CN104292129A - Dendritic monomer, treatment agent thereof, preparation method of dendritic monomer, and preparation method of treatment agent - Google Patents
Dendritic monomer, treatment agent thereof, preparation method of dendritic monomer, and preparation method of treatment agent Download PDFInfo
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Abstract
The invention relates to a dendritic monomer, a treatment agent thereof, a preparation method of the dendritic monomer, and a preparation method of the treatment agent, and belongs to the technical field of the synthesis and preparation of water soluble polymer materials. The treatment agent is prepared through the steps of aqueous solution polymerization of the dendritic monomer, a sulfonic acid monomer and an amide monomer in accordance with a molar ratio of (0.05-0.25):(0.10-0.35):(0.35-0.75) under a pH value of 6-9 under the action of a water-soluble azo initiator or/ and a redox initiator system, and drying. The treatment agent has strong temperature and salt resistance, can be used as a polymer filtrate loss reduction treatment agent in chloride calcium drilling fluids, has good water solubility, has good thickening and filtrate loss reduction characteristics at above 180 DEG C under saturated brine and high calcium conditions, has good high temperature stability, and has a good thickening effect in a calcium chloride solution.
Description
Technical field
The present invention relates to a kind of dendroid monomer, the treatment agent adopting this monomer and preparation method thereof, belong to water-soluble high-molecular material synthesis preparing technical field, or rather, be a kind of high temperature resistance anticalcium polymer drilling fluid finishing agent containing dendritic branch and preparation method thereof.
Background technology
Develop to deep for oil-gas exploration and development, drilling strata becomes increasingly complex, the practical problems that the difficulty that brill completion faces is increasing, and Chinese scholars, around the needs of superhigh temperature water base drilling fluid, has carried out a series of activities in the treatment agent of oil field.Focus on the modification of acrylamido copolymer, introduce new monomer and acrylamide copolymerization, prepare various fluid loss agent.But because synthesis monomer and method do not change, treatment agent performance there is no obvious progress, at present with or the treatment agent of research and development be still straight chain linear polymer, due to the restriction of molecular heat stability and shear stability,, also there is gap with needing of safeguarding of property of drilling fluid under ultra-high temperature condition in treatment agent temperature resistance limited ability.Want the heat and salinity tolerance performance improving deep-well, ultra-deep well drilling liquid, just must increase its consumption, but along with dosage improves the viscosity turn increasing drilling fluid, particularly when content of calcium and magnesium is high, mud property control is more difficult, and existing additive for drilling fluid can not meet the needs of drilling well completely.And containing the polymkeric substance of dendritic branch structure compared with traditional flexible-chain polymer, due to influencing each other of group in the steric effect of side chain and side chain, the thermostability of macromolecular structure can significantly improve, group abundant on molecule side chain ensure that treatment agent has good absorption and hydrating capacity, thus improve temperature resistance and the anti-shear ability for the treatment of agent, " China and foreign countries' energy " 2013,18 (1): 36-46 disclosed " high performance drilling treatment agent mentalities of designing " are the developing direction of following high performance drilling treatment agent.For this reason, the present invention adopts the dendroid monomer of synthesis and the monomer such as acrylamide, 2-acrylamide-2-methylpro panesulfonic acid to be raw material, preparation is containing the multipolymer of dendritic branch, and this multipolymer, as high temperature resistant drilling fluids treatment agent, has stronger filtrate reducing effect and good heat and salinity tolerance ability.
Summary of the invention
The object of the invention is to overcome the restriction of existing water-base drilling fluid treatment agent due to molecular heat stability and shear stability, cause water-base drilling fluid treatment agent heat and salinity tolerance limited ability and a kind of dendroid monomer and a kind of drilling fluid the polymer treatment agent and the preparation method of the two that contain dendritic branch are provided, the needs of the safety drilling construction under shaft bottom high temperature and/or high salt (sodium-chlor) high calcium environment can be met, rheological, suspension stability and filter loss under water-base drilling fluid high-temperature and high-pressure conditions can be controlled.
A kind of dendroid monomer, is characterized in that: its general structure is as shown in formula I:
In formula, R
1expression carbonatoms is H, methyl, and q is the integer of 2 ~ 8, and p is the integer of 4 ~ 8.
The polymer drilling fluid finishing agent of drilling fluid containing dendritic branch, its general structure is as formula II:
In formula, R
1expression carbonatoms is H, methyl, R
2-R
5identical or different, independently of one another for H, carbonatoms are the alkyl or phenyl of 1-4, X is NH or O, and q is the integer of 2 ~ 8, and p is the integer of 4 ~ 8, and n is the integer of 1 ~ 4; 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) by water, sodium hydroxide or potassium hydroxide add reactor, after it dissolves, add dendroid monomer (I), sulfonic acid monomer (III), after stirring, with the sodium hydroxide of massfraction 10% ~ 20% or potassium hydroxide solution, the pH value of system is adjusted to 6.0 ~ 9.0, then amide monomer (IV) is added, stirring makes it dissolve, wherein dendroid monomer (I), sulfonic acid or carboxylic acid monomer (III) and amide monomer (IV) anabolic reaction monomer mixture A, control reaction monomers mixture A massfraction in aqueous 20% ~ 50%, wherein, dendroid monomer (I): sulfonic acid or carboxylic acid monomer (III): amount of substance ratio=(0.05 ~ 0.25) of amide monomer (IV): (0.10 ~ 0.35): (0.35 ~ 0.75).
(2) under agitation add water-soluble azo initiator or/and add redox initiation system to the aqueous solution of step (1) gained, wherein, water-soluble azo initiator accounts for 0.05% ~ 0.5% of reaction monomers mixture A total mass; The oxygenant of redox initiation system, reductive agent respectively account for 0.10% ~ 0.75% of reaction monomers mixture A total mass;
(3) starting temperature of the polyreaction of the aqueous solution of regulating step (2) gained is 30 ~ 60 DEG C, maintains polyreaction 15 ~ 60 minutes, obtains thickness or gum-like product;
(4) namely thickness step (3) obtained or gum-like product oven dry, amidation, pulverizing at 140 ~ 160 DEG C obtain the polymer treatment agent of drilling fluid containing dendritic branch.
Described dendroid monomer (I): sulfonic acid or carboxylic acid monomer (III): amide monomer (IV), structural formula is as follows respectively:
In formula I ~ (IV), R
1expression carbonatoms is H, methyl, R
2-R
5identical or different, independently of one another for H, carbonatoms are the alkyl or phenyl of 1-4, X is NH or O, and q is the integer of 2 ~ 8, and p is the integer of 4 ~ 8, and n is the integer of 1 ~ 4.
In described formula III, X is NH, R
1and R
2for CH
3, n is 1; Or X is NH, R
2and R
3for H, n are 1; Or X is O, R
2and R
3for CH
3, n is 1; Or X is O, R
2and R
3for H, n are 3.
In described formula IV, R
4and R
5for H; Or, R
4and R
5for CH
3; Or, R
4and R
5for CH
2cH
3; Or, R
4for H, R
5for CH (CH
3) CH
3, or, R
4for H, R
5for C (CH
3)
2cH
3.
In the preparation method of drilling fluid of the present invention with the polymer treatment agent containing dendritic branch, step (1) described water consumption is water: monomer total mass=(8 ~ 5): (2 ~ 5) (mass ratio), namely controls monomer mass mark 20% ~ 50%.
In the preparation method of drilling fluid of the present invention with the polymer treatment agent containing dendritic branch, step (1) described sodium hydroxide (or potassium hydroxide) consumption is (3 × dendroid monomer molar number+sulfonic acid monomer mole number).
Described sulfonic acid monomer is 2-acrylamide-2-methylpro panesulfonic acid, 2-acrylamido ethyl sulfonic acid or 2-acrylamide oxygen-2-methyl propane sulfonic acid.
Described amide monomer is acrylamide, N,N-DMAA, N, N-acrylamide, N-isopropylacrylamide or isobutyl-acrylamide monomer.
Described initiator is azo two isobutyl imidazoline hydrochloride, azo diisobutyl amidine hydrochloride, azo dicyano valeric acid or azo di-isopropyl tetrahydroglyoxaline, and water-soluble azo initiator is 0.05% ~ 0.5% of monomer total mass; The oxygenant of oxidation-reduction trigger system is Potassium Persulphate or ammonium persulphate, and reductive agent is the one in sodium bisulfite, Sodium Pyrosulfite, S-WAT or Sulfothiorine, and oxygenant and reductive agent are respectively account for monomer total mass 0.10% ~ 0.75%.
The dendroid monomer of described formula I, is reacted by the intermediate of formula (V) structure polymeric amide and acrylate chloride:
Wherein, in formula (V), q is the integer of 2 ~ 8, and p is the integer of 4 ~ 8.
Described general formula is the dendroid monomer of formula I, and adopt process for acylating preparation, its process is as follows:
The intermediate of formula (V) structure polymeric amide, organic solvent and bundle acid agent being added is equipped with in the reaction flask of refrigerating unit, be cooled to 5 DEG C, then slowly acrylate chloride is added, wherein, the intermediate of formula (V) structure polymeric amide: organic solvent: restraint sour agent: the mol ratio of acrylate chloride is 6:18 ~ 22:1.0 ~ 1.1:1.0 ~ 1.05.In adition process, temperature is no more than 15 DEG C, after acrylate chloride adds, at 10 DEG C, react 1 ~ 7h.Reactant is left standstill, separates organic phase, wash for several times with the neutralization of saturated salt sodium hydrogen carbonate solution, with anhydrous sodium sulfate drying, steam organic solvent and namely obtain crude product, crude product is further purified, obtain the dendroid monomer (I) of polymerization-grade.
Described organic solvent is N,N-DIMETHYLACETAMIDE, methylene dichloride, trichloromethane or ethylene dichloride.
Described bundle acid agent is triethylamine, three n-propyl amine or tri-n-butyl amines.
The intermediate of described formula (V) structure polymeric amide directly adopts commodity; also reaction well known in the art can be adopted; obtained through Michael addition, acylation reaction by the Michael reaction product of methyl acrylate, thanomin and quadrol, methyl acrylate, its concrete steps are:
(1) methyl acrylate, thanomin and methyl alcohol is added in a kettle.; be warming up to 30 ~ 40 DEG C after first stirring 10 ~ 60min under 10 ~ 25 DEG C and logical shielding gas situation and keep 3 ~ 7h; then underpressure distillation is to remove methyl alcohol, obtain such as formula (V a) shown in the product of structure.
(2) by formula (V a) shown in the product of structure and methyl alcohol add in reactor, under 10 ~ 40 DEG C of agitation conditions, drip quadrol, then 20 ~ 35h is reacted at this temperature, then underpressure distillation is to remove methyl alcohol, namely obtains formula (V intermediate product b) shown in structure.
(3) by formula (V b) shown in the intermediate product of structure and methyl alcohol add in reactor, under 10 ~ 40 DEG C of agitation conditions, drip methyl acrylate, reaction 20 ~ 35h, underpressure distillation removing methyl alcohol, must such as formula (V c) shown in the intermediate product of structure.
(4) (V c) intermediate product of structure and methyl alcohol add in reactor modus ponens, under 10 ~ 40 DEG C of agitation conditions, drip diamine, reaction 20 ~ 35h, underpressure distillation, to remove methyl alcohol, obtains such as formula (V intermediate product d) shown in structure.
(5) modus ponens (V d) intermediate product of structure and diprotic acid be the ratio of 1:1 ~ 1.05 according to mol ratio, at 110 ~ 160 DEG C, react 2 ~ 6h, obtain the dendroid intermediate such as formula (V) structure.
The invention has the beneficial effects as follows: the monomer and the sulfonic acid monomer that adopt dendritic structure, amide monomer copolymerization, the polymer treatment agent containing dendritic branch obtained, monomer due to dendritic structure has abundant imido grpup, carbonyl, the groups such as carboxyl, and molecular chain rigidity is strong, both there is stronger heat and salinity tolerance ability, the polymer filtrate reducer in calcium chloride drilling liquor can be used as again, product good water solubility, adopt the preparation of aqueous solution rapid polymerization method, reaction process easily controls, simple to operate, constant product quality, production and drying course consume energy low, environmentally safe, under high temperature (more than 180 DEG C) high salt (saturated brine) and high calcium condition, there is good thickening, suppress and filtrate reducing characteristic, high-temperature stability is good, there is good Efficient Adhesive Promotion in calcium chloride solution.
Embodiment
Below in conjunction with specific embodiment, the present invention and effect thereof are described further.
Embodiment 1
The preparation example 1 of dendroid monomer:
(1) methyl acrylate, thanomin and methyl alcohol is added in a kettle., first at 25 DEG C and logical N
2be warming up to 40 DEG C after stirring 10min in situation and keep 3h, then underpressure distillation is remove methyl alcohol, obtains such as formula (the product of V a) shown structure.
(2) by formula (V a) shown in the product of structure and methyl alcohol add in reactor, under 10 DEG C of agitation conditions, drip quadrol, then react 35h at this temperature, then underpressure distillation is to remove methyl alcohol, namely obtains formula (V intermediate product b) shown in structure.
(3) by formula (V b) shown in the intermediate product of structure and methyl alcohol add in reactor, under 40 DEG C of agitation conditions, drip methyl acrylate, reaction 35h, underpressure distillation removing methyl alcohol, must such as formula (V c) shown in the intermediate product of structure.
(4) modus ponens (V c) intermediate product of structure and methyl alcohol add in reactor, under 40 DEG C of agitation conditions, drip butanediamine, reaction 20h, underpressure distillation, to remove methyl alcohol, obtains such as formula (V intermediate product d) shown in structure.
(5) modus ponens (V d) intermediate product of structure and hexanodioic acid be the ratio of 1:1.05 according to mol ratio, at 160 DEG C, react 2h, obtain the branch intermediate such as formula (V) structure.
(6) dendroid intermediate: N,N-DIMETHYLACETAMIDE: triethylamine: acrylate chloride is 6:18:1.0:1.0 (mol ratio), the dendritic intermediate of formula (V) structure tree, N,N-DIMETHYLACETAMIDE and triethylamine being added is equipped with in the reaction flask of refrigerating unit, be cooled to 5 DEG C, then slowly acrylate chloride is added, in adition process, temperature is no more than 15 DEG C, after acrylate chloride adds, at 10 DEG C, react 1h.Reactant is left standstill, separates organic phase, wash for several times with the neutralization of saturated salt sodium hydrogen carbonate solution, with anhydrous sodium sulfate drying, steam N,N-DIMETHYLACETAMIDE and namely obtain crude product, crude product is further purified, obtain the dendroid monomer of polymerization-grade.
Water (its consumption is to make monomer mass mark 20%), the sodium hydroxide of 0.55 mole are added reactor, after it dissolves, 0.05 mole of preparation example 1 is obtained add reactor containing dendritic branch monomer and 0.35 mole of 2-acrylamide-2-methylpro panesulfonic acid, after stirring, with the potassium hydroxide solution of massfraction 20%, the pH value of system is adjusted to 9.0, then add and 0.35 mole percent acrylamide, stirring makes it dissolve and obtains reaction mixture.Under agitation add account for total monomer weight 0.15% ammonium persulphate, account for total monomer weight 0.15% sodium bisulfite, the starting temperature of polyreaction is 60 DEG C, maintain polymerization reaction time be 120 minutes, finally obtain gum-like product.The gum-like product obtained is dried at 140 DEG C, pulverizes and obtain the polymer treatment agent of drilling fluid containing dendritic branch.
Embodiment 2
Dendroid monomer preparation example 2:
(1) methyl acrylate, thanomin and methyl alcohol is added in a kettle., first at 25 DEG C and logical N
2be warming up to 30 DEG C after stirring 60min in situation and keep 7h, then underpressure distillation is remove methyl alcohol, obtains such as formula (the product of V a) shown structure.
(2) by formula (V a) shown in the product of structure and methyl alcohol add in reactor, under 10 DEG C of agitation conditions, drip quadrol, then react 20h at this temperature, then underpressure distillation is to remove methyl alcohol, namely obtains formula (V intermediate product b) shown in structure.
(3) by formula (V b) shown in the intermediate product of structure and methyl alcohol add in reactor, under 10 DEG C of agitation conditions, drip methyl acrylate, reaction 20h, underpressure distillation removing methyl alcohol, must such as formula (V c) shown in the intermediate product of structure.
(4) modus ponens (V c) intermediate product of structure and methyl alcohol add in reactor, under 10 DEG C of agitation conditions, drip quadrol, reaction 20h, underpressure distillation, to remove methyl alcohol, obtains such as formula (V intermediate product d) shown in structure.
(5) modus ponens (V d) intermediate product of structure and suberic acid be the ratio of 1:1 according to mol ratio, at 110 DEG C, react 6h, obtain the branch intermediate such as formula (V) structure.
(6) dendroid intermediate: methylene dichloride: triethylamine: acrylate chloride is 6:22:1.1:1.05 (mol ratio), the dendritic intermediate of formula (V) structure tree, methylene dichloride and triethylamine being added is equipped with in the reaction flask of refrigerating unit, be cooled to 5 DEG C, then slowly acrylate chloride is added, in adition process, temperature is no more than 10 DEG C, after acrylate chloride adds, at 10 DEG C, react 7h.Reactant is left standstill, separates organic phase, wash for several times with the neutralization of saturated salt sodium hydrogen carbonate solution, with anhydrous sodium sulfate drying, steam methylene dichloride and namely obtain crude product, crude product is further purified, obtain the dendroid monomer of polymerization-grade.
Water (its consumption is to make monomer mass mark 50%), the sodium hydroxide of 1.1 moles are added reactor, after it dissolves, 0.25 mole of preparation example 2 is obtained add reactor containing dendritic branch monomer and 0.10 mole of 2-acrylamide-2-methylpro panesulfonic acid, after stirring, with the sodium hydroxide solution of massfraction 15%, the pH value of system is adjusted to 7.0, then add and 0.75 mole percent acrylamide, stirring makes it dissolve and obtains reaction mixture.Under agitation add account for total monomer weight 1.0% ammonium persulphate, account for total monomer weight 1.0% sodium bisulfite, the starting temperature of polyreaction is 30 DEG C, maintain polymerization reaction time be 45 minutes, finally obtain viscous product.The viscous product obtained is dried at 160 DEG C, pulverizes and obtain the polymer treatment agent of drilling fluid containing dendritic branch.
Embodiment 3
Dendroid monomer preparation example 3:
(1) methyl acrylate, thanomin and methyl alcohol is added in a kettle., first at 20 DEG C and logical N
2be warming up to 35 DEG C after stirring 50min in situation and keep 5h, then underpressure distillation is remove methyl alcohol, obtains such as formula (the product of V a) shown structure.
(2) by formula (V a) shown in the product of structure and methyl alcohol add in reactor, under 25 DEG C of agitation conditions, drip quadrol, then react 30h at this temperature, then underpressure distillation is to remove methyl alcohol, namely obtains formula (V intermediate product b) shown in structure.
(3) by formula (V b) shown in the intermediate product of structure and methyl alcohol add in reactor, under 35 DEG C of agitation conditions, drip methyl acrylate, reaction 30h, underpressure distillation removing methyl alcohol, must such as formula (V c) shown in the intermediate product of structure.
(4) modus ponens (V c) intermediate product of structure and methyl alcohol add in reactor, under 35 DEG C of agitation conditions, drip octamethylenediamine, reaction 30h, underpressure distillation, to remove methyl alcohol, obtains such as formula (V intermediate product d) shown in structure.
(5) modus ponens (V d) intermediate product of structure and succinic acid be the ratio of 1:1.02 according to mol ratio, at 140 DEG C, react 4h, obtain the dendroid intermediate such as formula (V) structure.
(6) dendroid intermediate: trichloromethane: tri-n-butyl amine: acrylate chloride is 6:20:1.05:1.0 ~ 1.025 (mol ratios), the dendritic intermediate of formula (V) structure tree, trichloromethane and tri-n-butyl amine being added is equipped with in the reaction flask of refrigerating unit, be cooled to 5 DEG C, then slowly acrylate chloride is added, in adition process, temperature is no more than 12 DEG C, after acrylate chloride adds, at 10 DEG C, react 6h.Reactant is left standstill, separates organic phase, wash for several times with the neutralization of saturated salt sodium hydrogen carbonate solution, with anhydrous sodium sulfate drying, steam trichloromethane and namely obtain crude product, crude product is further purified, obtain the dendroid monomer of polymerization-grade.
Water (its consumption is to make monomer mass mark 40%), the potassium hydroxide of 0.80 mole are added reactor, after it dissolves, 0.15 mole of preparation example 3 is obtained add reactor containing dendritic branch monomer and 0.20 mole of 2-acrylamide-2-methylpro panesulfonic acid, after stirring, with the sodium hydroxide solution of massfraction 10%, the pH value of system is adjusted to 8.0, then add and 0.60 mole of N-isopropylacrylamide, stirring makes it dissolve and obtains reaction mixture.Under agitation add account for total monomer weight 0.45% Potassium Persulphate, account for total monomer weight 0.45% Sodium Pyrosulfite, the starting temperature of polyreaction is 40 DEG C, maintain polymerization reaction time be 90 minutes, finally obtain gum-like product.The gum-like product obtained is dried at 160 DEG C, pulverizes and obtain the polymer drilling fluid finishing agent containing dendritic branch.
Embodiment 4
Dendroid monomer preparation example 4:
(1) methyl acrylate, thanomin and methyl alcohol is added in a kettle., first at 15 DEG C and logical N
2be warming up to 32 DEG C after stirring 40min in situation and keep 4h, then underpressure distillation is remove methyl alcohol, obtains such as formula (the product of V a) shown structure.
(2) by formula (V a) shown in the product of structure and methyl alcohol add in reactor, under 30 DEG C of agitation conditions, drip quadrol, then react 25h at this temperature, then underpressure distillation is to remove methyl alcohol, namely obtains formula (V intermediate product b) shown in structure.
(3) by formula (V b) shown in the intermediate product of structure and methyl alcohol add in reactor, under 250 DEG C of agitation conditions, drip methyl acrylate, reaction 30h, underpressure distillation removing methyl alcohol, must such as formula (V c) shown in the intermediate product of structure.
(4) modus ponens (V c) intermediate product of structure and methyl alcohol add in reactor, under 25 DEG C of agitation conditions, drip hexanediamine, reaction 30h, underpressure distillation, to remove methyl alcohol, obtains such as formula (V intermediate product d) shown in structure.
(5) modus ponens (V d) intermediate product of structure and pentanedioic acid be the ratio of 1:1.01 according to mol ratio, at 130 DEG C, react 3h, obtain the dendroid intermediate such as formula (V) structure.
(6) dendroid intermediate: ethylene dichloride: three n-propyl amine: methacrylic chloride is 6:22:1.1:1.0 (mol ratio), the dendritic intermediate of formula (V) structure tree, ethylene dichloride and three n-propyl amine being added is equipped with in the reaction flask of refrigerating unit, be cooled to 5 DEG C, then slowly methacrylic chloride is added, in adition process, temperature is no more than 15 DEG C, after acrylate chloride adds, at 10 DEG C, react 4h.Reactant is left standstill, separates organic phase, wash for several times with the neutralization of saturated salt sodium hydrogen carbonate solution, with anhydrous sodium sulfate drying, steam ethylene dichloride and namely obtain crude product, crude product is further purified, obtain the dendroid monomer of polymerization-grade.
Water (its consumption is to make monomer mass mark 40%), the sodium hydroxide of 0.85 mole are added reactor, after it dissolves, what 0.15 mole of preparation example 4 obtained adds reactor containing dendritic branch monomer and 0.25 mole of 2-acrylamide-2-methylpro panesulfonic acid, after stirring, with the sodium hydroxide solution of massfraction 20% by system
ph value is adjusted to 8.0, then adds 0.75 mole percent acrylamide, and stirring makes it dissolve and obtains reaction mixture.Under agitation add account for total monomer weight 0.45% ammonium persulphate, account for total monomer weight 0.45% sodium bisulfite, the starting temperature of polyreaction is 40 DEG C, maintain polymerization reaction time be 90 minutes, finally obtain gum-like product.The gum-like product obtained is dried at 160 DEG C, pulverizes and obtain the polymer drilling fluid finishing agent containing dendritic branch.
Embodiment 5-10, according to the synthesis condition of embodiment 4 and formula, only replaces partial reaction thing, as shown in table 1 below:
The list of table 1 embodiment 5-10 partial reaction thing
Comparative example 1:
According to synthesis condition and the formula of embodiment 4, just remove dendroid monomer, synthesis copolymer.
The product that different embodiment obtains in composite salt aqueous drilling fluid filtrate reducing effect and 1% Aqueous Solution Viscosity in table 2.
The preparation of compound salt-water basic slurry: add 15.75g sodium-chlor in 350ml distilled water, 1.75g Calcium Chloride Powder Anhydrous, 4.6g magnesium chloride, 52.5g calcium bentonite and 3.15g anhydrous sodium carbonate, high-speed stirring 20min, room temperature places aging 24h.
Add the sample of 1.5% during evaluation, high-speed stirring 5 minutes, then at 180 DEG C of aging 16h that roll, be cooled to room temperature, measure the filter loss of drilling fluid.The API filtration that base is starched after 180 DEG C of aging 16h that roll is 228 milliliters.Prepare 1% aqueous solution, the apparent viscosity AV at measuring 25 DEG C, in 1% aqueous solutions of polymers, add the calcium chloride of 5% simultaneously, stir, measure Calcium treatment rear solution apparent viscosity AV
1, and calculate retention of viscosity rate:
Retention of viscosity rate=add calcium chloride aqueous solutions of polymers viscosity/aqueous solutions of polymers viscosity × 100%
Table 2 embodiment and comparative example effect comparison
As can be seen from Table 2, the retention of viscosity rate average out to 31.15% of the embodiment of the present invention, much larger than the retention of viscosity rate 21.52% of comparative example, effect is obviously better than comparative example, thus find out that the present invention had both had stronger heat and salinity tolerance ability, can treatment agent fall the polymkeric substance be used as in calcium chloride drilling liquor again, product good water solubility, more than 180 DEG C, under saturated brine and high calcium condition, there is good thickening and filtrate reducing characteristic, high-temperature stability is good, has good Efficient Adhesive Promotion in calcium chloride solution.
Claims (15)
1. a dendroid monomer, is characterized in that: its general structure is as shown in formula I:
In formula, R
1represent H or methyl, q is the integer of 2 ~ 8, and p is the integer of 4 ~ 8.
2. the polymer drilling fluid finishing agent of drilling fluid containing dendritic branch, is characterized in that: its general structure is as formula II:
In formula, R
1expression carbonatoms is H, methyl, R
2-R
5identical or different, independently of one another for H, carbonatoms are the alkyl or phenyl of 1-4, X is NH or O, and q is the integer of 2 ~ 8, and p is the integer of 4 ~ 8, and n is the integer of 1 ~ 4; M is K or Na; A:b:c=(0.5 ~ 2.5): (1 ~ 3.5): (3.5 ~ 7.5).
3. a drilling fluid preparation method for the polymer treatment agent containing dendritic branch, is characterized in that: comprise the following steps:
(1) by water, sodium hydroxide or potassium hydroxide add reactor, after it dissolves, add dendroid monomer (I), sulfonic acid monomer (III), after stirring, with the sodium hydroxide of massfraction 10% ~ 20% or potassium hydroxide solution, the pH value of system is adjusted to 6.0 ~ 9.0, then amide monomer (IV) is added, stirring makes it dissolve, wherein dendroid monomer (I), sulfonic acid or carboxylic acid monomer (III) and amide monomer (IV) anabolic reaction monomer mixture A, control reaction monomers mixture A massfraction in aqueous 20% ~ 50%, wherein, dendroid monomer (I): sulfonic acid or carboxylic acid monomer (III): amount of substance ratio=(0.05 ~ 0.25) of amide monomer (IV): (0.10 ~ 0.35): (0.35 ~ 0.75),
(2) under agitation add water-soluble azo initiator or/and add redox initiation system to the aqueous solution of step (1) gained, wherein, water-soluble azo initiator accounts for 0.05% ~ 0.5% of reaction monomers mixture A total mass; The oxygenant of redox initiation system, reductive agent respectively account for 0.10% ~ 0.75% of reaction monomers mixture A total mass;
(3) starting temperature of the polyreaction of the aqueous solution of regulating step (2) gained is 30 ~ 60 DEG C, maintains polyreaction 15 ~ 60 minutes, obtains thickness or gum-like product;
(4) namely thickness step (3) obtained or gum-like product oven dry, amidation, pulverizing at 140 ~ 160 DEG C obtain the polymer treatment agent of drilling fluid containing dendritic branch.
4. the drilling fluid according to claim 3 preparation method of the polymer treatment agent containing dendritic branch, it is characterized in that: described dendroid monomer (I): sulfonic acid or carboxylic acid monomer (III): amide monomer (IV), structural formula is as follows respectively:
In formula II ~ (IV), R
1expression carbonatoms is H, methyl, R
2-R
5identical or different, independently of one another for H, carbonatoms are the alkyl or phenyl of 1-4, X is NH or O, and q is the integer of 2 ~ 8, and p is the integer of 4 ~ 8, and n is the integer of 1 ~ 4.
5. the drilling fluid according to claim 3 preparation method of the polymer treatment agent containing dendritic branch, is characterized in that: in described formula III, X is NH, R
1and R
2for CH
3, n is 1; Or X is NH, R
2and R
3for H, n are 1; Or X is O, R
2and R
3for CH
3, n is 1; Or X is O, R
2and R
3for H, n are 3.
6. the drilling fluid according to claim 3 preparation method of the polymer treatment agent containing dendritic branch, is characterized in that: in described formula IV, R
4and R
5for H; Or, R
4and R
5for CH
3; Or, R
4and R
5for CH
2cH
3; Or, R
4for H, R
5for CH (CH
3) CH
3, or, R
4for H, R
5for C (CH
3)
2cH
3.
7. the drilling fluid according to claim 3 preparation method of the polymer treatment agent containing dendritic branch, is characterized in that: described sulfonic acid monomer is 2-acrylamide-2-methylpro panesulfonic acid, 2-acrylamido ethyl sulfonic acid or 2-acrylamide oxygen-2-methyl propane sulfonic acid.
8. the drilling fluid according to claim 3 preparation method of the polymer treatment agent containing dendritic branch, it is characterized in that: described amide monomer is acrylamide, N, N-DMAA, N, N-acrylamide, N-isopropylacrylamide or isobutyl-acrylamide monomer.
9. the drilling fluid according to claim 3 preparation method of the polymer treatment agent containing dendritic branch, it is characterized in that: described initiator is water-soluble azo initiator, be specially azo two isobutyl imidazoline hydrochloride, azo diisobutyl amidine hydrochloride, azo dicyano valeric acid or azo di-isopropyl tetrahydroglyoxaline, water-soluble azo initiator is 0.05% ~ 0.5% of reaction monomers mixture A total mass.
10. the drilling fluid according to claim 3 preparation method of the polymer treatment agent containing dendritic branch, it is characterized in that: described initiator is oxidation-reduction trigger system, wherein oxygenant is Potassium Persulphate or ammonium persulphate, reductive agent is the one in sodium bisulfite, Sodium Pyrosulfite, S-WAT or Sulfothiorine, and oxygenant and reductive agent are respectively account for reaction monomers mixture A total mass 0.10% ~ 0.75%.
The 11. drilling fluid according to claim 3 preparation methods of the polymer treatment agent containing dendritic branch, is characterized in that: described sodium hydroxide (or potassium hydroxide) consumption is (3 × dendroid monomer molar number+sulfonic acid monomer mole number).
The preparation method of 12. 1 kinds of dendroid monomers as claimed in claim 1; it is characterized in that: described dendroid monomer (I); be obtained by reacting by the intermediate of formula (V) structure polymeric amide and acrylate chloride, adopt process for acylating preparation process as follows:
(1) intermediate of formula (V) structure polymeric amide, organic solvent and bundle acid agent is added and is equipped with in the reaction flask of refrigerating unit, be cooled to 5 DEG C, then slowly acrylate chloride is added, wherein, the intermediate of formula (V) structure polymeric amide: organic solvent: restraint sour agent: the mol ratio of acrylate chloride is 6:18 ~ 22:1.0 ~ 1.1:1.0 ~ 1.05; In adition process, temperature is no more than 15 DEG C, after acrylate chloride adds, at 10 DEG C, react 1 ~ 7h;
(2) reactant of step (1) gained leaves standstill, separate organic phase, wash for several times with the neutralization of saturated salt sodium hydrogen carbonate solution, with anhydrous sodium sulfate drying, steam organic solvent and namely obtain crude product, crude product is further purified, obtains the dendroid monomer (I) of polymerization-grade.
The preparation method of 13. dendroid monomers according to claim 12, is characterized in that: the intermediate of described formula (V) structure polymeric amide is:
In formula (V), q is the integer of 2 ~ 8, and p is the integer of 4 ~ 8.
The preparation method of 14. dendroid monomers according to claim 12, is characterized in that: described organic solvent is N,N-DIMETHYLACETAMIDE, methylene dichloride, trichloromethane or ethylene dichloride.
The preparation method of 15. dendroid monomers according to claim 12, is characterized in that: described bundle acid agent is triethylamine, three n-propyl amine or tri-n-butyl amines.
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| CN106519254A (en) * | 2016-11-03 | 2017-03-22 | 中国石油大学(华东) | Dendritic quaternary ammonium salt shale inhibitor as well as preparation method and application thereof |
| CN110938414A (en) * | 2019-11-25 | 2020-03-31 | 长江大学 | Temperature-resistant anti-collapse multi-polymer filtrate reducer and preparation method thereof |
| WO2023092242A1 (en) * | 2021-11-29 | 2023-06-01 | The Governing Council Of The University Of Toronto | Multi-motif dendrons and their supramolecular structures and uses thereof |
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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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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106519254A (en) * | 2016-11-03 | 2017-03-22 | 中国石油大学(华东) | Dendritic quaternary ammonium salt shale inhibitor as well as preparation method and application thereof |
| CN110938414A (en) * | 2019-11-25 | 2020-03-31 | 长江大学 | Temperature-resistant anti-collapse multi-polymer filtrate reducer and preparation method thereof |
| US20210155730A1 (en) * | 2019-11-25 | 2021-05-27 | Yangtze University | Temperature-resistant and anti-collapse multi-branched polymer fluid loss reducer and preparation method thereof |
| CN110938414B (en) * | 2019-11-25 | 2022-07-12 | 长江大学 | Temperature-resistant anti-collapse multi-polymer filtrate reducer and preparation method thereof |
| US11447589B2 (en) * | 2019-11-25 | 2022-09-20 | Yangtze University | Temperature-resistant and anti-collapse multi-branched polymer fluid loss reducer and preparation method thereof |
| WO2023092242A1 (en) * | 2021-11-29 | 2023-06-01 | The Governing Council Of The University Of Toronto | Multi-motif dendrons and their supramolecular structures and uses thereof |
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