阅读说明：本技术 一种含苯酚聚醚酯的组合物及其制备方法和应用 (Composition containing phenol polyether ester and preparation method and application thereof ) 是由 沈之芹 李应成 吴春芳 马俊伟 于 2020-06-09 设计创作，主要内容包括：本发明公开了一种含苯酚聚醚酯的组合物及其制备方法和应用,所述组合物包括式(I)所示含苯酚聚醚酯中的至少一种和式(II)所示取代苯类化合物中的至少一种：R-(1)和R-(2)各自独立地选自氢、C-(1)～C-(32)的烃基、C-(1)～C-(32)的取代烃基、酯基、羟基、胺基或烷氧基；R-(3)、R-(4)和R-(5)各自独立选自羟基、氢或烷基；R-(6)选自C-(1)～C-(31)的烃基、C-(1)～C-(31)的取代烃基；a＝0～50,b＝0～50,c＝0～50,且a、b和c不同时为0；d＝0或1；j＝0、1或2；R-(7)选自氢、C-(1)～C-(32)的烃基、C-(1)～C-(32)的取代烃基、烷氧基、酯基、胺基和羟基中的一种；y为1～6中的任一整数,当y＞1时每个R-(7)相同或不同。(The invention disclosesA composition containing phenol polyether ester and a preparation method and application thereof, wherein the composition comprises at least one of phenol polyether ester shown in a formula (I) and at least one of substituted benzene compounds shown in a formula (II): r 1 And R 2 Each independently selected from hydrogen and C 1 ～C 32 A hydrocarbon group of 1 ～C 32 Substituted hydrocarbyl, ester, hydroxyl, amino or alkoxy groups of (a); r 3 、R 4 And R 5 Each independently selected from hydroxy, hydrogen or alkyl; r 6 Is selected from C 1 ～C 31 A hydrocarbon group of 1 ～C 31 Substituted hydrocarbyl groups of (a); a is 0-50, b is 0-50, c is 0-50, and a, b and c are not 0 at the same time; d is 0 or 1; j is 0, 1 or 2; r 7 Selected from hydrogen, C 1 ～C 32 A hydrocarbon group of 1 ～C 32 One of substituted hydrocarbyl, alkoxy, ester, amino and hydroxyl; y is any integer of 1 to 6, and each R is R when y > 1 7 The same or different.)

1. a composition containing a phenol-containing polyether ester, which comprises at least one of the phenol-containing polyether ester shown in a formula (I) and at least one of substituted benzene compounds shown in a formula (II):

in the formula (I), R₁And R₂Each independently selected from hydrogen and C₁～C₃₂Or C is a hydrocarbon group₁～C₃₂Substituted hydrocarbyl, ester, hydroxyl, amino or alkoxy groups of (a); and/or, R₃、R₄And R₅Each independently selected from hydroxy, hydrogen or alkyl; and/or, R₆Is selected from C₁～C₃₁Or C is a hydrocarbon group₁～C₃₁Substituted hydrocarbyl groups of (a); and/or, a is 0-50, b is 0-50, c is 0-50, and a, b and c are not 0 at the same time; and/or, d ═ 0 or 1; and/or, j ═ 0, 1, or 2;

in the formula (II), R₇Selected from hydrogen, C₁～C₃₂A hydrocarbon group of₁～C₃₂One of substituted hydrocarbyl, alkoxy, ester, amino and hydroxyl; and/or, y is any integer of 1 to 6, when y > 1, each R₇The same or different.

2. The composition comprising phenol polyether ester according to claim 1, wherein in formula (I),

R₁and R₂Each independently selected from hydrogen and C₁～C₂₈A hydrocarbon group of₁～C₂₈Substituted hydrocarbyl, alkoxy, ester, amine or hydroxyl groups; preferably, the alkoxy group is OR₈，R₈Is (CHR)₀)_eH，R₀Is hydrogen, methyl or ethyl, e is any integer of 1-12; and/or the ester group is COOR₉，R₉Is (CHR'₀)_fH，R’₀Is hydrogen, methyl or ethyl, and f is any integer of 1-18; more preferably, R₁And R₂Each independently selected from hydrogen and C₁～C₁₈A hydrocarbon group of₁～C₁₈Substituted hydrocarbyl of (2), COO (CHR'₀)_fH or amino, R'₀Is hydrogen or methyl, f is an integer of 1-12; and/or

R₃、R₄And R₅Each independently selected from hydroxy, hydrogen or C₁～C₈Alkyl of (3), preferably from hydroxy, hydrogen or C₁～C₄More preferably from hydroxy, hydrogen or C₁～C₂Alkyl groups of (a); and/or

R₆Is selected from C₁～C₂₃Or C is a hydrocarbon group₁～C₂₃A substituted hydrocarbon group of (2), furtherPreferably selected from C₁～C₁₇Or C is a hydrocarbon group₁～C₁₇A substituted hydrocarbyl group of (a).

3. The composition containing phenol polyether ester according to claim 1, wherein in formula (I), a is 0 to 20, b is 0 to 20, c is 0 to 20, and a, b and c are not 0 at the same time.

4. The composition of claim 1, wherein in formula (II), R is₇Selected from hydrogen, C₁～C₂₄A hydrocarbon group of₁～C₂₄One of the hydrocarbon group, alkoxy group, ester group, amine group and hydroxyl group of (1); and/or, y is any integer of 1 to 3, when y > 1, each R₇The same or different;

preferably, the alkoxy group is OR₁₀，R₁₀Is (CHR)₀)_gH，R₀Is hydrogen, methyl or ethyl, g is any integer of 1-32; and/or the ester group is COOR₁₁，R₁₁Is (CHR'₀)_hH，R’₀Is hydrogen, methyl or ethyl, and h is any integer of 1-32.

5. The composition containing phenol polyether ester as claimed in any one of claims 1 to 4, wherein the molar ratio of the phenol polyether ester represented by formula (I) to the substituted benzene compound represented by formula (II) in the composition is 1 (0.01 to 50), preferably 1 (0.05 to 10).

6. A method for preparing the composition containing phenol polyether ester in claim 1-5, which comprises the following steps: obtaining phenol-containing polyether ester shown in a formula (I), and then mixing the phenol-containing polyether ester with substituted benzene compounds shown in a formula (II) to obtain the phenol-containing polyether ester composition;

wherein the phenol-containing polyether ester shown in the formula (I) is obtained as follows:

step 1, taking a compound shown as a formula (I-1), optionally reacting with a halogenated epoxy compound, and carrying out aftertreatment to obtain a glycidyl ether intermediate;

step 2, in the presence of a catalyst, reacting the compound shown in the formula (I-1) or the glycidyl ether intermediate with an epoxy compound to obtain a polyether intermediate product shown in the formula (I-2);

step 3, in the presence of a catalyst, reacting the polyether intermediate product shown in the formula (I-2) with a blocking agent to obtain phenol-containing polyether ester shown in the formula (I);

wherein, in formula (I-1) and formula (I-2), j is 1 or 2.

7. The process according to claim 6, wherein in the formulae (I-1) and (I-2):

R₁and R₂Selected from hydrogen, C₁～C₃₂Or C is a hydrocarbon group₁～C₃₂The substituted hydrocarbyl, ester, hydroxyl, amino or alkoxy of (A) is preferably selected from hydrogen, C₁～C₂₈A hydrocarbon group of₁～C₂₈Substituted hydrocarbyl, alkoxy, ester, amine or hydroxyl groups; preferably, the alkoxy group is OR₈，R₈Is (CHR)₀)_eH，R₀Is hydrogen, methyl or ethyl, e is any integer of 1-12; and/or the ester group is COOR₉，R₉Is (CHR'₀)_fH，R’₀Is hydrogen, methyl or ethyl, and f is any integer of 1-18; more preferably, R₁And R₂Selected from hydrogen, C₁～C₁₈A hydrocarbon group of₁～C₁₈Substituted hydrocarbyl of (2), COO (CHR'₀)_fH or amino, R'₀Is hydrogen or methyl, f is an integer of 1-12; and/or

R₃、R₄And R₅Each independently selected from hydroxy, hydrogen or C₁～C₈Alkyl of (3), preferably from hydroxy, hydrogen or C₁～C₄More preferably from hydroxy, hydrogen or C₁～C₂Alkyl groups of (a); and/or

a is 0-50, b is 0-50, c is 0-50, preferably a is 0-20, b is 0-20, c is 0-20, and a, b and c are not 0 at the same time; and/or

d is 0 or 1.

8. The production method according to claim 6, wherein, in step 1,

the halogenated epoxy compound is selected from at least one of epichlorohydrin, epoxy chlorobutane and epoxy chloropentane, and is preferably epichlorohydrin; and/or

The post-treatment comprises an open loop treatment: and adding an alkali solution for ring opening treatment to obtain the glycidyl ether intermediate.

9. The production method according to claim 6,

in step 2, the catalyst is an alkaline catalyst, preferably at least one of potassium hydroxide, anhydrous potassium carbonate, sodium hydroxide and sodium bicarbonate; and/or

In step 2, the epoxy compound is selected from at least one of ethylene oxide, propylene oxide, butylene oxide, pentylene oxide, hexylene oxide, heptylene oxide and octylene oxide, preferably at least one of ethylene oxide, propylene oxide and butylene oxide; and/or

In step 3, the catalyst is selected from at least one of alkali metals, alkali metal hydroxides, and alkali metal carbonates, preferably at least one selected from sodium hydroxide, potassium hydroxide, sodium carbonate, and potassium carbonate.

10. The method according to claim 6, wherein in step 3, the end-capping reagent is selected from compounds represented by formula (I-3) and/or formula (I-4):

wherein, in the formulae (I-3) and (I-4)，X₁Selected from hydroxy, halogen or C₁～C₈Alkoxy of (3), preferably from hydroxy, Cl, Br, or C₁～C₅More preferably from hydroxy, Cl, CH₃O or C₂H₅O; and/or, X₂Is O; and/or, R₆Is selected from C₁～C₃₁A hydrocarbon group of₁～C₃₁Substituted hydrocarbon radicals of, preferably from C₁～C₂₃Or C is a hydrocarbon group₁～C₂₃More preferably from C₁～C₁₇Or C is a hydrocarbon group₁～C₁₇A substituted hydrocarbyl group of (a).

11. The preparation method according to claim 6, wherein in step 3, the molar ratio of the polyether intermediate product to the end-capping reagent is 1 (1-1.5), preferably 1 (1-1.2), wherein the molar amount of the polyether intermediate product is calculated as the molar amount of the hydroxyl group therein, and the molar amount of the end-capping reagent is calculated as the molar amount of the R group therein₆Based on the molar amount of (a).

12. The process according to any one of claims 6 to 11, wherein when in formula (II), y is not less than 2 and one of R is₇Selected from O (CHR)₀)_gH, the substituted benzene compound shown in the formula (II) is prepared as follows: reacting a compound of the formula (II') with X₃(CHR₀)_gH reacts in the presence of a catalyst to obtain the substituted benzene compound shown as a formula (II' -1);

in the formula (II'), R₇Selected from hydrogen, C₁～C₃₂A hydrocarbon group of₁～C₃₂When y-x is one of substituted hydrocarbyl, ester, amino and hydroxyl>At 1, each R₇The same or different; x and y are respectively any integer of 1-6, and x is less than or equal to y; preferably, x and y are each optionally any integer from 1 to 3, and x ≦ y.

13. The production method according to claim 12,

at X₃(CHR₀)_gIn H, X₃Selected from hydroxy, halogen or alkoxy, preferably from hydroxy, halogen or C₁～C₈More preferably from hydroxy, Cl, Br, or C₁～C₅Most preferably selected from OH, Cl, CH₃O or C₂H₅O; and/or

At X₃(CHR₀)_gH and in the formula (II' -1), R₀Is hydrogen, methyl or ethyl, g is any integer of 1-32; preferably, R₀Is hydrogen or methyl, g is any integer of 1-24; and/or

In the formulae (II ') and (II' -1), R₇Selected from hydrogen, C₁～C₂₄A hydrocarbon group of₁～C₂₄One of the hydrocarbon group, ester group, amine group and hydroxyl group of (a); and/or

A compound of the formula (II') with X₃(CHR₀)_gThe molar ratio of H is 1 (1-1.5), preferably 1 (1-1.2), wherein the molar amount of the compound shown as the formula (II') is calculated by the molar amount of hydroxyl, and X is₃(CHR₀)_gMolar amount of H in which X₃Based on the molar amount of (a).

14. The process according to any one of claims 6 to 11, wherein when in formula (II), y is not less than 2 and one of R is₇Is selected from-COO (CHR'₀)_hH, the substituted benzene compound shown in the formula (II) is prepared as follows: reacting a compound of formula (II ' -1) or (II ' -2) with HO (CHR '₀)_hH reacts in the presence of a catalyst to obtain the substituted benzene compound, and the structures of the substituted benzene compound are respectively shown as a formula (II '-3) and a formula (II' -4):

in the formulae (II '-1) to (II' -4), R₇Selected from hydrogen, C₁～C₃₂A hydrocarbon group of₁～C₃₂When y-x is one of substituted hydrocarbyl, alkoxy, amino and hydroxy>At 1, each R₇The same or different; x and y are respectively any integer of 1-6, and x is less than or equal to y; preferably, x and y are each optionally any integer from 1 to 3, and x ≦ y.

15. The method of claim 14,

in the formula (II' -1), X₃Selected from hydroxy, halogen or alkoxy, preferably from hydroxy, halogen or C₁～C₈More preferably from hydroxy, Cl, Br, or C₁～C₅Most preferably selected from hydroxy, Cl, CH₃O or C₂H₅O; and/or

In formula (II' -2), X₄Is O; and/or

At HO (CHR'₀)_hH. R 'in the formulae (II' -3) and (II '-4)'₀Is hydrogen, methyl or ethyl, h is any integer of 1 to 32, preferably R'₀Is hydrogen or methyl, h is any integer of 1-24; and/or

In the formulae (II '-1) to (II' -4), R₇Selected from hydrogen, C₁～C₂₄A hydrocarbon group of₁～C₂₄One of the hydrocarbon group, ester group, amine group and hydroxyl group of (a); and/or

A compound of formula (II '-1) with HO (CHR'₀)_hThe molar use ratio of H is 1 (1-1.5), preferably 1 (1-1.2), wherein the molar amount of the compound shown as the formula (II' -1) is the molar amount of X₃Calculated as mol of HO (CHR)'₀)_hThe molar amount of H is based on the molar amount of its molecules; and/or

A compound of formula (II '-2) with HO (CHR'₀)_hThe molar ratio of H is 1 (2-3), preferably 1 (2-2.5), wherein the molar amount of the compound represented by the formula (II '-2) and HO (CHR'₀)_hMolar amounts of H are allBased on the molar amount of the molecule.

16. The application of the composition containing phenol polyether ester in any one of claims 1 to 5 or the composition containing phenol polyether ester obtained by the preparation method in any one of claims 6 to 15 in cold recovery of heavy oil, wherein the oil reservoir temperature is preferably 40 to 100 ℃, the formation pressure is preferably 5 to 25MPa, and the crude oil viscosity is preferably 1000 to 20,000 mPa.s.

17. The use according to claim 16, performed by: and injecting the composition slug containing the phenol polyether ester and the carbon dioxide slug into the thick oil in sequence, or dissolving the composition containing the phenol polyether ester in the carbon dioxide and then injecting the slug into the thick oil.

Technical Field

The invention belongs to the field of cold recovery of thick oil, and particularly relates to a composition containing phenol polyether ester, a preparation method of the composition and application of the composition in cold recovery of thick oil.

Background

The low-permeability oil reservoir has the characteristics of poor reservoir physical property, low porosity, low permeability and serious heterogeneity, the initial capacity of the oil reservoir is low, the yield is reduced rapidly, particularly for the low-permeability heavy oil reservoir, the low-permeability heavy oil reservoir is influenced by the low permeability and the high crude oil viscosity, and the conventional methods such as steam flooding can not realize effective exploitation.

CO₂The flooding is used as a traditional method for improving the recovery efficiency of crude oil, can effectively improve the injection capacity, avoids the water sensitivity phenomenon, and is one of the ways for improving the recovery efficiency of low-permeability oil reservoirs. At a certain temperature and pressure, CO₂The intermediate molecular weight hydrocarbons in the crude oil can be evaporated and extracted in limited quantity, so that the injected gas is gradually enriched. Although this limited amount of vaporization is not sufficient to cause CO to vaporize₂Achieves multi-stage contact miscible phase with the thickened oil at the displacement front, but can effectively reduce CO₂The interfacial tension with crude oil, and the non-miscible flooding recovery ratio is improved. At present, CO₂Lifting thick oilThe technical aspects of reservoir recovery still face a number of bottlenecks, especially for deep low permeability heavy oil reservoirs. Therefore, in order to obtain a good oil displacement effect, the interaction between carbon dioxide and thickened oil needs to be enhanced through a chemical agent, the viscosity of the thickened oil is reduced, the residual oil is contacted and started to the maximum extent so as to improve the oil washing efficiency, and finally, the aim of economically and efficiently improving the recovery ratio of the deep low-permeability thickened oil reservoir is fulfilled. For the ultra-thick oil with deep burial and thin reservoir, the traditional development means is difficult to take effect, and there are few successful cases reported at home and abroad. HDCS is a multi-element composite huff and puff technology, and represents four terms of Horizontal well (Horizontal well), oil-soluble composite viscosity reducer (dispolver), Carbon dioxide (Carbon dioxide) and Steam (Steam), respectively. According to the technology, an oil-soluble viscosity reducing agent, three slugs of carbon dioxide and steam are injected in sequence, then the well is stewed, the viscosity reducing effect of a chemical agent and the carbon dioxide, the expansion effect of the carbon dioxide and the heat transfer effect of the steam are utilized to improve the fluidity of crude oil, the sweep range is enlarged, the saturation of residual oil is reduced, and finally the well is opened for recovery. By means of the technology, the super heavy oil reservoir can be exploited, and the exploitation effect is ideal. Li bingfei et al reported a case of successfully implementing HDCS technology in zheng 411 super heavy oil reservoirs of a victory oil field. The application of the technology realizes the exploitation of the ultra-heavy oil reservoir with the viscosity of more than 300,000mPa/s (50 ℃), the burial depth of more than 1300m and the average thickness of an oil layer of less than 8 m. The viscosity of the thick oil is reduced by injecting an SLKF series oil-soluble viscosity reducer developed by petroleum development center of the Shengli petroleum administration. And constructing 31 wells successively until 11 months in 2006, and increasing 13268 tons of crude oil by accumulation and 428 tons of oil by average single well.

The Zhang Ding Yong carries out reservoir numerical simulation analysis aiming at the wide 9 blocks of thickened oil in the victory oil field, and researches the mechanism of an oil-soluble viscosity reducer, carbon dioxide and steam in the viscosity reducing action of the thickened oil. The heavy oil reservoir has the buried depth of 837m, the stratum pressure of 8.46MPa, the effective thickness of 8-14 m, the average porosity of 33 percent and the average permeability of 5000 transmittance^-3 30²The viscosity of the crude oil at 500 ℃ is generally 50,000 to 80,000 mPas. Laboratory researches find the acting radius, the effective viscosity and the acting radius of the viscosity reducer, the carbon dioxide and the steam on the viscosity reduction of the thickened oilThe injection amount of the HDCS throughput period is optimized, and finally, a scheme of performing HNS throughput after 8 HDCS throughput periods is provided, so that the economic effect of the whole scheme is improved through optimization. The scheme is implemented in a wide 9-block CNP49 well, the production period is 12 cycles, and the cumulative oil production is 2578 tons.

Although the oil-soluble viscosity reducer is adopted to assist carbon dioxide to produce thick oil in the reports to achieve certain effects, the viscosity reducer is high in use concentration and cost, and steam is required to be used, so that the application is greatly limited. The invention relates to a composition with stable structure under oil reservoir conditions, a preparation method and application thereof.

Disclosure of Invention

The invention provides a composition containing phenol polyether ester, aiming at solving the problems of large use concentration and high cost of chemical agent assisted carbon dioxide cold recovery for increasing the yield of thickened oil in the prior art. The composition containing the phenol polyether ester has good carbon dioxide affinity and thickened oil affinity, can effectively reduce the viscosity of thickened oil due to low use concentration, and has a viscosity reduction rate reaching 99.6% in cooperation with carbon dioxide, so that thickened oil can be started, the thickened oil displacement efficiency is improved, and the application prospect of improving the recovery ratio is good.

One of the objects of the present invention is to provide a phenol-containing polyether ester composition, which comprises at least one phenol-containing polyether ester shown in formula (I) and at least one substituted benzene compound shown in formula (II):

in the formula (I), R₁And R₂Independently selected from hydrogen, C₁～C₃₂Or C is a hydrocarbon group₁～C₃₂Substituted hydrocarbyl, ester, hydroxyl, amino (amino) or alkoxy groups of (a); and/or, R₃、R₄And R₅Each independently selected from hydroxy, hydrogen or alkyl; and/or, R₆Is selected from C₁～C₃₁A hydrocarbon group of₁～C₃₁Substituted hydrocarbyl groups of (a); and/orA is 0-50, b is 0-50, c is 0-50, and a, b and c are not 0 at the same time; and/or, d ═ 0 or 1; and/or, j ═ 0, 1, or 2.

In the formula (II), R₇Selected from hydrogen, C₁～C₃₂A hydrocarbon group of₁～C₃₂One of substituted hydrocarbyl, alkoxy, ester group, amino (amino) and hydroxyl; and/or, y is any integer of 1 to 6, when y > 1, each R₇The same or different.

In a preferred embodiment, in formula (I), R₁And R₂Each independently selected from hydrogen and C₁～C₂₈A hydrocarbon group of₁～C₂₈Substituted hydrocarbyl, alkoxy, ester, amine or hydroxyl groups;

preferably, the alkoxy group is OR₈，R₈Is (CHR)₀)_eH，R₀Is hydrogen, methyl or ethyl, e is any integer of 1-32; and/or the ester group is COOR₉，R₉Is (CHR'₀)_fH，R’₀Is hydrogen, methyl or ethyl, and f is any integer of 1-18. More preferably, R₀Is hydrogen or methyl, e is an integer of 1 to 24, and/or, R'₀Is hydrogen or methyl.

In a further preferred embodiment, in formula (I), R₁And R₂Each independently selected from hydrogen and C₁～C₁₈A hydrocarbon group of₁～C₁₈Substituted hydrocarbyl of (2), COO (CHR'₀)_fH or amino, R'₀Is hydrogen or methyl, and f is an integer of 1 to 12.

In a preferred embodiment, in formula (I), R₃、R₄And R₅Each independently selected from hydroxy, hydrogen or C₁～C₈Alkyl group of (1).

In a further preferred embodiment, in formula (I), R₃、R₄And R₅Each independently selected from hydroxy, hydrogen or C₁～C₄Alkyl group of (1).

In a still further preferred embodiment, in formula (I), R₃、R₄And R₅Each independently selected from hydroxy, hydrogen or C₁～C₂Alkyl group of (1).

In a preferred embodiment, in formula (I), R₆Is selected from C₁～C₂₃Or C is a hydrocarbon group₁～C₂₃More preferably from C₁～C₁₇Or C is a hydrocarbon group₁～C₁₇A substituted hydrocarbyl group of (a).

In a preferred embodiment, in formula (I), a is 0 to 20, b is 0 to 20, and c is 0 to 20, and a, b, and c are not 0 at the same time.

Wherein a, b and c are the addition number of polyether segments, j is the number of phenolic ether groups, and j is 1 or 2.

In a preferred embodiment, in formula (II), R₇Selected from hydrogen, C₁～C₂₄A hydrocarbon group of₁～C₂₄One of a hydrocarbon group, an alkoxy group, an ester group, an amino (amino) group and a hydroxyl group; and/or, y is any integer of 1 to 3, when y > 1, each R₇The same or different.

In a further preferred embodiment, the alkoxy group is OR₁₀，R₁₀Is (CHR)₀)_gH，R₀Is hydrogen, methyl or ethyl, g is any integer of 1-32; and/or the ester group is COOR₁₁，R₁₁Is (CHR'₀)_hH，R’₀Is hydrogen, methyl or ethyl, and h is any integer of 1-32.

In a preferred embodiment, the molar ratio of the phenol-containing polyether ester shown in the formula (I) to the substituted benzene compound shown in the formula (II) in the composition is 1 (0.01-50).

In a further preferred embodiment, the molar ratio of the phenol-containing polyether ester shown in the formula (I) to the substituted benzene compound shown in the formula (II) in the composition is 1 (0.05-10).

For example, the molar ratio of the phenol-containing polyether ester shown in the formula (I) to the substituted benzene compound shown in the formula (II) is 1:0.05, 1:0.1, 1:0.5, 1:1, 1:2, 1:3, 1:4, 1:5, 1:6, 1:8 or 1: 10.

In a preferred embodiment, the composition optionally further comprises a pour point depressant and/or a viscosity reducing agent.

In a further preferred embodiment, the composition optionally further comprises at least one of an ethylene acrylate copolymer, an acrylate long carbon chain ester copolymer, an anionic surfactant, a nonionic surfactant, and a built surfactant.

Wherein the pour point depressant and viscosity reducing agent may also be selected from other types commonly used in the art.

The second object of the present invention is to provide a process for preparing the phenol polyether ester-containing composition of the first object of the present invention, which comprises: obtaining phenol-containing polyether ester shown in a formula (I), and then mixing the phenol-containing polyether ester with substituted benzene compounds shown in a formula (II) to obtain the phenol-containing polyether ester composition; the phenol-containing polyether ester of the formula (I) is obtained as follows:

step 1, taking a compound shown as a formula (I-1), optionally reacting with a halogenated epoxy compound, and carrying out aftertreatment to obtain a glycidyl ether intermediate;

step 2, in the presence of a catalyst, reacting the compound shown in the formula (I-1) or the glycidyl ether intermediate with an epoxy compound to obtain a polyether intermediate product shown in the formula (I-2);

and 3, reacting the polyether intermediate product shown in the formula (I-2) with a blocking agent in the presence of a catalyst to obtain the phenol-containing polyether ester shown in the formula (I).

Wherein, in formula (I-1) and formula (I-2), j is 1 or 2.

In a preferred embodiment, in formula (I-1) and formula (I-2):

R₁and R₂Each independently hydrogen, C₁～C₃₂Or C is a hydrocarbon group₁～C₃₂The substituted hydrocarbyl, ester, hydroxyl, amino or alkoxy of (A) is preferably selected from hydrogen, C₁～C₂₈A hydrocarbon group of₁～C₂₈Substituted hydrocarbyl, alkoxy, ester, amino (amino) or hydroxy groups of (a); preferably, the alkoxy group is OR₈，R₈Is (CHR)₀)_eH，R₀Is hydrogen, methyl or ethyl, e is any integer of 1-12; and/or the ester group is COOR₉，R₉Is (CHR'₀)_fH，R’₀Is hydrogen, methyl or ethyl, and f is any integer of 1-18; more preferably, R₁And R₂Each independently selected from hydrogen and C₁～C₁₈A hydrocarbon group of₁～C₁₈Substituted hydrocarbyl of (2), COO (CHR'₀)_fH or amino, R'₀Is hydrogen or methyl, f is an integer of 1-12; and/or

R₃、R₄And R₅Each independently selected from hydroxy, hydrogen or C₁～C₈Alkyl of (3), preferably from hydroxy, hydrogen or C₁～C₄More preferably from hydroxy, hydrogen or C₁～C₂Alkyl groups of (a); and/or

a is 0-50, b is 0-50, c is 0-50, preferably a is 0-20, b is 0-20, c is 0-20, and a, b and c are not 0 at the same time; and/or

d is 0 or 1.

Wherein, in step 2, when a compound represented by formula (I-1) is used to directly react with an epoxy compound, d ═ 0 is obtained in the product; when the glycidyl ether compound intermediate is used in the reaction with an epoxy compound, d-1 is obtained as a product.

In a preferred embodiment, in step 1, the halogenated epoxy compound is selected from at least one of epichlorohydrin, chloroepoxybutane and chloroepoxypentane, and is preferably epichlorohydrin.

In a preferred embodiment, in step 1, the post-treatment comprises an open loop treatment: and adding an alkali solution for ring opening treatment to obtain the glycidyl ether intermediate.

Wherein, the reaction conditions for preparing the intermediate of the glycidyl ether by the reaction of the compound shown as the formula (I-1) and the halogenated epoxy compound are disclosed in the prior art.

In a preferred embodiment, in step 2, the catalyst is a basic catalyst, preferably at least one selected from potassium hydroxide, anhydrous potassium carbonate, sodium hydroxide, and sodium bicarbonate.

In a preferred embodiment, in step 2, the epoxy compound is selected from at least one of ethylene oxide, propylene oxide, butylene oxide, pentylene oxide, hexylene oxide, heptylene oxide and octylene oxide, preferably at least one of ethylene oxide, propylene oxide and butylene oxide.

In a preferred embodiment, in step 3, the catalyst is selected from at least one of alkali metals, alkali metal hydroxides, alkali metal carbonates, preferably at least one selected from sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate.

In step 3, a Williamson etherification reaction is carried out on the polyether intermediate product shown in the formula (I-2) and a blocking agent to realize the blocking of the terminal hydroxyl.

In a preferred embodiment, in step 3, the blocking agent is selected from compounds represented by formula (I-3) and/or formula (I-4):

wherein, in the formulae (I-3) and (I-4), X₁Selected from hydroxy, halogen or C₁～C₈Alkoxy of (3), preferably from hydroxy, Cl, Br, or C₁～C₅More preferably from hydroxy, Cl, CH₃O or C₂H₅O; and/or, X₂Is O; and/or, R₆Is selected from C₁～C₃₁Or C is a hydrocarbon group₁～C₃₁Substituted hydrocarbon radicals of, preferably from C₁～C₂₃Or C is a hydrocarbon group₁～C₂₃Is gotSubstituted hydrocarbyl, more preferably selected from C₁～C₁₇Or C is a hydrocarbon group₁～C₁₇A substituted hydrocarbyl group of (a).

In a preferred embodiment, in step 3, the molar ratio of the polyether intermediate product to the end-capping reagent is 1 (1-1.5), preferably 1 (1-1.2), wherein the molar amount of the polyether intermediate product is calculated by the molar amount of the hydroxyl groups therein, and the molar amount of the end-capping reagent is calculated by the molar amount of the hydroxyl groups therein₆Based on the molar amount of (a).

In the present invention, the substituted benzene compound represented by the formula (II) may be purchased and used directly from the market, or may be obtained by a conventional etherification, esterification or the like reaction.

In a preferred embodiment, when y.gtoreq.2 and one of R in formula (II)₇Selected from O (CHR)₀)_gH, the substituted benzene compound shown in the formula (II) is prepared as follows (can be directly purchased): reacting a compound of the formula (II') with X₃(CHR₀)_gH reacts in the presence of a catalyst to obtain the substituted benzene compound shown as the formula (II' -1).

In the formula (II'), R₇Selected from hydrogen, C₁～C₃₂A hydrocarbon group of₁～C₃₂When y-x is one of substituted hydrocarbyl, ester, amino and hydroxyl>At 1, each R₇The same or different; x and y are respectively any integer of 1-6, and x is less than or equal to y; preferably, x and y are each optionally any integer from 1 to 3, and x ≦ y.

In a preferred embodiment, at X₃(CHR₀)_gIn H, X₃Selected from hydroxy, halogen or alkoxy, preferably from hydroxy, halogen or C₁～C₈More preferably from hydroxy, Cl, Br, or C₁～C₅Most preferably selected from hydroxy, Cl, CH₃O or C₂H₅O。

In a preferred embodimentIn X₃(CHR₀)_gH and in the formula (II' -1), R₀Is hydrogen, methyl or ethyl, g is any integer of 1-32; preferably, R₀Is hydrogen or methyl, and g is an integer of 1 to 24.

In a preferred embodiment, in formula (II ') and formula (II' -1), R₇Selected from hydrogen, C₁～C₂₄A hydrocarbon group of₁～C₂₄One of a hydrocarbon group, an ester group, an amine group and a hydroxyl group.

In a preferred embodiment, a compound of the formula (II') is reacted with X₃(CHR₀)_gThe molar ratio of H is 1 (1-1.5), preferably 1 (1-1.2), wherein the molar amount of the compound shown as the formula (II') is calculated by the molar amount of hydroxyl, and X is₃(CHR₀)_gMolar amount of H in which X₃Based on the molar amount of (a).

In a preferred embodiment, when y.gtoreq.2 and one of R in formula (II)₇Is selected from-COO (CHR'₀)_hH, the substituted benzene compound shown in the formula (II) is prepared as follows (can be directly purchased): reacting a compound of formula (II ' -1) or (II ' -2) with HO (CHR '₀)_hH reacts in the presence of a catalyst to obtain the substituted benzene compound, and the structures of the substituted benzene compound are respectively shown as a formula (II '-3) and a formula (II' -4).

In the formulae (II '-1) to (II' -4), R₇Selected from hydrogen, C₁～C₃₂A hydrocarbon group of₁～C₃₂When y-x is one of substituted hydrocarbyl, alkoxy, amino and hydroxy>At 1, each R₇The same or different; x and y are respectively any integer of 1-6, and x is less than or equal to y; preferably, x and y are each optionally any integer from 1 to 3, and x ≦ y.

Wherein formula (II ' -1) and formula (II ' -2) are respectively reacted with HO (CHR '₀)_hAnd performing esterification reaction on the H.

In a preferred embodiment, in formula (II' -1), X₃Selected from hydroxy, halogen or alkoxy, preferably from hydroxy, halogen or C₁～C₈More preferably from hydroxy, Cl, Br, or C₁～C₅Most preferably selected from hydroxy, Cl, CH₃O or C₂H₅O; and/or, in the formula (II' -2), X₄Is O.

In a preferred embodiment, at HO (CHR'₀)_hH. R 'in the formulae (II' -3) and (II '-4)'₀Is hydrogen, methyl or ethyl, h is any integer of 1 to 32, preferably R'₀Is hydrogen or methyl, and h is any integer of 1-24.

In a preferred embodiment, R in the formulae (II '-1) to (II' -4)₇Selected from hydrogen, C₁～C₂₄A hydrocarbon group of₁～C₂₄One of a hydrocarbon group, an ester group, an amine group and a hydroxyl group.

In a preferred embodiment, the compound of formula (II '-1) is reacted with HO (CHR'₀)_hThe molar use ratio of H is 1 (1-1.5), preferably 1 (1-1.2), wherein the molar amount of the compound shown as the formula (II' -1) is the molar amount of X₃Calculated as mol of HO (CHR)'₀)_hThe molar amount of H is based on the molar amount of its molecules.

In a preferred embodiment, the compound of formula (II '-2) is reacted with HO (CHR'₀)_hThe molar ratio of H is 1 (2-3), preferably 1 (2-2.5), wherein the molar amount of the compound represented by the formula (II '-2) and HO (CHR'₀)_hThe molar amount of H is based on the molar amount of the molecule.

The third object of the present invention is to provide the use of the composition according to the first object of the present invention or the composition obtained by the preparation method according to the second object of the present invention in cold production of heavy oil.

Wherein the oil reservoir temperature is 40-100 ℃, the stratum pressure is 5-25 MPa, and the crude oil viscosity is 1000-20,000 mPa.s.

In a preferred embodiment, the thick oil is injected by sequentially injecting a slug of the composition containing the phenol polyetherester and a slug of carbon dioxide, or the thick oil is injected by a slug after dissolving the composition containing the phenol polyetherester in carbon dioxide.

In a further preferred embodiment, the carbon dioxide solubility in the thick oil is measured after a period of time after mixing with the thick oil and the carbon dioxide solubilization rate is calculated by comparison with the solubility measured for the carbon dioxide slug alone.

The thickened oil viscosity-reducing composition can be applied according to the prior art, can be used independently, and can also be used in combination with the existing chemical agent of an oil field.

The composition prepared by the invention has a flexible and adjustable structure, and the interaction of carbon dioxide and thickened oil is enhanced by introducing oxygen atoms, nitrogen atoms and benzene ring groups, so that the dosage of the existing chemical agent can be greatly reduced, and deep low-permeability thickened oil can be effectively started.

The invention relates to the situation of the content or concentration of the composition, which refers to the total concentration of the components of the phenol polyether ester and the substituted benzene compound (II) with the molecular general formula (I) in the technical scheme.

Compared with the prior art, the invention has the following beneficial effects:

(1) the composition prepared by the invention has a flexible and adjustable structure, and the interaction of carbon dioxide and thickened oil is enhanced by introducing oxygen atoms, nitrogen atoms and benzene ring groups, so that the dosage of the existing chemical agent can be greatly reduced, and the thickened oil can be effectively started;

(2) the composition is used for cold production of deep heavy oil reservoirs with the formation temperature of 40-100 ℃, the formation pressure of 5-25 MPa and the crude oil viscosity of 1000-10,000 mPa.s. According to the mass percentage, the common viscosity reduction rate of the composition with the dosage of 2 percent to the thickened oil can reach 99.2 percent, the synergistic viscosity reduction rate of the composition with the dosage of 0.5 percent by weight and the carbon dioxide can reach 99.6 percent, and better technical effect is obtained.

Drawings

The phenol polyether ester compound prepared by the invention can be applied to an American Nicolet-5700 spectrometer and is subjected to infrared spectrum analysis (scanning range 4) by adopting total reflection infrared spectroscopy (ATR)000～400cm^-1) And determining the chemical structure of the tested sample so as to achieve infrared characterization of the compound.

FIG. 1 is an infrared spectrum of octylphenol polyoxypropylene (5) n-hexanoate prepared in example 1.

Wherein, 2969.4cm^-1And 2868.5cm^-1Is a characteristic peak of C-H stretching of methyl and methylene, 1722.3cm^-1Is the C ═ O stretching vibration absorption peak in the ester group, 1511.6cm^-1And 1603.7cm^-1Is the stretching vibration peak of benzene ring, 1098.8cm^-1Is a C-O-C stretching vibration peak of 690-720 cm^-1Is the in-plane rocking absorption peak of CH plane in the benzene ring.

Fig. 2 and fig. 3 are viscosity-temperature and viscosity-shear rate graphs of the 1# crude oil, respectively.

Detailed Description

While the present invention will be described in detail with reference to the following examples, it should be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the present invention.

The raw materials used in the examples and comparative examples are disclosed in the prior art if not particularly limited, and may be, for example, directly purchased or prepared according to the preparation methods disclosed in the prior art.

The viscosity reduction rate of the thickened oil at normal pressure is determined by referring to the viscosity reduction rate of oil-soluble oil in standard Q/SH 10201519-2016. Keeping the temperature of the thick oil at 50 thick for 1-2 h, stirring to remove free water and bubbles in the thick oil, and rapidly measuring the viscosity mu of the thick oil under 50 stirring by using a rheometer₀. Weighing a certain amount of thickened oil, adding the composition according to the percentage, keeping the temperature at 50 ℃ for 1h, placing a stirring paddle in the center of a beaker and at a distance of (2-3) mm from the bottom, adjusting the rotating speed to 250r/min, stirring for 2min under the constant temperature condition to fully mix the thickened oil, rapidly measuring the viscosity mu of the thickened oil by using a rheometer, and calculating the viscosity reduction rate according to a formula (1):

wherein, f: viscosity reduction rate; mu.s₀: viscosity of the thick oil sample at 50 ℃, mPa & s; μ: and adding the viscosity of the thick oil emulsion, mPa & s after the sample solution is added.

The viscosity reducing rate of the thickened oil at high temperature and high pressure can better represent the viscosity reducing effect of the composition and carbon dioxide on the thickened oil. Firstly, the viscosity mu of the thick oil under high temperature and high pressure is measured₀And then measuring the viscosity mu of the thickened oil after the composition and the carbon dioxide are added, and calculating the viscosity reduction rate according to the formula (1).

[ example 1 ]

Adding 206.0 g (1 mol, M is 206) of octylphenol and 5.6 g of potassium hydroxide into a 2L pressure reactor provided with a stirring device, heating to 80-90 ℃, starting a vacuum system, dehydrating for 1 hour under high vacuum, then replacing for 3-4 times by nitrogen, adjusting the reaction temperature of the system to 150 ℃, slowly introducing 293.0 g (5.05 mol) of propylene oxide, and controlling the pressure to be less than or equal to 0.60 MPa. After the reaction was completed, the temperature was reduced to 90 ℃, and low boiling point substances were removed in vacuo, and the reaction mixture was cooled, neutralized and dehydrated to obtain 487.2 g of octylphenol polyoxypropylene (5) (M ═ 496), and the yield was 98.2%.

② under the protection of nitrogen, adding 248.0 g (0.5 mol) of octylphenol polyoxypropylene (5) into a reaction bottle with an alkali liquor absorption device, heating to 40, slowly dropwise adding 67.3 g (0.5 mol, M is 134.5) of hexanoyl chloride, after finishing dropping to 70L, reacting for 3 hours, obtaining octylphenol polyoxypropylene (5) hexanoate, sampling and carrying out infrared spectrum analysis, and the figure is 1.

③ mixing the octyl phenol polyoxypropylene (5) hexanoate obtained in the step (II) with mesitylene according to the molar ratio of 1:0.3, and uniformly stirring to obtain the phenol-containing polyether ester composition M01.

[ example 2 ]

Adding 262.1 g (1 mol, M is 260) of dodecylphenol and 5.4 g of potassium hydroxide into a 2L pressure reactor provided with a stirring device, heating to 80-90 ℃, starting a vacuum system, dehydrating for 1 hour under high vacuum, then replacing for 3-4 times by nitrogen, adjusting the reaction temperature of the system to 150 ℃, slowly introducing 116.2 g (2.0 mol) of propylene oxide, controlling the pressure to be less than or equal to 0.60MPa, adjusting the temperature to 140 ℃ after the propylene oxide reaction is finished, slowly introducing 132.9 g (3.02 mol) of ethylene oxide, cooling to 90 ℃ after the reaction is finished, removing low-boiling substances in vacuum, cooling, neutralizing and dehydrating to obtain 482.1 g of dodecyl phenol polyoxypropylene (2) (M is 508), wherein the yield is 94.9%.

Under the protection of nitrogen, 254.0 g (0.5 mol) of dodecylphenol polyoxypropylene (3) polyoxyethylene (2) is added into a reaction bottle with an alkali liquor absorption device, 47.7 g (0.5 mol, M is 92.5) of isopropionyl chloride is slowly dripped into 30, and the temperature is raised to 60 ℃ after dripping to react for 5 hours to obtain dodecylphenol polyoxypropylene (3) polyoxyethylene (2) isopropionyl ester.

③ mixing the dodecylphenol polyoxypropylene (3), polyoxyethylene (2), isopropyl ester and N, N-dipropyl p-methylaniline which are obtained in the step II according to the molar ratio of 1:0.05, and stirring uniformly to obtain the phenol-containing polyether ester composition M02.

[ example 3 ]

Adding 344.1 g (1 mol, M is 344) of octadecyl phenol and 7.1 g of potassium hydroxide into a 2L pressure reactor provided with a stirring device, heating to 80-90 ℃, starting a vacuum system, dehydrating for 1 hour under high vacuum, then replacing for 3-4 times by nitrogen, adjusting the reaction temperature of the system to 140 ℃, slowly introducing 224.4 g (5.1 mol) of ethylene oxide, controlling the pressure to be less than or equal to 0.40MPa, adjusting the temperature to 150 ℃ after the reaction of the ethylene oxide, slowly introducing 58.0 g (1 mol) of propylene oxide, cooling to 90 ℃ after the reaction is finished, removing low-boiling-point substances in vacuum, cooling, neutralizing and dehydrating to obtain 598.4 g of octadecyl phenol polyoxyethylene (5) polyoxypropylene (1) (M is 622), wherein the yield is 96.2%.

② under the protection of nitrogen, adding 311.1 g (0.5 mol) of octadecyl phenol polyoxyethylene (5) polyoxypropylene (1) into a reaction flask with an alkali liquor absorption device, slowly adding 39.3 g (0.5 mol, M is 78.5) of acetyl chloride dropwise at 20 ℃, after finishing dropping, raising the temperature to 75 ℃ and reacting for 6 hours, obtaining the octadecyl phenol polyoxyethylene (5) polyoxypropylene (1) acetate.

③ mixing the octadecyl phenol polyoxyethylene (5) polyoxypropylene (1) acetate obtained in the step (II) and n-propyl o-methoxybenzoate according to the molar ratio of 1:0.5, and stirring uniformly to obtain the phenol-containing polyether ester composition M03.

[ example 4 ]

Adding 166.1 g (1 mol, M is 166) of tert-butyl diphenol and 14.5 g of potassium hydroxide into a 2L pressure reactor provided with a stirring device, heating to 80-90 ℃, starting a vacuum system, dehydrating for 1 hour under high vacuum, then replacing for 3-4 times by nitrogen, adjusting the reaction temperature of the system to 160 ℃, slowly introducing 288.2 g (4.0 mol) of epoxy butane, controlling the pressure to be less than or equal to 0.60MPa, adjusting the temperature to 150 ℃ after the epoxy butane reaction is finished, slowly introducing 585.5 g (10.1 mol) of epoxy propane, cooling to 90 ℃ after the reaction is finished, removing low-boiling substances in vacuum, cooling, neutralizing and dehydrating to obtain 962.6 g of tert-butyl diphenol polyoxybutylene (4) polyoxypropylene (10) (M is 1034), wherein the yield is 93.1%.

Under the protection of nitrogen, 517.1 g (0.5 mol) of tert-butyl diphenol polyoxybutylene (4) polyoxypropylene (10) is added into a reaction bottle with an alkali liquor absorption device, 108.5 g (0.9 mol, M is 120.5) of n-valeryl chloride is slowly dripped when the temperature is controlled to 40 ℃, and after dripping is finished and the temperature is raised to 80 ℃, the tert-butyl diphenol polyoxybutylene (4) polyoxypropylene (10) di-n-valerate is obtained after 4 hours of reaction.

③ mixing the tert-butyl diphenol polyoxybutylene (4), polyoxypropylene (10), di-n-valerate and hexadecyl benzene obtained in the step (II) according to the molar ratio of 1:0.1, and stirring uniformly to obtain the phenol-containing polyether ester composition M04.

[ example 5 ]

Adding 122.0 g (1 mol, M is 122) of dimethylphenol and 5.9 g of potassium hydroxide into a 2L pressure reactor provided with a stirring device, heating to 80-90 ℃, starting a vacuum system, dehydrating for 1 hour under high vacuum, then replacing for 3-4 times by nitrogen, adjusting the reaction temperature of the system to 160 ℃, slowly introducing 223.2 g (3.1 mol) of epoxybutane, controlling the pressure to be less than or equal to 0.60MPa, adjusting the temperature to 140 ℃ after the reaction of the epoxybutane is finished, slowly introducing 132.1 g (3.0 mol) of epoxyethane, controlling the pressure to be less than or equal to 0.60MPa, adjusting the temperature to 150 ℃ after the reaction of the epoxyethane is finished, slowly introducing 116.0 g (2.0 mol) of epoxypropane, cooling to 90 ℃, removing low-boiling substances in vacuum, cooling, neutralizing and dehydrating to obtain dimethylphenol polyoxybutylene (3) polyoxyethylene (3) polyoxypropylene (2) (M is 586.5 g), the yield thereof was found to be 90.7%.

Under the protection of nitrogen, 293.2 g (0.5 mol) of dimethylphenol polyoxybutylene (3), polyoxyethylene (3) and polyoxypropylene (2) are added into a reaction bottle with an alkali liquor absorption device, isooctyl chloride 81.3 g (0.5 mol, M is 162.5) is slowly dripped when heating to 40 ℃, and after dripping is finished and the temperature is raised to 85 ℃, the dimethyl phenol polyoxybutylene (3), polyoxyethylene (3), polyoxypropylene (2) isooctanoate is obtained after reaction for 5 hours.

③ mixing the dimethylphenol polyoxybutylene (3), polyoxyethylene (3), polyoxypropylene (2), isooctanoate and di-tert-butyl benzene obtained in the step (II) according to the molar ratio of 1:0.4, and stirring uniformly to obtain the phenol-containing polyether ester composition M05.

[ example 6 ]

Adding 137.1 g (1 mol, M is 137) of N, N-dimethyl hydroxyaniline and 15.9 g of potassium hydroxide into a 2L pressure reactor with a stirring device, heating to 80-90 ℃, starting a vacuum system, dehydrating for 1 hour under high vacuum, then replacing for 3-4 times by nitrogen, adjusting the reaction temperature of the system to 150 ℃, slowly introducing 1116.2 g (15.5 mol) of propylene oxide, controlling the pressure to be less than or equal to 0.60MPa, cooling to 90 ℃ after the reaction is finished, removing low-boiling-point substances in vacuum, neutralizing and dehydrating after cooling to obtain 1019.4 g of (N, N-dimethyl) aminophenol polyoxypropylene (15) (M is 1217), wherein the yield is 89.6%.

(N, N-dimethyl) aminophenol polyoxypropylene (15)608.5 g (0.5 mol) is added into a reaction bottle with an alkali liquor absorption device under the protection of nitrogen, 92.3 g (0.5 mol, M is 190.5 mol) of N-decanoyl chloride is slowly dripped after the mixture is heated to 40 ℃, and after the dripping is finished and the temperature is raised to 80 ℃, the mixture is reacted for 7 hours to obtain (N, N-dimethyl) aminophenol polyoxypropylene (15) N-decanoate.

③ mixing the (N, N-dimethyl) aminophenol polyoxypropylene (15) N-decanoate obtained in the step (II) with octyl benzene according to the molar ratio of 1:0.7, and stirring uniformly to obtain the phenol-containing polyether ester composition M06.

[ example 7 ]

Adding 110.1 g (1 mol, M is 110) of benzenediol and 15.2 g of potassium hydroxide into a 2L pressure reactor provided with a stirring device, heating to 80-90 ℃, starting a vacuum system, dehydrating for 1 hour under high vacuum, then replacing for 3-4 times by nitrogen, adjusting the reaction temperature of the system to 150 ℃, slowly introducing 1189.0 g (20.5 mol) of propylene oxide, controlling the pressure to be less than or equal to 0.60MPa, cooling to 90 ℃ after the reaction is finished, removing low-boiling-point substances in vacuum, cooling, neutralizing and dehydrating to obtain 1182.4 g of benzenediol polyoxypropylene (20) (M is 1270), wherein the yield is 93.1%.

② under the protection of nitrogen, 591.7 g (0.5 mol) of benzenediol polyoxypropylene (20) is added into a reaction bottle with an alkali liquor absorption device, 106.5 g (1.0 mol, M is 106.5) of n-butyl chloride is slowly dripped when the temperature is raised to 30 ℃, and after the dripping is finished and the temperature is raised to 65 ℃, di-n-butyrate is obtained after the reaction is carried out for 5 hours.

③ mixing the dihydroxybenzene polyoxypropylene (20) di-n-butyrate obtained in the step (II) with the methyl diphenyl ether according to the molar ratio of 1:1.5, and stirring the mixture evenly to obtain the phenol-containing polyether ester composition M07.

[ example 8 ]

Adding 110.1 g (1 mol, M is 110) of benzenediol and 18.5 g of potassium hydroxide into a 2L pressure reactor provided with a stirring device, heating to 80-90 ℃, starting a vacuum system, dehydrating for 1 hour under high vacuum, then replacing for 3-4 times by nitrogen, adjusting the reaction temperature of the system to 140 ℃, slowly introducing 624.8 g (14.2 mol) of ethylene oxide, controlling the pressure to be less than or equal to 0.60MPa, adjusting the temperature to 160 ℃ after the reaction of the ethylene oxide, slowly introducing 734.2 g (10.2 mol) of butylene oxide, and controlling the pressure to be less than or equal to 0.60 MPa. After the reaction, the temperature was reduced to 90 ℃, and the low boiling point product was removed in vacuo, and after cooling, neutralization and dehydration were carried out to obtain 1038.2 g of benzenediol polyoxyethylene (14) polyoxybutylene (10) (M ═ 1444), with a yield of 90.6%.

Adding 722.2 g (0.5 mol) of benzenediol polyoxyethylene (14) polyoxybutylene (10) into a reaction bottle with an alkali liquor absorption device under the protection of nitrogen, heating to 30 ℃, slowly dropwise adding 162.5 g (1.0 mol, M is 162.5) of n-octanoyl chloride, and after the dropwise adding is finished and the temperature is increased to 75 ℃, reacting for 7 hours to obtain benzenediol polyoxyethylene (14) polyoxybutylene (10) di-n-octanoic acid ester.

③ mixing the benzenediol polyoxyethylene (14), polyoxybutylene (10), di-n-caprylate obtained in the step (II) and toluylene according to the molar ratio of 1:2, and stirring uniformly to obtain the phenol-containing polyether ester composition M08.

[ example 9 ]

Adding 110.1 g (1 mol, M is 110) of benzenediol and 6.2 g of potassium hydroxide into a 2L pressure reactor provided with a stirring device, heating to 80-90 ℃, starting a vacuum system, dehydrating for 1 hour under high vacuum, then replacing for 3-4 times by nitrogen, adjusting the reaction temperature of the system to 160 ℃, slowly introducing 583.2 g (8.1 mol) of epoxybutane, controlling the pressure to be less than or equal to 0.60MPa, cooling to 90 ℃ after the reaction is finished, removing low-boiling-point substances in vacuum, cooling, neutralizing and dehydrating to obtain 632.5 g of benzenediol polyoxybutylene (8) (M is 686) with the yield of 92.2%.

② under the protection of nitrogen, 343.1 g (0.5 mol) of benzenediol polyoxybutylene (8) is added into a reaction bottle with an alkali liquor absorption device, 218.5 g (1.0 mol, M is 218.5) of lauroyl chloride is slowly dripped when the heating is carried out to 40 ℃, and the temperature is raised to 90 ℃ after the dripping is finished and the reaction is carried out for 8 hours, thus obtaining the benzenediol polyoxybutylene (8) dilaurate.

③ mixing the benzenediol polyoxybutylene (8) dilaurate obtained in the step (II) and the amyl hydroxybenzoate according to the molar ratio of 1:0.2, and uniformly stirring to obtain the phenol-containing polyether ester composition M09.

[ example 10 ]

Adding 124.2 g (1 mol, M is 124) of hydroxyanisole and 7.9 g of potassium hydroxide into a 2L pressure reactor provided with a stirring device, heating to 80-90 ℃, starting a vacuum system, dehydrating for 1 hour under high vacuum, then replacing for 3-4 times with nitrogen, adjusting the reaction temperature of the system to 160 ℃, slowly introducing 655.2 g (9.1 mol) of epoxybutane, controlling the pressure to be less than or equal to 0.60MPa, cooling to 90 ℃ after the reaction is finished, removing low-boiling-point substances in vacuum, cooling, neutralizing and dehydrating to obtain 697.8 g of methoxyphenol polyoxybutylene (9) (M is 772), wherein the yield is 90.4%.

Under the protection of nitrogen, 386.1 g (0.5 mol) of methoxyphenol polyoxybutylene (9) is added into a reaction bottle with an alkali liquor absorption device, isooctyl chloride 81.3 g (0.5 mol, M is 162.5) is slowly dripped when the heating is carried out to 40 ℃, and after the dripping is finished and the temperature is raised to 85 ℃, the reaction is carried out for 6.5 hours, and then methoxyphenol polyoxybutylene (9) isooctanoate is obtained.

③ mixing the methoxyphenol polyoxybutylene (9) isooctanoate obtained in the step (II) and octyl benzene according to the molar ratio of 1:0.35, and stirring uniformly to obtain the phenol-containing polyether ester composition M10.

[ example 11 ]

222.0 g (1 mol, M: 222) of hydroxyphenyl n-octyl ether and boron trifluoride ethyl ether complex were put into a three-necked flask equipped with a stirring dropping funnel and stirred uniformly. When the temperature is raised to a certain temperature, 101.8 g (1.1 mol, M is 92.5) of epichlorohydrin is slowly added dropwise, and after the dropwise addition is finished, the reaction is maintained for 2 hours. Vacuum distilling to remove unreacted epichlorohydrin, adding ethanol solution of sodium hydroxide, and stirring. Filtering to remove the generated sodium chloride, then distilling under reduced pressure to remove ethanol, water and the like, and filtering to remove residual sodium chloride while the solution is hot to obtain the octyloxyphenol glycidyl ether.

Adding 256.0 g (1 mol, M is 256) of octyloxyphenol glycidyl ether and 15.8 g of potassium hydroxide into a 2L pressure reactor provided with a stirring device, heating to 80-90 ℃, starting a vacuum system, dehydrating for 1 hour under high vacuum, then replacing for 3-4 times by nitrogen, adjusting the reaction temperature of the system to 150 ℃, slowly introducing 899.0 g (15.5 mol) of propylene oxide, and controlling the pressure to be less than or equal to 0.60 MPa. After the reaction, the temperature was reduced to 80 ℃ and the low boiling point product was removed in vacuo, followed by cooling, neutralization and dehydration to obtain 1007.7 g of octyloxyphenol hydroxypolyoxypropylene (1) polyoxypropylene (15) (M. 1126), with a yield of 89.5%.

③ adding 0.5 mol of octoxyphenol hydroxyl polyoxypropylene (1) polyoxypropylene (15)563.1 g into a reaction bottle with an alkali liquor absorption device under the protection of nitrogen, slowly adding 78.5 g of acetyl chloride (1.0 mol, M is 78.5) dropwise at 20 ℃, and reacting for 7 hours after the acetyl chloride is completely added to 85 ℃ to obtain the octoxyphenol polyoxypropylene (16) diacetate.

Fourthly, mixing the octyloxyphenol polyoxypropylene (16) diacetate obtained in the step II with N, N-diethylaniline according to the molar ratio of 1:8.5, and uniformly stirring to obtain the phenol-containing polyether ester composition M11.

[ example 12 ]

166.0 g (1 mol, M is 166) of methyl p-hydroxybenzoate and 4.9 g of potassium hydroxide are added into a 2L pressure reactor provided with a stirring device, a vacuum system is started when the temperature is heated to 80-90 ℃, a high vacuum is performed for dehydration for 1 hour, then nitrogen is used for replacing for 3-4 times, the reaction temperature of the system is adjusted to 160 ℃, 223.2 g (3.1 mol) of epoxy butane is slowly introduced, the pressure is controlled to be less than or equal to 0.60MPa, after the reaction is finished, the temperature is reduced to 90 ℃, low boiling substances are removed in vacuum, after cooling, neutralization and dehydration are performed, 364.0 g of p-methoxyacyl phenol polyoxybutylene (3) (M is 382), and the yield is 95.3%.

Under the protection of nitrogen, 191.0 g (0.5 mol) of p-methoxyacyl phenol polyoxybutylene (3) is added into a reaction bottle with an alkali liquor absorption device, 150.2 g (0.5 mol, M is 300.5) of oleoyl chloride is slowly dripped when the heating is carried out to 40 ℃, and the p-methoxyacyl phenol polyoxybutylene (3) oleate is obtained after the oleoyl chloride is dripped to 70 ℃ and reacts for 9 hours.

③ mixing the p-methoxylphenol polyoxybutylene (3) oleate obtained in the step (II) with diphenyl ether according to the molar ratio of 1:2.7, and stirring uniformly to obtain the phenol-containing polyether ester composition M12.

[ example 13 ]

Adding 194.2 g (1 mol, M is 194) of n-butyl p-hydroxybenzoate and 11.1 g of potassium hydroxide into a 2L pressure reactor provided with a stirring device, heating to 80-90 ℃, starting a vacuum system, dehydrating under high vacuum for 1 hour, then replacing 3-4 times with nitrogen, adjusting the reaction temperature of the system to 150 ℃, slowly introducing 881.6 g (15.2 mol) of propylene oxide, controlling the pressure to be less than or equal to 0.60MPa, cooling to 90 ℃ after the reaction is finished, removing low-boiling-point substances in vacuum, cooling, neutralizing and dehydrating to obtain 967.1 g of p-butoxy acyl phenol polyoxypropylene (15) (M is 1064), wherein the yield is 90.9%.

Under the protection of nitrogen, 532.1 g (0.5 mol) of p-butoxy acylphenol polyoxypropylene (15) is added into a reaction bottle, 51.1 g (0.5 mol, M is 102) of acetic anhydride is slowly dripped after the reaction bottle is heated to 30 ℃, and the temperature is raised to 65 ℃ after the dripping is finished, so that p-butoxy acylphenol polyoxypropylene (15) acetate is obtained after 8 hours of reaction.

③ mixing the p-butoxy acyl phenol polyoxypropylene (15) acetate obtained in the step (II) with dodecyl benzene according to the molar ratio of 1:1.2, and stirring uniformly to obtain the phenol-containing polyether ester composition M13.

[ example 14 ]

Adding 306.4 g (1 mol, M is 306) of n-dodecyl p-hydroxybenzoate and 13.4 g of potassium hydroxide into a 2L pressure reactor provided with a stirring device, heating to 80-90 ℃, starting a vacuum system, dehydrating for 1 hour under high vacuum, then replacing for 3-4 times by nitrogen, adjusting the reaction temperature of the system to 130 ℃, slowly introducing 88.0 g (2.0 mol) of ethylene oxide, controlling the pressure to be less than or equal to 0.60MPa, adjusting the temperature to 160 ℃ after the reaction of the ethylene oxide, slowly introducing 511.2 g (7.1 mol) of butylene oxide, cooling to 90 ℃ after the reaction is finished, removing low-boiling substances in vacuum, cooling, neutralizing and dehydrating to obtain 818.9 g of n-dodecyl oxyphenol polyoxyethylene (2) (M is 898), wherein the yield is 91.2%.

Adding 449.2 g (0.5 mol) of p-dodecyl oxyacyl phenol polyoxyethylene (2) polyoxybutylene (7) into a reaction bottle with an alkali liquor absorption device under the protection of nitrogen, heating to 30 ℃, slowly dropwise adding 47.7 g (0.5 mol, M is 92.5) of propionyl chloride, and after finishing dropping and rising to 60 ℃, reacting for 5 hours to obtain p-dodecyl oxyacyl phenol polyoxyethylene (2) polyoxybutylene (7) propionate.

③ mixing the p-dodecyl-oxy-acylphenol polyoxyethylene (2) polyoxybutylene (7) propionate obtained in the step (II) and the tert-butyl anisole according to the molar ratio of 1:5.5, and stirring the mixture evenly to obtain the phenol-containing polyether ester composition M14.

[ COMPARATIVE EXAMPLE 1 ]

The same as [ example 1 ] except that the octylphenol polyoxypropylene (5) hexanoate ester in M01 was replaced with an equal amount of mesitylene to give composition D1, which was subjected to performance tests and the results are shown in tables 1 and 2.

[ COMPARATIVE EXAMPLE 2 ]

The same as [ example 1 ] except that mesitylene in M01 was replaced with the same amount of octylphenol polyoxypropylene (5) n-hexanoate to give composition D2, which was subjected to performance tests and the results are shown in tables 1 and 2.

[ COMPARATIVE EXAMPLE 3 ]

The difference is that the octyl phenol polyoxypropylene (5) hexanoate obtained in the step (II) and mesitylene are mixed according to the molar ratio of 1:10, and the mixture is uniformly stirred to obtain the phenol-containing polyether ester composition D3.

[ COMPARATIVE EXAMPLE 4 ]

The same as [ example 1 ] except that the commercially available oil-soluble viscosity-reducing agent SLYR-02 was used in place of M01 for the performance test, and the results are shown in tables 1 and 2.

[ Experimental example 1 ]

The viscosity of the thickened oils after the addition of 2% by weight of the compositions M01 to M14 at normal pressure was determined and compared with the viscosity of the thickened oils without addition, the results are shown in Table 1. The viscosity of the thickened oil is measured by a Sammer fly rotational rheometer Viscotester IQ Air, and the measuring conditions are as follows: 7.34s^-150 ℃ C. The heavy oil is dehydrated crude oil and comes from eastern oil field. The viscosity-temperature and viscosity-shear rate curves for crude oil # 1 are shown in fig. 2 and 3.

[ Experimental example 2 ]

The viscosity reducing effect of the compositions M01 to M14 and carbon dioxide prepared in examples 1 to 14 on thick oil at high temperature and high pressure was performed by the following steps: weighing 30g of preheated dehydrated thick oil, putting the preheated dehydrated thick oil into a high-pressure closed unit of a rheometer, filling nitrogen to remove oxygen, adjusting the pressure to 15MPa, heating to 90 ℃, and measuring the viscosity mu of the thick oil₀(ii) a Weighing 30g of preheated dehydrated thickened oil and 0.5 wt% of composition (accounting for the percentage of the dehydrated thickened oil) in a piston container, exhausting oxygen in the kettle, covering a piston kettle cover, and closing a top valve; injecting a certain volume of CO into a high-temperature high-pressure piston container by a booster pump₂Heating to 90 ℃; to be treated with CO₂After the pressure is stable, the movable plunger pump is connected with the high-temperature high-pressure piston container, and then CO with a certain volume is injected into the sample preparation kettle₂The pressure needs to be kept constant in the injection process; setting the plunger pump to a constant pressure mode, setting the pressure above the saturation pressure, and adjusting the stirring speed to enable CO to be in a CO stirring state₂Dissolving the mixture in the thick oil completely to complete sample preparation; thirdly, stopping stirring, placing an outlet valve of the sample preparation kettle at the upper end, and standing; the pressure of the sample preparation kettle is increased by 2MPa to prevent the valve from openingSudden pressure drop below saturation at the door results in CO₂Separating out; linking a middle piston container (a piston is firstly arranged at the top) with a sample preparation kettle; closing the valve of the intermediate piston container, and slightly loosening the nut between the pipeline and the intermediate piston container; slowly opening the sample preparation kettle and adding a small amount of CO₂Flowing out of the pipeline, and screwing the screw after the crude oil comes out; transferring crude oil at constant pressure above saturation pressure; filling nitrogen in a high-pressure closed unit of the rheometer to enable the pressure of the closed unit to be above the saturation pressure and below the experimental pressure; connecting the intermediate piston container with a closed unit, firstly discharging oxygen, and transferring crude oil at constant pressure; the pressure is adjusted to 15MPa, the viscosity mu of the thickened oil is measured by a rheometer, and the synergistic viscosity reduction rate is calculated, and the result is shown in Table 2. Wherein the sample preparation kettle is an HKY-3 high-temperature high-pressure sample preparation kettle produced by petroleum scientific research instruments ltd of Jiangsu Haian city, and the viscosity of the thickened oil is measured by an HAAKE MARS III rheometer of Germany Sammerfei company.

Table 1:

table 2: