Method and use of dihydroxy amido alcohol compounds

Abstract

Method and Use A method of making a polyolefin material, the method comprising at least one step of 5 polymerising at least one olefinic monomer in the presence of at least one polymerisation catalyst and at least one amido alcohol compound; wherein the or each amido alcohol compound is of the formula R1C(O)NR2R3, wherein R1 is an optionally substituted C5-23 hydrocarbyl group, and each of R2 and R3 is independently a hydrocarbyl group having at least three carbon atoms and wherein each hydrocarbyl group R2 and R3 is substituted by at least one hydroxy group and 10 optionally one or more further substituents.

Description

[0001] Method and use

[0002] Field of the Invention

[0003] The present invention relates to methods of making polyolefin materials and methods of providing improvements during olefinic polymerisation processes, in particular wherein the methods comprise polymerising olefinic monomers. The present invention also relates to uses of amido alcohol compounds and to methods of using amido alcohol compounds in the polymerisation of olefinic monomers, and to polymerisation reaction mixtures comprising amido alcohol compounds.

[0004] Background

[0005] During manufacture of polyolefins and especially heterophasic polymers (also known as impact copolymers) derived from olefinic monomers, growing polymer particles can adhere to each other and / or to surfaces of the reactor resulting in reactor fouling and / or poor product flowability. This can cause blockages in the reactor, which is particularly troublesome in continuous polymerisation processes. Reactor blockages can reduce the efficiency of the polymerisation reaction, such as by increasing resistance to the flow of reagents and products to and from the reactor (resulting in the need for increased pumping power) and / or by decreasing heat transfer efficiency (making temperature control more difficult). In some cases, reactor blockages may cause eventual shutdown of the reactor. Product quality can also be impaired, as growing polymer particles that adhere to the surfaces of the reactor can become dislodged resulting in differing reaction times and products of differing molecular weights. In addition, during the manufacture of heterophasic (impact) copolymers, formation of rubber on the surface of particles can cause an increase in product tackiness and a reduction in product pourability which can be a cause of fouling.

[0006] It is known to use an anti-fouling additive during the manufacture of polyolefins and heterophasic (impact) polymers derived from olefinic monomers in order to reduce or prevent the above issues. It is preferable in some polymerisation processes to use anti-fouling additives that can be additised into a process as liquids without requiring dilution. However, this can lead to process issues in low temperature environments as the liquid anti-fouling additives may solidify in storage tanks, pipelines, injection lines etc.

[0007] Current commercially available anti-fouling additives are increasingly being designated as reprotoxic, substantially limiting their use. For example downstream polymer products prepared using such anti-fouling additives cannot be used in applications that result in contact with humans or animals, such as in food contact applications or in medical applications.It is therefore desirable to provide an alternative additive that is liquid at low temperatures (for example below 0°C), and that can effectively reduce fouling in a polymer manufacturing process (especially within a reactor), whilst meeting the current and future regulatory constraints on polymerisation additives.

[0008] Summary

[0009] According to a first aspect of the present invention, there is provided a method of making a polyolefin material, the method comprising at least one step of polymerising at least one olefinic monomer in the presence of at least one polymerisation catalyst and at least one amido alcohol compound; wherein the or each amido alcohol compound is of the formula R1C(O)NR2R3, wherein R1is an optionally substituted C5-23 hydrocarbyl group, and each of R2and R3is independently a hydrocarbyl group having at least three carbon atoms and wherein each hydrocarbyl group R2and R3is substituted by at least one hydroxy group and optionally one or more further substituents.

[0010] According to a second aspect of the present invention, there is provided a use of an amido alcohol compound in an olefinic polymerisation process, wherein the olefinic polymerisation process comprises at least one step of the polymerisation of at least one olefinic monomer in the presence of at least one polymerisation catalyst; wherein the or each amido alcohol compound is of the formula R1C(O)NR2R3, wherein R1is an optionally substituted C5-23 hydrocarbyl group, and each of R2and R3is independently a hydrocarbyl group having at least three carbon atoms and wherein each hydrocarbyl group R2and R3is substituted by at least one hydroxy group and optionally one or more further substituents.

[0011] According to a third aspect of the present invention, there is provided a method of providing at least one improvement during an olefinic polymerisation process, the method comprising:

[0012] (a) providing a polymerisation reaction mixture comprising at least one olefinic monomer, at least one polymerisation catalyst and at least one amido alcohol compound; and (b) carrying out a polymerisation process;

[0013] wherein the or each amido alcohol compound is of the formula R1C(O)NR2R3, wherein R1is an optionally substituted C5-23 hydrocarbyl group, and each of R2and R3is independently a hydrocarbyl group having at least three carbon atoms and wherein each hydrocarbyl group R2and R3is substituted by at least one hydroxy group and optionally one or more further substituents.

[0014] According to a fourth aspect of the present invention, there is provided a use of an amido alcohol compound to provide at least one improvement during an olefinic polymerisation process, wherein the olefinic polymerisation process comprises the polymerisation of at least one olefinicmonomer in the presence of at least one polymerisation catalyst; wherein the or each amido alcohol compound is of the formula R1C(O)NR2R3, wherein R1is an optionally substituted C5-23 hydrocarbyl group, and each of R2and R3is independently a hydrocarbyl group having at least three carbon atoms and wherein each hydrocarbyl group R2and R3is substituted by at least one hydroxy group and optionally one or more further substituents.

[0015] According to a fifth aspect of the present invention, there is provided a polymerisation reaction mixture comprising:

[0016] (i) at least one olefinic monomer;

[0017] (ii) at least one polymerisation catalyst; and

[0018] (iii) at least one amido alcohol compound,

[0019] wherein the or each amido alcohol compound is of the formula R1C(O)NR2R3, wherein R1is an optionally substituted C5-23 hydrocarbyl group, and each of R2and R3is independently a hydrocarbyl group having at least three carbon atoms and wherein each hydrocarbyl group R2and R3is substituted by at least one hydroxy group and optionally one or more further substituents.

[0020] According to a sixth aspect of the present invention, there is provided a polyolefin composition comprising a polyolefin material and a detectable amount of at least one amido alcohol compound and / or a derivative thereof, wherein the or each amido alcohol compound is of the formula R1C(O)NR2R3, wherein R1is an optionally substituted C5-23 hydrocarbyl group, and each of R2and R3is independently a hydrocarbyl group having at least three carbon atoms and wherein each hydrocarbyl group R2and R3is substituted by at least one hydroxy group and optionally one or more further substituents, and wherein the detectable amount is 2000 ppm or less.

[0021] According to a seventh aspect of the present invention, there is provided a polyolefin composition obtained by conducting the method of the first aspect or obtained by polymerisation of the polymerisation reaction mixture according to the fifth aspect.

[0022] According to an eighth aspect of the present invention, there is provided a polyolefin material obtained by conducting the method of the first aspect or obtained by polymerisation of the polymerisation reaction mixture according to the fifth aspect.

[0023] According to a ninth aspect of the present invention, there is provided an article made from the polyolefin composition according to the sixth or seventh aspect or made from the polyolefin material according to the eighth aspect.

[0024] Detailed descriptionUnless otherwise stated, the following terms used in the specification and claims have the meanings set out below.

[0025] The terms “alkyl” and “alkenyl” include both straight and branched chain alkyl and alkenyl groups respectively unless otherwise stated.

[0026] The term “aryl” as used herein relates to an organic radical derived from an aromatic hydrocarbon by removal of one hydrogen, and includes any monocyclic, bicyclic or polycyclic carbon ring of up to 7 members in each ring, wherein at least one ring is aromatic.

[0027] The term “aralkyl” as used herein relates to alkyl radicals substituted with an aryl group, wherein the aryl group is an organic radical derived from an aromatic hydrocarbon by removal of one hydrogen, and includes any monocyclic, bicyclic or polycyclic carbon ring of up to 7 members in each ring, wherein at least one ring is aromatic. An example of an aralkyl group is a benzyl group.

[0028] As used in the specification and the appended claims, the singular forms "a", "an," and "the" include both singular and plural referents unless the context clearly dictates otherwise.

[0029] Throughout this specification, the term “comprising” or “comprises” means including the component(s) specified but not to the exclusion of the presence of other components. The term “consisting essentially of’ or “consists essentially of’ means including the components specified but excluding other components except for components added for a purpose other than achieving the technical effect of the invention. The term “consisting of’ or “consists of’ means including the components specified but excluding other components.

[0030] Whenever appropriate, depending upon the context, the use of the term “comprises” or “comprising” may also be taken to include the meaning “consists essentially of’ or “consisting essentially of’, and also may also be taken to include the meaning “consists of’ or “consisting of’.

[0031] As used herein, unless otherwise expressly specified, all numbers such as those expressing values, ranges, amounts of percentages may be read as if prefaced by the word “about”, even if the term does not expressly appear.

[0032] The recitation of numerical ranges by endpoints includes all integer numbers and, where appropriate, fractions subsumed within that range (e.g. 1 to 5 can include 1 , 2, 3, 4 when referring to, for example, a number of elements, and can also include 1.5, 2, 2.75 and 3.80,when referring to, for example, measurements). The recitation of end points also includes the end point values themselves (e.g. from 1.0 to 5.0 includes both 1.0 and 5.0). Any numerical range recited herein is intended to include all sub-ranges subsumed therein.

[0033] The optional features set out herein may be used either individually or in combination with each other where appropriate and particularly in the combinations as set out in the accompanying claims. The optional features for each exemplary aspect of the invention, as set out herein are also applicable to any other aspects or exemplary aspects of the invention, where appropriate. In other words, the skilled person reading this specification should consider the optional features for each aspect or embodiment of the invention as interchangeable and combinable between different aspects of the invention.

[0034] As used herein, the term "and / or," when used in a list of two or more items, means that any one of the listed items can be employed by itself or any combination of two or more of the listed items can be employed. For example, if a list is described as comprising group A, B, and / or C, the list can comprise A alone, B alone, C alone, A and B in combination, A and C in combination, B and C in combination, or A, B, and C in combination.

[0035] Unless otherwise mentioned all references to ppm in this specification are to parts per million by weight.

[0036] Unless otherwise stated herein, the reference to “liquid” and “solid” refer to a state at 25°C and standard pressure (101 ,325 Pa).

[0037] According to a first aspect of the present invention, there is provided a method of making a polyolefin material, the method comprising at least one step of polymerising at least one olefinic monomer in the presence of at least one polymerisation catalyst and at least one amido alcohol compound; wherein the or each amido alcohol compound is of the formula R1C(O)NR2R3, wherein R1is an optionally substituted C5-23 hydrocarbyl group, and each of R2and R3is independently a hydrocarbyl group having at least three carbon atoms and wherein each hydrocarbyl group R2and R3is substituted by at least one hydroxy group and optionally one or more further substituents.

[0038] By a “method of making a polyolefin material” we mean a method comprising reacting at least one olefinic monomer intended to polymerise to form a polyolefin material.

[0039] By a “polyolefin material” we mean a material that comprises or consists essentially of one or more polyolefins.The polyolefin material (for example as formed by the method of the first aspect) may comprise one or more than one polyolefin.

[0040] The polyolefin material (for example as formed by the method of the first aspect) may consist essentially of or consist of one or more than one polyolefin. The polyolefin material (for example as formed by the method of the first aspect) may consist essentially of or consist of one (i.e. a single) polyolefin.

[0041] The polyolefin material may be a heterophasic (impact) copolymer.

[0042] The method of the first aspect may comprise one or more than one polymerisation step, i.e. polymerisation of at least one olefinic monomer. For example, the method of the first aspect may comprise more than one sequential polymerisation steps, such as two sequential polymerisation steps (to provide a sequential polymerisation reaction), for example to make a heterophasic (impact) copolymer.

[0043] By a “polyolefin” we mean a polymer that is prepared by polymerising at least one olefinic monomer, preferably that is prepared by polymerising monomers that consist essentially of or consist of at least one olefinic monomer.

[0044] The polyolefin material may be a homopolymer, such that the method of the first aspect may comprise polymerising one olefinic monomer to make a polyolefin material that is a homopolymer.

[0045] The polyolefin material may be a copolymer, such that the method of the first aspect may comprise polymerising two or more (preferably two) olefinic monomers to make a polyolefin material that is a copolymer. The copolymer may be a random copolymer.

[0046] The polyolefin material may be a heterophasic (impact) copolymer, such that that method of the first aspect may comprise two sequential polymerisation steps to make a polyolefin material that is a heterophasic (impact) copolymer. The polyolefin material may be a heterophasic (impact) polypropylene copolymer (also referred to as a heterophasic (impact) polypropylene ethylenepropylene copolymer). The heterophasic (impact) polypropylene copolymer may comprise from 1 to 60 wt%, preferably, from 20 to 45 wt%, of an ethylene-propylene copolymer (especially an ethylene-propylene copolymer rubber).

[0047] Heterophasic (impact) copolymers are well known to persons skilled in the art. As would be well known to persons skilled in the art, a heterophasic (impact) copolymer comprises polymeric components in separate domains. Typically, a heterophasic (impact) copolymer comprises asemi-crystalline homopolymer matrix and a copolymer (for example in the form of rubber) dispersed in the homopolymer matrix. The homopolymer may preferably be polypropylene and the copolymer may preferably be an ethylene-propylene copolymer (such as an ethylenepropylene rubber). Thus, the heterophasic (impact) copolymer is preferably a heterophasic (impact) polypropylene copolymer that comprises a semi-crystalline matrix of polypropylene and an ethylene-propylene copolymer (for example in the form of rubber) dispersed in the polypropylene matrix.

[0048] By “semi-crystalline” we mean that the homopolymer matrix has both amorphous and crystalline regions, as would be well known to persons skilled in the art.

[0049] References herein to “rubber” are intended to mean a polymer with a high amorphous and low crystalline content, as would be well known to persons skilled in the art.

[0050] When the polyolefin material is a heterophasic (impact) copolymer, the method of the first aspect may be used to make any polymeric component thereof. For example, when the polyolefin material is a heterophasic (impact) copolymer, the method of the first aspect may be used to make a semi-crystalline homopolymer matrix and / or a copolymer to be dispersed in the homopolymer matrix.

[0051] When the polyolefin material is a heterophasic (impact) polypropylene copolymer, the method of the first aspect may be used to make the semi-crystalline polypropylene matrix and / or to make the ethylene-propylene copolymer component of the heterophasic (impact) polypropylene copolymer. Preferably, the method of the first aspect may be used to make the ethylene-propylene copolymer component of a heterophasic (impact) polypropylene copolymer.

[0052] When the polyolefin material is a heterophasic (impact) polypropylene copolymer, the method of the first aspect may comprise a polymerisation step that is conducted in the presence of a pre-formed polypropylene, wherein the polymerisation step makes an ethylene-propylene copolymer dispersed in the polypropylene (i.e. to prepare the heterophasic (impact) polypropylene copolymer).

[0053] The method of the first aspect makes use of at least one amido alcohol compound of the formula R1C(O)NR2R3, wherein R1is an optionally substituted C5-23 hydrocarbyl group, and each of R2and R3is independently a hydrocarbyl group having at least three carbon atoms and wherein each hydrocarbyl group R2and R3is substituted by at least one hydroxy group and optionally one or more further substituents. The method of the first aspect may use two or more such amido alcohol compounds.For the avoidance of doubt, when we refer to an optionally substituted C5-23 hydrocarbyl group, we mean that the hydrocarbyl group (without any optional substituents) contains from 5 to 23 carbon atoms, such that any substituents may contain further carbon atoms in addition to the 5 to 23 carbon atoms of the hydrocarbyl group. The same applies to the C11-17 or C3-6 etc. hydrocarbyl groups as defined herein.

[0054] In the formula R1C(O)NR2R3, R1is an optionally substituted C5-23 hydrocarbyl group. For example, R1may suitably be an optionally substituted C7-23 or C7-17 hydrocarbyl group, or preferably an optionally substituted Cn-17 hydrocarbyl group.

[0055] Suitably, R1may be optionally substituted with any suitable substituents. Examples of suitable substituents may include hydroxy, C1-4 alkoxy and / or halo groups.

[0056] Suitably, R1may be an optionally substituted C5-23 (suitably C7-23 or Cn-17) alkyl, cycloalkyl, alkenyl, cycloalkenyl, aryl, or alkaryl group.

[0057] Preferably, R1may be an optionally substituted C5-23 (suitably C7-23 or Cn-17) alkyl or alkenyl group.

[0058] More preferably, R1may be an optionally substituted C5-23 (suitably C7-23 or Cn-17) alkyl group.

[0059] More preferably, R1may be an optionally substituted C5-23 (suitably C7-23 or Cn-17) alkenyl group.

[0060] Preferably, when R1is an optionally substituted C5-23 (suitably C7-23 or Cn-17) alkyl or alkenyl group, the alkyl or alkenyl group is linear.

[0061] For example, R1may be an optionally substituted Cn or C17 alkyl or alkenyl group, more preferably an optionally substituted linear Cn or C17 alkyl or alkenyl group.

[0062] For example, the group R1C(O)- may be derived from an unsaturated fatty acid or reactive equivalent thereof, such as derived from dodecenoic acid, oleic acid, elaidic acid, palmitoleic acid, petroselic acid, ricinoleic acid, eleostearic acid, linoleic acid, linolenic acid, galoleic acid, erucic acid or hypogeic acid.

[0063] Preferably, the group R1C(O)- may be derived from oleic acid, elaidic acid, palmitoleic acid, petroselic acid, ricinoleic acid, eleostearic acid, linoleic acid, linolenic acid, galoleic acid, erucic acid or hypogeic acid.

[0064] Preferably, R1is an unsubstituted group.Preferably, R1is an unsaturated group. For example, R1may be a mono, di, tri or polyunsaturated group.

[0065] More preferably, R1is a monounsaturated group.

[0066] Preferably, R1is a lineargroup.

[0067] More preferably, R1is a linear unsaturated group. For example, R1may be a linear mono, di, tri or polyunsaturated group, most preferably a linear mono unsaturated group.

[0068] Preferably, R1may be an unsubstituted C5-23 (suitably C7-23 or Cn-17) alkyl or alkenyl group.

[0069] More preferably, R1may be an unsubstituted C5-23 (suitably C7-23 or Cn-17) alkyl group.

[0070] More preferably, R1may be an unsubstituted C5-23 (suitably C7-23 or Cn-17) alkenyl group.

[0071] Preferably, R1may be an unsubstituted linear C5-23 (suitably C7-23 or Cn-17) alkyl or alkenyl group.

[0072] More preferably, R1may be an unsubstituted linear C5-23 (suitably C7-23 or Cn-17) alkyl group.

[0073] More preferably R1may be an unsubstituted linear C5-23 (suitably C7-23 or Cn-17) alkenyl group.

[0074] For example, R1may be an unsubstituted Cn or C17 alkyl or alkenyl group, more preferably an unsubstituted linear Cn or C17 alkyl or alkenyl group.

[0075] In the formula R1C(O)NR2R3, each of R2and R3is independently a hydrocarbyl group having at least three carbon atoms and wherein each hydrocarbyl group R2and R3is substituted by at least one hydroxy group and optionally one or more further substituents. Thus, the groups R2and R3are each substituted by at least one hydroxy group, and may be substituted by two or more hydroxy groups. The groups R2and R3may optionally be substituted by one or more further substituents in addition to the at least one hydroxy group. Examples of suitable further such substituents may include one or more of C1-4 alkoxy, halo and / or amino groups.

[0076] Preferably, each of R2and R3is substituted by only one (i.e. a single) hydroxy group.

[0077] Preferably, each of R2and R3is substituted by at least one hydroxy group and is not further substituted.Preferably, each of R2and R3is substituted by only one (i.e. a single) hydroxy group and is not further substituted.

[0078] R2and R3may be the same or different. Preferably R2and R3are the same.

[0079] Suitably, each of R2and R3is independently an alkyl, alkenyl, aryl, cycloalkyl or cycloalkenyl group having at least three carbon atoms or an alkaryl group having at least six carbon atoms, wherein each of R2and R3is substituted by at least one hydroxy group and optionally one or more further substituents.

[0080] Preferably, each of R2and R3is independently an alkyl, alkenyl, cycloalkyl or cycloalkenyl group having at least three carbon atoms, wherein each group is substituted by at least one hydroxy group and optionally one or more further substituents.

[0081] More preferably, each of R2and R3is independently an alkyl or alkenyl group having at least three carbon atoms, wherein each alkyl or alkenyl group is substituted by at least one hydroxy group and optionally one or more further substituents.

[0082] Even more preferably, each of R2and R3is independently an alkyl group having at least three carbon atoms, wherein each alkyl group is substituted by at least one hydroxy group and optionally one or more further substituents.

[0083] Suitably, R2and R3may each independently represent a C3-20 hydrocarbyl group, for example a C3-16 hydrocarbyl group or a C3-12 hydrocarbyl group, preferably a C3-8 hydrocarbyl group, most preferably a C3-6 hydrocarbyl group, wherein each hydrocarbyl group R2and R3is substituted by at least one hydroxy group and optionally one or more further substituents.

[0084] Suitably, each of R2and R3is independently a C3-20 (for example C3-16 or C3-12, preferably C3-8, most preferably C3-6) alkyl, alkenyl, aryl, cycloalkyl or cycloalkenyl group, or a Ce-20 (for example Ce-ie or Ce-12, preferably a Ce-s) alkaryl group, wherein each alkyl, alkenyl, aryl, alkaryl, cycloalkyl or cycloalkenyl group is substituted by at least one hydroxy group and optionally one or more further substituents.

[0085] Preferably, each of R2and R3is independently a C3-20 (for example C3-16 or C3-12, preferably C3-8, most preferably C3-6) alkyl, alkenyl, cycloalkyl or cycloalkenyl group, wherein each alkyl, alkenyl, cycloalkyl or cycloalkenyl group is substituted by at least one hydroxy group and optionally one or more further substituents.More preferably, each of R2and R3is independently a C3-20 (for example C3-16 or C3-12, preferably C3-8, most preferably C3-6) alkyl or alkenyl group, wherein each alkyl or alkenyl group is substituted by at least one hydroxy group and optionally one or more further substituents.

[0086] Even more preferably, each of R2and R3is independently a C3-20 (for example C3-16 or C3-12, preferably C3-8, most preferably C3-6) alkyl group, wherein each alkyl group is substituted by at least one hydroxy group and optionally one or more further substituents.

[0087] More preferably, each of R2and R3is independently a C3-8, preferably a C3-6, alkyl, alkenyl, cycloalkyl or cycloalkenyl group, wherein each alkyl, alkenyl, cycloalkyl or cycloalkenyl group is substituted by at least one hydroxy group and optionally one or more further substituents.

[0088] More preferably, each of R2and R3is independently a C3-8, preferably a C3-6, alkyl or alkenyl group, wherein each alkyl or alkenyl group is substituted by at least one hydroxy group and optionally one or more further substituents.

[0089] Even more preferably, each of R2and R3is independently a C3-8, preferably a C3-6, alkyl group, wherein each alkyl group is substituted by at least one hydroxy group and optionally one or more further substituents.

[0090] Preferably, R1is an unsubstituted linear C5-23 (suitably C7-23 or C11-17) alkyl or alkenyl group and each of R2and R3is independently an alkyl, alkenyl, aryl, cycloalkyl or cycloalkenyl group having at least three carbon atoms, or an alkaryl group having at least six, or at least eight, carbon atoms, wherein each of R2and R3is substituted by at least one hydroxy group and optionally one or more further substituents.

[0091] Preferably, R1is an unsubstituted linear C5-23 (suitably C7-23 or Cn-17) alkyl or alkenyl group and each of R2and R3is independently an alkyl or alkenyl group having at least three carbon atoms, or an alkaryl group having at least six, or at least eight, carbon atoms, wherein each of R2and R3is substituted by at least one hydroxy group and optionally one or more further substituents.

[0092] Preferably, R1is an unsubstituted linear C5-23 (suitably C7-23 or Cn-17) alkyl or alkenyl group and each of R2and R3is independently a C3-8, preferably a C3-6, alkyl or alkenyl group, wherein each alkyl or alkenyl (R2and R3) group is substituted by at least one hydroxy group and optionally one or more further substituents.

[0093] Preferably, the or each amido alcohol compound may be of the formula (I):

[0094]

[0095] wherein R1is as defined herein and R4and R5are each independently an optionally substituted C1-6 alkyl, C2-6 alkenyl, C3-8 cycloalkyl, C3-8 cycloalkenyl or Cs- aryl group.

[0096] R4and R5may be the same or different. Preferably R4and R5are the same.

[0097] Suitably, R4and R5are each independently an optionally substituted C1-6 alkyl, C2-6 alkenyl or CB-IO aryl group, preferably an optionally substituted C1-6 alkyl or Cs- aryl group.

[0098] Preferably, R4and R5are each independently selected from a methyl, ethyl, propyl, phenyl or cyclohexyl group, more preferably from a methyl, ethyl, propyl or phenyl group.

[0099] Preferably each of R4and R5is a methyl group.

[0100] Preferably in the formula (I), R1is an optionally substituted C5-23 (suitably C7-23 or Cn-17) alkyl or alkenyl group.

[0101] Preferably in the formula (I), R1is an optionally substituted C5-23 (suitably C7-23 or Cn-17) alkyl or alkenyl group and R4and R5are each independently an optionally substituted C1-6 alkyl or Cs-aryl group.

[0102] Preferably in the formula (I), R1is an optionally substituted C5-23 (suitably C7-23 or Cn-17) alkyl or alkenyl group and R4and R5are each independently selected from a methyl, ethyl, propyl, phenyl or cyclohexyl group, more preferably from a methyl, ethyl, propyl or phenyl group.

[0103] Where R1comprises one or more alkenyl groups, the alkene functional groups may be in the cis or trans configuration. Preferably the alkene functional groups are in the cis configuration.

[0104] Preferably, where R1comprises one or more alkenyl groups, the molar ratio of cis-isomers to trans-isomers is at least 2:1 , for example at least 2.5:1 , such as at least 3:1 , or at least 3.5:1 , preferably at least 4:1 .

[0105] For example, where the or each amido alcohol compound is A / -oleyl-N,N-di(isopropanol)amide or / V-dodecyl N,N-di(isopropanol)amide, the molar ratio of cis-isomers to trans-isomers ispreferably at least 2:1 , for example at least 2.5:1 , such as at least 3:1 , or at least 3.5:1 , preferably at least 4:1. Where the or each amino alcohol compound is A / -oleyl-N,N-di(isopropanol)amide or / V-dodecyl N,N-di(isopropanol)amide, the molar ratio of cis-isomers to trans-isomers is preferably up to 20:1 , for example up to 10:1. For example, the molar ratio of cis-isomers to trans-isomers is preferably from 2:1 to 20:1 , preferably from 2:1 to 10:1 , or from 4:1 to 10:1.

[0106] As would be appreciated by persons skilled in the art, the compound of formula (I) may include isomers thereof, which isomer would depend on the route of manufacture. For example an isomer of formula (I’) may be present:

[0107]

[0108] OH OH (|’)

[0109] wherein R1, R4and R5are as defined herein in relation to formula (I).

[0110] Preferably, the or each amido alcohol compound may be selected from one or more of / V-oleyl-N,N-di(isopropanol)amide and / V-dodecyl N,N-di(isopropanol)amide.

[0111] The or each amido alcohol compound may be commercially available or can be readily prepared using procedures well known to those skilled in the art.

[0112] For example, the or each amido alcohol compound may be prepared by reacting a fatty acid or reactive equivalent thereof with a primary or secondary amino alcohol compound. Preferably the or each amido alcohol compound is prepared by reacting a fatty acid or reactive equivalent thereof with a secondary amino alcohol of formula NHR2R3, wherein R2and R3are as defined herein.

[0113] Any suitable fatty acid or reactive equivalent thereof may be used. Examples of suitable fatty acids include lauric acid, oleic acid, elaidic acid, palmitoleic acid, petroselic acid, ricinoleic acid, eleostearic acid, linoleic acid, linolenic acid, eicosanoic acid, galoleic acid, erucic acid, and hypogeic acid. Preferred examples of fatty acids include oleic acid, elaidic acid, palmitoleic acid, petroselic acid, ricinoleic acid, eleostearic acid, linoleic acid, linolenic acid, eicosanoic acid, galoleic acid, erucic acid, and hypogeic acid. Reactive equivalents of such fatty acids may also be used, as would be appreciated by a person skilled in the art.

[0114] Preferably the fatty acid or reactive equivalent thereof is oleic acid or a reactive equivalent thereof.The skilled person will appreciate that an amido alcohol compound that is prepared by an industrial, especially alkoxylation, process may have a distribution of alcohol substituents therein.

[0115] The or each amido alcohol compound may be used in the method of the first aspect in any form suitable for dosing into the polymerisation reaction. Preferably, the or each amido alcohol compound is used in the method of the first aspect as a neat additive, i.e. without being formulated into an additive composition. For example the or each amido alcohol compound may be used in the method of the first aspect in the form of a solid, a powder, a gel, a solution, or a liquid.

[0116] Alternatively, for example, the or each amido alcohol compound may be used in the method of the first aspect in the form of a solution. Suitable solutions may comprise any suitable solvents), such as a non-polar aprotic solvent (such as n-pentane, n-hexane or n-heptane).

[0117] Preferably, the or each amido alcohol compound is a liquid at 25°C and standard pressure (101 ,325 Pa).

[0118] Preferably, the or each amido alcohol compound is a liquid at standard pressure and at a temperature of from 0°C to 80°C, more preferably at a temperature of from -5°C to 80°C, even more preferably at a temperature of from -15°C to 80°C or -20°C to 80°C, most preferably at a temperature of from -25°C to 80°C. This offers advantages for low temperature storage and / or handling of the amido alcohol in use, for example enabling the polymerisation method to be conveniently conducted in lower temperature environments.

[0119] The use of at least one amido alcohol compound as described in the first aspect of the invention has surprisingly been found to reduce reactor fouling and / or to increase product pourability during or after the polymerisation of at least one olefinic monomer to make a polyolefin material.

[0120] The or each amido alcohol compound may be used in the method of the first aspect in amounts typical of an additive, and the particular amount used will depend on the nature of the olefinic monomer(s) and on the reaction conditions used.

[0121] For example, the amido alcohol compound(s) may be used in an amount of from 1 to 2,000 ppm, such as from 1 to 1 ,500 ppm, such as from 1 to 1 ,000 ppm, for example from 20 to 1000 ppm, based on the total weight of the olefinic monomer(s) to be polymerised (in each polymerisation step). The amounts stated refer to the total amount of amido alcohol compound when one or more such compound is used.When the method of the first aspect is for making homopolypropylene (i.e. wherein the one or more olefinic monomers is propylene), the amido alcohol compound(s) may be used in an amount of from 10 to 200 ppm, such as from 15 to 150 ppm, suitably from 20 to 120 ppm, based on the total weight of the olefinic monomer to be polymerised (in each polymerisation step).

[0122] When the method of the first aspect is for making an ethylene-propylene copolymer (i.e. wherein the one or more olefinic monomers are ethylene and propylene), the amido alcohol compound(s) may be used in an amount of from 1 to 2000 ppm, such as from 20 to 1500 ppm, preferably from 60 to 1 ,000 ppm, based on the total weight of the olefinic monomer to be polymerised (in each polymerisation step).

[0123] When the method of the first aspect is for making a copolymer component of a heterophasic (impact) polypropylene copolymer (such as wherein the one or more olefinic monomers are propylene and ethylene), the amido alcohol compound(s) may be used in an amount of from 1 to 2,000 ppm, such as from 100 to 1 ,000 ppm, based on the total weight of the olefinic monomer to be polymerised (in each polymerisation step).

[0124] When the method of the first aspect is for making an ethylene-propylene copolymer component of a heterophasic (impact) polypropylene copolymer (wherein the one or more olefinic monomers are propylene and ethylene), the amido alcohol compound(s) may be used in an amount of from 60 to 450 ppm based on the total weight of the polypropylene homopolymer present at the start of the polymerisation reaction.

[0125] The polymerisation catalyst(s) is suitably used in the method of the first aspect in a weight excess compared to the amido alcohol compound(s). For example, the weight ratio of the total polymerisation catalyst(s) to the total amido alcohol compound(s) may be from 10:1 to 1.2:1 , suitably from 5:1 to 1.5:1 , preferably from 3:1 to 2:1.

[0126] Suitably, the or each amido alcohol compound does not affect the melt flow rate (MFR) of the polyolefin material obtained by the method of the first aspect.

[0127] Suitably the or each amido alcohol compound does not affect the polymer powder bulk density (BD) of the polyolefin material obtained by the method of the first aspect.

[0128] Suitably the or each amido alcohol compound does not affect the xylene soluble response (XS) of the polyolefin material obtained by the method of the first aspect.

[0129] The method of making a polyolefin material according to the first aspect comprises at least one step of polymerising at least one olefinic monomer, i.e. to obtain the polyolefin material. Themethod of making a polyolefin material may comprise polymerising only one olefinic monomer, i.e. to produce a homopolymer. Alternatively, the method of making a polyolefin material may comprise polymerising at least two different olefinic monomers, i.e. to produce a copolymer, for example a homogeneous copolymer (also known as a random copolymer) or a copolymer that is a component of a heterophasic (impact) copolymer.

[0130] The polyolefin material formed by the method of the first aspect may be a homopolymer.

[0131] The polyolefin material formed by the method of the first aspect may be a copolymer

[0132] The polyolefin material formed by the method of the first aspect may be polypropylene homopolymer.

[0133] The polyolefin material formed by the method of the first aspect may be a heterophasic (impact) copolymer.

[0134] The polyolefin material formed by the method of the first aspect may be a component of a heterophasic (impact) copolymer. For example the polyolefin material formed by the method of the first aspect may be a semi-crystalline homopolymer (for example polypropylene) component of a heterophasic (impact) copolymer. For example, the polyolefin material formed by the method of the first aspect may be a copolymer (for example an ethylene-propylene copolymer) component of a heterophasic (impact) copolymer.

[0135] Suitably, the method of the first aspect may comprise polymerising at least two different olefinic monomers.

[0136] The polyolefin material formed by the method of the first aspect may be a copolymer, such as a homogeneous (random) copolymer or a copolymer component of a heterophasic (impact) copolymer .

[0137] The polyolefin material formed by the method of the first aspect may be a polypropylene copolymer, preferably a propylene copolymer component of a heterophasic (impact) polypropylene copolymer.

[0138] The polyolefin material formed by the method of the first aspect may be an ethylene-propylene copolymer component of a heterophasic (impact) polypropylene copolymer.

[0139] The polyolefin material formed by the method of the first aspect may be an ethylene-propylene copolymer, such as a random ethylene-propylene copolymer.The polyolefin material formed by the method of the first aspect may be a free-flowing powder.

[0140] Suitably, the at least one olefinic monomer (i.e. to be polymerised in the method of the first aspect) is at least one olefin, preferably at least one a-olefin. Suitably, the at least one olefinic monomer is at least one C2 to C24 a-olefin, preferably at least one C2 to C20 a-olefin or at least one C2 to C12 a-olefin, for example at least one C2 to Ce a-olefin.

[0141] The at least one olefinic monomer may be selected from one or more of ethylene and propylene (including mixtures thereof), and a C4 to C24 a-olefin, such as a C4 to C12 a-olefin.

[0142] Suitably, the at least one olefinic monomer may comprise one or more of ethylene, propylene, butylene and isobutylene (including mixtures of two or more thereof) in an amount of at least 60 wt%, such as at least 70 wt%, such as at least 80 wt%, for example at least 90 wt%, based on the total weight of the at least one olefinic monomer.

[0143] Suitably, the at least one olefinic monomer may comprise one or more of ethylene, propylene and butylene, (including mixtures of two or more thereof) in an amount of at least 60 wt%, such as at least 70 wt%, such as at least 80 wt%, for example at least 90 wt%, based on the total weight of the at least one olefinic monomer.

[0144] Suitably, the at least one olefinic monomer may comprise one or more of ethylene and propylene (including mixtures thereof) in an amount of at least 60 wt%, such as at least 70 wt%, such as at least 80 wt%, for example at least 90 wt%, based on the total weight of the at least one olefinic monomer.

[0145] Suitably the at least one olefinic monomer may be selected from one or more of ethylene, propylene, butylene and isobutylene (including mixtures of two or more thereof).

[0146] Preferably, the at least one olefinic monomer may be selected from one or more of ethylene, propylene and butylene (including mixtures of two or more thereof).

[0147] More preferably, the at least one olefinic monomer may be selected from one or more of ethylene and propylene (including mixtures thereof). For example, the at least one olefinic monomer may be a mixture of ethylene and propylene.

[0148] Preferably, the at least one olefinic monomer is ethylene or propylene.

[0149] Most preferably, the at least one olefinic monomer is propylene. In this case, the polyolefin material made by the method of the first aspect is homopolypropylene.Optionally, one or more higher a-olefins can be included, for example to modify the density and / or other physical properties of the produced polyolefin material. Examples of suitable higher a-olefins may include hexene, octene and decene. When such higher a-olefins are included, they are typically present in a minor amount such as less than 10 wt%, suitably less than 5 wt% (based on the total weight of olefinic monomers).

[0150] The or each olefinic monomer may be purified prior to use in the method of the first aspect. Methods for purifying the olefinic monomer would be well known to persons skilled in the art.

[0151] Suitably the at least one olefinic monomer used in the method of the first aspect may have a content of carbon monoxide (CO) of up to 50 vol. ppb or up to 25 vol. ppb, for example up to 15 vol. ppb, suitably up to 10 vol. ppb.

[0152] Suitably the at least one olefinic monomer used in the method of the first aspect may have a content of carbonyl sulfide (COS) of up to 50 vol. ppb, or up to 25 vol. ppb, for example up to 15 vol. ppb, suitably up to 10 vol. ppb.

[0153] Suitably the at least one olefinic monomer used in the method of the first aspect may have a content of water of up to 10 vol. ppm, or up to 5 vol. ppm, for example up to 1 vol. ppm, suitably up to 0.5 vol. ppm, or up to 0.1 vol. ppm.

[0154] Suitably the at least one olefinic monomer used in the method of the first aspect may have a content of oxygen of up to 10 vol. ppm, or up to 5 vol. ppm, for example up to 1 vol. ppm, suitably up to 0.5 vol. ppm, or up to 0.1 vol. ppm.

[0155] The method of the first aspect is conducted in the presence of at least one polymerisation catalyst. Any suitable polymerisation catalyst may be used. For example the or each polymerisation catalyst may comprise a Ziegler-Natta catalyst and / or a metallocene catalyst. Additional suitable catalysts include chromium-based catalysts such as Phillips catalyst.

[0156] Preferably the or each polymerisation catalyst comprises a Ziegler-Natta catalyst.

[0157] A Ziegler-Natta catalyst typically comprises a transition metal compound which is used in combination with or pre-treated with an organoaluminium compound (i.e. co-catalyst). The transition metal compound may comprise one or more of a titanium, chromium, vanadium or zirconium compound. In particular, the transition metal compound may comprise a titanium halide compound, such as a titanium chloride compound, for example Ti(lll)Ch orTi(IV)Cl4. The organoaluminium compound may comprise triisobutylaluminium (TIBAI), trimethylaluminium (TMA) triethylaluminium, diethylaluminium chloride or aluminium chloride (AlCh). For example,the organoaluminium compound may comprise triethylaluminium, diethylaluminium chloride or aluminium chloride (AlCh) (most preferably triethylaluminium). The Zeigler-Natta catalyst may be provided on a suitable support, such as a magnesium halide support (for example MgCh). The Zeigler-Natta catalyst may additionally comprise a suitable external donor compound, such as an ester / silane external donor compound (for example cyclohexylmethyldimethoxysilane (C HMD MS)).

[0158] Suitably the or each polymerisation catalyst comprises a metallocene catalyst.

[0159] A metallocene catalyst typically comprises a transition metal compound having an oxidised transition metal centre (M) (for example in the oxidation state II) bonded to two cyclopentadienyl anions, i.e. having the general formula M(CsH5)2. The transition metal may be selected from one or more of, chromium, titanium, hafnium, and zirconium.

[0160] Suitably the or each polymerisation catalyst does not comprise a single site catalyst.

[0161] Examples of further suitable polymerisation catalysts for use in the method of the first aspect include chromium-based catalysts, for example Phillips catalyst.

[0162] The or each polymerisation catalyst may be a supported catalyst. For example the polymerisation catalyst may be an MgCh-supported catalyst.

[0163] Preferably the or each polymerisation catalyst may be an MgCh-supported Zeigler-Natta catalyst.

[0164] Suitably the or each polymerisation catalyst may be supported on a polyolefin carrier. For example the or each polymerisation catalyst may be supported on a polypropylene carrier.

[0165] For example, the polyolefin carrier (such as a polypropylene carrier) may be a component of a heterophasic (impact) copolymer (such as of a heterophasic (impact) polypropylene copolymer).

[0166] Suitably the or each polymerisation catalyst may be provided as a dispersion in a suitable medium, such as a mineral oil.

[0167] The polymerisation catalyst may be used in any suitable amount, as would be well known to persons skilled in the art. For example, a suitable loading of catalyst may be in the range of from 0.02 to 0.2 g, for example from 0.05 to 0.2 g, of active catalyst per kg of total olefinic monomer.The method of the first aspect may be conducted in the presence of a suitable chain transfer agent. Examples of suitable chain transfer agents include hydrogen, silanes, boranes and diethyl zinc (with hydrogen being preferred).

[0168] The method of the first aspect may be conducted using any suitable reaction conditions.

[0169] For example, the method may be conducted in a suitable reaction medium, as would be appreciated by persons skilled in the art. In some cases, a suitable reaction medium may be a suitable polymerisation solvent.

[0170] Processes used for polymer manufacture may include suspension polymerisation, bulk polymerisation, gas phase, condensed phase and slurry processes. Suitably, the polymerisation reaction is conducted in the gaseous phase.

[0171] The method of the first aspect may be carried out as a suspension polymerisation. Suitably the reaction medium for the suspension polymerisation is a solvent. For example the solvent may be an organic solvent such as an alkane, for example selected from one or more of propane, butane, pentane, hexane, heptane (including mixtures thereof).

[0172] The method of the first aspect may be carried out as a bulk polymerisation. Suitably the reaction medium for the bulk polymerisation is a liquid olefinic monomer. For example the reaction medium in a propylene homopolymerisation is suitably liquid propylene.

[0173] The method of the first aspect may be carried out as a gas phase polymerisation.

[0174] Where the method of the first aspect provides an ethylene-propylene random copolymer (for example in the form of rubber), the method is preferably carried out in the gaseous phase.

[0175] As the skilled person will appreciate, heterophasic (impact) copolymers are typically prepared by multi-step polymerisation methods, such as methods that comprise two or more sequential steps. For example the first step suitably involves producing a homopolymer, and this homopolymer may then be subsequently transferred to a second reaction step wherein copolymerisation occurs on the particles of the homopolymer.

[0176] The method of the first aspect may be applied in any and / or each stage of such a multi-step process. The method of the first aspect may further be applied in a transfer line as a reaction mixture is metered between steps of such a method.The method of the first aspect may comprise a first step comprising polymerising one olefinic monomer in the presence of at least one polymerisation catalyst and optionally at least one amido alcohol compound to prepare a homopolymer; and a second step comprising polymerising at least two different olefinic monomers in the presence of the homopolymer prepared in the first step and in the presence of at least one polymerisation catalyst and at least one amido alcohol compound to prepare a heterophasic (impact) copolymer; wherein the or each amido alcohol compound is of the formula R1C(O)NR2R3, wherein R1is an optionally substituted C5-23 hydrocarbyl group, and each of R2and R3is independently a hydrocarbyl group having at least three carbon atoms and wherein each hydrocarbyl group R2and R3is substituted by at least one hydroxy group and optionally one or more further substituents. The first and second steps may use the same or different, preferably the same, amido alcohol compound. Examples of well-known polymerisation processes, for example, which may be used in the method of the first aspect may include Novolen [Lummus Novolen], Innovene PP [Ineos], Spheripol [Lyondell Basell], Hypol and Hypol II [Mitsui]; Unipol PP [Grace]; JPP Horizone [JapanPP Corp.]; Sumitomo [Sumitomo]; Borstar PP [Borealis]; ExxonMobil [ExxonMobil]; Spherizone [Lyondell Basell],

[0177] The method of the first aspect may be carried out at any suitable temperature and pressure. For example, the method may be carried out at temperatures of from 25 to 150°C, or from 40 to 100°C, suitably from 50 to 90°C, preferably from 60 to 80°C, or from 70 to 80°C. For example, the method of the first aspect may be carried out at a pressure of from 1 to 5 MPa, for example from 1.5 to 3 MPa, or from 1.8 to 2.5 MPa, suitably from 2 to 2.4 MPa, or from 2.1 to 2.3 MPa.

[0178] The method of the first aspect may provide the polyolefin material as a component of a polyolefin composition. In other words, the method of the first aspect may provide a polyolefin composition comprising the polyolefin material. The polyolefin composition may, for example, in addition to the polyolefin material comprise residual olefinic monomer(s) and other components of the polymerisation reaction mixture, such as the or each amido alcohol compound and / or a derivative thereof, and / or the or each polymerisation catalyst and / or a derivative thereof. The polyolefin composition may be purified to separate the polyolefin material from other components thereof.

[0179] Suitably the method according to the first aspect provides the polyolefin material and / or a polyolefin composition in the form of a free-flowing powder.

[0180] Suitably the method according to the first aspect provides at least one improvement selected from:

[0181] a reduction in reactor fouling;

[0182] a reduction in reactor static; and / or• an improvement in product powder pourability;

[0183] compared to an equivalent method without the or each amido alcohol compound present as discussed herein.

[0184] According to a second aspect of the present invention, there is provided a use of an amido alcohol compound in an olefinic polymerisation process, wherein the olefinic polymerisation process comprises at least one step of the polymerisation of at least one olefinic monomer in the presence of at least one polymerisation catalyst; wherein the or each amido alcohol compound is of the formula R1C(O)NR2R3, wherein R1is an optionally substituted C5-23 hydrocarbyl group, and each of R2and R3is independently a hydrocarbyl group having at least three carbon atoms and wherein each hydrocarbyl group R2and R3is substituted by at least one hydroxy group and optionally one or more further substituents.

[0185] Preferred features of the second aspect are as defined in relation to the first aspect. In particular, preferred features of the polymerisation reaction, the or each amido alcohol compound, the at least one olefinic monomer and the at least one polymerisation catalyst in relation to the use of the second aspect are as set out herein in relation to the first aspect.

[0186] The use of the second aspect may provide, via the olefinic polymerisation process, a polyolefin material as disclosed herein in relation to the first aspect. For example, the use may provide a heterophasic (impact) copolymer, such as a heterophasic (impact) polypropylene copolymer.

[0187] According to a third aspect of the present invention, there is provided a method of providing at least one improvement during an olefinic polymerisation process, the method comprising:

[0188] (a) providing a polymerisation reaction mixture comprising at least one olefinic monomer, at least one polymerisation catalyst and at least one amido alcohol compound; and (b) carrying out a polymerisation process;

[0189] wherein the or each amido alcohol compound is of the formula R1C(O)NR2R3, wherein R1is an optionally substituted C5-23 hydrocarbyl group, and each of R2and R3is independently a hydrocarbyl group having at least three carbon atoms and wherein each hydrocarbyl group R2and R3is substituted by at least one hydroxy group and optionally one or more further substituents.

[0190] The reaction mixture may be prepared by any suitable method in step (a) of the method of the third aspect. For example, the at least one olefinic monomer, at least one polymerisation catalyst and at least one amido alcohol compound may be admixed sequentially in any suitable order, or two or more of the at least one olefinic monomer, at least one polymerisation catalyst and at least one amido alcohol compound may be admixed simultaneously to provide the polymerisation reaction mixture.In the method of the third aspect, the polymerisation process may be conducted in step (b) using any suitable reaction conditions and / or process steps, for example as discussed above in relation to the first aspect.

[0191] In the method of the third aspect, the polymerisation process in step (b) may provide a polyolefin material or a polyolefin composition as disclosed herein.

[0192] According to a fourth aspect of the present invention, there is provided a use of an amido alcohol compound to provide at least one improvement during an olefinic polymerisation process, wherein the olefinic polymerisation process comprises the polymerisation of at least one olefinic monomer in the presence of at least one polymerisation catalyst; wherein the or each amido alcohol compound is of the formula R1C(O)NR2R3, wherein R1is an optionally substituted C5-23 hydrocarbyl group, and each of R2and R3is independently a hydrocarbyl group having at least three carbon atoms and wherein each hydrocarbyl group R2and R3is substituted by at least one hydroxy group and optionally one or more further substituents.

[0193] Preferred features of the third and fourth aspects are as defined in relation to the first aspect. In particular, preferred features of the polymerisation process, the at least one olefinic monomer, the at least one polymerisation catalyst, and the at least one amido alcohol compound of the third and fourth aspects are as set out herein in relation to the first aspect. Preferred features of the polyolefin composition of the third aspect are as set out herein in relation to the first, sixth or seventh aspect.

[0194] For the avoidance of doubt, by “polymerisation reaction mixture” we mean a composition comprising components intended to polymerise to form a polymer.

[0195] The polymerisation reaction mixture comprises at least one olefinic monomer, at least one polymerisation catalyst and at least one amido alcohol compound as disclosed herein.

[0196] For example, the polymerisation reaction mixture may comprise:

[0197] (i) at least one olefinic monomer;

[0198] (ii) at least one polymerisation catalyst; and

[0199] (iii) at least one amido alcohol compound R1C(O)NR2R3as defined herein.

[0200] For example, the polymerisation reaction mixture may comprise:

[0201] (i) at least one olefinic monomer;

[0202] (ii) at least one polymerisation catalyst comprising a Ziegler-Natta catalyst; and (iii) at least one amido alcohol compound R1C(O)NR2R3as defined herein.Preferably, the polymerisation reaction mixture may comprise:

[0203] (i) propylene and ethylene;

[0204] (ii) at least one polymerisation catalyst; and

[0205] (iii) at least one amido alcohol compound R1C(O)NR2R3as defined herein.

[0206] Preferably, the polymerisation reaction mixture may comprise:

[0207] (i) propylene and ethylene;

[0208] (ii) at least one polymerisation catalyst comprising a Ziegler-Natta catalyst; and (iii) at least one amido alcohol compound R1C(O)NR2R3as defined herein.

[0209] Preferably, the polymerisation reaction mixture may comprise:

[0210] (i) propylene;

[0211] (ii) at least one polymerisation catalyst; and

[0212] (iii) at least one amido alcohol compound R1C(O)NR2R3as defined herein.

[0213] Preferably, the polymerisation reaction mixture may comprise:

[0214] (i) propylene;

[0215] (ii) at least one polymerisation catalyst comprising a Ziegler-Natta catalyst; and (iii) at least one amido alcohol compound R1C(O)NR2R3as defined herein.

[0216] For example, the polymerisation reaction mixture may comprise:

[0217] (i) at least one olefinic monomer;

[0218] (ii) at least one polymerisation catalyst comprising a MgCh-supported Ziegler-Natta catalyst; and

[0219] (iii) at least one amido alcohol compound R1C(O)NR2R3as defined herein.

[0220] For example, the polymerisation reaction mixture may comprise:

[0221] (i) propylene and ethylene;

[0222] (ii) at least one polymerisation catalyst comprising a MgCh-supported Ziegler-Natta catalyst; and

[0223] (iii) at least one amido alcohol compound R1C(O)NR2R3as defined herein.

[0224] For example, the polymerisation reaction mixture may comprise:

[0225] (i) propylene;

[0226] (ii) at least one polymerisation catalyst comprising a MgCh-supported Ziegler-Natta catalyst; and

[0227] (iii) at least one amido alcohol compound R1C(O)NR2R3as defined herein.

[0228] For example, the polymerisation reaction mixture may comprise:(i) at least one olefinic monomer;

[0229] (ii) at least one polymerisation catalyst; and

[0230] (iii) at least one amido alcohol compound of the formula (I) as defined herein for example wherein R1is an optionally substituted C5-23 alkyl or alkenyl group and R4and R5are each independently an optionally substituted C1-6 alkyl or Ce- aryl group (for example at least one amido alcohol compound of the formula (I) selected from one or more of A / -oleyl-N,N-di(isopropanol)amide and / V-dodecyl N,N-di(isopropanol)amide).

[0231] For example, the polymerisation reaction mixture may comprise:

[0232] (i) at least one olefinic monomer;

[0233] (ii) at least one polymerisation catalyst comprising a Ziegler-Natta catalyst; and (iii) at least one amido alcohol compound of the formula (I) as defined herein for example wherein R1is an optionally substituted C5-23 alkyl or alkenyl group and R4and R5are each independently an optionally substituted C1-6 alkyl or Ce- aryl group (for example at least one amido alcohol compound of the formula (I) selected from one or more of A / -oleyl-N,N-di(isopropanol)amide and / V-dodecyl N,N-di(isopropanol)amide).

[0234] Preferably, the polymerisation reaction mixture may comprise:

[0235] (i) propylene and ethylene;

[0236] (ii) at least one polymerisation catalyst; and

[0237] (iii) at least one amido alcohol compound of the formula (I) as defined herein for example wherein R1is an optionally substituted C5-23 alkyl or alkenyl group and R4and R5are each independently an optionally substituted C1-6 alkyl or Ce- aryl group (for example at least one amido alcohol compound of the formula (I) selected from one or more of / V-oleyl-N,N-di(isopropanol)amide and / V-dodecyl N,N-di(isopropanol)amide).

[0238] Preferably, the polymerisation reaction mixture may comprise:

[0239] (i) propylene and ethylene;

[0240] (ii) at least one polymerisation catalyst comprising a Ziegler-Natta catalyst; and (iii) at least one amido alcohol compound of the formula (I) as defined herein for example wherein R1is an optionally substituted C5-23 alkyl or alkenyl group and R4and R5are each independently an optionally substituted C1-6 alkyl or Ce- aryl group (for example at least one amido alcohol compound of the formula (I) selected from one or more of / V-oleyl-N,N-di(isopropanol)amide and / V-dodecyl N,N-di(isopropanol)amide).Preferably, the polymerisation reaction mixture may comprise:

[0241] (i) propylene;

[0242] (ii) at least one polymerisation catalyst; and

[0243] (iii) at least one amido alcohol compound of the formula (I) as defined herein for example wherein R1is an optionally substituted C5-23 alkyl or alkenyl group and R4and R5are each independently an optionally substituted C1-6 alkyl or Ce- aryl group; (for example at least one amido alcohol compound of the formula (I) selected from one or more of A / -oleyl-N,N-di(isopropanol)amide and / V-dodecyl N,N-di(isopropanol)amide).

[0244] Preferably, the polymerisation reaction mixture may comprise:

[0245] (i) propylene;

[0246] (ii) at least one polymerisation catalyst comprising a Ziegler-Natta catalyst; and (iii) at least one amido alcohol compound of the formula (I) as defined herein for example wherein R1is an optionally substituted C5-23 alkyl or alkenyl group and R4and R5are each independently an optionally substituted C1-6 alkyl or Ce- aryl group; (for example at least one amido alcohol compound of the formula (I) selected from one or more of A / -oleyl-N,N-di(isopropanol)amide and / V-dodecyl N,N-di(isopropanol)amide).

[0247] For example, the polymerisation reaction mixture may comprise:

[0248] (i) at least one olefinic monomer;

[0249] (ii) at least one polymerisation catalyst comprising a MgCh-supported Ziegler-Natta catalyst; and

[0250] (iii) at least one amido alcohol compound of the formula (I) as defined herein for example wherein R1is an optionally substituted C5-23 alkyl or alkenyl group and R4and R5are each independently an optionally substituted C1-6 alkyl or Ce- aryl group; (for example at least one amido alcohol compound of the formula (I) selected from one or more of / V-oleyl-N,N-di(isopropanol)amide and / V-dodecyl N,N-di(isopropanol)amide).

[0251] For example, the polymerisation reaction mixture may comprise:

[0252] (i) propylene and ethylene;

[0253] (ii) at least one polymerisation catalyst comprising a MgCh-supported Ziegler-Natta catalyst; and

[0254] (iii) at least one amido alcohol compound of the formula (I) as defined herein for example wherein R1is an optionally substituted C5-23 alkyl or alkenyl group and R4and R5are each independently an optionally substituted C1-6 alkyl or Ce- aryl group; (for example at least one amido alcohol compound of the formula (I)selected from one or more of A / -oleyl-N,N-di(isopropanol)amide and / V-dodecyl N,N-di(isopropanol)amide).

[0255] For example, the polymerisation reaction mixture may comprise:

[0256] (i) propylene;

[0257] (ii) at least one polymerisation catalyst comprising a MgCh-supported Ziegler-Natta catalyst; and

[0258] (iii) at least one amido alcohol compound of the formula (I) as defined herein for example wherein R1is an optionally substituted C5-23 alkyl or alkenyl group and R4and R5are each independently an optionally substituted C1-6 alkyl or Ce- aryl group; (for example at least one amido alcohol compound of the formula (I) selected from one or more of A / -oleyl-N,N-di(isopropanol)amide and / V-dodecyl N,N-di(isopropanol)amide).

[0259] The polymerisation reaction mixture may comprise a suitable reaction medium as discussed above.

[0260] The polymerisation reaction mixture may suitably be in the form of a suspension. The suspension may comprise a suitable solvent. For example the solvent may be an organic solvent such as an alkane, for example selected from one or more of propane, butane, pentane, hexane, heptane (including mixtures thereof).

[0261] The polymerisation reaction mixture may suitably be a bulk polymerisation reaction mixture. Suitably the bulk polymerisation reaction mixture comprises a liquid olefinic monomer. For example the bulk polymerisation reaction mixture in a propylene homopolymerisation suitably comprises liquid propylene.

[0262] The polymerisation reaction mixture may suitably be a gas phase reaction mixture. This may be suitable when the polymerisation reaction mixture is intended to provide an ethylene-propylene random copolymer (for example in the form of rubber).

[0263] Suitably the at least one improvement of the third aspect is selected from one or more of:

[0264] • a reduction in reactor fouling;

[0265] • a reduction in reactor static; and / or

[0266] • an improvement in product powder pourability;

[0267] compared to an equivalent method or use without the or each amido alcohol compound present.

[0268] A reduction in reactor fouling may be determined visually by a reduction in the amount of polymer deposits on the surfaces in and around a reactor vessel after conducting the method;compared to conducting the method without the or each amido alcohol compound present. The surfaces in and around the reactor vessel may include the reactor covers, stirrers, walls, cooling coils, and space immediately surrounding openings in the reactor.

[0269] A reduction in reactor static may be measured by way of monitoring the electrostatic charge accumulated in the reactor during a polymerisation process. Methods of monitoring electrostatic charge will be known to the skilled person, such as by the use of an electrostatic probe.

[0270] An improvement in product powder pourability may be determined by an improvement in the pourability score, for example as measured according to ASTM D 1895 standard method. By the product we mean a polyolefin composition or a polyolefin material as disclosed herein.

[0271] According to a fifth aspect of the present invention, there is provided a polymerisation reaction mixture comprising:

[0272] (i) at least one olefinic monomer;

[0273] (ii) at least one polymerisation catalyst; and

[0274] (iii) at least one amido alcohol compound,

[0275] wherein the or each amido alcohol compound is of the formula R1C(O)NR2R3, wherein R1is an optionally substituted C5-23 hydrocarbyl group, and each of R2and R3is independently a hydrocarbyl group having at least three carbon atoms and wherein each hydrocarbyl group R2and R3is substituted by at least one hydroxy group and optionally one or more further substituents.

[0276] The polymerisation reaction mixture of the fifth aspect may further comprise one or more polyolefin materials, such as polyolefin materials formed by polymerisation of the at least one olefinic monomer once the polymerisation reaction begins.

[0277] The polymerisation reaction mixture of the fifth aspect may further comprise one or more suitable chain transfer agents, such as hydrogen, silanes, boranes and diethyl zinc (preferably hydrogen).

[0278] Preferred features of the fifth aspect are as defined in relation to the first aspect. In particular, preferred features of the at least one olefinic monomer, the at least one polymerisation catalyst, and the at least one amido alcohol compound of the fifth aspect are as set out herein in relation to the first aspect.

[0279] The polymerisation reaction mixture of the fifth aspect may, for example, comprise:

[0280] (i) at least one olefinic monomer;

[0281] (ii) at least one polymerisation catalyst; and(iii) at least one amido alcohol compound R1C(O)NR2R3as defined herein.

[0282] The polymerisation reaction mixture of the fifth aspect may comprise:

[0283] (i) at least one olefinic monomer;

[0284] (ii) at least one polymerisation catalyst comprising a Ziegler-Natta catalyst; and (iii) at least one amido alcohol compound R1C(O)NR2R3as defined herein.

[0285] Preferably, the polymerisation reaction mixture of the fifth aspect may comprise:

[0286] (i) propylene and ethylene;

[0287] (ii) at least one polymerisation catalyst; and

[0288] (iii) at least one amido alcohol compound R1C(O)NR2R3as defined herein.

[0289] Preferably, the polymerisation reaction mixture of the fifth aspect may comprise:

[0290] (i) propylene and ethylene;

[0291] (ii) at least one polymerisation catalyst comprising a Ziegler-Natta catalyst; and (iii) at least one amido alcohol compound R1C(O)NR2R3as defined herein.

[0292] Preferably, the polymerisation reaction mixture of the fifth aspect may comprise:

[0293] (i) propylene;

[0294] (ii) at least one polymerisation catalyst; and

[0295] (iii) at least one amido alcohol compound R1C(O)NR2R3as defined herein.

[0296] Preferably, the polymerisation reaction mixture of the fifth aspect may comprise:

[0297] (i) propylene;

[0298] (ii) at least one polymerisation catalyst comprising a Ziegler-Natta catalyst; and (iii) at least one amido alcohol compound R1C(O)NR2R3as defined herein.

[0299] For example, the polymerisation reaction mixture of the fifth aspect may comprise:

[0300] (i) at least one olefinic monomer;

[0301] (ii) at least one polymerisation catalyst comprising a MgCh-supported Ziegler-Natta catalyst; and

[0302] (iii) at least one amido alcohol compound R1C(O)NR2R3as defined herein.

[0303] For example, the polymerisation reaction mixture of the fifth aspect may comprise:

[0304] (i) propylene and ethylene;

[0305] (ii) at least one polymerisation catalyst comprising a MgCh-supported Ziegler-Natta catalyst; and

[0306] (iii) at least one amido alcohol compound R1C(O)NR2R3as defined herein.For example, the polymerisation reaction mixture of the fifth aspect may comprise:

[0307] (i) propylene;

[0308] (ii) at least one polymerisation catalyst comprising a MgCh-supported Ziegler-Natta catalyst; and

[0309] (iii) at least one amido alcohol compound R1C(O)NR2R3as defined herein.

[0310] For example, the polymerisation reaction mixture of the fifth aspect may comprise:

[0311] (i) at least one olefinic monomer;

[0312] (ii) at least one polymerisation catalyst; and

[0313] (iii) at least one amido alcohol compound of the formula (I) as defined herein for example wherein R1is an optionally substituted C5-23 alkyl or alkenyl group and R4and R5are each independently an optionally substituted C1-6 alkyl or Ce- aryl group; (for example at least one amido alcohol compound of the formula (I) selected from one or more of A / -oleyl-N,N-di(isopropanol)amide and / V-dodecyl N,N-di(isopropanol)amide).

[0314] For example, the polymerisation reaction mixture of the fifth aspect may comprise:

[0315] (i) at least one olefinic monomer;

[0316] (ii) at least one polymerisation catalyst comprising a Ziegler-Natta catalyst; and (iii) at least one amido alcohol compound of the formula (I) as defined herein for example wherein R1is an optionally substituted C5-23 alkyl or alkenyl group and R4and R5are each independently an optionally substituted C1-6 alkyl or Ce- aryl group; (for example at least one amido alcohol compound of the formula (I) selected from one or more of / V-oleyl-N,N-di(isopropanol)amide and / V-dodecyl N,N-di(isopropanol)amide).

[0317] Preferably, the polymerisation reaction mixture of the fifth aspect may comprise:

[0318] (i) propylene and ethylene;

[0319] (ii) at least one polymerisation catalyst; and

[0320] (iii) at least one amido alcohol compound of the formula (I) as defined herein for example wherein R1is an optionally substituted C5-23 alkyl or alkenyl group and R4and R5are each independently an optionally substituted C1-6 alkyl or Ce- aryl group; (for example at least one amido alcohol compound of the formula (I) selected from one or more of / V-oleyl-N,N-di(isopropanol)amide and / V-dodecyl N,N-di(isopropanol)amide).

[0321] Preferably, the polymerisation reaction mixture of the fifth aspect may comprise:

[0322] (i) propylene and ethylene;

[0323] (ii) at least one polymerisation catalyst comprising a Ziegler-Natta catalyst; and(iii) at least one amido alcohol compound of the formula (I) as defined herein for example wherein R1is an optionally substituted C5-23 alkyl or alkenyl group and R4and R5are each independently an optionally substituted C1-6 alkyl or Ce- aryl group; (for example at least one amido alcohol compound of the formula (I) selected from one or more of A / -oleyl-N,N-di(isopropanol)amide and / V-dodecyl N,N-di(isopropanol)amide).

[0324] Preferably, the polymerisation reaction mixture of the fifth aspect may comprise:

[0325] (i) propylene;

[0326] (ii) at least one polymerisation catalyst; and

[0327] (iii) at least one amido alcohol compound of the formula (I) as defined herein for example wherein R1is an optionally substituted C5-23 alkyl or alkenyl group and R4and R5are each independently an optionally substituted C1-6 alkyl or Ce- aryl group; (for example at least one amido alcohol compound of the formula (I) selected from one or more of A / -oleyl-N,N-di(isopropanol)amide and / V-dodecyl N,N-di(isopropanol)amide).

[0328] Preferably, the polymerisation reaction mixture of the fifth aspect may comprise:

[0329] (i) propylene;

[0330] (ii) at least one polymerisation catalyst comprising a Ziegler-Natta catalyst; and (iii) at least one amido alcohol compound of the formula (I) as defined herein for example wherein R1is an optionally substituted C5-23 alkyl or alkenyl group and R4and R5are each independently an optionally substituted C1-6 alkyl or Ce- aryl group; (for example at least one amido alcohol compound of the formula (I) selected from one or more of / V-oleyl-N,N-di(isopropanol)amide and / V-dodecyl N,N-di(isopropanol)amide).

[0331] For example, the polymerisation reaction mixture of the fifth aspect may comprise:

[0332] (i) at least one olefinic monomer;

[0333] (ii) at least one polymerisation catalyst comprising a MgCh-supported Ziegler-Natta catalyst; and

[0334] (iii) at least one amido alcohol compound of the formula (I) as defined herein for example wherein R1is an optionally substituted C5-23 alkyl or alkenyl group and R4and R5are each independently an optionally substituted C1-6 alkyl or Ce- aryl group; (for example at least one amido alcohol compound of the formula (I) selected from one or more of / V-oleyl-N,N-di(isopropanol)amide and / V-dodecyl N,N-di(isopropanol)amide).

[0335] For example, the polymerisation reaction mixture of the fifth aspect may comprise:(i) propylene and ethylene;

[0336] (ii) at least one polymerisation catalyst comprising a MgCh-supported Ziegler-Natta catalyst; and

[0337] (iii) at least one amido alcohol compound of the formula (I) as defined herein for example wherein R1is an optionally substituted C5-23 alkyl or alkenyl group and R4and R5are each independently an optionally substituted C1-6 alkyl or Ce- aryl group; (for example at least one amido alcohol compound of the formula (I) selected from one or more of A / -oleyl-N,N-di(isopropanol)amide and / V-dodecyl N,N-di(isopropanol)amide).

[0338] For example, the polymerisation reaction mixture of the fifth aspect may comprise:

[0339] (i) propylene;

[0340] (ii) at least one polymerisation catalyst comprising a MgCh-supported Ziegler-Natta catalyst; and

[0341] (iii) at least one amido alcohol compound of the formula (I) as defined herein for example wherein R1is an optionally substituted C5-23 alkyl or alkenyl group and R4and R5are each independently an optionally substituted C1-6 alkyl or Ce- aryl group; (for example at least one amido alcohol compound of the formula (I) selected from one or more of / V-oleyl-N,N-di(isopropanol)amide and / V-dodecyl N,N-di(isopropanol)amide).

[0342] There may be provided a polyolefin composition comprising a polyolefin material and a detectable amount of at least one amido alcohol compound and / or a derivative thereof, wherein the or each amido alcohol compound is of the formula R1C(O)NR2R3, wherein R1is an optionally substituted C5-23 hydrocarbyl group, and each of R2and R3is independently a hydrocarbyl group having at least three carbon atoms and wherein each hydrocarbyl group R2and R3is substituted by at least one hydroxy group and optionally one or more further substituents.

[0343] The polyolefin composition as disclosed herein, such as according to the sixth aspect, may be obtained by carrying out an olefinic polymerisation process on at least one olefinic monomer. The or each amido alcohol compound may be added before, during or after the olefinic polymerisation process. Suitably the or each amido alcohol compound is added before or during the olefinic polymerisation process. A derivative of the amido alcohol compound may be formed during the olefinic polymerisation process, as would be appreciated by persons skilled in the art.

[0344] When added after the polymerisation process, the amido alcohol compound may be added during extrusion of the polyolefin material, such as during granulation of the polyolefin material or during conversion into an article. In this case, the polyolefin composition may comprise oneor more additional components, such as one more components selected from a dye, pigment, lubricant, stabiliser, impact modifier, and flame retardant.

[0345] In one embodiment, the detectable amount of at least one amido alcohol compound and / or a derivative thereof is 2000 ppm or less. Thus, according to a sixth aspect of the present invention, there is provided a polyolefin composition comprising a polyolefin material and a detectable amount of at least one amido alcohol compound and / or a derivative thereof, wherein the or each amido alcohol compound is of the formula R1C(O)NR2R3, wherein R1is an optionally substituted C5-23 hydrocarbyl group, and each of R2and R3is independently a hydrocarbyl group having at least three carbon atoms and wherein each hydrocarbyl group R2and R3is substituted by at least one hydroxy group and optionally one or more further substituents, and wherein the detectable amount is 2000 ppm or less.

[0346] Suitably, the polyolefin composition of the sixth aspect is prepared according to the method of the first aspect.

[0347] The polyolefin composition of the sixth aspect comprises a polyolefin material. Suitably, the polyolefin composition of the sixth aspect comprises a polyolefin material as prepared according to the method of the first aspect.

[0348] Preferred features of the sixth aspect are as defined in relation to the first aspect. In particular, preferred features of the polyolefin material, polyolefin composition and the at least one amido alcohol compound of the sixth aspect are as set out herein in relation to the first and fifth aspects.

[0349] The polyolefin composition according to the sixth aspect comprises a detectable amount of the at least one amido alcohol compound and / or a derivative thereof. The detectable amount is 2000 ppm or less and will be readily detectable by a skilled person using detection means known in the art. Examples of suitable such methods includes CHNO (combustion) analysis, pyrolysis GC-MS and digestion followed by HPLC. However the detectable amount of amido alcohol compound and / or derivative thereof will not substantially affect the properties of the polyolefin composition, or of the polyolefin material therein.

[0350] The polyolefin composition according to the sixth aspect may comprise a heterophasic (impact) polypropylene copolymer, wherein the heterophasic (impact) polypropylene copolymer comprises from 1 to 60 wt%, preferably, from 20 to 45 wt%, of an ethylene-propylene copolymer (especially an ethylene-propylene copolymer rubber), and a detectable amount of the at least one amido alcohol compound and / or a derivative thereof.The polyolefin composition according to the sixth aspect is preferably obtained according to a method as defined herein in relation to the first aspect of the invention. Suitably, the polyolefin composition according to the sixth aspect is obtained by carrying out an olefinic polymerisation process on at least one olefinic monomer in the presence of an amido alcohol compound and a polymerisation catalyst as defined herein. Preferably the polymerisation catalyst is not a single site catalyst.

[0351] The polyolefin composition according to the sixth aspect is typically suitable for use in applications that contact humans, such as in food contact or in medical applications.

[0352] The polyolefin composition according to the sixth aspect may comprise one or more polyolefin materials obtained by the polymerisation reaction of the first aspect, for example wherein the polymerisation reaction produces a mixture of polyolefin materials.

[0353] The polyolefin composition according to the sixth aspect may further comprise residual olefinic monomer(s) and / or other components of the polymerisation reaction mixture, such as the polymerisation catalyst and / or a derivative thereof. The polyolefin composition may be purified to separate the polyolefin material from other components.

[0354] According to a seventh aspect of the present invention, there is provided a polyolefin composition obtained by conducting the method of the first aspect or obtained by polymerisation of the polymerisation reaction mixture according to the fifth aspect.

[0355] According to an eighth aspect of the present invention, there is provided a polyolefin material obtained by conducting the method of the first aspect or obtained by polymerisation of the polymerisation reaction mixture according to the fifth aspect. The polyolefin material may be obtained by purification of the polyolefin composition as defined herein.

[0356] The skilled person will appreciate that polyolefin compositions, and polyolefin materials, are commonly defined using particular properties familiar in the art, including melt flow rate (MFR), xylene soluble fraction (XS), polymer powder bulk density (BD), and polymer powder pourability. The skilled person will be familiar with methods of measuring these properties, however for the avoidance of doubt suitable methods for assessing the polyolefin composition according to the sixth or seventh aspect, or the polyolefin material according to the eighth aspect, are outlined below.

[0357] Melt flow rate (MFR) is suitably determined according to ISO 1133 standard method, measured at 230°C with 21 N load.Xylene soluble fraction (XS) is suitably determined according to ISO 16152 standard method.

[0358] Polymer powder bulk density (BD) is suitably determined according to ISO 60 standard method.

[0359] Polymer powder pourability is suitably determined according to ASTM D 1895 standard method using a 9.5 mm to 18 mm cone neck diameter.

[0360] The polyolefin composition according to the sixth or seventh aspect suitably comprises a homopolymer (for example polyethylene or polypropylene) or a copolymer, for example a homogeneous (random) copolymer or a heterophasic (impact) copolymer, as disclosed herein.

[0361] The polyolefin material according to the eighth aspect may is suitably a homopolymer (for example polyethylene or polypropylene) or a copolymer, for example a homogeneous (random) copolymer, as disclosed herein.

[0362] The polyolefin material according to the eighth aspect may suitably be a heterophasic (impact) copolymer, as disclosed herein.

[0363] The homopolymer suitably has a melt flow rate (MFR) according to ISO 1133 standard method at 230°C and 21 N of from 75 to 100 g / 10min, for example from 80 to 100 g / 10min, or from 80 to 95 g / 1 Omin, suitably from 85 to 95 g / 1 Omin.

[0364] The homopolymer suitably has a xylene soluble fraction (XS) according to ISO 16152 standard method of from 1.1 to 1.5 wt%, for example from 1 .2 to 1.4 wt%, or from 1.25 to 1.35 wt%.

[0365] The homopolymer suitably has a polymer powder bulk density (BD) according to ISO 60 standard method of from 350 to 450 g L-1, for example from 380 to 440 g L-1, or from 400 to 430 g L’1, suitably from 410 to 425 g L’1.

[0366] The copolymer (preferably the heterophasic (impact) copolymer) suitably has a melt flow rate (MFR) according to ISO 1133 standard method at 230°C and 21 N of from 10 to 40 g / 1 Omin, for example from 10 to 35 g / 1 Omin.

[0367] The copolymer (preferably the heterophasic (impact) copolymer) suitably has a polymer powder bulk density (BD) according to ISO 60 standard method of from 350 to 450 g L-1, for example from 380 to 440 g L’1.

[0368] The copolymer (preferably the heterophasic (impact) copolymer) suitably has a polymer powder pourability according to ASTM D 1895 through a 9.5 mm neck cone diameter of up to 50seconds, for example up to 40 seconds, or up to 30 seconds, suitably up to 25 seconds, or up to 20 seconds, preferably up to 15 seconds, or up to 12 seconds, suitably up to 10 seconds.

[0369] The copolymer (preferably the heterophasic (impact) copolymer) suitably has a polymer powder pourability according to ASTM D 1895 through a 12 mm neck cone diameter of up to 25 seconds, for example up to 20 seconds, or up to 15 seconds, suitably up to 10 seconds, or up to 8 seconds, preferably up to 7 seconds, or up to 5 seconds.

[0370] The copolymer (preferably the heterophasic (impact) copolymer) suitably has a polymer powder pourability according to ASTM D 1895 through a 14 mm neck cone diameter of up to 20 seconds, for example up to 15 seconds, or up to 10 seconds, suitably up to 5 seconds, or up to 4 seconds, preferably up to 3 seconds.

[0371] The copolymer (preferably the heterophasic (impact) copolymer) suitably has a polymer powder pourability according to ASTM D 1895 through a 16 mm neck cone diameter of up to 15 seconds, for example up to 10 seconds, or up to 5 seconds, suitably up to 4 seconds, or up to 3 seconds, preferably up to 2.5 seconds.

[0372] The copolymer (preferably the heterophasic (impact) copolymer) suitably has a polymer powder pourability according to ASTM D 1895 through an 18 mm neck cone diameter of up to 10 seconds, for example up to 5 seconds, or up to 4 seconds, suitably up to 3 seconds, or up to 2.5 seconds, preferably up to 2 seconds.

[0373] The copolymer (preferably the heterophasic (impact) copolymer) suitably has a pourability of less than 20 seconds as measured according to ASTM 1895 using a 9.5 mm cone.

[0374] The copolymer (preferably the heterophasic (impact) copolymer) suitably has a xylene soluble fraction (XS) according to ISO 16152 standard method of from 15 to 35 wt%, for example from 20 to 35 wt%.

[0375] According to a ninth aspect of the present invention, there is provided an article made from the polyolefin composition according to the sixth or seventh aspect or made from the polyolefin material according to the eighth aspect.

[0376] Suitably the article according to the ninth aspect is a packaging product, an automotive product, a textile product, a medical product, a concrete reinforcement product, a piping product and / or an electrical cable product.The article according to the ninth aspect is typically suitable for use in applications that contact humans, such as in contact with food or in medical applications.

[0377] The article is suitably a packaging product for one or more of food, cosmetics, medical products, and laboratory items. The packaging product may be a flexible or rigid packaging product.

[0378] Preferably the article is a food packaging product.

[0379] Preferably the article is a medical product, for example a syringe product or medical packaging product.

[0380] The article is suitably an automotive product selected from one or more of instrument panels, bumpers, door trim, and other interior plastics.

[0381] The article is suitably a tape product, continuous filament product, strapping product, or raffia product for use in the fabric industry for clothing and nappies (diapers).

[0382] Brief description of the figures

[0383] For a better understanding of the invention, and to show how exemplary embodiments of the same may be carried into effect, reference will be made, by way of example only, to the accompanying diagrammatic Figures, in which:

[0384] Figures 1 and 2 show the degree of reactor fouling during gas-phase homopolymerisation of propylene in Example 1 , when no amido alcohol compound is present.

[0385] Figures 3 and 4 show the degree of reactor fouling during the gas-phase homopolymerisation of propylene in Example 1 , at a treat rate of 60 ppm wt. (based on the amount of propylene present) of / V-oleyl N,N-di(isopropanol)amide.

[0386] Figure 5 shows the effect of / V-oleyl N,N-di(isopropanol)amide on the electric current generated during the gas-phase homopolymerisation of propylene in Example 1 , compared to the electric current generated when no amido alcohol compound is present.

[0387] The invention will now be further described with reference to the following non-limiting examples.

[0388] ExamplesPolymerisation-grade propylene was further purified by passing through six purification columns. The content of each of CO and COS in propylene after purification was below 10 vol. ppb, and water and oxygen levels were below 0.1 vol. ppm.

[0389] Commercial polymerisation-grade ethylene was purified in the same manner and to the same impurities specification as the polymerisation-grade propylene.

[0390] Triethylaluminium (TEA) with ultra-low aluminium hydride content (< 0.05 wt.%) was used as a co-catalyst in an n-heptane solution at a concentration of 200 mg / ml. It was stored in a glass vessel under nitrogen.

[0391] Cyclohexylmethyldimethoxysilane (C HMD MS) was used as an external donor compound and was diluted in n-heptane at a concentration of 0.2 mmol / ml and stored in a glass vessel under nitrogen.

[0392] Commercial MgCh-supported Ziegler-Natta catalyst was dispersed in white mineral oil with a concentration of 11 wt%.

[0393] All of the amido alcohol compounds were diluted in n-heptane to a suitable concentration and stored in glass vessels under nitrogen. For homopolymerisation, the amido alcohol compounds were diluted in n-heptane to 18 mg / ml. For heterophasic copolymerization, the amido alcohol compounds were diluted in n-heptane to 244 mg / ml.

[0394]

[0395] 1 : Gas-Phase

[0396] A 2-litre stainless steel reactor was purified by nitrogen flushing at 95°C for about 30 minutes. Then a 15-minute pressure test at 95°C and 3.0 MPa was performed. Subsequently, the reactor was cooled down to 40°C under continuous nitrogen flushing.

[0397] TEA and CHMDMS in n-heptane were charged to the reactor by micropipette. The reactor was then charged with 65 g of propylene. An initial dose of hydrogen 110 mmol was charged at 0.8 MPa. The catalyst as a mineral oil slurry in the amount shown below in Table 1 was then injected by micropipette into the charging device and flushed into the pressurised reactor at 40°C with 25 g of liquid propylene.

[0398] After component dosing, the reactortemperature was raised from 40°C to 75°C in 3 to 5 minutes. The polymerisation was performed at 75°C and 2.2 MPa(g) in the gas phase for 70 to 90 minutes until the target weight of 240 to 260 g of polypropylene was produced. Hydrogen was continuously supplemented during the polymerization reaction. The amido alcohol compoundwas flushed with 5 g propylene at 10 minutes after catalyst injection (approximately 6 to 7 minutes after propylene evaporation, i.e. once the propylene has become a gas upon heating). The amido alcohol compound was added to the reactor in a weight ratio relative to the weight of propylene present in the reactor (ppm wt.).

[0399] Summary of homopolymerisation conditions:

[0400] TEA / Ti = 100 mol / mol

[0401] CHMDMS / Ti = 10 mol / mol

[0402] H2 = 110 mmol

[0403] Temperature = 75°C

[0404] Pressure = 2.2 Mpa(g)

[0405] Melt flow rate = 90 to 100 g / IOmin

[0406] The results of the reactor fouling are shown in Figures 1 to 4, as discussed below.

[0407] The effect of the amido alcohol on reactor fouling was determined visually by observing the severity of polymer powder deposits on the surfaces in and around a reactor vessel after conducting the homopolymerisation reaction.

[0408] The severity of reactor fouling was categorised as follows:

[0409] No fouling: minimal residual power deposits on the reactor cover, stirrer, walls, and the space immediately surrounding the opening in the reactor.

[0410] Low fouling: minor powder deposits on the reactor stirrer and walls. Minimal powder deposits on the reactor cover and the space immediately surrounding the opening in the reactor.

[0411] Moderate fouling: Significant powder deposits on the reactor cover, stirrer and walls. A small quantity of powder was ejected from the reactor upon opening due to static repulsion and deposited on the space immediately surrounding the opening in the reactor.

[0412] Severe fouling: Heavy powder deposits on the reactor cover, stirrer and walls including agglomeration of powder into lumps. A significant quantity of powder was ejected from the reactor upon opening due to static repulsion and deposited on the space immediately surrounding the opening in the reactor.

[0413] The effect of the amido alcohol compounds on static was also determined by measuring the electrical current generated during the polymerisation process, particularly after 10 minutes.Measurement of Electrostatic Charge

[0414] The electrostatic charge generated on the polymer particles during polymerisation was collected by the stirrer and shaft, both electrically isolated from the grounded magnetic coupling and the reactor body. The probe of the Statometer III device (HAUG, Germany) was placed near a metal disc held in a small chamber under nitrogen outside the reactor. The Statometer III measured potential corresponded to the voltage between the insulated stirrer and the grounded reactor body.

[0415] The capacitor was periodically grounded, which removed the accumulated charge. The slope of the charge was evaluated from each profile of the capacitor charge. The determined value of the charging slope then corresponded to the instantaneous rate of voltage generation during polymerisation.

[0416] The fouling and static reduction results are shown in Table 1.

[0417] Table 1

[0418] Treat-rate Catalyst

[0419] (PPm by amount

[0420] Amido alcohol Visual reactor Static after 10 weight based (mg)

[0421] compound fouling results minutes

[0422] on

[0423] propylene)

[0424] Severe fouling.

[0425] 19 nA

[0426] None (reference)* N / A 10 Shown in figures

[0427] See Figure 5 1&2

[0428] / V-oleyl N,N- No fouling.

[0429] 2.3 nA di(isopropanol)amide 60 7 Shown in figures

[0430] See Figure 5 3&4

[0431]

[0432] *Repeat of example 1 without an amido alcohol compound.

[0433] Example 2: Gas-Phase Sequential Copolymerisation for Heterophasic Copolymer (HCP)

[0434] Polypropylene homopolymer was prepared according to the process in Example 1 using 10mg catalyst and without the addition of an amido alcohol compound. The homopolymerisation was performed until the desired homopolypropylene material was synthesised. After the homopolymerisation phase, the reactor was depressurised below 0.01 MPa(g) and suitable amounts of amido alcohol compound, hydrogen, ethylene and propylene were introduced into the reactor within 90 seconds to provide the desired gas-phase composition andcopolymerisation pressure. The amido alcohol was flushed into the reactor with liquid propylene during the 90 second transition period in the desired weight ratio to the polypropylene synthesised during the homopolymerisation phase.

[0435] The temperature and pressure during the copolymerisation phase was 75°C and 2.2 MPa(g). Hydrogen and ethylene were continuously supplemented to the reactor to maintain constant gas-phase composition during the copolymerisation. The gas-phase composition was checked by GC analysis every 23 minutes. The copolymerisation phase was carried out until a fixed amount of ethylene-propylene copolymer / rubber (EPR) content was achieved [25 or 35 wt%].

[0436] Summary of copolymerisation conditions:

[0437] Propylene = 52 g

[0438] Ethylene = 7.5 g

[0439] Hydrogen = 11 mmol

[0440] Temperature = 75°C

[0441] Pressure = 2.2 MPa(g)

[0442] Ethylene in EPR = 35 wt%

[0443] Amido alcohol compound: (A) / V-oleyl- / V, / V-di(isopropanol)amide

[0444] After polymerisation, the reactor was depressurised and cooled to 40°C. The polymer powder was then removed from the reactor, placed in a vacuum oven and dried at 70°C for 2 hours.

[0445] A polymer powder pourability test was performed according to ASTM D 1895 standard method and the results are summarised in Table 2 below.

[0446] Table 2

[0447] Amount Pourability (seconds) Amido

[0448] (PPm by EPR 9.5 12 14 16 18 Polymer alcohol

[0449] weight / H wt%* mm mm mm mm mm compound

[0450] PP) Cone Cone Cone Cone Cone Homo- None 0 N / A 8.3 4.6 2.9 2.1 1.7 PP

[0451] None 0 24.7 999.0 999.0 43.0 9.6 4.5 HCP

[0452] A 101 35.4 9.1 4.7 3.0 2.3 1.8

[0453]

[0454] wt% EPR by mass of overall polymerTable 2 shows that the HCP polymer prepared without an amido alcohol compound added is sticky and does not flow or pour. In contrast, the HCP polymer prepared with the amido alcohol compounds added has a similar flow time as the homopolypropylene.

[0455] The present invention is not restricted to the details of the foregoing embodiment(s). The invention extends to any novel one, or any novel combination, of the features disclosed in this specification (including any accompanying claims, abstract and drawings), or to any novel one, or any novel combination, of the steps of any method or process so disclosed.

Claims

Claims1. A method of making a polyolefin material, the method comprising at least one step of polymerising at least one olefinic monomer in the presence of at least one polymerisation catalyst and at least one amido alcohol compound; wherein the or each amido alcohol compound is of the formula R1C(O)NR2R3, wherein R1is an optionally substituted C5-23 hydrocarbyl group, and each of R2and R3is independently a hydrocarbyl group having at least three carbon atoms and wherein each hydrocarbyl group R2and R3is substituted by at least one hydroxy group and optionally one or more further substituents.

2. Use of an amido alcohol compound in an olefinic polymerisation process, wherein the olefinic polymerisation process comprises at least one step of the polymerisation at least one olefinic monomer in the presence of at least one polymerisation catalyst; wherein the or each amido alcohol compound is of the formula R1C(O)NR2R3, wherein R1is an optionally substituted C5-23 hydrocarbyl group, and each of R2and R3is independently a hydrocarbyl group having at least three carbon atoms and wherein each hydrocarbyl group R2and R3is substituted by at least one hydroxy group and optionally one or more further substituents.

3. A method of providing at least one improvement during an olefinic polymerisation process, the method comprising:(a) providing a polymerisation reaction mixture comprising at least one olefinic monomer, at least one polymerisation catalyst and at least one amido alcohol compound; and (b) carrying out a polymerisation process;wherein the or each amido alcohol compound is of the formula R1C(O)NR2R3, wherein R1is an optionally substituted C5-23 hydrocarbyl group, and each of R2and R3is independently a hydrocarbyl group having at least three carbon atoms and wherein each hydrocarbyl group R2and R3is substituted by at least one hydroxy group and optionally one or more further substituents.

4. Use of an amido alcohol compound to provide at least one improvement during an olefinic polymerisation process, wherein the olefinic polymerisation process comprises the polymerisation of at least one olefinic monomer in the presence of at least one polymerisation catalyst; wherein the or each amido alcohol compound is of the formula R1C(O)NR2R3, wherein R1is an optionally substituted C5-23 hydrocarbyl group, and each of R2and R3is independently a hydrocarbyl group having at least three carbon atoms and wherein each hydrocarbyl group R2and R3is substituted by at least one hydroxy group and optionally one or more further substituents.

5. A method or use according to claim 3 or 4, wherein the at least one improvement is selected from one or more of:• a reduction in reactor fouling;• a reduction in reactor static; and• an improvement in product powder pourability;compared to an equivalent method or use without the or each amido alcohol compound present.

6. A polymerisation reaction mixture comprising:(i) at least one olefinic monomer;(ii) at least one polymerisation catalyst; and(iii) at least one amido alcohol compound,wherein the or each amido alcohol compound is of the formula R1C(O)NR2R3, wherein R1is an optionally substituted C5-23 hydrocarbyl group, and each of R2and R3is independently a hydrocarbyl group having at least three carbon atoms and wherein each hydrocarbyl group R2and R3is substituted by at least one hydroxy group and optionally one or more further substituents.

7. A method, use or polymerisation reaction mixture according to any preceding claim, wherein R1is an optionally substituted C7-23 or Cn-17 alkyl, cycloalkyl, alkenyl, cycloalkenyl, aryl, or alkaryl group, preferably an optionally substituted C7-23 or Cn-17 alkyl or alkenyl group.

8. A method, use or polymerisation reaction mixture according to any preceding claim, wherein R1is a C5-23 alkyl group, preferably a linear C5-23 alkyl group, or wherein R1is an unsaturated group, preferably a linear unsaturated group.

9. A method, use or polymerisation reaction mixture according to any preceding claim, wherein the or each amido alcohol compound is of the formula (I):NHO OH (I) wherein R1is as defined in any of claims 1 to 4, 6, 7 or 8 and R4and R5are each independently an optionally substituted C1-6 alkyl, C2-6 alkenyl, C3-8 cycloalkyl, C3-8 cycloalkenyl or Cs- aryl group.

10. A method, use or polymerisation reaction mixture according to claim 9, wherein R4and R5are each independently selected from a methyl, ethyl, propyl, phenyl or cyclohexenyl group.

11. A method, use or polymerisation reaction mixture according to any preceding claim, wherein the or each amido alcohol compound is a liquid at 25°C and standard pressure (101325Pa).

12. A method, use or polymerisation reaction mixture according to any preceding claim, wherein the or each amido alcohol compound is a liquid at standard pressure and at a temperature of from 0°C to 80°C, more preferably at a temperature of from -5°C to 80°C, even more preferably at a temperature of from -15°C to 80°C or from -20°C to 80°C.

13. A method, use or polymerisation reaction mixture according to any preceding claim, wherein the or each olefinic monomer is a C2-20 a-olefin, preferably selected from one or more of ethylene, propylene, butylene and isobutylene (including mixtures thereof).

14. A method, use or polymerisation reaction mixture according to claim 13, wherein the or each olefinic monomer is selected from one or more of ethylene and propylene (including mixtures thereof).

15. A method, use or polymerisation reaction mixture according to any preceding claim, wherein the at least one olefinic monomer is selected from at least two different olefinic monomers.

16. A method or use according to any one of claims 1 to 5 and 7 to 14, wherein the polyolefin material formed by the method or use is a homopolymer.

17. A method or use according to any one of claims 1 to 5 and 7 to 15, wherein the polyolefin material formed by the method or use is a copolymer, preferably a homogeneous (random) copolymer or a heterophasic (impact) copolymer.

18. A method or use according to any one of claims 1 to 5 and 7 to 17, wherein the polyolefin material formed by the method or use is a free-flowing powder.

19. A method, use or polymerisation reaction mixture according to any preceding claim, wherein the or each polymerisation catalyst comprises a Ziegler-Natta catalyst and / or a metallocene catalyst.

20. A polyolefin composition comprising a polyolefin material and a detectable amount of at least one amido alcohol compound and / or a derivative thereof, wherein the or each amido alcohol compound is of the formula R1C(O)NR2R3, wherein R1is an optionally substituted C5-23 hydrocarbyl group, and each of R2and R3is independently a hydrocarbyl group having at least three carbon atoms and wherein each hydrocarbyl group R2and R3is substituted by at least one hydroxy group and optionally one or more further substituents, and wherein the detectable amount is 2000 ppm or less.

21. A polyolefin composition obtained by conducting the method of claim 1 or obtained by polymerisation of the polymerisation reaction mixture according to the claim 6.

22. A polyolefin material obtained by conducting the method of claim 1 or obtained by polymerisation of the polymerisation reaction mixture according to the claim 6.

23. A polyolefin composition according to claim 20, or a polyolefin material according to claim 22, wherein the polyolefin material is a heterophasic (impact) copolymer with a pourability of less than 20 seconds as measured according to ASTM 1895 using a 9.5 mm cone.

24. An article comprising the polyolefin composition of claim 20, 21 or 23, or the polyolefin material of claim 22 or 23.

25. An article according to claim 24, wherein the article is a packaging product.

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