Method and use

Abstract

Method and Use 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 amino alcohol compound; wherein the or each polymerisation catalyst comprises a Ziegler-Natta catalyst and wherein the or each amino alcohol compound is of the formula NR1R2R3, wherein R1 is an optionally substituted C6-20 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 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 the amino alcohol compounds and to methods of using the amino alcohol compounds in the polymerisation of olefinic monomers, and to polymerisation reaction mixtures comprising amino 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.

[0008] 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 reactor and / or particle fouling in a polymer manufacturing process, whilst meeting the current and future regulatory constraints on polymerisation additives.

[0009] Summary

[0010] 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 amino alcohol compound; wherein the or each polymerisation catalyst comprises a Ziegler-Natta catalyst and wherein the or each amino alcohol compound is of the formula NR1R2R3, wherein R1is an optionally substituted Ce-2o 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 second aspect of the present invention, there is provided a use of an amino 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 polymerisation catalyst comprises a Ziegler-Natta catalyst and wherein the or each amino alcohol compound is of the formula NR1R2R3, wherein R1is an optionally substituted Ce-2o 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.

[0012] 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:

[0013] (a) providing a polymerisation reaction mixture comprising at least one olefinic monomer, at least one polymerisation catalyst and at least one amino alcohol compound; and

[0014] (b) carrying out a polymerisation process; wherein the or each polymerisation catalyst comprises a Ziegler-Natta catalyst and wherein the or each amino alcohol compound is of the formula NR1R2R3, wherein R1is an optionally substituted Ce-2o 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 fourth aspect of the present invention, there is provided a use of an amino 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 polymerisation catalyst comprises a Ziegler-Natta catalyst and wherein the or each amino alcohol compound is of the formula NR1R2R3, wherein R1is an optionally substituted Ce-2o 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.

[0016] According to a fifth aspect of the present invention, there is provided a polymerisation reaction mixture comprising:

[0017] (i) at least one olefinic monomer;

[0018] (ii) at least one polymerisation catalyst; and

[0019] (iii) at least one amino alcohol compound, wherein the or each polymerisation catalyst comprises a Ziegler-Natta catalyst and wherein the or each amino alcohol compound is of the formula NR1R2R3, wherein R1is an optionally substituted Ce-2o 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 amino alcohol compound and / or a derivative thereof, wherein the or each amino alcohol compound is of the formula NR1R2R3, wherein R1is an optionally substituted Ce-2o 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. 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.

[0023] Detailed description

[0024] Unless 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’. 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.

[0031] 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.

[0032] 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.

[0033] 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.

[0034] Unless otherwise mentioned all references to ppm in this specification are to parts per million by weight.

[0035] Unless otherwise stated herein, the reference to “liquid” and “solid” refer to a state at 25°C and standard pressure (101 ,325 Pa).

[0036] 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 amino alcohol compound; wherein the or each polymerisation catalyst comprises a Ziegler-Natta catalyst and wherein the or each amino alcohol compound is of the formula NR1R2R3, wherein R1is an optionally substituted Ce-2o hydrocarbyl group, and each of R2and R3is independently a hydrocarbyl group having at least three carbon atoms and wherein each hydrocarbyl group R2 and R3is substituted by at least one hydroxy group and optionally one or more further substituents.

[0037] 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.

[0038] By a “polyolefin material” we mean a material that comprises or consists essentially of one or more polyolefins.

[0039] 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 homo polymer, such that the method of the first aspect may comprise polymerising one olefinic monomer to make a polyolefin material that is a homo polymer.

[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 a semi-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 ethylene- propylene 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 / orto 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 amino alcohol compound of the formula NR1R2R3, wherein R1is an optionally substituted Ce-2o 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 amino alcohol compounds.

[0054] For the avoidance of doubt, when we refer to an optionally substituted Ce-2o hydrocarbyl group, we mean that the hydrocarbyl group (without any optional substituents) contains from 6 to 20 carbon atoms, such that any substituents may contain further carbon atoms in addition to the 6 to 20 carbon atoms of the hydrocarbyl group. The same applies to the Cs-is or C3-6 etc hydrocarbyl groups as defined herein.

[0055] In the formula NR1R2R3, R1is an optionally substituted Ce-20 hydrocarbyl group. For example, R1may suitably be an optionally substituted Cs-is hydrocarbyl group, or preferably an optionally substituted C8-12 hydrocarbyl group, or preferably an optionally substituted C12-18 hydrocarbyl group.

[0056] Suitably, R1may be optionally substituted with any suitable substituents. Examples of suitable substituents may include hydroxy, C1-4 alkoxy and / or halo groups.

[0057] Preferably, R1may be an optionally substituted C6-20 (for example Cs-is, C8-12 or C12-18) alkyl, cycloalkyl, alkenyl, cycloalkenyl, aryl, or alkaryl group.

[0058] More preferably, R1may be an optionally substituted C6-20 (suitably Cs-is, C8-12 or C12-18) alkyl or alkenyl group.

[0059] More preferably, R1may be an optionally substituted C6-20 (suitably Cs- orCs-^) alkyl group.

[0060] More preferably, R1may be an optionally substituted C6-20 (suitably Cs-is or C12-18) alkenyl group.

[0061] Preferably, when R1is an optionally substituted C6-20 (suitably Cs-is, C8-12 or C12-18) alkyl or alkenyl group, the alkyl or alkenyl group is linear.

[0062] For example, R1may be an optionally substituted octyl, dodecyl, or oleyl group, more preferably an optionally substituted n-octyl, n-dodecyl, or n-oleyl group. Most preferably R1is an oleyl group, preferably an n-oleyl group.

[0063] Preferably R1is unsubstituted.

[0064] Preferably, R1may be an unsubstituted Ce-2o (suitably Cs-is, Cs-12 or C12-18) alkyl or alkenyl group.

[0065] More preferably, R1may be an unsubstituted C6-20 (suitably Cs-is orCs-12) alkyl group.

[0066] More preferably, R1may be an unsubstituted C6-20 (suitably Cs-is or Ci2-is) alkenyl group.

[0067] Preferably, R1may be an unsubstituted linear C6-20 (suitably Cs-is, C8-12 or C12-18) alkyl or alkenyl group.

[0068] More preferably, R1may be an unsubstituted linear C6-20 (suitably Cs-is orCs-12) alkyl group.

[0069] More preferably, R1may be an unsubstituted linear C6-20 (suitably Cs-is or C12-18) alkenyl group.

[0070] Preferably, R1is an unsubstituted octyl, dodecyl, or oleyl group, more preferably an unsubstituted n-octyl, n-dodecyl, or n-oleyl group.

[0071] Most preferably R1is an unsubstituted oleyl group, preferably an unsubstituted n-oleyl group.

[0072] In the formula NR1R2R3, 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.

[0073] Preferably, each of R2and R3is substituted by only one (i.e. a single) hydroxy group.

[0074] Preferably, each of R2and R3is substituted by at least one hydroxy group and is not further substituted.

[0075] Preferably, each of R2and R3is substituted by only one (i.e. a single) hydroxy group and is not further substituted.

[0076] R2and R3may be the same or different. Preferably R2and R3are the same. 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.

[0077] 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.

[0078] 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.

[0079] 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.

[0080] 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.

[0081] 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 C36-20 (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.

[0082] 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.

[0083] 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. 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.

[0084] 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.

[0085] 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.

[0086] 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.

[0087] Preferably, R1is an unsubstituted linear C6-20 (suitably Cs-is, C8-12 or C12-18) 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 carbon atoms, wherein each of R2and R3is substituted by at least one hydroxy group and optionally one or more further substituents.

[0088] Preferably, R1is an unsubstituted linear C6-20 (suitably Cs-is, C8-12 or C12-18) 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 carbon atoms, wherein each of R2and R3is substituted by at least one hydroxy group and optionally one or more further substituents.

[0089] Preferably, R1is an unsubstituted linear C6-20 (suitably Cs-is, C8-12 or C12-18) 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.

[0090] Preferably, R1is an unsubstituted linear C6-20 (suitably C12-18) 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.

[0091] Preferably, the or each amino alcohol compound may be of the formula (I): 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.

[0092] R4and R5may be the same or different. Preferably R4and R5are the same.

[0093] 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.

[0094] 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.

[0095] Preferably each of R4and R5is a methyl group.

[0096] Preferably in the formula (I), R1is an optionally substituted C6-20 alkyl or alkenyl group.

[0097] Preferably in the formula (I), R1is an optionally substituted C6-20 alkyl or alkenyl group and R4and R5are each independently an optionally substituted C1-6 alkyl or Cs- aryl group.

[0098] Preferably in the formula (I), R1is an optionally substituted C6-20 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.

[0099] 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: wherein R1, R4and R5are as defined herein in relation to formula (I). Preferably, the or each amino alcohol compound may be selected from one or more of / V-octyl N,N-di(isopropanol)amine, / V-oleyl-N,N-di(isopropanol)amine and / V-dodecyl N,N- di(isopropanol)amine. More preferably the amino alcohol is / V-oleyl-N,N-di(isopropanol)amine.

[0100] The or each amino alcohol compound may be commercially available or can be readily prepared using procedures well known to those skilled in the art.

[0101] For example the or each amino alcohol compound may be the reaction product of an amine of formula NHR2R3and a compound of formula R1X, wherein X is a halogen group, preferably bromine and R1, R2and R3are as defined herein.

[0102] However, preferably the or each amino alcohol compound is the reaction product of an amine of formula NH2R1(wherein R1is as defined herein) and one or more alkylene oxide compounds having at least 3 carbon atoms, for example propylene oxide.

[0103] Suitably the or each amino alcohol compound is the reaction product of an amine of formula NH2R1(wherein R1is as defined herein) and at least 2 molar equivalents of one or more alkylene oxide compound having at least 3 carbon atoms, for example propylene oxide.

[0104] Suitably the or each amino alcohol compound is the reaction product of an amine of formula NH2R1(wherein R1is as defined herein) and at least 2 molar equivalents of propylene oxide.

[0105] Suitably the or each amino alcohol compound is the reaction product of an amine of formula NH2R1(wherein R1is as defined herein) and from 2 to 4 molar equivalents of one or more alkylene oxide compound having at least 3 carbon atoms, for example propylene oxide.

[0106] Suitably the or each amino alcohol compound is the reaction product of an amine of formula NH2R1(wherein R1is as defined herein) and from 2 to 4 molar equivalents of propylene oxide.

[0107] Preferably the or each amino alcohol compound is the reaction product of / V-octyl amine, / V-oley I amine or / V-dodecyl amine (preferably / V-oleyl amine) and at least 2 molar equivalents of propylene oxide.

[0108] Preferably the or each amino alcohol compound is the reaction product of / V-octyl amine, / V-oleyl amine or / V-dodecyl amine (preferably / V-oleyl amine) and from 2 to 4 molar equivalents of propylene oxide. The skilled person will appreciate that commercial sources of reactants for preparing the amino alcohol compounds (such as discussed above) may be provided as mixtures of compounds and / or isomers thereof.

[0109] For example, when an amine of formula NH2R1is used to prepare the amino alcohol compound (by reaction with one or more alkylene oxide compounds) and R1is an optionally substituted Ce- 20 alkenyl group, the alkenyl group may comprise a distribution of chain lengths, so as to provide the amino alcohol compound having such a distribution of chain lengths. For example, when R1represents an oleyl group, the oleyl group may comprise a distribution of chain lengths. Preferably when R1represents an oleyl group at least 75 mol% of the R1groups are C alkenyl groups, more preferably at least 85 mol%, or at least 90 mol%.

[0110] 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.

[0111] 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 .

[0112] For example, where the or each amino alcohol compound is / V-oleyl-N,N-di(isopropanol)amine, the molar ratio of cis-isomers to trans-isomers is preferably 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 / V-oleyl-N,N-di(isopropanol)amine, 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.

[0113] Preferably the or each amino alcohol compound has an iodine value of at least 70 g I2 / I OO g, such as at least 75 g I2 / I OO g, or at least 80 g I2 / I OO g, for example at least 85 g I2 / I OO g, preferably at least 90 g I2 / 100 g.

[0114] Preferably the or each amino alcohol compound has an iodine value of from 70 to 120 g I2 / I OO g, such as from 75 to 120 g I2 / I OO g, or from 80 to 120 g I2 / I OO g, for example from 85 to 110 g I2 / 100 g, preferably from 90 to 100 g I2 / 100 g.

[0115] The skilled person will appreciate that an amino alcohol compound that is prepared by an industrial, especially alkoxylation, process may have a distribution of alcohol substituents therein. The amino alcohol compound prepared by this process may additionally comprise one or more (such as one) alkoxy substituents and may have a distribution of alkoxy substituents. The alkoxy substituent may occur due to the reaction of a double bond in the R1group with the alkylene oxide compound having at least 3 carbon atoms (for example propylene oxide).

[0116] The or each amino 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 amino alcohol compound is used in the method of the first aspect as a single additive, i.e. without being formulated into an additive composition. For example the or each amino 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.

[0117] Alternatively, for example, the or each amino alcohol compound may be used in the method of the first aspect in the form of a solution. Suitable solutions may comprise any suitable solvent(s), such as a non-polar aprotic solvent (such as n-pentane, n-hexane or n-heptane).

[0118] Preferably, the or each amino alcohol compound is a liquid at 25°C and standard pressure (101 ,325 Pa).

[0119] Preferably, the or each amino 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, most preferably at a temperature of from -25°C to 80°C. This offers advantages for low temperature storage and / or handling of the amino alcohol in use, for example enabling the polymerisation method to be conveniently conducted in lower temperature environments.

[0120] The use of at least one amino 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.

[0121] The or each amino 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.

[0122] For example, the amino 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 amino alcohol compound when one or more such compound is used. When the method of the first aspect is for making homo polypropylene (i.e. wherein the one or more olefinic monomers is propylene), the amino 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).

[0123] 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 amino alcohol compound(s) may be used in an amount of from 1 to 2000 ppm, such as from 60 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 a copolymer component of a heterophasic (impact) polypropylene copolymer (such as wherein the one or more olefinic monomers are propylene and ethylene), the amino 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).

[0125] 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 amino 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.

[0126] The polymerisation catalyst(s) is suitably used in the method of the first aspect in a weight excess compared to the amino alcohol compound(s). For example, the weight ratio of the total polymerisation catalyst(s) to the total amino 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 .

[0127] Suitably, the or each amino alcohol compound does not affect the melt flow rate (MFR) of the polyolefin material obtained by the method of the first aspect.

[0128] Suitably the or each amino alcohol compound does not affect the polymer powder bulk density (BD) of the polyolefin material obtained by the method of the first aspect.

[0129] Suitably the or each amino alcohol compound does not affect the xylene soluble response (XS) of the polyolefin material obtained by the method of the first aspect.

[0130] 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. The method 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.

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

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

[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.

[0140] The polyolefin material formed by the method of the first aspect may be a free-flowing powder. 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 homo polypropylene. 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 wherein the or each polymerisation catalyst comprises a Ziegler-Natta catalyst. Any suitable polymerisation catalyst comprising a Ziegler-Natta catalyst may be used.

[0156] 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(l I l)Ch or Ti(l V)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 (CHMDMS)).

[0157] Suitably the or each polymerisation catalyst does not comprise a single site catalyst.

[0158] Examples of further suitable polymerisation catalysts for use in the method of the first aspect include chromium-based catalysts.

[0159] The or each polymerisation catalyst may be a supported catalyst. For example the polymerisation catalyst may be an MgCh-supported catalyst.

[0160] Suitably the or each polymerisation catalyst may be an MgCh-supported Zeigler-Natta catalyst.

[0161] 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.

[0162] 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).

[0163] Suitably the or each polymerisation catalyst may be provided as a dispersion in a suitable medium, such as a mineral oil.

[0164] 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.

[0165] 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, diethyl zinc (with hydrogen being preferred).

[0166] The method of the first aspect may be conducted using any suitable reaction conditions.

[0167] 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. 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.

[0168] 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).

[0169] 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.

[0170] The method of the first aspect may be carried out as a gas phase polymerisation.

[0171] 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.

[0172] 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, which homopolymer is subsequently transferred to a second reaction step wherein copolymerisation occurs on the particles of the homopolymer.

[0173] 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.

[0174] 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 amino 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 amino alcohol compound to prepare a heterophasic (impact) copolymer; wherein the or each polymerisation catalyst comprises a Ziegler-Natta catalyst and wherein the or each amino alcohol compound is of the formula NR1R2R3, wherein R1is an optionally substituted Ce-2o 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. 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],

[0175] 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.

[0176] The method of the first aspect may provide the polyolefin material as a component of a polyolefin composition. In otherwords, 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 amino 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.

[0177] 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.

[0178] Suitably the method according to the first aspect provides at least one improvement selected from:

[0179] • a reduction in reactor fouling;

[0180] • a reduction in reactor static; and / or

[0181] • an improvement in product powder pourability; compared to an equivalent method without the or each amino alcohol compound present as discussed herein.

[0182] According to a second aspect of the present invention, there is provided a use of an amino 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 polymerisation catalyst comprises a Ziegler-Natta catalyst and wherein the or each amino alcohol compound is of the formula NR1R2R3, wherein R1is an optionally substituted Ce-2o 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.

[0183] 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 amino 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.

[0184] 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.

[0185] 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:

[0186] (a) providing a polymerisation reaction mixture comprising at least one olefinic monomer, at least one polymerisation catalyst and at least one amino alcohol compound; and

[0187] (b) carrying out a polymerisation process; wherein the or each polymerisation catalyst comprises a Ziegler-Natta catalyst and wherein the or each amino alcohol compound is of the formula NR1R2R3, wherein R1is an optionally substituted Ce-2o 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.

[0188] 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 amino 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 amino alcohol compound may be admixed simultaneously to provide the polymerisation reaction mixture.

[0189] 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.

[0190] 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.

[0191] According to a fourth aspect of the present invention, there is provided a use of an amino 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 polymerisation catalyst comprises a Ziegler-Natta catalyst and wherein the or each amino alcohol compound is of the formula NR1R2R3, wherein R1is an optionally substituted Ce-2o 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.

[0192] 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 amino 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.

[0193] For the avoidance of doubt, by “polymerisation reaction mixture” we mean a composition comprising components intended to polymerise to form a polymer.

[0194] The polymerisation reaction mixture comprises at least one olefinic monomer, at least one polymerisation catalyst and at least one amino alcohol compound as disclosed herein.

[0195] For example, the polymerisation reaction mixture may comprise:

[0196] (i) at least one olefinic monomer;

[0197] (ii) at least one polymerisation catalyst comprising a Ziegler-Natta catalyst; and

[0198] (iii) at least one amino alcohol compound NR1R2R3as defined herein.

[0199] Preferably, the polymerisation reaction mixture may comprise:

[0200] (i) propylene and ethylene;

[0201] (ii) at least one polymerisation catalyst comprising a Ziegler-Natta catalyst; and

[0202] (iii) at least one amino alcohol compound NR1R2R3as defined herein.

[0203] Preferably, the polymerisation reaction mixture may comprise:

[0204] (i) propylene;

[0205] (ii) at least one polymerisation catalyst comprising a Ziegler-Natta catalyst; and

[0206] (iii) at least one amino alcohol compound NR1R2R3as defined herein.

[0207] For example, the polymerisation reaction mixture may comprise:

[0208] (i) at least one olefinic monomer; (ii) at least one polymerisation catalyst comprising a MgCh-supported Ziegler-Natta catalyst; and

[0209] (iii) at least one amino alcohol compound NR1R2R3as defined herein.

[0210] For example, the polymerisation reaction mixture may comprise:

[0211] (i) propylene and ethylene;

[0212] (ii) at least one polymerisation catalyst comprising a MgCh-supported Ziegler-Natta catalyst; and

[0213] (iii) at least one amino alcohol compound NR1R2R3as defined herein.

[0214] For example, the polymerisation reaction mixture may comprise:

[0215] (i) propylene;

[0216] (ii) at least one polymerisation catalyst comprising a MgCh-supported Ziegler-Natta catalyst; and

[0217] (iii) at least one amino alcohol compound NR1R2R3as defined herein.

[0218] For example, the polymerisation reaction mixture may comprise:

[0219] (i) at least one olefinic monomer;

[0220] (ii) at least one polymerisation catalyst comprising a Ziegler-Natta catalyst; and

[0221] (iii) at least one amino alcohol compound of the formula (I) as defined herein for example wherein R1is an optionally substituted Ce-2o alkyl or alkenyl group and R4and R5are each independently an optionally substituted Ci-e alkyl or Ce- aryl group (for example at least one amino alcohol compound of the formula (I) selected from one or more of / V-octyl N,N-di(isopropanol)amine, / V-oleyl-N,N- di(isopropanol)amine and / V-dodecyl N,N-di(isopropanol)amine).

[0222] Preferably, the polymerisation reaction mixture may comprise:

[0223] (i) propylene and ethylene;

[0224] (ii) at least one polymerisation catalyst comprising a Ziegler-Natta catalyst; and

[0225] (iii) at least one amino alcohol compound of the formula (I) as defined herein for example wherein R1is an optionally substituted Ce-2o alkyl or alkenyl group and R4and R5are each independently an optionally substituted Ci-e alkyl or Ce- aryl group (for example at least one amino alcohol compound of the formula (I) selected from one or more of / V-octyl N,N-di(isopropanol)amine, / V-oleyl-N,N- di(isopropanol)amine and / V-dodecyl N,N-di(isopropanol)amine).

[0226] Preferably, the polymerisation reaction mixture may comprise:

[0227] (i) propylene;

[0228] (ii) at least one polymerisation catalyst comprising a Ziegler-Natta catalyst; and (iii) at least one amino alcohol compound of the formula (I) as defined herein for example wherein R1is an optionally substituted Ce-2o alkyl or alkenyl group and R4and R5are each independently an optionally substituted Ci-e alkyl or Ce- aryl group; (for example at least one amino alcohol compound of the formula (I) selected from one or more of / V-octyl N,N-di(isopropanol)amine, / V-oleyl-N,N- di(isopropanol)amine and / V-dodecyl N,N-di(isopropanol)amine).

[0229] For example, the polymerisation reaction mixture may comprise:

[0230] (i) at least one olefinic monomer;

[0231] (ii) at least one polymerisation catalyst comprising a MgCh-supported Ziegler-Natta catalyst; and

[0232] (iii) at least one amino alcohol compound of the formula (I) as defined herein for example wherein R1is an optionally substituted Ce-2o alkyl or alkenyl group and R4and R5are each independently an optionally substituted Ci-e alkyl or Ce- aryl group; (for example at least one amino alcohol compound of the formula (I) selected from one or more of / V-octyl N,N-di(isopropanol)amine, / V-oleyl-N,N- di(isopropanol)amine and / V-dodecyl N,N-di(isopropanol)amine).

[0233] For example, the polymerisation reaction mixture may comprise:

[0234] (i) propylene and ethylene;

[0235] (ii) at least one polymerisation catalyst comprising a MgCh-supported Ziegler-Natta catalyst; and

[0236] (iii) at least one amino alcohol compound of the formula (I) as defined herein for example wherein R1is an optionally substituted Ce-2o alkyl or alkenyl group and R4and R5are each independently an optionally substituted Ci-e alkyl or Ce- aryl group; (for example at least one amino alcohol compound of the formula (I) selected from one or more of / V-octyl N,N-di(isopropanol)amine, / V-oleyl-N,N- di(isopropanol)amine and / V-dodecyl N,N-di(isopropanol)amine).

[0237] For example, the polymerisation reaction mixture may comprise:

[0238] (i) propylene;

[0239] (ii) at least one polymerisation catalyst comprising a MgCh-supported Ziegler-Natta catalyst; and

[0240] (iii) at least one amino alcohol compound of the formula (I) as defined herein for example wherein R1is an optionally substituted Ce-2o alkyl or alkenyl group and R4and R5are each independently an optionally substituted Ci-e alkyl or Ce- aryl group; (for example at least one amino alcohol compound of the formula (I) selected from one or more of / V-octyl N,N-di(isopropanol)amine, / V-oleyl-N,N- di(isopropanol)amine and / V-dodecyl N,N-di(isopropanol)amine). The polymerisation reaction mixture may comprise a suitable reaction medium as discussed above.

[0241] 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, isobutane, pentane, hexane, heptane (including mixtures thereof).

[0242] 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.

[0243] 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).

[0244] Suitably the at least one improvement of the third and fourth aspects is selected from one or more of:

[0245] • a reduction in reactor fouling;

[0246] • a reduction in reactor static; and / or

[0247] • an improvement in product powder pourability; compared to an equivalent method or use without the or each amino alcohol compound present.

[0248] A reduction in reactor fouling may be determined visually by a reduction in the number 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 amino alcohol compound present. The surfaces in and around the reactor vessel may include the reactor covers, stirrers, walls, and space immediately surrounding openings in the reactor.

[0249] 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.

[0250] 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. According to a fifth aspect of the present invention, there is provided a polymerisation reaction mixture comprising:

[0251] (i) at least one olefinic monomer;

[0252] (ii) at least one polymerisation catalyst; and

[0253] (iii) at least one amino alcohol compound, wherein the or each polymerisation catalyst comprises a Ziegler-Natta catalyst and wherein the or each amino alcohol compound is of the formula NR1R2R3, wherein R1is an optionally substituted Ce-2o 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.

[0254] 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.

[0255] The polymerisation reaction mixture of the fifth aspect may further comprise one or more suitable chain transfer agents, such as hydrogen, silanes, boranes, diethyl zinc (preferably hydrogen).

[0256] 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 amino alcohol compound of the fifth aspect are as set out herein in relation to the first aspect.

[0257] The polymerisation reaction mixture of the fifth aspect may, for example, comprise:

[0258] (i) at least one olefinic monomer;

[0259] (ii) at least one polymerisation catalyst comprising a Ziegler-Natta catalyst; and

[0260] (iii) at least one amino alcohol compound NR1R2R3as defined herein.

[0261] Preferably, the polymerisation reaction mixture of the fifth aspect may comprise:

[0262] (i) propylene and ethylene;

[0263] (ii) at least one polymerisation catalyst comprising a Ziegler-Natta catalyst; and

[0264] (iii) at least one amino alcohol compound NR1R2R3as defined herein.

[0265] Preferably, the polymerisation reaction mixture of the fifth aspect may comprise:

[0266] (i) propylene;

[0267] (ii) at least one polymerisation catalyst comprising a Ziegler-Natta catalyst; and

[0268] (iii) at least one amino alcohol compound NR1R2R3as defined herein.

[0269] For example, the polymerisation reaction mixture of the fifth aspect may comprise: (i) at least one olefinic monomer;

[0270] (ii) at least one polymerisation catalyst comprising a MgCh-supported Ziegler-Natta catalyst; and

[0271] (iii) at least one amino alcohol compound NR1R2R3as defined herein.

[0272] For example, the polymerisation reaction mixture of the fifth aspect may comprise:

[0273] (i) propylene and ethylene;

[0274] (ii) at least one polymerisation catalyst comprising a MgCh-supported Ziegler-Natta catalyst; and

[0275] (iii) at least one amino alcohol compound NR1R2R3as defined herein.

[0276] For example, the polymerisation reaction mixture of the fifth aspect may comprise:

[0277] (i) propylene;

[0278] (ii) at least one polymerisation catalyst comprising a MgCh-supported Ziegler-Natta catalyst; and

[0279] (iii) at least one amino alcohol compound NR1R2R3as defined herein.

[0280] For example, the polymerisation reaction mixture of the fifth aspect may comprise:

[0281] (i) at least one olefinic monomer;

[0282] (ii) at least one polymerisation catalyst comprising a Ziegler-Natta catalyst; and

[0283] (iii) at least one amino alcohol compound of the formula (I) as defined herein for example wherein R1is an optionally substituted Ce-2o alkyl or alkenyl group and R4and R5are each independently an optionally substituted Ci-e alkyl or Ce- aryl group; (for example at least one amino alcohol compound of the formula (I) selected from one or more of / V-octyl N,N-di(isopropanol)amine, / V-oleyl-N,N- di(isopropanol)amine and / V-dodecyl N,N-di(isopropanol)amine).

[0284] Preferably, the polymerisation reaction mixture of the fifth aspect may comprise:

[0285] (i) propylene and ethylene;

[0286] (ii) at least one polymerisation catalyst comprising a Ziegler-Natta catalyst; and

[0287] (iii) at least one amino alcohol compound of the formula (I) as defined herein for example wherein R1is an optionally substituted Ce-2o alkyl or alkenyl group and R4and R5are each independently an optionally substituted Ci-e alkyl or Ce- aryl group; (for example at least one amino alcohol compound of the formula (I) selected from one or more of / V-octyl N,N-di(isopropanol)amine, / V-oleyl-N,N- di(isopropanol)amine and / V-dodecyl N,N-di(isopropanol)amine).

[0288] Preferably, the polymerisation reaction mixture of the fifth aspect may comprise:

[0289] (i) propylene; (ii) at least one polymerisation catalyst comprising a Ziegler-Natta catalyst; and

[0290] (iii) at least one amino alcohol compound of the formula (I) as defined herein for example wherein R1is an optionally substituted Ce-2o alkyl or alkenyl group and R4and R5are each independently an optionally substituted Ci-e alkyl or Ce- aryl group; (for example at least one amino alcohol compound of the formula (I) selected from one or more of / V-octyl N,N-di(isopropanol)amine, / V-oleyl-N,N- di(isopropanol)amine and / V-dodecyl N,N-di(isopropanol)amine).

[0291] For example, the polymerisation reaction mixture of the fifth aspect may comprise:

[0292] (i) at least one olefinic monomer;

[0293] (ii) at least one polymerisation catalyst comprising a MgCh-supported Ziegler-Natta catalyst; and

[0294] (iii) at least one amino alcohol compound of the formula (I) as defined herein for example wherein R1is an optionally substituted Ce-2o alkyl or alkenyl group and R4and R5are each independently an optionally substituted Ci-e alkyl or Ce- aryl group; (for example at least one amino alcohol compound of the formula (I) selected from one or more of / V-octyl N,N-di(isopropanol)amine, / V-oleyl-N,N- di(isopropanol)amine and / V-dodecyl N,N-di(isopropanol)amine).

[0295] For example, the polymerisation reaction mixture of the fifth aspect may comprise:

[0296] (i) propylene and ethylene;

[0297] (ii) at least one polymerisation catalyst comprising a MgCh-supported Ziegler-Natta catalyst; and

[0298] (iii) at least one amino alcohol compound of the formula (I) as defined herein for example wherein R1is an optionally substituted Ce-2o alkyl or alkenyl group and R4and R5are each independently an optionally substituted Ci-e alkyl or Ce- aryl group; (for example at least one amino alcohol compound of the formula (I) selected from one or more of / V-octyl N,N-di(isopropanol)amine, / V-oleyl-N,N- di(isopropanol)amine and / V-dodecyl N,N-di(isopropanol)amine).

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

[0300] (i) propylene;

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

[0302] (iii) at least one amino alcohol compound of the formula (I) as defined herein for example wherein R1is an optionally substituted Ce-2o alkyl or alkenyl group and R4and R5are each independently an optionally substituted Ci-e alkyl or Ce- aryl group; (for example at least one amino alcohol compound of the formula (I) selected from one or more of / V-octyl N,N-di(isopropanol)amine, / V-oleyl-N,N- di(isopropanol)amine and / V-dodecyl N,N-di(isopropanol)amine).

[0303] There may be provided a polyolefin composition comprising a polyolefin material and a detectable amount of at least one amino alcohol compound and / or a derivative thereof, wherein the or each amino alcohol compound is of the formula NR1R2R3, wherein R1is an optionally substituted Ce-2o 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.

[0304] 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 amino alcohol compound may be added before, during or after the olefinic polymerisation process. Suitably the or each amino alcohol compound is added before or during the olefinic polymerisation process. A derivative of the amino alcohol compound may be formed during the olefinic polymerisation process, as would be appreciated by persons skilled in the art.

[0305] When added after the polymerisation process, the amino 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 one or more additional components, such as one more components selected from a dye, pigment, lubricant, stabiliser, impact modifier, and flame retardant.

[0306] In one embodiment, the detectable amount of at least one amino 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 amino alcohol compound and / or a derivative thereof, wherein the or each amino alcohol compound is of the formula NR1R2R3, wherein R1is an optionally substituted Ce- 20 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.

[0307] Suitably, the polyolefin composition of the sixth aspect is prepared according to the method of the first aspect.

[0308] 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. 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 amino alcohol compound of the sixth aspect are as set out herein in relation to the first and fifth aspects.

[0309] The polyolefin composition according to the sixth aspect comprises a detectable amount of the at least one amino 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, in this embodiment, the detectable amount of amino alcohol compound and / or derivative thereof will not substantially affect the properties of the polyolefin composition, or of the polyolefin material therein.

[0310] In another embodiment, the detectable amount of amino alcohol compound and / or derivative thereof is 1000 ppm or more, such as more than 2000 ppm. In this embodiment the amino alcohol compound and / or derivative thereof may affect one or more properties of the polyolefin composition, or of the polyolefin material therein. For example, the amino alcohol compound and / or derivative thereof may affect one or more properties selected from antistatic, appearance (e.g. colour), lubricity, anti-fog, mould release, impact properties, durability, anti-slip, corrosion inhibition, UV resistance, thermal resistance, and chemical resistance (preferably one or more properties selected from antistatic, lubricity, anti-fog and mould release). In a preferred embodiment the amino alcohol compound may affect the antistatic properties of the polyolefin composition, or of the polyolefin material therein.

[0311] The polyolefin composition as disclosed herein may be a masterbatch composition, such as a solid masterbatch.

[0312] 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 amino alcohol compound and / or a derivative thereof.

[0313] 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 amino alcohol compound and a polymerisation catalyst as defined herein. Preferably the polymerisation catalyst is not a single site catalyst. 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.

[0314] 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.

[0315] 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.

[0316] 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.

[0317] 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.

[0318] 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.

[0319] Melt flow rate (MFR) is suitably determined according to ISO 1133 standard method, measured at 230 °C with 21 N load.

[0320] Xylene soluble fraction (XS) is suitably determined according to ISO 16152 standard method.

[0321] Polymer powder bulk density (BD) is suitably determined according to ISO 60 standard method.

[0322] Polymer powder pourability is suitably determined according to ASTM D 1895 standard method using a 9.5 mm to 18 mm cone neck diameter. 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.

[0323] The polyolefin material according to the eighth aspect is suitably a homopolymer (for example polyethylene or polypropylene) or a copolymer, for example a homogeneous (random) copolymer, as disclosed herein.

[0324] The polyolefin material according to the eighth aspect may suitably be a heterophasic (impact) copolymer, as disclosed herein.

[0325] The homopolymer suitably has a melt flow rate (MFR) according to ISO 1133 standard method at 230°C and 21 N of from 70 to 100 g / 10min, 75 to 100 g / 10min, for example from 80 to 100 g / 10min, or from 80 to 95 g / 10min, suitably from 85 to 95 g / 10min.

[0326] 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%.

[0327] The homopolymer suitably has a polymer powder bulk density (BD) according to ISO 60 standard method of from 350 to 450 g L1, for example from 380 to 440 g L1, or from 400 to 430 g L1, suitably from 410 to 425 g L1.

[0328] 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 / 10min, for example from 10 to 35 g / 10min, preferably from 11 to 35 g / 10min or from 12 to 33 g / 10min.

[0329] 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 L1, for example from 380 to 440 g L1.

[0330] 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 50 seconds, 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.

[0331] 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. The copolymer (preferably the heterophasic (impact) copolymer) suitably has a polymer powder pourability according toASTM 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.

[0332] The copolymer (preferably the heterophasic (impact) copolymer) suitably has a polymer powder pourability according toASTM 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.

[0333] 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.

[0334] The copolymer (preferably the heterophasic (impact) copolymer) suitably has a pourability of less than 20 seconds as measured according to ASTM 1895 using a 9.5mm cone.

[0335] 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%.

[0336] 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.

[0337] 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.

[0338] 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.

[0339] 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.

[0340] Preferably the article is a food packaging product. Preferably the article is a medical product, for example a syringe product or medical packaging product.

[0341] The article is suitably an automotive product selected from one or more of instrument panels, bumpers, door trim, and other interior plastics.

[0342] 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).

[0343] Brief description of the figures

[0344] 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:

[0345] Figures 1 and 2 show the degree of reactor fouling during gas-phase homopolymerisation of propylene in Example 1 , when no amino alcohol compound is present.

[0346] Figures 3 and 4 show the degree of reactor fouling during gas-phase homopolymerisation of propylene in Example 1 , at a treat rate of 40 ppm wt. (based on the amount of propylene present) of / V-octyl N,N-di(isopropanol)amine.

[0347] Figures 5 and 6 show the degree of reactor fouling during the gas-phase homopolymerisation of propylene in Example 1 , at a treat rate of 40 ppm wt. (based on the amount of propylene present) of / V-dodecyl N,N-di(isopropanol)amine.

[0348] Figures 7 and 8 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)amine.

[0349] Figure 9 shows the effect of / V-octyl N,N-di(isopropanol)amine on the electric current generated during the gas-phase homopolymerisation of propylene in Example 1 , compared to the electric current generated when no amino alcohol compound is present.

[0350] Figure 10 shows the effect of / V-dodecyl N,N-di(isopropanol)amine on the electric current generated during the gas-phase homopolymerisation of propylene in Example 1 , compared to the electric current generated when no amino alcohol compound is present. Figure 11 shows the effect of / V-oleyl N,N-di(isopropanol)amine on the electric current generated during the gas-phase homopolymerisation of propylene in Example 1 , compared to the electric current generated when no amino alcohol compound is present.

[0351] Figures 12 and 13 show the degree of reactor fouling during gas-phase homopolymerisation of propylene in Example 3, at a treat rate of 40 ppm wt. (based on the amount of propylene present) of / V-oleyl N,N-di(isopropanol)amine derived from a commercially available distilled vegetable based oleyl amine having an iodine value of 90 to 115 g k / 100g.

[0352] Figures 14 and 15 show the degree of reactor fouling during gas-phase homopolymerisation of propylene in Example 3, at a treat rate of 40 ppm wt. (based on the amount of propylene present) of / V-oleyl N,N-di(isopropanol)amine derived from a commercially available distilled animal based oleyl amine having an iodine value of > 85 g l2 / 100 g.

[0353] Figures 16 and 17 show the degree of reactor fouling during gas-phase homopolymerisation of propylene in Example 3, at a treat rate of 40 ppm wt. (based on the amount of propylene present) of Atmer 163.

[0354] Figures 18 and 19 show the degree of reactor fouling during gas-phase homopolymerisation of propylene in Example 3, at a treat rate of 60 ppm wt. (based on the amount of propylene present) of Atmer 163.

[0355] Figure 20 shows the effect of / V-oleyl N,N-di(isopropanol)amine derived from a commercially available distilled vegetable based oleyl amine having an iodine value of 90 to 115 g I2 / 100g on the electric current generated during the gas-phase homopolymerisation of propylene in Example 3, compared to the electric current generated when no amino alcohol compound is present.

[0356] Figure 21 shows the effect of / V-oleyl N,N-di(isopropanol)amine derived from a commercially available distilled animal based oleyl amine having an iodine value of > 85 g l2 / 100 g on the electric current generated during the gas-phase homopolymerisation of propylene in Example 3, compared to the electric current generated when no amino alcohol compound is present.

[0357] Figure 22 shows the effect of Atmer 163 at different treat rates, on the electric current generated during the gas-phase homopolymerisation of propylene in Example 3, compared to the electric current generated when no amino alcohol compound is present.

[0358] The invention will now be further described with reference to the following non-limiting examples. Examples

[0359] Polymerisation-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.

[0360] Commercial polymerisation-grade ethylene was purified in the same manner and to the same impurities specification as the polymerisation-grade propylene.

[0361] Triethylaluminium (TEA) with ultra-low aluminum 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.

[0362] Cyclohexylmethyldimethoxysilane (CHMDMS) 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.

[0363] Commercial MgCh-supported Ziegler-Natta catalyst was dispersed in white mineral oil with a concentration of 11 wt%.

[0364] All of the amino alcohol compounds were diluted in n-heptane to a suitable concentration and stored in glass vessels under nitrogen. For homopolymerisation, the amino alcohol compounds were diluted in n-heptane to 18 mg / ml. For heterophasic copolymerization, the amino alcohol compounds were diluted in n-heptane to 244 mg / ml.

[0365] 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.

[0366] 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.

[0367] After component dosing, the reactor temperature 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 amino alcohol compound was 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 amino alcohol compound was added to the reactor in a weight ratio relative to the weight of propylene present in the reactor (ppm wt.).

[0368] Each of the amino alcohol compounds used in Table 1 was prepared by reacting diisopropyl amine (DIPA) with the appropriate 1 -bromo alkyl reactant to give the listed amino alcohol compound.

[0369] Summary of homopolymerisation conditions:

[0370] TEA / Ti = 100 mol / mol

[0371] CHMDMS / Ti = 10 mol / mol

[0372] H2 = 110 mmol

[0373] Temperature = 75°C

[0374] Pressure = 2.2 Mpa(g)

[0375] The results of the reactor fouling for Example 1 are shown in Figures 1 to 8, as discussed below.

[0376] The effect of the amino 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.

[0377] The severity of reactor fouling was categorised as follows:

[0378] No fouling: minimal residual powder deposits on the reactor cover, stirrer, walls, and the space immediately surrounding the opening in the reactor.

[0379] 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.

[0380] 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.

[0381] 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.

[0382] The effect of the amino alcohol compounds on static was also determined by measuring the electrical current generated during the polymerisation process, particularly after 10 minutes.

[0383] Measurement of Electrostatic Charge

[0384] 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.

[0385] 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.

[0386] The fouling and static reduction results are shown in Table 1 .

[0387] Table 1

[0388] Example 2: Gas-Phase Sequential Copolymerisation for Heterophasic Copolymer (HOP)

[0389] Polypropylene homopolymer was prepared according to the process in Example 1 using 10mg catalyst and without the addition of an amino 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 amino alcohol compound, hydrogen, ethylene and propylene were introduced into the reactor within 90 seconds to provide the desired gas-phase composition and copolymerisation pressure. The amino 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.

[0390] 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 GO analysis every 2 / 3 minutes. The copolymerisation phase was carried out until a fixed amount of ethylene-propylene copolymer / rubber (EPR) content was achieved [25, 35 or 40 wt%].

[0391] Summary of copolymerisation conditions:

[0392] Propylene = 52 g

[0393] Ethylene = 7.5 g

[0394] Hydrogen = 11 mmol

[0395] Temperature = 75°C

[0396] Pressure = 2.2 MPa(g)

[0397] Ethylene in EPR = 35 wt%

[0398] Amino alcohol compound: (A) / V-dodecyl- / V, / \ / -di(isopropanol)amine or (B) / V-oleyl- / V, / \ / - di(isopropanol)amine

[0399] 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.

[0400] A polymer powder pourability test was performed according to ASTM D 1895 standard method and the results are summarised in Table 2 below. It is desirable to obtain shorter pouring times. Table 2 wt% EPR by mass of overall polymer

[0401] ‘‘Determined according to ISO 1133 standard method at 230°C and 21 N

[0402] ‘“Determined according to ISO 16152 standard method

[0403] ““Determined according to ISO 60 standard method.

[0404] Table 2 shows that the HCP polymer prepared without an amino alcohol compound added is sticky and does not flow or pour. In contrast, the HCP polymer prepared with the amino alcohol compounds added has a similar flow time as the homopolypropylene.

[0405] Example 3: Gas-Phase Homopolymerisation (HPP)

[0406] The homopolymerisation process of Example 1 was repeated using the amino alcohol compounds, dosing rates and catalyst loadings shown in Table 3.

[0407] The reactor fouling severity results and static reduction results for Example 3 were determined in the same way as for Example 1 , and are shown in Figures 12 to 22 and Table 3.

[0408] Table 3

[0409] *Prepared via the reaction of 2 moles of propylene oxide and 1 mole of oleyl amine derived from a commercially available distilled vegetable based oleyl amine having an iodine value of 90 to 115 g l2 / 100g.

[0410] **Prepared via the reaction of 2 moles of propylene oxide and 1 mole of oleyl amine derived from a commercially available distilled animal based oleyl amine having an iodine value of > 85 g I2 / IOO g.

[0411] ***Commercially available / V, / V-bis(2-hydroxyethyl)alkyl (C13-C15) amine Table 3 shows that homopolymerisation of propylene in the presence of an amino alcohol compound of the present invention leads to significantly reduced fouling compared to equivalent and higher doses ofAtmer 163. Example 4: Gas-Phase Sequential Copolymerisation

[0412] The copolymerisation of Example 2 was repeated using the following amino alcohol compounds:

[0413] (C) / V-oleyl- / V, / \ / -di(isopropanol)amine prepared via the reaction of 2 moles of propylene oxide and 1 mole of oleyl amine derived from a commercially available distilled vegetable based oleyl amine having an iodine value of 90 to 115 g h / 100g;

[0414] (D) / V-oleyl- / V, / \ / -di(isopropanol)amine prepared via the reaction of 2 moles of propylene oxide and 1 mole of oleyl amine derived from a commercially available distilled animal based oleyl amine having an iodine value of > 85 g l2 / 100 g; (E) Atmer 163 (commercially available / V, / V-bis(2-hydroxyethyl)alkyl (C13-C15) amine).

[0415] A polymer powder pourability test was performed according to ASTM D 1895 standard method and the results are summarised in Table 4 below. It is desirable to obtain shorter pouring times.

[0416] Table 4 wt% EPR by mass of overall polymer ‘‘Determined according to ISO 1133 standard method at 230°C and 21 N ‘“Determined according to ISO 16152 standard method ““Determined according to ISO 60 standard method.

[0417] Table 4 shows that the HCP polymer prepared in the presence of an amino alcohol compound of the present invention is less sticky and has improved flowability and pourability compared to the HCP polymer prepared with Atmer 163. 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 amino alcohol compound; wherein the or each polymerisation catalyst comprises a Ziegler-Natta catalyst and wherein the or each amino alcohol compound is of the formula NR1R2R3, wherein R1is an optionally substituted Ce-2o 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 amino 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 polymerisation catalyst comprises a Ziegler-Natta catalyst and wherein the or each amino alcohol compound is of the formula NR1R2R3, wherein R1is an optionally substituted Ce-2o 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 amino alcohol compound; and(b) carrying out a polymerisation process; wherein the or each polymerisation catalyst comprises a Ziegler-Natta catalyst and wherein the or each amino alcohol compound is of the formula NR1R2R3, wherein R1is an optionally substituted Ce-2o 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 amino 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 polymerisation catalyst comprises a Ziegler-Natta catalyst and wherein the or each amino alcohol compound is of the formula NR1R2R3, wherein R1is an optionally substituted Ce-2o hydrocarbyl group, and each of R2and R3is independently ahydrocarbyl 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 amino 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 amino alcohol compound, wherein the or each polymerisation catalyst comprises a Ziegler-Natta catalyst and wherein the or each amino alcohol compound is of the formula NR1R2R3, wherein R1is an optionally substituted Ce-2o 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 a Ce-2o alkyl group, preferably a linear Ce-2o alkyl group.

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

9. A method, use or polymerisation reaction mixture according to claim 8, wherein R4and R5are each independently selected from a methyl, ethyl, propyl, phenyl or cyclohexenyl group.

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

11. A method, use or polymerisation reaction mixture according to any preceding claim, wherein the or each amino alcohol compound is a liquid at standard pressure and at a temperature of from 0°C to 25°C, more preferably at a temperature of from -5°C to 25°C, even more preferably at a temperature of from -15°C to 25°C, most preferably at a temperature of from -25°C to 25°C.

12. 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).

13. A method, use or polymerisation reaction mixture according to claim 12, wherein the or each olefinic monomer is selected from one or more of ethylene and propylene (including mixtures thereof).

14. 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.

15. A method or use according to any one of claims 1 to 5 and 7 to 13, wherein the polyolefin material formed by the method or use is a homopolymer.

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 copolymer, preferably a homogeneous (random) copolymer or a heterophasic (impact) copolymer.

17. A method or use according to any one of claims 1 to 5 and 7 to 16, wherein the polyolefin material formed by the method or use is a free-flowing powder.

18. A method, use or polymerisation reaction mixture according to any preceding claim, wherein the or each polymerisation catalyst is a Zeigler-Natta catalyst.

19. A polyolefin composition comprising a polyolefin material and a detectable amount of at least one amino alcohol compound and / or a derivative thereof, wherein the or each amino alcohol compound is of the formula NR1R2R3, wherein R1is an optionally substituted Ce- 2o 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.

20. 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.

21. 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.

22. A polyolefin composition according to claim 19, or a polyolefin material according to claim 21 , wherein the polyolefin material is a heterophasic (impact) copolymer with a pourability of less than 20 as measured according to ASTM 1895 using a 9.5mm cone.

23. An article comprising the polyolefin composition of claim 19, 20 or 22, or the polyolefin material of claim 21 or 22.

24. An article according to claim 23, wherein the article is a packaging product.

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