Novel composition

FIELD: chemistry.

SUBSTANCE: composition includes, at least, two components a and b. Component a) contains, at least, one mono- and/or multifunctional thiol. Component b) contains, at least, one mono- and/or multifunctional -ene. The molar ratio between the thiol and -ene groups constitutes from 1:0.9 to 1:10. Also described are: element of soaked wood; method of soaking the wooden element, including soaking wood with the said composition with further hardening.

EFFECT: increased water resistance and improved mechanical properties of wood.

13 cl, 10 tbl, 10 ex

 

The technical field to which the invention relates.

The present invention relates to a composition which is a mixture containing at least two components a) and b), where component a) comprises at least one mono and/or multifunctional thiol and component b) contains at least one mono - and/or multi-Yong, to the composition, which is a set containing at least two components a) and b), where component a) comprises at least one mono and/or multifunctional thiol and component b) contains at least one mono - and/or multi-Yong, and to the element of impregnated wood, obtained by impregnation of an element from the tree composition, and by the impregnation method.

The level of technology

Chemistry of free radicals thiol-ENES known of the early works, Dating from the late 30-ies of XX century. Browse Thiol-enes: Chemistry of The Past with Promise for the Future", written by Charles E. Hoyle, Tai Yeon Lee, Todd Roper, J. Polym.Sci.Part A: Polym.Chem.: Vol.42 (2004). Thiol-ENES are applied in the following areas: a transparent protective coatings, pigmented coatings, photoinitiator materials with liquid crystal structure and adhesives.

Impregnation/tree modification is described in many applications and patents. The main objective of these applications is to protect the wood from decay and fungi by increasing its water resistance. PEFC is dnia years, special attention is paid to to replace the old ways of impregnation of new, environmentally friendly technologies. Several promising technologies based on the processing of wood furfuryl (WPT/Kebony), acetyl (Accoya/Accsys/Titanwood), phenol (Fibron, C-K composites, Permali and so on) or urea/melamine/formaldehyde resin (BASF/Belmadur).

Technology impregnation water/soaking water based largely depend on the controlled swelling of the cells of wood for energy-intensive process, including prolonged use of high temperature and pressure. Some of these technologies have shown good results regarding improved water resistance, but so far none of them was profitable. In addition, the well-known disadvantages are the limited penetration of the impregnating liquid, bleaching and some degree of swelling of the products from the impregnated wood.

Impregnation of organic oils, such as Tung and linseed oil, has historically been the preferred technology for the impregnation of wood. On curing oils properly affects the mechanism of slow oxidation by air. Penetration is limited, often resulting in insufficient water resistance.

Wood is the preferred material for furniture production. However, massive on the wooden structures have limited mechanical strength compared with such materials, as metal and various composite materials. Therefore, in those cases in which there are thin design, the developers of furniture are forced to use other materials.

In addition, the rapid deforestation of the tropical rain forest, combined with a strong climate change forces us to think about how to replace the dark tropical wood in such applications as flooring, furniture, decks of ships. In some modern technologies impregnation mentioned earlier, the resulting tree is usually darkened and/or discolored. This side effect can be used to obtain copies of some species of tropical trees by impregnation lighter/soft wood. However, this staining is difficult to control for exact copying the appearance of a tropical tree.

Therefore, an improvement of the properties of wood products in several directions. Examples are the resistance, increased hardness, dimensional stability, mechanical strength, hardness and colour. Staining in combination with high mechanical strength will be an important direction for future developments. The task consists in the replacement of rainforest wood in many applications to save its limited and endangered resources.

The nature and the attainment

The present invention is the creation of an element from the impregnated wood for various applications with improved properties and characteristics, such as resistance, hardness, dimensional stability, mechanical strength, rigidity, high value of the coefficient E and staining. This is achieved by using the composition, which is used for the impregnation of wood.

Thus, the present invention relates to a composition which is a mixture containing at least two components a) and b), where component a) comprises at least one mono and/or multifunctional thiol and component b) contains at least one mono - and/or multi-Yong, where the molar ratio between the thiol groups and the ene groups is 1:0.1 to 1.100.

In addition, the present invention relates to compositions, which is a collection of many components containing at least two components a) and b), where component a) comprises at least one mono and/or multifunctional thiol and component b) contains at least one mono - and/or multi-Yong, where the molar ratio between the thiol groups and the ene groups is 1:0.1 to 1:100, and the components a) and b) are separated from each other.

Additionally, in the present invention VK is uceni also an element of impregnated wood, obtained by impregnation of the wood with a composition composed of a mixture according to the present invention, or a mixture of the components of the composition, which is a collection of many components, according to the present invention, followed by curing of the composition or mixture.

In addition, the present invention relates to a method for impregnating wood, where the element of wood is impregnated with a composition composed of a mixture according to the present invention, or a mixture of the components of the composition, which is a collection of many components, according to the present invention.

In addition, the present invention also includes the use of a composition composed of a mixture or mixture of components of the composition, which is a collection of many components, according to the present invention.

The term "thiol" refers to a compound that contains the functional group composed of a sulfur atom and a hydrogen atom, i.e., the group-SH. This functional group is called here or Tilney group or sulfhydryl group. Thiols also called mercaptans.

The term "-ene" means a compound that contains at least one functional group having an unsaturated bond, i.e., double bond or triple bond between carbon atoms. This functionality the other group is called here-ene group.

The term "monofunctional" refers to a molecule having one functional group. In respect of thiols this means the molecule thiol having one Tilney group. The same applies to enum, i.e., the molecule has one unsaturated bond.

The term "multifunctional" means a molecule having two or more functional groups. In respect of thiols this means the molecule thiol having two or more tirinya group. The same applies to enum, i.e., the molecule has two or more unsaturated linkages.

The term "thiol-ENES" is an expression concerning solution containing compounds having tirinya group, and compounds having-ENOVIA group. This expression can sometimes be used for compositions containing two components a) and b). However, it may be applied only in the case when the components a) and b) are in the mix.

The expression "composition, which is a collection of many components" means that, for example, included in the composition at least two components, which are located separately from each other. They can be separated by storage in two separate vessels or in a vessel having a dividing wall that can be removed or broken subsequently, when the application of the composition. Separation can be used for two components is tov, which could react, when this is undesirable, for example, before their use in the impregnation process. It depends on the choice of components and the retention time.

The expression "composition composed of a mixture" is used when at least two components are in the composition in the mixture.

The element of the tree can represent any piece or part of wood, pressed or unpressed, wood hard rock, soft rock or wood of any type.

The implementation of the invention

The present invention relates to a composition which is a mixture containing at least two components a) and b), where component a) comprises at least one mono and/or multifunctional thiol and component b) contains at least one mono - and/or multi-Yong, where the molar ratio between the thiol groups and the ene groups is 1:0.1 to 1:100. Different molar ratio between the thiol and Yong allows the operator to control the curing process and to adjust the properties of the impregnated element of wood. More efficient conversion of reactive tylnej groups and anovich groups is achieved for the molar ratio of thiol and ene in the range of from 1:0.9 to 1:10. At low ratios of thiol to a greater extent acts as the initiator and the agent re the ACI circuit, at higher ratios of thiol increasingly operates as comonomer. The composition used for impregnation of wood. Very good penetration reaches through the use of ordinary autoclave for impregnation in vacuum pressure. Curing is carried out at 60 to 150°C. when using any conventional heat source, such as a heating furnace, camera/drying chamber for drying wood, high-frequency/heat press and so on, Received item in the tree will have significantly better mechanical properties. Northern rock solid wood, such as alder, beech and birch, are all after impregnation to have a hardness in the range of 8-15 on Brunel initiated the construction depending on the source the wood texture (orientation of the annual rings, knots, original hardness and so on). Tests of Flexural strength show elevated values up to 70% for the same species. For example, bending strength for birch increased from 115 MPa to 160 MPa, and the molded birch bending strength increased from 141 MPa to 239 MPa (see table 8, example 9).

In addition, the present invention relates to compositions, which is a set containing at least two components a) and b), where component a) comprises at least one mono and/or multifunctional thiol and component b) contains at least one mono - is/or multi-Yong, where the molar ratio between the thiol groups and the ene groups is 1:0.1 to 1:100, and the components a) and b) are separated from each other. As mentioned above, it is sometimes necessary to separate the components, because tirinya group and ENOVIA groups can react with each other before, when required. Some mixtures of components a) and b) react very quickly, while others are a mixture of two components a) and b) cannot react with such speed. Such a compound or composition has a longer shelf life. It is clear that the mixture of two components a) and b) in the composition, which is a set of equivalent composition in the form of a mixture containing the components (a) and (b).

As disclosed above, more efficient conversion of reactive tylnej groups and anovich groups is achieved for the molar ratio of thiol and ene in the range of 1:0.9 to 1:10. Regular and controlled polymer chain can be obtained in a narrower interval. The degree of cure can also be improved.

Further, when using the expression "composition", as it relates to compositions composed of a mixture or composition, which is a set, unless otherwise indicated.

As mentioned, the properties of wood enhanced by impregnating composition according to the present invention. Compositions with tilenum the groups and - ene groups were previously known, and they are often referred to as "thiol-s", as mentioned above. The scope of thiol-ENES was transparent protective coatings, pigmented coatings, photoinitiator materials with liquid crystal structure and adhesives. The authors of the present invention unexpectedly found that a composition according to the present invention, containing at least two components a) and b), where component a) comprises at least one mono and/or multifunctional thiol and component b) contains at least one mono - and/or multi-Yong, where the molar ratio between the thiol groups and the ene groups is 1:0.1 to 1:100, you can apply for items impregnation of wood, and it gives the element of wood with very good properties. In addition, the scope of the tree can be expanded. The molar ratio between the thiol groups and the ene groups may range from 1:0.9 to 1:10.

The composition represents a mixture containing component containing at least one mono and/or multifunctional Tilney group, and the component containing at least one mono - and/or multi-envoy group, according to the present invention, can be overiden by free-radical mechanism (see scheme 1 below) at room is the temperature.

Scheme 1. The General case of process thiol-ene polymerization.

Scheme 1. The General case of process thiol-ene of photopolymerization.

The overall rate of conversion of the thiol-ene reaction is directly related to electron density-ene, enriched with electrons-Yong is consumed more quickly than the poor electron-ENES. The major exception to this rule is that the double bond with a high degree of conjugation copolymerized with thiols very slowly. A number of the reactivity of different-ENES by the reaction with thiols is presented in scheme 2 below. The thiol-based mercaptopropionate esters copolymerized with data-Yong faster than mercaptoacetate esters, which, in turn, react faster than simple alkalemia thiols.

Scheme 2. The reactivity of various-ENES towards thiols. The norbornene > simple Vinyl ether > Propenyl > Alkene ~ Vinyl ester > N-vinylamide > Allyl simple ether ~ Illistration > Arylisocyanate > acrylate > Unsaturated esters > N-substituted maleinimide > Acrylonitrile ~ Methacrylate > styrene > Related dieny

A composition composed of a mixture according to the present invention can thus be adjusted by selecting different combinations of tio is a and-s, or using inhibitors, or free-radical initiators. If the reaction starts too quickly, it is necessary to apply the composition, which is a collection of many components, and to obtain a mixture with the impregnation of wood. In a set you can use the various components in different vessels or vessel containing at least two compartments. When the composition should be mixed, mix the contents of different vessels or the contents of the different compartments of the vessel. Partition between different departments can be destroyed, or the components can be mixed in a separate vessel. If the components don't act quickly, you can contain components in a single vessel. However, you may need to add a free-radical initiator, if the reaction needs to be run when, for example, it flows too slowly. In addition, instead of applying different vessels or premises components in different departments, you can apply the inhibitor. The reaction between the components, if necessary, can be ingibirovany.

Thiols can be selected from the group comprising esters of mercaptopropionate, esters of mercaptoacetate and mixtures thereof. These thiols are appropriate because they provide an opportunity to monitor shelf life and the process from which eridania. In addition, it is possible to find properties when it is saturated.

-ENES can be selected from the group comprising norbornene, simple vinyl ether, propenyl, alkene, vinyl ester, N-vinylamide, allyl ethers, illistration, arylisocyanate, acrylate, unsaturated esters, N-substituted maleinimide, Acrylonitrile, methacrylate, styrene, conjugate diene and mixtures thereof. Data-ENES are appropriate because they provide an opportunity to monitor shelf life and the curing process. In addition, you can also, of course, specifically to pick up properties when it is saturated.

The present invention also relates to compositions, which is a set containing at least two components a) and b), where component a) comprises at least one mono and/or multifunctional thiol selected from the group comprising esters of mercaptopropionate, esters of mercaptoacetate and mixtures thereof, and component b) contains at least one mono - and/or multi-Yong, selected from the group comprising norbornene, simple vinyl ether, propenyl, alkene, vinyl ester, N-vinylamide, allyl ethers, illistration, arylisocyanate, acrylate, unsaturated esters, N-substituted maleinimide, Acrylonitrile, methacrylate, styrene, conjugate diene and with whom thou art, the molar ratio between the thiol groups and the ene groups is 1:0.1 to 1:100; and components (a) and (b) are separated from each other.

In addition, at least one of components a) and b) may contain dyes, finely ground pigments and/or pigments. Dyes are preferred because of their small particle size and high penetrating ability, which allows control over the coloring process.

At least one of components a) and b) may contain additives selected from among the initiators, inhibitors and other additives. Initiators and inhibitors can regulate the reaction. The initiators may be activated, for example by heating (IR, convection, microwave waves), light (UV/visible) or with radiation (e, gamma or beta).

The present invention relates also to an element of impregnated wood, which can be obtained by impregnation of an element from the tree composition composed of a mixture, or a mixture of the components of the composition, which is a set, and subsequent curing of the composition or mixture. Above explained, that the mixture of the components of the composition, which is a set, as defined above, is equivalent to a composition composed of a mixture as defined above.

Thus, the present invention relates the I to an element of impregnated wood, which can be obtained by impregnation of an element from the tree composition composed of a mixture, or a mixture containing at least two components a) and b), where component a) comprises at least one mono and/or multifunctional thiol selected from the group comprising esters of mercaptopropionate, esters of mercaptoacetate and mixtures thereof, and component b) contains at least one mono - and/or multi-Yong, selected from the group comprising norbornene, simple vinyl ether, propenyl, alkene, vinyl ester, N-vinylamide, allyl ethers, illistration, arylisocyanate, acrylate, unsaturated esters, N-substituted maleinimide, Acrylonitrile, methacrylate, styrene, conjugate diene and mixtures thereof, the molar ratio between the thiol groups and the ene groups is 1:0.1 to 1:100; and curing the composition or mixture.

The composition for impregnation method can have all the properties disclosed above. Element from the impregnated wood can represent the element of pressed wood.

The element of impregnated wood has excellent properties after impregnation composition or a mixture according to the present invention. Some tests were performed nezavisimim technological Institute SWEREA IVF, Gothenburg. Tests on solid the spine were performed on several hard rock. The results are presented in table 8.

Tests show that the usual wood solids reaches a higher mechanical properties in terms of hardness, which increases by up to 600%, and Flexural strength, which increases by up to 70%. For example, the hardness of the alder increased from 2.1 to Brunel initiated the construction of up to 15.2 at Brunel initiated the construction of, and for birch hardness increased from 2.6 to Brunel initiated the construction of up to 14.9 at Brunel initiated the construction. Bending strength for birch increased from 115 MPa to 160 MPa, and for alder bending strength increased from 90 MPa to 121 MPa. The pressed samples (according to the patent Calignum EP 0729401B1) impregnated wood has reached increasing the hardness by up to 300% and increasing values of Flexural strength by up to 150%. For example, the hardness pressed for beech increased from 7.2 to Brunel initiated the construction to 11.7 by Brunel initiated the construction of, and the molded birch hardness increased from 4.5 to Brunel initiated the construction of up to 11.9 at Brunel initiated the construction.

A bending strength of the molded birch increased from 141 MPa to 239 MPa, and pressed beech bending strength increased from 175 to 202 MPa MPa. These values do not limit the present invention. Alternatively, the use of different types of wood and pressed wood in combination with different compositions according to the present invention can provide a higher value.

All the elements of wood, impregnated according to the given patent, can be processed (grinding, moulding, sawing and so on) similarly very hard natural wood. This means that the wood can be processed using any woodworking tools or mechanisms. However, since the impregnated wood is very solid, the tools must be properly sharpened and maintained in proper condition.

Impregnated wood will have improved dimensional stability and water resistance.

The element of impregnated wood may contain from about 1 to about 80 wt.% the composition or mixture, calculated on the total weight of the element from the impregnated wood. These values represent a wide range of composition, which can be absorbed by the tree. Low amount of the composition can be used only to make an already solid and has good mechanical properties, element wood nice color, superior protection against water, while the tree may already have enough good water. It is also very porous tree can absorb up to about 80 wt.% of the composition. It may be necessary to achieve the desired properties of such element from the tree. If the element of wood is porous, it must be strengthened by using the composition. It may also be necessary primitivising water, what can be achieved by using high quantities of the composition. The amount of the composition or mixture, absorbed by the element of the tree depends on the tree and from the composition. In addition, it is the method which is described below.

The impregnation method of the element of wood can also include a stage of a certain kind of pressing. The pressing may be performed before or after step impregnation. For example, the element of wood may be subjected to pressing in any direction,

There are additional ways of pressing elements of wood. Examples of items pressed wood are disclosed in EP 0729401 B1. This method is used isostatic pressing. The tree, called the pressed wood is very solid. The link to the document EP relates to a method of obtaining such items from the tree. The element of wood, impregnated with the composition according to the present invention, will be particularly hard and will have a high mechanical strength. The stage of compression may be performed before or after impregnation of the element from the tree.

The element of the tree can be selected from the group which consists of soft wood species and wood solids. Suit both varieties of wood. Examples of soft wood species are pine and spruce. Wood hard rock mo the ut to be birch, alder, aspen, beech or oak.

These elements of wood are ideal for most wood products intended for use indoors, such as flooring, stairs and furniture, for which use solid, beautiful surface with a high degree of resistance to wear and ischerpyvanii. Usually all wooden structures for use in space have the advantage of superior mechanical properties such as bending strength. Increased resistance in combination with high strength makes them good material for outdoor use, such as wood for building structures, street furniture and so on

The present invention also relates to a method for impregnating wood, where the wood is impregnated with a composition composed of a mixture according to the present invention, or a mixture of the components of the composition, which is a collection of many components, according to the present invention.

Further, the present invention relates to a method for impregnation of an element from the tree where the element of wood is impregnated with a composition which is a mixture containing at least two components a) and b), where component a) comprises at least one mono and/or multifunctional thiol selected from the group comprising esters of mercaptopropionate, the false esters mercaptoacetate and mixtures thereof, and component b) contains at least one mono - and/or multi-Yong, selected from the group comprising norbornene, simple vinyl ether, propenyl, alkene, vinyl ester, N-vinylamide, allyl ethers, illistration, arylisocyanate, acrylate, unsaturated esters, N-substituted maleinimide, Acrylonitrile, methacrylate, styrene, conjugate diene and mixtures thereof, the molar ratio between the thiol groups and the ene groups is 1:0.1 to 1:100.

In addition, the present invention relates to a method for impregnation of an element from the tree where the element of wood is impregnated with the mixture, which is a set containing at least two components a) and b), where component a) comprises at least one mono and/or multifunctional thiol selected from the group comprising esters of mercaptopropionate, esters of mercaptoacetate and mixtures thereof, and component b) contains at least one mono - and/or multi-Yong, selected from the group comprising norbornene, vinyl simple ether, propenyl, alkene, vinyl ester, N-vinylamide, allyl ethers, illistration, arylisocyanate, acrylate, ninasimone esters, N-substituted maleinimide, Acrylonitrile, methacrylate, styrene, conjugate diene and mixtures thereof, the molar ratio between the thiol is a group-ene groups is 1:0.1 to 1:100; where the components a) and b) are separated from each other in the form of a party to the release, and they are mixed with one another with formation of a mixture of components (a) and (b) in the impregnation.

Components a) and b) can be mixed immediately prior to impregnation. These methods differ in that the composition in the beginning of the second method is a composition in the form of a set in which the two components a) and b) are separated from each other. When it is necessary to impregnate the element of wood, the two components a) and b) are mixed with one another with formation of a mixture. In the first method, the composition of the two components is a mixture already in the beginning of this method. When the use of a composition in the form of a set of components usually react with each other faster and have a shorter shelf life.

Impregnation of wood is well known to specialists in this field of technology. Typically, treatment includes the steps of degassing and application of high pressure in the autoclave to achieve penetration of the impregnating liquid into the product from the tree. Then the impregnated wood is usually subjected to curing by means of heat to complete the polymerization of the impregnating fluid (inside the cellular structure of the tree). Although the method is well-known, here are a few examples of how to achieve impregnation.

The element of wood can be impregnated with the-label phase i, ii, iii, vii, viii, and, optionally, one or more stages iv, v and vi in random order:

i) loading wood into a treatment chamber,

ii) applying the composition or mixture in the camera

iii) degassing element of the tree in the camera

iv) impact on the element of wood normal pressure,

v) impact on the element of wood of high pressure,

vi) the degassing element of wood,

vii) removing an element from the tree of the camera and

viii) heating the impregnated element of wood to a temperature of at least 40°C for at least 5 minutes.

The composition or mixture may be fed into the chamber under a vacuum, to an alternative stage of the process. Then the element of the tree can be loaded into the chamber separately, prior to the application of vacuum. Other process steps are the same and can be applied in any order.

Step viii), representing sobi stage heating or curing begins the process of curing of the composition. Curing can be carried out at a temperature from room temperature up to about 180°C. However, can be applied even higher temperatures depending on the wood substrate and thiol-ene compositions. During heating and curing depends on what components a) and b) are used, and the temperature. Hotwired the tion at room temperature requires a longer curing time.

The number of compositions that can be absorbed by the element of wood, can be adjusted using the various steps of the method. A deeper vacuum can contribute to easier absorption of the composition tree, and the high pressure can propel the song into the tree. The stages can also affect the amount of a composition which is absorbed by the element of wood.

In addition, the present invention relates to the use of a composition composed of a mixture according to the present invention, as disclosed above, or a mixture of the components of the composition, which is a set, according to the present invention, as described above, for impregnation of an element from the tree.

The present invention particularly relates to the use of a composition composed of a mixture containing at least two components a) and b); or a mixture of at least two components a) and b) of the composition, representing a set, where the components a) and b) are separated from each other prior to the application; where component a) comprises at least one mono and/or multifunctional thiol selected from the group comprising esters of mercaptopropionate, esters of mercaptoacetate and mixtures thereof, and component b) contains at least one mono - and/or multi-Yong, selected from the group comprising norbornene, vinyl simple ether, propenyl, alkene, vinyl ester, N-vinylamide, allyl ethers, illistration, arylisocyanate, acrylate, unsaturated esters, N-substituted maleinimide, Acrylonitrile, methacrylate, styrene, conjugate diene and mixtures thereof, the molar ratio between the thiol groups and the ene groups is 1:0.1 to 1:100.

Here are the following, not limiting the present invention to the examples.

EXAMPLES

1. An example of the reactivity of various thiols and ENES.

1a) Were tested 10-gram samples of the compositions of the thiol MRMR and different-ENES in a molar ratio between the thiol groups and the ene groups is 1:1 and were marked with a different speed of reaction. The compositions were placed in the vessels. The temperature is first maintained at the level of RT (room temperature, 20°C) for 20 minutes, then at 78°C for 25 minutes and at the end at 100°C until completion of the reaction (curing). Sometimes it is necessary to heat to a higher temperature, because the song was already utverzhdenii (FTIR, conversion of double bonds in >90%).

The results are shown in table 1 below:

Table 1A. Different types-ENES with TMRM (trimethylolpropane-3-mercaptopropionate) at a molar ratio of 1:1
Type-sRT (min)78°C (minutes)100°C (min)The hardness of the coreFTIR(%)
TEGDMA Triethyleneglycol-acrylate2012Solid, elastic96
MRTMA Trimethylolpropane-methacrylate209Solid93
HDDMA Hexaniacinate202530Rubber91
TMRCA Trimethylolpropane-triacrylate206Solid92
HDDA Hexaniacinate206Solid, elastic97
TMPDA Trim tilaran-dellroy simple ether 202530Elastic90
HDDVE Hexaniacinate simple ether15Elastic91
The norbornene10Elasticy, viscous89
DVB Divinylbenzene202540Viscous86
THE Tung oil202560Not cured68

Using FTIR measure the conversion of double bonds in %. Hardness was measured pressure of the rod against the surface and the bending of the sample.

The above results show that the difference in reactivity depends on the type of the applied-ene (unsaturated). Increased functionality-novyh groups in the same molecule increases the rate of re the options.

1b) Were tested 10-gram samples of compositions of various thiol-ene TMRCA in a molar ratio between the thiol groups and the ene groups is 1:1 and were marked with a different speed of reaction. The compositions were placed in the vessels. The temperature was maintained at 80°C. until completion of reaction (curing means >90% conversion of double bonds according to the FTIR measurements).

Table 1b. Different types of thiols with TMRCA (trimethylolpropane) in a molar ratio of 1:1
The type of thiol80°C (minutes)The hardness of the coreFTIR (%)
MRMR Trimethylolpropane-3-mercaptopropionate7Solid, has the flexibility96
REMR Pentaerythrityl-mercaptopropionate3Solid, has the flexibility94
RETMA Pentaerythrityl-mercaptoaceticbSolid, has the flexibility94

Presented in table 1b results show that h is on the increase in functionality tylnej groups in the same molecule increases the reaction rate. It is also shown that mercaptopropionate thiols more reactive compared to mercaptoacetate thiols.

2. An example of the different molar ratio tylnej groups to anawim.

Received 10-gram samples of the compositions of the thiol TMRM (trimethylolpropane-3-mercaptopropionate) and-s TMRCA (trimethylolpropane) in various molar ratios to study the resulting hardness and surface properties. The curing conditions were 80°C for 6 minutes. Cm. table 2A.

Table 2A. Curing at 80°C for 6 minutes for different molar ratio between the thiol (MRMR = trimethylolpropane-3-mercaptopropionate) and Yong (TMRCA = trimethylolpropane)
ThiolENThe molar ratio between the thiol and ene groupsNotes
MRMRTMRCA1:1Solid, flexible, rough surface
MRMRTMRCA1:1,3Solid, with some flexibility, stronger than 1:1, cher is howeta surface
MRMRTMRCA1:2,3Solid, with some flexibility, stronger than 1:1,3, rough surface
MRMRTMRCA1:3,6Hard, harder than 1:2,3, dry, smooth surface
MRMRTMRCA1:6,5Very hard, harder than 1:3,6, dry, smooth surface

The above results show that different molar ratio between the functionality of thiols and ENES give products with different properties. Increased functionality-ENES gives, in combination MRMR and TMRCA, increased hardness. Various combinations of thiols and ENES give different mechanical properties depending on their molar ratio and functionality. Composition REMR (pentaerythritoltetranitrate) and TEGDA (triethylenemelamine) gives a more solid film with high molar ratio for REMR (Cm. table 2b).

Table 2b. Curing at 80°C for 6 minutes for different molar ratio between the thiol (Penta is eroticamateurcouplephoto) and TEGDA (triethylenemelamine)
ThiolENThe molar ratio between the thiol and ene groupsNotes
MRMRTEGDA1:0,7Solid
MRMRTEGDA1:1Rigid with some flexibility
MRMRTEGDA1:2,3Flexible with some hardness

3. An example of the different temperature curing

The influence of different temperature curing was investigated for the composition of thiol TMRM (trimethylolpropane-3-mercaptopropionate) and-s TMRCA (trimethylolpropane). The molar ratio between the thiol and ene groups was 1:1.

Pieces of wood pressure-treated alder (50×150×4 mm) were impregnated with the composition specified above. The parameters of the technological process of impregnation were as follows:

The pressure in the vacuum: 0,2 bar for 4 minutes

Normal pressure for 6 minutes

High blood pressure: 2 bar for 10 minutes

Normal pressure: within 2 hours.

Curing was carried out in convec the ion furnace at different temperatures and for different times. Cm. tables 3A and 3b.

Table 3A
SampleThe curing conditions (°C, clock)Wt.% thiol-ene compositions pieces of woodTest pressure (1-5)Grinding test (1-5)The resistance (1-5)
120,7231524
2100, 0,534534
3100,4832544
4125, 0,1732534

You should note that the scale from 1 to 5 means that the value 1 is poor and 5 is excellent. A pressure test is a test in which some librecode squeezed from a piece of wood. Grinding test is carried out in a grinding machine with paper 120. The resistance is measured as the degree of deformity/swelling with water when placed in water on a polished surface with a size of 10×20 mm

Table 3b
SampleConditions overide-tion (°C, clock)Wt.% thiol-ene compositions pieces of woodTest pressure (1-5)Grinding test (1-5)The resistance (1-5)
140,7232524
2RUR 60,7232534
380,7233545
4110,7232555

Should education is to build attention, what scale from 1 to 5 means that the value 1 is poor and 5 is excellent. A pressure test is a test in which any liquid squeezed from a piece of wood. Grinding test is carried out in a grinding machine with paper 120. The resistance is measured as the degree of deformity/swelling with water when placed in water on a polished surface with a size of 10×20 mm

In table 3C presents an additional example. Studied composition represented thiol TMRM (trimethylolpropane-3-mercaptopropionate) and-EN TMRCA (trimethylolpropane). The molar ratio was 1:5,6 between the thiol and ene groups.

Pieces of wood pressure-treated alder (50×150×4 mm) were impregnated with the composition specified above. The parameters of the technological process of impregnation were as follows:

The pressure in the vacuum: 0.1 bar for 6 minutes

Normal pressure: within 15 minutes

Table 3C
The conditions of curing at 100°C (hours)Wt.% thiol-ene compositions pieces of woodThe appearance of the surfaceTest pressure (1-5)
31 Dry1
727Dry4
1529Dry4
3629Dry4

You should note that the scale from 1 to 5 means that the value 1 is poor and 5 is excellent. A pressure test is a test in which any liquid squeezed from a piece of wood.

The findings of these tests is such that as the curing temperature and the curing time are set. In General, when higher temperatures are achieved by increasing the reaction rate and decrease the curing time. The curing time should be optimized for each composition of thiol-ene. In tables 3A, 3b and 3C presents the effect of temperature cure.

4. An example of the various sources of heat/UV radiation for curing.

Have been investigated by various curing conditions. Compared curing under the action of heat generated in a convection oven, the heat generated by the infrared lamps and mikrovolnovaya furnace. It was also spirano influence of UV-lamps. The results are presented in table 4.

Studied composition represented thiol TMRM (trimethylolpropane-3-mercaptopropionate) and-EN TMRCA (trimethylolpropane). The molar ratio between the thiol and ene groups was 1:1,3.

Pieces of wood pressure-treated alder (50×150×4 mm) were impregnated with the composition specified above. The parameters of the technological process of impregnation were as follows:

The pressure in the vacuum: 0.1 bar for 10 minutes

Normal pressure: within 2 minutes

High blood pressure: 1.5 bar for 8 minutes

Normal pressure: within 4 hours

Table 4. Comparison of different curing conditions
SampleThe conditions of curingWt.% thiol-ene compositions pieces of woodTest pressure (1-5)
1UV (mercury lamps)331 (dry surface)
2UV+IR354
3IR30 3
4100°C, 6 hours345
5Microwaves324

You should note that the scale from 1 to 5 means that the value 1 is poor and 5 is excellent. A pressure test is a test in which any liquid squeezed from a piece of wood. When testing with UV lamps in the composition was added 1% Igracure 2100.

From the above we can conclude that UV radiation affects the superficial layers of the piece of wood, and a combination of UV and IR radiation gives a good curing in the entire piece of wood. Use only the IR radiation curing, which needs further improvement. Curing in a microwave oven and a convection oven (100°C, 6 hours) gives good conditions for curing pieces of impregnated wood.

5. An example of regulation of shelf life. Various thiols/-ENES, inhibitors and/or free-radical initiators.

In the process of impregnation shelf life of the composition is important from the point of view of time spent on different stages of the process, and from the point of view of possible applications of one and the same company who flies several times during the process.

There are several ways to control the shelf life of the composition. Some of them are as follows:

• choice of thiols and ENES (type, functionality, molar ratio)

• inhibitors

• the use of free-radical initiators (UV - and heat-sensitive initiators, reducing shelf life when activated)

• for the two components may be a variety of vessels.

Table 5 shows a few examples.

Table 5. Examples of regulatory retention thiol-ene compositions
SampleThiol/-ENThe type of controlShelf life
1RETMA/TMRCA, 1:1Functionality in comparison with sample 135 minutes
2MRMR/TMRCA, 1:1The type of thiol compared with sample 116 hours
3TMPMP/TEGDA, 1:1Type-s in comparison with sample 235 hours
4 TMPMP/TEGDA, 1:2The molar ratio compared to sample 343 PM
5MRMR/TMRCA, 1:1Hydroquinone as inhibitorShelf-life by 17% longer than the shelf life of the sample 2
6MRMR/TMRCA, 1:1Of benzoyl peroxide as free-radical initiatorShelf life at 23% shorter compared to the shelf life of the sample 2
RETMA (4 tirinya group), MRMR (3 tirinya group), TMRCA (3-ENOVIA group), TEGDA (2-ENOVIA group).

6. Example impregnation of various types of wood as a natural and pressed.

Table 6 presents the results of examples impregnation of various types of wood as a natural and pressed.

Composition for the study represented a thiol TMRM (trimethylolpropane-3-mercaptopropionate) and-ENES TMRCA (trimethylolpropane) and HDDA (hexaniacinate), the molar ratio of between-s was 8:2. The molar ratio between the thiol and ene groups was 1:2.

Pieces of wood (2000×200×4 mm) were impregnated with the composition, is shown above. The parameters of the technological process of impregnation were as follows:

The pressure in the vacuum: 0.15 bar for 6 minutes

Normal pressure: within 15 minutes

High blood pressure: 1.3 bar within 15 minutes

The pressure in the vacuum: 0.15 bar for 6 minutes

Normal pressure: within 24 hours

Curing at 100°C, 24 hours

Table 6. Examples of impregnation of various types of wood as a natural and pressed
TreeWt.% thiol-ene compositions pieces of woodTest pressure (1-5)Grinding test (1-5)
Aspen2855
Birch4355
Oak1555
Beech3755
Pressed beech135 5
Molded alder3055

You should note that the scale from 1 to 5 means that the value 1 is poor and 5 is excellent. A pressure test is a test in which any liquid squeezed from a piece of wood. Grinding test is carried out in a grinding machine with paper 120. Beech is compressed to 65%, alder up to 60% in terms of uncompressed chunks of wood.

According to the above examples and tests, it is shown that the process of impregnation thiol-Yong can be used for all types of wood. The tree can be both natural and pressed.

7. An example of a natural or pressed wood, impregnated painted thiol-ene composition having properties equal to the properties of wood rain forests, or the best. Painted thiol-ANOVA composition obtained by the use of dyes, powdered pigments and/or pigments.

Colored composition obtained using dyes, powdered pigments and/or pigments. Below are examples of natural and pressed wood, impregnated painted compositions having properties equal to the properties of the tree rainforest, or better, than the tree rain forest of the century

The composition according to the present invention, represented thiol TMRM (trimethylolpropane-3-mercaptopropionate) and-ENES TMRCA (trimethylolpropane) and TEGDA (triethylenemelamine), the molar ratio of between-s is 9:1. The molar ratio between the thiol and ene groups was 1:2. To the composition was added orange dye and black dye.

Pieces of pressed wood (2000 x 200 x 4 mm) were impregnated with the above composition. The parameters of the technological process of impregnation were as follows:

The pressure in the vacuum: 0.15 bar for 6 minutes

Normal pressure: within 15 minutes

High blood pressure: 1.3 bar within 15 minutes

The pressure in the vacuum: 0.15 bar for 6 minutes

Normal pressure: within 24 hours

Curing at 100°C, 24 hours

Table 7 presents the results for different image painted impregnated wood.

Table 7. Painted pieces of impregnated wood and pressed wood
TreeWt.% thiol-ene compositions pieces of woodSmooth staining from the surface to the middle element of the treeNote the
Alder52YesSmooth color White spots available
Beech35YesSmooth color White spots available
Birch41YesSmooth color White spots available
Pressed beech23YesSmooth color White spots available
Molded alder30YesSmooth color White spots available

8. An example of mechanical properties.

For different pieces of wood were determined mechanical properties: hardness Brunel initiated the construction (SS-EN 1534) and Flexural strength (ISO 3133). For several solid rock were tested hardness. The results are presented in table 8 below.

All values represent the average results of measurements for a given set of samples.

Table 8. The hardness Brunel initiated the construction (SS-EN 1534) and coloring strength is ü Flexural strength (ISO 3133)
Mechanical propertiesBeechAlderBirch
toaftertoaftertoafter
Hardness (Brunel initiated the construction)the 3.88,62,115,22,614,9
Bending strength (MPa)12516990121115160
Mechanical propertiesPressed beechMolded alderMolded birch
toaftertoaftertoafter
Hardness (Brunel initiated the construction) 7,211,74,1*4,511,9
Bending strength (MPa)175202128*141239
* the measurements were not carried out

The above results show that as the hardness Brunel initiated the construction and Flexural strength for different elements of impregnated wood give a great improvement in mechanical properties compared with pieces of wood.

Conventional solid wood had significantly higher mechanical properties related to the hardness, which is growing particularly strongly (by up to 600%), and bending strength, which significantly increases (by up to 70%). Pressed (according to the patent Calignum EP 0729401B1) samples impregnated wood had an average increase of hardness (by up to 300%) and from high to very high ascending values of Flexural strength (by up to 150%.)

9. An example of the different number of thiol-ene compositions, varying from 0 to 80% thiol-ene compositions in the wood.

Table 9 below presents the RA is a personal number thiol-ene compositions in the wood, ranging from 0 to 80 wt.%. Studied composition represented thiol TMRM (trimethylolpropane-3-mercaptopropionate) and-ENES TMRCA (trimethylolpropane) and HDDA (hexaniacinate), the molar ratio of between-s is 9:1. The molar ratio between the thiol and ene groups was 1:2.

The pieces of wood (2000×200×4 mm) were impregnated with the above composition. The parameters of the technological process of impregnation were as follows:

The pressure in the vacuum: 0,10 bar for 8 minutes

Normal pressure: within 15 minutes

High blood pressure: 1.2 bar for 20 minutes

The pressure in the vacuum: 0.15 bar for 6 minutes

Normal pressure: within 24 hours

Curing at 100°C, 24 hours

Table 9. Different amounts of thiol-ene compositions in the wood
Wt.% thiol-ene compositions in the woodCuring the surfaceFTIR(%)
1Yes93
11Yes96
23Yes 95
41Yes94
59Yes95
78Yes93

The data of table 9 show a good picture of curing for various amounts of thiol-ene compositions, varying from 0 to about 80 wt.% thiol-ene compositions in the wood.

10. Different molar ratio between the thiol and-Yong.

Table 10 below presents the different molar ratio between the thiol and-Yong in the elements of wood, varying from 1:0.1 to 1:100. Studied composition represented thiol TMRM (trimethylolpropane-3-mercaptopropionate) and-EN TMRCA (trimethylolpropane).

The pieces of wood (2000×200×4 mm) were impregnated with the above composition. The parameters of the technological process of impregnation were as follows:

The pressure in the vacuum: 0.15 bar for 6 minutes

Normal pressure: within 20 minutes

High blood pressure: 1,4 bar within 15 minutes

The pressure in the vacuum: 0.15 bar for 10 minutes

Normal pressure: 10 hours

Curing at 100°C, 24 hours in a convection oven

td align="right" namest="c0" nameend="c2"> Table 10. Different molar ratio between the thiol and Yong
The molar ratio between the thiol and-Yong song, pieces of woodCuring the surfaceFTIR('%)
1:0,1Yes, a little sticky91
1:1Yes95
1:5Yes97
1:20Yes94
1:50Yes91
1:100Yes88

The results show a good picture of curing for the molar ratio of the thiol-ene varying from 1:0.1 to 1:100.

1. The impregnation method of the element of wood, characterized in that the element of wood is impregnated with a composition which is a mixture containing at least two components a) and b), where component a) comprises at least one mono and/or multifunctional thiol selected from the group comprising esters of mercaptopropionate, esters of mercaptoacetate and MESI, and component b) contains at least one mono - and/or multi-Yong, selected from the group comprising norbornene, simple vinyl ether, propenyl, alkene, vinyl ester, N-vinylamide, allyl ethers, illistration, arylisocyanate, acrylate, unsaturated esters, N-substituted maleinimide, Acrylonitrile, methacrylate, styrene, conjugate diene and mixtures thereof, and the molar ratio between the thiol groups and the ene groups is 1:0.1 to 1:100, and wood impregnated with the use of the following stages i, ii, iii, vii, viii, and, optionally, one or more stages iv, v and vi, performed in random order:
i) loading wood into a treatment chamber,
ii) applying the composition or mixture in the camera
iii) degassing element of the tree in the camera
iv) impact on the element of wood normal pressure,
v) impact on the element of wood of high pressure,
vi) the degassing element of wood,
vii) removing an element from the tree of the camera and
viii) heating the impregnated element of wood to a temperature of at least 40°C for at least 5 minutes.

2. The impregnation method of the element of wood, characterized in that the element of wood is impregnated with a composition, which is a set containing at least two components a) and b), where component is (a) contains at least one mono and/or multifunctional thiol, selected from the group comprising esters of mercaptopropionate, esters of mercaptoacetate and mixtures thereof, and component b) contains at least one mono - and/or multi-Yong, selected from the group comprising norbornene, simple vinyl ether, propenyl, alkene, vinyl ester, N-vinylamide, allyl ethers, illistration, arylisocyanate, acrylate, unsaturated esters, N-substituted maleinimide, Acrylonitrile, methacrylate, styrene, conjugate diene and mixtures thereof, moreover, the molar ratio between the thiol groups and the ene groups is 1:0.1 to 1:100; where components (a) and (b) in the set are separated from each other prior to impregnation, and they are mixed with one another with formation of a mixture of components (a) and (b) in the impregnation and wood impregnated with the use of the following stages i, ii, iii, vii, viii, and, optionally, one or more stages iv, v and vi, performed in random order:
i) loading wood into a treatment chamber,
ii) applying the composition or mixture in the camera
iii) degassing element of the tree in the camera
iv) impact on the element of wood normal pressure,
v) impact on the element of wood of high pressure,
vi) the degassing element of wood,
vii) removing an element from the tree of the camera and
viii) heating the impregnated element of wood is about the temperature at least 40°C for at least 5 minutes.

3. The element of impregnated wood, characterized in that it is obtained by the method according to p. 1 or 2 by impregnation of an element from the tree composition composed of a mixture containing at least two components a) and b), where component a) comprises at least one mono and/or multifunctional thiol selected from the group comprising esters of mercaptopropionate, esters of mercaptoacetate and mixtures thereof, and component b) contains at least one mono - and/or multi-Yong, selected from the group which includes norbornene, simple vinyl ether, propenyl, alkene, vinyl ester, N-vinylamide, allyl ethers, illistration, arylisocyanate, acrylate, unsaturated esters, N-substituted maleinimide, Acrylonitrile, methacrylate, styrene, conjugate diene and mixtures thereof, and the molar ratio between the thiol groups and the ene groups is 1:0.1 to 1:100; and curing the composition or mixture.

4. The element of impregnated wood under item 3, characterized in that at least one of components a) and b) contains dyes, finely ground pigments and/or pigments.

5. The element of impregnated wood under item 3, characterized in that at least one of components a) and b) may contain additives selected from among the initiators, inhibitors and other add the K.

6. The element of impregnated wood under item 3, characterized in that it contains from about 1 to about 80 wt.% the composition or mixture, calculated on the total weight of the element from the impregnated wood.

7. The element of impregnated wood under item 3, characterized in that the tree is chosen from the group comprising wood soft rocks and wood solids.

8. The element of impregnated wood according to any one of paragraphs.3-7, characterized in that the molar ratio between the thiol groups and the ene groups is 1:0.9 to 1:10.

9. Composition for impregnation of an element from the tree, obtained by the method according to p. 1 or 2, which is a set containing at least two components a) and b), where component a) comprises at least one mono and/or multifunctional thiol selected from the group comprising esters of mercaptopropionate, esters of mercaptoacetate and mixtures thereof, and component b) contains at least one mono - and/or multi-Yong, selected from the group comprising norbornene, simple vinyl ether, propenyl, alkene, vinyl ester, N-vinylamide, allyl ethers, illistration, arylisocyanate, acrylate, unsaturated esters, N-substituted maleinimide, Acrylonitrile, methacrylate, styrene, conjugate diene and mixtures thereof, and the molar ratio between the thiol gruppie-ene groups is 1:0.1 to 1:100; and components a) and b) are separated from each other.

10. The composition according to p. 9, characterized in that at least one of components a) and b) contains dyes, finely ground pigments and/or pigments.

11. Composition under item 9 or 10, characterized in that at least one of components a) and b) contains an additive selected from initiators, inhibitors and other additives.

12. The composition according to p. 11, characterized in that the molar ratio between the thiol groups and the ene groups is 1:0.9 to 1:10.

13. The use of a composition according to PP.9-11, which is a mixture containing at least two components a) and b); or a mixture of at least two components a) and b) of the composition, representing a set, where the components a) and b) are separated from each other prior to the application; where component a) comprises at least one mono and/or multifunctional thiol selected from the group comprising esters of mercaptopropionate, esters of mercaptoacetate and mixtures thereof, and component b) contains at least one mono - and/or multi-Yong, selected from the group comprising norbornene, simple vinyl ether, propenyl, alkene, vinyl ester, N-vinylamide, allyl ethers, illistration, arylisocyanate, acrylate, unsaturated esters, N-substituted maleinimide, Acrylonitrile, methacrylate, the Tyrol, related diene and mixtures thereof, and the molar ratio between the thiol groups and the ene groups is 1:0.1 to 1:100, for impregnation of wood.



 

Same patents:

FIELD: chemistry.

SUBSTANCE: method involves bringing into contact at least one bitumen or a mixture of bitumens with at least one copolymer based on conjugated diene units and aromatic monovinyl hydrocarbon units, and at least one cross-linking agent at temperature ranging from 100°C to 230°C and stirring. The cross-linking agent being represented by the general formula HS-R-SH, where R is selected from a group consisting of a saturated or unsaturated, linear or branched, and/or an aromatic hydrocarbon group containing 8-40 carbon atoms, and a similar group but containing 2-40 carbon atoms and containing one or more heteroatoms, and not containing C=O and/or O-C-O functional groups. The invention also relates to use of said cross-linking agent to reduce emission of hydrogen sulphide when producing cross-linked bitumen-copolymer compositions and to a bitumen-copolymer composition obtained using said method.

EFFECT: obtained compositions have rheological properties which match bitumen-polymer compositions that are cross-linked with sulphur, particularly with respect to elasticity and consistency, and have reduced or even zero emission of hydrogen sulphide during cross-linking thereof.

28 cl, 5 tbl, 8 ex

FIELD: chemistry.

SUBSTANCE: disclosed rubber mixtures can be used to make rubber components used in various types of seal assemblies of machines and mechanisms and in other fields, e.g. for making seals for double-glazed windows in regions with a cold climate. The rubber mixture contains the following, pts.wt: propylene oxide rubber SKPO - 100.0; sulphur - 1.5; stearic acid - 1.0; zinc oxide - 5.0; thiuram disulphide - 1.0; dibenzothiazole disulphide (altax) - 1.5; dibutoxy ethyl adipate - 10.0; technical carbon P-803 - 60.0; phenyl-β-naphthylamine (neozone D) - 2.0; and natural bentonites - 0.5; 1.0; 3.0; 5.0; 10.0.

EFFECT: high frost resistance and low compression set of rubber seals made from the rubber mixture.

2 tbl

FIELD: chemistry.

SUBSTANCE: invention relates to production of composition material based on hydrogenated butadiene-nitrile rubber and acrylic rubber and can be used in making heat-resistant rubber plates, rubber-coated shafts and rubber sealing components. The composite material based on hydrogenated butadiene-nitrile rubber and acrylic rubber contains a metal stearate, sulphenamide TS, thiuram, D, a quaternary ammonium base, stearic acid, zinc oxide, a mixture of diaphene FP and acetonanyl R, technical carbon, N,N'-dithiodimorpholine, 2,2-dibenzthiazole disulphide, 1,2-polybutadiene, N-cyclohexyl thiophthalimide and a process additive.

EFFECT: invention improves rheologic properties, widens the range of physical-mechanical and low-temperature properties of the composite material while retaining deformation properties, as well as the possibility of processing by a moulding and non-moulding technique.

3 cl, 2 tbl

FIELD: chemistry.

SUBSTANCE: elastomeric composition contains a polymer obtained from a first composition. The first composition contains a non-cross-linked elastomeric polymer obtained from olefin, conjugated olefin and combinations thereof, and a sulphide modifier. The modifier has formula 1: AS-Y-Zm, where Y is (C12-C100) aralkyl, (C12-C100) aryl, (C12-C100) alkyl, or (C12-C100) dialkylether (alkyl-O-alkyl), and where each may be optionally substituted with (C1-C4) alkyl, (C1-C4) alkoxy, (C7-C16) aryl, (C7-C16) aralkyl, nitrile, amine, NO2, alkoxy, or thioalkyl; S is sulphur; A is hydrogen, -(S)p-R1 or -MR2R3R4; Z is -SH, -S-MR5R6R7, -S-(S)P-R8, -NR9R10, -NR11COR12, -O-CO-R13, -NCO or -COOR14; M is silicon or tin; N is nitrogen; O is oxygen; m is the number one, two or three; p is the number one, two, three, four or five; R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13 and R14 are the same or different, and are each, independently, selected from hydrogen (H), (C1-C16) alkyl, (C6-C16) aryl, (C7-C16) aralkyl or (C3-C30) tri(hydrocarbyl)silyl, and where the hydrocarbyl groups are each independently selected from (C1-C16) alkyl, (C6-C16) aryl, or (C7-C16) aralkyl.

EFFECT: use of the modified non-cross-linked elastomeric polymers disclosed by the invention improves processability, reduces heating-up during dynamic deformation, increases maximum tensile stress and modulus of elasticity of vulcanisates.

30 cl, 9 tbl

Polymer composition // 2443731

FIELD: chemistry.

SUBSTANCE: polymer composition contains the following components in pts.wt: butadiene-nitrile rubber SKN-40ASM 100, stearic acid 1.5-3.0, zinc oxide 4.0-7.5, technical carbon N550 25-35, white soot BS-120 17-30, dibutoxyethyl adipate 12-18, vulcacite SZ/EG-C 1.5-2.5, dithiodimorpholine 1.5-3.0, thiuram D 0.5-1.0, santograd PVI 0.5-1.0, asphaltene-containing mixture with 73.0-92.5 wt % asphaltene content 10-15, taurit TS-D 10-15. Taurit TS-D is an ecologically clean filler and contains silicon dioxide and carbon.

EFFECT: invention increases the service life of the polymer composition in oil and gas aggressive media.

3 tbl, 1 ex

FIELD: machine building.

SUBSTANCE: invention refers to manufacture of thermo-shrinking materials on base of stabilised and radiation-cross-linked polyethylene designed for packing food products, various items, and thermo-shrinking tubes for protection of cable connections. It can be used at manufacture of items (straps, bands) for protection of pipelines from corrosion. According to the disclosed procedure for manufacture of thermo-shrinking materials a stabiliser chosen from poly-hydro-kinone-di-sulphide, poly-resorcin-di-sulphide or poly-pyro-catechine-di-sulphide is introduced into polyethylene. For uniform distribution of the stabiliser in volume of material the latter is introduced into polyethylene in form of super-concentrate corresponding to granulated source polyethylene containing specified stabiliser with concentration of 5-8%. Produced material is radiated with γ-radiation Co60 or accelerated electrons with absorbed dose 0.05-0.1 MGr. Radiated material is subjected to thermo-drawing at temperature above temperature of non-radiated polyethylene melting in a lengthwise direction at 10-30%, and in a crosswise direction at 5-8%. Tubes are blown out in diametrical direction for not less, than at 50%.

EFFECT: thermo-shrinking materials with reduced concentration of applied stabiliser, increased strength and elasticity.

4 cl, 1 tbl, 23 ex

FIELD: chemistry.

SUBSTANCE: rubber mixture based on butadiene-nitrile rubber BNKS-18 is prepared. 2-5 pts.wt synthetic magnesium nano-spinel with particle size less than 100 nm is added to 10 pts.wt powdered ultra-high molecular weight polyethylene per 100 pts.wt rubber and then mixed for 2-3 minutes in a blade mixer. The obtained composition is added to the rubber mixture on rollers or rubber mixer. The rubber mixture also contains natural rubber, sulphur, N,N-diphenylguanidine, di-(2-benzothiazolyl)-disulphide, zinc oxide, aldol-α-naphthylamine, N-(4-hydroxyphenyl)-naphthylamine-2, N-(1,3-dimethylbutyl)-N-phenylenediamine-1,4, technical carbon P803, stearic acid, dibutyl phthalate.

EFFECT: invention enables to obtain rubber with given level of operational properties with high and stable complex of operational characteristics.

2 tbl

FIELD: chemistry.

SUBSTANCE: invention relates to use of an antioxidant to increase resistance of a polyolefin composition meant for making pipes to decomposition caused by contact with water, which contains CIO2. The antioxidant is selected from a) a group of phenols of formula I, where R is an unsubstituted or substituted aliphatic or aromatic hydrocarbon radical which can contain heteroatoms, or R is a heteroatom, R' and R" independently denote an unsubstituted or substituted hydrocarbon radical which can contain heteroatoms, or H, X1, X2 and X3 independently denote an unsubstituted or substituted hydrocarbon radical which can contain heteroatoms, or H or OH, where at least X1, X2 or X3 is OH, n assumes values from 1 to 4, and at least one of the phenol substitutes R, R' and/or R" contains at least one sulphur, phosphorus and/or nitrogen heteroatom or from b) amine compounds of formula II, where R1, R2, R3, R4, R5 and R6 independently denote a hydrogen atom or an aliphatic or aromatic hydrocarbon radical, possibly containing heteroatoms, or selected from c) sulphur-containing compounds of formula Ra-S-Rb III, where Ra and Rb independently denote an aliphatic or aromatic hydrocarbon radical, possibly containing heteroatoms.

EFFECT: antioxidant used has low susceptibility to extraction with water carried by a pipe made from such a polyolefin composition.

7 cl, 1 tbl, 2 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a rubber mixture for filling sides and tyres with a side filler made from the said rubber mixture. The said rubber mixture contains the following: 5-25 pts. wt phenol resin and/or modified phenol resin; 5.1-7.0 pts wt sulphur; 0.5-2.5 pts. wt hexamethylenetetramine; 2.0-5.0 pts. wt sulfenamide vulcanisation accelerator and/or thiazole vulcanisation accelerator; 0.1-5 pts. wt of at least one auxiliary substances for accelerating vulcanisation selected from a group consisting of citraconimide based compounds, a product of condensation of alkylphenol and sulphur chloride, an organic thiosulphate compound and a compound of the following basic formula: R'-S-S-A-S-S-R2, where A is an alkylene group containing 2-10 carbon atoms, and each of R1 and R2 is a univalent organic group containing a nitrogen atom per 100 pts. wt of diene rubber.

EFFECT: higher technological effectiveness of extrusion through optimisation of the rate of vulcanisation, improved hardness, stability of controlling an automobile and reduced specific fuel consumption.

6 cl, 6 ex, 2 tbl, 5 dwg

FIELD: insulation materials.

SUBSTANCE: invention relates to polyethylene composition for insulation of conductors and cables, which exhibits improved scorching resistance and consists of (i) polyethylene and scorching inhibitor having melting point under atmospheric pressure below 50°C and being compound depicted by general formula I, wherein R1 represents optionally phenyl-substituted С120-alkyl, С220-alkenyl, С320-alkynyl, С39-cycloalkyl, phenyl, or tolyl; R2 and R3, independently from each other, represent С120-alkyl optionally substituted by following substituents: phenyl, one or two hydroxyls, cyano group, formyl, acetyl, and -O-COR5; R5 represents С120-alkyl, С220-alkenyl, С320-alkynyl, or optionally hydroxyl-substituted С39-cycloalkyl; phenyl, 4-chlorophenyl, 2-methoxycarbonylphenyl, p-tolyl, 1,3-benzothiazol-2-yl, -(CHR6)nCOOR7, or -(CHR6)nCONR8R9, wherein n=1 or 2, R6 represents hydrogen atom or С16-alkyl; R7 С120-alkyl optionally interrupted with 1-5 O or S atoms, С57-cycloalkyl, phenyl, benzyl, or tolyl; R8 and R9 each represents hydrogen atom or С16-alkyl; R4 represents hydrogen atom or methyl; and (ii) organic peroxide. Composition may be extruded with minimum preliminary cross-linking, even at sufficient cross-linking rate. Polyethylene composition for insulation of conductors and cables with improved scorching resistance is described, which composition additionally contains an amine selected from group consisting of diphenylamine, 4-tert-butyldiphenylamine, 4-tert-octyldiphenylamine, 4,4'-di-tert-butyldiphenylamine, 2,4,4'-tris-tert-butyldiphenylamine, 4-tert-butyl-4'-tert-octyldiphenylamine, o,o', m,m'- or p,p'-di-tert-octyldiphenylamine, 2,4-di-tert-butyl-4'-tert-octyldiphenylamine, 4.4'-di-tert-octyldiphenylamine, 2,4-di-tert-octyl-4'-tert-butyldiphenylamine. This composition may be extruded with minimum preliminary cross-linking, even at sufficient cross-linking rate. Method for preparing cross-linked polyethylene composition is also disclosed. (I).

EFFECT: enhanced resistance against preliminary vulcanization at simultaneously preserved satisfactory vulcanization rate and density of cross linkages formed.

3 cl, 5 tbl

FIELD: process engineering.

SUBSTANCE: invention relates to using wax water dispersion as oil-wetting agent in producing wood-base materials. Wax dispersion contains soft wax with content of oil exceeding 20% by wt as solid phase or its component. Note here that soft wax is solid at, at least, 10°C and below, and features softening temperature below 65°C, and contains 0.5-10 % by wt of urea per wax dispersion weight. Soft wax-to-urea weight ratio varies from 100:0.3 to 100:6. Wax dispersion is brought in contact with wood chippings or fibers. Invention covers also wood-base material produced in using binders, soft wax and urea, and method of its production.

EFFECT: higher oil-wetting effect and better physical and chemical properties.

28 cl, 1 tbl, 2 dwg, 1 ex

FIELD: chemistry.

SUBSTANCE: invention relates to use of alkoxylated amines to treat wood in order to improve water-repellent properties of wood or reduce the amount of water absorbed by wood. Treatment is carried out with alkoxylated amines of formula where R1 denotes C8-20-alkyl; R2 denotes -[CH2CH(X)O]bH (a-1) or n is an integer from 1 to 4; each of a, b and c independently denotes an integer ranging from 1 to 20; each X is independently selected from a group comprising hydrogen, methyl, ethyl and phenyl. Alkoxylated amines of formula (I), particularly N,N',N' -tris(2-hydroxyethyl)-N-cocoalkyl-1,3-diaminopropane or N,N',N'-tris(2-hydroxyethyl)-N-tall alkyl-1,3-diaminopropane can be used in the composition for treating wood in amount of 0.1-90 wt %.

EFFECT: use of alkoxylated amines of formula (I) to treat wood improves water-repellent properties of wood and reduces the amount of water absorbed by wood.

10 cl, 2 tbl

FIELD: woodworking industry.

SUBSTANCE: proposed method comprises impregnating wood blanks, drying, compaction and thermal treatment. Blanks impregnation is carried out with 30-40%-water solution of carbamide containing pre-condensate of carbamide-formaldehyde oligomer in amount of 10-12% of dry carbamide weight. Note here that hardener, i.e. "ПКП-52"-carbamide-formaldehyde resin is added to impregnating solution in amount of 21-25% of carbamide-formaldehyde oligomer weight. Before thermal treatment, timber is subjected to pulse magnetic field for 30 s with amplitude of 0.5 T, pulse repetition frequency of 50 Hz and duration of triangular pulses of 30 mcs. Thermal treatment is performed at 140-160°C.

EFFECT: reduction in volumetric swelling of modified timber in water.

1 dwg, 1 tbl, 2 ex

FIELD: construction.

SUBSTANCE: method for manufacture of wood products with increased durability, stability of size and hardness of surface, which consists in the fact that non-treated wood product is impregnated with aqueous solution A) of impregnating substance selected from group that includes 1,3-bis(hydroxymethyl)-4,5-dihydroxyimidazolidinone-2, modified with C1-5-alcohol, polyol or their mixtures 1,3-bis(hydroxymethyl)-4,5-dihydroxyimidazolidinone-2, 1,3-dimethyl-4,5-dihydroxyimidazolidinone-2, dimethyl urea, bis(methoxymethyl)urea, tetramethylol-acetylene diurea, 1,3-bis(hydroxymethyl)imidazolidinone-2, methylolmethylurea or their mixtures, and B) catalyst selected from group including salts of metals or ammonia, organic or inorganic acids and their mixtures, and afterwards wood product is exposed to hardening at the temperature of 70-130°C and relative air humidity from 40 to 100%.

EFFECT: exclusion of crooking and cracking of wood product.

17 cl, 4 tbl, 4 ex

FIELD: technological processes.

SUBSTANCE: method is described for production of modified wood from fresh log of soft hardwoods with defective area, which includes impregnation of fresh cylindrical workpiece by oily antiseptic from the end under pressure and simultaneous drying-pressing, at that healthy area of wood is impregnated with oily antiseptic, and defective zone is impregnated by mixture of oily antiseptic and hardening solution that contains dissolvent - kerosene or white spirit and hardening substance selected for the group comprising the following substances: rubber production wastes - vat residues of butadiene rectification, vat residues of toluene rectification, phenolic alcohols, at that amount of hardening solution is determined according to the following formula: where M is amount of hardening solution, l, Hh is hardness of healthy zone, N/mm2, Hd is hardness of defective zone, N/mm2, C is concentration of hardening solution in defective zone, l/m3, V is volume of defective zone, m3, k is coefficient that accounts for reduction of defective zone diameter from log butt part to top part, 0.8≤k≤1.

EFFECT: higher indicators of strength and hardness in all section, higher wear resistance.

2 dwg, 2 ex

FIELD: technological processes, construction.

SUBSTANCE: method of modified wood manufacture includes drying of natural wood, plasticization, three-sided sealing, fixation of form and stabilization of dimensions, at that drying of wood up to absolutely dry condition is carried in microwave field by exposure to pulse flux with specific capacity of 0.08-0.12 W/cm2 and flux density of 1.0-1.2 W/cm2 with duration of 30 s with intervals of 60 s with final treatment by means of convective method at the temperature of 115-120°C, plasticization is carried out by means of ultrasound effect with field intensity of 25-30 W/cm2 for 80-100 s, and stabilization of dimensions is carried out by effect to wood frozen with liquid nitrogen with pulse magnet field with series from N=1500 to N=3000 of symmetrical triangular pulses with duration of 10 microsecond, amplitude B0=0.3 T and repetition frequency of 10 ms for 30-60 seconds.

EFFECT: reduction of technological process duration.

1 tbl, 1 ex

FIELD: technological processes.

SUBSTANCE: wood is modified by means of introduction of metal into its porous structure during thermal decomposition of nickel tetracarbonyl vapours inside wood, vapours of nickel tetracarbonyl are supplied into bottom part of wood stock with the speed of not more than 20 l/hr per 1 cm2 of cross section area in process of heating zone displacement downright with the speed of 12-15 cm/hr, at that for modification wood is used with humidity of not more than 2 wt %.

EFFECT: increase of wood heat conductivity and increase of resource of its operation in friction units.

2 cl, 1 dwg, 2 tbl, 7 ex

FIELD: finishing building materials, used for evening out facade surfaces of buildings and surfaces inside rooms.

SUBSTANCE: in the method for producing knifing filler, siliceous binding substance is prepared by grinding sand in ball mill with addition of alkaline admixture. Grinding of sand is performed by quartzitic pebbles at moisture level of 14-30% and temperature of 20-80°C. Then stabilization of siliceous binding substance is performed for at least 12 hours, and then siliceous binding substance is mixed with, successively, dispersion of acryl and sodium formate with following ratio of components, %: siliceous binding substance 90-94, acryl dispersion 5-8, sodium formate 1-2.

EFFECT: increased hardness of finishing materials, amplified stability thereof to effect of environment, many times decreased amount of components and improved ecological properties thereof.

1 ex

The invention relates to woodworking industry and can be used for the manufacture of shaft lining and the friction parts of the modified wood
The invention relates to chemical treatment of wood, in particular to the production of blanks for the woodworking industry from low-value wood

FIELD: process engineering.

SUBSTANCE: invention relates to woodworking, particularly, to wood dyeing and modification. Birchwood is refined by treatment by water solutions of chemicals. At first step, birchwood is impregnated with water solution of p-phenylenediamine or o- phenylenediamine. At second step, it is impregnated with solution of copper or iron sulfate combined with carbamide solution at 18-22°C.

EFFECT: better decorative properties, longer life.

3 ex

Up!