WO2018210262A1 - 一种酯基聚合物、其制备方法及用途 - Google Patents

一种酯基聚合物、其制备方法及用途 Download PDF

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WO2018210262A1
WO2018210262A1 PCT/CN2018/087068 CN2018087068W WO2018210262A1 WO 2018210262 A1 WO2018210262 A1 WO 2018210262A1 CN 2018087068 W CN2018087068 W CN 2018087068W WO 2018210262 A1 WO2018210262 A1 WO 2018210262A1
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group
different
acid
same
linear
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PCT/CN2018/087068
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English (en)
French (fr)
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李�诚
田松柏
王小伟
章群丹
李虎
朱新宇
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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石油化工科学研究院
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Priority to EP18802833.6A priority Critical patent/EP3626753B1/en
Priority to US16/614,723 priority patent/US11440982B2/en
Priority to CA3062575A priority patent/CA3062575A1/en
Publication of WO2018210262A1 publication Critical patent/WO2018210262A1/zh
Priority to SA519410537A priority patent/SA519410537B1/ar

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/14—Esterification
    • 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
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/04—Monomers containing three or four carbon atoms
    • C08F110/08—Butenes
    • C08F110/10—Isobutene
    • 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
    • C08F267/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated polycarboxylic acids or derivatives thereof as defined in group C08F22/00
    • C08F267/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated polycarboxylic acids or derivatives thereof as defined in group C08F22/00 on to polymers of anhydrides
    • 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
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
    • C08F8/32—Introducing nitrogen atoms or nitrogen-containing groups by reaction with amines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L95/00—Compositions of bituminous materials, e.g. asphalt, tar, pitch
    • 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
    • C09K8/52—Compositions for preventing, limiting or eliminating depositions, e.g. for cleaning
    • C09K8/524—Compositions for preventing, limiting or eliminating depositions, e.g. for cleaning organic depositions, e.g. paraffins or asphaltenes
    • 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
    • C08F2810/00—Chemical modification of a polymer
    • C08F2810/40—Chemical modification of a polymer taking place solely at one end or both ends of the polymer backbone, i.e. not in the side or lateral chains

Definitions

  • This invention relates to a polymer, and more particularly to an ester-based polymer suitable for use as a dispersant and/or polymerization inhibitor.
  • Asphaltene is generally defined as a petroleum component that is insoluble in n-heptane and soluble in toluene. It is a class of substances defined by solubility. It is the highest molecular weight, the most polar and the most difficult to process in heavy oil. Component. The presence of asphaltenes makes heavy oils have the characteristics of colloidal systems. When the temperature, pressure or composition changes and the environment of asphaltenes changes, the asphaltenes are prone to flocculation and deposition, giving oil production, storage, transportation and processing. Bringing adverse effects.
  • Asphaltene dispersants known in the art are, for example, combinations of alkylphenol-formaldehyde resins disclosed in patents CA 2029465C and CA 2075749C with hydrophilic-parophilic vinyl polymers. Dodecylbenzene is described in U.S. Patent 4,414,035 A and published papers DLChang, HSFogler (SPE Paper No. 25185, 1993) and Francia Marcano (Energy & Fuels, 2015, 29(5): 2813-2822) and the like. Sulfonic acid (DBSA) has the property of dispersing asphaltenes.
  • DBSA Sulfonic acid
  • the present invention satisfies the above needs in the art, and provides a novel ester-based polymer suitable for use as a dispersant and/or polymerization inhibitor, particularly as an asphaltene dispersant and/or polymerization inhibitor, and preparation thereof Method and use.
  • the present invention provides an ester-based polymer having the structure shown by the following formula (I):
  • a group T represents the backbone of the ester-based polymer
  • Each group B is the same or different from each other, and each is independently selected from O or S;
  • Each group R is the same or different from each other, each independently representing a C 1-10 alkylene group, and each group R is optionally substituted with a group selected from the group consisting of an alkoxy group, a hydroxyl group, an amino group and a fluorenyl group;
  • Each group A is the same or different from each other, and each is independently selected from O, S or NR";
  • each of the groups R ' are the same or different, each independently represent a C 1-10 alkylene group, each group R' is selected from optionally substituted alkoxy, hydroxy, a substituted amino group and a mercapto group;
  • Each group N b is the same or different from each other, each independently selected from H or -R′′′-B′H, wherein at least one of the two N b on the same nitrogen atom is —R′′′-B′H;
  • Each group R" is the same or different from each other, and each is independently selected from H or a C 1-10 hydrocarbon group;
  • Each group R''' is the same or different from each other, each independently representing a C1-10 hydrocarbylene group, and each group R''' is optionally substituted with a group selected from the group consisting of an alkoxy group, a hydroxyl group, an amino group and a fluorenyl group;
  • Each group B' is the same or different from each other, and each is independently selected from O or S;
  • Each y is the same or different from each other, each independently representing an integer between 1 and 6;
  • n is an integer between 1-10.
  • the backbone represented by the group T in the ester-based polymer of the present invention is selected from the group consisting of polyolefins, polyethers and polyesters.
  • the present invention provides a process for the preparation of an ester-based polymer comprising the step of esterifying a parent polymer with at least one compound of the following formula (II):
  • the parent polymer refers to a -COOH group and/or Group of polymers
  • Group B is selected from O or S;
  • Each group R is the same or different from each other, each independently representing a C 1-10 alkylene group, and each group R is optionally substituted with a group selected from the group consisting of an alkoxy group, a hydroxyl group, an amino group and a fluorenyl group;
  • Each group A is the same or different from each other, and each is independently selected from O, S or NR";
  • the group R ' represents C 1-10 alkylene, the group R' is selected from optionally substituted alkoxy, hydroxy, a substituted amino group and a mercapto group;
  • Each group N b is the same or different from each other, each independently selected from H or -R""-B'H, at least one of which is -R""-B'H;
  • Each group R" is the same or different from each other, and each is independently selected from H or a C 1-10 hydrocarbon group;
  • each group R "' are the same or different from each other, each independently represent a C 1-10 alkylene group, each group R"' is selected from optionally substituted alkoxy, hydroxy, a substituted amino group and a mercapto group;
  • Each group B' is the same or different from each other, each independently selected from O or S;
  • y represents an integer between 1-6.
  • the preparation method of the present invention further comprises at least one compound represented by the following formula (III),
  • Each group N b is the same or different from each other, each independently selected from H or -R""-B'H, at least one of which is -R""-B'H;
  • Each group R''' is the same or different from each other, each independently representing a C1-10 hydrocarbylene group, and each group R''' is optionally substituted with a group selected from the group consisting of an alkoxy group, a hydroxyl group, an amino group and a fluorenyl group;
  • Each group B' is the same or different from each other, and each is independently selected from O or S;
  • Each group B is the same or different from each other, and each is independently selected from O or S;
  • Each group R is the same or different from each other, each independently representing a C 1-10 alkylene group, and each group R is optionally substituted with a group selected from the group consisting of an alkoxy group, a hydroxyl group, an amino group and a fluorenyl group;
  • Each group A is the same or different from each other, and each is independently selected from O, S or NR";
  • Each group R' is the same or different from each other, each independently represents a C 1-10 alkylene group, and each group R' is optionally substituted with a group selected from the group consisting of an alkoxy group, a hydroxyl group, an amino group and a fluorenyl group;
  • Each group R" is the same or different from each other, each independently selected from H or a C 1-10 hydrocarbon group;
  • Each y is the same or different from each other, and each independently represents an integer between 1-6.
  • the invention provides the use of an ester-based polymer according to the invention and/or an ester-based polymer prepared according to the process of the invention as a dispersant and/or a polymerization inhibitor, in particular as an asphaltene dispersion Use of a agent and/or a polymerization inhibitor.
  • the ester-based polymer of the present invention exhibits excellent dispersion and polymerization properties when used as a dispersant and/or a polymerization inhibitor, particularly an asphaltene dispersant and/or a polymerization inhibitor, compared to existing materials, for example More effectively reduce or solve the phenomenon of flocculation deposition caused by changes in external conditions of asphaltenes.
  • Figure 2 is a liquid chromatography (LCMS) spectrum of the intermediate compound 3;
  • Figure 5 is an infrared spectrum of the product polymer 8 prepared in Example 2;
  • Figure 6 is an infrared spectrum of the product polymer 10 prepared in Example 3.
  • Figure 8 is an infrared spectrum of the product polymer 14 prepared in Comparative Example 1;
  • Figure 9 is an infrared spectrum of the product polymer D-02 prepared in Comparative Example 2.
  • any specific numerical values (including the endpoints of the numerical ranges) disclosed herein are not limited to the precise value of the numerical value, but should be understood to cover the value close to the precise value. Moreover, for the disclosed numerical range, one or more new ones can be obtained between the endpoint values of the range, the endpoint values and the specific point values in the range, and the specific point values. Numerical ranges, these new numerical ranges are also considered to be specifically disclosed herein.
  • the molecular weight of all polymers is the number average molecular weight Mn, if not indicated to the contrary.
  • the present invention provides an ester-based polymer having the structure represented by the following formula (I):
  • a group T represents the backbone of the ester-based polymer
  • Each group B is the same or different from each other, each independently selected from O or S, preferably O;
  • Each group R is the same or different from each other, each independently represent a C 1-10 alkylene, preferably C 1-6 straight-chain or branched alkylene group, more preferably a C 1-4 straight-chain or branched alkylene group, each of The group R is optionally substituted by a group selected from alkoxy, hydroxy, amino and thiol groups, preferably unsubstituted;
  • Each group A is the same or different from each other, each independently selected from O, S or NR", preferably O or S, more preferably O;
  • Each group R' is the same or different from each other, and each independently represents a C 1-10 alkylene group, preferably a C 1-6 linear or branched alkylene group, further preferably a C 1-4 linear or branched alkylene group, Each group R' is optionally substituted by a group selected from alkoxy, hydroxy, amino and thiol groups, preferably unsubstituted;
  • N b each group the same or different, are each independently selected from H or -R "'-B'H, wherein two N b on the same nitrogen atom, at least one of -R"' - B'H, preferably Two N b are each independently -R""-B'H;
  • Each group R" is identical or different from each other, each independently selected from H or C 1-10 hydrocarbyl groups, preferably selected from H or C 1-6 straight or branched alkyl groups, further preferably selected from H or C 1-4 a linear or branched alkyl group, most preferably H;
  • Each group R'"' is the same or different from each other, and each independently represents a C 1-10 alkylene group, preferably a C 1-6 linear or branched alkylene group, further preferably a C 1-4 linear or branched alkylene group.
  • each group R"" is optionally substituted with a group selected from alkoxy, hydroxy, amino and thiol groups, preferably unsubstituted;
  • Each group B' is the same or different from each other, each independently selected from O or S, preferably O;
  • Each y is the same or different from each other, each independently representing an integer between 1-6, preferably an integer between 1-3, most preferably 1;
  • n is an integer between 1-10, preferably an integer between 1 and 5, most preferably 2.
  • the group B represents O; each group R is the same or different from each other, and each independently represents a C 1-6 linear or branched alkylene group; each group A is mutually The same or different, each independently selected from O or S; each group R' is the same or different from each other, and each independently represents a C 1-6 linear or branched alkylene group; each group N b is the same or different from each other, Each independently represents -R""-B'H; each group R'"' is the same or different from each other, each independently representing a C1-6 straight or branched alkylene group; the group B' represents O; each y The same or different from each other, each independently represents an integer between 1 and 3; and m is an integer between 1 and 5.
  • the group B represents O; each group R is the same or different from each other, and each independently represents a C 1-4 linear or branched alkylene group; Represents O; each group R' is the same or different from each other, and each independently represents a C 1-4 straight or branched alkylene group; each group N b is the same or different from each other, and each independently represents -R′′′-B 'H; each group R''' is the same or different from each other, each independently representing a C 1-4 straight or branched alkylene group; the group B' represents O; y is 1; and m is 2.
  • the backbone represented by the group T in the ester-based polymer of the invention is selected from the group consisting of polyolefins, polyethers and polyesters, preferably polyolefins, including but not limited to homopolymers of C 2-20 olefins. Or a copolymer, more preferably a homopolymer or copolymer of a C 2-10 olefin such as polyethylene, polypropylene, polybutene, polyisobutylene, polypentene, polyhexene, polyoctene, polydecene and poly Terpene.
  • the ester-based polymer of the present invention has a number average molecular weight of from about 600 to about 10,500, more preferably from about 800 to about 4,500.
  • the present invention provides a process for the preparation of an ester-based polymer comprising the step of esterifying a parent polymer with at least one compound of the following formula (II):
  • the parent polymer refers to a -COOH group and/or Group of polymers
  • the group B is selected from O or S, preferably O;
  • Each group R is the same or different from each other, and each independently represents a C 1-10 alkylene group, preferably a C 1-6 linear or branched alkylene group, further preferably a C 1-4 linear or branched alkylene group, each of which The group R is optionally substituted by a group selected from alkoxy, hydroxy, amino and thiol groups, preferably unsubstituted;
  • Each group A is the same or different from each other, each independently selected from O, S or NR", preferably O or S, more preferably O;
  • the group R' represents a C 1-10 alkylene group, preferably a C 1-6 linear or branched alkylene group, further preferably a C 1-4 linear or branched alkylene group, the group R' being optionally selected Substituted from alkoxy, hydroxy, amino and thiol groups, preferably unsubstituted;
  • Each group N b is the same or different from each other, each independently selected from H or -R""-B'H, at least one of which is -R""-B'H, preferably each independently -R""-B 'H;
  • radicals R are each independently selected from H or C 1-10 hydrocarbon group, preferably selected from H or C 1-6 straight-chain or branched-chain alkyl group, more preferably selected from H or C 1-4 a linear or branched alkyl group, most preferably H;
  • Each group R'"' is the same or different from each other, and each independently represents a C 1-10 alkylene group, preferably a C 1-6 linear or branched alkylene group, further preferably a C 1-4 linear or branched alkylene group.
  • each group R"" is optionally substituted with a group selected from alkoxy, hydroxy, amino and thiol groups, preferably unsubstituted;
  • Each group B' is the same or different from each other, each independently selected from O or S, preferably O;
  • y represents an integer between 1-6, preferably an integer between 1-3, most preferably 1.
  • the preparation method of the present invention further comprises at least one compound represented by the following formula (III),
  • Each group N b is the same or different from each other, each independently selected from H or -R""-B'H, at least one of which is -R""-B'H, preferably each independently -R""-B 'H; and
  • Each group R'"' is the same or different from each other, and each independently represents a C 1-10 alkylene group, preferably a C 1-6 linear or branched alkylene group, further preferably a C 1-4 linear or branched alkylene group.
  • each group R"" is optionally substituted with a group selected from alkoxy, hydroxy, amino and thiol groups, preferably unsubstituted;
  • Each group B' is the same or different from each other, each independently selected from O or S, preferably O;
  • Each group B is the same or different from each other, each independently selected from O or S, preferably O;
  • Each group R is the same or different from each other, and each independently represents a C 1-10 alkylene group, preferably a C 1-6 linear or branched alkylene group, further preferably a C 1-4 linear or branched alkylene group, each of which The group R is optionally substituted by a group selected from alkoxy, hydroxy, amino and thiol groups, preferably unsubstituted;
  • Each group A is the same or different from each other, each independently selected from O, S or NR", preferably O or S, more preferably O;
  • Each group R' is the same or different from each other, and each independently represents a C 1-10 alkylene group, preferably a C 1-6 linear or branched alkylene group, further preferably a C 1-4 linear or branched alkylene group, Each group R' is optionally substituted by a group selected from alkoxy, hydroxy, amino and thiol groups, preferably unsubstituted;
  • Each group R" is identical or different from each other, each independently selected from H or C 1-10 hydrocarbyl groups, preferably selected from H or C 1-6 straight or branched alkyl groups, further preferably selected from H or C 1-4 a linear or branched alkyl group, most preferably H;
  • Each y is the same or different from each other, each independently representing an integer between 1-6, preferably an integer between 1-3, most preferably one.
  • the group B represents O; each group R is the same or different from each other, and each independently represents a C 1-6 linear or branched alkylene group; each group A is identical to each other or Different, each independently selected from O or S; each group R' is the same or different from each other, and each independently represents a C 1-6 linear or branched alkylene group; each group N b is the same or different from each other, and is independently -R""-B'H; each group R'"' is the same or different from each other, each independently represents a C1-6 straight or branched alkylene group; the group B' represents O; and each y is mutually The same or different, each independently represents an integer between 1-3.
  • the group B represents O; each group R is the same or different from each other, each independently represents a C 1-4 linear or branched alkylene group; and the group A represents O.
  • Each group R' is the same or different from each other, and each independently represents a C 1-4 linear or branched alkylene group; each group N b is the same or different from each other, and each independently represents -R′′′-B′H
  • Each group R'"' is the same or different from each other, each independently representing a C1-4 straight or branched alkylene group; the group B' represents O; and y is 1.
  • the compound of the formula (III) is selected from the group consisting of an alkanolamine, a thiolamine, or a mixture thereof, preferably an alkanolamine comprising two hydroxyl groups, a mercaptan amine comprising two mercapto groups, or a mixture thereof, more preferably A C1-C10 alcohol amine containing two hydroxyl groups, a C1-C10 thiol amine containing two mercapto groups, or a mixture thereof, for example, ethanolamine, propanolamine, butanolamine, pentanolamine, hexanolamine, ethylene-2 Alcoholamine, propylene glycol amine, butanediol amine, pentylene glycolamine, hexanediol amine, ethanethiolamine, propyl thiolamine, butyl thiolamine, pentyl thiolamine, hexyl thiolamine, ethanedit
  • the compound of the formula (IVA) is selected from one or more of an ether substance containing a hydroxyl group and a carboxyl group, an ether substance containing a mercapto group and a carboxyl group, and an ether substance containing an amine group and a carboxyl group.
  • an etherification product of an alkylene glycol and a hydroxy acid an etherification product of an alkylene dithiol and a hydroxy acid, and an etherification product of an alcohol amine and a hydroxy acid, more preferably C1-C5 Etherification of alkylene glycol with C1-C5 hydroxy acid, etherification product of C1-C5 alkylene dithiol with C1-C5 hydroxy acid and etherification of C1-C5 alcohol amine with C1-C5 hydroxy acid
  • One or more of the products for example, 2-(2-hydroxyethoxy)-acetic acid, 3-(2-hydroxyethoxy)-propionic acid, 3-(2-hydroxyethoxy)- Butyric acid, 2-(3-hydroxypropoxy)-acetic acid, 2-(4-hydroxybutoxy)-propionic acid, 2-(2-hydroxyethylthio)-acetic acid, 3-(2-hydroxyethyl) One of thio)-propionic acid
  • the compound of the formula (IVB) is selected from one or more of oxalactone, thialactone and azalide, preferably oxalactone; for example, oxaprone may be used.
  • the compound of formula (III) is selected from the group consisting of the compounds of formula (V):
  • R 1 and R 2 may be the same or different and are each independently selected from a C1-C10 alkylene group, preferably a C1-C6 alkylene group, more preferably a C1-C4 alkylene group, and R 1 and R 2 are optionally selected.
  • the ground is substituted with a group selected from alkoxy, hydroxy, amino and thiol groups, preferably unsubstituted.
  • the compound of formula (IVB) is selected from the group consisting of compounds of formula (VI):
  • R 3 and R 4 may be the same or different and are each independently selected from H or a C1-C8 alkyl group, preferably H or a C1-C4 alkyl group, wherein the alkyl group is optionally selected from the group consisting of an alkoxy group and a hydroxyl group.
  • the group of the amino group and the fluorenyl group is substituted, preferably unsubstituted.
  • a compound of formula (III) and a compound of formula (IVA) and formula (IVB) The molar ratio between the total amount is from about 1:0.1 to 10, preferably from about 1:0.5 to about 5, more preferably from about 1:0.9 to about 1.1.
  • the reaction temperature of the acylation reaction is about 50 to 150 ° C, more preferably about 80 to 120 ° C; the reaction pressure is about 0.1 to 10 MPa, more preferably about 0.1 to 5 MPa; and the reaction time is about 0.1 to 10 hours. More preferably, it is about 4h-8h.
  • the reaction temperature of the acylation reaction is about 80 to 120 ° C; the reaction pressure is about 0.1 to 5 MPa; and the reaction time is about 4 to 8 hours.
  • an inert gas may be introduced into the acylation reaction, more preferably nitrogen gas is introduced.
  • a solvent may or may not be added to the acylation reaction.
  • the solvent is optionally added, butane, cyclobutane, pentane, cyclopentane, hexane, cyclohexane, heptane, n-heptane, octane, cyclooctane, decane, undecane may be added.
  • the amount of the solvent is not particularly limited, and is preferably about 10 to 200% by mass of the compound of the formula (III). The solvent can be removed after completion of the reaction by methods known to those skilled in the art.
  • a catalyst may or may not be added to the acylation reaction.
  • the catalyst is optionally added, one or more of silica, clay, magnesium silicate, alumina, silica gel and molecular sieve may be added, preferably silica.
  • the amount of the catalyst is preferably from about 0.1% to about 20%, preferably from about 0.5% to about 2%, by mass of the compound of formula (III).
  • the -COOH group is contained and/or
  • the polymer of the group contains q-COOH groups in the molecule and/or a polymer of a group, wherein q represents a -COOH group in the polymer and/or
  • the ratio of the total number of groups to the number of polymer molecules, since it is an average value, can be a non-integer number.
  • a preferred range of value of q is 1 ⁇ q ⁇ 10, more preferably 1 ⁇ q ⁇ 5.
  • the polymer is a polyolefin, a polyether or a polyester.
  • said -COOH group and / or The polymer of the group has a number average molecular weight of from about 500 to 10,000, more preferably from about 600 to 6,000, still more preferably from about 600 to 3,000.
  • the esterification reaction in the containing -COOH group and / or In the esterification reaction of the polymer of the group with the compound of the formula (II), with a -COOH group and/or
  • the molar ratio of the polymer to the compound of formula (II) is calculated from the group of from about 1: 0.1 to 10, preferably from about 1: 0.5 to about 5, more preferably from about 1: 0.9 to about 1.1.
  • the esterification reaction has a reaction temperature of about 100 to 300 ° C, more preferably about 120 to 200 ° C; a reaction pressure of about 0.1 to 10 MPa, more preferably about 0.1 to 5 MPa; and a reaction time of about 0.1 to 10 hours. More preferably, it is about 2h-8h.
  • the esterification reaction has a reaction temperature of about 120 to 200 ° C; a reaction pressure of about 0.1 to 5 MPa; and a reaction time of about 2 to 8 hours.
  • an inert gas may be introduced into the esterification reaction, more preferably nitrogen gas is introduced.
  • a solvent may or may not be added to the esterification reaction.
  • the solvent is optionally added, butane, cyclobutane, pentane, cyclopentane, hexane, cyclohexane, heptane, n-heptane, octane, cyclooctane, decane, undecane may be added.
  • the amount of the solvent is not particularly limited, and it is preferably the -COOH group and/or The polymer of the group is about 10-200% by mass.
  • the solvent can be removed after completion of the reaction by methods known to those skilled in the art.
  • a catalyst may or may not be added to the esterification reaction.
  • the catalyst is optionally added, one or more of silica, clay, magnesium silicate, alumina, silica gel and molecular sieve may be added, preferably silica.
  • the amount of the catalyst is preferably the -COOH group and/or The polymer mass of the group is from about 0.1% to about 20%, more preferably from about 0.5% to about 2%.
  • the -COOH group is contained and/or
  • the preferred range of value of u is 1 ⁇ u ⁇ 10, more preferably 1 ⁇ u ⁇ 5.
  • the alkenyl acid and/or alkenyl anhydride is a C 3-10 alkenyl acid and/or an alkenyl acid anhydride, more preferably a C 4-10 alkenyl diacid and/or an alkenyl group.
  • the dianhydride may, for example, be acrylic acid, crotonic acid, pentenoic acid, hexenoic acid, heptenoic acid, octenoic acid, decenoic acid, decenoic acid, butenedioic acid, glutaconic acid or hexenedioic acid.
  • heptenedioic acid heptenedioic acid, octenedioic acid, decenedioic acid, decenedioic acid, maleic anhydride, butenedic anhydride, glutaconic anhydride, hexenedicarboxylic acid anhydride, heptylene dianhydride, octenate dianhydride, One or more of terpene dianhydride and terpene dianhydride.
  • the temperature is about 100-350 ° C, more preferably about 200-300 ° C;
  • the reaction pressure is about 0.1-10 MPa, more preferably about 0.1-5 MPa; and the reaction time is about 0.1 h - 10 h, more preferably about 0.5 h - 10 h.
  • the reaction temperature is about 200-300 ° C; the reaction pressure is about 0.1-5 MPa; and the reaction time is about 0.5 h - 10 h.
  • an inert gas is introduced during the reaction, more preferably nitrogen gas is introduced.
  • water, DMF, NMP, acetone, DMSO, butane, cyclobutane, pentane, cyclopentane, hexane, cyclohexane, heptane, n-heptane, octane, ring may be added.
  • the solvent can be removed after completion of the reaction by methods known to those skilled in the art.
  • the catalyst is optionally added, one or more of silica, clay, magnesium silicate, alumina, silica gel and molecular sieve may be added, preferably silica.
  • the ester-based polymer is obtained by removing the catalyst and the solvent which may be present from the finally obtained reaction mixture by any means conventionally known.
  • ester-based polymers of the present invention are suitable for use as dispersants and/or polymerization inhibitors, and are particularly suitable for use as asphaltene dispersants and/or polymerization inhibitors.
  • the invention also provides the use of an ester-based polymer according to the invention and/or an ester-based polymer prepared according to the process of the invention as a dispersant and/or a polymerization inhibitor, in particular as an asphaltene Use of dispersants and/or polymerization inhibitors.
  • ester-based polymer of the present invention When used as a dispersant and/or a polymerization inhibitor, particularly an asphaltene dispersant and/or a polymerization inhibitor, it has very excellent dispersion and polymerization properties.
  • the invention provides the following technical solutions:
  • a group T represents the backbone of the ester-based polymer
  • Each group B is the same or different from each other, each independently selected from O or S, preferably O;
  • Each group R is the same or different from each other, and each independently represents a C 1-10 alkylene group, preferably a C 1-6 linear or branched alkylene group, further preferably a C 1-4 linear or branched alkylene group;
  • Each group A is the same or different from each other, each independently selected from O, S or NH, preferably O or S, more preferably O;
  • Each group R' is the same or different from each other, and each independently represents a C 1-10 alkylene group, preferably a C 1-6 linear or branched alkylene group, further preferably a C 1-4 linear or branched alkylene group;
  • N b each group the same or different, are each independently selected from H or -R "'-B'H, wherein the repeating unit is the same, i.e., on the same nitrogen atom, two of the at least one of N b -R"'-B'H, more preferably two N b are each independently -R'"-B'H;
  • Each group R'"' is the same or different from each other, and each independently represents a C 1-10 alkylene group, preferably a C 1-6 linear or branched alkylene group, further preferably a C 1-4 linear or branched alkylene group. ;
  • Each group B' is the same or different from each other, each independently selected from O or S, preferably O;
  • Each y is the same or different from each other, each independently representing an integer between 1-6, preferably an integer between 1-3, most preferably 1;
  • n is an integer between 1-10, preferably an integer between 1 and 5, most preferably 2.
  • the ester-based polymer according to the first aspect characterized in that the main chain represented by the group T is selected from one or more of a polyolefin, a polyether and a polyester, preferably a polyolefin.
  • ester-based polymer according to any one of claims 1 to 3, characterized in that
  • the group T represents a polyolefin chain
  • Group B represents O
  • Each group R is the same or different from each other, and each independently represents a C 1-6 linear or branched alkylene group
  • Each group A is the same or different from each other, and each is independently selected from O or S;
  • Each of the groups R ' are the same or different, each independently represent a C 1-6 straight-chain or branched alkylene group
  • Each group N b is the same or different from each other, and each independently represents -R′′′-B′H;
  • Each group R'"' is the same or different from each other, and each independently represents a C1-6 straight or branched alkylene group
  • Group B' represents O
  • Each y is the same or different from each other, each independently representing an integer between 1-3;
  • n 1-5.
  • the group T represents a polyolefin chain
  • Group B represents O
  • Each group R is the same or different from each other, and each independently represents a C 1-4 straight or branched alkylene group
  • Group A represents O;
  • Each group R' is the same or different from each other, and each independently represents a C 1-4 straight or branched alkylene group
  • Each group N b is the same or different from each other, and each independently represents -R′′′-B′H;
  • Each group R'"' is the same or different from each other, and each independently represents a C1-4 straight or branched alkylene group
  • Group B' represents O
  • y 1;
  • ester-based polymer according to any one of claims 1 to 5, wherein the ester-based polymer has a number average molecular weight of from about 600 to about 10,500, preferably from about 800 to about 4,500.
  • the parent polymer refers to a -COOH group and/or a polymer of a group
  • the group B is selected from O or S, preferably O;
  • Each group R is the same or different from each other, and each independently represents a C 1-10 alkylene group, preferably a C 1-6 linear or branched alkylene group, further preferably a C 1-4 linear or branched alkylene group;
  • Each group A is the same or different from each other, each independently selected from O, S or NH, preferably O or S, more preferably O;
  • the group R' represents a C 1-10 alkylene group, preferably a C 1-6 linear or branched alkylene group, further preferably a C 1-4 linear or branched alkylene group;
  • Each group N b is identical or different from each other, each independently selected from H or -R""-B'H, at least one of which is -R""-B'H, more preferably each independently -R""- B'H;
  • Each group R'"' is the same or different from each other, and each independently represents a C 1-10 alkylene group, preferably a C 1-6 linear or branched alkylene group, further preferably a C 1-4 linear or branched alkylene group. ;
  • Each group B' is the same or different from each other, each independently selected from O or S, preferably O;
  • y represents an integer between 1-6, preferably an integer between 1-3, most preferably 1.
  • Each group N b is identical or different from each other, each independently selected from H or -R""-B'H, at least one of which is -R""-B'H, more preferably each independently -R""- B'H;
  • Each group R'"' is the same or different from each other, and each independently represents a C 1-10 alkylene group, preferably a C 1-6 linear or branched alkylene group, further preferably a C 1-4 linear or branched alkylene group. ;
  • Each group B' is the same or different from each other, each independently selected from O or S, preferably O;
  • Each group B is the same or different from each other, each independently selected from O or S, preferably O;
  • Each group R is the same or different from each other, each independently represent a C 1-10 alkylene, preferably C 1-6 straight-chain or branched alkylene group, more preferably a C 1-4 straight-chain or branched alkylene group;
  • Each group A is the same or different from each other, each independently selected from O, S or NH, preferably O or S, more preferably O;
  • Each group R' is the same or different from each other, and each independently represents a C 1-10 alkylene group, preferably a C 1-6 linear or branched alkylene group, further preferably a C 1-4 linear or branched alkylene group; and
  • Each y is the same or different from each other, each independently representing an integer between 1-6, preferably an integer between 1-3, most preferably one.
  • the group B represents O; the groups R are the same or different from each other, and each independently represents a C 1-6 linear or branched alkylene group;
  • the groups A are identical or different from each other, each independently selected from O or S; each group R' is the same or different from each other, each independently representing a C 1-6 straight or branched alkylene group; each group N b is mutually The same or different, each independently represents -R""-B'H; each group R'"' is the same or different from each other, each independently represents a C1-6 straight or branched alkylene group; the group B' represents O; and each y is the same or different from each other, and each independently represents an integer between 1-3.
  • the group B represents O; the groups R are identical or different from each other, each independently representing a C 1-4 linear or branched alkylene group; Represents O; each group R' is the same or different from each other, and each independently represents a C 1-4 straight or branched alkylene group; each group N b is the same or different from each other, and each independently represents -R′′′-B 'H; each group R''' is the same or different from each other, each independently representing a C1-4 straight or branched alkylene group; the group B' represents O; and y is 1.
  • the compound of the formula (III) is an alcoholamine and/or a thiolamine, preferably an alcoholamine comprising two hydroxyl groups and/or comprises The two mercapto thiol amines, more preferably a C1-C10 alcohol amine comprising two hydroxyl groups and/or a C1-C10 thiol amine comprising two mercapto groups.
  • an ether compound of a base group and a carboxyl group preferably an etherification product of an alkylene glycol and a hydroxy acid, an etherification product of an alkylene dithiol and a hydroxy acid, and an ether of an alcohol amine and a hydroxy acid
  • One or more of the products more preferably an etherified product of a C1-C5 alkylene glycol with a C1-C5 hydroxy acid, an etherified product of a C1-C5 alkylenedithiol and a C1-C5 hydroxy acid
  • the etherification products of a C1-C5 alkanolamine and a C1-C5 hydroxy acid preferably an etherification product of an alkylene glycol and a hydroxy acid, an etherification product of an alkylene dithiol and a hydroxy acid, and an ether of an alcohol amine and a hydroxy acid
  • the compound of formula (III) is selected from the group consisting of ethanolamine, propanolamine, butanolamine, pentanolamine, hexanolamine, and ethylene Alcoholamine, propylene glycol amine, butanediol amine, pentylene glycolamine, hexanediol amine, ethanethiolamine, propyl thiolamine, butyl thiolamine, pentyl thiolamine, hexyl thiolamine, ethanedithiol
  • the compound of formula (IVA) is selected from the group consisting of 2-(2-hydroxyethoxy) - acetic acid, 3-(2-hydroxyethoxy)-propionic acid, 3-(2-hydroxyethoxy)-butyric acid
  • R 1 and R 2 may be the same or different and are each independently selected from a C1-C10 alkylene group, preferably a C1-C4 alkylene group.
  • R 3 and R 4 may be the same or different and are each independently selected from H or a C1-C10 alkyl group, preferably H or a C1-C4 alkyl group.
  • any of aspects 7-16 wherein the -COOH group is contained and/or
  • the polymer of the group contains q-COOH groups in the molecule and/or a polymer of a group, wherein q represents a -COOH group in the polymer and/or The ratio of the total number of groups to the number of polymer molecules, 1 ⁇ q ⁇ 10, preferably 1 ⁇ q ⁇ 5, particularly preferably the polymer is a polyolefin, a polyether or a polyester.
  • the polymer of the group has a number average molecular weight of from about 500 to 10,000, preferably from about 600 to 6,000, further preferably from about 600 to 3,000.
  • the molar ratio of the compound to the total amount of the compound of the formula (IVA) and the formula (IVB) is from about 1: 0.1 to 10, preferably from about 1: 0.5 to 5, more preferably from about 1: 0.9 to 1.1; and the reaction temperature is about 50 - 150 ° C, preferably about 80-120 ° C; reaction pressure is about 0.1-10 MPa, preferably about 0.1-5 MPa; reaction time is about 0.1h-10h, preferably about 4h-8h.
  • the molar ratio of the polymer to the compound of formula (II) is calculated from the group of from about 1: 0.1 to 10, preferably from about 1: 0.5 to 5, more preferably from about 1: 0.9 to 1.1; and the reaction temperature is from about 100 to 300 ° C. Preferably, it is about 120-200 ° C; the reaction pressure is about 0.1-10 MPa, preferably about 0.1-5 MPa; and the reaction time is about 0.1 h-10 h, preferably about 2 h-8 h.
  • alkenyl acid and/or alkenyl anhydride is a C 3-10 alkenyl acid and/or alkenyl anhydride, more preferably C 4-10 alkenyl acid and / or alkenyl anhydride.
  • alkenyl acid and/or alkenyl anhydride is selected from the group consisting of acrylic acid, crotonic acid, pentenoic acid, hexenoic acid, and glyoxygen.
  • ester-based polymer of any one of the embodiments 1 to 6 and/or the ester-based polymer prepared by the method according to any one of the schemes 7 to 26 as a dispersing agent and/or a polymerization inhibitor
  • Diethanolamine analytical grade (standard 98%), purchased from Beijing Coupling Technology Co., Ltd.;
  • Diisopropanolamine analytical grade (standard 98%), purchased from Beijing Coupling Technology Co., Ltd.;
  • Triethanolamine (TEA) analytical grade (standard 98%), purchased from Beijing Coupling Technology Co., Ltd.;
  • 1,4-dioxan-2-one analytical grade (standard 98%), purchased from Beijing Coupling Technology Co., Ltd.;
  • Valerolactone analytically pure (standard 98%), purchased from Beijing Coupling Technology Co., Ltd.;
  • Infrared spectrum obtained by Nicolet 6700 Fourier transform infrared spectrometer manufactured by Thermo Fisher Scientific, USA;
  • LCMS Liquid chromatography
  • the specific experimental procedure was to prepare a sample solution of oil sample-toluene having a mass ratio of 1:9. Weigh a certain amount of the sample solution, add a certain amount of dispersant, stir with a magnetic stirrer for 30 min, transfer 2 mL of the sample solution containing the dispersant and 23 mL of n-heptane, and immediately transfer to the sample cell, using Turbiscan stability. An analyzer (Turbiscan Lab Stability Analyzer, manufactured by Formulaction, France) was used for the measurement. The experimental measurement temperature was 30 ° C, the scanning time was 3 h, and the scanning interval was 1 min.
  • X i is the average of the backscattered light intensity (or transmitted light intensity) obtained at different heights of each scanned sample cell
  • n is the number of scans, which is 181.
  • the ISP value reflects the degree of instability of the system, and the larger the value, the more unstable the system, the more easily the asphaltenes flocculate and settle. Define the degree of change in ISP value (C ISP ) to visually and quantitatively compare the extent of dispersion of dispersed asphaltenes, see equation (2):
  • ISP 0 is the ISP value of the sample before the addition of the dispersant
  • ISP i is the ISP value of the sample after the addition of the dispersant i. Therefore, only when C ISP ⁇ 0, the dispersant has the effect of dispersing and stabilizing the asphaltene, and the smaller the C ISP , the more remarkable the effect of the dispersant.
  • the example reaction is as follows:
  • the 1 H NMR spectrum of the intermediate compound 3 obtained in the first step of the reaction of Example 1 is shown in Fig. 1, and its liquid chromatography (LCMS) spectrum is shown in Fig. 2, and the infrared spectrum of the product polymer 5 is shown in Fig. 3. in.
  • LCMS liquid chromatography
  • the example reaction is as follows:
  • the example reaction is as follows:
  • the example reaction is as follows:
  • n (PIBSA) / n (TEA) 1: 2
  • PIBSA preheated to 160 ° C in a nitrogen atmosphere slowly added TEA while stirring, control the feed rate, after the completion of the addition reaction 3.5 hour.
  • the Tahe Vacuum Residue (THVR) (provided by Sinopec Institute of Petrochemical Technology, composition and properties as shown in Table 1 below) with boiling point above 540 °C was used as the test object to evaluate the above asphaltene dispersants L-01, L- 02, L-03, D-01, D-02, commercially available dispersant F110 (purchased from Croda), dodecylbenzenesulfonic acid (DBSA, purity 90%, lyon reagent) and Lubricating oil ashless dispersant polyisobutylene amide T154 (produced by Jinzhou Petrochemical Co., Ltd.) in the amount of addition (the ratio of additive mass to vacuum residue quality) of 50 ppm, 200 ppm, 500 ppm and 1000 ppm to n-heptane-toluene-vacuum residue system The dispersion effect of asphaltenes.

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Abstract

本发明公开了一种酯基聚合物、其制备方法及用途。本发明的酯基聚合物具有下式 (I) 所示的结构：其中，基团T表示所述酯基聚合物的主链；各基团B各自独立地选自O 或 S；各基团 R 各自独立地表示 C1-10 亚烃基；各基团A各自独立地选自 O、S 或NR"；各基团 R' 各自独立地表示 C1-10 亚烃基；各基团 Nb 各自独立地选自H或- R"'-B'H，其中同一氮原子上的两个 Nb 中至少一个为- R"'-B'H；各基团 R"各自独立地选自 H 或 C1-10 烃基；各基团 R"' 各自独立地表示 C1-10 亚烃基；各基团 B' 各自独立地选自O 或 S；各个y各自独立地表示 1-6 之间的整数；并且m为 1-10 之间的整数。当本发明的酯基聚合物用作分散剂和/或阻聚剂时，具有非常优异的分散和阻聚性能。

Description

一种酯基聚合物、其制备方法及用途 技术领域
本发明涉及一种聚合物，特别涉及一种适合用作分散剂和/或阻聚剂的酯基聚合物。
背景技术
沥青质一般被定义为不溶于正庚烷、而溶于甲苯的石油组分，是按溶解度定义的一类物质，它是重质油中相对分子质量最高，极性最强和最难加工的组分。沥青质的存在使得重质油具有胶体体系的特性，当温度、压力或组分发生变化而导致沥青质所处环境发生改变时，沥青质容易发生絮凝沉积，给石油的生产、储运和加工带来不利的影响。在石油的开采过程中，沥青质的絮凝沉积会导致岩石的渗透性降低、润湿性反转，造成永久性油藏损害，同时也会导致井管、分离器等外围设备的堵塞，使生产效率严重降低；在石油的运输储备过程中，沥青质的絮凝沉积会导致泵送的管路及其相关处理设备结垢，严重影响传输效率；在石油的加工过程中，沥青质作为生焦前驱物在热固体表面(如反应器器壁、加热炉炉管、换热器器壁)沉积，会造成催化剂的结焦失活或者装置的结焦、结垢，导致生产效率降低，给重质油加工和利用带来了困难。
阻止沥青质絮凝沉积最经济有效的方式之一是添加化学添加剂(分散剂和/或阻聚剂)。常见的化学添加剂包括烷基酚、烷基磺酸、烷基吡咯烷酮、烷基酚聚氧乙烯醚、脂肪酸酯多元醇、烷基酚醛树脂、油溶性聚合物以及新型离子液体等。对于化学添加剂的分散和阻聚效果，文献结论不尽相同，这可能与沥青质的种类和结构、溶剂条件及化学添加剂的评价方法有关。虽然各种化学添加剂已被油田使用多年，但仍有大量的研究工作在进行，其目的是找到更有效、更经济(价格低廉、原料易得的材料)、对人更安全、对环境更友好的化学添加剂。
现有技术中已知的沥青质分散剂例如专利CA 2029465C和CA 2075749C中公开的烷基酚-甲醛树脂与亲水-亲酯的乙烯基聚合物的组合。在美国专利US 4414035A和公开发表的论文D.L.Chang、H.S.Fogler(SPE论文第25185号，1993)及Francia Marcano(Energy&Fuels， 2015，29(5)：2813-2822)等中描述了十二烷基苯磺酸(DBSA)具有分散沥青质的性质。
本领域中仍然需要用作分散剂和/或阻聚剂，特别是用作沥青质分散剂和/或阻聚剂时，具有优异的分散和阻聚性能的新型材料。
发明内容
本发明满足了本领域的上述需求，提供了一种适合用作分散剂和/或阻聚剂，特别是用作沥青质分散剂和/或阻聚剂的新型的酯基聚合物、其制备方法及用途。
在一个方面，本发明提供了一种酯基聚合物，其具有下式(I)所示的结构：
Figure PCTCN2018087068-appb-000001
其中，
基团T表示所述酯基聚合物的主链；
各基团B彼此相同或不同，各自独立地选自O或S；
各基团R彼此相同或不同，各自独立地表示C 1-10亚烃基，各基团R任选地被选自烷氧基、羟基、氨基和巯基的基团取代；
各基团A彼此相同或不同，各自独立地选自O、S或NR″；
各基团R′彼此相同或不同，各自独立地表示C 1-10亚烃基，各基团R′任选地被选自烷氧基、羟基、氨基和巯基的基团取代；
各基团N b彼此相同或不同，各自独立地选自H或-R″′-B′H，其中同一氮原子上的两个N b中至少一个为-R″′-B′H；
各基团R″彼此相同或不同，各自独立地选自H或C 1-10烃基；
各基团R″′彼此相同或不同，各自独立地表示C 1-10亚烃基，各基团R″′任选地被选自烷氧基、羟基、氨基和巯基的基团取代；
各基团B′彼此相同或不同，各自独立地选自O或S；
各个y彼此相同或不同，各自独立地表示1-6之间的整数；并且
m为1-10之间的整数。
在优选的实施方式中，本发明酯基聚合物中的基团T表示的主链 选自聚烯烃、聚醚和聚酯。
在另一方面，本发明提供了一种酯基聚合物的制备方法，包括使母体聚合物与至少一种下式(II)所示的化合物进行酯化反应的步骤：
Figure PCTCN2018087068-appb-000002
其中，
所述母体聚合物指含有-COOH基团和/或
Figure PCTCN2018087068-appb-000003
基团的聚合物，
基团B选自O或S；
各基团R彼此相同或不同，各自独立地表示C 1-10亚烃基，各基团R任选地被选自烷氧基、羟基、氨基和巯基的基团取代；
各基团A彼此相同或不同，各自独立地选自O、S或NR″；
基团R′表示C 1-10亚烃基，基团R′任选地被选自烷氧基、羟基、氨基和巯基的基团取代；
各基团N b彼此相同或不同，各自独立地选自H或-R″′-B′H，其中至少一个为-R″′-B′H；
各基团R″彼此相同或不同，各自独立地选自H或C 1-10烃基；
各基团R″′彼此相同或不同，各自独立地表示C 1-10亚烃基，各基团R″′任选地被选自烷氧基、羟基、氨基和巯基的基团取代；
各基团B′彼此相同或不同，各自独立地选自O或S；并且
y表示1-6之间的整数。
在优选的实施方式中，本发明的制备方法进一步包括使至少一种下式(III)所示的化合物，
Figure PCTCN2018087068-appb-000004
其中：
各基团N b彼此相同或不同，各自独立地选自H或-R″′-B′H，其中至少一个为-R″′-B′H；且
各基团R″′彼此相同或不同，各自独立地表示C 1-10亚烃基，各基团R″′任选地被选自烷氧基、羟基、氨基和巯基的基团取代；
各基团B′彼此相同或不同，各自独立地选自O或S；
与至少一种下式(IVA)所示的化合物和/或至少一种下式(IVB)所示的化合物进行酰化反应生成至少一种式(II)所示化合物的步骤，
Figure PCTCN2018087068-appb-000005
其中：
各基团B彼此相同或不同，各自独立地选自O或S；
各基团R彼此相同或不同，各自独立地表示C 1-10亚烃基，各基团R任选地被选自烷氧基、羟基、氨基和巯基的基团取代；
各基团A彼此相同或不同，各自独立地选自O、S或NR″；
各基团R′彼此相同或不同，各自独立地表示C 1-10亚烃基，各基团R′任选地被选自烷氧基、羟基、氨基和巯基的基团取代；
各基团R″彼此相同或不同，各自独立地选自H或C 1-10烃基；并且
各个y彼此相同或不同，各自独立地表示1-6之间的整数。
在又一方面，本发明提供了根据本发明的酯基聚合物和/或按照本发明方法制备的酯基聚合物用作分散剂和/或阻聚剂的用途，特别是用作沥青质分散剂和/或阻聚剂的用途。
与现有材料相比，本发明的酯基聚合物用作分散剂和/或阻聚剂，特别是沥青质分散剂和/或阻聚剂时，显示出优异的分散和阻聚性能，例如更有效地减少或解决沥青质由于外在条件发生改变所导致的絮凝沉积现象。
附图说明
图1为实施例1制备的中间化合物3的 1HNMR谱图；
图2为所述中间化合物3的液质(LCMS)谱图；
图3为实施例1制备的产物聚合物5的红外谱图；
图4为实施例2制备的中间化合物7的 1HNMR谱图；
图5为实施例2制备的产物聚合物8的红外谱图；
图6为实施例3制备的产物聚合物10的红外谱图；
图7为对比例1制备的中间化合物13的 1HNMR谱图；
图8为对比例1制备的产物聚合物14的红外谱图；
图9为对比例2制备的产物聚合物D-02的红外谱图。
具体实施方式
以下对本发明的具体实施方式进行详细说明。应当理解的是，此处所描述的具体实施方式仅用于说明和解释本发明，并不用于限制本发明。
在本文中所披露的任何具体数值(包括数值范围的端点)都不限于该数值的精确值，而应当理解为还涵盖了接近该精确值的值。并且，对于所披露的数值范围而言，在该范围的端点值之间、端点值与范围内的具体点值之间，以及各具体点值之间可以任意组合而得到一个或多个新的数值范围，这些新的数值范围也应被视为在本文中具体公开。
在本文中提及的所有专利和非专利文献，包括但不限于教科书和期刊文章等，均通过引用方式全文并入本文。
在本文中，如无相反表示，所有聚合物的分子量均为数均分子量Mn。
在第一方面，本发明提供了一种酯基聚合物，其具有下式(I)所示的结构：
Figure PCTCN2018087068-appb-000006
其中，
基团T表示所述酯基聚合物的主链；
各基团B彼此相同或不同，各自独立地选自O或S，优选O；
各基团R彼此相同或不同，各自独立地表示C 1-10亚烃基，优选C 1-6直链或支链亚烷基，进一步优选C 1-4直链或支链亚烷基，各基团R任选地被选自烷氧基、羟基、氨基和巯基的基团取代，优选为未取代的；
各基团A彼此相同或不同，各自独立地选自O、S或NR″，优选O或S，更优选O；
各基团R′彼此相同或不同，各自独立地表示C 1-10亚烃基，优选C 1-6直链或支链亚烷基，进一步优选C 1-4直链或支链亚烷基，各基团R′任选地被选自烷氧基、羟基、氨基和巯基的基团取代，优选为未取代的；
各基团N b彼此相同或不同，各自独立地选自H或-R″′-B′H，其中同一氮原子上的两个N b中至少一个为-R″′-B′H，优选两个N b各自独立地为-R″′-B′H；
各基团R″彼此相同或不同，各自独立地选自H或C 1-10烃基，优选选自H或C 1-6直链或支链烷基，进一步优选选自H或C 1-4直链或支链烷基，最优选H；
各基团R″′彼此相同或不同，各自独立地表示C 1-10亚烃基，优选C 1-6直链或支链亚烷基，进一步优选C 1-4直链或支链亚烷基，各基团R″′任选地被选自烷氧基、羟基、氨基和巯基的基团取代，优选为未取代的；
各基团B′彼此相同或不同，各自独立地选自O或S，优选O；
各个y彼此相同或不同，各自独立地表示1-6之间的整数，优选1-3之间的整数，最优选1；并且
m为1-10之间的整数，优选1-5之间的整数，最优选2。
在本发明酯基聚合物的优选实施方式中，基团B表示O；各基团R彼此相同或不同，各自独立地表示C 1-6直链或支链亚烷基；各基团A彼此相同或不同，各自独立地选自O或S；各基团R′彼此相同或不同，各自独立地表示C 1-6直链或支链亚烷基；各基团N b彼此相同或不同，各自独立地表示-R″′-B′H；各基团R″′彼此相同或不同，各自独立地表示C 1-6直链或支链亚烷基；基团B′表示O；各个y彼此相同或不同，各自独立地表示1-3之间的整数；并且m为1-5之间的整数。
在本发明酯基聚合物的进一步优选的实施方式中，基团B表示O；各基团R彼此相同或不同，各自独立地表示C 1-4直链或支链亚烷基；基团A表示O；各基团R′彼此相同或不同，各自独立地表示C 1-4直链或支链亚烷基；各基团N b彼此相同或不同，各自独立地表示-R″′-B′H；各基团R″′彼此相同或不同，各自独立地表示C 1-4直链或支链亚烷基；基团B′表示O；y为1；并且m为2。
在优选的实施方式中，本发明酯基聚合物中的基团T表示的主链选自聚烯烃、聚醚和聚酯，优选聚烯烃，包括但不限于C 2-20烯烃的均聚物或共聚物，更优选C 2-10烯烃的均聚物或共聚物，例如聚乙烯、聚丙烯、聚丁烯、聚异丁烯、聚戊烯、聚己烯、聚辛烯、聚壬烯和聚癸烯。
在优选的实施方式中，本发明酯基聚合物的数均分子量为约600-10500，更优选约800-4500。
在第二方面，本发明提供了一种酯基聚合物的制备方法，包括使母体聚合物与至少一种下式(II)所示的化合物进行酯化反应的步骤：
Figure PCTCN2018087068-appb-000007
其中，
所述母体聚合物指含有-COOH基团和/或
Figure PCTCN2018087068-appb-000008
基团的聚合物，
基团B选自O或S，优选O；
各基团R彼此相同或不同，各自独立地表示C 1-10亚烃基，优选C 1-6直链或支链亚烷基，进一步优选C 1-4直链或支链亚烷基，各基团R任选地被选自烷氧基、羟基、氨基和巯基的基团取代，优选为未取代的；
各基团A彼此相同或不同，各自独立地选自O、S或NR″，优选O或S，更优选O；
基团R′表示C 1-10亚烃基，优选C 1-6直链或支链亚烷基，进一步优选C 1-4直链或支链亚烷基，基团R′任选地被选自烷氧基、羟基、氨基和巯基的基团取代，优选为未取代的；
各基团N b彼此相同或不同，各自独立地选自H或-R″′-B′H，其中至少一个为-R″′-B′H，优选各自独立地为-R″′-B′H；
各基团R″彼此相同或不同，各自独立地选自H或C 1-10烃基，优选选自H或C 1-6直链或支链烷基，进一步优选选自H或C 1-4直链或支链烷基，最优选H；
各基团R″′彼此相同或不同，各自独立地表示C 1-10亚烃基，优选 C 1-6直链或支链亚烷基，进一步优选C 1-4直链或支链亚烷基，各基团R″′任选地被选自烷氧基、羟基、氨基和巯基的基团取代，优选为未取代的；
各基团B′彼此相同或不同，各自独立地选自O或S，优选O；并且
y表示1-6之间的整数，优选1-3之间的整数，最优选1。
在优选的实施方式中，本发明的制备方法进一步包括使至少一种下式(III)所示的化合物，
Figure PCTCN2018087068-appb-000009
其中：
各基团N b彼此相同或不同，各自独立地选自H或-R″′-B′H，其中至少一个为-R″′-B′H，优选各自独立地为-R″′-B′H；且
各基团R″′彼此相同或不同，各自独立地表示C 1-10亚烃基，优选C 1-6直链或支链亚烷基，进一步优选C 1-4直链或支链亚烷基，各基团R″′任选地被选自烷氧基、羟基、氨基和巯基的基团取代，优选为未取代的；
各基团B′彼此相同或不同，各自独立地选自O或S，优选O；
与至少一种下式(IVA)所示的化合物和/或至少一种下式(IVB)所示的化合物进行酰化反应生成至少一种式(II)所示化合物的步骤，
Figure PCTCN2018087068-appb-000010
其中：
各基团B彼此相同或不同，各自独立地选自O或S，优选O；
各基团R彼此相同或不同，各自独立地表示C 1-10亚烃基，优选C 1-6直链或支链亚烷基，进一步优选C 1-4直链或支链亚烷基，各基团R任选地被选自烷氧基、羟基、氨基和巯基的基团取代，优选为未取代的；
各基团A彼此相同或不同，各自独立地选自O、S或NR″，优选O或S，更优选O；
各基团R′彼此相同或不同，各自独立地表示C 1-10亚烃基，优选C 1-6直链或支链亚烷基，进一步优选C 1-4直链或支链亚烷基，各基团R′任选地被选自烷氧基、羟基、氨基和巯基的基团取代，优选为未取代的；
各基团R″彼此相同或不同，各自独立地选自H或C 1-10烃基，优选选自H或C 1-6直链或支链烷基，进一步优选选自H或C 1-4直链或支链烷基，最优选H；并且
各个y彼此相同或不同，各自独立地表示1-6之间的整数，优选1-3之间的整数，最优选1。
在本发明制备方法的优选实施方式中，基团B表示O；各基团R彼此相同或不同，各自独立地表示C 1-6直链或支链亚烷基；各基团A彼此相同或不同，各自独立地选自O或S；各基团R′彼此相同或不同，各自独立地表示C 1-6直链或支链亚烷基；各基团N b彼此相同或不同，各自独立地表示-R″′-B′H；各基团R″′彼此相同或不同，各自独立地表示C 1-6直链或支链亚烷基；基团B′表示O；且各个y彼此相同或不同，各自独立地表示1-3之间的整数。
在本发明制备方法的进一步优选的实施方式中，基团B表示O；各基团R彼此相同或不同，各自独立地表示C 1-4直链或支链亚烷基；基团A表示O；各基团R′彼此相同或不同，各自独立地表示C 1-4直链或支链亚烷基；各基团N b彼此相同或不同，各自独立地表示-R″′-B′H；各基团R″′彼此相同或不同，各自独立地表示C 1-4直链或支链亚烷基；基团B′表示O；且y为1。
在优选的实施方式中，所述式(III)化合物选用醇胺、硫醇胺、或其混合物，优选包含两个羟基的醇胺、包含两个巯基的硫醇胺、或其混合物，更优选包含两个羟基的C1-C10醇胺、包含两个巯基的C1-C10硫醇胺、或其混合物，例如可以选用乙醇胺、丙醇胺、丁醇胺、戊醇胺、己醇胺、乙二醇胺、丙二醇胺、丁二醇胺、戊二醇胺、己二醇胺、乙硫醇胺、丙硫醇胺、丁硫醇胺、戊硫醇胺、己硫醇胺、乙二硫醇胺、丙二硫醇胺、丁二硫醇胺、戊二硫醇胺和己二硫醇胺中的一种或多种。
在优选的实施方式中，所述式(IVA)化合物选用含有羟基和羧基的醚类物质、含有巯基和羧基的醚类物质和含有胺基和羧基的醚类物质 中的一种或多种，优选亚烷基二醇与羟基酸的醚化产物、亚烷基二硫醇与羟基酸的醚化产物和醇胺与羟基酸的醚化产物中的一种或多种，更优选C1-C5亚烷基二醇与C1-C5羟基酸的醚化产物、C1-C5亚烷基二硫醇与C1-C5羟基酸的醚化产物和C1-C5醇胺与C1-C5羟基酸的醚化产物中的一种或多种，例如可以选用2-(2-羟基乙氧基)-乙酸、3-(2-羟基乙氧基)-丙酸、3-(2-羟基乙氧基)-丁酸、2-(3-羟基丙氧基)-乙酸、2-(4-羟基丁氧基)-丙酸、2-(2-羟基乙硫基)-乙酸、3-(2-羟基乙硫基)-丙酸、3-(2-羟基乙硫基)-丁酸、2-(3-羟基丙硫基)-乙酸和2-(4-羟基丁硫基)-丙酸中的一种或多种。
在优选的实施方式中，所述式(IVB)化合物选用氧杂内酯、硫杂内酯和氮杂内酯中的一种或多种，优选氧杂内酯；例如可以选用氧杂丙内酯、氧杂丁内酯(二氧六环二酮)、氧杂戊内酯、氧杂己内酯、氧杂庚内酯、氧杂辛内酯、硫杂丙内酯、硫杂丁内酯、硫杂戊内酯、硫杂己内酯、硫杂庚内酯、硫杂辛内酯、氮杂丙内酯、氮杂丁内酯、氮杂戊内酯、氮杂己内酯、氮杂庚内酯和氮杂辛内酯中的一种或多种。
在进一步优选的实施方式中，所述式(III)化合物选自如下通式(V)的化合物：
Figure PCTCN2018087068-appb-000011
其中，R 1和R 2可以相同或不同，分别独立地选自C1-C10亚烷基，优选C1-C6的亚烷基，更优选C1-C4的亚烷基，R 1和R 2任选地被选自烷氧基、羟基、氨基和巯基的基团取代，优选为未取代的。
在进一步优选的实施方式中，所述式(IVB)化合物选自如下通式(VI)的化合物：
Figure PCTCN2018087068-appb-000012
其中，R 3和R 4可以相同或不同，分别独立地选自H或C1-C8烷基，优选H或C1-C4烷基，其中所述烷基任选地被选自烷氧基、羟基、氨基和巯基的基团取代，优选为未取代的。
在优选的实施方式中，在式(III)化合物与式(IVA)和/或式(IVB)化合物的所述酰化反应中，式(III)化合物与式(IVA)和式(IVB)化合物的总量 之间的摩尔比为约1∶0.1-10，优选约1∶0.5-5，更优选约1∶0.9-1.1。进一步优选地，所述酰化反应的反应温度为约50-150℃，更优选约80-120℃；反应压力为约0.1-10MPa，更优选约0.1-5MPa；反应时间为约0.1h-10h，更优选约4h-8h。特别优选地，所述酰化反应的反应温度为约80-120℃；反应压力为约0.1-5MPa；且反应时间为约4h-8h。
在优选的实施方式中，在所述酰化反应中可通入惰性气体，更优选通入氮气。
在所述酰化反应中可加入溶剂，也可不加入溶剂。当选择加入溶剂时，可以加入丁烷、环丁烷、戊烷、环戊烷、已烷、环已烷、庚烷、正庚烷、辛烷、环辛烷、壬烷、十一烷、十二烷、苯、甲苯、二甲苯、异丙基苯、植物油、四氯化碳、二氯乙烷和液体石蜡中的一种或多种，优选甲苯和/或二甲苯。所述溶剂的量没有特别限制，优选为所述式(III)化合物质量的约10-200％。所述溶剂可在反应结束后以本领域人员所公知的方法脱除。
在所述酰化反应中可加入催化剂，也可不加入催化剂。当选择加入催化剂时，可以加入二氧化硅、白土、硅酸镁、氧化铝、硅胶和分子筛中的一种或多种，优选加入二氧化硅。所述催化剂的量优选为所述式(III)化合物质量的约0.1-20％，优选约0.5％-2％。
在优选的实施方式中，所述含有-COOH基团和/或
Figure PCTCN2018087068-appb-000013
基团的聚合物为分子中含有q个-COOH基团和/或
Figure PCTCN2018087068-appb-000014
基团的聚合物，其中q表示聚合物中-COOH基团和/或
Figure PCTCN2018087068-appb-000015
基团的总数与聚合物分子数的比值，因其为平均值，故可以为非整数。q的优选取值范围是1≤q≤10，更优选1≤q≤5。进一步优选地，所述聚合物为聚烯烃、聚醚或聚酯。特别优选地，所述含有-COOH基团和/或
Figure PCTCN2018087068-appb-000016
基团的聚合物的数均分子量为约500-10000，更优选约600-6000，进一步优选约600-3000。
在优选的实施方式中，在所述含有-COOH基团和/或
Figure PCTCN2018087068-appb-000017
基团的聚合物与所述式(II)化合物的酯化反应中，以-COOH基团和/或
Figure PCTCN2018087068-appb-000018
基团计算，所述聚合物与式(II)化合物的摩尔比为约1∶0.1-10，优选约1∶0.5-5，更优选约1∶0.9-1.1。进一步优选地，所述酯化反应的反应温度为约100-300℃，更优选约120-200℃；反应压力为约0.1-10MPa，更优选约0.1-5MPa；反应时间为约0.1h-10h，更优选约2h-8h。特别优选地，所述酯化反应的反应温度为约120-200℃；反应压力为约0.1-5MPa；且反应时间为约2h-8h。
在优选的实施方式中，在所述酯化反应中可通入惰性气体，更优选通入氮气。
在所述酯化反应中可加入溶剂，也可不加入溶剂。当选择加入溶剂时，可以加入丁烷、环丁烷、戊烷、环戊烷、已烷、环已烷、庚烷、正庚烷、辛烷、环辛烷、壬烷、十一烷、十二烷、苯、甲苯、二甲苯、异丙基苯、植物油、四氯化碳、二氯乙烷和液体石蜡中的一种或多种。所述溶剂的量没有特别限制，优选为所述含有-COOH基团和/或
Figure PCTCN2018087068-appb-000019
基团的聚合物质量的约10-200％。所述溶剂可在反应结束后以本领域人员所公知的方法脱除。
在所述酯化反应中可加入催化剂，也可不加入催化剂。当选择加入催化剂时，可以加入二氧化硅、白土、硅酸镁、氧化铝、硅胶和分子筛中的一种或多种，优选加入二氧化硅。所述催化剂的量优选为所述含有-COOH基团和/或
Figure PCTCN2018087068-appb-000020
基团的聚合物质量的约0.1-20％，更优选约0.5％-2％。
在优选的实施方式中，所述含有-COOH基团和/或
Figure PCTCN2018087068-appb-000021
基团的聚合物为含有-C＝C-键的聚合物与烯基酸和/或烯基酸酐进行加成反应的产物，更优选分子中含有u个-C＝C-键的聚合物与烯基酸和/或烯基酸酐进行加成反应的产物，其中所述的u表示聚合物中-C＝C-基团的总数与聚合物分子数的比值，因其为平均值，故可以为非整数。u的优选取值范围是1≤u≤10，更优选地1≤u≤5。进一步优选地，所述聚合物为分子中含有u个-C＝C-键的聚烯烃、聚醚和/或聚酯与烯基酸和/或烯基酸酐进行加成反应的产物。
在进一步优选的实施方式中，所述含有-C＝C-键的聚合物为分子中含有1-2个-C＝C-键的聚合物，更优选分子中含有1-2个-C＝C-键的聚烯烃，进一步优选烯烃聚合后分子中含有一个-C＝CH 2键的聚α-烯烃。特别地，所述含有1-2个-C＝C-键的聚烯烃优选C 2-20烯烃的均聚物或共聚物，更优选C 2-20α-烯烃的聚合物。
特别优选地，所述含有-C＝C-键的聚合物的数均分子量为约500-10000，更优选约600-6000，进一步优选约600-3000。
在进一步优选的实施方式中，所述的烯基酸和/或烯基酸酐为C 3-10烯基酸和/或烯基酸酐，更优选C 4-10烯基二酸和/或烯基二酸酐，例如可以选用丙烯酸、丁烯酸、戊烯酸、己烯酸、庚烯酸、辛烯酸、壬烯酸、癸烯酸、丁烯二酸、戊烯二酸、己烯二酸、庚烯二酸、辛烯二酸、壬烯二酸、癸烯二酸、马来酸酐、丁烯二酸酐、戊烯二酸酐、己烯二酸酐、庚烯二酸酐、辛烯二酸酐、壬烯二酸酐和癸烯二酸酐中的一种或多种。
在进一步优选的实施方式中，所述含有-C＝C-键的聚合物与所述烯基酸和/或烯基酸酐之间的摩尔比(以-C＝C-键计算)为约1∶0.1-10，优选约1∶0.5-5，更优选约1∶0.9-1.1；所述含有-C＝C-键的聚合物与所述烯基酸和/或烯基酸酐之间的反应温度为约100-350℃，更优选约200-300℃；反应压力为约0.1-10MPa，更优选约0.1-5MPa；反应时间为约0.1h-10h，更优选约0.5h-10h。进一步优选地，所述含有-C＝C-键的聚合物与所述烯基酸和/或烯基酸酐之间的摩尔比(以-C＝C-键计算)为约1∶0.9-1.1；反 应温度为约200-300℃；反应压力为约0.1-5MPa；反应时间为约0.5h-10h。特别优选地，在反应过程中通入惰性气体，更优选通入氮气。
所述含有-C＝C-键的聚合物与所述烯基酸和/或烯基酸酐之间的反应中可加入溶剂，也可不加入溶剂。当选择加入溶剂时，可以加入水、DMF、NMP、丙酮、DMSO、丁烷、环丁烷、戊烷、环戊烷、已烷、环已烷、庚烷、正庚烷、辛烷、环辛烷、壬烷、十一烷、十二烷、苯、甲苯、二甲苯、异丙基苯、植物油、四氯化碳和二氯乙烷中的一种或多种，优选甲苯和/或二甲苯。所述溶剂的量没有特别限制，优选为所述含有-C＝C-键的聚合物质量的约10-200％。所述溶剂可在反应结束后以本领域人员所公知的方法脱除。
所述含有-C＝C-键的聚合物与所述烯基酸和/或烯基酸酐之间的反应中可加入催化剂，也可不加入催化剂。当选择加入催化剂时，可以加入二氧化硅、白土、硅酸镁、氧化铝、硅胶和分子筛中的一种或多种，优选加入二氧化硅。所述催化剂的量优选为所述含有-C＝C-键的聚烯烃质量的约0.1-20％，更优选约0.5％-2％。
根据本发明，在所述酯基聚合物的制备方法结束后，通过常规已知的任何方式从最终获得的反应混合物中除去催化剂和可能存在的溶剂后，即获得酯基聚合物。
本发明的酯基聚合物适合于用作分散剂和/或阻聚剂，特别适于用作沥青质分散剂和/或阻聚剂。
在第三方面，本发明还提供了根据本发明的酯基聚合物和/或按照本发明方法制备的酯基聚合物用作分散剂和/或阻聚剂的用途，特别是用作沥青质分散剂和/或阻聚剂的用途。
当本发明的酯基聚合物用作分散剂和/或阻聚剂特别是沥青质分散剂和/或阻聚剂时，具有非常优异的分散和阻聚性能。
在特别优选的实施方式中，本发明提供了以下的技术方案：
方案1.一种酯基聚合物，其具有下式(I)所示的结构：
Figure PCTCN2018087068-appb-000022
其中，
基团T表示所述酯基聚合物的主链；
各基团B彼此相同或不同，各自独立地选自O或S，优选O；
各基团R彼此相同或不同，各自独立地表示C 1-10亚烃基，优选C 1-6直链或支链亚烷基，进一步优选C 1-4直链或支链亚烷基；
各基团A彼此相同或不同，各自独立地选自O、S或NH，优选O或S，更优选O；
各基团R′彼此相同或不同，各自独立地表示C 1-10亚烃基，优选C 1-6直链或支链亚烷基，进一步优选C 1-4直链或支链亚烷基；
各基团N b彼此相同或不同，各自独立地选自H或-R″′-B′H，其中同一重复单元内，即同一氮原子上，的两个N b中至少一个为-R″′-B′H，更优选两个N b各自独立地为-R″′-B′H；
各基团R″′彼此相同或不同，各自独立地表示C 1-10亚烃基，优选C 1-6直链或支链亚烷基，进一步优选C 1-4直链或支链亚烷基；
各基团B′彼此相同或不同，各自独立地选自O或S，优选O；
各个y彼此相同或不同，各自独立地表示1-6之间的整数，优选1-3之间的整数，最优选1；并且
m为1-10之间的整数，优选1-5之间的整数，最优选2。
方案2.按照方案1所述的酯基聚合物，其特征在于，基团T表示的主链选自聚烯烃、聚醚和聚酯中的一种或多种，优选聚烯烃。
方案3.按照方案2所述的酯基聚合物，其特征在于，所述聚烯烃为C 2-20烯烃的均聚物或共聚物。
方案4.按照方案1-3中任一项所述的酯基聚合物，其特征在于，
基团T表示聚烯烃链；
基团B表示O；
各基团R彼此相同或不同，各自独立地表示C 1-6直链或支链亚烷基；
各基团A彼此相同或不同，各自独立地选自O或S；
各基团R′彼此相同或不同，各自独立地表示C 1-6直链或支链亚烷基；
各基团N b彼此相同或不同，各自独立地表示-R″′-B′H；
各基团R″′彼此相同或不同，各自独立地表示C 1-6直链或支链亚烷基；
基团B′表示O；
各个y彼此相同或不同，各自独立地表示1-3之间的整数；并且
m为1-5之间的整数。
方案5.按照方案4所述的酯基聚合物，其特征在于，
基团T表示聚烯烃链；
基团B表示O；
各基团R彼此相同或不同，各自独立地表示C 1-4直链或支链亚烷基；
基团A表示O；
各基团R′彼此相同或不同，各自独立地表示C 1-4直链或支链亚烷基；
各基团N b彼此相同或不同，各自独立地表示-R″′-B′H；
各基团R″′彼此相同或不同，各自独立地表示C 1-4直链或支链亚烷基；
基团B′表示O；
y为1；并且
m为2。
方案6.按照方案1-5中任一项所述的酯基聚合物，其特征在于，所述酯基聚合物的数均分子量为约600-10500，优选约800-4500。
方案7.一种酯基聚合物的制备方法，包括使母体聚合物与下式(II)所示的化合物进行酯化反应的步骤：
Figure PCTCN2018087068-appb-000023
其中，
所述母体聚合物指含有-COOH基团和/或
Figure PCTCN2018087068-appb-000024
基团的聚合物；
基团B选自O或S，优选O；
各基团R彼此相同或不同，各自独立地表示C 1-10亚烃基，优选C 1-6直链或支链亚烷基，进一步优选C 1-4直链或支链亚烷基；
各基团A彼此相同或不同，各自独立地选自O、S或NH，优选O或S，更优选O；
基团R′表示C 1-10亚烃基，优选C 1-6直链或支链亚烷基，进一步优选C 1-4直链或支链亚烷基；
各基团N b彼此相同或不同，各自独立地选自H或-R″′-B′H，其中至少一个为-R″′-B′H，更优选各自独立地为-R″′-B′H；
各基团R″′彼此相同或不同，各自独立地表示C 1-10亚烃基，优选C 1-6直链或支链亚烷基，进一步优选C 1-4直链或支链亚烷基；
各基团B′彼此相同或不同，各自独立地选自O或S，优选O；并且
y表示1-6之间的整数，优选1-3之间的整数，最优选1。
方案8.按照方案7所述的制备方法，进一步包括使下式(III)所示的化合物，
Figure PCTCN2018087068-appb-000025
其中：
各基团N b彼此相同或不同，各自独立地选自H或-R″′-B′H，其中至少一个为-R″′-B′H，更优选各自独立地为-R″′-B′H；
各基团R″′彼此相同或不同，各自独立地表示C 1-10亚烃基，优选C 1-6直链或支链亚烷基，进一步优选C 1-4直链或支链亚烷基；
各基团B′彼此相同或不同，各自独立地选自O或S，优选O；
与下式(IVA)所示的化合物和/或下式(IVB)所示的化合物进行酰化反应生成式(II)所示化合物的步骤，
Figure PCTCN2018087068-appb-000026
其中：
各基团B彼此相同或不同，各自独立地选自O或S，优选O；
各基团R彼此相同或不同，各自独立地表示C 1-10亚烃基，优选C 1-6直链或支链亚烷基，进一步优选C 1-4直链或支链亚烷基；
各基团A彼此相同或不同，各自独立地选自O、S或NH，优选O或S，更优选O；
各基团R′彼此相同或不同，各自独立地表示C 1-10亚烃基，优选C 1-6直链或支链亚烷基，进一步优选C 1-4直链或支链亚烷基；并且
各个y彼此相同或不同，各自独立地表示1-6之间的整数，优选1-3之间的整数，最优选1。
方案9.按照方案7或8所述的方法，其特征在于，基团B表示O；各基团R彼此相同或不同，各自独立地表示C 1-6直链或支链亚烷基；各基团A彼此相同或不同，各自独立地选自O或S；各基团R′彼此相同或不同，各自独立地表示C 1-6直链或支链亚烷基；各基团N b彼此相同或不同，各自独立地表示-R″′-B′H；各基团R″′彼此相同或不同，各自独立地表示C 1-6直链或支链亚烷基；基团B′表示O；且各个y彼此相同或不同，各自独立地表示1-3之间的整数。
方案10.按照方案9所述的方法，其特征在于，基团B表示O；各基团R彼此相同或不同，各自独立地表示C 1-4直链或支链亚烷基；基团A表示O；各基团R′彼此相同或不同，各自独立地表示C 1-4直链或支链亚烷基；各基团N b彼此相同或不同，各自独立地表示-R″′-B′H；各基团R″′彼此相同或不同，各自独立地表示C 1-4直链或支链亚烷基；基团B′表示O；且y为1。
方案11.按照方案8-10中任一项所述的方法，其特征在于，所述式(III)化合物为醇胺和/或硫醇胺，优选包含两个羟基的醇胺和/或包含两个巯基的硫醇胺，更优选包含两个羟基的C1-C10醇胺和/或包含两个巯基的C1-C10硫醇胺。
方案12.按照方案8-11中任一项所述的方法，其特征在于，所述式(IVA)化合物选自含有羟基和羧基的醚类物质、含有巯基和羧基的醚类物质和含有胺基和羧基的醚类物质中的一种或多种，优选亚烷基二醇与羟基酸的醚化产物、亚烷基二硫醇与羟基酸的醚化产物和醇胺与羟基酸的醚化产物中的一种或多种，更优选C1-C5亚烷基二醇与C1-C5羟基酸的醚化产物、C1-C5亚烷基二硫醇与C1-C5羟基酸的醚化产物和C1-C5醇胺与C1-C5羟基酸的醚化产物中的一种或多种。
方案13.按照方案8-12中任一项所述的方法，其特征在于，所述式(IVB)化合物选自氧杂内酯、硫杂内酯和氮杂内酯中的一种或多种，优选氧杂内酯。
方案14.按照方案8-13中任一项所述的方法，其特征在于，所述式(III)化合物选自乙醇胺、丙醇胺、丁醇胺、戊醇胺、己醇胺、乙二醇胺、丙二醇胺、丁二醇胺、戊二醇胺、己二醇胺、乙硫醇胺、丙硫醇胺、丁硫醇胺、戊硫醇胺、己硫醇胺、乙二硫醇胺、丙二硫醇胺、丁二硫醇胺、戊二硫醇胺和己二硫醇胺中的一种或多种；所述式(IVA)化合物选自2-(2-羟基乙氧基)-乙酸、3-(2-羟基乙氧基)-丙酸、3-(2-羟基乙氧基)-丁酸、2-(3-羟基丙氧基)-乙酸、2-(4-羟基丁氧基)-丙酸、2-(2-羟基乙硫基)-乙酸、3-(2-羟基乙硫基)-丙酸、3-(2-羟基乙硫基)-丁酸、2-(3-羟基丙硫基)-乙酸和2-(4-羟基丁硫基)-丙酸中的一种或多种；以及，所述式(IVB)化合物选自氧杂丙内酯、氧杂丁内酯(二氧六环二酮)、氧杂戊内酯、氧杂己内酯、氧杂庚内酯、氧杂辛内酯、硫杂丙内酯、硫杂丁内酯、硫杂戊内酯、硫杂己内酯、硫杂庚内酯、硫杂辛内酯、氮杂丙内酯、氮杂丁内酯、氮杂戊内酯、氮杂己内酯、氮杂庚内酯和氮杂辛内酯中的一种或多种。
方案15.按照方案8-13中任一项所述的方法，其特征在于，所述式(III)化合物选自如下通式(V)的化合物：
Figure PCTCN2018087068-appb-000027
其中，R 1和R 2可以相同或不同，分别独立地选自C1-C10亚烷基，优选C1-C4的亚烷基。
方案16.按照方案8-13或15中任一项所述的方法，其特征在于，所述式(IVB)化合物选自如下通式(VI)的化合物：
Figure PCTCN2018087068-appb-000028
其中，R 3和R 4可以相同或不同，分别独立地选自H或C1-C10烷基，优选H或C1-C4烷基。
方案17.按照方案7-16中任一项所述的方法，其特征在于，所述 含有-COOH基团和/或
Figure PCTCN2018087068-appb-000029
基团的聚合物为分子中含有q个-COOH基团和/或
Figure PCTCN2018087068-appb-000030
基团的聚合物，其中q表示聚合物中-COOH基团和/或
Figure PCTCN2018087068-appb-000031
基团的总数与聚合物分子数的比值，1≤q≤10，优选1≤q≤5，特别优选地所述聚合物为聚烯烃、聚醚或聚酯。
方案18.按照方案7-17中任一项所述的方法，其特征在于，所述含有-COOH基团和/或
Figure PCTCN2018087068-appb-000032
基团的聚合物的数均分子量为约500-10000，优选约600-6000，进一步优选约600-3000。
方案19.按照方案8-18中任一项所述的方法，其特征在于，在式(III)化合物与式(IVA)和/或式(IVB)化合物的酰化反应中，式(III)化合物与式(IVA)和式(IVB)化合物总量之间的摩尔比为约1∶0.1-10，优选约1∶0.5-5，更优选约1∶0.9-1.1；反应温度为约50-150℃，优选约80-120℃；反应压力为约0.1-10MPa，优选约0.1-5MPa；反应时间为约0.1h-10h，优选约4h-8h。
方案20.按照方案7-19中任一项所述的方法，其特征在于，在所述含有-COOH基团和/或
Figure PCTCN2018087068-appb-000033
基团的聚合物与所述式(II)化合物的酯化反应中，以-COOH基团和/或
Figure PCTCN2018087068-appb-000034
基团计算，所述聚合物与式(II)化合物的摩尔比为约1∶0.1-10，优选约1∶0.5-5，更优选约1∶0.9-1.1；反应温度为约100-300℃，优选约120-200℃；反应压力为约0.1-10MPa，优选约0.1-5MPa；反应时间为约0.1h-10h，优选约2h-8h。
方案21.按照方案7-20中任一项所述的方法，其特征在于，所述含有-COOH基团和/或
Figure PCTCN2018087068-appb-000035
基团的聚合物为含有-C＝C-键的聚合 物与烯基酸和/或烯基酸酐进行加成反应的产物，优选分子中含有u个-C＝C-键的聚合物与烯基酸和/或烯基酸酐进行加成反应的产物，进一步优选分子中含有u个-C＝C-键的聚烯烃、聚醚和/或聚酯与烯基酸和/或烯基酸酐进行加成反应的产物，其中u表示聚合物中-C＝C-基团的总数与聚合物分子数的比值，1≤u≤10，优选地1≤u≤5。
方案22.按照方案21所述的方法，其特征在于，所述含有-C＝C-键的聚合物为分子中含有1-2个-C＝C-键的聚合物，更优选分子中含有1-2个-C＝C-键的聚烯烃，进一步优选分子中含有一个-C＝CH 2键的聚α-烯烃。
方案23.按照方案21或22所述的方法，其特征在于，所述含有-C＝C-键的聚合物的数均分子量为约500-10000，更优选约600-6000，进一步优选约600-3000。
方案24.按照方案21-23中任一项所述的方法，其特征在于，所述含有-C＝C-键的聚烯烃选自C 2-20烯烃的均聚物或共聚物，优选C 2-20α-烯烃的聚合物。
方案25.按照方案21-24中任一项所述的方法，其特征在于，所述的烯基酸和/或烯基酸酐为C 3-10烯基酸和/或烯基酸酐，更优选C 4-10烯基二酸和/或烯基二酸酐。
方案26.按照方案21-25中任一项所述的方法，其特征在于，所述的烯基酸和/或烯基酸酐选自丙烯酸、丁烯酸、戊烯酸、己烯酸、庚烯酸、辛烯酸、壬烯酸、癸烯酸、丁烯二酸、戊烯二酸、己烯二酸、庚烯二酸、辛烯二酸、壬烯二酸、癸烯二酸、马来酸酐、丁烯二酸酐、戊烯二酸酐、己烯二酸酐、庚烯二酸酐、辛烯二酸酐、壬烯二酸酐和癸烯二酸酐中的一种或多种。
方案27.方案1-6中任一项所述的酯基聚合物和/或由方案7-26中任一项所述的方法制备得到的酯基聚合物用作分散剂和/或阻聚剂的用途，特别是用作沥青质分散剂和/或阻聚剂的用途。
实施例
下面将结合实施例对本发明予以进一步说明，但并不因此而限制 本发明。
试剂和仪器
本申请实施例中所用的试剂和仪器如下：
二乙醇胺：分析纯(standard 98％)，购自北京偶合科技有限公司；
二异丙醇胺：分析纯(standard 98％)，购自北京偶合科技有限公司；
三乙醇胺(TEA)：分析纯(standard 98％)，购自北京偶合科技有限公司；
1，4-二氧六环-2-酮：分析纯(standard 98％)，购自北京偶合科技有限公司；
戊内酯：分析纯(standard 98％)，购自北京偶合科技有限公司；
聚异丁烯马来酸酐(n＝15，Mn＝994)：南京扬子石化-巴斯夫有限责任公司产品；以及
聚异丁烯马来酸酐(n＝18，Mn＝1162)：南京扬子石化-巴斯夫有限责任公司产品。
1H NMR谱图：采用Bruker公司的布鲁克AVANCE III HD系列核磁共振(NMR)波谱仪得到；
红外谱图：采用美国Thermo Fisher Scientific公司生产的Nicolet 6700傅里叶变换红外光谱仪得到；
液质(LCMS)谱图：使用岛津公司的日本岛津液相色谱质谱联用仪LCMS-2020，采用ELSD检测器得到。
测试方法
在以下实施例中，采用了ASTM D7061-2012的制样方法及文献“化学添加剂对沥青质的稳定分散效果”，李诚等，石油学报(石油加工)，2016，32(5)，1005-1012页，中记载的沥青质化学添加剂的评价方法对所测试的各分散剂的分散效果进行评价。
具体的实验过程为：制备质量比为1∶9的油样-甲苯的样品溶液。称取一定量的该样品溶液，加入一定量的分散剂，利用磁力搅拌器搅拌30min，移取2mL含有分散剂的样品溶液与23mL正庚烷混合，立即转移至样品池中，利用Turbiscan稳定性分析仪(Turbiscan Lab稳定 性分析仪，法国Formulaction公司生产)进行测量。实验测定温度为30℃，扫描时间为3h，扫描间隔为1min。
定义3h内光强度的变化程度为ISP，见式(1)：
Figure PCTCN2018087068-appb-000036
式中：X i为每次扫描样品池不同高度处所得背散射光光强度(或透射光强度)的平均值；X T为X i的平均值，即X T＝(X 1+X 2+…+X n)/n；n为扫描次数，为181。
ISP值反映了体系不稳定的程度，其值越大，表明体系越不稳定，沥青质越容易絮凝沉降。定义ISP值变化程度(C ISP)，来直观定量地比较分散剂分散稳定沥青质的程度，见式(2)：
Figure PCTCN2018087068-appb-000037
式中：ISP 0为加入分散剂前样品的ISP值，ISP i为加入分散剂i后样品的ISP值。因此，仅当C ISP＜0时，分散剂才具有分散稳定沥青质的效果，且C ISP越小，分散剂的效果越显著。
文献结果表明当样品的ISP＜3，或C ISP＜-75％时，样品分层不明显，说明样品中沥青质浓度低或者分散剂能基本分散烃混合物中的沥青质沉淀。
实施例1根据本发明的酯基聚合物的制备
将10.5克的二乙醇胺(化合物1)和10.2克的1，4-二氧六环-2-酮(化合物2)均匀混合后加入到50毫升的圆底烧瓶中，加热到100℃反应6个小时，加热过程中化合物1和2处于熔融状态，冷却静置得到20克的N，N-二-(2-羟乙基)-2-羟乙氧基乙酰胺(中间化合物3)无色油状物，不需要纯化，直接用于下一步反应。
把相对于中间化合物3为0.5当量的聚异丁烯马来酸酐(化合物4，n＝15，Mn＝994)加入到50毫升的圆底烧瓶中，先通氮气5分钟，然后加热到160℃，在160℃下搅拌30分钟，将中间化合物3加入到该溶液中，在160℃下继续反应3.5小时，冷却到室温得产物聚合物5，即黄色油状物L-01。
示例反应式如下：
Figure PCTCN2018087068-appb-000038
实施例1第一步反应所得的中间化合物3的 1HNMR谱图显示在图1中，其液质(LCMS)谱图显示在图2中，产物聚合物5的红外谱图则显示在图3中。由图1和图2可见，反应的转化率很高，第一步反应结束后，中间化合物3的收率近99％。
实施例2根据本发明的酯基聚合物的制备
将13.3克的二异丙醇胺(化合物6)和10.2克的1，4-二氧六环-2-酮(化合物2)均匀混合后加入到50毫升的圆底烧瓶中，加热到100℃反应6个小时，加热过程中化合物1和2处于熔融状态，冷却静置得到23克的N，N-二-(2-羟异丙基)-2-羟乙氧基乙酰胺(中间化合物7)无色油状物，不需要纯化，直接用于下一步反应。
把相对于中间化合物7为0.5当量的聚异丁烯马来酸酐PIBSA(化合物4，n＝15，Mn＝994)加入到50毫升的圆底烧瓶中，先通氮气5分钟，然后加热到160℃，在160℃下搅拌30分钟，将中间化合物7加入到该溶液中，在160℃下继续反应3.5小时，冷却到室温得产物聚合物8，即黄色油状物L-03。
示例反应式如下：
Figure PCTCN2018087068-appb-000039
实施例2制备的中间化合物7的 1HNMR谱图显示在图4中，产物聚合物8的红外谱图则显示在图5中。
实施例3根据本发明的酯基聚合物的制备
将10.5克的二乙醇胺(化合物1)和10.2克的1，4-二氧六环-2-酮(化合物2)均匀混合后加入到50毫升的圆底烧瓶中，加热到100℃反应6个小时，加热过程中化合物1和2处于熔融状态，冷却静置得到20克的N，N-二-(2-羟甲基)-2-羟乙氧基乙酰胺(中间化合物3)无色油状物，不需要纯化，直接用于下一步反应。
把相对于中间化合物3为0.5当量的聚异丁烯马来酸酐(化合物9，n＝18，Mn＝1162)加入到50毫升的圆底烧瓶中，先通氮气5分钟，然后加热到160℃，在160℃下搅拌30分钟，将中间化合物3加入到该溶液中，在160℃下继续反应3.5小时，冷却到室温得产物聚合物10，即黄色油状物L-02。
示例反应式如下：
Figure PCTCN2018087068-appb-000040
实施例3制备的产物聚合物10的红外谱图显示在图6中。
对比例1非本发明的酯基聚合物的制备
将10.5克的二乙醇胺(化合物1)和10.0克的戊内酯(化合物11)均匀混合后加入到50毫升的圆底烧瓶中，加热到100℃反应6个小时，加热过程中化合物1和2处于熔融状态，冷却静置得到20克的5-羟基-N，N-二-(2-羟乙基)-戊酰胺(中间化合物13)无色油状物，不需要纯化，直接用于下一步反应。
把相对于中间化合物13为0.5当量的聚异丁烯马来酸酐(化合物4，n＝15，Mn＝994)加入到50毫升的圆底烧瓶中，先通氮气5分钟，然后加热到160℃，在160℃下搅拌30分钟，将中间化合物13加入到该溶液中，在160℃下继续反应3.5小时，冷却到室温得产物聚合物14，即黄色油状物D-01。
示例反应式如下：
Figure PCTCN2018087068-appb-000041
对比例1制备的中间化合物13的 1HNMR谱图显示在图7中，产物聚合物14的红外谱图则显示在图8中。
对比例2非本发明的酯基聚合物的制备
参照文献“聚异丁烯丁二酸醇胺绿色合成及应用研究”，程刘锁，硕士学位论文，南京理工大学，2014年，第28页倒数第二段，将聚异丁烯马来酸酐PIBSA(化合物4，n＝15，Mn＝994)与2倍当量的三乙醇胺(TEA)进行酯化反应得到产物聚合物D-02。
具体反应条件为：n(PIBSA)/n(TEA)＝1∶2，在氮气氛围中，将PIBSA预热至160℃，边搅拌边缓慢加入TEA，控制加料速度，滴加完成后 保温反应3.5小时。
对比例2制备的产物聚合物D-02的红外谱图显示在图9中。
实施例4分散性能测试
以沸点高于540℃的塔河减压渣油(THVR)(中国石化石油化工科学研究院提供，组成和性质见下表1)为测试对象，评价上述沥青质分散剂L-01、L-02、L-03、D-01、D-02、市售分散剂F110(购自英国禾大(Croda)公司)、十二烷基苯磺酸(DBSA，纯度为90％，百灵威试剂)和润滑油无灰分散剂聚异丁烯酰胺T154(锦州石化生产)在添加量(添加剂质量与减压渣油质量之比)为50ppm、200ppm、500ppm和1000ppm时对正庚烷-甲苯-减压渣油体系中沥青质的分散效果。
空白试验及加入添加剂后的试验结果如表2所示。
表1测试用塔河减压渣油(THVR)的组成和性质
Figure PCTCN2018087068-appb-000042
表2各分散剂的分散效率评价结果(含空白试验)
Figure PCTCN2018087068-appb-000043
Figure PCTCN2018087068-appb-000044
对于加入化学添加剂后的样品，当ISP＜3，且C ISP＜-75％时，样品无沉淀产生。由表2的测试结果可以看到，相同添加量下本发明的沥青质分散剂的C ISP值均小于-75％，且低添加浓度时(如50ppm)C ISP值明显小于对比例，说明本发明的分散剂能够更有效地分散烃混合物中的沥青质沉淀。
在上文的说明书中，已经参照特定的实施方式描述了本发明的构思。然而，本领域技术人员可以理解，在不脱离所附的权利要求中限定的本发明范围的情况下可以做出各种修改和变更。因此，说明书和附图应认为是说明性的，而不是限制性的，并且所有这类修改和变更应当涵盖在本发明的范围之内。
可以理解，本文为清楚起见以独立的多个实施方式的形式描述的某些特征也可以作为组合提供在单一的实施方式中。相反，为简要起见以单一实施方式的形式描述的多个不同特征也可以单独地或以任何子组合的形式提供。

Claims (19)

  1. 一种酯基聚合物，其具有下式(I)所示的结构：
    Figure PCTCN2018087068-appb-100001
    其中，
    基团T表示所述酯基聚合物的主链；
    各基团B彼此相同或不同，各自独立地选自O或S，优选O；
    各基团R彼此相同或不同，各自独立地表示C 1-10亚烃基，优选C 1-6直链或支链亚烷基，进一步优选C 1-4直链或支链亚烷基，各基团R任选地被选自烷氧基、羟基、氨基和巯基的基团取代；
    各基团A彼此相同或不同，各自独立地选自O、S或NR″，优选O或S，更优选O；
    各基团R′彼此相同或不同，各自独立地表示C 1-10亚烃基，优选C 1-6直链或支链亚烷基，进一步优选C 1-4直链或支链亚烷基，各基团R′任选地被选自烷氧基、羟基、氨基和巯基的基团取代；
    各基团N b彼此相同或不同，各自独立地选自H或-R″′-B′H，其中同一氮原子上的两个N b中至少一个为-R″′-B′H，优选两个N b各自独立地为-R″′-B′H；
    各基团R″彼此相同或不同，各自独立地选自H或C 1-10烃基，优选选自H或C 1-6直链或支链烷基，进一步优选选自H或C 1-4直链或支链烷基，最优选H；
    各基团R″′彼此相同或不同，各自独立地表示C 1-10亚烃基，优选C 1-6直链或支链亚烷基，进一步优选C 1-4直链或支链亚烷基，各基团R″′任选地被选自烷氧基、羟基、氨基和巯基的基团取代；
    各基团B′彼此相同或不同，各自独立地选自O或S，优选O；
    各个y彼此相同或不同，各自独立地表示1-6之间的整数，优选1-3之间的整数，最优选1；并且
    m为1-10之间的整数，优选1-5之间的整数，最优选2。
  2. 按照权利要求1所述的酯基聚合物，其特征在于，基团T表示 的主链选自聚烯烃、聚醚和聚酯，优选聚烯烃。
  3. 按照权利要求2所述的酯基聚合物，其特征在于，基团T表示的主链为聚烯烃链，且所述聚烯烃为C 2-20烯烃的均聚物或共聚物。
  4. 按照权利要求1-3中任一项所述的酯基聚合物，其特征在于，
    基团B表示O；
    各基团R彼此相同或不同，各自独立地表示C 1-4直链或支链亚烷基；
    基团A表示O；
    各基团R′彼此相同或不同，各自独立地表示C 1-4直链或支链亚烷基；
    各基团N b彼此相同或不同，各自独立地表示-R″′-B′H；
    各基团R″′彼此相同或不同，各自独立地表示C 1-4直链或支链亚烷基；
    基团B′表示O；
    y为1；并且
    m为2。
  5. 按照权利要求1-4中任一项所述的酯基聚合物，其特征在于，所述酯基聚合物的数均分子量为600-10500，优选800-4500。
  6. 一种酯基聚合物的制备方法，包括使母体聚合物与至少一种下式(II)所示的化合物进行酯化反应的步骤：
    Figure PCTCN2018087068-appb-100002
    其中，
    所述母体聚合物指含有-COOH基团和/或
    Figure PCTCN2018087068-appb-100003
    基团的聚合物，
    基团B选自O或S，优选O；
    各基团R彼此相同或不同，各自独立地表示C 1-10亚烃基，优选C 1-6直链或支链亚烷基，进一步优选C 1-4直链或支链亚烷基，各基团R任选地被选自烷氧基、羟基、氨基和巯基的基团取代；
    各基团A彼此相同或不同，各自独立地选自O、S或NR″，优选O或S，更优选O；
    基团R′表示C 1-10亚烃基，优选C 1-6直链或支链亚烷基，进一步优选C 1-4直链或支链亚烷基，基团R′任选地被选自烷氧基、羟基、氨基和巯基的基团取代；
    各基团N b彼此相同或不同，各自独立地选自H或-R″′-B′H，其中至少一个为-R″′-B′H，优选各自独立地为-R″′-B′H；
    各基团R″彼此相同或不同，各自独立地选自H或C 1-10烃基，优选选自H或C 1-6直链或支链烷基，进一步优选选自H或C 1-4直链或支链烷基，最优选H；
    各基团R″′彼此相同或不同，各自独立地表示C 1-10亚烃基，优选C 1-6直链或支链亚烷基，进一步优选C 1-4直链或支链亚烷基，各基团R″′任选地被选自烷氧基、羟基、氨基和巯基的基团取代；
    各基团B′彼此相同或不同，各自独立地选自O或S，优选O；并且
    y表示1-6之间的整数，优选1-3之间的整数，最优选1。
  7. 按照权利要求6所述的制备方法，进一步包括使至少一种下式(III)所示的化合物，
    Figure PCTCN2018087068-appb-100004
    其中：
    各基团N b彼此相同或不同，各自独立地选自H或-R″′-B′H，其中至少一个为-R″′-B′H，优选各自独立地为-R″′-B′H；且
    各基团R″′彼此相同或不同，各自独立地表示C 1-10亚烃基，优选C 1-6直链或支链亚烷基，进一步优选C 1-4直链或支链亚烷基，各基团R″′任选地被选自烷氧基、羟基、氨基和巯基的基团取代；
    各基团B′彼此相同或不同，各自独立地选自O或S，优选O；
    与至少一种下式(IVA)所示的化合物和/或至少一种下式(IVB)所示的化合物进行酰化反应生成至少一种式(II)所示化合物的步骤，
    Figure PCTCN2018087068-appb-100005
    Figure PCTCN2018087068-appb-100006
    其中：
    各基团B彼此相同或不同，各自独立地选自O或S，优选O；
    各基团R彼此相同或不同，各自独立地表示C 1-10亚烃基，优选C 1-6直链或支链亚烷基，进一步优选C 1-4直链或支链亚烷基，各基团R任选地被选自烷氧基、羟基、氨基和巯基的基团取代；
    各基团A彼此相同或不同，各自独立地选自O、S或NR″，优选O或S，更优选O；
    各基团R′彼此相同或不同，各自独立地表示C 1-10亚烃基，优选C 1-6直链或支链亚烷基，进一步优选C 1-4直链或支链亚烷基，各基团R′任选地被选自烷氧基、羟基、氨基和巯基的基团取代；
    各基团R″彼此相同或不同，各自独立地选自H或C 1-10烃基，优选选自H或C 1-6直链或支链烷基，进一步优选选自H或C 1-4直链或支链烷基，最优选H；并且
    各个y彼此相同或不同，各自独立地表示1-6之间的整数，优选1-3之间的整数，最优选1。
  8. 按照权利要求7所述的方法，其特征在于，所述至少一种式(III)化合物选自醇胺、硫醇胺、或其混合物，优选选自包含两个羟基的醇胺、包含两个巯基的硫醇胺、或其混合物，更优选选自包含两个羟基的C1-C10醇胺、包含两个巯基的C1-C10硫醇胺、或其混合物，特别优选选自乙醇胺、丙醇胺、丁醇胺、戊醇胺、己醇胺、乙二醇胺、丙二醇胺、丁二醇胺、戊二醇胺、己二醇胺、乙硫醇胺、丙硫醇胺、丁硫醇胺、戊硫醇胺、己硫醇胺、乙二硫醇胺、丙二硫醇胺、丁二硫醇胺、戊二硫醇胺和己二硫醇胺中的一种或多种。
  9. 按照权利要求7或8所述的方法，其特征在于，所述至少一种式(IVA)化合物选自含有羟基和羧基的醚类物质、含有巯基和羧基的醚类物质和含有胺基和羧基的醚类物质中的一种或多种，优选亚烷基二醇与羟基酸的醚化产物、亚烷基二硫醇与羟基酸的醚化产物和醇胺与羟基酸的醚化产物中的一种或多种，更优选C1-C5亚烷基二醇与C1-C5羟基酸的醚化产物、C1-C5亚烷基二硫醇与C1-C5羟基酸的醚化产物 和C1-C5醇胺与C1-C5羟基酸的醚化产物中的一种或多种，特别优选选自2-(2-羟基乙氧基)-乙酸、3-(2-羟基乙氧基)-丙酸、3-(2-羟基乙氧基)-丁酸、2-(3-羟基丙氧基)-乙酸、2-(4-羟基丁氧基)-丙酸、2-(2-羟基乙硫基)-乙酸、3-(2-羟基乙硫基)-丙酸、3-(2-羟基乙硫基)-丁酸、2-(3-羟基丙硫基)-乙酸和2-(4-羟基丁硫基)-丙酸中的一种或多种。
  10. 按照权利要求7-9中任一项所述的方法，其特征在于，所述至少一种式(IVB)化合物选自氧杂内酯、硫杂内酯和氮杂内酯中的一种或多种，优选氧杂内酯，特别优选选自氧杂丙内酯、氧杂丁内酯(二氧六环二酮)、氧杂戊内酯、氧杂己内酯、氧杂庚内酯、氧杂辛内酯、硫杂丙内酯、硫杂丁内酯、硫杂戊内酯、硫杂己内酯、硫杂庚内酯、硫杂辛内酯、氮杂丙内酯、氮杂丁内酯、氮杂戊内酯、氮杂己内酯、氮杂庚内酯和氮杂辛内酯中的一种或多种。
  11. 按照权利要求7所述的方法，其特征在于，所述至少一种式(III)化合物选自如下通式(V)的化合物：
    Figure PCTCN2018087068-appb-100007
    其中，R1和R2可以相同或不同，分别独立地选自C 1-10亚烷基，优选C 1-6亚烷基，更优选C 1-4亚烷基，R 1和R 2任选地被选自烷氧基、羟基、氨基和巯基的基团取代。
  12. 按照权利要求7或11所述的方法，其特征在于，所述至少一种式(IVB)化合物选自如下通式(VI)的化合物：
    Figure PCTCN2018087068-appb-100008
    其中，R 3和R 4可以相同或不同，分别独立地选自H或C 1-8烷基，优选H或C 1-4烷基，其中所述烷基任选地被选自烷氧基、羟基、氨基和巯基的基团取代。
  13. 按照权利要求6-12中任一项所述的方法，其特征在于，所述母体聚合物为分子中含有q个-COOH基团和/或
    Figure PCTCN2018087068-appb-100009
    基团的聚合物，其中q表示所述聚合物中-COOH基团和/或
    Figure PCTCN2018087068-appb-100010
    基团的总数 与聚合物分子数的比值，1≤q≤10，优选1≤q≤5，特别优选地所述聚合物选自聚烯烃、聚醚和聚酯。
  14. 按照权利要求6-13中任一项所述的方法，其特征在于，所述母体聚合物为含有-C＝C-键的聚合物与烯基酸和/或烯基酸酐进行加成反应的产物，优选分子中含有u个-C＝C-键的聚合物与烯基酸和/或烯基酸酐进行加成反应的产物，其中u表示聚合物中-C＝C-基团的总数与聚合物分子数的比值，1≤u≤10，优选1≤u≤5，特别优选地，所述聚合物选自聚烯烃、聚醚和聚酯，尤其特别优选地，所述含有-C＝C-键的聚合物为分子中含有1-2个-C＝C-键的聚烯烃，进一步优选分子中含有1个-C＝CH 2键的聚α-烯烃。
  15. 按照权利要求14所述的方法，其特征在于，所述含有1-2个-C＝C-键的聚烯烃选自C 2_20烯烃的均聚物或共聚物，优选C 2-20α-烯烃的均聚物或共聚物。
  16. 按照权利要求14-15中任一项所述的方法，其特征在于，所述的烯基酸和/或烯基酸酐为C 3-10烯基酸和/或烯基酸酐，更优选C 4-10烯基二酸和/或烯基二酸酐。
  17. 按照权利要求14-16中任一项所述的方法，其特征在于，所述的烯基酸和/或烯基酸酐选自丙烯酸、丁烯酸、戊烯酸、己烯酸、庚烯酸、辛烯酸、壬烯酸、癸烯酸、丁烯二酸、戊烯二酸、己烯二酸、庚烯二酸、辛烯二酸、壬烯二酸、癸烯二酸、马来酸酐、丁烯二酸酐、戊烯二酸酐、己烯二酸酐、庚烯二酸酐、辛烯二酸酐、壬烯二酸酐和癸烯二酸酐中的一种或多种。
  18. 按照方案6-17中任一项所述的方法，其特征在于，所述母体聚合物的数均分子量为约500-10000，优选约600-6000，进一步优选约600-3000。
  19. 权利要求1-5中任一项所述的酯基聚合物和/或按照权利要求6-18中任一项所述的方法制备的酯基聚合物用作分散剂和/或阻聚剂的用途，特别是用作沥青质分散剂和/或阻聚剂的用途。
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