WO2019037743A1 - 一种含淀粉微球及其制备方法和应用 - Google Patents

一种含淀粉微球及其制备方法和应用 Download PDF

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WO2019037743A1
WO2019037743A1 PCT/CN2018/101771 CN2018101771W WO2019037743A1 WO 2019037743 A1 WO2019037743 A1 WO 2019037743A1 CN 2018101771 W CN2018101771 W CN 2018101771W WO 2019037743 A1 WO2019037743 A1 WO 2019037743A1
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Prior art keywords
starch
parts
particle size
added
size distribution
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PCT/CN2018/101771
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English (en)
French (fr)
Inventor
杨超
王晨
尹泽群
刘全杰
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中国石油化工股份有限公司
中国石油化工股份有限公司大连石油化工研究院
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Priority claimed from CN201710720844.7A external-priority patent/CN109422887B/zh
Priority claimed from CN201710720864.4A external-priority patent/CN109422853B/zh
Priority claimed from CN201710720850.2A external-priority patent/CN109423264B/zh
Priority claimed from CN201710720862.5A external-priority patent/CN109422852B/zh
Priority claimed from CN201710720851.7A external-priority patent/CN109422851B/zh
Priority claimed from CN201710720863.XA external-priority patent/CN109423266B/zh
Priority to CA3073777A priority Critical patent/CA3073777C/en
Priority to US16/641,504 priority patent/US20210032373A1/en
Application filed by 中国石油化工股份有限公司, 中国石油化工股份有限公司大连石油化工研究院 filed Critical 中国石油化工股份有限公司
Priority to EP18847661.8A priority patent/EP3670540B1/en
Priority to EA202090492A priority patent/EA202090492A1/ru
Publication of WO2019037743A1 publication Critical patent/WO2019037743A1/zh
Priority to US17/658,173 priority patent/US11891458B2/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B31/00—Preparation of derivatives of starch
    • C08B31/003—Crosslinking of starch
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B31/00—Preparation of derivatives of starch
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B31/00—Preparation of derivatives of starch
    • C08B31/08—Ethers
    • C08B31/12—Ethers having alkyl or cycloalkyl radicals substituted by heteroatoms, e.g. hydroxyalkyl or carboxyalkyl starch
    • 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
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/12—Powdering or granulating
    • 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
    • C09K8/42—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells
    • C09K8/426—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells for plugging
    • 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
    • C09K8/50—Compositions for plastering borehole walls, i.e. compositions for temporary consolidation of borehole walls
    • C09K8/504—Compositions based on water or polar solvents
    • C09K8/506—Compositions based on water or polar solvents containing organic compounds
    • C09K8/508—Compositions based on water or polar solvents containing organic compounds macromolecular compounds
    • C09K8/514—Compositions based on water or polar solvents containing organic compounds macromolecular compounds of natural origin, e.g. polysaccharides, cellulose
    • 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
    • C09K8/50—Compositions for plastering borehole walls, i.e. compositions for temporary consolidation of borehole walls
    • C09K8/516—Compositions for plastering borehole walls, i.e. compositions for temporary consolidation of borehole walls characterised by their form or by the form of their components, e.g. encapsulated material
    • E—FIXED CONSTRUCTIONS
    • E21—EARTH OR ROCK DRILLING; MINING
    • E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
    • E21B21/00—Methods or apparatus for flushing boreholes, e.g. by use of exhaust air from motor
    • E21B21/003—Means for stopping loss of drilling fluid
    • E—FIXED CONSTRUCTIONS
    • E21—EARTH OR ROCK DRILLING; MINING
    • E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
    • E21B33/00—Sealing or packing boreholes or wells
    • E21B33/10—Sealing or packing boreholes or wells in the borehole
    • E21B33/13—Methods or devices for cementing, for plugging holes, crevices or the like
    • E21B33/138—Plastering the borehole wall; Injecting into the formation

Definitions

  • the invention belongs to the technical field of microspheres, and particularly relates to starch-containing microspheres and a preparation method and application thereof.
  • Shielding temporary blocking protection oil and gas layer drilling technology (referred to as shielding temporary blocking technology) is mainly used to solve the problem of multi-pressure stratum stratum protection oil and gas layer in open hole section, that is, two damages to the oil and gas layer during the process of drilling oil and gas layers Unfavorable factors (pressure difference and solid solution particles of drilling fluid), which are converted into favorable factors for protecting oil and gas layers, to reduce the damage of drilling fluid, cement slurry, pressure difference and soaking time to oil and gas layers.
  • the basic idea of shielding the temporary plugging protection oil and gas layer drilling technology is to use the pressure difference formed between the drilling liquid liquid column pressure and the oil layer pressure when the oil and gas layer is drilled, and force the artificially added solid in the drilling fluid in a very short time.
  • the particles temporary plugging agent
  • the thickness of the occlusion zone must be much less than the depth of the perforation so that it can be blocked by the perforation when the completion is completed.
  • Microsphere compounds are currently used as a temporary plugging agent for oil and gas layer protection, and starch-containing microspheres have also been extensively studied.
  • the prior art has many researches on monodisperse or polydisperse starch-containing microspheres, and CN201010546156.1 and CN201410236878.5 describe the preparation methods of two monodisperse starch-containing microspheres.
  • CN201510151917.6 describes a preparation method of nano-scale polydisperse starch-containing microspheres.
  • CN201510175382.6 provides a preparation method of polymer microspheres with particle size gradient characteristics.
  • CN107129560A discloses a preparation method of a particle temporary blocking agent, which firstly stirs and mixes corn starch, glutinous polysaccharide, etc., and adds a sodium hydroxide solution at a low temperature to carry out a reaction, and then adds a chloroacetic acid solution to perform heating mixing and filtration.
  • the filtrate is dialyzed and concentrated to obtain a concentrated liquid.
  • the concentrated liquid is mixed with absolute ethanol at a low temperature and filtered, and the filter residue is dried, and then mixed with water or the like to obtain a mixed liquid A, which is then made of acrylic acid, ammonia water or the like.
  • the mixture is mixed to obtain a mixed liquid B, which is added to the mixed liquid A, and a surfactant or the like is added thereto to prepare a viscous liquid. Finally, the viscous liquid is cooled, placed, dried, and pulverized.
  • the temporary plugging agent obtained by using this method has a good temporary plugging effect when used in some formations, and the temporary plugging effect is not good when used in other formations.
  • WO03035793A1 discloses a drilling fluid comprising the use of epichlorohydrin-crosslinked starch as a bridging agent to form a filter cake which can be easily removed under very mild conditions.
  • the present invention provides a starch-containing microsphere and a preparation method and application thereof, the starch-containing microspheres having uniform distribution, low polydispersity, low cost, and excellent use in various formations. Temporary blocking effect and other advantages.
  • the first aspect of the invention provides a starch-containing microsphere, wherein the starch-containing microspheres have a uniform distribution of polydispersity in a particle size distribution interval, and the particle size distribution in the particle size distribution interval has the following characteristics:
  • the particle size distribution interval is divided into n intervals, and the proportion of microspheres in each interval is: Where n is an integer greater than one.
  • a second aspect of the invention provides a method for preparing a starch-containing microsphere, the preparation method comprising the steps of:
  • a further aspect of the invention provides the use of the starch-containing microspheres prepared by the above method and the above-described starch-containing microspheres for protecting the temporary plugging agent of the oil and gas layer.
  • the starch-containing microsphere provided by the invention can have a good effect under the dosage of the drilling fluid mass fraction of 0.5 to 5 wt%, has good sealing ability for different formations, can effectively block pores or micro-cracks, and form The dense mud cake prevents the filtrate from infiltrating into the formation and reduces the fluid loss.
  • the starch-containing microspheres of the present invention are microdispersions having a uniform particle size distribution, when the starch-containing microspheres are used.
  • the porosity of the reservoir is very different due to the wide variety of geological structures.
  • the microspheres with monodisperse particle size are difficult to meet the requirements of broad spectrum, the use effect cannot meet the industrial requirements.
  • the existing polydisperse microspheres exhibit a normal distribution, the effective range of the particle diameter is narrow, and the effect is also significantly limited.
  • the uniformly distributed polydisperse starch-containing microspheres provided by the invention can solve these problems well, that is, the microspheres have the same proportion in any particle size interval, the microsphere content is high, the temporary plugging effect is remarkable, and the broad spectrum can be satisfied. Requirements.
  • the method for preparing starch-containing microspheres can prepare starch-containing microspheres having a polydispersity with uniform particle size distribution (ie, the ratio of microspheres is equal in any particle size interval), which may be because Through the combined action of triethanolamine and epichlorohydrin, especially the operation of adding epichlorohydrin in two steps, the linear and branched portions of the starch have the same structural size and have similar molecular sizes.
  • the prepared microspheres are more controllable and have uniform particle size distribution.
  • the particle size of the prepared starch-containing microspheres is combined under the action of the starch.
  • the size changes linearly, and polydisperse starch-containing microspheres with uniform particle size distribution are prepared.
  • the starch-containing microsphere preparation method By adding a monomer (including one or more of a cationic monomer, an anionic monomer, a zwitterionic monomer, and a nonionic monomer) to the starch-containing microsphere preparation method, the starch is copolymerized and modified to make micro The ball has been significantly improved in resistance to salt and temperature, inhibition of core hydration and dispersion, and stabilization of the well wall.
  • a monomer including one or more of a cationic monomer, an anionic monomer, a zwitterionic monomer, and a nonionic monomer
  • Figure 1 is a graph showing the particle size distribution of the starch-containing microspheres of the present invention.
  • Figure 2 is an infrared spectrum of the starch-containing microspheres of the present invention.
  • Figure 3 is an infrared spectrum of a starch material used in an embodiment of the present invention.
  • the uniform distribution of the particle diameter means that the number of particles of each particle diameter is equivalent in the concentration distribution range of the particle diameter.
  • the particle size concentration distribution interval refers to an area where the particle size distribution is approximately linear, and does not include the areas with obvious inflection points at both ends, as shown in FIG. This interval can be determined by the particle size distribution map obtained by the particle size distribution tester.
  • the particle size distribution is measured by a Malvern 3000 particle size analyzer, and the test method is a wet method.
  • the present invention divides the particles in the particle size distribution interval into n intervals, wherein n can be any integer greater than 1, and the result includes
  • n can be any integer greater than 1, and the result includes
  • the proportion of starch microspheres is basically the same, both:
  • n is preferably an integer between 4 and 10 in the embodiment of the present invention.
  • the starch-containing microspheres have a particle diameter controllable range of 0.1 to 500 ⁇ m, and may be, for example, 0.1 to 5 ⁇ m, 20 to 260 ⁇ m, 50 to 300 ⁇ m, and 150 to 500 ⁇ m. That is, in the above particle size range, the proportion of the starch-containing microspheres in each particle size interval in the particle size concentration distribution range satisfies the above requirements.
  • the particle size distribution of the starch microspheres is any one or more of the following: the particle size concentration distribution interval is 10 to 170 ⁇ m, n is 4, and each interval is micro.
  • the ball proportion is 24.5% to 25.5%; the particle size concentration distribution interval is 120-400 ⁇ m, n is 4, and the microsphere ratio in each interval is 24.5% to 25.5%; the particle size concentration distribution interval is 50. ⁇ 300 ⁇ m, n is 5, and the proportion of microspheres in each interval is 18.5% to 21.5%; the concentration distribution range of the particle diameter is 150 to 500 ⁇ m, n is 7, and the proportion of microspheres in each interval is 13.5%.
  • the concentration distribution interval is 70-270 ⁇ m, n is 5
  • the proportion of microspheres in each interval is 18.5% to 21.0%; the concentration distribution interval is 20 to 260 ⁇ m, n is 6, and the proportion of microspheres in each interval is 15.0% to 18.0%;
  • the concentration distribution interval is 0.1 to 4.9 ⁇ m, n is 6, and the proportion of microspheres in each interval is 15.5% to 18.0%.
  • the infrared spectrum of the starch-containing microspheres has a small peak near the position of 1025 to 1250 cm -1 , which is a vibration characteristic peak of CN, and appears in the vicinity of the position of 1150 to 1350 cm -1 .
  • the infrared spectrum of the starch material is shown in Fig. 3, and there are no characteristic peaks at the above two positions.
  • the infrared spectrum in the present invention was obtained by analysis on a Frontier type Fourier transform infrared spectrometer manufactured by Perkin-Elmer.
  • the starch-containing microspheres of the present invention contain a zwitterionic surfactant, and the zwitterionic surfactant has the following structural formula:
  • m is an integer between 2 and 6, preferably m is 3 or 4; and R is a saturated carbon chain having 1 to 18 carbon atoms and preferably 12 to 18 carbon atoms.
  • the zwitterionic surfactant carbon chain contains a monosubstituted functional group.
  • the group may be a hydroxyl group, an amino group or a carboxyl group. That is, the R is preferably a saturated carbon chain having 1 to 18 carbon atoms, preferably having 12 to 18 carbon atoms, having one or more carbons having a hydroxyl group, an amino group or a carboxyl group as a substituent, in addition to the terminal carbon.
  • the zwitterionic surfactant is dimethyldodecylsulfonyl ammonium salt, dimethylhexadecylsulfonyl ammonium salt, dimethyloctadecylsulfonium ammonium salt One or more of dimethyl (3-hydroxydodecyl)sulfonyl ammonium salt and dimethyl (6-aminotetradecyl) sulfoethyl ammonium salt.
  • the starch-containing microspheres of the present invention mainly contain a starch structural unit in which the content of the starch structural unit is not less than 35 wt% to 95 wt%, preferably 38 wt% to 85 wt%.
  • the starch-containing microspheres further comprise a polymerized monomer structural unit, the polymerization monomer being an anionic monomer, a cationic monomer, and a non- At least one of an ionic monomer and a zwitterionic monomer.
  • the polymerized monomer structural unit forms a graft copolymer with the starch structural unit.
  • the zwitterionic monomer is DMAPS (methacryloyloxyethyl-N,N-dimethylpropane sulfonate), DAPS (N,N-dimethylallylamine propane sulfonate) , one of VPPS (4-vinylpyridinium sulfonate), MAPS (N-methyldiallylpropane sulfonate), and MABS (N-methyldiallylbutanesulfonate) Or a plurality; the cationic monomer is DMC (methacryloyloxyethyltrimethylammonium chloride), DAC (acryloyloxyethyltrimethylammonium chloride), DBC (acryloyloxyethyldiamide) One or more of methylbenzylammonium chloride), DMDAAC (dimethyldiallylammonium chloride), DEDAAC (diethyldiallylammonium chloride); AA (acrylic acid),
  • the starch-containing microspheres further comprise at least one of a starch structural unit and a crosslinking agent structural unit and a polymeric monomer structural unit, and the total amount of the starch-containing microspheres is The basis, wherein the content of the starch structural unit is 35 to 95% by weight, preferably 36.6 to 90.4% by weight, more preferably 38 to 85% by weight, still more preferably 39.6 to 82.7% by weight.
  • the content of the polymerized monomer structural unit is 0 to 50% by weight, preferably 5 to 45.2% by weight, and the content of the crosslinking member structural unit is 6 to 35% by weight, preferably 5 to 30% by weight, more preferably 8.2% to 26.7%. .
  • the content of the starch structural unit is from 39.6 wt% to 82.7 wt%
  • the content of the polymerized monomer structural unit is from 8.3 wt% to 36.6 wt%
  • the content of the crosslinker structural unit is from 9.4 wt% to 20.6 wt%.
  • Starch-containing microspheres having preferred ingredients have better salt and temperature resistance.
  • the starch structural unit refers to a structural unit provided by starch in the starch-containing microsphere
  • the polymerized monomer structural unit refers to a structural unit provided by the polymerization monomer in the starch-containing microsphere.
  • the presence of each structural unit can be determined by a method characterized by Fourier transform infrared spectroscopy.
  • the content of the structural unit can be calculated from the amount of raw material charged.
  • the invention provides a preparation method of the above starch-containing microspheres, and the preparation method comprises the following steps:
  • the method further comprises the step (1 to 1) being added between the step (1) and the step (2): adding a polymerization monomer and an initiator to carry out a copolymerization reaction. That is, the polymerization monomer is added to the solution obtained in the step (1), fully dissolved and uniformly mixed, and then the initiator is added, and reacted at 60 to 80 ° C for 3 to 6 hours, and then the zwitterionic surfactant is added to carry out the step (2). ).
  • the starch-containing microspheres thus obtained have better temperature and salt resistance, stable well wall properties and the like.
  • the polymerizable monomer may be one or more of a cationic monomer, an anionic monomer, a zwitterionic monomer, and a nonionic monomer as described above. The details have been described above and will not be described here.
  • the initiator may be a persulfate type initiator such as any one or more of potassium persulfate, sodium persulfate, and ammonium persulfate.
  • the conditions for the copolymerization reaction with the polymerizable monomer include a temperature of preferably 30 to 80 ° C, a time of preferably 2 to 8 hours, further preferably a temperature of 45 to 65 ° C, and a time of 3 to 5 hours.
  • the weight ratio of starch to water may be from 1 to 20:100, preferably from 5 to 15:100.
  • the starch is one or more of mung bean starch, tapioca starch, sweet potato starch, sweet potato starch, potato starch, wheat starch, water chestnut starch, glutinous starch, corn starch, preferably corn starch and/or Potato starch.
  • the water is preferably deionized water.
  • the solubilizing agent may be various substances capable of increasing the solubility/swellability of starch in water to increase the degree of contact of starch with water to prevent agglomeration of starch, preferably containing a hydroxyl group and a tertiary N and having 1 to 10 carbon atoms. Further, it is preferably one or more of trimethylamine amine, triethanolamine, tripropanolamine, N,N-diethanolamine, isopropanolamine, and diglycolamine, and it is particularly preferred that the solubilizing agent is Triethanolamine.
  • the weight ratio of the starch to the solubilizer is from 1 to 20:10 to 50, preferably from 5 to 15:20 to 40.
  • the temperature at which the starch is brought into contact with water or a solubilizing agent is preferably 20 to 80 ° C, and more preferably 30 to 60 ° C.
  • the first crosslinking agent and the second crosslinking agent are the same or different, and each of them is an epichlorohydrin, an N,N-methylene bisallylamine, a phosphorus oxychloride, a triple bias.
  • the first crosslinking agent and the second crosslinking agent are the same. From the viewpoint of crosslinking efficiency, it is preferred that both the first crosslinking agent and the second crosslinking agent are epichlorohydrin.
  • the conditions of the step (1) crosslinking reaction include a temperature of preferably 20 to 80 ° C, a time of preferably 0.5 to 4 hours, further preferably a temperature of 30 to 60 ° C, and a time of 1 to 3 hours.
  • the type of the zwitterionic surfactant is as described above, and will not be described herein.
  • the zwitterionic surfactant is used in an amount of from 0.05 to 10 parts by weight, preferably from 5 to 15 parts by weight, based on 1 to 20 parts by weight of the starch, and the zwitterionic surfactant is used in an amount of from 1 to 6 parts by weight.
  • the conditions of the step (2) mixing include a temperature of preferably 20 to 80 ° C, a time of preferably 0.5 to 6 hours, further preferably a temperature of 30 to 50 ° C, and a time of 1 to 3 hours.
  • the temperature of the reaction in the step (3) may be from 20 to 80 ° C, preferably from 30 to 60 ° C.
  • the inorganic salt solution and the second crosslinking agent are simultaneously added to the reaction system, and a slow uniform rate is added to the method of preferably uniform dropping.
  • the dropwise addition time may be 2 to 20 hours, preferably 5 to 15 hours.
  • the inorganic salt solution is used in an amount of from 0.5 to 200 parts by weight, preferably from 5 to 15 parts by weight, based on 1 to 20 parts by weight of the starch, and the inorganic salt solution is used in an amount of from 50 to 150 parts by weight.
  • the content of the inorganic salt solute is from 0.025 to 50 parts by weight, preferably from 0.5 to 30 parts by weight.
  • the inorganic salt may be various soluble inorganic salts, and for example, the inorganic salt may be one or more of a sodium salt, a potassium salt, an ammonium salt, a calcium salt, and a magnesium salt.
  • the inorganic salt is a sodium salt, it may specifically be one of sodium chloride, sodium bromide, sodium sulfate, sodium sulfite, sodium carbonate, sodium hydrogencarbonate, sodium nitrate, sodium phosphate, sodium hydrogen phosphate or sodium silicate. Or a variety.
  • the inorganic salt when the inorganic salt is a potassium salt, it may specifically be potassium chloride, potassium bromide, potassium sulfate, potassium sulfite, potassium carbonate, potassium hydrogencarbonate, potassium nitrate, potassium phosphate, potassium hydrogen phosphate or potassium silicate. kind or more.
  • the inorganic salt when the inorganic salt is an ammonium salt, it may specifically be one or more of ammonium chloride, ammonium bromide, and ammonium nitrate.
  • the inorganic salt when the inorganic salt is a calcium salt, it may specifically be calcium chloride and/or calcium bromide.
  • the inorganic salt when the inorganic salt is a magnesium salt, it may specifically be one or more of magnesium chloride, magnesium bromide, magnesium sulfate, and magnesium nitrate.
  • the total amount of the first crosslinking agent and the second crosslinking agent is from 0.105 to 14.6 parts by weight, preferably from 5 to 15 parts by weight of the starch, the first crosslinking agent and the second, relative to 1 to 20 parts by weight of the starch.
  • the total amount of the crosslinking agent is from 1.04 to 7.8 parts by weight.
  • Step (3) is continued for 1 to 5 hours, preferably 1.5 to 3 hours, after completion of the dropwise addition.
  • solid-liquid separation may be further carried out as needed (for example, considering long-distance transportation of the product), and the separated solid is dried to obtain a solid product containing starch microspheres.
  • the drying conditions include a temperature of 30 to 110 ° C, a time of 2 to 12 hours, preferably a temperature of 40 to 80 ° C, and a time of 5 to 9 hours.
  • the raw material for preparing the starch-containing microspheres comprises the following components in parts by weight: 100 parts of deionized water, 1-20 parts of starch, 10 to 50 parts of triethanolamine, 0.105- 14.6 parts of epichlorohydrin, 0.05-10 parts of zwitterionic surfactant, 0.5-200 parts of inorganic salt solution, wherein the inorganic salt solute accounts for 0.025-50 parts.
  • the starch-containing microsphere-containing raw material comprises the following components in parts by weight: 100 parts of deionized water, 5-15 parts of starch, 20-40 parts of triethanolamine, 1.04 to 7.8 parts of epichlorohydrin, 1 to 6 parts of zwitterionic surfactant, 50 to 150 parts of inorganic salt solution, wherein the inorganic salt solute accounts for 0.5 to 30 parts.
  • the starch-containing microsphere-containing raw material further comprises an initiator and a monomer
  • the starch-containing microsphere-containing raw material comprises the following components in parts by weight: 100 parts of deionized water. 1-20 parts starch, 10-50 parts triethanolamine, 0.105-14.6 parts epichlorohydrin, 0.05-10 parts zwitterionic surfactant, 0.1-20 parts monomer, 0.001-0.2 parts initiator, 0.5-200
  • An ionic surfactant 5 to 15 parts of a monomer, 0.02 to 0.105 parts of an initiator, and 50 to 150 parts of an inorganic salt solution, wherein the inorganic salt solute accounts for 0.5 to 30 parts.
  • the preparation method comprises the following steps:
  • step (3) slowly and uniformly add the inorganic salt solution and epichlorohydrin to the liquid obtained in the step (2) at a temperature of 30 to 60 ° C, and continue the reaction after the inorganic salt solution and the epichlorohydrin are added, to obtain a Starch microspheres.
  • the amount of the deionized water, starch, triethanolamine, epichlorohydrin, zwitterionic surfactant, and inorganic salt solution may be 100 parts by weight of deionized water, 1 to 20 parts of starch, and 10 parts by weight, respectively.
  • the fraction of the epichlorohydrin in the step (1) is from 0.005 to 0.6 parts, preferably from 0.04 to 3 parts.
  • the fraction of the epichlorohydrin in the step (3) is from 0.1 to 14 parts, preferably from 1 to 7.5 parts.
  • the preparation method includes the following steps:
  • step (3) slowly and uniformly add the inorganic salt solution and epichlorohydrin to the liquid obtained in the step (2) at a temperature of 30 to 60 ° C, and continue the reaction after the inorganic salt solution and the epichlorohydrin are added, to obtain a Starch microspheres.
  • the monomer in the step (1 to 1) may be one or more of a cationic monomer, an anionic monomer, a zwitterionic monomer, and a nonionic monomer. The details have been described above and will not be described here.
  • the particle size of the starch-containing microspheres prepared by the above method has a uniform distribution of polydispersity in the concentrated distribution range of the particle diameter, and the particle size distribution in the concentrated distribution range of the particle diameter has the following characteristics: Divided into n intervals, the proportion of microspheres in each interval is: Wherein n is an integer greater than 1, and preferably n is an integer between 4 and 10.
  • the particle size of the starch-containing microspheres can be controlled in the range of 0.1 to 500 ⁇ m.
  • the infrared spectrum of the starch-containing microspheres has a small peak near the position of 1025 to 1250 cm -1 , which is a vibration characteristic peak of CN.
  • the starch-containing microspheres of the invention act as a component in the drilling fluid system and serve to shield the temporary plugging.
  • the starch-containing microspheres may be used in an amount of 0.5 to 5% by weight based on the total amount of the drilling fluid system.
  • starch-containing microspheres of the present invention and the preparation method and application thereof are further described below by way of specific examples, but are not intended to limit the invention.
  • the particle size of the starch-containing microspheres in the examples of the present invention was measured by a Malvern 3000 particle size analyzer, and the test method was a wet method.
  • the cross-linked structure and the graft polymerization structure were determined by Frontier-type Fourier transform infrared spectrometer of PerkiN-Elmer, and the content of each structural unit in the starch-containing microspheres was calculated by the amount of feed.
  • the particle size ranges (a ⁇ m to b ⁇ m) in all of the following examples and comparative examples are represented by a ⁇ D ⁇ b, and D represents the diameter of a specific starch granule, that is, when the two ranges have coincident end points, the endpoint value belongs to The latter range is not the previous one.
  • amphoteric cationic surfactant and the polymerized monomer are all commercially available.
  • Examples 1-1 to 1-5 and Comparative Examples 1-1 to 1-4 were used to illustrate the preparation of starch-containing microspheres without polymerization monomers.
  • the reaction was continued for 2 hours to obtain a uniformly distributed polydisperse starch-containing microsphere, and the content of the starch structural unit was 70.4% by weight.
  • the particle size distribution is as shown in FIG. 1 , wherein the starch-containing microspheres have a particle size distribution interval of 150 to 500 ⁇ m ⁇ m (96.0% of the particle diameter is within this interval), and the particle size is distributed within the interval.
  • the diameter distribution has the following characteristics: (150 ⁇ m to 200 ⁇ m): 13.8%; (200 ⁇ m to 250 ⁇ m): 13.9%; (250 ⁇ m to 300 ⁇ m): 15.4%; (300 ⁇ m to 350 ⁇ m): 14.8%; (350 ⁇ m to 400 ⁇ m): 14.2% (400 ⁇ m to 450 ⁇ m): 13.7%; (450 ⁇ m to 500 ⁇ m): 14.2%; and (150 ⁇ m to 185 ⁇ m): 10.2%; (185 ⁇ m to 220 ⁇ m): 9.1%; (220 ⁇ m to 255 ⁇ m): 9.9%; (255 ⁇ m - 290 ⁇ m): 9.8%; (290 ⁇ m to 325 ⁇ m): 10.1%; (325 ⁇ m to 360 ⁇ m): 10.3%; (360 ⁇ m to 395 ⁇ m): 10.0%; (395 ⁇ m to 430 ⁇ m): 9.8%; (430 ⁇ m to 465 ⁇ m)
  • the starch-containing microspheres have a particle size distribution interval of 50 to 210 ⁇ m (95.1% of the particle diameter is within this interval), and the particle size distribution in the particle size distribution interval has the following characteristics: (50 ⁇ m to 90 ⁇ m): 25.4%; (90 ⁇ m - 130 ⁇ m): 25.1%; (130 ⁇ m - 170 ⁇ m): 24.6%; (170 ⁇ m - 210 ⁇ m): 24.9%; and (50 ⁇ m - 70 ⁇ m): 13.4%; (70 ⁇ m - 90 ⁇ m): 12.0%; 90 ⁇ m to 110 ⁇ m): 13.7%; (110 ⁇ m to 130 ⁇ m): 11.4%; (130 ⁇ m to 150 ⁇ m): 12.3%; (150 ⁇ m to
  • the starch-containing microspheres have a particle size distribution interval of 70 to 350 ⁇ m (92.2% of the particle diameter is in this interval), and the particle size distribution in the particle size distribution interval has the following characteristics: (70 ⁇ m to 140 ⁇ m): 24.5%; (140 ⁇ m to 210 ⁇ m): 26%; (210 ⁇ m to 280 ⁇ m): 25.1%; (280 ⁇ m to 350 ⁇ m): 24.4%; and (70 ⁇ m to 110 ⁇ m): 14.5%; (110 ⁇ m to 150 ⁇ m): 15.2%; 150 ⁇ m to 190 ⁇ m): 14.9%; (190 ⁇ m to 230 ⁇ m): 15.0%; (230 ⁇ m to 270 ⁇ m): 13.9%; (270 ⁇ m to 310 ).
  • the particle size distribution range of the starch-containing microspheres is 50 to 300 ⁇ m (93.7% of the particle diameter is in this interval), and the particle size distribution in the particle size distribution interval has the following characteristics: (50 ⁇ m to 100 ⁇ m): 19.4%; (100 ⁇ m to 150 ⁇ m): 18.8%; (150 ⁇ m to 200 ⁇ m): 21%; (200 ⁇ m to 250 ⁇ m): 20.0%; (250 ⁇ m to 300 ⁇ m): 20.8%; and (50 ⁇ m to 75 ⁇ m): 10.2%; 75 ⁇ m to 100 ⁇ m): 9.2%; (100 ⁇ m to 125 ⁇ m): 9.6%; (125 ⁇ m to 150 ⁇ m): 9.7%; (150 ⁇ m to 175 ⁇ m): 11.0%; (175 ⁇ m to 200 ⁇ m): 9.5%; (200 ⁇ m to 225 ⁇ m): 9.8%; (225 ⁇ m to 250 ⁇ m): 10.2%; (250 ⁇
  • sweet potato starch was weighed into 100 parts of deionized water, and then 50 parts of triethanolamine was added, and it was fully dissolved at 50 °C. Then, 0.34 parts of epichlorohydrin was added, and after mixing, the reaction was carried out for 2.5 hours.
  • 0.025 parts of NaCl was weighed into 0.5 part of an inorganic salt solution, and 0.1 part of epichlorohydrin was added dropwise to the starch solution at 55 ° C, and the mixture was added dropwise at a constant rate for 9 hours.
  • the particle size distribution range of the starch-containing microspheres is 0.1 to 1.3 ⁇ m (93.5% of the particle diameter is in this interval), and the particle size distribution in the particle size distribution interval has the following characteristics: (0.1 ⁇ m to 0.3) ⁇ m): 17.5%; (0.3 ⁇ m to 0.5 ⁇ m): 15.9%; (0.5 ⁇ m to 0.7 ⁇ m): 16.5%; (0.7 ⁇ m to 0.9 ⁇ m): 16.5%; (0.9 ⁇ m to 1.1 ⁇ m): 16.4%; (1.1 ⁇ m to 1.3 ⁇ m): 17.2%; and (0.1 ⁇ m to 0.2 ⁇ m): 9.1%; (0.2 ⁇ m to 0.3 ⁇ m): 8.2%; (0.3 ⁇ m to 0.4 ⁇ m): 8.6%; (0.4 ⁇ m to 0.5) ⁇ m): 7.5%; (0.5 ⁇ m to 0.6 ⁇ m): 9.0%; (0.6 ⁇ m to 0.7 ⁇ m): 7.5%; (0.7 ⁇ m to
  • the starch-containing microspheres have a particle size distribution range of 50 to 350 ⁇ m (97.5% of the particle diameter is in this interval), and the particle size distribution in the particle size distribution interval has the following characteristics: (50 ⁇ m to 100 ⁇ m): 10.2%; (100 ⁇ m to 300 ⁇ m): 80.6%; (300 ⁇ m to 350 ⁇ m): 9.2%.
  • the starch-containing microspheres were prepared according to the method of Example 1-2 except that 0.005 parts of epichlorohydrin was not added before adding 6 parts of dimethyldodecylsulfonyl ammonium salt to obtain a uniformly distributed polydisperse content.
  • the particle size distribution range of the starch-containing microspheres is 10 to 210 ⁇ m (92.5% of the particle diameter is in this interval), and the particle size distribution in the particle size distribution interval has the following characteristics: (10 ⁇ m to 60 ⁇ m): 31.8%; (60 ⁇ m to 110 ⁇ m): 19.0%; (110 ⁇ m to 160 ⁇ m): 18.7%; (160 ⁇ m to 210 ⁇ m): 30.5%.
  • the starch-containing microspheres were prepared according to the method of Example 1-2 except that the inorganic salt aqueous solution and 1 part of epichlorohydrin were simultaneously added to the starch solution at one time to obtain uniformly distributed polydisperse starch-containing microspheres.
  • the particle size distribution range of the starch-containing microspheres is 10 to 210 ⁇ m (96.8% of the particle diameter is in this interval), and the particle size distribution in the particle size distribution interval has the following characteristics: (10 ⁇ m to 60 ⁇ m): 7.5%; (60 ⁇ m to 110 ⁇ m): 40.2%; (110 ⁇ m to 160 ⁇ m): 43.5%; (160 ⁇ m to 210 ⁇ m): 8.8%.
  • Starch-containing microspheres were prepared according to the procedure of Example 1-2 except that triethanolamine was not added to obtain uniformly distributed polydisperse starch-containing microspheres.
  • the particle size distribution range of the starch-containing microspheres is 20 to 200 ⁇ m (95.3% of the particle diameter is in this interval), and the particle size distribution in the particle size distribution interval has the following characteristics: (20 ⁇ m to 65 ⁇ m): 35.6%; (65 ⁇ m to 110 ⁇ m): 21.1%; (110 ⁇ m to 155 ⁇ m): 20.9%; (155 ⁇ m to 200 ⁇ m): 22.4%.
  • the particle size distribution range of the starch-containing microspheres is 10 to 170 ⁇ m (94.2% of the particle diameter is in this interval), and the particle size distribution in the particle size distribution interval has the following characteristics: (10 ⁇ m to 50 ⁇ m): 24.9%; (50 ⁇ m to 90 ⁇ m): 25.6%; (90 ⁇ m to 130 ⁇ m): 25.1%; (130 ⁇ m to 170 ⁇ m): 24.4%; and (10 ⁇ m to 30 ⁇ m): 13.7%; (30 ⁇ m to 50 ⁇ m): 11.3%; 50 ⁇ m to 70 ⁇ m): 13.3%; (70 ⁇ m to 90 ⁇ m): 12.3%; (90 ⁇ m to 110 ⁇ m): 12.1%; (110 ⁇ m to 130 ⁇ m): 13.0%; (130 ⁇ m to 150 ⁇ m): 12.2%; (150 ⁇ m to 170 ⁇ m): 12.1%.
  • the infrared spectrum has a C-N peak and a S-
  • the particle size distribution range of the starch-containing microspheres is 120-400 ⁇ m (97.1% of the particle diameter is in this interval), and the particle size distribution in the particle size distribution interval has the following characteristics: (120 ⁇ m - 190 ⁇ m): 26%; (190 ⁇ m to 260 ⁇ m): 24.5%; (260 ⁇ m to 330 ⁇ m): 25.1%; (330 ⁇ m to 400 ⁇ m): 24.4%; and (120 ⁇ m to 160 ⁇ m): 14.5%; (160 ⁇ m to 200 ⁇ m): 13.8%; 200 ⁇ m to 240 ⁇ m): 13.3%; (240 ⁇ m to 280 ⁇ m): 13.9%; (280 ⁇ m to 320 ⁇ m): 14.3%; (320 ⁇ m to 360 ⁇ m): 14.8%; (360 ⁇ m to 400 ⁇ m): 15.4%.
  • there are CN peak and S O peak in the infrared spectrum.
  • the particle size distribution interval of the starch-containing microspheres is 50 to 300 ⁇ m ⁇ m (95.4% of the particle diameter is in this interval), and the particle size distribution in the particle size distribution interval has the following characteristics: (50 ⁇ m to 100 ⁇ m): 19.5%; (100 ⁇ m to 150 ⁇ m): 18.7%; (150 ⁇ m to 200 ⁇ m): 21%; (200 ⁇ m to 250 ⁇ m): 20.0%; (250 ⁇ m to 300 ⁇ m): 20.8%; and (50 ⁇ m to 75 ⁇ m): 10.3%; 75 ⁇ m to 100 ⁇ m): 9.2%; (100 ⁇ m to 125 ⁇ m): 9.2%; (125 ⁇ m to 150 ⁇ m): 9.5%; (150 ⁇ m to 175 ⁇ m): 10.9%; (175 ⁇ m to 200 ⁇ m): 10.1%; (200 ⁇ m to 225 ⁇ m): 9.5%; (225 ⁇ m to 250 ⁇ m): 10.5%; (
  • the particle size distribution range of the starch-containing microspheres is 150 to 500 ⁇ m (96.2% of the particle diameter is in this interval), and the particle size distribution in the particle size distribution interval has the following characteristics: (150 ⁇ m to 200 ⁇ m): 13.5%; (200 ⁇ m to 250 ⁇ m): 14.2%; (250 ⁇ m to 300 ⁇ m): 15.4%; (300 ⁇ m to 350 ⁇ m): 14.7%; (350 ⁇ m to 400 ⁇ m): 13.9%; (400 ⁇ m to 450 ⁇ m): 14.7%; (450 ⁇ m) ⁇ 500 ⁇ m): 13.6%.
  • there are CN peak and S O peak in the infrared spectrum. Starch and VPPS were grafted.
  • sweet potato starch was weighed into 100 parts of deionized water, and then 50 parts of triethanolamine was added, and it was fully dissolved at 50 °C. Then 0.15 parts of epichlorohydrin was added and mixed for 2.5 hours. Weigh 0.1 part of MAPS and add it to the starch solution, and fully dissolve and mix. 0.001 parts of ammonium persulfate was added at 65 ° C for 4 h. Add 0.05 parts of dimethyl(6-aminotetradecyl)sulfoethylammonium salt (Zhongguo Group Chemical Reagent Co., Ltd.) and mix well.
  • the particle size distribution interval of the starch-containing microspheres is 0.1 to 3.7 ⁇ m (95.0% of the particle diameter is in this interval), and the particle size distribution in the particle size distribution interval has the following characteristics: (0.1 ⁇ m to 0.7) ⁇ m): 16.5%; (0.7 ⁇ m to 1.3 ⁇ m): 15.9%; (1.3 ⁇ m to 1.9 ⁇ m): 17.2%; (1.9 ⁇ m to 2.5 ⁇ m): 17.5%; (2.5 ⁇ m to 3.1 ⁇ m): 16.4%; (3.1 ⁇ m to 3.7 ⁇ m): 16.5%; and (0.1 ⁇ m to 0.5 ⁇ m): 11.9%; (0.5 ⁇ m to 0.9 ⁇ m): 11.7%; (0.9 ⁇ m to 1.3 ⁇ m): 10.6%; (1.3 ⁇ m to 1.7) ⁇ m): 11.4%; (1.7 ⁇ m to 2.1 ⁇ m): 10.2%; (2.1 ⁇ m to 2.5 ⁇ m): 11.0%; (2.5 ⁇ m to 2.9
  • the starch-containing microspheres have a particle size distribution interval of 70 to 270 ⁇ m (91.2% of the particle diameter is within this interval), and the particle size distribution in the particle size distribution interval has the following characteristics: (70 ⁇ m to 110 ⁇ m): 20.7%; (110 ⁇ m to 150 ⁇ m): 20.6%; (150 ⁇ m to 190 ⁇ m): 20.1%; (190 ⁇ m to 230 ⁇ m): 19.8%; (230 ⁇ m to 270 ⁇ m): 18.8%; and (70 ⁇ m to 90 ⁇ m): 11.7%; 90 ⁇ m to 110 ⁇ m): 11.0%; (110 ⁇ m to 130 ⁇ m): 11.3%; (130 ⁇ m to 150 ⁇ m): 10.3%; (150 ⁇ m to 170 ⁇ m): 11.2%; (170 ⁇ m to 190 ⁇ m): 10.9%; (190 ⁇ m to 210 ⁇ m): 11.4%; (210 ⁇ m to 230 ⁇ m):
  • the particle size distribution interval of the starch-containing microspheres is 0.1 to 4.9 ⁇ m (95.6% of the particle diameter is in this interval), and the particle size distribution in the particle size distribution interval has the following characteristics: (0.1 ⁇ m to 0.9) ⁇ m): 16.8%; (0.9 ⁇ m to 1.7 ⁇ m): 17.6%; (1.7 ⁇ m to 2.5 ⁇ m): 16.8%; (2.5 ⁇ m to 3.3 ⁇ m): 15.9%; (3.3 ⁇ m to 4.1 ⁇ m): 17.4%; (4.1 ⁇ m to 4.9 ⁇ m): 15.5%.
  • there are CN peak and S O peak in the infrared spectrum.
  • the starch is graft polymerized with the zwitterionic monomer.
  • the particle size distribution range of the starch-containing microspheres is 120-400 ⁇ m (92.2% of the particle diameter is in this interval), and the particle size distribution in the concentrated distribution range of the particle diameter has the following characteristics: (120 ⁇ m - 170 ⁇ m): 13.4%; (170 ⁇ m to 350 ⁇ m): 75.4%; (350 ⁇ m to 400 ⁇ m): 11.2%.
  • the starch structural unit content is 60.4% by weight, the DMAPS structural unit content is 32.5wt%, and the starch and DMAPS are grafted and polymerized.
  • the starch-containing microspheres were prepared in the same manner as in Example 2-1 except that 0.013 parts of epichlorohydrin was not added before adding 7 parts of DMAPS to obtain uniformly distributed polydisperse-containing starch microspheres.
  • the particle size distribution range of the starch-containing microspheres is 20-180 ⁇ m (91.8% of the particle diameter is in this interval), and the particle size distribution in the concentrated distribution range of the particle diameter has the following characteristics: (20 ⁇ m - 60 ⁇ m): 32.8%; (60 ⁇ m to 100 ⁇ m): 17.5%; (100 ⁇ m to 140 ⁇ m): 19.2%; (140 ⁇ m to 180 ⁇ m): 30.5%.
  • the content of the starch structural unit was 61.0% by weight, the content of the DMAPS structural unit was 31.9wt%, and the starch was graft-polymerized with DMAPS.
  • the starch-containing microspheres were prepared in the same manner as in Example 2-1 except that the inorganic salt aqueous solution and 1.5 parts of epichlorohydrin were simultaneously added to the starch solution at one time to obtain uniformly distributed polydisperse starch-containing microspheres.
  • the particle size distribution range of the starch-containing microspheres is 10 to 190 ⁇ m (96.2% of the particle diameter is in this interval), and the particle size distribution in the particle size distribution interval has the following characteristics: (10 ⁇ m to 55 ⁇ m): 9.9%; (55 ⁇ m to 100 ⁇ m): 37.2%; (100 ⁇ m to 145 ⁇ m): 42.1%; (145 ⁇ m to 190 ⁇ m): 10.8%.
  • the content of the starch structural unit was 60.4% by weight, and the content of the DMAPS structural unit was 32.3% by weight.
  • the starch was graft-polymerized with DMAPS.
  • Starch-containing microspheres were prepared as in Example 2-1 except that triethanolamine was not added to obtain uniformly distributed polydisperse starch-containing microspheres.
  • the particle size distribution range of the starch-containing microspheres is 5 to 205 ⁇ m (94.2% of the particle diameter is in this interval), and the particle size distribution in the particle size distribution interval has the following characteristics: (5 ⁇ m to 55 ⁇ m): 36.3%; (55 ⁇ m to 105 ⁇ m): 22.1%; (105 ⁇ m to 155 ⁇ m): 19.9%; (155 ⁇ m to 205 ⁇ m): 21.7%.
  • the content of the starch structural unit was 59.6 wt%, and the content of the DMAPS structural unit was 34.0 wt%, and the starch was graft-polymerized with DMAPS.
  • Examples 3-1 to 3-8 and Comparative Examples 3-1 to 3-4 are examples of the addition of cationic monomers.
  • the particle size distribution range of the starch-containing microspheres is 10 to 170 ⁇ m (95.6% of the particle diameter is in this interval), and the particle size distribution in the particle size distribution interval has the following characteristics: (10 ⁇ m to 50 ⁇ m): 24.4%; (50 ⁇ m to 90 ⁇ m): 25.6%; (90 ⁇ m to 130 ⁇ m): 25.1%; (130 ⁇ m to 170 ⁇ m): 24.9%; and (10 ⁇ m to 26 ⁇ m): 10.3%; (26 ⁇ m to 42 ⁇ m): 10.9%; 42 ⁇ m to 58 ⁇ m): 9.8%; (58 ⁇ m to 74 ⁇ m): 9.7%; (74 ⁇ m to 90 ⁇ m): 9.2%; (90 ⁇ m to 106 ⁇ m): 10.9%; (106 ⁇ m to 122 ⁇ m): 9.2%; (122 ⁇ m to 138 ⁇ m): 9.6%; (138 ⁇ m to 154 ⁇ m): 10.4%
  • the starch was graft polymerized with DEDAAC.
  • sweet potato starch was weighed into 100 parts of deionized water, and then 50 parts of triethanolamine was added, and it was fully dissolved at 50 °C. Then, 0.015 parts of epichlorohydrin was added, and after mixing, the reaction was carried out for 2.5 hours. 0.1 part of DBC was weighed into the starch solution, and fully dissolved and mixed. 0.001 parts of ammonium persulfate was added at 65 ° C for 4 h. 0.05 part of dimethyl(6-aminotetradecyl)sulfoethylammonium salt was added and mixed well.
  • the particle size distribution range of the starch-containing microspheres is 0.1 to 6.1 ⁇ m (the particle diameter of 96.0% is in this interval), and the particle size distribution in the concentrated distribution range of the particle diameter has the following characteristics: (0.1 ⁇ m to 1.1) ⁇ m): 17.5%; (1.1 ⁇ m to 2.1 ⁇ m): 15.9%; (2.1 ⁇ m to 3.1 ⁇ m): 17.2%; (3.1 ⁇ m to 4.1 ⁇ m): 16.5%; (4.1 ⁇ m to 5.1 ⁇ m): 16.4%; (5.1 ⁇ m to 6.1 ⁇ m): 16.5%.
  • there are C-N peak and S O peak in the infrared spectrum.
  • Starch and DBC have undergone graft polymerization.
  • the particle size distribution range of the starch-containing microspheres is 0.1 to 7.3 ⁇ m (96.3% of the particle diameter is in this interval), and the particle size distribution in the particle size distribution interval has the following characteristics: (0.1 ⁇ m to 1.3) ⁇ m): 16.6%; (1.3 ⁇ m to 2.5 ⁇ m): 17.6%; (2.5 ⁇ m to 3.7 ⁇ m): 17.0%; (3.7 ⁇ m to 4.9 ⁇ m): 16.4%; (4.9 ⁇ m to 6.1 ⁇ m): 17.4%; (6.1 ⁇ m to 7.3 ⁇ m): 16.0%; and (0.1 ⁇ m to 0.7 ⁇ m): 8.2%; (0.7 ⁇ m to 1.3 ⁇ m): 8.4%; (1.3 ⁇ m to 1.9 ⁇ m): 8.6%; (1.9 ⁇ m to 2.5) Mm): 9.0%; (2.5 ⁇ m to 3.1 ⁇ m): 8.5%; (3.1 ⁇ m to 3.7 ⁇ m): 8.5%; (3.7 ⁇ m to 4.3 ⁇
  • the particle size distribution range of the starch-containing microspheres is 120 to 400 ⁇ m (94.1% of the particle diameter is in this interval), and the particle size distribution in the particle size distribution interval has the following characteristics: (120 ⁇ m to 170 ⁇ m): 11.0%; (170 ⁇ m to 350 ⁇ m): 79.8%; (350 ⁇ m to 400 ⁇ m): 9.2%.
  • the starch structural unit content was 46.6 wt%
  • the DMDAAC structural unit content was 45.8 wt%.
  • Starch-containing microspheres were prepared as in Example 3-1 except that 0.009 parts of epichlorohydrin were not added prior to the addition of DMDAAC to obtain uniformly distributed polydisperse starch-containing microspheres.
  • the particle size distribution range of the starch-containing microspheres is 20 to 180 ⁇ m (95.1% of the particle diameter is in this interval), and the particle size distribution in the particle size distribution interval has the following characteristics: (20 ⁇ m to 60 ⁇ m): 32.7%; (60 ⁇ m to 100 ⁇ m): 18.0%; (100 ⁇ m to 140 ⁇ m): 19.3%; (140 ⁇ m to 180 ⁇ m): 30.0%.
  • the starch structural unit content was 46.0% by weight
  • the DMDAAC structural unit content was 45.2% by weight.
  • the starch was graft-polymerized with DMDAAC.
  • the starch-containing microspheres were prepared according to the method of Example 3-1 except that the inorganic salt was added to the starch solution at a time with 1 part of epichlorohydrin to obtain a uniformly distributed polydisperse starch-containing microsphere.
  • the particle size distribution range of the starch-containing microspheres is 30 to 190 ⁇ m (92.7% of the particle diameter is in this interval), and the particle size distribution in the particle size distribution interval has the following characteristics: (30 ⁇ m to 70 ⁇ m): 9.9%; (70 ⁇ m to 110 ⁇ m): 37.2%; (110 ⁇ m to 150 ⁇ m): 42.1%; (150 ⁇ m to 190 ⁇ m): 10.8%.
  • the starch structural unit content was 45.2% by weight, and the DMDAAC structural unit content was 46.1% by weight.
  • the starch was graft-polymerized with DMDAAC.
  • Starch-containing microspheres were prepared according to the procedure of Example 3-1, except that triethanolamine was not added to obtain uniformly distributed polydisperse starch-containing microspheres.
  • the particle size distribution range of the starch-containing microspheres is 15 to 215 ⁇ m (95.4% of the particle diameter is in this interval), and the particle size distribution in the particle size distribution interval has the following characteristics: (15 ⁇ m to 65 ⁇ m): 36.3%; (65 ⁇ m to 115 ⁇ m): 21.7%; (115 ⁇ m to 165 ⁇ m): 19.9%; (165 ⁇ m to 215 ⁇ m): 22.1%.
  • the starch structural unit content was determined to be 44.9 wt%, and the content of the DMDAAC structural unit was 45.6 wt%, and the starch was graft-polymerized with DMDAAC.
  • Examples 4-1 to 4-8 and Comparative Example 4-1 to Comparative Example 4-4 are examples of the addition of an anionic monomer.
  • KCl KCl was weighed into 130 parts of an inorganic salt solution, and added dropwise to the starch solution at 55 ° C with 2 parts of epichlorohydrin, and the mixture was added dropwise at a constant rate for 5 hours. After the completion of the dropwise addition, the reaction was continued for 2 hours to obtain a uniformly distributed polydisperse starch-containing microsphere having a starch structural unit content of 56.9 wt% and an AMPS structural unit content of 30.8 wt%.
  • the particle size distribution range of the starch-containing microspheres is 10 to 170 ⁇ m (92.9% of the particle diameter is in this interval), and the particle size distribution in the particle size distribution interval has the following characteristics: (10 ⁇ m to 50 ⁇ m): 25.4%; (50 ⁇ m to 90 ⁇ m): 24.6%; (90 ⁇ m to 130 ⁇ m): 25.3%; (130 ⁇ m to 170 ⁇ m): 24.7%; and (10 ⁇ m to 20 ⁇ m): 6.2%; (20 ⁇ m to 30 ⁇ m): 6.4%; 30 ⁇ m to 40 ⁇ m): 5.9%; (40 ⁇ m to 50 ⁇ m): 6.8%; (50 ⁇ m to 60 ⁇ m): 6.0%; (60 ⁇ m to 70 ⁇ m): 6.3%; (70 ⁇ m to 80 ⁇ m): 6.8%; (80 ⁇ m to 90 ⁇ m): 5.9%; (90 ⁇ m to 100 ⁇ m): 6.5%; (100 ⁇ m to
  • the particle size distribution interval of the starch-containing microspheres is 150 to 500 ⁇ m (96.1% of the particle diameter is in this interval), and the particle size distribution in the particle size distribution interval has the following characteristics: (150 ⁇ m to 200 ⁇ m): 14.7%; (200 ⁇ m to 250 ⁇ m): 13.6%; (250 ⁇ m to 300 ⁇ m): 15.4%; (300 ⁇ m to 350 ⁇ m): 13.9%; (350 ⁇ m to 400 ⁇ m): 14.7%; (400 ⁇ m to 450 ⁇ m): 14.2%; (450 ⁇ m) ⁇ 500 ⁇ m): 13.5%.
  • there are CN peak and S O peak in the infrared spectrum. Starch and SSS were graft polymerized.
  • sweet potato starch was weighed into 100 parts of deionized water, and then 50 parts of triethanolamine was added, and it was fully dissolved at 50 °C. Then, 0.38 parts of epichlorohydrin was added, and after mixing, the reaction was carried out for 2.5 hours. Weigh 0.1 part of AIOAS into the starch solution and dissolve it thoroughly. 0.001 parts of ammonium persulfate was added at 65 ° C for 4 h. 0.05 part of dimethyl(6-aminotetradecyl)sulfoethylammonium salt was added and mixed well.
  • the particle size distribution interval of the starch-containing microspheres is 0.1 to 6.7 ⁇ m (92.8% of the particle diameter is in this interval), and the particle size distribution in the concentration distribution interval has the following characteristics: (0.1 ⁇ m to 1.2) ⁇ m): 17.0%; (1.2 ⁇ m to 2.3 ⁇ m): 15.5%; (2.3 ⁇ m to 3.4 ⁇ m): 17.2%; (3.4 ⁇ m to 4.5 ⁇ m): 17.0%; (4.5 ⁇ m to 5.6 ⁇ m): 16.8%; (5.6 ⁇ m to 6.7 ⁇ m): 16.5%.
  • Starch and AOIAS have undergone graft polymerization.
  • the particle size distribution range of the starch-containing microspheres is 20 to 260 ⁇ m (94.7% of the particle diameter is in this interval), and the particle size distribution in the particle size distribution interval has the following characteristics: (20 ⁇ m to 60 ⁇ m): 17.3%; (60 ⁇ m to 100 ⁇ m): 16.2%; (100 ⁇ m to 140 ⁇ m): 16.4%; (140 ⁇ m to 180 ⁇ m): 17.4%; (180 ⁇ m to 220 ⁇ m): 17.4%; (220 ⁇ m to 260 ⁇ m): 15.3%.
  • there are CN peak and S O peak in the infrared spectrum. Starch and AMPS undergo graft polymerization.
  • the particle size distribution range of the starch-containing microspheres is 0.1 to 8.5 ⁇ m (94.3% of the particle diameter is in this interval), and the particle size distribution in the particle size distribution interval has the following characteristics: (0.1 ⁇ m to 1.5) ⁇ m): 16.4%; (1.5 ⁇ m to 2.9 ⁇ m): 17.6%; (2.9 ⁇ m to 4.3 ⁇ m): 17.1%; (4.3 ⁇ m to 5.7 ⁇ m): 16.2%; (5.7 ⁇ m to 7.1 ⁇ m): 17.6%; (7.1 ⁇ m to 8.5 ⁇ m): 16.1%; and (0.1 ⁇ m to 0.7 ⁇ m): 7.2%; (0.7 ⁇ m to 1.3 ⁇ m): 7.8%; (1.3 ⁇ m to 1.9 ⁇ m): 7.0%; (1.9 ⁇ m to 2.5) ⁇ m): 7.3%; (2.5 ⁇ m to 3.1 ⁇ m): 7.4%; (3.1 ⁇ m to 3.7 ⁇ m): 6.6%; (3.7 ⁇ m to 4.3
  • the particle size distribution range of the starch-containing microspheres is 120-400 ⁇ m (95.8% of the particle diameter is in this interval), and the particle size distribution in the particle size distribution interval has the following characteristics: (120 ⁇ m - 170 ⁇ m): 11.6%; (170 ⁇ m to 350 ⁇ m): 78.6%; (350 ⁇ m to 400 ⁇ m): 9.8%.
  • the content of the starch structural unit is 57.6 wt%, and the content of the AMPS structural unit is 31.2 wt%, and the starch and the AMPS are graft polymerized.
  • Starch-containing microspheres were prepared as in Example 4-1 except that epichlorohydrin was not added prior to the addition of AMPS to obtain uniformly distributed polydisperse starch-containing microspheres.
  • the particle size distribution range of the starch-containing microspheres is 20 to 180 ⁇ m (94.4% of the particle diameter is in this interval), and the particle size distribution in the particle size distribution interval has the following characteristics: (20 ⁇ m to 60 ⁇ m): 31.7%; (60 ⁇ m to 100 ⁇ m): 18.1%; (100 ⁇ m to 140 ⁇ m): 19.2%; (140 ⁇ m to 180 ⁇ m): 31.0%.
  • the content of the starch structural unit is 58.0% by weight, and the content of the AMPS structural unit is 30.7% by weight, and the starch and the AMPS are graft polymerized.
  • the starch-containing microspheres were prepared according to the method of Example 4-1 except that the inorganic salt solution and the 2 parts of epichlorohydrin were simultaneously added to the starch solution at one time to obtain uniformly distributed polydisperse starch-containing microspheres.
  • the particle size distribution range of the starch-containing microspheres is 10 to 210 ⁇ m (93.9% of the particle diameter is in this interval), and the particle size distribution in the particle size distribution interval has the following characteristics: (10 ⁇ m to 60 ⁇ m): 9.9%; (60 ⁇ m to 110 ⁇ m): 38.1%; (110 ⁇ m to 160 ⁇ m): 41.2%; (160 ⁇ m to 210 ⁇ m): 10.8%.
  • the content of the starch structural unit is 57.8 wt%, and the content of the AMPS structural unit is 31.5 wt%, and the starch and the AMPS are graft polymerized.
  • Starch-containing microspheres were prepared according to the procedure of Example 4-1 except that triethanolamine was not added to obtain uniformly distributed polydisperse starch-containing microspheres.
  • the particle size distribution range of the starch-containing microspheres is 5 to 205 ⁇ m (92.5% of the particle diameter is in this interval), and the particle size distribution in the particle size distribution interval has the following characteristics: (5 ⁇ m to 55 ⁇ m): 35.2%; (55 ⁇ m to 105 ⁇ m): 21.6%; (105 ⁇ m to 155 ⁇ m): 20.0%; (155 ⁇ m to 205 ⁇ m): 23.2%.
  • the starch structural unit content is 57.4 wt%, the AMPS structural unit content is 31.3 wt%, and starch and AMPS are graft polymerized.
  • Examples 5-1 to 5-8 and Comparative Example 5-1 to Comparative Example 5-4 are examples of the addition of a nonionic monomer.
  • the starch-containing microspheres have a particle size distribution range of 50 to 210 ⁇ m (95.0% of the particle diameter is in this interval), and the particle size distribution in the particle size distribution interval has the following characteristics: (120 ⁇ m to 400 ⁇ m): 24.2%; (190 ⁇ m to 260 ⁇ m): 26.1%; (260 ⁇ m to 330 ⁇ m): 24.7%; (330 ⁇ m to 400 ⁇ m): 25.0%.
  • there are CN peak and S O peak in the infrared spectrum.
  • Starch and AN have undergone graft polymerization.
  • the particle size distribution range of the starch-containing microspheres is 150 to 500 ⁇ m (96.2% of the particle diameter is in this interval), and the particle size distribution in the particle size distribution interval has the following characteristics: (150 ⁇ m to 200 ⁇ m): 14.8%; (200 ⁇ m to 250 ⁇ m): 13.7%; (250 ⁇ m to 300 ⁇ m): 15.2%; (300 ⁇ m to 350 ⁇ m): 14.0%; (350 ⁇ m to 400 ⁇ m): 14.6%; (400 ⁇ m to 450 ⁇ m): 14.2%; (450 ⁇ m) ⁇ 500 ⁇ m): 13.5%.
  • there are CN peak and S O peak in the infrared spectrum.
  • Starch and NVA have undergone graft polymerization.
  • sweet potato starch was weighed into 100 parts of deionized water, and then 50 parts of triethanolamine was added, and it was fully dissolved at 50 °C. Then, 0.51 parts of epichlorohydrin was added, and after mixing, the reaction was carried out for 2.5 hours.
  • 0.1 part of AN was weighed into the starch solution, and fully dissolved and mixed. 0.001 parts of ammonium persulfate was added at 65 ° C for 4 h. 0.05 part of dimethyl(6-aminotetradecyl)sulfoethylammonium salt was added and mixed well.
  • the particle size distribution range of the starch-containing microspheres is 0.1 to 7.9 ⁇ m (93.8% of the particle diameter is in this interval), and the particle size distribution in the particle size distribution interval has the following characteristics: (0.1 ⁇ m to 1.4) ⁇ m): 17.1%; (1.4 ⁇ m to 2.7 ⁇ m): 16.0%; (2.7 ⁇ m to 4.0 ⁇ m): 17.0%; (4.0 ⁇ m to 5.3 ⁇ m): 17.1%; (5.3 ⁇ m to 6.6 ⁇ m): 16.8%; (6.6 ⁇ m to 7.9 ⁇ m): 16.0%.
  • Starch and AN have undergone graft polymerization.
  • the particle size distribution range of the starch-containing microspheres is 20 to 260 ⁇ m (92.5% of the particle diameter is in this interval), and the particle size distribution in the particle size distribution interval has the following characteristics: (20 ⁇ m to 60 ⁇ m): 17.0%; (60 ⁇ m to 100 ⁇ m): 16.3%; (100 ⁇ m to 140 ⁇ m): 16.7%; (140 ⁇ m to 180 ⁇ m): 17.3%; (180 ⁇ m to 220 ⁇ m): 17.4%; (220 ⁇ m to 260 ⁇ m): 15.3%.
  • there are CN peak and S O peak in the infrared spectrum.
  • Starch and NVP have undergone graft polymerization.
  • the particle size distribution range of the starch-containing microspheres is 0.1 to 10.3 ⁇ m (93.3% of the particle diameter is in this interval), and the particle size distribution in the particle size distribution interval has the following characteristics: (0.1 ⁇ m to 1.8) ⁇ m): 16.0%; (1.8 ⁇ m to 3.5 ⁇ m): 17.5%; (3.5 ⁇ m to 5.2 ⁇ m): 17.3%; (5.2 ⁇ m to 6.9 ⁇ m): 16.6%; (6.9 ⁇ m to 8.6 ⁇ m): 17.5%; (8.6 ⁇ m to 10.3 ⁇ m): 16.1%.
  • there are CN peak and S O peak in the infrared spectrum. Starch and nonionic monomers undergo graft polymerization.
  • the content of the starch structural unit was 60.3 wt%, and the content of the NVP structural unit was 27.9% by weight.
  • the particle size distribution range of the starch-containing microspheres is 120-400 ⁇ m (94.5% of the particle diameter is in this interval), and the particle size distribution in the particle size distribution interval has the following characteristics: (120 ⁇ m - 170 ⁇ m): 12.8%; (170 ⁇ m to 350 ⁇ m): 78.3%; (350 ⁇ m to 400 ⁇ m): 8.9%.
  • Starch and NVP have undergone graft polymerization.
  • Starch-containing microspheres were prepared as in Example 5-1 except that 0.23 parts of epichlorohydrin was not added prior to the addition of NVP to obtain uniformly distributed polydisperse starch-containing microspheres.
  • the particle size distribution interval of the starch-containing microspheres is 20 to 180 ⁇ m (92.5% of the particle diameter is in this interval), and the particle size distribution in the particle size distribution interval has the following characteristics: (20 ⁇ m to 60 ⁇ m): 31.5%; (60 ⁇ m to 100 ⁇ m): 18.0%; (100 ⁇ m to 140 ⁇ m): 19.3%; (140 ⁇ m to 180 ⁇ m): 31.2%.
  • the starch structural unit content is 58.8 wt%, and the NVP structural unit content is 29.0 wt%, and starch and NVP are graft polymerized.
  • the starch-containing microspheres were prepared according to the method of Example 5-1 except that the inorganic salt solution and the 2.2 parts of epichlorohydrin were simultaneously added to the starch solution at one time to obtain uniformly distributed polydisperse starch-containing microspheres.
  • the particle size distribution interval of the starch-containing microspheres is 30 to 230 ⁇ m (91.8% of the particle diameter is in this interval), and the particle size distribution in the particle size distribution interval has the following characteristics: (30 ⁇ m to 80 ⁇ m): 9.8%; (80 ⁇ m to 130 ⁇ m): 38.2%; (130 ⁇ m to 180 ⁇ m): 41.1%; (180 ⁇ m to 230 ⁇ m): 10.9%.
  • the content of the starch structural unit is 59.1% by weight, and the content of the NVP structural unit is 29.4% by weight, and the starch and the NVP are graft-polymerized.
  • Starch-containing microspheres were prepared according to the procedure of Example 5-1 except that triethanolamine was not added to obtain uniformly distributed polydisperse starch-containing microspheres.
  • the starch-containing microspheres have a particle size distribution interval of 20 to 200 ⁇ m (93.2% of the particle diameter is in this interval), and the particle size distribution in the particle size distribution interval has the following characteristics: (20 ⁇ m to 65 ⁇ m): 35.0%; (65 ⁇ m to 110 ⁇ m): 21.8%; (110 ⁇ m to 155 ⁇ m): 19.8%; (155 ⁇ m to 200 ⁇ m): 23.4%.
  • the starch structural unit content is 58.6 wt%, and the NVP structural unit content is 28.7% wt%, and starch and NVP are graft polymerized.
  • Examples 6-1 to 6-10 and Comparative Examples 6-1 to 6-4 are examples in which two or more monomers are added.
  • the particle size distribution range of the starch-containing microspheres is 10 to 170 ⁇ m (94.5% of the particle diameter is in this interval), and the particle size distribution in the particle size distribution interval has the following characteristics: (10 ⁇ m to 50 ⁇ m): 25.4%; (50 ⁇ m to 90 ⁇ m): 25.1%; (90 ⁇ m to 130 ⁇ m): 25.1%; (130 ⁇ m to 170 ⁇ m): 24.4%; and (10 ⁇ m to 30 ⁇ m): 11.3%; (30 ⁇ m to 50 ⁇ m): 13.2%; 50 ⁇ m to 70 ⁇ m): 12.8%; (70 ⁇ m to 90 ⁇ m): 12.2%; (90 ⁇ m to 110 ⁇ m): 13.5%; (110 ⁇ m to 130 ⁇ m): 11.6%; (130 ⁇ m to 150 ⁇ m): 12.2%; (150 ⁇ m to 170 ⁇ m): 13.2%.
  • the content of the starch structural unit is 47.5 wt%, the content of the functional monomer structural unit is 37.9 wt%, wherein the content of the MAPS structural unit is 11.8 wt%, the content of the NVF structural unit is 12.5% by weight, and the content of the AA structural unit is 13.6 wt. %.
  • Starch was grafted with MAPS, NVF and AA.
  • the content of the starch structural unit was 26.9 wt%, the content of the DMC structural unit was 10.7 wt%, and the content of the SSS structural unit was 20.12 wt%, and the starch was graft-polymerized with DMC and SSS.
  • the content of the starch structural unit was 38.9 wt%, and the content of the functional monomer structural unit was 33.1 wt%, wherein the content of the FA structural unit was 24.2 wt%, and the content of the NVA structural unit was 8.2 wt%.
  • Starch was grafted with FA and NVA.
  • the particle size distribution range of the starch-containing microspheres is 150 to 500 ⁇ m (96.2% of the particle diameter is in this interval), and the particle size distribution in the particle size distribution interval has the following characteristics: (150 ⁇ m to 200 ⁇ m): 13.5%; (200 ⁇ m to 250 ⁇ m): 14.1%; (250 ⁇ m to 300 ⁇ m): 15.4%; (300 ⁇ m to 350 ⁇ m): 14.8%; (350 ⁇ m to 400 ⁇ m): 14.0%; (400 ⁇ m to 450 ⁇ m): 14.7%; (450 ⁇ m) ⁇ 500 ⁇ m): 13.5%.
  • there are CN peak and S O peak in the infrared spectrum.
  • the content of the starch structural unit was 32.1% by weight, the content of the functional monomer structural unit was 42.9 wt%, and the contents of the DAPS, DBC, AMPS, and NVP structural units were 15.2 wt%, 8.6 wt%, 15.0 wt%, and 7.8 wt%, respectively.
  • Starch was grafted with DAPS, DBC, AMPS and NVP.
  • the particle size distribution range of the starch-containing microspheres is 0.2 to 6.2 ⁇ m (92.7% of the particle diameter is in this interval), and the particle size distribution in the particle size distribution interval has the following characteristics: (0.2 ⁇ m to 1.2) ⁇ m): 16.5%; (1.2 ⁇ m to 2.2 ⁇ m): 15.9%; (2.2 ⁇ m to 3.2 ⁇ m): 17.2%; (3.2 ⁇ m to 4.2 ⁇ m): 17.5%; (4.2 ⁇ m to 5.2 ⁇ m): 16.4%; (5.2 ⁇ m to 6.2 ⁇ m): 16.5%.
  • the content of the starch structural unit was 71.9 wt%, the content of the functional monomer structural unit was 7.2 wt%, and the contents of the MABS, DMDAAC, AA, and AN structural units were 1.7 wt%, 1.9 wt%, 1.6 wt%, and 2.0 wt%, respectively.
  • Starch was grafted with MABS, DMDAAC, AA and AN.
  • the starch-containing microspheres have a particle size distribution interval of 70 to 290 ⁇ m (92.1% of the particle diameter is in this interval), and the particle size distribution in the particle size distribution interval has the following characteristics: (70 ⁇ m to 114 ⁇ m): 20.5%; (114 ⁇ m to 158 ⁇ m): 20.8%; (158 ⁇ m to 202 ⁇ m): 20.0%; (202 ⁇ m to 246 ⁇ m): 19.9%; (246 ⁇ m to 290 ⁇ m): 18.8%.
  • there are CN peak and S O peak in the infrared spectrum.
  • the content of the starch structural unit was 49.8 wt%, the content of the functional monomer structural unit was 14.3 wt%, and the contents of the VPPS, DAC, AAOAS, and NVA structural units were 2.1 wt%, 2.3 wt%, 7.1 wt%, and 2.8 wt%, respectively.
  • Starch was grafted with VPPS, DAC, AIOAS and NVA.
  • the content of the starch structural unit was 25.2% by weight, the content of the functional monomer structural unit was 21.7 wt%, and the contents of the MAPS, DMC, FA, and NVP structural units were 9.4 wt%, 3.3 wt%, 2.9 wt%, and 6.1 wt%, respectively.
  • Starch was grafted with MAPS, DMC, FA and NVP.
  • the particle size distribution range of the starch-containing microspheres is 0.1 to 12.1 ⁇ m (94.5% of the particle diameter is in this interval), and the particle size distribution in the concentration distribution interval has the following characteristics: (0.1 ⁇ m to 2.1) ⁇ m): 16.6%; (2.1 ⁇ m to 4.1 ⁇ m): 17.4%; (4.1 ⁇ m to 6.1 ⁇ m): 16.8%; (6.1 ⁇ m to 8.1 ⁇ m): 16.3%; (8.1 ⁇ m to 10.1 ⁇ m): 17.4%; (10.1 ⁇ m to 12.1 ⁇ m): 15.5%.
  • there are CN peak and S O peak in the infrared spectrum.
  • the content of the starch structural unit was 27.0% by weight, the content of the functional monomer structural unit was 21.8% by weight, and the contents of the AN and NVP structural units were 11.1% by weight and 10.7% by weight, respectively.
  • Starch was grafted with MAPS, AN and NVP.
  • the content of the starch structural unit was 38.5 wt%, the content of the functional monomer structural unit was 43.2 wt%, and the contents of the MAPS, DEDAAC, AMPS, and AN structural units were 10.7 wt%, 10.9 wt%, 11.7 wt%, and 9.9 wt%, respectively.
  • Starch was grafted with MAPS, DEDAAC, AMPS and AN.
  • the particle size distribution range of the starch-containing microspheres is 40 to 280 ⁇ m (93.6% of the particle diameter is in this interval), and the particle size distribution in the particle size distribution interval has the following characteristics: (40 ⁇ m to 88 ⁇ m): 20.8%; (88 ⁇ m to 136 ⁇ m): 20.8%; (136 ⁇ m to 184 ⁇ m): 20.0%; (184 ⁇ m to 232 ⁇ m): 19.6%; (232 ⁇ m to 280 ⁇ m): 18.8%.
  • the content of the starch structural unit was 51.6 wt%, the content of the functional monomer structural unit was 24.2 wt%, and the contents of the DMAPS, MAPS, and NVF structural units were 4.1 wt%, 8.2 wt%, and 11.9 wt%, respectively.
  • Starch was grafted with DMAPS, MAPS and NVF.
  • Starch-containing microspheres were prepared as in Example 6-1 except that triethanolamine was replaced by the same weight of trimethylamine to obtain uniformly distributed polydisperse starch-containing microspheres.
  • the particle size distribution range of the starch-containing microspheres is 10 to 170 ⁇ m (94.5% of the particle diameter is in this interval), and the particle size distribution in the particle size distribution interval has the following characteristics: (10 ⁇ m to 50 ⁇ m): 25.4%; (50 ⁇ m to 90 ⁇ m): 25.1%; (90 ⁇ m to 130 ⁇ m): 25.1%; (130 ⁇ m to 170 ⁇ m): 24.4%; and (10 ⁇ m to 30 ⁇ m): 11.3%; (30 ⁇ m to 50 ⁇ m): 13.7%; 50 ⁇ m to 70 ⁇ m): 13.7%; (70 ⁇ m to 90 ⁇ m): 11.8%; (90 ⁇ m to 110 ⁇ m): 13.5%; (110 ⁇ m to 130 ⁇ m): 11.6%; (130
  • the content of the starch structural unit was 47.2% by weight, the content of the functional monomer structural unit was 37.0% by weight, the content of the MAPS structural unit was 11.7% by weight, the content of the NVF structural unit was 12.1% by weight, and the content of the AA structural unit was 13.2.
  • Gt% starch was grafted with MAPS, NVF and AA.
  • Starch-containing microspheres were prepared as in Example 6-1 except that epichlorohydrin was replaced by the same weight of phosphorus oxychloride to obtain uniformly distributed polydisperse starch-containing microspheres.
  • the particle size distribution range of the starch-containing microspheres is 10 to 170 ⁇ m (94.5% of the particle diameter is in this interval), and the particle size distribution in the particle size distribution interval has the following characteristics: (10 ⁇ m to 50 ⁇ m): 25.4%; (50 ⁇ m to 90 ⁇ m): 25.1%; (90 ⁇ m to 130 ⁇ m): 25.1%; (130 ⁇ m to 170 ⁇ m): 24.4%; and (10 ⁇ m to 30 ⁇ m): 13.2%; (30 ⁇ m to 50 ⁇ m): 13.3%; 50 ⁇ m to 70 ⁇ m): 12.9%; (70 ⁇ m to 90 ⁇ m): 11.5%; (90 ⁇ m to 110 ⁇ m): 13.1%; (110 ⁇ m to 130 ⁇ m
  • the content of the starch structural unit was 47.2% by weight, the content of the functional monomer structural unit was 37.9 wt%, the content of the MAPS structural unit was 11.7% by weight, the content of the NVF structural unit was 13.5 wt%, and the content of the AA structural unit was 12.7. Gt%, starch was grafted with MAPS, NVF and AA.
  • the particle size distribution range of the starch-containing microspheres is 120-400 ⁇ m (95.9% of the particle diameter is in this interval), and the particle size distribution in the particle size distribution interval has the following characteristics: (120 ⁇ m - 170 ⁇ m): 12.4%; (170 ⁇ m to 350 ⁇ m): 79.4%; (350 ⁇ m to 400 ⁇ m): 8.2%.
  • the content of the starch structural unit is 45.6 wt%, the content of the functional monomer structural unit is 32.9 wt%, the content of the MAPS structural unit is 7.6 wt%, the content of the NVF structural unit is 14.1 wt%, and the content of the AA structural unit is 11.2 wt%.
  • Starch was grafted with MAPS, NVF and AA.
  • the particle size distribution range of the starch-containing microspheres is 20 to 180 ⁇ m (95.3% of the particle diameter is in this interval), and the particle size distribution in the particle size distribution interval has the following characteristics: (20 ⁇ m to 60 ⁇ m): 32.8%; (60 ⁇ m to 100 ⁇ m): 17.5%; (100 ⁇ m to 140 ⁇ m): 18.2%; (140 ⁇ m to 180 ⁇ m): 31.5%.
  • the content of the starch structural unit is 47.9 wt%
  • the content of the functional monomer structural unit is 33.6 wt%
  • the content of the MAPS structural unit is 10.2 wt%
  • the content of the NVF structural unit is 11.1 wt%
  • the content of the AA structural unit is 12.3 wt%.
  • Starch was grafted with MAPS, NVF and AA.
  • the starch-containing microspheres were prepared according to the method of Example 6-1 except that the inorganic salt solution and the 3 parts of epichlorohydrin were simultaneously added to the starch solution at one time to obtain uniformly distributed polydisperse starch-containing microspheres.
  • the particle size distribution range of the starch-containing microspheres is 20 to 200 ⁇ m (93.8% of the particle diameter is in this interval), and the particle size distribution in the particle size distribution interval has the following characteristics: (20 ⁇ m to 65 ⁇ m): 9.9%; (65 ⁇ m to 110 ⁇ m): 37.1%; (110 ⁇ m to 155 ⁇ m): 42.2%; (155 ⁇ m to 200 ⁇ m): 10.8%.
  • the content of the starch structural unit is 47.4 wt%
  • the content of the functional monomer structural unit is 37.6 wt%
  • the content of the MAPS structural unit is 11.6 wt%
  • the content of the NVF structural unit is 13.8 wt%
  • the content of the AA structural unit is 12.2 wt%.
  • Starch was grafted with MAPS, NVF and AA.
  • Starch-containing microspheres were prepared as in Example 6-1 except that triethanolamine was not added to obtain uniformly distributed polydisperse starch-containing microspheres.
  • the particle size distribution range of the starch-containing microspheres is 8 to 200 ⁇ m (91.7% of the particle diameter is in this interval), and the particle size distribution in the particle size distribution interval has the following characteristics: (8 ⁇ m to 56 ⁇ m): 36.3%; (56 ⁇ m to 104 ⁇ m): 21.7%; (104 ⁇ m to 152 ⁇ m): 19.9%; (152 ⁇ m to 200 ⁇ m): 22.1%.
  • the content of the starch structural unit is 45.3 wt%, the content of the functional monomer structural unit is 38.2 wt%, the content of the MAPS structural unit is 11.6 wt%, the content of the NVF structural unit is 12.7 wt%, and the content of the AA structural unit is 13.9 wt%.
  • Starch was grafted with MAPS, NVF and AA.
  • micron-sized starch microspheres prepared in the above examples and comparative examples were each evaluated as a temporary plugging agent by a sand bed plugging test.
  • Experimental equipment drilling fluid sand bed filter, stirrer, oven.
  • Experimental materials Well granule (weight 1.19 g/cm 3 ) of the Well 860 of Henan Oilfield, Sinopec, sample samples, comparative samples and 20-40 mesh sand samples.
  • Drilling fluid was prepared according to the well slurry + 3 wt% of the example sample or the comparative sample.
  • the fluid loss FL 1 is basically stable after the drilling fluid invades the sand bed to the depth D. After the stable mud cake is formed, the drilling fluid is drained from the pressure, and the water is added to the position of 400 mL, and the fluid loss FL 2 after 30 minutes is measured by pressurization (0.69 mPa). The experimental results are shown in Tables 1 to 6.
  • the temperature and salt resistance of the above examples and comparative examples were evaluated using a medium temperature medium pressure filter.
  • Experimental equipment medium temperature medium pressure filter, agitator, aging kettle, roller heating furnace.
  • Experimental materials Well granule (weight 1.19 g/cm 3 ) of the Well 860 of Henan Oilfield, Sinopec, sample of the example, comparative sample.
  • Drilling fluid was prepared according to the well slurry + 5 wt% NaCl + 5 wt% CaCl 2 + 3 wt% of the example sample or the comparative sample.
  • the fluid loss of the drilling fluid was FL 3 after 30 minutes from the start of the evaluation, and the experimental results are shown in Tables 1 to 6.
  • Comparative example 1-2 0 310 12 60 49 Comparative example 1-3 3 350 60 58 49 Comparative example 1-4 0 330 20 55 46
  • Example Filtration loss FL 1 /ml Depth D/mm Filtration loss FL 2 /ml Filtration loss FL 3 /ml R2% Example 2-1 0 135 0 5 20
  • Example 2-2 0 170 0 2 17
  • Example 2-3 0 190 0 2 16
  • Example 2-4 0 200 0 1 14
  • Example 2-5 0 220 0 10 twenty three
  • Example 2-6 0 205 0 3 13
  • Example 2-8 0 205 0 1 18 Comparative example 2-1 2 350 65 45 43
  • Comparative Example 2-2 0 310 15 40 40 Comparative example 2-3 3 350 73 39
  • Comparative example 2-4 0 330 twenty two 33 36
  • Example 3-5 0 205 0 25 17
  • Example 3-6 0 200 0 twenty one 14
  • Example 3-7 0 150 0 16 11
  • Example 3-8 0 190 0 twenty four 17 Comparative example 3-1 2 350 70 60
  • Comparative example 3-2 0 330 twenty two
  • Comparative 3-3 3 350
  • Comparative 3-4 0 315 13 49 30
  • Example 4-1 0 130 0 11 twenty one
  • Example 4-2 0 175 0 13 twenty two
  • Example 4-3 0 170 0 10
  • Example 4-4 0 210 0 6 17
  • Example 4-5 0 200 0 20 26
  • Example 4-6 0 165 0 16 twenty three
  • Example 4-7 0 210 0 15 twenty three
  • Comparative Example 4-1 2 350 80 55 46 Comparative Example 4-2 0 340 twenty four 51 43
  • Comparative Example 4-3 3 350 55 50 38 Comparative Example 4-4 0 300 20 44 40
  • Example 5-8 0 200 0 3 twenty one Comparative example 5-1 4 350 75 50 49 Comparative Example 5-2 0 300 8 44 46 Comparative Example 5-3 3 350 40 45 43
  • the water loss at a pressure of 0.69 mPa in 30 min is lower than that in the comparative example under the same conditions, indicating that the water temperature is lower.
  • the drilling fluid is under the pressure of 0.69mPa, and the filtration loss can reach up to 65ml in 30min.

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Abstract

公开了一种含淀粉微球及其制备方法和应用，所述含淀粉微球粒径在粒径集中分布区间内呈均匀分布的多分散性，所述粒径集中分布区间内的粒径分布具有如下特征：将粒径集中分布区间均分成n个区间，每个区间的微球占比为：(I) 其中n为大于1的整数。所述制备方法为，首先将淀粉与低浓度环氧氯丙烷反应，然后与表面活性剂作用，最后再进行交联得到微球。本发明制备的含淀粉微球是粒径均匀分布的多分散含淀粉微球，粒径为0.1～500μm。

Description

一种含淀粉微球及其制备方法和应用 技术领域
本发明属于微球技术领域，具体涉及含淀粉微球及其制备方法和应用。
背景技术
屏蔽暂堵保护油气层钻井技术(简称屏蔽暂堵技术)，主要是用来解决裸眼井段多压力层系地层保护油气层的问题，即利用钻井油气层过程中对油气层发生损害的两个不利因素(压差和钻井液固相颗粒)，将其转化为保护油气层的有利因素，达到减少钻井液、水泥浆、压差和浸泡时间对油气层损害的目的。
屏蔽暂堵保护油气层钻井技术的基本构思是利用油气层被钻开时，钻井液液柱压力与油气层压力之间形成的压差，在极短时间内，迫使钻井液中人为加入的固体粒子(暂堵剂)进入油气层孔喉，在井壁附近快速、浅层、有效的形成一个堵塞带，防止钻井液继续侵入油气层，减少钻井液对油气层的损害。堵塞带的厚度必须大大小于射孔深度，以便在完井投产时，通过射孔解堵。
微球类化合物是目前较常用的一种油气层保护的暂堵剂，其中含淀粉微球也受到了广泛的研究。现有技术对单分散或多分散的含淀粉微球研究较多，CN201010546156.1和CN201410236878.5介绍了两种单分散含淀粉微球的制备方法。CN201510151917.6介绍了一种纳米级多分散含淀粉微球的制备方法。CN201510175382.6提供了一种具粒度梯度特性聚合物微球的制备方法。
CN107129560A公开了一种颗粒暂堵剂的制备方法，首先将玉米淀粉、茯苓多糖等进行搅拌混合，并在低温下滴加氢氧化钠溶液进行反应后，滴加氯乙酸溶液进行加热混合并过滤，将滤液进行透析后浓缩，得到浓缩液，接着将浓缩液与无水乙醇在低温下混合并过滤，将滤渣干燥后，与水等进行混合，得混合液A，再以丙烯酸、氨水等为原料进行混合，得混合液B，并将其加入混合液A中，同时加入表面活性剂等，制得粘稠液，最后将粘稠液降温放置后干燥并粉碎即可。然而，使用该方法获得的颗粒暂堵剂使用于某些地层时暂堵效果不错，使用于其他地层时暂堵效果不佳。
WO03035793A1公开了一种钻井液，其中包括使用经过环氧氯丙烷交联的淀粉作为桥接剂，形成的滤饼能够很容易在非常温和的条件下去除。
发明内容
针对现有技术的不足，本发明提供一种含淀粉微球及其制备方法和应用，所述含淀粉微球具有均匀分布的多分散性、成本低廉、用于各种地层均可获得优异的暂堵效果等优点。
本发明第一方面提供一种含淀粉微球，所述含淀粉微球在粒径集中分布区间内呈均匀分布的多分散性，所述粒径集中分布区间内的粒径分布具有如下特征：将粒径集中分布区间均分成n个区间，每个区间的微球占比为：
Figure PCTCN2018101771-appb-000001
其中n为大于1的整数。
本发明第二方面提供了一种含淀粉微球的制备方法，所述制备方法包括如下步骤：
(1)将淀粉加入到水中，然后加入增溶剂混合均匀，再在交联反应条件下加入第一交联剂进行反应；
(2)向步骤(1)得到的料液中加入两性离子表面活性剂，混合均匀；
(3)在30～60℃条件下，向步骤(2)得到的料液中加入无机盐溶液和第二交联剂进行反应，其中，第一交联剂和第二交联剂相同或不同。
本发明另外的方面提供了由上述方法制得的含淀粉微球以及上述含淀粉微球在油气层保护暂堵剂中的应用。
本发明提供的含淀粉微球在钻井液质量分数0.5～5wt％的加量下可以起到良好的效果，对于不同的地层均具有良好的封堵能力，能有效封堵孔隙或微裂隙，形成致密泥饼，防止滤液大量渗入地层，降低滤失量。究其原因，可能是因为与现有技术制备的单分散和多分散含淀粉微球不同，本发明所述含淀粉微球为具有粒径均匀分布的多分散性的微球，当含淀粉微球在油气层保护暂堵剂领域应用时，由于地质结构千差万别，储层孔隙度跨度大，如果仅靠单分散粒径的微球很难满足广谱性的要求，使用效果无法满足工业要求。另外，现有的多分散微球呈现正态分布，粒径的有效范围窄，效果也明显受限。而本发明提供的均匀分布的多分散含淀粉微球可以很好解决这些问题，即在任意粒径区间内，微球占比相当，微球含量高，暂堵效果显著，可以满足广谱性的要求。
本发明提供的含淀粉微球的制备方法能够制备具有粒径均匀分布的多分散性(即在任意粒径区间内，微球占比相当)的含淀粉微球，究其原因，可能是因为通过三乙醇胺和环氧氯丙烷的共同作用，尤其是环氧氯丙烷分两步分别加入的操作方式，使得淀粉中的直链部分和支链部分的结构大小相当，具有相近的分子尺寸，保证制备的微球更加易 控，粒径分布具有均匀性。然后在后面的淀粉交联成微球过程中，通过使用两性离子表面活性剂，并同时缓慢匀速加入无机盐和环氧氯丙烷，在它们的共同作用下，使得制备的含淀粉微球粒径大小呈现线性变化，进而制备得到粒径均匀分布的多分散含淀粉微球。通过在所述含淀粉微球制备方法中加入单体(包括阳离子单体、阴离子单体、两性离子单体、非离子单体中的一种或多种)对淀粉进行共聚改性，使微球在抗盐抗温、抑制岩心水化分散即稳定井壁等性能方面有了显著的提升。
附图说明
图1为本发明的含淀粉微球的粒径分布图。
图2为本发明的含淀粉微球的红外谱图。
图3为本发明实施例使用的淀粉原料的红外谱图。
具体实施方式
在本文中所披露的范围的端点和任何值都不限于该精确的范围或值，这些范围或值应当理解为包含接近这些范围或值的值。对于数值范围来说，各个范围的端点值之间、各个范围的端点值和单独的点值之间，以及单独的点值之间可以彼此组合而得到一个或多个新的数值范围，这些数值范围应被视为在本文中具体公开。
本发明中，粒径均匀分布是指在粒径集中分布区间内各个粒径的粒子数量相当。其中，粒径集中分布区间是指粒径分布呈近似直线分布的区域，不包括两端的具有明显拐点的区域，如图1所示。该区间可以通过粒径分布测试仪获得的粒径分布图确定。
本发明中，所述粒径分布通过马尔文3000粒度分析仪进行测量，测试方法为湿法测定。
本发明中，为便于考察/描述本发明中的粒径均匀分布特征，本发明将粒径集中分布区间内的粒子分成n个区间，其中n可以为任意大于1的整数，结果各个区间的含淀粉微球占比基本相同，均为：
Figure PCTCN2018101771-appb-000002
为减少不必要的测试、统计工作，本发明实施例中优选n为4～10之间的整数。
本发明中，所述含淀粉微球的粒径可控范围为0.1～500μm，例如可以为0.1～5μm、20～260μm、50～300μm、150～500μm。即在上述粒径范围内，粒径集中分布区间内各个粒径区间的含淀粉微球占比均满足上述要求。根据本发明的具体实施方式，所述淀粉 微球的粒径分布为下述中的任意一种或多种：所述粒径集中分布区间为10～170μm，n为4，每个区间的微球占比为24.5％～25.5％；所述粒径集中分布区间为120～400μm，n为4，每个区间的微球占比为24.5％～25.5％；所述粒径集中分布区间为50～300μm，n为5，每个区间的微球占比为18.5％～21.5％；所述粒径集中分布区间为150～500μm，n为7，每个区间的微球占比为13.5％～15.5％；所述粒径集中分布区间为0.7～3.7μm，n为6，每个区间的微球占比为15.5％～17.5％；所述粒径集中分布区间为70～270μm，n为5，每个区间的微球占比为18.5％～21.0％；所述粒径集中分布区间为20～260μm，n为6，每个区间的微球占比为15.0％～18.0％；所述粒径集中分布区间为0.1～4.9μm，n为6，每个区间的微球占比为15.5％～18.0％。
本发明中，如图2所示，所述含淀粉微球的红外光谱在1025～1250cm ～1位置附近出现小尖峰，为C-N的振动特征峰，在1150～1350cm ～1位置附近出现与C-N特征峰强度相近的特征峰，归属于S＝O双键的伸缩振动。而淀粉原料的红外谱图如图3所示，在上述两个位置没有特征峰。
本发明中的红外谱图采用在Perkin-Elmer公司生产的Frontier型傅立叶变换红外光谱仪上分析获得。
优选地，本发明中所述含淀粉微球含有两性离子表面活性剂，所述两性离子表面活性剂的结构式如下：
Figure PCTCN2018101771-appb-000003
其中：m为2～6之间的整数，优选m为3或4；R为碳数1～18优选碳数12～18的饱和碳链。优选地，除端基碳外，所述两性离子表面活性剂碳链上含有单取代的功能基团。所述基团可以为羟基、氨基或羧基。即所述R优选为除端基碳外其中一个或多个碳上具有羟基、氨基或羧基作为取代基的碳数1～18优选碳数12～18的饱和碳链。特别优选地，所述两性离子表面活性剂为二甲基十二烷基磺丙基铵盐、二甲基十六烷基磺乙基铵盐、二甲基十八烷基磺丁基铵盐、二甲基(3～羟基十二烷基)磺丙基铵盐、二甲基(6-氨基十四烷基)磺乙基铵盐中的一种或多种。
本发明中的含淀粉微球主要含有淀粉结构单元，其中淀粉结构单元的含量不低于35wt％～95wt％，优选38wt％～85wt％。为了进一步提高含淀粉微球用于钻井液时的抗温抗盐性，优选地，该含淀粉微球还含有聚合单体结构单元，所述聚合单体为阴离子单 体、阳离子单体、非离子单体和两性离子单体中的至少一种。优选所述聚合单体结构单元与淀粉结构单元形成接枝共聚物。
优选地，所述两性离子单体为DMAPS(甲基丙烯酰氧乙基-N,N-二甲基丙磺酸盐)、DAPS(N,N-二甲基烯丙基胺丙磺酸盐)、VPPS(4～乙烯基吡啶丙磺酸盐)、MAPS(N-甲基二烯丙基丙磺酸盐)、MABS(N-甲基二烯丙基丁磺酸盐)中的一种或多种；所述阳离子单体为DMC(甲基丙烯酰氧乙基三甲基氯化铵)、DAC(丙烯酰氧乙基三甲基氯化铵)、DBC(丙烯酰氧乙基二甲基苄基氯化铵)、DMDAAC(二甲基二烯丙基氯化铵)、DEDAAC(二乙基二烯丙基氯化铵)中的一种或多种；所述阴离子单体为AA(丙烯酸)、AMPS(2-甲基-2-丙烯酰氨基丙磺酸)、FA(反丁烯二酸)、SSS(烯丙基磺酸钠)、AOIAS(2-丙烯酰氧异戊烯磺酸钠)中的一种或多种；所述非离子单体为NVP(N-乙烯基吡咯烷酮)、AN(丙烯腈)、NVF(乙烯基甲酰胺)、NVA(乙烯基乙酰胺)中的一种或多种。上述聚合单体均可商购获得。
根据本发明一种特别优选的实施方式，所述含淀粉微球还含有淀粉结构单元以及交联剂结构单元和聚合单体结构单元中的至少一种，且以含淀粉微球的总量为基准，其中淀粉结构单元的含量为35～95wt％，优选为36.6wt％～90.4wt％，更优选为38～85wt％，更进一步优选为39.6wt％～82.7wt％。聚合单体结构单元的含量为0～50wt％，优选为5wt％～45.2wt％，交联剂结构单元的含量为6～35wt％，优选为5～30wt％，更优选为8.2％～26.7％。优选地，淀粉结构单元的含量为39.6wt％～82.7wt％，聚合单体结构单元的含量为8.3wt％～36.6wt％，交联剂结构单元的含量为9.4wt％～20.6wt％。具有优选成分的含淀粉微球具有更好的抗盐耐温性能。
本发明中，淀粉结构单元是指含淀粉微球中由淀粉提供的结构单元，聚合单体结构单元是指含淀粉微球中由聚合单体提供的结构单元。其中各结构单元的存在可以通过傅立叶红外光谱表征的方法确定。结构单元的含量可以通过原料投料量计算得到。
本发明提供了上述含淀粉微球的制备方法，该制备方法包括如下步骤：
(1)将淀粉加入到水中，然后加入增溶剂混合均匀，再在交联反应条件下加入第一交联剂进行反应；
(2)向步骤(1)得到的料液中加入两性离子表面活性剂，混合均匀；
(3)在30～60℃条件下，向步骤(2)得到的料液中加入无机盐溶液和第二交联剂进行反应，其中，第一交联剂和第二交联剂相同或不同。
根据本发明的优选实施方式，该方法还包括在步骤(1)与步骤(2)之间增加步骤 (1～1)：加入聚合单体和引发剂进行共聚反应。即将聚合单体加入到步骤(1)得到的溶液中，充分溶解混合均匀后加入引发剂，在60～80℃下反应3～6h，然后加入所述两性离子表面活性剂进行所述步骤(2)。由此制得的含淀粉微球具有更好的抗温抗盐性、稳定井壁性等。
所述聚合单体如上所述，可以为阳离子单体、阴离子单体、两性离子单体、非离子单体中的一种或多种。具体已在上文中进行了描述，在此不再赘述。
所述引发剂可以为过硫酸盐型引发剂，例如为过硫酸钾、过硫酸钠、过硫酸铵中的任一种或多种。
与聚合单体进行共聚反应的条件包括温度优选为30～80℃，时间优选为2～8小时，进一步优选温度为45～65℃，时间为3～5小时。
本发明中，淀粉与水的重量比可以为1～20:100，优选5～15:100。
本发明中，所述的淀粉为绿豆淀粉、木薯淀粉、甘薯淀粉、红薯淀粉、马铃薯淀粉、麦类淀粉、菱角淀粉、藕淀粉、玉米淀粉中的一种或几种，优选玉米淀粉和/或马铃薯淀粉。
本发明中，水优选为去离子水。
本发明中，所述增溶剂可以是各种能够增加淀粉在水中溶解性/溶胀性从而提高淀粉与水接触程度防止淀粉团聚的物质，优选为含有羟基和叔N且碳原子数为1～10的物质，进一步优选为三甲醇胺、三乙醇胺、三丙醇胺、N,N-双二乙醇胺、异丙醇胺、二甘醇胺中的一种或多种，特别优选所述增溶剂为三乙醇胺。
本发明中，淀粉与增溶剂的重量比为1～20:10～50，优选5～15:20～40。
本发明中，淀粉与水、增溶剂接触的温度优选为20～80℃，进一步优选温度为30～60℃。
本发明中，所述第一交联剂和第二交联剂相同或不同，各自独立的为环氧氯丙烷、N,N-亚甲基双烯丙基胺、三氯氧磷、三偏磷酸钠、己二酸、六偏磷酸钠中的一种或多种。优选第一交联剂和第二交联剂相同。从交联效率角度考虑，优选为第一交联剂和第二交联剂均为环氧氯丙烷。
所述步骤(1)交联反应的条件包括温度优选为20～80℃，时间优选为0.5～4小时，进一步优选温度为30～60℃，时间为1～3小时。
本发明中，两性离子表面活性剂的种类如上所述，在此不再赘述。相对于1～20重量份的淀粉，两性离子表面活性剂的用量为0.05～10重量份，优选相对于5～15重量份 的淀粉，两性离子表面活性剂的用量为1～6重量份。
步骤(2)混合的条件包括温度优选为20～80℃，时间优选为0.5～6小时，进一步优选温度为30～50℃，时间为1～3小时。
步骤(3)反应的温度可以为20～80℃，优选为30～60℃。
步骤(3)中无机盐溶液与第二交联剂同时加入反应体系中，并采用缓慢匀速加入优选匀速滴加的方式。滴加的时间可以为2～20小时，优选为5～15小时。
相对于1～20重量份的淀粉，无机盐溶液的用量为0.5～200重量份，优选相对于5～15重量份的淀粉，无机盐溶液的用量为50～150重量份。其中无机盐溶质的含量为0.025～50重量份，优选0.5～30重量份。
本发明中，所述无机盐可以为各种可溶性无机盐，例如所述无机盐可以为钠盐、钾盐、铵盐、钙盐、镁盐中的一种或多种。当所述无机盐为钠盐时，具体可以为氯化钠、溴化钠、硫酸钠、亚硫酸钠、碳酸钠、碳酸氢钠、硝酸钠、磷酸钠、磷酸氢钠、硅酸钠中的一种或多种。当所述无机盐为钾盐时，具体可以为氯化钾、溴化钾、硫酸钾、亚硫酸钾、碳酸钾、碳酸氢钾、硝酸钾、磷酸钾、磷酸氢钾、硅酸钾的一种或多种。当所述无机盐为铵盐时，具体可以为氯化铵、溴化铵、硝酸铵的一种或多种。当所述无机盐为钙盐时，具体可以为氯化钙和/或溴化钙。当所述无机盐为镁盐时，具体可以为氯化镁、溴化镁、硫酸镁、硝酸镁的一种或多种。
相对于1～20重量份的淀粉，第一交联剂和第二交联剂的总用量为0.105～14.6重量份，优选相对于5～15重量份的淀粉，第一交联剂和第二交联剂的总用量为1.04～7.8重量份。
步骤(3)在滴加完成后继续反应1～5小时，优选1.5～3小时。
步骤(3)完成后根据需要(如考虑产品远途运输)可以进一步进行固液分离，并将分离得到的固体进行干燥，得到含淀粉微球固体产品。干燥的条件包括温度为30～110℃，时间为2～12小时，优选温度为40～80℃，时间为5～9小时。
根据本发明的一种实施方式，以重量份数计，制备所述含淀粉微球的原料包括如下组分：100份去离子水、1～20份淀粉、10～50份三乙醇胺、0.105～14.6份环氧氯丙烷、0.05～10份两性离子表面活性剂、0.5～200份无机盐溶液，其中无机盐溶质占0.025～50份。优选地，以重量份数计，所述含淀粉微球的原料包括如下组分：100份去离子水、5～15份淀粉、20～40份三乙醇胺、1.04～7.8份环氧氯丙烷、1～6份两性离子表面活性剂、50～150份无机盐溶液，其中无机盐溶质占0.5～30份。
根据本发明的另一种实施方式，所述含淀粉微球的原料还包括引发剂和单体，以重量份数计，所述含淀粉微球的原料包括如下组分：100份去离子水、1～20份淀粉、10～50份三乙醇胺、0.105～14.6份环氧氯丙烷、0.05～10份两性离子表面活性剂、0.1～20份单体、0.001～0.2份引发剂、0.5～200份无机盐溶液，其中无机盐溶质占0.025～50份；优选为100份去离子水、5～15份淀粉、20～40份三乙醇胺、1.04～7.8份环氧氯丙烷、1～6份两性离子表面活性剂、5～15份单体、0.02～0.105份引发剂、50～150份无机盐溶液，其中无机盐溶质占0.5～30份。
根据本发明提供的含淀粉微球的制备方法的一种实施方式，所述制备方法包括如下步骤：
(1)称取一定量的淀粉加入到水中，然后加入一定量的三乙醇胺，在20～80℃下混合均匀，再加入环氧氯丙烷进行反应；
(2)向步骤(1)得到的料液中加入两性离子表面活性剂，混合均匀；
(3)在30～60℃条件下，向步骤(2)得到的料液中缓慢匀速加入无机盐溶液和环氧氯丙烷，待无机盐溶液和环氧氯丙烷加入完毕后继续反应，得到含淀粉微球。
以重量份数计，所述去离子水、淀粉、三乙醇胺、环氧氯丙烷、两性离子表面活性剂、无机盐溶液的用量分别可以为：100份去离子水、1～20份淀粉、10～50份三乙醇胺、0.105～14.6份环氧氯丙烷、0.05～10份两性离子表面活性剂、0.5～2000份，优选0.5～120份无机盐溶液，其中无机盐溶质占0.025～50份，优选0.025～30份；优选为100份去离子水、5～15份淀粉、20～40份三乙醇胺、1.04～7.8份环氧氯丙烷、1～6份两性离子表面活性剂、50～150份，优选50～100份无机盐溶液，其中无机盐溶质占0.5～30份，优选2.5～25份。
本发明方法中，步骤(1)中所述环氧氯丙烷的份数为0.005～0.6份，优选份数为0.04～3份。
本发明方法中，步骤(3)中所述环氧氯丙烷的份数为0.1～14份，优选份数为1～7.5份。
根据本发明的另一种方式，当所述淀粉原料中包括单体和引发剂时，所述制备方法包括如下步骤：
(1)称取一定量的淀粉加入到水中，然后加入一定量的三乙醇胺，在20～80℃下充分混合均匀，再加入环氧氯丙烷进行反应；
(1～1)将单体加入到步骤(1)得到的溶液中，充分溶解混合均匀后加入引发剂， 在60～80℃下反应3～6h；
(2)向步骤(1～1)得到的料液中加入两性离子表面活性剂，混合均匀；
(3)在30～60℃条件下，向步骤(2)得到的料液中缓慢匀速加入无机盐溶液和环氧氯丙烷，待无机盐溶液和环氧氯丙烷加入完毕后继续反应，得到含淀粉微球。
步骤(1～1)中所述单体可以为阳离子单体、阴离子单体、两性离子单体、非离子单体中的一种或多种。具体已在上文中描述，在此不再赘述。
本发明另外的方面还提供了由上述方法制得的含淀粉微球和上述含淀粉微球在油气层保护暂堵剂中的应用。
采用上述方法制得的含淀粉微球粒径在粒径集中分布区间内呈均匀分布的多分散性，所述粒径集中分布区间内的粒径分布具有如下特征：将粒径集中分布区间均分成n个区间，每个区间的微球占比为：
Figure PCTCN2018101771-appb-000004
其中n为大于1的整数，优选n为4～10之间的整数。所述含淀粉微球的粒径可控范围为0.1～500μm。
所述含淀粉微球的红外光谱在1025～1250cm ～1位置附近出现小尖峰，为C-N的振动特征峰，在1150～1350cm ～1位置附近出现与C-N特征峰强度相近的特征峰，归属于S＝O双键的伸缩振动。本发明的含淀粉微球作为钻井液体系中的一种组分，起到屏蔽暂堵的作用。以钻井液体系的总量为基准，所述含淀粉微球的用量可以为0.5～5重量％。
下面通过具体实施例对本发明所述含淀粉微球及其制备方法和应用做进一步描述，但并不构成对本发明的限制。
本发明实施例中所述含淀粉微球粒径通过马尔文3000粒度分析仪进行测量，测试方法为湿法测定。采用PerkiN-Elmer的Frontier型傅立叶变换红外光谱仪确定交联结构和接枝聚合结构，通过投料量计算含淀粉微球中各结构单元的含量。
以下所有实施例和对比例中的粒径范围(aμm～bμm)所示含义为a≤D＜b，D表示具体淀粉颗粒的直径，即当两个范围有重合的端点时，该端点值属于后一个范围而非前一个范围。
以下所有实施例和对比例中的份表示重量份，％均表示wt％。除非另有说明，其中的温度和压力表示环境温度(20～25℃)和压力(1.0个大气压)或密闭条件下的自生压力。
以下实施例中，两性阳离子表面活性剂和聚合单体均为市售品。
实施例1-1至实施例1-5以及对比例1-1至对比例1-4用于说明不加聚合单体的含淀粉微球的制备。
实施例1-1
称取15份绿豆淀粉加入100份去离子水中，再加入40份三乙醇胺，在60℃下充分溶解。然后加入0.6份环氧氯丙烷，混合后反应1.5h。加入4.5份二甲基(3-羟基十二烷基)磺丙基铵盐(国药集团化学试剂有限公司)，充分混合。称取30份K 2SO 4配制成105份无机盐溶液，在30℃下与5.7份环氧氯丙烷同时滴加入淀粉溶液中，匀速滴加时间7h。滴加完毕后继续反应2h，得到均匀分布的多分散含淀粉微球，淀粉结构单元的含量为70.4wt％。所述粒径分布如图1所示，其中所述含淀粉微球的粒径集中分布区间为150～500μmμm(96.0％的粒径在这个区间内)，所述粒径集中分布区间内的粒径分布具有如下特征：(150μm～200μm)：13.8％；(200μm～250μm)：13.9％；(250μm～300μm)：15.4％；(300μm～350μm)：14.8％；(350μm～400μm)：14.2％；(400μm～450μm)：13.7％；(450μm～500μm)：14.2％；以及(150μm～185μm)：10.2％；(185μm～220μm)：9.1％；(220μm～255μm)：9.9％；(255μm～290μm)：9.8％；(290μm～325μm)：10.1％；(325μm～360μm)：10.3％；(360μm～395μm)：10.0％；(395μm～430μm)：9.8％；(430μm～465μm)：10.1％；(465μm～500μm)：10.7％。其中红外谱图如图2所示，存在C-N峰、S＝O峰。淀粉原料的红外谱图如图3所示，不存在C-N峰、S＝O峰。
实施例1-2
称取10份玉米淀粉加入100份去离子水中，再加入10份三乙醇胺，在80℃下充分溶解。然后加入0.005份环氧氯丙烷，混合后反应3h。加入6份二甲基十二烷基磺丙基铵盐(国药集团化学试剂有限公司)，充分混合。称取50份NaCl配制成200份无机盐水溶液，在50℃下与1份环氧氯丙烷同时滴加入淀粉溶液中，匀速滴加时间5h。滴加完毕后继续反应2h，得到均匀分布的多分散含淀粉微球，淀粉结构单元的含量为90.8wt％。所述含淀粉微球的粒径集中分布区间为50～210μm(95.1％的粒径在这个区间内)，所述粒径集中分布区间内的粒径分布具有如下特征：(50μm～90μm)：25.4％；(90μm～130μm)：25.1％；(130μm～170μm)：24.6％；(170μm～210μm)：24.9％；以及(50μm～70μm)：13.4％；(70μm～90μm)：12.0％；(90μm～110μm)：13.7％；(110μm～130μm)：11.4％；(130μm～150μm)：12.3％；(150μm～170μm)：12.3％；(170μm～190μm)：13.6％；(190μm～210μm)：11.3％。其中红外谱图与图2类似，存在C-N峰、S＝O峰。
实施例1-3
称取5份马铃薯淀粉加入100份去离子水中，再加入31份三乙醇胺，在室温下充分溶解。然后加入0.04环氧氯丙烷，混合后反应2h。加入1份二甲基十六烷基磺乙基铵盐(国药集团化学试剂有限公司)，充分混合。称取0.5份CaCl 2配制成58份无机盐溶液，在60℃下与7.5份环氧氯丙烷同时滴加入淀粉溶液中，匀速滴加时间8h。滴加完毕后继续反应2h，得到均匀分布的多分散含淀粉微球，淀粉结构单元的含量为39.8wt％。所述含淀粉微球的粒径集中分布区间为70～350μm(92.2％的粒径在这个区间内)，所述粒径集中分布区间内的粒径分布具有如下特征：(70μm～140μm)：24.5％；(140μm～210μm)：26％；(210μm～280μm)：25.1％；(280μm～350μm)：24.4％；以及(70μm～110μm)：14.5％；(110μm～150μm)：15.2％；(150μm～190μm)：14.9％；(190μm～230μm)：15.0％；(230μm～270μm)：13.9％；(270μm～310μm)：15.2％；(310μm～350μm)：11.3％。其中红外谱图与图2类似，存在C-N峰、S＝O峰。
实施例1-4
称取20份木薯淀粉加入100份去离子水中，再加入20份三乙醇胺，在40℃下充分溶解。然后加入0.3份环氧氯丙烷，混合后反应1h。加入10份二甲基十八烷基磺丁基铵盐(国药集团化学试剂有限公司)，充分混合。称取21份MgCl 2配制成150份无机盐溶液，在40℃下与14份环氧氯丙烷同时滴加入淀粉溶液中，匀速滴加时间10h。滴加完毕后继续反应2h，经过滤、在80℃下干燥5h后得到均匀分布的多分散含淀粉微球，淀粉结构单元的含量为58.3wt％。所述含淀粉微球的粒径集中分布区间为50～300μm(93.7％的粒径在这个区间内)，所述粒径集中分布区间内的粒径分布具有如下特征：(50μm～100μm)：19.4％；(100μm～150μm)：18.8％；(150μm～200μm)：21％；(200μm～250μm)：20.0％；(250μm～300μm)：20.8％；以及(50μm～75μm)：10.2％；(75μm～100μm)：9.2％；(100μm～125μm)：9.6％；(125μm～150μm)：9.7％；(150μm～175μm)：11.0％；(175μm～200μm)：9.5％；(200μm～225μm)：9.8％；(225μm～250μm)：10.2％；(250μm～275μm)：10.4％；(275μm～300μm)：10.4％。其中红外谱图与图2类似，存在C-N峰、S＝O峰。
实施例1-5
称取1份甘薯淀粉加入100份去离子水中，再加入50份三乙醇胺，在50℃下充分溶解。然后加入0.34份环氧氯丙烷，混合后反应2.5h。加入0.05份二甲基(6-氨基十四烷基)磺乙基铵盐(国药集团化学试剂有限公司)，充分混合。称取0.025份NaCl配制成0.5份无机盐溶液，在55℃下与0.1份环氧氯丙烷同时滴加入淀粉溶液中，匀速滴加时间9h。滴加完毕后继续反应2h，经过滤、在70℃下干燥6.5h后得到均匀分布的多分散含淀粉微球，淀粉结构单元的含量为69.4wt％。所述含淀粉微球的粒径集中分布区间为0.1～1.3μm(93.5％的粒径在这个区间内)，所述粒径集中分布区间内的粒径分布具有如下特征：(0.1μm～0.3μm)：17.5％；(0.3μm～0.5μm)：15.9％；(0.5μm～0.7μm)：16.5％；(0.7μm～0.9μm)：16.5％；(0.9μm～1.1μm)：16.4％；(1.1μm～1.3μm)：17.2％；以及(0.1μm～0.2μm)：9.1％；(0.2μm～0.3μm)：8.2％；(0.3μm～0.4μm)：8.6％；(0.4μm～0.5μm)：7.5％；(0.5μm～0.6μm)：9.0％；(0.6μm～0.7μm)：7.5％；(0.7μm～0.8μm)：8.8％；(0.8μm～0.9μm)：7.7％；(0.9μm～1.0μm)：8.2％；(1.0μm～1.1μm)：8.2％；(1.1μm～1.2μm)：9.0％；(1.2μm～1.3μm)：8.2％。其中红外谱图与图2类似，存在C-N峰、S＝O峰。
对比例1-1
取10份玉米淀粉加入100份去离子水中，在80℃下充分溶解30min，之后将其降温至50℃备用。加入6份二甲基十二烷基磺丙基铵盐(国药集团化学试剂有限公司)，充分溶解混合。称取1份环氧氯丙烷并将其加入淀粉溶液中，在50℃下连续反应时间7h。过滤、在110℃下干燥2h后得到均匀分布的多分散含淀粉微球。所述含淀粉微球的粒径集中分布区间为50～350μm(97.5％的粒径在这个区间内)，所述粒径集中分布区间内的粒径分布具有如下特征：(50μm～100μm)：10.2％；(100μm～300μm)：80.6％；(300μm～350μm)：9.2％。
对比例1-2
按照实施例1-2的方法制备含淀粉微球，不同的是，加入6份二甲基十二烷基磺丙基铵盐之前不加入0.005份环氧氯丙烷，得到均匀分布的多分散含淀粉微球。所述含淀粉微球的粒径集中分布区间为10～210μm(92.5％的粒径在这个区间内)，所述粒径集中分布区间内的粒径分布具有如下特征：(10μm～60μm)：31.8％；(60μm～110μm)：19.0％；(110μm～160μm)：18.7％；(160μm～210μm)：30.5％。
对比例1-3
按照实施例1-2的方法制备含淀粉微球，不同的是，无机盐水溶液和1份环氧氯丙烷同时一次性加入淀粉溶液中，得到均匀分布的多分散含淀粉微球。所述含淀粉微球的粒径集中分布区间为10～210μm(96.8％的粒径在这个区间内)，所述粒径集中分布区间内的粒径分布具有如下特征：(10μm～60μm)：7.5％；(60μm～110μm)：40.2％；(110μm～160μm)：43.5％；(160μm～210μm)：8.8％。
对比例1-4
按照实施例1-2的方法制备含淀粉微球，不同的是，不加入三乙醇胺，得到均匀分布的多分散含淀粉微球。所述含淀粉微球的粒径集中分布区间为20～200μm(95.3％粒径在这个区间内)，所述粒径集中分布区间内的粒径分布具有如下特征：：(20μm～65μm)：35.6％；(65μm～110μm)：21.1％；(110μm～155μm)：20.9％；(155μm～200μm)：22.4％。
实施例2-1至实施例2-8以及对比例2-1至对比例2-4制备含有两性离子单体的含淀粉微球
实施例2-1
称取13份马铃薯淀粉加入100份去离子水中，再加入10份三乙醇胺，在75℃下充分溶解。然后加入0.013份环氧氯丙烷，混合后反应2.5h。称取7份DMAPS溶解混合。在65℃下加入0.03份过硫酸钾，反应5h。加入5份二甲基十二烷基磺丁基铵盐(国药集团化学试剂有限公司)，充分混合。称取38份NaCl配制成170份无机盐溶液，在40℃下与1.5份环氧氯丙烷同时滴加入淀粉溶液中，匀速滴加时间6h。滴加完毕后继续反应2h，得到均匀分布的多分散含淀粉微球，淀粉结构单元含量为61.8wt％，DMAPS结构单元的含量为34.6wt％。所述含淀粉微球的粒径集中分布区间为10～170μm(94.2％的粒径在这个区间内)，所述粒径集中分布区间内的粒径分布具有如下特征：(10μm～50μm)：24.9％；(50μm～90μm)：25.6％；(90μm～130μm)：25.1％；(130μm～170μm)：24.4％；以及(10μm～30μm)：13.7％；(30μm～50μm)：11.3％；(50μm～70μm)：13.3％；(70μm～90μm)：12.3％；(90μm～110μm)：12.1％；(110μm～130μm)：13.0％；(130μm～150μm)：12.2％；(150μm～170μm)：12.1％。其中红外谱图存在C-N峰、S＝O峰。淀粉与DMAPS发生了接枝聚合。
实施例2-2
称取5份马铃薯淀粉加入100份去离子水中，再加入22份三乙醇胺，在室温下充分溶解。然后加入0.04环氧氯丙烷，混合后反应2h。称取6份MAPS加入淀粉溶液中，充分溶解混合。在70℃下加入0.07份过硫酸铵，反应4h。加入1份二甲基十六烷基磺乙基铵盐(国药集团化学试剂有限公司)，充分混合。称取0.5份CaCl 2配制成33份无机盐溶液，在60℃下与7.5份环氧氯丙烷同时滴加入淀粉溶液中，匀速滴加时间8h。滴加完毕后继续反应2h，得到均匀分布的多分散含淀粉微球，淀粉结构单元含量26.9wt％，MAPS结构单元的含量为32.3wt％。所述含淀粉微球的粒径集中分布区间为120～400μm(97.1％的粒径在这个区间内)，所述粒径集中分布区间内的粒径分布具有如下特征：(120μm～190μm)：26％；(190μm～260μm)：24.5％；(260μm～330μm)：25.1％；(330μm～400μm)：24.4％；以及(120μm～160μm)：14.5％；(160μm～200μm)：13.8％；(200μm～240μm)：13.3％；(240μm～280μm)：13.9％；(280μm～320μm)：14.3％；(320μm～360μm)：14.8％；(360μm～400μm)：15.4％。其中红外谱图存在C-N峰、S＝O峰。淀粉与MAPS发生了接枝聚合。
实施例2-3
称取20份木薯淀粉加入100份去离子水中，再加入20份三乙醇胺，在40℃下充分溶解。然后加入0.3份环氧氯丙烷，混合后反应1h。称取13份DAPS加入淀粉溶液中，充分溶解混合。在80℃下加入0.105份过硫酸钠，反应3h。加入10份二甲基十八烷基磺丁基铵盐(国药集团化学试剂有限公司)，充分混合。称取16份MgCl 2配制成150份无机盐溶液，在40℃下与14份环氧氯丙烷同时滴加入淀粉溶液中，匀速滴加时间10h。滴加完毕后继续反应2h，得到均匀分布的多分散含淀粉微球，淀粉结构单元含量42.3wt％，DAPS结构单元的含量为27.5wt％。所述含淀粉微球的粒径集中分布区间为50～300μmμm(95.4％的粒径在这个区间内)，所述粒径集中分布区间内的粒径分布具有如下特征：(50μm～100μm)：19.5％；(100μm～150μm)：18.7％；(150μm～200μm)：21％；(200μm～250μm)：20.0％；(250μm～300μm)：20.8％；以及(50μm～75μm)：10.3％；(75μm～100μm)：9.2％；(100μm～125μm)：9.2％；(125μm～150μm)：9.5％；(150μm～175μm)：10.9％；(175μm～200μm)：10.1％；(200μm～225μm)：9.5％；(225μm～250μm)：10.5％；(250μm～275μm)：10.4％；(275μm～300μm)：10.4％。其中红外谱图存在C-N峰、S＝O峰。淀粉与DAPS发生了接枝聚合。
实施例2-4
称取15份绿豆淀粉加入100份去离子水中，再加入40份三乙醇胺，在60℃下充分溶解。然后加入0.6份环氧氯丙烷，混合后反应1.5h。称取20份VPPS加入淀粉溶液中，充分溶解混合。在75℃下加入0.2份过硫酸钾，反应5h。加入4.5份二甲基(3～羟基十二烷基)磺丙基铵盐(国药集团化学试剂有限公司)，充分混合。称取30份K 2SO 4配制成135份无机盐溶液，在30℃下与9.5份环氧氯丙烷同时滴加入淀粉溶液中，匀速滴加时间7h。滴加完毕后继续反应2h，得到均匀分布的多分散含淀粉微球，淀粉结构单元含量33.3wt％，VPPS结构单元的含量为44.3wt％。所述含淀粉微球的粒径集中分布区间为150～500μm(96.2％的粒径在这个区间内)，所述粒径集中分布区间内的粒径分布具有如下特征：(150μm～200μm)：13.5％；(200μm～250μm)：14.2％；(250μm～300μm)：15.4％；(300μm～350μm)：14.7％；(350μm～400μm)：13.9％；(400μm～450μm)：14.7％；(450μm～500μm)：13.6％。其中红外谱图存在C-N峰、S＝O峰。淀粉与VPPS发生了接枝聚合。
实施例2-5
称取1份甘薯淀粉加入100份去离子水中，再加入50份三乙醇胺，在50℃下充分溶解。然后加入0.15份环氧氯丙烷，混合后反应2.5h。称取0.1份MAPS加入淀粉溶液中，充分溶解混合。在65℃下加入0.001份过硫酸铵，反应4h。加入0.05份二甲基(6-氨基十四烷基)磺乙基铵盐(国药集团化学试剂有限公司)，充分混合。称取0.025份NaCl配制成0.5份无机盐溶液，在55℃下与0.1份环氧氯丙烷同时滴加入淀粉溶液中，匀速滴加时间9h。滴加完毕后继续反应2h，过滤、在110℃下干燥2h后得到均匀分布的多分散含淀粉微球，淀粉结构单元含量74.0wt％，MAPS结构单元的含量为7.4wt％。所述含淀粉微球的粒径集中分布区间为0.1～3.7μm(95.0％的粒径在这个区间内)，所述粒径集中分布区间内的粒径分布具有如下特征：(0.1μm～0.7μm)：16.5％；(0.7μm～1.3μm)：15.9％；(1.3μm～1.9μm)：17.2％；(1.9μm～2.5μm)：17.5％；(2.5μm～3.1μm)：16.4％；(3.1μm～3.7μm)：16.5％；以及(0.1μm～0.5μm)：11.9％；(0.5μm～0.9μm)：11.7％；(0.9μm～1.3μm)：10.6％；(1.3μm～1.7μm)：11.4％；(1.7μm～2.1μm)：10.2％；(2.1μm～2.5μm)：11.0％；(2.5μm～2.9μm)：10.7％；(2.9μm～3.3μm)：11.5％；(3.3μm～3.7μm)：11.0％。其中红外谱图存在C-N峰、S＝O峰。淀粉与MAPS发生了接 枝聚合。
实施例2-6
称取17份淀粉(玉米:绿豆＝2:1重量比)加入100份去离子水中，再加入30份三乙醇胺，在72℃下充分溶解。然后加入0.28份环氧氯丙烷，混合后反应0.5h。称取11.5份DMAPS加入淀粉溶液中，充分溶解混合。在68℃下加入0.009份过硫酸钾，反应5h。加入7份二甲基十二烷基磺丁基铵盐(国药集团化学试剂有限公司)，充分混合。称取45份无机盐(NaCl:CaCl 2＝1:1重量比)配制成50份无机盐溶液，在57℃下与12份环氧氯丙烷同时滴加入淀粉溶液中，匀速滴加时间4.5h。滴加完毕后继续反应2h，后得到均匀分布的多分散含淀粉微球，淀粉结构单元含量41.6wt％，DMAPS结构单元的含量为28.1wt％。所述含淀粉微球的粒径集中分布区间为70～270μm(91.2％的粒径在这个区间内)，所述粒径集中分布区间内的粒径分布具有如下特征：(70μm～110μm)：20.7％；(110μm～150μm)：20.6％；(150μm～190μm)：20.1％；(190μm～230μm)：19.8％；(230μm～270μm)：18.8％；以及(70μm～90μm)：11.7％；(90μm～110μm)：11.0％；(110μm～130μm)：11.3％；(130μm～150μm)：10.3％；(150μm～170μm)：11.2％；(170μm～190μm)：10.9％；(190μm～210μm)：11.4％；(210μm～230μm)：10.4％；(230μm～270μm)：11.8％。其中红外谱图存在C-N峰、S＝O峰。淀粉与DMAPS发生了接枝聚合。
实施例2-7
称取6份淀粉(木薯:玉米＝3:1重量比)加入100份去离子水中，再加入14份三乙醇胺，在65℃下充分溶解。然后加入0.025份环氧氯丙烷，混合后反应1.6h。称取2份DMAPS加入淀粉溶液中，充分溶解混合。在72℃下加入0.022份过硫酸铵，反应4h。加入0.8份二甲基羟基十六烷基磺丙基铵盐(国药集团化学试剂有限公司)，充分混合。称取10份KNO 3配制成64份无机盐溶液，在45℃下与7份环氧氯丙烷同时滴加入淀粉溶液中，匀速滴加时间6h。滴加完毕后继续反应2h，过滤、在110℃下干燥2h后得到均匀分布的多分散含淀粉微球，淀粉结构单元含量39.9wt％，DMAPS结构单元的含量为13.3wt％。所述含淀粉微球的粒径集中分布区间为20～260μm(93.7％的粒径在这个区间内)，所述粒径集中分布区间内的粒径分布具有如下特征：(20μm～60μm)：16.6％；(60μm～100μm)：17.8％；(100μm～140μm)：15.9％；(140μm～180μm)：17.5％； (180μm～220μm)：17.0％；(220μm～260μm)：15.2％。其中红外谱图存在C-N峰、S＝O峰。淀粉与DMAPS发生了接枝聚合。
实施例2-8
称取18份麦类淀粉加入100份去离子水中，再加入24份三乙醇胺，在45℃下充分溶解。然后加入0.013份环氧氯丙烷，混合后反应2.75h。称取3.5份单体(DMAPS：MAPS＝1:1重量比)加入淀粉溶液中，充分溶解混合。在67.5℃下加入0.01份引发剂(过硫酸钠：过硫酸钾＝1:1重量比)，反应6h。加入5.5份二甲基十二烷基磺丙基铵盐(国药集团化学试剂有限公司)，充分混合。称取7份Na 2CO 3配制成130份无机盐溶液，在42℃下与2份环氧氯丙烷同时滴加入淀粉溶液中，匀速滴加时间6.5h。滴加完毕后继续反应2h，得到均匀分布的多分散含淀粉微球，淀粉结构单元含量76.5wt％，DMAPS单体结构单元的含量为6.2wt％，MAPS单体结构单元的含量为6.1wt％。所述含淀粉微球的粒径集中分布区间为0.1～4.9μm(95.6％的粒径在这个区间内)，所述粒径集中分布区间内的粒径分布具有如下特征：(0.1μm～0.9μm)：16.8％；(0.9μm～1.7μm)：17.6％；(1.7μm～2.5μm)：16.8％；(2.5μm～3.3μm)：15.9％；(3.3μm～4.1μm)：17.4％；(4.1μm～4.9μm)：15.5％。其中红外谱图存在C-N峰、S＝O峰。淀粉与两性离子单体发生了接枝聚合。
对比例2-1
取13份马铃薯淀粉加入100份去离子水中，在75℃下充分溶解30min，之后将其降温备用。称取7份DMAPS加入淀粉溶液中，充分溶解混合。在65℃下加入0.03份过硫酸钾，反应5h。加入5份二甲基十二烷基磺丁基铵盐(国药集团化学试剂有限公司)，充分溶解混合。称取1.5份环氧氯丙烷并将其加入淀粉溶液中，在40℃下连续反应时间6h，得到均匀分布的多分散含淀粉微球。所述含淀粉微球的粒径集中分布区间为120～400μm(92.2％的粒径在这个区间内)，所述粒径集中分布区间内的粒径分布具有如下特征：(120μm～170μm)：13.4％；(170μm～350μm)：75.4％；(350μm～400μm)：11.2％。其中淀粉结构单元含量为60.4wt％，DMAPS结构单元的含量为32.5wt％，淀粉与DMAPS发生了接枝聚合。
对比例2-2
按照实施例2-1的方法制备含淀粉微球，不同的是，加入7份DMAPS之前不加入0.013份环氧氯丙烷，得到均匀分布的多分散含淀粉微球。所述含淀粉微球的粒径集中分布区间为20～180μm(91.8％的粒径在这个区间内)，所述粒径集中分布区间内的粒径分布具有如下特征：(20μm～60μm)：32.8％；(60μm～100μm)：17.5％；(100μm～140μm)：19.2％；(140μm～180μm)：30.5％。其中淀粉结构单元含量为61.0wt％，DMAPS结构单元的含量为31.9wt％，淀粉与DMAPS发生了接枝聚合。
对比例2-3
按照实施例2-1的方法制备含淀粉微球，不同的是，无机盐水溶液和1.5份环氧氯丙烷同时一次性加入淀粉溶液中，得到均匀分布的多分散含淀粉微球。所述含淀粉微球的粒径集中分布区间为10～190μm(96.2％的粒径在这个区间内)，所述粒径集中分布区间内的粒径分布具有如下特征：(10μm～55μm)：9.9％；(55μm～100μm)：37.2％；(100μm～145μm)：42.1％；(145μm～190μm)：10.8％。其中淀粉结构单元含量为60.4wt％，DMAPS结构单元的含量为32.3wt％，淀粉与DMAPS发生了接枝聚合。
对比例2-4
按照实施例2-1的方法制备含淀粉微球，不同的是，不加入三乙醇胺，得到均匀分布的多分散含淀粉微球。所述含淀粉微球的粒径集中分布区间为5～205μm(94.2％的粒径在这个区间内)，所述粒径集中分布区间内的粒径分布具有如下特征：(5μm～55μm)：36.3％；(55μm～105μm)：22.1％；(105μm～155μm)：19.9％；(155μm～205μm)：21.7％。其中淀粉结构单元含量为59.6wt％，DMAPS结构单元的含量为34.0wt％，淀粉与DMAPS发生了接枝聚合。
实施例3-1至实施例3-8以及对比例3-1至对比例3-4为加入阳离子单体的实施情况。
实施例3-1
称取8份木薯淀粉加入100份去离子水中，再加入17份三乙醇胺，在55℃下充分溶解。然后加入0.009份环氧氯丙烷，混合后反应3h。称取8份DMDAAC加入淀粉溶液中，充分溶解混合。在70℃下加入0.1份过硫酸钠，反应4.5h。加入5份二甲基羟基十二烷基磺丙基铵盐，充分混合。称取62份NaNO 3配制成90份无机盐溶液，在45℃ 下与1份环氧氯丙烷同时滴加入淀粉溶液中，匀速滴加时间5h。滴加完毕后继续反应2h，得到均匀分布的多分散含淀粉微球，淀粉结构单元含量47.0wt％，DMDAAC结构单元的含量为47.1wt％。所述含淀粉微球的粒径集中分布区间为10～170μm(95.6％的粒径在这个区间内)，所述粒径集中分布区间内的粒径分布具有如下特征：(10μm～50μm)：24.4％；(50μm～90μm)：25.6％；(90μm～130μm)：25.1％；(130μm～170μm)：24.9％；以及(10μm～26μm)：10.3％；(26μm～42μm)：10.9％；(42μm～58μm)：9.8％；(58μm～74μm)：9.7％；(74μm～90μm)：9.2％；(90μm～106μm)：10.9％；(106μm～122μm)：9.2％；(122μm～138μm)：9.6％；(138μm～154μm)：10.4％；(154μm～170μm)：10.0％。其中红外谱图存在C-N峰、S＝O峰。淀粉与DMDAAC发生了接枝聚合。
实施例3-2
称取5份马铃薯淀粉加入100份去离子水中，再加入15份三乙醇胺，在室温下充分溶解。然后加入0.04环氧氯丙烷，混合后反应2h。称取6份DEDAAC加入淀粉溶液中，充分溶解混合。在70℃下加入0.04份过硫酸铵，反应4h。加入1份二甲基十六烷基磺乙基铵盐，充分混合。称取0.5份CaCl 2配制成20份无机盐溶液，在60℃下与7.5份环氧氯丙烷同时滴加入淀粉溶液中，匀速滴加时间8h。滴加完毕后继续反应2h，得到均匀分布的多分散含淀粉微球，淀粉结构单元含量38.3wt％，DEDAAC结构单元的含量为46.3wt％。所述含淀粉微球的粒径集中分布区间为120～400μm(93.7％的粒径在这个区间内)，所述粒径集中分布区间内的粒径分布具有如下特征：(120μm～190μm)：24.5％；(190μm～260μm)：26％；(260μm～330μm)：24.4％；(330μm～400μm)：25.1％。其中红外谱图存在C-N峰、S＝O峰。淀粉与DEDAAC发生了接枝聚合。
实施例3-3
称取20份木薯淀粉加入100份去离子水中，再加入20份三乙醇胺，在40℃下充分溶解。然后加入0.3份环氧氯丙烷，混合后反应1h。称取10份DMC加入淀粉溶液中，充分溶解混合。在80℃下加入0.105份过硫酸钠，反应3h。加入10份二甲基十八烷基磺丁基铵盐，充分混合。称取40份MgCl 2配制成150份无机盐溶液，在40℃下与14份环氧氯丙烷同时滴加入淀粉溶液中，匀速滴加时间10h。滴加完毕后继续反应2h，过滤、在110℃下干燥2h后得到均匀分布的多分散含淀粉微球，淀粉结构单元含量45.2wt％，DMC结构单元的含量为22.5wt％。所述含淀粉微球的粒径集中分布区间为50～300μm (90.8％的粒径在这个区间内)，所述粒径集中分布区间内的粒径分布具有如下特征：(50μm～100μm)：20.0％；(100μm～150μm)：18.7％；(150μm～200μm)：21％；(200μm～250μm)：19.5％；(250μm～300μm)：20.8％。其中红外谱图存在C-N峰、S＝O峰。淀粉与DMC发生了接枝聚合。
实施例3-4
称取15份绿豆淀粉加入100份去离子水中，再加入40份三乙醇胺，在60℃下充分溶解。然后加入0.6份环氧氯丙烷，混合后反应1.5h。称取20份DAC加入淀粉溶液中，充分溶解混合。在75℃下加入0.2份过硫酸钾，反应5h。加入8份二甲基(3～羟基十二烷基)磺丙基铵盐，充分混合。称取30份K 2SO 4配制成120份无机盐溶液，在30℃下与8份环氧氯丙烷同时滴加入淀粉溶液中，匀速滴加时间7h。滴加完毕后继续反应2h，过滤、在110℃下干燥2h后得到均匀分布的多分散含淀粉微球，淀粉结构单元含量38.9wt％，DAC结构单元的含量为51.8wt％。所述粒径分布为所述含淀粉微球的粒径集中分布区间为150～500μm(94.3％的粒径在这个区间内)，所述粒径集中分布区间内的粒径分布具有如下特征：(150μm～200μm)：14.7％；(200μm～250μm)：13.6％；(250μm～300μm)：15.4％；(300μm～350μm)：14.7％；(350μm～400μm)：13.9％；(400μm～450μm)：13.5％；(450μm～500μm)：14.2％。其中红外谱图存在C-N峰、S＝O峰。淀粉与DAC发生了接枝聚合。
实施例3-5
称取1份甘薯淀粉加入100份去离子水中，再加入50份三乙醇胺，在50℃下充分溶解。然后加入0.015份环氧氯丙烷，混合后反应2.5h。称取0.1份DBC加入淀粉溶液中，充分溶解混合。在65℃下加入0.001份过硫酸铵，反应4h。加入0.05份二甲基(6-氨基十四烷基)磺乙基铵盐，充分混合。称取0.025份NaCl配制成0.5份无机盐溶液，在55℃下与0.1份环氧氯丙烷同时滴加入淀粉溶液中，匀速滴加时间9h。滴加完毕后继续反应2h，得到均匀分布的多分散含淀粉微球，淀粉结构单元含量82.3wt％，DBC结构单元的含量为8.2wt％。所述含淀粉微球的粒径集中分布区间为0.1～6.1μm(96.0％的粒径在这个区间内)，所述粒径集中分布区间内的粒径分布具有如下特征：(0.1μm～1.1μm)：17.5％；(1.1μm～2.1μm)：15.9％；(2.1μm～3.1μm)：17.2％；(3.1μm～4.1μm)：16.5％；(4.1μm～5.1μm)：16.4％；(5.1μm～6.1μm)：16.5％。其中红外 谱图存在C-N峰、S＝O峰。淀粉与DBC发生了接枝聚合。
实施例3-6
称取9份淀粉(玉米:绿豆＝2:1重量比)加入100份去离子水中，再加入25份三乙醇胺，在72℃下充分溶解。然后加入0.35份环氧氯丙烷，混合后反应0.5h。称取6.5份DMDAAC加入淀粉溶液中，充分溶解混合。在68℃下加入0.025份过硫酸钾，反应5h。加入3.6份二甲基十二烷基磺丁基铵盐，充分混合。称取12份无机盐(NaCl:CaCl 2＝1:1重量比)配制成50份无机盐溶液，在57℃下与8.5份环氧氯丙烷同时滴加入淀粉溶液中，匀速滴加时间4.5h。滴加完毕后继续反应2h，得到均匀分布的多分散含淀粉微球，淀粉结构单元含量36.9wt％，DMDAAC结构单元的含量为26.15wt％。所述含淀粉微球的粒径集中分布区间为70～280μm(97.1％的粒径在这个区间内)，所述粒径集中分布区间内的粒径分布具有如下特征：(70μm～112μm)：20.7％；(112μm～154μm)：20.6％；(154μm～196μm)：20.1％；(196μm～238μm)：19.8％；(238μm～280μm)：18.8％。其中红外谱图存在C-N峰、S＝O峰。淀粉与DMDAAC发生了接枝聚合。
实施例3-7
称取16份淀粉(木薯:玉米＝3:1重量比)加入100份去离子水中，再加入45份三乙醇胺，在65℃下充分溶解。然后加入0.025份环氧氯丙烷，混合后反应1.6h。称取6份DMDAAC加入淀粉溶液中，充分溶解混合。在72℃下加入0.016份硫酸铵，反应4h。加入4.5份二甲基羟基十六烷基磺丙基铵盐，充分混合。称取3525份KNO 3配制成50份无机盐溶液，在45℃下与12.5份环氧氯丙烷同时滴加入淀粉溶液中，匀速滴加时间6h。滴加完毕后继续反应2h，过滤、在110℃下干燥2h后得到均匀分布的多分散含淀粉微球，淀粉结构单元含量46.3wt％，DMDAAC结构单元的含量为17.4wt％。所述含淀粉微球的粒径集中分布区间为20～260μm(92.8％的粒径在这个区间内)，所述粒径集中分布区间内的粒径分布具有如下特征：(20μm～60μm)：17.8％；(60μm～100μm)：16.6％；(100μm～140μm)：15.9％；(140μm～180μm)：17.0％；(180μm～220μm)：17.5％；(220μm～260μm)：15.2％。其中红外谱图存在C-N峰、S＝O峰。淀粉与DMDAAC发生了接枝聚合。
实施例3-8
称取3份麦类淀粉加入100份去离子水中，再加入22.5份三乙醇胺，在45℃下充分溶解。然后加入0.009份环氧氯丙烷，混合后反应2.75h。称取2份单体(DMDAAC：DMC＝1:1重量比)加入淀粉溶液中，充分溶解混合。在67.5℃下加入0.004份引发剂(过硫酸钠：过硫酸钾＝1:1重量比)，反应6h。加入4份二甲基十二烷基磺丙基铵盐，充分混合。称取5.5份Na 2CO 3配制成160份无机盐溶液，在42℃下与3份环氧氯丙烷同时滴加入淀粉溶液中，匀速滴加时间6.5h。滴加完毕后继续反应2h，得到均匀分布的多分散含淀粉微球，淀粉结构单元含量37.6wt％，DMDAAC结构单元的含量为6.3wt％，DMC结构单元的含量为6.2wt％。所述含淀粉微球的粒径集中分布区间为0.1～7.3μm(96.3％的粒径在这个区间内)，所述粒径集中分布区间内的粒径分布具有如下特征：(0.1μm～1.3μm)：16.6％；(1.3μm～2.5μm)：17.6％；(2.5μm～3.7μm)：17.0％；(3.7μm～4.9μm)：16.4％；(4.9μm～6.1μm)：17.4％；(6.1μm～7.3μm)：16.0％；以及(0.1μm～0.7μm)：8.2％；(0.7μm～1.3μm)：8.4％；(1.3μm～1.9μm)：8.6％；(1.9μm～2.5μm)：9.0％；(2.5μm～3.1μm)：8.5％；(3.1μm～3.7μm)：8.5％；(3.7μm～4.3μm)：8.0％；(4.3μm～4.9μm)：8.4％；(4.9μm～5.5μm)：8.6％；(5.5μm～6.1μm)：7.8％；(6.1μm～6.7μm)：7.9％；(6.7μm～7.3μm)：8.1％。其中红外谱图存在C-N峰、S＝O峰。淀粉与阳离子单体发生了接枝聚合。
对比例3-1
取8份木薯淀粉加入100份去离子水中，在55℃下充分溶解30min备用。称取8份DMDAAC加入淀粉溶液中，充分溶解混合。在70℃下加入0.1份过硫酸钠，反应4.5h。加入5份二甲基羟基十二烷基磺丙基铵盐，充分溶解混合。称取1份环氧氯丙烷并将其加入淀粉溶液中，在45℃下连续反应时间7h，得到均匀分布的多分散含淀粉微球。所述含淀粉微球的粒径集中分布区间为120～400μm(94.1％的粒径在这个区间内)，所述粒径集中分布区间内的粒径分布具有如下特征：(120μm～170μm)：11.0％；(170μm～350μm)：79.8％；(350μm～400μm)：9.2％。其中测得淀粉结构单元含量46.6wt％，DMDAAC结构单元的含量为45.8wt％，淀粉与DMDAAC发生了接枝聚合。
对比例3-2
按照实施例3-1的方法制备含淀粉微球，不同的是，加入DMDAAC之前不加入0.009份环氧氯丙烷，得到均匀分布的多分散含淀粉微球。所述含淀粉微球的粒径集中分布区 间为20～180μm(95.1％的粒径在这个区间内)，所述粒径集中分布区间内的粒径分布具有如下特征：(20μm～60μm)：32.7％；(60μm～100μm)：18.0％；(100μm～140μm)：19.3％；(140μm～180μm)：30.0％。其中测得淀粉结构单元含量46.0wt％，DMDAAC结构单元的含量为45.2wt％，淀粉与DMDAAC发生了接枝聚合。
对比例3-3
按照实施例3-1的方法制备含淀粉微球，不同的是，无机盐与1份环氧氯丙烷同时一次性加入淀粉溶液中，得到均匀分布的多分散含淀粉微球。所述含淀粉微球的粒径集中分布区间为30～190μm(92.7％的粒径在这个区间内)，所述粒径集中分布区间内的粒径分布具有如下特征：(30μm～70μm)：9.9％；(70μm～110μm)：37.2％；(110μm～150μm)：42.1％；(150μm～190μm)：10.8％。其中测得淀粉结构单元含量45.2wt％，DMDAAC结构单元的含量为46.1wt％，淀粉与DMDAAC发生了接枝聚合。
对比例3-4
按照实施例3-1的方法制备含淀粉微球，不同的是，不加入三乙醇胺，得到均匀分布的多分散含淀粉微球。所述含淀粉微球的粒径集中分布区间为15～215μm(95.4％的粒径在这个区间内)，所述粒径集中分布区间内的粒径分布具有如下特征：(15μm～65μm)：36.3％；(65μm～115μm)：21.7％；(115μm～165μm)：19.9％；(165μm～215μm)：22.1％。其中测得淀粉结构单元含量44.9wt％，DMDAAC结构单元的含量为45.6wt％，淀粉与DMDAAC发生了接枝聚合。
实施例4-1至实施例4-8和对比例4-1至对比例4-4为加入阴离子单体的实施情况。
实施例4-1
称取11份玉米淀粉加入100份去离子水中，再加入21份三乙醇胺，在40℃下充分溶解。然后加入0.35份环氧氯丙烷，混合后反应2h。称取6份AMPS加入淀粉溶液中，充分溶解混合。在80℃下加入0.22份过硫酸铵，反应6h。加入6份二甲基氨基十四烷基磺丙基铵盐，充分混合。称取62份KCl配制成130份无机盐溶液，在55℃下与2份环氧氯丙烷同时滴加入淀粉溶液中，匀速滴加时间5h。滴加完毕后继续反应2h，得到均匀分布的多分散含淀粉微球，淀粉结构单元含量56.9wt％，AMPS结构单元的含量为30.8wt％。所述含淀粉微球的粒径集中分布区间为10～170μm(92.9％的粒径在这个区间 内)，所述粒径集中分布区间内的粒径分布具有如下特征：(10μm～50μm)：25.4％；(50μm～90μm)：24.6％；(90μm～130μm)：25.3％；(130μm～170μm)：24.7％；以及(10μm～20μm)：6.2％；(20μm～30μm)：6.4％；(30μm～40μm)：5.9％；(40μm～50μm)：6.8％；(50μm～60μm)：6.0％；(60μm～70μm)：6.3％；(70μm～80μm)：6.8％；(80μm～90μm)：5.9％；(90μm～100μm)：6.5％；(100μm～110μm)：6.6％；(110μm～120μm)：5.7％；(120μm～130μm)：6.2％；(130μm～140μm)：6.5％；(140μm～150μm)：6.1％；(150μm～160μm)：6.2％；(160μm～170μm)：5.9％。其中红外谱图存在C-N峰、S＝O峰。淀粉与AMPS发生了接枝聚合。
实施例4-2
称取5份马铃薯淀粉加入100份去离子水中，再加入16份三乙醇胺，在室温下充分溶解。然后加入0.04环氧氯丙烷，混合后反应2h。称取6份AA加入淀粉溶液中，充分溶解混合。在70℃下加入0.12份过硫酸铵，反应4h。加入1份二甲基十六烷基磺乙基铵盐，充分混合。称取0.5份CaCl 2配制成62份无机盐溶液，在60℃下与7.5份环氧氯丙烷同时滴加入淀粉溶液中，匀速滴加时间8h。滴加完毕后继续反应2h，得到均匀分布的多分散含淀粉微球，淀粉结构单元含量26.9wt％，AA结构单元的含量为31.8wt％。所述含淀粉微球的粒径集中分布区间为120～240μm(93.5％的粒径在这个区间内)，所述粒径集中分布区间内的粒径分布具有如下特征：(120μm～190μm)：24.1％；(190μm～260μm)：26％；(260μm～330μm)：24.8％；(330μm～400μm)：25.1％。其中红外谱图存在C-N峰、S＝O峰。淀粉与AA发生了接枝聚合。
实施例4-3
称取20份木薯淀粉加入100份去离子水中，再加入20份三乙醇胺，在40℃下充分溶解。然后加入0.3份环氧氯丙烷，混合后反应1h。称取5.5份FA加入淀粉溶液中，充分溶解混合。在80℃下加入0.105份过硫酸钠，反应3h。加入10份二甲基十八烷基磺丁基铵盐，充分混合。称取29份MgCl 2配制成150份无机盐溶液，在40℃下与14份环氧氯丙烷同时滴加入淀粉溶液中，匀速滴加时间10h。滴加完毕后继续反应2h，得到均匀分布的多分散含淀粉微球，淀粉结构单元含量50.2wt％，FA结构单元的含量为13.8wt％。所述含淀粉微球的粒径集中分布区间为50～300μm(95.2％的粒径在这个区间内)，所述粒径集中分布区间内的粒径分布具有如下特征：(50μm～100μm)：20.0％； (100μm～150μm)：18.7％；(150μm～200μm)：20.5％；(200μm～250μm)：20.0％；(250μm～300μm)：20.8％。其中红外谱图存在C-N峰、S＝O峰。淀粉与FA发生了接枝聚合。
实施例4-4
称取15份绿豆淀粉加入100份去离子水中，再加入40份三乙醇胺，在60℃下充分溶解。然后加入0.6份环氧氯丙烷，混合后反应1.5h。称取20份SSS加入淀粉溶液中，充分溶解混合。在75℃下加入0.2份过硫酸钾，反应5h。加入3.7份二甲基(3～羟基十二烷基)磺丙基铵盐，充分混合。称取30份K 2SO 4配制成95份无机盐溶液，在30℃下与5份环氧氯丙烷同时滴加入淀粉溶液中，匀速滴加时间7h。滴加完毕后继续反应2h，得到均匀分布的多分散含淀粉微球，淀粉结构单元含量36.9wt％，SSS结构单元的含量为50.1wt％。所述含淀粉微球的粒径集中分布区间为150～500μm(96.1％的粒径在这个区间内)，所述粒径集中分布区间内的粒径分布具有如下特征：(150μm～200μm)：14.7％；(200μm～250μm)：13.6％；(250μm～300μm)：15.4％；(300μm～350μm)：13.9％；(350μm～400μm)：14.7％；(400μm～450μm)：14.2％；(450μm～500μm)：13.5％。其中红外谱图存在C-N峰、S＝O峰。淀粉与SSS发生了接枝聚合。
实施例4-5
称取1份甘薯淀粉加入100份去离子水中，再加入50份三乙醇胺，在50℃下充分溶解。然后加入0.38份环氧氯丙烷，混合后反应2.5h。称取0.1份AOIAS加入淀粉溶液中，充分溶解混合。在65℃下加入0.001份过硫酸铵，反应4h。加入0.05份二甲基(6-氨基十四烷基)磺乙基铵盐，充分混合。称取0.025份NaCl配制成0.5份无机盐溶液，在55℃下与0.1份环氧氯丙烷同时滴加入淀粉溶液中，匀速滴加时间9h。滴加完毕后继续反应2h，过滤、在110℃下干燥2h后得到均匀分布的多分散含淀粉微球，淀粉结构单元含量63.2wt％，AOIAS结构单元的含量为6.2wt％。所述含淀粉微球的粒径集中分布区间为0.1～6.7μm(92.8％的粒径在这个区间内)，所述粒径集中分布区间内的粒径分布具有如下特征：(0.1μm～1.2μm)：17.0％；(1.2μm～2.3μm)：15.5％；(2.3μm～3.4μm)：17.2％；(3.4μm～4.5μm)：17.0％；(4.5μm～5.6μm)：16.8％；(5.6μm～6.7μm)：16.5％。其中红外谱图存在C-N峰、S＝O峰。淀粉与AOIAS发生了接枝聚合。
实施例4-6
称取11份淀粉(玉米:绿豆＝2:1重量比)加入100份去离子水中，再加入33份三乙醇胺，在72℃下充分溶解。然后加入0.25份环氧氯丙烷，混合后反应0.5h。称取6.7份AMPS加入淀粉溶液中，充分溶解混合。在68℃下加入0.014份过硫酸钾，反应5h。加入6.8份二甲基十二烷基磺丁基铵盐，充分混合。称取34份无机盐(NaCl:CaCl 2＝1:1重量比)配制成70份无机盐溶液，在57℃下与12.5份环氧氯丙烷同时滴加入淀粉溶液中，匀速滴加时间4.5h。滴加完毕后继续反应2h，得到均匀分布的多分散含淀粉微球，淀粉结构单元含量36.1wt％，AMPS结构单元的含量为21.9wt％。所述含淀粉微球的粒径集中分布区间为70～270μm(97.8％的粒径在这个区间内)，所述粒径集中分布区间内的粒径分布具有如下特征：(70μm～110μm)：19.8％；(110μm～150μm)：20.6％；(150μm～190μm)：20.1％；(190μm～230μm)：20.7％；(230μm～270μm)：18.8％。其中红外谱图存在C-N峰、S＝O峰。淀粉与AMPS发生了接枝聚合。
实施例4-7
称取18份淀粉(木薯:玉米＝3:1重量比)加入100份去离子水中，再加入12份三乙醇胺，在65℃下充分溶解。然后加入0.025份环氧氯丙烷，混合后反应1.6h。称取3.1份AMPS加入淀粉溶液中，充分溶解混合。在72℃下加入0.044份过硫酸铵，反应4h。加入1.2份二甲基羟基十六烷基磺丙基铵盐，充分混合。称取12份KNO 3配制成81份无机盐溶液，在45℃下与6份环氧氯丙烷同时滴加入淀粉溶液中，匀速滴加时间6h。滴加完毕后继续反应2h，过滤、在110℃下干燥2h后得到均匀分布的多分散含淀粉微球，淀粉结构单元含量66.3wt％，AMPS结构单元的含量为11.3wt％。所述含淀粉微球的粒径集中分布区间为20～260μm(94.7％的粒径在这个区间内)，所述粒径集中分布区间内的粒径分布具有如下特征：(20μm～60μm)：17.3％；(60μm～100μm)：16.2％；(100μm～140μm)：16.4％；(140μm～180μm)：17.4％；(180μm～220μm)：17.4％；(220μm～260μm)：15.3％。其中红外谱图存在C-N峰、S＝O峰。淀粉与AMPS发生了接枝聚合。
实施例4-8
称取2份麦类淀粉加入100份去离子水中，再加入35份三乙醇胺，在45℃下充分溶解。然后加入0.014份环氧氯丙烷，混合后反应2.75h。称取4.7份单体(AMPS：AA＝1:1 重量比)加入淀粉溶液中，充分溶解混合。在67.5℃下加入0.02份引发剂(过硫酸钠：过硫酸钾＝1:1重量比)，反应6h。加入7.4份二甲基十二烷基磺丙基铵盐，充分混合。称取6.5份Na 2CO 3配制成115份无机盐溶液，在42℃下与4份环氧氯丙烷同时滴加入淀粉溶液中，匀速滴加时间6.5h。滴加完毕后继续反应2h，得到均匀分布的多分散含淀粉微球，淀粉结构单元含量18.3wt％，阴离子单体结构单元的含量为43.6wt％。所述含淀粉微球的粒径集中分布区间为0.1～8.5μm(94.3％的粒径在这个区间内)，所述粒径集中分布区间内的粒径分布具有如下特征：(0.1μm～1.5μm)：16.4％；(1.5μm～2.9μm)：17.6％；(2.9μm～4.3μm)：17.1％；(4.3μm～5.7μm)：16.2％；(5.7μm～7.1μm)：17.6％；(7.1μm～8.5μm)：16.1％；以及(0.1μm～0.7μm)：7.2％；(0.7μm～1.3μm)：7.8％；(1.3μm～1.9μm)：7.0％；(1.9μm～2.5μm)：7.3％；(2.5μm～3.1μm)：7.4％；(3.1μm～3.7μm)：6.6％；(3.7μm～4.3μm)：7.2％；(4.3μm～4.9μm)：7.0％；(4.9μm～5.5μm)：7.5％；(5.5μm～6.1μm)：6.7％；(6.1μm～6.7μm)：7.5％；(6.7μm～7.3μm)：7.2％；(7.3μm～7.9μm)：7.0％；(7.9μm～8.5μm)：6.6％。其中红外谱图存在C-N峰、S＝O峰。淀粉与阴离子单体发生了接枝聚合。
对比例4-1
取11份玉米淀粉加入100份去离子水中，在40℃下充分溶解30min备用。称取6份AMPS加入淀粉溶液中，充分溶解混合。在80℃下加入0.22份过硫酸铵，反应6h。加入6份二甲基氨基十四烷基磺丙基铵盐，充分溶解混合。称取2份环氧氯丙烷并将其加入淀粉溶液中，在55℃下连续反应时间7h，得到均匀分布的多分散含淀粉微球。所述含淀粉微球的粒径集中分布区间为120～400μm(95.8％的粒径在这个区间内)，所述粒径集中分布区间内的粒径分布具有如下特征：(120μm～170μm)：11.6％；(170μm～350μm)：78.6％；(350μm～400μm)：9.8％。其中淀粉结构单元含量为57.6wt％，，AMPS结构单元的含量为31.2wt％，淀粉与AMPS发生了接枝聚合。
对比例4-2
按照实施例4-1的方法制备含淀粉微球，不同的是，加入AMPS之前不加入环氧氯丙烷得到均匀分布的多分散含淀粉微球。所述含淀粉微球的粒径集中分布区间为20～180μm(94.4％的粒径在这个区间内)，所述粒径集中分布区间内的粒径分布具有如下特征：(20μm～60μm)：31.7％；(60μm～100μm)：18.1％；(100μm～140μm)：19.2％； (140μm～180μm)：31.0％。其中淀粉结构单元含量为58.0wt％，，AMPS结构单元的含量为30.7wt％，淀粉与AMPS发生了接枝聚合。
对比例4-3
按照实施例4-1的方法制备含淀粉微球，不同的是，无机盐溶液与2份环氧氯丙烷同时一次性加入淀粉溶液中，得到均匀分布的多分散含淀粉微球。所述含淀粉微球的粒径集中分布区间为10～210μm(93.9％的粒径在这个区间内)，所述粒径集中分布区间内的粒径分布具有如下特征：(10μm～60μm)：9.9％；(60μm～110μm)：38.1％；(110μm～160μm)：41.2％；(160μm～210μm)：10.8％。其中淀粉结构单元含量为57.8wt％，，AMPS结构单元的含量为31.5wt％，淀粉与AMPS发生了接枝聚合。
对比例4-4
按照实施例4-1的方法制备含淀粉微球，不同的是，不加入三乙醇胺，得到均匀分布的多分散含淀粉微球。所述含淀粉微球的粒径集中分布区间为5～205μm(92.5％的粒径在这个区间内)，所述粒径集中分布区间内的粒径分布具有如下特征：(5μm～55μm)：35.2％；(55μm～105μm)：21.6％；(105μm～155μm)：20.0％；(155μm～205μm)：23.2％。其中淀粉结构单元含量为57.4wt％，AMPS结构单元的含量为31.3wt％，淀粉与AMPS发生了接枝聚合。
实施例5-1至实施例5-8与对比例5-1至对比例5-4为加入非离子单体的实施情况。
实施例5-1
称取14份麦类淀粉加入100份去离子水中，再加入17份三乙醇胺，在72℃下充分溶解。然后加入0.23份环氧氯丙烷，混合后反应3h。称取7份NVP加入淀粉溶液中，充分溶解混合。在65℃下加入0.14份过硫酸钾，反应6h。加入6份二甲基十六烷基磺丁基铵盐，充分混合。称取43份NaCl配制成70份无机盐溶液，在43℃下与2.2份环氧氯丙烷同时滴加入淀粉溶液中，匀速滴加时间5h。滴加完毕后继续反应2h，得到均匀分布的多分散含淀粉微球，淀粉结构单元含量为59.7wt％，NVP结构单元的含量为29.6wt％。所述含淀粉微球的粒径集中分布区间为10～170μm(93.5％的粒径在这个区间内)，所述粒径集中分布区间内的粒径分布具有如下特征：(10μm～50μm)：25.3％；(50μm～90μm)：24.7％；(90μm～130μm)：25.1％；(130μm～170μm)：24.9％。其中红外 谱图存在C-N峰、S＝O峰。淀粉与NVP发生了接枝聚合。
实施例5-2
称取5份马铃薯淀粉加入100份去离子水中，再加入41份三乙醇胺，在室温下充分溶解。然后加入0.04环氧氯丙烷，混合后反应2h。称取6份AN加入淀粉溶液中，充分溶解混合。在70℃下加入0.019份过硫酸铵，反应4h。加入1份二甲基十六烷基磺乙基铵盐，充分混合。称取0.5份CaCl 2配制成100份无机盐溶液，在60℃下与7.5份环氧氯丙烷同时滴加入淀粉溶液中，匀速滴加时间8h。滴加完毕后继续反应2h，得到均匀分布的多分散含淀粉微球，淀粉结构单元含量为26.9wt％，AN结构单元的含量为32.8wt％。所述含淀粉微球的粒径集中分布区间为50～210μm(95.0％的粒径在这个区间内)，所述粒径集中分布区间内的粒径分布具有如下特征：(120μm～400μm)：24.2％；(190μm～260μm)：26.1％；(260μm～330μm)：24.7％；(330μm～400μm)：25.0％。其中红外谱图存在C-N峰、S＝O峰。淀粉与AN发生了接枝聚合。
实施例5-3
称取20份木薯淀粉加入100份去离子水中，再加入20份三乙醇胺，在40℃下充分溶解。然后加入0.3份环氧氯丙烷，混合后反应1h。称取7份NVF加入淀粉溶液中，充分溶解混合。在80℃下加入0.105份过硫酸钠，反应3h。加入10份二甲基十八烷基磺丁基铵盐，充分混合。称取3份MgCl 2配制成150份无机盐溶液，在40℃下与14份环氧氯丙烷同时滴加入淀粉溶液中，匀速滴加时间10h。滴加完毕后继续反应2h，得到均匀分布的多分散含淀粉微球。淀粉结构单元含量为48.4wt％，NVF结构单元的含量为16.8wt％。所述含淀粉微球的粒径集中分布区间为50～300μm(91.2％的粒径在这个区间内)，所述粒径集中分布区间内的粒径分布具有如下特征：(50μm～100μm)：20.1％；(100μm～150μm)：18.8％；(150μm～200μm)：20.4％；(200μm～250μm)：20.1％；(250μm～300μm)：20.6％。其中红外谱图存在C-N峰、S＝O峰。淀粉与NVF发生了接枝聚合。
实施例5-4
称取15份绿豆淀粉加入100份去离子水中，再加入40份三乙醇胺，在60℃下充分溶解。然后加入0.6份环氧氯丙烷，混合后反应1.5h。称取20份NVA加入淀粉溶液中， 充分溶解混合。在75℃下加入0.2份过硫酸钾，反应5h。加入2.1份二甲基(3～羟基十二烷基)磺丙基铵盐，充分混合。称取30份K 2SO 4配制成84份无机盐溶液，在30℃下与2份环氧氯丙烷同时滴加入淀粉溶液中，匀速滴加时间7h。滴加完毕后继续反应2h，过滤、在110℃下干燥2h后得到均匀分布的多分散含淀粉微球，淀粉结构单元含量为39.8wt％，NVA结构单元的含量为53.2wt％。所述含淀粉微球的粒径集中分布区间为150～500μm(96.2％的粒径在这个区间内)，所述粒径集中分布区间内的粒径分布具有如下特征：(150μm～200μm)：14.8％；(200μm～250μm)：13.7％；(250μm～300μm)：15.2％；(300μm～350μm)：14.0％；(350μm～400μm)：14.6％；(400μm～450μm)：14.2％；(450μm～500μm)：13.5％。其中红外谱图存在C-N峰、S＝O峰。淀粉与NVA发生了接枝聚合。
实施例5-5
称取1份甘薯淀粉加入100份去离子水中，再加入50份三乙醇胺，在50℃下充分溶解。然后加入0.51份环氧氯丙烷，混合后反应2.5h。称取0.1份AN加入淀粉溶液中，充分溶解混合。在65℃下加入0.001份过硫酸铵，反应4h。加入0.05份二甲基(6-氨基十四烷基)磺乙基铵盐，充分混合。称取0.025份NaCl配制成0.5份无机盐溶液，在55℃下与0.1份环氧氯丙烷同时滴加入淀粉溶液中，匀速滴加时间9h。滴加完毕后继续反应2h，过滤、在110℃下干燥2h后得到均匀分布的多分散含淀粉微球。淀粉结构单元含量为58.4wt％，AN结构单元的含量为5.8wt％。所述含淀粉微球的粒径集中分布区间为0.1～7.9μm(93.8％的粒径在这个区间内)，所述粒径集中分布区间内的粒径分布具有如下特征：(0.1μm～1.4μm)：17.1％；(1.4μm～2.7μm)：16.0％；(2.7μm～4.0μm)：17.0％；(4.0μm～5.3μm)：17.1％；(5.3μm～6.6μm)：16.8％；(6.6μm～7.9μm)：16.0％。其中红外谱图存在C-N峰、S＝O峰。淀粉与AN发生了接枝聚合。
实施例5-6
称取3份淀粉(玉米:绿豆＝2:1重量比)加入100份去离子水中，再加入23份三乙醇胺，在72℃下充分溶解。然后加入0.06份环氧氯丙烷，混合后反应0.5h。称取10份NVP加入淀粉溶液中，充分溶解混合。在68℃下加入0.01份过硫酸钾，反应5h。加入4.1份二甲基十二烷基磺丁基铵盐，充分混合。称取38份无机盐(NaCl:CaCl 2＝1:1重量比)配制成50份无机盐溶液，在57℃下与13份环氧氯丙烷同时滴加入淀粉溶液中，匀 速滴加时间4.5h。滴加完毕后继续反应2h，得到均匀分布的多分散含淀粉微球。淀粉结构单元含量为11.5wt％，NVP结构单元的含量为37.5wt％。所述含淀粉微球的粒径集中分布区间为70～320μm(97.5％的粒径在这个区间内)，所述粒径集中分布区间内的粒径分布具有如下特征：(70μm～120μm)：19.7％；(120μm～170μm)：20.5％；(170μm～220μm)：20.1％；(220μm～270μm)：20.5％；(270μm～320μm)：19.2％。其中红外谱图存在C-N峰、S＝O峰。淀粉与NVP发生了接枝聚合。
实施例5-7
称取12份淀粉(木薯:玉米＝3:1重量比)加入100份去离子水中，再加入16份三乙醇胺，在65℃下充分溶解。然后加入0.025份环氧氯丙烷，混合后反应1.6h。称取3.6份NVP加入淀粉溶液中，充分溶解混合。在72℃下加入0.066份过硫酸铵，反应4h。加入2份二甲基羟基十六烷基磺丙基铵盐，充分混合。称取12份KNO 3配制成57份无机盐溶液，在45℃下与3.4份环氧氯丙烷同时滴加入淀粉溶液中，匀速滴加时间6h。滴加完毕后继续反应2h，后得到均匀分布的多分散含淀粉微球。淀粉结构单元含量为62.9wt％，NVP结构单元的含量为18.8wt％。所述含淀粉微球的粒径集中分布区间为20～260μm(92.5％的粒径在这个区间内)，所述粒径集中分布区间内的粒径分布具有如下特征：(20μm～60μm)：17.0％；(60μm～100μm)：16.3％；(100μm～140μm)：16.7％；(140μm～180μm)：17.3％；(180μm～220μm)：17.4％；(220μm～260μm)：15.3％。其中红外谱图存在C-N峰、S＝O峰。淀粉与NVP发生了接枝聚合。
实施例5-8
称取19份麦类淀粉加入100份去离子水中，再加入27份三乙醇胺，在45℃下充分溶解。然后加入0.013份环氧氯丙烷，混合后反应2.75h。称取5.2份单体(NVP:NVF＝1:1重量比)加入淀粉溶液中，充分溶解混合。在67.5℃下加入0.017份引发剂(过硫酸钠：过硫酸钾＝1:1重量比)，反应6h。加入8份二甲基十二烷基磺丙基铵盐，充分混合。称取9份Na 2CO 3配制成108份无机盐溶液，在42℃下与5份环氧氯丙烷同时滴加入淀粉溶液中，匀速滴加时间6.5h。滴加完毕后继续反应2h，得到均匀分布的多分散含淀粉微球。淀粉结构单元含量为64.9wt％，非离子单体结构单元的含量为17.7wt％。所述含淀粉微球的粒径集中分布区间为0.1～10.3μm(93.3％的粒径在这个区间内)，所述粒径集中分布区间内的粒径分布具有如下特征：(0.1μm～1.8μm)：16.0％；(1.8μm～3.5μm)：17.5％； (3.5μm～5.2μm)：17.3％；(5.2μm～6.9μm)：16.6％；(6.9μm～8.6μm)：17.5％；(8.6μm～10.3μm)：16.1％。其中红外谱图存在C-N峰、S＝O峰。淀粉与非离子单体发生了接枝聚合。
对比例5-1
取14份麦类淀粉加入100份去离子水中，在72℃下充分溶解30min，之后将其降温备用。称取7份NVP加入淀粉溶液中，充分溶解混合。在65℃下加入0.14份过硫酸钾，反应6h。加入6份二甲基十六烷基磺丁基铵盐，充分溶解混合。称取2.2份环氧氯丙烷并将其加入淀粉溶液中，在43℃下连续反应时间7h，得到均匀分布的多分散含淀粉微球。其中淀粉结构单元含量为60.3wt％，NVP结构单元的含量为27.9wt％。所述含淀粉微球的粒径集中分布区间为120～400μm(94.5％的粒径在这个区间内)，所述粒径集中分布区间内的粒径分布具有如下特征：(120μm～170μm)：12.8％；(170μm～350μm)：78.3％；(350μm～400μm)：8.9％。淀粉与NVP发生了接枝聚合。
对比例5-2
按照实施例5-1的方法制备含淀粉微球，不同的是，加入NVP之前不加入0.23份环氧氯丙烷，得到均匀分布的多分散含淀粉微球。所述含淀粉微球的粒径集中分布区间为20～180μm(92.5％的粒径在这个区间内)，所述粒径集中分布区间内的粒径分布具有如下特征：(20μm～60μm)：31.5％；(60μm～100μm)：18.0％；(100μm～140μm)：19.3％；(140μm～180μm)：31.2％。其中淀粉结构单元含量为58.8wt％，NVP结构单元的含量为29.0wt％，淀粉与NVP发生了接枝聚合。
对比例5-3
按照实施例5-1的方法制备含淀粉微球，不同的是，无机盐溶液与2.2份环氧氯丙烷同时一次性加入淀粉溶液中，得到均匀分布的多分散含淀粉微球。所述含淀粉微球的粒径集中分布区间为30～230μm(91.8％的粒径在这个区间内)，所述粒径集中分布区间内的粒径分布具有如下特征：(30μm～80μm)：9.8％；(80μm～130μm)：38.2％；(130μm～180μm)：41.1％；(180μm～230μm)：10.9％。其中淀粉结构单元含量为59.1wt％，NVP结构单元的含量为29.4wt％，淀粉与NVP发生了接枝聚合。
对比例5-4
按照实施例5-1的方法制备含淀粉微球，不同的是，不加入三乙醇胺，得到均匀分布的多分散含淀粉微球。所述含淀粉微球的粒径集中分布区间为20～200μm(93.2％的粒径在这个区间内)，所述粒径集中分布区间内的粒径分布具有如下特征：(20μm～65μm)：35.0％；(65μm～110μm)：21.8％；(110μm～155μm)：19.8％；(155μm～200μm)：23.4％。其中淀粉结构单元含量为58.6wt％，NVP结构单元的含量为28.7wt％，淀粉与NVP发生了接枝聚合。
实施例6-1至实施例6-10和对比例6-1至对比例6-4为加入两种以上单体的实施情况。
实施例6-1
称取10份甘薯淀粉加入100份去离子水中，再加入25份三乙醇胺，在80℃下充分溶解。然后加入0.05份环氧氯丙烷，混合后反应3h。称取8份单体(MAPS:NVF:AA＝1:1:1重量比)加入淀粉溶液中，充分溶解混合。在62℃下加入0.15份过硫酸钠，反应6h。加入4份二甲基羟基十四烷基磺丙基铵盐，充分混合。称取50份NaCl配制成150份无机盐溶液，在44℃下与3份环氧氯丙烷同时滴加入淀粉溶液中，匀速滴加时间5h。滴加完毕后继续反应2h，得到均匀分布的多分散含淀粉微球。所述含淀粉微球的粒径集中分布区间为10～170μm(94.5％的粒径在这个区间内)，所述粒径集中分布区间内的粒径分布具有如下特征：(10μm～50μm)：25.4％；(50μm～90μm)：25.1％；(90μm～130μm)：25.1％；(130μm～170μm)：24.4％；以及(10μm～30μm)：11.3％；(30μm～50μm)：13.2％；(50μm～70μm)：12.8％；(70μm～90μm)：12.2％；(90μm～110μm)：13.5％；(110μm～130μm)：11.6％；(130μm～150μm)：12.2％；(150μm～170μm)：13.2％。其中红外谱图存在C-N峰、S＝O峰。淀粉结构单元含量为47.5wt％，功能单体结构单元的含量为37.9wt％，其中MAPS结构单元的含量为11.8wt％，NVF结构单元的含量为12.5wt％，AA结构单元的含量为13.6wt％。淀粉与MAPS、NVF和AA发生了接枝聚合。
实施例6-2
称取5份马铃薯淀粉加入100份去离子水中，再加入33份三乙醇胺，在室温下充分溶解。然后加入0.04环氧氯丙烷，混合后反应2h。称取6份单体(DMC:SSS＝1:2重量比)加入淀粉溶液中，充分溶解混合。在70℃下加入0.17份过硫酸铵，反应4h。加 入1份二甲基十六烷基磺乙基铵盐，充分混合。称取0.5份CaCl 2配制成120份无机盐溶液，在60℃下与7.5份环氧氯丙烷同时滴加入淀粉溶液中，匀速滴加时间8h。滴加完毕后继续反应2h，得到均匀分布的多分散含淀粉微球。所述含淀粉微球的粒径集中分布区间为120～400μm(95.4％的粒径在这个区间内)，所述粒径集中分布区间内的粒径分布具有如下特征：(120μm～190μm)：25.8％；(190μm～260μm)：24.5％；(260μm～330μm)：25.3％；(330μm～400μm)：24.4％。其中红外谱图存在C-N峰、S＝O峰。淀粉结构单元含量为26.9wt％，DMC结构单元的含量为10.7wt％，SSS结构单元的含量为20.12wt％，淀粉与DMC和SSS发生了接枝聚合。
实施例6-3
称取20份木薯淀粉加入100份去离子水中，再加入20份三乙醇胺，在40℃下充分溶解。然后加入0.3份环氧氯丙烷，混合后反应1h。称取17份单体(FA:NVA＝3:1重量比)加入淀粉溶液中，充分溶解混合。在80℃下加入0.105份过硫酸钠，反应3h。加入10份二甲基十八烷基磺丁基铵盐，充分混合。称取26份MgCl 2配制成150份无机盐溶液，在40℃下与14份环氧氯丙烷同时滴加入淀粉溶液中，匀速滴加时间10h。滴加完毕后继续反应2h，过滤、在110℃下干燥2h后得到均匀分布的多分散含淀粉微球。所述含淀粉微球的粒径集中分布区间为50～300μm(95.2％的粒径在这个区间内)，所述粒径集中分布区间内的粒径分布具有如下特征：(50μm～100μm)：19.5％；(100μm～150μm)：18.7％；(150μm～200μm)：21％；(200μm～250μm)：20.0％；(50μm～100μm)：20.8％。其中红外谱图存在C-N峰、S＝O峰。淀粉结构单元含量为38.9wt％，功能单体结构单元的含量为33.1wt％，其中FA结构单元的含量为24.2wt％，NVA结构单元的含量为8.2wt％。淀粉与FA、NVA发生了接枝聚合。
实施例6-4
称取15份绿豆淀粉加入100份去离子水中，再加入40份三乙醇胺，在60℃下充分溶解。然后加入0.6份环氧氯丙烷，混合后反应1.5h。称取20份单体(DAPS:DBC:AMPS:NVP＝2:1:2:1重量比)加入淀粉溶液中，充分溶解混合。在75℃下加入0.2份过硫酸钾，反应5h。加入7.3份二甲基(3～羟基十二烷基)磺丙基铵盐，充分混合。称取19份K 2SO 4配制成135份无机盐溶液，在30℃下与11份环氧氯丙烷同时滴加入淀粉溶液中，匀速滴加时间7h。滴加完毕后继续反应2h，得到均匀分布的多 分散含淀粉微球。所述含淀粉微球的粒径集中分布区间为150～500μm(96.2％的粒径在这个区间内)，所述粒径集中分布区间内的粒径分布具有如下特征：(150μm～200μm)：13.5％；(200μm～250μm)：14.1％；(250μm～300μm)：15.4％；(300μm～350μm)：14.8％；(350μm～400μm)：14.0％；(400μm～450μm)：14.7％；(450μm～500μm)：13.5％。其中红外谱图存在C-N峰、S＝O峰。淀粉结构单元含量为32.1wt％，功能单体结构单元的含量为42.9wt％，DAPS、DBC、AMPS、NVP结构单元的含量分别为15.2wt％、8.6wt％、15.0wt％、7.8wt％。淀粉与DAPS、DBC、AMPS和NVP发生了接枝聚合。
实施例6-5
称取1份甘薯淀粉加入100份去离子水中，再加入50份三乙醇胺，在50℃下充分溶解。然后加入0.19份环氧氯丙烷，混合后反应2.5h。称取0.1份单体(MABS:DMDAAC:AA:AN＝1:1:1:1重量比)加入淀粉溶液中，充分溶解混合。在65℃下加入0.001份过硫酸铵，反应4h。加入0.05份二甲基(6-氨基十四烷基)磺乙基铵盐，充分混合。称取0.025份NaCl配制成0.5份无机盐溶液，在55℃下与0.1份环氧氯丙烷同时滴加入淀粉溶液中，匀速滴加时间9h。滴加完毕后继续反应2h，得到均匀分布的多分散含淀粉微球。所述含淀粉微球的粒径集中分布区间为0.2～6.2μm(92.7％的粒径在这个区间内)，所述粒径集中分布区间内的粒径分布具有如下特征：(0.2μm～1.2μm)：16.5％；(1.2μm～2.2μm)：15.9％；(2.2μm～3.2μm)：17.2％；(3.2μm～4.2μm)：17.5％；(4.2μm～5.2μm)：16.4％；(5.2μm～6.2μm)：16.5％。其中红外谱图存在C-N峰、S＝O峰。淀粉结构单元含量为71.9wt％，功能单体结构单元的含量为7.2wt％，MABS、DMDAAC、AA、AN结构单元的含量分别为1.7wt％、1.9wt％、1.6wt％、2.0wt％。淀粉与MABS、DMDAAC、AA和AN发生了接枝聚合。
实施例6-6
称取7份淀粉(玉米:绿豆＝2:1重量比)加入100份去离子水中，再加入32份三乙醇胺，在72℃下充分溶解。然后加入0.08份环氧氯丙烷，混合后反应0.5h。称取2份单体(VPPS:DAC:AOIAS:NVA＝1:1:4:1重量比)加入淀粉溶液中，充分溶解混合。在68℃下加入0.09份过硫酸钾，反应5h。加入3.1份二甲基十二烷基磺丁基铵盐，充分混合。称取45份无机盐(NaCl:CaCl 2＝1:1重量比)配制成76份无机盐溶液，在57℃下与4.9份环氧氯丙烷同时滴加入淀粉溶液中，匀速滴加时间4.5h。滴加完毕后继续反应2h， 得到均匀分布的多分散含淀粉微球。所述含淀粉微球的粒径集中分布区间为70～290μm(92.1％的粒径在这个区间内)，所述粒径集中分布区间内的粒径分布具有如下特征：(70μm～114μm)：20.5％；(114μm～158μm)：20.8％；(158μm～202μm)：20.0％；(202μm～246μm)：19.9％；(246μm～290μm)：18.8％。其中红外谱图存在C-N峰、S＝O峰。淀粉结构单元含量为49.8wt％，功能单体结构单元的含量为14.3wt％，VPPS、DAC、AOIAS、NVA结构单元的含量分别为2.1wt％、2.3wt％、7.1wt％、2.8wt％。淀粉与VPPS、DAC、AOIAS和NVA发生了接枝聚合。
实施例6-7
称取3份淀粉(木薯:玉米＝3:1重量比)加入100份去离子水中，再加入23份三乙醇胺，在65℃下充分溶解。然后加入0.025份环氧氯丙烷，混合后反应1.6h。称取2.6份单体(MAPS:DMC:FA:NVP＝3:1:1:2重量比)加入淀粉溶液中，充分溶解混合。在72℃下加入0.13份过硫酸铵，反应4h。加入2份二甲基羟基十六烷基磺丙基铵盐，充分混合。称取11份KNO 3配制成87份无机盐溶液，在45℃下与6.2份环氧氯丙烷同时滴加入淀粉溶液中，匀速滴加时间6h。滴加完毕后继续反应2h，得到均匀分布的多分散含淀粉微球。所述含淀粉微球的粒径集中分布区间为20～260μm(95.7％的粒径在这个区间内)，所述粒径集中分布区间内的粒径分布具有如下特征：15.2％；(60μm～100μm)：15.9％；(100μm～140μm)：17.8％；(140μm～180μm)：17.5％；(180μm～220μm)：17.0％；(220μm～260μm)：16.6％。其中红外谱图存在C-N峰、S＝O峰。淀粉结构单元含量为25.2wt％，功能单体结构单元的含量为21.7wt％，MAPS、DMC、FA、NVP结构单元的含量分别为9.4wt％、3.3wt％、2.9wt％、6.1wt％。淀粉与MAPS、DMC、FA和NVP发生了接枝聚合。
实施例6-8
称取5份麦类淀粉加入100份去离子水中，再加入36份三乙醇胺，在45℃下充分溶解。然后加入0.34份环氧氯丙烷，混合后反应2.75h。称取4份单体(AN:NVP＝1:1重量比)加入淀粉溶液中，充分溶解混合。在67.5℃下加入0.012份引发剂(过硫酸钠：过硫酸钾＝1:1重量比)，反应6h。加入8份二甲基十二烷基磺丙基铵盐，充分混合。称取8份Na 2CO 3配制成66份无机盐溶液，在42℃下与9份环氧氯丙烷同时滴加入淀粉溶液中，匀速滴加时间6.5h。滴加完毕后继续反应2h，得到均匀分布的多分散含淀粉微 球。所述含淀粉微球的粒径集中分布区间为0.1～12.1μm(94.5％的粒径在这个区间内)，所述粒径集中分布区间内的粒径分布具有如下特征：(0.1μm～2.1μm)：16.6％；(2.1μm～4.1μm)：17.4％；(4.1μm～6.1μm)：16.8％；(6.1μm～8.1μm)：16.3％；(8.1μm～10.1μm)：17.4％；(10.1μm～12.1μm)：15.5％。其中红外谱图存在C-N峰、S＝O峰。淀粉结构单元含量为27.0wt％，功能单体结构单元的含量为21.8wt％，AN、NVP结构单元的含量分别为11.1wt％、10.7wt％。淀粉与MAPS、AN和NVP发生了接枝聚合。
实施例6-9
称取7份麦类淀粉加入100份去离子水中，再加入18份三乙醇胺，在55℃下充分溶解。然后加入0.16份环氧氯丙烷，混合后反应3h。称取8份单体(MAPS:DEDAAC:AMPS:AN＝1:1:1:1重量比)加入淀粉溶液中，充分溶解混合。在68℃下加入0.1份引发剂过硫酸钠，反应6.5h。加入9份二甲基十四烷基磺丙基铵盐，充分混合。称取10份K 2CO 3配制成70份无机盐溶液，在44℃下与3份环氧氯丙烷同时滴加入淀粉溶液中，匀速滴加时间8h。滴加完毕后继续反应2h，过滤、在110℃下干燥2h后得到均匀分布的多分散含淀粉微球。所述含淀粉微球的粒径集中分布区间为120～380μm(90.5％的粒径在这个区间内)，所述粒径集中分布区间内的粒径分布具有如下特征：(120μm～185μm)：25.6％；(185μm～250μm)：24.8％；(250μm～315μm)：25.3％；(315μm～380μm)：24.3％。其中红外谱图存在C-N峰、S＝O峰。淀粉结构单元含量为38.5wt％，功能单体结构单元的含量为43.2wt％，MAPS、DEDAAC、AMPS、AN结构单元的含量分别为10.7wt％、10.9wt％、11.7wt％、9.9wt％。淀粉与MAPS、DEDAAC、AMPS和AN发生了接枝聚合。
实施例6-10
称取15份玉米淀粉加入100份去离子水中，再加入44份三乙醇胺，在65℃下充分溶解。然后加入0.02份环氧氯丙烷，混合后反应3h。称取7份单体(DMAPS:AMPS:NVF＝1:2:3重量比)加入淀粉溶液中，充分溶解混合。在73℃下加入0.012份引发剂(过硫酸铵：过硫酸钾＝1:2重量比)，反应4h。加入4份二甲基十二烷基磺丙基铵盐，充分混合。称取25份NaCl配制成110份无机盐溶液，在40℃下与7份环氧氯丙烷同时滴加入淀粉溶液中，匀速滴加时间7h。滴加完毕后继续反应2h，得 到均匀分布的多分散含淀粉微球。所述含淀粉微球的粒径集中分布区间为40～280μm(93.6％的粒径在这个区间内)，所述粒径集中分布区间内的粒径分布具有如下特征：(40μm～88μm)：20.8％；(88μm～136μm)：20.8％；(136μm～184μm)：20.0％；(184μm～232μm)：19.6％；(232μm～280μm)：18.8％。其中红外谱图存在C-N峰、S＝O峰。淀粉结构单元含量为51.6wt％，功能单体结构单元的含量为24.2wt％，DMAPS、MAPS、NVF结构单元的含量分别为4.1wt％、8.2wt％、11.9wt％。淀粉与DMAPS、MAPS、NVF发生了接枝聚合。
实施例6-11
按照实施例6-1的方法制备含淀粉微球，不同的是，三乙醇胺由相同重量的三甲醇胺代替，得到均匀分布的多分散含淀粉微球。所述含淀粉微球的粒径集中分布区间为10～170μm(94.5％的粒径在这个区间内)，所述粒径集中分布区间内的粒径分布具有如下特征：(10μm～50μm)：25.4％；(50μm～90μm)：25.1％；(90μm～130μm)：25.1％；(130μm～170μm)：24.4％；以及(10μm～30μm)：11.3％；(30μm～50μm)：13.7％；(50μm～70μm)：13.7％；(70μm～90μm)：11.8％；(90μm～110μm)：13.5％；(110μm～130μm)：11.6％；(130μm～150μm)：12.2％；(150μm～170μm)：12.2％。其中红外谱图存在C-N峰、S＝O峰。测得淀粉结构单元含量为47.2wt％，功能单体结构单元的含量为37.0wt％，MAPS结构单元的含量为11.7wt％，NVF结构单元的含量为12.1wt％，AA结构单元的含量为13.2wt％，淀粉与MAPS、NVF和AA发生了接枝聚合。
实施例6-12
按照实施例6-1的方法制备含淀粉微球，不同的是，环氧氯丙烷由相同重量的三氯氧磷代替，得到均匀分布的多分散含淀粉微球。所述含淀粉微球的粒径集中分布区间为10～170μm(94.5％的粒径在这个区间内)，所述粒径集中分布区间内的粒径分布具有如下特征：(10μm～50μm)：25.4％；(50μm～90μm)：25.1％；(90μm～130μm)：25.1％；(130μm～170μm)：24.4％；以及(10μm～30μm)：13.2％；(30μm～50μm)：13.3％；(50μm～70μm)：12.9％；(70μm～90μm)：11.5％；(90μm～110μm)：13.1％；(110μm～130μm)：11.6％；(130μm～150μm)：12.4％；(150μm～170μm)：12.0％。其中红外谱图存在C-N峰、S＝O峰。测得淀粉结构单元含量为47.2wt％，功能单体结构单元的含量为37.9wt％，MAPS结构单元的含量为11.7wt％，NVF结构单元的含量为13.5wt％，AA结构单元的含量为 12.7wt％，淀粉与MAPS、NVF和AA发生了接枝聚合。
对比例6-1
取10份甘薯淀粉加入100份去离子水中，在80℃下充分溶解30min，之后将其降温备用。称取8份单体(MAPS:NVF:AA＝1:1:1重量比)加入淀粉溶液中，充分溶解混合。在62℃下加入0.15份过硫酸钠，反应6h。加入4份二甲基羟基十四烷基磺丙基铵盐，充分溶解混合。称取3份环氧氯丙烷并将其加入淀粉溶液中，在44℃下连续反应时间7h，得到均匀分布的多分散含淀粉微球。所述含淀粉微球的粒径集中分布区间为120～400μm(95.9％的粒径在这个区间内)，所述粒径集中分布区间内的粒径分布具有如下特征：(120μm～170μm)：12.4％；(170μm～350μm)：79.4％；(350μm～400μm)：8.2％。其中淀粉结构单元含量为45.6wt％，功能单体结构单元的含量32.9wt％，MAPS结构单元的含量为7.6wt％，NVF结构单元的含量为14.1wt％，AA结构单元的含量为11.2wt％，淀粉与MAPS、NVF和AA发生了接枝聚合。
对比例6-2
按照实施例6-1的方法制备含淀粉微球，不同的是，加入单体(MAPS:NVF:AA＝1:1:1)之前不加入0.05份环氧氯丙烷，得到均匀分布的多分散含淀粉微球。所述含淀粉微球的粒径集中分布区间为20～180μm(95.3％的粒径在这个区间内)，所述粒径集中分布区间内的粒径分布具有如下特征：(20μm～60μm)：32.8％；(60μm～100μm)：17.5％；(100μm～140μm)：18.2％；(140μm～180μm)：31.5％。其中淀粉结构单元含量为47.9wt％，功能单体结构单元的含量33.6wt％，MAPS结构单元的含量为10.2wt％，NVF结构单元的含量为11.1wt％，AA结构单元的含量为12.3wt％。淀粉与MAPS、NVF和AA发生了接枝聚合。
对比例6-3
按照实施例6-1的方法制备含淀粉微球，不同的是，无机盐溶液与3份环氧氯丙烷同时一次性加入淀粉溶液中，得到均匀分布的多分散含淀粉微球。所述含淀粉微球的粒径集中分布区间为20～200μm(93.8％的粒径在这个区间内)，所述粒径集中分布区间内的粒径分布具有如下特征：(20μm～65μm)：9.9％；(65μm～110μm)：37.1％；(110μm～155μm)：42.2％；(155μm～200μm)：10.8％。其中淀粉结构单元含量为47.4wt％， 功能单体结构单元的含量37.6wt％，MAPS结构单元的含量为11.6wt％，NVF结构单元的含量为13.8wt％，AA结构单元的含量为12.2wt％。淀粉与MAPS、NVF和AA发生了接枝聚合。
对比例6-4
按照实施例6-1的方法制备含淀粉微球，不同的是，不加入三乙醇胺，得到均匀分布的多分散含淀粉微球。所述含淀粉微球的粒径集中分布区间为8～200μm(91.7％的粒径在这个区间内)，所述粒径集中分布区间内的粒径分布具有如下特征：(8μm～56μm)：36.3％；(56μm～104μm)：21.7％；(104μm～152μm)：19.9％；(152μm～200μm)：22.1％。其中淀粉结构单元含量为45.3wt％，功能单体结构单元的含量38.2wt％，MAPS结构单元的含量为11.6wt％，NVF结构单元的含量为12.7wt％，AA结构单元的含量为13.9wt％，淀粉与MAPS、NVF和AA发生了接枝聚合。
性能测试
1、屏蔽暂堵性能测试
采用砂床封堵实验将上述实施例和对比例制得的微米级淀粉微球各自作为暂堵剂进行评价。实验仪器：钻井液砂床滤失仪、搅拌器、烘箱。实验材料：中石化河南油田楼860井井浆(密度1.19g/cm 3)、实施例样品、对比例样品和20～40目砂样。
实验步骤：
(1)配浆：按井浆+3重量％实施例样品或对比例样品制得钻井液。
(2)制作砂床：用20～40目砂子加到筒体中350mm处，摇匀；
(3)加入上述步骤1配好的钻井液(400mL～500mL)，固定在仪器架上并封固好上下通道；
(4)打开气源压力调至0.69mPa，同时打开上下开关，测量半个小时过程中钻井液侵入砂床的情况。
实验结果：
加入配方30min后滤失量FL 1，钻井液侵入砂床至深度D处后基本稳定。形成稳定的泥饼后，泄压倒出钻井液，加入清水至400mL位置，加压(0.69mPa)测量30min后的滤失量FL 2，实验结果见表1～表6。
2、耐温抗盐性性能测试例
采用中温中压滤失仪对上述实施例和对比例的耐温抗盐性能进行评价。实验仪器：中温中压滤失仪、搅拌器、陈化釜、滚式加热炉。实验材料：中石化河南油田楼860井井浆(密度1.19g/cm 3)、实施例样品、对比例样品。
实验步骤：
(1)配浆：按井浆+5重量％NaCl+5重量％CaCl 2+3重量％实施例样品或对比例样品制得钻井液。
(2)钻井液的高温老化：量取步骤(1)中的钻井液350ml，装入陈化釜。之后将陈化釜放入滚式加热炉，使加入了微球的钻井液在180℃的温度下老化16h。
(3)耐温抗盐性能评价：将老化后的钻井液冷却至室温后倒入评价罐，之后将评价罐安装在中温中压滤失仪上。打开气源压力调至0.69mPa，之后打开进气开关，测量半小时过程中钻井液的失水量。
实验结果：
评价实验开始30min后钻井液的滤失量为FL 3，实验结果见表1～表6。
3、粘土线性膨胀率测试例
取5g钙膨润土(河北沃阳矿产品贸易有限公司)于6MPa下按压5min，即为实验用粘土块。使用青岛恒泰达机电设备有限公司的页岩膨胀仪测定3h内粘土块在清水或不同改性含淀粉微球的悬浮液中的膨胀量，从而分别计算得出线性膨胀率R1、R2(胀率＝膨胀量/初始高度×100％)，其中R1为56％。
实验材料：中石化河南油田楼860井井浆(密度1.19g/cm 3)、页岩膨胀仪、实施例样品、对比例样品。测试结果如表1至表6所示。
表1
实施例 滤失量FL 1/ml 深度D/mm 滤失量FL 2/ml 滤失量FL 3/ml R2％
实施例1-1 0 200 0 25 23
实施例1-2 0 120 0 12 29
实施例1-3 0 180 0 30 32
实施例1-4 0 150 0 21 25
实施例1-5 0 205 0 25 29
对比例1-1 2 350 55 65 52
对比例1-2 0 310 12 60 49
对比例1-3 3 350 60 58 49
对比例1-4 0 330 20 55 46
表2
实施例 滤失量FL 1/ml 深度D/mm 滤失量FL 2/ml 滤失量FL 3/ml R2％
实施例2-1 0 135 0 5 20
实施例2-2 0 170 0 2 17
实施例2-3 0 190 0 2 16
实施例2-4 0 200 0 1 14
实施例2-5 0 220 0 10 23
实施例2-6 0 205 0 3 13
实施例2-7 0 145 0 1 17
实施例2-8 0 205 0 1 18
对比例2-1 2 350 65 45 43
对比例2-2 0 310 15 40 40
对比例2-3 3 350 73 39 39
对比例2-4 0 330 22 33 36
表3
实施例 滤失量FL 1/ml 深度D/mm 滤失量FL 2/ml 滤失量FL 3/ml R2％
实施例3-1 0 125 0 11 9
实施例3-2 0 160 0 15 11
实施例3-3 0 210 0 10 8
实施例3-4 0 220 0 8 7
实施例3-5 0 205 0 25 17
实施例3-6 0 200 0 21 14
实施例3-7 0 150 0 16 11
实施例3-8 0 190 0 24 17
对比例3-1 2 350 70 60 37
对比例3-2 0 330 22 54 33
对比例3-3 3 350 54 55 32
对比例3-4 0 315 13 49 30
表4
实施例 滤失量FL 1/ml 深度D/mm 滤失量FL 2/ml 滤失量FL 3/ml R2％
实施例4-1 0 130 0 11 21
实施例4-2 0 175 0 13 22
实施例4-3 0 170 0 10 20
实施例4-4 0 210 0 6 17
实施例4-5 0 200 0 20 26
实施例4-6 0 165 0 16 23
实施例4-7 0 210 0 15 23
实施例4-8 0 200 0 11 20
对比例4-1 2 350 80 55 46
对比例4-2 0 340 24 51 43
对比例4-3 3 350 55 50 38
对比例4-4 0 300 20 44 40
表5
实施例 滤失量FL 1/ml 深度D/mm 滤失量FL 2/ml 滤失量FL 3/ml R2％
实施例5-1 0 160 0 6 23
实施例5-2 0 180 0 2 20
实施例5-3 0 135 0 5 23
实施例5-4 0 220 0 2 20
实施例5-5 0 210 0 15 29
实施例5-6 0 210 0 10 26
实施例5-7 0 170 0 6 23
实施例5-8 0 200 0 3 21
对比例5-1 4 350 75 50 49
对比例5-2 0 300 8 44 46
对比例5-3 3 350 40 45 43
对比例5-4 0 340 20 38 43
表6
Figure PCTCN2018101771-appb-000005
Figure PCTCN2018101771-appb-000006
通过上述结果可知，当采用实施例的样品时，清水在0.69mPa压力下，在屏蔽暂堵性能测试中，30min内滤失量均显著低于采用对比例样品的滤失量，表明其封堵效果好。当采用对比例的样品时，清水在0.69mPa压力下，屏蔽暂堵性能测试中，30min内滤失量可达40ml，说明效果不好。
在耐温抗盐性能的评价中，当采用实施例的样品时，清水在0.69mPa压力下，30min内滤失量相比于对比例在相同条件下的滤失量更低，说明其耐温抗盐性能优异。当采用对比例的样品时，钻井液在0.69mPa压力下，30min滤失量最大可达65ml。
通过上述R1和R2的结果可知，当采用实施例样品时，粘土块在含改性含淀粉微球的悬浮液中线性膨胀率最大仅为8％，抑制粘土水化分散作用显著，在应用中可有效提高井壁稳定性。当采用对比例的样品时，粘土块在含改性含淀粉微球的悬浮液中线性膨胀率最大可达52％，仅比在清水中的线性膨胀率略低，在应用中不能对井壁粘土起到良好的抑制水化分散作用。

Claims (26)

  1. 一种含淀粉微球，所述含淀粉微球的粒径在粒径集中分布区间内呈均匀分布的多分散性，具有如下特征：将粒径集中分布区间均分成n个区间，每个区间的微球占比为：
    Figure PCTCN2018101771-appb-100001
    其中n为大于1的整数。
  2. 按照权利要求1所述的含淀粉微球，其中，所述含淀粉微球的粒径可控范围为0.1～500μm。
  3. 按照权利要求1或2所述的含淀粉微球，其中，n为4～10之间的整数。
  4. 按照权利要求1～3中任意一项所述的含淀粉微球，其中，所述含淀粉微球的红外光谱在1025～1250cm ～1位置有归属C-N的峰，在1150～1350cm ～1位置有归属S＝O的峰。
  5. 按照权利要求1～4中任意一项所述的含淀粉微球，其中，所述含淀粉微球含有两性离子表面活性剂，所述两性离子表面活性剂的结构式如下：
    Figure PCTCN2018101771-appb-100002
    其中：m为2～6之间的整数，优选m为3或4；R为碳数1～18优选碳数12～18的饱和碳链。
  6. 按照权利要求5所述的含淀粉微球，其中，除端基碳外，所述两性离子表面活性剂碳链上含有羟基、氨基或羧基，且同一个碳上为单取代。
  7. 按照权利要求5或6所述的含淀粉微球，其中，所述两性离子表面活性剂为二甲基十二烷基磺丙基铵盐、二甲基十六烷基磺乙基铵盐、二甲基十八烷基磺丁基铵盐、二甲基(3～羟基十二烷基)磺丙基铵盐、二甲基(6-氨基十四烷基)磺乙基铵盐中的一种或多种。
  8. 按照权利要求1～7中任意一项所述的含淀粉微球，其中，该含淀粉微球中淀粉结构单元的含量为35wt％～95wt％，优选38wt％～85wt％。
  9. 按照权利要求1～8中任意一项所述的含淀粉微球，其中，该含淀粉微球还含有聚合单体结构单元，所述聚合单体结构单元与淀粉结构单元形成接枝共聚物，所述聚合单体为阴离子单体、阳离子单体、非离子单体和两性离子单体中的至少一种；优选地，
    所述两性离子单体为甲基丙烯酰氧乙基-N,N-二甲基丙磺酸盐、N,N-二甲基烯丙基胺丙磺酸盐、4～乙烯基吡啶丙磺酸盐、N-甲基二烯丙基丙磺酸盐、N-甲基二烯丙基丁磺 酸盐中的一种或多种；所述阳离子单体为甲基丙烯酰氧乙基三甲基氯化铵、丙烯酰氧乙基三甲基氯化铵、丙烯酰氧乙基二甲基苄基氯化铵、二甲基二烯丙基氯化铵、二乙基二烯丙基氯化铵)中的一种或多种；所述阴离子单体为丙烯酸、2-甲基-2-丙烯酰氨基丙磺酸、反丁烯二酸、烯丙基磺酸钠、2-丙烯酰氧异戊烯磺酸钠中的一种或多种；所述非离子单体为N-乙烯基吡咯烷酮、丙烯腈、乙烯基甲酰胺、乙烯基乙酰胺中的一种或多种。
  10. 一种含淀粉微球的制备方法，所述制备方法包括如下步骤：
    (1)将淀粉加入到水中，然后加入增溶剂混合均匀，再在交联反应条件下加入第一交联剂进行反应；
    (2)向步骤(1)得到的料液中加入两性离子表面活性剂，混合均匀；
    (3)在30～60℃条件下，向步骤(2)得到的料液中加入无机盐溶液和第二交联剂进行反应，其中，第一交联剂和第二交联剂相同或不同。
  11. 按照权利要求10所述的制备方法，其中，所述制备方法还包括在步骤(1)和步骤(2)之间增加步骤(1～1)：将聚合单体加入到步骤(1)得到的溶液中，充分溶解混合均匀后加入引发剂，在60～80℃下反应3～6h，然后加入所述两性离子表面活性剂进行所述步骤(2)。
  12. 按照权利要求10或11所述的制备方法，其中，步骤(1～1)中所述聚合单体为阳离子单体、阴离子单体、两性离子单体、非离子单体中的一种或多种；优选地，阳离子单体为甲基丙烯酰氧乙基三甲基氯化铵、丙烯酰氧乙基三甲基氯化铵、丙烯酰氧乙基二甲基苄基氯化铵、二甲基二烯丙基氯化铵、二乙基二烯丙基氯化铵中的一种或多种；所述阴离子单体为丙烯酸、2-甲基-2-丙烯酰氨基丙磺酸、反丁烯二酸、烯丙基磺酸钠、2-丙烯酰氧异戊烯磺酸钠中的一种或多种；所述两性离子单体为甲基丙烯酰氧乙基～N,N-二甲基丙磺酸盐、N,N-二甲基烯丙基胺丙磺酸盐、4-乙烯基吡啶丙磺酸盐、N-甲基二烯丙基丙磺酸盐、N-甲基二烯丙基丁磺酸盐中的一种或多种；所述的非离子单体为N-乙烯基吡咯烷酮、丙烯腈、乙烯基甲酰胺、乙烯基乙酰胺中的一种或多种；所述引发剂为过硫酸钾、过硫酸钠、过硫酸铵中的任一种。
  13. 按照权利要求10～12中任意一项所述的制备方法，其中，步骤(1)中所述淀粉为绿豆淀粉、木薯淀粉、红薯淀粉、甘薯淀粉、马铃薯淀粉、麦类淀粉、菱角淀粉、藕淀粉、玉米淀粉中的一种或多种，优选玉米淀粉和/或马铃薯淀粉。
  14. 按照权利要求10～13中任意一项所述的制备方法，其中，步骤(1)中加入增溶剂进行混合的温度为20～80℃，优选为30～60℃，淀粉与增溶剂的重量比为1～20：10～ 50，优选5～15:20～40。
  15. 按照权利要求10～14中任意一项所述的制备方法，其中，所述增溶剂为含有羟基和叔氮的化合物，优选为三甲醇胺、三乙醇胺、三丙醇胺、N,N-双二乙醇胺中的一种或多种。
  16. 按照权利要求10～15中任意一项所述的制备方法，其中，步骤(1)中反应时间为0.5～4h，优选为1～3h；反应温度为20～80℃，优选为30～60℃。
  17. 按照权利要求10～16中任意一项所述的制备方法，其中，步骤(2)所述的两性离子表面活性剂的结构式如下：
    Figure PCTCN2018101771-appb-100003
    其中：m为2～6之间的整数，优选m为3或4；R为碳数1～18优选12～18的饱和碳链；优选地，所述两性离子表面活性剂碳链除端基碳上含有取代的羟基、氨基或羧基，且同一个碳上为单取代；进一步优选地，所述两性离子表面活性剂为二甲基十二烷基磺丙基铵盐、二甲基十六烷基磺乙基铵盐、二甲基十八烷基磺丁基铵盐、二甲基(3-羟基十二烷基)磺丙基铵盐、二甲基(6～氨-十四烷基)磺乙基铵盐中的一种或多种。
  18. 按照权利要求10～17中任意一项所述的制备方法，其中，步骤(3)所述的无机盐为氯化钠、溴化钠、硫酸钠、亚硫酸钠、碳酸钠、碳酸氢钠、硝酸钠、磷酸钠、磷酸氢钠、硅酸钠、氯化钾、溴化钾、硫酸钾、亚硫酸钾、碳酸钾、碳酸氢钾、硝酸钾、磷酸钾、磷酸氢钾、硅酸钾、氯化铵、溴化铵、硝酸铵、氯化钙、溴化钙、氯化镁、溴化镁、硫酸镁、硝酸镁的一种或多种。
  19. 按照权利要求10～18中任意一项所述的制备方法，其中，所述第一交联剂和第二交联剂相同，各自独立的为环氧氯丙烷、N,N-亚甲基双丙烯酰胺、三氯氧磷、三偏磷酸钠、己二酸、六偏磷酸钠中的一种或多种。
  20. 按照权利要求10～19中任意一项所述的制备方法，其中，所述增溶剂为三乙醇胺，所述第一交联剂和第二交联剂为环氧氯丙烷，以重量份数计，所述水、淀粉、三乙醇胺、环氧氯丙烷、两性离子表面活性剂、无机盐溶液的用量分别为：100份水、1～20份淀粉、10～50份三乙醇胺、0.105～14.6份环氧氯丙烷、0.05～10份两性离子表面活性剂、0.5～200份无机盐溶液，其中无机盐溶质占0.025～50份；优选为100份水、5～15份淀粉、20～40份三乙醇胺、1.04～7.8份环氧氯丙烷、1～6份两性离子表面活性剂、 50～150份无机盐溶液，其中无机盐溶质占0.5～30份。
  21. 按照权利要求11～19中任意一项所述的制备方法，其中，所述增溶剂为三乙醇胺，所述第一交联剂和第二交联剂为环氧氯丙烷，以重量份数计，所述水、淀粉、三乙醇胺、环氧氯丙烷、两性离子表面活性剂、单体、引发剂、无机盐溶液的用量分别为：100份水、1～20份淀粉、10～50份三乙醇胺、0.105～14.6份环氧氯丙烷、0.05～10份两性离子表面活性剂、0.1～20份聚合单体、0.001～0.2份引发剂、0.5～200份无机盐溶液，其中无机盐溶质占0.025～50份；优选为100份水、5～15份淀粉、20～40份三乙醇胺、1.04～7.8份环氧氯丙烷、1～6份两性离子表面活性剂、5～15份单体、0.02～0.105份引发剂、50～150份无机盐溶液，其中无机盐溶质占0.5～30份。
  22. 按照权利要求10～21中任意一项所述的制备方法，其中，相对于100重量份的水，步骤(1)中所述第一交联剂的份数为0.005～0.6份，优选份数为0.04～0.3份，步骤(3)中所述第二交联剂的份数为0.1～14份，优选份数为1～7.5份。
  23. 由权利要求10～22中任意一项所述的制备方法制得的含淀粉微球。
  24. 按照权利要求23所述的含淀粉微球，其中，该所述含淀粉微球粒径在粒径集中分布区间内呈均匀分布的多分散性，具有如下特征：将粒径集中分布区间均分成n个区间，每个区间的微球占比为：
    Figure PCTCN2018101771-appb-100004
    其中n为大于1的整数，优选n为4～10之间的整数。
  25. 按照权利要求23或24所述的含淀粉微球，其中，所述含淀粉微球的粒径可控范围为0.1～500μm。
  26. 权利要求1～9和23～25中任一项所述的含淀粉微球在油气层保护暂堵剂中的应用。
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