CN106188446B - A kind of modification sulphonation phenolic resin and the treating agent of drilling mud comprising it - Google Patents

A kind of modification sulphonation phenolic resin and the treating agent of drilling mud comprising it Download PDF

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CN106188446B
CN106188446B CN201610562597.8A CN201610562597A CN106188446B CN 106188446 B CN106188446 B CN 106188446B CN 201610562597 A CN201610562597 A CN 201610562597A CN 106188446 B CN106188446 B CN 106188446B
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phenolic resin
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CN106188446A (en
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梁吉营
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Henan Tianfu Chemical Co Ltd
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Henan Tianfu Chemical Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
    • C08G8/28—Chemically modified polycondensates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F120/52—Amides or imides
    • C08F120/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F120/56—Acrylamide; Methacrylamide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
    • C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
    • C08G8/08—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ
    • C08G8/24—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ with mixtures of two or more phenols which are not covered by only one of the groups C08G8/10 - C08G8/20
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/02—Well-drilling compositions
    • C09K8/03—Specific additives for general use in well-drilling compositions
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/02—Well-drilling compositions
    • C09K8/03—Specific additives for general use in well-drilling compositions
    • C09K8/032—Inorganic additives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/02—Well-drilling compositions
    • C09K8/03—Specific additives for general use in well-drilling compositions
    • C09K8/035—Organic additives

Abstract

The present invention provides a kind of modification sulphonation phenolic resin to be prepared as follows in parts by weight：(1) phenol, dihydric phenol, formaldehyde are added in a kettle, is warming up to 97 105 DEG C, 20% hydrochloric acid is added and reacts 10 15 minutes；(2) 20% sodium hydroxide solution is added thereto, sulfonating agent is then added, is heated to 97 105 DEG C, reacts 80 100 minutes；(3) second of addition sulfonating agent, formaldehyde, organic polymer nano-particle, silane coupling agent react 80 100 minutes at 97 105 DEG C；(4) sulfonating agent is added in third time, is reacted 80 100 minutes at 97 105 DEG C；(5) the 4th addition sulfonating agents, react 80 100 minutes at 97 105 DEG C；(6) after the completion of reacting, modification sulphonation phenolic resin is obtained using spray drying；The present invention also provides the treating agent of drilling mud for including above-mentioned modification sulphonation phenolic resin.

Description

A kind of modification sulphonation phenolic resin and the treating agent of drilling mud comprising it
Technical field
The invention belongs to field of oilfield chemistry more particularly to a kind of modification sulphonation phenolic resin, and include the modified sulphur Change the treating agent of drilling mud of phenolic resin.
Background technology
With the increase of world energy sources demand, World Petroleum Exploration ＆ Development gradually develops to deep formation.Drilling stratum day Become complicated, higher requirement is put forward to stability of the drilling fluid in high temperature and high salinity environment.
Sulfonated phenol formaldehyde resin is a kind of mud conditioner that developed recently gets up, and there is salt resistance, high temperature resistance, control mud to lose Water and the performances such as anti-collapse, are used primarily in deep-well brine system.But the sulfonated phenol formaldehyde resin prepared according to existing method is in height In use, that there are service efficiencies is low, inhibition is poor and poor in middle-deep well section using effect in warm high pressure and high salinity media Defect, high temperature resistance, salt resistance and caving-preventing ability are poor, have been unable to meet brine and saturated salt-water drilling fluid high temperature under ultra-high temperature condition The needs of high pressure Filtrate Loss Control and rheology.
Therefore, to adapt to increasingly complex environment in drilling process, need to develop new modification sulphonation phenolic resin and Drilling mud shaking inorganic agent.
Invention content
To solve the problems of the prior art, the present invention provides a kind of modification sulphonation phenolic resin, have excellent resist High temperature, the performance of salt resistance and excellent anti-filtration property.The present invention also provides a kind for the treatment of agent of drilling mud, have anti- High temperature, salt resistance function, while thickening power will not be caused without flocculation to clay particle object；It is easy especially suitable for deep Collapse stratum, salt cream mud bad ground oil-gas Layer probing, it is free from environmental pollution.
According to an aspect of the invention, there is provided a kind of modification sulphonation phenolic resin, by weight, the modified sulphur Change phenolic resin to be prepared via a method which：
(1) 1.8-3.2 parts of phenol, 0.9-1.1 parts of dihydric phenol, first are sequentially added in the reaction kettle for being equipped with reflux 1.5-3 parts of aldehyde is warming up to 97-105 DEG C, and 0.02-0.06 parts of 20% hydrochloric acid is added, and reacts 10-15 minutes；
(2) 0.5-1.3 parts of 20% sodium hydroxide solution is added thereto, 1.4-1.7 parts of sulfonating agent is then added, is heated to It 97-105 DEG C, reacts 80-100 minutes under reflux；
(3) 1.4-1.7 parts of sulfonating agent, 0.02-0.09 parts of formaldehyde, organic polymer nano-particle 0.03- is added second 0.07 part, 0.01-0.05 parts of silane coupling agent, back flow reaction 80-100 minutes at 97-105 DEG C；
(4) 1.4-1.7 parts of sulfonating agent is added in third time, back flow reaction 80-100 minutes at 97-105 DEG C；
(5) the 4th 1.4-1.7 parts of sulfonating agents of addition, back flow reaction 80-100 minutes at 97-105 DEG C；
(6) after the completion of reacting, modification sulphonation phenolic resin is obtained using spray drying；
Wherein, the group of the sulfonating agent becomes：18 parts of water, 36.5 parts of formaldehyde, 45.5 parts of sodium pyrosulfite.
The dihydric phenol is one or more in catechol, resorcinol and hydroquinone.
The organic polymer nano-particle is selected from by (methyl) acrylic acid, (methyl) methyl acrylate, (methyl) propylene A kind of monomer polymerization in acetoacetic ester, (methyl) butyl acrylate, (methyl) acrylamide, styrene, sodium p styrene sulfonate Or several monomers are copolymerized generated polymer nano-particle.
The silane coupling agent is selected from gamma-methyl allyl acyloxypropyl trimethoxysilane, γ-methacryloxypropyl third Ethyl triethoxy silicane alkane, vinyltrimethoxysilane, vinyltriethoxysilane, gamma-amino propyl trimethoxy silicane, γ aminopropyltriethoxy silane, γ-glycidoxypropyltrimewasxysilane, three ethoxy of 3- isocyanates propyl It is one or more in base silane.
The grain size of the organic polymer nano-particle is 20~80nm.
Wherein, in above-mentioned steps (1), hydrochloric acid can be added portionwise, such as be added in four times.
In above-mentioned steps (2)-(5), during which repeatedly to sample to control viscosity, if viscosity is excessively high, can suitably add Water is to control viscosity rise.
Modification sulphonation phenolic resin according to the present invention has anti-excellent high temperature resistance, the performance of salt resistance and excellent Anti- filtration property is primarily adapted for use in high salinity anti-saturation salt water base mud system, and anti-sodium salt reaches 36%, is more than in well depth At 7000 meters, using effect is more preferably.Dosage is only 50% or so of similar phenolic resin.
The present invention also provides the preparation methods of the modification sulphonation phenolic resin.
By weight, the modification sulphonation phenolic resin is prepared via a method which：
(1) 1.8-3.2 parts of phenol, 0.9-1.1 parts of dihydric phenol, first are sequentially added in the reaction kettle for being equipped with reflux 1.5-3 parts of aldehyde is warming up to 97-105 DEG C, and 0.02-0.06 parts of 20% hydrochloric acid is added, and reacts 10-15 minutes；
(2) 0.5-1.3 parts of 20% sodium hydroxide solution is added thereto, 1.4-1.7 parts of sulfonating agent is then added, is heated to It 97-105 DEG C, reacts 80-100 minutes under reflux；
(3) 1.4-1.7 parts of sulfonating agent, 0.02-0.09 parts of formaldehyde, organic polymer nano-particle 0.03- is added second 0.07 part, 0.01-0.05 parts of silane coupling agent, back flow reaction 80-100 minutes at 97-105 DEG C；
(4) 1.4-1.7 parts of sulfonating agent is added in third time, back flow reaction 80-100 minutes at 97-105 DEG C；
(5) the 4th 1.4-1.7 parts of sulfonating agents of addition, back flow reaction 80-100 minutes at 97-105 DEG C；
(6) after the completion of reacting, modification sulphonation phenolic resin is obtained using spray drying；
Wherein, the group of the sulfonating agent becomes：18 parts of water, 36.5 parts of formaldehyde, 45.5 parts of sodium pyrosulfite.
The meaning of the dihydric phenol, organic polymer nano-particle and silane coupling agent is as described above.
According to another aspect of the present invention, a kind for the treatment of agent of drilling mud is provided, is grouped by the group of following parts by weight At：
16-22 parts of modification sulphonation phenolic resin, 8-12 parts of hydroxypropyl azochlorosulfonate acid sodium, 6-10 parts of oleamide hydroxy sulfo lycine, 5-8 parts of trifluoro propyl methyl cyclotrisiloxane, 12-18 parts of acrylamide, 0.02-0.1 parts of ammonium persulfate, nano-titanium dioxide 1- 5 parts, 3-6 parts of sodium bicarbonate.
Preferably, the treating agent of drilling mud is grouped as by the group of following parts by weight：
18 parts of modification sulphonation phenolic resin, 10 parts of hydroxypropyl azochlorosulfonate acid sodium, 8 parts of oleamide hydroxy sulfo lycine, trifluoro propyl 6 parts of methyl cyclotrisiloxane, 15 parts of acrylamide, 0.05 part of ammonium persulfate, 2 parts of nano-titanium dioxide, 5 parts of sodium bicarbonate.
Wherein, modification sulphonation phenolic resin is prepared according to above-mentioned preparation method.
The raw material of production modification sulphonation phenolic resin is generally phenol and formaldehyde, and there are unreacted formaldehyde in product, together When in the product in the presence of the active group methylol that high temperature can be caused to be thickened, the hydroxypropyl azochlorosulfonate acid sodium that the present invention uses can drop Methylol in low sulfonated phenolic resin enhances the hydrophily of sulfonated phenol formaldehyde resin, and the high temperature that can effectively improve drilling fluid is steady It is qualitative.
Oleamide hydroxy sulfo lycine has the structure of following chemical formula 1, and oleamide hydroxy sulfo lycine is as lubrication breast Agent has the characteristics that emulsifying capacity is strong, performance is stable, lubricity is good, not blistering, has good lubrication drag reduction effect.
[chemical formula 1]
The trifluoro propyl methyl cyclotrisiloxane that the present invention uses has the following effects that：Excellent filtrate reducing and retaining wall is anti-collapse Performance；Viscosity effect is small, can adjust the rheological characteristic of drilling fluid well；Temperature resistance ability is strong；Reduce the phase interaction between clay With effectivelying prevent the hydration swelling of clay.
Nanometer titanic oxide material can enter the micro-pore of mud shale stratum and split because of its Nano Particle relationship Among seam, to improve the plugging effect of water-base drilling fluid, slows down after infiltration and stratum of the drilling fluid to stratum absorb water and expand, fall The trend of block, to improve borehole wall stability.In addition, nano-titanium dioxide can make base starch to form more thin and compact mud cake, Filtrate reducing is with obvious effects, and the temperature resistance ability for the base slurry being added after nano-titanium dioxide is increased to 200 DEG C from 120 DEG C or so.Therefore, Nano-titanium dioxide is alternatively arranged as a kind of high temperature resistance filtrate reducing while effectively reducing mud shale permeability, reducing water erosion Agent uses.
In the present invention, the grain size of nano-titanium dioxide is 20~100nm.
CO in the sodium bicarbonate used in the present invention3 2-、HCO3 -With the Soluble Ca in rock salt stratum2+、Mg2+Occur anti- It answers, generates calcium carbonate, carbonic acid magnesium precipitate, on the one hand eliminate Ca2+、Mg2+Ion reduces salinity, this is to a certain extent It eliminates because high salinity reduces the influence factor of other component functioning efficiencies；On the other hand calcium carbonate superfine powder, the carbonic acid generated Magnesium coordinates sealing agent that can realize strong block to microcrack mud shale stratum.
In the present invention, acrylamide occurs instead with nano-titanium dioxide under the action of sodium bicarbonate and ammonium persulfate It answers, obtains polyacrylamide nano composite titania material.
Polyacrylamide organic phase is mutually compound in the form of chemical bonding by chemically reacting with nano titanium oxide inorganic, obtains To high performance drilling fluid additive, reach thickening, filtrate reducing effect, especially high-temperature resisting and salt-resisting and reservoir protection and the borehole wall is steady Fixed effect.
The present invention also provides a kind of preparation methods for the treatment of agent of drilling mud, include the following steps：
(1) following parts by weight are pressed and prepares raw material
16-22 parts of modification sulphonation phenolic resin, 8-12 parts of hydroxypropyl azochlorosulfonate acid sodium, 6-10 parts of oleamide hydroxy sulfo lycine, 5-8 parts of trifluoro propyl methyl cyclotrisiloxane, 12-18 parts of acrylamide, 0.02-0.1 parts of ammonium persulfate, nano-titanium dioxide 1- 5 parts, 3-6 parts of sodium bicarbonate；
(2) modification sulphonation phenolic resin is prepared
(a) 1.8-3.2 parts of phenol, 0.9-1.1 parts of dihydric phenol, first are sequentially added in the reaction kettle for being equipped with reflux 1.5-3 parts of aldehyde is warming up to 97-105 DEG C, and 0.02-0.06 parts of 20% hydrochloric acid is added, and reacts 10-15 minutes；
(b) 0.5-1.3 parts of 20% sodium hydroxide solution is added thereto, 1.4-1.7 parts of sulfonating agent is then added, is heated to It 97-105 DEG C, reacts 80-100 minutes under reflux；
(c) 1.4-1.7 parts of sulfonating agent, 0.02-0.09 parts of formaldehyde, organic polymer nano-particle 0.03- is added second 0.07 part, 0.01-0.05 parts of silane coupling agent is heated to 97-105 DEG C, reacts 80-100 minutes under reflux；
(d) 1.4-1.7 parts of sulfonating agent is added in third time, is heated to 97-105 DEG C, reacts 80-100 minutes under reflux；
(e) the 4th 1.4-1.7 parts of sulfonating agent of addition, is heated to 97-105 DEG C, reacts 80-100 minutes under reflux；
(f) after the completion of reacting, modification sulphonation phenolic resin is obtained using spray drying；
(3) sulfonated phenol formaldehyde resin and hydroxypropyl azochlorosulfonate acid sodium prepared by step (2) are mixed under stiring, it is anti-at 50-70 DEG C It answers 10-20 minutes；
(4) oleamide hydroxy sulfo lycine and trifluoro propyl methyl cyclotrisiloxane are added into the product of step (3)；
(5) polyacrylamide nano composite titania material is prepared
Acrylamide, nano-titanium dioxide, sodium bicarbonate and 60-200ml water are added in reactor, stirred evenly, Then ammonium persulfate is added, reacts 1-2 hours, then heats to 70-90 DEG C and reacts 1-2 hours；After reaction, product is through dry It is dry to obtain polyacrylamide nano composite titania material；
(6) polyacrylamide nano composite titania material prepared by step (5) is added to the product of step (4) In, obtain treating agent of drilling mud.
Wherein, the group of the sulfonating agent becomes：18 parts of water, 36.5 parts of formaldehyde, 45.5 parts of sodium pyrosulfite.
The dihydric phenol is one or more in catechol, resorcinol and hydroquinone.
The organic polymer nano-particle is selected from by (methyl) acrylic acid, (methyl) methyl acrylate, (methyl) propylene A kind of monomer polymerization in acetoacetic ester, (methyl) butyl acrylate, (methyl) acrylamide, styrene, sodium p styrene sulfonate Or several monomers are copolymerized generated polymer nano-particle.
The silane coupling agent is selected from gamma-methyl allyl acyloxypropyl trimethoxysilane, γ-methacryloxypropyl third Ethyl triethoxy silicane alkane, vinyltrimethoxysilane, vinyltriethoxysilane, gamma-amino propyl trimethoxy silicane, γ aminopropyltriethoxy silane, γ-glycidoxypropyltrimewasxysilane, three ethoxy of 3- isocyanates propyl It is one or more in base silane.
Advantageous effect
1, modification sulphonation phenolic resin of the invention is suitable for fresh water, brine and the water base mud system of high salinity, has High temperature resistance, salt resistance function, and have certain anticalcium effect, drop high temperature and pressure worry vector it is particularly significant.
2, the hydrophily of sulfonated phenol formaldehyde resin is enhanced using hydroxypropyl azochlorosulfonate acid sodium, hydration is strong, associated water bond energy Height enhances the water solubility of sulfonated phenol formaldehyde resin, effectively improves the high-temperature stability of drilling fluid.
3, so that polyacrylamide and nano-titanium dioxide is formed composite material, reach thickening, filtrate reducing effect, it is especially anti- The effect of high-temperature salt-resistant and reservoir protection and wellbore stability.
4, treating agent of drilling mud of the invention can temperature resistance up to 200 DEG C, mud thermal stability is strong, and conversion is safeguarded and processing Mud is convenient.
5, the additive amount for the treatment of agent of drilling mud of the invention is generally 1.0-3.0%, and additive amount is only similar product 50%, production cost is reduced, and reduce mud usage amount.
6, free from environmental pollution especially suitable for probings, reservoir protections such as the deep stratum Yi Ta, salt cream mud bad grounds.
Specific implementation mode
With reference to embodiment, the present invention is further illustrated.
Prepare modification sulphonation phenolic resin
Embodiment 1
(1) phenol 2.6g, catechol 1.0g, formaldehyde 2.0g are sequentially added in the reaction kettle for being equipped with reflux, 99 DEG C are warming up to, 20% hydrochloric acid 0.03g is added in four times, is reacted 10 minutes, solution becomes milky；
(2) 20% sodium hydroxide solution 0.8g is added thereto, then sulfonating agent is added in the pH value for adjusting reaction solution 1.5g is heated to 99 DEG C, reacts 90 minutes under reflux, and reaction solution becomes clear；Wherein, the group of sulfonating agent becomes：Water 18g, formaldehyde 36.5g, sodium pyrosulfite 45.5g；
(3) sulfonating agent 1.5g, formaldehyde 0.06g, polymethyl methacrylate nano particle is added thereto for the second time 0.05g, gamma-methyl allyl acyloxypropyl trimethoxysilane 0.03g, back flow reaction 90 minutes at 99 DEG C；
(4) sulfonating agent 1.5g, back flow reaction 90 minutes at 99 DEG C are added in third time；
(5) the 4th addition sulfonating agent 1.5g, back flow reaction 90 minutes at 99 DEG C；
(6) after the completion of reacting, modification sulphonation phenolic resin is obtained using spray drying.
Wherein, after sulfonating agent is added every time, the viscosity of the multiple sampling monitoring solution of timing can be mended suitably as viscosity is excessively high Add tap water to control viscosity rise.
Embodiment 2
(1) phenol 3.0g, hydroquinone 1.1g, formaldehyde 2.3g are sequentially added in the reaction kettle for being equipped with reflux, 102 DEG C are warming up to, 20% hydrochloric acid 0.05g is added in four times, is reacted 10 minutes, solution becomes milky；
(2) 20% sodium hydroxide solution 1.2g is added thereto, then sulfonating agent is added in the pH value for adjusting reaction solution 1.6g is heated to 102 DEG C, reacts 90 minutes under reflux, and reaction solution becomes clear；Wherein, the group of sulfonating agent becomes：Water 18g, formaldehyde 36.5g, sodium pyrosulfite 45.5g；
(3) sulfonating agent 1.6g, formaldehyde 0.07g, polystyrene nanoparticle 0.06g, γ-methyl is added thereto for the second time Acryloxypropyl trimethoxy silane 0.04g, back flow reaction 90 minutes at 102 DEG C；
(4) sulfonating agent 1.6g, back flow reaction 90 minutes at 102 DEG C are added in third time；
(5) the 4th addition sulfonating agent 1.6g, back flow reaction 90 minutes at 102 DEG C；
(6) after the completion of reacting, modification sulphonation phenolic resin is obtained using spray drying.
Wherein, after sulfonating agent is added every time, the viscosity of the multiple sampling monitoring solution of timing can be mended suitably as viscosity is excessively high Add tap water to control viscosity rise.
Prepare treating agent of drilling mud
Embodiment 3
(1) sulfonated phenol formaldehyde resin and 10g hydroxypropyl azochlorosulfonate acid sodiums prepared by 18g embodiments 1 are mixed under stiring, at 55 DEG C Reaction 15 minutes；
(2) 8g oleamides hydroxy sulfo lycine and three silica of 6g trifluoro propyl methyl ring are added into the product of step (1) Alkane stirs evenly；
(3) polyacrylamide nano composite titania material is prepared
15g acrylamides, 2g nano-titanium dioxides, 5g sodium bicarbonates and 100ml water are added in reactor, stirring is equal It is even；Then 0.05g ammonium persulfates are added, react 2 hours, then heats to 90 DEG C and reacts 2 hours；After reaction, product passes through It is dried to obtain polyacrylamide nano composite titania material；
(4) polyacrylamide nano composite titania material prepared by step (3) is added to the product of step (2) In, obtain treating agent of drilling mud.
Embodiment 4
(1) modification sulphonation phenolic resin and 10g hydroxypropyl azochlorosulfonate acid sodiums prepared by 20g embodiments 2 are mixed under stiring, 60 DEG C are reacted 15 minutes；
(2) 6g oleamides hydroxy sulfo lycine and three silica of 8g trifluoro propyl methyl ring are added into the product of step (1) Alkane stirs evenly；
(3) polyacrylamide nano composite titania material is prepared
16g acrylamides, 3g nano-titanium dioxides, 4g sodium bicarbonates and 100ml water are added in reactor, stirring is equal It is even；Then 0.03g ammonium persulfates are added, react 2 hours, then heats to 85 DEG C and reacts 2 hours；After reaction, product passes through It is dried to obtain polyacrylamide nano composite titania material；
(4) polyacrylamide nano composite titania material prepared by step (3) is added to the product of step (2) In, obtain treating agent of drilling mud.
Comparative example
Prepare sulfonated phenol formaldehyde resin
Comparative example 1
(1) 1 mole of phenol, 1 mole of formaldehyde and 0.1 molar sodium hydroxide are sequentially added into the cooling of the reflux with blender In the reaction kettle of device, 119 DEG C are stirred 10 minutes, and cooling maintains the temperature at 109 DEG C, then sequentially adds 1 mole of formaldehyde, Jiao Ya As sulfonating agent, sulfonation time is 3 hours, 1 moles of formaldehyde is eventually adding, at 97 DEG C -104 DEG C by 0.5 mole of sodium sulphate, water 40ml Lower back flow reaction 3-4 hours；
(2) viscosity change of observing response object at any time, optionally appropriate supplement water；
(3) cooling at the end of reacting, it is cooled to 60 DEG C of -70 DEG C of dischargings；
(4) dry, obtain sulfonated phenol formaldehyde resin.
Prepare treating agent of drilling mud
Comparative example 2
Other than not using hydroxypropyl azochlorosulfonate acid sodium, treating agent of drilling mud is prepared according to the same manner as in Example 3.
Comparative example 3
Other than not using trifluoro propyl methyl cyclotrisiloxane, drilling well is prepared according to the same manner as in Example 3 Mud conditioner.
Comparative example 4
Other than not using acrylamide, ammonium persulfate and titanium dioxide, prepare according to the same manner as in Example 3 Treating agent of drilling mud.
Wherein, embodiment 1-2 is modification sulphonation phenolic resin prepared according to the methods of the invention；Comparative example 1 is basis Sulfonated phenol formaldehyde resin prepared by routine techniques.Comparative example 2-4 is the brill obtained by one or more ingredients in omission embodiment 3 Well mud conditioner.
Below to embodiment 1-2 and comparative example 1 sulfonated phenol formaldehyde resin prepared and embodiment 3-4 and comparative example 2-4 systems Standby treating agent of drilling mud performance is tested.
Base is starched：4.5 parts by weight of bentonite, 0.5 parts by weight of soda ash, 100 parts by weight of water.
In above-mentioned base slurry, the product of 2% 1-2 of the embodiment of the present invention, embodiment 3-4 and comparative example 1-4 preparations is added, It stirs evenly.According to GB/T 16783.1-2006 standards, the apparent viscosity of testing experiment slurry, yield value, is ingressed at plastic viscosity Power/10-minute gel strength, static filtration and high temperature and high pressure filter loss.Properties test result is shown in Table 1.
Table 1
From the results shown in Table 1, treating agent of drilling mud according to the present invention has good high temperature resistance stability And rheological property, drop high temperature and pressure worry vector is particularly significant, disclosure satisfy that quick, safety and efficient drilling well requirement.

Claims (8)

1. a kind of modification sulphonation phenolic resin, by weight, the modification sulphonation phenolic resin is to be prepared via a method which 's：
(1) 1.8-3.2 parts of phenol, 0.9-1.1 parts of dihydric phenol, formaldehyde are sequentially added in the reaction kettle for being equipped with reflux 1.5-3 parts, it is warming up to 97-105 DEG C, 0.02-0.06 parts of 20% hydrochloric acid is added, is reacted 10-15 minutes；
(2) 0.5-1.3 parts of 20% sodium hydroxide solution is added thereto, 1.4-1.7 parts of sulfonating agent is then added, is heated to 97- It 105 DEG C, reacts 80-100 minutes under reflux；
(3) 1.4-1.7 parts of sulfonating agent, 0.02-0.09 parts of formaldehyde, organic polymer nano-particle 0.03-0.07 is added second Part, 0.01-0.05 parts of silane coupling agent, back flow reaction 80-100 minutes at 97-105 DEG C；
(4) 1.4-1.7 parts of sulfonating agent is added in third time, back flow reaction 80-100 minutes at 97-105 DEG C；
(5) the 4th 1.4-1.7 parts of sulfonating agents of addition, back flow reaction 80-100 minutes at 97-105 DEG C；
(6) after the completion of reacting, modification sulphonation phenolic resin is obtained using spray drying；
Wherein, the group of the sulfonating agent becomes：18 parts of water, 36.5 parts of formaldehyde, 45.5 parts of sodium pyrosulfite；Wherein, described organic Polymer nano-particle is selected from by (methyl) acrylic acid, (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) propylene A kind of monomer polymerization or the copolymerization of several monomers in acid butyl ester, (methyl) acrylamide, styrene, sodium p styrene sulfonate are given birth to At polymer nano-particle.
2. modification sulphonation phenolic resin according to claim 1, wherein the dihydric phenol is selected from catechol, isophthalic It is one or more in diphenol and hydroquinone.
3. modification sulphonation phenolic resin according to claim 1, wherein the silane coupling agent is selected from γ-methyl-prop Alkene monomethacryloxypropyl trimethoxy silane, gamma-methyl allyl acyloxypropyl triethoxysilane, vinyltrimethoxysilane, second Alkenyl triethoxysilane, gamma-amino propyl trimethoxy silicane, γ aminopropyltriethoxy silane, γ-glycidol It is one or more in oxygroup propyl trimethoxy silicane, 3- isocyanate propyl triethoxysilanes.
4. a kind for the treatment of agent of drilling mud is grouped as by the group of following parts by weight：
16-22 parts of claim 1-3 any one of them modification sulphonation phenolic resin,
8-12 parts of hydroxypropyl azochlorosulfonate acid sodium,
6-10 parts of oleamide hydroxy sulfo lycine,
5-8 parts of trifluoro propyl methyl cyclotrisiloxane,
12-18 parts of acrylamide,
0.02-0.1 parts of ammonium persulfate,
1-5 parts of nano-titanium dioxide,
3-6 parts of sodium bicarbonate.
5. treating agent of drilling mud according to claim 4 is grouped as by the group of following parts by weight：
18 parts of modification sulphonation phenolic resin,
10 parts of hydroxypropyl azochlorosulfonate acid sodium,
8 parts of oleamide hydroxy sulfo lycine,
6 parts of trifluoro propyl methyl cyclotrisiloxane,
15 parts of acrylamide,
0.05 part of ammonium persulfate,
2 parts of nano-titanium dioxide,
5 parts of sodium bicarbonate.
6. treating agent of drilling mud according to claim 4 or 5, wherein the grain size of nano-titanium dioxide be 20~ 100nm。
7. a kind of preparation method of the treating agent of drilling mud described in claim 4, including：
(1) sulfonated phenol formaldehyde resin is prepared
(a) 1.8-3.2 parts of phenol, 0.9-1.1 parts of dihydric phenol, formaldehyde are sequentially added in the reaction kettle for being equipped with reflux 1.5-3 parts, it is warming up to 97-105 DEG C, 0.02-0.06 parts of 20% hydrochloric acid is added, is reacted 10-15 minutes；
(b) 0.5-1.3 parts of 20% sodium hydroxide solution is added thereto, 1.4-1.7 parts of sulfonating agent is then added, is heated to 97- It 105 DEG C, reacts 80-100 minutes under reflux；
(c) 1.4-1.7 parts of sulfonating agent, 0.02-0.09 parts of formaldehyde, organic polymer nano-particle 0.03-0.07 is added second Part, 0.01-0.05 parts of silane coupling agent, back flow reaction 80-100 minutes at 97-105 DEG C；
(d) 1.4-1.7 parts of sulfonating agent is added in third time, back flow reaction 80-100 minutes at 97-105 DEG C；
(e) the 4th 1.4-1.7 parts of sulfonating agent of addition, back flow reaction 80-100 minutes at 97-105 DEG C；
(f) after the completion of reacting, modification sulphonation phenolic resin is obtained using spray drying；
Wherein, the group of the sulfonating agent becomes：18 parts of water, 36.5 parts of formaldehyde, 45.5 parts of sodium pyrosulfite；
(2) modification sulphonation phenolic resin and hydroxypropyl azochlorosulfonate acid sodium prepared by step (1) are mixed under stiring, it is anti-at 50-70 DEG C It answers 10-20 minutes；
(3) oleamide hydroxy sulfo lycine and trifluoro propyl methyl cyclotrisiloxane are added into the product of step (2)；
(4) polyacrylamide nano composite titania material is prepared
Acrylamide, nano-titanium dioxide, sodium bicarbonate and 60-200ml water are added in reactor, stirred evenly, then Ammonium persulfate is added, reacts 1-2 hours, then heats to 70-90 DEG C and reacts 1-2 hours；After reaction, product is through dry To polyacrylamide nano composite titania material；
(5) polyacrylamide nano composite titania material prepared by step (4) is added in the product of step (3), is obtained To treating agent of drilling mud；
Wherein, the organic polymer nano-particle is selected from by (methyl) acrylic acid, (methyl) methyl acrylate, (methyl) propylene A kind of monomer polymerization in acetoacetic ester, (methyl) butyl acrylate, (methyl) acrylamide, styrene, sodium p styrene sulfonate Or several monomers are copolymerized generated polymer nano-particle.
8. according to the preparation method described in claim 7, wherein
The dihydric phenol is one or more in catechol, resorcinol and hydroquinone；
The silane coupling agent is selected from gamma-methyl allyl acyloxypropyl trimethoxysilane, gamma-methyl allyl acyloxypropyl three Ethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, gamma-amino propyl trimethoxy silicane, γ- Aminopropyltriethoxywerene werene, γ-glycidoxypropyltrimewasxysilane, 3- isocyanates propyl-triethoxysilicanes It is one or more in alkane.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104130361A (en) * 2014-08-13 2014-11-05 江苏苏博特新材料股份有限公司 Preparation method of highly-sulfonated and highly-concentrated aliphatic superplasticizer
CN104788634A (en) * 2015-05-08 2015-07-22 天津中油渤星工程科技有限公司 Preparation method of high-temperature-resistant modified sulfonated phenol formaldehyde resin for drilling fluids
CN104892877A (en) * 2015-06-09 2015-09-09 中国林业科学研究院林产化学工业研究所 Phenolated lignin modified expandable resorcinol-phenol-formaldehyde resin and preparation method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104130361A (en) * 2014-08-13 2014-11-05 江苏苏博特新材料股份有限公司 Preparation method of highly-sulfonated and highly-concentrated aliphatic superplasticizer
CN104788634A (en) * 2015-05-08 2015-07-22 天津中油渤星工程科技有限公司 Preparation method of high-temperature-resistant modified sulfonated phenol formaldehyde resin for drilling fluids
CN104892877A (en) * 2015-06-09 2015-09-09 中国林业科学研究院林产化学工业研究所 Phenolated lignin modified expandable resorcinol-phenol-formaldehyde resin and preparation method thereof

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