EP4634247A1 - Procédé de préparation d'un polymère vinyl aromatique à haute résistance aux chocs - Google Patents

Procédé de préparation d'un polymère vinyl aromatique à haute résistance aux chocs

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Publication number
EP4634247A1
EP4634247A1 EP23817132.6A EP23817132A EP4634247A1 EP 4634247 A1 EP4634247 A1 EP 4634247A1 EP 23817132 A EP23817132 A EP 23817132A EP 4634247 A1 EP4634247 A1 EP 4634247A1
Authority
EP
European Patent Office
Prior art keywords
reaction mixture
initiator compound
polymer
total weight
compound
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP23817132.6A
Other languages
German (de)
English (en)
Inventor
Basavaraju KOTTAGALU CHIKKALINGAIAH
Mahesh VIRUPASANDRA SHIVARAMU
Bander Fahad M ALFARHOOD
Naif Mohammed AL-AJMI
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
SABIC Global Technologies BV
Original Assignee
SABIC Global Technologies BV
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Filing date
Publication date
Application filed by SABIC Global Technologies BV filed Critical SABIC Global Technologies BV
Publication of EP4634247A1 publication Critical patent/EP4634247A1/fr
Pending legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
    • C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/28—Oxygen or compounds releasing free oxygen
    • C08F4/32—Organic compounds
    • C08F4/34—Per-compounds with one peroxy-radical
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers

Definitions

  • the invention relates to a process for preparing a polymer and in particular a process for preparing a high impact vinyl aromatic or styrenic polymer.
  • the invention further relates to a polymer such as a styrenic polymer, obtainable by the process of the present invention and to the use of a peroxyester, in the process of the present invention, for improving the impact strength of a polymer.
  • rubber-reinforced polymers derived from vinyl aromatic compounds such as styrene, alpha-methyl-styrene and ring-substituted sytrenes are suitable as monomers for a variety of industrial application.
  • polybutadiene rubber-reinforced polystyrene can be used in a variety of applications including refrigerator linings, packaging applications, furniture, household appliances and toys.
  • the conventional term for such rubber-reinforced polymers is "high impact polystyrene" or "HIPS".
  • HIPS high impact polystyrene
  • the physical characteristics and mechanical properties of HIPS are often dependent upon many factors such as the amount of impurities, which may be present in the starting vinyl aromatic monomer.
  • Styrene for example, is often produced by the dehydrogenation of ethylbenzene (EB) and during such production, phenyl acetylene (PA) is an undesirable by-product that is formed.
  • EB ethylbenzene
  • PA phenyl acetylene
  • the styrene so produced may be contaminated with phenyl acetylene (PA) and toluene as impurities.
  • Toluene may be removed by distillation but the presence of phenyl acetylene (PA) beyond a certain limit is a concern, as phenyl acetylene (PA) can affect styrene polymerization and impede molecular weight build-up and reduce product yield.
  • HPS high impact polystyrene
  • PA phenyl acetylene
  • phenyl acetylene may affect the extent to which rubber particles graft onto polystyrene resulting in a HIPS product having low impact strength.
  • the polymer obtained has a suitable flow property and thermal resistivity for using such polymers in injection moulding, extrusion & thermoforming applications and often attempts to enhance impact properties of a polymer has come at the cost of sacrificing other polymer properties.
  • Another, objective of the present invention is to provide a polymer having sufficiently high impact, flow and thermal properties obtained from a vinyl aromatic monomer without the need of removing phenyl acetylene from such a monomer.
  • the one or more objectives of the present invention is achieved by a process for preparing a polymer, comprising the steps of:
  • reaction mixture comprising: i. at least one vinyl aromatic monomer present in an amount from > 85.0 wt.% and ⁇ 98.0 wt.% based on the total weight of the reaction mixture; and ii. at least one elastomeric compound present in an amount from > 2.0 wt.% and ⁇ 15.0 wt.% based on the total weight of the reaction mixture; (b) heating the reaction mixture to a temperature of > 50°C and adding at least one initiator compound to the reaction mixture to obtain a pre-polymerization mixture; and
  • the initiator compound has an active oxygen content of > 1.0 wt.% and ⁇ 8.0 wt.% based on the total weight of the initiator compound;
  • the amount of initiator compound added to the reaction mixture in step (b) is > 300 and ⁇ 610 parts per million by weight based on the total weight of the reaction mixture;
  • the amount of initiator compound added to the reaction mixture in step (b) is > 20 and ⁇ 200 parts per million by weight based on the total weight of the reaction mixture; and wherein the active oxygen content of the initiator compound is determined in accordance with ASTM D 2180- 89(2008).
  • the vinyl aromatic monomer has a phenyl acetylene content of > 10 and ⁇ 150, preferably > 80 and ⁇ 110, parts per million by weight based on the total weight of the vinyl aromatic monomer.
  • the process for preparing the polymer comprises the steps of:
  • reaction mixture comprising: i. at least one vinyl aromatic monomer present in an amount from > 85.0 wt.% and ⁇ 98.0 wt.% based on the total weight of the reaction mixture; and ii. at least one elastomeric compound present in an amount from > 2.0 wt.% and ⁇ 15.0 wt.% based on the total weight of the reaction mixture;
  • the initiator compound has an active oxygen content of > 1.0 wt.% and ⁇ 8.0 wt.% based on the total weight of the initiator compound; and • wherein if the active oxygen content of the initiator compound is > 1.0 wt.% and ⁇ 4.0 wt.% based on the total weight of the initiator compound, the amount of initiator compound added to the reaction mixture in step (b) is > 300 and ⁇ 610 parts per million by weight based on the total weight of the reaction mixture; and
  • the amount of initiator compound added to the reaction mixture in step (b) is > 20 and ⁇ 200 parts per million by weight based on the total weight of the reaction mixture; and wherein the active oxygen content of the initiator compound is determined in accordance with ASTM D 2180- 89(2008).
  • the polymer is a styrenic polymer, preferably wherein the polymer is polystyrene. More preferably the polymer is a high impact polystyrene (HIPS).
  • HIPS high impact polystyrene
  • the process of the present invention when used for the production of a polymer, the resultant polymer obtained has a desired impact property even without purifying the starting vinyl aromatic monomer.
  • the process of the present invention enables a skilled person to use commercially available vinyl aromatic monomer, (e.g. commercial grade styrene) having relatively high concentration of phenyl acetylene, for the production of polymers such as polystyrene or high impact polystyrene without having to purify the commercial grade monomer.
  • the process of the present invention helps in optimizing operating costs and renders the process of making polymers derived from vinyl aromatic compounds more efficient.
  • the vinyl aromatic monomer may have a phenyl acetylene content of ⁇ 150, preferably ⁇ 120, preferably ⁇ 100 parts per million (ppm) by weight, based on the total weight of the vinyl aromatic monomer.
  • the phenyl acetylene content may be determined using gas chromatography. Accordingly, even when the vinyl aromatic monomer has a phenyl acetylene content as high as 150 ppm by weight, the process of the present invention results in a polymer having the desired Notched Impact strength property.
  • the vinyl aromatic monomer ranges has a phenyl acetylene content of > 10 ppm by weight and ⁇ 150 ppm by weight, preferably > 50 ppm by weight and ⁇ 120 ppm by weight, preferably > 50 ppm by weight and ⁇ 100 ppm by weight, based on the total weight of the vinyl aromatic monomer.
  • the reaction mixture may be obtained by the dissolution under agitation, at least one elastomeric compound in at least one vinyl aromatic monomer along with optional amounts of a processing aid, a mineral oil compound and one or more additives, to obtain the reaction mixture.
  • the agitation may be carried out at stages at a rotation per minute (RPM) of > 40 and ⁇ 310, preferably > 50 and ⁇ 250.
  • the reaction mixture comprises:
  • At least one elastomeric compound present in an amount from > 2.0 wt.% and ⁇ 15.0 wt.%, preferably > 2.0 wt.% and ⁇ 13.0 wt.%, preferably > 5.0 wt.% and ⁇ 10.0 wt.%, based on the total weight of the reaction mixture.
  • the vinyl aromatic monomer may be selected from the group consisting of styrene, a-methyl styrene, dibromostyrene, vinyltoluene, vinylxylene, butylstyrene, p- hydroxystyrene, methoxystyrene, and any combinations thereof.
  • the vinyl aromatic monomer is selected from styrene, a-methyl styrene, and any combinations thereof. More preferably the vinyl aromatic monomer is styrene.
  • the elastomeric compound may be a polymeric rubber selected from polybutadiene, an elastomeric copolymer comprising polymeric units derived from 1 ,3 butadiene and styrene, an elastomeric copolymer comprising polymeric units derived from butadiene and acrylonitrile, and an elastomeric terpolymer comprising polymeric units derived from styrene, butadiene and acrylonitrile.
  • the polymeric rubber is selected from polybutadiene, an elastomeric copolymer comprising polymeric units derived from 1 ,3 butadiene and styrene, an elastomeric copolymer comprising polymeric units derived from butadiene and acrylonitrile. More preferably the polymeric rubber is polybutadiene.
  • the reaction mixture may further comprise of at least one processing aid compound present in an amount of ⁇ 5.0 wt.%, preferably ⁇ 4.0 wt.%, based on the total weight of the reaction mixture.
  • the reaction mixture comprises at least one processing aid compound present in an amount of > 0.0 and ⁇ 5.0 wt.%, preferably > 0.0 and ⁇ 4.0 wt.%, preferably > 1.0 and ⁇ 4.0 wt.%, based on the total weight of the reaction mixture.
  • the processing aid compound is ethyl benzene.
  • the processing aid such as ethyl benzene, functions as a diluent and helps to maintain the viscosity of the reaction mixture during the course of agitation.
  • the reaction mixture may further comprise at least one mineral oil compound present in an amount of ⁇ 3.0 wt.%, preferably ⁇ 2.0 wt.%, based on the total weight of the reaction mixture.
  • the reaction mixture comprises at least one mineral oil compound present in an amount of > 0.0 and ⁇ 3.0 wt.%, preferably > 0.0 and ⁇ 2.0 wt.%, preferably > 1.0 and ⁇ 2.0 wt.%, based on the total weight of the reaction mixture.
  • the mineral oil compound may be selected from paraffin oil, naphtha based hydrocarbon solvent, and petroleum based solvent.
  • the mineral oil compound is paraffin oil.
  • the mineral oil compound is petroleum based solvent.
  • the mineral oil compound may aid in maintaining the viscosity of the reaction mixture and in addition function as an internal mold release agent during processing of the reaction mixture.
  • the reaction mixture comprises one or more additives present in an amount of > 0.0 and ⁇ 1.0 wt.%, preferably > 0.0 and ⁇ 0.8 wt.%, preferably > 0.01 and ⁇ 0.1 wt.%, preferably > 0.01 and ⁇ 0.08 wt.%, based on the total weight of the reaction mixture.
  • the one or more additives are selected from anti-oxidants, UV stabilizers, color stabilizers and combinations thereof.
  • the additive is an anti-oxidant. The anti-oxidant may aid in preventing undesirable oxidation of the elastomeric compound during the step of polymerization.
  • reaction mixture comprises:
  • reaction mixture comprises:
  • the reaction mixture obtained after the dissolution of the elastomeric compound may be in the form of a clear solution.
  • the process involves the step of, heating the reaction mixture to a temperature of > 50°C, preferably > 60°C.
  • the process involves the step of heating the reaction mixture to any temperature of > 50°C and ⁇ 80°C, preferably to a temperature of > 50°C and ⁇ 70°C.
  • the process involves the step of adding at least one initiator compound to the reaction mixture to obtain a pre-polymerization mixture.
  • the initiator compound is added to the reaction mixture when the temperature of the reaction mixture is > 50°C and ⁇ 80°C, preferably > 50°C and ⁇ 70°C.
  • active oxygen content means the weight percentage of active or peroxide oxygen present in the initiator compound.
  • the active oxygen content of the initiator compound is determined in accordance with ASTM D 2180-89(2008). It is preferred that the initiator compound has an active oxygen content of > 1.0 wt.% and ⁇ 8.0 wt.% based on the total weight of the initiator compound.
  • the present inventors found that, depending on the active oxygen content of the initiator compound, the initiator compound may be added to the reaction mixture at a certain concentration in order to counter the effect of phenyl acetylene present in the vinyl aromatic monomer during the polymerization of the vinyl aromatic monomer.
  • the amount of initiator compound added to the reaction mixture is > 300 and ⁇ 610 parts per million (ppm) by weight, preferably > 320 and ⁇ 600 parts per million (ppm) by weight, preferably > 350 and ⁇ 550 parts per million (ppm) by weight, preferably > 380 and ⁇ 450 parts per million (ppm) by weight, preferably > 390 and ⁇ 450 parts per million (ppm) by weight, based on the total weight of the reaction mixture.
  • the active oxygen content of the initiator compound is > 2.5 wt.% and ⁇ 3.9 wt.% based on the total weight of the initiator compound and the amount of initiator compound added to the reaction mixture is > 310 and ⁇ 500 parts per million (ppm) by weight, preferably > 390 and ⁇ 450 parts per million (ppm) by weight, based on the total weight of the reaction mixture.
  • the active oxygen content of the initiator compound is > 2.8 wt.% and
  • ⁇ 3.9 wt.% based on the total weight of the initiator compound and the amount of initiator compound added to the reaction mixture is > 310 and ⁇ 500 parts per million (ppm) by weight, preferably > 390 and ⁇ 450 parts per million (ppm) by weight, based on the total weight of the reaction mixture.
  • the active oxygen content of the initiator compound is > 3.0 wt.% and
  • ⁇ 3.9 wt.% based on the total weight of the initiator compound and the amount of initiator compound added to the reaction mixture is > 380 and ⁇ 450 parts per million (ppm) by weight, preferably > 390 and ⁇ 410 parts per million (ppm) by weight, based on the total weight of the reaction mixture.
  • the amount of initiator compound added to the reaction mixture may be > 20 and ⁇ 200 parts per million (ppm) by weight, preferably > 50 and ⁇ 150 parts per million (ppm) by weight, preferably > 60 and ⁇ 100 parts per million (ppm) by weight, preferably > 60 and ⁇ 80 parts per million (ppm) by weight based on the total weight of the reaction mixture.
  • the active oxygen content of the initiator compound is > 5.0 wt.% and
  • ⁇ 6.5 wt.% based on the total weight of the initiator compound and the amount of initiator compound added to the reaction mixture is > 50 and ⁇ 80 parts per million (ppm) by weight, preferably > 60 and ⁇ 80 parts per million (ppm) by weight, based on the total weight of the reaction mixture.
  • the initiator compound may be added to the reaction mixture in the form a solution having 40.0 to 60.0 wt.%, preferably 50.0 wt.% of the initiator compound.
  • the solvent used may be any suitable inert hydrocarbon solvent such as paraffin oil, petroleum based oil, and naphtha based hydrocarbon solvent.
  • the inventors found that when the initiator compound is added to the reaction mixture in the range prescribed in accordance with the invention, the resultant polymer is produced at a suitable yield and at high monomer conversion with suitable molecular weight build up. Further, the resultant polymer has the desired impact property and a desired molecular weight as may be expected for a high impact polymer such as HIPS.
  • the amount of initiator compound is below the limit prescribed, the desired impact property and monomer conversion is not achieved.
  • the amount of the initiator compound is above the range prescribed, the desired molecular weight, thermal resistivity property and flow property of the polymer is not achieved along with reduced monomer conversion as evidenced from the examples shown in this disclosure.
  • the polymer obtained has high flow rate and is often not suitable for injection molding application. Further, the resultant polymer has lower thermal resistive property indicated by the lower Vicat Softening Temperature.
  • the amount of initiator compound that is added is calibrated with the amount of active oxygen content that is present. For example, with high active oxygen content, for example > 4.0 wt.% and ⁇ 8.0 wt.%, the amount of initiator compound that may be added is > 20 and ⁇ 200 parts per million by weight based on the total weight of the reaction mixture. Above this amount thermal resistivity (indicated by Vicat softening temperature) and flow property may be affected while below this level the desired conversion and molecular weight build-up may not take places as desired.
  • the amount of initiator compound added to the reaction mixture may be > 300 and ⁇ 610 parts per million by weight based on the total weight of the reaction mixture in order to obtain the desired properties of impact strength, molecular weight build up, flow property for processing and thermal resistivity.
  • the initiator compound may be selected from the group consisting of peroxyester, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, 3-di-t-butylperoxide, t-dicumylperoxide, 2,5- dimethyl-2,5-di(t-butylperoxy)hexyne, dicumylperoxide, a,a'-bis(t- butylperoxyisopropyl)benzene, n-butyl-4,4-bis(t-butylperoxy)butane, 2,2-di(tert- butylperoxy)butane, 1 ,1-bis(t-butylperoxy)cyclohexane, tertiarybutylperoxy-2-ethylhexyl carbonate, 1 ,6-di(t-butylperoxycarbonyloxy)hexane, and combinations thereof.
  • the initiator compound is a peroxyester.
  • the peroxyester is selected from i) t-butyl peroctoate, ii) t-butylperoxy 2-ethylhexanoate, iii) ethyl 3,3-di(tert-butylperoxy)butyrate, iv) hexaneperoxoic acid, 2- ethyl-, 1 ,1 -dimethylethyl ester, v) t-butylperoxybenzoate, and combinations thereof.
  • the peroxyester is selected from i) ethyl 3, 3-d i (tert- butyl peroxy) butyrate, or ii) hexaneperoxoic acid, 2-ethyl-, 1 ,1 -dimethylethyl ester. More preferably the peroxyester is hexaneperoxoic acid, 2-ethyl-, 1 ,1 -dimethylethyl ester.
  • the vinyl aromatic monomer is styrene; the elastomeric compound is polybutadiene; and the initiator compound is hexaneperoxoic acid, 2-ethyl-, 1 ,1 -dimethylethyl ester.
  • the process for preparing the polymer of the present invention comprises the steps of:
  • the initiator compound has an active oxygen content of > 1 .0 wt.% and ⁇ 8.0 wt.% based on the total weight of the initiator compound;
  • the active oxygen content of the initiator compound is > 1.0 wt.% and ⁇ 4.0, wt.% based on the total weight of the initiator compound, preferably > 2.5 wt.% and ⁇ 3.9 wt.% based on the total weight of the initiator compound, and the amount of initiator compound added to the reaction mixture in step (b) is > 300 and ⁇ 610 parts per million by weight based on the total weight of the reaction mixture, preferably > 310 and ⁇ 500 parts per million (ppm) by weight based on the total weight of the reaction mixture; and
  • the amount of initiator compound added to the reaction mixture in step (b) is > 20 and ⁇ 200 parts per million by weight based on the total weight of the reaction mixture; and wherein the active oxygen content of the initiator compound is determined in accordance with ASTM D 2180-89(2008); and wherein the initiator compound is a peroxyester, preferably wherein the the peroxyester is selected from i) t-butyl peroctoate, ii) t- butylperoxy 2-ethylhexanoate, iii) ethyl 3,3-di(tert-butylperoxy)butyrate, iv) hexaneperoxoic acid, 2-ethyl-, 1 ,1 -dimethylethyl ester, v) t-butylperoxy
  • the peroxyester is selected from i) ethyl 3,3-di(tert-butylperoxy)butyrate, or ii) hexaneperoxoic acid, 2-ethyl-, 1,1 -dimethylethyl ester, more preferably the peroxyester is hexaneperoxoic acid, 2-ethyl-, 1 ,1 -dimethylethyl ester.
  • the process for preparing the polymer of the present invention comprises the steps of:
  • the initiator compound has an active oxygen content of > 1.0 wt.% and ⁇ 8.0 wt.% based on the total weight of the initiator compound;
  • the active oxygen content of the initiator compound is > 2.5 wt.% and ⁇ 3.9 wt.% based on the total weight of the initiator compound, and the amount of initiator compound added to the reaction mixture in step (b) is > 310 and ⁇ 500 parts per million (ppm) by weight based on the total weight of the reaction mixture; and wherein the active oxygen content of the initiator compound is determined in accordance with ASTM D 2180-89(2008); and wherein the initiator compound is a peroxyester, preferably the peroxyester is hexaneperoxoic acid, 2-ethyl-, 1 ,1 -dimethylethyl ester.
  • the invention is directed to the use of a peroxyester selected from i) t-butyl peroctoate, ii) t-butylperoxy 2-ethylhexanoate, iii) ethyl 3,3-di(tert- butylperoxy)butyrate, iv) hexaneperoxoic acid, 2-ethyl-, 1 ,1 -dimethylethyl ester, v) t- butylperoxybenzoate, and combinations thereof, preferably from i) ethyl 3,3-di(tert- butylperoxy)butyrate, or ii) hexaneperoxoic acid, 2-ethyl-, 1 ,1 -dimethylethyl ester, more preferably the peroxyester is hexaneperoxoic acid, 2-ethyl-, 1 ,1 -dimethyl
  • the process involves the step of heating the pre- polymerization mixture at a temperature of > 110°C and ⁇ 200°C, preferably > 112°C and ⁇ 170°C, preferably > 115°C and ⁇ 170°C for time period of > 2.0 hours and ⁇ 10.0 hours, preferably > 4.0 hours and ⁇ 8.0 hours and obtaining the polymer.
  • the process involves the step of heating the pre-polymerization mixture at a temperature of > 115°C and ⁇ 170°C for time period of > 4.0 hours and ⁇ 7.0 hours and obtaining the polymer.
  • the resultant pre-polymerization mixture may be heated to a temperature of > 115°C and ⁇ 120°C for a time period of about 2.5 hours to 3.0 hours. Thereafter, the heating of the pre-polymerization mixture may take place over four different stages. [0051] In the first stage (R1), the pre-polymerization mixture may be heated at a temperature of > 140°C and ⁇ 150°C for about 40-55 minutes and at an agitator speed of > 140 rpm and ⁇ 155 rpm.
  • the pre-polymerization mixture may be subjected to a second stage (R2) of heating, at a temperature of > 140°C and ⁇ 150°C for about 40-55 minutes and at an agitator speed of > 40 rpm and ⁇ 50 rpm. Thereafter, the pre-polymerization mixture may be subjected to a third stage (R3) of heating, at a temperature of > 150°C and ⁇ 160°C for about 40-55 minutes and at an agitator speed of > 20 rpm and ⁇ 30 rpm.
  • R2 second stage
  • R3 third stage
  • the pre-polymerization mixture may be subjected to a fourth stage (R4) of heating, at a temperature of > 160°C and ⁇ 170°C for about 40-55 minutes and at an agitator speed of > 20 rpm and ⁇ 30 rpm to obtain the polymer.
  • the heating of the pre-polymerization mixture over the four stages of heating results in the polymerization of the vinyl aromatic monomer allowing steady molecular weight build up.
  • the invention relates to a polymer obtained by or obtainable by the process of the present invention.
  • the polymer is a styrenic polymer, preferably wherein the polymer is polystyrene. More preferably the polymer is a high impact polystyrene (HIPS).
  • HIPS high impact polystyrene
  • the polymer may be derived from a vinyl aromatic monomer having a phenyl acetylene content of > 10 and ⁇ 150 parts, preferably > 80 and ⁇ 110 parts, per million by weight based on the total weight of the vinyl aromatic monomer; wherein the polymer is derived from a vinyl aromatic monomer having a phenyl acetylene content of > 10 and ⁇ 150 parts per million by weight based on the total weight of the vinyl aromatic monomer; and
  • an article prepared from the polymer has or selected to have a Notched Izod Impact strength of > 6.0 kJ/m 2 , preferably > 6.0 kJ/m 2 and ⁇ 13.0 kJ/m 2 preferably > 7.5 kJ/m 2 and ⁇ 13.0 kJ/m 2 , preferably > 6.0 kJ/m 2 and ⁇ 12.0 kJ/m 2 determined in accordance with ASTM D256; and/or (b) wherein the polymer has a melt volume flow rate (MVR) of > 2.5 cm 3 /10 min and
  • polystyrene has weight average molecular weight from > 220,000 g/mol and ⁇ 260,000 g/mol, preferably > 220,000 g/mol and ⁇ 250,000 g/mol, preferably 230,000 g/mol to 260,000 g/mol determined with gel permeation chromatography using polystyrene standard in accordance with ASTM D5296-11.
  • the polymer may be derived from the vinyl aromatic monomer having the phenyl acetylene content of > 10 and ⁇ 150, preferably > 80 and ⁇ 110, parts per million by weight based on the total weight of the vinyl aromatic monomer; and
  • an article prepared from the polymer has or selected to have a Notched Izod Impact strength of > 6.0 kJ/m 2 , preferably > 6.0 kJ/m 2 and ⁇ 13.0 kJ/m 2 preferably > 7.5 kJ/m 2 and ⁇ 13.0 kJ/m 2 , preferably > 6.0 kJ/m 2 and ⁇ 12.0 kJ/m 2 determined in accordance with ASTM D256;
  • melt volume flow rate (b) wherein the polymer has a melt volume flow rate (MVR) of > 2.5 cm 3 /10 min and
  • the polymer has weight average molecular weight from > 220,000 g/mol and ⁇ 260,000 g/mol, preferably > 220,000 g/mol and ⁇ 250,000 g/mol, preferably 230,000 g/mol to 260,000 g/mol determined with gel permeation chromatography using polystyrene standard in accordance with ASTM D5296-11 , preferably the vinyl aromatic monomer is styrene and the polymer is derived with a peroxyester initiator compound having an active oxygen content of > 1.0 wt.% and ⁇ 8.0 wt.% based on the total weight of the initiator compound.
  • the polymer obtained at the end of stage (R4) stage may be pulverized to form polymeric powder (3-4 mm) to facilitate smooth feeding in an extruder. Thereafter, the pulverized polymer, which may contain 2-3 wt.% of residual vinyl aromatic monomer, may be passed through an extruder with high vacuum (100-200 mbar) at 200-220 °C so as to remove the unreacted monomer. The final extruded polymer pellets may contain 500- 1000 ppm of residual vinyl aromatic monomer.
  • the present invention will now be further elucidated based on the following nonlimiting examples.
  • HIPS High Impact Polystyrene
  • the reaction mixture obtained was a clear solution. Subsequently, the reaction mixture was agitated at 300 rpm, and heated at a temperature of 60-70 °C. Once after internal reaction temperature reached 60 °C, the initiator compound was added to obtain the pre-polymerization mixture. The addition of the initiator compound was done in the form of a solution containing 50.0 wt.% of the initiator compound. The amount of initiator compound added is shown in the samples below in Table 1 and Table 2.
  • the pre-polymerization mixture was then heated to a temperature of 115 °C and the temperature was maintained under agitation for -174 minutes.
  • Second stage (R2) The mixture was then heated at a temperature of 145 °C and the agitation speed was maintained at 50 rpm for 48 minutes.
  • Second stage (R4) The mixture was heated at a temperature of 165 °C, with an agitation of 25 rpm and maintained for -48 min to obtain the high impact polystyrene polymer (HIPS). Then HIPS obtained was subjected to vacuum (-200 mbar) for 10 minutes to take out the un-reacted styrene and diluent ethylbenzene. After breaking the vacuum, HIPS polymer was removed as lumps in hot condition and chopped into small pieces (1-2 cm). The HIPS polymer obtained was pulverized to powder (3-4 mm) to facilitate smooth feeding into an extruder.
  • HIPS high impact polystyrene polymer
  • the pulverized HIPS contained 2-3 % of residual styrene monomer, to remove this unreacted styrene, the powder was passed through an extruder with high vacuum (100-200 mbar) at 200-220 °C. A 10 barrel, twin screw extruder setup with vacuum port was used and the temperature range was maintained at 150-220 °C. The extruded HIPS pellets obtained contained 500-1000 ppm of residual styrene, which was further tested.
  • T able 1 provides the data for the deterioration of impact properties of the high impact polystyrene obtained by varying the amount of phenyl acetylene present in the starting styrene monomer.
  • the amount of initiator compound added during the process was 300 ppm.
  • the resultant polymer or articles prepared from the resultant polymer has significantly lowered impact property.
  • the sample CE5 having 150 ppm of phenyl acetylene has -67% lower impact property than that of the sample CE1. Accordingly, the amount of phenyl acetylene present in the starting monomer had a direct influence in the impact property.
  • Table 2 provides the properties of high impact polystyrene obtained by varying the amount of initiator compound that is added during polymer production while keeping the amount of phenyl acetylene present in the starting styrene monomer constant at 100 ppm by weight.
  • the impact strength of the polymer obtained (IE1 , IE2) using the process of the present invention starting from styrene having 100 ppm of phenyl acetylene is higher compared to the polymer (CE6) obtained from styrene, which was purified to lower the content of phenyl acetylene.

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

L'invention concerne un procédé de préparation d'un polymère tel qu'un polymère styrénique. Le procédé comprend les étapes consistant : (a) obtenir un mélange réactionnel, comprenant au moins un monomère vinyl aromatique et au moins un composé élastomère; (b) chauffer le mélange réactionnel et ajouter au moins un composé initiateur au mélange réactionnel pour obtenir un mélange de pré-polymérisation; et (c) chauffer le mélange de pré-polymérisation et obtenir le polymère. L'invention concerne en outre un polymère tel qu'un polymère styrénique pouvant être obtenu par le procédé de la présente invention et l'utilisation d'un peroxyester dans le procédé de la présente invention pour améliorer la résistance au choc Izod entaillé du polymère.
EP23817132.6A 2022-12-15 2023-12-01 Procédé de préparation d'un polymère vinyl aromatique à haute résistance aux chocs Pending EP4634247A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
IN202241072469 2022-12-15
EP23157842 2023-02-21
PCT/EP2023/083880 WO2024126090A1 (fr) 2022-12-15 2023-12-01 Procédé de préparation d'un polymère vinyl aromatique à haute résistance aux chocs

Publications (1)

Publication Number Publication Date
EP4634247A1 true EP4634247A1 (fr) 2025-10-22

Family

ID=89068841

Family Applications (1)

Application Number Title Priority Date Filing Date
EP23817132.6A Pending EP4634247A1 (fr) 2022-12-15 2023-12-01 Procédé de préparation d'un polymère vinyl aromatique à haute résistance aux chocs

Country Status (3)

Country Link
EP (1) EP4634247A1 (fr)
CN (1) CN120530149A (fr)
WO (1) WO2024126090A1 (fr)

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6703460B1 (en) * 2003-03-04 2004-03-09 Fina Technology, Inc. Use of sequential polyperoxides to produce polystyrene with high grafting
US7754817B2 (en) * 2005-10-31 2010-07-13 Fina Technology, Inc. Low temperature initiators for improving the rubber phase volume of HIPS formulations

Also Published As

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WO2024126090A1 (fr) 2024-06-20
CN120530149A (zh) 2025-08-22

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