RU2515248C1 - Method of making articles from polydicyclopentadiene by centrifugal moulding - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: described is a method of producing polymer articles based on polydicyclopentadiene by centrifugal moulding, which involves mixing dicyclopentadiene with a ruthenium-containing catalyst and modifying additives, placing the mixture into a mould, rotating the mould while heating to temperature of 40-110°C and holding said temperature for 5-60 minutes, and then removing the article from the mould, heating to temperature of 150-300°C and holding at said temperature for 5-120 minutes.

EFFECT: low consumption of catalyst and enabling control of the polymerisation process.

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Description

The invention relates to the chemistry of macromolecular compounds, in particular to a technology for producing polymer products based on polydicyclopentadiene by centrifugal molding.

Centrifugal casting of polymers is a technology for producing hollow products, as a rule, in the form of bodies of revolution by molding under the influence of centrifugal force.

The centrifugal casting process is carried out at high rotational speeds of the mold, therefore, under the action of centrifugal forces, the polymer experiences significant pressure and the product removed from the mold is not subject to significant shrinkage. This method is most widely used in the production of thin-walled or large-diameter products from polyamides, polyesters and other thermoplastics with low melt viscosity. Moreover, due to the tendency of these polymers to oxidize, the mold cavity is filled with an inert gas.

Two stages of the molding process itself can be distinguished - shaping and fixing the shape of the product. The process of shaping is the distribution of feedstock over the surface of the mold as a result of the application of centrifugal forces. The main determining factors characterizing this process are the viscosity of the raw materials, surface tension, the speed and uniformity of curing, the nature of the temperature change of these properties. Fixation of the mold is the final hardening of the polymer in the injection mold. The nature of this process, which determines the properties of the hardened product, is mainly determined by the composition of the polymer, the type of product, the temperature at which the final cure occurs.

During centrifugal molding of polymer products, the chemical composition of the feedstock, the type and material of the molds, the nature of their contact with the polymer mass during molding, the temperature conditions of the molding process, and cooling conditions are crucial. Each of these factors affects the rate of hardening of the mass, which determines the quality of the product and the productivity of the molding.

The choice of frequency of rotation of the mold must be consistent with the rate of increase in viscosity. If the rate of polymerization, and hence the rate of increase in viscosity, is large, then at low rotational speeds the entire polymer cannot be evenly distributed over the surface of the mold.

The use of dicyclopentadiene as the basis for the preparation of polymer products by centrifugal molding compares favorably with other materials by low viscosity, the absence of the need to use inert gases during molding, controllability of polymerization conditions, and high physicomechanical characteristics of the obtained products, provided that certain types of catalysts are used.

A known method of producing products from polydicyclopentadiene by centrifugal molding, including heating the mold, feeding it a mixture of dicyclopentadiene, a catalyst and modifying additives and subsequent rotation of the mold during the polymerization of dicyclopentadiene (Rotational molding of a dicyclopentadiene reactive liquid polymer. N. Corrigan, E. Harkin- Jones and RJ Crawford. Dept. of Mechanical & Manufacturing Engineering, Queen's University of Belfast, Northern Ireland. ANTEC, 2002).

The disadvantage of this method is the use of Telene catalysts with high sensitivity to monomer quality and unstable in air. The polymerization rate in the presence of Telene catalysts is too high, as a result of which the polymerization process begins before the starting material is evenly distributed on the surface of the mold, which leads to uneven geometric and physico-mechanical characteristics of the finished product.

A known method of centrifugal molding of products from polydicyclopentadiene, comprising feeding a mixture of dicyclopentadiene, a catalyst and modifying additives and polymerizing dicyclopentadiene by rotating the mold (US Patent No. 5266370, 1993).

The main disadvantage of this method are the properties of the used catalysts, which do not allow to provide all the advantages of centrifugal molding technology. Centrifugal forces, combined with the nature of the polymerization processes, the initial viscosity of the material, the temperature and polymerization rate, largely determine the properties of the molded products. The catalysts used in the known solution are not stable in air. This leads to the need for molding in an inert atmosphere.

In addition, since the polymerization of dicyclopentadiene is exothermic, in the production of thick-walled products, the temperature in the mass of the initial mixture of monomer and catalyst will be uneven, not only due to the unevenness of the polymerization reaction in the mass of the substance due to the mentioned properties of the catalyst, but also from -for increased heat transfer in the surface layers of the molded mass. In thin-walled products, high heat transfer due to the small wall thickness leads to a decrease in the speed and completeness of polymerization, an increase in shrinkage deformation of the finished product.

The closest technical solution to the proposed one is a method for producing products from polydicyclopentadiene by centrifugal molding, including mixing dicyclopentadiene with a catalyst, placing the mixture in a rotating form, polymerizing dicyclopentadiene during rotation and unloading the polymer product from the mold (US Patent No. 6410110, 1998).

The disadvantages of the method include the use of expensive and ineffective catalysts - ruthenium carbene complexes of the first generation. In the manufacture of products from polydicyclopentadiene (PDCPD) by centrifugal molding using these catalysts, it is necessary to use additives of inhibitors to control the start time of the polymerization, otherwise the polymer formed too early increases the viscosity of the initial mixture, complicating the process of forming and increasing the number of formed defects of the product.

The problem solved by the claimed invention is to improve the quality of the finished product, expressed in increasing geometric accuracy and physico-mechanical properties through the use of a series of ruthenium catalysts that thermally control the beginning of the polymerization process while using small amounts of catalyst and affect the polymerization process while applying forced heating of the reaction mass in the declared mode.

The technical result consists in providing the ability to control the start time and speed of polymerization, reducing catalyst consumption, purposefully improving the physicomechanical characteristics of the finished product, the ability to polymerize in air and not in an inert gas environment, reducing the unevenness and shrinkage of the finished product.

, где заместитель L выбран из группы:The solution of the problem and the achievement of the technical result are ensured by the fact that a compound of the general formula is used as a catalyst

where the Deputy L is selected from the group:

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, при этом после заливки смеси дициклопентадиена и катализатора во вращающуюся форму, последнюю нагревают до температуры 40-110°C и выдерживают при данной температуре в течение 5-60 мин, а после выгрузки из формы изделие нагревают до температуры 150-300°C и выдерживают при данной температуре в течение 5-120 мин, после чего изделие охлаждают до комнатной температуры.

in this case, after pouring the mixture of dicyclopentadiene and the catalyst into a rotating mold, the latter is heated to a temperature of 40-110 ° C and maintained at this temperature for 5-60 minutes, and after unloading from the mold, the product is heated to a temperature of 150-300 ° C and maintained at this temperature for 5-120 minutes, after which the product is cooled to room temperature.

These distinctive features are significant, and their combination ensures the achievement of a technical result and the solution of the task.

The use of these catalysts allows you to evenly dissolve them in the monomer without the active initiation of polymerization, which begins only after heating the mixture to a predetermined temperature, and maintaining this temperature during polymerization due to external heating leads to the uniformity of this process. Moreover, the separation of the heating of the molded material into two stages - during the molding period and after unloading the product, significantly reduces the deformation of the product by preventing significant thermal expansion of the mold material at high temperatures, and also increases the physicomechanical characteristics of the finished product, providing a denser polymer structure.

To obtain products with different physical and mechanical properties, dicyclopentadiene is used, containing polymer modifiers, which can be used as the following compounds or mixtures thereof:

- ethylidene norbornene (ENB) or trimers and tetramers of cyclopentadiene (OLCPD), norbornene, norbornadiene, cyclooctene, cyclooctadiene, diisocyanates (e.g. TDI, MDI), styrene-isoprene-styrene, and Styrene-butadiene copolymer styrene (e.g. styrene-styrene) Kraton 1104, Taipol 1307, Europrene SOL T 9113, etc.), polydimethisiloxane (CKTN), (allyl methacrylate (AlMAK), glycidyl methacrylate (GMA), ethylene dimethacrylate (DMEG), diethylene glycol dimethacrylate (DGDMA), tri-dimethyl tri-dimethacrylate) ethoxylated bisphenol A dimethacrylate (E2BADMA), three etilolpropantrimetakrilat (TMPTMA), divinylbenzene, diisopropenylbenzene (DVB), bisphenol-A epoxy resin (ED)) - from 0.5 to 60.0% wt .;

- polymer stabilizer, which is used as the following compounds or mixtures thereof (in parentheses after each name is an abbreviation): tetrakis [methylene (3,5-di-tert-butyl-4-hydroxyhydrocinnamate)] methane (1010), 2 , 6-di-tert-butyl-4- (dimethylamino) phenol (703), 1,3,5-trimethyl-2,4,6-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'-dif enyl-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-phenyl) phenol (234) - from 0.1 to 3.0% by weight .;

- a radical initiator, which is used as the following compounds or mixtures thereof: di-tert-butyl peroxide (B), dicumyl peroxide (BTs4M1), 2,3-dimethyl-2,3-diphenyl-butane (30), triphenylmethane (TFM) - from 0.1 to 4.0% of the mass.

The resulting material is tested according to the following indicators.

Glass transition temperature (Tg)

- A from 251 to 350 ° C

- B from 191 to 250 ° C

- B 141 to 190 ° C

- D from 80 to 140 ° C

Modulus of elasticity in bending (E), GPa

- A from 1.71 to 2.1

- B from 1.5 to 1.7

Tensile Strength (GOST 11262), MPa

- A from 56 to 66

- B from 40 to 55

Izod impact strength on notched specimens, KJ / m2

- A 31 to 60

- B from 16 to 30

- B from 5 to 15

- G less than 4

This technical solution is illustrated by the following examples.

Example 1

A solution of catalyst N in dicyclopentadiene (molar ratio 1: 70,000) containing, in addition to the above-mentioned polymer stabilizers 1010 (0.5 wt.%, 770 (0.5 wt.%), 168 (0.5 wt.%) And the ENB modifier (3 wt.%).

The mold is closed and rotated at a speed of 300-800 rpm at a temperature of a heated mold of 80 ° C for 20 minutes. The product is removed from the company and heated at 200 ° C for 30 minutes. Get the product with high-quality internal and external surfaces without defects. Tg (B), E (B), tensile strength (A), Izod impact strength on notched specimens (B).

Example 2

A solution of catalyst N1 in dicyclopentadiene (molar ratio 1: 70,000) containing, in addition to the aforementioned, polymer stabilizers 1010 (0.4% by weight), 168 (0.1% by weight) and 770 (0.5% wt.) And the ENB modifier (3% wt.).

The mold is closed and rotated at a speed of 300-800 rpm at a temperature of the heated mold of 60 ° C for 40 minutes. The product is removed from the mold and heated at 200 ° C for 30 minutes. Get the product with high-quality internal and external surfaces without defects. Tg (B), E (B), tensile strength (A), Izod impact strength on notched specimens (B).

Example 3

A solution of catalyst N2 in dicyclopentadiene (molar ratio 1: 100000) containing, in addition to the aforementioned, polymer stabilizers 1010 (0.4% by weight), 168 (0.4% by weight), is placed in a mold for centrifugal molding at 25 ° C, modifier OLCPD (10% wt.), radical initiators BTsFF (1% wt.) and 30 (1% wt.). The mold is closed and rotated at a speed of 300-800 rpm at a temperature of the heated mold of 50 ° C for 60 minutes. The product is removed from the mold and heated at 270 ° C for 120 minutes. Get the product with high-quality internal and external surfaces without defects. Tg (B), E (A), tensile strength (A), Izod impact strength on notched specimens (G).

Example 4

A solution of catalyst N3 in dicyclopentadiene (molar ratio 1: 75000) containing, in addition to the aforementioned polymer stabilizers 1010 (0.5% wt.), 168 (0.5% wt.), Is placed in a centrifugal molding mold at 25 ° C, 770 (0.5% wt.) And the ENB modifier (3% wt.).

The mold is closed and rotated at a speed of 300-800 rpm at a temperature of the heated mold of 70 ° C for 20 minutes. The product is removed from the mold and heated at 200 ° C for 30 minutes. Get the product with high-quality internal and external surfaces without defects. Tg (B), E (B), tensile strength (A), Izod impact strength on notched specimens (B).

Example 5

A solution of catalyst N4 in dicyclopentadiene (molar ratio 1: 50,000) is placed in a centrifugal molding mold at 25 ° C. containing, in addition to the above, polymer stabilizers 1010 (0.5% wt.), 168 (0.5% wt.), 770 (0.5% wt.) and an OLCCP modifier (10% wt.).

The mold is closed and rotated at a speed of 300-800 rpm at a temperature of the heated mold of 70 ° C for 30 minutes. The product is removed from the mold and heated at 150 ° C for 30 minutes. Get the product with high-quality internal and external surfaces without defects. Tg (B), E (B), tensile strength (A), Izod impact strength on notched specimens (B).

Example 6

A solution of catalyst N5 in dicyclopentadiene (molar ratio 1: 70,000) containing, in addition to the aforementioned, polymer stabilizers 1010 (0.5% wt.), 168 (0.5% wt.), Is placed in a mold for centrifugal molding at 10 ° C, and 292 (0.5% wt.) and the ENB modifier (3% wt.).

The mold is closed and rotated at a speed of 300-800 rpm at a temperature of the heated mold of 40 ° C for 15 minutes. The product is removed from the mold and heated at 200 ° C for 30 minutes. Get the product with high-quality internal and external surfaces without defects. Tg (B), E (B), tensile strength (A), Izod impact strength on notched specimens (B).

Example 7

A solution of N1a catalyst in dicyclopentadiene (molar ratio 1: 70,000) containing, in addition to the aforementioned, polymer stabilizers 14 (0.5% wt.), 168 (0.5% wt.) And 770 (0.5% wt.), Modifiers ENB (3% wt.) And Vector 41 PA (4% wt.). The mold is closed and rotated at a speed of 300-800 rpm at a temperature of the heated mold of 70 ° C for 15 minutes. The product is removed from the mold and heated at 180 ° C for 30 minutes. Get the product with high-quality internal and external surfaces without defects. Tg (C), E (B), tensile strength (B), Izod impact strength on notched specimens (A).

Example 8

A solution of N2a catalyst in dicyclopentadiene (molar ratio 1: 70,000) containing, in addition to the aforementioned, polymer stabilizers 1010 (0.5 wt%), 168 (0.4 wt%) and 770 (0.4% wt.) And the ENB modifier (3% wt.), Radical initiators B (0.7% wt.) And 30 (1% wt.). The mold is closed and rotated at a speed of 300-800 rpm at a temperature of the heated mold of 70 ° C for 15 minutes. The product is removed from the mold and heated at 250 ° C for 30 minutes. Get the product with high-quality internal and external surfaces without defects. Tg (B), E (A), tensile strength (A), Izod impact strength on notched specimens (G).

Example 9

A solution of N3a catalyst in dicyclopentadiene (molar ratio 1: 76000) is placed in a centrifugal molding mold at 25 ° C, containing, in addition to the above, polymer stabilizers 1010 (0.4 wt%), THPP (1 wt%), 123 ( 1% of the mass.) And the modifier OLCPD (10% of the mass.).

The mold is closed and rotated at a speed of 300-800 rpm at a temperature of the heated mold 110 ° C for 15 minutes. The product is removed from the mold and heated at 200 ° C for 30 minutes. Get the product with high-quality internal and external surfaces without defects. Tg (B), E (B), tensile strength (A), Izod impact strength on notched specimens (G).

Example 10

A solution of N4a catalyst in dicyclopentadiene (molar ratio 1: 100000) containing, in addition to the aforementioned, polymer stabilizers 330 (0.4% by weight), 327 (0.2% by weight), is placed in a mold for centrifugal molding at 25 ° C, 770 (0.5% wt.) And the ENB modifier (3% wt.).

The mold is closed and rotated at a speed of 300-800 rpm at a temperature of the heated mold of 80 ° C for 15 minutes. The product is removed from the mold and heated at 200 ° C for 30 minutes. Get the product with high-quality internal and external surfaces without defects. Tg (B), E (B), tensile strength (A), Izod impact strength on notched specimens (G).

Example 11

A solution of N5a catalyst in dicyclopentadiene (1: 70,000 molar ratio) containing, in addition to the above, polymer stabilizers 330 (0.4% by weight), 168 (0.5% by weight) and 234 (0.2%) mass.), ENB modifiers (5% mass.) And DMEG (3% mass.), BC-FF radical initiators (1.5% mass.) And 30 (1.5% mass. ) The mold is closed and rotated at a speed of 300-800 rpm at a temperature of a heated mold of 40 ° C for 5 minutes. The product is removed from the mold and heated at 300 ° C for 5 minutes. Get the product with high-quality internal and external surfaces without defects. Tg (A), E (A), tensile strength (A), Izod impact strength on notched specimens (G).

Example 12

A solution of N6a catalyst in dicyclopentadiene (molar ratio 1: 70,000) containing, in addition to the aforementioned, polymer stabilizers 1010 (0.5 wt%), 168 (0.5 wt%) and ENB modifier (3% wt.).

The mold is closed and rotated at a speed of 300-800 rpm at a temperature of the heated mold of 80 ° C for 15 minutes. The product is removed from the mold and heated at 200 ° C for 30 minutes. Get the product with high-quality internal and external surfaces without defects. Tg (B), E (B), tensile strength (A), Izod impact strength on notched specimens (G).

Example 13

A solution of N7a catalyst in dicyclopentadiene (1: 50,000 molar ratio) containing, in addition to the aforementioned, polymer stabilizers 1010 (0.5% by weight), 168 (0.5% by weight) and ENB modifier (3% wt.).

The mold is closed and rotated at a speed of 300-800 rpm at a temperature of the heated mold of 60 ° C for 15 minutes. The product is removed from the mold and heated at 200 ° C for 30 minutes. Get the product with high-quality internal and external surfaces without defects. Tg (B), E (B), tensile strength (A), Izod impact strength on notched specimens (G).

Example 14

A solution of N8a catalyst in dicyclopentadiene (1: 70,000 molar ratio) containing, in addition to the polymer stabilizers 1010 (0.4% by weight), THPP (0.4% by weight) and 770 (0.4% wt.), Modifiers ENB (3% wt.) And Kraton 1104 (5% wt.). The mold is closed and rotated at a speed of 300-800 rpm at a temperature of the heated mold of 70 ° C for 15 minutes. The product is removed from the mold and heated at 150 ° C for 60 minutes. Get the product with high-quality internal and external surfaces without defects. Tg (C), E (B), tensile strength (B), Izod impact strength on notched specimens (A).

Example 15

A solution of N9a catalyst in dicyclopentadiene (molar ratio 1: 70,000) containing, in addition to the above-mentioned polymer stabilizers 1010 (0.4% by weight), 168 (0.4% by weight), is placed in a mold for centrifugal molding at 15 ° C, 770 (0.4% by weight) and the ENB modifier (3% by weight).

The mold is closed and rotated at a speed of 300-800 rpm at a temperature of the heated mold of 80 ° C for 15 minutes. The product is removed from the mold and heated at 200 ° C for 30 minutes. Get the product with high-quality internal and external surfaces without defects. Tg (B), E (B), tensile strength (A), Izod impact strength on notched specimens (B).

Example 16

A solution of N10a catalyst in dicyclopentadiene (1: 70,000 molar ratio) containing, in addition to the polymer stabilizers 1010 (0.45% by weight), 168 (0.453% by weight), 770 (in addition to the above) is placed in a centrifugal molding mold at 5 ° C 0.45% wt.) And the modifier OLCPD (15% wt.).

The mold is closed and rotated at a speed of 300-800 rpm at a temperature of a heated mold of 40 ° C for 5 minutes. The product is removed from the mold and heated at 200 ° C for 30 minutes. Get the product with high-quality internal and external surfaces without defects. Tg (B), E (B), tensile strength (A), Izod impact strength on notched specimens (B).

Example 17

A solution of N11a catalyst in dicyclopentadiene (molar ratio 1: D000,) containing, in addition to the aforementioned, polymer stabilizers 1010 (0.45% by weight), 168 (0.45% by weight), is placed in a mold for centrifugal molding at 25 ° C, 770 (0.45% wt.) And the ENB modifier (3% wt.).

The mold is closed and rotated at a speed of 300-800 rpm at a temperature of the heated mold of 70 ° C for 15 minutes. The product is removed from the mold and heated at 200 ° C for 5 minutes. Get the product with high-quality internal and external surfaces without defects. Tg (G), E (B), tensile strength (A), Izod impact strength on notched specimens (B).

Example 18

A solution of N12a catalyst in dicyclopentadiene (molar ratio 1: 70,000) containing, in addition to the aforementioned, polymer stabilizers 330 (0.35% by weight), 327 (0.2% by weight) and 770 (0.5%) mass.), ENB modifiers (3% mass.) And Taipol 1307 (3% mass.). The mold is closed and rotated at a speed of 300-800 rpm at a temperature of the heated mold of 70 ° C for 15 minutes. The product is removed from the mold and heated at 170 ° C for 30 minutes. Get the product with high-quality internal and external surfaces without defects. Tg (C), E (B), tensile strength (B), Izod impact strength on notched specimens (A).

Example 19

A solution of N13a catalyst in dicyclopentadiene (1: 70,000 molar ratio) containing, in addition to the polymer stabilizers 1010 (0.45% by weight), THPP (0.45% by weight), is placed in a centrifugal molding mold at 25 ° C, 292 (0.45% wt.) And the ENB modifier (3% wt.), Radical initiators BTs-FF (2% wt.). The mold is closed and rotated at a speed of 300-800 rpm at a temperature of the heated mold of 70 ° C for 15 minutes. The product is removed from the mold and heated at 220 ° C for 45 minutes. Get the product with high-quality internal and external surfaces without defects. Tg (B), E (A), tensile strength (A), Izod impact strength on notched specimens (G).

Example 20

A solution of N14a catalyst in dicyclopentadiene (molar ratio 1: 150,000) containing, in addition to the aforementioned, polymer stabilizers 1010 (0.4% by weight), 168 (0.8% by weight) and 770 (0.4% wt.), Modifiers ENB (3% wt.), GMA (0.5% wt.) And ED (2% wt.), Radical initiators BC-FF (1.5% wt.) and 30 (1% of the mass.). The mold is closed and rotated at a speed of 300-800 rpm at a temperature of the heated mold of 70 ° C for 15 minutes. The product is removed from the mold and heated at 250 ° C for 30 minutes. Get the product with high-quality internal and external surfaces without defects. Tg (B), E (A), tensile strength (A), Izod impact strength on notched specimens (G).

Example 21

A solution of N15a catalyst in dicyclopentadiene (1: 70,000 molar ratio) containing, in addition to the above, polymer stabilizers 330 (0.2% by weight), 168 (0.5% by weight) and 123 (0.5% wt.), Modifiers ENB (3% wt.), GMA (0.5% wt.), TDI (2% wt.) And ED (2% wt.), BC-FF radical initiators (1% of the mass.) And 30 (1% of the mass.). The mold is closed and rotated at a speed of 300-800 rpm at a temperature of the heated mold of 70 ° C for 15 minutes. The product is removed from the mold and heated at 270 ° C for 30 minutes. Get the product with high-quality internal and external surfaces without defects. Tg (A), E (A), tensile strength (A), Izod impact strength on notched specimens (G).

Example 22

A solution of N16a catalyst in dicyclopentadiene (molar ratio 1: 100000) containing, in addition to the above-mentioned, polymer stabilizers 703 (0.2 wt%), THPP (0.5 wt%) and 292 (0.5% wt.), Modifiers ENB (3% wt.) And BGDMA (3% wt.), Radical initiators BTsFF (2% wt.). The mold is closed and rotated at a speed of 300-800 rpm at a temperature of the heated mold of 70 ° C for 15 minutes. The product is removed from the mold and heated at 200 ° C for 30 minutes. Get the product with high-quality internal and external surfaces without defects. Tg (B), E (A), tensile strength (A), Izod impact strength on notched specimens (G).

Example 23

A solution of catalyst N17a in dicyclopentadiene (molar ratio 1: 70,000) containing, in addition to the aforementioned, polymer stabilizers 14 (0.2% by weight), 168 (0.5% by weight), is placed in a mold for centrifugal molding at 10 ° C, 292 (0.5% wt.) And the modifier OLCPD (15% wt.).

The mold is closed and rotated at a speed of 300-800 rpm at a temperature of a heated mold of 40 ° C for 10 minutes. The product is removed from the mold and heated at 200 ° C for 30 minutes. Get the product with high-quality internal and external surfaces without defects. Tg (B), E (B), tensile strength (A), Izod impact strength on notched specimens (B).

Example 24

A solution of N18a catalyst in dicyclopentadiene (molar ratio 1: 70,000) containing, in addition to the above, polymer stabilizers 702 (0.4% by weight), 168 (0.8% by weight) and 770 (0.4% wt.), Modifiers ENB (3% wt.) And SKTN (3% wt.). The mold is closed and rotated at a speed of 300-800 rpm at a temperature of the heated mold of 80 ° C for 15 minutes. The product is removed from the mold and heated at 200 ° C for 30 minutes. Get the product with high-quality internal and external surfaces without defects. Tg (C), E (B), tensile strength (B), Izod impact strength on notched specimens (B).

Example 25

A solution of N19a catalyst in dicyclopentadiene (1: 70,000 molar ratio) containing, in addition to the above, DFA polymer stabilizers (0.2 wt%), 168 (0.5 wt%), is placed in a centrifugal molding mold at 0 ° C, 292 (0.5% wt.) And the ENB modifier (5% wt.).

The mold is closed and rotated at a speed of 300-800 rpm at a temperature of a heated mold of 40 ° C for 5 minutes. The product is removed from the mold and heated at 200 ° C for 30 minutes. Get the product with high-quality internal and external surfaces without defects. Tg (B), E (B), tensile strength (A), Izod impact strength on notched specimens (B).

Example 26

A solution of N20a catalyst in dicyclopentadiene (molar ratio 1: 70,000) containing, in addition to the aforementioned, polymer stabilizers 5057 (0.4 wt%), 168 (0.5 wt%), is placed in a centrifugal molding mold at 25 ° C, 770 (0.5% wt.) And the ENB modifier (3% wt.).

The mold is closed and rotated at a speed of 300-800 rpm at a temperature of the heated mold of 70 ° C for 15 minutes. The product is removed from the mold and heated at 200 ° C for 30 minutes. Get the product with high-quality internal and external surfaces without defects. Tg (B), E (B), tensile strength (A), Izod impact strength on notched specimens (B).

Example 27

A solution of N1b catalyst in dicyclopentadiene (molar ratio 1: 70,000) containing, in addition to the aforementioned, polymer stabilizers 354 (0.4 wt%), THPP (0.8 wt%) and modifier OLCPD (10% of the mass.).

The mold is closed and rotated at a speed of 300-800 rpm at a temperature of the heated mold of 70 ° C for 15 minutes. The product is removed from the mold and heated at 200 ° C for 15 minutes. Get the product with high-quality internal and external surfaces without defects. Tg (B), E (B), tensile strength (A), Izod impact strength on notched specimens (B).

Example 28

A solution of N2b catalyst in dicyclopentadiene (molar ratio 1: 70,000) containing, in addition to the aforementioned, polymer stabilizers 168 (1 wt%), 770 (0.5 wt%) and ENB modifier, is placed in a centrifugal molding mold at 25 ° C (3% of the mass.).

The mold is closed and rotated at a speed of 300-800 rpm at a temperature of the heated mold of 70 ° C for 15 minutes. The product is removed from the mold and heated at 200 ° C for 30 minutes. Get the product with high-quality internal and external surfaces without defects. Tg (B), E (B), tensile strength (A), Izod impact strength on notched specimens (B).

Example 29

A solution of N3b catalyst in dicyclopentadiene (molar ratio 1: 100000) containing, in addition to the aforementioned, polymer stabilizers 1010 (0.358% wt.), 168 (0.717% wt.), 123 (0.451%), is placed in a mold for centrifugal molding at 25 ° C ) mass.) and the ENB modifier (5% mass.).

The mold is closed and rotated at a speed of 300-800 rpm at a temperature of the heated mold of 100 ° C for 15 minutes. The product is removed from the mold and heated at 150 ° C for 45 minutes. Get the product with high-quality internal and external surfaces without defects. Tg (B), E (B), tensile strength (A), Izod impact strength on notched specimens (B).

Example 30

A solution of N4b catalyst in dicyclopentadiene (molar ratio 1: 70,000) containing, in addition to the aforementioned, polymer stabilizers 702 (0.365% wt.), 168 (0.730%) wt.), 770 (0.365) is placed in a mold for centrifugal molding at 25 ° C %) mass.) and the ENB modifier (5% mass.).

The mold is closed and rotated at a speed of 300-800 rpm at a temperature of the heated mold of 80 ° C for 15 minutes. The product is removed from the mold and heated at 200 ° C for 30 minutes. Get the product with high-quality internal and external surfaces without defects. Tg (B), E (B), tensile strength (A), Izod impact strength on notched specimens (B).

Example 31

A solution of N5b catalyst in dicyclopentadiene (molar ratio 1: 70,000) containing, in addition to the above-mentioned polymer stabilizers 168 (0.450%) mass.), 770 (0.450% mass.) And ENB modifier (is placed in a centrifugal molding mold at 10 ° C) 3% of the mass.).

The mold is closed and rotated at a speed of 300-800 rpm at a temperature of the heated mold of 60 ° C for 15 minutes. The product is removed from the mold and heated at 200 ° C for 30 minutes. Get the product with high-quality internal and external surfaces without defects. Tg (B), E (B), tensile strength (A), Izod impact strength on notched specimens (B).

Example 32

A solution of N1c catalyst in dicyclopentadiene (molar ratio 1: 70,000) containing, in addition to the aforementioned, polymer stabilizers 1040 (0.373% wt.), 168 (0.093% wt.), 770 (0.466%), is placed in a mold for centrifugal molding at 25 ° C mass.) and the modifier ENB (3% of the mass.).

The mold is closed and rotated at a speed of 300-800 rpm at a temperature of the heated mold of 80 ° C for 15 minutes. The product is removed from the mold and heated at 200 ° C for 30 minutes. Get the product with high-quality internal and external surfaces without defects. Tg (B), E (B), tensile strength (A), Izod impact strength on notched specimens (B).

This invention allows to obtain composite materials with high mechanical properties, thermal and chemical stability while reducing catalyst consumption and thermal control of the beginning of the polymerization process.

These effects are provided by a combination of distinctive features, special properties of the catalyst, which, at a given temperature and quantity, activates the polymerization of dicyclopentadiene and the physicochemical interaction of the listed modifying additives with it to form polydicyclopentadiene with the corresponding modifiers included in the polymer structure.

Claims (1)

A method for producing products from polydicyclopentadiene by centrifugal molding, comprising mixing dicyclopentadiene with a catalyst and modifying additives, placing the mixture in the mold, rotating the mold, polymerizing dicyclopentadiene and unloading the polymer product from the mold, characterized in that a compound of the general formula is used as a catalyst

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where the Deputy L is selected from the group:

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at the same time, during the rotation of the mold, it is heated to a temperature of 40-110 ° C and maintained at this temperature for 5-60 minutes, and after unloading from the mold, the product is heated to a temperature of 150-300 ° C and maintained at this temperature for 5- 120 min, after which the product is cooled to room temperature.