WO2022162694A1 - Copolymère greffé et procédé de préparation associé - Google Patents

Copolymère greffé et procédé de préparation associé Download PDF

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WO2022162694A1
WO2022162694A1 PCT/IN2022/050064 IN2022050064W WO2022162694A1 WO 2022162694 A1 WO2022162694 A1 WO 2022162694A1 IN 2022050064 W IN2022050064 W IN 2022050064W WO 2022162694 A1 WO2022162694 A1 WO 2022162694A1
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Prior art keywords
copolymer
acrylate
range
methacrylate
polyolefin
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PCT/IN2022/050064
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English (en)
Inventor
Pravin Gopal Kadam
Bennet CHELLIAHN
Ramachandrarao BOJJA
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Hindustan Petroleum Corporation Limited
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Publication of WO2022162694A1 publication Critical patent/WO2022162694A1/fr

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    • 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
    • C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
    • C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms

Definitions

  • the present disclosure broadly relates to the field of grafted copolymers, and in particular relates to acrylate grafted polyolefin.
  • the present disclosure discloses an acrylate grafted polyolefin with high melt flow index and a method of preparing the same.
  • Polypropylene (PP) is characterized by excellent physicomechanical properties, yet due to lack of any polar functional group in the polymeric chain, it is also characterized with poor adhesive properties, lack of reactive sites and poor resistance to UV.
  • Copolymerizing with other monomers, bearing unsaturated polar functional groups, either as blocks or grafts over polypropylene backbone has been evident in improving properties of polypropylene.
  • Grafting functional monomers over the polyolefin backbone can be achieved by inducing free radicals. These free radicals are furnished in the reaction by use of initiators.
  • MFI melt flow index
  • W02008066168A1 discloses a polyolefin grafted with hydrolyzable silane groups and a method for grafting hydrolyzable and crosslinkable groups to polymers.
  • W02014023603 Al discloses a process for preparation of polypropylene in a sequential polymerization process, in presence of a Ziegler-Natta catalyst, for improved productivity.
  • the prior arts lack at obtaining grafted copolymers with high melt flow index.
  • there are other issues with methods of preparing copolymers such as the complex preparation processes involving multiple steps, purification of the final product from the reactant mixture and so on.
  • a graft copolymer of high melt flow index comprising: (a) a polyolefin as backbone; and (b) an acrylate grafted to the backbone, wherein the copolymer has melt flow index in the range of 1 g/10 min to 17 g/10 min, the polyolefin is in the weight percentage range of 90.0 to 99.5%; and the acrylate is in the weight percentage range of 0.5 to 10.0%.
  • a method of preparing the copolymer comprising: (a) premixing the polyolefin with an initiator to obtain a first mixture; (b) adding the acrylate and the first mixture in an extruder to obtain an extrudate; and (c) cooling and granulating the extrudate to obtain the copolymer, wherein adding the acrylate and the first mixture in the extruder to obtain an extrudate is carried out at a temperature in the range of 150°C to 250°C and at a screw speed in the range of 5 to 250 rpm.
  • an article comprising the copolymer with high melt flow index, the copolymer comprising: (a) a polyolefin as backbone; and (b) an acrylate grafted to the backbone, wherein the copolymer has melt flow index in the range of 1 g/10 min to 17 g/10 min, the polyolefin is in the weight percentage range of 90.0 to 99.5%; the acrylate is in the weight percentage range of 0.5 to 10.0%, and the copolymer is obtained by the method comprising: (a) premixing the polyolefin with an initiator to obtain a first mixture; (b) adding the acrylate and the first mixture in an extruder to obtain an extrudate; and (c) cooling and granulating the extrudate to obtain the copolymer, wherein adding the acrylate and the first mixture in the extruder to obtain an extrudate is carried out at a temperature in the range of 150°C to 250°
  • Figure 1 depicts the melt flow indices measured at 230°C for the graft copolymer samples HR0003, SAPP-0, SAPP-1, SAPP-2, SAPP-3 and SAPP-4, in accordance with an implementation of the present disclosure.
  • Figure 2 depicts the tensile strength (MPa) and % elongation at yield for the graft copolymer samples HR0003, SAPP-0, SAPP-1, SAPP-2, SAPP-3 and SAPP-4, in accordance with an implementation of the present disclosure.
  • Figure 3 depicts the impact strength (J/m) for the graft copolymer samples HR0003, SAPP-0, SAPP-1, SAPP-2, SAPP-3 and SAPP-4 , in accordance with an implementation of the present disclosure.
  • Figure 4 depicts the HDT (heat deflection temperature) and VI CAT for the graft copolymer samples HR0003, SAPP-0, SAPP-1, SAPP-2, SAPP-3 and SAPP-4, in accordance with an implementation of the present disclosure.
  • graft copolymer refers to branched macromolecules or polymers in which the branches are different from the backbone of the polymer.
  • the graft copolymer refers to acrylate grafted polyolefin, wherein the polyolefin is the polymer backbone and the acrylate is the branching monomer.
  • reactive extrusion refers to a method to synthesize polymers, involving the chemical steps of polymer synthesis together with extrusion process of melting, shaping, etc., in a single process.
  • reactive extrusion method is used to synthesize the graft copolymer comprising polyolefin as the backbone and acrylate grafted to the backbone.
  • polyolefin refers to a polymeric compound produced from an alkene as a monomer.
  • polyolefin includes, but not limited to, polypropylene, polyethylene, combination of polyprolpylene and polyethylene.
  • acrylate refers to monomers comprising an ester with a vinyl group attached to carbonyl carbon of the ester group.
  • the term “acrylate” includes, but not limited, to stearyl acrylate (SA), cyclohexyl methacrylate, stearyl meth acrylate, cetyl eicosyl methacrylate, stearyl methacrylate, lauryl methacrylate, iso-decylmethacrylate, iso-bornyl methacrylate, methacrylate acid, acrylic acid, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate, i-propyl methacrylate, n-butyl methacrylate, t-butyl methacrylate, or 2-ethylhexyl methacryl
  • the term “initiator” refers to any chemical compound reacting with the monomers to form intermediate compounds capable of successive linking of monomers to form a polymer.
  • the initiator generates free radicals to produce free radicals on the host polymer.
  • the term “initiator” includes but not limited to cumene hydroperoxide (CHP), methyl ethyl ketone peroxide, di-t-butyl peroxide, 1,1 - bis (t-butylperoxy)-3,3,5-trimethyl cyclohexane, n-butyl-4,4-bis (t-butylperoxy) valerate, 2.5- dimethylhexane-2,5-dihydroperoxide, l,l'-bis (t-butylperoxy-m- isopropyl) benzene, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 2,5-dimethyl-2,5-di-buty
  • ASTM refers to technical standards for materials, products, systems and services set forth by an international organization known as American Society for Testing and Materials.
  • ASTM is used to refer to different standards of testing used for different properties of the grafted copolymer.
  • melt flow index refers to mass of melt polymer, in grams, flowing through a capillary of specific dimensions, in 10 minutes, depicting the ease of flow of the polymer melt.
  • MFI Melt flow index
  • MFI of the copolymer is measured according to ASTM DI 238 and is measured in terms of g/10 min (grams per 10 minutes).
  • tensile strength refers to force per unit area externally applied on a polymer to break under the stress. It measures the ability of the polymer to resist breaking. In the present disclosure, tensile strength of the copolymer is measured according to ASTM D638.
  • elongation at yield or “percentage elongation at yield” refers to the ratio between the increased length and the initial length of the polymer at the yield point. Elongation at yield refers to the ability of the polymer to resist changes of shape before it irreversibly deforms. In the present disclosure, elongation at yield of the copolymer is measured according to ASTM D638.
  • impact strength refers to the energy absorbed by a polymeric material upon collision by a known weight, without undergoing a deformation or rupture.
  • impact strength of the copolymer is measured according to ASTM D256 and is measured in J/m (Joule/metre).
  • VICAT Vicat softening temperature or Vicat hardness refers to a temperature at which a polymer is penetrable to 1 mm depth, by a flat-end needle of 1 mm 2 cross-section, under applied load.
  • VICAT test is used to determine the temperature at which the prepared copolymer softens.
  • the VICAT of the copolymer is measured according to ASTM DI 525.
  • HDT heat deflection temperature refers to a temperature at which a polymer under applied load, distorts or deforms.
  • HDT test is used to determine the temperature at which the prepared copolymer loses its load bearing ability and softens.
  • the HDT of the copolymer is measured according to ASTM D648.
  • grafting index refers to the ratio of the grafted monomer to the backbone polyolefin.
  • grafting index refers to the ratio of acrylate grafted to polypropylene and is measured from FTIR(Fourier transform infrared spectroscopy) absorbance values corresponding to carbonyl group of acrylate and methyl group of polypropylene.
  • injection molding refers to a process for producing articles/parts by injecting a molten material into a mold.
  • the graft copolymer is subjected to injection molding and the articles such as thin wall injection molded parts and automotive parts are obtained.
  • Ratios, concentrations, amounts, and other numerical data may be presented herein in a range format. It is to be understood that such range format is used merely for convenience and brevity and should be interpreted flexibly to include not only the numerical values explicitly recited as the limits of the range, but also to include all the individual numerical values or sub-ranges encompassed within that range as if each numerical value and sub-range is explicitly recited.
  • a temperature in the range of about 150°C to 250 °C should be interpreted to include not only the explicitly recited limits of about 150 °C to about 250 °C but also to include sub-ranges, such as 150°C to 185°C, 217 °C to 250°C and so forth, as well as individual amounts, including fractional amounts, within the specified ranges, such as 160.2 °C, 195 °C, and 236 °C for example.
  • the present disclosure provides a graft copolymer having high melt flow index in the range of lg/10 min to 17g/l 0 min which widens the applicability of the graft copolymers for manufacturing thin wall injection molding parts and automobile parts.
  • the graft copolymer disclosed in the present disclosure comprises a polyolefin as the backbone and an acrylate is grafted to the polyolefin backbone.
  • the polyolefin present in the weight range of 90.0 to 99.5% is grafted with 0.5 to 10% of an acrylate which enables to achieve high MFI in the resulting graft copolymer.
  • MFI is inversely related to molecular weight and to viscosity of the polymer and is considered as a measure of polymer processability and its rheological properties, as it is correlated to other polymer properties, including tensile strength, impact strength, thermal stability, hardness, gloss, and so on.
  • a high MFI makes the present graft copolymer capable for application in injection molding process for making thin walled parts and also articles with improved tensile properties and impact strength.
  • the present disclosure further provides an efficient method of preparing the graft copolymer of high melt flow index by the process of reactive extrusion method. The process involves synthesis of graft copolymer and its extrusion in a single continuous step, and does not include addition of any solvents.
  • the disclosed method is a simple, fast, easy to perform, and energy efficient route to prepare the graft copolymer of the present disclosure.
  • the present disclosure provides a low cost, high quality graft copolymer having high melt flow index, that is economical and thus a potential candidate to substitute the conventionally used polymers in the field of thin walled parts manufacturing.
  • a graft copolymer of high melt flow index comprising: (a) a polyolefin as backbone; and (b) an acrylate grafted to the backbone; wherein the copolymer has melt flow index in the range of 1 g/10 min to 17 g/10 min, the polyolefin is in the weight percentage range of 90.0 to 99.5% ; and the acrylate is in the weight percentage range of 0.5 to 10.0%.
  • a graft copolymer of high melt flow index comprising: (a) a polyolefin as backbone; and (b) an acrylate grafted to the backbone; wherein the copolymer has melt flow index in the range of 1 g/10 min to 17 g/10 min, the polyolefin is in the weight percentage range of 91.0 to 99.3% ; and the acrylate is in the weight percentage range of 0.8 to 7.5%.
  • a graft copolymer of high melt flow index comprising: (a) a polyolefin as backbone; and (b) an acrylate grafted to the backbone; wherein the copolymer has melt flow index in the range of 3.5 g/10 min to 15.5 g/10 min, the polyolefin is in the weight percentage range of 90.0 to 99.5% ; and the acrylate is in the weight percentage range of 0.5 to 10.0%.
  • a graft copolymer of high melt flow index as described herein wherein the polyolefin is selected from polypropylene, polyethylene, or combinations thereof.
  • a graft copolymer of high melt flow index as described herein wherein the polyolefin is polypropylene.
  • a graft copolymer of high melt flow index as described herein wherein the polyolefin is polyethylene.
  • a graft copolymer of high melt flow index comprising: (a) a polyolefin selected from polypropylene, polyethylene, or combinations thereof, as backbone; and (b) an acrylate grafted to the backbone; wherein the copolymer has melt flow index in the range of 1 g/10 min to 17 g/10 min, the polyolefin is in the weight percentage range of 90.0 to 99.5% ; and the acrylate is in the weight percentage range of 0.5 to 10.0%.
  • a graft copolymer of high melt flow index as described herein, wherein the acrylate is selected from stearyl acrylate, cyclohexyl methacrylate, stearyl meth acrylate, cetyl eicosyl methacrylate, stearyl methacrylate, lauryl methacrylate, iso-decylmethacrylate, isobornyl methacrylate, methacrylate acid, acrylic acid, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate, i-propyl methacrylate, n-butyl methacrylate, t-butyl methacrylate or 2- ethylhexyl methacrylate.
  • the acrylate is selected from stearyl acrylate, cyclohexyl methacryl
  • a graft copolymer of high melt flow index comprising: (a) a polyolefin as backbone; and (b) an acrylate selected from stearyl acrylate, cyclohexyl methacrylate, stearyl meth acrylate, cetyl eicosyl methacrylate, stearyl methacrylate, lauryl methacrylate, iso- decylmethacrylate, iso-bornyl methacrylate, methacrylate acid, acrylic acid, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate, i-propyl methacrylate, n-butyl methacrylate, t-butyl methacrylate or 2-ethylhexy
  • a graft copolymer of high melt flow index comprising: (a) a polyolefin selected from polypropylene, polyethylene, or combinations thereof, as backbone; and (b) an acrylate selected from stearyl acrylate, cyclohexyl methacrylate, stearyl meth acrylate, cetyl eicosyl methacrylate, stearyl methacrylate, lauryl methacrylate, iso-decylmethacrylate, iso-bornyl methacrylate, methacrylate acid, acrylic acid, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate, i-propyl methacrylate, n-butyl methacrylate, t-buty
  • a graft copolymer of high melt flow index comprising: (a) polypropylene as backbone; and (b) stearyl acrylate grafted to the backbone; wherein the copolymer has melt flow index in the range of 1 g/10 min to 17 g/10 min, the polyolefin is in the weight percentage range of 90.0 to 99.5% ; and the acrylate is in the weight percentage range of 0.5 to 10.0%.
  • a graft copolymer of high melt flow index as described herein wherein the copolymer has grafting index in the range of 0.1 to 2.5.
  • a graft copolymer of high melt flow index as described herein wherein the copolymer has grafting index in the range of 0.5 to 1.5.
  • a graft copolymer of high melt flow index comprising: (a) a polyolefin as backbone; and (b) an acrylate grafted to the backbone; wherein the copolymer has melt flow index in the range of 1 g/10 min to 17 g/10 min, the polyolefin is in the weight percentage range of 90.0 to 99.5%, the acrylate is in the weight percentage range of 0.5 to 10.0%, and the copolymer has grafting index in the range of 0.1 to 2.5.
  • a graft copolymer of high melt flow index comprising: (a) a polyolefin is polypropylene as backbone; and (b) an acrylate is stearyl acryate grafted to the backbone; wherein the copolymer has melt flow index in the range of 1 to 17 g/10 min, the polyolefin is in the weight percentage range of 90.0 to 99.5%, the acrylate is in the weight percentage range of 0.5 to 10.0%, and the copolymer has grafting index in the range of 0.1 to 2.5.
  • a method of preparing the copolymer as described herein comprising: (a) premixing the a polyolefin with an initiator in a mixer to obtain a first mixture; (b) adding the acrylate and the first mixture in an extruder to obtain an extrudate; (c) cooling and granulating the extrudate to obtain the copolymer, wherein the adding the acrylate and the first mixture in the extruder to obtain an extrudate is carried out at a temperature in the range of 150°C to 250°C and at a screw speed in the range of 5 to 250 rpm.
  • a method of preparing the copolymer as described herein wherein adding the acrylate and the first mixture in the extruder to obtain an extrudate is carried out at a temperature in the range of 155°C to 240°C and at a screw speed in the range of 9 to 230 rpm.
  • theadding the acrylate and the first mixture in the extruder to obtain an extrudate is carried out at a temperature in the range of 160 to 230°C from feed zone to die zone of the extruder and wherein the die temperature of the extruder is maintained at a temperature in the range of 220 to 240°C.
  • a method of preparing the copolymer the method as described herein, wherein the initiator is selected from cumene hydroperoxide, methyl ethyl ketone peroxide, di-t-butyl peroxide, 1,1-bis (t-butylperoxy)-3,3,5-trimethyl cyclohexane, n-butyl-4,4-bis (t- butylperoxy) valerate, 2.5- dimethylhexane-2,5-dihydroperoxide, 1,1 -bis (t- butylperoxy-m-isopropyl) benzene, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 2,5- dimethyl-2,5-di(t-butylperoxy) hexine-3 or benzoyl peroxide.
  • the initiator is selected from cumene hydroperoxide, methyl ethyl ketone peroxide, di-t-but
  • a method of preparing the copolymer as described herein comprising: (a) premixing the polyolefin with an initiator selected from cumene hydroperoxide, methyl ethyl ketone peroxide, di-t-butyl peroxide, 1,1 -bis (t-butylperoxy)-3,3,5-trimethyl cyclohexane, n- butyl-4,4-bis (t-butylperoxy) valerate, 2.5- dimethylhexane-2,5-dihydroperoxide, 1,1- bis (t-butylperoxy-m-isopropyl) benzene, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 2,5-dimethyl-2,5-di(t-butylperoxy) hexine-3 or benzoyl peroxide, in a mixer to obtain an initiator selected from cumene hydroperoxide, methyl eth
  • a method of preparing the copolymer as described herein comprising: (a) premixing the polyolefin with an initiator selected from cumene hydroperoxide, methyl ethyl ketone peroxide, di-t-butyl peroxide, 1,1 -bis (t-butylperoxy)-3,3,5-trimethyl cyclohexane, n- butyl-4,4-bis (t-butylperoxy) valerate, 2,5-dimethylhexane-2,5-dihydroperoxide, 1,1'- bis (t-butylperoxy-m-isopropyl) benzene, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 2,5-dimethyl-2,5-di(t-butylperoxy) hexine-3 or benzoyl peroxide, in a mixer
  • a method of preparing the copolymer the method as described herein, wherein the initiator is in the weight percentage range of 0.01 to 0.03%.
  • a method of preparing the copolymer the method as described herein, wherein the initiator is in the weight percentage range of 0.01 to 0.02%.
  • a method of preparing the copolymer as described herein comprising: (a) premixing the polyolefin with an initiator in a mixer to obtain a first mixture; (b) adding the acrylate and the first mixture in the extruder to obtain an extrudate; (c) cooling and granulating the extrudate to obtain the copolymer, wherein adding the acrylate and the first mixture in the extruder to obtain an extrudate is carried out at a temperature in the range of 150°C to 250°C and at a screw speed in the range of 5 to 250 rpm, wherein the initiator is cumene hydroperoxide in the weight percentage range of 0.01 to 0.03%.
  • a method of preparing the copolymer as described herein comprising: (a) premixing the polyolefin with at least one initiator in a mixer to obtain a first mixture; (b) adding the acrylate and the first mixture in the extruder to obtain an extrudate; (c) cooling and granulating the extrudate to obtain the copolymer, wherein adding the acrylate and the first mixture in the extruder to obtain an extrudate is carried out at a temperature in the range of 150°C to 250°C and at a screw speed in the range of 5 to 250 rpm, wherein the polyolefin is polypropylene, the acrylate is stearyl acrylate and the initiator is cumene hydroperoxide in the weight percentage range of 0.01 to 0.03%.
  • a method of preparing the copolymer as described herein comprising: (a) premixing the polyolefin with an initiator in a mixer to obtain a first mixture; (b) adding the acrylate and the first mixture in an extruder to obtain an extrudate; (c) cooling and granulating the extrudate in the form of pellets or granules, to obtain the copolymer, wherein adding the at least one acrylate and the first mixture in the extruder to obtain an extrudate is carried out at a temperature in the range of 150°C to 250°C and at a screw speed in the range of 5 to 250 rpm.
  • a method of preparing the copolymer as described herein comprising: (a) premixing the polyolefin with an initiator in a mixer to obtain a first mixture; (b) adding the acrylate and the first mixture in the extruder at a temperature in the range of 150°C to 250°C and at a screw speed in the range of 5 to 250 rpm to obtain an extrudate; (c) cooling and granulating the extrudate to obtain the copolymer, and (d) injection molding the copolymer to obtain thin wall injection molded parts.
  • a method of preparing the copolymer as described herein comprising: (a) premixing the polyolefin in the weight percentage range of 90.0 to 99.5% with an initiator, selected from cumene hydroperoxide in the weight percentage range of 0.01 to 0.03%, in a mixer to obtain a first mixture; (b) adding the acrylate in the weight percentage range of 0.5 to 10.0% and the first mixture in the extruder to obtain an extrudate; (c) cooling and granulating the extrudate, in the form of pellets or granules, to obtain the copolymer, wherein adding the acrylate and the first mixture in the extruder to obtain an extrudate is carried out at a temperature in the range of 150°C to 250°C and at a screw speed in the range of 5 to 250 rpm, and wherein the method further comprises injection molding of the copolymer at a temperature in the range of 180°C to 240°
  • an article comprising the graft copolymer with high melt flow index, the graft copolymer comprising: (a) polypropylene in the weight percentage range of 90.0 to 99.5% as backbone; and (b) stearyl acryate in the weight percentage range of 0.5 to 10.0% grafted to the backbone with the melt flow index of the copolymer is in the range of 1 to 17 g/10 min, wherein the copolymer has grafting index in the range of 0.1 to 2.5, and the graft copolymer is obtained by the method comprising: (a) premixing the polypropylene with cumene hydroperoxide initiator in the weight percentage range of 0.01 to 0.03%, in a mixer to obtain a first mixture; (b) adding stearylacrylate and the first mixture in an extruder to obtain an extrudate; (c) cooling and granulating the extrudate in the form of pellets or granule
  • an article comprising the graft copolymer with high melt flow index, the graft copolymer comprising: (a) polypropylene in the weight percentage range of 90.0 to 99.5% as backbone; and (b) stearyl acryate in the weight percentage range of 0.5 to 10.0% grafted to the backbone with the melt flow index of the copolymer is in the range of 1 to 17 g/10 min, wherein the copolymer has grafting index in the range of 0.1 to 2.5, and the graft copolymer is obtained by the method comprising: (a) premixing the polypropylene with cumene hydroperoxide initiator in the weight percentage range of 0.01 to 0.03%, in a mixer to obtain a first mixture; (b) adding stearylacrylate and the first mixture in an extruder to obtain an extrudate; (c) cooling and granulating the extrudate in the form of pellets or granule
  • the forthcoming examples explains that how the present disclosure provides a copolymer comprising a polypropylene backbone and stearyl acrylate grafted to the backbone and method of preparing the graft copolymer.
  • the method of preparation comprises premixing the polypropylene with cumene hydroperoxide as initiator to form a first mixture, followed by addition of stearyl acrylate to this first mixture in an extruder to obtain extrudate, and further cooling and granulating the extrudate in form of pellets or granules to obtain the copolymer.
  • the examples show variation in the measured properties of the obtained copolymer upon variation in the amount of reactants in the formulations prepared.
  • the graft copolymer in the present disclosure is prepared using a reactive extrusion method. It is one of the most economical and commercial method to functionalize polyolefins, using single- or twin-screw extruder.
  • the method of the present disclosure involves a continuous process, with no use of solvents, low costs and faster reaction time.
  • the present invention further discloses an article comprising the said graft copolymer, using thin wall injection molding.
  • Tensile properties were measured using a universal testing machine (Model 50 ST, Tinius Olsen, UK), according to ASTM procedures D638.
  • HDT and VICAT tests were performed by means of a HDT/VICAT testing equipment (HV6M, Instron, Italy), according to ASTM D648 (using a load of 1.82 MPa and a heating rate of 120°C/h), and ASTM DI 525 (Method A, load IO N, and heating rate of 120°C/h), respectively.
  • FUR spectra were recorded with PerkinElmer Spectrum GX equipment (Waltham, Massachusetts, USA).
  • the graft copolymer was prepared from stearyl acrylate as the graft monomer, polypropylene as the backbone and the cumene hydroperoxide as the initator.
  • the graft copolymer was prepared by the reactive extrusion method. Reactive extrusion of polypropylene was performed on a co-rotating twin-screw extruder (Boolani Engineering Corporation, Mumbai, India) equipped with eight heating zones having screw diameter of 30 mm, L/D of 48/1. Polypropylene was premixed with cumene hydroperoxide in a high speed mixer for 10 minutes to obtain a first mixture. Concentration of cumene hydroperoxide was kept constant at 200 ppm in polypropylene.
  • the first mixture was then fed into the extruder through an hopper. Temperature profile in the eight heating zones of the extruder was maintained as 160°C, 175°C, 190°C, 200°C, 210°C, 220°C, 225°C, 230 °C, respectively, from feed zone to the die zone, where 230°C is the die temperature. Feeder screw and extruder screw speeds were set at 10 and 225 rpm, respectively.
  • SA Stearyl acrylate
  • Table 1 shows the various stearyl acrylate (SA) grafted polypropylene (PP) having 2 kg(2000g) of polypropylene with amounts of stearyl acrylate in the range of 19.5 to 156 g (0.5 to 9%), each prepared using 0.4 g (200 ppm) of cumene hydroperoxide (CHP).
  • SA stearyl acrylate
  • PP grafted polypropylene
  • HR003 and SAPP-0 were prepared for comparative examples.
  • HR003 is polypropylene without sterayl acrylate prepared in the absence of cumene hydroperoxide
  • SAPP-0 is the polypropylene without sterayl acrylate prepared in the presence of cumene hydroperxide.
  • SAPP-1 was prepared from 2kg (99.0%) of PP with 19.5 g(0.97%) of SA in the presence of 0.4g (0.02%) of CHP.
  • SAPP- 2, SAPP-3, and SAPP-4 were prepared from 2 kg of PP corresponding to 98.1%, 96.2%, 92.8 % with 39.0g (1.9%), 78.0g(3.8%), and 156g (7.2%) of SA, respectively.
  • the weight % of CHP were varied from 0.01 to 0.02 which correspond to 0.4g as shown in Table 1 and the various graft copolymers were obtained.
  • the grafted copolymer was further subjected to injection molding.
  • Injection molding (Arburg All Rounder 410C, Germany) was performed by maintaining the temperature profile as 190°C, 210°C and 230°C from the hopper to the ejection nozzle. Throughout the molding process, parameters such as injection pressure, packing pressure and cooling time were maintained constant at 240 bar, 1000 bar, and 20 seconds, respectively to prepare ASTM test specimens. Injection molding of the graft copolymer can be used to prepare desired articles such as thin wall injection molded parts and automotive parts.
  • melt flow index (MFI) (expressed in g/10 min) of the prepared graft copolymers was determined using a melt flow indexer (Model Ceast MF20, Instron, UK) at 230°C utilizing a load of 2.16 kg according to ASTM D1238. MFI values as reported in Figure 1 are average of 10 measurements for each of the graft copolymers HR003, SAPP-0, SAPP-1, SAPP-2, SAPP-3 and SAPP-4.
  • Figure 1 and Table 1 shows the melt flow indices of the graft copolymers.
  • HR003 exhibited the least MFI and SAPP-0 the polypropylene in the presence of CHP exhibited a slight increase in MFI.
  • SAPP-1 to SAPP-4 exhibited a gradual increase in MFI. It can be observed that MFI increased as the concentration of SA increased from SAPP-1 to SAPP-4. Further it can be clearly deduced that SAPP-4 possessed the higher MFI compared to HR003 and SAPP-0, which indicated that grafting copolymers exhibit higher MFI than the polymers itself and the MFI further increased with increase in weight % of the grafting monomer (SA).
  • SA grafting monomer
  • Grafting index 741730
  • A1730 is the absorbance at 1730 cm’ 1 , characteristic of carbonyl group proportional to the amount of stearyl acrylate grafted onto the polypropylene backbone
  • A2722 is the absorbance at 1 1 cm’ 1 , characteristic of methyl (CH3) groups proportional to the amount of polypropylene in the copolymer.
  • Table 2 illustrates the calculated grafting index values as per the FTIR results, for the samples SAPP-1, SAPP-2, SAPP-3 and SAPP-4.
  • Example 1 The graft copolymer samples prepared in Example 1 were further subjected to understand their tensile properties such as tensile strength and elongation at yield. Following examples explain the properties of the copolymer and variations of the properties observed in different compositions.
  • Tensile properties were measured using a universal testing machine (Model 50 ST, Tinius Olsen, UK), according to ASTM procedures D638, at a crosshead speed of 50 mm/min.
  • the specimen consists of Type 1, which is a dog-bone shaped specimen with 165 mm overall length, 50 mm gauge length, 13 mm width and 3.2 mm thickness. A minimum of five specimens were tested for each reported value in Figure 2.
  • Figure 2 shows an increase in percentage elongation at yield and a comparable tensile strength, with respect to increasing amount of stearyl acrylate in the copolymer composition from SAPP-1 to SAPP-4.
  • Tensile strength depends on the melt flow index of the copolymer, such that tensile strength decreases with increase in melt flow index. The decrease in the tensile strength favors the melt flow index as well as in the preparation of melt flow injection molding.
  • SAPP-1 to SAPP-4 graft copolymers exhibited comparable tensile strength and elongation yield compared to HR003 and SAPP-0. Also, elongation at yield of the copolymer increased with increase in melt flow index and grafting index of the copolymer.
  • SAPP-4 exhibited higher percentage elongation at yield in the range of 25 to 30%, and lowest tensile strength in the range of 20 to 24%, compared to other graft copolymers.
  • Notched Izod impact strength was determined according to ASTM standard D256, using impact tester (Model IT503, Tinius Olsen, UK) having striking velocity of 3.46 m/s, employing a 2.7 J striker. A minimum of five specimens were tested for each reported value in Figure 3. [0089] HR003 has the higher impact strength in the range of 40 to 43 J/m. Impact strength decreases for SAPP-0, SAPP-1 and SAPP-2 and then shows an increasing trend for SAPP-3 and SAPP-4 with impact strength in the range of 33 to 37 J/m. As can be seen from Table 1, cumene hydroperoxide was added in constant concentration in all the copolymers i.e.
  • HDT and VICAT tests were performed by means of a HDT/VICAT testing equipment (HV6M, Instron, Italy).
  • HDT test was performed according to ASTMD648, using a load of 1.82 MPa and a heating rate of 120°C/h.
  • VICAT test was performed according to ASTM DI 525, using Method A, a load of 10 N, and heating rate of 120°C/h. Samples were dried in an air oven at 105 °C for about 18 h, to expel any adsorbed moisture, prior to testing. The reported values for HDT and VICAT tests are shown in Figure 4.
  • Figure 4 shows comparable variation in HDT and VICAT values for the copolymers.
  • Left axis represent the VICAT values and the right axis represent the HDT values.
  • High values of HDT and VICAT corresponds to suitable high temperature applications.
  • HR003 and SAPP-0 without SA have higher HDT and VICAT values.
  • the graft copolymers SAPP-1 to SAPP-4 did not show much of variation in their HDT and VICAT values, which indicated that grafting SA to PP do not affect copolymer properties while still possessing the high MFI values compared to HR003 and SAPP-0. It can be observed that the HDT and VICAT values did not decrease much, however the MFI had increased multi-fold.
  • the present disclosure discloses a graft copolymer with high melt flow index, a method of preparing the graft copolymer and an article comprising the graft copolymer.
  • the melt fow index of the graft copolymers are in the range of 1 g/10 min to 17 g/10 min and the grafting indices are in the range of 0.5 to 2.5.
  • High melt flow index of the graft copolymer in the present disclosure is advantageous for processing of thin wall injection molding parts.
  • the reacting acrylate monomer, polyolefin and initiator are reasily available and inexpensive.
  • the graft copolymer is prepared using reactive extrusion method in the presence of cumene hydroperoxide as an initiator, thereby the method of preparation is a simple, one step continuous process without involving any complex or multiple steps for the polymer synthesis. Moreover, the disclosed method does not include use of any solvent. Hence, the graft copolymer prepared using the disclosed method incurs low cost, is environmentally friendly, energy efficient and involves short reaction time. Therefore, the graft copolymer dislcosed in the present disclosure is suitable for large-scale production of thin wall injection molded parts of the graft copolymer.

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Abstract

La présente invention concerne un copolymère greffé à indice de fluidité élevé, le copolymère comprenant : (a) une polyoléfine en tant que squelette ; et (b) un acrylate greffé sur le squelette, le copolymère ayant un indice de fluidité dans la plage de 1 à 17 g/10 min, la polyoléfine étant dans la plage de pourcentages en poids de 90,0 à 99,5 % ; et l'acrylate étant dans la plage de pourcentages en poids de 0,5 à 10,0 %. La présente invention concerne également un procédé de préparation d'un copolymère greffé. L'invention concerne en outre un article comprenant un copolymère greffé.
PCT/IN2022/050064 2021-01-27 2022-01-27 Copolymère greffé et procédé de préparation associé WO2022162694A1 (fr)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1217231A (en) * 1967-01-13 1970-12-31 Asahi Chemical Ind Modified polymer composition and a process for producing the same
EP0725090A2 (fr) * 1995-01-10 1996-08-07 PCD-Polymere Gesellschaft m.b.H. Procédé de préparation de polymères greffés de polypropylène à haute viscosité
US5561196A (en) * 1992-12-10 1996-10-01 Den Norske Stats Oljeselskap A.S. Polypropylene materials grafted with an epoxyalkyl acrylate compound
WO2008066168A1 (fr) 2006-12-01 2008-06-05 Idemitsu Kosan Co., Ltd. Copolymère greffé, composition de résine thermoplastique comprenant le copolymère greffé, et leur procédé de production
WO2014023603A1 (fr) 2012-08-07 2014-02-13 Borealis Ag Procédé pour la préparation de polypropylène présentant une productivité améliorée

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1217231A (en) * 1967-01-13 1970-12-31 Asahi Chemical Ind Modified polymer composition and a process for producing the same
US5561196A (en) * 1992-12-10 1996-10-01 Den Norske Stats Oljeselskap A.S. Polypropylene materials grafted with an epoxyalkyl acrylate compound
EP0725090A2 (fr) * 1995-01-10 1996-08-07 PCD-Polymere Gesellschaft m.b.H. Procédé de préparation de polymères greffés de polypropylène à haute viscosité
WO2008066168A1 (fr) 2006-12-01 2008-06-05 Idemitsu Kosan Co., Ltd. Copolymère greffé, composition de résine thermoplastique comprenant le copolymère greffé, et leur procédé de production
WO2014023603A1 (fr) 2012-08-07 2014-02-13 Borealis Ag Procédé pour la préparation de polypropylène présentant une productivité améliorée

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