulb equipped with cooling device In, 5 DEG C are cooled to, is then slowly added into acryloyl chloride, temperature is no more than 12 DEG C, after acryloyl chloride adds in adition process, in 6h is reacted at 10 DEG C.Reactant is stood, separates organic phase, is neutralized and is washed for several times with saturated salt sodium bicarbonate solution, with anhydrous sulphur Sour sodium is dried, and is steamed chloroform and is produced crude product, crude product is further purified, produces the dendroid monomer of polymer grade.
Water (its dosage is so that monomer mass fraction is counted 40%), 0.80 mole of potassium hydroxide are added into reactor, treated After it dissolves, 0.15 mole of preparation example 3 is obtained into monomer containing dendritic branch and 0.20 mole of 2- acrylamido -2- methyl-prop Sulfonic acid adds reactor, after stirring, with the sodium hydroxide solution of mass fraction 10% by the pH value regulation of system to 8.0, Then add and 0.60 mole of N-isopropylacrylamide, stirring make its dissolving obtain reaction mixture.Add under agitation and account for list The potassium peroxydisulfate of body gross weight 0.45%, the sodium pyrosulfite of total monomer weight 0.45% is accounted for, the initial temperature of polymerisation is 40 DEG C, it is 90 minutes to maintain polymerization reaction time, finally obtains gum-like product.Obtained gum-like product is dried at 160 DEG C, powder It is broken to produce the polymer drilling fluid finishing agent containing dendritic branch.
Embodiment 4
Dendroid monomer preparation example 4：
(1) methyl acrylate, monoethanolamine and methanol are added in a kettle, first in 15 DEG C and logical N2In the case of stir 32 DEG C of holding 4h are warming up to after 40min, are then evaporated under reduced pressure the product for remove methanol, obtaining the structure as shown in formula (V a).
(2) product of structure shown in formula (V a) and methanol are added in reactor, under 30 DEG C of stirring conditions, second is added dropwise Diamines, then reacts 25h at this temperature, is then evaporated under reduced pressure the centre to remove methanol, that is, obtained shown in formula (V b) structure Product.
(3) intermediate product of structure shown in formula (V b) and methanol are added in reactor, under 250 DEG C of stirring conditions, are added dropwise Methyl acrylate, 30h is reacted, be evaporated under reduced pressure and remove methanol, obtain the intermediate product of the structure as shown in formula (V c).
(4) intermediate product of modus ponens (V c) structure and methanol are added in reactor, under 25 DEG C of stirring conditions, oneself are added dropwise two Amine, 30h is reacted, is evaporated under reduced pressure the intermediate product to remove methanol, obtained as shown in formula (V d) structure.
(5) intermediate product of modus ponens (V d) structure is 1 according to mol ratio with glutaric acid：1.01 ratio, at 130 DEG C 3h is reacted, is obtained such as the dendroid intermediate of formula (V) structure.
(6) dendroid intermediate：Dichloroethanes：Three n-propyl amine：Methacrylic chloride is 6：22：1.1：1.0 (mole Than), formula (V) structure dendroid intermediate, dichloroethanes and three n-propyl amine are added in the reaction bulb equipped with cooling device, 5 DEG C are cooled to, is then slowly added into methacrylic chloride, temperature is no more than 15 DEG C, after acryloyl chloride adds in adition process, in 4h is reacted at 10 DEG C.Reactant is stood, separates organic phase, is neutralized and is washed for several times with saturated salt sodium bicarbonate solution, with anhydrous sulphur Sour sodium is dried, and is steamed dichloroethanes and is produced crude product, crude product is further purified, produces the dendroid monomer of polymer grade.
Water (its dosage is so that monomer mass fraction is counted 40%), 0.85 mole of sodium hydroxide are added into reactor, treated After it dissolves, the monomer containing dendritic branch that 0.15 mole of preparation example 4 is obtained and 0.25 mole of 2- acrylamido -2- methyl Propane sulfonic acid adds reactor, after stirring, with the sodium hydroxide solution of mass fraction 20% by systempH value regulations are arrived 8.0,0.75 mole percent acrylamide is then added, stirring makes its dissolving obtain reaction mixture.It is total to account for monomer for addition under agitation The ammonium persulfate of weight 0.45%, the sodium hydrogensulfite of total monomer weight 0.45% is accounted for, the initial temperature of polymerisation is 40 DEG C, dimension Polymerization reaction time is held as 90 minutes, finally obtains gum-like product.Obtained gum-like product is dried at 160 DEG C, crushing is The polymer drilling fluid finishing agent of dendritic branch must be contained.
Embodiment 5-10 is according to the synthesis condition and formula of embodiment 4, and only replacement partial reaction thing, as shown in table 1 below：
The embodiment 5-10 partial reaction thing lists of table 1
Comparative example 1：
According to the synthesis condition and formula of embodiment 4, simply remove dendroid monomer, synthesize bipolymer.
The product that different embodiments obtain filtrate reducing effect and 1% Aqueous Solution Viscosity in compound salt-water drilling fluid are shown in Table 2.
The preparation of compound salt-water basic slurry：The addition 15.75g sodium chloride in 350ml distilled water, 1.75g anhydrous calcium chlorides, 4.6g magnesium chlorides, 52.5g calcium bentonites and 3.15g natrium carbonicum calcinatums, high-speed stirred 20min, room temperature place aging 24h.
1.5% sample is added during evaluation, high-speed stirred 5 minutes, then aging 16h is rolled at 180 DEG C, is cooled to room Temperature, determine the filter loss of drilling fluid.API filtration after 180 DEG C of rolling aging 16h of base slurry is 228 milliliters.It is water-soluble to prepare 1% Liquid, the apparent viscosity AV at 25 DEG C is determined, while 5% calcium chloride is added in 1% aqueous solutions of polymers, stirred, survey Determine Calcium treatment rear solution apparent viscosity AV1, and calculate viscosity conservation rate：
Viscosity conservation rate=plus calcium chloride aqueous solutions of polymers viscosity/aqueous solutions of polymers viscosity × 100%
The embodiment of table 2 and comparative example Contrast on effect
As can be seen from Table 2, the viscosity conservation rate average out to 31.15% of the embodiment of the present invention, much larger than comparative example Viscosity conservation rate 21.52%, application effect is substantially better than comparative example, so as to find out the present invention both there is stronger heat and salinity tolerance Ability, the polymer drop inorganic agent in calcium chloride drilling liquor, product good water solubility, more than 180 DEG C, saturated salt are can act as again There is preferably thickening and filtrate reducing characteristic, high-temperature stability is good, has in calcium chloride solution good under the conditions of water and high calcium Efficient Adhesive Promotion.

Claims (13)

  1. A kind of 1. dendroid monomer, it is characterised in that：Shown in its general structure such as formula (I)：
    In formula, R1H or methyl are represented, q is 2~8 integer, and p is 4~8 integer.
  2. A kind of 2. polymer drilling fluid finishing agent of drilling fluid containing dendritic branch, it is characterised in that：Its general structure such as formula (Ⅱ)：
    In formula, R1Represent H or methyl, R2-R5It is identical or different, it is each independently H, the alkyl or benzene that carbon number is 1-4 Base, the integer that X is NH or O, q are 2~8, p are 4~8 integer, and n is 1~4 integer；M is K or Na；a：b：C=(0.5~ 2.5)：(1~3.5)：(3.5~7.5).
  3. 3. a kind of preparation method of polymer treatment agent of the drilling fluid containing dendritic branch as claimed in claim 2, it is special Sign is：Comprise the following steps：
    (1) water, sodium hydroxide or potassium hydroxide are added into reactor, after its dissolving, adds dendroid monomer (I), sulfonic acid list Body (III), after stirring, the pH value of system is adjusted with the sodium hydroxide or potassium hydroxide solution of mass fraction 10%~20% Save to 6.0~9.0, then add amide monomer (IV), stirring makes its dissolving, wherein dendroid monomer (I), sulfonic acid or carboxylic acid list Body (III) and amide monomer (IV) anabolic reaction monomer mixture A, the quality point of control reaction monomers mixture A in aqueous Count 20%~50%, wherein, dendroid monomer (I)：Sulfonic acid or carboxylic acid monomer (III)：The amount ratio of the material of amide monomer (IV) =(0.05~0.25)：(0.10~0.35)：(0.35~0.75)；
    (2) add water-soluble azo initiator to the aqueous solution obtained by step (1) under agitation or/and add Redox Initiator System, wherein, water-soluble azo initiator accounts for the 0.05%~0.5% of reaction monomers mixture A gross masses；Redox Initiator Oxidant, the reducing agent of system respectively account for the 0.10%~0.75% of reaction monomers mixture A gross masses；
    (3) initial temperature of the polymerisation of the aqueous solution obtained by regulating step (2) is 30~60 DEG C, maintenance polymerisation 15~ 60 minutes, obtain sticky or gum-like product；
    (4) the sticky or gum-like product for obtaining step (3) at 140~160 DEG C drying, amidatioon, crush and produce drilling fluid With the polymer treatment agent containing dendritic branch；
    Described dendroid monomer (I), sulfonic acid or carboxylic acid monomer (III), the structural formula difference of amide monomer (IV) are as follows：
    In formula (I), (III), (IV), R1Represent H or methyl, R2-R5It is identical or different, it is each independently H, carbon number 1- 4 alkyl or phenyl, the integer that X is NH or O, q are 2~8, p are 4~8 integer, and n is 1~4 integer.
  4. 4. the drilling fluid according to claim 3 preparation method of the polymer treatment agent containing dendritic branch, its feature It is：X is NH, R in described formula (III)2And R3For CH3, n 1；Or X NH, R2And R3For H, n 1；Or X O, R2And R3For CH3, n 1；Or X O, R2And R3For H, n 3.
  5. 5. the drilling fluid according to claim 3 preparation method of the polymer treatment agent containing dendritic branch, its feature It is：In described formula (IV), R4And R5For H；Or R4And R5For CH3；Or R4And R5For CH2CH3；Or R4For H, R5 For CH (CH3)CH3；Or R4For H, R5For C (CH3)2CH3。
  6. 6. the drilling fluid according to claim 3 preparation method of the polymer treatment agent containing dendritic branch, its feature It is：Described sulfonic acid monomer is 2- acrylamide-2-methylpro panesulfonic acids, 2- acrylamidos ethyl sulfonic acid or 2- acrylamides Oxygen -2- methyl propane sulfonic acids.
  7. 7. the drilling fluid according to claim 3 preparation method of the polymer treatment agent containing dendritic branch, its feature It is：Described amide monomer is acrylamide, N,N-DMAA, N, N- acrylamides, isopropyl third Acrylamide or isobutyl group acrylamide monomer.
  8. 8. the drilling fluid according to claim 3 preparation method of the polymer treatment agent containing dendritic branch, its feature It is：Described water-soluble azo initiator is the isobutyl imidazoline hydrochloride of azo two, azo diisobutyl amidine hydrochloride, azo Dicyano valeric acid or azo dicyclohexyl formonitrile HCN, water-soluble azo initiator are reaction monomers mixture A gross masses 0.05%~0.5%.
  9. 9. the drilling fluid according to claim 3 preparation method of the polymer treatment agent containing dendritic branch, its feature It is：Oxidant is potassium peroxydisulfate or ammonium persulfate in described redox initiation system, and reducing agent is sodium hydrogensulfite, Jiao One kind in sodium sulfite, sodium sulfite or sodium thiosulfate, oxidant are respectively to account for the total matter of reaction monomers mixture A with reducing agent The 0.10%~0.75% of amount.
  10. 10. the drilling fluid according to claim 3 preparation method of the polymer treatment agent containing dendritic branch, its feature It is：The dosage of the sodium hydroxide or potassium hydroxide is (3 × dendroid monomer molar number+sulfonic acid monomer molal quantity).
  11. A kind of 11. preparation method of dendroid monomer as claimed in claim 1, it is characterised in that：Described dendroid monomer, React to obtain with acryloyl chloride by the intermediate of formula (V) structure polyamide, it is as follows using process for acylating preparation process：
    (1) intermediate of formula (V) structure polyamide, organic solvent and the agent of beam acid are added in the reaction bulb equipped with cooling device, 5 DEG C are cooled to, then adds acryloyl chloride, wherein, the intermediate of formula (V) structure polyamide：Organic solvent：Beam acid agent：Propylene The mol ratio of acyl chlorides is 6：18~22：1.0~1.1：1.0~1.05；Temperature is no more than 15 DEG C in adition process, and acryloyl chloride adds After complete, 1~7h is reacted at 10 DEG C；
    (2) reactant obtained by step (1) is stood, and separates organic phase, is neutralized and is washed for several times with saturated salt sodium bicarbonate solution, with nothing Aqueous sodium persulfate is dried, and is steamed organic solvent and is produced crude product, crude product is further purified, produces the dendroid list of polymer grade Body；
    In formula (V), q is 2~8 integer, and p is 4~8 integer.
  12. 12. the preparation method of dendroid monomer according to claim 11, it is characterised in that：Described organic solvent is two Methylacetamide, dichloromethane, chloroform or dichloroethanes.
  13. 13. the preparation method of dendroid monomer according to claim 11, it is characterised in that：Described beam acid agent is three second Amine, three n-propyl amine or tri-n-butyl amine.
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WO2011147054A1 (en) * 2010-05-24 2011-12-01 中国石油天然气股份有限公司 Dendritic comb-shaped polymeric thickening agent, preparation and use thereof

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