CN108409923B - Macromolecule complex and preparation method and application - Google Patents

Macromolecule complex and preparation method and application Download PDF

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CN108409923B
CN108409923B CN201810187118.8A CN201810187118A CN108409923B CN 108409923 B CN108409923 B CN 108409923B CN 201810187118 A CN201810187118 A CN 201810187118A CN 108409923 B CN108409923 B CN 108409923B
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initiator
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CN108409923A (en
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邱正松
候伟超
钟汉毅
夏孝杰
王洪磊
黄维安
赵欣
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China University of Petroleum East China
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    • 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
    • C08F289/00—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds not provided for in groups C08F251/00 - C08F287/00
    • 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

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Abstract

The present invention relates to oil and gas well drilling technical fields, and in particular to a kind of macromolecule complex and preparation method and application.Macromolecule complex disclosed by the invention includes macromolecular ligand and central ion, macromolecular ligand is modified lignin mahogany sulfonate, central ion is copper ion, wherein, monomer of the modified lignin mahogany sulfonate by lignosulfonates and containing functional group is graft-polymerized, the monomer containing functional group includes the monomer of phosphinylidyne-containing amine group and/or sulfonic acid group and the monomer of carboxy-containing acid group, and the part that modified lignin mahogany sulfonate and copper ion are coordinated has planar topologies.Add the drilling fluid of macromolecule complex of the present invention, with stronger hydrophily, elecrtonegativity and temperature resistance salt resistance ability, make organic salt drilling fluid in drilling process, performance is more stable, it is easy to adjust, and then meets the drillng operation needs of the complex stratum conditions such as high temperature and pressure saliferous cream.

Description

Macromolecule complex and preparation method and application
Technical field
The present invention relates to oil and gas well drilling technical fields, and in particular to a kind of macromolecule complex and preparation method And application.
Background technique
With the drilling to deep formation, drillng operation bores a possibility that meeting the bad grounds such as high temperature and pressure saliferous cream will be by Edge up height.The bad grounds such as the mud shale that organic salt drilling fluid disperses in deep-well, ultradeep well and big section saline bed and easy aquation There is unique advantage when drilling.But common water-base drilling fluid regulator cannot be preferably organic suitable for high-temperature high-density Salt drilling fluid normally results in inorganic agent failure under the conditions of high temperature, high salinity.In addition, being aggravated using barite organic Salt drilling fluid still has thickening and the problem of viscosity, shear force reduce after high temperature ageing under the conditions of high solid loading.It therefore, is suitable High-temperature high-density organic salt drilling fluid system is answered, needs to develop the drilling fluid conditioner for capableing of temperature resistance salt tolerant.
Summary of the invention
The purpose of the invention is to overcome organic salt drilling fluid of the existing technology to increase under the conditions of high solid loading The problem of viscosity, shear force reduce after thick and high temperature ageing provides a kind of macromolecule complex and preparation method and application.
To achieve the goals above, first aspect present invention discloses a kind of macromolecule complex, including macromolecular ligand And central ion, macromolecular ligand are modified lignin mahogany sulfonate, central ion is copper ion, wherein modified lignin resin sulfonic acid Monomer of the salt by lignosulfonates and containing functional group is graft-polymerized, and the monomer containing functional group includes containing The monomer of the monomer and carboxy-containing acid group of amide group and/or sulfonic acid group, modified lignin mahogany sulfonate and copper ion coordination Part has planar topologies.
Second aspect of the present invention discloses a kind of method for preparing macromolecule complex, this method comprises: in polymerisation in solution Under reaction condition, initiator is added in the mixed solution of lignosulfonates, mantoquita and the monomer containing functional group and is carried out Reaction, the monomer containing functional group includes monomer and the carboxy-containing acid group of phosphinylidyne-containing amine group and/or sulfonic acid group Monomer.
Third aspect present invention discloses macromolecule complex made from the preparation method.
Fourth aspect present invention discloses application of the macromolecule complex in drilling fluid
By compared with prior art, the invention has the following advantages that
1) central ion of macromolecule complex of the invention is copper ion, and macromolecule complex has flat topology knot Structure；Gained macromolecule complex molecule has strongly hydrophilic, strong elecrtonegativity and certain chain rigidity after introducing functional group.
2) drilling fluid for adding macromolecule complex of the invention has stronger temperature resistance salt resistance ability, makes organic salt drilling well For liquid in drilling process, performance is more stable, is easy to adjust, and can satisfy the complex stratum conditions such as drilling high temperature and pressure saliferous cream Drillng operation need；Additionally one layer of stable solvation film can be formed on the solid phase particles surface of organic salt drilling fluid, Reduce the interior frictional resistance of solid phase particles, there is certain lubricity.
3) the temperature resistance ability of product of the present invention is strong, and the temperature resistance of organic salt drilling fluid system can be enable after addition product of the present invention Power is increased to 200 DEG C or so.
Detailed description of the invention
Fig. 1 is the schematic diagram of lignosulfonates graft in the macromolecule complex A of embodiment 1；
Fig. 2 is the signal for the complex that lignosulfonates and copper ion are formed in the macromolecule complex A of embodiment 1 Figure.
Specific embodiment
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more New numberical range, these numberical ranges should be considered as specific open herein.
First aspect present invention discloses a kind of macromolecule complex, including macromolecular ligand and central ion, feature It is, macromolecular ligand is modified lignin mahogany sulfonate, and central ion is copper ion, wherein modified lignin mahogany sulfonate is by wood Mahogany sulfonate and monomer containing functional group are graft-polymerized, and the monomer containing functional group includes amide-containing The monomer of the monomer and carboxy-containing acid group's (carboxyl) of group and/or sulfonic acid group, modified lignin mahogany sulfonate and copper ion coordination Part has planar topologies.
" planar topologies ", which refer to, only considers the shape of atom or intermolecular relative positional relationship without considering them With the planar structure of size.
Lignosulfonates are the natural polymers that molecular weight is 1000-30000.By the leftover bits and pieces of production paper pulp It after fermented extraction alcohol, then is formed with alkali neutralization, mainly there is calcium lignosulfonate, sodium lignin sulfonate, lignin sulfonic acid Magnesium etc., wherein most widely used calcium lignosulfonate is exactly to use made of lignosulfite.Lignin of the present invention Sulfonate can be the conventional selection of this field, preferably calcium lignosulfonate and/or sodium lignin sulfonate, further preferably Ground, calcium lignosulfonate are Eucalyptus calcium lignosulfonate, and sodium lignin sulfonate is Eucalyptus sodium lignin sulfonate.
Heretofore described central ion is copper ion, Hybridization type dsp2Type, the cooperation species of formation Type is inner-orbital complex, and intensity is higher than outer-orbital complex, and temperature tolerance is stronger, and steric configuration is planar shape, to make Macromolecule complex forms the planar topologies centered on copper ion in the structure, is more advantageous to macromolecule complex molten Form is sprawled in liquid, enhancing macromolecule complex solid particles surface adsorption capacity, thus in solid particles surface shape At stablizing and having electronegative solvent hydration shell, interior frictional resistance of the solid particle under flow regime is reduced, is enhanced organic The settlement stability performance of solid phase particles in salt drilling fluid.
Copper ion of the present invention and macromolecular ligand weight ratio are preferably 1:42.5-51.It is of the present invention to contain acyl The monomer of amine groups and/or sulfonic acid group can be the conventional selection of this field, preferably 2- acrylamido-2- methyl-1- At least one of propane sulfonic acid, acrylamide and vinyl sulfonic acid sodium, further preferably 2- acrylamido-2- methyl-1-the third Sulfonic acid.
The monomer of carboxy-containing acid group of the present invention can be this field conventional selection, preferably acrylic acid and/or Methacrylic acid.
The monomer of above-mentioned phosphinylidyne-containing amine group and/or sulfonic acid group, wherein including strong anionic property, water-soluble sulfonic group The amide group of group and/or hydrolytic stability, antiacid, alkali resistant and good thermal stability, enhances lignosulfonate molecules Rigidity and thermal stability.The monomer of carboxy-containing acid group contains strongly hydrophilic and electronegative carboxylic acid aquation group, improves wooden The adsorption capacity of plain sulfonate is easy to adsorb to form solvation film in solid particles surface, and then by strong elecrtonegativity and other Particle forms electrostatic repulsion, enhances the stability of organic salt drilling fluid.
The molar ratio of the monomer of the monomer and carboxy-containing acid group of above-mentioned phosphinylidyne-containing amine group and/or sulfonic acid group is preferably 1: 4-6。
Second aspect of the present invention discloses a kind of method for preparing macromolecule complex, this method comprises: in polymerisation in solution Under reaction condition, initiator is added in the mixed solution of lignosulfonates, mantoquita and the monomer containing functional group and is carried out Reaction, the monomer containing functional group includes the monomer of phosphinylidyne-containing amine group and/or sulfonic acid group and the list of carboxy-containing acid group Body.
Preferably, the copper ion in above-mentioned mantoquita, lignosulfonates, the monomer containing functional group and initiator Weight ratio is 1:23.5-28.5:18.5-21:0.5-1.5.
Preferably, lignosulfonates be at least one of calcium lignosulfonate and/or sodium lignin sulfonate, further Preferably, calcium lignosulfonate is Eucalyptus calcium lignosulfonate, and sodium lignin sulfonate is Eucalyptus sodium lignin sulfonate.
Preferably, the molar ratio of the monomer of the monomer and carboxy-containing acid group of phosphinylidyne-containing amine group and/or sulfonic acid group is 1:4- 6。
Preferably, the monomer of phosphinylidyne-containing amine group and/or sulfonic acid group is 2-acrylamido-2-methyl-1-propanesulfonic acid, third At least one of acrylamide and vinyl sulfonic acid sodium, further preferably 2-acrylamido-2-methyl-1-propanesulfonic acid, it is described The monomer of carboxy-containing acid group is acrylic monomers and/or methacrylic acid.
Preferably, the initiator is persulfuric acid salt initiator, it is highly preferred that the initiator is potassium peroxydisulfate, mistake At least one of sodium sulphate and ammonium persulfate.
Preferably, it is 50-90 DEG C, time 1-3h that the condition of solution polymerization, which includes: temperature, inert atmosphere.
By the preparation method of above-mentioned preferred macromolecule complex, obtained macromolecule complex has better temperature resistance Anti-salt property.
Initiator is added in the mixed solution of lignosulfonates, mantoquita and the monomer containing functional group and is reacted When, the engagement sequence of initiator and lignosulfonates, mantoquita, monomer containing functional group is not required particularly, but It is, in order to obtain the more excellent macromolecule complex of performance, functional group first to be contained into lignosulfonates, mantoquita and part Monomer and initiator contact, then remaining monomer and initiator containing functional group is added dropwise.Pass through addition gradually in this way Monomer and initiator solution can make lignosulfonates have better grafting rate, thus the modified lignin resin sulphur made Hydrochlorate has more sulfonic acid groups, amide group and carboxylic acid group, so that macromolecule complex has better temperature resistance Anti-salt property.
Therefore, the preferred preparation method of macromolecule complex of the present invention includes:
(1) monomer containing functional group is configured to monomer solution, it is molten that lignosulfonates, mantoquita are made into raw material mixing Liquid, initiator are configured to initiator solution；
(2) under an inert atmosphere, partial monosomy solution and part initiator solution, heating are added into raw material mixed solution To 50-60 DEG C, remaining monomer solution is slowly added dropwise at such a temperature, and (drop rate can be 2- with remaining initiator solution 4mL/min), it is warming up to 80-90 DEG C after the two drips, and reacts 1.5-2.5h at this temperature, in the step, is first added Partial monosomy solution and the residual monomer solution that is added afterwards between weight ratio be preferably 1:3-5, the part being first added is caused Weight ratio between agent solution and the remaining initiator solution being added afterwards is preferably 1:6-8；
(3) reaction product for using alkali neutralization step (2) is separated by solid-liquid separation and dry.
In above-mentioned steps (1), the concentration of each solution is not required particularly, for example, containing functional base in monomer solution The concentration of the monomer of group can be 0.9-1.1g/mL；The concentration of lignosulfonates and mantoquita can be in raw material mixed solution 0.4-0.55g/mL；The concentration of initiator can be 0.04-0.06g/mL in initiator solution.
Alkali described in above-mentioned step (3) can be sodium hydroxide and/or potassium hydroxide, the weight and sulfomethylated lignin of alkali The weight ratio of hydrochlorate is 1:1.46-1.58.
It is usually water that the solvent of solution is prepared in the preparation method of macromolecule complex.
Inert atmosphere in the present invention is usually provided by nitrogen, argon gas etc..
Third aspect present invention discloses the macromolecule complex as made from above-mentioned preparation method.
Fourth aspect present invention discloses application of the above-mentioned macromolecule complex in drilling fluid.
The present invention will be described in detail by way of examples below.
Embodiment 1
1) by the deionized water dissolving of the 2-acrylamido-2-methyl-1-propanesulfonic acid monomer 40ml of 15g, then to its The middle acrylic monomers that 25g is added, is uniformly mixing to obtain the monomer mixed solution of 1g/ml；
2) potassium peroxydisulfate of 2g is obtained into 0.05g/ml initiator solution with the deionized water dissolving of 40ml；
3) the Eucalyptus calcium lignosulfonate of 52g (manufacturer: Aladdin, the trade mark: C106637, similarly hereinafter) is slowly added into In the deionized water of 120ml, after the completion of to be dissolved, the copper sulphate of 5g is added, stirs evenly, obtains the mixing of 0.48g/ml raw material Liquid；
4) under nitrogen protection, raw material mixed liquor is put into reaction kettle, 1/4 parts by weight are then added while stirring The above-mentioned initiator solution of above-mentioned monomer mixed solution and 1/7 parts by weight, then heats to 60 DEG C, is slowly added dropwise at such a temperature (rate of addition 2mL/min) remaining monomer mixed solution and initiator solution are warming up to 90 DEG C of reactions after the two adds 2.5h obtains reaction mixture；
5) after neutralizing reaction mixture with 33.54g sodium hydroxide, after filtering, drying, crushing, macromolecular cooperation is obtained Object A.Fig. 1 is the schematic diagram of lignosulfonates graft.Fig. 2 is the complex that lignosulfonates and copper ion are formed Schematic diagram.
Embodiment 2
1) by the deionized water dissolving of the 2-acrylamido-2-methyl-1-propanesulfonic acid monomer 42ml of 13g, then to its The middle acrylic monomers that 26g is added, is uniformly mixing to obtain the monomer mixed solution of 0.93g/ml；
2) potassium peroxydisulfate of 1.8g is obtained into 0.045g/ml initiator solution with the deionized water dissolving of 40ml；
3) the Eucalyptus calcium lignosulfonate of 50g is added in batches in the deionized water of 120ml, after the completion of to be dissolved, is added The copper sulphate for entering 5.1g, stirs evenly, and obtains 0.46g/ml raw material mixed liquor；
4) under nitrogen protection, raw material mixed liquor is put into reaction kettle, 1/5 parts by weight are then added while stirring The above-mentioned initiator solution of above-mentioned monomer mixed solution and 1/8 parts by weight, then heats to 50 DEG C, is slowly added dropwise at such a temperature (rate of addition 3mL/min) remaining monomer mixed solution and initiator solution are warming up to 80 DEG C of reactions after the two adds 2.0h obtains reaction mixture；
5) after neutralizing reaction mixture with 33.54g sodium hydroxide, after drying, crushing, macromolecule complex B is obtained.Its In, the schematic diagram of lignosulfonates graft is similar with Fig. 1, and the complex that lignosulfonates and copper ion are formed shows It is intended to similar with Fig. 2.
Embodiment 3
1) by the deionized water dissolving of the 2-acrylamido-2-methyl-1-propanesulfonic acid monomer 40ml of 16g, then to its The middle acrylic monomers that 24g is added, is uniformly mixing to obtain the monomer mixed solution of 1g/ml；
2) potassium peroxydisulfate of 2.12g is obtained into the initiator solution of 0.053g/ml with the deionized water dissolving of 40ml；
3) the Eucalyptus calcium lignosulfonate of 54g is added in batches in the deionized water of 120ml, after the completion of to be dissolved, is added The copper sulphate for entering 4.9g, stirs evenly, and obtains 0.49g/ml raw material mixed liquor；
4) under the protection of nitrogen, raw material mixed liquor is put into reaction kettle, 1/6 parts by weight are then added while stirring Above-mentioned monomer mixed solution and 1/9 parts by weight above-mentioned initiator solution, then heat to 60 DEG C, be slowly added dropwise at such a temperature (rate of addition 4mL/min) remaining monomer mixed solution and initiator solution, are warming up to 90 DEG C, in nitrogen after the two adds Protection is lower to react 1.5h, obtains reaction mixture；
5) after neutralizing reaction mixture with 33.48g potassium hydroxide, after filtering, drying, crushing, macromolecular cooperation is obtained Object C, wherein the schematic diagram of lignosulfonates graft is similar with Fig. 1, the cooperation that lignosulfonates and copper ion are formed The schematic diagram of object is similar with Fig. 2.
Embodiment 4
Macromolecule complex is prepared according to the method for embodiment 1, unlike, 2- acrylamido -2- first in step (1) The dosage of base -1- sulphonic acid monomer is 20g, and the dosage of acrylic acid is 20g, obtains macromolecule complex D.
Embodiment 5
Macromolecule complex is prepared according to the method for embodiment 1, unlike, the dosage of Eucalyptus calcium lignosulfonate is 60g, the dosage of potassium peroxydisulfate are 1g, so that the copper ion, lignosulfonates, organic functions monomer, initiator in mantoquita Mass ratio is 1:40:20:0.5, obtains macromolecule complex E.
Embodiment 6
Macromolecule complex is prepared according to the method for embodiment 1, unlike, in step (4), it is directly added into whole lists Body mixed liquor and initiator solution obtain macromolecule complex F.
Embodiment 7
Macromolecule complex is prepared according to the method for embodiment 1, unlike, acrylic monomers replaces with 4- penetenoic acid list Body obtains macromolecule complex G.
Embodiment 8
Macromolecule complex is prepared according to the method for embodiment 1, unlike, 2- acrylamido -2- the-the third sulphur of methyl-1 Acid replaces with vinyl sulfonic acid sodium, obtains macromolecule complex H.
Comparative example 1
Macromolecule complex is prepared according to the method for embodiment 1, is not both, and copper sulphate replaces with ferric sulfate, is divided greatly Sub- complex I.
Test case 1
(1) the macromolecule complex A-I that testing example and comparative example provide respectively is 2.0g/cm in density3Organic salt Application effect in drilling fluid.
Configuration density 2.0g/cm first3Organic salt drilling fluid (solute include following component (be with the total weight of solute Benchmark): 2 weight % attapulgites (producer: Fei Zhou new material Co., Ltd, trade mark FZ-80)+0.5 weight %NaCO3+ 0.2 weight Measure %NaOH+1 weight % thickening fluid loss additive (producer: snow teflon, trade mark Driscal)+4% weight sulfonated phenol formaldehyde resin (factory Family: Shi great Creative Technology Ltd., trade mark SD102) (producer: Shi great Creative Science and Technology Co. Ltd is limited for+4% weight sulfonated phenol formaldehyde resin Company, trade mark SD202)+3% weight sulfonated gilsonite (producer: snow teflon, trade mark Soltex)+50 weight %KCOOH+32.3 weight % barite (producer: West China miberal powder Co., Ltd, trade mark api class barite) 500mL is measured, is then matched respectively to without macromolecular It closes the organic salt drilling fluid of object and is added to the sample solution of 0.8 weight % macromolecule complex, stirred in the speed of 8000r/min After mixing 20min, it is tested for the property at room temperature, meanwhile, it is tested for the property again after 200 DEG C of heat rolling 16h, wherein AV (is bored The apparent viscosity of well liquid) by six fast rotary viscometer measurements, PV (plastic viscosity of drilling fluid) passes through six fast rotational viscometers Measurement, YP/PV=(AV-PV)/PV are ratio of dynamic shear force/yield value to plastic viscosity, and FL (filter loss) is committed a breach of etiquette measurement by middle filters pressing.Test result such as 1 institute of table Show:
Table 1
(2) the macromolecule complex sample A-I that testing example and comparative example provide respectively is 2.3g/cm in density3Have Application effect in machine salt drilling fluid.
Configuration density 2.3g/cm first3Organic salt drilling fluid (the same step of solute (1)) 500mL, then respectively to being free of The organic salt drilling fluid of macromolecule complex and the sample solution for being added to 0.8 weight % macromolecule complex, in 8000r/min Speed stirring 20min after, be tested for the property at room temperature, meanwhile, 200 DEG C heat rolling 16h after be tested for the property again, survey Test result is as shown in table 2:
Table 2
Alphabetical meaning in table are as follows: AV: the apparent viscosity of drilling fluid, PV: the plastic viscosity of drilling fluid, FL: filter loss, YP/ PV: ratio of dynamic shear force/yield value to plastic viscosity.
It is compared with the property of drilling fluid for not adding macromolecule complex it is found that not adding macromolecular by addition 0.8%A-C Viscosity is larger at normal temperature for the drilling fluid of complex, and viscosity is very low after 200 DEG C, heat rolling 16h, and it is impossible to meet drilling fluid scenes Demand, and be added to the drilling fluid of 0.8% macromolecule complex A-C viscosity reduce at normal temperature, 200 DEG C, heat rolling 16h still Be able to maintain certain viscosity, meet the demand of drilling fluid at high temperature, be still able to maintain after high temperature ageing good rheological characteristic with Thixotropy.Meanwhile the drilling fluid of 0.8% macromolecule complex A-C is added in 2.0g/cm3And 2.3/cm3Highdensity item The above performance can be showed under part, it was demonstrated that macromolecule complex of the invention is suitable for highdensity organic salt drilling fluid.
It is compared by addition 0.8%A-C and the property of drilling fluid for adding 0.8% macromolecule complex D-H it is found that in mantoquita Copper ion, lignosulfonates, the monomer containing functional group and initiator weight ratio be 1:23.5-28.5:18.5- The molar ratio of the monomer of the monomer and carboxy-containing acid group of 21:0.5-1.5, phosphinylidyne-containing amine group and/or sulfonic acid group is 1:4-6, system For Preparation Method according to preferred embodiment of the invention, the monomer containing functional group uses preferred compound, by limiting the above item The drilling fluid that the macromolecular ligand of part preparation is added has better temperature resistance salt resistant character.
By addition 0.8%A-H and 0.8% macromolecule complex I comparison is added it is found that the central ion of complex is copper When ion, macromolecule complex is added in drilling fluid, and drilling fluid has better temperature resistance salt tolerance.
In summary, the drilling fluid of macromolecule complex of the present invention, which is added, has good thermo-salt resistance Energy.
The preferred embodiment of the present invention has been described above in detail, and still, the present invention is not limited thereto.In skill of the invention In art conception range, can with various simple variants of the technical solution of the present invention are made, including each technical characteristic with it is any its Its suitable method is combined, and it should also be regarded as the disclosure of the present invention for these simple variants and combination, is belonged to Protection scope of the present invention.

Claims (13)

1. a kind of application of macromolecule complex in organic salt drilling fluid, including macromolecular ligand and central ion, feature It is, macromolecular ligand is modified lignin mahogany sulfonate, and central ion is copper ion, the weight ratio of copper ion and macromolecular ligand For 1:42.5-51, wherein monomer of the modified lignin mahogany sulfonate by lignosulfonates and containing functional group be graft-polymerized and At the monomer containing functional group includes the monomer of phosphinylidyne-containing amine group and/or sulfonic acid group and the list of carboxy-containing acid group The monomer of body, the phosphinylidyne-containing amine group and/or sulfonic acid group is 2-acrylamido-2-methyl-1-propanesulfonic acid and vinyl sulfonic acid At least one of sodium, the monomer of the carboxy-containing acid group are acrylic acid and/or methacrylic acid, phosphinylidyne-containing amine group and/or sulphur The molar ratio of the monomer of the monomer and carboxy-containing acid group of acid groups is 1:4-6, what modified lignin mahogany sulfonate and copper ion were coordinated Part has planar topologies；
The preparation method of the macromolecule complex includes: that sulfomethylated lignin is added in initiator under the conditions of solution polymerization It is reacted in the mixed solution of hydrochlorate, mantoquita and the monomer containing functional group, the monomer containing functional group includes The monomer of the monomer and carboxy-containing acid group of phosphinylidyne-containing amine group and/or sulfonic acid group, wherein first by lignosulfonates, mantoquita Monomer and initiator with part containing functional group contact, then remaining monomer and initiator containing functional group is added dropwise.
2. application according to claim 1, wherein the lignosulfonates are calcium lignosulfonate and/or lignin Sodium sulfonate.
3. application according to claim 2, wherein calcium lignosulfonate is Eucalyptus calcium lignosulfonate, lignin sulfonic acid Sodium is Eucalyptus sodium lignin sulfonate.
4. application according to claim 1, wherein the monomer of the phosphinylidyne-containing amine group and/or sulfonic acid group is 2- propylene Amide groups-2- methyl-1-propane sulfonic acid.
5. application according to claim 1, wherein copper ion, lignosulfonates in mantoquita contain functional group The weight ratio of monomer and initiator is 1:23.5-28.5:18.5-21:0.5-1.5.
6. application according to claim 1, wherein the monomer and carboxy-containing acid group of phosphinylidyne-containing amine group and/or sulfonic acid group Monomer molar ratio be 1:4-6.
7. application according to claim 1, wherein the initiator is persulfuric acid salt initiator.
8. application according to claim 7, wherein the initiator is in potassium peroxydisulfate, ammonium persulfate and sodium peroxydisulfate At least one.
9. application according to claim 1, wherein the condition of solution polymerization includes: that temperature is 50-90 DEG C, the time For 1-3h, inert atmosphere.
10. application according to claim 1, wherein the described method includes:
(1) monomer containing functional group being configured to monomer solution, lignosulfonates and mantoquita are made into raw material mixed solution, Initiator is configured to initiator solution；
(2) under an inert atmosphere, partial monosomy solution and part initiator solution are added into raw material mixed solution, is warming up to 50-60 DEG C, remaining monomer solution and remaining initiator solution are slowly added dropwise at such a temperature, heats up after the two drips To 80-90 DEG C, and 1.5-2.5h is reacted at this temperature；
(3) reaction product for using alkali neutralization step (2) is separated by solid-liquid separation and dry.
11. application according to claim 10, wherein in step (2), the partial monosomy solution that is first added be added afterwards Weight ratio between residual monomer solution is 1:3-5.
12. application according to claim 11, wherein the part initiator solution being first added in step (2) and rear addition Remaining initiator solution between weight ratio be 1:6-8.
13. application according to claim 10, wherein alkali described in step (3) is sodium hydroxide and/or potassium hydroxide.
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CN116041005B (en) * 2022-12-05 2023-08-11 潮州市金嘉达陶瓷实业有限公司 Cement mixed with ceramic fragments and good in freezing resistance and preparation method thereof

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CN1110707A (en) * 1995-02-11 1995-10-25 毛伟汉 Diluent of drilling liquid
CN1840604A (en) * 2005-12-01 2006-10-04 天津科技大学 Process for preparing drilling fluid thinner by modification of alkaline pulp black liquor
CN106381137A (en) * 2016-09-05 2017-02-08 西安石油大学 Method for improving dissolvability of glycan drilling fluid treatment agent

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1110707A (en) * 1995-02-11 1995-10-25 毛伟汉 Diluent of drilling liquid
CN1840604A (en) * 2005-12-01 2006-10-04 天津科技大学 Process for preparing drilling fluid thinner by modification of alkaline pulp black liquor
CN106381137A (en) * 2016-09-05 2017-02-08 西安石油大学 Method for improving dissolvability of glycan drilling fluid treatment agent

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