Polybutyl acrylate and method of preparation and asa resin

Abstract

The application provides a kind of polybutyl acrylate and preparation method and ASA resin.The preparation method of polybutyl acrylate includes the following steps: S1: butyl acrylate, RAFT reagent, emulsifier, optional electrolyte and water are mixed, then initiator, reducing agent is added to react, PBA seed emulsion is obtained;S2: butyl acrylate, RAFT reagent, emulsifier, initiator and water are mixed into pre-emulsion;S3: reducing agent, pre-emulsion is added to PBA seed emulsion to react, polybutyl acrylate is prepared.The polybutyl acrylate prepared by the application has high molecular weight, narrow molecular weight distribution, high branching degree, good rubber toughening effect, and can prepare super high impact ASA resin with less amount of glue powder, impact strength greater than 400J / m, and excellent weather resistance, dE less than 15 after 500h of ultraviolet aging test.

Description

Technical Field

[0001] This invention belongs to the field of polymers, and relates to a method for preparing polybutyl acrylate (PBA) and its application, specifically involving a hyperbranched high molecular weight narrow distribution PBA and its preparation method, as well as the ASA resin prepared therefrom. Background Technology

[0002] ASA resin is a high-performance engineering plastic. It is a graft copolymer of acrylonitrile, butyl acrylate, and styrene, and has a core-shell structure. The butyl acrylate rubber phase forms the core, which can toughen the resin and provide impact resistance. The styrene-acrylonitrile resin (SAN) forms the shell, which enhances the compatibility between the dispersed phase and the continuous phase.

[0003] Compared to ABS, ASA resin uses butyl acrylate as the rubber core instead of butadiene. This results in a rubber without excess double bonds, giving it better weather resistance and making it widely used in outdoor applications such as home appliances, automobiles, and traffic signs. However, butyl acrylate lacks excess double bonds, leading to poor toughening properties in butyl acrylate rubber. Furthermore, styrene and acrylonitrile are difficult to graft onto the outer layer, resulting in lower impact strength for ASA resin, thus limiting its applications.

[0004] Leading ASA resin manufacturers such as LG and Benlin often add crosslinking and grafting agents, such as methyl methacrylate, ethylene glycol dimethacrylate, divinylbenzene, and diallyl maleate, during PBA polymerization to provide crosslinking double bonds and grafting sites. The resulting ASA resin has an impact strength of less than 250 J / m. To improve the impact strength of ASA resin, a common practice is to blend small 100 nm particles with large 400 nm particles, utilizing the synergistic effect of particle size mixing to enhance impact resistance. However, this complicates the polymerization process. Most domestic manufacturers choose to increase the amount of ASA binder powder added to improve impact strength. However, excessive binder powder weakens the resin's processing performance and increases the difficulty of dispersing the binder powder in the SAN matrix, resulting in a decrease in the impact strength of the ASA resin, with a maximum not exceeding 400 J / m.

[0005] In summary, PBA polymerization mainly employs redox and thermally initiated free radical polymerization. The PBA polymerization process requires the addition of crosslinking agents and grafting agents to form a rubber core and a fully grafted shell. The polymerization process is complex, and the resulting ASA resin has low impact strength. Summary of the Invention

[0006] In view of the above-mentioned problems in the prior art, one of the objectives of the present invention is to provide a method for preparing polybutyl acrylate (PBA) by using RAFT reagent. On the one hand, it introduces excess double bonds into the PBA molecular chain to crosslink it into a rubber structure. On the other hand, it is used for grafting styrene and acrylonitrile to increase the compatibility between the rubber phase and the resin phase and improve the mechanical properties of the resin.

[0007] The second objective of this invention is to provide a polybutyl acrylate prepared by the above method, which has a high molecular weight and narrow molecular weight distribution, as well as a high degree of branching, high rubber elasticity, and better toughening effect.

[0008] A third objective of this invention is to provide an ASA resin prepared from the aforementioned polybutyl acrylate, which has ultra-high impact strength (greater than 400 J / m) and excellent weather resistance (500h UV aging test, dE less than 15), and can be applied to home appliances, office supplies, outdoor equipment and automobiles.

[0009] To achieve the above-mentioned objectives, the technical solution adopted by the present invention is as follows:

[0010] In a first aspect, the present invention provides a method for preparing polybutyl acrylate (PBA), comprising the following steps:

[0011] S1: Mix butyl acrylate, RAFT reagent, emulsifier, optional electrolyte and water, then add initiator and reducing agent to react and obtain PBA seed emulsion;

[0012] S2: Mix butyl acrylate, RAFT reagent, emulsifier, initiator and water to form a pre-emulsion;

[0013] S3: Add a reducing agent and a pre-emulsion to the PBA seed emulsion to prepare polybutyl acrylate.

[0014] In one embodiment of the present invention, based on a total of 100 parts of butyl acrylate added in steps S1 and S2, the raw material composition by mass is as follows:

[0015] Step S1 includes: 1-10 parts butyl acrylate, 0.01-0.5 parts RAFT reagent, 0.003-0.1 parts emulsifier, 0-1 part electrolyte, 50-150 parts water, 0.01-0.05 parts initiator, and 0.2-1.5 parts reducing agent;

[0016] Step S2 includes: 90-99 parts butyl acrylate, 5-10 parts RAFT reagent, 0.15-3 parts emulsifier, 0.1-10 parts water, and 0.15-3 parts initiator;

[0017] Step S3 includes: 0.1-10 parts of reducing agent. Specifically, in step S1, the butyl acrylate includes, but is not limited to, 1 part, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, or any combination thereof;

[0018] The RAST reagent includes, but is not limited to, 0.01 parts, 0.05 parts, 0.1 parts, 0.15 parts, 0.2 parts, 0.25 parts, 0.3 parts, 0.35 parts, 0.4 parts, 0.45 parts, 0.5 parts, or any combination thereof;

[0019] The emulsifier includes, but is not limited to, 0.003 parts, 0.005 parts, 0.01 parts, 0.02 parts, 0.03 parts, 0.04 parts, 0.05 parts, 0.06 parts, 0.07 parts, 0.08 parts, 0.09 parts, 0.1 parts, or any combination thereof.

[0020] The electrolyte includes, but is not limited to, 0 parts, 0.001 parts, 0.01 parts, 0.1 parts, 0.2 parts, 0.3 parts, 0.4 parts, 0.5 parts, 0.6 parts, 0.7 parts, 0.8 parts, 0.9 parts, 1 part, or a range consisting of any two of these.

[0021] The water includes, but is not limited to, 50 parts, 60 parts, 70 parts, 80 parts, 90 parts, 100 parts, 110 parts, 120 parts, 130 parts, 140 parts, 150 parts, or any combination thereof;

[0022] The initiator includes, but is not limited to, 0.01 parts, 0.015 parts, 0.02 parts, 0.025 parts, 0.03 parts, 0.035 parts, 0.04 parts, 0.045 parts, 0.05 parts, or any combination thereof;

[0023] The reducing agent includes, but is not limited to, 0.2 parts, 0.4 parts, 0.6 parts, 0.8 parts, 1.0 parts, 1.2 parts, 1.4 parts, 1.5 parts, or any combination thereof.

[0024] Specifically, in step S2: the butyl acrylate includes, but is not limited to, 90 parts, 91 parts, 92 parts, 93 parts, 94 parts, 95 parts, 96 parts, 97 parts, 98 parts, 99 parts, or any combination thereof;

[0025] The RAST reagent includes, but is not limited to, 5 parts, 5.5 parts, 6 parts, 6.5 parts, 7 parts, 7.5 parts, 8 parts, 8.5 parts, 9 parts, 9.5 parts, 10 parts, or any combination thereof;

[0026] The emulsifier includes, but is not limited to, 0.15 parts, 0.2 parts, 0.5 parts, 0.8 parts, 1 part, 1.2 parts, 1.5 parts, 1.8 parts, 2 parts, 2.3 parts, 2.5 parts, 2.8 parts, 3 parts, or any combination thereof;

[0027] The water includes, but is not limited to, 0.1 parts, 0.5 parts, 1 part, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, or any combination thereof;

[0028] The initiator includes, but is not limited to, 0.15 parts, 0.2 parts, 0.5 parts, 0.8 parts, 1 part, 1.2 parts, 1.5 parts, 1.8 parts, 2 parts, 2.3 parts, 2.5 parts, 2.8 parts, 3 parts, or any combination thereof.

[0029] Specifically, in step S3: the reducing agent includes, but is not limited to, 0.1 parts, 0.5 parts, 1 part, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, or any combination thereof.

[0030] In one embodiment of the present invention, the RAFT reagent is a reversible addition-fragmentation chain transfer reagent with a branched chain structure. Specifically, the RAFT reagent is selected from thioester compounds, preferably Bi s-MPA-RAFT dendrimer, pentaerythritol tetrakis[2-(dodecylthiocarbonylthiothio)-2-methylpropionate, methyl 2-((((2-(((dodecylthio)thiothio)thio)-2-methylpropionyl)oxy)methyl)-2-methylpropane-1,3-diylbis((2-((((dodecylthio)thiocarbonyl)thio)-2-propionate)).

[0031] The preparation method described in this invention also includes conventional auxiliary agents such as emulsifiers, electrolytes, initiators, and reducing agents, which can be conventionally selected in the field, and this invention does not have any special requirements.

[0032] In one embodiment of the present invention, the emulsifier is an anionic emulsifier, preferably one or more of potassium oleate, potassium disproportionate, sodium dodecyl sulfate, sodium dodecylbenzene sulfonate, and sodium dioctyl sulfonate.

[0033] In one embodiment of the present invention, the electrolyte is an inorganic salt, preferably one or more of potassium bicarbonate, potassium carbonate, sodium bicarbonate, sodium carbonate, and sodium tripolyphosphate.

[0034] In one embodiment of the present invention, the initiator is selected from inorganic peroxides and / or organic peroxides, preferably one or more of potassium persulfate, sodium persulfate, ammonium persulfate, dicumyl peroxide, and cumyl hydroperoxide.

[0035] In one embodiment of the present invention, the reducing agent is selected from one or more of ferrous sulfate, glucose, sodium pyrophosphate, disodium ethylenediaminetetraacetate, and sodium formaldehyde sulfoxylate.

[0036] In one embodiment of the present invention, the reaction in step S1 is carried out at a temperature of 50-80°C for a time of 0.3-1h; specifically, the temperature includes, but is not limited to, 50°C, 55°C, 60°C, 65°C, 70°C, 75°C, 80°C or any two of these ranges; the time includes, but is not limited to, 0.3h, 0.4h, 0.5h, 0.6h, 0.7h, 0.8h, 0.9h, 1h or any two of these ranges.

[0037] In one embodiment of the present invention, the pre-emulsion in S3 is fed by continuous dripping, and the feeding time is 2-5h, including but not limited to 2h, 2.5h, 3h, 3.5h, 4h, 4.5h, 5h or any combination thereof.

[0038] In one embodiment of the present invention, the reaction in step S3 is carried out at a temperature of 50-80°C for a time of 0.5-3 hours; specifically, the temperature includes, but is not limited to, 50°C, 55°C, 60°C, 65°C, 70°C, 75°C, 80°C, or any combination thereof; the time includes, but is not limited to, 0.5 hours, 1 hour, 1.5 hours, 2 hours, 2.5 hours, 3 hours, or any combination thereof.

[0039] Specifically, the reaction time is started from the end of the pre-emulsion feeding.

[0040] Secondly, the present invention provides a polybutyl acrylate (PBA) prepared by the method described above. Specifically, the product prepared by the above method is a PBA latex.

[0041] The polybutyl acrylate of this invention has the characteristics of high molecular weight, narrow molecular weight distribution and hyperbranching; wherein, the molecular weight can be as high as 20w or more; the molecular weight distribution is between 1 and 1.2.

[0042] A swelling ratio of 30 or higher indicates a high degree of branching in rubber. Because rubber has a three-dimensional network cross-linked structure, the degree of molecular chain branching cannot be directly measured by instruments; however, the swelling ratio can be used to indirectly characterize the degree of branching.

[0043] Thirdly, the present invention also provides the use of the polybutyl acrylate in the preparation of ASA resin.

[0044] In one embodiment of the present invention, the ASA resin is obtained by grafting, coagulating, dehydrating, and drying the polybutyl acrylate latex (PBA) with styrene and acrylonitrile as described above to obtain ASA powder, and then blending and extruding it with SAN resin.

[0045] The method for preparing ASA resin from PBA latex is an existing process, in which grafting, coagulation, dehydration, drying, blending, and extrusion are all conventional techniques in the field. The relevant operations and process conditions in the preparation method of this invention, as well as the apparatus used, can all be carried out using corresponding conventional selections in the field, and there are no particular restrictions. Those skilled in the art can combine, screen, and optimize existing processes according to actual needs to obtain the desired results; this invention will not elaborate further.

[0046] In this invention, an ASA resin prepared from the aforementioned polybutyl acrylate has an ultra-high impact strength of more than 400 J / m and excellent weather resistance. After 500 hours of ultraviolet aging test, the dE value is less than 15.

[0047] The ASA resin described in this invention can be applied to home appliances, office supplies, automobiles and other fields, and is especially suitable for the automotive industry.

[0048] As described above, the method provided by this invention first prepares hyperbranched high molecular weight narrow-distribution PBA latex using RAFT polymerization, then grafts styrene and acrylonitrile onto the surface of the rubber core to obtain ASA latex. The latex is then coagulated and powdered, and the ASA powder is blended with SAN resin to obtain ultra-high impact ASA resin. This method uses RAFT as a crosslinking agent and grafting agent to polymerize polybutyl acrylate. The RAFT reagent introduces excess double bonds into the PBA molecular chain, causing it to crosslink into a rubber structure. It can also be used for grafting styrene and acrylonitrile, increasing the compatibility between the rubber and resin phases and improving the mechanical properties of the resin.

[0049] Compared with the prior art, the beneficial effects of the technical solution of the present invention are as follows:

[0050] This invention utilizes a branched RAFT reagent, enabling PBA polymerization without the need for additional crosslinking and grafting agents. This allows styrene and acrylonitrile to be grafted onto the rubber core. PBA prepared by polymerization with the RAFT reagent exhibits ultra-high molecular weight and a narrow molecular weight distribution. The highly branched PBA molecular chains facilitate crosslinking and the formation of a three-dimensional network structure. Furthermore, PBA rubber demonstrates excellent toughening properties, and ultra-high impact ASA resin can be prepared using only a small amount of ASA powder. The ASA resin prepared from this method exhibits excellent impact performance, with an impact strength greater than 400 J / m, and also demonstrates excellent weather resistance, with a dE of less than 15 after 500 hours of UV aging testing. Detailed Implementation

[0051] To better understand the technical solution of the present invention, the following embodiments further illustrate the content of the present invention, but the content of the present invention is not limited to the following embodiments.

[0052] The raw material source information in the embodiments and comparative examples of the present invention is as follows. Unless otherwise specified, the raw materials used in the embodiments or comparative examples are obtained from ordinary commercial channels.

[0053] Butyl acrylate, Wanhua Chemical;

[0054] Sodium dodecyl sulfate, 99%, purchased from Aladdin;

[0055] Cumene hydroperoxide, 80%, purchased from Aladdin;

[0056] tert-butyl hydroperoxide, 70%, purchased from Aladdin;

[0057] Potassium oleate, BM-400, purchased from Ino Reagents;

[0058] Ferrous sulfate, 99%, purchased from Xilong Chemical.

[0059] Glucose, 99%, purchased from Xilong Chemical;

[0060] Sodium pyrophosphate, 99%, purchased from Aladdin;

[0061] Allyl methacrylate, 99%, purchased from Aladdin;

[0062] n-Octamethasone, purchased from Aladdin;

[0063] RAFT reagents were all purchased from Si GMA Reagents.

[0064] Example 1

[0065] Five parts by weight of butyl acrylate, 0.05 parts by weight of pentaerythritol tetrakis[2-(dodecylthiocarbonylthiothiothio)-2-methylpropionate reagent, 0.025 parts by weight of sodium dodecyl sulfate, 0.5 parts by weight of sodium carbonate, and 100 parts by weight of deionized water were added to a reactor and mixed. The mixture was kept at 70°C. Then, 0.025 parts by weight of cumene hydroperoxide and 1 part by weight of ferrous sulfate were added to the reactor and reacted for 0.5 h to prepare PBA seed emulsion.

[0066] A preemulsion was prepared by mixing 95 parts by weight of butyl acrylate, 8 parts by weight of pentaerythritol tetrakis[2-(dodecylthiocarbonylthiothiothio)-2-methylpropionate reagent, 1 part by weight of sodium dodecyl sulfate, 1.5 parts by weight of cumene hydroperoxide and 5 parts by weight of deionized water.

[0067] One part by weight of ferrous sulfate and four parts by weight of glucose were added to the PBA seed emulsion, and then a pre-emulsion was added dropwise over a period of 3 hours. The mixture was then kept at 75°C for 2 hours to prepare polybutyl acrylate latex.

[0068] Example 2

[0069] 10 parts by weight of butyl acrylate, 0.5 parts by weight of Bis-MPA-RAFT dendrimer reagent, 0.1 parts by weight of potassium oleate, 1 part by weight of potassium carbonate and 150 parts by weight of deionized water were added to a reactor and mixed and kept at 80°C. Then, 0.05 parts by weight of cumene hydroperoxide, 0.1 parts by weight of ferrous sulfate and 0.1 parts by weight of sodium pyrophosphate were added to the reactor and reacted for 1 hour to prepare PBA seed emulsion.

[0070] A preemulsion was prepared by mixing 90 parts by weight of butyl acrylate, 10 parts by weight of Bi s-MPA-RAFT dendrimer reagent, 3 parts by weight of sodium dodecyl sulfate, 3 parts by weight of tert-butyl hydrogen peroxide and 10 parts by weight of deionized water.

[0071] 0.1 parts by weight of ferrous sulfate were added to PBA seed emulsion, and then pre-emulsion was added dropwise over a period of 5 hours. The mixture was kept at 80°C for 0.5 hours to prepare polybutyl acrylate latex.

[0072] Example 3

[0073] One part by weight of butyl acrylate, 0.01 parts by weight of 2-((((2-((((dodecylthio)thiothio)thio)-2-methylpropanoyl)oxy)methyl)-2-methylpropane-1,3-dimethylbis((2-((((dodecylthio)thiocarbonyl)thio)-2-propanoate methyl ester) reagent, 0.003 parts by weight of sodium dodecyl sulfate and 50 parts by weight of deionized water were added to a reactor and mixed and kept at 50°C. Then, 0.01 parts by weight of tert-butyl hydroperoxide, 0.2 parts by weight of ferrous sulfate, 0.3 parts by weight of glucose and 1 part by weight of sodium pyrophosphate were added to the reactor and reacted for 0.3 h to prepare PBA seed emulsion.

[0074] A preemulsion was prepared by mixing 99 parts by weight of butyl acrylate, 5 parts by weight of 2-((((2-((((dodecylthio)thiothio)thio)-2-methylpropanoyl)oxy)methyl)-2-methylpropane-1,3-dimethylbis((2-((((dodecylthio)thiocarbonyl)thio)-2-propanoate methyl ester) reagent, 0.15 parts by weight of sodium dodecyl sulfate, 0.15 parts by weight of tert-butyl hydrogen peroxide, and 0.1 parts by weight of deionized water.

[0075] Ten parts by weight of glucose were added to PBA seed emulsion, and then pre-emulsion was added dropwise over a period of 2 hours. The mixture was kept at 50°C for 3 hours to prepare polybutyl acrylate latex.

[0076] Comparative Example 1

[0077] The method of Example 1 was followed, except that pentaerythritol tetra[2-(dodecylthiocarbonylthiothiothio)-2-methylpropionate (RAFT reagent) was not used, but replaced with an equal amount of 4-cyano-4-[[(dodecylthio)thiononemethyl]thio]pentane. All other operations and conditions were the same as in Example 1, and polybutyl acrylate latex was prepared.

[0078] Comparative Example 2

[0079] The method of Example 1 was followed, except that pentaerythritol tetra[2-(dodecylthiocarbonylthiothiothio)-2-methylpropionate (RAFT reagent) was not used, but replaced with an equal amount of crosslinking agent allyl methacrylate. Other operations and conditions were the same as in Example 1, and polybutyl acrylate latex was obtained.

[0080] Comparative Example 3

[0081] The method of Example 1 was followed, except that pentaerythritol tetra[2-(dodecylthiocarbonylthiothiothio)-2-methylpropionate (RAFT reagent) was not used, but replaced with an equal amount of chain transfer agent n-octyl mercaptan. All other operations and conditions were the same as in Example 1, and polybutyl acrylate latex was prepared.

[0082] PBA Latex Test Examples

[0083] The performance parameters of the PBA latexes prepared in Examples 1-3 and Comparative Examples 1-3 were tested using the following methods, and the results are shown in Table 1:

[0084] PBA molecular weight test: PBA is swollen in acetone solvent, filtered to obtain a clear liquid, and dried in acetone to obtain uncrosslinked PBA. Testing its molecular weight can indirectly characterize the molecular weight of crosslinked PBA rubber.

[0085] PBA swelling ratio test: Dry the PBA latex, weigh the PBA (referred to as A), soak the PBA in toluene until it swells, filter after 24 hours, and weigh the mass of the swollen body (referred to as B).

[0086] Swelling ratio = B / A.

[0087] Table 1. Test results of PBA performance parameters prepared in the examples and comparative examples.

[0088] Molecular weight Mw Molecular weight distribution swelling ratio Example 1 20w 1.12 30 Example 2 22w 1.16 35 Example 3 20w 1.09 31 Comparative Example 1 18w 1.1 22 Comparative Example 2 12w 2.93 14 Comparative Example 3 10w 2.45 11

[0089] Example of ASA resin preparation

[0090] ASA resin powder was prepared using the PBA latex prepared in Examples 1-3 and Comparative Examples 1-3, and then blended with SAN resin and extruded and injection molded into ASA resin test strips. The specific steps are as follows:

[0091] 1) Preparation of ASA latex

[0092] Add 60 kg (by solids) of polybutyl acrylate latex, 120 kg of deionized water, 0.001 kg of FeSO4·7H2O, 0.01 kg of sodium pyrophosphate, and 0.1 kg of glucose to the reactor and start stirring. After heating the reactor to 70°C, continuously add a mixed pre-emulsion consisting of 0.2 kg of cumene hydroperoxide, 30 kg of styrene, 10 kg of acrylonitrile, 0.5 kg of tert-dodecyl mercaptan, 2.5 kg of potassium oleate, and 10 kg of deionized water. The continuous feeding time is 3 hours. After the feeding is completed, heat the reactor to 80°C and continue the reaction for 3 hours. Then cool to room temperature and stop stirring. Filter to obtain ASA grafted latex.

[0093] 2) Preparation of ASA adhesive powder

[0094] Add 2 kg of MgSO4 and 200 kg of deionized water to the coagulation vessel and start stirring to fully dissolve the MgSO4. Heat the coagulation vessel to 75°C and continuously feed 100 kg of ASA grafted latex prepared in step 1) into the coagulation vessel for 1 hour. After feeding, heat the coagulation vessel to 90°C and keep it at that temperature for 1 hour. Then, cool the coagulated slurry to room temperature, filter, wash, and dehydrate to obtain ASA wet latex powder. Dry the ASA wet latex powder in a fluidized bed dryer at 65°C until the moisture content is <1% to obtain ASA latex powder.

[0095] 3) ASA resin preparation and injection molding

[0096] A twin-screw extruder was used with three temperature sections of 190℃, 210℃ and 220℃. SAN resin of LG Chem brand SA 30 was used as the continuous phase for blending, and ASA rubber powder prepared in step 2) was used as the dispersed phase for blending. The ASA resin was obtained by blending, extrusion and granulation according to a polybutyl acrylate rubber content of 24%.

[0097] Various test specimens of the above-mentioned ASA resin were prepared at 210°C on an injection molding machine, and their properties were tested according to the following methods. The results are shown in Table 2:

[0098] Impact strength value: Tested according to ASTM D2560 standard.

[0099] ASA grafting rate test: Weigh a certain amount of ASA gum powder (denoted as C), put the gum powder into acetone and heat to boiling for 2 hours, centrifuge to separate the supernatant and the lower precipitate, and record the dry weight of the lower precipitate (denoted as D).

[0100] Grafting rate = (DC * percentage of formulated rubber) × % / (C * percentage of formulated rubber).

[0101] Cantilever beam notched impact: Standard ASTM D256, 23°C, using Italian CEAST 9050.

[0102] UV aging performance test: standard GB / T 16422.3-2022, light source: UVA-340nm, irradiance: 0.76W / m2.nm60℃, cycling conditions: 8h of light exposure, 4h of condensation at 50℃.

[0103] Table 2. Performance test results of ASA resins prepared in the examples and comparative examples.

[0104]

[0105]

[0106] The test results of Examples 1-3 and Comparative Examples 1-3 show that the PBA rubber prepared using the present invention has a higher molecular weight, a narrower molecular weight distribution, and a larger swelling ratio, which can indirectly show a higher degree of branching. The ASA resin prepared from it has ultra-high impact strength and excellent weather resistance. The impact strength is greater than 400 J / m, and the dE after 500 h of UV aging test is less than 15.

[0107] Obviously, the above embodiments are merely illustrative examples for clear explanation and are not intended to limit the implementation. Those skilled in the art will recognize that other variations or modifications can be made based on the above description. It is neither necessary nor possible to exhaustively list all possible implementations here. However, obvious variations or modifications derived therefrom are still within the scope of protection of this invention.

Claims

1. A method for preparing polybutyl acrylate, characterized in that, Includes the following steps: S1: Mix butyl acrylate, RAFT reagent, emulsifier, electrolyte and water, then add initiator and reducing agent to react and obtain PBA seed emulsion; S2: Mix butyl acrylate, RAFT reagent, emulsifier, initiator and water to form a pre-emulsion; S3: Add a reducing agent and a pre-emulsion to PBA seed emulsion and react to prepare polybutyl acrylate; The RAFT reagent is selected from one or more of Bis-MPA-RAFTdendrimer, pentaerythritol tetra[2-(dodecylthiocarbonylthiothio)-2-methylpropionate], and 2-(((2-(((dodecylthio)thiothio)thio)-2-methylpropionyl)oxy)methyl)-2-methylpropane-1,3-dimethylbis(2-(((dodecylthio)thiocarbonyl)thio)-2-propionate methyl ester).

2. The preparation method according to claim 1, characterized in that, Based on 100 parts of butyl acrylate added in steps S1 and S2, the raw material composition by mass is as follows: Step S1 includes: 1-10 parts butyl acrylate, 0.01-0.5 parts RAFT reagent, 0.003-0.1 parts emulsifier, 0-1 part electrolyte, 50-150 parts water, 0.01-0.05 parts initiator, and 0.2-1.5 parts reducing agent; Step S2 includes: 90-99 parts butyl acrylate, 5-10 parts RAFT reagent, 0.15-3 parts emulsifier, 0.1-10 parts water, and 0.15-3 parts initiator; Step S3 includes: 0.1-10 parts of reducing agent.

3. The preparation method according to claim 1, characterized in that, The emulsifier is an anionic emulsifier; and / or The electrolyte is an inorganic salt; and / or The initiator is selected from inorganic peroxides and / or organic peroxides; and / or The reducing agent is selected from one or more of ferrous sulfate, glucose, sodium pyrophosphate, disodium ethylenediaminetetraacetate, and sodium formaldehyde sulfoxylate.

4. The preparation method according to claim 3, characterized in that, The emulsifier is selected from one or more of potassium oleate, potassium disproportionate, sodium dodecyl sulfate, sodium dodecylbenzene sulfonate, and sodium dioctyl sulfonate.

5. The preparation method according to claim 3, characterized in that, The electrolyte is selected from one or more of potassium bicarbonate, potassium carbonate, sodium bicarbonate, sodium carbonate, and sodium tripolyphosphate.

6. The preparation method according to claim 3, characterized in that, The initiator is selected from one or more of potassium persulfate, sodium persulfate, ammonium persulfate, dicumyl peroxide, and cumyl hydroperoxide.

7. The preparation method according to claim 1, characterized in that, The reaction described in step S1 is carried out at a temperature of 50-80℃ for a time of 0.3-1h.

8. The preparation method according to claim 1, characterized in that, The preemulsion described in S3 is fed continuously over a period of 2-5 hours; and / or The reaction described in S3 is carried out at a temperature of 50-80℃ for a time of 0.5-3h.

9. A polybutyl acrylate, characterized in that, It is prepared by the method described in any one of claims 1-8.

10. The polybutyl acrylate according to claim 9, characterized in that, It is a type of PBA latex.

11. Use of the polybutyl acrylate of claim 9 in the preparation of ASA resin.

12. An ASA resin, characterized in that, It is prepared by grafting, coagulating, dehydrating and drying the polybutyl acrylate latex as described in claim 9 with styrene and acrylonitrile to obtain ASA adhesive powder, and then blending and extruding it with SAN resin.

13. The application of the ASA resin of claim 12 in the fields of home appliances, office supplies, and automobiles.

14. The application according to claim 13, characterized in that, Applicable to the automotive industry.

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