Polyolefin plant polymeric antifouling agent, and preparation method and application thereof

Abstract

The present application relates to a kind of polyolefin device with polymerization anti-fouling agent and its preparation method and application, polymerization anti-fouling agent includes: the first component of the synthesis of alkyl sulfonic acid and alkyl quaternary ammonium salt;The second component of the synthesis of alkyl sulfonic acid and alkyl alcohol amine;Metal organic compound is the third component;Long-chain alpha-olefin is the fourth component;Solvent is the fifth component;The weight ratio of first component and second component is (0.01-100):1, the weight ratio of the sum of the mass of the first component and the second component and the third component is (0.01-100):1, the mass content of the long-chain alpha-olefin is 0.01%-10%, and the mass content of the solvent is 1-99%.Compared with the prior art, the present application has little effect on catalyst activity, and is introduced into the polymerization reaction device by a new method, reduces the contact time of anti-fouling agent and catalyst, and is easy to implement, with good operability.

Description

Technical Field

[0001] This invention relates to the field of polymeric antiscaling agents, and in particular to a polymeric antiscaling agent for polyolefin plants, its preparation method, and its application. Background Technology

[0002] In continuous polymerization processes, particularly gas-phase processes, used for olefin polymerization, polymer agglomeration in the polymerization reactor is a challenge. See U.S. Patent Nos. 5,436,304 and 5,405,922. Flakes are formed when molten catalyst and resin particles adhere to the reactor walls. The problem is characterized by the formation of large clumps of polymer solids on the reactor walls. These solids, or polymer flakes, eventually detach from the walls and fall into the reaction chamber, where they impede fluidization, clog the product outlet, and ultimately force the reactor to shut down.

[0003] Several anti-scaling agents have been developed to address polymer agglomeration problems during continuous olefin polymerization, among which alkyl sulfonic acids can effectively eliminate the positive charge generated in the system. Patent US9303095B2 discloses an anti-scaling agent (trade name Statsafe6000) containing alkyl sulfonic acids to control scaling problems during polyolefin production.

[0004] Alkyl alcohol amines can effectively eliminate the negative charge generated in the system. Patent No. WO 97 / 46599 discloses a method of introducing an anti-scaling agent containing alkyl diethanolamines (such as the product trade name Atmer 163) into an olefin polymerization unit after blending with a catalyst to control static electricity generated during the production process.

[0005] Because the catalysts and co-catalysts used in the polymerization reaction are chemically active, they can react rapidly with the core components of traditional polymerization anti-scaling agents. This not only leads to a significant decrease in the activity of the catalyst, but also causes problems such as delayed static elimination and failure of the polymerization anti-scaling agent, which seriously affects the anti-scaling effect of traditional polymerization anti-scaling agents.

[0006] Meanwhile, during the switching of production of different grades of resin, especially when different catalysts are required for production of different grades, the resin particles are quite different, which makes it very easy to generate static electricity, causing scaling and affecting the long-term operation of the equipment. Traditional polymer anti-scaling agents cannot cope with this switching process, and the equipment can only be shut down for cleaning and then switched back to production, which increases the cost of switching production. Summary of the Invention

[0007] The purpose of this invention is to overcome at least one of the defects of the prior art and provide a polymeric anti-scaling agent for polyolefin plants that has little impact on catalyst activity, is widely applicable to static elimination, is easy to implement, and has good operability, as well as its preparation method and application.

[0008] In this invention, by forming ionic liquids from the components, the effect of the polymeric antiscaling agent is reduced while maintaining its function. The polymeric antiscaling agent obtained by this patented technology exhibits superior electrostatic elimination adaptability compared to traditional polymeric antiscaling agents, demonstrating excellent electrostatic elimination capabilities for various resin grades.

[0009] The objective of this invention is achieved through the following technical solution:

[0010] The first aspect of this invention provides a polymeric anti-scaling agent for polyolefin equipment, the polymeric anti-scaling agent comprising:

[0011] The first component is the compound of alkyl sulfonic acid and alkyl quaternary ammonium salt;

[0012] The compound of alkyl sulfonic acid and alkyl alcoholamine is the second component;

[0013] Organometallic compounds are the third component;

[0014] Long-chain α-olefins are the fourth component;

[0015] The solvent is the fifth component;

[0016] The weight ratio of the first component to the second component is (0.01-100):1, the weight ratio of the sum of the masses of the first component and the second component to the third component is (0.01-100):1, the mass content of the long-chain α-olefin is 0.01%-10%, and the mass content of the solvent is 1-99%.

[0017] Furthermore, the weight ratio of the first component to the second component is 0.1 to 10:1.

[0018] Furthermore, the compound formed by the alkyl sulfonic acid and the alkyl quaternary ammonium salt is an ionic liquid formed by the alkylbenzene sulfonic acid and the alkyl quaternary ammonium salt;

[0019] The synthesis of the alkyl sulfonic acid and alkyl alcoholamine salt is an ionic liquid formed by alkyl benzene sulfonic acid and alkyl quaternary ammonium salt.

[0020] Furthermore, in the first component, the weight ratio of the alkyl sulfonic acid to the alkyl quaternary ammonium salt is (0.1-10):1;

[0021] In the second component, the weight ratio of the alkyl sulfonic acid to the alkyl alcoholamine is (0.1-10):1.

[0022] Further, the alkyl sulfonic acid is one or more of benzenesulfonic acid or sulfonic acid of the general formula R-C6H4-SO3H, wherein R is an alkyl group containing 1-20 carbon atoms;

[0023] More preferably, R contains 6-16 carbon atoms, and most preferably 8-12 carbon atoms.

[0024] The general formula of the alkyl quaternary ammonium salt is R1 (R3). 3-n NR2X n One or more of the quaternary ammonium salts, wherein R1 and R2 may be the same or different, R1 and R2 are alkyl groups containing 1-20 carbon atoms, R3 is an alkyl group containing 1-7 carbon atoms, X is fluorine, chlorine, bromine, iodine, RCOO, SO3 or NO3, and n is 1-3;

[0025] The alkyl alcoholamine has the general formula of one or more of R1NH2OH, R1R2NH(OH)2 or R1R2R3N(OH)3, wherein R1, R2, and R3 may be the same or different, and R1, R2, and R3 are alkyl groups containing 1 to 20 carbon atoms.

[0026] Furthermore, the organometallic compound is one or more of alkylaluminum and its halides, alkylzinc and its halides, and alkylmagnesium and its halides;

[0027] The long-chain α-olefin is one or more of α-olefins containing 4-50 carbon atoms;

[0028] More preferably, the number of carbon atoms is 8-20.

[0029] The solvent includes one or more of hexane, heptane, toluene, xylene, cyclohexane, petroleum ether, mineral oil, polyols, polyacids, or polyol esters.

[0030] Furthermore, the alkyl sulfonic acid includes octylbenzene sulfonic acid, nonylbenzene sulfonic acid, decylbenzene sulfonic acid, undecylbenzene sulfonic acid, and dodecylbenzene sulfonic acid; preferably dodecylbenzene sulfonic acid.

[0031] The alkyl quaternary ammonium salt includes dicosyldimethylammonium chloride, didodecyldimethylammonium chloride, didodecyldimethylammonium bromide, ditetradecyldimethylammonium chloride, and dilauryldimethylammonium bromide; preferably dicosyldimethylammonium chloride and didodecyldimethylammonium chloride.

[0032] The alkyl alcoholamines include ethanolamine, diethanolamine, triethanolamine, propanolamine, dipropanolamine, tripropanolamine, isopropanolamine, diisopropanolamine, triisopropanolamine, butanolamine, dibutanolamine, tributanolamine, isobutanolamine, diisobutanolamine, triisobutanolamine, alkoxypropyl dihydroxyethylamine, stearyl bis(2-hydroxyethyl)amine, bis(β-hydroxyethyl)cocoylamine, bis(β-hydroxyethyl)stearamine, or bis(β-hydroxyethyl)tartamine; preferably diethanolamine or triethanolamine.

[0033] The organometallic compounds include trimethylaluminum, triethylaluminum, triisobutylaluminum, dimethylaluminum chloride, diethylaluminum chloride, dimethylzinc, diethylzinc, dibutylzinc, dimethylmagnesium, diethylmagnesium, and dibutylmagnesium. Triethylaluminum and diethylaluminum chloride are preferred.

[0034] A second aspect of the present invention provides a method for preparing a polymeric antiscaling agent for polyolefin equipment as described above, comprising the following steps:

[0035] Alkyl sulfonic acid and alkyl quaternary ammonium salt are mixed in a certain proportion and stirred to form a homogeneous solution, namely the ionic liquid BAQ formed by alkyl sulfonic acid and alkyl quaternary ammonium salt.

[0036] Alkyl sulfonic acid and alkyl alcoholamine are mixed in a certain proportion and stirred to form a homogeneous solution, namely the ionic liquid BAA formed by alkyl sulfonic acid and alkyl alcoholamine;

[0037] The BAQ, BAA, organometallic compounds, long-chain α-olefins, and solvents are mixed and stirred to obtain a polymeric anti-scaling agent for polyolefin devices.

[0038] Furthermore, the stirring temperature is -50 to 150°C, preferably 0 to 80°C.

[0039] More preferably, the stirring temperature is 0-100℃, more preferably 10-50℃.

[0040] A third aspect of the present invention provides an application of the polymeric antiscaling agent for polyolefin equipment as described above, the application process comprising:

[0041] The specific steps for applying the polymeric anti-scaling agent to the anti-scaling reaction of ethylene polymerization are as follows: the polymeric anti-scaling agent is fed through an independent feed line, and after being atomized by an atomizing device, it is introduced into the seed bed of the reaction device for direct reaction, or it is pre-contacted with the resin in the seed bed and then fluidized in the reaction device.

[0042] Furthermore, the amount of the polymer anti-scaling agent added is 0.1-5000 ppm of the weight of the polyolefin powder in the polymerization reactor, and the pre-contact time of the polymer anti-scaling agent with the seed bed is 0.1-24 h.

[0043] More preferably, the amount of the polymeric antiscaling agent added is 1-1000 ppm, and the contact time is 0.5-5 h.

[0044] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0045] (1) The present invention introduces organometallic compounds into the anti-scaling agent, thereby improving the activity of the catalyst and reducing the influence of the anti-scaling agent on the catalyst activity. Compared with the prior art, the added organometallic compounds do not have an adverse effect on the static elimination effect of the anti-scaling agent.

[0046] (2) The polymeric antiscaling agent obtained by the technology of the present invention has a wider range of applications for static elimination and has a significant static elimination effect on various types of polyethylene resins. Detailed Implementation

[0047] Overall, this invention provides a polymeric antiscaling agent for polyolefin equipment, its preparation method, and its application. The polymeric antiscaling agent composition comprises: a first component is BAQ; a second component is BAA; a third component is an organometallic compound; a fourth component is a long-chain α-olefin; and a fifth component is a solvent. The preparation method includes:

[0048] (1) Mix the components in the specified proportions and stir to form a homogeneous solution. The stirring temperature is -50 to 150°C, preferably 0 to 80°C; the weight ratio between the first and second components is (0.01-100):1, preferably (0.5-2):1. The weight ratio of the sum of the first and second components to the third component is (0.01-100):1, preferably (1-100):1. The mass content of the fourth component is 0.01%-10%, preferably 0.1%-5%. The mass content of the fifth component is 1-99%.

[0049] (2) The alkyl sulfonic acid is benzenesulfonic acid or has the general formula R-C6H4-SO3H, wherein R is an alkyl group containing 1-20 carbon atoms, preferably an alkylbenzenesulfonic acid with 6-16 carbon atoms. Alkyl quaternary ammonium salts refer to those with the general formula R1 (R3). 3-n NR2X nThe quaternary ammonium salt, wherein R1 and R2 may be the same or different, R1 and R2 are alkyl groups containing 1-18 carbon atoms, R3 is an alkyl group containing 1-7 carbon atoms, X is fluorine, chlorine, bromine, iodine, RCOO, SO3 or NO3, and n is 1-3. Preferably, it is dicocarbamate dimethylammonium chloride, didodecyl dimethylammonium chloride, didodecyl dimethylammonium bromide, ditetradecyl dimethylammonium chloride, or dilauryl dimethylammonium bromide. More preferably, it is dicocarbamate dimethylammonium chloride or didodecyl dimethylammonium chloride. The general formula of the alkyl alcoholamine is one or more of R1NH2OH, R1R2NH(OH)2 or R1R2R3N(OH)3, wherein R1, R2, and R3 may be the same or different, and R1, R2, and R3 are alkyl groups containing 1-20 carbon atoms. Ethanolamine, diethanolamine, triethanolamine, propanolamine, dipropanolamine, tripropanolamine, isopropanolamine, diisopropanolamine, triisopropanolamine, butanolamine, dibutanolamine, tributanolamine, isobutanolamine, diisobutanolamine, triisobutanolamine, alkoxypropyl dihydroxyethylamine, stearyl bis(2-hydroxyethyl)amine, bis(β-hydroxyethyl)cocoylamine, bis(β-hydroxyethyl)stearamine, or bis(β-hydroxyethyl)tartrazine; more preferably diethanolamine and triethanolamine. The organometallic compound is alkylaluminum and its halides, alkylzinc and its halides, alkylmagnesium and its halides, preferably trimethylaluminum, triethylaluminum, triisobutylaluminum, dimethylaluminum chloride, diethylaluminum chloride, dimethylzinc, diethylzinc, dibutylzinc, dimethylmagnesium, diethylmagnesium, or dibutylmagnesium. More preferably triethylaluminum and diethylaluminum chloride. The long-chain α-olefin is one or more of α-olefins containing 4-50 carbon atoms, preferably 8-20 carbon atoms. The solvent is hexane, heptane, toluene, xylene, cyclohexane, petroleum ether, mineral oil, polyol, polyacid, polyol ester or mixture thereof, preferably heptane, cyclohexane or castor oil.

[0050] The method of use is as follows: The anti-scaling agent composition is fed independently of the catalyst through a separate feed line. After being atomized by an atomizing device, the anti-scaling agent composition is introduced into the seed bed of the reaction device for direct reaction, or it can be pre-contaminated with the resin in the seed bed before fluidization in the reaction device. The contact time is 0.01-24 hours, preferably 0.5-5 hours. Based on the weight of polyolefin powder in the polymerization reactor, the amount of anti-scaling agent composition added is 0.1-5000 ppm, preferably 1-1000 ppm.

[0051] Evaluation of the anti-scaling effect of the device:

[0052] The prepared antiscaling agent mixture was atomized in an atomizing device and added to the seed bed via a separate pipeline, independent of the catalyst. After contacting the polyethylene powder in the seed bed for 4 hours, it was introduced into a metal fluidized bed. The amount of antiscaling agent relative to the mass ratio of polyethylene powder in the reactor was 200 ppm. The polyethylene powder was selected from one or more grades of polyethylene, namely mPE1810 (produced with metallocene catalyst), 7042 (produced with magnesium-titanium catalyst), or 5502 (produced with chromium catalyst).

[0053] After the anti-scaling agent was introduced into the fluidized bed, the particle charge-to-mass ratio was measured by sampling and using an electrostatic analyzer. Samples were taken 5 min, 10 min, and 60 min after the anti-scaling agent was injected, and the charge-to-mass ratio of the polyethylene particles was analyzed. The results are listed in Tables 1-4. The charge-to-mass ratio represents the amount of electrostatic charge carried by each kilogram of polyethylene particles; a positive value indicates that the polyethylene particles are positively charged, and a negative value indicates that the polyethylene particles are negatively charged.

[0054] Polymerization activity evaluation:

[0055] The polymerization activity of the catalyst was evaluated using ethylene slurry polymerization. The polymerization reactor had a volume of 2L and was purged with nitrogen several times beforehand. After purging the reaction vessel several times with nitrogen, 1L of hexane solvent, 10-100mg of a self-made polyethylene catalyst, a co-catalyst, and a certain amount of anti-scaling agent were added sequentially. Nitrogen gas was introduced to purge the solvent and catalyst into the anhydrous and oxygen-free reactor. Ethylene was introduced at a reaction pressure of 0.8MPa, stirring was started, and the temperature was gradually increased. The reaction was maintained at the specified temperature for 2 hours. The temperature inside the reactor was controlled using a water bath. Finally, the ethylene was shut off, and after cooling, the polymerization product was removed, dried, weighed, and the catalyst activity was calculated. Evaluation tests were conducted by adding anti-scaling agent concentrations of 50, 200, and 5000ppm to the polymerization system.

[0056] The present invention will now be described in detail with reference to specific embodiments, but this is by no means a limitation thereof. Any preparation methods, materials, structures, or compositional ratios not explicitly described in this technical solution are considered common technical features disclosed in the prior art.

[0057] Example 1a

[0058] The components and proportions of Example 1a are shown in Tables 1 and 2.

[0059] Step 1: Mix alkyl sulfonic acid and alkyl quaternary ammonium salt in a certain proportion and stir to synthesize BAQ. The mixing temperature is 30℃.

[0060] Step 2: Mix alkyl sulfonic acid and alkyl alcoholamine in a certain proportion and stir to synthesize BAA. The mixing temperature is 30℃.

[0061] Step 3: Mix BAQ, BAA, organometallic compounds, long-chain α-olefins and solvents to obtain K1, a polymeric anti-scaling agent for polyolefin devices, at a mixing temperature of 30°C.

[0062] The evaluation results of the anti-scaling effect and polymerization activity of the K1 device are listed in Tables 1 and 2.

[0063] Example 1b

[0064] The components and proportions of Example 1b are shown in Tables 1 and 2. The steps are the same as in Example 1a, with a mixing temperature of 10°C, to obtain K2, a polymeric anti-scaling agent for polyolefin plants. The evaluation results of the anti-scaling effect and polymerization activity of K2 are listed in Tables 1 and 2.

[0065] Example 1c

[0066] The components and proportions of Example 1c are shown in Tables 1 and 2. The steps are the same as in Example 1a, with a mixing temperature of 50°C, to obtain K3, a polymeric anti-scaling agent for polyolefin plants. The evaluation results of the anti-scaling effect and polymerization activity of K3 are listed in Tables 1 and 2.

[0067] Example 1d

[0068] The components and proportions of Example 1d are shown in Tables 1 and 2. The steps are the same as in Example 1a, with a mixing temperature of 0°C, to obtain K4, a polymeric anti-scaling agent for polyolefin plants. The evaluation results of the anti-scaling effect and polymerization activity of K4 are listed in Tables 1 and 2.

[0069] Example 1e

[0070] The components and proportions of Example 1e are shown in Tables 1 and 2. The steps are the same as in Example 1a, with a mixing temperature of 50°C, to obtain K5, a polymeric anti-scaling agent for polyolefin plants. The evaluation results of the anti-scaling effect and polymerization activity of K5 are listed in Tables 1 and 2.

[0071] Example 1f

[0072] The components and proportions of Example 1f are shown in Tables 1 and 2. The steps are the same as in Example 1a, with a mixing temperature of 20°C, to obtain K6, a polymeric anti-scaling agent for polyolefin plants. The evaluation results of the anti-scaling effect and polymerization activity of K6 are listed in Tables 1 and 2.

[0073] Example 1g

[0074] The components and proportions of Example 1g are shown in Tables 1 and 2. The steps are the same as in Example 1a, with a mixing temperature of 60°C, to obtain K7, a polymeric anti-scaling agent for polyolefin plants. The evaluation results of the anti-scaling effect and polymerization activity of K7 are listed in Tables 1 and 2.

[0075] Example 1h

[0076] The components and proportions of Example 1h are shown in Tables 1 and 2. The steps are the same as in Example 1a, with a mixing temperature of 80°C, to obtain K8, a polymeric anti-scaling agent for polyolefin plants. The evaluation results of the anti-scaling effect and polymerization activity of K8 are listed in Table 1.

[0077] Example 1i

[0078] The components and proportions of Example 1i are shown in Tables 1 and 2. The steps are the same as in Example 1a, with a mixing temperature of 40°C, to obtain K9, a polymeric anti-scaling agent for polyolefin plants. The evaluation results of the anti-scaling effect and polymerization activity of K9 are listed in Tables 1 and 2.

[0079] Example 1j

[0080] The components and proportions of Example 1j are shown in Tables 1 and 2. The steps are the same as in Example 1a, with a mixing temperature of 100°C, to obtain K10, a polymeric anti-scaling agent for polyolefin plants. The evaluation of the anti-scaling effect of K10 and the results of its polymerization activity are listed in Tables 1 and 2.

[0081] Example 1k

[0082] The components and proportions of Example 1k are shown in Tables 1 and 2. The steps are the same as in Example 1a, with a mixing temperature of 50°C, to obtain K11, a polymeric anti-scaling agent for polyolefin plants. The evaluation of the anti-scaling effect of K11 and the results of its polymerization activity are listed in Tables 1 and 2.

[0083] Comparative Example 1-1

[0084] The components and proportions of Comparative Example 1-1 are shown in Tables 1 and 2. The mixture was stirred and blended with a solvent at 30°C to obtain polymeric anti-scaling agent C1 for polyolefin plants. The evaluation results of the anti-scaling effect and polymerization activity of C1 are listed in Tables 1 and 2.

[0085] Comparative Examples 1-2

[0086] Comparative Examples 1 and 2, without the addition of polymeric antiscaling agent, served as blank control samples.

[0087] Compared with Comparative Example 1-1, all examples showed significantly improved polymerization activity due to the use of organometallic compounds, which reduced the inhibitory effect of antiscaling agents on catalyst activity.

[0088] Table 1 shows the formulations and mass-to-charge ratio test results of the examples and comparative examples using different organometallic compounds.

[0089]

[0090]

[0091]

[0092] Table 2 shows the formulations and catalyst activity evaluation results of the examples and comparative examples using different organometallic compounds.

[0093]

[0094]

[0095]

[0096] Example 2a

[0097] The components and proportions of Example 2a are shown in Tables 3 and 4. The steps are the same as in Example 1a, with a mixing temperature of 30°C, to obtain K12, a polymeric anti-scaling agent for polyolefin plants. The evaluation results of the anti-scaling effect and polymerization activity of K12 are listed in Tables 3 and 4.

[0098] Example 2c

[0099] The components and proportions of Example 2c are shown in Tables 3 and 4. The steps are the same as in Example 1a, with a mixing temperature of 50°C, to obtain K13, a polymeric anti-scaling agent for polyolefin plants. The evaluation results of the anti-scaling effect and polymerization activity of K13 are listed in Tables 3 and 4.

[0100] Example 2d

[0101] The components and proportions of Example 2d are shown in Tables 3 and 4. The steps are the same as in Example 1a, with a mixing temperature of 10°C, to obtain K14, a polymeric anti-scaling agent for polyolefin plants. The evaluation results of the anti-scaling effect and polymerization activity of K14 are listed in Tables 3 and 4.

[0102] Example 2e

[0103] The components and proportions of Example 2e are shown in Tables 3 and 4. The steps are the same as in Example 1a, with a mixing temperature of 0°C, to obtain K15, a polymeric anti-scaling agent for polyolefin plants. The evaluation results of the anti-scaling effect and polymerization activity of K15 are listed in Tables 3 and 4.

[0104] Example 2f

[0105] The components and proportions of Example 2f are shown in Tables 3 and 4. The steps are the same as in Example 1a, with a mixing temperature of 100°C, to obtain K16, a polymeric anti-scaling agent for polyolefin plants. The evaluation results of the anti-scaling effect and polymerization activity of K16 are listed in Tables 3 and 4.

[0106] Example 2g

[0107] The components and proportions of Example 2g are shown in Tables 3 and 4. The steps are the same as in Example 1a, with a mixing temperature of 60°C, to obtain K17, a polymeric anti-scaling agent for polyolefin plants. The evaluation results of the anti-scaling effect and polymerization activity of K17 are listed in Tables 3 and 4.

[0108] Example 2h

[0109] The components and proportions of Example 2h are shown in Tables 3 and 4. The steps are the same as in Example 1a, with a mixing temperature of 20°C, to obtain K18, a polymeric anti-scaling agent for polyolefin plants. The evaluation results of the anti-scaling effect and polymerization activity of K18 are listed in Tables 3 and 4.

[0110] Comparative Example 2

[0111] The components and proportions of Comparative Example 2 are shown in Tables 3 and 4. The mixture was stirred and blended with a solvent at 30°C to obtain Polyolefin Plant Anti-scaling Agent C2. The evaluation results of the anti-scaling effect and polymerization activity of C2 are listed in Tables 3 and 4.

[0112] All embodiments used a combination of BAQ and BAA, while Comparative Example 2 used only BAA. The antiscaling agents obtained in each embodiment had better electrostatic elimination effects than Comparative Example 2 to varying degrees.

[0113] Table 3 shows the formulations and charge-to-mass ratio test results for the examples and comparative examples using different BAQs.

[0114]

[0115]

[0116] Table 4 shows the formulations and catalyst activity evaluation results of the examples and comparative examples using different BAQs.

[0117]

[0118]

[0119]

[0120] Example 3a

[0121] The components and proportions of Example 3a are shown in Tables 5 and 6. The steps are the same as in Example 1a, with a mixing temperature of 30°C, to obtain K19, a polymeric anti-scaling agent for polyolefin plants. The evaluation results of the anti-scaling effect and polymerization activity of K19 are listed in Tables 5 and 6.

[0122] Example 3b

[0123] The components and proportions of Example 3b are shown in Tables 5 and 6. The steps are the same as in Example 1a, with a mixing temperature of 50°C, to obtain K20, a polymeric anti-scaling agent for polyolefin plants. The evaluation results of the anti-scaling effect and polymerization activity of K20 are listed in Tables 5 and 6.

[0124] Example 3c

[0125] The components and proportions of Example 3c are shown in Tables 5 and 6. The steps are the same as in Example 1a, with a mixing temperature of 10°C, to obtain K21, a polymeric anti-scaling agent for polyolefin plants. The evaluation results of the anti-scaling effect and polymerization activity of K21 are listed in Tables 5 and 6.

[0126] Example 3d

[0127] The components and proportions of Example 3d are shown in Tables 5 and 6. The steps are the same as in Example 1a, with a mixing temperature of 0°C, to obtain K22, a polymeric anti-scaling agent for polyolefin plants. The evaluation results of the anti-scaling effect and polymerization activity of K22 are listed in Tables 5 and 6.

[0128] Example 3e

[0129] The components and proportions of Example 3e are shown in Tables 5 and 6. The steps are the same as in Example 1a, with a mixing temperature of 100°C, to obtain K23, a polymeric anti-scaling agent for polyolefin plants. The evaluation results of the anti-scaling effect and polymerization activity of K23 are listed in Tables 5 and 6.

[0130] Example 3f

[0131] The components and proportions of Example 3f are shown in Tables 5 and 6. The steps are the same as in Example 1a, with a mixing temperature of 20°C, to obtain K24, a polymeric anti-scaling agent for polyolefin plants. The evaluation results of the anti-scaling effect and polymerization activity of K24 are listed in Tables 5 and 6.

[0132] Example 3g

[0133] The components and proportions of Example 3g are shown in Tables 5 and 6. The steps are the same as in Example 1a, with a mixing temperature of 50°C, to obtain K25, a polymeric anti-scaling agent for polyolefin plants. The evaluation results of the anti-scaling effect and polymerization activity of K25 are listed in Tables 5 and 6.

[0134] Comparative Example 3

[0135] The components and proportions of Comparative Example 3 are shown in Tables 5 and 6. The mixture was stirred and blended with a solvent at 30°C to obtain Polyolefin Plant Anti-scaling Agent C3. The evaluation results of the anti-scaling effect and polymerization activity of C3 are listed in Tables 5 and 6.

[0136] All embodiments used a combination of BAQ and BAA, while Comparative Example 3 used only BAQ. The antiscaling agents obtained in each embodiment had better electrostatic elimination effects than Comparative Example 3 to varying degrees.

[0137] Table 5 shows the formulations and charge-to-mass ratio test results for the examples and comparative examples using different BAQs.

[0138]

[0139]

[0140] Table 6 shows the formulations and catalyst activity evaluation results of the examples and comparative examples using different BAQs.

[0141]

[0142]

[0143] Example 4a

[0144] The components and proportions of Example 4a are shown in Tables 7 and 8. The steps are the same as in Example 1a, with a mixing temperature of 30°C, to obtain K26, a polymeric anti-scaling agent for polyolefin plants. The evaluation results of the anti-scaling effect and polymerization activity of K26 are listed in Tables 7 and 8.

[0145] Example 4b

[0146] The components and proportions of Example 4b are shown in Tables 7 and 8. The steps are the same as in Example 1a, with a mixing temperature of 50°C, to obtain K27, a polymeric anti-scaling agent for polyolefin plants. The evaluation results of the anti-scaling effect and polymerization activity of K27 are listed in Tables 7 and 8.

[0147] Example 4c

[0148] The components and proportions of Example 4c are shown in Tables 7 and 8. The steps are the same as in Example 1a, and the mixing temperature of the components is 10°C, resulting in K28, a polymeric anti-scaling agent for polyolefin plants. The evaluation results of the anti-scaling effect and polymerization activity of K28 are listed in Tables 7 and 8.

[0149] Example 4d

[0150] The components and proportions of Example 4d are shown in Tables 7 and 8. The steps are the same as in Example 1a, with a mixing temperature of 0°C, to obtain K29, a polymeric anti-scaling agent for polyolefin plants. The evaluation results of the anti-scaling effect and polymerization activity of K29 are listed in Tables 7 and 8.

[0151] Example 4e

[0152] The components and proportions of Example 4e are shown in Tables 7 and 8. The steps are the same as in Example 1a, with a mixing temperature of 20°C, to obtain K30, a polymeric anti-scaling agent for polyolefin plants. The evaluation results of the anti-scaling effect and polymerization activity of K30 are listed in Tables 7 and 8.

[0153] Example 4f

[0154] The components and proportions of Example 4f are shown in Tables 7 and 8. The steps are the same as in Example 1a, and the mixing temperature of the components is 60°C, resulting in K31, a polymeric anti-scaling agent for polyolefin plants. The evaluation results of the anti-scaling effect and polymerization activity of K31 are listed in Tables 7 and 8.

[0155] Comparative Example 4

[0156] The components and proportions of Comparative Example 4 are shown in Tables 7 and 8. The mixture was stirred and blended with a solvent at 30°C to obtain C4, a polymeric anti-scaling agent for polyolefin plants. The evaluation results of the anti-scaling effect and polymerization activity of C4 are listed in Tables 7 and 8.

[0157] Compared to Comparative Example 4, all examples showed that the use of long-chain α-olefins reduced the impact of organometallic compounds on the static elimination effect. In contrast, Comparative Example 4, which did not use long-chain α-olefins, resulted in antiscaling agents in each example exhibiting better static elimination effects than those in Comparative Example 4 to varying degrees.

[0158] Table 7 shows the formulations and mass-to-charge ratio test results of the examples and comparative examples using different long-chain α-olefins.

[0159]

[0160]

[0161] Table 8 shows the formulations and catalyst activity evaluation results of examples and comparative examples using different long-chain α-olefins.

[0162]

[0163]

[0164] The above description of the embodiments is provided to enable those skilled in the art to understand and use the invention. It will be apparent to those skilled in the art that various modifications can be made to these embodiments, and the general principles described herein can be applied to other embodiments without inventive effort. Therefore, the present invention is not limited to the above embodiments, and any improvements and modifications made by those skilled in the art based on the disclosure of the present invention without departing from the scope of the invention should be within the protection scope of the present invention.

Claims

1. A polymeric anti-scaling agent for polyolefin equipment, characterized in that, Polymer antiscaling agents include: The ionic liquid formed by alkylbenzene sulfonic acid and alkyl quaternary ammonium salt is the first component; The ionic liquid formed by alkylbenzene sulfonic acid and alkyl alcoholamine is the second component; The third component is an organometallic compound selected from one or more of alkylaluminum and its halides, alkylzinc and its halides, and alkylmagnesium and its halides; Long-chain α-olefins are the fourth component; The solvent is the fifth component; The weight ratio of the first component to the second component is (0.01-100):1, the weight ratio of the sum of the masses of the first component and the second component to the third component is (0.01-100):1, the mass content of the long-chain α-olefin is 0.01%-10%, and the mass content of the solvent is 1-99%. The alkylbenzene sulfonic acid is one or more of benzene sulfonic acid or sulfonic acid of the general formula R-C6H4-SO3H, wherein R is an alkyl group containing 1-20 carbon atoms; The alkyl quaternary ammonium salt includes one of dicosyldimethylammonium chloride, didodecyldimethylammonium chloride, didodecyldimethylammonium bromide, ditetradecyldimethylammonium chloride, and dilauryldimethylammonium bromide; The alkyl alcoholamine is one or more of the following: ethanolamine, diethanolamine, triethanolamine, propanolamine, dipropanolamine, tripropanolamine, isopropanolamine, diisopropanolamine, triisopropanolamine, butanolamine, dibutanolamine, tributanolamine, isobutanolamine, diisobutanolamine, triisobutanolamine, alkoxypropyl dihydroxyethylamine, bis(β-hydroxyethyl)cocoagulamine, bis(β-hydroxyethyl)stearamine, or bis(β-hydroxyethyl)tartrazine.

2. The polymeric anti-scaling agent for polyolefin equipment according to claim 1, characterized in that, In the first component, the weight ratio of the alkylbenzene sulfonic acid to the alkyl quaternary ammonium salt is (0.1-10): 1; In the second component, the weight ratio of the alkylbenzene sulfonic acid to the alkyl alcoholamine is (0.1-10):

1.

3. The polymeric anti-scaling agent for polyolefin equipment according to claim 1, characterized in that, The long-chain α-olefin is one or more of α-olefins containing 4-50 carbon atoms; The solvent includes one or more of hexane, heptane, toluene, xylene, cyclohexane, petroleum ether, polyols, polyacids, or polyol esters.

4. The polymeric anti-scaling agent for polyolefin equipment according to claim 1, characterized in that, The alkylbenzene sulfonic acid includes octylbenzene sulfonic acid, nonylbenzene sulfonic acid, decylbenzene sulfonic acid, undecylbenzene sulfonic acid, and dodecylbenzene sulfonic acid; The organometallic compounds include trimethylaluminum, triethylaluminum, triisobutylaluminum, dimethylaluminum chloride, diethylaluminum chloride, dimethylzinc, diethylzinc, dibutylzinc, dimethylmagnesium, diethylmagnesium, and dibutylmagnesium.

5. A method for preparing a polymeric antiscaling agent for polyolefin equipment as described in any one of claims 1 to 4, comprising the following steps: Alkylbenzene sulfonic acid and alkyl quaternary ammonium salt are mixed in a certain proportion and stirred to form a homogeneous solution, namely the ionic liquid BAQ formed by alkylbenzene sulfonic acid and alkyl quaternary ammonium salt; Alkylbenzene sulfonic acid and alkyl alcoholamine are mixed in a certain proportion and stirred to form a homogeneous solution, namely the ionic liquid BAA formed by alkylbenzene sulfonic acid and alkyl alcoholamine; The BAQ, BAA, organometallic compounds, long-chain α-olefins, and solvents are mixed and stirred to obtain a polymeric anti-scaling agent for polyolefin devices.

6. The application of a polymeric antiscaling agent for a polyolefin plant as described in any one of claims 1 to 4, characterized in that, The application process includes: The specific steps for applying the polymeric anti-scaling agent to the anti-scaling reaction of ethylene polymerization are as follows: the polymeric anti-scaling agent is fed through an independent feed line, and after being atomized by an atomizing device, it is introduced into the seed bed of the reaction device for direct reaction, or it is pre-contacted with the resin in the seed bed and then fluidized in the reaction device.

7. The application of the polymeric anti-scaling agent for polyolefin equipment according to claim 6, characterized in that, The amount of the polymer anti-scaling agent added is 0.1-5000 ppm of the weight of the polyolefin powder in the polymerization reactor, and the pre-contact time of the polymer anti-scaling agent with the seed bed is 0.1-24 h.

8. The application of the polymeric antiscaling agent for polyolefin equipment according to claim 7, characterized in that, The amount of the polymeric antiscaling agent added is 1-1000 ppm, and the contact time is 0.5-5 h.

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