RU2528834C1 - Polydicyclopentadiene microspheres and methods for production thereof - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: microspheres with sphericity of not less than 0.9, average size of which lies in the range of 0.25-1.1 mm and bulk density in the range of 0.4-0.7 g/cm³ are obtained. The method of producing the microspheres includes preparing a liquid polymer mixture by successively mixing dicyclopentadiene of purity of not less than 98% with a polymer stabiliser, a polymer modifier, a radical initiator and a catalyst. The obtained polymer mixture is held at 10-50°C for 1-40 minutes. Water, which is preheated to a temperature not below the temperature of the mixture and containing cationic and anionic surfactants, is then added in the form of a laminar stream. The spheres are formed while constantly mixing the liquid medium. The formed microspheres are separated from the solution, heated to 150-340°C and held at said temperature for 1-360 minutes.

EFFECT: obtaining microspheres from polydicyclopentadiene with improved physical and mechanical properties and compression strength of not less than 90 MPa.

5 cl, 2 dwg, 32 ex

Description

The invention relates to the field of macromolecular compounds, and in particular to a technology for producing polymer microspheres from polydicyclopentadiene for a wide range of applications.

Modern industry imposes stringent requirements on composite materials capable of fully functioning under conditions of high temperatures and physico-mechanical loads, chemically active media, various kinds of electromagnetic and radiation radiation, while improving the specific characteristics of the material or product.

Polymeric microspheres with similar properties have a wide range of applications in the oil and gas industry as proppants, in construction for the production of ultralight concrete, mortar, mortar, coatings, insulation and roofing materials, in mechanical engineering and the chemical industry for the production of filled and reinforced materials with special properties.

The main characteristics of the microspheres are uniformity in size and shape, compressive strength, resistance to high temperatures and aggressive environments.

A known method of producing microspheres from a polymer by controlled coalescence of droplets in a laminar fluid stream, followed by polymerization in a dispersion medium in a column with a downward flow of liquid to obtain solidified granules, which are then heated for 6-8 hours to complete the polymerization. The material for the microspheres is a copolymer of styrene and divinylbenzene, and the dispersion medium is an aqueous solution of calcium chloride containing bentonite and sodium lignosulfonate (US Patent No. 4424318).

The disadvantage of this method is the high duration of the polymerization process, which in a downward flow of liquid leads to a large uneven size of the resulting microspheres, the formation in the stagnant zones of hardened aggregates (sticky granules), and the material itself does not have high physical and mechanical characteristics.

Polymer microspheres and a method for their preparation are known, including feeding tetrafluoroethylene copolymer latex into an aqueous solution of a coagulant, mixing them at elevated temperature, and unloading microspheres (RF Patent No. 2271366).

A disadvantage of the known microspheres and method is a wide range of sizes of the obtained product under the same conditions for the implementation of the technology, low physical and mechanical characteristics of the granules.

A known method of producing monodispersed carboxylated polymer microspheres in the form of an aqueous suspension, characterized in that the solution in the vinyl monomer of the surfactant is azo-bis- (10-carboxydecyl) polydimethylsiloxane containing from 6 to 60 siloxane units and taken in an amount of 0.5 -1.9%, or its mixture with polyoxyalkylene polysiloxane in an amount of 0.9-2.6% by weight of the monomer, is intensively mixed in bidistilled water in an inert atmosphere while heating the mixture to 50-75 ° C and a volume ratio of monomer: water and in the range of 1: (2-9), with the preliminary addition of 0.8-1.3% (by weight of monomer) of the radical polymerization initiators — a mixture of potassium persulfate with azotisisobutyric acid dinitrile or benzoyl peroxide, to the formation of a direct emulsion with subsequent polymerization for 2-5 hours under the action of an initiator of drops of monomer into polymer particles, with a temperature increase of 10 ° C an hour before the end of the process (RF Patent No. 2459834).

The disadvantages of the method include the complexity of the process using a particularly clean medium - bidistilled water and carrying out the process in an inert gas environment, as well as obtaining microspheres not higher than 0.65 microns.

A known method of producing individual solid granules of a polymeric material, comprising forming a combined stream from a heated stream of a polymerizable liquid starting material and a heated stream of a liquid dispersion medium with which the liquid starting substance is substantially or completely unmiscible, the polymerized liquid starting material in said combined stream start to polymerize; processing the combined stream to disperse the polymerizable liquid starting material in the form of droplets in a dispersion medium; ensuring the polymerization of droplets in the laminar flow of the dispersion medium at a given polymerization temperature in order to form separate solid granules that are not capable of agglomeration; extracting these granules from a dispersion medium (RF Patent No. 2466931).

This technology cannot be used to obtain granules from polydicyclopentadiene, since the environment and modes that do not meet the requirements for the formation of non-coalescing granules during the polymerization of dicyclopentadiene are used.

The closest technical solution is the method of producing microspheres from polydicyclopeptadiene, including mixing dicyclopentadiene with a catalyst and dispersing the mixture in ethylene glycol containing surfactants by blowing the dispersion with an inert gas (Ring Opening Metathesis Polymerisation and Related Chemistry State of the Art and Visions for the New Century , Proceedings of the NATO Advanced Study Institute, held in Polaica-Zdroj, Poland, 3-15 September 2000. Khosravi, Ezat; Szymanska-Buzar, T. (Eds.) 2002, 516 p.).

The disadvantage of this method is the low quality of the resulting microspheres, at least 82% of which has a size of less than 1 μm, and the need to purge the reaction medium with an inert gas to prevent oxidation of the polymerization products. These disadvantages are due to the type of catalyst used, the medium used, in which dicyclopentadiene is partially dissolved, and the type of surfactant used - hydroxypropyl cellulose.

The objective of the present invention is to obtain from polydicyclopentadiene microspheres, the average size of which is in the range of 0.25-1.1 mm, and bulk density is in the range of 0.5-0.7 g / cm ³ .

The technical result achieved by the present invention is the improvement of the physicomechanical properties of the obtained microspheres, expressed in sphericity of at least 0.9 for at least 70% by weight, the average size of which is in the range of 0.25-1.1 mm, and in bulk density in the range of 0.5-0.7 g / cm ³ and compressive strength not worse than 90 MPa.

The technical result is achieved by the fact that the method of producing microspheres from polydicyclopentadiene involves obtaining a liquid polymer mixture by sequentially mixing dicyclopentadiene with a polymer stabilizer, which is used as the following compounds or their mixtures (in parentheses after each item a short designation is given): tetrakis [methylene (3 , 5-di-tert-butyl-4-hydroxyhydrocinnamate)] methane (1010), 2,6-di-tert-butyl-4- (dimethylamino) phenol (703), 1,3,5-trimethyl-2,4 , b-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene (330), tris ( 4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate (14), 3,5-di-tert-butyl-4-hydroxyanisole (354), 4,4'-methylenebis (2,6-di tert-butylphenol) (702), diphenylamine (DPA), para-di-tert-butylphenylenediamine (5057), N, N'-diphenyl-1,4-phenylenediamine (DPPD), tris (2,4-di-tert -butylphenyl) phosphite (168), tris (nonylphenyl) phosphite (THPP), bis (2,2,6,6-tetramethyl-4-piperidinyl) sebacinate (770), bis (1-octyloxy-2,2,6, 6-tetramethyl-4-piperidinyl) sebacinate (123), bis (1-methyl-2,2,6,6-tetramethyl-4-piperidinyl) sebacinate (292), 2-tert-butyl-6- (5-chloro -2H-benzotriazol-2-yl) -4-methylphenol (327), 2- (2H-benzotriazol-2-yl) -4,6-bis (1-methyl-1-pheni k) phenol (234), a radical initiator, which is used as the following compounds or mixtures thereof: di-tert-butyl peroxide (B), dicumyl peroxide (BC-FF), 2,3-dimethyl-2,3-diphenyl-butane ( 30), triphenylmethane (TFM), a polymer modifier, which are selected as the following compounds or mixtures thereof: ethylidene norbornene (ENB), norbornene (NB), norbornadiene (NBD), diisocyanates (TDI, MDI), styrene-isoprene-styrene and styrene -butadiene-styrene block copolymers (Vector 4111A, Kraton 1104, Taipol 1307, Europrene SOL T 9113), polydimethysiloxane (CKTH), (allyl methacrylate (AlMAK), glycidyl methacrylate (GM ) Etilendimetakrilat (EGDM), diethylene glycol (DGDMA) butilenglikoldimetakrilat (BGDMA) tritsiklodekandimetanoldimetakrilat (TTSDDMA), ethoxylated bisphenol A dimethacrylate (E2BADMA), trimethylolpropane trimethacrylate (TMPTMA), divinylbenzene, diisopropenylbenzene (DVB), bisphenol-A epoxy resin (ED) and a catalyst , which is used as a compound of General formula:

where the Deputy L is selected from the group:

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the resulting polymer mixture is kept at a temperature of 0-50 ° C for 1-40 min, after which it is introduced as a laminar stream into water preheated at a temperature not lower than the temperature of the mixture containing cationic or anionic surfactants, with constant stirring of water, the microspheres formed separated from the solution, heated to a temperature of 150-340 ° C and maintained at this temperature for 1-360 minutes The components of the polymer mixture are in the following quantitative ratio,% wt .:

polymer stabilizer 0.1-4.5;

polymer modifier 0.1-20.5;

radical initiator 0.1-4;

catalyst 0.002-0.02;

dicyclopentadiene - the rest.

In addition, the technical result is achieved in that the concentration of surfactants in water does not exceed 1%, and the ratio of the polymer mixture to water with surfactants is not more than 0.5.

These distinguishing features are significant.

The use of the above catalysts provides polymerization of the monomer in a liquid medium under specified processing conditions, in which high uniformity of the obtained microspheres and high compressive strength are achieved, and the use of the indicated surface-active substances at the indicated temperatures in combination with the composition of the polymer mixture provides a high yield of the finished product and the specified characteristics of sphericity and roundness.

Figure 1 shows the image of the microspheres - fraction 0.355-0.855 mm Figure 2 shows the image of the obtained microspheres - fraction of 0.855-1.00 mm

The method is implemented as follows.

The components of the polymer mixture in the following quantitative ratio,% mass .: polymer stabilizer 0.1-4.5; polymer modifier 0.1-20.5; radical initiator 0.1-4; catalyst 0.002-0.02; dicyclopentadiene - the rest is successively mixed, introducing into the dicyclopentadiene first a stabilizer, and then a modifier, a radical initiator and, last, a catalyst. The resulting polymer mixture is kept at a temperature of 0-50 ° C for 1-40 minutes, after which it is introduced in the form of a laminar stream into water preheated at a temperature not lower than the temperature of the mixture containing cationic or anionic surfactants with constant stirring of water. The concentration of surfactants in water is maintained no higher than 1%, and the ratio of the polymer mixture to water with surfactants is not more than 0.5. In the process of mixing, an emulsion is formed from drops of the polymer mixture, which are formed into microspheres during the polymerization and under the influence of surfactants. The resulting microspheres are separated from the solution, heated to a temperature of 150-340 ° C and maintained at this temperature for 1-360 minutes.

The result is microspheres of polydicyclopentadiene having a roundness and sphericity of at least 0.9 for at least 70% by weight, the average size of which is in the range of 0.25-1.1 mm, and bulk density is in the range of 0.5-0 7 g / cm ³ .

The material is characterized by the following indicators:

Glass transition temperature (Tg)

- A 251 to 350 ° C

- B from 191 to 250 ° C

- B 141 to 190 ° C

- D from 80 to 140 ° C

Compressive strength, MPa

- And more than 250

- B from 170 to 249

- B 100 to 169

- g less than 100

Target fraction (0.25-1.1 mm),%

- And more than 75

- B from 70 to 74

- In less than 70

The method is illustrated by the following examples.

Example 1

In a separate container, a solution is prepared containing dicyclopentadiene (87.685% by mass), polymer stabilizers 1010 (0.5% by mass), 168 (0.4% by mass), 770 (0.4% by mass), BC radical initiator -FF (2% wt.), Modifiers ENB (5% wt.), GMA (1% wt.), MDI (3% wt.). Catalyst N2a (0.0151% by weight) was added at 30 ° C. The resulting mixture was stirred for 20 minutes, after which it was introduced as a laminar stream into water (polymer mixture / water 0.1) containing a dodecyl sulfate sodium surfactant (0.1% wt.) At 40 ° C. With constant stirring, the water is heated to 70 ° C and held for 15 minutes. The microspheres are separated, heated to 250 ° C and maintained at this temperature for 30 minutes. Get microspheres 98%, the target fraction (A), Tg (B), compressive strength (A), sphericity of 0.9.

Example 2

In a separate container, a solution is prepared containing dicyclopentadiene (98.290% by weight), polymer stabilizers 1010 (0.5% by weight), 168 (0.5% by weight), 770 (0.5% by weight), and radical initiator B (0.1% of the mass.), DVB modifiers (0.1% of the mass.). Catalyst N (0.0095% by weight) was added at 35 ° C. The resulting mixture was stirred for 40 minutes, after which it was introduced in the form of a laminar stream into water (polymer mixture / water 0.1) containing a dodecyl sulfate sodium surfactant (0.2% wt.) At 40 ° C. With constant stirring, the water is heated to 100 ° C and incubated for 10 minutes. The microspheres formed are separated from the solution, heated to a temperature of 200 ° C and maintained at this temperature for 30 minutes. Microspheres of 97% are obtained, target fraction (A), Tg (B), compressive strength (B), sphericity 0.9.

Example 3

In a separate container, a solution is prepared containing dicyclopentadiene (89.791% by weight), polymer stabilizers 1010 (0.5% by weight), 168 (0.5% by weight), BC-FF radical initiator (1% by weight), modifiers ENB (3% wt.), DMEG (0.2% wt.), Kraton 1104 (5% wt.). Catalyst N7a (0.0093% by weight) was added at 25 ° C. The resulting mixture was stirred for 10 minutes, after which it was introduced in the form of a laminar stream into water (polymer mixture / water 0.05) containing the surfactant cetyltrimethylammonium chloride (0.1% wt.) At 35 ° C. With constant stirring, the water is heated to 60 ° C and incubated for 15 minutes. The microspheres are separated, heated to 150 ° C and maintained at this temperature for 20 minutes. Microspheres of 97% are obtained, target fraction (A), Tg (B), compressive strength (B), sphericity 0.9.

Example 4

In a separate container, a solution is prepared containing dicyclopentadiene (96.888% by weight), polymer stabilizers 1010 (0.02% by weight), 168 (0.04% by weight), 770 (0.04% by weight), and radical initiator B (1% wt.), ENB modifiers (2% wt.). Catalyst N1 (0.0123% by weight) was added at 50 ° C. The resulting mixture was stirred for 5 minutes, after which it was introduced in the form of a laminar stream into water (polymer mixture / water 0.1) containing a surfactant dodecyl sulfate sodium (0.1% wt.) At 55 ° C. With constant stirring, the water is heated to 60 ° C and incubated for 45 minutes. The microspheres are separated, heated to 200 ° C and maintained at this temperature for 360 minutes. Microspheres of 89% are obtained, target fraction (A), Tg (B), compressive strength (B), sphericity 0.9.

Example 5

In a separate container, a solution is prepared containing dicyclopentadiene (91.191% by weight), polymer stabilizers 1010 (0.4% by weight), 168 (0.4% by weight), BC-FF radical initiator (1% by weight), modifiers ENB (5% wt.), DMEG (2% wt.). Catalyst N2 (0.0092% by weight) was added at 25 ° C. The resulting mixture was stirred for 10 minutes, after which it was introduced in the form of a laminar stream into water (polymer mixture / water 0.15) containing a surfactant cetyltrimethylammonium chloride (0.2% wt.) At 35 ° C. With constant stirring, the water is heated to 100 ° C and incubated for 15 minutes. The microspheres are separated, heated to 270 ° C and maintained at this temperature for 45 minutes. Microspheres of 96% are obtained, target fraction (A), Tg (A), compressive strength (B), sphericity 0.92.

Example 6

In a separate container, a solution is prepared containing dicyclopentadiene (88.392% wt.), Polymer stabilizers 1010 (0.4% wt.), 168 (0.8% wt.), 770 (0.4% wt.), BC radical initiator -FF (1.5% mass.), 30 (2.5% mass.), Modifiers ENB (5% mass.), TMPPTMA (1% mass.), Catalyst N14a (0.0081% mass.) Contribute at 25 ° C. The resulting mixture was stirred for 10 minutes, after which it was introduced in the form of a laminar stream into water (polymer mixture / water 0.1) containing a surfactant dodecyl sulfate sodium (0.05% wt.) At 35 ° C. With constant stirring, the water is heated to 95 ° C and incubated for 15 minutes. The microspheres are separated, heated to 250 ° C and maintained at this temperature for 45 minutes. Get microspheres 98%, the target fraction (A), Tg (B), compressive strength (B), sphericity of 0.9.

Example 7

In a separate container, a solution is prepared containing dicyclopentadiene (92.984% by mass), polymer stabilizers 1010 (0.5% by mass), 168 (0.5% by mass), 770 (0.5% by mass), and radical initiator B (0.5% wt.), NBD modifiers 2% wt.), DMEG (3% wt.). Catalyst N4 (0.0161% by weight) was added at 25 ° C. The resulting mixture was stirred for 10 minutes, after which it was introduced in the form of a laminar stream into water (polymer mixture / water 0.2), containing the surfactant ammonium lauryl sulfate (0.25% wt.) At 35 ° C. With constant stirring, the water is heated to 75 ° C and incubated for 30 minutes. The microspheres are separated, heated to 150 ° C and maintained at this temperature for 30 minutes. Microspheres of 95% are obtained, target fraction (B), Tg (C), compressive strength (B), sphericity 0.9.

Example 8

In a separate container, a solution is prepared containing dicyclopentadiene (87.994% wt.), Polymer stabilizers 1010 (0.5% wt.), 168 (0.5% wt.), 770 (0.5% wt.), BC radical initiator -FF (1% wt.), Modifiers ENB (5% wt.), GMA (1.5% wt.), TDI (3% wt.). Catalyst N5 (0.0057% wt.) Was added at 10 ° C. The resulting mixture was stirred for 5 minutes, after which it was introduced as a laminar stream into water (polymer mixture / water 0.1) containing a dodecyl sulfate sodium surfactant (0.1% wt.) At 30 ° C. With constant stirring, the water is heated to 100 ° C and incubated for 15 minutes. The microspheres are separated, heated to 200 ° C and maintained at this temperature for 30 minutes. Microspheres of 97% are obtained, target fraction (A), Tg (B), compressive strength (A), sphericity 0.92.

Example 9

In a separate container, a solution is prepared containing dicyclopentadiene (85.788% by mass), polymer stabilizers 330 (0.2% by mass), 168 (0.5% by mass), 123 (0.5% by mass), BC radical initiator -FF (1% wt.), Modifiers ENB (5% wt.), DMEG (2% wt.). Taipol 1307 (5% wt.). Catalyst N15a (0.0116% by weight) was added at 25 ° C. The resulting mixture was stirred for 10 minutes, after which it was introduced in the form of a laminar stream into water (polymer mixture / water 0.1) containing a surfactant dodecyl sulfate sodium (0.1% wt.) At 35 ° C. With constant stirring, the water is heated to 70 ° C and held for 60 minutes. The microspheres are separated, heated to 170 ° C and maintained at this temperature for 30 minutes. Microspheres of 97% are obtained, target fraction (A), Tg (B), compressive strength (A), sphericity 0.9.

Example 10

In a separate container, a solution is prepared containing dicyclopentadiene (92.797% wt.), Polymer stabilizers 14 (0.1% wt.), The radical initiator BTsFF (0.1% wt.), 30 (1.5% wt.) , ENB modifiers (3% wt.), BGDMA (2.5% wt.). Catalyst N1a (0.0031% by weight) was added at 30 ° C. The resulting mixture was stirred for 10 minutes, after which it was introduced in the form of a laminar stream into water (polymer mixture / water 0.1) containing the surfactant cetyltrimethylammonium chloride (0.1% wt.) At 40 ° C. With constant stirring, the water is heated to 70 ° C and incubated for 15 minutes. The microspheres are separated, heated to 280 ° C and maintained at this temperature for 1 min. Get the microspheres 90%, the target fraction (B), Tg (B), compressive strength (B), sphericity of 0.9.

Example 11

In a separate container, a solution is prepared containing dicyclopentadiene (69.494% by weight), polymer stabilizers 1010 (1.5% by weight), THPP (1% by weight), 123 (2% by weight), radical initiator B (2% by weight) .), 30 (2% wt.), NB modifiers 10% wt.), TTsDMA (12% wt.). Catalyst N3a (0.0204% by weight) was added at 25 ° C. The resulting mixture was stirred for 4 minutes, after which it was introduced in the form of a laminar stream into water (polymer mixture / water 0.1) containing the surfactant cetyltrimethylammonium chloride (0.3% wt.) At 40 ° C. With constant stirring, the water is heated to 100 ° C and incubated for 15 minutes. The microspheres are separated, heated to 260 ° C and maintained at this temperature for 40 minutes. Microspheres of 91% are obtained, target fraction (B), Tg (A), compressive strength (C), sphericity 0.9.

Example 12

In a separate container, a solution is prepared containing dicyclopentadiene (91.143% by mass), polymer stabilizers 330 (0.4% by mass), 168 (0.5% by mass), 234 (0.2% by mass), and radical initiator B (1% wt.), Modifiers ENB (3% wt.), DVB (0.75% wt.), DMEG (3% wt.). Catalyst N5a (0.0070% by weight) was added at 10 ° C. The resulting mixture was stirred for 2 minutes, after which it was introduced in the form of a laminar stream into water (polymer mixture / water 0.1) containing a surfactant sodium lauryl sarcosinate (0.1% wt.) At 35 ° C. With constant stirring, the water is heated to 80 ° C and incubated for 1 minute. The microspheres are separated, heated to 200 ° C and maintained at this temperature for 30 minutes. Microspheres of 94% are obtained, target fraction (A), Tg (B), compressive strength (A), sphericity 0.9.

Example 13

In a separate container, a solution is prepared containing dicyclopentadiene (86.787% wt.), Polymer stabilizers DFA (0.2% wt.), 168 (0.5% wt.), 292 (0.5% wt.), Radical initiator 30 (3% wt.), Data center modifiers (3% wt.), E2BADMA (6% wt.). Catalyst N19a (0.0130% by weight) was added at 0 ° C. The resulting mixture was stirred for 1 minute, after which it was introduced in the form of a laminar stream into water (polymer mixture / water 0.1) containing a surfactant cetyltrimethylammonium chloride (0.1% wt.) At 30 ° C. With constant stirring, the water is heated to 50 ° C and incubated for 40 minutes. The microspheres are separated, heated to 265 ° C and maintained at this temperature for 60 minutes. Microspheres of 93% are obtained, target fraction (B), Tg (B), compressive strength (A), sphericity 0.9.

Example 14

In a separate container, a solution is prepared containing dicyclopentadiene (91.480% by weight), polymer stabilizers 1010 (0.5% by weight), 168 (0.5% by weight), radical initiator B (1% by weight), 30 (1 % wt.), ENB modifiers (3% wt.), MPPTMA (2.5% wt.). Catalyst N6a (0.0201% wt.) Was added at 25 ° C. The resulting mixture was stirred for 10 minutes, after which it was introduced as a laminar stream into water (polymer mixture / water 0.1) containing a surfactant cetyltrimethylammonium chloride (0.1% wt.) At 35 ° C. With constant stirring, the water is heated to 80 ° C and incubated for 15 minutes. The microspheres are separated, heated to 300 ° C and maintained at this temperature for 30 minutes. Microspheres of 97% are obtained, target fraction (A), Tg (A), compressive strength (B), sphericity 0.9.

Example 15

In a separate container, a solution is prepared containing dicyclomentadiene (94.290% by weight), polymer stabilizers 1010 (0.4% by weight), THPP (0.4% by weight), 770 (0.4% by weight), BC radical initiator -FF (1% wt.), Modifiers ENB (3% wt.), DMEG (0.5% wt.). Catalyst N8a (0.0099% by weight) was added at 25 ° C. The resulting mixture was stirred for 10 minutes, after which it was introduced in the form of a laminar stream into water (polymer mixture / water 0.15) containing the surfactant cetyltrimethylammonium chloride (0.2% wt.) At 35 ° C. With constant stirring, the water is heated to 70 ° C and incubated for 15 minutes. The microspheres are separated, heated to 170 ° C and maintained at this temperature for 240 minutes. Microspheres of 98% are obtained, target fraction (B), Tg (C), compressive strength (B), sphericity 0.9.

Example 16

In a separate container, a solution is prepared containing dicyclopentadiene (92.590% by weight), polymer stabilizers 1010 (0.4% by weight), 168 (0.4% by weight), 770 (0.4% by weight), BC radical initiator -FF (1% mass.), TFM (1% mass.), ENB modifiers (3% mass.), TTsDMA (1.2% mass.). Catalyst N9a (0.0097% wt.) Was added at 15 ° C. The resulting mixture was stirred for 10 minutes, after which it was introduced as a laminar stream into water (polymer mixture / water 0.01) containing the surfactant cetyltrimethylammonium chloride (0.1% wt.) At 35 ° C. With constant stirring, the water is heated to 80 ° C and incubated for 15 minutes. The microspheres are separated, heated to 270 ° C and maintained at this temperature for 30 minutes. Microspheres of 97% are obtained, target fraction (A) 76, Tg (A), compressive strength (B), sphericity 0.9.

Example 17

In a separate container, a solution is prepared containing dicyclopentadiene (90.343% by weight), polymer stabilizers 1010 (0.45% by weight), 168 (0.45% by weight), 770 (0.45% by weight), BC radical initiator -FF (0.5% wt.), Modifiers of NBD (2% wt.), TTsDMA (0.8% wt.). Vector 41 ON (5% wt.). Catalyst N10a (0.0066% by weight) was added at 5 ° C. The resulting mixture was stirred for 10 minutes, after which it was introduced as a laminar stream into water (polymer mixture / water 0.3) containing a surfactant cetyltrimethylammonium chloride (0.2% wt.) At 35 ° C. With constant stirring, the water is heated to 95 ° C and incubated for 5 minutes. The microspheres are separated, heated to 170 ° C and maintained at this temperature for 30 minutes. Get microspheres 98%, the target fraction (A), Tg (C), compressive strength (B), sphericity of 0.9.

Example 18

In a separate container, a solution is prepared containing dicyclopentadiene (93.142% wt.), Polymer stabilizers 1010 (0.45% wt.), 168 (0.45% wt.), 770 (0.45% wt.), BC radical initiator -FF (0.5% wt.), Modifiers ENB (3% wt.), DMEG (2% wt.). Catalyst N11a (0.0080% by weight) was added at 25 ° C. The resulting mixture was stirred for 10 minutes, after which it was introduced as a laminar stream into water (polymer mixture / water 0.1) containing a surfactant cetyltrimethylammonium chloride (0.1% wt.) At 35 ° C. With constant stirring, the water is heated to 95 ° C and incubated for 15 minutes. The microspheres are separated, heated to 200 ° C and maintained at this temperature for 60 minutes. Microspheres of 99% are obtained, target fraction (A), Tg (G), compressive strength (B), sphericity 0.9.

Example 19

In a separate container, a solution is prepared containing dicyclopentadiene (90.960% wt.), Polymer stabilizers 1010 (0.36% wt.), 168 (0.72% wt.), 123 (0.45% wt.), Radical initiator% mass.), 30 (2% mass.), ENB modifiers (3% mass.), DMEG (2.5% mass.). Catalyst N3b (0.0096% by weight) was added at 30 ° C. The resulting mixture was stirred for 10 minutes, after which it was introduced as a laminar stream into water (polymer mixture / water 0.1) containing a surfactant octenidine hydrochloride (0.1% wt.) At 40 ° C. With constant stirring, the water is heated to 100 ° C and incubated for 15 minutes. The microspheres are separated, heated to 250 ° C and maintained at this temperature for 30 minutes. Microspheres of 97% are obtained, target fraction (A), Tg (A), compressive strength (B), sphericity 0.9.

Example 20

In a separate container, a solution is prepared containing dicyclopentadiene (91.640% by mass), polymer stabilizers 330 (0.35% by mass), 327 (0.2% by mass), 770 (0.5% by mass), and radical initiator B (0.1% wt.), 30 (2% wt.), Modifier ENB (3% wt.), BGDMA (2.2% wt.). Catalyst N12a (0.0097% by weight) was added at 25 ° C. The resulting mixture was stirred for 10 minutes, after which it was introduced in the form of a laminar stream into water (polymer mixture / water 0.2) containing a surfactant cetyltrimethylammonium chloride (0.1% wt.) At 35 ° C. With constant stirring, the water is heated to 95 ° C and incubated for 15 minutes. The microspheres are separated, heated to 270 ° C and maintained at this temperature for 30 minutes. Microspheres of 97% are obtained, target fraction (B), Tg (A), compressive strength (B), sphericity 0.9.

Example 21

In a separate container, a solution is prepared containing dicyclopentadiene (84.393% by mass), polymer stabilizers 1010 (0.5% by mass), 168 (0.5% by mass), 770 (0.5% by mass), and radical initiator B (0.1% wt.), Modifiers ENB (5% wt.), DGDMA (4% wt.), Europrene SOL T 9113 (5% wt.). Catalyst N3 (0.0070% by weight) was added at 25 ° C. The resulting mixture was stirred for 10 minutes, after which it was introduced in the form of a laminar stream into water (polymer mixture / water 0.1) containing a surfactant dodecyl sulfate sodium (0.1% wt.) At 35 ° C. With constant stirring, the water is heated to 75 ° C and incubated for 20 minutes. The microspheres are separated, heated to 180 ° C and maintained at this temperature for 30 minutes. Microspheres of 97% are obtained, target fraction (A), Tg (C), compressive strength (B), sphericity 0.9.

Example 22

In a separate container, a solution is prepared containing dicyclopentadiene (86.642% wt.), Polymer stabilizers 1010 (0.45% wt.), THPP (0.45% wt.), 292 (0.45% wt.), Radical initiator B (1% wt.), Modifiers ENB (5% wt.), DMEG (1% wt.), SKTN (5% wt.). Catalyst N13a (0.0078% by weight) was added at 25 ° C. The resulting mixture was stirred for 10 minutes, after which it was introduced in the form of a laminar stream into water (polymer mixture / water 0.1) containing a surfactant dodecyl sulfate sodium (0.1% wt.) At 35 ° C. With constant stirring, the water is heated to 95 ° C and incubated for 15 minutes. The microspheres are separated, heated to 220 ° C and maintained at this temperature for 30 minutes. Microspheres of 97% are obtained, target fraction (A), Tg (B), compressive strength (B), sphericity 0.92.

Example 23

In a separate container, a solution is prepared containing dicyclopentadiene (91.288% by weight), polymer stabilizers 703 (0.2% by weight), THPP (0.5% by weight), 292 (0.5% by weight), BC radical initiator -FF (1% mass.), 30 (2% mass.), Modifiers ENB (3% mass.), TMPPTMA (1.5% mass.). Catalyst N16a (0.0124% by weight) was added at 30 ° C. The resulting mixture was stirred for 1 minute, after which it was introduced as a laminar stream into water (polymer mixture / water 0.4) containing a surfactant benzalkonium chloride (0.2% wt.) At 40 ° C. With constant stirring, the water is heated to 75 ° C and incubated for 15 minutes. The microspheres are separated, heated to 260 ° C and maintained at this temperature for 30 minutes. Microspheres of 95% are obtained, target fraction (B), Tg (A), compressive strength (B), sphericity 0.9.

Example 24

In a separate container, a solution is prepared containing dicyclopentadiene (92.787% wt.), Polymer stabilizers 14 (0.2% wt.), 168 (0.5% wt.), 292 (0.5% wt.), Radical initiator B (1% wt.), 30 (2% wt.), CO modifiers (1% wt.), BGDMA (1% wt.), DPB (1% wt.). Catalyst N17a (0.0128% by weight) was added at 20 ° C. The resulting mixture was stirred for 5 minutes, after which it was introduced in the form of a laminar flow into water (polymer mixture / water 0.1) containing a surfactant benzalkonium chloride (0.1% wt.) At 30 ° C. With constant stirring, the water is heated to 50 ° C and incubated for 10 minutes. The microspheres are separated, heated to 340 ° C and maintained at this temperature for 10 minutes. Microspheres of 97% are obtained, target fraction (B), Tg (A), compressive strength (G), sphericity 0.9.

Example 25

In a separate container, a solution is prepared containing dicyclopentadiene (92.387% wt.), Polymer stabilizers 702 (0.4% wt.), 168 (0.8% wt.), 770 (0.4% wt.), BC radical initiator -FF (1% wt.), Modifiers ENB (3% wt.), DMEG (2% wt.). Catalyst N18a (0.0130% by weight) was added at 10 ° C. The resulting mixture was stirred for 5 minutes, after which it was introduced in the form of a laminar flow into water (polymer mixture / water 0.1) containing a surfactant benzalkonium chloride (0.1% wt.) At 30 ° C. With constant stirring, the water is heated to 80 ° C and incubated for 15 minutes. The microspheres are separated, heated to 200 ° C and maintained at this temperature for 30 minutes. Microspheres of 98% are obtained, target fraction (A), Tg (B), compressive strength (A), sphericity 0.9.

Example 26

In a separate container, a solution is prepared containing dicyclopentadiene (89.895% by weight), polymer stabilizers 330 (0.4% by weight), 327 (0.2% by weight), 770 (0.5% by weight), BC radical initiator -FF (1% wt.), Modifiers ENB (3% wt.), E2BADMA (5% wt.). Catalyst N4a (0.0047% by weight) was added at 25 ° C. The resulting mixture was stirred for 10 minutes, after which it was introduced as a laminar stream into water (polymer mixture / water 0.1) containing a surfactant cetyltrimethylammonium chloride (0.1% wt.) At 35 ° C. With constant stirring, the water is heated to 80 ° C and incubated for 15 minutes. The microspheres are separated, heated to 200 ° C and maintained at this temperature for 30 minutes. Microspheres of 92% are obtained, target fraction (B), Tg (C), compressive strength (A), sphericity 0.9.

Example 27

In a separate container, a solution is prepared containing dicyclopentadiene (90.593% by weight), polymer stabilizers 5057 (0.4% by weight), 168 (0.5% by weight), 770 (0.5% by weight), BC radical initiator -FF (1% wt.), 30 (1% wt.), Modifiers ENB (3% wt.), BGDMA (3% wt.). Catalyst N20a (0.0071% by weight) was added at 15 ° C. The resulting mixture was stirred for 10 minutes, after which it was introduced in the form of a laminar stream into water (polymer mixture / water 0.1) containing a surfactant octepidine hydrochloride (0.1% wt.) At 40 ° C. With constant stirring, the water is heated to 70 ° C and incubated for 15 minutes. The microspheres are separated, heated to 255 ° C and maintained at this temperature for 30 minutes. Microspheres of 97% are obtained, target fraction (A), Tg (B), compressive strength (A), sphericity 0.9.

Example 28

In a separate container, a solution is prepared containing dicyclopentadiene (93.793% wt.), Polymer stabilizers 354 (0.4% wt.), THPP (0.8% wt.), Radical initiator B (2% wt.), Data center modifiers ( 2% of the mass.), DMEG (1% of the mass.). Catalyst N1b (0.0066% by weight) was added at 30 ° C. The resulting mixture was stirred for 10 minutes, after which it was introduced as a laminar stream into water (polymer mixture / water 0.1) containing a surfactant octenidine hydrochloride (0.1% wt.) At 40 ° C. With constant stirring, the water is heated to 70 ° C and incubated for 15 minutes. The microspheres are separated, heated to 200 ° C and maintained at this temperature for 120 minutes. Microspheres of 96% are obtained, target fraction (B), Tg (C), compressive strength (B), sphericity 0.9.

Example 29

In a separate container, a solution is prepared containing dicyclopentadiene (86.498% wt.), Polymer stabilizers 168 (1% wt.), 770 (0.5% wt.), The radical initiator BTsFF (1% wt.), 30 (1 % wt.), ENB modifiers (2% wt.), TMPPTMA (8% wt.). Catalyst N2b (0.0020% by weight) was added at 45 ° C. The resulting mixture was stirred for 10 minutes, after which it was introduced in the form of a laminar stream into water (polymer mixture / water 0.5) containing a surfactant cetyltrimethylammonium chloride (0.5% wt.) At 50 ° C. With constant stirring, the water is heated to 70 ° C and incubated for 15 minutes. The microspheres are separated, heated to 275 ° C and maintained at this temperature for 30 minutes. Microspheres of 92% are obtained, the target fraction (B), Tg (G), compressive strength (A), sphericity 0.9.

Example 30

In a separate container, a solution is prepared containing dicyclopentadiene (93.521% by weight), polymer stabilizers 702 (0.37% by weight), 168 (0.73% by weight), 770 (0.37% by weight), BC radical initiator -FF (1% wt.), Modifiers ENB (3% wt.), DMEG (1% wt.). Catalyst N4b (0.0090% by weight) was added at 30 ° C. The resulting mixture was stirred for 10 minutes, after which it was introduced in the form of a laminar stream into water (polymer mixture / water 0.1) containing a surfactant dodecyl sulfate sodium (0.5% wt.) At 40 ° C. With constant stirring, the water is heated to 80 ° C and incubated for 15 minutes. The microspheres are separated, heated to 200 ° C and maintained at this temperature for 60 minutes. Get microspheres 96%, the target fraction (C), Tg (C), compressive strength (B), sphericity of 0.9.

Example 31

In a separate container, a solution is prepared containing dicyclopentadiene (92.593% by weight), polymer stabilizers 168 (0.45% by weight), 770 (0.45% by weight), BC-FF radical initiator (1% by weight), 30 (1.5% wt.), Modifiers ENB (3% wt.), DMEG (1% wt.). Catalyst N5b (0.0072% by weight) was added at 30 ° C. The resulting mixture was stirred for 10 minutes, after which it was introduced in the form of a laminar stream into water (polymer mixture / water 0.1) containing the surfactant cetyltrimethylammonium chloride (0.1% wt.) At 40 ° C. With constant stirring, the water is heated to 60 ° C and incubated for 15 minutes. The microspheres are separated, heated to 260 ° C and maintained at this temperature for 30 minutes. Microspheres of 97% are obtained, target fraction (A), Tg (B), compressive strength (B), sphericity 0.9.

Example 32

In a separate container, a solution is prepared containing dicyclopentadiene (86.550% by mass), polymer stabilizers 1010 (0.37% by mass), 168 (0.1% by mass), 770 (0.47% by mass), BC radical initiator -FF (1% mass.), 30 (1% mass.), Modifiers ENB (3% mass.), ED (2.5% mass.), GMA (5% mass.). Catalyst N1c (0.0102% by weight) was added at 20 ° C. The resulting mixture was stirred for 5 minutes, after which it was introduced in the form of a laminar flow into water (polymer mixture / water 0.2) containing a surfactant cetyltrimethylammonium chloride (0.1% wt.) At 40 ° C. With constant stirring, the water is heated to 80 ° C and incubated for 15 minutes. The microspheres are separated, heated to 310 ° C and maintained at this temperature for 5 minutes. Microspheres of 93% are obtained, target fraction (B), Tg (A), compressive strength (C), sphericity 0.92.

The proposed technology allows to obtain microspheres from polydicyclopentadiene with a high degree of sphericity - not less than 0.9 and high compressive strength - not worse than 90 MPa with a bulk density in the range of 0.5-0.7 g / cm ³ .

Claims (5)

1. Microspheres of polydicyclopentadiene having a roundness and sphericity of at least 0.9 for at least 70% by weight, the average size of which is in the range of 0.25-1.1 mm, and bulk density is in the range of 0.40-0, 70 g / cm ³ . 2. The method of producing microspheres from polydicyclopentadiene according to claim 1, comprising obtaining a liquid polymer mixture by sequentially mixing dicyclopentadiene with a polymer stabilizer, which is used as the following compounds or mixtures thereof: 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-butylfe nol), 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) sebacinate, bis (1-octyloxy-2,2,6,6-tetramethyl-4-piperidinyl) sebacinate, bis (1-methyl-2,2,6,6- tetramethyl-4-piperidinyl) sebacinate, 2-tert-butyl-6- (5-chloro-2H-benzotriazol-2-yl) -4-methylphenol, 2- (2H-benzotriazol-2-yl) -4,6- bis (1-methyl-1-phenyl) phenol, a radical initiator, which is used as the following compounds or mixtures thereof: di-tert-butyl peroxide, dicumyl peroxide, 2,3-dimethyl-2,3-diphenyl-bu tan, triphenylmethane, with a polymer modifier, which are selected as the following compounds or mixtures thereof: ethylidene norbornene, norbornene, norbornadiene, cyclooctene, cyclooctadiene, diisocyanates, styrene-isoprene-styrene, and styrene-butadiene-styrene-block copolymethyl acrylate, polymethyl acrylate, polymethyl ethylene dimethacrylate, diethylene glycol dimethacrylate, butylene glycol dimethacrylate, tricyclodecane dimethanol dimethacrylate, ethoxylated bisphenol A dimethacrylate, trimethylol propane trimethacrylate, divinylbenzene, diisopropenylben Evil and a catalyst, which is used as a compound of General formula:

where the Deputy L is selected from the group:

,

,

,

,

,

,
the resulting polymer mixture is kept at a temperature of 10-50 ° C for 1-40 minutes, after which it is introduced in the form of a laminar stream into water preheated at a temperature not lower than the temperature of the mixture containing cationic or anionic surfactants, with constant stirring of the liquid medium, the resulting microspheres are separated from the solution, heated to a temperature of 150-340 ° C and maintained at this temperature for 1-360 minutes 3. The method according to claim 2, characterized in that the components of the polymer mixture are in the following quantitative ratio, wt.%:
polymer stabilizer 0.1-4.5;
polymer modifier 0.1-20.5;
radical initiator 0.1-4;
catalyst 0.002-0.02;
dicyclopentadiene - the rest. 4. The method according to claim 2, characterized in that the concentration of surfactants in the water does not exceed 1%. 5. The method according to claim 2, characterized in that the ratio of the polymer mixture to water with surfactants is not more than 0.5.

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