Liquid composition comprising three 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 three initiators. In particular the present invention relates to a liquid composition comprising a monomer, a (meth)acrylic polymer and at least three 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) three initiators (Ini1), (Ini2) and (Ini3),
said liquid composition having a dynamic viscosity of between 10 mPa*s and 10,000 mPa*s at 25° C.,
wherein the three initiators (Ini1), (Ini2) and (Ini3) have at any given temperature different half-life times t 1/2 ,
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.,
wherein the second initiator (Ini2) has a half-life time t 1/2 of 1 hour at a temperature between 70° C. and 100° C. and a half-life time t 1/2 that is at least two times the half-life time t 1/2 of the first initiator (Ini1) at a given temperature (T 1 ), and
wherein the third initiator (Ini3) has a half-life time t 1/2 of 1 hour at a temperature between 75° C. and 160° C. and a half-life time t 1/2 that is at least two times the half-life time t 1/2 of the second initiator (Ini2) at the given temperature (T 1 ),
wherein the given temperature (T 1 ) is between 40° C. and 160° C.
2. The liquid composition as claimed in claim 1 , wherein the level of the three initiators (Ini1), (Ini2) and (Ini3) together in the composition is between 0.1 phr and 15 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 given temperature T 1 is between 40° C. and 140° C.
4. 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 50° C. and 75° C.
5. The liquid composition according to claim 1 , wherein the temperature for a given half-life time between the initiators (Ini3), (Ini2) and (Ini1) is different by at least 5K.
6. The liquid composition according to claim 1 , wherein the temperature for a given half-life time between the initiators (Ini3) and (Ini1) is different by 10K to 50K.
7. The liquid composition according to claim 1 , wherein the temperature for a given half-life time between the initiators (Ini2) and (Ini1) is different by 6K to 40K.
8. The liquid composition according to claim 1 , wherein the initiators (Ini3), (Ini2) and (Ini1) 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-amyl peroxyneodecanoate, 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-butylperoxy-2-ethylhexanoate, tert-butyl peroxydiethylacetate, tert-butylperoxyisobutyrate, 1, 1-di-(tert-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-di(tert-amylperoxy)cyclohexane, 1,1-di-(tert-butylperoxy)-cyclohexane, tert-amylperoxy-2-ethylhexylcarbonate, tert-amyl peroxyacetate, tert-butyl peroxy-3,5,5-trimethylhexanoate, 2,2-di-(tert-butylperoxy)-butane, tert-butylperoxyisopropylcarbonate, tert-butyl peroxy-2-ethylhexylcarbonate, tert-amylperoxybenzoate, 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, tertbutylcumylperoxide, 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′-azobisisobutyronitrile (AIBN), 2,2′-azodi-(2-methylbutyronitrile), azobisisobutyramide, 2,2′-azobis(2,4-dimethylvaleronitrile), 1,1′-Azodi(hexahydrobenzonitrile), and 4,4′-azobis(4-cyanopentanoic).
9. The liquid composition according to claim 1 , wherein the initiator (Ini1) is selected from the group consisting of 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-amyl peroxyneodecanoate, 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, and 1,1,3,3-tetramethylbutyl peroxy-2-ethylhexanoate.
10. The liquid composition according to claim 1 , wherein the initiator (Ini2) is selected from the group consisting of 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-butylperoxyisopropyl)-benzene, 2,5-dimethyl-2,5-di-(tert-butylperoxy)-hexane, tertbutylcumyl peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexyne-3, di-tert-butyl peroxide, and 3,6,9-triethyl-3,6,9-trimethyl-1,4,7-triperoxonane.
11. The liquid composition according to claim 1 , wherein the initiator (Ini3) is selected from the group consisting of 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, and 3,6,9-triethyl-3,6,9-trimethyl-1,4,7-triperoxonane.
12. The liquid composition according to claim 1 , wherein the (meth)acrylic polymer (P1) comprises at least 50% by weight of methyl methacrylate (MMA).
13. The liquid composition according to claim 1 , wherein the (meth)acrylic monomer is selected from the group consisting of methyl methacrylate, ethyl methacrylate, methyl acrylate, ethyl acrylate, methacrylic acid, acrylic acid, n-butyl acrylate, isobutyl acrylate, cyclohexyl acrylate, cyclohexyl methacrylate, isobornyl acrylate and isobornyl methacrylate, and mixtures thereof.
14. The liquid composition according to claim 1 , wherein the (meth)acrylic monomer(s) (M1) in the liquid composition or (meth)acrylic syrup are present in proportions of between 40% and 90% by weight of the composition comprising (meth)acrylic monomer(s) (M1) and (meth)acrylic polymer (P1).