Photoinitiated multipolymerization of scale inhibitors and method of making same

Abstract

The application discloses a light-initiated multi-polymerization traceable scale inhibitor, and a preparation method thereof.The general structure of the light-initiated multi-polymerization traceable scale inhibitor is as follows: an organic solvent is added into a photo-polymerization reactor, then acrylic acid derivatives, maleic acid, 2-acrylamido-2-methylpropane sulfonic acid and allyl polyethylene glycol are added into the organic solvent and stirred uniformly, then a photo-polymerization initiator is added to carry out a first polymerization reaction to obtain an intermediate, and then N-allyl-4-alkoxy-1,8-naphthalimide derivatives are added into the intermediate to carry out a second polymerization reaction.The light-initiated multi-polymerization traceable scale inhibitor solves the problems of poor scale inhibition effect, single function, and poor temperature resistance and salt resistance of the existing scale inhibitors.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of traceable scale inhibitors, and relates to a photoinitiated multi-polymerization traceable scale inhibitor. BACKGROUND

[0002] With the continuous advancement of secondary and tertiary oil and gas recovery technologies, the water cut is continuously rising. Meanwhile, water injection oil and gas recovery technologies are also widely applied. Due to the incompatibility between water qualities and the thermodynamic changes of water quality in the flow process, scaling is easily caused, which can cause pipeline blockage in severe cases, affecting the normal production of oil and gas fields, and thus it is necessary to adopt a plugging removal method for descaling, which seriously shortens the production cycle of oil and gas fields.

[0003] In order to solve the scaling problem and prolong the normal operation time of oil and gas pipelines, most oil and gas fields adopt the method of adding scale inhibitors for scale prevention, so as to prevent the massive deposition of inorganic scale and prolong the normal production cycle of oil and gas fields. At present, the types of scale inhibitors that are more commonly used include organic phosphonic acid, polyepoxysuccinic acid or polyamino acid, and organic acid multi-polymer scale inhibitors. However, due to the phosphorus content of organic phosphonic acid, it does not meet the environmental protection requirements, and thus it is less used. Polyepoxysuccinic acid or polyamino acid has poor scale inhibition effect on barium sulfate. At present, the more commonly used scale inhibitors are organic acid multi-polymer scale inhibitors. However, this type of scale inhibitor has single functionality, and due to the difference in polymerization monomers, the scale inhibition performance is also different. Moreover, due to the conditions such as high salinity and high concentration of scale-forming ions in the water in individual oilfields, most scale inhibitors have poor temperature resistance and salt tolerance, and thus it is difficult to achieve good scale prevention effect. SUMMARY

[0004] The purpose of the present application is to provide a photoinitiated multi-polymerization traceable scale inhibitor, which solves the problems of poor scale inhibition effect, single functionality, and poor temperature resistance and salt tolerance of the existing scale inhibitors.

[0005] Another purpose of the present application is to provide a preparation method of the scale inhibitor.

[0006] The technical solution adopted by the present application is that the photoinitiated multi-polymerization traceable scale inhibitor has a structure general formula as shown in formula 1.

[0007]

[0008] In the formula, R is -H, -CH3 or -CH2CH3; R1 is -OCH3 or -OC2H5; the value of a is an integer in the range of 150-200; the value of b is an integer in the range of 200-300; the value of c is an integer in the range of 100-150; d is an integer in the range of 30-60; the value of e is an integer in the range of 10-15; and f is an integer in the range of 5-10.

[0009] Another technical solution adopted by the present application is a preparation method of the light-initiated multi-polymerization traceable scale inhibitor, and the steps are as follows:

[0010] Step 1: add an organic solvent into a photopolymerization reactor, then add an acrylic acid derivative, maleic acid, 2-acrylamido-2-methylpropane sulfonic acid and allyl polyethylene glycol into the organic solvent, stir uniformly, then add a photopolymerization initiator, stir and then perform a first polymerization reaction to obtain an intermediate;

[0011] Step 2: add an N-allyl-4-alkoxy-1,8-naphthalimide derivative into the intermediate obtained in Step 1 to perform a second polymerization reaction, thereby obtaining the light-initiated multi-polymerization traceable scale inhibitor with a structural formula as shown in Formula 1:

[0012]

[0013] In the formula, R is -H, -CH3 or -CH2CH3; R1 is -OCH3 or -OC2H5; the value of a is an integer of 150-200; the value of b is an integer of 200-300; the value of c is an integer of 100-150; d is an integer of 30-60; the value of e is an integer of 10-15; and f is an integer of 5-10.

[0014] The present application also has the following characteristics:

[0015] The structural general formula of the acrylic acid derivative in Step 1 is shown in Formula 2:

[0016]

[0017] In the formula, R is -H, -CH3 or -CH2CH3.

[0018] The acrylic acid derivative is used as a basic component, and the molar ratio of the acrylic acid derivative to maleic acid in Step 1 is 1:1.5-2, the molar ratio of the acrylic acid derivative to 2-acrylamido-2-methylpropane sulfonic acid is 1:0.5-1, and the molar ratio of the acrylic acid derivative to allyl polyethylene glycol is 1:0.2-0.3.

[0019] The organic solvent in Step 1 is any one of isopropyl alcohol, ethanol or dimethylformamide, and the mass of the organic solvent is 1-1.5 times the total mass of the acrylic acid derivative, maleic acid, 2-acrylamido-2-methylpropane sulfonic acid and allyl polyethylene glycol.

[0020] The photopolymerization initiator in Step 1 is any one of benzoin, benzoin dimethyl ether, benzoin ethyl ether, benzoin isopropyl ether or benzoin butyl ether, and the mass of the photopolymerization initiator is 0.1%-0.2% of the total mass of the acrylic acid derivative, maleic acid, 2-acrylamido-2-methylpropane sulfonic acid and allyl polyethylene glycol.

[0021] The molar ratio of the N-allyl-4-alkoxy-1,8-naphthalimide derivative to the acrylic acid derivative in step 2 is 1:0.05-0.1.

[0022] The general structure of the N-allyl-4-alkoxy-1,8-naphthalimide derivative in step 2 is shown in formula 3:

[0023]

[0024] In the formula, R is -OCH3 or -OCH2CH3.

[0025] The first polymerization process is carried out in a photopolymerization reactor with ultraviolet light, at room temperature, with full-time stirring at a stirring rate of 100-120 r / min, an ultraviolet wavelength of 360-420 nm, and a reaction time of 3-4 h.

[0026] The second polymerization process is carried out in a photopolymerization reactor with ultraviolet light, at room temperature, with full-time stirring at a stirring rate of 100-120 r / min, an ultraviolet wavelength of 360-420 nm, and a reaction time of 2-3 h.

[0027] The present application has the following beneficial effects:

[0028] 1. The scale inhibitor of the present application is a five-membered polymeric copolymer, which has good chelation scale inhibition ability for inorganic scales such as calcium carbonate, calcium sulfate, and barium sulfate. The scale inhibitor has a wide application range, good temperature resistance and salt tolerance, and strong dispersing ability. By copolymerization with a fluorescent substance, the polymer itself has fluorescent properties. According to the linear relationship between the polymer concentration and the fluorescent light intensity, quantitative tracing analysis of the scale inhibitor application process can be realized.

[0029] 2. The scale inhibitor of the present application is copolymerized from multiple polymerization monomers, which can produce good chelation with metal ions. The scale inhibitor molecules are subjected to multi-polymerization by photopolymerization, which has the characteristics of mild reaction rate, controllable reaction, and easy operation compared to traditional thermal polymerization. DETAILED DESCRIPTION

[0030] The present application will be described in detail below in conjunction with specific embodiments.

[0031] The general structure of the scale inhibitor subjected to traceable photoinitiated multi-polymerization is shown in formula 1:

[0032]

[0033] Wherein, R is -H, -CH3 or -CH2CH3; R1 is -OCH3 or -OC2H5; a is an integer of 150-200; b is an integer of 200-300; c is an integer of 100-150; d is an integer of 30-60; e is an integer of 10-15; and f is an integer of 5-10.

[0034] The preparation method of the light-initiated multi-polymerization traceable scale inhibitor comprises the following steps:

[0035] Step 1: adding an organic solvent into a photopolymerization reactor with ultraviolet light, then adding acrylic acid derivatives, maleic acid, 2-acrylamido-2-methylpropane sulfonic acid and allyl polyethylene glycol into the organic solvent, stirring uniformly, then adding a photopolymerization initiator, and performing a first polymerization reaction to obtain an intermediate, and the reaction formula is as follows:

[0036]

[0037] The acrylic acid derivatives are basic components, the molar ratio of the acrylic acid derivatives to the maleic acid is 1:1.5-2, the molar ratio of the acrylic acid derivatives to the 2-acrylamido-2-methylpropane sulfonic acid is 1:0.5-1, the molar ratio of the acrylic acid derivatives to the allyl polyethylene glycol is 1:0.2-0.3, and the general formula of the acrylic acid derivatives is as follows:

[0038]

[0039] In the formula, R is -H, -CH3 or -CH2CH3.

[0040] The organic solvent is any one of isopropyl alcohol, ethanol and dimethylformamide, and the mass of the organic solvent is 1-1.5 times the total mass of the acrylic acid derivatives, the maleic acid, the 2-acrylamido-2-methylpropane sulfonic acid and the allyl polyethylene glycol.

[0041] The photopolymerization initiator is any one of benzoin, benzoin dimethyl ether, benzoin ethyl ether, benzoin isopropyl ether and benzoin butyl ether, and the mass of the photopolymerization initiator is 0.1-0.2% of the total mass of the acrylic acid derivatives, the maleic acid, the 2-acrylamido-2-methylpropane sulfonic acid and the allyl polyethylene glycol, wherein the first polymerization process is that the reaction process is stirred at a stirring rate of 100-120 r / min, the ultraviolet wavelength is 360-420 nm, and the first polymerization reaction time is 3-4 h.

[0042] Step 2: adding N-allyl-4-alkoxy-1,8-naphthalimide derivatives into the intermediate to perform a second polymerization reaction, so as to obtain the light-initiated multi-polymerization traceable scale inhibitor, and the reaction formula is as shown in the following formula 5:

[0043]

[0044] In the formula, R is -H, -CH3 or -CH2CH3; R1 is -OCH3 or -OC2H5; the value of a is an integer in 150-200; the value of b is an integer in 200-300; the value of c is an integer in 100-150; d is an integer in 30-60; the value of e is an integer in 10-15; and f is an integer in 5-10.

[0045] The molar ratio of the N-allyl-4-alkoxy-1,8-naphthalimide derivative to the acrylic acid derivative is 1:0.05-0.1, and the structural general formula of the N-allyl-4-alkoxy-1,8-naphthalimide derivative is shown in formula 3.

[0046]

[0047] In the formula, R1 is -OCH3 or -OCH2CH3.

[0048] The second polymerization reaction process is: room temperature reaction, full-time stirring during the reaction, the stirring rate is 100-120 r / min, the ultraviolet wavelength is 360-420 nm, and the second polymerization reaction time is 2-3 h.

[0049] The scale inhibitor is copolymerized by a plurality of polymerization monomers, can produce good chelation with metal ions, has a plurality of carboxyl groups in the molecule, can be dissociated into a plurality of negative ions in water, can make the inorganic scale particle surface carry negative electricity, increase the repulsive force between the scale particles, and play a good dispersion effect; in addition, the sulfonic acid group is introduced into the polymer molecule, the salt resistance and temperature resistance of the scale inhibitor molecule are enhanced; the allyl polyethylene glycol is used as the polymerization monomer, the polyethylene glycol structure can make the formed polymer have stronger dispersibility and solubility.

[0050] The N-allyl-4-alkoxy-1,8-naphthalimide derivative is used as a polymerization monomer, can make the polymer have fluorescence performance, the linear relationship between the polymer concentration and the fluorescence intensity can realize quantitative tracing analysis of the scale inhibitor application process; in addition, the N-allyl-4-alkoxy-1,8-naphthalimide derivative can produce fluorescence under ultraviolet light irradiation, enhances the self light intensity in the reaction system, is beneficial to promoting the positive progress of the photopolymerization reaction, and secondly, the light polymerization is used to carry out the multi-polymerization of the scale inhibitor molecules, compared with the traditional thermal polymerization reaction, has the characteristics of mild reaction rate, controllable and easy-to-operate reaction.

[0051] Example 1

[0052] Into the photopolymerization reactor, solvent dimethylformamide was added, then acrylic acid, maleic acid, 2-acrylamido-2-methylpropane sulfonic acid, allyl polyethylene glycol were added in a molar ratio of 1:2:1:0.3, the mass of the organic solvent dimethylformamide was 1.5 times the total mass of acrylic acid, maleic acid, 2-acrylamido-2-methylpropane sulfonic acid, and allyl polyethylene glycol, and stirring was performed at room temperature until the mixture was uniform, then benzoin dimethyl ether was added in an amount of 0.2% of the total mass of the reaction monomers, and a UV light source was turned on, with the UV wavelength set at 420 nm, and the reaction was stirred at room temperature for 4 h at a stirring rate of 120 r / min;

[0053] N-allyl-4-alkoxy-1,8-naphthalimide derivative was continuously added in a molar ratio of 1:0.05 with respect to acrylic acid, and the reaction was continuously performed under UV light for 2 h to obtain a final reaction product, wherein the general structure of the N-allyl-4-alkoxy-1,8-naphthalimide derivative is shown in Formula 6:

[0054]

[0055] Example 2

[0056] Into the photopolymerization reactor, solvent dimethylformamide was added, then acrylic acid, maleic acid, 2-acrylamido-2-methylpropane sulfonic acid, allyl polyethylene glycol were added in a molar ratio of 1:2:1:0.3, the mass of the organic solvent dimethylformamide was 1.5 times the total mass of acrylic acid, maleic acid, 2-acrylamido-2-methylpropane sulfonic acid, and allyl polyethylene glycol, and stirring was performed at room temperature until the mixture was uniform, then benzoin dimethyl ether was added in an amount of 0.2% of the total mass of the reaction monomers, and a UV light source was turned on, with the UV wavelength set at 420 nm, and the reaction was stirred at room temperature for 4 h at a stirring rate of 120 r / min;

[0057] N-allyl-4-alkoxy-1,8-naphthalimide derivative was continuously added in a molar ratio of 1:0.1 with respect to acrylic acid, and the reaction was continuously performed under UV light for 3 h to obtain a final reaction product, wherein the general structure of the N-allyl-4-alkoxy-1,8-naphthalimide derivative is shown in Formula 6:

[0058]

[0059] Example 3

[0060] Into the photopolymerization reactor, solvent isopropanol is added, then acrylic acid, maleic acid, 2-acrylamido-2-methylpropane sulfonic acid, allyl polyethylene glycol are added in a molar ratio of 1:2:0.8:0.25, the mass of the organic solvent isopropanol is 1.2 times the total mass of acrylic acid, maleic acid, 2-acrylamido-2-methylpropane sulfonic acid, allyl polyethylene glycol, stirring at room temperature, after mixing uniformly, benzoin is added accounting for 0.15% of the total mass of the reaction monomers, and the ultraviolet light source is turned on, the ultraviolet wavelength is set at 400 nm, and the reaction is stirred at room temperature for 3.5 h at a stirring rate of 110 r / min;

[0061] N-allyl-4-alkoxy-1,8-naphthalimide derivative in a molar ratio of 1:0.08 with acrylic acid is continuously added, and the reaction is continuously carried out under ultraviolet light for 2.5 h to obtain the final reaction product, wherein the general structure of the N-allyl-4-alkoxy-1,8-naphthalimide derivative is shown in formula 6:

[0062]

[0063] Example 4

[0064] Into the photopolymerization reactor, solvent isopropanol is added, then acrylic acid, maleic acid, 2-acrylamido-2-methylpropane sulfonic acid, allyl polyethylene glycol are added in a molar ratio of 1:1.8:1:0.2, the mass of the organic solvent isopropanol is 1 times the total mass of acrylic acid, maleic acid, 2-acrylamido-2-methylpropane sulfonic acid, allyl polyethylene glycol, stirring at room temperature, after mixing uniformly, benzoin isopropanol is added accounting for 0.1% of the total mass of the reaction monomers, and the ultraviolet light source is turned on, the ultraviolet wavelength is set at 380 nm, and the reaction is stirred at room temperature for 4 h at a stirring rate of 120 r / min;

[0065] N-allyl-4-alkoxy-1,8-naphthalimide derivative in a molar ratio of 1:0.05 with acrylic acid is continuously added, and the reaction is continuously carried out under ultraviolet light for 2 h to obtain the final reaction product, wherein the general structure of the N-allyl-4-alkoxy-1,8-naphthalimide derivative is shown in formula 6:

[0066]

[0067] Example 5

[0068] Into a photopolymerization reactor, solvent isopropanol is added, followed by acrylic acid, maleic acid, 2-acrylamido-2-methylpropanesulfonic acid, and allyl polyethylene glycol in a molar ratio of 1:1.5:1:0.3. The mass of the organic solvent isopropanol is 1.5 times the total mass of acrylic acid, maleic acid, 2-acrylamido-2-methylpropanesulfonic acid, and allyl polyethylene glycol. The mixture is stirred at room temperature until uniform, followed by the addition of benzoin dimethyl ether accounting for 0.2% of the total mass of the reaction monomers. The UV light source is turned on, and the UV wavelength is set at 390 nm. The reaction is stirred at room temperature for 4 h at a stirring rate of 110 r / min.

[0069] N-allyl-4-alkoxy-1,8-naphthalimide derivative is continuously added in a molar ratio of 1:0.1 with respect to acrylic acid. The reaction is continuously carried out under UV light for 3 h to obtain the final reaction product. The general structure of the N-allyl-4-alkoxy-1,8-naphthalimide derivative is shown in Formula 6.

[0070]

[0071] Example 6

[0072] Into a photopolymerization reactor, solvent isopropanol is added, followed by acrylic acid, maleic acid, 2-acrylamido-2-methylpropanesulfonic acid, and allyl polyethylene glycol in a molar ratio of 1:1.5:1:0.3. The mass of the organic solvent isopropanol is 1.5 times the total mass of acrylic acid, maleic acid, 2-acrylamido-2-methylpropanesulfonic acid, and allyl polyethylene glycol. The mixture is stirred at room temperature until uniform, followed by the addition of benzoin dimethyl ether accounting for 0.2% of the total mass of the reaction monomers. The UV light source is turned on, and the UV wavelength is set at 390 nm. The reaction is stirred at room temperature for 4 h at a stirring rate of 110 r / min.

[0073] N-allyl-4-alkoxy-1,8-naphthalimide derivative is continuously added in a molar ratio of 1:0.1 with respect to acrylic acid. The reaction is continuously carried out under UV light for 2 h to obtain the final reaction product. The general structure of the N-allyl-4-alkoxy-1,8-naphthalimide derivative is shown in Formula 6.

[0074]

[0075] Example 7

[0076] The preparation process of the scale inhibitor is the same as that in Example 1, except that the organic reaction solvent isopropanol is replaced by ethanol.

[0077] Example 8

[0078] The preparation process of the scale inhibitor is the same as that in Example 1, except that the photopolymerization initiator benzoin dimethyl ether is replaced by benzoin ether.

[0079] Example 9

[0080] The preparation process of the scale inhibitor is the same as that of Example 1, except that the acrylic acid derivative is replaced by methacrylic acid.

[0081] Example 10

[0082] The preparation process of the scale inhibitor is the same as that of Example 1, except that the polymerization monomer, i.e. N-allyl-4-alkoxy-1,8-naphthalimide derivative is replaced by

[0083] Comparative Example 1

[0084] The scale inhibitor is prepared according to the method of Example 1, except that no allyl polyethylene glycol is added.

[0085] Comparative Example 2

[0086] The scale inhibitor is prepared according to the method of Example 1, except that no 2-acrylamido-2-methylpropane sulfonic acid is added.

[0087] Comparative Example 3

[0088] The scale inhibitor is prepared according to the method of Example 1, except that no maleic acid is added.

[0089] Comparative Example 4

[0090] The scale inhibitor is prepared by a thermal polymerization method, and no is included in the polymerization monomer, and the photopolymerization initiator is replaced by a thermal polymerization initiator.

[0091] Under the same conditions, the scale inhibitors prepared in Examples 1-10 and Comparative Examples 1-4 are subjected to scale inhibition rate tests for calcium carbonate, calcium sulfate and barium sulfate, respectively, and the results of the scale inhibition rate tests are shown in Table 1 below:

[0092] Table 1 Scale Inhibition Test Results

[0093]

[0094]

[0095] As can be seen from the above table, the scale inhibitor is a pentapolymer copolymer, and has good chelation scale inhibition ability for inorganic scales such as calcium carbonate, calcium sulfate and barium sulfate, and can reach more than 90%. The scale inhibitor has a wide application range, good temperature resistance and salt resistance, and strong dispersion ability. By copolymerization with a fluorescent substance, the polymer itself has fluorescent properties, and according to the linear relationship between the polymer concentration and the fluorescent light intensity, quantitative tracing analysis of the application process of the scale inhibitor can be realized.

Claims

1. A process for the preparation of a photo-initiated multi-functional polymerizable traceable scale inhibitor, characterized in that, The steps are as follows: Step 1: add an organic solvent to a photopolymerization reactor, then add an acrylic acid derivative, maleic acid, 2-acrylamido-2-methylpropane sulfonic acid, and allyl polyethylene glycol to the organic solvent, stir until uniform, then add a photopolymerization initiator, stir, and then perform a first polymerization reaction to obtain an intermediate; Step 2: add an N-allyl-4-alkoxy-1,8-naphthalimide derivative to the intermediate obtained in Step 1 to perform a second polymerization reaction, thereby obtaining a photoinitiated multi-polymerization traceable scale inhibitor having a structure as shown in Formula 1: (Formula 1) In the formula, R is -H, -CH3, or -CH2CH3; R1 is -OCH3 or -OC2H5; a is an integer of 150-200; b is an integer of 200-300; c is an integer of 100-150; d is an integer of 30-60; e is an integer of 10-15; and f is an integer of 5-10.

2. The production method according to claim 1, characterized by, The acrylic acid derivative in Step 1 has a general structure as shown in Formula 2: (Formula 2) In the formula, R is -H, -CH3, or -CH2CH3.

3. The production method according to claim 1 or 2, characterized by, The molar ratio of the acrylic acid derivative to maleic acid in Step 1 is 1:1.5-2, the molar ratio of the acrylic acid derivative to 2-acrylamido-2-methylpropane sulfonic acid is 1:0.5-1, and the molar ratio of the acrylic acid derivative to allyl polyethylene glycol is 1:0.2-0.

3.

4. The production method according to claim 1, characterized by, The organic solvent in Step 1 is any one of isopropyl alcohol, ethanol, or dimethylformamide; and the mass of the organic solvent is 1-1.5 times the total mass of the acrylic acid derivative, maleic acid, 2-acrylamido-2-methylpropane sulfonic acid, and allyl polyethylene glycol.

5. The method of claim 1, wherein, The photopolymerization initiator in Step 1 is any one of benzoin, benzoin dimethyl ether, benzoin ethyl ether, benzoin isopropyl ether, or benzoin butyl ether; and the mass of the photopolymerization initiator is 0.1%-0.2% of the total mass of the acrylic acid derivative, maleic acid, 2-acrylamido-2-methylpropane sulfonic acid, and allyl polyethylene glycol.

6. The method of claim 1, wherein, The molar ratio of the N-allyl-4-alkoxy-1,8-naphthalimide derivative to the acrylic acid derivative in Step 2 is 1:0.05-0.

1.

7. The production method according to claim 1 or 6, characterized by, The N-allyl-4-alkoxy-1,8-naphthalimide derivative in Step 2 has a general structure as shown in Formula 3: (Formula 3) In the formula, R1 is -OCH3 or -OCH2CH3.

8. The method of claim 1, wherein, The first polymerization reaction process is performed in a photopolymerization reactor with ultraviolet light, at room temperature, with stirring at a rate of 100-120 r / min, an ultraviolet wavelength of 360-420 nm, and a reaction time of 3-4 h.

9. The method of claim 1, wherein, The second polymerization reaction process is performed in a photopolymerization reactor with ultraviolet light, at room temperature, with stirring at a rate of 100-120 r / min, an ultraviolet wavelength of 360-420 nm, and a reaction time of 2-3 h.

10. The photo-initiated multi-polymerizable scale-inhibitor prepared according to the method of claim 1, characterized in that, The general structure is shown in Formula 1: (Formula 1) wherein R is -H, -CH3, or -CH2CH3; R1is -OCH3or -OC2H5; a is an integer from 150 to 200; b is an integer from 200 to 300; c is an integer from 100 to 150; d is an integer from 30 to 60; e is an integer from 10 to 15; and f is an integer from 5 to 10.

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