Quaternary ammonium salt and preparation method and application thereof

Abstract

The invention discloses a quaternary ammonium salt and a preparation method and application thereof, the quaternary ammonium salt is a hydroxyl-containing water-soluble polyoxyethylene quaternary ammonium salt cationic surfactant, and a phosphorus-free corrosion and scale inhibition bactericide comprises the following components in parts by weight: 0.1-15 parts of the quaternary ammonium salt, 0.1-10 parts of polyaspartic acid or polyaspartate, 0.1-5 parts of gluconate and 0.1-5 parts of inorganic zinc salt. 0.1 to 5 parts of citric acid; and 60 to 99.5 parts of a solvent. The non-phosphorus corrosion and scale inhibition bactericide has the characteristics of good mildew resistance, good sterilization effect and low probability of bubbles, and the variety of a non-phosphorus medicament system is expanded.

Description

Technical Field

[0001] The invention relates to the technical field of water treatment, and in particular to a quaternary ammonium salt and a preparation method and application thereof. Background Art

[0002] Natural gas purification plants bear the important responsibility of desulfurizing and decarbonizing natural gas. The thermal cycle of process media is a key link in the entire process. Therefore, the stable operation of the circulating water system is of great significance to the safe production of natural gas purification plants. Natural gas purification plants in Sichuan and Chongqing generally use open circulating cooling water systems. Measures need to be taken to control corrosion, scaling and sterilization problems in daily operation.

[0003] For corrosion, scaling and sterilization control, adding water treatment agents is the most common practice at present. It is simple to operate, low cost and effective. Among them, phosphorus-based agents are the most mature. However, with the updating and iteration of agent technology itself and the increasingly stringent requirements of environmental protection laws and policies, the first-level discharge standard of GB 8978-1996 "Comprehensive Sewage Discharge Standard" requires phosphate (in terms of P) ≤ 0.5mg / L, and phosphorus-free water treatment agents have become an inevitable trend.

[0004] In recent years, the phosphorus-free agent system has also been rapidly developed. At present, carboxylic acid polymers represented by polyepoxysuccinic acid and polyaspartic acid have been widely used. In addition, Publication No. CN 112320978A discloses a corrosion-inhibiting and scale-inhibiting bactericide, wherein the composition contains modified polyaspartic acid, sodium myristoyl glutamate, benzotriazole, and sodium tungstate; Publication No. CN 110330122A discloses a composite corrosion-inhibiting and scale-inhibiting bactericide, comprising the following components: a modified nanocellulose quaternary ammonium salt mixed solution, an oxidized nanocellulose mixed solution, an alkylamine emulsion, and a betaine-type surfactant; Publication No. CN114314865A discloses a multifunctional water treatment agent with corrosion-inhibiting and scale-inhibiting functions, which is prepared by compounding polyglutamic acid with a molecular weight of 15±0.5kDa, imidazoline, benzyldimethyltetradecyl ammonium chloride (BDTAC) and zinc salt.

[0005] In general, the types and quantities of available phosphorus-free agent systems are still relatively small, and there are still certain defects in the actual application process, such as the possibility of mildew after the agent is left for a long time, poor bactericidal effect, severe foaming and other problems. Summary of the invention

[0006] The technical problem to be solved by the present invention is that the types and quantities of existing phosphorus-free agent systems are still relatively small.

[0007] The first object of the present invention is to provide a quaternary ammonium salt, the structure of which is shown in formula (I):

[0008]

[0009] In the formula, the value range of m is 0 to 100, the value range of n is 0 to 100, and both m and n are integers.

[0010] The quaternary ammonium salt in formula (I) is a cationic surfactant with good bactericidal effect, low surface tension and good water solubility. It can be seen that it can be used as a bactericide, expanding the types of phosphorus-free agents.

[0011] The second object of the present invention is to provide a method for preparing the quaternary ammonium salt, comprising:

[0012] 10 to 20 parts by weight of triazine, 30 to 40 parts by weight of chloromethylnaphthylamine and 10 to 15 parts by weight of zinc chloride are subjected to a reverse substitution reaction in the presence of a first initiator and a first catalyst to obtain triaminonaphthylmethyltriazine;

[0013] reacting triaminonaphthylmethyl triazine and ethylene oxide in the presence of a second initiator and a second catalyst at a reaction temperature of 150 to 220° C. to obtain the quaternary ammonium salt;

[0014] The weight portion of the triaminonaphthylmethyl triazine is 10 to 15 parts, and the weight portion of ethylene oxide is 80 to 90 parts.

[0015] The third object of the present invention is to provide a phosphorus corrosion inhibitor, scale inhibitor and fungicide, which contains the above-mentioned quaternary ammonium salt.

[0016] As a possible design, the phosphorus corrosion and scale inhibitor bactericide also contains polyaspartic acid or polyaspartate.

[0017] The beneficial effects of the present invention are as follows: the phosphorus corrosion and scale inhibition bactericide obtained by compounding polyaspartic acid or polyaspartate and quaternary ammonium salt has good mildew resistance, good bactericidal effect and is not easy to form bubbles, thereby expanding the types of phosphorus-free agent systems. DETAILED DESCRIPTION

[0018] In order to make the purpose, technical solutions and advantages of the present invention more clearly understood, the present invention is further described in detail below in conjunction with embodiments. The illustrative embodiments of the present invention and their description are only used to explain the present invention and are not intended to limit the present invention.

[0019] It should be noted that when an element is referred to as being "fixed to" or "disposed on" another element, it can be directly on the other element or indirectly on the other element. When an element is referred to as being "connected to" another element, it can be directly connected to the other element or indirectly connected to the other element.

[0020] In addition, the terms "first" and "second" are used for descriptive purposes only and should not be understood as indicating or implying relative importance or implicitly indicating the number of the indicated technical features. Therefore, the features defined as "first" and "second" may explicitly or implicitly include one or more of the features. In the description of the present invention, the meaning of "multiple" is two or more, unless otherwise clearly and specifically defined. The meaning of "several" is one or more, unless otherwise clearly and specifically defined.

[0021] In the description of the present invention, it should be noted that, unless otherwise clearly specified and limited, the terms "installed", "connected", and "connected" should be understood in a broad sense, for example, it can be a fixed connection, a detachable connection, or an integral connection; it can be a mechanical connection or an electrical connection; it can be a direct connection or an indirect connection through an intermediate medium, it can be the internal connection of two elements or the interaction relationship between two elements. For ordinary technicians in this field, the specific meanings of the above terms in the present invention can be understood according to specific circumstances.

[0022] The present invention aims at solving the problem that the types and quantities of available phosphorus-free agent systems are relatively small, and provides a quaternary ammonium salt as shown in formula (I).

[0023]

[0024] In the formula, m and n are both integers, wherein m ranges from 0 to 100, for example, 2, 10, 15, 22, 27, 35, 55, 76, 89 and 99, preferably 0 to 45; n ranges from 0 to 100, for example, 2, 10, 15, 22, 27, 35, 55, 76, 89 and 99, preferably 0 to 55.

[0025] The synthetic route of the quaternary ammonium salt shown in formula (I) is as follows:

[0026]

[0027]

[0028] The specific synthesis method of the quaternary ammonium salt shown in formula (I) is as follows:

[0029] S1. 10 to 20 parts by weight of triazine, 30 to 40 parts by weight of chloromethylnaphthylamine and 10 to 15 parts by weight of zinc chloride are subjected to a reverse substitution reaction in the presence of a first initiator and a first catalyst to obtain triaminonaphthylmethyl triazine;

[0030] S2. The triaminonaphthylmethyl triazine and ethylene oxide are reacted in the presence of a second initiator and a second catalyst at a reaction temperature of 150 to 220 ° C to obtain the quaternary ammonium salt;

[0031] The weight portion of the triaminonaphthylmethyl triazine is 10 to 15 parts, and the weight portion of ethylene oxide is 80 to 90 parts.

[0032] In the present invention, a multi-step substitution reaction mainly occurs in step S1, wherein zinc chloride is used as a catalyst, the first initiator can be an organic peroxide compound, the amount of the initiator is generally 20 to 25 parts, preferably benzoyl peroxide; the reaction conditions are normal temperature and pressure. After the reaction is completed, the triaminonaphthylmethyl triazine can also be purified by extraction and filtration.

[0033] In the present invention, in step S2, the second initiator is generally an organic peroxide compound, the second catalyst is generally an aromatic compound, the amount of the second initiator is generally 30 to 35 parts, preferably benzoyl peroxide; the amount of the second catalyst is generally 20 to 30 parts, preferably toluene.

[0034] Step S2 can be obtained by two-step reaction, as follows:

[0035] S21. After the triaminonaphthylmethyl triazine and part of the ethylene oxide are reacted at 150 to 180°C;

[0036] S22. Add the second catalyst and the remaining ethylene oxide therein to react at 200-220°C.

[0037] The entire reaction process is carried out in an oxygen-free environment, specifically in a closed environment.

[0038] In step S21, generally, ethylene oxide is introduced into a closed environment containing triaminonaphthylmethyl triazine. Before introducing ethylene oxide, the closed environment containing triaminonaphthylmethyl triazine may be evacuated, and then heated to 150-220° C., and then ethylene oxide is added, and finally the reaction temperature is raised to 150-180° C.

[0039] In order to prevent the temperature of the reaction system from dropping too quickly after adding ethylene oxide, the reaction system may be heated to a certain temperature, for example, 55 to 70° C., before adding ethylene oxide.

[0040] In order to avoid excessive pressure in the closed environment and affect the safety of the synthesis process, ethylene oxide can be continuously introduced until the amount introduced meets the requirements. During the continuous introduction process, the pressure of the closed environment is maintained at 0.2-0.3Mpa as much as possible. When the amount of ethylene oxide added is completed, until the pressure of the closed environment becomes negative pressure, it indicates that the reaction process is completed and tris[(N,N)-hydroxyethylnaphthylmethyl]-triazinium is obtained.

[0041] In step S22, before adding the remaining ethylene oxide, the tris[(N,N)-hydroxyethylnaphthylmethyl]-triazinium obtained in step S21 can be cooled to 70-80°C and a catalyst can be added at the same time. When the pressure of the closed environment becomes negative pressure, it indicates that the reaction process is complete, and the material can be discharged after cooling. The temperature after cooling is generally 70-80°C.

[0042] The invention also discloses a phosphorus corrosion and scale inhibition bactericide, which comprises a quaternary ammonium salt represented by formula (I).

[0043] In the present invention, the phosphorus corrosion and scale inhibition bactericide may also include polyaspartic acid or polyaspartate salts. By compounding the quaternary ammonium salt and polyaspartic acid or polyaspartate salts, it not only has a good bactericidal effect, but also has stable performance and is not easy to form bubbles.

[0044] In the present invention, the phosphorus corrosion inhibitor and scale inhibitor can also include gluconate, inorganic zinc salt, citric acid and solvent, and the specific weight parts are: 0.1 to 15 parts of the aforementioned quaternary ammonium salt, 0.1 to 10 parts of polyaspartic acid or polyaspartate, 0.1 to 5 parts of gluconate, 0.1 to 5 parts of inorganic zinc salt, 0.1 to 5 parts of citric acid, and 60 to 99.5 parts of solvent.

[0045] The preferred phosphorus-free corrosion and scale inhibitor bactericide comprises the following components in parts by weight: 5 to 10 parts of the aforementioned quaternary ammonium salt, 2 to 5 parts of polyaspartic acid or polyaspartate, 1 to 3 parts of gluconate, 2 to 4 parts of inorganic zinc salt, 2 to 3 parts of citric acid, and 19 to 84 parts of solvent.

[0046] Example 1

[0047] (1) At room temperature and pressure, 35 g of s-triazine, 90 g of chloromethylnaphthylamine and 30 g of zinc chloride are placed in a five-necked flask for reaction. After a multi-step substitution reaction, trisaminonaphthylmethyltriazinium is obtained by extraction and filtration;

[0048] (2) Add the product triaminonaphthylmethyl triazinium obtained in (1) into a dry reaction kettle equipped with a stirrer, a vacuum-pressure coupling meter, a vacuum pipe, a thermometer insert and an EO tube (EO is ethylene oxide). Vacuum the kettle to remove air, start stirring and heat the kettle to 150-160°C. When the temperature of the ethylene oxide water bath rises to 55-60°C, open the valve of the EO tube, slowly introduce a measured amount of EO gas into the kettle, maintain the pressure in the kettle at 0.2-0.3Mpa, and keep the temperature in the kettle at 170-200°C. When negative pressure appears in the kettle, it indicates that the reaction process is completed. Cool to 70-80°C and discharge the material to obtain tris[(N,N)-hydroxyethylnaphthylmethyl]-triazinium.

[0049] (3) Using this as the initiator and adding a catalyst, additional EO gas is introduced under the above process conditions, and the temperature in the kettle is maintained at about 200°C. When negative pressure appears in the kettle, it indicates that the reaction process is complete. Cool to 70-80°C and discharge to obtain product 1.

[0050] Example 2

[0051] (1) At room temperature and pressure, 45 g of s-triazine, 110 g of chloromethylnaphthylamine and 40 g of zinc chloride are placed in a five-necked flask for reaction. After a multi-step substitution reaction, triaminonaphthylmethyltriazinium is obtained by extraction and filtration;

[0052] (2) Add the product triaminonaphthylmethyl triazinium obtained in (1) into a dry reaction kettle equipped with a stirrer, a vacuum-pressure coupling meter, a vacuum pipe, a thermometer insert and an EO tube (EO is ethylene oxide). Vacuum the kettle to remove air, start stirring and heat the kettle to 180-210°C. When the temperature of the ethylene oxide water bath rises to 60-65°C, open the EO tube valve and slowly introduce a measured amount of EO gas into the kettle, maintain the pressure in the kettle at 0.2-0.3Mpa, and keep the temperature in the kettle at 150-180°C. When negative pressure appears in the kettle, it indicates that the reaction process is completed. Cool to 70-80°C and discharge the material to obtain tris[(N,N)-hydroxyethylnaphthylmethyl]-triazinium.

[0053] (3) Using this as the initiator and adding a catalyst, additional EO gas is introduced under the above process conditions, and the temperature in the kettle is maintained at about 210°C. When negative pressure appears in the kettle, it indicates that the reaction process is complete. Cool to 70-80°C and discharge to obtain product 2.

[0054] Example 3

[0055] (1) Under normal temperature and pressure, 55 g of s-triazine, 130 g of chloromethylnaphthylamine and 50 g of zinc chloride are placed in a five-necked flask for reaction. After a multi-step substitution reaction, triaminonaphthylmethyltriazinium is obtained by extraction and filtration;

[0056] (2) Add the product triaminonaphthylmethyl triazinium obtained in (1) into a dry reaction kettle equipped with a stirrer, a vacuum-pressure coupling meter, a vacuum pipe, a thermometer insert and an EO pipe (EO is ethylene oxide). Evacuate the air in the kettle, start stirring and heat the kettle to 190-220°C. When the temperature of the ethylene oxide water bath rises to 65-70°C, open the valve of the EO pipe and slowly introduce a measured amount of EO gas into the kettle, maintain the pressure in the kettle at 0.2-0.3Mpa, and keep the temperature in the kettle at 150-180°C. When negative pressure appears in the kettle, it indicates that the reaction process is completed. Cool to 70-80°C and discharge the material to obtain tris[(N,N)-hydroxyethylnaphthylmethyl]-triazinium.

[0057] (3) Using this as the initiator and adding a catalyst, additional EO gas is introduced under the above process conditions, and the temperature in the kettle is maintained at about 220°C. When negative pressure appears in the kettle, it indicates that the reaction process is complete. Cool to 70-80°C and discharge to obtain product 3.

[0058] Example 4

[0059] This example uses the hydroxyl-containing water-soluble polyoxyethylene quaternary ammonium salt cationic surfactant obtained in Example 1 as an example to prepare a phosphorus-free corrosion and scale inhibitor.

[0060] 5 parts by weight of a hydroxyl-containing water-soluble polyoxyethylene quaternary ammonium salt cationic surfactant, 5 parts of polyaspartic acid, 2 parts of sodium gluconate, 2 parts of zinc sulfate, 2 parts of citric acid and 84 parts of water are placed in a container and mixed evenly to obtain a phosphorus-free corrosion and scale inhibitor.

[0061] Example 5

[0062] This example uses the hydroxyl-containing water-soluble polyoxyethylene quaternary ammonium salt cationic surfactant obtained in Example 2 as an example to prepare a phosphorus-free corrosion and scale inhibitor.

[0063] 8 parts by weight of a hydroxyl-containing water-soluble polyoxyethylene quaternary ammonium salt cationic surfactant, 2 parts of polyaspartic acid, 3 parts of sodium gluconate, 3 parts of zinc sulfate, 3 parts of citric acid and 79 parts of water are placed in a container and mixed evenly to obtain a phosphorus-free corrosion and scale inhibitor.

[0064] Example 6

[0065] This example uses the hydroxyl-containing water-soluble polyoxyethylene quaternary ammonium salt cationic surfactant obtained in Example 3 as an example to prepare a phosphorus-free corrosion and scale inhibitor.

[0066] 10 parts by weight of a hydroxyl-containing water-soluble polyoxyethylene quaternary ammonium salt cationic surfactant, 2 parts of polyaspartic acid, 1 part of sodium gluconate, 4 parts of zinc sulfate, 2 parts of citric acid and 81 parts of water are placed in a container and mixed evenly to obtain a phosphorus-free corrosion and scale inhibitor.

[0067] Experimental Testing

[0068] Experimental Example 1

[0069] Experimental solution: Standard prepared water recommended in the standard

[0070] Drug: the above-mentioned embodiments 4, 5, 6, three embodiments

[0071] Evaluation method: Refer to GB / T18175-2014 "Determination of corrosion inhibition performance of water treatment agents"

[0072] Experimental temperature: 45℃

[0073] Drug concentration: 80ppm

[0074] Experimental period: 72h

[0075] The test method uses RCC-Ⅱ rotating coupon corrosion tester for evaluation. The test material is 20# carbon steel with a surface area of ​​28cm 2 The coupons rotate at a rate of 75 rpm and are naturally exposed to air (without other continuous ventilation devices). The corrosion test is carried out in a 2L beaker with two coupons installed at the same time, and the calculation results are averaged.

[0076] Table 1 Determination of corrosion rate

[0077] name Corrosion rate, mm / a blank 0.5621 Example 4 0.0083 Example 5 0.0108 Example 6 0.0057

[0078] It can be seen from Table 1 that the phosphorus-free corrosion and scale inhibitor bactericide prepared by the present invention has good corrosion inhibition performance.

[0079] Experimental Example 2

[0080] Experimental solution: standard test solution water quality

[0081] Experimental reagents: the above 4, 5, 6, three examples

[0082] Evaluation method: Refer to GB / T16632-2008 "Determination of scale inhibition performance of water treatment agents"

[0083] Experimental temperature: 80℃

[0084] Drug concentration: 80ppm

[0085] Experimental period: 10h

[0086] The test method adopts static scale inhibition method for evaluation, and the calcium ion content is determined by EDTA titration method.

[0087] Table 2 Evaluation of scale inhibition rate

[0088] name Scale inhibition rate, % Example 4 93.6 Example 5 95.0 Example 6 92.3

[0089] It can be seen from Table 2 that the phosphorus-free corrosion and scale inhibition bactericide prepared by the present invention has good scale inhibition performance, reaching more than 92%.

[0090] Experimental Example 3

[0091] Experimental solution: water injected into a gas field in southern Sichuan

[0092] Experimental reagents: Examples 4, 5, and 6 above, dodecyl dimethyl benzyl ammonium chloride, tetrakis hydroxymethyl phosphonium sulfate

[0093] Evaluation method: SY / T5329 "Water quality indicators and analysis methods for injection into clastic reservoirs", SY / T5890 "Bactericide performance evaluation method"

[0094] Experimental temperature: 40℃

[0095] Drug concentration: 100mg / L

[0096] Cultivation time: 168 hours

[0097] Sulfate reducing bacteria (SRB) number: 20×10 3 Pieces / mL

[0098] Number of saprophytic bacteria (TGB): 70×10 4 Pieces / mL

[0099] Number of iron bacteria (FB): 70×10 4 Pieces / mL

[0100] The test results are as follows:

[0101] Table 3 Bactericidal effect test

[0102]

[0103] It can be seen from the results in Table 3 that the phosphorus-free corrosion and scale inhibition bactericide prepared by the present invention has good compatibility with the gas field water system in the treatment of gas field water, and its comprehensive bactericidal effect is better than that of the other two bactericides.

[0104] Experimental Example 4

[0105] Experimental solution: tap water

[0106] Experimental reagents: 4, 5, 6 above, three examples, sample 1, sample 2

[0107] Evaluation method: 200ml liquid, 11000 rpm, stirring for 1min, testing the foam volume after 10s

[0108] Experimental temperature: room temperature

[0109] Drug concentration: 1%

[0110] Table 4 Foaming performance evaluation

[0111] name Foam volume, ml Example 4 0 Example 5 0 Example 6 0 Sample 1 60 Sample 2 0

[0112] It can be seen from the results in Table 4 that the phosphorus-free corrosion and scale inhibitor bactericide prepared by the present invention has low surface tension and is not easy to foam.

[0113] Experimental Example 5

[0114] Experimental agents: Examples 4, 5, 6, three examples, sample 1, sample 2;

[0115] Evaluation method: The test agent is exposed to the air

[0116] Experimental temperature: 30℃

[0117] Experimental time: 30 days

[0118] Table 5 Evaluation of anti-mildew performance

[0119]

[0120] It can be seen from Table 5 that the phosphorus-free corrosion and scale inhibitors prepared in Examples 4-6 have good anti-mildew performance and did not mildew after being placed for 30 days. The above-described specific implementations further explain the purpose, technical scheme and beneficial effects of the present invention in detail. It should be understood that the above description is only a specific implementation of the present invention and is not intended to limit the scope of protection of the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the scope of protection of the present invention.

Claims

1. A quaternary ammonium salt represented by formula (I), In the formula, the value range of m is 0 to 100, the value range of n is 0 to 100, and both m and n are integers.

2. The quaternary ammonium salt according to claim 1, characterized in that The value range of m is 0-100, preferably 0-45; the value range of n is 0-100, preferably 0-55.

3. The method for preparing a quaternary ammonium salt according to claim 1 or 2, wherein: The preparation method comprises: 10 to 20 parts by weight of triazine, 30 to 40 parts by weight of chloromethylnaphthylamine and 10 to 15 parts by weight of zinc chloride are subjected to a reverse substitution reaction in the presence of a first initiator and a first catalyst to obtain triaminonaphthylmethyltriazine; 10-15 parts of triaminonaphthylmethyl triazine and 80-90 parts of ethylene oxide are reacted in the presence of a second initiator and a second catalyst at a reaction temperature of 150-220° C. to obtain the quaternary ammonium salt; The weight portion of the triaminonaphthylmethyl triazine is 10 to 15 parts, and the weight portion of ethylene oxide is 80 to 90 parts.

4. The preparation method according to claim 3, characterized in that: The reaction of triaminonaphthylmethyl triazine and ethylene oxide is carried out in two steps, specifically including: After the triaminonaphthylmethyl triazine and part of ethylene oxide are reacted at 150-180° C., the second catalyst and the remaining ethylene oxide are added thereto and reacted at 200-220° C.

5. The preparation method according to claim 4, characterized in that: After the reaction of triaminonaphthylmethyl triazine and part of ethylene oxide is completed, the mixture is cooled to 70-80°C, and then the second catalyst and the remaining ethylene oxide are added thereto to react at 200-220°C.

6. The preparation method according to claim 4, characterized in that: Triaminonaphthylmethyl triazine reacts with part of ethylene oxide, specifically: Ethylene oxide is added to triaminonaphthylmethyltriazine, and the reaction is terminated when the pressure in the reaction vessel becomes negative.

7. The preparation method according to claim 4, characterized in that: Before the ethylene oxide and triaminonaphthylmethyl triazine are mixed, the temperature of the ethylene oxide is 55 to 70°C.

8. A phosphorus-free corrosion and scale inhibitor bactericidal agent comprising the quaternary ammonium salt according to claim 1 or 2.

9. The phosphorus-free corrosion and scale inhibitor bactericide according to claim 8, characterized in that: The composition comprises the following components in parts by weight:

10. The phosphorus-free corrosion and scale inhibitor bactericide according to claim 9, characterized in that: The composition comprises the following components in parts by weight:

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