Stabilizing silane group-containing cross-linked polymers

FIELD: organic chemistry, polymers, chemical technology.

SUBSTANCE: invention relates to a composition used for cross-linking and stabilizing a polymer containing hydrolysable silane groups wherein this composition comprises sulfonic acid as a catalyst for condensation of silanols. Invention describes using the composition comprising sulfonic acid as a catalyst for condensation of silanols wherein sulfonic acid represents a compound of the formula (III): ArSO3H (III) or its precursor wherein Ar means hydrocarbyl-substituted aryl group, and compound comprises in total from 14 to 28 carbon atoms and wherein a compound used as a stabilizing agent represents neutral or acidic compound, it doesn't comprise ester groups and represents compound described by the formula (I):

wherein R means unsubstituted or substituted aliphatic or aromatic hydrocarbyl radical that can comprise heteroatoms; R' means hydrocarbyl radical; R'' means hydrocarbyl radical, and R' and/or R'' mean a bulky radical; X1, X2 and X3 are similar or different and represent hydrogen atom (H) of hydroxyl group (-OH) wherein at least X1, X2 or X3 mean -OH; n is in the range from 1 to 4. The composition is used for cross-linking and stabilizing a polymer comprising hydrolysable silane groups. Invention provides enhancing resistance of polymer against aging, absence of mercaptan or other odor and formation of cracks in material.

EFFECT: valuable properties of composition.

24 cl, 4 tbl

 

The present invention relates to compositions for crosslinking and stabilization of polymers containing hydrolyzable silane groups, which contains as a catalyst for condensation of silanols sulfonic acid. In addition, the present invention relates to stabilised polymer containing a crosslinked silane group, where stapling is carried out using as catalyst for the condensation of silanols sulfonic acid, and to a method of crosslinking and stabilization of polymers containing silane groups, when used as a catalyst for condensation of silanols sulfonic acid.

Crosslinking of polymers by using additives known, since it improves the properties of the polymer, such as mechanical strength and resistance to chemical agents and heat. Stitching can be done in the result of the condensation of silanol groups contained in the polymer, which can be obtained by hydrolysis Milanovich groups. For stitching such polymers it is necessary to use a catalyst for the condensation of silanols. Commonly used catalysts, such as ORGANOTIN compounds, such as dilaurate dibutyrate (DBTDL). In addition, it is known that the fusion process is advantageously carried out in the presence of acid condensation catalysts silanols. Unlike usually the IP is alzhemed ORGANOTIN catalysts, acid catalysts allow binding to take place rapidly even at room temperature. Such acid catalysts for the condensation of silanols are described, for example, in WO 95/17463. The contents of this document is incorporated herein by reference.

It is known that to ensure long-term stability of the polymer in the polymer to add stabilizers to prolong its service life. In particular, the polymer type stabilizers that protect it from degradation caused by thermooxidation, UV-irradiation, technological processing and penetration of metal ions such as copper ions.

It is clear that the stabilization of crosslinked polymer stabilizer must be added to the polymer before the stage of stitching. In the case of polymers containing silane groups, where the binding occurs as a result of condensation Milanovich groups, the stabilizer is usually added to the polymer together with a catalyst for condensation of silanols, preferably in the form of masterbatches.

Therefore, the stabilizer must be compatible with the catalyst for the condensation of silanols, i.e. it must not undergo degradation when introduced into contact with the catalyst, as this may lead to wypadaniu, i.e. migration of the stabilizer or its fragments on the surface of the composition or polymer. Wypadanie can occur already in masterbatches, which will lead to problems during p is rerabotka polymer, that is, in the extruder during the extrusion of the polymer containing silane groups, mixed with cross-linking composition is clogging of the feeder, conducting the flow of catalyst. Such a blockage can lead to a decrease in the amount of catalyst added to the polymer, and thus, to uncontrolled degradation of the end of the resulting polymer.

The destruction of the stabilizer can also lead to the emergence of volatile low molecular weight substances that evaporate, once in the air, and thus cause an unpleasant smell. In addition, the destruction of the stabilizer affects the resistance of polymer aging, since the polymer will be present in a smaller amount of an initial stabilizer.

In addition, the stabilizer should not inhibit or reduce the activity of the catalyst or adversely affect other properties of the polymer when introduced into contact with the catalyst.

The most commonly used stabilizers for cross-linked polymers include compounds containing ester group, such as Irganox 1010, Irganox 1035, and Irganox 1076 from Ciba-Geigy. Currently, however, found that these commonly used stabilizers when mixed with acidic condensation catalysts silanols undergo degradation, e.g. the, in masterbatches, which in result leads to sweating. This takes place even when exposed to water in the fallopian mix counteract by introducing absorbing water additive that inhibits the cleavage of ester, acid catalyzed.

In addition, it was found that the use of stabilizers containing basic groups or metal-containing soap, inhibits the activity of a catalyst for condensation of silanols-based sulfonic acid. Stabilizers containing aromatic sulfur-containing groups, i.e. groups in which the sulfur atom is directly linked to the aromatic group, will also destroy in the presence of acid condensation catalysts silanols, resulting in an unpleasant odor.

Therefore, the aim of the present invention is to provide a stabilizer for cross-linkable compositions containing as catalysts for the condensation of silanols derived sulfonic acid, cross-linked polymers containing silane groups, the stitching which was held in the presence of a catalyst based on sulfonic acid, as well as for the method for crosslinking polymers containing silane groups, in the presence of a catalyst based on sulfonic acid, where the stabilizer will not cause problems with vpotevanie, does not become a cause for the effect to an unpleasant smell, no inhibits the activity of the catalyst and allows to achieve the desired improvement of the resistance of the polymer ageing, in particular in regard to thermo-oxidative degradation.

The present invention is based on the discovery that such a stabilizer should be neutral or acidic, must contain spatial zatrudnieniu phenolic group or aliphatic sulfur-containing group, and must not contain ester groups.

Therefore, the present invention relates to compositions for crosslinking and stabilization of polymers containing hydrolyzable silane groups containing as a catalyst for condensation of silanols sulfonic acid which contains a stabilizer, which is neutral or acidic, does not contain ester groups and is a compound described by formula (I):

where

R is unsubstituted or substituted aliphatic or aromatic hydrocarbonyl radical, which may contain heteroatoms;

R' means hydrocarbonyl radical

R" means hydrocarbonyl radical

and R' and/or R" means a bulky moiety

X1, X2and X3the same or different, being H or HE, where at least X1, X2or X3mean IT,

and n is located range from 1 to 4;

or a compound described by formula (II):

R"'-(S)p-R'", (II)

where

R"' represents an aliphatic hydrocarbonyl radical, and

R is in the range from 1 to 6.

Preferably, R would be unsubstituted. However, if R is substituted, it is preferably to contain as substituents only hydroxyradicals.

R may also be present and heteroatoms, such as O-atoms forming the group of simple ether, for example, if the regulator is derived from phenolic compounds during the reaction of oligomerization, or S atoms, which, however, should not be directly linked to the aromatic group.

In addition, it is preferable that n in the formula (I) would be equal to 2 or 3.

R' preferably denotes voluminous hydrocarbonyl radical.

In addition, it is preferable that X1in the formula (I) would have meant IT.

Is preferred that R in the formula (II) would be equal to 1 or 2.

In addition, the present invention relates to stabilised polymer, which contains a crosslinked silane group, where stapling is carried out using as catalyst for the condensation of silanols sulfonic acid, which contains a stabilizer listed above for compositions of the present invention. In addition, the invention relates to a method of crosslinking and stabilization of polymers, containing the x silane group, when used as a catalyst for condensation of silanols sulfonic acid, where the method is implemented in the presence of the stabilizer indicated above for the compositions of this invention.

The composition, the polymer or the method of this invention, the stabilizer can include either individual connection as described above, or a mixture of such compounds.

In the composition, the polymer or the method of the present invention bleed either does not occur or it occurs only to a very small extent. This prevents the occurrence of problems in the processing caused by vpotevanie, for example, during extrusion of the polymer containing silane groups, mixed with cross-linking composition.

In addition, in the case of the composition, of a polymer or of the method of the present invention evaporation and getting into the air of volatile substances does not occur and, thus, the odor does not appear.

Since the stabilizer in the composition of the present invention is not subjected to degradation, it is possible to achieve desirable to improve the resistance of polymer aging.

In a preferred implementation, the composition of this invention contains a stabilizer, which is neutral or acidic, does not contain ester groups and is a compound described the " formula (I),

where R is aliphatic hydrocarbonyl radical, which may contain a hydroxy-group,

X1IT means, X2and X3mean N,

R' is a bulky aliphatic hydrocarbonyl radical

R" means aliphatic hydrocarbonyl radical

n is equal to 2;

or a compound described by formula (II), where

R"' represents an aliphatic hydrocarbonyl radical in the range from C12to C20and

p is 1 or 2.

R in the formula (I) preferably by means of CH2.

In addition, preferred that R in the formula (II) would be equal to 2.

These stabilizers also preferred for the polymer, and method of the present invention.

In another preferred implementation, the composition of this invention contains a stabilizer that is selected from the group consisting of 2,2'-methylene-bis(6-(1-methylcyclohexyl)paracresol) (corresponding to the compound described by formula (I), where R is CH2, R' is 1-methylcyclohexyl, R" means CH3, X1IT means, X2and X3mean N, and n is 2), 2,2'-methylene-bis(4-methyl-6-tert-butylphenol) (corresponding to the compound described by formula (I), where R is CH2, R' is tert-butyl, R" means CH3, X1IT means, X2and X3means N, and n is 2) and diktat is ridiculed (corresponding to the connection, described by formula (II), where R"' means octadecyl, and R is 2).

In addition, this stabilizer is also preferred in the polymer and method of the present invention.

In a particularly preferred variant of realization of the composition of the present invention as a stabilizer contains 2,2'-methylene-bis(6-(1-methylcyclohexyl)paracresol). Also especially preferred that the polymer of the present invention, and the method of the present invention contain the stabilizer.

This particularly preferred stabilizer can be used with success in a mixture of 2,2'-methylene-bis(4-methyl-6-tert-butylphenol). The composition of the present invention, it is preferable to add a link polymer in the form of masterbatches, i.e. additives such as a catalyst and a stabilizer, mixed with such a polymer, such as Homo - or copolymer of ethylene, for example, low density polyethylene or a copolymer of polyethylene-methyl-ethyl-butyl acrylate containing from 1 to 50 weight percent of acrylate, and mixtures thereof. Additional ingredients in masterbatches can be, for example, the desiccant and the inhibitor premature polymerization.

Uterine mixture contains a minor amount of a stabilizer, generally in the range from 0.01 to 4% (mass.), preferably from about 0.02 to 2% (mass.).

In the final polymer stabilizer in the General case is present in a quantity at most, equal to 2% (mass.), preferably in the range of from 0.1 to 0.5% (mass.), and most preferably from 0.15 to 0.3% (mass.).

Preferably, the catalyst condensation silanols would be a derivative of sulfonic acids described by formula (III):

ArSO3H, (III)

or its predecessor, and Ar denotes a substituted hydrocarbon aryl group, and a compound in combination contains from 14 to 28 carbon atoms.

Preferably, the group Ar was benzene or naphthalene ring, substituted hydrocarbon, and hydrocarbonyl radical or radicals contain from 8 to 20 carbon atoms in the case of benzene and from 4 to 18 atoms in the case of naphthalene.

In addition, it is preferable that hydrocarbonyl radical would alkyl substituent having from 10 to 18 carbon atoms, and still more preferably alkyl substituent would be 12 carbon atoms and selected from dodecyl and tetrapropyl. For reasons of commercial availability, it is most preferable that the aryl group has been substituted benzene group with alkyl Deputy containing 12 carbon atoms.

At the moment the most preferred compounds are described by formula (III)are dodecylbenzensulfonate acid and tetrabromobenzoate acid.

The amount of catalyst condensation silanols, preferable with respect to the composition stitched polymer is in the range from 0.0001 to 3%(mass.), more preferably from 0.001 to 2%(mass.), and most preferably 0.005 to 1% (mass.) in relation to the number of polymers containing silanol groups in the composition.

An effective amount of catalyst depends on the molecular weight of the used catalyst. Thus, fewer catalyst with a low molecular weight in comparison with the quantities of catalysts with high molecular weight.

If the catalyst is contained in masterbatches, it is preferred that it would contain the catalyst in amounts in the range from 0.02 to 5% (mass.), more preferably from about 0.05 to 2% (mass.)

In General the present invention relates to stapling polymers containing hydrolyzable silane groups. More preferably, the stitching polymer would be a polyolefin, and more preferably, they would be polyethylene.

Hydrolyzable silane groups can be introduced into the polymer by copolymerization, for example, ethylene monomers with comonomers containing silane groups, or by grafting, i.e. by chemical modification of the polymer by adding Milanovich groups, mainly during radical reactions. State of the art is well known for both methods.

The polymer containing silane groups, preferably get in the copolymerization. In the case of polyolefins, preferably polyethylene, the copolymerization is preferably carried out with an unsaturated celanova compound described by the formula:

R1SiR2qY3-q(IV)

where R1means Ethylenediamine hydrocarbonous, hydrocarbonate - or (meth)Acrylonitrile group,

R2means aliphatic saturated hydrocarbonous group,

Y, which may be identical or different, means hydrolyzable organic group, and

q is 0, 1 or 2.

Special examples of unsaturated salanova what about the connection are those in which R1meansvinyl, allyl, Isopropenyl, butenyl, cyclohexenyl or gamma - (meth)Acrylonitrile; Y represents methoxy, ethoxy, formyloxy-, acetoxy-, propionyloxy - or alkyl - or killingray; and R2if present, means methyl, ethyl, through decile or phenyl group.

Preferred unsaturated silane compound described by the formula:

CH2=CHSi(OA)3(V)

where A denotes hydrocarbonous group having 1-8 carbon atoms, preferably 1-4 carbon atoms.

The most preferred compounds are VINYLTRIMETHOXYSILANE, visibilitysensor, vinyltriethoxysilane, gamma - (meth)acrylonitrilebutadiene, gamma - (meth)aryloxypropanolamine and vinyltriethoxysilane.

The copolymerization of the olefin, such as ethylene and an unsaturated silane compounds can be carried out at any suitable conditions, resulting in copolymerization of the two monomers.

Moreover, the copolymerization can be carried out in the presence of one or more other comonomers that can be copolymerisate with two monomers. Such comonomers include (a) esters of vinylcarbazole, such as vinyl acetate and vinylbilt, (b) alpha-olefins, such as propene, 1-butene, 1-hexane, 1-octene and 4-methyl-1-penten, (C) meth)acrylates, such as methyl(meth)acrylate, ethyl(meth)acrylate and butyl(meth)acrylate, (d) carboxylic acid with the unsaturated olefinic type, such as (meth)acrylic acid, maleic acid and fumaric acid, (e) derivatives of (meth)acrylic acid such as (meth)Acrylonitrile and (meth)acrylamide, (f) simple vinyl esters, such as vinylethylene ether and finalfantasy ether, and (g) aromatic vinyl compounds such as styrene and alpha-atillery.

Among these comonomers are preferred complex vinyl esters of monobasic carboxylic acids containing 1-4 carbon atoms, such as vinyl acetate, and (meth)akilattirattu containing 1-4 carbon atoms, such as methyl(meth)acrylate.

Particularly preferred comonomers are butyl acrylate, acrylate and methyl acrylate.

Two or more such compounds with olefinic unsaturation of the type can be used in combination. The term "(meth)acrylic acid" is intended to include both acrylic acid and methacrylic acid. The content of the co monomer in the copolymer may reach 70% (mass.) from the copolymer, preferably be in the range of from about 0.5 to 35% (mass.), most preferably from about 1 to 30% (mass.).

In the case of grafted polymer can be obtained, for example, by any of the two methods on sannich US 3646155 and US 4117195 respectively.

Selectarray polymer, corresponding to this invention, in a suitable case contains 0.001 to 15% (mass.) silane derivative, preferably 0.01 to 5%(mass.), most preferably 0.1 to 2% (mass.).

The polymer composition of this invention can optionally contain various additives such as a compatible thermoplastics, other stabilizers, lubricants, fillers, colouring agents and foaming agents.

To further illustrate the present invention in this document introduced the following examples.

Examples

1.To illustrate the operation of the stabilizing compositions of this invention using a mixer periodic action Brabender volume of 250 ml at 160°C for 15 minutes was prepared and was then granulated masterbatches containing stabilizers with addition of a catalyst for condensation of silanols-based sulfonic acid (dodecylbenzenesulfonic acid) (composition 2) and without the inclusion of the catalyst (composition 1), corresponding to table 1:

Table 1
Composition 1Composition 2Composition 3
The copolymer EVA

(ethylenebutylene)
98%96,3%96,3%
17% In the (butyl acrylate)
Stabilizer2%2%2%
Sulfonic acid1,7%
Dilaurate dibutylamine1,7%
(DBTDL)

As stabilizers used compounds 4,4'-THIOBIS(2-tert-butyl-5-METHYLPHENOL) (Lowinox TBM6P), 2,2'-thiodiethanol(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (Irganox), octadecyl-3-(3',5'-di-tert-butyl-4-hydroxyphenyl)propionate (Irganox 1076), delayintolerant (Irganox PS 802) and Tris(2-tert-butyl-4-thio(2'-methyl-4'-hydroxy-5'-tert-butyl)phenyl-5-methyl)phenylphosphate (Hostanox OSP1) as comparative examples, and 1,3,5-trimethyl-2,4,6-Tris(3,5-di-tert-butyl-4-hydroxyphenyl)benzene (Irganox 1330), dictatorially (Hostanox SE10), bottled reaction product of p-cresol and Dicyclopentadiene, corresponding to the formula VI (Lowinox CPL):

and 2,2'-methylene-bis(6-(1-methylcyclohexyl)paracresol) (Lowinox WSP), corresponding to the present invention.

2.To test the resistance of the stabilizers to the effects of acid medium in accordance with the following further method tests were conducted with extraction by HPLC method.

Samples of pellets were obtained in accordance with example 1 and kept for 7 days at 23°or within 21 days at 55°C and 7 days at 23°in termosvarenny sealed plastic bags in foil of Al. Before and after this processing in glass chemical glass has introduced a 20 gram sample of the granules and 50 ml of isopropyl alcohol. The mixture was stirred using a magnetic stirrer for 5 minutes. Thus isopropyl alcohol were extracted from the surface of the granules stabilizer. 2 ml of the liquid phase was filtered into a test tube.

10 μl of the sample taken from a test tube, was injected into HPLC column (type HPLC: Waters Aliace 2690, type of column: Bond SB-C8, 4.6 mm H 125 mm, mobile phase: 1. isopropyl alcohol with 0.5 mmol/l of bromide of alkyltrimethylammonium, 2. deionized water), which can distinguish different stabilizers and their detection with a UV detector (225 nm).

The results for these tests are shown in table 2. Base, for example, the initial concentration before conducting tests on aging, obtained using the HPLC method was taken as 100%. The table describes the % remaining in the compositions of the stabilizer relative to the initial level. Therefore, the data in the table represent a direct measure of the tendency of the stabilizer to destruction.

Table 2
Composition 2Composition 3
After 1 week at 23°:
Irganox 1035 (for comparison)80%>99%
Lowinox TBM 6P (for comparison)95%>99%
Irganox 1330>99%>99%
Lowinox WSP>99%>99%
After 3 weeks at 55°and 1 week at 23°:
Irganox 1035 (for comparison)<5%>99%
Lowinox TBM 6P (for comparison)75%>99%
Irganox 1330>99%>99%
Lowinox WSP>99%>99%

The results of these tests show a decrease in concentration of the stabilizer, i.e. degradation, even at low temperatures in the composition 2 containing sulfonic acid, for the cases of the comparative compositions containing Irganox 1035 and Lowinox TBM6P. In contrast, compositions containing stabilizers corresponding to the invention, not obnarujivayutsya and thus, the reduction of the concentration of the stabilizer and even when stored for longer periods of time at elevated temperature.

3.Five weight percent of granules of compositions from table 1 and 95 weight percent of granules LDPE-silane copolymer (the content of VTMS (vinyltrimethylsilane)=1,9% (mass.), MFR2(the flow rate of the melt)=1 g/10 min) prepared dry mixes. The mixture of pellets was extrudible in a laboratory extruder over solid copper conductor 1.5 mm2obtaining an insulated cable with an insulation layer of plastic with a thickness of 0.7 mm

100 g of the cables together with 5 g of water was collected in plastic bags in foil of Al. The bags were subjected to the sealing with the receipt of the sealed envelope.

Cables are kept and sewed together in this package within one week at 23°C.

4.For crosslinked samples obtained in accordance with 1 and 3, conducted a test of the odor, while in this test group test, consisting of three independent person, opened the bag and smelled the samples. The results for this test are shown in table 3.

Table 3
5% of the composition 1+95% silane copolymer5% of the composition 2+95% silane copolymer5% ohms is osili 3+95% silane copolymer
Lowinox BM6P (for comparison)The smell is missingStrong sour

smell
The smell is missing
Irganox 1330Smell

no
Smell

no
Smell

no
Lowinox WSPSmell

no
Smell

no
Smell

no
Hostanox SE10Smell

no
Smell

no
Smell

no

The results of this test demonstrate that the sulfur-containing stabilizers with grey, directly connected with phenol (benzene) ring (Lowinox TBM6P), are subjected to degradation in the environment sulfonic acid and, thus, cause a strong sour smell.

All the stabilizers used in the composition and the polymer corresponding to the invention did not cause the appearance of the mercaptan odor or other odor in the presence of a catalyst based on sulfonic acid.

5.For testing susceptibility to thermal oxidative degradation masterbatches stabilizers prepared in accordance with the method described in 1 (composition 2), but using the amount of the stabilizers indicated in t the blitz 4. Then masterbatches in the amount indicated in table 4, were mixed with celanova copolymer was extrudible and was made in accordance with 3. The samples were kept in conditions conducive to the flow of thermo-oxidative degradation, at 150°in the furnace with cells (Elastocon, 15-fold air exchange per hour), which is specially designed to withstand the conditions of aging.

Every day survive in conditions of aging the samples in accordance with the test for resistance to bending, described in IEC 60811-1-2, tested to detect cracks in the insulation.

The results for these tests are shown in table 4.

Table 4
The day of the occurrence of cracks in the polymer composition
Irganox 1035 (FF) (for comparison)12
Lowinox CLP15
Irganox 1330 (FF)15
Irganox PS 802 (for comparison)23
Hostanox SE1026
Irganox 1076 (for comparison)31
Lowinox WSP34

1.Uterine mixture contained equal stoichiometric amounts of phenolic groups (6.8 mmol per 100 g) indicated in the data stabilizers, 2% (mass.) Hostanox OSP1 and 3% (mass.) Irganox PS 802. To the silane copolymer was added 5% (mass.) masterbatches.

2.Uterine mixture contained equal stoichiometric amount of sulfur-containing groups (4.4 mmol per 100 g) in the above stabilizers, 2% (mass.) Hostanox OSP1 and 1.75% (mass.) Irganox 1330. To the silane copolymer was added 5% (mass.) masterbatches.

3.Uterine mixture contained equal stoichiometric amounts of phenolic groups (0,mol 100g) in the above stabilizers. To the silane copolymer was added 5% (mass.) masterbatches.

This test shows that the comparison with the comparative compositions imply higher efficiency stabilizing compositions corresponding to the invention, containing Irganox 1330, Hostanox SE 10 and Lowinox WSP, in terms of improving the resistance of polymer aging.

1. The use of a composition containing as catalyst for the condensation of silanols sulfonic acid, where the sulfonic acid is a compound of formula (III)

or its predecessor, where Ar denotes a substituted hydrocarbon aryl group, and a compound in combination contains from 14 to 28 carbon atoms, and as a stabilizer compound that is neutral or acidic, does not contain ester groups and others who dstanley a connection, described by formula (I):

where

R is unsubstituted or substituted aliphatic or aromatic hydrocarbonyl radical, which may contain heteroatoms;

R' means hydrocarbonyl radical

R" means hydrocarbonyl radical, and R' and/or R" means volumetric radical

X1, X2and X3the same or different, being H or HE, where, at

least X1X2or X3mean IT,

and n is in the range from 1 to 4

for crosslinking and stabilization of polymer containing hydrolyzable silane groups.

2. The use of a composition containing as catalyst for the condensation of silanols sulfonic acid as a stabilizer compound which is a compound described by formula (II)

where

R"' represents an aliphatic hydrocarbonyl radical, and

R is in the range from 1 to 6;

for crosslinking and stabilization of polymer containing hydrolyzable silane groups.

3. The use according to claim 1, characterized in that the stabilizer is a compound described by formula (I), where R is aliphatic hydrocarbonyl radical, which may contain hydroxyprop is s, X1IT means, X2and X3mean N, R' means objekty aliphatic hydrocarbonyl radical, R means an aliphatic hydrocarbonyl radical, and n is 2.

4. The use according to claim 2, characterized in that the stabilizer is a compound described by formula (II), where R"' represents an aliphatic hydrocarbonyl radical in the range from C12to C20and p is 1 or 2.

5. The use according to claim 3, characterized in that the stabilizer is a compound described by formula (I), where R is CH2, R' is 1-methylcyclohexyl or tert-butyl, and R" means CH3.

6. The use according to claim 2, characterized in that the stabilizer is a compound described by formula (II)wherein R'" means octadecyl, and p is 2.

7. The use according to claim 3, characterized in that the stabilizer is a compound described by formula (I), where R' is 1-methylcyclohexyl or tert-butyl, and R" means CH3.

8. The use according to claim 2, characterized in that the composition further comprises a stabilizer which is neutral or acidic, does not contain ester groups and is a compound described by formula (I):

where

R is unsubstituted or substituted aliphatic or

aromatic hydrocarbonyl radical, which may contain heteroatoms;

R' means hydrocarbonyl radical

R" means hydrocarbonyl radical

and R' and/or R" means volumetric radical

X1, X2and X3the same or different, being H or HE, where at least X1, X2or X3mean IT, and n is in the range from 1 to 4.

9. Stabilised polymer containing a crosslinked silane group, where stapling is performed using as catalyst for the condensation of silanols sulfonic acid, where the sulfonic acid is a compound of formula (III)

or its predecessor, where Ar denotes a substituted hydrocarbon aryl group, and a compound in combination contains from 14 to 28 carbon atoms, characterized in that it contains a stabilizer which is neutral or acidic, does not contain ester groups and is a compound described by formula (I)

where

R is unsubstituted or substituted aliphatic or aromatic hydrocarbonyl radical, which may contain heteroatoms;

R' means hydrocarbonyl radical

R" means hydrocarbonyl radical

and R' and/or R" means volumetric radical

X1X2and X3the same or different, being H or HE, where at least X1, X2or X3mean IT,

and n is in the range from 1 to 4.

10. Stabilised polymer containing a crosslinked silane groups, where the crosslinking is carried out with the use of sulfonic acid as a catalyst for condensation of silanols, characterized in that it contains a stabilizer which is a compound described by formula (II)

or a compound described by formula (II)

where R"' represents an aliphatic hydrocarbonyl radical, and

R is in the range from 1 to 6.

11. The polymer according to claim 9, characterized in that the stabilizer is a compound described by formula (I), where R is aliphatic hydrocarbonyl radical, which may contain a hydroxy-group, X1IT means, X2and X3mean N, R' stands for the volume of aliphatic hydrocarbonyl radical, R means an aliphatic hydrocarbonyl radical, n is equal to 2.

12. The polymer of claim 10, wherein the stabilizer is a compound described by formula (II), where

R"' represents an aliphatic hydrocarbonyl radical in the range of C12to C20a

p is 1 or 2.

13. The polymer according to claim 9, characterized in that the stabilizer is a compound described by formula (I), where R is CH2, R' is 1-methylcyclohexyl or tert-butyl, and R" means CH3;

14. The polymer of claim 10, wherein the stabilizer is a compound described by formula (II), where R"' means octadecyl, and p is 2.

15. The polymer according to item 13, wherein the stabilizer is a compound described by formula (I), where R' is 1-methylcyclohexyl or tert-butyl, and R" means CH3.

16. The polymer of claim 10, characterized in that it further contains a stabilizer, which is neutral or acidic, does not contain ester groups and is a compound described by formula (I):

where

R is unsubstituted or substituted aliphatic or aromatic hydrocarbonyl radical, which may contain heteroatoms;

R' means hydrocarbonyl radical

R" means hydrocarbonyl radical

and R' and/or R" means volumetric radical

X1, X2and X3the same or different, being H or HE, where at least X1, X2or X3mean IT,

and n is in the range from 1 to 4;

17. With whom persons crosslinking and stabilization of polymers, containing silane groups, when used as a catalyst for condensation of silanols sulfonic acid, where the sulfonic acid is a compound of formula (III)

or its predecessor, where Ar denotes a substituted hydrocarbon aryl group, and a compound in combination contains from 14 to 28 carbon atoms,

characterized in that the method is carried out in the presence of the stabilizer, which is neutral or acidic, does not contain ester groups and is a compound described by formula (I):

where

R is unsubstituted or substituted aliphatic or aromatic hydrocarbonyl radical, which may contain heteroatoms;

R' means hydrocarbonyl radical

R" means hydrocarbonyl radical

and R' and/or R" means volumetric radical

X1X2and X3the same or different, being H or HE, where at least X1X2or X3mean IT,

and n is in the range from 1 to 4.

18. The method of crosslinking and stabilization of polymers containing compression group, when used as a catalyst for condensation of silanols sulfonic acid

characterized in that the persons carried out in the presence of the stabilizer, which is a compound described by formula (II):

where R"'means aliphatic hydrocarbonyl radical, and

R is in the range from 1 to 6.

19. The method according to 17, characterized in that the stabilizer is a compound described by formula (I), where R is aliphatic hydrocarbonyl radical, which may contain a hydroxy-group, X1IT means, X2and X3mean N, R' stands for the volume of aliphatic hydrocarbonyl radical, R means an aliphatic hydrocarbonyl radical, and n is 2.

20. The method according to p, characterized in that the stabilizer is a compound described by formula (II), where R"' represents an aliphatic hydrocarbonyl radical in the range of C12to C20a p equal to 1 or 2.

21. The method according to 17, characterized in that the stabilizer is a compound described by formula (I), where R is CH2, R' is 1-methylcyclohexyl or tert-butyl, and R" means CH3;

22. The method according to p, characterized in that the stabilizer is a compound described by formula (II), where R"' means octadecyl, and p is 2.

23. The method according to item 21, wherein the stabilizer is a compound described by formula (I), where R' is 1-methylcyclohex the l or tert-butyl, and R" means CH3.

24. The method according to p, characterized in that it is carried out in the presence of an additional stabilizer, which is neutral or acidic, does not contain ester groups and is a compound described by formula (I):

where R is unsubstituted or substituted aliphatic or aromatic hydrocarbonyl radical, which may contain heteroatoms;

R' means hydrocarbonyl radical

R" means hydrocarbonyl radical

and R' and/or R" means volumetric radical

X1, X2and X3the same or different, being H or HE, where at least X1, X2or X3mean IT,

and n is in the range from 1 to 4.



 

Same patents:
Sealing composition // 2288925

FIELD: sealing materials.

SUBSTANCE: sealing composition comprising fluorosiloxane rubber, mineral filler, tin diethylcaprylate, and polyethylhydrosiloxane is characterized by that above fluorosiloxane rubber is, more specifically, polydimethylmethyltrifluoropropylsiloxane rubber and composition additionally contains calcium stearate and iron oxide with following amounts of components, wt parts: rubber 100, mineral filler 90-300, tin diethylcaprylate 1-4. polyethylhydrosiloxane 4-8, calcium stearate 0.2-0.5, and iron oxide 0.5-1.

EFFECT: increased resistance to heat and fuel and reduced coefficient of linear thermal dilatation allowing composition to be used as intrajoint hermetic.

3 cl, 1 tbl, 4 ex

FIELD: chemistry of polymers.

SUBSTANCE: invention describes a polymeric composition based on synthetic low-molecular dimethylsiloxane rubber SKTN of sort A, cold hardening catalyst № 68 that comprises additionally epoxide diane resin ED-20, amine hardening agent AF-2 representing a product of interaction of phenol, formaldehyde and ethylenediamine, organic solvents chosen from mixture of xylene and ethyl alcohol in the ratio = 2:1 in the following ratio of components, mas. p. p.: epoxide diane resin ED-20 (All-Union State Standard, AUSS) 10587-84, 90-110; synthetic low-molecular dimethylsiloxane rubber of sort A, AUSS 13835-73, 90-110; hardening agent AF-2 as a product of interaction of phenol, formaldehyde and ethylenediamine, specify 2494-511-00203521, 9-11; cold hardening catalyst № 68, OST 38.03239-81, 2.5-3.5; organic solvent as a mixture of xylene, AUSS 9410, and ethyl alcohol, AUSS 18300 taken in the ratio = 2:1, 10-20.

EFFECT: valuable properties of composition.

2 tbl, 3 ex

FIELD: chemical industry, in particular composites useful in production of general mechanical rubber goods, such as cables, electrical conductors, etc.

SUBSTANCE: clamed material is obtained from rubber mixture containing as base blend of low molecular methylvinylsiloxane rubber having molecular mass of 20000-70000 and high molecular methylvinylsiloxane rubber; α,ω-dihydropolydimethylsiloxane as anti-structuring agent; aerosil, pulverized quartz; organic peroxide; waterproofing organosilicone liquid; optionally stearic acid and dehydrating agent; calcium and magnesium, or barium, or aluminum oxides, or zeolite, fire proofing agent, such as hydrated calcium, or magnesium, or aluminum hydroxides; calcium or aluminum carbonates in specific mass ratio.

EFFECT: material with decreased residual compression deformation; increased frost, water, and moisture resistance, low combustibility.

2 tbl, 1 ex

FIELD: construction industry; compositions for an elastic coating of the molds at manufacture of the production tools for construction and decorative works.

SUBSTANCE: the invention is pertaining to the field of manufacture of the elastic, in particular, the rubber-silicon technological fittings used in production by small series of geometrically-complex artistically-applied details, in the works at manufacture of the technical-decorative products and restoration works. The composition for manufacture of the elastic coating for molds used for manufacture of the technological fittings contains the high-molecular silicone rubber in amount of 2-35 mass %, the curing agent - up to 0.5 mass % and the organic solvent - the rest. The technical result of the invention is production of the composition ensuring the increase of the operational life of the elastic technological fittings and possibility of the multiple restoration of their form up to the operational state.

EFFECT: the invention allows to produce the composition ensuring the increase of the operational life of the elastic technological fittings and possibility of the multiple restoration of their form up to the operational state.

2 tbl

FIELD: optical materials.

SUBSTANCE: invention provides composition, whose refractory index can be varied by a simple way and which may manifest sufficiently large refractory index difference and provide stable refractory index configuration and optical material irrespective of conditions of their use and way of refractory index configuration and optical material formation. Composition, in particular, contains: (i) destructible compound, (ii) alcoholate hydrolyzate such as, for example, tetrabutoxytitanium, tetramethoxyzirconium, tetramethoxygermanium, or tetramethoxysilane, or halogen-containing compound such as tetrachlorosilane, and (iii) radiation-sensitive destructor.

EFFECT: achieved preparation of stable refractory index varying optical materials.

12 cl, 2 tbl, 4 ex

FIELD: polyorganosiloxane applications.

SUBSTANCE: compositions for treating and modifying surfaces contain siloxane polymers with functional side residues including two or more anionic groups, of which at least one being carboxyl group. Surface treated with such composition acquires hydrophobicity owing to deposited siloxane polymer with anionic functionality. The latter imparts a number of advantages to surface such as easiness of cleaning, removal of impurities, removal and prevention of spots, conditioning, and so forth. Moreover, siloxane polymer with anionic functionality acts as carrier when active agents are applied onto surface and improves retention and efficacy of active agents on treated surface.

EFFECT: enlarged assortment of surface-modification substances.

9 cl, 11 ex

FIELD: polyorganosiloxane applications.

SUBSTANCE: compositions for treating and modifying surfaces contain siloxane polymers with functional side residues including two or more anionic groups, of which at least one being carboxyl group. Surface treated with such composition acquires hydrophobicity owing to deposited siloxane polymer with anionic functionality. The latter imparts a number of advantages to surface such as easiness of cleaning, removal of impurities, removal and prevention of spots, conditioning, and so forth. Moreover, siloxane polymer with anionic functionality acts as carrier when active agents are applied onto surface and improves retention and efficacy of active agents on treated surface.

EFFECT: enlarged assortment of surface-modification substances.

9 cl, 11 ex

FIELD: synthetic rubbers.

SUBSTANCE: invention relates to composition based on fluorosiloxane rubber (100 wt parts), which composition further includes 25-35 wt parts silica filler, 5-10 wt parts polyorganosiloxane liquid, 0.5-0.2 wt parts organic peroxide, and additionally 5-10 wt parts iron oxide, said fluorosiloxane rubber being, in particular, poly(methyl-3,3,3-trifluoropropylmethylvinyl)siloxane rubber having molecular weight 900-1500 and molar portion of methylvinylsiloxane units 0.15-0.25 mol %, and said polyorganosiloxane liquid being diorganodialkoxysilane.

EFFECT: increased oil and fuel resistance of composition, which allows lifetime of technical rubber parts in immovable and restrictedly movable connections in air, fuel, and lube oil media to be considerably increased.

FIELD: polymer materials.

SUBSTANCE: composition represents biphasic silicone-hydrogel material in the form of in series arranged interpenetrating lattices consisting of cross-linked (i) polysiloxane, which is reaction product of vinyl-containing component including oligosiloxane/polysiloxane mixture and hydride-containing component, which is oligomer, and (ii) hydrophilic polymer, which is cross-linked (co)polymer of N-vinylpyrrolidone, 2-hydroxyethyl methacrylate, acrylamide, and dimethylacrylamide.

EFFECT: improved performance characteristics of polymer composition and simplified method for preparation thereof.

2 tbl, 11 ex

FIELD: aeronautical engineering and rocketry; manufacture of rocket antenna domes and radioparent ports; manufacture of articles resistant to stable heating up to 800°C.

SUBSTANCE: proposed method includes impregnation of multi-layer glass fabric with organic binder, molding and hardening of binder; after hardening of binder, it is subjected to heat treatment at temperature of 250-350°C continued for 1-2 h and followed by holding in acetone for 1-2 h and impregnation with silicon organic resin and polymerization at temperature of 250-350°C for 3-4 h. Proposed method enhances heat stability of articles made from glass-reinforced plastics working under conditions of one-sided intensive heating up to 800°C at retained strength properties and dielectric characteristics.

EFFECT: enhanced efficiency; retained high strength properties and dielectric characteristics.

1 tbl, 12 ex

The invention relates to suitable for re-dispersion in water pulverulent composition containing at least one naphthalenesulfonate General formula I, in which X and X' denote IT or NH2Y denotes SO3-M+, where M is an alkali metal; x=0,1; x'=0.1 and x+x'=1; y=0,1; y'=0.1 and y+y'=1, and at least one ethyleneamine monomer, both of the above monomer to form at least one water-insoluble film-forming polymer

The invention relates to the rubber industry

The rubber mixture // 2125067

The invention relates to the production of foamed polymeric materials

The invention relates to water-based organosilicon composition, particularly to a translucent or transparent composition with an average particle size of 1 μm on the basis of polyorganosiloxane having in a molecule at least one polar group associated with the atom through a Si-C-bond, comprising the emulsifier, stabilizer and water

The invention relates to the manufacture of polymeric materials on the basis of phenol-formaldehyde resins rezol type and can be used in the construction industry

The invention relates to the manufacture of polymeric materials on the basis of phenol-formaldehyde resins rezol type and can be used in the construction industry

The invention relates to methods of producing foamed polyvinylchloride (PVC) material, used as vibration, sound-, acoustic-, heat-shielding materials in the automotive, shipbuilding, aviation and other industries
Rubber composition // 2266930

FIELD: rubber composition for production of cup-type seals.

SUBSTANCE: claimed butadiene-nitrile rubber composition contains (mass pts): powdered fluoroplastic as antiwear additive 10-18; sulfur 2.5; altax 2.7; zinc white 7.5; diphenylguanidine 0.25; aldol-α-naphthylamine 4.0; neozone D 1.0; furnace carbon black 120; dibutilsibacinate 20; santoflex IP 1.0; stearic acid 1.0.

EFFECT: cup-type seals with increased abrasive resistance, durability and reduced friction coefficient.

3 tbl

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