Process of free-radical polymerization or crosslinking in the presence of a selected organic peroxide prepared by an ex situ process

1. A process of free-radical polymerization or cross-linking comprising the steps of contacting:

a) at least one polymerizable monomer or at least one compound to be cross-linked and

b) at least one organic peroxide selected from the group consisting of di(n-propyl) peroxydicarbonate, di(sec-butyl) peroxydicarbonate, di(2-ethylhexyl) peroxydicarbonate, 1,1-dimethyl-3-hydroxybutyl peroxyneodecanoate, α-cumyl peroxyneodecanoate, α-cumyl peroxyneoheptanoate, tert-amyl peroxyneodecanoate, tert-butyl peroxyneodecanoate, tert-amyl peroxypivalate, tert-butyl peroxypivalate, 2,5-dimethyl-2,5-di(2-ethylhexanoylperoxy)hexane, tert-amyl peroxy-2-ethylhexanoate, tert-butyl peroxy-2-ethyl hexanoate, tert-amyl peroxyacetate, tert-butyl peroxyacetate, tert-amyl perbenzoate, tert-butyl perbenzoate, OO-tert-amyl-O(2-ethylhexyl) monoperoxycarbonate, OO-tert-butyl-O-isopropyl monoperoxycarbonate, OO-tert-butyl 1-(2-ethylhexyl) monoperoxycarbonate, poly(tert-butyl peroxycarbonate) polyether, decanoyl peroxide, lauroyl peroxide, succinic acid peroxide, benzoyl peroxide, 1,1-di(tert-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-di(tert-butylperoxy)cyclohexane, 1,1-di(tert-amylperoxy)cyclohexane, n-butyl 4,4-di(tert-butylperoxy)valerate, ethyl 3,3-di(tert-amylperoxy)butyrate, tert-butyl peroctoate, ethyl 3,3-di(tert-butylperoxy)butyrate, cumene hydroperoxide, and tert-butyl hydroperoxide, and mixtures thereof;

wherein the organic peroxide is prepared continuously by an ex situ process with the aid of a closed plate exchanger and reagents for forming the organic peroxide are introduced into the closed plate exchanger at a rate ranging from 1 liter/hour to 2000 liters/hour,

the closed plate exchanger comprising plates and a plate separation device allowing the plates to move apart, wherein said plate separation device is selected from the group consisting of i) a system of nuts and bolts which are mounted with springs that undergo compression if the pressure in the reactor exceeds a predetermined value or ii) a system of nuts and bolts which are mounted with elastic washers of Belleville type such that the plates separate by a predetermined distance if the pressure exceeds a defined value.

2. The process according to claim 1 , characterized in that the organic peroxide is prepared at a temperature ranging from about 0° C. to about 100° C.

3. The process according to claim 1 , characterized in that the organic peroxide is prepared at a temperature ranging from about 5° C. to about 60° C.

4. The process according to claim 1 , characterized in that the plate exchanger comprises at least two inlet points for the reagents.

5. The process according to claim 1 , characterized in that the plate exchanger comprises at least three inlet points.

6. The process according to claim 1 , characterized in that the organic peroxide is introduced continuously during the free-radical polymerization or cross-linking reaction.

7. The process according to claim 1 , characterized in that the free-radical polymerization or cross-linking is selected from polymerization or copolymerization of vinyl monomers, the thermosetting of unsaturated polyester resins and elastomers, the cross-linking of polyolefins, or the grafting of polymers with the aid of vinyl monomers.

8. A process of suspension polymerization comprising the steps of contacting vinyl chloride and at least one organic peroxide selected from the group consisting of di(n-propyl) peroxydicarbonate, di(sec-butyl) peroxydicarbonate, di(2-ethylhexyl) peroxydicarbonate, 1,1-dimethyl-3-hydroxybutyl peroxyneodecanoate, α-cumyl peroxyneodecanoate, α-cumyl peroxyneoheptanoate, tert-amyl peroxyneodecanoate, tert-butyl peroxyneodecanoate, tert-amyl peroxypivalate, and tert-butyl peroxypivalate, and mixtures thereof;

wherein the organic peroxide is prepared continuously by an ex situ process in a closed plate exchanger and reagents for forming the organic peroxide are introduced into the closed plate exchanger at a rate ranging from 1 liter/hour to 2000 liters/hour,

the closed plate exchanger comprising plates and a plate separation device allowing the plates to move apart, wherein said plate separation device is selected from the group consisting of i) a system of nuts and bolts which are mounted with springs that undergo compression if the pressure in the reactor exceeds a predetermined value or ii) a system of nuts and bolts which are mounted with elastic washers of Belleville type such that the plates separate by a predetermined distance if the pressure exceeds a defined value.

9. The process according to claim 8 , characterized in that the organic peroxide is introduced continuously during the polymerization reaction.

10. A process of suspension polymerization of styrene comprising the steps of contacting styrene and at least one organic peroxide selected from the group consisting of 2,5-dimethyl-2,5-di(2-ethylhexanoylperoxy)hexane, tert-butyl peroxy-2-ethyl hexanoate, tert-amyl perbenzoate, tert-butyl perbenzoate, OO-tert-amyl-O(2-ethylhexyl) monoperoxycarbonate, OO-tert-butyl-O-isopropyl monoperoxycarbonate, OO-tert-butyl 1-(2-ethylhexyl) monoperoxycarbonate, poly(tert-butyl peroxycarbonate) polyether, decanoyl peroxide, lauroyl peroxide, succinic acid peroxide, 1,1-di(tert-butylperoxy)-3,3,5-trimethylcyclohexane;

wherein the organic peroxide is prepared continuously by an ex situ process in a closed plate exchanger, the closed plate exchanger comprising plates and a plate separation device allowing the plates to move apart, wherein said plate separation device is selected from the group consisting of i) a system of nuts and bolts which are mounted with springs that undergo compression if the pressure in the reactor exceeds a predetermined value or ii) a system of nuts and bolts which are mounted with elastic washers of Belleville type such that the plates separate by a predetermined distance if the pressure exceeds a defined value.

11. A process of polymerization of acrylic monomers comprising the steps of contacting one or more acrylic monomers and at least one organic peroxide selected from the group consisting of 2,5-dimethyl-2,5-di(2-ethylhexanoylperoxy)hexane, tert-amyl peroxy-2-ethylhexanoate, tert-butyl peroxy-2-ethylhexanoate, tert-amyl peroxyacetate, tert-butyl peroxyacetate, tert-amyl perbenzoate;

wherein the organic peroxide is prepared continuously by an ex situ process in a closed plate exchanger, the closed plate exchanger comprising plates and a plate separation device allowing the plates to move apart, wherein said plate separation device is selected from the group consisting of i) a system of nuts and bolts which are mounted with springs that undergo compression if the pressure in the reactor exceeds a predetermined value or ii) a system of nuts and bolts which are mounted with elastic washers of Belleville type such that the plates separate by a predetermined distance if the pressure exceeds a defined value.

12. A process of free-radical polymerization or cross-linking comprising the steps of contacting at least one polymerizable monomer or a compound to be cross-linked and at least one organic peroxide selected from the group consisting of di(n-propyl) peroxydicarbonate, di(sec-butyl) peroxydicarbonate, di(2-ethylhexyl) peroxydicarbonate, 1,1-dimethyl-3-hydroxybutyl peroxyneodecanoate, α-cumyl peroxyneodecanoate, α-cumyl peroxyneoheptanoate, tert-amyl peroxyneodecanoate, tert-butyl peroxyneodecanoate, tert-amyl peroxypivalate, tert-butyl peroxypivalate, 2,5-dimethyl-2,5-di(2-ethylhexanoylperoxy)hexane, tert-amyl peroxy-2-ethylhexanoate, tert-butyl peroxy-2-ethyl hexanoate, tert-amyl peroxyacetate, tert-butyl peroxyacetate, tert-amyl perbenzoate, tert-butyl perbenzoate, OO-tert-amyl-O(2-ethylhexyl) monoperoxycarbonate, OO-tert-butyl-O-isopropyl monoperoxycarbonate, OO-tert-butyl 1-(2-ethylhexyl) monoperoxycarbonate, poly(tert-butyl peroxycarbonate) polyether, decanoyl peroxide, lauroyl peroxide, succinic acid peroxide, benzoyl peroxide, 1,1-di(tert-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-di(tert-butylperoxy)cyclohexane, 1,1-di(tert-amylperoxy)cyclohexane, n-butyl 4,4-di(tert-butylperoxy)valerate, ethyl 3,3-di(tert-amylperoxy)butyrate, tert-butyl peroctoate, ethyl 3,3-di(tert-butylperoxy)butyrate, cumene hydroperoxide, and tert-butyl hydroperoxide, and mixtures thereof, wherein the process further comprises:

(a) preparing a selected organic peroxide continuously in a closed plate exchanger, wherein reagents for forming the selected organic peroxide are introduced into the closed plate exchanger at a rate ranging from 1 liter/hour to 2000 liters/hour, the closed plate exchanger comprising plates and a plate separation device allowing the plates to move apart, wherein said plate separation device is selected from the group consisting of i) a system of nuts and bolts which are mounted with springs that undergo compression if the pressure in the reactor exceeds a predetermined value or ii) a system of nuts and bolts which are mounted with elastic washers of Belleville type such that the plates separate by a predetermined distance if the pressure exceeds a defined value,

(b) optionally transferring the organic peroxide from step (a) to a purification unit,

(c) optionally transferring the organic peroxide obtained in step (a) or in step (b) to a polymerization or cross-linking reactor, and

(d) free-radical polymerizing or cross-linking the at least one polymerizable monomer or the at least one compound to be cross-linked, with one or more organic peroxides from steps (a), (b) or (c).