Liquid composition comprising two initiators, its process of polymerization, use and material or composition obtained following polymerization of composition
The present invention relates to a liquid composition comprising a monomer, a (meth)acrylic polymer and at least two initiators. In particular the present invention relates to a liquid composition comprising a monomer, a (meth)acrylic polymer and at least two initiators that have a different half life time. That liquid composition can be used as a syrup and especially as a syrup for impregnation of fibres or fibrous material. Also concerned is a thermoplastic material obtained after polymerization of the liquid composition. The invention also relates to a process for manufacturing such a liquid composition. The invention also relates to a process for impregnating a fibrous substrate of long fibres with said liquid composition. The invention also relates to a fibrous substrate impregnated with said liquid composition which is useful for manufacturing composite parts. The present invention also relates to a process for manufacturing mechanical parts or structural elements made of composite material and to mechanical parts or structural elements made of composite material obtained via a process using such a liquid composition.
1. A liquid composition comprising,
a) a (meth)acrylic polymer (P1),
b) a (meth)acrylic monomer (M1), and
c) two different initiators (Ini1) and (Ini2) having at any given temperature T 1 different half-life times t 1/2 ,
said liquid composition is having a dynamic viscosity of between 10 mPa*s and 10,000 mPa*s at 25° C.,
wherein the quantity of said two initiators (Ini1) and (Ini2) together in the composition is between 0.75 phr and 15 phr relative to the sum of the (meth)acrylic monomer (M1) and (meth)acrylic polymer (P1), and
wherein the two initiators (Ini1) and (Ini2) are selected from the group consisting of diacyl peroxides, peroxy esters, peroxydicarbonates, dialkyl peroxides, peroxyacetals, hyperperoxide, and peroxyketale, and
wherein the first initiator (Ini1) has a half-life time t 1/2 of 1 hour at a temperature between 40° C. and 90° C., and wherein the second initiator (Ini2) has a half-life time t 1/2 of 1 hour at a temperature of at least 70° C.
2. The liquid composition as claimed in claim 1 , wherein the quantity of said two initiators (Ini1) and (Ini2) together in the composition is between 0.75 phr and 8 phr relative to the sum of (meth)acrylic monomer (M1) and (meth)acrylic polymer (P1).
3. The liquid composition according to claim 1 , wherein the second initiator (Ini2) has at a given temperature T 1 a half-life time t 1/2 that is at least two times of the half-life time t 1/2 of the first initiator (Ini1).
4. The liquid composition according to claim 1 , wherein the second initiator (Ini2) has at a given temperature T 1 a half-life time t 1/2 that is at least six times of the half-life time t 1/2 of the first initiator (Ini1).
5. The liquid composition according to claim 1 , wherein the first initiator (Ini1) has a half-life time t 1/2 of 1 hour at a temperature between 45° C. and 80° C.
6. The liquid composition according to claim 1 , wherein the second initiator (Ini2) has a half-life time t 1/2 of at least 1 hour at a temperature of at least 75° C.
7. The liquid composition according to claim 1 , wherein the difference of the temperature for a given half time life between the initiator (Ini2) and (Ini1) is between 5K and 50K.
8. The liquid composition according to claim 1 , wherein the weight ratio between the two initiators (Ini2) and (Ini1) is between 1/10 and 10/1.
9. The liquid composition according to claim 1 , wherein the two initiators (Ini1) and (Ini2) are selected from the group consisting of diisobutyryl peroxide, cumyl peroxyneodecanoate, di(3-methoxybutyl) peroxydicarbonate, 1,1,3,3-Tetramethylbutyl peroxyneodecanoate, cumyl peroxyneoheptanoate, di-n-propyl peroxydicarbonate, tert-amyl peroxyneodecanoate, di-sec-butyl peroxydicarbonate, diisopropyl peroxydicarbonate, di(4-tert-butylcyclohexyl) peroxydicarbonate, di-(2-ethylhexyl)-peroxydicarbonate, tert-butyl peroxyneodecanoate, di-n-butyl peroxydicarbonate, dicetyl peroxydicarbonate, dimyristyl peroxydicarbonate, 1,1,3,3-tetramethylbutylperoxypivalate, tert-butyl peroxyneoheptanoate, tert-amyl peroxypivalate, tert-butyl peroxypivalate, di-(3,5,5-trimethylhexanoyl)-peroxide, dilauroyl peroxide, didecanoyl peroxide, 2,5-dimethyl-2,5-di(2-ethylhexanoylperoxy)-hexane, 1,1,3,3-tetramethylbutyl peroxy-2-ethylhexanoate, tert-amyl peroxy-2-ethylhexanoate, dibenzoyl peroxide, tert-butyl peroxy-2-ethylhexanoate, tert-butyl peroxydiethylacetate, tert-butyl peroxyisobutyrate, 1,1-di-(tert-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-di(tert-amylperoxy)cyclohexane, 1,1-di-(tert-butylperoxy)-cyclohexane, tert-amyl peroxy-2-ethylhexylcarbonate, tert-amyl peroxyacetate, tert-butyl peroxy-3,5,5-trimethylhexanoate, 2,2-di-(tert-butylperoxy)-butane, tert-butyl peroxyisopropylcarbonate, tert-butyl peroxy-2-ethylhexylcarbonate, tert-amyl peroxybenzoate, tert-butyl peroxyacetate, butyl 4,4-di(tert-butylperoxy)valerate, tert-butyl peroxybenzoate, di-tert-amylperoxide, dicumyl peroxide, di-(2-tert-butyl-peroxyisopropyl)-benzene, 2,5-dimethyl-2,5-di-(tert-butylperoxy)-hexane, tert-butylcumyl peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexyne-3, di-tert-butyl peroxide, 3,6,9-triethyl-3,6,9-trimethyl-1,4,7-triperoxonane, 2,2′-azobis-isobutyronitrile (AIBN), 2,2′-azodi-(2-methylbutyronitrile), azobisiso-butyramide, 2,2′-azo-bis(2,4-dimethylvaleronitrile), 1,1′-Azodi(hexahydrobenzonitrile), and 4,4′-azobis(4-cyanopentanoic).
10. The liquid composition according to claim 1 , wherein the initiator (Ini1) is a peroxydicarbonate.
11. The liquid composition according to claim 1 , wherein the initiator (Ini1) has the following general formula (1):
wherein R 1 and R 2 each are present and said alkyl group could be linear, branched or cyclic, or a combination of the three, having at least 6 carbon atoms.
12. The liquid composition according to claim 11 , wherein the groups R 1 and R 2 each have between 10 and 30 carbon atoms.
13. The liquid composition according to claim 1 , wherein the initiator (Ini1) is chosen from di(4-tert-butylcyclohexyl) peroxydicarbonate, dicetyl peroxydicarbonate and dimyristyl peroxydicarbonate and initiator (Ini2) is chosen from benzoyl peroxide, t-butylperoxy 2-ethylhexanoate, dilauroyl peroxide, 2,5-dimethyl-2,5-di(2-ethylhexanoyl peroxy)hexane and didecanoyl peroxide.
14. The liquid composition according to claim 1 , wherein the initiator (Ini1) is chosen from di(4-tert-butylcyclohexyl) peroxydicarbonate and initiator (Ini2) is chosen from benzoyl peroxide, t-butylperoxy 2-ethylhexanoate, dilauroyl peroxide and didecanoyl peroxide.
15. The liquid composition according to claim 1 , wherein the initiator (Ini1) is chosen from dicetyl peroxydicarbonate and initiator (Ini2) is chosen from benzoyl peroxide, t-butylperoxy 2-ethylhexanoate, dilauroyl peroxide and didecanoyl peroxide.
16. The liquid composition according to claim 1 , wherein the initiator (Ini1) is chosen from dimyristyl peroxydicarbonate and initiator (Ini2) is chosen from benzoyl peroxide, t-butylperoxy 2-ethylhexanoate, dilauroyl peroxide and didecanoyl peroxide.
17. The liquid composition according to claim 1 , wherein the (meth)acrylic polymer (P1) comprises at least 50% by weight of methyl methacrylate (MMA).
18. The liquid composition according to claim 1 , characterized in that the (meth)acrylic monomer (M1) is selected from the group consisting of acrylic acid, methacrylic acid, alkyl acrylic monomers and alkyl methacrylic monomers, and mixtures thereof, the alkyl group containing from 1 to 22 linear, branched or cyclic carbons; the alkyl group preferably containing from 1 to 12 linear, branched, and cyclic carbons.
19. The liquid composition as claimed in claim 18 , wherein the (meth)acrylic monomer is chosen from methyl methacrylate, ethyl methacrylate, methyl acrylate, ethyl acrylate, methacrylic acid, acrylic acid, n-butyl acrylate, isobutyl acrylate, n-butyl methacrylate, isobutyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, isobornyl acrylate and isobornyl methacrylate, and mixtures thereof.
20. An impregnation process for impregnating a fibrous substrate, said fibrous substrate consisting of fibres having an aspect ratio of at least 1000, wherein said process comprises a step of impregnating said fibrous substrate with liquid composition according to claim 1 .