Polymer proppant and method for producing same

Abstract

The polymer proppant and method for producing the same relate to oil and gas production technology using materials of high-molecular weight compounds with higher requirements for physical and mechanical properties. The proppant is used as propping granules utilized in the oil and gas production by a method of hydraulic fracturing of formation. The technical result achieved by implementation of the present invention is an increase in thermal strength of the proppant whose material provides a compressive strength of at least 150 MPa at a temperature of not less than 100° C. The polymer proppant represents microspheres of metathesis-radically cross-linked mixture of oligocyclopentadienes.

Claims

1. A method for producing a proppant, including obtaining a mixture of oligocyclopentadienes by heating dicyclopentadiene to a temperature of 150-220° C. and holding at this temperature for 15-360 minutes, cooling the mixture down to 20-50° C., sequentially adding the following components to the resulting mixture of oligocyclopentadienes: at least one polymer stabilizers selected from the following compounds: tetrakis[methylene(3,5-di-tert-butyl-4-hydroxyhydrocinnamate)]methane, 2,6-di-tert-butyl-4-(dimethylamino)phenol, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate, 3,5-di-tert-butyl-4-hydroxyanisole, 4,4′-methylenebis(2,6-di-tert-butylphenol), diphenylamine, para-di-tert-butylphenylenediamine, N,N′-diphenyl-1,4-phenylenediamine, tris(2,4-di-tert-butylphenyl)phosphite, tris(nonylphenyl)phosphite, bis(2,2,6,6-tetramethyl-4-piperidinyl)sebacate, bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidinyl)sebacate, bis(1-methyl-2,2,6,6-tetramethyl-4-piperidinyl)sebacate, 2-tert-butyl-6-(5-chloro-2H-benzotriazol-2-yl)-4-methylphenol, and 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenyl)phenol; at least one radical initiators selected from the following compounds or mixtures thereof: di-tert-butyl peroxide, dicumyl peroxide, 2,3-dimethyl-2,3-diphenylbutane, and triphenylmethane; and a catalyst which is a compound of the following general formula: ##STR00008## wherein a substituent L is selected from the following group: ##STR00009## ##STR00010## ##STR00011## wherein the components of the polymer matrix are present in the following amounts, wt. %: the at least one polymer stabilizer 0.1-3; the at least one radical initiator 0.1-4; the catalyst 0.001-0.02; the mixture of oligocyclopentadienes being the balance, the resulting polymer matrix is held at a temperature of 20-50° C. for 1-40 minutes, and thereafter is introduced as a laminar flow into an aqueous solution preheated to a temperature not lower than that of the matrix, said aqueous solution containing a surfactant which is cetyltrimethylammonium chloride or sodium dodecyl sulfate or ammonium lauryl sulfate or sodium lauryl sarcosinate or octenidine hydrochloride or benzalkonium chloride; while constantly stirring, the aqueous solution is heated up to 50-100° C., while still continuing stirring for 1-60 minutes; microspheres formed are separated from the aqueous solution, are heated in an inert gas atmosphere to a temperature of 150-340° C. and are held under said atmosphere at this temperature for 1-360 minutes.

2. A polymer proppant, characterized in that it is produced by the method according to claim 1.

Description

BEST MODE FOR CARRYING OUT THE INVENTION

(1) The polymer proppant is produced as follows.

(2) A mixture of oligocyclopentadienes is produced by heating dicyclopentadiene to a temperature of 150-220° C. and holding thereof at this temperature for 15-360 minutes.

(3) ##STR00005##

(4) The mixture of oligomers is cooled down to 20-50° C., and polymer stabilizers, radical initiators and a catalyst are successively added thereto. A polymer matrix is thereby obtained with the following composition, wt. %: the polymer stabilizers 0.1-3; the radical initiators 0.1-4; the catalyst 0.001-0.02; the mixture of oligocyclopentadienes being the balance.

(5) The polymer matrix is held at a temperature of 0-50° C. for 1-40 minutes, and thereafter is introduced as a laminar flow into water containing a surfactant and preheated to a temperature not lower than that of the matrix, while constantly stirring the water. The water is heated up to 50-100° C., while still continuing stirring for 1-60 minutes. During the stirring process, a metathesis polymerization of the matrix occurs to form the microspheres. Polymerization of the oligomers of cyclopentadiene proceeds according to the following scheme:

(6) ##STR00006##

(7) The microspheres formed are separated from the liquid, are heated up to a temperature of 150-340° C. under an inert gas atmosphere and are held under said atmosphere at this temperature for 1-360 minutes. During the process of heating and holding at this temperature, radical cross-linking of the polymer occurs as follows:

(8) ##STR00007##

(9) The heating of the microspheres under an inert gas atmosphere prevents them from oxidation and destruction. It is preferable to use nitrogen or argon as the inert gas.

(10) The properties of the proppant material are classified by the following characteristics:

(11) Glass transition temperature (Tg) A more than 250° C. B 201 to 250° C. C 170 to 200° C. D less than 170° C.

(12) Compressive strength, MPa A more than 220 B 170 to 219 C 120 to 169

(13) Target fraction (0.1-1.5 mm), % A more than 77 B 74 to 77 C 70 to 74

(14) Swelling in oil (100° C./1 week), % A less than 1 B 1.1 to 3 C 3.1 to 5.

EXAMPLE EMBODIMENTS OF THE INVENTION

Example 1

(15) Dicyclopentadiene is heated in an autoclave to 170° C., is held at the predetermined temperature for 60 minutes, and is cooled down to room temperature. Polymer stabilizers 1010 (0.30 wt. %), 168 (0.40 wt. %) and 770 (0.40 wt. %), and radical initiators B (2.0 wt. %), 30 (2.0 wt. %) are added to the resulting mixture. Catalyst N3a (0.0278 wt. %) is added at 25° C. The resulting mixture is stirred for 10 minutes, and thereafter is introduced as a laminar flow into water (a polymer mixture/water-and-surfactant ratio being 0.2) containing a surfactant of sodium dodecyl sulfate (0.2 wt. %) at 40° C. While constantly stirring, the water is heated up to 100° C. and is held for 10 minutes. Microspheres are separated from the water, are heated up to 260° C. and are held at this temperature under nitrogen atmosphere for 40 minutes. The microspheres thereby produced are as follows: yield of 97%, average size (B), Tg (B), compressive strength (B), sphericity of 0.9, bulk density of 0.6 g/cm.sup.3, and swelling (B).

Example 2

(16) Dicyclopentadiene is heated in an autoclave to 160° C., is held at the predetermined temperature for 60 minutes, and is cooled down to room temperature. Polymer stabilizers 330 (0.50 wt. %) and 168 (0.50 wt. %), and a radical initiator B (0.1 wt. %) are added to the resulting mixture. Catalyst N (0.0096 wt. %) is added at 35° C. The resulting mixture is stirred for 40 minutes, and thereafter is introduced as a laminar flow into water (a polymer mixture/water-and-surfactant ratio being 0.1) containing a surfactant of sodium lauryl sarcosinate (0.1 wt. %) at 35° C. While constantly stirring, the water is heated up to 100° C. and is held for 1 minute. Microspheres are separated from the water, are heated up to 200° C., and are held at this temperature under nitrogen atmosphere for 30 minutes. The microspheres thereby produced are as follows: yield of 94%, average size (A), Tg (C), compressive strength (B), sphericity of 0.9, bulk density of 0.6 g/cm.sup.3, and swelling (C).

Example 3

(17) Dicyclopentadiene is heated in an autoclave to 155° C., is held at the predetermined temperature for 240 minutes, and is cooled down to room temperature. Polymer stabilizers 1010 (0.40 wt. %), 168 (0.40 wt. %) and 770 (0.50 wt. %), and a radical initiator BC-FF (1.5 wt. %) are added to the resulting mixture. Catalyst N7a (0.0072 wt. %) is added at 25° C. The resulting mixture is stirred for 10 minutes, and thereafter is introduced as a laminar flow into water (a polymer mixture/water-and-surfactant ratio being 0.3) containing a surfactant of cetyltrimethylammonium chloride (0.3 wt. %) at 40° C. While constantly stirring, the water is heated up to 100° C. and is held for 15 minutes. Microspheres are separated from the water, are heated up to 150° C., and are held at this temperature under nitrogen atmosphere for 20 minutes. The microspheres thereby produced are as follows: yield of 91%, the average size (C), Tg (C), compressive strength (B), sphericity of 0.9, bulk density of 0.6 g/cm.sup.3, and swelling (C).

Example 4

(18) Dicyclopentadiene is heated in an autoclave to 150° C., is held at the predetermined temperature for 60 minutes, and is cooled down to room temperature. Polymer stabilizers 702 (0.30 wt. %) and 168 (0.50 wt. %), and a radical initiator B (1.0 wt. %) are added to the resulting mixture. Catalyst N5a (0.0132 wt. %) is added at 10° C. The resulting mixture is stirred for 2 minutes, and thereafter is introduced as a laminar flow into water (a polymer mixture/water-and-surfactant ratio being 0.05) containing a surfactant of sodium dodecyl sulfate (0.1 wt. %) at 55° C. While constantly stirring, the water is heated up to 60° C. and is held for 45 minutes. Microspheres are separated from the water, are heated up to 200° C., and are held at this temperature under nitrogen atmosphere for 30 minutes. The microspheres thereby produced are as follows: yield of 89%, average size (A), Tg (A), compressive strength (A), sphericity of 0.9, bulk density of 0.6 g/cm.sup.3, and swelling (A).

Example 5

(19) Dicyclopentadiene is heated in an autoclave to 150° C., is held at the predetermined temperature for 160 minutes, and is cooled down to room temperature. Polymer stabilizers 1010 (0.20 wt. %), TNPP (0.50 wt. %) and 292 (0.50 wt. %), and a radical initiator B (1.0 wt. %) are added to the resulting mixture. Catalyst N1 (0.0099 wt. %) is added at 50° C. The resulting mixture is stirred for 5 minutes, and thereafter is introduced as a laminar flow into water (a polymer mixture/water-and-surfactant ratio being 0.1) containing a surfactant of benzalkonium chloride (0.1 wt. %) at 30° C. While constantly stirring, the water is heated up to 50° C. and is held for 10 minutes. Microspheres are separated from the water, are heated up to 200° C., and are held at this temperature under nitrogen atmosphere for 360 minutes. The microspheres thereby produced are as follows: yield of 97%, average size (B), Tg (C), compressive strength (B), sphericity of 0.9, bulk density of 0.6 g/cm.sup.3, and swelling (C).

Example 6

(20) Dicyclopentadiene is heated in an autoclave to 160° C., is held at the predetermined temperature for 180 minutes, and is cooled down to room temperature. Polymer stabilizers 330 (0.50 wt. %) and 168 (1.00 wt. %), and radical initiators BC-FF (1.5 wt. %) and 30 (2.5 wt. %) are added to the resulting mixture. Catalyst N14a (0.0087 wt. %) is added at 25° C. The resulting mixture is stirred for 10 minutes, and thereafter is introduced as a laminar flow into water (a polymer mixture/water-and-surfactant ratio being 0.15) containing a surfactant of octenidine hydrochloride (0.1 wt. %) at 40° C. While constantly stirring, the water is heated up to 100° C. and is held for 15 minutes. Microspheres are separated from the water, are heated up to 250° C., and are held at this temperature under nitrogen atmosphere for 45 minutes. The microspheres thereby produced are as follows: yield of 97%, average size (A), Tg (A), compressive strength (A), sphericity of 0.9, bulk density of 0.6 g/cm.sup.3, and swelling (A).

Example 7

(21) Dicyclopentadiene is heated in an autoclave to 150° C., is held at the predetermined temperature for 240 minutes, and is cooled down to room temperature. Polymer stabilizers 1010 (0.40 wt. %), 168 (0.80 wt. %) and 770 (0.40 wt. %), and radical initiators B (1.0 wt. %) and 30 (2.0 wt. %) are added to the resulting mixture. Catalyst N17a (0.0088 wt. %) is added at 20° C. The resulting mixture is stirred for 5 minutes, and thereafter is introduced as a laminar flow into water (a polymer mixture/water-and-surfactant ratio being 0.1) containing a surfactant of cetyltrimethylammonium chloride (0.1 wt. %) at 35° C. While constantly stirring, the water is heated up to 60° C. and is held for 15 minutes. Microspheres are separated from the water, are heated up to 340° C., and are held at this temperature under nitrogen atmosphere for 10 minutes. The microspheres thereby produced are as follows: yield of 97%, average size (A), Tg (A), compressive strength (B), sphericity of 0.9, bulk density of 0.6 g/cm.sup.3, and swelling (A).

Example 8

(22) Dicyclopentadiene is heated in an autoclave to 150° C., is held at the predetermined temperature for 60 minutes, and is cooled down to room temperature. Polymer stabilizers 702 (0.20 wt. %), 168 (0.50 wt. %) and 123 (0.50 wt. %), and a radical initiator B (0.5 wt. %) are added to the resulting mixture. Catalyst N4 (0.0170 wt. %) is added at 25° C. The resulting mixture is stirred for 10 minutes, and thereafter is introduced as a laminar flow into water (a polymer mixture/water-and-surfactant ratio being 0.1) containing a surfactant of ammonium lauryl sulfate (0.25 wt. %) at 35° C. While constantly stirring, the water is heated up to 75° C. and is held for 30 minutes. Microspheres are separated from the water, are heated up to 150° C., and are held at this temperature under nitrogen atmosphere for 30 minutes. The microspheres thereby produced are as follows: yield of 95%, average size (B), Tg (C), compressive strength (B), sphericity of 0.9, bulk density of 0.6 g/cm.sup.3, and swelling (C).

Example 9

(23) Dicyclopentadiene is heated in an autoclave to 160° C., is held at the predetermined temperature for 120 minutes, and is cooled down to room temperature. Polymer stabilizers 1010 (0.20 wt. %), 168 (0.75 wt. %) and 292 (0.45 wt. %), and a radical initiator BC-FF (1.0 wt. %) are added to the resulting mixture. Catalyst N5 (0.0126 wt. %) is added at 10° C. The resulting mixture is stirred for 5 minutes, and thereafter is introduced as a laminar flow into water (a polymer mixture/water-and-surfactant ratio being 0.1) containing a surfactant of sodium dodecyl sulfate (0.1 wt. %) at 30° C. While constantly stirring, the water is heated up to 100° C. and is held for 15 minutes. Microspheres are separated from the water, are heated up to 200° C., and are held at this temperature under nitrogen atmosphere for 30 minutes. The microspheres thereby produced are as follows: yield of 97%, average size (A), Tg (C), compressive strength (B), sphericity of 0.9, bulk density of 0.6 g/cm.sup.3, and swelling (C).

Example 10

(24) Dicyclopentadiene is heated in an autoclave to 180° C., is held at the predetermined temperature for 60 minutes, and is cooled down to room temperature. Polymer stabilizers DPA (0.40 wt. %), 168 (0.50 wt. %) and 234 (0.20 wt. %), and radical initiators B (1.0 wt. %) and 30 (3.0 wt. %) are added to the resulting mixture. Catalyst N19a (0.0247 wt. %) is added at 0° C. The resulting mixture is stirred for 1 minute, and thereafter is introduced as a laminar flow into water (a polymer mixture/water-and-surfactant ratio being 0.1) containing a surfactant of cetyltrimethylammonium chloride (0.1 wt. %) at 35° C. While constantly stirring, the water is heated up to 80° C. and is held for 15 minutes. Microspheres are separated from the water, are heated up to 265° C., and are held at this temperature under nitrogen atmosphere for 60 minutes. The microspheres thereby produced are as follows: yield of 97%, average size (B), Tg (A), compressive strength (B), sphericity of 0.9, bulk density of 0.6 g/cm.sup.3, and swelling (A).

Example 11

(25) Dicyclopentadiene is heated in an autoclave to 150° C., is held at the predetermined temperature for 180 minutes, and is cooled down to room temperature. Polymer stabilizers 702 (0.50 wt. %) and 168 (0.50 wt. %), and a radical initiator BC-FF (2.0 wt. %) are added to the resulting mixture. Catalyst N2a (0.0167 wt. %) is added at 30° C. The resulting mixture is stirred for 20 minutes, and thereafter is introduced as a laminar flow into water (a polymer mixture/water-and-surfactant ratio being 0.1) containing a surfactant of sodium dodecyl sulfate (0.1 wt. %) at 40° C. While constantly stirring, the water is heated up to 70° C. and is held for 15 minutes. Microspheres are separated from the water, are heated up to 250° C., and are held at this temperature under nitrogen atmosphere for 30 minutes. The microspheres thereby produced are as follows: yield of 98%, average size (A), Tg (B), compressive strength (A), sphericity of 0.9, bulk density of 0.6 g/cm.sup.3, and swelling (B).

Example 12

(26) Dicyclopentadiene is heated in an autoclave to 160° C., is held at the predetermined temperature for 120 minutes, and is cooled down to room temperature. Polymer stabilizers 1010 (0.20 wt. %), 168 (0.50 wt. %) and 292 (0.50 wt. %), and radical initiators BC-FF (0.1 wt. %) and 30 (1.5 wt. %) are added to the resulting mixture. Catalyst N1a (0.0033 wt. %) is added at 30° C. The resulting mixture is stirred for 10 minutes, and thereafter is introduced as a laminar flow into water (a polymer mixture/water-and-surfactant ratio being 0.1) containing a surfactant of cetyltrimethylammonium chloride (0.1 wt. %) at 40° C. While constantly stirring, the water is heated up to 70° C. and is held for 15 minutes. Microspheres are separated from the water, are heated up to 280° C., and are held at this temperature under nitrogen atmosphere for 1 minute. The microspheres thereby produced are as follows: yield of 90%, the average size (C), Tg (B), compressive strength (B), sphericity of 0.9, bulk density of 0.6 g/cm.sup.3, and swelling (B).

Example 13

(27) Dicyclopentadiene is heated in an autoclave to 155° C., is held at the predetermined temperature for 280 minutes, and is cooled down to room temperature. Polymer stabilizer 702 (0.10 wt. %) and radical initiators BC-FF (1.0 wt. %) and 30 (1.0 wt. %) are added to the resulting mixture. Catalyst N1c (0.0116 wt. %) is added at 20° C. The resulting mixture is stirred for 5 minutes, and thereafter is introduced as a laminar flow into water (a polymer mixture/water-and-surfactant ratio being 0.1) containing a surfactant of cetyltrimethylammonium chloride (0.1 wt. %) at 30° C. While constantly stirring, the water is heated up to 50° C. and is held for 40 minutes. Microspheres are separated from the water, are heated up to 310° C., and are held at this temperature under nitrogen atmosphere for 5 minutes. The microspheres thereby produced are as follows: yield of 93%, average size (B), Tg (A), compressive strength (B), sphericity of 0.9, bulk density of 0.6 g/cm.sup.3, and swelling (A).

Example 14

(28) Dicyclopentadiene is heated in an autoclave to 150° C., is held at the predetermined temperature for 60 minutes, and is cooled down to room temperature. Polymer stabilizers 1010 (0.37 wt. %), 168 (0.10 wt. %) and 770 (0.47 wt. %), and radical initiators B (1.0 wt. %) and 30 (1.0 wt. %) are added to the resulting mixture. Catalyst N6a (0.0061 wt. %) is added at 25° C. The resulting mixture is stirred for 10 minutes, and thereafter is introduced as a laminar flow into water (a polymer mixture/water-and-surfactant ratio being 0.1) containing a surfactant of cetyltrimethylammonium chloride (0.1 wt. %) at 40° C. While constantly stirring, the water is heated up to 80° C. and is held for 15 minutes. Microspheres are separated from the water, are heated up to 300° C., and are held at this temperature under nitrogen atmosphere for 30 minutes. The microspheres thereby produced are as follows: yield of 93%, average size (C), Tg (A), compressive strength (B), sphericity of 0.9, bulk density of 0.6 g/cm.sup.3, and swelling (A).

Example 15

(29) Dicyclopentadiene is heated in an autoclave to 150° C., is held at the predetermined temperature for 240 minutes, and is cooled down to room temperature. Polymer stabilizers 702 (0.50 wt. %) and 168 (0.50 wt. %), and radical initiators BC-FF (1.0 wt. %) and TPM (1.0 wt. %) are added to the resulting mixture. Catalyst N9a (0.0023 wt. %) is added at 15° C. The resulting mixture is stirred for 10 minutes, and thereafter is introduced as a laminar flow into water (a polymer mixture/water-and-surfactant ratio being 0.1) containing a surfactant of cetyltrimethylammonium chloride (0.1 wt. %) at 35° C. While constantly stirring, the water is heated up to 80° C. and is held for 15 minutes. Microspheres are separated from the water, are heated up to 270° C., and are held at this temperature under nitrogen atmosphere for 30 minutes. The microspheres thereby produced are as follows: yield of 97%, average size (B), Tg (C), compressive strength (B), sphericity of 0.9, bulk density of 0.6 g/cm.sup.3, and swelling (C).

Example 16

(30) Dicyclopentadiene is heated in an autoclave to 170° C., is held at the predetermined temperature for 180 minutes, and is cooled down to room temperature. Polymer stabilizers 5057 (0.20 wt. %), 168 (0.40 wt. %) and 770 (0.40 wt. %), and a radical initiator BC-FF (1.0 wt. %) are added to the resulting mixture. Catalyst N2 (0.0124 wt. %) is added at 25° C. The resulting mixture is stirred for 10 minutes, and thereafter is introduced as a laminar flow into water (a polymer mixture/water-and-surfactant ratio being 0.1) containing a surfactant of cetyltrimethylammonium chloride (0.2 wt. %) at 35° C. While constantly stirring, the water is heated up to 95° C. and is held for 5 minutes. Microspheres are separated from the water, are heated up to 270° C., and are held at this temperature under nitrogen atmosphere for 45 minutes. The microspheres thereby produced are as follows: yield of 98%, average size (B), Tg (C), compressive strength (A), sphericity of 0.9, bulk density of 0.6 g/cm.sup.3, and swelling (C).

Example 17

(31) Dicyclopentadiene is heated in an autoclave to 160° C., is held at the predetermined temperature for 360 minutes, and is cooled down to room temperature. Polymer stabilizers 1010 (0.35 wt. %), 327 (0.20 wt. %) and 770 (0.50 wt. %), and a radical initiator BC-FF (0.5 wt. %) are added to the resulting mixture. Catalyst N10a (0.0072 wt. %) is added at 5° C. The resulting mixture is stirred for 10 minutes, and thereafter is introduced as a laminar flow into water (a polymer mixture/water-and-surfactant ratio being 0.1) containing a surfactant of sodium dodecyl sulfate (0.1 wt. %) at 35° C. While constantly stirring, the water is heated up to 95° C. and is held for 15 minutes. Microspheres are separated from the water, are heated up to 170° C., and are held at this temperature under nitrogen atmosphere for 30 minutes. The microspheres thereby produced are as follows: yield of 98%, average size (A), Tg (C), compressive strength (B), sphericity of 0.9, bulk density of 0.6 g/cm.sup.3, and swelling (C).

Example 18

(32) Dicyclopentadiene is heated in an autoclave to 160° C., is held at the predetermined temperature for 160 minutes, and is cooled down to room temperature. Polymer stabilizers 330 (0.40 wt. %) and TNPP (0.80 wt. %), and a radical initiator BC-FF (0.5 wt. %) are added to the resulting mixture. Catalyst N11a (0.0102 wt. %) is added at 25° C. The resulting mixture is stirred for 10 minutes, and thereafter is introduced as a laminar flow into water (a polymer mixture/water-and-surfactant ratio being 0.1) containing a surfactant of cetyltrimethylammonium chloride (0.1 wt. %) at 35° C. While constantly stirring, the water is heated up to 95° C. and is held for 15 minutes. Microspheres are separated from the water, are heated up to 200° C., and are held at this temperature under nitrogen atmosphere for 60 minutes. The microspheres thereby produced are as follows: yield of 99%, average size (A), Tg (C), compressive strength (B), sphericity of 0.9, bulk density of 0.6 g/cm.sup.3, and swelling (C).

Example 19

(33) Dicyclopentadiene is heated in an autoclave to 190° C., is held at the predetermined temperature for 50 minutes, and is cooled down to room temperature. Polymer stabilizers 702 (0.45 wt. %), 168 (0.45 wt. %) and 770 (0.40 wt. %), and radical initiators BC-FF (0.5 wt. %) and 30 (2.0 wt. %) are added to the resulting mixture. Catalyst N3b (0.0072 wt. %) is added at 30° C. The resulting mixture is stirred for 10 minutes, and thereafter is introduced as a laminar flow into water (a polymer mixture/water-and-surfactant ratio being 0.1) containing a surfactant of cetyltrimethylammonium chloride (0.1 wt. %) at 40° C. While constantly stirring, the water is heated up to 60° C. and is held for 15 minutes. Microspheres are separated from the water, are heated up to 250° C., and are held at this temperature under nitrogen atmosphere for 30 minutes. The microspheres thereby produced are as follows: yield of 97%, average size (B), Tg (A), compressive strength (B), sphericity of 0.9, bulk density of 0.6 g/cm.sup.3, and swelling (A).

Example 20

(34) Dicyclopentadiene is heated in an autoclave to 155° C., is held at the predetermined temperature for 280 minutes, and is cooled down to room temperature. Polymer stabilizers 168 (0.45 wt. %) and 168 (0.45 wt. %), and radical initiators BC-FF (1.0 wt. %) and 30 (1.5 wt. %) are added to the resulting mixture. Catalyst N5b (0.0131 wt. %) is added at 30° C. The resulting mixture is stirred for 10 minutes, and thereafter is introduced as a laminar flow into water (a polymer mixture/water-and-surfactant ratio being 0.1) containing a surfactant of cetyltrimethylammonium chloride (0.1 wt. %) at 35° C. While constantly stirring, the water is heated up to 95° C. and is held for 15 minutes. Microspheres are separated from the water, are heated up to 260° C., and are held at this temperature under nitrogen atmosphere for 30 minutes. The microspheres thereby produced are as follows: yield of 97%, average size (B), Tg (A), compressive strength (B), sphericity of 0.9, bulk density of 0.6 g/cm.sup.3, and swelling (A).

Example 21

(35) Dicyclopentadiene is heated in an autoclave to 160° C., is held at the predetermined temperature for 180 minutes, and is cooled down to room temperature. Polymer stabilizers 1010 (0.36 wt. %), 168 (0.72 wt. %) and 123 (0.45 wt. %), and the radical initiators B (0.1 wt. %) and 30 (2.0 wt. %) are added to the resulting mixture. Catalyst N12a (0.0085 wt. %) is added at 25° C. The resulting mixture is stirred for 10 minutes, and thereafter is introduced as a laminar flow into water (a polymer mixture/water-and-surfactant ratio being 0.1) containing a surfactant of sodium dodecyl sulfate (0.1 wt. %) at 35° C. While constantly stirring, the water is heated up to 70° C. and is held for 60 minutes. Microspheres are separated from the water, are heated up to 270° C., and are held at this temperature under nitrogen atmosphere for 30 minutes. The microspheres thereby produced are as follows: yield of 97%, average size (A), Tg (A), compressive strength (B), sphericity of 0.9, bulk density of 0.6 g/cm.sup.3, and swelling (A).

Example 22

(36) Dicyclopentadiene is heated in an autoclave to 160° C., is held at the predetermined temperature for 120 minutes, and is cooled down to room temperature. Polymer stabilizers 703 (0.45 wt. %) and 770 (0.45 wt. %), and a radical initiator BC-FF (1.0 wt. %) are added to the resulting mixture. Catalyst N15a (0.0106 wt. %) is added at 25° C. The resulting mixture is stirred for 10 minutes, and thereafter is introduced as a laminar flow into water (a polymer mixture/water-and-surfactant ratio being 0.1) containing a surfactant of octenidine hydrochloride (0.1 wt. %) at 40° C. While constantly stirring, the water is heated up to 70° C. and is held for 15 minutes. Microspheres are separated from the water, are heated up to 170° C., and are held at this temperature under nitrogen atmosphere for 30 minutes. The microspheres thereby produced are as follows: yield of 96%, average size (B), Tg (A), compressive strength (A), sphericity of 0.9, bulk density of 0.6 g/cm.sup.3, and swelling (A).

Example 23

(37) Dicyclopentadiene is heated in an autoclave to 150° C., is held at the predetermined temperature for 60 minutes, and is cooled down to room temperature. Polymer stabilizers 1010 (0.02 wt. %), 168 (0.04 wt. %) and 770 (0.04 wt. %), and a radical initiator BC-FF (1.0 wt. %) are added to the resulting mixture. Catalyst N4a (0.0130 wt. %) is added at 25° C. The resulting mixture is stirred for 10 minutes, and thereafter is introduced as a laminar flow into water (a polymer mixture/water-and-surfactant ratio being 0.1) containing a surfactant of cetyltrimethylammonium chloride (0.1 wt. %) at 35° C. While constantly stirring, the water is heated up to 80° C. and is held for 15 minutes. Microspheres are separated from the water, are heated up to 200° C., and are held at this temperature under nitrogen atmosphere for 30 minutes. The microspheres thereby produced are as follows: yield of 92%, average size (A), Tg (C), compressive strength (B), sphericity of 0.9, bulk density of 0.6 g/cm.sup.3, and swelling (C).

Example 24

(38) Dicyclopentadiene is heated in an autoclave to 155° C., is held at the predetermined temperature for 180 minutes, and is cooled down to room temperature. Polymer stabilizers 14 (0.40 wt. %) and 168 (0.80 wt. %), and a radical initiator B (0.1 wt. %) are added to the resulting mixture. Catalyst N3 (0.0098 wt. %) is added at 25° C. The resulting mixture is stirred for 10 minutes, and thereafter is introduced as a laminar flow into water (a polymer mixture/water-and-surfactant ratio being 0.1) containing a surfactant of benzalkonium chloride (0.1 wt. %) at 30° C. While constantly stirring, the water is heated up to 80° C. and is held for 15 minutes. Microspheres are separated from the water, are heated up to 180° C., and are held at this temperature under nitrogen atmosphere for 30 minutes. The microspheres thereby produced are as follows: yield of 98%, average size (A), Tg (C), compressive strength (B), sphericity of 0.9, bulk density of 0.6 g/cm.sup.3, and swelling (C).

Example 25

(39) Dicyclopentadiene is heated in an autoclave to 150° C., is held at the predetermined temperature for 60 minutes, and is cooled down to room temperature. Polymer stabilizers 1010 (0.50 wt. %), 168 (0.50 wt. %) and 770 (0.50 wt. %), and radical initiators BC-FF (1.0 wt. %) and 30 (2.0 wt. %) are added to the resulting mixture. Catalyst N16a (0.0086 wt. %) is added at 30° C. The resulting mixture is stirred for 1 minute, and thereafter is introduced as a laminar flow into water (a polymer mixture/water-and-surfactant ratio being 0.1) containing a surfactant of sodium dodecyl sulfate (0.1 wt. %) at 35° C. While constantly stirring, the water is heated up to 75° C. and is held for 20 minutes. Microspheres are separated from the water, are heated up to 260° C., and are held at this temperature under nitrogen atmosphere for 30 minutes. The microspheres thereby produced are as follows: yield of 97%, average size (A), Tg (A), compressive strength (A), sphericity of 0.9, bulk density of 0.6 g/cm.sup.3, and swelling (A).

Example 26

(40) Dicyclopentadiene is heated in an autoclave to 155° C., is held at the predetermined temperature for 300 minutes, and is cooled down to room temperature. Polymer stabilizers 330 (0.45 wt. %), TNPP (0.45 wt. %) and 292 (0.45 wt. %), and radical initiators BC-FF (1.0 wt. %) and 30 (1.0 wt. %) are added to the resulting mixture. Catalyst N20a (0.0053 wt. %) is added at 15° C. The resulting mixture is stirred for 10 minutes, and thereafter is introduced as a laminar flow into water (a polymer mixture/water-and-surfactant ratio being 0.1) containing a surfactant of cetyltrimethylammonium chloride (0.1 wt. %) at 50° C. While constantly stirring, the water is heated up to 70° C. and is held for 15 minutes. Microspheres are separated from the water, are heated up to 255° C., and are held at this temperature under nitrogen atmosphere for 30 minutes. The microspheres thereby produced are as follows: yield of 92%, average size (C), Tg (A), compressive strength (B), sphericity of 0.9, bulk density of 0.6 g/cm.sup.3, and swelling (A).

Example 27

(41) Dicyclopentadiene is heated in an autoclave to 155° C., is held at the predetermined temperature for 300 minutes, and is cooled down to room temperature. Polymer stabilizers 702 (0.40 wt. %) and 327 (0.20 wt. %), and a radical initiator B (2.0 wt. %) are added to the resulting mixture. Catalyst N1b (0.0069 wt. %) is added at 30° C. The resulting mixture is stirred for 10 minutes, and thereafter is introduced as a laminar flow into water (a polymer mixture/water-and-surfactant ratio being 0.1) containing a surfactant of benzalkonium chloride (0.2 wt. %) at 40° C. While constantly stirring, the water is heated up to 75° C. and is held for 15 minutes. Microspheres are separated from the water, are heated up to 200° C., and are held at this temperature under nitrogen atmosphere for 120 minutes. The microspheres thereby produced are as follows: yield of 95%, average size (C), Tg (C), compressive strength (B), sphericity of 0.9, bulk density of 0.6 g/cm.sup.3, and swelling (C).

Example 28

(42) Dicyclopentadiene is heated in an autoclave to 175° C., is held at the predetermined temperature for 180 minutes, and is cooled down to room temperature. Polymer stabilizers 330 (0.40 wt. %), 168 (0.50 wt. %) and 770 (0.50 wt. %), and a radical initiator B (1.0 wt. %) are added to the resulting mixture. Catalyst N13a (0.0105 wt. %) is added at 25° C. The resulting mixture is stirred for 10 minutes, and thereafter is introduced as a laminar flow into water (a polymer mixture/water-and-surfactant ratio being 0.1) containing a surfactant of octenidine hydrochloride (0.1 wt. %) at 40° C. While constantly stirring, the water is heated up to 70° C. and is held for 15 minutes. Microspheres are separated from the water, are heated up to 220° C., and are held at this temperature under nitrogen atmosphere for 30 minutes. The microspheres thereby produced are as follows: yield of 97%, average size (A), Tg (B), compressive strength (A), sphericity of 0.9, bulk density of 0.6 g/cm.sup.3, and swelling (B).

Example 29

(43) Dicyclopentadiene is heated in an autoclave to 220° C., is held at the predetermined temperature for 15 minutes, and is cooled down to room temperature. Polymer stabilizers 1010 (1.50 wt. %), TNPP (1.00 wt. %) and 123 (1.50 wt. %), and a radical initiator BC-FF (1.0 wt. %) are added to the resulting mixture. Catalyst N18a (0.0134 wt. %) is added at 10° C. The resulting mixture is stirred for 5 minutes, and thereafter is introduced as a laminar flow into water (a polymer mixture/water-and-surfactant ratio being 0.1) containing a surfactant of cetyltrimethylammonium chloride (0.2 wt. %) at 35° C. While constantly stirring, the water is heated up to 100° C. and is held for 15 minutes. Microspheres are separated from the water, are heated up to 200° C., and are held at this temperature under nitrogen atmosphere for 30 minutes. The microspheres thereby produced are as follows: yield of 96%, average size (A), Tg (C), compressive strength (B), sphericity of 0.9, bulk density of 0.6 g/cm.sup.3, and swelling (C).

Example 30

(44) Dicyclopentadiene is heated in an autoclave to 155° C., is held at the predetermined temperature for 300 minutes, and is cooled down to room temperature. Polymer stabilizers 354 (1.00 wt. %) and 770 (0.50 wt. %), and radical initiators BC-FF (1.0 wt. %) and 30 (1.0 wt. %) are added to the resulting mixture. Catalyst N2b (0.0070 wt. %) is added at 45° C. The resulting mixture is stirred for 10 minutes, and thereafter is introduced as a laminar flow into water (a polymer mixture/water-and-surfactant ratio being 0.1) containing a surfactant of sodium dodecyl sulfate (0.1 wt. %) at 35° C. While constantly stirring, the water is heated up to 95° C. and is held for 15 minutes. Microspheres are separated from the water, are heated up to 275° C., and are held at this temperature under nitrogen atmosphere for 30 minutes. The microspheres thereby produced are as follows: yield of 97%, average size (A), Tg (A), compressive strength (B), sphericity of 0.9, bulk density of 0.6 g/cm.sup.3, and swelling (A).

Example 31

(45) Dicyclopentadiene is heated in an autoclave to 200° C., is held at the predetermined temperature for 60 minutes, and is cooled down to room temperature. Polymer stabilizers 1010 (0.40 wt. %), TNPP (0.40 wt. %) and 770 (0.40 wt. %), and a radical initiator BC-FF (1.0 wt. %) are added to the resulting mixture. Catalyst N8a (0.0103 wt. %) is added at 25° C. The resulting mixture is stirred for 10 minutes, and thereafter is introduced as a laminar flow into water (a polymer mixture/water-and-surfactant ratio being 0.1) containing a surfactant of cetyltrimethylammonium chloride (0.2 wt. %) at 35° C. While constantly stirring, the water is heated up to 70° C. and is held for 15 minutes. Microspheres are separated from the water, are heated up to 170° C., and are held at this temperature under nitrogen atmosphere for 240 minutes. The microspheres thereby produced are as follows: yield of 98%, average size (B), Tg (C), compressive strength (B), sphericity of 0.9, bulk density of 0.6 g/cm.sup.3, and swelling (C).

Example 32

(46) Dicyclopentadiene is heated in an autoclave to 165° C., is held at the predetermined temperature for 240 minutes, and is cooled down to room temperature. Polymer stabilizers 702 (0.37 wt. %), 168 (0.73 wt. %) and 770 (0.37 wt. %), and a radical initiator BC-FF (1.0 wt. %) are added to the resulting mixture. Catalyst N4b (0.0094 wt. %) is added at 30° C. The resulting mixture is stirred for 10 minutes, and thereafter is introduced as a laminar flow into water (a polymer mixture/water-and-surfactant ratio being 0.1) containing a surfactant of sodium dodecyl sulfate (0.5 wt. %) at 40° C. While constantly stirring, the water is heated up to 80° C. and is held for 15 minutes. Microspheres are separated from the water, are heated up to 200° C., and are held at this temperature under nitrogen atmosphere for 60 minutes. The microspheres thereby produced are as follows: yield of 96%, average size (C), Tg (C), compressive strength (B), sphericity of 0.9, bulk density of 0.6 g/cm.sup.3, and swelling (C).

Example 33

(47) Dicyclopentadiene is heated in an autoclave to 155° C., is held at the predetermined temperature for 300 minutes, and is cooled down to room temperature. Polymer stabilizers DPPD (0.37 wt. %), 168 (0.73 wt. %) and 770 (0.37 wt. %), and a radical initiator BC-FF (1.0 wt. %) are added to the resulting mixture. Catalyst N1 (0.0095 wt. %) is added at 30° C. The resulting mixture is stirred for 10 minutes, and thereafter is introduced as a laminar flow into water (a polymer mixture/water-and-surfactant ratio being 0.1) containing a surfactant of sodium dodecyl sulfate (0.4 wt. %) at 45° C. While constantly stirring, the water is heated up to 100° C. and is held for 15 minutes. Microspheres are separated from the water, are heated up to 270° C., and are held at this temperature under nitrogen atmosphere for 60 minutes. The microspheres thereby produced are as follows: yield of 96%, average size (C), Tg (B), compressive strength (B), sphericity of 0.9, bulk density of 0.6 g/cm.sup.3, and swelling (C).

INDUSTRIAL APPLICABILITY

(48) As seen from the examples, the present technology allows for producing proppants with high physical and mechanical properties required for implementation of the technology of formation hydraulic fracturing and hydrocarbon production, primarily, those properties being thermal resistance and strength.