Formulations of random polymers for improving crude petroleum flow

Abstract

The present invention is related to the use of formulations of new random copolymers and terpolymers, synthesized by a method of semi continuous emulsion polymerization, and that function as flow improvers, lowering the pour point and reducing the viscosity of Mexicans crude oils, which have gravities within the range of 9 to 30 API.

Claims

1. A method for producing random polystyrene-polyacetate polymers, wherein said method comprises a semi-continuous emulsion polymerization in a main reactor by feeding a pre-emulsion of styrene and acetate monomers and a transfer agent from one or several tanks by a respective metering pump, at a reaction temperature in the range between 50 and 95 C., where the feed rate of the pre-emulsion is from 0.003 to 0.009 g/mL*min, where the amount of monomers used is between 5 and 95% by weight, and the amount of transfer agent is up to 12 grams per 100.0 grams of the mixture of monomers, wherein the random polymers are copolymers having the following formula: ##STR00005## where: R.sub.1, R.sub.2 and R.sub.4 are represented by independent radical groups listed below: R.sub.1=C.sub.6H.sub.5, CH.sub.3C.sub.6H.sub.4, (CH.sub.3).sub.3C.sub.6H.sub.3, (CH.sub.3).sub.3C.sub.6H.sub.2, (CH.sub.3).sub.3CC.sub.6H.sub.4; R.sub.2=H, CH.sub.3; R.sub.4=H, CN; m=from 10 to 700; n=from 1 to 220.

2. The method of claim 1, wherein the rate of addition of the preemulsion is from 0.004 to 0.007 g/mL.Math.min, and the amount of monomers used is between 10 and 90 weight %.

3. The method according to claim 1, wherein m is from 20 to 650 and n is from 10 to 200.

4. The method according to claim 1, wherein m is from 40 to 620 and n is from 20 to 170.

5. The method according to claim 1, wherein said random polymer formulation comprises a mixture of copolymers having number average molecular weights ranging between 2,000 to 90,000 Daltons.

6. The method according to claim 1, wherein said random polymers have number average molecular weights ranging between 5,000 and 80,000 Daltons.

7. A method for producing random polyacrylate-polyacetate polymers, wherein said method comprises a semi-continuous emulsion polymerization process in a main reactor by feeding a pre-emulsion of acrylate and acetate monomers and a transfer agent to the main reactor at a rate of 0.003 to 0.009 g/mL.Math.min, at a reaction temperature of 50 to 90 C., the amount of monomers is between 5 and 95% by weight, and the amount of transfer agent is up to 12 grams per 100.0 grams of monomers, wherein said random polymer formulation comprises random copolymers having the formula: ##STR00006## where: R.sub.2, R.sub.3 and R.sub.4 are represented by independent radical groups listed below: R.sub.2=H, CH.sub.3; R.sub.3=CH.sub.3, C.sub.2H.sub.5, C.sub.4H.sub.9, C.sub.6H.sub.13, C.sub.8H.sub.17, C.sub.10H.sub.21, C.sub.12H.sub.25, C.sub.18H.sub.37; R.sub.4=H, CN; u=from 1 to 220; and v=from 1 to 50.

8. The method according to claim 7, wherein u is from 10 to 200 and v is from 10 to 40.

9. The method according to claim 7, wherein u is from 30 to 170 and v is from 15 to 30.

10. The method according to claim 7, wherein said random polymer formulation comprises a mixture of copolymers having molecular weights ranging between 2,000 to 90,000 Daltons.

11. The method according to claim 10, wherein said molecular weights range between 5,000 and 80,000 Daltons.

12. A method for producing random polystyrene-polyacrylate-polyacetate terpolymers, wherein said method comprises a semi-continuous emulsion polymerization process in a main reactor by feeding a pre-emulsion of styrene, acrylate and acetate monomers and a transfer agent to the main reactor at a rate of 0.003 to 0.009 g/mL-min, at a reaction temperature of 50 to 90 C., the amount of monomers is between 5 and 95% by weight, and the amount of transfer agent is up to 12 grams per 100.0 grams of monomers, wherein said random polymer formulation comprises a random terpolymer having the formula: ##STR00007## where: R.sub.1, R.sub.2, R.sub.3 and R.sub.4 are represented by independent radical groups listed below: R.sub.1=C.sub.6H.sub.5, CH.sub.3C.sub.6H.sub.4, (CH.sub.3).sub.2C.sub.6H.sub.3, (CH.sub.3).sub.3C.sub.6H.sub.2, (CH.sub.3).sub.3CC.sub.6H.sub.4; R.sub.2=H, CH.sub.3; R.sub.3=CH.sub.3, C.sub.2H.sub.5, C.sub.4H.sub.9, C.sub.6H.sub.13, C.sub.8H.sub.17, C.sub.10H.sub.21, C.sub.12H.sub.25, C.sub.18H.sub.37; R.sub.4=H, CN; x=from 2 to 900; Z=from 1 to 300; y=from 1 to 226.

13. The method according to claim 12, wherein x is from 20 to 850, z is from 10 to 235 and y is from 10 to 210.

14. The method according to claim 12, wherein x is from 25 to 700, z is from 20 to 220 and y is from 20 to 200.

15. The method according to claim 12, wherein the number average molecular weights are in a range from 1,000 to 140,000 Daltons.

16. The method according to claim 12, wherein the molecular weights are in number range from 2,000 to 100,000 Daltons.

17. A process for producing a random polymer or copolymer selected from the group consisting of ##STR00008## where: R.sub.1, R.sub.2 and R.sub.4 are represented by independent radical groups listed below: R.sub.1=C.sub.6H.sub.5, CH.sub.3C.sub.6H.sub.4, (CH.sub.3).sub.2C.sub.6H.sub.3, (CH.sub.3).sub.3C.sub.6H.sub.2, (CH.sub.3).sub.3CC.sub.6H.sub.4; R.sub.2=H, CH3; R.sub.3=CH.sub.3, C.sub.2H.sub.5, C.sub.4H.sub.9, C.sub.6H.sub.13, C.sub.8H.sub.17, C.sub.10H.sub.21, C.sub.12H.sub.25, C.sub.18H.sub.37; R.sub.4=H, CN; m=from 10 to 700; n=from 1 to 220; u=from 1 to 220; v=from 1 to 50; x=from 2 to 900; y=from 1 to 226; z=from 1 to 300; said method comprising the steps of preparing a reaction mixture of monomers selected from the group consisting of acrylate, styrene, and acetate monomers, at least one surfactant, a transfer agent and a buffer solution, and feeding said reaction mixture into a reactor at a temperature of about 50 to 95 C. at a rate of about 0.003 to 0.009 g/ml.Math.min to obtain said random polymer or copolymer, the reaction mixture including said at least one monomer in an amount of 5 to 95% by weight and the amount of the transfer agent in an amount of up to 12 grams per 100 grams of the at least one monomer, wherein said random polymer is effective in reducing the viscosity and depressing the pour point of crude oil having an API gravity of 9 to 30 API.

18. The method according to claim 17, wherein said random polymer or copolymer has a molecular weight of about 2,000 to 90,000 Daltons.

19. The method according to claim 18, wherein m is 20 to 650; n is 10 to 200; u is 10 to 200; v is 10 to 40; x is 20 to 850; z is 10 to 235; and y is 20 to 200.

20. A method for producing random polystyrene-polyacrylate polymers, wherein said method comprises a semi-continuous emulsion polymerization process in a main reactor by feeding a pre-emulsion of styrene and acrylate monomers and a transfer agent to the main reactor at a rate of from 0.003 to 0.009 g/mL-min, at a reaction temperature of 50 to 90 C., the amount of monomers is between 5 and 95% by weight, and the amount of transfer agent is up to 12 grams per 100.0 grams of monomers, wherein said random polymer formulation comprises random copolymers having the formula: where, ##STR00009## R.sub.1=C.sub.6H.sub.5, CH.sub.3C.sub.6H.sub.4, (CH.sub.3).sub.2C.sub.6H.sub.3, (CH.sub.3).sub.3C.sub.6H.sub.2, (CH.sub.3).sub.3CC.sub.6H.sub.4; R.sub.2=H, CH.sub.3; R.sub.3=CH.sub.3, C.sub.2H.sub.9, C.sub.4H.sub.9, C.sub.6H.sub.13, C.sub.8H.sub.17, C.sub.10H.sub.21, C.sub.12H.sub.25, C.sub.18H.sub.37; p=from 1 to 700; q=from 1 to 50.

21. The method of claim 1, wherein said reaction mixture includes a monomer mixture consisting essentially of a styrene monomer selected from the group consisting of styrene, 2,4,6-trimethyl-styrene, 2,4-dimethyl-styrene, 3-methyl-styrene, 4-methyl-styrene, 2-methyl-styrene, 4-tert-butyl-styrene, ,2-dimethyl-styrene, -methyl-styrene, and methyl styrene, and an acetate monomer selected from the group consisting of vinyl acetate, and cyanovinyl acetate.

22. The method of claim 7, wherein said reaction mixture includes a monomer mixture consisting essentially of an acetate monomer selected from the group consisting of vinyl acetate and cyanovinyl acetate, and an acrylate monomer selected from the group consisting of methyl acrylate, tert-butyl methacrylate, butyl acrylate, butyl methacrylate, hexyl acrylate, hexyl methacrylate, iso-butyl acrylate, iso-butyl methacrylate, ethyl acrylate, ethyl methacrylate, tert-butyl acrylate, 3,5,5-trimethyl-hexyl acrylate, iso-decyl acrylate, iso-decyl methacrylate, iso-octyl acrylate, lauryl acrylate, lauryl methacrylate, octadecyl acrylate, 2-ethyl-hexyl acrylate, and 2-ethyl-hexyl methacrylate.

23. The method of claim 12, wherein said reaction mixture includes a monomer mixture consisting essentially of a styrene monomer selected from the group consisting of styrene, 2,4,6-trimethyl-styrene, 2,4-dimethyl-styrene, 3-methyl-styrene, 4-methyl-styrene, 2-methyl-styrene, 4-tert-butyl-styrene, ,2-dimethyl-styrene, -methyl-styrene, and methyl styrene, an acrylate monomer selected from the group consisting of methyl acrylate, tert-butyl methacrylate, butyl acrylate, butyl methacrylate, hexyl acrylate, hexyl methacrylate, Iso-butyl acrylate, iso-butyl methacrylate, ethyl acrylate, ethyl methacrylate, tert-butyl acrylate, 3,5,5-trimethyl-hexyl acrylate, iso-decyl acrylate, iso-decyl methacrylate, iso-octyl acrylate, lauryl acrylate, lauryl methacrylate, octadecyl acrylate, 2-ethyl-hexyl acrylate, 2-ethyl-hexyl methacrylate and an acetate monomer selected from the group consisting of vinyl acetate, and cyanovinyl acetate.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) The following figures are given in order to understand clearly the performance of the formulation of random polymers for improving crude petroleum flow and are used as reference of the application examples.

(2) FIG. 1 shows the effect of the pour point decrease activity in light crude oil of examples E1-E4, evaluated between 200 and 4,000 ppm, and compared to the commercial product COM-01.

(3) FIG. 2 shows the effect of the pour point decrease activity in middle crude oils, evaluated from 250 to 4,000 ppm.

(4) FIG. 3 exhibits the effect of the reducing viscosity activity at 20 C. in heavy crude oil in examples 6, 7, 8, 9 and 10, evaluated at 1,000 ppm.

(5) FIG. 4 presents the effect of the viscosity decrease activity at 20 C. in heavy crude oil of examples 11, 14 and 16 evaluated at 1,000 ppm.

(6) FIG. 5 exposes the effect of the viscosity decrease activity in heavy crude oil at different temperatures of examples 11, 12 and 16 evaluated at 500 and 1,000 ppm.

(7) FIG. 6 shows the effect of the decrease activity of the activity in heavy crude oil at different temperatures of examples 12, COM-01 and COM-02, evaluated at 1,000 ppm.

DETAILED DESCRIPTION OF THE INVENTION

(8) The present invention consists of the synthesis of new random copolymers and terpolymers by semicontinuous emulsion polymerization and the preparation of formulations (random copolymers and terpolymers combined with organic solvents) and their application as flow improvers and viscosity reducers. The invention is also directed to a process of reducing the viscosity and depressing the pour point of crude oil by mixing the crude oil with an effective amount of the random copolymers and terpolymers to reduce the viscosity and depress the pour point. In schemes 1 to 3 the copolymer structure (random combination of a couple of monomers) are shown and in scheme 4 the terpolymer structure obtained from three monomers combination are shown:

(9) ##STR00001##
Copolymers

(10) ##STR00002##

(11) ##STR00003##
Terpolymers

(12) ##STR00004##
where:
R.sub.1, R.sub.2, R.sub.3 and R.sub.4 are represented by independent radical groups listed below:
R.sub.1=C.sub.6H.sub.5, CH.sub.3C.sub.6H.sub.4, (CH.sub.3).sub.2C.sub.6H.sub.3, (CH.sub.3).sub.3C.sub.6H.sub.2, (CH.sub.3).sub.3CC.sub.6H.sub.4;
R.sub.2=H, CH.sub.3;
R.sub.3=CH.sub.3, C.sub.2H.sub.5, C.sub.4H.sub.9, C.sub.6H.sub.13, C.sub.8H.sub.17, C.sub.10H.sub.21, C.sub.12H.sub.25, C.sub.18H.sub.37;
R.sub.4=H, CN.
and where:
x, y, z, m, n, p, q, u and v are numbers within the following ranges:
x=from 2 to 900, preferably from 20 to 850, even more preferably from 25 to 700;
z=from 1 to 300, preferably from 10 to 235, still more preferably from 20 to 220;
y=from 1 to 226, preferably from 10 to 210, still more preferably from 20 to 200;
m=from 10 to 700, preferably from 20 to 650, still more preferably from 40 to 620;
n=from 1 to 220, preferably from 10 to 200, still more preferably from 20 to 170;
p=from 1 to 700, preferably from 25 to 650, still more preferably from 60 to 620;
q=from 1 to 50, preferably from 5 to 45, even more preferably from 10 to 40;
u=from 1 to 220, preferably from 10 to 200, more preferably from 30 to 170;
v=from 1 to 50, preferably from 10 to 40, more preferably from 15 to 30.

(13) Additionally, the molecular weights are in the following ranges, from 1,000 to 100,000 Daltons, preferably between 5,000 and 90,000 Daltons for the case of copolymers and from 1,000 to 140,000, preferably from 2,000 to 100,000 Daltons in the case of random terpolymers.

(14) The copolymers and terpolymers of the present invention are prepared by emulsion polymerization technique, which presents ecological advantages when using water as dispersion medium avoiding the use of large amounts of organic solvents during the synthesis stage. Emulsion polymerization is widely used for the synthesis of adhesives, paints and varnishes, but has not reported used as improvers in crudes oil (Charles Ad 2003).

(15) The following describes by way of example, it does not imply any limitation, the monomers used in the synthesis of polymers object of this invention: methyl acrylate, tert-butyl methacrylate, butyl acrylate, butyl methacrylate, hexyl acrylate, hexyl methacrylate, iso-butyl acrylate, iso-butyl methacrylate, ethyl acrylate, ethyl methacrylate, tert-butyl acrylate, 3,5,5-trimethyl-hexyl acrylate, iso-decyl acrylate, iso-decyl methacrylate, iso-octyl acrylate, lauryl acrylate, lauryl methacrylate, octadecyl acrylate, 2-ethyl-hexyl acrylate, 2-ethyl-hexyl methacrylate, styrene, 2,4,6-trimethyl-styrene, 2,4-dimethyl-styrene, 3-methyl-styrene, 4-methyl-styrene, 2-methyl-styrene, 4-tert-butyl-styrene, ,2-dimethyl-styrene, -methyl-styrene, methyl styrene, vinyl acetate, and cyanovinyl acetate.

(16) The synthesis of polymers (random copolymers and terpolymers) of the present invention, which are effective in the lowering of the pour point and viscosity reduction of light, median and mainly heavy crudes oil, comprising seven stages:

(17) 1) Preparation of the initiator.

(18) 2) Preparation of surfactant solutions ((Anionic(A) and/or nonionic (B))

(19) 3) Preparation of buffer solution

(20) 4) Preparation of the monomers (combination of two monomers for copolymers and three monomers for terpolymers)

(21) 5) Preparation of Cuba or foot main reactor.

(22) 6) Preparation tank addition.

(23) 7) Polymerization of combinations of two or three monomers.

(24) The synthesis of polymers using the semicontinuous method was used (Reyes-Mercado Y. et al.) which is described below. This method is illustrative but not limiting:

(25) 1) Initiator Preparation:

(26) In a balloon flask equipped with magnetic stirring, is placed a suitable amount of initiator, and dissolved in deionized water and kept stirring for 10 minutes. These amounts can vary between 0.5 and 15.0 g of initiator per 100.0 g of deionized water. As initiators, potassium, sodium or ammonium persulfates, as well as sodium or potassium methabisulfite and benzoyl hydroperoxide can be used.

(27) 2) Preparation of Surfactant Solutions.

(28) In a flask equipped with magnetic stirring, are placed an appropriate amount of surfactant A (ionic) and surfactant B (nonionic), both are dissolved in deionized water and kept stirring for 40 minutes. These amounts can vary between 0.5 and 50.0 g of surfactant per 100.0 g of deionized water.

(29) 3) Preparation of Buffer Solution.

(30) The buffer ensures no abrupt changes in the pH of the system. In a balloon flask equipped with magnetic stirring ball, is placed an appropriate amount of buffer, (for example sodium or potassium bicarbonate) dissolved in deionized water and kept stirring for 10 minutes. These amounts can vary between 0.5 and 15.0 g of initiator per 100.0 g of deionized water.

(31) 4) Preparation of the Monomers.

(32) In a volumetric flask, is placed the appropriate amount of monomer or monomers required (two monomers for copolymers and three monomers for terpolymers). The compositions of each monomer in the mixture can vary between 1% and 99%, preferably between 5% and 90% compared to total monomer. It requires a transfer agent (for example dodecyl or terdodecyl mercaptane) to control the molecular weights of polymers. The transfer agent is added to the mixture of monomers. The amount of transfer agent can vary between 0.0 and 12.0 g per 100.0 g of monomer, according to the desired molecular weight. This mixture is stirred for about 5 minutes.

(33) 5) Preparation of Cuba or Foot Main Reactor:

(34) The reactions were conducted in a glass reactor of one liter capacity with a heating jacket through which water is recirculated at constant temperature. Agitation is achieved by a propeller of two sheets of Teflon-coated material, moved by a mechanical stirrer of varying acceleration. The reactor also has a condensation system, with connections for temperature monitoring, connection for inert gas injection and sampling connection. The reactor is filled with a solution of appropriate amounts of surfactant A and surfactant B, buffer solution, deionized water and a small amount of mixture of monomers. These amounts can vary between 1.0 and 25.0 g of solution per 100.0 g of monomers. Deionized water is added, which can vary between 70 and 300 g. Subsequently, the reactor is pressurized with nitrogen to ensure inert atmosphere. The temperature was set between 50 and 90 C. to ensure the smooth progress of polymerization. After 10 to 40 minutes of stirring, is added the appropriate amount of initiator solution. This amount can vary between 1.0 and 20.0 g of initiator solution. Again, the reactor is pressurized with nitrogen to ensure polymerization.

(35) 6) Preparation Tank Addition.

(36) The addition tank was carried out in a glass flask of one liter capacity with connection to suction of dosing pump and with controlled magnetic stirring. Once the preparation of the foot of cuba proceed to slowly add the remaining monomer mixture, solutions of surfactant A, B and the remaining buffer in addition to the tank. Finally, deionized water is added, which can vary between 70.0 and 300.0 g per 100.0 g of monomers.

(37) 7) Copolymerization or Terpolymerization of Monomers.

(38) It connects the addition tank to the main reactor (foot of cuba), through a metering pump. The ratio of feed addition tank ranges from 0.003 to 0.009 g/mL-min, more preferably 0.004 to 0.007 g/mL-min. This rate of addition guarantees the existence of monomer deficiency in the main reactor and ensures that the pairs or trios of monomers react with each other and respectively forming random copolymers or terpolymers. Do not place the addition in the range of speeds of addition, as this will form large sequences of a single monomer within the chains and even form mixtures of homopolymers.

(39) To obtain the desired molecular weight after the addition of the monomers, it is necessary to complete the reaction by adding small amounts of initiator and increasing the temperature to 90 and 95 C. for one hour. The copolymer or terpolymer was subsequently placed in sealed containers. Random copolymer or terpolymer reactions achieve conversions between 98.00-99.99% by weight (Castro L V et al, 2008). The products obtained have latex form. The dispersion of latex in water is easier to process and avoids the use of organic solvents, without health and the environment risks. Stressing further that without this synthesis procedure, it is virtually impossible to obtain the random polymers (copolymers and terpolymers).

(40) Once obtained copolymers and terpolymers were characterized using the instrumental methods:

(41) 1.Infrared brand model Thermo Nicolet AVATAR 330 Spectrometer Fourier Transform using the method of film technique with software version 7.0 OMNIC.

(42) 2.Nuclear Magnetic Resonance Jeol Eclipse equipment, operating at 300 MHz and 75 MHz for .sup.1H and .sup.13C spectra respectively, using deuterated chloroform as solvent; the shifts are indicated in parts per million, about tetramethylsilane (TMS) signal, as internal standard.
3.Size exclusion chromatograph Agilent model 1100 (CET), with PLgel column and using tetrahydrofuran (THF) as eluent, to calculate the molecular distribution of copolymers and terpolymers and the polydispersity index (I).

(43) Molecular masses, polydispersity indices and spectroscopic characteristics are now described in Tables 1 and 2, which does not mean limitation:

(44) TABLE-US-00001 TABLE 1 Copolymers number molecular masses (Mn) and polydispersity index (I) measured by (CET). Polydispersity Copolymers Mn (g/mol) Index I Physical State E-1 2938 1.4 Viscous semi solid E-2 2213 1.2 Viscous semi solid E-3 9279 2.1 Viscous semi solid E-4 1691 1.5 Viscous semi solid E-5 55278 2.8 Viscous semi solid

(45) TABLE-US-00002 TABLE 2 Terpolymers number molecular masses (Mn) and polydispersity index (I) measured by (CET). Polydispersity Terpolymers Mn (g/mol) Index I Physical state E-6 1448 1.9 Viscous semi solid E-7 1109 3.3 Viscous semi solid E-8 139900 2.3 Viscous semi solid E-9 2057 1.8 Viscous semi solid E-10 23488 1.7 Viscous semi solid E-11 2223 3.3 Viscous semi solid E-12 21547 2.1 Viscous semi solid E-13 2954 1.7 Viscous semi solid E-14 20701 1.9 Viscous semi solid E-15 1184 2.0 Viscous semi solid E-16 6816 2.7 Viscous semi solid

EXAMPLES

(46) The following examples are presented to illustrate the best mode of random polymer synthesis, formulation and implementation as flow improvers in crudes oil with API gravities ranging from 9 to 30. These examples should not be regarded as limiting what is claimed.

E-1

(47) Poly(styrene).sub.p-poly(acrylate).sub.q (R.sub.1=phenyl, R.sub.2=Hydrogen, R.sub.3=butyl acrylate), with the following composition 30 g of monomer A and 70 g of monomer B, with 8% of transfer agent: viscous semisolid; I.R. cm.sup.1: 3082.7, 3060.3, 3026.5, 2926.3, 2854.5, 1943.5, 1870.6, 1801.7, 1729.9, 1601.6, 1493.4, 1452.6, 1355.4, 1252.3, 1160, 1068.2, 1029.08, 944.4, 841.3, 759.6, 699.6, 543.8; .sup.13C RMN (CDCl.sub.3): 170.5, 145.4, 128.1, 127.8, 125.8, 70.6, 40.5, 32.0, 29.7, 28.9, 22.8, 21.0, 14.2.

E-2

(48) Poly(acetate).sub.u-poly(acrylate).sub.v (R.sub.2=Hydrogen, R.sub.3=butyl acrylate, R.sub.4=Hydrogen), with the following composition 30 g of monomer A and 70 g of monomer B, with 8% of transfer agent: viscous semisolid; I.R. cm.sup.1: 2959.4, 2931.7, 2873.6, 1736.6, 1459.9, 1371.7, 1237.7, 1167.6, 1119.1, 1023.5, 942.9; .sup.13C RMN (CDCl.sub.3): 174.7, 170.3, 70.5, 69.9, 64.6, 62.2, 41.5, 40.4, 39.5, 31.9, 39.65, 29.7, 29.4, 28.9, 22.7, 20.9, 19.2, 14.1, 13.8.

E-3

(49) Poly(styrene).sub.m-poly(acetate).sub.n (R.sub.1=phenyl, R.sub.2=Hydrogen, R.sub.4=Hydrogen), with the following composition 30 g of monomer A and 70 g of monomer B, with 2% of transfer agent: viscous semisolid; I.R. cm.sup.1: 3445.7, 3081.8, 3059.5, 3025.5, 2923.6, 2851.5, 1943.8, 1870.5, 1803.3, 1736.2, 1601.1, 1492.8, 1452.0, 1372.2, 1244.8, 1118.5, 1028.2, 757.4, 698.6, 540.2; .sup.13C RMN (CDCl.sub.3): 145.3, 128.0, 125.7, 70.6, 44.0, 40.6.

E-4

(50) Poly(styrene).sub.m-poly(acetate).sub.n (R.sub.1=phenyl, R.sub.2=Hydrogen, R.sub.4=Hydrogen), with the following composition 30 g of monomer A and 70 g of monomer B, with 8% of transfer agent: viscous semisolid; I.R. cm.sup.1: 3059.7, 3025.5, 2923.8, 2852.3, 1943.4, 1871.6, 1738.2, 1601.1, 1492.8, 1452.1, 1372.8, 1243.1, 1108.7, 1027.9, 757.2, 698.9, 540.3; .sup.13C RMN (CDCl.sub.3): 170.5, 145.4, 128.1, 127.8, 125.6, 70.6, 40.6, 31.9, 29.6, 22.8, 21.0, 14.2.

E-5

(51) Poly(styrene).sub.m-poly(acetate).sub.n (R.sub.1=phenyl, R.sub.2=Hydrogen, R.sub.4=Hydrogen), with the following composition 70 g of monomer A and 30 g of monomer B, with 0% of transfer agent: Solid; I.R. cm.sup.1: 3453.6, 3025.4, 2922.8, 1943.9, 1870.8, 1732.2, 1601.4, 1493.3, 1452.7, 1373.4, 1242.9, 1119.8, 1025.9, 946.2, 757.6, 698.5, 539.4; .sup.13C RMN (CDCl.sub.3): 170.4, 145.4, 128.0, 125.7, 70.6, 69.7, 67.1, 40.6, 39.3, 21.1.

E-6

(52) Poly(styrene).sub.x-poly(acetate).sub.y-poly(acrylate).sub.z (R.sub.1=phenyl, R.sub.2=Hydrogen, R.sub.3=C.sub.4H.sub.9, R.sub.4=Hydrogen), with the following composition 30 g of monomer A, 20 g of monomer B and 50 g of monomer C, with 8% of transfer agent: viscous semisolid; I.R. cm.sup.1: 2958.1, 2929.9, 2872.9, 1731.2, 1453.5, 1372.3, 1238.8, 1163.3, 1066.6, 1028.6, 700.8; .sup.13C RMN (CDCl.sub.3): 175.3, 128.4, 127.8, 126.4, 70.5, 69.8, 64.3, 41.7, 41.2, 39.5, 31.9, 30.7, 29.7, 29.4, 28.9, 22.7, 21.0, 19.2, 13.8.

E-7

(53) Poly(styrene).sub.x-poly(acetate).sub.y-poly(acrylate).sub.z (R.sub.1=phenyl, R.sub.2=Hydrogen, R.sub.3=tert-butyl, R.sub.4=hydrogen): with the following composition 30 g of monomer A, 50 g of monomer B and 20 g of monomer C, with 8% of transfer agent: viscous semisolid; I.R. cm.sup.1: 3026.4, 2926.3, 1731.6, 1493.4, 1372.0, 1452.6, 1242.1, 1161.0, 1028.4, 759.7, 699.8; .sup.13C RMN (CDCl.sub.3): 175.9, 170.5, 145.2, 143.8, 128.3, 113.9, 70.5, 63.8, 43.1, 1.2, 39.2, 33.8, 32.0, 29.7, 22.8, 21.1, 19.2, 14.2, 13.8.

E-8

(54) Poly(styrene).sub.x-poly(acetate).sub.y-poly(acrylate).sub.z (R.sub.1=C.sub.6H.sub.4CH.sub.3, R.sub.2=hydrogen, R.sub.4=hydrogen, R.sub.5=C.sub.4H.sub.9): with the following composition 30 g of monomer A, 50 g of monomer B and 20 g of monomer C, with 0% of transfer; viscous semisolid; I.R. cm.sup.1: 3438.5, 3059.9, 3026.9, 2925.8, 1945.8, 1873.8, 1803.1, 1729.5, 1602.1, 1492.5, 1451.1, 1356.4, 1249.7, 1156.9, 944.6, 840.9, 758.5, 700, 541.6; .sup.13C RMN (CDCl.sub.3): 175.8, 170.5, 145.3, 128.1, 127.7, 125.9, 70.6, 63.8, 41.8, 30.6, 21.0, 19.1, 13.8.

E-9

(55) Poly(styrene).sub.x-poly(acetate).sub.y-poly(acrylate).sub.z (R.sub.1=C.sub.6H.sub.4CH.sub.3, R.sub.2=hydrogen, R.sub.3=C.sub.4H.sub.9, R.sub.4=hydrogen): with the following composition 20 g of monomer A, 50 g of monomer B and 30 g of monomer C, with 8% of transfer agent; viscous semisolid; I.R. cm.sup.1: 3442.0, 3082.9, 3026.7, 2928.6, 1944.4, 1870.9, 1731.5 16017, 1493.7, 1453.0, 1373.0, 1242.0, 1160.7, 1028.0, 943.9, 841.3, 759.9, 841.3, 759.9, 699.0, 544.7; .sup.13C RMN (CDCl.sub.3): 175.2, 128.4, 64.2, 41.3, 34.8, 31.9, 30.7, 29.7, 28.9, 22.7, 21.1, 19.2, 13.8.

E-10

(56) Poly(styrene).sub.x-poly(acetate).sub.y-poly(acrylate).sub.z (R.sub.1=C.sub.6H.sub.5, R.sub.2=hydrogen, R.sub.3=C.sub.6H.sub.13, R.sub.4=hydrogen), with the following composition 20 g of monomer A, 50 g of monomer B and 30 g of monomer C, with 1% of transfer agent; viscous semisolid; I.R. cm.sup.1: 3437.9, 3026.5, 2926.6, 1944.7, 1873.3, 1728.5, 1601.6, 1493.0, 1451.5, 1354.8, 1250.3, 1155.4, 1028.3, 759.3, 699.3; .sup.13C RMN (CDCl.sub.3): 176.0, 170.6, 144.3, 128.3, 125.9, 70.5, 63.9, 41.2, 31.9, 29.7, 28.9, 22.8, 21.1.

E-11

(57) Poly(styrene).sub.x-poly(acetate).sub.y-poly(acrylate).sub.z (R.sub.1=C.sub.6H.sub.4CH.sub.3, R.sub.2=hydrogen, R.sub.3=C.sub.2H.sub.5, R.sub.4=hydrogen), with the following composition 20 g of monomer A, 70 g of monomer B and 10 g of monomer C, with 8% of transfer agent; viscous semisolid; I.R. cm.sup.1: 3059.9, 3025.9, 2924.8, 2852.9, 1943.4, 1871.3, 1802.9, 1730.9, 1493.0, 1452.3, 1243.9, 1154.9, 1028.6, 758.0, 699.2, 541.1; .sup.13C RMN (CDCl.sub.3): 175.9, 170.4, 145.3, 128.2, 125.8, 70.6, 63.8, 46.3, 40.6, 32.0, 30.5, 29.7, 29.4, 22.8, 13.8.

E-12

(58) Poly(styrene).sub.x-poly(acetate).sub.y-poly(acrylate).sub.z (R.sub.1=C.sub.6H.sub.5, R.sub.2=hydrogen, R.sub.3=C.sub.4H.sub.9, R.sub.4=hydrogen), with the following composition 20 g of monomer A, 70 g of monomer B and 10 g of monomer C, with 1% of transfer agent; viscous semisolid; I.R. cm.sup.1: 3026.3, 2923.6, 1944.5, 1873.0, 1803.8, 1730.3, 1601.6, 1492.2, 1449.6, 1371.2, 1243.4, 1152.7, 1027.7, 945.0, 908.5, 757.1, 700.3, 539.9; .sup.13C RMN (CDCl.sub.3): 145.3, 128.0, 125.7, 70.6, 63.9, 44.3, 41.1, 40.5, 30.6, 19.1, 13.8.

E-13

(59) Poly(styrene).sub.x-poly(acetate).sub.y-poly(acrylate).sub.z (R.sub.1=C.sub.6H.sub.5, R.sub.2=hydrogen, R.sub.3=C.sub.6H.sub.13, R.sub.4=hydrogen), with the following composition 20 g of monomer A, 10 g of monomer B and 70 g of monomer C, with 8% of transfer agent; viscous semisolid; I.R. cm.sup.1: 3447.2, 2959.4, 2870.5, 1730.9, 1604.2, 1456.5, 1371.6, 1239, 1164.3, 1065.91026.3, 944.6, 840.4, 759.7, 702.0; .sup.13C RMN (CDCl.sub.3): 175.2, 128.4, 64.2, 41.3, 34.8, 31.9, 30.7, 29.7, 28.9, 22.7, 21.1, 19.2, 13.8.

E-14

(60) Poly(styrene).sub.x-poly(acetate).sub.y-poly(acrylate).sub.z (R.sub.1=C.sub.6H.sub.4CH.sub.3, R.sub.2=hydrogen, R.sub.3=C.sub.4H.sub.9, R.sub.4=hydrogen), with the following composition 20 g of monomer A, 10 g of monomer B and 70 g of monomer C, with 1% of transfer agent; viscous semisolid; I.R. cm.sup.1: 3446.2, 2959.0, 2873.5, 1732.2, 1453.0, 1372.9, 1239.5, 1163.8, 1117.9, 1066.3, 1024.2, 943.9, 701.6; .sup.13C RMN (CDCl.sub.3): 175.0, 170.2, 0.5, 64.6, 41.4, 39.1, 35.3, 30.7, 20.9, 19.2, 13.8.

E-15

(61) Poly(styrene).sub.x-poly(acetate).sub.y-poly(acrylate).sub.z (R.sub.1=C.sub.6H.sub.5, R.sub.2=hydrogen, R.sub.3=C.sub.6H.sub.13, R.sub.4=hydrogen), with the following composition 60 g of monomer A, 30 g of monomer B and 10 g of monomer C, with 8% of transfer agent; viscous semisolid; I.R. cm.sup.1: 3026.6, 2925.9, 2854.3, 1732.9, 1601.6, 1492.8, 1451.4, 1372.2, 1241.3, 1156.9, 1026.6, 945.7, 758.2, 700.5; .sup.13C RMN (CDCl.sub.3): 170.5, 128.3, 70.5, 41.2, 39.3, 31.9, 29.4, 22.8, 14.2, 13.8.

E-16

(62) Poly(styrene).sub.x-poly(acetate).sub.y-poly(acrylate).sub.z (R.sub.1=C.sub.6H.sub.5, R.sub.2=hydrogen, R.sub.3=C.sub.4H.sub.9, R.sub.4=hydrogen), with the following composition 60 g of monomer A, 30 g of monomer B and 10 g of monomer C, with 1% of transfer agent; viscous semisolid; I.R. cm.sup.1: 3442.9, 3026.0, 2921.8, 1944.4.

(63) The random polymers (copolymers and terpolymers) of the present invention were formulated using various solvents and assessed as flow improvers, either reducing the viscosity and/or reducing the pour point in Mexican crude oils whose API gravity is between 9 to 30, the following results are illustrative way do not mean any limitation.

Formulations of Copolymers and their Assessment as Pour Point Reducing Agents for Light and Medium Crude Oils

(64) Different concentrated solutions of alternating copolymers of 1 to 60% by weight, preferably 5 to 40% by weight, were prepared using solvents whose boiling point falls within the range of 35 to 200 C., preferably xylene, toluene, benzene, methyl ethyl ketone, kerosene, turbosine, naphtha, individually or in mixtures, so added small volumes of dissolution and avoided the effect of the solvent influenced in the evaluation of the pour point. Alternating copolymers were evaluated in concentrations in the range of 100 to 4,000 ppm.

(65) Light crude oil used in the present invention was characterized as shown below in Table 3.

(66) TABLE-US-00003 TABLE 3 Physicochemical and physical characterization of light, medium and heavy crude oils (Castro L V et al, 2009). Parameter Light Medium Heavy API density 29.6 21.3 15.8 Salt content 23.0 kg/1,000 bls 1090 kg/1,000 bls 1.1 kg/1,000 bls Wax content 3.02 3.83 4.27 (wt %) Water by 0.8 1.8 0.10 distillation (vol %) Pour Point 21 24 2 ( C.) SARA Analysis (wt %) Saturates 38.44 26.53 10.49 Aromatics 14.59 14.74 9.0 Resins 41.44 47.60 64.12 Asphaltenes 5.53 11.13 16.39

(67) The copolymers were evaluated simultaneously with commercial copolymers type EVA (ethylene-vinyl acetate), as reducing agents of the pour point and as a reference.

(68) The assessment procedure is described below: the sealed bottles with insert number and lid is indicated by the number of compounds to assess plus one that corresponds to the crude oil without additives; each of them was added with crude oil to the 80 mL mark. All the bottles were placed in a water bath at a controlled temperature in 60 C. for 30 minutes, at the end of that time was added above the aliquot of the dissolution alternating copolymers and the commercial copolymers formulations; all the bottles shook for 4 minutes at a rate of 2 beats per second and later placed for 20 minutes in ultrasonic bath with controlled temperature of 60 C. After agitation, the test pieces were placed according to the method ASTM D-97 and left at least 22 hours at room temperature, the evaluation was the performed. All the copolymers, the reason of this invention, and commercial formulations were assessed at different concentrations in the range from 200 to 4,000 ppm. As reference was also prepared a sample of crude oil only with the solvent (without polymer addition) and which is referred to as untreated.

(69) As a demonstration, which does not involve limitation, results are displayed, in FIGS. 1 and 2, the evaluation of copolymers of examples 1-4, for a concentration range of 200 and 4,000 ppm, crude light and medium respectively; commercial formulations are follows:

(70) COM-01: {copolymer of ethylene and 75/25, vinyl acetate MN=38678 Daltons (20%) with solvent (80%).}

(71) COM-02: {ethylene and vinyl 60/40 (p./p.), MN acetate copolymers=52383 Daltons (20%) with solvent (80%).}

(72) FIG. 1 presents the outcome of examples E1-E4 as pour point depressants in light crude. Example 4 is the only one that reduces in greater proportion the pour point, corresponding to the example that has lower molecular weight number. The pour point is significantly reduced in dosages for example 4 and COM-1 between 500 and 2,000 ppm regarding oil without adding with copolymers (untreated).

(73) E1 and E2 examples do not have an effect as pour point depressants. This can be explained by the lack of interaction between acrylates units of copolymers with components of crude oil, especially with waxes, while styrene-vinyl copolymers have better affinity with crude oil.

(74) FIG. 2 presents the results of examples E1-E4 as pour point depressants in medium crude oil. The example E4 showed the best performance to be evaluated in medium crude oil, which contains more aromatic components and more content of asphaltenes compared to the light crude oil.

(75) The effect of molecular mass in examples 3 and 4 is present to compare results in FIG. 2, this last being the most satisfactory.

(76) The copolymer COM-1 presents some reduction at the pour point in medium crude oil, but not in the same way did it with light crude oil. This difference in behavior can be attributed to the increase of asphaltenes in the medium crude oil (11.13% by weight), as well as the increase in molecular mass of these.

(77) Random Terpolymers Formulation and their Evaluation as Viscosity Reducing Agents in Heavy Crude Oil.

(78) Tests consisted in the realization of temperature sweeps to determine the behavior of the viscosity of the heavy crude with added random polymers, depending on temperature; all crude oil samples were subjected to a constant shear rate of =50 sec.sup.1, in a temperature range of 20 to 80 C.

(79) Prepared different concentrated solutions of each of the random terpolymers at 5 to 40% by weight, using solvents whose boiling point falls within the range of 35-200 C., preferably xylene, toluene, benzene, methyl ethyl ketone, kerosene, turbosine, naphtha, individually or in mixtures, so added small volumes of dissolution and found that the effect of the solvent did not influence the assessment of viscosity. Random terpolymers were evaluated simultaneously with commercial type EVA copolymers (vinyl, with 25 and 40% ethylene-acetate copolymers weight of vinyl acetate), as reducing agents of viscosity in concentrations in the range of 250 to 4,000 ppm. The characterization of heavy crude oil used in this evaluation is indicated in Table 3.

(80) The assessment procedure described below: the sealed bottles with insert number and lid is indicated by the number of compounds to assess plus one that corresponds to the crude without additives; each of them added crude oil to the 80 mL mark. All the bottles were placed in a water bath at a controlled temperature in 40 C. for 15 minutes, at the end of that time was added above the aliquot of the dissolution of the random terpolymers and the commercial copolymers formulations; all the bottles shook during 4 minutes, 2 beats per second and later 20 minutes in ultrasonic bath with controlled temperature of 60 C. After agitated remained at rest at room temperature, then perform the evaluation. All the terpolymers reason for this invention and commercial formulations were assessed at different concentrations in the ranger of 250 to 1,000 ppm for a solution to 20% of polymer in any solvents or mixtures of them mentioned above although preferably used xylene or toluene. Crude oil samples without polymer were used as untreated or reference.

(81) An important parameter to reduce the viscosity of crude oil and improve fluidity is the manipulation of temperature. The temperature strongly influences the viscosity of high molecular mass of crude oil components. Increasing temperature increases the level of clutter the structures of the components of crude oil, resulting in reduce the viscosity drastically (Borthakur a. et al, 1996).

(82) Heavy oil samples were performed rotational testing at different temperatures which provide information about the flow material properties and its behavior respect to temperature.

(83) For this part of the evaluation it was used a rheometer to study the influence of the terpolymers on the behavior of heavy oil with temperature and rotational tests. The influence of polymers was evaluated at concentrations preferably from 250 to 10,000 ppm (Nuez S M et al 2001, Ronningsen H P et al 1991).

(84) It was used a rheometer (Anton Parr) Physica MCR301 model. It was performed the measurement of viscosity at 20 C. using a cutting speed range of 0.1 to 300 sec.sup.1, with these measurements was made graphic representation of the coefficient of viscosity depending on cutting speed , called viscosity curve =f(), similarly the measurement was made of shear depending on cutting speed (Nuez S M et al 2001, Bharambe D P et al 2006).

(85) By way of demonstration, which does not imply any limitation, are shown in FIGS. 3, 4, 5 and 6, the results of the evaluation described above, dosing at 500 and 1,000 ppm of a 20% solution of polymer at a temperature of 20 C. (Torres E et al 2004, Ahlers W et al 2007):

(86) FIG. 3 in the top, shows the evolution of the viscosity of heavy oil without an additive (white) versus the cutting speed. It is also clear that all the tested terpolymers (E6-E10) reduced the oil viscosity along the selected shear rate range, from 0.1 to 300 s.sup.1, at a constant temperature of 20 C.

(87) The terpolymer which exhibits the best performance is the P(BuA-co-AV-co-S) 20/30/50 (E7), that has a low molecular weight (M.sub.w=3705 Daltons). Compositionally speaking is the one with greater styrene content, less composition of acetates and median acrylate groups.

(88) In order to compare the terpolymers with the best viscosity reducing effect, reference is made to FIG. 4, where evaluations of heavy crude oil without an additive (white) and with terpolymers E12, E14 and E16 additives are reported, all of them of high molecular weight. The order of reduction of viscosity is E12>E16>E14. The above results clearly demonstrate the magnitude of the molecular mass number (M.sub.w) that must have the terpolymer. For a terpolymer is a good viscosity reducer it appears that must have a high composition of styrenic polymers, considerable composition of acrylate groups and low composition of acetate groups.

(89) FIG. 5 shows the viscosity curve of heavy crude with polymers E11, E12 and E16, at temperatures from 20 to 32 C. and dosages of 1,000 ppm, and is observed that the sample of heavy oil with additive E12 presents an initial reduction of 23.5%, and as the temperature increases to 30 C., reduced viscosity is about 25.1%. In the same Figure, a way of comparison were included the results of percentage reduction of E16 and E11.

(90) FIG. 6 shows the general behavior of heavy oil without an additive (untreated) and with different concentrations of polymer additives, and that is where it can ratify the behavior of viscosity reduction with increasing temperature on added oil. It is necessary to highlight the fact that at low temperatures (from 20 to 40 C.) the viscosity of heavy oil is reduced and at temperatures above 50 C. is noted that oil is no longer sensitive to these polymers.

(91) However, it is important to note that the main interest of this invention is focused on reducing the viscosity of heavy oil in the temperature range of 20 to 30 C., since this range represents the normal operating conditions at platforms and refineries.

(92) The same Figure presents the results of the evaluation of two commercial copolymers (COM-01 and COM-02) as viscosity reducers. Neither reduces the viscosity of heavy crude. One of them has any influence even as viscosity reducer (COM-02). Even worse, the commercial copolymer (COM-01) increases the viscosity; in contrast, the random terpolymer E-12 significantly reduces the viscosity of heavy oil.

(93) With the different sets of tests using synthesized terpolymer and copolymers and added to different types of Mexican crude, it was possible to identify both the effect that caused each of the monomers and the effective polymer molecular mass range (M.sub.w). Also, it was possible to establish to the characterization tests should have been submitted crude oil, if it wanted to evaluate the pour point or viscosity reduction.

(94) For Mexican crudes, commercial copolymer COM-01 is a good pour point depressant but not so good viscosity reducer. When there are significant amounts of asphaltenes in crude oils, the rheological behavior of the structure of the copolymer COM-1 is considerably reduced (Castro M F et al, 2008). In contrast, E4 and E12 polymers proved to be good pour point depressants and viscosity reducers under conditions of processing various crudes oil used into platforms and refineries.