WO2022126907A1 - 取代的硬葡聚糖、其制造方法及其应用 - Google Patents

取代的硬葡聚糖、其制造方法及其应用 Download PDF

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WO2022126907A1
WO2022126907A1 PCT/CN2021/083303 CN2021083303W WO2022126907A1 WO 2022126907 A1 WO2022126907 A1 WO 2022126907A1 CN 2021083303 W CN2021083303 W CN 2021083303W WO 2022126907 A1 WO2022126907 A1 WO 2022126907A1
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chemical formula
substituent
substituted
scleroglucan
represented
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PCT/CN2021/083303
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English (en)
French (fr)
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司西强
王中华
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中国石油化工股份有限公司
中石化石油工程技术服务有限公司
中石化中原石油工程有限公司钻井工程技术研究院
中石化中原石油工程有限公司
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Priority to US18/253,874 priority Critical patent/US20240018275A1/en
Publication of WO2022126907A1 publication Critical patent/WO2022126907A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
    • C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
    • C08B37/0024—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid beta-D-Glucans; (beta-1,3)-D-Glucans, e.g. paramylon, coriolan, sclerotan, pachyman, callose, scleroglucan, schizophyllan, laminaran, lentinan or curdlan; (beta-1,6)-D-Glucans, e.g. pustulan; (beta-1,4)-D-Glucans; (beta-1,3)(beta-1,4)-D-Glucans, e.g. lichenan; Derivatives thereof
    • 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
    • C08F251/00—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
    • 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
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/06—Hydrocarbons
    • C08F212/08—Styrene
    • 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
    • C08F220/00—Copolymers 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
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/04—Acids; Metal salts or ammonium salts thereof
    • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
    • 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
    • C08F220/00—Copolymers 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
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/52—Amides or imides
    • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F220/56—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
    • C08F220/00—Copolymers 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
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/52—Amides or imides
    • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F220/58—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing oxygen in addition to the carbonamido oxygen, e.g. N-methylolacrylamide, N-(meth)acryloylmorpholine
    • 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
    • C08F226/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
    • C08F226/06—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a heterocyclic ring containing nitrogen
    • C08F226/10—N-Vinyl-pyrrolidone
    • 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
    • C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
    • C08F230/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
    • C08F230/08—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L5/00—Compositions of polysaccharides or of their derivatives not provided for in groups C08L1/00 or C08L3/00
    • 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
    • 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
    • C09K8/04—Aqueous well-drilling compositions
    • C09K8/14—Clay-containing compositions
    • C09K8/18—Clay-containing compositions characterised by the organic compounds
    • C09K8/22—Synthetic organic compounds
    • C09K8/24—Polymers

Definitions

  • the present invention relates to substituted scleroglucans, and more particularly to a substituted scleroglucan or a mixture of substituted scleroglucans.
  • the present invention also relates to a method for producing the substituted scleroglucan, and a drilling fluid composition produced from the substituted scleroglucan.
  • the conventional drilling fluid treatment agent generally has a conflict between the environmental protection performance and the stability performance.
  • modified natural materials or biomass materials have good environmental protection properties, are non-toxic, and are easily biodegradable, but their temperature resistance needs to be improved, such as starch, cellulose, and xanthan gum; high-molecular polymer treatment agents are stable Good performance, but there are environmental problems, high toxicity, difficult to biodegrade, such as acrylamides, polyamines.
  • substituted scleroglucan can be prepared by gelatinization and grafting reaction on multiple hydroxyl active sites of the scleroglucan molecule. Glycan products.
  • the inventors of the present invention also found that the product has good high temperature resistance, viscosity enhancement and shear improvement effect, and is green and environmentally friendly, which is of great significance in eliminating environmental protection pressure, reducing downhole complexity, and reducing drilling costs. The present invention has been completed based on this finding.
  • the present invention relates to the following aspects.
  • substituent C comprises
  • the group R 3 is selected from C2-6 or C2-3 straight or branched chain alkylene (preferably ethylene or propylene), and the group L 1 is selected from (preferably the number of carbon atoms does not exceed 10) any linking group (preferably single bond or C1-10 or C1-4 straight or branched alkylene, especially single bond), R 1 is selected from hydrogen atom, alkali metal (such as K or Na), alkaline earth metals (such as Ca or Mg), ammonium (NH 4 ) and C1-10 or C1-4 straight or branched alkyl groups),
  • the substituent B is represented by the following chemical formula (B-1), chemical formula (B-11), chemical formula (B-12), chemical formula (B-2), chemical formula (B-21), chemical formula (B-22), chemical formula (B-3), chemical formula (B-31) or chemical formula (B-32) represent,
  • the groups R 4 , R 41 , R 42 are the same or different from each other, and are each independently selected from C2-6 or C2-3 linear or branched alkylene groups (preferably ethylene or propylene)
  • the groups L 2 , L 21 , L 22 are the same or different from each other, each independently selected from (preferably the number of carbon atoms does not exceed 10) any linking group (preferably a single bond or a C1-10 or C1-4 straight chain or branched alkylene, especially single bond)
  • M is an alkali metal (such as K or Na), alkaline earth metal (such as Ca or Mg) or ammonium ( NH4 )
  • R2 is selected from hydrogen atoms and optionally substituted C1 -10 or C1-4 straight or branched chain alkyl
  • R 2 ' is a hydrogen atom
  • the substituent C is represented by the following chemical formula (C-1), chemical formula (C-2) or chemical formula (C-3),
  • the group R 5 is selected from C2-6 or C2-3 straight or branched chain alkylene (preferably ethylene or propylene), and the group L 3 is selected from (preferably the number of carbon atoms does not exceed 10) any linking group (preferably single bond or C1-10 or C1-4 linear or branched alkylene, especially single bond), Ra, Rb and Rc are the same or different from each other, each independently selected from hydrogen atom and a C1-10 or C1-4 straight or branched chain alkyl group (preferably a hydrogen atom),
  • the substituent D is represented by the following chemical formula (D-1) or chemical formula (D-2),
  • the group L 4 is selected from (preferably the number of carbon atoms does not exceed 10) any linking group (preferably a single bond or a C1-10 or C1-4 linear or branched alkylene group, especially a single bond ),
  • Ar is selected from C6-20 aryl (preferably phenyl),
  • the substituent E is represented by the following chemical formula (E-1) or chemical formula (E-2),
  • the group L 5 is selected from (preferably the number of carbon atoms does not exceed 10) any linking group (preferably a single bond or a C1-10 or C1-4 linear or branched alkylene group, especially a single bond ),
  • Rs is a siloxane group represented by -Si(OR') 3 (wherein R' is a C1-4 straight or branched chain alkyl group, preferably methyl or ethyl).
  • the mixture of a kind of substituted scleroglucan or a plurality of substituted scleroglucans described in any one of the foregoing or the following chemical formula (I) is a substituted scleroglucan or its multiple a mixture of species,
  • n is 2000-20000, preferably 5000-10000, most preferably 6000-8000
  • each Z is the same or different from each other, and each independently represents a hydrogen atom, the substituent A, the substituent B, The substituent C, the substituent D, the substituent E, or a combination of these substituents, provided that at least one Z is not a hydrogen atom
  • each formula (I) let the substitution
  • the average number of groups A is o', let the average number of the substituents B be x', let the average number of the substituents C be p', let the average number of the substituents D be y', let the The average number of the substituent E is z', then o' is any value from 1-40 (preferably 1-15), p' is any value from 1-20 (preferably 1-10), and x' is 1-40 (preferably 1-20), y' is any value from 0-20 (preferably 1-15), and z' is any value from 0-20 (preferably 1-5).
  • the mixture of a substituted scleroglucan or a plurality of substituted scleroglucans described in any one of the foregoing or the following chemical formula (I-1) is a substituted scleroglucan represented by the following chemical formula (I-1) or its various mixtures,
  • n is 2000-20000, preferably 5000-10000, most preferably 6000-8000, each Z' is the same or different from each other, each independently represents a hydrogen atom, and is represented by chemical formula (A-3) Substituent A (referred to as Substituent A'), Substituent B represented by Chemical Formula (B-22) (referred to as Substituent B'), Substituent B represented by Chemical Formula (B-32) (referred to as Substituent B"), the substituent C represented by chemical formula (C-3) (referred to as substituent C'), the substituent D represented by chemical formula (D-2) (referred to as substituent D'), and the chemical formula (E -2) Substituent E (referred to as Substituent E') represented by, or a combined group of these substituents, provided that at least one Z' is not a hydrogen atom, and in each chemical formula (I-1), set the Let the average number of the substituents A' be o, let
  • the mixture of a kind of substituted scleroglucan or a plurality of substituted scleroglucans described in any one of the foregoing or the following chemical formula (I-2) is a substituted scleroglucan schematically represented by the following chemical formula (I-2). sugar or mixtures thereof,
  • M is hydrogen, alkali metal (such as K or Na), alkaline earth metal (such as Ca or Mg) or ammonium (NH 4 ), and * represents a covalent bonding site.
  • n is 2000-20000, preferably 5000-10000, most preferably 6000-8000,
  • the represented pyrrolidone monomer, the optional phenyl monomer represented by the chemical formula (X-5), and the optional siloxane-based monomer represented by the chemical formula (X-6) are in a base (preferably selected from alkali metals) At least one of hydroxides and alkaline earth metal hydroxides, especially at least one selected from sodium hydroxide, potassium hydroxide and calcium hydroxide) is mixed with water (preferably homogeneously mixed) to obtain a mixed monomer, and
  • sclerodextran gel and the mixed monomer at least one selected from a radical polymerization initiator (preferably selected from a peroxide-based initiator, an azo-based initiator and a redox-based initiator); , especially selected from at least one of hydrogen peroxide, ammonium persulfate, azobisisobutyronitrile, ceric ammonium nitrate, and at least one of sodium bisulfite and ammonium persulfate in parts by mass 1:2) base polymerization reaction, optionally drying, to obtain the substituted scleroglucan or a mixture of a plurality of substituted scleroglucans,
  • a radical polymerization initiator preferably selected from a peroxide-based initiator, an azo-based initiator and a redox-based initiator
  • a radical polymerization initiator especially selected from at least one of hydrogen peroxide, ammonium persulfate, azobisisobutyronitrile, ceric ammonium
  • groups L 1 , L 21 , L 22 , L 3 , L 4 , L 5 are the same or different from each other, each independently selected from (preferably the number of carbon atoms) no more than 10) any linking group (preferably a single bond or a C1-10 or C1-4 straight or branched alkylene group, especially a single bond),
  • M is an alkali metal (such as K or Na)
  • Ra, Rb and Rc are the same or different from each other, each independently selected from a hydrogen atom and a C1-10 or C1-4 straight or branched chain alkyl group (preferably a hydrogen atom)
  • R 1 is selected from hydrogen atoms, alkali metals (such as K or Na), alkaline earth metals (such as Ca or Mg), ammonium (NH 4 ) and C1-10 or C1-4 straight or branched chain alkyl groups (preferably hydrogen atoms
  • the mass ratio of the sclerodextran, water and the alkali is 12:(180-220):(4 -8), and/or, in the step 1), the reaction temperature is 60-70 ° C, the reaction time is 0.5-2h, and/or, in the step 2), the chemical formula (X- 1)
  • the mass ratio of the sulfonic acid monomer, the base and the water is 20:(15-18):(54-64):(27-36):(6-8):(50-80), and/or,
  • the mass ratio of the agent is (152-198): 12: (0.8-1.6), and/or, in the step 3), the pH value of the polymerization reaction system is controlled to be 8-10, and the reaction temperature is 40-70 ° C , the reaction time is 4-10h, and/or, in the step 3), the drying temperature is 80-100°C.
  • a drilling fluid composition comprising a substituted scleroglucan, a base slurry and optionally at least one treating agent, wherein the substituted scleroglucan is one of the preceding or following aspects.
  • the mass percentage content of the substituted scleroglucan is 0.5-10.0 wt% (preferably 1.5-5.0 wt%).
  • a method for manufacturing a drilling fluid composition comprising mixing substituted scleroglucan, base slurry and optionally at least one treating agent (preferably mixing the substituted sclerodextran and the base slurry first, The obtained mixture is then mixed with the optional at least one treating agent) to obtain the drilling fluid composition, wherein the substituted scleroglucan is one of the aforementioned or the following aspects.
  • the sugar mixture, and, optionally, the obtained drilling fluid composition is subjected to an aging treatment (preferably at a treatment temperature of 120-200°C or 140-180°C, preferably 155-165°C, and a treatment time of 10-30 hours or 15- 20 hours, preferably 15-17 hours).
  • the substituted scleroglucan of the present invention shows excellent viscosity-increasing and shear-lifting performance under high temperature conditions, and also has excellent fluid loss reduction performance, and is green and environmentally friendly, and is especially suitable for deep well and ultra-deep well drilling construction with high formation temperature Use drilling fluid.
  • the manufacturing method of the substituted scleroglucan of the present invention has mild reaction conditions, simple process operation, no discharge of waste water, waste gas and waste residue, and is environmentally friendly.
  • FIG. 1 is an infrared spectrum of scleroglucan used in Examples and Comparative Examples.
  • FIG. 2 is the infrared spectrum of the substituted scleroglucan obtained in Example 1.
  • aryl refers to C6-20 aryl, preferably phenyl, unless otherwise specified.
  • the expression “optionally substituted” means that it is optionally selected by one or more (such as 1 to 5, 1 to 4, 1 to 3, 1 to 2 or 1) selected from Substituents for hydroxyl, C1-4alkoxy, amino and sulfo (-SO 3 M) are substituted, preferably sulfo (-SO 3 M).
  • M is an alkali metal (such as K or Na), an alkaline earth metal (such as Ca or Mg) or ammonium (NH 4 ).
  • the measurement of the HLB value includes: weighing 1.0 g (accurate to 0.0001 g) of the sample to be tested, putting it into a clean and dry 250 mL conical flask, accurately weighing 99.0 g deionized water, and placing it into the above-mentioned In a conical flask, prepare a 1.0% aqueous solution of the sample to be tested.
  • the above conical flask is gradually heated in a constant temperature water bath.
  • the temperature in the conical flask is the cloud point T of the sample to be tested. Cloud point measurement was performed by randomly selecting 3 batches of samples to be tested.
  • T - cloud point of the sample to be tested in degrees Celsius (°C).
  • the measurement of the amine value includes: weighing 0.5 g (accurate to 0.0001 g) of the sample to be tested, putting it into a clean and dry 250 mL conical flask, adding 50 mL deionized water and recording the total mass m 1 .
  • the amine value was measured by randomly selecting 3 batches of samples to be tested. Calculate the amine value according to formula (2):
  • V the value of the volume of the hydrochloric acid-isopropanol standard solution consumed by the sample to be tested, in milliliters (mL);
  • V blank the value of the volume of the blank test hydrochloric acid solution, in milliliters (mL);
  • any two or more embodiments of the present invention can be combined arbitrarily, and the technical solutions formed thereby belong to a part of the original disclosure content of this specification, and also fall within the protection scope of the present invention.
  • a substituted scleroglucan refers to the substituted scleroglucan in the form of a single compound
  • mixture of substituted scleroglucans refers to the A mixture formed by mixing two or more (ie, multiple) substituted scleroglucans together.
  • the substituted scleroglucan exists independently in the form of each compound or exists in the form of a mixture with each other can achieve the intended purpose of the present invention, and is not particularly limited. Therefore, the present invention sometimes collectively refers to the mixture of the one substituted scleroglucan and the plurality of substituted scleroglucans as substituted scleroglucan.
  • the scleroglucan (or scleroglucan backbone) may be represented by the following chemical formula (A).
  • A the presence of the scleroglucan can be confirmed by an infrared analysis method. For example, on the infrared spectrum of the substituted scleroglucan, if characteristic peaks are displayed at or near 3405, 2878, 1387, and 1064 cm ⁇ 1 , the existence of the scleroglucan can be confirmed.
  • n is 2000-20000, preferably 5000-10000, most preferably 6000-8000.
  • the substituted scleroglucans carry substituents A, B and C, each or a combination, and optionally, each or a combination of D and E , that is, the substituent D and the substituent E are optional substituents.
  • each with means that the substituent A, the substituent B, the substituent C, the substituent D (if any), and the substituent E (if any) are respectively located in On different sclerodextran molecules, and the so-called combination with, refers to the substituent A, the substituent B, the substituent C, the substituent D (if any), the substituent The groups E (if any) can be located on different scleroglucan molecules respectively, or can be located on different or the same sclerodextran molecule according to any combination (for example, two or three combinations or three at the same time).
  • R 1 is selected from hydrogen atoms, Alkali metals (such as K or Na), alkaline earth metals (such as Ca or Mg), ammonium ( NH4 ) and C1-10 or C1-4 straight or branched chain alkyl groups.
  • R 1 is selected from hydrogen atoms, Alkali metals (such as K or Na), alkaline earth metals (such as Ca or Mg), ammonium ( NH4 ) and C1-10 or C1-4 straight or branched chain alkyl groups.
  • the presence of these units or the substituent A can be confirmed by an infrared analysis
  • the substituent A may be represented by the following chemical formula (A-1), chemical formula (A-2) or chemical formula (A-3).
  • the group R 3 is selected from C2-6 or C2-3 linear or branched alkylene groups, preferably ethylene or propylene.
  • the group L 1 is selected from any linking group, preferably any linking group with no more than 10 carbon atoms, particularly preferably a single bond or a C1-10 or C1-4 linear or branched alkylene group, especially a single bond.
  • R 1 is selected from hydrogen atoms, alkali metals (such as K or Na), alkaline earth metals (such as Ca or Mg), ammonium (NH 4 ) and C1-10 or C1-4 straight or branched chain alkyl groups.
  • R 2 is selected from hydrogen atom and optionally substituted C1-10 or C1-4 straight or branched chain alkyl.
  • the presence of these units or the substituent B can be confirmed by an infrared analysis method.
  • the presence of these units or the substituent B can be confirmed by showing characteristic peaks at or near 1195 cm ⁇ 1 on the infrared spectrum of the substituted scleroglucan.
  • the substituent B can be represented by the following chemical formula (B-1), chemical formula (B-11), chemical formula (B-12), chemical formula (B-2), chemical formula (B-21) , chemical formula (B-22), chemical formula (B-3), chemical formula (B-31) or chemical formula (B-32).
  • the groups R 4 , R 41 , and R 42 are the same or different from each other, and are each independently selected from C2-6 or C2-3 straight or branched chain alkylene, preferably ethylene or propylene .
  • the groups L 2 , L 21 , and L 22 are the same or different from each other, and are each independently selected from any linking group, preferably any linking group with no more than 10 carbon atoms, particularly preferably a single bond or C1-10 or C1-4 Linear or branched alkylene, especially single bonds.
  • M is an alkali metal (such as K or Na), an alkaline earth metal (such as Ca or Mg) or ammonium ( NH4 ).
  • R 2 is selected from a hydrogen atom and an optionally substituted C1-10 or C1-4 straight or branched chain alkyl group
  • R 2 ' is a hydrogen atom
  • R 2 " is selected from an optionally substituted C1-10 or C1-4 straight chain Chain or branched alkyl.
  • the substituent C comprises a unit in its structure wherein Ra, Rb and Rc are the same or different from each other, and are each independently selected from a hydrogen atom and a C1-10 or C1-4 straight or branched chain alkyl group, preferably a hydrogen atom.
  • the presence of the unit or the substituent C can be confirmed by an infrared analysis method.
  • the presence of the unit or the substituent C can be confirmed by showing a characteristic peak at or near 1674 cm -1 on the infrared spectrum of the substituted scleroglucan.
  • the substituent C may be represented by the following chemical formula (C-1), chemical formula (C-2) or chemical formula (C-3).
  • the group R 5 is selected from C2-6 or C2-3 linear or branched alkylene, preferably ethylene or propylene.
  • the group L 3 is selected from any linking group, preferably any linking group with no more than 10 carbon atoms, particularly preferably a single bond or a C1-10 or C1-4 linear or branched alkylene group, especially a single bond.
  • Ra, Rb and Rc are the same or different from each other, and are each independently selected from a hydrogen atom and a C1-10 or C1-4 straight or branched chain alkyl group, preferably a hydrogen atom.
  • all the groups and numerical values that are not clearly defined herein are directly applicable to the corresponding definitions given for the substituent C in the previous part of the specification.
  • the substituent D comprises an aryl group, preferably a phenyl group, in its structure.
  • the presence of these units or the substituent D can be confirmed by an infrared analysis method.
  • the presence of these units or the substituent D can be confirmed by showing characteristic peaks at or near 1453 cm -1 on the infrared spectrum of the substituted scleroglucan.
  • the substituent D may be represented by the following chemical formula (D-1) or chemical formula (D-2).
  • the group L 4 is selected from any linking group, preferably any linking group with no more than 10 carbon atoms, particularly preferably a single bond or a C1-10 or C1-4 linear or branched alkylene group , especially single keys.
  • Ar is selected from C6-20 aryl, preferably phenyl.
  • the substituent E contains a siloxane group in its structure, preferably a siloxane group represented by -Si(OR') 3 , wherein R' is a C1-4 straight chain or Branched alkyl, preferably methyl or ethyl.
  • R' is a C1-4 straight chain or Branched alkyl, preferably methyl or ethyl.
  • R' is a C1-4 straight chain or Branched alkyl, preferably methyl or ethyl.
  • the presence of these units or the substituent E can be confirmed by infrared analysis methods.
  • the presence of these units or the substituent E can be confirmed by showing characteristic peaks at or near 2150 cm ⁇ 1 on the infrared spectrum of the substituted scleroglucan.
  • the substituent E may be represented by the following chemical formula (E-1) or chemical formula (E-2).
  • the group L 5 is selected from any linking group, preferably any linking group with no more than 10 carbon atoms, particularly preferably a single bond or a C1-10 or C1-4 linear or branched alkylene group , especially single keys.
  • Rs is a siloxane group represented by -Si(OR') 3 , wherein R' is a C1-4 straight or branched chain alkyl group, preferably methyl or ethyl.
  • the substituted scleroglucan is a substituted scleroglucan represented by the following chemical formula (I) or a mixture thereof.
  • any scleroglucan molecule or any substituted scleroglucan molecule is drawn for ease of understanding only, and is not intended to limit the present invention. Indeed, these molecules may be in any steric configuration without departing from the spirit of the present invention.
  • n represents the degree of polymerization of a sclerodextran molecule, which is generally 2000-20000, preferably 5000-10000, and most preferably 6000-8000.
  • Each Z is the same as or different from each other, and each independently represents a hydrogen atom, the substituent A, the substituent B, the substituent C, the substituent D, the substituent E, or a combination of these substituents group, provided that at least one Z is not a hydrogen atom, that is, at least one hydrogen atom on -OH in a scleroglucan molecule is substituted by one of these substituents.
  • the so-called “combined group” refers to the same substituent or different substitution among the substituent A, the substituent B, the substituent C, the substituent D, and the substituent E.
  • a chain-like structure formed by combining two or more groups in any order of bonding a specific schematic example is shown below, but the present invention is not limited thereto.
  • the present invention does not specifically limit the bonding order between the same or different substituents, for example, the same or different substituents can be bonded in any order to form chains such as random, block or alternating. like structure.
  • each chemical formula (I) let the average number of the substituents A be o', let the average number of the substituents B be x', let the average number of the substituents C be x'
  • the average number is p', let the average number of the substituents D be y', let the average number of the substituents E be z', then o' is any value from 1-40 (preferably 1-15), p ' is any value from 1-20 (preferably 1-10), x' is any value from 1-40 (preferably 1-20), y' is any value from 0-20 (preferably 1-15), and z' is Any value from 0-20 (preferably 1-5).
  • the present invention does not intend to control or limit the specific number of a certain substituent on a sclerodextran molecule, so in the context of this specification, the so-called "average number" of a certain substituent refers to the substituent Relative to the statistical average number of all scleroglucan molecules. This quantity can be an integer or a non-integer.
  • the substituted scleroglucan is a substituted scleroglucan represented by the following chemical formula (I-1) or a mixture of various thereof.
  • n represents the degree of polymerization of a sclerodextran molecule, which is generally 2,000-20,000, preferably 5,000-10,000, and most preferably 6,000-8,000.
  • Each Z' is the same as or different from each other, and each independently represents a hydrogen atom, a substituent A represented by the chemical formula (A-3) (referred to as a substituent A'), a substituent B represented by a chemical formula (B-22) (referred to as a substituent A').
  • Substituent B' Substituent B represented by Chemical Formula (B-32) (referred to as Substituent B"), Substituent C represented by Chemical Formula (C-3) (referred to as Substituent C'), Substituent D represented by Chemical Formula (D-2) (referred to as Substituent D'), Substituent E represented by Chemical Formula (E-2) (referred to as Substituent E'), or a combination of these substituents,
  • the premise is that at least one Z' is not a hydrogen atom, that is, at least one hydrogen atom on -OH in a sclerodextran molecule is substituted by one of these substituents.
  • the so-called “combination group” refers to are the same or different among the substituents A', the substituents B', the substituents B", the substituents C', the substituents D', and the substituents E'
  • a chain-like structure formed by combining two or more substituents in any order of bonding a specific schematic example is shown above, but the present invention is not limited thereto.
  • the present invention does not specifically limit the bonding order between the same or different substituents, for example, the same or different substituents can be bonded in any order to form chains such as random, block or alternating. like structure.
  • each chemical formula (I-1) let the average number of the substituents A' be o, let the average number of the substituents B' be q, let the substituents Let the average number of B" be w, let the average number of the substituents C' be p, let the average number of the substituents D' be y, let the average number of the substituents E' be z, then o is Any value of 1-20 (preferably 1-15), p is any value of 1-20 (preferably 1-10), q is any value of 1-20 (preferably 1-15), w is 1-20 (preferably 1-10), y is any value from 0-20 (preferably 1-15), and z is any value from 0-20 (preferably 1-5).
  • the present invention is not intended to control or The specific number of a certain substituent on a sclerodextran molecule is limited, so in the context of this specification, the so-called "average number" of a certain substituent refers to the substituent relative to all scleroglucans.
  • all groups and values that are not clearly defined here are directly applicable to the corresponding definitions given for the chemical formula (1) earlier in this specification.
  • the substituted scleroglucan is a substituted scleroglucan schematically represented by the following chemical formula (I-2) or a mixture of various thereof.
  • the so-called “schematic” means that the same and different substituents are all grouped in a chain structure for the convenience of understanding only, and in the chain structure, the same substitution The groups form a block structure with the respective average number as the number of repeating units.
  • M is hydrogen, an alkali metal (such as K or Na), an alkaline earth metal (such as Ca or Mg), or ammonium (NH 4 ).
  • * represents a covalent bonding site, that is, the chain structure will be covalently bonded to the scleroglucan molecule via the free end represented by the * (replacing a certain structure on the sclerodextran molecule). a hydroxyl hydrogen atom).
  • the amine value of the substituted scleroglucan is 0.2-0.6 mmol/g.
  • the HLB value of the substituted scleroglucan is 15.0-20.0.
  • the substituted scleroglucan can be produced according to the method for producing a substituted scleroglucan or a mixture of a plurality of substituted scleroglucans of the present invention.
  • the manufacturing method may include the following steps.
  • the base is selected from at least one of alkali metal hydroxides and alkaline earth metal hydroxides, especially selected from sodium hydroxide, potassium hydroxide and At least one of calcium hydroxide.
  • the mass ratio of the scleroglucan, water and the alkali is generally 12:(180-220):(4-8).
  • the reaction temperature is generally 60-70° C.
  • the reaction time is generally 0.5-2 h.
  • the scleroglucan ie, a scleroglucan molecule
  • the scleroglucan can be represented by the following chemical formula (A).
  • n is 2000-20000, preferably 5000-10000, most preferably 6000-8000.
  • the base is selected from at least one of alkali metal hydroxides and alkaline earth metal hydroxides, especially selected from sodium hydroxide, potassium hydroxide and At least one of calcium hydroxide.
  • groups L 1 , L 21 , L 22 , L 3 , L 4 , L 5 are the same or different from each other, and are each independently selected from any linking group, Any linking group with a carbon number of not more than 10 is preferred, preferably a single bond or a C1-10 or C1-4 straight-chain or branched alkylene group, especially a single bond.
  • M is an alkali metal (such as K or Na), an alkaline earth metal (such as Ca or Mg) or ammonium ( NH4 ).
  • Ra, Rb and Rc are the same or different from each other, and are each independently selected from a hydrogen atom and a C1-10 or C1-4 straight or branched chain alkyl group, preferably a hydrogen atom.
  • R 1 is selected from hydrogen atoms, alkali metals (such as K or Na), alkaline earth metals (such as Ca or Mg), ammonium (NH 4 ) and C1-10 or C1-4 straight or branched chain alkyl groups, preferably hydrogen atoms.
  • Ar is C6-20 aryl, preferably phenyl.
  • Rs is a siloxane group represented by -Si(OR') 3 , wherein R' is a C1-4 straight or branched chain alkyl group, preferably methyl or ethyl.
  • the carboxylic acid monomer represented by chemical formula (X-1), the pyrrolidone monomer represented by chemical formula (X-4), the The mass ratio of the amide monomer represented by the chemical formula (X-2), the sulfonic acid monomer represented by the chemical formula (X-3), and the base to water is 20:(15-18):(54-64) :(27-36):(6-8):(50-80).
  • the carboxylic acid monomer represented by the chemical formula (X-1), the benzene represented by the chemical formula (X-5) The mass ratio of the base monomer to the siloxane-based monomer represented by the chemical formula (X-6) is 20:(27-45):(9-15).
  • the mixing temperature is generally 30-40°C.
  • the sclerodextran gel and the mixed monomer are subjected to a radical polymerization reaction in the presence of a radical polymerization initiator, and optionally dried to obtain the substituted scleroglucan.
  • drying is an optional step.
  • the free radical polymerization initiator is selected from at least one of peroxide-based initiators, azo-based initiators and redox-based initiators, especially It is at least one selected from the group consisting of hydrogen peroxide, ammonium persulfate, azobisisobutyronitrile, ceric ammonium nitrate, and 1:2 parts by mass of sodium bisulfite and ammonium persulfate.
  • the mixed monomers based on the total weight of all monomers
  • the sclerodextran gel based on the weight of the sclerodextran
  • the mass ratio of the free radical polymerization initiator is generally (152-198): 12: (0.8-1.6).
  • the pH value of the polymerization reaction system is generally controlled to be 8-10, for example, by adding an aqueous sodium hydroxide solution.
  • the reaction temperature of the polymerization reaction system is generally 40-70° C.
  • the reaction time is generally 4-10 h.
  • the drying temperature is generally 80-100°C. This drying can be carried out in an oven. After drying, pulverization can be performed.
  • the step 1) to the step 3) may be performed in the presence of stirring.
  • the stirring speed of the stirring is generally 800-4000 r/min, preferably 1000-1100 r/min.
  • the present invention also relates to a drilling fluid composition
  • a substituted scleroglucan comprising a substituted scleroglucan, a base slurry and optionally at least one treatment agent.
  • the substituted scleroglucan may be any one of the substituted scleroglucans as described above in the present invention or a mixture of a plurality of substituted scleroglucans or any of the substituted scleroglucans described above by the present invention.
  • the mass percentage content of the substituted scleroglucan is generally 0.5-10.0 wt%, preferably 1.5-5.0 wt%.
  • the present invention also relates to a method for manufacturing a drilling fluid composition.
  • the manufacturing method includes a step (referred to as a mixing step) of mixing substituted scleroglucan, base slurry, and optionally at least one treatment agent to obtain the drilling fluid composition.
  • the substituted scleroglucan may be any one of the substituted scleroglucans as described above in the present invention or a mixture of a plurality of substituted scleroglucans or any of the substituted scleroglucans described above by the present invention.
  • any treatment agent conventionally used in drilling fluid compositions in the art can be used, for example, a treatment agent selected from the group consisting of viscosifiers, flow regulators, At least one of a fluid loss reducer, a high temperature stabilizer, a plugging agent, an inhibition enhancer and a pH adjuster.
  • a treatment agent selected from the group consisting of viscosifiers, flow regulators, At least one of a fluid loss reducer, a high temperature stabilizer, a plugging agent, an inhibition enhancer and a pH adjuster.
  • the types and amounts of these treating agents can be directly applied to those known in the art, and are not particularly limited.
  • the substituted scleroglucan and the base slurry are first mixed, and then the obtained The mixture is admixed with the optional at least one treatment agent.
  • the mixing is performed under high-speed stirring, for example, the rotation speed of the high-speed stirring is preferably 5000r/min-10000r/min, and the time is preferably 10min-30min.
  • the manufacturing method of the drilling fluid composition further includes a step of aging the drilling fluid composition obtained in the mixing step (referred to as an aging step).
  • the treatment temperature is generally 120-200°C or 140-180°C, preferably 155-165°C, and the treatment time is generally 10-30 hours or 15-20 hours, Preferably 15-17 hours.
  • the raw materials used in the following examples and comparative examples are all commercially available products.
  • 3405cm -1 is the stretching vibration peak of the OH bond of scleroglucan.
  • 2878cm -1 is the CH bond stretching vibration absorption peak of methyl and methylene, which can determine the structure containing sclerodextran
  • 1387cm -1 is -CH-symmetric bending vibration absorption peak
  • 1064cm -1 is CO stretching Vibration absorption peak
  • the infrared spectrum better reflects the main characteristic absorption peak of sclerodextran.
  • Body aqueous solution mix the above sclerodextran gel with the monomer aqueous solution, stir evenly at a stirring speed of 1000r/min, adjust the pH value of the reaction solution to 8 with a 40% sodium hydroxide aqueous solution, and add 0.12 g of hydrogen peroxide initiator Add to the reaction solution and react at 40°C for 4 hours to obtain a milky yellow translucent viscous liquid, which is dried and pulverized at 80°C in an oven to obtain the substituted scleroglucan anti-high temperature viscosity-increasing and cutting agent.
  • the product yield was 92.81%.
  • the product has an amine value of 0.20 mmol/g and an HLB value of 15.0.
  • the product produced in this example is subjected to infrared detection, and the detection result (as shown in Figure 2) is that a characteristic peak is displayed at 2938cm -1 , confirming the existence of the substituent A or the substituent A', and at 1195cm- 1 place shows a characteristic peak, confirms the existence of the substituent B', shows a characteristic peak at 1049, 1195cm -1 , confirms the existence of the substituent B", shows a characteristic peak at 1674cm -1 , confirms the substitution The presence of the group C or the substituent C' shows a characteristic peak at 1453 cm -1 , confirming the existence of the substituent D or the substituent D', showing a characteristic peak at 2150 cm -1 , confirming the substitution the presence of the group E or said substituent E'.
  • the substituted scleroglucan prepared in Example 1 of the present invention has the schematic structure shown in Formula 1:
  • n 7400-7600, o is 10.5, p is 8.4, q is 12.5, w is 8.2, y is 0, z is 0, and M is Na.
  • Body aqueous solution mix the above sclerodextran gel with the monomer aqueous solution, stir evenly at a stirring speed of 1100 r/min, adjust the pH value of the reaction solution to 9 with 40% potassium hydroxide aqueous solution, and add 0.16 g of ammonium persulfate initiator Add to the reaction solution and react at 50°C for 5 hours to obtain a milky yellow translucent viscous liquid, which is dried and pulverized at 90°C in an oven to obtain the substituted scleroglucan anti-high temperature viscosity-increasing and cutting agent.
  • the product yield was 93.64%.
  • the product has an amine value of 0.26 mmol/g and an HLB value of 15.2.
  • the product produced in this example is subjected to infrared detection, and the detection result is that a characteristic peak is displayed at 2939 cm -1 , the existence of the substituent A or the substituent A' is confirmed, and a characteristic peak is displayed at 1196 cm -1 , confirming that The existence of the substituent B' shows characteristic peaks at 1048 and 1196 cm -1 , confirming the existence of the substituent B", showing a characteristic peak at 1675 cm -1 , confirming the substituent C or the substituent The presence of C' shows a characteristic peak at 1454 cm -1 , confirming the existence of the substituent D or the substituent D', showing a characteristic peak at 2151 cm -1 , confirming the substituent E or the substituent the existence of E'.
  • the substituted scleroglucan prepared in Example 2 of the present invention has the schematic structure shown in Formula 2:
  • n 7400-7600, o is 11.2, p is 8.8, q is 12.9, w is 8.7, y is 0, z is 0, and M is K.
  • Body aqueous solution mix the above sclerodextran gel with the monomer aqueous solution, stir evenly at a stirring speed of 1100 r/min, adjust the pH value of the reaction solution to 10 with 40% calcium hydroxide aqueous solution, and add 0.20 g of azobisisobutyl
  • the nitrile initiator was added to the reaction solution and reacted at 60°C for 7 hours to obtain a milky yellow translucent viscous liquid, which was dried and pulverized at 100°C in an oven to obtain the substituted scleroglucan anti-high temperature viscosity-increasing and cutting agent. .
  • the product yield was 93.87%.
  • the product has an amine value of 0.35 mmol/g and an HLB value of 16.8.
  • the product produced in this example is subjected to infrared detection, and the detection result is that a characteristic peak is displayed at 2937 cm -1 , the existence of the substituent A or the substituent A' is confirmed, and a characteristic peak is displayed at 1195 cm -1 , confirming that The existence of the substituent B' shows characteristic peaks at 1046 and 1198 cm -1 , confirming the existence of the substituent B", showing a characteristic peak at 1676 cm -1 , confirming the substituent C or the substituent The presence of C' shows a characteristic peak at 1455 cm -1 , confirming the existence of the substituent D or the substituent D', showing a characteristic peak at 2152 cm -1 , confirming the substituent E or the substituent the existence of E'.
  • the substituted scleroglucan prepared in Example 3 of the present invention has the schematic structure shown in Formula 3:
  • n 7400-7600, o is 12.5, p is 9.6, q is 13.5, w is 9.2, y is 0, z is 0, and M is Ca.
  • Body aqueous solution mix the above sclerodextran gel with the monomer aqueous solution, stir evenly at a stirring speed of 1100 r/min, adjust the pH value of the reaction solution to 10 with 40% sodium hydroxide aqueous solution, and add 0.28 g of ceric ammonium nitrate initiator Add to the reaction solution and react at 70°C for 9 hours to obtain a milky yellow translucent viscous liquid, which is dried and pulverized at 100°C in an oven to obtain the substituted scleroglucan anti-high temperature viscosity-increasing and cutting agent.
  • the product yield was 94.57%.
  • the product has an amine value of 0.44 mmol/g and an HLB value of 17,3.
  • the product manufactured in this example is subjected to infrared detection, and the detection result is that a characteristic peak is displayed at 2936 cm -1 , the existence of the substituent A or the substituent A' is confirmed, and a characteristic peak is displayed at 1196 cm -1 , confirming that The existence of the substituent B' shows characteristic peaks at 1048 and 1197 cm -1 , confirming the existence of the substituent B", showing a characteristic peak at 1677 cm -1 , confirming the substituent C or the substituent The presence of C' shows a characteristic peak at 1456 cm -1 , confirming the presence of the substituent D or the substituent D', showing a characteristic peak at 2154 cm -1 , confirming the substituent E or the substituent the existence of E'.
  • the substituted scleroglucan prepared in Example 4 of the present invention has the schematic structure shown in Formula 4:
  • n 7400-7600, o is 13.1, p is 9.7, q is 13.8, w is 9.4, y is 0, z is 0, and M is Na.
  • Body aqueous solution mix the above sclerodextran gel with the monomer aqueous solution, stir evenly at a stirring speed of 1100r/min, adjust the pH value of the reaction solution to 10 with a 40% aqueous sodium hydroxide solution, mix 0.12g of sodium bisulfite, 0.24g of ammonium persulfate initiator was added to the reaction solution and reacted at 70°C for 10h to obtain a milky yellow translucent viscous liquid, which was dried and pulverized at 100°C in an oven to obtain the substituted scleroglucan with high temperature resistance. Sticky cutting agent. The product yield was 96.20%.
  • the product has an amine value of 0.49 mmol/g and an HLB value of 18.0.
  • the product produced in this example is subjected to infrared detection, and the detection result is that a characteristic peak is displayed at 2939 cm -1 , the existence of the substituent A or the substituent A' is confirmed, and a characteristic peak is displayed at 1198 cm -1 , confirming that The existence of the substituent B' shows characteristic peaks at 1049 and 1197 cm -1 , confirming the existence of the substituent B", showing a characteristic peak at 1678 cm -1 , confirming the substituent C or the substituent The presence of C' shows a characteristic peak at 1457 cm -1 , confirming the presence of the substituent D or the substituent D', showing a characteristic peak at 2156 cm -1 , confirming the substituent E or the substituent the existence of E'.
  • the substituted scleroglucan prepared in Example 5 of the present invention has the schematic structure shown in Formula 5:
  • n 7400-7600, o is 13.7, p is 9.9, q is 13.9, w is 9.7, y is 0, z is 0, and M is Na.
  • the product has an amine value of 0.52 mmol/g and an HLB value of 18.6.
  • the product produced in this example is subjected to infrared detection, and the detection result is that a characteristic peak is displayed at 2938 cm -1 , the existence of the substituent A or the substituent A' is confirmed, and a characteristic peak is displayed at 1199 cm -1 , confirming that The existence of the substituent B' shows characteristic peaks at 1046 and 1195 cm -1 , confirming the existence of the substituent B", showing a characteristic peak at 1677 cm -1 , confirming the substituent C or the substituent The presence of C' shows a characteristic peak at 1459 cm -1 , confirming the presence of the substituent D or the substituent D', showing a characteristic peak at 2157 cm -1 , confirming the substituent E or the substituent the existence of E'.
  • the substituted scleroglucan prepared in Example 6 of the present invention has the schematic structure shown in Formula 6:
  • n 7400-7600, o is 13.9, p is 10.6, q is 14.4, w is 9.8, y is 10.9, z is 3.3, and M is Na.
  • the product has an amine value of 0.60 mmol/g and an HLB value of 20.0.
  • the product produced in this example is subjected to infrared detection, and the detection result is that a characteristic peak is displayed at 2936 cm -1 , the existence of the substituent A or the substituent A' is confirmed, and a characteristic peak is displayed at 1197 cm -1 , confirming that The existence of the substituent B' shows characteristic peaks at 1047 and 1196 cm -1 , confirming the existence of the substituent B", showing a characteristic peak at 1678 cm -1 , confirming the substituent C or the substituent The presence of C' shows a characteristic peak at 1458 cm -1 , confirming the presence of the substituent D or the substituent D', showing a characteristic peak at 2159 cm -1 , confirming the substituent E or the substituent the existence of E'.
  • the substituted scleroglucan prepared in Example 7 of the present invention has the schematic structure shown in Formula 7:
  • n 7400-7600, o is 15.0, p is 14.2, q is 14.9, w is 9.9, y is 14.9, z is 4.9, and M is Na.
  • the initiator was added to the reaction solution and reacted at 40°C for 4 hours to obtain a milky yellow translucent viscous liquid, which was dried and pulverized at 80°C in an oven to obtain substituted chitosan.
  • the product yield was 86.14%.
  • the initiator was added to the reaction solution and reacted at 40°C for 4 hours to obtain a milky yellow translucent viscous liquid, which was dried and pulverized at 80°C in an oven to obtain the substituted cyclodextrin.
  • the product yield was 85.73%.
  • the pH value of the reaction solution was adjusted to 8 with 40% sodium hydroxide aqueous solution, 0.12 g of sodium bisulfite and 0.24 g of ammonium persulfate initiator were added to the reaction solution, and the reaction was carried out at 40 ° C for 4 h to obtain a milky yellow
  • the transparent viscous liquid is dried and pulverized at 80°C in an oven to obtain the substituted scleroglucan.
  • the product yield was 90.90%.
  • the substituted scleroglucan with a mass concentration of 0.3% prepared in Examples 1-7 of the present invention was heated in a 4% soil slurry at 150° C. for 16 hours, and the viscosity-increasing and cutting performance, filtration reduction performance and biological toxicity EC were tested. 50 value, and the test results are shown in Table 1.
  • the drilling fluid composition was added to the sodium chloride solution with a mass concentration of 3%, and were respectively prepared into 0 mg.dm -3 , 5000 mg.dm -3 , 10000 mg.dm -3 , 25000 mg.dm -3 , and 50000 mg.dm -3 . , 10mL of each 100000mg.dm -3 sample solution to be tested, let stand for 60min;
  • the 0.3% substituted sclerodextran sample can increase the apparent viscosity of 4% soil slurry from 3.0mPa.s to ⁇ 20mPa.s after aging at 150°C for 16h, and the apparent viscosity increases.
  • the high rate is ⁇ 566.67%
  • the initial shear force of static shear increases from 0.5Pa to ⁇ 1.5Pa
  • the initial shear increase rate is ⁇ 200%
  • the final shear force of static shear force increases from 0.5Pa to ⁇ 4.5Pa
  • API fluid loss decreased from 40mL to ⁇ 9.2mL, and the reduction rate of fluid loss was ⁇ 77%, showing good fluid loss reduction performance.
  • the EC 50 values of these substituted scleroglucan samples are more than 530,000 mg/L (much greater than the emission standard of 30,000 mg/L), non-biological toxicity, and environmentally friendly. Compared with the comparative samples, these substituted scleroglucan samples have greatly improved the viscosity-increasing and cutting-lifting properties and the fluid loss-reducing properties.
  • the substituted scleroglucan of the present invention has excellent anti-high temperature viscosity-increasing and cutting-lifting properties; at the same time, it has good fluid loss reduction properties and is environmentally friendly. Moreover, the substituted scleroglucan of the present invention is particularly suitable for the control of the viscosity-cutting performance and filtration reduction performance of high-temperature drilling fluids in deep and ultra-deep wells, so as to realize green, safe and efficient drilling in high-temperature formations.

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Abstract

本发明涉及取代的硬葡聚糖、其制造方法及其在钻井液组合物制造中的应用。本发明的取代的硬葡聚糖各自或组合带有取代基A、取代基B和取代基C，并且任选各自或组合带有取代基D和取代基E，其中所述取代基A在其结构中包含单元-C(＝O)-O-，所述取代基B在其结构中包含单元-C(＝O)-NH-，所述取代基C在其结构中包含单元（I），所述取代基D在其结构中包含芳基，所述取代基E在其结构中包含硅氧烷基，各取代基的定义如说明书所述。本发明的取代的硬葡聚糖具有优异的抗高温增黏提切性能，兼具良好的降滤失性能，绿色环保。

Description

取代的硬葡聚糖、其制造方法及其应用 技术领域
本发明涉及取代的硬葡聚糖，更具体地涉及一种取代的硬葡聚糖或者多种取代的硬葡聚糖的混合物。本发明还涉及所述取代的硬葡聚糖的制造方法、以及由所述取代的硬葡聚糖制造的钻井液组合物。
背景技术
随着世界环保要求的日益严格，国内外为实现绿色钻井液的目标开展了大量的工作，绿色钻井液的关键是钻井液处理剂及材料的绿色化。随着2015年以来我国《新环保法》的实施，对钻井液处理剂提出了更高的环保要求，当前钻井液处理剂正朝着绿色化的方向发展，除了环保因素之外，随着勘探开发过程中钻探深井、超深井及复杂地层的情况越来越多，现场对钻井液处理剂的性能要求也越来越高。
但是，现有技术的钻井液处理剂普遍存在着环保性能与稳定性能相冲突的现状。具体来说，改性天然材料或生物质材料环保性能好，无毒，易生物降解，但抗温性能有待提高，如淀粉类、纤维素类、黄原胶；高分子聚合物类处理剂稳定性能较好，但存在环保问题，毒性较高，难生物降解，如丙烯酰胺类、聚胺类。
发明内容
本发明的发明人发现，利用硬葡聚糖的高温黏切稳定性、环保型，在硬葡聚糖分子的多个羟基活性位上，通过糊化及接枝反应，制备得到取代的硬葡聚糖产品。本发明的发明人还发现，该产品具有较好的抗高温增粘提切效果，且绿色环保，对于消除环保压力、减少井下复杂、降低钻井成本等方面具有重要意义。本发明基于该发现而完成。
具体而言，本发明涉及以下方面的内容。
1.一种取代的硬葡聚糖或者多种取代的硬葡聚糖的混合物，各自或组合带有取代基A、取代基B和取代基C，并且任选各自或组合带有取代基D和取代基E，其中所述取代基A在其结构中包含单元-C(＝O)-O-(优选包含单元-C(＝O)-O-R 1，其中R 1选自氢原子、碱金属(比如K或Na)、碱土金属(比如Ca或Mg)、铵(NH 4)和C1-10或C1-4直链或支链烷基)，所述取代基B在其结构中包含单元-C(＝O)-HN-(优选包含单元-C(＝O)-NH-R 2，其中R 2选自氢原子和任选取代的C1-10或C1-4直链或支链烷基)，所述取代基C在其结构中包含单元
Figure PCTCN2021083303-appb-000001
(其中Ra、Rb和Rc彼此相同或不同，各自独立地选自氢原子和C1-10或C1-4直链或支链烷基，优选氢原子)，所述取代基D在其结构中包含芳基(优选苯基)，所述取代基E在其结构中包含硅氧烷基(优选用-Si(OR′) 3表示的硅氧烷基，其中R′是C1-4直链或支链烷基，优选甲基或乙基)。
2.前述或后述任一方面所述的一种取代的硬葡聚糖或者多种取代的硬葡聚糖的混合物，其中所述取代基A用以下化学式(A-1)、化学式(A-2)或者化学式(A-3)表示，
Figure PCTCN2021083303-appb-000002
在前述化学式中，基团R 3选自C2-6或C2-3直链或支链亚烷基(优选亚乙基或亚丙基)，基团L 1选自(优选碳原子数不超过10的)任意连接基团(优选单键或者C1-10或C1-4直链或支链亚烷基，特别是单键)，R 1选自氢原子、碱金属(比如K或Na)、碱土金属(比如Ca或Mg)、铵(NH 4)和C1-10或C1-4直链或支链烷基)，
所述取代基B用以下化学式(B-1)、化学式(B-11)、化学式(B-12)、化学式(B-2)、化学式(B-21)、化学式(B-22)、化学式(B-3)、化学式(B-31)或者化学式(B-32)表示，
Figure PCTCN2021083303-appb-000003
在前述化学式中，基团R 4、R 41、R 42彼此相同或不同，各自独立地选自C2-6或C2-3直链或支链亚烷基(优选亚乙基或亚丙基)，基团L 2、L 21、L 22彼此相同或不同，各自独立地选自(优选碳原子数不超过10的)任意连接基团(优选单键或者C1-10或C1-4直链或支链亚烷基，特别是单键)，M是碱金属(比如K或Na)、碱土金属(比如Ca或Mg)或铵(NH 4)，R 2 选自氢原子和任选取代的C1-10或C1-4直链或支链烷基，R 2′是氢原子，R 2″选自任选取代的C1-10或C1-4直链或支链烷基，
所述取代基C用以下化学式(C-1)、化学式(C-2)或者化学式(C-3)表示，
Figure PCTCN2021083303-appb-000004
在前述化学式中，基团R 5选自C2-6或C2-3直链或支链亚烷基(优选亚乙基或亚丙基)，基团L 3选自(优选碳原子数不超过10的)任意连接基团(优选单键或者C1-10或C1-4直链或支链亚烷基，特别是单键)，Ra、Rb和Rc彼此相同或不同，各自独立地选自氢原子和C1-10或C1-4直链或支链烷基(优选氢原子)，
所述取代基D用以下化学式(D-1)或者化学式(D-2)表示，
Figure PCTCN2021083303-appb-000005
在前述化学式中，基团L 4选自(优选碳原子数不超过10的)任意连接基团(优选单键或者C1-10或C1-4直链或支链亚烷基，特别是单键)，Ar选自C6-20芳基(优选苯基)，
所述取代基E用以下化学式(E-1)或者化学式(E-2)表示，
Figure PCTCN2021083303-appb-000006
在前述化学式中，基团L 5选自(优选碳原子数不超过10的)任意连接基团(优选单键或者C1-10或C1-4直链或支链亚烷基，特别是单键)，Rs是用-Si(OR′) 3表示的硅氧烷基(其中R′是C1-4直链或支链烷基，优选甲基或乙基)。
3.前述或后述任一方面所述的一种取代的硬葡聚糖或者多种取代的硬葡聚糖的混合物，是用以下化学式(I)表示的取代的硬葡聚糖或其多种的混合物，
Figure PCTCN2021083303-appb-000007
在化学式(I)中，n为2000-20000，优选5000-10000，最优选6000-8000，各个Z彼此相同或不同，各自独立地代表氢原子、所述取代基A、所述取代基B、所述取代基C、所述取代基D、所述取代基E、或者这些取代基的组合基团，前提是至少一个Z不是氢原子，并且在每个化学式(I)中，设所述取代基A的平均数目是o′，设所述取代基B的平均数目是x′，设所述取代基C的平均数目是p′，设所述取代基D的平均数目是y′，设所述取代基E的平均数目是z′，则o′为1-40(优选1-15)的任意数值，p′为1-20(优选1-10)的任意数值，x′为1-40(优选1-20)的任意数值，y′为0-20(优选1-15)的任意数值，z′为0-20(优选1-5)的任意数值。
4.前述或后述任一方面所述的一种取代的硬葡聚糖或者多种取代的硬葡聚糖的混合物，是用以下化学式(I-1)表示的取代的硬葡聚糖或其多种的混合物，
Figure PCTCN2021083303-appb-000008
在化学式(I-1)中，n为2000-20000，优选5000-10000，最优选6000-8000，各个Z′彼此相同或不同，各自独立地代表氢原子、用化学式(A-3)表示的取代基A(称为取代基A′)、用化学式(B-22)表示的取代基B(称为取代基B′)、用化学式(B-32)表示的取代基B(称为取代基B″)、用化学式(C-3)表示的取代基C(称为取代基C′)、用化学式(D-2)表示的取代基D(称为取代基D′)、用化学式(E-2)表示的取代基E(称为取代基E′)、或者这些取代基的组合基团，前提是至少一个Z′不是氢原子，并且在每个化学式(I-1)中，设所述取代基A′的平均数目是o，设所述取代基B′的平均数目是q，设所述取代基B″的平均数目是w，设所述取代基C′的平均数目是p，设所述取代基D′的平均数目是y，设所述取代基E′的平均数目是z，则o为1-20(优选1-15)的任意数值，p为1-20(优选1-10)的任意数值，q为1-20(优选1-15)的任意数值，w为1-20(优选1-10)的任意数值，y为0-20(优选1-15)的任意数值，z为0-20(优选1-5)的任意数值。
5.前述或后述任一方面所述的一种取代的硬葡聚糖或者多种取代的硬葡聚糖的混合物，是用以下化学式(I-2)示意性表示的取代的硬葡聚糖或其多种的混合物，
Figure PCTCN2021083303-appb-000009
在化学式(I-2)中，M是氢、碱金属(比如K或Na)、碱土金属(比如Ca或Mg)或铵(NH 4)，*代表共价键合位点。
6.前述或后述任一方面所述的一种取代的硬葡聚糖或者多种取代的硬葡聚糖的混合物，其胺值为0.2-0.6mmol/g，和/或，其HLB值为15.0-20.0。
7.一种取代的硬葡聚糖或者多种取代的硬葡聚糖的混合物的制造方法，包括以下步骤：
1)使以下化学式(A)表示的硬葡聚糖在碱(优选选自碱金属氢氧化物和碱土金属氢氧化物中的至少一种，特别是选自氢氧化钠、氢氧化钾和氢氧化钙中的至少一种)和水的存在下发生糊化反应，得到硬葡聚糖凝胶，
Figure PCTCN2021083303-appb-000010
在化学式(A)中，n为2000-20000，优选5000-10000，最优选6000-8000，
2)使用化学式(X-1)表示的羧酸单体、用化学式(X-2)表示的酰胺单体、用化学式(X-3)表示的磺酸单体、用化学式(X-4)表示的吡咯烷酮单体、任选的用化学式(X-5)表示的苯基单体、以及任选的用化学式(X-6)表示的硅氧烷基单体在碱(优选选自碱金属氢氧化物和碱土金属氢氧化物中的至少一种，特别是选自氢氧化钠、氢氧化钾和氢氧化钙中的至少一种)的存在下与水混合(优选均匀混合)，获得混合单体，和
3)使所述硬葡聚糖凝胶与所述混合单体在自由基聚合引发剂(优选选自过氧化物类引发剂、偶氮类引发剂和氧化还原类引发剂中的至少一种，特别是选自过氧化氢、过硫酸铵、偶氮二异丁腈、硝酸铈铵、以及质量份1∶2的亚硫酸氢钠和过硫酸铵中的至少一种)的存在下发生自由基聚合反应，任选进行干燥，获得所述一种取代的硬葡聚糖或者多种取代的硬葡聚糖的混合物，
Figure PCTCN2021083303-appb-000011
在化学式(X-1)至化学式(X-6)中，基团L 1、L 21、L 22、L 3、L 4、L 5彼此相同或不同，各自独立地选自(优选碳原子数不超过10的)任意连接基团(优选单键或者C1-10或C1-4直链或支链亚烷基，特别是单键)，M是 碱金属(比如K或Na)、碱土金属(比如Ca或Mg)或铵(NH 4)，Ra、Rb和Rc彼此相同或不同，各自独立地选自氢原子和C1-10或C1-4直链或支链烷基(优选氢原子)，R 1选自氢原子、碱金属(比如K或Na)、碱土金属(比如Ca或Mg)、铵(NH 4)和C1-10或C1-4直链或支链烷基(优选氢原子)，Ar是C6-20芳基(优选苯基)，Rs是用-Si(OR′) 3表示的硅氧烷基(其中R′是C1-4直链或支链烷基，优选甲基或乙基)。
8.前述或后述任一方面所述的制造方法，其中在所述步骤1)中，所述硬葡聚糖、水与所述碱的质量比为12∶(180-220)∶(4-8)，和/或，在所述步骤1)中，反应温度为60-70℃，反应时间为0.5-2h，和/或，在所述步骤2)中，所述用化学式(X-1)表示的羧酸单体、所述用化学式(X-4)表示的吡咯烷酮单体、所述用化学式(X-2)表示的酰胺单体、所述用化学式(X-3)表示的磺酸单体、所述碱与水的质量比为20∶(15-18)∶(54-64)∶(27-36)∶(6-8)∶(50-80)，和/或，在所述步骤2)中，所述用化学式(X-1)表示的羧酸单体、所述用化学式(X-5)表示的苯基单体与所述用化学式(X-6)表示的硅氧烷基单体的质量比为20∶(27-45)∶(9-15)，和/或，在所述步骤2)中，混合温度为30-40℃，和/或，在所述步骤3)中，所述混合单体(以全部单体的总重量为计)、所述硬葡聚糖凝胶(以硬葡聚糖的重量为计)与所述自由基聚合引发剂的质量比为(152-198)∶12∶(0.8-1.6)，和/或，在所述步骤3)中，聚合反应体系的pH值控制为8-10，反应温度为40-70℃，反应时间为4-10h，和/或，在所述步骤3)中，干燥温度为80-100℃。
9.一种钻井液组合物，包含取代的硬葡聚糖、基浆和任选的至少一种处理剂，其中所述取代的硬葡聚糖是前述或后述任一方面所述的一种取代的硬葡聚糖或者多种取代的硬葡聚糖的混合物或者通过前述或后述任一方面所述的制造方法制造的一种取代的硬葡聚糖或者多种取代的硬葡聚糖的混合物。
10.前述或后述任一方面所述的钻井液组合物，其中以所述钻井液组合物的总质量为100wt％计，所述取代的硬葡聚糖的质量百分含量为0.5-10.0wt％(优选1.5-5.0wt％)。
11.一种钻井液组合物的制造方法，包括混合取代的硬葡聚糖、基浆和任选的至少一种处理剂(优选先混合所述取代的硬葡聚糖与所述基浆，然后再将所获得的混合物与所述任选的至少一种处理剂混合)而获得所述钻井液组合物，其中所述取代的硬葡聚糖是前述或后述任一方面所述的一种取代的硬葡聚糖或者多种取代的硬葡聚糖的混合物或者通过前述或后述任一方面所述的制造方法制造的一种取代的硬葡聚糖或者多种取代的硬葡聚糖的混合物，和，任选将所获得的钻井液组合物进行老化处理(优选处理温度为120-200℃或140-180℃，优选155-165℃，处理时间为10-30小时或15-20小时，优选15-17小时)。
技术效果
本发明的取代的硬葡聚糖在高温条件下显示出优异的增黏提切性能，同时具有优异的降滤失性能，并且绿色环保，特别适用于地层温度较高的深井、超深井钻井施工用钻井液。
本发明的取代的硬葡聚糖的制造方法的反应条件温和、工艺操作简单，无废水废气废渣排放，绿色环保。
附图说明
图1为实施例和比较例中使用的硬葡聚糖的红外图谱。
图2为实施例1得到的取代的硬葡聚糖的红外图谱。
具体实施方式
下面对本发明的具体实施方式进行详细说明，但是需要指出的是，本发明的保护范围并不受这些具体实施方式的限制，而是由附录的权利要求书来确定。
本说明书提到的所有出版物、专利申请、专利和其它参考文献全都引于此供参考。除非另有定义，本说明书所用的所有技术和科学术语都具有本领域技术人员常规理解的含义。在有冲突的情况下，以本说明书的定义为准。
当本说明书以词头“本领域技术人员公知”、“现有技术”或其类似用语来导出材料、物质、方法、步骤、装置或部件等时，该词头导出的对象涵盖本申请提出时本领域常规使用的那些，但也包括目前还不常用，却将变成本领域公认为适用于类似目的的那些。
在本说明书的上下文中，在没有特别明确的情况下，芳基指的是C6-20芳基，优选苯基。
在本说明书的上下文中，表述“任选取代”指的是任选被一个或多个(比如1至5个、1至4个、1至3个、1至2个或者1个)选自羟基、C1-4烷氧基、氨基和磺基(-SO 3M)的取代基取代，优选磺基(-SO 3M)。在此，M是碱金属(比如K或Na)、碱土金属(比如Ca或Mg)或铵(NH 4)。
在本说明书的上下文中，HLB值的测量包括：称取待测样品1.0g(精确至0.0001g)，放入洁净干燥的250mL锥形瓶中，精确称量99.0g去离子水，放入上述锥形瓶中，配成1.0％待测样品的水溶液。将上述锥形瓶在恒温水浴中逐渐加热，当待测样品水溶液透明度降低而变混浊时，锥形瓶内的温度就是待测样品的浊点T。通过随机抽取3批次待测样品进行浊点测量。按式(1)计算HLB值：
HLB值＝0.0980T+4.02    (1)
式中：
T-待测样品浊点，单位为摄氏度(℃)。
在本说明书的上下文中，胺值的测量包括：称取待测样品0.5g(精确至0.0001g)，放入洁净干燥的250mL锥形瓶中，加入50mL去离子水并记录总质量m 1。在上述待测液中加入溴甲酚绿-甲基红指示剂5滴，摇匀，用盐酸标准溶液逐滴匀速滴定，边均匀摇动边仔细观察溶液的颜色变化，当溶液颜色由绿色变为暗红色即为滴定终点。记录消耗盐酸标准溶液体积V。同时做空白试验。通过随机抽取3批次待测样品进行胺值测量。按式(2)计算胺值：
Figure PCTCN2021083303-appb-000012
式中：
总胺值-以H +计，单位为毫摩尔每克(mmol/g)；
C HCl-所用盐酸标准溶液的浓度，单位为摩尔每升(mol/L)；
V-待测样品消耗盐酸-异丙醇标准溶液的体积的数值，单位为毫升(mL)；
V 空白-空白试验盐酸溶液的体积的数值，单位为毫升(mL)；
m-称取待测样品质量的准确数值，单位为克(g)。
在没有明确指明的情况下，本说明书内所提到的所有百分数、份数、比率等都是以重量为基准的，而且压力是表压。
在本说明书的上下文中，本发明的任何两个或多个实施方式都可以任意组合，由此而形成的技术方案属于本说明书原始公开内容的一部分，同时也落入本发明的保护范围。
根据本发明的一个实施方式，涉及一种取代的硬葡聚糖或者多种取代的硬葡聚糖的混合物。在此，所谓“一种取代的硬葡聚糖”，指的是以单独化合物形式存在的取代的硬葡聚糖，而所谓“多种取代的硬葡聚糖的混合物”，则指的是两种以上(即多种)取代的硬葡聚糖混合在一起而形成的混合物。对于本发明而言，取代的硬葡聚糖是以各自化合物的形式分别独立存在，还是以彼此混合物的形式存在，都能够实现本发明的预期目的，并没有特别的限定。因此，本发明有时将所述一种取代的硬葡聚糖与所述多种取代的硬葡聚糖的混合物统称为取代的硬葡聚糖。
根据本发明的一个实施方式，所述硬葡聚糖(或硬葡聚糖骨架)可以用以下化学式(A)表示。在此，所述硬葡聚糖的存在可以通过红外分析方法予以确认。比如，在所述取代的硬葡聚糖的红外谱图上，在3405、2878、1387、1064cm -1处或其附近显示特征峰，就可以确认所述硬葡聚糖的存在。
Figure PCTCN2021083303-appb-000013
在化学式(A)中，n为2000-20000，优选5000-10000，最优选6000-8000。
根据本发明的一个实施方式，所述取代的硬葡聚糖各自或组合带有取代基A、取代基B和取代基C，并且任选地，各自或组合带有取代基D和取代基E，也即所述取代基D和所述取代基E是非必要的取代基。在此，所谓各自带有，指的是所述取代基A、所述取代基B、所述取代基C、所述取代基D(如有)、所述取代基E(如有)分别位于不同的硬葡聚糖分子上，而所谓组合带有，则指的是所述取代基A、所述取代基B、所述取代基C、所述取代基D(如有)、所述取代基E(如有)既可以分别位于不同的硬葡聚糖分子上，也可以按照任意的组合(比如两两组合或者三个同时)位于不同或同一个硬葡聚糖分子上。
根据本发明的一个实施方式，所述取代基A在其结构中包含单元-C(＝O)-O-，优选包含单元-C(＝O)-O-R 1，其中R 1选自氢原子、碱金属(比如K或Na)、碱土金属(比如Ca或Mg)、铵(NH 4)和C1-10或C1-4直链或支链烷基。在此，所述这些单元或者所述取代基A的存在可以通过红外分析方法予以确认。比如，在所述取代的硬葡聚糖的红外谱图上，在2938cm -1处或其附近显示特征峰，就可以确认这些单元或所述取代基A的存在。
根据本发明的一个实施方式，所述取代基A可以用以下化学式(A-1)、化学式(A-2)或者化学式(A-3)表示。
Figure PCTCN2021083303-appb-000014
在前述这些化学式中，基团R 3选自C2-6或C2-3直链或支链亚烷基，优选亚乙基或亚丙基。基团L 1选自任意连接基团，优选碳原子数不超过10的任意连接基团，特别优选单键或者C1-10或C1-4直链或支链亚烷基，特别是单键。R 1选自氢原子、碱金属(比如K或Na)、碱土金属(比如Ca或Mg)、铵(NH 4)和C1-10或C1-4直链或支链烷基。另外，此处所有没有明确定义的基团和数值，直接适用本说明书前文针对所述取代基A给出的相应定义。
根据本发明的一个实施方式，所述取代基B在其结构中包含单元-C(＝O)-NH-，优选包含单元-C(＝O)-NH-R 2，其中R 2选自氢原子和任选取代的C1-10或C1-4直链或支链烷基。在此，所述这些单元或者所述取代基B的存在可以通过红外分析方法予以确认。比如，在所述取代的硬葡聚糖的红外谱图上，在1195cm -1处或其附近显示特征峰，就可以确认这些单元或所述取代基B的存在。
根据本发明的一个实施方式，所述取代基B可以用以下化学式(B-1)、化学式(B-11)、化学式(B-12)、化学式(B-2)、化学式(B-21)、化学式(B-22)、化学式(B-3)、化学式(B-31)或者化学式(B-32)表示。
Figure PCTCN2021083303-appb-000015
Figure PCTCN2021083303-appb-000016
在前述这些化学式中，基团R 4、R 41、R 42彼此相同或不同，各自独立地选自C2-6或C2-3直链或支链亚烷基，优选亚乙基或亚丙基。基团L 2、L 21、L 22彼此相同或不同，各自独立地选自任意连接基团，优选碳原子数不超过10的任意连接基团，特别优选单键或者C1-10或C1-4直链或支链亚烷基，特别是单键。M是碱金属(比如K或Na)、碱土金属(比如Ca或Mg)或铵(NH 4)。R 2选自氢原子和任选取代的C1-10或C1-4直链或支链烷基，R 2′是氢原子，R 2″选自任选取代的C1-10或C1-4直链或支链烷基。另外，此处所有没有明确定义的基团和数值，直接适用本说明书前文针对所述取代基B给出的相应定义。
根据本发明的一个实施方式，所述取代基C在其结构中包含单元
Figure PCTCN2021083303-appb-000017
其中Ra、Rb和Rc彼此相同或不同，各自独立地选自氢原子和C1-10或C1-4直链或支链烷基，优选氢原子。在此，所述单元或者所述取代基C的存在可以通过红外分析方法予以确认。比如，在所述取代的硬葡聚糖的红外谱图上，在1674cm -1处或其附近显示特征峰，就可以确认所述单元或所述取代基C的存在。
根据本发明的一个实施方式，所述取代基C可以用以下化学式(C-1)、化学式(C-2)或者化学式(C-3)表示。
Figure PCTCN2021083303-appb-000018
在前述这些化学式中，基团R 5选自C2-6或C2-3直链或支链亚烷基，优选亚乙基或亚丙基。基团L 3选自任意连接基团，优选碳原子数不超过10的任意连接基团，特别优选单键或者C1-10或C1-4直链或支链亚烷基，特别是单键。Ra、Rb和Rc彼此相同或不同，各自独立地选自氢原子和C1-10 或C1-4直链或支链烷基，优选氢原子。另外，此处所有没有明确定义的基团和数值，直接适用本说明书前文针对所述取代基C给出的相应定义。
根据本发明的一个实施方式，所述取代基D在其结构中包含芳基，优选苯基。在此，所述这些单元或者所述取代基D的存在可以通过红外分析方法予以确认。比如，在所述取代的硬葡聚糖的红外谱图上，在1453cm -1处或其附近显示特征峰，就可以确认这些单元或所述取代基D的存在。
根据本发明的一个实施方式，所述取代基D可以用以下化学式(D-1)或者化学式(D-2)表示。
Figure PCTCN2021083303-appb-000019
在前述这些化学式中，基团L 4选自任意连接基团，优选碳原子数不超过10的任意连接基团，特别优选单键或者C1-10或C1-4直链或支链亚烷基，特别是单键。Ar选自C6-20芳基，优选苯基。另外，此处所有没有明确定义的基团和数值，直接适用本说明书前文针对所述取代基D给出的相应定义。
根据本发明的一个实施方式，所述取代基E在其结构中包含硅氧烷基，优选包含用-Si(OR′) 3表示的硅氧烷基，其中R′是C1-4直链或支链烷基，优选甲基或乙基。在此，所述这些单元或者所述取代基E的存在可以通过红外分析方法予以确认。比如，在所述取代的硬葡聚糖的红外谱图上，在2150cm -1处或其附近显示特征峰，就可以确认这些单元或所述取代基E的存在。
根据本发明的一个实施方式，所述取代基E可以用以下化学式(E-1)或者化学式(E-2)表示。
Figure PCTCN2021083303-appb-000020
在前述这些化学式中，基团L 5选自任意连接基团，优选碳原子数不超过10的任意连接基团，特别优选单键或者C1-10或C1-4直链或支链亚烷基，特别是单键。Rs是用-Si(OR′) 3表示的硅氧烷基，其中R′是C1-4直链或支链烷基，优选甲基或乙基。另外，此处所有没有明确定义的基团和数值，直接适用本说明书前文针对所述取代基E给出的相应定义。
根据本发明的一个实施方式，所述取代的硬葡聚糖是用以下化学式(I)表示的取代的硬葡聚糖或其多种的混合物。
在本说明书的上下文中，任何硬葡聚糖分子或任何取代的硬葡聚糖分子的立体构型仅仅是为了方便理解而绘制的，并不用来限定本发明。实际上，这些分子可以是任意的立体构型而不脱离本发明的主旨。
Figure PCTCN2021083303-appb-000021
在化学式(I)中，以n代表一个硬葡聚糖分子的聚合度，则一般为2000-20000，优选5000-10000，最优选6000-8000。各个Z彼此相同或不同，各自独立地代表氢原子、所述取代基A、所述取代基B、所述取代基C、所述取代基D、所述取代基E、或者这些取代基的组合基团，前提是至少一个Z不是氢原子，也即一个硬葡聚糖分子中至少有一个-OH上的氢原子被这些取代基中的某一个所取代。在此，所谓“组合基团”，指的是所述取代基A、所述取代基B、所述取代基C、所述取代基D、所述取代基E中的相同取代基或不同取代基之间两个或多个以任意键合顺序组合而形成的链状结构，具体的示意性举例比如如下所示，但本发明并不限于此。而且，本发明对于相同或不同取代基之间的键合顺序也没有特别的限定，比如可以 举出相同或不同取代基之间以任何顺序键合而形成比如无规、嵌段或交替等链状结构。
Figure PCTCN2021083303-appb-000022
根据本发明的一个实施方式，在每个化学式(I)中，设所述取代基A的平均数目是o′，设所述取代基B的平均数目是x′，设所述取代基C的平均数目是p′，设所述取代基D的平均数目是y′，设所述取代基E的平均数目是z′，则o′为1-40(优选1-15)的任意数值，p′为1-20(优选1-10)的任意数值，x′为1-40(优选1-20)的任意数值，y′为0-20(优选1-15)的任意数值，z′为0-20(优选1-5)的任意数值。本发明并不意在控制或限定某一个取代基在一个硬葡聚糖分子上的具体数量，因此在本说明书的上下文中，所谓某一个取代基的“平均数目”，指的是所述取代基相对于全部硬葡聚糖分子的统计平均数量。该数量可以是整数，也可以是非整数。
根据本发明的一个实施方式，所述取代的硬葡聚糖是用以下化学式(I-1)表示的取代的硬葡聚糖或其多种的混合物。
Figure PCTCN2021083303-appb-000023
在化学式(I-1)中，以n代表一个硬葡聚糖分子的聚合度，则一般为2000-20000，优选5000-10000，最优选6000-8000。各个Z′彼此相同或不同，各自独立地代表氢原子、用化学式(A-3)表示的取代基A(称为取代基A′)、用化学式(B-22)表示的取代基B(称为取代基B′)、用化学式(B-32)表示的取代基B(称为取代基B″)、用化学式(C-3)表示的取代基C(称为取代基C′)、用化学式(D-2)表示的取代基D(称为取代基D′)、用化学式(E-2)表示的取代基E(称为取代基E′)、或者这些取代基的组合基团，前提是至少一个Z′不是氢原子，也即一个硬葡聚糖分子中至少有一个-OH上的氢原子被这些取代基中的某一个所取代。在此，所谓“组合基团”，指的是所述取代基A′、所述取代基B′、所述取代基B″、所述取代基C′、所述取代基D′、所述取代基E′中的相同取代基或不同取代基之间两个或多个以任意键合顺序组合而形成的链状结构，具体的示意性举例比如如前文所示，但本发明并不限于此。而且，本发明对于相同或不同取代基之间的键合顺序也没有特别的限定，比如可以举出相同或不同取代基之间以任何顺序键合而形成比如无规、嵌段或交替等链状结构。
根据本发明的一个实施方式，在每个化学式(I-1)中，设所述取代基A′的平均数目是o，设所述取代基B′的平均数目是q，设所述取代基B″的平均数目是w，设所述取代基C′的平均数目是p，设所述取代基D′的平均数目是y，设所述取代基E′的平均数目是z，则o为1-20(优选1-15)的 任意数值，p为1-20(优选1-10)的任意数值，q为1-20(优选1-15)的任意数值，w为1-20(优选1-10)的任意数值，y为0-20(优选1-15)的任意数值，z为0-20(优选1-5)的任意数值。如前所述，本发明并不意在控制或限定某一个取代基在一个硬葡聚糖分子上的具体数量，因此在本说明书的上下文中，所谓某一个取代基的“平均数目”，指的是所述取代基相对于全部硬葡聚糖分子的统计平均数量。该数量可以是整数，也可以是非整数。另外，此处所有没有明确定义的基团和数值，直接适用本说明书前文针对所述化学式(1)给出的相应定义。
根据本发明的一个实施方式，所述取代的硬葡聚糖是用以下化学式(I-2)示意性表示的取代的硬葡聚糖或其多种的混合物。在本说明书的上下文中，所谓“示意性”，指的是仅为了方便理解起见，将相同和不同的取代基全部集合在一个链状结构中，并且在所述链状结构中，相同的取代基以各自的平均数目作为重复单元数目而形成嵌段结构。但是，这示意性表达并不意味着在本发明的取代的硬葡聚糖分子上或其混合物中必然存在这种链状结构，也不意味着相同的取代基必然以各自的平均数目作为重复单元数目而形成独立的嵌段，而且也不意味着不同的取代基(包括不同的嵌段)必须按照所述化学式所示的特定顺序进行键合。实际上，根据本发明的精神主旨，相同的取代基或不同的取代基可以按照任意的组合方式键合在一个或多个硬葡聚糖分子上，比如以单独或任意的组合方式取代硬葡聚糖分子上某一个羟基的氢原子。作为所述组合方式，比如可以举出以任何顺序键合而形成比如无规、嵌段或交替等链状结构。这些实施方式都属于本发明的预期范围，并没有特别的限定。本说明书中的其他化学式均可以类似理解。
Figure PCTCN2021083303-appb-000024
在化学式(I-2)中，M是氢、碱金属(比如K或Na)、碱土金属(比如Ca或Mg)或铵(NH 4)。另外，*代表共价键合位点，也即所述链状结构将经由所述*代表的自由端与所述硬葡聚糖分子实现共价键合(替代硬葡聚糖分子结构上某个羟基的氢原子)。另外，此处所有没有明确定义的基团和数值，直接适用本说明书前文针对所述化学式(I)或所述化学式(I-1)给出的相应定义。
根据本发明的一个实施方式，所述取代的硬葡聚糖的胺值为0.2-0.6mmol/g。
根据本发明的一个实施方式，所述取代的硬葡聚糖的HLB值为15.0-20.0。
根据本发明的一个实施方式，所述取代的硬葡聚糖可以按照本发明的一种取代的硬葡聚糖或者多种取代的硬葡聚糖的混合物的制造方法进行制造。
根据本发明的一个实施方式，所述制造方法可以包括以下步骤。
1)使硬葡聚糖在碱和水的存在下发生糊化反应，得到硬葡聚糖凝胶。
根据本发明的一个实施方式，在所述步骤1)中，所述碱选自碱金属氢氧化物和碱土金属氢氧化物中的至少一种，特别是选自氢氧化钠、氢氧化钾和氢氧化钙中的至少一种。
根据本发明的一个实施方式，在所述步骤1)中，所述硬葡聚糖、水与所述碱的质量比一般为12∶(180-220)∶(4-8)。
根据本发明的一个实施方式，在所述步骤1)中，反应温度一般为60-70℃，反应时间一般为0.5-2h。
根据本发明的一个实施方式，在所述步骤1)中，所述硬葡聚糖(即一个硬葡聚糖分子)可以用以下化学式(A)表示。
Figure PCTCN2021083303-appb-000025
在化学式(A)中，n为2000-20000，优选5000-10000，最优选6000-8000。
2)使用化学式(X-1)表示的羧酸单体、用化学式(X-2)表示的酰胺单体、用化学式(X-3)表示的磺酸单体、用化学式(X-4)表示的吡咯烷酮单体、任选的用化学式(X-5)表示的苯基单体、以及任选的用化学式(X-6)表示的硅氧烷基单体在碱的存在下与水混合，获得混合单体。在此，作为所述混合，优选均匀混合
根据本发明的一个实施方式，在所述步骤2)中，所述碱选自碱金属氢氧化物和碱土金属氢氧化物中的至少一种，特别是选自氢氧化钠、氢氧化钾和氢氧化钙中的至少一种。
Figure PCTCN2021083303-appb-000026
在化学式(X-1)至化学式(X-6)中，基团L 1、L 21、L 22、L 3、L 4、L 5彼此相同或不同，各自独立地选自任意连接基团，优选碳原子数不超过10的任意连接基团，优选单键或者C1-10或C1-4直链或支链亚烷基，特别是单键。M是碱金属(比如K或Na)、碱土金属(比如Ca或Mg)或铵(NH 4)。Ra、Rb和Rc彼此相同或不同，各自独立地选自氢原子和C1-10或C1-4直链或支链烷基，优选氢原子。R 1选自氢原子、碱金属(比如K或Na)、碱土金属(比如Ca或Mg)、铵(NH 4)和C1-10或C1-4直链或支链烷基，优选氢原子。Ar是C6-20芳基，优选苯基。Rs是用-Si(OR′) 3表示的硅氧烷基，其中R′是C1-4直链或支链烷基，优选甲基或乙基。
根据本发明的一个实施方式，在所述步骤2)中，所述用化学式(X-1)表示的羧酸单体、所述用化学式(X-4)表示的吡咯烷酮单体、所述用化学式(X-2)表示的酰胺单体、所述用化学式(X-3)表示的磺酸单体、所述碱与水的质量比为20∶(15-18)∶(54-64)∶(27-36)∶(6-8)∶(50-80)。
根据本发明的一个实施方式，在所述步骤2)中，在使用的情况下，所述用化学式(X-1)表示的羧酸单体、所述用化学式(X-5)表示的苯基单 体与所述用化学式(X-6)表示的硅氧烷基单体的质量比为20∶(27-45)∶(9-15)。
根据本发明的一个实施方式，在所述步骤2)中，混合温度一般为30-40℃。
3)使所述硬葡聚糖凝胶与所述混合单体在自由基聚合引发剂的存在下发生自由基聚合反应，任选进行干燥，获得所述取代的硬葡聚糖。在此，干燥是任选步骤。
根据本发明的一个实施方式，在所述步骤3)中，所述自由基聚合引发剂选自过氧化物类引发剂、偶氮类引发剂和氧化还原类引发剂中的至少一种，特别是选自过氧化氢、过硫酸铵、偶氮二异丁腈、硝酸铈铵、以及质量份1∶2的亚硫酸氢钠和过硫酸铵中的至少一种。
根据本发明的一个实施方式，在所述步骤3)中，所述混合单体(以全部单体的总重量为计)、所述硬葡聚糖凝胶(以硬葡聚糖的重量为计)与所述自由基聚合引发剂的质量比一般为(152-198)∶12∶(0.8-1.6)。
根据本发明的一个实施方式，在所述步骤3)中，所述聚合反应体系的pH值一般控制为8-10，比如可以通过加入氢氧化钠水溶液的方式进行。
根据本发明的一个实施方式，在所述步骤3)中，所述聚合反应体系的反应温度一般为40-70℃，反应时间一般为4-10h。
根据本发明的一个实施方式，在所述步骤3)中，干燥温度一般为80-100℃。该干燥可以在烘箱中进行。在干燥之后，可以进行粉碎。
根据本发明的一个实施方式，所述步骤1)至所述步骤3)可以在搅拌的存在下进行。为此，所述搅拌的搅拌速度一般为800-4000r/min，优选1000-1100r/min。
根据本发明的一个实施方式，还涉及一种钻井液组合物，其包含取代的硬葡聚糖、基浆和任选的至少一种处理剂。在此，所述取代的硬葡聚糖可以是本发明如前所述的任意一种取代的硬葡聚糖或者多种取代的硬葡聚糖的混合物或者通过本发明如前所述的任意制造方法制造的一种取代的硬葡聚糖或者多种取代的硬葡聚糖的混合物。
根据本发明的一个实施方式，在所述钻井液组合物中，以所述钻井液组合物的总质量为100wt％计，所述取代的硬葡聚糖的质量百分含量一般为0.5-10.0wt％，优选1.5-5.0wt％。
根据本发明的一个实施方式，还涉及一种钻井液组合物的制造方法。所述制造方法包括混合取代的硬葡聚糖、基浆和任选的至少一种处理剂而获得所述钻井液组合物的步骤(称为混合步骤)。在此，所述取代的硬葡聚糖可以是本发明如前所述的任意一种取代的硬葡聚糖或者多种取代的硬葡聚糖的混合物或者通过本发明如前所述的任意制造方法制造的一种取代的硬葡聚糖或者多种取代的硬葡聚糖的混合物。
根据本发明的一个实施方式，作为所述至少一种处理剂，可以使用本领域在钻井液组合物中常规使用的任何处理剂，具体比如可以举出选自增粘剂、流型调节剂、降滤失剂、高温稳定剂、封堵剂、抑制增强剂和pH调节剂中的至少一种。这些处理剂的类型和用量可以直接适用本领域已知的那些，并没有特别的限定。
根据本发明的一个优选实施方式，为了更为优异地实现本发明的技术效果，在所述混合步骤中，先混合所述取代的硬葡聚糖与所述基浆，然后再将所获得的混合物与所述任选的至少一种处理剂混合。
根据本发明的一个实施方式，在所述混合步骤中，所述混合在高速搅拌下进行，比如所述高速搅拌的转速优选为5000r/min-10000r/min，时间优选为10min-30min。
根据本发明的一个优选实施方式，所述钻井液组合物的制造方法还包括将所述混合步骤获得的钻井液组合物进行老化处理的步骤(称为老化步骤)。
根据本发明的一个实施方式，在所述老化步骤中，处理温度一般为120-200℃或140-180℃，优选155-165℃，而处理时间一般为10-30小时或15-20小时，优选15-17小时。
实施例
以下将通过实施例和比较例对本发明进行进一步的详细描述，但本发明不限于以下实施例。
以下实施例和比较例所用的原料均为市售商品。具体来说，以下实施例和比较例所用的硬葡聚糖(n＝7400-7600)如图1所示，在其红外光谱中，3405cm -1处是硬葡聚糖O-H键的伸缩振动峰，2878cm -1是甲基和亚甲基的C-H键伸缩振动吸收峰，可确定含有硬葡聚糖的结构；1387cm -1处为-C-H-对称弯曲振动吸收峰，1064cm -1处为C-O伸缩振动吸收峰，该红外图谱较好地反映了硬葡聚糖的主要特征吸收峰。
实施例1
将12g硬葡聚糖、180g水、4g氢氧化钠加入聚合釜，控制搅拌速度在1000r/min，温度60℃下碱化糊化0.5h，得到硬葡聚糖凝胶；将20g丙烯酸、15g乙烯基吡咯烷酮、54g丙烯酰胺、27g 2-丙烯酰胺-2-甲基丙磺酸、6g氢氧化钠、50g水加入混合釜，控制搅拌速度在1000r/min，温度30℃下搅拌均匀，得到单体水溶液；将上述硬葡聚糖凝胶与单体水溶液混合，在搅拌速度1000r/min下搅拌均匀，用40％氢氧化钠水溶液调节反应液pH值至8，将0.12g过氧化氢引发剂加入反应液中，在40℃下反应4h，得到乳黄色半透明黏稠状液体，在烘箱中于80℃下干燥、粉碎，即得取代的硬葡聚糖抗高温增黏提切剂。产品收率为92.81％。
该产品的胺值为0.20mmol/g，HLB值为15.0。
将该例制造得到的产品进行红外检测，检测结果(如图2所示)为，在2938cm -1处显示特征峰，确认所述取代基A或所述取代基A′的存在，在1195cm -1处显示特征峰，确认所述取代基B′的存在，在1049、1195cm -1处显示特征峰，确认所述取代基B″的存在，在1674cm -1处显示特征峰，确认所述取代基C或所述取代基C′的存在，在1453cm -1处显示特征峰，确认所述取代基D或所述取代基D′的存在，在2150cm -1处显示特征峰，确认所述取代基E或所述取代基E′的存在。
本发明实施例1制备得到的取代的硬葡聚糖具有式1所示的示意性结构：
Figure PCTCN2021083303-appb-000027
式1中：n为7400-7600，o为10.5，p为8.4，q为12.5，w为8.2，y为0，z为0，M为Na。
实施例2
将12g硬葡聚糖、190g水、5g氢氧化钾加入聚合釜，控制搅拌速度在1100r/min，温度62℃下碱化糊化1.0h，得到硬葡聚糖凝胶；将20g丙烯酸、16g乙烯基吡咯烷酮、58g丙烯酰胺、30g 2-丙烯酰胺-2-甲基丙磺酸、7g氢氧化钾、60g水加入混合釜，控制搅拌速度在1100r/min，温度35℃下搅拌均匀，得到单体水溶液；将上述硬葡聚糖凝胶与单体水溶液混合，在搅拌速度1100r/min下搅拌均匀，用40％氢氧化钾水溶液调节反应液pH值至9，将0.16g过硫酸铵引发剂加入反应液中，在50℃下反应5h，得到乳黄色半透明黏稠状液体，在烘箱中于90℃下干燥、粉碎，即得取代的硬葡聚糖抗高温增黏提切剂。产品收率为93.64％。
该产品的胺值为0.26mmol/g，HLB值为15.2。
将该例制造得到的产品进行红外检测，检测结果为，在2939cm -1处显示特征峰，确认所述取代基A或所述取代基A′的存在，在1196cm -1处显示特征峰，确认所述取代基B′的存在，在1048、1196cm -1处显示特征峰，确认所述取代基B″的存在，在1675cm -1处显示特征峰，确认所述取代基C 或所述取代基C′的存在，在1454cm -1处显示特征峰，确认所述取代基D或所述取代基D′的存在，在2151cm -1处显示特征峰，确认所述取代基E或所述取代基E′的存在。
本发明实施例2制备得到的取代的硬葡聚糖具有式2所示的示意性结构：
Figure PCTCN2021083303-appb-000028
式2中：n为7400-7600，o为11.2，p为8.8，q为12.9，w为8.7，y为0，z为0，M为K。
实施例3
将12g硬葡聚糖、200g水、6g氢氧化钙加入聚合釜，控制搅拌速度在1100r/min，温度64℃下碱化糊化1.5h，得到硬葡聚糖凝胶；将20g丙烯酸、17g乙烯基吡咯烷酮、60g丙烯酰胺、32g 2-丙烯酰胺-2-甲基丙磺酸、8g氢氧化钙、70g水加入混合釜，控制搅拌速度在1100r/min，温度40℃下搅拌均匀，得到单体水溶液；将上述硬葡聚糖凝胶与单体水溶液混合，在搅拌速度1100r/min下搅拌均匀，用40％氢氧化钙水溶液调节反应液pH值至10，将0.20g偶氮二异丁腈引发剂加入反应液中，在60℃下反应7h，得到乳黄色半透明黏稠状液体，在烘箱中于100℃下干燥、粉碎，即得取代的硬葡聚糖抗高温增黏提切剂。产品收率为93.87％。
该产品的胺值为0.35mmol/g，HLB值为16.8。
将该例制造得到的产品进行红外检测，检测结果为，在2937cm -1处显示特征峰，确认所述取代基A或所述取代基A′的存在，在1195cm -1处显示特征峰，确认所述取代基B′的存在，在1046、1198cm -1处显示特征峰，确认所述取代基B″的存在，在1676cm -1处显示特征峰，确认所述取代基C或所述取代基C′的存在，在1455cm -1处显示特征峰，确认所述取代基D或所述取代基D′的存在，在2152cm -1处显示特征峰，确认所述取代基E或所述取代基E′的存在。
本发明实施例3制备得到的取代的硬葡聚糖具有式3所示的示意性结构：
Figure PCTCN2021083303-appb-000029
式3中：n为7400-7600，o为12.5，p为9.6，q为13.5，w为9.2，y为0，z为0，M为Ca。
实施例4
将12g硬葡聚糖、210g水、7g氢氧化钠加入聚合釜，控制搅拌速度在1100r/min，温度66℃下碱化糊化2.0h，得到硬葡聚糖凝胶；将20g丙烯酸、18g乙烯基吡咯烷酮、64g丙烯酰胺、36g 2-丙烯酰胺-2-甲基丙磺酸、8g氢氧化钠、80g水加入混合釜，控制搅拌速度在1100r/min，温度40℃ 下搅拌均匀，得到单体水溶液；将上述硬葡聚糖凝胶与单体水溶液混合，在搅拌速度1100r/min下搅拌均匀，用40％氢氧化钠水溶液调节反应液pH值至10，将0.28g硝酸铈铵引发剂加入反应液中，在70℃下反应9h，得到乳黄色半透明黏稠状液体，在烘箱中于100℃下干燥、粉碎，即得取代的硬葡聚糖抗高温增黏提切剂。产品收率为94.57％。
该产品的胺值为0.44mmol/g，HLB值为17，3。
将该例制造得到的产品进行红外检测，检测结果为，在2936cm -1处显示特征峰，确认所述取代基A或所述取代基A′的存在，在1196cm -1处显示特征峰，确认所述取代基B′的存在，在1048、1197cm -1处显示特征峰，确认所述取代基B″的存在，在1677cm -1处显示特征峰，确认所述取代基C或所述取代基C′的存在，在1456cm -1处显示特征峰，确认所述取代基D或所述取代基D′的存在，在2154cm -1处显示特征峰，确认所述取代基E或所述取代基E′的存在。
本发明实施例4制备得到的取代的硬葡聚糖具有式4所示的示意性结构：
Figure PCTCN2021083303-appb-000030
式4中：n为7400-7600，o为13.1，p为9.7，q为13.8，w为9.4，y为0，z为0，M为Na。
实施例5
将12g硬葡聚糖、220g水、8g氢氧化钠加入聚合釜，控制搅拌速度在1100r/min，温度70℃下碱化糊化2.0h，得到硬葡聚糖凝胶；将20g丙烯酸、18g乙烯基吡咯烷酮、64g丙烯酰胺、36g 2-丙烯酰胺-2-甲基丙磺酸、8g氢氧化钠、80g水加入混合釜，控制搅拌速度在1100r/min，温度40℃下搅拌均匀，得到单体水溶液；将上述硬葡聚糖凝胶与单体水溶液混合，在搅拌速度1100r/min下搅拌均匀，用40％氢氧化钠水溶液调节反应液pH值至10，将0.12g亚硫酸氢钠、0.24g过硫酸铵引发剂加入反应液中，在70℃下反应10h，得到乳黄色半透明黏稠状液体，在烘箱中于100℃下干燥、粉碎，即得取代的硬葡聚糖抗高温增黏提切剂。产品收率为96.20％。
该产品的胺值为0.49mmol/g，HLB值为18.0。
将该例制造得到的产品进行红外检测，检测结果为，在2939cm -1处显示特征峰，确认所述取代基A或所述取代基A′的存在，在1198cm -1处显示特征峰，确认所述取代基B′的存在，在1049、1197cm -1处显示特征峰，确认所述取代基B″的存在，在1678cm -1处显示特征峰，确认所述取代基C或所述取代基C′的存在，在1457cm -1处显示特征峰，确认所述取代基D或所述取代基D′的存在，在2156cm -1处显示特征峰，确认所述取代基E或所述取代基E′的存在。
本发明实施例5制备得到的取代的硬葡聚糖具有式5所示的示意性结构：
Figure PCTCN2021083303-appb-000031
式5中：n为7400-7600，o为13.7，p为9.9，q为13.9，w为9.7，y为0，z为0，M为Na。
实施例6
将12g硬葡聚糖、220g水、8g氢氧化钠加入聚合釜，控制搅拌速度在1100r/min，温度70℃下碱化糊化2.0h，得到硬葡聚糖凝胶；将20g丙烯酸、18g乙烯基吡咯烷酮、64g丙烯酰胺、36g 2-丙烯酰胺-2-甲基丙磺酸、27g苯乙烯、9g乙烯基三甲氧基硅烷、8g氢氧化钠、80g水加入混合釜，控制搅拌速度在1100r/min，温度40℃下搅拌均匀，得到单体水溶液；将上述硬葡聚糖凝胶与单体水溶液混合，在搅拌速度1100r/min下搅拌均匀，用40％氢氧化钠水溶液调节反应液pH值至10，将0.12g亚硫酸氢钠、0.24g过硫酸铵引发剂加入反应液中，在70℃下反应10h，得到乳黄色半透明黏稠状液体，在烘箱中于100℃下干燥、粉碎，即得取代的硬葡聚糖抗高温增黏提切剂。产品收率为96.54％。
该产品的胺值为0.52mmol/g，HLB值为18.6。
将该例制造得到的产品进行红外检测，检测结果为，在2938cm -1处显示特征峰，确认所述取代基A或所述取代基A′的存在，在1199cm -1处显示特征峰，确认所述取代基B′的存在，在1046、1195cm -1处显示特征峰，确 认所述取代基B″的存在，在1677cm -1处显示特征峰，确认所述取代基C或所述取代基C′的存在，在1459cm -1处显示特征峰，确认所述取代基D或所述取代基D′的存在，在2157cm -1处显示特征峰，确认所述取代基E或所述取代基E′的存在。
本发明实施例6制备得到的取代的硬葡聚糖具有式6所示的示意性结构：
Figure PCTCN2021083303-appb-000032
式6中：n为7400-7600，o为13.9，p为10.6，q为14.4，w为9.8，y为10.9，z为3.3，M为Na。
实施例7
将12g硬葡聚糖、220g水、8g氢氧化钠加入聚合釜，控制搅拌速度在1100r/min，温度70℃下碱化糊化2.0h，得到硬葡聚糖凝胶；将20g丙烯酸、18g乙烯基吡咯烷酮、64g丙烯酰胺、36g 2-丙烯酰胺-2-甲基丙磺酸、45g苯乙烯、15g乙烯基三乙氧基硅烷、8g氢氧化钠、80g水加入混合釜，控制搅拌速度在1100r/min，温度40℃下搅拌均匀，得到单体水溶液；将上述硬葡聚糖凝胶与单体水溶液混合，在搅拌速度1100r/min下搅拌均匀，用40％氢氧化钠水溶液调节反应液pH值至10，将0.12g亚硫酸氢钠、0.24g过硫酸铵引发剂加入反应液中，在70℃下反应10h，得到乳黄色半透明黏 稠状液体，在烘箱中于100℃下干燥、粉碎，即得取代的硬葡聚糖抗高温增黏提切剂。产品收率为96.69％。
该产品的胺值为0.60mmol/g，HLB值为20.0。
将该例制造得到的产品进行红外检测，检测结果为，在2936cm -1处显示特征峰，确认所述取代基A或所述取代基A′的存在，在1197cm -1处显示特征峰，确认所述取代基B′的存在，在1047、1196cm -1处显示特征峰，确认所述取代基B″的存在，在1678cm -1处显示特征峰，确认所述取代基C或所述取代基C′的存在，在1458cm -1处显示特征峰，确认所述取代基D或所述取代基D′的存在，在2159cm -1处显示特征峰，确认所述取代基E或所述取代基E′的存在。
本发明实施例7制备得到的取代的硬葡聚糖具有式7所示的示意性结构：
Figure PCTCN2021083303-appb-000033
式7中：n为7400-7600，o为15.0，p为14.2，q为14.9，w为9.9，y为14.9，z为4.9，M为Na。
对比例1
将12g壳聚糖、180g水、4g氢氧化钠加入聚合釜，控制搅拌速度在1000r/min，温度60℃下碱化糊化0.5h，得到壳聚糖水溶液；将20g丙烯 酸、15g乙烯基吡咯烷酮、54g丙烯酰胺、27g 2-丙烯酰胺-2-甲基丙磺酸、6g氢氧化钠、50g水加入混合釜，控制搅拌速度在1000r/min，温度30℃下搅拌均匀，得到单体水溶液；将上述壳聚糖水溶液与单体水溶液混合，在搅拌速度1000r/min下搅拌均匀，用40％氢氧化钠水溶液调节反应液pH值至8，将0.12g亚硫酸氢钠、0.24g过硫酸铵引发剂加入反应液中，在40℃下反应4h，得到乳黄色半透明黏稠状液体，在烘箱中于80℃下干燥、粉碎，即得取代的壳聚糖。产品收率为86.14％。
对比例2
将12g环糊精、180g水、4g氢氧化钠加入聚合釜，控制搅拌速度在1000r/min，温度60℃下碱化糊化0.5h，得到环糊精水溶液；将20g丙烯酸、15g乙烯基吡咯烷酮、54g丙烯酰胺、27g 2-丙烯酰胺-2-甲基丙磺酸、6g氢氧化钠、50g水加入混合釜，控制搅拌速度在1000r/min，温度30℃下搅拌均匀，得到单体水溶液；将上述环糊精水溶液与单体水溶液混合，在搅拌速度1000r/min下搅拌均匀，用40％氢氧化钠水溶液调节反应液pH值至8，将0.12g亚硫酸氢钠、0.24g过硫酸铵引发剂加入反应液中，在40℃下反应4h，得到乳黄色半透明黏稠状液体，在烘箱中于80℃下干燥、粉碎，即得取代的环糊精。产品收率为85.73％。
对比例3
将12g硬葡聚糖、180g水、4g氢氧化钠加入聚合釜，控制搅拌速度在1000r/min，温度60℃下碱化糊化0.5h，得到硬葡聚糖凝胶；将20g丙烯酸、6g氢氧化钠、50g水加入混合釜，控制搅拌速度在1000r/min，温度30℃下搅拌均匀，得到单体水溶液；将上述硬葡聚糖凝胶与单体水溶液混合，在搅拌速度1000r/min下搅拌均匀，用40％氢氧化钠水溶液调节反应液pH值至8，将0.12g亚硫酸氢钠、0.24g过硫酸铵引发剂加入反应液中，在40℃下反应4h，得到乳黄色半透明黏稠状液体，在烘箱中于80℃下干燥、粉碎，即得取代的硬葡聚糖。产品收率为90.90％。
对比例4
将12g硬葡聚糖、180g水、4g氢氧化钠加入聚合釜，控制搅拌速度在1000r/min，温度60℃下碱化糊化0.5h，得到硬葡聚糖凝胶；将54g丙烯酰胺、6g氢氧化钠、50g水加入混合釜，控制搅拌速度在1000r/min，温度30℃下搅拌均匀，得到单体水溶液；将上述硬葡聚糖凝胶与单体水溶液混合，在搅拌速度1000r/min下搅拌均匀，用40％氢氧化钠水溶液调节反应液pH值至8，将0.12g亚硫酸氢钠、0.24g过硫酸铵引发剂加入反应液中，在40℃下反应4h，得到乳黄色半透明黏稠状液体，在烘箱中于80℃下干燥、粉碎，即得取代的硬葡聚糖。产品收率为91.57％。
对比例5
将12g硬葡聚糖、180g水、4g氢氧化钠加入聚合釜，控制搅拌速度在1000r/min，温度60℃下碱化糊化0.5h，得到硬葡聚糖凝胶；将15g乙烯基吡咯烷酮、6g氢氧化钠、50g水加入混合釜，控制搅拌速度在1000r/min，温度30℃下搅拌均匀，得到单体水溶液；将上述硬葡聚糖凝胶与单体水溶液混合，在搅拌速度1000r/min下搅拌均匀，用40％氢氧化钠水溶液调节反应液pH值至8，将0.12g亚硫酸氢钠、0.24g过硫酸铵引发剂加入反应液中，在40℃下反应4h，得到乳黄色半透明黏稠状液体，在烘箱中于80℃下干燥、粉碎，即得取代的硬葡聚糖。产品收率为91.65％。
应用实施例
本发明实施例1-7制备得到的质量浓度为0.3％的取代的硬葡聚糖在4％土浆中，150℃热滚16h，测试增黏提切性能、降滤失性能及生物毒性EC 50值，测试结果如表1所示。
按照GB/T 16783.1-2014《石油天然气工业钻井液现场测试第1部分：水基钻井液》的标准，测试钻井液组合物的表观粘度、塑性粘度、动切力、静切力、中压滤失量。
按照下述方法测试钻井液组合物的生物毒性：
将钻井液组合物加入到质量浓度为3％氯化钠溶液中，分别配制成0mg.dm -3、5000mg.dm -3、10000mg.dm -3、25000mg.dm -3、50000mg.dm -3、100000mg.dm -3的待测样品溶液各10mL，静置60min；
向上述待测样品溶液中依次加入发光细菌T3粉末10mg充分震荡混匀后，以质量浓度为3％的氯化钠溶液作为对比分别测定发光菌与待测样品溶液接触15min后的生物毒性EC 50值。
表1取代的硬葡聚糖样品增黏提切、降滤失及生物毒性测试结果
Figure PCTCN2021083303-appb-000034
由表1中数据可知，在150℃高温老化16h后，0.3％的取代的硬葡聚糖样品可使4％土浆表观粘度由3.0mPa.s提至≥20mPa.s，表观黏度升高率≥566.67％，静切力的初切由0.5Pa升高至≥1.5Pa，初切升高率≥200％，静 切力的终切由0.5Pa升高至≥4.5Pa，终切升高率≥800％，表现出较好的增黏提切性能。另外，API滤失量由40mL降至≤9.2mL，滤失量降低率≥77％，表现出较好的降滤失性能。而且，这些取代的硬葡聚糖样品EC 50值＞530000mg/L(远大于排放标准30000mg/L)，无生物毒性，绿色环保。这些取代的硬葡聚糖样品跟对比例样品相比，增黏提切性能、降滤失性能均有大幅提升。
如前所述，本发明的取代的硬葡聚糖具有优异的抗高温增黏提切性能；同时，兼具良好的降滤失性能，绿色环保。而且，本发明的取代的硬葡聚糖特别适用于深井超深井高温钻井液的黏切性能及降滤失性能控制，实现高温地层的绿色、安全、高效钻进。

Claims (11)

  1. 一种取代的硬葡聚糖或者多种取代的硬葡聚糖的混合物，各自或组合带有取代基A、取代基B和取代基C，并且任选各自或组合带有取代基D和取代基E，其中所述取代基A在其结构中包含单元-C(＝O)-O-(优选包含单元-C(＝O)-O-R 1，其中R 1选自氢原子、碱金属(比如K或Na)、碱土金属(比如Ca或Mg)、铵(NH 4)和C1-10或C1-4直链或支链烷基)，所述取代基B在其结构中包含单元-C(＝O)-NH-(优选包含单元-C(＝O)-NH-R 2，其中R 2选自氢原子和任选取代的C1-10或C1-4直链或支链烷基)，所述取代基C在其结构中包含单元
    Figure PCTCN2021083303-appb-100001
    (其中Ra、Rb和Rc彼此相同或不同，各自独立地选自氢原子和C1-10或C1-4直链或支链烷基，优选氢原子)，所述取代基D在其结构中包含芳基(优选苯基)，所述取代基E在其结构中包含硅氧烷基(优选用-Si(OR′) 3表示的硅氧烷基，其中R′是C1-4直链或支链烷基，优选甲基或乙基)。
  2. 权利要求1所述的一种取代的硬葡聚糖或者多种取代的硬葡聚糖的混合物，其中所述取代基A用以下化学式(A-1)、化学式(A-2)或者化学式(A-3)表示，
    Figure PCTCN2021083303-appb-100002
    在前述化学式中，基团R 3选自C2-6或C2-3直链或支链亚烷基(优选亚乙基或亚丙基)，基团L 1选自(优选碳原子数不超过10的)任意连接基团(优选单键或者C1-10或C1-4直链或支链亚烷基，特别是单键)，R 1选 自氢原子、碱金属(比如K或Na)、碱土金属(比如Ca或Mg)、铵(NH 4)和C1-10或C1-4直链或支链烷基)，
    所述取代基B用以下化学式(B-1)、化学式(B-11)、化学式(B-12)、化学式(B-2)、化学式(B-21)、化学式(B-22)、化学式(B-3)、化学式(B-31)或者化学式(B-32)表示，
    Figure PCTCN2021083303-appb-100003
    在前述化学式中，基团R 4、R 41、R 42彼此相同或不同，各自独立地选自C2-6或C2-3直链或支链亚烷基(优选亚乙基或亚丙基)，基团L 2、L 21、L 22彼此相同或不同，各自独立地选自(优选碳原子数不超过10的)任意连 接基团(优选单键或者C1-10或C1-4直链或支链亚烷基，特别是单键)，M是碱金属(比如K或Na)、碱土金属(比如Ca或Mg)或铵(NH 4)，R 2选自氢原子和任选取代的C1-10或C1-4直链或支链烷基，R 2′是氢原子，R 2″选自任选取代的C1-10或C1-4直链或支链烷基，
    所述取代基C用以下化学式(C-1)、化学式(C-2)或者化学式(C-3)表示，
    Figure PCTCN2021083303-appb-100004
    在前述化学式中，基团R 5选自C2-6或C2-3直链或支链亚烷基(优选亚乙基或亚丙基)，基团L 3选自(优选碳原子数不超过10的)任意连接基团(优选单键或者C1-10或C1-4直链或支链亚烷基，特别是单键)，Ra、Rb和Rc彼此相同或不同，各自独立地选自氢原子和C1-10或C1-4直链或支链烷基(优选氢原子)，
    所述取代基D用以下化学式(D-1)或者化学式(D-2)表示，
    Figure PCTCN2021083303-appb-100005
    在前述化学式中，基团L 4选自(优选碳原子数不超过10的)任意连接基团(优选单键或者C1-10或C1-4直链或支链亚烷基，特别是单键)，Ar选自C6-20芳基(优选苯基)，
    所述取代基E用以下化学式(E-1)或者化学式(E-2)表示，
    Figure PCTCN2021083303-appb-100006
    在前述化学式中，基团L 5选自(优选碳原子数不超过10的)任意连接基团(优选单键或者C1-10或C1-4直链或支链亚烷基，特别是单键)，Rs是用-Si(OR′) 3表示的硅氧烷基(其中R′是C1-4直链或支链烷基，优选甲基或乙基)。
  3. 权利要求1所述的一种取代的硬葡聚糖或者多种取代的硬葡聚糖的混合物，是用以下化学式(I)表示的取代的硬葡聚糖或其多种的混合物，
    Figure PCTCN2021083303-appb-100007
    在化学式(I)中，n为2000-20000，优选5000-10000，最优选6000-8000，各个Z彼此相同或不同，各自独立地代表氢原子、所述取代基A、所述取代基B、所述取代基C、所述取代基D、所述取代基E、或者这些取代基的组合基团，前提是至少一个Z不是氢原子，并且在每个化学式(I)中，设所述取代基A的平均数目是o′，设所述取代基B的平均数目是x′，设所述取代基C的平均数目是p′，设所述取代基D的平均数目是y′，设所述取代基E的平均数目是z′，则o′为1-40(优选1-15)的任意数值，p′为1-20(优 选1-10)的任意数值，x′为1-40(优选1-20)的任意数值，y′为0-20(优选1-15)的任意数值，z′为0-20(优选1-5)的任意数值。
  4. 权利要求1所述的一种取代的硬葡聚糖或者多种取代的硬葡聚糖的混合物，是用以下化学式(I-1)表示的取代的硬葡聚糖或其多种的混合物，
    Figure PCTCN2021083303-appb-100008
    在化学式(I-1)中，n为2000-20000，优选5000-10000，最优选6000-8000，各个Z′彼此相同或不同，各自独立地代表氢原子、用化学式(A-3)表示的取代基A(称为取代基A′)、用化学式(B-22)表示的取代基B(称为取代基B′)、用化学式(B-32)表示的取代基B(称为取代基B″)、用化学式(C-3)表示的取代基C(称为取代基C′)、用化学式(D-2)表示的取代基D(称为取代基D′)、用化学式(E-2)表示的取代基E(称为取代基E′)、或者这些取代基的组合基团，前提是至少一个Z′不是氢原子，并且在每个化学式(I-1)中，设所述取代基A′的平均数目是o，设所述取代基B′的平均数目是q，设所述取代基B″的平均数目是w，设所述取代基C′的平均数目是p，设所述取代基D′的平均数目是y，设所述取代基E′的平均数目是z，则o为1-20(优选1-15)的任意数值，p为1-20(优选1-10)的任意数值，q为1-20(优选1-15)的任意数值，w为1-20(优选1-10)的任意数值，y为0-20(优选1-15)的任意数值，z为0-20(优选1-5)的任意数值。
  5. 权利要求4所述的一种取代的硬葡聚糖或者多种取代的硬葡聚糖的混合物，是用以下化学式(I-2)示意性表示的取代的硬葡聚糖或其多种的混合物，
    Figure PCTCN2021083303-appb-100009
    在化学式(I-2)中，M是氢、碱金属(比如K或Na)、碱土金属(比如Ca或Mg)或铵(NH 4)，*代表共价键合位点。
  6. 权利要求1所述的一种取代的硬葡聚糖或者多种取代的硬葡聚糖的混合物，其胺值为0.2-0.6mmol/g，和/或，其HLB值为15.0-20.0。
  7. 一种取代的硬葡聚糖或者多种取代的硬葡聚糖的混合物的制造方法，包括以下步骤：
    1)使以下化学式(A)表示的硬葡聚糖在碱(优选选自碱金属氢氧化物和碱土金属氢氧化物中的至少一种，特别是选自氢氧化钠、氢氧化钾和氢氧化钙中的至少一种)和水的存在下发生糊化反应，得到硬葡聚糖凝胶，
    Figure PCTCN2021083303-appb-100010
    在化学式(A)中，n为2000-20000，优选5000-10000，最优选6000-8000，
    2)使用化学式(X-1)表示的羧酸单体、用化学式(X-2)表示的酰胺单体、用化学式(X-3)表示的磺酸单体、用化学式(X-4)表示的吡咯烷酮单体、任选的用化学式(X-5)表示的苯基单体、以及任选的用化学式(X-6)表示的硅氧烷基单体在碱(优选选自碱金属氢氧化物和碱土金属氢氧化物中的至少一种，特别是选自氢氧化钠、氢氧化钾和氢氧化钙中的至少一种)的存在下与水混合(优选均匀混合)，获得混合单体，和
    3)使所述硬葡聚糖凝胶与所述混合单体在自由基聚合引发剂(优选选自过氧化物类引发剂、偶氮类引发剂和氧化还原类引发剂中的至少一种，特别是选自过氧化氢、过硫酸铵、偶氮二异丁腈、硝酸铈铵、以及质量份1∶2的亚硫酸氢钠和过硫酸铵中的至少一种)的存在下发生自由基聚合反应，任选进行干燥，获得所述一种取代的硬葡聚糖或者多种取代的硬葡聚糖的混合物，
    Figure PCTCN2021083303-appb-100011
    在化学式(X-1)至化学式(X-6)中，基团L 1、L 21、L 22、L 3、L 4、L 5彼此相同或不同，各自独立地选自(优选碳原子数不超过10的)任意连接基团(优选单键或者C1-10或C1-4直链或支链亚烷基，特别是单键)，M是 碱金属(比如K或Na)、碱土金属(比如Ca或Mg)或铵(NH 4)，Ra、Rb和Rc彼此相同或不同，各自独立地选自氢原子和C1-10或C1-4直链或支链烷基(优选氢原子)，R 1选自氢原子、碱金属(比如K或Na)、碱土金属(比如Ca或Mg)、铵(NH 4)和C1-10或C1-4直链或支链烷基(优选氢原子)，Ar是C6-20芳基(优选苯基)，Rs是用-Si(OR′) 3表示的硅氧烷基(其中R′是C1-4直链或支链烷基，优选甲基或乙基)。
  8. 权利要求7所述的制造方法，其中在所述步骤1)中，所述硬葡聚糖、水与所述碱的质量比为12∶(180-220)∶(4-8)，和/或，在所述步骤1)中，反应温度为60-70℃，反应时间为0.5-2h，和/或，在所述步骤2)中，所述用化学式(X-1)表示的羧酸单体、所述用化学式(X-4)表示的吡咯烷酮单体、所述用化学式(X-2)表示的酰胺单体、所述用化学式(X-3)表示的磺酸单体、所述碱与水的质量比为20∶(15-18)∶(54-64)∶(27-36)∶(6-8)∶(50-80)，和/或，在所述步骤2)中，所述用化学式(X-1)表示的羧酸单体、所述用化学式(X-5)表示的苯基单体与所述用化学式(X-6)表示的硅氧烷基单体的质量比为20∶(27-45)∶(9-15)，和/或，在所述步骤2)中，混合温度为30-40℃，和/或，在所述步骤3)中，所述混合单体(以全部单体的总重量为计)、所述硬葡聚糖凝胶(以硬葡聚糖的重量为计)与所述自由基聚合引发剂的质量比为(152-198)∶12∶(0.8-1.6)，和/或，在所述步骤3)中，聚合反应体系的pH值控制为8-10，反应温度为40-70℃，反应时间为4-10h，和/或，在所述步骤3)中，干燥温度为80-100℃。
  9. 一种钻井液组合物，包含取代的硬葡聚糖、基浆和任选的至少一种处理剂，其中所述取代的硬葡聚糖是权利要求1所述的一种取代的硬葡聚糖或者多种取代的硬葡聚糖的混合物或者通过权利要求7所述的制造方法制造的一种取代的硬葡聚糖或者多种取代的硬葡聚糖的混合物。
  10. 权利要求9所述的钻井液组合物，其中以所述钻井液组合物的总质量为100wt％计，所述取代的硬葡聚糖的质量百分含量为0.5-10.0wt％(优选1.5-5.0wt％)。
  11. 一种钻井液组合物的制造方法，包括混合取代的硬葡聚糖、基浆和任选的至少一种处理剂(优选先混合所述取代的硬葡聚糖与所述基浆，然后再将所获得的混合物与所述任选的至少一种处理剂混合)而获得所述钻井液组合物，其中所述取代的硬葡聚糖是权利要求1所述的一种取代的硬葡聚糖或者多种取代的硬葡聚糖的混合物或者通过权利要求7所述的制造方法制造的一种取代的硬葡聚糖或者多种取代的硬葡聚糖的混合物，和，任选将所获得的钻井液组合物进行老化处理(优选处理温度为120-200℃或140-180℃，优选155-165℃，处理时间为10-30小时或15-20小时，优选15-17小时)。
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