Process for the preparation of a composition comprising at least a mixture of at least one peroxydicarbonate and at least one peroxyester

Abstract

The present invention relates to a process for the preparation of an organic peroxide composition comprising a mixture of at least one peroxydicarbonate and at least one peroxyester, preferably at least one hydroxyperoxyester; said composition being prepared prior to contact with one or more ethylenically unsaturated monomers, preferably one or more halogenated vinyl monomers and more preferentially vinyl chloride. The present invention also relates to a process for the polymerization of one or more ethylenically unsaturated monomers, comprising in succession the preparation of a composition as defined above, and the contact of said composition with one or more ethylenically unsaturated monomers.

Description

[0001] The present invention relates to a method for preparing an organic peroxide composition comprising at least one peroxydicarbonate and at least one peroxy ester, preferably at least one hydroxyperoxy ester; the composition is prepared prior to contact with one or more monomers comprising olefinic unsaturations, preferably one or more halogenated vinyl monomers and more preferably vinyl chloride.

[0002] The present invention also relates to a method for polymerizing one or more olefinically unsaturated monomers, the method comprising, sequentially, preparing a composition as defined above, and contacting the composition with one or more olefinically unsaturated monomers.

[0003] The present invention also relates to halogenated vinyl polymers obtained by polymerization of at least one halogenated olefinic unsaturated monomer in the presence of the composition as defined above.

[0004] Organic peroxides, in liquid or solid form, are commonly used as polymerization initiators for olefinic unsaturated monomers to synthesize various types of polymers, such as halogenated vinyl polymers, like polyvinyl chloride.

[0005] However, their use often presents a number of problems. This is because organic peroxides generally constitute highly unstable entities, as they decompose relatively easily under the influence of heat, mechanical energy (friction or shock), and / or the slight contribution of incompatible contaminants. Therefore, under uncontrolled increases in their storage temperature, some organic peroxides can undergo auto-accelerated exothermic decomposition, which can lead to ignition and / or violent explosion. Additionally, under these conditions, some of these organic peroxides can release flammable vapors capable of reacting with any ignition source, which can dramatically increase, and in fact even accelerate, the risk of a violent explosion. Consequently, it is crucial to take appropriate safety precautions during the storage and transportation of organic peroxides.

[0006] To overcome these various drawbacks, organic peroxides are sometimes stored at temperatures well below 0°C before being used as polymerization initiators. Therefore, organic peroxides are specifically packaged as aqueous emulsions (which may contain antifreeze). This is because the presence of water allows the energy generated during the exothermic decomposition of the organic peroxide to be absorbed and dissipated, while the antifreeze keeps the emulsion in liquid form at temperatures below -10°C, typically below -15°C, thus limiting the risk of unintentional exothermic decomposition of the organic peroxide.

[0007] In addition, aqueous emulsions typically contain at least one emulsifier, which has the advantage of reducing the interfacial tension between the aqueous phase and the organic peroxide. The aim is to promote the dispersion of the peroxide in droplet form and to maintain its size over time. This is because, over time, peroxide droplets can aggregate, increasing their average and maximum size. In some cases, this can lead to partial or complete phase separation, resulting in overall instability of the emulsion.

[0008] Furthermore, mixtures of organic peroxides can also be used as polymerization initiators. For this purpose, the organic peroxides can be injected separately into the reaction medium containing the olefinically unsaturated monomers during polymerization, or they can be prepared upstream in a separate reactor for addition at the start of polymerization. In other words, in some cases, mixtures of organic peroxides, also known as premixes, are prepared upstream in a suitable reactor before being added to the polymerization reactor. Such peroxide premixes are typically packaged in aqueous emulsions.

[0009] However, the preparation of these premixes is typically carried out at temperatures higher than the storage temperature of the organic peroxides—that is, at temperatures where the organic peroxides are at risk of decomposition. Similarly, such premixes may also be stored for hours, and in fact even days, in the reactors in which they were prepared before use at temperatures higher than the storage temperature of the organic peroxides, which increases the risk of thermal decomposition of the organic peroxides.

[0010] Therefore, the preparation of premixes of organic peroxides often results in unstable compositions in which the organic peroxides can decompose with temperature changes, leading to a reduction in the amount of free radicals that can be generated during polymerization, which can result in a decline in the quality of the obtained polymer.

[0011] Therefore, one of the objects of the present invention is to prepare a mixture of organic peroxides that does not exhibit the above-mentioned disadvantages, and is particularly stable under thermal conditions and over time.

[0012] In particular, one object of the present invention is to provide a method for preparing a stable mixture of organic peroxides in which thermal degradation (or decomposition) of the peroxides is minimized. In other words, one object of the present invention is to develop a method capable of ensuring, and in fact even improving, the activity of organic peroxides during polymerization.

[0013] Therefore, the subject of this invention is a method for preparing a composition of organic peroxides, the method comprising mixing at least one peroxydicarbonate and at least one peroxy ester before contacting the composition with one or more olefinically unsaturated monomers.

[0014] In particular, the method according to the invention includes a stage of mixing at least one peroxydicarbonate and at least one peroxy ester and then contacting the resulting composition with one or more olefinic unsaturated monomers intended to be polymerized together.

[0015] Therefore, the method according to the invention exhibits the advantage of producing a stable composition in which the thermal degradation of the organic peroxide over time is minimized.

[0016] The method according to the invention enables the preparation of a mixture of organic peroxides upstream of their introduction into the polymerization reactor, which can be stored and transported in a stable manner at a temperature above the storage temperature of the organic peroxides to the final polymer production site so that they can be used as polymerization initiators as is.

[0017] In particular, the method according to the invention enables the preparation of stable compositions of organic peroxides in suitable reactors present at the production site of the final polymer at temperatures higher than the storage temperature of the organic peroxides, and allows them to be placed in such reactors for longer or shorter periods of time before being effectively used as polymerization initiators.

[0018] In other words, this method minimizes the formation of free radicals in the premix of organic peroxides, which ensures the quality of the obtained polymer and better yield.

[0019] Therefore, the composition obtained by the method according to the invention can be transported safely within the factory to produce polymers, particularly from one point in the factory to another, and can produce polymer materials of good quality.

[0020] More specifically, the addition of peroxy esters allows for the effective stabilization of peroxydicarbonates.

[0021] Furthermore, the method according to the invention produces a polymer that, in the polymerization reactor, leads to a more uniform distribution of organic peroxides, which improves reaction time and promotes the acquisition of polymers of better quality. Such uniformity has been particularly observed with the addition of peroxyesters to polymerization reactors containing peroxydicarbonates.

[0022] Furthermore, the method according to the invention can be advantageously carried out in a factory to produce polymers, which constitutes a time saving from an industrial perspective.

[0023] The composition of organic peroxides obtained according to the method of the invention can advantageously be kept at temperatures higher than the storage temperature for several hours, and in fact even several days, which provides operators with greater flexibility in the production of polymers.

[0024] In particular, the possibility of storing such compositions for extended periods at temperatures above the storage temperature of peroxides allows for savings in the amount of organic peroxides required for polymer production.

[0025] The method according to the invention also exhibits industrial advantages in that it can prepare stable compositions that allow polymerization of olefinic unsaturated monomers to be initiated at similar rates under reproducible conditions from one polymerization reactor to another, and to obtain polymers with similar quality and / or uniform mechanical and chemical properties.

[0026] Furthermore, the composition obtained by the method according to the invention can be used several times within hours, or even days, after its preparation, while maintaining good stability.

[0027] Another subject of the present invention is a polymerization method for one or more olefinically unsaturated monomers, comprising sequentially:

[0028] (i) Prepare the composition as defined above.

[0029] (ii) Contact the composition with one or more olefinic unsaturated monomers.

[0030] This polymerization method allows for the preparation of high-quality polymers under reproducible conditions. This is because the polymerization reaction time has been improved.

[0031] Another subject of the invention is the use of the compositions as defined above for the polymerization or copolymerization of one or more olefinic unsaturated monomers, particularly vinyl monomers, preferably halogenated vinyl monomers, and more preferably vinyl chloride.

[0032] Compositions containing mixtures of organic peroxides can therefore be used as polymerization initiators for the synthesis of polymers or copolymers obtained from one or more olefinic unsaturated monomers.

[0033] In addition, the present invention also relates to halogenated vinyl polymers obtained by polymerization of at least one halogenated olefinic unsaturated monomer in the presence of the composition described above.

[0034] Other features and advantages of the present invention will become more apparent from the following description and embodiments.

[0035] In the following text and unless otherwise stated, the limits of the range of values ​​are included within this range.

[0036] The expression "at least one (at least one)" is equivalent to the expression "one or more (one or more)".

[0037] Within the meaning of this invention, the expression "R" is used. n and R mRepresenting C x -C x4 "alkyl" means R n and R m Can represent C x C x1 C x2 C x3 and C x4 That is to say, including C x and C x4 The limit.

[0038] Preparation method of the composition

[0039] As described above, the method according to the invention comprises mixing at least one peroxydicarbonate and at least one peroxy ester before contacting the composition with one or more olefinic unsaturated monomers.

[0040] Preferably, the peroxydicarbonate corresponds to the following formula (I):

[0041]

[0042] In equation (I), R 1 and R 2 They are the same or different, representing straight chain, branched chain, or cyclic C1-C. 20 Alkyl groups may contain one or more heteroatoms, preferably one or more oxygen atoms.

[0043] Preferably, R 1 and R 2 They are the same or different, representing straight chain, branched chain, or cyclic C1-C. 16 C3-C is given higher priority. 12 Especially C3-C 10 Alkyl groups may contain one or more heteroatoms, preferably one or more oxygen atoms, preferably interrupted by one or more heteroatoms, preferably one or more oxygen atoms.

[0044] Preferably, R 1 and R 2 Whether they are the same or different, they represent straight chains C1-C. 16 C3-C is given higher priority. 12 Especially C3-C 10 Alkyl groups may contain one or more heteroatoms, preferably one or more oxygen atoms.

[0045] Preferably, R 1 and R 2 Whether they are the same or different represents the branches C1-C. 16 C3-C is given higher priority. 12 Especially C3-C 10Alkyl groups may contain one or more heteroatoms, preferably one or more oxygen atoms.

[0046] Preferably, R 1 and R 2 Whether they are the same or different, they represent cyclic C3-C 12 Especially C3-C 10 Alkyl groups may contain one or more heteroatoms, preferably one or more oxygen atoms.

[0047] Preferably, R 1 and R 2 They may be the same or different, representing alkyl groups as defined above, which may be interrupted by one or more heteroatoms, preferably one or more oxygen atoms.

[0048] Within the meaning of this invention, the term "cyclic alkyl" is understood to mean a straight-chain or branched alkyl group comprising a ring, preferably an aromatic ring (preferably comprising 5 or 6 ring members).

[0049] Preferably, the heteroatom is an oxygen atom.

[0050] Preferably, R 1 and R 2 They are the same and represent straight chains or branches, with preferred branches C2-C. 16 Especially C3-C 12 C3-C is given even higher priority. 10 alkyl.

[0051] Priority, R 1 and R 2 They are the same and represent straight-chain or branched chains, preferably branched C2-C8 alkyl groups.

[0052] The peroxydicarbonate is preferably selected from di(2-ethylhexyl) peroxydicarbonate, di(sec-butyl) peroxydicarbonate, bis(1-methylheptyl) peroxydicarbonate, di(n-propyl) peroxydicarbonate, di(3-methoxybutyl) peroxydicarbonate, diethyl peroxydicarbonate, and mixtures thereof, with di(2-ethylhexyl) peroxydicarbonate and di(sec-butyl) peroxydicarbonate being the most preferred.

[0053] Advantageously, peroxydicarbonate is selected from products listed under the trade name 223 sold di(2-ethylhexyl) peroxydicarbonate and under the trade name 225 Peroxydicarbonate di(sec-butyl) ester sold.

[0054] Preferably, the peroxide ester corresponds to the following formula (II):

[0055]

[0056] In equation (II), R3 and R 4 They are the same or different, representing straight chain, branched chain, or cyclic C1-C. 20 Alkyl groups may contain one or more heteroatoms, preferably one or more oxygen atoms, and / or optionally be substituted with one or more hydroxyl groups.

[0057] Preferably, R 3 and R 4 Whether they are the same or different, they represent straight chains or branched chains C4-C. 20 C7-C is preferred. 20 C7-C is preferred. 16 Especially C7-C 10 Alkyl groups may contain one or more heteroatoms, preferably one or more oxygen atoms, and / or optionally be substituted with one or more hydroxyl groups.

[0058] Preferably, R 3 and R 4 Whether they are the same or different, they represent straight-chain C4-C. 20 C7-C is preferred. 20 C7-C is preferred. 16 Especially C7-C 10 Alkyl groups may contain one or more heteroatoms, preferably one or more oxygen atoms, and / or optionally be substituted with one or more hydroxyl groups.

[0059] Preferably, R 3 and R 4 Whether they are the same or different, they represent the C4-C branch. 20 C7-C is preferred. 20 C7-C is preferred. 16 Especially C7-C 10 Alkyl groups may contain one or more heteroatoms, preferably one or more oxygen atoms, and / or optionally be substituted with one or more hydroxyl groups.

[0060] Preferably, R 3 and R 4 Whether they are the same or different, they represent cyclic C4-C. 20 C7-C is preferred. 20 C7-C is preferred. 16 Especially C7-C 10 Alkyl groups may contain one or more heteroatoms, preferably one or more oxygen atoms, and / or optionally be substituted with one or more hydroxyl groups.

[0061] Within the meaning of this invention, the term "cyclic alkyl" is understood to mean a straight-chain or branched alkyl group that additionally comprises a ring, preferably an aromatic ring (preferably comprising 5 or 6 ring members).

[0062] In other words, within the meaning of this invention, cyclic alkyl groups comprise straight or branched chains, preferably C2-C4 alkyl groups and rings, preferably aromatic rings, and preferably containing 5 or 6 ring members.

[0063] Preferably, the cyclic alkyl group comprises branched chains, preferably C2-C4 alkyl groups, and aromatic rings (preferably containing 5 or 6 ring members).

[0064] Preferably, R 3 and R 4 They are the same or different, representing alkyl groups as defined above, which may be interrupted by one or more heteroatoms, preferably one or more oxygen atoms, and / or optionally substituted by one or more hydroxyl groups.

[0065] Preferably, R 3 and R 4 They are the same or different, representing straight chain, branched chain, or cyclic C1-C. 20 Alkyl groups, which may optionally be substituted with one or more hydroxyl groups.

[0066] Preferably, R 3 Represents straight or branched C4-C 20 C7-C is preferred. 20 C7-C is preferred. 16 Especially C7-C 10 Alkyl groups, which may contain one or more heteroatoms, preferably one or more oxygen atoms, preferably interrupted by one or more heteroatoms, preferably one or more oxygen atoms, and R 4 Represents a straight-chain or branched C1-C7, preferably C2-C6 alkyl group, optionally substituted with one or more hydroxyl groups, or a cyclic C7-C... 16 Especially C7-C 10 alkyl.

[0067] Preferably, R 3 Represents branch C7-C 20 C4-C is preferred. 20 C7-C is preferred. 16 Especially C7-C 10 Alkyl groups, which may contain one or more heteroatoms, preferably one or more oxygen atoms, preferably interrupted by one or more heteroatoms, preferably one or more oxygen atoms, and R 4 Represents branched C1-C7, preferably C2-C6 alkyl groups, which may optionally be substituted with one or more hydroxyl groups.

[0068] Preferably, the heteroatom is an oxygen atom.

[0069] Preferably, in formula (II):

[0070] -R 3 Represents straight chain, branched chain, or cyclic chain; preferred branched chain C4-C.20 C7-C is preferred. 20 C7-C is preferred. 16 Especially C7-C 10 Alkyl groups may contain one or more oxygen atoms, preferably one oxygen atom, preferably interrupted by one or more oxygen atoms, preferably one oxygen atom;

[0071] -R 4 represent:

[0072] i) Straight chain or branched chain, preferably branched chain C7-C 20 C7-C is preferred. 16 In particular, C7-C9 alkyl groups may contain one or more oxygen atoms, preferably one oxygen atom, preferably interrupted by one or more oxygen atoms, preferably one oxygen atom;

[0073] ii) Straight-chain or branched, preferably branched C1-C7, preferably C2-C6 alkyl, optionally substituted with one or more hydroxyl groups,

[0074] iii) Circular C7-C 10 Especially cyclic C9 alkyl groups.

[0075] Prior to this, in equation (II), R 3 Represents straight chains or branches, with preferred branch C4-C. 20 C7-C is preferred. 20 C7-C is preferred. 16 Especially C7-C 10 alkyl.

[0076] Prior to this, in equation (II), R 4 represent:

[0077] - Straight-chain or branched, preferably branched C1-C7, preferably C2-C6, particularly C4 or C6 alkyl, optionally substituted with one or more hydroxyl groups,

[0078] - cyclic C7-C 10 Especially C9 alkyl.

[0079] Prior to, in equation (II), when R 4 Represents cyclic C7-C 10 When alkyl, R 4 It comprises a straight or branched chain, preferably a branched C2-C4 chain, particularly a C3 alkyl chain, and a ring, preferably an aromatic ring, preferably containing 5 or 6 ring members.

[0080] Even more preferably, R 4 Represents a straight or branched chain, preferably branched C1-C7, preferably C2-C6, particularly C6 alkyl, which is substituted with one or more hydroxyl groups, particularly one hydroxyl group.

[0081] Advantageously, in equation (II):

[0082] -R 3 Represents straight chains or branches, with preferred branch C4-C. 20 C7-C is preferred. 20 C7-C is preferred. 16 Especially C7-C 10 alkyl,

[0083] -R 4 Represents a straight or branched chain, preferably a branched C1-C7, preferably C2-C6 alkyl group, optionally substituted with one or more hydroxyl groups.

[0084] The peroxide ester is preferably selected from α-isopropylphenyl peroxyneodecanoate, α-isopropylphenyl peroxyneoheptanoate, 2,4,4-trimethylpentyl-2-yl peroxyneodecanoate, tert-butyl peroxy(n-heptanoate), tert-butyl peroxyneodecanoate, α-isopropylphenyl peroxy(n-heptanoate), tert-pentyl peroxy(n-heptanoate), tert-butyl peroxyneoheptanoate, and 2,5-dimethyl-2,5-di(2-ethylhexanoylperoxy) Hexane, tert-amyl peroxy(2-ethylhexanoate), tert-butyl peroxy(2-ethylhexanoate), 1,1,3,3-tetramethylbutyl peroxy(2-ethylhexanoate), hydroxyperoxy ester, tert-amyl peroxyneodecanate, 1,1,3,3-tetramethylbutyl peroxyneodecanate, 1,1,3,3-tetramethylbutyl peroxynepentanoate, tert-hexyl peroxyneodecanate, tert-hexyl peroxynepentanoate, and mixtures thereof.

[0085] Preferably, the peroxide ester is selected from hydroxyperoxide esters.

[0086] Hydroxyperoxide esters are advantageously selected from 4-hydroxy-2-methylpentyl peroxynedecanoate, 4-hydroxy-2-methylpentyl peroxyneoheptanoate, 4-hydroxy-2-methylpentyl peroxy(2-ethylhexanoate), 4-hydroxy-2-methylpentyl peroxy(2-phenylbutyric acid), 4-hydroxy-2-methylpentyl peroxy(2-phenoxypropionic acid), 4-hydroxy-2-methylpentyl peroxy(2-butyloctanoate), 4-hydroxy-2-methylpentyl peroxyneohexanoate, 4-hydroxy-2-methylpentyl peroxyneohexanoate, 4-hydroxy-2-methylpentyl peroxyneohexanoate, and 4-hydroxy-2-methylhexyl peroxyneohexanoate. 4-hydroxy-2-methylhexyl peroxynedecanoate, 5-hydroxy-1,3,3-trimethylcyclohexyl peroxynedecanoate, 4-hydroxy-2,6-dimethyl-2,6-di(neohexanoylperoxy)heptane, 4-hydroxy-2,6-dimethyl-2,6-di(neohexanoylperoxy)heptane, 3-hydroxy-1,1-dimethyl butyl peroxy(2-ethylhexanoate), 3-hydroxy-1,1-dimethyl butyl peroxynedecanoate, 3-hydroxy-1,1-dimethyl butyl peroxynedecanoate, and mixtures thereof, preferably 3-hydroxy-1,1-dimethyl butyl peroxynedecanoate.

[0087] Preferably, the peroxide ester is selected from tert-butyl peroxyneodecanate, tert-amyl peroxyneodecanate, α-isopropylphenyl peroxyneoheptanoate, hydroxyperoxide ester, and mixtures thereof.

[0088] Preferably, the peroxide ester is selected from Arkema under the trade name. The 3-hydroxy-1,1-dimethyl butyl peroxyneodecanoate sold by 610, under the trade name The α-isopropylphenyl peroxyneoheptanoate sold by 188, under the trade name 546 sells tert-amyl peroxyneodecanate, and Arkema sells it under the brand name... 10. Tert-butyl peroxyneodecanate sold, and mixtures thereof.

[0089] Preferably, the peroxide ester is selected from Arkema under the trade name. 610 sells 3-hydroxy-1,1-dimethyl butyl peroxyneodecanoate, and Arkema sells it under the trade name... 10. Tert-butyl peroxyneodecanate sold, and mixtures thereof.

[0090] Advantageously, peroxide esters are produced by Arkema under the trade name... 610 sells 3-hydroxy-1,1-dimethyl butyl peroxyneodecanoate.

[0091] Preferably, the weight ratio of peroxydicarbonate / peroxyester varies from 1 / 99 to 99 / 1, and more preferably from 2 / 98 to 98 / 2.

[0092] According to another embodiment, the weight ratio of peroxydicarbonate / peroxyester varies from 10 / 90, particularly from 20 / 80 to 50 / 50.

[0093] According to another embodiment, the weight ratio of peroxydicarbonate / peroxyester varies from 99 / 1, particularly from 97 / 3, particularly from 90 / 10, and preferably from 80 / 20 to 50 / 50.

[0094] Peroxydicarbonates and peroxyesters advantageously have a one-hour half-life temperature of 90°C or less, preferably less than 90°C.

[0095] In addition, peroxydicarbonates and peroxyesters have the advantage of a storage temperature below 0°C.

[0096] Preferably, the method according to the invention includes mixing:

[0097] (i) at least one organic peroxide of formula (I):

[0098]

[0099] In equation (I), R 1 and R 2 They are the same or different, representing straight chain, branched chain, or cyclic C1-C. 20 Alkyl groups, which may contain one or more heteroatoms, preferably one or more oxygen atoms; and

[0100] (ii) at least one organic peroxide of formula (II):

[0101]

[0102] In equation (II), R 3 and R 4 They are the same or different, representing straight chain, branched chain, or cyclic C1-C. 20 Alkyl groups may contain one or more heteroatoms, preferably one or more oxygen atoms, and / or optionally be substituted with one or more hydroxyl groups.

[0103] Preferably, the method according to the invention includes mixing:

[0104] (I) At least one organic peroxide of formula (I):

[0105]

[0106] In equation (I), R 1 and R 2 They are the same and represent straight chains or branches, with preferred branches C1-C. 16 Especially C3-C 12C3-C is given even higher priority. 10 Alkyl; and

[0107] (ii) at least one organic peroxide of formula (II):

[0108]

[0109] In equation (II):

[0110] -R 3 Represents straight chain, branched chain, or cyclic chain; preferred branched chain C4-C. 20 C7-C is preferred. 20 C7-C is preferred. 16 In particular, C7-C9 alkyl groups may contain one or more oxygen atoms, preferably one oxygen atom, preferably interrupted by one or more oxygen atoms, preferably one oxygen atom;

[0111] -R 4 represent:

[0112] i) Straight chain or branched chain, preferably branched chain C7-C 20 C7-C is preferred. 16 Especially C7-C 10 Alkyl groups may contain one or more oxygen atoms, preferably one oxygen atom, preferably interrupted by one or more oxygen atoms, preferably one oxygen atom;

[0113] ii) Straight-chain or branched, preferably branched C1-C7, preferably C2-C6 alkyl, optionally substituted with one or more hydroxyl groups,

[0114] iii) Circular C7-C 10 Especially cyclic C9 alkyl groups.

[0115] Advantageously, according to this preferred embodiment, in formula (I), R 1 and R 2 They are the same and represent straight or branched chains, preferably branched C1-C6, and particularly C1-C4 alkyl.

[0116] Again, advantageously, according to this preferred embodiment, in formula (I), R 1 and R 2 They are the same and represent straight chains or branches, with branched chains preferred (C7-C). 16 Especially C7-C 12 Furthermore, C7-C9 alkyl groups are preferred.

[0117] Again, advantageously, according to this preferred embodiment, in formula (II), R 4 Represents a straight or branched chain, preferably a branched C1-C7, preferably C2-C6 alkyl group, optionally substituted with one or more hydroxyl groups.

[0118] Again, advantageously, according to this preferred embodiment, in formula (II), R 4 Represents a straight or branched chain, preferably a branched C1-C7, preferably a C2-C6 alkyl group, which is substituted with one or more hydroxyl groups, particularly one hydroxyl group.

[0119] More advantageously, the method according to the invention includes mixing:

[0120] (a) at least one organic peroxide of formula (I), selected from di(2-ethylhexyl) peroxydicarbonate, particularly under the trade name 223 is sold as di(sec-butyl) peroxydicarbonate, specifically under the trade name. 225 for sale, and its mixtures; and

[0121] (b) at least one organic peroxide of formula (II), selected from those trade names 10. Tert-butyl peroxyneodecanate sold under the trade name 546 sells tert-amyl peroxyneodecanate, under the trade name 188 sells α-isopropylphenyl peroxyneoheptanoate and hydroxyperoxy esters as defined above, preferably 3-hydroxy-1,1-dimethylbutyl peroxyneoheptanoate, specifically under the trade name 610 sales.

[0122] According to this advantageous embodiment, the organic peroxide of formula (II) is selected from tert-butyl peroxyneodecanate and hydroxyperoxy ester.

[0123] Again, advantageously, according to this embodiment, the organic peroxide of formula (II) is a hydroxyperoxide ester, preferably 3-hydroxy-1,1-dimethylbutyl peroxynedecanoate.

[0124] Preferably, the method according to the invention includes mixing:

[0125] (i) at least one peroxydicarbonate as defined above, and

[0126] (ii) at least one peroxide ester of formula (II) as defined above, preferably selected from tert-butyl peroxyneodecanate, particularly by trade name 10. Sales, by product name 546 sells tert-amyl peroxyneodecanate, under the trade name 546 sells tert-amyl peroxyneodecanate and hydroxyperoxy ester, preferably 3-hydroxy-1,1-dimethylbutyl peroxyneodecanate, specifically under the trade name 610 sells 3-hydroxy-1,1-dimethyl butyl peroxyneodecanoate.

[0127] Preferably, the method according to the invention comprises mixing at least one peroxydicarbonate and at least one peroxy ester as defined above in an aqueous phase.

[0128] The aqueous phase preferably contains at least one emulsifier and water.

[0129] Water may be present in an amount ranging from 50% to 98% by weight, relative to the total weight of the composition.

[0130] Preferably, the method according to the invention includes adding at least one emulsifier.

[0131] Preferably, the emulsifier is selected from cellulose ether derivatives, partially hydrolyzed poly(vinyl acetate), nonionic surfactants, and mixtures thereof.

[0132] The nonionic surfactant (which may or may not be oxyalkylated) is preferably selected from fatty alcohols, fatty acids, (hydrogenated or non-hydrogenated) vegetable or animal oils, glucoside esters, sorbitol esters (Span), alkoxylated sorbitol esters (Tween); or mixtures thereof.

[0133] Preferably, the emulsifier is selected from partially hydrolyzed poly(vinyl acetate).

[0134] More preferably, the emulsifier is selected from poly(vinyl acetate) having a degree of hydrolysis ranging from 70% to 90% or from 40% to 60%.

[0135] The method according to the invention may further include the addition of one or more additives, intended to provide a final composition having specific properties / characteristics. These additives will ideally be present for the final polymerization or copolymerization.

[0136] Additives can be selected from defoamers, chain transfer agents, chain extenders, pH adjusters, plasticizers, and mixtures thereof.

[0137] Preferably, the method according to the invention includes adding at least one plasticizer, preferably selected from phthalate (salt), adipate (salt), benzoate (salt) and hydrogenated derivatives of these molecules, particularly including diisononylcyclohexane and diisononyl cyclohexane dicarboxylate and mixtures thereof.

[0138] Preferably, in the method according to the invention, the mixture of at least one peroxydicarbonate and at least one peroxy ester as defined above is used at a temperature ranging from -10°C to 50°C, particularly at a temperature ranging from 0°C to 30°C.

[0139] Preferably, the composition obtained according to the method of the invention is a liquid, particularly at temperatures ranging from -10°C to 50°C, and especially at temperatures ranging from 0°C to 30°C.

[0140] Preferably, the method according to the invention includes at least:

[0141] (a) Mixing at least one peroxydicarbonate and at least one peroxy ester as defined above in an aqueous phase as defined above.

[0142] (b) Emulsification of the mixture.

[0143] Specifically, the method according to the present invention comprises, sequentially:

[0144] (a) Mixing at least one peroxydicarbonate and at least one peroxy ester as defined above in an aqueous phase as defined above.

[0145] (b) Emulsification of the mixture.

[0146] More specifically, the method according to the invention comprises, sequentially:

[0147] - Add at least one emulsifier as defined above to water to obtain an aqueous phase.

[0148] - Mix at least one peroxydicarbonate and at least one peroxy ester as defined above in an aqueous phase.

[0149] - Emulsification of the mixture.

[0150] Preferably, the peroxydicarbonate and / or peroxyester are diluted with at least one organic solvent or in the form of an aqueous emulsion before mixing according to the method according to the invention.

[0151] In other words, before mixing, peroxydicarbonate and / or peroxyester can be diluted in the composition, which is in liquid form, by at least one organic solvent or placed in an aqueous emulsion.

[0152] Preferably, the peroxydicarbonate and peroxyester are diluted with at least one organic solvent or in the form of an aqueous emulsion before being mixed according to the method of the invention.

[0153] More preferably, the peroxydicarbonate and peroxyester are in the form of an aqueous emulsion before being mixed according to the method of the invention.

[0154] In other words, the method for preparing the composition of organic peroxides includes mixing at least one peroxydicarbonate and at least one peroxy ester as defined above before contacting the composition with one or more olefinically unsaturated monomers; at least one of the organic peroxides, preferably the organic peroxides, is in the form of an aqueous emulsion.

[0155] Preferably, the method for preparing the composition of the organic peroxide comprises mixing at least one peroxydicarbonate as defined above in the form of an aqueous emulsion and at least one peroxy ester as defined above in the form of an aqueous emulsion, and then contacting the composition thus obtained with one or more olefinically unsaturated monomers.

[0156] Alternatively, peroxydicarbonates and / or peroxyesters are in pure form.

[0157] In particular, peroxydicarbonate and peroxyester are in their pure form.

[0158] According to one embodiment, a method for preparing an organic peroxide composition includes mixing at least one peroxydicarbonate as defined above in pure form and at least one peroxy ester as defined above in pure form, and then contacting the resulting composition with one or more olefinically unsaturated monomers.

[0159] According to a preferred feature of the invention, the method for preparing the composition comprises mixing at least one peroxydicarbonate and at least one peroxyester, and then introducing the composition thus obtained into a polymerization reactor, which preferably contains one or more olefinically unsaturated monomers.

[0160] Therefore, the method advantageously employs a mixture prepared prior to injecting the composition into a polymerization reactor, which preferably contains one or more olefinic unsaturated monomers.

[0161] According to another preferred feature, the method according to the invention comprises mixing at least one peroxydicarbonate and at least one peroxy ester in an aqueous phase in the absence of the aforementioned olefinic unsaturated monomers.

[0162] Preferably, the olefinic unsaturated monomer is selected from vinyl halide monomers (i.e., halogenated vinyl monomers) and more preferably vinyl chloride.

[0163] Advantageously, the method according to the invention includes adding at least one peroxy ester as defined above to a composition comprising at least one peroxy dicarbonate as defined above.

[0164] Therefore, the stage of mixing organic peroxides is advantageously the stage of adding at least one peroxy ester as defined above to the composition comprising at least one peroxy dicarbonate as defined above.

[0165] According to this advantageous embodiment, the weight ratio of peroxydicarbonate / peroxyester is preferably from 99 / 1, particularly from 97 / 3, especially from 90 / 10 and preferably from 80 / 20 to 50 / 50.

[0166] According to this embodiment, the addition of at least one peroxide ester improves the stability of the peroxide dicarbonate.

[0167] Aggregation methods

[0168] Another subject of the present invention is a polymerization method for one or more olefinically unsaturated monomers, comprising sequentially:

[0169] (i) Prepare the composition according to the method described above.

[0170] (ii) Contact the composition with one or more olefinic unsaturated monomers.

[0171] Preferably, the contact phase (ii) is performed at least 30 minutes after phase (i), and more preferably at least 1 hour after phase (i).

[0172] Preferably, the method is a method for polymerizing one or more vinyl monomers, preferably halogenated vinyl monomers, and more preferably vinyl chloride.

[0173] As olefinic unsaturated monomers, acrylates, vinyl esters, vinyl halide monomers, vinyl ethers, butadiene, or vinyl aromatic compounds such as styrene may be mentioned.

[0174] Preferably, the olefinic unsaturated monomer is selected from vinyl halide monomers (i.e., halogenated vinyl monomers) and more preferably vinyl chloride.

[0175] Preferably, contacting the composition with one or more olefinically unsaturated monomers includes introducing the composition into a polymerization reactor containing olefinically unsaturated monomers.

[0176] Preferably, the composition is prepared according to the above method in a separate reactor, different from the reactor used to contact the composition with the above-described olefinic unsaturated monomer.

[0177] Preferably, stage (i) of preparing the composition can be used for several polymerizations. In other words, stage (i) of preparing the composition can be followed by several stages (ii) of contacting the composition with one or more olefinically unsaturated monomers.

[0178] use

[0179] The present invention also relates to the use of the compositions as defined above for the polymerization or copolymerization of one or more olefinic unsaturated monomers, particularly vinyl monomers, preferably halogenated vinyl monomers and more preferably vinyl chloride.

[0180] In particular, the composition is used to manufacture halogenated vinyl polymers, preferably poly(vinyl chloride).

[0181] Preferably, the present invention relates to the use of at least one peroxy ester as described above for improving the stability of at least one peroxy dicarbonate as described above.

[0182] polymer

[0183] Another subject of the invention relates to halogenated vinyl polymers obtained by polymerization of at least one olefinically unsaturated monomer as described above in the presence of the composition described above.

[0184] Preferably, the present invention relates to poly(vinyl chloride) obtained by polymerization of vinyl chloride in the presence of a composition obtained by a method defined according to the invention, particularly in the presence of a mixture of organic peroxides as defined above.

[0185] The following examples are used to illustrate the present invention, but are not intended to be limiting. Example

[0186] Example 1

[0187] Composition I below is prepared from the ingredients mentioned in the table below, the amounts of which are shown as weight percentages relative to the total weight of the composition.

[0188] [Table 1]

[0189]

[0190] The tests conducted:

[0191] Peroxydicarbonate (di(2-ethylhexyl) peroxydicarbonate) was measured over a period of 96 hours at 15°C. 223) weight content:

[0192] - In composition I, in the peroxide ester (peroxyneodecanoate 3-hydroxy-1,1-dimethylbutyl ester – In the presence of 610),

[0193] - In a composition identical to composition I but without the peroxide ester; the peroxide ester is replaced by water.

[0194] Figure 1 On the one hand, the weight content of di(2-ethylhexyl) peroxydicarbonate alone is presented as a function of time (curve reference Lx 223), and on the other hand, the weight content of peroxydicarbonate in the presence of 2% by weight of 3-hydroxy-1,1-dimethylbutyl peroxyneodecanoate is presented (curve reference Lx 223,610).

[0195] result

[0196] Figure 1The results showed that, in the presence of 3-hydroxy-1,1-dimethylbutyl peroxynedecanoate, the weight content of di(2-ethylhexyl) peroxydicarbonate decreased less rapidly over a period of 96 hours at 15°C compared to when di(2-ethylhexyl) peroxydicarbonate was present alone in the composition.

[0197] Therefore, the results indicate that di(2-ethylhexyl) peroxydicarbonate is more stable in the presence of 3-hydroxy-1,1-dimethylbutyl peroxynedecanoate than it is alone in the same composition.

[0198] Example II

[0199] In the following examples, the weight content of di(2-ethylhexyl) peroxydicarbonate was measured over a period of 96 hours at 15°C:

[0200] - In composition I, in the peroxide ester (peroxyneodecanoate 3-hydroxy-1,1-dimethylbutyl ester – In the presence of 610),

[0201] -In a composition identical to composition I but without the peroxide ester,

[0202] -In a composition identical to composition I but containing 1% by weight of a peroxide ester,

[0203] -In a composition identical to composition I but containing 3% by weight of a peroxide ester,

[0204] -In a composition identical to composition I but containing 5% by weight of a peroxide ester,

[0205] -In a composition identical to composition I but containing 10% by weight of a peroxide ester,

[0206] Figure 2 Presented as a function of time:

[0207] - Weight content of di(2-ethylhexyl) peroxydicarbonate alone, curve reference Lx 223,

[0208] - The weight content of peroxydicarbonate in the presence of 1% by weight of 3-hydroxy-1,1-dimethylbutyl peroxyneodecanoate, curve reference Lx 223,610 (1%).

[0209] - Peroxydicarbonate weight content in the presence of 2% by weight of 3-hydroxy-1,1-dimethylbutyl peroxyneodecanoate, curve reference Lx 223,610 (2%).

[0210] - Peroxydicarbonate weight content in the presence of 3% by weight of 3-hydroxy-1,1-dimethylbutyl peroxyneodecanoate, curve reference Lx 223,610 (3%).

[0211] - Peroxydicarbonate weight content in the presence of 5% by weight of 3-hydroxy-1,1-dimethylbutyl peroxyneodecanoate, curve reference Lx 223,610 (5%).

[0212] - Peroxydicarbonate weight content in the presence of 10% by weight of 3-hydroxy-1,1-dimethylbutyl peroxynedecanoate, curve reference Lx 223,610 (10%).

[0213] result

[0214] Figure 2 The results showed that, in the presence of 3-hydroxy-1,1-dimethylbutyl peroxynedecanoate, the weight content of di(2-ethylhexyl) peroxydicarbonate decreased less rapidly over a period of 96 hours at 15°C compared to when di(2-ethylhexyl) peroxydicarbonate was present alone in the composition.

[0215] Therefore, the results indicate that di(2-ethylhexyl) peroxydicarbonate is more stable in the presence of 3-hydroxy-1,1-dimethylbutyl peroxynedecanoate than it is alone in the same composition.

[0216] Example III

[0217] In the following examples, the weight content of di(2-ethylhexyl) peroxydicarbonate was measured over a period of 96 hours at 15°C:

[0218] - In composition I, 2% by weight of the peroxide ester (peroxyneodecanoate 3-hydroxy-1,1-dimethylbutyl ester) In the presence of 610),

[0219] -In a composition identical to composition I but without the peroxide ester,

[0220] - In the same composition as Composition I but containing 2.5% by weight of tert-butyl peroxyneodecanate ( In the composition of 10).

[0221] Figure 3 Presented as a function of time:

[0222] - Weight content of di(2-ethylhexyl) peroxydicarbonate alone, curve reference Lx 223,

[0223] - Peroxydicarbonate weight content in the presence of 2% by weight of 3-hydroxy-1,1-dimethylbutyl peroxynedecanoate, curve reference Lx 223,610 (2%).

[0224] - Peroxydicarbonate content in the presence of 2.5% by weight of tert-butyl peroxyneodecanate, curve reference Lx 223, Lup10 (2.5%).

[0225] result

[0226] Figure 3 The results showed that, in the presence of peroxy esters, the weight content of di(2-ethylhexyl) peroxydicarbonate decreased less rapidly over a period of 96 hours at 15°C compared to when di(2-ethylhexyl) peroxydicarbonate was present alone in the composition.

[0227] Therefore, the results indicate that di(2-ethylhexyl) peroxydicarbonate is more stable in the presence of peroxy esters than when it is alone in the same composition and under the same conditions.

[0228] Furthermore, it was found that di(2-ethylhexyl) peroxydicarbonate is more stable in the presence of hydroxyperoxy esters, namely peroxyneodecanoate 3-hydroxy-1,1-dimethylbutyl ester.

Claims

1. A method for preparing a composition of organic peroxides, the method comprising mixing at least one peroxydicarbonate and at least one peroxy ester before introducing the composition into a polymerization reactor and before contacting the composition with one or more olefinically unsaturated monomers, wherein the composition is stored and transported in a stable manner at a temperature above the storage temperature of organic peroxides.

2. The method according to claim 1, characterized in that... Peroxydicarbonate corresponds to the following formula (I): In equation (I), R1 and R2 may be the same or different, representing straight chain, branched chain, or cyclic C1-C 20 Alkyl groups, which may contain one or more heteroatoms.

3. The method according to claim 2, characterized in that... The one or more heteroatoms are one or more oxygen atoms.

4. The method according to claim 2, characterized in that... R1 and R2 may be the same or different, representing straight chains or branched chains C1-C. 16 Alkyl groups, which may contain one or more heteroatoms.

5. The method according to claim 4, characterized in that... R1 and R2 may be the same or different, representing straight chains or branched chains C3-C. 12 alkyl.

6. The method according to claim 5, characterized in that... R1 and R2 may be the same or different, representing straight chains or branched chains C3-C. 10 alkyl.

7. The method according to claim 4, characterized in that... R1 and R2 may be the same or different, representing straight chains or branched chains C1-C. 16 Alkyl groups may contain one or more oxygen atoms.

8. The method according to claim 4, characterized in that R1 and R2 may be the same or different, representing straight chains or branched chains C1-C. 16 Alkyl groups, which can be interrupted by one or more heteroatoms.

9. The method according to claim 8, characterized in that... R1 and R2 may be the same or different, representing straight chains or branched chains C1-C. 16 Alkyl groups can be interrupted by one or more oxygen atoms.

10. The method according to any one of claims 1 to 9, characterized in that... R1 and R2 are the same and represent straight-chain or branched C2-C8 alkyl groups.

11. The method according to claim 10, characterized in that... R1 and R2 are the same and represent branched C2-C8 alkyl groups.

12. The method according to any one of claims 1 to 9, characterized in that... The peroxydicarbonate is selected from di(2-ethylhexyl) peroxydicarbonate, di(sec-butyl) peroxydicarbonate, bis(1-methylheptyl) peroxydicarbonate, di(n-propyl) peroxydicarbonate, di(3-methoxybutyl) peroxydicarbonate, diethyl peroxydicarbonate, and mixtures thereof.

13. The method according to any one of claims 1 to 9, characterized in that... Peroxyesters correspond to the following general formula (II): In formula (II), R3 and R4 may be the same or different, representing straight chain, branched chain, or cyclic C1-C 20 Alkyl groups, which may contain one or more heteroatoms and / or optionally be substituted with one or more hydroxyl groups.

14. The method according to claim 13, characterized in that... In formula (II), R3 and R4 may be the same or different, representing straight chain, branched chain, or cyclic C1-C 20 Alkyl groups may contain one or more oxygen atoms.

15. The method according to claim 13, characterized in that... In formula (II), R3 and R4 may be the same or different, representing straight chain, branched chain, or cyclic C1-C 20 Alkyl groups, which can be interrupted by one or more heteroatoms.

16. The method according to claim 15, characterized in that... In formula (II), R3 and R4 may be the same or different, representing straight chain, branched chain, or cyclic C1-C 20 Alkyl groups can be interrupted by one or more oxygen atoms.

17. The method according to claim 13, characterized in that: -R3 represents straight, branched, or cyclic C4-C. 20 Alkyl groups, which may contain one or more oxygen atoms; -R4 represents: i) Straight chain or branched chain C7-C 20 Alkyl groups, which may contain one or more oxygen atoms; ii) Straight-chain or branched C1-C7 alkyl groups, optionally substituted with one or more hydroxyl groups; iii) Circular C7-C 10 alkyl.

18. The method according to claim 17, characterized in that... R3 represents the C4-C branch. 20 alkyl.

19. The method according to claim 17, characterized in that... R3 represents straight-chain, branched, or cyclic C7-C. 20 alkyl.

20. The method according to claim 19, characterized in that... R3 represents straight-chain, branched, or cyclic C7-C. 16 alkyl.

21. The method according to claim 20, characterized in that... R3 represents straight-chain, branched, or cyclic C7-C. 10 alkyl.

22. The method according to claim 17, characterized in that... R3 represents straight-chain, branched, or cyclic C4-C. 20 Alkyl groups may contain one oxygen atom.

23. The method according to claim 17, characterized in that... R3 represents straight-chain, branched, or cyclic C4-C. 20 Alkyl groups can be interrupted by one or more oxygen atoms.

24. The method according to claim 23, characterized in that R3 represents straight-chain, branched, or cyclic C4-C. 20 Alkyl groups can be interrupted by an oxygen atom.

25. The method according to claim 17, characterized in that... R4 represents i) branch C7-C 20 alkyl.

26. The method according to claim 17, characterized in that... R4 represents i) straight chain or branched chain C7-C 16 alkyl.

27. The method according to claim 26, characterized in that... R4 represents i) straight chain or branched chain C7-C 10 alkyl.

28. The method according to claim 17, characterized in that... R4 represents i) straight chain or branched chain C7-C 20 Alkyl groups may contain one oxygen atom.

29. The method according to claim 17, characterized in that... R4 represents i) straight chain or branched chain C7-C 20 Alkyl groups can be interrupted by one or more oxygen atoms.

30. The method according to claim 29, characterized in that... R4 represents i) straight chain or branched chain C7-C 20 Alkyl groups can be interrupted by an oxygen atom.

31. The method according to claim 17, characterized in that... R4 represents ii) branched C1-C7 alkyl groups.

32. The method according to claim 17, characterized in that... R4 represents ii) straight-chain or branched C2-C6 alkyl.

33. The method according to claim 17, characterized in that... R4 represents (iii) cyclic C9 alkyl.

34. The method according to any one of claims 1 to 9, characterized in that... Peroxy esters are selected from α-isopropylphenyl peroxyneodecanoate, α-isopropylphenyl peroxyneoheptanoate, 2,4,4-trimethylpentyl-2-yl peroxyneodecanoate, tert-butyl peroxy(n-heptanoate), tert-butyl peroxyneodecanoate, α-isopropylphenyl peroxy(n-heptanoate), tert-pentyl peroxy(n-heptanoate), tert-butyl peroxyneoheptanoate, and 2,5-dimethyl-2,5-di(2-ethylhexanoylperoxy)hexyl Alkane, tert-amyl peroxy(2-ethylhexanoate), tert-butyl peroxy(2-ethylhexanoate), 1,1,3,3-tetramethylbutyl peroxy(2-ethylhexanoate), hydroxyperoxy ester, tert-amyl peroxyneodecanate, 1,1,3,3-tetramethylbutyl peroxyneodecanate, 1,1,3,3-tetramethylbutyl peroxynepentanoate, tert-hexyl peroxyneodecanate, tert-hexyl peroxynepentanoate, and mixtures thereof.

35. The method according to any one of claims 1 to 9, characterized in that... Peroxide esters are hydroxyperoxide esters, selected from peroxyneodecanoate 4-hydroxy-2-methylpentyl ester, peroxyneohepanoate 4-hydroxy-2-methylpentyl ester, peroxy(2-ethylhexanoate) 4-hydroxy-2-methylpentyl ester, peroxy(2-phenylbutyric acid) 4-hydroxy-2-methylpentyl ester, peroxy(2-phenoxypropionic acid) 4-hydroxy-2-methylpentyl ester, peroxy(2-butyloctanoate) 4-hydroxy-2-methylpentyl ester, peroxyneohexanoate 4-hydroxy-2-methylpentyl ester, peroxynetridecanoate 4-hydroxy-2-methylpentyl ester, peroxyneohex ... 2-Hydroxy-2-methylhexyl ester, 4-hydroxy-2-methylhexyl peroxyneodecanonical, 5-hydroxy-1,3,3-trimethylcyclohexyl peroxyneodecanonical, 4-hydroxy-2,6-dimethyl-2,6-di(neohexanoylperoxy)heptane, 4-hydroxy-2,6-dimethyl-2,6-di(neohexanoylperoxy)heptane, 3-hydroxy-1,1-dimethyl butyl peroxy(2-ethylhexanoic acid), 3-hydroxy-1,1-dimethyl butyl peroxyneodecanonical, 3-hydroxy-1,1-dimethyl butyl peroxyneodecanonical, and mixtures thereof.

36. The method according to claim 35, characterized in that... The peroxy ester is selected from 3-hydroxy-1,1-dimethyl butyl peroxyneodecanoate.

37. The method according to any one of claims 1 to 9, characterized in that... The peroxide esters are selected from tert-butyl peroxyneodecanate, tert-amyl peroxyneodecanate, α-isopropylphenyl peroxyneoheptanoate, and hydroxyperoxide esters.

38. The method according to any one of claims 1 to 9, characterized in that... It includes mixing at least one peroxydicarbonate and at least one peroxy ester in an aqueous phase.

39. The method according to any one of claims 1 to 9, characterized in that... Peroxydicarbonates and / or peroxyesters are diluted with at least one organic solvent or are in the form of an aqueous emulsion.

40. The method according to any one of claims 1 to 9, characterized in that... It includes the addition of at least one emulsifier.

41. The method according to claim 40, characterized in that At least one emulsifier is selected from cellulose ether derivatives, partially hydrolyzed poly(vinyl acetate), nonionic surfactants, and mixtures thereof.

42. The method according to any one of claims 1 to 9, characterized in that... The mixture was prepared at a temperature ranging from -10°C to 50°C.

43. The method according to claim 42, characterized in that The mixture was prepared at a temperature ranging from 0°C to 30°C.

44. The method according to any one of claims 1 to 9, characterized in that... The mixture is prepared before injecting the composition into a polymerization reactor containing one or more olefinic unsaturated monomers.

45. A method for polymerizing one or more olefinically unsaturated monomers, comprising sequentially: (i) The composition is prepared according to the method defined in any one of claims 1 to 43. (ii) Contact the composition with one or more olefinic unsaturated monomers.

46. ​​Use of the composition obtained according to any one of claims 1 to 41 for the polymerization or copolymerization of one or more olefinic unsaturated monomers.

47. The use according to claim 46, characterized in that... Alkene unsaturated monomers are halogenated vinyl monomers.

48. The use according to claim 47, characterized in that The olefinic unsaturated monomer is vinyl chloride.

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