MACROMONOMER, METHOD FOR OBTAINING SAME AND COPOLYMER CONTAINING SAME

Abstract

This invention relates to an LCST macromonomer, obtained by a reaction between an LCST telomere and a compound containing a carbon-carbon double bond. The invention also relates to an LCST copolymer, obtained by a reaction between the LCST macromonomer and a water-soluble monomer.

Claims

1. A Lower Critical Solution Temperature (LCST macromonomer of formula (I): ##STR00010## wherein, R.sub.1, R.sub.2, and R.sub.3 are independently hydrogen, methyl group, C(?O)YR.sub.5, CH.sub.2C(?O)YR.sub.5, C(?O)O.sup.?M.sup.+, or CH.sub.2C(?O)O.sup.?M.sup.+; Y is NR.sub.5 or O; R.sub.5, R.sub.5 are independently a hydrogen atom or a carbon radical, saturated or unsaturated, optionally aromatic, linear, branched or cyclic, comprising 1 to 30 carbon atoms, comprising from 0 to 4 heteroatoms chosen from the group comprising 0, N, and S; R.sub.4 is CH.sub.2, C(?O), C.sub.6H.sub.4C(CH.sub.3).sub.2NHC(?O) where C.sub.6H.sub.4 is a disubstituted benzene ring, C(?O)OCH.sub.2CH(OH)CH.sub.2, or CH.sub.2OCH.sub.2CH(OH)CH.sub.2; M.sup.+ is an alkali metal cation, an alkaline earth metal cation, or an ammonium; X is chosen from the groups of formula ZR.sub.8S wherein Z is O, NH, OC(?O), OC(?O)CH(NH.sub.2) and R.sub.8 is a C.sub.nH.sub.2n group with integer n between 1 and 30, monomer A is of formula (II): ##STR00011## monomer B is of formula (III): ##STR00012## wherein, R.sub.6, R.sub.6, and R.sub.7 are independently a carbon radical, saturated or unsaturated, optionally aromatic, linear, branched, or cyclic, comprising 1 to 30 carbon atoms, comprising from 0 to 4 heteroatoms chosen from the group comprising O, N, and S; monomer C is at least one anionic monomer and/or at least one cationic monomer and/or at least one nonionic monomer, u, v, and w are the molar proportions of the monomers, such that u+v+w=100 mol %, and u is between 50 and 99 mol %, preferably between 60 and 98 mol %, more preferably between 70 and 95 mol % relative to all of the molar proportions of monomers A, B, and C, v is between 1 and 20 mol %, preferably between 1 and 15 mol %, more preferably between 2 and 10 mol % with respect to the total molar proportions of monomers A, B, and C, w is between 0 and 30 mol %, preferably between 1 and 25 mol %, more preferably between 3 and 20 mol % with respect to the total molar proportions of monomers A, B, and C.

2. The macromonomer of claim 1, wherein: R.sub.1, R.sub.2, and R.sub.3 independently are a hydrogen atom, or a methyl group; R.sub.4 is CH.sub.2, C(?O),C.sub.6H.sub.4C(CH.sub.3).sub.2NHC(?O) where C.sub.6H.sub.4 is a disubstituted benzene ring, C(?O)OCH.sub.2CH(OH)CH.sub.2 or CH.sub.2OCH.sub.2CH(OH)CH.sub.2; X is of the formula ZR.sub.8S wherein Z is O or NH and R.sub.8 is a C.sub.nH.sub.2n group with n being an integer between 1 and 30; R.sub.6 and R.sub.6 are independently a carbon radical, saturated or unsaturated, comprising between 2 and 10 carbon atoms; R.sub.7 is a carbon radical, saturated or unsaturated, linear or branched comprising between 3 and 10 carbon atoms.

3. The macromonomer according to claim 1, wherein monomer C is an anionic monomer.

4. The macromonomer according to claim 1, wherein monomer C comprises at least one anionic monomer selected from acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, 2-acrylamido 2-methylpropane sulfonic acid, vinylsulfonic acid, vinylphosphonic acid, allyl sulfonic acid, allyl phosphonic acid, styrene sulfonic acid; and the water-soluble salts of these monomers such as their alkali metal, alkaline earth metal, or ammonium salts.

5. The macromonomer according to claim 1, wherein: R.sub.1, R.sub.2, and R.sub.3 are independently a hydrogen atom or a methyl group; R.sub.4 is CH.sub.2, C(?O), C.sub.6H.sub.4C(CH.sub.3).sub.2NHC(?O) where C.sub.6H.sub.4 is a disubstituted benzene ring, C(?O)OCH.sub.2CH(OH)CH.sub.2, or CH.sub.2OCH.sub.2CH(OH)CH.sub.2; X is of formula ZR.sub.8S wherein Z is an O or NH and R.sub.8 is a C.sub.nH.sub.2n group with n being an integer between 1 and 18; monomer C is 2-acrylamido-2-methylpropane sulfonic acid and/or its alkali metal, alkaline-earth metal, or ammonium salt; R.sub.6 and R.sub.6 are the CH.sub.2CH.sub.3 group; R.sub.7 is the C(CH.sub.3).sub.3 group.

6. The macromonomer according to claim 1, wherein monomer C is 2-acrylamido-2-methylpropane sulfonic acid and/or its alkali metal, alkaline-earth metal, or ammonium salt.

7. A method of preparing at least one LCST macromonomer according to claim 1 comprising: the preparation of at least one LCST telomer from at least one A monomer of formula (II), at least one B monomer of formula (III), at least one C monomer, and a telogenic agent, the preparation of a macromonomer by reaction between the LCST telomer obtained and a compound containing a carbon-carbon double bond, wherein the carbon-carbon double bond is always present in the LCST macromonomer obtained after said reaction.

8. The method of preparing at least one LCST macromonomer according to claim 7, wherein the telogenic agent is selected from compounds of the formula ZR.sub.8SH wherein Z is OH, NH.sub.2, HOC(?O)CH(NH.sub.2) or C(?O)OH, and R.sub.8 is a C.sub.nH.sub.2n group with n being an integer between 1 and 30.

9. The method of preparing at least one LCST macromonomer according to claim 7, wherein the telogenic agent is selected from compounds of formula ZR.sub.8SH wherein Z is OH or NH.sub.2 and R.sub.8 is a C.sub.nH.sub.2n group with n being an integer between 1 and 30.

10. The method of preparing at least one LCST macromonomer according to claim 7, wherein the telogenic agent is selected from compounds of the formula ZR.sub.10SH wherein Z is OH or NH.sub.2 and R.sub.10 is a C.sub.nH.sub.2n group with n being an integer between 1 and 18.

11. The method of preparing at least one LCST macromonomer according to claim 7, wherein the compound containing a carbon-carbon double bond is selected from acryloyl chloride, acrylic acid, methacryloyl chloride, methacrylic acid, maleic anhydride, methacrylic anhydride, aliphatic unsaturated isocyanates, allyl chloride, allyl bromide, glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether, and metallyl glycidyl ether.

12. A heat-sensitive copolymer, comprising: 95 mol % to 99.99999 mol % of at least one water-soluble monomer, and 10.sup.?5 mol % to 5 mol % of at least one LCST macromonomer according to claim 1.

13. The heat-sensitive copolymer according to claim 12, wherein the water-soluble monomer is chosen from nonionic monomers, anionic monomers, and/or cationic monomers.

14. The heat-sensitive copolymer according to claim 12, wherein the water-soluble monomer is a non-ionic monomer chosen from the group comprising water-soluble vinyl monomers, preferably acrylamide; N-isopropylacrylamide; N,N-dimethylacrylamide; N-vinylformamide; acryloyl morpholine; N,N-diethyl acrylamide; N-tert-butyl acrylamide; N-vinylpyrrolidone; N-vinyl caprolactam; and diacetone acrylamide.

15. The heat-sensitive copolymer of claim 12, wherein the water-soluble monomer is an anionic monomer selected from the group consisting of acrylic acid; acrylic acid; methacrylic acid; itaconic acid; crotonic acid; maleic acid; fumaric acid; monomers of strong acid type having, for example, a function of the sulfonic acid or phosphonic acid type, such as 2-acrylamido-2-methylpropane sulfonic acid, vinyl sulfonic acid, vinylphosphonic acid, allyl sulfonic acid, allyl phosphonic acid, styrene sulfonic acid, 2-acrylamido-2-methylpropane sulfonic acid; and the water-soluble salts of these monomers such as their alkali metal, alkaline earth metal, or ammonium salts.

16. The heat-sensitive copolymer according to claim 12, wherein the water-soluble monomer is a cationic monomer chosen from the group comprising quaternized or salified dimethylaminoethyl acrylate (ADAME) and dimethylaminoethyl methacrylate (MADAME), dimethyldiallylammonium chloride (DADMAC), acrylamido propyltrimethyl ammonium chloride (APTAC) and methacrylamido propyltrimethyl ammonium chloride (MAPTAC).

17. The macromonomer according to claim 2, wherein monomer C is an anionic monomer.

18. The macromonomer according to claim 2, wherein monomer C comprises at least one anionic monomer selected from acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, 2-acrylamido 2-methylpropane sulfonic acid, vinylsulfonic acid, vinylphosphonic acid, allyl sulfonic acid, allyl phosphonic acid, styrene sulfonic acid; and the water-soluble salts of these monomers such as their alkali metal, alkaline earth metal, or ammonium salts.

19. The macromonomer according to claim 18, wherein: R.sub.1, R.sub.2, and R.sub.3 are independently a hydrogen atom or a methyl group; R.sub.4 is CH.sub.2, C(?O), C.sub.6H.sub.4C(CH.sub.3).sub.2NHC(?O) where C.sub.6H.sub.4 is a disubstituted benzene ring, C(?O)OCH.sub.2CH(OH)CH.sub.2, or CH.sub.2OCH.sub.2CH(OH)CH.sub.2; X is of formula ZR.sub.8S wherein Z is an O or NH and R.sub.8 is a C.sub.nH.sub.2n group with n being an integer between 1 and 18; monomer C is 2-acrylamido-2-methylpropane sulfonic acid and/or its alkali metal, alkaline-earth metal, or ammonium salt; R.sub.6 and R.sub.6 are the CH.sub.2CH.sub.3 group; R.sub.7 is the C(CH.sub.3).sub.3 group.

20. The macromonomer according to claim 2, wherein monomer C is 2-acrylamido-2-methylpropane sulfonic acid and/or its alkali metal, alkaline-earth metal, or ammonium salt.

Description

DESCRIPTION OF THE FIGURES

[0122] The figures below illustrate, in a non-limitative manner, the advantages and characteristics of the invention:

[0123] FIG. 1 is a graph that plots viscosity versus temperature for a P1 polymer solution at pH=1 and pH=8.

[0124] FIG. 2 is a graph that plots viscosity versus temperature for a P2 polymer solution.

EXAMPLES OF EMBODIMENTS OF THE INVENTION

1/Synthesis of the T1 Telomere

[0125] To make a telomere called T1, the following process is performed.

[0126] In a jacketed reactor: [0127] Deionized water (410 g), and 2-acrylamido-2-methylpropane sulfonic acid (ATBS, 48.3 g, i.e., 0.21 mol), tert-butyl acrylamide (TBA, 6.7 g, or 0.05 mol) and diethylacrylamide (DEA, 114 g, or 0.89 mol) are added. [0128] The mixture is stirred. [0129] The pH of the mixture is adjusted between 4.0 and 5.0 using a solution of 40% NaOH by weight in water. [0130] The mixture obtained is heated to 50? C. [0131] It is deoxygenated with a nitrogen sparge for 40 minutes. [0132] Aminoethanethiol HCl (2.5 g) is added. [0133] 2,2-azobis(2-methylpropionamidine) dihydrochloride (0.22 g) is added to initiate telomerization. [0134] After stabilization of the temperature, the mixture is stirred for 2 hours and then cooled to 25? C.

[0135] The telomere obtained is of formula (VI):

##STR00008##

[0136] Wherein u=85 mol %, v=5 mol %, and w=10 mol %, relative to the total number of moles of the three monomers.

2/Synthesis of Macromonomer M1

[0137] To make a macromonomer called M1, the following method is performed.

[0138] In a jacketed reactor: [0139] we add 400 g of the T1 telomer solution at 23% by weight in water. [0140] The solution is stirred. [0141] The pH is adjusted to 7.5 using a solution of 40% NaOH by weight in water. [0142] It is cooled to 5? C. [0143] Using a burette, 1.5 g of acryloyl chloride is added drop by drop. [0144] The pH is continuously adjusted between 7 and 9 using a solution of 40% NaOH by weight in water. [0145] The temperature is maintained at 5? C. throughout the reaction. [0146] The mixture is stirred for 2 hours after the end of the reaction while continuing to check the pH.

[0147] A concentrated viscous solution containing 25% by weight of macromonomer M1 of formula (VII) is obtained.

##STR00009##

[0148] Of course, u, v, and w, remain unchanged and are thus such that u=85 mol %, v=5 mol %, and w=10 mol %, relative to the total number of moles of the three monomers.

3/Synthesis of the Heat-Sensitive Copolymer in the P1 Solution

[0149] The heat-sensitive copolymer is prepared by radical polymerization.

[0150] Into a 1 liter adiabatic reactor: [0151] 189 g of dimethylaminoethyl methacrylate (MADAME) solution at 100% by weight in water, 290 g of macromonomer M1 solution at 25% by weight in water, and 20 g of water are added. [0152] The solution is stirred. [0153] It is deoxygenated with a nitrogen sparge for 30 minutes. [0154] Polymerization is initiated at low temperature with Mohr's salt oxidizing-reducing couplesodium persulfate and does not exceed 30? C. [0155] A P1 polymer is obtained.

4/Viscosity Test of a P1 Polymer

[0156] An aqueous solution of P1 polymer at 1% by weight is prepared in deionized water at pH=8 adjusted using a solution of NaOH 40% by weight in water, and a solution of P1 polymer whose pH was lowered to 1 using a concentrated acid solution.

[0157] The viscosity of the 2 solutions is measured with a rheometer (cone-plane module 6 cm, angle 2?) with a shear at 10 s.sup.?1 according to a temperature ramp ranging from 5 to 80? C. In this way, we obtain the graph in FIG. 1.

[0158] On this graph, we observe that the aqueous solution has an increase in viscosity V (cps) with the temperature T (? C.), until reaching a maximum threshold around 80? C. of about 900 centipoises (cps) for the solution at pH=1 and about 650 cps for the solution at pH=8.

[0159] The presence of gel particles is evaluated by passing the copolymer solution through a 200 ?m filter and observing the number of gel points on the filter.

[0160] For the aqueous solution of a P1 polymer, we note the absence of gel particles.

5/Synthesis of a P2 Polymer in Solution

[0161] The copolymer is prepared by radical polymerization.

[0162] In a 1 liter adiabatic reactor: [0163] 78 g of acrylamide (AM) solution at 50% by weight in water, 109 g of 2-acrylamido-2-methylpropane sulfonic acid (ATBS) at 50%, 237.6 g of a solution of macromonomer M1 at 25% by weight in water and 574 g of water are added. The transfer agent is added. [0164] The solution is stirred. [0165] It is deoxygenated with a nitrogen sparge for 30 minutes. [0166] Polymerization is initiated at low temperature with an oxidizing-reducing couple Mohr's saltsodium persulfate and does not exceed 30? C. [0167] A P2 polymer is obtained.

6/P2 Polymer Viscosity Test

[0168] An aqueous solution of a P2 polymer at 4% by weight in a brine comprising 60 g/l of NaCl is prepared.

[0169] The viscosity of the 2 solutions is measured with a rheometer (cone-plane module 6 cm, angle 2?) with a shear at 7 s.sup.?1 according to a temperature ramp ranging from 20 to 80? C. In this way, we obtain the graph in FIG. 2.

[0170] On this graph, it is observed that the aqueous solution exhibits an increase in viscosity V (cps) with the temperature T(? C.), until reaching a maximum threshold around 45? C. of about 17,000 cps. Above this threshold, the viscosity decreases.

[0171] By repeating the previously described protocol, we note the absence of gel particles for the aqueous P2 polymer solution.

[0172] Thus, these examples show that the copolymer of the invention has a significant and satisfactory thickening power for use as a thickening agent, and also has the advantage of being free of gel particles during its use.