Pyrimidine derivatives as hardness stabilizing agents

FIELD: organic chemistry, rubber industry.

SUBSTANCE: invention relates to a vulcanizing composition comprising rubber vulcanized with sulfur, sulfuric vulcanizing agent, accelerating agent taken among a group comprising of non-thiazolsulfenamide accelerating agents and agent providing stabilization of hardness that comprises derivative of pyrimidine of the formula (I):

wherein X represents hydrogen atom (H), radical from R1 to R4, NR3R4, OR5, SR5, SO2R6, M, (SO3)zM (wherein M represents metal ion); n and z can be similar or different and = 1, 2 or 3 depending on the corresponding valence of X and M = 1, 2 or 3; radicals from R1 to R4 are similar or different and taken among the group comprising of H, halogen atom, -OH, -NH2, alkyl, cycloalkyl, aryl, alkylaryl, alkylaryl, aralkyl and each among substitutes has optionally additional functional groups taken among the group consisting of -NH2, -OH, substituted amino-group, substituted hydroxyl, halogen atom and carbonyl-containing group; R3 and R4 in the same link in common with nitrogen atom (N) can form a heterocyclic group; R5 can mean any radical from R1 to R4 formed by carbon-base heterocyclic group comprising at least one sulfur (S) or nitrogen (N) atom or both S and N; R6 is taken among any radical from R1 to R4, -OH, -OM, -OR5, -NH2, NR3R4. The corresponding amount of accelerating agent and hardness stabilizing agent is effective in order to not inhibit vulcanization and to stabilize hardness property of indicated rubber after vulcanization. The amount of accelerating agent in indicated composition is above about 0.6 part per 100 parts of rubber when indicated rubber represents butadiene styrene rubber (SBR), and at least 0.5 part per 100 parts of rubber when indicated rubber represents the natural rubber, and the amount of the hardness stabilizing agent is at least about 0.5 part per 100 parts of rubber. Also, invention involves a method for enhancing hardness stabilization of the composition comprising rubber vulcanized with sulfur by addition of above indicated accelerating agents and pyrimidine derivative to the composition.

EFFECT: valuable properties of compounds.

28 cl, 8 tbl, 4 ex

 

The scope of the invention

The invention relates to pyridine derivative for use as stabilizers hardness of rubber compounds and to a method of improving the stabilization of the hardness of the rubber by adding a derivative of pyrimidine and related accelerators to the unvulcanized rubber composition.

Prior art

Vulcanization of the rubber compositions by heating vulkanizetas grey rubber composition with sulfur and/or sulfur donor and the vulcanization accelerator known for many years. This way you can get the vulcanizates having acceptable physical properties, including ultimate tensile strength, elasticity and fatigue strength, but such vulcanizates have a tendency, manifested in the lack of good aging properties. A typical phenomenon of aging is hardness, which is explained below.

Unvulcanized and vulcanized rubbers tend to the effects of aging. Unsaturated groups in the diene rubbers, for example the best choice rubber (SBR) or a mixture of SBR and natural rubber, butadiene rubber, or both, make it capable of sulfur vulcanization, but at the same time, they show sensitivity to oxygen, ozone and other reactive substances that cause changes, such as the solid is ity of the vulcanizate. Not affected by the aging of diene rubbers contain free double bonds, which remain sensitive to the above-mentioned reactive substances even after vulcanization. Higher temperatures make these effects even more noticeable. Furthermore, since the unreacted double bonds present in the rubber vulcanizate, there is the possibility of further interaction with sulfur that causes curing, i.e. additional stitching, vulcanizate.

The use of antioxidants will slow-induced oxygen aging vulcanizate, but will not affect the increase in hardness due to induced gray stitching.

L.H.Davis et al. in Rubber Chemistry and Technology, Vol. 60, 1987, 125-139, described the use of N-oxide, 2,2'-dithiobiurea and zinc salts of N-oxide pyridine-2-thiol as the main accelerator, taken separately or in combination with a small amount of accelerator benzothiazol-2-sulfenamide when sulfur vulcanization branch, Rubezhnoe, Ukraine, for example, of natural rubber compounds.

In U.S. patent No. 3574213 described accelerators of vulcanization of rubbers, including pyrimidinylpiperazine, especially 1-(4,6-dimethyl-2-pyrimidinyl)phthalazine, the application of which is achieved by reduction of podocarpaceae.

C.J.Rostek et al. in Rubber Chemistry and Technology, Vol. 69, 1996, 180-202, described the use of the new the x accelerators of sulfur vulcanization based mercaptopyridine, -pyrazine and-pyrimidine. This link refers to the branch, Rubezhnoe, Ukraine rubber, which is not otverzhdajutsja.

In U.S. patent No. 3839303 described inhibiting premature vulcanization of natural or synthetic diene rubbers by including vulcanizing composition of accelerators, such as thiazole accelerators, and connections, including some pyrimidinylidene, such as N-cyclohexyl-4,6-dimethyl-2-pyrimidinamine. The connection of the link is manufactured in such a way that it was effective in inhibiting premature vulcanization in vulkanizetas composition to which it is added.

Summary of the invention

In one implementation of the present invention includes vulcanizing composition comprising volcanically grey rubber, sulfur vulcanizing agent, an accelerator selected from the group consisting of nationalcultural accelerators, and the stabilizing agent of hardness, including pyrimidine derivative of the formula

where X is H, the radical R1to R4, NR3R3OR5, SR5, SO2R6, M, (SO3)zM (M represents a metal ion and n and z may be the same or different and is 1, 2 or 3, depending on whether the corresponding valency of X and M is 1, 2 or 3, adically from R 1to R4are the same or different and selected from the group consisting of substituents H, halogen, HE, NH2, alkyl, cycloalkyl, aryl, alkylaryl, aralkyl, each of such substituents optionally has an additional functional group selected from the group consisting of NH2HE, substituted amino, substituted hydroxyl, halogen and carbonyl-containing group, R3and R4in the same parts (the group) together with N may form a heterocyclic group, R5is the same as any of the radicals from R1to R4or a radical derived from a heterocyclic group-based carbon containing at least one S or N, or both S and N, R6selected from any of the radical R1to R4HE, OHM, OR5, NH2, NR3R4and the corresponding amount of the accelerator agent and the stabilizing hardness is effective to substantially inhibit cure and stabilize the properties of the specified hardness of the rubber after vulcanization, the amount of accelerator in the specified composition is greater than approximately 0, 6 parts per 100 parts of rubber (phr), when the said rubber is the best choice rubber (SBR), and at least 0.5 parts per 100 parts of rubber when the rubber is natural rubbers is kOhm, and the number of agent stabilizing the hardness is at least about 0.5 parts per 100 parts of rubber.

In the second implementation of the present invention includes a method for improving the stabilization of the hardness of rubber, which comprises adding the above-mentioned composition to the unvulcanized rubber composition and subsequent vulcanization of the rubber composition.

Other embodiment of the invention include certain derivatives of pyrimidine, accelerators, details of the relative quantities of reactants and unvulcanized rubber compositions, all of which are further described in the following discussion of each of the aspects of the present invention.

Detailed description of the invention

In accordance with the present invention it was found that by adding suitable quantities of some pyrimidine derivatives and accelerators nationalconference type to vulkanizetas rubber composition comprising natural rubber or other rubber, you can get the vulcanizates, which can be fabricated, for example, pneumatic tires having improved properties. These combinations of accelerators and pyrimidine derivatives have the effect of stabilizing the properties of hardness of the rubber vulcanizate, for example, during the life of pneumatic tires, without inhibit the tion or deceleration vulcanization, i.e. increasing the time "podocarpaceae", upon receipt of the bus. Thus, stabilization of hardness reach without slowing down the curing process, thus avoiding the loss in performance.

In this application, the abbreviation "phr" means parts per 100 parts of rubber. In the case of a mixture of rubbers based on 100 parts of total rubber.

In the method of the invention can be used either natural rubber (NR), the best choice rubber (SBR), or a mixture of NR and SBR or NR and SBR with one or more other rubbers, and it is clear that for the purposes of this invention, the term "rubber" means the elastomer containing hydrocarbon link, which is a polymer with a certain content of unsaturated chemical bonds. In a typical use of SBR, a mixture of SBR and natural rubber (NR), a mixture of SBR with polybutadiene rubber or butadiene rubber (BR), or a mixture of SBR with NR and BR. The type of rubber or mixture of rubbers will have some influence on the exact amount of the accelerator and pyrimidine derivative, suitable for achieving the stabilization of hardness without inhibition of vulcanization.

In a typical case, the number of pyrimidine derivative as an agent for stabilizing the hardness used in the method of the present invention should be at least about 0.5 parts per 100 parts of the aucuba. The preferred upper limit is approximately 10.0 parts per 100 parts of rubber, very preferably of 3.0 parts per 100 parts of rubber.

In the method of the present invention use sulfur and/or sulfur vulcanization agent. The amount of sulfur, which is mixed with rubber, is usually from 0.1 to 10 parts per 100 parts of rubber, preferably more than about 1 part per 100 parts of rubber. If you use a sulfur donor, the amount should be calculated based on the number of sulfur.

Typical examples of sulfur donors that can be used in the method of the present invention include dithiodimorpholine, caprolactamate, tetramethylthiuramdisulphide and dipentaerythrityl. The Complainant refers to W. Hofmann, Rubber Technology Handbook, Hanser Publishers, Munich 1989, especially on pages 231-233.

Particularly preferred pyrimidine derivatives for use in the compositions and method of the present invention have the following chemical structural formulas.

2-Benzothiazolyl-4,6-dimethyl-2-pyrimidinedione

N-Cyclohexyl-4,6-dimethyl-2-pyrimidinylidene

S-(4,6-Dimethyl-2-pyrimidyl)-p-colortoalpha.c

Preferably, alkyl, cycloalkyl, aryl, alcylaryl kalkilya group of the above formula I had from 2 to about 15 carbon atoms and, very preferably from 2 to about 8 carbon atoms.

Preferred radicals formed of the heterocyclic group for R5the formula I are 2-benzothiazolyl and pyrimidine.

The following preferred pyrimidine derivative of the formula I for use in the compositions and method of the present invention is 2,2'-dithiobis[4,6-dimethylpyrimidin]disulfide.

The preferred metal, which may be in the compound of formula I selected from the group consisting of Zn, Ni, Mg, and Na.

Preferred carbonyl-containing groups of formula I include carboxylic acid or its salt, ester, amide, ketone or aldehyde.

Typical agents acceleration (accelerators) vulcanization nationalconference type suitable for use in the invention include accelerators based benzothiazole, especially mercaptobenzothiazole derived tiofosfornoy acids, tirami, dithiocarbamate, diphenylguanidine (DPG), di-o-tolylguanidine, xanthate and mixtures of one or more of such accelerators. The vulcanization accelerator preferably includes mercaptobenzothiazole, very preferably 2-mercaptobenzothiazoles (MW). A particularly preferred catalyst is bis(dibenzyldithiocarbamate)disulfide.

Particularly effective vulcanizate grey rubber composition according to the present image is the shadow include composition, including the best choice rubber, 2-pyrimidinylidene and a mixture of accelerators, bis(dibenzyldithiocarbamate)disulfide and 2-mercaptobenzothiazoles, or a composition comprising natural rubber, 2-pyrimidinylidene and, as accelerator, 2-mercaptobenzothiazoles.

The inventors have discovered that for SBR amount of the accelerator should be more than approximately 0.6 part per 100 parts of rubber and natural rubber should be at least about 0.5 parts per 100 parts of rubber, with upper limits in any case preferably about 10.0 parts per 100 parts of rubber and very preferably approximately 3.0 parts per 100 parts of rubber. Natural rubber has more reactive allylic sites for cross-linking than SBR, and usually requires less accelerator for efficient crosslinking.

Can be effectively instead of direct introduction of a pyrimidine derivative of the formula I in the composition of the invention to introduce the precursors of such derivatives. Especially preferred derivatives of thiazole and 2-mercaptopyrimidine, which leads to the formation of such derivatives in situ. Derivatives for which the formation in situ is particularly useful is 2-benzothiazolyl-4,6-dimethyl-2-pyrimidinemethanol.

According to the present invention in vulcanizing grey kuchukova the composition may also include conventional additives to the rubber. Examples include reinforcing fillers such as carbon black, silica, clay, chalk, and other mineral fillers, oil for processing, shellac, paraffin, phenol antioxidants, phenylenediamine antioxidants, antiozonants, pigments, for example titanium dioxide, resins, plasticizers, factice and vulcanization activators such as stearic acid and zinc oxide. These conventional additives for rubbers can be added in amounts known to experts in the field of preparation of rubber mixtures. The Complainant refers to examples, which are described below.

Further details of these typical additives for rubber and vulcanization retarders see W.Hofmann, Rubber Technology Handbook, Hanser Publishers, Munich 1989.

Finally, in certain applications it may be desirable for the inclusion of adhesion promoters steel cord, such as cobalt salts and ditosylate, in the conventional, known quantities.

Method of sulfur vulcanization of the present invention can be performed using tools and equipment that are well known to the person skilled in the art. Suitable vulcanization procedure described in W.Hofmann, Rubber Technology Handbook, Hanser Publishers, Munich 1989.

A typical method includes obtaining masterbatches, consisting of rubber, carbon black, a vulcanization activator and oil for processing in a closed rubber mixer, t the com as a Bunbury mixer or mixer of the Werner-Pfleiderer, and then add the vulcanization system comprising sulfur and a vulcanization accelerator, and stabilizing the hardness pyrimidine derivative of the present invention to masterbatches or in the mixer at a low temperature, or double-roll mill, i.e. the productive stage of mixing. Unvulcanized rubber composition then vulcanized by heating, for example, in the mold for direct compression.

The vulcanization process according to the invention is typically carried out at a temperature of 110-200, preferably 120-190, more preferably 140-180°during the period of time up to 12, preferably up to 6, more preferably up to 1 hour.

The composition of the present invention is useful for the production of many products, including pneumatic tires, for example, for passenger cars, trucks, and industrial rubber products which includes rubber vulcanizer, obtained by the method of the invention.

The invention is illustrated by the following examples.

Example 1

This example illustrates the synthesis of two particularly preferred pyrimidine derivatives of the present invention, 2-benzothiazolyl-4,6-dimethyl-2-pyrimidinedione and S-(4,6-dimethyl-2-pyrimidyl)-p-colortoalpha.c.

Synthesis of the third particularly preferred pyrimidine derivative, N-is illogical-4,6-dimethyl-2-pyrimidinylidene, can be found in the existing literature.

For the synthesis of 2-benzothiazolyl-4,6-dimethyl-2-pyrimidinedione mixture of 4,6-dimethyl-2-mercaptopyrimidine (2.8 g), 2-(4-morpholinothio)benzothiazole (5.0 g) and triperoxonane acid (2.3 g) in tetrahydrofuran (100 ml) was stirred at room temperature for ten minutes and incubated overnight. The mixture is evaporated under reduced pressure, thus obtaining a residue, which was purified column chromatography using silica gel and a mixed solvent of ethyl acetate and hexanol obtaining 2.4 g (40%) of product, TPL 85-86°C.

For the synthesis of S-(4,6-dimethyl-2-pyrimidyl)-p-colortoalpha.c receive a mixture of N,N-DICYCLOHEXYL-4,6-dimethyl-2-pyrimidinediamine (1.6 g), p-toluensulfonate sodium (1.8 g) and triperoxonane acid (1.1 g) in ethanol (60 ml) and the mixture is stirred at room temperature for 30 minutes and filtered. The filtered solid is dried, thus obtaining 0,48 g (33%) of product, TPL 114-116°C.

Example 2

Royal mix the rubber, carbon black, stearic acid, zinc oxide, oil for processing and antioxidant receive in a closed rubber mixer. Sulfur, accelerators and stabilizers hardness mix on twin roll mill at approximately 50-70°C. Rubber compounds vulcanized direct pressing at 145°during periodaverage, equal to 1,7xt90. After cooling the vulcanized sheet rubber for 24 hour samples for testing cut and analyze.

Rheological properties were determined on a Monsanto rheometer MDR2000E, arc 0,5°C, 145°C/60 min Time podocarpaceae (ts2) and (t5) is the time to increase torque 2 dNm and 5 Mu, respectively, above the minimum torque (ML). The optimum vulcanization time (t90) is the time at 90% of maximum torque (MH). Tendis the time of the rheometer, it is set for 1 hour. Torque Delta (Delta S) is the difference between the minimum and maximum torques. Tilt rogramme between MLand MHa test of the speed of vulcanization (RH). Hysteresis is the percentage of energy loss per cycle of deformation. The relation module of the loss to storage modulus is defined as the mechanical loss, and it corresponds to the tangent Delta (tan d).

Pieces of rubber for testing were subjected to aging in an oven with circulation of hot air within 3 days (72 hours) at 100°to model solidification during use, for example, as a bus.

Characteristics stabilize the hardness was determined by calculating the so-called stabilization module (MS).

The stabilization module is the ratio of mo is Ulya when the elongation of 200% (Mod200) examinees pieces subjected and not subjected to the aging of rubber and is expressed as a percentage by multiplying this ratio by 100%. The lower the ratio d200podology aging/d200not subjected to agingthe better preservation of the module or stabilization of hardness. Mod200 was obtained from a tensile test stress-strain, which was performed according to ISO 37-1994 (type 2 dumbbells).

Uterine mixture used in the compositions were prepared as shown in table 1. Different source compositions had the compositions as shown in table 2. Rheological properties and stabilization module (criterion stabilizing the hardness of the action of a derivative of pyrimidine) are shown in table 3.

Table 1

Royal blend
parts per 100 parts of rubber
SBR137,5
N-220160,0
6PPD21,0
Stearic acid2,0
Zinc oxide3,0
Just 203,5
1Carbon black

2N-(1,3-Dimethylbutyl)-N'-phenyl-p-phenylenediamine

Table 2
Original song
no original songs 12345678
Royal blend HS203,5203,5203,5203,5203,5203,5203,5203,5
Sulfur1,81,81,81,81,81,81,81,8
DPG30,30,30,30,30,30,30,30,3
TBBS40,81,01,01,20,50,5
MBTS50,20,20,2
CDMPS61,00,50,51,01,01,01,0
MW70,50,30,50,3
3N,N'-Diphenylguanidine

4N-tert-Butyl-2-benzothiazolesulfenamide

52,2'-Dithiobis(benzothiazole)

6N-Cyclohexyl-4,6-dimethyl-2-pyrimidinylidene

72-Mercaptobenzothiazoles
Table 3
Rheological properties at 145°C/60 min, and the stabilization module (refer to table 2 for the original songs)
No. source

song
12345678
Test

podolinskiy
t5 @ 135°C (min)13,9021,60to 18.0123,0916,7121,0914,94 19,55
t35 @ 135°C (min)19,7629,0024,8331,0220,6926,0819,5725,19
Min. vasc. (mu)36,6936,0536,5536,6136,4536,5535,6635,96
The rheometer @ 145°
Rmax (dNM)13,9915,0414,8715,02of 13.7513,2114,92of 14.57
Rmin (dNm)of 2.212,182,182,23,24 2,222,232,25
Rmax-Rmin (dNM)36,6936,0536,5536,6136,4536,5535,6635,96
t2 (min)10,4415,1813,1616,1710,8613,6410,2213,04
t25 (min)11,3816,4914,3417,56are 11.6214,5311,0713,28
t90 (min)26,6628,8825,5129,5926,8532,7423,2927,40
The maximum speed1,201,80 1,701,601,601,101,901,60
(dNM/m)

Table 3, continued
These stress-strain
A. Not undergone
aging
1. Tensile strength (MPa):
Module is, 100%1,631,911,881,961,601,581,871,79
The module 200%4,555,415,335,764,57or 4.315,325,01
The module 300%9,2710,54the 10.4011,049,108,7110,279,79
The ultimate tensile strength26,7325,9426,2326,2419,5921,3620,2522,59
2. Elongation (%)
Limit631564582570512550485542
extension
C. Subject
aging
-24 hour-
1. Tensile strength (MPa)
Module, 100%2,392,472,552,532,172,092.532,35
The module 200%to 6.807,157,44the 7.436,375,867,386,87
The module 300%of 12.3313,0113,30to 13.2911,7811,0013,0712,41
The ultimate tensile strength24,9122,0723,6722,7817,0819,6819,3717,97
2. Elongation (%)ÈA;
Limit

extension
524453471465400460415400
-72 hours-
1. Tensile strength (MPa)
Module, 100%2,772,852,892,98of 2.512,533.04 from2,70
The module 200%7,818,138,208,427,157,056,697,68
The module 300%13,4814,0714,1914,3712,5012,3414,5313,32
The ultimate coloring strength is ü rupture 21,9919,8421,2221,6915,4817,2516,6817,95
2. Elongation (%)
Ultimate elongation460400421425357398350389
Module stabilization (MS)
MS24*, %149132140129139136139137
MS72*, %172150154146156164163153
*MS24 and MS72 represent MS at 24 and 72 hours of aging, respectively.

With regard to table 2, the original composition having a composition in accordance with the present invention, is an original composition No. 5. This original composition contains accelerators nationalconference type in the number, eff is active to accelerate vulcanization and sufficient so that essentially no inhibition of vulcanization, and the amount of the pyrimidine derivative of the formula I, as described above, effective to increase the stabilization of the hardness of the rubber after vulcanization, all of which are shown in table 3. The total number of such accelerators is 0.8 parts per 100 parts of rubber (from 0.3 part to DPG and 0.5 parts MW to 100 parts of rubber) and the amount of the pyrimidine derivative (CDMPS) is 1.0 part per 100 parts of rubber.

Control, shown in table 2, is the initial composition No. 1, which is a composition containing thiazolecarboxamide accelerator (TBBS) and MBTS and does not contain the stabilizer hardness.

The data in table 3 show the original composition No. 5, which does not cause significant inhibition of vulcanization (see Rmax, t2, t25 and t90) compared with the control, and also allows you to achieve high hardness stabilization (see modules stabilization MS24 and MS72). It can be the opposite to all the other original compositions when compared with the original composition No. 1, because no other source composition does not reach a significant inhibition of vulcanization and increased stabilization of hardness. The original composition, the closest to the original composition No. 5, is the source composition No. 6, because the original composition No. 6 includes a number of proizvedeniya formula I and nationalholiday accelerator, but the latter is present in a quantity effective to accelerate vulcanization and significantly inhibits the cure.

In the original composition No. 2 use a pyrimidine derivative as a stabilizer hardness, but unlike that, as required by the present invention, do not use nationalholiday accelerators. On the contrary, it uses thiazolecarboxamide (TBBS) accelerator MBTS. As shown in table 3, there is significant inhibition of vulcanization for this original composition.

Example 3

Two compounds were included in the composition to obtain the original compositions No. 1 and original compositions No. 2 and tested for this example, the compositions are summarized in table 4. Rheological properties (data vulcanization) are given in table 5 and the modules stabilization properties (stress-strain) are given in table 6. The main difference between the compositions of this example and example 1 is that in this example used a natural rubber (NR).

Table 4
Original song
no songs12
NR100,00100,0
Soot50,0050,00
ZnO5,005,00
Stearic acid2,002,00
6PPD*1,001,00
CDMPS*-1,50
MW*-1,50
CBS81,50-
Sulfur3,003,00
*Cm. notes 2, 6 and 7 for abbreviations 6PPD, CDMPS and MW, respectively.
8N-Cyclohexyl-2-benzothiazolesulfenamide.
Table 5
Rheological properties at 145°
no original songs12
Delta S, Nm2,752,68
ML, Nm0,260,26
Ts2, min 4,272,60
T90, min10,157,40
The rate of vulcanization, Nm/min0,100,11
Tan Delta, t900,0750,087
Tan Delta, 60'0,0680,075

td align="center"> 172
Table 6
Properties the stress-strain (vulcanized @ 150°C/t90)
no original songs12
A. Not subjected to aging
Tensile strength (MPa)27,30increased by 28.70
Module, 100%4,784,49
The module 200%11,9011,10
Elongation (%)407451
Century Subjected to aging (48 hours at 100°)

Tensile strength (MPa)
16,1022,80
Module, 100%8,287,03
The module 200%-16,4
Elongation (%)275
C. the stabilization Module (MS) on the basis of 100% of the module

MS (%)
173157

Based on the data it is clear that the present invention effectively with natural rubber. Original composition No. 2 having the composition of the present invention in that it contains nationalholiday accelerator (MW) in an amount effective to accelerate vulcanization and sufficient to significantly inhibit vulcanization, shown in table 5 and the amount of the pyrimidine derivative of formula I (CDMPS), effective to increase the stabilization of the hardness of the rubber after vulcanization, as shown in table 6. Original composition No. 1 is outside the present invention in that it does not contain a pyrimidine derivative of the formula I and also contains thiazolecarboxamide accelerator (CBS).

Tables 5 and 6 show the properties of the original composition No. 2, which meets the requirements of the present invention, compared with the original composition 1, i.e. does not cause inhibition of vulcanization and provides increased stabilization of hardness.

Example 4

Two compounds were included in the composition to obtain the original compositions No. 1 and original compositions No. 2 and tested for this example, the compositions are summarized in table 7. Rheological with the STS (data vulcanization) and stabilization of the module properties (stress-strain) are given in table 8. This example compares the properties of the original composition No. 2, which is a composition in accordance with the present invention and which contains bis(dibenzyldithiocarbamate)disulfide (TBzTD) as accelerator.

Table 7
Original song
no original songs12
Royal blend HS203,5203,5
Sulfur1,81,8
DPG0,30,3
TBBS0,80
MBTS0,20
TBzTD900,20
CDMPS03,0
MW00,5
9Bis(dibenzyldithiocarbamate)disulfid

Table 8
Data vulcanization at 145°
PropertiesOriginal composition No. 1Original composition No. 2
Delta S, Nm0,951,16
ML, Nm 0,160,15
Ts2, min9,17,0
T90, min25,920,3
The rate of vulcanization, ts2 t9016,713,3
Not subjected to aging
M 100, Mrand1,41,8
M 200, Mrand3,04,4
M 300, Mrandthe 5.78,2
TS, Mrand20,921,6
Elongation, %720590
Subjected to aging, 2 d/100°C
M 100, Mrand2,82,6
M 200, Mrand7,06,4
M 300, Mrand11,710,8
TS, Mrand20,120,1
Elongation, %465490
MS, % (based on 200 M)233145

PropertiesSource composition No. 1 Original composition No. 2
Not subjected to aging
Fatigue to failure, KS88128
Tear resistance, kN/m3843
Loss resistance, %1110
Subjected to aging, 2 d/100°C
Fatigue to failure, KS2935
Tear resistance, kN/m3543


Viscoelastic
Properties (vulcanization 145°C/30')
Not subjected to aging
The dynamic modulus, E', Mrand6,18
The loss modulus, E", Mrand1,631,65
Tan Deltato 0.2630,261
Subjected to aging, 2 d/100°C
The dynamic is RCM modulus of elasticity, E', Mrandof 7.697,49
The loss modulus, E", MPa1.781,77
Tan Delta0,2310.237
Properties (vulcanization 145°s/60')
Not subjected to aging
M 100, Mrand1,51,3
M 200, Mrand3,43,0
M 300, Mrand6,55,8
TS, Mrandof 21.220,5
Elongation, %670705
Subjected to aging, 2 d/100°C
M 100, Mrand2,52,1
M 200, Mrand6,14,8
M 300, Mrand10,48,4
TS, Mrand20,018,5
Elongation, %520560
MS, % (based on 200 M) 179160

Table 8 shows the properties of the original composition No. 2, which are consistent with the purposes of the present invention, compared with the original composition No. 1, i.e. no inhibition of vulcanization and has increased stabilization of hardness. It turned out that TBzTD is a very effective accelerator to achieve the above purpose, especially when mixed with CDMPS as stabilizowanego agent.

1. Vulcanicola composition comprising volcanically grey rubber, sulfur vulcanizing agent, an accelerator selected from the group consisting of nationalcultural accelerators, and the stabilizing agent of hardness, including pyrimidine derivative of the formula

where X is H, the radical R1to R4, NR3R4OR5, SR5, SO2R6, M, (SO3)zM (M represents a metal ion and n and z may be the same or different and is 1, 2 or 3 depending on whether the corresponding valency of X and M is 1, 2 or 3, radicals from R1to R4are the same or different and selected from the group consisting of substituents H, halogen, HE, NH2, alkyl, cycloalkyl, aryl, alkylaryl, aralkyl, each of such substituents optionally has additional functional GRU is dust, selected from the group consisting of NH2HE, substituted amino, substituted hydroxyl, halogen and carbonyl-containing group, R3and R4in the same parts (the group) together with N may form a heterocyclic group, R5is the same as any of the radicals from R1to R4or a radical derived from a heterocyclic group-based carbon containing at least one S or N, or both S and N, R6selected from any of the radical R1to R4HE, OHM, OR5, NH2, NR3R4and the corresponding amount of the accelerator agent and the stabilizing hardness is effective to essentially does not inhibit the cure and stabilize the properties of the specified hardness of the rubber after vulcanization, the amount of accelerator in the specified composition is greater than approximately 0.6 part per 100 parts of rubber when the rubber is the best choice rubber SBR, and at least 0.5 parts per 100 parts of rubber when the rubber is natural rubber, and the number of agent stabilizing the hardness is at least about 0.5 parts per 100 parts of rubber.

2. The composition according to claim 1, where R5represents a pyrimidine.

3. The composition according to claim 1, where R5is 2-benzothiazolyl or pyrimidine.

4. the song according to claim 1, where a compound of formula I is 2,2'-bis(4,6-dimethylpyrimidin)disulfide.

5. The composition according to claim 1, where the specified nationalholiday accelerators selected from the group consisting of accelerators on the basis of benzothiazole derivatives tiofosfornoy acids, Turnov, dithiocarbamates, xanatos and mixtures of one or more of these accelerators.

6. The composition according to claim 1, where the specified nationalholiday accelerators selected from the group consisting of mercaptobenzothiazole, diphenylguanidine (DPG) and di-o-tolylguanidine and mixtures of one or more of the following accelerators.

7. The composition according to claim 1, where the number of the specified sulfur vulcanizing agent is more than about 1 part per 100 parts of rubber in the specified composition.

8. The composition according to claim 1, where the compound of formula I has the formula

9. The composition according to claim 1, where the compound of formula I has the formula

10. The composition according to claim 1, where the compound of formula I has the formula

11. The composition according to claim 1, where the specified accelerator includes 2-mercaptobenzothiazoles.

12. The composition according to claim 1, where the amount of the compounds of the formula I is at least about 0.5 parts per 100 parts of rubber to about 10.0 parts per 10 parts of rubber.

13. The composition according to claim 1, where the amount of the compounds of the formula I is at least about 0.5 parts per 100 parts of rubber to about 3.0 parts per 100 parts of rubber.

14. The composition according to claim 1, including the best choice rubber, 2-pyrimidinylidene and a mixture of accelerators, bis(dibenzyldithiocarbamate)disulfide and 2-mercaptobenzothiazoles.

15. The composition according to claim 9, including the best choice rubber and a mixture of accelerators, bis(dibenzyldithiocarbamate)disulfide and 2-mercaptobenzothiazoles.

16. The composition according to claim 1, comprising natural rubber and accelerators 2-mercaptobenzothiazoles and 2-pyrimidinylidene.

17. The composition according to claim 9, including natural rubber and accelerator 2-mercaptobenzothiazoles.

18. The composition according to claim 1, including SBR rubber and more than about 0.6 parts per 100 parts of rubber to about 10.0 parts per 100 parts of rubber accelerator.

19. The composition according to claim 1, including the best choice SBR rubber and more than about 0.6 parts per 100 parts of rubber to about 3.0 parts per 100 parts of rubber accelerator.

20. The composition according to claim 1, comprising natural rubber and at least about 0.5 part per 100 parts of rubber to about 10.0 parts per 100 parts of rubber accelerator.

21. The composition according to claim 1, comprising natural rubber and m is Nisha least from about 0.5 parts per 100 parts of rubber to about 3.0 parts per 100 parts of rubber accelerator.

22. The composition according to claim 1, where M is selected from the group consisting of Zn, Ni, Mg, Co, and Na.

23. The composition according to claim 1, where these carbonyl-containing groups are carboxylic acid or salt, ester, amide, ketone or aldehyde carboxylic acid.

24. The composition according to claim 1, where these alkyl, cycloalkyl, aryl and kalkilya groups have from 2 to about 15 carbon atoms.

25. The composition according to claim 1, where these alkyl, cycloalkyl, aryl and kalkilya groups have from 2 to about 8 carbon atoms.

26. The composition according to claim 1, where the specified accelerator includes bis(dibenzyldithiocarbamate)disulfide.

27. The composition according to claim 1, where the specified agent stabilizing the hardness includes N-cyclohexyl-4,6-dimethyl-2-pyrimidinamine and the specified accelerator includes bis(dibenzyldithiocarbamate)disulfide.

28. The way to increase the stabilization of the hardness of the rubber by adding to the unvulcanized vulkanizmom grey rubber composition comprising a sulfur vulcanizing agent, an accelerator selected from the group consisting of nationalcultural accelerators, and the stabilizing agent of hardness, including pyrimidine derivative of the formula I

where X is N, the radical R1to R4, NR3R4OR5, SR5, SO2R6M (SO3)zM (M represents a metal ion and n and z may be the same or different and is 1, 2 or 3 depending on whether the corresponding valency of X and M is 1, 2 or 3, radicals from R1to R4are the same or different and selected from the group consisting of substituents H, halogen, HE, NH2, alkyl, cycloalkyl, aryl, alkylaryl, aralkyl, each of such substituents optionally has an additional functional group selected from the group consisting of NH2HE, substituted amino, substituted hydroxyl, halogen and carbonyl-containing group, R3and R4in the same parts (the group) together with N may form a heterocyclic group, R5is the same as any of the radicals from R1to R4or a radical derived from a heterocyclic group-based carbon containing at least one S or N, or both S and N, R6selected from any of the radical R1to R4HE, OHM, OR5, NH2, NR3R4.



 

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2 cl, 2 tbl

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7 cl, 1 tbl, 9 ex

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EFFECT: valuable properties of composition.

15 cl, 2 ex

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14 cl, 1 dwg, 4 tbl, 30 ex

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EFFECT: material with increased elongation, tensile strength, decreased water adsorption, attrition, controllable coat hardness and elasticity.

7 ex, 1 tbl

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2 cl, 9 ex

FIELD: chemical industry; production of polymeric structural materials from hermosetting compositions based on polyisocyanurates.

SUBSTANCE: the invention is pertaining to the field of chemical industry, in particular, to production of polymeric structural materials from thermosetting compositions based on polyisocyanurates. The offered composition for production of the polymeric structural materials contains 100 mass % of a low-molecular quick-tenacious polymer with the terminal hydroxyl groups, 22.5-400 mass % of aromatic diisocyanate, 0.08-20 mass % of dimethylbenzylamine, 0.8-20 mass % of epoxydiane resins, 55-30 mass % of acetone, 2.0-22.5 mass % of a high-porous polymeric filler. At that in the capacity of the indicated polymeric filler they use a flexible polyurethane foam or a synthetic felt material (sintepone - synthetic winterizer). From the indicated composition by an industrial method for a short cycle of hot pressing produce polymeric items with a gradient modulus of elasticity (in any given direction) from 3 up to 2000 MPa. At that the material saves its elastic properties at any value of the modulus in the interval of temperatures from -50 up to 120°C, and may be used in shoe industry and tire industry, instrument-making industry and radio industry.

EFFECT: the invention allows to produce polymeric items with a gradient modulus of elasticity in any given direction within 3 up to 2000 Mpa, the material saves its elastic properties at any value of the modulus at temperatures of -50 °C up to 120°C.

3 cl, 5 ex, 1 tbl

FIELD: chemical industry; production of polymeric structural materials from hermosetting compositions based on polyisocyanurates.

SUBSTANCE: the invention is pertaining to the field of chemical industry, in particular, to production of polymeric structural materials from thermosetting compositions based on polyisocyanurates. The offered composition for production of the polymeric structural materials contains 100 mass % of a low-molecular quick-tenacious polymer with the terminal hydroxyl groups, 22.5-400 mass % of aromatic diisocyanate, 0.08-20 mass % of dimethylbenzylamine, 0.8-20 mass % of epoxydiane resins, 55-30 mass % of acetone, 2.0-22.5 mass % of a high-porous polymeric filler. At that in the capacity of the indicated polymeric filler they use a flexible polyurethane foam or a synthetic felt material (sintepone - synthetic winterizer). From the indicated composition by an industrial method for a short cycle of hot pressing produce polymeric items with a gradient modulus of elasticity (in any given direction) from 3 up to 2000 MPa. At that the material saves its elastic properties at any value of the modulus in the interval of temperatures from -50 up to 120°C, and may be used in shoe industry and tire industry, instrument-making industry and radio industry.

EFFECT: the invention allows to produce polymeric items with a gradient modulus of elasticity in any given direction within 3 up to 2000 Mpa, the material saves its elastic properties at any value of the modulus at temperatures of -50 °C up to 120°C.

3 cl, 5 ex, 1 tbl

The invention relates to the rubber industry
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