TW201217402A - adopting a continuous stirred-tank reactor (CSTR) and/or a plug flow reactor (PFR) to prepare high impact polystyrene (HIPS), thereby the product stream can have an ESCR value at least 10% toughness retained with smaller than 10 wt% rubber content - Google Patents

Abstract

A method of preparing high impact polystyrene includes: feeding at least one vinyl aromatic monomer, an elastomer and a free radical initiator to a first linear flow reactor to form a reaction mixture; polymerizing the reaction mixture in the first linear flow reactor to a point below the point of phase transition to prepare a first polymerization mixture; feeding the first polymerization mixture from the first linear flow reactor to a second linear flow reactor; polymerizing the reaction mixture in the second linear flow reactor to at least the phase transition point of the mixture to prepare a second polymerization mixture; and feeding the second polymerization mixture from the second linear flow reactor to at least a third linear flow reactor to carry out post-conversion polymerization of the second polymerization mixture. Thereby, the product stream can have an ESCR value at least 10% toughness retained with smaller than 10 wt% rubber content.

Description

201217402 IV. Designated representative map: (1) The representative representative of the case is: (2). (2) A brief description of the symbol of the representative figure: 205~feed line; 215~output line; 222~motor; 2 2 5~ pipeline; 2 3 5~ pipeline; 2 4 5~ pipeline; 2 5 5~ pipeline . 200 to reactor system; 210 to first linear flow reactor 220 to polymerization reactor; 224 to agitator; 230 to second polymerization reactor; 240 to third polymerization reactor; 250 to fourth polymerization reactor; 5. If there is a chemical formula in this case, please disclose the best and no features of the invention. PREPARATION VI. DESCRIPTION OF THE INVENTION: TECHNICAL FIELD OF THE INVENTION The present invention relates generally to the manufacture of polystyrene. More specifically, the present invention relates to the manufacture of high impact polystyrene using a continuous stirred tank reactor or a piston flow reactor or a combination thereof. [Prior Art] Elastomer-reinforced polymers of monovinylidene aromatic compounds such as styrene, α-methylstyrene and % substituted styrene are widely used for a wide range of commercial applications. For example 'discrete elastomer particles such as cross-linked rubber 201217402 Elastomer-reinforced styrene polymers dispersed throughout the stupid ethylene polymer matrix are available: a wide range of applications including food packaging, office enamel, automotive parts, household goods and consumer goods , building insulation and cosmetic packaging. Such elastomer-reinforced polymers are commonly referred to as high impact polystyrene (Hips). A method of producing a polymer such as HIPS may employ a polymerization using a continuous flow method. The continuous flow process relates to an apparatus comprising a plurality of reactors arranged one after the other, wherein the degree of polymerization increases from one reactor to the next. The type of reactor used in the manufacture of HIPS may include a continuous stirred tank reactor ((iv)) and/or a plug flow reactor (PFR). Factors such as the arrangement of the reaction vessel and the reaction conditions affect the properties of the manufactured HIps. The degree of polymerization within each reactor, which results in different mechanical and/or optical properties, and the amount of elastomeric content can determine the level of HIPS produced. The physical and mechanical properties of the cis depends on many factors such as the particle size of the crosslinked rubber particles. The important quality of Ding Lu is the strength of such materials. This force must be combined with the characteristics of high impact strength so that it can be used in articles such as sigma, such as 谷 00 00. In addition, other important properties of such articles include flexural strength and tensile strength. It is particularly important for the properties of the HIPS or any other thermoplastic polymer that is used to prepare the 〇 〇 〇 T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T T The food contents of the k-like polymer container taken from the Μ Μ 通常 通常 通常 通常 通常 通常 通常 通常 通常 通常 通常 或者 或者 或者 或者 或者 或者 HT HT HT HT HT HT HT HT HT HT HT HT HT 制成 HT HT HT 制成 制成 制成 制成 制成 制成When the material is thermoformed from the extruded sheet, the stress is locked in the molding σ_lL ^ , 2 ports. These stresses cause the polymer to begin to attack by the Lu's sputum material, which is usually unaffected by the composition. Such articles made from styrene polymers modified with rubber to improve the impact strength of 201217402 are susceptible to stress cracking when contacted with common materials such as fats and oils present in organic foods. Similarly, such products undergo stress cracking when contacted with fluorine-containing organic blowing agents such as functional hydrocarbons. These polymers are usually present in household goods such as refrigerators. When the cavity in the refrigerator is filled with a polym bundle, it can be cracked due to the foaming agent employed in the above foam. Through j, the effort to prevent or mitigate environmental stress cracking is usually related to the middle intermediate layer of the polymer between the polystyrene layer and the blowing agent or between the materials. The complex composition of the layer's multilayer polymer structure. Such a material layer for isolating the above styrene from these materials is a ternary copolymer material called ABS or acrylonitrile-butadiene-styrene. Other attempts to improve high impact monoolefinic properties include stress cracking, the amount of rubber incorporated in the poly delta. However, the rubber content of the second:: can reduce the tensile and flexural strength and will typically increase the cost. The type of method 'and the elastomer used == delete manufacturing costs. Accordingly, it is desirable to develop an apparatus and method for manufacturing a reduced and modified amount of _ with mechanical properties such as impact strength, ductility, and coffee. It is also expected to be developed for manufacturing. Equipment and methods for environmentally resistant stress cracking HIPS. SUMMARY OF THE INVENTION One embodiment including = Ming is a method for producing a high impact polystyrene, feeding at least an ethylene-based aromatic monomer, an elastomer, and a radical-initiating agent 4 201217402 to the first The linear flow reactor was used to form a reaction mixture. The above reaction mixture in the above first linear flow reactor is polymerized to a point below the point at which phase transformation occurs to produce a first polymerization mixture. Feeding the first polymerization mixture from the first linear flow reactor described above to a second line I"raw-grip reactor' in the second linear flow reactor to further polymerize the first polymerization mixture to at least the above The phase inversion point of the mixture is used to make a second polymerization mixture. The second polymerization mixture from the second linear flow reactor described above is then fed to a third linear flow reactor and optionally more reactors for post-conversion polymerization of the second polymerization mixture described above. One embodiment of the present invention is a method of making high impact polystyrene comprising feeding at least one vinyl aromatic monomer, an elastomer, and a free radical initiator to a canister to form a reaction mixture, followed by the above reaction The mixture was fed from the above mixing tank to the first linear flow reactor and was carried out as in the above method. An alternative embodiment of the present invention comprises feeding at least one vinyl aromatic precursor, an elastomer, and a free radical initiator to a heated mixing tank to form a reaction mixture; and the above-described heated mixing tank The reaction mixture is heated, after which the above reaction mixture is fed from the above mixing tank to the first linear flow reactor and as in the above process. Further, a continuous process for feeding at least one vinyl aromatic single:::, free radical initiator to a series of polymerization reactors is also disclosed herein. The series of polymerization reactors described above may comprise at least two linear flow reactors. After polymerization, the product can be devolatilized using a preheater operating at a reduced temperature of 201217402. The preheater described above can be operated at temperatures below 470 °F to achieve an increased eSCR value. Embodiments of the present invention can produce a product having an ESCR value of at least 10% toughness retained with a rubber content of less than 10%. Embodiments of the present invention can produce products having a rubber particle size (RPS) above 5 #m. [Embodiment] Figure 1 illustrates a prior art high impact polystyrene (HIPS) manufacturing process of U.S. Patent No. 4,777,210, the entire disclosure of which is incorporated herein by reference. The process comprises a continuous stirred tank reactor (CSTR) pre-conversion reactor R100' followed by a CSTR conversion reactor R101 followed by at least one piston flow post-conversion reactor R-丨. The output is sent to the conventional devolatilizer DV-i after the conventional heater H-1'. Figure 2 depicts a schematic of a reactor system 200 for the continuous manufacture of elastomer-reinforced polymers. In one embodiment, the reactor system 2 can be used in a continuous HIPS manufacturing process. Referring to Figure 2, a reaction mixture comprising styrene, an elastomer such as polybutadiene rubber, and a free radical initiator can be fed to the first linear flow through one or more feed lines generally indicated as 2〇5. Reactor 21G. In an alternate embodiment, the reaction mixture comprises a styrene elastomer such as a polybutadiene rubber, a chain transfer agent, and additional components such as those known in the art of HIPS manufacturing. In another embodiment, the reaction mixture comprises: styrene; an elastomer such as polybutadiene rubber; a combination of a free radical initiator and a chain transfer agent; and additional composition examples > those known in the manufacturing field 6 201217402 . The selection and amount of free radicals, chain transfer agents, and additional components used to make the hips can be included as known to those skilled in the art. , 'knife j % In one embodiment, the reaction mixture fed to the itch 7 inch main continuous hips manufacturing process may include about 75% to about 99% of the stem 7 secret M / t) the present, about 1% ~ about polybutadiene, about 0.001% ~ about 勹〇. 2 / 6 free radical initiator and additional components to give any desired physical properties. There are weight percentages for all components. The term linear flow reactor includes a piston flow reaction H (sharp). The first linear flow reactor or PFR 21G can be operated at any point that allows the polymerization to proceed until the phase transition occurs. In one embodiment, the first linear flow reactor 2H is operated under pre-conversion conditions, gp, wherein the continuous phase is stupid; the if-rubber solution and the discontinuous phase are: In the k example, the styrene diluent may include other diluents such as ethylbenzene, toluene, hydrazine, and combinations thereof. In one embodiment, the first linear flow reactor 210 or the pre-conversion reactor (piR) is located directly in front of the polymerization reactor' such that the stupid ethylene polybutane, the free radical initiator and other components are fed to the PIR 210 and exit The mixture of PIR is then fed to polymerization reactor 220. In one embodiment, polymerization reactor 22 is a second linear flow reactor. In one embodiment, the linear flow reactor described above comprises a plug flow reactor (PFR). In one embodiment, the polymerization reactor 22 or the second PFR is vertically arranged. In another embodiment, the second pFR 22 is horizontally arranged. In one embodiment, the polymerization reactor 22 or the second linear flow inverse / 7 201217402 can be operated under the following conditions: 'allowing the polymerization to proceed until at least the ruthenium reaction mixture is introduced to any additional polymerization oxime Phase transition point. Thus, polymerization reactor 220 is referred to as a plug flow conversion reactor (PFIR). In other words, the reactants in polymerization reactor 22 are subjected to phase inversion before leaving the reactor (herein referred to as PFIR 22).

彳Transformation# The morphological transformation that occurs during the preparation of ΗIPS. The starting materials for the η I preparation generally comprise a polydiene rubber and a styrene monomer. These two components are usually miscible. In the pre-conversion stage of manufacture, a mixture of #ethylene and polybutadiene forms a continuous phase of a mixture of polystyrene and styrene dispersed therein. As the reaction of styrene to the polystyrene progresses and the amount of stilbene increases, the phase inversion occurs, after which the polystyrene/stupid ethylene blend forms a continuous phase in which the rubber particles are dispersed. This phase transformation results in the formation of the rubber particles in the bean in the form of a film surrounding the film of the occluded polystyrene. The size and distribution of the rubber particles can affect the physical and mechanical properties of the coffee. In one embodiment, the polymerization reactor 220 can be operated at any point that allows the polymerization to proceed until the phase inversion occurs. In one embodiment the 'polymerization reactor, 220 is operated under pre-conversion conditions, i.e., the continuous phase in the beans is a stupid ethylene-rubber solution and discontinuous octopus equine ethylene-polystyrene. In another embodiment, the first linear stream is initially transported by Is 210 and polymerization reactor 220 under pre-conversion conditions. +, .^ . In a further embodiment, the first linear flow reactor 210, the polymerization anti-injection 2200 and any directly sequential PFR are each run under pre-conversion conditions. In one aspect, the first linear flow reactor 210 and any other reaction 8 201217402 at pf 丨 R am are each operated under pre-conversion conditions. It can be operated in a wide range of temperatures. In one embodiment, (iv) operates at a temperature of 230 F or higher. In another embodiment, the coffee is at 230 F. Run at 300 F. In a more specific embodiment, pm is at a temperature of 240 ° F to 280 ° F, Fan - Shi #

Under the order. In a further embodiment, the PFIR operates at a temperature of 260T to 270T. Piston grip characteristics can be used in the conversion reactor to optimize the formation of rubber particles. Referring again to Figure 2, PF ΤΡ 99 Π - Γ A A , solid < 〇 IR 220 may include agitator 224 driven by motor 222. Such agitators can promote radial dispersion of the reactants, but are not intended to provide axial mixing to minimize back mixing in the reactor. In one embodiment, the agitator purple leaf configuration in a linear flow reactor can be adjusted to improve piston flow characteristics. In one embodiment, the (iv) number of the piston flow reactor is operated to: a shear rate below. In one embodiment, the piston flow reaction & (four) mixer operates at a shear rate of 8 s to 15 () s. In another embodiment, the agitator of the plug flow reactor operates at an f = rate of 8 s. 1 〜. In one embodiment, the stirrer of the piston flow reaction H is operated at a shear rate of 2 5 s -1 to 7 5 s-1. In a further embodiment, the agitator of the plug flow reactor is transported at a shear rate of ~^, which is at a shear rate below ππ. run. In another aspect, the mR mixer operates at a shear rate of 35 to 90 s]. In an alternative aspect, the PFIR is at a dose of 5. ~70s-, the shear rate runs. The ability to alter the shear rate at the transformation point within the system can result in improved product morphology. Counter 201217402 The reactor size, manufacturing rate, agitator speed, and agitator configuration are factors that can be varied to control the shear rate at the conversion point within the system and result in improved product morphology. Referring again to Figure 2, a reactor process 2 is illustrated in which the output line 215 from the linear flow pre-conversion reactor PIR 210 can be directed to the polymerization reactor 220. The output from reactor 220 can be directed to second polymerization reactor 230 via line 225. The output from reactor 230 can be directed to third polymerization reactor 240 via line 235. The output from reactor 240 can be directed to fourth polymerization reactor 250 via line 245. In one embodiment, the above polymerization reactors are each a linear flow reactor. In another embodiment, the first polymerization reactor 220 is a conversion reactor. In a further embodiment, the first polymerization reactor 230 is a conversion reactor. In the case where the output from the polymerization reactor 220 is fed to the additional polymerization reactors 230, 240 and 250 via lines 225, 235 and 245, respectively, the polymerization of styrene to polystyrene can be continued. In one embodiment, reactors 23, 240, and 250 can be linear flow reactors such as piston flow reactors, which can also be equipped with an agitator driven by an electric motor. In the embodiment shown in Figure 2, three linear flow reactors 23, and 250 are positioned horizontally and connected in series with polymerization reactor 22, as desired by the user. One skilled in the art can determine the number of linear flow reactors, positioning (e.g., level or vertical), and connectivity (e.g., in series or in parallel) based on, for example, the required manufacturing capabilities or the desired degree of product conversion. The resulting η I polymer and any other remaining compounds may be withdrawn from the final reactor, such as reactor 2 5 via a line 2 5 5 , and may then be subjected to a HIps polymer and 10 201217402 and optionally further processed to the crucible, for example Granulation. In one embodiment, the linear flow reactor described above includes at least two reactors arranged in series directly after the pre-conversion reactor. In another embodiment, '2 to 1 G of reactors arranged in series are located directly after the pre-conversion reactor. In an advanced embodiment, the 4 Μ reactors arranged in series are located directly after the pre-conversion reactor. The above linear flow reactors may be arranged in series or in parallel, in each of the above embodiments, the <> of the above-mentioned linear flow reactors, and two of them are arranged in parallel. In an alternate embodiment, referring to Figure 2, one or more of the reactors 210, 220, 230, 240, 250 represent more than one reactor in parallel. For example, reactor 23A can represent two reactors in parallel and reactor 240 can represent three reactors in parallel. Figure 3 depicts a schematic of a reactor system 300 for the continuous manufacture of an elastomer-enhanced polymer with a mixing tank 306 added prior to the reactor scheme of Figure 2. In one embodiment, the reactor system 300 can be used in a continuous Η IPS manufacturing process. Referring to Figure 3, a reaction mixture comprising a styrene 'elastomer such as a polybutadiene rubber, and a free radical initiator can be fed to the mixing tank 306 through one or more feed lines, generally indicated at 305, and can include Agitator 318 driven by motor 316. In one embodiment, the mixing tank 3 〇 6 precedes the linear flow reactor system of FIG. In Figure 3, the output line 307 from the mixing tank is passed to a linear flow pre-reforming reactor PIR 310. The output from PIR 310 can be directed via line 315 to polymer reactor 302 (conversion reactor), which can include agitator 324 driven by motor 322. The output from reactor 320 can be directed to second polymerization reactor 330 via line 325. The output from the reaction state 330 can be directed to the third polymerization reactor 340 via line 335. The output from reactor 34A can be directed via line to fourth polymerization II 350. The output from reactor 35A can exit the above process via line 355. In one embodiment, the above polymerization reactors are each a line 1 &< IL dynamic reactor. In another embodiment, the first polymerization reactor 320 is a conversion reactor. In the embodiment, the second polymerization reactor 330 is a conversion reactor. The polymerization of styrene to polystyrene can be continued in the case where the output from the poly-sigma reaction benefit 320 is fed to the additional polymerization reactors 330, 340 and 350, respectively, via a line. In one embodiment, reactors (10), 34G, and 35G can be linear flow reactors such as piston flow reactors. They can also be equipped with a stirrer driven by an electric motor. In the embodiment shown in item 3, the three linear flow reactors 330 340 and 350 are positioned horizontally and in series with the polymerization reactor 32, and those skilled in the art can based on, for example, the required manufacturing capabilities or: desired products. The degree of conversion requirements breaks the number of linear flow reactors (eg, level or vertical) and connectivity (eg, tandem or parallel:). From the final reactor, such as reactor 35, via line 355. The desired HIPS polymer and any other remaining compounds are removed and the HIPS polymer can then be taken and optionally further processed, such as granulated. In one embodiment, the mixing tank 306 is a stirred tank reactor such as a CSTR. In one embodiment, the ratio of the internal volume of the mixing tank to the linear flow reactor is 1:4 to 8: In an alternative embodiment, the ratio of the volume of the mixing tank to the linear flow reactor is 1 : 2 to 4: In a further embodiment, the ratio of the volume of the mixing tank to the linear flow reactor is Η 12 201217402 2 ··1. In one embodiment, the mixing tank has a liquid level percentage of 100% of the tank volume. 9%。 In another embodiment, the mixing tank has a liquid level percentage of 5 to 99.9%. In an alternate embodiment, the mixing tank has a liquid level of from 1 〇 to 95%. In a further embodiment the liquid level of the mixing tank is from 25 to 9 %. In another embodiment in which the mixing tank is a CSTR, the liquid level is at a minimum level sufficient to completely immerse the stirrer of the CSTR. In one embodiment, the mixing tank 3 〇 6 is not subjected to heat from an external source. In such an embodiment, the only heat supplied to the mixing tank is from the feed stream. In another embodiment, the mixing tank is applied via an external source: the external heat source includes a steam jacket and any other known equipment for heating the mixing tank. In one embodiment, the mixture in the mixing tank is heated to a temperature below 2,f. In another embodiment, the mixture is heated to 15 Torr to 225. ?temperature. In a further embodiment the mixture is heated to a temperature of from 1 75 °F to 220 °F. In one embodiment, the product leaving the final polymerization reactor is passed: to a devolatilizer to remove the volatile component from the molten polymer product prior to the extrusion step. The above devolatilization 11 may include a preheater. The devolatilizer and/or pre = above may be selected from any suitable devolatilizer design and devolatilizer preheater tube devolatilizer and plate devolatilizer. In the case of (four), the above =^=47_ temperature is called. ...step embodiment of the lower run off ~ ~ 45GF temperature. It has been found that embodiments can result in improved product morphology. The following examples are given as a general description of the embodiments. 13 201217402 DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The above-described embodiments are described by way of example and the scope of the claims. It is understood that the description is not intended to limit the description in any way. In one embodiment, as shown in her six ESW r container V-1A phase mixture, such as CSTRe, in an embodiment, the ratio to the flow reactor is w~2 ten in /... The volume and linearity of the mixing tank and the ratio of the two alternative embodiments in the case of the 机动 踝 机动 机动 机动 机动 机动 i i i i i i i i i i i i i i i 实施 实施 实施 实施 实施 HU HU Line (4) Movement 1: 1 to 2: 1 〇, 匕 is a container spoiler such as CSTR as shown in Figures 4, 5 and 6 in an embodiment. In one embodiment, the ratio of the internal volume of the Bu 2 to the linear flow reactor is 1:1 to 8:1. In an alternative embodiment: the ratio of the volume of the mixing tank to the linear flow reactor is 2:1 to 6: In the embodiment of the advanced step, the ratio of the volume of the mixing tank to the linear flow reactor is 3 : 1 ~ 5 : 1. Example 1 High impact polystyrene was produced using a first level piston flow conversion reactor (HPFIR) process. As shown in Figure 4, the baseline method begins with two CSTRs followed by three or four HPFIRs. The rubber used is Texas, Orange's Firestone Diene 55 (D55) and Lanxess

Corp's Tactene (1202). Table 1 contains the results of a test using Lacqrene 7240 (commercial HIPS polystyrene grade available from Total Petrochemicals Europe) in a baseline method configuration: 14 201217402 Test No. 1 2 3 4 5 6 7 Sample Description 50% D55 50% 1202 75%D55 25%1202, 100%D55 100%D55 Baseline is fed at the top of V-2 and recirculated to reduce V-2 agitation, 141s] Reduced Rb R4 agitated rubber type (concentration 9%) 50% D55 50%1202 75%D55 25%1202 100%D55 100%D55 100%D55 100%D55 100%D55 W thinner,% 6.3 6.9 6. 5 6.7 6.6 6. 6 6 Manufacturing rate, pounds per hour 91 91 91.5 91 91 91 93 Gardner Impact 82.8 100.5 116.8 125.6 133.6 119.6 136.7 . Notched Izod Impact 3.47 3. 35 3.17 3. 02 2.9 3. 04 3.19 Melt Flow Rate 3.97 4.15 4.01 4.43 4.38 4.37 3. 88 _Rubber Particle Size 5. 22 4.41 4.51 3.62 3.65 3.84 3. 83 _ tensile modulus 235100 232700 235900 266600 257100 240000 245100 yield tensile strength 3146 3254 3242 3177 3017 3368 3328 tensile strength at break 3049 3011 3122 2989 2937 3190 3059 elongation at break 52.5 50.8 50.1 57.3 56.5 50.9 49.4 Flexural modulus 354600 353900 346000 288700 277900 347700 344200 Flexural strength 6987 7146 7191 5884 5752 7409 7349 Swelling index 14 13 13 13 12 13 13 __ Gel content 20.11 21.39 21.75 23.45 24. 23 23.51 23.78 Grafting 130.4 143.6 151.4 167.4 171 167.2 171.5 _gel: rubber 2. 30 2.44 2.51 2.67 2.71 2.67 2.71 _ Μ 837 81837 82096 77559 75205 72569 76731 76165 _ Mw 196983 196432 188307 178653 173682 182794 183167 Polydispersity 2.4 2.4 2.4 2.4 2.4 2.4 2.4 Gloss, 20° 7.7 10.8 12.5 17.8 19.7 16.1 20.7 _Gloss, 60° 33 42.5 47.2 55.6 58.7 52.6 59 ... RPVF 29.8 27.5 29.9 28.3 31.1 29.6 Example 2 The test was then carried out using the new configuration shown in Figures 5 and 6. Figure 5 is depicted as having a first CSTR (Vl) followed by first and second HPFIR (R-1 and R-2) followed by a second CSTRCV-2) followed by a third and fourth HPFIR (R -3 and R-4). For these experiments, two grades of 825E PS and 7240 PS available from the commercial HIPS polystyrene grade of Total Petrochemicals Europe were selected. Two tests were performed using the 7240 grade. Test 8 uses the method configured as shown in FIG. Runs 9 and 8 were identical except that V-1 was removed so that the feed was delivered to R-1 as shown in FIG. 15 201217402 Table 2 shows the key process conditions and properties obtained. Test No. 8 9 Description Heat 7240, using V-1 Heat 7240, omitting V-.1 Using V-1? Is V-2 used? Yes, manufacturing rate, pounds per hour 68 82 Melt flow rate 2.7 3 pellets RPS 3.9 4.4 tensile modulus, psi 258900 278420 elongation at break, % 42.4 37.4 flexural modulus, psi 311940 298980 swelling index 11 10 gel content 23.72 23.02 graft 182.1 175 gel: rubber 2.88 2.75 RPVF 20.9 20.8 Example 3 In Example 3, reactors V-1 and V-2 were removed, resulting in no CSTR in the process, as shown in FIG. This change produces a gel: improvement in rubber ratio. Two tests were performed. Run 12 was configured using this new method, but with V-1 and V-2 removed, as shown in FIG. Run 13 was the same as Test 12, but was initiated with Luperso 1 L233. Table 3 shows the results of Example 3. Table 3 also shows that the method of Example 3 achieves a higher gel: rubber ratio than the prior art method in Table 1 and the method of Example 2 in Table 2. Test No. 12 13 Description 7240 Heat 7240 W/L233 Initiator L233 Initiator Concentration, ppm 100 Manufacturing Rate, Pounds/Hour 56 63 16 201217402 Melt Flow Rate 3.6 4.3 Pellet RPS 4.1 4 Tensile Modulus, psi 258000 251200 Fracture Elongation, % 49.3 58.4 Flexural modulus, psi 288400 283100 Swelling index 12 12 Gel content 24.87 24. 88 Grafting 182 203.5 Gel: Rubber 2.8 3.03 RPVF 21.3 26.7 Example 4 Using a first vertical piston flow conversion reactor The (VPFIR) method produces high impact polystyrene. An experiment was conducted to determine the ESCR value of the product of the VPFIR method. The results are not in Table 5 below: Test No. 23 24 25 26 Product / Description 8260 8260 High PFIR solids using V-2 using V-2? No No No Recirculation flow rate 19 25 21.7 26.8 Manufacturing rate, lb / Hours 76 71 73 74 pellets RPS, / / (volume) 5.85 8. 77 9.08 8.08 glare flow, dg/10min 3.3 4.3 3.6 3.2 tensile modulus 224640 243370 257850 255100 flexural modulus 292850 267340 284890 284810 swelling index 13 15 14 10 Gel: Rubber 2.79 2.58 2.65 2.97 RPVF 33.6 37.1 35.1 30.6 ESCR, Residual Toughness % 1 4.6 2.5 1.3 The test using the first vertical piston flow conversion reactor resulted in a poor ESCR value. Example 5 A high impact polystyrene was produced using the HPFIR process with four level piston flow reactors as shown in Figure 7, wherein the second level reactor was a 17 201217402 conversion reactor. The product leaving the fourth reactor is sent to two devolatilizers and the removed volatile components from the devolatilizer described above are recycled back to the feed. Test 31 was carried out in this method. The 5% of the value of the product is very high, with a value of about 26.5%. The RPS distribution is significantly narrower than those typically obtained under CSTR transformation.

Table 6A Test No. 31 32 33 34 Flow Configuration HPFIR HPFIR HPFIR HPFIR Product / Evaluation Baseline Low Conversion Rate Feed Composition Product Characterization Melt Flow, dg/10min 4.45 4.2 3. 22 3.4 Rubber Content, % 8. 52 8.58 8.32 8.57 Material RPS, mm 2. 73 8.82 5.12 6.55 Swelling index 10 14 10 10 Gel content 27.9 25.5 29.8 31.1 Μη 68375 69151 67555 66118 Mw 180153 178272 180612 Polydispersity 2.6 2.6 2.7 2.7 RPVF 28.2 35.8 36.6 40 Notched cantilever beam break 1.7 2.06 1.62 1.63 Tensile modulus 255193 233134 221436 215765 Yield tensile strength 3107 2511 2604 2480 Tensile strength at break 3274 3190 3567 3342 Elongation at break 46.5 57.4 65.2 55.7 Flexural modulus 275550 259081 243284 236660 Flexural strength 6400 5668 5874 5684 ESCR Toughness untreated 815 1119 1090 ESCR toughness treated 175 45 65 ESCR, residual toughness % 21.5 4 6

Test No. 35 36 Flow Configuration HPFIR HPFIR 18 201217402 Product/Evaluation Feed Composition Recirculation Flow Rate, Pounds/Hour 21.1 21.0 Manufacturing Rate, Pounds/Hour 68 67 Product Characterization Solution Flow, dg/10min 3.76 4. 05' Rubber Content , % 8.53 8.41 Pellet RPS, μιη 7.07 8.82 Swelling index 11 11 Gel content 31 30.8 Μη 65753 66589 Mw 177539 172753 Polydispersity 2.7 2.6 RPVF 40.7 40.9 Notched cantilever beam fracture 1.63 1.76 Tensile modulus 211718 210802 Yield stretch Strength 2348 2329 Tensile strength at break 3348 3371 Elongation at break 62.3 63 Flexural modulus 235965 231541 Flexural strength 5413 5386 ESCR suitability, untreated 1219 1036 ESCR toughness, treated 139 113 ESCR, residual toughness % 11.4 10.9 Example 7 High impact polystyrene was produced using the HPF IR process with 4 level piston flow reactors, where the second level reactor was a conversion reactor. The product leaving the fourth reactor is sent to two devolatilizers and the removed volatile components from the devolatilizer described above are recycled back to the feed. Sample 38 from Example 5 achieved excellent rubber utilization and ESCR performance. Sample 38 was made at the above described conversion reactor at an elevated reactor temperature of 300 °F. This high temperature results in a very high solids content (34.8%) in the reactor and thus results in a relatively high average pellet RPS of 6.81 μηη. In this example 19 201217402, the sample 38 - Γ ^ ^ . is present at a lower temperature. At the new lower temperature - Μ 8 towels, the conditions and results of the above test were compared to test 38 of Example 5. ', Reproduction of the sample 38 from Example 5 at a lower temperature achieved a lower, still satisfactory rubber utilization. A 1:1 ratio of a mixture of a low temperature catalyst and a high temperature catalyst does not result in better or worse results than a single low temperature catalyst system.

The elevated conversion reactor temperature of 29 rF was used in sample 52 and the feed was the same as the feed in 38 except that no piB was used in sample 52. α 52 achieves a narrow particle size distribution of the reactor contents and a rubber particle size of U6; & However, in the product pellets, the particle size distribution is broad, indicating the deterioration of morphology in the final manufacturing stage. The results of sample 52 are shown in the graph of Fig. 9. Lacqrene 8260 available from Total Petrochemicals Europe was used in this example and in Example 5. The residual percent toughness values for this formulation are plotted against Rps for Runs 33-39, 48, 5 and 51'.

Table 8A __3 Test No. 38 48 49 _Product / Description / Evaluation Manufacturing rate, broken / hour 67 65 58 _ Melt flow i pro-4.2 4.2 5.8 4 rubber particle size 6.81 5.57 4. 87 _ dad stretch modulus 206590 211850 229730 Yield tensile strength 2370 2450 2620 — if tensile strength 3170 2880 3020 ___^ Split elongation _ Flexural modulus 70.5 58.1 65.6 228700 233770 2470040 20 201217402

Flexural strength 5130 5020 5380 Swelling index 11 12 12 Gel: Rubber 3.41 3.24 3.10 RPVF 39.9 35.5 33.8 ESCR serviceability, untreated 1125 954 ESCii toughness, treated 288 154 ESCR, residual toughness % 25.6 16.1 Table 8B Test No. 50 51 52 Product / Description / Evaluation Ref 48 Manufacturing rate, pounds per hour 66 61 61 Melt flow rate 3.6 3.7 3.6 Rubber particle size 5.54 6.2 7. 76 Tensile modulus 211040 221570 211820 Yield tensile strength 2430 2510 2380 Tensile strength at break 3020 3100 3130 Elongation at break 64.1 44.1 44.7 Flexural modulus 224000 240550 230200 Flexural strength 5070 5390 5340 Swelling index 11 10 10 Gel: Rubber 3. 26 3.47 3.61 RPVF 36.4 36.7 40.2 ESCR, untreated 1128 1016 ESCR toughness Treated 246 50 ESCR, Residual Toughness % 21.8 4.9 Example 9 Improved RPVF can be achieved using a method with three or more level piston flow reactors, wherein the conversion reactor is one of the above-described level piston flow reactors And rubber utilization. The ability to isolate the above described conversion reactor and operate it at a controlled agitation rate improves the control of rubber particle size and desired morphology. The advantage of a smaller and more reactor is the ability to control the rate of agitation at the conversion. The use of multiple HPF reactors enables a more controlled process in which the amount of pre-conversion, conversion, and post-return 21 201217402 conversion reactions can be controlled to a greater extent, enabling rubber particle size, rubber utilization, and resulting morphology. Greater control of physical properties. The ESCR value can be further improved by using the devolatilizer preheater at a reduced temperature in the manner described herein. In one embodiment, the escr value can be improved by using a devolatilizer preheater at 480 Torr or lower in the methods described herein. Embodiments may include using a devolatilizer preheating at 46 (TF or lower, optionally 44 Torr or lower, optionally 43 (TF or lower, optionally F or lower) Determination of Gel Percentage and Swelling Index The swelling index of high impact polystyrene is determined as the ratio of the weight of the swollen gel (extracted with toluene) to the weight of the xerogel. The dry weight of the gel after the toluene extraction of the polystyrene sample is determined by dividing the total weight of the sample. It is usually reported as a percentage. The percentage of grafting and the percentage of rubber are determined by extraction with methyl ethyl ketone (MEK). The polystyrene (ungrafted, uncrosslinked) is separated from the "insolubles" (ie, rubber, grafted, and crosslinked polystyrene). The resulting residue is dissolved in the dichlorocarbyl and The percentage of rubber is determined. 曰 Grafting: The percentage of rubber t匕 is defined as the weight of the grafted polystyrene divided by the weight of the rubber yoke multiplied by 1 〇〇. The percentage of rubber in HIPS is obtained by making the double bond in the rubber. Determined by reaction with excess deuterated iodine (IC1) The amount of rubber that undergoes this reaction is determined by rumination of excess (6) with standardized thiosulfate and comparison to blank titration of IC1. 22 201217402 ESCR test determination: at 65. 匚 (149 ± In an oven of 2 卞), the tensile splines were exposed to margarine (no salt) for different times. The ESCR was determined by measuring the percent elongation. The ESCR using residual toughness was determined by comparison of exposed and unexposed tensile splines. The ES using residual toughness used herein (: r grade is .0-9 poor; 10-19 is good; 20-30 is very good; and > 3 is excellent. Sample preparation: Samples are compression molded according to ASTM program. Ten stretched splines are molded without the use of an organic germanium release agent. Oil, slick or other chemicals should not be in contact with the sample to be tested. Do not touch the margarine to be exposed. The surface should be left in the sample for a few hours before the test. Test: Place the stretched strip in the sample holder. Then apply a thin margarine coating to the spline from their midpoint ±1” (ie Spread the above Approx. 2"Range> Expose the above sample to an oven at 65 ° C (149 ° C.) Remove the margarine from the sample as soon as the sample is removed from the oven. Allow the sample to be sampled before determining the percent elongation according to the ASTM program. Hold for 1 to 2 hours. Calculate the maximum strain (ASTM D-790) according to the following formula: strain = (6Dd/L2), where D = maximum deflection of the center beam (deflection, deflecti〇n), L = bracket span (support span 'and d = depth or thickness of the sample. Experimental determination of RPVF The final polymer composite undergoes dynamic mechanical analysis (DMA). From DMA results 'Using Stephane Jouenne et al. in Macromolecules 2008' Vol. 41, pp. 9823-9830 The technique discussed in the publication can calculate the rubber phase volume fraction RPVF. 23 201217402 Test Standards and Notes 1) Cantilever beam impact is tested by ASTM D256 2) Solution flow is tested by astm D1238 3) Rubber particle size (units, micrometers) is measured by Malvern 2 (10) using methyl ethyl ketone as solvent. Instrument 4) Tensile properties tested by ASTM D638 5) Flexural properties tested by astm D790 6) Dissolution index, gel content and grafting are described herein and in 4, m, 210, the patent is fully incorporated herein. Reference. , National Standard 7) The ESCR value is determined according to U.S. Patent No. 4,777,2, which is incorporated herein by reference. 8) All tests are carried out by standard... unless otherwise stated. Depending on the context, 'in this context, the present invention, in some cases, is only relevant to some specific embodiments. In other cases, it may be related to one or more (but not necessarily all) of the scope of the patent application. The subject matter recited, although the embodiments, variations, and embodiments of the present invention are described above, including that the present invention can be used and utilized by those of ordinary skill in the art, in conjunction with the information and techniques available. The invention is not limited to the specific embodiments, modifications and embodiments, and other and further embodiments, modifications and embodiments of the invention are conceivable without departing from the basic scope of the invention and the scope of the invention is The scope of the appended patent application is determined. 24 201217402 BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic view of a prior art HIPS manufacturing method. Fig. 2 is a schematic view of an embodiment of the HPFIR method of the present invention. Fig. 3 is a view of the present invention including a mixing tank. Schematic diagram of an embodiment of the hpF丨R method. Figure 4 is a schematic diagram of a prior art method used in Example 1. Figure 5 is an implementation A schematic diagram of the method used in the first experiment of Example 2. Figure 6 is a schematic diagram of the method used in the second experiment of Example 2. Figure 7 is a schematic diagram of the method used in the experiment of Example 3. Figure 8 is the residual toughness Figure Percentage as a function of Rps. Figure 9 is a graph of the reactor contents and the average particle size distribution of the resulting product pellets in the multi-reactor process. Figure 1 is the ESCR value (% residual toughness) versus devolatilizer [Main component symbol description of heat exchanger temperature] R100~Continuous stirred tank reactor (CSTR) pre-conversion reactor; H-1~heater; 200~reactor system; 215~output pipeline; 225~ pipeline; 235~ Pipeline; 2 4 5~ pipeline; 2 5 5~ pipeline;

Rl〇l~CSTR conversion reactor; DV-de-vortexing device; 21 0~first linear flow reactor; 220~polymerization reactor; 230~second polymerization reactor; 240~third polymerization reactor; ~4th polymerization reactor; 25 201217402 300~reactor system; 302~polymer reactor 3 0 5~feed line; 306~mix tank; 310~ linear flow pre-conversion reactor; 315~ pipeline; 316~ motor 318~ stirrer; 320~first polymerization reactor; 322~motor; 324~ stirrer; 325~ pipeline; 330~second polymerization reactor; 335~ pipeline; 340~third polymerization reactor; 350~4th polymerization reactor; 3 5 5~ pipeline. 26

Claims (1)

201217402 - VII. Patent Application Range: 1 'A method for producing high impact polystyrene comprising: feeding at least one vinyl aromatic monomer, elastomer, and free radical initiator to a first linear flow reaction To form a reaction mixture; polymerizing the above reaction mixture in the first linear flow reactor to a point below the point at which phase inversion occurs to produce a first polymerization mixture; and the first polymerization mixture from the first line described above a flow reactor is fed to the second linear flow reactor; the first polymerization mixture in the second linear flow reactor is polymerized to at least a phase inversion point of the mixture to produce a second polymerization mixture; and the second The polymerization mixture is fed from the second linear flow reactor described above to at least a third linear flow reactor for post-conversion polymerization of the second polymerization mixture described above. 2. The method of claim 1, wherein the method comprises at least two linear flow reactors arranged in series. 3. The method of claim 1, wherein each linear flow reactor is level-positioned. 4. The method of claim 3, wherein the second linear flow reactor is operated at a temperature above 230T. 5. The method of claim 1, wherein the product stream exits the at least third linear flow reactor and is passed to a devolatilizer preheater operating at a temperature of no more than 47 Torr. 6. The method of claim 1, wherein the feed head 27 201217402 is first delivered to the mixing tank prior to the first linear flow reactor. 7. The method of claim i, further comprising flowing the product away from said at least third linear flow reactor, wherein said product stream has an ESCR value of at least 20% residual toughness. 8. The method of claim 7, wherein the product stream has an ESCR value of at least 25% residual toughness. 9. The method of claim 7 wherein said product stream has an ESCR value of at least 20% residual toughness at a rubber content of less than 1% by weight. The method of claim 8, wherein the product stream has an escr value of at least 25% residual toughness of less than 5% by weight of the rubber content. 11. The method of claim 5, wherein the product stream exits the second linear flow reactor as described above, having an Rps greater than 5 " m. 12. A method of making high impact polystyrene comprising: feeding at least one vinyl aromatic monomer, an elastomer, and a free radical initiator to a mixing tank to form a reaction mixture; and reacting the above reaction mixture from the above mixing tank Feeding to the first linear flow reactor; polymerizing the above reaction mixture in the first linear flow reactor to a point below the point at which phase inversion occurs to produce a first polymerization mixture; Feeding from the first linear flow reactor to the second linear flow reactor; polymerizing the first polymerization mixture in the second linear flow reactor to at least a phase inversion point of the above mixture to produce a second polymerization mixture; And 28 201217402 feeding the second polymerization mixture from the second linear flow reactor to the at least third linear flow reactor for post-conversion polymerization of the second polymerization mixture. 13. The method of claim 12, wherein the method comprises at least two linear flow reactors arranged in series. 14_ The method of claim 12, wherein each of the linear flow reactors is level positioned. The method of claim 12, wherein the second linear flow reactor is operated at a temperature higher than 23 Torr. 16. The method of claim 12, wherein the mixing tank is not subjected to a heat source. 17. The method of claim 12, wherein the reaction mixture in the above mixing tank is heated to a temperature below 2 3 Torr. 18. The method of claim 12, wherein the product stream exits the at least second linear flow reactor and is delivered to a devolatilizer preheater operating at a temperature below 4 7 Torr. 19. The method of claim 12, further comprising the product stream exiting said at least third linear flow reactor, wherein said product stream has an ESCR value of at least 10% residual toughness. The method of claim 19, wherein the product stream has an ESCR value of at least 15% residual toughness. 21. The method of claim 19, wherein the product stream has an ESCR value of at least 10% residual toughness at less than 10% rubber content. 22_ The method of claim 2, wherein the above product stream 29 201217402 has an ESCR value of at least 1 5% residual toughness of less than 10% rubber content. 23. The method of claim 19, wherein the product stream has an RPS greater than 5 #m. 30